Synthesis of Biguanidines and Triazines, and Biguanidino-Aluminium Complexes As Intermediates

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(11) EP 2 231 679 B1

(12) EUROPEAN PATENT SPECIFICATION

(45) Date of publication and mention (51) Int Cl.: of the grant of the patent: C07F 5/06 (2006.01) C07D 413/04 (2006.01) 16.11.2011 Bulletin 2011/46 C07D 251/54 (2006.01) C07D 401/04 (2006.01) C07D 403/04 (2006.01) C07D 405/12 (2006.01) (2006.01) (21) Application number: 08862791.4 C07D 403/12

(22) Date of filing: 25.11.2008 (86) International application number: PCT/EP2008/009962

(87) International publication number: WO 2009/077059 (25.06.2009 Gazette 2009/26)

(54) SYNTHESIS OF BIGUANIDINES AND TRIAZINES, AND BIGUANIDINO-ALUMINIUM COMPLEXES AS INTERMEDIATES SYNTHESE VON BIGUANIDEN UND TRIAZINEN SOWIE BIGUANIN-ALUMINIUM-KOMPLEXE ALS ZWISCHENPRODUKTE SYNTHÈSE DE BIGUANIDINES ET DE TRIAZINES ET COMPLEXES DE BIGUANIDINO- ALUMINIUM COMME INTERMÉDIAIRES

(84) Designated Contracting States: (72) Inventor: FORD, Mark, James AT BE BG CH CY CZ DE DK EE ES FI FR GB GR 61389 Schmitten-Oberreifenberg (DE) HR HU IE IS IT LI LT LU LV MC MT NL NO PL PT RO SE SI SK TR (56) References cited: • DATABASECA[Online]CHEMICALABSTRACTS (30) Priority: 14.12.2007 EP 07024256 SERVICE, COLUMBUS, OHIO, US; NANDI, S. D. ET AL: "Complexes of aluminum(III) and (43) Date of publication of application: beryllium(II) with biguanide" XP002476492 29.09.2010 Bulletin 2010/39 retrieved from STN Database accession no. 81: 144912 & ZEITSCHRIFT FUER (73) Proprietor: Bayer CropScience AG NATURFORSCHUNG, TEIL B: ANORGANISCHE 42789 Monheim (DE) CHEMIE, ORGANISCHE CHEMIE, BIOCHEMIE, BIOPHYSIK, BIOLOGIE , 29(5-6), 347-8 CODEN: ZENBAX; ISSN: 0044-3174, 1974,

Note: Within nine months of the publication of the mention of the grant of the European patent in the European Patent Bulletin, any person may give notice to the European Patent Ofﬁce of opposition to that patent, in accordance with the Implementing Regulations. Notice of opposition shall not be deemed to have been ﬁled until the opposition fee has been paid. (Art. 99(1) European Patent Convention). EP 2 231 679 B1

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Description

[0001] The invention is related to the technical field of chemical processes for the preparation of heterocyclic compounds, particularly to the preparation of symmetrical triazines (s-triazines), and intermediates therefor, by ring-formation 5 of the triazine ring. The s-triazines preferably are active ingredients in the pharmaceutical, agrochemical or fine chemicals field or are intermediates thereof. [0002] It is well documented in the literature that biguanidine salts may be prepared from the reaction of cyanamide and guanidine salts or cyanoguanidine and ammonium salts at high temperatures in solution or as a melt. Even in the simplest of cases these syntheses are however often unspecific, lead to low yield and give mixtures from which the 10 product is difficult to obtain. This is primarily due to the fact that the temperature required for reaction, often very much in excess of 120˚C, is such that the biguanidine product itself reversibly decomposes to give the related guanidine and cyanamide derivatives which may themselves further take part in the reaction. In addition from the side products produced these decompositions may be extremely exothermic and as such preclude operating such a reaction on a technical scale. An example of which is that, in some cases it has been documented that under virtually identical reaction conditions 15 some amines yield unpredictably only the mono-guanidine product in low yield (J. Amer. Chem. Soc. 81, 3728, 1959, see example on page 3735 with 2-cyclohexylethylamine). Alternatively, for those cases where fusion or boiling in strong acid are not appropriate the use of copper salts (e.g. copper sulfate) is known to promote the formation of the biguanidine as the bisguanidino copper complex, albeit in only poor to modest yields (Ber. 62B, 1398 (1929) and J. Amer. Chem. Soc. 81, 3728, example on page 3735 with 2-pyrid-2-ylethylamine). Furthermore such complexes, including those, for 20 example, of nickel, cobalt and chromium, are so stable that they have been considered to be pseudoaromatic in character (J. Indian Chem. Soc. 54, 127 (1977)). As such, expectedly and unfortunately, excess H2S gas or related sulfur derivates must be used in order to liberate the biguanidine from the strongly bound biguanidino heavy metal complex such as the copper complex (Inorg. Synth. 7, 56 (1963)). Such syntheses are therefore of little technical value. [0003] Nevertheless, substituted biguanidines and the triazines derived from them have found widespread application 25 as pharmaceuticals, biocides and agrochemicals. Thus the formation and reaction of biguanidines under mild, clean, high yielding conditions is of great importance and a remaining technical challenge. [0004] Complexes of aluminum and biguanidine have been described in an article by Nandi, S.D: et al. in Zeitschrift für Naturforschung, Part B: Anorganische Chemie, Organische Chemie, Biochemie, Biophysik, Biologie (1974), 29 (5-6), pages 347-8 (this document is abstracted and indexed by CAS in Chemical Abstract Number: 81:144912 in the CA file). 30 [0005] Remarkably and surprisingly it has been found that aluminium derivatives are particularly suitable for the formation of biguanidines from amines and cyanoguanidines. The reaction is mild, proceeds cleanly, most often under conditions which would not have been expected, based on literature precedent, to lead to addition products, and is of a general nature with respect to the amine (Scheme 1).

50 [0006] The ligands X and Y of the aluminium complex shown in formula (I) may be furnished from the aluminium source, the solvent or other added components of the reaction mixture. Formula (I) shows only one of the possible resonance structures of the aluminium complex. For instance, the positive charge can also be located at the N-atom linked to the group R5 or at the N-atom of the group NR3R4. The formula (I) shall represent all resonance structures or 55 tautomers of the aluminium complex, which are in equilibrium with the one shown in formula (I) explicitly or can easily be formed therefrom in the reaction mixture. The same shall be valid also for other chemical formulae considered below. [0007] In case of R6 or R5 or both being hydrogen atoms in formula (III) the starting material is represented by formulae (IIIA) or (IIIB) or (IIIC), respectively, and the reaction can proceed to compounds of formula (I) which are not in a salt

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form; see compounds of formula (IA), (IB) or (IC) in Schemes 1 a, 1 b or 1 c, respectively (in each case only one of the resonance or tautomeric structures for the aluminium complexes is shown).

Especially, in case of formula (IC) the hydrogen atom in the complex formed can move and then forms tautomers where the saturated hydrogen atom is linked to any of the N-atoms in the compound, mainly to the N-atoms in the ring. The 50 main tautomers in case of R5 and R6 both being hydrogen atoms are the following:

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15 The tautomers together and addition salts thereof (HX added) are also represented by formula (Ia) (non-salt form) or (Ib) (salt form, aluminium complex as anion) or (Ic) (salt form = HX addition salt = aluminium complex as internal salt with higher coordination having four ligands at the Al-atom):

[0008] The compounds of the general formula (I) in which R5 and R6 are both hydrogen shall also represent tautomers (Ia) in the non-salt form and salt forms (Ib) and (Ic) and respective resonance structures, and addition complexes of higher coordination (see e. g. complexes with 5 ligands further below), unless specific tautomers or complex structures 50 are specifically considered. The same applies in cases when R5 or R6 or both being different from hydrogen, accordingly. [0009] The invention is thus directed or related to novel aluminium complexes of formula (I), or salts, dimers or polymers thereof (in short "salts thereof"),

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10 in which

1 R is (C1-C18)alkyl, (C2-C18)alkenyl or (C2-C18)alkynyl, wherein each of the last-mentioned three radicals is unsubstituted or substituted, preferably unsubstituted or substituted by one or more radicals selected from the group 15 consisting of halogen, hydroxy, nitro, carbamoyl, sulfo and radicals of the formulae -O-R1a, -S-R1b, -S(=O)-R1c,-S 1d 1e 1f 1g 1h 1i 1j 1k 1a 1a 1b 1c 1d (=O)2-R ,-NR R , -C(=O)-NHR , -C(=O)-NR R , -NHC(=O)-NR R and A , wherein R ,R ,R ,R , 18 1f 1g 1h 1i 1j 1k R ,R ,R ,R ,R ,R , and R , independently of one another, are (C1-C6)alkyl, (C1-C6)haloalkyl, (C1-C6) 1b 1 1 alkoxy-(C1-C6)alkyl or a radical of the formula A , or is a group of the formula A or B , 2 R is H, (C1-C18)alkyl, (C2-C16)alkenyl or (C2-C18)alkynyl, wherein each of the last-mentioned three radicals is 20 unsubstituted or substituted, preferably unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, hydroxy, nitro, carbamoyl, sulfo and radicals of the formulae- O-R2a, -S-R2b, -S(=O)-R2c,-S 2d 2e 2f 2g 2h 2i 2j 2k 2a 2a 2b 2c 2d (=O)2-R ,-NR R , -C(=O)-NHR , -C(=O)-NR R , -NHC(=O)-NR R and A , wherein R ,R ,R ,R , 2e 2f 2g 2h 2i 2j 2k R ,R ,R ,R ,R ,R , and R , independently of one another, are (C1-C6)alkyl, (C1-C6)haloalkyl, (C1-C6) 2b alkoxy-(C1-C6)alkyl or a radical of the formula A , 25 or is a group of the formula A2, 3 R is H, (C1-C1a)alkyl, (C2-C18)alkenyl or (C2-C18)alkynyl, wherein each of the last-mentioned three radicals is unsubstituted or substituted, preferably unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, hydroxy, nitro, carbamoyl, sulfo and radicals of the formulae -O-R3a, -S-R3b, -S(=O)-R3c,-S 3d 3e 3f 3g 3h 3i 3j 3k 3b 3a 3b 3c 3d (=C)2-R ,-NR R , -C(=O)-NHR , -C(=O)-NR R , -NHC(=O)-NR R and A , wherein R ,R ,R ,R , 30 3e 3f 3g 3h 3i 3j 3k R ,R ,R ,R ,R ,R , and R , independently of one another, are (C1-C6)alkyl, (C1-C6)haloalkyl, (C1-C6) 3b alkoxy-(C1-C6)alkyl or a radical of the formula A , or is a group of the formula A3, 4 R is H, (C1-C18)alkyl, (C2-C18)alkenyl or (C2-C18)alkynyl, wherein each of the last-mentioned three radicals is unsubstituted or substituted, preferably unsubstituted or substituted by one or more radicals selected from the group 35 consisting of halogen, hydroxy, nitro, carbamoyl, sulfo and radicals of the formulae -O-R4a, -S-R4b, -S(=O)-R4c,-S 4d 4e 4f 4g 4h 4i 4j 4k 4a 4a 4b 4c 4d (=O)2-R ,-NR R , -C(=O)-NHR , -C(=O)-NR R , -NHC(=O)-NR R and A , wherein R ,R ,R ,R , 4e 4f 4g 4h 4i 4j 4k R ,R ,R ,R ,R ,R , and R , independently of one another, are (C1-C6)alkyl, (C1-C6)haloalkyl, (C1-C6) 4b alkoxy-(C1-C6)alkyl or a radical of the formula A , or is a group of the formula A4, 40 5 R is H, (C1-C18)alkyl, (C2-C18)alkenyl or (C2-C18)alkynyl, wherein each of the last-mentioned three radicals is unsubstituted or substituted, preferably unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, hydroxy, nitro, carbamoyl, sulfo and radicals of the formulae- O-R5a, -S-R5b, -S(=O)-R5c,-S 5d 5e 5f 5g 5h 5i 5j 5k 5a a 5b 5c 5d 5e (=O)2-R ,-NR R , -C(=O)-NHR , -C(=O)-NR R , -NHC(=O)-NR R and A , wherein R ,R ,R ,R ,R , 5f 5g 5h 5i 5j 5k R ,R ,R ,R,R, and R , independently of one another, are (C1-C6)alkyl, (C1-C5)haloalkyl, (C1-C6) 45 5b 5 alkoxy-(C1-C6)alkyl or a radical of the formula A , or is a group of the formula A , 6 R is H, (C1-C18)alkyl, (C2-C18)alkenyl or (C2-C18)alkynyl, wherein each of the last-mentioned three radicals is unsubstituted or substituted, preferably unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, hydroxy, nitro, carbamoyl, sulfo and radicals of the formulae -O-R6a, -S-R6b, -S(=O)-R6c,-S 6d 6e 6f 6g 6h 6i 6j 6k 6a 6a 6b 6c 6d 6e (=O)2-R ,-NR R , -C(=O)-NHR , -C(=O)-NR R , -NHC(=O)NR R and A , wherein R ,R ,R ,R ,R , 50 ef 6g 6h 6i 6j 6k R ,R ,R ,R,R, and R , independently of one another, are (C1-C6)alkyl, (C1-C6)haloalkyl, (C1-C6) 6b alkoxy-(C1-C6)alkyl or a radical of the formula A , or is a group of the formula A6, or R1 and R2 or R3 and R4 together with the N-atom linked to each other form a N-heterocyclic ring having 3 to 7 ring atoms and optionally having one or more additional hetero atoms selected from the group consisting of N, O and 55 S and which is unsubstituted or substituted, preferably unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, hydroxy, nitro, carbamoyl, sulfo, (C1-C6)alkyl, (C1-C6)haloalkyl, (C1-C6) alkoxy-(C1-C6)alkyl, (C1-C6)alkoxy, (C1-C6)haloalkoxy, (C1-C6)alkoxy-(C1-C6)alkoxy, (C1-C6)alkylthio, (C1-C6)alkyl- suffinyl, (C1-C6)haloalkylsulfinyl, (C1-C6)alkylsulfonyl, (C1-C6)haloalkylsulfonyl, di-[(C1-C4)alkyl]-amino, (C1-C4)

5 EP 2 231 679 B1

alkylamino-carbonyl, di-[(C1-C4)alkyl]-amino-carbonyl, (C1-C4)alkylamino-carbonylamino, di-[(C1-C4)alkyl]-aminocarbonylamino and oxo, A1,A1a,A1b,A2,A2a,A2b,A3,A3a,A3b,A4,A4a,A4b,A5,A5a,A5b,A6,A6a, and A6b, independently of one another, are (C3-C9)cycloalkyl, (C4-C9)cycloalkenyl, (C5-C9)cycloalkinyl, aryl or heterocyclyl as a basic cyclic moiety, wherein 5 the basic cyclic moiety is unsubstituted or substituted, preferably

(a) is unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, hydroxy, nitro, carbamoyl, sulfo, (C1-C6)alkyl, (C1-C6)haloalkyl, (C1-C6)alkoxy-(C1-C6)alkyl, (C1-C6)alkoxy, (C1-C6)haloalkoxy, (C1-C6)a)koxy-(C1-C6)alkoxy, (C1-C6)alkylthio, (C1-C6)alkylsulfinyl, (C1-C6)haloalkylsulfi- 10 nyl, (C1-C6)alkylsulfonyl, (C1-C6)haloalkylsulfonyl, di-[(C1-C4)alkyl]-amino, (C1-C4)alkylamino-carbonyl, di-[(C1-C4)alkyl]-amino-carbonyl, (C1-C4)alkylamino-carbonylamino and di-[(C1-C4)alkyl]-amino-carbonylamino and, in case of heterocyclyl, also oxo attached to heteroring atoms N or S or in alpha-position of an N-atom as heteroring atom, or

15 (b) is substituted by or substituted additionally to one or more of the substituents mentioned in (a) by a bridge linked geminal (a 1,1-position), vicinal (a 1,2-position) or in a 1,3-position at the basic cyclic moiety thus forming another carbocyclic or heterocyclic ring together with the part of the basic cyclic moiety between the atoms linked to the bridge, preferably by a bridge linked in a vicinal position of the basic cyclic moiety thus forming a carbocyclic or heterocyclic ring condensed with the basic cyclic moiety, 20 wherein the carbocyclic or heterocyclic ring formed is saturated, partly unsaturated, unsaturated, aromatic or heteroaromatic and wherein the bridge is further unsubstituted or substituted, preferably is further unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, hydroxy, nitro, carbamoyl, sulfo, (C1-C6)alkyl, (C1-C6)haloalkyl, (C1-C6)alkoxy-(C1-C6)alkyl, (C1-C6)alkoxy, (C1-C6)haloalkoxy, (C1-C6) alkoxy-(C1-C6)alkoxy, (C1-C6)alkylthio, (C1-C6)alkylsulfinyl, (C1-C6)haloalkylsulfinyl, (C1-C6)alkylsulfonyl, 25 (C1-C6)haloalkylsuffonyl, di-[(C1-C4)alkyl]-amino, (C1-C4)alkylamino-carbonyl, di-[(C1-C4)alkyl]-amino-carbonyl, (C1-C4)alkylamino-carbonylamino and di-[(C1-C4)alkyl]-aminocarbonylamino,

B1 is a group as defined for R1 further linked to the amino group of the group of the formula (I*)

40 wherein R2*,R3*,R4*,R5*,R6*, X* and Y* are independently as defined in formula (I) for R2,R3,R4,R5,R6, X and Y, respectively, X and Y each, independently of one another, are selected from the group consisting of

(i) amino, 45 (ii) a group of the formula NR7R8 in which R7 is a radical selected from the group consisting of radicals as defined for and independently of R1, and in which R8 is a radical selected from the group consisting of radicals as defined for and independently of R2, preferably a group of the formulae NR7R8 which is defined as the group NR1R2 in formula (I), (iii) hydroxy, 50 (iv) (C1-C6)alkoxy, (C1-C6)haloalkoxy, (C1-C6)alkoxy-(C1-C6)alkoxy and (C1-C6)alkylthio, (v) (C1-C6)alkoxy, (C1-C6)haloalkoxy, (C1-C6)alkoxy-(C1-C6)alkoxy and (C1-C6)alkylthio, wherein each of the latter 4 radicals is substituted by one or more radicals selected from the group consisting of (C3-C6)cycloalkyl, (C3-C6) cycloalkoxy, wherein each of the last-mentioned 2 radicals is unsubstituted or substituted by one or more radicals selected from 55 the group consisting of halogen, hydroxy, carbamoyl, (C1-C6)alkyl, (C1-C6)haloalkyl, (C1-C6)alkoxy-(C1-C6)alkyl, (C1-C6)alkoxy, (C1-C6)haloalkoxy and (C1-C6)alkoxy-(C1-C6)alkoxy, aryl and aryloxy, wherein each of the last-mentioned 2 radicals is unsubstituted or substituted by one or more radicals selected from

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the group consisting of halogen, hydroxy, nitro, carbamoyl, sulfo, (C1-C6)alkyl, (C1-C6)haloalkyl, (C1-C6) alkoxy-(C1-C6)alkyl, (C1-C6)alkoxy, (C1-C6)haloalkoxy, (C1-C6)alkow-(C1-C8)alkoxy, (C1-C8)alkylthio, (C1-C6)alkylsulfinyl, (C1-C6)haloalkylsulfinyl, (C1-C6)alkylsulfonyl, (C1-C6)haloalkylsulfonyl, di-[(C1-C4)alkyl]-amino, (C1-C4) alkylamino-carbonyl, di-[(C1-C4)alkyl]-amino-carbonyl, (C1-C4)alkylamino-carbonylamino and di-[(C1-C4)alkyl]-ami- 5 nocarbonylamino, (vi) (C3-C6)cycloalkoxy which is unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, hydroxy, carbamoyl, (C1-C6)alkyl, (C1-C6)haloalkyl, (C1-C6)alkoxy-(C1-C6)alkyl, (C1-C6)alkoxy, (C1-C6)haloalkoxy and (C1-C6)alkoxy-(C1-C6)alkoxy, (vii) aryloxy which is unsubstituted or substituted, preferably unsubstituted or substituted by one or more radicals 10 selected from the group consisting of halogen, hydroxy, nitro, carbamoyl, sulfo, (C1-C6)alkyl, (C1-C6)haloalkyl, (C1-C6)alkoxy-(C1-C6)alkyl, (C1-C6)alkoxy, (C1-C6)haloalkoxy, (C1-C6)alkoxy-(C1-C6)alkoxy, (C1-C6)alkylthio, (C1-C6)alkylsulfinyl, (C1-C6)haloalkylsulfinyl, (C1-C6)alkylsulfonyl, (C1-C6)haloalkylsulfonyl, di-[(C1-C4)alkyl]-amino, (C1-C4)alkylamino-carbonyl, di-[(C1-C4)alkyl]-amino-carbonyl, (C1-C4)alkylamino-carbonylamino and di-[(C1-C4) alkyl]-aminocarbonylamino, 15 and (viii) acyloxy, acylthio or acylamino, preferably acyloxy,

more preferably are each selected from the above groups (ii), (iv), (v), (vi), (vii) and (viii), more preferably from the above groups (ii), (iv) and (v), or 20 X and Y together are a divalent group of the formula -U1-D*-U2- in which

D* is a hydrocarbon bridge, optionally interrupted by one or more divalent groups of the formula U3 defined below, or, preferably, is a linear alkylene bridge, a linear (C2-C10)alkenylene bridge, a linear (C2-C10)alkynylene bridge, a (C3-C9)cycloalkylene bridge, a phenylene bridge or a bridge consisting of a combination of two or more of said linear 25 acyclic and cyclic moieties having in total 4 to 24 carbon atoms, wherein the bridge in each case is unsubstituted or substituted, preferably unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, hydroxy, nitro, carbamoyl, sulfo, (C1-C6)alkyl, (C1-C6)haloalkyl, (C1-C6)alkoxy-(C1-C6)alkyl, (C1-C6) alkoxy, (C1-C6)haloalkoxy, (C1-C8)alkoxy-(C1-C6)alkoxy, (C1-C6)alkylthio, (C1-C6)alkylsulfinyl, (C1-C6)haloalkylsulfinyl, (C1-C6)alkylsulfonyl, (C1-C6)haloalkylsulfonyl, di-[(C1-C4)alkyl]-amino, (C1-C4)alkylamino-carbonyl, 30 di-[(C1-C4)alkyl]-amino-carbonyl, (C1-C4)alkylamino-carbonylamino and di-[(C1-C4)alkyl]-aminocarbonylamino, and U1,U2 and U3, independently of each other are selected from the group consisting of NH, NR’ , O and S, wherein R’ is (C1-C6)alkyl, hydroxy-(C1-C6)alky or (C1-C6)alkoxy-(C1-C6)alkyl, or X is a radical as defined above and Y is an organic ligand based on a compound of the formula Y’-H, Y’-RL or RL-U3-D**-U4-RLL wherein D** is a divalent group as defined for the group D* above, Y’ is a radical as defined for 35 Y, U3 is a divalent group as defined for U1 above, U4 is a divalent group as defined for U2 above, each of RL and LL R is a radical group selected from the group consisting of (C1-C6)alky, hydroxy-(C1-C6)alky or (C1-C6) alkoxy-(C1-C6)alkyl, and wherein the organic ligand is coordinated to the aluminium atom of the complex by a free electron pair of a hetero atom contained therein and selected from the group consisting of N, O and S, or 40 X and Y together are a radical of the formula -U1-D*-U2-RLLL in which U1,U2 and D* are as defined above, and LLL R is a radical selected from the group consisting of (C1-C6)alkyl, hydroxy-(C1-C6)alky or (C1-C6)alkoxy-(C1-C6) alky, and wherein the radical -U1-D*-U2-RLLL is additionally coordinated to the aluminium atom of the complex by a free electron pair located at a hetero atom contained in the radical (position represented by Y), preferably located at the heteroatom of the divalent group U2. 45 [0010] In the present patent specification, including the accompanying claims, the aforementioned substituents have the following meanings:

Halogen means fluorine, chlorine, bromine or iodine. In case of a radical "halogen" means a fluorine, chlorine, 50 bromine or iodine atom. The term "halo" before the name of a radical means that this radical is partially or completely halogenated, that is to say substituted by F, Cl, Br or I in any combination. The expression "(C1-C6)alkyl" means an unbranched or branched non-cyclic saturated hydrocarbon radical having 1, 2, 3, 4, 5 or 6 carbon atoms (indicated by a range of C-atoms in the parenthesis), such as, for example a methyl, ethyl, propyl, isopropyl, 1-butyl, 2-butyl, 2-methylpropyl 55 or tert-butyl radical. The same applies to alkyl groups in composite radicals such as "alkoxyalkyl". Alkyl radicals and also in composite groups, unless otherwise defined, preferably have 1 to 4 carbon atoms. "(C1-C6)Haloalkyl" means an alkyl group mentioned under the expression "(C1-C6)alkyl" in which one or more hydrogen atoms are replaced by the same number of identical or different halogen atoms, such as monohaloalkyl,

7 EP 2 231 679 B1

perhaloalkyl, CF3, CHF2,CH2F, CHFCH3,CF3CH2,CF3CF2, CHF2CF2,CH2FCHCl, CH2Cl, CCl3, CHCl2 or CH2CH2Cl. "[(C1-C4)alkoxy](C1-C6)alkyl" means (C1-C6)alkyl which is substituted by (C1-C4)alkoxy. "(C1-C6)Alkoxy" means an alkoxy group whose carbon chain has the meaning given under the expression "(C1-C6)alkyl". "Haloalkoxy" is, for 5 example, OCF3, OCHF2, OCH2F, CF3CF2O, OCH2CF3 or OCH2CH2Cl. "(C2-C6)Alkenyl" means an unbranched or branched non-cyclic carbon chain having a number of carbon atoms which corresponds to this stated range and which contains at least one double bond which can be located in any position of the respective unsaturated radical. "(C2-C6)alkenyl" accordingly denotes, for example, the vinyl, allyl, 2- methyl-2-propenyl, 2-butenyl, pentenyl, 2-methylpentenyl or the hexenyl group. "(C2-C6)alkynyl" means an un- 10 branched or branched non-cyclic carbon chain having a number of carbon atoms which corresponds to this stated range and which contains one triple bond which can be located in any position of the respective unsaturated radical. "(C2-C6)alkynyl" accordingly denotes, for example, the propargyl, 1-methyl-2-propynyl, 2-butynyl or 3-butynyl group. yclohexadienyl.

15 [0011] A hydrocarbon radical or bridge is a monovalent or divalent group, respectively, which consists of carbon and hydrogen atoms and which is a linear or branched acyclic or a cyclic group or a group consisting of acyclic and cyclic moieties, and which group is saturated, partly unsaturated, fully unsaturated or aromatic or which group consists of two or more of said structural moieties linked to each other. [0012] Cycloalkyl is a carbocyclic saturated ring system having preferably 3-8 carbon atoms, for example cyclopropyl, 20 cyclobutyl, cyclopentyl or cyclohexyl. In the case of substituted cycloalkyl, cyclic systems with substituents are included, where the substituents are bonded by a double bond on the cycloalkyl radical, for example an alkylidene group such as methylidene. In the case of substituted cycloalkyl, polycyclic aliphatic systems are also included, for example bicyclo [1.1.0]butan-1-yl, bicyclo[1.1.0]butan-2-yl, bicyclo[2.1.0]pentan-1-yl, bicyclo[2.1.0]pentan-2-yl, bicyclo[2.1.0]pentan-5- yl, adamantan-1-yl and adamantan-2-yl. 25 [0013] Cycloalkenyl is a carbocyclic, nonaromatic, partially unsaturated ring system having preferably 4-8 carbon atoms, for example 1-cyclobutenyl, 2-cyclobutenyl, 1-cyclopentenyl, 2-cyclopentenyl, 3-cyclopentenyl, or 1-cyclohexenyl, 2-cyclohexenyl, 3-cyclohexenyl, 1,3-cyclohexadienyl or 1,4-cyclohexadienyl. In the case of substituted cycloalkenyl, the explanations for substituted cycloalkyl apply correspondingly. [0014] Haloalkyl, -alkenyl and -alkynyl are, respectively, alkyl, alkenyl and alkynyl substituted partly or fully by identical 30 or different halogen atoms, preferably from the group of fluorine, chlorine and bromine, in particular from the group of fluorine and chlorine, for example monohaloalkyl, perhaloalkyl, CF3, CHF2,CH2F, CF3CF2,CH2FCHCl, CCl3, CHCl2, CH2CH2Cl; haloalkoxy is, for example OCF3, OCHF2, OCH2F, CF3CF2O, OCH2CF3 and OCH2CH2Cl; the same applies to haloalkenyl and other halogen-substituted radicals. [0015] Aryl is a mono-, bi- or polycyclic aromatic system, for example phenyl, naphthyl, tetrahydronaphthyl, indenyl, 35 indanyl, pentalenyl, fluorenyl and the like, preferably phenyl. [0016] A heterocyclic radical or ring (heterocyclyl) can be saturated, partially unsaturated, unsaturated or heteroaromatic; unless defined otherwise, it preferably contains one or more, in particular 1, 2 or 3, heteroatoms in the heterocyclic ring, preferably from the group of N, O and S; it is preferably an aliphatic heterocyclyl radical having from 3 to 7 ring atoms or a heteroaromatic radical having 5 or 6 ring atoms. The heterocyclic radical may, for example, be a heteroaromatic 40 radical or ring (heteroaryl), for example a mono-, bi- or polycyclic aromatic system in which at least one ring contains one or more heteroatoms. It is preferably a heteroaromatic ring having a heteroatom from the group of N, O and S, for example pyridyl, pyrrolyl, thienyl or furyl; it is also preferably a corresponding heteroaromatic ring having 2 or 3 heteroatoms, for example pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, thiazolyl, thiadiazolyl, oxazolyl, isoxazolyl, pyrazolyl, imidazolyl and triazolyl. It is also preferably a partially or fully hydrogenated heterocyclic radical having one heteroatom 45 from the group of N, O and S, for example oxiranyl, oxetanyl, oxolanyl (= tetrahydrofuryl), oxanyl, pyrrolinyl, pyrrolidyl or piperidyl. [0017] It is also preferably a partially or fully hydrogenated heterocyclic radical having 2 heteroatoms from the group of N, O and S, for example piperazinyl, dioxolanyl, oxazolinyl, isoxazolinyl, oxazolidinyl, isoxazolidinyl and morpholinyl. [0018] Possible substituents for a substituted heterocyclic radical include the substituents specified below, and addi- 50 tionally also oxo. The oxo group may also occur on the ring heteroatoms which may exist in various oxidation states, for example in the case of N and S. [0019] Preferred examples of heterocyclyl are a heterocyclic radical having from 3 to 6 ring atoms from the group of pyridyl, thienyl, furyl, pyrrolyl, oxiranyl, 2-oxetanyl, 3-oxetanyl, oxolanyl (= tetrahydrofuryl), pyrrolidyl, piperidyl, especially oxiranyl, 2-oxetanyl, 3-oxetanyl or oxolanyl, or is a heterocyclic radical having two or three heteroatoms, for example 55 pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, thienyl, thiazolyl, thiadiazolyl, oxazolyl, isoxazolyl, pyrazolyl, triazolyl, piperazinyl, dioxolanyl, oxazolinyl, isoxazolinyl, oxazolidinyl, isoxazolidinyl or morpholinyl. [0020] When a base structure is substituted "by one or more radicals " from a list of radicals (= group) or a generically defined group of radicals, this in each case includes simultaneous substitution by a plurality of identical and/or structurally

8 EP 2 231 679 B1

different radicals. [0021] Substituted radicals, such as a substituted alkyl, alkenyl, alkynyl, aryl, phenyl, benzyl, heterocyclyl and heteroaryl radical, are, for example, a substituted radical derived from the unsubstituted base structure, where the substituents are, for example, one or more, preferably 1, 2 or 3, radicals from the group of halogen, alkoxy, alkylthio, hydroxyl, amino, 5 nitro, carboxyl, cyano, azido, alkoxycarbonyl, alkylcarbonyl, formyl, carbamoyl, mono- and dialkylaminocarbonyl, substituted amino such as acylamino, mono- and dialkylamino, alkylsulfinyl, alkylsulfonyl and, in the case of cyclic radicals, also alkyl, haloalkyl, alkylthioalkyl, alkoxyalkyl, optionally substituted mono- and dialkylaminoalkyl and hydroxyalkyl; in the term "substituted radicals", such as substituted alkyl, etc., substituents include, in addition to the saturated hydrocarbon radicals mentioned, corresponding unsaturated and aromatic radicals, such as optionally substituted alkenyl, 10 alkynyl, alkenyloxy, alkynyloxy, phenyl, phenoxy, etc. [0022] In the case of substituted cylic radicals having aliphatic moieties in the ring, cyclic systems with those substituents which are bonded on the ring by a double bond are also included, for example substituted by an alkylidene group such as methylidene or ethylidene. [0023] It should be noted that in the present case those of the above groups which can easily react under the reaction 15 conditions with the cyanoguanidine of formula (III) or with the amino group of the compound (II) in the process for preparing a compound of the formula (I) are not preferred or need to be masked by a "protective group" if such a functional group shall be implemented. [0024] The substituents mentioned by way of example ("first substituent level") may, when they contain hydrocarbon moieties, optionally be further substituted there ("second substituent level"), for example by one of the substituents as 20 defined for the first substituent level. Corresponding further substituent levels are possible. The term "substituted radical" preferably includes only one or two substituent levels. [0025] Preferred substituents for the substituent levels are, for example, amino, hydroxyl, halogen, nitro, cyano, mer- capto, carboxyl, carbonamide, SF5, aminosulfonyl, alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, monoalkylamino, dialkylamino, N-alkanoylamino, alkoxy, alkenyloxy, alkynyloxy, cycloalkoxy, cycloalkenyloxy, alkoxycarbonyl, alkeny- 25 loxycarbonyl, alkynyloxycarbonyl, aryloxycarbonyl, alkanoyl, alkenylcarbonyl, alkynylcarbonyl, arylcarbonyl, alkylthio, cycloalkylthio, alkenylthio, cycloalkenylthio, alkynylthio, alkylsulfinyl, alkylsulfonyl, monoalkylaminosulfonyl, dialkylami- nosulfonyl, N-alkylaminocarbonyl, N,N-dialkylaminocarbonyl, N-alkanoylaminocarbonyl, N-alkanoyl-N-alkylaminocarbonyl, aryl, aryloxy, benzyl, benzyloxy, benzylthio, arylthio, arylamino and benzylamino. [0026] In the case of radicals with carbon atoms, preference is given to those having from 1 to 6 carbon atoms, 30 preferably from 1 to 4 carbon atoms, in particular 1 or 2 carbon atoms. In general, preferred substituents are those from the group of halogen, e.g. fluorine and chlorine, (C1-C4)alkyl, preferably methyl or ethyl, (C1-C4)haloalkyl, preferably trifluoromethyl, (C1-C4)alkoxy, preferably methoxy or ethoxy, (C1-C4)haloalkoxy, nitro and cyano. Preference is given to the substituents methyl, methoxy, fluorine and chlorine. [0027] Substituted amino, such as mono- or disubstituted amino, is a radical from the group of the substituted amino 35 radicals which are N-substituted, for example, by one or two identical or different radicals from the group of alkyl, alkoxy, acyl and aryl; preferably mono- and dialkylamino, mono- and diarylamino, acylamino, N,N-diacylamino, N-alkyl-N-arylamino, N-alkyl-N-acylamino and N-heterocycles; preference is given to alkyl radicals having from 1 to 4 carbon atoms; aryl is preferably phenyl or substituted phenyl; acyl is as defined below, preferably (C1-C4)alkanoyl. The same applies to substituted hydroxytamino or hydrazino. 40 [0028] Optionally substituted phenyl is preferably phenyl which is unsubstituted or mono- or polysubstituted, preferably up to trisubstituted, by identical or different radicals from the group of halogen, (C1-C4)alkyl, (C1-C4)alkoxy, (C1-C4) haloalkyl, (C1-C4)haloalkoxy and nitro, for example o-, m- and p-tolyl, dimethylphenyls, 2-, 3- and 4-chlorophenyl, 2-, 3- and 4-trifluoro- and -trichlorophenyl, 2,4-, 3,5-, 2,5- and 2,3-dichlorophenyl, o-, m- and p-methoxyphenyl. [0029] The invention also provides all stereoisomers which are encompassed by formula (I) and mixtures thereof. 45 Such compounds of the formula (I) contain one or more asymmetric carbon atoms or else double bonds which are not stated specifically in the general formulae (I). The possible stereoisomers defined by their specific three-dimensional shape, such as enantiomers, diastereomers, Z- and E-isomers, are all encompassed by the formula (I) and can be obtained from mixtures of the stereoisomers by customary methods or else prepared by stereoselective reactions in combination with the use of stereochemically pure starting materials. 50 [0030] The expression "one or more radicals selected from the group consisting of" in the definition is to be understood as meaning in each case one or more identical or different radicals selected from the stated group of radicals, unless specific limitations are defined expressly. [0031] Acyl is a radical of an organic acid which arises in a formal sense by removal of a hydroxyl group on the acid function, and the organic radical in the acid may also be bonded to the acid function via a heteroatom. Examples of acyl 55 are the -CO-R radical of a carboxylic acid HO-CO-R and radicals of acids derived therefrom, such as those of thiocar- boxylic acid, optionally N-substituted iminocarboxylic acids or the radical of carbonic monoesters, N-substituted carbamic acid, sulfonic acids, sulfinic acids, N-substituted sulfonamide acids, phosphonic acids or phosphinic acids. [0032] Acyl is, for example, formyl, alkylcarbonyl such as [(C1-C4)alkyl]carbonyl, phenylcarbonyl, alkyloxycarbonyl,

9 EP 2 231 679 B1

phenyloxycarbonyl, benzyloxycarbonyl, alkylsulfonyl, alkylsulfinyl, N-alkyl-1-iminoalkyl and other radicals of organic acids. The radicals may each be substituted further in the alkyl or phenyl moiety, for example in the alkyl moiety by one or more radicals from the group of halogen, alkoxy, phenyl and phenoxy; examples of substituents in the phenyl moiety are the substituents already mentioned above in general for substituted phenyl. 5 [0033] Acyl is preferably an acyl radical in the narrower sense, i.e. a radical of an organic acid in which the acid group is bonded directly to the carbon atom of an organic radical, for example formyl, alkylcarbonyl such as acetyl or [(C1-C4) alkyl]carbonyl, optionally substituted phenylcarbonyl, such as benzoyl, alkylsulfonyl, such as methylsulfonyl, alkylsulfinyl, optionally substituted arylsulfonyl, such as phenylsulfonyl or p-tolylsulfonyl and other radicals of organic acids. [0034] The invention also provides all stereoisomers which are encompassed by formula (I) and mixtures thereof. 10 Such compounds of the formula (I) contain one or more asymmetric carbon atoms or else double bonds which are not stated specifically in the general formulae (I). The possible stereoisomers defined by their specific three-dimensional shape, such as enantiomers, diastereomers, Z- and E-isomers, are all encompassed by the formula (I) and can be obtained from mixtures of the stereoisomers by customary methods or else prepared by stereoselective reactions in combination with the use of stereochemically pure starting materials. 15 [0035] Compounds of the stated formula (I) according to the invention in which individual radicals have one of the preferred meanings which have already been stated or are stated hereinbelow and particularly those shown in the Table examples, or in particular those in which two or more of the preferred meanings which have already been stated or which are stated hereinbelow are combined, are of particular interest, mainly because of the ease of preparation or efficacy in the process of forming the aluminium complexes or in the process of forming triazines from the aluminium 20 complexes. [0036] Of particular interest are compounds of formula (I) where a radical selected from the group of radicals R1,R2, R3, R4, R5, R6, X and Y is preferably defined as set forth below. [0037] In the following preferred definitions it is generally to be understood that where symbols are not specifically defined for a specific group of compounds they are to be defined as defined for the compounds in formula (I) or the 25 respective generic formula or for preferred compounds of formula (I) or the respective preferred formula in the description.

1 R preferably is (C1-C12)alkyl, (C2-C12)alkenyl or (C2-C12)alkynyl, more preferably (C1-C6)alkyl, (C2-C6)alkenyl or (C2-C6)alkynyl, wherein each of the last-mentioned six radicals is unsubstituted or substituted, preferably unsubstituted or substituted 30 by one or more radicals selected from the group consisting of halogen, hydroxy, nitro, carbamoyl, sulfo and radicals 1a 1b 1c 1d 1e 1f 1g 1h 1i of the formulae -O-R , -S-R , -S(=O)-R , -S(=O)2-R ,-NR R , -C(=O)-NHR , -C(=O)-NR R , -NHC (=O)-NR1jR1k and A1a, more preferably by one or more radicals selected from the group consisting of halogen, hydroxy and radicals of the 1a 1b 1c 1d 1e 1f 1a formulae -O-R , -S-R , -S(=O)-R , -S(=O)2-R , -NR R and A , 35 more preferably by one or more radicals selected from the group consisting of halogen, hydroxy and radicals of the formula -O-R1a and A1a, 1a 1b 1c 1d 1e 1f 1g 1h 1i 1j 1k wherein R ,R ,R ,R ,R ,R ,R ,R ,R ,R , and R , independently of one another, are (C1-C6)alkyl, 1b (C1-C6)haloalkyl, (C1-C6)alkoxy-(C1-C6)alkyl or a radical of the formula A , preferably are (C1-C4)alkyl, (C1-C4) 1b haloalkyl, (C1-C4)alkoxy-(C1-C4)alkyl or a radical of the formula A , 40 1b more preferably are (C1-C4)alkyl or a radical of the formula A , or is a group of the formula A1 or B1, preferably of the formula A1, or R1 and R2 together with the N-atom linked to each other form a N-heterocyclic ring having 5 or 6 ring atoms and optionally having 1, 2 or 3 additional hetero atoms selected from the group consisting of N, O and S and which is 45 unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, hydroxy, nitro, carbamoyl, sulfo, (C1-C6)alkyl, (C1-C6)haloalkyl, (C1-C6)alkoxy-(C1-C6)alkyl, (C1-C6)alkoxy, (C1-C6)haloalkoxy, (C1-C6)alkoxy-(C1-C6)alkoxy, (C1-C6)alkylthio, (C1-C6)alkylsulfinyl, (C1-C6)haloalkylsulfinyl, (C1-C6)alkylsulfonyl, (C1-C6)haloalkylsulfonyl, di-[(C1-C4)alkyl]-amino, (C1-C4)alkylamino-carbonyl di-[(C1-C4)alkyl]-amino-carbonyl, (C1-C4)alkylamino-carbonylamino, di-[(C1-C4)alkyl]-aminocarbonylamino and oxo, 50 preferably unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, hydroxy, nitro, (C1-C4)alkyl, (C1-C4)haloalkyl, (C1-C4)alkoxy-(C1-C4)alkyl, (C1-C4)alkoxy, (C1-C4)haloalkoxy, (C1-C4)alkow-(C1-C4)a)koxy, (C1-C4)alkylthio, (C1-C4)alkylsulfonyl, (C1-C4)haloalkylsulfonyl and oxo, more preferably unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, (C1-C4)alkyl, (C1-C4)haloalkyl, (C1-C4)alkoxy, (C1-C4)alkylsulfonyl, (C1-C4)haloalkylsulfonyl and oxo, 55 1 1a 1b A ,A and A , independently of one another, are (C3-C9)cycloalkyl, (C4-C9)cycloalkenyl, (C5-C9)cycloalkinyl, aryl or heterocyclyl as a basic cyclic moiety, wherein the basic cyclic moiety is unsubstituted or substituted, preferably

(a) is unsubstituted or substituted by one or more radicals selected from the group consisting of halogen,

10 EP 2 231 679 B1

hydroxy, nitro, carbamoyl, sulfo, (C1-C6)alkyl, (C1-C6)haloalkyl, (C1-C6)alkoxy-(C1-C6)alkyl, (C1-C6)alkoxy, (C1-C6)haloalkoxy, (C1-C6)alkoxy-(C1-C6)alkoxy, (C1-C6)alkylthio, (C1-C6)alkylsulfinyl, (C1-C6)haloalkylsulfinyl, (C1-C6)alkylsulfonyl, (C1-C6)haloalkylsulfonyl, di-[(C1-C4)alkyl]-amino, (C1-C4)alkylamino-carbonyl di-[(C1-C4) alkyl]-amino-carbonyl, (C1-C4)alkylamino-carbonylamino and di-[(C1-C4)alkyl]-amino-carbonylamino and, in 5 case of heterocyclyl, also oxo attached to heteroring atoms N or S or in alpha-position of an N-atom as heteroring atom, more preferably is unsubstituted or substituted in the cyclic moiety by one or more radicals selected from the group consisting of halogen, hydroxy, nitro, sulfo, (C1-C4)alkyl, (C1-C4)haloalkyl, (C1-C4)alkoxy-(C1-C4)alkyl, (C1-C4)alkoxy, (C1-C4)haloalkoxy, (C1-C4)alkoxy-(C1-C4)alkoxy, (C1-C4)alkylthio, (C1-C4)alkylsulfinyl, (C1-C4) 10 haloalkyl-sulfinyl, (C1-C4)alkylsulfonyl and (C1-C4)haloalkylsulfonyl, more preferably is unsubstituted or substituted in the cyclic moiety by one or more radicals selected from the group consisting of halogen, hydroxy, nitro, (C1-C4)alkyl, (C1-C4)haloalkyl, (C1-C4)alkoxy-(C1-C4)alkyl, (C1-C4)alkoxy, (C1-C4)haloalkoxy, (C1-C4) alkoxy-(C1-C4)alkoxy, (C1-C4)alkylthio, (C1-C4)alkylsulfonyl and (C1-C4)haloalkylsulfonyl, more preferably is unsubstituted or substituted in the cyclic moiety by one or more radicals selected from the group consisting of 15 halogen, (C1-C4)alkyl, (C1-C4)haloalkyl, (C1-C4)alkoxy, (C1-C4)haloalkoxy, (C1-C4)alkylthio and (C1-C4)alkylsulfonyl, or

(b) is substituted by or substituted additionally to one or more of the substituents mentioned in (a) by a bridge 20 linked geminal (a 1,1-position), vicinal (a 1,2-position) or in a 1,3-position at the basic cyclic moiety thus forming another carbocyclic or heterocyclic ring together with the part of the basic cyclic moiety between the atoms linked to the bridge, preferably by a bridge linked in a vicinal position of the basic cyclic moiety thus forming a carbocyclic or heterocyclic ring condensed with the basic cyclic moiety, wherein the carbocyclic or heterocyclic ring formed is saturated, partly unsaturated, unsaturated having 3 to 9 ring atoms or is aromatic or heteroaromatic 25 having 5 or 6 ring atoms and wherein the bridge is further unsubstituted or substituted, preferably wherein the bridge forming a ring is further unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, hydroxy, nitro, carbamoyl, sulfo, (C1-C6)alkyl, (C1-C6)haloalkyl, (C1-C6)alkoxy-(C1-C6) alkyl, (C1-C6)alkoxy, (C1-C6)haloalkoxy, (C1-C6)alkoxy-(C1-C6)alkoxy, (C1-C6)alkylthio,

30 (C1-C6)alkylsulfinyl, (C1-C6)haloalkylsulfinyl, (C1-C6)alkylsulfonyl, (C1-C6)haloalkylsulfonyl, di-[(C1-C4)alkyl]-amino, (C1-C4)alkylamino-carbonyl, di-[(C1-C4)alkyl]-amino-carbonyl, (C1-C4)alkylamino-carbonylamino and di-[(C1-C4) alkyl]-amino-carbonylamino and, in case of heterocyclyl, also oxo attached to heteroring atoms N or S or in alpha- position of an N-atom as heteroring atom, or is further benzocondensated wherein the additional annellated benzene ring is unsubstituted or further substituted by one or more radicals as defined for substitution of the bridge which is 35 benzocondensated, more preferably the bridge forming a ring is further unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, hydroxy, nitro, sulfo, (C1-C4)alkyl, (C1-C4)haloalkyl, (C1-C4)alkoxy-(C1-C4) alkyl, (C1-C4)alkoxy, (C1-C4)haloalkoxy, (C1-C4)alkoxy-(C1-C4)alkoxy, (C1-C4)alkylthio, (C1-C4)alkylsulfinyl, (C1-C4) haloalkyl-sulfinyl, (C1-C4)alkylsulfonyl and (C1-C4)haloalkylsulfonyl, 40 more preferably the bridge forming a ring is further unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, hydroxy, nitro, (C1-C4)alkyl, (C1-C4)haloalkyl, (C1-C4)alkoxy-(C1-C4)alkyl, (C1-C4)alkoxy, (C1-C4)haloalkoxy, (C1-C4)alkoxy-(C1-C4)alkoxy, (C1-C4)alkylthio, (C1-C4)alkylsulfonyl and (C1-C4) haloalkylsulfonyl, more preferably the bridge forming a ring is further unsubstituted or substituted by one or more radicals selected 45 from the group consisting of halogen, (C1-C4)alkyl, (C1-C4)haloalkyl, (C1-C4)alkoxy, (C1-C4)haloalkoxy, (C1-C4)alkylthio and (C1-C4)alkylsulfonyl, B1 is a group as defined for R1 further linked to the amino group of the group of the formula (I*),

11 EP 2 231 679 B1

wherein R2*, R3*, R4*,R5*, R6*, X and Y are independently as defined in formula (I) for R2,R3,R4,R5,R6, X and Y, respectively. [0038] Examples for R1 are (C1-C12)alkyl, (C2-C12)alkenyl or (C2-C12)alkynyl, more preferably (C1-C6)alkyl, 5 (C2-C6)alkenyl or (C2-C6)alkynyl, wherein each of the last-mentioned six radicals is unsubstituted or substituted, preferably unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, hydroxy, nitro, carbamoyl, sulfo, (C1-C6)alkoxy, (C1-C6)haloalkoxy, (C1-C6)alkoxy-(C1-C6)alkoxy, (C1-C6)alkylthio, (C1-C6)alkylsulfinyl), (C1-C6)haloalkylsulfinyl, (C1-C6)alkylsulfonyl, (C1-C6)haloalkylsulfonyl, di-[(C1-C4)alkyl]-amino, (C1-C4)alkylamino-carbonyl, di-[(C1-C4) 10 alkyl]-amino-carbonyl, (C1-C4)alkylamino-carbonylamino and di-[(C1-C4)alkyl]-amino-carbonylamino, (C3-C6)cycloalkyl, (C5-C6)cycloalkenyl, phenyl, naphthyl, heterocyclyl, benzocondensated heterocycyl, benzo-(C5-C6)cycloalkyl, benzo-(C5-C6)cycloalkenyl, (C3-C5)cycloalkoxy, benzo-(C5-C6)cycloalkoxy, (C5-C6)cycloalkenyloxy, benzo-(C5-C6)cycloalkenyloxy, phenoxy, naphthoxy, phenylthio, heterocyclyloxy, benzocondensated heterocyclyloxy, heterocyclylthio, benzocondensated heterocyclylthio 15 wherein each of the last-mentioned 19 radicals is unsubstituted or substituted in the cyclic moiety by one or more radicals selected from the group consisting of halogen, hydroxy, nitro, carbamoyl, sulfo, (C1-C4)alkyl, (C1-C4)haloalkyl, (C1-C4) alkoxy-(C1-C4)alkyl, (C1-C4)alkoxy, (C1-C4)haloalkoxy, (C1-C4)alkoxy-(C1-C4)alkoxy, (C1-C4)alkylthio, (C1-C4)alkylsulfinyl, (C1-C4)haloalkylsulfinyl, (C1-C4)alkylsulfonyl, (C1-C4 )haloalkylsulfonyl, di-[(C1-C4)alkyl]-amino, (C1-C4)alkylamino- carbonyl di-[(C1-C4)alkyl]-amino-carbonyl, (C1-C4)alkylamino-carbonylamino and di-[(C1-C4)alkyl]-amino-carbonylami- 20 no and, in case of heterocyclyl, also oxo attached to heteroring atoms N or S or in alpha-position of an N-atom as heteroring atom, or are (C3-C6)cycloalkyl, benzo-(C5-C6)cycloalkyl, (C5-C6)cycloalkenyl, benzo-(C5-C6)cycloalkenyl, phenyl, naphthyl, heterocyclyl, benzocondensated heterocyclyl, wherein each of the last-mentioned 8 radicals is unsubstituted or substituted in the cyclic moiety by one or more radicals 25 selected from the group consisting of halogen, hydroxy, nitro, carbamoyl, sulfo, (C1-C4)alkyl, (C1-C4)haloalkyl, (C1-C4) alkoxy-(C1-C4)alkyl, (C1-C4)alkoxy, (C1-C4)haloalkoxy, (C1-C4)alkoxy-(C1-C4)alkoxy, (C1-C4)alkylthio, (C1-C4)alkylsulfinyl, (C1-C4)haloalkylsulfinyl, (C1-C4)alkylsulfonyl, (C1-C4)haloalkylsulfonyl, di-[(C1-C4)alkyl]-amino, (C1-C4)alkylamino- carbonyl di-[(C1-C4)alkyl]-amino-carbonyl, (C1-C4)alkylamino-carbonylamino and di-[(C1-C4)alkyl]-amino-carbonylamino and, in case of heterocyclyl, also oxo attached to heteroring atoms N or S or in alpha-position of an N-atom as 30 heteroring atom. [0039] "Heterocyclyl" for the above radicals or substitutents preferably is a heterocyclic saturated, partly saturated, unsaturated or heteroaromatic ring having 3 to 9 ring atoms, preferably 5 or 6 ring atoms in case of a saturated ring or having 5 to 9, preferably 5 or 6 ring atoms in case of partly saturated, unsaturated or heteroaromatic ring, preferably a ring having 1, 2, 3 or 4 hetero ring atoms selected from the group consisting of N, O and S. 35 [0040] Preferably optionally substituted heterocyclyl is saturated heterocyclyl or heteroaryl or benzocondensated derivatives thereof which may be further substituted. [0041] Preferably heteroaryl is: pyrrole, imidazole, triazole, tetrazole, thiophene, thiazole, thiadiazole, oxazole, oxa- diazole, pyridine, pyrimidine, piperazine, triazine, tetrazine, benzocondensated derivatives thereof and bicyclic combi- 1 nations thereof. Preferably R is (C1-C6)alkyl, (C1-C6)haloalkyl, phenyl, naphthyl, phenyl(C1-C6)alkyl, such as benzyl 40 or phenethyl, (C2-C6)alkenyl, phenyl(C2-C6)alkenyl, (C2-C6)alkynyl, phenyl(C2-C6)alkynyl, (C3-C6)cycloalkyl, benzo (C5-C6)cycloalkyl, such as tetrahydronaphthyl, indanyl, indenyl, fluorenyl, heteroaryl, wherein the radicals are unsubstituted or substituted in the cyclic moiety, preferably unsubstituted or substituted by one or more radicals mentioned as substituents for A1 above. [0042] Preferably R1 and R2 together with the N-atom linked to each other are a saturated heterocyclic ring having 5 45 or 6 ring atoms and can have 1 or 2 additional hetero atoms selected from the group consisting of N, O and S and which is unsubstituted or substituted, for example pyrrolidino, morpholino, piperidino, dihydroindolino, dihydroisoindolino, tet- rahydroquinolino, tetrahydroisoquinolino, which all may be further substituted, preferably unsubstituted or substituted by one or more radicals mentioned as substituents for A1 above. [0043] Preferably R2 50 is H, (C1-C12)alkyl, (C2-C12)alkenyl or (C2-C12)alkynyl, more preferably H, (C1-C6)alkyl, (C2-C6)alkenyl or (C2-C6)alkynyl, more preferably H and (C1-C4)alkyl, in particular H, wherein each of the carbon-containing radicals is unsubstituted or substituted, preferably unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, hydroxy, nitro, carbamoyl, sulfo and radicals of the formulae 55 2a 2b 2c 2d 2e 2f 2g -O-R , -S-R , -S(=O)-R , -S(=O)2-R ,-NR R , -C(=O)-NHR ,

-C(=O)-NR2hR2i, -NHC(=O)-NR2jR2k and A2a,

12 EP 2 231 679 B1

more preferably by one or more radicals selected from the group consisting of halogen, hydroxy and radicals of the formulae

5 2a 2b 2c 2d 2a -O-R , -S-R , -S(=O)-R , -S(=O)2-R and A ,

more preferably by one or more radicals selected from the group consisting of halogen, hydroxy and radicals of the formula -O-R2a and A2a, 2a 2b 2c 2d 2e 2f 2g 2h 2i 2j 2k wherein R ,R ,R ,R ,R ,R ,R ,R ,R ,R , and R , independently of one another, are (C1-C6)alkyl, (C1-C6) 10 2b haloalkyl, (C1-C6)alkoxy-(C1-C6)alkyl or a radical of the formula A , 2b preferably are (C1-C4)alkyl, (C1-C4)haloalkyl, (C1-C4)alkoxy-(C1-C4)alkyl or a radical of the formula A , 2b more preferably are (C1-C4)alkyl or a radical of the formula A , or is a group of the formula A2, wherein A2, A2a and A2b, independently of one another, are as defined for A1, A1a and A1b, above, preferably wherein 15 2 2a 2b A ,A and A independently of one another, are (C3-C6)cycloalkyl, phenyl, heterocyclyl, wherein each of the last- mentioned 3 radicals is unsubstituted or substituted in the cyclic moiety, preferably is unsubstituted or substituted in the cyclic moiety by one or more radicals selected from the group consisting of halogen, hydroxy, nitro, carbamoyl, sulfo, (C1-C6)alkyl, (C1-C6)haloalkyl, (C1-C6)alkoxy-(C1-C6)alkyl, (C1-C6)alkoxy, (C1-C6)haloalkoxy, (C1-C6)alkoxy-(C1-C6) alkoxy, (C1-C6)alkylthio, (C1-C6)alkylsulfinyl, (C1-C6)haloalkylsulfinyl, (C1-C6)alkylsulfonyl, (C1-C6)haloalkylsulfonyl, 20 di-[(C1-C4)alkyl]-amino, (C1-C4)alkylamino-carbonyl di-[(C1-C4)alkyl]-amino-carbonyl, (C1-C4)alkylamino-carbonylamino and di-[(C1-C4)alkyl]-amino-carbonylamino and, in case of heterocyclyl, also oxo attached to heteroring atoms N or S or in alpha-position of an N-atom as heteroring atom, more preferably is unsubstituted or substituted in the cyclic moiety by one or more radicals selected from the group consisting of halogen, hydroxy, nitro, sulfo, (C1-C4)alkyl, (C1-C4)haloalkyl, (C1-C4)alkoxy-(C1-C4)alkyl, (C1-C4)alkoxy, 25 (C1-C4)haloalkoxy, (C1-C4)alkoxy-(C1-C4)alkoxy, (C1-C4)alkylthio, (C1-C4)alkylsulfinyl, (C1-C4)haloalkyl-sulfinyl, (C1-C4)alkylsulfonyl and (C1-C4)haloalkylsulfonyl, more preferably is unsubstituted or substituted in the cyclic moiety by one or more radicals selected from the group consisting of halogen, hydroxy, nitro, (C1-C4)alkyl, (C1-C4)haloalkyl, (C1-C4)alkoxy-(C1-C4)alkyl, (C1-C4)alkoxy, (C1-C4) haloalkoxy, (C1-C4)alkoxy-(C1-C4)alkoxy, (C1-C4)alkylthio, 30 (C1-C4)alkylsulfonyl and (C1-C4)haloalkylsulfonyl, more preferably is unsubstituted or substituted in the cyclic moiety by one or more radicals selected from the group consisting of halogen, (C1-C4)alkyl, (C1-C4)haloalkyl, (C1-C4)alkoxy, (C1-C4)haloalkoxy, (C1-C4)alkylthio and (C1-C4) alkylsulfonyl, or R2 together with R1 and the N-atom linking them are as defined for NR1R2 above. 35 2 1 [0044] Examples for R are H or radicals as preferably defined for R , particularly H, (C1-C4)alkyl, (C2-C4)alkenyl or (C2-C4)alkynyl, (C1-C4)haloalkyl, phenyl, naphthyl, phenyl(C1-C4)alkyl, such as benzyl or phenethyl, or (C3-C6)cycloalkyl. wherein each of the last-mentioned 6 radicals is unsubstituted or substituted in the cyclic moiety, preferably unsubstituted or substituted by one or more radicals as defined for substituents at the cyclic groups A2, A2a or A2b. [0045] R3,R4,R5 and R6, independently of each other and of R’ and R2, are preferably as defined for R2 or preferably 40 defined for R2. 3 4 5 6 [0046] More preferred R , R , R and R , independently of each other, are H or (C1-C4)alkyl, particularly H. [0047] R3 and R4, together with the N-atom may form a ring and then, independently of NR1R2 are a cyclic group as defined above for R’ and R2 together with the N-atom forming a ring. [0048] X and Y, independently of one another, preferably are each selected from the group consisting of 45 (i) amino, (ii) a group of the formula NR7R8 in which R7 is a radical selected from the group consisting of radicals as defined for and independently of R1, and in which R8 is a radical selected from the group consisting of radicals as defined for and independently of R2, preferably a group of the formula NR7R8 which is defined as the group NR1R2 in formula 50 (I), (iii) hydroxy, (iv) (C1-C4)alkoxy, (C1-C4)haloalkoxy, (C1-C4)a)koxy-(C1-C4)alkoxy and (C1-C4)alkylthio, (v) (C1-C4)alkoxy, (C1-C4)haloalkoxy, (C1-C4)alkoxy-(C1-C4)alkoxy and (C1-C4)alkylthio, wherein each of the latter 4 radicals is substituted by one or more radicals selected from the group consisting of (C3-C6)cycloalkyl, (C3-C6) 55 cycloalkoxy, wherein each of the last-mentioned 2 radicals is unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, hydroxy, carbamoyl, (C1-C4)alkyl, (C1-C4)haloalkyl, (C1-C4)alkoxy-(C1-C4)alkyl, (C1-C4)alkoxy, (C1-C4)haloalkoxy and (C1-C4)alkoxy-(C1-C4)alkoxy,

13 EP 2 231 679 B1

aryl and aryloxy, preferably phenyl or phenoxy, wherein each of the last-mentioned 4 radicals is unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, hydroxy, nitro, carbamoyl, sulfo, (C1-C4)alkyl, (C1-C4)haloalkyl, (C1-C4) alkoxy-(C1-C4)alkyl, (C1-C4)alkoxy, (C1-C4)haloalkoxy, (C1-C4)alkoxy-(C1-C4)alkoxy, (C1-C4)alkylthio, (C1-C4)alkyl- 5 sulfinyl, (C1-C4)haloalkylsulfinyl, (C1-C4)alkylsulfonyl, (C1-C4)haloalkylsulfonyl, di-[(C1-C4)alkyl]-amino, (C1-C4) alkylamino-carbonyl, di-[(C1-C4)alkyl]-amino-carbonyl, (C1-C4)alkylamino-carbonylamino and di-[(C1-C4)alkyl]-aminocarbonylamino, (vi) (C3-C6)cycloalkoxy which is unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, hydroxy, carbamoyl, (C1-C4)alkyl, (C1-C4)haloalkyl, (C1-C4)alkoxy-(C1-C4)alkyl, (C1-C4)alkoxy, 10 (C1-C4)haloalkoxy and (C1-C4)alkoxy-(C1-C4)alkoxy, and (vii) aryloxy, preferably phenoxy, wherein each of the last-mentioned two radicals is unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, hydroxy, nitro, carbamoyl, sulfo, (C1-C4)alkyl, (C1-C4)haloalkyl, 15 (C1-C4)alkoxy-(C1-C4)alkyl, (C1-C4)alkoxy, (C1-C4)haloalkoxy, (C1-C4)alkoxy-(C1-C4)alkoxy, (C1-C4)alkylthio, (C1-C4)alkylsulfinyl, (C1-C4)haloalkylsulfinyl, (C1-C4)alkylsulfonyl, (C1-C4)haloalkylsulfonyl, di-[(C1-C4)alkyl]-amino, (C1-C4)alkylamino-carbonyl, di-[(C1-C4)alkyl]-amino-carbonyl, (C1-C4)alkylamino-carbonylamino and di-[(C1-C4) alkyl]-aminocarbonylamino, and 20 (viii) acyloxy, acylthio or acylamino, preferably acyloxy, wherein the last-mentioned four groups having 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, and wherein acyl in each group preferably is formyl, (C1-C6)alkylcarbonyl, (C1-C6)alkylsulfonyl or optionally substituted arylsulfonyl, more preferably, acyl is acetyl, n- or i-propionyl, n-, iso-, sec- or tert.-butylcarbonyl, or methylsulfonyl, ethylsulfonyl, n-propylsulfonyl, n-butylsulfonyl or phenylsulfonyl the latter of which is unsubstituted or substituted by one or more radicals selected from the group consisting of 25 halogen, (C1-C4)alkyl, (C1-C4)haloalkyl, (C1-C4)alkoxy-(C1-C4)alkyl, (C1-C4)alkoxy, (C1-C4)haloalkoxy, (C1-C4) alkoxy-(C1-C4)alkoxy and (C1-C4)alkylthio, preferably selected from the group consisting of methyl and ethyl,

more preferably X and Y are each selected from the above groups (ii), (iv), (v), (vi), (vii) and (viii), more preferably from the above groups (ii), (iv) and (v), 30 or

X and Y together are a divalent group of the formula

-O-D*-O-, -S-D*-S-, -NH-D*-NH-, -O-D*-NH-, -O-D*-S-, 35

-N(CH3)-D*-N(CH3), -NH-D*-N(CH3)-, -N(C2H5)-D*-N(C2H5)-

40 -NH-D*-N(C2H5)-,

wherein D* in each of the last-mentioned 9 divalent groups is a linear alkylene bridge, a linear (C2-C10)alkenylene bridge, a linear (C2-C10)alkynylene bridge, a (C3-C9)cycloalkylene bridge, a phenylene bridge or a bridge consisting of a combination of two or more of said linear acyclic and cyclic moieties having in total 4 to 18 carbon atoms, 45 wherein the bridge in each case is unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, hydroxy, nitro, carbamoyl, sulfo, (C1-C4)alkyl, (C1-C4)haloalkyl, (C1-C4)alkoxy-(C1-C4)alkyl, (C1-C4)alkoxy, (C1-C4)haloalkoxy, (C1-C4)alkoxy-(C1-C4)alkoxy, (C1-C4)alkylthio, (C1-C4)alkylsulfinyl, (C1-C4) haloalkylsulfinyl, (C1-C4)alkylsulfonyl, (C1-C4)haloalkylsulfonyl, di-[(C1-C4)alkyl]-amino, (C1-C4)alkylamino-carbonyl, di-[(C1-C4)alkyl]-amino-carbonyl, (C1-C4)alkylamino-carbonylamino and di-[(C1-C4)alkyl]-aminocarbonylamino, 50 or

X is a radical as defined above and Y is an organic ligand based on a compound of the formula Y’-H, Y’-RL or RL-O- LL L LL L LL L LL L LL L LL D**-O-R ,R-S-D**-S-R ,R-NH-D**-NH-R ,R-O-D**-NH-R ,R-O-D**-S-R ,R-N(CH3)D**-N(CH3)-R , L LL L LL L LL R -NH-D**-N(CH3)R ,R -N(C2H5)-D**-N(C2H5)-R or R -NH-D**-N(C2H5)-R , wherein D** in each of the 9 last- 55 mentioned compounds is a divalent group as defined for the group D* above, Y’ is a radical as defined for Y, and L LL each of R and R is a radical group selected from the group consisting of (C1-C6)alkyl, hydroxy-(C1-C6)alkyl or (C1-C6)alkoxy-(C1-C6)alkyl, and wherein the organic ligand is coordinated to the aluminium atom of the complex by a free electron pair of a hetero atom contained therein and selected from the group consisting of N, O and S,

14 EP 2 231 679 B1

X and Y together are a radical of the formula -O-D**-O-RLLL, -S-D**-S-RLLL, -NH-D**-NH-RLLL, -O-D**-NH-RLLL, LLL LLL LLL LLL LLL -NH-D**-O-R , -O-D**-S-R , -S-D**-O-R , -N(CH3)-D**-N(CH3)-R , -NH-D**-N(CH3)-R , -N(CH3)-D**- 5 LLL LLL LLL LLL NH-R ,-N(C2H5)-D**-N(C2H5)R , -NH-D**-N(C2H5)-R or -N(C2H5)-D**-NH-R , wherein D* in the 13 last- LLL mentioned radicals is as defined above, and R is a radical selected from the group consisting of (C1-C4)alkyl, hydroxy-(C1-C4)alkyl or (C1-C4)alkoxy-(C1-C4)alkyl, and wherein the radical is additionally coordinated to the aluminium atom of the complex by a free electron pair located at a hetero atom contained in the radical (position represented by Y), preferably located at the heteroatom attached to the group RLLL in the divalent group. 10 [0049] More preferred are compounds (I) in which X and Y, independently of one another, are each selected from the group consisting of

(i) amino, 15 (ii) a group of the fomnula NR7R8 which is defined as the group NR1R2 in formula (I), (iii) hydroxy, (iv) (C1-C6)alkoxy and (C1-C4)alkoxy-(C1-C4)alkoxy, preferably (C1-C4)alkoxy and (C1-C4)alkoxy-(C1-C4)alkoxy in which the O-Atom of the alkoxy group linked directly to the aluminium atom is two carbon atoms away from the O- atom of the terminal alkoxy group; more preferably isopropoxy, 2-butoxy, 2-methoxy-ethoxy, 2-ethoxy-ethoxy, 2- 20 methoxy-1-methyl-ethoxy, 2-ethoxy-1-methyl-ethoxy, (v) (C1-C4)alkoxy, (C1-C4)haloalkoxy, (C1-C4)alkoxy-(C1-C4)alkoxy and (C1-C4)alkylthio, wherein each of the latter 4 radicals is substituted by one or more radicals selected from the group consisting of (C3-C6)cycloalkyl, (C3-C6) cycloalkoxy, wherein each of the last-mentioned 2 radicals is unsubstituted or substituted by one or more radicals selected from the group consisting of (C1-C4)alkyl and (C1-C4)alkoxy, 25 (vi) (C3-C6)cycloalkoxy which is unsubstituted or substituted by one or more radicals selected from the group consisting of (C1-C4)alkyl and (C1-C4)alkoxy, and (vii) phenoxy which is unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, nitro, (C1-C4)alkyl, (C1-C4)haloalkyl, (C1-C4)alkoxy-(C1-C4)alkyl, (C1-C4)alkoxy, (C1-C4)haloalkoxy, 30 (C1-C4)alkoxy-(C1-C4)alkoxy, (C1-C4)alkylthio, (C1-C4)alkylsulfinyl, (C1-C4)alkylsulfonyl, di-[(C1-C4)alkyl]-amino, and (viii) acyloxy, acylthio or acylamino, preferably acyloxy, wherein the last-mentioned four groups having 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, and wherein acyl in each group preferably is formyl, (C1-C6)alkylcarbonyl or (C1-C6)alkylsulfonyl or phenylsulfonyl, 35 the latter of which is unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, (C1-C4)alkyl and (C1-C4)alkoxy, more preferably, acyl is acetyl, n- or i-propionyl, n-, iso-, sec- or tert.-butylcarbonyl, or methylsulfonyl, ethylsulfonyl, n-propylsulfonyl, n-butylsulfonyl, phenylsulfonyl, o-, m- or p-tolylsulfonyl, more preferably X and Y are each selected from the above groups (ii), (iv), (v), (vi), (vii) and (viii), more preferably from the above groups (ii), (iv) and (v), or 40 X and Y together are a divalent group of the formula -O-D*-O-, -S-D*-S-, -NH-D*-NH-, -O-D*-NH-, wherein D* in each of the last-mentioned 4 divalent groups is a linear alkylene bridge, a linear (C2-C6)alkenylene bridge, a linear (C2-C6)alkynylene bridge, a (C3-C6)cycloalkylene bridge, a 1,2-phenylene bridge or a bridge consisting of a combination of two or more of said linear acyclic and cyclic moieties having in total 4 to 12 carbon atoms, wherein the bridge in each case is unsubstituted or substituted by one or more radicals selected from the group consisting of 45 halogen, hydroxy, (C1-C4)alkyl, (C1-C4)alkoxy-(C1-C4)alkyl, (C1-C4)alkoxy, (C1-C4)alkoxy-(C1-C4)alkoxy, (C1-C4) alkylsulfonyl and di-[(C1-C4)alkyl]-amino; or X is a radical as defined above and Y is an organic ligand based on a compound of the formula Y’-H, Y’-RL or RL-O- D**-O-RLL, RL-S-D**-S-RLL, 50 RL-NH-D**-NH-RLL, RL-O-D**-NH-RLL, RL-O-D**-S-RLL, L LL L LL R -N(CH3)-D**-N(CH3)-R , R -NH-D**-N(CH3)-R , L LL L LL R -N(C2H5)-D**-N(C2H5)-R or R -NH-D**-N(C2H5)-R , wherein D** in each of the 9 last-mentioned compounds is a divalent group as defined for the group D* above, Y’ L LL is a radical as defined for Y, and each of R and R is a radical group selected from the group consisting of (C1-C6) 55 alkyl, hydroxy-(C1-C4)alkyl or (C1-C4)alkoxy-(C1-C4)alkyl, and wherein the organic ligand is coordinated to the aluminium atom of the complex by a free electron pair of a hetero atom contained therein and selected from the group consisting of N, O and S, or

15 EP 2 231 679 B1

X and Y together are a radical of the formula -O-D**-O-RLLL, -S-D**-S-RLLL, -NH-D**-NH-RLLL, -O-D**-NH-RLLL, LLL LLL LLL LLL LLL -NH-D**-O-R , -O-D**-S-R , -S-D**-O-R , -N(CH3)-D**-N(CH3)-R , -NH-D**-N(CH3)-R , -N(CH3)-D**- LLL LLL LLL LLL NH-R ,-N(C2H5)-D**-N(C2H5)R , -NH-D**-N(C2H5)-R or -N(C2H5)-D**-NH-R , wherein D* in the 13 last- LLL mentioned radicals is as defined above, and R is a radical selected from the group consisting of (C1-C4)alkyl, 5 hydroxy-(C1-C4)alkyl or (C1-C4)alkoxy-(C1-C4)alkyl, and wherein the radical is additionally coordinated to the aluminium atom of the complex by a free electron pair located at a hetero atom contained in the radical (position represented by Y), preferably located at the heteroatom attached to the group RLLL in the divalent group.

[0050] Further preferred are compounds (I) in which 10 R1, X and Y are as defined above, R2 is hydrogen, R3 is hydrogen, R4 is hydrogen, 15 R5 is hydrogen and R6 is hydrogen.

[0051] From Al27-NMR studies it has been shown that the stereochemical structure of the aluminium complex depends on the ligands X and Y and ligands present in solutions of compounds (I) that in the case that X and Y or other ligands 20 with oxygen atoms are linked to the aluminium atom that the aluminium atom is tetrahedral 4-coordinated or also 5- coordinated, as is known from other cases in aluminium chemistry (see Scheme 2, showing the case for R3 to R5 each being H).

45 [0052] In mono-coordinating solvents such as simple alcohols, for example: methanol, ethanol, isopropanol, 1-butanol, 2-butanol etc. the complex may be variably monomeric or dimeric in nature, depending on the complex concentration in solution or whether the complex is in the solid form (Scheme 3, showing case for R3 to R6 each being H):

16 EP 2 231 679 B1

[0053] In the presence of more complex solvents which are capable of offering a second coordination site, for example alkoxyalcohols, the complex has been shown (e. g. by H1-NMR and IR) to be monomeric (Scheme 4), and thus being chiral at the aluminium centre. For example, in the presence of 2-ethoxyethanol the aluminium complex formed is shown 20 in Scheme 4, wherein X = O, R" = Et and R’ = R = H and 1-methoxy-2-propanol X = O, R" = R = Me, R" = H, and R4 to R6 in formula (I) are H (only one diastereoisomer at the aluminium centre is shown).

[0054] Each structure shown in schemes 1 through 4 is a non limiting graphical representation of all tautomeric isomers of that structure. Furthermore, if the coordinating solvent is chiral then diastereomeric mixtures of complexes may be 40 formed in varying ratios. [0055] Another object of the invention is a process for the preparation of bisguanidine-aluminium complexes of the formula (I) or salts thereof,

in which R1 to R6 and X and Y are as defined above, 55 characterized in that a compound (an amine) of the formula (II) or a salt thereof,

17 EP 2 231 679 B1

in which R1 and R2 are defined as in the compound of formula (I) to be prepared, is reacted to a compound of the formula (III) or a salt thereof,

in which R3,R4,R5 and R6 are defined as in the compound of formula (I) to be prepared, and an aluminium(III) source, optionally, in the presence of a protic additive or solvent selected from the group consisting of alcohols or amines, 20 preferably an aluminium(III) source selected from

(i) aluminium salts of the formula (IV),

30 in which X and Y are as defined in the compound of formula (I) to be prepared, and Z, independently of X, is a leaving group selected from the group of radicals as defined for X or Y, or

(ii) aluminium salts of the formula (IV’), 35

40 in which X’, Y’ and Z’ each are selected from the group consisting of radicals as defined for X, Y or Z, respectively and radicals which generate said group X, Y or Z, respectively in the presence of a protic additive or solvent X-H, Y-H or Z-H, respectively, with the proviso that 1, 2 or 3 of the radicals X’, Y’ and Z’ are selected from said radicals which 45 generate radicals X, Y and Z, respectively, in combination with a protic additive or solvent X-H, Y-H or Z-H wherein each of X, Y and Z are defined as set forth for X and Y in formula (I), and addition salts thereof.

[0056] Preferably, the amines of formula (II) are monoamines. If the amines of formula (II) contain another primary or 50 secondary amino group this group may react like the first amino group with the compound of formula (III). In such a case, preferably in case of a diamine with two primary amino groups and where both amino groups react, the compound of formula (I) is obtained where R1 is a group of the formula (B1). Suitable radicals X, Y and Z in compounds (IV) are selected from the group consisting of radicals (i), (ii), (iii), (iv), (v), (vi) and (vii) set forth above for X and Y of the compounds of formula (I). 55 [0057] Suitable radicals X’, Y’ and Z’ in formula (IV’) which generate a radical X, Y and Z in the presence of a protic additive or solvent are H, halogen, (C1-C18)alkyl which is unsubstituted or substituted, preferably which is unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, (C1-C6)alkoxy, (C3-C6)cycloalkyl, aryl and substituted aryl, or is aryl which is unsubstituted or substituted, preferably which is unsubstituted or substituted

18 EP 2 231 679 B1

by one or more radicals selected from the group consisting of halogen, (C1-C6)alkyl and (C1-C6)alkoxy, and the protic additive or solvent is selected from the type X-H, Y-H or Z-H where X, Y and Z are as defined for X or Y, or preferably defined for X or Y, in the compound (I). Such protic additives are of the type HO-alkyl, HO-aryl, HO-alkylaryl, 1 2 1 2 NH3 or HNR R to generate groups X, Y and Z of the type -O-alkyl, -O-aryl, -0-alkylaryl, -amino or-NR R , respectively. 5 [0058] Suitable radicals X’, Y’ and Z’ in formula (IV’) which generate a radical X, Y and Z in the presence of a protic additive or solvent preferably are H, halogen, cyano, (C1-C6)alkyl which is unsubstituted or substituted, preferably which is unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, (C1-C6)alkoxy, (C3-C6)cycloalkyl, phenyl and substituted phenyl (preferably phenyl substituted by one or more radicals selected from the group consisting of halogen, 10 (C1-C6)alkyl and (C1-C6)alkoxy), or are phenyl which is unsubstituted or substituted, preferably which is unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, (C1-C6)alkyl and (C1-C6)alkoxy. [0059] Suitable radicals X’, Y’ and Z’ in formula (IV’) which generate a radical X, Y and Z in the presence of a protic additive or solvent are also those selected from the group consisting of radicals (i), (ii), (iii), (iv), (v), (vi) and (vii) set forth 15 above for X and Y of the compounds of formula (I) if they are used in combination with a protic additive or solvent of the type X-H, Y-H or Z-H if the group X, Y and Z in the protic additive or solvent is more nucleophilic than X’, Y’ or Z’ in the compound of formula (IV’) or if the protic additive or solvent is present in a large excess so that an exchange of the ligands occurs. [0060] Suitable compounds of formula (IV) are aluminium trimethoxide [Al(OCH3)3] aluminium triethoxide [Al(OC2H5)3], 20 aluminium tri(n-propoxide) [Al(O-n-C3H7)3], aluminium tri(i-propoxide) [Al(O-i-C3H7)3], aluminium tri(n-butoxide) [Al(O- n-C4H9)3], aluminium tri(sec-butoxide) [Al(O-sec-C4H9)3], aluminium tri(i-butoxide) [Al(O-i-C4H9)3], aluminium tri(tert- butoxide) [Al(O-tert-C4H9)3], aluminium tri(2-methoxy-ethoxide) [Al(O-CH2CH2-O-CH3)3], aluminium tri(2-ethoxy-ethoxide) [Al(O-CH2CH2-O-C2H5)3], aluminium tri(2-methoxy-1-methyl-ethoxide) [Al(O-CH(CH3)CH2-O-CH3)3], aluminium tri (2-ethoxy-1-methyl-ethoxide) {Al[O-CH(CH3)CH2-O-C2H5]3}, or aluminium compounds with mixed radicals such as Al 25 (OCH3)2(OC2H5), Al(OCH3)(OC2H5)2, Al(OCH3)(O-n-C3H7)2, Al(OCH3)2(O-n-C3H7), Al(OC5H5)(O-n-C3H7)2,Al (OC2H5)2(O-n-C3H7), Al(OCH3)(O-i-C3H7)2, Al(OCH3)2(O-i-C3H7), Al(OC2H5)(O-i-C3H7)2, Al(OC2H5)2(O-i-C3H7). [0061] The above compounds (IV) are also suitable aluminium(III) sources of the formula (IV’) in the presence of a protic additive or solvent selected from alcohols and/or amines of the type X-H, Y-H or Z-H. [0062] Additionally suitable compounds (IV’) which are used in the presence of a protic additive or solvent selected 30 from alcohols and/or amines of the type X-H, Y-H or Z-H are aluminium compounds such as trimethylaluminium [Al (CH3)3], triethylaluminium [Al(C2H5)3], triphenylaluminium [Al(C6H5)3], aluminium hydrides and addition salts thereof such as aluminiumhydride [AlH3], lithiumaluminiumhydride [LiAlH4], alkylaluminiumhydrides such as (CH3)AlH2, (CH3)2AlH, (C2H5)AlH2,(C2H5)2AlH, (n-C3H7)AlH2, (n-C3H7)2AlH, (i-C3H7)AlH2, (i-C3H7)2AlH, (n-C4H9)AlH2, (n- C4H9)2AlH, (sec-C4H9)AlH2, (sec-C4H9)2AlH, (i-C4H9)AlH2, (i-C4H9)2AlH [DIBAL], 35 [0063] The reaction can also be performed in substance or in the presence of a solvent or mixtures of solvents. As mentioned above some of the solvents may function as a reactant to form a ligand of the aluminium complex. [0064] Suitable solvents are for example but not limited to:

Organic solvents selected from the group consisting of the chemical class of 40 - ethers, such as dialkylethers (e. g. diethylether) or cyclic aliphatic ethers (e. g. tetrahydrofuran), - saturated or unsaturated aliphatic hydrocarbons, which may be unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, nitro and alkoxy, preferably (C1-C4)alkoxy, i.e. solvents such as alkanes, alkenes, haloalkanes, nitroalkanes, 45 - aromatic hydrocarbons, which may be unsubstituted or substituted by one or more radicals selected from the group consisting of alkyl (preferably (C1-C4)alkyl), alkoxy (preferably (C1-C4)alkoxy), halogen and nitro, i.e. solvents such as aromates, alkylaromates, haloaromates, nitroaromates, alkoxyaromates, - alcohols, particularly aliphatic alcohols, such as alkanoles, ω-dioles or ω-polyoles, which may be unsubstituted or substituted, preferably unsubstituted or substituted by one or more radicals from the group consisting of 50 alkoxy (preferably (C1-C4)alkoxy), halogen, nitro, amino, (C1-C4)alkylamino, and di-[(C1-C4)alkyl]-amino, - heteroaromates, such as heteroaromatic compounds having 5 or 6 ring atoms and 1 or 2 heteroatoms, particularly 1 heteroatom, selected from the group consisting of N, O and S, such as pyridine or thiophene, - sulfones, such as sulfolane, - sulfoxides, such as dimethylsulfoxide and 55 - amines, such as monoamines, diamines or polyamines.

[0065] Preferred are alcohols or mixtures which include an alcohol or alkoxyalcohol are preferred, such as, propanol, isopropanol, isobutanol, cyclohexanol, 2-ethoxy-ethan-1-ol, 2-methoxy-ethan-1-ol, 2-isopropoxy-ethan-1-ol, 2-methoxy-

19 EP 2 231 679 B1

1-methyl-ethan-1-ol (= 1-methoxy-isopropanol), 2-ethoxy-1-methyl-ethan-1-ol (= 1-ethoxy-isopropanol). These solvents may also function as protic additives/solvents which determine the ligands of the aluminium complex. [0066] The process of complex formation can be performed at relatively moderate temperatures such as between 50˚C and 140˚C and preferably between 70˚C and 130˚C and especially between 90 and 120˚C. 5 [0067] The complex formation preferably is performed with 0.1 to 10.0 equivalents cyanoguanidine of formula (III), more preferably with 1.0 to 3.0 equivalents cyanoguanidine of formula (III). more preferably with 1.0 to 2.0 equivalents of the cyanoguanidine and especially with 1.0 to 1.6 equivalents of the cyanoguanidine, based on 1 equivalent of compound (II) (amine) or salt thereof. [0068] The complex formation is preferably performed with 0.1 to 10.0 equivalents of the aluminium reagent of the 10 formula (IV), more preferably with 1.0 to 3.0 equivalents of the aluminium reagent of the formula (IV), more preferably with 1.0 to 2.0 equivalents of the aluminium reagent and especially with 1.0 to 1.6 equivalents of the aluminium reagent, based on 1 equivalent of compound (II) or salt thereof. [0069] It is known already from Anorg. Chemie, Org. Chemie, Biochem, Biophys., Biol, 347, 1974 that the unsubstituted aluminium biguanidine complex can be prepared from aluminium chloride (AlCl3) and biguanidine (C2N5H7). The prep- 15 aration of substituted complexes has not been known so far. [0070] The compounds of formula (I) or salts thereof (in short "compounds (I)") are aluminium complexes of biguanides and are suitable as intermediates for the preparation of products which otherwise can be prepared also by reaction of the respective free biguanides. [0071] The compounds (I) are preferably suitable for the preparation of heterocyclic compounds, where the aluminium 20 atom is replaced with an optionally substituted carbon atom or heteroaromatic derivatives thereof, such as s-triazines. [0072] Another object of the invention is thus the use of compounds of formula (I) or salts thereof for the preparation of heterocyclic compounds corresponding to formula (I), wherein the aluminium group Al(X)(Y) is replaced with an optionally substituted carbon atom or s-triazine derivatives thereof. [0073] For example, the latter heterocyclic compounds can be prepared by reacting compounds of formula (I) or salts 25 thereof with ketones, wherein the triazine ring is formed by incorporating the carbon atom of the ketone carbonyl group and the oxygen atom of the carbonyl group of the ketone is replaced with the substituted biguanide moiety contained in the compound of formula (I); see, for example, analogous reaction from biguanide and ketone according to J. Med. Chem. 1985, 28, 1728-1740. [0074] More preferred are preparations of heteroaromatic compounds, particularly s-triazines, using compounds (I) 30 in which R5 and R8 are hydrogen. [0075] The novel biguanidino-aluminium complexes of formula (I) and salts thereof (= salts, dimers and polymers thereof) are particularly suitable for the preparation of N-substituted 2,4-diamino-s-triazines by the process as described below. [0076] Another object of the present invention is thus a process for the preparation of compounds of the formula (V) 35 or salts thereof,

45 in which R1, R2, R3 and R4 are as defined above, and Q is 50

a) hydrogen, (C1-C12)alkyl, (C2-C12)alkenyl or (C2-C12)alkynyl, more preferably (C1-C6)alkyl, (C2-C6)alkenyl or (C2-C6)alkynyl, wherein each of the last-mentioned six radicals is unsubstituted or substituted, preferably unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, hydroxy, -CN, -NO2, -OCN, -SCN, amino, carbamoyl, (C1-C6)alkoxy, (C1-C6)haloalkoxy, (C1-C6)alkoxy-(C1-C6)alkoxy, (C1-C6)alkylthio, 55 (C1-C6)alkylsulfinyl, (C1-C6)haloalkylsulfinyl, (C1-C6)alkylsulfonyl, (C1-C6)haloalkylsulfonyl, (C1-C4)alkyl-amino, di-[(C1-C4)alkyl]-amino, (C1-C4)alkylamino-carbonyl, di-[(C1-C4)alkyl]-amino-carbonyl, (C1-C4)alkylamino-carbonylamino and di-[(C1-C4)alkyl]-amino-carbonylamino, oxo, thiooxo, imino, N-(C1-C6)alkyl-imino, N-[phenyl-(C1-C4) alkyl]-imino, N-(C3-C6)cycloalkyl-imino, N-[(C3-C6)cycloalkyl-(C1-C4)alkyl]-imino, [(C1-C6)alkoxy]-carbonyl, (C3-C6)

20 EP 2 231 679 B1

cycloalkyl, (C5-C6)cycloalkenyl, phenyl, naphthyl, heterocyclyl, benzocondensated heterocycyl, benzo-(C5-C6)cycloalkyl, benzo-(C5-C6)cycloalkenyl, (C3-C6)cycloalkoxy, benzo-(C5-C6)cycloalkoxy, (C5-C6)cycloalkenyloxy, benzo-(C5-C6)cycloalkenyloxy, phenoxy, naphthoxy, phenylthio, heterocyclyloxy, benzocondensated heterocyclyloxy, heterocyclylthio, and benzocondensated heterocyclylthio 5 wherein each of the last-mentioned 19 radicals is unsubstituted or substituted in the cyclic moiety by one or more radicals selected from the group consisting of halogen, hydroxy, -CN, NO2, -OCN, -SCN, amino, carbamoyl, (C1-C4) alkyl, (C1-C4)haloalkyl, (C1-C4)alkoxy-(C1-C4)alkyl, (C1-C6)alkoxy, (C1-C4)haloalkoxy, (C1-C4)alkoxy-(C1-C4) alkoxy, (C1-C4)alkylthio, (C1-C4)alkylsulfinyl, (C1-C4)haloalkylsulfinyl, (C1-C4)alkylsulfonyl, (C1-C4)haloalkylsulfonyl, (C1-C4)alkyl-amino, di-[(C1-C4)alkyl]-amino, (C1-C4)alkylamino-carbonyl, di-[(C1-C4)alkyl]-amino-carbonyl and 10 (C1-C4)alkylamino-carbonylamino, or, preferably, is hydrogen, (C1-C6)alkyl, (C1-C6)haloalkyl, hydroxy-(C1-C6)alkyl or (C1-C6)alkoxy-(C1-C6)alkyl; more preferably is (C1-C4)alkyl or (C1-C4)haloalkyl, hydroxy-(C1-C4)alkyl or (C1-C4) alkoxy-(C1-C4)alkyl; more preferably is (C1-C4)haloalkyl, b) or is (C3-C6)cycloalkyl, benzo-(C5-C6)cycloalkyl, (C5-C6)cycloalkenyl, benzo-(C5-C6)cycloalkenyl, phenyl, naph- 15 thyl, heterocyclyl, benzocondensated heterocycyl, wherein each of the last-mentioned 8 radicals is unsubstituted or substituted in the cyclic moiety, preferably unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, hydroxy, -CN, -NO2, -OCN, -SCN, amino, carbamoyl, (C1-C4)alkyl, (C1-C4)haloalkyl, (C1-C4)alkoxy-(C1-C4)alkyl, (C1-C4)alkoxy, (C1-C4) haloalkoxy, (C1-C4)alkoxy-(C1-C4)alkoxy, (C1-C4)alkylthio, (C1-C4)alkylsulfinyl, (C1-C4)haloalkylsulfinyl, (C1-C4) 20 alkylsulfonyl, (C1-C4)haloalkylsulfonyl, (C1-C4)alkyl-amino, di-[(C1-C4)alkyl]-amino, (C1-C4)alkylamino-carbonyl, di-[(C1-C4)alkyl]-amino-carbonyl, (C1-C4)alkylamino-carbonylamino and di-[(C1-C4)alkyl]-amino-carbonylamino, [(C1-C6)alkoxy]-carbonyl, (C3-C6)cycloalkyl, (C5-C6)cycloalkenyl, phenyl, naphthyl, heterocyclyl, (C3-C6)cycloalkoxy, (C5-C6)cycloalkenyloxy, phenoxy, naphthoxy, phenylthio, heterocyclyloxy and heterocyclylthio, 25 wherein each of the last-mentioned 12 radicals is unsubstituted or substituted in the cyclic moiety by one or more radicals selected from the group consisting of halogen, hydroxy, -CN, NO2, -OCN, -SCN, amino, carbamoyl, (C1-C4) alkyl, (C1-C4)haloalkyl, (C1-C4)alkoxy-(C1-C4)alkyl, (C1-C6)alkoxy, (C1-C4)haloalkoxy, (C1-C4)alkoxy-(C1-C4) alkoxy, (C1-C4)alkylthio, (C1-C4)alkylsulfinyl, (C1-C4)haloalkylsulfinyl, (C1-C4)alkylsulfonyl, (C1-C4)haloalkylsulfonyl, (C1-C4)alkyl-amino, di-[(C1-C4)alkyl]-amino, (C1-C4)alkylamino-carbonyl, di-[(C1-C4)alkyl]-amino-carbonyl and 30 (C1-C4)alkylamino-carbonylamino, and, in case of heterocyclyl, also oxo attached to heteroring atoms N or S or in alpha-position of an N-atom as heteroring atom, or, preferably, is (C3-C6)cycloalkyl which is unsubstituted or substituted by one or more radicals selected from the group consisting of halogen and (C1-C4)alkyl, 35 c) or is COR, COOR, C(=S)R, C(=O)SR, C(=S)OR, C(=S)SR, wherein R in each of the 6 last-mentioned radicals being (C1-C18)alkyl, (C3-C6)cycloalkyl or phenyl, the latter three radicals being unsubstituted or substituted, preferably unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, CN, nitro, (C1-C6)alkoxy, (C1-C4)haloalkoxy. (C1-C4)alkoxy-(C1-C4)alkoxy, (C1-C4)alkylthio and in case of cyclic basic radicals also (C1-C4)alkyl, (C1-C4)haloalkyl and (C1-C4)alkoxy-(C1-C4)alkyl, or is CONR’R" or C(=S)NR’R", wherein each of 40 R’ and R" in the two last-mentioned radicals, independently of each other, being hydrogen, (C1-C18)alkyl, (C3-C9) cycloalkyl or phenyl, the latter three radicals being unsubstituted or substituted, preferably unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, CN, nitro, (C1-C6)alkoxy, (C1-C4) haloalkoxy, (C1-C4)alkoxy-(C1-C4)alkoxy, (C1-C4)alkylthio and in case of cyclic basic radicals also (C1-C4)alkyl, (C1-C4)haloalkyl and (C1-C4)alkoxy-(C1-C4)alkyl, or 45 R’ and R" together with the nitrogen atom form a 3 to 6-membered heterocyclic ring which can contain one or two additional hetero atoms selected from N, O and S, and which is unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, CN, (C1-C4)alkyl, (C1-C4)haloalkyl, (C1-C4)alkoxy-(C1-C4)alkyl, (C1-C4)alkoxy, (C1-C4)haloalkoxy, (C1-C4)alkoxy-(C1-C4)alkoxy and (C1-C4)alkylthio,

50 characterized in that a compound of the formula (I) or a salt thereof

21 EP 2 231 679 B1

10 in which R1, R2, R3 and R4 are as defined in the compound of formula (V) to be prepared and R5 and R6 are hydrogen, is reacted with a compound of the formula (VI)

15 Q-W* (VI)

in which

Q is as defined in the compound of formula (V) to be prepared and 20 W* is a carbon atom which bears 3 additional bonds to 1, 2 or 3 leaving groups which are linked by hetero atoms, preferably heteroatoms selected from the group consisting of O, N, F, Cl, Br, I, S, P, Si and metal atoms, (i. e. the carbon atom is linked to 3 leaving groups, each via a single bond, linked to two leaving groups via a single bond and a double bond, respectively, and is linked to one leaving group via a triple bond), and is preferably the functional group 25 -CO-X1 (acid halide group, X1 = F, Cl, Br), -CO-CN (acyl nitrile group), -CO-O-COR* (anhydride, R* = Q or R), 2 -CO-O-X (O)n(OmR)t (mixed anhydride, X = S, P, B, n = 0, 1, 2, 3, m = 0, 1,2,t=1,2), -CO-O-R (ester group), 30 -CO-O-N=R (acyloxime group) -CO-NR’R" (amide group, R’, R" = H, OR, NR, SR or R, or R’ and R" form a ring), -CN (nitrile group), -C(=NR’)NR" (amidine group, R’, R" = H or R, or R and R’ form a ring), -C(=NH)OR (iminoether, imidacid esters), 35 -C(=NR’)OR (iminiumether R’ = R (independently)), -C(=O)SR or -C(=S)OR or -C(=S)SR (thio ester), -C(=S)NR’R" or -C(=NR’)SR (thio amide or iminothioether R’, R" = H or R, or R and R’ form a ring or R’ and R" form a ring) -C(=NR)X1 (haloimidate group, X = F, Cl, Br), -C(=N+RR’)X1- (haloimidium group, R’ = R (independently), or R and R’ form a ring, X1 = F, Cl-, Br-), 40 -C(-OR)(-OR’)X1 (haloacetal group, R’ = R (independently or R and R’ form a ring, X1 = F, Cl, Br), wherein in each subformula group of W* the group R being (C1-C18)alkyl, (C3-C6)cycloalkyl or phenyl, the latter three radicals being unsubstituted or substituted, preferably unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, CN, nitro, (C1-C6)alkoxy, (C1-C4)haloalkoxy, (C1-C4)alkoxy-C4)alkoxy, (C1-C4) alkylthio and in case of cyclic basic radicals also (C1-C4)alkyl, (C1-C4)haloalkyl and (C1-C4)alkoxy-C4)alkyl, 45 and in case of a ring formed by R and R’ or R’ and R" the ring having preferably 3 to 6 ring atoms and being unsubstituted or subsituted by one or more radicals selected from the group consisting of halogen, CN, (C1-C4)alkyl, (C1-C4)haloalkyl, (C1-C4)alkoxy-(C1-C4)alkyl, (C1-C4)alkoxy, (C1-C4)haloalkoxy, (C1-C4)alkoxy-(C1-C4)alkoxy and (C1-C4)alkylthio,

to give the compound of the formula (V) or a salt thereof. 50 [0077] The triazine formation can also be performed in substance or in the presence of a solvent or mixture of solvents, preferably non-aqueous solvent or solvent mixture, for example in an organic solvent or solvent mixture, which have been mentioned above as suitable for the preparation of compounds of formula (I) too. [0078] Preferred as solvents are alcohols or mixtures which include an alcohol, preferably an alcohol such as methanol, ethanol, propanol, isopropanol, butanol, iso-butanol, tert-butanol, pentanol, hexanol and cyclohexanol and mixtures 55 thereof, more preferably methanol, ethanol, propanol or butanol and mixtures thereof. [0079] The triazine formation preferably is performed between -20˚C and 140˚C, more preferably between 0˚C and 120˚C and especially between 20˚C and 100˚C. [0080] The triazine formation preferably is performed with 1.0 to 10 equivalents, more preferably with 1.0 to 3.0

22 EP 2 231 679 B1

equivalents of the species Q-W, more preferably with 1.0 to 2.0 equivalents of the species Q-W and especially with 1.0 to 1.6 equivalents of the species Q-W, based on 1 equivalent of compound (I) or salt thereof. [0081] The triazine formation can also be performed without or preferably in the presence of one or more additives selected from the group consisting of bases and compounds having polar funtional groups such hydroxy or amino groups 5 the latter two of which are polar but not particularly basic. The additive often helps in speeding up the reaction, improving the yield, providing the reaction to be performed cleaner and/or at a lower temperature compared to the reaction without the additive. [0082] The following bases can be used as additives for example but not limited to:

10 a) salts such as an alkoxylate (alkoxide), carbonate, hydrogencarbonate, fluoride, phosphate, hydrogenphosphate, dihydrogenphosphate or hydroxide, where the counter-ion can be a cation of metal derived from metals, for example, alkali metals such as lithium, sodium, potassium, cesium (= caesium), or alkaline earth metals such as magnesium, calcium, or other metals such as aluminium, 15 or the counter-ion can be ammonium, phosphonium, ammonium or phosphonium substituted by organic groups or can be another organic cation, b) a tertiary or aromatic amine or mixtures thereof,

[0083] Reaction mixtures which include one or more alkoxides selected from the group consisting of metal methoxide, 20 metal ethoxide, metal propoxide, metal isopropoxide, metal butoxide, metal iso-butoxide and metal tert-butoxide are especially preferred as base. [0084] The alkoxide, when present, is used preferably in an amount of 0.01 to 5 equivalents and preferably between 0.01 to 2 equivalents, based on 1 equivalent of compound of formula (I) or salt thereof. [0085] The triazine formation can also be performed in the presence of one or more compounds having polar (functional) 25 groups which are of less basic nature than said alkoxides above. Such compounds are preferably selected from the group consisting of polyols, aminoalcohols and polyamines. [0086] Examples for compounds having polar groups are the following compounds including all of their isomers:

ethanediol, propandiol, propantriol, aminoethanol, N-mono- and N,N-disubstituted-aminoethanol, aminopropanol, 30 N-mono- and N,N-disubstituted-aminopropanol, butandiol, butantriol, aminobutanol, N-mono- and N,N-disubstituted-aminobutanol, diethanolamine, N-substituted-diethanolamine, triethanolamine, dipropanolamine, N-substituted- dipropanolamine, ethanediamine, mono-, di-, tri- or terta-substituted-ethanediamine, propanediamine and mono-, di-, tri- and tetra-substituted-propanediamine, preferably ethanediol, propanediol and butanediol, and mixtures thereof. Especially preferred are 1,2-ethanediol, 1,2-propanediol, 1,2-butanediol and 1-methyl-1,2-propanediol, 1,4-bu- 35 tanediol.

[0087] The substance with polar groups, when present, preferably is used in an amount of from 0.01 to 20 equivalents, more preferably of from 0.01 to 10 equivalents and especially of from 0.01 to 5 equivalents, based on 1 equivalent of compound (I) or salt thereof. 40 [0088] The triazine formation can also be performed in the presence of both, one or more base and one or more substances with polar groups, of which mixtures which include one or more of ethanediol, propanediol or butanediol and one or more (metal) methoxide, ethoxide, propoxide, isopropoxide, butoxide, iso-butoxide and tert-butoxide are preferred. [0089] The substance having polar groups, such as the diol, aminoalcohol or diamine, and the (metal) alkoxide often works synergistically resulting in reactions which are quicker and/or cleaner and/or may progress at a lower temperature 45 than may be achieved by either reagent separately. [0090] The triazine formation can also be performed in the presence of an additional salt which may act as a dehydrating agent, for example but not limited to:

sodium sulfate (Na2SO4), calcium sulfate (CaSO4), calcium halides (CaCl2, CaBr2), magnesium sulfate (MgSO4), 50 magnesium halides (MgCl2, MgBr2). The additional salt is preferably used in stoichiometric or sub-stoichiometric quantities based on the amount of compound of formula (I).

[0091] The triazine formation can also be performed in the presence of a zeolite, clay or other water absorbing substance which may act as a dehydrating agent. 55 [0092] The triazine formation can also be performed in the presence of one or more of the above mentioned additives. [0093] The amine of the formula (II) can also be used in the form of the free base or as a salt or mixed salt of an acid such as, for example: HF, HCl, HBr, HI, H2SO4,H3PO4, RSO3H, RSO2H, RPO3H2, or a complex with AlX3,BX3,CO2, SO2,SO3,PX3, POX3,PX5, SiX4 where X is halogen, a halogen analogue, alkyloxy, aryloxy, alkylamino, alkylarylamino

23 EP 2 231 679 B1

or arylamino or derivatives thereof, where the alkyl groups having 1 to 6 carbon atoms are preferred, and aryl being phenyl is preferred. [0094] The salt of the amine (II) can optionally be used together with the addition of an equivalent amount or less or more than equivalent amount of an organic or inorganic base, preferably a non-aqueous base. 5 [0095] The process for the formation of the triazine can be combined directly with the process for preparing the Al- complex of formula (I) without isolation (or purification) of the compound of formula (I), optionally in a one-pot process. [0096] Preferably, the invention provides a process for the preparation of compounds of formula (V) or salts thereof, characterized in that

10 (a) a compound of the formula (II) or a salt thereof,

in which R1 and R2 are defined as in the compound of formula (V) to be prepared, is reacted to a compound of the formula (IIIa) or a salt thereof, 20

in which R3 and R4 are defined as in the compound of formula (I) to be prepared, 30 and an aluminium(III) source, optionally, in the presence of a protic additive or solvent selected from the group consisting of alcohols or amines, preferably an aluminium(III) source selected from

(i) aluminium salts of the formula (IV),

40 in which X and Y are as defined in the compound of formula (I) to be prepared, and Z, independently of X, is a leaving group selected from the group of radicals as defined for X or Y, or

45 (ii) aluminium salts of the formula (IV’),

in which X’, Y’ and Z’ each are selected from the group consisting of radicals as defined for X, Y or Z, respectively and 55 radicals which generate said group X, Y or Z, respectively in the presence of a protic additive or solvent X-H, Y-H or Z-H, respectively, with the proviso that 1, 2 or 3 of the radicals X’, Y’ and Z’ are selected from said radicals which generate radicals X, Y and Z, respectively, in combination with a protic additive or solvent X-H, Y-H or Z-H wherein each of X, Y and Z are defined as set forth for X and Y in formula (I),

24 EP 2 231 679 B1

and addition salts thereof, to give a compound of the formula (Ia) or a salt thereof,

in which R1,R2,R3 and R4, are defined as in the compound of formula (V) to be prepared, and in which Y is as 15 defined in formula (I) further above, and

(b) the compound of formula (I) obtained in step (a), optionally without isolation and purification, is reacted with a compound of the formula (VI)

20 Q-W* (VI)

in which Q is defined as for Q in formula (V) to be prepared, and W* is defined formula (VI) defined further above, to give a the compound of the formula (V) or a salt thereof.

25 [0097] The process for the preparation of compounds (V) via compounds (I) proceeds with high yield and purity at moderate reaction conditions. [0098] In the following non-limiting examples the amounts and percentages are related to weight unless defined otherwise specifically.

30 A) Preparation examples

[0099] Abbreviations used in the examples:

hr(s) = hour(s) 35 ml = milliliter mp = melting point

A1) 4-Morpholino-6-[(1S)-1-chloroethyl]-1,3,5-triazine-2-amine

40 [0100] A1a) A mixture of 108 g morpholine, 163 g cyanoguanidine, 347 g aluminium isopropoxide and 267 g 1-methoxy- 2-propanol were stirred under nitrogen and heated to 90 ˚C for 22,5 hrs (see example la-1.181 of Table II). [0101] A1 b) The reaction mixture obtained in A1a was cooled to 70 ˚C, and 530 g methanol was added carefully. After complete addition 178 g methyl (2S)-2-chloro-propionate was added. After 22 hrs at 70 ˚C the internal the reaction mixture was added to 2400 ml 10% acetic acid at 70 ˚C. Low boiling solvents were removed under a light vacuum (840 45 ml). The suspension was then cooled to 30 ˚C, filtered and washed with 2 x 240 g 10% acetic acid and then 2 x 480 g water. The solid was then dried in vacuo. Product: 199 g, yield 68%, mp: 177-8˚C (see example V-1 of Table 1).

A2) N-Benzyl-6-[(S)-1-hydroxyethyl]-1,3,5-triazine-2,4-diamine

50 [0102] A2a) 130 g benzylamine, 163 g cyanoguanidine and 347 g aluminium isopropoxide were suspended in 267 g 1-methoxy-2-propanol and heated to 90 ˚C for 10 hrs (see example la-1.182 of Table II). [0103] A2b) The reaction mixture obtained in A2b was cooled to 75˚C, and 530 g methanol and 153 g methyl S-lactate were added. After 22 hrs the reaction mixture was added to 2400 g 10% acetic acid which had been pre-heated to 70 ˚C. Up to an internal temperature of 88 ˚C 740 ml solvent was removed by distillation, the mixture cooled to 20˚C and 55 extracted 3 times with 2000 ml ethyl acetate. The combined organic layers were dried over sodium sulfate, filtered and concentrated in vacuo. The resulting product was an oil. Yield of the product: 260 g, 83 % (see example V-2 of Table I).

25 EP 2 231 679 B1

A3) N-Cyclohexyl-6-methoxymethyl-1,3,5-triazine-2,4-diamine

[0104] A3a) 50 g cyclohexylamine, 68 g cyanoguanidine and 144 g aluminium isopropoxide were suspended in 110 g 1-methoxy-2-propanol and heated to 90 ˚C for 4 hrs (see example la-1.183 of Table II). 5 [0105] A3b) The reaction mixture obtained in A3a was then cooled to 75 ˚C, and 220 g methanol and 63,7 g methyl methoxyacetate were added. After 16 hrs the reaction mixture was added to 1000 g 10% acetic acid which had been pre-heated to 70 ˚C. Up to an internal temperature of 88 ˚C 330 ml solvent was removed by distillation, the mixture cooled to 20 ˚C and extracted 3 times with 1000 ml toluene. The combined organic layers were dried over sodium sulfate, filtered and concentrated in vacuo. The resulting product was an oil which solidified on standing. Product yield: 101 g 10 (85 %). mp: 103-6 ˚C (see example V-3 of Table I).

A4) N-[(1R)- 2,3-Dihydro-6-methyl-1H-inden-1-yl]-6-[(1R)-1-fluoroethyl]-1,3,5-triazine-2,4-diamine

[0106] A4a) A mixture of 53,1 g 1 R-1-amino-6-methylindane, 56,5 g cyanoguanidine, 127 g aluminium isopropoxide 15 and 75 g isopropanol were stirred under nitrogen and heated to reflux for 22,5 hrs (see example la-1.5 of Table II). [0107] A4b) The reaction mixture obtained in A4a was cooled to 75 ˚C, and 70 g 1,2-propandiol and 182 g methanol were added carefully. After complete addition 45,5 g methyl (2R)-2-fluoro-propionate was added. After 23 hrs at 70 ˚C the internal temperature the reaction mixture was then added to 870 g 10 % acetic acid at 70 ˚C. The suspension was then cooled to 20 ˚C, filtered and washed twice with 160 g 5 % acetic acid and then twice with 160 g water. The solid 20 was then dried in vacuo. Product yield: 81,7 g (81 %), mp: 135-136˚C (see example V-4 of Table I).

A5) 4-[1,2,3,4-tetrahydoisoquinolin-2-yl]-6-[(1R)-1-fluoroethyl]-1,3,5-triazine-2-amine

[0108] A5a) A mixture of 48 g 1,2,3,4-tetrahydoisoquinoline, 56,5 g cyanoguanidine, 128 g aluminium isopropoxide 25 and 75 g isopropanol were stirred under nitrogen and heated to reflux for 22 hrs (see example la-1.8 of Table II). [0109] A5b) The reaction mixture obtained in A5a was cooled to 75 ˚C, and 70 g 1,2-propandiol and 182 g methanol were added carefully. After complete addition 45,5 g methyl (2R)-2-fluoro-propionate was added. After 23 hrs at 70 ˚C the internal temperature the reaction mixture was then added to 862 g 10% acetic acid at 70 ˚C. The suspension was then cooled to 20 ˚C, filtered and washed with 2x 160 g 5 % acetic acid and then twice with 160g water. The solid was 30 then dried in vacuo. Product yield: 68,5 g (71 %), mp: 186-9˚C (see example V-5 of Table I).

A6) N-[1,2,3,4-Tetrahydronaphth-1-yl]-6-[(1S)-1-chloroethyl]-1,3,5-triazine-2,4-diamine

[0110] A6a) 136,6 g 1,2,3,4-Tetrahydronaphthaline, 122 g cyanoguanidine and 260 g aluminium isopropoxide were 35 suspended in 203 g 1-methoxy-2-propanol and heated to 90 ˚C for 24 hrs (see example Ia-1.189 of Table II). [0111] A6b) The reaction mixture obtained in A6a was cooled to 75 ˚C, and 400 g methanol and 134 g methyl (2S)- 2-chloropropionate were added. After 23 hrs the reaction mixture was added to 1800 g 10 % acetic acid which had been pre-heated to 70 ˚C. Up to an internal temperature of 86 ˚C 550 ml solvent was removed by distillation, the mixture cooled to 20 ˚C and filtered and washed twice with 180 g 5 % acetic acid and then twice with 180g water. The solid was 40 then dried in vacuo. Product yield: 209 g (76 %), mp: 169-70˚C (see example V-6 of Table I).

A7) 4-[1,2,3,4-tetrahydoisoquinolin-2-yl]-6-isopropyl-1,3,5-triazine-2-amine

[0112] A7a) A mixture of 68,7 g 1,2,3,4-tetrahydoisoquinoline, 67,9 g cyanoguanidine and 144 g aluminium isopro- 45 poxide were suspended in 111 g 2-ethoxyethanol and heated to 90 ˚C for 21 hrs (see example la-1.224 of Table II). [0113] A7b) The reaction mixture obtained in A7a was cooled to 75 ˚C, and 222 g methanol, 65 g methyl isobutyrate and 90 g 30 % sodium methoxide were added. After 23 hrs the reaction mixture was added to 1000 g 10 % acetic acid which had been pre-heated to 70 ˚C. Up to an internal temperature of 86 ˚C 430 ml solvent was removed by distillation, the mixture cooled to 20 ˚C and filtered and washed with 2x 240 g 5 % acetic acid and then twice with 240 g water. The 50 solid was then dried in vacuo. Product yield: 107 g (79 %), mp: >255 ˚C (see example V-7 of Table I).

A8) N-[(1R,2S)-2,6-Dimethyl-2,3-dihydro-1H-inden-1-yl]-6-difluoromethyl-1,3,5-triazine-2,4-diamine

[0114] A8a) A mixture of 87 g 1R,2S-1-amino-2,6-dimethylindane, 67,9 g cyanoguanidine and 146 g aluminium iso- 55 propoxide were suspended in 111 g 1-methoxy-2-propanol and heated to 90 ˚C for 24 hrs (see example Ia-1.192 of Table II). [0115] A8b) The reaction mixture obtained in A8a was cooled to 70 ˚C and 222 g methanol, 104 g 1,2 propandiol and 68,9 g methyl difluoropropionate were added. After 23 hrs the reaction mixture was added to 1000 g 10 % acetic acid

26 EP 2 231 679 B1

and 1000 ml toluene which had been pre-heated to 70 ˚C. Up to an internal temperature of 87 ˚C 370 ml solvent was removed by distillation, the mixture cooled to 20 ˚C, the phases separated and the organic phase extracted twice with 500ml toluene. The combined phases were dried over sodium sulfate and evaporated. The solid was then dried in vacuo. Product yield: 134 g (81 %), mp: 87-88˚C (see example V-8 of Table I). 5 A9) N-[(1R,2S)-2,4,6-Trimethyl-2,3-dihydro-1H-inden-1-yl]-6-[(1S)-1-chloroethyl]-1,3,5-triazine-2,4-diamine

[0116] A9a) A mixture of 7,6 g 1R,2S-1-amino-2,4,6-trimethylindane, 5,6 g cyanoguanidine and 12,0 g aluminium isopropoxide were suspended in 8,8 g 1-methoxy-2-propanol and heated to 90 ˚C for 16 hrs (s. expl. Ia-1-198 of Table 10 II). A9b) The reaction mixture obtained in A9a was cooled to 70 ˚C, and 18,2 g methanol and 6,1 g methyl (2S)-2- chloropropionate were added. After 22 hrs the reaction mixture was added to 10 % 85g acetic acid which had been pre- heated to 70 ˚C. Up to an internal temperature of 87 ˚C 20 ml solvent was removed by distillation. The mixture was then cooled to 20 ˚C and filtered and washed twice with 10 g 10 % acetic acid and then twice with 20g water. The solid was then dried in vacuo. Product yield: 6,3 g (45 %), mp: 85-87˚C (see example V-9 of Table I). 15 A10) N-[(1S,2R)-2,6-Dimethyl-2,3-dihydro-1H-inden-1-yl]-biguanidino-aluminiummethoxyisopropoxide

[0117] A mixture of 2.62 g (1S,2R)-1-amino-2,6-dimethylindane. 1.40 g cyanoguanidine, 3.40 g aluminium isopropoxide and 2.54 g 1-methoxy-2-propanol were stirred under nitrogen and heated to 103 ˚C. After 22 hrs the reaction was 20 cooled to 50˚C and concentrated in vacuo. The residue was suspended in toluene 20 ml and re-evaporated. The amorphous solid was then dried in vacuo. Structural confirmation was made with Al27-NMR, H1-NMR and C13-NMR in D8-Isopropanol (see example la-1.199 in Table II).

A11) N-[(1R)-cyclobutyl-2-phenyleth-1-yl]-biguandinoaluminiummethoxy-isopropoxide 25 [0118] A mixture of 3.08 g (1 R)-cyclobutyl-2-phenyleth-1-yl-amine, 1.42 g cyanoguanidine, 3.40 g aluminium isopropoxide and 2.54 g 1-methoxy-2-propanol were stirred under nitrogen and heated to 103 ˚C. After 22 hrs the reaction was cooled to 50˚C and concentrated in vacuo. The residue was suspended in toluene 20 ml and re-evaporated. The amorphous solid was then dried in vacuo. Structural confirmation was made with Al27-NMR, H1-NMR and C13-NMR in 30 D8-Isopropanol (see example la-1.215 in Table II).

A12) N-pent-3-ylbiguanidinoaluminiummethoxyisopropoxide

[0119] A mixture of 1.37 g 3-pentylamine, 1.40 g cyanoguanidine, 3.40 g aluminium isopropoxide and 3 g isopropanol 35 were stirred under nitrogen and heated to 85˚C. After 22 hrs the reaction was cooled to 50˚C and concentrated in vacuo. The residue was suspended in toluene 20 ml and re-evaporated. The amorphous solid was then dried in vacuo. Structural 27 1 13 confirmation was made with Al -NMR, H -NMR and C -NMR in D8-Isopropanol (see example la-1.33 in Table II). [0120] The compounds of formula (V) of the following Table I were prepared analogously to the preparation examples A1 (a, b) to A9 (a, b) and A10 to A12 from respective compounds of formula (I) as shown in Table II. 40 Table I: Compounds of formula (Va)

50 Cpd. Q NR1R2 NR3R4 Additive Solvent

V-1 (1S)-1-chloroethyl morpholin-yl NH2 -CH3OH

V-2 (1S)-1-hydroxyethyl benzylamino NH2 -CH3OH 55 V-3 methoxymethyl cyclohexylamino NH2 -CH3OH

27 EP 2 231 679 B1

(continued)

Cpd. Q NR1R2 NR3R4 Additive Solvent

V-4 (1R)-1-fluoroethyl (1R)-2,3-dihydro-6- NH2 1,2-propanediol CH3OH 5 methyl-1H-inden- 1yl-amino

V-5 (1R)-1-fluoroethyl 1,2,3,4-tetrahydro- NH2 1,2-propanediol CH3OH isoquinolin-2-yl 10 V-6 (1S)-1-chloroethyl (1RS)-1,2,3,4- NH2 -CH3OH tetrahydro-napht-1- yl-amino

V-7 isopropyl 1,2,3,4-tetrahydro- NH2 NaOCH3 CH3OH isoquinolin-2-yl 15

V-8 difluoromethyl (1R,2S)-2,3-dihydro- NH2 1,2-propanediol CH3OH 2,6-dimethyl-1H- inden-1yl-amino

V-9 (1S)-1-chloroethyl (1R,2S)-2,3-dihydro- NH2 -CH3OH 20 2,4,6-trimethyl-1H- inden-1yl-amino

V-10 (1R)-1-fluoroethyl (1R,2S)-2,3-dihydro- NH2 NaOCH3 CH3OH 2,6-dimethyl-1H- 25 inden-1yl-amino

V-11 (1S)-1-fluoroethyl (1R,2S)-2,3-dihydro- NH2 NaOC2H5 C2H5OH 2,6-dimethyl-1H- inden-1yl-amino V-12 (1R)-1-fluoroethyl (1R,2S)-2,3-dihydro- NH 1,2-propanediol CH OH 30 2 3 2-methyl-1H-inden- 1yl-amino

V-13 difluoromethyl (1R,2S)-2,3-dihydro- NH2 NaOCH3 CH3OH 2,6-dimethyl-1H- 35 inden-1yl-amino

V-14 (1R)-1-fluoroethyl (1RS)-1,2,3,4- NH2 NaOCH3, 1,2- CH3OH tetrahydro-napht-1- propanediol yl-amino

40 V-15 (1R)-1-fluoroethyl 1,2,3,4-tetrahydro- NH2 NaOCH3, 1,2- CH3OH iso-quinolin-2-yl propanediol)

V-16 (1R)-1-fluoroethyl (1R,2R)-2,3-dihydro- NH2 NaOCH3, 1,2- CH3OH 2,6-dimethyl-1H- propanediol inden-1yl-amino 45 V-17 difluoromethyl (1R)-2,3-dihydro-6- NH2 NaOCH3,CH3OCH(CH3)2 methyl-1H-inden- 1yl-amino

V-18 difluoromethyl 1,2,3,4-tetrahydro- NH2 NaOCH3,CH3OCH(CH3)2 50 iso-quinolin-2-yl

V-19 1-fluoro-1- (1R)-2,3-dihydro-6- NH2 NaOCH3, 1,2- CH3OCH(CH3)2 methylethyl methyl-1H-inden- propanediol 1yl-amino

55 V-20 1-fluoro-1- (1R,S)-1-cyclobutyl- NH2 NaOCH3, 1,2- CH3OCH(CH3)2 methylethyl 2-phenyleth-1-yl- propanediol amino

28 EP 2 231 679 B1

(continued)

Cpd. Q NR1R2 NR3R4 Additive Solvent

V-21 1-fluoro-1- (1R)-cyclobutyl-2- NH2 NaOCH3, 1,2- C2H5OC2H4OH 5 methylethyl phenyleth-1-yl- propanediol amino

V-22 (1R)-1-fluoroethyl (1R)-cyclobutyl-2- NH2 NaOCH3, 1,2- CH3OCH(CH3)2 phenyleth-1-yl- propanediol 10 amino

V-23 (1S)-1-fluoroethyl (1R)-cyclobutyl-2- NH2 NaOCH3, 1,2- CH3OCH(CH3)2 phenyleth-1-yl- propanediol amino V-24 1-fluoro-1- (2R,S)-1-methyl- NH NaOCH CH OH 15 2 3 3 methylethyl 2-(3,5- dimethylphenyloxy) eth-1-yl-amino

V-25 1-fluoro-1- (1R)-1-methyl- NH2 NaOCH3 C2H5OC2H4OH 20 methylethyl 2-(3,5- dimethylphenyloxy) eth-1-yl-amino

V-26 1-fluoro-1- (1S)-1-methyl- NH2 NaOCH3 CH3OH methylethyl 2-(3,5- 25 dimethylphenyloxy) eth-1-yl-amino

V-27 1-fluoro-1- 1,1- NH2 NaOCH3 CH3OH methylethyl dicyclopropylmethyl- 30 amino

V-28 1-fluoro-1- pent-3-ylamino NH2 NaOCH3 CH3OH methylethyl

V-29 1-fluoro-1- (4RS)-3,4-dihydro- NH2 NaOCH3 CH3OH methylethyl 2H-chromen-4-yl- 35 amino

V-30 1-fluoro-1- (4R)-3,4-dihydro-2H- NH2 NaOCH3 CH3OH methylethyl chromen-4-yl-amino

V-31 1-fluoro-1- (4S)-3,4-dihydro-2H- NH2 NaOCH3 CH3OH 40 methylethyl chromen-4-yl-amino

V-32 1-fluoro-1- (3RS, 4RS)-3- NH2 NaOCH3, 1,2- CH3OCH(CH3)2 methylethyl methyl-3,4-dihydro- propanediol 2H-chromen-4-yl- 45 amino

V-33 1-fluoro-1- (3R, 4R)-3-methyl- NH2 NaOCH3, 1,2- CH3OCH(CH3)2 methylethyl 3,4-dihydro-2H- propanediol chromen-4-yl-amino V-34 1-fluoro-1- (3S, 4S)-3-methyl- NH NaOCH , 1,2- CH OCH(CH ) 50 2 3 3 3 2 methylethyl 3,4-dihydro-2H- propanediol chromen-4-yl-amino

V-35 1-fluoro-1- (1 RS)-1- NH2 NaOCH3 CH3OH methylethyl cyclopropylethyl- 55 amino

29 EP 2 231 679 B1

(continued)

Cpd. Q NR1R2 NR3R4 Additive Solvent

V-36 1-fluoro-1- (1R)-1- NH2 NaOCH3 CH3OH 5 methylethyl cyclopropylethyl- amino

V-37 1-fluoro-1- (1S)-1- NH2 NaOCH3 CH3OH methylethyl cyclopropylethyl- 10 amino

V-38 1-fluoro-propyl (1RS)-1-(4- NH2 NaOCH3 C2H5OC2H,OH chlorphenyl)eth-1-yl- amino V-39 1-fluoro-propyl (1R)-1-(4- NH NaOCH C H OC H OH 15 2 3 2 5 2 4 chlorphenyl)eth-1-yl- amino

V-40 1-fluoro-propyl (1S)-1-(4- NH2 NaOCH3 C2H5OC2H4OH chlorphenyl)eth-1-yl- 20 amino

V-41 (1S)-1-chloroethyl (1R)-1,2,3,4- NH2 -CH3OH tetrahydro-napht-1- yl-amino

25 V-42 (1S)-1-chloroethyl (1S)-1,2,3,4- NH2 -CH3OH tetrahydro-napht-1- yl-amino

V-43 (1R)-1-fluoroethyl (1 R)-1,2,3,4- NH2 NaOCH3, 1,2- CH3OH tetrahydro-napht-1- propanediol 30 yl-amino

V-44 (1R)-1-fluoroethyl (1S)-1,2,3,4- NH2 NaOCH3, 1,2- CH3OH tetrahydro-napht-1- propanediol yl-amino

35 V-45 (1S)-1-chloroethyl morpholin-yl NHBz - CH3OH

V-46 (1S)-1-hydroxyethyl benzylamino NHBz - CH3OH

V-47 methoxymethyl cyclohexylamino NHBz - CH3OH

V-48 (1R)-1-fluoroethyl (1R)-2,3-dihydro-6- NHBz 1,2-propanediol CH3OH 40 methyl-1H-inden- 1yl-amino

V-49 (1 R)-1-fluoroethyl 1,2,3,4-tetrahydro- NHBz 1,2-propanediol CH3OH isoquinolin-2-yl

45 V-50 (1S)-1-chloroethyl 1,2,3,4-tetrahydro- NHBz - CH3OH napht-1-yl-amino

V-51 (1S)-1-fluoroethyl 1,2,3,4-tetrahydro- NHBz NaOCH3 CH3OH isoquinolin-2-yl

50 V-52 difluoromethyl (1R,2S)-2,3-dihydro- NHBz 1,2-propanediol CH3OH 2,6-dimethyl-1H- inden-1yl-amino

V-53 (1S)-1-chloroethyl (1R,2S)-2,3-dihydro- NHBz - CH3OH 2,4,6-trimethyl-1H- 55 inden-1yl-amino

30 EP 2 231 679 B1

(continued)

Cpd. Q NR1R2 NR3R4 Additive Solvent

V-54 (1R)-1-fluoroethyl (1R,2S)-2,3-dihydro- NHBz NaOCH3 CH3OH 5 2,6-dimethyl-1H- inden-1yl-amino

V-55 (1S)-1-fluoroethyl (1R,2S)-2,3-dihydro- NHBz NaOC2H5 C2H5OH 2,6-dimethyl-1H- 10 inden-1yl-amino

V-56 (1R)-1-fluoroethyl (1R,2S)-2,3-dihydro- NHBz 1,2-propanediol CH3OH 2-methyl-1H-inden- 1yl-amino V-57 difluoromethyl (1R,2S)-2,3-dihydro- NHBz NaOCH CH OH 15 3 3 2,6-dimethyl-1H- inden-1yl-amino

V-58 (1R)-1-fluoroethyl 1,2,3,4-tetrahydro- NHBz NaOCH3, 1,2- CH3OH napht-1-yl-amino propanediol 20 V-59 (1R)-1-fluoroethyl 1,2,3,4-tetrahydro- NHBz NaOCH3, 1,2- CH3OH isoquinolin-2-yl propanediol

V-60 (1R)-1-fluoroethyl (1R,2R)-2,3-dihydro- NHBz NaOCH3. 1,2- CH3OH 2,6-dimethyl-1H- propanediol 25 inden-1 yl-amino

V-61 difluoromethyl (1R)-2,3-dihydro-6- NHBz NaOCH3.CH3OCH(CH3)2 methyl-1H-inden- 1yl-amino V-62 difluoromethyl 1,2,3,4-tetrahydro- NHBz NaOCH ,CHOCH(CH ) 30 3 3 3 2 isoquinolin-2-yl

V-63 1-fluoro-1- (1R)-2,3-dihydro-6- NHBz NaOCH3, 1,2- CH3OCH(CH3)2 methylethyl methyl-1H-inden- propanediol 1yl-amino 35 V-64 1-fluoro-1- (1RS)-1-cyclobutyl- NHBz NaOCH3, 1,2- CH3OCH(CH3)2 methylethyl 2-phenyleth-1-yl- propanediol amino

V-65 1-fluoro-1- (1R)-cyclobutyl-2- NHBz NaOCH3, 1,2- C2H5OC2H4OH 40 methylethyl phenyleth-1-yl- propanediol amino

V-66 (1R)-1-fluoroethyl (1R)-cyclobutyl-2- NHBz NaOCH3, 1,2- CH3OCH(CH3)2 phenyleth-1-yl- propanediol amino 45 V-67 (1S)-1-fluoroethyl (1R)-cyclobutyl-2- NHBz NaOCH3, 1,2- CH5OCH(CH3)2 phenyleth-1-yl- propanediol amino

V-68 1-fluoro-1- 1-methyl-2-(3,5- NHBz NaOCH3 CH3OH 50 methylethyl dimethylphenyloxy) eth-1-yl-amino

V-69 1-fluoro-1- (1R)-1-methyl- NHBz NaOCH3 C2H5OC2H4OH methylethyl 2-(3,5- dimethylphenyloxy) 55 eth-1-yl-amino

31 EP 2 231 679 B1

(continued)

Cpd. Q NR1R2 NR3R4 Additive Solvent

V-70 1-fluoro-1- (1S)-1-methyl- NHBz NaOCH3 CH3OH 5 methylethyl 2-(3,5- dimethylphenyloxy) eth-1-yl-amino

V-71 1-fluoro-1- 1,1- NHBz NaOCH3 CH3OH 10 methylethyl dicyclopropylmethyl- amino

V-72 1-fluoro-1- pent-3-ylamino NHBz NaOCH3 CH3OH methylethyl V-73 1-fluoro-1- 3,4-dihydro-2H- NHBz NaOCH CH OH 15 3 3 methylethyl chromen-4-yl-amino

V-74 1-fluoro-1- (4R)-3,4-dihydro-2H- NHBz NaOCH3 CH3OH methylethyl chromen-4-yl-amino

V-75 1-fluoro-1- (4S)-3,4-dihydro-2H- NHBz NaOCH3 CH3OH 20 methylethyl chromen-4-yl-amino

V-76 1-fluoro-1- (3RS, 4RS)-3- NHBz NaOCH3 CH3OH methylethyl methyl-3,4-dihydro- 2H-chromen-4-yl- 25 amino

V-77 1-fluoro-1- (3R, 4R)-3-methyl- NHBz NaOCH3 CH3OH methylethyl 3,4-dihydro-2H- chromen-4-yl-amino V-78 1-fiuoro-1- (3S, 4S)-3-methyl- NHBz NaOCH CH OH 30 3 3 methylethyl 3,4-dihydro-2H- chromen-4-yi-amino

V-79 1-fluoro-1- (1RS)-1- NHBz NaOCH3 CH3OH methylethyl cyclopropylethyl- 35 amino

V-80 7-fluoro-1- (1R)-1- NHBz NaOCH3 CH3OH methylethyl cyclopropylethyl- amino

40 V-81 1-fluoro-1- (1S)-1- NHBz NaOCH3 CH3OH methylethyl cyclopropylethyl- amino

V-82 1-fluoro-propyl (1RS)-1-(4- NHBz NaOCH3 CH3OH chlorphenyl)eth-1-yl- 45 amino

V-83 1-fluoro-propyl (1R)-1-(4- NHBz NaOCH3 CH3OH chlorphenyl)eth-1-yl- amino

50 V-84 1-fluoro-propyl (1S)-1-(4- NHBz NaOCH3 CH3OH chlorphenyl)eth-1-yl- amino

V-85 (1S)-1-chloroethyl (1R)-1,2,3,4- NHBz - CH3OH tetrahydro-napht-1- 55 yl-amino

32 EP 2 231 679 B1

(continued)

Cpd. Q NR1R2 NR3R4 Additive Solvent

V-86 (1S)-1-chloroethyl (1S)-1,2,3,4- NHBz - CH3OH 5 tetrahydro-napht-1- yl-amino

V-87 (1R)-1-fluoroethyl (1R)-1,2,3,4- NHBz NaOCH3, 1,2- CH3OH tetrahydro-napht-1- propanediol 10 yl-amino

V-88 (1R)-1-fluoroethyl (1S)-1,2,3,4- NHBz NaOCH3, 1,2- CH3OH tetrahydro-napht-1- propanediol yl-amino V-89 (1S)-1-chloroethyl morpholin-yl NBz NaOCH CH OH 15 2 3 3

V-90 (1S)-1-hydroxyethyl benzylamino NBz2 NaOCH3 CH3OH

V-91 methoxymethyl cyclohexylamino NBz2 NaOCH3 CH3OH

V-92 (1R)-1-fluoroethyl (1R)-2,3-dihydro-6- NBz2 NaOCH3 CH3OH 20 methyl-1H-inden- 1yl-amino

V-93 (1R)-1-fluoroethyl 1,2,3,4-tetrahydro- NBz2 NaOCH3 CH3OH iso-quinolin-2-yl V-94 (1S)-1-chloroethyl (1RS)-1,2,3,4- NBz NaOCH CH OH 25 2 3 3 tetrahydro-napht-1- yl-amino

V-95 (1S)-1-fluoroethyl 1,2,3,4-tetrahydro- NBz2 NaOCH3 CH3OH isoquinolin-2-yl 30 V-96 difluoromethyl (1R,2S)-2,3-dihydro- NBz2 NaOCH3 CH3OH 2,6-dimethyl-1H- inden-1yl-amino

V-97 (1S)-1-chloroethyl (1R,2S)-2,3-dihydro- NBz2 NaOCH3 CH3OH 35 2,4,6-trimethyl-1H- inden-1yl-amino

V-98 (1R)-1-fluoroethyl (1R,2S)-2,3-dihydro- NBz2 NaOCH3 CH3OH 2,6-dimethyl-1H- inden-1yl-amino 40 V-99 (1S)-1-fluoroethyl (1 R,2S)-2,3-dihydro- NBz2 NaOCH3 CH3OH 2,6-dimethyl-1H- inden-1yl-amino

V-100 (1R)-1-fluoroethyl (1R,2S)-2,3-dihydro- NBz2 NaOCH3 CH3OH 45 2-methyl-1H-inden- 1yl-amino

V-101 difluoromethyl (1R,2S)-2,3-dihydro- NBzz NaOCH3 CH3OH 2,6-dimethyl-1H- inden-1yl-amino 50 V-102 (1R)-1-fluoroethyl (1RS)-1,2,3,4- NBZ2 NaOCH3 CH3OH tetrahydro-napht-1- yl-amino

V-103 (1R)-1-fluoroethyl 1,2,3,4-tetrahydro- NBz2 NaOCH3 CH3OH 55 isoquinolin-2-yl

33 EP 2 231 679 B1

(continued)

Cpd. Q NR1R2 NR3R4 Additive Solvent

V-104 (1R)-1-fluoroethyl (1R,2R)-2,3-dihydro- NBz2 NaOCH3 CH3OH 5 2,6-dimethyl-1H- inden-1yl-amino

V-105 difluoromethyl (1R)-2,3-dihydro-6- NBz2 NaOCH3 CH3OH methyl-1H-inden- 10 1yl-amino

V-106 difluoromethyl 1,2,3,4-tetrahydro- NBz2 NaOCH3 CH3OH isoquinolin-2-yl

V-107 1-fluoro-1- (1R)-2,3-dihydro-6- NBz2 NaOCH3 CH3OH methylethyl methyl-1H-inden- 15 1yl-amino

V-108 1-fluoro-1- 1-cyclobutyl-2- NBz2 NaOCH3 CH3OH methylethyl phenyleth-1-yl- amino 20 V-109 1-fluoro-1- (1R)-cyclobutyl-2- NBz2 NaOCH3 CH3OH methylethyl phenyleth-1-yl- amino

V-110 (1R)-1-fluoroethyl (1R)-cyclobutyl-2- NBz2 NaOCH3 CH3OH 25 phenyleth-1-yl- amino

V-111 (1S)-1-fluoroethyl (1 R)-cyclobutyl-2- NBz2 NaOCH3 CH30H phenyleth-1-yl- amino 30 V-112 1-fluoro-1- 1-methyl-2-(3,5- NBz2 NaOCH3 CH3OH methylethyl dimethylphenyloxy) eth-1-yl-amino

V-113 1-fluoro-1- (1R)-1-methyl- NBz2 NaOCH3 CH3OH 35 methylethyl 2-(3,5- dimethylphenyloxy) eth-1-yl-amino

V-114 1-fluoro-1- (1S)-1-methyl- NBz2 NaOCH3 CH3OH methylethyl 2-(3,5- 40 dimethylphenyloxy) eth-1-yl-amino

V-115 1-fluoro-1- 1,1- NBz2 NaOCH3 CH3OH methylethyl dicyclopropylmethyl- 45 amino

V-116 1-fluoro-1- pent-3-ylamino NBz2 NaOCH3 CH3OH methylethyl

V-117 1-fluoro-1- (4RS)-3,4-dihydro- NBz2 NaOCH3 CH3OH methylethyl 2H-chromen-4-yl- 50 amino

V-118 1-fluoro-1- (4R)-3,4-dihydro-2H- NBz2 NaOCH3 CH3OH methylethyl chromen-4-yl-amino

V-119 1-fluoro-1- (4S)-3,4-dihydro-2H- NBz2 NaOCH3 CH3OH ˚ 55 methylethyl chromen-4-yl-amino

34 EP 2 231 679 B1

(continued)

Cpd. Q NR1R2 NR3R4 Additive Solvent

V-120 1-fluoro-1- (3RS, 4RS)-3- NBz2 NaOCH3 CH3OH 5 methylethyl methyl-3,4-dihydro- 2H-chromen-4-yl- amino

V-121 1-fluoro-1- (3R, 4R)-3-methyl- NBz2 NaOCH3 CH3OH 10 methylethyl 3,4-dihydro-2H- chromen-4-yl-amino

V-122 1-fluoro-1- (4S, 4S)-3-methyl- NBz2 NaOCH3 CH3OH methylethyl 3,4-dihydro-2H- chromen-4-yl-amino 15 V-123 1-fluoro-1- (1RS)-1- NBz2 NaOCH3 CH3OH methylethyl cyclopropylethyl- amino

V-124 1-fluoro-1- (1R)-1- NBz2 NaOCH3 CH3OH 20 methylethyl cyclopropylethyl- amino

V-125 1-fluoro-1- (1S)-1- NBz2 NaOCH3 CH3OH methylethyl cyclopropylethyl- amino 25 V-126 1-fluoro-propyl (1RS)-1-(4- NBz2 NaOCH3 CH3OH chlorphenyl)eth-1-yl- amino

V-127 1-fluoro-propyl (1R)-1-(4- NBz2 NaOCH3 CH3OH 30 chlorphenyl)eth-1-yl- amino

V-128 1-fluoro-propyl (1S)-1-(4- NBz2 NaOCH3 CH3OH chlorphenyl)eth-1-yl- amino 35

V-129 (1S)-1-chloroethyl (1R)-1,2,3,4- NBz2 -CH3OH tetrahydro-napht-1- yl-amino

V-130 (1S)-1-chloroethyl (1 S)-1,2,3,4- NBz2 -CH3OH 40 tetrahydro-napht-1- yl-amino

V-131 (1R)-1-fluoroethyl (1 R)-1,2,3,4- NBz2 NaOCH3, 1,2- CH3OH tetrahydro-napht-1- propanediol 45 yl-amino

V-132 (1R)-1-fluoroethyl (1 S)-1,2,3,4- NBz2 NaOCH3, 1,2- CH3OH tetrahydro-napht-1- propanediol yl-amino V-133 (1S)-1-chloroethyl (3S, 4R)-3-methyl- NH -CHOH 50 2 3 3,4-dihydro-2H- chromen-4-yl-amino

V-134 (1S)-1-chloroethyl (4R, 4S)-3-methyl- NH2 -CH3OH 3,4-dihydro-2H- 55 chromen-4-yl-amino

35 EP 2 231 679 B1

(continued)

Cpd. Q NR1R2 NR3R4 Additive Solvent

V-135 (1R)-1-fluoroethyl (3S, 4R)-3-methyl- NH2 1,2-propanediol CH3OH 5 3,4-dihydro-2H- chromen-4-yl-amino

V-136 (1R)-1-fluoroethyl (4R, 4S)-3-methyl- NH2 1,2-propanediol) CH3OH 3,4-dihydro-2H- 10 chromen-4-yl-amino

V-137 1-fluoro-1- (3S, 4R)-3-methyl- NH2 NaOCH3, 1,2- CH3OCH(CH3)2 methylethyl 3,4-dihydro-2H- propanediol chromen-4-yl-amino V-138 1-fluoro-1- (4R, 4S)-3-methyl- NH NaOCH , 1,2- CH OCH(CH ) 15 2 3 3 3 2 methylethyl 3,4-dihydro-2H- propanediol chromen-4-yl-amino

V-139 difluoromethyl (3S, 4R)-3-methyl- NH2 NaOCH3 CH3OH 3,4-dihydro-2H- 20 chromen-4-yl-amino

V-140 difluoromethyl (4R, 4S)-3-methyl- NH2 NaOCH3 CH3OH 3,4-dihydro-2H- chromen-4-yl-amino

25 [0121] Abbreviations in Table I:

Bz = benzyl NHBz = benzylamino

30 NBz2 = dibenzylamino

[0122] Reaction conditions as to examples in Table I:

1) Reaction temperature of 70 to 75 ˚C in all experiments used

35 2) Yield generally in the range of percent 70 to 85 of theory, sometimes less yield when additive has been omitted

Table II: Compounds of formula (la-1)

Cpd. no. Y NR1R2 NR3R4 Al-source Solvent (la-1.1) O-i-Pr morpholin-yl NH Al(O-i-Pr) (CH ) CHOH 50 2 3 3 2

(la-1.2) O-i-Pr benzylamino NH2 Al(O-i-Pr)3 (CH3)2CHOH

(la-1.3) O-i-Pr cyclohexylamino NH2 Al(O-i-Pr)3 (CH3)2CHOH

(la-1.4) O-i-Pr (1RS)-2,3-dihydro-6- NH2 Al(O-i-Pr)3 (CH3)2CHOH 55 methyl-1H-inden-1yl- amino

36 EP 2 231 679 B1

(continued)

Cpd. no. Y NR1R2 NR3R4 Al-source Solvent

(la-1.5) O-i-Pr (1R)-2,3-dihydro-6- NH2 Al(O-i-Pr)3 (CH3)2CHOH 5 methyl-1H-inden-1yl- amino

(la-1.6) O-i-Pr (1S)-2,3-dihydro-6- NH2 Al(O-i-Pr)3 (CH3)2CHOH methyl-1H-inden-1yl- 10 amino

(la-1.7) O-i-Pr 1,2,3,4-tetrahydro- NH2 Al(O-i-Pr)3 (CH3)2CHOH quinolin-1-yl

(la-1.8) O-i-Pr 1,2,3,4-tetrahydro- NH2 Al(O-i-Pr)3 (CH3)2CHOH 15 isoquinolin-2-yl

(la-1.9) O-i-Pr (1RS)-1,2,3,4- NH2 Al(O-i-Pr)3 (CH3)2CHOH tetrahydro-napht-1-yl- amino (la-1.10) O-i-Pr (1R)-1,2,3,4- NH Al(O-i-Pr) (CH ) CHOH 20 2 3 3 2 tetrahydro-napht-1-yl- amino

(la-1.11) O-i-Pr (1S)-1,2,3,4- NH2 Al(O-i-Pr)3 (CH3)2CHOH tetrahydro-napht-1-yl- 25 amino

(la-1.12) O-i-Pr (1R,2S)-2,3-dihydro- NH2 Al(O-i-Pr)3 (CH3)2CHOH 2,6-dimethyl-1H- inden-1yl-amino

30 (la-1.13) O-i-Pr (1S,2R)-2,3-dihydro- NH2 Al(O-i-Pr)3 (CH3)2CHOH 2,4,6-trimethyl-1H- inden-1 yl-amino

(la-1.14) O-i-Pr (1R,2R)-2,3-dihydro- NH2 Al(CH3)3 (CH3)2CHOH 2,6dimethyl-1H-inden- 35 1yl-amino

(la-1.15) O-i-Pr (1S,2S)-2,3-dihydro- NH2 Al(CH3)3 (CH3)2CHOH 2,6-dimethyl-1H- inden-1yl-amino 40 (la-1.16) O-i-Pr (1R,2S)-2,3-dihydro- NH2 Al(O-i-Pr)3 (CH3)2CHOH 2-methyl-1H-inden- 1yl-amino

(la-1.17) O-i-Pr (1R,2R)-2,3-dihydro- NH2 Al(O-i-Pr)3 (CH3)2CHOH 45 2-methyl-1H-inden- 1yl-amino

(la-1.18) O-i-Pr (1R,2S)-2,3-dihydro- NH2 Al(O-i-Pr)3 (CH3)2CHOH 2,4,6-trimethyl-1H- inden-1yl-amino 50 (la-1.19) O-i-Pr (1 S,2R)-2,3-dihydro- NH2 Al(O-i-Pr)3 (CH3)2CHOH 2,6-methyl-1 H-inden- 1 yl-amino

(la-1.20) O-i-Pr (3RS, 4RS)-3-methyl- NH2 Al(O-i-Pr)3 (CH3)2CHOH 55 3,4-dihydro-2H- chromen-4-yl-amino

37 EP 2 231 679 B1

(continued)

Cpd. no. Y NR1R2 NR3R4 Al-source Solvent

(la-1.21) O-i-Pr (3R, 4R)-3-methyl-3,4- NH2 Al(O-i-Pr)3 (CH3)2CHOH 5 dihydro-2H-chromen- 4-yl-amino

(la-1.22) O-i-Pr (3S, 4S)-3-methyl-3,4- NH2 Al(O-i-Pr)3 (CH3)2CHOH dihydro-2H-chromen- 10 4-yl-amino

(la-1.23) O-i-Pr (1RS)-1- NH2 Al(O-i-Pr)3 (CH3)2CHOH cyclopropylethyl- amino

15 (la-1.24) O-i-Pr (1 R)-cyclopropylethyl- NH2 Al(O-i-Pr)3 (CH3)2CHOH amino

(la-1.25) O-i-Pr (1 S)-cyclopropylethyl- NH2 Al(O-i-Pr)3 (CH3)2CHOH amino (la-1.26) O-i-Pr (1RS)-1-(4- NH Al(O-i-Pr) (CH ) CHOH 20 2 3 3 2 chlorphenyl)eth-1-yl- amino

(la-1.27) O-i-Pr (1R)-(4-chlorphenyl) NH2 Al(O-i-Pr)3 (CH3)2CHOH eth-1-yl-amino 25 (la-1.28) O-i-Pr (1S)-(4-chlorphenyl) NH2 Al(O-i-Pr)3 (CH3)2CHOH eth-1-yl-amino

(la-1.29) O-i-Pr (1 RS)-1-methyl- NH2 Al(O-i-Pr)3 (CH3)2CHOH 2-(3,5- 30 dimethylphenyloxy) eth-1-yl-amino

(la-1.30) O-i-Pr (1R)-1-methyl-2-(3,5- NH2 Al(O-i-Pr)3 (CH3)2CHOH dimethylphenyloxy) eth-1-yl-amino 35 (la-1.31) O-i-Pr (1 S)-1-methyl-2-(3,5- NH2 Al(O-i-Pr)3 (CH3)2CHOH dimethylphenyloxy) eth-1-yl-amino

(la-1.32) O-i-Pr 1,1- NH2 Ai(O-i-Pr)3 (CH3)2CHOH 40 dicyclopropylmethyl- amino

(la-1.33) O-i-Pr pent-3-ylamino NH2 Al(O-i-Pr)3 (CH3)2CHOH

(la-1.34) O-i-Pr (1RS)-1-cyclobutyl-2- NH2 Al(O-i-Pr)3 (CH3)2CHOH 45 phenyleth-1-yl-amino

(la-1.35) O-i-Pr (1R)-cyclobutyl-2- NH2 Al(O-i-Pr)3 (CH3)2CHOH phenyleth-1-yl-amino

(la-1.36) O-i-Pr (1S)-cyclobutyl-2- NH2 Al(O-i-Pr)3 (CH3)2CHOH 50 phenyleth-1-yl-amino

(la-1.37) -OCH(CH3)CH2OCH3 morpholin-yl NHBz Al(O-i-Pr)3 HOCH(CH3) CH2OCH3

(la-1.38) -OCH(CH3)CH2OCH3 benzylamino NHBz Al(O-i-Pr)3 HOCH(CH3) 55 CH2OCH3

(la-1.39) -OCH(CH3)CH2OCH3 cyclohexylamino NHBz Al(O-i-Pr)3 HOCH(CH3) CH2OCH3

38 EP 2 231 679 B1

(continued)

Cpd. no. Y NR1R2 NR3R4 Al-source Solvent

(la-1.40) -OCH(CH3)CH2OCH3 2,3-dihydro-6-methyl- NHBz Al(O-i-Pr)3 HOCH(CH3) 5 1H-inden-1yl-amino CH2OCH3

(la-1.41) -OCH(CH3)CH2OCH3 (1R)-2,3-dihydro-6- NHBz Al(O-i-Pr)3 HOCH(CH3) methyl-1H-inden-1yl- CH2OCH3 amino 10 (la-1.42) -OCH(CH3)CH2OCH3 (1 S)-2,3-dihydro-6- NHBz Al(O-i-Pr)3 HOCH(CH3) methyl-1H-inden-1 yl- CH2OCH3 amino

(la-1.43) -OCH(CH3)CH2OCH3 1,2,3,4-tetrahydro- NHBz Al(O-i-Pr)3 HOCH(CH3) 15 quinolin-1-yl CH2OCH3

(la-1.44) -OCH(CH3)CH2OCH3 1,2,3,4-tetrahydro- NHBz Al(O-i-Pr)3 HOCH(CH3) isoquinolin-2-yl CH2OCH3

(la-1.45) -OCH(CH3)CH2OCH3 1,2,3,4-tetrahydro- NHBz Al(O-i-Pr)3 HOCH(CH3) napht-1-yl-amino CH OCH 20 2 3

(la-1.46) -OCH(CH3)CH2OCH3 (1 R)-1,2,3,4- NHBz Al(O-i-Pr)3 HOCH(CH3) tetrahydro-napht-1-yl- CH2OCH3 amino (la-1.47) -OCH(CH )CH OCH (1 S)-1,2,3,4- NHBz Al(O-i-Pr) HOCH(CH ) 25 3 2 3 3 3 tetrahydro-napht-1-yl- CH2OCH3 amino

(la-1.48) -OCH(CH3)CH2OCH3 (1R,2S)-2,3-dihydro- NHBz Al(O-i-Pr)3 HOCH(CH3) 2,6dimethyl-1H-inden- CH2OCH3 30 1yl-amino

(la-1.49) -OCH(CH3)CH2OCH3 (1S,2R)-2,3-dihydro- NHBz Al(O-i-Pr)3 HOCH(CH3) 2,4,6-trimethyl-1H- CH2OCH3 inden-1yl-amino

35 (l a-1.50) -OCH(CH3)CH2OCH3 (1R,2R)-2,3-dihydro- NHBz Al(O-i-Pr)3 HOCH(CH3) 2,6-dimethyl-1H- CH2OCH3 inden-1yl-amino

(la-1.51) -OCH(CH3)CH2OCH3 (1S,2S)-2,3-dihydro- NHBz AI(O-i-Pr)3 HOCH(CH3) 2,6-dimethyl-1H- CH2OCH3 40 inden-1yl-amino

(la-1.52) -OCH(CH3)CH2OCH3 (1R,2S)-2,3-dihydro- NHBz Al(O-i-Pr)3 HOCH(CH3) 2-methyl-1H-inden- CH2OCH3 1yl-amino

45 (la-1.53) -OCH(CH3)CH2OCH3 (1R,2R)-2,3-dihydro- NHBz Al(O-i-Pr)3 HOCH(CH3) 2-methyl-1H-inden- CH2OCH3 1yl-amino

(la-1.54) -OCH(CH3)CH2OCH3 (1R,2S)-2,3-dihydro- NHBz Al(O-i-Pr)3 HOCH(CH3) 2,4,6-trimethyl-1H- CH OCH 50 2 3 inden-1yl-amino

(la-1.55) -OCH(CH3)CH2OCH3 (1S,2R)-2,3-dihydro- NHBz Al(O-i-Pr)3 HOCH(CH3) 2,6-methyl-1H-inden- CH2OCH3 1yl-amino 55 (la-1.56) -OCH(CH3)CH2OCH3 (3RS, 4RS)-3-methyl- NHBz Al(O-i-Pr)3 HOCH(CH3) 3,4-dihydro-2H- CH2OCH3 chromen-4-yl-amino

39 EP 2 231 679 B1

(continued)

Cpd. no. Y NR1R2 NR3R4 Al-source Solvent

(la-1.57) -OCH(CH3)CH2OCH3 (3R, 4R)-3-methyl-3,4- NHBz Al(O-i-Pr)3 HOCH(CH3) 5 dihydro-2H-chromen- CH2OCH3 4-yl-amino

(la-1.58) -OCH(CH3)CH2OCH3 (3S, 4S)-3-methyl-3,4- NHBz Al(O-i-Pr)3 HOCH(CH3) dihydro-2H-chromen- CH2OCH3 10 4-yl-amino

(la-1.59) -OCH(CH3)CH2OCH3 1-cyclopropylethyl- NHBz Al(O-i-Pr)3 HOCH(CH3) amino CH2OCH3

(la-1.60) -OCH(CH3)CH2OCH3 (1 R)-cyclopropylethyl- NHBz Al(O-i-Pr)3 HOCH(CH3) 15 amino CH2OCH3

(la-1.61) -OCH(CH3)CH2OCH3 (1 S)-cyclopropylethyl- NHBz Al(O-i-Pr)3 HOCH(CH3) amino CH2OCH3

(la-1.62) -OCH(CH3)CH2OCH3 1-(4-chlorphenyl)eth- NHBz Al(O-i-Pr)3 HOCH(CH3) 1-yl-amino CH OCH 20 2 3

(la-1.63) -OCH(CH3)CH2OCH3 (1R)-(4-chlorphenyl) NHBz Al(O-i-Pr)3 HOCH(CH3) eth-1-yl-amino CH2OCH3

(la-1.64) -OCH(CH3)CH2OCH3 (1S)-(4-chlorphenyl) NHBz Al(O-i-Pr)3 HOCH(CH3) eth-1-yl-amino CH OCH 25 2 3 (la-1.65) -OCH(CH3)CH2OCH3 1-methyl-2-(3,5- NHBz Al(O-i-Pr)3 HOCH(PH3) dimethylphenyloxy) CH2OCH3 eth-1-yl-amino

(la-1.66) -OCH(CH3)CH2OCH3 (1R)-1-methyl-2-(3,5- NHBz Al(O-i-Pr)3 HOCH(CH3) 30 dimethylphenyloxy) CH2OCH3 eth-1-yl-amino

(la-1.67) -OCH(CH3)CH2OCH3 (1S)-1-methyl-2-(3,5- NHBz Al(O-i-Pr)3 HOCH(CH3) dimethylphenyloxy) CH2OCH3 35 eth-1-yl-amino

(la-1.68) -OCH(CH3)CH2OCH3 1,1- NHBz Al(O-i-Pr)3 HOCH(CH3) dicyclopropylmethyl- CH2OCH3 amino

40 (la-1.69) -OCH(CH3)CH2OCH3 pent-3-ylamino NHBz Al(O-i-Pr)3 HOCH(CH3) CH2OCH3

(la-1.70) -OCH(CH3)CHzOCH3 1-cyclobutyl-2- NHBz Al(O-i-Pr)3 HOCH(CH3) phenyleth-1-yl-amino CH2OCH3 (la-1.71) -OCH(CH )CH OCH (1R)-cyclobutyl-2- NHBz Al(O-i-Pr) HOCH(CH ) 45 3 2 3 3 3 phenyleth-1-yl-amino CH2OCH3

(la-1.72) -OCH(CH3)CH2OCH3 (1S)-cyclobutyl-2- NHBz Al(O-i-Pr)3 HOCH(CH3) phenyleth-1-yl-amino CH2OCH3

(la-1.73) -OCH2CH2OC2H5 morpholin-yl NBz2 Al(O-i-Pr)3 HOCH2CHzOC2H5 50 (la-1.74) -OCH2CH2OC2H5 benzylamino NBz2 Al(O-i-Pr)3 HOCH2CH2OC2H5

(la-1.75) -OCH2CH2OC2H5 cyclohexylamino NBz2 Al(O-i-Pr)3 HOCH2CH2OC2H5

(la-1.76) -OCH2CH2OC2H5 2,3-dihydro-6-methyl- NBz2 Al(O-i-Pr)3 HOCH2CH2OC2H5 55 1H-inden-1yl-amino

40 EP 2 231 679 B1

(continued)

Cpd. no. Y NR1R2 NR3R4 Al-source Solvent

(la-1.77) -OCH2CH2OC2H5 (1R)-2,3-dihydro-6- NBZ2 Al(O-i-Pr)3 HOCH2CH2OC2H5 5 methyl-1H-inden-1yl- amino

(la-1.78) -OCH2CH2OC2H5 (1S)-2,3-dihydro-6- NBz2 Al(O-i-Pr)3 HOCH2CH2OC2H5 methyl-1H-inden-1yl- 10 amino

(la-1.79) -OCH2CH2OC2H5 1,2,3,4-tetrahydro- NBz2 Al(O-i-Pr)3 HOCH2CH2OC2H5 quinolin-1-yl

(la-1.80) -OCH2CH2OC2H5 1,2,3,4-tetrahydro-iso- NBz2 Al(O-i-Pr)3 HOCH2CH2OC2H5 15 quinolin-2-yl

(la-1.81) -OCH2CH2OC2H5 1,2,3,4-tetrahydro- NBz2 Al(O-i-Pr)3 HOCH2CH2OC2H5 napht-1-yl-amino

(la-1.82) -OCH2CH2OC2H5 (1R)-1,2,3,4- NBz2 Al(O-i-Pr)3 HOCH2CH2OC2H5 tetrahydro-napht-1-yl- 20 amino

(la-1.83) -OCH2CH2OC2H5 (1 S)-1,2,3,4- NBz2 Al(O-i-Pr)3 HOCH2CH2OC2H5 tetrahydro-napht-1-yl- amino 25 (la-1.84) -OCH2CH2OC2H5 (1R,2S)-2,3-dihydro- NBz2 Al(O-i-Pr)3 HOCH2CH2Oc2H5 2,6-dimethyl-1H- inden-1yl-amino

(la-1.85) -OCH2CH2OC2H5 (1S,2R)-2,3-dihydro- NBz2 Al(O-i-Pr)3 HOCH2CH2OC2H5 30 2,4,6-trimethyl-1H- inden-1yl-amino

(la-1.86) -OCH2CH2OC2H5 (1R,2R)-2,3-dihydro- NBz2 Al(O-i-Pr)3 HOCH2CH2OC2H5 2,6-dimethyl-1H- inden-1yl-amino 35 (la-1.87) -OCH2CH20C2H5 (1S,2S)-2,3-dihydro- NBz2 Al(O-i-Pr)3 HOCH2CH2OC2H5 2,6-dimethyl-1H- inden-1yl-amino

(la-1.88) -OCH2CH2OC2H5 (1 R,2S)-2,3-dihydro- NBz2 Al(O-i-Pr)3 HOCH2CH2OC2H5 40 2-methyl-1 H-inden- 1yl-amino

(la-1.89) -OCH2CH2OC2H5 (1R,2R)-2,3-dihydro- NBz2 Al(O-i-Pr)3 HOCH2CH2OC2H5 2-methyl-1H-inden-lyl-

45 amino

(la-1.90) -OCH2CH2OC2H5 (1R,2S)-2,3-dihydro- NBzz Al(O-i-Pr)3 HOCH2CH2OC2H5 2,4,6-trimethyl-1H- inden-1yl-amino (la-1.91) -OCH CH OC H (1S,2R)-2,3-dihydro- NBz Al(O-i-Pr) HOCH CH OC H 50 2 2 2 5 2 3 2 2 2 5 2,6-methyl-1H-inden- 1yl-amino

(la-1.92) -OCH2CH2OC2H5 (3RS, 4RS)-3-methyl- NBz2 Al(O-i-Pr)3 HOCH2CH2OC2H5 3,4-dihydro-2H- 55 chromen-4-yl-amino

41 EP 2 231 679 B1

(continued)

Cpd. no. Y NR1R2 NR3R4 Al-source Solvent

(la-1.93) -OCH2CH2OC2H5 (3R, 4R)-3-methyl-3,4- NBz2 Al(O-i-Pr)3 HOCH2CH2OC2H5 5 dihydro-2H-chromen- 4-yl-amino

(la-1.94) -OCH2CH2OC2H5 (3S, 4S)-3-methyl-3,4- NBz2 Al(O-i-Pr)3 HOCH2CH2OC2H5 dihydro-2H-chromen- 10 4-yl-amino

(la-1.95) -OCH2CH2OC2H5 1-cyclopropylethyl- NBz2 Al(O-i-Pr)3 HOCH2CH2OC2H5 amino

(la-1.96) -OCH2CH2OC2H5 (1R)-cyclopropylethyl- NBz2 Al(O-i-Pr)3 HOCH2CH2OC2H5 15 amino

(la-1.97) -OCH2CH2OC2H5 (1 S)-cyclopropylethyl- NBz2 Al(O-i-Pr)3 HOCH2CH2OC2H5 amino

(la-1.98) -OCH2CH2OC2H5 1-(4-chlorphenyl)eth- NBz2 Al(O-i-Pr)3 HOCH2CH2OC2H5 1-yl-amino 20

(la-1.99) -OCH2CH2OC2H5 (1R)-(4-chlorphenyl) NBz2 Al(O-i-Pr)3 HOCH2CH2OC2H5 eth-1-yl-amino

(la-1.100) -OCH2CH2OC2H5 (1S)-(4-chlorphenyl) NBz2 Al(O-i-Pr)3 HOCH2CH2OC2H5 eth-1-yl-amino 25 (la-1.101) -OCH2CH2OC2H5 1-methyl-2-(3,5- NBz2 Al(O-i-Pr)3 HOCH2CH2OC2H5 dimethylphenyloxy) eth-1-yl-amino

(la-1.102) -OCH2CH2OC2H5 (1R)-1-methyl-2-(3,5- NBz2 Al(O-i-Pr)3 HOCH2CH2OC2H5 30 dimethylphenyloxy) eth-1-yl-amino

(la-1.103) -OCH2CH2OC2H5 (1S)-1-methyl-2-(3,5- NBz2 Al(O-i-Pr)3 HOCH2CH2OC2H5 dimethylphenyloxy) 35 eth-1-yl-amino

(la-1.104) -OCH2CH2OC2H5 1,1- NBz2 Al(O-i-Pr)3 HOCH2CH2OC2H5 dicyclopropylmethyl- amino

40 (la-1.105) -OCH2CH2OC2H5 pent-3-ylamino NBz2 Al(O-i-Pr)3 HOCH2CH2OC2H5

(la-1.106) -OCH2CH2OC2H5 1-cyclobutyl-2- NBz2 Al(O-i-Pr)3 HOCH2CH2OC2H5 phenyleth-1-yl-amino

(la-1.107) -OCH2CH2OC2H5 (1 R)-cyclobutyl-2- NBz2 Al(O-i-Pr)3 HOCH2CH2OC2H5 phenyleth-1-yl-amino 45

(la-1.108) -OCH2CH2OC2H5 (1 S)-cyclobutyl-2- NBz2 Al(O-i-Pr)3 HOCH2CH2OC2H5 phenyleth-1-yl-amino

(la-1.109) -OCH(CH3)C2H5 morpholin-yl NH2 Al(O-i-Bu)3 HOCH(CH3)C2H5

50 (la-1.110) -OCH(CH3)C2H5 benzylamino NH2 Al(O-i-Bu)3 HOCH(CH3)C2H5

(la-1.111) -OCH(CH3)C2H5 cyclohexylamino NH2 Al(O-i-Bu)3 HOCH(CH3)C2H5

(la-1.112) -OCH(CH3)C2H5 2,3-dihydro-6-methyl- NH2 Al(O-i-Bu)3 HOCH(CH3)C2H5 1H-inden-1yl-amino 55 (la-1.113) -OCH(CH3)C2H5 (1R)-2,3-dihydro-6- NH2 Al(O-i-Bu)3 HOCH(CH3)C2H5 methyl-1H-inden-1yl- amino

42 EP 2 231 679 B1

(continued)

Cpd. no. Y NR1R2 NR3R4 Al-source Solvent

(la-1.114) -OCH(CH3)C2H5 (1S)-2,3-dihydro-6- NH2 Al(O-i-Bu)3 HOCH(CH3)C2H5 5 methyl-1H-inden-1yl- amino

(la-1.115) -OCH(CH3)C2H5 1,2,3,4-tetrahydro- NH2 Al(O-i-Bu)3 HOCH(CH3)C2H5 quinolin-1-yl 10 (la-1.116) -OCH(CH3)C2H5 1,2,3,4-tetrahydro- NH2 Al(O-i-Bu)3 HOCH(CH3)C2H5 isoquinolin-2-yl

(la-1.117) -OCH(CH3)C2H5 1,2,3,4-tetrahydro- NH2 Al(O-i-Bu)3 HOCH(CH3)C2H5 napht-1-yl-amino

15 (la-1.118) -OCH(CH3)C2H5 (1R)-1,2,3,4- NH2 Al(O-i-Bu)3 HOCH(CH3)C2H5 tetrahydro-napht-1-yl- amino

(la-1.119) -OCH(CH3)C2H5 (1S)-1,2,3,4- NH2 Al(O-i-Bu)3 HOCH(CH3)C2H5 tetrahydro-napht-1-yl- 20 amino

(la-1.120) -OCH(CH3)C2H5 (1R,2S)-2,3-dihydro- NH2 Al(O-i-Bu)3 HOCH(CH3)C2H5 2,6-dimethyl-1H- inden-1yl-amino 25 (la-1.121) -OCH(CH3)C2H5 (1S,2R)-2,3-dihydro- NH2 Al(O-i-Bu)3 HOCH(CH3)C2H5 2,4,6-trimethyl-1H- inden-1yl-amino

(la-1.122) -OCH(CH3)C2H5 (1R,2R)-2,3-dihydro- NH2 Al(O-i-Bu)3 HOCH(CH3)C2H5 30 2,6-dimethyl-1H- inden-1yl-amino

(la-1.123) -OCH(CH3)C2H5 (1S,2S)-2,3-dihydro- NH2 Al(O-i-Bu)3 HOCH(CH3)C2H5 2,6-dimethyl-1H- inden-1yl-amino 35 (la-1.124) -OCH(CH3)C2H5 (1R,2S)-2,3-dihydro- NH2 Al(O-i-Bu)3 HOCH(CH3)C2H5 2-methyl-1H-inden- 1yl-amino

(la-1.125) -OCH(CH3)C2H5 (1R,2R)-2,3-dihydro- NH2 Al(O-i-Bu)3 HOCH(CH3)C2H5 40 2-methyl-1H-inden- 1yl-amino

(la-1.126) -OCH(CH3)C2H5 (1R,2S)-2,3-dihydro- NH2 Al(O-i-Bu)3 HOCH(CH3)C2H5 2,4,6-trimethyl-1H-

45 inden-1yl-amino

(la-1.127) -OCH(CH3)C2H5 (1S,2R)-2,3-dihydro- NH2 Al(O-i-Bu)3 HOCH(CH3)C2H5 2,6-methyl-1H-inden- 1yl-amino (la-1.128) -OCH(CH )C H (3RS, 4RS)-3-methyl- NH Al(O-i-Bu) HOCH(CH )C H 50 3 2 5 2 3 3 2 5 3,4-dihydro-2H- chromen-4-yl-amino

(la-1.129) -OCH(CH3)C2H5 (3R, 4R)-3-methyl-3,4- NH2 Al(O-i-Bu)3 HOCH(CH3)C2H5 dihydro-2H-chromen- 55 4-yl-amino

43 EP 2 231 679 B1

(continued)

Cpd. no. Y NR1R2 NR3R4 Al-source Solvent

(la-1.130) -OCH(CH3)C2H5 (3S, 4S)-3-methyl-3,4- NH2 Al(O-i-Bu)3 HOCH(CH3)C2H5 5 dihydro-2H-chromen- 4-yl-amino

(la-1.131) -OCH(CH3)C2H5 1-cyclopropylethyl- NH2 Al(O-i-Bu)3 HOCH(CH3)C2H5 amino 10 (la-1.132) -OCH(CH3)C2H5 (1R)-cyclopropylethyl- NH2 Al(O-i-Bu)3 HOCH(CH3)C2H5 amino

(la-1.133) -OCH(CH3)C2H5 (1S)-cyclopropylethyl- NH2 Al(O-i-Bu)3 HOCH(CH3)C2H5 amino

15 (la-1.134) -OCH(CH3)C2H5 1-(4-chlorphenyl)eth- NH2 Al(O-i-Bu)3 HOCH(CH3)C2H5 1-yl-amino

(la-1.135) -OCH(CH3)C2H5 (1R)-(4-chlorphenyl) NH2 Al(O-i-Bu)3 HOCH(CH3)C2H5 eth-1-yl-amino

20 (la-1.136) -OCH(CH3)C2H5 (1S)-(4-chlorphenyl) NH2 Al(O-i-Bu)3 HOCH(CH3)C2H5 eth-1-yl-amino

(la-1.137) -OCH(CH3)C2H5 1-methyl-2-(3,5- NH2 Al(O-i-Bu)3 HOCH(CH3)C2H5 dimethylphenyloxy) eth-1-yl-amino 25 (la-1.138) -OCH(CH3)C2H5 (1R)-1-methyl-2-(3,5- NH2 Al(O-i-Bu)3 HOCH(CH3)C2H5 dimethylphenyloxy) eth-1-yl-amino

(la-1.139) -OCH(CH3)C2H5 (1S)-1-methyl-2-(3,5- NH2 Al(O-i-Bu)3 HOCH(CH3)C2H5 30 dimethylphenyloxy) eth-1-yl-amino

(la-1.140) -OCH(CH3)C2H5 1,1- NH2 Al(O-i-Bu)3 HOCH(CH3)C2H5 dicyclopropylmethyl- 35 amino

(la-1.141) -OCH(CH3)C2H5 pent-3-ylamino NH2 Al(O-i-Bu)3 HOCH(CH3)C2H5

(la-1.142) -OCH(CH3)C2H5 1-cyclobutyl-2- NH2 Al(O-i-Bu)3 HOCH(CH3)C2H5 phenyleth-1-yl-amino

40 (la-1.143) -OCH(CH3)C2H5 (1R)-cyclobutyl-2- NH2 Al(O-i-Bu)3 HOCH(CH3)C2H5 phenyleth-1-yl-amino

(la-1.144) -OCH(CH3)C2H5 (1S)-cyclobutyl-2- NH2 Al(O-i-Bu)3 HOCH(CH3)C2H5 phenyleth-1-yl-amino

45 (la-1.145) O-i-Pr morpholin-yl NHBz Al(O-i-Pr)3 (CH3)2CHOH

(la-1.146) O-i-Pr benzylamino NHBz Al(O-i-Pr)3 (CH3)2CHOH

(la-1.147) O-i-Pr cyclohexylamino NHBz Al(O-i-Pr)3 (CH3)2CHOH

(la-1.148) O-i-Pr 2,3-dihydro-6-methyl- NHBz Al(O-i-Pr)3 (CH3)2CHOH 50 1H-inden-1yl-amino

(la-1.149) O-i-Pr (1R)-2,3-dihydro-6- NHBz Al(O-i-Pr)3 (CH3)2CHOH methyl-1H-inden-1yl- amino 55 (la-1.150) O-i-Pr (1S)-2,3-dihydro-6- NHBz Al(O-i-Pr)3 (CH3)2CHOH methyl-1H-inden-1yl- amino

44 EP 2 231 679 B1

(continued)

Cpd. no. Y NR1R2 NR3R4 Al-source Solvent

(la-1.151) O-i-Pr 1,2,3,4-tetrahydro- NHBz Al(O-i-Pr)3 (CH3)2CHOH 5 quinolin-1-yl

(la-1.152) O-i-Pr 1,2,3,4-tetrahydro- NHBz Al(O-i-Pr)3 (CH3)2CHOH isoquinolin-2-yl

(la-1.153) O-i-Pr 1,2,3,4-tetrahydro- NHBz Al(O-i-Pr)3 (CH3)2CHOH 10 napht-1-yl-amino

(la-1.154) O-i-Pr (1R)-1,2,3,4- NHBz Al(O-i-Pr)3 (CH3)2CHOH tetrahydro-napht-1-yl- amino

15 (la-1.155) O-i-Pr (1S)-1,2,3,4- NHBz Al(O-i-Pr)3 (CH3)2CHOH tetrahydro-napht-1-yl- amino

(la-1.156) O-i-Pr (1R,2S)-2,3-dihydro- NHBz Al(O-i-Pr)3 (CH3)2CHOH 2,6-dimethyl-1H- 20 inden-1yl-amino

(la-1.157) O-i-Pr (1S,2R)-2,3-dihydro- NHBz Al(O-i-Pr)3 (CH3)2CHOH 2,4,6-trimethyl-1H- inden-1yl-amino 25 (la-1.158) O-i-Pr (1R,2R)-2,3-dihydro- NHBz Al(CH3)3 (CH3)2CHOH 2,6-dimethyl-1H- inden-1yl-amino

(la-1.159) O-i-Pr (1S,2S)-2,3-dihydro- NHBz Al(CH3)3 (CH3)2CHOH 30 2,6-dimethyl-1H- inden-1yl-amino

(la-1.160) O-i-Pr (1R,2S)-2,3-dihydro- NHBz Al(O-i-Pr)3 (CH3)2CHOH 2-methyl-1H-inden- 1yl-amino 35 (la-1.161 ) O-i-Pr (1R,2R)-2,3-dihydro- NHBz Al(O-i-Pr)3 (CH3)2CHOH 2-methyl-1H-inden- 1yl-amino

(la-1.162) O-i-Pr (1R,2S)-2,3-dihydro- NHBz Al(O-i-Pr)3 (CH3)2CHOH 40 2,4,6-trimethyl-1H- inden-1yl-amino

(la-1.163) O-i-Pr (1S,2R)-2,3-dihydro- NHBz Al(O-i-Pr)3 (CH3)2CHOH 2,6-methyl-1H-inden-

45 1yl-amino

(la-1.164) O-i-Pr (3RS, 4RS)-3-methyl- NHBz Al(O-i-Pr)3 (CH3)2CHOH 3,4-dihydro-2H- chromen-4-yl-amino (la-1.165) O-i-Pr (3R, 4R)-3-methyl-3,4- NHBz Al(O-i-Pr) (CH ) CHOH 50 3 3 2 dihydro-2H-chromen- 4-yl-amino

(la-1.166) O-i-Pr (3S, 4S)-3-methyl-3,4- NHBz Al(O-i-Pr)3 (CH3)2CHOH dihydro-2H-chromen- 55 4-yl-amino

(la-1.167) O-i-Pr 1-cyclopropylethyl- NHBz Al(O-i-Pr)3 (CH3)2CHOH amino

45 EP 2 231 679 B1

(continued)

Cpd. no. Y NR1R2 NR3R4 Al-source Solvent

(la-1.168) O-i-Pr (1R)-cyclopropylethyl- NHBz Al(O-i-Pr)3 (CH3)2CHOH 5 amino

(la-1.169) O-i-Pr (1S)-cyclopropylethyl- NHBz Al(O-i-Pr)3 (CH3)2CHOH amino

(la-1.170) O-i-Pr 1-(4-chlorphenyl)eth- NHBz Al(O-i-Pr)3 (CH3)2CHOH 10 1-yl-amino

(la-1.171) O-i-Pr (1R)-(4-chlorphenyl) NHBz Al(O-i-Pr)3 (CH3)2CHOH eth-1-yl-amino

(la-1.172) O-i-Pr (1S)-(4-chlorphenyl) NHBz Al(O-i-Pr)3 (CH3)2CHOH 15 eth-1-yl-amino

(la-1.173) O-i-Pr 1-methyl-2-(3,5- NHBz Al(O-i-Pr)3 (CH3)2CHOH dimethylphenyloxy) eth-1-yl-amino

20 (la-1.174) O-i-Pr (1R)-1-methyl-2-(3,5- NHBz Al(O-i-Pr)3 (CH3)2CHOH dimethylphenyloxy) eth-1-yl-amino

(la-1.175) O-i-Pr (1S)-1-methyl-2-(3,5- NHBz Al(O-i-Pr)3 (CH3)2CHOH dimethylphenyloxy) 25 eth-1-yl-amino

(la-1.176) O-i-Pr 1,1- NHBz Al(O-i-Pr)3 (CH3)2CHOH dicyclopropylmethyl- amino 30 (la-1.177) O-i-Pr pent-3-ylamino NHBz Al(O-i-Pr)3 (CH3)2CHOH

(la-1.178) O-i-Pr 1-cyclobutyl-2- NHBz Al(O-i-Pr)3 (CH3)2CHOH phenyleth-1-yl-amino

(la-1.179) O-i-Pr (1R)-cyclobutyl-2- NHBz Al(O-i-Pr)3 (CH3)2CHOH 35 phenyleth-1-yl-amino

(la-1.180) O-i-Pr (1S)-cyclobutyl-2- NHBz Al(O-i-Pr)3 (CH3)2CHOH phenyleth-1-yl-amino

(la-1.181) -OCH(CH3)CH2OCH3 morpholin-yl NH2 Al(O-i-Pr)3 HOCH(CH3) 40 CH2OCH3

(la-1.182) -OCH(CH3)CH2OCH3 benzylamino NH2 Al(O-i-Pr)3 HOCH(CH3) CH2OCH3

(la-1.183) -OCH(CH3)CH2OCH3 cyclohexylamino NH2 Al(O-i-Pr)3 HOCH(CH3) 45 CH2OCH3

(la-1.184) -OCH(CH3)CH2OCH3 2,3-dihydro-6-methyl- NH2 Al(O-i-Pr)3 HOCH(CH3) 1H-inden-1yl-amino CH2OCH3

(la-1.185) -OCH(CH3)CH2OCH3 (1R)-2,3-dihydro-6- NH2 Al(O-i-Pr)3 HOCH(CH3) 50 methyl-1H-inden-1yl- CH2OCH3 amino

(la-1.186) -OCH(CH3)CH2OCH3 (1S)-2,3-dihydro-6- NH2 Al(O-i-Pr)3 HOCH(CH3) methyl-1H-inden-1yl- CH2OCH3 amino 55 (la-1.187) -OCH(CH3)CH2OCH3 1,2,3,4-tetrahydro- NH2 Al(O-i-Pr)3 HOCH(CH3) quinolinyl CH2OCH3

46 EP 2 231 679 B1

(continued)

Cpd. no. Y NR1R2 NR3R4 Al-source Solvent

(la-1.188) -OCH(CH3)CH2OCH3 1,2,3,4-tetrahydro- NH2 Al(O-i-Pr)3 HOCH(CH3) 5 isoquinolin-2-yl CH2OCH3

(la-1.189) -OCH(CH3)CH2OCH3 (1RS)-1,2,3,4- NH2 Al(O-i-Pr)3 HOCH(CH3) tetrahydro-napht-1-yl- CH2OCH3 amino 10 (la-1.190) -OCH(CH3)CH2OCH3 (1R)-1,2,3,4- NH2 Al(O-i-Pr)3 HOCH(CH3) tetrahydro-napht-1-yl- CH2OCH3 amino

(la-1.191) -OCH(CH3)CH2OCH3 (1S)-1,2,3,4- NH2 Al(O-i-Pr)3 HOCH(CH3) 15 tetrahydro-napht-1-yl- CH2OCH3 amino

(la-1.192) -OCH(CH3)CH2OCH3 (1R,2S)-2,3-dihydro- NH2 Al(O-i-Pr)3 HOCH(CH3) 2,6-dimethyl-1H- CH2OCH3 inden-1yl-amino 20 (la-1.193) -OCH(CH3)CH2OCH3 (1S,2R)-2,3-dihydro- NH2 Al(O-i-Pr)3 HOCH(CH3) 2,4,6-trimethyl-1H- CH2OCH3 inden-1yl-amino

(la-1.194) -OCH(CH3)CH2OCH3 (1R,2R)-2,3-dihydro- NH2 Al(O-i-Pr)3 HOCH(CH3) 25 2,6-dimethyl-1H- CH2OCH3 inden-1yl-amino

(la-1.195) -OCH(CH3)CH2OCH3 (1S,2S)-2,3-dihydro- NH2 Al(O-i-Pr)3 HOCH(CH3) 2,6-dimethyl-1H- CH2OCH3 inden-1yl-amino 30 (la-1.196) -OCH(CH3)CH2OCH3 (1R,2S)-2,3-dihydro- NH2 Al(O-i-Pr)3 HOCH(CH3) 2-methyl-1H-inden- CH2OCH3 1yl-amino

(la-1.197) -OCH(CH3)CH2OCH3 (1R,2R)-2,3-dihydro- NH2 Al(O-i-Pr)3 HOCH(CH3) 35 2-methyl-1H-inden- CH2OCH3 1yl-amino

(la-1.198) -OCH(CH3)CH2OCH3 (1R,2S)-2,3-dihydro- NH2 Al(O-i-Pr)3 HOCH(CH3) 2,4,6-trimethyl-1H- CH2OCH3 40 inden-1yl-amino

(la-1.199) -OCH(CH3)CH2OCH3 (1S,2R)-2,3-dihydro- NH2 Al(O-i-Pr)3 HOCH(CH3) 2-methyl-1H-inden- CH2OCH3 1yl-amino

45 (la-1.200) -OCH(CH3)CH2OCH3 (3RS, 4RS)-3-methyl- NH2 Al(O-i-Pr)3 HOCH(CH3) 3,4-dihydro-2H- CH2OCH3 chromen-4-yl-amino

(la-1.201) -OCH(CH3)CH2OCH3 (3R, 4R)-3-methyl-3,4- NH2 Al(O-i-Pr)3 HOCH(CH3) dihydro-2H-chromen- CH2OCH3 50 4-yl-amino

(la-1.202) -OCH(CH3)CH2OCH3 (3S, 4S)-3-methyl-3,4- NH2 Al(O-i-Pr)3 HOCH(CH3) dihydro-2H-chromen- CH2OCH3 4-yl-amino

55 (la-1.203) -OCH(CH3)CH2OCH3 1-cyclopropylethyl- NH2 Al(O-i-Pr)3 HOCH(CH3) amino CH2OCH3

47 EP 2 231 679 B1

(continued)

Cpd. no. Y NR1R2 NR3R4 Al-source Solvent

(la-1.204) -OCH(CH3)CH2OCH3 (1R)-cyclopropylethyl- NH2 Al(O-i-Pr)3 HOCH(CH3) 5 amino CH2OCH3

(la-1.205) -OCH(CH3)CH2OCH3 (1S)-cyclopropylethyl- NH2 Al(O-i-Pr)3 HOCH(CH3) amino CH2OCH3

(la-1.206) -OCH(CH3)CH2OCH3 1-(4-chlorphenyl)eth- NH2 Al(O-i-Pr)3 HOCH(CH3) 10 1-yl-amino CH2OCH3

(la-1.207) -OCH(CH3)CH2OCH3 (1R)-(4-chlorphenyl) NH2 Al(O-i-Pr)3 HOCH(CH3) eth-1-yl-amino CH2OCH3

(la-1.208) -OCH(CH3)CH2OCH3 (1S)-(4-chlorphenyl) NH2 Al(O-i-Pr)3 HOCH(CH3) 15 eth-1-yl-amino CH2OCH3

(la-1.209) -OCH(CH3)CH2OCH3 1-methyl-2-(3,5- NH2 Al(O-i-Pr)3 HOCH(CH3) dimethylphenyloxy) CH2OCH3 eth-1-yl-amino

20 (la-1.210) -OCH(CH3)CH2OCH3 (1R)-1-methyl-2-(3,5- NH2 Al(O-i-Pr)3 HOCH(CH3) dimethylphenyloxy) CH2OCH3 eth-1-yl-amino

(la-1.211) -OCH(CH3)CH2OCH3 (1S)-1-methyl-2-(3,5- NH2 Al(O-i-Pr)3 HOCH(CH3) dimethylphenyloxy) CH OCH 25 2 3 eth-1-yl-amino

(la-1.212) -OCH(CH3)CH2OCH3 1,1- NH2 Al(O-i-Pr)3 HOCH(CH3) dicyclopropylmethyl- CH2OCH3 amino 30 (la-1.213) -OCH(CH3)CH2OCH3 pent-3-ylamino NH2 Al(O-i-Pr)3 HOCH(CH3) CH2OCH3

(la-1.214) -OCH(CH3)CH2OCH3 1-cyclobutyl-2- NH2 Al(O-i-Pr)3 HOCH(CH3) phenyleth-1-yl-amino CH2OCH3 35 (la-1.215) -OCH(CH3)CH2OCH3 (1R)-cyclobutyl-2- NH2 Al(O-i-Pr)3 HOCH(CH3) phenyleth-1-yl-amino CH2OCH3

(la-1.216) -OCH(CH3)CH2OCH3 (1S)-cyclobutyl-2- NH2 Al(O-i-Pr)3 HOCH(CH3) phenyleth-1-yl-amino CH2OCH3 40 (la-1.217) -OCH2CH2OC2H5 morpholin-yl NH2 Al(O-i-Pr)3 HOCH2CH2OC2H5

(la-1.218) -OCH2CH2OC2H5 benzylamino NH2 Al(O-i-Pr)3 HOCH2CH2OC2H5

(la-1.219) -OCH2CH2OC2H5 cyclohexylamino NH2 Al(O-i-Pr)3 HOCH2CH2OC2H5

(la-1.220) -OCH2CH2OC2H5 (1RS)-2,3-dihydro-6- NH2 Al(O-i-Pr)3 HOCH2CH2OC2H5 45 methyl-1H-inden-1yl- amino

(la-1.221) -OCHzCH2OC2H5 (1R)-2,3-dihydro-6- NH2 Al(O-i-Pr)3 HOCH2CH2OC2H5 methyl-1H-inden-1yl- 50 amino

(la-1.222) -OCH2CH2OC2H5 (1S)-2,3-dihydro-6- NH2 Al(O-i-Pr)3 HOCH2CH2OC2H5 methyl-1H-inden-1yl- amino

55 (la-1.223) -OCH2CH2OC2H5 1,2,3,4-tetrahydro- NH2 Al(O-i-Pr)3 HOCH2CH2OC2H5 quinlin-1-yl

48 EP 2 231 679 B1

(continued)

Cpd. no. Y NR1R2 NR3R4 Al-source Solvent

(la-1.224) -OCH2CH2OC2H5 1,2,3,4-tetrahydro- NH2 Al(O-i-Pr)3 HOCH2CH2OC2H5 5 isoquinolin-2-yl

(la-1.225) -OCH2CH2OC2H5 1,2,3,4-tetrahydro- NH2 Al(O-i-Pr)3 HOCH2CH2OC2H5 napht-1-yl-amino

(la-1.226) -OCH2CH2OC2H5 (1R)-1,2,3,4- NH2 Al(O-i-Pr)3 HOCH2CH2OC2H5 10 tetrahydro-napht-1-yl- amino

(la-1.227) -OCH2CH2OC2H5 (1S)-1,2,3,4- NH2 Al(O-i-Pr)3 HOCH2CH2OC2H5 tetrahydro-napht-1-yl-

15 amino

(la-1.228) -OCH2CH2OC2H5 (1R,2S)-2,3-dihydro- NH2 Al(O-i-Pr)3 HOCH2CH2OC2H5 2,6-dimethyl-1H- inden-1yl-amino (la-1.229) -OCH CH OC H (1S,2R)-2,3-dihydro- NH Al(O-i-Pr) HOCH CH OC H 20 2 2 2 5 2 3 2 2 2 5 2,4,6-trimethyl-1H- inden-1yl-amino

(la-1.230) -OCH2CH2OC2H5 (1R,2R)-2,3-dihydro- NH2 Al(O-i-Pr)3 HOCH2CH2OC2H5 2,6-dimethyl-1H- 25 inden-1yl-amino

(la-1.231) -OCH2CH2OC2H5 (1S,2S)-2,3-dihydro- NH2 Al(O-i-Pr)3 HOCH2CH2OC2H5 2,6-dimethyl-1H- inden-1yl-amino

30 (la-1.232) -OCH2CH2OC2H5 (1R,2S)-2,3-dihydro- NH2 Al(O-i-Pr)3 HOCH2CH2OC2H5 2-methyl-1H-inden- 1yl-amino

(la-1.233) -OCH2CH2OC2H5 (1R,2R)-2,3-dihydro- NH2 Al(O-i-Pr)3 HOCH2CH2OC2H5 2-methyl-1H-inden- 35 1yl-amino

(la-1.234) -OCH2CH2OC2H5 (1R,2S)-2,3-dihydro- NH2 Al(O-i-Pr)3 HOCH2CH2OC2H5 2,4,6-trimethyl-1H- inden-1yl-amino 40 (la-1.235) -OCH2CH2OC2H5 (1S,2R)-2,3-dihydro- NH2 Al(O-i-Pr)3 HOCH2CH2OC2H5 2,6-methyl-1H-inden- 1yl-amino

(la-1.236) -OCH2CH2OC2H5 (3RS, 4RS)-3-methyl- NH2 Al(O-i-Pr)3 HOCH2CH2OC2H5 45 3,4-dihydro-2H- chromen-4-yl-amino

(la-1.237) -OCH2CH2OC2H5 (3R, 4R)-3-methyl-3,4- NH2 Al(O-i-Pr)3 HOCH2CH2OC2H5 dihydro-2H-chromen- 4-yl-amino 50 (la-1.238) -OCH2CH2OC2H5 (3S, 4S)-3-methyl-3,4- NH2 Al(O-i-Pr)3 HOCH2CH2OC2H5 dihydro-2H-chromen- 4-yl-amino

(la-1.239) -OCH2CH2OC2H5 1-cyclopropylethyl- NH2 Al(O-i-Pr)3 HOCH2CH2OC2H5 55 amino

(la-1.240) -OCH2CH2OC2H5 (1R)-cyclopropylethyl- NH2 Al(O-i-Pr)3 HOCH2CH2OC2H5 amino

49 EP 2 231 679 B1

(continued)

Cpd. no. Y NR1R2 NR3R4 Al-source Solvent

(la-1.241) -OCH2CH2OC2H5 (1S)-cyclopropylethyl- NH2 Al(O-i-Pr)3 HOCH2CH2OC2H5 5 amino

(la-1.242) -OCH2CH2OC2H5 1-(4-chlorphenyl)eth- NH2 Al(O-i-Pr)3 HOCH2CH2OC2H5 1-yl-amino

(la-1.243) -OCH2CH2OC2H5 (1R)-(4-chlorphenyl) NH2 Al(O-i-Pr)3 HOCH2CH2OC2H5 10 eth-1-yl-amino

(la-1.244) -OCH2CH2OC2H5 (1S)-(4-chlorphenyl) NH2 Al(O-i-Pr)3 HOCH2CH2OC2H5 eth-1-yl-amino

(la-1.245) -OCH2CH2OC2H5 1-methyl-2-(3,5- NH2 Al(O-i-Pr)3 HOCH2CH2OC2H5 15 dimethylphenyloxy) eth-2-yl-amino

(la-1.246) -OCH2CH2OC2H5 (1R)-1-methyl-2-(3,5- NH2 Al(O-i-Pr)3 HOCH2CH2OC2H5 dimethylphenyloxy) eth-2-yl-amino 20

(la-1.247) -OCH2CH2OC2H5 (1S)-1-methyl-2-(3,5- NH2 Al(O-i-Pr)3 HOCH2CH2OC2H5 dimethylphenyloxy) eth-2-yl-amino (la-1.248) -OCH CH OC H 1,1- NH Al(O-i-Pr) HOCH CH OC H 25 2 2 2 5 2 3 2 2 2 5 dicyclopropylmethyl- amino

(la-1.249) -OCH2CH2OC2H5 pent-3-ylamino NH2 Al(O-i-Pr)3 HOCH2CH2OC2H5

(la-1.250) -OCH2CH2OC2H5 1-cyclobutyl-2- NH2 Al(O-i-Pr)3 HOCH2CH2OC2H5 30 phenyleth-1-yl-amino

(la-1.251) -OCH2CH2OC2H5 (1R)-cyclobutyl-2- NH2 Al(O-i-Pr)3 HOCH2CH2OC2H5 phenyleth-1-yl-amino

(la-1.252) -OCH2CH2OC2H5 (1S)-cyclobutyl-2- NH2 Al(O-i-Pr)3 HOCH2CH2OC2H5 35 phenyleth-1-yl-amino

(la-1.253) -OCH2CH2OC2H5 (1R,2R)-2,3-dihydro- NH2 Al(O-i-Pr)3 HOCH2CH2OC2H5 2,4,6-trimethyl-1H- inden-1yl-amino

40 (la-1.254) -OCH2CH2OC2H5 (1S,2S)-2,3-dihydro- NH2 Al(O-i-Pr)3 HOCH2CH2OC2H5 2,4,6-trimethyl-1H- inden-1yl-amino

(la-1.255) -OCH2CH2OC2H5 (1S,2R)-2,3-dihydro- NH2 Al(O-i-Pr)3 HOCH2CH2OC2H5 2-methyl-1H-inden- 45 1yl-amino

(la-1.256) -OCH2CH2OC2H5 (1S,2S)-2,3-dihydro- NH2 Al(O-i-Pr)3 HOCH2CH2OC2H5 2-methyl-1H-inden-1 yl-amino 50 (la-1.257) -OCH(CH3)C2H5 morpholin-yl NHBz Al(O-i-Bu)3 HOCH(CH3)C2H5

(la-1.258) -OCH(CH3)C2H5 benzylamino NHBz Al(O-i-Bu)3 HOCH(CH3)C2H5

(la-1.259) -OCH(CH3)C2H5 cyclohexylamino NHBz Al(O-i-Bu)3 HOCH(CH3)C2H5

55 (la-1.260) -OCH(CH3)C2H5 2,3-dihydro-6-methyl- NHBz Al(O-i-Bu)3 HOCH(CH3)C2H5 1H-inden-1yl-amino

50 EP 2 231 679 B1

(continued)

Cpd. no. Y NR1R2 NR3R4 Al-source Solvent

(la-1.261) -OCH(CH3)C2H5 (1R)-2,3-dihydro-6- NHBz Al(O-i-Bu)3 HOCH(CH3)C2H5 5 methyl-1H-inden-1yl- amino

(la-1.262) -OCH(CH3)C2H5 (1S)-2,3-dihydro-6- NHBz Al(O-i-Bu)3 HOCH(CH3)C2H5 methyl-1H-inden-1yl- 10 amino

(la-1.263) -OCH(CH3)C2H5 1,2,3,4-tetrahydro- NHBz Al(O-i-Bu)3 HOCH(CH3)C2H5 quinolin-1-yl

(la-1.264) -OCH(CH3)C2H5 1,2,3,4-tetrahydro- NHBz Al(O-i-Bu)3 HOCH(CH3)C2H5 15 isoquinolin-2-yl

(la-1.265) -OCH(CH3)C2H5 1,2,3,4-tetrahydro- NHBz Al(O-i-Bu)3 HOCH(CH3)C2H5 napht-1-yl-amino

(la-1.266) -OCH(CH3)C2H5 (1R)-1,2,3,4- NHBz Al(O-i-Bu)3 HOCH(CH3)C2H5 tetrahydro-napht-1-yl- 20 amino

(la-1.267) -OCH(CH3)C2H5 (1S)-1,2,3,4- NHBz Al(O-i-Bu)3 HOCH(CH3)C2H5 tetrahydro-napht-1-yl- amino 25 (la-1.268) -OCH(CH3)C2H5 (1R,2S)-2,3-dihydro- NHBz Al(O-i-Bu)3 HOCH(CH3)C2H5 2,6-dimethyl-1H- inden-1yl-amino

(la-1.269) -OCH(CH3)C2H5 (1S,2R)-2,3-dihydro- NHBz Al(O-i-Bu)3 HOCH(CH3)C2H5 30 2,4,6-trimethyl-1H- inden-1yl-amino

(la-1.270) -OCH(CH3)C2H5 (1R,2R)-2,3-dihydro- NHBz Al(O-i-Bu)3 HOCH(CH3)C2H5 2,6-dimethyl-1H- inden-1yl-amino 35 (la-1.271) -OCH(CH3)C2H5 (1S,2S)-2,3-dihydro- NHBz Al(O-i-Bu)3 HOCH(CH3)C2H5 2,6-dimethyl-1H- inden-1yl-amino

(la-1.272) -OCH(CH3)C2H5 (1R,2S)-2,3-dihydro- NHBz Al(O-i-Bu)3 HOCH(CH3)C2H5 40 2-methyl-1H-inden- 1yl-amino

(la-1.273) -OCH(CH3)C2H5 (1R,2R)-2,3-dihydro- NHBz Al(O-i-Bu)3 HOCH(CH3)C2H5 2-methyl-1H-inden-

45 1yl-amino

(la-1.274) -OCH(CH3)C2H5 (1R,2S)-2,3-dihydro- NHBz Al(O-i-Bu)3 HOCH(CH3)C2H5 2,4,6-trimethyl-1H- inden-1yl-amino (la-1.275) -OCH(CH )C H (1S,2R)-2,3-dihydro- NHBz Al(O-i-Bu) HOCH(CH )C H 50 3 2 5 3 3 2 5 2,6-methyl-1H-inden- 1yl-amino

(la-1.276) -OCH(CH3)C2H5 (3RS, 4RS)-3-methyl- NHBz Al(O-i-Bu)3 HOCH(CH3)C2H5 3,4-dihydro-2H- 55 chromen-4-yl-amino

51 EP 2 231 679 B1

(continued)

Cpd. no. Y NR1R2 NR3R4 Al-source Solvent

(la-1.277) -OCH(CH3)C2H5 (3R, 4R)-3-methyl-3,4- NHBz Al(O-i-Bu)3 HOCH(CH3)C2H5 5 dihydro-2H-chromen- 4-yl-amino

(la-1.278) -OCH(CH3)C2H5 (3S, 4S)-3-methyl-3,4- NHBz Al(O-i-Bu)3 HOCH(CH3)C2H5 dihydro-2H-chromen- 10 4-yl-amino

(la-1.279) -OCH(CH3)C2H5 1-cyclopropylethyl- NHBz Al(O-i-Bu)3 HOCH(CH3)C2H5 amino

(la-1.280) -OCH(CH3)C2H5 (1R)-cyclopropylethyl- NHBz Al(O-i-Bu)3 HOCH(CH3)C2H5 15 amino

(la-1.281) -OCH(CH3)C2H5 (1S)-cyclopropylethyl- NHBz Al(O-i-Bu)3 HOCH(CH3)C2H5 amino

(la-1.282) -OCH(CH3)C2H5 1-(4-chlorphenyl)eth- NHBz Al(O-i-Bu)3 HOCH(CH3)C2H5 1-yl-amino 20

(la-1.283) -OCH(CH3)C2H5 (1R)-(4-chlorphenyl) NHBz Al(O-i-Bu)3 HOCH(CH3)C2H5 eth-1-yl-amino

(la-1.284) -OCH(CH3)C2H5 (1S)-(4-chlorophenyl) NHBz Al(O-i-Bu)3 HOCH(CH3)C2H5 eth-1-yl-amino 25 (l a-1.285) -OCH(CH3)C2H5 1-methyl-2-(3,5- NHBz Al(O-i-Bu)3 HOCH(CH3)C2H5 dimethylphenyloxy) eth-1-yl-amino

(la-1.286) -OCH(CH3)C2H5 (1R)-1-methyl-2-(3,5- NHBz Al(O-i-Bu)3 HOCH(CH3)C2H5 30 dimethylphenyloxy) eth-1-yl-amino

(la-1.287) -OCH(CH3)C2H5 (1S)-1-methyl-2-(3,5- NHBz Al(O-i-Bu)3 HOCH(CH3)C2H5 dimethylphenyloxy) 35 eth-1-yl-amino

(la-1.288) -OCH(CH3)C2H5 1,1- NHBz Al(O-i-Bu)3 HOCH(CH3)C2H5 dicyclopropylmethyl- amino

40 (la-1.289) -OCH(CH3)C2H5 pent-3-ylamino NHBz Al(O-i-Bu)3 HOCH(CH3)C2H5

(la-1.290) -OCH(CH3)C2H5 1-cyclobutyl-2- NHBz Al(O-i-Bu)3 HOCH(CH3)C2H5 phenyleth-1-yl-amino

(la-1.291) -OCH(CH3)C2H5 (1R)-cyclobutyl-2- NHBz Al(O-i-Bu)3 HOCH(CH3)C2H5 phenyleth-1-yl-amino 45

(la-1.292) -OCH(CH3)C2H5 (1S)-cyclobutyl-2- NHBz Al(O-i-Bu)3 HOCH(CH3)C2H5 phenyleth-1-yl-amino

(la-1.293) -OCH(CH3)C2H5 (3S, 4R)-3-methyl-3,4- NHBz Al(O-i-Bu)3 HOCH(CH3)C2H5 dihydro-2H-chromen- 50 4-yl-amino

(la-1.294) -OCH(CH3)C2H5 (3R, 4S)-3-methyl-3,4- NHBz Al(O-i-Bu)3 HOCH(CH3)C2H5 dihydro-2H-chromen- 4-yl-amino 55 (la-1.295) -OCH2CH2OC2H5 (3S, 4R)-3-methyl-3,4- NH2 Al(O-i-Pr)3 HOCH2CH2OC2H5 dihydro-2H-chromen- 4-yl-amino

52 EP 2 231 679 B1

(continued)

Cpd. no. Y NR1R2 NR3R4 Al-source Solvent

(la-1.296) -OCH2CH2OC2H5 (3R, 4S)-3-methyl-3,4- NH2 Al(O-i-Pr)3 HOCH2CH2OC2H5 5 dihydro-2H-chromen- 4-yl-amino

(la-1.297) -O- i- Pr (3S, 4R)-3-methyl-3,4- NH2 Al(O-i-Pr)3 (CH3)2CHOH dihydro-2H-chromen- 10 4-yl-amino

(la-1.298) -O- i- Pr (3R, 4S)-3-methyl-3,4- NH2 Al(O-i-Pr)3 (CH3)2CHOH dihydro-2H-chromen- 4-yl-amino

15 [0123] Reaction Conditions as to Table II:

1) Reaction temperature of 90 to 100 ˚C 2) Al-source used in an amount of 1 to 2 eq based on amine

20 3) cyanoguanidine used in an amount of 1 to 2 eq based on amine

[0124] Abbreviations as to Table II:

-O-i-Pr = Isopropoxy

25 Bz = benzyl NHBz = benzylamino NBz2 = dibenzylamino

30 Claims

1. Compounds of formula (I) or salts thereof,

in which

45 1 R is (C1-C18)alkyl, (C2-C18)alkenyl or (C2-C18)alkynyl, wherein each of the last-mentioned three radicals is unsubstituted or substituted, or is a group of the formula A1 or B1, 2 R is H, (C1-C18)alkyl, (C2-C18)alkenyl or (C2-C18)alkynyl, 50 wherein each of the last-mentioned three radicals is unsubstituted or substituted, or is a group of the formula A2, 3 R is H, (C1-C18)alkyl, (C2-C18)alkenyl or (C2-C18)alkynyl, wherein each of the last-mentioned three radicals is unsubstituted or substituted, or is a group of the formula A3, 4 55 R is H, (C1-C18)alkyl, (C2-C18)alkenyl or (C2-C18)alkynyl, wherein each of the last-mentioned three radicals is unsubstituted or substituted, or is a group of the formula A4, 5 R is H, (C1-C18)alkyl, (C2-C18)alkenyl or (C2-C18)alkynyl,

53 EP 2 231 679 B1

wherein each of the last-mentioned three radicals is unsubstituted or substituted, or is a group of the formula A5, 6 R is H, (C1-C18)alkyl, (C2-C18)alkenyl or (C2-C18)alkynyl, wherein each of the last-mentioned three radicals is unsubstituted or substituted, 5 or is a group of the formula A6, or R1 and R2 or R3 and R4 together with the N-atom linked to each other form a N-heterocyclic ring having 3 to 7 ring atoms and optionally having one or more additional hetero atoms selected from the group consisting of N, O and S and which is unsubstituted or substituted, 1 2 3 4 5 6 A ,A,A,A,A and A , independently of one another, are (C3-C9)cycloalkyl, (C4-C9)cycloalkenyl, (C5-C9) 10 cycloalkinyl, aryl or heterocyclyl as a basic cyclic moiety, wherein the basic cyclic moiety is unsubstituted or substituted, B1 is a group as defined for R1 further linked to the amino group of the group of the formula (I*),

wherein R2*, R3*, R4*, R5*, R6*, X* and Y* are independently as defined in formula (I) for R2,R3,R4,R5,R6, X and 25 Y, respectively, X and Y each, independently of one another, are selected from the group consisting of

(i) amino, (ii) a group of the formula NR7R8 in which R7 is a radical selected from the group consisting of radicals as 30 defined for and independently of R1, and in which R8 is a radical selected from the group consisting of radicals as defined for and independently of R2, (iii) hydroxy, (iv) (C1-C6)alkoxy, (C1-C6)haloalkoxy, (C1-C6)alkoxy-(C1-C6)alkoxy and (C1-C6)alkylthio, (v) (C1-C6)alkoxy, (C1-C6)haloalkoxy, (C1-C6)alkoxy-(C1-C6)alkoxy and (C1-C6)alkylthio, wherein each of the 35 latter 4 radicals is substituted by one or more radicals selected from the group consisting of (C3-C6)cycloalkyl, (C3-C6)cycloalkoxy, wherein each of the last-mentioned 2 radicals is unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, hydroxy, carbamoyl, (C1-C6)alkyl, (C1-C6)haloalkyl, (C1-C6)alkoxy-(C1-C6)alkyl, (C1-C6)alkoxy, (C1-C6)haloalkoxy and (C1-C6)alkoxy-(C1-C6)alkoxy, aryl and aryloxy, 40 wherein each of the last-mentioned 2 radicals is unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, hydroxy, nitro, carbamoyl, sulfo, (C1-C6)alkyl, (C1-C6)haloalkyl, (C1-C6) alkoxy-(C1-C6)alkyl, (C1-C6)alkoxy, (C1-C6)haloalkoxy, (C1-C6)alkoxy-(C1-C6)alkoxy, (C1-C6)alkylthio, (C1-C6) alkylsulfinyl, (C1-C6)haloalkylsulfinyl, (C1-C6)alkylsulfonyl, (C1-C6)haloalkylsulfonyl, di-[(C1-C4)alkyl]-amino, (C1-C4)alkylamino-carbonyl, di-[(C1-C4)alkyl]-amino-carbonyl, (C1-C4)alkylamino-carbonylamino and 45 di-[(C1-C4)alkyl]-aminocarbonylamino, (vi) (C3-C6)cycloalkoxy which is unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, hydroxy, carbamoyl, (C1-C6)alkyl, (C1-C6)haloalkyl, (C1-C6)alkoxy-(C1-C6)alkyl, (C1-C6) alkoxy, (C1-C6)haloalkoxy and (C1-C6)alkoxy-(C1-C6)alkoxy, (vii) aryloxy which is unsubstituted or substituted, and 50 (viii) acyloxy, acylthio or acylamino, or

X and Y together are a divalent group of the formula -U1-D*-U2- in which

55 D* is a hydrocarbon bridge, optionally interrupted by one or more divalent groups of the formula U3 defined below, and U1,U2 and U3, independently of each other are selected from the group consisting of NH, NR’ , O and S, wherein R’ is (C1-C6)alkyl, hydroxy-(C1-C6)alkyl or (C1-C6)alkoxy-(C1-C6)alkyl,

54 EP 2 231 679 B1

or X is a radical as defined above and Y is an organic ligand based on a compound of the formula Y’-H, Y’-RL or RL-U3-D**-U4-RLL wherein D** is a divalent group as defined for the group D* above, Y’ is a radical as defined for Y, U3 is a divalent group as defined for U1 above, U4 is a divalent group as defined for U2 above, each of 5 L LL R and R is a radical group selected from the group consisting of (C1-C6)alkyl, hydroxy-(C1-C6)alkyl or (C1-C6) alkoxy-(C1-C6)alkyl, and wherein the organic ligand is coordinated to the aluminium atom of the complex by a free electron pair of a hetero atom contained therein and selected from the group consisting of N, O and S, or X and Y together are a radical of the formula -U1-D*-U2-RLLL in which U1,U2 and D* are as defined above, and 10 LLL R is a radical selected from the group consisting of (C1-C6)alkyl, hydroxy-(C1-C6)alkyl or (C1-C6) 1 2 LLL alkoxy-(C1-C6)alkyl, and wherein the radical -U -D*-U -R is additionally coordinated to the aluminium atom of the complex by a free electron pair located at a hetero atom contained in the radical (position represented by Y).

2. Compound as claimed in claim 1, characterized in that 15 1 R is (C1-C18)alkyl, (C2-C18)alkenyl or (C2-C18)alkynyl, wherein each of the last-mentioned three radicals is unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, hydroxy, nitro, carbamoyl, sulfo and radicals of the formulae -O-R1a,-S- 1b 1c 1d 1e 1f 1g 1h 1i 1j 1k 1a R , -S(=O)-R , -S(=O)2-R ,-NR R , -C(=O)-NHR , -C(=O)-NR R , -NHC(=O)-NR R and A , 20 1a 1b 1c 1d 1e 1f 1g 1h 1i 1j 1k wherein R ,R ,R ,R ,R ,R ,R ,R ,R ,R , and R , independently of one another, are (C1-C6) 1b alkyl, (C1-C6)haloalkyl, (C1-C6)alkoxy-(C1-C6)alkyl or a radical of the formula A , or is a group of the formula A1 or B1, 2 R is H, (C1-C18)alkyl, (C2-C18)alkenyl or (C2-C18)alkynyl, wherein each of the last-mentioned three radicals is unsubstituted or substituted by one or more radicals selected 25 from the group consisting of halogen, hydroxy, nitro, carbamoyl, sulfo and radicals of the formulae- O-R2a,-S- 2b 2c 2d 2e 2f 2g 2h 2i 2j 2k 2a R , -S(=O)-R , -S(=O)2-R ,-NR R , -C(=O)-NHR , -C(=O)-NR R , -NHC(=O)-NR R and A , wherein 2a 2b 2c 2d 2e 2f 2g 2h 2i 2j 2k R ,R ,R ,R ,R ,R ,R ,R ,R ,R , and R , independently of one another, are (C1-C6)alkyl, (C1-C6) 2b haloalkyl, (C1-C6)alkoxy-(C1-C6)alkyl or a radical of the formula A , or is a group of the formula A2, 30 3 R is H, (C1-C18)alkyl, (C2-C18)alkenyl or (C2-C18)alkynyl, wherein each of the last-mentioned three radicals is unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, hydroxy, nitro, carbamoyl, sulfo and radicals of the formulae -O-R3a,-S- 3b 3c 3d 3e 3f 3g 3h 3i 3j 3k 3b R , -S(=O)-R , -S(=O)2-R ,-NR R , -C(=O)-NHR , -C(=O)-NR R , -NHC(=O)-NR R and A , 3a 3b 3c 3d 3e 3f 3g 3h 3i 3j 3k wherein R ,R ,R ,R ,R ,R ,R ,R ,R ,R , and R , independently of one another, are (C1-C6) 35 3b alkyl, (C1-C6)haloalkyl, (C1-C6)alkoxy-(C1-C6)alkyl or a radical of the formula A , or is a group of the formula A3, 4 R is H, (C1-C18)alkyl, (C2-C18)alkenyl or (C2-C18)alkynyl, wherein each of the last-mentioned three radicals is unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, hydroxy, nitro, carbamoyl, sulfo and radicals of the formulae -O-R4a,-S- 40 4b 4c 4d 4e 4f 4g 4h 4i 4j 4k 4a R , -S(=O)-R , -S(=O)2-R ,-NR R , -C(=O)-NHR , -C(=O)-NR R , -NHC(=O)-NR R and A , 4a 4b 4c 4d 4e 4f 4g 4h 4i 4j 4k wherein R ,R ,R ,R ,R ,R ,R ,R ,R ,R , and R , independently of one another, are (C1-C6) 4b 4 alkyl, (C1-C6)haloalkyl, (C1-C6)alkoxy-(C1-C6)alkyl or a radical of the formula A , or is a group of the formula A , 5 R is H, (C1-C18)alkyl, (C2-C18)alkenyl or (C2-C18)alkynyl, wherein each of the last-mentioned three radicals is unsubstituted or substituted by one or more radicals selected 45 from the group consisting of halogen, hydroxy, nitro, carbamoyl, sulfo and radicals of the formulae -O-R5a,-S- 5b 5c 5d 5e 5f 5g 5h 5i 5j 5k 5a R , -S(=O)-R , -S(=O)2-R ,-NR R , -C(=O)-NHR , -C(=O)-NR R , -NHC(=O)-NR R and A , 5a 5b 5c 5d 5e 5f 5g 5h 5i 5j 5k wherein R ,R ,R ,R ,R ,R ,R ,R ,R ,R , and R , independently of one another, are (C1-C6) 5b alkyl, (C1-C6)haloalkyl, (C1-C6)alkoxy-(C1-C6)alkyl or a radical of the formula A , or is a group of the formula A5, 50 6 R is H, (C1-C18)alkyl, (C2-C18)alkenyl or (C2-C18)alkynyl, wherein each of the last-mentioned three radicals is unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, hydroxy, nitro, carbamoyl, sulfo and radicals of the formulae -O-R6a,-S- 6b 6c 6d 6e 6f 6g 6h 6i 6j 6k 6a R , -S(=O)-R , -S(=O)2-R ,-NR R , -C(=O)-NHR , -C(=O)-NR R , -NHC(=O)-NR R and A , 6a 6b 6c 6d 6e 6f 6g 6h 6i 6j 6k wherein R ,R ,R ,R ,R ,R ,R ,R ,R ,R , and R , independently of one another, are (C1-C6) 55 6b alkyl, (C1-C6)haloalkyl, (C1-C6)alkoxy-(C1-C6)alkyl or a radical of the formula A , or is a group of the formula A6, or R1 and R2 or R3 and R4 together with the N-atom linked to each other form a N-heterocyclic ring having 3 to 7 ring atoms and optionally having one or more additional hetero atoms selected from the group consisting of N,

55 EP 2 231 679 B1

O and S and which is unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, hydroxy, nitro, carbamoyl, sulfo, (C1-C6)alkyl, (C1-C6)haloalkyl, (C1-C6)alkoxy-(C1-C6)alkyl, (C1-C6) alkoxy, (C1-C6)haloalkoxy, (C1-C6)alkoxy-(C1-C6)alkoxy, (C1-C6)alkylthio, (C1-C6)alkylsulfinyl, (C1-C6) haloalkylsulfinyl, (C1-C6)alkylsulfonyl, (C1-C6)haloalkylsulfonyl, di-[(C1-C4)alkyl]-amino, (C1-C4)alkylamino-car- 5 bonyl,di-[(C1-C4)alkyl]-amino-carbonyl,(C1-C4)alkylamino-carbonylamino,di-[(C1-C4)alkyl]-aminocarbonylamino and oxo, A1,A1a,A1b,A2,A2a,A2b,A3,A3a,A3b,A4,A4a,A4b,A5,A5a,A5b,A6,A6a, and A6b, independently of one another, are (C3-C9)cycloalkyl, (C4-C9)cycloalkenyl, (C5-C9)cycloalkinyl, aryl or heterocyclyl as a basic cyclic moiety, wherein the basic cyclic moiety 10 (a) is unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, hydroxy, nitro, carbamoyl, sulfo, (C1-C6)alkyl, (C1-C6)haloalkyl, (C1-C6)alkoxy-(C1-C6)alkyl, (C1-C6)alkoxy, (C1-C6)haloalkoxy, (C1-C6)alkoxy-(C1-C6)alkoxy, (C1-C6)alkylthio, (C1-C6)alkylsulfinyl, (C1-C6)haloalkylsulfinyl, (C1-C6)alkylsulfonyl, (C1-C6)haloalkylsulfonyl, di-[(C1-C4)alkyl]-amino, (C1-C4)alkylamino-carbon- 15 yl, di-[(C1-C4)alkyl]-amino-carbonyl, (C1-C4)alkylamino-carbonylamino and di-[(C1-C4)alkyl]-amino-carbonylamino and, in case of heterocyclyl, also oxo attached to heteroring atoms N or S or in alpha-position of an N-atom as heteroring atom, or (b) is substituted by or substituted additionally to one or more of the substituents mentioned in (a) by a 20 bridge linked geminal (a 1,1-position), vicinal (a 1,2-position) or in a 1,3-position at the basic cyclic moiety thus forming another carbocyclic or heterocyclic ring together with the part of the basic cyclic moiety between the atoms linked to the bridge, wherein the carbocyclic or heterocyclic ring formed is saturated, partly unsaturated, unsaturated, aromatic or heteroaromatic and wherein the bridge is further unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, hydroxy, nitro, carbamoyl, 25 sulfo, (C1-C6)alkyl, (C1-C6)haloalkyl, (C1-C6)alkoxy-(C1-C6)alkyl, (C1-C6)alkoxy, (C1-C6)haloalkoxy, (C1-C6)alkoxy-(C1-C6)alkoxy, (C1-C6)alkylthio, (C1-C6)alkylsulfinyl, (C1-C6)haloalkylsulfinyl, (C1-C6)alkylsulfonyl, (C1-C6)haloalkylsulfonyl, di-[(C1-C4)alkyl]-amino, (C1-C4)alkylamino-carbonyl, di-[(C1-C4) alkyl]-amino-carbonyl, (C1-C4)alkylamino-carbonylamino and di-[(C1-C4)alkyl]-aminocarbonylamino,

30 B1 is a group as defined for R1 further linked to the amino group of the group of the formula (I*),

wherein R2*, R3*, R4*, R5*, X* and Y* are independently as defined in formula (I) for R2,R3,R4,R5, X and Y, respectively,

45 X and Y each, independently of one another, are selected from the group consisting of

(i) amino, (ii) a group of the formula NR7R8 in which R7 is a radical selected from the group consisting of radicals as defined for and independently of R1, and in which R8 is a radical selected from the group consisting of radicals 50 as defined for and independently of R2, (iii) hydroxy, (iv) (C1-C6)alkoxy, (C1-C6)haloalkoxy, (C1-C6)alkoxy-(C1-C6)alkoxy and (C1-C6)alkylthio, (v) (C1-C6)alkoxy, (C1-C6)haloalkoxy, (C1-C6)alkoxy-(C1-C6)alkoxy and (C1-C6)alkylthio, wherein each of the latter 4 radicals is substituted by one or more radicals selected from the group consisting of (C3-C6)cycloalkyl, 55 (C3-C6)cycloalkoxy, wherein each of the last-mentioned 2 radicals is unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, hydroxy, carbamoyl, (C1-C6)alkyl, (C1-C6)haloalkyl, (C1-C6)alkoxy-(C1-C6) alkyl, (C1-C6)alkoxy, (C1-C6)haloalkoxy and (C1-C6)alkoxy-(C1-C6)alkoxy,

56 EP 2 231 679 B1

aryl and aryloxy, wherein each of the last-mentioned 2 radicals is unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, hydroxy, nitro, carbamoyl, sulfo, (C1-C6)alkyl, (C1-C6)haloalkyl, (C1-C6) alkoxy-(C1-C6)alkyl, (C1-C6)alkoxy, (C1-C6)haloalkoxy, (C1-C6)alkoxy-(C1-C6)alkoxy, (C1-C6)alkylthio, (C1-C6) 5 alkylsulfinyl, (C1-C6)haloalkylsulfinyl, (C1-C6)alkylsulfonyl, (C1-C6)haloalkylsulfonyl, di-[(C1-C4)alkyl]-amino, (C1-C4)alkylamino-carbonyl, di-[(C1-C4)alkyl]-amino-carbonyl, (C1-C4)alkylamino-carbonylamino and di-[(C1-C4)alkyl]-aminocarbonylamino, (vi) (C3-C6)cycloalkoxy which is unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, hydroxy, carbamoyl, (C1-C6)alkyl, (C1-C6)haloalkyl, (C1-C6)alkoxy-(C1-C6)alkyl, (C1-C6) 10 alkoxy, (C1-C6)haloalkoxy and (C1-C6)alkoxy-(C1-C6)alkoxy, (vii) aryloxy which is unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, hydroxy, nitro, carbamoyl, sulfo, (C1-C6)alkyl, (C1-C6)haloalkyl, (C1-C6)alkoxy-(C1-C6)alkyl, (C1-C6) alkoxy, (C1-C6)haloalkoxy, (C1-C6)alkoxy-(C1-C6)alkoxy, (C1-C6)alkylthio, (C1-C6)alkylsulfinyl, (C1-C6) haloalkylsulfinyl, (C1-C6)alkylsulfonyl, (C1-C6)haloalkylsulfonyl, di-[(C1-C4)alkyl]-amino, (C1-C4)alkylamino-car- 15 bonyl, di-[(C1-C4)alkyl]-amino-carbonyl, (C1-C4)alkylamino-carbonylamino and di-[(C1-C4)alkyl]-aminocarbonylamino, and (viii) acyloxy, acylthio or acylamino, each having 1 to 12 carbon atoms,

20 or X and Y together are a divalent group of the formula -U1-D*-U2- in which

D* is a linear alkylene bridge, a linear (C2-C10)alkenylene bridge, a linear (C2-C10)alkynylene bridge, a (C3-C9) cycloalkylene bridge, a phenylene bridge or a bridge consisting of a combination of two or more of said linear 25 acyclic and cyclic moieties having in total 4 to 24 carbon atoms, wherein the bridge in each case is unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, hydroxy, nitro, carbamoyl, sulfo, (C1-C6)alkyl, (C1-C6)haloalkyl, (C1-C6)alkoxy-(C1-C6)alkyl, (C1-C6)alkoxy, (C1-C6)haloalkoxy, (C1-C6) alkoxy-(C1-C6)alkoxy, (C1-C6)alkylthio, (C1-C6)alkylsulfinyl, (C1-C6)haloalkylsulfinyl, (C1-C6)alkylsulfonyl, (C1-C6)haloalkylsulfonyl, di-[(C1-C4)alkyl]-amino, (C1-C4)alkylamino-carbonyl, di-[(C1-C4)alkyl]-amino-carbon- 30 yl, (C1-C4)alkylamino-carbonylamino and di-[(C1-C4)alkyl]-aminocarbonylamino, and U1,U2 and U3, independently of each other are selected from the group consisting of NH, NR’ , O and S, wherein R’ is (C1-C6)alkyl, hydroxy-(C1-C6)alkyl or (C1-C6)alkoxy-(C1-C6)alkyl, or X is a radical as defined above and Y is an organic ligand based on a compound of the formula Y’-H, Y’-RL or RL-U3-D**-U4-RLL wherein D** is a divalent group as defined for the group D* above, Y’ is a radical as defined 35 for Y, U3 is a divalent group as defined for U1 above, U4 is a divalent group as defined for U2 above, each of L LL R and R is a radical group selected from the group consisting of (C1-C6)alkyl, hydroxy-(C1-C6)alkyl or (C1-C6) alkoxy-(C1-C6)alkyl, and wherein the organic ligand is coordinated to the aluminium atom of the complex by a free electron pair of a hetero atom contained therein and selected from the group consisting of N, O and S, or 40 X and Y together are a radical of the formula -U1-D*-U2-RLLL in which U1,U2 and D* are as defined above, and LLL R is a radical selected from the group consisting of (C1-C6)alkyl, hydroxy-(C1-C6)alkyl or (C1-C6) alkoxy-(C1-C6)alkyl, and wherein the radical -U1-D*-U2-RLLL is additionally coordinated to the aluminium atom of the complex by a free electron pair located at a hetero atom contained in the radical (position represented by Y), preferably located 45 at the heteroatom of the divalent group U2.

3. Compound as claimed in claim 1 or 2, characterized in that

1 R is (C1-C12)alkyl, (C2-C12)alkenyl or (C2-C12)alkynyl, 50 wherein each of the last-mentioned three radicals is unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, hydroxy, nitro, carbamoyl, sulfo and radicals of the formulae -O-R1a,-S- 1b 1c 1d 1e 1f 1g 1h 1i 1j 1k 1a R , -S(=O)-R , -S(=O)2-R ,-NR R , -C(=O)-NHR , -C(=O)-NR R , -NHC(=O)-NR R and A , wherein 1a 1b 1c 1d 1e 1f 1g 1h 1i 1j 1k R ,R ,R ,R ,R ,R ,R ,R ,R ,R , and R , independently of one another, are (C1-C6)alkyl, (C1-C6) 1b haloalkyl, (C1-C6)alkoxy-(C1-C6)alkyl or a radical of the formula A , 55 or is a group of the formula A1 or B1, or R1 and R2 together with the N-atom linked to each other form a N-heterocyclic ring having 5 or 6 ring atoms and optionally having 1, 2 or 3 additional hetero atoms selected from the group consisting of N, O and S and which is unsubstituted or substituted by one or more radicals selected from the group consisting of halogen,

57 EP 2 231 679 B1

(a) is unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, 10 hydroxy, nitro, carbamoyl, sulfo, (C1-C6)alkyl, (C1-C6)haloalkyl, (C1-C6)alkoxy-(C1-C6)alkyl, (C1-C6)alkoxy, (C1-C6)haloalkoxy, (C1-C6)alkoxy-(C1-C6)alkoxy, (C1-C6)alkylthio, (C1-C6)alkylsulfinyl, (C1-C6)haloalkylsulfinyl, (C1-C6)alkylsulfonyl, (C1-C6)haloalkylsulfonyl, di-[(C1-C4)alkyl]-amino, (C1-C4)alkylamino-carbonyl di-[(C1-C4)alkyl]-amino-carbonyl, (C1-C4)alkylamino-carbonylamino and di-[(C1-C4)alkyl]-amino-carbonylamino and, in case of heterocyclyl, also oxo attached to heteroring atoms N or S or in alpha-position of 15 an N-atom as heteroring atom, or (b) is substituted by or substituted additionally to one or more of the substituents mentioned in (a) by a bridge linked geminal (a 1,1-position), vicinal (a 1,2-position) or in a 1,3-position at the basic cyclic moiety thus forming another carbocyclic or heterocyclic ring together with the part of the basic cyclic moiety between 20 the atoms linked to the bridge, wherein the carbocyclic or heterocyclic ring formed is saturated, partly unsaturated, unsaturated having 3 to 9 ring atoms or is aromatic or

heteroaromatic having 5 or 6 ring atoms and wherein the bridge is further unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, hydroxy, nitro, carbamoyl, sulfo, (C1-C6)alkyl, 25 (C1-C6)haloalkyl, (C1-C6)alkoxy-(C1-C6)alkyl, (C1-C6)alkoxy, (C1-C6)haloalkoxy, (C1-C6)alkoxy-(C1-C6)alkoxy, (C1-C6)alkylthio, (C1-C6)alkylsulfinyl, (C1-C6)haloalkylsulfinyl, (C1-C6)alkylsulfonyl, (C1-C6)haloalkylsulfonyl, di-[(C1-C4)alkyl]-amino, (C1-C4)alkylamino-carbonyl, di-[(C1-C4)alkyl]-amino-carbonyl, (C1-C4)alkylamino-carbonylamino and di-[(C1-C4)alkyl]-amino-carbonylamino and, in case of heterocyclyl, also oxo attached to heteroring atoms N or S or in alpha-position of an N-atom as heteroring atom, or is further benzocondensated 30 wherein the additional annellated benzene ring is unsubstituted or further substituted by one or more radicals as defined for substitution of the bridge which is benzocondensated, B1 is a group as defined for R1 further linked to the amino group of the group of the formula (I*),

wherein R2*, R3*, R4*, R5*, R6*, X* and Y* are independently as defined in formula (I) for R2,R3,R4,R5,R6, X and 45 Y, respectively.

4. Compound as claimed in any of claims 1 to 3, characterized in that

2 R is H, (C1-C4)alkyl, (C2-C4)alkenyl or (C2-C4)alkynyl, (C1-C4)haloalkyl, phenyl, naphthyl, phenyl(C1-C4)alkyl 50 or (C3-C6)cycloalkyl, wherein each of the last-mentioned 4 radicals is unsubstituted or substituted in the cyclic moiety by one or more radicals as defined for substituents at the cyclic group A2, and R3, R4, R5 and R6 each are H,

5. Compound as claimed in any of claims 1 to 4, characterized in that X and Y, independently of one another, are 55 each selected from the group consisting of

(i) amino, (ii) a group of the formula NR7R8 which is defined as the group NR1R2 in formula (I),

58 EP 2 231 679 B1

(iii) hydroxy, (iv) (C1-C4)alkoxy, (C1-C4)haloalkoxy, (C1-C4)alkoxy-(C1-C4)alkoxy and (C1-C4)alkylthio, (v) (C1-C4)alkoxy, (C1-C4)haloalkoxy, (C1-C4)alkoxy-(C1-C4)alkoxy and (C1-C4)alkylthio, wherein each of the latter 4 radicals is substituted by one or more radicals selected from the group consisting of (C3-C6)cycloalkyl, 5 (C3-C6)cycloalkoxy, wherein each of the last-mentioned 2 radicals is unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, hydroxy, carbamoyl, (C1-C4)alkyl, (C1-C4)haloalkyl, (C1-C4)alkoxy-(C1-C4) alkyl, (C1-C4)alkoxy, (C1-C4)haloalkoxy and (C1-C4)alkoxy-(C1-C4)alkoxy, phenyl or phenoxy, wherein each of the last-mentioned 2 radicals is unsubstituted or substituted by one or more radicals selected 10 from the group consisting of halogen, hydroxy, nitro, carbamoyl, sulfo, (C1-C4)alkyl, (C1-C4)haloalkyl, (C1-C4) alkoxy-(C1-C4)alkyl, (C1-C4)alkoxy, (C1-C4)haloalkoxy, (C1-C4)alkoxy-(C1-C4)alkoxy, (C1-C4)alkylthio, (C1-C4) alkylsulfinyl, (C1-C4)haloalkylsulfinyl, (C1-C4)alkylsulfonyl, (C1-C4)haloalkylsulfonyl, di-[(C1-C4)alkyl]-amino, (C1-C4)alkylamino-carbonyl, di-[(C1-C4)alkyl]-amino-carbonyl, (C1-C4)alkylamino-carbonylamino and di-[(C1-C4)alkyl]-aminocarbonylamino, 15 (vi) (C3-C6)cycloalkoxy which is unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, hydroxy, carbamoyl, (C1-C4)alkyl, (C1-C4)haloalkyl, (C1-C4)alkoxy-(C1-C4)alkyl, (C1-C4) alkoxy, (C1-C4)haloalkoxy and (C1-C4)alkoxy-(C1-C4)alkoxy, and (vii) phenoxy, which is unsubstituted or substituted by one or more radicals selected from the group consisting 20 of halogen, hydroxy, nitro, carbamoyl, sulfo, (C1-C4)alkyl, (C1-C4)haloalkyl, (C1-C4)alkoxy-(C1-C4)alkyl, (C1-C4) alkoxy, (C1-C4)haloalkoxy, (C1-C4)alkoxy-(C1-C4)alkoxy, (C1-C4)alkylthio, (C1-C4)alkylsulfinyl, (C1-C4) haloalkylsulfinyl, (C1-C4)alkylsulfonyl, (C1-C4)haloalkylsulfonyl, di-[(C1-C4)alkyl]-amino, (C1-C4)alkylamino-carbonyl, di-[(C1-C4)alkyl]-amino-carbonyl, (C1-C4)alkylamino-carbonylamino and di-[(C1-C4)alkyl]-aminocarbonylamino, 25 and (viii) acyloxy, acylthio or acylamino, wherein acyl in the last-mentioned three groups is formyl, (C1-C6)alkylcarbonyl, (C1-C6)alkylsulfonyl or phenylsulfonyl, the latter of which is unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, (C1-C4)alkyl, (C1-C4)haloalkyl, (C1-C4)alkoxy-(C1-C4)alkyl, (C1-C4)alkoxy, (C1-C4)haloalkoxy, (C1-C4) 30 alkoxy-(C1-C4)alkoxy and (C1-C4)alkylthio, or X and Y together are a divalent group of the formula -O-D*-O-, -S-D*-S-, -NH-D*-NH-, -O-D*-NH-, -O-D*-S-, -N(CH3)-D*-N(CH3)-, -NH-D*-N(CH3)-, -N(C2H5)-D*-N(C2H5)- or -NH-D*-N(C2H5)-, wherein D* in each of the last-mentioned 9 divalent groups is a linear alkylene bridge, a linear (C2-C10)alkenylene bridge, a linear (C2-C10) 35 alkynylene bridge, a (C3-C9)cycloalkylene bridge, a phenylene bridge or a bridge consisting of a combination of two or more of said linear acyclic and cyclic moieties having in total 4 to 18 carbon atoms, wherein the bridge in each case is unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, hydroxy, nitro, carbamoyl, sulfo, (C1-C4)alkyl, (C1-C4)haloalkyl, (C1-C4)alkoxy-(C1-C4)alkyl, (C1-C4) alkoxy, (C1-C4)haloalkoxy, (C1-C4)alkoxy-(C1-C4)alkoxy, (C1-C4)alkylthio, (C1-C4)alkylsulfinyl, (C1-C4) 40 haloalkylsulfinyl, (C1-C4)alkylsulfonyl, (C1-C4)haloalkylsulfonyl, di-[(C1-C4)alkyl]-amino, (C1-C4)alkylamino-carbonyl, di-[(C1-C4)alkyl)-amino-carbonyl, (C1-C4)alkylamino-carbonylamino and di-[(C1-C4)alkyl]-aminocarbonylamino, or X is a radical as defined above and Y is an organic ligand based on a compound of the formula Y’-H, Y’-RL or RL-0-D**-O-RLL , RL-S-D**-S-RLL, 45 RL-NH-D**-NH-RLL RL-O-D**-NH-RLL, RL-O-D**-S-RLL, L LL L LL L LL L R -N(CH3)-D**-N(CH3)-R ,R-NH-D**-N(CH3)-R ,R-N(C2Hs)-D**-N(C2Hs)-R or R -NH-D**-N LL (C2H5)-R , wherein D** in each of the 9 last-mentioned compounds is a divalent group as defined for the group D* above, Y’ is a radical as defined for Y, and each of RL and RLL is a radical group selected from the group consisting 50 of (C1-C6)alkyl, hydroxy-(C1-C6)alkyl or (C1-C6)alkoxy-(C1-C6)alkyl, and wherein the organic ligand is coordinated to the aluminium atom of the complex by a free electron pair of a hetero atom contained therein and selected from the group consisting of N, O and S, or X and Y together are a radical of the formula -O-D**-O-RLLL, -S-D**-S-RLLL, -NH-D**-NH-RLLL -O-D**-NH-RLLL, 55 LLL LLL LLL LLL LLL -NH-D**-O-R -O-D**-S-R -S-D**-O-R , -N(CH3)-D**-N(CH3)-R , -NH-D**-N(CH3)-R -N(CH3)-D**- LLL LLL LLL LLL NH-R ,-N(C2H5)-D**-N(C2H5)-R , -NH-D**-N(C2Hs)-R or -N(C2H5)-D**-NH-R , wherein D* in the 13 LLL last-mentioned radicals is as defined above, and R is a radical selected from the group consisting of (C1-C4) alkyl, hydroxy-(C1-C4)alkyl or (C1-C4)alkoxy-(C1-C4)alkyl, and wherein the radical is additionally coordinated

59 EP 2 231 679 B1

to the aluminium atom of the complex by a free electron pair located at a hetero atom contained in the radical (position represented by Y), preferably located at the heteroatom attached to the group RLLL in the divalent group.

6. Process for the preparation of a compound of formula (I) or salts thereof according to any of claims 1 to 5, 5

15 in which R1 to R6 and X and Y are as defined in formula (I), characterized in that a compound (an amine) of the formula (II) or a salt thereof,

25 in which R1 and R2 are defined as in the compound of formula (I) to be prepared, is reacted to a compound of the formula (III) or a salt thereof,

35 in which R3,R4,R5 and R6 are defined as in the compound of formula (I) to be prepared, and an aluminium(III) source, optionally, in the presence of a protic additive or solvent selected from the group consisting of alcohols or amines.

40 7. Process as claimed in claim 6, characterized in that the aluminium(III) source is selected from

(i) aluminium salts of the formula (IV),

50 in which X and Y are as defined in the compound of formula (I) to be prepared, and Z, independently of X, is a leaving group selected from the group of radicals as defined for X or Y, or (ii) aluminium salts of the formula (IV’),

60 EP 2 231 679 B1

in which X’, Y’ and Z’ each are selected from the group consisting of radicals as defined for X, Y or Z, respectively and radicals which generate said group X, Y or Z, respectively in the presence of a protic additive or solvent X-H, 10 Y-H or Z-H, respectively, with the proviso that 1, 2 or 3 of the radicals X’, Y’ and Z’ are selected from said radicals which generate radicals X, Y and Z, respectively, in combination with a protic additive or solvent X-H, Y-H or Z-H wherein each of X, Y and Z are defined as set forth for X and Y in formula (1).

15 8. Use of a compound of formula (I) or salts thereof as defined in claim 1 for the preparation of heterocyclic compounds corresponding to formula (I), wherein the aluminium group Al(X)(Y) is replaced with an optionally substituted carbon atom, or s-triazine derivatives thereof.

9. A process for the preparation of compounds of the formula (V) or salts thereof, 20

30 in which R1, R2, R3 and R4 are as defined in formula (I) according to claim 1, and

Q is 35

a) hydrogen, (C1-C12)alkyl, (C2-C12)alkenyl or (C2-C12)alkynyl, wherein each of the last-mentioned three radicals is unsubstituted or substituted, b) or is (C3-C6)cycloalkyl, benzo-(C5-C6)Cycloalkyl, (C5-C6)cycloalkenyl, benzo-(C5-C6)cycloalkenyl, phenyl, naphthyl, heterocyclyl or benzocondensated heterocycyl, wherein each of the last-mentioned 8 radicals 40 is unsubstituted or substituted in the cyclic moiety, c) or is COR, COOR, C(=S)R, C(=O)SR, C(=S)OR, C(=S)SR, wherein R in each of the 6 last-mentioned radicals being (C1-C18)alkyl, (C3-C6)cycloalkyl or phenyl, the latter three radicals being unsubstituted or substituted,

45 characterized in that a compound of the formula (I) or a salt thereof

in which R1, R2, R3 and R4 are as defined in the compound of formula M to be prepared and R5 and R6 are hydrogen,

61 EP 2 231 679 B1

is reacted with a compound of the formula (VI)

Q-W* (VI)

5 in which

Q is as defined in the compound of formula (V) to be prepared and W* is a carbon atom which bears 3 additional bonds to 1, 2 or 3 leaving groups which are linked by hetero atoms,

10 to give the compound of the formula (V) or a salt thereof.

10. Process as claimed in claim 9, characterized in that the compound (I) is prepared according to the process of claim 6 or 7 and directly used without isolation for the preparation of the compound of formula (V), optionally in a one-pot process. 15

Patentansprüche

1. Verbindungen der Formel (I) oder Salze hievon 20

wobei

1 R (C1-C18)Alkyl, (C2-C18)Alkenyl oder (C2-C18)Akinyl darstellt, wobei jeder der letztgenannten drei Reste 35 unsubstituiert oder substituiert ist, oder eine Gruppe der Formal A1 oder B1 ist, 2 R H, (C1-C18)Alkyl, (C2-C18)Alkenyl oder (C2-C18)Akinyl darstellt, wobei jeder der letztgenannten drei Reste unsubstituiert oder substituiert ist, oder eine Gruppe der Formal A2 ist, 40 3 R H, (C1-C18)Alkyl, (C2-C18)Alkenyl oder (C2-C18)Akinyl darstellt, wobei jeder der letztgenannten drei Reste unsubstituiert oder substituiert ist, oder eine Gruppe der Formal A3 ist, 4 R H, (C1-C18)Alkyl, (C2-C18)Alkenyl oder (C2-C18)Akinyl darstellt, wobei jeder der letztgenannten drei Reste unsubstituiert oder substituiert ist, 45 oder eine Gruppe der Formal A4 ist, 5 R H, (C1-C18)Alkyl, (C2-C18)Alkenyl oder (C2-C18)Akinyl darstellt, wobei jeder der letztgenannten drei Reste unsubstituiert oder substituiert ist, oder eine Gruppe der Formal A5 ist, 6 R H, (C1-C18)Alkyl, (C2-C18)Alkenyl oder (C2-C18)Akinyl darstellt, 50 wobei jeder der letztgenannten drei Reste unsubstituiert oder substituiert ist, oder eine Gruppe der Formal A6 ist, oder R1 und R2 oder R3 und R4 gemeinsam mit dem N-Atom aneinander ge bunden einen N-heterocyclischen Ring mit 3 bis 7 Ringatomen und wahlweise einem oder mehreren zusätzlichen Hetero-atomen, ausgewählt von der Gruppe, bestehend aus N, O und S, und welcher substituiert oder unsubstituiert ist, ausbilden, 55 1 2 3 4 5 6 A ,A ,A ,A ,A und A unabhängig voneinander (C3-C9) Cycloalkyl, (C4-C9) Cycloalkenyl, (C5-C9)Cycloalkinyl, Aryl oder Heterocyclyl als ein cyclischer Basisrest sind, wobei der cyclische Basisrest unsubstituiert oder substituiert ist, B1 eine Gruppe ist, wie sie für R1 definiert ist, die weiter an die Aminogruppe von der Gruppe von Formel (I*),

62 EP 2 231 679 B1

10 gebunden ist, wobei R2*, R3*, R4*, R5*, R6*, X und Y unabhängig wie in Formel (I) für R2,R3,R4,R5,R6, X bzw. Y definiert sind, X und Y jeweils unabhängig voneinander von der Gruppe ausgewählt sind, bestehend aus

15 (i) Amino, (ii) einer Gruppe der Formel NR7R8, wobei R7 ein Rest ist, ausgewählt von der Gruppe, bestehend aus Resten wie sie für R1 definiert sind und unabhängig von R1, und in welcher R8 ein Rest ist, ausgewählt von der Gruppe, bestehend aus Resten, wie sie für R2 definiert sind und unabhängig von R2, (iii) Hydroxy, 20 (iv) (C1-C6)Alkoxy, (C1-C6)Haloalkoxy, (C1-C6)Alkoxy-(C1-C6)alkoxy und (C1-C6)Alkylthio, (v) (C1-C6)Alkoxy, (C1-C6)Haloalkoxy, (C1-C6) Alkoxy-(C1-C6)alkoxy und (C1-C6)alkylthio, wobei jeder der letztgenannten 4 Reste durch einen oder mehrere Reste substituiert ist, ausgewählt von der Gruppe, bestehend aus (C3-C6)Cycloalkyl, (C3-C6)Cycloalkoxy, wobei jeder der letztgenannten zwei Reste unsubstituiert oder mit einem oder mehreren Resten substituiert ist, 25 ausgewählt von der Gruppe, bestehend aus Halogen, Hydroxy, Carbamoyl, (C1-C6)Alkyl, (C1-C6)Haloalkyl, (C1-C6)Alkoxy-(C1-C6)alkyl, (C1-C6)Alkoxy, (C1-C6)Haloalkoxy und (C1-C6)Alkoxy-(C1-C6)alkoxy, Aryl und Aryloxy, wobei jeder der letztgenannten zwei Reste unsubstituiert oder mit einem oder mehreren Resten substituiert ist, ausgewählt von der Gruppe, bestehend aus Halogen, Hydroxy, Nitro, Carbamoyl, Sulfo, (C1-C6)Alkyl, (C1-C6) 30 Haloalkyl, (C1-C6)Alkoxy-(C1-C6)alkyl, (C1-C6)Alkoxy, (C1-C6)-Haloalkoxy, (C1-C6)Alkoxy-(C1-C6)alkoxy, (C1-C6)Alkylthio, (C1-C6)Alkylsulfinyl, (C1-C6) -Haloalkylsulfinyl, (C1-C6)Alkylsulfonyl, (C1-C6)-Haloalkylsulfo- nyl, Di-[(C1-C4)alkyl]-amino, (C1-C4)Alkylaminocarbonyl, Di- [(C1-C4)alkyl]-aminocarbonyl, (C1-C4)Alkylamino- carbonylamino und Di-[(C1-C4)alkyl]-aminocarbonylamino, (vi) (C3-C6)Cycloalkoxy, welches unsubstituiert oder mit einem oder mehreren Resten substituiert ist, ausge- 35 wählt von der Gruppe, bestehend aus Halo- gen, Hydroxy, Carbamoyl, (C1-C6)Alkyl, (C1-C6) Haloalkyl, (C1-C6) Alkoxy-(C1-C6)alkyl, (C1-C6)Alkoxy, (C1-C6)Haloalkoxy und (C1-C6)Alkoxy-(C1-C6)alkoxy, (vii) Aryloxy, welches unsubstituiert oder substituiert ist, und (viii)Acyloxy, Acylthio oder Acylamino, oder 40 X und Y gemeinsam eine zweiwertige Gruppe der Formel -U1-D*-U2 sind, wobei

D* eine Kohlenwasserstoffbrücke ist, wahlweise unterbrochen durch eine oder mehrere zweiwertige Gruppen der nachstehend definierten Formel U3, und 45 U1,U2 und U3 unabhängig voneinander von der Gruppe, bestehend aus NH, NR’, O und S, ausgewählt sind, wobei R’ (C1-C6)Alkyl, Hydroxy-(C1-C6)alkyl oder (C1-C6)Alkoxy-(C1-C6) alkyl ist, X ein Rest ist, wie er vorstehend definiert ist, und Y ein organischer Ligand ist, basierend auf einer Verbindung der Formel Y’ -H, Y’ -RL oder RL-U3-D**-U4-RLL, wobei D** eine zweiwertige Gruppe ist, wie sie für die vorste- hende Gruppe D* definiert ist, Y’ ein Rest ist, wie er für Y definiert ist, U3 eine zweiwertige Gruppe ist, wie sie 50 vorstehend für U1 definiert ist, U4 eine zweiwertige Gruppe ist, wie sie vorstehend für U2 definiert ist, wobei L LL jedes R und R ein Rest ist, ausgewählt von der Gruppe, bestehend aus (C1-C6)Alkyl, Hydroxy- (C1-C6) alkyl oder (C1-C6)Alkoxy-(C1-C6)alkyl, und wobei der organische Ligand an das Aluminiumatom des Komplexes durch ein freies Elektronenpaar eines Heteroatoms, das darin enthalten und von der Gruppe, bestehend aus N, O und S, ausgewählt ist, koordiniert ist, oder 55 X und Y gemeinsam ein Rest der Formel -U1-D*-U2-RLLL sind, wobei U1,U2 und D* wie vorstehend definiert LLL sind, und R ein Rest ist, ausgewählt von der Gruppe, bestehend aus (C1-C6)Alkyl, Hydroxy-(C1-C6)alkyl 1 2 LLL oder (C1-C6)Alkoxy-(C1-C6)alkyl, und wobei der Rest -U -D*-U -R zusätzlich an das Aluminiumatom des Komplexes durch ein freies Elektronenpaar koordiniert ist, welches am im Rest enthaltenen Heteroatom loka-

63 EP 2 231 679 B1

lisiert ist (Stellung dargestellt durch Y).

2. Verbindung nach Anspruch 1, dadurch gekennzeichnet, dass

5 1 R (C1-C18)Alkyl, (C2-C18)Alkenyl oder (C2-C18)Akinyl ist, wobei jeder der letztgenannten drei Reste unsubstituiert oder mit einem oder mehreren Resten substituiert ist, ausgewählt von der Gruppe, bestehend aus Halogen, Hydroxy, Nitro, Carbamoyl, Sulfo und Resten der Formeln 1a 1b 1c 1d 1e 1f 1g 1h 1i 1j 1k -O-R ,S-R ,-S(=O)-R , - S(=O)2-R ,-NR R -C(=O)-NHR , -C(=O)-NR R , -NHC(=O)-NR R und A1a, 10 1a 1 1c 1d 1e 1f 1g 1h 1i 1j 1k wobei R ,Rb, R R ,R ,R ,R ,R ,R ,R und R unabhängig voneinander (C1-C6)Alkyl, (C1-C6) 1b Haloalkyl, (C1-C6)Alkoxy-(C1-C6)Alkyl oder ein Rest der Formel A sind, oder eine Gruppe der Formel A1 oder B1 ist, 2 R H, (C1-C18)Alkyl, (C2-C15)Alkenyl oder (C2-C18)Akinyl ist, wobei jeder der letztgenannten drei Reste unsubstituiert oder mit einem oder mehreren Resten substituiert ist, 15 ausgewählt von der Gruppe, bestehend aus Halogen, Hydroxy, Nitro, Carbamoyl, Sulfo und Resten der Formeln 2a 2b 2c 2d 2e 2f 2g 2h 2i 2j 2k -O-R , -S-R , -S(=O)-R , S(=O)2-R ,-NR R , -C(=O)-NHR , -C(=O)-NR R , -NHC(=O)-NR R und 2a 2a 2b 2c 2a 2e 2f 2g 2n 2i 2j 2k A wobei R ,2 ,R ,R ,R ,R ,R ,R ,R ,R und R unabhängig voneinander (C1-C6) Alkyl, (C1-C6) 2b Haloalkyl, (C1-C6) Alkoxy-(C1-C6)Alkyl oder ein Rest der Formel A sind, oder eine Gruppe der Formel A2 ist, 20 3 R H, (C1-C18)Alkyl, (C2-C18)Alkenyl oder (C2-C18)Akinyl ist, wobei jeder der letztgenannten drei Reste unsubstituiert oder mit einem oder mehreren Resten substituiert ist, ausgewählt von der Gruppe, bestehend aus Halogen, Hydroxy, Nitro, Carbamoyl, Sulfo und Resten der Formeln 3a 3b 3c 3d 3e 3f 3g 3h 3i 3j 3k -O-R , -S-R , -S(=O)-R , -S(=O)2-R ,-NR R , -C(=O)-NHR , -C(=O)-NR R , -NHC(=O)-NR R und 3a 3a 3b 3c 3d 3e 3f 3g 3h, 3i 3j 3k A wobei R ,R ,R ,R ,R ,R ,R ,R R ,R und R unabhängig voneinander (C1-C6)Alkyl, (C1-C6) 25 3b Haloalkyl, (C1-C6)Alkoxy-(C1-C6)Alkyl oder ein Rest der Formel A sind, oder eine Gruppe der Formel A3 ist, 4 R H, (C1-C18)Alkyl, (C2-C18)Alkenyl oder (C2-C18)Akinyl ist, wobei jeder der letztgenannten drei Reste unsubstituiert oder mit einem oder mehreren Resten substituiert ist, ausgewählt von der Gruppe, bestehend aus Halogen, Hydroxy, Nitro, Carbamoyl, Sulfo und Resten der Formeln -O-R4a, -S-R4b, 30 4d 4e 4f 4g -S(=O)-R4C, -S(=O)2-R ,-NR R , -C(=O)-NHR , -C (=O) -NR4hR4i, -NHC (=O) -NR4jR4k und A4a, wobei R4a,R4b, R4c, R4d,R4e,R4f,R4g,R4h,R4i,R4j und R4k unabhängig voneinander (C1-C6)Alkyl, (C1-C6)Haloalkyl, (C1-C6)-Alkoxy-(C1-C6) Alkyl oder ein Rest der Formel A4b sind, oder eine Gruppe der Formel A4 ist, 35 5 R H, (C1-C18)Alkyl, (C2-C18)Alkenyl oder (C2-C18)Akinyl ist, wobei jeder der letztgenannten drei Reste unsubstituiert oder mit einem oder mehreren Resten substituiert ist, ausgewählt von der Gruppe, bestehend aus Halogen, Hydroxy, Nitro, Carbamoyl, Sulfo und Resten der Formeln 5a 5b 5c 5d 5e 5f 5g 5h 5i 5j 5k -O-R , -S-R , -S(=O)-R , -S(=O)2-R ,-NR R , -C(=O)-NHR , -C(=O)-NR R , -NHC(=O)-NR R und 5a 5a 5b 5c 5d 5e 5f 5g 5h 5i 5j 5k A wobei R ,R ,R ,R ,R ,R ,R ,R ,R ,R und R unabhängig voneinander (C1-C6)Alkyl, (C1-C6) 40 5b Haloalkyl, (C1-C6;)Alkoxy-(C1-C6)Alkyl oder ein Rest der Formel A sind, oder eine Gruppe der Formel A5 ist, 6 R H, (C1-C18)Alkyl, (C2-C18)Alkenyl oder (C2-C18)Akinyl ist, wobei jeder der letztgenannten drei Reste unsubstituiert oder mit einem oder mehreren Resten substituiert ist, ausgewählt von der Gruppe, bestehend aus Halogen, Hydroxy, Nitro, Carbamoyl, Sulfo und Resten der Formeln 45 6a sb 6c 6d 6e 6f 6g 6h 6i 6j 6k -O-R , -S-R , -S(=O)-R , -S(=O)2-R ,-NR R , -C(=O)-NHR , -C(=O)-NR R , -NHC(=O)-NR R und 6a 6a 6b 6c 6d 6e 6f 6g 6h 6i 6j 6k A , wobel R ,R ,R ,R , R ,R ,R ,R ,R ,R und R unabhängig voneinander (C1-C6)Alkyl, (C1-C6) 6b Haloalkyl, (C1-C6)Alkoxy- (C1-C6)Alkyl oder ein Rest der Formel A sind, oder eine Gruppe der Formel A6 ist, oder R1 und R2 oder R3 und R4 gemeinsam mit dem N-Atom aneinander gebunden einen N-heterocyclischen Ring 50 mit 3 bis 7 Ring atomen und wahlweise einem oder mehreren zusätzlichen Heteroatomen, ausgewählt von der Gruppe, bestehend aus N, O und S, ausbilden und welcher unsubstituiert oder mit einem oder mehreren Resten substituiert ist, ausgewählt von der Gruppe, bestehend aus Halogen, Hydroxy, Nitro, Carbamoyl, Sulfo, (C1-C6) Alkyl, (C1-C6)Haloalkyl, (C1-C6)Alkoxy-(C1-C6)alkyl, (C1-C6)Alkoxy, (C1-C6)Haloalkoxy, (C1-C6)Alkoxy-(C1-C6) alkoxy, (C1-C6)Alkylthio, (C1-C6)Alkylsulfinyl, (C1-C6)Haloalkylsulfinyl, (C1-C6)Alkylsulfonyl, (C1-C6)Halo-al- 55 kylsulfonyl, Di-[(C1-C4)alkyl]-amino, (C1-C4)Alkylamino-carbonyl, Di-[(C1-C4)alkyl]-aminocarbonyl, (C1-C4)Al- kyl-amino-carbonylamino, Di-[(C1-C4)alkyl]-aminocarbonylamino und Oxo, A1,A1a,A1b,A2,A2a,A2b,A3,A3a,A3b,A4,A4a,A4b,A5,A5a,A5b,A6,A6a und A6b unabhängig voneinander (C3-C9)Cycloalkyl, (C4-C9)Cycloalkenyl, (C5-C9)Cycloalkinyl, Aryl oder Hetero-cyclyl als cyclischer Basisrest

64 EP 2 231 679 B1

sind, wobei der cyclische Basisrest

(a) unsubstituiert oder mit einem oder mehreren Resten substituiert ist, ausgewählt von der Gruppe, bestehend aus Halogen, Hydroxy, Nitro, Carbamoyl, Sulfo, (C1-C6)Alkyl, (C1-C6)Haloalkyl, (C1-C6)Alk- 5 oxy-(C1-C6)alkyl, (C1-C6)Alkoxy, (C1-C6)Haloalkoxy, (C1-C6)Alkoxy-(C1-C6)alkoxy, (C1-C6)Alkylthio, (C1-C6)Alkylsulfinyl, (C1-C6)Haloalkylsulfinyl, (C1-C6)Alkylsulfonyl, (C1-C6)Haloalkylsulfonyl, Di-[(C1-C4)alkyl]-amino, (C1-C4)Alkylaminocarbonyl, Di-[(C1-C4)alkyl]-aminocarbonyl, (C1-C4)Alkylamino-carbonylamino, Di-[(C1-C4)alkyl]-aminocarbonylamino und, im Fall von Heterocyclyl, auch Oxo, welches an Heteror- ingatome N oder S oder in alpha-Stellung eines N-Atoms als Heteroringatom gebunden ist, 10 oder (b) substituiert oder zusätzlich zu einem oder mehreren der in (a) genannten Substituenten substituiert ist durch eine Brücke, welche geminal (einer 1,1-Stellung), vicinal (einer 1,2-Stellung) oder in einer 1,3-Stellung an den cyclischen Basisrest gebunden ist, um so einen weiteren carbocyclischen oder heterocyclischen Ring gemeinsam mit dem Teil des cyclischen Basisrestes zwischen den an die Brücke gebundenen Atomen 15 auszubilden, wobei der ausgebildete carbocyclische oder heterocyclische Ring gesättigt, teilweise ungesättigt, ungesät- tigt, aromatisch oder heteroaromatisch ist, und wobei die Brücke ferner unsubstituiert oder mit einem oder mehreren Resten substituiert ist, ausgewählt von der Gruppe, bestehend aus Halogen, Hydroxy, Nitro, Carbamoyl, Sulfo, (C1-C6)Alkyl, (C1-C6)Haloalkyl, (C1-C6)-Alkoxy-(C1-C6)alkyl, (C1-C6)Alkoxy, (C1-C6)Ha- 20 lo-alkoxy, (C1-C6)Alkoxy-(C1-C6)alkoxy, (C1-C6)Alkylthio, (C1-C6)Alkylsulfinyl, (C1-C6)Haloalkyl-sulfinyl, (C1-C6)Alkylsulfonyl, (C1-C6)Haloalkyl-sulfonyl, Di-[(C1-C4)alkyl]-amino, (C1-C4)Alkyl-aminocarbonyl, Di-[(C1-C4)alkyl]-aminocarbonyl,C1-C4)Alkylamino-carbonylaminoundDi-[(C1-C4)-alkyl]-aminocarbonylamino,

25 B1 eine Gruppe ist, wie sie für R1 definiert ist, die ferner an die Aminogruppe der Gruppe der Formel (I*)

gebunden ist, wobei R2*, R3*, R4*, R5*, R6*, X* und Y* unabhängig wie in Formel (I) für R2,R3,R4,R5,R6, X bzw. Y definiert sind, X und Y jeweils unabhängig voneinander von der Gruppe ausgewählt sind, bestehend aus 40 (i) Amino, (ii) einer Gruppe der Formel NR7R8, wobei R7 ein Rest ist, ausgewählt von der Gruppe, bestehend aus Resten, wie sie für R1 definiert sind und unabhängig von R1, und in welcher R8 ein Rest ist, ausgewählt von der Gruppe, bestehend aus Resten, wie sie für R2 definiert sind und unabhängig von R2 45 (iii) Hydroxy, (iv) (C1-C6)Alkoxy, (C1-C6)Haloalkoxy, (C1-C6)Alkoxy-(C1-C6)alkoxy und (C1-C6)Alkylthio, (v) (C1-C6) Alkoxy, (C1-C6)Haloalkoxy, (C1-C6)Alkoxy- (C1-C6)alkoxy und (C1-C6)alkylthio, wobei jeder der letzt-genannten 4 Reste mit einem oder mehreren Resten substituiert ist, ausgewählt von der Gruppe, bestehend aus (C3-C6)Cycloalkyl, (C3-C6)Cycloalkoxy, wobei jeder der letztgenannten zwei Reste unsub- 50 stituiert oder mit einem oder mehreren Resten

substituiert ist, ausgewählt von der Gruppe, be-stehend aus Halogen, Hydroxy, Carbamoyl, (C1-C6)Alkyl, (C1-C6)Haloalkyl, (C1-C6)Alkoxy-(Cl-C6)alkyl, (C1-C6)Alkoxy, (C1-C6)Haloalkoxyund (C1-C6)Alkoxy- (C1-C6) alkoxy, 55 Aryl und Aryloxy, wobei jeder der letztgenannten zwei Reste unsubstituiert oder mit einem oder mehreren Resten substituiert ist, ausgewählt von der Gruppe, bestehend aus Halogen, Hydroxy, Nitro, Carbamoyl, Sulfo, (C1-C6)Alkyl, (C1-C6) Haloalkyl, (C1-C6)-Alkoxy-(C1-C6)alkyl, (C1-C6)Alkoxy, (C1-C6) -Haloalkoxy, (C1-C6)Alkoxy-(C1-C6)alkoxy,

65 EP 2 231 679 B1

(C1-C6) -Alkylthio, (C1-C6)Alkylsulfinyl, (C1-C6)Haloalkylsulfinyl, (C1-C6)Alkylsulfonyl, (C1-C6) -Haloalkylsulfo- nyl, Di-[(C1-C4)alkyl]-amino, (C1-C4)Alkylaminocarbonyl, Di-[(C1-C4)alkyl]-amino-carbonyl, (C1-C4)Alkylamino- carbonylamino und Di- [(C1-C4)alkyl]-aminocarbonylamino, (vi) (C3-C6)Cycloalkoxy, welches unsubstituiert oder mit einem oder mehreren Resten substituiert ist, ausge- 5 wählt von der Gruppe, bestehend aus Halogen, Hydroxy, Carbamoyl, (C1-C6)Alkyl, (C1-C6) -Haloalkyl, (C1-C6) Alkoxy-(C1-C6)alkyl, (C1-C6)-Alkoxy, (C1-C6)Haloalkoxy und (C1-C6)Alkoxy-(C1-C6)alkoxy, (vii) Aryloxy, welches unsubstituert oder mit einem oder mehreren Resten substituiert ist, ausgewählt von der Gruppe, bestehend aus Halogen, Hydroxy, Nitro, Carbamoyl, Sulfo, (C1-C6)Alkyl, (C1-C6) -Haloalkyl, (C1-C6) Alkoxy-(C1-C5)alkyl, (C1-C6)Alkoxy, (C1-C6)Haloalkoxy, (C1-C6)Alkoxy-(C1-C6)alkoxy, (C1-C6)Alkylthio, 10 (C1-C6)Alkyl-sulfinyl, (C1-C6)Haloalkylsulfinyl, (C1-C6)Alkyl-sulfonyl, (C1-C6)Haloalkylsulfonyl, Di-[(C1-C4)- alkyl]-amino, (C1-C4)Alkylaminocarbonyl, Di-[(C1-C4)alkyl]-aminocarbonyl, (C1-C4)Alkylamino-carbonylamino und Di-[(C1-C4)alkyl]-amino-carbonylamino, und (viii) Acyloxy, Acylthio oder Acylamino mit jeweils 1 bis 12 Kohlenstoffatomen, 15 oder X und Y gemeinsam eine zweiwertige Gruppe der Formel -U1-D*-U2- sind, wobei

D* eine lineare Alkylenbrücke, eine lineare (C2-C10)-Alkenylenbrücke, eine lineare (C2-C10)Alkinylenbrücke, eine (C3-C9)Cycloalkylenbrücke, eine Phenylenbrücke oder eine Brücke ist, bestehend aus einer Kombi- 20 nation von zwei oder mehreren der linearen acyclischen und cyclischen Reste mit insgesamt 4 bis 24 Kohlenstoffatomen, wobei die Brücke in jedem Fall unsubstituiert oder mit einem oder mehreren Resten substituiert ist, ausgewählt von der Gruppe, bestehend aus Halogen, Hydroxy, Nitro, Carbamoyl, Sulfo, (C1-C6)Alkyl, (C1-C6)Haloalkyl, (C1-C6)Alkoxy- (C1-C6)alkyl, (C1-C6)-Alkoxy, (C1-C6)Haloalkoxy, (C1-C6) Alkoxy- (C1-C6)alkoxy, (C1-C6)Alkylthio, (C1-C6)Alkylsulfinyl, (C1-C6)Halo-alkylsulfinyl, (C1-C6)Alkylsulfo- 25 nyl,(C1-C6)Halo-alkylsulfonyl,Di-[(C1-C4)alkyl]-amino,(C1-C4)Alkyl-aminocarbonyl,Di-[(C1-C4)alkyl]-aminocarbonyl, (C1-C4)Alkylamino-carbonylamino und Di- [(C1-C4)alkyl] -aminocarbonylamino, und U1,U2 und U3 unabhängig voneinander von der Gruppe ausgewählt sind, bestehend aus NH, NR’, 0 und S, wobei R’ (C1-C6)Alkyl, Hydroxy-(C1-C6)alkyl oder (C1-C6)Alkoxy-(C1-C6)Alkyl ist, oder

30 X ein Rest ist, wie er vorstehend definiert ist, und Y ein organischer Ligand ist, basierend auf einer Verbindung der Formel Y’-H, Y’-RL oder RL-U3-D**-U4-RLL, wobei D** eine zweiwertige Gruppe ist, wie sie für die Gruppe D* vorstehend definiert ist, Y’ ein Rest ist, wie er für Y definiert ist, U3 eine zweiwertige Gruppe ist, wie sie für U1 vorstehend definiert ist, U4 eine zweiwertige Gruppe ist, wie sie für U2 vorstehend definiert ist, jedes RL und LL R ein Rest ist, ausgewählt von der Gruppe, bestehend aus (C1-C6)Alkyl, Hydroxy-(C1-C6)alkyl oder (C1-C6) 35 Alkoxy-(C1-C6)Alkyl, und wobei der organische Ligand an das Aluminiumatom des Komplexes durch ein freies Elektronenpaar eines Heteroatoms koordiniert ist, welches darin enthalten und von der Gruppe, bestehend aus N, O und S, ausgewählt ist, oder X und Y gemeinsam ein Rest der Formel -U1-D*-U2-RLLL sind, wobei U1,U2 und D* wie vorstehend definiert LLL sind, und R ein Rest ist, ausgewählt von der Gruppe, bestehend aus (C1-C6)Alkyl, Hydroxy-(C1-C6)alkyl 40 1 2 LLL oder (C1-C6)Alkoxy-(C1-C6)Alkyl, und wobei der Rest U -D*-U -R zusätzlich an das Aluminiumatom des Komplexes durch ein freies Elektronenpaar koordiniert ist, welches am Heteroatom, das im Rest enthalten ist (Position dargestellt durch Y) lokalisiert ist, welches vorzugsweise am Heteroatom der zweiwertigen Gruppe U2 lokalisiert ist.

45 3. Verbindung nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass

1 R (C1-C12)Alkyl, (C2-C12)Alkenyl oder (C2-C12)Akinyl ist, wobei jeder der letztgenannten drei Reste unsubstituiert oder mit einem oder mehreren Resten substituiert ist, ausgewählt von der Gruppe, bestehend aus Halogen, 1a 1b 1c 1d 1e 1f Hydroxy, Nitro, Carbamoyl, Sulfo und Resten der Formeln -O-R , -S-R , S(=O)-R , -S(=O)2-R ,- NR R , 50 -C(=O) -NHR1g, -C(=O) -NR1hR1i, -NHC (=O) -NR1jR1k und A1a, wobei R1a,R1b,R1c,R1a,R1e,R1f,R1g,R1n, 1i 1j 1k R ,R und R unabhängig voneinander (C1-C6)Alkyl, (C1-C6)Haloalkyl, (C1-C6)Alkoxy-(C1-C6)alkyl oder ein Rest der Formel A1b sind, oder eine Gruppe der Formel A1 oder B1 ist, oder 55 R1 und R2 gemeinsam mit dem N-Atom aneinander gebunden einen heterocyclischen Ring mit 5 bis 6 Ringa- tomen und wahlweise 1, 2 oder 3 zusätzlichen Heteroatomen ausbilden, ausgewählt von der Gruppe, bestehend aus N, O und S, und welcher unsubstituiert oder mit einem oder mehreren Resten substituiert ist, ausgewählt von der Gruppe, bestehend aus Halogen, Hydroxy, Nitro, Carbamoyl, Sulfo, (C1-C6)Alkyl, (C1-C6)Haloalkyl,

66 EP 2 231 679 B1

(C1-C6)Alkoxy-(C1-C6)alkyl, (C1-C6)Alkoxy, (C1-C6)Haloalkoxy, (C1-C6)Alkoxy-(C1-C6)alkoxy, (C1-C6)-Al- kylthio, (C1-C6)Alkylsulfinyl, (C1-C6)Haloalkylsulfinyl, (C1-C6)Alkylsulfonyl, (C1-C6)Haloalkylsulfonyl, Di-[(C1-C4)alkyl]-amino, (C1-C4)Alkylaminocarbonyl, Di-[(C1-C4)-alkyl]-aminocarbonyl, (C1-C4)Alkylamino-carbonylamino und Di-[(C1-C4)alkyl]-aminocarbonylamino und Oxo, 5 1 1a 1b A ,A und A unabhängig voneinander (C3-C9)Cycloalkyl, (C4-C9)Cycloalkenyl, (C5-C9)Cycloalkinyl, Aryl oder Heterocyclyl als cyclischer Basisrest sind, wobei der cyclische Basisrest

(a) unsubstituiert oder mit einem oder mehreren Resten substituiert ist, ausgewählt von der Gruppe, bestehend aus Halogen, Hydroxy, Nitro, Carbamoyl, Sulfo, (C1-C6)Alkyl, (C1-C6)Haloalkyl, (C1-C6)Alk- 10 oxy-(C1-C6) -allkyl, (C1-C6)Alkoxy, (C1-C6)Haloalkoxy, (C1-C6)Alkoxy-(C1-C6)alkoxy, (C1-C6)Alkylthio, (C1-C6)Alkylsulfinyl, (C1-C6)Haloalkylsulfinyl, (C1-C6)Alkylsulfonyl, (C1-C6)Haloalkylsulfonyl, Di-[(C1-C4)alkyl]-amino, (C1-C4)Alkylaminocarbonyl, Di- [(C1-C4)alkyl] -aminocarbonyl, (C1-C4)Alkylamino-carbonylamino und Di-[(C1-C4)alkyl]-aminocarbonylamino und, im Fall von Heterocyclyl, auch Oxo, gebunden an die Heteroringatome N oder S oder in alpha-Stellung eines N-Atoms als Heteroringatom, 15 oder (b) substituiert oder zusätzlich zu einem oder mehreren der in (a) genannten Substituenten substituiert ist durch eine Brücke, welche geminal (einer 1,1-Stellung), vicinal (einer 1,2-Stellung) oder in einer 1,3-Stellung an den cyclischen Basisrest gebunden ist, um so einen weiteren carbocyclischen oder heterocyclischen Ring gemeinsam mit dem Teil des cyclischen Basisrestes zwischen den an die Brücke gebundenen Atomen 20 auszubilden, wobei der ausgebildete carbocyclische oder heterocyclische Ring gesättigt, teilweise unge- sättigt, ungesättigt mit 3 bis 9 Ringsatomen ist, oder aromatisch oder heteroaromatisch mit 5 oder 6 Ringa- tomen ist, und wobei die Brücke ferner unsubstituiert oder mit einem oder mehreren Resten substituiert ist, ausgewählt von der Gruppe, bestehend aus Halogen, Hydroxy, Nitro, Carbamoyl, Sulfo, (C1-C6)Alkyl, (C1-C6)Haloalkyl, (C1-C6)Alkoxy-(C1-C6)alkyl, (C1-C6)Alkoxy, (C1-C6) Haloalkoxy, (C1-C6) -Alkoxy-(C1-C6) 25 alkoxy, (C1-C6)Alkylthio, (C1-C6) -Alkylsulfinyl, (C1-C6)Haloalkylsulfinyl, (C1-C6) -Alkylsulfonyl, (C1-C6) Ha- loalkylsulfonyl, Di-[(C1-C4)alkyl]-amino, (C1-C4)Alkylaminocarbonyl, Di-[(C1-C4)alkyl]-aminocarbonyl, (C1-C4)Alkylamino-carbonylamino und Di-[(C1-C4)alkyl]-aminocarbonylamino, und, im Fall von Heterocyc- lyl, auch Oxo, welches an die Heteroringatome N oder S oder in alpha-Stellung eines N-Atoms als Heter- oringatom gebunden ist, oder ferner benzokondensiert ist, wobei der zusätzliche kondensierte Benzolring 30 unsubstituiert oder ferner mit einem oder mehreren Resten, wie sie für die

Substitution der Brücke definiert sind, welche benzokondensiert ist, substituiert sind, B1 eine Gruppe ist, wie sie für R1 definiert ist, ferner gebunden an die Aminogruppe der Gruppe der Formel (I*)

45 wobei R2*,R3* R4*,R5*,R6*, X* und Y* unabhängig wie in Formel (I) für R2,R3,R4,R5,R6, X bzw. Y definiert sind.

4. Verbindung nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass

50 2 R H, (C1-C4)Alkyl, (C2-C4)Alkenyl oder (C2-C4)Akinyl, (C1-C4)Haloalkyl, Phenyl, Naphthyl, Phenyl(C1-C4)alkyl oder (C3-C6)Cycloalkyl ist, wobei jeder der letztgenannten vier Reste unsubstituiert oder im cyclischen Rest mit einem oder mehreren Resten substituiert ist, wie sie für die Substituenten an der cyclischen Gruppe A2 definiert sind, und R3, R4, R5 und R6 jeweils H sind. 55 5. Verbindung nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass X und Y jeweils unabhängig voneinander von der Gruppe ausgewählt sind, bestehend aus

67 EP 2 231 679 B1

(i) Amino, (ii) einer Gruppe der Formel NR7R8, welche wie die Gruppe NR1R2 in Formel (I) definiert ist, (iii) Hydroxy, (iv) (C1-C4)Alkoxy, (C1-C4)Haloalkoxy, (C1-C4)Alkoxy-(C1-C4)alkoxy und (C1-C4)Alkylthio, 5 (v) (C1-C4)Alkoxy, (C1-C4)Haloalkoxy, (C1-C4)Alkoxy-(C1-C4)alkoxy und (C1-C4)Alkylthio, wobei jeder der vier letztgenannten Reste mit einem oder mehreren Resten substituiert ist, ausgewählt von der Gruppe, bestehend aus (C3-C6)Cycloalkyl, (C3-C6)Cycloalkoxy, wobei jeder der letztgenannten zwei Reste unsubstituiert oder mit einem oder mehreren Resten substituiert ist, ausgewählt von der Gruppe, bestehend aus Halogen, Hydroxy, Carba- 10 moyl, (C1-C4)Alkyl, (C1-C4)Haloalkyl, (C1-C4)Alkoxy-(C1-C4)alkyl, (C1-C4)Alkoxy, (C1-C4) Haloalkoxy und (C1-C4)Alkoxy-(C1-C4)alkoxy, Phenyl oder Phenoxy, wobei jeder der letztgenannten zwei Reste unsubstituiert oder mit einem oder mehreren Resten substituiert ist, ausgewählt von der Gruppe, bestehend aus Halogen, Hydroxy, Nitro, Carbamoyl, Sulfo, (C1-C4)Alkyl, (C1-C4) 15 Haloalkyl, (C1-C4)-Alkoxy-(C1-C4)alkyl, (C1-C4)Alkoxy, (C1-C4)Halo-alkoxy, (C1-C4)Alkoxy-(C1-C4)alkoxy, (C1-C4) -Alkylthio, (C1-C4)Alkylsulfinyl, (C1-C4)Halo-alkylsulfinyl, (C1-C4)Alkylsulfonyl, (C1-C4)-Haloalkylsulfo- nyl, Di-[(C1-C4)alkyl]-amino, (C1-C4)Alkylaminocarbonyl, Di- [(C1-C4)alkyl]-aminocarbonyl, (C1-C4)Alkylamino- carbonylamino und Di-[(C1-C4)alkyl]-aminocarbonylamino, (vi) (C3-C6)Cycloalkoxy, welches unsubstituiert oder mit einem oder mehreren Resten substituiert ist, ausge- 20 wählt von der Gruppe, bestehend aus Halogen, Hydroxy, Carbamoyl, (C1-C4)Alkyl, (C1-C4)Haloalkyl, (C1-C4) Alkoxy- (C1-C4) alkyl, (C1-C4)Alkoxy, (C1-C4)Haloalkoxy und (C1-C4) -Alkoxy-(C1-C4)alkoxy, und (vii) Phenoxy, welches unsubstituiert oder mit einem oder mehreren Resten substituiert ist, ausgewählt von der Gruppe, bestehend aus Halogen, Hydroxy, Nitro, Carbamoyl, Sulfo, (C1-C4)Alkyl, (C1-C4)-Haloalkyl, (C1-C4) 25 Alkoxy-(C1-C4)alkyl, (C1-C4)-Alkoxy, (C1-C4)Haloalkoxy, (C1-C4)Alkoxy-(C1-C4)alkoxy, (C1-C4)Alkylthio, (C1-C4)Alkyl-sulfinyl, (C1-C4)Haloalkylsulfinyl, (C1-C4)-Alkylsulfonyl, (C1-C4)Haloalkylsulfonyl, Di-[(C1-C4)alkyl]-amino, (C1-C4)Alkylaminocarbonyl, Di-[(C1-C4)alkyl] -aminocarbonyl, (C1-C4)Alkylamino-carbonylamino und Di-[(C1-C4)alkyl]-aminocarbonylamino, und 30 (viii) Acyloxy, Acylthio oder Acylamino sind, wobei Acyl in den letztgenannten drei Gruppen Formyl, (C1-C6) Alkylcarbonyl, (C1-C6)Alkylsulfonyl oder Phenyl-sulfonyl ist, wobei die letztgenannte unsubstituiert oder mit einem oder mehreren Resten substituiert ist, aus gewählt von der Gruppe, bestehend aus Halogen, (C1-C4)Alkyl, (C1-C4)Haloalkyl, (C1-C4)Alkoxy-(C1-C4)alkyl, (C1-C4)Alk- oxy, (C1-C4)Haloalkoxy, (C1-C4)Alkoxy- (C1-C4)alkoxy und (C1-C4)Alkylthio, 35 oder X und Y gemeinsam eine zweiwertige Gruppe der Formel -O-D*-O-, -S-D*-S-, -NH-D*-NH-, -O-D*-NH-, -O-D*-S-, -N(CH3)-D*-N(CH3)-, -NH-D*-N(CH3)-, -N(C2H5)-D*-N(C2H5)-oder -NH-D*-N(C2H5)- sind, wobei D* in jeder der letztgenannten 9 zweiwertigen Gruppen eine lineare Al-kylenbrücke, eine lineare (C2-C10)Alkenylenbrücke, 40 eine lineare (C2-C10)Alkinylenbrücke, eine (C3-C9)Cyclo-alkylenbrücke, eine Phenylenbrücke oder eine Brücke ist, bestehend aus einer Kombination von zwei oder mehreren der linearen acyclischen und cyclischen Reste mit insgesamt 4 bis 18 Kohlenstoffatomen, wobei die Brücke in jedem Fall unsubstituiert oder mit einem oder mehreren Resten substituiert ist, ausgewählt von der Gruppe, bestehend aus Halogen, Hydroxy, Nitro, Carb- amoyl, Sulfo, (C1-C4)Alkyl, (C1-C4)Haloalkyl, (C1-C4)Alkoxy-(C1-C4)alkyl, (C1-C4)Alkoxy, (C1-C4)Haloalkoxy, 45 (C1-C4)Alkoxy-(C1-C4)alkoxy, (C1-C4)-Alkylthio, (C1-C4)Alkylsulfinyl, (C1-C4)Haloalkylsulfinyl, (C1-C4)Alkylsul- fonyl, (C1-C4)Haloalkylsulfonyl, Di-[(C1-C4)alkyl]-amino, (C1-C4)Alkylaminocarbonyl, Di-[(C1-C4)alkyl]-amino- carbonyl, (C1-C4)Alkylamino-carbonylamino und Di-[(C1-C4)alkyl]-aminocarbonylamino, oder X ein Rest ist, wie er vorstehend definiert ist, und Y ein organischer Ligand ist, basierend auf einer Verbindung der Formel Y’-H, Y’-RL oder RL-O-D**-O-RLL,RL-S-D**-S-RLL,RL-NH-D**-NH-RLL,RL-O-D**-NH-RLL,RL-O- 50 ID**-S-RLL, L LL L LL R -N(CH3)-D**-N(CH3)-R , R -NH-D**-N(CH3)-R , L LL L R -N(C2H5)-D**-N(C2H5)-R oder R LL -NH-D**-N (C2H5)-R , wobei D** in jeder der 9 letztgenannten Verbindungen eine zweiwerti-e Gruppe ist, wie sie für die Gruppe D* vorstehend defi-iert ist, Y’ ein Rest ist, wie er für Y definiert ist, und jedes RL und RLL ein 55 Rest ist, ausgewählt von der Gruppe, bestehend aus (C1-C6)Alkyl, Hydroxy-(C1-C6)alkyl oder (C1-C6)Alk- oxy-(C1-C6)alkyl, und wobei der organische Ligand an das Aluminiumatom des Komplexes durch ein freies Elektronenpaar eines Heteroatoms koordiniert ist, welches darin enthalten und von der Gruppe, bestehend aus N, O und S, ausgewählt ist,

68 EP 2 231 679 B1

oder X und Y gemeinsam ein Rest der Formel -O-D**-O-RLLL, -S-D**-S-RLLL, NH-D**-NH-RLLL, -O-D**-NH-RLLL, LLL LLL LLL LLL LLL -NH-D**-O-R , -O-D**-S-R , S-D**-O-R , -N(CH3)-D**-N(CH3)-R , -NH-D**-N(CH3)-R ,-N LLL LLL LLL LLL (CH3)-D**-NH-R ,-N(C2H5)-D**-N(C2H5)-R , -NH-D**-N(C2H5)-R oder- N(C2H5)-D**-NH-R sind, wo- 5 bei D* in den 13 letztgenannten Resten wie vorstehend definiert ist, und RLLL ein Rest ist, ausgewählt von der Gruppe, bestehend aus (C1-C4)Alkyl, Hydroxy-(C1-C4)alkyl oder (C1-C4)Alkoxy-(C1-C4)alkyl und wobei der Rest zusätzlich an das Aluminiumatom des Komplexes durch ein freies Elektronenpaar koordiniert ist, welches an einem Heteroatom lokalisiert ist, das im Rest enthalten ist (Stellung dargestellt durch Y), vorzugsweise am Heteroatom lokalisiert ist, welches an die Gruppe RLLL in der zweiwertigen Gruppe gebunden ist. 10 6. Verfahren zur Herstellung einer Verbindung der Formel (I) oder von deren Salzen nach einem der Ansprüche 1 bis 5

wobei R1 bis R6 und X und Y wie in Formel (I) definiert sind, dadurch gekennzeichnet, dass eine Verbindung (ein 25 Amin) der Formel (II) oder ein Salz hievon

wobei R1 und R2 wie in der herzustellenden Verbindung der Formel (I) definiert sind, mit einer Verbindung der Formel (III) oder einem Salz hievon 35

45 wobei R3,R4,R5 und R6 wie in der herzustellenden Verbindung der Formel (I) definiert sind, und einer Aluminium (III)quelle, wahlweise in Gegenwart eines protischen Additivs oder eines Lösungsmittels, ausgewählt von der Grup- pe, bestehend aus Alkoholen oder Aminen, umgesetzt wird.

7. Verfahren nach Anspruch 6, dadurch gekennzeichnet, dass die Aluminium(III)quelle von 50 (i) Aluminiumsalzen der Formel (IV),

69 EP 2 231 679 B1

wobei X und Y wie in der herzustellenden Verbindung der Formel (I) definiert sind, und Z unabhängig von X eine Abgangsgruppe ist, ausgewählt von der Gruppe von Resten, wie sie für X oder Y definiert sind, oder (ii) Aluminiumsalzen der Formel (IV’) 5

ausgewählt ist, wobei X’, Y’ und Z’ jeweils von der Gruppe, bestehend aus Resten, wie sie für X, Y bzw. Z definiert sind, und Resten, welche die Gruppe X, Y bzw. Z in Gegenwart eines protischen Additivs oder Lösungsmittels X-H, Y-H bzw. Z- 15 H erzeugen, ausgewählt sind, mit der Maßgabe, dass 1, 2 oder 3 der Reste X’, Y’ und Z’ von den genannten Resten ausgewählt sind, welche die Reste X, Y bzw. Z erzeugen, in Kombination mit einem protischen Additiv oder Lösungsmittel X-H, Y-H oder Z-H, wobei jeder von X, Y und Z definiert ist, wie es für X und Y in Formel (I) angeführt ist.

20 8. Verwendung einer Verbindung der Formel (I) oder von Salzen hievon, wie im Anspruch 1 definiert, zur Herstellung von heterocyclischen Verbindungen entsprechend der Formel (I), wobei die Aluminiumgruppe Al(X)(Y) mit einem wahlweise substituierten Kohlenstoffatom substituiert ist, oder von S-Triazin-Derivaten hievon.

9. Verfahren zur Herstellung von Verbindungen der Formel (V) oder von Salzen hievon 25

35 wobei R1, R2, R3 und R4 wie in Formel (I) nach Anspruch 1 def iniert sind, und Q

40 a) Wasserstoff, (C1-C12)Alkyl, (C2-C12)Alkenyl oder (C2-C12)Alkinyl, wobei jeder der letztgenannten drei Reste unsubstituiert oder substituiert ist, b) oder (C3-C6)Cycloalkyl, Benzo-(C5-C6)cycloalkyl, (C5-C6)Cycloalkenyl, Benzo-(C5-C6)cycloalkenyl, Phenyl, Naphthyl, Heterocyclyl oder benzokondensiertes Heterocycyl, wobei jeder der letztgenannten acht Reste unsubstituiert oder im cyclischen Rest substituiert ist, 45 c) oder COR, COOR, C(=S)R, C(=O)SR, C(=S)OR, C(=S)SR ist, wobei R in jedem der sechs letztgenannten Reste (C1-C18)Alkyl, (C3-C6)Cycloalkyl oder Phenyl ist, wobei die letztgenannten drei Reste unsubstituiert oder substituiert sind,

dadurch gekennzeichnet, dass eine Verbindung der Formel (I) oder ein Salz hievon 50

70 EP 2 231 679 B1

wobei R1,R2,R3 und R4 wie in der herzustellenden Verbindung der Formel (V) definiert sind, und R5 und R6 Wasserstoff sind, 15 mit einer Verbindung der Formel (VI)

Q-W* (VI)

umgesetzt wird, 20 wobei

Q wie in der herzustellenden Verbindung der Formel (V) definiert ist, und W* ein Kohlenstoffatom ist, welches drei zusätzliche Bindungen zu 1, 2 oder 3 Abgangsgruppen trägt, welche durch Heteroatome gebunden sind, um die Verbindung der Formel (V) oder ein Salz hievon zu ergeben. 25 10. Verfahren nach Anspruch 9, dadurch gekennzeichnet, dass die Verbindung (I) gemäß dem Verfahren von An- spruch 6 oder 7 hergestellt und direkt ohne Isolierung zur Herstellung der Verbindung der Formel (V), wahlweise in einem Eintopfverfahren, verwendet wird.

30 Revendications

1. Composés de la formule (I) ou sels de ceux-ci,

45 dans laquelle

1 R est un groupe alkyle en C1-C18, alcényle en C2-C18 ou alcynyle en C2-C18, où chacun des trois radicaux cités en dernier lieu est non substitué ou substitué, ou est un groupe de la formule A1 ou B1, 50 2 R est H, un groupe alkyle en C1-C18, alcényle en C2-C18 ou alcynyle en C2-C18, où chacun des trois radicaux cités en dernier lieu est non substitué ou substitué, ou est un groupe de la formule A2, 3 R est H, un groupe alkyle en C1-C18, alcényle en C2-C18 ou alcynyle en C2-C18, où chacun des trois radicaux cités en dernier lieu est non substitué ou substitué, ou est un groupe de la formule A3, 4 R est H, un groupe alkyle en C1-C18, alcényle en C2-C18 ou alcynyle en C2-C18, où chacun des trois radicaux 55 cités en dernier lieu est non substitué ou substitué, ou est un groupe de la formule A4, 5 R est H, un groupe alkyle en C1-C18, alcényle en C2-C18 ou alcynyle en C2-C18, où chacun des trois radicaux cités en dernier lieu est non substitué ou substitué, ou est un groupe de la formule A5, 6 R est H, un groupe alkyle en C1-C18, alcényle en C2-C18 ou alcynyle en C2-C18, où chacun des trois radicaux

71 EP 2 231 679 B1

cités en dernier lieu est non substitué ou substitué, ou est un groupe de la formule A6, ou R1 et R2 ou R3 et R4 avec l’atome N lié aux uns et aux autres forment un cycle N-hétérocyclique ayant de 3 à 7 atomes de cycle et présentant éventuellement un ou plusieurs hétéroatomes supplémentaires choisis dans le groupe constitué de N, 0 et S et lequel est non substitué ou substitué, 5 1 2 3 4 5 6 A ,A ,A ,A ,A et A , indépendamment les uns des autres, sont un groupe cycloalkyle en C3-C9, cycloalcényle en C4-C9, cycloalcynyle en C5-C9, aryle ou hétérocyclyle comme moitié cyclique basique, où la moitié cyclique basique est non substituée ou substituée, B1 est un groupe comme défini pour R1 de plus lié au groupe amino du groupe de la formule (I*)

20 dans laquelle R2*,R3*,R4*,R5*,R6*, X* et Y* sont indépendamment comme définis dans la formule (I) respectivement pour R2, R3, R4, R5, R6, X et Y, X et Y sont chacun indépendamment l’un de l’autre choisis dans le groupe constitué de

25 (i) un groupe amino, (ii) un groupe de la formule NR7R8, dans laquelle R7 est un radical choisi dans le groupe constitué de radicaux comme définis pour et indépendamment de R1, et dans laquelle R8 est un radical choisi dans le groupe constitué de radicaux comme définis pour et indépendamment de R2, (iii) un groupe hydroxy, 30 (iv) un groupe alcoxy en C1-C6, haloalcoxy en C1-C6, (alcoxy en C1-C6)-(alcoxy en C1-C6) et alkylthio en C1-C6, (v) un groupe alcoxy en C1-C6, haloalcoxy en C1-C6, (alcoxy en C1-C6)-(alcoxy en C1-C6) et alkylthio en C1-C6, où chacun des derniers quatre radicaux est substitué par un ou plusieurs radicaux choisis dans le groupe constitué d’un groupe cycloalkyle en C3-C6, cycloalcoxy en C3-C6, 35 où chacun des 2 radicaux cités en dernier lieu est non substitué ou substitué par un ou plusieurs radicaux choisis dans le groupe constitué d’un atome d’halogène, d’un groupe hydroxy, carbamoyle, alkyle en C1-C6, haloalkyle en C1-C6 (alcoxy en C1-C6)-(alkyle en C1-C6), alcoxy en C1-C6, haloalcoxy en C1-C6 et (alcoxy en C1-C6)-(alcoxy en C1-C6), aryle et aryloxy, où chacun des 2 radicaux cités en dernier lieu est non substitué ou substitué par un ou plusieurs radicaux 40 choisis dans le groupe constitué d’un atome d’halogène, d’un groupe hydroxy, nitro, carbamoyle, sulfo, alkyle en C1-C6, haloalkyle en C1-C6, (alcoxy en C1-C6)-(alkyle en C1-C6), alcoxy en C1-C6, haloalcoxy en C1-C6, (alcoxy en C1-C6)-(alcoxy en C1-C6), alkylthio en C1-C6, alkylsulfinyle en C1-C6, haloalkylsulfinyle en C1-C6, alkylsulfonyle en C1-C6, haloalkylsulfonyle en C1-C6, di-[alkyle en C1-C4]-amino, (alkyle en C1-C4) aminocarbonyle, di-[alkyle en C1-C4]-aminocarbonyle, (alkyle en C1-C4)amino-carbonylamino et di-[alkyle 45 en C1-C4]-aminocarbonylamino, (vi) cycloalcoxy en C3-C6 qui est non substitué ou substitué par un ou plusieurs radicaux choisis dans le groupe constitué d’un atome d’halogène, d’un groupe hydroxy, carbamoyle, alkyle en C1-C6, haloalkyle en C1-C6, (alcoxy en C1-C6)-(alkyle en C1-C6), alcoxy en C1-C6, haloalcoxy en C1-C6 et (alcoxy en C1-C6)-(alcoxy en C1-C6), 50 (vii) aryloxy qui est non substitué ou substitué, et (viii) acyloxy, acylthio ou acylamino,

ou X et Y sont ensemble un groupe divalent de la formule -U1-D*-U2- dans laquelle 55 D* est un pont hydrocarboné, éventuellement interrompu par un ou plusieurs groupes divalents de la formule U3 définie ci-dessous, et U1,U2 et U3 sont indépendamment l’un de l’autre choisis dans le groupe constitué de NH, NR’, 0 et S, où

72 EP 2 231 679 B1

R’ est un groupe alkyle en C1-C6, hydroxy-(alkyle en C1-C6) ou (alcoxy en C1-C6)-(alkyle en C1-C6),

X est un radical comme défini ci-dessus et Y est un ligand organique basé sur un composé de la formule Y’- H, Y’-RL ou RL-U3-D**-U4-RLL, dans laquelle D** est un groupe divalent comme défini pour le groupe D* ci- 5 dessus, Y’ est un radical comme défini pour Y, U3 est un groupe divalent comme défini pour U1 ci-dessus, U4 est un groupe divalent comme défini pour U2 ci-dessus, chacun de RL et RLL est un groupe radicalaire choisi dans le groupe constitué d’un groupe alkyle en C1-C6, hydroxy-(alkyle en C1-C6 ) ou (alcoxy en C1-C6)-(alkyle en C1-C6), et où le ligand organique est coordonné à l’atome d’aluminium du complexe par une paire d’électrons libres d’un hétéroatome contenu dans celui-ci et choisi dans le groupe constitué de N, 0 et S, 10 ou X et Y sont ensemble un radical de la formule -U1-D*-U2-RLLL, dans laquelle U1,U2 et D* sont comme définis LLL ci-dessus, et R est un radical choisi dans le groupe constitué d’un groupe alkyle en C1-C6, hydroxy-(alkyle 1 2 LLL en C1-C6) ou (alcoxy en C1-C6)-(alkyle en C1-C6), et où le radical -U -D*-U -R est de plus coordonné à l’atome d’aluminium du complexe par une paire d’électrons libres disposée sur un hétéroatome contenu dans 15 le radical (position représentée par Y).

2. Composé selon la revendication 1, caractérisé en ce que

1 R est un groupe alkyle en C1-C18, alcényle en C2-C18 ou alcynyle en C2-C18, 20 où chacun des trois radicaux cités en dernier lieu est non substitué ou substitué par un ou plusieurs radicaux choisis dans le groupe constitué d’un atome d’halogène, d’un groupe hydroxy, nitro, carbamoyle, sulfo et des 1a 1b 1c 1d 1e 1f 1g 1h 1i radicaux des formules -O-R , -S-R , -S(=O)-R , -S(=O)2-R ,-NR R , -C(=O)-NHR , -C(=O)-NR R , -NHC(=O)-NR1jR1k et A1a,oùR1a,R1b,R1c,R1d,R1e,R1f,R1g,R1h,R1i,R1j et R1k sont indépendamment l’un de l’autre un groupe alkyle en C1-C6, haloalkyle en C1-C6, (alcoxy en C1-C6)-(alkyle en C1-C6) ou un radical 25 de la formule A1b, ou est un groupe de la formule A1 ou B1, 2 R est H, un groupe alkyle en C1-C18, alcényle en C2-C18 ou alcynyle en C2-C18, où chacun des trois radicaux cités en dernier lieu est non substitué ou substitué par un ou plusieurs radicaux choisis dans le groupe constitué d’un atome d’halogène, d’un groupe hydroxy, nitro, carbamoyle, sulfo et des 30 2a 2b 2c 2d 2e 2f 2g 2h 2i radicaux des formules -O-R , -S-R , -S(=O)-R , -S(=O)2-R ,-NR R , -C(=O)-NHR , -C(=O)-NR R , -NHC(=O)-NR2jR2k et A2a,oùR2a R2b,R2c,R2d,R2e,R2f,R2g,R2h,R2i,R2j et R2k sont indépendamment l’un de l’autre un groupe alkyle en C1-C6, haloalkyle en C1-C6, (alcoxy en C1-C6)-(alkyle en C1-C6) ou un radical de la formule A2b, ou est un groupe de la formule A2, 35 3 R est H, un groupe alkyle en C1-C18, alcényle en C2-C18 ou alcynyle en C2-C18, où chacun des trois radicaux cités en dernier lieu est non substitué ou substitué par un ou plusieurs radicaux choisis dans le groupe constitué d’un atome d’halogène, d’un groupe hydroxy, nitro, carbamoyle, sulfo et des radicaux des formules -O-R3a,-S- 3b 3c 3d 3e 3f 3g 3h 3i 3j 3k 3a 3a R , -S(=O)-R , -S(=O)2-R ,-NR R , -C(=O)-NHR , -C(=O)-NR R , -NHC(=O)-NR R et A ,oùR , 3b 3c 3d 3e 3f 3g 3h 3i 3j 3k R ,R ,R ,R ,R ,R ,R ,R ,R et R sont indépendamment l’un de l’autre un groupe alkyle en C1-C6, 40 3b haloalkyle en C1-C6, (alcoxy en C1-C6)-(alkyle en C1-C6) ou un radical de la formule A , ou est un groupe de la formule A3, 4 R est H, un groupe alkyle en C1-C18, alcényle en C2-C18 ou alcynyle en C2-C18, où chacun des trois radicaux cités en dernier lieu est non substitué ou substitué par un ou plusieurs radicaux choisis dans le groupe constitué d’un atome d’halogène, d’un groupe hydroxy, nitro, carbamoyle, sulfo et des 45 4a 4b 4c 4d 4e 4f 4g 4h 4i radicaux des formules -O-R , -S-R , -S(=O)-R , -S(=O)2-R ,-NR R , -C(=O)-NHR , -C(=O)-NR R , -NHC(=O)-NR4jR4k et A4a, où R4a,R4b,R4c,R4d,R4e,R4f,R4g,R4h,R4i,R4j et R4k sont indépendamment l’un de l’autre un groupe alkyle 4b en C1-C6, haloalkyle en C1-C6, (alcoxy en C1-C6)-(alkyle en C1-C6) ou un radical de la formule A , ou est un groupe de la formule A4, 50 5 R est H, un groupe alkyle en C1-C18, alcényle en C2-C18 ou alcynyle en C2-C18, où chacun des trois radicaux cités en dernier lieu est non substitué ou substitué par un ou plusieurs radicaux choisis dans le groupe constitué d’un atome d’halogène, d’un groupe hydroxy, nitro, carbamoyle, sulfo et des 5a 5b 5c 5d 5 5f 5g 5h 5i radicaux des formules -O-R , -S-R , -S(=O)-R , -S(=O)2-R ,-NR R , -C(=O)-NHR , -C(=O)-NR R , -NHC(=O)-NR5jR5k et A5a, 55 où R5a,R5b,R5c,R5d,R5e,R5f,R5g,R5h,R5i,R5j et R5k sont indépendamment l’un de l’autre un groupe alkyle 5b en C1-C6, haloalkyle en C1-C6, (alcoxy en C1-C6)-(alkyle en C1-C6) ou un radical de la formule A , ou est un groupe de la formule A5, 6 R est H, un groupe alkyle en C1-C18, alcényle en C2-C18 ou alcynyle en C2-C18, où chacun des trois radicaux

73 EP 2 231 679 B1

cités en dernier lieu est non substitué ou substitué par un ou plusieurs radicaux choisis dans le groupe constitué d’un atome d’halogène, d’un groupe hydroxy, nitro, carbamoyle, sulfo et des radicaux des formules -O-R6a,-S- 6b 6c 6d 6e 6f 6g 6h 6i 6j 6k 6a R , -S(=O)-R , -S(=O)2-R ,-NR R , -C(=O)-NHR , -C(=O)-NR R , -NHC(=O)-NR R et A , où R6a,R6b,R6c,R6d,R6e,R6f,R6g,R6h,R6i,R6j et R6k sont indépendamment l’un de l’autre un groupe alkyle 5 6b en C1-C6, haloalkyle en C1-C6, (alcoxy en C1-C6)-(alkyle en C1-C6) ou un radical de la formule A , ou est un groupe de la formule A6, ou R1 et R2 ou R3 et R4 avec l’atome N lié aux uns et aux autres forment un cycle N-hétérocyclique ayant de 3 à 7 atomes de cycle et ayant éventuellement un ou plusieurs hétéroatomes supplémentaires choisis dans le groupe constitué de N, O et S et lequel est non substitué ou substitué par un ou plusieurs radicaux choisis dans 10 le groupe constitué d’un atome d’halogène, d’un groupe hydroxy, nitro, carbamoyle, sulfo, alkyle en C1-C6, haloalkyle en C1-C6, (alcoxy en C1-C6)-(alkyle en C1-C6), alcoxy en C1-C6, haloalcoxy en C1-C6, (alcoxy en C1-C6)-(alcoxy en C1-C6), alkylthio en C1-C6, alkylsulfinyle en C1-C6, haloalkylsulfinyle en C1-C6, alkylsulfonyle en C1-C6, haloalkylsulfonyle en C1-C6, di-[alkyle en C1-C4]-amino, (alkyle en C1-C4)amino-carbonyle, di-[alkyle en C1-C4]-aminocarbonyle, (alkyle en C1-C4)aminocarbonylamino, di-[alkyle en C1-C4]-aminocarbonylamino 15 et oxo, A1,A1a,A1b,A2,A2a,A2b,A3,A3a,A3b,A4,A4a,A4b,A5,A5a,A5b,A6,A6a et A6b sont indépendamment l’un de l’autre un groupe cycloalkyle en C3-C9, cycloalcényle en C4-C9, cycloalcynyle en C5-C9, aryle ou hétérocyclyle comme moitié cyclique basique, où la moitié cyclique basique,

20 (a) est non substituée ou substituée par un ou plusieurs radicaux choisis dans le groupe constitué d’un atome d’halogène, d’un groupe hydroxy, nitro, carbamoyle, sulfo, alkyle en C1-C6, haloalkyle en C1-C6, (alcoxy en C1-C6)-(alkyle en C1-C6), alcoxy en C1-C6, haloalcoxy en C1-C6, (alcoxy en C1-C6)-(alcoxy en C1-C6), alkylthio en C1-C6, alkylsulfinyle en C1-C6, haloalkylsulfinyle en C1-C6, alkylsulfonyle en C1-C6, haloalkylsulfonyle en C1-C6, di-[alkyle en C1-C4]-amino, alkylaminocarbonyle en C1-C4, di-[alkyle en 25 C1-C4)-aminocarbonyle, (alkyle en C1-C4)aminocarbonylamino et di-[alkyle en C1-C4)-aminocarbonylamino, et, dans le cas d’un groupe hétérocyclyle, également oxo lié aux atomes d’hétérocycle N ou S ou en position alpha d’un atome N comme atome d’hétérocycle, ou (b) est substituée ou substituée de plus sur un ou plusieurs des substituants cités dans (a) par un pont lié 30 géminal (une position 1,1), vicinal (une position 1,2) ou dans une position 1,3 sur la moitié cyclique basique formant ainsi un autre cycle carbocyclique ou hétérocyclique avec la partie de la moitié cyclique basique entre les atomes liés au pont, où le cycle carbocyclique ou hétérocyclique formé est saturé, partiellement insaturé, insaturé, aromatique ou hétéroaromatique et où le pont est de plus non substitué ou substitué par un ou plusieurs radicaux choisis dans le groupe constitué d’un atome d’halogène, d’un groupe hydroxy, 35 nitro, carbamoyle, sulfo, alkyle en C1-C6, haloalkyle en C1-C6, (alcoxy en C1-C6)-(alkyle en C1-C6), alcoxy en C1-C6, haloalcoxy en C1-C6, (alcoxy en C1-C6)-(alcoxy en C1-C6), alkylthio en C1-C6, alkylsulfinyle en C1-C6, haloalkylsulfinyle en C1-C6, alkylsulfonyle en C1-C6, haloalkylsulfonyle en C1-C6, di-[alkyle en C1-C4]-amino, (alkyle en C1-C4)aminocarbonyle, di-[alkyle en C1-C4]-aminocarbonyle, (alkyle en C1-C4) aminocarbonylamino et di-[alkyle en C1-C4]-aminocarbonylamino, 40 B1 est un groupe comme défini pour R1 de plus lié au groupe amino du groupe de la formule (I*)

dans laquelle R2*, R3*, R4*, R5*, R6*, X* et Y* sont indépendamment comme définis dans la formule (I) respectivement 55 pour R2, R3, R4, R5, R6, X et Y, X et Y sont chacun indépendamment l’un de l’autre choisis dans le groupe constitué de

(i) un groupe amino,

74 EP 2 231 679 B1

(ii) un groupe de la formule NR7R8, dans laquelle R7 est un radical choisi dans le groupe constitué de radicaux comme définis pour et indépendamment de R1, et dans laquelle R8 est un radical choisi dans le groupe constitué de radicaux comme définis pour et indépendamment de R2, (iii) un groupe hydroxy, 5 (iv) un groupe alcoxy en C1-C6, haloalcoxy en C1-C6, (alcoxy en C1-C6)-(alcoxy en C1-C6) et alkylthio en C1-C6, (v) un groupe alcoxy en C1-C6, haloalcoxy en C1-C6, (alcoxy en C1-C6)-(alcoxy en C1-C6) et alkylthio en C1-C6, où chacun des derniers 4 radicaux est substitué par un ou plusieurs radicaux choisis dans le groupe constitué d’un groupe cycloalkyle en C3-C6, cycloalcoxy en C3-C6, où chacun des 2 radicaux cités en dernier lieu est non substitué ou substitué par un ou plusieurs radicaux 10 choisis dans le groupe constitué d’un atome d’halogène, d’un groupe hydroxy, carbamoyle, alkyle en C1-C6, haloalkyle en C1-C6 (alcoxy en C1-C6)-(alkyle en C1-C6), alcoxy en C1-C6, haloalcoxy en C1-C6 et (alcoxy en C1-C6)-(alcoxy en C1-C6), aryle et aryloxy, où chacun des 2 radicaux cités en dernier lieu est non substitué ou substitué par un ou plusieurs radicaux 15 choisis dans le groupe constitué d’un atome d’halogène, d’un groupe hydroxy, nitro, carbamoyle, sulfo, alkyle en C1-C6, haloalkyle en C1-C6, (alcoxy en C1-C6)-(alkyle en C1-C6), alcoxy en C1-C6, haloalcoxy en C1-C6, (alcoxy en C1-C6)-(alcoxy en C1-C6), alkylthio en C1-C6, alkylsulfinyle en C1-C6, haloalkylsulfinyle en C1-C6, alkylsulfonyle en C1-C6, haloalkylsulfonyle en C1-C6, di-[alkyle en C1-C4]-amino, (alkyle en C1-C4)aminocarbonyle, di-[alkyle en C1-C4]-aminocarbonyle, (alkyle en C1-C4)amino-carbonylamino et di-[alkyle en C1-C4]-ami- 20 nocarbonylamino, (vi) cycloalcoxy en C3-C6 qui est non substitué ou substitué par un ou plusieurs radicaux choisis dans le groupe constitué d’un atome d’halogène, d’un groupe hydroxy, carbamoyle, alkyle en C1-C6, haloalkyle en C1-C6, (alcoxy en C1-C6)-(alkyle en C1-C6), alcoxy en C1-C6, haloalcoxy en C1-C6 et (alcoxy en C1-C6)-(alcoxy en C1-C6), 25 (vii) aryloxy qui est non substitué ou substitué par un ou plusieurs radicaux choisis dans le groupe constitué d’un atome d’halogène, d’un groupe hydroxy, nitro, carbamoyle, sulfo, alkyle en C1-C6, haloalkyle en C1-C6, (alcoxy en C1-C6)-(alkyle en C1-C6), alcoxy en C1-C6, haloalcoxy en C1-C6, (alcoxy en C1-C6)-(alcoxy en C1-C6), alkylthio en C1-C6, alkylsulfinyle en C1-C6, haloalkylsulfinyle en C1-C6, alkylsulfonyle en C1-C6, haloalkylsulfonyle en C1-C6, di-[alkyle en C1-C4]-amino, (alkyle en C1-C4)aminocarbonyle, di-[alkyle en C1-C4]-aminocarbo- 30 nyle, (alkyle en C1-C4)amino-carbonylamino et di-[alkyle en C1-C4]-aminocarbonylamino, et (viii) acyloxy, acylthio ou acylamino ayant chacun de 1 à 12 atomes de carbone, ou

35 X et Y sont ensemble un groupe divalent de la formule -U1-D*-U2- dans laquelle

D* est un pont alkylène linéaire, un pont alcénylène en C2-C10 linéaire, un pont alcynylène en C2-C10 linéaire, un pont cycloalkylène en C3-C9, un pont phénylène ou un pont constitué d’une combinaison de deux ou plusieurs desdites moitiés acycliques et cycliques linéaires ayant au total de 4 à 24 atomes de carbone, où le pont est 40 dans chaque cas non substitué ou substitué par un ou plusieurs radicaux choisis dans le groupe constitué d’un atome d’halogène, d’un groupe hydroxy, nitro, carbamoyle, sulfo, alkyle en C1-C6, haloalkyle en C1-C6, (alcoxy en C1-C6)-(alkyle en C1-C6), alcoxy en C1-C6, haloalcoxy en C1-C6, (alcoxy en C1-C6)-(alcoxy en C1-C6), alkylthio en C1-C6, alkylsulfinyle en C1-C6, haloalkylsulfinyle en C1-C6, alkylsulfonyle en C1-C6, haloalkylsulfonyle en C1-C6, di-[alkyle en C1-C4]-amino, (alkyle en C1-C4)aminocarbonyle, di-[alkyle en C1-C4]-aminocarbo- 45 nyle, (alkyle en C1-C4)aminocarbonylamino et di-[alkyle en C1-C4]-aminocarbonylamino, et U1,U2 et U3 sont indépendamment l’un de l’autre choisis dans le groupe constitué de NH, NR’, O et S, où R’ est un groupe alkyle en C1-C6, hydroxy-(alkyle en C1-C6) ou (alcoxy en C1-C6)-(alkyle en C1-C6), ou X est un radical comme défini ci-dessus et Y est un ligand organique sur la base d’un composé de la formule 50 Y’-H, Y’-RL ou RL-U3-D**-U4-RLL, dans laquelle D** est un groupe divalent comme défini pour le groupe D* ci- dessus, Y’ est un radical comme défini pour Y, U3 est un groupe divalent comme défini pour U1 ci-dessus, U4 est un groupe divalent comme défini pour U2 ci-dessus, chacun de RL et RLL est un groupe de radical choisi dans le groupe constitué d’un groupe alkyle en C1-C6, hydroxy-(alkyle en C1-C6) ou (alcoxy en C1-C6)-(alkyle en C1-C6), et où le ligand organique est coordonné à l’atome d’aluminium du complexe par une paire d’électrons 55 libres d’un hétéroatome contenu dans celui-ci et choisi dans le groupe constitué de N, 0 et S, ou X et Y sont ensemble un radical de la formule -U1-D*-U2-RLLL, dans laquelle U1,U2 et D* sont comme définis LLL ci-dessus, et R est un radical choisi dans le groupe constitué d’un groupe alkyle en C1-C6, hydroxy-(alkyle

75 EP 2 231 679 B1

1 2 LLL en C1-C6) ou (alcoxy en C1-C6)-(alkyle en C1-C6), et dans laquelle le radical -U -D*-U -R est de plus coor- donné à l’atome d’aluminium du complexe par une paire d’électrons libres disposée sur un hétéroatome contenu dans le radical (position représentée par Y), de préférence disposée sur l’hétéroatome du groupe divalent U2.

5 3. Composé selon la revendication 1 ou 2, caractérisé en ce que

1 R est un groupe alkyle en C1-C12, alcényle en C2-C12 ou alcynyle en C2-C12, où chacun des trois radicaux cités en dernier lieu est non substitué ou substitué par un ou plusieurs radicaux choisis dans le groupe constitué d’un atome d’halogène, d’un groupe hydroxy, nitro, carbamoyle, sulfo et des 10 1a 1b 1c 1d 1e 1f 1g 1h 1i radicaux des formules -O-R , -S-R , -S(=O)-R , -S(=O)2-R ,-NR R , -C(=O)-NHR , -C(=O)-NR R , -NHC(=O)-NR1jR1k et A1a, où R1a,R1b,R1c,R1d,R1e,R1f,R1g,R1h,R1i,R1j et R1k sont indépendamment l’un de l’autre un groupe alkyle 1b en C1-C6, haloalkyle en C1-C6, (alcoxy en C1-C6)-(alkyle en C1-C6) ou un radical de la formule A , ou est un groupe de la formule A1 ou B1, 15 ou R1 et R2 avec l’atome N lié à l’un et à l’autre forment un cycle N-hétérocyclique ayant 5 ou 6 atomes de cycle et présentant éventuellement 1, 2 ou 3 hétéroatomes supplémentaires choisis dans le groupe constitué de N, 0 et S et lequel est non substitué ou substitué par un ou plusieurs radicaux choisis dans le groupe constitué d’un atome d’halogène, d’un groupe hydroxy, nitro, carbamoyle, sulfo, alkyle en C1-C6, haloalkyle en C1-C6, 20 (alcoxy en C1-C6)-(alkyle en C1-C6), alcoxy en C1-C6, haloalcoxy en C1-C6, (alcoxy en C1-C6)-(alcoxy en C1-C6), alkylthio en C1-C6, alkylsulfinyle en C1-C6, haloalkylsulfinyle en C1-C6, alkylsulfonyle en C1-C6, haloalkylsulfonyle en C1-C6, di-[alkyle en C1-C4]-amino, (alkyle en C1-C4)aminocarbonyle, di-[alkyle en C1-C4]-aminocarbonyle, (alkyle en C1-C4)aminocarbonylamino, di-[alkyle en C1-C4]-aminocarbonylamino et oxo, 1 1a 1b A ,A ,etA sont indépendamment l’un de l’autre un groupe cycloalkyle en C3-C9, cycloalcényle en C4-C9, 25 cycloalcynyle en C5-C9, aryle ou hétérocyclyle comme moitié cyclique basique, où la moitié cyclique basique,

(a) est non substituée ou substituée par un ou plusieurs radicaux choisis dans le groupe constitué d’un atome d’halogène, d’un groupe hydroxy, nitro, carbamoyle, sulfo, alkyle en C1-C6, haloalkyle en C1-C6, (alcoxy en C1-C6)-(alkyle en C1-C6), alcoxy en C1-C6, haloalcoxy en C1-C6, (alcoxy en C1-C6)-(alcoxy en 30 C1-C6), alkylthio en C1-C6, alkylsulfinyle en C1-C6, haloalkylsulfinyle en C1-C6, alkylsulfonyle en C1-C6, haloalkylsulfonyle en C1-C6, di-[alkyle en C1-C4]-amino, (alkyle en C1-C4)aminocarbonyle, di-[alkyle en C1-C4]-aminocarbonyle, (alkyle en C1-C4)amino-carbonylamino et di-[alkyle en C1-C4]-aminocarbonylamino, et, dans le cas d’un groupe hétérocyclyle, également oxo lié aux atomes d’hétérocycle N ou S ou en position alpha d’un atome N comme atome d’hétérocycle, 35 ou (b) est substituée ou substituée de plus sur un ou plusieurs des substituants cités dans (a) par un pont lié géminal (une position 1,1), vicinal (une position 1,2) ou dans une position 1,3 sur la moitié cyclique basique formant ainsi un autre cycle carbocyclique ou hétérocyclique avec la partie de la moitié cyclique basique entre les atomes liés au pont, où le cycle carbocyclique ou hétérocyclique formé est saturé, partiellement 40 saturé, insaturé ayant de 3 à 9 atomes de cycle ou est aromatique ou hétéroaromatique ayant 5 ou 6 atomes de cycle, et où le pont est de plus non substitué ou substitué par un ou plusieurs radicaux choisis dans le groupe constitué d’un atome d’halogène, d’un groupe hydroxy, nitro, carbamoyle, sulfo, alkyle en C1-C6, haloalkyle en C1-C6, (alcoxy en C1-C6)-(alkyle en C1-C6), alcoxy en C1-C6, haloalcoxy en C1-C6, (alcoxy en C1-C6)-(alcoxy en C1-C6), alkylthio en C1-C6, alkylsulfinyle en C1-C6, haloalkylsulfinyle en C1-C6, 45 alkylsulfonyle en C1-C6, haloalkylsulfonyle en C1-C6, di-[alkyle en C1-C4]-amino, (alkyle en C1-C4)aminocarbonyle, di-[alkyle en C1-C4]-aminocarbonyle, (alkyle en C1-C4)-aminocarbonylamino et di-[alkyle en C1-C4]-aminocarbonylamino, et, dans le cas d’un groupe hétérocyclyle, également oxo lié aux atomes d’hétérocycle N ou S ou en position alpha d’un atome N comme atome d’hétérocycle, ou est de plus benzocondensé où le cycle benzène condensé supplémentaire est non substitué ou de plus substitué par 50 un ou plusieurs radicaux comme définis pour la substitution du pont qui est benzocondensé,

B1 est un groupe comme défini pour R1 de plus lié au groupe amino du groupe de la formule (I*),

76 EP 2 231 679 B1

dans laquelle R2*, R3*, R4*, R5*, R6*, X* et Y* sont indépendamment comme définis dans la formule (I) respectivement pour R2, R3, R4, R5, R6, X et Y.

15 4. Composé selon l’une quelconque des revendications 1 à 3, caractérisé en ce que

2 R est H, un groupe alkyle en C1-C4, alcényle en C2-C4 ou alcynyle en C2-C4, haloalkyle en C1-C4, phényle, naphtyle, phényl(alkyle en C1-C4) ou cycloalkyle en C3-C6, où chacun des 4 radicaux cités en dernier lieu est non substitué ou substitué dans la moitié cyclique par un ou plusieurs radicaux comme définis pour les subs- 20 tituants sur le groupe cyclique A2, et R3, R4, R5 et R6 sont chacun H.

5. Composé selon l’une quelconque des revendications 1 à 4, caractérisé en ce que X et Y sont indépendamment l’un de l’autre chacun choisi dans le groupe constitué de 25 (i) un groupe amino, (ii) un groupe de la formule NR7R8 qui est défini comme le groupe NR1R2 dans la formule (I), (iii) un groupe hydroxy, (iv) un groupe alcoxy en C1-C4, haloalcoxy en C1-C4, (alcoxy en C1-C4)-(alcoxy en C1-C4) et alkylthio en C1-C4, 30 (v) un groupe alcoxy en C1-C4, haloalcoxy en C1-C4, (alcoxy en C1-C4)-(alcoxy en C1-C4) et alkylthio en C1-C4, où chacun des derniers 4 radicaux est substitué par un ou plusieurs radicaux choisis dans le groupe constitué d’un groupe cycloalkyle en C3-C6, cycloalcoxy en C3-C6, où chacun des 2 radicaux cités en dernier est non substitué ou substitué par un ou plusieurs radicaux choisis dans le groupe constitué d’un atome d’halogène, d’un groupe hydroxy, carbamoyle, alkyle en C1-C4, haloalkyle 35 en C1-C4 (alcoxy en C1-C4)-(alkyle en C1-C4), alcoxy en C1-C4, haloalcoxy en C1-C4 et (alcoxy en C1-C4)-(alcoxy en C1-C4), phényle et phénoxy, où chacun des 2 radicaux cités en dernier lieu est non substitué ou substitué par un ou plusieurs radicaux choisis dans le groupe constitué d’un atome d’halogène, d’un groupe hydroxy, nitro, carbamoyle, sulfo, alkyle 40 en C1-C4, haloalkyle en C1-C4, (alcoxy en C1-C4)-(alkyle en C1-C4), alcoxy en C1-C4, haloalcoxy en C1-C4, (alcoxy en C1-C4)-(alcoxy en C1-C4), alkylthio en C1-C4, alkylsulfinyle en C1-C4, haloalkylsulfinyle en C1-C4, alkylsulfonyle en C1-C4, haloalkylsulfonyle en C1-C4, di-[alkyle en C1-C4]-amino, (alkyle en C1-C4)aminocarbonyle, di-[alkyle en C1-C4]-aminocarbonyle, (alkyle en C1-C4)amino-carbonylamino et di-[alkyle en C1-C4]-aminocarbonylamino, 45 (vi) cycloalcoxy en C3-C6 qui est non substitué ou substitué par un ou plusieurs radicaux choisis dans le groupe constitué d’un atome d’halogène, d’un groupe hydroxy, carbamoyle, alkyle en C1-C4, haloalkyle en C1-C4, (alcoxy en C1-C4)-(alkyle en C1-C4), alcoxy en C1-C4, haloalcoxy en C1-C4 et (alcoxy en C1-C4)-(alcoxy en C1-C4), et 50 (vii) un groupe phénoxy, qui est non substitué ou substitué par un ou plusieurs radicaux choisis dans le groupe constitué d’un atome d’halogène, d’un groupe hydroxy, nitro, carbamoyle, sulfo, alkyle en C1-C4, haloalkyle en C1-C4, (alcoxy en C1-C4)-(alkyle en C1-C4), alcoxy en C1-C4, haloalcoxy en C1-C4, (alcoxy en C1-C4)-(alcoxy en C1-C4), alkylthio en C1-C4, alkylsulfinyle en C1-C4, haloalkylsulfinyle en C1-C4, alkylsulfonyle en C1-C4, haloalkylsulfonyle en C1-C4, di-[alkyle en C1-C4]-amino, (alkyle en C1-C4)-aminocarbonyle, di-[alkyle en 55 C1-C4]-aminocarbonyle, (alkyle en C1-C4)-aminocarbonylamino et di-[alkyle en C1-C4]-aminocarbonylamino, et, (viii) acyloxy, acylthio ou acylamino, où le groupe acyle dans les trois groupes cités en dernier lieu est un groupe formyle, alkylcarbonyle en C1-C6, alkylsulfonyle en C1-C6 ou phénylsulfonyle, dont le dernier est non substitué

77 EP 2 231 679 B1

ou substitué par un ou plusieurs radicaux choisis dans le groupe constitué d’un atome d’halogène, d’un groupe alkyle en C1-C4, haloalkyle en C1-C4, (alcoxy en C1-C4)-(alkyle en C1-C4), alcoxy en C1-C4, haloalcoxy en C1-C4, (alcoxy en C1-C4)-(alcoxy en C1-C4) et alkylthio en C1-C4, ou 5 X et Y sont ensemble un groupe divalent de la formule -O-D*-O-, -S-D*-S-, -NH-D*-NH-, -O-D*-NH-, -O-D*-S-, -N(CH3)-D*-N(CH3)-, -NH-D*--N(CH3)-, -N(C2H5)-D*-N(C2H5)-ou -NH-D*-N(C2H5)-, où D* dans chacun des 9 groupes divalents cités en dernier lieu est un pont alkylène linéaire, un pont alcénylène en C2-C10 linéaire, un pont alcynylène en C2-C10 linéaire, un pont cycloalkylène en C3-C9, un pont phénylène ou un pont constitué 10 d’une combinaison de deux ou plusieurs desdites moitiés acycliques et cycliques linéaires ayant au total de 4 à 18 atomes de carbone, où le pont dans chaque cas est non substitué ou substitué par un ou plusieurs radicaux choisis dans le groupe constitué d’un atome d’halogène, d’un groupe hydroxy, nitro, carbamoyle, sulfo, alkyle en C1-C4, haloalkyle en C1-C4, (alcoxy en C1-C4)-(alkyle en C1-C4), alcoxy en C1-C4, haloalcoxy en C1-C4, (alcoxy en C1-C4)-(alcoxy en C1-C4), alkylthio en C1-C4, alkylsulfinyle en C1-C4, haloalkylsulfinyle en C1-C4, 15 alkylsulfonyle en C1-C4, haloalkylsulfonyle en C1-C4, di-[alkyle en C1-C4]-amino, (alkyle en C1-C4)-aminocarbonyle, di-[alkyle en C1-C4]-aminocarbonyle, (alkyle en C1-C4)aminocarbonylamino et di-[alkyle en C1-C4]-aminocarbonylamino, ou X est un radical comme défini ci-dessus et Y est un ligand organique basé sur un composé de la formule Y’- 20 H, Y’-RL ou RL-O-D**-O-RLL,RL-S-D**-S-RLL,RL-NH-D**-NH-RLL,RL-O-D**-NH-RLL,RL-O-D**-S-RLL,RL-N LL L LL L LL L LL (CH3)-D**-N(CH3)-R ,R -NH-D**-N(CH3)-R ,R -N-(C2H5)-D**-N(C2H5)-R ou R -NH-D**-N(C2H5)-R où D** est dans chacun des 9 composés cités en dernier lieu un groupe divalent comme défini pour le groupe D* ci-dessus, Y’ est un radical comme défini pour Y et chacun de RL et RLL est un groupe de radical choisi dans le groupe constitué d’un groupe alkyle en C1-C6, hydroxy-(alkyle en C1-C6) ou (alcoxy en C1-C6)-(alkyle en 25 C1-C6), et où le ligand organique est coordonné à l’atome d’aluminium du complexe par une paire d’électrons libres d’un hétéroatome contenu dans celui-ci et choisi dans le groupe constitué de N, O et S, ou X et Y sont ensemble un radical de la formule -O-D**-ORLLL, -S-D**-S-RLLL, -NH-D**-NH-RLLL, -O-D**-NHRLLL, LLL LLL LLL LLL LLL -NH-D**-O-R , -O-D**-S-R , -S-D**-O-R , -N-(CH3)-D**-N(CH3)-R , -NH-D**-N(CH3)-R ,-N LLL LLL LLL LLL (CH3)-D**-NH-R ,-N(C2H5)-D**-N(C2H5)-R , -NH-D**-N(C2H5)-R ou -N(C2H5)-D**-NH-R ,oùD* 30 dans les 13 radicaux cités en dernier lieu est comme défini ci-dessus, et RLLL est un radical choisi dans le groupe constitué d’un groupe alkyle en C1-C4, hydroxy-(alkyle en C1-C4) ou (alcoxy en C1-C4)-(alkyle en C1-C4), et où le radical est de plus coordonné à l’atome d’aluminium du complexe par une paire d’électrons libres disposée sur un hétéroatome contenu dans le radical (position représentée par Y), de préférence disposée sur l’hétéroatome fixé au groupe RLLL dans le groupe divalent. 35 6. Procédé pour la préparation d’un composé de la formule (I) ou de sels de ceux-ci selon l’une quelconque des revendications 1 à 5,

dans laquelle R1 à R6 et X et Y sont comme définis dans la formule (I), 50 caractérisé en ce que l’on fait réagir un composé (une amine) de la formule (II) ou un sel de celui-ci,

dans laquelle R1 et R2 sont comme définis dans le composé de la formule (I) à préparer,

78 EP 2 231 679 B1

en un composé de la formule (III) ou un sel de celui-ci,

dans laquelle R3,R4,R5 et R6 sont comme définis dans le composé de la formule (I) à préparer, et une source d’aluminium (III), éventuellement en présence d’un additif ou d’un solvant protique choisi dans le groupe constitué d’alcools ou d’amines. 15 7. Procédé selon la revendication 6, caractérisé en ce que la source d’aluminium (III) est choisie parmi

(i) des sels d’aluminium de la formule (IV),

25 dans laquelle X et Y sont comme définis dans le composé de la formule (I) à préparer, et Z, indépendamment de X, est un groupe qui s’éloigne choisi dans le groupe de radicaux comme définis pour X ou Y, ou (ii) des sels d’aluminium de la formule (IV’), 30

dans laquelle X’, Y’ et Z’ sont chacun choisis dans le groupe constitué de radicaux comme définis pour X, Y ou Z respectivement et de radicaux qui génèrent ledit groupe X, Y ou Z respectivement en présence d’un additif ou d’un solvant 40 protique X-H, Y-H ou Z-H respectivement à condition que 1, 2 ou 3 des radicaux X’, Y’ et Z’ sont choisis parmi lesdits radicaux qui génèrent respectivement les radicaux X, Y et Z, en combinaison avec un additif ou un solvant protique X-H, Y-H ou Z-H, où chacun de X, Y et Z est défini comme donné pour X et Y dans la formule (I).

45 8. Utilisation d’un composé de la formule (I) ou de sels de celui-ci comme défini dans revendication 1 pour la préparation de composés hétérocycliques correspondant à la formule (I), dans laquelle le groupe d’aluminium AI(X)(Y) est remplacé par un atome de carbone éventuellement substitué ou des dérivés de s-triazine de celui-ci.

9. Procédé pour la préparation de composés de la formule (V) ou de sels de ceux-ci, 50

79 EP 2 231 679 B1

dans laquelle R1, R2, R3 et R4 sont comme définis dans la formule (I) selon la revendication 1, et Q est

5 a) l’hydrogène, un groupe alkyle en C1-C12, alcényle en C2-C12 ou alcynyle en C2-C12, où chacun des trois radicaux cités en dernier lieu est non substitué ou substitué, b) ou est un groupe cycloalkyle en C3-C6, benzo(cycloalkyle en C5-C6), cycloalcényle en C5-C6, benzo-(cycloal- cényle en C5-C6), phényle, naphtyle, hétérocyclyle ou hétérocyclyle benzocondensé, ou chacun des 8 radicaux cités en dernier lieu est non substitué ou substitué dans la moitié cyclique, 10 c) ou est COR, COOR, C(=S)R, C(=O)SR, C(=S)OR, C(=S)SR, où R dans chacun des 6 radicaux cités en dernier lieu est un groupe alkyle en C1-C18, cycloalkyle C3-C6 ou phényle, les trois derniers radicaux étant non substitués ou substitués,

caractérisé en ce que l’on fait réagir un composé de la formule (I) ou un sel de celui-ci 15

dans laquelle R1, R2, R3 et R4 sont comme définis dans le composé de la formule (V) à préparer et R5 et R6 sont l’hydrogène, 30 avec un composé de la formule (VI)

Q-W* (VI)

dans laquelle 35 Q est comme défini dans le composé de la formule (V) à préparer et W* est un atome de carbone qui porte 3 liaisons supplémentaires à 1, 2 ou 3 groupes qui s’éloignent, lesquels sont liés par des hétéroatomes,

40 pour fournir le composé de la formule (V) ou un sel de celui-ci.

10. Procédé selon la revendication 9, caractérisé en ce que le composé (I) est préparé selon le procédé selon la revendication 6 ou 7 et est directement utilisé sans isolement pour la préparation du composé de la formule (V), éventuellement dans un procédé en un pot. 45

80 EP 2 231 679 B1

REFERENCES CITED IN THE DESCRIPTION

This list of references cited by the applicant is for the reader’s convenience only. It does not form part of the European patent document. Even though great care has been taken in compiling the references, errors or omissions cannot be excluded and the EPO disclaims all liability in this regard.

Non-patent literature cited in the description

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