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

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Synthesis of Biguanidines and Triazines, and Biguanidino-Aluminium Complexes As Intermediates (19) *EP002070934A1* (11) EP 2 070 934 A1 (12) EUROPEAN PATENT APPLICATION (43) Date of publication: (51) Int Cl.: 17.06.2009 Bulletin 2009/25 C07F 5/06 (2006.01) C07D 413/04 (2006.01) C07D 251/54 (2006.01) C07D 401/04 (2006.01) (2006.01) (2006.01) (21) Application number: 07024256.5 C07D 403/04 C07D 405/12 C07D 403/12 (2006.01) (22) Date of filing: 14.12.2007 (84) Designated Contracting States: (71) Applicant: Bayer CropScience AG AT BE BG CH CY CZ DE DK EE ES FI FR GB GR 40789 Monheim (DE) HU IE IS IT LI LT LU LV MC MT NL PL PT RO SE SI SK TR (72) Inventor: Ford, Mark. Dr Designated Extension States: 61389 Schmitten-Oberreifenberg (DE) AL BA HR MK RS (54) Synthesis of biguanidines and triazines, and biguanidino-aluminium complexes as intermediates (57) Compounds of formula (I) or salts thereof, in which R1,R2,R3,R4,R5,R6, X and Y are defined as in claim 1, can be prepared by a process characterized in that a compound of the formula (II) or a salt thereof, is reacted to a compound of the formula (III) or a salt thereof, and an aluminium(III) source, optionally, in the presence of a protic additive or solvent selected from the group consisting of alcohols or amines. The compounds (I) are suitable to be used for the preparation of heterocyclic compounds corresponding to (I) where the group AI(X)(Y) is replaced with an optionally substituted carbon atom, or s-triazine derivatives thereof. EP 2 070 934 A1 Printed by Jouve, 75001 PARIS (FR) EP 2 070 934 A1 Description [0001] The invention is related to the technical field of chemical processes for the preparation of heterocyclic com- pounds, 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] 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 30 a general nature with respect to the amine (Scheme 1). 35 40 45 50 [0005] 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 tautomers of the aluminium complex, which are in equilibrium with the one shown in formula (I) explicitly or can easily 55 be formed therefrom in the reaction mixture. The same shall be valid also for other chemical formulae considered below. [0006] 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 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 2 EP 2 070 934 A1 resonance or tautomeric structures for the aluminium complexes is shown). 5 10 15 20 25 30 35 40 45 50 [0007] 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 main tautomers in case of R5 and R6 both being hydrogen atoms are the following: 55 3 EP 2 070 934 A1 5 10 15 [0008] 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): 20 25 30 35 40 45 [0009] The compounds of the general formula (I) in which R5 and R6 are both hydrogen shall also represent tautomers 50 (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 are specifically considered. The same applies in cases when R5 or R6 or both being different from hydrogen, accordingly. [0010] The invention is thus directed or related to novel aluminium complexes of formula (I), or salts, dimers or polymers thereof (in short "salts thereof’), 55 4 EP 2 070 934 A1 5 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, 15 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 1a 1b 1c 1d 1e 1f 1g -O-R , -S-R , -S(=O)-R , -S(=O)2-R ,-NRR , -C(=O)-NHR ,-C (=O)-NR1hR1i, -NHC(=O)-NR1jR1k and A1a, 20 wherein R1a,R1b,R1c,R1d,R1e,R1f,R1g,R1h,R1i,R1j, and R1k, independently of one another, are (C1-C6)alkyl, (C1-C6)haloalkyl, (C1-C6)alkoxy-(C1-C6)alkyl or a radical of the formula A1b, or is a group of the formula A1 or B1, 2 R is H, (C1-C18)alkyl, (C2-C18)alkenyl or (C2-C18)alkynyl, 25 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 2a 2b 2c 2d 2e 2f 2g -O-R , -S-R , -S(=O)-R , -S(=O)2-R ,-NRR , -C(=O)-NHR ,-C 30 (=O)-NR2hR2i, -NHC(=O)-NR2jR2k and A2a, wherein R2a,R2b,R2c,R2d,R2e,R2f,R2g,R2h,R2i,R2j, and R2k, independently of one another, are (C1-C6)alkyl, (C1-C6)haloalkyl, (C1-C6)alkoxy-(C1-C6)alkyl or a radical of the formula A2b, or is a group of the formula A2, 35 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, 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 40 3a 3b 3c 3d 3e 3f 3g -O-R , -S-R , -S(=O)-R , -S(=O)2-R ,-NRR , -C(=O)-NHR ,-C (=O)-NR3hR3i, -NHC(=O)-NR3jR3k and A3b, wherein R3a,R3b,R3c,R3d,R3e,R3f,R3g,R3h,R3i,R3j, and R3k, independently of one another, are (C1-C6)alkyl, (C1-C6)haloalkyl, (C1-C6)alkoxy-(C1-C6)alkyl or a radical of the formula A3b, 45 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 consisting of halogen, hydroxy, nitro, carbamoyl, sulfo and radicals of the 50 formulae 4a 4b 4c 4d 4e 4f 4g -O-R , -S-R , -S(=O)-R , -S(=O)2-R ,-NRR , -C(=O)-NHR ,-C (=O)-NR4hR4i, -NHC(=O)-NR4jR4k and A4a, wherein
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