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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) TZZ ¥__T (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 Printed by Jouve, 75001 PARIS (FR) EP 2 231 679 B1 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] 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). 35 40 45 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 2 EP 2 231 679 B1 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). 5 10 15 20 25 30 35 40 45 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: 55 3 EP 2 231 679 B1 5 10 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): 20 25 30 35 40 45 [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"), 55 4 EP 2 231 679 B1 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 unsub- stituted 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
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