Glycine-N,N-diacetic acid derivative preparation in high yield

摘要

Preparation of long-chain substituted glycine-N,N-diacetic acid derivatives (IX) and their intermediates, e.g. from aldehydes and hydrogen cyanide (or alkali metal cyanide) and other reagents such as iminodiacetic acid or ammonia and/or by hydrolysis of corresponding nitriles, is carried out under elevated pressure and/or in presence of additives such as emulsifiers. Several classes of intermediate compounds are new. Preparation of long-chain substituted glycinonitrile-N,N-diacetonitrile compounds of formula (IIb) by reaction of imino-diacetonitrile with aldehydes of formula RCHO and hydrogen cyanide (or alkali metal cyanide) is carried out: (a) in the absence of an organic solvent and in presence of a Lewis or Bronsted acid; (b) in the presence or absence of an organic solvent and in presence of an emulsifier; or (c) in the presence or absence of an organic solvent and under a pressure of 1-40 bar. R = 6-30C alkyl or 6-30C alkenyl, both optionally substituted by 1-5 of OH, CHO, 1-4C alkoxy, phenoxy and (1-4C) alkoxycarbonyl and optionally interrupted by 1-5 non-adjacent O; or -(CH2)kO(A1)n-Y; A1,A2 = 2-4C 1,2-alkylene; Y = H, 1-12C alkyl, phenyl or (1-4C) alkoxycarbonyl; k =1-3; m,n = 0-50, provided that m + n = at least 4. Independent claims are included for the following processes and novel compounds. (1) Preparation of long-chain substituted glycinonitrile compounds of formula R-CH(NH2)(CN) (IIa) by reaction of RCHO with M'CN (M' = H or alkali metal) and ammonia in presence of organic base is carried out under a pressure of 1-40 bars. (2) Preparation of (IIb) by reaction of (IIa) (which may be prepared as above) with formaldehyde and M'CN is carried out in the presence or absence of a solvent under a pressure of 1-40 bars. (3) Preparation of long chain-substituted glycine-N,N-diacetic acid (or its salts) of formula MOOC-CH(R)-N(CH2COOM)2 (IX) by reaction of (IIb) (which may be prepared as above) with alkali metal hydroxide, and optionally solutions providing ions M, is carried out under a pressure of 1-40 bars. M = H, alkali metal, alkaline earth metal or optionally substituted ammonium. (4) Preparation of long-chain substituted glycines (or their salts) of formula R-CH(NH2)(COOM) (IV) by reaction of (IIa) (which may be prepared as above) with alkali metal hydroxide, and optionally solutions providing ions M and/or 3-9C aliphatic ketones, is carried out under a pressure of 1-40 bars. (5) Preparation of (IX) by reaction of (IV) (which may be prepared as above) with HCHO and M'CN followed by reaction with alkali metal hydroxide, and optionally solutions providing ions M, is carried out under a pressure of 1-40 bars. (6) Further preparations of (IX) involve: (6i) reacting iminodiacetic acid derivatives of formula X-CH2-NH-CH2-Y (XI) with RCHO and M'CN or with a cyanohydrin R-CH(OH)CN, in the presence or absence of an organic solvent and under a pressure of 1-40 bar; (6ii) reaction of glycine with RCHO and M'CN for mono-substitution, followed by reaction with HCHO and M'CN or with HOCH2CN, in the presence or absence of an organic solvent and under a pressure of 1-40 bar; or (6iii) reaction of glycine with HCHO and M'CN or with OHH2CN for mono-substitution, followed by reaction with RCHO and M'CN, in the presence or absence of an organic solvent and under a pressure of 1-40 bar. Any nitrile or amide functions present may be subsequently hydrolysed, suitably under a pressure of 1-40 bars. X,Y = COOM, (1-12C) alkoxycarbonyl, CONH2 or CN. Compounds of formulae (I), (IIa; R = R1), (III), (IV; R = R1), (V)-(VIII), (X) and (XII)-(XVI) are new, with the exception of (IV; R = 17-20C alkenyl), (V; R1 = 17-20C alkenyl), (I; R1 = n-9-decenyl), (VIII; R1 = 6-10C alkenyl), (IV; R1 = 2-(5-20C alkoxy)-ethyl) and (X; R1 = 2-(5-8C alkoxy)-ethyl). R1 = 6-20C alkenyl or CH2CH2OR3; R2 = 2-6C alkyl; R3 = 3-20C alkyl or 3-20C alkenyl.