Patent GB-810126-A (GB)
Title: Improvements relating to amino acetic acids and their use
Filed: 1955-11-10
Abstract: The invention comprises amino acetic acids having the general formula <FORM:0810126/IV (b)/1> wherein of X1, X2, X3 and X4 at least one represents a 2-hydroxycyclohexyl radical, at least one X represents the acetic acid radical -CH2COOH and the other X's or X represent(s) a 2-hydroxy cyclohexyl radical, an acetic acid radical -CH2COOH, a methyl, ethyl or hydroxyethyl group, R1 and R2 represent hydrogen or methyl or together represent a 1,4-alkylene radical and n represents a whole number of the value 0 to 3 and complexes thereof with a co-ordinative polyvalent metal, the ions of which have a co-ordination number of at least 2.  A process for the production of amino acetic acids is characterized by reacting compounds of the general formula <FORM:0810126/IV (b)/2> wherein of X1, X2, X3 and X4 at least one X represents a 2-hydroxycyclohexyl radical, at least a further X represents hydrogen, the other X's or X represent hydrogen, a methyl, ethyl or hydroxyethyl group, a 2-hydroxy-cyclohexyl or an acetic acid radical -CH2COOH, R1 and R2 represent hydrogen, methyl or together they represent a 1,4-alkylene radical, and n represents a whole number of the value 0 to 3, with monohalogen, e.g. chloro or bromo-, acetic acids, formaldehyde cyanohydrin or mixtures of alkali cyanides and formaldehyde.  In a modified process compounds of the general formula <FORM:0810126/IV (b)/3> wherein of X1, X2, X3 and X4 at least one X represents the acetic acid radical -CH2COOH and at least one further X represent(s) hydrogen, the other X's or X represents a methyl, ethyl or hydroxyethyl group or an acetic acid radical -CH2COOH, R1 and R2 represent hydrogen, methyl or together a 1,4-alkylene radical and n represents a whole number of value from 0 to 3 are reacted with 1-halogen-2-hydroxycyclohexanes, or cyclohexane-1,2-epoxides. Amine starting materials mentioned include 2 - hydroxycyclohexylamine, bis - (2 - hydroxycyclohexyl)-amine, the reaction products of compounds introducing in an amine the 2-hydroxycyclohexyl radical, with 1,2-diaminoethane, 1,2 - diaminocyclohexane, diethylene triamines, triethylene tetramines, 21-aminoethyl - 1 : 2 - diaminocyclohexanes, the reaction products of compounds introducing the 2-hydroxycyclohexyl radical, with partly acylated polyamines of the type listed after saponification of the acylamino groups, e.g. reaction products of 1-halogen-2-hydroxycyclohexane or cyclohexane-1,2-epoxide with ethylene diamine, 1,2-propylene diamine, 1,2- or 2,3-butylene diamine, diethylene triamine, triethylene tetramine, with monoacetyl derivatives of these compounds after subsequent saponification, with N-mono-methyl- or N-mono-hydroxyethyl derivatives of these compounds. Examples of suitable amino acetic acids are those obtained by introducing the 2-hydroxycyclohexyl radical into iminodiacetic acid, N,N1-diacetic acids of ethylene diamine, of 1,2-propylene diamine, of 1,2- or 2,3-butylene diamine or 1,2-diaminocyclohexane, the N,N11-diacetic acids of bisaminoethyl-methyl-, -ethyl- or hydroxyethylamine, diethylene triamine-N,N1,N11-triacetic acid, ethylene diamine-N,N-diacetic acid, N1-methyl-, ethyl- or hydroxy-ethylene diamine-N,N-diacetic acid or N-methyl-, -ethyl- or -hydroxyethyl-ethylene diamine-N,N1-diacetic acid.  The formation of complexes with alkaline earth and heavy metal ions, especially those of the metals of the iron group, are referred to.  In examples: N - (2 - hydroxycyclohexyl) - iminodiacetic acid is obtained by reacting 2-aminohexanol with monochloracetic acid in the presence of caustic soda and heating the product with hydrochromic acid (1); N-(2-hydroxycyclohexyl)-ethylene diamine-N,N1,N1-triacetic acid is obtained similarly from N-(2-hydroxy - cyclohexyl) - ethylene diamine and monochloracetic acid; N-(2-hydroxy-5-methylcyclohexyl)-ethylene diamine-N,N1,N11-triacetic acid is similarly obtained (2); N,N1-bis-(2-hydroxycyclohexyl)-ethylene diamine-N,N1-diacetic acid is obtained by reacting N,N1-bis-(2-hydroxy-cyclohexyl)-ethylene diamine dihydrochloride with formaldehyde and sodium cyanide, saponifying the dinitrile with hydrochloric acid and treating an aqueous paste of the dihydrochloride with caustic soda; a similar compound is prepared in which the cyclohexyl radicals have 5-methyl substituents (3); the sodium salt of N,N11-bis-(2-hydroxycyclohexyl)-diethylene triamine-N,N1,N11-triacetic acid is obtained by reacting N,N11-bis-(2-hydroxy-cyclohexyl)-diethylene triamine trihydrochloride with sodium cyanide and formaldehyde, treating the product with hydrochloric acid and working up to form the sodium salt; in a similar process the tetrahydrochloride of N,N1111-bis-(2-hydroxy-cyclohexyl)-triethylene tetramine is employed (4); the sodium salt of bis-(2-hydroxycyclohexyl)-aminoacetic acid is obtained by reacting inactive or d,l-bis-(2-hydroxycyclohexyl)-amine hydrochloride with formaldehyde and sodium cyanide, hydrolysing the product with hydrochloric acid and treating with caustic soda; N,b  - hydroxyethyl - N - 2 - hydroxycyclohexyl-amino-N-acetic acid is obtained in a similar process employing N-2-hydroxycyclohexyl-N,b -hydroxyethylamine obtained from 1,2-chlorhydroxycyclohexane and monoethanolamine (5); the sodium salt of N-(hydroxyethyl)-N1-(2-hydroxycyclohexyl)-ethylene diamine-N,N1-diacetic acid is obtained by reacting N-(hydroxyethyl) - N1 - (2 - hydroxycyclohexyl)-ethylene diamine and the sodium salt of monochloracetic acid in the presence of caustic soda (6); N - (2 - hydroxycyclohexyl) - iminodiacetic acid is obtained by reacting iminodiacetic acid and 1,2-cyclohexene oxide in caustic soda solution (7); N,N-bis-(2-hydroxycyclohexyl)-ethylene diamine-N,N1-diacetic acids are obtained by reacting ethylene diamine-N,N1-diacetic acid with 1,2-cyclohexene oxide (8); N,N1-bis-(2-hydroxycyclohexyl) - 1,2 - propylene diamine-N,N1-diacetic acids are obtained similarly from 1,2-cyclohexene oxide and 1,2-propylene diamine-N,N1-diacetic acid; other complex-forming aqueous solutions are formed using 2,3-butylene diamine-N,N1-diacetic acid or 1,2-diaminocyclohexane - N,N1 - diacetic acid as starting material (9).