SYNTHESIS OF AMINO ACIDS FROM SUBSTITUTED CYANOACETIC ESTERS
Authors: Gagnon Paul E. , Nolin Benoit 
Published: April 2011

α-Substituted cyanoacetic esters have been used to prepare hydrazides, azides, urethanes, and the 10 following α-amino acids: dl-α-aminocaprylic acid, dl-α-aminopelargonic acid, dl-α-aminocapric acid, dl-α-aminolauric acid, dl-α-(2-ethyl-n-butyl)-α-aminoacetic acid, dl-α-(2-ethyl-n-hexyl)-α-aminoacetic acid dl-α-amino-γ-phenylbutyric acid, dl-α-amino-γ-benzylbutyric acid, dl-C-cyclohexylglycine, and dl-α-amino-β-1-naphthylpropionic acid. When a mixture of formic and hydrochloric acids and water was used, instead of hydrochloric acid, as hydrolyzing agent to transform the urethanes into amino acids, the period of heating was relatively short. The following compounds, as far as the authors are aware, have been prepared for the first time: ethyl α-cyanocaprylate, α-cyanocaprylamide, α-cyanocaprylic hydrazide, anisal α-cyanocaprylic hydrazide, benzal α-cyanocaprylic hydrazide, α-cyanocaprylic azide, α-carbethoxyaminocaprylonitrile, 5-(n-hexyl)-hydantoin, ethyl α-cyanopelargonate, α-cyanopelargonic hydrazide, anisal α-cyanopelargonic hydrazide, benzal α-cyanopelargonic hydrazide, isopropylidene α-cyanopelargonic hydrazide, α-cyanopelargonic azide, α-carbethoxyaminopelargonitrile, 5-(n-heptyl)-hydantoin, α-cyanocapric hydrazide, anisal α-cyanocapric hydrazide, benzal α-cyanocapric hydrazide, α-cyanocapric azide, α-carbethoxyaminocapronitrile, dl-α-phenylureidocapric acid, ethyl α-cyanolaurate, α-cyanolauric hydrazide, anisal α-cyanolauric hydrazide, α-cyanolauric azide, α-carbethoxyaminolauronitrile, dl-α-phenylureidolauric acid, ethyl-α-(2-ethyl-n-butyl)-α-cyanoacetate, α-(2-ethyl-n-butyl)-α-cyanoacetic hydrazide, anisal α-(2-ethyl-n-butyl)-α-cyanoacetic hydrazide, benzal α-(2-ethyl-n-butyl)-α-cyanoacetic hydrazide, α-(2-ethyl-n-butyl)-α-cyanoacetic azide, α-(2-ethyl-n-butyl)-α-carbethoxyaminoacetonitrile, dl-α-(2-ethyl-n-butyl)-α-aminoacetic acid, dl-α-(2-ethyl-n-butyl)-α-phenylureidoacetic acid, 5-(2-ethyl-n-butyl)-hydantoin, ethyl α-(2-ethyl-n-hexyl)-α-cyanoacetate, α-(2-ethyl-n-hexyl)-α-cyanoacetic hydrazide, anisal α-(2-ethyl-n-hexyl)-α-cyanoacetic hydrazide, α-(2-ethyl-n-hexyl)-α-cyanoacetic azide, α-(2-ethyl-n-hexyl)-α-carbethoxyaminoacetonitrile, dl-α-(2-ethyl-n-hexyl)-α-aminoacetic acid, 5-(2-ethyl-n-hexyl)-hydantoin, dl-α-(2-ethyl-n-hexyl)-α-phenylureidoacetic acid, ethyl α-cyano-γ-phenylbutyrate, α-cyano-γ-phenylbutyrhydrazide, anisal α-cyano-γ-phenylbutyrhydrazide, benzal α-cyano-γ-phenylbutyrhydrazide, α-cyano-γ-phenylbutyric azide, α-carbethoxyamino-γ-phenylbutyronitrile, 5-(β-phenylethyl)-hydantoin, dl-α-phenylureido-γ-phenylbutyric acid, ethyl α-cyano-γ-benzylbutyrate, α-cyano-γ-benzylbutyrhydrazide, anisal α-cyano-γ-benzylbutyrhydrazide, α-cyano-γ-benzylbutyric azide, α-carbethoxyamino-γ-benzylbutyronitrile, 5-(γ-phenylpropyl)-hydantoin, α-cyclohexyl-α-cyanoacetamide, α-cyclohexyl-α-cyanoacetic hydrazide, anisal α-cyclohexyl-α-cyanoacetic hydrazide, α-cyclohexyl-α-cyanoacetic azide, α-cyclohexyl-α-carbethoxyaminoacetonitrile, dl-α-cyclohexyl-α-phenylureidoacetic acid, ethyl α-cyano-β-1-naphthylpropionate, α-cyano-β-1-naphthylpropionhydrazide, anisal α-cyano-β-1-naphthylpropionhydrazide, α-cyano-β-1-naphthylpropionic azide, α-carbethoxyamino-β-1-naphthylpropionitrile, and dl-α-phenylureido-β-1-naphthylpropionic acid.