Synthesis of Amino Acids From Substituted Cyanoacetic Esters

Abstract

Nine α-amino acids, namely, dl-α-aminoundecylic acid, dl-α-aminostearic acid, dl-α-amino-β-methylcaproic acid, dl-α-amino-β-ethylvaleric acid, dl-α-amino-β-methylenanthic acid, dl-α-amino-α-acetylacetic acid, dl-α-amino-γ-cyclohexylbutyric acid, dl-α-(1-indanyl)-α-aminoacetic acid, and dl-proline have been prepared from ethyl alkylcyanoacetates. When a mixture of formic and hydrochloric acids and water was used, instead of hydrochloric acid, as hydrolyzing agent, α-amino-β-ethylvaleric acid and α-(1-indanyl)-α-aminoacetic acid were obtained with better yields. The following compounds, as far as the authors are aware, have been prepared for the first time: ethyl α-cyanoundecylate, α-cyanoundecylic hydrazide, anisal α-cyanoundecylic hydrazide, α-cyanoundecylic azide, α-carbethoxyaminoundecylonitrile, dl-α-aminoundecylic acid, 5-(n-nonyl)-hydantoin, α-cyanostearic hydrazide, anisal α-cyanostearic hydrazide, α-cyanostearic azide, α-carbethoxyaminostearonitrile, α-cyano-β-methylcaproic hydrazide, anisal α-cyano-β-methylcaproic hydrazide, α-cyano-β-methylcaproic azide, α-carbethoxyamino-β-methylcaproonitrile, dl-α-amino-β-methylcaproic acid and its copper salt, α-cyano-β-ethylvaleric hydrazide, anisal α-cyano-β-ethylvaleric hydrazide, α-cyano-β-ethylvaleric azide, α-carbethoxyamino-β-ethylvaleronitrile, dl-α-amino-β-ethylvaleric acid, and its copper salt, ethyl α-cyano-β-methylenanthate, α-cyano-β-methylenanthic hydrazide, anisal α-cyano-β-methylenanthic hydrazide, α-cyano-β-methylenanthic azide, α-carbethoxyamino-β-methylenanthonitrile, dl-α-amino-β-methylenanthic acid, and its copper salt, α-cyano-α-acetylacetic hydrazone, anisal α-cyano-α-acetylacetic hydrazone, α-cyano-α-acetylacetic azide, α-carbethoxyamino-α-acetylacetonitrile, dl-α-amino-α-acetylacetic acid, ethyl-α-cyano-γ-cyclohexylbutyrate, α-cyano-γ-cyclohexylbutyric hydrazide, anisal α-cyano-γ-cyclohexylbutyric hydrazide, α-cyano-γ-cyclohexylbutyric azide, α-carbethoxyamino-γ-cyclohexylbutyronitrile, 5-(β-cyclohexylethyl)-hydantoin, 1-in-danyl bromide, ethyl α-(1-indanyl)-α-cyanoacetate, α-(1-indanyl)-α-cyanoacetic hydrazide, anisal α-(1-indanyl)-α-cyanoacetic hydrazide, α-(1-indanyl)-α-cyanoacetic azide, α-(1-indanyl)-α-carbethoxyaminoacetonitrile, dl-α-(1-indanyl)-α-aminoacetic acid, and its copper salt, ethyl δ-chloro-α-cyanovalerate, δ-chloro-α-cyanovaleric hydrazide, anisal δ-chloro-α-cyanovaleric hydrazide, δ-chloro-α-cyanovaleric azide, δ-chloro-α-carbethoxyaminovaleronitrile.

SYNTHESES AND ABSORPTION SPECTRA OF 2-SUBSTITUTED-3-HYDROXY-5-PYRAZOLONES: 4-n-HEXYL-5-PYRAZOLONES-4-C14

“…The spectra exhibited by many pyrazolones have been studied intensively b y Gagnon and co-workers (4,5,6,8). These authors related the position of the double bond in the pyrazolone ring to the wave length and the intensity of the absorption.…”

Contribution to the Study of Pyrazolones

“…'The spectra of 4-monosubstituted-3-hydroxy-2-cu-naphth~~1-5-pyrazolones (R = C8H17 or C6H5CH2) and 4-monosubstituted-3-hydrox~~-2-~-naphthyl-5-pyrazolones (R = C4H9, C5Hl1, C6H13, CiH15, CsH17, or CsHsCHz) (Fig. 4) are greatly influenced by the absorption of the naphthalene chro~nophore (3,8). However, these pyrazolones probably have struct~ires similar to the previous ones X X I I I or XXIV.…”

SYNTHESIS OF Α-Amino ACIDS FROM ETHYL CYANOACETATE

“…This method was used many times (4,5,6,7,8,9,10,11) and was found of wide application even if the yields were occasionally rather low.The purpose of the present work was to synthesize, frorn ethyl cyanoacetic ester, new a-amino acids substituted by phenoxyalkyl groups. Modifications of the Darapsky method were also studied in the hope of decreasing the over-all time of reaction and of obtaining better yields in a larger number of cases.…”

“…This method was used many times (4,5,6,7,8,9,10,11) and was found of wide application even if the yields were occasionally rather low.…”