GB1195174A - Amino-Substituted Esters and their Reactions - Google Patents

Abstract

1,195,174. Indolyl derivatives; amino valerates. MERCK & CO. Inc. 23 May, 1968 [27 May, 1967], No. 24759/68. Heading C2C. Compounds of the general formula where R is C 1-5 alkyl or aralkyl, and R<SP>1</SP> is hydrogen or p-chlorobenzoyl, are prepared by reacting a compound of formula with an alkali metal ferricyanide or a nitrosodisulphonate of formula NO(SO 3 X) 2 , where X is sodium, potassium or lithium. The aminovalerate starting materials are claimed per se, and are prepared by condensing ethyl bromoacetate with 2-benzylamino-2<SP>1</SP>-methoxypropiophenone, followed by demethylation and ring closure to yield 4-(α-benzylamino)-ethylcoumarin which is subjected to base hydrolysis to give 3 - (2<SP>1</SP>- hydroxyphenyl) - 4 - benzylaminopent - 2-enoic acid which is then esterified and reduced to yield 3 - (2<SP>1</SP>- hydroxyphenyl) - 4 - aminovalerate. The 4-p-chlorobenzamido derivatives are produced by treatment of the free amino compound with p-chlorobenzoic acid anhydride. 5-Methoxy derivatives of the indole compounds of the first general formula above are prepared by treating the 5-hydroxy compound with a methylating agent. The indole derivatives wherein R<SP>1</SP> is p-chlorobenzoyl may be prepared directly from the compounds wherein R<SP>1</SP> is hydrogen, by treatment with p-chlorobenzoyl halide or p-chlorobenzoic acid anhydride, and the free acids may be prepared by de-esterification. 4 - (Alpha - benzylamino) - ethyl - coumarin is prepared by treating carbethoxymethylenetriphenyl phosphorane with 2-benzylamino-2<SP>1</SP>- methoxypropiophenone, followed by hydriodic acid and red phosphorus.