Optical stability of tetrahydro-2-naphthylamine and 9-aminofluorene-2-carboxylic ester.

(1) The Optical stability of 1:2:3:4-Tetrahydro-2-naphthyl-amine. (2) The Optical stability of (+) Methyl 9-aminofluorene -2-carboxylate. (3) The Rearrangement of para substituted Phenylhydroxy1-amines to Quinols. The occurence of alkyl-oxygen fission during hydrolysis of carboxylic esters of suitably substituted alcohols is now well established. It appeared of interest to inquire if an analogous reaction existed in which the bond undergoing fission was the C-N bond an "alky1-nitrogen fission". With this in view two reports in the literature, in which such a mechanism might be operative have been studied. The extensive racemisation of (+)1:2:3:4-tetra-hydro-2-naphthylamine found by Pope and Harvey has been critically re-examined. The conclusions are that this compound is optically quite stable, and that Pope and Harvey were mistaken in their belief that their starting material was optically pure. The other example of optical instability was reported by Ray and Kreiser who found that (+) methyl 9-amino fluorene-2-carboxylate racemised readily even on standing, and that recrystallisation was impossible without loss of optical activity. This has been shown to be due to chemical instability, and not due to any spontaneous racemisation. (+) Methyl 9-aminofluorene-2-carboxylate is optically stable when kept in the dark and in an atmosphere of nitrogen. Some of its decomposition products have been isolated and identified. An attempt has been made to obtain some insight into the rearrangement of para substituted phenyl-hydroxylamines, where an alkyl group migrates to a neighbouring ortho position. By carrying out the reaction with an optically active migrating group - (-)sec butylone could throw light on the mechanism of this rearrangement . A procedure for the preparation of p-sec-butylphenylhydroxylamine and its reaction with dilute sulphuric acid is described. The resulting products however proved unsuitable for determinations of optical rotatory power