Aromatische N,N-disubstituierte Thioncarbamate und Thiolcarbamate sowie Verfahren zur Umwandlung dieser Thioncarbamate in die Thiolcarbamate

摘要

1,159,340. Thion- and thiol-carbamate derivatives. BOARD OF TRUSTEES OF THE OHIO STATE UNIVERSITY. 14 April, 1967 [4 May, 1966], No. 17296/67. Headings C2C and C2U. A process for transforming a thioncarbamate to a thiolcarbamate comprises reacting a compound containing at least one thiocarbamoyloxy moiety of formula = N-CS-O- wherein the O is attached to an aromatic ring carbon and the N is attached to two different carbon atoms, each of which is saturated with hydrogen atoms, other carbon atoms or a combination of those or is an aromatic ring carbon atom in the liquid phase at an elevated temperature preferably under nitrogen, until a substantial proportion of the thioncarbamate is rearranged to give the thiolcarbamate containing at least one carbamoylthio moiety of formula =N-CO-S-. The attachments to the N may be C 1-8 alkyl, C 3-8 alkenyl, excluding 1-alkenyl moieties, C 3-8 cycloalkyl, C 7-14 aralkyl, phenyl, halophenyl, nitrophenyl, C 7-14 alkylphenyl, C 7-14 alkoxyphenyl or C 1-8 alkylene radicals which are linked together through carbon, oxygen or nitrogen to form heterocyclic rings. The aromatic species attached to the -O- atom in the thioncarbamate or the -S- atom in the thiolcarbamate may be hetero- or homocyclic, substituted or unsubstituted. Compounds of formulae (III) wherein R 1, R 2 and R 3 are as defined above for the suggested substituents in the N atom except that R 3 can not be an alkylene radical are claimed per se. Compounds of Formula (IV) when reacted with a mixture of chlorine and water, then aqueous ammonia lead to the preparation of saccharin. The thiolcarbamates prepared by the above process may be converted into the corresponding thiophenols by reaction with aqueous alkali in a solvent such as methanol or ethanol and isolating the resulting thiophenol by acidification and extraction. The preparations of numerous thioncarbamates are described including some where the nitrogen atom is in a ring by the following two general methods: where Ar is the appropriate substituted or unsubstituted aromatic moiety and R and R1 the appropriate substituents on the N atom. p - Tertiary - butylphenyl chlorothionformate is prepared as an intermediate from thiophosgene and p-tert-butyl phenol. The preparations of 17-oxoestra-1,3,5(10)- trien - 3 - yl dimethylthioncarbamate, 17- hydroxyestra - 1,3,5(10) - trien - 3 - yl dimethylthioncarbamate and 17 - acetoxyestra - 1,3,5(10) - trien - 3 - yl dimethylthioncarbamate are described as well as their re-arrangements to the corresponding thiolcarbamates.