Patent GB-770376-A (GB)
Title: Ethinyl carbinol derivatives
IPC: C07C271/06
Filed: 1955-04-21
Abstract: The invention comprises carbamates of the formula <FORM:0770376/IV(b)/1> wherein R is an alkyl group having 1 to 8 carbon atoms or an alkenyl or haloalkenyl group having from 2 to 8 carbon atoms; R1 is an alkyl group of from 1 to 7 carbon atoms, preferably an ethyl group; and R11 is hydrogen, an alkyl group of from 1 to 6 carbon atoms or halogen, preferably chlorine or bromine. The group R may be of the formula R1111XC=CH- in which R1111 is hydrogen or an alkyl group of from 1 to 6 carbon atoms and X is halogen, preferably chlorine or bromine.  Such compounds are obtained by treating a tertiary carbinol of the general formula <FORM:0770376/IV(b)/2> (obtained by treating an appropriate alkyl, alkenyl or haloalkenyl ketone with an alkali metal salt of an acetylenic compound) with an aromatic chloroformate in the presence of a tertiary organic base and treating with ammonia the carbonate obtained, of the formula <FORM:0770376/IV(b)/3> in which R111 is an aromatic group.  Specific carbinols listed contain as groups represented by R1, methyl, ethyl, propyl, isopropyl, butyl, hexyl, and heptyl groups, and by R, b -chlorovinyl, b -chloropropenyl, b -chloroheptenyl, b -chloro - octenyl, b  - bromobutenyl, b  - bromohexenyl, methyl, ethyl, propyl, butyl, octyl, vinyl, hexenyl and octenyl groups.  Phenyl, alkylated phenyl, chlorophenyl, nitrophenyl and a - and b -naphthyl chloroformates are referred to.  In examples: (1) to (3) phenyl chloroformate and ethyl b -chlorovinyl ethinyl carbinol are reacted in pyridine to form the phenyl carbonate of the ethyl b -chlorovinyl ethinyl carbinol.  The carbonate is treated with ammonia to form the carbamate of ethyl-b -chlorovinyl ethinyl carbinol.  In a generally similar manner there are prepared the carbamates of (4) to (6) methyl, n-propyl and isopropyl b -chlorovinyl ethinyl carbinols, (7) methyl ethyl ethinyl carbinol, (8) methyl vinyl ethinyl carbinol, (9) ethyl vinyl ethinyl carbinol, (10) isopropyl vinyl ethinyl carbinol, and (11) methyl ethyl chlorethinyl carbinol.ALSO:A medicinal composition comprises a pharmaceutical carrier and a carbamate of the formula <FORM:0770376/VI/1> wherein R is an alkyl group having 1 to 8 carbon atoms or an alkenyl or haloalkenyl group having from 2 to 8 carbon atoms; R1 is an alkyl group of from 1 to 7 carbon atoms, preferably an ethyl group; and R11 is hydrogen an alkyl group of from 1 to 6 carbon atoms, preferably chlorine or bromine.  The group R may be of the formula R1111XC=CH- in which R1111 is hydrogen or an alkyl group of from 1 to 6 carbon atoms and X is halogen, preferably chlorine or bromine.  Compounds are listed containing as groups represented by R1, methyl, ethyl, propyl, isopropyl, butyl, hexyl and heptyl groups and by R, b -chlorovinyl, b -chloropropenyl, b -chloro-heptenyl, b -chloro-octenyl b -bromobutenyl, b -bromopentenyl, b -bromohexenyl, methyl, ethyl, propyl, butyl, octyl, vinyl, hexenyl and octenyl groups.  The carbamates may be incorporated with solid diluents, sweetening or flavouring agents, or oils or with biologically active materials in tablets, capsules, elixirs or solutions.  The preparation of the carbamates is described (see Group IV(b)).