Patent GB-799634-A (GB)
Title: Improvements in or relating to unsaturated tertiary carbinols and preparation thereof
Filed: 1954-11-03
Abstract: Vinyl ethinyl tertiary carbinols having the general formula: <FORM:0799634/IV (b)/1> wherein R1 represents halogen, or an alkyl group, e.g. having from 1-7 carbon atoms, R2 R3 and R5 are hydrogen or alkyl groups having from 1 to 7 carbon atoms, and R4 is an alkyl group having from 1 to 7 carbon atoms or an alkenyl group having from 2 to 7 carbon atoms, or R1 may also be hydrogen provided that when both R1 and R2 are hydrogen and R5 is alkyl, R3 is an alkyl group having from 2 to 7 carbon atoms and/or R4 is an alkyl group having from 3 to 7 carbon atoms or an alkenyl group having from 2 to 7 carbon atoms, are prepared by condensing under anhydrous conditions an alkyl b -haloalkyl ketone of formula X.C(R1)(R2).CH(R3).CO.R4, and alkyl b ,b -dihaloalkyl ketone of formula X2C(R2).CH(R3)CO.R4, a b ,b 1-dihaloalkyl ketone of formula X.C(R1)(R2).CH(R3).CO.CH2.CH(X)R, a b ,b ,b 1-trihaloalkyl ketone of formula X2.C(R2).CH(R3).CO.CH2.CH(X).R, or a b -haloalkyl, b 1-haloalkenyl ketone of formula X.C(R2) = C(R3).CO.CH2.CH(X).R, R, R, R1, R2 and R3 being hydrogen or alkyl, R4 being alkyl and X being halogen, preferably chlorine or bromine, with at least 2 equivalents of a metal acetylide or a monoalkyl substituted metal acetylide wherein the alkyl group has from 1 to 7 carbon atoms.  Compounds having the general formula (I) in which R1 is halogen, R2, R3 and R5 are hydrogen or alkyl groups having 1 to 7 carbon atoms, and R4 is an alkyl or alkenyl group having 2-7 carbon atoms are novel compounds. Specific novel compounds mentioned are: 3-isopropylpentene - 1 - yne - 4 - ol - 3, 3 - n - butylpentene-1 - yne - 4 - ol - 3, 3 - vinylpentene - 1 - yne - 4-ol - 3, 1 - chloro - 3 - vinylpentene - 1 - yne - 4-ol-3 and 1-chloro-3-ethylpentene-1-yne-4-ol-3.  Numerous examples of suitable b -halo-ketones of various types are given. Alkali metal and alkaline earth metal acetylides are highly effective, lithium acetylide being preferred.  Liquid ammonia is a suitable solvent for the reaction, but may be diluted with an inert solvent such as diethyl ether.  In general, the reaction is conducted at the boiling point of liquid ammonia, but when a low boiling solvent is used, temperatures up to the boiling point of the solvent may be employed.  The products may be isolated by allowing the liquid ammonia to evaporate and pouring the resulting suspension into a mixture of ice and a suitable acid, say acetic acid.  The products are then extracted with ether and purified by distillation under reduced pressure.  In examples: (1) 3-isopropylpentene - 1 - yne - 4 - ol - 3 is obtained from lithium acetylide and isopropyl b -chloroethyl ketone; (2) 3-n-butylpentene-1-yne-4-ol-3 is similarly obtained from n-butyl b -chlorethyl ketone; (3) 3-vinylpentene-1-yne-4-ol-3 is obtained from 3-b -chloroethyl ketone; (4) 1-chloro - 3 - vinylpentene - 1 - yne - 4 - ol - 3 is obtained from b -chloroethyl, b 1-chlorovinyl ketone.  3 - Methylpentene - 1 - yne - 4 - ol - 3, 3 - ethylpentene - 1 - yne - 4 - ol - 3, 3 - n-propylpentene - 1 - yne - 4 - ol - 3, and 1-chloro - 3 - ethylpentene - 1 - yne - 4 - ol - 3 are obtained by similar methods. The products are useful as intermediates, solvents and as hypnotic and anticonvulsant agents.