Patent GB-735828-A (GB)
Title: Process for the manufacture of organic halides
IPC: C07C17/02
Filed: 1953-08-26
Abstract: A process for the manufacture of organic halides of the general formula <FORM:0735828/IV (b)/1> wherein R1 represents an aliphatic (including cycloaliphatic) hydrocarbon radical and R2 represents a hydrogen atom or the methyl radical and X represents a chlorine or bromine atom comprises reacting a carbinol of the general formula <FORM:0735828/IV (b)/2> with aqueous hydrogen chloride or hydrogen bromide.  In preferred embodiments R2 represents a hydrogen atom and R1 is an isopropenoid radical (that is a radical of the structure CH3-(C(CH3)=CH-CH2-CH2)n (wherein n is 1, 2 or 3) or a corresponding saturated radical, or the second general formula represents a methyl- or dimethyl-butenol, e.g. 2-methyl - buten - (3) - ol - (2) or 2,3 - dimethylbuten-(3)-ol-(2).  Suitable concentrations of the hydrogen halides are 20 to 43 per cent, e.g. 37 per cent by weight, for the hydrogen chloride, and 30 to 55 per cent, e.g. 48 per cent by weight for the hydrogen bromide, and 3-molar proportions per mol. of carbinol are ordinarily used.  Reaction temperatures of between -5 DEG C. and 40 DEG  C., preferably 20 DEG  to 25 DEG  C. are specified.  The products may be used in further syntheses, e.g. acetoacetic ester syntheses with little or no purification. In examples (1) 2-methyl-buten-(3)-ol-(2) and 48 per cent aqueous hydrogen bromide are reacted at 20 DEG  C. to give 1-bromo-3-methyl-butene-(2); (2) racemic 3,7-dimethyl-octadien-(1,6)-ol-3 and 48 per cent hydrogen bromide are reacted to give 1-bromo-3,7-dimethyl-octadiene-(2,6); (3) racemic 3,7,11-trimethyl-dodecen-(1)-ol-(3) and 48 per cent hydrogen bromide are reacted to give 1-bromo-3,7,11-trimethyl-dodecene-(2); (4) 2,3-dimethylbuten-(3)-ol-(2) and 48 per cent hydrogen bromide are reacted to give 1-bromo-2,3-dimethyl-butene-(2); (5) 2-methyl-buten-(3)-ol-(2) and 37 per cent aqueous hydrogen chloride are reacted to give 1-chloro-3-methyl-butene-(2); (6) 3,7-dimethyl-octadien-(1,6)-ol-(3) and 37 per cent hydrogen chloride are reacted to give 1-chloro-3,7-dimethyl-octadiene-(2,6); (7) racemic-3,7,11-trimethyl-dodecen-(1)-ol-(3) and 37 per cent hydrochloric acid are reacted to give 1-chloro-3,7,11-trimethyl-dodecene-(2); (8) 2,3-dimethyl-buten-(3)-ol-(2) and hydrochloric acid are reacted to give 1-chloro-2,3-dimethyl-butene-(2); (9) 3-methyl-penten-(1)-yn-(4)-ol-(3) and 37 per cent hydrochloric acid and reacted to give 1-chloro-3-methyl-penten-(2)-yne-(4); 37 per cent hydrochloric acid is reacted with 3-methyl-pentadien-(1,4)-ol-(3) (obtained by the reduction with a palladium-lead hydrogenation catalyst of 3-methyl-penten-(1)-yn-(4)-ol-(3)) to give 1-chloro-3-methyl-pentadiene-(2,4); (11) 37 per cent hydrochloric acid and 3,7,11,15-tetramethylhexadecen-(1)-ol-(3) (isophytol) are reacted to give 1 - chloro - 3,7,11,15 - tetramethyl - hexadecene-(2) (phytyl chloride); (12) 3,7-dimethyl-octen-(1)-ol-(3) and 48 per cent hydrobromic acid are reacted to give 1-bromo-3,7-dimethyl-octene-(2). The products of examples 1 to 6, 8 and 10, are condensed with ethyl acetoacetate and the products are subjected to ketonic hydrolysis giving (1) and (5), 6-methyl-hepten-(5)-one-(2); (2) and (6), geranyl acetone; (3), 6,10,14 - trimethyl - pentadecen - (5) - one - (2); (4) and (8), 5,6-dimethyl-hepten-(5)-one-(2); (10), 6-methyl-octadien-(5,7)-one-(2).