Patent GB-952733-A (GB)
Title: Unsaturated aliphatic alcohols
IPC: C07C69/587
Filed: 1960-06-23
Abstract: The invention comprises compounds of the general formula: <FORM:0952733/C2/1> wherein R is a saturated or unsaturated straight chain aliphatic radical other than the n-propyl radical, and the geometric isomers thereof.  The compounds may be prepared by reacting an appropriate halogen-alk-2-ene of the general formula. <FORM:0952733/C2/2> wherein R is as defined above with triphenyl phosphine to give a triphenyl phosphonium halide which is then reacted with a proton acceptor to give a phosphorane which is (a) reacted with 1-acyloxy-decon-10-al and the conjugated unsaturated ester thus obtained is saponified with alkali, or is (b) reacted with a adecon- -10- al -1-oic acid ester and the ester thus obtained reduced to the desired alcohol with a complex metal hydride. The 1-halogen -alki -2- ene may be used in a sterically homogeneous form or in the form of mixtures of the stereoisomers. The intermediate or end products of the process may be separated into their geometric isomers, for example by fractional crystallisation.  Decon -10- al -1- oic acid methyl ester can be prepared by oronolysis of under -10- ene -1- oic acid methyl ester. 1-Acyloxy - decon -10- als may be obtained by oxonolysis of acylated undec -10- en -1- ol which is prepared by reduction of unec -10- ene -1- oic acid methyl ester by means of complex metal hydrides followed by acylation of the alcohol in known manner.  In examples (1) isotyl alcohol is reacted with phosphorus tribromide to give 1-bromo -but -2- ene which is reacted with triphenylphosphine to produce triphenyl but -2- enyl phorphonium bromide; this on treatment with n-butyl lithium gives a blood-red solution of the phosphorone which is reacted with 1-acetocy-decon -10- al to give triphenylphosphine oxide and 1-acetoxy-tetradeca-10, 12-diene which is saponified and the resultant acid separated into its isomers by fractional crystallisation:  (2) n-butyl lithium is added to triphenyl but -2- enyl phosphonium bromide and the resulting phosphorane is reacted with decon -10- al -1- acid methyl ester and, after removal of triphenylphosphine oxide, the resultant tetradeca -10, 12-diene -1- acid methyl ester is saponified and the acid produced is fractionally crystallised; the isomers are separately reacted with diazomethane to give the corresponding methyl esters which are then reduced to the corresponding isomers of tetradeca -10, 12-dien -1- ol with lithium aluminium hydride:  (3) in a manner similar to that of Example (1) triphenyl hexa -2, 4-dienyl phosphonium bromide is prepared from hexa-2, 4-dien-1-ol and is then treated with n-butyl lithium the phosphorane is reacted with 1-acetoxy-decon -10- al to give 1-acetoxy-hexadeca-10, 12, 14 triene which no saponification gives hexadeca-10, 12, 14-trien -1- ol. Reference has been directed by the Comptroller to Specifications 874,581 and 911,107.ALSO:Insect attractants of the general formula R-CH = CH-CH = CH-(CH2)8-CH2OH wherein R is a saturated or unsaturated straight chain aliphatic radical other than the n-propyl radical (see Division C2) can be added to pest control agents, particularly to insecticides.  Reference has been directed by the Comptroller to Specifications 874,581 and 911,107.