Patent GB-1209906-A (GB)
Title: Long chain hydrocarbon halides and process for their production
IPC: C07C31/44
Filed: 1967-08-30
Abstract: 1,209,906. Long branched-chain hydrocarbon halides. ZOECON CORP. 30 Aug., 1967 [29 Dec., 1966; 24 Feb., 1967], No. 33004/69. Divided out of 1,209,902. Heading C2C. [Also in Division A5] The invention comprises halides of the formula wherein X is Br, Cl or F, each of R<SP>1-4</SP> is a C 1-5  alkyl group, Z<SP>2</SP> is H or OH, Z<SP>3</SP> is H, OH, Cl, Br, F or C 1-5  alkoxy or when taken together with Z<SP>2</SP> represents a carbon-carbon double bond, -O-, -CH 2 -, -CCl 2 - or -CF 2 -, Z<SP>6</SP> is H, OH, Br, Cl or F, Z<SP>7</SP> is H, OH, Br, Cl, F or C 1-5  alkoxy or when taken together with Z<SP>6</SP> represents a carbon-carbon double bond, -O-, -CH 2 -, -CCl 2 - or -CF 2 -, Z<SP>10</SP> is H, OH, Br, Cl or F and Z<SP>11</SP> is H, OH, Br, Cl, F or C 1-5  alkoxy or when taken together with Z<SP>10</SP> represents a carbon-carbon double bond, -O-, -CH 2 -, -CCl 2 - or -CF 2 -, provided that (1) when Z<SP>3</SP> is H, then Z<SP>2</SP> is H, (2) when Z<SP>7</SP> is H, then Z<SP>6</SP> is H, (3) when Z<SP>11</SP> is H, then Z<SP>10</SP> is H, (4) when each of R<SP>1</SP> and R<SP>2</SP> is methyl and either R<SP>3</SP> or R<SP>4</SP> is methyl and the other C 1-5  alkyl, Z<SP>7</SP> is H and Z<SP>11</SP> is H, then Z<SP>3</SP> is OH, Cl, Br, F or C 1-5  alkoxy or, together with Z<SP>2</SP>, is -O-, -CH 2 -, -CCl 2 - or -CF 2 -, (5) when each of R<SP>1</SP> and R<SP>2</SP> is methyl and either R<SP>3</SP> or R<SP>4</SP> is methyl and the other C 1-5  alkyl, Z<SP>3</SP> and Z<SP>2</SP> together is a double bond, Z<SP>7</SP> and Z<SP>6</SP> together is a double bond, then Z<SP>11</SP> is OH, Br, Cl, F or C 1-5  alkoxy or, together with Z<SP>10</SP>, is -O-, -CH 2 -, -CCl 2 -, -CF 2 -, and (6) when each of R<SP>1</SP> and R<SP>2</SP> is methyl and either R<SP>3</SP> or R<SP>4</SP> is methyl and the other C 1-5  alkyl, Z<SP>2</SP> and Z<SP>3</SP> together is a double bond and Z<SP>11</SP> and Z<SP>10</SP> together is a double bond, then Z<SP>7</SP> is OH, Br, Cl, F or C 1-5  alkoxy or, together with Z<SP>6</SP>, is -O-, -CH 2 -, -CCl 2 - or -CF 2 -. The halides are prepared by reacting a ketone of the formula with vinyl magnesium bromide in an inert organic solvent and treating the resultant 1-en-3-ols with PBr 3  or PCl 3  in basic solution to obtain those compounds in which X is Br or Cl and Z<SP>2</SP> and Z<SP>3</SP> are a double bond. The fluorides are obtained by reaction of the bromide with silver or potassium fluoride. The Z<SP>2</SP>-Z<SP>3</SP> double bond in these halides and any Z<SP>6</SP>-Z<SP>7</SP> or Z<SP>10</SP>- Z<SP>11</SP> double bond in these halides or the starting ketone may be subjected to various reactions to introduce the alternative values of the groups Z, e.g. hydrogenation, epoxidation (using m-chloroperbenzoic acid), addition of fused -CH 2 - group (using CH 2 I 2  and a Zn/Cu couple), addition of fused -CF 2 - group (using trimethyltrifluoromethyl tin in the presence of NaI), addition of the fused -CCl 2 - group (using phenyldichlorobromo mercury), hydration (using aqueous formic acid or H 2 SO 4 ), halogenation or hydrohalogenation. Other derivatives may be obtained by, e.g., reduction of the epoxide to give the mono-hydroxy compounds, cleavage of the epoxide ring using perchloric acid to give the vic-bis-hydroxy compound, and treatment of the unsaturated compounds with N-bromo- or N-chloro-succinimide in an aqueous solvent to give the vic-Cl or Br-hydroxy compounds. The C 1-5  alkoxy derivative can be prepared by conventional etherification processes or by conducting any of the above processes yielding hydroxy compounds in the presence of a C 1-5  alkanol. Specified halides include 1-chloro, bromo and fluoro-3,11-dimethyl - 7 - ethyl - trideca - 2,6,10 - triene. Examples include the preparation of compounds excluded by the provisos from the above definition, viz., 1-halo-3,7,11-trimethyldodeca- 2,6,10 - trienes and 1 - halo - 3,7,11 - trimethyltrideca-2,6,10-trienes. The long chain halides inhibit the maturation of arthropods and are useful as insecticides (see Division A5).