Patent GB-1209904-A (GB)
Title: Long chain hydrocarbon alcohols and esters and ethers and process for their production
IPC: C07C45/62
Filed: 1967-08-30
Abstract: 1,209,904. Long chain hydrocarbon alcohols; ethers and esters thereof. ZOECON CORP. 30 Aug., 1967 [16 Nov., 1966; 24 Feb., 1967], No. 55859/68. Divided out of 1,209,902. Heading C2C. [Also in Division A5] The invention comprises compounds of the formula in which R is the group -CH 2 OR<SP>6</SP>, wherein R<SP>6</SP> is hydrogen, C 1-12  acyl or C 1-6  alkyl, and each of R<SP>1-4</SP> is a C 1-6  alkyl group, Z<SP>2</SP> is H or OH, Z<SP>3</SP> is H, OH, Cl, Br, F or C 1-6  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 1-6  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 1-6  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>, R<SP>2</SP>, R<SP>3</SP> and R<SP>4</SP> is methyl, Z<SP>3</SP> together with Z<SP>2</SP> is a double bond, Z<SP>7</SP> together with Z<SP>6</SP> is a double bond or the group -O- and Z<SP>11</SP> together with Z<SP>10</SP> is a double bond or the group -O-, then R<SP>6</SP> is C 2-6  alkyl, (5) when R<SP>1</SP> is methyl, one of R<SP>3</SP> or R<SP>4</SP> is methyl, Z<SP>3</SP> is hydrogen or, together with Z<SP>2</SP>, a double bond, Z<SP>7</SP> is hydrogen or, together with Z<SP>6</SP>, a double bond, and Z<SP>11</SP> is hydrogen or, together with Z<SP>10</SP>, a double bond, then R<SP>2</SP> is C 2-6  alkyl, and (6) when R<SP>1</SP> and R<SP>2</SP> are methyl, one of R<SP>3</SP> or R<SP>4</SP> is methyl, Z<SP>7</SP> is hydrogen or, together with Z<SP>6</SP>, a double bond, and Z<SP>11</SP> hydrogen or, together with Z<SP>10</SP>, a double bond, then Z<SP>3</SP> is taken together with Z<SP>2</SP> to form the group -CH 2 -, -CCl 2 - or -CF 2 -. Those compounds in which R<SP>6</SP> is hydrogen and Z<SP>2</SP>, together with Z<SP>3</SP>, is a double bond, are prepared by reduction, e.g. with LiAlH 4 , of esters of the formula The Z<SP>2</SP>-Z<SP>3</SP> double in the starting ester or product alcohol and any Z<SP>6</SP>-Z<SP>7</SP> or Z<SP>10</SP>-Z<SP>11</SP> double bond in the ester or alcohol 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 fused -CCl 2 - group (using phenyldichlorobromo mercury), hydration (using aqueous formic acid or H 2 SO 4 ), halogenation or hydrohalogenation. Other derivatives are obtained by, e.g., reduction of the epoxide to give the mono-hydroxy compounds, cleavage of the epoxide ring using HClO 4 . to give the vic-dihydroxy compounds and treatment of the unsaturated compounds with N-Br- or N-Cl-succinimide in an aqueous solvent to give the vic-Cl or Br-hydroxy compounds. The ethers and esters of compounds containing -OH groups are made by conventional etherification and esterification processes. The C 1-5  alkoxy derivatives can also be prepared by conducting any of the above processes yielding -OH compounds in the presence of a C 1-6  alkanol. Examples describe the preparation of a large number of alcohols and the ethers and esters thereof, including some compounds such as farnesol which are excluded by the provisos from the definition above. Specified compounds include derivatives of farnesol (3,7,11-trimethyldodeca - 2,6,10 - trien - 1 - ol), 3,7,11 - trimethyltrideca - 2,6,10 - trien - 1 - ol and 3,11 - dimethyl - 7 - ethyltrideca - 2,6,10 - trien - 1 - ol. The alcohols, ethers and esters. are arthropod maturation inhibitors (see Division A5).