Patent GB-1209903-A (GB)
Title: Long chain hydrocarbon esters and acids and process for their production
IPC: C07C45/62
Filed: 1967-08-30
Abstract: 1,209,903. Long chain hydrocarbon acids and esters thereof. ZOECON CORP. 30 Aug., 1967 [15 Sept., 1966; 28 Oct., 1966; 7 Nov., 1966; 24 Feb., 1967], No. 55858/68. Heading C2C. [Also in Division A5] The invention comprises compounds of the. formula in which R<SP>5</SP> is hydrogen or C 1-6  alkyl, 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 -, the metal salts of the acids and the carboxylic esters, tetrahydropyranyl ethers and tetrahydrofuranyl ethers of compounds containing OH groups, provided that (1) when Z<SP>3</SP> is H, then Z<SP>2</SP> is H, when Z' is H, then Z<SP>6</SP> is H, when Z<SP>11</SP> is H, then Z<SP>10</SP> is H, (2) when each of R<SP>1</SP>, R<SP>2</SP>, R<SP>3</SP>, R<SP>4</SP> is methyl, Z<SP>3</SP> together with Z<SP>2</SP> and Z<SP>7</SP> together with Z 6  are double bonds and Z<SP>11</SP> together with Z<SP>10</SP> is -O-, then R<SP>5</SP> is not hydrogen or methyl, (3) when R<SP>1</SP> is methyl, R<SP>2</SP> is ethyl, one of R<SP>3</SP> or R<SP>4</SP> is methyl and the other is ethyl, Z<SP>3</SP> together with Z<SP>2</SP> and Z<SP>7</SP> together with Z<SP>6</SP> are double bonds and Z<SP>11</SP> together with Z<SP>10</SP> is -O-, then R<SP>5</SP> is not methyl, (4) when each of R<SP>1</SP>, R<SP>2</SP>, R<SP>3</SP>, R<SP>4</SP> is methyl Z<SP>3</SP> together with Z<SP>2</SP> and Z<SP>11</SP> together with. Z<SP>10</SP> are double bonds and Z<SP>7</SP> together with Z<SP>6</SP> is -O-, then R<SP>5</SP> is not hydrogen or methyl, (5) when each of R<SP>1</SP>, R<SP>2</SP>, R<SP>3</SP>, R<SP>4</SP> is methyl, Z<SP>7</SP> together with Z<SP>6</SP> and Z<SP>11</SP> together with Z<SP>10</SP> are double bonds then Z<SP>3</SP> is not OH or, together with Z<SP>2</SP>, -O-, (6) when each of R<SP>1</SP>, R<SP>2</SP>, R<SP>3</SP>, R<SP>4</SP> is methyl, Z' is hydrogen, Z<SP>11</SP> is hydrogen or, together with Z<SP>10</SP>, a double bond, then Z<SP>3</SP> is not OH, (7) when R<SP>1</SP> is m-butyl, each of R<SP>2</SP>, R<SP>3</SP>, R<SP>4</SP> is methyl and Z<SP>7</SP> and. Z<SP>11</SP> are hydrogen, then Z<SP>3</SP> is not hydroxy, (8) when each of R<SP>1</SP> and R<SP>2</SP> is methyl, one of R<SP>3</SP> or R<SP>4</SP> is methyl and the other is 4-methylpentyl; Z<SP>11</SP> is hydrogen and Z<SP>7</SP> together with Z<SP>6</SP> is a double bond, then Z<SP>3</SP> is not OH or halogen, (9) when R<SP>1</SP> is ethyl, Z<SP>3</SP> together with Z<SP>2</SP>, Z<SP>7</SP> together with Z<SP>6</SP> and Z<SP>11</SP> together with Z<SP>10</SP> are all double bonds, then one of R<SP>2</SP>, R<SP>3</SP>, R<SP>4</SP> is not methyl, (10) when 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 one of R<SP>1</SP> or R<SP>2</SP> is not methyl, and (11) when Z<SP>3</SP> together with Z<SP>2</SP> is a double bond, Z<SP>6</SP> and Z<SP>10</SP> are hydrogen and Z<SP>7</SP> or Z<SP>11</SP> are Cl and R<SP>5</SP> is alkyl, then one of R<SP>1</SP>, R<SP>2</SP>, R<SP>3</SP>, R<SP>4</SP> is not methyl; and a process for preparing acids and esters of the formula where R<SP>1</SP>, R<SP>2</SP>, R<SP>3</SP>, R<SP>4</SP>, R<SP>5</SP>, Z<SP>6</SP>, Z<SP>7</SP>, Z<SP>10</SP> and Z<SP>11</SP> are as defined above, excepting provisos (2) to (11), comprising reacting a ketone of the formula with (A) a carbalkoxymethylphosphonate in-the presence of an alkali metal anhydride, or (B) a cyanomethylphosphonate followed by hydrolysis and/or esterification of the terminal cyano group or, optionally, hydrolysis of the terminal ester group. The Z<SP>2</SP>-Z<SP>3</SP> double bond in the above product and any Z<SP>6</SP>-Z<SP>7</SP> or Z<SP>10</SP>-Z<SP>11</SP> double bond in the acid, ester or 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 fused -CCl 2 - group (using phenyldichlorobromo mercury), hydration (using aqueous formic acid or H 2 SO 4 ), halogenation or hydrohalogenation. In addition, the fused -CH 2 - group may be selectively introduced in the 2,3-position by reaction with dimethylsulphoxonium methylide base in dimethylsulphoxide and the fused -O- group may be selectively introduced in the 2,3-position by using H 2 O 2  in an aqueous alkali medium. 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 1-6  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 acids and esters, most of which are derivatives of 3,7,11-trimethyldodeca- 2,6,10-trienoic, 3,7,11-trimethyltrideca-2,6,10- trienoic and 3,11 - dimethyl - 7 - ethyltrideca - 2,6,10-trienoic acids. The acids and esters are arthropod maturation inhibitors (see Division A5). In preparations 1-3, the synthesis of some of the starting ketones is described, including the hydrogenation of 6,10-dimethyldodeca-5,9-dien- 2-one to a mixture of 6,10-dimethyldodeca- 5 - en - 2 - one, 6,10 - dimethyldodeca - 9 - en - 2 - one and 6,10-dimethyldodecan-2-one.