Patent GB-1209905-A (GB)
Title: Long chain hydrocarbon amides and process for their production
IPC: C07C17/20
Filed: 1967-08-30
Abstract: 1,209,905. Long chain hydrocarbon amides. ZOECON CORP. 30 Aug., 1967 [29 Dec., 1966; 24 Feb., 1967], No. 55860/68. Divided out of 1,209,902. Heading C2C. [Also in Division A5] The invention comprises amides of the formula in which each of R<SP>7</SP> and R<SP>8</SP> is hydrogen, C 1-6  alkyl, C 1-5 -hydroxyalkyl, C 1-6 -alkoxy-C 1-6 -alkyl, phenyl or together represent pyrrolidino, morpholino, piperidino, piperazino or 4-C 1-6 -alkylpiperazino, 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-, or -CH 2 -, Z<SP>6</SP> is H, OH, Br, Cl or F, Z' 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 -, and the carboxylic esters, tetrahydropyranyl ethers and tetrahydrofuranyl ethers of the compounds having a free OH group, provided that (1) when Z<SP>3</SP> is H, then Z<SP>2</SP> is H, when Z<SP>7</SP> 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 Z<SP>2</SP> is hydrogen then Z<SP>3</SP> is not Br, Cl or F, (3) when Z<SP>2</SP> together with Z<SP>3</SP> and Z<SP>6</SP> together with Z<SP>7</SP> are double bonds, each of R<SP>1</SP> and R<SP>2</SP> is methyl and one of R<SP>3</SP> or R<SP>4</SP> is methyl, then Z<SP>11</SP> is not hydrogen or, together with Z<SP>10</SP>, a double bond, and (4) when R<SP>1</SP>, R<SP>2</SP> and R<SP>3</SP> are methyl, R<SP>4</SP> is 4- methylpentyl and Z<SP>3</SP>, Z<SP>7</SP> and Z<SP>11</SP> are hydrogen then at least one of R<SP>7</SP> and R<SP>8</SP> is other than hydrogen. The amides are prepared (A) by treating an ester of the formula in which R<SP>5</SP> is C 1-6  alkyl, with an alkali metal salt of the amine NHR<SP>7</SP>R<SP>8</SP> in an inert organic solvent, or (B) by treating the acid halide corresponding to the acid moiety of the above ester with an amine NHR<SP>7</SP>R<SP>8</SP> in a non-aqueous, inert solvent. Any double bonds at the Z<SP>2</SP>-Z<SP>3</SP>, Z<SP>6</SP>-Z<SP>7</SP> or Z<SP>10</SP>-Z<SP>11</SP> positions in the starting ester or product-amide 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. Selective introduction of an epoxide or fused -CH 2 - group at the Z<SP>2</SP>-Z<SP>3</SP> position may be achieved using hydrogen peroxide in aqueous alkali or dimethylsulphoxonium methylide base in dimethyl sulphoxide, respectively. 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. The examples relate to the preparation of a large number of compounds particularly, derivatives of 3,7,11 - trimethyldodeca - 2,6,10 - trieriamide, 3,7,11 -trimethyltrideca - 2,6,10 - trienamide and 3,11 - dimethyl - 7 - ethyltrideca - 2,6,10 - trienamide. The amides are used as arthropod maturation inhibitors (see Division A5).