Patent GB-1209907-A (GB)
Title: Long chain hydrocarbon amines and process for their production
IPC: C07D303/42
Filed: 1967-08-30
Abstract: 1,209,907. Long chain hydrocarbon amines. ZOECON CORP. 30 Aug., 1967 [29 Dec., 1966; 24 Feb., 1967], No. 33146/69. Divided out of 1,209,902. Heading C2C. [Also in Division A5] The invention comprises amines of the formual wherein R represents the group -CH 2 R<SP>7</SP>R<SP>8</SP>, where R<SP>7</SP> and R<SP>8</SP> are hydrogen, C 1-6  alkyl, C 1-6 - hydroxyalkyl, C 1-6  -alkoxy-C 1-6 -alkyl or together are the pyrrolidino. morpholino, piperidino, piperazino or a 4-C 1-6 -alkylpiperazino group, each of R<SP>1</SP>-R<SP>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 carboncarbon 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 -, and the acid addition salts thereof, 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, one of R<SP>3</SP> or R<SP>4</SP> is methyl, Z' is hydrogen and Z<SP>11</SP> is hydrogen, then Z<SP>3</SP> is OH, alkoxy, Br, Cl, F or, taken with Z<SP>2</SP> is a -O-, -CH 2 -, -CCl 2 - or -CF 2 - group, (5) 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, 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, then Z<SP>11</SP> is OH, alkoxy, Br, Cl, F or, taken 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, one of R<SP>3</SP> or R<SP>4</SP> is methyl, Z<SP>3</SP> together with Z<SP>2</SP> is a double bond and Z<SP>11</SP> together with Z<SP>10</SP> is a double bond, then Z<SP>7</SP> is OH, alkoxy, Br, Cl, F or, taken with Z<SP>6</SP>, a -O-, -CH 2 -, -CC 2 l- or -CF 2 - group. The amines can be prepared (1) by reduction of the corresponding amide in which R is a group -CONR<SP>7</SP>R<SP>8</SP> with LiAlH 4  or (2) by reaction of the corresponding halide in which R is a group -CH 2 X, where X is Br or Cl, with ammonia or an amine HNR<SP>7</SP>R<SP>8</SP>. Any 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> double bond in the starting amide or halide or in the amine 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 attack at the 2,3-position in the starting amides can be achieved using H 2 O 2  in aqueous alkali (to introduce a fused -O- group) and dimethylsulphoxonium methylide base in dimethylsulphoxide (to introduce a fused -CH 2 - group). Other derivatives are obtained by, e.g., reduction of the epoxide to give the monohydroxy 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 Brhydroxy compounds. The ethers of compounds containing -OH groups are made by conventional etherification 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. The example describes the preparation of amines derived from 3,7,11-trimethyldodeca-2,6,10-trienyl-, 3,7,11 - trimethyltrideca - 2,6,10 - trienyl - and 3,11 - dimethyl - 7 - ethyltrideca - 2,6,10 - trienyl-amines and includes the preparation of amines excluded by the provisos from the above definition. The preparation of a large number of amides from which the amines can be obtained by reduction is also disclosed. The amines possess insecticidal properties (see Division A5).