Patent GB-1209902-A (GB)
Title: Long chain hydrocarbon phosphonates and processes for their preparation
IPC: C07C31/44
Filed: 1967-08-30
Abstract: 1,209,902. Long-chain hydrocarbon phosphonates. ZOECON CORP. 30 Aug., 1967 [15 Sept., 1966; 28 Oct., 1966; 7 Nov., 1966; 16 Nov., 1966; 29 Dec., 1966 (2); 24 Feb., 1967 (3)], No. 39601/67. Heading C2C. [Also in Division A5] The invention comprises phosphonates of the formula where R is the group -CH 2 PO(OR<SP>9</SP>) 2 , wherein R<SP>9</SP> is an alkyl or phenyl group, R<SP>1-4</SP> represent C 1-6  alkyl groups, Z<SP>2</SP> is hydrogen or -OH, Z<SP>3</SP> is hydrogen, -OH, C 1-6  alkoxy, Br, Cl, F, or, 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 hydrogen, -OH, Br, Cl or F, Z<SP>7</SP> is hydrogen, -OH, C 1-6  alkoxy, Br, Cl or F, or, 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 hydrogen, -OH, Br, Cl or F, Z<SP>11</SP> is hydrogen, -OH, Br, Cl or F or, together with Z<SP>10</SP>, represents a carbon-carbon double bond, -O-, -CH 2 -, -CCl 2 - or -CF 2 -, and the corresponding carboxylic esters, tetrahydropyranyl ethers and tetrahydrofuranyl ethers of the compounds containing -OH groups, provided that, Z<SP>2</SP> is hydrogen when Z<SP>3</SP> is hydrogen, Z<SP>6</SP> is hydrogen when Z' is hydrogen and Z<SP>10</SP> is hydrogen when Z<SP>11</SP> is hydrogen. The phosphonates are prepared by reacting a halide of the formula where X represents Br or Cl, each of Z<SP>6'</SP> and Z<SP>7'</SP> is hydrogen, or, when taken together, a double bond, and each of Z<SP>10'</SP> and Z<SP>11'</SP> is hydrogen or, when taken together, a double bond, with an alkyl or phenyl phisphite to give a phosphonate of the formula The Z<SP>2</SP>-Z<SP>3</SP> double bond in this phosphonate and any Z<SP>6</SP>-Z<SP>7</SP> or Z<SP>10</SP>-Z<SP>11</SP> double bond in the phosphonate or starting halide is 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-Clsuccinimide 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  alkanlo. Specified compounds include derivatives of 3,7,11-trimethyldodeca-2,6,10-trienyl-, 3,11-dimethyl - 7 - ethyltrideca - 2,6,10 - trienyl- and 3,7,11 - trimethyltrideca - 2,6,10 - trienyl - phosphonates. The phosphonates possess insecticidal properties (see Division A5).