Patent GB-1241208-A (GB)
Title: Unsaturated branched-chain hydrocarbon derivatives
IPC: C07D303/36
Filed: 1968-08-27
Abstract: 1,241,208. Unsaturated C 12 _ 17  branched-chain hydrocarbon derivatives. ZOECON CORP. 27 Aug., 1968 [8 Sept., 1967], No. 40860/68. Heading C2C. [Also in Division A5] Novel unsaturated C 12 _ 17  branched-chain compounds of the formulµ in which [A] is one of the groups [B] is one of the groups [C] is one of the groups of the formulµ A<SP>1</SP>, A<SP>2</SP> above, [D] is one of the groups of the formulµ B<SP>1</SP> ,  B<SP>2</SP> above, each of R<SP>1</SP>, R<SP>2</SP>, R<SP>3</SP> and R<SP>4</SP> is hydrogen or C 1 _ 5  alkyl, R<SP>10</SP> is one of the groups -COOR<SP>11</SP>, -CH 2 R<SP>12</SP>, -CONR<SP>13</SP>R<SP>14</SP>, -CH 2 NR<SP>13</SP>R<SP>14</SP> or -CH 2 PO(OR<SP>15</SP>) 2 , R<SP>11</SP> is hydrogen, C 1 _ 5  alkyl or an alkali metal cation, R<SP>12</SP> is hydroxy or an ether or carboxylic ester thereof; each of R<SP>13</SP> and R<SP>14</SP> is hydrogen, C 1 _ 5  alkyl, hydroxy-C 1 _ 6  alkyl, C 1 _ 8  alkoxyl- C 1 _ 8  alkyl or phenyl or R<SP>13</SP> and R<SP>14</SP> together complete a pyrrolidino, piperidino, piperazino, morpholino or 4<SP>1</SP>-C 1 _ 5  alkyl-piperazino ring, each of R<SP>15</SP> is C 1 _ 5  alkyl, each of Z<SP>2</SP> and Z<SP>3</SP> is hydrogen or together Z<SP>2</SP> and Z<SP>3</SP> represent a double bond or a group each of W<SP>6</SP> and W<SP>10</SP> is hydrogen or hydroxy provided that W<SP>6</SP> is hydrogen when W<SP>7</SP> is hydrogen and W<SP>10</SP> is hydrogen when W<SP>11</SP> is hydrogen, each of W<SP>61</SP>, W<SP>7</SP>, W<SP>101</SP> and W<SP>11</SP> is hydrogen, hydroxy or an ether of carboxylic ester thereof, each of Z<SP>7</SP> and Z<SP>11</SP> is hydroxy or a ether or carboxylic ester thereof or W<SP>6</SP> and W<SP>7</SP> together represent a double bond or a group >0, >CH 2 , >CCl 2  or >CF 2  or W<SP>10</SP> and W<SP>11</SP> together represent a double bond or a group >O, >CH 2 , >CCl 2  or >CF 2 ; and the acid addition salts of the amines, are prepared by dehydrohalogenation of corresponding halogenated compounds as represented by the following partial structures where C, C<SP>1</SP>, C<SP>2</SP>, C<SP>3</SP> and C<SP>4</SP> represent the C-7<SP>1</SP>, C-5, C-6, C-7 and C-8 carbon atoms, or the C-11<SP>1</SP>, C-9, C-10, C-11, C-12 carbon atoms respectively, R represents R<SP>2</SP> or R<SP>3</SP>, Z represents hydrogen or Z<SP>7</SP> or Z<SP>11,</SP> W represents W<SP>6</SP> or W<SP>61</SP> or W<SP>10</SP> or W<SP>101 </SP>and X represents halogen. When Z or W are other than hydrogen, the partial structures (2) or (7) respectively, cannot be obtained. Also, any hydroxy groups in an α-position to X must be protected by etherification or esterification before dehydrohalogenation to avoid forming the oxirane ring. The protecting groups may be removed after formation of the double bond. The reaction is effected by treatment of the halo compound with at least a molar equivalent of a basic reagent per mol. halogen present, e.g. a tertiary amine, an alkali metal alkoxide, hydroxide, carbonate or halide. The reaction product usually contains a mixture of compounds corresponding to the two or more different modes of hydrogen halide elimination. The compounds can be separated by conventional methods. Specific compounds may be identified by chemical methods, e.g. ozonolysis. Thus, ozonolysis of ethyl 3,11-dimethyl-7- ethyl - 10,11 - oxido - trideca - 6 - enoate and 3,11 - dimethyl - 7 - ethyl - 10,11 - oxidotridec- 7-enoate followed by Zn dust reduction yields a mixture of 6,7-oxido-7-methylnonan-3-one and ethyl 3-methyl-5-formylpentanoate and a mixture of 3,4-oxido-4-methyl-hexanol and ethyl 3-methyl-7-oxononanoate respectively. Examples relate to the preparation of a number of unsaturated acids, esters, amides and amines. The products possess arthropod maturation inhibiting properties (see Division A5).