Neue Verbindungen und Verfahren zu deren Herstellung

摘要

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 A1, A2 above, [D] is one of the groups of the formulµ B1 , B2 above, each of R1, R2, R3 and R4 is hydrogen or C 1 _ 5 alkyl, R10 is one of the groups -COOR11, -CH 2 R12, -CONR13R14, -CH 2 NR13R14 or -CH 2 PO(OR15) 2 , R11 is hydrogen, C 1 _ 5 alkyl or an alkali metal cation, R12 is hydroxy or an ether or carboxylic ester thereof; each of R13 and R14 is hydrogen, C 1 _ 5 alkyl, hydroxy-C 1 _ 6 alkyl, C 1 _ 8 alkoxyl- C 1 _ 8 alkyl or phenyl or R13 and R14 together complete a pyrrolidino, piperidino, piperazino, morpholino or 41-C 1 _ 5 alkyl-piperazino ring, each of R15 is C 1 _ 5 alkyl, each of Z2 and Z3 is hydrogen or together Z2 and Z3 represent a double bond or a group each of W6 and W10 is hydrogen or hydroxy provided that W6 is hydrogen when W7 is hydrogen and W10 is hydrogen when W11 is hydrogen, each of W61, W7, W101 and W11 is hydrogen, hydroxy or an ether of carboxylic ester thereof, each of Z7 and Z11 is hydroxy or a ether or carboxylic ester thereof or W6 and W7 together represent a double bond or a group >0, >CH 2 , >CCl 2 or >CF 2 or W10 and W11 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, C1, C2, C3 and C4 represent the C-71, C-5, C-6, C-7 and C-8 carbon atoms, or the C-111, C-9, C-10, C-11, C-12 carbon atoms respectively, R represents R2 or R3, Z represents hydrogen or Z7 or Z11, W represents W6 or W61 or W10 or W101 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).