PREPARATION OF MACROCYCLIC COMPOUNDS

1,194,117. Cycloalkenes by intramolecular condensation. GOODYEAR TIRE & RUBBER CO. 31 July, 1968 [1 Sept., 1967], No. 36507/68. Heading C5E. Compounds containing an alicyclic ring having at least 12 carbon atoms and containing at least 1 carbon-carbon double bond, are prepared by contacting an acyclic unsaturated hydrocarbon of formula in which R1 and R11 are hydrooarbyl radicals or H, and Z is a hydrocarbon fragment containing at least 9 carbon atoms in linear succession between the methylidene group and the methylene group and contains single and/or double bonds which are not conjugated, in a solution of concentration not more than 10% in an inert diluent with a catalyst comprising (a) at least one organometallic compound of Groups Ia, IIa, IIb or IIIa of the Periodic Table, (b) at least one molybdenum or tungsten salt and (c) at least one compound of the general formula RYH, where Y is O or S and R is H or an alkyl, aryl, aralkyl, alkaryl or alkenyl radical which radicals may or may not be substituted by a YH group or a YR111 group wherein R111 is alkyl, aralkyl or alkaryl. Preferred catalyst components are (a) an organoaluminium compound; (b) a tungsten halide; (c) an alcohol. The Z groups may be substituted by hydrocarbyl radicals and the carbon atoms in the linear succession may form part of an aromatic or alicyclic ring, e.g. cyclohexane, cyclohexene, bicycloheptane, or benzene. Examples describe the preparation of compounds of the formula from a polyoctane prepared by chain-opening polymerization of cyclo-octene; and of compounds of the formula which are claimed per se when n is an integer greater than 1, from a polybutadiene formed by chain-opening polymerization of 1,5-cyclo-octadiene. The catalyst for the intramolecular condensation in each example was EtAlCl 2 / WCl 6 /C 2 H 5 OH.