Arylation of olefin(s)

摘要

Prodn. of substd. olefins (I), comprises reaction of aryl- diazonium salts (II) with olefins in the presence of a Pd catalyst. Substd. olefins (with Z = -CH=CHR) are pref. obtd. by reaction of a cpd. of formula (I) (with Z = -N2(+)G(-)) with an olefin of formula R-CH=CH2; (where R = H, 1-12C alkyl, opt. substd. 6-10C aryl, opt. substd. heteroaryl with 3-5C and 1-3 O, S or N atoms, or CN, COOM, COO(1-12C alkyl) or SO3M; M = a normal cation; n = 0 or 1 (if n = 0, free valency on ring A is occupied by H); m = 1 or 2; rings A-D and (hetero)aryl gps. are opt. substd. with 1 or more F, Cl, Br, I, 1-12C alk(ox)yl, CF3, OCF3, CN, nitro, COOM, COO(1-12C alkyl), SO3M, CO(1-12C alkyl), CO(6-10C aryl), 6-10C aryl, heteroaryl or opt. 1-12C alkyl-substd. amino gps.; G = normal counterion); reaction is carried out in the presence of a base, with metallic Pd and/or organic or inorganic Pd cpds., opt. combined with complex-forming cpds.; reaction medium is water or an alcohol, with Pd or a salt as catalyst, or in water in presence of a Pd complex derived from a cpd. with hydrophilic gps., pref. sulphonic acid gp(s). esp. a bis-(dibenzylidene acetone) Pd complex with 1-8 sulphonic acid gps.; pref. (I) is of formula RCH=CH-(A)-(-(B)-CH=CHR)n (with rings A, B as above), with R = H or opt. substd. Ph; (II) are sulphobenzene- diazonium salts; the ethylene is introduced into the mixt. with an intensive gassing device, pref. a surface or bulk gasifier, opt. with additional mechanical mixing.