GB624047A - Process for the manufacture of unsaturated halogen compounds and products of dehalogenation thereof - Google Patents

Abstract

Halogen compounds are made by heating a di- or poly-olefine containing conjugated double bonds and at least one methylene, methyl or methine group in a -position with respect to the conjugated system with a carboxylic imide, amide or arylamide halogenated at the nitrogen while exposing the reactants to light and if desired splitting of hydrogen halide from the resulting halogen compound. As starting materials there may be used 1 : 1-diphenyl-pentadiene-1 : 3, 1 : 1-diphenyl-4-methyl-pentadiene - 1 : 3, 1 : 1 - diphenyl - hexadiene - 1 : 3, octadiene-3 : 5, cyclohexadiene-1 : 3, a -terpenene, a - or b -phellandrene, di-, tetra- or hexahydroarerophthol esters, steroids having conjugated double bonds in the ring structure and/or in the side chain, such as D 2 : 4-, D 3 : 5-, D 5 : 7-, D 7 : 14-, D 16 : 20-, D 20 : 23-, D 22 : 24-compounds, e.g. D 16 : 20-3-acyloxy- or 3-keto-21-oxy-norallocholadienic acid lactones, D 20 : 23-3-acyloxy- or 3 : 12-diacyloxy- or 3 : 7 : 12-triacyloxy-24 : 24-diphenyl-choladienes, D 20 : 23-3-keto- or 3 : 11 - diketo- or 3 : 12-diketo- or 3 : 7 : 12-triketo-24 : 24-diphenyl choladienes, D 20 : 23-3-acyloxy - 11 - or 12-keto-24 : 24 - diphenyl - choladienes, D 20 : 23- 3 - acyloxy - 11 - or 12 - keto - 24 : 24 - diphenyl-choladienes, D 20 : 23-3-keto - 11 - or 12-oxy- (or acyloxy-) 24 : 24-diphenyl-choladienes, D 5 : 20 : 23- 3 - acyloxy - 24 : 24 - diphenyl - chola - trienes, D 4 : 20 : 23- 3 - keto - 24 : 24 - diphenylcholatriene, D 4 : 20 : 23- 3 - keto - 11 - or 12 - oxy-(or acyloxy-) 24 : 24 - diphenyl - cholatrienes, D 4 : 20 : 23- 3 : 11- or 3 : 12 - diketo - 24 : 24 - diphenyl - cholatrienes, D 22 : 24- 3 : 12 - diacyloxy-25 : 25-diphenyl-homocholadienes, D 5 : 22 : 24-3-acyloxy - 25 : 25 - diphenyl (or dimethyl) or 25-phenyl - 25 - methyl - homocholatrienes. Any nuclear bonds which are present may be protected, for example, by saturation with halogen. As halogenating agents there may be used N-halogen-succimides, -phthamides, -parabanic acids, -cyanuric acids, -hydantoins and -barbituric acids, -acetamide, -propionamide, -diacetamide, -acetanilide and -benzanilide. Hydrogen halide may be split off from the halogenated products to introduce a further conjugated double bond, e.g. by means of pyridine, collidine, quinoline or dimethylaniline. The newly-formed double bond may be split oxidatively by means of chromic acid, ozonization or the action of peroxides. Sensitive substituents in the starting materials such as hydroxyl groups may be protected by esterification or etherification. At a stage after halogenation, the protected nuclear double bonds may be regenerated.