1,180,400. Perfluoro carbon substituted aromatic compounds. MINNESOTA MINING & MFG. CO. 15 June, 1967, No. 51224/66. Heading C2C. [Also in Division C3] Perfluoro carbon groups are introduced directly into aromatic carbocyclic rings of organic compounds by heating at 100-225‹ C. and under free radical conditions a mixture of (1) a compound which contains an aromatic carbocycle with available hydrogen thereon and which is:- (a) a benzene ring, the algebraic sum of the Hammett sigma (para) parameters of the substitutents on the benzene ring being not greater than 0À5; or (b) a six-membered aromatic ring which is part of a fused ring system, the algebraic sum of the Hammett sigma (para) parameters of the substituents on the ring system being not greater than 0.8; and (2) a perfluoro carbonsulphonyl chloride or bromide having 1-18 carbon atoms in the molecule, until substantial reaction has occurred and recovering the perfluorocarbon-substituted aromatic compound from the resulting mixture. An available hydrogen on the ring of the aromatic compound is replaced by the perfluoro - carbon group with the loss of one molecule each of sulphur dioxide and hydrogen chloride or bromide. The term " under free radical conditions " means that the reaction is effected in the presence of free radicals which may be generated by application of heat, by a free radical generating catalyst or by ultra-violet light. The aromatic compounds used as starting materials may carry alkyl substituents or may be, for example, aromatic ethers, polyethers, sulphides, ketones, amines, phenols, naphthols, monohalophenols, polyhydroxy benzenes, mono- and di-halo aromatic hydrocarbons or polyphenyls. Suitable perfluoro carbon sulphonyl halides are those in which the perfluorocarbon group is, for example, perfluoro alkyl, perfluorocyclohexyl, or perfluoro(alkyl cyclohexyl). Examples are given of the introduction of perfluorocarbon groups into acenaphthene, indene, di- and tri-phenyl, various hydrocarbon compounds containing fused aromatic rings; pchlorophenol, m- and p-dihydroxy benzene, α- and -naphthol, 4-chlomaphthol- 1, 2,2-diparahydroxyphenylpropane, 8 - hydroxy quinoline, diphenyl ketone, diphenyl ether, diphenyl sulphide, diphenylamine, 2,6 - dimethyl naphthalene, quinoline, 1 - chloro - 4 - methoxy naphthalene, benzene, phenyl 2,4 - dihydroxyphenyl ketone; 1,2,3 - trihydroxy benzene, 5 - nitroacenaphthene, 4 - methoxy - 1- hydroxy naphthalene, N - acetylaniline, 1,2- dichlorobenzene, naphthalic acid anhydride and 1,3-dimethoxybenzene.
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