Patent GB-959605-A (GB)
Title: Process for the arylation of aromatic compounds
Inventor: BAIN PETER JAMES STRATFORD
IPC: C07D333/38
Filed: 1961-10-10
Abstract: An aryl (carbocyclic or heterocyclic) group is introduced into an aromatic (carbocyclic or heterocyclic) compound by heating the latter with an aromatic compound containing a nuclear-bound sulphonyl halide or sulphonic acid group or a salt of the latter which decomposes under the reaction conditions, in the presence of a catalyst that is a metal, a metal compound, an organic nitrogen compound, a polyhydric phenol, a quinone or a compound containing an aliphatic group of 6 or more carbon atoms. Reaction temperatures of 125-300 DEG C. and catalyst proportions of 0.0001-0.5 gm. mol. per gm. mol. of arylating agent are specified. Metal catalysts specified are copper, platinum, palladium, ruthenium, sodium, potassium, calcium, cobalt, lead, manganese, mercury, silver, titanium and compounds thereof. Organic nitrogen catalysts include amines, amine salts, amides, azo compounds and nitro compounds. Catalytic polyhydric phenols include polyhydroxy-benzenes and naphthalenes, hydroquinone and pyrogallol. Catalytic quinones include benzo- and naphtho-quinones.  The catalyst containing an aliphatic group of 6 or more carbon atoms may have the group as a straight or branched chain or as a cycloaliphatic system e.g. a saturated or unsaturated hydrocarbon, a halogeno hydrocarbon, an alcohol, a carboxylic acid, an ester or an ether. The aromatic compounds that may be arylated include furan, benzofuran, thiophene, benzothiophene, dibenzothiophene, chlorobenzene, bromobenzene, p-chlorotoluene, o-dichlorobenzene, 2-chloronaphthalene, 4-dichlorodiphenyl, anisole, phenetole, diphenyl ether, 2-ethyl-thiophene, 2-phenylthiophene, thiophene -2- carboxylicethyl ester, 4-methylbenzofuran, 5-bromobenzofuran, 6 methoxybenzofuran, 4-phenylbenzofuran, 1-cyclohexyldibenzofuran, 1-phenyldibenzofuran, 2, 8-dichlorodibenzofuran, 2-ethoxybenzothiophene, 1-cyclohexyldibenzothiophene, 2-phenyldibenzothiophene, 4-bromodibenzothiophene, 2-phenoxydibenzothiophene and nitrogen containing aromatic compounds.  The aromatic radical of the arylating agent may be a chlorophenyl, nitrophenyl, furyl, thienyl, pyridyl, benzothienyl, dibenzothienyl or quinolinyl radical which radical may contain a substituent e.g. an aryl group, a halogen atom, a nitro group, a carboxylic ester group, an alkoxy group or an aryloxy group. Specified arylating agents include p-nitrobenzenesulphonyl chloride and pyridine -3- sulphonyl chloride. Examples describe the preparation of phenylated diphenyl ether, 2, 4, 6-tribromodiphenyl 2, 3, 5, 6-tetrachlorodiphenyl, monophenylated m-diphenoxybenzenes, phenyldibenzofurans, and 2, 5-dibromodiphenyl.ALSO:An aryl (carbocyclic or heterocyclic) group is introduced into an aromatic (carbocyclic or heterocyclic) compound by heating the latter with an aromatic compound containing a nuclear-bound sulphonyl halide or sulphonic acid group or a salt of the latter which decomposes under the reaction conditions, in the presence of a catalyst that is a metal, a metal compound, an organic nitrogen compound, a polyhydric phenol, a quinone or a compound containing an aliphatic group of 6 or more carbon atoms.  Reaction temperatures of 125-300 DEG  C. and catalyst proportions of 0.0001-0.5 gm. mol. per gm. mol. of arylating agent are specified.  Metal catalysts specified are copper, platinum, palladium, ruthenium, sodium, potassium, calcium, cobalt, lead, manganese, mercury, silver, titanium and compounds thereof. Organic nitrogen catalysts include amines, amine salts, amides, azo compounds and nitro compounds.  Catalytic polyhydric phenols include polyhydroxy-benzenes and naphthalenes, hydroquinone and pyrogallol. Catalytic quinones include benzo- and naphtho-quinones. The catalyst containing an aliphatic group of 6 or more carbon atoms may have the group as a straight or branched chain or as a cycloaliphatic system, e.g. a saturated or unsaturated hydrocarbon, a halogeno hydrocarbon, an alcohol, a carboxylic acid, an ester or an ether. Examples describe various methods of the preparation of terphenyls.