Acrylic acid Chlorobenzenes

In 1972 Wright prepared 3-chlorothieno[3,2-6]thiophene-2-carbonyl chloride (94) in 11-13% yield by heating 3-(2-thienyl)acrylic acid, thionyl chloride, and pyridine, a method of synthesis of benzo[6]-thiophene-2-carbonyl chloride derivatives. " Methyl 3,5-dichloro-thieno[3,2-6]thiophene-2-carboxylate (95) and methyl 2-chloro-3-(5-chloro-2-thienyl)acrylate were also isolated. When fte reaction was carried out in refluxing toluene or chlorobenzene, the acid chloride (94)... 

Bimetallic Pd/Ni [121] andPd/Co [122] systems have exhibited considerable catalytic activity in the Heck reaction of nonactivated chloroarenes with ethyl acrylate, acrylonitrile, and acrylic acid. For instance, ethyl acrylate and acrylonitrile reacted smoothly with chlorobenzene in the presence of Nal and catalytic amounts of NiBr2, Pd2(dba)3, and o-Tol3P in DMF to give E-isomers of ethyl cinnamate and cinnamonitrile, respectively [121]. The reaction occurred via the nickel-catalyzed halogen exchange between ArCl and Nal, followed by the conventional palladium-catalyzed olefination of the iodoarene generated in situ. 

The Heck reaction is compatible with water, and water-soluble catalysts have successfully been employed (entry 10). Alkali metal salts (NaHCOj, K2CO3, and KOAc) are effective bases in the smooth reactions of acrylic acid with o-, m-, or p-iodobenzoic acid or p-iodophenol in which water-soluble salts are formed and very high yields are encountered (entry 11). Activated heteroaryl chlorides are good arylpalladium precursors (entry 12) while nonactivated aryl chlorides have to date been considered to be less useful in the Heck reaction. In entry 13, the recent protocol devised by Littke and Fu for arylation with nonactivated chlorobenzenes is shown. ... 

Enamines W-153, W-154, and W-155 and propiolactone or acrylic acids form dihydropyridones, W3-56 -157, and XI1-1S8, when boiled i chlorobenzene. ... 

Benzotrichloride Method. The central carbon atom of the dye is supplied by the trichloromethyl group fromy>-chlorobenzotrichloride. Both symmetrical and unsymmetrical triphenylmethane dyes suitable for acrylic fibers are prepared by this method. 4-Chlorobenzotrichloride is condensed with excess chlorobenzene in the presence of a Lewis acid such as aluminium chloride to produce the intermediate aluminium chloride complex of 4,4, 4"-trichlorotriphenylmethyl chloride (18). Stepwise nucleophilic substitution of the chlorine atoms of this intermediate is achieved by successive reactions with different a.rylamines to give both symmetrical (51) and unsymmetrical dyes (52), eg, N-(2-chlorophenyl)-4-[(4-chlorophenyl) [4-[(3-methylphenyl)imino]-2,5-cyclohexadien-l-yhdene]methyl]benzenaminemonohydrochloride [85356-86-1] (19) from / -toluidine and a-chloroaniline. 

Phenylcarboxylic acid. See Benzoic acid Phenyl Cellosolve acrylate. See 2-Phenoxyethyl acrylate Phenyl chloride. See Chlorobenzene Phenylchloroform. See Benzotrichloride Phenyl chloromercury. See Phenylmercuric chloride... 

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