Phenyl p-chlorobenzoate

During the reaction, we observed the formation of phenyl p-chlorobenzoate as byproduct (Scheme 14.2). 

Scheme 14.2 Formation of phenyl p-chlorobenzoate during the benzoylation of phenetole.

Also obtained by photo-Fries rearrangement of phenyl p-chlorobenzoate in cyclohexane or in benzene between 46° and 52° (42 9%) [72],... 

Preparation by Fries rearrangement of p-fluoro-phenyl p-chlorobenzoate,... 

Preparation by Fries rearrangement of 4-chloro-2-ethyl-phenyl p-chlorobenzoate with alumin-Ci ium chloride at 160° for 15 min [1107]. 

Preparation by Fries rearrangement of 3,4-(hethyl-phenyl p-chlorobenzoate with alumininm chloride in tetrachloroethane at 125 for 6 h [710]. 

Willstatter s method (Volume I, pp. 278 285-286) to a-methyltropidine, i.e. (+ )-5-dimethylamino-l,3-cycloheptadiene (LXXXIV). Resolution of the latter with dibenzoyltartaric acid followed by (a) isomerization of each antimer into )3-methyltropidines (LXXXV), (b) hydrolysis, (c) partial hydrogenation of the cycloheptenone, and (d) Grignard reaction with the cycloheptanones (LXXXVI) gave the phenyl-, and p-chlorophenyl-l-cycloheptenes (LXXXVII). The product of oxidation, arising from (+ )-LXXXI V, contained the whole radioactivity, while the benzoic and p-chlorobenzoic acids from the levorotatory form were radioinactive. This proved that the whole label from ornithine-a-i C was either in C-1 or in C-5 in hyoscyamine (80, 81). 

The relation between the constant of the para acid and that of the ortho or meta acid varies with the nature of the substituent. While p-nitrobenzoic acid is a slightly stronger acid than m-nitro-benzoic acid, the constant of p-chlorobenzoic acid is only about one-half that of the meta acid. The case of p-hydroxybenzoic acid is a striking one while o-hydroxybenzoic acid and m-hy-droxybenzoic acid are more highly ionized than benzoic acid, the constant of the para acid is less than half that of benzoic acid. A satisfactory explanation of such facts as these would, no doubt, materially advance organic chemistry. The effect of a phenyl radical on a carboxyl group in a side-chain, is shown by the constants for phenylacetic acid, hydrocinnamic acid, and cinnamic acid. 

Preparation by Fries rearrangement of 2-chloro-6-methyl-phenyl o-chlorobenzoate with alnminium chloride in chloro-benzene for 20 min at 140-150° or in nitrobenzene for 24 h at 75° [480]. m.p. 164-165° [480] Spectra (NA). 

Seeger M, M Zielinski, KN Timmis, B Hofer (1999) Regiospecificity of dioxygenation of di- to pentachlorobi-phenyls and the degradation to chlorobenzoates by the f>p/j-encoded catabolic pathway of Burkholderia sp. strain LB400. Appl Environ Microbiol 65 3614-3621. 

C7H3C12F3 2,4-DICHLOROBENZOTRIFLUORIDE 3,4-DICHLOROPHENYL ISOCYANATE p-CHLOROBENZOTRIFLUORIDE m-CHLOROBENZOYL CHLORIDE 3-NITROBENZOTRI FLUORIDE BENZOYL CHLORIDE o-CHLOROBENZOIC ACID BENZOTRI CHLORIDE BENZOTRI FLUORIDE BENZONITRILE PHENYL ISOCYANATE 2,4,6-TRINITROTOLUENE... 

DICHLOROPHENYL ISOCYANATE p-CHLOROBENZOTRI FLUORIDE m-CHLOROBENZOYL CHLORIDE 3-NITROBENZOTRIFLUORIDE BENZOYL CHLORIDE 0-CHLOROBENZOIC ACID BENZOTRICHLORIDE BENZOTRIFLUORIDE BENZONITRILE PHENYL ISOCYANATE 2,4,6-TRINITROTOLUENE BENZYL DICHLORIDE... 

Other water-soluble chloroarenes, like all three chlorophenols, 2,4-dichlorophenol and 3-nitro-4-chlorobenzoic acid, can also be made to react. The reaction with water-insoluble aryl chlorides, such as p-chloroanisole or p-chloroacetophenone, can be run in aqueous organic solvents, such as DMF or HMPA at 130-140°C in the presence of Na2C03. In the absence of water in DMF, the yield of phenylation product is half of that obtained with a small amount of water (DMF H20= 13 1) added to the solvent. Though the yields are usually moderate (40-60%, based on chloroarene), it is evident that the... 

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