Benzoyl chloride purification

Benzotriazole, 20,16 Benzoylacetic ester, 23, 35 Benzoylation of acetoacetic ester by ethyl benzoate, 23, 35 Benzoyl chloride, 24, 14 purification of, 24, 15 Benzoyl Cyanide, 24,14, 16 Benzoyleormic acid, 24,16 Benzoyl-o-toluidines, conversion to indoles, 22, 95... 

A wide variety of monomers, such as (3,5-dibromophenyl)boronic acid, 3,5-bis(trimethylsiloxy)benzoyl chloride, 3,5-diacetoxybenzoic acid, and 2,2-dimethylol propionic acid have been used for the synthesis of hyperbranched polymers. A selection of these polymers are described in Sect. 3. The majority of the polymers are synthesized via step-wise polymerizations where A B monomers are bulk-polymerized in the presence of a suitable catalyst, typically an acid or a transesterification reagent. To accomphsh a satisfactory conversion, the low molecular weight condensation product formed during the reaction has to be removed. This is most often achieved by a flow of argon or by reducing the pressure in the reaction flask. The resulting polymer is usually used without any purification or, in some cases, after precipitation of the dissolved reaction mixture into a non-solvent. 

The benzoyl chloride, obtained from British Drug House (Canada) Ltd., was purified4 by washing a benzene solution with 5% aqueous sodium bicarbonate solution, drying over calcium chloride, and fractional distillation through a 40-cm. Vigreux column, b.p. 69-71° (12 mm.). The checkers used a fresh bottle, from Matheson Coleman and Bell, without purification. 

The benzanilide should be of good quality, or tarry material will form and interfere with purification of the product. Benzanilide is readily made by the Schotten-Baumann procedure from aniline, 10% aqueous sodium hydroxide, and benzoyl chloride in the proportions 6 30 5, and after crystallization from 95% ethanol is sufficiently pure. 

Benzoyl chloride (8.6 ml) and 4 drops of concentrated H2S04 were added to the solution of l,6,8-trichlor-3-o-carbomethoxybenzoylpyrene (5.73 g) in nitrobenzene (170 ml) at 100°C. This mixture was heated to 180°C and stirred for 40 min. The cooled solution was filtered and washed by methanol. Yield 4.32 g (80.7%) of l,6,8-trichloro-2,3-phthaloylpyrene mp 339-340°C. This material was used without further purification in the next step. 

Treatment of the crude reaction mixture containing compounds 718, 719 and ferrocene without purification with benzoyl chloride (70 °C) followed by hydrolysis of the resulting benzoylated pyrrole 720 using tetrabutylammonium hydroperoxide (TBAH) furnished pharmaceutical agent (6 )-Ketorolac (ToradoT and Acular, 721, ee 90% determined by chiral HPLC, 25% isolated yield over three steps) along with recovered chiral auxiliary. 

Benzoyl chloride was obtained from Merck Company, Inc., and used without purification. 

To a solution of o>-(2,2-dibromocyclopropyl)alkanol (1.0 mmol) in dry EtjO (5 mL) was slowly added MeLi in EtjO (2.0 mmol) at — 85 °C under Nj. The reaction mixture was gradually warmed up to 0°C over a period of 5 h, and quenched by the addition of H O. After extraction with EtjO, the organic layer was dried (NajSOJ, and concentrated in vacuo. After a capillary GC analysis, the residual oil was subjected to flash chromatography (EtOAc/petroleum ether) to give a mixture of insertion products and allenyl alcohol (if formed). Analytically pure products were obtained after purification by preparative GC. In one case the reaction mixture was quenched by adding benzoyl chloride (1.2 mmol) at 0°C and then stirring further for 14 h at rt. 

THF served as an inexpensive, readily available starting material. Ring opening using sodium iodide and benzoyl chloride in acetone [36], followed by alkylation of acetyl acetone, the addition of paraformaldehyde and deacylative methylenation in DMSO, afforded vinyl ketone 99 [37]. This material was most conveniently used without purification in a sequence consisting of ketalization, removal of the benzoate, and Doering oxidation to provide aldehyde 97 in a 60% yield overall [38],... 

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