Anisole → (4-Methoxyphenyl)(3-methylphenyl)methanone

関与物質

反応条件

反応手順

In sequence, 1,000 mL of carbon disulfide, 384 g (3.55 mole; 10% excess) of anisole, and 500 g (3.23 mole) of m-toluoyl chloride were placed in a 5 L flask, and the contents were cooled to about 10° C. Then 500 g AlCl3 was added in small increments with stirring over a 3 hr period. The stirred mixture was kept at room temperature for 2 days during which 500 mL more of carbon disulfide was added by maintain fluidity. After adding ice-water to decompose the complex, carbon disulfide was removed by steam distillation and the product was extracted with methylene chloride. The extract was washed with water and then distilled at 170° C./1.2 mm Hg to yield 642 g of 4-methoxy-3'-methylbenzophenone. Half of the product (1.42 mole) was mixed with 1500 mL of pyridine and a solution of 75 g sodium hydroxide in 1500 mL of water. This mixture was heated to 80°-90° C. and 500 g potassium permanganate was added stepwise over a 4 hr period. Refluxing continued one more hour. Sludge was filtered out and washed well with hot water. Acidification of the filtrate yielded a precipitate of 4-methoxy-3'-carboxybenzophenone. After recrystallization from ethanol, melting temperature was 183°-186° C. A total of 392 g (1.53 mole) of so prepared 4-methoxy-3'-carboxybenzophenone was added to a premixture of 1150 mL of 48% HBr/575 mL acetic anhydride/575 mL acetic acid, and the mixture was refluxed for 15 hr. Pouring the contents into water precipitated 4-hydroxy-3'-carboxybenzophenone which, after filtration and drying, yielded 350 g (1.45 mole) of crude product. Mixing this product with 1050 mL of acetic anhydride containing 1.5 mL of concentrated sulfuric acid and heating for 30 min at 100° C. yielded 4-acetoxy-3'-carboxybenzophenone which was isolated by precipitation in excess ice-water, filtration, and drying. Recrystallization first from dioxane and then chloroform provided 4-acetoxy-3'-carboxybenzophenone melting at 190°-193° C.

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