Oxalyl chloride → 4-(4-oxocyclohexyl)benzoyl Chloride

温度

2 °C

A suspension of 133.3 g of aluminium chloride in 250 ml of methylene chloride was treated dropwise at 20° C. while cooling and gassing with nitrogen with a solution of 174.2 g of 4-phenylcyclohexanone in 250 ml of methylene chloride. The reaction mixture was stirred for a further 30 minutes until a clear solution was obtained. In the meanwhile, a suspension of 133.3 g of aluminium chloride in 500 ml of methylene chloride was treated with 172 ml of oxalyl chloride while gassing with nitrogen. This mixture was subsequently treated dropwise at 20°-25° C. within 1 hour with the above solution of the 4-phenylcyclohexanone-aluminium chloride complex. The reaction mixture was stirred for a further 30 minutes, then cooled to 2° C. and added dropwise within 20 minutes while stirring to a solution of 300 g of calcium chloride in 1 l of water. The mixture was stirred at room temperature for a further 1.5 hours and then poured on to 500 ml of ice/water. The organic phase was separated and washed with 500 ml of semi-saturated sodium chloride solution. The aqueous phases were back-extracted twice with 500 ml of methylene chloride each time. The combined organic phase was dried over sodium sulfate, filtered and concentrated. The oily 4-(4-oxocyclohexyl)benzoyl chloride obtained was dissolved in 400 ml of toluene and this solution was added dropwise to a mixture of 150 ml of methanol, 200 ml of pyridine and 1 l of toluene. The reaction mixture was left to stand overnight and then washed in succession with water, 3N hydrochloric acid, semi-saturated sodium hydrogen carbonate solution and again with water, dried over sodium sulfate, filtered and concentrated. Recrystallization of the residue from toluene at -25° C. gave 128 g of pure methyl 4-(4-oxocyclohexyl)-benzoate with m.p. 91°-92° C.

1. additionwas treated dropwise at 20° C.
2. temperaturewhile cooling
3. customwas obtained
4. additionThis mixture was subsequently treated dropwise at 20°-25° C. within 1 hour with the above solution of the 4-phenylcyclohexanone-aluminium chloride complex
5. stirringThe reaction mixture was stirred for a further 30 minutes
6. additionadded dropwise within 20 minutes
7. stirringThe mixture was stirred at room temperature for a further 1.5 hours
8. customThe organic phase was separated
9. washwashed with 500 ml of semi-saturated sodium chloride solution
10. extractionThe aqueous phases were back-extracted twice with 500 ml of methylene chloride each time
11. dry with materialThe combined organic phase was dried over sodium sulfate
12. filtrationfiltered
13. concentrationconcentrated

ORDレコード

ord-57a6e117f81f46d6afa2825b94cc5761

出典データセット

uspto-grants-1992_12

DOI

10.6084/m9.figshare.5104873.v1

特許番号

US05174921