反应详情

4,4-Dimethyl-1,3-cyclohexanedione [14.0 grams (g), 0.1 mole], 20.0 g (0.1 mole) 2,4-dichlorobenzoyl cyanide and 13.6 (0.11 mole) anhydrous, powdered zinc chloride were combined in 100 milliliters (ml) methylene chloride. Triethylamine (10.1 g, 0.12 mole) was slowly added with cooling. The reaction mixture was stirred at room temperature for 5 hours and then poured into 2N hydrochloric acid. The aqueous phase was discarded and the organic phase was washed with 150 ml 5% Na2CO3 four times. The aqueous washings were combined and acidified with HCl, extracted with methylene chloride, dried and concentrated to yield 25.3 g of crude product. The crude product was chromatographed (2% AcOH/CH2Cl2) in 5 g aliquots then reduced on rotavap under reduced pressure at 50° C. for 30 minutes to remove AcOH. This yielded an oil (40% yield). The structure was confirmed by instrumental analysis.

1. temperaturewith cooling
2. washthe organic phase was washed with 150 ml 5% Na2CO3 four times
3. extractionextracted with methylene chloride
4. customdried
5. concentrationconcentrated
6. customto yield 25.3 g of crude product
7. customThe crude product was chromatographed (2% AcOH/CH2Cl2) in 5 g aliquots
8. waitthen reduced on rotavap under reduced pressure at 50° C. for 30 minutes
9. customto remove AcOH