反应详情

Dichlorocyclobutanone 3 (128 g, 0.48 mol) was dissolved in 520 mL of 1:1 isopropanol-water in a 2 L, 3-neck flask with an overhead stirrer. Zinc granules (126 g, 1.9 mol, −30+100 mesh) were added in one portion. After 60 min at room temperature, 130 mL of AcOH plus 260 mL of water were added dropwise via addition funnel (ca. 4 mL are added initially, followed by a 10 min hold to check for exotherms; 20 ml were then added, followed by another 10 min hold; once any exotherm has abated, the remaining acid solution was added dropwise; the entire addition takes 1.5-2 h). After 16 h, the mixture was transferred to a separatory funnel, decanting away from most of the zinc (several small isopropanol rinses were used). The isopropanol-AcOH-water mixture was then extracted with 5 portions of toluene (250 mL each), which are combined and concentrated to provide 51.7 g of product as a dark, orange-brown oil (85% crude mass balance, ca. 85% pure by 1H nmr). This material is suitable for subsequent reactions, or can be purified by distillation, which provided 29.4 g (0.23 mol, 49% yield) of product as a clear, colorless oil (b.p. 65-75° C. at 1.2 mm). It's spectral properties (1H nmr, GC/MS) were identical to samples prepared by the oxymercurafion route of Chandrasekaran (Synthetic Communications 1984, 14, 339-345).

1. additionare added initially
2. waitfollowed by a 10 min
3. addition20 ml were then added
4. waitfollowed by another 10 min
5. additionthe remaining acid solution was added dropwise
6. additionthe entire addition
7. waittakes 1.5-2 h
8. waitAfter 16 h
9. customthe mixture was transferred to a separatory funnel
10. customdecanting away from most of the zinc (several small isopropanol rinses were used)
11. extractionThe isopropanol-AcOH-water mixture was then extracted with 5 portions of toluene (250 mL each), which
12. concentrationconcentrated