Blomquist大环化反应
链状双烯酮类化合物聚合关环接着脱羧得到大环脂肪酮的反应。
反应机理
先进行分子间的Staudinger烯酮环加成，接着水解，脱羧得到产物。
反应操作
1,8-Cyclotetradecanedione (4). Suberic acid 1 (3 g, 1.7 mmol) and SOCl2 (0.4 g, 3.4 mmol) were heated at 55 C for 2 h and then on a water bath until gas evolution ceased. Excess SOCl2 was removed in vacuo and the acid chloride was diluted with Et2O (200–300 mL). This was added to Et3N
(10–20 mL) in Et2O (500–600 mL) over 26 h under gentle reflux. The decanted solution was washed with dil HCl and water, dried (MgSO4) and distilled. The yellow residue was treated with EtOH (5 mL) and KOH solution (1.8 g in 20 mL EtOH). After 10 h at r.t. and 2 h reflux, the mixture was diluted with water, extracted with Et2O and the solvent evaporated to afford two crops of 4, total yield 10%, mp 147.5–148 C.
【Blomquist A, J Am Chem Soc., 1948, 70, 30】
相关文献
1 Blomquist AT J Am Chem Soc 1947 69 472
2 Blomquist AT J Am Chem Soc 1948 70 30
3 Belenky LI Russ Chem Bull 1957 6 1287
4 Dang Y Org Prep Proced Int 1993 309
5 Tykwinski RR J Am Chem Soc 2000 122 6917
编译自：Organic Syntheses Based On Name Reactions, 3RdEd, A. Hassner, Page 50.
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