3-羥甲基環(huán)己酮

中文別名:

英文別名:(3-Oxocyclohex-1-yl)methanol;3-(Hydroxymethyl)cyclohexan-1-one

次氯酸化合物，甲硫基乙酸酯和堿依次加入到苯胺或取代苯胺中一鍋法得到3-甲硫基羥吲哚的反應(yīng)被稱為Gassman羥吲哚合成反應(yīng)。甲硫基可以氫化去掉或者用Raney鎳還原。

反應(yīng)機(jī)理

次氯酸化合物先氧化苯胺得到N-氯代苯胺，β-羰基硫化物親核進(jìn)攻N-氯代苯胺，生成锍鎓離子，堿拔羧基α位氫，接著進(jìn)行兩次[2,3]-單電子重排（Sommelet-Hauser）關(guān)環(huán)，得到產(chǎn)物。

Oxindole (5). To a stirred, cooled (65 C) solution of aniline 1 (4.099 m, 44 mmol) in DCM (150 mL) was added dropwise t-butyl hypochlorite (4.77 g, 44 mmol) in DCM (20 mL). After 10 min, ethyl methylthioacetate 2 (5.89 g, 44 mmol) in DCM (20 mL) was added (exothermic) and stirring was continued for 1 h. Et3N (4.44 g, 44 mmol) in DCM (20 mL) was added. The mixture was allowed to warm to r.t., water (50 mL) was added and the organic layer was evaporated. The residue was redissolved in Et2O (150 mL) and was stirred with 2N HCl (20 mL) for 24 h. Filtration afforded 6.61 g of 4 (84%). A solution of 4 (2 g, 11 mmol) in anhyd EtOH (50 mL) was stirred and refluxed with W-2 Raney nickel (12 g) for 2 h. The supernatant and the washings were evaporated and the residue was dissolved in DCM (20 mL). Drying and evaporation gave 1.13 g of 5 (76%), mp 116–117 C.

【Gassman PG, J Am Chem Soc, 1974, 96, 5506】

相關(guān)文獻(xiàn)

1 Gassman PG J Am Chem Soc 1973 95 2718

2 Gassman PG J Am Chem Soc 1974 96 5506

3 Johnson PD J Org Chem 1990 55 1374

4 Wright SM Tet Lett 1996 37 4631

5 Teng D Molecules 2006 11 700

6 Yu Y J Combin Chem 2007 9 566

編譯自：Organic Syntheses Based On Name Reactions, 3RdEd, A. Hassner, Page 177.

相關(guān)反應(yīng)

Gassman吲哚合成反應(yīng)