Freunderberg-Schonberg硫酚合成

苯酚在硫代氨基甲酸酯化或者硫代碳酸酯化后，经过加热重排与水解合成硫酚的反应。

硫代碳酸酯：

硫代氨基甲酸酯：

反应机理

反应实例

O-p-t-Butylphenyl dimethylthiocarbamate (8). To dimethylthiocarbamoyl chloride 7 (21 g, 0.17 mol) in DMF (140 mL) at 14 C was added all at once dry sodium p-t-butylphenolate 6 (17.6 g, 0.1 mol) (exothermic, temp 26 C). The mixture was stirred for 1.5 h at 30–34 C, added to water (300 mL) and extracted with PhH/Skellysolve B (4:1). Workup, evaporation and recrystallization from MeOH (100 mL) afforded 21.4 g of 8 (95%), mp 97–99 C.

Pyrolysis. Heating 8 neat at 270 C until by TLC the starting material is absent, afforded 9 in a 95%yield.

p-t-Butylphenylthiol (10). A solution of 9 in MeOH was heated under N2 with excess NaOH to give 10 (85%), bp 102–105 C/7–8 mm.

【Newman RC， J Am Chem Soc， 1967， 89， 3412】

相关文献

1 Freundenberg K Chem Ber 1927 60 232

2 Schonberg A Chem Ber 1930 63 178

3 Schulenberg JW Org React 1965 14 1

4 Kwart R J Org Chem 1966 31 410

5 Newman MS J Org Chem 1966 31 3980

6 Newman RC J Am Chem Soc 1967 89 3412

7 Reeles HM J Org Chem 1968 33 2249

8 Kawata Chem Pharm Bull 1973 21 604

9 Wiersum UE J Org Chem 1989 54 5811

10 Newman, M. S.; Hetzel, F. W. Org. Synth. Coll. Vol. 6: 824 (1990)

参考文献

一、Organic Syntheses Based On Name Reactions, 3RdEd, A. Hassner, Page 165-166.

二、化学空间：https://cn.chem-station.com/reactions/2015/11/post-7553.html