【Atherton, F. R. et al. J. Chem. Soc. 1945, 660. DOI:10.1039/jr9450000660】
反应机理
碱先拔掉亚磷酸二酯的氢，形成的亚磷酸二酯负离子进攻四氯化碳得到产物。
文献报道还有另外一种机理，利用叔胺做碱时，在反应引发阶段胺并不是拔氢而是先烷基化。【Phosphorus, Sulfur & Silicon and Related Elements, 1993, 83, 157】
反应实例
【Atherton, F. R.; Openshaw, H. T. and Todd, A. R., J. Chem. Soc., 1945, 660】
Diethyl N-phenylphosphoramide (4). To an ice cold stirred suspension of formylanilide 1 (605 mg,5 mmol) in CCl4 (25 mL) was added 30% NaOH (10 mL) and TEBAB (0.2 g). Diethyl phosphite 2(828 mg, 6 mmol) in CCl4 (5 mL) was added dropwise. After 1 h at 0 ℃ and 4 h at 20 ℃, the organic layer gave 4, after crystallization, 0.687 g (60%), mp 96–97 ℃.
【Lukanow LK, Synthesis, 1985, 671】
【J. Med. Chem., 2002, 45, 5797】
Diethyl phophoramide (5). Into vigorously stirred liquid NH3 (15–20 mL), 1.0 mmol of iodoform and 1.1 equiv of dialkyl phosphite 2 were added simultaneously at 33 C. After 5–10 min of stirring at 33 C, the cooling bath was removed and stirring was continued until NH3 was distilled off. The product was dissolved in dry chloroform and the mixture was filtered through Celite. After evaporation of the solvent, crystallization or distillation afforded 5 (83%).
【Mielniczak G, Syn Comm., 2003, 33, 3851】
【Chen H, Huang Z, Hu X, Tang G, Xu P, Zhao Y, Cheng C-H. J. Org. Chem. 2011, 76, 2338. DOI: 10.1021/jo2000034】
相关文献
1 Atherton FR, Todd AR J Chem Soc 1945 660
2 Wadsworth WS J Am Chem Soc 1962 64 1316
3 Zwierzak A Synthesis 1982 922
4 Lukanow LK Synthesis 1985 671
5 Hovalla D Tet Lett 1992 33 2817
6 Garrigue B Syn Comm 1995 25 871
7 Liu LZ Org Prep Proc Int 1996 28 490
8 Zhao YF J Chem Res S 2003 262
9 Mielniczak G Syn Comm 2003 33 3851
10 Zhao YF Synlett 2005 1927
11 Ju Y Synthesis 2007 407
12 Donghi M Bioorg Med Chem Lett 2009 19 1392
13 Jaffrès, P.-A. et al, Beilstein J. Org. Chem. 2014, 10, 1166. DOI: 10.3762/bjoc.10.117
参考文献
一、Organic Syntheses Based On Name Reactions, 3RdEd, A. Hassner, 14.
二、化学空间：https://cn.chem-station.com/reactions/%e5%8f%96%e4%bb%a3%e5%8f%8d%e5%ba%94/2015/02/atherton-todd%e5%8f%8d%e5%ba%94atherton-todd-reaction.html
三、Comprehensive Organic Name Reactions and Reagents, by Zerong Wang，114-118
