由胺制备腈
最近几年也文献报道其他由伯胺制备腈的方法。如NNN/Ru(II)催化下伯胺和仲胺脱氢生成腈和亚胺并放出氢气【326】。氮氧化物盐氧化伯胺得到腈【327】 。DL-苏氨酸和水杨醛反应得到席夫碱，接着和Fe络合生成离子液体，其作为绿色催化剂，在无溶剂有氧条件下氧化伯胺得到腈【328】。有文献报道钒络合催化剂在离子液体中可以氧化伯胺得到腈，另外还有铜催化的过氧化氢水溶液氧化方法和锌类络合物催化的光诱导氧气氧化法【329】。
相关实例
Benzonitrile (Table 1, entry 1) To a flame-dried, nitrogen/argonflushed, 250-mL round bottom flask containing a magnetic stir bar wasadded 12.06 g (40 mmol) of 4-acetamido-2,2,6,6-tetramethylpiperidine1-oxoammoniumtetrafluoroborate (1), 150 mL of dry dichloromethane(distilled from calcium hydride just prior to use), and 6.33 g (80 mmol)of dry pyridine. A solution of benzylamine (1.070 g, 10 mmol) in 20 mL of dry dichloromethane (0.5 M)was then added by syringe pump at a rate of 20 mL per hour. The reaction, which was monitored byfollowing the colorimetric changes noted above, was stirred at room temperature for 12 hours. Themajority of the solvent was removed at room temperature on a rotary evaporator and 100 mL of diethylether was added to the resulting slurry. The mixture was stirred for 20 minutes to precipitate nitroxide 2,filtered through coarse filter paper directly into a separatory funnel, and the flask was rinsed with twoadditional 25-mL portions of diethyl ether. As detailed below, nitroxide 2 may be recovered from thesolid residue consisting of impure 2 and pyridinium tetrafluoroborate, and this material may be used toregenerate 1. The light orange ethereal solution was washed at least five times with 50-mL portions of 10% aq hydrochloric acid solution until the aqueous layer remained clear. The organic layer was rinsedwith 50 mL of saturated brine, dried over sodium sulfate, and filtered into a round bottom flask. Thesolution was concentrated under reduced pressure until ~ 10 mL remained to which 250-500 mg ofSilaBond® amine was added. The mixture was stirred for 1 hour to remove any aldehyde byproduct(typically 0 - 10% of aldehyde was generated due to residual moisture). The mixture was filtered througha pipette containing 0.500 g of silica gel using a 50% ether/pentane solution as an eluent. The solventwas removed to afford 0.946 g (91%) of the title compound as a light yellow oil.
【Org. Lett. 2014, 16, 6484】
参考文献
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318 Chiampanichayakul, S.; Pohmakotr, M.; Reutrakul, V.; Jaipetch, T.; Kuhakarn, C. Synthesis 2008, 2045.
319 Yamazaki, S. Synth. Commun. 1997, 27, 3559; Jursic, B. J. Chem. Res. (S) 1988, 168.
320 Leggio, A.; Belsito, E.L.; Gallo, S.; Liguori, A. Tetrahedron Lett. 2017, 58, 1512.
321 Natte, K.; Jagadeesh, R.V.; Sharif, M.; Neumann, H.; Beller, M. Org. Biomol. Chem. 2016, 14, 3356.
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324 Iida, S.; Togo, H. Tetrahedron 2007, 63, 8274.
325 Biondini, D.; Brinchi, L.; Germani, R.; Goracci, L.; Savelli, G. Eur. J. Org. Chem. 2005, 3060.
326 See Tseng, K.-N.T.; Szymczak, N.K. Synlett 2014, 25, 2385. Also see Biafora, A.; Patureau, F.W. Synlett 2014,25, 2525.
327 Lambert, K.M.; Bobbitt, J.M.; Eldirany, S.A.; Wiberg, K.B.; Bailey, W.F. Org. Lett. 2014, 16, 6484.
328 Varyani, M.; Khatri, P.K.; Jain, S.L. Tetrahedron Lett. 2016, 57, 723.
329 Marui, K.; Nomoto, A.; Akashi, H.; Ogawa, A. Synthesis 2016, 48, 31.
编译自：March’s advanced organic chemistry : reactions, mechanisms, and structure. Eighth edition / Michael B Smith，P1460-1461.