由胺製備腈

腈的製備方法有很多，本號在之前文章中匯總過【腈的製備匯總】。由伯胺脫氫可以直接得到腈，此類反應也是很好製備腈的方法。常見的製備方法有：一、碘/氨水在60℃中可以將伯胺、仲胺和叔胺氧化為腈【317】；

二、2-碘醯基苯甲酸 (IBX)/碘在DMSO中65℃反應【318】；六、重鉻酸菸鹼（nicotinium dichromate） 【322】；八、碘/DIH(1,3-diiodo-5,5-dimethylhydantoin)/氨水條件下，伯胺和伯醇都可以轉化為腈【324】。

最近幾年也文獻報導其他由伯胺製備腈的方法。如NNN/Ru(II)催化下伯胺和仲胺脫氫生成腈和亞胺並放出氫氣【326】。氮氧化物鹽氧化伯胺得到腈【327】   。DL-蘇氨酸和水楊醛反應得到席夫鹼，接著和Fe絡合生成離子液體，其作為綠色催化劑，在無溶劑有氧條件下氧化伯胺得到腈【328】。有文獻報導釩絡合催化劑在離子液體中可以氧化伯胺得到腈，另外還有銅催化的過氧化氫水溶液氧化方法和鋅類絡合物催化的光誘導氧氣氧化法【329】。

相關實例

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】

參考文獻

317 Iida, S.; Togo, H. Synlett 2006, 2633. 

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. 

322 Sobhani, S.; Aryanejad, S.; Maleki, M.F. Helv. Chim. Acta 2012, 95, 613. 

323 Yamaguchi, K.; Mizuno, N. Angew. Chem. Int. Ed. 2003, 42, 1480. 

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. 

編譯自：March’s advanced organic chemistry : reactions, mechanisms, and structure.  Eighth edition / Michael B Smith，P1460-1461.