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DOI: 10.1055/s-2006-951491
Direct and Facile Oxidative Conversion of Primary, Secondary, and Tertiary Amines to Their Corresponding Nitriles
Publikationsverlauf
Publikationsdatum:
22. September 2006 (online)
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Abstract
Molecular iodine in aqueous ammonia at 60 °C efficiently oxidized various primary, secondary, and tertiary amines to their corresponding nitriles in good yields.
Key words
amines - iodine - nitriles - aqueous ammonia
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1a
Cohen MA.Sawden J.Turner NJ. Tetrahedron Lett. 1990, 31: 7223 -
1b
Murahashi S.-I. Synthesis from Nitriles with Retention of the Cyano Group, In Science of Synthesis Vol. 19:Murahashi S.-I. Georg Thieme Verlag; Stuttgart: 2004. p.345-402 -
1c
Collier SJ.Langer P. Applications of Nitriles as Reagents for Organic Synthesis with Loss of the Nitrile Functionality (Including Cycloaddition Reactions), In Science of Synthesis Vol. 19:Murahashi S.-I. Georg Thieme Verlag; Stuttgart: 2004. p.403-425 - 2
Fabiani ME. Drug News Perspect. 1999, 12: 207 - 3
Comprehensive Organic Transformation
Larock RC. VCH Publishers, Inc./VCH Verlagsgesellschaft; New York/Weinheim: 1989. p.976-993 -
4a
Clarke TG.Hampson NA.Lee JB.Morley JR.Scanlon B. Tetrahedron Lett. 1968, 5685 -
4b
Vargha L.Remenyi M. J. Chem. Soc. 1951, 1068 -
4c
Cason J. Org. Synth., Coll. Vol. III Wiley; New York: 1955. p.3 -
4d
Mihailović ML.Stojiljković A.Andrejević V. Tetrahedron Lett. 1965, 461 -
4e
Stojiljković A.Andrejević V.Mihailović ML. Tetrahedron 1967, 23: 721 -
4f
Below JS.Garza C.Mathieson JW. J. Chem. Soc. D 1970, 634 -
4g
Troyanskii EI.Svitanko IV.Ioffe VA.Nikishin GI. Izv. Akad. Nauk SSSR, Ser. Khim. 1982, 2180 -
4h
Yamazaki S.Yamazaki Y. Bull. Chem. Soc. Jpn. 1990, 63: 301 -
4i
Biondini D.Brinchi L.Germani R.Goracci L.Savelli G. Eur. J. Org. Chem. 2005, 3060 -
4j
Chen E.Peng Z.Fu H.Liu J.Shao L. J. Chem. Res., Synop. 1999, 726 -
4k
Lee GA.Freedman HH. Tetrahedron Lett. 1976, 1641 -
4l
Yamazaki S. Synth. Commun. 1997, 27 -
4m
Jursic B. J. Chem. Res., Synop. 1988, 168 -
4n
Nikishin GI.Troyanskii EI.Joffe VA. Izv. Akad. Nauk SSSR, Ser. Khim. 1982, 2758 -
4o
Kametani T.Takahashi K.Ohsawa T.Ihara M. Synthesis 1977, 245 -
4p
Capdevielle P.Lavigne A.Maumy M. Synthesis 1989, 453 -
4q
Capdevielle P.Lavigne A.Sparfel D.Baranne-Lafont J.Nguyen KC.Maumy M. Tetrahedron Lett. 1990, 31: 3305 -
4r
Maeda Y.Nishimura T.Uemura S. Bull. Chem. Soc. Jpn. 2003, 76: 2399 -
4s
Tang R.Diamond SE.Neary N.Mares F. J. Chem. Soc., Chem. Commun. 1978, 562 -
4t
Schröder M.Griffith WP. J. Chem. Soc., Chem. Commun. 1979, 58 -
4u
Bailey AJ.James BR. Chem. Commun. 1996, 2343 -
4v
Mori K.Yamaguchi K.Mizugaki T.Ebitani K.Kaneda K. Chem. Commun. 2001, 461 -
4w
Yamaguchi K.Mizuno N. Angew. Chem. Int. Ed. 2003, 42: 1480 -
4x
Moriarty RM.Vaid RK.Duncan MP.Ochiai M.Inenaga M.Nagao Y. Tetrahedron Lett. 1988, 29: 6913 -
4y
Chen F.Kuang Y.Dai H.Lu L.Huo M. Synthesis 2003, 2629 -
5a
Mori N.Togo H. Synlett 2004, 880 -
5b
Mori N.Togo H. Tetrahedron 2005, 61: 5915 - 6
Mori N.Togo H. Synlett 2005, 1456 - 7
Ishihara M.Togo H. Synlett 2006, 227 - 8
Goosen A.McCleland CW.Sipamla AM. J. Chem. Res. (M) 1995, 311
References and Notes
Oxidative Conversion of Primary Amines to Nitriles; Typical Procedure: To a mixture of 4-methylbenzylamine (121.2 mg, 1 mmol) and aq NH3 (3.0 mL, 45 mmol) under an empty balloon was added I2 (533.0 mg, 2.1 mmol) at r.t. The resulting mixture was stirred at 60 °C. After 2 h at the same temperature, the reaction mixture was quenched with H2O (20 mL) and a sat. aq solution of Na2SO3 (3 mL) at 0 °C. The product was extracted with Et2O (3 × 15 mL). The organic layer was washed with brine and dried over Na2SO4 to provide p-tolunitrile in 80% yield in an almost pure state. If necessary, the product was purified by column chromatography (silica gel; hexane-EtOAc, 4:1) to give pure p-tolunitrile as a colorless solid; mp 25 °C. IR (NaCl): 2230 cm-1. 1H NMR (400 MHz, CDCl3): δ = 2.42 (3 H, s), 7.27 (2 H, d, J = 7.9 Hz), 7.55 (2 H, d, J = 7.9 Hz). The identity of the product was confirmed by comparison of its analytical data with a sample of the commercially available authentic compound.Oxidative Conversion of Tertiary Amines to Nitriles; Typical Procedure: To a mixture of N,N-dimethyl-3-phenylpropylamine (163.2 mg, 1 mmol) and aq NH3 (3.0 mL, 45 mmol) under an empty balloon was added I2 (888.3 mg, 3.5 mmol) at r.t. The resulting mixture was stirred at 60 °C. After 0.5 h at the same temperature, the reaction mixture was quenched with H2O (20 mL) and a sat. aq solution of Na2SO3 (3 mL) at 0 °C. The product was extracted with Et2O (3 × 15 mL). The organic layer was washed with brine and dried over Na2SO4 to provide 3-phenylpropionitrile in 71% yield in an almost pure state. If necessary, the product was purified by column chromatog-raphy (silica gel; (hexane-EtOAc, 4:1) to give pure 3-phenylpropionitrile as a colorless oil. IR (NaCl): 2250 cm-1. 1H NMR (400 MHz, CDCl3): δ = 2.62 (2 H, t, J = 7.4 Hz), 2.96 (2 H, t, J = 7.4 Hz), 7.23 (2 H, d, J = 8.1 Hz), 7.28 (1 H, t, J = 8.2 Hz) 7.34 (2 H, t, J = 8.2 Hz). The identity of the product was confirmed by comparison of its analytical data with a sample of the commercially available authentic compound.Oxidative Conversion of Tris(4-methylbenzyl)amine to p -Tolunitrile: To a mixture of tris(4-methylbenzyl)amine (329.5 mg, 1 mmol) and aq NH3 (3.0 mL, 45 mmol) under an empty balloon was added I2 (1.650 g, 6.5 mmol) at r.t. The resulting mixture was stirred at 60 °C. After 4 h at the same temperature, the reaction mixture was quenched with H2O (20 mL) and a sat. aq solution of Na2SO3 (3 mL) at 0 °C. The product was extracted with Et2O (3 × 15 mL). The organic layer was washed with brine and dried over Na2SO4 to provide p-tolunitrile in 84% yield in an almost pure state. If necessary, the product was purified by column chromatog-raphy (silica gel; hexane-EtOAc, 4:1) to give pure p-tolu-nitrile as a colorless solid; mp 25 °C. IR (NaCl): 2230 cm-1. 1H NMR (400 MHz, CDCl3): δ = 2.42 (3 H, s), 7.27 (2 H, d, J = 7.9 Hz), 7.55 (2 H, d, J = 7.9 Hz).