Simple microwave-assisted method for the synthesis of primary thioamides from nitriles

Synlett

Volumn , Issue 14, 2004, Pages 2615-2617

  Bagley, Mark C ^a   Chapaneri, Krishna ^a   Glover, Christian ^a   Merritt, Eleanor A ^a  

^a CARDIFF UNIVERSITY   (United Kingdom)

Author keywords

Microwaves; Nitriles; Thioamides

Indexed keywords

AMMONIUM SULFATE; AROMATIC NITRO COMPOUND; METHANOL; NITRILE; SULFIDE; THIOAMIDE;

ANALYTIC METHOD; ARTICLE; CHROMATOGRAPHY; HYPERBARISM; MICROWAVE RADIATION; PRODUCTIVITY; PURIFICATION; SYNTHESIS;

EID: 9644268880     PISSN: 09365214     EISSN: None     Source Type: Journal    
DOI: 10.1055/s-2004-834812     Document Type: Article

References (37)

1. (a) Takahata, H.; Yamazaki, T. Heterocycles 1988, 27, 1953.
2. (b) Hurd, R. N.; Delamater, G. T. Chem. Rev. 1961, 61, 45.
3. Brillon, D. Sulfur Rep. 1992, 12, 297.
4. Cava, M. P.; Levinson, M. I. Tetrahedron 1985, 41, 5061.
5. Hartke, K.; Gerber, H.-D. J. Prakt. Chem. 1996, 338, 763.
6. Charette, A. B.; Grenon, M. J. Org. Chem. 2003, 68, 5792.
7. Walter, W.; Bode, K. D. Angew. Chem., Int. Ed. Engl. 1996, 5, 447.
8. Fairfull, A. E. S.; Lowe, J. L.; Peak, D. A. J. Chem. Soc. 1952, 742.
9. (a) Kindler, K. Liebigs Ann. Chem. 1923, 431, 187.
10. (b) Wang, C.-H.; Hwang, F.-Y.; Horng, J.-M.; Chen, C.-T. Heterocycles 1979, 12, 1191.
11. Gabriel, S.; Heymann, P. Ber. Dtsch. Chem. Ges. 1890, 23, 157.
12. Erlenmeyer,H.;Degen, K. Helv. Chim. Acta 1946, 29, 1080.
13. Albert, A. Ber. Dtsch. Chem. Ges. 1915, 48, 470.
14. Taylor, E. C.; Zoltewicz, J. A. J. Am. Chem. Soc. 1960, 82, 2656.
15. Liboska, R.; Zyka, D.; Bobek, M. Synthesis 2002, 1649.
16. Brillon, D. Synth. Commun. 1992, 22, 1397.
17. Shiao, M. J.; Lai, L. L.; Ku, W. S.; Lin, P. Y.; Hwu, J. R. J. Org. Chem. 1993, 58, 4742.
18. Reviews on microwave chemistry include: (a) Gabriel, C.; Gabriel, S.; Grant, E. H.; Halstead, B. S. J.; Mingos, D. M. P. Chem. Soc. Rev. 1998, 27, 213.
19. (b) Kuhnert, N. Angew. Chem. Int. Ed. 2002, 41, 1863.
20. (c) Lidström, P.; Tierney, J.; Wathey, B.; Westman, J. Tetrahedron 2001, 57, 9225.
21. (d) Loupy, A.; Petit, A.; Hamelin, J.; Texier-Boullet, F.; Jacquault, P.; Mathé, D. Synthesis 1998, 1213.
22. (e) Galema, S. A. Chem. Soc. Rev. 1997, 26, 233.
23. (f) Caddick, S. Tetrahedron 1995, 51, 10403.
24. (g) Strauss, C. R.; Trainor, R. W. Aust. J. Chem. 1995, 48, 1665.
25. (h) Microwaves in Organic Synthesis; Loupy, A., Ed.; Wiley VCH: Weinheim, 2002.
26. Zbruyev, O. I.; Stiasni, N.; Kappe, C. O. J. Comb. Chem. 2003, 5, 145.
27. Varma, R. S.; Kumar, D. Org. Lett. 1999, 1, 697.
28. Bagley, M. C.; Dale, J. W.; Jenkins, R. L.; Bower, J. Chem. Commun. 2004, 102.
29. Bagley, M. C.; Dale, J. W.; Xiong, X.; Bower, J. Org. Lett. 2003, 5, 4421.
30. 4) and evaporated in vacuo to give thioamide 2.
31. 4) and evaporated in vacuo to give thioamide 2.
32. Feiring, A. E. J. Org. Chem. 1976, 41, 148.
33. Walter, W.; Curts, J. Chem. Ber. 1960, 93, 1511.
34. Inami, K.; Shiba, T. Bull Chem. Soc. Jpn. 1985, 58, 352.
35. The nitriles depicted in Figure 1 gave only unreacted starting material under ambient and microwave-assisted conditions, according to methods A and B, respectively, except for acrylonitrile which instead reacted by conjugate addition with ammonium sulfide.
36. The reaction of 2-cyanopyridine(1a) with ammonium sulfide according to method A has been conducted on a larger scale (10 mmol) to give thioamide 2a without any reduction in yield.
37. With a volatile aliphatic nitrile, such as 1c, evaporation in vacuo after an aqueous work-up removed unreacted starting material. For reactions that were not quantitative, purification by column chromatography on silica was usually required. For experiments that gave >98% yield (Table 2, entries 1-5, 10, 14, 15, and 26), no purification on silica or recrystallisation of the product was necessary.