A new and convenient method of generating alkyl isocyanates from alcohols, thiols, and trimethylsilyl ethers using a 2,4,6-trichloro [1,3,5] triazine/n-$Bu_4NOCN$

Alkyl isocyanates are prepared in good to excellent yields by treatment of alcohols, thiols, and trimethylsilyl ethers with 2,4,6-trichloro[l,3,5] triazine/n-Bu4NOCN in acetonitrile. This method is highly selective for conversion of 1° alcohols to alkyl isocyanates in the presence of 2° and 3° alcohols, thiols, and trimethylsilyl ethers.

PDF

___

1. H. Ulrich, "Chemistry and Technology of Isocyanates", Wiley, New York (1996).
2. S. Ozaki, Chem. Rev. 72, 457-69 (1977).
3. B.A. Arbuzov and N.N. Zobova, Synthesis. 7, 433-50 (1982).
4. W. Hentschel, Chem. Ber. 17, 1284 (1884).
5. S. Werner, Annalen. 562, 75 -136 (1949).
6. R.J. Slocombe, E.E. Hardy, J.H. Saunder and R.L. Jenkins, J. Am. Chem. Soc. 72, 1888-89 (1950).
7. K. Kurita and Y. Iwakura, J. Org. Chem. 41, 2070-71 (1976).
8. K. Kurita and Y. Iwakura, Org. Synth. Coll. 6, 715-19 (1988).
9. H. Eckert and B. Forster, Angew. Chem., Int. Ed. Engl. 26, 894-95 (1987).
10. L. Cotarca, P. Delogu, A. Nardelli and C.V. Sunji, Synthesis. 553-76 (1996).
11. H.R. Kricheldorf, Synthesis. 649-50 (1970).
12. H.R. Kricheldorf, Angew. Chem. 84, 107 (1972).
13. M. Sakamoto, M. Mochizuki and M. Yoshioka, JP10072428 (1998).
14. G. Greber and H.R. Kricheldorf, Angew. Chem. 80, 1028-29 (1968).
15. H.A. Staab and W. Benz, Angew. Chem. 73, 66 (1961).
16. R. Bonjouklian and R.A. Ruden, J. Org. Chem. 42, 4095-4103 (1977).
17. C. Kaiser and J. Weinstock, Org. Synth. 51, 48 (1971).
18. S. Heyden and G. Wilbert, Chem. Ind. 33, 1406 (1967).
19. S. Bittner, S. Grinberg and I. Kartoon, Tetrahedron Lett. 15, 1965-68 (1974).
20. F.A. Daniher, J. Org. Chem. 34, 2908-11 (1969).
21. N. Iranpoor, H. Firouzabadi, Gh. Aghapour and A.R. Vaezzade, Tetrahedron. 58, 8689-93 (2002).
22. N. Iranpoor, H. Firouzabadi, B. Akhlaghinia and N. Nowrouzi, J. Org. Chem. 69, 2562-64 (2004).
23. N. Iranpoor, H. Firouzabadi, B. Akhlaghinia, and N. Nowrouzi, Tetrahedron Lett. 45, 3291-94 (2004).
24. B. Akhlaghinia and A.R. Pourali, Synthesis. 1747-49 (2004).
25. B. Akhlaghinia, Phosphorous, Sulfur Silicon Rel. 179, 1783-86 (2004).
26. B. Akhlaghinia, Phosphorous, Sulfur Silicon Rel .180,1601-04 (2005).
27. B. Akhlaghinia, Synthesis. 1955-58 (2005).
28. B. Akhlaghinia and E. Roohi, Lett. Org. Chem. 2, 725-30 (2005).
29. B. Akhlaghinia and E. Roohi, Lett. Org. Chem. 3, 220-24 (2006).
30. K. Venkataraman and D.R. Wagle, Tetrahedron Lett. 20,3037-40 (1979).
31. Z.J. Kaminski, P. Paneth and J. Rudzinski, J. Org. Chem. 63, 4248-55 (1998).
32. J.E. Kaminska, Z.J. Kaminski and J. Gora, Synthesis. 593-96 (1999).
33. S. Masala and M. Taddei, Org. Lett. 1355-57 (1999).
34. L. De Luca, G. Giacomelli and M. Taddei, J. Org. Chem. 66, 2534-37 (2001).
35. M. Falorni, A. Porcheddu and M. Tadei, Tetrahedron Lett. 40, 4395-96 (1999).
36. M. Falorni, G. Giacomelli, A. Porcheddu and M. Taddei, J. Org. Chem. 64, 8962-64 (1999).
37. L. De Luca, G. Giacomelli and A. Porcheddu, Org. Lett. 4, 553-55 (2002).
38. B.P. Bandgar and S. Pandit, Tetrahedron Lett. 43, 3413-14 (2002).