A New and Convenient Method of Generating Alkyl Isocyanates from Alcohols­, Thiols and Trimethylsilyl Ethers Using Triphenylphosphine/2,3-Dichloro-5,6-dicyanobenzoquinone/Bu₄NOCN

Abstract

Alkyl isocyanates are prepared in good to excellent yields by treatment of alcohols, thiols and trimethylsilyl ethers with triphenylphosphine/2,3-dichloro-5,6-dicyanobenzoquinone/Bu₄NOCN in acetonitrile. This method is highly selective for conversion of primary alcohols to alkyl isocyanates in the presence of secondary and tertiary alcohols, thiols and trimethysilyl ethers.

Key words

triphenylphosphine - 2,3-dichloro-5,6-dicyanobenzoquinone - alcohol - thiol - trimethylsilyl ether - alkyl isocyanate

References

• Books and reviews on isocyanates:
• 1a Ulrich H. Chemistry and Technology of Isocyanates   Wiley; New York: 1996. 
• 1b Ozaki S. Chem. Rev.  1977,  72:  457 
• 1c Arbuzov BA. Zobova NN. Synthesis  1982,  433 
• 2a Hentschel W. Ber. Dtsch. Chem. Ges.  1884,  17:  1284 
• 2b Werner S. Liebigs Ann. Chem.  1949,  562:  75 
• 2c Slocombe RJ. Hardy EE. Saunder JH. Jenkins RL. J. Am. Chem. Soc.  1950,  72:  1888 
• 3a Kurita K. Iwakura Y. J. Org. Chem.  1976,  41:  2070 
• 3b Kurita K. Iwakura Y. Org. Synth. Coll. Vol. VI   Wiley; New York: 1988.  p.715 
• 4a Eckert H. Forster B. Angew. Chem., Int. Ed. Engl.  1987,  26:  894 
• 4b Cotarca L. Delogu P. Nardelli A. Sunji CV. Synthesis  1996,  553 
• 5a Kricheldorf HR. Synthesis  1970,  649 
• 5b Kricheldorf HR. Angew. Chem., Int. Ed. Engl.  1972,  11:  128 
• 5c Sakamoto M, Mochizuki M, and Yoshioka M. inventors; Japanese Patent  10072428.  ; Chem. Abstr. , 129,
• 6 Greber G. Kricheldorf HR. Angew. Chem., Int. Ed. Engl.  1968,  7:  941 
• 7 Staab HA. Benz W. Angew. Chem.  1961,  73:  66 
• 8a Bonjouklian R. Ruden RA. J. Org. Chem.  1977,  42:  4095 
• 8b Kaiser C. Weinstock J. Org. Synth.  1971,  51:  48 
• 8c Heyden S. Wilbert G. Chem. Ind. (London)  1967,  1406 
• 9a Bittner S. Grinberg S. Kartoon I. Tetrahedron Lett.  1974,  15:  1965 
• 9b Daniher FA. J. Org. Chem.  1969,  34:  2908 
• 10a Iranpoor N. Firouzabadi H. Aghapour Gh. Vaezzade AR. Tetrahedron  2002,  58:  8689 
• 10b Iranpoor N. Firouzabadi H. Akhlaghinia B. Nowrouzi N. J. Org. Chem.  2004,  69:  2562 
• 10c Iranpoor N. Firouzabadi H. Akhlaghinia B. Nowrouzi N. Tetrahedron Lett.  2004,  45:  3291 
• 10d Akhlaghinia B. Pourali AR. Synthesis  2004,  1747 
• 10e Akhlaghinia B. Phosphorous, Sulfur Silicon Rel. Elem.  2004,  179:  1783 
• 10f Akhlaghinia B. Phosphorous, Sulfur Silicon Rel. Elem.  2005,  180:  in press 
• 11a Wang W. Li Y. Attardo G. J. Org. Chem.  1997,  62:  6598 
• 11b Becker HD. Bjork A. Adler EJ. J. Org. Chem.  1980,  45:  1596