Synthesis of 2-Hydroxymethyl-1H-imidazoles from 1,3-Dihydroimidazole-2-thiones

Abstract

1,3-Dihydroimidazole-2-thiones 1a-d were desulfurized by hydrogen peroxide in either acid or neutral medium to afford 1H-imidazoles 3a-d. Reaction of 3b,d with dimethylsulfamoyl chloride furnished N,N-dimethylsulfamoylimidazoles 5 and 6a,b. Lithiation of 5 and 6a,b followed by formylation and reduction yielded the 2-hydroxymethyl derivatives 7 and 8a,b. 4-Alkyl-5-cyclohexylmethyl-1H-imidazol-2-yl)methanols 9a,b were obtained by hydrolysis of 7 and 8a,b.

Key words

1,3-dihydroimidazole-2-thiones - desulfurization - imidazole-2-sulfinic acids - 2-hydroxymetylimidazoles

References

• 1 Belen’kii LI. In Chemistry of Organosulfur Compounds: General Problems   Belen’kii LI. Ellis Horwood; Chichester: 1990.  Chap. 9.
• 2 Becker S. Fort Y. Vanderesse R. Caubère P. J. Org. Chem.  1989,  54:  4848 
• 3 Luh T.-Y. Ni Z.-J. Synthesis  1990,  89 
• 4 Capps HH. Dehn WM. J. Am. Chem. Soc.  1932,  54:  4301 
• 5 Ainsworth C. Org. Synth., Coll Vol. V   Wiley; New York: 1973.  p.1070 
• 6 Kim YH. Yon GH. J. Chem. Soc., Chem. Commun.  1983,  715 
• 7 Kim YH. Kim HJ. Yon GH. J. Chem. Soc., Chem. Commun.  1984,  1064 
• 8 Crestini C. Saladino R. Nicoletti R. Tetrahedron, Lett.  1993,  34:  1631 
• 9 Claudia C. Mincione E. Saladino R. Nicoletti R. Tetrahedron  1994,  50:  3259 
• 10 Abdou WM. Sidky MM. Wamhoff H. Z. Naturforsch., B: Chem. Sci.  1987,  42:  1153 
• 11 Crank G. Nursyidi A. J. Photochem. Photobiol. A: Chem.  1992,  64:  263 
• 12 Evans RM. Jones PG. Palmer PJ. Stephens FF. J. Chem. Soc.  1956,  4106 
• 13 Kalm MJ. J. Org. Chem.  1961,  26:  2925 
• 14 Song Z. DeMarco A. Zhao M. Corley EG. Thompson AS. McNamara J. Li Y. Rieger D. Sohar P. Mathre DJ. Tschaem DM. Reamer RA. Huntington MF. Ho G.-J. Tsay F.-R. Emerson K. Shuman R. Grabowski JJ. Reider PJ. J. Org. Chem.  1999,  39:  375 
• 15 Bullerwell RAF. Lawson A. J. Chem. Soc.  1952,  1350 
• 16 Loksha YM. Jørgensen PT. Pedersen EB. El-Badawi MA. El-Barbary AA. Nielsen C. J. Heterocycl. Chem.  2002,  39:  375 
• 17 Loksha YM. El-Badawi MA. El-Barbary AA. Pedersen EB. Nielsen C. Arch. Pharm. Pharm. Med. Chem.  2003,  336:  175 
• 18 Bredereck H. Gompper R. Reich F. Chem. Ber.  1960,  93:  723