One-Pot Synthesis of Imidazolidine-2-Thiones, Hydantoins and Thiohydantoins under Solvent-Free and Grinding Conditions

Mohammad M. Ghanbari^1*, Zahra Roohi¹, Javad Safari²

¹Young Researchers and Elite Club, Sarvestan Branch, Islamic Azad University, Sarvestan, Iran.
²Department of Chemistry, Faculty of Science, University of Kashan, Kashan, Iran.

DOI: 10.4236/oalib.1100705                

Abstract

A convenient, environmentally friendly and mild green synthesis of imidazolidine-2-thiones, hy-dantoin and thiohydantoin derivatives was developed by the one-pot reaction of benzils, urea or thiourea derivatives, and strong base at with grinding. The key advantages are the short reaction times, excellent yields, simple workup, and easy purification in the solvent-free condition. The present method aimed to overcome the limitations and drawbacks of the reported methods such as hard work-up, low yield, hazardous solvent and long reaction time.

Keywords

Green Synthesis, Imidazolidine-2-Thiones, Hydantoin, Thiohydantoin, Grinding, Solvent-Free

Conflicts of Interest

The authors declare no conflicts of interest.

References

[1]	Colacino, E., Lamaty, F., Martinez, J. and Parrot, I. (2007) Microwave-Assisted Solid-Phase Synthesis of Hydantoin Derivatives. Tetrahedron Letters, 48, 5317-5320. http://dx.doi.org/10.1016/j.tetlet.2007.05.084
[2]	Chenga, C.-K., Wu, J., Liu, Y., Lee, T.-S., Kang, S.-J., Sheu, M.-T. and Lee, W.-S. (2008) Structure and Anti-Proliferation Function of 5,5-Diphenyl-2-Thiohydantoin (DPTH) Derivatives in Vascular Endothelial Cells. Vascular Pharmacology, 48, 138-142. http://dx.doi.org/10.1016/j.vph.2008.01.007
[3]	Nefzi, A., Giulianotti, M.A. and Houghten, R.A. (2000) Solid-Phase Synthesis of Branched Thiohydantoin Benzimidazolinethiones and Branched Thiohydantoin Tetrahydroquinoxalinediones. Tetrahedron Letters, 41, 2283-2287. http://dx.doi.org/10.1016/S0040-4039(00)00162-3
[4]	Katritzky, A.R., Strah, S. and Belyakov, S.A. (1998) The Preparation of Functionalized Amines and Amides Using Benzotriazole Derivatives and Organozinc Reagents. Tetrahedron, 54, 7167-7178. http://dx.doi.org/10.1016/S0040-4020(98)00353-6
[5]	Kumar, R. and Chauhan, P.M.S. (2008) A One-Pot Chemoselective S-Alkylation and Acetylation of Thiohydantoins Using the Alkyl Orthoformate-ZnCl2-Ac2O Reagent System. Tetrahedron Letters, 49, 5475-5479. http://dx.doi.org/10.1016/j.tetlet.2008.07.020
[6]	Moshtaghi, Z.A. and Moghani, D. (2011) Synthesis of 1,4-Dihydropyridine Derivatives under Solvent-Free and Grinding Conditions. Synthetic Communications, 41, 2152-2160. http://dx.doi.org/10.1080/00397911.2010.499488
[7]	Safari, J., Naeimi, H., Ghanbari, M.M. and Sabzi-Fini, O. (2009) Preparation of Phenytoin Derivatives under SolventFree Conditions Using Microwave Irradiation. Russian Journal of Organic Chemistry, 45, 477-479. http://dx.doi.org/10.1134/S1070428009030270
[8]	Safari, J., Arani, N.M. and Isfahani, A.R. (2010) Ultrasound-Enhanced Green Synthesis of 5,5-Diphenylhydantoin Derivatives Using Symmetrical or Unsymmetrical Benzils. Chinese Journal of Chemistry, 28, 255-258. http://dx.doi.org/10.1002/cjoc.201090062
[9]	Arani, N.M. and Safari, J. (2011) A Rapid and Efficient Ultrasound-Assisted Synthesis of 5,5-Diphenylhydantoins and 5,5-Diphenyl-2-Thiohydantoins. Ultrasonics Sonochemistry, 18, 640-643. http://dx.doi.org/10.1016/j.ultsonch.2010.09.001
[10]	Ghanbari, M.M., Mahdavinia, G.H., Safari, J., Naeimi, H. and Zare, M. (2010) Microwave-Assisted Solid-Phase Synthesis of 4,5-Dihydroxy-1,3-Dialkyl-4,5-Diarylimidazolidine-2-Thione and Thiohydantoins. Synthetic Communications, 41, 2414-2420. http://dx.doi.org/10.1080/00397911.2010.503000
[11]	Muccioli, G.G., Poupaert, J.H., Wouters, J., Norberg, B., Poppitz, W., Scriba, G.K.E. and Lambert, D.M. (2003) A Rapid and Efficient Microwave-Assisted Synthesis of Hydantoins and Thiohydantoins. Tetrahedron, 59, 1301-1307. http://dx.doi.org/10.1016/S0040-4020(03)00033-4
[12]	Yavari, I., Ghanbari, M.M., Azizian, J. and Sheikholeslami, F. (2011) A One-Pot Synthesis of Functionalised 1-Azadienes Containing 2-Thioxoimidazolidin-4-Ones. Journal of Chemical Research, 35, 87-88. http://dx.doi.org/10.3184/174751911X12964930076520
[13]	Ghanbari, M.M. (2011) Three-Component Reaction between 5,5-Diarylthiohydantoins and Acetylenic Esters in the Presence of Trialkyl Phosphite. Chemical Monthly, 142, 794-752.
[14]	Yavari, I., Ghanbari, M.M., Shahvelayati, A.S. and Ghazvini, M. (2010) Chemoselective Synthesis of Functionalized 2,5-Dihydro-5,5-diaryl-2-thioxo-1H-imidazoles from 5,5-Diarylthiohydantoins, Activated Acetylenes, and Ph3P. Phosphorus, Sulfur, and Silicon, 185, 2551-2557. http://dx.doi.org/10.1080/10426501003752179
[15]	Butler, A.R. and Broan, J. (1989) Mechanistic Studies in the Chemistry of Thiourea. Part 1. Reaction with Benzil under Alkaline Conditions. Journal of the Chemical Society Perkin Transactions 2, 731-740.