Abstract
An operationally simple and entirely green protocol for the synthesis of thiourea derivatives by the reaction of carbon disulfide with primary amines in pure water is developed. This reaction is a highly atom-economic process for production of highly pure, hindered thioureas without any catalyst and tedious work-up.
Similar content being viewed by others
References
Li CJ (2005) Organic reactions in aqueous media with a focus on carbon–carbon bond formations: a decade update. Chem Rev 105: 3095–3166. doi:10.1021/cr030009u
Manabe K, Limura S, Sun XM, Kobayashi S (2002) Dehydration reactions in water brønsted acid–surfactant-combined catalyst for ester, ether, thioether, and dithioacetal formation in Water. J Am Chem Soc 124: 11971–11978. doi:10.1021/ja026241j
Chankeshwara SV, Chakraborti AK (2006) Catalyst-free chemoselective N-tert-butyloxycarbonylation of amine. Org Lett 8: 3259–3262. doi:10.1021/ol0611191
Khatik GL, Kumar R, Chakraborti AK (2006) Catalyst-free conjugated addition of thiols to α, β-unsaturated carbonyl compounds in water. Org Lett 8: 2433–2436. doi:10.1021/ol060846t
Tobe Y, Sasaki SI, Mizuno M, Hirose K, Naemura K (1998) Novel self-assembly of m-xylylene type dithioureas by head-to-tail hydrogen bonding. J Org Chem 63: 7481–7489. doi:10.1021/jo980441p
Mamoru K, Hideharu I (2006) Thiourea and selenourea and their applications. Curr Org Synth 3: 439–455. doi:10.1107/S160053680706134X
Liav A, Angala SK, Brennan PJ, Jackson M (2008) Aldopentofuranosyl-N′-[p-(isoamyloxy)phenyl]-thiourea derivatives: Potential anti-TB therapeutic agents. Bioorg Med Chem Lett 8: 2649–2651. doi:10.1016/j.bmcl.2008.03.033
Joly GD, Jacobsen EN (2004) Thiourea-catalyzed enantioselective hydrophosphonylation of imines: practical access to enantiomerically enriched α-amino phosphonic acids. J Am Chem Soc 126: 4102–4103. doi:10.1021/ja0494398
Wenzel AG, Jacobsen EN (2002) Asymmetric catalytic Mannich reactions catalyzed by urea derivatives: enantioselective synthesis of β-aryl-β-amino acids. J Am Chem Soc 124: 12964–12965. doi:10.1021/ja028353g
Fuerst DE, Jacobsen EN (2005) Thiourea-catalyzed enantioselective cyanosilylation of ketones. J Am Chem Soc 127: 8964–8965. doi:10.1021/ja052511x
Yamaoka Y, Miyabe H, Takemoto Y (2007) Catalytic enantioselective petasis-type reaction of quinolines catalyzed by a newly designed thiourea catalyst. J Am Chem Soc 129: 6686–6687. doi:10.1021/ja071470x
Dunn AD, Rudorf WD (1997) Carbon disulphide in organic chemistry. Ellis Horwood limited, Chichester, pp 226–315 ISBN: 0470214414/0-470-21441-4
Ozaki S (1972) Recent advances in isocyanate chemistry. Chem Rev 72: 457–496. doi:10.1021/cr60279a002
Herr RJ, Kuhler JL, Meckler H, Opalka CJ (2000) A Convenient method for the preparation of primary and symmetrical N,N′-disubstituted thioureas. Synthesis 1569–1574. doi:10.1055/s-2000-7607
Ballabeni M, Ballini R, Bigi F, Maggi R, Parrini M, Predieri G, Sartori G (1999) Synthesis of symmetrical N,N-disubstituted thioureas and heterocyclic thiones from amines and CS2 over a ZnO/Al2O3 composite as heterogeneous and reusable catalyst. J Org Chem 64: 1029–1032. doi:10.1021/jo981629b
Ballini R, Bosica G, Fiorini D, Maggi R, Righi P, Sartori G, Sartorio R (2002) MCM-41-TBD as a new, efficient, supported heterogeneous catalyst for the synthesis of thioureas. Tetrahedron Lett 43: 8445–8447. doi:10.1016/S0040-4039(02)02100-7
Mohanta PK, Dhar S, Samal SK, Ila H, Junjappa H (2000) 1-(Methyldithiocarbonyl)imidazole: a useful thiocarbonyl transfer reagent for synthesis of substituted thioureas. Tetrahedron 56: 629–637. doi:10.1016/S0040-4020(99)01026-1
Maddani M, Prabhu KR (2007) A convenient method for the synthesis of substituted thioureas. Tetrahedron Lett 48: 7151–7154. doi:10.1016/j.tetlet.2007.07.212
Vázquez J, Bernès S, Reyes Y, Moya M, Sharma P, Alvarez C, Gutiérrez R, (2004) Solvent-free synthesis of chiral N,N′-disubstituted thioureas by ‘just mixing’ the reagents. Synthesis 1955–1958. doi:10.1055/s-2004-829167
Azizi N, Saidi MR (2005) Highly chemoselective addition of amines to epoxides in water. Org Lett 7: 3649–3651. doi:10.1021/ol051220q
Azizi N, Aryanasab F, Torkiyan L, Ziyaei A, Saidi MR (2006) One-pot synthesis of dithiocarbamates accelerated in water. J Org Chem 71: 3634–3635. doi:10.1021/jo060048g
Azizi N, Torkiyan L, Saidi MR (2006) Highly efficient one-pot three-component Mannich reaction in water catalyzed by heteropoly acids. Org Lett 8: 2079–2082. doi:10.1021/ol060498v
Azizi N, Aryanasab F, Saidi MR (2006) Straightforward and highly efficient catalyst-free one-pot synthesis of dithiocarbamates under solvent-free conditions. Org Lett 8: 5275–5278. doi:10.1021/ol0620141
Zhao Y, Pe’rez-Segarra W, Shi Q, Wei A (2005) Dithiocarbamate assembly on gold. J Am Chem Soc 127: 7328–7329. doi:10.1021/ja050432f
Author information
Authors and Affiliations
Corresponding author
Electronic Supplementary Material
The Below is the Electronic Supplementary Material.
Rights and permissions
About this article
Cite this article
Azizi, N., Khajeh-Amiri, A., Ghafuri, H. et al. Toward a practical and waste-free synthesis of thioureas in water. Mol Divers 15, 157–161 (2011). https://doi.org/10.1007/s11030-010-9236-7
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s11030-010-9236-7