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Tin-Catalyzed Urea Alcoholysis With β-Citronellol: A Simple and Selective Synthesis of Carbamates

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Abstract

Tin(II) chloride is a stable and water tolerant Lewis acid, commercially available and less corrosive than Brønsted acid catalysts. Our proposal was demonstrated that SnCl2 was an efficient catalyst on the urea alcoholysis with β-citronellol. We investigated the effects of main reaction parameters such as concentration and tin(II) catalyst nature, reagents stoichiometry and reaction temperature. In homogenous conditions with DMSO as solvent, the SnCl2-catalyzed urea alcoholysis reactions under air flux achieved high conversion and selectivity for β-citronellyl carbamate (ca. 90 and 95 %, respectively). Among tin(II) catalysts assessed, SnCl2 was more active due to its total solubility. Possible intermediates of active Sn(II) species were discussed based on the results of catalytic runs and FT-IR spectroscopy measurements of the liquid phase after the reaction. FT-IR spectroscopy data showed that the active species could be a complex of a Sn(II) atom coordinated with N=C=O. This novel and phosgene-free selective process provide an inexpensive and attractive route to synthesize terpenic carbamates through inexpensive and renewable reactant (i.e. urea). Moreover, SnCl2 was also an efficient catalyst on synthesis of β-citronellyl carbonate.

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References

  1. Gallezot P (2007) Catal Today 121:76

    Article  CAS  Google Scholar 

  2. Carari DM, Da Silva MJ (2012) Catal Lett 142:251

    Article  CAS  Google Scholar 

  3. Chapuis C, Jacoby D (2001) Appl Catal A 221:93

    Article  CAS  Google Scholar 

  4. Lenardao EJ, Botteselle GV, Azambuja F, Perin G, Jacob RG (2007) Tetrahedron 63:6671

    Article  CAS  Google Scholar 

  5. Ortar G, Moriello AS, Morera E, Nallia M, Di Marzo V, De Petrocellis L (2014) Bioorg Med Chem Lett 24:5507

    Article  CAS  Google Scholar 

  6. Wua X, Kanga M, Yina Y, Wang F, Zhao N, Xiao F, Wei W, Suna Y (2014) Appl Catal A 473:13

    Article  Google Scholar 

  7. Zhang C, Lu B, Wang X, Zhao J, Cai Q (2012) Catal Sci Technol 2:309

    Google Scholar 

  8. Cornely J, Ham LMS, Meade DE, Dragojlovic V (2003) Green Chem 5:34

    Article  CAS  Google Scholar 

  9. Wang D, Yang B, Zhai X, Zhou L (2007) Fuel Process Technol 88:807

    Article  CAS  Google Scholar 

  10. Wang P, Liu X, Zhue F, Yang B, Alshammari AS, Deng Y (2015) RSC Adv 5:19534

    Article  CAS  Google Scholar 

  11. Saleh RY, Michaelson RC, Suciu EN, Kuhlmann B (1996) US Patent No. 5561094

  12. Bhanage BM, Fujita S, He Y, Ikushima Y, Shirai M, Torii K, Arai M (2002) Catal Lett 83:137

    Article  CAS  Google Scholar 

  13. Leino E, Mäki-Arvela P, Eta V, Murzin DY, Salmi T, Mikkola JP (2010) Appl Catal A 383:1

    Article  CAS  Google Scholar 

  14. Wang M, Wang H, Zhao N, Wei W, Sun Y (2007) Ind Eng Chem Res 46:2683

    Article  CAS  Google Scholar 

  15. Woods G (1994) The ICI polyurethanes book. Wiley, New York

    Google Scholar 

  16. Rice PJ, Coats JR (1994) Pestic Sci 41:195

    Article  CAS  Google Scholar 

  17. Rios ER, Rocha NF, Carvalho AM, Vasconcelos LF, Dias ML, De Sousa DP, de Sousa FC, Fonteles MM (2013) Chem Biol Interact 203:573

    Article  CAS  Google Scholar 

  18. Wuts PGM, Greene TW (2007) Greene’s Protective Groups in organic synthesis. Wiley, Hoboken

    Google Scholar 

  19. El-Zemity SR (2006) J Appl Sci Res 2:86

    Google Scholar 

  20. Da Silva MJ, Da Silva ML, Figueiredo AP, Cardoso AL, Natalino R (2011) J Am Oil Chem Soc 88:1431

    Article  CAS  Google Scholar 

  21. Menezes FL, Guimaraes MDO, Da Silva MJ (2013) Ind Eng Chem Res 52:16709

    Article  CAS  Google Scholar 

  22. Radwan MA, El-Zemity SR, Mohamed SA, Sherby SM (2008) Ecotoxicol Environ Safe 71:889

    Article  CAS  Google Scholar 

  23. Suciu EN, Kuhlmann B, Knudsen GA, Michaelson RC (1998) J Organomet Chem 556:41

    Article  CAS  Google Scholar 

  24. Cardoso AL, Neves SCG, Da Silva MJ (2009) Energ Fuel 23:1718

    Article  CAS  Google Scholar 

  25. Da Silva MJ, Goncalves CE, Laier LO (2011) Catal Lett 141:1111

    Article  Google Scholar 

  26. Yamaguchi S, Motokura K, Sakamoto Y, Miyaji A, Baba T (2014) Chem Commun 50:4600

    Article  CAS  Google Scholar 

  27. Golets M, Ajaikumar S, Blomberg D, Grundberg H, Wärnå J, Salmi T, Mikkola J-P (2012) Appl Catal A 43:435

    Google Scholar 

  28. Ferreira AB, Cardoso AL, Da Silva MJ (2013) Catal Lett 143:1240

    Article  CAS  Google Scholar 

  29. Wang D, Zhang X, Ma J, Yu H, Shen J, Wei W (2016) Catal Sci Technol 6:1530

    Article  CAS  Google Scholar 

  30. Nath M, Pokharia S, Song X, Eng G, Gielen M, Kemmer M, Biesemans M, Willem R, de Vos D (2003) Appl Organometal Chem 17:305

    Article  CAS  Google Scholar 

  31. Aggarwal RC, Singh PP (1964) J Inorg Nucl Chem 26:2185

    Article  CAS  Google Scholar 

  32. Fujita S-I, Yamanishi Y, Arai M (2013) J Catal 297:137

    Article  CAS  Google Scholar 

  33. Zhao W, Peng W, Wang D, Zhao N, Li J, Xiao F, Wei W, Sun Y (2009) Catal Commun 10:655

    Article  CAS  Google Scholar 

  34. Taimsalu P, Wood JL (1984) Spectrochim Acta 20:1043

    Article  Google Scholar 

  35. Leles LA, Zabula AV, Bukalov SS, Koroteev OS, Maslennikova OS, Egorov MP, Nefedov OM (2005) Russ Chem Bull 54:1117

    Article  Google Scholar 

  36. Fujita SI, Yamanishi Y, Arai M (2013) J Catal 297:137

    Article  CAS  Google Scholar 

  37. Wu X, Kanga M, Yina Y, Wanga F, Zhaoa N, Xiao F, Weic W, Suna Y (2014) Appl Catal A 473:13

    Article  CAS  Google Scholar 

  38. Niknam K, Zolfigol MA, Saberi D, Molaee H (2009) J Chin Chem Soc 56:1257

    Article  CAS  Google Scholar 

  39. Abu-Samn RH (1983) J Chem Soc Pak 5:23

    CAS  Google Scholar 

Download references

Acknowledgments

The authors are grateful for the financial support from CAPES, CNPq, and FAPEMIG (Brazil).

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Authors and Affiliations

  1. Chemistry Department, Federal University of Viçosa, Viçosa, MG, 36590-000, Brazil

    Diego Chaves Morais & Márcio José da Silva

  2. Departamento de Química, Universidade Federal de Viçosa (UFV), Campus Universitário, Avenida P.H. Rolfs, s/n, Viçosa, MG, Brazil, 36570-000

    Márcio José da Silva

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  1. Diego Chaves Morais
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  2. Márcio José da Silva
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Correspondence to Márcio José da Silva.

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Morais, D.C., da Silva, M.J. Tin-Catalyzed Urea Alcoholysis With β-Citronellol: A Simple and Selective Synthesis of Carbamates. Catal Lett 146, 1517–1528 (2016). https://doi.org/10.1007/s10562-016-1769-7

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