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A highly efficient electrochemical route for the conversion of aldehydes to nitriles

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Abstract

Using NH4I as the supporting electrolyte as well as the precursor of an I2 promoter and nitrogen source, a highly efficient electrochemical route was developed to convert aldehydes to nitriles with excellent yields under mild reaction conditions. This electrochemical process could effectively avoid the direct use of NH3 gas, molecular iodine, and oxidants.

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References

  1. Friedrich K, Waaensfesl K. The Chemistry of the Cyano Group. New York: Wiley-Interscience, 1970

    Google Scholar 

  2. Fatiadi AJ. Preparation and Synthetic Applications of Cyano Compounds. New York: Wiley, 1983

    Book  Google Scholar 

  3. Chihiro M, Nagamoto H, Takemura I, Kitano K, Komatsu H, Sekiguchi K, Tabuse F, Mori T, Tominaga M, Yabuuchi Y. Novel thiazole derivatives as inhibitors of superoxide production by human neutrophils: synthesis and structure-activity relationships. J Med Chem, 1995, 38: 353–358

    Article  CAS  Google Scholar 

  4. Serrano J, Sierra T, Gonzalez Y, Bolm C, Weickhardt K, Magnus A, Moli G. Improving FLC properties. Simplicity, planarity, and rigidity in new chiral oxazoline derivatives. J Am Chem Soc, 1995, 117: 8312–8321

    Article  CAS  Google Scholar 

  5. Medwid JB, Paul R, Baker JS. Preparation of triazolo[1,5-c]pyrimidines as potential antiasthma agents. J Med Chem, 1990, 33: 1230–1241

    Article  CAS  Google Scholar 

  6. Friedman L, Shechter H. Preparation of nitriles from halides and sodium cyanide. An advantageous nucleophilic displacement in dimethyl sulfoxide. J Org Chem, 1960, 25: 877–879

    Article  CAS  Google Scholar 

  7. Bini L, Muller C, Wilting J, Chrzanowski L, Spek AL, Vogt D. Highly selective hydrocyanation of butadiene toward 3-pentenenitrile. J Am Chem Soc, 2007, 129: 12622–12623

    Article  CAS  Google Scholar 

  8. Yang SH, Chang S. Highly efficient and catalytic conversion of aldoximes to nitriles. Org Lett, 2001, 3: 4209–4211

    Article  CAS  Google Scholar 

  9. Harrison C, Hodge P, Rogers W. Conversion of carboxamides and oximes to nitriles or imidoyl chlorides using a polymer-supported phosphine and carbon tetrachloride. Synthesis, 1977, 1: 41–43

    Article  Google Scholar 

  10. Cho BR, Chung HS, Cho NS. Elimination reactions of (E)-and (Z)-benzaldehyde o-benzoyloximes. Transition state differences for the syn- and anti-eliminations forming nitriles. J Org Chem, 1998, 63: 4685–4690

    CAS  Google Scholar 

  11. Maeyama K, Kobayashi M, Kato H, Yonezawa N. Nickel/zinc-media ted synthesis of aromatic nitriles from aromatic oxime ethers. Synthetic Commun, 2002, 32: 2519–2525

    Article  CAS  Google Scholar 

  12. Stevens TE. The use of organodilithium compounds for the synthesis of 1,1-dimethylsilacyclopentane and 1,1-dimethylsilacyclohexane. J Org Chem, 1961, 26: 2530–2531

    Article  Google Scholar 

  13. Iida S, Ohmura R, Togo H. Direct oxidative conversion of alkyl halides into nitriles with molecular iodine and 1,3-diiodo-5,5-dimethylhydantoin in aq ammonia. Tetrahedron, 2009, 65: 6257–6262

    Article  CAS  Google Scholar 

  14. Leadbeater NE, Torenius HM, Tye H. Ionic liquids as reagents and solvents in conjunction with microwave heating: rapid synthesis of alkyl halides from alcohols and nitriles from aryl halides. Tetrahedron, 2003, 59: 2253–2258

    Article  CAS  Google Scholar 

  15. Brackman W, Smit PJ. A new synthesis of nitriles. Recl Trav Chim, 1963, 82: 757–762

    Article  CAS  Google Scholar 

  16. Misono A, Osa T, Koda S. The synthesis of nitriles from aldehydes. Bull Chem Soc Jpn, 1966, 39: 854

    Article  CAS  Google Scholar 

  17. Erman MB, Snow JW, Williams MJ. A new efficient method for the conversion of aldehydes into nitriles using ammonia and hydrogen peroxide. Tetrahedron Lett, 2000, 41: 6749–6752

    Article  CAS  Google Scholar 

  18. Carmeli M, Shefer N, Rozen S. From aldehydes to nitriles, a general and high yielding transformation using HOF·CH3CN complex. Tetrahedron Lett, 2006, 47: 8969–8972

    Article  CAS  Google Scholar 

  19. Arote ND, Bhalerao DS, Akamanchi KG. Direct oxidative conversion of aldehydes to nitriles using IBX in aqueous ammonia. Tetrahedron Lett, 2007, 48: 3651–3653

    Article  CAS  Google Scholar 

  20. Telvekar VN, Patel KN, Kundaikar HS. A novel system for the synthesis of nitriles from aldehydes using aqueous ammonia and sodium dichloroiodate. Tetrahedron Lett, 2008, 49: 2213–2215

    Article  CAS  Google Scholar 

  21. Rajender Reddy K, Uma Maheswari C, Venkateshwar M. Catalytic oxidative conversion of alcohols, aldehydes and amines into nitriles using KI/I2-TBHP system. Tetrahedron Lett, 2009, 50: 2050–2053

    Article  CAS  Google Scholar 

  22. Zhu C, Ji L, Wei Y. A facile and efficient one-pot synthesis of nitriles from aldehydes using hypervalent iodine (III) reagents in aqueous ammonium acetate. Synthesis, 2010, 18: 3121–3125

    Google Scholar 

  23. Zolfigol MA, Hajjami M, Ghorbani-Choghamarani A. A simple and one-pot oxidative conversion of alcohols or aldehydes to the nitriles using NaIO4/KI in aqueous NH3. Bull Korean Chem Soc, 2011, 32: 4191–4191

    Article  CAS  Google Scholar 

  24. Bose DS, Narsaiah AV. Efficient one pot synthesis of nitriles from aldehydes in solid state using peroxymonosulfate on alumina. Tetrahedron Lett, 1998, 39: 6533–6534

    Article  CAS  Google Scholar 

  25. Sridhar M, Reddy MKK, Sairam VV. Acetohydroxamic acid: a new reagent for efficient synthesis of nitriles directly from aldehydes using Bi(OTf)3 as the catalyst. Tetrahedron Lett, 2012, 53: 3421–3424

    Article  CAS  Google Scholar 

  26. Enthaler S, Weidauer M, Schröder F. Straightforward zinc-catalyzed transformation of aldehydes and hydroxylamine hydrochloride to nitriles. Tetrahedron Lett, 2012, 53: 882–885

    Article  CAS  Google Scholar 

  27. Talukdar S, Hsu JL, Chou TC. Direct transformation of aldehydes to nitriles using iodine in ammonia water. Tetrahedron Lett, 2001, 42: 1103–1105

    Article  CAS  Google Scholar 

  28. Movassagh B, Shokri S. An efficient and convenient KF/Al2O3 mediated synthesis of nitriles from aldehydes. Tetrahedron Lett, 2005, 46: 6923–6925

    Article  CAS  Google Scholar 

  29. Chill ST, Mebane RC. A facile one-pot conversion of aldehydes into nitriles. Synthetic Commun, 2009, 39: 3601–3606

    Article  CAS  Google Scholar 

  30. Sharghi H, Sarvari MH. A direct synthesis of nitriles and amides from aldehydes using dry or wet alumina in solvent free conditions. Tetrahedron, 2002, 58: 10323–10328

    Article  CAS  Google Scholar 

  31. Madhusudana Reddy MB, Pasha MA. Environment friendly protocol for the synthesis of nitriles from aldehydes. Chinese Chem Lett, 2010, 21: 1025–1028

    Article  CAS  Google Scholar 

  32. Frontana-Uribe BA, Little RD, Ibanez JG, Palma A, Vasquez-Medrano R. Organic electrosynthesis: a promising green methodology in organic chemistry. Green Chem, 2010, 12: 2099–2119

    Article  CAS  Google Scholar 

  33. Yoshida J, Kataoka K, Horcajada R, Nagaki A. Modern strategies in electroorganic synthesis. Chem Rev, 2008, 108: 2265–2299

    Article  CAS  Google Scholar 

  34. Shono T, Matsumura Y, Tsubata K, Kamada T, Kishi K. Electrochemical transformation of aldoximes to nitriles using halogen ions as mediators: intermediary formation of nitrile oxides. J Org Chem, 1989, 54: 2249–2251

    Article  CAS  Google Scholar 

  35. Francke R, Little RD. Redox catalysis in organic electrosynthesis: basic principles and recent developments. Chem Soc Rev, 2014, 43: 2492–2521

    Article  CAS  Google Scholar 

  36. Gao X, Yuan G, Chen H, Jiang H, Li Y, Qi C. Efficient conversion of CO2 with olefins into cyclic carbonates via a synergistic action of I2 and base electrochemically generated in situ. Electrochem Commun, 2013, 34: 242–245

    Article  CAS  Google Scholar 

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Authors and Affiliations

  1. School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou, 510640, China

    Qinghui Qu, Xiaofang Gao, Jian Gao & Gaoqing Yuan

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  1. Qinghui Qu
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  2. Xiaofang Gao
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  3. Jian Gao
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  4. Gaoqing Yuan
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Correspondence to Gaoqing Yuan.

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Qu, Q., Gao, X., Gao, J. et al. A highly efficient electrochemical route for the conversion of aldehydes to nitriles. Sci. China Chem. 58, 747–750 (2015). https://doi.org/10.1007/s11426-015-5331-z

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  • DOI: https://doi.org/10.1007/s11426-015-5331-z

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