IJOC  Vol.4 No.3 , September 2014
Dehydrosulfurization of Aromatic Thioamides to Nitriles Using Indium(III) Triflate
ABSTRACT
The efficient dehydrosulfurization of thioamides to nitriles was carried out using indium(III) triflate as a catalyst. Based on the results of the initial study, the optimal reaction conditions required 5 mol% of indium(III) triflate with toluene as the practical solvent. Various thioamides were successfully converted to nitriles in high yields.

Cite this paper
Mineno, T. , Takebe, Y. , Tanaka, C. and Mashimo, S. (2014) Dehydrosulfurization of Aromatic Thioamides to Nitriles Using Indium(III) Triflate. International Journal of Organic Chemistry, 4, 169-173. doi: 10.4236/ijoc.2014.43018.
References
[1]   Satchell, D.P.N. (1977) Metal-Ion-Promoted Reactions of Organo-Sulphur Compounds. Chemical Society Reviews, 6, 345-371.
http://dx.doi.org/10.1039/CS9770600345

[2]   Suzuki, H., Tani, H. and Takeuchi, S. (1985) Desulfurization of Thioketones and Thioamides with Diphosphorus Tetraiodide. Bulletin of the Chemical Society of Japan, 58, 2421-2422.
http://dx.doi.org/10.1246/bcsj.58.2421

[3]   Kondo, K., Komamura, C., Murakami, M. and Takemoto, K. (1985) 2,4-Dichloro-5-nitropyrimidine as a New Dehydrating or Desulfhydrating Reagent. Synthetic Communications, 15, 171-177.
http://dx.doi.org/10.1080/00397918508063784

[4]   Bose, D.S. and Goud, P.R. (1999) Aryl Chlorothionoformate: A New Versatile Reagent for the Preparation of Nitriles and Isonitriles under Mild Conditions. Tetrahedron Letters, 40, 747-748.
http://dx.doi.org/10.1016/S0040-4039(98)02361-2

[5]   Sato, R., Itoh, K., Itoh, K., Nishina, H., Goto, T. and Saito, M. (1984) Novel Conversion of Aromatic Thioamides and Aldehydes into Nitriles with Elemental Sulfur and Sodium Nitrite in Liquid Ammonia. Chemistry Letters, 11, 1913-1916.
http://dx.doi.org/10.1246/cl.1984.1913

[6]   Funakoshi, Y., Takido, T. and Itabashi, K. (1985) Facile Conversion of Primary Thioamides into Nitriles with Benzyl Chloride under Phase Transfer Conditions. Synthetic Communications, 15, 1299-1303.
http://dx.doi.org/10.1080/00397918508077278

[7]   Avalos, M., Babiano, R., Duran, C.J., Jimenez, J.L. and Palacios, J.C. (1994) Reaction of Thioamides with Silver Carboxylates in Aprotic Media. A Nucleophilic Approach to the Synthesis of Imides, Amides, and Nitriles. Tetrahedron Letters, 35, 477-480.
http://dx.doi.org/10.1016/0040-4039(94)85085-2

[8]   Avalos, M., Babiano, R., Cintas, P., Duran, C.J., Higes, F.J., Jimenez, J.L., Lopez, I. and Palacios, J.C. (1997) Reaction of Thioamides with Metal Carboxylates in Organic Media. Tetrahedron, 53, 14463-14480.
http://dx.doi.org/10.1016/S0040-4020(97)00938-1

[9]   Yamaguchi, K., Yajima, K. and Mizuno, N. (2012) Facile Synthesis of Nitriles via Manganese Oxide Promoted Oxidative Dehy-drosulfurization of Primary Thioamides. Chemical Communications, 48, 11247-11249.
http://dx.doi.org/10.1039/c2cc36635e

[10]   Lim, M.-I., Ren, W.-Y. and Klein, R.S. (1982) Facile Conversion of Primary Thioamides into Nitriles with Butyltin Oxides. Journal of Organic Chemistry, 47, 4594-4595.
http://dx.doi.org/10.1021/jo00144a043

[11]   Hu, N.X., Aso, Y., Otsubo, T. and Ogura, F. (1985) Mild and Selective Oxidations with Polystyrene-Bound Diaryl Selenoxide. Chemistry Letters, 14, 603-606.
http://dx.doi.org/10.1246/cl.1985.603

[12]   Hu, N.X., Aso, Y., Otsubo, T. and Ogura, F. (1986) Polymer-Supported Diaryl Selenoxide and Telluroxide as Mild and Selective Oxidizing Agents. Bulletin of the Chemical Society of Japan, 59, 879-884.
http://dx.doi.org/10.1246/bcsj.59.879

[13]   Hu, N.X., Aso, Y., Otsubo, T. and Ogura, F. (1986) Novel Oxidizing Properties of p-Methoxybenzenetellurinic Acid Anhydride. Tetrahedron Letters, 27, 6099-6102.
http://dx.doi.org/10.1016/S0040-4039(00)85408-8

[14]   Fukumoto, T., Matsuki, T., Hu, N.X., Aso, Y., Otsubo, T. and Ogura, F. (1990) Benzenetellurinic Mixed Anhydrides as Mild Oxidizing Agents. Chemistry Letters, 19, 2269-2272.
http://dx.doi.org/10.1246/cl.1990.2269

[15]   Aso, Y., Omote, K., Takagi, S., Otsubo, T. and Ogura, F. (1995) Mild and Efficient Dehydrosulfurization of Thioamides to Nitriles Induced by Tellurium or Selenium Tetrachloride with Triethylamine. Journal of Chemical Research, Synopses, No. 4, 152-153.

[16]   Enthaler, S. (2011) Straightforward Iron-Catalyzed Synthesis of Nitriles by Dehydration of Primary Amides. European Journal of Organic Chemistry, 2011, 4760-4763.
http://dx.doi.org/10.1002/ejoc.201100754

[17]   Enthaler, S. and Inoue, S. (2012) An Efficient Zinc-Catalyzed Dehydration of Primary Amides to Nitriles. Chemistry—An Asian Journal, 7, 169-175.
http://dx.doi.org/10.1002/asia.201100493

[18]   Mineno, T. (2002) A Fast and Practical Approach to Tetrahydro-pyranylation and Depyranylation of Alcohols Using Indium Triflate. Tetrahedron Letters, 43, 7975-7978.
http://dx.doi.org/10.1016/S0040-4039(02)01864-6

[19]   Mineno, T. and Kansui, H. (2006) High Yielding Methyl Esterification Catalyzed by Indium(III) Chloride. Chemical & Pharmaceutical Bulletin, 54, 918-919.
http://dx.doi.org/10.1248/cpb.54.918

[20]   Mineno, T., Nikaido, N. and Kansui, H. (2009) One-Step Transformation of Tetrahydropyranyl Ethers Using Indium(III) Triflate as the Catalyst. Chemical & Pharmaceutical Bulletin, 57, 1167-1170.
http://dx.doi.org/10.1248/cpb.57.1167

[21]   Mineno, T., Sakai, M., Ubukata, A., Nakahara, K., Yoshimitsu, H. and Kansui, H. (2013) The Effect of Indium(III) Triflate in Oxone-Mediated Oxidative Methyl Esterification of Aldehydes. Chemical & Pharmaceutical Bulletin, 61, 870-872.
http://dx.doi.org/10.1248/cpb.c13-00072

[22]   Mineno, T., Tsukagoshi, R., Iijima, T., Watanabe, K., Miyashita, H. and Yoshimitsu, H. (2014) Reductive Coupling Reaction of Aldehydes Using Indium(III) Triflate as the Catalyst. Tetrahedron Letters, 55, 3765-3767.
http://dx.doi.org/10.1016/j.tetlet.2014.05.079

[23]   Mineno, T., Yoshino, S. and Ubukata, A. (2014) Oxone-Mediated Oxidative Esterification of Heterocyclic Aldehydes Using Indium(III) Triflate. Green and Sustainable Chemistry, 4, 20-23.
http://dx.doi.org/10.4236/gsc.2014.41004

[24]   Mineno, T., Shinada, M., Watanabe, K., Yoshimitsu, H., Miyashita, H. and Kansui, H. (2014) Highly-Efficient Conversion of Primary Amides to Nitriles Using Indium(III) Triflate as the Catalyst. International Journal of Organic Chemistry, 4, 1-6.
http://dx.doi.org/10.4236/ijoc.2014.41001

[25]   Littke, A., Soumeillant, M., Kaltenbach III, R.F., Cherney, R.J., Tarby, C.M. and Kiau, S. (2007) Mild and General Methods for the Palladium-Catalyzed Cyanation of Aryl and Heteroaryl Chlorides. Organic Letters, 9, 1711-1714.
http://dx.doi.org/10.1021/ol070372d

[26]   Grossman, O. and Gelman, D. (2006) Novel Trans-Spanned Palladium Complexes as Efficient Catalysts in Mild and Amine-Free Cyanation of Aryl Bromides under Air. Organic Letters, 8, 1189-1191.
http://dx.doi.org/10.1021/ol0601038

[27]   Yang, C. and Williams, J.M. (2004) Palladium-Catalyzed Cyanation of Aryl Bromides Promoted by Low-Level Organotin Compounds. Organic Letters, 6, 2837-2840.
http://dx.doi.org/10.1021/ol049621d

[28]   Katritzky, A.R., Akue-Gedu, R. and Vakulenko, A.V. (2007) C-Cyanation with 1-cyanobenzotriazole. ARKIVOC, 2007, 5-12.
http://dx.doi.org/10.3998/ark.5550190.0008.302

 
 
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