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Thiocarbamoylation of amine-containing compounds

5. The mechanism of reactions of tetramethylthiuram disulfide with aliphatic amines

  • Organic Chemistry
  • Published:
Russian Chemical Bulletin Aims and scope

Abstract

Thiocarbamoylation of aliphatic amines with tetramethylthiuram disulfide (TMTD) was studied. The reactions were established to proceed according to a two-stage mechanism. In the first stage,S-(thiocarbamoyl)thiohydroxylamines and dimethyl dithiocarbamates are formed. The latter exist in equilibrium with dimethyldithiocarbamic acid, which can undergo decomposition to give dimethylamine and carbon disulfide. In the second stage, several competitive transformations of these intermediates into the final products occur,viz., (1) the reactions of CS2 with primary amines on heating (70–110 °C) yield mixed and symmetrical thioureas and the reactions of CS2 with secondary amines give symmetrical dithiocarbamates, and (2) insertion of CS2 intoS-(thiocarbamoyl)thiohydroxylamines affords thiuram disulfides. Thiuram disulfides formed from primary amines decompose to give isothiocyanates, which are converted into thioureas by condensation with amines, whereas thiuram disulfides which are obtained in the reactions with secondary amines and which cannot form thioureas react with amines analogously to TMTD.

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References

  1. Luu Van Boi,Izv. Akad. Nauk, Ser. Khim., 1999, 2319 [Russ. Chem. Bull., 1999,48, 2294 (Engl. Transl.)].

  2. I. Gutu, Luu Van Boi, and N. A. Barba,Conferenta de chemie si ingenerie chimica, Universitetea Politehnica, Bucuresti, 1995,2, 516.

  3. A. Zadorojnii, N. A. Barba, I. Gutu, and L. V. Boi,Conferenta de chemie si ingenerie chimica, Universitetea Politehnica, Bucuresti, 1995,2, 529.

  4. I. Gutu, L. V. Boi, S. Maiga, and N. Barba, inA 22a Sesiune de comunicari stiintifice, Centrul de cercetari Oltchim, Olanesti, Valcea, 1996, 404.

    Google Scholar 

  5. N. Barba, M. Botnaru, I. Gutu, L. V. Boi and A. Hamdan,Anale stiintifice, ser. Stiinte reale, Universitetea State Moldova, Chisinau, 1997, 165.

    Google Scholar 

  6. Luu Van Boi, N. Barba, and V. Florea,Anale stiintifice, ser. Stiinte reale, Universitetea State Moldova, Chisinau, 1997, 171.

    Google Scholar 

  7. Luu Van Boi, A. Khamdan, M. Botnaru, and N. Barba,Anale stiintifice, ser. Stiinte reale, Universitetea State Moldova, Chisinau, 1998, 65.

    Google Scholar 

  8. Luu Van Boi, I. Korzha, and N. Barba,Izv. Akad. Nauk, Ser. Khim., 1999, 743 [Russ. Chem. Bull., 1999,48, 739 (Engl. Transl.)].

  9. Luu Van Boi, A. Zadorozhnyi, and N. Barba,Izv. Akad. Nauk, Ser. Khim., 1999, 771 [Russ. Chem. Bull., 1999,48, 767 (Engl. Transl.)].

  10. Luu Van Boi and H. Al-Ebaisat,Izv. Akad. Nauk, Ser. Khim., 1999, 2315 [Russ. Chem. Bull., 1999,48, 2290 (Engl. Transl.)].

  11. Luu Van Boi and L. A. Vlad,Anale stiintifice, ser. Stiinte chimico-biologie, Universitetea State Moldova, Chisinau, 1999, 185.

    Google Scholar 

  12. G. V. Nair,J. Indian Chem. Soc., 1965,42, 359.

    CAS  Google Scholar 

  13. A. N. Lazovenko, V. A. Ignatov, and I. V. Zhelovkova,Zh. Obshch. Khim., 1981,51, 679 [J. Gen. Chem. USSR, 1981,51 (Engl. Transl.)].

    CAS  Google Scholar 

  14. A. N. Lazovenko, V. A. Ignatov, E. A. Kachergina, and N. V. Chebeneva,Zh. Obshch. Khim., 1983,53, 97 [J. Gen. Chem. USSR, 1983,53 (Engl. Transl.)].

    CAS  Google Scholar 

  15. A. Rivkind,Dokl. Akad. Nauk SSSR, 1955,100, 933 [Dokl. Chem., 1955 (Engl. Transl.)].

    CAS  Google Scholar 

  16. J. Zyka,Prazska Univ. Moskevske Univ. Sb. Vyroci, Praha, 1955, 326.

  17. Luu Van Boi,Izv. Akad. Nauk, Ser. Khim., 2000, in press [Russ. Chem. Bull., 2000,49, in press (Engl. Transl.)].

  18. Comprehensive Organic Chemistry, Eds. D. Barton and W. D. Ollis, Pergamon Press, Oxford-New York, 1979,3.

    Google Scholar 

  19. D. A. Armitage and M. J. Clark,J. Chem. Soc., C, 1971, 2840.

  20. E. Kuhle,Synthesis, 1971, 563; 617.

    Article  Google Scholar 

  21. B. Adhicari, D. Pal, and D. K. Basu,Rubber Chem. and Technol., 1983,56, 326.

    Google Scholar 

  22. E. S. Blake,J. Am. Chem. Soc., 1943,65, 1267.

    Article  CAS  Google Scholar 

  23. J. J. D'Amico and E. Morita,Phosphorus and Sulfur, 1977,3, 255.

    Google Scholar 

  24. M. M. Clifford and J. G. Lichty,J. Am. Chem. Soc., 1932,54, 1163.

    Article  CAS  Google Scholar 

  25. Houben-Weyl,Methoden der Org. Chem., 1955,9, 823.

    Google Scholar 

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Authors and Affiliations

  1. N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 47 Leninsky prosp., 117913, Moscow, Russian Federation

    Luu Van Boi

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  1. Luu Van Boi
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For Part 4, see Ref. 1.

Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 334–342, February, 2000.

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Van Boi, L. Thiocarbamoylation of amine-containing compounds. Russ Chem Bull 49, 335–343 (2000). https://doi.org/10.1007/BF02494685

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  • DOI: https://doi.org/10.1007/BF02494685

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