2-Alkyl-1,2,3,4-benzotetrazinium salts: Synthesis and NMR studies of the novel 2-alkyl-1,2,3,4-tetrazinium/ortho-(alkylazo)diazonium equilibrium

European Journal of Organic Chemistry

Volumn , Issue 22, 2002, Pages 3821-3826

  Lipilin, Dmitry L ^a   Belyakov, Pavel A ^a   Strelenko, Yuri A ^a   Churakov, Aleksandr M ^a   Smirnov, Oleg Yu ^a   Ioffe, Sema L ^a   Tartakovsky, Vladimir A ^a  

^a N D ZELINSKY INSTITUTE OF ORGANIC CHEMISTRY   (Russian Federation)

Author keywords

Azo compounds; Diazonium salts; Nitrogen heterocycles; Ring chain tautomerism

Indexed keywords

1,2,3,4 BENZOTETRAZINIUM; DIAZONIUM COMPOUND; UNCLASSIFIED DRUG;

ANALYTIC METHOD; ARTICLE; CARBON NUCLEAR MAGNETIC RESONANCE; CHEMICAL REACTION; DERIVATIZATION; MOLECULAR INTERACTION; REACTION ANALYSIS; SIGNAL TRANSDUCTION; SYNTHESIS;

EID: 0036856582     PISSN: 1434193X     EISSN: None     Source Type: Journal    
DOI: 10.1002/1099-0690(200211)2002:22<3821::AID-EJOC3821>3.0.CO;2-Y     Document Type: Article

References (21)

1. F. R. Benson, The High Nitrogen Compounds, John Wiley & Sons, New York, 1984, pp. 181-182.
2. For partly reduced 1,2,3,4-tetrazines see: P. J. Mackert, K. Hafner, N. Nimmerfroh, K. Banert, Chem. Ber. 1994, 127, 1479-1488 and references cited therein.
3. T. Kaihoh, T. Itoh, K. Yamaguchi, A. Ohsawa, J. Chem. Soc., Perkin Trans. 1 1991, 2045-2048.
4. D. L. Lipilin, O. Yu. Smirnov, A. M. Churakov, Y. A. Strelenko, S. L. Ioffe, V. A. Tartakovsky, Eur. J. Org. Cheto. 2002, 3435-3446.
5. A. M. Churakov, O. Yu. Smirnov, S. L. Ioffe, Yu. A. Strelenko, V. A. Tartakovsky, Eur. J. Org. Cheto. 2002, 2342-2349.
6. For ring-chain tautomerism in 2H-cyclopenta-2-R-1,2,3,4-tetrazines see ref. [2].
7. D. L. Lipilin, A. M. Churakov, Yu. A. Strelenko, V. A. Tartakovsky, Izv. Akad. Nauk. Ser. Khim. 2002, 295-303 (Russ. Chem. Bull. 2002, 51, 311-318).
8. D. L. Lipilin, A. M. Churakov, Yu. A. Strelenko, V. A. Tartakovsky, Izv. Akad. Nauk. Ser Khim. 2002, 295-303 (Russ. Chem. Bull. 2002, 51, 311-318).
9. [8a] H. Bauer, G. R. Bedford, A. R. Katritzky, J. Chem. Soc. 1964, 751-755. For previous discussion of ring-chain tautomerism of this type of diazonium salts see: [8b] J. Ribka, Angew. Chem. 1958, 70, 241-244. [8c] J. F. Bunnett, E. Buncel, K. V. Nahadedian, J. Am. Chem. Soc. 1962, 84, 4136-4140.
10. [8a] H. Bauer, G. R. Bedford, A. R. Katritzky, J. Chem. Soc. 1964, 751-755. For previous discussion of ring-chain tautomerism of this type of diazonium salts see: [8b] J. Ribka, Angew. Chem. 1958, 70, 241-244. [8c] J. F. Bunnett, E. Buncel, K. V. Nahadedian, J. Am. Chem. Soc. 1962, 84, 4136-4140.
11. [8a] H. Bauer, G. R. Bedford, A. R. Katritzky, J. Chem. Soc. 1964, 751-755. For previous discussion of ring-chain tautomerism of this type of diazonium salts see: [8b] J. Ribka, Angew. Chem. 1958, 70, 241-244. [8c] J. F. Bunnett, E. Buncel, K. V. Nahadedian, J. Am. Chem. Soc. 1962, 84, 4136-4140.
12. I. E. Filatov, Ph.D. Dissertation, Ural State Technical Univ., 1993. The article will be published in due course.
13. It is noteworthy that the investigated salts 3/4, which exist in solutions as mixtures of tautomers, did not exhibit the absorption band of the diazonium group in the solid-state 1R spectrum (KBr), indicating that they exist in closed forms in the solid state.
14. R. O. Duthaler, H. G. Förster, J. D. Roberts, J. Am. Chem. Soc. 1978, 100, 4974-4979.
15. G. C. Levy, R. L. Lichter, Nitrogen-15 Nuclear Magnetic Resonance Spectroscopy, Wiley, New York, 1984, Chapter 3.8.
16. 13C NMR signals of the methyl groups of the salts 3h/4h and 3i/4i are in the same region as in anilines 2h and 2i. These signals are not suitable for study of the 31 4 equilibrium.
17. 6]acetone for NMR study, owing to the instability of 3h/4h and 3i/4i in acetone solutions.
18. D. F. Ewing, Org. Magn. Reson. 1979, 12, 499-524.
19. E. T. Apasov, B. A. Djetigenov, Yu. A. Strelenko, A. V. Kalinin, V. A. Tartakovsky, Izv. Akad. Nauk SSSR, Ser. Khim. 1991, 1394-1397 (Bull. Acad. Sci. USSR, Div Chem. Sci., 1991, 40, 1234-1237).
20. E. T. Apasov, B. A. Djetigenov, Yu. A. Strelenko, A. V. Kalinin, V. A. Tartakovsky, Izv. Akad. Nauk SSSR, Ser. Khim. 1991, 1394-1397 (Bull. Acad. Sci. USSR, Div. Chem. Sci., 1991, 40, 1234-1237).
21. 13C NMR signals were made by: [17a] SPT. [17b] DEPT. [17c] Experiments without proton decoupling. [17d] Selective decoupling experiments. [17e] C,H COSY. [17d] HSQC-qs and HMBC-qs experiments.