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EPR and ESEEM Identification of Free Radicals and Molecular Structure of the Oligomers Formed During Polycondensation of 1-Chloro-4-nitrobenzene with Sodium Sulfides in N-Methyl-2-pyrrolidone

Identyfikatory
Warianty tytułu
Języki publikacji
EN
Abstrakty
EN
The synthesis of derivative of poly (4-hydrazo-diphenylenedisulfide) by reaction of 1-chloro-4-nitrobenzene with sodium sulfide and disulfide in N-methyl-2-pyrrolidone leads to oligomeric products with average molecular weight of the homogeneous chains 1182 g/mol and 690 g/mol, respectively. The mechanisms of the reactive intermediates polycondensation reaction are described. The products were characterized by IR, 1H NMR, and EPR spectroscopy and by elemental analysis. The final amorphous oligomer products contain mostly diamagnetic species and about 1% of paramagnetic species. The latter produce strong isotropic EPR signal at g = 2.0025 from free radical with concentration of about 1018 radicals/gram. Pulsed EPR spectroscopy allowed identifying the radical by analysis of the electron spin echo envelope modulation spectrum. The radical is localized on the carbon atom of the C=O-group of the N-methyl-2-pyrrolidone moiety with broken internal C-N bond of the lactam ring.
Rocznik
Strony
87--98
Opis fizyczny
Bibliogr. 17 poz., rys.
Twórcy
autor
  • Institute of Molecular Physics, Polish Academy of Sciences, Smoluchowskiego 17, PL-60179 Poznan, Poland, Fax: 48-61-8684 524
autor
  • August Cieszkowski Agricultural University, Faculty of Wood Technology, Department of Chemistry, Wojska Polskiego 75, PL-60625, Poznañ, Poland
autor
  • Institute of Molecular Physics, Polish Academy of Sciences, Smoluchowskiego 17, PL-60179 Poznan, Poland, Fax: 48-61-8684 524
autor
autor
  • Institute of Molecular Physics, Polish Academy of Sciences, Smoluchowskiego 17, PL-60179 Poznan, Poland, Fax: 48-61-8684 524
  • August Cieszkowski Agricultural University, Faculty of Wood Technology, Institute of Chemical Wood Technology, Wojska Polskiego 28, PL-60637, Poznań, Poland
Bibliografia
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  • 2. Hanczak H. and Wejchan-Judek M., Polymer Degr. Stab., 29, 247 (1990).
  • 3. Hashimoto K., Progr. Polym. Sei., 225, 1411 (2000).
  • 4. Ränby B. and Rabek J.F., “ESR Spectroscopy in Polymer Research", Springer Verlag, Berlin, 1977, chapter 4.
  • 5. Bogert M.T. and Stull A., in “Organic Syntheses, Collective", Vol. 1, Wiley, NY, 1944, p. 220.
  • 6. Fuson R.C. and Melamed S., J. Org. Chem., 13, 690 (1948).
  • 7. Montanari S., Paradisi C. and Scorrano G., J. Org. Chem., 56, 4274 (1991).
  • 8. Koch H. and Heitz W„ Makromol. Chem., 184, 779 (1983).
  • 9. Lehmann T., Michel D., Glaenzel M., Waibel R. and Gmeiner P., Heterocycles, 51,1389 (1999).
  • 10. Kobayashi K., Kitamura T. and Nakahashi R., Heterocycles, 53, 1021 (2000).
  • 11. Taplick T. and Rätzsch M., Faserforsch. Textiltechnik, 29, 579 (1978).
  • 12. Gordy W., “Theory and Application of Electron Spin Resonance", Wiley, NY, 1980, chapter 8.
  • 13. Dikanov S.A. and Tsvetkov Yu.D., “Electron Spin Echo Envelope Modulation (ESEEM) Spectroscopy”, CRC Press, Boca Raton, 1992.
  • 14. Dikanov S.A. and Astashkin A.V., in “Advanced EPR. Applications in Biology and Biochemistry", A.J. Hoff Ed., Elsevier, Amsterdam, 1989, chapter 2.
  • 15. Deligiannakis Y., Laoloudi M. and Hadjiliadis N., Coord. Chem. Rev., 204, 1 (2000).
  • 16. McCracken J., Pember S., Benkovic S.J., Villafranca J.J., Miller R.J. and Peisach J., J. Am. Chem. Soc., 110, 1069(1988).
  • 17. Bender Ch. J., Casimiro D.R., Peisach J. and Dyson H. J.,J. Chem. Soc. Farad. Trans., 93,3967 (1997).
Typ dokumentu
Bibliografia
Identyfikator YADDA
bwmeta1.element.baztech-article-BUJ1-0023-0066
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