Structure and Rearrangement of Ring Substituted N0Methyl-N-phenylnitramines

• Autorzy: Daszkiewicz Z. , Zaleski J. , Nowakowska E. M. , Kyzioł J. B.
• Języki publikacji: EN

Abstrakty

EN

The mechanism of the acid catalyzed nitramine rearrangement must account for the unusual sensitivity of the reaction of N-methyl-N-phenylnitramine derivatives to the ring substituents. Spectral analyses indicate the lack of interaction between the nitramino group and the second substituent through the aromatic ring. X-ray analyses confirm the spectral data: there is no conjugation between the aromatic and nitramine sextets of _-electrons. X-ray structural data also indicate that the nitramino group cannot behave as the basic centre. A reconsideration of the rearrangement rate constants of the series of ring substituted N-methyl-N-phenylnitramines lead to the conclusion that migration of the N-nitro group precedes protonation. The influence of the substituents on the reaction rates is determined by their influence on the basicity of the imino nitrogen in an intermediate. The CIDNP effect, observed in the rearrangement, results from the transformation of mobile nitrito group into the stable nitro substituent.

Słowa kluczowe

EN

nitramines; rearrangement; reaction mechanism

• Wydawca: Polskie Towarzystwo Chemiczne
• Czasopismo: Polish Journal of Chemistry
• Rocznik: 2002
• Tom: Vol. 76 / nr 8
• Strony: 1113--1125
• Opis fizyczny: Bibliogr. 28 poz., rys.

Twórcy

autor

Daszkiewicz Z.

• Institute of Chemistry, University of Opole, 45-052 Opole, ul. Oleska 48, Poland

autor

Zaleski J.

• Institute of Chemistry, University of Opole, 45-052 Opole, ul. Oleska 48, Poland

autor

Nowakowska E. M.

• Institute of Chemistry, University of Opole, 45-052 Opole, ul. Oleska 48, Poland

autor

Kyzioł J. B.

• Institute of Chemistry, University of Opole, 45-052 Opole, ul. Oleska 48, Poland

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