Сибирский федеральный университет

Тип публикации: статья из журнала

Год издания: 2012

Идентификатор DOI: 10.1016/j.molstruc.2011.09.053

Ключевые слова: Hexasubstituted nitrosophenols, Alkylation, Nitroso phenols, Alkyl ethers of 1,4-benzoquinone-1-oximes, Polycrystalline X-ray diffraction analysis, Hartree-Fock quantum-chemical calculations, Alkyl ethers, Nitroso, Polycrystalline, Quantum-chemical calculation, Benzene, Mass spectrometry, Molecular structure, Molecules, Nitrogen compounds, Nuclear magnetic resonance spectroscopy, Organic compounds, Oxygen, Phenols, Quantum chemistry, Rietveld method, X ray powder diffraction, Ethers

Аннотация: Theoretical and experimental approaches were applied for the investigation of the reactivity of persubstituted 4-nitrosophenols in the reaction with alkyl iodides, in particular the potassium salt of 2,6-di(alkoxycarbonyl)-3,5-dimethyl-4-nitrosophenol. Hartre-Fock calculations showed that the anion negative charge was located mostly on the oxygen of hydroxyl group, while estimation of the total energy of the alkylated products pointed out the benefit of alkylation on the oxygen atom of the nitroso group yielding p-benzoquinone monoxime alkyl ethers. Methylation and ethylation of persubstituted nitrosophenols were carried out. The products obtained were investigated using X-ray diffraction, H-1 NMR spectroscopy and mass spectrometry. The crystal structure of the methyl ether of 2,6-di(alkoxycarbonyl)-3,5-dimethyl-1,4-benzoquinone-1-oxime (C15H19NO6) (I) was determined by the X-ray powder diffraction technique. The unit cell parameters were: a = 7.3322(6) angstrom, b = 10.5039(12) angstrom, c = 21.1520(20) angstrom, beta = 93.742(6)degrees, V = 1625.58(2) angstrom(3) Z = 4, Sp.Gr. P2(1)/c. The structure modeling was made in direct space by the Monte-Carlo approach using rigid and soft restrictions. The structure refinement was completed by the Rietveld method. It was established that the alkylation occurred on the oxygen atom of the nitroso group. The molecules (I) in the crystal structure were packed in columns along the axis a with pairwise convergence in a column up to the distance of 3.63 angstrom due to a 180 degrees turn of every second molecule around the column axis. In the molecular structure the methyloxime group was oriented in the benzene plane and had pi-conjugation with the ring. The ethoxycarbonyl groups were turned nearly perpendicular to the ring. Other compounds obtained had the structure of the alkyl ethers of 1.4-benzoquinone-1-oxime, which was proved by H-1 NMR spectroscopy and mass-spectrometry. (C) 2011 Elsevier B.V. All rights reserved.

Журнал: JOURNAL OF MOLECULAR STRUCTURE

Выпуск журнала: Vol. 1015

Номера страниц: 173-180

ISSN журнала: 00222860

Место издания: AMSTERDAM

Издатель: ELSEVIER SCIENCE BV

• Slaschinin D.G. (Siberian State Technological University)
• Ilushkin D.I. (Siberian State Technological University)
• Tovbis M.S. (Siberian State Technological University)
• Alemasov Y.A. (Institute of Chemistry and Chemical Technology)
• Sokolenko W.A. (Institute of Chemistry and Chemical Technology)
• Kirik S.D. (Siberian Federal University)

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