Persubstituted p-benzoquinone monoxime alkyl ethers and their molecular structure

• Published in: Journal of molecular structure 2012-05, Vol.1015, p.173-180
• Main Authors: Slaschinin, D.G., Alemasov, Y.A., Ilushkin, D.I., Sokolenko, W.A., Tovbis, M.S., Kirik, S.D.
• Format: Article
• Language: English
• Subjects: Alkyl ethers of 1,4-benzoquinone-1-oximes; Alkylation; benzene; benzoquinones; crystal structure; energy; ethers; Hartree–Fock quantum-chemical calculations; Hexasubstituted nitrosophenols; iodides; mass spectrometry; methylation; Nitroso phenols; nuclear magnetic resonance spectroscopy; oxygen; Polycrystalline X-ray diffraction analysis; potassium; X-radiation; X-ray diffraction
• ISSN: 0022-2860; 1872-8014
• DOI: 10.1016/j.molstruc.2011.09.053

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, 1Н 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 (С15H19NO6) (I) was determined by the X-ray powder diffraction technique. The unit cell parameters were: a=7.3322(6)Å, b=10.5039(12)Å, c=21.1520(20)Å, β=93.742(6)°, V=1625.58(2)Å3Z=4, Sp.Gr. P21/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 3.63Å due to a 180° turn of every second molecule around the column axis. In the molecular structure the methyloxime group was oriented in the benzene plane and had π-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 1Н NMR spectroscopy and mass-spectrometry.