A study of the process of lignification of one-year willow wood

Conclusions 1. The content of lignin in the wood ofSalix viminalis andSalix acutifolia increases with the growth of the shoots during shortened days and also in drier climatic periods.2. The monosaccharides, glucose, fructose, and arabinose take part in the synthesis of the lignin of young wood ofSalix viminalis andSalix acutifolia. The formation of lignin of one-year willow wood takes place from May to January (with a maximum in June–July). The content of methoxyl groups in it gradually rises.Khimiya Prirodnykh Soedinenii, Vol. 5, No. 6, pp. 546–550, 1969     

Infrared spectra of cyclic ethers and their derivatives

Data for the characteristic bands of cyclic ethers are reviewed. The infrared spectra of a number of 2-mono- and 2, 5-di-substituted derivatives of tetrahydrofuran are investigated. Absorption bands at about 900 cm⁻¹ are related to pulsation vibrations, and those at about 1200 cm⁻¹ to antisymmetric skeletal vibrations, of the tetrahydrofuran ring. It is shown that to confirm the presence of a tetrahydrofuran ring in a molecule, it is necessary to take into account not only the band of valence antisymmetric vibrations of the group C-O-C (ν _C-O-C ^as 1075 cm⁻¹), but also bands due to ring pulsation vibrations (ring symmetric valence vibrations ν _sk ^s ∼ 900 cm¹).     

Pyridylethylation of cyclic thioamides and amides. I. Pyridylethylation in the tetrazole and 1, 2, 4-triazole series

1-Aryltetrazoline-5-thiones and 4-aryl-1, 2, 4-triazolyl-3-thiones which are cyclic amides and potential mercapto compounds have been 2-pyridylethylated for the first time. It is shown that in the compounds prepared the 2-pyridylethyl-2 group is on the nitrogen atom of the thioamide group, so that the above compounds react as thiones.     

Catalytic isomerization of olefins on BeO, I

The catalytic activity of BeO for the double bond shift of 1-pentene has been investigated. The maximum activity was exhibited by samples calcined at 1173 K. The effect of pyridine, CO₂ and CCl₄ on the activity was also studied. Lewis acid-base site pairs appear to be active for the isomerization.

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BeO 1- . , 1173 . , CO₂ CCl₄ . - .

     

Conversions of 2-thioxo-1,3-dithiol-4,5-dicarboxylic acid dimethyl ester — The path to a new heterocyclic system, (4H,6H)-1,3-dithiolo[4,5-d]pyrimidine-2,5,7-trione and 5,6-dimercaptouracil derivatives

The conversions of 2-thioxo-1,3-dithiol-4,5-dicarboxylic acid methyl ester into anhydride, mono- and diamide, and monoamide methyl ester were demonstrated. The new heterocyclic system, (4H,6H)-1,3-dithiolo[4,5-d]pyrimidine-2,5,7-trione, was obtained by oxidative rearrangement-cyclization of 2-oxo-1,3-dithiol-4,5-dicarboxylic acid diamide with phenyliodosyl(hydroxy)tosylate and used to synthesize previously unknown 5,6-dimercaptouracil derivatives, including nickel dithiolene complex.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1270–1275, September, 1992.     

Deuteron magnetic resonance study of single crystals of NaDSeO3

A deuteron magnetic resonance study of a single crystal of NaDSeO₃ at room temperature is reported. The observed electric field gradient tensors correspond to two nonequivalent hydrogen bonds. The quadrupole coupling constants ($\text{eQq}\text{h}$) and asymmetry parameters (η) are found to be 172.8 and 0.07 kHz for D(1), and 152.5 and 0.08 kHz for D(2). D(2) are ordered, but D(1) are found to be dynamically disordered. The DMR results are consistent with recent X-ray reinvestigation. No phase transitions have been encountered in the temperature range 336 to 77 K.     

The synthesis of 1,2-diacetyl- and 1,2-diethylferrocenes

A method is described for the preparation of 1,2-diacetylferrocene, in which ferrocene is acetylated with acetyl chloride in the presence of AlCl₃ in methylene chloride. Addition of the ferrocene to an excess of the acetylation mixture over a prolonged period was found to be most favourable. The 1,2-diacetylferrocene formed proved to be free of the 1,3-isomer. It was reduced with LiAlH₄/AlCl₃ to 1,2-diethylferrocene.     

Special features in the chemical structure of phosphorus isocyanates

The UV and IR absorption spectra and the NMR and NQR spectra of certain isocyanates of three- and four-coordinated phosphorus have been investigated. The reciprocal effect of the phosphorus atom and the NCO group is discussed on the basis of spectral analysis, quantum chemical calculations of the electron systems, and calculations of the normal vibrational forms. Comparison of the (PO) frequencies in the IR spectra of the phosphorus isocyanates with the Taft gives a linear relationship which testifies to the predominant inductive effect of the NCO group on the P(O)R₁R₂ grouping. A similar relationship is observed between the resonance frequency _res in the NMR spectra and for C1P(O)R₁R₂ compounds. The effect of the phosphorus atom on the electronic system in the NCO group is shown by the hypsochromic shift of the absorption band in the210-m region and an appreciable increase in its intensity, compared with alkyl isocyanates. This fact, which agrees with the NMR spectral data and the quantum chemical calculations, indicates the presence of conjugation in the P-N bond. We found the order of the P-N bond to be approximately 1.2. This partial double-bond nature of the P-N bond results from the interaction of the p electrons of nitrogen in the NCO group with the d orbitals of the phosphorus atom.We are grateful to our colleagues at the Kazan Physicotechnical Institute AS USSR A. I. Rivkind, S. G. Salikhov, and I. A. Safin for recording the spectra.