Features of light attenuation in crystals under violation of the Bouguer law

A computer simulation and measurements of the light transmittance of germanium and paratellurite crystals of different thickness were used to show that, at scattering probabilities of photons comparable to their absorption probabilities, the standard methods for calculating light extinction coefficients on the basis of the Bouguer law lead to rough errors in estimation of the optical quality of a material.     

Synthesis and structure of novel derivatives of thieno[2,3-b]thiocine. An unusual product of intramolecular cycloaddition of 2-homomethallylthio-5-methyl-3-thiophenecarbonitrile oxide

9-Methyl-3,3a,4,5-tetrahydro-6H-thieno[2,3-b]thiocino[4,5-c]isoxazole and 9-hydroxyimino-2-methyl-7-methylene-6, 7,8,9-tetrahydro-5H-thieno[2,3-b]thiocine have been prepared for the first time by the oxidation of 2--alkenylthio-3-thiophenecarbaldoximes with NaOCl. X-ray structural investigations of thieno[2,3-b]thiocine and 2-homomethallylthio-5-methyl-3-thiophenecarbaldoxime have been carried out.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1262–1266, July, 1993.     

Photochromic dihetarylethenes. 13. Optimization of conditions for the acylation of 2,5-dimethylthiophene with squaric acid dichloride

The conditions for acylation of 2,5-dimethylthiophene with squaric acid dichloride were optimized, and 3,4-bis(2,5-dimethylthiophen-3-yl)cyclobut-3-ene-1,2-dione was obtained in good yield. X-ray diffraction analysis demonstrated that the by-product has the structure of 1a,1b-dichloro-5-(2,5-dimethylthiophen-3-yl)-3-hydroxy-4,5a-dimethyl-1b,4a,5,5a-tetrahydro-1aH-1-thiacyclopropa[a]pentalen-2-one.     

Molecular and crystal structure of the intracomplex 2-[(dibutylboryloxy)(Butyl) borylamino]-4-methylpyridine with boron atoms of differing hybridization in the chelate ring

X-ray diffraction has been used to establish the crystalline and molecular structure of the intracomplex 2-[(dibutylboryloxy)(butyl)borylamino]4-methylpyridine. In the crystal, the molecule forms weak intermolecular N(H)...O hydrogen bonds. The bicyclic portion of the molecule is nearly planar. From the bond lengths in the ring, which incorporates boron atoms of differing hybridization (sp³ and sp²), it follows that delocalization of electron density extends only over the amidine fragment. Quantum chemical calculations (MO LCAO, version CNINDO/2) show that the electron density at the endocyclic nitrogen of the aminopyridine system coordinated with boron is lower than that at the endocyclic nitrogen of the aminopyridine.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 1, pp. 173–177, January, 1991.     

Structures of boron chelates of mono- and diacylketene aminals

The molecular and crystal structures of diphenylboron chelates of acetylketeneN-benzoylaminal and 2-(N-benzoyl)diaminomethylene-4-dimethylaminomethylenecyclohexane-1,3-dione and the structure of the difluoroboron complex of diacetylketeneN-benzoylaminal were established. It was found that the aminovinylcarbonyl fragment of the ligand is involved in the formation of a boron-containing ring. A delocalized -electron system over the NCCCO fragment of the chelate ring is characteristic of the molecules studied both in crystals and solutions.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2541–2546, October, 1996.     

Crystal and molecular structures of [10]-α-cyclothienone-1

Journal of Structural Chemistry -     

Structure and conformational features of tetrahydrothienothiepinoisoxazole as a novel heterocyclic system

The crystal and molecular structure of a novel heterocyclic system, 8-methyl-3,3a,4,5-tetrahydrothieno[3,2:6,7]thiepino[4,5-c]isoxazole, has been determined by X-ray analysis. The seven-membered ring has the boat conformation (B), while the isoxazoline cycle has the flat chair conformation (₃E). There are strong steric strains between the vicinal protons at the C(3a), C(3), and C(4) atoms.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1795–1797, October, 1994.     

Synthesis and X-ray study of a bis-diphenylboron chelate of 3-(diaminomethylene)pentane-2,4-dione

A bis-diphenylboron chelate has been synthesized from 3-(diaminomethylene)pentane-2,4-dione through the action of (butylthio)diphenylborane and its molecular and crystal structures have been determined. The two boron -containing rings have the same six-membered skeleton but differ substantially in conformation and geometric parameters.Translated fromlzvestiva Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2733–2735, November, 1996,     

Synthesis of novel mono- and diaryl-substituted [2.2]paracyclophanes

The cross-coupling reactions of 4-bromo[2.2]paracyclophane withp-tolylmagnesium bromide in the presence of various palladium and nickel complexes have been studied. It was found that [1,1 -bis(diphenylphosphinoferrocene)]palladium dichloride (PdCl₂ · dppf) shows the highest catalitic activity in this reaction. A series of new mono- and diaryl [2.2]paracyclophane derivatives with various substituents in the arene ring have been synthesized using this catalyst. It was shown that it is possible to cross-couple organozinc [2.2]paracyclophane derivatives with aromatic bromides. The composition and structure of the compounds obtained have been established on the basis of elemental analysis and spectral data. Some correlations between the structure and spectral parameters of mono- and diarylsubstituted [2.2]paracyclophanes have been found.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1081–1085, June, 1994.The present work was financially supported by the Russian Foundation for Basic Research (Project No. 93-03-5246).The authors wish to express their gratitude to Prof. N. A. Bumagin for his scientific interest and helpful discussions.     

Novel ligands based on bromosubstituted hydroxycarbonyl [2.2]paracyclophane derivatives: synthesis and application in asymmetric catalysis

New planar-chiral hydroxycarbonyl [2.2]paracyclophane derivatives, 4-acetyl-13-bromo-5-hydroxy[2.2]paracyclophane (Br-АНРС, 63%) and 4-benzoyl-13-bromo-5-hydroxy[2.2]paracyclophane (Br-BHPC, 53%), were synthesized and reacted with the enantiomers of α-phenylethylamine to form corresponding Schiff bases, 12-bromo-4-hydroxy-5[1-(1-phenyl-ethylimino)-ethyl]-[2.2]paracyclophane and 12-bromo-4-hydroxy-5[1-(1-phenyl-ethylimino)-(phenyl)methylen-[2.2]paracyclophane. The diastereomers of the imines were resolved and their absolute configurations and consequently the corresponding configurations of the enantiomers of Br-АНРС were determined by X-ray diffraction. Enantiomerically pure Schiff bases were applied as ligands to form catalysts for the enantioselective addition reaction of diethylzinc with benzaldehyde where 1-phenylpropanol was obtained with 77–91% ee.