Inductive interaction of weak dipoles in unsaturated and aromatic hydrocarbons and their derivatives

1. Calculation of induction according to the field effect mechanism is applicable to compounds containing differently hybridized carbon atoms. 2. The "zero" moments of the bonds Csp 3-Csp 2, Csp 3-Csp, and Csp 2-Csp were calculated according to the molecular orbital method as a linear combination of atomic orbitals (MO LCAO). 3. The dipole moments of a number of alkylbenzenes and their chloro-derivatives were calculated, in agreement with the experimental data. 4. An effect of saturation of induction is observed for fluoro-derivatives. © 1968 Consultants Bureau

Three-dimensional structure of phosphorus-containing heterocycles Communication 3. The gauche-orientation of the alkoxy group in 3-alkoxy-1-thia-3-phosphethanes

1. The dipole moments and Kerr constants of five 3-methoxy- and 3-phenoxy-l-thia-3-phosphethanes with a tetracoordinated phosphorus atom were determined. 2. On the basis of a graphical treatment of the data of these methods it was shown that the four-membered ring is bent, and the two-faced angle varies from 140 to 165°. The phosphoryl (or thiophosphoryl) group occupies a pseudoequatorial position; the methoxy and phenoxy radicals have a gaucheorientation. © 1974 Consultants Bureau

Steric structure of phosphorus-containing heterocycles - Communication 4. Axial arrangement of the alkoxy group in 1,3, 2-dioxaphosphorinanes according to the data of the method of dipole moments

1. The dipole moment of 2-alkoxy- and 2-phenoxy-l, 3,2-dioxaphosphorinanes and their spiro analogs with a tricoordinated phosphorus atom were determined. 2. A graphical method was proposed for the analysis of the data of the method of dipole moments of cyclic compounds. 3. In all the compounds studied, a chair conformation with axial (or diaxial for the spiro compound) arrangement of the alkoxy group with a gauche-orientation of the methoxyl and ethoxyl radicals and a cisorientation of the phenoxy group is realized. © 1974 Consultants Bureau

Steric structure of phosphorus-containing heterocycles - Comunication 11. Aryl pyrocatechinphosphites

1. Para-substituted phenyl pyrocatechinphosphites were synthesized and their dipole moments and Kerr constants were determined. 2. A nonplanar structure of the benzodioxaphospholene ring with a dihedral bend angle of 155° and an axial phenoxyl substituent, gauche-oriented relative to the unshared pair of the phosphorus atom, was established from the joint examination of dipole moment data for the three p-X-aryl pyrocatechinphosphites. 3. Using the Kerr effect a change in orientation of the benzene ring was established upon going from pyrocatechin phenylphosphite to the o,o,p-tritert-butylphenyl derivative. © 1976 Plenum Publishing Corporation

Three-dimensional structure of phosphorus-containing heterocycles - II. Dipole moments and Kerr constants of some 2-thiono-1,3,2-dioxaphosphorinanes

The three-dimensional structure of a number of 2-thiono-1,3,2-dioxaphosphorinanes was studied by means of dipole moments, the Kerr effect, and theoretical conformational analysis with P31 NMR data. 2,4-Dimethyl- and 2-chloro-2-thiono-1,3,2-dioxaphosphorinanes have the chair conformation with an equatorial thionophosphoryl group; the 2-methyl derivative exist as an equilibrium mixture of the axial and equatorial conformers with predominance of the former. The participation of the boat form in the conformational equilibrium was established for 2-chloro-4-methyl derivative. © 1974 Consultants Bureau

Dipole moments, molar Kerr constants, and structure of epoxy derivatives of terpinolene

1. The primary oxidation of terpinolene at the semicyclic double bond was confirmed, and it was shown that the dioxide has a trans-structure. 2. Terpinolene monoxide exists in solution in the form of a mixture of two half-chair forms; for the dioxide the boat conformation is stable. © 1971 Consultants Bureau

Geometrical structures of the gem-dichlorocyclopropyl aryl selenides

1. The para-substituted gem-dichloropropyl aryl selenides have been synthesized, for the first time, and studied through their13C NMR spectra and their dipole moments and Kerr constants. 2. These compounds exist as gauche conformers with syn and anti orientation of the aromatic ring with respect to the geminal C-Cl bonds. 3. Determination has been made of the dipole moment of the {Mathematical expression} bond. © 1980 Plenum Publishing Corporation

Polarizations, polarizabilities, and conformations of the aryl methyl disulfides

1. Each of the aryl methyl disulfides exists in skew conformation with a C-S-S-C dihedral angle of 70-90°. 2. The angle of rotation of the p-XC6H4, fragment relative to the plane of the Car-S-S bonds varies from molecule to molecule, depending on the nature of the X substituent. © 1977 Plenum Publishing Corporation

Conformation of unsymmetrical diaryl disulfides

1. In solution the unsymmetrical p-substituted diaryl disulfides have a skewed conformation with a dihedral angle of ∼80°. 2. The angles of rotation of the aryl fragments relative to the planes of the Car-S-S bonds in the molecules of different compounds depend on the nature of the p-substituents. © 1978 Plenum Publishing Corporation

Kerr constants and steric structure of acetylenic thio- and selenoethers

1. The axes of the polarizability ellipoids of the Csp-S and Csp-Se bonds were determined. 2. The steric structure of a number of acetylenic thio- and selenoethers p-XC6H4E-C≡CC6H5 was studied. The benzene ring attached to the triple bond is located in the plane of the {Mathematical expression} bonds, while the aromatic fragment attached to the heteroatom (S or Se) lies outside this plane by ∼30-40°. © 1979 Plenum Publishing Corporation