Ⅶ 援助ネットワークの広がりとその規定要因 ―「助け合いの輪」は何によって広がるのか―

1. The PMR spectra and conformations of dimethyl orthophthalate and dimethyl isophthalate were studied. 2. A theoretical estimation was made of the constants in the equation relating the value of the chemical shift to the charge distribution. 3. The experimental distribution of charge in dimethyl orthophthalate, dimethyl isophthalate, and methyl benzoate was obtained and is in qualitative agreement with the theoretical data. © 1970 Consultants Bureau

Study of the proton chemical shifts and charge distribution in derivatives of aromatic carboxylic acids

1. The PMR spectra and conformations of dimethyl orthophthalate and dimethyl isophthalate were studied. 2. A theoretical estimation was made of the constants in the equation relating the value of the chemical shift to the charge distribution. 3. The experimental distribution of charge in dimethyl orthophthalate, dimethyl isophthalate, and methyl benzoate was obtained and is in qualitative agreement with the theoretical data. © 1970 Consultants Bureau

NMR spectral and quantum-chemical structural study of phosphorinane derivatives

1. Nonempirical calculations were carried out for the first time for substituted phosphorinanes. The conformer with an axial methyl group at the phosphorus atom predominates in 5-methyl-1,3,5-dioxaphosphorinanes as well as in the 5-oxa and 5-thio derivatives. The conformer with an equatorial methyl group at the phosphorus atoms and axial N-H bonds predominates in 5-thio-5-methyl-1,3,5-diazaphosphorinanes. 2. CNDO/2 and ab initio calculations for 5-methyl-1,3,5-dioxaphosphorinanes and its 5-oxo derviatives show the same trend for change in the energies of the favored conformers. 3. The conformer with an axial phenyl group oriented approximately in the symmetry plane of the molecule predominates in 5-phenyl-1,3,5-dioxaphosphorinanes and their 5-oxo derivatives, while the conformer with an equatorial phenyl group oriented approximately in the molecular symmetry plane is favored in 1,3,5-triphenyl-1,3,5-diazaphosphorinane. © 1985 Plenum Publishing Corporation

Reactions of Phosphorylsulfenyl Chlorides with 2H-1,2,3-Diazaphospholes

Formation of a quasiphosphonium salt in reaction of phosphorylsulfenyl chlorides with 1,2,3-diazaphospholes was established by dynamic 31P NMR spectroscopy. The salt is formed by addition of 2 mol of phosphorylsulfenyl chloride to the σ2λ3P=C endocyclic fragment by the 1,1- and 1,2-addition schemes. Decomposition of the salt yields mainly O,O-dialkyl phosphothiochloridate and, to a lesser extent, dialkyl phosphochloridate

Reaction of Trichloro(o-phenylenedioxy)phosphorane with 1,2-Alkadienylphosphonates

Trichloro(o-phenylenedioxy)phosphorane reacts with 1,2-alkadienylphosphonates with selective replacement of the alkoxy group in the phosphinoyl moiety, yielding the corresponding 1,2-alkadienylchlorophosphonates and o-phenylene chlorophosphate

On the mechanism of acetone and diacetyl reactions with halogenophosphoranes

In this study the interaction of acetone and diacetyl with pyrocatecholtrihalogenophosphoranes (PTHP) containing a five-membered cycle which improves the stability of pentacoordinated phosphorus state was first observed. Using NMR spectroscopy technique the reaction of PTHP with acetone is shown to be a quantitative unidirectional process without formation of any stable intermediates. Unlike acetone, diacetyl interaction with phosphoranes results in formation of relatively stable pentacoordinated intermediates, the products of both carbonyl groups reaction

Peculiar features of reaction of 2-tert-butoxy-5,6-benzo-1,3,2-dioxaphosphinin-4-one with chloral. Steric structure of 2-chloro-3-trichloromethyl-6,7-benzo-1,4,2λ ⁵-dioxaphopshepin-5-one 2-oxide

The reaction of 2-tert-butoxy-5,6-benzo-1,3,2-dioxaphosphinin-4-one with chloral involves expansion of the six-membered heteroring to form 2-hydroxy-3-trichloromethyl-6,7-benzo-1,4,2λ 5-dioxaphosphepin-5-one 2-oxide as a single diastereomer. The product was chlorinated with thionyl chloride to obtain (RS,SR)-2-chloro-3-trichloromethyl-6,7-benzo-1,4,2λ 5-dioxaphosphepin-5-one 2-oxide

Study of the proton chemical shifts and charge distribution in derivatives of aromatic carboxylic acids

1. The PMR spectra and conformations of dimethyl orthophthalate and dimethyl isophthalate were studied. 2. A theoretical estimation was made of the constants in the equation relating the value of the chemical shift to the charge distribution. 3. The experimental distribution of charge in dimethyl orthophthalate, dimethyl isophthalate, and methyl benzoate was obtained and is in qualitative agreement with the theoretical data. © 1970 Consultants Bureau

NMR spectral and quantum-chemical structural study of phosphorinane derivatives

1. Nonempirical calculations were carried out for the first time for substituted phosphorinanes. The conformer with an axial methyl group at the phosphorus atom predominates in 5-methyl-1,3,5-dioxaphosphorinanes as well as in the 5-oxa and 5-thio derivatives. The conformer with an equatorial methyl group at the phosphorus atoms and axial N-H bonds predominates in 5-thio-5-methyl-1,3,5-diazaphosphorinanes. 2. CNDO/2 and ab initio calculations for 5-methyl-1,3,5-dioxaphosphorinanes and its 5-oxo derviatives show the same trend for change in the energies of the favored conformers. 3. The conformer with an axial phenyl group oriented approximately in the symmetry plane of the molecule predominates in 5-phenyl-1,3,5-dioxaphosphorinanes and their 5-oxo derivatives, while the conformer with an equatorial phenyl group oriented approximately in the molecular symmetry plane is favored in 1,3,5-triphenyl-1,3,5-diazaphosphorinane. © 1985 Plenum Publishing Corporation