Electric moments, sulfur bonding, and conformations of substituted thiochloroformate esters in benzene solutions

1969 ◽  
Vol 47 (2) ◽  
pp. 343-348 ◽  
Author(s):  
A. Queen ◽  
T. A. Nour ◽  
E. Bock
Keyword(s):  
Sulfur Atom ◽  
Halogen Atom ◽  
Benzene Solution ◽  
Dipole Moments ◽  
Vector Model ◽  
Hydrocarbon Group ◽  
Electron Release ◽  
D Orbitals

The dipole moments of a series of aryl and alkyl thiochloroformate esters have been determined in benzene solution at 25 °C and compared with the corresponding values for chloroformate and fluoroformate esters. The results have been interpreted in terms of conjugative and hyperconjugative electron release by the hydrocarbon group to the d-orbitals of the sulfur atom in the thio compounds. Vector model, bond moment calculations indicate that, as in the cases of the chloroformate and fluoroformate esters, the preferred conformations of the thiochloroformates are those in which the hydrocarbon group and the halogen atom are cis to each other.

A Study of d-Orbital Effects in Esters of Trifluorothiolacetic Acid. A Comparison of Evidence from Dipole Moment and Kinetic Data

1974 ◽  
Vol 52 (17) ◽  
pp. 3113-3118 ◽  
Author(s):  
E. Bock ◽  
A. Queen ◽  
S. Brownlee ◽  
T. A. Nour ◽  
M. N. Paddon-Row
Keyword(s):  
Dipole Moment ◽  
Trifluoroacetic Acid ◽  
Kinetic Data ◽  
Benzene Solution ◽  
Dipole Moments ◽  
Aqueous Acetone ◽  
Electron Release ◽  
Hydrolysis Of ◽  
D Orbitals

The dipole moments of a series of esters of trifluoroacetic acid and trifluorothiolacetic acid have been determined in benzene solution at 25 °C. The results are consistent with conjugative and hyperconjugative electron release by the hydrocarbon groups to the d-orbitals of sulfur. This conclusion is supported by data for the hydrolysis of these compounds in water or aqueous acetone.

Dipole moments of substituted chloroformates in dilute benzene solutions

1967 ◽  
Vol 45 (24) ◽  
pp. 3177-3179 ◽  
Author(s):  
E. Bock ◽  
D. Iwacha
Keyword(s):  
Chlorine Atom ◽  
Benzene Solution ◽  
Dipole Moments ◽  
Experimental Results ◽  
Methyl Ethyl ◽  
Hydrocarbon Group

The dipole moments of methyl, ethyl, n-propyl, n-butyl, amyl, and phenyl chloroformate as well as n-butyl formate in dilute benzene solution at 25 °C were determined. The experimental results suggest that the configuration of the chloro-esters differs from the configuration of the unchloroinated esters, viz. the ester hydrocarbon group and the chlorine atom are cis to each other.

Dipole moments induced in larger molecule. Long-chain aliphatic esters

1982 ◽  
Vol 47 (1) ◽  
pp. 29-34 ◽  
Author(s):  
Otto Exner ◽  
Ayfer Bapçum
Keyword(s):  
Benzene Solution ◽  
Dipole Moments ◽  
Straight Chain ◽  
Basic Assumptions ◽  
Donor Acceptor ◽  
Eyring Theory ◽  
Aliphatic Esters ◽  
Long Chain

Dipole moments of straight-chain aliphatic esters Ia-Ic and IIa-IIf were measured in benzene solution. The observed trends are poorly reproduced by the classical Smith-Eyring theory; the reason may be partly the unknown conformation, partly even donor-acceptor complexes with the solvent. No deviations were observed with the highest members of the series, attributable to violation of some basic assumptions of the theory of dielectrics.

The Stereochemistry of Chloro-bis(N-morpholino)phenylsilane

1999 ◽  
Vol 54 (1) ◽  
pp. 18-20 ◽  
Author(s):  
Gerald Huber ◽  
Annette Schier ◽  
Hubert Schmidbaur
Keyword(s):  
Time Scale ◽  
Title Compound ◽  
Halogen Atom ◽  
Benzene Solution ◽  
Mirror Plane ◽  
Free Rotation ◽  
The Third ◽  
Nitrogen Inversion ◽  
Sterical Hindrance ◽  
Independent Molecules

Treatment of phenyltrichlorosilane with an excess of morpholine and N-lithium-morpholide in pentane/toluene affords only the disubstitution product Cl(Ph)Si(Mor)2 with Mor = O(CH2CH2)2N-. The third halogen atom is not replaced owing to sterical hindrance. The title compound crystallizes with two independent molecules in the unit cell. These two molecules can be classified as enantiomers, because a disrotatory twist of the two morpholino ligands away from the potential mirror plane induces a chiral conformation. In benzene solution there is racemization owing to completely free rotation, chair/boat interconversion, and nitrogen inversion of the morpholino groups on the NMR time scale, but all CH2 protons remain anisochronous (diastereotopic).

Dipole moments and conformation of α-disulphones. The gauche effect

1985 ◽  
Vol 50 (10) ◽  
pp. 2245-2251 ◽  
Author(s):  
Otto Exner ◽  
Václav Jehlička
Keyword(s):  
Dihedral Angle ◽  
Graphical Method ◽  
Benzene Solution ◽  
Dipole Moments ◽  
Statistical Treatment ◽  
X Ray ◽  
Gauche Effect

The dipole moments of substituted diphenyl disulphones I-III were measured in benzene solution and interpreted by the previously described graphical method. The results suggest an equilibrium of the ap and sc conformations in the ratio 3 : 1, at variance with various empirical rules and theories of the so-called gauche effect. A statistical treatment of X-ray data of various sulphonyl derivatives revealed essentially two preferred conformations: the more stable sc, with a broadened dihedral angle, and the less stable ap.

PHOSPHONITRILIC COMPOUNDS: PART I. THE MECHANISM OF PHOSPHONITRILIC CHLORIDE POLYMERIZATION CAPACITANCE, CONDUCTANCE, AND ELECTRON-SPIN RESONANCE STUDIES

1964 ◽  
Vol 42 (2) ◽  
pp. 447-455 ◽  
Author(s):  
H. R. Allcock ◽  
R. J. Best
Keyword(s):  
Free Radicals ◽  
Electron Spin Resonance ◽  
Electron Spin ◽  
Benzene Solution ◽  
Dipole Moments ◽  
Ring Cleavage ◽  
Preliminary Step ◽  
Polymerization Mechanism ◽  
Spin Resonance ◽  
Nitrogen Ring

Capacitance and conductance measurements were carried out with molten (NPCl2)3 and [NP(OC6H5)2]3 and dipole moments were determined in benzene solution. Attempts to detect free radicals in molten samples of the same compounds were unsuccessful. Evidence was obtained that homolytic or heterolytic phosphorus–nitrogen ring cleavage is not involved in the primary initiation process. The results favor, instead, a polymerization mechanism for (NPCl2)3 in which phosphorus–chlorine ionization is a preliminary step.

Hydrogen bonding, configuration and conformation of substituted α-oxo oximes and hydrazones

1979 ◽  
Vol 44 (8) ◽  
pp. 2494-2506 ◽  
Author(s):  
Otto Exner ◽  
Jorga Smolíková ◽  
Václav Jehlička ◽  
Ahmad S. Shawali
Keyword(s):  
Hydrogen Bond ◽  
Hydrogen Bonding ◽  
Carbonyl Group ◽  
Intramolecular Hydrogen Bond ◽  
Benzene Solution ◽  
Dipole Moments ◽  
H Nmr ◽  
Intramolecular Hydrogen ◽  
Derivatives Of ◽  
Configuration And Conformation

Substituted 2-bromo-1-phenylglyoxal 2-phenylhydrazones IIIa-f exist in tetrachloromethane or benzene solutions prevailingly in E-configuration and in conformation A with an intramolecular hydrogen bond. The latter was evidenced by the N-H valence frequency at 3 290 cm-1 and by 1H NMR shifts with reference to derivatives without a carbonyl group - α-chlorobenzaldehyde phenylhydrazones V. From dipole moments of IIIa-d, measured in benzene solution, the contribution of the hydrogen bond (μH) was evaluated to 17 . 10-30 C m. This quantity is twice larger than in any other reported compound but the direction of the vector is as usual: approximately from H to N. In structurally similar derivatives of hydroxylamine, substituted 2-phenylglyoxylhydroximoyl chlorides IVa-d, no intramolecular hydrogen bond was detected; the dipole moments found were interpreted in terms of the Z-configuration and the prevailing conformation G.

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