The dipole moments of some tri-n-butylammonium and triethylammonium salts in benzene solution

Author(s):  
K. Bauge ◽  
J. W. Smith
1982 ◽  
Vol 47 (1) ◽  
pp. 29-34 ◽  
Author(s):  
Otto Exner ◽  
Ayfer Bapçum

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.


1985 ◽  
Vol 50 (10) ◽  
pp. 2245-2251 ◽  
Author(s):  
Otto Exner ◽  
Václav Jehlička

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.


1964 ◽  
Vol 42 (2) ◽  
pp. 447-455 ◽  
Author(s):  
H. R. Allcock ◽  
R. J. Best

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.


1979 ◽  
Vol 44 (8) ◽  
pp. 2494-2506 ◽  
Author(s):  
Otto Exner ◽  
Jorga Smolíková ◽  
Václav Jehlička ◽  
Ahmad S. Shawali

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.


1984 ◽  
Vol 49 (10) ◽  
pp. 2382-2386 ◽  
Author(s):  
Gejza Suchár ◽  
Milan Dzurilla ◽  
Pavol Kristian

The dipole moments have been measured of various substituted isothiocyanates of 1,3-diphenyl-2-propen-1-one in benzene solution. The measured values have been compared with the dipole moments obtained by the vector addition of the bond dipole moments, and the comparison has been used for a discussion of their electronic structure and interactions of the NCS group.


1989 ◽  
Vol 54 (5) ◽  
pp. 1291-1298 ◽  
Author(s):  
Drahomír Hnyk ◽  
Radek Fajgar ◽  
Václav Všetečka ◽  
Otto Exner

Dipole moments of stereoisomeric 3-methoxypropenenitriles (I,II), substituted 2-methoxybenzonitriles (III-VI) and substituted 2-chlorophenyl methyl ethers (VII-X) were measured in benzene solution and analyzed in terms of group moments. Aromatic derivatives III-X exist in the prevailing conformation ap (CH3 trans to Cl or to CN). Any minor conformation was not detected; small differences between experimental and calculated dipole moments were explained by induction of the two adjacent dipoles. Conformations of 3-methoxypropenenitriles were estimated to prevailing sp for I and practically only ap for II. Irrespective of the conformations, dipole moments revealed a strong conjugation of the CN and OCH3 groups in I and II. The intensity of this conjugation in various derivatives thus decreases steeply in the series: olefinic E > olefinic Z > aromatic para > aromatic ortho.


1969 ◽  
Vol 47 (2) ◽  
pp. 343-348 ◽  
Author(s):  
A. Queen ◽  
T. A. Nour ◽  
E. Bock

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.


1974 ◽  
Vol 52 (17) ◽  
pp. 3113-3118 ◽  
Author(s):  
E. Bock ◽  
A. Queen ◽  
S. Brownlee ◽  
T. A. Nour ◽  
M. N. Paddon-Row

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.


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