Substituent effects on the rate of reaction of aqueous hydrogen (tritium) atoms with aromatic compounds

1971 ◽  
pp. 148 ◽  
Author(s):  
C. L. Brett ◽  
V. Gold
Keyword(s):  
Aromatic Compounds ◽  
Substituent Effects ◽  
Rate Of Reaction

Infrared spectra of aqueous sodium benzoates and salicylates in the carboxyl-stretching region: chelation in aqueous sodium salicylates

1969 ◽  
Vol 47 (24) ◽  
pp. 4577-4588 ◽  
Author(s):  
G. E. Dunn ◽  
R. S. McDonald
Keyword(s):  
Salicylic Acid ◽  
Carbon Tetrachloride ◽  
Infrared Spectra ◽  
Aromatic Compounds ◽  
Deuterium Oxide ◽  
Substituent Effects ◽  
Good Evidence ◽  
Frequency Region ◽  
Aqueous Sodium ◽  
Substituent Constants

Infrared spectra in the frequency region 1300–1760 cm−1 are reported for 41 substituted sodium benzoates and 10 substituted sodium salicylates in deuterium oxide solution, and for 9 substituted salicylic acids in chloroform and carbon tetrachloride solutions. Carboxylate stretching frequencies of benzoates and salicylates correlate poorly with substituent constants, but the asymmetric frequencies of benzoates and salicylates correlate well with each other, and the asymmetric frequencies of benzoates correlate well with the asymmetric frequencies of the corresponding nitrobenzenes. It is suggested that, among substituted aromatic compounds, group vibrations which couple with the ring vibrations may correlate well with similar vibrations of other groups, but not with coupled vibrations of different symmetry, uncoupled vibrations, or substituent constants. Chelation in chloroform solutions of salicylic acid dimers can be detected by its influence on substituent effects, but infrared spectra provide no good evidence for chelation in aqueous sodium salicylates.

The Iodination of Aromatic Compounds. I. The Action of Iodine on Aniline in the Presence of Mercuric Oxide

1949 ◽  
Vol 2 (1) ◽  
pp. 111
Author(s):  
L Jurd
Keyword(s):  
Zinc Oxide ◽  
Aromatic Compounds ◽  
Mercuric Oxide ◽  
Mercuric Iodide ◽  
Rate Of Reaction ◽  
Ferric Oxides

A satisfactory process for the preparation of p-iodo- and 2,4-diiodo-aniline has been developed, aniline being treated with iodine in the presence of mercuric oxide. Acetanilide was also iodinated by this procedure. When lead, calcium, and ferric oxides were employed the yields of p-iodo-aniline proved to be only slightly greater than that obtained by the action of iodine alone, whilst zinc oxide lowered the yield considerably. The influence of added iodides, acids, and mercuric iodide on the rate of reaction of iodine and aniline was investigated. A theory has been proposed to explain the role of mercuric oxide in effecting the iodination of aniline.

Stabilities of Carbonium-Ions. IV. Steric Effects in the Solvolysis of Substituted Diphenylmethyl Chlorides

1986 ◽  
Vol 39 (4) ◽  
pp. 625 ◽  
Author(s):  
R Bolton ◽  
RE Burley ◽  
NJ Williams
Keyword(s):  
Electronic Effect ◽  
Substituent Effects ◽  
Methyl Chloride ◽  
Steric Effects ◽  
Methyl Groups ◽  
Hydrogen Atoms ◽  
Carbonium Ions ◽  
Rate Of Reaction ◽  
Resonance Stabilization ◽  
Planar Transition

The replacement of ortho-hydrogen atoms by methyl groups in diphenylmethyl chloride has three distinguishable results upon the rate of solvolysis . Firstly, the alkyl groupactivates by its electronic effect; secondly, steric interactions diminish all observed substituent effects regardless of the position of the substituent in the aryl system; and thirdly, steric acceleration of the solvolysis can be seen in the rate of reaction of bis (2,6-dimethylphenyl)methyl chloride. The ortho-methyl substituents inhibit the formation of the planar transition state necessary to allow the greatest resonance stabilization by the aryl substituents of the incipient carbocation. Greater degrees of twist are reflected both in the variations in the rates of solvolysis of the poly(orthomethyl ) diphenylmethyl chlorides and in the consistent fall in the value of p+ with successive ortho-substitution.

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