scholarly journals Substituent Effects in the Noncovalent Bonding of SO2 to Molecules Containing a Carbonyl Group. The Dominating Role of the Chalcogen Bond

2014 ◽  
Vol 118 (21) ◽  
pp. 3835-3845 ◽  
Author(s):  
Luis Miguel Azofra ◽  
Steve Scheiner
Keyword(s):  
Carbonyl Group ◽  
Substituent Effects ◽  
Chalcogen Bond ◽  
Noncovalent Bonding

Role of the carbonyl group of local anesthetics in their anesthetic effect

1972 ◽  
Vol 73 (5) ◽  
pp. 553-556
Author(s):  
V. M. Belobrov ◽  
I. V. Komissarov ◽  
L. E. Makarova ◽  
N. Z. Rudenko ◽  
E. V. Titov
Keyword(s):  
Carbonyl Group ◽  
Local Anesthetics ◽  
Anesthetic Effect

On the Mechanism and Substituent Effects of the Tl(III) Oxidation of Phenylethylenes in Methanol

1973 ◽  
Vol 51 (14) ◽  
pp. 2366-2374 ◽  
Author(s):  
L. Nadon ◽  
M. Tardat ◽  
M. Zador ◽  
S. Fliszar
Keyword(s):  
Substituent Effects ◽  
Oxidation Products ◽  
Rate Determining Step ◽  
Mechanism Of Reaction

The oxidation of phenylethylenes by Tl(NO3)3 in methanol proceeds rapidly and selectively to give the products resulting from the migration of aryl groups, i.e., (i) the 1,1-dimethoxy-2-phenylethanes from the corresponding styrenes, (ii) the phenylacetones from the α-methylstyrenes, and (iii) the two possible deoxybenzoines from the 1,1,-diphenylethylenes. The kinetic results, which indicate the formation of the thallic–organic intermediate to be the rate determining step, are discussed in terms of the mechanism of reaction and show the role of the coordination of Tl(III). Hammett's relationship, with ρ = −4.2, describes the substituent effects for the competitive oxidation of ring-substituted styrenes and α-methylstyrenes. The relative migratory aptitudes of aryl groups, as determined from the oxidation products of ring-substituted 1,1-diphenylethylenes, is correlated to Brown's σ+ constants, with ρ+ = −2.27.

A MNDO study of planar thioacyl-substituted carbocations

1992 ◽  
Vol 70 (1) ◽  
pp. 111-115 ◽  
Author(s):  
Jack Leon Ginsburg ◽  
Richard Francis Langler ◽  
Raj Kumar Raheja ◽  
Laura Precedo
Keyword(s):  
Gas Phase ◽  
Substituent Effects ◽  
Mndo Method ◽  
Saturation Effect ◽  
Semiempirical Calculations ◽  
Isodesmic Reactions ◽  
Electron Population ◽  
Resonance Saturation ◽  
Carbonium Ions

Relative gas phase stabilities of pairs of planar regioisomeric thioacyl-substituted carbocations have been calculated using the MNDO method. These systems are stabilized by good π donors. The role of S π-electron population as a gauge of substituent effects is examined. Similar results were obtained using isodesmic reactions to gauge substituent effects. Results of this and earlier studies are consistent with the resonance saturation effect. Keywords: semiempirical calculations, carbonium ions.

Sign in / Sign up

Export Citation Format

Share Document