Effects of Bromine Substituents on Rates of Acetate-promoted Enolization of Ketones

1972 ◽  
Vol 50 (19) ◽  
pp. 3242-3247 ◽  
Author(s):  
R. A. Cox ◽  
J. Warkentin
Keyword(s):  
Transition State ◽  
Carbonyl Group ◽  
Substituent Effects ◽  
Steric Effects ◽  
Ionization Constants ◽  
Polar Substituent ◽  
Methylene Group ◽  
Better Than

Effects of bromine substituents on rates of acetate-catalyzed bromination of ketones are reported. Approximate polar contributions to the rates were obtained, based on the approximation that the steric effects of bromine and methyl are identical. Such polar substituent effects are quite large at the α′-position of an α-bromo ketone, leading to the conclusion that the carbonyl group is much better than the methylene group in transmitting polar effects.Rate enhancements caused by α-bromine substituents are largely entropic in origin and rates correlate well with ionization constants of α-bromo acids. These results are interpreted as indicative of an enolate-like transition state for acetate-catalyzed enolization.

Kinetics of reactions of para-substituted phenyl isocyanates with amines and alcohols

1991 ◽  
Vol 56 (8) ◽  
pp. 1662-1670 ◽  
Author(s):  
Ivan Danihel ◽  
Falk Barnikol ◽  
Pavol Kristian
Keyword(s):  
Transition State ◽  
Solvent Effects ◽  
Rate Constants ◽  
Substituent Effects ◽  
Steric Effects ◽  
Stopped Flow ◽  
Partial Charges ◽  
Hammett Correlation ◽  
One Step ◽  
Kinetics Of

The reaction of para-substituted phenyl isocyanates with amines and alcohols was studied by stopped-flow method. The Hammett correlation obtained showed that the sensitivity of the above mentioned reactions toward substituent effects is the same as that of analogous reactions of phenyl isothiocyanates (ρ ~ 2). The rate constants of these reactions were found to be affected more by steric effects than by solvent effects. An one step multicentre mechanism with partial charges in transition state has been proposed for the title reactions.

Thermodynamic functions of ionization of t-butyl-substituted and methoxysubstituted phenols

1972 ◽  
Vol 25 (1) ◽  
pp. 75 ◽  
Author(s):  
PD Bolton ◽  
FM Hall ◽  
J Kudrynski
Keyword(s):  
Aqueous Solution ◽  
Thermodynamic Functions ◽  
Spectrophotometric Method ◽  
Substituent Effects ◽  
Steric Effects ◽  
Ionization Process ◽  
Ionization Constants ◽  
Temperature Range

Thermodynamic ionization constants of 2-t-butylphenol, 3-t-butylphenol, 4-t-butylphenol, 3,5-di-t-butylphenol, and 3,5-dimethoxyphenol have been measured in aqueous solution by an e.m.f./spectrophotometric method within the temperature range 5-60�C and the thermodynamic functions of ionization ΔG25, ΔH25, ΔS25, and ΔCp25 calculated. These results confirm the additivity of substituent effects noted previously for the ionization of 3,5-disubstituted phenols and indicate that this ionization process is relatively insensitive to steric effects.

Substituent effects on the ionization constants of phenylazobenzaldoximes

1976 ◽  
Vol 54 (20) ◽  
pp. 3260-3266 ◽  
Author(s):  
Ahmad S. Shawali ◽  
Baheega M. Altahou
Keyword(s):  
Substituent Effects ◽  
Solution Phase ◽  
Ionization Constants ◽  
Water Medium ◽  
Hammett Equation ◽  
Substituent Constant ◽  
Polar Substituent ◽  
Linear Correlations

Ionization constants, pKa, for a set of 12 phenylazobenzaldoximes (1) have been determined in 50 vol% ethanol–water medium at 25 ± 0.1 °C and a μ of 0.1. Excellent linear correlations are obtained when pKa values are plotted against the substituent constant, σx, and the polar substituent constant, σ*XC6H4, for substituted phenyl groups. The regression lines are: pKa = 9.905–0.737σX; and pKa = 10.489 − 1.01σ* XC6H4 respectively. The pKa values have also been correlated with the extended Hammett equation. The correlation follows the equation: PKa =9.987 − 0.713σI,X−0.734 σR,X. It is concluded that EE and ZE forms of 1 exist in equilibrium in solution phase.

Substituent Rate Effects in Sigmatropic Homodienyl [1,5]-Hydrogen Migrations

1990 ◽  
Vol 43 (8) ◽  
pp. 1357 ◽  
Author(s):  
GG Pegg ◽  
GV Meehan
Keyword(s):  
Transition State ◽  
Charge Separation ◽  
Substituent Effect ◽  
Substituent Effects ◽  
Aryl Group ◽  
Rate Enhancement ◽  
Polar Substituent ◽  
Rate Effects ◽  
Electronic Perturbation

The small but systematic polar substituent effect on the rates of [1,5]- homodienyl hydrogen migrations previously observed for the series of alkenylcyclopropane substrates (1) has been further explored through two additional substrate series (4) and (6) bearing the aryl probe at C4 and at the migration origin C1 respectively. However, negligible substituent effects were apparent at these positions. It now seems that the substituent effect originally observed at C5 reflects electronic perturbation by the substituent, rather than an inherent charge separation in the transition state for homodienyl rearrangement. The aryl group at C1 of the series (6) does, however, afford a substantial rate enhancement relative to the parent cis-1-methyl-2-vinylcyclopropane. In addition, exclusive formation of (1E,4Z)-1-arylhexa-1,4-diene rearrangement products is observed. These kinetic and stereochemical observations are interpreted in terms of a stereoelectronically favoured equatorial conformation for the aryl group in the transition state for rearrangement.

ChemInform Abstract: POLAR SUBSTITUENT EFFECTS IN ADDITIONS OF ALKYL RADICALS TO ALKENES

1981 ◽  
Vol 12 (37) ◽  
Author(s):  
B. GIESE ◽  
J. MEIXNER
Keyword(s):  
Substituent Effects ◽  
Alkyl Radicals ◽  
Polar Substituent

Nuclear magnetic resonance characterization of the ring conformations of monosubstituted derivatives of 1,3-dioxa-5,6-benzocycloheptene

1983 ◽  
Vol 61 (1) ◽  
pp. 109-115 ◽  
Author(s):  
R. St-Amour ◽  
M. St-Jacques
Keyword(s):  
Nuclear Magnetic Resonance ◽  
Magnetic Resonance ◽  
Substituent Effects ◽  
Steric Effects ◽  
Slow Exchange ◽  
Conformational Properties ◽  
Derivatives Of ◽  
Ring Conformations ◽  
Twist Boat

The conformational properties of 2-alkyl (Me, Et, i-Pr, and t-Bu) and 2-phenyl derivatives of 1,3-dioxa-5,6-benzocycloheptene (1) were studied by 13C dnmr. Analysis of slow exchange spectra at 100.6 MHz indicates that all derivatives except tert-butyl exist in an equilibrium of chair (major) and twist-boat (minor) conformations. Substituent effects on the position of the equilibrium are rationalized in terms of steric effects.

Nucleophilic cleavage of diaryl disulphides

1973 ◽  
Vol 26 (1) ◽  
pp. 121 ◽  
Author(s):  
DAR Happer ◽  
JW Mitchell ◽  
GJ Wright
Keyword(s):  
Transition State ◽  
Reaction Rate ◽  
Substituent Effects ◽  
Butyl Alcohol ◽  
Sulphur Atom ◽  
Cyanide Ion ◽  
Benzene Rings ◽  
Nucleophilic Cleavage ◽  
Rapid Equilibrium ◽  
Electron Withdrawal

The rates of cleavage of 14 symmetrically substituted diaryl disulphides by cyanide ion have been measured in 60% aqueous t-butyl alcohol at pH 9.2. A plot of log k against σ� shows that while the reaction rate is accelerated by inductive electron withdrawal from the benzene rings, substituents capable of conjugative interaction are not correlated by their σ� parameters. +R substituents cause reaction to occur much faster than predicted on the basis of their σ� values, while -R substituents react more slowly than predicted. Measurement of rates of cleavage of three series of unsymmetrically substituted disulphides by cyanide or hydroxide shows that these unusual substituent effects arise from substituents in the thiocyanate-forming aryl ring. This behaviour is explained in terms of a change in the electronic behaviour of the thio- cyanate-forming sulphur atom from -I, + R in the disulphide to -I,-R in the rate-determining transition state for the reaction. The study does not show whether the cleavage involves an SN2 process or rapid equilibrium formation of a pentacovalent intermediate.

Polar substituent effects on13C NMR spectra in ethylcis-2-substituted cyclopropane carboxylates

1982 ◽  
Vol 20 (3) ◽  
pp. 159-161 ◽  
Author(s):  
Yoshiaki Kusuyama ◽  
Satoru Inoshita ◽  
Ginjiro Okada ◽  
Minoru Yanagi ◽  
Kenjiro Tokami ◽  
...  
Keyword(s):  
Nmr Spectra ◽  
Substituent Effects ◽  
Polar Substituent

Etude par spectrométrie infrarouge de l'action de solvants aprotiques sur l'association ester–eau et ester–Ba2+. Discussion du rôle catalytique du solvant et de l'ion Ba2+ dans l'hydrolyse alcaline du propionate de methyle

1979 ◽  
Vol 57 (4) ◽  
pp. 400-403 ◽  
Author(s):  
Anne Le Narvor ◽  
Pierre Saumagne
Keyword(s):  
Ir Spectra ◽  
Charge Density ◽  
Carbonyl Group ◽  
Alkaline Hydrolysis ◽  
Experimental Results ◽  
Methyl Propionate ◽  
Orbital Control ◽  
Different Types ◽  
Kinetics Of ◽  
Better Than

The ir spectra of mixtures of methyl propionate/water and methyl propionate/Ba2+ in dimethylsulfoxide and in acetonitrile have been recorded in the region of the νCO mode of the ester. Evidence is presented to indicate the presence of different types of complexes; their concentration was determined as a function of the composition of the medium. The spectroscopic results are compared to those from the kinetics of the alkaline hydrolysis in the same conditions. It is demonstrated that the orbital control explains the experimental results better than does the charge density on the carbon of the carbonyl group. [Journal translation]

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