Chlorine kinetic isotope effect models. I. Isotopic dependence in nominal carbon-chlorine stretching vibrations of aliphatic chlorides and vibrational analysis of the tert-butyl chloride ground state

1973 ◽  
Vol 95 (6) ◽  
pp. 1710-1714 ◽  
Author(s):  
Robert C. Williams ◽  
James W. Taylor
Keyword(s):  
Isotope Effect ◽  
Ground State ◽  
Kinetic Isotope Effect ◽  
Vibrational Analysis ◽  
Butyl Chloride ◽  
Tert Butyl ◽  
Kinetic Isotope ◽  
Stretching Vibrations ◽  
Isotopic Dependence ◽  
Tert Butyl Chloride

SOME DEUTERIUM KINETIC ISOTOPE EFFECTS: IV. β-DEUTERIUM EFFECTS IN WATER SOLVOLYSIS OF ETHYL, ISOPROPYL, AND tert-BUTYL COMPOUNDS

1960 ◽  
Vol 38 (11) ◽  
pp. 2171-2177 ◽  
Author(s):  
K. T. Leffek ◽  
J. A. Llewellyn ◽  
R. E. Robertson
Keyword(s):  
Isotope Effect ◽  
Kinetic Isotope Effect ◽  
Isotope Effects ◽  
Kinetic Isotope Effects ◽  
Alkyl Halides ◽  
Tert Butyl ◽  
Kinetic Isotope ◽  
Deuterium Isotope Effects ◽  
Intramolecular Forces

The secondary β-deuterium isotope effects have been measured in the water solvolytic reaction of alkyl halides and sulphonates for primary, secondary, and tertiary species. In every case the kinetic isotope effect was greater than unity (kH/kD > 1). This isotope effect may be associated with varying degrees of hyperconjugation or altered non-bonding intramolecular forces. The experiments make it difficult to decide which effect is most important.

scholarly journals Vibrational analysis of a rate-slowing conformational kinetic isotope effect

Tetrahedron ◽  
2019 ◽  
Vol 75 (5) ◽  
pp. 545-550 ◽  
Author(s):  
O. Maduka Ogba ◽  
Zichen Liu ◽  
Daniel J. O'Leary
Keyword(s):  
Isotope Effect ◽  
Kinetic Isotope Effect ◽  
Vibrational Analysis ◽  
Kinetic Isotope

Primary kinetic isotope effect in the gas phase photochlorination of ethyl chloride-1-d1

1984 ◽  
Vol 62 (5) ◽  
pp. 899-906 ◽  
Author(s):  
Jan Niedzielski ◽  
T. Yano ◽  
E. Tschuikow-Roux
Keyword(s):  
Activation Energy ◽  
Gas Phase ◽  
Isotope Effect ◽  
Ground State ◽  
Rate Constants ◽  
Kinetic Isotope Effect ◽  
Kinetic Isotope ◽  
Primary Reference ◽  
Hydrogen Deuterium ◽  
Increasing Temperature

The abstraction of hydrogen/deuterium from CH3CHDCl by ground state chlorine atoms produced photolytically from Cl2 has been investigated at temperatures betwen 280 and 368 K. The relative rates for the internal competition[Formula: see text]are found to conform to an Arrhenius rate law:[Formula: see text]These data, taken together with the external competition results for the C2H5Cl/CH3CHDCl system, in conjunction with the competitive results using CH4 as a primary reference, have yielded the rate constants (cm3 s−1):[Formula: see text]The relatively weak primary kinetic isotope effect, kH/kD, decreases with increasing temperature from 1,855 at 280 K to 1.66 at 365 K. The results are compared with those obtained based on the BEBO method. While both the trend and the magnitude of the kinetic isotope effect are satisfactorily predicted, the activation energy is not.

ChemInform Abstract: CALCULATION OF CARBON-14, CHLORINE-37, AND DEUTERIUM KINETIC ISOTOPE EFFECTS IN THE SOLVOLYSIS OF TERT-BUTYL CHLORIDE

1977 ◽  
Vol 8 (32) ◽  
pp. no-no
Author(s):  
G. W. BURTON ◽  
L. B. SIMS ◽  
J. C. WILSON ◽  
A. FRY
Keyword(s):  
Isotope Effects ◽  
Kinetic Isotope Effects ◽  
Butyl Chloride ◽  
Tert Butyl ◽  
Carbon 14 ◽  
Kinetic Isotope ◽  
Tert Butyl Chloride

CHLORINE ISOTOPE EFFECT IN REACTIONS OF TERT-BUTYL CHLORIDE

1954 ◽  
Vol 32 (10) ◽  
pp. 979-983 ◽  
Author(s):  
Rosalie M. Bartholomew ◽  
F. Brown ◽  
M. Lounsbury
Keyword(s):  
Silver Nitrate ◽  
Sodium Hydroxide ◽  
Isotope Effect ◽  
Butyl Chloride ◽  
Tert Butyl ◽  
Chlorine Isotope ◽  
Tert Butyl Chloride

When tert-butyl chloride reacts with either alcoholic silver nitrate or aqueous alcoholic sodium hydroxide the Cl35 compound reacts faster than the Cl37 compound. The ratio of the rates of reaction is[Formula: see text]

Sterically Hindered Aromatic Compounds. VI. A Remote ε-Deuterium Kinetic Isotope Effect in the Solvolysis of Perdeutero-2,4,6-tri-tert-butylbenzyl Chloride

1975 ◽  
Vol 53 (21) ◽  
pp. 3171-3174 ◽  
Author(s):  
L. Ross C. Barclay ◽  
John R. Mercer ◽  
Peter J. MacAulay
Keyword(s):  
Transition State ◽  
Isotope Effect ◽  
Aromatic Compounds ◽  
Kinetic Isotope Effect ◽  
Inductive Effect ◽  
Steric Effects ◽  
Deuterium Isotope Effect ◽  
Tert Butyl ◽  
Kinetic Isotope ◽  
Sterically Hindered

2,4,6-Tri-tert-butylbenzyl chloride deuterated at the three tert-butyl groups was synthesized. Conductimetric solvolysis studies of the normal and perdeutero-2,4,6-tri-tert-butylbenzyl chloride at 30.06 °C in 80% ethanol–water provides evidence for an inverse remote ε-deuterium isotope effect, kH/kD = 0.873−0.874. Under the same conditions the α-deuterium isotope effect was kH/kαD = 1.166 per deuterium, indicative of limiting solvolytic behavior. The remote ε-deuterium isotope effect for the perdeutero compound is discussed in terms of the inductive effect of deuterium and steric effects on the transition state conformation.

Calicheamicin γ1I and phenyl tert-butyl nitrone (PBN): observation of a kinetic isotope effect by an ESR study

2010 ◽  
Vol 46 (5) ◽  
pp. 737-739 ◽  
Author(s):  
Toyonobu Usuki ◽  
Mari Kawai ◽  
Koji Nakanishi ◽  
George A. Ellestad
Keyword(s):  
Isotope Effect ◽  
Kinetic Isotope Effect ◽  
Tert Butyl ◽  
Kinetic Isotope

Calculation of carbon-14, chlorine-37, and deuterium kinetic isotope effects in the solvolysis of tert-butyl chloride

1977 ◽  
Vol 99 (10) ◽  
pp. 3371-3379 ◽  
Author(s):  
Graham W. Burton ◽  
Leslie B. Sims ◽  
Joe C. Wilson ◽  
Arthur Fry
Keyword(s):  
Isotope Effects ◽  
Kinetic Isotope Effects ◽  
Butyl Chloride ◽  
Tert Butyl ◽  
Carbon 14 ◽  
Kinetic Isotope ◽  
Tert Butyl Chloride
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