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.

Solvolysis of specifically deuterated 7-chloro- and 7-bromo-exo-2-norbornyl brosylates; unusually large γ-kinetic isotope effects in the absence of σ-participation

1980 ◽  
Vol 58 (16) ◽  
pp. 1738-1750 ◽  
Author(s):  
Nick Henry Werstiuk ◽  
George Timmins ◽  
Frank Peter Cappelli
Keyword(s):  
Isotope Effect ◽  
Kinetic Isotope Effect ◽  
Isotope Effects ◽  
Kinetic Isotope Effects ◽  
Kinetic Isotope

A series of specifically deuterated syn-7-chloro-, anti-7-chloro-, syn-7-bromo-, and anti-7-bromo-exo-2-norbornyl brosylates have been prepared and solvolyzed in NaOAc-buffered 80:20 EtOH–H2O. For solvolysis at 25 °C the γ-kinetic isotope effects (KIE's) for syn-7-chloro-exo-2-norbornyl brosylate-endo-6-d (1e), anti-7-chloro-exo-2-norbornyl brosylate-endo-6-d (2c), syn-7-bromo-exo-2-norbornyl brosylate-endo-6-d (1f), anti-7-bromo-exo-2-norbornyl brosylate-endo-6-d (2d), syn-7-chloro-exo-2-norbornyl brosylate-exo,exo-5,6-d2 (1g), anti-7-chloro-exo-2-norbornyl brosylate-exo,exo-5,6-d2 (2e) are 1.125 ± 0.007, 1.128 ± 0.005, 1.063 ± 0.008, 1.149 ± 0.020, 1.119 ± 0.011, and 1.115 ± 0.013, respectively. There is no detectable γ-kinetic isotope effect for solvolysis of anti-7-chloro-endo-2-norbornyl brosylate-endo-6-d(3a) and the β-KIE for anti-7-chloro-exo-2-norbornyl brosylate-exo-3-d(4a) is 1.111 ± 0.011. From a consideration of the possible sources of the unusually large secondary KIE's, we conclude that the exo-6-d and endo-6-d γ-KIE's likely are derived from a combination of effects rather than from participation of the C1—C6 bond in the ionization step.

Kinetic evidence for the importance of solvent-separated ion pairs during the solvolyses of adamantylideneadamantyl derivatives

2004 ◽  
Vol 82 (9) ◽  
pp. 1336-1340
Author(s):  
Xicai Huang ◽  
Andrew J Bennet
Keyword(s):  
Ionic Strength ◽  
Transition State ◽  
Isotope Effect ◽  
Kinetic Isotope Effect ◽  
Isotope Effects ◽  
Ion Pairs ◽  
Kinetic Isotope Effects ◽  
Ion Pair ◽  
Salt Effects ◽  
Kinetic Isotope

The aqueous ethanolysis reactions of adamantylideneadamantyl tosylate, -bromide, and -iodide (1-OTs, 1-Br and 1-I) were monitored as a function of ionic strength. Special salt effects are observed during the solvolyses of both homoallylic halides, but not in the case of the tosylate 1-OTs. The measured α-secondary deuterium kinetic isotope effects for the solvolysis of 1-Br in 80:20 and 60:40 v/v ethanol–water mixtures at 25 °C are 1.110 ± 0.018 and 1.146 ± 0.009, respectively. The above results are consistent with the homoallylic halides reacting via a virtual transition state in which both formation and dissociation of a solvent-separated ion pair are partially rate-determining. While the corresponding transition state for adamantylideneadamantyl tosylate involves formation of the solvent-separated ion pair.Key words: salt effects, kinetic isotope effect, internal return, solvolysis, ion pairs.

scholarly journals Kinetic isotope effects for fast deuterium and proton exchange rates

2016 ◽  
Vol 18 (15) ◽  
pp. 10144-10151 ◽  
Author(s):  
Estel Canet ◽  
Daniele Mammoli ◽  
Pavel Kadeřávek ◽  
Philippe Pelupessy ◽  
Geoffrey Bodenhausen
Keyword(s):  
Exchange Rates ◽  
Isotope Effect ◽  
Kinetic Isotope Effect ◽  
Isotope Effects ◽  
Kinetic Isotope Effects ◽  
Proton Exchange ◽  
Kinetic Isotope ◽  
Spin Pairs

By monitoring the effect of deuterium decoupling on the decay of transverse 15N magnetization in D–15N spin pairs during multiple-refocusing echo sequences, we have determined fast D–D exchange rates kD and compared them with fast H–H exchange rates kH in tryptophan to determine the kinetic isotope effect as a function of pH and temperature.

Carbon-13 kinetic isotope effects. V. Substituent effects on k12/k13 for alcoholysis of 1-phenyl-1-bromoethane

1969 ◽  
Vol 47 (13) ◽  
pp. 2506-2509 ◽  
Author(s):  
Jan Bron ◽  
J. B. Stothers
Keyword(s):  
Isotope Effect ◽  
Phenyl Ring ◽  
Kinetic Isotope Effect ◽  
Isotope Effects ◽  
Isotopic Fractionation ◽  
Substituent Effects ◽  
Kinetic Isotope Effects ◽  
Kinetic Isotope ◽  
Factor Governing

As a test of our earlier interpretations of the 13C kinetic isotope effects found for alcoholysis of 1-phenyl-1-bromoethane, we have examined the effect of the p-methyl and p-bromo substituents on the 13C fractionations in ethanol and methanol. Isotopic fractionation at the α-carbon is found to be substituent dependent, and the observed trend is consistent with the proposal that stabilization of the cationic center by the phenyl ring is a major factor governing the isotope effect in these systems. The first example of an inverse primary kinetic isotope effect for carbon (k12/k13 < 1) is described.

Secondary deuterium isotope effects on both rate and product determining steps in the thermolysis of 4-methylene-1-pyrazoline

1981 ◽  
Vol 59 (16) ◽  
pp. 2556-2567 ◽  
Author(s):  
Moon Ho Chang ◽  
Robert J. Crawford
Keyword(s):  
Isotope Effect ◽  
Kinetic Isotope Effect ◽  
Isotope Effects ◽  
Bond Rupture ◽  
Cleavage Process ◽  
Kinetic Isotope ◽  
Product Distributions ◽  
Deuterium Isotope Effects ◽  
Allylic Radical

The secondary deuterium kinetic isotope effect in the thermolysis of 4-methylene-1-pyrazoline and four of its deuterated isomers has been studied. The value of δΔG≠/n is 142 cal mol−1 if it is a single C—N cleavage process or 71 cal mol−1 if it is a concerted rupture of two C—N bonds. The product distributions can only be rationalized in terms of a mechanism involving a rate determining C—N bond rupture to form a diazenyl diradical intermediate which then can close to methylenecyclopropanes by three possible modes. This requires a secondary isotope effect in the product determining step of 1.33 ± 0.05, for the rotation of CH2 (CD2) out of the plane of the allylic radical in the intermediate.

Kinetics and Stereochemistry of Elimination of Nitrous-Acid From 1-Para-Nitrophenyl-2-Nitroethyl Derivatives

1986 ◽  
Vol 39 (2) ◽  
pp. 281 ◽  
Author(s):  
RK Norris ◽  
TA Wright
Keyword(s):  
Isotope Effect ◽  
Nitrous Acid ◽  
Kinetic Isotope Effect ◽  
Isotope Effects ◽  
Kinetic Isotope Effects ◽  
Positive Entropy ◽  
Kinetic Isotope ◽  
Entropy Of Activation ◽  
Large Primary

The eliminations of nitrous acid from the compounds (1) and (6) are E2 processes, which proceed with a large primary kinetic isotope effect and with antiperiplanar stereochemistry. The rate of elimination of HNO2 from (1) is intermediate between the rate of elimination of HCl from (4) and HBr from (5). This order of nucleofugality , namely Br- > NO2- > Cl -, results from a more positive entropy of activation for the elimination of nitrous acid. The presence of an α-chlorine, as in compounds (8), (28) and (29), leads to elimination processes which are E1cB-like, with low primary kinetic isotope effects and with lack of stereospecificity.

Sign in / Sign up

Export Citation Format

Share Document