Carbon-13 Kinetic Isotope Effects Research Articles

Carbon-14 Kinetic Isotope Effects in the Menschutkin-Type Reaction of Benzyl Benzenesulfonates with N,N-Dimethylanilines. Variation of the Effects with Substituents - Correction

Carbon-14 Kinetic Isotope Effects in the Menschutkin-Type Reaction of Benzyl Benzenesulfonates with N,N-Dimethylanilines. Variation of the Effects with Substituents - Correction

MINDO/3 Calculations of Kinetic Isotope Effects in Heterolysis of Neopentyl Alcohol

Abstract Geometrical optimization of the protonated neopentyl alcohol and the transition state of its heterolysis was carried out using the MINDO/3 SCF-MO method. A cyclic structure was predicted for the transition state. Agreement between the calculated and experimental values for the carbon-14 kinetic isotope effects was excellent.

ChemInform Abstract: THE BECKMANN REARRANGEMENT IN CONCENTRATED SULFURIC ACID. STUDIES BY MEANS OF NMR AND KINETIC ISOTOPE EFFECT

The mechanism of the Beckmann rearrangement of acetophenone (a) and 1-phenyl-2-propanone (b) oximes in concd sulfuric acid was elucidated by means of NMR spectroscopy and the carbon-14 kinetic isotope effect. For (a), the postulated reactive species acetophenone oxime hydrogensulfate was detected, the absence of hydrolysis of the oxime during the course of the reaction being verified. Positive carbon-14 kinetic isotope effect at the phenyl-1, k12/k14=1.026 at 40 °C and 1.019±0.005 at 60 °C, confirmed a definite change in bonding of the phenyl-1 carbon in the transition state of the reaction. Concertedness of the rearrangement was thus established. For (b), sulfonation of the benzene ring prior to the rearrangement was observed, kinetic isotope effect study being found to be useless.

The Beckmann Rearrangement in Concentrated Sulfuric Acid. Studies by Means of NMR and Kinetic Isotope Effect

Abstract The mechanism of the Beckmann rearrangement of acetophenone (a) and 1-phenyl-2-propanone (b) oximes in concd sulfuric acid was elucidated by means of NMR spectroscopy and the carbon-14 kinetic isotope effect. For (a), the postulated reactive species acetophenone oxime hydrogensulfate was detected, the absence of hydrolysis of the oxime during the course of the reaction being verified. Positive carbon-14 kinetic isotope effect at the phenyl-1, k12/k14=1.026 at 40 °C and 1.019±0.005 at 60 °C, confirmed a definite change in bonding of the phenyl-1 carbon in the transition state of the reaction. Concertedness of the rearrangement was thus established. For (b), sulfonation of the benzene ring prior to the rearrangement was observed, kinetic isotope effect study being found to be useless.

Carbon-14 kinetic isotope effects in the Menschutkin-type reaction of benzyl benzenesulfonates with N,N-dimethylanilines. Variation of the effects with substituents

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTCarbon-14 kinetic isotope effects in the Menschutkin-type reaction of benzyl benzenesulfonates with N,N-dimethylanilines. Variation of the effects with substituentsHiroshi Yamataka and Takashi AndoCite this: J. Am. Chem. Soc. 1979, 101, 1, 266–267Publication Date (Print):January 1, 1979Publication History Published online1 May 2002Published inissue 1 January 1979https://doi.org/10.1021/ja00495a069RIGHTS & PERMISSIONSArticle Views35Altmetric-Citations15LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (281 KB) Get e-Alerts Get e-Alerts

Neighboring group participation in solvolysis. VIII methyl participation in acetolysis of 2-methyl-2-adamantylmethyl p-bromobenzenesulfonate. angular dependence of β-methyl carbon-14 and deuterium kinetic isotope effects

Neighboring group participation in solvolysis. VIII methyl participation in acetolysis of 2-methyl-2-adamantylmethyl p-bromobenzenesulfonate. angular dependence of β-methyl carbon-14 and deuterium kinetic isotope effects

Carbon-13 kinetic isotope effects on pyruvate decarboxylation. 2. Solvent effects in model systems

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTCarbon-13 kinetic isotope effects on pyruvate decarboxylation. 2. Solvent effects in model systemsFrank Jordan, Donald J. Kuo, and Ernst U. MonseCite this: J. Org. Chem. 1978, 43, 14, 2828–2830Publication Date (Print):July 1, 1978Publication History Published online1 May 2002Published inissue 1 July 1978https://doi.org/10.1021/jo00408a017RIGHTS & PERMISSIONSArticle Views62Altmetric-Citations10LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (380 KB) Get e-Alerts Get e-Alerts

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

Chemischer InformationsdienstVolume 8, Issue 32 Preparative Organic Chemistry ChemInform Abstract: CALCULATION OF CARBON-14, CHLORINE-37, AND DEUTERIUM KINETIC ISOTOPE EFFECTS IN THE SOLVOLYSIS OF TERT-BUTYL CHLORIDE G. W. BURTON, G. W. BURTONSearch for more papers by this authorL. B. SIMS, L. B. SIMSSearch for more papers by this authorJ. C. WILSON, J. C. WILSONSearch for more papers by this authorA. FRY, A. FRYSearch for more papers by this author G. W. BURTON, G. W. BURTONSearch for more papers by this authorL. B. SIMS, L. B. SIMSSearch for more papers by this authorJ. C. WILSON, J. C. WILSONSearch for more papers by this authorA. FRY, A. FRYSearch for more papers by this author First published: August 9, 1977 https://doi.org/10.1002/chin.197732104AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinked InRedditWechat No abstract is available for this article. Volume8, Issue32August 9, 1977 RelatedInformation

Variations of carbon-14 kinetic isotope effects in the menschutkin type reaction of benzyl arenesulfonates

Variations of carbon-14 kinetic isotope effects in the menschutkin type reaction of benzyl arenesulfonates

Carbon-13 kinetic isotope effect in the thermal isomerization of methyl isocyanide

Carbon-13 kinetic isotope effect in the thermal isomerization of methyl isocyanide

Carbon-13 kinetic isotope effect in the structural isomerization of cyclopropane. Temperature and pressure dependence

Carbon-13 kinetic isotope effect in the structural isomerization of cyclopropane. Temperature and pressure dependence

CARBON-13 KINETIC ISOTOPE EFFECTS IN BIMOLECULAR REACTIONS

Carbon-13 kinetic isotope effects have been measured for the bimolecular reaction of 1-phenyl-1-bromoethane (I) and benzyl bromide (II) with alkoxide ion in alcohol solution. Compound I gave an effect, k12/k13, of 1.0032 ± 0.0005 for reaction with ethoxide ion in ethanol, while II gave k12/k13 = 1.0531 ± 0.0004 for reaction with methoxide ion in methanol. These surprisingly different effects are tentatively interpreted in terms of a model for the transition state having varying degrees of ionic character.

CARBON-13 KINETIC ISOTOPE EFFECTS IN THE SOLVOLYSIS OF 1-BROMO-1-PHENYLETHANE

Carbon-13 kinetic isotope effects have been measured for the solvolysis in methanol and ethanol of 1-bromo-1-phenylethane of natural isotopic abundance. Methanolysis of the bromide at 25 °C gave a kinetic isotope effect (k12/k13) of 1.0065 ± 0.0006, and ethanolysis at 45 °C gave 1.0064 ± 0.0010. These surprisingly low effects for a bond-rupture process have been interpreted in terms of a model for the transition state in which the bonding of the isotopic. carbon is strengthened by conjugation of the electron deficient center with the ring. The results are considered to provide support for the mass fragment model for evaluation of the effective mass term of the Bigeleisen expression for the theoretical calculation of kinetic isotope effects.