Simultaneous H/D and 13C/12C Anomalous Kinetic Isotope Effects during the Sonolysis of Water in the Presence of Carbon Monoxide

2021 ◽  
pp. 42-48
Author(s):  
Sergey I. Nikitenko ◽  
Tony Chave ◽  
Matthieu Virot ◽  
Rachel Pflieger
Keyword(s):  
Carbon Monoxide ◽  
Isotope Effects ◽  
Kinetic Isotope Effects ◽  
Kinetic Isotope

The thermally induced rearrangements of 2-vinyloxirane

1976 ◽  
Vol 54 (21) ◽  
pp. 3364-3376 ◽  
Author(s):  
Robert J. Crawford ◽  
Stuart B. Lutener ◽  
Robert D. Cockcroft
Keyword(s):  
Carbon Monoxide ◽  
Gas Phase ◽  
Isotope Effects ◽  
Kinetic Isotope Effects ◽  
Thermally Induced ◽  
Rate Determining Step ◽  
Kinetic Isotope ◽  
Carbonyl Ylide ◽  
Structural Isomerization ◽  
Kinetics Of

The kinetics of the gas phase thermolysis of 2-vinyloxirane (4) have been studied over the temperature range 270–310 °C. The racemization of chiral 4 occurs six times faster than the structural isomerization to 2,3-dihydrofuran, (E)- and (Z)-2-butenal, and 3-butenal. The butenals undergo a slow thermolysis to propene and carbon monoxide. cis-Deuterio- and trans-3-deuterio-vinyloxirane have been synthesized and their interconversion is slow. Deuterium kinetic isotope effects on mono- and dideuterio-4 suggest that for the formation of the butenals the rate determining step involves rupture of the oxirane C—O bond. The dihydrofuran is produced by thermolysis of the oxirane C—C bond. The preferred mechanistic interpretation is that a carbon–oxygen diradical serves as an intermediate for butenal formation, and that a carbonyl-ylide is involved in the formation of the dihydrofuran.The relative rates, at 307.4 °C, of cis–trans-5-isomerization:dihydrofuran formation:racemization: butenal formation for 3-deuterio-2-vinyloxirane are 1.0:0.88:40.2:5.94, respectively.

Theoretical Simulations of Heavy-Atom Kinetic Isotope Effects in Aliphatic Claisen Rearrangement

2020 ◽  
Vol 124 (51) ◽  
pp. 10678-10686
Author(s):  
Yuqing Xu ◽  
Kin-Yiu Wong ◽  
Meishan Wang ◽  
Desheng Liu ◽  
Wenkai Zhao ◽  
...  
Keyword(s):  
Claisen Rearrangement ◽  
Isotope Effects ◽  
Heavy Atom ◽  
Kinetic Isotope Effects ◽  
Kinetic Isotope ◽  
Theoretical Simulations

Direct dynamics calculations of reaction rate and kinetic isotope effects in enzyme catalysed reactions

2002 ◽  
Vol 122 ◽  
pp. 223-242 ◽  
Author(s):  
Gary Tresadern ◽  
Sara Nunez ◽  
Paul F. Faulder ◽  
Hong Wang ◽  
Ian H. Hillier ◽  
...  
Keyword(s):  
Reaction Rate ◽  
Isotope Effects ◽  
Kinetic Isotope Effects ◽  
Direct Dynamics ◽  
Kinetic Isotope

Interpretation of Transient-State Kinetic Isotope Effects†

Biochemistry ◽  
1996 ◽  
Vol 35 (1) ◽  
pp. 83-88 ◽  
Author(s):  
Harvey F. Fisher ◽  
Swapan K. Saha
Keyword(s):  
Isotope Effects ◽  
Transient State ◽  
Kinetic Isotope Effects ◽  
Kinetic Isotope ◽  
State Kinetic
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