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Stereochemistry of the Thermal Conversion of 1‐Vinyl‐2,3‐ cis ‐dideuteriocyclobutane to Butadiene and 1,2‐Dideuterioethylenes
Author(s) -
Lewis David K.,
Hutchinson Avery,
Lever Steven J.,
Spaulding Eric L.,
Bonacorsi Samuel J.,
Baldwin John E.
Publication year - 1996
Publication title -
israel journal of chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.908
H-Index - 54
eISSN - 1869-5868
pISSN - 0021-2148
DOI - 10.1002/ijch.199600033
Subject(s) - chemistry , deuterium , thermal decomposition , ethylene , decomposition , cyclohexene , fourier transform infrared spectroscopy , analytical chemistry (journal) , spectroscopy , cis–trans isomerism , photochemistry , stereochemistry , organic chemistry , catalysis , quantum mechanics , physics
This study has examined the stereochemistry of the decomposition at 900–1000 K in a single‐pulse shock tube of 1‐vinyl‐2,3‐ cis ‐dideuteriocyclobutane to ethylenes and buta‐1,3‐dienes. The deuterated ethylenes formed during the decomposition, CHDCH 2 , ( E )‐CHDCHD, and ( Z )‐CHDCHD, were quantified via two independent techniques, FTIR and IR absorption spectroscopy using a tunable diode laser spectrometer. The results of both analyses indicated that equal amounts of ( E )‐CHDCHD and ( Z )‐CHDCHD were formed from the cis‐labeled reactant. In an earlier shock tube study of the decomposition at 1000–1200 K of two deuterium‐labeled cyclohexenes to ethylenes plus buta‐1,3‐dienes, a pathway via a vinylcyclobutane intermediate was implicated in a significant fraction of the decomposition events; the measured ratios of ( E )‐CHDCHD to ( Z )‐CHDCHD in that study were consistent with a complex mechanistic model in which the stereochemistry of deuterium labels in the cyclohexene reactant was lost in ethylene products formed via vinylcyclobutane. The present results provide additional support for that model.