ISSN:
0009-2940
Keywords:
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Influence of XCH2 and X2CH Rests upon Equilibrium Compositions Among Monosubstituted Bullvalenes and CycloheptatrienesCycloheptatrienylmethyl methyl ethers (5) and cycloheptatriene-carboxaldehyde dimethyl acetals (7) were equilibrated at 160-180°C (1,5-H shift). While 7 approaches a statistical (“hydrogen-like”) distribution of the CHX2 group, the methoxymethyl group of 5 strongly prefers position 1. In contrast, the NMR spectra of the analogous bullvalenes (2 and 9) indicate a nearly statistical distribution of CH2X, but not of CHX2. We conclude that electronic substituent effects on sigmatropic equilibria should not be generalized.
Additional Material:
2 Tab.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/cber.19861190919
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