The Thermal Decomposition of Cyclobutanone¹

Abstract

Thermal Decomposition of Cyclobutanone 6271 tetramethylene biradicals which have been assumed to be intermediates in the photolysis of cyclopentanone.5•6 The formation of butene and ethylene from the tetramethylene biradical has been observed by Bawn and Milsted30 in their study of the reaction of 1,4-dibromobutane and sodium at 300°.In spite of the data which are available the com-(30) C. E, H, Bawn and J. Milsted, Trans. Faraday Soc., 35, 889 (1939).plexity of the cyclopentanone decomposition precludes a thorough consideration of the detailed mechanism at the present time.Acknowledgment.-The authors wish to thank Mr. Carl Whiteman for making the infrared measurements and Dr. F. L. Mohler of the National Bureau of Standards for the mass spectrometric analyses.

Pyrolysis Reactions of 3-Oxetanone

“…One alternate pathway is CO + ethylene oxide ((CH 2 ) 2 O), a product channel analogous to the C 3 pathway 8,22 leading to CO + c-C 3 H 6 in the decomposition of cyclobutanone. Hydrogen migrations during thermal decomposition of 3-oxetanone could lead to acetaldehyde or methanol.…”

The decomposition of cyclobutanone vapor induced by infrared radiation from a pulsed CO2 TEA laser

“…Ketene, which is a probable product, was not detected by this analysis. 2These expressions are based on the measurements of k, by Das et al (7) and on values of kl/k, obtained by Blades (8). The later study by McGee and Schleifer (9) gave almost identical values of k,, while their relative rate data when replotted with those of Blades show no significant differences and cover a much narrower range of temperature.…”

“…A molecule that appears well suited to such a study is cyclobutanone. It is well established (7)(8)(9)(10) from conventional thermal decomposition studies that there are two clean, nonradical unimolecular modes of decomposition :…”

Stochastic Processes in Physical Chemistry

“…The thermal decomposition of cyclobutanone has been investigated by Das et al (239) and yields essentially ethylene and ketene as reaction products. A rear rangement mechanism is proposed by them, and they find that propylene and nitric oxide do not decrease the rate of reaction.…”