Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases p. 2195 - 2204 (1982)
Update date:2022-08-17
Topics:
Hammonds, Paul
Holbrook, Kenneth A.
The thermolysis of 2-methyloxetan has been reinvestigated at temperatures between 429.5 and 483.2 deg C and initial reactant pressures from 6.0 to 14.2 Torr.Two parallel unimolecular reactions occur producing either propene and formaldehyde or ethene and acetaldehyde.The ratio of propene to ethene is 1.31+/-0.03 within this temperature range.The total rate constant for dissapearance of reactant is given by log10(k/s-1)=(14.89+/-0.36)-(249.8+/-4.7KJ mol-1)/2.303 RT.The thermolysis of 2,2-dimethyloxetan was studied in the same apparatus at temperatures between 402.2 and 471.3 deg C and at reactant pressures from 7.2 to 9.2 Torr.The reactant disappears by two parallel unimolecular paths to give either isobutene and formaldehyde or ethene and acetone.Minor products of methane, propene and isobutane were also detected.The ratio of isobutene to ethene was found to differ considerably from unity and to be strongly temperature-dependent.The following rate expressions were derived for the overall rate of disapperance of reactant (k2,2) and for the rate constants for the individual reactions producing isobutene (k3) and ethene (k4) log10(k2,2/s-1)=(13.78+/-0.24)-(226.0+/-2.7 kJ mol-1)/2.303 RT log10(k3/s-1)=(13.48+/-0.25)-(222.1+/-2.9 kJ mol-1)/2.303 RT log10(k4/s-1)=(15.56+/-0.34)-(270.6+/-4.4 kJ mol-1)/2.303 RT.The differences observed between the thermolyses of these two compounds are noted and compared with previously obtained results for other methyl-substituted oxetans.A possible explanation for the difference in Arrhenius parameters for the two paths in the case of the 2,2-disubstituted compound is suggested.
View MoreSuzhou BEC Fine Chemicals Co., Ltd.
website:http://www.bek.com.cn
Contact:0512-68095917 18913193865
Address:6, Jin Shan Road, Suzhou New District, 215011 China Suzhou Nations Pharmaceutical Innovation Center Inside
Jewim Pharmaceutical (Shandong) Co., Ltd
Contact:+8615621883869
Address:山东省泰安市高新技术产业开发区配天门大街西首
Taizhou Chemedir Biopharm-tech Co., Ltd
Contact:+86 523 86200218
Address:G09, No. 1 Avenue China Medical City, Taizhou,Jiangsu, China
Shanghai Science Peptide Biological Technology Co.,ltd
website:http://www.scipeptide.com
Contact:+86-21-51099675
Address:No.8 Changyang Rd
Contact:+86 512 6287 2180
Address:398 Ruoshui Road, Suzhou Industrial Park, Suzhou, Jiangsu, P. R. China
Doi:10.1063/1.1723640
(1942)Doi:10.1016/S0040-4039(00)75545-6
(1968)Doi:10.1039/j39670001622
(1967)Doi:10.1134/S0023158413040113
(2013)Doi:10.1016/S0040-4039(01)99819-3
(1983)Doi:10.1021/jo00034a008
(1992)
