Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases p. 1415 - 1424 (1985)
Update date:2022-08-17
Topics:
Awan, Iftikhar A.
Flowers, Michael C.
In the temperature range 665-737 K the thermal decomposition of 1-methoxy-1-methylcyclopropane follows first-order kinetics with a rate constant given by the equation k/s-1 = 1014.76 +/- 0.81 exp(-252 +/- 10 kJ mol-1/RT).The presence of the 1-methyl substituent destablises the transition state for reaction.Secondary decomposition of the initially formed isomeric products precludes the determination of their individual rates of formation.Cis- and trans-1-methoxy-2-methylcyclopropane undergo first-order, reversible, geometric isomerisation in competition with structural isomerisation to give cis- and trans-1-methoxybut-1-ene and 1-methoxy-2-methylpropene in the temperature range 597-689 K: kcis -> trans/s-1 = 1015.25 +/- 0.23 exp(-235.4 +/- 2.8 kJ mol-1/RT), ktrans -> cis/s-1 = 1014.99 +/- 0.80 exp(-233.7 +/- 9.9 kJ mol-1/RT), kcis -> cis-1-methoxybut-1-ene/s-1 = 1013.79 +/- 0.29 exp(-233.1 +/- 3.6 kJ mol-1/RT), kcis -> trans-1-methoxybut-1-ene/s-1 = 1013.29 +/- 0.66 exp(-234.4 +/- 8.1 kJ mol-1/RT), kcis -> 1-methoxy-2-methylpropene/s-1 = 1012.4 +/- 1.0 exp(-225 +/- 12 kJ mol-1/RT), ktrans -> cis-1-methoxybut-1-ene/s-1 = 1014.05 +/- 0.62 exp(-243.7 +/- 7.8 kJ mol-1/RT), ktrans -> trans-1-methoxybut-1-ene/s-1 = 1013.0 +/- 0.9 exp(-233 +/- 11kJ mol-1/RT), ktrans -> 1-methoxy-2-methylpropane/s-1 = 1013.5 +/- 1.0 exp(-235 +/- 13 kJ mol-1/RT).On the basis of a biradical mechanism the results provide evidence for the formation of distinguishable biradicals on opening the cis- and trans-1-methoxy-2-methylcyclopropane ring.Estimates are made of the relative rates of ring closing, internal rotation and hydrogen-atom transfer of the biradicals.
View More
Jinan Hongfangde Pharmatech Co.,Ltd
Contact:86-531-88870908
Address:F Bldg. West Unit North Area of Univ. Tech. Garden Xinyu Rd. Jinan New & High Tech Industry Development Zone Shandong, China
Shanghai Dynamic Industrial Co.,Ltd.
website:http://www.shdynamic.com
Contact:86-021 3392 6680
Address:Room 805 Information Tower, No.1403 Minsheng Road, Pudong New Area, Shanghai 200135, P. R. China
website:https://www.bocsci.com/
Contact:1-631-485-4226
Address:Ramsey Road
Tianjin Tongde Biological Technology Co., Ltd.
Contact:86-22-23309138
Address:Room 402, bulidingE3 Detection certification park, XiQingDistrict, Tianjin City
Jiangxi Lanqi Fine Chemical S&T Co., Ltd.
Contact:+86-21-64891143
Address:XinJiShan Industrial Area, Zhangshu City, JiangXi Province, China
Doi:10.1021/acs.analchem.6b01788
(2016)Doi:10.1021/ja01244a015
(1943)Doi:10.1055/s-2007-1000937
(2008)Doi:10.1021/om100503v
(2010)Doi:10.1021/acs.joc.8b02494
(2019)Doi:10.1055/s-1980-29007
(1980)
