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- W2807141724 abstract "PART I: The Thermal Rearrangement of 3, 3-Dimethylcyclopropene The thermal rearrangement of 3, 3-dimethylcyclopropene wasinvestigated by entering the energy surface for the reaction by two routes:thermal isomerization of the cyclopropene and pyrolysis of a diazo compound precursor, 3-methyl-1-diazo-2-butene. Theproducts from both reactions are identical; however the proportions vary greatly. Greater than 95% of the product from the diazo compound is the cyclopropene, and the remainder of the product isisoprene and isopropylacetylene in a 5:2 ratio, with trace gem-dimethylallene.The products from isomerization of the cyclopropene are isopropylacetylene, isoprene, and gem-dimethylallene in a ratio of500:50:1. From these data it is concluded that two intermediatesexist for the isomerization, gem-dimethylvinylcarbene, (CH 3 ) 2 C=CH CH,and a 90° rotamer, designated as a diradical, (CH 3 ) 2 ĊCH=ĊH.Relative rates of interconversion and cyclization and an energy surface are determined and the results are compared with Huckel and CNDO/2 calculations on vinylcarbene. PART II. Interaction of Remote Functional Groups in the Ion Chemistry of Bifunctional Ethers An Ion Cyclotron Resonance examination of bifunctional ethers of the form CH 3 O(CH 2 ) n OR, where n = 1 - 6 and R = H, CH 3 , or C 2 H 5 ,reveals a large number of mass spectral processes and ion-moleculereactions in which the interaction of remote functional groups plays aprominent role.Chainlength effects are particularly pronounced:6-member cyclic intermediates are inf erred in rarrangements of odd electron species, while larger cycles appear pref erred in rearrangements of many even electron species." @default.
- W2807141724 created "2018-06-13" @default.
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- W2807141724 date "1973-01-01" @default.
- W2807141724 modified "2023-09-23" @default.
- W2807141724 title "Organic Reactions in the Gas Phase. I. The Thermal Rearrangement of 3, 3-Dimethylcyclopropene. II. Interaction of Remote Functional Groups in the Ion Chemistry of Bifunctional Ethers" @default.
- W2807141724 hasPublicationYear "1973" @default.
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