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Thermal Rearrangements, XIX. The Kinetics of the Thermal Isomerization of 1-Ethynyl-2,2,3,3-tetramethylcyclopropane

✍ Scribed by Hopf, Henning ;Wachholz, Gerhard ;Walsh, Robin ;de Meijere, Armin ;Teichmann, Stefan

Publisher
Wiley (John Wiley & Sons)
Year
1989
Tongue
English
Weight
515 KB
Volume
122
Category
Article
ISSN
0009-2940

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✦ Synopsis

B 371 1 -Ethynyl-2,2,3,3-tetramethylcyclopropane (9) has been prepared and subjected to gas phase pyrolysis. Above 200°C the hydrocarbon rearranges to 4,4,5-trimethyl-I ,2,5-hexatriene (10) and 5,6dimethyl-5-hepten-I-yne (11). Whereas the allene is produced directly from 9 by a 1,Shydrogen shift, the alkyne is a secondary product formed from 10 by a [3,3] sigmatropic rearrangement.

The activation parameters (Ea, Ig A) for both processes have been determined for the 210 to 250°C temperature range. The data are discussed and compared with those for other concerted reactions of alkynes and alkenes.

Thermal reactions of acetylenic hydrocarbons have received growing attention in recent years'-4), and many studies have shown that these processes are chemically as varied and preparatively as useful as those of their olefinic counterpart^^-^). In contrast to these latter systems kinetic data for acetylenic molecules are conspicously lacking''. A comparison between the two classes of hydrocarbons aimed at elucidating the effect caused by replacement of a double bond by the geometrically distinctly different triple bond group is thus hampered. A case in point is provided by cis-I-ethenyl-2-methylcyclopropane (1) and cis-1 -ethynyl-2methylcyclopropanc (3). respectively.

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