17574-84-4Relevant articles and documents
METHOD FOR PRODUCING UNSATURATED ETHER COMPOUND
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Page/Page column 4, (2008/06/13)
The present invention provides a method for producing an unsaturated ether compound represented by general formula (2) below, the method comprising reacting an acetal represented by general formula (1) below in the presence of an aliphatic or aromatic sulfonic acid and an organic base having a total carbon number of 3 to 7. (In the formulae, R1, R2, and R3 may be the same or different and each represent substituted or unsubstituted alkyl, substituted or unsubstituted aryl, or substituted or unsubstituted aralkyl, or R1 and R2 form cycloalkyl together with the adjacent carbon atom.)
Kinetics of the Gas-phase Thermal Decompositions of 1-Methoxy-1-methylcyclopropane and cis- and trans-1-Methoxy-2-methylcyclopropane
Awan, Iftikhar A.,Flowers, Michael C.
, p. 1415 - 1424 (2007/10/02)
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.