58049-91-5Relevant articles and documents
MECHANISM OF SOLVOLYSIS OF 2,2-DIMETHYLCYCLOPENTYL P-BROMOBENZENESULFONATE
Shiner, V. J.,Imhoff, Michael A.
, p. 2121 - 2124 (1985)
Solvolysis of the title compound in ethanol-water, trifluoroethanol-water, and hexafluoroisopropyl alcohol-water mixtures yields > 90 percent products of methyl migration.The rate of solvolysis relative to the cyclopentyl analogue is 0.19 in 80 percent ethanol-water, 4.0 in 97 percent trifluoroethanol-water, and 10.0 in 90 percent hexafluoroisopropyl alcohol-water.The α-d and β-d2 rate effects in solvolysis range respectively from 1.19-1.20 to 1.26-1.30.The results are interpreted in terms of a mechanism which involves reversible formatin of the tight ion pair followed by rate-determining methyl migration.
Studies on the Thermal Conversion of Long-chain Alkynes at High Temperatures in the Gas Phase
Ondruschka, B.,Zimmermann, G.,Ziegler, U.,Kopinke, F.-D.,Teuber, M.
, p. 273 - 284 (2007/10/02)
In the gas phase pyrolysis of long-chain alkynes C5 to C9 at 773 to 873 K, a remarkable portion of molecular reaction (retro-ene analogous decompositions as well as cycloisomerizations of the parent alkynes to cyclopentenes alkylated in 3-position) takes place besides the thermal conversion of the starting compounds via radical chain processes.The different products were separated by GC and the main products identified by means of different methods.The mechanisms of formation of the major products are discussed.
On 1.2-Shift Reactions and C-H-Insertions of Acyclic Alkylidene Carbenes
Ondruschka, Bernd,Remmler, Matthias,Zimmermann, Gerhard,Krueger, Christian
, p. 49 - 54 (2007/10/02)
Two series of acyclic terminal vinyl bromides (1...4 and 5...7) were tested in the reaction with potassium tert-butoxide as precursors of alkylidene carbenes.As expected 1 up to 4 only give 1-alkynes whereas the 2-methylated vinyl bromides 5, 6 and 7 yield 1-methylated cyclopentenes predominantly besides 2-alkynes.The formation of cyclopentenes indicates a reaction route via alkylidene carbenes and 1,5-C-H-insertion reactions, that of 2-alkynes is convincing evidence for 1,2-alkyl shift reactions in 2-methyl substituted alkylidene carbenes.The selectivity of 1,5-C-H-insertion depends on the degree of alkyl substitution of the C-5-atom.At 240 deg C the selectivity is 1deg:2deg:3deg ca. 1:54:240.