1462-03-9Relevant articles and documents
Taft et al.
, p. 4735 (1952)
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Brown,Yoon
, p. 2686 (1968)
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Deciphering Reactivity and Selectivity Patterns in Aliphatic C-H Bond Oxygenation of Cyclopentane and Cyclohexane Derivatives
Martin, Teo,Galeotti, Marco,Salamone, Michela,Liu, Fengjiao,Yu, Yanmin,Duan, Meng,Houk,Bietti, Massimo
supporting information, p. 9925 - 9937 (2021/06/30)
A kinetic, product, and computational study on the reactions of the cumyloxyl radical with monosubstituted cyclopentanes and cyclohexanes has been carried out. HAT rates, site-selectivities for C-H bond oxidation, and DFT computations provide quantitative information and theoretical models to explain the observed patterns. Cyclopentanes functionalize predominantly at C-1, and tertiary C-H bond activation barriers decrease on going from methyl- and tert-butylcyclopentane to phenylcyclopentane, in line with the computed C-H BDEs. With cyclohexanes, the relative importance of HAT from C-1 decreases on going from methyl- and phenylcyclohexane to ethyl-, isopropyl-, and tert-butylcyclohexane. Deactivation is also observed at C-2 with site-selectivity that progressively shifts to C-3 and C-4 with increasing substituent steric bulk. The site-selectivities observed in the corresponding oxidations promoted by ethyl(trifluoromethyl)dioxirane support this mechanistic picture. Comparison of these results with those obtained previously for C-H bond azidation and functionalizations promoted by the PINO radical of phenyl and tert-butylcyclohexane, together with new calculations, provides a mechanistic framework for understanding C-H bond functionalization of cycloalkanes. The nature of the HAT reagent, C-H bond strengths, and torsional effects are important determinants of site-selectivity, with the latter effects that play a major role in the reactions of oxygen-centered HAT reagents with monosubstituted cyclohexanes.
Diester acid protection structure monomer and preparation method thereof
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Paragraph 0076-0082; 0096-0102; 0106-0112; 0119-0125, (2020/01/03)
The invention relates to the field of optical materials and in particular to a diester acid protection structure monomer and a preparation method thereof. The diester acid protection structure monomeris used as a raw material of a photoresist required in integrated circuit manufacturing. Due to a diester long side chain, the photoresist has a better film-forming property; due to the fact that small-size and high-acid-sensitivity groups hung outside can improve the deprotection reaction efficiency in the photoetching process, the quality of a photoetched product is improved; and in addition, the diester acid protection structure monomer prepared through the process method has high yield and purity, and the performance of the photoresist is further guaranteed.
PROCESS FOR THE PREPARATION OF 1-METHYLCYCLOPENTANE DERIVATIVES
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, (2012/05/04)
Process for the preparation of 1-methylcyclopentene by thermal reaction of cyclohexanol or cyclohexene or mixtures of both compounds to give 1-methylcyclopentene, wherein the resulting by-products 3-methylcyclopentene and 4-methylcyclopentene (double-bond isomers of 1-methylcyclopentene) are returned to the reaction.
