43087-10-1Relevant articles and documents
Catalytic Condensation of Carbonyl Compounds during the Synthesis of Cyclohexanone in the Production of Caprolactam
Martynenko,Levanova,Glazko,Morgun
, p. 889 - 894 (2018/10/15)
Abstract: Kinetic features of the condensation processes of carbonyl and unsaturated impurities in cyclohexanone have been studied using model mixtures in a heterophase system in the presence and absence of phase-transfer catalysts. It has been shown that linear aldehydes are condensed with cyclohexanone in the heterophase system in the presence and absence of phase-transfer catalysts under mild conditions (30–50°C). Noncarbonyl unsaturated compounds (e.g., 2-cyclohexene-1-ol) can be removed only at temperatures above 100°C in the presence of acidic catalysts (e.g., high-temperature sulfonated cation-exchange resins). Unsaturated cyclic ketones are characterized by both alkylation reactions over acid catalysts and aldol condensation reactions in the presence of an alkali, thereby suggesting the possibility of their elimination at different cyclohexanone purification steps. The theoretical models built can be used to develop an effective cyclohexanone purification technology that will substantially enhance the manufacturability of high-purity caprolactam and polyamide.
MECHANISM OF THE γ-RADIOLYSIS OF 2-PROPANOL SOLUTIONS OF CYCLOHEXANONES
Alipour, E.,Vidril, D.,Micheau, J. C.,Paillous, N.,Lattes, A.,et al.
, p. 2807 - 2814 (2007/10/02)
The γ-radiolysis of 2-propanol solutions of cyclohexanone gives mainly hydrogen, acetone, pinacol, methane derived from 2-propanol, and cyclohexanol, 2-(2-cyclohexanonyl)-cyclohexanone, and 3-(2-hydroxy-2-propyl)cyclohexanone derived from cyclohexanone.The radiolytic yields of all these products were highly dependent on the initial cyclohexanone concentration.The formation of cyclic alcohols by radioreduction has been extended to various substituted cyclohexanones.Radiolytically generated solvated electrons are scavenged by cyclohexanone, leading to the corresponding radical anions.The protonation of these radical anions gives rise to cyclohexanol via the dismutation of the hydroxycyclohexyl radicals.Steady state radiolysis measurements were complemented by pulse radiolysis in dilute solution.It was established that radical-anions and hydroxylated radicals decayed according to a second order rate law.When ketone concentration was lower than 0.1M, radiolytic yields were in agreement with the mechanism mentioned above.However, in concentrated media the large increase in G(cyclohexanol) cannot be only accounted for by the involvement of radiolytically generated solvated electrons; probably it is due to an electron transfer from the cyclohexanone enolate to cyclohexanone itself, thus generating extra amounts of cyclohexanone radical anions.
