An efficient conversion of olefins to ketones was achieved by the use of molecularoxygen and triethylsilane in the presence of a catalytic amount of cobalt(II) complex of porphyrin. The oxidation was accelerated remarkably in alcohols and had chemoselectivity for conjugated olefins.
在催化量的卟啉钴 (II) 络合物存在下,通过使用分子氧和三乙基硅烷,实现了烯烃到酮的有效转化。在醇中氧化显着加速并且对共轭烯烃具有化学选择性。
Selective catalytic aerobic oxidation of substituted ethylbenzenes under mild conditions
Ethylbenzene is oxidized to the corresponding hydroperoxide (PEHP) with high selectivity, under mild conditions, by means of a metal-free catalytic system consisting of an aldehyde and N-hydroxyphthalimide (NHPI). The process occurs via a freeradical mechanism by in situ generation of the phthalimido-N-oxyl (PINO) radical. The protocol is applied with success on a wide range of substituted ethylbenzenes
A novel and direct synthesis of hydroperoxy compounds from various types of conjugated olefins was established via cobalt(II) porphyrin-catalyzed hydroperoxygenation. The reaction of α,β,γ,δ-unsaturated carbonyl compounds, acrylic esters, α-substituted acrylic esters and styrene derivatives with molecular oxygen and triethylsilane in the presence of a catalytic amount of cobalt(II) porphyrin proceeded
free-radical chain oxidation of 1-isopropyl-4-methoxybenzene (1a) and 1-ethyl-4-methoxybenzene (1b) with oxygen in the liquid phase to yield 1-methyl-1-(4-methoxyphenyl)ethyl hydroperoxide (2a) and 1-(4-methoxyphenyl)ethyl hydroperoxide (2b). The oxidizability of 1a and 1b was studied over the temperature range 50–100°C. Long-term oxidations of 1a and 1b to the corresponding hydroperoxides were carried out
Synthesis of alkyl hydroperoxides by hydroperoxymercuriation and reduction
作者:A. J. Bloodworth、Christopher J. Cooksey、Despoina Korkodilos
DOI:10.1039/c39920000926
日期:——
Alkyl hydroperoxides, R1R2C(OOH)CH2R3, have been prepared from 30% hydrogen peroxide by hydroperoxymercuriation of the corresponding alkenes, R1R2CCHR3, followed by addition to 2-methoxypropene, reductive demercuriation with basic sodium borohydride and deprotection of the resultant 2-methoxyprop-2-yl derivatives, R1R2C(OOCMe2OMe)CH2R3, with aqueous acetic acid.
烷基氢过氧化物R 1 R 2 C(OOH)CH 2 R 3是由30%过氧化氢通过相应的烯烃R 1 R 2 C CHR 3的氢过氧化汞化反应制得的,然后加至2-甲氧基丙烯中,用碱式硼氢化钠和所得的2-甲氧基丙-2-基衍生物R 1 R 2 C(OOCMe 2 OMe)CH 2 R 3用乙酸水溶液脱保护。