The selective functionalization of saturated hydrocarbons. Part 40. Aspects of FeII based peroxide fragmentation in pyridine solution
摘要:
The Haber-Weiss mechanism does not apply to the Fe-II induced fragmentation of primary and secondary hydroperosides in pyridine. However, it does apply to tertiary hydroperoxides. Steric bulk is an important factor in Fe-II induced dialkyl peroxide decomposition in pyridine. On the contrary in tetrahydrofuran a different relatively unhindered electron transfer process predominates where the Fe-II becomes a catalyst. (C) 1997 Elsevier Science Ltd.
Tri-liquid system in the synthesis of dialkyl peroxides using tetraalkylammonium salts as phase-transfer catalysts
作者:Stefan Baj、Agnieszka Siewniak
DOI:10.1016/j.apcata.2010.07.015
日期:2010.9.15
system using tetraalkylammonium salts as phase-transfercatalysts is reported. This process was conducted in the presence of highly concentrated aqueous KOH solutions and cyclohexane as an organic solvent. In a liquid–liquid–liquid system, the phase-transfercatalyst forms an insoluble third-liquid phase between the organic and aqueous phases that enables the catalyst to be recycled multiple times.
A fluorinated phosphite traps alkoxy radicals photogenerated at the air/solid interface of a nanoparticle
作者:Goutam Ghosh、Alexander Greer
DOI:10.1002/poc.4115
日期:2020.12
alkoxy radical formation, and 31P NMR readily enabled this exploration, but other phosphites of the series such as the p‐MeO phosphite were limited by hydrolysis reactions catalyzed by surface silanol groups. Fluorinated silica nanoparticles helped to suppress the hydrolysis reaction although adventitious water also plays a role in hindering efficient capture of the alkoxy radicals by the phosphite traps
为了研究在自然和人造表面上形成烷氧基的兴趣,利用哈米特系列亚磷酸三芳基酯(p- MeO,H,p- F和p- Cl)进行了物理有机研究,以将吸附的烷氧基捕获在二氧化硅上纳米粒子。结果表明,在过氧化枯基乙基过氧化物致敏的均相反应中涉及PhC(Me)2 O•和EtO•捕集的机理是一致的。该对- ˚F亚磷酸酯能够间接地监测烷氧基自由基的形成,和31 P NMR容易启用此探索,但该系列的其它亚磷酸酯,如对-亚磷酸MeO受到表面硅烷醇基催化的水解反应的限制。氟化二氧化硅纳米颗粒有助于抑制水解反应,尽管不定水在阻碍亚磷酸盐捕集器有效捕获烷氧基方面也发挥了作用。
Zur alkylierung von hydroperoxiden mit diazoalkanen