The cobalt carbonyl catalyzed reaction of oxetanes with HSiR3 and CO took place at 25°C under 1 atm to give not only 1,4-disiloxybutanes but also 1-siloxypropanes. The product ratio was highly dependent on the solvent used.
The ylides generated from carbenes (:CH2, :CHCO2Et, :CHPh) and oxetane in the presence of methanol undergo Stevens rearrangement and protonation competitively, yielding tetrahydrofurans and 1,3-dialkoxycyclopropanes as major products.
Reactions of methyl radicals with 3-methyloxetane, 3,3-dimethyloxetane and 2,2-dimethyloxetane
作者:Martin G. Duke、Kenneth A. Holbrook
DOI:10.1039/f19848003391
日期:——
The reactions of methylradicals with 3-methyloxetane, 3,3-dimethyloxetane and 2,2-dimethyloxetane have been studied. The overall rates of hydrogen-atom abstraction from these three compounds have been obtained over the temperature range 100–200 °C by assuming the value of Quinn and coworkers (J. Chem. Soc., Faraday Trans. 1, 1976, 72, 1935) for the rate of recombination of methylradicals. The following
研究了甲基与3-甲基氧杂环丁烷,3,3-二甲基氧杂环丁烷和2,2-二甲基氧杂环丁烷的反应。氢原子抽象从这三种化合物的总率已经通过假定昆和同事(的值而获得的温度范围内100-200℃ J.化学会志,法拉第反式1,1976年,72,1935年)表示甲基的重组率。发现以下速率表达式:log 10(k 4 / cm 3 mol –1 s –1)(3ox) = 11.69(±0.20)–38.23(±0.84)kJ mol –1 /2.303 R T log 10(k4 / cm 3摩尔–1 s –1)(3,3ox) = 11.72(±0.20)–39.47(±1.0)kJ摩尔–1 /2.303 R T log 10( k 4 / cm 3摩尔–1 s –1)(2,2ox) = 11.99(±0.23)-41.24(±1.13)千焦摩尔-1 /2.303 ř Ť。从这些速率表达式以及先前从其他三个氧
Synthesis of cyclic trithiocarbonates from cyclic ethers and carbon disulfide catalyzed by titanium complex
This work deals with reaction of oxetane derivatives with carbondisulfide in the presence of (2-propanolato) titanatrane. It afforded six-membered cyclic trithiocarbonates in good yields. Reaction of propylene oxide with carbondisulfide also proceeded in a similar manner to give a five-membered cyclic trithiocarbonate in excellent yield.
3-Halogenoalkoxytributyltin compounds prepared from 1,3-halogenohydrins and tributyltin ethoxyde decompose at 200° leading to the corresponding oxetanes. This reaction is a very convenient method of preparation of this kind of heterocycles.