Solvent-free oxidation of dec-1-ene using gold/graphite catalyst using an in situ generated oxidant
Solvent-free oxidation of dec-1-ene using gold/graphite catalyst using an in situ generated oxidant
复制标题
使用金/石墨催化剂和原位产生的氧化剂对 dec-1-ene 进行无溶剂氧化
DOI：
10.1039/c4cy01355g
复制
发表时间：
2015
影响因子：
5
通讯作者：
Gupta U
中科院分区：
文献类型：
--
作者：
Gupta U
在无溶剂条件下，使用石墨负载的金纳米颗粒，在自由基引发剂存在下，使用空气中的氧气作为末端氧化剂，在间歇反应器中研究了 dec-1-ene 的氧化。产物随反应时间的演变表明存在初始诱导期，在此期间形成很少的环氧化物并且烯丙基氧化产物占主导地位。随后，由于选择性氧化反应形成的副产物水的存在，在水解形成二醇之前，环氧化物成为主要产物。据认为，烯丙基氧化产物部分原位转化为醛，在诱导期形成过酸；随着转化率的增加，过酸导致环氧化物形成作为主要产物。研究了添加多种醛的影响，当少量添加时，所有醛都会导致环氧化物的形成增强。环氧化物产率的摩尔增加可以接近最初添加的醛量的两倍。这种行为与早期的研究形成鲜明对比，早期的研究使用大于化学计量的醛作为牺牲反应物。原位醛形成的重要性也通过添加苯甲醇来证明，苯甲醇在反应条件下快速产生苯甲醛并增强环氧化物的形成。讨论了观察结果的可能机制解释。
The oxidation of dec-1-ene is investigated under solvent-free conditions using gold nanoparticles supported on graphite and in a batch reactor in the presence of a radical initiator using oxygen from air as the terminal oxidant. The evolution of the products with reaction time shows that there is an initial induction period and during this time very little epoxide is fomed and the products of allylic oxidation are dominant. Subsequently the epoxide becomes the major product prior to the diol being formed from hydrolysis due to the presence of by-product water formed from the selective oxidation reaction. It is considered that the allylic oxidation products are in part converted in situ into aldehydes which form peracids during the induction period; the peracid leads to epoxide formation as the major product as the conversion is increased. The effect of addition of a number of aldehydes is investigated, all leading to enhanced epoxide formation when added in small amounts. Molar enhancements of epoxide yield can approach twice the amount of aldehyde initially added. This behaviour is in contrast to earlier studies which utilise aldehydes in greater than stoichiometric amounts as sacrificial reactants. The importance of in situ aldehyde formation is also demonstrated by the addition of benzyl alcohol which under the reaction conditions rapidly gives benzaldehyde and enhanced epoxide formation. Possible mechanistic interpretations of the observations are discussed.
光学活性 Salen-锰 (III) 配合物催化非官能化烯烃的有氧对映选择性环氧化反应
影响因子：
4
作者：
T. Yamada;K. Imagawa;T. Nagata;T. Mukaiyama
通讯作者：
T. Mukaiyama
环尺寸对负载型金属催化剂选择性氧化环烯烃的影响
DOI：
--
发表时间：
2013
期刊：
影响因子：
--
作者：
Hamed M. Alshammari;Peter J. Miedziak;D. Knight;D. Willock;G. Hutchings
通讯作者：
G. Hutchings