钯催化的烯烃与三嗪烷氢胺羰基化反应研究

酰胺类化合物广泛应用于医药、农药、材料、合成化学等领域,因此,新型且高效合成酰胺的方法一直具有很高的关注度.我们首次使用环状脂肪三级胺类化合物—1,3,5-三嗪烷作胺源,成功解决了钯催化的烯烃氢胺羰基化反应领域中脂肪胺对钯催化剂的毒化问题,合成了多种烷基支链酰胺化合物,并提出了可能的反应机理.

钯催化2,5-二氢呋喃的氢胺羰基化反应

以氯化钯为催化剂,三苯基膦为配体,对甲苯磺酸为助催化剂,通过2,5-二氢呋喃与具有不同取代基的芳香胺、一氧化碳的氢胺羰基化反应,合成了一系列四氢呋喃-3-甲酰胺类化合物。用IR、1HNMR、13CNMR、HRMS对产物进行了结构表征。并考察了不同芳香胺底物的适应性,当苯胺上的取代基为烷基、卤素、甲氧基以及硝基时,均能得到四氢呋喃-3-甲酰胺类衍生物,收率为54.3%～93.2%。

钯催化的三取代烯烃钯催化的三取代烯烃的对映和非对映选择性氢羧基化反应

报道了一种钯催化三取代烯烃的不对称分子间氢羧基化反应,以中等到优秀的产率、对映选择性以及优异的非对映选择性得到了一系列含有两个手性中心的琥珀酸衍生物.所得手性丁二酸酯类化合物通过简单的衍生化即可制备高光学纯度的γ-丁内酯类化合物,彰显了该催化方法在有机合成中的潜在应用.

钯-膦-酸催化剂体系催化烯烃的氢羧基化反应

烯烃的氢羧基化反应是制备有机羧酸的重要途径之一．我们用Ｐｄ（ＯＡｃ）２、三苯基膦（ＰＰｈ３）和对甲基苯磺酸（ｐ－Ｔｓ）催化剂体系，研究了在相转移试剂的存在下，烯烃的氢羧基化反应．对影响反应的各种因素如反应温度、压力、相转移试剂的加入量、不同相转移试剂等作了考察．实验结果表明，较适宜的条件为温度１３０℃、压力４．０ＭＰａ、反应时间为２４ｈ．在此两相反应中，相转移试剂是不可少的，较理想的相转移试剂是十二烷基苯磺酸钠；而当使用β－环糊精作为反应相的转移试剂时，得到的产物基本上是正构物．并将此催化体系用于不同结构烯烃的氢羧基化反应，发现有如下的活性顺序：苯乙烯＞庚烯＞环己烯．

Selenium-catalyzed oxidative carbonylation of 2-aminobenzyl alcohol to give 1,4-dihydro-2H-3,1-benzoxazin-2-one

An efficient,economical,and phosgene-free approach was developed for the preparation of l,4-dihydro-2H-3,l-benzoxazin-2-one from 2-aminobenzyl alcohol.In terms of its key features,this reaction uses the cheap and recyclable non-metal selenium as a catalyst instead of the noble metal palladium;carbon monoxide as a carbonylation agent instead of virulent phosgene or one of its derivatives;and oxygen as an oxidant.The selenium-catalyzed oxidative carbonylation reaction of2-aminobenzyl alcohol proceeded efficiently in a single pot in the presence of triethylamine to afford l,4-dihydro-2H-3,l-benzoxazin-2-one in 87%yield.Furthermore,the selenium catalyst was readily recovered and recycled,affording a product yield of 80%after five cycles.

Emissions of Biogenic Sulfur Gases(H2S,COS)from Phragmites australis Coastal Marsh in the Yellow River Estuary of China

Emissions of biogenic sulfur gases(hydrogen sulfide(H_2S) and carbonyl sulfide(COS)) from Phragmites australis coastal marsh in the Yellow River estuary of China were determined during April to December in 2014 using static chamber-gas chromatography technique with monthly sampling. The results showed that the fluxes of H_2S and COS both had distinct seasonal and diurnal variations. The H_2S fluxes ranged from 0.09 μg/(m^2·h) to 7.65 μg/(m^2·h), and the COS fluxes ranged from –1.10 μg/(m^2·h) to 3.32 μg/(m^2·h). The mean fluxes of H_2S and COS from the P. australis coastal marsh were 2.28 μg/(m^2·h), and 1.05 μg/(m^2·h), respectively. The P. australis coastal marsh was the emission source of both H_2S and COS over the whole year. Fluxes of H_2S and COS were both higher in plant growing season than in the non-growing season. Temperature had a dramatic effect on the H_2S emission flux, while the correlations between COS flux and the environmental factors were not found during sampling periods. More in-depth and comprehensive research on other related factors, such as vegetation, sediment substrates, and tidal action is needed to discover and further understand the key factors and the release mechanism of sulfur gases.

Linear-regioselective hydromethoxycarbonylation of styrene using Ru-clusters/CeO2 catalyst

Hydroalkoxycarbonylation of olefins has been considered to be one of the most attractive methods to synthesize esters. Controlling the regioselectivities of linear esters(L) and branched esters(B) is a challenging project for researchers working in this reaction. Although most of the attention has been paid to control the regioselectivity through ligand design in homogeneous catalytic systems, study in the area is still limited. Herein, Ru-clusters/CeO2 is employed as a heterogeneous catalyst for the hydromethoxycarbonylation of styrene without any additives. After optimization of the reaction conditions, the conversion of styrene is > 99% with 83% and 12% regioselectivity of linear and branched ester, respectively. By using different supports(CeO2(nanoparticle), CeO2-rod, and CeO2-cube), three catalysts including Ru-clusters/CeO2, Ru/CeO2-rod, and Ru/CeO2-cube are prepared and applied in the reaction. Structural characterizations demonstrate that the L/B ratio is related to the Ru size of supported Ru catalysts. Further Raman characterization and NH3-TPD demonstrate that the metal-support interaction and the concentration of oxygen vacancy of the catalyst have a great influence on the Ru size. The mechanism and kinetic analysis for this reaction are also investigated in this work.

Identifying the active sites in C-N codoped TiO_(2) electrode for electrocatalytic water oxidation to produce H_(2)O_(2)

Unveiling the active site of an electrocatalyst is fundamental for the development of efficient electrode material.For the two-electron water oxidation to produce H_(2)O_(2),competitive reactions,including four-and one-electron water oxidation and surface reconstruction derived from the high-oxidative environment co-existed,leading to great challenges to identify the real active sites on the electrode.In this work,Ti/TiO_(2)-based electrodes calcined under air,nitrogen,or urea atmospheres were selected as electrocatalysts for two-electron water oxidation.Electrochemical analyses were applied to evaluate the catalytic activity and selectivity.The morphological and current change on the electrode surface were determined by scanning electrochemical microscopy,while the chemical and valence evolutions with depth distributions were tested by XPS combined with cluster argon ion sputtering.The results demonstrated that Ti/TiO_(2) nanotube arrays served as the support,while the functional groups of carbonyl groups and pyrrolic nitrogen derived from the co-pyrolysis with urea were the active sites for the H_(2)O_(2) production.This finding provided a new horizon to design efficient catalysts for H_(2)O_(2) production.