Oxidative carbonylation of phenol to diphenyl carbonate catalyzed by palladium complexes bridged with N,N‐ligands over functionalized silica

Heterogeneous palladium catalysts anchored on functionalized silica were prepared by sol–gel methods and their catalytic properties for the oxidative carbonylation of phenol to diphenyl carbonate (DPC) were investigated. The catalysts were characterized by means of IR, XPS, EA and BET. The Pd loading in the heterogeneous catalysts and leaching in solution were detected by atomic absorption. The effects of different reaction parameters such as temperature, solvent and inorganic cocatalyst on the yield of DPC and Pd leaching were also studied. It was found that Cu₂O and tetrahydrofuran (THF) were the best partners with these heterogeneous catalysts. In the presence of 3 Å molecular sieves as dehydrating agent, the heterogeneous palladium catalyst prepared from 2‐acylpyridine revealed excellent catalytic performance and stability at 110 °C for 5 h, giving 13.7% yield of DPC based on phenol and 4.0% Pd loss in solution. The heterogeneous catalyst was more active and stable compared with traditional supported Pd? C catalyst under the same reaction conditions. Copyright © 2005 John Wiley & Sons, Ltd.     

Oxidative carbonylation of phenol with a Pd-O/CeO2-nanotube catalyst

CeO2 nanotubes (CeO2-NT) were synthesized using carbon nanotubes as template by a liquid phase deposition and hydrothermal method. X-ray diffraction, transmission electron microscopy, and N2 adsorption-desorption were used to characterize the CeO2-NT. The wall of CeO2-NT was composed of small interconnected nanocrystallites ranging from 4 to 9 nm in size. The specific surface area of CeO2-NT was 108.8 m2/g with an outer diameter of 25 nm and length > 300 nm. Supported Pd cata-lyst, Pd-O/CeO2-NT, was prepared using CeO2-NT as the support. Temperature-programmed reduc-tion analysis showed that the surface oxygen on Pd-O/CeO2-NT could be reduced at low tempera-ture, therefore it showed high activity in the reaction. Pd-O/CeO2-NT was used as the catalyst for the oxidative carbonylation of phenol. It has better activity and DPC selectivity than Pd-O/CeO2-P, which was prepared by supporting Pd on zero dimensional CeO2particles. Under the optimized conditions, phenol conversion was 67.7% with 93.3% DPC selectivity with Pd-O/CeO2-NT. However, its catalyt-ic activity decreased when the catalyst was used for the second time. This was attributed to the destruction of the tubular structure of Pd-O/CeO2-NT and Pd leaching during the reaction.     

Fe(III)EDTA作为氧化羰化苯酚合成碳酸二苯酯一种有效的氧化还原催化助剂

研究了氧化羰化苯酚合成碳酸二苯酯反应。发现了Fe(III)EDTA 在PdCl2/Fe(III)EDTA/1,4 苯醌/ 四丁基溴化铵催化体系中具有很好的助催化效果。讨论了上述催化体系中的每一组分的作用，并提出了一个催化反应机理。氧化羰化苯酚合成碳酸二苯酯反应的最佳温度为100℃～120℃。当反应在100℃、PCO=2.0MPa、PO2=0.5MPa、苯酚 0.5mol、 PdCl2 0.28mmol、n(PdCl2)∶n(Fe(III)EDTA)∶n(苯醌)∶n(四丁基溴化铵)=1∶1∶10∶40、 4A 分子筛 5.0g、 4h进行时，碳酸二苯酯的产率和选择性分别为8.35%和97.5%。压力越高对生成碳酸二苯酯越有利。     

有机-无机杂化材料负载钯催化苯酚氧化羰化合成碳酸二苯酯

 采用溶胶-凝胶法合成了有机-无机杂化材料(OIH),通过与PdCl2(PhCN)2反应,制备了固载化PdCl2/OIH非均相催化剂. 考察了此催化剂在苯酚直接氧化羰化合成碳酸二苯酯反应中的催化活性,并与均相PdCl2催化体系进行了比较. 结果表明,负载型催化剂的催化活性与均相体系相当. 当使用Cu2O和四氢呋喃分别作无机助剂和溶剂时,PdCl2/OIH催化剂重复使用5次后,碳酸二苯酯的产率基本保持不变,钯流失量仅为12.3%.     

钯催化苯酚氧化羰基化合成碳酸二苯酯反应机理的研究进展

综述了Pd2 催化苯酚氧化羰基化合成碳酸二苯酯反应机理的最新研究进展,详细介绍了对催化机理的验证和如何实现Pd催化体系的高效循环.苯酚氧化羰基化合成碳酸二苯酯催化机理的研究表明,碳酸二苯酯是通过CO对Pd-O键的插入和中间体Pd(COOPh)(OPh)的还原消除而生成的.在Pd催化剂体系中引入配体和氧化还原助剂,能防止Pd0的聚集,提高Pd0再生为活性Pd2 的速率,加速催化循环.分析总结了Pd催化剂体系目前存在的问题,并提出了催化剂体系的研究方向.     

Fe(III)EDTA作为氧化羰化苯酚合成碳酸二苯酯一种有效的氧化还原催化助剂(英文)

研究了氧化羰化苯酚合成碳酸二苯酯反应。发现了Fe(III)EDTA在PdCl2/Fe(III)EDTA/1,4-苯醌/四丁基溴化铵催化体系中具有很好的助催化效果。讨论了上述催化体系中的每一组分的作用,并提出了一个催化反应机理。氧化羰化苯酚合成碳酸二苯酯反应的最佳温度为100℃~120℃。当反应在100℃、PCO=2.0 MPa、PO2=0.5 MPa、苯酚0.5 mol、PdCl20.28 mmol、n(PdCl2)∶n(Fe(III)EDTA)∶n(苯醌)∶n(四丁基溴化铵)=1∶1∶10∶40、4A分子筛5.0 g、4 h进行时,碳酸二苯酯的产率和选择性分别为8.35%和97.5%。压力越高对生成碳酸二苯酯越有利。     

苯酚氧化羰基化反应产物的高效液相色谱分析

采用高效液相色谱法分析了苯酚氧化羰基化反应产物,确定了色谱条件:KromasilTM C18色谱柱(150 mm×4.6 mm,5μm),检测波长254 nm,流动相V(甲醇):V(水)=65:35,流速0.6 mL/min.对碳酸二苯酯(DPC)和苯酚进行了定量分析,DPC和苯酚的外标曲线相关系数分别为0.99966...     

常压气相氧化羰基化合成碳酸二乙酯

碳酸二乙酯是一种重要的有机化工原料,可广泛用于合成农药如脱叶灵,医药如喹啉酮衍生物,中间体3-氧硫代羧酸酯,还可用于电子管阴极的镀层[1-3]。生产碳酸二乙酯的传统方法为:无水乙醇与光气反应生成氯甲酸乙酯,氯甲酸乙酯继续与乙醇反应生成碳酸二乙酯后经水洗蒸馏制成。使用光气为原料对设备的要求较高。我们在常压下气相羰基化合成碳酸二乙酯[4]:2ＮＯ+Ｃ2Ｈ5ＯＨ+0.5Ｏ2→2Ｃ2Ｈ5ＯＮＯ+Ｈ2Ｏ(1)ＣＯ+2Ｃ2Ｈ5ＯＮＯ→(Ｃ2Ｈ5Ｏ)2ＣＯ+2ＮＯ(2)产生的一氧化氮可与氧气和乙醇进行反应再生为亚硝酸乙酯,符合原子经济反应且几乎不放出对…     

苯酚氧化羰化合成碳酸二苯酯的新型PdCl2-Co(Pyca)2催化体系

研究了新型的Ｐｄ－Ｃｏ催化体系催化氧化碳化苯酚合成碳酸二苯酯。当ｎ（ＰｄＣｌ２）：ｎ「Ｃｏ（Ⅱ）」：ｎ（四丁基化铵）：ｎ（苯醌）＝１：１：１０：２５,Ｔ＝１２０,Ｐ＝２．５ＭＰａ（Ｐｃｏ／Ｐｏ２＝４：１）,反应时间８ｈ,ＰｄＣｌ２－Ｃｏ（Ｐｙｃａ）２比ＰｄＣｌ２－Ｃｏ（ＯＡｃ）２的催化活性高。当使用ＰｄＣｌ２－Ｃｏ（Ｐｙｃａ）２催化剂时,ＤＰＣ的产率为６．０３％。最佳的反应温度是１２０℃,ＤＰＣ的产率随着体系的总压增加而增大,当压力升到３．５ＭＰａ时,ＤＰＣ产率为８．５３％。     

PdCl_2-Mn(OAc)_2催化苯酚氧化羰基化合成碳酸二苯酯

碳酸二苯酯 ( DPC)是重要的有机碳酸酯 ,它可用于合成许多有机化合物、医药、农药、高分子材料等 [1] .最近日本 Ashia公司与意大利Enichem公司联合开发了双酚 A与 DPC经熔融聚合法制备聚碳酸酯的非光气法新工艺 [2 ] ,使得聚碳酸酯生产工艺朝“绿色化清洁生产”方向取得突破性进展 ,也使得 DPC的合成成为研究的热点 .合成 DPC的方法有光气法、酯交换法及氧化羰基化法 ,其中 ,氧化羰基化法更是引人注目 [1,3 ] ,它是用苯酚与 CO、O2 反应一步合成 DPC的方法 ,具有工艺简单 ,原料易得等优点 ,且避免了使用剧毒的光气 ,是一条“绿色…     

Oxidative carbonylation of styrene to ethyl cinnamate

A detailed study was made of the products of oxidative carbonylation of styrene in the presence of the catalyst system PdCl ₂ -CuCl ₂ -Cu(OAc) ₂ -Mn(OAC) ₂ at 100°C and 3.2 MPa. The target product, ethyl cinnamate, reached a molar proportion of 95%. The principal side reaction products were acetophenone and diethylphenyl succinate. Investigation of the influence of the composition of the catalyst system on the yield of target product and the selectivity of the reaction showed that Mn(OAc) ₂ was of greatest importance as a co-catalyst in the multicomponent Pd catalyst system. The results are discussed with reference to an alcoholate mechanism for oxidative carbonylation of olefins.A. V. Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences, Moscow 117912. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 3, pp. 552–557, March, 1992.     

催化剂对碳酸二甲酯与苯酚酯交换反应的影响

甲基苯基碳酸酯;碳酸二苯酯;催化剂对碳酸二甲酯与苯酚酯交换反应的影响     

Pd(PPh3)2Cl2-CuCl2/AC催化乙醇氧化羰化合成碳酸二乙酯

采用浸渍法制备了乙醇直接气相氧化羰化合成碳酸二乙酯的负载型催化剂,并在连续流动固定床反应装置上评价了催化剂的反应活性,考察了催化剂活性组分、载体、活性组分负载量等因素对催化反应活性的影响。结果表明,活性炭是较好的载体,CuCl2是较好的铜盐前驱体,添加了Pd(PPh3)2Cl2的CuCl2/AC催化剂活性更高。当Cu负载量为9.0%,Pd负载量为0.5%时,催化剂的活性较好。在优化的催化剂制备条件下,乙醇的转化率超过30%,碳酸二乙酯（DEC）的选择性达到95%。     

有机阴离子柱撑水滑石催化酯交换合成碳酸二苯酯

 A series of organic anion-pillared hydrotalcites were synthesized by the ion exchange method and characterized by X-ray diffraction and Fourier transform infrared spectroscopy. The hydrotalcite precursor and pillared hydrotalcites with different anions was tested as catalysts in transesterification of dimethyl carbonate (DMC) with phenol. The results show that the catalytic selectivity of this transesterification reaction over these organic anion-pillared hydrotalcites is significantly improved. The catalytic selectivities of C4H4O4-, C6H8O4-, C10H16O4-, 1,4-C8H4O4-, and C7H5O2-pillared hydrotalcites for transesterified products (diphenyl carbonate and methyl phenyl carbonate) are all greater than 90%, at least 10% higher than that of the hydrotalcite precursor. Under the conditions of n(phenol)/n(DMC)=4, catalyst amount=1.5%, and t=10 h, the C6H8O4-pillared hydrotalcite presents the best catalytic performance, and the DMC conversion and the selectivity for transesterified products reach 43.8% and 93.2%, respectively.     

Copper supported on phenanthroline-functionalized porous polymer as an active catalyst for the oxidative carbonylation of methanol

Porous organic polymer has recently attracted tremendous interest because of its potential to combine the best features of homogeneous and heterogeneous catalysts. In this study, copper supported on phenanthroline-functionalized porous polymer (Cu@PCP-Phen) was prepared by a co-polymerization method and used as a heterogeneous catalyst for dimethyl carbonate synthesis via the oxidative carbonylation of methanol. The catalyst was characterized by N₂ adsorption, scanning electron microscopy, transmission electron microscopy, ¹³C solid-state nuclear magnetic resonance, and X-ray photoelectron spectroscopy, which suggested that it possessed a big surface area, hierarchical porous structure, and strong electron-donating effect toward copper species. The Cu@PCP-Phen catalyst showed high catalytic activity, which was significantly higher than those achieved with Cu-based catalysts under similar reaction conditions. In addition, the catalyst can be easily separated and reused at least six times with only a slight decrease in activity. The salient features of this protocol are the simplicity in handling of the catalyst, high catalytic activity, excellent selectivity, low copper leaching, and good catalyst recyclability.     

二丁基氧化锡催化碳酸二甲酯与苯酚酯交换反应机理研究

研究了二丁基氧化锡催化碳酸二甲酯与苯酚酯交换合成碳酸二苯酯的反应机理, 发现原料苯酚和产物DPC都能与二丁基氧化锡生成同一种中间体, 并测定了其晶体结构. 该晶体属于单斜晶系, P2₁/n空间群; 晶胞参数: a＝1.3336(2) nm, b＝1.7208(2) nm, c＝1.3759(3) nm, β＝101.00(2)°; V＝3.0993(9) nm³; D_c＝1.432 g/cm³; Z＝4; F(000)＝1352; μ＝1.635 mm^－1. 分析结果显示该中间体是一种新型的二聚四烃基二锡氧烷化合物[Bu₂Sn(OPh)OSnBu₂O(Ph)]₂ (I), 该化合物具有中心对称的层状结构. MS和XPS结果证实I在酯交换反应条件下能稳定存在. 基于实验结果, 本文提出了一个合理的酯交换反应机理.     

液相氧化羰基化合成碳酸二乙酯的新型催化体系CuCl/1,10-菲罗啉/N-甲咪唑

Diethyl carbonate (DEC) is one of the important green chemicals widely used for organic synthesis because of its various functional groups. DEC is a better octane blending fuel, and has more oxygen in the molecule than methyl tert-butyl ether (MTBE), 40.6% versus 18.2%, which reduces emissions from gasoline and diesel engine. For these reasons many studies on the production of DEC have been extensively carried out.     

钯/掺杂锰氧八面体分子筛催化一步合成碳酸二苯酯

采用浸渍法制备出Ce3＋, Cu2＋, Pb2＋, Ag＋, Fe3＋掺杂锰氧八面体分子筛, 负载钯后用于一步氧化羰基化合成碳酸
二苯酯(DPC)反应. Pd/Cu-OMS-2 催化活性最高, DPC 收率为12.1%. 通过X 射线衍射(XRD), 扫描电镜(SEM), 氮气吸
附(BET)和X 射线光电子能谱(XPS)对催化剂样品进行了表征. 表征结果表明, 不同金属离子掺杂后, 催化剂的晶型仍
保持隐钾锰矿结构. 从电位滴定测试数据来看, 杂质离子引入后, 锰的平均氧化态增加. 在催化反应过程中, Mn4＋/
Mn2＋和Pd2＋/Pd0 构成了氧化还原循环链, Mn3＋的存在可以补充反应过程中消耗掉的Mn4＋. XPS 分析了晶体中氧物种的
存在形式, 化学吸附氧/(晶格氧＋化学吸附氧)的比值越高, 催化活性越好.     

Oxidative carbonylation reactions: organometallic compounds (R-M) or hydrocarbons (R-H) as nucleophiles

Oxidative carbonylation reactions have attracted broad interest from both academia and industry in recent years. Enormous efforts have gone into the syntheses of carbonate and urea derivatives through the oxidative carbonylation of alcohols and amines. Very recently, organometallic reagents (R-M) and hydrocarbons(R-H) were directly employed as nucleophiles to construct a C-C bond in oxidative carbonylation reactions. This Minireview summarizes this novel type of oxidative carbonylation reaction.     

杂原子介孔分子筛Me-HMS催化酯交换合成碳酸二苯酯

以水热合成法制备了杂原子介孔分子筛Me-HMS(Me指金属杂原子),用于催化碳酸二甲酯与苯酚酯交换合成碳酸二苯酯的反应.小角度的X射线衍射显示,所有样品均具有典型的HMS介孔结构.Me-HMS中,Ti-HMS显示最好的催化性能,其活性与骨架钛含量密切相关,当溶胶中Ti/Si比达1/30时,骨架钛趋于饱和,苯酚转化率达到最大值31.4%,酯交换选择性为99.9%.