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…     

中国科学院成都有机化学有限公司化工清洁生产技术与工程事业部

中国科学院成都有机化学有限公司化工清洁生产技术与工程事业部（简称清洁生产事业部）致力于研发绿色化学及化工清洁生产技术,在碳酸二甲酯及下游产品的非光气合成技术研发方面取得了较显著的成绩,已在清洁合成有机碳酸酯、异氰酸酯等大宗化工品方面形成了显著特色和明显优势。     

中国科学院成都有机化学有限公司化工清洁生产技术与工程事业部

中国科学院成都有机化学有限公司化工清洁生产技术与工程事业部（简称清洁生产事业部）致力于研发绿色化学及化工清洁生产技术,在碳酸二甲酯及下游产品的非光气合成技术研发方面取得了较显著的成绩,已在清洁合成有机碳酸酯、异氰酸酯等大宗化工品方面形成了显著特色和明显优势。     

中国科学院成都有机化学有限公司化工清洁生产技术与工程事业部

中国科学院成都有机化学有限公司化工清洁生产技术与工程事业部（简称清洁生产事业部）致力于研发绿色化学及化工清洁生产技术,在碳酸二甲酯及下游产品的非光气合成技术研发方面取得了较显著的成绩,已在清洁合成有机碳酸酯、异氰酸酯等大宗化工品方面形成了显著特色和明显优势。     

光气法制备酰氯的催化剂研究进展

酰氯是一类用途非常广泛的重要有机合成中间体,在工业上制备酰氯主要使用的氯化剂包括PCl3、PCl5、SOCl2、光气等,充分反应后通过过滤、蒸馏等工艺进行脱色提纯制得酰氯。光气法由于对环境污染较低,是目前最常用的方法。三光气可以分解成光气,其优良的物理、化学性质以及便捷的储存和运输条件是光气的最佳替代化学品。但由于光气活性较低,在使用过程中添加催化剂必不可少,本文将重点介绍目前光气法制备酰氯时所使用的各种催化剂及其性能。     

非光气制异氰酸酯绿色过程

异氰酸酯是聚氨酯合成的主要原料.目前,工业上主要采用光气法制备异氰酸酯.该工艺使用剧毒的光气同时副产大量腐蚀性的氯化氢.非光气制异氰酸酯是绿色化学及相关过程的最重要的内容,它的实现将导致传统的光气工艺乃至聚氨酯行业产生革命性的变化.本文主要介绍了本课题组多年来不同羰源下催化羰化制N-取代氨基甲酸烷基酯、热裂解制备异氰酸两步反应的研究进展及存在的问题,特别是近两年本课题组在脂肪族N-取代氨基甲酸烷基酯热裂解过程中聚合物的形成与解聚方面的思路,提出了具有工业实际应用价值的非光气制异氰酸酯的三步反应过程.     

改性羟基磷灰石催化尿素醇解合成碳酸丙烯酯

<正>碳酸丙烯酯(PC)是性能优良的有机溶剂和有机合成原料。PC的合成方法包括环氧丙烷环加成法、光气法和尿素醇解法,其中以尿素和1,2-丙二醇为原料的尿素醇解法,因环境友好、反应条件温和、操作安全,还能有效避免环氧丙烷环加成法对石油的依赖和光气法的剧毒,被认为是PC合成的绿色工艺。     

KF负载型固体碱催化合成氨基甲酸酯的研究

氨基甲酸酯是合成农药、医药及异氰酸酯的重要中间体^[1,2]．传统的氨基甲酸酯的制备是以光气及其衍生物和胺为原料^[3],该工艺使用剧毒的光气,同时副产腐蚀性的HCl．因此,对环境友好的非光气法合成氨基甲酸酯成为当今发展的主流^[4,5]．由胺与碳酸二甲酯反应合成氨基甲酸酯是近年发展起来的非光气法,用碳酸二甲酯代替光气合成氨基甲酸酯可以实现环保要求,反应过程中的唯一副产物甲醇可以循环利用．该反应通常在硝酸铅^[6]、γ—Al2O3^[7]、Zn（OAc）2和三氟化镱^[8,9]等催化条件下进行．但上述催化剂存在催化活性低,     

离子液体-水体系中二苯甲酮的合成

二苯甲酮是一种重要的精细化工中间体和添加剂[1,2],主要应用于光敏剂、化学合成药物、香料香精、涂料、日用化工及电子化学品等领域。目前,二苯甲酮在工业上有多种合成工艺路线[3-6],其中包括光气法、苯甲酰氯法、三氯甲苯法、苯甲酸法、格式试剂法等。然而这些方法在不同程度     

聚碳酸酯合成工艺开发的新进展

本文从工艺开发的角度，简要评介了目前聚碳酸酯两大工业生产工艺，即光气化界面缩聚工艺和熔融酯交换缩聚工艺的研究开发新动向。     

Ir-in-CeO_2催化剂上CO氧化过程中表面碳酸盐的量热研究

应用Tian-Calvet热流量热仪与脉冲微反系统相结合的脉冲量热装置研究了Ir-in-CeO2(Ir主要包裹在CeO2里)催化剂上CO氧化过程表面碳酸盐的形成及其转化.结果表明,碳酸盐的吸附强度与CeO2表面价态直接相关.在反应中首先形成约0.07个单层覆盖度的不可逆吸附碳酸盐,随后形成约0.02个单层覆盖度的可逆吸附碳酸盐并随着Ce3+转变为Ce4+而分解.     

Halovinylene Carbonates in Organic Synthesis. New synthetic methods (2)

Monohalo- and dihalovinylene carbonates constitute a new class of cyclophiles which permit simultaneous introduction of masked α-hydroxyketo and α-diketo functions, respectively, into the cycloadducts. Demasking can be performed by simple hydrolysis. Solvolytic opening of the carbonate ring leads to glycolic acid derivatives in the case of the monohalo compounds and to glyoxylic acid derivatives with the dihalo compounds. Preparation of the title compounds, their potential as synthetic reagents, and the chemistry of their simple reaction products are surveyed from a preparative viewpoint.     

环状碳酸酯低聚物的合成及其开环聚合的研究

环状碳酸酯低聚物的合成及其开环聚合的研究陈雨萍魏玮李革（中国科学院化学研究所工程塑料国家重点实验室北京１０００８０）关键词环状碳酸酯低聚物，聚碳酸酯，开环聚合环状单体的开环聚合在合成高聚物方面具有突出的优点，即在聚合过程中没有副产物、热效应低、聚合...     

Convenient synthesis of ethylene carbonates from carbon dioxide and 1,2-diols at atmospheric pressure of carbon dioxide

An efficient and convenient synthesis of ethylene carbonates was achieved by the reaction of carbon dioxide with 1,2-diols in the presence of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), followed by treatment with 1-bromobutane. This DBU-promoted transformation proceeded at an atmospheric pressure of carbon dioxide at 25 °C and gave ethylene carbonates in good yields.     

Synthesis of allyl aryl sulphides by palladium(0)-mediated alkylation of thiols

Various allylic aryl sulphides are readily prepared in high yields by the palladium(0)-catalyzed S-alkylation of allylic carbonates by various aromatic thiols.     

Silver(I)‐Catalyzed Three‐Component Reaction of Propargylic Alcohols,Carbon Dioxide and Monohydric Alcohols: Thermodynamically Feasible Access to β‐Oxopropyl Carbonates

A silver(I)‐catalyzed three‐component reaction of propargylic alcohols, CO₂, and monohydric alcohols was successfully developed for the synthesis of β‐oxopropyl carbonates. As such, a series of β‐oxopropyl carbonates were exclusively produced in excellent yields (up to 98 %), even under atmospheric pressure of CO₂. The silver catalyst works efficiently for both the carboxylative cyclization of propargylic alcohols with CO₂ and subsequent transesterification of α‐alkylidene cyclic carbonates with monohydric alcohols; thus this tandem process performs smoothly under mild conditions. This work provides a versatile and thermodynamically favorable approach to dissymmetric dialkyl carbonates.     

Convenient Reductive Methylation of Amines with Carbonates at Room Temperature

Methylation of amines is a fundamental and commonly used reaction in organic synthesis. Many methods are known including various reductive methylations using formaldehyde, formic acid, or carbon dioxide in the presence of reductants. However, several of these methods suffer from limited substrate scope and chemoselectivity because of the different nucleophilicities of substrates. In this respect, the combination of carbonates and hydrosilanes is a valuable methylation source in the presence of Pt‐based catalysts. This highly tunable method allows for methylation of both aromatic and aliphatic amines, and chemoselective methylation of aminoalcohols and diamines. Notably, the in situ‐formed catalyst can also be used for the reduction of carbonates to methanol at room temperature. Mechanistic insights on intermediates formed during the reaction pathway were obtained by using ESI mass spectrometry.     

Roman ceramics of hydraulic mortars used to build the Mithraeum house of Mérida (Spain)

Roman ceramics of two hydraulic mortars used to build the pond and water channel of Mithraeum house from Mérida (Spain) have been studied. The sizes of the ceramic fragments found were different in both of the samples studied, showing different behaviour in the reactions with the lime. The X-ray diffraction of the ceramic shows the presence of quartz, mica (biotite), anorthite and hematite accompanied by amorphous phase, being observed scarce vitrification. The presence of mica confirms a firing temperature for manufacturing the ceramic below 900°C. In one of the ceramics studied, X-ray diffraction did not show calcite. However, in the FTIR appear bands that could be assigned to carbonates absorptions and likewise, carbonates were identified in the DTA-TG curves. Ca and small quantities of Si and Al were also identified by SEM-EDX on the surface of the pores that could be due to an amorphous phase formed in the reaction of lime with the Si and Al of the ceramic. On the other hand, in other ceramic samples carbonates (about 10%) were detected. The carbonates have been found filling the pores, sometimes accompanied by a new calcium-aluminium-silicate phase produced by the reaction between the lime and the amorphous phase of the ceramic. The carbonates and the new phases formed inside the pores are responsible for the decrease of the porosity and for the formation of new phases during the heating of the ceramics.     

Sodium carbonate as carbon dioxide source for the synthesis of cyclic carbonates containing the trifluoromethyl group

Trifluoromethylated cyclic carbonates were prepared through the palladium-promoted reaction of tertiary trifluoromethylated propargylic alcohols and sodium carbonate.     

Stereospecific Pd‐Catalyzed Intermolecular C(sp3)–C(sp) Cross‐Coupling of Diarylmethyl Carbonates and Terminal Alkynes Under Base‐Free Conditions

A palladium‐catalyzed intermolecular decarboxylative C(sp³)–C(sp) coupling of diarylmethyl carbonates and terminal alkynes has been developed. The reaction proceeds smoothly under external base‐free conditions to deliver the corresponding alkynylated diarylmethanes with the liberation of CO₂ and MeOH as the sole byproducts. Moreover, enantioenriched diarylmethyl carbonates are stereospecifically converted to optically active cross‐coupling products with inversion of configuration. Thus, the stereospecific palladium catalysis can provide new and unique access to the alkynylated chiral tertiary stereocenters, which are relatively difficult to construct by conventional methods.