Copper(I)‐Catalyzed Desulfinative Carboxylation of Sodium Sulfinates using Carbon Dioxide

A copper(I)‐catalyzed desulfinative carboxylation of sodium sulfinates using carbon dioxide has been developed. This reaction showed wide functional group tolerance. A series of sodium aryl‐ and alkenylsulfinates could be converted into the corresponding carboxylic acids in good to excellent yields. Additionally, the reaction mechanism was studied by in situ NMR analysis and isotopic labeling experiments.

     

溶剂羧化法合成2－羟基－3－萘甲酸工艺的研究

本文根据Ｋｏｌｂｅ－Ｓｃｈｍｉｔｔ羧化反应原理和溶剂法工艺的特征，分析了合成２－羟基－３－萘甲酸的反应机理。研究了数种溶剂的应用性能，确定了适宜的溶剂。根据工艺参数的正交优化实验结果，确定了适宜的工艺参数，为溶剂法工艺的实施提供了理论依据和可行的工艺参数。     

高度单分散氰基聚倍半硅氧烷微球的可控合成及羧基化

在水溶液中,以氰乙基三乙氧基硅烷(CTES)为前驱体,氨水为催化剂,通过一步法合成聚氰基倍半硅氧烷(PCSQ)微球,并通过进一步酸化实现了氰基到羧基的转化.通过扫描电子显微镜(SEM)、傅里叶变换红外光谱(FTIR)、热重(TG)分析对所得微球的形貌、有机功能基及热性能进行了表征,研究表明CTES的用量与催化剂氨水的浓度对PCSQ微球的形貌和粒径有着重要影响,当去离子水为30 mL、CTES为1mL、氨水为1 mL时,可以制备出平均粒径在600 nm、高度单分散的PCSQ微球.将所制备的PCSQ微球分散在30％硫酸溶液中,65℃搅拌24 h可以将微球上负载的氰基水解酸化为羧基.     

An unexpected ring carboxylation in the electrocarboxylation of aromatic ketones

The electrocarboxylation of various aromatic ketones, carried out in N-methyl-2-pyrrolidone (NMP) in a diaphragmless cell equipped with a carbon cathode and an aluminium sacrificial anode, yielded, among the products, the target hydroxy acids, the corresponding alcohols and pinacols and, quite surprisingly, detectable amounts of substituted benzoic acids and cycloexene carboxylic acids. These compounds arise from a never reported before electrocarboxylation on the aromatic ring, respectively, for substitution of an aromatic hydrogen and from an addition reaction. For example, the electrocarboxylation of acetophenone gave rise to the substituted benzoic acids in ortho, para and meta positions, while for 2,2-dimethylpropiophenone the substituted benzoic acid in meta position and the cyclohex-5en-1,3-dicarboxylic acid derivative were detected among the products.     

CO2插入C—H(sp)键制备丙炔酸衍生物的研究进展

丙炔酸类化合物是一类用途广泛的有机中间体,以CO₂为羧基化试剂,将其插入到端基炔烃的C—H(sp)键是制备丙炔酸类化合物的一条新型路线,其绿色化程度显著高于传统方法。本文在系统分析CO₂路线制备丙炔酸类化合物反应机理的基础上,梳理了该反应催化体系的研究进展,并总结了近年来与该反应实际应用密切相关的前瞻研究。基于上述总结,本文认为后续研究应开展的工作包括：①从实际工况角度（耐强碱性反应体系、耐强极性溶剂等）出发进行催化剂的设计;②强化反应机理研究,明确不同催化剂上的反应路径和中间体形态差异,夯实理论基础;③强化潜在技术瓶颈问题的突破,尤其是湿度敏感、碱助剂循环、下游合成网络衔接等。     

Anionic synthesis of aromatic carboxyl functionalized polymers. Chain-end functionalization of poly(styryl)lithium with 4,5-dihydro-4,4-dimethyl-2-[4-(1-phenylethenyl)phenyl] oxazole

The novel syntheses of 4-(4,5-dihydro-4,4-dimethyl-2-oxazolyl)benzophenone, 1-[4-(4,5-dihydro-4,4-dimethyl-2-oxazolyl)phenyl]-1-phenylethanol and 4,5-dihydro-4,4-dimethyl-2-[4-(1-phenylethenyl)phenyl]oxazole ( 1 ) are described. ω-Oxazolyl polystyrene ( 2 ) was synthesized in quantitative yields by the reaction of poly(styryl)lithium with stoichiometric amounts of 4,5-dihydro-4,4-dimethyl-2-[4-(1-phenylethenyl)phenyl]oxazole ( 1 ) in toluene/tetrahydrofuran (4 : 1 v/v) at −78°C. Deblocking of the oxazoline protecting group by acid hydrolysis followed by saponification quantitatively provides the corresponding aromatic carboxyl chain-end functionalized polystyrene ( 3 ). The functionalization agent and functionalized polymers were characterized by HPLC, thin layer chromatography, size exclusion chromatography, vapor phase osmometry, spectroscopy (¹H NMR, ¹³C NMR and FTIR), potentiometry and elemental analysis.     

从生物质衍生原料到2,5-呋喃二甲酸产品的合成研究进展

2,5-呋喃二甲酸（2,5-FDCA）作为呋喃的衍生物,是一种具有良好稳定性和高附加值的生物基平台化合 物,在聚酯、聚酰胺、聚氨酯、热固性材料和塑化剂等众多领域都得到了广泛应用,如何绿色高效地制备 2,5-FDCA是近年来的研究重点。本文综述了以5-羟甲基糠醛（HMF）、糠酸、己糖二酸等生物质衍生原料合成 2,5-FDCA的方法及特点。己糖二酸等其他路线产率较低,不利于工业化的发展。HMF路线与之相比具有产率高和副产物少的优势,但由于原料来源与食品行业相冲突且生产成本较高,所以利用不可食用的生物质衍生原料糠酸低成本合成目标产物将成为未来可持续发展的重要研究方向。在此基础上,本文通过对比糠酸各路线的优缺点后发现,CO{}_{\mathrm{3}}^{\mathrm{2}-}促进的糠酸羧基化合成方法无需反应溶剂,催化剂组分简单可再生,这些都有利于低成本合成产品。且由于工艺流程简单,产物选择性和收率高,糠酸羧基化方法将成为绿色大规模生产2,5-FDCA极具潜力的路线。     

阿霉素在羧基化纳米金刚石表面的负载与释放性能研究

利用高温氧化法实现纳米金刚石表面羧基化,以提高其对阿霉素药物的负载率。通过考查高温氧化条件、药物浓度、溶液pH值等因素对其载药效果的影响规律,得出最佳载药条件,制备了负载量为425 μg/mg的纳米金刚石-阿霉素体系。探索了不同pH环境下该载药体系的药物释放规律,结果表明,羧基化纳米金刚石负载阿霉素后,可高效释药,最高释放率可达91%,说明纳米金刚石在改善药效发挥、降低药量、减少毒副作用等方面具有巨大潜力。     

Effective Guanidine‐Catalyzed Synthesis of Carbonate and Carbamate Derivatives from Propargyl Alcohols in Supercritical Carbon Dioxide

The reactions of propargyl alcohols with carbon dioxide in supercritical carbon dioxide or in acetonitrile with gaseous carbon dioxide in the presence of organic bases as catalysts have been examined. Bicyclic guanidines are effective catalysts for the formation of α‐methylene cyclic carbonates under mild reaction conditions. Oxoalkyl carbonates, oxoalkyl carbamates or α‐methyleneoxazolidinones are obtained in high yields and good selectivities in one‐step starting from propargyl alcohols and an external nucleophile (alcohols or amines) using bicyclic guanidines as catalysts in supercritical carbon dioxide. Propargylic diols under the same reaction conditions underwent a rearrangement process instead of carbon dioxide insertion whereas in the presence of an external nucleophile the formation of oxocarbonates, oxocarbamates or cyclic carbamates was achieved in satisfactory yields.