芳甲酸氰基芳甲酯的合成

芳甲酸氰基芳甲酯是重要的有机合成中间体,其现有合成方法采用剧毒氰化物为氰源来合成。 本研究以K₄[Fe(CN)₆]为绿色氰化试剂,芳酰氯为原料,采用一锅两步反应合成芳甲酸氰基芳甲酯。 通过改变第二步反应温度、反应时间、硼氢化钠和催化剂的用量获得最佳反应条件,以61.7%~80.3%的产率合成了10种芳甲酸氰基芳甲酯(2a~2j),产物结构通过傅里叶变换红外光谱仪(FTIR)、核磁共振波谱仪(NMR)分析确认。 根据实验结果,提出了可能的反应机理。 该法避免了对剧毒氰化剂的使用,具有产率高、操作简单、后处理方便等优点。     

(2,2-双二茂铁基丙烷)-6-甲酸酯的合成与表征

以2,2-双二茂铁基丙烷作为母体制得对应的甲酸,并以此合成了一系列未见文献报道的（2,2-双二茂铁基丙烷）-6．甲酸酯,其结构经1^H NMR,IR及元素分析表征。     

Synthesis of novel phosphinic acid-containing polymers

Three arylene difluoride monomers containing phosphine oxide ( 1 ), phosphinic acid ( 2 ), or phosphinate ester ( 3 ) groups were prepared and polymerized with bisphenol A to give novel poly-(arylene ether)s ( 4 , 5 , and 6 ). The polymers obtained had moderate molecular weights (η_inh: 0.14–0.30 dL g⁻¹ in N-methylpyrrolidinone) and glass-transition temperatures (T_g: 102–200 °C), depending on the phosphine group in the main chain. Using bis(4-fluorophenyl)sulfone as a comonomer improved the polymerization to give copolymers with higher solution viscosities. The stoichiometric investigation revealed that 7 mol % excess of fluoride monomer gave the highest molecular weight copolymer 8 with η_inh of 0.78 dL g⁻¹, which had a T_g of 176 °C, a T of 432 °C, and formed a hard film by casting from solution. © 2001 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 1854–1859, 2001     

Synthesis Characterization and Application of Polyglycerol Esters of Fatty Acids: Biodegradable Surfactants

Surfactant-based separations are attracting interest due to simple operations and viable economics. The present work focuses on the synthesis of two nonionic surfactants, polyglycerol fatty acid esters of cotton seed oil and castor seed oil, its characterization using Fourier transform infrared spectroscopy and liquid spectroscopy-mass spectroscopy. The synthesized surfactant is used in breaking azeotropic composition of n-propanol–water mixture via cloud point separation. The separation obtained from the synthesized surfactants is compared with the separation obtained from Tween 20 and it is found that both the synthesized surfactants are capable of breaking the azeotrope of n-propanol–water mixture.     

Synthesis from Polyprenols and Biological Activity of Polyprenylacetic Esters

Narrow fractions of polyprenols isolated from birch (C₃₅-C₄₅) and fir (C₇₀-C₈₅) greenery were used to prepare esters of polyprenylacetic acids that exhibited high anti-ulcer activity comparable and in several instances exceeding that of the known anti-ulcer preparation omeprazole (omez).     

相转移催化合成苯基烷氧羰基甲基次膦酸酯和二苯基烷氧羰基甲基氧化叔膦

液-液相转移催化 P-烷基化反应的研究工作还不多。Kem 等曾用亚磷酸二烷基酯或二烷基氧化膦与氯代的取代乙酰胺通过液-液相转移法合成了取代胺基羰基与甲基膦酸酯及氧化叔膦。我们曾研究了亚膦酸二烷基酯与氯     

Synthesis and Characterization of Novel Methacrylate Monomers Having Pendant Oxime Esters and Their Copolymerization with Styrene

New methacrylate monomers, 2‐{[(diphenylmethylene)amino]oxy}‐2‐oxoethyl methacrylate (DPOMA) and 2‐{[(1‐phenylethylidene)ami no]oxy}‐2‐oxoethyl methacrylate (MMOMA) were prepared by reaction of sodium methacrylate with diphenylmethanone O‐(2‐chloroacetyl) oxime and 1‐phenylethanone O‐(2‐chloroacetyl) oxime, respectively. They were obtained from a reaction of chloroacetyl chloride with benzophenone oxime or acetophenone oxime. The free‐radical‐initiated copolymerization of (DPOMA) and (MMOMA) with styrene (St) were carried out in 1,4‐dioxane solution at 65°C using 2,2‐azobisisobutyronitrile (AIBN) as an initiator with different monomer‐to‐monomer ratios in the feed. The monomers and copolymers were characterized by FTIR, ¹H‐ and ¹³C‐NMR spectral studies. The copolymer compositions were evaluated by nitrogen content in polymers. The reactivity ratios of the monomers were determined by the application of Fineman–Ross and Kelen–Tüdös methods. The molecular weights (M¯_w and M¯_n) and polydispersity index of the polymers were determined by using gel permeation chromatography. Thermogravimetric analysis of the polymers reveals that the thermal stability of the copolymers increases with an increase in the mole fraction of St in the copolymers. The activation energies of the thermal degradation of the polymers were calculated with the MHRK method. Glass transition temperatures of the copolymers were found to decrease with an increase in the mole fraction of DPOMA or MMOMA in the copolymers. The antibacterial and antifungal effects of the monomers and polymers were also investigated on various bacteria and fungi. The photochemical properties of the polymers were investigated by UV and FTIR spectra.     

Synthesis and Characterization of Novel Aryl Cyclitols: Polycyclitols

New polycyclitols were synthesized starting from 1,4-naphthoquinone. An endo-selective Diels–Alder cycloaddition between 1,4-naphthoquinone and 1-acetoxybutadiene afforded a diketone. Reduction of the diketone with a NaBH₄-CeCl₃ · 7H₂O system gave a new cyclitol analog diol acetate. Acetylation of this compound afforded a triacetate. Oxidation of the double bond of the triacetate compound with OsO₄ followed by acetylation of hydroxyl groups gave the pentaacetate, whose structure was established unequivocally via application of x-ray crystallographic methods. Hydrolysis of ester groups of pentaacetate under basic condutions furnished the desired and another novel aryl cyclitol.

[Supplementary materials are available for this article. Go to the publisher's online edition of Synthetic Communications® for the following free supplemental resource: Full experimental and spectral details.]     

协同催化合成磷酸酯的研究

由磷酸和醇直接酯化合成了磷酸酯，探讨了无机盐及其复合体系的催化特性，发现Ｎａ＿２ＳＯ＿４－ＴｉＯ＿２－Ｈ＿２ＳＯ＿４和Ｎａ＿２ＳＯ＿４－Ａｌ＿２Ｏ＿３－Ｈ＿２ＳＯ＿４两种复合体系具有协同催化作用和较高的活性。     

Synthesis of D-Mannite Esters

Mono- and diesters of D-mannite with aromatic acids are synthesized. The structures of the resulting compounds are confirmed by IR spectroscopy, PMR, and ¹³ C NMR.     

Synthesis of Saccharose Esters

Di- and triesters of saccharose with aromatic acids are synthesized by transesterification of the methyl esters of the corresponding acids with saccharose. The structures of the resulting compounds are confirmed by IR spectroscopy, PMR, and ¹³ C NMR.     

Synthesis and Characterization of a Novel Cyclomatrix Phosphazene Polymer

Novel phosphazene cyclomatrix network polymers were synthesized via the nucleophilic displacement of activated nitro groups of tri(4-nitrophenoxy)tri(phenoxy)cyclotriphosphazene and hexa(p-nitrophenoxy) cyclotriphosphazene with hydroxyls of bisphenol A. Both monomers and polymers were characterized by Fourier transform infrared spectroscopy, ¹H nuclear magnetic resonance, and elemental analysis measurements, and their structures were identified. Thermal properties of polymers were investigated using dynamic thermogravimetric analysis in air. The results demonstrated that both cyclomatrix phosphazene polymers 4 and 6 were of excellent thermal stability, and their char yields in air at 800°C were 45.1 and 43.2%, respectively. According to combustion phenomenon, polymer 4 was supposed to be processed with a good flame-retardant property because of its excellent crosslinked structure during pyrolysis or combustion. However, polymer 6 yielded the opposite result. Translated from the Journal of Beijing University of Chemical Technology, 2005, 32(2) (in Chinese) This study was supported by the National High Technology Research and Development Foundation (2002AADF3202)     

Synthesis of Alkynes from Enol Esters

Eliminations leading from enol sulfonates, enol phosphates, and enol phosphonium salts to alkynes are reviewed. Olefin eliminations are usually the rate-determining step in the formation of the triple bond. Enol esters may also play a role in the biosynthesis of alkynes.     

硫酸铜催化合成二元酸系列酯

以硫酸铜为催化剂,合成了２０种二元酸系列酯,结果表明,该催化剂具有活性好、操作简便、无三度污染、酯收率高、可多次重复使用等优点。经正交试验得出已下酯较佳的合成工艺条件。     

荧光法快速测定邻苯二甲酸酯的总量

基于邻苯二甲酸酯在浓硫酸下荧光增强的原理构建了一种测定邻苯二甲酸酯总量的荧光分析新方法。 体系的荧光强度与邻苯二甲酸酯的浓度在5.00~600 μg/L的范围内呈线性关系,方法的检出限为0.57 μg/L,回收率在91.6%~105.1%之间。 该方法简单、快速、灵敏度高、线性范围宽。 用于塑料水杯和聚氯乙烯水管中邻苯二甲酸酯总量的测定,结果令人满意。     

Synthesis and Reactions of Cyanic Esters

In 1963, it was found that sterically unhindered esters of cyanic acid, which had previously been considered unobtainable, could be easily prepared from phenols and cyanogen halides. Another synthesis, involving the thermolysis of thiatriazole derivatives, was discovered in 1964. The aryl cyanates in particular have since been found to have many uses as starting materials for the preparation of numerous new classes of compounds [e.g. derivatives of esters of imidocarbonic acid (esters, amides, imides, hydrazides, hydroxylamides, sulfamides, sulfhydrazides, semicarbazides); esters of imidocarboxylic acids; s-triazines, pyrimidines, tetrazoles, triazoles, triazolones, oxadiazoles, thiadiazoles, benzoxazinones, etc.], mainly by addition of nucleophilic or 1,3-dipolar reactants, or as aids e.g. in the elimination of H₂O or H₂S or in the transfer of CN groups.     

新型单取代苯磺酰内脲衍生物的合成及表征

以2-氯-5-氯甲基吡啶和不同取代基的苯磺酰氯为原料, 合成了7个新型的苯磺酰内脲类衍生物, 并用FT-IR, 1H NMR, 13C NMR, 元素分析对其结构进行了表征, 同时对合成目标化合物的反应条件进行了探究.