2-吲哚酮和5-甲基-2-吲哚酮的无溶剂法制备

以苯胺和氯乙酰氯为原料在NaOH存在下酰化合成N-氯乙酰基苯胺,然后N-氯乙酰基苯胺在无水AICI,催化下环化合成2-吲哚酮．对由N-氯乙酰基苯胺合成2-吲哚酮的工艺条件进行了改进．结果表明合成2-吲哚酮的最佳条件为：反应温度为220℃,反应时间为60min,加料时温度为180℃,N-氯乙酰基苯胺与氯化钠,无水AlCl3的重量比为1：1：5．5．改进后的合成2-吲哚酮收率达到88．3％,纯度99％,收率比原工艺提高了24．6％．在此基础上,还合成了5-甲基-2-吲哚酮,并得到其最佳条件为：反应温度为190℃,反应时间为30min,加料时温度为180℃,4-甲基-N-氯乙酰基苯胺与氯化钠,无水AlCl3的重量比为1：1：5．5,收率达到83．1％,纯度为99％．     

维生素A的生物有机化学研究进展

本文综述了近年来对维生素A生理功能的新认识和有关的化学反应:自由基反应,酶催化反应,电子转移反应,光化学反应,以及微观环境效应等方面的研究进展。     

三芳胺合成的研究进展

三芳胺化合物的合成方法主要有3种:(1)非金属催化的胺化反应;(2)铜催化的Ullnann反应,包括使用过量铜粉为催化剂的传统的Ullmann反应、使用相转移催化剂的Ullmann反应以及使用配体的post-Ullmann反应;(3)钯催化的Buchwald-Hartwig反应.该类反应活性的关键是配体的选择,根据配体结构的不同可分为双膦螯合型配体、单膦配体和非膦配体.对该类化合物的这几种合成方法的研究进展进行了总结.     

Study on the alkylation reaction of guanine and N-acetylguanine and the synthesis of 1''''-C alkylated carba-DHPG analogues

The alkylation reaction of guanine and N-acetylguanine with model compounds such as isopropyl bromide or 4-heptyl tosylate were studied. The reaction conditions such as temperature, solvent, base, and catalyst were examined for their effects on the reaction rate, and the yield and regioselectivity of the coupling reaction. The highest yield was obtained by using DMSO as the solvent. The reaction proceeded in a homogenous manner to give higher yield of 9-N and 7-N substituted product in a mole ratio of 1:1. The ratio could be raised to 2:1 if dibenzo-18-crown-6 was used as a catalyst. Using the above procedure, three carba-DHPG analogues bearing different 1'-C alkyl side chains were synthesized.     

Determining optimum conditions for lipase-catalyzed synthesis of triethanolamine (TEA)-based esterquat cationic surfactant by a Taguchi robust design method

A Taguchi robust design method with an L? orthogonal array was implemented to optimize experimental conditions for the biosynthesis of triethanolamine (TEA)-based esterquat cationic surfactants using an enzymatic reaction method. The esterification reaction conversion% was considered as the response. Enzyme amount, reaction time, reaction temperature and molar ratio of substrates, [oleic acid: triethanolamine (OA:TEA)] were chosen as main parameters. As a result of the Taguchi analysis in this study, the molar ratio of substrates was found to be the most influential parameter on the esterification reaction conversion%. The amount of enzyme in the reaction had also a significant effect on reaction conversion%.     

Preparation of biodiesel catalysed by KF/CaO with ultrasound

Biodiesel, chemically consists of fatty acid methyl ester (FAME) produced by methanolysis of natural triglycerides, such as animal fats and vegetable oils, is a kind of biomass energy, which is renewable and ecofriendly. In this article, KF/CaO was used as solid base catalyst for transesterification of soya bean oil and methanol, while ultrasound as supplementary means. Compared to mechanical stirring, ultrasound treatment is an effective method to increase the yield of FAME and shorten reaction time. By single-factor method, the optimisation of reaction conditions has been studied. The research showed that the optimum reaction conditions were: w(catalyst)/w(oil): 3%, reaction temperature: 65°C, n(methanol)/n(oil): 12, reaction time: 1?h, sound intensity: 1.01?W?cm(-2), frequency: 20?kHz, the yield of FAME could be 97%.     

Brønsted guanidine acid-base ionic liquids: novel reaction media for the palladium-catalyzed Heck reaction

[reaction: see text]. Br?nsted acid-base ionic liquids (GILs) based on guanidine and acetic acid are efficient reaction media for palladium-catalyzed Heck reactions. They offer the advantages of high activity and reusability. GIL2 plays multiple roles in the reaction: it could act as solvent, as a strong base to facilitate beta-hydride elimination, and as a ligand to stabilize activated Pd species.     

磺化聚苯乙烯的无溶剂制备及其催化性能研究

本文以聚苯乙烯为底物,发烟硫酸为磺化剂,在无溶剂和无催化剂条件下制得了磺化聚苯乙烯,对其酸度和结构性能进行了表征,并详细研究了其催化肉桂酸与正丁醇酯化反应的性能。在醇酸摩尔比为15∶1、环己烷作带水剂的条件下,分别考察了催化剂用量、回流温度、回流时间对酯化反应的影响,优化了反应条件,并在优化条件下,探究了其重复催化使用性能,结果表明,该催化剂重复使用15次,产率基本保持不变,仍可达到69.6%。该催化剂对肉桂酸与其他低级脂肪醇的酯化反应也具有良好的催化效果,是一种环境友好型具有潜在应用价值的固体酸催化剂。     

The kinetics of the epoxy amine cure reaction from a solvation perspective

This article investigates the role of solvation effects in the autocatalysis reaction of the epoxy–amine cure reaction. A single‐phase three component model was developed encompassing a two‐component reaction mix and a single polymeric product. The reaction was modelled as an S_N2 reaction. Association of the nucleophile with each component in the reaction was defined via a binding constant. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 3579–3586, 2004     

六苯氧基环三磷腈的合成及其在层压板中的阻燃应用

以六氯环三磷腈（HCCTP）粗产物、苯酚、NaOH为反应原料,四丁基氯化铵（TBAC）为相转移催化剂,氯苯和水为溶剂,合成了六苯氧基环三磷腈（HPCTP）,考察了反应温度、反应时间、反应溶剂、物料配比对收率的影响。结果表明,在最佳原料配比n(NaOH): n(苯酚): n(TBAC): n(HCCTP粗产物)=7.5: 6.3: 0.15: 1,30 ℃反应4 h,回流反应6 h,HPCTP的收率达到75％。采用红外光谱、核磁氢谱、碳谱、磷谱、X射线衍射分析、示差扫描量热分析、热重分析测试技术对产物进行了表征分析,并首次用于苯并噁嗪树脂玻璃布层压板,当HPCTP的质量分数为10％时,燃烧等级达到V-0级,平行击穿电压为47 kV,热态弯曲强度为596 MPa。     

合成苯并咪唑类化合物的工艺改进

邻苯二胺磷酸盐与脂肪酸在无溶剂的条件下回流反应合成了苯并咪唑类化合物,其结构经IR确证。正交试验确定最佳反应条件为:邻苯二胺50 mmol,n(邻苯二胺):n(甲酸)=1.0:1.5,磷酸4 g,回流反应7 h。在最佳反应条件下做放大实验,产率89.3%。     

RuCl3催化氧化γ-甲基吡啶合成γ-吡啶羧酸的研究

吡啶类含氧化合物是一类很重要的有机化合物 ,在药物、食品和饲料添加剂、染料工业等诸多领域应用极为广泛。关于吡啶羧酸的制备 ,实验室和工业上都有较多的研究报道[1 ] 。但不外乎两大类 ,一类反应是化学计量氧化法 ,如高锰酸钾氧化法[1 ] 和硝酸氧化法[2 ,3] ,这类方法原料消耗量大 ,成本高 ,不适合于规模生产。另一类反应是催化氧化法 ,对这类反应研究的报道 ,工业上普遍采用的一种生产工艺是氨氧化法[1 ] ,此法是工业上生产烟酰胺和烟酸的重要方法之一 ,其条件苛刻。文献[4～ 6] 报道以醋酸作溶剂、以醋酸钴、醋酸锰和溴化物作催化剂 ,…     

“讲一练二考三”理念在有机化学实验教学中的运用——以苯甲酸的制备为例

采用微波辐射及相转移催化剂改进了高锰酸钾氧化制备苯甲酸实验,系统研究了微波功率、反应温度、反应时间、反应物物质的量比、催化剂用量等因素对产率的影响,并同电热套加热方式进行了比较.结果表明,该反应的最佳条件为:微波辐射时间40 min,微波功率80 W,反应温度80℃,相转移催化剂氯化苄基三乙铵用量为甲苯的0.2当量,高锰酸钾与甲苯的物质的量比为4.5:1.与电热套加热方式相比,微波辐射法缩短了反应时间,并显著提高了反应效率.以苯甲酸制备实验为例介绍了“讲一练二考三”教学新理念及其在有机化学实验教学实践中的运用.     

SYNTHESIS OF FUNCTIONAL MACROMOLECULE INTERMEDIATE THROUGH ACYLATION CATALYZED BY [Emim]Cl-AlCl3 IONIC LIQUID

Acylation reaction of anthracene with oxalyl chloride in the presence of [Emim]Cl-AlCl3 ionic liquid has been investigated. Pure 1,2-aceanthryenedione, which is used as intermediate of functional aromatic polymer material, was obtained by recrystalling the reaction mixture with aether and was determined by GC/MS, 1↑HNMR and FTIR analysis. The influences of various parameters, such as the contents of AlCl3 in [Emim]Cl-AlCl3, the amount of acylation agent, amount of [Emim]Cl-AlCl3, reaction temperature and reaction time were investigated. The optimum conditions were as follows： the molar fraction of AlCl3 in ionic liquid [x（AlCl3）] being 0.67, molar ratio of ionic liquid to anthracene being 2：1, molar ratio of oxalyl chloride to anthracene being 2：1, reaction temperature being 40℃ and reaction time being 6h. Under above conditions, the yield and selectivity of 1,2-aceanthrylenedione can reach 91.5% and 98.3% respectively. Further more, [Emim]Cl-AlCl3 ionic liquid, compared with metal halides such as AlCl3, was found to catalyze the reaction as a novel environmental friendly catalyst and solvent and can be reused.     

Novel process for synthesis of 1,1,3,3-tetrabutyl-1-methoxy-3-isocyanatodistannoxane

A new process for synthesis of 1,1,3,3-tetrabutyl-1-methoxy-3-isocyanatodistannoxane (TBMI) from dibutyltin oxide (DSnO), methyl carbamate and methanol was proposed. The structure of the TBMI was confirmed by UV-Vis, elemental analyses, FTIR and HPLC. The effects of various conditions, such as reaction temperature, pressure, reaction time, molar ratio of the reactants and the stirring speed were investigated in the terms of TBMI yield. The experimental results indicated that the optimal reaction conditions were the molar ratio of methyl carbamate:DSnO of 2:1, the reaction time of 3 h, the reaction temperature of 433 K, the methanol:DSnO molar ratio of 2:1, the initial pressure of 0.4 MPa and the stirring speed of 1000 rpm, respectively. TBMI yield of 96.9% was obtained in the optimal reaction conditions. This process shows some advantages like easy to operate, higher yield, shorter reaction time and lower cost.     

苯并噻唑-2-甲醛合成方法的改进

以邻氨基苯硫酚为原料,先与羟基乙酸反应合成2-羟甲基苯并噻唑,然后通过氧化反应生成苯并噻唑-2-甲醛。对比了几种氧化剂的效果,发现二氧化锰氧化的效果最好。优化的反应条件为,2-羟甲基苯并噻唑与二氧化锰的摩尔比为1∶8,回流反应8h,产率可达90.2%。该方法适合苯并噻唑-2-甲醛及其衍生物的大规模生产。     

微波辅助法合成Hantzsch酯

以芳香醛、乙酰丙酮及碳酸氢铵为原料,固载路易斯酸蒙脱土为催化剂,通过微波辅助法催化合成了5个Hantzsch酯类化合物,其结构经¹H NMR和IR确证。考察了催化剂、溶剂、温度、时间和氮源对产率的影响。结果表明：反应温度60 ℃,微波辐照时间10 min, n(芳香醛) :n(乙酰乙酸乙酯) :n(碳酸氢铵)=2.0:2.0:1.0,氯化镍固载蒙脱土为催化剂（10%）,产率高达97.8%。     

Addition reaction of spiro orthoesters with electrophiles: A model reaction for the development of novel polyaddition accompanying ring-opening isomerization

The addition reaction of spiro orthoesters (SOEs) with electrophiles accompanying ring-opening isomerization was investigated as a model reaction for polyaddition of bifunctional SOEs with bifunctional electrophiles. Among several electrophiles such as carboxylic acids and carboxylic anhydrides, acid halides showed particularly high reactivities to SOEs. An equimolar reaction of SOEs with acid chlorides took place selectively, leading to the corresponding 1 : 1 adducts. SOEs with seven-membered cyclic ether rings—1,4,6-trioxaspiro[5.6]undecane derivatives—showed higher reactivities than SOEs with six- and five-membered cyclic ether rings. The reaction accompanied zero shrinkage in volume. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 4502–4509, 1999     

Divergent pathways in the reaction of Fischer carbenes and palladium

[reaction: see text] The Pd-catalyzed reaction of beta-arylaminochromium(0) carbene complexes produces by transmetalation the first isolated and X-ray structurally characterized bis-Pd(II) carbene complex, as well as other alternative reaction pathways, such as the oxidative addition-transmetalation sequence, not seen before in this chemistry.     

线型二甲基硅氧烷低聚物的制备

以八甲基环四硅氧烷(D₄)、六甲基二硅氧烷(MM)为原料, 采用固体超强酸(SA)TiO₂/SO42-为催化剂合成线型二甲基硅氧烷四聚体(MD₄M), 通过均匀设计实验和单因素实验分别研究了反应时间、反应温度、相对分子质量调节剂MM量和催化剂添加量对反应转化率和MD₄M含量的影响, 结果表明, 当D₄与MM的摩尔配比为0.75:1, 反应温度为100 ℃, 反应时间为7 h, 催化剂(SA)用量为反应物总质量的2%时, D₄开环聚合制备线型二甲基硅氧烷低聚物的反应转化率为87%, 其中MD₄M的收率为16.8%, 较硫酸催化体系提高了1.6%, 催化剂SA循环套用3次以上, 催化活性基本不变, 采用准均相体系建立了固体超强酸非均相催化D₄开环聚合的宏观动力学模型。