Studies on Catalytic Side-Chain Oxidation of Nitroaromatics to Aldehydes with Oxygen

The side-chain oxidation of 2-nitrotoluene in liquid phase in the presence of catalytic amount of manganese sulfate and stoichiometric amount of potassium hydroxide with oxygen was studied. In the most favorable conditions, over 80% of conversion of 2-nitrotoluene and 50% of selectivity to 2-nitrobenzaldehyde was achieved. Effects of the reaction parameters on the conversion of the reactant and the selectivity of the product were examined. These results, together with EPR spectroscopic study, show that a benzyl anion was formed in the early stage of the reaction, which was then converted to the final product via a free radical mechanism.     

氧气液相氧化一元取代甲苯制备芳香醛

研究了在酸碱不同体系下气氛液相氧化对氯甲苯、邻硝基甲苯制取相应芳香醛的反应 ,比较了反应温度、反应时间、氧气流量、底物浓度对各自反应的影响。初步研究了反应在酸碱不同条件下的反应机理 ,认为在醋酸体系下是自由基反应 ,而在有机胺体系下应是碳负离子反应。     

以天然产物为先导化合物开发的农药品种(Ⅱ)--杀虫杀螨剂

概述了以天然产物为先导化合物进行的杀虫杀螨剂的创制研究以及开发的品种，涉及的化合物或类别如氨基甲酸酯、拟除虫菊酯、沙蚕毒素类似物、吡咯类、新烟碱类、保幼激素类似物、双酰肼(蜕皮激素类似物)、鱼藤酮类似物、二烯酰胺、季酮酸类、嘧螨酯、灭螨醌等，并对部分化合物的生物活性和创制经纬等进行了概述。     

新型2-芳氧基-3H-喹唑啉-4-酮的合成

利用膦亚氨试剂的氮杂Wittig反应在喹唑啉酮的2位导入取代基，制得了9个2-芳氧基喹唑啉酮的新衍生物。探讨了碳二亚胺与不同酚在固体碳酸钾催化下的反应活性。     

取代2-四氢萘酮的一步合成新方法研究

本文介绍了一步法制备取代2-四氢萘酮的新方法,与常规合成方法相比,该法具有明显的优点:不需要先将羧酸转化成酰氯,避免了三氯化铝以及含氯溶剂的应用,并使催化剂得以循环利用。因此,该方法安全、环保,有望取代常规的付-克反应在工业上的应用。     

1，3－取代方酸衍生物的光谱研究及二聚体、簇集体的形成

本文合成了１，３－取代方酸衍生物：１，３－双［４－二甲胺苯基］－２，４二羟基环丁二烯氢氧双内盐（ＤＭＣＳ），１，３－双［４－双十六烷胺苯基］－２，４二羟基环丁二烯氢氧双内盐（ＤＨＣＳ）。研究了ＤＭＣＳ和ＤＨＣＳ在不同溶剂中的光物理行为，估算了ＤＭＣＳ、ＤＨＣＳ的基态与激发态之间偶极矩差值。在ＣＴＡＢ胶束中，除ＤＭＣＳ单体分子外，ＤＭＣＳ形成了二聚体。在二氧六环－水体系中，研究了ＤＨＣＳ的簇集行为，并测定了ＤＨＣＳ的临界簇集组成（Ｃ＿ψ）及临界簇集浓度（Ｃ＿Ａ）     

3-取代苯基-5-羟基-5-三氟甲基异噁唑啉的合成

3 取代苯基 5 羟基 5 三氟甲基异口恶唑啉是合成具有异口恶唑结构的原卟啉原氧化酶抑制剂类除草剂的重要中间体。通过以下途径制得4个具有不同取代基的异口恶唑啉中间体:首先,在回流状态,n(甲醇钠)∶n(取代苯乙酮)=2∶1的甲醇钠存在下,取代苯乙酮与三氟乙酸乙酯缩合得到取代苯基 4,4,4 三氟 1,3 丁二酮;后者可在室温下,于二氯甲烷溶剂中,用氯化硫酰氯化,在侧链上引入氯原子;最后,以乙酸作溶剂,回流下,具有不同取代基的苯基 1,3 丁二酮与盐酸羟胺闭环得到产物。反应总收率大于95%。产品结构经质谱、核磁共振氢谱、碳谱确认正确。     

以天然产物为先导化合物开发的农药品种(Ⅰ)--杀菌剂

研究天然产物的重点不是直接利用它，而是以其为先导化舍物开发活性更优的天然产物替代品。只有如此，才能保护有限的资源，更好的为人类持续发展服务。在农药创制研究中以天然产物为先导化合物进行研究、开发新农药品种的方法仍将是一种有效的方法；因为以具有活性的天然产物为先导化合物不仅可以更快、更经济的发现活性更优的类似物，而且因其内在的性能是产品更易符合环境保护与持续发展之需要。本文概述了以天然产物为先导化合物进行的新农药创制研究以及开发的农药品种，其中杀菌剂包括乙蒜素、稻瘟灵、恶霉灵、肉桂酸衍生物、吡咯类化合物、甲氧基丙烯酸酯类等。旨在吸取他人成功经验，利用其研究之成果研制我们自己的新农药品种。     

Copolymerization of phenylacetylene with various acetylenes by W- and Mo-based catalysts

In the copolymerization of phenylacetylene with various acetylenes catalysed by WCl₆·Ph₄Sn, the relative reactivity of monomer decreased with increasing steric effect of monomer, e.g. HC  Cn-Bu, HC  Cn-Hex > HC  CPh, HC  Cs-Bu > HC  Ct-Bu, MeCCPh, CICCPh. While 1-chloro-2-phenylacetylene (a disubstituted acetylene) showed high reactivity in the homopolymerization by Mobased catalysts, the reactivity was remarkably depressed in the presence of phenylacetylene as comonomer. Based on these results, the relative reactivity of the acetylenic monomers in copolymerization was explained in terms of competitive coordination of monomers to the propagating end.     

Synthesis,characterization, and thermal behavior study of methyl methacrylate polymers containing 4‐carbazole substitutes

A new polymerizable monomer, [4‐(9‐ethyl)carbazolyl]methyl methacrylate ( 2 ), was synthesized by reacting of methacrylic acid and 4‐hydroxymethyl‐9‐ethyl carbazole ( 1 ) by esterification procedure in the presence of N,N′‐dicyclohexylcarbodiimide. The resulting monomer was then polymerized free‐radically to form the poly(methyl methacrylate) containing 4‐(9‐ethyl)carbazolyl pend ent groups. Also, copolymerization of monomer 2 with various acrylic monomers such as methyl methacrylate, ethyl methacrylate, methyl acrylate, ethyl acrylate, and n‐butyl acrylate by azobisisobutyronitrile as a free radical polymerization initiator gave the related copolymers in high yields. The structure of all the resulted compounds was characterized and confirmed by FTIR and ¹H NMR spectroscopic techniques. The average molecular weight of the obtained polymers was determined by gel permeation chromatography using tetrahydrofurane as the solvent. The thermal gravimetric analysis and differential scanning calorimeter instruments were used for studying of thermal properties of polymers. It was found that, with the incorporation of bulky 4‐(9‐ethyl)carbazolyl substitutes in side chains of methyl methacrylate polymers, thermal stability and glass transition temperature of polymers are increased. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4989–4995, 2006