几种新型聚合物配体的合成及其固载化铑催化剂的醛化性能研究

本文使用交联聚苯乙烯为载体合成了几种新型的聚合物配体和固载化铑催化剂,考察了它们对二异丁烯和戊烯-1氢甲酰化反应的催化性能,探讨了催化剂的铑脱落现象。     

含芘环的缩氨基硫脲类化合物的合成及其对汞离子的识别

合成了芘甲醛-4-甲基缩氨基硫脲(1)、芘甲醛-4-(4-乙苯基)缩氨基硫脲(2)、芘甲醛-4,4-二甲基缩氨基硫脲(3)三个化合物,并通过质谱、元素分析、傅立叶红外光谱和核磁共振氢谱进行了结构表征.利用荧光激发和发射光谱,对其荧光活性进行研究,并考察了对溶液中汞离子的识别作用.在分别向三种化合物的溶液中逐步滴加汞离子时,其特征的荧光发射波长处对应的强度值都呈现规律性变化.因此可利用比率荧光法实现对汞离子配合过程的观测.结果表明,三种化合物都能与汞离子形成1:1的配合物,配合常数分别为4.57×104,5.54×104和2.12×104L/mol,其检测下限分别为4.56×10-6,2.61×10-6和5.49×10-6mol/L.     

Catalytic Properties of Heteropolytungstates with 3<Emphasis Type="Italic">d</Emphasis> Elements and Their Thermolysis Products

The catalytic properties of the potassium salts of heteropolytungstates with the general formulas K_m[X₂W₁₁(H₂O)O₃₉] (X = Fe³⁺, Co²⁺, and Zn²⁺) and K₅[H₂W₁₁Cr(H₂O)₂O₃₈] with the Keggin anion structure and K_n[XH_nW₆O₂₄] (X = Ni²⁺ and Mn⁴⁺) with the Anderson anion structure and their thermolysis products were studied in the reaction of isopropanol oxidation to acetone by atmospheric oxygen. Changes in their catalytic properties depending on their constituent 3d elements were established. The test heteropolytungstates and the thermolysis products of their potassium salts—phases with the structures of the types of pyrochlore and hexagonal tungsten bronzes—are promising compounds for the preparation of catalysts for organic synthesis reactions. The results of the studies can be useful for the prognostication of the properties of new catalytic systems based on these compounds.     

Synthesis and Properties of Some New Nicotinoyl Isocyanates and Their Fragmentation under Electron Impact

A convenient preparative route for synthesis has been developed and nicotinoyl isocyanates (NIC) have been obtained for the first time by the action of oxalyl chloride on amides of substituted nicotinic acids. A procedure has been found for suppressing the formation of hydrochlorides of nicotinoyl amides by the competing reaction of HCl with the initial amides of nicotinic acids. The special features of the fragmentation of nicotinoyl isocyanates under electron impact have been studied.__________Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 549–553, April, 2005.     

Synthesis of Some Surfactants Based on Polytriethanolamine and Investigation of Their Surface Active Properties

New modified surfactants were developed by esterification of ethoxylated polytriethanolamine with oleic acid. Triethanolamine was polymerized at three different times 1.30, 2.30, and 3.30 hours to give (P₄, P₆, and P₈) where 4, 6, and 8 refer to the degree of polymerization. The prepared polymer (P₈) was ethoxylated at three different molar ratios of ethylene oxide (40, 100, and 120) and named E(en)P₈. Then the ethoxylated polymers were esterified with oleic acid and abbreviated as E(en)P₈O_m. The surface properties for these surfactants were determined by measuring the surface tension. The structure was confirmed using the elemental analysis, (FTIR, ¹H, ¹³C NMR) spectroscopic.     

大孔交联聚苯乙烯吸附树脂的合成及其对叶绿素铜的吸附性能

通过改变苯乙烯-二乙烯苯共聚物的交联度和使用不同结构的二乙烯苯,合成了树脂Ⅰ-Ⅵ,在工业二乙烯苯共聚体系中加入少量丙烯酸甲酯合成了树脂Ⅶ;交联聚苯乙烯经Friedel-Grafts酰化反应在其苯环上引入乙酰基制备了树脂Ⅷ。用物理技术和化学方法表征了树脂的结构。树脂对叶绿素铜的吸附量不仅与其二乙烯苯含量有关,还与二乙烯基的位置(间-,对-)异构有关,树脂骨架极性的增加,不利于树脂对叶绿素铜的吸附。     

NMR Study of Some Sesquiterpene Alcohols and Their Oxidation Products

Oxidations of α-cadinol, T-cadinol, T-muurolol and δ-cadinol with SeO₃ gave corresponding ketols and diols. Reductions of the ketols with NaBH₄ gave epidiols. NMR data of these sixteen compounds are compared.     

芳吡唑啉乙烯基(口恶)唑烷并二氢吲哚的合成和变色性

某些芳乙烯基取代的(口恶)唑烷并二氢吲哚具有光(热)和电致变色性质,在非银盐成像等领域有应用价值.芳基吡唑啉是较强的电子给体,若用它替换上述化合物中的芳基,可能对其光谱及变色性产生有益的影响。为此,我们用Vilsmeier反应将3种芳基吡唑琳甲酰化得到醛     

取代酰胺类化合物的合成及其生物活性

为优化抗倒胺结构。合成了３０种化合物，用ＩＲ，１ＨＮＭＲ及元素分析确定了结构，并进行了水稻发芽试验及田间试验。     

Synthesis of Methyl p-Alkoxyphenylcarbamates and Some Their Reactions

Alkylation of methyl p-hydroxyphenylcarbamate with allyl bromide and 1,4-dibromobutane leads to formation of the corresponding methyl p-alkoxyphenylcarbamates. Reactions of methyl p-allyloxyphenylcarbamate with benzaldehyde, p-methoxybenzaldehyde, p-nitrobenzaldehyde, and p-chlorobenzaldehyde oximes in boiling ethanol in the presence of N-chlorobenzenesulfonamide sodium salt yields 3-aryl-5- (p-methoxycarbonylaminophenoxymethyl)-4,5-dihydroisoxazoles. Methyl p-(4-bromobutoxy)phenylcarbamate reacts with morpholine in benzene to give methyl p-(4-morpholinobutoxy)phenylcarbamate.     

Synthesis and Some Properties of 1,2-Dinitroguanidine

1,2-Dinitroguanidine is a product of nitroguanidine nitration with nitric acid and its mixtures with sulfuric acid and oleum. It is a diacid (pK _a 1.11, 11.5) and at the same time a weak base undergoing protonation at the nitrogen of the amino group (pK _BH+ -5.81). The decomposition kinetics of 1,2-dinitroguanidine was studied by spectrophotometric method both in acid and alkaline media, and the mechanism of the process was assumed. In the media of high acidity (H_o > -8) the 1,2-dinitroguanidine suffers reversible denitration into nitroguanidine. At lower acidity its conjugate acid or molecular form undergoes hydrolysis yielding nitrourea. Monoanion of 1,2-dinitroguanidine in a weak acid or in an alkali is hydrolyzed into N,N'-dinitrourea. The reaction of 1,2-dinitroguanidine with alkali in alcohol provides its salts, with nitrogen-containing bases form both salts and derivatives of 2-nitroguanidine. The treatment of 1,2-dinitroguanidine with haloalkanes results in its N-alkylated products.     

Synthesis of Azacalixarenes and Development of Their Properties

This review focuses on the synthesis, structure, and interactions of metal ions, the detection of some weak interactions using the structure, and the construction of supramolecules of azacalixarenes that have been reported to date. Azacalixarenes are characterized by the presence of shallow or deep cavities, the simultaneous presence of a basic nitrogen atom and an acidic phenolic hydroxyl group, and the ability to introduce various side chains into the cyclic skeleton. These molecules can be given many functions by substituting groups on the benzene ring, modifying phenolic hydroxyl groups, and converting side chains. The author discusses the evidence of azacalixarene utilizing these characteristics.     

Enantiospecific Synthesis of Trisubstituted Butyrolactone Natural Products and Their Analogs

A general methodology for the synthesis of highly substituted butyrolactones in enantiomerically pure form has been developed. The application of this process in a highly efficient synthesis of lactone natural products blastmycinone (1), NFX-2 (2), antimycinone (3), and NFX-4 (4) and two lipid metabolites (5, 6) are described. Additionally, the total synthesis of 5-epi-blastmycinone (22), 5-epi-NFX-2 (21b), 5-epi-NFX-4 (21c), and lipid metabolite analogs (19, 20) are also described. The overall yields for the target molecules are the highest reported so far in the literature.     

Synthesis of New Carboxy Lactones and Some Their Transformations

Alkylation of 2-ethoxycarbonyl-4-pentanolides with ethyl chloroacetate gave 2-ethoxycarbonyl-2-ethoxycarbonylmethyl-4-pentanolides. Alkaline hydrolysis of the latter afforded 2-carboxymethyl-4-pentanolides which were converted into the corresponding acyl chlorides in high yield by treatment with thionyl chloride in the presence of a catalytic amount of dimethylformamide. Reaction of 2-chloroformylmethyl-4-pentanolides with thiosemicarbazide, followed by treatment with alkali, resulted in formation of 2-(5-mercapto-1,2,4-triazol-3-ylmethyl)-4-pentanolides.     

新型吡唑甲酰脲类化合物的合成及其生物活性

５－氯－１，３－二甲基吡唑－４－甲酰基异氰酸酯同胺类化合物反应，合成了２３个新型吡唑甲酰脲类化合物，其化学结构经ＩＲ、１ＨＮＭＲ、ＭＳ和元素分析确证。所有化合物均具有一定的杀菌活性，部分化合物具有较好的杀虫活性。     

Synthesis and Properties of meso-Alkyltetrabenzotriazaporphyrins and Their Zinc Complexes

1,3-Diiminoisoindoline was reacted with aliphatic carboxylic acids in the presence of zinc oxide to obtain a mixture of meso-alkyl-substituted tetrabenzoazoporphyrins, from which zinc complexes of meso-alkyltetrabenzotriazaporphyrins were isolated.     

Synthesis of Some Novel Methoxyacrylates and Their Biological Activities

Methoxyacrylate fungicides which came from natural product have an excellent,broad spectrum of activities, highly safety and selective to target because of their unique mode of action-inhibit mitochonidrial respiration by blocking electron transfer between cytochrome b and cytochrome c₁, so more attention was paid by many companies in agrochemicals and at least 300 patents was applied until now. For the action of blocking electron transfer,some one suggests this kind of chemicals should not only work on fungi,but also on insects (sure) and weeds. Up to now,no herbicidal activity was reported. So the following compounds Ⅰ (X=O,NR,in patent:X=O,S rarely X=N) were designed and synthesized by introduced some fragment of herbicide.     

二茂钛苄氧基衍生物的合成及性质研究

Ｃｐ２ＴｉＣｌ２及（ＭｅＣｐ）２ＴｉＣｌ２在Ｅｔ３Ｎ或ＮａＮＨ２存在下与苄醇类化合物反应，高产率地合成了６个未见文献报道的二茂钛（Ⅳ）苄氧基衍生物，甲基二茂钛（Ⅳ）苄氧基化合物，经元素分析，ＨＮＭＲ和ＩＲ光谱确定了化合物的结构，并对其部分性质进行了讨论。