ZSM-5分子筛上烷基化过程中“反向效应”的产生及其克制方法

在综述甲苯择形烷基化机理并分析产生“反效应”的原因的基础上,提出了克制的“反向效应”的设想。Ｓｂ２Ｏ３,ＴｉＣｌ４,ＳｉＣｌ４,Ｈ３ＰＯ４,Ｍｇ（Ａｃ）２等化合物对分子筛进行改性,测定改性前后分子筛的表面酸性与孔结构,关联乙基化反应结果,证实中强酸中心在乙基化反应中的重要作用,认为保持孔道的畅通是解决“反应效应”的关键。并采用了Ｋ－Ｍｇ改性,制备出对甲苯乙基化具有高初活性和高对位选择性的催化剂。     

手性-3, 5-二取代-1', 2', 4'-三唑-[3', 4'-b]-2, 4-二氢间 噻二嗪的合成及 生物活性

以3-芳基-5-巯基-1,2,4-均三唑为原料,和甲醛及S-(-)-α-苯乙胺在酸催化作用下合成了6种新的化合物。研究了合成反应的条件。通过元素分析、IR、^1HNMR、和MS确证了其结构,测定了比旋光度和生物活性。结果表明,一些化合物具有一定的抗菌活性。     

Synthesis and characterization of 3-methyl-5-oxo-N,1-diphenyl-4,5-dihydro-1-H-pyrazole-4-carbothioamide and its metal complexes

The molecular parameters have been calculated to confirm the geometry of 3-methyl-5-oxo-N,1-diphenyl-4,5-dihydro-1-H-pyrazole-4-carbothioamide, HL. The compound is introduced as a new chelating agent for complexation with Cr(III), Fe(III), Co(II), Ni(II) and Cu(II) ions. The isolated chelates were characterized by partial elemental analyses, magnetic moments, spectra (IR, UV–vis, ESR; ¹H NMR) and thermal studies. The protonation constant of HL (5.04) and the stepwise stability constants of its Co(II), Cu(II), Cr(III) and Fe(III) complexes were calculated. The ligand coordinates as a monobasic bidentate through hydroxo and thiol groups in all complexes except Cr(III) which acts as a monobasic monodentate through the enolized carbonyl oxygen. Cr(III) and Fe(III) complexes measured normal magnetic moments; Cu(II) and Co(II) measured subnormal while Ni(II) complex is diamagnetic. The data confirm a high spin and low spin octahedral structures for the Fe(III) and Co(II) complexes. The ESR spectrum of the Cu(II) complex support the binuclear structure. The molecular parameters have also been calculated for the Cu(II) and Fe(III) complexes. The thermal decomposition stages of the complexes confirm the MS to be the residual part. Also, the thermodynamic and kinetic parameters were calculated for some decomposition steps.     

等级孔微孔-介孔Fe2O3/ZSM-5中空分子筛催化材料的制备及催化苄基化性能

ZSM-5分子筛具有极其均匀的孔道结构、 良好的形状选择性和催化活性及耐水热稳定性, 是一种高效、 绿色的固体催化剂, 被广泛应用于石油催化裂化、 精细化工和环境保护等领域. 但其单一的微孔结构大大降低了客体分子的流通扩散性, 导致由大分子参与的芳烃烷基化反应受到极大限制. 本文采用NaOH/四丙基氢氧化铵(TPAOH)混合碱处理微孔ZSM-5, 制备了具备高结晶度、 高比表面积的等级孔微孔-介孔ZSM-5中空分子筛材料, 该材料在保持微孔孔道良好水热稳定性和大量活性中心的同时, 还通过介孔的引入进一步促进反应物及产物的扩散, 使间三甲苯苄基化反应的转化率提高了3.8倍. 通过在等级孔微孔-介孔ZSM-5中空材料上负载Fe, 开发出了具有双功能的等级孔微孔-介孔Fe₂O₃/ZSM-5中空催化剂, 该催化剂在苯的苄基化反应中表现出优异的催化性能, 当Fe负载量(质量分数)为6.67%, 反应温度为75 ℃, 反应时间为15 min时, 转化率高达98.3%, 选择性为81.6%, 最终收率达到80.2%.     

Fe-Cu/ZSM-5催化剂的NH_3-SCR脱硝性能

通过浸渍法制备了Fe和Cu含量比不同的系列Fe-Cu/ZSM-5催化剂,利用XRD、H2-TPR、NH3-TPD和原位DRIFTS等技术对催化剂进行了表征,并对其NH3-SCR脱硝性能进行了研究。结果表明,双金属改性的Fe-Cu/ZSM-5催化剂活性温度窗口拓宽,其中,Fe-Cu/ZSM-5 1∶4催化剂脱硝性能优异,250-450℃下脱硝效率均超过90%,335℃时脱硝效率达到最大值96.46%。铜和铁物种能以无定型氧化物良好分散于载体表面,双金属负载改性催化剂保留了ZSM-5的晶体结构。Fe-Cu/ZSM-5 1∶4催化剂具备丰富的酸性位、良好的氧化还原性能,一定温度条件下NH3-SCR反应过程中同时存在E-R机理和L-H机理,且E-R机理反应起始温度低于L-H机理;200℃为催化脱硝反应的起活温度。     

2,5-取代-1,3,4-噁二唑化合物库的固相合成

本文使用组合化学方法以聚苯乙烯亚磺酸钠树脂（1）为载体合成了2，5-取代-1，3，4-二唑化合物库。树脂1首先与溴代乙酸乙酯反应生成聚合物支载的乙酸酯（2）。肼解后所得的肼树脂进一步与取代的苄氯反应得双欧讲树脂（4）。树脂4与三氯氧磷回流得聚合物支载的2，5-取代-1，3，4-二唑（5）。用W-溴代乙酰苯酮烷基化后聚合物支载的产物用三乙胺解脱得2-芳基-5-芳甲酰亚乙烯基-1，3，4-二唑化合物库，产率15％-36％。     

Synthesis of 1, 4-Bis[3-N-propionyl-2-aryl-1, 3, 4- oxadiazoline-5-yl]phenylenes

1, 3, 4-Oxadiazoline derivatives are found to possess significant biological activities such as antifungal1, insecticidal2, CNS depressant3-5, anticonvulsant effects and plant growth accelerator. They are highly important heterocycles, and have been used …     

3—芳基—5—巯基—1,2,4—均三唑的双—Mannich反应研究

研究了在氯化氢－乙醇溶液中，３－芳基－５－巯基－１，２，４－均三唑与甲醛和伯胺（芳胺或脂肪胺）的双Ｍａｎｎｉｃｈ反应，合成了１３的的稠杂环化合物３，５－二取代０四氢均三唑并「３，４－ｂ」「１，３，５」噻二嗪，经元素分析、Ｉ手ＭＳ确定了结构，初步测定了该类化合物的生物活性。     

PMTFP与中性磷萃取剂对钇(Ⅲ)的协同萃取

本文用萃取法测定了(Ⅰ)Y(Ⅲ)/0.5MNaClO_4/PMTFP—C_6H_6和(Ⅱ)Y(Ⅲ)/0.5MNaClO_4/PMTFP—TBP—C_6H_6及(Ⅲ)Y(Ⅲ)/0.5MNaClO_4/PMTFP—TOPO—C_6H_6体系的萃取平衡常数和协苹平衡常数,结果如下: 体系(Ⅰ)的1gK3_(30)=-3.36;体系(Ⅱ)的1gK_(32)=4.47; 体系(Ⅲ)的1gK_(31)=6.65、1gK_(32)=9.08。     

Amine electrosynthesis from 1-ethyl-4-nitro-3-cyanopyrazole

Polarography and preparative electrolysis are used to show that the electrochemical behavior of 1-ethyl-4-nitro-3-cyanopyrazole (1) in acidic aqueous-alcoholic solutions resembles the behavior of nitrobenzene. By varying the parameters of the electroreduction (ER) of compound 1, one can obtain either 1-ethyl-4-amino-3-cyanopyrazole (2) or 1-ethyl-4-amino-3-cyano-5-chloropyrazole (3). Compound 2 is formed during the ER of compound 1 in the presence of a mediator (titanium(III)) at temperatures below 10°C. Compound 3 is produced by the direct reduction of compound 1 on a lead electrode (30% ethanol, 10% HCl). The yield of amine chlorohydrates 2 and 3 is 56 and 92%, respectively. The mediated ER of compound 1 at catholite temperatures higher than 10°C yields a mixture of compounds 2 and 3; the proportion of the latter increases with temperature to become the major product at 60°C. Compound 3 is formed due to the rearrangement of the hydroxylamine derivative produced by the ER of compound 1, followed by the substitution of chlorine for the hydroxy group.     

3, 6-二芳基-5, 6-二氢均三唑[3, 4-b][1, 3, 4]噻二唑的合成 及生物活性

研究了在L-(+)-酒石酸存在下3-芳基-4-氨基-5-巯基-1,2,4-均三唑与醛的Mannich反应及分子内的加成反应,合成了15个新的手性稠杂环化合物3,6-二芳基-5,6-二氢均三唑[3,4-b][1,3,4]噻二唑,利用IR、^1HNMR和MS确证了其结构,并测试了部分化合物的生物活性。     

Oxidative Diels-Alder reaction of 2, 5-dihydroxybenzoic acid with 1, 3-cyclopentadiene

The electrochemical oxidation of 2,5-dihydroxybenzoic acid (1) has been studied in the presence of 1,3-cyclopentadiene (2) as a diene in water/ethanol (40/60, v/v) mixture using cyclic voltammetry and controlled-potential coulometry. A plausible mechanism for the oxidation of 1 in the presence of 2 is presented. Compound 1 was converted into bis-adduct 5 via electrooxidation, Diels-Alder reaction of 2 to anodically generated 3,6-dioxocyclohexa-1,4-dienecarboxylic acid (1ox), decarboxylation reaction, electrooxidation and Diels-Alder reaction. The electrochemical synthesis of 5 was performed in a onepot reaction, without toxic reagents, at a carbon electrode in a simple cell using an environmentally friendly method.     

(4R,5S)-5-羟基-4-甲基-3-己酮的合成

农业害虫药材甲Stegobium panicem Linnae在我国各省区都有分布,主要危害谷类、食品、药材、图书、档案等.我国一般每年可以发2～3代,温度较高的地区可发生4代[1] .     

Synthesis and Crystal Structure of Trans-4-[(5-(2,4-Dichlorophenoxy)-3-methyl-1-phenyl-1H-pyrazol-4-yl)methyleneamino]-1,5-dimethyl-2-phenyl-1,2-dihydropyrazol-3-one

The title compound trans-4-[(5-(2,4-dichlorophenoxy)-3-methyl-1-phenyl-1H-pyra-zol-4-yl)methyleneamino]-1,5-dimethyl-2-phenyl-1,2-dihydropyrazol-3-one 3 (C28H23Cl2N5O2, Mr = 532.41) has been synthesized and its crystal structure was determined by single-crystal X-ray diffraction analysis. It crystallizes in triclinic, space group P1 with a = 8.9438(4), b = 11.6065(5), c = 14.2215(6) , α = 112.566(1), β = 92.324(2), γ = 102.91(1)o, V = 1315.65(10) 3, Z = 2, Dc = 1.344 g/cm3, μ(MoKα) = 0.282 mm-1, λ = 0.71073 , F(000) = 552, the final R = 0.0587 and wR = 0.1578 for 5071 observed reflections (I > 2σ(I)). X-ray analysis reveals that the product is a thermodynamically stable trans isomer. Intra-and intermolecular C(12)-H(12)···O(1) and C(28)-H(28)···O(1)#1 hydrogen bonds were observed in the title compound.     

Synthesis of 4-Arylhydrazono-3-arylthiomethyl-4,5-dihydro-1H-1-R-5-pyrazolones

It has been established that interacting ethyl 2-arylhydrazono-4-arylthio-3-oxobutyrates with hydrazine, methylhydrazine, and phenylhydrazine forms 4-arylhydrazono-3-arylthiomethyl-4,5-dihydro-1H-1-R-pyrazolones.     

Reaction of 1-Aryl-3-methylpyrazol-5-ones with 2-Cyanoaryldiazonium Bisulfates

2-Cyanoaryldiazonium bisulfates, obtained by the action of nitrosyl sulfuric acid on isatin 3-hydrazone and its 5-bromo and 5-nitro derivatives, couple with 1-aryl-3-methylpyrazol-5-ones and form 4-arylhydrazones of 1-aryl-3-methylpyrazole-4,5-diones. It was established on the basis of data of IR, UV, and ¹H NMR spectra and of X-ray structural analysis that the coupling products exist in the hydrazone form stabilized by an intramolecular hydrogen bond.__________Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 210–215, February, 2005.     

Thermal decomposition of copper complexes of 1-phenyl-3-methyl-4-acyl-5-pyrazolone in air atmosphere

Copper complexes of some 1-phenyl-3-methyl-4-acyl-5-pyrazolones have been prepared. The complexes were characterized by elemental analyses and thermal analyses. It was shown that the melting points decrease linearly in increasing the molecular weight of the complexes.     

3-(2-卓二唑啉基) - 色酮类化合物的合成研究

报道了取代的邻羟基苯乙酮(1a～1e)经Vilsmeier-Haack反应一步制得3－醛基色酮(2a～2e),2a～2e与取代的芳酰肼(3a～3c)缩合制得15个酰腙类化合物(4a～4o),4a～4o在醋酸酐作用下关环得15个3-(2-卓二唑啉基)-色酮(5a～5o),并通过元素分析,IR,^1^HNMR和MS谱数据确证了上述化合物的结构。     

Synthesis and anti-TMV activity of novel N-(3-alkyl-1H-pyrazol-4-yl)-3-alkyl-4-substituted-1H-pyrazole-5-carboxamides

In order to investigate the biological activity of novel bis-pyrazole compounds,a series of N-（3-alkyl-5-（N-methylcarbamyl）- 1H-pyrazol-4-yl）-3-alkyl-4-substituted-1H-pyrazole-5-carboxamides were designed and synthesized with ethyl 3-alkyl-1H-pyrazole -5-carboxylate 1 as starting materials.N-Methyl-3-alkyl-4-amino-1H-pyrazole-5-carboxamides 6 were obtained from 1 via 5 steps.3-Alkyl-4-substitued-1H-pyrazole-5-carboxyl chlorides 4a,4b,11a,11b,11c or 12 were also obtained from 1 via several steps.Target compounds 7a-7g were obtained after the reaction of 6 with the above 1H-pyrazole-5-carboxyl chlorides.Preliminary bioassay showed some compounds possessing good inactivation effect against TMV（tobacco mosaic virus）.Compound 7a showed higher activity superior to ningnanmycin at a concentration of 5.0×10^-4 g/mL and equal activity at 1.0×10^-4 g/mL;7b and 7c showed equal activity to virazole both at concentrations of 5.0×10^-4 g/mL and 1.0×10^-4 g/mL.     

1-(2-羟基-3,5-二硝基苯基)-3-[4-(苯基偶氮)苯基]-三氮烯与锌的显色反应及其应用

研究了 1 (2 羟基 3,5 二硝基苯基 ) 3 [4 (苯基偶氮 )苯基 ] 三氮烯 (HDNPAPT)与锌(Ⅱ )的显色条件。在乳化剂OP存在下的氢氧化钠介质中 ,在 5 2 5nm波长处 ,锌与HDNPAPT形成稳定的 1∶2的红色配合物 ,表观摩尔吸光系数ε52 5=9.15× 10 4 L·mol- 1·cm- 1,锌 (Ⅱ )浓度在 0～ 10 μg/ 2 5ml范围内符合比耳定律。方法已应用于人发、面粉中微量锌的测定 ,结果满意