尾式1,3-二烷基卟啉及其金属配合物的合成与表征

在特定的条件下以桂皮醛、二苯基壬四烯酮和氢溴酸为原料合成出了一种环状β-卤代缩醛类化合物---2(2-溴-2-苯乙基)-1,3-二烷,在无水碳酸钾的存在下与5-对羟基苯基-10,15,20-三苯基卟啉反应合成出了一种新型尾式卟啉-5-{对-[2-(2苯乙基)-1,3-二烷]氧基苯基}-10,15,20-三苯基卟啉,同时合成了其锌、钌、钯金属配合物,并通过电子光谱、元素分析、1HNMR、IR等光谱手段进行了表征.     

尾式5-{对-[2-(2-甲乙基)-1,3-二噁烷]苯氧基}-10,15,20- 三苯基卟啉及其金属配合物的合成与表征

2-(2-溴-2-甲乙基)-1,3-二噁烷与存在无水K2CO3的DMF溶剂中的5-(4-羟基苯基)-10,15,20-三苯基卟啉反应,合成出了一种新型卟啉5-{对-[2-(2-甲乙基)-1,3-二噁烷]苯氧基}-10,15,20-三苯基卟啉,并据此制得了锌、钯、钌配合物.对化合物的结构分别用UV-Vis、IR、1HNMR、元素分析等手段进行了表征.     

双卟啉及其单铜和双铜络合物的合成

一种新双卟啉及其单铜和双铜络合物的合成。用1,3-二溴丙烷分两步反应联接两个5,10,15-三苯基-20-对羟基苯基卟啉Ⅰ,合成双卟啉Ⅲ。以卟啉Ⅰ的铜络合物与5-[4-(3-溴-1-丙氧基)苯基]-10,15,20-三苯基卟啉Ⅱ反应合成了双卟啉Ⅲ的单钢络合物Ⅴ。化合物Ⅴ与醋酸铜在吡啶中反应,得双卟啉Ⅲ双铜络合物Ⅵ。双卟啉Ⅲ和Ⅴ对某些金属离子的灵敏度大幅度提高。     

苹果蠹蛾性信息素的合成及活性测试

[目的]探索苹果蠹蛾性信息素的合成方法,为苹果蠹蛾性信息素田间应用提供化合物.[方法]以E,E-2,4-己二烯-1-醇和1,6-己二醇为起始原料,通过Coupling偶联反应合成出苹果蠹蛾性信息素E,E-8,10-十二碳二烯-1-醇.关键步骤为CuC12.2LiCl催化的6-溴代-1-己醇四氢吡喃醚Grignard试剂与E,E-2,4-己二烯-1-醇乙酯反应,得到了目标化合物.[结果]合成出了以烯醇计产率可达60％的目标化合物.田间活性试验表明合成化合物在剂量为0.5 mg诱芯时对苹果蠹蛾的引诱活性与标准诱芯相当.[结论]利用偶联反应合成的苹果蠹蛾性信息素可直接用于田间防治.     

尾式1，3—二恶烷基卟啉及金属配合物的合成与表征

在特定的条件下以桂皮醛、二苯基壬四烯酮和氢溴酸为原料合成出了一种环状β－卤代缩醛类化合物－2－2－溴－2－苯乙基）－1,3－二恶烷,在无水碳酸钾的存在下与5－对羟基苯基－10,15,20－三苯基卟啉反应合成出了一种新型尾式卟啉－5－（对－[2-（2－苯惭基）－1,3－二恶烷]氧基苯基＿－10,15,20－三苯基卟啉,同时合成了其锌、钌、钯金属配合物,并通过电子光谱,元素分析,1HNMR,IR等光谱手段进行了表征。     

用Witting反应合成三苯甲基取代烯烃

利用Wittig反应,合成了(E)-5,5,5-三苯基-2-戊烯和2-甲基-5,5,5-三苯基-2-戊烯两种三苯甲基取代的烯烃。探讨了影响反应的各种因素,并找到了较好的合成条件。     

5-溴-1,3-二[2-（4＇-叔丁基苯基）-1,3,4-（二唑基-5）]苯的合成

以5-氨基-1,3-苯二甲酸和对叔丁基苯甲酰肼为原料合成了一种新型电致磷光材料中间体5-溴-1,3-二[2-（4＇-叔丁基苯基）-1,3,4-噁二唑基-5）]苯,探讨了反应条件对合成反应的影响,反应的总收率为20.0%,方法可行.     

柑桔香型化合物2-(1,3—戊二烯-1)1,3—二氧环戊烷的合成

2—(1,3—戊二烯—1)1,3—二氧环戊烷,分子式C_8H_(12)O_2,分子量140.18,沸点82℃/8.5mm,折光率n_D~(20)1.4975,无色液体,具有柑桔香味,它是瑞士Givaudan公司1973年提出的香料新品种,用于配制日用和食用的柑桔型香精,它的合成,除了该公司申请的一篇专利外,至今未见国内外文献再有报导。我们在合成烯醛型系列香料的基础上,以2,4—己二烯醛为原料,与乙二醇缩环化,合成了该化合物。合成反应如下:     

5-溴-1,3-二[2-(4'-叔丁基苯基)-1,3,4-((口恶)二唑基-5)]苯的合成

以5-氨基-1,3-苯二甲酸和对叔丁基苯甲酰肼为原料合成了一种新型电致磷光材料中间体5-溴-1,3-二[2-(4'-叔丁基苯基)-1,3,4-(口恶)二唑基-5)]苯,探讨了反应条件对合成反应的影响,反应的总收率为20.0%,方法可行.     

厨于氟橡胶的硫化促进剂TTC和DBMI的合成和配方试验

本文主要介绍用于氟橡胶的硫化促进剂:2,3,5-三苯基四唑氯化物(简称TTC)、及1,3-二苄基-2-甲基咪唑(简称DBMI)的合成路线和配方试验结果。以苯肼、苯甲醛和重氮盐为原料,通过三步法合成TTC,并对其配方效果进行了试验。     

Synthesis of ethylene-propylene-diene terpolymers with supported Ziegler-Natta catalyst

Terpolymerizations of ethylene, propylene and diene (1,3-butadiene, 1,5-hexadiene or 1,7-octadiene) by MgH₂/TiCl₄–AlEt₃ catalyst system were carried out. The compositions of the obtained terpolymers were evaluated. The effect of diene concentration in the reaction medium for each polymerization system on the terpolymer composition was observed. The structure of the diene repeat units was also investigated.     

Addition of thianthrene cation radical to non-conjugated dienes—Part I: Addition to one double bond

Reaction of thianthrene cation radical tetrafluoroborate and hexafluorophosphate with an excess of 1,4-hexadiene, 1,5-hexadiene, 1,7-octadiene, 1,8-nonadiene and 1,9-decadiene gave, in each case, a mixture of bis- and monoadduct from addition to one of the diene’s double bonds. Addition to both double bonds did not occur. The monoadduct of each diene and the bisadduct (7a) of 1,5-hexadiene were isolated. All monoadducts and 7a were characterized with ¹H and ¹³C NMR spectroscopy. By reaction on activated alumina adducts were converted into (E)- and (Z)-(5-thianthreniumyl)dienes, all of which were characterized with ¹H and ¹³C NMR spectroscopy. The monoadduct (6a) of 1,4-hexadiene and the bisadduct 7a were characterized with X-ray crystallography.     

Syntheses and radical ring-opening polymerizations of 1,1-bis(hydroxymethyl)-2-vinylcyclopropane and 1,1-bis(methoxymethyl)-2-vinylcyclopropane

Homo- and copolymerizations of 1,5-hexadiene with ethene and styrene using halfsandwich metallocene catalyst Me₂Si(Me₄Cp)(N-tert.-butyl)TiCl₂/MAO (Cp = cyclopentadienyl, Me = methyl, MAO = methylalumoxane) were investigated. According to ¹³C-NMR spectroscopic microstructure analysis, cyclopolymerization of 1,5-hexadiene afforded randomly distributed cis- and trans-cyclopentane rings in the homo- and copolymer backbone. 1,5-hexadiene incorporation reached 52 mol-%. The ratio of vinyl side chains to cyclopentane rings was controlled by 1,5-hexadiene concentration, where low 1,5-hexadiene concentration promoted cyclopolymerization. Copolymer glass transition temperatures increased with increasing content of cyclic units in the backbone. Styrene was used successfully as termonomer in ethene/1,5-hexadiene polymerization, resulting in a semicrystalline terpolymer with cyclic and styrenic units in the polymer backbone. Received: 5 September 1996/Accepted: 11 November 1996     

Co- and terpolymerizations of α-olefins and dienes with MgH2-supported Ziegler catalyst

Copolymerizations of ethylene or propylene with butadiene, 1,5-hexadiene or 1,7-octadiene by MgH₂/TiCl₄-AlEt₃ catalyst system were carried out. The effect of diene concentration in the reaction medium for each polymerization system on catalytic activity was observed. The compositions of the obtained copolymers were evaluated and the reactivity ratios were determined. Ethylene-propylene-diene terpolymerizations with the same catalyst system were also investigated.     

Hydrogenation of 2,5-dimethyl-2,4-hexadiene and cis-2-heptene on palladium black modified by lead,thallium and cadmium

The competitive hydrogenation of 2,5-dimethyl-2,4-hexadiene and cis-2-heptene catalysed by palladium black modified by lead, thallium and cadmium to various degrees of surface coverage, was investigated. An electrochemical method was used to determine the amounts of hydrogen dissolved and adsorbed on the catalyst. The effect of ad-atoms of lead, thallium and cadmium on the kinetics of the competitive hydrogenation is discussed in terms of measured values of the reaction selectivity.     

13C-NMR characterization of poly(1,5-hexadiene)

Poly(1,5-hexadiene) was prepared and its structure characterized by high-field ¹³C nuclear magnetic resonance. The polymer was shown to contain repeating five-membered rings separated by methylene bridges, with both cis and trans placements present in a 54 : 46 ratio. The result is compatible with the Marvel-Garrison two-step reaction mechanism.     

Crystalline structures and thermal properties of poly(ethylene-co-α,ω-nonconjugated diene)s prepared by zirconocene catalysts

Crystalline structures and thermal properties of poly(ethylene-co-α,ω-nonconjugated diene)s, [diene=1,5-hexadiene (HD), 1,7-octadiene (OD), and 1,9-decadiene (DD)] have been investigated in relation to insertion mode of the dienes. In the case of poly(ethylene-co-HD), the copolymer containing high cis-1,3-cyclopentane units shows lower melting point depression with increasing the comonomer content than the copolymers containing high trans-1,3-cyclopentane units. In the case of poly(ethylene-co-OD) and poly(ethylene-co-DD), the copolymers containing pendant vinyl groups show higher ΔH_m than that of the copolymers with cyclic units or branching structures. Thermal degradation of the copolymers has been investigated under nitrogen atmosphere and the degradation of the copolymers containing the cyclic structures begins at lower temperature than the copolymers containing pendant vinyl groups.     

八碳烯分离过程的脱水研究

本文运用残余曲线图对八碳烯分离过程进行了分析研究,提出了采用非均相共沸精馏的方法脱除待分离物系中的水的新工艺。研究结果表明,该方法即节省了原工艺中脱水所需的一些设备,又降低了分离能耗,并且可大幅度提高脱水效率,改善产品质量。     

Oxidative dimerisation of propene to 1,5-hexadiene on Bi-Zn-O catalysts

The oxidative dimerisation of propene to 1,5-hexadiene has been investigated on Bi-Zn-O catalysts. The Bi₄₈ZnO₇₃ phase, observed in the catalysts calcined at 700 ° C is an active and selective catalyst for the formation of 1,5-hexadiene. The best catalytic performance (1,5-hexadiene selectivity 64%) has been obtained at 525 ° C, with a propene to oxygen ratio of 26, on a catalyst formed by Bi₄₈ZnO₇₃ with a small excess of ZnO.     

Dehydrocyclization of n-hexane on a bifunctional catalyst

Dehydrocyclization of n-hexane was investigated in the temperature range 400–500 °C, pressure range 3–20 atm, and at space velocities 10–150 (g feed/g cat × hr) on a commercial $\text{Pt}\text{Al}{}_2\text{O}{}_3$ catalyst in a fixed bed reactor. From product distributions of the individual conversions of n-hexane, 1-hexene, 2-methylpentane, 2-methyl-1-pentene, 1,5-hexadiene, and methylcyclopentane at the same reaction conditions and from experiments with variation of residence time at constant temperature and pressure, a reaction mechanism for the dehydrocyclization of n-hexane is proposed, in which at least four different reaction paths for the aromatization are possible: 5- and 6-membered ring closure and cyclization of cis-2-hexene and 1,5-hexadiene.