(Z)-3-丁烯基-4-羟基苯酞的合成

（Ｚ）－３－丁烯基－４－羟基苯酞的合成李绍白,王志伟,方小平,李裕林（兰州大学应用有机化学国家重点实验室,兰州,７３００００）关键词（Ｚ）－３－丁烯基－４－羟基苯酞,苯酞,３－丙基－５－羟基异香豆素,异香豆素,合成（Ｚ）－３－丁烯基－４－羟基苯酞（１...     

6,7—取代—1H—苯并（de）异喹啉—1,3（2H）二酮的合成

从二氢苊出发合成了６－溴－７－氨基２－（２′，４′－二甲基）苯基－１Ｈ－苯并（ｄｅ）异喹啉－１，３（２Ｈ）－二酮，６－甲氧基－７－氨基－２－（２′，４′－二甲基）苯基－１Ｈ－苯并（ｄｅ）异喹啉－１，３（２Ｈ）－二酮和６，７－二氨基－２－（２′，４′－二甲基）苯基－１Ｈ－苯并（ｄｅ）异喹啉－１，３（２Ｈ）－二酮，测定了它们的荧光量子产率，讨论了分子内重原子溴和给电子基对化合物荧光性质的影响。     

温度和压力对六氟二酐型聚酰亚胺的透气性能的影响

本文研究了温度和压力对五种六氟二酐（６ＦＤＡ）型聚酰亚胺膜对Ｈ_２、ＣＯ_２、Ｏ_２、Ｎ_２和ＣＨ_４五种气体透过性能的影响．在３０－１００℃区间，五种聚酰亚胺的透气系数与温度的关系均符合Ａｒｒｈｅｎｉｕｓ关系式；在０．３－１．２ＭＰａ区间，压力对透气系数的影响很小．６ＦＤＡ－４，４＇－二氨基二苯酮（ＤＡＢＰ）和６ＦＤＡ－３，３＇－二甲基二苯甲烷二胺（ＤＭＭＤＡ）在１００℃仍然具有较大的透气选择系数，是比较好的气体分离膜材料．     

铂－锇共显色衍生配合物的高效液相色谱研究

研究了Ｏｓ（Ⅱ）和４，４’二（二乙氨基）苯硫酮与Ｐｔ（Ⅱ）共显色所衍生的配合物，于ＮｕｃｌｅｏｓｉｌＣ＿８柱上，用含３×１０￣（－３）ｍｏｌ／ＬＤＬ－樟脑－１０－磺酸和０．０２ｍｏｌ／ＬＨＡｃ－ＮａＡｃ（ｐＨ３．５）的乙腈－丙酮－水（７２：５：２３，Ｖ／Ｖ）作流动相（１．０ｍＬ／ｍｉｎ）分离并检测。线性范围为０．２～４．０μｇ／ｍＬＰｔ；检测限为１．０ｎｇＰｔ。此方法已应用于抗癌药物顺铂和卡铂的分析。     

二苯醚系高分子单体的新合成路线

二苯醚系高分子单体的新合成路线张志强，田正华（鞍山钢铁学院化工系，ｌｌ４００２）４，４’─二苯醚二甲酸，４，４’─二氨基二苯醚，３，３＇４，４’─二苯醚四甲酸二酐等取代二苯醚是一类重要的高分子单体，用于制备聚酰胺、聚酰亚胺和聚芳酯，在耐高温塑料、液晶...     

4,4′-二偶氮苯重氮氨基苯与钴的显色反应研究及应用

研究了新试剂４,４′－二偶氮苯重氮氨基苯（ＢＡＢＤＢ）与钴的显色反应。在ＴｒｉｔｏｎＸ－１００ 的存在下,ｐＨ ９．５～１０．３ 的Ｎａ２Ｂ４Ｏ７－ＮａＯＨ 缓冲溶液中,钴与试剂形成１∶２ 型鲜红色配合物,最大的吸收波长为５３５ ｎｍ ,表观摩尔吸光系数为１．４５×１０５ Ｌ· ｍ ｏｌ－ １·ｃｍ － １。用拟定的方法测定了维生素Ｂ１２中钴含量,结果令人满意。     

3-吡唑基-6-取代均三唑并[3,4-b]-1,3,4-噻二唑的合成及生物活性

以１－甲基－３－乙基（－４－氯）－５－吡唑甲酰肼作原料，经两步得到４－氨基－３－（１－甲基－３－乙基（－４－氯）－５－吡唑基）－１，２，４－三唑－５－硫酮（３），３再与取代羧酸反应，得到一系列３－（１－甲基－３－乙基（－４－氯）－５－吡唑基）－６－取代均三唑并［３，４－ｂ］－１，３，４－噻二唑（４、５、６）．元素分析、１ＨＮＭＲ、ＩＲ和ＭＳ确定了它们的结构．初步生测结果表明：３具有植物生长调节活性，４ｂ、４ｄ、６具有杀菌活性．     

胺基铪茂催化乙烯/1-辛烯无规共聚合的研究

在亚乙基双（ 茚基） 二胺化茂铪（ｒａｃ Ｃ２Ｈ４（Ｉｎｄ）２Ｈｆ（ＮＭｅ２）２ ,简称１ ,Ｉｎｄ ＝ 茚基,Ｍｅ＝ 甲基） 催化作用下,对乙烯（Ｅ） 与１ 辛烯（Ｏ） 无规共聚合进行了研究．作为比较,利用异亚丙基（ 环戊二烯基）（１ 芴基） 二甲基锆茂催化体系（（ＣＨ３）２Ｃ（Ｆｌｕｏ）（Ｃｐ）ＺｒＭｅ２ ,简称２ ,Ｆｌｕｏ ＝ 芴基,Ｃｐ ＝ 环戊二烯基） 对乙烯／１ 辛烯在相同共聚合条件下进行了共聚合．结果表明,在单体浓度比［Ｏ］／［Ｅ］ 较小时共聚合速率随单体浓度比增加而增加,进一步增加单体浓度比则导致共聚合速率降低．催化体系１／Ａｌ（ｉＢｕ）２Ｈ／［Ｐｈ３Ｃ］［Ｂ（Ｃ６Ｆ５）４］（３） 催化共聚活性比２／ ＭＡＯ高得多．共聚物中辛烯含量随反应单体１ 辛烯含量的增加而增加,两单体竞聚率乘积（ ｒＥ×ｒｏ） 小于１ ,表明聚合物为无规共聚物．相同共聚单体浓度比下１／Ａｌ（ｉＢｕ）２Ｈ／３ 催化共聚物中辛烯含量比２／ ＭＡＯ 共聚物中辛烯含量高,表明前者具有更强的共聚合能力．所得无规共聚物熔点温度、结晶度、本体粘度及密度随共聚物中辛烯含量的增加而显著降低．辛烯含量较高时共聚物呈现明显无结晶行为．差示扫描量热分析显示,同乙烯均聚?     

冠醚化双西佛碱钴的合成及性能研究

由苯并－１５－冠－５经二硝基化后还原制得的４’，５’－二氨基苯并－１５－冠－５与水杨醛及其衍生物反应，合成了冠醚化双西佛碱Ｌ￣１～Ｌ￣４，并制备了它们的钴（Ⅱ）配合物及其分子氧加合物，研究了钴配合物ＣｏＬ￣１～ＣｏＬ￣４对异丙苯的催化氧化作用。     

Lewis酸催化1,4-脱水-2,3-二-氧-(对迭氮基苯甲基)-α-D-核糖的选择性开环聚合反应

在低温下用三氟化硼乙醚催化１，４－脱水－２，３－二－氧－（对迭氮基苯甲基）－α－Ｄ－核糖（ＡＤＡＢＲ）的阳离子选择性开环聚合反应，首次合成了具有１，５－开环α－结构的聚合物。单体ＡＤＡＢＲ由１，４－脱水－α－Ｄ－核糖在ＤＭＦ溶剂中与对溴甲基迭氮基苯反应获得。聚合物的结构由比旋光度、１Ｈ－ＮＭＲ和１３Ｃ－ＮＭＲ及ＩＲ谱确认。用五氟化锑为催化剂则得到了同时含有α－呋喃单元和β－吡喃单元混合结构的聚合物。研究了催化剂及其用量、聚合反应时间对聚合反应的影响，讨论了聚合反应机理。为研究１，４－脱水－２，３－二－氧－（对迭氮基苯甲基）－α－Ｄ－吡喃核糖的聚合活性以及便于测试迭氮基的含量对聚合物光刻性能的影响，还初步研究了单体ＡＤＡＢＲ与１，４－脱水－２，３－二－氧－苯甲基－α－Ｄ－吡喃核糖（ＡＤＢＲ）的共聚反应。从共聚物的结构分析可以认定共聚物具有１，５－α－结构，并且单体１，４－脱水－２，３－二－氧－苯甲基－α－Ｄ－吡喃核糖在实验条件下具有较高的活性。     

Preparation of polyimides utilizing the Diels–Alder reaction,II: Bis[N-(butadienyl-2-methyl)] amino arylenes with bismaleimides

Four new bisdienes were prepared from 2-bromomethyl-1,3-butadiene and N,N-diethyl benzidine; bis[4-(N-ethyl) aminophenyl]-p-diisopropylbenzene, 1,4-diamino-2,3,5,6-tetramethylbenzene and α,α′ bis(4-amino-3,5-dimethyl phenyl)-p-diisopropyl benzene. Polyimides were synthesized by the Diels–Alder reaction of these bisdienes and bis(4-maleimidylphenyl)methane and bis(3-maleimidylphenyl) sulfone. The polymers were soluble in m -cresol, dimethyl sulfoxide and chlorinated hydrocarbon solvents. Moderate thermal stability was observed by thermogravimetric analysis in air and nitrogen.     

New liquid‐crystal alignment agents based on fluorinated polyimides with trifluoromethyl‐substituted benzene or diphenylether in the side chain

Fluorinated copolyimides derived from 4,4′‐oxydiphthalic anhydride (ODPA) with 4,4′‐oxydianline (ODA) and trifluoromethyl‐containing aromatic diamines have been synthesized and characterized. The trifluoromethyl‐containing diamines include 2,4‐diamino‐3′‐trifluoromethylazobenzene, 2,4‐diamino‐1‐[(4′‐trifluoromethylphenoxy) phenyl] aniline, 3,5‐diamino‐1‐[(4′‐trifluoromethylphenoxy) phenyl] benzamide, 3,5‐diamino‐1‐[(3′‐trifluoromethyl) phenyl] benzamide, 1,4‐bis(4′‐aminophenoxy)‐2‐(3′‐trifluoromethylphenyl) benzene, 3,5‐diaminobenzenetrifluoride, 4,4′‐diamino‐4″‐(p‐trifluoromethyl phenoxy) triphenylamine, and 4‐[(4′‐trifluoromethylphenoxy) phenyl]‐2,6‐bis(4″‐aminophenyl)pyridine. Strong and flexible copolyimide films, produced by casting the polyamic acid solution followed by thermal imidization, exhibited great thermal stability and high mechanical properties. The polyimides had an ultraviolet–visible absorption cutoff at 330–340 nm and pretilt angles as high as 20° for nematic liquid crystals, making them great potential candidates for advanced liquid‐crystal display applications. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1583–1593, 2002     

含亚甲基和双二氮杂萘酮结构的聚芳酮的合成与性能

聚芳醚酮是一类重要的具有优异综合性能的工程塑料 ,它具有高的热稳定性、尺寸稳定性、耐溶剂性、好的加工性能和电性能 ,因而它经常作为复合材料的基质、粘合剂等被广泛的应用于航空、航天和电子等领域 .近几十年来 ,人们付出了很大的努力去开发聚芳醚酮新品种[1,2 ] .本研究组以 4 (4′ 羟基苯氧基 ) 2 ,3 二氮杂萘 1 (2Ｈ) 酮为缩聚单体制备了一系列的性能优良的聚芳醚酮[3～ 6] ,在主链中引入高密度的氮杂萘酮结构是获得高热稳定性和良好溶解性的重要途径 .由单体中含有更多的氮杂萘酮结构获得可溶解且耐温等级更高的聚芳酮是人们期…     

含4-苯基二氮杂萘酮结构共聚芳酯的合成及性能

以4-[4-(4羧基苯氧基)苯基]-2-(4-羧基苯基)二氮杂萘-1-酮(DHPZ-DA)、4,4'-二羧基二苯醚(DAPE)和2,2'-二(4-羟基苯基)丙烷(PBA)为原料,采用溶液缩聚法,合成了一系列聚芳酯,其数均分子量在1.2×104～1.7×104之间.通过FTIR和1H-NMR对聚芳酯结构进行了表征.该系列...     

Isolation and Crystal Structure of Trans-2,2′,4,4′-tetramethyl-6,6′-dinitro Azobenzene

Trans-2,2′,4,4′-tetramethyl-6,6′-dinitro azobenzene (C16H16N4O4, Mr = 328.32) was isolated from benzene extract of the leaves of Aconitum sungpanense Hand. Mazz. as a new compound, and characterized by spectral methods and X-ray diffraction analysis. It crystallizes in monoclinic system, space group P21/c with a = 8.544(1), b = 13.997(2), c = 7.161(1) A, β = 112.97(1), V = 788.4(2)A3, Z = 4, Dc = 1.383 g/cm3, F(000) = 344 and μ(MoKα) = 0.102 mm-1. The final R = 0.0395 and wR = 0.1140 for 1913 independent reflections with Rint = 0.0109 and 1329 observed reflections with I > 2((I). The molecule is composed of two phenyl rings through trans N=N.     

Synthesis and characterization of organosoluble ditrifluoromethylated aromatic polyimides

Two novel diamine monomers, 1,4‐bis (4‐aminophenoxy)‐2‐[(3′,5′‐ditrifluoromethyl)phenyl]benzene and 1,4‐bis [2′‐cyano‐3′(4″‐amino phenoxy)phenoxy]‐2‐[(3′,5′‐ditrifluoromethyl)phenyl] benzene, were synthesized from (3,5‐ditrifluoromethyl)phenylhydroquinone. A series of ditrifluoromethylated aromatic polyimides derived from the diamines were prepared through a typical two‐step polymerization method. These polyimides had a high thermal stability, and the temperatures at 10% weight loss were above 507 °C in nitrogen. Most of the polymers showed good solubility in anhydrated 1‐methyl‐2‐pyrrolidone, N,N‐dimethylacetamide, N,N‐dimethylformamide, chloroform, and tetrahydrofuran at room temperature. All the polymers formed transparent, strong, and flexible films with tensile strengths of 63.6–95.8 MPa, elongations at break of 5–10%, and Young's moduli of 2.38–2.96 GPa. The dielectric constants estimated from the average refractive indices are 2.69–2.89. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 3018–3029, 2005     

Synthesis,Characterization, and Magnetic Behaviour of Dinuclear Nickel(II) Complexes of N,N′‐Substituted Dithiooxamides derived from α‐Amino Acids

New dinuclear complexes of the types [Ni₂(L)(H₂O)₂] and [Ni₂(L)(H₂O)₆] [H₄L = N,N′‐bis(carboxymethyl) dithiooxamide (H₄GLYDTO), N,N′‐bis(1‐carboxyethyl) dithiooxamide (H₄ALADTO), N,N′‐bis(1‐carboxy‐2‐methylpropyl) dithiooxamide (H₄VALDTO) and N,N′‐bis(1‐carboxy‐3‐methylbutyl) dithiooxamide (H₄LEUDTO)] have been prepared and characterized by IR and electronic absorption spectroscopy, and the structure of [Ni₂(ALADTO)(H₂O)₆] crystals has been determined by single crystal X‐ray analysis. This compound is composed of discrete dinuclear units in which two Ni^II atoms with NO₄S kernels are linked by a single [ALADTO]^4– group that coordinates through its carboxylato oxygen, amino nitrogen and thiolato sulphur atoms. In each dimer unit the two nickel(II) ions in distorted octahedral coordination are separated by 5.863(2) Å The temperature dependence of the magnetic susceptibility of the new compounds was measured over the range 2 to 300 K. In the complexes of [GLYDTO]^4– and [ALADTO]^4– the two Ni atoms are antiferromagnetically coupled, with J = –23.51(4) and –20.95(8) cm^–1, respectively. By constrast, [Ni₂(VALDTO)(H₂O)₂], [Ni₂(VALDTO)(H₂O)₆] and [Ni₂(LEUDTO)(H₂O)₂] remain paramagnetic down to 2 K, with magnetic moment values between 2.8 and 3.3 M.B.     

Synthesis and properties of new organo‐soluble and strictly alternating aromatic poly(ester‐imide)s from 3,3‐bis[4‐(trimellitimidophenoxy)phenyl]phthalide and bisphenols

A series of new strictly alternating aromatic poly(ester‐imide)s having inherent viscosities of 0.20–0.98 dL/g was synthesized by the diphenylchlorophosphate (DPCP) activated direct polycondensation of the preformed imide ring‐containing diacid, 3,3‐bis[4‐(trimellitimidophenoxy)phenyl]phthalide (I), with various bisphenols in a medium consisting of pyridine and lithium chloride. The diimide–diacid I was prepared from the condensation of 3,3‐bis[4‐(4‐aminophenoxy)phenyl]phthalide and trimellitic anhydride. Most of the resulting polymers showed an amorphous nature and were readily soluble in a variety of organic solvents such as N‐methyl‐2‐pyrrolidone (NMP) and N,N‐dimethylacetamide (DMAc). Transparent and flexible films of these polymers could be cast from their DMAc solutions. The cast films had tensile strengths ranging 66–105 MPa, elongations at break from 7–10%, and initial moduli from 1.9–2.4 GPa. The glass‐transition temperatures of these polymers were recorded between 208–275 °C. All polymers showed no significant weight loss below 400 °C in the air or in nitrogen, and the decomposition temperatures at 10% weight loss all occurred above 460 °C. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 1090–1099, 2000     

STRUCTURE AND PROPERTIES OF PHOSPHROUS-CONTAINING POLY（ARYL ETHER KETONE） WITH BISPHENOL-A MOIETY

A phosphrous-containing poly(aryl ether ketone)was synthesized derived from bisphenol-A and bis[4-(4- fluorobenzoyl)phenyl] phenyl phosphine oxide(FPPPO)by nucleophilic substitution reaction.The structure of the polymer was characterized by FT-IR,~1H-NMR and ~(31)p-NMR.The thermal property of the PAEK was measured by DSC and TGA. The glass transition temperature(T_g)of the polymer was 205℃,and the 5% weight loss temperature under nitrogen was 475℃.Good solubility of the polymer in organic solvents,such as N-methylpyrrolidone,dimethylformamide, dimethylacetamide,dimethylsulfoxide and chloroalkanes was observed,flexible film was obtained from the polymer's CH_2Cl_2 solution.The limiting oxygen index(LOI)of the PAEK was 40,which indicated that organic phosphorus moiety can offer good flame retardant property to the polymer.     

Structural aspects of two α‐dihydrazones displaying a complete survey of intermolecular interactions

The compounds (2′E,2′E)‐2,2′‐(propane‐1,2‐diylidene)bis[1‐(2‐nitrophenyl)hydrazine], C₁₅H₁₄N₆O₄, (I), and (2Z,3Z)‐ethyl 3‐[2‐(2‐nitrophenyl)hydrazinylidene]‐2‐[2‐(4‐nitrophenyl)hydrazinylidene]butanoate tetrahydrofuran hemisolvate, C₁₈H₁₈N₆O₆·0.5C₄H₈O, (II), are puzzling outliers deviating from a general synthetic route aimed at the preparation of substituted pyrazoles. Possible reasons for this outcome, which is exceptional in an otherwise firmly established synthetic procedure, are analyzed. Compound (I) is unsolvated, while compound (II) crystallizes with a tetrahydrofuran solvent molecule lying on an inversion centre. The ethoxycarbonyl chain of (II), in turn, appears disordered into two equally populated (50%) moieties. In both structures, a plethora of different commonly occurring weak intermolecular interactions [viz. π(phenyl)...π(phenyl), π(C=N)...π(C=N), π(phenyl)...π(C=N), N—H...O and C—H...O] appear responsible for the crystal stability. Much less common are the short O(nitro)...O(nitro) contacts which are observed in the structure of (I), an example of unusual `electron donor–acceptor' (EDA) interactions.