对苯二胺类与2,2′-二噻吩共轭共聚物的金属催化法合成与表征

以1,3-二(二苯基膦)丙烷二氯化镍(Ⅱ)作为催化剂,分别合成了2,2′-二噻吩与N,N′-二氯对苯醌二亚胺和2,5-二甲基-N,N′-二氯对苯醌二亚胺的共轭交替共聚物:聚(N,N′-对苯醌二亚胺-2,2′-二噻吩)和聚(2,5-二甲基-N,N′-对苯醌二亚胺-2,2′-二噻吩)。利用红外光谱、紫外可见光谱、循环伏安等测试方法对这2种共聚物进行了表征和性能研究。结果表明:这2种共聚物分别在263、315、410、261、3214、03 nm处出现了紫外吸收峰,对苯二胺上的甲基对共聚物电化学活性具有一定的影响。     

联苯胺类共轭共聚物的金属配合物催化法合成及性质

联苯二胺 ,3,3′ 二甲基联苯二胺在次氯酸钠介质中氧化制备了相应的N ,N′ 二氯联苯醌二亚胺 ,3,3′ 二甲基 N ,N′ 二氯联苯醌二亚胺 .通过红外 (FT IR) ,核磁共振 (1 H NMR)等进行了表征 .研究了此化合物在二价镍配合物存在下 ,与 2 ,5 二溴噻吩制成的Grignard试剂共聚的方法 ,并得到了联苯醌二亚胺与噻吩交替共聚的共轭聚合物 .该合成方法所得聚合物的纯收率分别为 6 3% ,88% .循环伏安测定表明该类聚合物具有一定的电化学活性 ,紫外 可见光谱中分别在 310nm ,4 5 0nm处 (共聚物Ⅰ )和 2 90nm ,4 30nm处 (共聚物Ⅱ )出现吸收峰 .根据聚合物的粉末X 射线衍射图 (XRD) ,对所得聚合物的结晶性也做了初步探讨 .     

对苯醌二亚胺与吡啶共聚物的金属配合物催化法合成及性能

在二氯-1,3-双(二苯基磷)丙烷基镍(Ⅱ)存在下,通过N,N′-二氯苯醌二亚胺和2,5-二甲基-N,N′-二氯苯醌二亚胺与2,5-二溴吡啶的格氏(Grignard)试剂共聚,得到了两种新型共轭聚合物。采用FT-IR1、H-NMR、UV-Vis、XRD、循环伏安、充放电对共聚物进行结构与性能测试。结果表明:该类共聚物具有一定的电化学活性,每种聚合物均在-1.0~2.0 V出现一对氧化-还原峰。聚(N,N′-二氯苯醌二亚胺-吡啶)和聚(2,5-二甲基-N,N′-二氯苯醌二亚胺-吡啶)的比电容分别为126 F/g和63 F/g。     

含苯并硒二唑聚咔唑/芴类共轭聚电解质及其前驱体的合成与性能研究

采用Suzuki偶合反应合成了一系列新型的咔唑、芴和2,1,3-苯并硒二唑的共聚物——聚[3,6-(N-(2-乙基己基))咔唑-2,1,3-苯并硒二唑-9,9-双(N,N-二甲基胺丙基)芴](PCzN-BSeD)及其相应的聚电解质衍生物——聚[3,6-(N-(2-乙基己基))咔唑-2,1,3-苯并硒二唑-9,9-(双(3′-(N,N-二甲基)-N-乙基铵)丙基)芴]二溴(PCzNBr-BSeD).在聚咔唑和芴中引入不同比例的2,1,3-苯并硒二唑(BSeD)单元,引起了由咔唑和芴链段向窄带隙苯并硒二唑(BSeD)单元有效的能量转移.通过对聚合物电致发光性能的研究,发现用聚(3,4-亚乙基二氧基噻吩)(PEDOT)或聚(3,4-亚乙基二氧基噻吩)/聚乙烯咔唑(PEDOT/PVK)作为空穴传输层时,器件的性能相差不大,表明咔唑的引入较明显的改善了聚合物的空穴注入性能.而且几乎所有的聚合物用高功函数铝作阴极的器件和用钡/铝作阴极的器件具有相近的发光性能,表明这类聚合物具有良好的电子注入性能.     

苯并噻二唑与苯胺类聚合物的金属镍配合物催化法合成与表征

以1,3-二(二苯基膦)丙烷二氯化镍(Ⅱ)[Ni(dppp)Cl2]作催化剂,通过4,7-二溴-2,1,3-苯并噻二唑格氏(Grignard)试剂分别与3,3′-二甲基联苯二胺、对苯二胺共聚得到了两种新型主链含刚性和柔性链结构的苯并噻二唑类共轭聚合物。通过FT-IR、1H-NMR、UV-Vis、XRD、TGA等测试手段对聚合物的化学结构和性能进行了表征。结果表明:聚合物的紫外-可见最大吸收波长分别在306 nm和380 nm处出现,荧光激发峰分别出现在378 nm和463 nm,相应的荧光发射峰分别在493、562 nm处出现。共轭聚合物具有一定的结晶性和热稳定性。     

联苯二胺类与噻吩共聚物的金属配合物催化法合成

联苯二胺,3,3′-二甲基联苯二胺在二价镍配合物存在下,直接与2,5-二溴噻吩的格氏(Grignard)试剂共聚,用红外光谱、核磁共振等对共聚物进行了表征。该合成方法所得联苯二胺与噻吩共聚物、3,3′-二甲基联苯二胺与噻吩共聚物的收率分别为63．4％和70.8％。在25℃测得的特性粘度分别为O．75dL／g和O.67dL／g。聚合物的循环伏安测定表明该类聚合物具有一定的电化学活性,每种聚合物均在O～O．8V之问出现两对氧化一还原峰。紫外一可见吸收光谱测试结果表明共聚物分别在415nm和450nm处有最大吸收峰。     

对苯醌二亚胺与对苯乙炔共聚物的金属配合物催化法合成与表征

在金属配合物的存在下,通过N,N′-二氯对苯醌二亚胺与1,4-二炔基-2,5-二（烷氧基）苯共聚,得到了一系列新型交替共聚物聚[N,N′-对苯醌二亚胺-1,4-二炔基-2,5-二（烷氧基）苯]（PAn-PPE）。采用FT-IR、1H-NMR、GPC、XRD、UV-Vis、PL、TGA等测试手段对共聚物的化学结构和性能进...     

基于3,5-二胺基-N（N′,N′-正二丁基甲酰胺基苯基）-苯甲酰胺的聚酰亚胺的溶解性、热稳定性和取向性能

用制得的大体积双侧基3,5-二胺基-N（N′,N′-正二丁基甲酰胺基苯基）-苯甲酰胺（DAPDM）,与3,3′-二甲基-4,4′-二氨基二苯甲烷（DMMDA）、3,3′,4,4′-二苯醚四甲酸二酐（ODPA）采用一步法共缩聚制得聚酰亚胺共聚物。采用核磁共振对该共聚物进行了表征,对其溶解性、热稳定性、预倾角进行了分析。结...     

1,2,3,4-四(6,′7′,-二甲基苯并噁唑)环丁烷光谱特性研究

本文测定并对1,2,3,4-四(6′,7′-二甲基苯并嗯唑)环丁烷(1)及其模型化合物反-1,2-二(6′,7′-二甲基苯并(口恶)嗯唑-1′,3′-基-2′)乙烯(2),1,2-二(6′,7′-二甲基苯并(口恶)唑-1′,3′-基-2′)乙烷(3),2-甲基苯并(口恶)唑(4)的紫外吸收光谱和荧光发射光谱进行对比。研究了化合物1由于跨环共轭效应所引起的电子光谱的变化,并从溶剂效应及晶体结构进行了探讨。     

给体-受体-给体窄带隙染料掺杂聚芴发光二极管

合成了一系列给体-受体-给体型窄带隙荧光分子, 并将其作为掺杂剂与主体(Host)宽带隙聚芴共混制备发光二极管. 荧光分子为4,7-二呋喃-苯并噻二唑(O-S)、4,7-二噻吩-苯并噻二唑(S-S)、4,7-二(N-甲基吡咯)-苯并噻二唑(N-S)、4,7-二硒吩-苯并噻二唑(Se-S)和4,7-二(N-甲基吡咯)-苯并硒二唑(N-Se). 溶液中荧光分子的紫外-可见吸收峰位于447~472 nm, 荧光发射峰位于563~637 nm. 该系列荧光分子掺杂聚芴(PFO)发光器件的电致发光峰位于580~633 nm. 当器件结构为ITO/PEDOT/PVK/PFO+N-Se/Ba/Al时, 最大外量子效率为1.28%, 电流效率1.31 cd/A.     

Synthesis and structure of hydroxyisoxazolidines and derivatives of hydroxylamine and alkenals

The reactions of N-substituted hydroxylamines with alkenals serve as a method for the synthesis of the corresponding 2-substituted 3(5)-hydroxyisoxazolidines. The reaction pathway is determined by the nature of the substituent attached to the nitrogen atom. Ring-chain isomerism has been detected in these newly obtained compoundsTranslated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1270–1276, September, 1987.     

Synthesis and characterization of triazenide and triazene complexes of ruthenium and osmium

Triazenide [M(eta2-1,3-ArNNNAr)P4]BPh4 [M = Ru, Os; Ar = Ph, p-tolyl; P = P(OMe)3, P(OEt)3, PPh(OEt)2] complexes were prepared by allowing triflate [M(kappa2-OTf)P4]OTf species to react first with 1,3-ArN=NN(H)Ar triazene and then with an excess of triethylamine. Alternatively, ruthenium triazenide [Ru(eta2-1,3-ArNNNAr)P4]BPh4 derivatives were obtained by reacting hydride [RuH(eta2-H2)P4]+ and RuH(kappa1-OTf)P4 compounds with 1,3-diaryltriazene. The complexes were characterized by spectroscopy and X-ray crystallography of the [Ru(eta2-1,3-PhNNNPh){P(OEt)3}4]BPh4 derivative. Hydride triazene [OsH(eta1-1,3-ArN=NN(H)Ar)P4]BPh4 [P = P(OEt)3, PPh(OEt)2; Ar = Ph, p-tolyl] and [RuH{eta1-1,3-p-tolyl-N=NN(H)-p-tolyl}{PPh(OEt)2}4]BPh4 derivatives were prepared by allowing kappa1-triflate MH(kappa1-OTf)P4 to react with 1,3-diaryltriazene. The [Os(kappa1-OTf){eta1-1,3-PhN=NN(H)Ph}{P(OEt)3}4]BPh4 intermediate was also obtained. Variable-temperature NMR studies were carried out using 15N-labeled triazene complexes prepared from the 1,3-Ph15N=N15N(H)Ph ligand. Osmium dihydrogen [OsH(eta2-H2)P4]BPh4 complexes [P = P(OEt)3, PPh(OEt)2] react with 1,3-ArN=NN(H)Ar triazene to give the hydride-diazene [OsH(ArN=NH)P4]BPh4 derivatives. The X-ray crystal structure determination of the [OsH(PhN=NH){PPh(OEt)2}4]BPh4 complex is reported. A reaction path to explain the formation of the diazene complexes is also reported.     

Investigation of adhesion and mobility of polyurethane and epoxy-rubber glues and adhesives

The values of activation parameters in uncured and cured epoxy resins, rubbers, and blends thereof are investigated. The dependences of activation energy and adhesion strength of epoxy-rubber compositions on rubber content are determined. The correlation of adhesion and activation energy values for polyurethane rubber and epoxy-rubber compositions is shown.     

Mass and NMR spectra of haplophyllidine and perforine and of their derivatives

Conclusions The mass and NMR spectra of haplophyllidine, perforine, and their derivatives have been studied. The influence of the open and cyclic forms of the molecular ion on the nature of the fragmentation has been discussed. The main routes of fragmentation of the compounds considered are due to the presence of substituents at C₈ and C₄.Khimiya Prirodnykh Soedinenii, Vol. 5, No. 4, pp. 273–279, 1969     

Crystal and molecular structure of aroyl- and acetylhydrazones of acet- and benzaldehydes

Aroyl- and acetylhydrazones of acet- (I) and benzaldehydes (IV) and benzoylhydrazones of acet- (II) and benzaldehydes (III) were studied by x-ray structural and quantum-chemical methods in order to establish their structures. Compund (I) was the EEZ structure in the crystal. Calculations and spectral data showed that the EEE form occurs in nonpolar solvents and in the gas phase. According to crystallographic data molecules (I)–(IV) are the E-isomers (relative to the N-N bond) and the hydrazone fragments are planar. Intermolecular N-H...O H-bonds from in the crystals. The data obtained suggest that the majority of acylhydrazones are conformationally rigid on dissolution although exceptions do occur. Apparently the reasons for the difference of acetyl- and benzoylhydrazones in electrocarboxylation reactions are electronic and not steric factors.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 1, pp. 75–81, January, 1991.     

Glycolate and Thioglycolate Complexes of Rhenium and Their Oxidative Elimination of Ethylene and of Glycol

Selenium dioxide and osmium tetroxide are effective reagents and catalysts for olefin oxidation, although, owing to their toxicity, reservations remain as to their applicability.^[1] We are therefore seeking more easily handled metal oxides that are soluble in organic solvents and that are as effective as osmium tetroxide in carrying out stereospecific cis hydroxylation of olefins. The rhenium(VII ) oxide 1 , which has meanwhile become readily accessible, is a favorable candidate.^[2]     

The chemical transport of molybdenum and tungsten and of their dioxides and sulfides

Experiments have been made and an extensive thermodynamic discussion has taken place concerning the chemical transport of Mo, W, MoO₂, WO₂, MoS₂ and WS₂ in the presence of iodine. Efforts have been made to find the species via which Mo and W can migrate within the gas phase.Results: In each case the transport proceeds via the oxide iodides MoO₂J₂ and WO₂J₂ respectively, as already known for the dioxides. Thus the chemical transport of Mo, W, MoS₂ and WS₂ needs not only J₂ but also H₂O, usually liberated from the wall of the quartz ampoule.By means of J₂ + H₂O, the metals can be transported into the high temperature region of the ampoule (e.g., 1050 → 1150°C), whereas the transport of the sulfides proceeds in the opposite direction (e.g., 900 → 700°C).For the sulfide-transport the influence of the ratio of the transport agents $\text{J}{}_2\text{H}{}_2\text{O}$ has been discussed.The water content of the quartz glass out of which the ampoules are made is an important source for water, influencing the reactions.The addition of graphite which considerably lowers the H₂O partial pressure prevents any transport of the metals or the sulfides, which proves that the use of J₂ alone as a transport agent is insufficient in these cases.The gaseous iodides MoJ_x and WJ_z are without any importance under the experimental conditions used for the transport of the metals, their dioxides and sulfides.The partial pressures of MoO₂(OH)₂ and WO₂(OH)₂ under the experimental conditions chosen may usually be neglected. But in the system $\text{MoO}{}_2\text{H}{}_2\text{O}$ the transport via MoO₂(OH)₂ (1000 → 800°C) has been observed.The synthesis of MoO₂ and WO₂, starting with the elements or with powder of metal and trioxide is promoted by the addition of J₂. The reaction steps involved are discussed.