N-乙烯基咔唑的光聚合

N-乙烯基咔唑的三氯甲烷溶液经光照后可以获得聚N-乙烯基咔唑,这一结论已经通过荧光光谱和NMR谱得到证实,产率很高可达70％。又通过荧光淬灭实验证实:这一反应首先在光照下形成激基复合物,由激基复合物分解产生自由基而引发N-乙烯基咔唑的聚合,此外,本文还研究了光强、N-乙烯基咔唑的浓度和光照时间对产率的影响。     

光促进温和条件下溴代烷烃与甲酸甲酯的羰基化反应

研究了光促进温和条件下,以甲酸甲酯为C1源,非贵金属钴盐、铜盐催化的溴代烷烃的羰基化反应.实验表明,在光促进下,钴盐、铜盐均可催化溴代烷烃与甲酸甲酯的羰基化反应,得到相应的羧酸甲酯.钴盐催化下,碱性添加物NaOAc对反应有很好的促进作用,直链溴代烷烃在反应中除了得到相应的正构酯外,还有少量异构酯生成;铜盐催化下,直链溴代烷烃在反应中主要生成相应的正构酯.机理研究表明,在光照下甲酸甲酯先分解为CO和CH3OH,再与溴代烷烃进行羰基化反应.     

季铵盐对碘代全氟烷烃的卤键吸附作用

通过红外光谱、紫外光谱及核磁共振波谱表征了四丁基碘化铵盐对正己烷溶液中二碘四氟乙烷(C_2F_4I_2)的卤键吸附作用.结果表明,固液两相间卤键作用引起的光谱变化同溶液中形成卤键复合物的光谱变化一致;四丁基氯化铵的吸附作用强于四丁基溴化铵和四丁基碘化铵,而具有较长烷烃链的季铵盐——十六烷基三甲基氯/溴化铵对C_2F_4I_2则完全没有吸附作用.对四丁基氯化铵与4种碘代全氟烷烃间卤键作用强度的测定结果显示,尽管溶液中一碘代全氟烷烃与氯阴离子间的卤键作用强于二碘代全氟烷烃,但在固液两相间四丁基氯化铵对二碘代全氟烷烃的吸附强于一碘代全氟烷烃.利用拉曼光谱研究该体系时,发现卤键的形成可增强碘代全氟烷烃的拉曼光谱.     

RAFT聚合制备结构明确的荧光标识聚甲基丙烯酸甲酯

以铁氰化钾为氧化剂,通过N-咔唑二硫代甲酸钠的水相氧化制备了高纯度的中间体二硫化双(N-咔唑硫代甲酰)(DTCD),DTCD以晶体的形式从水中析出,提纯简单,性质稳定.通过DTCD与偶氮二异丁腈(AIBN)或偶氮二氰基戊酸(ACVA)的反应合成了2种性能优异的叔丁腈酯基RAFT试剂,N-咔唑二硫代甲酸异丁腈酯(CYCBD)和N-咔唑二硫代甲酸氰基戊酸(CVCBD),新合成工艺的副反应和杂质被大量减少,最终产物的收率可达80%以上.以CYCBD和CVCBD为可逆加成断裂链转移(RAFT)试剂,研究了它们对甲基丙烯酸甲酯(MMA)RAFT聚合的控制能力,结果表明CYCBD和CVCBD是性能优异的RAFT试剂,可以很好地用于制备结构明确、分子量分布窄的链末端咔唑标记的聚甲基丙烯酸甲酯(CPMMA),由它们所制得的CPMMA的PDI小于1.2.研究结果还表明CYCBD和CVCBD及由其合成的CPMMA在四氢呋喃(THF)溶液中具有显著的荧光特性,CPMMA在358nm处有很强的荧光发射峰,而且,在浓度范围为0.1～20μmol/L的THF溶液中,CPMMA的荧光发射强度与其浓度具有良好的线性关系.通过CYCBD和CVCBD可以方便地制备结构明确且具荧光标识的功能聚合物。     

新型四齿膦配体在钯催化的Suzuki偶联反应中的应用

由廉价易得的1,2-环己二胺作为起始原料,通过简单的合成步骤制备了一种新型的四齿膦配体1,并将该配体应用于钯催化的Suzuki交叉偶联反应中.在仅为0.1 mol%的催化剂用量下,成功地实现了多种氯/溴代芳烃、氯/溴代杂环芳烃以及溴代烷烃底物与苯硼酸的交叉偶联反应,产率最高可达99%.     

2-糠醛缩N-乙基-3,6-二氨基咔唑双席夫碱的合成及其性能

以咔唑为起始原料经N-取代、硝化和还原反应制备中间体N-乙基-3,6-二氨基咔唑,然后以其与2-糠醛发生缩合反应制得新型双席夫碱化合物N-乙基-3,6-二(2-亚糠基亚氨基)咔唑,产率为72.36%。通过元素分析、FTIR、UV-Vis、1H NMR、溶液及固体荧光光谱、循环伏安(CV)和TG-DTA分析研究了标题化合物的分子结构、光物理特性、电化学特性和热稳定性。结果表明,化合物的DMF稀溶液在200~400 nm波段有较宽较强的紫外吸收;在365nm波长激发下,溶液发射深蓝色荧光,λem为446nm,固体荧光为λem=467nm的蓝色荧光,与溶液荧光相比固体荧光红移了21nm。由循环伏安测试得到产物的Eg=2.19e V,IP=4.99e V以及EA=2.80e V,说明其具有良好的空穴和电子传输材料性能。TG-DTA测试显示目标产物具有良好的热稳定性。该化合物在有机荧光、空穴注入传输材料以及电子传输材料方面具有潜在应用前景。     

经由Domino脱HCl/Pd（OAc）2催化的Heck反应合成查尔酮

通过Domino脱HCl/Pd(OAc)2催化的Heck反应实现了β-氯代烷基芳基酮、酯和酰胺与卤代芳烃的交叉偶联反应,高效合成了查尔酮类化合物。利用原位生成烯酮为中间体进行反应的策略,减少副反应的发生,从而提高反应的效率。该方法对各种官能团的容忍性好,为从氯代烷烃出发直接合成查尔酮类化合物提供了一条新途径。     

经由Domino脱HCl/Pd（OAc）2催化的Heck反应合成查尔酮

通过Domino脱HCl/Pd(OAc)2催化的Heck反应实现了β-氯代烷基芳基酮、酯和酰胺与卤代芳烃的交叉偶联反应,高效合成了查尔酮类化合物。利用原位生成烯酮为中间体进行反应的策略,减少副反应的发生,从而提高反应的效率。该方法对各种官能团的容忍性好,为从氯代烷烃出发直接合成查尔酮类化合物提供了一条新途径。     

新型咔唑取代齐聚芴的合成及其性能

碘代芴中间体在碱性条件下与咔唑发生偶联反应,合成了两种新型的有机小分子发光材料2-咔唑-9,9-二丁基芴(CZF)与2,7-二咔唑-9,9-二丁基芴(DCZF),其结构经¹H NMR, ¹³C NMR和MS表征。采用FL, UV-Vis和TGA研究了CZF和DCZF的性能。结果表明：CZF和DCZF溶液与固体的荧光发射峰分别位于360 nm, 368 nm和370 nm, 389 nm, DCZF在390 nm和410 nm处存在两个较宽肩峰。CZF和DCZF的热稳定性较好,热分解温度分别为350 ℃和420 ℃。     

利用激光诱导荧光技术研究Ca(~1S_0)与氯代乙烷的反应

碱土金属原子与卤代烷烃的反应有许多特有的反应动力学性质,引起人们对它的广泛兴趣。我们曾研究了碱土金属Ba、Ca原子与氯代甲烷的反应,得到一些有趣的结果。为了寻求碱土金属原子与卤代烷烃反应的一般规律,本实验室准备进行更全面的探讨。本文报导反应Ca(~1S_0)+C_2H_(6-n)Cl_n(n=2,3,4)的研究结果。这个反应与Ca(~1S_0)+CH__(4-n)Cl_n反应相比较,有一个显著的不同点,即反应物分子氯代乙烷有两个碳原子,氯原子可与不同的碳原子结合,提供了考察反应物结构对反应的影响以及反应物分子中官能团间的相互影响的机会。我们研究了下述的反应通道:     

N-Arylation of carbazole by microwave-assisted ligand-free catalytic CuI reaction

N-Arylation of carbazole has been achieved in high yields within 1 h using a microwave-assisted catalytic CuI reaction with no organic ligand. The N-arylation can be performed by various arylhalides, such as phenyl, pyridine, thiophene, and thiazole moieties. Specifically, N-arylated bromocarbazoles were converted into useful synthetic intermediates for functionalized carbazole materials.     

A Green Synthesis of 2‐Amino‐4‐(9H‐carbazole‐3‐yl)thiophene‐3‐carbonitriles by a Step‐wise and One‐pot Three‐component Gewald Reaction

An eco‐friendly method has been developed for the synthesis of 2‐amino‐4‐(9H‐carbazole‐3‐yl)thiophene‐3‐carbonitriles from preliminary carbazole ( 1 ) through an intermediate of 2‐(1‐(9H‐carbazole‐3‐yl)ethylidene)malononitriles using the Knoevenagel condensation followed by the Gewald reaction. On the other hand, the target compounds could also be prepared in a one‐pot three‐component manner by treating equimolar quantities of 1‐(9H‐carbazole‐3‐yl)ethanone ( 3 ), malononitrile, and elemental sulfur. The merits of this preparation are mild reaction conditions. The Gewald reaction is executed with inorganic base NaHCO₃ (H₂O) in tetrahydrofuran, easy work‐up procedure with good yields.     

Synthesis and electrochemical properties of peripheral carbazole functional Ter(9,9-spirobifluorene)s

A facile approach for synthesis of spirobifluorene trimers with peripheral carbazole functional groups by utilizing Suzuki coupling as the key reaction has been developed. These novel compounds exhibit blue emission with high quantum yields in solution and thin films, and excellent spectral stability upon photoirradiation and annealing in air. By the introduction of carbazole groups, the oxidation potentials of spirobifluorene trimers S TCPC-6 and STCPC-4 were significantly lower than that of model compound STHPH without peripheral carbazole groups, which reflect that the title compounds process higher HOMO energy level and better hole-injection ability. Highly luminescent films were obtained by electrochemical coupling between carbazole units. Pure blue-emission single-layer LEDs based on electrochemical deposition films as light emitting layers were achieved.     

Synthesis and characterization of deep blue emitters from starburst carbazole/fluorene compounds

A series of well-defined, highly fluorescent starburst compounds with a carbazole core and oligo(2,7-fluorene ethynylene) arms have been synthesized by Sonogashira coupling reaction and fully characterized. These conjugated compounds exhibit good solubility, high thermal stability, and excellent fluorescence quantum yields (up to 0.99). The incorporation of carbazole core interrupted the main-chain conjugation and resulted in blue-shifted absorption and emission. Moreover, deep blue light has been approached from organic light-emitting diodes (OLEDs) adopting these compounds as emitting layer.     

Synthesis of putative clausenal from carbazole using sequential C–H borylations

A synthesis of the putative clausenal structure has been achieved from commercially available carbazole using a five-step sequence that features three iridium-catalyzed C–H borylation reactions. This conceptually disparate approach to carbazole synthesis further demonstrates the utility of the iridium-catalyzed borylation reaction in heteroaromatic C–H functionalization. The spectroscopic data of the synthetic sample casts doubt on the structure assigned to the natural product.     

咔唑双乙酰化衍生物的合成及其电子光谱

以咔唑为原料,通过SN1亲核取代和Friedel-Crafts亲电取代反应合成了咔唑双乙酰化衍生物——3,6-二乙酰基-N-乙基咔唑和3,6-二乙酰基-N-丁基咔唑,其结构经1H NMR,IR,MS和元素分析表征,并讨论了它们的电子吸收光谱。     

Hydrogen atom transfer reaction from excited carbazole to pyridine

The hydrogen bonding interaction between excited carbazole and pyridine was investigated in cyclohexane by an emission—absorption flash technique. Triplet carbazole is deactivated by pyridine with a rate constant of 4.9 × 10⁷ M⁻¹ s⁻¹, yielding the carbazyl radical with a reaction yield of unity. The triplettriplet absorption of carbazole hydrogen bonded with pyridine was not observed. By means of the triplet energy transfer from N-ethylcarbazole to the hydrogen-bonded carbazole it was found that the triplet state of the hydrogen-bonded carbazole yields the carbazyl radical wtih a reaction yield of 0.7. Excited singlet carbazole is deactivated by pyridine with a diffusion-controlled rate, yielding the carbazyl radical with a reaction yield of 0.1. Flashing of the hydrogen-bonded carbazole does not yield carbazyl radical. The difference in the reaction yields between the free and the hydrogen-bonded species indicates that the dynamic hydrogen atom transfer reaction occurs from the encounter state in competition with hydrogen bond formation.     

Simple synthesis of substituted pyrroles

Simple synthesis of substituted pyrroles using iodine-catalyzed and montmorillonite KSF-clay-induced modified Paal-Knorr methods has been accomplished with excellent yields. N-Substituted carbazole has also been prepared by following this method. If one of the reactants is a liquid, the reaction proceeds exceedingly well without a solvent. This method gives pyrroles with less nucleophilic multicyclic aromatic amines at room temperature.     

Combined directed ortho and remote metalation-cross-coupling strategies. General method for benzo[a]carbazoles and the synthesis of an unnamed indolo[2,3-a]carbazole alkaloid

[reaction: see text] An efficient route to benzo[a]carbazoles via a metalation-cross-coupling sequence has been demonstrated and its application to the synthesis of the antitumor and antiviral alkaloid 6-cyano-5-methoxy-12-methylindolo[2,3-a]carbazole has been achieved.     

Synthesis of Carbazole Alkaloids by Ring‐Closing Metathesis and Ring Rearrangement–Aromatization

Aprocess for the assembly of carbazole alkaloids has been developed on the basis of ring‐closing metathesis (RCM) and ringrearrangement–aromatization (RRA) as the key steps. This method is based on allyl Grignard addition to isatin derivatives to provide smooth access to 2,2‐diallyl 3‐oxindole derivatives through a 1,2‐allyl shift. The diallyl derivatives were used as RCM precursors to afford a novel class of spirocyclopentene‐3‐oxindole derivatives, which underwent a novel RRA reaction to afford carbazole derivatives. The synthetic sequence to carbazoles was shortened by combining the RCM and RRA steps in an orthogonal tandem catalytic process. The utility of this methodology was further demonstrated by the straightforward synthesis of carbazole alkaloids, including amukonal derivative, girinimbilol, heptaphylline, and bis(2‐hydroxy‐3‐methylcarbazole).