新型蒽类聚方酸菁的合成及其性能

以蒽为起始原料,经溴代反应和Witting-Horner反应制得单体9,10-双[2-(1-辛基-1H-吡咯-2-基)乙烯基]蒽(3);3与芳酸缩聚合成了一个新型的蒽类聚方酸菁(4),其结构和性能经UV-Vis,1HNMR,13CNMR,IR,XRD,SEM和TG表征。4在氯仿中的λmax位于700nm;4为非晶态结构;4的初始分解温度为297.1℃。     

胺蒽类有机电致发光材料的合成和发光性能的研究

芳基伯胺与芳基溴在Pd(dba)2/P(t-Bu)3催化下于80℃甲苯溶液中反应生成芳基仲胺,芳基仲胺再与溴代蒽在Pd(OAc)2/P(t-Bu)3催化下于120℃邻二甲苯溶液中反应生成蒽类芳胺有机电致发光材料,产物的结构经1H NMR,13CNMR,13C(DEPT),MS(HREI和EI)光谱所证实.用UV-vis,PL,DSC测定了蒽类芳胺化合物的发光性能.     

傅克反应的异常产物

苯和草酰氯单乙酯在三氯化铝作用下发生傅克反应,在低温(0 ℃)条件下生成苯乙酮酸乙酯,而在高温(70 ℃)条件下首次得到了9,10-二甲基蒽,其结构经1H NMR,13C NMR和单晶X-衍射仪表征.     

新型正丁醛杯[4]芳烃醚衍生物的合成

以正丁醛间苯二酚杯[4]芳烃为原料,经酯化、水解、酰氯化后再与9-蒽甲醇反应,合成了蒽单取代的正丁醛间苯二酚型杯[4]芳烃醚衍生物。其结构经1H NMR和IR表征。     

CAN/PEG-400体系催化合成氧杂蒽二酮类衍生物

以硝酸铈铵(CAN)为催化剂,PEG-400为溶剂,芳香醛与β-环己二酮于85℃反应2.0 h～3.0 h合成了一系列氧杂蒽类衍生物,收率83%～96%,其结构经1H NMR和13C NMR确证。CAN/PEG-400可回收套用4次。     

6-溴-7-异丙基-1,10-二甲基-1,2,3,4-四氢蒽-1-羧酸的合成

以脱氢松香酸为原料,经酯化、溴代、氧化、异构化、水解等反应,合成了一种新型的四氢蒽羧酸类衍生物———6-溴-7-异丙基-1,10-二甲基-1,2,3,4-四氢蒽-1-羧酸,其结构经1H NMR,13C NMR,MS和元素分析表征。     

辽河和孤岛渣油供氢与生焦趋势

首先以蒽为化学探针对孤岛,辽河和胜利减压渣油及其四组分的氢转移能力进行表征,原理是,蒽与渣油在３５０－４００℃热反应,渣油向蒽供氢,使蒽率成９,１０－二氢蒽,用气相色谱分析定量测定热反应产物中的９,１０－二氢蒽,并计算出单位重量油样供氢量;然后在４００℃下热处理测定三种渣油的生焦诱导期。     

苯并[de]蒽-7-酮类叔芳胺的合成及其发光性能的研究

芳基伯胺与芳基溴在Pd(dba)2/P(t-Bu)3催化下于80 ℃甲苯溶液中反应生成芳基仲胺, 芳基仲胺再与3-溴苯并[de]蒽-7-酮在Pd(OAc)2/P(t-Bu)3催化下于120 ℃邻二甲苯溶液中反应生成苯并[de]蒽-7-酮类叔芳胺有机电致发光材料; 3-二苯基氨基苯并[de]蒽-7-酮与丙二腈反应生成2-(3-二苯基氨基)苯并[de]蒽-7-基亚基丙二腈. 产物的结构经1H NMR, 13C NMR, 13C (DEPT), HRMS光谱所证实. 用UV-Vis, PL, DSC测定了化合物的发光性能.     

2，3-二氯-5，6-二氰基-1，4-苯醌／NaNO2催化9，10-二氢蒽氧化脱氢

设计了一种由2,3-二氯-5,6-二氰基-1,4-苯醌（DDQ）和NaN02组成的复合催化剂,该催化剂在9,10-二氢葸氧化脱氢生成蒽的反应中表现出很高的催化活性和选择性．在120℃和1．3MPaO2下反应8h,9,10二氢蒽转化率达到99％以上,葸的选择性为99％．采用红外光谱和核磁共振方法对催化氧化脱氢的反应历程进行了研究．结果表明,9,10-二氢蒽氧气氧化脱氢生成蒽的反应是通过DDQ／DDQH2和NO2／NO两个氧化还原对的电子传递来推动的,以DDQ／NaNO2为催化剂可以有效催化9,10-二氢蒽氧化脱氢生成蒽．     

Dowson型钼钒磷杂多酸催化H2O2氧化蒽制备蒽醌

合成了5种Dowson型杂多酸催化剂(Pn),并用于催化H2O2氧化蒽制备蒽醌的反应.结果表明Hs[P2Mo14V4O62H2](P5)的催化活性最好.最佳的氧化反应条件为:蒽5.6 mmol,n(蒽):n(H2O2)=1:11,P530 mg,溶剂正丁醇,于70 ℃反应1 h,产率达93.2%.     

A carbanion induced synthesis of highly congested pyrazole and imidazole containing heterocycles

An efficient approach to the synthesis of highly congested di, penta and hexacyclic pyrazoles as well as imidazole fragment containing novel heterocyclic molecule has been developed through a carbanion induced transformation of suitably functionalized 2H-pyran-2-ones, benzo[h]chromene and thiochromeno[4,3-b]pyrans. Due to the presence of fluorescence, we report their prime application metal sensor as off/on switching in ferric ions.     

Selective synthesis of 4,5-dihydroimidazo- and imidazo[1,5-a]quinoxalines via modified Pictet–Spengler reaction

An efficient tandem approach for the selective synthesis of 4,5-dihydroimidazo[1,5-a]quinoxalines 6a–g and imidazo[1,5-a]quinoxalines 7a–h by the reaction of 2-imidazolyl anilines 4a–c with aryl aldehydes 5a–k under mild reaction conditions is described. Introduction of electron releasing alkyl groups in substrates 4a–b was found to be instrumental for the success of the reaction.     

Understanding the Diels-Alder reactivity of 1,2-azaborine analogues

The Diels-Alder reactivity of 1,2-heteroborines (H₄C₄B(H)X, X?=?NH, PH, AsH; O, S, Se) has been computationally explored by means of Density Functional Theory (DFT) calculations. The influence of the HB?=?X fragment on the reactivity of the system has been quantitatively analyzed in detail by means of the so-called Activation Strain Model (ASM) of reactivity. It is found that the interaction between these species and the dienophile is significantly stronger than that computed for their all-carbon isoelectronic counterpart, benzene. In addition, the strain energy plays a key role in the observed reactivity trends. The role of the aromaticity strength of these heteroarenes on the reactivity is also assessed.     

Synthesis of N-substituted carbazolones from α-iodo enaminones via Pd(0)-catalyzed intramolecular coupling under microwave irradiation

A variety of N-aryl and N-alkyl carbazolones were conveniently achieved in good to high yields via Pd₂(dba)₃-mediated intramolecular coupling of N-substituted α-iodo enaminones under microwave irradiation. The Pd(0)-catalyzed cyclization was found to proceed favorably with the more electron-deficient phenyl ring during the reactions involving unsymmetrical N,N-diaryl α-iodo enaminones. This unique property enables the construction of carbazolone skeleton containing nitro substituted benzenoid ring.     

Synthesis of substituted 2,4,5,6-tetrahydrocyclopenta[c]pyrazoles and 2,4,5,6-tetrahydropyrrolo[3,4-c]pyrazoles by intramolecular nitrilimine cycloaddition

Both substituted 2,4,5,6-tetrahydrocyclopenta[c]pyrazoles and 2,4,5,6-tetrahydropyrrolo[3,4-c]pyrazoles have been synthesized by the 3+2 intramolecular dipolar cycloaddition of nitrilimines to alkynes. This cyclization has been extended to more versatile 3-bromo derivatives by the use of alkynylbromides as dipolarophiles.     

Catalyst free,visible-light promoted photoaddition reactions between C60 and N-trimethylsilylmethyl-substituted tertiary amines for synthesis of aminomethyl-1,2-dihydrofullerenes

An efficient and benign method for the preparation of aminomethyl-substituted fullerenes has been developed. The process, involving catalyst free, visible-light irradiation of 10% EtOH-toluene solutions containing fullerene C₆₀ and N-trimethylsilylmethyl-substituted amines by using a 20 W compact fluorescent lamp, leads to formation of aminomethyl-substituted fullerene adducts in a highly efficient manner. The photoaddition reaction takes place via a pathway initiated by visible light absorption by C₆₀, followed by SET from the amine to the triplet excited state of C₆₀. Ethanol-promoted desilylation of the resulting a minimum radical then generates the corresponding α-amino radical which couples with the C₆₀ radical anion to form the anion precursor of the fullerene adducts. The new approach using visible-light takes place under mild conditions and it does not require the use of photocatalysts. Thus, the method developed in this effort could broadens the range of functionalized fullerene derivatives that can be readily prepared.     

Highly efficient and stereoselective cycloaddition of nitrones to indolyl- and pyrrolylacrylates

The reactions of various nitrones with indolyl- and pyrrolylacrylates proceeds regioselectively with high diastereoselectivity in the case of aldonitrones, and represents an effective method for obtaining new indolyl- and pyrrolyl-substituted isoxazolidine carboxylates stabilized by weak (CH?O) and moderate (NH?N) strength intramolecular hydrogen bonding. The resulting cycloadducts exhibit promising in vitro anti-influenza activities.     

Transition metal-free direct amination of benzoxazoles using formamides as nitrogen sources

A transition metal-free method for the direct amination of benzoxazoles using formamides as nitrogen sources is reported, which was mediated by an inexpensive and environmentally friendly tetrabutylammonium iodide/tert-butyl hydroperoxide system and gave the 2-aminobenzoxazole derivatives with moderate to good yields.     

l-Proline-catalyzed five-component domino reaction leading to multifunctionalized 1,2,3,4-tetrahydropyridines

Multifunctionalized 1,2,3,4-tetrahydropyridines are concisely synthesized in good yields via l-proline-catalyzed or l-proline/FeCl₃-cocatalyzed one-pot multicomponent reactions (MCRs). The MCRs involve a domino hydroamination/prins reaction/Mannich-type reaction/intramolecular dehydration-cyclization process. The molecular structure of 5baa, one of multifunctionalized 1,2,3,4-tetrahydropyridines, was confirmed by single-crystal X-ray diffraction.     

Exploring the scope of the Gewald reaction: Expansion to a four-component process

An efficient four-component reaction was developed to take advantage of the reactivity of the 2-aminothiophene-3-carbonitrile functionality, which is obtained during the classical three-component Gewald reaction. Various α-methylene bearing ketones were reacted with malononitrile, elemental sulfur, and aryl/heteroarylnitrile derivatives in t-BuOH/NaOH to afford 2-arylthieno[2,3-d]pyrimidin-4-amines in high yields. Preliminary studies revealed the photophysical properties of the products and their potential for use as metal sensors.