三芳基吡唑啉噁二唑类衍生物的合成及其荧光光谱研究

提出了一种新的合成1,3,4-噁二唑化合物的方法,并通过Wittig反应将其与1,3,5-三芳基-2-吡唑啉相连合成了6种新的三芳基吡唑啉噁二唑类化合物.用红外光谱、质谱、核磁共振谱和元素分析对合成化合物进行了结构表征.用荧光光谱仪对它们的荧光性能进行了测试,测试结果表明目标产物具有良好的荧光性,其荧光发射波长均在437～511nm范围内,荧光量子产率最大可达0.36.     

2,2'-二苯并噁唑衍生物的合成和光性能研究

合成了16种2,2-二苯并(口恶)唑衍生物,测定了化合物的熔点、红外光谱、紫外吸收光谱、荧光发射光谱以及荧光量子产率,与1,4-二(苯并(口恶)唑1′,3′-基-2′)苯和1,4-二(苯并(口恶)唑-1′,3′-基-2′)乙烯衍生物进行了比较,讨论了它们之间光谱特性的差异.     

8,10-二氢-7H-4b,8,10-三氮杂苯薁衍生物的合成

苯并咪唑类化合物具有广泛的生物活性,其合成和应用研究一直十分活跃.以2-氨甲基苯并眯唑二盐酸盐与α,β-不饱和酮在三乙胺存在下,以正丁醇为溶剂反应,合成了4种8,10-氢-7H-4b,8,10-三氮杂苯并奠类衍生物,产率61%～67%.反应产物结构通过NMR、MS、元素分析和IR表征.     

聚芴基苯并唑类共聚物的合成和光物理性能

通过溶液缩聚法合成了一系列不同组分的无规共聚物--聚对苯撑苯并二噁唑-co-聚(9,9-二辛基芴苯并二噁唑)(PBO-co-PBOF).利用X射线衍射、紫外-可见光吸收光谱、光致荧光光谱研究了不同组分和结构变化对聚合物形态和光物理性能的影响.结果表明:聚合物主链上辛基芴基团的引入使聚合物结构从晶态转变为非晶态.共聚物分...     

具有大的双光子吸收截面的A-A-A型双苯乙烯基苯类化合物的合成

合成了A-A-A型双苯乙烯基苯类化合物FR[2,5-二氰基-1,4-二(4'-氟苯乙烯基)苯],并采用核磁共振、红外光谱和元素分析等手段对其进行了表征.用飞秒脉冲诱导荧光光谱法分别研究了2个A-A-A型双苯乙烯基苯类化合物FR与CY[2,5-二氰基-1,4-二(4'-氰基苯乙烯基)苯]以及2个D-A-D型双苯乙烯基苯类化合物MO[2,5-二氰基-1,4-二(4'-甲氧基苯乙烯基)苯]和MA[2,5-二氰基-1,4-二(4'-二甲胺基苯乙烯基)苯]的单、双光子吸收与发射特性.实验结果表明,最大单光子吸收与发射波长随末端取代基供电子能力的增强而增大,末端强吸电子基化合物FR和CY具有相当高的荧光量子产率(分别为0.92与0.89)、较长的荧光寿命(分别为5.8与6.1 ns)及较大的双光子吸收系数(分别为19.1与20.5).末端带强吸电子基的化合物FR与CY的双光子吸收截面(δ,分别为6350 GM和6870 GM)比末端带供电子基的化合物MO和MA的δ(分别为270 GM与1790 GM)要大得多,表明A-A-A型双苯乙烯基苯类化合物具有异常大的δ.     

苯并唑类共聚物与共混物的能量转移与激子空间限制研究

通过3-氨基-4-羟基苯甲酸盐酸盐(AHBAH),2,5-二氨基-1,4-苯硫醇盐酸盐(DABDT)和2,5-噻吩二羧酸(TDA)在多聚磷酸中缩聚,合成了一系列不同组成的高、低带隙无规共聚物聚(2,5-苯并噁唑)-co-聚(2,5-噻吩基苯并二噻唑)(ABPBO-co-PBZTT),并制备了一系列由ABPBO和PBZTT组成的共混物.通过紫外-可见吸收光谱、光致荧光光谱研究了聚合物不同组成和结构变化对光物理性能的影响.随着共聚物中PBZTT含量的增加,共聚物的发射波长红移,并发生了明显的ABPBO结构吸收能量向PBZTT转移的现象,共聚物膜的量子效率比纯PBZTT膜的量子效率有明显提高.共混物虽然也发生了能量转移现象,但其更易于形成集聚体,量子效率与纯的PBZTT聚合物相比,并没有明显提高.     

一类新型环金属配体——(口恶)二唑衍生物的化学结构及其性能

合成了5个2,5-二芳基-1,3,4-(口恶)二唑衍生物环金属配合物配体,其化学结构经1H NMR、IR和元素分析得到确证. 利用紫外光谱、荧光光谱、差热分析(DSC)和循环伏安法测试技术分别研究了它们的光谱性能、热性能和电化学性能. 结果表明,该类衍生物在二氯甲烷溶液中的最大紫外吸收波长在268～327 nm范围,在二氯甲烷溶液和固体膜中的最大荧光发射波长分别在332～390 nm和359～439 nm范围;DSC分析结果表明,5个(口恶)二唑衍生物的起始吸热峰位于120～328 ℃之间,其中对称结构的(口恶)二唑衍生物显示了较高的熔融温度;由循环伏安图和相关计算结果表明,5个(口恶)二唑衍生物的还原电位位于-1.03～-0.98 V,其相应的最低非占有分子轨道能级(LUMO)在-3.71～-3.76 eV之间.     

一类新型环金属配体——二唑衍生物的化学结构及其性能

合成了5个2,5-二芳基-1,3,4-噁二唑衍生物环金属配合物配体,其化学结构经1HNMR、IR和元素分析得到确证。利用紫外光谱、荧光光谱、差热分析(DSC)和循环伏安法测试技术分别研究了它们的光谱性能、热性能和电化学性能。结果表明,该类衍生物在二氯甲烷溶液中的最大紫外吸收波长在268～327nm范围,在二氯甲烷溶液和固体膜中的最大荧光发射波长分别在332～390nm和359～439nm范围;DSC分析结果表明,5个噁二唑衍生物的起始吸热峰位于120～328℃之间,其中对称结构的噁二唑衍生物显示了较高的熔融温度;由循环伏安图和相关计算结果表明,5个噁二唑衍生物的还原电位位于-1.03～-0.98V,其相应的最低非占有分子轨道能级(LUMO)在-3.71～-3.76eV之间。     

两个含双膦配体和[2,3-f]吡嗪并[1,10]菲咯啉的Cu髣配合物的合成、结构及光谱学性质（英文）

合成了2个新的铜髣配合物,[Cu(dppBz)(dpq)]ClO_4(1)和[Cu(dppe)(dpq)]ClO4(2)(dppBz=1,2-双(二苯基膦)苯,dppe=1,2-双(二苯基膦)乙烷,dpq=[2,3-f]吡嗪并[1,10]菲咯啉),通过X射线单晶衍射分析、元素分析、红外光谱、紫外吸收光谱、荧光光谱、核磁共振光谱和太赫兹时域光谱对其进行了分析和表征。1的中心Cu髣离子通过二亚胺配体和双膦配体共同螯合形成变形四面体结构,2的结构与1类似。配合物2的发光光谱表明它的发光具有金属-配体电荷转移(MLCT)特性。对配合物1和2在0.2～2.8 THz范围内进行了太赫兹时域光谱分析,结果表明0.40～0.90 THz的吸收与中心Cu髣离子的配位有关。     

两个双四唑胺的铜配合物的合成、结构及荧光性质(英文)

用Demko-Sharpless方法自制的双四唑胺配体,再混以乙二胺和丙二胺螯合配体,合成了2个新颖的铜的配合物Cu(bta)(en)(H2O)(1)与Cu(bta)(1,3-pda)(H2O)(2)。X-射线单晶衍射表征了2个配合物的结构。2个配合物的水溶液都表现出了双四唑胺配体的特征吸收波长与荧光发射波长。     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

Synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives

Different approaches for the synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives from simple amino acids have been investigated. A library of 33 precursors for the preparation of N-hydroxy pyrazinones was obtained in moderate to good yields.     

Toward new camptothecins. Part 6: Synthesis of crucial ketones and their use in Friedländer reaction

In the context of the preparation of camptothecin and luotonin A analogs, the synthesis of some key keto-precursors and their use in Friedländer condensation are described. This paper also focuses on the stability of these keto intermediates and emphasizes the major differences between indolizinones and pyrroloquinazolinones series. Noteworthy is also the report of some original structures isolated as by-products of some experiments.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.     

Highly regioselective Buchwald–Hartwig amination at C-2 of 2,4-dichloropyridine enabling a novel approach to 2,4-bisanilinopyridine (BAPyd) libraries

The highly regioselective Buchwald–Hartwig amination at C-2 of the cheap and readily accessible reagent, 2,4-dichloropyridine with a range of anilines and heterocyclic amines is described. This new methodology is robust and provides a facile access to 4-chloro-N-phenylpyridin-2-amines on 0.25 mol scale. These intermediates undergo a further Buchwald–Hartwig amination at higher temperature to enable rapid exploration of the chemical space at C-4 and to provide a library of 2,4-bisaminopyridines.     

KMnO4-mediated oxidative CN bond cleavage of tertiary amines: Synthesis of amides and sulfonamides

KMnO₄-mediated oxidative CN bond cleavage of tertiary amines producing secondary amine was introduced, which was trapped by electrophiles (acyl chloride and sulfonyl chloride) to form amides and sulfonamides. The reaction could take place at mild condition, tolerating a wide range of function groups and affording products in moderate to excellent yields.     

Chemistry of heterocyclic compounds at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, over 50 years (Review)

The review contains a concise historical account and information on the most significant researches undertaken by the staff at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences on the Chemistry of Heterocyclic Compounds. Dedicated to Academician of the Russian Academy of Sciences B. A. Trofimov on his 70th jubilee. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1443–1502, October, 2008.     

A general and convenient synthesis of 4-(tosylmethyl)semicarbazones and their use in amidoalkylation of hydrogen,heteroatom, and carbon nucleophiles

A general synthesis of previously unknown semicarbazone-based α-amidoalkylating reagents, 4-(tosylmethyl)semicarbazones, has been developed. The synthesis involved three-component condensation of semicarbazones of aliphatic or aromatic aldehydes with the same or other aldehydes and p-toluenesulfinic acid. The scope and limitations of this reaction were investigated. The compounds obtained were demonstrated to be an efficient α-(4-semicarbazono)alkylating agents. They were reacted with H- (sodium borohydride), O- (sodium methylate), S- (sodium phenylthiolate), N- (pyrrolidine, sodium succinimide), P- (trialkyl phosphites), and C-nucleophiles (sodium diethyl malonate) to give the corresponding products of the tosyl group substitution, 4-substituted semicarbazones, including analogues of nitrofurazone. Among the prepared compounds tested in vitro for antibacterial and antifungal activity, three nitrofuryl-containing semicarbazones exhibited high biological activities with minimum inhibitory concentration (MIC) values of 8–32 μg/mL.     

Sulfur-directed metal-free and regiospecific methyl C(sp3)–H imidation of thioanisoles

Regiospecific and direct imidation of the methyl C(sp³)–H bond of thioanisoles is realized under mild and metal-free conditions with N-fluorobis(benzenesulfonyl)imide as an oxidant and nitrogen source. Proposed mechanism suggests that thionium ion intermediates and a Pummerer-type reaction are involved. The imidation has advantages such as high step-economy, excellent functionality tolerance, and regiospecificity, giving structurally diverse imidation products.     

Synthesis of novel chiral bidentate hydroxyalkyl-N-heterocyclic carbene ligands and their application in palladium-catalyzed Mizoroki–Heck couplings and asymmetric addition of diethylzinc to benzaldehyde

A small library of new chiral bidentate hydroxyalkyl-imidazolium salts 1 is conveniently synthesized on multi-gram scale from inexpensive and commercially available chiral pool amino acids. The corresponding carbenes, generated by deprotonation of imidazolium salts 1, in combination with palladium(II) chloride were tested in the Mizoroki–Heck coupling reaction. The most significant results in terms of yields and reactivities were achieved with low catalyst loading. The catalytic activities of these imidazolium salts were also investigated in the asymmetric addition of diethylzinc to benzaldehyde. The use of MgO nanoparticles as an additive in conjunction with these ligands played a crucial role in increasing the efficiency of these reactions.