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.     

新的N-苯并噻唑基香豆素酰胺类化合物的合成及光谱特性

用具有光学活性和生物学活性的2类化合物(取代)香豆素-3-甲酰氯和2-氨基苯并噻唑作用合成了4种新的兼具香豆素骨架和苯并噻唑基的化合物(3a-3d),用HRMS,IR和1H NMR对化合物结构进行了表征,确定了化合物的结构,并对其紫外吸收光谱和荧光光谱与分子结构的关系进行了讨论.研究发现:在紫外光谱中,新化合物(3a-3d)和2种原料化合物相比,因共轭链的增长而使其最大吸收波长(λmax)红移;4种化合物表现出比原料化合物较强的荧光性能,其中3c的荧光强度最大.文中给出了稀溶液中紫外光谱和荧光光谱相关的一些信息.     

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.     

苯并咪唑苯并异喹啉酮及其衍生物的电子结构和光谱性质的理论研究

采用密度泛函、含时密度泛函和单激发组态相互作用(CIS)方法研究了苯并咪唑苯并异喹啉酮(1)及其衍生物的电子结构特性和光谱性质,并用极化连续模型考虑了溶剂的影响.结果表明,化合物1及其衍生物的吸收和荧光发射过程的电子垂直跃迁是由于分子内的电荷迁移.化合物1中取代基的位置及给吸电子能力影响其HOMO-LUMO能隙和电荷迁移量.在分子中引入吸电子和给电子取代基,均使最大吸收波长和最大荧光发射波长红移,计算的结果与实验结果吻合得较好.     

二种氧氮杂环戊二烯类化合物的合成及其光性能研究

本文合成了对-(2-苯基-1,3,4,-噁二唑基-5)-(5’-苯基噁唑基-2’)苯和对-(2-苯基-1,3,4-噁二唑基-5)-(2’-苯基q罨唑基-5’)苯二类共12种化合物,测试了它们的紫外、荧光、红外光谱和激光转换效率.     

新型含二茂铁基螺噁嗪类光致变色化合物的合成及其光谱研究

合成了一种新的含二茂铁基螺噁嗪类光致变色化合物，并研究了其吸收光谱和荧光光谱。发现在分子内引入二茂铁基团提高了热不可逆性，发生光致变色反应前后化合物结构的不同对其荧光特性影响很大。     

插烯噁唑类化合物的研究(Ⅰ)——反-1,2-双[2′-(5′-苯基噁唑基)]乙烯及其衍生物的合成与光性能的研究

本文合成了12种反-1,2-双[2’-(5’-苯基嚼唑基)]乙烯(简称POEOP)及其衍生物。讨论了化合物的结构同其红外光谱、紫外光谱、荧光光谱、荧光量子产率及激光转换效率间的关系,并与POOP类化合物的光性能进行了比较。     

共轭刚性苯并二噁唑类聚合物的合成及其光物理性能研究

设计并合成了一系列共轭高分子———聚亚苯基苯并二唑 (PBO) ,聚亚乙烯基苯并二唑 (PBOV)和聚亚丁二唑 (PBODV) ,并对它们进行了表征 .用紫外吸收光谱和荧光光谱对聚合物的溶液和薄膜进行了详细的研究 ,研究结果表明分子结构中双键的引入可以降低聚合物的光带能隙 ,λmax从PBO溶液的 4 2 8 5nm (Eg=2 76eV) ,到PBOV溶液的 4 80 5nm (Eg=2 4 6eV) ,再到PBODV溶液的 4 96 0nm (Eg=2 38eV) .共轭程度的增加使得聚合物溶液更容易发生集聚从而导致荧光自熄灭 .     

香豆素酰胺类化合物的合成及光谱特性

用(取代)香豆素-3-甲酰氯(Ⅰa～Ⅰc)和取代2-氨基苯并噻唑(Ⅱa～Ⅱd)作用合成了12种新的目标化合物(Ⅲa～Ⅲl),用HRMS、IR、1H NMR对化合物结构进行了表征,确定了化合物的结构,并对其紫外吸收光谱和荧光光谱进行了分析。研究发现:在紫外光谱中,新化合物(Ⅲa～Ⅲl)和原料化合物(Ⅰa～Ⅰc)相比,因共轭链的增长而使其最大吸收波长(λmax)红移;12种化合物表现出比原料化合物(Ⅰa～Ⅰc)较强的荧光性能。     

2-(取代苯乙烯基)-5-取代苯并噁唑的合成及其光性能的研究

通过2-甲基苯并噁唑或2-甲基-5-叔丁基苯并噁唑在KOH/DMF介质中与苯甲醛或取代苯甲醛反应,合成了22个标题化合物,其中13个未见报道。测定了它们的结构和紫外光谱、荧光光谱、荧光量子产率,并对母体化合物的溶剂效应进行了研究。     

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%.     

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.     

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.     

Selective syntheses of 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones via temperature-dependent Rh(II)-carbenoid-mediated 2H-azirine-ring expansion

The Rh(II)-catalyzed reaction of 2-carbonyl-substituted 2H-azirines with ethyl 2-cyano-2-diazoacetate or 2-diazo-3,3,3-trifluoropropionate provides an easy access to 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones. These compounds can be selectively prepared from the same starting material using temperature as the only varied parameter. The 2-azabuta-1,3-diene intermediate, a common precursor for both heterocyclic products, isomerizes into 2H-1,3-oxazine under kinetic control, while 1H-pyrrol-3(2H)-one is the sole product of the reaction at elevated temperatures. According to DFT-calculations a one-atom oxazine ring contraction involving ring-opening to a 2-azabuta-1,3-diene intermediate, followed by a 1,5- and 1,2-prototropic shift leads to the consecutive formation of imidoylketene and azomethine ylide, which then further undergo cyclization to the pyrrole derivative.     

Copper catalyzed/mediated synthetic methodology for ebselen and related isoselenazolones

Scope of the copper catalyzed/mediated selenium-nitrogen coupling reaction has been studied for the synthesis of isoselenazolones. It is noticed that the 2-chloro, 2-bromo-, and 2-iodo-aryl amides substrates can be exploited in the selenium-nitrogen coupling reaction by employing 25-100 mol % of CuI/1,10-phenanthroline (L) and potassium carbonate as a base in DMF. Furthermore, electron rich 2-chloro-arylamides also underwent selenium-nitrogen coupling reaction to give biologically important selenium-nitrogen heterocycles. Also, copper-catalyzed selenium-nitrogen coupling reaction has been meticulously applied for the synthesis of diaryl diselenides having methoxy, amine, and amide functionality from respective aryl iodides in the presence of stoichiometric amount of succinimide as an external Se-N coupling partner.     

Knoevenagel condensation catalyzed by novel Nmm-based ionic liquids in water

A series of novel N-methyl morpholine (Nmm) based ionic liquids with 1,2-propanediol group were synthesized and used as catalysts for Knoevenagel condensation at room temperature in water. Under the effect of the catalyst, various aldehydes or aliphatic ketones could react with a wide range of activated methylene compounds well, including malononitrile, alkyl cyanoacetate, cyanoacetamide, β-diketone, barbituric acid, 2-arylacetonitrile and thiazolidinedione. Furthermore, most of the products could be separated just by filtrating and washing with water. Additionally, the catalyst is recyclable and applicable for the large-scale synthesis.     

Construction of polyheterocyclic spirotetrahydrothiophene derivatives via sulfa-Michael/aldol cascade reaction

A series of polyheterocyclic spirotetrahydrothiophene derivatives were obtained in moderate to excellent yields via a catalyst-free sulfa-Michael/aldol cascade reaction of chalcones 1 and commercially available 1,4-dithiane-2,5-diol 2 under mild conditions. We also present the first asymmetric sulfa-Michael/aldol cascade reaction of chalcones 1 and commercially available 1,4-dithiane-2,5-diol 2 with moderate to good enantioselectivities catalyzed by readily available chiral phase-transfer catalysts (PTCs).     

Suzuki-Miyaura reactions of the soluble guanylate cyclase inhibitor NS2028: a non-product specific route to C-8 substituted analogues

Both soluble guanylate cyclase (sGC) inhibitors ODQ 1 and NS2028 2 are synthesized via improved protocols. In the former case treating 3,4-dihydroquinoxalin-2(1H)-one oxime 8, which can be prepared in two steps from 1,2-benzenediamine, with 1,1′-carbonyldiimidazole (CDI) gives the dihydro-ODQ 10 that in the presence of KMnO₄ oxidises to give ODQ 1 in an overall yield of 46% starting from 1,2-benzenediamine. In the latter case, the synthesis affords NS2028 2 from 2-amino-4-bromophenol 3 in three steps with an overall yield of 85% and avoids the need for chromatography. Furthermore, Suzuki-Miyaura reaction conditions are described that enable the preparation of 8-aryl and 8-heteroaryl derivatives of NS2028 directly from NS2028 2. Finally, demethylation of the 8-(methoxyphenyl) substituted analogues afforded the 8-(hydroxyphenyl) derivatives 40-42. All new products are fully characterised.