新型氟代缺联吡啶环蕃的合成

以1,3-二溴甲基-5-氟苯为原料,在低温条件下利用模板效应制得"联吡啶环蕃化合物"(1);1经过连续萃取及离子交换合成了新型氟代缺电子联吡啶环蕃单体——环蕃F-CPQT,收率7.6%,其结构经1H NMR和13C NMR表征。     

新型手性季鏻盐的合成

以(S)-联萘酚为原料,与三氟甲磺酸酐反应制得联萘酚三氟甲磺酸酯(2);2在Ni(dppp)Cl2催化下与碘甲烷格氏试剂反应得2,2’-二甲基联萘(3);3经溴代反应得2,2’-二溴甲基联萘4;4与1,3-双(二苯基膦)丙烷(dppp)在甲苯中回流合成了一个新型的联萘酚衍生的双中心手性季鏻盐,其结构经1H NMR,31P NMR和FT-IR表征。     

新型四阳离子型1,2,3-三唑鎓环蕃的合成

以间苯二酚为原料,经5步反应制得中间体4,4′-［4,6-双(己氧基)-1,3亚苯基］双{1-［4-(叠氮甲基)苯基］-1H-1,2,3-三氮唑}(6); 6与1,5-二乙炔基-1,4-二(己氧基)苯在高度稀释的条件下经Click反应环合制得1,2,3-三唑环蕃(7); 7与三甲基氧鎓四氟硼酸盐反应合成了全甲基化的新型1,2,3-三唑鎓环蕃,其结构经¹H NMR, ¹³C NMR和HR-ESI-MS表征。     

氟醚链的合成及超分子性能研究

以2,3,5,6-四氟-1,4-苯二甲醇为原料,经选择性单醚化、溴代及酯化反应合成了一种新型的氟醚链(Ⅰ),通过IR、MS、1H NMR对目标化合物和中间体结构进行了确证.以此作为富π电子供体和缺π电子联吡啶大环化合物环双(百草枯-亚苯基)四阳离子环蕃(CPQT)自组装形成新型准轮烷Ⅱ(I-CPOT),并利用1HNMR化学位移变化跟踪该准轮烷在温度调控下的分子开关功能.     

“黑洞型”缺电子联吡啶环蕃的合成

利用2,3,5,6-四氟-1,4-苯二甲酸为原料, 经过酯化、还原及溴代, 合成1,4-二溴甲基-2,3,5,6-四氟苯. 以其为原料在低温下利用模板效应合成高度缺电子的“黑洞型”缺电子联吡啶环蕃化合物, 经过连续液液萃取及离子交换得到“黑洞型”缺电子联吡啶环蕃单体. 产品经¹H NMR, ¹³C NMR, MS表征. 利用变温核磁共振技术研究“黑洞型”缺电子联吡啶环蕃与经典的双环(百草枯-对苯撑)型缺电子联吡啶环蕃在溶液中的变化.     

含硫希夫碱的合成研究

合成了一种含硫希夫碱—1，4-双[(2’-甲醛缩硫代氨基脲基)苯氧甲基]乙烷及其中间产物1，4-双[(2’-甲醛)苯氧甲基]乙烷．其结构经元素分析，IR和1H NMR表征。     

可光固化单体2,7-二溴-9,9-双[4’-(3″-乙基-3″-氧杂环丁烷甲氧基己基氧基)苯基]芴的合成

以芴为原料,经溴代和氧化反应制得2,7-二溴芴酮(3);3与苯酚反应合成2,7-二溴-9,9-双(4’-羟基苯基)芴(4);4与3-(6’-溴己氧基甲基)-3-乙基氧杂环丁烷经醚化反应合成了可光固化单体2,7-二溴-9,9-双[4’-(3″-乙基-3″-氧杂环丁烷甲氧基己基氧基)苯基]芴,总收率67%,其结构经1H NMR,13C NMR和元素分析表征。     

新型联萘衍生物的合成及其光电性能

以咔唑和4,4’-二氨基-1,1’-联萘为初始原料,经重氮化反应、Ullmann反应、NBS亲电取代反应和Suzuki偶联反应,合成了两种新型空穴传输材料——4,4’-双[(9-对甲基苯基)-9H-3-咔唑基]-1,1’-联萘(4a)和4,4’-双[(9-对联苯基)-9H-3-咔唑基]-1,1’-联萘(4b),其结构经1H NMR和元素分析表征。研究了4a和4b在二氯甲烷中的UV和荧光性质。结果表明,4a和4b的最大发射波长分别为429 nm和427 nm。     

新型萘酰亚胺衍生物的合成

N-(N’,N’-二甲基氨基乙基)-4-硝基-1,8-萘酰亚胺和2,3-二甲基苯并噻唑碘化盐在痕量水存在下经亲核取代反应合成了一个新型的萘酰亚胺衍生物——N-(N’,N’-二甲基氨基乙基)-4-[2-(2,3-二氢-2,3-二甲基苯并噻唑)氧基]-1,8-萘酰亚胺,其结构经1H NMR,13C NMR和ESI-MS表征。并对反应机理进行了初步研究。     

2-叔丁基-4-氟-苯并氧杂卓并[3,4-b]喹啉并[9,11]二氧戊环-14（6H）-酮的合成

以2-溴甲基-6,7-亚甲二氧基-3-喹啉酸乙酯(1)为原料,经三步合成了2-叔丁基-4-氟-苯并氧杂卓并[3,4-b]喹啉并[9,11]二氧戊环-14(6H)-酮(4)。其中,6-(2-氟-4-叔丁基-苯氧甲基)-[1,3]二氧戊环并[4,5-g]喹啉-7-羧酸是经一锅法合成的。它的分子内闭环反应是在Eaton’s reagent(P2O5-CH3SO3H)的作用下,在较温和的条件下进行的。所得新化合物3和4的结构经IR1、H NMR和元素分析得以证实。     

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.     

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.     

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).