α′-乙酰基-α-噻吩基苯乙炔六羰基二钴和α′-乙酰基-α-噻吩基-P-乙酰基苯乙炔六羰基二钴的合成及结构

本文研究了α-噻吩基苯乙炔六羰基二钴同乙酰氯的傅氏酰化反应,证明噻吩核较苯核有更强的亲电酰化活性,而苯核又较乙酰化的噻吩核有更强的亲电酰化活性;通过酰化反应合成了两个新钴碳簇合物,即α′-乙酰基-α-噻吩基苯乙炔六羰基二钴Ⅰ和α′-乙酰基-α-噻吩基-P-乙酰基苯乙炔六羰基二钴Ⅱ。除用碳氢分析、IR和~1HNMR推得Ⅰ和Ⅱ的结构外,还测得Ⅱ的单晶结构。Ⅱ晶体属单斜晶系,空间群为PZ_1╱n,晶胞参数a=8.037(2),b=16.347(3),c=17.823(2),β=102.68(2)°,D_c=1.61g·cm~(-3),Z=4。最终偏离因子R=0.040。     

杂环膦亚胺钛配合物的合成及催化乙烯聚合（英文）

首先合成单取代和双取代杂环膦化合物R-PPh_2[R=2-吡啶基(3a),2-噻吩基(3b),2-呋喃基(3c)]和Ph_2P-R'-PPh_2[R'=2,6-吡啶基(6a),2,5-噻吩基(6b),2,5-呋喃基(6c)].然后与叠氮三甲基硅烷发生Staudinger反应生成相应的杂环膦亚胺配体R-PPh_2(NSiMe_3)和(Me_3SiN)Ph_2P-R'-PPh2(NSiMe_3).最后与环戊二烯三氯化钛反应脱去三甲基氯硅烷后得到具有烯烃聚合催化活性的杂环膦亚胺钛配合物.所有配合物结构都经过核磁的确认,为了进一步确定配合物分子结构,利用单晶X射线衍射解析了所有钛配合物的晶体结构.在助催化剂甲基铝氧烷(MAO)活化作用下,双钛中心配合物6a~6c比单钛中心类似配合物3a~3c表现出更高的催化乙烯聚合活性,所得聚合物具有较宽分子量分布呈双峰分布,6b在较低聚合温度下就可以制备超高分子量聚乙烯.     

2—肉桂酰噻吩的晶体结构

标题化合物进行了X—射线分析。该化合物晶体属正交晶系,Pbcm空间群,a=10.984(3),b=11.808(3),c=17.224(4)A,Z=8。1035个Ⅰ≥2σ(Ⅰ)的反射数据用于结构确定和修正,最终R=0.059。噻吩基平面与羰基平面的二面角略小于苯乙烯基平面与羰基平面的二面角,表明噻吩基与羰基的共轭倾向比苯乙烯基与羰基的略强,或者近乎相当。这一结果支持了噻吩基的端基当量为3的观点。     

2,3-二取代-4-(1H-1,2,4-三唑-1-基)-5-苯基氨基噻吩的合成及生物活性研究

合成了九个以噻吩为母体环的含三唑环的化合物--2,3-二取代-4-(1H-1,2,4-三唑-1-基)-5-苯基氨基噻吩(2a～2i),并测定了2a的晶体结构.晶体为三斜晶系,P-1空间群,晶胞参数为:a=0.79816(15)nm,b=1.00259(13)nm,c=1.4478(4)nm,α=100.326(16)°,β=94.69(2)°,γ=106.083(9)°,V=1.0845(4)nm3,Z=2,Dc=1.396g/cm3.初步生物活性表明所有目标化合物杀菌活性较低,有一定的植物生长调节活性.     

己基取代的1,4-二(2-噻吩基)苯并[c]哒嗪合成与光谱性质研究

本文设计并合成了一系列含氮原子的缺电子芳香片段,包括以苯并哒嗪作为核心、以富电子噻吩衍生物作为共轭延长链的有机共轭小分子1,4-二(2-噻吩基)苯并[c]哒嗪(5a)、1,4-二[2-(3-己基噻吩基)]苯并[c]哒嗪(5b)和1,4-二[2-(5-己基噻吩基)]苯并[c]哒嗪(5c).通过紫外光谱和荧光光谱研究,证明在共轭体系中的不同位置引入烷基链,可以有效影响化合物的能隙,调节化合物的光电性质.     

固相法合成新型三联噻吩与噻吩衍生物共聚物

采用固相合成法,分别用4,7-二噻基-2,1,3-苯并噻二唑, 1,4-二噻基-苯和3,6-二噻基-哒嗪与三联噻吩反应合成了三种三联噻吩与噻吩衍生物共聚物(2a~2c),其结构和电化学性质经 UV-Vis, IR, SEM和CV表征。结果表明：与均聚物相比,2a~2c的最大吸收峰无明显红移;氧化电位（0.53～0.51 V）较均聚物负移。     

噻吩桥联香豆素衍生物的制备及性能研究

本文合成了三个噻吩桥联香豆素衍生物,7-N,N-二乙氨基-3-(5-(芘-1-基)噻吩-2-基)-香豆素(Py-Th-NC),7-(N,N-二乙氨基)-3-(4-(5-(7-(N,N-二乙氨基)-香豆素-3-基)噻吩-2-基)苯基)-香豆素(NCTh-Ph-NC)和3-(4-(5-(7-(N,N-二乙氨基)-香豆素-3-基)噻吩-2-基)苯基)-香豆素(NC-Th-Ph-C),分别采用HRMS、1H NMR和IR对其结构进行了表征,并研究了三个化合物的发光性能、电化学性能及热稳定性。结果表明,这些香豆素衍生物具备很好的热稳定性,并在二氯甲烷溶液中显示蓝绿色或绿色荧光。     

噻吩桥联香豆素衍生物的制备及性能研究（英文）

本文合成了三个噻吩桥联香豆素衍生物,7-N,N-二乙氨基-3-(5-(芘-1-基)噻吩-2-基)-香豆素(Py-Th-NC),7-(N,N-二乙氨基)-3-(4-(5-(7-(N,N-二乙氨基)-香豆素-3-基)噻吩-2-基)苯基)-香豆素(NCTh-Ph-NC)和3-(4-(5-(7-(N,N-二乙氨基)-香豆素-3-基)噻吩-2-基)苯基)-香豆素(NC-Th-Ph-C),分别采用HRMS、1H NMR和IR对其结构进行了表征,并研究了三个化合物的发光性能、电化学性能及热稳定性。结果表明,这些香豆素衍生物具备很好的热稳定性,并在二氯甲烷溶液中显示蓝绿色或绿色荧光。     

基于2,5-噻吩二羧酸的稀土配合物的合成和表征

以2,5-噻吩二甲酸和稀土盐为原料,通过水热反应,合成了3个稀土金属配位聚合物{[La(OH)(SO4)]}n(1),{[La2(TDC)2(SUC)]}n(2)和{[Gd2(TDC)2(ox)(H_2O)4]·2H_2O}n(3)(H_2TDC=2,5-噻吩二甲酸,SUC=丁二酸,ox=草酸),分别用X射线单晶衍射、元素分析、红外光谱对配合物2和3进行了表征。实验结果表明:配合物2和3均呈现三维网络结构,其中配合物2属于正交晶系,空间群为Pbca,a=1.372 8(4)nm,b=0.704 0(2)nm,c=2.136 2(6)nm,Z=8;配合物3属于单斜晶系,空间群为C2/c,a=1.934 3(4)nm,b=0.990 5(2)nm,c=1.252 8(3)nm,β=107.463(4)°,Z=4。     

配位聚合物{Zn[(BTDC)_2(DMF)_2]}_4·(DMF)_4的合成及其晶体结构

2,2′-联二噻吩-5,5′-二羧酸(H2BTDC)与硝酸锌经水热合成制得新型配位聚合物{Zn[(BTDC)2(DMF)2]}4.(DMF)4(1),其结构经X-射线单晶衍射和元素分析表征。1属单斜晶系,空间群P2(1)/c,晶胞参数a=6.5913(13),b=22.813(5),c=16.315(3),V=2 450.5(9)3,Z=4,F(000)=1 112,cρalcd=1.455 g.cm-3,R1=0.040 2,wR2=0.082 4[I2σ(I)]。晶胞中每个锌原子与两个配体、两个配位的DMF溶剂分子和一个自由的DMF分子配位,共同组成zigzag一维链状结构。     

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%.     

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.     

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.