5-卤代-1H-1,2,4-三氮唑-3-羧酸乙酯及其衍生物的合成

以5-氨基-1H1,2,4-三氮唑-3-羧酸乙酯为原料,经Sandmeyer反应合成了5-X-1H-1,2,4-三氮唑-3-羧酸乙酯(X=C1,Br,I)(1a-1c),1a-1c再分别与α-2′,4′-二氟苯乙酮反应合成了3个5-卤代-1-1H-1,2,4-三氮唑-3-羧酸乙酯衍生物(2a-2c),其结构通过元素分析,IR,UV和^1H NMR进行了表征。     

3-甲基-4-氨基-5-[二-(4-氟苯基)]甲硫基-1,2,4-三氮唑席夫碱的微波合成及表征

微波辐射下,二氨基硫脲与乙酸反应制得3-甲基-4-氨基-1,2,4-三氮唑-5-硫酮(1),在无水乙醇中以三乙胺作为反应的缚酸剂,1与[二-(4-氟苯基)]甲基氯经微波辐射制得中间体3-甲基-4-氨基-5-[二-(4-氟苯基)]甲硫基-1,2,4-三氮唑(2),然后中间体2与芳香醛经缩合反应制得了10个Schiff碱3a～3j.合成的10个目标化合物通过熔点测定和质谱、红外光谱、核磁共振氢谱分析、元素分析对其结构进行确证.     

三氮唑配合物[Cu2(CH3COO)4(C4H8N4)2]·2CH3CN的合成及晶体结构

Cu(CH3COO)2 和4 氨基 3,5 二甲基 1,2,4 三氮唑反应制得标题化合物的单晶[Cu2(CH3COO)4(C4H8N4)2]·2CH3CN。晶体属三斜晶系 ,空间群 ,a=8.266(2),b=8.585(2),c=10.741(2) ,α=75.58(3),β=88.46(3),γ=86.35(3)°,V=736.7(3) 3 ,Z=1,Dc=1.509g·cm 3,F(000)=346,μ=1.502mm 1 。X 射线衍射结构分析表明 ,Cu2(CH3COO)4(C4H8N4)2 单元是中心对称的双核配合物 ,两个铜原子间距为2.698 。每个金属原子被围成四方锥的配位结构 ,四个乙酸根配体中最近的四个氧原子处在底面上[Cu O=1.965(3)～1.986(3) ] ,一个4 氨基 3,5 二甲基 1,2,4 三氮唑配体位于顶点位置Cu N=2.172 。     

1-[3′-(4"-甲氧基苯基)-5′-甲基异噁唑-4′-甲酰基]-4-芳基氨基硫脲及其衍生物的合成

以3,5-二取代异噁唑-4-甲酰肼为基本原料制备关键中间体1-(3-对甲氧基苯基-5-甲基异噁唑-4-基)-4-芳基氨基硫脲(3a～3c);3在不同条件下经关环反应制得含有3,5-二取代异噁唑的2-芳氨基噻二唑(4a～4c),2-芳氨基噁二唑(5a～5c)和3-[3′-(4"-甲氧基苯基)-5′-甲基-异噁唑4′-基)-4-芳基-1,2,4-三唑-5-硫酮(6a～6c);6与碘甲(乙)烷反应合成了4-芳基-5-[3′-(4″-甲氧基苯基)-5′-甲基异噁唑-4′-基]-3-甲(乙)硫基-1,2,4-三唑(7a～8c),其结构经1H NMR,IR,MS和元素分析表征,其中4,5,7和8未见文献报道.     

一些含三氮杂茂偶氮染料O,N供体的Zr(Ⅱ)配合物的合成、表征和抗微生物活性(英文)

合成了9种3-(2-羟基萘基-1-偶氮)-1,2,4-三氮唑(HL1),3-(2,4-二羟苯基-1-偶氮)-1,2,4-三氮唑(HL2),3-(2-羟基-3-羧基萘基-1-偶氮)-1,2,4-三氮唑(HL3),3-(2-羟基-5-溴苯基-1-偶氮)-1,2,4-三氮唑(HL4)和3-(2-羟基-5-甲基苯基-1-偶氮)-1,2,4-1,2,4-三氮唑(HL5)的Zr(Ⅱ)配合物并用元素分析,摩尔电导,磁矩,IR,UV-Vis,1H-NMR以及热分析(TGA和DTA)对其进行了表征。结果表明HL1-HL5以二齿一元配体方式通过偶氮的氮原子和羟基基团的氧原子与Zr(Ⅱ)离子配位生成单核配合物。用4种革兰氏阴性菌,即大肠杆菌(Escherichia coli),粘质沙雷氏菌(Serratia marcescens),阴沟肠杆菌(Enterobacter cloacae)和普通变形杆菌(Proteus vulgaris),以及2种真菌,即白色念珠菌(Candida albicans)和黑曲霉菌(Aspergillus niger)对配体及其配合物的生物学活性进行了研究。最小抑菌浓度(MICs)用纸上杯碟琼脂扩散法测定,结果表明在大多数情况下,金属化的配合物的抗微生物活性与自由配体相比有所增强。     

1-[3’-(4″-甲氧基苯基)-5’-甲基异噁唑-4’-甲酰基]-4-芳基氨基硫脲及其衍生物的合成

以3,5-二取代异噁唑-4-甲酰肼为基本原料制备关键中间体1-(3-对甲氧基苯基-5-甲基异噁唑-4-基)-4-芳基氨基硫脲(3a～3c);3在不同条件下经关环反应制得含有3,5-二取代异噁唑的2-芳氨基噻二唑(4a～4c),2-芳氨基噁二唑(5a～5c)和3-[3’-(4″-甲氧基苯基)-5’-甲基-异噁唑-4’-基)-4-芳基-1,2,4-三唑-5-硫酮(6a～6c);6与碘甲(乙)烷反应合成了4-芳基-5-[3’-(4″-甲氧基苯基)-5’-甲基异噁唑-4’-基]-3-甲(乙)硫基-1,2,4-三唑(7a～8c),其结构经1H NMR,IR,MS和元素分析表征,其中4,5,7和8未见文献报道。     

聚乙二醇支持的异噁唑啉衍生物的液相合成及其晶体结构

通过可溶性聚乙二醇支持的丙烯酸酯与由醛肟原位产生的腈氧化物进行1,3-偶极环加成反应,合成了PEG支持的异噁唑啉衍生物(3);3用甲醇钠-甲醇溶液解脱,高产率(84%～95%)地合成了4个3,5-二取代异噁唑啉衍生物(4a～4d),其结构经1H NMR, IR, EI-MS表征.采用X-射线单晶衍射测定了4d的晶体结构,4d属单斜晶系,C2/c空间群,晶胞参数:a=26.965 5(17)(A), b=9.370 5(6)(A), c=8.946 5(6)(A), α=γ=90°, β=97.226(2) °, V=2 242.6(3)(A)3, Z=8, Dc=1.299 mg·m-3, μ=0.094 mm-1, F(000)=928, R1=0.041 5, wR2=0.106 4.     

含1,2,4-三唑和1,3,4-噁二唑硫醚类化合物的合成及结构表征

在KOH溶液中,芳甲酰肼(2)与CS2生成钾盐3;然后3在水合肼作用下经过环化、取代、肼解得3-巯基-4-氨基-5-苯基-4H-1,2,4-三唑-乙酸酰肼(6),6再与CS2回流成环生成化合物5-(4-氨基-5-苯基-4H-1,2,4-三唑-3-硫烷基)-1,3,4-噁二唑-2-硫醇(7),最后7与取代苄基氯反应得目标化合物A1～A6,与芳基甲醛反应得终产物B1～B15.目标化合物的结构均经1H NMR,13C NMR,IR,MS或HRMS确证结构.     

C(3)-1,2,4-三氮唑取代的1,5-苯并硫氮杂■的合成及抑菌活性

设计合成了3类C(3)-1,2,4-三氮唑取代的1,5-苯并硫氮杂■化合物,2,3-二氢/2,5-二氢/2,3,4,5-四氢-3-(1,2,4-三氮唑)-4-芳基-1,5-苯并硫氮杂■.研究了中间体及目标产物的合成条件,确定了其中2个副产物的结构.目标产物的抑菌活性测试表明,2,3-二氢/2,5-二氢-3-(1,2,4-三氮唑)-4-芳基-1,5-苯并硫氮杂■对新生隐球菌和白色念珠菌表现出很高的抑制作用,在200μg/disc的浓度下,有4个化合物对新生隐球菌的抑制作用高于对照药物氟康唑,有3个化合物对白色念珠菌的抑制活性高于对照药物氟康唑.初步抑真菌构效关系研究表明,1,2,4-三氮唑环和C=N双键是2,3-二氢-3-(1,2,4-三氮唑)-4-芳基-1,5-苯并硫氮杂■抑真菌活性的关键药效团.     

3,5-二烷基-1,2,4-三唑衍生物构筑的两个Cu_4I_4簇配合物的合成、结构和荧光性质（英文）

以3,5-二甲(丙)基-4-氨基-1,2,4-三唑为配体,与CuI在H_2O/MeCN混合溶剂热合成了2个构型不同的Cu4I4超分子化合物{[Cu_2(aadmtrz)I2]·CH_3CN}n(1)和[Cu_2(dptrz)I]n(2)(aadmtrz=4-((1-氨乙基)-氨基)-3,5-二甲基-1,2,4-三唑,dptrz=3,5-二丙基-1,2,4-三唑),并进行了元素分析,红外,X射线粉末衍射及单晶衍射等表征。2个配合物中Cu4I4构型不同,配合物1中,Cu4I4簇连结成一个8环椅式-椅式结构,通过配体连接成(4,4)二维菱形格子结构;而配合物2中,Cu4I4簇呈畸变的立方烷结构,构成了含有19.5%孔隙率三维孔洞聚合物,其结构可简化为(3,4)-连接的拓朴结构。同时,在常温下研究了2个配合物的固体荧光性质。     

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.