酰氨基硫脲及其相关杂环衍生物的研究(Ⅴ)——1-(吡啶-4′-甲酰基)-4-芳基氨基硫脲及其相应的氮、硫、氧五员杂环化合物的合成

本文合成了一些新的1-(吡啶-4'-甲酰基)-4-芳基氨基硫脲(Ⅰ)、1,2,4-三唑啉-5-硫酮(Ⅱ)、1,3,4-噻二唑(Ⅲ)和1,3,4-嗯二唑(Ⅳ)衍生物。实验表明化合物(Ⅰ)在低浓度时对小麦、黄瓜等农作物的生长有显著的促进作用。     

N-5-(3-羧基-1,2,4-三唑基)-N'-芳酰基脲的合成与植物生长调节活性

20世纪 80年代以来 ,科学家发现三唑类化合物具有杀菌、除草和植物生长调节作用[1～ 3] ,酰基脲类化合物所表现出来的优良生物活性已引起化学家的重视[4～ 7] ,我们在对三唑席夫碱的研究中发现其中不少化合物具有较高的植物生长调节活性[8\〗,而含三唑环的芳酰基脲还未见报道。为了寻找高活性的新型植物生长调节物质 ,本文采用亚结构连接法 ,在芳酰基脲结构中引入三唑环 ,设计合成了 8个新的含三唑基的芳酰基脲 ,其合成路线如下 :ArCONCO　Ⅰ+H2 N NNNHCOOH DMF～ 60℃ ArCONHCONH NNNHCOOH　ⅡAr :Ⅱa　C6H5—Ⅱb　o BrC6…     

含三唑啉硫酮槟榔碱衍生物的合成和生物活性

烟酸经酯化、肼解、与取代芳酸异硫氰酸酯缩合成 1 (3 吡啶甲酰基 ) 4 芳基氨基硫脲 (2 ) ,2经环合生成 2 (3 吡啶 ) 4 芳基 1,3,4 三唑啉 5 硫酮 (3) ,接着用碘甲烷对吡啶环季铵化得相应的季铵盐 4 ,4用硼氢化钠还原可得目标物 2 (1 甲基 1,2 ,5 ,6 四氢吡啶 3 基 ) 4 芳基 1,2 ,4 三唑啉 5 硫酮 (5 ) .对所合成的目标化合物进行了舒张血管活性实验     

含吡啶环大环多胺的合成及其与Cu(Ⅱ)的络合行为

本文以2,6-二溴甲基吡啶和对甲苯磺酰胺钠盐合成含吡啶环大环多胺,得到了尚未见文献报道的含四个吡啶环的三十二环胺. 2,6-二溴甲基-吡啶与甲苯磺酰胺钠盐在无水乙醇回流温度下得到1,9,17,25-四甲苯磺酰基大环多胺.用浓硫酸脱去N-甲苯磺酰基化合物的甲苯磺酰基, 生成标题大环多胺化合物. 配体与Cu(Ⅱ)的络合由紫外吸收光谱测定. 实验结果表明配体确与Cu^2^+以1:2络合成为双核络合物.     

酰氨基硫脲及其相关杂环衍生物的研究(Ⅹ)——1-(4′-吡啶甲酰基)-4-芳酰胺基硫脲类化合物环化反应的研究

本文研究1-(4′-吡啶甲酰基)-4-芳酰胺基硫脲(Ⅰ)在碱催化条件下的环化反应。结果表明,当(Ⅰ)芳环连接吸电子基如硝基、卤素或推电子取代基如甲基和甲氧基等时,均环化为3-(4′-吡啶基)-4-芳酰基-1,2,4-三唑啉-5-硫酮(Ⅱ),通过质谱裂解碎片分析确定其结构,并初步评价部分化合物对结核菌的抑制作用。     

一种具备巯基点击化学功能的二硫代酯RAFT链转移剂的合成

以2,2-二硫二吡啶,2-巯基乙醇为原料,醋酸为催化剂,合成了2-羟乙基-二硫吡啶(PⅠ)。以PⅠ、4-氰基-4-(硫代苯甲酰)戊酸(PⅡ)为原料,1-(3-二甲氨基丙基)-3-乙基碳二亚胺盐酸盐(EDC)、4-二甲氨基吡啶(DMAP)为催化剂,合成了一种新的可逆加成-断裂链转移自由基聚合(RAFT)链转移剂4-氰基-4-(硫代苯甲酰)戊酸-2-二硫吡啶乙酯(PⅢ)。以PⅢ为RAFT链转移剂,偶氮二异丁腈(AIBN)为引发剂,甲基丙烯酸甲酯(MMA)为单体,采用RAFT制备了聚甲基丙烯酸甲酯(PMMA)。用1 H-NMR分析了链转移剂的的分子结构,用GPC测得PMMA聚合物的分子量及其分布。结果表明:能用于巯基点击化学的二硫吡啶基团被接到PⅡ的末端,成功制备了一种具备巯基点击化学功能的二硫代酯RAFT链转移剂(PⅢ),利用PⅢ,通过RAFT聚合制备了分子量分布狭窄的PMMA聚合物。     

1,3—二氧戊环—4—甲醇酯—1H—咪唑相转移催化合成法的研究

1,3-二氧戊环-1H-咪唑类化合物是一类高效、广谱、低毒的杀菌剂。我们以(Ⅰ)为先体,合成了一系列4-甲醇酯类化合物(Ⅱ),其中多数化合物尚未见报道。以吡啶为溶剂的合成方法,反应周期长,收率较低。在相转移催化条件下,用酰氯与(Ⅰ)作用合成(Ⅱ),反应条件温和,操作简便,产物收率较高。     

6,6-二烷基富烯同α-吡啶甲基锂和α-吡啶基锂的反应——吡啶基取代环戊二烯及其铁衍生物的合成和结构

6,6-二烷基富烯和6,6-多亚甲基富烯同α-吡啶甲基锂发生环外双键的加成反应。形成的取代环戊二烯基锂经水解或与二氯化铁反应,分别制得α-吡啶烷基环戊二烯和α-吡啶烷基二茂铁。α-吡啶基锂与6,6-四亚甲基富烯进行α-摄氢反应,与6,6-五亚甲基富烯则发生环外双键的加成反应。 测定了双(η~5-1-(α-吡啶甲基)环戊基环戊二烯基)铁的分子结构。晶胞中含有三个分子,每个分子处在各自独立的位置。根据分子中两个环戊二烯基环上取代基的相对指向,分子Ⅰ与Ⅱ可以认为具有相同的构象,而分子Ⅲ则是它们的镜像。     

三个稀土-主族三金属Ln(Ⅲ)-Sr(Ⅱ)-K(Ⅰ)配合物的结构与发光性质

用2,4,6-吡啶三甲酸和稀土钐、镝或钆的高氯酸盐溶液、碳酸锶、碳酸钾在180℃水热条件下进行反应,制备出3个含有3种金属离子的配位聚合物[Ln Sr K(ptc)2(H2O)]n(Ln=Sm(1)、Dy(2)、Gd(3),H3ptc=2,4,6-吡啶三甲酸)。X射线单晶衍射分析表明三者具有相同的结构,属三斜晶系,P1空间群。配合物中配体2,4,6-吡啶三甲酸根以2种不同的配位方式与3种金属离子配位,一种方式中连接了7个金属离子,另一种方式中连接了8个金属离子。Ln(Ⅲ)为八配位,与羧基上的6个氧原子和2个吡啶环上的2个氮原子配位;Sr(Ⅱ)也是八配位,配位原子均为氧原子;K(Ⅰ)与5个氧原子配位。荧光发射光谱表明,钐和镝的配合物在紫外光激发下均发射Sm(Ⅲ)和Dy(Ⅲ)两种离子的特征荧光,钆的配合物在紫外光激发下由于发生荷移跃迁而发射绿色荧光。     

葛根素衍生物的合成、表征及衍生化反应机理

合成了葛根素的7,4'-二丙基(Ⅰ), 7-单丙基(Ⅱ)和4'-单丙基(Ⅲ)三种取代衍生物. 其中7-丙基葛根素Ⅱ属于新型取代衍生物; 变温1H NMR和理论计算结果表明, 在300 K时, 葛根素和4'-丙基葛根素(Ⅲ)以单一构型存在; 而7,4'-二丙基葛根素(Ⅰ)和7-丙基葛根素(Ⅱ)则存在两种核磁可分辨的旋转异构体, 当温度升至330 K时, 两种异构体可以相互转化; 通过对比分析葛根素及其衍生物脱质子产物的紫外可见吸收光谱并结合理论计算, 确定了A环上7位酚羟基比B环上4'位酚羟基先脱去质子, 并由此进一步阐明了葛根素衍生化反应机理以及在抗氧化作用中可能的活性位点和结构活性关系.     

二氟亚烷基卡宾与甲醛环加成反应机理的理论研究

用二阶微扰理论研究单重态二氟亚烷基卡宾与甲醛发生的环加成反应机理,采用MP2/6-31G*方法计算了势能面上各驻点的构型参数、振动频率和能量.结果表明,单重态二氟亚烷基卡宾与甲醛的环加成反应主要有两种反应通道,通道1中,两个反应物经a,b和c三条反应途径生成三元环构型的产物P1,其中途径c是主反应途径,该途径有两步组成:(Ⅰ)二氟亚烷基卡宾与甲醛生成了1个富能中间体(INT1c),是无势垒放热反应,放出能量为219.18kJ/mol;(Ⅱ)中间体(INT1c)异构化为产物二氟亚烷基环氧乙烷,其势垒为134.71kJ/mol.通道2的反应途径由三步组成:(Ⅰ)反应物首先生成了1个富能中间体(INT1b),为无势垒的放热反应,放出的能量142.77kJ/mol;(Ⅱ)中间体(INT1b)异构化成另一中间体(INT2),其势垒为22.31kJ/mol;(Ⅲ)中间体(INT2)异构化成四元环构型产物P2,其势垒为11.98kJ/mol.     

双异薄荷醇黄原酸镍的吡啶加合物(英)

The reaction of homochiral bis(2-isopropyl-5-methylcyclohexyl xanthalato) nickel(Ⅱ) with pyridine yields an chiral adduct bis(2-isopropyl-5-methylcyclohexyl xanthalato)(dipyridine) nickel(Ⅱ) (Ⅰ) in which the coordination geometry of the central Ni atom displays a slightly distorted octahedron composed of four S atoms from two xanthalato ligands and two N atoms from pyridine rings. CCDC: 252342.     

Assembly of zinc metallacrowns with an α-amino hydroxamic acid ligand

In the assembly of metallacrowns for molecular recognition, luminescence, and molecular magnetism applications, substituting the ring ion can have profound effects on the structure, stability, and physical properties of the inorganic macrocycle. The assembly of Zn(Ⅱ) metallacrowns with an α-amino hydroxamic acid ligand (pheHA) was investigated to compare the assembly behavior with the well studied metallacrowns containing Cu(Ⅱ) and Ni(Ⅱ). Electrospray ionization mass spectrometry reveals that the benchmark species Zn5(pheHA)42+ and LnZn5(pheHA)53+ assemble in pyridine, which is consistent with the behavior of Cu(Ⅱ) and Ni(Ⅱ). A LnZn4(pheHA)43+ species is also observed in a 1:1 DMF-pyridine mixture. An unprecedented La(Ⅲ)[16-MCZn(Ⅱ),pheHA,HpheHA-6]5+ complex was crystallographically characterized that possesses unusual C2 symmetry. These results provide insights into the design of functional metallacrowns through ring ion substitution.     

Synthesis of proton‐ionizable acyclic,macrocyclic and macrobicyclic compounds containing one or two triazole groups

New acyclic, macrocyclic and macrobicyclic compounds containing one or two proton‐ionizable triazole groups are prepared and characterized. The series includes six podands, a macrocycle with one triazole and one pyridine unit in the ring, a bis‐triazolo macrocycle with four pentafluorobenzyl substitutents, and two bis(crown ethers) with a triazolo group connecting the two polyether rings. The solid‐state structure and solubility in supercritical carbon dioxide are determined for the bis‐triazolo macrocycle with pendant pentafluorobenzyl groups.     

若干杂环模型化合物的热氧化稳定性

<正> 自五十年代以来,耐热的杂环高分子取得了很多进展。曾报道聚酰亚胺、聚苯并咪唑、聚苯并噻唑、聚苯并噁唑、聚喹噁林及聚苯并噁嗪酮等都是性能较好的耐热高分子,而有些在工业上已得到应用。我们在进行芳杂环二腈聚合的工作中,曾将上述杂环结构引入二腈,以期获得性能优良的耐热高分子,所得结果已陆续报道。     

烟酸铬(Ⅲ)的配位结构与生物活性关系

合成了2种新型吡啶-3-羧酸(烟酸)铬(Ⅲ)螯合物,通过元素分析、热分析、红外光谱和电子光谱证明烟酸作为双齿配位体,形成具有3个六员环的螯合物Cr(Nic)3和具有2个六员环与2个H2O单体的混型配合物[Cr(Nic)2(H2O)2]Cl。通过使用效能等试验表明,在猪饲料中添加不同配位结构的烟酸铬均有明显提高饲料利用率、促进生长和显著提高机体对葡萄糖的清除率等作用。试验还表明,双齿配位的烟酸铬具有较高的生物活性、无毒、饲用后在肌体内无残留,作为饲料添加剂具有广阔的应用前景。     

异双核X-M之间的磁耦合交换作用: Keggin型杂多酸衍生物[M(H2O)XW11O39]7-(X=FeⅢ, CoⅢ; M=CoⅡ)的密度泛函研究

采用DFT-BS方法研究异双核的Keggin型杂多酸衍生物[M(H2O)XW11O39]7-(Ⅰ: X=FeⅢ, M=CoⅡ; Ⅱ: X=CoⅢ, M=CoⅡ)的磁耦合作用, 计算得到耦合常数(J)为负值, 表明所研究体系具有反铁磁性; J值大小顺序为|J(Ⅰ)|<|J(Ⅱ)|, 说明磁耦合作用增强; 体系Ⅰ与Ⅱ相比, X由FeⅢ变成CoⅢ, M不变, 桥氧原子Ob和Ob2(O′b2)上的自旋密度增大, 进一步从相关BS态的磁轨道比较得出, 体系Ⅱ中轨道重叠程度大于体系Ⅰ, 结果使X-M之间的反铁磁耦合作用加强.     

Triazole: a unique building block for the construction of functional materials

Over the past 50 years, numerous roads towards carbon-based materials have been explored, all of them being paved using mainly one functional group as the brick: acetylene. The acetylene group, or the carbon-carbon triple bond, is one of the oldest and simplest functional groups in chemistry, and although not present in any of the naturally occurring carbon allotropes, it is an essential tool to access their synthetic carbon-rich family. In general, two strategies towards the synthesis of π-conjugated carbon-rich structures can be employed: (a) either the acetylene group serves as a building block to access acetylene-derived structures or (b) it serves as a synthetic tool to provide other, usually benzenoid, structures. The recently discovered copper-catalysed azide-alkyne cycloaddition (CuAAC) reaction, however, represents a new powerful alternative: it transforms the acetylene group into a five-membered heteroaromatic 1H-1,2,3-triazole (triazole) ring and this gives rise to new opportunities. Compared with all-carbon aromatic non-functional rings, the triazole ring possesses three nitrogen atoms and, thus, can serve as a ligand to coordinate metals, or as a hydrogen bond acceptor and donor. This Feature Article summarises examples of using the triazole ring to construct conjugation- and/or function-related heteroaromatic materials, such as tuneable multichromophoric covalent ensembles, macrocyclic receptors or responsive foldamers. These recent examples, which open a new sub-field within organic materials, started to appear only few years ago and represent "a few more bricks" on the road to carbon-rich functional materials.     

Syntheses and Crystal Structures of 4-Amino-3- （3-hyd roxyp ropyl）- 1H-1,2,4-triazole-5（4H）-thione and 6-（4-Biphenylyl）-3-（3-hydroxypropyl）-7H-1,2,4-triazolo[3,4-b][1,3,4]thiadiazine

1INTRODUCTION It has been reported that3,6-disubstituted-7H-1,2,4-triazolo[3,4-b][1,3,4]thiadiazines have a broad spec-trum of bioactivities,such as antimicrobial[1],antibac-terial,antifungal[2],anti-inflammatory[3],diuretic[4],an-thelmintic and analgesic[5].They can also be used as plant-growth regulating agents[6],photographic coup-lers,dyes for improved preservability and absorption characteristics,and inhibitors of malignant cellularZOU K.H.et al.:Syntheses and Crystal Structures o…     

Synthesis and Crystal Structure of N-[(3aR,4R,4aR,5aS,6S,6aS)-1,3-Dioxooctahydro-4,6-ethenocyclopropa[f]lisoindol-2(1H)-yl]-3-(trifluoromethyl)phenylmethanimine

The crystal structure of the title compound (C19H15F3N2O2, Mr= 360.33) was determined by single-crystal X-ray diffraction. The crystal belongs to triclinic, space group P(1), with a = 6.5604(7), b = 13.9614(16), c = 18.1790(18) (A), α = 102.749(7),β = 97.542(6), γ = 94.355(4)°, V= 1600.5(3) (A)3, Z = 4, Dc = 1.495 g/cm3, λ(MoKα) = 0.71070, F(000) = 744, μ(MoKα) = 0.122mm-1, R = 0.0434 and wR = 0.1051. A total of 7590 unique reflections were collected, of which 5429 with |F|2 ≥ 2σ|F|2 were observed. The two cyclohexene rings in the molecule adopt boat-boat conformations with the deviations of ring atoms C(9) and C10 from the C(5)/C(6)/C(7)/C(8) plane (Ⅰ) by 1.1204 (0.0023) and 1.1132 (0.0023) (A), respectively, whereas from the C(2)/C(3)/C(5)/C(8)plane (Ⅱ) by 1.1627 (0.0022) and 1.1818 (0.0021) (A), respectively. In the cyclopropane and lactam rings, atoms C(11) and N(1) point towards the double bond of C(9)-C(10) and the dihedral angle between the ring plane (Ⅲ) containing C(1), C(2), C(3) and C(4) and plane (Ⅳ) consisting of C(6),C(7) and C(11) is 55.76 (0.07)°. The dihedral angles between planes Ⅳ and Ⅰ and Ⅱ and Ⅲ are 63.58 (0.07)° and 58.10 (0.06)°, respectively. The dihedral angle between the benzene ring C(13)～C(18) and plane Ⅳ is 42.41 (0.06)°.