Formation of 2D water morphologies in the lattice of the salt with [Cu2(OH)2(H2O)2(phen)2]2+ as cation and 4,6-dimethyl-1,2,3-triazolo[4,5-d]pyrimidin-5,7-dionato as anion

The crystal structure of the compound [Cu₂(OH)₂(H₂O)₂(phen)₂](dmax)₂·10H₂O is presented, where phen = 1,10-phenanthroline and dmax  =  4,6-dimethyl-1,2,3-triazolo[4,5-d]pyrimidin-5,7-dionato. The cationic species is a dinuclear hydroxo bridged Cu(II) complex, the charge of which is balanced by the heterocyclic anionic ligand. The main focus of the work is the analysis of the H-bond network, which includes two different two-dimensional morphologies, mostly built by water molecules. The first one includes a monodimensional tape superstructure built exclusively by interstitial water, with alternating four-member and six-member water clusters, the tapes being linked by the cationic complexes via coordinated water and hydroxyl groups. The second is formed by water molecules and the triazolopyrimidine anions. Both morphologies include H-bond rings of different sizes.     

微波辐射合成5-氨基-噻唑[4,5-d]嘧啶-2(3H)-酮

以硫脲和氯乙酸为原料,在无溶剂和350 W微波辐射4 m in条件下,缩合生成中间体2,4-噻唑烷二酮(Ⅰ)产率91.5%;随后在无溶剂和400 W微波辐射5 m in条件下,通过V ilsm e ier甲酰化反应,生成中间体4-氯-5-甲酰基噻唑-2(3H)-酮(Ⅱ),产率86.7%;最后以正丙醇为溶剂,450 W微波辐射7 m in条件下,成环得到5-氨基-噻唑[4,5-d]嘧啶-2(3H)-酮(Ⅲ),产率80.5%。反应总产率为63.9%。合成产物与中间体的结构经1HNMR,MS和元素分析确认。     

噻吩并[3,2-d]嘧啶-4(3H)-酮的合成工艺研究

报道了一种噻吩并[3,2-d]嘧啶-4(3H)-酮的简便、高效合成新工艺。巯基乙酸乙酯和2-氯丙烯腈在乙醇钠作用下进行环合制得3-氨基噻吩-2-甲酸乙酯,然后在乙酸乙酯中与氯化氢气体成盐进行分离。3-氨基噻吩-2-甲酸乙酯的盐酸盐直接与过量的甲酰胺关环制得噻吩并[3,2-d]嘧啶-4(3H)-酮,两步总产率约80%。     

5-(4-叠氮呋咱基)-[1,2,3]三唑[4,5-c]并呋咱内盐的合成、晶体结构及性能

以3,4-二氨基呋咱为原料,经重氮化-叠氮化、氧化-环化等反应合成了一种新型无氢富氮含能材料5-(4-叠氮呋咱基)-[1,2,3]三唑[4,5-c]并呋咱内盐(AFTF);采用红外光谱、核磁共振、元素分析等方法表征了目标物的结构;获得了AFTF的单晶并进行了晶体结构解析;采用DSC方法研究了AFTF的热稳定性,初步探讨了氧化-环化反应机理;采用Gaussian 09程序CBS-QB3方法计算了AFTF的固相生成热,基于晶体密度和固相生成热,利用EXPLO5爆轰软件预估了AFTF的爆轰性能。结果表明,化合物AFTF晶体为正交晶系,空间群为P 2(1)2(1)2(1),晶胞参数为:a=8.1782(17),b=8.6446(18),c=11.521(2),V=814.5(3)3,Z=4,μ=0.151 mm^-1,F(000)=440;AFTF的熔点为101.02℃,热分解温度为186.39℃;AFTF晶体密度为1.795 g/cm 3(296 K),氮含量为63.6%,理论爆速为8.982 km/s,爆压为33.5 GPa,生成热为1178.9 kJ/mol,爆热为6450.8 kJ/kg,表明AFTF是一种爆轰性能优良的无氢富氮高能量密度化合物,有望应用于高能推进剂或气体发生剂领域;低熔点特性有望使其作为熔铸炸药载体使用。     

Reaction of ethyl N-(6-ethoxycarbonyl-2-methylthiothieno[2,3-d]-pyrimidin-5-yl) formimidate with alkyl- and arylhydrazines: Formation of modified thieno[2,3-d]pyrimidines and thieno[2,3-d:4,5-d]dipyrimidin-4-ones

The reaction of ethyl N-(6-ethoxycarbonyl-2-methyl-thiothieno[2,3-d]pyrimidin-5-yl)formimidate ( 1 ) with methyl-hydrazine, N,N′-dimethyl- and N,N′-diphenylhydrazines separately in refluxing ethanol resulted in hydrolysis of formimidate group to give ethyl 5-amino-2-methylthiothieno[2,3-d] pyrimidine-6-carboxylate ( 2 ). The reaction on 1 with methyl-hydrazine without solvent afforded ethyl 5-amino-2-(1-methyl-hydrazino)thieno[2,3-d]pyrimidine-6-carboxylate ( 3 ), which underwent hydrazone formation with p-nitrobenzaldehyde to give 4 . Treatment of 1 with N,N-dimethylhydrazine afforded a mixture of 3-dimethylamino-7-methylthiothieno[2,3-d:4,5-d']dipyrimidin-4(3H)-one ( 5 ) and 2 . Displacement of methylthio group in 5 with morpholine, piperidine and 4-methylpiperazine gave the corresponding 7-substituted derivatives 6a-c . The reaction of 1 with para-substituted phenylhydrazines resulted in the formation of 3-(p-substituted phenylamino)7-methylthiothieno[2,3-d:4,5-d']dipyrimidin-4 (3H)ones ( 7a-c ).     

萘并吡喃并[2,3-d]嘧啶-4(3H)-酮衍生物的合成与表征

通过氮杂Wittig反应合成了7种萘并吡喃并[2,3-d]嘧啶-4(3H)-酮衍生物。首先用2-萘酚、氰乙酸乙酯和芳醛通过Knoevenagl-Cope缩合得到2-氨基萘并吡喃(Ⅰ),(Ⅰ)再与三苯基膦反应得到膦亚胺中间体(Ⅱ)。(Ⅱ)与芳基异氰酸酯采用aza-Wittig反应得到碳二亚胺(Ⅲ)。(Ⅲ)再分别与胺、醇、酚反应合成了萘并吡喃并[2,3-d]嘧啶-4(3H)-酮Ⅳ(a-g)。目标化合物结构经1H-NMR、MS和IR进行了表征。试验考察了亲核试剂及反应条件对产品收率的影响。结果表明,亲核试剂空间位阻小反应速度较快,收率高;若有吸电子基团时,反应时间缩短。     

Lead(II) in a sulfur-rich environment: Synthesis and molecular structure of the first dinuclear bis(mercaptoimidazolyl)methane complex

The first dinuclear bis(mercaptoimidazolyl)methane metal complex, the lead(II) derivative [Pb₂(Bmm^Me)₅](ClO₄)₄, has been prepared and fully characterized using a combination of analytical and spectroscopic techniques. X-ray crystallography confirmed the presence in the solid state of two dicationic [Pb(Bmm^Me)₂]²⁺ fragments bridged by the fifth Bmm^Me ligand, which uses an unprecedented unidentate:bidentate (μ-κ¹-S:κ²-S,S) coordination mode to link the two metal centers.     

8-(3-氯苯基)-3-甲硫基-1-苯基-吡唑并[3,4-d][1,2,4]三唑并[1,5-a]嘧啶-4-酮衍生物的合成与表征

以吡唑膦亚胺、3-氯苯基异氰酸酯和取代苯氧乙(丙)酰肼为原料,通过串联氮杂Wittig关环反应合成了6个未见文献报道的化合物8-(3-氯苯基)-3-甲硫基-1-苯基-吡唑并[3,4-d][1,2,4]三唑并[1,5-a]嘧啶-4-酮衍生物((1)a～(1)f),通过核磁共振氢碳谱和HRMS等确证进行了表征.     

8-(3-氯苯基)-3-甲硫基-1-苯基-吡唑并[3,4-d][1,2,4]三唑并[1,5-a]嘧啶-4-酮衍生物的合成与表征

以吡唑膦亚胺、3-氯苯基异氰酸酯和取代苯氧乙(丙)酰肼为原料,通过串联氮杂Wittig关环反应合成了6个未见文献报道的化合物8-(3-氯苯基)-3-甲硫基-1-苯基-吡唑并[3,4-d][1,2,4]三唑并[1,5-a]嘧啶-4-酮衍生物((1)a～(1)f),通过核磁共振氢碳谱和HRMS等确证进行了表征.     

8-(3-氯苯基)-3-甲硫基-1-苯基-吡唑并[3,4-d][1,2,4]三唑并[1,5-a]嘧啶-4-酮衍生物的合成与表征

以吡唑膦亚胺、3-氯苯基异氰酸酯和取代苯氧乙(丙)酰肼为原料,通过串联氮杂Wittig关环反应合成了6个未见文献报道的化合物8-(3-氯苯基)-3-甲硫基-1-苯基-吡唑并[3,4-d][1,2,4]三唑并[1,5-a]嘧啶-4-酮衍生物((1)a～(1)f),通过核磁共振氢碳谱和HRMS等确证进行了表征.     

Reaction of pyridothiouracil with hydrazonoyl halides and the antimicrobial activity of the products,pyrido[2,3-d][1,2,4]triazolo-[4,3-a]pyrimidin-5(1H)-one derivatives

New functionalized pyrido[2,3-d][1,2,4]triazolo[4,3-a]pyrimidin-5(1H)-one derivatives were synthesized via reaction of the hydrazonoyl halides with 7-(4-nitrophenyl)-5-phenyl-2,3-dihydro-2-thioxopyrido[2,3-d]pyrimidin-4(1H)-one or its 2-methylthio derivative. The biological activity of the products has been evaluated. The mechanism and the regioselectivity of the studied reactions have been discussed.     

MgO-CeO2 nanocomposite: efficient catalyst for the preparation of 2-aminothiophenes and thieno[2,3-d]pyrimidin-4(3H)-one derivatives

MgO-CeO₂ nanocomposite was prepared by a co-precipitation method and characterized by X-ray diffraction (XRD), FE-SEM, and particle size distribution analysis. The XRD pattern shows the cubic phase of cerium oxide as the dominate phase. FE-SEM images show the homogeneity distribution of magnesium and cerium oxides in the sample. The mean particle size of nanocomposite determined by the dynamic light scattering technique is 66?nm. The catalytic activity of MgO-CeO₂ nanocomposite was examined on the synthesis of 2-aminothiophenes and thieno[2,3-d]pyrimidin-4(3H)-one derivatives. In all cases, products were obtained in good to excellent yields.     

Synthesis of (3aS,6aR) -1,3-dibenzyl-tetrahydro-4H-furo [ 3,4-d ] imidazole-2,4 ( 1H ) -dione by stereoselective reduction

以顺-1,3-二苄基-5-[( 1S,2S)-(+)-苏式-1-羟甲基-2-(对硝基苯基)-2-羟乙基]-四氢-4H-吡咯并[3,4-d]咪唑-2,4,6-三酮为原料,经单乙酰化、NaBH4还原和酸水解得到标题化合物,与直接还原或是先经双乙酰化再还原的工艺相比,单乙酰化后再还原的选择性高达97.25％.并对单乙酰化物和双乙酰化物结构做了X单晶衍射测定,单乙酰化物的原子空间排布更利于选择性还原.     

A first report of the complexes of 5,11,17,23-tetra-tert-butyl-25,27-diethoxycarboxymethoxy-26,28-dihydroxycalix[4]arene with Mn(II), Fe(III), Co(II), Ni(II), Cu(II) and Zn(II)

Totally six dinuclear complexes of Mn(II), Fe(III), Co(II), Ni(II), Cu(II) and Zn(II) of calix[4]arene derivatized with two pendants possessing terminal –COOH functions at two of its alternate phenolic –OH groups were synthesized for the first time and were well characterized.     

3-苯基-2-（4-叔丁基苯氧基）-3＇-氧环己烷并噻吩并[2，3-d]嘧啶-4（3H）-酮的合成及其与BSA的相互作用

通过Aza-Wittig反应。碳二亚胺与酚类化合物在碱性催化条件下成环,合成了3-苯基-2-（4-叔丁基苯氧基）-3’-氧环己烷并噻吩并[2,3-胡嘧啶-4（3H）-酮（PTP）。在生理条件下。采用紫外吸收光谱法及荧光光谱法研究了PTP与牛血清白蛋白（BSA）的相互作用。并采用同步荧光法考察了PTP的加入对BSA构象的影响。结果表明,PTP对BSA的荧光猝灭机理为静态猝灭过程。PTP与BSA的结合反应为自发进行,反应中主要作用力是氢键和范德华力,两者的结合位点数为1、结合距离为1．78nm．PTP的加入对BSA构象没有明显影响。     

吡唑并嘧啶酮氧苯氧丙酸甲酯类化合物的合成与除草活性

膦亚胺与芳基异氰酸酯、取代酚的连续aza—Wittig反应和关环反应合成了新的2-[4-(1-苯基-3-苄硫(砜)基-5-取代芳基-4(5H)-酮-1H-吡唑[3,4-d]并嘧啶-6-氧)苯氧基]丙酸甲酯类化合物,其产物结构经元素分析、^1HNMR、EI—MS和IR确证。初步生物活性表明,部分化合物对单子叶和双子叶杂草的根具有很好的抑制作用。     

Opto-electrical and density functional theory analysis of poly(2,7-carbazole-alt-thieno[3,4-c]pyrrole-4,6-dione) and photovoltaic behaviors of bulk heterojunction structure

To increase open-circuit voltage (V_oc), we introduced thieno[3,4-c]pyrrole-4,6-dione (TPD) moieties which has unsubstituted and substituted thiophene spacers. Poly(2,7-carbazole-alt-TPD) derivatives, namely PCDTTPD and PCDHTTPD, were copolymerized with 2,7-carbazole through Suzuki coupling reaction. An increase in the molecular weight and a decrease in the highest occupied molecular orbital (HOMO) energy level are confirmed. Steric hindrance caused by rotational dynamics was measured by density functional theory calculation. When the resulting polymers, PCDHTTPD, were used to fabricate a bulk heterojunction device with PC₇₁BM, V_oc increased to 0.84 V, whereas the short-circuit current density (J_sc) decreased to 0.93 mA/cm² because of poor charge dissociation.     

Synthesis and properties of dysprosium complex with 2-(5-nitro-1H-benzo [d] [1,2,3] triazol-l-yl ) acetic acid ligand and 1,10-phenanthroline

采用溶液合成法,合成了标题化合物,通过元素分析、摩尔电导率、紫外光谱、红外光谱和热分析法确定配合物的组成为Dy(L) 3phen·1.5H2O(HL =5-硝基苯并三唑-1-乙酸;phen=1,10-邻菲啰啉).荧光光谱表明:镝配合物的荧光强度较强,说明配体5-硝基苯并三唑-1-乙酸和1,10-邻菲啰啉是很好的敏化剂.     

Formation of an unusual copper(II) complex from the degradation of a novel tricopper(II) carbohydrazone complex

An unusual copper(II) complex [Cu(L^1a)₂Cl₂] CH₃OH·H₂O·H₃O⁺Cl⁻ (1a) was isolated from a solution of a novel tricopper(II) complex [Cu₃(HL¹)Cl₂]Cl₃·2H₂O (1) in methanol, where L^1a is 3-(2-pyridyl)triazolo[1,5-a]-pyridine, and characterized with single crystal X-ray diffraction study. The tricopper(II) complex of potential ligand 1,5-bis(di-2-pyridyl ketone) carbohydrazone (H₂L¹) was synthesized and physico-chemically characterized, while the formation of the complex 1a was followed by time-dependant monitoring of the UV–visible spectra, which reveals degradation of ligand backbone as intensity loss of bands corresponding to O → Cu(II) charge transfer.     

Phase behavior and optical- and mechanical properties of the binary system isotactic polypropylene and the nucleating/clarifying agent 1,2,3-trideoxy-4,6:5,7-bis-O-[(4-propylphenyl) methylene]-nonitol

The phase behavior and optical- and selected mechanical properties of the binary system consisting of isotactic polypropylene (i-PP) and a new sorbitol-based nucleating and clarifying agent, 1,2,3-trideoxy-4,6:5,7-bis-O-[(4-propylphenyl) methylene]-nonitol (TBPMN), were investigated. Temperature/composition diagrams of the binary were found to be of the simple monotectic type, similar to those of, among others, the previously investigated i-PP/1,3:2,4-bis(3,4-dimethyldibenzylidene)sorbitol (DMDBS). Liquid-liquid phase separation was observed in binaries comprising more than ∼5% w/w TBPMN, indicative of enhanced miscibility of the new additive with i-PP when compared with that of DMDBS. At TBPMN contents ≥0.1% w/w the optical properties haze and clarity progressively improved to remarkable levels with increasing concentration of the nucleating agent up to the onset of liquid-liquid phase separation, above which they deteriorated. The enhanced solubility in i-PP of the new clarifying agent on the one hand required uneconomically higher concentrations than previous members of the sorbitol family to be effective, but on the other, the superior optical properties of the system may permit manufacturing of clarified products of increased thickness.