Synthesis and Crystal Structure of the Copper(Ⅱ) Complex with 1,10-Phenanthroline-5,6-dione

The complex Cu(phon)(NO3)2(CH3CN) (phon = 1,10-phenanthroline-5,6-dione) has been synthesized and characterized by elemental analysis, infrared and UV-Vis spectra. X-ray diffraction analysis at room temperature indicates that the complex crystallizes in orthorhombic system, space group P212121 with a = 8.353(1), b = 11.299(2), c = 17.764(2) A, V= 1676.5(4) A3, Z = 4, C14H9CuN5O8, Mr = 438.8, Dc = 1.739 g/cm3, F(000) = 884 and μ(MoKα) = 1.361 mm-1. The final R and wR factors for the observed reflections with I > 2σ(I) are 0.0353 and 0.0855, respectively. R = 0.0432 and wR = 0.0899 for all data. The structure of the title complex consists of a neutral mononuclear entity. The central Cu (II) atom is five-coordinated by two nitrogen donors of one ligand, two unidentate NO3- ions and one CH3CN molecule. The coordination geometry of Cu (II) can be considered as a distorted trigonal bipyramidal configuration. The complex ability of the NO3-ion has more effect than that of the ClO4- ion on the structure of the complex.

Sol-Gel Derived Carbon Ceramic Electrode Bulk-Modified with Tris(1,10-phenanthroline-5,6-dione)iron(II) Hexafluorophos-phate and Its Use as an Amperometric Iodate Sensor

A surface-renewable tris(1, 10-phenanthroline-5,6-dione)iron (Ⅱ)hexafluorophosphate (FePD) modified carbon ceramic electrode was constructed by dispersing FePD andgraphite powder in methyltrimethoxysilane (MTMOS) based gels. The FePD-modified electrode presentedpH-dependent voltammetric behavior, and its peak currents were diffusion-controlled in 0.1 mol/LNa_2SO_4 + H_2SO_4 solution (pH = 0.4). In the presence of iodate, clear electrocatalytic reductionwaves were observed and thus the chemically modified electrode was used as an amperometric sensorfor iodate in common salt. The linear range, sensitivity, detection limit and response time of theiodate sensor were 5 x 10^(-6)―1 x 10~2 mol/L, 7.448 μA·L/mmol, 1.2 x 10^(-6) mol/L and 5 s,respectively. A distinct advantage of this sensor is its good reproducibility of surface-renewal bysimple mechanical polishing.

Synthesis,Crystal Structure and Cytotoxic Activities of 1-(Prop-2-yn-1-yl)-7,8-dihydro-1H-benzo[d][1,3]-thiazine-2,5(4H,6H)-dione Derivatives

The important synthetic precursor（Ⅲ）, 1-（prop-2-yn-1-yl）-7,8-dihydro-1Hbenzo[d][1,3]thiazine-2,5（4H,6H）-dione（C（11）H（11）NO2S）, was prepared through a three-component reaction, which was further transferred into cytotoxic triazoles by alkylation and ＂click＂ synthesis in satisfactory yields of 87%^95%. Their structures were characterized by IR, H-RESI-MS and NMR analysis. Meanwhile, the crystal of Ⅲ was obtained and determined by X-ray single-crystal diffraction. Crystal data： orthorhombic system, space group P212121, a = 5.189（4）, b = 8.661（6）, c = 23.498（17） A, V = 1056.2（13） A^3, Z = 4, F（000） = 464, Dc = 1.392 g/cm^3, μ =0.284 mm^-1, R = 0.0637 and wR = 0.1668 for 8182 independent reflections（R（int） = 0.1580） and 2166 observed ones（I 〉 2σ（I））.

Solvent-Free Synthesis of 5-Alkenyl-2,2-butylidene-1, 3-dioxane-4,6-diones under Ultrasonic Irradiation with o-Phthalimide-N-Sulfonic Acid as Catalyst

5-Alkenyl-2,2-butylidene-1,3-dioxane-4,6-diones were synthesized by the Knoevenagel condensation reaction of aromatic aldehydes with 2,2-butylidene-1,3-dioxane-4,6-dione using o-phthalimide-N-sulfonic acid as catalyst, without solvent under ultrasonic irradiation. The present method has some notable advantages such as mild reaction conditions, short reaction times, less catalyst dosage and high yields with the green aspects by avoiding toxic catalysts and solvents. Further, the catalyst can be reused for five times without any noticeable decrease in the catalytic activity.

Facile synthesis of[1,2,4]triazino[4,3-b][1,2,4,5]tetrazepin derivatives by a one-pot reactions using 4-amino-3-hydrazinyl-6-methyl-1,2,4-triazin-5(4H)-one

4-Amino-3-mercapto-6-methyl-l,2,4-triazin-5（4H）-one 1 converted to 4-amino-6-methy-3-（methylthio）-1,2,4-triazin-5（4H）-one by methylation with methyl iodide.Controlled hydrazination of the resulting compound afforded 4-amino-3-hydrazinyl-6- methyl-l,2,4-triazin-5（4H）-one 2 as a building block,to the synthesis of some novel derivatives of[1,2,4]triazino- [4,3,b][1,2,4,5]tetrazepine 3-6,by the reaction with 3-chloropentane-2,4-dione,chloro acetonitrile,1,3-dichloroacetone,and methyl bromoacetate.This general synthetic procedure can be extended to the preparation of wide variety of tetrazepines using 1,2- bielectrophiles derivatives.

Facile microwave-assisted synthesis of 1H-pyrazino[1,2-a]quinoxaline-1,5(6H)-dione derivatives via a nucleophilic substitution reaction

A series of compounds containing the 1H-pyrazino[1,2-a]quinoxaline-1,5(6H)-dione scaffold have been synthesized using a one-pot procedure under microwave irradiation. This new strategy allowed for the facile synthesis of target compounds in good yields and could be readily applied to the construction of diverse libraries of compounds for high throughput screening in medicinal chemistry.

Facile and efficient synthesis of 5,7-disubstituted thiazolo[5,4-d] pyrimidine-4,6(5H,7H)-diones

A facile and efficient approach was developed to access 5, 7-disubstitued thiazolo[5,4-d]pyrimidine-4, 6（5H, 7H）-diones through condensation of N-substituted 5-amino-4-carbethoxythiazole with structurally diverse isocyanates in the presence of sodium hydride. The easy availability of substrates and tolerance of structural diversity in this reaction make it attractive to be used for construction of libraries in drug discovery process.

Improved microwave-assisted catalyst-free synthesis of9-aryl-5,9-dihydropyrimido[4,5-d][1,2,4]triazolo[1,5-a]pyrimidine-6,8(4H,7H)-dione derivatives

Agreen regioselective synthesis of some new and known 9-aryl-5,9-dihydropyrimido[4,5-d][l,2,4]triazolo[1,5-a]pyrimidine-6,8（4H,7H）-diones has been described via the microwave-assisted one-pot reaction of 3-amino-1H-1,2,4-triazoles,aromatic aldehydes and barbituric acids under solvent- and catalyst-free conditions.This operationally simple procedure is less laborious and provides a better scope than previously reported procedures.

Synthesis of Some Hexahydroquinazolinones Using K₃AlF₆(Al₂O₃/KF) as an Efficient Catalyst in Some Hexahydroquinazolinone Derivatives

A protocol for the synthesis of some 4-Aryl-1,3,4,6,7,8-hexahydroquinazolin-2,5(1H,6H)-diones (HHQs) was developed by means of a three-component condensation reaction of an aromatic aldehyde, 1,3-cylohexadione and urea in the presence of K3AlF6 (Al2O3/KF) as catalyst. This reaction is carried out under different conditions including 1) solvent free;2) reflux in acetonitrile;3) reflux in ethanol;4) reflux in chloroform;and 5) reflux in water. In all conditions, the desired products are obtained in high yields after relatively short reaction times. Nevertheless, the reactions proceed faster and in higher yields when they were carried out in acetonitrile. This adopted protocol for some Biginelli-type products has offered the advantages of reusability of the catalyst, high yields and ease of separation of pure products. Furthermore, the catalyst is easily prepared, stabilized and efficiently used under reaction conditions.

Effect of Temperature on the Reaction of 2-(N-acetylamine)-3-(3,5-di-<i>tert</i>-butyl-4-hydroxyphenyl)-propionic Acid with Oxygen in an Alkaline Condition

Results of oxidation 2-(N-acetylamine)-3-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid oxygen depend on temperature. At 55℃?- 60℃, 2,4-di-tert-butylbicyclo(4,3,1)deca-4,6-dien-8-(N-acetylamine)-3,9-dion-1-oxa is formed. The constitution is based on dates of spectrums 1Н and 13С NMR. At 95℃?- 97℃, mixtures of 2,4-di-tert-butylbicyclo(4,3,1)deca-4,6-dien-8-(N-acetylamine)-3,9-dion-1-oxa and of 6,8-di-tert-butyl-3-(N-acetylamine)spiro(4,5)deca-1-oxa-5,8-dien-2,7-dione are produced. Structures are calculated by the method of Hartrii-Foka. Values of enthalpies and of entropies allow to assume dynamic isomerism.

阳桃根中苯醌类化合物的分离鉴定与含量测定

目的：研究阳桃根（ACLR）中苯醌类化学成分的类型及含量测定方法。方法：利用色谱分离法、核磁共振技术对阳桃根药材60％乙醇提取物中的环己烷萃取部位进行分离、鉴定，并应用HPLC法对药材中的苯醌类化学成分进行含量测定。结果：分离得到2个苯醌类化合物：2-methoxy-6-nonyl-cyclohexa．2，5-diene-1，4-dione（MNDD）；2-dodecyl-6-methoxy-cyclohexa-2，5-diene-1，4-dione（DMDD）；MNDD，DMDD分别在0．177～2．657斗g和0．094～1．416μg进样量与峰面积有良好的线性关系；平均加样回收率为98．96％（RSD1．59％），99．55％（RSD0．98％）。结论：首次从植物中分离得到2个苯醌类化合物；HPLC测定方法简便、快速、稳定、准确可靠、重复性好，可用于阳桃根药材中MNDD，DMDD的质量控制。