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.

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.

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.

Argentum 5-Hydroxy-7-methoxy-2-phenyl-4H-chromen-4-one-6-sulfonate:Synthesis,Crystal Structure and Antitumor Activity

In order to improve the water solubility and bioavailability of 5-hydroxy-7-methoxyflavone,argentum 5-hydroxy-7-methoxy-2-phenyl-4H-chromen-4-one-6-sulfonate[Ag4(H2O)6](C(16)H(11)O4SO3)4·H2O(1,C(16)H(11)O4SO3=5-hydroxy-7-methoxy-2-phenyl-4H-chromen-4-one-6-sulfonate)was synthesized by sulfonation reaction.The structure of 1 was characterized by FT-IR,elemental analysis and X-ray single-crystal diffraction.Complex 1 belongs to the triclinic system,space group P1,a=8.077(4),b=12.365(4),c=17.735(7)A,V=1685.0(12)A3,Z=1,μ=1.372 mm^–1,Dc=1.936 g/cm^3,F(000)=984,the final R=0.0819 and wR=0.2332 with I>2σ(I).3D structure of 1 exhibits alternating organic and inorganic regions.O–H×××O hydrogen bonds and Ag–O coordination interactions exist among crystal water,coordinated water and sulfo group,which constructed an organic zone.Flavone skeletons form organic region of 1.Sulfo group is the bridge linking these two regions.The in vitro antitumor activity of 1 against human lymphoma cells U937 and human breast cancer cells MCF-7 were evaluated with CCK-8 assay.The result shows that 1 showed inhibitory activity against tumour cell U937 and MCF-7,and indicated that flavone sulfonate derivatives may be potential leads for further biological screenings and may generate drug-like molecules.

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.

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。