A Green Protocol for Efficient Synthesis of 1,8-Dioxo-Octahydroxanthenes Using Ionic Liquid

A clean, simple, efficient synthesis of 1,8-dioxo-octahydroxanthenes derivatives using ionic liquid 1-butyl, 3-me- thylimidazolium perchlorate ([bmim] ClO4) has been developed. The method provides several advantages such as simple work up, environmental friendliness and excellent yields in short reaction time. The ionic liquid [bmim] ClO4 used was recovered and reused for three times.

Interaction between Bifunctional Dioxo Macrocyclic Polyamine Co(II) Complex and DNA in Metallomicellar System

The cleavage of DNA (pUC18) by lipophilic macrocyclic polyamine Co(II) complex was investigated in metallomicellar system. The results showed that the conversion of plasmid DNA (pUC18) increases with the increase of the concentration of complex under physiological conditions.

Synthesis, Structure and Third-order Non-linear Optical Properties of Tungsten Dioxo Complex with 8-Hydroxyquinoline Ligand WO_2(C_9H_6NO)_2

Tungsten dioxo complex WO 2(C 9H 6NO) 2 was obtained via the low temperature solid-state reaction of(NH 4) 2WS 4, 8-hydroxyquinoline(8-hq) and(CH 3) 4NI, and it was characterized by means of elemental analyses, IR spectroscopy and X-ray diffraction analysis. The crystal of the title compound belongs to monoclinic, space group C2/c, with the crystal cell parameters: a=1.3316(3) nm, b=0.94444(19) nm, c=1.3485(3) nm, β=109.66(3)°, V=1.5970(6) nm 3, Z=6. The title compound possesses a supramolecular structure formed through hydrogen bonds and π-π stacking interactions. The third-order non-linear optical(NLO) properties of the title compound were also investigated. The third-order non-linear absorption coefficient α 2 and refractive index n 2 are 0.85×10 -11 m/W -1 and -1.5×10 -19 m 2/W, respectively. The third-order non-linear susceptibility χ (3) is 3.03×10 -13 esu for 3.8×10 -5 mol/L sample concentration.

SELECTIVE REDUCTION OF 3,17—DIOXO—STEROIDS TO 17β-HYDROXY-3-OXO-STEROIDS

11β-Hydroxy-androst-4-en-3,17-dione(1a),androst-4,9(11)-dien-3,17- dione-(2a),androst-4-en-3,11,17-trione(3a),11α-methoxy-androst-4-en-3,17-dione (4a)and 11β-metboxy-androst-4-en-3,17-dione(Sa)were selectively reduced to the corresponding 17β-OH derivatives in one step without the protection of 3- oxo(and 11-oxo,in the case of 3a)group with the yields ranging from 65% to 79%.In these reactions,the ditute NaBH_4(or KBH_4)solution in methanol was added dropwise to the 3,17-dioxo-steroids solution in methanol-benzene-pyridine, while the reaction mixtures were well stirred at -5～5℃.Acid(such as gtacial acetic acid)was added to quench the reactions.The resulted testosterone derivatives(1b～5b)were purified by flash chromatography. This method appties to the reduction of other 3,17-dioxo-steroids such as△~1 -3-one,△^(1.4)-3-one,△^(4.6)-3-one,△^(1.4.6)-3-one containing compounds.

Synthesis of Spiro Dihydrofurans and 1,8-Dioxo-xanthenes via DABCO Catalyzed Tandem Reaction of Aldehyde with Cyclohexane-1,3-dione and Dimedone

The 1,4-diazabicyclo[2.2.2]octane（DABCO） catalyzed reaction of cyclohexane-1,3-dione or dimedone with various aldehydes in acetonitrile resulted in the polysubstituted tetraketones, spiro dihydrofurans or 1,8-dioxo-xanthenes derivatives as main products respectively according to the structure of reactants and reaction conditions.

α-Oxoketene Cyclic S,S-Acetals Chemistry──Reaction of α,α′-Dioxo (ester)ketene Cyclic S,S-Acetals with Ethylenediamine

α, α′ -Dioxo (ester ) ketene cyclic S, S-acetais 2 were reacted withethyleneddriine to chrd α, α′-dioxo (ester)ketene cyclic N, N-acetals 3 Thisprocess provides a new method for the synthesis of 3 in gnd yteld under mildcondition. All products are confirmed with elementai analpeis, IR, 1H NMR and13~C NMR

Synthesis and Crystal Structure of Tert-butyl 4-[(E)-4-(1,3-Dioxo-1,3-dihydro-2H-isoindol-2-yl)-1-butenyl] Benzoate

The title compound tert-butyl 4-[（E）-4-（1,3-dioxo-1,3-dihydro-2H-isoindol-2-yl）- 1-butenyl] benzoate has been synthesized and characterized by X-ray crystallography. It crystallizes in monoclinic, space group C2/c with a = 14.875（3）, b = 8.9796（13）, c = 34.736（6） A°, β = 95.981（4）°, V= 4614.4（14）A°^3, Z= 8, Dc = 1.213 g/cm^3, F（000） = 1792,μ（MoKα） = 0.084 mm^-1, R = 0.0602 and wR = 0.1445 for 4613 unique reflections with 2272 observed ones （I〉 2σ（I））. The results of crystal structure determination show that the title compound has a layer structure, and the two benzene rings in molecule are parallel to each other.

Synthesis and antiangiogenic activities of 5-amino-1,3-dihydro-1,3-dioxo-2H-isoindole-2-propanoic acid derivatives

基于结构活动关系和包含 RGD 肽的 antiangiogenic 机制，一系列 5-amino-1,3-dihydro-1,3-dioxo-2H-isoindole 衍生物被综合。结构被描绘由(1 ) H NMR， MS 和元素分析。在那里，禁止 angiogenesis 的能力被小鸡胚胎 chorioallantoic 膜试金在 10 点评估(? 5 ) mol/L。混合物 7a 和 7b 显示了明显的 antiangiogenic 活动。

Crystal Structure and EPR Spectra of cis-Dioxo-molybdenum(V) Complex with o-Aminophenol

The paramagnetic cis dioxo molybdenum(V) complex, [NH 2~CH 2~CH 2~NH 3] 3[Mo VO 2(HNC 6H 4O) 2] was obtained by the reaction of tetra butyl ammonium β octamolybdate with o aminophenol and ethylenediamine in the mixed solvent of CH 3OH and CH 3CN, and characterized by IR, NMR, EPR spectroscopy and X ray diffraction analysis. The determination of single crystal X ray analysis revealed that the central Mo V ion metal center exhibits distorted octahedral coordination with cis dioxo o aminophenol. The EPR spectra of both the complex and flavoenzyme show similarly. Thus it suggests that the complex anion [Mo VO 2(HNC 6H 4O) 2] 3- and flavoenzyme have related structure feature.

Synthesis, Crystal Structure of Cis-dioxo-catecholatotungsten(VI) Complex and Its NMR Studies on the Interaction with ATP

Cis dioxo catecholatotungsten(VI) complex anion [W (VI) O 2 (OC 6H 4O) 2] 2- was obtained with discrete protonated ethylenediamine (NH 2CH 2CH 2NH 3) + cations by the reaction of tetra butyl ammonium decatungstate with catechol in the mixed solvent of CH 3OH, CH 3CN and ethylenediamine, and compared with its molybdenum analogue [Mo (V) O 2(OC 6H 4O) 2] 3- by crystal structure, UV, EPR. The results of the UV and EPR spectra show that tungsten is less redox active than molybdenum since the molybdenum is reduced from Mo(VI) to Mo(V) but tungsten stays in the original highest oxidized state Mo(VI) when they are crystallized from the solution above. It is worthy to note that [W (VI) O 2(OC 6H 4O) 2] 2- shows the same coordination structure as its molybdenum analogue in which the metal center exhibits distorted octahedral coordination geometry with two cis dioxocatecholate ligands and might have the related coordination structure feature with the cofactor of flavoenzyme because [Mo (V) O 2(OC 6H 4O) 2] 3- presented essentially the same EPR spectra as flavoenzyme. The NMR studies on the interaction of the title complex with ATP reveal that the reduction of W(VI) to W(V) occurs when the title complex is dissolved in D 2O and the W(V) is oxidized again when ATP solution is mixed with original solution and the hydrolysis of the catecholato ligand take places at mean time being monitored by 1H NMR and 13 C NMR spectra.

Silicon-mediated highly efficient synthesis of 1,8-dioxo-octahydroxanthenes and their transformation to novel functionalized pyrano-tetrazolo[1,5-a]azepine derivatives

A facile and highly efficient protocol for the synthesis of 1,8-dioxo-octahydroxanthene derivatives was achieved through cascade Knoevenagel-Michael condensations and cyclo-dehydration reaction utilizing tetrachlorosilane（TCS） as catalyst under mild conditions.Reaction of the titled compounds with TCSNaN_3 to give novel functionalized pyrano[3,2-c]tetrazolo[1,5-a]azepine derivatives is also described.

Ceric ammonium nitrate supported HY-zeolite:An efficient catalyst for the synthesis of 1,8-dioxo-octahydroxanthenes

Ceric ammonium nitrate （CAN） supported HY-zeolite has been used as an efficient catalyst for the one- pot synthesis of 1,8-dioxo-octahydroxanthenes from the readily available 1,3-diketone and aromatic aldehydes under solvent-free conditions. The present methodology is cost-effective in addition to other advantages like high yields of products in shorter reaction time and simple workup procedure without the use of any injurious solvents.

Synthesis and Herbicidal Activity of Novel N-（2-Fluoro-5（3- methyl-2,6-dioxo-4-（trifluoromethyl）-2,3-dihydro-pyrimidin- l（6H）-yl）phenyl）-2-phenoxyacetamide Derivatives

Thirteen novel N-（2-fluoro-5-（3-methyl-2,6-dioxo-4-（trifluoromethy）-2,3-dihydropyrimidin-1（6H）-yl）phenyl）- 2-phenoxy）acetamides were designed and synthesized utilizing 4-fluoro-aniline and ethyl 3-amino-4,4,4-trifluoro-but-2-enoate as starting materials. The chemical structures of all compounds were confirmed by IH NMR, IR, mass spectrum and elemental analyses. Subsequently, the herbicidal activities of the as-prepared compounds were evalu-ated in the greenhouse. Bioassay results indicated that most of compounds had better herbicidal activities against dicotyledonous weeds. Among all the tested compounds, compounds 4a--4i showed good herbicidal activities at both pre-emergence and post-emergence treatment against two or three kinds of dicotyledonous weeds, such as Abutilon theophrasti Medic, Amaranthus ascendens L, and Chenopodium album L at the dosage of 75 g ai/ha.

THE SYNTHESIS AND STRUCTURE OF 4,5-DIOXO-2-THIO-1,3,2,4-DIAZADIPHOSPHOLANES

A new type of diphosphorus heterocycles, 4,5- dioxo- 2- thio- 1,3, 2,4- diazadiphospholanes,has been synthesized by the condensation of carbamyl phosphoryl amidate and 4- substitutedphenyl phosphine dichloride, and then sulfurization. The cis- and trans-isomers of the com-pounds were separated by HPLC, and their structures were studied with 1H NMR and 31PNMR. It has been found that the cis- and trans-isomers have different chemical shifts （δ） anddifferent coupling constants. The preliminary bioassay shows that some of them possessstrong herbicidal activity.

钯催化串联环化反应合成2-苄基-3,4-二羰基-6-苯基-9-乙烯基-2-氮杂螺[4.4]壬烷-7,7-二羧酸乙酯——介绍一个有机化学综合实验

开展有机化学综合实验有利于锻炼学生的实验技能,培养学生的创新能力,激发学生的独立思考能力和研究意识。本文介绍了一个有机化学综合实验,以2-乙烯基环丙烷-1,1-二甲酸二乙酯和1-苄基-4-亚苄基-2,3-吡咯烷酮为反应物,利用钯催化串联环化反应合成2-苄基-3,4-二羰基-6-苯基-9-乙烯基-2-氮杂螺[4.4]壬烷-7,7-二羧酸乙酯,并利用核磁共振氢谱(^(1)H NMR)、碳谱(^(13)C NMR)和高分辨质谱(HRMS)对产物结构进行表征。

Nano Nickel-Cobalt Ferrite Catalysed One-Pot Multi-Component Synthesis of Xanthenediones and Acridinediones

1,8-Dioxo-octahydroxanthenes (4a-4f) and 1,8-dioxohexahydroacridines (5a-5c) were synthesized by novel, simple and eco-friendly method with higher yields in the presence of magnetically separable nano nickel-cobalt ferrite catalyst (Ni0.5Co0.5Fe2O4). The former, 1,8-dioxo-octahydroxanthenes have been synthesized from dimedone and different aromatic aldehydes, while the latter from this mixture are along with ammonium acetate. The main advantage of this method is that the nano catalyst can be reused up to five reaction cycles without losing the catalytic activity.

肉苁蓉化学成分的研究

从列当科植物肉苁蓉 Ｃｉｓｔａｎｃｈｅ ｄｅｓｅｒｔｉｃｏｌａ中分得１０个化合物，通过理化常数、光谱数据及Ｘ－衍射分别鉴定为苁蓉素（Ⅰ）、梓醇（Ⅱ）、丁香苷（Ⅲ）、红景天苷（Ⅳ）、２，５－二氧－４－咪唑烷基－氨基甲酸（Ⅴ）、甘露醇（Ⅵ）、硬脂酸（Ⅶ）、β－谷甾醇（Ⅷ）、胡萝卜苷（Ⅸ）和甜菜碱（Ⅹ）。其中Ｖ为新的天然产物，Ⅱ为首次从本属植物中分得。Ｉ、Ⅲ、Ⅳ为首次从该种植物中分得。

1-[5-(1,3-二氧-4,5,6,7-四氢-1H-异吲哚-2-基)苯基]-3-取代脲衍生物的合成与除草活性研究

为了寻找高效低毒的原卟啉原氧化酶抑制剂(protox)类除草剂,设计并合成了一系列1-[5-(1,3-二氧-4,5,6,7-四氢-1H-异吲哚-2-基)苯基]-3-取代脲类衍生物4a～4d和5a～5g.化合物4a～4d经异氰酸酯法合成,收率、纯度高;化合物5a～5g利用固体光气一锅法合成,反应时间短.所得化合物结构经1HNMR,IR,质谱和元素分析表征.初步生物活性测试表明:化合物4c,5a,5b,5c在有效成分75g/hm2剂量下对苘麻、马刺苋、凹头苋等双子叶杂草表现出90%以上的防效.