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.

Molecular and Crystal Structure of 2, 3, 5, 6-dipropylene-r-pyrone

The title compound, C11H12O2, crystallizes in space group Pbcn (#60), a=8. 308(2), b=12. 812(3), c=8. 444(2) A, V=898. 8(6)A3, Z=4, Dc=1. 302 g/cm3, μ(MoKα) = 0. 88 cm-1, F (000) = 376. 00. The final R and Rw are0. 038 and 0. 045 for 401 observed reflections (I>3σ(I) ), respectively- The moleculeis nearly planar, having a 2-fold axis. Two-dimensional sheets are formed by weak in-termolecular hydrogen bonding. The sheets are antiparallelly packed by van der Waalsinteractions.

Synthesis and Characterization of Some Transition Metal Chelates of 5-(1-Hydroxy-6-Naphthylazo-3-Sodium Sulphonate) Thiobarbituric (L_1) and Barbituric (L_2) Acids

Some transition metal chelates of two ligands L1 and L2 were prepared and characterized by elemental analysis. The IR and 1H NMR spectra of several chelates of two ligands L1 and L2 showed the involvement of the azo group in chelation with the transition metaI ions, in most of the studied chelates, and that the two ligands L1 and L2 showed the involvement of the azo group in chelation with the transition metal ions, in most of the studied chelates, and that the two ligands L1 and L2 were coordinated either in the enol or the keto form. IR spetra also showed that Fe(III)-, Ni(II)-, Mn(II)-, VO(II)-L1 and Cu(II)-L2 chelates behaved in a bidentate manner, in contrast with the two (1:1) M:L cobalt chelates with the two ligands are tridentate.TG analysis indicated the presence of three to twelve water molecules of hydration eliminated on heating up to 150℃ and one or two coordinated water molecules removed at 150~180℃.The octahedral structure is proposed fOr all the chelates, except Cu(II)-L2 and Ni(II)-L1 chelates which have square planar geometry, based on their electronic spectra

Thermodynamic Study and Spectroscopic Analysis of a Charge-Transfer Complex between 3,5-Diamino-1,2,4-Triazole and 6-Methyl-1,3,5-Triazine-2,4-Diamine with Chloranilic Acid

Studying of charge-transfer (CT) and proton transfer interactions is essential due to their important role in many biological field and industrial applications. The current work will add more information’s about the nature of interaction between 3,5-diamino-1,2,4-triazole (DAT) and 6-methyl-1,3,5-triazine-2,4-diamine (MTDA) with 3,6-dichloro-2,5-dihydroxy-p-benzoquinone (chloranilic acid CLA) which was studied spectrophotometrically in Ethanol (EtOH) and Methanol (MeOH) solvents at different temperatures. The molecular composition of the formed complexes was studied by applying continuous variation and spectrophotometric titration methods and found to be 1:1 charge transfer complex for both Complex (DAT:CLA) and (MTDA:CLA) which are produced. Minimum-Maximum absorbance’s method has been applied to calculate the formation constant KCT and molecular extinction coefficient (ε);they recorded high values confirming high stability of the produced complexes. Oscillator strength (f), transition dipole moment (μ), ionization potential (IP) and dissociation energy (W) of the formed CT-complexes were also determined and evaluated;they showed solvent dependency. It is concluded that the formation constant (KCT) of the complexes is found to depend on the nature of both electron acceptor and donors and on the polarity of solvents.

A One-dimensional Cd(Ⅱ)Coordination Polymer Constructed from 1,4-Benzene-dicarboxylic Acid and 3-(2,6-Di(pyrazin-2-yl)pyridin-4-yl)-1H-indole:Synthesis,Structure and Photoluminescence

A new coordination polymer {[Cd（C_（21）H_（14）N_6）（C_8H_4O_4）]·H_2O}_n（1） was synthesized by an elaborate design via the reaction of 3-（2,6-di（pyrazin-2-yl）pyridin-4-yl）-1H-indole（bppi）,1,4-benzene-dicarboxylic acid（H2bdc） and cadmium（Ⅱ） nitrate in CH_3OH/H_2O mixed solvents. Complex 1 crystallizes in orthorhombic,space group Ccca with a = 20.012（4）,b = 31.881（6）,c = 19.808（4） ？,V = 12638（4） ？~3,Z = 16,C_（29）H_（20）CdN_6O_5,M_r = 644.91,D_c = 1.356 g·cm^（-3）,μ = 0.735 mm^（-1）,F（000） = 5184,GOOF = 1.046,the final R = 0.0405 and wR = 0.1063 for 6870 observed reflections（I 〉 2σ（I））. The Cd（Ⅱ） centre is hepta-coordinated by three N and four O atoms from one bppi terminal ligand and two bdc2– ligands,respectively,displaying a capped trigonal prism geometry. Structure extension gives coordination polymeric chains,in which the bdc2– linkers connect Cd（Ⅱ） cations into a one-dimensional（1D） coordination polymer along the c axis,giving zigzag chains with the Cd···Cd separation of 11.178（1） ？. The adjacent bppi terminal ligands in the chains are anti-periplanar conformation. The three-dimensional（3D） structure is stabilized by π···π stacking and hydrogen-bonding interactions to form a supramolecular self-penetrating network with 1D channels. In 1,there are voids 2999.7 ？~3 with 23.7% of per unit cell volume. Thermal analysis indicates that the framework of 1 is stable until 651 K and the photoluminescence of 1 in the solid shows very weak fluorescence at 382 and 560 nm upon excitation at 310 nm.

Structure and Photoluminescence of a 3D Coordination Polymer from Triazole and 2,6-Dimethylpyridine-3,5-dicarboxylic Acid

A new metal-organic coordination polymer [Zn2（trz）2（mpda）（H2O）]n（1, trz = 1,2,4-triazole, H2 mpda = 2,6-dimethylpyridine-3,5-dicarboxylic acid） was synthesized and characterized by single-crystal X-ray analyses. The crystal is of monoclinic system, space group P21/n, a = 9.619（3）, b = 8.920（3）, c = 22.159（6）, β = 96.897（4）°, V = 1887.3（9）3, Z = 4, Mr = 478.04, D3 c = 1.682 Mg/m, F（000） = 960, the final R = 0.0264 and wR = 0.0870（I 2σ（I））. Compound 1 consists of {[Zn4（trz）4]4＋}n layers, which are further connected by mpda2- to complete a three-dimensional structure. The title compound exhibits luminescence at λmax = 415 nm upon excitation at 364 nm.

Synthesis and Crystal Structure of Ethyl 3-(4-Chlorophenyl)-3,4-dihydro-6-methyl-4-oxo-2-(pyrrolidin-1-yl)furo[2,3-d]pyrimidine-5-carboxylate

The crystal structure of the title compound ethyl 3-（4-chlorophenyl）-3,4-dihydro-6- methyl-4-oxo-2-（pyrrolidin-1-yl）furo[2,3-d]pyrimidine-5-carboxylate （C20H20ClN3O4, Mr= 401.84） has been prepared and determined by single-crystal X-ray diffraction. The crystal is of monoclinic, space group P21/n with a = 20.6215（9）, b = 8.5311（4）, c = 21.6886（9） A^°, β = 91.607（1）°, V = 3814.0（3）A^°^3, Z = 8, Dc = 1.400 g/cm^3, F（000） = 1680, μ = 0.233 mm^-1, R = 0.0718 and wR = 0.1545 for 6717 observed reflections with I 〉 2σ（I）. X-ray diffraction analysis reveals two crystallographically independent molecules in the asymmetric unit.

A 3D-QSAR Study on C-3 Substituted 4,6-Dichloroindole-2- Carboxylic Acids with Comparative Molecular Field Analysis

Aim and Method Comparative molecular field analysis (CoMFA), a threedimensional quantitative structure-activity relationship (3D-QSAR) method was applied to a novelseries of C-3 substituted 4, 6-dichloioindole-2-carboxylic acids to study the relationship betweentheir structure and the affinity for the glycine site of the NMDA receptor. Result Hie coefficientsof cross-validation q^2 and non cross-validation r^2 for the model established by the study are0.744 and 0.993, respectively, the value of variance ratio F is 261.343, and standard error estimate(SE) is 0.039. Conclusion These values indicate that the CoMFA model may have a good prediction forthe activity of C-3 substituted 4, 6-dichloroin-dole-2-carboxylic acids. As a consequence, thepredicted activity values of new designed compounds supports our conclusion from the model.

SYNTHESIS OF 4,6-DISUBSTITUTED 5-THIOXO-1,2,4-TRIAZIN-3-ONE FROM BENZOTHIOFORMANILIDE

A method of synthesis of 4,6-disubstituted 5-thioxo-1,2,4-triazin- 3-ones from benzothioformanilides and semicarbazide is described.And six new compounds were synthesized by this method.

1-[2,5-二氯-4-(六氟丙氧基)苯基]-3-(2,6-二氟苯甲酰基)脲的合成研究

以2,5-二氯苯胺为原料,经重氮化及重氮盐水解反应,合成中间体2,5-二氯苯酚,经过硝酸硝化,硫化钠还原得到2,5-二氯4-氨基苯酚,再与六氟丙烯加成得到2,5-二氯-4-(1,1,2,3,3,3-六氟丙氧基)苯胺。2,6-二氟苯甲酰胺与草酰氯反应得到2,6-二氟苯甲酰异氰酸酯。最后2,5-二氯-4-(1,1,2,3,3,3-六氟丙氧基)苯胺与2,6-二氟苯甲酰异氰酸酯反应得到标题化合物,该步产率92%,该产品结构通过了1HNMR和IR的验证。该法反应条件温和,操作简便,收率稳定,适合工业化生产。

Efficacy of Topical versus Oral 5-Aminosalicylate for Treatment of 2,4,6-Trinitrobenzene Sulfonic Acid-induced Ulcerative Colitis in Rats

5-aminosalicylic acid（5-ASA） is drug of choice for the treatment of ulcerative colitis（UC）. In this study, the efficacy of topical versus oral 5-ASA for the treatment of UC was examined as well as the action mechanism of this medication. A flexible tube was inserted into the rat cecum to establish a topical administration model of 2,4,6-trinitrobenzene sulfonic acid（TNBS）-induced UC. A total of 60 rats were divided into sham operation group（receiving an enema of 0.9% saline solution instead of the TNBS solution via the tube）, model group, topical 5-ASA group, oral Etiasa group（a release agent of mesalazine used as positive control） and oral 5-ASA group（n=12 each）. Different treatments were administered 1 day after UC induction. The normal saline（2 mL） was instilled twice a day through the tube in the sham operation group and model group. 5-ASA was given via the tube in the topical 5-ASA group（7.5 g/L, twice per day, 100 mg/kg）, and rats in the oral Etiasa group and oral 5-ASA group intragastrically received Etiasa（7.5 g/L, twice per day, 100 mg/kg） and 5-ASA（7.5 g/L, twice per day, 100 mg/kg）, respectively. The body weight was recorded every day. After 7 days of treatment, blood samples were drawn from the heart to harvest the sera. Colonic tissues were separated and prepared for pathological and related molecular biological examinations. The concentrations of 5-ASA were detected at different time points in the colonic tissues, feces and sera in different groups by using the high pressure liquid chromatography（HPLC）. The results showed that the symptoms of acute UC, including bloody diarrhea and weight loss, were significantly improved in topical 5-ASA-treated rats. The colonic mucosal damage, both macroscopical and histological, was significantly relieved and the myeloperoxidase activity was markedly decreased in rats topically treated with 5-ASA compared with those treated with oral 5-ASA or Etiasa. The mRNA and protein expression of IL-1β, IL-6, and TNF-α was down-regulated in the colonic tissue of rats topically treated with 5-ASA, significantly lower than those from rats treated with oral 5-ASA or Etiasa. The concentrations of 5-ASA in the colonic tissue were significantly higher in the topical 5-ASA group than in the oral 5-ASA and oral Etiasa groups. It was concluded that the topical administration of 5-ASA can effectively increase the concentration of 5-ASA in the colonic tissue, decrease the expression of proinflammatory cytokines, alleviate the colonic pathological damage and improve the symptoms of TNBS-induced acute UC in rats.

The Synthesis of 2,4,6-Triisopropyl-1, 3,5-trioxane Catalyzed by Ionic Liquids

The synthesis of 2, 4, 6-triisopropyl-1, 3, 5-trioxane with high yield and desirable selec- tivity from solvent-free cyclotrimerization of isobutyraldehyde catalyzed by ionic liquids was reported in this work.

Synthesis,Crystal Structure,and Magnetic Property of One 3D Nickel Coordination Polymer Based on 2-Hydroxy-5-(3',5'-terephthalic acid)Pyridine and 1,4-Bis(1-imdazoly)benzene

One novel nickel coordination polymer, {[Ni（OTP）（bib）1.5（H2O）]·2H2O}n（1, H2 OTP = 2-hydroxy-5-（3＇,5＇-terephthalic acid） pyridine, bib = 1,4-bis（1-imdazoly）benzene）, has been synthesized and characterized by elemental analysis（EA）, IR, powder X-ray diffraction（PXRD）, and thermogravimetric（TG） analyses. The crystal of 1 crystallizes in monoclinic, space group P21/n with a = 12.2860（5）, b = 13.8246（6）, c = 19.0140（8） A, β = 104.3870（1）°, V = 3128.2（2） A3, Z = 4, C32H28N7 Ni O8, Mr = 697.32, Dc = 1.481 g/cm^3, F（000） = 1444 and μ（Mo Kα） = 0.684 mm-1. The final R = 0.0704 and w R = 0.1764 for 5485 observed reflections with I 2σ（I） and R = 0.1087 and wR = 0.2010 for all data. Topology analysis reveals that complex 1 is a 3D 2-fold interpenetrated {4^4·6^6}-nov net based on the 1D [Ni（OTP）]n chain and the 2D [Ni2（bib）3]n sql sheet. And the variable-temperature magnetic susceptibility measurements exhibit weak antiferromagnetic coupling interaction.

Critical Amino Acid Residues for Nicotine 5'-Hydroxylation in Human CYP2A Enzymes

Objective： We have continued previous work in which we demonstrated that #117 and #372 amino acids contributed to the high activities of human CYP2A13 in catalyzing 4-methylnitrosamino-1-（3-pyridyl）-1-butanone（NNK） and aflatoxin BI（AFB1） carcinogenic activation. The present study was designed to identify other potential amino acid residues that contribute to the different catalytic characteristics of two CYP2A enzymes, CYP2A6 and CYP2A13, in nicotine metabolism and provide insights of the substrate and related amino acid residues interactions. Methods： A series of reciprocally substituted mutants of CYP2A6lle^300→ Phe, CYP2A6Gly^301aAla, CYP2A6Ser^369 → Gly, CYP2A13Phe^300→ Ile, CYP2A13Ala^301 → Gly and CYP2A13Gly^369 → Set were generated by site-directed mutagenesis/baculovirus-Sf9 insect cells expression. Comparative kinetic analysis of nicotine 5＇hydroxylatin by wild type and mutant CYP2A proteins was performed. Results：All amino acid residue substitutions at 300, 301 and 369 caused significant kinetic property changes in nicotine metabolism. While CYP2A6Ile^300→ Phe and CYP2A6Gly^301→Ala mutations had notable catalytic efficiency increases compared to that for the wild type CYP2A6, CYP2A13Phe^300→Ile and CYP2A13Ala^301→Gly replacement introduced remarkable catalytic efficiency decreases. In addition, all these catalytic efficiency alterations were caused by Vmax variations rather than Km changes. Substitution of #369 residue significantly affected both Km and Vmax values. CYP2A6Ser^369 → Gly increase the catalytic efficiency via a significant Km decrease versus Vmax enhancement, while the opposite effects were seen with CYP2A13Gly^369 → Ser. Conclusion：#300, #301 and #369 residues in human CYP2A6/13 play important roles in nicotine 5＇ -oxidation. Switching #300 or #301 residues did not affect the CYP2A protein affinities toward nicotine, although these amino acids are located in the active center. Set369 to Gly substitution indirectly affected nicotine binding by creating more space and conformational flexibility for the nearby residues, such as Leu^370 which is crucial for many hydroxylations.

Syntheses,Crystal Structures and Properties of Co(Ⅱ) and Cu(Ⅱ) Complexes with 5-Nitro-1,2,3-benzenetricarboxylic Acid

Two new coordination polymers,{[Co（O2N-Hbtb）（phen）（H2O）3]·2H2O}n 1 and {[Cu3（O2N-btb）2（bipy）2（H2O）4]·4H2O}n 2（O2N-H3btb=5-nitro-1,2,3-benzenetricarboxylic acid,phen=1,10-phenanthroline,bipy=2,2＇-bipyridine）,were prepared through hydrothermal reactions of Co（Ⅱ） or Cu（Ⅱ） salt with O2N-H3btb in the presence of different auxiliary N-donor ligands.Their crystal structures were determined by single-crystal X-ray diffraction analysis and further characterized by elemental analysis and IR spectroscopy.In the two complexes,O2N-H3btb ligand acts as monodentate and bis-monodentate modes,respectively.Complex 1 displays a two-dimensional layered structure through the inter-and intramolecular hydrogen bonding interactions while complex 2 has an O2N-btb bridged one-dimensional chain which is extended into a three-dimensional network by hydrogen bonding interactions.The magnetic properties of complex 2 are investigated over the temperature range of 2～300 K and ferromagnetic interactions are observed.

Crystal and Molecular Structure, and Spectral Characteristics of Sodium 3,5-Bis(Hydroxyimino)-1-Methyl-2,4,6-Trioxocyclohexanide

Sodium 3,5-bis(hydroxyimino)-1-methyl-2,4,6-trioxocyclohexanide C7H5N2NaO5 (I) has been isolated as the only product of the reaction of nitrosation of methylphloroglucinol. The structure of the titled compound has been determined from single crystal X-ray diffraction data. The hydrated C7H5N2NaO52.5H2O crystallizes in the monoclinic space group C2/c, with a(?) 16.408(3);b(?) 12.446(3);c(?) 13.716(3);(o) 126.34(3). The planar organic anion exists in a triketo-dihydroxyimino form with the C–O and C–N distances from 1.220(2) to 1.271(2)?? and from 1.292(2) to 1.293?? respectively. In the IR spectrum of I, the sharp absorption band occurred at 1681 cm-1 due to C=O stretching indicating the strong H-interactions. The correlations of theoretical (DFT-B3LYP/aug-cc-pVDZ) and experimental UV-vis absorption spectra in neutral and alkaline ethanolic solutions showed the existence of hydroxyimino-nitroso tautomerism while ionization of I.

Synthesis and Crystal Structure of 3-(2-Hydroxy-phenyl)-5-(2-methyl-phenyl)-6-thoxycarbonyl-cyclohexen-2-one

Hydroxy-phenyl)-5-(2-methyl-phenyl)-6-ethoxycarbonyl-cyclohexen-2-one has been synthesized and characterized by elemental analysis, IR, UV, H NMR and MS, and its crystal 1 structure was determined by X-ray single-crystal diffraction method. The crystal belongs to the monoclinic system, space group P21/c with a = 14.6298(13), b = 5.8623(5), c = 22.255(2) ?, β = 105.855(2)o, V = 1836.0(3) ?3, Mr = 350.40, Z = 4, Dc = 1.268 g/cm3, F(000) = 744, μ(MoKα) = 0.086 mm-1, R = 0.0680 and wR = 0.1498. The crystal analysis results show that the cyclohexene unit of the title compound has a quasi-chair conformation, and a centrosymmetric dimer with a 16-membered ring is produced by the intermolecular hydrogen bonds.

Hydrothermal Syntheses and Crystal Structures of Six Complexes Constructed from 1,3,5-Benzenetricarboxylic Acid and 4'-(4-Pyridyl)-2,2':6',2''-terpyridine Mixed Ligands

Six new transition metal complexes, [Zn（HBTC）（PYTPY）]n·n PYTPY（1）, [Cu（HBTC）（PYTPY）]n·n PYTPY（2）, [Co（HBTC）（PYTPY）]n·n DMF（3）, [Mn（HBTC）（PYTPY）]n·n DMF（4）, [Cd（HBTC）（PYTPY）（H2O）]n·2nH2O（5）, and [Co（HBTC）（PYTPY）（H2O）2]（6）,（H3BTC = 1,3,5-benzenetricarboxylic acid, PYTPY = 4＇-（4-pyridyl）-2,2＇：6＇,2＇＇-terpyridine, DMF = N,N？-dimethylformamide）, have been synthesized and characterized by elemental analysis, IR and X-ray single-crystal diffraction. Complexes 1~5 all feature one-dimensional chain structures, and complex 6 exhibits a zero-dimensional structure. Complexes 1~5 present three-dimensional（3D） supramolecular frameworks via π-π stacking interactions, whenas 6 has also a 3D supramolecular structure assembled by hydrogen bonding. Meanwhile, complexes 1 ~ 6 exhibit the thermal stabilities and photoluminescent properties.

缩合试剂2-氯-4,6-二甲氧基-1,3,5-三嗪的合成与应用

2-氯-4,6-二甲氧基-1,3,5-三嗪(CDMT)是商品化的常用于羧酸的活化和酰胺合成的缩合试剂。CDMT制备简单,成本低廉,活性高,适合工业化生产使用。CDMT与羧酸在有机碱N-甲基吗啉(NMM)作用下生成活性脂。本文对2-氯-4,6-二甲氧基-1,3,5-三嗪的合成方法,和其在酰胺,肽,脂,酸酐,醛,酮,芳香酮,炔酮,芳基偶联物,3,5-二取代1,2,4-恶二唑合成中的应用进行了综述。

光稳定剂中间体2-氯-4,6-二(N-丁基-2,2,6,6-四甲基-4-哌啶胺基)-1,3,5-三嗪的合成研究

采用单因素法,以三聚氯氰、N-丁基-2,2,6,6-四甲基-4-哌啶胺和氢氧化钠为原料,二甲苯为溶剂,四丁基溴化铵为催化剂合成光稳定剂中间体2-氯-4,6-二(N-丁基-2,2,6,6-四甲基-4-哌啶胺基)-1,3,5-三嗪。结果表明该反应的最优工艺条件为第一阶段反应温度为5℃~8℃,反应时间2 h,第二阶段升温至60℃,反应时间5 h,原料物质的量之比n(三聚氯氰):n(N-丁基-2,2,6,6-四甲基-4-哌啶胺):n(氢氧化钠) = 1:2.15:2.15,催化剂四丁基溴化铵的用量0.20 g (相对0.05 mol三聚氯氰),产品产率为95.61%。