Regioselective Synthesis and Base Catalyzed Transacylation of Substituted 1H—Pyrazole—4—carboxamides

New type of substituted 1H-pyrazole-4-carboxamides were obtained by regioselective synthesis under the catalysis of different based.The stuctures of the title compounds were confirmed by elemental analysis,^1H NMR,IR,MS and X-ray crystallography.Compounds 1 were transcaylated into their corresponding.Compounds 1 were transacylated into their corresponding amides 3 in the prsence of sodium hydride.Preliminary bioassays indicated that some compounds showed fungicidal activities against Rhizoctonia solani and Sclerotinia sclerotiorum.     

1，3—Dipolar Cycloaddition of Substituted Benzonitrile Oxide to 5—（R）—（1—Menthyloxy）—2（5H）—furanone

Several isoxazoline compounds were obtained by the 1,3-dipolar cycloaddition of benzonitrile oxide to 5-(R)-(1-menthyloxy)-2(5H)-furanone. The reaction condition was investigated preliminarily, the structures of these compounds have been established via the analysis of NMR data (involved NOEID or HMBC) and the reaction seems occurred regioselectively.     

Study on the Synthesis of Metabolite of Clausenamide （CM1）

(-) Clausenamide (1) showed strong nootropic action, while its (+) antipode had no such an action. The content of CM1(2) in the metabolites of (-)1 is much higher than that of (+)11. For comparing the nootropic activity of enantiomers, (+) and (-) CM1 were synthesized. CM1 is the hydroxylated product of the N-methyl group of clausenamide. Oxidation of the C3-OH and C6-OH protected clausenamide to introduce the hydroxyl group into the methyl was tried but unsuccessful. Then de novo s…     

Synthesis of 5—Aryl—1,2—dihydro—1—pyrrolizinones

In order to search for new potent anti-inflammatory and analgesic agents in pyrrolizinones,the title compounds were designed and synthesized.A series of the compounds were prepared with two different synthetic schemes.Some of the compounds showed remarkable anti-inflammatory and/or analgesic activities on mice.     

Synthesis of Polyphosphonates Containing 5—Flouro—N^1—furanyl—N^3—glyceroalkyl—uracil and Formyl Groups

A series of novel polyphosphonates containing 5-flouro-N^1-furanyl-N^3-glyceroalkyl-uracil and formyl groups was synthesized by the condensation of 3-(ω-(1′-furanyl-5-flourouracil-3-yl) alkoxy)-1,2-dihydroxy propane with phosphonyl dichloride. The products were characterized by IR,^1H NMR,^31P NMR, M,and elemental analysis. The results of bioassay show that compound 8a possesses potential anticancer activity.     

Tuning the Excited—state Properties of Cyclometalated Platinum（Ⅱ）Complexes of 6—Pheny1—2,2’bipyridine by Ancillary Acetylide Ligand

A series of luminescent cyclometalated platinum(Ⅱ）complexes,(C^N^N)Pt(C≡CR)[HC^N^N=4-(4-tolyl)-6-phenyl-2,2’-bipyridine;R=4-chlorophenyl(1),phenyl(2) and 4-tolyl(3)],were synthesized,and their spectroscopic properties have been examined.These complexes are brightly emissive both in fluid solution and in the solid state,attributed to triplet metal-to-ligand charge transfer(^3MLCT)state.The excited state energy can be tuned by ancillary acetylide ligands.The emission lifetimes in dichloromethand solution at room temperature were up to 1.64 μs and the emission quantum yields were in the range of 0.03-0.15.     

Quantitative Structure—Activity Relationships in the Lithium and Sodium Affinities of n—Alkyl Fluorides

B3L YP/6-31 g(d,p)method was used to calculate the lithium and sodium affinities of n-alkyl fluoride. These affinities were found to obey the Holmes relationship, i.e.they correlate linearly with the quotient n/(n 1), where n is the number of carbon atoms in the alkyl chain. From the correlation the limiting values of lithium and sodium affinities for very long alkyl chain were predicted to be-153.3kJ/mol and -108.4kJ/mol,respectively.     

Photophysical and Photoelectric Properties of 2—{[4—（N—Hexadecyl—N—methylamino）phenyl]methylene}—propanedinitrile

2-{[4-(N-Hexadecyl-N-methylamino)phenyl]methylene}-propanedinitrile(HMAPN) with typical donor-π-acceptor(D-π-A）structure was synthesized.It could be easily assembled into stable films by LB technique.The photophysical properties of HMAPN were investigated in solution and on LB films.The photoelectric properties of HMAPN were examined and the anodic photocurrent of the ITO electrode modified by the monolayer LB film of HMAPN was measured as 835 nA/cm^2 under the white light of 218.2 mW/cm^2 without bias voltage.The effects of light intensity,bias voltage on the photocurrent were discussed.The possible mechanism of the photocurrent formation was given.     

The effect of polymerization conditions on crystalline of polybutene-1 catalyzed by metallocene catalyst

Polybutene-1 was synthesized stereoselectively with the precursorη5-(pentamethyl-cyclopentadienyl) tribenzyloxide titanium (Cp*Ti(OBz)3) and methylaluminoxane (MAO). The effects of polymerization conditions, trimethyl alumina (TMA) content in MAO and temperature on the crystalline and molecular weight of the products, and catalytic activity were investigated. The structural properties of the polybutene-1 were characterized with 13C NMR and WAXD.     

Studies on Agarofurans Ⅷ.Synthesis of the Metabolites of 4—Butyl—α—agarofuran

The structures of five metabolites (2-6) of agarofuran 1 were confirmed by synthesis. The configuration of the secondary hydroxyl in 7 was determined by Horeau′s method. The configuration of C-2 in compound 4 and 5 was determined by their stereochemistry and NMR.     

Investigation of Isomerization of 2—Seleno—1,3,2—diazaphospholidine Derivatives

For the first time the isomerization of 1,3,2-diazaphospholidine-2-sclenide dervatives in refluxing benzene in the presence of trace water was observed. The structures of isomerized products were determined by IR, ^1H NMR,^31P NMR, elemental analysis and X-ray crystallography. The mechanism of isomerization was also proposed.     

Synthesis of （1H）—3,4—Dithydropyrrolo[2,1—c][1,4]oxazin—1—one Derivatives

In search of new anti-inflammatory and analgesic agents,(1H)-3,4-dihydro-pyrrolo [2,1-c][1,4]oxazin-1-one(3) and its acyl derivatives were designed and prepared .Compound 3 was prepared by treatment of methyl 1-(2-bromoethyl) pyrrole-2-carboxylate with silver oxide and its derivatives were obtained by Friedel-Carftes reaction.Nine of 6-acyl derivatives of compound 3 were prepared.     

Enantiospecific Synthesis of All Four Stereoisomers of Novel Bicyclic Arylacetamides as κ—Opioid Agonists

Conformationally constrained bicyclic derivatives of the potent and selective κ-opioid receptor agonist 2-(3,4-dichlorophenyl)-N-methyl-N-[(1S)-1-Phenyl-2-(1-Pyrrolidinyl)-ethyl]acetamide(3,ICI-199,441)were designed to explore the effect of the conformational restriction and stereochemistry of the pharmacophoric ethylenediamine incorporated into the pyrrolidine on the affinity and κ-selectivity.A facile enantiosipecitfic synthetic route was extablished to afford all four stereoisomers starting from readily available amino acids through mild cyclization and amide formation.     

Synthesis of 3,7—Disubstituted 1,4—Benzodiazepin—2—one

A series of 3-methoxycarbonylpropoxy-7-(imidazol-4-ylpropinamide)-1,3-dihydrogen-1-methyl-5-phenyl-2H-1,4-benzodiazepin-2-ones,as farnesyltransferase(Ftase) inhibitors,were synthesized. The preparation of the key intermediate,7-amino-3-methoxycabonylpropoxy-1-methyl-5-phenyl-2H-1,4-benzodiazepin-2-one,was improved.     

The mechanism of asymmetric reduction catalyzed by a C_2 symmetric bis-amino alcohol catalyst——In situ NMR study of the structure of new type of dual-centered catalyst

By means of 1H, 13C, 11B NMR, polar transfer DEPT135, DEPT90 and 2D NMR experiments, IR, etc, the structure of the diaminodihydroxyl ligand and its derivatives used in the asymmetric reduction of prochiral ketones were detected. The catalysts derived from the ligand and bo-rane formed in situ were also studied and the structure transformations in solution were monitored.The structure of the catalyst was proved to be a new type of dual-centered catalyst——bis-oxazaborolidine.     

First Synthesis of a Series of New Natural Glucosides

Alkyl glucoside 1 and aryl glycosides 2-4 were highly stereospecifically synthesized over 4-6 steps from commercially available starting materials. The coupling reaction of the acetobromo-α-D-glucose with the unprotective dihydroxy aglycon in the presence of silver oxide, or with aromatic aglycon in the presence of sodium hydroxide produced the key intermediate. Only β-configuration glycosides were formed in this procedure. The synthesis of all these glycosides was reported for the first time.     

Catalytic Combustion of Methane over CO1-xMgxO/Al2O3/FeCrAl Monolithic Catalysts

A series of CoxMgxO/Al2O3/FeCrAl catalysts （x=0-1） were prepared. The structures of the catalysts were characterized using XRD, SEM, and TPR analyses. The catalytic activity of the catalysts for methane combustion was evaluated in a continuous flow microreactor. The results indicated that the active washcoats adhered well on the FeCrAl foils. The phases in the catalysts were Co--xMgxO solid solutions, α-Al2O3, and γ-Al2O3. The surface particle size of the catalysts varied with variations in the molar ratios of Co to Mg. The Co component of the Co1_xMgxO/Al2O3/FeCrAl catalysts played an important role in the catalytic activity for methane combustion. In the Co1-xMgxO/AluO3/FeCrAl series catalyst （x=0.2-0.8）, the catalytic activity in terms of x was in the order of 0.5〉0.2〉0.8 under the experimental conditions. The presence of Mg in these catalysts could promote the thermal stability to a large extent. There were strong interactions between the Co1-xMgxO oxides and the AluO3/FeCrAl supports.     

Microcalorimetric Studies of the Toxic Action of La^3＋ on Halobacterium Halobium R1 Growth

A microcalorimetric technique was used to evaluate the influence of La^3 on Halobacterium halobium R1 growth.By means of LKB-2277 bioactivity monitor,ampoule methos at 37℃,the thermogenic curves of Halobacterium halobium R1 growth were obtained.In order to analyze the results,the maximum power Pm and the growth rate constants k were determined,showing that values of Pm and k are linked to the concentration of La^3 .Addition of low concentration of La^3 can cause a decrease of the maximum heat production and growth rate constant.However,high concentration of La^3 may promote growth of Halobacterium halobium R1,but at much higher concentration of La^3 ,the growth of Halobacterium halobium R1 is inhibited again.For comparison,the shapes of Halobacterium halobium R1 cell were observed by means of transmission electron microscope.According to the thermogenic curves and TEM photos of Halobacterium halobium R1 under different conditions,it is clear that metabolic mechanism of Halobacterium halobium R1 growth is changed with the addition of La^3 .     

Preparation of Diphenyl Oxalate from Transesterification of Dimethyl Oxalate with Phenol over TS—1 Catalyst

Diphenyl oxalate was synthesized from transesterification of dimethyl oxalate with phenol over TS-1(2.5 wt% Ti)catalyst.TS-1 catalyst,as a beterogeneous catalyst,showed excellent selectivity of diphenyl oxalate and methylphenyl oxalate compared with other homogeneous catalysts.Lewis acid sites on TS-1 catalyst were the active sites for transesterification of dimethyl oxalate with phenol.the high selectivity was closely related to the weak acid sites over TS-1.     

Syntheses and Biological Activities of Novel 3-Bromo-1-（3-chloropy- ridin-2-yl）-N-hydroxy-N-aryl- 1H-pyrazole-5-carboxamides

A series of novel 3-bromo-1-（3-chloropyridin-2-yl）-N-hydroxy-N-aryl-lH-pyrazole-5-carboxamides was synthesized by the reaction of pyrazole carbonyl chloride with each of substituted phenylhydroxyamines. The latter ones were prepared in good yields by reducing substituted nitrobenzene compounds with Zn/NH4CI reductant system in alcohol. Structures of the title compounds were determined by IR, 1H NMR, and HRMS. Their insecticidal and fungicidal activities were evaluated by larvicidal test against oriental armyworm and the mycelium growth rate method, respectively.