Synthesis,Bioactivity and Crystal Structure Analysis of 2-(Benzo[d]isothiazol-3-yloxy)-N-(3-cyano-1-(4-fluorophenyl)-1H-pyrazol-5-yl) Acetamide

A novel benzisothiazolin-3-one derivative, 2-(benzo[d]isothiazol-3-yloxy)-N-(3-cyano-1-(4-fluorophenyl)-1H-pyrazol-5-yl) acetamide(8), was synthesized from the initial compound benzo[d]isothiazol-3(2H)-one(BIT) 1 and 4-fluoroaniline 3. The structure of the target compound 8 was determined by elemental analyses, IR and 1H NMR. The single crystals of intermediate compound 6 and the target compound 8 were obtained and determined by X-ray diffraction analysis. The preliminary biological activity was also evaluated and the results showed the target compound exhibited a good anti-microbial activity.     

苏型-N-苯甲酰基-3-苯基异丝氨酸甲酯的合成

紫杉醇;苏型-N-苯甲酰基-3-苯基异丝氨酸甲酯的合成     

基于环蕃类分子的铁氰化钾电化学存储和释放

通过利用合成的环蕃类化合物1与单壁碳纳米管(SWNTs)间的π-π共轭相互作用,将化合物1固定在SWNTs的表面,制备了1-SWNT修饰电极.利用化合物1氧化态和还原态与铁氰化钾分子之间不同强度的主客体相互作用,实现了铁氰化钾分子在1-SWNT修饰电极表面的电化学可控吸附和解吸.循环伏安和XPS实验结果表明,在本研究采用的实验条件下,铁氰化钾分子在电极表面20s内即可达到吸附平衡;当电极在0.70V下极化1000s后,大多数吸附的铁氰化钾可从电极表面解吸.基于此,制备了铁氰化钾的可控存储和释放的电化学器件,该器件不但可以重复进行铁氰化钾分子的存储和释放,而且多次重复操作表现出较好的稳定性和重现性.本研究在发展具有特殊用途的电化学纳米器件,例如分子搬运器、电化学开关等研究中具有重要意义.     

键合香豆素席夫碱基的杯[4]芳烃的合成及其对金属离子的荧光识别作用

通过5,17-二氨基杯[4]芳烃衍生物与7-羟基-8-甲酰基-4-甲基香豆素缩合,得到了一种以亚胺基团为离子载体、香豆素为荧光基团的新型杯芳烃荧光识别试剂。 采用IR、1H NMR、13C NMR和MS测试技术表征了合成化合物的结构。 通过紫外光谱和荧光光谱,研究了其对过渡金属和重金属离子的识别性能。 结果表明,该化合物对Fe3+和Cr3+离子具有选择识别能力,与Fe3+和Cr3+配合的化学计量比为1∶1,配合生成常数分别为4.1×105和1.07×105 L/mol。     

Syntheses of substituted-oxazolo-1,3,4-thiadiazoles, 1,3,4-oxadiazoles,and 1,2,4-triazoles

Starting from readily available methyl 5-methyloxazole-4-carboxylate ( 1 ) and 4-methyl-5-oxazolylcar-boxylic acid hydrazide ( 11 ) the title compounds were prepared. The reaction of compound 1 with hydrazine hydrate afforded the corresponding hydrazide 2 . The reaction of compound 2 with formic acid yielded 1-formyl-2-(5-methyloxazole-4-carboxyl)hydrazine ( 3 ). Refluxing of the latter with phosphorus pentasulfide in xylene gave compound 5 in 62% yield. The reaction of compound 3 with phosphorus pentoxide afforded compound 4 . Starting from hydrazide 11 , compounds 13 and 14 were prepared similarly. Reaction of compound 2 with substituted isothiocyanate yielded compound 9 which was cyclized in basic medium to 4-alkyl-5-(5-methyl-4-oxazolyl)-2,4-dihydro-3H-1,2,4-triazole-3-thione ( 10 ). The isomer 19 was prepared similarly. Methylation and subsequent oxidation of compound 19 gave compound 21 . Reaction of the acid 7 with thiosemicarbazide in the presence of phosphorus oxychloride gave 2-amino-5-(5-methyl-4-oxazolyl)1,3,4-thiadiazole ( 8 ). 2-Amino-5-(4-methyl-5-oxazolyl)-1,3,4-thiadiazole ( 17 ) was prepared from acyl chloride 15 by the usual method.     

3-氨基-2-羟基-4-苯基丁酸的合成

3-氨基-2-羟基-4-苯基丁酸的合成;乌苯美司;氨基羟基苯基丁酸;合成     

Synthesis, Crystal Structure and DNA Binding Studies of α,α'-Bis(3,5-bismethyl-1-pyrozolyl)- carbene-acetyl-isopropenyl Hydrazine

The title compound α,α'-bis(3,5-bismethyl-pyrozole-N-yl)-carbene-acetyl-isopro-penyl hydrazine (C16H22N6O, Mr = 314.40) has been prepared. It was characterized by elemental analysis as well as IR, MS, 1H-NMR and 13C-NMR spectra. Its crystal structure was determined by single-crystal X-ray diffraction, getting the following data: triclinic, space group P1 with a = 6.9734(16), b = 10.773(3), c = 12.001(3) A, α = 75.311(4), β = 82.695(4), γ = 77.143(4)°, Z = 2, V = 847.9(3) A3, Dc : 1.231 g/cm3, F(000) = 336 and μ(MoKα) = 0.082 mm-1 (λ = 0.71073 A). The results of crystal structure determination show that there exist intermolecular and intramolecular hydrogen bonds, resulting in a two-dimensional supramolecular framework of the title compound. The binding of the title compound to DNA was investigated by absorption, emission, and viscosity measurements. The title compound shows absorption hyperchromicity accompanied by a blue shift at about 254 nm. The binding constant Kb for the title compound has been determined to be 1.89 × 104 M-1 from absorption measurements. The addition of the title compound to DNA pretreated with EB causes appreciable reduction in the emission intensity, indicating that the DNA-bound EB fluorophore is partially replaced by the title compound. The value of K is 3.093 × 104 M-1. The relative viscosity of DNA decreased with the addition of the title compound. Results suggest that the title compound binds to DNA with a non-classical intercalative or groove interaction mode. The observed efficient nuclease activity of the title compound is interesting and may have further influences on the chemistry of DNA minor groove binders.     

新的核苷衍生物N2,N3-亚乙烯基腺嘌呤核苷的合成

描述了一条有效的合成新的荧光核苷衍生物N2,N3-亚乙烯基腺苷的合成路线.实验中首先通过6步制备了N2,N3-亚乙烯基鸟苷,然后经过氯化,再氨化得到标题化合物.标题化合物和新的中间化合物的结构分别通过1H NMR, MS和HRMS进行了确证,标题化合物的荧光性质初步得到证实.     

双核Pt(Ⅳ)配合物与Guanosine-5''''-Monophosphate和Glutathione反应的核磁共振光谱研究

合成了一个新型的双核Pt(Ⅳ)配合物{[cis-Pt(NH3)2Cl(OH)2]2(4,4'-methylenedianiline)}(NO3)2(化合物1)及相应的 15N标记化合物{[cis-Pt(15NH3)2Cl(OH)2]2(4,4'-methylenedianiline)}(NO3)2(化合物15N-1).利用1H NMR和ESMS进行了结构表征,化合物15N-1的2D[1H,15N]HSQC NMR发现,该化合物在水溶液中存在同分异构体.2D[1H,15N]HSQC NMR技术跟踪了化合物15N-1与Guanosine-5'-Monophosphate(5'-GMP)和Glutathione(GSH)的反应.结果显示,5'-GMP能在0.5 h内将化合物1还原,而GSH在6 h以后才能够部分的将化合物1还原.化合物1所表现出来的反应性能将有利于提高其治疗效果和降低毒副作用.     

Construction of the Skeleton of Phthalascidin, Mechanism of the Formation of the Key Tricyclic Lactam Intermediate

Phthalascidin is a structurally simplified version of Et-743, which is a potent anti-tumor marine natural product isolated from Ecteinascidia turbinata. Its antiproliferative activity is greater than that of the agents taxol, camptothecin, adriamycin, mitomycin C, cisplatin, bleomycin, and etoposide by 1-3 orders of magnitude. An elegant synthesis of Et-743 and phthalascidin has been reported by E. J. Corey and co-workers1,2. As part of our continuing program, we have also engaged in dev…     

Synthesis and luminescent properties of pyrenylvinylene-substituted tripylborane

A novel luminescent compound, bis((E)-2-pyren-1-yl-vinyl)-2,4,6-triisopropylphenylborane (3) was synthesized by hydroboration reaction and was fully characterized. The obtained compound was further investigated by single-crystal X-ray diffraction analysis and DFT calculations. The extended structure tells us their herringbone structures with closely faced pairs of the molecules. Comparing the photoluminescent spectra between solution-state and solid state, the spectrum of the solid state of the compound 3 exhibited dramatically red-shifted fluorescent emission. This change also supports the efficient π-stacking behavior of the compound 3.     

层状K4Ag2Sn3S9·2H2O的溶剂热合成与表征

用溶剂热法合成了K4Ag2Sn3S9·2H2O,通过单晶X射线衍射、DSC、TG、IR和紫外漫反射光谱等手段对其进行了表征.结果表明,K4Ag2Sn3S9·2H2O属单斜晶系,P21/m空间群,a=0.78071(2)nm,b=2.73508(1)nm,c=1.05008nm,α=90°,β=103.87(6)°,γ=90°,Z=4.其层状结构内具有一维孔道,钾离子分离在层间及层内孔道中.     

O,O-二乙基-N-[2-(3-乙酰基-2,2-二甲基-环丁基)-乙酰] 硫代磷酰胺合成及杀虫活性研究

α-蒎烯经过氧化、酰氯化制成蒎酮酰氯, 再与二乙基硫代膦酰胺反应, 合成了未见报道的标题化合物7, 经IR, MS, 1H NMR, 13C NMR等对标题化合物的结构进行了表征. 测试了标题化合物对甘蓝薄翅螟的毒力及其对敌百虫的增效作用. 初步生物活性测试结果表明, 标题化合物与敌百虫混合对甘蓝薄翅螟有明显的增效作用, 当标题化合物与敌百虫以3∶7的比例混合其增效作用最显著, 共毒系数(co-toxicity oefficient, CTC)为226.     

Novel synthesis of 2-butyl-5-chloro-3H-imidazole-4-carbaldehyde： A key intermediate of Losartan

A novel method for synthesis of 2-butyl-5-chloro-3H-imidazole-4-carbaldehyde 2, a key intermediate of Losartan was reported. The compound 2 was synthesized from starting material dimethyl malonate 6 and n-valeronitrile 8 by six steps with an overall yield of 40%.The key step including the reaction of compound $ with POCI3/DMF followed by hydrolysis to give compound 2 with the yield of 68%.     

Syntheses of 2-(2-arylethyl)-1-methylimidazoles

2-(2-Arylethyl)-1-memylimidazoles 3 could be prepared by different methods. The best method was the Wittig reaction of aryltriphenylphosphonium chloride 8 with 2-formyl-1-methylimidazole to give compound 6 . Reduction of compound 6 with Raney nickel gave compound 3 .     

Mass spectrometric identification of an azobenzene derivative produced by smectite-catalyzed conversion of 3-amino-4-hydroxyphenylarsonic acid

The compound 3-amino-4-hydroxyphenylarsonic acid (3-amino-HPAA) reacts with smectite to form a soluble azobenzene arsonic acid compound. This reaction is of particular interest because it provides a possible mechanism for the formation of a new type of arsenic compound in natural water systems. 3-Amino-HPAA is a degradation product excreted by chickens that are fed rations amended with roxarsone. Roxarsone is used to control coccidial intestinal parasites in most of the broiler chickens grown in the United States. The structure of the azobenzene arsonic acid compound was first inferred from negative-ion and positive-ion low-resolution mass-spectrometric analyses of the supernatant of the smectite suspension. Elemental composition of the parent ion determined by high-resolution positive-ion mass spectrometric measurements was consistent with the proposed structure of the azobenzene arsonic acid compound.     

Synthesis and biological evaluation of 3-chloro-1-carbacephem compounds

The 3-chloro-1-carbacephem nucleus was prepared for the first time from a 3H-1-carbacephem compound through a sequence of reactions involving addition of thiophenol, oxidation of sulfide to sulfoxide, and alpha-chlorination of the sulfoxide, followed by elimination of phenylsulfinic acid. The 2-beta-methyl analog was similarly prepared, but the 2 alpha-methyl analog was not obtained. Optical resolution of the 3-chloro-1-carbacephem compound was achieved by the employment of penicillin acylase. That is, the 7-phenylacetamido derivative was enantioselectively hydrolyzed to afford the optically active 7-amino-3-chloro-1-carbacephem compound. Carbacefaclor, the carbacephem analog of cefaclor, was directly and efficiently prepared by enzymatic phenylglycylation of the racemic 7-amino-3-chloro-1-carbacephem compound by using immobilized penicillin acylase. Carbacefaclor thus prepared exhibited comparable antibacterial activity against most gram positive bacteria tested and higher activity against typical gram negative bacteria as compared with cefaclor. Moreover, carbacefaclor possessed remarkably high chemical stability.     

4-氨基-5-[2-(4-氯苯氧甲基)苯并咪唑-1-亚甲基]-1,2,4-三唑-3-硫酮的核磁共振研究

在无水乙醇和KOH存在下,将2-(4-氯苯氧甲基-1-苯并咪唑乙酰肼(1)与CS2反应,合成出了中间体酰肼二硫代甲酸钾盐.此中间体再与过量的水合肼反应,经环化得到一种新化合物4-氨基-5-[2-(4-氯苯氧甲基)苯并咪唑-1-亚甲基]-1,2,4-三唑-硫酮.采用元素分析、IR及NMR技术确定了新化合物的结构,并利用2...     

Synthesis,Crystal Structure and DNA Binding Studies of α,α'-Bis(3,5-bismethyl-1-pyrozolyl)-carbene-acetyl-isopropenyl Hydrazine

The title compound α,α'-bis(3,5-bismethyl-pyrozole-N-yl)-carbene-acetyl-isopro- penyl hydrazine (C16H22N6O, Mr = 314.40) has been prepared. It was characterized by elemental analysis as well as IR, MS, 1H-NMR and 13C-NMR spectra. Its crystal structure was determined by single-crystal X-ray diffraction, getting the following data: triclinic, space group P1 with a = 6.9734(16), b = 10.773(3), c = 12.001(3) , α = 75.311(4), β = 82.695(4), γ = 77.143(4)o, Z = 2, V = 847.9(3) 3, Dc = 1.231 g/cm3, F(000) = 336 and μ(MoKα) = 0.082 mm-1 (λ = 0.71073 ). The results of crystal structure determination show that there exist intermolecular and intramolecular hydrogen bonds, resulting in a two-dimensional supramolecular framework of the title compound. The binding of the title compound to DNA was investigated by absorption, emission, and viscosity measurements. The title compound shows absorption hyperchromicity accompanied by a blue shift at about 254 nm. The binding constant Kb for the title compound has been determined to be 1.89 × 104 M-1 from absorption measurements. The addition of the title compound to DNA pretreated with EB causes appreciable reduction in the emission intensity, indicating that the DNA-bound EB fluorophore is partially replaced by the title compound. The value of K is 3.093 × 104 M-1. The relative viscosity of DNA decreased with the addition of the title compound. Results suggest that the title compound binds to DNA with a non-classical intercalative or groove interaction mode. The observed efficient nuclease activity of the title compound is interesting and may have further influences on the chemistry of DNA minor groove binders. Keywords: α,α'-bis(3,5-bismethyl-pyrozole-N-yl)-carbene-acetyl-isopropenyl, preparation, crystal structure, DNA binding     

Synthesis and study of beryllium bis{3-[β-(triethylsilyl)-β-chloroethylthio]-2,4-pentanedionate}

A silicon-containing metal chelate is prepared by the addition of beryllium bis(3-chlorothiopentane-2,4-dionate) to vinyltriethylsilane. The compound was isolated by chromatography, and its composition was determined by elemental analysis. The compound was identified as beryllium bis{3-[β-(triethylsilyl)-β-chloroethylthio]-2,4-pentanedionate}. To confirm this structure, the compound was converted into the pyrazole derivative by the reaction with hydrazine, and the product was examined by mass spectrometry.