一锅法合成3-芳基-1，5-双（2-羟基芳基）-戊二酮-1，5

2-羟基苯乙酮、芳醛、氢氧化钾“一锅”反应合成了3-芳基-1，5-双（2-羟基芳基）-戊二酮-1，5。     

2-叔丁基-4-氟-苯并氧杂卓并[3,4-b]喹啉并[9,11]二氧戊环-14（6H）-酮的合成

以2-溴甲基-6,7-亚甲二氧基-3-喹啉酸乙酯(1)为原料,经三步合成了2-叔丁基-4-氟-苯并氧杂卓并[3,4-b]喹啉并[9,11]二氧戊环-14(6H)-酮(4)。其中,6-(2-氟-4-叔丁基-苯氧甲基)-[1,3]二氧戊环并[4,5-g]喹啉-7-羧酸是经一锅法合成的。它的分子内闭环反应是在Eaton’s reagent(P2O5-CH3SO3H)的作用下,在较温和的条件下进行的。所得新化合物3和4的结构经IR1、H NMR和元素分析得以证实。     

乙酸酐、H2O2和1,5二-羟基萘酚一锅合成胡桃醌

由乙酸酐和H2O2在无硫酸存在下合成过氧乙酸,然后向其滴加1,5-二萘酚的甲醇溶液,在一锅内简便地合成了胡桃醌。产物用苯重结晶,其结构经HPLC、UV-Vis、FTIR、^1H NMR和^13C NMR测试技术进行了表征和证实。考察了原料摩尔比、反应温度和反应时间对产率的影响。最佳反应条件为：n（1,5-二萘酚）：n（乙酸酐）：n（H2O2）=1：4：8,反应温度为40-60℃,反应时间为5．5h,产率68％。结果表明,一锅法合成不用硫酸,无需真空蒸馏纯化过氧乙酸,是合成胡桃醌的简便方法。     

“一锅法”合成6-氯取代的2-苯氧甲基-3-喹啉甲酸衍生物（英文）

设计了以6-氯-2-氯甲基-3-喹啉甲酸乙酯(1)为起始化合物,在溶剂乙腈、缚酸剂无水碳酸钾的条件下,通过"一锅法"与苯酚及取代苯酚2a-o反应,合成了喹啉环上含有氯原子的6-氯-2-苯氧甲基-3-喹啉甲酸衍生物3a-o.所合成的化合物3a-o的结构经红外光谱、核磁共振氢谱、核磁共振碳谱和高分辨质谱得以证实.     

"一锅法"合成5-氟-2-羟基-苯乙酮

对合成5-氟-2-羟基-苯乙酮的方法进行改进,将原来的两步反应合并为一步,去掉了中间产物酯的繁琐分离和纯化,大大缩短了反应时间,操作简便,收率88．9％,适用于工业化生产。     

Synthesis and Crystal Structure of （E）-4-（3-oxo-3-（（4- （N-（pyrimidin-2-yl）-sulfamoyl）phenyl）amino）prop- 1-en-l-yl）-l,2-phenylene diacetate Dimethanol

The title compound, (E)-4-(3-oxo-3-((4-(N-(pyrimidin-2-yl)sulfamoyl)-phenyl)ami- no)prop- 1-en- 1-yl)- 1,2-phenylene diacetate dimethanol, was synthesized by the reaction of caffeic acid with sulfadiaz...     

一锅法合成2-（5-氨基-1,3,4-噻二唑）基丙酸乙酯

以丁二酸酐和氨基硫脲为原料，采用“一锅法”经脱水环合合成了重要医药中间体2-（5-氨基-1,3,4-噻二唑）基丙酸乙酯，其结构经¹H NMR， IR和MS确证。并对反应条件进行了优化，最佳反应条件为: n（氨基硫脲: n（丁二酸酐）: n（浓硫酸）=1: 2: 3，于80 ℃反应6 h，收率70%。     

一锅法合成4-(5-芳基-1,3,4-噻二唑-2-氨甲基)苯酚衍生物

以2-氨基-5-芳基噻二唑衍生物和对羟基苯甲醛为原料,经亲核加成/脱水、还原两步一锅法合成了一系列新的4-(5-芳基-1,3,4-噻二唑-2-氨甲基)苯酚衍生物,反应具有时间短、后处理简单等优点.采用元素分析,NMR,IR以及质谱等多种谱学技术对产物进行了详细表征.     

Reduced Species （HSO2^-, SO2^·-） Promoted One-Pot Efficient Synthesis of Phenyl Alkyl Selenides

Reduced species （HSO2^-, SO2^·-） promoted one-pot synthesis of phenyl alkyl selenides has been developed. This synthetic method was achieved by reactions of diphenyl diselenide with alkyl halides at room temperature. It is noteworthy that the reactions were operated under mild reaction conditions, required short time, and got good resuits. A single electron transfer reaction mechanism was proposed for the reaction.     

一锅法合成2，4，6-三氯喹唑啉和6-硝基-2，4-二氯喹唑啉

在五氯化磷的存在下,2-氨基-5-氯苯甲酸(1a)或2-氨基-5-硝基苯甲酸(1b)与尿素缩合,一锅法合成了2,4,6-三氯喹唑啉(2a)或6-硝基-2,4-二氯喹唑啉(2b),其结构经1H NMR和ESI-MS表征.合成2a的最佳反应条件为:1a 2.5 mmol,n(1a):n(PCl5):n(尿素)=1.0:6.0:2.2,回流反应1 h,收率41%.     

Rate coefficients for the reaction of OH with (E)-2-pentenal, (E)-2-hexenal, and (E)-2-heptenal

Rate coefficients for the gas-phase reaction of the OH radical with (E)-2-pentenal (CH(3)CH(2)CH[double bond]CHCHO), (E)-2-hexenal (CH(3)(CH(2))(2)CH[double bond]CHCHO), and (E)-2-heptenal (CH(3)(CH(2))(3)CH[double bond]CHCHO), a series of unsaturated aldehydes, over the temperature range 244-374 K at pressures between 23 and 150 Torr (He, N(2)) are reported. Rate coefficients were measured under pseudo-first-order conditions in OH with OH radicals produced via pulsed laser photolysis of HNO(3) or H(2)O(2) at 248 nm and detected by pulsed laser-induced fluorescence. The rate coefficients were independent of pressure and the room temperature rate coefficients and Arrhenius expressions obtained are (cm(3) molecule(-1) s(-1) units): k(1)(297 K)=(4.3 +/- 0.6)x 10(-11), k(1)(T)=(7.9 +/- 1.2)x 10(-12) exp[(510 +/- 20)/T]; k(2)(297 K)=(4.4 +/- 0.5)x 10(-11), k(2)(T)=(7.5 +/- 1.1)x 10(-12) exp[(520 +/- 30)/T]; and k(3)(297 K)=(4.4 +/- 0.7)x 10(-11), k(3)(T)=(9.7 +/- 1.5)x 10(-12) exp[(450 +/- 20)/T] for (E)-2-pentenal, (E)-2-hexenal and (E)-2-heptenal, respectively. The quoted uncertainties are 2sigma(95% confidence level) and include estimated systematic errors. Rate coefficients are compared with previously published room temperature values and the discrepancies are discussed. The atmospheric degradation of unsaturated aldehydes is also discussed.     

(E)- and (Z)-1-benzenesulfonyl-4-trimethylsilyl-2-butenes as (E)-1-(1,3-butadienyl) synthons

(E)- and (Z)-1-benzenesulfonyl-4-trimethylsilyl-2-butenes (E/Z=9), prepared from 4-trimethylsilyl-1-buten-3-ol, $\text{n}$-butyllithium and benzenesulfenyl chloride and oxidation of the intermediate (E)- and (Z)-1-benzenesulfinyl-4-trimethylsilyl-2-butenes with hydrogen peroxide, react with $\text{n}$-butyllithium and then primary halides to give 4-benzenesulfonyl-1-trimethylsilyl-2-alkenes which are rapidly 1,4-debenzenesulfonyltrimethylsilated to (E)-1,3-alkadienes by tetra-$\text{n}$-butylammonium fluoride at O°C.     

Bioanalysis of (E)-5-(2-bromovinyl)-2'-deoxyuridine

(E)-5-(2-Bromovinyl)-2'-deoxyuridine is an antiviral drug that is experimentally used for modulation of the antitumour effect of fluoropyrimidines, such as ftorafur and 5-fluorouracil. The isolation of the analyte, in the presence of 5-fluorouracil, from the matrix is performed either by means of a simple protein precipitation (plasma) or by means of a liquid-liquid extraction with ethyl acetate (urine). Following pretreatment, the analyte is analysed by reversed-phase chromatography and quantified by absorbance detection at 307 nm. The minimum detectable concentration in plasma and urine samples is ca. 6 ng/ml. The recovery after deproteination of plasma samples is 75%, while after liquid-liquid extraction of urine the recovery amounts 92%. The degree of protein binding of the analyte, measured by ultrafiltration, is found to be 97%. These data allow the bioanalysis of (E)-5-(2-bromovinyl)-2'-deoxyuridine for pharmacokinetic studies.     

One-Pot synthesis of (2E)- and (2E, 4E)- unsaturated carboxylic acid amides via organotellurium reagents

Di-n-butyl telluride, 2-bromoacetylisobutylamide (or 2-bromoacetylpiperidide) react directly with saturated or α,β-unsaturated aldehydes at room temperature in the presence of potassium carbonate(s) to afford (2E)-, or (2E, 4E)-unsaturated carboxylic acid amides, respectively, in excellent yields with high E stereoselectivity.     

Synthesis,spectral characterization,molecular docking studies,biological activity of (E)-2-((E)-3-(3,4,5-trimethoxyphenyl)allylidene) and (E)-N-phenyl 2-((E)-3-(3,4,5-trimethoxyphenyl)allylidene)hydrazinecarbothioamides and their Cu(II) complexes

Two slightly distorted octahedral complexes of copper(II) with (E)-2-((E)-3-(3,4,5-trimethoxyphenyl)allylidene)hydrazinecarbothioamide (L1) common name 3,4,5-trimethoxy-cinnamaldehydethiosemicarbazone and (E)-N-phenyl-2-((E)-3-(3,4,5-trimethoxyphenyl)-allylidene)hydrazinecarbothioamide (L2) common name 3,4,5-trimethoxycinnamaldehyde-4-phenylthiosemicarbazone have been synthesized. The two free ligands and their copper(II) complexes were characterized by spectroscopic techniques like FT-IR, FT-Raman, UV, EPR, Powder X-ray diffraction and cyclic voltammetry. The EPR spectra evidenced a rhombically distorted octahedron geometry for both the copper(II) complexes. The band gap calculations for the ligands L1, L2 and their complexes Cu(L1)₂Cl₂ and Cu(L2)₂Cl₂ were found to be 2.98, 2.61, 2.66 and 2.50 eV respectively. Cu(L1)₂Cl₂ and Cu(L2)₂Cl₂ have shown 50% of viability at 80 μg/ml and 60 μg/ml. The anti-oxidant activity study revealed that the compounds are good reductants of DPPH radical. Moderate to good anti-bacterial activity is shown by the compounds against the Gram-positive and Gram-negative bacteria. Molecular docking studies have been carried out to predict the orientation and binding mode of analysis in the active site. The synthesized ligand and complex well occupy (catalytic triad and adenine-binding site) in the active site of β-ketoacyl-acyl carrier protein synthase III enzyme, and also well occupy in helix 11 (in the DCS complex) of human estrogen receptor. Moreover they form water mediated hydrogen bond and hydrogen bond with Cys530 residue.     

A Convenient Regiospecific Syntheses of (E)-1-Alkanesulfonyl- and (E)-1-Arylsulfonyl-2-Phenylethenes

(E)-1-Alkanesulfonyl- and (E)-1-arylsulfonyl-2-phenylethenes (styryl sulfones) were obtained from good to excellent yields by the base-catalyzed elimination of the corresponding β-chlorosulfones. The latter were obtained, respectively, by additions of the alkanesulfonyl- and the arylsulfonyl chlorides to styrene under the catalytic action of copper chlorides.     

Stereoselective Syntheses and Biological Properties of (E)-α-(Methoxyimino)-2-[1-(aryloxy)methyl]-benzeneacetates

(E)-α-(Methoxyimino)-2-[1-(aryloxy)methyl]-benzeneacetates, the analogues of Kresoxim-methyl, were stereoselectively synthesized with the coupling reaction of 2-methylphenyldiazonium chloride and methyl 2-hydroxyiminoacetate in the presence of CuSO4/Na2SO3 as a key step, and it was first found that the coupling reaction could give the key intermediate material(E)- and(Z)-methyl 2-(hydroxyimino)-2-o-tolylacetate with a molar ratio of 14∶1. The(E)-configurations of all these compounds were assigned on the basis of their 2D-NOESY spectra of 1H NMR. The preliminary bioassays indicate that most of the compounds show an activity against a wide variety of fungi.     

Synthesis of (E)-2-chlorovinyltellurium trichloride and (E,E)-bis(2-chlorovinyl) ditelluride

The reaction of tellurium tetrachloride with acetylene in CCl₄ at atmospheric pressure and ambient temperature affords earlier unknown (E)-2-chlorovinyltellurium trichloride in 30% yield, whose reduction with sodium bisulfite gives (E,E)-bis(2-chlorovinyl) ditelluride in 64% yield.     

(E)-N-芳基-3-[2-(8-羟基喹啉基)-乙烯基]咔唑的合成、抗氧化活性及促进鼠骨髓间质干细胞增殖的研究

设计合成了3-[2-(8-羟基喹啉基)-乙烯基]-N-对甲苯基咔唑(8)和3-[2-(8-羟基喹啉基)-乙烯基]-N-对甲氧苯基咔唑(9)两个新的化合物, 用IR, MS, 1H NMR和元素分析确认其结构. 并利用DPPH•方法, 超氧阴离子自由基( )法, 羟基自由基HO•法和噻唑蓝比色法(MTT法)分别测定了目标产物的抗氧化活性和调控鼠骨髓间质干细胞(MSCs)的作用. 结果表明, 这两种化合物对DPPH•自由基、超氧阴离子自由基和羟基自由基具有较强的抗氧化活性, 化合物9在低浓度时对鼠骨髓间质干细胞增殖有很好的促进作用.     

(E)-1-alkyl-4-

(E)-1-Alkyl-4-[2-(alkylsulfonyl)-1-ethenyl]pyridinium salts were synthesized in two steps. These sulfones were stable at pH 7.3 and underwent a nucleophilic vinylic substitution (S(N)V) with mercaptans, including thiouracile, to give the corresponding 4-(thiovinyl)-pyridinium salts. The X-ray diffraction structure of (E)-1-methyl-4-[2-(ethylsulfanyl)-1-ethenyl]pyridinium iodide indicated conjugation of the sulfur with the pyridinium ring. (Z)-1-Methyl-4-[2-(methylsulfanyl)-1-ethenyl]pyridinium iodide, prepared from the corresponding thioether by reaction with methyl iodide in diethyl ether, underwent isomerization to the E isomer in a first-order reaction in deuterated [D6]DMSO with an activation energy of 14 kcalmol(-1). At pH 7, the (E)-1-methyl-4-[2-(methylsulfonyl)-1-ethenyl]pyridinium iodide (19) reacted specifically with thiols. The reaction of this sulfone with glutathione in a TES buffer at pH 7 was a second-order reaction (k = 4,100 M(-1)s(-1) at 30 degrees C) and gave the corresponding substitution product with an intense long wavelength absorption band (lambdamax=360 nm, epsilon = 27,500 M(-1)cm(-1)). The modification of different enzymes of known structure with 19 showed the high selectivity of this reagent towards thiol groups and its usefulness in the quantitative determination of free thiol groups in proteins.