N,N-二(邻硝基苯氨基乙基)甘氨酸糖酯的合成

在氢氧化钠和四丁基溴化铵存在下,将N,N-二(邻硝基苯氨基乙基)甘氨酸分别与O-乙酰基溴代葡萄糖、O-乙酰基溴代半乳糖、O-乙酰基溴代乳糖和O-乙酰基溴代木糖作用,制得N,N-二取代甘氨酸的对应乙酰基糖酯。由元素分析、IR、MS和¹HNMR确认了4个的糖酯的结构。关键词N,N-二(邻硝基苯氨基乙基)甘氨酸糖酯,溴代葡萄糖,溴代乳糖,溴代木糖,葡萄糖酸酯。     

N-（1H-3-羧基-1，2，4-三唑-5-基）-N′-芳氧乙酰基脲的合成及生物活性

通过5-氨基-1，2，4-三唑-3-羧酸与芳氧乙酰基异氰酸酯反应，合成了9个新的N-(1H-3-羧基-1，2，4-三唑-5-基)-N′-芳氧乙酰基脲，用核磁共振氢谱、红外光谱和元素分析证明了目标化合物的结构．室内的生物活性测定试验证明，部分目标化合物具有良好的植物生长调节活性．     

N-(1H-3-羧基-1,2,4-三唑-5-基)-N''''-芳氧乙酰基脲的合成及生物活性

通过5-氨基-1,2,4-三唑-3-羧酸与芳氧乙酰基异氰酸酯反应,合成了9个新的N-(1H-3-羧基-1,2,4-三唑-5-基)-N'-芳氧乙酰基脲,用核磁共振氢谱、红外光谱和元素分析证明了目标化合物的结构.室内的生物活性测定试验证明,部分目标化合物具有良好的植物生长调节活性.     

1-芳氨基乙酰基-4-芳乙酰基氨基硫脲的合成及结构表征

利用超声波辐射与相转移催化联用技术合成了6个1-芳氨基乙酰基-4-芳乙酰基氨基硫脲化合物,并用IR、1HNMR及元素分析进行了表征,确定了其空间结构,归属了酰氨基硫脲类化合物1HNMR谱中低场的3个NH质子的信号峰。这种合成方法具有反应条件温和、反应时间较短、产率较高等优点。     

5-取代苯氨基-6-甲基-1,2,4-三嗪-3-硫酮的合成

含有 1 ,2 ,4 三嗪结构的化合物具有广泛的生理活性。我们曾用α 乙酰基硫代甲酰芳胺为原料 ,合成了一系列三嗪类和其它杂环化合物 ,其中1 ,2 ,4 三嗪类有 4,6 二取代 5 硫酮 1 ,2 ,4三嗪 3 酮[1 ,2 ] ,3 氨基 5 取代苯氨基 6 苯基 1 ,2 ,4 三嗪[3] 等化合物。本文以α 乙酰基硫代甲酰芳胺为原料 ,进一步合成 5 取代苯氨基 6 甲基 1 ,2 ,4 三嗪 3 硫酮。当乙酰基硫代甲酰芳胺 1 (ａ ｇ)与氨基硫脲 2反应时 ,首先生成缩氨基硫脲 3(ａ ｇ) ,然后环化得到 5 取代苯氨基 6 甲基 1 ,2 ,4 三嗪 3硫酮 4(ａ ｇ) ,合成中发现 ,4(ａ ｇ)可…     

N-茄呢基胺类糖酯化合物的合成及生理活性

在氢氧化钠和四丁基溴化铵存在下,将化合物2-N-茄呢基胺基苯甲酸(3)和N-茄呢基己二酰胺酸(6)分别与O-乙酰基溴代葡萄糖、O-乙酰基溴代半乳糖、O-乙酰基溴代乳糖和O-乙酰基溴代麦芽糖反应制得对应的糖酯4a～4d和7a～7d,由元素分析,IR,1H NMR和MS确证了8个新化合物的结构,并对其中6个化合物(4a,4d和7a～7d)在三种癌细胞模型上进行了一些初步体外生理活性的测试.     

N-（1,3,4-噻二唑-2-基）-N′-芳氧乙酰基脲的合成及其生物活性

氨基噻二唑;芳氧乙酰基脲;合成;生物活性;生长素     

N-[5-(对三氟甲基苯基)-1,3,4-噻二唑-2-基]-N′-芳氧乙酰基硫脲的合成与生物活性

2-氨基-5-(对三氟甲基苯基)-1,3,4-噻二唑与芳氧乙酰基异硫氰酸酯反应,合成了10种新的芳氧乙酰基硫脲。其结构经1H NMR,IR和元素分析确证。初步的生物活性实验结果表明,部分化合物具有较好的植物生长调节活性。     

N-(5-对溴苯氧甲基-1,3,4-噻二唑-2-基)-N′-芳氧乙酰基硫脲的合成与生物活性

2-氨基-5-对溴苯氧甲基-1,3,4-噻二唑与芳氧乙酰基异硫氰酸酯反应,合成了9种新的芳氧乙酰基硫脲。其结构经1H NMR,IR和元素分析确证。初步的生物活性实验结果表明,部分化合物具有较好的植物生长调节活性。     

N-(5-对溴苯氧甲基-1,3,4-噻二唑-2-基)-N''''-芳氧乙酰基硫脲的合成与生物活性

2-氨基-5-对溴苯氧甲基-1,3,4-噻二唑与芳氧乙酰基异硫氰酸酯反应,合成了9种新的芳氧乙酰基硫脲.其结构经1H NMR, IR和元素分析确证.初步的生物活性实验结果表明,部分化合物具有较好的植物生长调节活性.     

Grignard试剂同6，6－二烷基富烯反应的研究

烯丙基卤化镁和环戊二烯基溴化镁同６，６－二烷基富烯分别进行富烯环外双键的加成和还原反应，生成的取代环戊二烯基负离子用（ＣｐＴｉＣｌ＿２）＿２Ｏ（Ｃｐ＝环戊二烯基）或ＴｉＣｌ４配合，合成通式为Ｃｐ（Ｃ＿５Ｈ＿１－ＣＲＲ￣１－ＣＨ＿２ＣＨ＝ＣＨ＿２）ＴｉＣｌ＿２和（Ｃ＿５Ｈ＿４ＣＨＲＲ￣１）＿２ＴｉＣｌ＿２的化合物。对烯丙基卤化镁、环戊二烯基溴化镁同富烯的反应机理进行了探讨。     

Easy access to N,N-bis(but-3-enyl)-, N-allyl-N-(but-3-enyl)-, and N-(but-3-ynyl)-N-(but-3-enyl)-amines

N,N-Bis(but-3-enyl)amines 5a-i were prepared in overall 74% yield from 1-(triphenylphosphoroylideneaminoalkyl)benzotriazole using an aza-Wittig reaction with aldehydes followed by a double Grignard reaction with allylmagnesium bromide. Use of vinyl or 1-propynylmagnesium bromide and allylmagnesium bromide in a sequential fashion also formed the expected doubly unsaturated amines 9a,b and 12, respectively.     

1-(5-萘酚-7-磺酸)-3-[4-(苯基偶氮)苯基]-三氮烯的合成及与阳离子表面活性剂的显色反应

报道了1-（5-萘酚-7-磺酸）-3-[4-（苯基偶氮）苯基]-三氮烯（NASAPAPT）的合成，研究了该试剂与阳离子表面活性剂溴化十二烷基二甲基苄铵（DDMBAB），溴化十六烷基三甲铵（CTMAB）、溴化十六烷基吡啶（CPB）、溴化十四烷基吡啶（TPB）显色反应的条件。测定了显色反应的灵敏度，符合比尔定律的范围。建立了光度法测定微量阳离子表面活性剂的新方法。     

Synthesis of 6-substituted pyrimidines by the wittig reaction. II . Via 2-acetamido-4-hydroxy-5-phenylbutylpyrimidine-6-carboxaldehyde

Wittig condensations of both stabilized and unstabilized ylides were successfully achieved with 2-acetamido-4-hydroxy-5-phenylbutylpyrimidine-6-carboxaldehyde (XI); functionalized Wittig reagents derived from dichloroacetone, ethyl 4-iodobutyrate, 4-bromobutyronitrile, phenylpropyl bromide, 3-bromopropylphthalimide, p - nitrobenzyl bromide, and p-nitrocinnamyl bromide were used. The resultant 6-substituted pyrimidines could be further transformed by reduction of the 6-side-chain double bond. Successful Wittig reactions were achieved with XI where the corresponding 2-amino-4-hydroxy-5-phenylbutylpyrimidine-6-carboxaldehyde (X) with its less electrophilic aldehyde group failed to give isolable yields of condensation products.     

Synthesis,Antiviral, and Antimicrobial Activity of 1,2,4-Triazole Thioglycoside Derivatives

Abstract

The reaction of 5-(2-methylthio)phenyl-1,2,4-triazole-3-thiol with glucosyl, galactosyl, lactosyl bromide, and peracetylated ribose under the conventional and microwave irradiation methods afforded the corresponding S-glycosides. Deacetylation of S-glycosides gave the corresponding deacetylated derivatives. Reaction of 5-(2-methylthio)phenyl-1,2,4-triazole-3-thiol with 4-acetoxybutyl bromide, 2-acetoxyethoxymethyl bromide, 3-chloropropanol, 1,3-dichloroopropan-2-ol, epichlorohydrin, allyl bromide, and propargayl bromide gave the corresponding S-acyclonucleosides, which were deacetylated to give the corresponding deacetylated compounds. All the newly synthesized compounds were characterized by the IR, ¹H, ¹³C NMR, and elemental analyses. Some of these compounds were screened for their antiviral and antimicrobial activity.

Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the related elements to view the free supplemental file.     

Synthesis of GDP-5-thiosugars and their use as glycosyl donor substrates for glycosyltransferases

Two thiopyranoside analogues of GDP-sugars, GDP-5-thio-d-mannose (14) and GDP-5-thio-l-fucose (15), were synthesized. The syntheses included the phosphorylations of tetra-O-acetyl-5-thio-d-mannosyl bromide (4) and tri-O-benzoyl-l-fucosyl bromide (6) with silver dibenzyl phosphate, deprotection of the phosphate groups, and condensation of the deprotected phosphates with GMP-imidazolidate (13) in the presence of MgCl(2). These GDP-sugar analogues were found to be donor substrates for alpha(1,2)mannosyltransferase and alpha(1,3)fucosyltransferase, affording a 5-thiomannose-containing disaccharide (18) and a 5-thiofucose-containing trisaccharide (21), respectively. The conformation of the disaccharide analogue 18 was similar to that of its native counterpart by ROESY. These findings for GDP-5-thiosugars together with previous demonstrations of enzymatic transfer from UDP-5-thiosugars will allow the production of panels of oligosaccharide analogues with hydrolase-resistant properties.     

Quenching and dequenching of pyrene fluorescence by nucleotide monophosphates in cationic micelles

The fluorescence behavior of pyrene solubilized in the hexadecyltrimethylammonium bromide aqueous micellar solution in the presence of adenosine 5'-monophosphate (AMP) and uridine 5'-monophosphate (UMP) was investigated. AMP and UMP were found to influence oppositely the fluorescence of micellized pyrene. UMP acts as quencher, while AMP acts as dequencher. Both effects saturate at high nucleotide concentration (about 40 mM). Dequenching of micellized pyrene fluorescence is induced also by addition of disodium hydrogen orthophosphate (Na 2HPO 4), while loading with sodium bromide (NaBr) quenches the fluorescence. Furthermore, in absence of micelles, pyrene fluorescence depends on the UMP, according to the Stern-Volmer relation, but is unaffected by AMP. Dynamic light scattering experiments showed that the size and shape of aggregates is not affected by different types of nucleotide loaded into the solution; thus, we conclude that the opposite photophysical effect exploited by AMP and UMP are uncorrelated to any change in micellar microstructure. The whole fluorescence data set was successfully accounted for by assuming that the anionic nucleotides compete with the surfactant counterion (bromide) for the surface of the micelle. Accordingly, substitution of bromide with the more effective quencher UMP results in a strong decrease of the pyrene fluorescence, while the substitution of bromide with the nonquencher AMP results in an increase in the pyrene fluorescence.     

HPLC法分析复方异丙托溴铵溶液雾化气溶胶成分

建立HPLC法同时测定吸入用复方异丙托溴铵溶液雾化气溶胶中硫酸沙丁胺醇和异丙托溴铵两组分的含量。采用C₁₈(4.6mm×250 mm,5μm)色谱柱,流动相为1.2 g/L的1-庚烷磺酸钠溶液(磷酸调节pH 3.2左右)(A)-乙腈(B),等度洗脱,流速为1.0 mL/min,进样量为50μL,分析时间15 min,柱温40℃,检测波长为210 nm。结果表明,硫酸沙丁胺醇和异丙托溴铵分别在0.1~2.0 mg/L和0.075~2.4 mg/L浓度范围线性良好(r值均大于0.999)。复方异丙托溴铵溶液雾化气溶胶中硫酸沙丁胺醇和异丙托溴铵加样回收率分别为97.8%和102.3%。雾化气溶胶中硫酸沙丁胺醇和异丙托溴铵提取方法的回收率分别为96.1%和97.1%。在吸入暴露装置中经雾化5 min和35 min后,气溶胶中硫酸沙丁胺醇含量分别为22.39和3.21 mg/m³,异丙托溴铵含量分别为22.34和3.23 mg/m³,回收率均不低于99.5%,RSD不大于1.9%,表明雾化5 min即达到稳定。本方法适用于吸入用复方异丙托溴铵溶液雾化气溶胶的药物含量测定,也可为吸入制剂雾化气溶胶供试品分析提供参考。     

Synthesis and Structure of Mixed Ba12F19ClδBr5–δ Crystals

In the structure Ba₁₂F₁₉Cl₅ [hexagonal space group P6 2m] the two chlorides on the sites Cl(1) and Cl(2) can partially be replaced by bromide ions. Single crystals of the type Ba₁₂F₁₉Cl_δBr_5–δ with a chloride to bromide ratio up to 2 : 3 could be obtained by cooling a flux of 75 mol% BaF₂ and 25 mol% BaX₂ with X = Cl, Br. The crystal quality decreases with increasing bromide concentration. Structural parameters of five selected single crystals with different chloride/bromide ratio were studied by single crystal X-ray diffraction methods. The refined total Cl^?/Br^? population ratio in the crystals is close to the one of the flux. The lattice parameters and interatomic distances change in various ways, when the smaller chloride ion is replaced by the bigger bromide ion. The refinements show a statistical disorder on the halide sites with preferential bromide substitution on site Cl(1).     

Synthesis and anticancer activity of some new s-glycosyl and s-alkyl 1,2,4-triazinone derivatives

A series of S-glycosyl and S-alkyl derivatives of 4-amino-3-mercapto-6-(2-(2-thienyl)vinyl)-1,2,4-triazin-5(4H)-one (1) were synthesized using different halo compounds such as preacetylated sugar bromide, 4-bromobutylacetate, 2-acetoxyethoxy-methyl bromide, 3-chloropropanol, 1,3-dichloro-2-propanol, epichlorohydrin, allyl bromide, propargyl bromide, phthalic and succinic acids in POCl3. The structures of the synthesized compounds have been deduced from their elemental analysis and spectral (IR, 1H-NMR, and 13C-NMR) data. Some of the synthesized compounds were screened as anticancer agents. Significant anticancer activities were observed in vitro for some members of the series, and compounds 4-Amino-3-(3-hydroxypropylthio)-6-(2-(2-thienyl)vinyl)-1,2,4-triazin-5(4H)-one (12) and 3-(4-Oxo-3-(2-(2-thienyl)vinyl)-4H-[1,3,4]thiadiazolo-[2,3-c][1,2,4]tr-iazin-7-yl)propanoic acid (18) are active cytotoxic agents against different cancer cell lines.