一些新的含连三唑环的Aza-Wittig试剂的合成与表征

报道以取代芳胺为原料经重氮化,叠氮化,1,3-偶极环加成反应得到1-代芳基-4-乙氧羰基-5-胺基-1,2,3-三唑,并以此为原料合成了一些新的Aza-Wittig试剂---1-取代芳基-4-乙氧羰基-5-三苯膦化亚胺基-1,2,3-三唑。     

几种新的氮杂-Wittig试剂. 1-取代芳基-4-乙氧羰基-5-三苯膦化亚胺基-1,2,3-三唑的合成与表征

以1-取代芳基-4-乙氧羰基-5-胺基-1,2,3-三唑为原料合成了5种新的氮杂-Wittig试剂--1-取代芳基-4-乙氧羰基-5-三苯膦化亚胺基-1,2,3-三唑.其结构经元素分析、IR,1H NMR和MS确定.     

1-取代芳基-4-乙氧羰基-5-二甲氨基亚甲基氨基-1,2,3-三唑衍生物的新法合成

以1-取代芳基-4-乙氧羰基-5-氨基-1,2,3-三唑衍生物为原料,用简单有效的方法在非常温和的条件下以较好的收率合成了一系列新型的1-取代芳基-4-乙氧羰基-5-二甲氨基亚甲基氨基-1,2,3-三唑及其衍生物,所得化合物未见文献报道.新化合物的结构用红外光谱、核磁共振、质谱和元素分析确证,同时初步研究了这些化合物的抑菌性能.     

稠杂环化合物的研究(Ⅳ)——5-醛胺基-1-芳基-1,2,3-连三唑[2,3-d]嘧啶-4-酮类衍生物的合成及抗菌性能

我们已报道了1-芳基-4-乙氧羰基-5-氨基-1,2,3-连三唑类衍生物(1)的合成及抗菌活性,为研究药物构效关系,我们利用1的酰肼3同甲酸反应,制得了尚未报道的5-醛胺基-1-芳基-1,2,3-连三唑[2,3-d]嘧啶-4-酮(4_(a-c))及5-氨基-6-羟基-7H-1-(间硝基)苯基-1,2,3-连三唑[2,3-d]嘧啶-4-酮(5_d).并观察了它们对枯草杆菌,金黄色葡萄球菌等繁殖的抑制作用。     

新的1-取代芳基-4-乙氧羰基-5-酰胺基-1,2,3-三唑的合成及抑菌性能

连三唑;酰氯;新的1-取代芳基-4-乙氧羰基-5-酰胺基-1;2;3-三唑的合成及抑菌性能     

1,4-二取代-1,2,3-三唑衍生物的合成

在超声波辐射下,端基炔与叠氮基(3,3-二甲基-2,4-二氧戊环基)甲烷通过1,3-偶极环加成合成了1-(3,3-二甲基-2,4-二氧戊环基甲基)-4-芳基-1,2,3-三唑(5);5在酸性条件下脱保护得1-(2,3-二羟基丙基)-4-芳基-1,2,3-三唑,其结构经1H NMR,13C NMR,MS和元素分析表征。     

2-芳胺基-5-[5'-氨基-1'-(4"-氯苯基)-1',2',3'-三唑-4'-基]-1,3,4-噻二唑的合成

1-[5'-氨基-1'-(4"-氯苯基)-1,2,3-三唑-4'-甲酰基]-4-芳基-3-氨基硫脲在浓硫酸催化下环化得到2-芳胺基-5-[5'-氨基-1'-(4"-氯苯基)-1',2',3',-三唑-4'-基]-1,3,4-噻二唑2a-i, 依此法合成了九个标题化合物, 收率为30-74%。化合物2i的结构用X-光衍射单晶分析确证。     

1-(2'-苯基-1', 2', 3'-三唑-4'-甲酰基)-4-芳基氨基硫脲及其 环化产物的合 成

以2-苯基-1,2,3-三唑-4-甲酰肼为原料合成了几种新的1-(2'-苯基-1',2',3'-三唑-4'-甲酰基)-4-芳基氨基硫脲,在不同条件下环化,制得一系列新的1,3,4-噻二唑、1,3,4-恶二唑和1,2,4-均三唑衍生物。化合物的结构经元素分析、IR、^1HNMR和MS确证,并对其波谱性质进行了讨论。     

1-甲基-4-苯基-1H-1,2,3-三唑-5-甲酸衍生物的定向合成

1-甲基-4-苯基-1H-1,2,3-三唑-5-甲酸是一类重要的三唑类衍生物,是多种药物合成的重要中间体.以苯乙炔为原料,设计出了一条定向合成1-甲基-4-苯基-1H-1,2,3-三唑-5-甲酸的新方法.首先苯乙炔与叠氮化钠、碘甲烷在碘化亚铜催化下反应生成1-甲基-4-苯基-1H-1,2,3-三唑,再依次与正丁基锂、甲酸乙酯反应生成中间体1-甲基-4-苯基-1H-1,2,3-三唑-5-甲醛后直接氧化生成目标化合物.该合成途径原料易得、总产率较高、后处理操作简便,具有较高的应用价值.     

2, 5-二取代基-1, 3, 4-恶二唑及恶二唑啉类化合物的合成

2-苯基-1,2,3-连三唑-4-甲酰肼(1)与芳酸在POCl~3催化下得到6种新的2-芳基-5-(2'-苯基-1',2',3'-连三唑-4'-基)-1,3,4-恶二唑(2)。1与羰基化合物缩合得到相应的酰腙(3),在Ac~2O作用下环化成2-取代基-3-乙酰基-5-(2'-苯基-1',2',3'-连三唑-4'-基)-1,3,4-恶二唑啉(4)。化合物的结构经元素分析,IR,^1HNMR和MS确证。     

1-乙酰胺基丙叉-1,1-二膦酸和1-丙酰胺基乙叉-1,1-二膦酸与碱土金属离子的螯合作用

用pH电位法研究了1-乙酰胺基丙叉-1,1-二膦酸(S-186)和1-丙酰胺基乙叉-1,1-二膦酸(S-106)与碱土金属的螯合作用(30±O.1℃).当金属离子与配体的摩尔浓度比为10∶1、1∶1和1∶2时,在水溶液中形成了MHL、ML、ML_2和M_2L等几种类型的配合物.分别测定了它们的稳定常数,其中S-186配合物稍高于S-106,说明配合物稳定性与螯合剂的碱度有平行关系.值得注意的是,这两种螯合剂与Sr~(2 )形成的双核配合物的稳定性均较其它碱土金属离子的为高.     

One-pot carbanionic synthesis of P1,P2-diglycosyl, P1,P1,P2-triglycosyl, and P1,P1,P2,P2-tetraribosyl methylenediphosphonates

Novel lithiated carbanions derived from ethyl glycosyl- and diglycosyl methylphosphonates were used in a direct and convenient synthesis of P1,P2-diglycosyl, P1,P1,P2-triglycosyl, and P1,P1,P2,P2-tetraribosyl methylenediphosphonates involving a one-pot methylidenediphosphonylation of sugars.     

Studies on 1, 2, 4-Benzothiadiazine 1, 1-Dioxide IX.1 Synthesis and Pharmacological Evaluation of 1, 2, 4-Benzothiadiazine 1, 1-Dioxide Biphenyl Tetrazoles as Angiotensin II Antagonists

In the course of our investigations on the development of cardiovascular agents, 3-butyl-2-[2′-(2H-tetrazol-5-yl)bipheny]-4-yl]methyl-2H-1, 2, 4-benzothiadiazine 1, 1-dioxide ( 2 ) was considered as a potential angiotensin II antagonist on the basis of bioisosteric replacement of the quinazoline ring of compound 1 with a 1, 2, 4-benzothiadiazine 1, 1-dioxide ring system. Alkylation of 6 with 4 afforded 7 and 8 in 24% and 28% yields, respectively. An attempt to remove the trityl group of compounds 7 and 8 under acidic condition gave the ring opened products 9 and 11 in 28% and 36% yields, respectively. However, compounds 2 and 10 were obtained in 46% and 85% yields when compounds 7 and 8 were refluxed in methanol. Preliminary assays of compounds 9 and 11 against angiotensin II receptors revealed weak activity with IC₅₀ values of 3.6 μM and 5.4 μM, respectively. Compound 10 (IC₅₀ = 87 nM) exhibited stronger binding affinity than compound 2 (IC₅₀ = 750 nM).     

Densities and viscosities for binary mixtures of phenetole with 1-pentanol, 1-hexanol, 1-heptanol, 1-octanol, 1-nonanol,and 1-decanol at different temperatures

Density (ρ) and viscosity (η) values of the binary mixtures of phenetole+1-pentanol, + 1-hexanol, + 1-heptanol, + 1-octanol, + 1-nonanol, and + 1-decanol over the entire range of mole fraction at 293.15, 298.15, 308.15, and 318.15 K have been measured at atmospheric pressure. The excess molar volume (V^E), viscosity deviations (Δη), and excess Gibbs energy of activation (G*^E) have been calculated from the experimental measurements. These results were fitted to Redlich and Kister polynomial equation to estimate the binary interaction parameters. The viscosity data were correlated with equations of Grunberg and Nissan, Hind et al., Frenkel, and McAllister. While the excess molar volumes of phenetole+1-pentanol, + 1-hexanol are positive, the remaining binary mixtures are negative. The viscosity deviations and excess Gibbs energy of activation are negative for all investigated systems. As the chain length of 1-alkanols increases, both viscosity deviations and excess molar volume values decrease while excess Gibbs energy of activation value increase. The temperature has no effect on excess molar volume, slight effect on excess Gibbs energy of activation, and significant effect on viscosity deviations. The calculated functions have been used to explain the intermolecular interaction between the mixing components.     

Photogeneration and reactivity of 1,n-diphenyl-1,n-azabiradicals

The 1,5-diphenyl-1,5-azapentanediyl biradical Ia was generated by photolysis of 1,2-diphenylazacyclopentane (pyrrolidine 1a). Among the reaction pathways followed by Ia, C-N bond reformation with ring closure was found to be the predominating process, as determined by separate irradiation of either of the pure enantiomers of 1a. Disproportionation was a minor process and took place only via H abstraction by the C5 benzylic radical. Another minor pathway was C5-aryl coupling, with formation of 5-phenyl-2,3,4,5-tetrahydro-1H-benzo[b]azepine (4a), which is equivalent to photo-Claisen rearrangement of 1a. Likewise, the 1,4-diphenyl-1,4-azabutanediyl biradical Ib was generated by photolysis of 1,2-diphenylazacyclobutane (azetidine 1b). This species underwent predominating C2-C3 cleavage, as indicated by the extensive styrene formation. Although N1-C4 bond reformation also took place, this is not the major pathway occurring from Ib. Besides, C4-aryl coupling to give 4-phenyl-1,2,3,4-tetrahydroquinoline (4b) was also observed. All the possible reaction pathways were theoretically studied at the UB3LYP/6-31G computational level; the results were found to be in good agreement with the experimental observations.     

STUDIES ON 1,2,3-DIAZAPHOSPHOLE Ⅳ REACTION OF 1,2,3-DIAZAPHOSPHOLE WITH ALCOHOLS

Rapid addition of alcohols to 1,2,3-diazaphosphole 1 easily gave tricoordinatedphosphorus compounds,which were sulfurized to tetracoordinated phosphorus compounds.When ethylene glycol and aminoethanol were used separately to react with 1,the tricoordinatedphosphorus compounds which formed,rearranged to pentacoordinated phosphorus compoundsand the substituents at N_2 affected the rearrangement significantly.     

Synthesis,characterization and self-assembly of novel fluorescent alkoxy-substituted 1, 4-diarylated 1, 2, 3-triazoles organogelators

Novel organogelators based on fluorescent alkoxy-substituted 1,4-diarylated 1, 2, 3-triazoles are reported. The findings monitored in the current study promoted the development of inventive compacted supramolecular architectures generated by self-assembly of the prepared triazole-based organogelators. The synthesis, characterization and gelation properties of the current novel alkoxy-substituted 1,4-diarylated 1, 2, 3-triazole arms were described. The synthesis procedures were accomplished by using Cu-catalyzed azide-alkyne cycloaddition (CuAAC) of alkoxy-substituted aryl azide with aryl bearing terminal alkyne subtituents and alkoxy chains of different lengths. The alkoxy-substituted of 1, 4-diarylated 1, 2, 3-triazole derivatives bearing different alkoxy chains were characterized by FTIR, ¹H/¹³C NMR, and elemental analysis. The 1, 4-diarylated 1, 2, 3-triazoles with longer alkoxy terminal groups demonstrated improved gelation properties compared to those with shorter alkoxy terminals. The morphologies of the self-assembled alkoxy-substituted 1, 4-diarylated 1, 2, 3-triazoles were investigated using scanning electron microscopy (SEM), which demonstrated arrangements of highly ordered nanofibers, forced by π-stacks and van der Waals interactions. The antibacterial activity and cytotoxicity of the newly synthesized triazoles was investigated to verify the potential use of the present triazole gelators for a variety of applications, such as drug delivery.     

Apparent molar volumes and expansibilities of 1-octanol, 1-nonanol,and 1-decanol in dilute cyclohexane solutions

The densities of solutions of 1-octanol, 1-nonanol, and 1-decanol in cyclohexane up to concentrations of 1.56 mol kg^–1 were measured at temperatures between 20 and 60°C. The apparent molar volumes and expansibilities were found to be linearly dependent on solute concentration. The excess molar volume and the excess thermal expansion coefficient of the solute were derived from the partial molar volume of the solute at infinite dilution and the solute densities. In addition, the limiting partial molar volume of the solute is discussed in terms of the scaled particle theory.     

EFFECTS OF SOME PHENYLETHYNYLSILICON COMPOUNDS ON HEAT-CURABLE SILICONE RUBBER Ⅲ 1, 1, 3, 3-TETRAMETHYL-1, 3-DIPHENYLETHYNYL-DISILOXANE*

We have shown that some phenylethynylsilicon compounds are good cure crosslinkersof heat-curable silicone rubber(HCSR). In this paper the effects of 1, 1, 3, 3-tetramethyl-1, 3-diphenylethynyldisiloxane (TMDPDS) as a crosslinker on HCSR were studied. Thevulcanizates with fine mechanical properties could be obtained with suitable amounts ofTMDPDS. Sol fractions, and crosslinking density of vulcanizates and vulcanizationretardation effect of TMDPDS on hydrosilation curing silicone rubber were also discussed.