胍基化合物在分子识别中的应用

对胍基化合物的结构、物理化学性质进行了简要说明，重点综述了胍基化合物的分子识别功能在主客体化学中的应用和最新研究进展。参考文献49篇。     

2，4，6－三苯基氧鎓盐分子内旋转受阻对其发光行为的影响

研究了４－位苯基取代基旋转受阻和旋转自由的２，４，６－三苯基氧盐的光物理性质。实验结果表明，当４－位苯基取代基旋转受阻时，氧盐化合物在激发态时引起的分子内极化程度比４－位取代基旋转自由的氧盐化合物大，即在激发态时旋转受阻氧盐化合物发生的分子内电荷转移能力较强；４－位取代基旋转自由的化合物的荧光量子产率随溶剂粘度的增大而有所增大，但旋转受阻化合物在相同的条件下则出现相反的结果。实验结果还表明，４－位取代苯基旋转受阻对化合物的荧光发射不利。     

有机化学新领域—固态化学的研究

介绍了有机化学新领域－固相光化学研究的重要意义的特点。通过色氨酸类、核酸碱基衍生物同稠环化合物异种分子间固态光化学的研究。提示出这种反应的高选择性和专一性。对反应历程也进行了初步研究。为合成化学提供了新方法。利用晶格控制物质，使不易进行光化学反应的物质可顺利地定向进行光化学反应，亦可直接用于合成Ｄ或Ｌ手性化合物，省去拆分。对Ｃ－Ｔ络合物（电荷转移）和分子化合物的固态化学也进行了研究。     

胍基配体的五核锡(Ⅱ)化合物的合成、结构及其对N,N''-二异丙基碳二亚胺加成苯胺反应的催化活性

通过苯胺的衍生物三甲基硅基取代的苯胺基锂与无水二氯化锡按物质的量之比1∶1.25在无水无氧的条件下反应,合成了基于胍基配体的五核锡化合物[PhNC(NMe)_2N(H)SnCl]_2[PhNC(NMe)_2NSnCl]_2Sn (1)。其结构分别用核磁共振氢谱、碳谱、元素分析和X射线单晶衍射技术进行了表征。化合物1在催化苯胺与碳二亚胺加成生成胍的反应中表现出较好的活性,以高收率得到了胍化合物。     

α、ω-双香豆素长链化合物激基缔合物的研究

通过α、ω－双香豆素长链化合物详细研究了香豆素激基缔合物的荧光行办，通过吸收光谱、荧光光谱和激发光谱，考察了香豆素激基缔合物的发光位置与激发波长，借助单光子技术确定了形成的是分子内的激基缔合物，通过1HNMR谱研究了不同双香豆素长链化合物的构象分布，揭示了在水溶液中由于疏水相互作用促进了长链化合物分子内激基缔合物的形成．     

新型α,β—不饱和羰基桥联双二茂铁衍生物的合成及其成膜性

由３－二茂铁基－２－丁烯酸酯经三步反应制得３－二茂铁基－２－丁烯酰氯，并由它与其自身及与单取代二茂铁经酰化反应合成了４种新的α、β－不饱和羧基共轭桥联双二茂铁衍生物，以＾１ＨＮＭＲ、ＩＲ光谱及元素分析表征了这些化合物，并研究了它们形成Ｌａｎｇｍｕｉｒ膜的成膜性，结果表明：这４种新的双二茂铁衍生物皆能在空气／水果面上形成Ｌａｎｇｍｕｉｒ膜。     

胍基稀土配合物[(CH2)5NC(NiPr)2]3Yb的合成及晶体结构

胍基可以通过改变氮上的取代基来调控配合物的空间及电荷效应，它们作为辅助配体用于稀土金属配合物的合成得到了人们的广泛关注。本文通过胍基锂盐和无水YbCl3以3：1的摩尔比进行复分解反应，合成了均配型稀土化合物[(CH2)5NC(N^iPr)2]3Yb，测得它为正交品系，     

喹诺酮类N1位定量构效关系研究

氟隆诺酮类化合物是抗菌药中的重要一类，由于它的许多突出特点，已引起越来越多的研究者的关注山．这类化合物骨架见图1．我们对该类化合物进行过一些研究［’‘l自发现诺氟沙星＊以后，几位取代基在寻找高效、广谱峻诺酮类化合物方面起重要作用，但在发现环丙基（1983年）、特丁基（1989年）以后，一直未发现新的有意义的取代基·在NI位定性与定星构效关系的研究中有二种观点：（1）古贺弘等k’］提出的由立体效应决定的观点；（z）Domagala［71、Chu问等主张的立体与电子效应共同起作用的观点·3D－QSAR研究中的比较分子力场分析（Co…     

新型α，β－不饱和羰基桥联双二茂铁衍生物的合成及其成膜性

由３－二茂铁基－２－丁烯酸酯经三步反应制得３－二茂铁基－２－丁烯酰氯，并由它与其自身及与单取代二茂铁经酰化反应合成了４种新的α，β－不饱和羧基共轭桥联汉二茂铁衍生物。以１ＨＮＭＲ、ＩＲ光谱及元素分析表征了这些化合物，并研究了它们形成Ｌａｎｇｍｕｉｒ膜的成膜性．结果表明：这４种新的双二茂铁衍生物皆能在空气／水界面上形成Ｌａｎｇｍｕｉｒ膜．     

新型的双阴离子型镱（III）胺化物{[Me2Si（NPh）2]2Yb[（N^iPr）2CN（SiMe3）2]}{Li（THF）2}2的合成及晶体结构

胍基稀土衍生物的合成、结构及反应性能是近年来稀土有机化学中的一个重要研究内容[1-5],大量文献报道了二胍基稀土氯化物可以与烷基锂盐或单胺基锂盐反应得到相应的烷基化合物和胺化物.     

The Preparation of Acylselenourea and Selenocarbamate Using Isoselenocyanate

Acyl isoselenocyanates were prepared by a reaction of acyl chloride with KSeCN. The acyl isoselenocyanates formed in situ were ready for further reaction without concentration. N-Acyl selenoureas were obtained by a reaction of acyl isoselenocyanates with amines. The reaction of acyl isoselenocyanates with nucleophiles gave the corresponding selenocarbamate. All the compounds were well characterized by using spectral data, such as ¹³C and ⁷⁷Se NMR and X-ray diffraction.     

Direct-gradient high-performance liquid chromatographic analysis and preliminary pharmacokinetics of flumequine and flumequine acyl glucuronide in humans: effect of probenecid.

A gradient high-performance liquid chromatographic analysis for the direct measurement of flumequine, with its acyl glucuronide, in plasma and urine of humans has been developed. In order to prevent hydrolysis and isomerization of flumequine acyl glucuronide, the samples were acidified by the oral intake of four 1.2-g amounts of ammonium chloride per day. In contrast to the acyl glucuronides of non-steroidal anti-inflammatory drugs, flumequine and its acyl glucuronide were stable in urine of pH 5.0-8.0. Flumequine acyl glucuronide is unstable at pH 1.5. In acidic urine (pH 5-6), almost no flumequine is excreted unchanged (1%): it is excreted chiefly as acyl glucuronide (84.2%). Probenecid co-medication reduces the renal excretion rate of flumequine acyl glucuronide from 662 to 447 micrograms/min (p = 0.00080), but not the percentage of glucuronidation.     

度洛西汀酰基衍生物的合成

抗抑郁药度洛西汀与取代酰氯反应合成了四个新的度洛西汀酰基衍生物——N-取代酰基-N-甲基-3-(1-萘氧基)-3-(2-噻吩基)丙胺,其结构经1H NMR,IR和MS表征。     

Cationic vesicles consisting of 1,2-dioleoyl-3-trimethylammonium propane (DOTAP) and phosphatidylcholines and their interaction with erythrocyte membrane

We studied the formation and stability of vesicles consisting of 1,2-dioleoyl-3-trimethylammonium propane (DOTAP) and phosphatidylcholines by electron spin resonance (ESR) analysis and observation of their hemolytic activities. In contrast with previous findings on dimethyldialkylammoniums, DOTAP formed vesicles at 37 degrees C with phosphatidylcholines containing either saturated acyl chains such as dimyristoylphosphatidylcholine (DMPC) or unsaturated acyl chains such as dilinoleoylphosphatidylcholine (DLPC). Phosphatidylcholines made the bilayer more rigid and significantly reduced the hemolytic activity of DOTAP. In the presence of equimolar concentration of DOTAP and phosphatidylcholines, formation of tightly aggregated structures of several erythrocytes was observed, as previously reported for the vesicles containing dimethyldipalmitylammonium. These findings indicate that DOTAP vesicles were stabilized by phosphatidylcholines with either saturated acyl chains or unsaturated acyl chains, and the interaction with the lipid bilayer of biological membranes as cationic vesicles became prominent with minimal membrane damage by DOTAP monomers.     

Rapid and facile synthesis of acyl azides from acyl halides using a polymer-supported azide ion under heterogeneous conditions

In this article a rapid and facile method for synthesis of acyl azide is described. The cross-linked poly(N-methyl-4-vinylpyridinium) azide ion, [P₄-VP]N₃ is prepared and used as an efficient polymeric reagent for synthesis of acyl azides from acyl halides at room temperature under heterogeneous conditions. Various benzoyl halides, with electron-withdrawing groups as well as electron-donating groups, were transformed into the corresponding benzoyl azides in high to excellent yields in short reaction times. The acyl azide products were characterized by FT-IR, and some of them were also characterized by ¹H-and/or ¹³C-NMR spectroscopy, and physical properties were compared to literature values of known compounds. The spent polymeric reagents can be regenerated and reused for several times without losing their activity. Relative to the reported methods, the present method has the advantages of operational simplicity, mild reaction conditions, fast reaction rates, simple reaction work-up and lower hazardous and potentially explosive nature. Also the present method is the first procedure for the synthesis of acyl azides from acyl halides by using a polymer-supported azide ion under heterogeneous conditions.     

Acyl Iodides in Organic Synthesis: III. Quantum-Chemical Study of the Reaction of Acyl Iodides and Acyl Chlorides with Methanol

The potential energy surface for reactions of acyl iodides and acyl chlorides with methanol was studied by quantum-chemical methods. Stereoelectronic parameters of the prereaction bimolecular complexes and possible reaction products were examined. Transition states were localized for the transformation of prereaction complexes into final products. Dual reactivity of acyl iodides toward methanol was explained in terms of similar activation parameters found for the four-center and S_N2 reaction mechanisms.     

Preparation of acyl fluorides with hydrogen fluoride-pyridine and 1,3-dicyclohexylcarbodiimide

This work presents an efficient procedure for preparing acyl fluorides by simply reacting carboxylic acid with hydrogen fluoride-pyridine and 1,3-dicyclohexylcarbodiimide (DCC) in dichloromethane. The acyl fluorides were converted in situ to the corresponding benzyl carboxylic esters by adding benzyl alcohol and triethylamine to the reaction mixture.     

Protease-catalyzed monoacylation of 2-O-alpha-D-Glucopyranosyl-L-ascorbic acid in pyridine

2-O-alpha-D-Glucopyranosyl-6-O-octanoyl-L-ascorbic acid was enzymatically synthesized from 2-O-alpha-D-glucopyranosyl-L-ascorbic acid (AA-2G) and vinyl octanoate with a protease from Bacillus subtilis in pyridine. Furthermore, with various linear saturated fatty acid vinylesters as acyl donors, AA-2G was also converted to their corresponding 6-O-acyl AA-2G in the same manner. The reactivities of transacylation decreased with increasing length of the acyl groups. Thus, short chain acyl groups were transferred to AA-2G by this protease more efficiently than were long chain acyl groups. This enzymatic method is recommended for the synthesis of 6-Acyl-AA-2G with short or medium length chain acyl groups.     

硝基苯酰基硫脲衍生物的合成与生物活性研究

酰氨基硫脲类化合物具有很好的生物活性,如消炎、抗菌、抗结核、抗癌、杀菌、杀虫及植物生长调节等[1-8],也是重要的有机合成中间体[9-12].因此,随着新型农药的开发研究,酰氨基硫脲类化合物又成为药物开发的热点之一.     

cis-Tetrahydrofuran-3,4-diol structure as a key skeleton of new protecting groups removable by self-cyclization under oxidative conditions

A variety of carbonate-type acyl groups having a cis-tetrahydrofuran-3,4-diol (1,4-anhydroerythritol) backbone structure and a TrS or MMTrS group have been examined as new "protected" protecting groups of the 5'-hydroxyl group of nucleosides. These acyl groups were designed in a manner where they could be deprotected by I(2)-promoted removal of the TrS or MMTrS group followed by self-cyclization involving an intramolecular attack of the once-generated neighboring hydroxyl group on the acyl carbon. It turned out that these acyl groups could be introduced into the 5'-hydroxyl group of a 3'-O-protected thymidine derivative by use of the corresponding acyl imidazolides or 4-nitrophenyl esters as well as by reaction with carbonyldiimidazole or 4-nitrophenyl chloroformate. Among the acyl groups tested, it was found that the CTFOC group could be easily introduced into the 5'-hydroxyl group of 3'-masked deoxyribonucleoside derivatives and rapidly removed under mild conditions using iodine.