链状双杂芳基乙烯化合物的合成与光化学性质研究

合成了1,n-双[4-[2-[2-(5-甲基苯并唑基)]乙烯基]苯氧基]烷烃(a:n=3;b:n=4;c:n=6)和2,2'-双[4-[2-[2-(5-甲基苯并唑基)]乙烯基]苯氧基]乙醚(d)4个新化合物.用元素分析、红外、紫外、核磁共振谱和质谱表征了其结构.用紫外吸收光谱跟踪研究了Ⅰa_Ⅰd在紫外灯照射下的变化,发现上述化合物在高压汞灯照射下可同时发生反顺异构化和[2+2]分子内光二聚两种反应,反顺异构化反应迅速可逆,而光二聚反应进行缓慢且不可逆.增加链长有助于提高分子内光二聚反应的速率.分子内光二聚反应不受空气中氧的影响的事实表明其是经激发单线态历程进行的.还发现分子内光二聚体在短波紫外光照射下容易进行逆[2+2]光解开环反应.上述化合物分子内光二聚和光解开环反应可以反复进行多次,表明该类化合物具有较高的光稳定性.     

Synthesis of phenoxyacetic acid derivatives as highly potent antagonists of gastrin/cholecystokinin-B receptors. III.

In order to improve the biological characteristics of DA-3934 (5), a novel gastrin/cholecystokinin (CCK)-B receptor antagonist, phenoxyacetic acid derivatives replacing the N-methyl-N-phenylcarbamoylmethyl moiety of 5 with various alkyl chains have been synthesized and their biological activity evaluated. The relationship between the structure of these compounds and their human gastrin receptor binding affinity showed that there should be the optimal size among the various N-alkyl chains. Also a significant increase in the receptor binding affinity was achieved by several compounds. Among those compounds, 2-[3-[3- [N-cyclohexylmethyl-N-[2-(N-methyl- N-phenylcarbamoylmethoxy)phenyl]carbamoylmethyl]ureido]pheny l]acetic acid (22c) and (+/-)-2-[3-[3-[N-[2-(N-methyl-N- phenylcarbamoylmethoxy)phenyl]-N-(3-methylpentyl)carbamoy lmethyl]ureido] phenyl]acetic acid (22h) exhibited high affinity for human gastrin receptors and were also more potent inhibitors in a pentagastrin-induced gastric acid secretion model than the parent compound, 5. The ED50 values of these compounds when administered intraduodenally to rats were 0.12 and 0.63 mg/kg, respectively.     

Cascade synthesis of polyoxygenated 6H,11H-[2]benzopyrano-[4,3-c][1]benzopyran-11-ones

2-(methoxymethoxymethyl)aryllead triacetates, obtained in situ from the corresponding arylboronic acids, reacted with 4-hydroxycoumarins, leading to 3-(2-methoxymethoxymethyl)aryl-4-hydroxycoumarin derivatives in good to high yields. These compounds underwent a cascade sequence of reactions, deprotection-halogenation-annulation, to afford polyoxygenated tetracyclic 6H,11H-[2]benzopyrano-[4,3-c] [1]benzopyran-11-ones in good yields. Some compounds showed a moderate cytotoxicity against human epithelial mammary HBL100 cells.     

Synthesis of diazipine and [3H]diazipine: novel dihydropyridines as photoaffinity probes of calcium channels.

Diazipine and [3H]diazipine were synthesized as new 1,4-dihydropyridine photoaffinity ligands containing a phenyldiazirine group. After simple high performance liquid chromatography separation, both compounds were purified in good overall yields. [3H]Diazipine (21.2 Ci/mmol) was synthesized in two steps from commercially available [3H]ethanolamine. Diazipine competitively inhibited [3H]PN200-110 binding to the calcium channel of cardiac membranes with high affinity.     

Surface Activities of Calix[4] resorcinarenes Bearing Four Hydrophobic Chains and Its Sol ubilization for Organic Compounds

ＩｎｔｒｏｄｕｃｔｉｏｎＩｎｃｌｕｓｉｏｎｃｏｍｐｏｕｎｄｓｈａｖｅｂｅｅｎｎｏｔｅｄｉｎｒｅｃｅｎｔｙｅａｒｓａｎｄｒｅｓｏｒｃｉｎｏｌ ｔｙｐｅｃａｌｉｘ [4 ]ａｒｅｎｅｈａｓｂｅｅｎｓｔｕｄｉｅｄｆｏｒｔｈｅｉｒｉｎｃｌｕｓｉｏｎａｂｉｌｉｔｉｅｓｂｙＳｃｈｅｉｄｅｒａｎｄＢｕｇｌｅｒｅｔａｌ[1— 3] .Ｔｈｅｐｏｌｙｏｌｍｏｉｅｔｉｅｓｉｎｃａｌｉｘ[4 ]ｒｅ ｓｏｒｃｉｎａｒｅｎｅｆｏｒｍｒｉｇｉｄｈｙｄｒｏｇｅｎ ｂｏｎｄｉｎｇｎｅｔｗｏｒｋｓ[4 ] ,ａｎｄｃａｌｉｘ [4 ]ｒｅｓｏｒｃｉｎａｒｅ…     

[1+1]-cyclization of 4-(1-adamantyl)-2,6-diformylphenol with 1,3-bis(aminoalkyl)adamantanes

Selective [1+1]-cyclization of 4-(1-adamantyl)-2,6-diformylphenol with 1,3-bis(aminoalkyl)-adamantane under high dilution conditions in methanol was used to synthesize a new type of adamantine araliphanes, macrocyclic nitrogen-containing compounds with phenolic and adamantane fragments incorporated in the macroring. The [1+1]-cyclization reaction proceeds unusually to form, along with macrocyclic Schiff bases, methanol addition products at one of the N=CH groups of these compounds. The [1+1]-cyclization pattern is shown to depend on the reaction conditions and the structure of the starting diamine.     

Synthesis and evaluation of 1-arylsulfonyl-3-piperazinone derivatives as factor Xa inhibitors IV. A series of new derivatives containing a spiro[5H-oxazolo[3,2-a]pyrazine-2(3H),4'-piperidin]-5-one skeleton

In the course of development of factor Xa (FXa) inhibitor in an investigation involving the synthesis of 1-arylsulfonyl-3-piperazinone derivatives, we found new compounds containing a unique spiro skeleton. Among such compounds, (-)-7-[(6-chloro-2-naphthalenyl)sulfonyl]tetrahydro-8a-(methoxymethyl)-1'-(4-pyridinyl)-spiro[5H-oxazolo[3,2-a]pyrazine-2(3H),4'-piperidin]-5-one (28, M55529) had activity more favorable than those of previously reported compounds. The inhibitory activity of M55529 for FXa is IC(50)=2 nM, with high selectivity for FXa over thrombin and trypsin.     

Syntheses of Some 2-(3,4-dihydro-α-pyranyl)-methoxysilanes

3,4-Dihydro-α-pyran-2-methanol was treated with different chlorosilanes to give different Si-O-C compounds. Five new compounds, trimethyl[2-(3,4-dihydro-α-pyranyl)methoxy]silane, dimethylbis[2-(3,4-dihydro-α-pyranyl)methoxy]silane, methyltris[2-(3,4-dihydro-α-pyranyl) methoxy]silane, methyldipheny [2-(3,4-dihydro-α-pyranyl) methoxy]silane, and methylphenylbis[2-(3,4-dihydro-α-pyranyl)methoxy]silane are described.     

两种新型双极有机小分子发光材料的合成与发光

设计和合成了两种新的具有“双极(bipolar)”性质和发光性能的有机小分子化合物N-[4-(5-(2-苯基喹啉-4)-1,3,4-噁二唑-2)苯基]-N'-苯基-N,N'-二苯基-1,1'-联苯基-4,4'-二胺(TPDOPQ)和N,N'-双{4-[5-(2-苯基喹啉-4-基)-1,3,4-噁二唑-2]苯基}-N,N'-二苯基-1,1'-联苯基-4,4'-二胺[TPD(OPQ)₂]. 用¹H NMR, MS和元素分析进行了表征, 研究了化合物的热稳定性和光致发光性质, 并用循环伏安法测定了其电化学性能. 结果表明, 这两种合成的有机化合物同时具备空穴传导和电子输入双重功能, 光致发光性能优良, 热稳定性好, 能形成均衡薄膜, 因此可作为制作有机电致发光器件的候选材料.     

含席夫碱和酰胺单元的新型双杯[4]芳烃的合成

对叔丁基杯[4]芳烃-1,3-二醛基衍生物2与对叔丁基杯[4]-1,3-二酰肼衍生物4在稀释条件下进行“1＋1”分子间缩合反应, 高产率地合成了含席夫碱和酰胺单元的新型双杯[4]芳烃衍生物5. 所有新化合物的结构经元素分析、质谱、核磁共振谱等表征证实, 杯[4]芳烃单元均为1,3-桥联且采取锥式构象.     

Ionic liquids with perfluorinated alkoxyaluminates

Ionic liquids with the weakly coordinating perfluoroalkoxyaluminate anions, Al(ORF)4-, are obtained by a metathesis reaction of LiAl(ORF)4 and [bmim]Cl or [bmpyr]Cl in high yields. The compounds [bmim][Al(hfip)4] and [bmpyr][Al(hfip)4] have surprisingly low viscosities at elevated temperatures (60 degrees C) and an exceptionally high electrochemical window, which might render them useful for certain applications.     

3-(D-葡萄糖-1-基)-6-芳基-7H-1，2，4-三唑并[3，4-b][1，3，4]噻二嗪类化合物的合成及波谱研究

ω-溴代芳香基乙酮与3-(D-葡萄糖-1-基)-4-氨基-5-巯基-1，2，4-三唑反应 合成了一系列新颖的3-(D-葡萄糖-1-基)-6-芳基-7H-1，2，4三唑并[3，4-b[1，3 ，4]噻二嗪．用元素分析，IR，NMR，MS对其结构进行了表征，研究了其NMR波谱特 征，并以^1H-^1H COSY，^13C-^1H COSY，COLOC二维NMR技术对其^1H NMR，^13C NMR的谱峰进行了全归属     

[F]Fluorophenyl organometallics as intermediates of no-carrier-added F-fluoroarylation reactions

Based on the recent availability of no-carrier-added (n.c.a.) 1-bromo-4-[¹⁸F]fluorobenzene with high radiochemical yield, the 4-[¹⁸F]fluorophenyl compounds of lithium, sodium and magnesium can now also effectively be prepared. Thus, [¹⁸F]fluoroarene reagents with a nucleophilic reaction centre are available and suitable among others for the formation of [¹⁸F]fluorophenyl compounds with electron donating substituents in the radiosynthesis of ¹⁸F-labelled complex organic structures. For these arylation reactions, however, the presence of macroscopic amounts of a haloarene as co-reactant is necessary with all n.c.a. [¹⁸F]fluorophenyl metallics. The ¹⁸F-fluoroarylation was verified for examples of aryl-carbon, -silicon, -sulphur, and -nitrogen bond formation with radiochemical yields of 20-25% related to the starting radioactivity of [¹⁸F]fluoride.     

Part 1: Synthesis of Polyfused Heterocyclic Systems Derived From 3-Phenyl-5,6,7,8-tetrahydro[1,2,4]triazolo[3,4- b ][1,3,4]thiadiazepine-6,8-dione

3-Phenyl-5,6,7,8-tetrahydro[1,2,4]triazolo[3,4- b ][1,3,4]thiadiazepine-6,8-dione ( 1 ) was condensed with o -aminothiophenol, 2-amino-ethanol or cystamine to afford compounds 2-4 respectively. Treatment of compound 1 with dimethylthiomethylenemalononitrile yielded the corresponding pyrano[3,2- f ][1,2,4]triazolo[3,4- b ]-[1,3,4]thiadiazepine derivative 5 . 7-[5-Amino-1,3-dithiolan-2-ylidene]-3-phenyl-5,6,7,8-tetrahydro[1,2,4]triazolo[3,4- b ][1,3,4]thiadiazepine-6,8-dione ( 6 ) was obtained by treating compound 1 with CS 2 and chloroacetonitrile. Thiation of compound 1 gave the corresponding thioanalog 7 , which in turn was condensed with malononitrile to give 3-phenyl-5,6,7,8-tetrahydro[1,2,4]triazolo[3,4- b ][1,3,4]thiadiazepine-6-one-8-ylidenemalononitrile ( 8 ). On treating compound 8 with benzaldehyde or p -nitrobenzaldehyde, pyrano[1,2,4]triazolo[1,3,4]thiadiazepin derivatives 9a , b , respectively, were obtained. Compound 8 was treated with CS 2 and methyl iodid to give the corresponding dithiomethylmethylene derivative 10 which was subjected to react with aniline to give pyrido[1,2,4]triazolo[1,3,4]thiadiazepine derivative 11 . Compound 8 was treated with 3-aminopyridine, o -aminothiophenol, or o -phenylenediamene to yield compounds 12 and 13a , b respectively. Finally, tertiary amines or activated phenols were condensed with compound 8 to yield compounds 14 and 15a , b respectively.     

Syntheses of fluorinated phencyclidine analogs

Syntheses of several fluorinated phencyclidine (PCP) analogs are described. These compounds are being used to probe PCP binding sites on N-methyl-d-aspartate (NMDA) receptors. The compounds were prepared in good yields by Grignard reaction of appropriate fluorine substituted bromobenzene with carbonitrile intermediates. Syntheses of the known compound 1-[1-(3-fluorophenyl)cyclohexyl]piperidine, and the novel compounds 1-[1-(4-fluorophenyl)cyclohexyl]piperidine, 1-[1-(3-fluorophenyl) cyclohexyl]pyrrolidine, and 1-[1-(4-fluorophenyl)cyclohexyl]pyrrolidine are reported.     

New mixed alkaline-earth nitridomolybdate(VI) nitride oxides with anion-ordered sub-structures

New molybdenum(VI) nitride oxides were synthesised by the reaction of strontium nitride and calcium nitride with molybdenum foil at high temperature in sealed stainless steel crucibles. The reactions yielded single crystalline products determined by X-ray diffraction to form complex structures in the triclinic space group P1(no. 2). The mixed alkaline earth compounds with composition Ca38Sr13[MoN4]12N8O3 and Ca36Sr15[MoN4]12N8O3 are isostructural with the quaternary nitride oxides Sr51[WN4]12N8O3 and Ca51[WN4]12N8O3. The structures contain isolated [MoN4](6-) tetrahedra, partially disordered alkaline earth cations and an ordered sublattice of N(3-) and O(2-) anions. Oxide anions are coordinated only to the alkaline earth metals. The title compounds are the first mixed alkaline earth metal nitride oxides.     

[Z]-1-[2-(三芳基锡基)乙烯基]环辛醇的合成和性质

本文用三苯基氢化锡、三对甲苯基氢化锡作为锡氢化试剂与1-乙炔基环辛醇进行反应, 合成了两个有机锡化合物: [Z]-1-[2-(三苯基锡基)乙烯基]环辛醇(1)和[Z]-1-[2-(三对甲苯基锡基)乙烯基]环辛醇(2), 并测定了1的晶体结构。1和2分别与ICl, Br2, I~2反应, 得到六个有机锡一卤化物和三个有机锡二卤化物(3-11)。有机锡二卤化物6和一卤化物5与KOH乙醇溶液反应, 分别得到相应的锡氧化物和锡氢氧化物(12, 13)。有机锡二卤化物8分别与含氮双齿配体[2,2'-联吡啶(Bipy),5-硝基-1,10-邻菲罗啉(Nphen),8-羟基喹啉(Oxin)]反应, 得到三个相应的配合物(14-16)。十六个新化合物通过元素分析、锡含量测定、IR、^1H NMR测定对其结构进行了表征, 同时提出了1和2的生成反应历程。     

Synthesis and characterization of orally active nonpeptide vasopressin V2 receptor antagonists.

The present study was undertaken to evaluate whether a novel series of 2,6-diaza-5-oxobicyclo[5.4.0]undeca-1(7),8,10-triene derivatives exhibited antagonistic activity for vasopressin V1 and V2 receptors. Most of these compounds were synthesized and showed a high affinity potential for V2 receptor and low to moderate affinity potential for V1 receptor. The most potent and V2-selective compound, N-[4-[2,6-diaza-6-[2-(4-methylpiperazinyl)-2-oxoethyl] -5- oxobicyclo[5.4.0]undeca-1(7),8,10-trien-2-yl]-carbonyl]pheny l][2-(4- methylphenyl)phenyl]-formamide (11b), exhibited IC50's of 2.9 nM for the V2 receptor and 200 nM for the V1 receptor, respectively. When administered orally to rat, 11b showed an approximately 18-fold increased urine volume in comparison with control rat.     

New synthetic approach to substituted isoindolo[2,1-a]quinoline carboxylic acids via intramolecular Diels-Alder reaction of 4-(N-furyl-2)-4-arylaminobutenes-1 with maleic anhydride

Acylation of substituted 4-(furyl-2)-4-arylaminobut-1-enes with maleic anhydride provided 2-allyl-6-carboxy-4-oxo-3-aza-10-oxatricyclo[5.2.1.0^1,5]dec-8-enes in high yield under mild reaction conditions. The Diels-Alder adducts are formed via an initial amide formation followed by a stereoselective intramolecular [4+2] exo-cycloaddition reaction. Treatment of the tricyclic compounds with phosphoric acid at high temperatures (70-120 °C) promoted cyclic ether opening, intramolecular cyclization and aromatization to give the corresponding tetracyclic compounds, 5,6,6a,11-tetrahydro-10-carboxyisoindolo[2,1-a]quinolines, in moderate yields. The influence of the acid and the reaction temperature on the cyclization reactions are also discussed.     

偶氮苯取代吡唑啉衍生物PMMA薄膜的光诱导双折射性质研究

芳香族偶氮化合物的顺反异构化反应长期以来一直受到人们的关注 [1,2 ] .当把偶氮生色团引入到聚合物中时 ,在线性偏振光的激发下 ,偶氮生色团能发生“反 -顺 -反”光异构化循环 ,并且偶氮发色团会沿着偏振光偏振方向的法线重新取向 ,从而导致光致双折射现象的发生 [3 ] .因此 ,这类聚合物在光学存储 [4 ] 、光学开关和全息光栅 [5] 等方面具有重要的应用价值 .为研究偶氮苯的结构对光诱导双折射性质的影响 ,本文制备了偶氮苯取代的三苯基吡唑啉衍生物 ,并把其掺杂入 PMMA中 ,研究了薄膜的偏振光诱导光致双折射性质 ,讨论了温度对其光致双…