吡啶乙炔苯甲腈类化合物的制备

对苯乙炔和吡啶乙炔类化合物的Heck反应进行了较全面的论述和仔细的研究,发现溶剂对催化体系有重要的影响。并成功的改进了一个Pd催化偶合反应。将该反应用于吡啶乙炔苯甲腈类化合物的合成。四个新的吡啶乙炔苯甲腈化合物被首次合成出来,从而为该类化合物的合成提供了一个有效而又方便的方法。     

噻吩基和呋喃基取代的1,2,3-硒二唑衍生物的合成

提供了一种合成噻吩基和呋喃基取代的衍生物的方法,并用其合成方法合成了四种未见文献报道的化合物,测定了四种化合物的红外光谱,核磁共振及元素分析值。     

基于苹果酰亚胺的不对称合成方法学研究进展

综述了以苹果酰亚胺为手性吡咯烷(酮)合成子等效体的合成方法学研究进展。通过新建立的高度区域和立体选择性的灵活多用的不对称还原烷基化方法,可方便地合成反式-5-烷基-4-羟基-2-吡咯烷酮,进而转化为反式-2-烷基-3-羟基(胺基)吡咯烷和反侧-Υ-烷基-Υ-氨基-β-羟基酸。由此打开了通向依莫必利,茴香霉素,pyrrolamA,hapalosin的Υ-氨基酸片断和statine类似物(3S,4R)-ACHPA活化形式的多用途合成路线。     

简便的"一锅法"合成氟代芳烃

本文采用改进的Schiemann反应, 合成了一些用Schiemann反应不易制得的氟代芳烃。本方法中, 芳烃氟硼酸重氮盐水溶液可不经分离, 室温下"一锅法"反应, 简便合成了对氟硝基苯、对氟苯乙酮, 氟代苯甲酸等, 分离产率为25-62%。     

3-间硝基苯基/对硝基苯基-6-芳基-1, 2, 4-三唑并[3, 4-b]-1, 3, 4-噻二唑衍 生物的合成

报道了以3-间硝基苯基/对硝基苯基-4-氨基-5-巯基-1,2,4-三唑与芳酸在磷酰氯的作用下,合成了16个标题化合物,并研究了合成反应的条件。观察了部分标题化合物对金黄色葡萄球菌和大肠杆菌有明显的抑菌作用。     

3-氨基-5-取代苯氨基-6-苯基-1,2,4-三嗪的合成

3-氨基-1,2,4-三嗪化合物具有广泛的生理活性,如:治疗支气管扩张、抑制乳酸菌和症原虫繁殖杀菌等,因此,研究这类化合物合成方法应运而生。本文以苯甲酰基硫代甲酰胺为原料,进一步合成了氨基-5-取代苯氨基-6-苯基-1,2,4-三嗪。     

并入两个四氢键组装单体的卟啉衍生物的合成研究

报道了一个新的卟啉四氢键超分子聚合物组装单体29的合成研究。通过对 Gong等最近报道的四氢键二聚体组装板块进行修饰，合成了两个相应的新的苯甲酸 衍生物中间体11和21，以间－硝基苯甲醛为原料以较高产率合成了一个二硝基四苯 基卟啉26，氯化亚锡还原得到另－卟啉二胺中间体28。以DCC为缩合剂，该卟啉二 胺与其中一个酸11发生缩合反应得到相应卟啉组装单体目标分子29。化合物29在弱 极性溶剂中具有良好的溶解度。     

水中3-甲基-6-氨基-5-氰基-4-芳基-1-苯基-1，4-二氢吡喃[2，3-c]吡唑的洁净合成

在水溶剂中并有三乙基苄基氯化铵（TEBA）存在下，取代芳亚甲基丙二腈与3- 甲基-1-苯基-2-吡唑啉-5-酮缩合成为3-甲基-6-氨基-5-氰基-4-芳基-1-苯基-1， 4-二氢吡喃[2,3-c]吡唑，此法为相应化合物的合成提供了一种快速、方便、高效 和洁净的方法。     

由光敏化环合反应合成若干取代菲啶

用苯乙酮做为光敏剂,从一系列2-溴-4,5-次甲二氧基-N-苯甲基取代苯胺4a～4d通过光环合反应合成了1,3,4-异丙氧基和2-甲基8,9-次甲二氧基菲啶5a～5d 4个目的化合物,与不使用光敏剂的光环合反应合成同样的取代菲啶相比较,结果表明光敏化环合反应不仅使产物5a～5d的收率明显提高,而且还合成了直接照射的光环合反应不能生成的1-异丙氧基-8,9-次甲二氧基菲啶5a。     

2-(N-三氟乙酰-N-三甲基硅烷基)氨基-3-三甲基硅烷氧基-羧酸三甲基硅烷酯和2-(N-三氟乙酰)-2,3-脱氢氨基酸的合成

利用三氟甲基磺酸三甲基硅烷酯, 我们合成了一种新的、化学活性很高的合成中间产物2-(N-三氟乙酰-N-三甲基硅烷基)氨基-1, 1-二(三甲基硅烷氧基)乙烯。脂肪醛或芳香醛发生碳碳成键的加成反应, 生成β碳原子上带有易离去基团三甲基硅烷氧基、N原子上带有保护基团三氟乙酰基的α氨基酸三甲基硅烷酯。消除反应得到了一个合成α、β脱氢氨基酸的可行途径。这类化合物是合成复杂多肽和肽生物碱的基元物。     

苯乙烯基取代的缩杂环卓酮类化合物的合成

本文研究了3-(3,4,5-三甲氧基)肉桂酰基卓酚酮和3-(3,4-亚甲二氧基)肉桂酰基卓酚酮与盐酸缩杂环卓酮类化合物, 并用光谱分析和元素分析证明了它们的结构 .     

苯乙烯基取代的缩杂环(艹卓)酮类化合物的合成

本文研究了3-(3,4,5-三甲氧基)肉桂酰基(艹卓)酚酮和3-(3,4-亚甲二氧基)肉桂酰基(艹卓)酚酮与盐酸缩杂环(艹卓)酮类化合物,并用光谱分析和元素分析证明了它们的结构。     

利用四氯乙烷胺化反应合成联氢化嘧啶衍生物的研究

利用均四氯乙及二氯甲烷的胺化反应,合成了联氢化嘧啶衍生物1～5,4a,8b-反-4,5,8a,9a-四氮杂全氢芴(6)和8b,8c-顺-3a,4a,7a,8a-四氮杂环戊并全氢芴(7)。化合物(6)和(7)的顺反异构体在酸催化下开环,异构生成较稳定的6b和7a。     

Synthesis of acyclic nucleoside analogs of 6-substituted 2-aminopurines and 2-amino-8-azapurines

Several new acyclonucleoside purine and 8-azapurine analogs have been prepared from 2-amino-4,6-dichloropyrimidine ( 1 ) and 3-amino-1,2-propanediol ( 2a ) and 4-amino-1-butanol ( 2b ), respectively, as the starting materials. The new target compounds are: 2-amino-6-chloro-9-(2,3-dihydroxypropyl)purine ( 6a ), 2-amino-6-chloro-9-(4-hydroxybutyl)purine ( 6b ), 2-amino-6-chloro-9-(2,3-dihydroxypropyl)-8-azapurine ( 7a ), 2-amino-6-chloro-9-(4-hydroxybutyl)-8-azapurine ( 7b ), 9-(2,3-dihydroxypropyl)-8-azaguanine ( 8a ), 9-(4-hydroxybutyl)-8-azaguanine ( 8b ), 9-(2,3-dihydroxypropyl)-8-azathioguanine ( 9a ), and 9-(4-hydroxybutyl)-8-azathioguanine ( 9b ). Also, the requisite intermediate pyrimidine derivatives, 2,5-diamino-4-(2,3-dihydroxypropylamino)-6-chloropyrimidine ( 5a ) and 2,5-diamino-4-(4-hydroxybutylamino)-6-chloropyrimidine ( 5b ) are novel.     

Formation of intramolecular rings in ferramonocarbollide complexes

Addition of PPh 2Cl and Tl[PF 6] to CH 2Cl 2 solutions of [N(PPh 3) 2][6,6,6-(CO) 3- closo-6,1-FeCB 8H 9] ( 1) affords the isomeric B-substituted species [6,6,6-(CO) 3- n-(PHPh 2)- closo-6,1-FeCB 8H 8] [ n = 7 ( 2a) or 10 ( 2b)]. Deprotonation (NaH) of the phosphine ligand in 2a, with subsequent addition of [IrCl(CO)(PPh 3) 2] and Tl[PF 6], yields the neutral, zwitterionic complex [6,6,6-(CO) 3-4,7-mu-{Ir(H)(CO)(PPh 3) 2PPh 2}- closo-6,1-FeCB 8H 7] ( 3), which contains a B-P-Ir- B ring. Alternatively, deprotonation using NEt 3, followed by addition of HC[triple bond]CCH 2Br, affords [6,6,6-(CO) 3-7-(PPh 2CCMe)- closo-6,1-FeCB 8H 8] ( 4). Addition of [Co 2(CO) 8] to CH 2Cl 2 solutions of the latter gives [6,6,6-(CO) 3-7-(PPh 2-{(mu-eta (2):eta (2)-CCMe)Co 2(CO) 6})- closo-6,1-FeCB 8H 8] ( 5), which contains a {C 2Co 2} tetrahedron. In the absence of added substrates, deprotonation of the PHPh 2 group in compounds 2, followed by reaction of the resulting anions with CH 2Cl 2 solvent, affords [6,6,6-(CO) 3- n-(PPh 2CH 2Cl)- closo-6,1-FeCB 8H 8] [ n = 7 ( 6a) or 10 ( 6b)] plus [6,6-(CO) 2-6,7-mu-{PPh 2CH 2PPh 2}- closo-6,1-FeCB 8H 8] ( 7, formed from 2a), of which the latter species possesses an intramolecular B-P-C-P- Fe ring. Addition of Me 3NO to CH 2Cl 2 solutions of 2a causes loss of an Fe-bound CO ligand and formation of [6,6-(CO) 2-6,7-mu-{NMe 2CH 2PPh 2}- closo-6,1-FeCB 8H 8] ( 8), which incorporates a B-P-C-N- Fe ring. A similar reaction in the presence of ligands L yields [6,6-(CO) 2-6-L-7-(PPh 2CH 2Cl)- closo-6,1-FeCB 8H 8] [L = PEt 3 ( 9) or CNBu (t) ( 10)], in addition to 8.     

Cyanide-melt synthesis of reduced molybdenum selenide clusters

The tightly cross-linked Mo(3n)Se(3n+2) (n = 2, 3,... infinity) cluster compounds react with alkali metal cyanide or cyanide salt mixtures at temperatures of 450-675 degrees C to yield cyanide-terminated molybdenum chalcogenide clusters, [Mo6Se8(CN)6]n- (1n-) (n = 6, 7) and [Mo4Se4(CN)12](8-) (2(8-)). The process by which discrete 1(n-) clusters are excised from a CN-linked intermediate chain compound, K6Mo6Se8(CN)5 (3), was investigated, and the cubane cluster 2(7-) plays an essential role. An efficient one-step synthesis for Na8[2(8-)] is presented. These clusters are stable in basic aqueous solutions. Cyclic voltammetric (CV) measurements in basic aqueous media show multiple reversible redox waves corresponding to 1(6-/7-), 1(7-/8-), and 1(8-/9-) redox couples with half-wave potentials of E(1/2) = -0.442, -0.876, and -1.369 V, respectively, versus SHE. Half-wave potentials (E(1/2)) for the [Mo4Se4)(CN)12](6-/7-) and [Mo4Se4(CN)12](7-/8-) couples are 0.233 and -0.422 V, respectively, versus SHE. The 2(8-) compounds are K7Na[2(8-)].5H2O.MeOH, Cs7Na4[2(8-)]Cl3, Na8[2(8-)], and K4Na4[2(8-)].12H2O. The products were characterized by X-ray crystallography, cyclic voltammetry, and UV-vis spectroscopy. Reduction potentials measured by voltammetry are consistent with conditions needed for isolating reduced species on a preparative scale but are much more negative than previously reported values. Na8[1(8-)].20H(2)O was isolated by reduction of 1(7-) with Zn in aqueous NaCN solution. Reduction potentials measured in basic NaCN solutions of 2(8-) also differ widely from previous reported values.     

8-羟基喹啉衍生物及其金属配合物的合成与光致发光特性

设计合成了三种新型的8-羟基喹啉衍生物配体: 5-[(4-E-苯乙烯基)-苯甲亚胺基]-8-羟基喹啉(1), 5-[(4-溴-2-氟)-苯甲亚胺基]-8-羟基喹啉(2)和N-乙基-3-[2-(8-羟基喹啉基)-乙烯基]咔唑(3), 以及它们相应的金属配合物, 产物经质谱(MS)、元素分析(EA)、红外光谱(IR)、紫外光谱(UV)、核磁共振氢谱(¹H NMR)进行表征, 并测定了它们的荧光性质. 结果与8-羟基喹啉比较表明, 5位和2位取代8-羟基喹啉衍生物的荧光发生了明显的红移. 同时测定了配合物(3)₂Zn的荧光寿命, 结果表明, N-乙基-3-[2-(8-羟基喹啉基)-乙烯基]咔唑锌配合物表现出较长的荧光寿命.     

Photochemical synthesis and reactivity studies of dirhenacarboranes

Ultraviolet irradiation of [PPh(4)][closo-1-CB(8)H(9)] with [Re(2)(CO)(10)] in THF (tetrahydrofuran) at ambient temperature affords the dirhenacarborane anion [6,10-{Re(CO)(4)}-10-(micro-H)-6,6,6-(CO)(3)-closo-6,1-ReCB(8)H(8)]-, isolated as its [PPh(4)]+ salt (1). Further irradiation of 1 yields a second isomeric anion [6,10-{Re(CO)(4)}-6-(micro-H)-10,10,10-(CO)(3)-closo-10,1-ReCB(8)H(8)]- that was characterized as a [N(PPh(3))(2)]+ salt (2). Reaction of 1 with NOBF(4) produces the neutral dirhenacarborane compound [8,10-{Re(CO)(4)}-8,10-(micro-H)2-6,6-(CO)(2)-6-NO-closo-6,1-ReCB(8)H(7)] (3). Compounds 1-3 all consist of a central {closo-ReCB(8)} cluster with a second rhenium center which is exo-polyhedral. Attempts to substitute the carbonyl ligands of 3 with other donor ligands such as phosphines, isocyanides, or alkynes resulted in loss of the exo-polyhedral rhenium moiety and formation of a monorhenium anion, [6,6-(CO)(2)-6-NO-closo-6,1-ReCB(8)H(9)]-, isolated as its [N(PPh(3))(2)]+ salt (4). The heterometallic dimetallacarborane species, [6,7,10-{Cu(PPh(3))}-7,10-(micro-H)2-6,6-(CO)(2)-6-NO-closo-6,1-ReCB(8)H(7)] (5) and [6,7-{Au(PPh(3))}-7-(micro-H)-6,6-(CO)(2)-6-NO-closo-6,1-ReCB(8)H(8)] (6) were formed from reactions of 4 with {Cu(PPh(3))}+ and {Au(PPh(3))}+, respectively. Similarly, reaction of 4 with {Ir(CO)(PPh(3))(2)}+ afforded two products, [6,10-{Ir(micro-PPh(2))(Ph)(CO)(PPh(3))}-10-(micro-H)-6-CO-6-NO-closo-6,1-ReCB(8)H(8)] (7) and [6,9,10-{Ir(micro-PPh(2))(H)(PPh(3))}-9-(micro-H)-6-CO-6-NO-10-Ph-closo-6,1-ReCB(8)H(8)] (8). The solid-state structures of compounds 1-8 were all unequivocally established by single-crystal X-ray diffraction experiments.     

Synthesis of 8-amino-9-β-D-ribofuranosylpurin-6-thione and related 6-substituted-8-aminopurine nucleosides

Acetylation of 8-amino-9-β-D-ribofuranosylpurin-6-one (III), followed by chlorination of the tetraacetyl derivative 8-acetamido-9-(2,3,5-tri-O-aeetyl-β-D-ribofuranosyl)purin-6-one (IV) with phosphorus oxychloride yielded 8-aeetamido-6-ehloro-9-(2,3,5-tri-O-acetyl-β-D-ribofuranosyl)-purine (V). The 6-chloro substitutent of V was readily displaced with thiourea to give, after treatment with sodium methoxide 8-acetamido-9-β-D-ribofuranosylpurine-6-thione (VIII). Chlorination of 8-bromo-9-(2,3,5-tri-O-acetyl-β-D-ribofuranosyl)purin-6-one (IX) yielded 6,8-dichloro-9-(2,3,5-tri-O-acetyl-β-D-ribofuranosyl)purine (X), which underwent nucleophilic displacement with ethanolic ammonia selectively in the 8 position. The resulting 8-amino-6-chloro-9-β-D-ribofuranosylpurine (VII) was converted to 8-amino-9-β-D-ribofuranosylpurine-6-thione (I), 8-amino-6-methylthio-9-β-D-ribofuranosylpurine (II), and to 8-amino-6-hydrazino-9-β-D-ribofuranosylpurine (XI).     

Phototransposition reactions of methyl-substituted benzotrifluorides: proof of the role of trifluoromethyl-substituted carbon

Irradiation in acetonitrile of any one of the six isomers of dimethylbenzotrifluoride 8 resulted in efficient photoisomerization to the others. The dominant processes in these phototransposition reactions divides the isomers into two triads. The first consists of 8-2,6 (2,6-dimethylbenzotrifluoride), 8-2,3, and 8-3,4; the second consists of 8-3,5, 8-2,4, and 8-2,5. Moreover, irradiation of 2,6-dideuterio-4-methylbenzotrifluoride 5-d(2) resulted in formation of 5,6-dideuterio-3-methylbenzotrifluoride 6-d(2). These observations demonstrate that it is the trifluoromethyl-substituted carbon that is the migratory one in these reactions.