2-[5-(3-羟基苯甲酰氨基)-1,3,4-噻二唑]基乙酸乙酯的合成

以丙二酸二乙酯为起始原料,经选择性皂化、酸化、氯化、环合和酰胺化反应合成了2-[5-(3-羟基苯甲酰氨基)-1,3,4-噻二唑]基乙酸乙酯(1),总收率37.2%,其结构经1H NMR,13C NMR,IR和LC-MS(ESI)确证。采用正交实验法[L_9(3~4)]优化了酰胺化反应的条件。结果表明:在最优反应条件{n[2-(5-氨基-[1,3,4]-噻二唑)基乙酸乙酯]∶n(三乙胺)∶n(间羟基苯甲酰氯)=1∶2∶3,于20℃反应8 h}下,1收率75.5%。     

新型2-甲基-5-羟基-7-氨基-吡唑[1,5-a]并嘧啶衍生物的合成

以3-甲基-5-氨基-吡唑和氰乙酸乙酯为原料,合成了2-甲基-5-羟基-7-氨基-吡唑[1,5-a]并嘧啶(2);2与芳胺的重氮盐溶液反应,合成了7个新型的2-甲基-5-羟基-6-芳基偶氮-7-亚氨基-吡唑[1,5-a]并嘧啶衍生物,收率87%~93%,其结构经~1H NMR,IR和ESI-MS表征。     

三有机锡(4R)-3-[[(2S)-5-氧-2-吡咯烷基]羰基]-4-噻唑烷甲酸酯的合成、结构和体外抗癌活性

利用三有机锡氢氧化物和手性配体(4R)-3-[[(2S)-5-氧-2-吡咯烷基]羰基]-4-噻唑烷甲酸(HL)反应合成了3个三有机锡(4R)-3-[[(2S)-5-氧-2-吡咯烷基]羰基]-4-噻唑烷甲酸酯R3SnL[1,R=c-C6H11(a),C6H5(b),C6H5C(CH3)2CH2(c)],通过元素分析、IR、1H NMR和X-射线单晶衍射表征了其结构。化合物1a属正交晶系,P212121空间群;化合物1b属单斜晶系,P21空间群。二者均为由羧基氧和内酰胺羰基氧桥联配位形成的右螺旋链状有机锡配位聚合物,锡原子具有五配位[SnC3O2]畸变三角双锥构型。化合物1a和1b对体外2种人癌细胞Colo205和Bcap37增殖均有强的抑制作用,其活性为1b1a。     

N-(噻唑-2-基)-2-[4-(芳氧基)苯氧基]丙酰胺的合成、晶体结构与除草活性

2-氨基噻唑衍生物与(R)-(+)-2-(4-羟基苯氧)丙酰氯反应合成18种N-(噻唑-2-基)-2-[4-(芳氧基)苯氧基]丙酰胺,其化学结构经~1H NMR、~(13)C NMR、元素分析、EI-MS和旋光度确证.采用单晶X射线衍射仪测定了(R)-N-(4-三氟甲基-5-乙氧羰基噻唑-2-基)-2-[4-(3-氟-5-氯吡啶-2-氧基)苯氧基]丙酰胺的晶体结构,该晶体属于四方晶系,空间群为P4_12_12,晶胞参数为:a=14.45502(18)A,b=14.45502(18)A,c=21.7813(5)A;Z=8,V=4551.14(15)A~3,D_c=1.558Mg/m~3,F(000)=2176,μ=3.013 mm~(-1),最终偏离因子R=0.0302,wR=0.0687.除草活性表明,在1500g/hm~2剂量下,大部分化合物对单子叶杂草马唐(Digitaria sanguinalis)和稗草(Echinochloa crusgalli)均具有较高的抑制活性,部分化合物对马唐和稗草的茎叶和土壤处理表现为100%的抑制活性.     

3-[N-(4-甲基苯基)氨基羰基]-5-[4-(4-甲酸基苯甲氧基)苯亚甲基]-2,4-噻唑烷二酮的合成

以对甲苯胺和对甲基苯甲酸甲酯为起始原料,经NBS溴化、亲核取代、酸水解和Knoevenagel缩合等6步反应合成了抗细菌生物膜化合物—3-[N-(4-甲基苯基)氨基羰基]-5-[4-(4-甲酸基苯甲氧基)苯亚甲基]-2,4-噻唑烷二酮,总收率57.3％,其结构经1H NMR,ESI-MS和元素分析确证.     

2-(3,3-二甲基双环[2.2.1]庚-2-亚基)乙醛肟的合成

以ω-甲酰基莰烯为主原料,与盐酸羟胺、三水合乙酸钠经亲核加成反应,合成目标化合物2-(3,3-二甲基双环[2. 2. 1]庚-2-亚基)乙醛肟。采用FT-IR、GC-MS、1H NMR和13C NMR等手段对产物进行了表征,确定了产物结构。探讨了溶剂及碱的种类、碱的用量、物料比、反应温度以及反应时间对原料转化率、产物选择性和产率的影响,得到了适宜的工艺条件为:碱为三水合乙酸钠,n(ω-甲酰基莰烯)∶n(盐酸羟胺)∶n(三水合乙酸钠)=1. 0∶1. 2∶2. 0,溶剂为20 m L的75%乙醇,反应温度为70℃,反应时间为2. 5 h。在上述条件下,产物的产率为83. 9%。     

苯桥连的双[噻唑并[4,5-d]嘧啶-7(6H)-酮]衍生物的合成

在乙醇钠的催化下,4-[(三苯基膦叶立德)氨基]-2,3-二氢-3-苯基-2-硫代噻唑-5-羧酸乙酯(膦亚胺1)与芳香基二异氰酸酯和亲核试剂的双氮杂Wittig反应制得苯桥连的双[噻唑并[4,5-d]嘧啶-7(6H)-酮]衍生物,产率为56%～92%.产物结构经IR,1H NMR,MS和元素分析确证.     

5-[5-(3-吡啶)-2H-四唑亚甲基]-2-芳酰氨基-1,3,4-噻二唑的合成

本文首先用5-(3-吡啶)-2H-四唑乙酰基酰肼与芳酰基异硫氰酸盐反应制备成化合物1-[5-(3-吡啶)-2H-四唑乙酰基]-4-芳酰氨基硫脲化合物1a～j, 然后用冰醋酸回流处理1a～j得到一系列化合物5-[5-(3-吡啶)-2H-四唑亚甲基]-2-芳酰氨基-1,3,4-噻二唑2a～j . 化合物1a～b在强碱介质中首先发生降解, 然后进行环化反应 .     

N-(4-叔丁基-5-苄基噻唑-2-基)氨基乙酰胺的合成与抗肿瘤活性

采用衍生法,在N-[4-叔丁基-5-(4-氯苄基)噻唑-2-基]脂肪酰胺酰基的α-位,插入氨基,设计合成了N-(4-叔丁基-5-苄基噻唑-2-基)氨基乙酰胺衍生物.以4,4-二甲基-1-芳基-3-戊酮为原料,经4-叔丁基-5-苄基-2-氨基噻唑(3),再经氯乙酰化和取代反应得21个N-(4-叔丁基-5-苄基噻唑-2-基)氨基乙酰胺(1),其结构经~1H NMR、~(13)C NMR和元素分析确证.噻唑蓝(MTT)法体外抗肿瘤活性测试表明,该类新化合物对肺癌细胞(A549)、宫颈癌细胞(Hela)和乳腺癌细胞(MCF-7)具有抗肿瘤活性.其中N-[4-叔丁基-5-(胡椒基)噻唑-2-基]吗啉基乙酰胺(1t)对Hela细胞的抑制活性最好;对优选化合物1t进行了AO/EB双染和细胞周期实验,流式细胞仪分析表明,化合物1t可显著诱导肿瘤细胞凋亡,阻滞Hela细胞有丝分裂在S期.     

配合物(BenzMeIm)_2[PtCl_4]的合成与表征（英文）

通过离子液体氯化1-苄基-3-甲基咪唑(BenzMeIm-Cl)与PtCl_2的反应,合成了配合物(BenzMeIm)_2[PtCl_4],并用元素分析、红外光谱、紫外-可见光谱、1H NMR、13C NMR和单晶X射线衍射对其进行了表征。单晶X射线分析表明,配合物结构属于P21/c空间群,晶胞参数和结构解析参数为:a=0.981 80(5)nm,b=0.861 47(3)nm,c=0.144 332(7)nm,β=92.480(2)°,V=121.96(1)nm3,R1=0.014 4,w R2=0.038 8。     

4-氧代-3（4H）-喹唑啉-5-羧酸的合成

以2-氨基-6-甲基苯甲酸为起始原料,通过合环反应生成两种4-氧代-3(4H)-喹唑啉-5-羧酸衍生物(1a, 1b), 1a, 1b分别经高锰酸钾氧化合成了4-氧代-3(4H)-喹唑啉-5-羧酸（2a, 2b）,其结构经¹H NMR, ¹³C NMR和MS表征。研究了投料比｛r［n(高锰酸钾) :n(5-甲基-3(4H)-喹唑啉-4-酮)］｝和反应温度等对收率的影响。结果表明：在最佳反应条件（r=7:1,中性高锰酸钾氧化,于90 ℃反应）下合成2总收率可达66%。     

Synthesis and characterization of cyano-substituted carborane-based compounds. Molecular structure of [1-(4-C7H7)-12-(C5H3-3-(CN)-3,4-(CH3)2)-C2B10H10

The reaction of cyanogen chloride with [1-(4-C(7)H(7))-12-(C(5)H(3)-3,4-(CH(3))(2))-C(2)B(10)H(10)] (7) was found to yield two new C(5)-substituted carborane cluster-based compounds, [1-(4-C(7)H(7))-12-(C(5)H(2)-3-(CN)-3,4-(CH(3))(2))-C(2)B(10)H(10)] (8) and [1-(4-C(7)H(7))-12-(C(5)H-2,4-(CN)(2)-3,4-(CH(3))(2))-C(2)B(10)H(10)] (9). This cyano-substitution pattern is in contrast to the known substitution for the analogous organic quinarene[5.6.7] system. The observed unique cluster-based products may be understood by a combination of steric and electronic effects. Compounds 8 and 9 were characterized by complete multinuclear NMR, (1)H-(1)H COSY NMR, (1)H-(13)C HMQC NMR, FTIR, UV-Vis, IR, MS data and a single crystal analysis for 8 [X-ray data for 8: C(17)H(25)B(10)N, monoclinic, space group P2(1)/n with cell constants a = 8.6794(17) ?, b = 11.021(2) ?, c = 43.175(9) ?, β = 91.00(3)°, V = 4129.2(14) ?(3), Z = 8, R(1) = 0.0729, wR(2) = 0.1464].     

One-pot multi-component synthesis of novel ethyl-2-(3-((2-(4-(4-aryl)thiazol-2-yl)hydrazono)methyl)-4-hydroxy/isobutoxyphenyl)-4-methylthiazole-5-carboxylate derivatives and evaluation of their in vitro antimicrobial activity

A novel series of ethyl-2-(3-((2-(4-(4-aryl)thiazol-2-yl)hydrazono)methyl)-4-hydroxy/isobutoxyphenyl)-4-methylthiazole-5-carboxylate derivatives ( 4a-f and 5a-f ) were synthesized by employing one-pot multi-component approach involving ethyl 2-(3-formyl-4-oxy/isobutoxyphenyl)-4-methylthiazole-5-carboxylate, thiosemicarbazide and various phenacyl bromides/3-(2-bromoacetyl)-2H-chromen-2-one/2-(2-bromoacetyl)-3H-benzo[f]chromen-3-onein ethanol in the presence of catalytic amount of acetic acid. The structures of all the synthesized compounds were confirmed with spectral analysis, ie, IR, 1H NMR, 13C NMR and mass spectrometry, and all the compounds were screened for their in vitro antimicrobial activity.     

新型光控保护基(2-重氮基-3-苯基-4H-磺酰基苯并噻喃)在氨基酸保护-光控脱保护反应中的应用

将新型磷酸基光控保护基(2-重氮基-3-苯基-4H-磺酰基苯并噻喃,PPG)应用于氨基酸［甘氨酸(1a), L 丙氨酸(1b), L 苯丙氨酸(1c)和L-脯氨酸(1d)］的保护 光控脱保护反应。产物结构经¹H NMR, ¹³C NMR和HR-FAB MS表征。研究了物料比r［n(PPG) : n(1a)］,催化剂和反应温度对2a收率的影响。结果表明：在最佳反应条件［1a 0.1 mmol, r=1.25,于室温反应65 h］下,2a收率80%。FL监测光控脱保护反应表明：反应在15 min内完成。     

双－（3－烷基／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性质

利用1，4－二溴丁二酮（1）分别与3－烷基／芳基－4－氨基－5－巯基－1， 2，4－三唑（2a-2n）反应，合成了14种新的双－（3－烷基／芳基）－7H－1，2， 4－三唑并[3,4-b]－1，3，3-噻二嗪类化合物（3a-3n），并利用EA、IR，~1H NMR和MS确定了其结构。     

2-[4-(2,6-二氟苯基)噻唑-2-基]-3-羟基丙烯腈衍生物的合成及生物活性

为了寻找生物活性良好的噻唑基丙烯腈类化合物, 利用2-[4-(2,6-二氟苯基)噻唑-2-基]乙腈(3)分别与取代氯甲酸酯4和取代苯基异氰酸酯6在碱存在下反应, 合成了8个2-[4-(2,6-二氟苯基)噻唑-2-基]-3-羟基-3-烃氧基丙烯腈化合物5和7个2-[4-(2,6-二氟苯基)噻唑-2-基]-3-羟基-3-取代苯胺基丙烯腈化合物7, 均为首次报道的丙烯腈类化合物. 化合物结构经1H NMR, IR, MS和元素分析表征. 初步生物活性测定结果表明, 在试验浓度下, 目标化合物均具有一定的杀虫和抑菌活性, 其中化合物5f和5h在100 mg/L浓度下对炭疽病菌的抑制率达95%; 化合物5g和7d在250 mg/L浓度下对棉红蜘蛛的致死率达85%.     

Synthesis and Characterization of nido-[1,1,2,2-(CO)(4)-1,2-(PPh(3))(2)-1,2-FeIrB(2)H(5)]: A Heterobimetallaborane Analogue of nido-[B(4)H(7)](-)

The synthesis and characterization of nido-[1,1,2,2-(CO)(4)-1,2-(PPh(3))(2)-1,2-FeIrB(2)H(5)] (1) is reported. 1 is formed in low yield as a degradation product from the reaction between [{&mgr;-Fe(CO)(4)}B(6)H(9)](-) and trans-Ir(CO)Cl(PPh(3))(2) in THF and is characterized from NMR, IR, and analytical data and by a single-crystal X-ray diffraction study. 1 crystallizes in the monoclinic space group P2(1)/n with a = 12.8622(12), b = 14.3313(12), c = 23.579(3) ?, beta = 97.12(2) degrees, Z = 4, V = 4257.0(8) ?(3), R(1) = 4.83%, and wR(2)()(F(2)) = 12.43%. The heterobimetallaborane structure may be viewed as a derivative of the binary boron hydride nido-[B(4)H(7)](-) and is related to the known homobimetallatetraborane analogues [Fe(2)(CO)(6)B(2)H(6)] and [Co(2)(CO)(6)B(2)H(4)]. 1 exhibits proton fluxionality in its (1)H NMR spectrum, which is related to that found in the latter two compounds.     

Synthesis and Crystal Structure of Ethyl 2-(6-(1,3-Dioxo-4,5,6,7-tetrahydro-1H-isoindol-2(3H)-yl)-7-fluoro-3-oxo-2H-benzo[b][1,4]oxazin-4(3H)-yl) Butanoate

The title compound ethyl 2-(6-(1,3-dioxo-4,5,6,7-tetrahydro-1H-isoindol-2(3H)-yl)-7-fluoro-3-oxo-2H-benzo[b][1,4]oxazin-4(3H)-yl) butanoate 3 was synthesized by the reaction of ethyl 2-(6-amino-7-fluoro-3-oxo-2H-benzo[b][1,4]oxazin-4(3H)-yl) butanoate with 4,5,6,7-tetraydrophthalic anhydride,and its structure was determined by X-ray single-crystal diffraction.The crystal belongs to the monoclinic system,space group P21/n with a = 9.3469(2),b = 16.7715(5),c = 13.7153(4) ,β = 104.9680(10)°,μ = 0.107 mm-1,Mr = 430.42,V = 2077.08(10) 3,Z = 4,Dc = 1.376 g/cm3,F(000) = 904,T = 296(2) K,R = 0.0508 and wR = 0.1478.     

Preparation and Crystal Structure of 3-（2-Hydroxyphenyl） -6- （4-nitrophenyl）-7H- 1,2,4-triazolo[3,4-b][1, 3,4]thiadiazine

Introduction3,6- Disubstituted- 7H- 1 ,2 ,4- triazolo[3,4- b][1 ,3,4]thiadiazines are amongst the various hete-rocycles that received considerable attention duringthe last two decades as potential biologically activeagents.This kind of N- bridged heterocycles hasbeen reported to possess the wide spectrum of bio-logical properties,such as antimicrobial[1] ,an-tibacterial,antifungal[2 ] ,antiinflammatory[3 ] ,di-uretic[4] ,anthelmintic,and analgesic properties[5] .They can be also used as plant…