Synthesis of 1-｛ Imidazo[ 1,2-a ] pyridin-2-yl ｝ guaiazulenes

以1-氯乙酰基愈创兰烃奠和取代2-氨基吡啶为原料,一锅法合成了一系列未见文献报道的1-{2-咪唑[1,2-a]吡啶基}愈创兰烃薁衍生物,收率47％ ～ 74％,其结构经1H NMR,IR和元素分析表征.     

1-(2-氨基-3,5-二氰基-4-芳基-4H-吡喃-6-基)愈创兰烃薁的合成

在醋酸铵作用下,通过1-氰乙酰基愈创兰烃薁、芳香醛、丙二腈的三组分反应,一锅法合成了一系列1-(2-氨基-3,5-二氰基-4-芳基-4H-吡喃-6-基)愈创兰烃薁衍生物.该反应操作简单、条件温和、收率良好.产物结构经NMR,MS,IR及元素分析等得以证实.     

1-(香豆素-3-酰基)愈创兰烃薁的合成及其抗菌活性

在醋酸铵作用下,通过1-氰乙酰基愈创兰烃薁与2-羟基苯甲醛类化合物的缩合反应,合成了一系列1-(香豆素-3-酰基)愈创兰烃薁衍生物.该反应操作简单、条件温和、收率良好.产物结构经NMR,IR,MS及元素分析数据得以证实.对所得化合物进行了抗菌活性测试,初步表明它们具有一定的活性.     

新型N-取代愈创兰烃薁-1-磺酰胺类衍生物的合成及抗胃溃疡活性研究

以愈创兰烃薁、氨基酸甲酯盐酸盐、水合肼、芳香醛为原料,合成了15种未见报道的新型N-取代愈创兰烃薁-1-磺酰胺类衍生物,其结构经1H NMR,IR,HRMS确证.初步生物活性测试结果表明,部分化合物具有明显的抗胃溃疡活性.     

3-(2-取代噻唑-4-基)愈创兰烃薁的合成及抗菌活性

以3-氯乙酰基愈创兰烃薁、硫脲或硫代酰胺为原料, 一锅法合成了一系列3-(2-取代噻唑-4-基)愈创兰烃薁衍生物. 该反应收率良好、操作简单、条件温和. 产物的结构通过红外光谱、核磁共振谱和元素分析证实. 对所合成化合物进行了抗菌活性测试, 初步表明具有活性.     

1-(2-苯并呋喃酰基)愈创兰烃薁的合成

在路易斯酸作用下, 以氯乙酰氯为酰基化试剂, 对愈创兰烃薁进行了酰化反应研究, 将氯乙酰化产物与水杨醛在温和反应条件下进行缩合, 以较好的收率、高选择性地得到1-(2-苯并[b]呋喃酰基)兰烃薁类衍生物, 其结构经1H NMR, IR及元素分析等得以证实.     

3,3-二甲基-2-(3-甲基薁乙烯基)-3H-吲哚衍生物的合成

1-甲酰基薁-3-甲酸甲酯和2,3,3-三甲基-3H-吲哚衍生物发生缩合反应,合成了一系列3,3-二甲基-2-(3-甲基薁乙烯基)-3H-吲哚衍生物,收率48%～64%,其结构经~1H NMR,IR和元素分析表征.     

新型2-苯并呋喃取代薁类衍生物的合成

以溴乙酰溴为酰化剂,对2-甲基薁进行酰基化反应,其酰化产物通过与水杨醛缩合,溴代反应及硫代乙酰胺的环化反应,以较好的收率,高选择性合成了新型的1-(2-苯并[6]呋喃酰基)薁和3-(2-苯并呋喃基)薁类[1,2-c]噻吩类衍生物,其结构经1H NMR,IR及元素分析表征.     

愈创木基丙三醇-β-愈创木基醚-[α-13C]的合成新方法及结构分析

本文研究了愈创木基丙三醇-β-愈创木基醚-[α-13C]的合成新路线,首次合成出α位带13C同位素标记的愈创木基丙三醇-β-愈创木基醚-[α-13C],并利用1H-NMR、13C-NMR等手段对其化学结构进行了分析。研究结果表明:利用乙醇作为反应溶剂使4-乙酰基愈创木酚-[α-13C]的溴代反应成为均相反应,溴代产物的产率可提高到90%以上。采用硅胶层析用乙酸乙酯和正己烷(1/2=V/V)做流动相可以分离得到该中间产物。通过利用过量愈创木酚和4-(α-溴代乙酰基)-愈创木酚-[α-13C]进行反应,可以得到β-0-4型木素模型化合物———愈创木基丙三醇-β-愈创木基醚-[α-13C]。     

1-(3-吡唑基)薁-3-甲酸甲酯类衍生物的合成

室温下,1-乙酰基薁-3-甲酸甲酯与N,N-二甲酰胺缩甲醛缩合后再与肼或苯肼反应,合成了6个新的1-(3-吡唑基)薁类衍生物,其结构经1HNMR,MS和元素分析表征。并对反应机理进行了探讨。     

[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。     

[Z]-2-(芳基锡基)-1-(9-芴醇)乙烯的合成、结构与性质

用三苯基氢化锡,三对甲苯基氢化锡作为锡氢化试剂与9-乙炔基-9-芴醇进行反应,合成了2个有机锡化合物:[Z]-2-(三苯基锡基)-1-(9-芴醇)乙烯(1)和[Z]-2-(三对甲苯基锡基)-1-(9-芴醇)乙烯(2)。化合物1和2分别与ICl,Br~2,I~2反应,得到6个有机锡一卤化物,6个有机锡二卤化物和2个有机锡混合卤化物(3-16)。有机锡一碘化物7,13和有机锡二碘化物8,14与KOH乙醇溶液反应,分别得到相应的有机锡氢氧化物17,18和有机锡氧化物19,20。有机锡二碘化物8,14分别与含氮双齿配体1,10-邻菲罗啉(Phen),2,2'-联吡啶(Bipy),8-羟基喹啉(Oxin)反应,得到6个相应的配合物21-26。26个新化合物通过元素分析,锡含量测定,IR,^1HNMR测定对其结构进行了表征。同时测定了化合物2的晶体结构,晶体属单斜晶系,空间群P2~1/c。化合物2是以Sn原子为中心扭曲的四面体构型。     

SBA-15负载金属[Co(Ⅱ),Zn(Ⅱ)]酞菁催化剂的制备及其催化氧化性能

以1,8-二氮杂双环[5,4,0]十一碳烯-7为催化剂,4,5-二丁氧基邻苯二甲腈为原料,用液相法合成了两种金属酞菁配合物——β-八(丁氧基)酞菁钴(1)和β-八(丁氧基)酞菁锌(2),其结构经UV-Vis和IR表征。采用浸渍法将1和2分别负载到有序介孔分子筛SBA-15上制得SBA-15负载金属酞菁催化剂SBA1-15和SBA2-15。以0.1 mol.L-1亚硫酸钠的氧化反应为探针反应,研究了常温常压、氧气气氛下,SBA1-15和SBA2-15的催化氧化活性,并考察了SBA1-15的用量对其催化活性的影响及重复利用性。结果表明,两种催化剂均具有良好的催化性能,在用量相同时,SBA1-15的催化氧化性能优于SBA2-15;SBA1-15的质量为溶液质量的0.16‰时,催化活性最佳,且可以重复使用。     

带有四个不同芳基的环丁烷的合成、结构及光化学性质

通过不同杂芳基乙烯分子间的交叉光二聚反应在硫酸溶液中和中压汞灯照射下,合成了4种含7个不同取代芳基的环丁烷衍生物.用紫外和红外光谱及¹H和¹³CNMR谱确定其结构为顺式头尾相对型二聚体.     

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 .     

Singlet and triplet photocycloaddition reactions of 2-pyridones with propenoate and 2,4-pentadienotes,and the frontier molecular orbital analysis

Regioselective photocycloadditions of 2-pyridones ( 1 ) with 2,4-pentadienoates ( 3 ) were analysed and compared with the reactions with propenoate ( 2 ), and origins of the different regioselectivities were inferred from frontier molecular orbital properties by the use of PM3-CI method. Direct photoreactions of 1 with 3 being α,β,γ,δ-unsaturated carboxylates gave four types of regio-selective [2+2]cycloadducts, 3-β:4-α-4, 5, 3-δ:4-γ-6,7,5-δ: 6-γ-8, 9 and 5-δ:6-γ-[2+2]cycloadducts 10,11. Sensitized photoreactions of 1 with 3 did not occur, and fluorescence of 1 was weakly quenched by 3. Otherwise, main cycloadducts in the sensitized reactions of 1 with 2 have been obtained as 5-α:6-β-[2+2]cycloadducts, which were different from main 3-β:4-α-[2+2]cycloadducts of the direct reactions, and these site-and regio-selectivities were inferred from the different frontier molecular orbital coefficients at the. 3-and 6-positions of 1 for the triplet and singlet states. Formations of 4–7 were also interpreted by both effects of frontier orbital HSOMO-LUMO interactions and of the electrostatic interaction between 1 and 3. The other site-and regioselective adducts 8–11 were inferred to be formed by the electrostatic interactions similar to 2-pyridone photodimerization.     

Application of N-(ω-bromoalkyl)tetrazoles for the preparation of bitopic ligands containing pyridylazole chelators or azole rings as building blocks for iron(II) spin crossover polymeric materials

1-(3-Bromopropyl)tetrazole, 2-(3-bromopropyl)tetrazole, 1-(4-bromobutyl)tetrazole, and 2-(4-bromobutyl)tetrazole were synthesized with the aim to prepare flexible bitopic ligands contaning 1- or 2-substituted tetrazole ring linked through 1,3-propylene or 1,4-butylene spacer with pyridylazole or azole unit. Twenty-six novel ligands i.e., α-(pyridylazolyl)-ω-(tetrazolyl)alkanes, α-(tetrazolyl)-ω-(1,2,3-triazolyl)alkanes, and α-(tetrazol-1-yl)-ω-(tetrazol-2-yl)alkanes were prepared by an alkylation of sodium salts of 5-(2-pyridyl)tetrazole, 3-(2-pyridyl)-1,2,4-triazole, 3-(2-pyridyl)pyrazole, 1,2,3-triazole, and 1,2,3,4-tetrazole with N-(ω-bromoalkyl)tetrazoles. An alkylation of 5-(2-pyridyl)tetrazole, 1,2,3,4-tetrazole, and 1,2,3-triazole afforded both N1- and N2-regioisomer whereas in the case of 3-(2-pyridyl)-1,2,4-triazole and 3-(2-pyridyl)pyrazole only N1 isomers were isolated. The positions of alkylation were confirmed by X-ray diffraction studies of 1-(5-(2-pyridyl)tetrazol-2-yl)-4-(tetrazol-1-yl)butane, 1-(3-(2-pyridyl)-1,2,4-triazol-1-yl)-4-(tetrazol-2-yl)butane, 1-(3-(2-pyridyl)pyrazol-1-yl)-4-(tetrazol-1-yl)butane, and 1-(tetrazol-1-yl)-4-(1,2,3-triazol-1-yl)butane. Preliminary investigations of magnetic properties of iron(II) complex with 1-(3-(2-pyridyl)-1,2,4-triazol-1-yl)-4-(tetrazol-1-yl)butane revealed that obtained product exhibit thermally induced spin transition accompanied by the thermochromic effect.     

N-甲基-2-(4-取代哌嗪)-N-[3-(萘氧基)-3-(2-噻吩基)丙基]乙酰胺衍生物的设计与合成

以N-甲基-3-(1-萘氧基)-3-(2-噻吩基)-丙胺(度洛西汀)为原料,通过N-酰氯化反应和N-烷基化反应,合成了5个新型的N-甲基-2-(4-取代哌嗪)-N-[3-(萘氧基)-3-(2-噻吩基)丙基]酰胺衍生物,其结构经1H NMR,IR和MS表征。     

顺式和反式-2-氨基-3-氰基-4-苯基-1-(4'-甲基苯基)-2-环戊烯-1-醇的合成和晶体结构

用低价钛试剂(TiCl4-Zn)与4, 4-二氰基-3-苯基-1-(4'-甲基苯基)-1-丁酮反应合成了顺式和反式-2-氨基-3-氰基-4-苯基-1-(4'-甲基苯基)-2-环戊烯-1-醇, 并用X射线衍射分析确定了这两个异构体的构型。     

Regioselectively nucleus and/or side-chain fluorinated 2-(Phenanthryl)propionic acids by an effective combination of radical and organometallic chemistry

Regioselectively nucleus and/or side-chain fluorinated 2-(phenanthr-1-yl)- and 2-(phenanthr-2-yl)propionic acids 1-5 were prepared using phenanthren-1(2H)-ones 6a-c as key intermediates. Thus, ethyl 2-(fluorophenanthryl)propionates 11 were obtained in good yields by Reformatsky reaction of 6a-c with ethyl 2-bromopropionate followed by dehydratation and DDQ-promoted aromatization of the resulting beta-hydroxyesters. Side-chain alkyl 2-hydroxy-2-(phenanthr-1-yl)propionates 14 were obtained by bromine/lithium permutation of dihydrophenanthryl bromides 12a-c with butyllithium followed by quenching of the lithiated intermediates with methyl pyruvate or ethyl 3,3,3-trifluoropyruvate and subsequent DDQ-promoted aromatization. The alkyl 2-hydroxy-2-(phenanthr-1-yl)propionates 25 were prepared by reacting 8-bromo-1,3-difluorophenanthrene 24 with butyllithium for 10 seconds at -110 degrees C and subsequent addition of the suitable pyruvate to the lithiated intermediates. Alkyl 2-hydroxy-2-(phenanthr-2-yl)propionates 26 and 29 were suitably obtained by site-selective metalation of 1,3-difluorophenanthrene 28 and the bromophenanthrene 24, respectively, with LDA followed by quenching of the metalated intermediates with the suitable alkyl pyruvate. Fluorination of the above alpha-hydroxypropionates with DAST, followed by the alkaline hydrolysis, allowed the expected 2-(phenanthryl)propionic acids 1-5 to be obtained in satisfactory overall yields.