5-(4-羟基苯基)-2,4-咪唑啉二酮酯类化合物的合成及其生物活性

在模拟AdSS酶天然抑制剂结构合成5-(4-羟基苄基)-2,4-咪唑啉二酮酯系列化合物的基础上,为优化其结构,以5-(4-羟基苯基)-2,4-咪唑啉二酮为中间体,合成了28个未见文献报道的5-(4-羟基苯基)-2,4-咪唑啉二酮羧酸酯类化合物,它们的结构均经IR,1HNMR和元素分析表征.初步生物活性测试表明目标化合物5-(4-羟基苯基)-2,4-咪唑啉二酮对叔丁基苯甲酸酯(2i)和2-噻吩酸酯(3b)在浓度200μg/mL时对拟南芥生长抑制率达70%..     

新型含偕二甲基结构的PAR-1拮抗剂的合成及其抗血小板聚集活性

以1-(5-叔丁基-4-羟基-3-溴苯基)乙酮和3,3-二甲基-5,6-二乙氧基-二氢异吲哚-1-亚胺为主要原料,设计并合成了3个新型的含有偕二甲基结构的PAR-1拮抗剂——1-(3-叔丁基-4-烷氧基-5-取代氨基苯基)-2-(5,6-二乙氧基-3,3-二甲基-1,3-二氢-1-亚胺基-2H-异吲哚-2-基)乙酮氢溴酸盐(2a～2c),其结构经1H NMR和13C NMR表征。TRAP诱导的人血小板聚集活性测试结果表明,2a～2c具有一定的抗血小板聚集作用。     

N-(2-氨基苯基)-2-喹唑啉酮乙酰胺盐酸盐的合成

本文通过2-溴-N-(2-硝基苯)乙酰胺和取代的喹唑啉酮在NaH催化下发生亲核取代反应,再经过氢化、酸化合成了4个新型常山碱类抗球虫药物-N-(2-氨基苯基)-2-喹唑啉酮乙酰胺盐酸盐(1∶1)。其中,2-溴-N-(2-硝基苯)乙酰胺通过溴乙酰氯与邻硝基苯胺反应制备,取代的喹唑啉酮使用取代的邻氨基苯甲酸与甲酰胺反应合成。所有目标化合物的结构均经1H NMR,IR和HRMS等方法确证。     

(αE,E)-α-(甲氧亚氨基)-2-[1-(芳香醛酮肟氧基)甲基]苯乙酸甲酯的立体选择性合成及生物活性研究

使用邻甲苯基重氮盐与乙醛酸甲酯肟偶联反应高立体选择性合成出 (E)-2-(羟基亚氨基)-2-邻甲基苯乙酸甲酯,经硫酸二甲酯的甲基化反应可得到重要的中间体(E)-2-(甲氧亚氨基)-2-邻甲基苯乙酸甲酯, 再经NBS溴化后与 (E)-芳香醛酮肟进行醚化反应最终得到目标物(αE,E)-α-(甲氧亚氨基)-2-[1-(芳香醛酮肟氧基)甲基]苯乙酸甲酯, 这些化合物多数具有很好的广谱杀菌活性.     

2-苯基-1-(4-(1-吡咯乙氧基)苯基)乙酮的合成

2-苯基-1-(4-(1-吡咯乙氧基)苯基)乙酮是合成抗骨质疏松药拉索昔芬重要的结构片段。以苯酚为原料经成醚,磺酰氯酯化得到磺酸酯,然后经亲核取代反应,傅-克酰基化反应高收率地合成了目标化合物,其结构通过NMR和HRMS进行了表征。     

(S)-(4-溴-2-甲苯)(3-甲基吗啉)甲酮的合成

以(S)-2-氨基丙醇和氯乙酰氯为起始原料,经酰化和环合反应制得(S)-5-甲基吗啉-3-酮（4）; 4经还原制得(S)-3-甲基吗啉(5); 5与4-溴-2-甲基苯甲酸酰化缩合合成了(S)-(4-溴2-甲基苯基)(3-甲基吗啉)-甲酮,总收率57%,其结构经¹H NMR 和 ¹³C NMR确证。     

1-(2,4二异丙氧基-5-甲氧苯基)乙酮的合成研究

本文设计一条新的合成路线,以价廉的异香兰素、间苯二酚为起始原料,通过Dakin反应、乙酰化、酚羟基醚化等系列反应得到目标化合物1-(2,4二异丙基氧基苯基)乙酮(5b)和新化合物1-(2,4二异丙基氧基-5-甲氧基苯基)乙酮(5a)。通过对化合物(5a)进行条件因素探索,得出合成(5a)的最佳反应条件,并通过1H NMR、MS、熔点等技术手段对其进行结构的确认与表征。     

合成4-叔丁基-4′-甲氧基二苯甲酰甲烷的新方法

对叔丁基苯甲醛与对甲氧基苯乙酮在甲醇钠作用下缩合生成1-(4-甲氧基苯基)-3-(4-叔丁基苯基)-2-丙烯-1-酮(1,收率91%);1经溴加成,甲醇钠脱溴合成4-叔丁基4′-甲氧基二苯甲酰甲烷(收率89%),总收率81%,其结构经UV-Vis和1H NMR表征.     

L-苯甘氨酸衍生物新型三齿手性氨基醇的合成

对叔丁基苯胺经二甲基化、甲酰化得到5-叔丁基-2-二甲氨基苯甲醛;L-苯甘氨酸经LiAlH4直接还原,得到的二齿手性氨基醇与上述醛经缩合、还原,得到新型三齿手性氨基醇(2S)-2-[(5-叔丁基-2-二甲氨基)苯基]甲氨基-2-苯基乙醇。用红外光谱(IR)、质谱(MS)和核磁共振氢谱(1H-NMR)等对产物进行了结构表征。     

1-(4-乙酰氨基苯基)-α-溴代-1-丙酮的合成

1-(4-乙酰氨基苯基)-α-溴代-1-丙酮(I)是合成强心药物匹莫苯(Pirnobendan)和新型抗抑郁类药物氨基酮的主要中间体，它可以1-(4-乙酰氨基苯基)丙酮(Ⅱ)为原料，通过α位溴代得到。主要方法有：(1)以冰醋酸作溶剂，滴加溴的醋酸溶液反应后，经氯仿萃取，硅胶G柱层析分离得产品。     

2-Substituted 5-oxo-5,6,7,8-tetrahydroquinazolines

Twenty novel 2-substituted 5-oxo-5,6,7,8-tetrahydroquinazolines in reactions of 2-formyl-1,3-cyclohexanedione and its 5,5-dimethyl- and 5-phenyl derivatives with 4-chloro- and 4-carbonylaminobenzamidines, 3- and 4-carbamidinopyridines, 2-carbamidinopyrazine, 2-carbamidino-5-trifluoromethylpyridine, 1-carbamidinopyrrolidine, 4-carbamidinomorpholine, and 1-carbamidino-3,5-dimethylpyrazole have been obtained.Riga Technical University, Riga LV-1658, Latvia; e-mail: marina@osi.lv. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 212–26, February, 2000.     

1-(2-噻唑)-3-(8-(5-对磺酸基苯基偶氮)喹啉)-三氮烯的合成及其与铜(Ⅱ)的显色反应

合成了新试剂1-(2-噻唑)-3-(8-(5-对磺酸基苯基偶氮)喹啉-三氮烯(TCPQT),并研究了其与Cu2+的显色反应。结果表明:在pH 7.5的磷酸盐缓冲溶液中,TCPQT与Cu2+形成摩尔比为1:1的紫红色络合物,该络合物在606.5nm处有一最大吸收峰,其表观摩尔吸光系数为3.36×105L.mol-1.cm-1,Cu2+的质量浓度在0～0.4μg/mL范围内符合比尔定律,相关系数r=0.9993。方法已用于测定食品中的微量铜。     

龙涎香的组成及降龙涎醚的合成研究进展

简要介绍了龙涎香的应用及其化学组成,重点介绍了以香紫苏醇为原料,通过不同的氧化-还原-环化途径合成降龙涎醚。     

1-(2-Quinoxalyl)-, 1-[3,5-Di(trifluoromethyl)phenyl]-, 1-(2-Carboxyphenyl)-, and 1-Ethoxycarbonyl-4-oxo-4,5,6,7-tetrahydroindazoles

The corresponding 1-(2-quinoxalyl)-, 1-[3,5-di(trifluoromethyl)phenyl]-, and 1-ethoxycarbonyl-3-methyl-4-oxo-4,5,6,7-tetrahydroindazoles have been obtained from reactions of 2-acetyl-1,3-cyclohexanedione, its 5,5-dimethyl and 5-(2-furyl) derivatives, with 2-hydrazinoquinoxaline, 3,5-di(trifluoromethyl)phenylhydrazine, and ethoxycarbonylhydrazine. On interaction with ethoxycarbonylhydrazine the intermediate 2-[1-(-ethoxycarbonyl)hydrazino]ethylidene-1,3-cyclohexanediones were also isolated. From the potassium salt of 2-formyldimedone and 2-carboxyphenylhydrazine hydrochloride, 2-(2-carboxyphenyl)hydrazinomethylene-5,5-dimethyl-1,3-cyclohexanedione was obtained, the cyclization of which in ethanol in the presence of HCl led to 1-(2-carboxyphenyl)- and 1-(2-ethoxycarbonylphenyl)-6,6-dimethyl-4-oxo-4,5,6,7-tetrahydroindazole.     

SYNTHESES AND MASS SPECTRAL REARRANGEMENTS OF UNSATURATED BIS-SULPHIDES AND BIS-SULPHONES

Abstract

The synthesis of (E)- and (Z)-1.2-bis(p-fluorophenylsulphenyl)stilbenes (2a and 2b) and 1,2-bis(p-fluorophenylsulphonyl)stilbenes (3a and 3b) was carried out and their configurations were consistent with their stereospecific synthesis. The isomeric 1,1-bis(p-fluorophenylsulphenyl)- and 1,1-bis(p-fluorophenylsulphonyl)-2,2-bis(phenyl)ethylenes (8 and 9) were also synthesised and configurations were established by degradative oxidation. Mass spectral rearrangements of all these compounds were examined. Mass spectra of 1,1-bis-sulphide and 1,1-bis-sulphone bears close relationship with those of (E)- and (Z)-isomeric counterparts. Smiles-type rearrangement observed in 1,2-bis-sulphides was absent in 1,2-bis-sulphones. McLafferty-type rearrangement involving hydrogen migration, from aryl group was noticed in both bis-sulphides and bis-sulphones. Vinyl migration to the sulphone oxygen predominates over aryl migration in three isomeric bis-sulphones.     

(R)-TTCA·K催化下环己酮与丙烯腈的加成反应

手性催化剂催化下的不对称合成反应是近年来不对称合成研究中受到重视的领域，如在手性催化剂如，在手性冠醚，手性镧配合物、手性硒、手性铑及手性脯氨酸铷盐等催化下，醛、酮与二烃基锌形成手性醇和不对称羟醛缩合反应等，催化下通过Michael加成反应合成手性化合物的方法近年来也有报道，     

Synthesis and Molecular Structure of (E)-1-(Morpholino)-2-(thiomethyl)-2-phenylvinylphosphonate

1 INTRODUCTION Phosphorus-containing vinyl compounds havebeen widely studied due to their versatile physiolo-gical activities and applications in transition metalchemistry, asymmetric catalysis and photorearrange-ment[1～4]. In our previous papers, we have reportedthe syntheses of 2,2,4,5-tetrasubstituted-1,3-dithio-les[5] and 2,5-bis(morpholino)-3,4-bis-(p-chloro-phe-nyl)thiophenes[6] by the reactions of α-thioaroyl-thiofor-mamide with trimethyl phosphite at room tempera-ture and in refl…     

Design,synthesis and antimicrobial activities of 1,2,3-triazole derivatives

Fifteen 1-(4-substituted phenyl)-4-(4-bromophenyl)-5-(halo-o-hydroxyphenyl)imino-1,2,3-triazoles were designed and synthesized based on rational combination of 1,2,3-triazoles and(halo)o-hydroxyphenyl group according to the superposition principle of reinforcement of biological activities.All the compounds were tested to an in vitro antimicrobial screening against M.a.and E.c..Compounds IIe-IIo exhibited more potent antimicrobial activities against M.a.and E.c.than triclosan and fluconazole,which provided valuable information to further study of novel antimicrobial research.     

1，5-二甲基-2-（S）-（1′-苯基乙基）-2-氮杂-8-氧杂-双环[3．3．0]辛烷-3，7-二酮的合成及其结构表征

利用 2 ,3 丁二酮与丙二腈缩合形成双甲基双氰基环并内酰胺 ,经酸性水解得到双甲基环并内酯 ,然后和 (S) ( -) ( 1 苯基乙基 )胺反应生成 1,5 二甲基 2 (S) ( 1′ 苯基乙基 ) 2 氮杂 8 氧杂 -双环 [3 .3 .0 ]辛烷 3 ,7 二酮 ,通过元素分析、红外光谱、核磁共振氢谱和质谱对其结构进行了表征 .用X射线单晶衍射法测定了目标产物的晶体结构 ,结果表明 ,晶体属单斜晶系 ,P2 1 空间群 ,a =0 8777( 18)nm ,b =1 0 10 2 ( 2 )nm ,c =0 90 0 9( 18)nm ,β =118 75 ( 3 )° ,V =0 70 0 3 ( 2 )nm3 ,Dc=1 2 96g·cm-3 ,μ =0 0 89mm-1 ,F( 0 0 0 ) =2 92 ,Z =2 ,R1 =0 0 3 93 ,wR2 =0 0 95 5 .     

Synthesis of 1-(alkylamino)- and 1-(dialkylamino)benzimidazoline-2-thiones

Unlike 1-aminobenzimidazoles, 1-alkylaminobenzimidazoles are thiolated on fusing with sulfur without elimination of theN-amino group, yielding the previously unknown 1-(alkylamino)benzimidazoline-2-thiones. These compounds can be more conveniently obtained on a preparative scale by thiolation of 1-alkylacetamidobenzimidazoles with subsequent hydrolytic elimination of the acetyl group. When 1-(dialkylamino)benzimidazoles are fused with sulfur, they are converted into 1-(dialkylamino)benzimidazoline-2-thiones. By alkylation of 1-(methylamino)- and 1-(diethylamino)benzimidazoline-2-thiones with methyl iodide in alkaline media the corresponding 2-(methylthio)benzimidazoles were prepared.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2231–2235, November, 1995.The authors are grateful to the Contest Center of Basic Natural Science at St. Petersburg University for financial support of this study.