吡嗪羧酸类化合物的合成方法概述

由于吡嗪羧酸及其金属配合物在医药、香精香料、染料、食品、高分子材料等领域中都有广泛的应用,所以对吡嗪羧酸类化合物的研究具有重要的意义。综述了2-吡嗪甲酸、2,3-吡嗪二甲酸、2,3,5,6-吡嗪四甲酸的制备方法,并比较了各种制备方法的优缺点。     

合成5-苄基-2,3-二甲吡嗪的新方法

以过硫酸铵和硝酸银为自由基引发剂 ,以 2 ,3 二甲吡嗪和苯乙酸为原料 ,首次采用自由基烃基化反应合成 5 苄基 2 ,3 二甲吡嗪。用正交实验确定了合成工艺的最佳条件是 :n( 2 ,3 二甲吡嗪 )∶n(苯乙酸 )∶n(硝酸银 )∶n(过硫酸铵 ) =2∶2∶1∶2 ,反应温度 80℃ ,时间 30min ,产率达 70 .5%。     

新方法合成6-N-羟基吡咯并[3,4-b]吡嗪-5,7-二酮

以吡嗪-2,3-二羧酸为起始原料合成2,3-吡嗪二酸酐,在过量盐酸羟胺和无水碳酸钠溶液中反应得到3-羧基-2-吡嗪羟肟酸,再与氯化亚砜回流反应得到标题化合物,收率68%,其结构经IR、1HNMR和13CNMR确证。     

2,3-二甲基吡嗪的合成与应用概述

本文论述了以丁二酮与乙二胺和丁二醇与乙二胺等不同物质为原料的多种合成2,3-二甲基吡嗪方法,并对其在医药、农药、香料和分析化学等方面的应用做了概述。本文认为,2,3-二甲基吡嗪的合成发展趋势应采用气固相催化反应的方法,建议以价廉的丁二酮取代以往气相法中以2,3-丁二醇为原料的路线。     

吡嗪-2,3-二羧酸的合成新工艺

介绍了以二氨基马来腈和乙二醛为原料,经环化合成2,3-二氰基吡嗪,再经水解生成吡嗪-2,3-二羧酸的反应过程,全程反应条件温和,产品总收率高于65%。     

2-乙酰基-7-甲胺基酮与TMB等取代芳香醛的反应

本文探讨了２－乙酰基－７－甲胺基卓酮与３，４，５－三甲氧基苯甲醛（ＴＭＢ）等取代芳香醛的羟醛缩合反应。２－乙酰基－７－甲胺基卓酮与ＴＭＢ、丁香醛、二溴醛等取代芳香醛进行反应分别生成了２－（３，４，５－三甲氧基）肉桂酰基－７－甲胺基卓酮；２－（４－羟基－３，５－二甲氧基）肉桂酰基－７－甲胺基卓酮；２－（４－羟基－３，５－二溴）肉桂酰基－７－甲胺基卓酮等三种尚未见文献报道的新化合物。它们的结构经红外光谱、核磁共振谱及元素分析得以证实。     

1-甲基吲哚-2,3-二酮合成方法的改进

N－甲基－α-甲硫基乙酰苯胺与高碘酸钠反应得到N－甲基－α－（甲亚磺酰基）乙酰苯胺（产率94％）,再在对甲苯磺酸作用下发生分子内Pummerer反应,得到1－甲基－3－甲硫基吲哚－2－酮（产率61％）,进一步与高碘酸钠反应,得到1－甲基吲哚－2,3－二酮,产率60％。通过IR、^1HNMR、^13CNMR等波谱分析方法证明了产物的结构。     

ZnFe2O4/ZnO气相法催化合成烷基吡嗪的研究

：改进的柠檬酸络合法制备了ZnFe2O4/ZnO催化剂,并用于乙二胺和2,3-丁二醇环化脱氢制备烷基吡嗪。用 X 射线衍射(XRD)、傅立叶红外光谱（FT-IR）对催化剂进行了表征。考察了Zn/Fe摩尔比、反应温度、载气空速对2,3-丁二醇转化率和烷基吡嗪选择性的影响。结果表明,在n(Zn):n(Fe)=2:1、反应温度380℃,原料液流速0.02mol/min,载气空速1440 h-1时,2,3-丁二醇的转化率为93.38%,烷基吡嗪的收率为85.47%,其中2,3-二甲基吡嗪的收率为22.16%、2-甲基吡嗪的收率为63.31%。     

N—（取代苯基）吡嗪—2,3—二羧亚胺的合成及其生物活性

由不同的取代苯胺和2,3-吡嗪二羧酐(通过二氨基马来酰腈与1,2-二酮缩合制备)出发合成了84种3-[(取代苯氨基)羰基]-2-吡嗪羧酸(3)和同样数量的N-(取代苯基)吡嗪-2,3-二羧亚胺(4),测定了它们的生物活性。(4)中有5个化合物对水稻白叶枯病具有一定的保护作用。8个化合物对稻瘟病具有保护作用。     

吡嗪并[1,10]菲咯啉类配体及其钯配合物的合成与表征

合成了两种吡嗪并[1,10]菲咯啉类配体-[2,3-f]吡嗪并[1,10]菲咯啉-2,3-二腈和[2,3-f]吡嗪并[1,10]菲咯啉-2,3-二羧酸,并将这两种配体与氯化钯反应,得到两种钯配合物.采用核磁共振谱和红外光谱表征了配体及其钯配合物的结构.     

噻吩并[2,3-d]嘧啶衍生物的研究现状

2,4-二氨基噻吩并[2,3-d]嘧啶类衍生物和2-氨基-4-氧代噻吩并[2,3-d]嘧啶类衍生物是一些重要生物活性化合物的母体结构,对这两类化合物进行了归纳,并对其合成方法逐一进行了简要阐述.     

Comprehensive and Facile Synthesis of Some Functionalized Bis-Heterocyclic Compounds Containing a Thieno[2,3-b]thiophene Motif

A comprehensive and facile method for the synthesis of new functionalized bis-heterocyclic compounds containing a thieno[2,3-b]thiophene motif is described. The hitherto unknown bis-pyrazolothieno[2,3-b]thiophene derivatives 2a-c, bis-pyridazin othieno[2,3-b]thiophene derivatives 4, bis-pyridinothieno[2,3-b]thiophene derivatives 6a,b, and to an analogous bis-pyridinothieno[2,3-b]thiophene nitrile derivatives 7 are obtained. Additionally, the novel bis-pyradazinonothieno[2,3-b]thiophene derivatives 9, and nicotinic acid derivatives 10, 11 are obtained via bis-dienamide 8. The structures of all newly synthesized compounds have been elucidated by (1)H, (13)C NMR, GCMS, and IR spectrometry. These compounds represent a new class of sulfur and Nitrogen containing heterocycles that should also be of interest as new materials.     

几种卤代吡啶类农药中间体的合成与应用

概述了3,5,6-三氯吡啶-2-醇、2,3-二氯吡啶、2-氯-5-氯甲基吡啶、2,3-二氟-5-氯吡啶和2,3-二氯-5-三氟甲基吡啶5种卤代吡啶类化合物的合成方法,并对其在农药工业中的应用做了简要介绍。     

Synthesis of 2,3-trans-3,4-cis- and 2,3-trans-3,4-trans-2,3,4-triphenyltetrahydrofurans

The synthesis of 2,3-trans-3,4-cis- and 2,3-trans-3,4-trans-2,3,4-triphenyltetrahydrofurans was undertaken because these compounds incorportae the essential structural features of certain 2,3-diphenyl-benzofurans and 1,2,3-triphenylalkanones reported earlier to have marked antifertility activity. The synthesis of the 2 tetrahydrofurans was achieved by the cyclization of corresponding 2,3,4-triphenylbutane-1,4-diols upon heating with dimethyl sulfoxide (DMSO). The butane 1,4-diols were in turn prepared either by direct litium aluminum hydride (LAH) reduction of methyl 3-benzoyl-2,3-diphenylpropionates or by conversion of these propionates to delta-3,4-butryrolactones followed by LAH reduction. The propionates were prepared from the Fiedel-Crafts reaction of 2,3-diphenylsuccinic anhydride with benzene. Tetrahydrofurans were tested for their antiimplantation activity in rats. 2,3-trans-3,4-cis-2,4-diphenyl-3-p -(beta-pyrrolidinoethoxy) phenyltetrahydrofuran oxalate was found to inhibit implantation completely at 50 mg/kg, but was inefective at a lower dose.     

Reaktionen von 2,3-Dichlormaleinimiden mit methylenaktiven Verbindungen

Reactions of 2,3-Dichloromaleimides with Methyleneactive Compounds 2,3-Dichloromaleimides 1 react with activated methylene compounds mainly under monosubstitution to give 2–6 . Replacement of the second chloroatom gives 2,3-disubstituted maleimides 9–15 and stable ylides 16–27 with pyridine and triphenylphosphine, respectively. A general synthesis for such maleimid-ylides was found in a one-batch reaction from 2,3-dichloromaleimides 1 with methyleneactive compounds and pyridine or triphenylphosphine.     

Stereospecific synthesis of chiral 2,3-dihydro-1,4-benzodithiine and methyl-2,3-dihydro-1,4-benzodithiine derivatives and their toxic effects on Trypanosoma brucei

Preparation of chiral 2,3-dihydro-1,4-benzodithiine and methyl-2,3-dihydro-1,4-benzodithiine derivatives with known absolute configurations from the easily accessible chiral synthons benzyl 4-O-trifloxy-2,3-anhydro-beta-L-ribopyranoside and benzyl 4-O-trifloxy-2,3-anhydro-alpha-D-ribopyranoside is described. These compounds showed significant in vitro toxicity of the bloodstream form of Trypanosoma brucei with an IC50 of 11 microM. The parasites' energy metabolism and consumption of oxygen were found to be affected during incubation.     

Polymerisation of different furanes with Cr(II) surface compounds on silicagel

Summary Reaction of different furanes (2,3- and 2,5-dihydrofurane, tetrahydrofurane, furane) were examined in the presence of Cr(II) surface compounds on silicagel as catalyst. In every case poly (2,3-dihydrofuran) was obtained. The products of the occuring hydrogenation, dehydrogenation and isomerisation reactions were detected by GC and NMR spectroscopy. A mechanism for the reactions is proposed.     

吡啶并吡嗪/咪唑杂环化合物的合成研究

以2,3-二氨基吡啶或2,3,5,6-四氨基吡啶盐酸盐等为原料合成了吡啶并吡嗪、吡啶并咪唑及吡啶并二咪唑氮杂环衍生物。探讨了反应条件对产物收率的影响,初步确定了优化反应条件。对2,3-二甲基吡啶并吡嗪及2,3-二乙基吡啶并吡嗪的合成,氯化铵-甲醇体系具有明显的催化效果。使用4,5-二羟基咪唑烷-2-酮代替乙二醛与2,3-二氨基吡啶反应,可显著提高吡啶并吡嗪的合成收率;对于吡啶并咪唑和2-甲基吡啶并咪唑的合成,以2,3-二氨基吡啶与原甲酸三乙酯或原乙酸三甲酯为原料,在磷钼酸催化下反应,收率达50%以上;对于吡啶并[2,3-b:5,6-b']二咪唑和2,6-二甲基吡啶并[2,3-b:5,6-b']二咪唑的合成,分别以2,3,5,6-四氨基吡啶盐酸盐与原甲酸三乙酯和原乙酸三甲酯为原料在磷钼酸催化下反应,收率可达68.7%和66.5%。     

含噻二唑环噻吩并[2,3-d]嘧啶类含氟衍生物的合成及抗肿瘤活性

通过2-氨基-3-氰基噻吩与三氟乙酸、三氯氧磷反应"一锅法"制得2-三氟甲基-4-氯噻吩并[2,3-d]嘧啶,收率为60%,再与2-氨基-5-(取代苄硫基)-1,3,4-噻二唑发生芳香族亲核取代反应合成10个含噻二唑环噻吩并[2,3-d]嘧啶类含氟衍生物,收率为64%~75%。目标化合物的结构经红外光谱、核磁共振氢谱、质谱与元素分析表征,并采用MTT法对其进行初步的体外抗肿瘤活性筛选。结果表明,化合物Ⅳc和Ⅳf对Hep G2和BGC-823细胞的抑制活性高于对照样吉非替尼。