香豆素酰胺类化合物的合成及光谱特性

用(取代)香豆素-3-甲酰氯(Ⅰa～Ⅰc)和取代2-氨基苯并噻唑(Ⅱa～Ⅱd)作用合成了12种新的目标化合物(Ⅲa～Ⅲl),用HRMS、IR、1H NMR对化合物结构进行了表征,确定了化合物的结构,并对其紫外吸收光谱和荧光光谱进行了分析。研究发现:在紫外光谱中,新化合物(Ⅲa～Ⅲl)和原料化合物(Ⅰa～Ⅰc)相比,因共轭链的增长而使其最大吸收波长(λmax)红移;12种化合物表现出比原料化合物(Ⅰa～Ⅰc)较强的荧光性能。     

N-(取代)-1,3,4-噻二唑基香豆素酰胺类化合物的合成及光谱特性

用6-氯香豆素-3-甲酰氯(Ⅰ)和5-(取代)-2-氨基-1,3,4-噻二唑(Ⅱa-Ⅱi)作用合成了9种新的目标化合物(Ⅲa-Ⅲi),用HRMS,IR和1 H NMR对化合物结构进行了表征,确定了化合物的结构,并对其紫外吸收光谱和荧光光谱进行了分析.研究发现:在紫外光谱中,新化合物(Ⅲa-Ⅲi)和2种原料化合物相比,因共轭链的增长而使其最大吸收波长(λmax)红移;9种化合物表现出比原料化合物(Ⅰ)较强的荧光性能.     

新型香豆素N-取代-1,3,4-噻二唑基酰胺类化合物的合成及其光学性能

8-甲氧基香豆素-3-甲酰氯(1)与5-取代-2-氨基-1,3,4-噻二唑经取代反应合成了9个新型的香豆素N-取代-1,3,4-噻二唑基酰胺类化合物(3a~3i),其结构经1H NMR,IR和HR-MS表征。UV-Vis和FL研究表明,3较1的λmax红移,吸收强度增强;3较1有更强的荧光性能。     

含苯并噻唑基香豆素酰胺类化合物的合成及其光谱研究

由取代香豆素-3-甲酰氯和5-氯-2-氨基苯并噻唑类化合物合成了4种N-(5-氯)苯并噻唑基香豆素酰胺类化合物Ⅲa～Ⅲd,经HRMS、IR、1H NMR对化合物结构进行了表征,考察了其紫外光谱,得到了各化合物的最大吸收波长(λmax)、摩尔吸收系数(εmax)、线性回归方程、线性范围及相关系数(R2),初步分析了紫外光谱与分子结构的关系。对所得产物的荧光分析发现,4种产物均有较强的荧光性能,其中Ⅲc的荧光强度最大;对产物稀溶液中荧光发射光谱强度和溶液浓度的关系进行了讨论,考察了金属离子对化合物荧光光谱的影响。     

N-苄基酰胺类化合物的合成

分别以3-甲氧基苄胺, （S）-α-苯乙胺, （R）-α-苯乙胺或苄胺为原料,对甲苯磺酸为催化剂,甲苯为溶剂,分别与正戊酸、软脂酸、己二酸和对硝基苯甲酸经酰化反应合成了6个N-苄基酰胺类化合物,收率10.7%～22.3%,其中N-(3-甲氧基苄基)戊酰胺为新化合物,其结构经¹H NMR, IR和元素分析表征。     

香豆素类化合物合成研究进展

香豆素类化合物在医药、分析、光学等领域均具有极其广泛的应用,其绿色高效的合成方法也在不断地探索之中。香豆素母核上具有多个活性位点,可以非常方便地对其进行结构修饰得到不同结构的衍生物。因此,香豆素类化合物拥有巨大的潜在应用研究价值。本文首先综述了香豆素母核结构的几种经典合成方法的研究进展,接着介绍了吡咯、吡啶、呋喃和吡喃等各种杂环修饰香豆素的合成,展望了香豆素衍生物合成和应用中可能出现的机遇及挑战,为相关研究提供参考。     

双香豆素类化合物的合成及表征

香豆素是一类具有重要生理活性的天然产物。本文通过4-羟基香豆素的合成,然后与醛缩合,制备了一类具有双香豆素结构的化合物,对其结构通过^1H NMR、IR及元素分析确证并对其波谱学特征予以了讨论。     

苯并香豆素酯类衍生物的合成及荧光性质研究

以2-羟基-1-萘甲醛为原料,采用改进的Knoevenagel反应合成了苯并香豆素-3-羧酸中间体和4种不同链长的脂肪酯和芳香酯衍生物,采用元素分析和红外光谱对其结构进行了表征.对所有化合物固体粉末的发光性能进行了研究.     

香豆素丙二酸二甲酯类化合物的合成

运用拼合原理将丙二酸酯类降糖活性化合物的药效基团丙二酸酯基与有降糖活性的香豆素拼合,设计合成3个新的了香豆素丙二酸甲酯类化合物,其结构经1H NMR,IR和MS表征。     

新型4-羟基香豆素衍生物的微波合成及其光谱性质

以4-羟基香豆素(a)为原料微波辐射合成了具有独特的生理活性和荧光性能的3,3′,3″,3′″-亚乙四基-4-羟基香豆素(b)、3,3′-苯亚甲基-双-4-羟基香豆素(c)和4-羟基香豆素-1,4-萘醌(d)系列4-羟基香豆素衍生物, 采用元素分析、红外光谱、核磁共振及质谱表征了产物的结构, 并对其紫外-可见吸收光谱及荧光光谱性质进行了研究, 探索了化合物的微观结构与其光学性能之间的关系. 研究结果表明, 具有“近平面”、大π共轭和对称型结构的化合物b具有较大的摩尔吸光系数及强荧光特性, 且浓度在0.50~1.50×10^-4 mol/L范围时, 其荧光强度随着浓度的降低而呈线性增加; 在pH=1.81~6.09时, 荧光强度随pH降低而减弱, 在pH 8.36~11.98时, 荧光强度随pH升高而减弱. 此外, 牛血清白蛋白(BSA)及脱氧核糖核酸(DNA)可与该化合物发生相互作用, 进而敏化增强该分子的内源荧光.     

Synthesis of some new fused coumarin derivatives

2-Hydrazino-4-hydroxy-5H- [1] -benzopyrano- [ 4,3-d ] -pyrim-idin-5-one (3) was prepared via condensation of 2 with hy-drazine hydrate. Treatment of 3 with methylene chloride, ethyl chloroformate, ethyl chloroacetate and benzaldehyde yielded the corresponding 2 - ( substituted ) hydrazino - 4 -hydro-xy-5H-[1]-benzopyrano-[4, 3-d]-pyrimidin-5-one (4, 5, 6, and 10), followed by cyclization of 4, 5 and 6 with dimethyl fonnamide and fused sodium acetate under reflux, while compound 10 was cyclized with bromine and sodium acetate in acetic acid. Compound 3 reacted with β-(toloyl) acrylic acid, ethyl α-cyano-p-methoxytinnamate, diethyl mal-onate and acetyl chloride affording the corresponding 2-(substituted) hydrazino-4-hydroxy-5H-[1]-benzopyrano-[4, 3-d]-pyrimidin-5-one (12, 13, 14, 15 and 16).     

Synthesis of a new coumarin dye for pH independent staining of lysosomes

A novel coumarin analogue, synthesized from 2-formylcinnamic acid and resorcinol via acid catalyzed condensation and intramolecular rearrangement, is used for pH-independent staining of lysosome in live cells via lysosomal esterase mediated fluorogenic deacetylation.     

微波辐射下香豆素葡萄糖酯化合物的合成与表征

香豆素是邻羟基桂皮酸的内酯,具有芳香气味,广泛分布于高等植物中.香豆素类化合物具有广泛的生理活性和多方面的临床用途,生物活性主要表现在光敏作用、抗病毒作用、抗菌作用、抗肿瘤作用、抗氧化作用、抗骨质疏松作用、对心血管系统的作用等[1].     

Synthesis of new condensed and cyclized coumarin derivatives

Condensation of 4-chloro-2-oxo-2H-chromene-3-carbonitrile with selected heteroarylamines in acetonitrile containing a catalytic amount of triethylamine, followed by intramolecular cyclization, gave the new coumarin derivatives with yields ranging from 43 % to 78 %. The novel compounds were subjected to acid hydrolysis giving the corresponding oxo derivatives in 66–70 % yield. The structural assignments of the synthesized compounds were based on elemental, IR, ¹H and ¹³C NMR analyses.     

Microwave-promoted automated synthesis of a coumarin library

A 30-membered library of coumarins has been synthesized in a microwave-assisted Pechmann reaction using neat trifluoroacetic acid both as an acidic reagent and a reaction medium. Alternatively, polymer-supported sulfonic acid Amberlyst-15 could also be employed to facilitate the formation of coumarins. The use of a specially-built microwave synthesizer with liquid handling tools rendered the automated synthesis of a coumarin library feasible. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 200–208, February, 2007.     

Synthesis and spectral properties of novel iminophosphoranes

Three new iminophosphoranes coded as FPZ1 (Ph–C≡C–C₆H₄–N = PPh₃), FPZ2 (Ph–N = P(C₆H₄–C≡C–Ph)₃) and FPZ3 (Ph–C≡C–C₆H₄–N = P(C₆H₄–C≡C–Ph)₃) were designed and synthesized by introducing different numbers of phenylene acetylene units to FPZ0 (Ph–N = PPh₃). The effect of structural modification was studied in detail analyzing the absorption spectra, the emission spectra, and the distributions of the electron density. The absorption spectra of the new iminophosphoranes are shown to be a linear combination of the spectra of each part by the artificial combinatorial absorption spectrum, which coincides with the real one. Most probably the individual parts can’t conjugate due to the tetrahedral structure. The probably formed excimer of FPZ0 and FPZ1 causes in their solid emission spectra an obvious bathochromic shift as compared to that of FPZ2 and FPZ3. The melting point data also showed that long branches of FPZ2 and FPZ3 will attenuate the interactions between the molecules. The results of quantum chemical calculations show that the electronic density in the HOMO of FPZ1, FPZ2, and FPZ3 is delocalized over the iminoaryl moieties. The electron density in the LUMO is delocalized over the triaryl phosphine moieties, but only concentrated on two branches, which directly determines the main direction of intramolecular charge transfer.     

荧光香豆素衍生物的合成及其光电性能研究

香豆素类衍生物是一类具有抗病毒等许多生理活性的化合物[1-3],其合成和性质的研究一直受到关注[4].