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。     

香豆素-亚胺型Cu~(2+)识别荧光探针的合成及性能

以2,4-二羟基水杨醛为原料经Knoevenagel缩合反应、脱乙酰化反应,再与4-二乙氨基水杨醛经缩合反应,进而通过甲基化合成了新型的香豆素荧光探针.利用核磁共振氢谱(1 H NMR)、碳谱(13 C NMR)和高分辩质谱对所合成的目标化合物进行了结构确认,并测定了其荧光光谱.结果表明,目标化合物对Cu2+有较好的选择性和灵敏度,且当Cu2+浓度在0.66~10μmol·L-1范围内时探针的荧光强度与其浓度有较好的线性关系.Job分析法表明探针与金属离子作用形成1∶1结合的络合物.     

内酯开环塔斯品碱香豆素酯衍生荧光化合物的合成及其抗癌活性

以异香草醛为原料,经溴代、苄基保护、氧化、Ulmman反应和还原等6步反应合成了塔斯品碱内酯开环衍生物（化合物8）。 通过在其结构中分别引入含有2种不同取代基的香豆素衍生物,设计、合成了2个新型荧光性的内酯开环塔斯品碱香豆素酯衍生物（化合物9a和9b）。 产物结构经IR、1H NMR和MS进行了表征。 同时,对产物的荧光特性及其对乳腺肿瘤细胞增殖的抑制活性进行了初步测定。     

吗啉基修饰的新型香豆素Fe~(3+)荧光探针化合物的合成及其性能

间苯二酚与乙酰乙酸乙酯经亲核取代反应制得7-羟基-4-甲基香豆素(1);1与碘甲烷在乙醚中反应制得7-甲氧基-4-甲基香豆素(2);2与N-溴代丁二酰亚胺在四氯化碳中经2步反应制得3-溴-4(溴甲基)-7-甲氧基香豆素(4);4在四氢呋喃溶剂中与吗啉反应合成了一种新型的基于香豆素的荧光探针化合物——3-溴-7-甲氧基-4-(吗啉代)-2H-吡喃-2-酮(5),其结构经~1H NMR,~(13)C NMR和MS表征。光学性能和金属离子识别性能研究结果表明:5的激发波长为340.15 nm,发射波长为408.35 nm;5对Fe~(3+)有良好的识别作用,在1.0×10-5mol·L~(-1)~9.0×10~(-5)mol·L~(-1)可定量检测Fe~(3+)含量。     

新型含吡唑香豆素结构的羟胺类荧光探针的合成及在醛类化合物检测中的应用研究

醛类化合物对人体健康和人类的生活质量有重要影响,开发高效、便捷的醛类物质检测方式有较强的现实意义。通过香豆素-悉尼酮与炔基化合物的点击反应,设计并合成了两种新型的含吡唑香豆素结构的羟胺类荧光探针（O-取代型和N-取代型）,其结构经¹H NMR, ¹³C NMR, IR及HR-MS表征。其中,N-取代型羟胺探针可与食品中3种常见的糠醛类化合物(糠醛、5-甲基糠醛和5-羟甲基糠醛)进行荧光衍生反应。采用高效液相色谱-荧光检测和高分辨质谱对反应进行了分析。结果表明：衍生产物具有良好的色谱学行为,以及较高的荧光强度和较强的质谱峰信号。      

含氟香豆素基哌嗪荧光探针的合成及其性能研究

以7-羟基-4-三氟甲基香豆素和哌嗪为原料,首次合成了具有双荧光侧臂的新型香豆素类荧光探针化合物,研究发现其中间隔基较少的化合物对Cu2+具有较高的选择性,并且对Cu2+的识别不受其它金属离子的干扰.Cu2+在2.0×10-6～1.0×10-4mol/L范围内,探针的荧光强度与其浓度有较好的线性关系.     

官能团化香豆素并[4,3-d]吡唑并[3,4-b]吡啶衍生物的合成及其对锌离子的选择性识别

在硫酸铜催化下,通过3-乙酰乙酰基香豆素与5-氨基吡唑的加成环化反应合成了一系列官能团化的香豆素并[4,3-d]吡唑并[3,4-b]吡啶衍生物3a~3h.合成得到的部分化合物具有很高的荧光量子产率.利用荧光光谱考察了其与Ag~+、Cr~(3+)、Co~(2+)、Cu~(2+)、Pb~(2+)、Sn~(4+)、Fe~(3+)、Zn~(2+)等金属离子的作用,结果表明化合物3a和3b对Zn~(2+)具有很好的选择性识别能力.     

两种新型氯代荧光素探针染料的合成和表征

研究了两种具有空间连接链的新型氯代荧光素探针染料4',5'-二氯-6-(5-羧基戊氨基羰基)荧光素和2',7'-二氯- 6-(5-羧基戊氨基羰基)荧光素的合成. 以氯代间苯二酚和苯三酸酐为起始原料经7步反应得到了目标化合物, 产率良好. 测定了目标产物的荧光性能, 结果显示该化合物具有很高的荧光量子产率, 与荧光素母体相比其激发和发射波长明显向长波方向移动. 所得产物结构经1H NMR, IR, MALDI-TOF MS以及元素分析进行了表征.     

一种简单、高效合成α-卤代甲基酮化合物的新方法

发展了一种简单、高效、温和的卤代炔烃水合反应体系.在阳离子金催化剂的催化作用下,以二氯乙烷为溶剂,室温下卤代炔烃发生水合反应,高收率、高区域选择性地得到单一的α-卤代甲基酮化合物(收率≥91%).该方法具有底物适用范围广、反应条件温和和环境友好等优点,为含α-卤代甲基酮结构单元的天然产物及复杂药物分子的合成提供了新方法.     

新型香豆素类荧光化合物的合成及荧光性质研究

合成了两种香豆素类荧光化合物6,8-二氯-7-羟基香豆素-3-羧酸（DClC）和6-氯-7-羟基香豆素-3-羧酸（MClC）,其中DClC未见文献报道,并通过红外光谱、核磁共振、质谱等手段对产物的结构进行了表征。同时首次研究了这两种香豆素衍生物的紫外、荧光性质,以及不同极性溶剂、pH值、表面活性剂等的影响。结果表明,pH对性质测定影响较大,当pH=10时,DClC和MClC的荧光强度明显增强。     

Synthesis of coumarin-nucleoside conjugates via Huisgen 1,3-dipolar cycloaddition

An efficient synthesis of fluorescent coumarin-nucleoside conjugates via Cu(I) catalysed Huisgen 1,3-dipolar cycloaddition is described. Starting from azidonucleosides and coumarin derivatives, products are obtained in good yields. The fluorescent properties of the newly prepared coumarin-nucleoside conjugates are determined.     

新型含取代乙烯基香豆素衍生物的合成及其光学性能

利用Perkin反应和Wittig反应设计并合成了两个新型的香豆素衍生物——3-(4’-溴苯基)-7-(N-辛基-3’-溴咔唑-6’-乙烯基)香豆素(6a)和3-(4’-溴苯基)-7-(4’-甲氧基苯基-1’-乙烯基)香豆素(6b),其结构经UV,1H NMR,IR,MS和荧光光谱表征。研究结果表明,6a和6b具有荧光强度大和Stokes位移(分别为115 nm和122 nm)大的特点。     

微波辅助1,4-迈克尔加成合成香豆素3-,4-并六元杂环衍生物

在微波辐射下,以1,4-二氧六环为介质,六甲基二硅基胺基钾(KHMDS)为碱使香豆素与杂环烯酮缩胺进行加成环化及脱氢芳构化反应合成多环香豆素类化合物.该法只需微波辐射20min,产率60%～87%.该法具有反应时间短,操作简便等特点.     

An efficient non-ionic surfactant catalyzed multicomponent synthesis of novel benzylamino coumarin derivative via Mannich type reaction in aqueous media

An efficient non-ionic surfactant catalyzed multicomponent synthesis of novel benzylamino coumarin derivatives has been developed from secondary amines, aromatic aldehyde, and 4-hydroxy coumarin via Mannich type reaction in aqueous media. In this Mannich type reaction, surfactant forms stable colloidal medium to stabilize iminium ion which undergoes nucleophilic addition of 4-hydroxy coumarin to give benzylamino coumarin in very good yields.     

Synthesis of 7-alkoxy-4-trifluoromethylcoumarins via the von Pechmann reaction catalyzed by molecular iodine

The synthesis of a series of 7-alkoxy-4-trifluoromethylcoumarins via the von Pechmann reaction catalyzed by molecular iodine is described. The reaction protocol is simple, inexpensive and leads to the formation of the corresponding coumarin derivatives in good yield and high purity. A key intermediate as well as several iodo byproducts were isolated.     

Pyrrolo-dC oligonucleotides bearing alkynyl side chains with terminal triple bonds: synthesis, base pairing and fluorescent dye conjugates prepared by the azide-alkyne "click" reaction

5-(Octa-1,7-diynyl)-2'-deoxyuridine was converted into the furano-dU derivative 7 by copper-catalyzed cyclization; the pyrolodC-derivative 3 was formed upon ammonolysis. The bicyclic nucleosides 3 and 7 as well as the corresponding non-cyclic precursors 4 and 6 all containing terminal C[triple bond]C bonds were conjugated with the non-fluorescent 3-azido-7-hydroxycoumarin 5 employing the copper(I)-catalyzed Huisgen-Sharpless-Meldal cycloaddition "click reaction". Strongly fluorescent 1H-1,2,3-triazole conjugates (30-33) are formed incorporating two fluorescent reporters-the pyrdC nucleoside and the coumarin moiety. Oligonucleotides incorporating 6-alkynyl and 6-alkyl 7H-pyrrolo[2,3-d]pyrimidin-2(3H)-one nucleosides (3 and 2f) have been prepared by solid-phase synthesis using the phosphoramidite building blocks 10 and 13 ; the pyrrolo-dC oligonucleotides are formed during ammonia treatment. The duplex stability of oligonucleotides containing 3 and related derivatives was studied. Oligonucleotides with terminal triple bonded nucleosides such as 3 are more stabilizing than those lacking a side chain with terminal unsaturation; open-chain derivatives (4) are even more efficient. The click reaction was also performed on oligonucleotides containing the pyrdC-derivative and the fluorescence properties of nucleosides, oligonucleotides and their coumarin conjugates were studied.     

Synthesis of Functionalized Dihydrofurocoumarin Derivatives from 3-Aminoalkyl-4-hydroxycoumarin

Some dihydrofuro-fused coumarin derivatives were synthesized from 3-aminoalkyl-4-hydroxycoumarin via in situ generation of N-ylide. The 3-aminoalkylated 4-hydroxycoumarin derivatives were synthesized from one-pot, three-component reaction of 4-hydroxycoumarin, aryl aldehydes, and secondary amines in ethanol at room temperature. Again, when salicylaldehyde was employed instead of benzaldehyde, interestingly pyranocoumarins were obtained. The reaction protocol can be further explored toward the synthesis of many other heterocyclic fused dihydrofurans.     

Synthesis and characterization of novel fluorescent N-glycoconjugates

Novel fluorescent N-glycoconjugates containing d-glucose, glycine and coumarin or naphthalenetriazole derivatives were prepared by peptide synthesis type methods. The fluorescence properties (spectra, quantum yields) of the compounds were evaluated.     

FeCl3-Catalyzed Cascade Reaction: An Efficient Approach to Functionalized Coumarin Derivatives

An efficient and environmentally benign synthesis of 3-substituted or 3,4-disubstituted coumarins was accomplished via iron(III) chloride–catalyzed cascade reactions of salicylaldehydes and activated methylene compounds. The reaction preceded cleanly under mild reaction conditions to provide the desired coumarin derivatives in good to excellent yields.