一种新型罗丹明基衍生物分子的合成

以罗丹明B为起始原料,首先与乙二胺经闭环反应制得中间体罗丹明B乙二胺(1),在K₂CO₃作用下与三聚氯嗪经亲核取代反应制得罗丹明B乙二胺-三聚氯嗪化合物(2),收率75.8%; 2与亚氨基二乙酸在K₂CO₃作用下,经氮气保护进一步发生亲核取代反应合成了一种新型罗丹明基衍生物分子--罗丹明B乙二胺-三聚氯嗪-亚氨基二乙酸,收率63.3%,三步总收率45.5%,其结构经¹H NMR、 ¹³C NMR、 IR和HR-MS(ESI)表征。     

一种基于罗丹明-硫脲类衍生物的新型活性染料的合成

首先以水合肼和异硫氰酸苯酯为原料,制得4-苯基-硫代氨基脲(M);再以罗丹明B和水合肼为原料,经闭环反应制备了罗丹明酰肼(1, RHa);然后在四氢呋喃溶剂中,化合物1在0~5 ℃条件下与三聚氯嗪经缩合取代反应,生成一缩产物罗丹明B酰肼-三聚氯嗪化合物(2, RHC);最后在氮气氛围下,化合物2进一步与M在45~50 ℃下回流,发生亲核取代反应生成文献尚未报道的新化合物--罗丹明B酰肼-三聚氯嗪-硫代氨基脲(3, RCP),其结构经¹H NMR、HRMS、IR和元素分析等表征确定。通过实验发现,RCP可在DMF-H₂O溶液[V(DMF)/V(H₂O)=1/1]中检测Hg²⁺,并且在5.0~9.0 μmol/L呈良好的线性关系。     

吡啶基三唑功能化罗丹明化合物的合成

以2-溴甲基吡啶氢溴酸盐和叠氮化钠为原料,合成中间体2-叠氮甲基吡啶（1）;对羟基苯甲醛和溴丙炔经取代反应合成中间体4-（丙-2-炔基丙氧基）苯甲醛（2）; 2与1经点击反应制得关键中间体BPT（3）; 3与罗丹明B酰肼经还原胺化反应得罗丹明类荧光探针,其结构经¹H NMR, IR和元素分析表征。     

罗丹明-三嗪衍生物的合成及探针性质

在控制反应温度的条件下, 用罗丹明B酰肼(或罗丹明B乙二胺)选择性分步取代三聚氯氰环上的活性氯, 合成了系列罗丹明-三嗪衍生物. 考察了不同取代获得的衍生物的探针识别性能, 发现所制备的衍生物能高灵敏、高选择性地识别Al³⁺, Cr³⁺或Cu²⁺离子, 是一类性能良好的金属离子荧光和比色增强型探针.     

新型2-取代氨基-3-氟-4-吡啶氟硼酸钾盐的合成

以2,3-二氟-5-氯吡啶为原料,依次经取代和还原反应制得2-取代氨基-3-氟吡啶化合物(2a~2g); 2a~2g与正丁基锂及硼酸三异丙酯经有机锂化法制得相应的硼酸化合物(3a~3g); 3a~3g分别与氟化氢钾经取代反应合成了7个新型的2-取代氨基-3-氟-4-吡啶氟硼酸钾盐,其结构经¹H NMR, ¹³C NMR, IR, ESI-MS和元素分析表征。     

两种季铵盐型离子液体钯配合物的合成

以苯甲酰肼和4-醛基吡啶为原料,经过缩合反应制备亚胺型化合物1,分别与苄氯和对二苄氯结合制备了两个新型的离子液体型亚胺配体2和3,配体2和3分别与醋酸钯反应得到新型离子液体型钯配合物4和离子液体型自组装钯配合物5,其结构经¹H NMR,¹³C NMR,IR和MS确证。      

6-氯-2-氯甲基-3-喹啉甲酸乙酯与胺的反应研究

以6-氯-2-氯甲基-3-喹啉甲酸乙酯(1)为底物,在溶剂无水乙醇中与胺及胺的衍生物2a-p反应,以较好的收率(64.8-77.7%)得到7-氯-2,3-二氢-1H-吡咯并[3,4-b]喹啉-1-酮衍生物,其中与芳胺反应生成N-芳基取代的化合物3a-i,与氨水、甲胺、乙胺和苄胺反应生成N-烷基取代的化合物3j-m,与乙二胺、丙二胺及丁二胺反应生成具有对称结构的化合物3n-p.该反应具有操作简便、条件温和等特点.所有化合物均为新化合物,其结构经IR、1H NMR、13C NMR、MS和HRMS得以证实.     

N'-取代苯磺酰基N-(4,6-二取代均-三氮苯-2-基)乙二胺的合成

N-芳基磺酰乙二胺与三聚氰氯反应获得三个新缩合产物, 缩合产物再与醇钠反应得到六个N-取代苯磺酰基-N'-取代均三嗪基乙二胺衍生物, 所有化合物都表现出对植物生长的抑制作用, 可用于筛选除草剂.     

新型吡虫啉类化合物的合成

以6-氯-3-氯甲基吡啶为原料,经水解和氧化制得6-氯-3-醛基吡啶(3);3与丙二腈反应制得关键中间体——2-(6-氯-3-亚甲基吡啶)丙二腈(4);4与杂环烯酮缩胺经加成-异构化-环化反应合成了5个新型的吡虫啉类化合物,其结构经1H NMR,13C NMR,IR,HR-EI-MS和MS表征。     

4-[3-(吡啶-4-基)-3-取代苯基丙烯酰]吗啉类化合物的合成及杀菌活性

为了寻找具有高活性的含吡啶杂环杀菌剂, 以烯酰吗啉为模板化合物, 以异烟酸为起始原料, 通过卤代反应、Friedel-Crafts酰基化反应、Wittig-Horner反应等, 将吡啶-4-基或2-氯吡啶-4-基引入到模板结构中, 设计合成了27个4-[3-(吡啶-4-基)-3-取代苯基丙烯酰]吗啉类化合物, 其结构通过1H NMR和元素分析确证. 对目标化合物的初步杀菌活性测定结果表明, 所有目标化合物对立枯丝核菌(Rhizoctonia solani Kuhn.)和掘氏疫霉菌(Phytophthora drechsler Tucker)均有较强的抑制作用, 其中4-20, 4-21, 4-22化合物对立枯丝核菌的EC50值分别为28.94, 5.27和0.87 μg/mL(对照药剂多菌灵为1.54 μg/mL, 烯酰吗啉为60.95 μg/mL); 对掘氏疫霉菌的EC50值分别为0.33, 0.27和0.09 μg/mL(对照药剂百菌清为20.39 μg/mL, 烯酰吗啉为0.24 μg/mL), 表明该类化合物具有重大的研究开发价值.     

罗丹明型荧光探针的合成及对Hg2+的识别

本文以罗丹明B-酰肼和2-氯-3-喹啉醛经缩合反应得到新型的罗丹明B衍生物3,其结构经1H NMR,MS,元素分析表征.通过荧光光谱法研究了目标物3在CH3CN-H2O溶液中与金属离子的识别特性.结果表明:目标物3可作为荧光探针选择性识别Hg2+,识别过程是不可逆的.     

A novel rhodamine-based turn-on probe for fluorescent detection of Au3+ and colorimetric detection of Cu2+

In this work, we design and synthesize the novel probe RC through introduction the 1-aza-4,13-dithia-15-crown-5 ring into the structure of rhodamine 6G hydrazide, where the N atom of crown ring is responsible for quenching of rhodamine fluorescence. The compound obtained behaves as multifunctional cation sensor providing selective fluorescent response to Au³⁺ and selective colorimetric response to Cu²⁺ ions in aqueous acetonitrile (1/1, v/v) at pH 7.0. The use of 10^?5?M RC solution allowed reliable determination of target cations in the presence of a wide range of environmentally relevant ions with detection limits of 2?×?10^?6?M and 5?×?10^?7?M for gold and copper, respectively.     

A highly selective fluorescence sensor for Tin (Sn(4+)) and its application in imaging live cells

A naphthalimide-rhodamine B derivative was synthesized as a fluorescence turn-ON chemodosimeter for Sn(4+). A colour change and marked enhancement of fluorescence was found in the presence of Sn(4+), Cu(2+) and Cr(3+) due to the ring open reaction of rhodamine and a fluorescence resonance energy transfer process. Addition of the strong chelating agent ethylenediaminetetraacetic acid disodium salt (EDTA) partly released the cation from the complex with Sn(4+) and restored the yellow fluorescence. In addition, the compound can be used as a fluorescent probe for Sn(4+) in biological systems and may act as a tool with which to study the physiological functions of tin or pathogenesis in the human body.     

An efficient rhodamine thiospirolactam-based fluorescent probe for detection of Hg2+ in aqueous samples

This paper described the optimized design, synthesis and application of a novel rhodamine thiospirolactam derivative as an 'off-on' fluorescent probe for the detection of Hg(2+) in aqueous samples. The 'off-on' fluorescence and color signal change of the probe is based on an Hg(2+)-triggered domino reaction which brings on the opened-ring form of the rhodamine spirolactam to regain the conjugated system of the rhodamine skeleton. In the well designed probe, the thiospirolactam serves as both Hg(2+) binding unit and electron-defect carbon centre, a phenolic hydroxyl with very strong nucleophilicity after deprotonation is chosen as the attacking unit, and a benzene ring is introduced on the linker to afford steric effects, which benefits an efficient nucleophilic reaction, with a high sensitivity towards Hg(2+). It exhibits a stable response for Hg(2+) from 1.0 × 10(-8) to 1.0 × 10(-6) M, with a detection limit of 3.0 × 10(-9) M. The response of the probe to Hg(2+) is highly selective and pH-insensitive, with a fast response time. All these unique features make it particularly favorable for cellular Hg(2+) imaging applications. It has been preliminarily used for highly sensitive monitoring of Hg(2+) levels in living cells with satisfying resolution.     

罗丹明6G衍生物基偏酸性“关开型”pH荧光探针

以罗丹明6G和水合肼为原料,先制备罗丹明6G酰肼,接着在乙醇中滴加少量冰醋酸做催化剂后与2,5-二甲氧基苯甲醛反应,合成了一种新型的pH荧光分子探针(RGSBD),进行了结构表征及荧光性能研究。结果表明,原本在氢离子浓度较低,即体系pH较高时(pH≥4.0),探针RGSBD内酰胺螺环闭环导致不显示荧光并且无色,然而在氢离子浓度较大即体系pH较低时(pH<4.0)时,其内酰胺螺环闭环产生了明显的颜色变化,发出强烈的荧光。pH 1.9时,探针的荧光强度达到最大,最大荧光峰发生显著的红移。进一步研究表明,探针RGSBD的荧光峰强度差值与pH在1.9~3.2范围内呈良好的线性关系,探针RGSBD识别H^+的选择性高,稳定性与可逆性强,可发展用作生物体内pH荧光传感材料。     

Syntheses and experimental studies on the relative stabilities of spiro, ansa, and bridged derivatives of cyclic tetrameric fluorophosphazene

Reactions of (CF2CH2OSiMe3)2 and CF2(CF2CH2OSiMe3)2 with N4P4F8 (1) in a 1:2.5 molar ratio resulted in the formation of monospiro compounds [(CF2CH2O)2PN](F2PN)3 (2) and [CF2(CF2)CH2O)2PN](F2PN)3 (4) as well as the intermolecular bridged compounds F7N4P4OCH2CF2CF2CH2OP4N4)F7 (3) and F7N4P4OCH2CF2CF2CF2CH2OP4N4F7 (5). An equimolar reaction of dilithiated 1,3-propanediol with 1 resulted in the 1,3-ansa-substituted compound CH2(CH2O)2[P(F)N]2(F2PN)2 (6) as the major product in good yield. However, an analogous reaction of the dilithiated 1,3-propanedithiol with 1 gave only the spirocyclic compound CH2(CH2S)2(PN)(F2PN)3 (8). The molecular structures of 2 and 6 were determined by single-crystal X-ray diffraction. In the presence of catalytic amounts of CsF in THF, the bridged compound 3 was converted to the spirocyclic compound 2 while the 1,3-ansa compound 6 under similar conditions transformed into the monospiro-substituted compound CH2(CH2O)2 (PN)(F2PN)3 (7). These transformations were monitored by time-dependent 19F and 31P NMR studies.     

A highly selective and sensitive fluorescence probe for the hypochlorite anion

A new rhodamine B-based fluorescent probe for the hypochlorite anion (OCl(-)) has been designed, synthesized, and characterized. The probe comprises a spectroscopic unit of rhodamine B and an OCl(-)-specific reactive moiety of dibenzoylhydrazine. The probe itself is nearly nonfluorescent because of its spirolactam structure. Upon reaction with OCl(-), however, a largely enhanced fluorescence is produced due to the opening of the spirolactam ring by the oxidation of the exocyclic hydrazide and subsequently the formation of the hydrolytic product rhodamine B. Most notably, the fluorescence-on reaction shows high sensitivity and extremely high selectivity for OCl(-) over other common ions and oxidants, which makes it possible for OCl(-) to be detected directly in their presence. In addition, the reaction mechanism has been investigated and proposed. The OCl(-) anion selectively oxidizes the hydrazo group in the probe, and forms the analogue of dibenzoyl diimide, which in turn hydrolyzes and releases the fluorophore. The reaction mechanism that is described here might be useful in developing excellent spectroscopic probes with cleavable active bonds for other species.     

A proton and optic dual-control molecular switch based on photochromic diarylethene bearing a rhodamine unit

A novel fluorescent switch based on rhodamine B and photochromic diarylethene, 1-[2-methyl-5-(4-methoxylphenyl)-3-thienyl]-2-[2-methyl-5-(4-rhodamine B hydrazine-Schiff base-phenyl)-3-thienyl]perfluorocyclopentene (1), has been successfully synthesized through the condensation of rhodamine B hydrazine and 1-[2-methyl-5-(4-methoxylphenyl)-3-thienyl]-2-[2-methyl-5-(4-formylphenyl)-3-thienyl]perfluorocyclopentene. UV and FL measurements reveal that the compound exhibits good photochromic properties responsive to proton and optic dual inputs. Upon irradiation with 297 nm light, the colorless solution of compound 1 turns blue, while the blue solution becomes colorless after irradiated with visible light (λ>450 nm). Furthermore, upon an addition of H⁺, the fluorescence resonance energy transfers from the rhodamine unit (FRET donor) to the closed-ring diarylethene unit (FRET acceptor), although no energy transfer occurs when the diarylethene is in the open-ring form. The emission intensity of the rhodamine can be modulated with proton and UV/vis light and molecular-level signal communication has been constructed, indicating high potentials of the compound in molecular switches or naked eye recognition systems.