吡啶酮结构分散染料的合成及其偶氮-腙式异色机理

研究了(N-乙基-3-氰基-4-甲基-5-(4-硝基偶氮苯)-6-羟基-2-吡啶酮)(D1)和(N-乙基-3-氰基-4-甲基-5-(2-氯4-硝基偶氮苯)-6-羟基-2-吡啶酮)(D2)这2种吡啶酮分散染料在溶剂(DMF和CH₂Cl₂)和织物(涤纶和锦纶)上的偶氮-腙式异构行为,分析染料在极性和非极性溶剂中的吸收光谱差异,染料在涤纶和锦纶织物上的异色行为。运用高斯计算模拟染料的优化构型以及在溶剂和无溶剂状态下的染料吸收光谱,研究吡啶酮染料在不同环境下的偶氮-腙式存在形式。核磁共振氢谱(¹H NMR)表明,吡啶酮结构分散染料在极性溶剂中以偶氮结构存在,在非极性溶剂中以腙式结构存在。染色结果结合量子计算表明,染料在涤纶织物以腙式结构存在,在锦纶织物以偶氮结构存在。此外,吡啶酮分散染料在涤纶织物表现出超高的耐光色牢度,而在锦纶织物上的耐光色牢度较差,染料在异种织物上耐光色牢度的巨大差异归因于染料在不同织物上呈现出不同的分子结构。     

SERS-HPLC联用技术对邻氨基苯硫酚与邻碘苯甲酰氯反应的监测

通过表面增强拉曼光谱(SERS)与高效液相色谱(HPLC)联用开展了在线监测催化剂对邻氨基苯硫酚(OATP)与邻碘苯甲酰氯反应的影响. 结果表明, 无催化剂时反应产物为1b{S-[2-(2碘苯甲酰氨基)苯基]-2-碘代苯硫酸盐}和2b{N,N′-[二硫(2, 1-亚苯基)]二(2-碘苯甲酰胺)}, 在醋酸铜催化下生成3b{10-(2-碘苯甲酰基)二苯并[b, f ][1, 4]硫氮杂-11(10H)-酮}; 无催化剂条件下经历亲核取代反应及硫自由基耦合的过程, 在醋酸铜催化下产物 1b 的结构发生变异生成3b. 所得结果与核磁质谱等常规非现场技术解析结构一致.     

噻唑橙类菁染料与生物大分子结合的光谱特性的研究

研究了两个噻唑橙类菁染料TO-1和TO-2与核酸、蛋白质结合的光谱特性.发现染料喹啉环中氮上取代基对染料标记生物大分子的荧光特性有着很大的影响.羧基的引入,使染料TO-2与核酸结合后的荧光性能下降,但同时也提高了它与蛋白质结合的光物理性能.研究表明:在喹啉环氮上引入适当的亲水性取代基,可以使噻唑橙类菁染料的应用范围拓展到蛋白质标记领域.并初步研究了蛋白质浓度的变化对染料TO-2的荧光光谱的影响以及TO-2在不同pH值的蛋白质溶液中的荧光性质.     

杂环-双氰乙基系列分散染料的合成、表征及染色性能

以4个杂环芳香胺为重氮组分, 3个N,N-二氰乙基芳香胺为偶合组分, 经重氮化、 偶合反应合成了12个杂环-双氰乙基系列偶氮物; 采用紫外-可见吸收光谱、 红外光谱及核磁共振氢谱等对其结构进行了表征; 还考察了它们在涤纶织物、 乙酰化杉改性木粉和氰乙基化改性木粉上的染色性能. 结果表明, 12个偶氮物为目标产物, 在N,N-二甲基甲酰胺(DMF)中的最大可见吸收波长为417～621 nm, 摩尔吸光系数均大于10⁴. 这些化合物染色涤纶织物的色光分属黄色、 红色、 紫红色和蓝色系列, 并具有高水洗牢度和高日晒牢度; 染色乙酰化木粉和氰乙基木粉的色光和水洗牢度与染色涤纶织物相近. 这12个分散染料具有色谱范围广、 色泽鲜艳、 高发色强度和高牢度等特点, 可用于多种纤维的染色.     

一类新型四酰胺杯[4]氮杂冠醚的合成及阴离子识别研究

合成了一类新型四酰胺杯[4]氮杂冠醚（4a，4b），其结构经~1H NMR、质谱及 元素分析证实。用紫外可见光谱研究了主体与阴离子之间的相互作用，并计算出其 配合常数。结果表明，四酰胺杯[4]氮杂冠醚（4a，4b）对四面体型阴离子（p - O_2GC_6OPO_3~2_4）没有识别性能，而对平面型阴离子（p - O_2NC_6H_4O）有较 好地选择性识别性能，且主客体间形成1：1配合物。     

二苯并[b,f][1,5]二氮杂芳辛四烯衍生物的合成及拆分

以邻氨基二苯甲酮为原料,经自身缩合环化合成了3种二苯并[1,5]二氮杂芳辛四烯衍生物(1a~1c);以邻苯二甲酸酐和溴苯为原料经傅-克反应制得中间体2-(4-溴苯甲酰溴)苯甲酸(M1);M1经叠氮化后自缩合制得6,12-二(4-溴苯基)二苯并[b,f][1,5]二氮杂环辛四烯(1d);以邻氨基苯甲酸甲酯为原料,经自身缩合环化制得中间体二苯并[b,f][1,5]二氮杂环辛四烯-6,12(5H,11H)-二酮(M2);M2经氯化合成6,12-二氯二苯并[b,f][1,5]二氮杂环辛四烯(1e),化合物1a~1e的结构经~1H NMR,~(13)C NMR和ESI-MS表征,其中化合物1c为新化合物。利用超临界色谱(SFC)技术对化合物1a~1e实现了手性拆分,获得5对具有高旋光度的光学活性异构体(ee99%)。     

新型杯[4]芳烃氨基苯酚类衍生物的合成及对La3 的选择性识别

设计合成了下缘连有氨基苯氧基结构的杯[4]芳烃衍生物:5,11,17,23-四叔丁基-25-[2-(2-氨基苯氧基)乙氧基]-27-(2-羟基乙氧基)-26,28-二羟基杯[4]芳烃(化合物C),增加了与阳离子的结合位点,有利于通过配位作用对金属离子进行识别。化合物C的结构通过红外光谱、1H NMR、13C NMR和质谱进行了表征。通过紫外可见光谱和荧光发射光谱对化合物C与24种金属阳离子的络合作用进行了研究,结果发现,其对La3+有特殊的识别作用,化合物C与La3+的络合比为1∶1。     

手性锌卟啉的圆二色光谱研究

用圆二色光谱（CD）研究了三种新型手性卟啉锌[α,β,α,β－四－[邻（叔丁氧羰L－丙氨酸）氨基苯基]卟啉锌α,β,α,β,－ZnT(o-BocAla)APP1、α,β,α,β-四－[邻（叔丁氧羰L－脯氨酸）氨基苯基]卟啉锌α,β,α,β－ZnT(o-BocPro)APP2和α,β,α,β－甲－[邻（苯甲酰L－谷酰胺）氨基苯基]卟啉锌α,β,α,β－ZnT(o-BenzoylGln)APP3]在CH2Cl2 中的光谱行为,并研究了1作为主体识别手性客体分子氨基酸甲酯前后的光谱,提出了光谱形成机理。     

干气制乙苯塔底高沸物组成的气相色谱和气相色谱-傅里叶变换红外光谱分析

炼厂干气含有许多组分,其中乙烯占12%～20%[1]。利用干气中的稀乙烯制取乙苯会产生副产物[2]。国内外对塔底高沸物组分研究的不多,仅利用气相色谱 质谱联用进行定性分析[3]。我们利用气相色谱(GC)、气相色谱 傅里叶变换红外光谱(GC FTIR)技术,对干气制乙苯工艺中多乙苯装置     

4-[2-(二甲氨基)乙氧基]-N-十八烷基-1,8-萘酰亚胺荧光染料的合成及其性能研究

以4-溴-1,8-萘酐为原料,合成脂溶性4-[2-(二甲氨基)乙氧基]-N-十八烷基-1,8-萘酰亚胺。对其进行了1H NMR和IR表征。考察了荧光染料在DMF、乙腈、丙酮、乙酸乙酯和乙醚5种溶剂中的荧光光谱和吸收光谱,发现由于溶剂效应,随溶剂极性由小到大,荧光光谱和吸收光谱的最大峰值波长逐渐红移。考察了不同金属离子和pH对荧光染料荧光光谱的影响,结果表明荧光强度随Fe3+、Zn2+、Co2+浓度增大而逐渐增强,Fe3+的影响最为显著;当pH<7时,荧光强度随着pH的降低逐渐增强;进一步考察了Fe3+、Zn2+、Co2+对吸收光谱的影响,结果发现吸收光谱均蓝移。分析认为荧光染料的光致电子转移被阻碍,实验结果表明,合成的新型荧光染料可用于溶液中金属离子和pH的检测。     

吡啶酮系偶氮染料解离平衡的^15NNMR和IR波谱

报道了四个富氮-15吡啶酮偶氮染料的氮-15核磁共振中β-氮原子的化学位移,研究了氮-15原子和pH值之间的关联.当样品溶液从酸性转成碱性,β-氮-15原子的化学位移从366-380PPM移到500PPM,相应于从腺型到偶氮阴离子结构.根据各种pH值的化学位移可计算腺结构的含量,用IR证实了这一系列化合物的酸碱离解平衡.在酸性或中性条件下,固态化合物的二个羰基吸收,在碱性条件下变成只有一个羰基吸收峰,其它官能团的吸收峰表明了与平衡的位移的相应变化.     

Dyeing of multiple types of fabrics with a single reactive azo disperse dye

Three novel reactive azo disperse dyes were prepared using 7-acetamide-4-hydroxy-2-naphthalene sodium sulphate as the precursor. The structure of the dyes has the combined characteristics of reactive, disperse, and cationic dyes. Under alkaline conditions (pH 9), the dyes can be applied to cotton, silk, wool, and nylon. Under neutral conditions, they can be used to dye polyester. Under acidic conditions (pH 4.5), they can colour acrylic fabric after conversion of the tertiary amine group to the quaternary ammonium cation. The colour-fastness of the dyed fabrics were also evaluated.     

Synthesis,Characterization of Novel Bisheteroaryl Bisazo Dyes,and Their Dyeing and Solvatochromic Behavior

4‐Phenyl‐2‐aminothaizole was diazotized and coupled with N‐(alkyl)‐2‐oxo‐3‐cyano‐4‐methyl‐6‐hydroxypyridine (2‐pyridone). The resultant dyes were named as N‐(alkyl)‐6‐hydroxy‐4‐methyl‐2‐oxo‐5‐((4‐phenylthiazole‐2‐yl)diazenyl)‐1,2‐dihydro pyridine‐3‐carbonitrite and duly characterized. The diazotized aryl amines were then coupled to a moiety of above‐mentioned dyes at 5‐position of thiazole. The obtained bisheteroaryl azo dyes were characterized by elemental analysis and spectral studies. Solvent effects on the visible absorption spectra of the dyes were evaluated. The color of the dyes is discussed with respect to the nature of the heterocyclic ring, aromatic amines, and substituents present therein. All these dyes were applied as disperse dyes on to polyester fabrics, and their fastness properties were evaluated. © 2013 Wiley Periodicals, Inc. Heteroatom Chem 24:208–220, 2013; View this article online at wileyonlinelibrary.com . DOI 10.1002/hc.21085     

镍铁类水滑石对偶氮阴离子染料的吸附脱色作用

采用镍铁类水滑石作为吸附剂,对偶氮阴离子染料酸性大红G、活性艳红X-3B和直接耐酸大红4BS废水进行脱色处理,研究了时间、镍与铁的物质的量之比、初始pH和无机电解质添加剂等因素对脱色率的影响,并结合红外光谱和X射线衍射分析结果讨论了其吸附脱色机理.结果表明,三种染料在镍铁类水滑石上的吸附均为层间的阴离子交换吸附和外表面的吸附.通过阴离子交换进入层间后,不同于直接耐酸大红4BS阴离子,酸性大红G和活性艳红X-3B两种阴离子与水滑石层间水分子之间产生氢键作用;在化学键合过程中,染料分子被镍铁类水滑石表面Fe3+氧化,同时偶氮键断裂导致脱色.     

Synthesis of 6-chloro and 6-fluoro-4-hydroxyl-2-quinolone and their azo disperse dyes

<正>In this study,6-chloro-4-hydroxy-2-quinolone and 6-flouro-4-hydroxy-2-quinolone were synthesized from corresponding dianilides.These compounds were coupled with some diazotized aromatic amines to give the corresponding azo disperse dyes.The structures of the quinolone derivatives and new azo dyes were confirmed by UV-vis,FT-IR,~1H NMR and elemental analysis.     

Synthesis, structure and solvatochromic properties of some novel 5-arylazo-6-hydoxy-4-phenyl-3-cyano-2-pyridone dyes

ABSTRACT: BACKGROUND: A series of some novel arylazo pyridone dyes was synthesized from the corresponding diazonium salt and 6-hydroxy-4-phenyl-3-cyano-2-pyridone using classical reaction for the synthesis of the azo compounds. RESULTS: The structure of the dyes was confirmed by UV-vis, FT-IR, 1H NMR, 13C NMR spectroscopic technique and elemental analysis. The solvatochromic behaviour of the dyes was evaluated with respect to visible absorption properties in various solvents. CONCLUSIONS: The azo-hydrazone tautomeric equilibration is found to depend upon substituents as well as on solvents. The geometry data of the investigated dyes were obtained using DFT quantum-chemical calculations. The obtained calculational results are in very good agreement with the experimental data.     

Synthesis and Application of 2-Arylazo-3-Cyano Thieno [2,3-b]Naphthoquinones

The paper describes the synthesis of 2-amino-3-cyanothieno[2,3-b]naphthoquinone and its utilisation to prepare range of azo disperse dyes. These novel arylazo dyes were studied with respect to their color and constitution relationship. Application of these dyes on polyester fibres and their fastness properties were stated. These dyes were characterised by PMR, IR and visible absorption spectra.     

Cathodic stripping voltammetry of copper-complexed reactive dyes at a hanging mercury drop electrode: Reactive violet 5

Reactive Violet 5 and its hydrolysis product, which is produced as a side product in the dyeing process, can be determined in an admixture at sub-ppb levels by cathodic stripping voltammetry because the potentials of their azo reduction peaks are separated sufficiently. For both dyes, at intermediate pH values the azo peak is preceded by a complexed -copper reduction peak at a less negative potential, which aids the identification of the dyes. The use of pH 6 EDTA buffer removes the complexed-copper peak, as does the use of an acidic buffer (pH < 3). This unusual use of EDTA as a pH buffer facilitates the determination of mixtures of the dye and its hydrolysis product.     

SYNTHESIS AND APPLICATION OF 2-(ARYLAZO)-8-NITRONAPHTHO[1,2-d] THIAZOLE DISPERSE DYES

Abstract

The paper describes the synthesis of 2-amino-8-nitronaphtho[1,2d]thiazole and its utilization to prepare a range of heterocyclic azo disperse dyes. These arylazo dyes were studied with respect to their color and constitution relationship. These dyes were applied on polyester fibre and their fastness properties were evaluated.