CN105753755B - 3,3′‑二甲硫基‑4,4′‑双(2,6‑二氯‑4‑硝基苯基重氮氨基)联苯及制备方法和应用 - Google Patents

3,3′‑二甲硫基‑4,4′‑双(2,6‑二氯‑4‑硝基苯基重氮氨基)联苯及制备方法和应用 Download PDF

Info

Publication number
CN105753755B
CN105753755B CN201610159722.0A CN201610159722A CN105753755B CN 105753755 B CN105753755 B CN 105753755B CN 201610159722 A CN201610159722 A CN 201610159722A CN 105753755 B CN105753755 B CN 105753755B
Authority
CN
China
Prior art keywords
reagent
benzidines
solution
biphenyl
double
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CN201610159722.0A
Other languages
English (en)
Other versions
CN105753755A (zh
Inventor
刘慧君
樊月琴
赵强
宋金萍
樊志会
马琦
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shanxi Datong University
Original Assignee
Shanxi Datong University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shanxi Datong University filed Critical Shanxi Datong University
Priority to CN201610159722.0A priority Critical patent/CN105753755B/zh
Publication of CN105753755A publication Critical patent/CN105753755A/zh
Application granted granted Critical
Publication of CN105753755B publication Critical patent/CN105753755B/zh
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
    • C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
    • C07C319/20—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by reactions not involving the formation of sulfide groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C245/00—Compounds containing chains of at least two nitrogen atoms with at least one nitrogen-to-nitrogen multiple bond
    • C07C245/20—Diazonium compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
    • C07C319/02—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
    • C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/23—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton
    • C07C323/31—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton
    • C07C323/33—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton having at least one of the nitrogen atoms bound to a carbon atom of the same non-condensed six-membered aromatic ring
    • C07C323/34—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton having at least one of the nitrogen atoms bound to a carbon atom of the same non-condensed six-membered aromatic ring the thio group being a mercapto group
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/23—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton
    • C07C323/31—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton
    • C07C323/33—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton having at least one of the nitrogen atoms bound to a carbon atom of the same non-condensed six-membered aromatic ring
    • C07C323/35—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton having at least one of the nitrogen atoms bound to a carbon atom of the same non-condensed six-membered aromatic ring the thio group being a sulfide group
    • C07C323/36—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton having at least one of the nitrogen atoms bound to a carbon atom of the same non-condensed six-membered aromatic ring the thio group being a sulfide group the sulfur atom of the sulfide group being further bound to an acyclic carbon atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
    • C07D277/62—Benzothiazoles
    • C07D277/68—Benzothiazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2
    • C07D277/82—Nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
    • G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64—Fluorescence; Phosphorescence
    • G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
    • G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1007—Non-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1014—Carbocyclic compounds bridged by heteroatoms, e.g. N, P, Si or B
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64—Fluorescence; Phosphorescence
    • G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
    • G01N2021/6432—Quenching

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Immunology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Biochemistry (AREA)
  • Analytical Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Pathology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Molecular Biology (AREA)
  • Optics & Photonics (AREA)
  • Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
  • Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)

Abstract

本发明属双三氮烯化合物技术领域，为解决现有三氮烯试剂光度分析检测重金属离子时共存离子干扰大、灵敏度和选择性不够理想，难作荧光试剂进行重金属离子的荧光检测的问题，提供一种3,3'‑二甲硫基‑4,4'‑双(2,6‑二氯‑4‑硝基苯基重氮氨基)联苯及制备方法和应用。将3,3'‑二甲硫基‑4,4'‑二氨基联苯和2,6'‑二氯‑4‑硝基苯通过三氮烯功能基‑N=N‑NH‑链接在一起，既是灵敏度、选择性好的光度分析试剂，又是荧光特性强的荧光分析试剂。提高试剂光度法测汞的灵敏度。灵敏度、选择性好的荧光测铅（Ⅱ）试剂。常见干扰离子的允许共存量有很大提高。合成方法简单，条件温和，固体试剂及试剂溶液与汞形成的络合物均稳定。

Description

3,3'-二甲硫基-4,4'-双(2,6-二氯-4-硝基苯基重氮氨基)联 苯及制备方法和应用
技术领域
本发明属于双三氮烯化合物技术领域，具体涉及一种3,3'-二甲硫基-4,4'-双(2,6-二氯-4-硝基苯基重氮氨基)联苯及制备方法和应用。
背景技术
三氮烯试剂是指R-N=N-NH-R'结构的所有试剂的总称。该试剂-N=N-NH-功能基在表面活性剂的存在下，易于ⅠB、ⅡB族金属离子配位，生成稳定的有色配合物，因此，该类试剂可用于金属离子的光度法检测。
目前，三氮烯试剂主要用于Ca2+、Ni2+、Hg2+、Cu2+、Co2+、Ag+等金属离子的光度法测定（腾思江，江万权，朱玉瑞等。化学试剂，1992，14（2）：109）。这类试剂因具有操作简单、灵敏度高、显色反应对比度大、配合物的稳定性好、试剂易合成等优点，备受广大化学工作者的关注。不足之处是共存离子干扰较大、选择性有待提高、灵敏度也存在提高的空间。另外这类试剂通常只用于离子的光度分析，很少作为荧光试剂，用于重金属离子的荧光检测。增大试剂分子的共轭程度及改变功能基-N=N-NH-邻位的取代基被认为是提高试剂的灵敏度的有效方法，试剂分子中吸电子基团的引入增强-NH-的离解，降低显色酸度被认为是提高试剂选择性的良好途径（胡红旗，刘俊康等，化学试剂，2008，30（5）335-337）。
发明内容
本发明为了解决现有三氮烯试剂光度分析检测重金属离子时存在共存离子干扰大、灵敏度和选择性不够理想，难以作为荧光试剂进行重金属离子的荧光检测的问题，提供了一种3,3'-二甲硫基-4,4'-双(2,6-二氯-4-硝基苯基重氮氨基)联苯及制备方法和应用。
本发明是由以下技术方案实现的，一种3,3'-二甲硫基-4,4'-双(2,6-二氯-4-硝基苯基重氮氨基)联苯，简称为DMSDCNPDP，其分子结构式为：
。
3,3'-二甲硫基-4,4'-双(2,6-二氯-4-硝基苯基重氮氨基)联苯的制备方法，包括下列步骤：
(1) 2,2'-二氨基联苯二噻唑的制备：在配有干燥管、冷凝管、滴液漏斗的三颈烧瓶中，依次加入18.4 g的4,4'-二氨基联苯，150 ml冰乙酸和79.6 g的硫氰酸钾，室温下搅拌20 min，然后量取9.0 ml溴溶解在120 ml冰乙酸中，将溴的冰乙酸溶液缓慢滴加到反应混合物中，保持反应温度60℃继续搅拌反应22 h，然后将三颈烧瓶中的混合物倒入冷水中，不断搅拌并向其中加入氨，调节pH值为8，静置，待溶液冷却后过滤，干燥；用V 乙酸乙酯︰V 乙醇 =1︰1的乙酸乙酯和乙醇混合溶液重结晶，60℃真空干燥，得灰白色固体2,2'-二氨基联苯二噻唑；
(2) 3,3'-二巯基-4,4'-联苯二胺的制备：三口烧瓶中，依次加入步骤（1）所制备的2,2'-二氨基联苯二噻唑，210 g 氢氧化钾，200 ml的水和15 g乙二醇，加热回流24 h后冷却到室温，过滤，滤液在搅拌下加入冰乙酸中和至pH 6，析出固体，过滤，用V 乙酸乙酯︰V 乙醇 =1︰1的乙酸乙酯和乙醇混合液洗涤，再用水洗，干燥后得到浅黄色固体3,3'-二巯基-4,4'-联苯二胺；
(3) 3,3'-二甲硫基-4,4'-联苯二胺的制备：三口烧瓶中依次加入步骤（2）制备的3,3'-二巯基-4,4'-联苯二胺，13.8 g无水K2CO3, 150 ml无水丙酮，室温下搅拌；将14.2 g碘甲烷溶于100 ml无水丙酮，置于恒压滴液漏斗中，然后将碘甲烷的无水丙酮溶液缓慢加入到三口烧瓶中，滴加2 h后加入完成，将三口烧瓶瓶移入油浴中， 60～70 ℃，搅拌反应12h，冷却至室温后，用4 mol/L的NaOH溶液调pH至7，过滤，用50 %乙醇洗涤三次，再用水洗，干燥得3,3'-二甲硫基-4,4'-联苯二胺；
(4) 3,3'-二甲硫基-4,4'-双(2,6-二氯-4-硝基苯基重氮氨基)联苯的制备：
(4.1) 烧杯中加入35 ml浓硫酸，将烧杯置于冰浴中冷却，然后缓慢加入4.97 gNaNO2，将烧杯放入75℃水浴中温热，NaNO2全部溶解，得黄绿色溶液，将14g 2,6'-二氯-4-硝基苯胺缓慢加入到上述黄绿色溶液中，变为糊状物，补加冷却的冰乙酸80 ml，反应2 h，得黄褐色重氮盐溶液；
(4.2) 将步骤(3)制备的3,3'-二甲硫基-4,4'-联苯二胺溶于冰乙酸中，将此冰乙酸溶液加入到上述黄褐色重氮盐溶液中，再加浓70 ml H2SO4反应2h后，用4mol/l的NaOH溶液调节pH值至4－5，搅拌反应1h后，静置过夜，抽滤，用30%的乙酸洗涤两次，再用水洗两次后抽滤，然后先用丙酮热溶解，过滤后滤液浓缩，浓缩物用乙酸热溶解，再过滤，除去不溶物，将滤液倒入300ml冰水中，析出产品，干燥得粗品，粗品经硅胶吸附，以乙酸乙酯和正己烷V 乙酸乙酯︰V 正己烷 = 2︰1的混合溶液为展开剂，经过硅胶柱层析分离，获得棕红色的3,3'-二甲硫基-4,4'-双(2,6-二氯-4-硝基苯基重氮氨基)联苯。
该化合物应用于对汞Ⅱ的分光光度法检测及对铅Ⅱ的荧光猝灭法检测。
产物检测数据如下：
元素分析结果按合成产物的分子式计算各元素的理论值（w ℅）并与测定值（w℅）比较，两值相符（括号内为理论值）：C, 41.75 (41.98); H, 2.60(2.66); N, 16.41(16.33); S, 9.37(9.33); O, 9.29(9.33)。
试剂的红外光谱数据（KBr压片）： 3286 cm-1处有-NH-吸收峰，3040处有Ar-H的特征吸收峰，1590cm-1和1457cm-1处有苯环骨架振动的特征吸收峰，1345cm-1处有-N=N-的特征吸收峰，654 cm-1处有苯环C-Cl键的特征吸收峰。经元素分析和红外光谱检验合成产物与目标分子结构相符。
本发明的优点与积极效果：本发明将具有荧光特性的3,3'-二甲硫基-4,4'-二氨基联苯和2,6'-二氯-4-硝基苯通过三氮烯功能基-N=N-NH-链接在一起，合成一种既是灵敏度、选择性好的光度分析试剂，又是荧光特性强的荧光分析试剂。
（1）光度法测汞（Ⅱ）的有机显色剂主要有双硫腙、若丹宁偶氮类试剂、卟啉类试剂、三氮烯类试剂。前两类显色剂选择性和灵敏度不够高（多数的摩尔吸光系数在104数量级），且操作繁琐。卟啉类试剂是测汞的高灵敏试剂，但大部分金属元素都能与其反应而形成稳定的络合物，所以选择性较差，且这类试剂合成难，产率低。三氮烯试剂具有合成简单、灵敏度高的特点。目前，用于金属离子测定的三氮烯只含有一个功能基（-N=N-NH-），属于单三氮烯试剂。3,3'-二甲硫基-4,4'-双(2,6-二氯-4-硝基苯基重氮氨基)联苯分子中含有两个-N=N-NH-功能基，增加了试剂与金属离子的配位能力，比一般的单三氮烯试剂的灵敏度更高。光度法测汞的摩尔吸光系数高达2.90×105，是光度法测汞的高灵敏显色剂之一。
（2）新试剂DMSDCNPDP通过两个三氮烯功能基（-N=N-NH-）将联苯和两个2,6-二氯-4-硝基苯基连接在一起，形成较大的共轭体系，增强共轭体系中π电子流动性，提高了试剂与金属离子的络合能力，从而提高了试剂光度法测汞的灵敏度。
（3）新试剂具有直线型双三氮烯配位功能结构单元，通过三氮烯结构，将具有荧光特性的联苯和苯基连接后，共轭体系进一步增大，从而使荧光产率增加，是灵敏度、选择性好的新型荧光测铅（Ⅱ）试剂。
（4）新试剂DMSDCNPDP中，功能基（-N=N-NH-）邻位的甲硫基（CH3-S-）也是金属离子的配位基，由于硫属于软碱，易于与软酸（Hg2+，Ag+等）配位，从而提高试剂的选择性。另一方面，分析功能基两个邻位的吸电子基（-Cl）和对位的吸电子基（-NO2）一起作用，使试剂中-NH-更易离解，从而增加了空间位阻和降低了显色酸度，提高了试剂的选择性。与其他同类试剂相比，常见干扰离子的允许共存量有很大提高（见表3）。
（5）新试剂DMSDCNPDP合成方法简单，条件温和，固体试剂及试剂溶液与汞形成的络合物均稳定，络合物可稳定24 h。
附图说明
图1为本发明所述DMSDCNPDP的合成路线流程图。
具体实施方式
一种3,3'-二甲硫基-4,4'-双(2,6-二氯-4-硝基苯基重氮氨基)联苯，简称为DMSDCNPDP，其分子结构式为：
。
所述3,3'-二甲硫基-4,4'-双(2,6-二氯-4-硝基苯基重氮氨基)联苯的制备方法，包括下列步骤：
(1) 2,2'-二氨基联苯二噻唑的制备：在配有干燥管、冷凝管、滴液漏斗的500 ml三颈烧瓶中，依次加入4,4'-二氨基联苯18.4 g (0.1 mol)，冰乙酸150 ml和79.6 g的硫氰酸钾，室温下搅拌20 min，然后量取9.0 ml溴溶解在120 ml冰乙酸，缓慢滴加到反应混合物中，保持反应温度60℃，继续搅拌反应22 h，将三颈烧瓶中的混合物倒入冷水中，不断搅拌下向其中加入氨，调节pH值为8，静置，待溶液冷却后过滤，干燥；用V 乙酸乙酯︰V 乙醇 = 1︰1的乙酸乙酯和乙醇混合溶液重结晶，60℃真空干燥，得灰白色固体2,2'-二氨基联苯二噻唑24 g；
(2) 3,3'-二巯基-4,4'-联苯二胺的制备：在500 ml的三口烧瓶中，依次加入2,2'-二氨基联苯二噻唑24 g，210 g 氢氧化钾，200 ml的水和15 g乙二醇，加热回流24 h后冷却到室温，过滤，滤液在搅拌下加入冰乙酸中和至pH 6，析出固体，过滤，用V 乙酸乙酯︰V 乙醇 =1︰1的乙酸乙酯和乙醇混合液洗涤，再用水洗，干燥后得到浅黄色固体3,3'-二巯基-4,4'-联苯二胺12 g；
(3) 3,3'-二甲硫基-4,4'-联苯二胺的制备：在250 ml的三口烧瓶中，依次加入步骤（2）制备的3,3'-二巯基-4,4'-联苯二胺12 g，无水K2CO3 13.8 g, 无水丙酮150 ml，在室温下搅拌，将14.2 g碘甲烷溶于100 ml无水丙酮中，置于恒压滴液漏斗中，然后将碘甲烷的无水丙酮溶液缓慢加入到三口烧瓶中，滴加2 h加入完成，滴加完成后，三口烧瓶移入油浴中，温度控制在60～70 ℃，搅拌反应12 h，冷却至室温后，用4 mol/L的NaOH溶液调至pH为7，过滤，用50 %乙醇洗涤三次，再用水洗，干燥得3,3'-二甲硫基-4,4'-联苯二胺9.4 g；
(4) 3,3'-二甲硫基-4,4'-双(2,6-二氯-4-硝基苯基重氮氨基)联苯的制备：
(4.1) 将35 ml浓硫酸倒入100 ml烧杯中，将烧杯置于冰浴中冷却，然后缓慢加入NaNO2 4.97 g，加完后将烧杯放入75 ℃左右水浴中温热，使NaNO2全部溶解，得黄绿色溶液，将14 g 2,6-二氯-4-硝基苯胺缓慢加入到上述黄绿色溶液中，变为糊状物，补加冷却的冰乙酸80 ml，反应2 h，的黄褐色重氮盐溶液；
(4.2) 将步骤(3)制备的3,3'-二甲硫基-4,4'-联苯二胺9.4 g溶于冰乙酸中，将此冰乙酸溶液加入到上述黄褐色重氮盐溶液中，再加浓H2SO4 70 ml反应2 h后，用4 mol/L的NaOH溶液调节pH值至4～5，搅拌反应1 h后，静置过夜，抽滤，用30%的乙酸洗涤两次，再用水洗两次后抽滤，以丙酮和乙酸微热溶解，除去不溶物，将滤液倒入300ml冰水中，析出产品，干燥得粗品13.9 g，粗品经硅胶吸附，以乙酸乙酯和正己烷V 乙酸乙酯︰V 正己烷 = 2︰1的混合溶液为展开剂，经过硅胶柱层析分离，获得棕红色的3,3'-二甲硫基-4,4'-双(2,6-二氯-4-硝基苯基重氮氨基)联苯。
实验例1：DMSDCNPDP对Hg2+的光度分析检测。
25 ml容量瓶中依次加入≤20 µg Hg（Ⅱ）的标准溶液，依次加入pH 10.0的硼砂-氢氧化钠缓冲溶液3.0 ml，30 g /L TritonX-100溶液2.0 ml，摇匀后，加入0.2 g /LDMSDCNPDP的DMF溶液2.0 ml，以水稀释至刻度，以试剂空白作参比，用1cm比色皿，在560nm处，测定络合物溶液的吸光度。
按文献[分析化学，郭忠先，1996年第24卷第1期65-68页]方法处理头发和水样，加入混合掩蔽剂1ml，按试验方法测定，结果见表1。本发明对汞的灵敏度与现有试剂对汞的灵敏度比较结果见表２，结果显示本发明所述化合物用于汞离子的检测灵敏度高。三氮烯试剂光度法测Hg2+(5µg)时选择性比较结果见表3，结果显示本发明与其他同类试剂相比，常见干扰离子的允许共存量有很大提高。
表1 样品中汞的测定结果（n=5）
样品 本法测定值(mg/L) 双硫腙法测定值(mg/L)
工业废水 0.186 0.190
头发 2.241 2.302
[注] 混合掩蔽剂2%NaF-2%乙二胺-2%Na2C2O4混合溶液。
表2 几种三氮烯试剂测汞的灵敏度比较
序号 试剂名称 表观摩尔吸光系数(L·mol-1·cm-1)
1 2-羟基-3-羧基-5-磺酸基苯基重氮氨基偶氮苯 1.63×105
2 1-(4-安替比林)-3-(对苯磺酸) 1..70×105
3 1-(6-乙氧基2-苯并噻唑基)-3-(4-硝基苯) 2.37×105
4 1-(4-安替比林)-3-(2-苯并噻唑) 5.46×104
5 1-偶氮苯-3-(6-甲氧基-2-苯并噻唑) 1.50×105
6 3,3'-二甲硫基-4,4'-双(2,6-二氯-4-硝基苯基重氮氨基)联苯 2.90×105
表3：三氮烯试剂光度法测Hg2+(5µg)时选择性比较
实验例2：DMSDCNPDP荧光淬灭法测定铅（Ⅱ）：在25 ml容量瓶中，依次加入含铅离子1.2×10-9～1.6×10-7 mol/L的铅（Ⅱ）溶液，3 ml 3 %的Tween-80水溶液，2.0 ml pH8.2的硼砂-氢氧化钠缓冲溶液，2.5 ml 2×10-5mol/L的DMSDCNPDP溶液，然后二次蒸馏水定容。使用1cm比色皿，在激发波长(λex) 246 nm、发射波长(λem) 440 nm处测其的荧光强度，计录ΔF(试剂空白的荧光吸光度为100)。
按文献[理化检验-化学分册，魏琴，寿崇琦等，2004年第40卷第1期12-14页]处理样品，然后垵实验方法测定。结果见表4。结果显示本发明所述试剂荧光淬灭法测定铅较现有试剂灵敏度、选择性好。
表4 样品中痕量铅的测定（n=5）
样品 本法测定值(µg/g) AAS法测定值(µg/g)
绿茶 0.342 0.338
蚕豆 0.143 0.139
爆米花 1.44 1.21

Claims (2)

1.一种3,3'-二甲硫基-4,4'-双(2,6-二氯-4-硝基苯基重氮氨基)联苯，简称为DMSDCNPDP，其特征在于：其分子结构式为：
；
制备方法包括如下步骤：
(1) 2,2'-二氨基联苯二噻唑的制备：在配有干燥管、冷凝管、滴液漏斗的三颈烧瓶中，依次加入18.4 g的4,4'-二氨基联苯，150 ml冰乙酸和79.6 g的硫氰酸钾，室温下搅拌20 min，然后量取9.0 ml溴溶解在120 ml冰乙酸中，将溴的冰乙酸溶液缓慢滴加到反应混合物中，保持反应温度60℃继续搅拌反应22 h，然后将三颈烧瓶中的混合物倒入冷水中，不断搅拌并向其中加入氨，调节pH值为8，静置，待溶液冷却后过滤，干燥；用V 乙酸乙酯︰V 乙醇 = 1︰1的乙酸乙酯和乙醇混合溶液重结晶，60℃真空干燥，得灰白色固体2,2'-二氨基联苯二噻唑；
(2) 3,3'-二巯基-4,4'-联苯二胺的制备：三口烧瓶中，依次加入步骤（1）所制备的2,2'-二氨基联苯二噻唑，210 g 氢氧化钾，200 ml的水和15 g乙二醇，加热回流24 h后冷却到室温，过滤，滤液在搅拌下加入冰乙酸中和至pH 6，析出固体，过滤，用V 乙酸乙酯︰V 乙醇 = 1︰1的乙酸乙酯和乙醇混合液洗涤，再用水洗，干燥后得到浅黄色固体3,3'-二巯基-4,4'-联苯二胺；
(3) 3,3'-二甲硫基-4,4'-联苯二胺的制备：三口烧瓶中依次加入步骤（2）制备的3,3'-二巯基-4,4'-联苯二胺，13.8 g无水K2CO3, 150 ml无水丙酮，室温下搅拌；将14.2 g碘甲烷溶于100 ml无水丙酮，置于恒压滴液漏斗中，然后将碘甲烷的无水丙酮溶液缓慢加入到三口烧瓶中，滴加2 h加入完成，将三口烧瓶瓶移入油浴中， 60～70 ℃，搅拌反应12 h，冷却至室温后，用4 mol/L的NaOH溶液调pH至7，过滤，用50 %乙醇洗涤三次，再用水洗，干燥得3,3'-二甲硫基-4,4'-联苯二胺；
(4) 3,3'-二甲硫基-4,4'-双(2,6-二氯-4-硝基苯基重氮氨基)联苯的制备：
(4.1) 烧杯中加入35 ml浓硫酸，将烧杯置于冰浴中冷却，然后缓慢加入4.97 g NaNO2，将烧杯放入75℃水浴中温热，NaNO2全部溶解，得黄绿色溶液，将14g 2,6'-二氯-4-硝基苯胺缓慢加入到上述黄绿色溶液中，变为糊状物，补加冷却的冰乙酸80 ml，反应2 h，得黄褐色重氮盐溶液；
(4.2) 将步骤(3)制备的3,3'-二甲硫基-4,4'-联苯二胺溶于冰乙酸中，将此冰乙酸溶液加入到上述黄褐色重氮盐溶液中，再加浓70 ml H2SO4反应2h后，用4mol/l的NaOH溶液调节pH值至4－5，搅拌反应1h后，静置过夜，抽滤，用30%的乙酸洗涤两次，再用水洗两次后抽滤，然后先用丙酮热溶解，过滤后滤液浓缩，浓缩物用乙酸热溶解，再过滤，除去不溶物，将滤液倒入300ml冰水中，析出产品，干燥得粗品，粗品经硅胶吸附，以乙酸乙酯和正己烷V 乙酸乙酯︰V 正己烷 = 2︰1的混合溶液为展开剂，经过硅胶柱层析分离，获得棕红色的3,3'-二甲硫基-4,4'-双(2,6-二氯-4-硝基苯基重氮氨基)联苯。
2.根据权利要求1所述的一种3,3'-二甲硫基-4,4'-双(2,6-二氯-4-硝基苯基重氮氨基)联苯，其特征在于：该化合物应用于对汞Ⅱ的分光光度法检测及对铅Ⅱ的荧光猝灭法检测。
CN201610159722.0A 2016-03-21 2016-03-21 3,3′‑二甲硫基‑4,4′‑双(2,6‑二氯‑4‑硝基苯基重氮氨基)联苯及制备方法和应用 Expired - Fee Related CN105753755B (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610159722.0A CN105753755B (zh) 2016-03-21 2016-03-21 3,3′‑二甲硫基‑4,4′‑双(2,6‑二氯‑4‑硝基苯基重氮氨基)联苯及制备方法和应用

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610159722.0A CN105753755B (zh) 2016-03-21 2016-03-21 3,3′‑二甲硫基‑4,4′‑双(2,6‑二氯‑4‑硝基苯基重氮氨基)联苯及制备方法和应用

Publications (2)

Publication Number Publication Date
CN105753755A CN105753755A (zh) 2016-07-13
CN105753755B true CN105753755B (zh) 2017-10-27

Family

ID=56345383

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610159722.0A Expired - Fee Related CN105753755B (zh) 2016-03-21 2016-03-21 3,3′‑二甲硫基‑4,4′‑双(2,6‑二氯‑4‑硝基苯基重氮氨基)联苯及制备方法和应用

Country Status (1)

Country Link
CN (1) CN105753755B (zh)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110590597A (zh) * 2019-09-25 2019-12-20 浙江工业大学 一种芳基三氮烯类化合物的制备方法
CN111423563B (zh) * 2020-05-25 2022-05-27 陕西师范大学 一种用于检测Fe3+的稠杂环共轭聚合物及其制备方法和应用
CN116218097B (zh) * 2022-09-07 2024-05-24 海啊科技股份有限公司 一种可控温度发泡的pvc材料及其制备方法与应用

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101270085A (zh) * 2008-05-16 2008-09-24 山西大同大学 双(8-喹啉重氮氨基)-联苯及其制备方法和应用
CN101440071A (zh) * 2008-12-13 2009-05-27 山西大同大学 4,4’-双[5,6-二氯-2-苯并噻唑偶氮氨基]联苯-3,3’-二磺酸及其制备方法和应用
CN102311404A (zh) * 2011-10-03 2012-01-11 山西大同大学 2, 2′-双(2-羟基-4-磺酸基-1-萘氨偶氮基) -5,5′-二甲基-4, 4′-联噻唑及其制备方法
CN102358722A (zh) * 2011-07-30 2012-02-22 山西大同大学 3,3′-二羟基-4,4′-二（1,1′-二萘氨偶氮基）偶氮苯及其制备方法和应用

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101270085A (zh) * 2008-05-16 2008-09-24 山西大同大学 双(8-喹啉重氮氨基)-联苯及其制备方法和应用
CN101440071A (zh) * 2008-12-13 2009-05-27 山西大同大学 4,4’-双[5,6-二氯-2-苯并噻唑偶氮氨基]联苯-3,3’-二磺酸及其制备方法和应用
CN102358722A (zh) * 2011-07-30 2012-02-22 山西大同大学 3,3′-二羟基-4,4′-二（1,1′-二萘氨偶氮基）偶氮苯及其制备方法和应用
CN102311404A (zh) * 2011-10-03 2012-01-11 山西大同大学 2, 2′-双(2-羟基-4-磺酸基-1-萘氨偶氮基) -5,5′-二甲基-4, 4′-联噻唑及其制备方法

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
何晓玲 等.新显色剂4, 4′-二( 2, 6-二溴-4-硝基苯基重氮氨基)联苯与汞显色反应的研究.《光谱实验室》.1998,第15卷(第5期),第35-37页. *
何晓玲 等.新试剂4, 4′-二(4 -硝基苯基重氮氨基)联苯与汞的显色反应.《岩矿测试》.2006,第25卷第42-44页. *
袁跃华 等.2-甲硫基苯基重氮氨基偶氮苯的合成及其与钴显色反应的研究.《冶金分析》.2004,第24卷(第5期),第5-7页. *

Also Published As

Publication number Publication date
CN105753755A (zh) 2016-07-13

Similar Documents

Publication Publication Date Title
Chen et al. A highly selective naked-eye and fluorescent probe for fluoride ion based on 1, 8-naphalimide and benzothizazole
CN105753755B (zh) 3,3′‑二甲硫基‑4,4′‑双(2,6‑二氯‑4‑硝基苯基重氮氨基)联苯及制备方法和应用
CN109988560B (zh) 一种新型香豆素衍生物的肼荧光探针
Chen et al. Dual-mode unsymmetrical squaraine-based sensor for selective detection of Hg 2+ in aqueous media
Karcı et al. Azocalixarenes. 1: synthesis, characterization and investigation of the absorption spectra of substituted azocalix [4] arenes
CN114591633B (zh) 一类氧杂蒽-半花菁近红外荧光染料，其合成方法及应用
CN107382905B (zh) 一种检测多种离子的探针及其应用
CN114315691B (zh) 一种用于识别铜离子的非对称方酸菁比色探针及其应用
Ni et al. Dual-state emission difluoroboron derivatives for selective detection of picric acid and reversible acid/base fluorescence switching
CN105541876A (zh) 蒽醌桥联的氮杂环卡宾金属配合物及其制备方法与应用
CN105481870B (zh) 一种吡啶乙烯基三苯胺‑罗丹明荧光分子PTRh及其制备方法和应用
CN111208125B (zh) 一种双模式传感器阵列及其区分识别肼和有机胺的应用
CN109030433A (zh) 卟啉化合物荧光分子的制备及其在检测过氧化氢和葡萄糖中的应用
CN106867271A (zh) 一种大斯托克斯位移和长发射波长的萘酰亚胺类荧光染料及其合成方法和应用
CN109490291A (zh) 基于吸电子基取代的1,8-萘酰亚胺类化合物作为氟离子的显色试剂的用途
CN109503604A (zh) 苯并咪唑并咪唑衍生物及其合成方法
CN104910138A (zh) 基于均三甲苯桥联的双苯并咪唑盐及其制备方法与应用
CN103980227B (zh) 2,2`-双（2-羧基-5-甲基-4-羟基苯偶氮）-6,6`-联苯并双噻唑及其制备方法和应用
Leslee et al. Unique carbazole–N, N-dimethylanline linked chalcone a colorimetric and fluorescent probe for picric acid explosive and its test strip analysis
CN102532017B (zh) 3,3′-二乙氧基-4,4′-二（8-羟基-5-喹啉氨偶氮基）偶氮苯及其制备方法和应用
CN102584857B (zh) 2,6-二- (1,1′-萘氨基偶氮基)苯并(1,2-d;4,5-d′)双噻唑及其制备方法和应用
CN114031532B (zh) 一种硫脲基修饰的芘衍生物荧光探针及其制备方法和应用
CN102358722B (zh) 3,3′-二羟基-4,4′-二（1,1′-二萘氨偶氮基）偶氮苯及其制备方法和应用
CN103664685B (zh) 3,3′-双(2-羟基-1-萘氨基偶氮基)-4,4′-联苯二酚及其制备方法和应用
CN107090191A (zh) 一类罗丹明荧光染料及其制备方法

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20171027

Termination date: 20190321