CN111303141A - 2-（2-羟基苯基）苯并噻唑衍生物及其制备方法与在荧光防伪中的应用 - Google Patents
2-（2-羟基苯基）苯并噻唑衍生物及其制备方法与在荧光防伪中的应用 Download PDFInfo
- Publication number
- CN111303141A CN111303141A CN202010150272.5A CN202010150272A CN111303141A CN 111303141 A CN111303141 A CN 111303141A CN 202010150272 A CN202010150272 A CN 202010150272A CN 111303141 A CN111303141 A CN 111303141A
- Authority
- CN
- China
- Prior art keywords
- counterfeiting
- hydroxyphenyl
- fluorescence
- benzothiazole derivative
- bromophenol
- 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.)
- Granted
Links
- MVVGSPCXHRFDDR-UHFFFAOYSA-N 2-(1,3-benzothiazol-2-yl)phenol Chemical class OC1=CC=CC=C1C1=NC2=CC=CC=C2S1 MVVGSPCXHRFDDR-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000000463 material Substances 0.000 claims abstract description 14
- 150000001412 amines Chemical class 0.000 claims abstract description 10
- 230000002441 reversible effect Effects 0.000 claims abstract description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 20
- ZYMZFYQTMLOGQG-UHFFFAOYSA-N 2-(1,3-benzothiazol-2-yl)-4-bromophenol Chemical compound OC1=CC=C(Br)C=C1C1=NC2=CC=CC=C2S1 ZYMZFYQTMLOGQG-UHFFFAOYSA-N 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 13
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims description 12
- 239000012298 atmosphere Substances 0.000 claims description 12
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 10
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 10
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 claims description 7
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 claims description 6
- OZDMFSDAVYNSHX-UHFFFAOYSA-N [4-(9h-carbazol-1-yl)phenyl]boronic acid Chemical compound C1=CC(B(O)O)=CC=C1C1=CC=CC2=C1NC1=CC=CC=C12 OZDMFSDAVYNSHX-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- 239000011541 reaction mixture Substances 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 230000001678 irradiating effect Effects 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 238000010791 quenching Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 239000012043 crude product Substances 0.000 claims description 2
- 238000002425 crystallisation Methods 0.000 claims description 2
- 230000008025 crystallization Effects 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 238000005516 engineering process Methods 0.000 abstract description 5
- 239000003086 colorant Substances 0.000 abstract description 2
- 238000002189 fluorescence spectrum Methods 0.000 description 5
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 3
- 238000007639 printing Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000002761 deinking Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- JGAVTCVHDMOQTJ-UHFFFAOYSA-N (4-carbazol-9-ylphenyl)boronic acid Chemical compound C1=CC(B(O)O)=CC=C1N1C2=CC=CC=C2C2=CC=CC=C21 JGAVTCVHDMOQTJ-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000001093 holography Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
- C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
- C07D417/10—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a carbon chain containing aromatic rings
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B42—BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
- B42D—BOOKS; BOOK COVERS; LOOSE LEAVES; PRINTED MATTER CHARACTERISED BY IDENTIFICATION OR SECURITY FEATURES; PRINTED MATTER OF SPECIAL FORMAT OR STYLE NOT OTHERWISE PROVIDED FOR; DEVICES FOR USE THEREWITH AND NOT OTHERWISE PROVIDED FOR; MOVABLE-STRIP WRITING OR READING APPARATUS
- B42D25/00—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof
- B42D25/30—Identification or security features, e.g. for preventing forgery
- B42D25/36—Identification or security features, e.g. for preventing forgery comprising special materials
-
- 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
-
- 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
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
-
- 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
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
- C09K2211/1037—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with sulfur
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Thiazole And Isothizaole Compounds (AREA)
Abstract
本发明涉及2‑(2‑羟基苯基)苯并噻唑衍生物及其制备方法与在荧光防伪中的应用，2‑(2‑羟基苯基)苯并噻唑衍生物，具有式(I)所示的结构，本发明的2‑(2‑羟基苯基)苯并噻唑衍生物荧光强度强，材料性质稳定，可以长时间放置，对胺蒸气和醋酸蒸汽响应快并且可逆，实现了双色荧光显示，两种颜色的荧光对比度高，用肉眼即可区分，作为荧光防伪材料使用，可以快速辨别，提高了防伪技术的效率和安全性。
Description
技术领域
本发明涉及2-(2-羟基苯基)苯并噻唑衍生物及其制备方法与在荧光防伪中的应用，属于荧光材料与防伪应用技术领域。
背景技术
随着全球经济的不断发展，假冒商品频繁出现，每年造成的经济损失严重，然而消费者无法明确辨别商品的真伪，导致伪造行为愈演愈烈。当今社会中，重要的、昂贵的商品几乎都能被假冒，其中包括纸币、证券、支票、文件、发票、药品、化妆品和食品等。假冒伪劣商品作为一种社会现象已成为世界各国普遍关注的问题，世界上很多国家特别是一些发达国家都投入很大力量开发各种防伪技术。
目前常用的防伪技术有：激光全息、荧光防伪、水印、条形码、磁码、二维码等；磁性防伪、激光全息防伪、二维码防伪存在成本高、操作繁琐和易复制的问题。而荧光防伪具有操作简便、省时和防伪性能强等优点，使其在高科技防伪技术方面应用非常广泛。
对于防伪用荧光材料，目前研究最多的是稀土金属络合物，这类化合物存在以下缺陷：1)长时间放置后荧光强度衰减较快；2)有机稀土荧光络合物由于荧光墨粘度小，极易在印刷中引起乳化而产生浮脏或墨辊脱墨现象，特别是无色透明墨，需常检查，以防止出现由于脱墨而产生的漏印现象，用于平印效果不理想，这类荧光墨一般不在平印中应用，应用范围窄；3)荧光墨流动性大，干燥较为缓慢，极不方便。此外，目前应用的荧光防伪材料多为单色荧光。因此，传统荧光防伪的有效性和安全性面临着严重挑战。
为进一步增强防伪效果，需要研发一种新型的荧光防伪材料。
发明内容
针对现有防伪用荧光材料的不足，本发明提供2-(2-羟基苯基)苯并噻唑衍生物及其制备方法与在荧光防伪中的应用。
本发明达到以下目的：
1、防伪用荧光材料荧光强度强，材料性质稳定，长时间放置荧光强度衰减较慢；
2、实现双色荧光显示，荧光颜色对比度高。
为达到以上目的本发明是通过如下技术方案实现的：
2-(2-羟基苯基)苯并噻唑衍生物，具有式(I)所示的结构：
本发明第二个目的是提供2-(2-羟基苯基)苯并噻唑衍生物的制备方法。
2-(2-羟基苯基)苯并噻唑衍生物的制备方法，包括步骤如下：
在氮气氛围下，2-苯并噻唑基-4-溴苯酚与4-(9H-咔唑基)苯硼酸在70～90℃下反应6～8小时，得到2-(2-羟基苯基)苯并噻唑衍生物。
具体的，2-(2-羟基苯基)苯并噻唑衍生物的制备方法，步骤如下：
在氮气氛围下，将2-苯并噻唑基-4-溴苯酚溶于四氢呋喃中，加入碱溶液，然后加入4-(9H-咔唑基)苯硼酸，使2-苯并噻唑基-4-溴苯酚与4-(9H-咔唑基)苯硼酸的摩尔比为1：1～1.2，将反应混合物搅拌10分钟后，再向反应混合物中加入催化剂，在70～90℃下反应6～8小时，加水淬灭反应，有机溶剂萃取，水洗涤，干燥，浓缩得粗产物溶液，放置结晶后得2-(2-羟基苯基)苯并噻唑衍生物。
根据本发明优选的，2-苯并噻唑基-4-溴苯酚与四氢呋喃的摩尔体积比为：1：5～15，单位，mmol/mL。
根据本发明优选的，所述的碱溶液为碳酸钾水溶液，碳酸钾水溶液的浓度为1～3mM。
根据本发明优选的，2-苯并噻唑基-4-溴苯酚与碳酸钾水溶液的摩尔体积比为：1：1～3，单位，mmol/mL。
根据本发明优选的，所述的催化剂为Pd(PPh3)4，2-苯并噻唑基-4-溴苯酚与Pd(PPh3)4的摩尔比为：1:0.01～0.2。
本发明第三个目的是提供2-(2-羟基苯基)苯并噻唑衍生物的应用。
2-(2-羟基苯基)苯并噻唑衍生物的应用，作为荧光防伪材料应用于纸币、证券、支票、文件、发票中。
根据本发明优选的，具体应用方法如下：
(1)配制2-(2-羟基苯基)苯并噻唑衍生物的四氢呋喃溶液，得防伪液；
(2)将防伪液设置于防伪商品上，干燥后，采用紫外光照射，设置防伪物质的部位发出黄色荧光；
(3)将防伪商品置于有机胺蒸汽氛围中，然后采用紫外光照射，设置防伪物质的部位发出蓝绿色荧光；
(4)将防伪商品在空气中放置一段时间或置于醋酸蒸汽氛围中，恢复黄色荧光，实现固态荧光可逆响应。
根据本发明优选的，步骤(1)中，防伪液中2-(2-羟基苯基)苯并噻唑衍生物的浓度为40～60μM。
根据本发明优选的，步骤(2)、步骤(3)中，紫外光波长为365nm。
根据本发明优选的，步骤(3)中，有机胺为哌啶、异丙胺、吡咯烷中的一种。
根据本发明优选的，步骤(3)中，防伪商品在有机胺蒸汽氛围中放置时间为20～30秒。
根据本发明优选的，步骤(4)中，在空气中放置时间为5分钟～5小时，置于醋酸蒸汽氛围中时间为20～30秒。
本发明的技术特点及优点：
1、本发明的2-(2-羟基苯基)苯并噻唑衍生物荧光强度强，材料性质稳定，可以长时间放置。
2、本发明的2-(2-羟基苯基)苯并噻唑衍生物对胺蒸气和醋酸蒸汽响应快并且可逆，实现了双色荧光显示，两种颜色的荧光对比度高，用肉眼即可区分，作为荧光防伪材料使用，可以快速辨别，提高了防伪技术的效率和安全性。
3、本发明荧光材料的制备过程中所涉及原料来源广泛，合成产率高，产物荧光性能稳定，便于大规模应用与推广，具有广阔的应用前景。
附图说明
图1为实施例1制得的2-(2-羟基苯基)苯并噻唑衍生物的核磁共振氢谱图；
图2为实施例1制得的2-(2-羟基苯基)苯并噻唑衍生物的核磁共振碳谱图；
图3为实施例1制得的2-(2-羟基苯基)苯并噻唑衍生物的质谱图；
图4为负载2-(2-羟基苯基)苯并噻唑衍生物的滤纸条反复置于异丙胺蒸汽中以及醋酸蒸汽中引起的荧光光谱改变图；
图5为负载2-(2-羟基苯基)苯并噻唑衍生物的滤纸条反复置于异丙胺蒸汽中以及醋酸蒸汽中引起的荧光比率改变图谱；
图6为2-(2-羟基苯基)苯并噻唑衍生物在防伪中的应用效果图：其中，a、在日光下图片，b、用哌啶蒸汽熏后日光下图片，c、在365nm紫外灯下图片，d、用哌啶蒸汽熏后365nm紫外灯下图片，e、暴露在空气中5分钟后日光下图片，f、暴露在空气中5分钟后365nm紫外灯下图片。
具体实施方式
为更好地理解本发明，下面结合具体实施例和附图来进一步说明。
实施例中使用的试剂如无特殊说明，均为现有技术。
实施例1.2-(2-羟基苯基)苯并噻唑衍生物的制备
在25mL圆底烧瓶中，将306mg(1mmol)2-苯并噻唑基-4-溴苯酚溶于10mL四氢呋喃中，然后在氮气氛围下加入碳酸钾水溶液2mL(浓度2mM)。接着将288mg(1mmol)4-(9-咔唑基)苯硼酸加入反应混合物中，在室温下搅拌10分钟后，再将Pd(PPh3)4(58mg，0.05mmol)加入反应溶液中。混合物在80℃下搅拌反应8小时后，加入5mL纯净水淬灭反应。用二氯甲烷萃取三次，合并的有机层用水洗涤并用硫酸钠干燥，过滤，滤液减压浓缩，放置结晶，得桔黄色2-(2-羟基苯基)苯并噻唑衍生物固体270mg，产率为57.6％。
合成路线如下式Ⅱ：
制得的2-(2-羟基苯基)苯并噻唑衍生物核磁共振氢谱图、核磁共振碳谱图、质谱图分别如图1、图2、图3所示。
产物光谱分析数据：
1H NMR(400MHz,DMSO-d6)δ11.75(s,1H),8.63(d,J＝2.2Hz,1H),8.28(d,J＝7.8Hz,2H),8.18(d,J＝7.8Hz,1H),8.12(d,J＝8.1Hz,1H),8.00(d,J＝8.4Hz,2H),7.88(dd,J＝8.5,2.2Hz,1H),7.75(d,J＝8.3Hz,2H),7.57(t,J＝7.3Hz,1H),7.47(dd,J＝9.1,4.6Hz,5H),7.38–7.22(m,3H).
13C NMR(100MHz,DMSO-d6)δ64.81,156.53,151.97,140.61,139.05,136.24,135.24,131.44,131.26,128.41,127.65,126.94,126.78,125.57,123.28,122.77,122.49,121.04,120.59,119.64,118.24,110.22.
HRMS(ESI)calcd for[M+H]+469.1375,found:469.1370。
2-(2-羟基苯基)苯并噻唑衍生物固体荧光量子产率Φf[％]为70。
实施例2.2-(2-羟基苯基)苯并噻唑衍生物在防伪中的应用
(1)配制浓度为50μM的2-(2-羟基苯基)苯并噻唑衍生物的四氢呋喃溶液，得防伪液；
(2)将防伪液设置于防伪商品上，干燥后，采用365nm紫外光照射，设置防伪物质的部位发出黄色荧光；
(3)将防伪商品置于胺蒸汽氛围中30秒，然后采用365nm紫外光照射，设置防伪物质的部位发出蓝绿色荧光；
(4)将防伪商品置于醋酸蒸汽氛围中熏30秒，恢复黄色荧光，实现固态荧光可逆响应。
实验例1：2-(2-羟基苯基)苯并噻唑衍生物传感性质测试
测试方法：将10μL浓度为50μM的2-(2-羟基苯基)苯并噻唑衍生物的四氢呋喃溶液滴加到0.8cm×1.5cm的滤纸条上，然后在空气中干燥24小时，制得负载荧光染料的滤纸条。
将异丙胺(15μL)装入1cm×1cm×4cm的石英比色皿中，密封，室温放置30分钟使其饱和来制备胺蒸汽。
将负载染料的滤纸条固定在一块玻璃板上，该玻璃板放在石英比色皿中。将安装有玻璃板的比色皿放置在荧光光谱仪的固体样品架上，测试其荧光光谱。将滤纸条在异丙胺蒸汽中放置30秒，然后测试其荧光光谱。取出滤纸条，用吹风机干燥1分钟，然后在醋酸蒸汽中放置30秒，再测试其荧光光谱。重复5次。
负载2-(2-羟基苯基)苯并噻唑衍生物的滤纸条反复置于异丙胺蒸汽中以及醋酸蒸汽中引起的荧光光谱改变及荧光比率改变图谱如图4、图5所示。
实验例2：2-(2-羟基苯基)苯并噻唑衍生物传感性质测试
将2-(2-羟基苯基)苯并噻唑衍生物配置成浓度为50μM的四氢呋喃溶液。
将该溶液注入干净的中性笔中，在练功券上写下HBT字样，将练功券在日光及365nm紫外灯下分别拍照。
将写字的练功券放入哌啶蒸汽氛围内30秒，在日光及365nm紫外灯下拍照。
将练功券从哌啶蒸汽氛围取出，吹风机干燥一分钟后在空气中放置5分钟，在日光及365nm紫外灯下分别拍照。
测试结果如图6所示。
Claims (10)
1.2-(2-羟基苯基)苯并噻唑衍生物，具有式(I)所示的结构：
2.2-(2-羟基苯基)苯并噻唑衍生物的制备方法，包括步骤如下：
在氮气氛围下，2-苯并噻唑基-4-溴苯酚与4-(9H-咔唑基)苯硼酸在70～90℃下反应6～8小时，得到2-(2-羟基苯基)苯并噻唑衍生物。
3.2-(2-羟基苯基)苯并噻唑衍生物的制备方法，步骤如下：
在氮气氛围下，将2-苯并噻唑基-4-溴苯酚溶于四氢呋喃中，加入碱溶液，然后加入4-(9H-咔唑基)苯硼酸，使2-苯并噻唑基-4-溴苯酚与4-(9H-咔唑基)苯硼酸的摩尔比为1：1～1.2，将反应混合物搅拌10分钟后，再向反应混合物中加入催化剂，在70～90℃下反应6～8小时，加水淬灭反应，有机溶剂萃取，水洗涤，干燥，浓缩得粗产物溶液，放置结晶后得2-(2-羟基苯基)苯并噻唑衍生物。
4.根据权利要求3所述的制备方法，其特征在于，2-苯并噻唑基-4-溴苯酚与四氢呋喃的摩尔体积比为：1：5～15，单位，mmol/mL。
5.根据权利要求3所述的制备方法，其特征在于，所述的碱溶液为碳酸钾水溶液，碳酸钾水溶液的浓度为1～3mM，2-苯并噻唑基-4-溴苯酚与碳酸钾水溶液的摩尔体积比为：1：1～3，单位，mmol/mL。
6.根据权利要求3所述的制备方法，其特征在于，所述的催化剂为Pd(PPh3)4，2-苯并噻唑基-4-溴苯酚与Pd(PPh3)4的摩尔比为：1:0.01～0.2。
7.权利要求1所述的2-(2-羟基苯基)苯并噻唑衍生物的应用，作为荧光防伪材料应用于纸币、证券、支票、文件、发票中。
8.根据权利要求7所述的应用，其特征在于，具体应用方法如下：
(1)配制2-(2-羟基苯基)苯并噻唑衍生物的四氢呋喃溶液，得防伪液；
(2)将防伪液设置于防伪商品上，干燥后，采用紫外光照射，设置防伪物质的部位发出黄色荧光；
(3)将防伪商品置于有机胺蒸汽氛围中，然后采用紫外光照射，设置防伪物质的部位发出蓝绿色荧光；
(4)将防伪商品在空气中放置一段时间或置于醋酸蒸汽氛围中，恢复黄色荧光，实现固态荧光可逆响应。
9.根据权利要求8所述的应用，其特征在于，步骤(1)中，防伪液中2-(2-羟基苯基)苯并噻唑衍生物的浓度为40～60μM。
10.根据权利要求8所述的应用，其特征在于，步骤(2)、步骤(3)中，紫外光波长为365nm；步骤(3)中，有机胺为哌啶、异丙胺、吡咯烷中的一种，防伪商品在有机胺蒸汽氛围中放置时间为20～30秒；步骤(4)中，在空气中放置时间为5分钟～5小时，置于醋酸蒸汽氛围中时间为20～30秒。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010150272.5A CN111303141B (zh) | 2020-03-06 | 2020-03-06 | 2-(2-羟基苯基)苯并噻唑衍生物及其制备方法与在荧光防伪中的应用 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010150272.5A CN111303141B (zh) | 2020-03-06 | 2020-03-06 | 2-(2-羟基苯基)苯并噻唑衍生物及其制备方法与在荧光防伪中的应用 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111303141A true CN111303141A (zh) | 2020-06-19 |
| CN111303141B CN111303141B (zh) | 2022-08-09 |
Family
ID=71149610
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010150272.5A Active CN111303141B (zh) | 2020-03-06 | 2020-03-06 | 2-(2-羟基苯基)苯并噻唑衍生物及其制备方法与在荧光防伪中的应用 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111303141B (zh) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112519444A (zh) * | 2020-11-14 | 2021-03-19 | 西北农林科技大学 | 苯并噻唑衍生物在防伪和食品检测上的应用 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102050798A (zh) * | 2010-12-07 | 2011-05-11 | 吉林大学 | 2-(2’-羟基苯基)-苯并噻唑衍生物发光材料 |
| CN106810511A (zh) * | 2017-01-18 | 2017-06-09 | 河南工业大学 | 基于2‑(2’‑羟基苯基)苯并噻唑衍生物的pH荧光探针及其制备方法和应用 |
-
2020
- 2020-03-06 CN CN202010150272.5A patent/CN111303141B/zh active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102050798A (zh) * | 2010-12-07 | 2011-05-11 | 吉林大学 | 2-(2’-羟基苯基)-苯并噻唑衍生物发光材料 |
| CN106810511A (zh) * | 2017-01-18 | 2017-06-09 | 河南工业大学 | 基于2‑(2’‑羟基苯基)苯并噻唑衍生物的pH荧光探针及其制备方法和应用 |
Non-Patent Citations (3)
| Title |
|---|
| DANDAN YAO，等: "Hydroxyphenyl-benzothiazole based full color organic emitting materials generated by facile molecular modification", 《JOURNAL OF MATERIALS CHEMISTRY》 * |
| VAN T. N. MAI,等: "Low Amplified Spontaneous Emission Threshold and Efficient Electroluminescence from a Carbazole Derivatized Excited-State Intramolecular Proton Transfer Dye", 《ACS PHOTONICS》 * |
| VIKAS S. PADALKAR，等: "AIE Active Carbazole-Benzothiazole Based ESIPT Motifs: Positional Isomers Directing the Optical and Electronic Properties", 《CHEMISTRY SELECT》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112519444A (zh) * | 2020-11-14 | 2021-03-19 | 西北农林科技大学 | 苯并噻唑衍生物在防伪和食品检测上的应用 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111303141B (zh) | 2022-08-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Knorr et al. | New Red‐Emitting Tetrazine‐Phenoxazine Fluorogenic Labels for Live‐Cell Intracellular Bioorthogonal Labeling Schemes | |
| Erdemir et al. | Dual-channel fluorescent probe based on bisphenol A-rhodamine for Zn2+ and Hg2+ through different signaling mechanisms and its bioimaging studies | |
| Li et al. | A reversible vapor-responsive fluorochromic molecular platform based on coupled AIE–ESIPT mechanisms and its applications in anti-counterfeiting measures | |
| Aranda et al. | Vinyl-diazine triphenylamines and their N-methylated derivatives: synthesis, photophysical properties and application for staining DNA | |
| Chen et al. | Dimethylamine substituted bisbenzocoumarins: solvatochromic, mechanochromic and acidochromic properties | |
| Li et al. | New Ruthenium (II) Complexes Functionalized with Coumarin Derivatives: Synthesis, Energy‐Transfer‐Based Sensing of Esterase, Cytotoxicity, and Imaging Studies | |
| Bian et al. | Imidazole-bearing tetraphenylethylene: fluorescent probe for metal ions based on AIE feature | |
| Meng et al. | A coumarin-based portable fluorescent probe for rapid turn-on detection of amine vapors | |
| Azab et al. | Synthesis and fluorescence properties of Eu-anthracene-9-carboxylic acid towards N-acetyl amino acids and nucleotides in different solvents | |
| CN111303141B (zh) | 2-(2-羟基苯基)苯并噻唑衍生物及其制备方法与在荧光防伪中的应用 | |
| WO2015077427A1 (en) | Highly Fluorescent Pyrrole-BF2 Chromophores | |
| Ziessel et al. | Design and synthesis of alkyne-substituted boron in dipyrromethene frameworks | |
| Mao et al. | Non-conjugated dendrimers with a porphyrin core and coumarin chromophores as peripheral units: Synthesis and photophysical properties | |
| Grzybowski et al. | Effects of Amino Group Substitution on the Photophysical Properties and Stability of Near‐Infrared Fluorescent P‐Rhodamines | |
| Lu et al. | Iridium (III) complex-based fluorescent probe for detection of thiophenols and its application in water samples | |
| Qian et al. | 4-Amino-1, 8-dicyanonaphthalene derivatives as novel fluorophore and fluorescence switches: efficient synthesis and fluorescence enhancement induced by transition metal ions and protons | |
| CN111337465B (zh) | 一种基于胺蒸汽可逆响应的固态荧光防伪方法 | |
| Huang et al. | BODIPY-based hydroxypyridyl derivative as a highly Ni2+-selective fluorescent chemosensor | |
| CN111440129B (zh) | 2-(2-羟基苯基)苯并噻唑衍生物htpa及其制备方法与在荧光防伪中的应用 | |
| US8889839B2 (en) | Pyridine-bis (oxazoline)(“pybox”) moiety as a chelator and sensitizer for lanthanide ion (Ln (III)) Luminescence | |
| CN110642882A (zh) | 一种兼具双氧水检测和光动力杀伤癌细胞活性的荧光探针及其制备方法和应用 | |
| Mishra et al. | A naphthalimide appended rhodamine based biocompatible fluorescent probe: Chemosensor for selective detection of Hg2+ ion, live cell imaging and DFT study | |
| CN113336778B (zh) | 基底上潜指纹荧光可视化识别探针及方法 | |
| Tamoto et al. | Photophysical properties and structural analysis of modified methylene blues as near infrared dyes | |
| Dai et al. | One‐Step Reaction for Screening of Chromophores to Improve the Luminescence of Lanthanide Complexes |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP03 | Change of name, title or address | ||
| CP03 | Change of name, title or address |
Address after: 250353 University Road, Changqing District, Ji'nan, Shandong Province, No. 3501 Patentee after: Qilu University of Technology (Shandong Academy of Sciences) Country or region after: China Address before: 250353 University Road, Changqing District, Ji'nan, Shandong Province, No. 3501 Patentee before: Qilu University of Technology Country or region before: China |