CN113773666A - 一类三线态系间窜越菁染料、其制备方法及应用 - Google Patents
一类三线态系间窜越菁染料、其制备方法及应用 Download PDFInfo
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- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title abstract description 4
- -1 salt ions Chemical class 0.000 claims abstract description 29
- 239000007787 solid Substances 0.000 claims abstract description 21
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 10
- 239000001301 oxygen Substances 0.000 claims abstract description 10
- 239000003504 photosensitizing agent Substances 0.000 claims abstract description 5
- 239000000975 dye Substances 0.000 claims description 55
- DXYYSGDWQCSKKO-UHFFFAOYSA-N methylbenzothiazole Natural products C1=CC=C2SC(C)=NC2=C1 DXYYSGDWQCSKKO-UHFFFAOYSA-N 0.000 claims description 34
- 238000003786 synthesis reaction Methods 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 230000015572 biosynthetic process Effects 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 16
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 15
- 229940118019 malondialdehyde Drugs 0.000 claims description 14
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 14
- WSMYVTOQOOLQHP-UHFFFAOYSA-N Malondialdehyde Chemical class O=CCC=O WSMYVTOQOOLQHP-UHFFFAOYSA-N 0.000 claims description 13
- 125000001424 substituent group Chemical group 0.000 claims description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 230000001699 photocatalysis Effects 0.000 claims description 11
- 238000007146 photocatalysis Methods 0.000 claims description 11
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 239000003153 chemical reaction reagent Substances 0.000 claims description 9
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- 210000004027 cell Anatomy 0.000 claims description 8
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- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 6
- 229910001488 sodium perchlorate Inorganic materials 0.000 claims description 6
- 230000003197 catalytic effect Effects 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 239000002932 luster Substances 0.000 claims description 5
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 4
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- 238000004519 manufacturing process Methods 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
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- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 4
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- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 claims description 4
- 239000011541 reaction mixture Substances 0.000 claims description 4
- 229920006395 saturated elastomer Polymers 0.000 claims description 4
- 239000001632 sodium acetate Substances 0.000 claims description 4
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- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 206010028980 Neoplasm Diseases 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 claims description 2
- 201000011510 cancer Diseases 0.000 claims description 2
- 210000000170 cell membrane Anatomy 0.000 claims description 2
- 125000003963 dichloro group Chemical group Cl* 0.000 claims description 2
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 230000013632 homeostatic process Effects 0.000 claims description 2
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims description 2
- 125000001624 naphthyl group Chemical group 0.000 claims description 2
- 230000003287 optical effect Effects 0.000 claims description 2
- 210000003463 organelle Anatomy 0.000 claims description 2
- 125000000168 pyrrolyl group Chemical group 0.000 claims description 2
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- 102000004169 proteins and genes Human genes 0.000 abstract description 2
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- 239000000243 solution Substances 0.000 description 11
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 3
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 2
- NRPFNQUDKRYCNX-UHFFFAOYSA-N 4-methoxyphenylacetic acid Chemical compound COC1=CC=C(CC(O)=O)C=C1 NRPFNQUDKRYCNX-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000003384 imaging method Methods 0.000 description 2
- HVTICUPFWKNHNG-UHFFFAOYSA-N iodoethane Chemical compound CCI HVTICUPFWKNHNG-UHFFFAOYSA-N 0.000 description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- IGGNSAVLXJKCNH-UHFFFAOYSA-N 2-(3,5-difluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC(F)=CC(F)=C1 IGGNSAVLXJKCNH-UHFFFAOYSA-N 0.000 description 1
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- 125000004211 3,5-difluorophenyl group Chemical group [H]C1=C(F)C([H])=C(*)C([H])=C1F 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- AGEZXYOZHKGVCM-UHFFFAOYSA-N benzyl bromide Chemical compound BrCC1=CC=CC=C1 AGEZXYOZHKGVCM-UHFFFAOYSA-N 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
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- 230000002779 inactivation Effects 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002428 photodynamic therapy Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
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- 238000012360 testing method Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明公开了一类三线态系间窜越菁染料、其制备方法及应用;本发明属于高效率三重态光敏剂技术领域,公开了一类具有不依赖重原子且高效率系间窜越的五甲川菁染料,该类染料在光催化领域、光动力治疗和磷光成像中有良好的应用前景,该类三重态染料在五甲川菁染料母体上构建了兼容类型丰富的活性基团和大位阻基团,限制了非辐射跃迁和较小了单重态‑三重态能级差。此分子在绝大多数有机溶剂、固体状态以及水溶液中均能稳定存在,分子可在盐离子、可见光、蛋白质以及细胞中具有优越的活性氧产生能力。这类分子能够吸收近红外光到达三重态,从而利用三重态产生电子能量、磷光信号和活性氧。
Description
技术领域
本发明属于精细化工技术领域,涉及一种菁染料,特别涉及一种三线态系间窜越菁染料及制备方法和应用。
背景技术
利用分子三重态性质是现代光催化领域、光动力领域以及磷光材料领域首要追求的性质以保证染料引发化学反应、产生活性氧以及磷光信号。高效的到达三重态的分子式推动工业和生命科学应用领域发挥的强大动力。
为了实现更高效率的三重态,构建高效发生系间窜越的分子成为当下应用领域的重中之重,为了满足应用需要,能够利用近红外光能的染料并高效到达三重态成为了当下应用的需要和研究热点,对近红外吸收的染料提出了更高的要求。此外,相比于传统可见光染料,近红外共轭更大,不稳定性增强,更令人担忧的是非辐射跃迁非常容易发生,使得染料的单重态失活途径更多,不利于系间窜越的发生,导致难度陡然增加,所以当下部分染料无法高效率完成对近红外光能的利用,无法满足对光能的多远需求。因此设计开有发近红外特性并可以高效率系间窜越的染料分子成为当下亟需攻克的难题。
五甲川菁染料是目前已知的吸光度最高,处于近红外区域,稳定性良好,应用广泛的一类经典染料母体,在荧光成像领域、染色领域等应用广泛。但是这类染料的一直没有非常卓越的系间窜越性能,导致五甲川菁染料无法在光催化领域、光动力领域、磷光材料领域等去作为主要分子结构材料。基于五甲川菁染料开发一系列适用于以上多个领域的高效系间窜越光敏剂是利用染料三重态性能的必经之路。
发明内容
针对现有技术中的不足之处,本发明属于高效率三重态光敏剂技术领域,公开了一类具有不依赖重原子且高效率系间窜越的五甲川菁染料,该类染料在光催化领域、光动力治疗和磷光成像中有良好的应用前景,该类三重态染料在五甲川菁染料母体上构建了兼容类型丰富的活性基团和大位阻基团,限制了非辐射跃迁和较小了单重态-三重态能级差。此分子在绝大多数有机溶剂、固体状态以及水溶液中均能稳定存在,分子可在盐离子、可见光、蛋白质以及细胞中具有优越的活性氧产生能力。这类分子能够吸收近红外光到达三重态,从而利用三重态产生电子能量、磷光信号和活性氧。
本发明第一方面提供了一类用于高效系间窜越菁染料,其如结构通式I所示:
其中:
X-是卤素负离子,包括:Cl-、Br-、I-;
Y和Z为相同或不同的苯环不确定位置的取代基,具体为H、CH3、OMe、F、Cl、CN、NH2、COOH、NO2;
R1和R3为相同或不同的取代基,具体为H、CmH2m+1、CmH2m、CmH2m-1、CmH2m-3,吡啶基,吡咯基,苯基、萘基、蒽基、芘中的任一基团,或带有单个或多个二级取代基的衍生结构。
R2为-CO-R4、-Ph-R5、-Naph-R5;其中:
R4为H、CmH2m+1、CmH2m、CmH2m-1、CmH2m-3;
R5为nCF3、nF、nNO2、nCOOH、nCH3、nNH2、nNHR4;
其中,上文所述的m是1-20之间的整数;n是0-5之间的整数。
本发明第二方面还提供了上文所述的一类用于高效系间窜越菁染料的合成方法,其合成步骤如下:
步骤一:2-甲基苯并噻唑季铵盐的合成
将带有Y取代基修饰的2甲基苯并噻唑与带有R1取代基的卤代亚甲基衍生物按照摩尔比1:1-10比例混合,加入溶剂乙腈或者甲苯,升温至60-80℃过夜反应后,得到固体粉末带有Y和R1取代基的2-甲基苯并噻唑季铵盐;
用同样的方法,将带有Z取代基修饰的2甲基苯并噻唑与带有R3取代基的卤代亚甲基衍生物按照摩尔比1:1-10比例混合,加入溶剂乙腈或者甲苯,升温至60-80℃过夜反应后,得到固体粉末带有Z和R3取代基的2-甲基苯并噻唑季铵盐;
步骤二:带有R2取代基的丙二醛的合成
在冰水浴中,将三氯氧磷滴加到DMF中,搅拌1-5小时,然后将混合物在室温下充分混合。随后在混合物中加入带有R2取代基乙酸,将澄清溶液加热至反应完全,然后将反应混合物冷却至室温,将碎冰加入到深色混合物中,然后加入NaClO4,得到的白色结晶固体经过过滤,用饱和的NaClO4溶液洗涤,得到中间产物,无需进一步提纯即可在下一步中使用;将中间产物加入NaOH溶液中,加热条件下充分搅拌后,冷却,加入酸调至酸性,有固体析出,过滤得到化合物R2取代基的丙二醛固体粉末。
步骤三:五甲川菁染料的合成
将步骤一得到的2-甲基苯并噻唑季铵盐与步骤二中得到的丙二醛以摩尔比2:1-4混合,向其中加入试剂A,再加入催化量级试剂B,再升温至50-80℃反应至少5小时,用薄层色谱板检测反应的进行,直至反应产物不再增加;减压除去溶剂,色谱柱层析得到金属光泽的产物即为具有高效系间窜越的五甲川菁染料,所述试剂A选自乙醇、乙酸酐或乙酸中的至少一种;所述试剂B选自乙酸钠、吡啶或碳酸钾中的至少一种。
进一步优选的情况下,所述的步骤三中将溶剂减压蒸除后,还包括步骤:再溶于乙醇中得到蓝色溶液,加入硅胶蒸除溶剂并用薄层色谱柱纯化,洗脱剂极性配比为甲醇和二氯的1:8-50,得到带有金属光泽固体,即为五甲川菁染料(产率约为80-90%)。
进一步优选的情况下,所述步骤一中2-甲基苯并噻唑与卤化物三氯氧磷摩尔比为1:1-8。
进一步优选的情况下,所述步骤二中三氯氧磷和R2取代基乙酸摩尔比为3:1-10:1。
进一步优选的情况下,将步骤一得到的2-甲基苯并噻唑季铵盐与步骤二中得到的丙二醛以摩尔比2:1-8:1。
进一步优选的情况下,乙酸钠或者吡啶或碳酸钾与丙二醛的比例为3-20:1。
本发明第三方面还提供了上文所述的此类用于高效系间窜越菁染料的应用,包括在光催化领域、作为近红外区域发光材料、在生命科学领域、有机光催化领域、光解水制氢以及生物成像及传感领域的应用。
进一步优选的情况下,所述的应用具体包括:
1、能够作为三重态光敏剂,在光催化领域引发化学反应、光动力领域生成活性氧、磷光材料领域产生磷光信号。
2、这类染料分子的光信号在近红外二区成像系统中尤为突出,该系列菁染料的发光强度是普通菁染料Cy5的10倍,BODIPY染料的30倍,可以作为近红外区域发光材料。
3、这类染料分子在水相溶解性能优良,能够快速高效穿过细胞膜,进入细胞中并富集到亚细胞器内,通过低光密度的近红外光照射,高效产生活性氧物质,破坏细胞内稳态平衡,在低至纳摩尔级别高效率杀伤癌症细胞,可以应用在生命科学领域、有机光催化领域、光解水制氢以及生物成像及传感领域。
与现有技术相比,本发明具有如下有益效果:
1、这类染料通过在五甲川菁染料母体上的中位和边位上进行化学修饰,使其具备高效率的系间窜越的性能,不论是作为固体材料还是水相或者细胞中,都有优良的三重态性能。相比于不加入修饰的五甲川菁染料,系间窜越效率提高了数十倍甚至百倍千倍,用单线态氧指示剂测试表明可以高效产生活性氧等物质,验证了系间窜越的高效性;在有机溶液中,用氙灯照射10min-300min,荧光强度和吸收强度基本保持不变。
2、这类染料在空气条件下进行测试,可以长时间维持良好的三重态的性能。
3、这类染料具有合成原料低廉、方法简单并且容易进行衍生等优点。
附图说明
图1是本发明的实施例2中近红外II区域固体染料成像对比,该区域为波长大于1000纳米,其中:图1A为BODIPY,Cy5-H,TCy5-2F荧光染料固体,图1B为信号强度比对柱状图;由此证明TCy5-2F在近红外二区有很强发光信号。
图2是本发明的实施例2中TCy5-2F在二氯甲烷中的紫外吸收光谱;
图3是本发明的实施例2中TCy5-2F在二氯甲烷中的荧光发射光谱;
图4是本发明的实施例2中TCy5-2F在二甲基四氢呋喃中的磷光发射光谱
图5是本发明的实施例2中TCy5-2F在水中产生单线态氧曲线。
具体实施方式
下面结合附图,对本发明的具体实施方式进行详细地描述,但应当理解本发明的保护范围并不受具体实施方式的限制。
本发明中,除非另有其他明确说明,否则百分比、百分含量均以质量计。如无特殊说明,所使用的实验方法均为常规方法,所用材料、试剂等均可从商业途径购买。
实施例1
步骤一:2-甲基苯并噻唑季铵盐的合成
将2甲基苯并噻唑与卞溴按照摩尔比1:1比例混合,加入溶剂乙腈,升温至70℃过夜反应后,得到固体粉末2-甲基苯并噻唑季铵盐;
步骤二:带有R2取代基的丙二醛的合成
在冰水浴中,将三氯氧磷(3当量)滴加到DMF中,搅拌5小时,然后将混合物在室温下充分混合。随后在混合物中加入4-甲氧基苯乙酸(1当量),将澄清溶液加热至反应完全,然后将反应混合物冷却至室温,将碎冰加入到深色混合物中,然后加入NaClO4,得到的白色结晶固体经过过滤,用饱和的NaClO4溶液洗涤,得到中间产物,无需进一步提纯即可在下一步中使用;将中间产物加入NaOH溶液中,加热条件下充分搅拌后,冷却,加入酸调至酸性,有固体析出,过滤得到化合物4-甲氧基苯基丙二醛固体粉末。
步骤三:五甲川菁染料的合成
将2-甲基苯并噻唑季铵盐与4-甲氧基苯基丙二醛以摩尔比2:1混合,向其中加入乙醇,再加入催化量级哌啶,再升温至50℃反应至少10小时,用薄层色谱板检测反应的进行,直至反应产物不再增加;减压除去溶剂,色谱柱层析得到金属光泽的产物即为具有高效系间窜越的4-甲氧基苯基五甲川菁染料(产率约为82%)。
实施例2
步骤一:2-甲基苯并噻唑季铵盐的合成
将2甲基苯并噻唑与碘乙烷按照摩尔比1:8比例混合,加入溶剂乙腈,升温至70℃过夜反应后,得到固体粉末2-甲基苯并噻唑季铵盐;
步骤二:带有R2取代基的丙二醛的合成
在冰水浴中,将三氯氧磷(10当量)滴加到DMF中,搅拌5小时,然后将混合物在室温下充分混合。随后在混合物中加入3,5-二氟苯乙酸(1当量),将澄清溶液加热至反应完全,然后将反应混合物冷却至室温,将碎冰加入到深色混合物中,然后加入NaClO4,得到的白色结晶固体经过过滤,用饱和的NaClO4溶液洗涤,得到中间产物,无需进一步提纯即可在下一步中使用;将中间产物加入NaOH溶液中,加热条件下充分搅拌后,冷却,加入酸调至酸性,有固体析出,过滤得到化合物3,5-二氟苯基丙二醛固体粉末。
步骤三:五甲川菁染料的合成
将2-甲基苯并噻唑季铵盐与3,5-二氟苯基丙二醛以摩尔比4:1混合,向其中加入乙醇,再加入催化量级哌啶,再升温至50℃反应至少6小时,用薄层色谱板检测反应的进行,直至反应产物不再增加;减压除去溶剂,色谱柱层析得到金属光泽的产物即为具有高效系间窜越的3,5-二氟苯基五甲川菁染料(产率约为89%)。
对比例1
步骤一:2-甲基苯并噻唑季铵盐的合成
将2甲基苯并噻唑与碘乙烷按照摩尔比1:5比例混合,加入溶剂甲醇,在高压反应釜中过夜反应后,无法得到2-甲基苯并噻唑季铵盐;
对比例2
五甲川菁染料的合成
将2-甲基苯并噻唑季铵盐与3,5-二氟苯基丙二醛以摩尔比4:1混合,向其中加入乙醇,再加入催化量级吡啶,再升温至80℃反应至少12小时,同时再延长反应时间,未得到任何目标产物。
以上所述,仅为本发明较佳的具体实施方式,但本发明的保护范围并不局限于此,本领域的技术人员在本发明披露的技术范围内,可轻易想到的变化或替换,都应涵盖在本发明的保护范围之内。因此,本发明的保护范围应该以权利要求书的保护范围为准。
Claims (10)
1.一类用于高效系间窜越菁染料,其特征在于,所述染料如结构通式I所示:
其中:
X-是卤素负离子;
Y和Z为相同或不同的苯环不确定位置的取代基,分别选自H、CH3、OMe、F、Cl、CN、NH2、COOH、NO2;
R1和R3为相同或不同的取代基,分别选自H、CmH2m+1、CmH2m、CmH2m-1、CmH2m-3,吡啶基,吡咯基,苯基、萘基、蒽基、芘中的任一基团,或带有单个或多个二级取代基的衍生结构;
R2选自-CO-R4、-Ph-R5、-Naph-R5;其中:
R4选自H、CmH2m+1、CmH2m、CmH2m-1或CmH2m-3;
R5选自nCF3、nF、nNO2、nCOOH、nCH3、nNH2或nNHR4;
其中,R4或R5中的m选自1-20之间的整数;n选自0-5之间的整数。
2.根据权利要求1所述的一类用于高效系间窜越菁染料的合成方法,其特征在于:包括如下合成步骤:
步骤一:2-甲基苯并噻唑季铵盐的合成
将带有Y或Z取代基修饰的2甲基苯并噻唑与带有R1或R3取代基的卤代亚甲基衍生物按照摩尔比1:1-10比例混合,加入溶剂乙腈或者甲苯,升温至60-80℃过夜反应后,得到固体粉末2-甲基苯并噻唑季铵盐;
步骤二:带有R2取代基的丙二醛的合成
在冰水浴中,将三氯氧磷滴加到DMF中,搅拌1-5小时,然后将混合物在室温下充分混合;随后在混合物中加入带有R2取代基乙酸,将澄清溶液加热至反应完全,然后将反应混合物冷却至室温,将碎冰加入到深色混合物中,然后加入NaClO4,得到的白色结晶固体经过过滤,用饱和的NaClO4溶液洗涤,得到中间产物,无需进一步提纯即可在下一步中使用;将中间产物加入NaOH溶液中,加热条件下充分搅拌后,冷却,加入酸调至酸性,有固体析出,过滤得到化合物R2取代基的丙二醛固体粉末;
步骤三:五甲川菁染料的合成
将步骤一得到的2-甲基苯并噻唑季铵盐与步骤二中得到的丙二醛以摩尔比2:1-4混合,向其中加入试剂A,再加入催化量级试剂B,再升温至50-80℃反应至少5小时,用薄层色谱板检测反应的进行,直至反应产物不再增加;减压除去溶剂,色谱柱层析得到金属光泽的产物即为具有高效系间窜越的五甲川菁染料,所述试剂A选自乙醇、乙酸酐或乙酸中的至少一种;所述试剂B选自乙酸钠、吡啶或碳酸钾中的至少一种。
3.根据权利要求2所述的合成方法,其特征在于:所述的步骤三中将溶剂减压蒸除后,还包括步骤:再溶于乙醇中得到蓝色溶液,加入硅胶蒸除溶剂并用薄层色谱柱纯化,得到终产品。
4.根据权利要求3所述的合成方法,其特征在于:所述的步骤三中薄层色谱柱的洗脱剂极性配比为甲醇和二氯按照体积比1:8-50。
5.根据权利要求2所述的合成方法,其特征在于:所述的步骤一中2-甲基苯并噻唑与卤化物三氯氧磷摩尔比为1:1-8。
6.根据权利要求2所述的合成方法,其特征在于:所述的步骤二中三氯氧磷和R2取代基乙酸摩尔比为3-10:1。
7.根据权利要求2所述的合成方法,其特征在于:所述的步骤一得到的2-甲基苯并噻唑季铵盐与步骤二中得到的丙二醛以摩尔比2:1-8:1。
8.根据权利要求2所述的合成方法,其特征在于:所述的乙酸钠或吡啶或碳酸钾与丙二醛的比例为3-20:1。
9.如权利要求1所述的用于高效系间窜越菁染料的应用,包括在光催化领域、作为近红外区域发光材料、在生命科学领域、有机光催化领域、光解水制氢以及生物成像及传感领域的应用。
10.根据权利要求9所述的用于高效系间窜越菁染料的应用,其特征在于:所述染料作为三重态光敏剂,在光催化领域引发化学反应、光动力领域生成活性氧、磷光材料领域产生磷光信号;或者利用所述染料在水相中的溶解性能,快速高效穿过细胞膜,进入细胞中并富集到亚细胞器内;或者所述染料通过低光密度的近红外光照射,产生活性氧物质,破坏细胞内稳态平衡,在低至纳摩尔级别高效率杀伤癌症细胞,在生命科学领域、有机光催化领域、光解水制氢以及生物成像及传感领域的应用。
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