CN105175310B - 不对称氮杂二异吲哚亚甲基化合物及其氟硼化合物的合成和用途 - Google Patents
不对称氮杂二异吲哚亚甲基化合物及其氟硼化合物的合成和用途 Download PDFInfo
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- CN105175310B CN105175310B CN201510273887.6A CN201510273887A CN105175310B CN 105175310 B CN105175310 B CN 105175310B CN 201510273887 A CN201510273887 A CN 201510273887A CN 105175310 B CN105175310 B CN 105175310B
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- diisoindole
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- -1 methylene compound Chemical class 0.000 title claims abstract description 25
- 230000015572 biosynthetic process Effects 0.000 title abstract description 15
- 238000003786 synthesis reaction Methods 0.000 title abstract description 15
- 229910015900 BF3 Inorganic materials 0.000 title abstract description 8
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- 150000001875 compounds Chemical class 0.000 claims abstract description 57
- 239000002904 solvent Substances 0.000 claims abstract description 25
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims abstract description 9
- 238000010791 quenching Methods 0.000 claims abstract description 8
- 230000000171 quenching effect Effects 0.000 claims abstract description 5
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- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
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- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 9
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- 150000002825 nitriles Chemical class 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 125000001424 substituent group Chemical group 0.000 claims description 8
- 125000003277 amino group Chemical group 0.000 claims description 6
- YFSQMOVEGCCDJL-UHFFFAOYSA-N boron monofluoride Chemical class F[B] YFSQMOVEGCCDJL-UHFFFAOYSA-N 0.000 claims description 6
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
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- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 abstract description 16
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- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical class FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 abstract description 4
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
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- MJEKVEOTULGSAG-UHFFFAOYSA-N 4-tert-butylsulfanylbenzene-1,2-dicarbonitrile Chemical compound CC(C)(C)SC1=CC=C(C#N)C(C#N)=C1 MJEKVEOTULGSAG-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
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- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical compound [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明涉及一类不对称氮杂二异吲哚亚甲基化合物及其氟硼化合物的合成和应用。本发明所提供的化合物及其氟硼化合物具有荧光量子产率高、摩尔消光系数大、Stokes位移大等特点。此外,由于其独特的“电子给体‑π共轭体系‑电子受体”型不对称结构,本发明所提供的化合物在二氯甲烷等不含N,O的溶剂中,滴入三氟乙酸或三氟甲基磺酸等强酸后会发生褪色及荧光淬灭的现象,在此无色溶液中加入含有N或O的有机溶剂或化合物可以恢复原色和荧光,因此可用作检测含有N原子或O原子的物质。同时,本发明所提供的不对称氮杂二异吲哚亚甲基化合物及其氟硼化合物在荧光传感、细胞成像、光动力治疗等方面也有重要应用价值。
Description
技术领域
本发明涉及荧光染料及其制备方法和应用,特别是一系列不对称氮杂二异吲哚亚甲基类化合物及其氟硼化合物的制备方法和在检测含氮含氧化合物中的应用。
背景技术
二吡咯亚甲基氟硼化合物(BODIPY)是一种新型荧光化合物。它具有较高的荧光量子产率和摩尔消光系数,并且表现出很好的稳定性,因而在染色、荧光标记、荧光分析、光化学传感、免疫标记、生物成像、数据存储和电致发光等领域有很好的应用。氮杂二吡咯亚甲基氟硼化合物(Aza-BODIPY)比二吡咯亚甲基氟硼化合物(BODIPY)的吸收红移而且不失BODIPY优异的光谱性质。因而可以很好的应用与生物分析和生物成像。
合成aza-BODIPY主要有以下三种方法:1)2,4-二苯基吡咯和它的亚硝基衍生物反应或者吡咯衍生物在亚硝酸钠,乙酸,乙酸酐条件下得到aza-BODIPY中间体,然后在碱性和三氟化硼乙醚条件下得到aza-BODIPY;2)氰的迈克尔加成产物在甲酸氨作用下形成氨基吡咯中间体,加热生成aza-BODIPY中间体;3)通过苯邻二氰与格氏试剂反应生成氮杂二异吲哚亚甲基化合物,然后与氟硼配位,得到芳环共轭的aza-BODIPY。通过方法1)和2)只能得到1,3,5和(或)7位取代修饰的aza-BODIPY,无法得到芳环共轭的aza-BODIPY。与1,3,5和(或)7位取代修饰aza-BODIPY相比,芳环共轭的aza-BODIPY拥有更新颖的光学性质和研究前景。[参见:(a)A.Gorman,J.Killoran,C.O’Shea,T.Kenna,W.M.Gallagher,D.F.O’Shea,J.Am.Chem.Soc.2004,126,10619;(b)S.O.McDonnell,D.F.O’Shea,Org.Lett.2006,8,3493;(c)W.M.Gallagher,L.T.Allen,C.O’Shea,T.Kenna,M.Hall,A.Gorman,J.Killoran,D.F.O’Shea,Br.J.Cancer.2005,92,1702;(d)S.O.McDonnell,M.J.Hall,L.T.Allen,A.Byrne,W.M.Gallagher,D.F.OShea,J.Am.Chem.Soc.2005,127,16360;(e)M.J.Hall,L.T.Allen,D.F.O’Shea,Org.Biomol.Chem.2006,4,776;(f)J.Killoran,D.F.O’Shea,Chem.Commun.2006,1503;(f)J.Murtagh,D.O.Frimannsson,D.F.O’Shea,Org.Lett.2009,11,5386;(g)A.Palma,M.Tasior,D.O.Frimannsson,T.Truc Vu,R.Méallet-Renault,D.F.O’Shea,Org.Lett.2009,11,3638;(h)G.Sathyamoorthi,M.L.Soong,T.W.Ross,J.H.Boyer,Heteroat.Chem.1993,4,603;(i)E.B.Knott,J.Chem.Soc.1947,1196;(j)V.F.Donyagina,S.Shimizu,N.Kobayashi,E.A.Lukyanets,Tetra.Lett.2008,49,6152.]
然而,目前的方法一方面还比较繁琐,而且产率较低。另一方面,这些方法不能用于合成不对称结构的aza-BODIPY。上述方法1)虽然可以利用某些吡咯衍生物得到不对称的二吡咯亚甲基化合物,但还是无法用于合成芳环共轭的不对称氮杂二异吲哚亚甲基化合物及其氟硼化合物。
发明内容
本发明的目的在于提供一系列不对称氮杂二异吲哚亚甲基化合物及其氟硼化合物。
为了实现上述目的,本发明的技术方案如下:
不对称氮杂二异吲哚亚甲基化合物及其氟硼化合物,它有如下结构:
取代基R=H或烷基;取代基Rx为以下之一:H,烷基,芳基,烷氧基,芳氧基,烷巯基,芳巯基。
一种制备上述的不对称氮杂二异吲哚亚甲基化合物及其氟硼化合物的方法,它可以按如下反应制备:
取代基R=烷基;取代基Rx为以下之一:H,烷基,芳基,烷氧基,芳氧基,烷巯基,芳巯基。
它包含以下步骤:
在反应容器中加入叔丁醇钾的N,N-二甲基甲酰胺溶液,Rx-取代的邻苯二腈溶解于N,N-二甲基甲酰胺,所述的Rx取代基是H、烷基、芳基、烷氧基、芳氧基、烷巯基、芳巯基。常温或更低温度下,Rx-取代的邻苯二腈溶液滴加到叔丁醇钾的溶液中,点板检测直到Rx-取代的邻苯二腈完全耗尽,继续搅拌60分钟,得到的深色溶液滴加到足量的冰水中,静置过夜,过滤,用100-140目硅胶装柱分离,洗脱剂为二氯甲烷和甲醇,蒸干溶剂后,得到红色固体,为氨基取代的不对称氮杂二异吲哚亚甲基化合物。
氨基取代的不对称氮杂二异吲哚亚甲基化合物加入到反应容器中,再加入溶有RNHR亚胺的四氢呋喃溶液,其中R为烷基,回流反应至原料点消失,旋干,用100-140目硅胶装柱分离,洗脱剂为二氯甲烷,蒸干溶剂后,用二氯甲烷/正己烷重结晶得到紫红色固体,为二烷基氨取代的不对称氮杂二异吲哚亚甲基化合物。
将所得到的上述不对称氮杂二异吲哚亚甲基化合物溶于二氯甲烷中,加入过量的三乙胺(TEA)和三氟化硼-乙醚溶液(BF3·Et2O),搅拌回流反应,点板检测直到原料完全耗尽,得到蓝紫色溶液后用水淬灭反应,反应混合物用蒸馏水、饱和碳酸氢钠水溶液、饱和食盐水依次洗涤,随后干燥后蒸发浓缩,用100-140目硅胶装柱分离,洗脱剂为二氯甲烷,蒸干溶剂后,得到紫红色化合物,为不对称氮杂二异吲哚亚甲基氟硼化合物。
用1H-NMR、UV-Vis、fluorescence spectral、ESI-MS及晶体结构表征并证实了该类不对成化合物的结构(见附图)。Bruker DRX500型核磁共振仪,溶剂为d-DMSO、CD2Cl2、CDCl3。岛津UV-2700型紫外-可见分光光度计,CH2Cl2为溶剂,扫描范围为250-800nm;LCQ电喷雾质谱仪(ESI-S,Thermo Finnigan);
一种利用所述不对称氮杂二异吲哚亚甲基化合物及其氟硼化合物检测和鉴别含有N原子或者O原子的分子的方法。步骤是;将不对称的aza-BODIPY在二氯甲烷等不含N,O的溶剂中,滴入三氟乙酸或三氟甲基磺酸等强酸发生褪色及荧光淬灭。如果在此无色溶液中在加入含有N或者O的有机溶剂或者化合物可以使溶液恢复原色和荧光,则证明含有N原子或者O原子的分子。
本发明与现有技术相比,其显著优点是:1.首次利用叔丁醇钾的N,N-二甲基甲酰胺溶液作为碱与邻苯二腈及其衍生物进行反应。由邻苯二腈及其衍生物合成氮杂二异吲哚亚甲基化合物及其氟硼化合物,该反应条件温和、步骤简单、产率高且能够大批量合成;2)首次合成了具有“电子给体-π共轭体系-电子受体”型不对称结构的氮杂二异吲哚亚甲基化合物及其氟硼化合物,这类化合物具有独特的变色性质;3)本发明所提供的不对称aza-BODIPY化合物在二氯甲烷等不含N,O的溶剂中,滴入三氟乙酸或三氟甲基磺酸等强酸后会发生褪色及荧光淬灭的现象,而在此无色溶液在加入含有N或者O的有机溶剂或者化合物可以恢复原色,而且荧光恢复,因此可以用作检测含有N原子或者O原子的物质。
附图说明
图1为化合物I-1的核磁谱图谱。
图2为化合物I-2的核磁谱图谱。
图3为化合物II-2的核磁谱图谱。
图4为化合物II-2的晶体结构。
图5为化合物I-1、I-2和II-2在CH2Cl2溶液中的吸收光谱。
图6化合物II-2的二氯甲烷溶液滴加三氟乙酸的光谱及颜色变化。
图7化合物II-2的二氯甲烷溶液(a)及滴加三氟乙酸后的II-2的二氯甲烷溶液对于结构类似化合物的区分。
具体实施方式
本发明的有机荧光材料在合成过程中都用到了邻苯二腈及其衍生物。通过下述实施例将有
助于进一步理解本发明,但不限制本发明的内容。
实施例1.化合物I-1的合成:
在反应容器中加入叔丁醇钾(0.106g,50mmol),溶解于50ml N,N-二甲基甲酰胺中,然后将邻苯二腈(6.4g,50mmol)溶于50mlN,N-二甲基甲酰胺的溶液滴加至上述溶液中,冰浴下搅拌3小时,之后将反应得到的深色溶液滴加到500g的冰水中,静置过夜。将固体过滤出来,水洗三次,烘干,得到深红色固体,为化合物I-1的粗品。将粗品溶于二氯甲烷中,用100-140目硅胶装柱分离,洗脱剂为二氯甲烷和甲醇,蒸干溶剂后然后用二氯甲烷/正己烷重结晶得到目标化合物I-1。I-1为深红色固体(4.4g,产率69%);MS(ESI):m/z 385.5[M-H]-;紫外吸收538nm(溶剂为二氯甲烷);1H NMR(500MHz,CDCl3)δ(ppm):13.18(s),8.22(1H,d).8.07(1H,d),7.91(1H,d),7.82(1H,d).7.69~7.74(2H,m),7.60(1H,d),7.54(1H,t),7.36~7.41(2H,m),7.21(1H,dd),3.71(3H,s),3.61(3H,s),其核磁图谱见附图1。
实施例2.化合物I-2的合成:
在反应容器中加入化合物I-1(3.90g,10.1mmol),再加入100ml二甲胺的四氢呋喃溶液(2mol/L),加热至回流,反应12小时后,旋干溶剂。将旋干得到的固体溶于二氯甲烷中,用100-140目硅胶装柱分离,洗脱剂为二氯甲烷,蒸干溶剂后然后用二氯甲烷/正己烷重结晶得到目标化合物I-2。I-2为紫红色固体(2.85g,产率69%)。MS(ESI):m/z 413.3[M-H]-;紫外吸收538nm(溶剂为二氯甲烷);1H NMR(500MHz,CDCl3)δ(ppm):13.18(s),8.22(1H,d).8.07(1H,d),7.91(1H,d),7.82(1H,d).7.69~7.74(2H,m),7.60(1H,d),7.54(1H,t),7.36~7.41(2H,m),7.21(1H,dd),3.71(3H,s),3.61(3H,s),其核磁图谱见附图2。
实施例3.化合物II-2的合成:
在反应容器中加入化合物I-2(2.07g,5mmol),溶解于100ml二氯甲烷中,加入过量的三乙胺(TEA)6ml搅拌均匀后,分三次加入三氟化硼-乙醚溶液(BF3·Et2O)9ml,继续搅拌回流反应,得到蓝紫色溶液,点板检测至未配位产物耗尽,随后用水淬灭反应。反应混合物用蒸馏水、饱和碳酸氢钠水溶液、饱和食盐水依次洗涤,有机层使用无水硫酸钠干燥后经旋转蒸发仪浓缩。用100-140目硅胶装柱分离,洗脱剂为二氯甲烷,蒸干溶剂后然后用二氯甲烷/正己烷重结晶得到目标化合物II-2。II-2为紫红色固体,(1.86g,产率80%)。MS(ESI):m/z 947.08[2M+Na]+;1H NMR(500MHz,CDCl3)δ(ppm):8.27(1H,d),7.90(1H,d),7.84(2H,d),7.72(1H,m),7.70(1H,m),7.62(1H,d),7.55~7.58(2H,m),7.48(1H,dd),7.11(1H,dd),3.78(6H,s);紫外吸收591nm,荧光发射为654nm(溶剂为二氯甲烷);其核磁图谱见附图3;单晶结构见附图4。
实施例4.化合物I-7的合成:
在单口瓶中,加入2.28g叔丁醇钾(20mmol)并加5ml无水DMF,在0℃通氮气保护。将1.84g的4-叔丁基邻苯二腈(10mmol)溶于5ml无水DMF,并逐滴滴加到上述溶液中,反应体系立刻变成蓝黑色。利用紫外吸收光谱监控反应进行的程度,具体方法是用移液枪移取10μL反应液加入到20μL的水中,形成红色浑浊液,向该悬浊液中加入5ml二氯甲烷,充分搅拌,形成红色溶液,检测该二氯甲烷溶液在500~600nm处的吸收光谱,当最强吸收处的强度随着时间的增加开始有减弱的趋势时,向反应液中加入50g冰水淬灭反应。过滤并用水洗,收集固体,真空下干燥,得到深红色油状物质,无需处理,直接溶在20ml二甲胺的四氢呋喃溶液(2mol/L)中,氮气保护下回流反应12小时。待反应结束,真空下旋干溶剂,粗品经硅胶作为填充材料柱层析提纯,以二氯甲烷为洗脱剂,得到红色固体粉末,为化合物I-7(585mg,收率:30%)。MS(ESI):m/z 581.5[M-H]-.Anal.Calcd.for C38H42N6:C,78.32;H,7.26;N,14.42.Found:C,78.10;H,7.48;N,14.49.
实施例5.化合物I-12的合成:
在单口瓶中,加入2.28g叔丁醇钾(20mmol)并加入5ml无水DMF,在0℃通氮气保护。将2.16g的4-叔丁巯基邻苯二腈(10mmol)溶于5ml无水DMF,并逐滴滴加到上述溶液中,反应体系立刻变成蓝黑色。利用紫外吸收光谱监控反应进行的程度,具体方法是用移液枪移取10μL反应液加入到20μL的水中,形成红色浑浊液,向该悬浊液中加入5ml二氯甲烷,充分搅拌,形成红色溶液,检测该二氯甲烷溶液在500~600nm处的吸收光谱,当最强吸收处的强度随着时间的增加开始有减弱的趋势时,向反应液中加入50g冰水淬灭反应。过滤并用水洗,收集固体,真空下干燥,得到深红色油状物质,无需处理,直接溶在20ml二甲胺的四氢呋喃溶液(2mol/L)中,氮气保护下回流反应12小时。待反应结束,真空下旋干溶剂,粗品经硅胶作为填充材料柱层析提纯,以二氯甲烷为洗脱剂,得到红色固体粉末,为化合物I-12(746mg,收率:33%)。Yield:33%.MS(ESI):m/z 677.3[M-H]-.Anal.Calcd.for C38H42N6S3:C,67.22;H,6.23;N,12.38.Found:C,67.42;H,6.12;N,12.26.
实施例6.化合物I-17的合成:
在单口瓶中,加入2.28g叔丁醇钾(20mmol)并加入5ml无水DMF,在0℃通氮气保护。将3.04g的4,4’-叔丁基邻苯二腈(10mmol)溶于5ml无水DMF,并逐滴滴加到上述溶液中,反应体系立刻变成蓝黑色。利用紫外吸收光谱监控反应进行的程度,具体方法是用移液枪移取10μL反应液加入到20μL的水中,形成红色浑浊液,向该悬浊液中加入5ml二氯甲烷,充分搅拌,形成红色溶液,检测该二氯甲烷溶液在500~600nm处的吸收光谱,当最强吸收处的强度随着时间的增加开始有减弱的趋势时,向反应液中加入50g冰水淬灭反应。过滤并用水洗,收集固体,真空下干燥,得到深红色油状物质,无需处理,直接溶在20ml二甲胺的四氢呋喃溶液(2mol/L)中,氮气保护下回流反应12小时。待反应结束,真空下旋干溶剂,粗品经硅胶作为填充材料柱层析提纯,以二氯甲烷为洗脱剂,得到红色固体粉末,为化合物I-17(880mg,收率:28%)。Yield:28%.1H NMR(500MHz,CD2Cl2)δ(ppm):12.99(s),8.41(1H,s),8.04(1H,s),7.97(1H,s),7.94(1H,s),7.90(1H,s),3.68(3H,s),3.49(3H,s),1.58(9H,s),1.49(9H,s),1.44(9H,s),1.39(9H,s),1.38(9H,s),0.96(9H,s).MS(ESI):m/z 941.3[M-H]-.Anal.Calcd.for C50H66N6S6:C,63.65;H,7.05;N,8.91 Found:C,63.80;H,6.93;N,8.76.
实施例7.化合物II-7的合成:
在单口瓶中,将116mg化合物I-7(0.2mmol)溶于10ml无水二氯甲烷,并分别加入0.2g三乙胺(2mmol)和180μL三氟化硼乙醚络合物(1.6mmol),氮气保护下回流搅拌5小时。待反应结束,真空下旋干溶剂,粗品经硅胶作为填充材料柱层析提纯,以石油醚/乙酸乙酯为洗脱剂,得到黑色固体粉末,为化合物II-7(83.2mg,收率:66%)。MS(ESI):m/z 581.5[M-H]-.Anal.Calcd.for C38H42N6:C,78.32;H,7.26;N,14.42.Found:C,78.10;H,7.48;N,14.49.
实施例8.化合物II-12的合成:
在单口瓶中,将136mg化合物I-12(0.2mmol)溶于10ml无水二氯甲烷,并分别加入0.2g三乙胺(2mmol)和180μL三氟化硼乙醚络合物(1.6mmol),氮气保护下回流搅拌5小时。待反应结束,真空下旋干溶剂,粗品经硅胶作为填充材料柱层析提纯,以石油醚/乙酸乙酯为洗脱剂,得到黑色固体粉末,为化合物II-12(102mg,收率:70%)。MS(ESI):m/z 1475.3[2M+Na]+.Anal.Calcd.for C38H41N6BF2S3:C,62.80;H,5.69;N,11.56.Found:C,62.71;H,5.58;N,11.63.
实施例9.化合物II-17的合成:
在单口瓶中,将188mg化合物I-17(0.2mmol)溶于10ml无水二氯甲烷,并分别加入0.2g三乙胺(2mmol)和180μL三氟化硼乙醚络合物(1.6mmol),氮气保护下回流搅拌5小时。待反应结束,真空下旋干溶剂,粗品经硅胶作为填充材料柱层析提纯,以石油醚/乙酸乙酯为洗脱剂,得到黑色固体粉末,为化合物II-17(142mg,收率:72%)。1H NMR(500MHz,CD2Cl2)δ(ppm):8.47(1H,s),8.15(1H,s),8.07(1H,m),7.95(1H,s),7.93(1H,s),3.76(6H,s),1.67(9H,s),1.50(9H,s),1.44(9H,s),1.40(9H,s),1.32(97H,s),1.04(9H,s).MS(ESI):m/z1013.3[M+Na]+.Anal.Calcd.for C50H65N6BF2S6:C,60.58;H,6.61;N,8.48.Found:C,60.73;H,6.74;N,8.30.
实施例10.化合物II-2的及含三氟乙酸的二氯甲烷溶液对结构类似化合物的检测:
将化合物II-2(4.63mg)溶于100ml二氯甲烷,得到浓度为10-4mol/L的红色溶液,分两份溶液分别滴加少量醋酸及三氟乙酸。滴加醋酸的溶液颜色没有变化,而滴加三氟乙酸的二氯甲烷溶液,500~600nm处吸收逐渐减弱,300~400nm处吸收逐渐增强,溶液为无色(见附图6)。取上述无色溶液,逐滴加入少量环己烷或二恶烷,十二硫醇或十二醇,苯或吡啶,通过肉眼观察颜色变化。能够发现加入少量的含氮或含氧的化合物使无色溶液变成红色。因此可以通过肉眼观察,很好的区分两种结构类似的化合物。
Claims (4)
3.权利要求1或2所述的不对称氮杂二异吲哚亚甲基化合物及其氟硼化合物的制备方法,其特征在于,按照如下反应步骤进行:
i)在反应容器中加入叔丁醇钾的N,N-二甲基甲酰胺溶液,Rx-取代的邻苯二腈溶解于N,N-二甲基甲酰胺,所述的Rx取代基是H、烷基、烷氧基、烷巯基,常温或更低温度下,Rx-取代的邻苯二腈溶液滴加到叔丁醇钾的溶液中,点板检测直到Rx-取代的邻苯二腈完全耗尽,得到的深色溶液滴加到足量的冰水中,静置过夜,过滤,用100-140目硅胶装柱分离,洗脱剂为二氯甲烷和甲醇,蒸干溶剂后,得到红色固体,为氨基取代的不对称氮杂二异吲哚亚甲基化合物;
ii)氨基取代的不对称氮杂二异吲哚亚甲基化合物加入到反应容器中,再加入溶有RNHR亚胺的四氢呋喃溶液,其中R为烷基,回流反应至原料点消失,旋干,用100-140目硅胶装柱分离,洗脱剂为二氯甲烷,蒸干溶剂后,用二氯甲烷/正己烷重结晶得到紫红色固体,为二烷基氨取代的不对称氮杂二异吲哚亚甲基化合物;
iii)将上述的得到的不对称氮杂二异吲哚亚甲基化合物溶于二氯甲烷中,加入之后加入过量的三乙胺和三氟化硼-乙醚溶液,搅拌回流反应,点板检测直到原料完全耗尽,得到蓝紫色溶液后用水淬灭反应,反应混合物用蒸馏水、饱和碳酸氢钠水溶液、饱和食盐水依次洗涤,随后干燥后蒸发浓缩,用100-140目硅胶装柱分离,洗脱剂为二氯甲烷,蒸干溶剂后,得到紫红色化合物,为不对称氮杂二异吲哚亚甲基氟硼化合物。
4.权利要求1或2所述的不对称氮杂二异吲哚亚甲基氟硼化合物在荧光传感中的应用。
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