CN108947910B - 双苯并咪唑六氟磷酸盐化合物及其制备方法与应用 - Google Patents
双苯并咪唑六氟磷酸盐化合物及其制备方法与应用 Download PDFInfo
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- -1 Bis-benzimidazole hexafluorophosphate compound Chemical class 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
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- VTZDTOPXDKOPKC-UHFFFAOYSA-N 1,8-bis(2-bromoethoxy)anthracene-9,10-dione Chemical compound O=C1C2=CC=CC(OCCBr)=C2C(=O)C2=C1C=CC=C2OCCBr VTZDTOPXDKOPKC-UHFFFAOYSA-N 0.000 claims abstract description 13
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims abstract description 12
- PAAZPARNPHGIKF-UHFFFAOYSA-N 1,2-dibromoethane Chemical compound BrCCBr PAAZPARNPHGIKF-UHFFFAOYSA-N 0.000 claims abstract description 10
- WNXANRQKWHCFBB-UHFFFAOYSA-N 1,8-bis[2-(benzimidazol-1-yl)ethoxy]anthracene-9,10-dione Chemical compound N1(C=NC2=C1C=CC=C2)CCOC1=CC=CC=2C(C3=CC=CC(=C3C(C1=2)=O)OCCN1C=NC2=C1C=CC=C2)=O WNXANRQKWHCFBB-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000003960 organic solvent Substances 0.000 claims abstract description 10
- XHXHCMZDXGCNQP-UHFFFAOYSA-N 1-(2-bromoethoxy)-8-hydroxyanthracene-9,10-dione Chemical compound BrCCOC1=CC=CC=2C(C3=CC=CC(=C3C(C1=2)=O)O)=O XHXHCMZDXGCNQP-UHFFFAOYSA-N 0.000 claims abstract description 7
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Abstract
本发明公开了新的双苯并咪唑盐的制备方法及其应用。它是在有机溶剂中以1,8‑二羟基‑9,10‑蒽醌为原料,与1,2‑二溴乙烷反应得到1‑(2‑溴乙氧基)‑8‑羟基‑9,10‑蒽醌(I)和1,8‑二(2‑溴乙氧基)‑9,10‑蒽醌(II),将(II)与苯并咪唑反应得到1,8‑二[2‑(苯并咪唑‑1‑基)乙氧基]‑9,10‑蒽醌(III),然后将其与(I)反应得到的溴化物,再将溴化物与六氟磷酸盐反应得到1,8‑二{2‑{N‑[2’‑(8’‑羟基‑9,10‑蒽醌‑1’‑基氧基)乙基]苯并咪唑甲基}‑9’,10’‑蒽醌六氟磷酸盐(IV)。本发明的双苯并咪唑盐化合物(IV)制备简洁、结构可调整、荧光感光效果明显的优点,可以用来制作荧光分子识别体系,主要应用于荧光识别技术领域。
Description
关于资助研究或开发的声明
本发明是在国家自然科学基金(基金号:21572159)的资助下进行的。
技术领域
本发明属于有机化学技术领域,涉及通过1,8-二羟基-9,10-蒽醌、1,2-二溴乙烷、苯并咪唑作为原料的双苯并咪唑六氟磷酸盐化合物(IV),更具体的说是双苯并咪唑六氟磷酸盐化合物(IV)的制备方法及其在荧光识别性能的研究。
背景技术
苯并咪唑及其衍生物的研究已经超过一个世纪。自1955年发现5,6-二甲基苯并咪唑是维生素B12的组成部分以来,因了解到苯并咪唑类化合物低毒且能够抑制菌类生长,其应用越来越广泛。苯并咪唑类衍生物具有良好的生物活性和抗蚀性,如抗癌、抗真菌、消炎、治疗低血糖和生理紊乱等, 在药物化学中具有非常重要的意义,并可用于模拟天然超氧化物歧化酶(SOD)的活性部位研究生物活性, 以及环氧树脂新型固化剂、催化剂和某些金属的表面处理剂, 还可作为有机合成反应的中间体。苯并咪唑盐类化合物之所以成为热点关注,源于它自身灵活的构造,苯并咪唑的咪唑环结构中拥有两个sp2杂化轨道氮原子, 一个氮原子可以作为离子配位点, 另一个氮原子可作为反应性位点使探针分子易于共价修饰于材料表面。通常,在进行预先的实验设计路线过程中,最常见的就是通过引入不同的桥链,而改变其原先自带的固有特性,使其发挥自身更多优势。近年来, 因荧光分析法具有很高的灵敏度和选择性, 并且苯并咪唑化合物具有较好的荧光特性,其在荧光探针领域得到了大量研究。随着研究的深入和研究范围的拓展,苯并咪唑盐类化合物作为荧光开关的主题化合物必将在化学学科、生命学科、环境分析和临床医学等领域得到应用。
发明内容
本发明的目的在于提供一种新的双苯并咪唑六氟磷酸盐化合物及其制备方法。
本发明更进一步涉及了双苯并咪唑六氟磷酸盐化合物在荧光识别领域中的应用。
为完成上述各项发明目的,本发明技术方案如下:
一种具有下述结构的双苯并咪唑盐的化合物:
IV
本发明进一步公开了苯并咪唑六氟磷酸盐化合物(IV)的制备方法,其特征在于按如下的步骤进行:
(1)在有机溶剂中以1,8-二羟基-9,10-蒽醌为原料,与1,2-二溴乙烷反应得到1-(2-溴乙氧基)-8-羟基-9,10-蒽醌(I)和1,8- 二(2-溴乙氧基)-9,10-蒽醌(II);其中1,8-二羟基-9,10-蒽醌与1,2-二溴乙烷的摩尔比为1:1和1:2;
(2)在有机溶剂中将得到的1,8- 二(2-溴乙氧基)-9,10-蒽醌(II)与苯并咪唑在碱性条件下反应得到1,8-二[2-(苯并咪唑-1-基)乙氧基] -9,10-蒽醌(III),其中(II)与苯并咪唑的摩尔比为1:2;
(3)将1,8-二[2-(苯并咪唑-1-基)乙氧基] -9,10-蒽醌(III)与1- (2-溴乙氧基)-8-羟基-9,10-蒽醌(I)反应得到的溴化物再与NH4PF6以摩尔比为1:1.5的比例加入到反应器皿内,用有机溶剂溶解后,在室温温度下反应1天,过滤,洗涤,得到1,8-二{2- {N- [2’- (8’ - 羟基-9,10 - 蒽醌-1’-基氧基)乙基]苯并咪唑甲基} -9’,10’ - 蒽醌六氟磷酸盐(IV)。其中所述的原料为1,8-二羟基-9,10-蒽醌、1,2-二溴乙烷、碳酸钾、苯并咪唑、六氟磷酸铵、四丁基溴化铵。
所述的有机溶剂选自二氯甲烷、丙酮、甲醇、***、乙腈、乙酸乙酯中的一种或几种的混合物。
一种典型的苯并咪唑化合物:
典型的双苯并咪唑盐化合物(IV)的分子式为C64H46F12N4O12P2。
特别加以说明的是双苯并咪唑盐化合物(IV)的单晶数据如下(采用Bruker APEXII CCD衍射仪进行测定):
本发明所述双苯并咪唑盐化合物(IV)晶体的制备方法,其特征在于将双苯并咪唑盐化合物(IV)溶于乙腈后放入试管中,在非良性溶剂中扩散令其缓慢结晶得到其淡黄色晶体。所述的非良性溶剂指的是***。
本发明更进一步公开了双苯并咪唑六氟磷酸盐化合物(IV)及其晶体在荧光识别领域中的应用;所述的荧光识别指的是主体(IV)对Co2+具有选择性识别能力;在25˚C下,主体(IV)的乙腈溶剂中分别加入不同种类的硝酸盐作为客体(不同种类的硝酸盐,如:Li+,Na+, K+, NH4 +, Ca2+, Co2+, Ni2+, Cu2+, Zn2+, Cd2+, Cr3+, Al3+, Pb2+ and Hg2+),在25℃下,将主体和客体溶解在有机溶剂中,在一定浓度下,将主体溶液分别和不同的客体溶液混合,测定其荧光光谱,找出主体能够识别的客体。对于主体能够识别的客体,用不同的浓度的客体对主体进行滴定(5.0 × 10-6 mol L-1),测定其荧光光谱。用微量注射器加入浓度逐渐增大的硝酸盐溶液(0-20 × 10-6 mol L-1)。主体溶液的激发波长为410 nm,发射光谱在488-710 nm有发射峰。每次添加后,8-10分钟达到反应平衡测定相应的荧光强度。本发明作为主体的双苯并咪唑六氟磷酸盐化合物(特别是晶体)对硝酸盐化合物的荧光感光效果明显,在荧光光谱中的在488-710 nm 有明显的荧光发射,(图2)可以用来制作荧光探针,有望在荧光化学领域得到应用。
本发明提出的双苯并咪唑六氟磷酸盐化合物(IV)是一种在标准状态下可以稳定存在的高级荧光材料,具有制备简洁、结构可调整和荧光感光效果明显的优点,可以用来制作荧光材料和荧光分子识别体系,有望在荧光化学领域得到应用。
附图说明:
图1为含双苯并咪唑盐化合物(IV)(实施例1)的晶体结构图;
图2为含双苯并咪唑六氟磷酸盐化合物(IV) (实施例1)在25˚C下,乙腈作为溶剂中加入不同种类的硝酸盐作为客体(不同种类的硝酸盐,如:Li+, Na+, K+, NH4 +, Ca2+, Co2 +, Ni2+, Cu2+, Zn2+, Cd2+, Cr3+, Al3+, Pb2+ and Hg2+)后的荧光光谱图;结果表明主体(IV)对Co2+具有选择性识别能力;
图3为双苯并咪唑六氟磷酸盐化合物(IV)(实施例1)在25˚C下,乙腈作为溶剂中加入不同浓度的硝酸钴溶液后的荧光滴定光谱图;结果表明随着Co2+浓度的增加主体的荧光逐渐降低,当Co2+浓度达到一定数值后荧光不再有明显的降低。
具体实施方式
下面通过具体的实施方案叙述本发明。除非特别说明,本发明中所用的技术手段均为本领域技术人员所公知的方法。另外,实施方案应理解为说明性的,而非限制本发明的范围,本发明的实质和范围仅由权利要求书所限定。对于本领域技术人员而言,在不背离本发明实质和范围的前提下,对这些实施方案中的物料成分和用量进行的各种改变或改动也属于本发明的保护范围。本发明所用原料及试剂均有市售;其中
1,8-二羟基-9,10-蒽醌、1,2-二溴乙烷、碳酸钾、苯并咪唑、六氟磷酸铵、四丁基溴化铵等均可以从市场上买到或容易地通过已知的方法制得。
制备本发明化合物所用到的试剂全部来源于天津市科锐思化工有限公司,级别为分析纯。
另外需要加以说明的是:所有的实验操作运用Schlenk技术,溶剂经过标准流程纯化。所有用于合成和分析的试剂都是分析纯,并没有经过进一步的处理。熔点通过Boetius区截机测定。1H 和 13C{1H}NRM谱通过汞变量Vx400分光光度计记录,测量区间:400 MHzand 100 MHz。化学位移,参考国际标准的TMS测定。荧光光谱通过Cary Eclipse荧光分光光度计测定。
实施例1
1- (2-溴乙氧基)-8-羟基-9,10-蒽醌(I)的制备:
将1,8-二羟基-9,10-蒽醌(0.500 g,2.0 mmol),无水K2CO3(0.150 g,1.0 mmol)和无水TBAB(0.100 g,0.3 mmol)的丙酮(150 mL)溶液搅拌半回流一小时。待冷却后,将1,2-二溴乙烷(0.400 g,2.0 mmol)缓慢加入到上述混合物中,并在40 ˚C下连续搅拌48小时。过滤所得溶液并浓缩至5mL,将其通过硅胶快速色谱法使用石油醚和乙酸乙酯(石油醚/乙酸乙酯= 99:1)的混合物溶剂作为洗脱剂纯化。得到1-(2-溴乙氧基)-8-羟基-9,10-蒽醌(I),为黄色粉末。产率:0.190 g (51%),熔点:161-163 ˚C。 Calcd for C16H11O4Br: C,55.35; H, 3.19%. Found: C, 54.98; H, 3.14%。1H NMR (CDCl3, 400 MHz): δ3.80 (t,J = 6.8 Hz, 2H, CH 2), 4.50 (t, J = 3.4 Hz, 2H, CH 2), 7.26 (s, 1H, ArH), 7.31(q, J = 3.0 Hz, 1H, ArH), 7.36 (d, J = 8.4 Hz, 1H, ArH), 7.62 (t, J = 8.4 Hz,1H, ArH), 7.79 (m, 2H, ArH), 8.03 (d, J = 2.9 Hz, 1H, ArH), 12.93 (s, 1H,ArOH)。13C NMR (CDCl3, 100 MHz): δ188.0 (CO), 182.1 (CO), 162.1 (ArC), 158.9(ArC), 135.5 (ArC), 135.4 (ArC), 135.2 (ArC), 132.3 (ArC), 124.3 (ArC), 121.4(ArC), 120.8 (ArC), 120.3 (ArC), 118.4 (ArC), 116.6 (ArC), 69.6 (CH2), 27.9(CH2)。
1,8- 二(2-溴乙氧基)-9,10-蒽醌(II)的制备:
将50 mL的1,8-二羟基蒽醌(5.000 g, 20.8 mmol)、无水K2CO3 (14.384 g, 109.0mmol)和四丁基溴化铵(0.162 g, 2.1 mmol)的经过处理的CH3CN悬浊液在室内温度下先行搅拌30分钟。用滴用恒压漏斗盛放1,2-二溴乙烷(20.300 g, 100.5 mmol),滴加,回流条件下反应3天。反应完成后,将体系冷却直至室温,过滤,旋干多余溶剂,最终得到黄色的呈现油状性质的物质。用CH2Cl2(20 mL)溶解此油状物质,并加水充分洗涤,随后将水层和二氯甲烷混合溶液分液,加无水Mg2SO4除去有机相里的多余水分,保持干燥。旋干旋干溶剂并用乙酸乙酯重结晶得到1,8-二(2-溴丙氧基)蒽醌产物淡黄色固体,产量4.813 g, 产率: 4.813g (75%), 熔点:122-124 ˚C。 Anal. Calcd for C18H14Br2O4: C, 47.61; H, 3.11%.Found: C, 47.84; H, 3.44%. 1H NMR (400 MHz, DMSO-d 6): δ 3.86 (t, J = 5.6 Hz,4H, CH 2), 4.50 (t, J = 5.6 Hz, 4H, CH 2), 7.58 (q, J = 3.4 Hz, 2H, ArH), 7.76(t, J = 2.6 Hz, 4H, ArH)。
1,8-二[2-(苯并咪唑-1-基)乙氧基] -9,10-蒽醌(III)的制备:
将苯并咪唑(2.600 g,22.0 mmol),KOH(1.802 g,32.0 mmol),TBAB(0.305 g,0.9mmol)和1,8-二(2-溴乙氧基)-9,10蒽醌(1.001 g,2.2 mmol)的THF(120 mL)悬浮液在40 ˚C下搅拌24小时后。过滤,在真空下除去溶剂。然后用THF重结晶,得到1,8-二[2-(苯并咪唑-1-基)乙氧基]-9,10-蒽醌,为黄色针状晶体。产率:0.922 g (77.6%),熔点:205-207 ˚C。Anal. Calcd forC32H28O4N4: C, 72.16; H, 5.29; N, 10.51%. Found: C, 72.06; H,5.55; N, 10.82%.1H NMR (400 MHz, DMSO-d 6): δ 4.52 (t, J = 4.8 Hz, 4H, CH 2),4.91 (t , J = 5.0 Hz, 4H, CH 2), 7.20 (m,2H, ArH), 7.27 (m,2H, ArH), 7.71 (m,6H, ArH), 7.80 (d, J = 8.0 Hz, 2H, ArH), 8.67 (s, 2H, 2-bimH) (bimi =benzimidazole)。
1,8-二{2- {N- [2’- (8’ - 羟基-9,10 - 蒽醌-1-基氧基)乙基]苯并咪唑甲基}-9’ ,10’-蒽醌六氟磷酸盐(IV)的制备:
将1- (2-溴乙氧基)-8-羟基-9,10-蒽醌(I)(0.305 g,1.0 mmol)和1,8-二[2-(苯并咪唑-1-基)乙氧基] -9,10-蒽醌(III)的CH3CN(100 mL)溶液将乙氧基]-9,10-蒽醌(0.101 g,0.5 mmol)在回流下搅拌4天,形成黄色沉淀。过滤后,将该沉淀(0.302 g,0.3mmol)溶解于甲醇(40 mL)中,加入NH4PF6(0.133 g,0.8 mmol)的甲醇(20 mL)溶液。将混合溶液在室温下搅拌2天以沉淀出黄色固体。过滤收集固体,用***(5mL)洗涤,得到黄色粉末1,8-二{2- {N- [2’ -(8’ - 羟基-9,10 - 蒽醌-1-基氧基)乙基]苯并咪唑甲基} -9’,10’- 蒽醌六氟磷酸盐(IV)。产率:0.240 g (80%),熔点:283-285 ˚C。 Anal. Calcd forC64H46N4O12F12P2: C, 56.81; H, 3.42; N, 4.14%. Found: C, 56.69; H, 3.55; N,4.02%. 1H NMR (400 MHz, DMSO-d 6): δ 4.47 (t, J = 4.4 Hz, 4H, CH 2), 4.63 (t, J = 4.4 Hz, 4H, CH 2), 4.99 (t, J = 1.6 Hz, 4H, CH 2), 5.08 (t, J = 2.0 Hz, 4H,CH 2), 6.85 (m, 4H, ArH), 6.90 (t, J = 4.0 Hz, 2H, ArH), 7.01 (d, J = 8.0 Hz,2H, ArH), 7.07 (d, J = 7.2 Hz, 4H, ArH), 7.17 (d, J = 8.0 Hz, 2H, ArH), 7.44(t, J = 3.6 Hz, 2H, ArH), 7.52 (t, J = 4.0 Hz, 2H, ArH), 7.68(m, 4H, ArH),8.23 (d, J = 8.4 Hz, 2H, ArH), 8.35 (d, J = 8.8 Hz, 2H, ArH), 9.72 (s, 2H, 2-bimiH), 11.86 (s, 2H, OH). 13C NMR (100 MHz, DMSO-d 6): δ186.7 (CO), 180.6(CO), 160.8 (ArC), 157.4 (ArC), 156.8 (ArC), 143.1 (ArC), 136.2 (ArC), 133.6(ArC), 132.4 (ArC), 131.7 (ArC), 131.0 (ArC), 126.4 (ArC), 124.1 (ArC), 120.2(ArC), 119.8 (ArC), 119.2 (ArC), 118.5 (ArC), 118.1 (ArC), 115.8 (ArC), 113.5(ArC), 65.6 (CH2), 45.9 (CH2)。
晶体结构见说明书附图1:
实施例1双苯并咪唑盐化合物(IV)的晶体,其晶体结构参数如下:
晶体数据和结构精修参数包含在支持性信息中。在Bruker APEX II CCD衍射仪上进行,实验温度为150 (10)K, 在50kV 和20mA下,用Mo-Ka 辐射(0.71073 Å)操作,用SMART和SAINT软件进行数据收集和还原,q 的范围是 1.8 < q < 25º。应用SADABS 程序进行经验吸收矫正。晶体结构由直接方法解出,用SHELXTL包对全部非氢原子坐标各向异性热参数进行全矩阵最小二乘法修正。
应用实例1
在25˚C下,用双苯并咪唑六氟磷酸盐化合物(IV)的乙腈作溶剂中分别加入不同种类的硝酸盐作为客体(不同种类的硝酸盐,如:Li+, Na+, K+, NH4 +, Ca2+, Co2+, Ni2+, Cu2 +, Zn2+, Cd2+, Cr3+, Al3+, Pb2+ and Hg2+),见附图2,从附图2中可以看出主体(IV)对Co2+具有选择性识别能力;
荧光滴定通过Cary Eclipse荧光分光光度计用1cm路径长的石英槽测定的。滴定的进行是将主体(5 × 10-6 mol/L)放入4 mL的比色皿中,并用微量注射器加入浓度逐渐增大的硝酸钴溶液(0-20 × 10-6 mol L-1)。主体溶液的激发波长为410 nm,发射光谱在488-710 nm有发射峰。每次添加后,8-10分钟达到反应平衡才可记录相应的荧光光谱,数据分析使用Origin 8.0,见附图3,从附图3中可以看出:随着Co2+浓度的增加主体的荧光逐渐降低,当Co2+浓度达到一定数值后荧光不再有明显的降低。
综上所述,本发明的内容并不局限在实例中,相同领域内的有识之士可以在本发明的技术指导思想之内可以轻易提出其他的实例,但这种实例都包括在本发明的范围之内。
Claims (7)
2.权利要求1所述双苯并咪唑盐的制备方法,其特征在于按如下的步骤进行:
(1)在有机溶剂中以1,8-二羟基-9,10-蒽醌为原料,与1,2-二溴乙烷反应得到1-(2-溴乙氧基-)-8-羟基-9,10-蒽醌和1,8-二(2-溴乙氧基)-9,10-蒽醌;其中1,8-二羟基-9,10-蒽醌与1,2-二溴乙烷的摩尔比为1:1和1:2;
(2)在有机溶剂中将得到的1,8-二(2-溴乙氧基)-9,10-蒽醌与苯并咪唑在碱性条件下反应得到1,8-二[2-(苯并咪唑-1-基)乙氧基]-9,10-蒽醌,其中1,8-二(2-溴乙氧基)-9,10-蒽醌与苯并咪唑的摩尔比为1:2;
(3)将1,8-二[2-(苯并咪唑-1-基)乙氧基]-9,10-蒽醌与1-(2-溴乙氧基)-8--羟基-9,10-蒽醌反应得到的溴化物再与NH4PF6以摩尔比为1:1.5的比例加入到反应器皿内,用有机溶剂溶解后,在室温温度下反应1天,过滤,洗涤,得到:
3.权利要求2所述的制备方法,其中所述的有机溶剂选自二氯甲烷、丙酮、甲醇、***、乙腈、乙酸乙酯中的一种或几种的混合物。
5.权利要求4所述双苯并咪唑盐化合物IV晶体的制备方法,其特征在于用得到的双苯并咪唑盐化合物IV,将其溶于乙腈后放入试管中,在非良性溶剂中扩散令其缓慢结晶得到其黄色晶体;所述的非良性溶剂指的是***。
6.权利要求1所述的双苯并咪唑六氟磷酸盐化合物IV在制备荧光识别方面的应用;所述的荧光识别指的是对Co2+的识别。
7.权利要求4所述双苯并咪唑盐IV的晶体在制备荧光探针方面的应用;所述的荧光识别指的是对Co2+的识别。
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