CN105669644A - 一种苯并咪唑喹啉衍生物，制备方法及其应用 - Google Patents
一种苯并咪唑喹啉衍生物，制备方法及其应用 Download PDFInfo
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- GEJVGFCMKRDIAC-UHFFFAOYSA-N 1h-benzimidazole;quinoline Chemical class C1=CC=C2NC=NC2=C1.N1=CC=CC2=CC=CC=C21 GEJVGFCMKRDIAC-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims abstract description 55
- 229910001431 copper ion Inorganic materials 0.000 claims abstract description 43
- ZGNCKIDXVHSMJL-UHFFFAOYSA-N 2-methylquinoline-8-carboxylic acid Chemical compound C1=CC=C(C(O)=O)C2=NC(C)=CC=C21 ZGNCKIDXVHSMJL-UHFFFAOYSA-N 0.000 claims abstract description 7
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims abstract description 6
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzenecarboxaldehyde Natural products O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims abstract description 5
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims abstract description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 16
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 11
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical group N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 10
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- 150000007530 organic bases Chemical class 0.000 claims description 2
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- 150000003141 primary amines Chemical group 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 239000001117 sulphuric acid Substances 0.000 claims description 2
- 235000011149 sulphuric acid Nutrition 0.000 claims description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims 1
- 239000000523 sample Substances 0.000 abstract description 21
- 238000001514 detection method Methods 0.000 abstract description 15
- 238000010521 absorption reaction Methods 0.000 abstract description 12
- WLNIBLNYTGOTBN-UHFFFAOYSA-N 8-(1h-benzimidazol-2-yl)-2-methylquinoline Chemical compound C1=CC=C2NC(C3=CC=CC4=CC=C(N=C43)C)=NC2=C1 WLNIBLNYTGOTBN-UHFFFAOYSA-N 0.000 abstract description 5
- 238000000862 absorption spectrum Methods 0.000 abstract description 5
- RWZYAGGXGHYGMB-UHFFFAOYSA-N anthranilic acid Chemical compound NC1=CC=CC=C1C(O)=O RWZYAGGXGHYGMB-UHFFFAOYSA-N 0.000 abstract 2
- 238000009833 condensation Methods 0.000 abstract 2
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- 229910021645 metal ion Inorganic materials 0.000 description 8
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- 230000004044 response Effects 0.000 description 4
- 239000012085 test solution Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
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- 239000010949 copper Substances 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 241000894007 species Species 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
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- 241000206602 Eukaryota Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 208000008948 Menkes Kinky Hair Syndrome Diseases 0.000 description 1
- 208000012583 Menkes disease Diseases 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- ZIALXKMBHWELGF-UHFFFAOYSA-N [Na].[Cu] Chemical compound [Na].[Cu] ZIALXKMBHWELGF-UHFFFAOYSA-N 0.000 description 1
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- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
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Abstract
本发明提供一种苯并咪唑喹啉衍生物，制备方法及在铜离子检测上的应用。具体涉及一种基于2-(4-N,N-二取代苯乙烯基)-8-(1H-苯并咪唑)喹啉衍生物，具体是将2-氨基苯甲酸制备出2-甲基喹啉-8-羧酸，再与邻苯二胺缩合得到2-甲基-8-(2-苯并咪唑基)喹啉，进一步与N,N-二取代苯甲醛缩合得到本发明的衍生物。该探针与铜离子有很好的络合作用，铜离子存在时，裸眼观察到溶液衍生迅速从黄色变成紫色，且紫外可见吸收光谱上的418nm处的吸收减弱，在550nm处出现已新的吸收峰且随着铜离子浓度的增加逐渐增强；本发明可用于复杂样品的实时和快速测量，也能用于不同来源的环境样品微/痕量Cu2+的半定量检测。
Description
技术领域
本发明属于分析化学技术领域，涉及一种苯并咪唑喹啉衍生物及其合成方法，并将其应用于铜离子荧光剂上。
背景技术
铜是生命有机体中的一种重要的过渡金属元素，是30多种酶的活性成分，在生命体的新陈代谢中起到十分重要的作用。在生物体内，铜主要以Cu2+的形式存在。Cu2+在人体中的含量过多或者过少，都会引起很多疾病，例如阿尔茨海默氏症、帕金森氏病、Menkes氏综合症、威尔逊氏综合症等，危害人体健康。铜对低等生物和农作物毒性较大，其浓度大于0.1～0.2mg/L(约2μM)可使鱼类致死。世界卫生组织规定，考虑到其毒性，1.5mg/L(约25μM)作为铜离子在饮用水中允许的最大浓度。我国地表水环境质量标准(GB38382002)规定，I类水域铜离子的标准限值为0.01mg/L，II-V类水域铜离子的标准限值为1mg/L。饮用水的标准规定，铜离子的含量不得超过20μM。
目前用于检测铜离子的仪器和方法有原子吸收分光光度法(AAS)、电感耦合等离子体-原子发射光谱法(ICP-AES)、电感耦合等离子体质谱分析(ICP-MS)和原子荧光光谱分析(AFS)等。但是，现有常规检测方法由于需要昂贵的大型仪器，复杂的样品前处理过程，以及专业技术人员专业的操作。因此，存在检样慢，不适用于现场检测或大规模推广应用。发展成本低廉、操作简便、选择性好、灵敏度高、响应速度快、检测限低的二价铜离子的检测方法仍是一个挑战性的任务。
发明内容
本发明的目的在于提供一种苯并咪唑喹啉衍生物，该衍生物的结构式如下：
该苯并咪唑喹啉衍生物，进一步优选为2-(4-N,N-二取代苯乙烯基)-8-(1H-苯并咪唑)喹啉，具体结构式如下：
本发明的另一目的在于提供一种苯并咪唑喹啉衍生物的制备方法，包括如步骤：
(1)2-甲基喹啉-8-羧酸和邻苯二胺，多聚磷酸混合后，搅拌回流反应4小时以上，经分离、纯化后，得到中间体(1)，即，2-甲基-8-(1H-苯并咪唑)喹啉；
(2)将中间体I和取代醛溶于极性溶剂中，加入哌啶和催化剂，隔绝空气，搅拌回流5小时以上，固体析出，抽滤，甲醇水溶液重结晶，抽滤得到苯并咪唑喹啉衍生物；具体的反应式如下：
步骤(1)中，2-甲基喹啉-8-羧酸和邻苯二胺的摩尔比为1:1.1；步骤(2)中中间体I和取代醛的摩尔比为1:1。
步骤(1)中，搅拌回流反应6小时；所述的分离步骤是将反应液加入到盛有大量水的容器中，用碱调pH为中性，搅拌，固体析出后抽滤即可完成分离步骤，其中碱为氨水；所述的纯化步骤是将分离后的固体在二氯甲烷与石油醚的洗脱液中洗脱。
其中，二氯甲烷与石油醚的体积比为0-1：3-100；所述的洗脱液还可以为乙酸乙酯与石油醚的混合液，其中，乙酸乙酯与石油醚的体积比为0-1：3-100。
所述的纯化步骤还可以为将分离后的固体用醇的水溶液重结晶，醇的水溶液为体积浓度为20-80％的乙醇水溶液。
步骤(2)中，所述的取代醛为对位氨基、对位伯胺基或对位仲胺基取代的苯甲醛，结构式为R、R1为氢原子或CnH2n+1或杂原子取代的烃基。
所述的步骤(2)中，哌啶还包括吡啶或N,N-二甲基吡啶的有机碱或碳酸钠、碳酸钾的无机碱；所述的催化剂包括乙酸、乙酸酐或硫酸。
本发明的又一目的在于苯并咪唑喹啉衍生物在铜离子Cu2+显色指示剂上的应用。
本发明的苯并咪唑喹啉衍生物铜离子荧光探针，该探针与铜离子有很好的络合作用，响应快。铜离子存在时，裸眼观察到溶液迅速从无色变成黄色，且紫外可见吸收光谱上的418nm处吸收峰减弱，在550nm处出现已新的吸收峰且随着铜离子浓度的增加逐渐增强。在荧光发射光谱中，随着铜离子浓度的增加，荧光强度逐渐降低。它对其他金属离子(Zn2+，Cr3+，Fe3+，Cd2+，Mn2+，Hg2+，Fe2+，Pb2+，Ba2+，Ag+)的抗干扰能力强，适用pH范围为弱酸性到中性，是一种高效的Cu2+显色指示剂；该Cu2+显色指示剂对Cu2+的响应时间在20s，最低检测限为2.82×10-8mol/L。故本探针即可制备成检测试纸等裸眼即可对铜离子检测，也可用于紫外-可见光分光光度法对铜离子检测，还可用于荧光分光光度计法对铜离子的痕量检测。
本发明的制备方法具有合成工艺简单、收率高、纯度高、成本低廉、操作简便优点。
与现有技术相比本发明的优点：本发明的铜离子光谱探针合成方法简单，易于生产；与铜离子络合作用很强，对铜离子选择性好，响应快，灵敏度高；检测方法多样，并且检测过程简单、快速、结果准确，应用前景广泛等优点，可用于复杂样品的实时和快速测量，也能用于不同来源的样品微/痕量Cu2+的定性、定量检测。
附图说明
图1为实施例1所制备的BMQS的核磁共振氢谱。
图2为实施例1所制备的BMQS的紫外可见吸收光谱。
图3为实施例1所制备的BMQS的荧光光谱。
图4为实施例1所制备的BMQS溶液及加入铜离子后的溶液颜色变化，A为自然光下；B为紫外灯下。
图5为实施例1所制备的BMQS检测铜离子的吸收光谱。
图6为实施例1所制备的BMQS检测铜离子的荧光光谱。
图7为实施例1所制备的BMQS及其检测铜离子的吸收光谱。
图8为实施例1所制备的BMQS及其检测铜离子的荧光光谱。
图9为实施例1所制备的BMQS对各种金属离子选择性测试的紫外吸收光谱。
图10为实施例1所制备的BMQS在其它离子时对铜离子测定影响的紫外吸收光谱。
图11为实施例1所制备的BMQS紫外吸收比率(A550/A418)随Cu2+浓度变化线性关系图。
具体实施方式
实施例1
(A)制备2-甲基-8-(2-苯并咪唑基)喹啉(1)
2-甲基喹啉-8-羧酸(4.8620g，26mol)、倍当量的邻苯二胺(3.0888，28.6mol)和多聚磷酸(26.3562，78mol)混合后，搅拌回流6小时以上，冷却后，将反应液加入到盛有大量水的烧杯中，用氨水调pH为中性，搅拌，有固体析出，抽滤，60％乙醇重结晶，产率70.54％，熔点173.5～174.3℃。核磁共振图谱氢谱1HNMR(400MHz,CDCl3):δ:13.72(br,1H),9.11(d,1H),8.16(d,1H),7.86(d,2H),7.65(t,2H),7.39(d,1H),7.29-7.31(m,2H),2.91(s,3H)。
(B)2-(4-N,N-二甲基苯乙烯基)-8-(1H-苯并咪唑)喹啉(铜离子荧光探针)
将2-甲基-8-苯并咪唑基喹啉(0.8750g,3.38mmol)，N,N-二甲基苯甲醛(2.0210g，13.5mmol)加入50mL两口瓶中，氮气保护下，依次加入哌啶(1.35mL，13.5mmol)，无水甲醇(10.0mL)、冰乙酸(0.78mL，13.5mmol)，回流12h，冷却，有橘黄色固体析出。抽滤得固体，重结晶，得产物0.83g，产率：63％，熔点191～193℃。对BMQS核磁共振图谱分析1HNMR(400MHz,CDCl3):δ13.93(s,1H),9.08-9.06(m,1H),8.15(d,J＝8.80Hz,1H),7.91(s,1H),7.90(t,J＝2.80,1H),7.82-7.58(m,6H),7.34-7.30(m,2H),6.80(d,J＝2.80,2H),3.06(s,6H)。API-ES-MS,m/z(％):390.18(100)[M+H+]
实施例2
测试液的配制程序：在10mL样品瓶中，加入5.0mL双蒸水，再加入0.1mol/L现配置的Cu2+标准溶液(20μL，20eq)，再加入5.0mL乙腈，混匀(pH＝6.40)；最后加入100μL1×10-3探针BMQS的乙腈溶液，再次混匀。放置10分钟后，于420nm为激发波长，测定紫外吸收和荧光发射。如上的操作，不加入金属离子溶液，即为空白试液的配制。测定紫外吸收和荧光发射。
紫外光谱和荧光光谱：探针BMQS的空白试液在418nm处有较强吸收，在550nm处没有吸收；当存在铜离子时，418nm处的吸收显著减弱，550nm处的吸收明显增强，见图7。探针BMQS的空白试液在610nm有较强的荧光发射峰，加入铜离子后，荧光减弱甚至淬灭，见图8。
选择性：当同样浓度的各种金属离子分别与探针1作用时，唯有铜离子能引起探针BMQS在418nm处吸收显著减弱，在550nm吸收明显增强，并且两个吸收峰达到完全分离。其他金属离子与探针BMQS作用时，相比较于探针BMQS的空白试液，其在418nm处吸收的比值无明显变化，仅Al3+,Cr3+,Fe3+在535nm左右有一定的吸收。这表明，就紫外吸收光度法而言，探针BMQS对铜离子的传感具有高度的特异性选择。见图9。
共存离子对铜离子测定的影响：为进考察探针BMQS对铜离子传感的选择性，尝试了性质相近的各种金属离子与铜离子共存时对体系吸光度的影响。在图10中标“Cu2+”为2.0×10-4mol/L的铜离子单独存在时体系的紫外吸收，其余为同等浓度铜离子与相同浓度倍数的各种金属离子共存时体系的紫外吸收。各金属离子分别为：Al3+，Ca2+，Cr3+，Mn2+，Fe3+,Co2+,Ni2+,Cu2+,Zn2+,Ag+,Cd2+,Ba2+,Hg2+,及Pb2+。由图10可见，其他金属离子对铜离子的检测几乎无影响。
检测铜离子的滴定实验：线性拟合得出检测铜离子的紫外吸收-剂量曲线，见图11。根据最低检出限公式(DL＝3σ/b)计算，在紫外紫外分光光度法探针BMQS对铜离子的DL为：2.82×10-8mol/L。
Claims (10)
1.一种苯并咪唑喹啉衍生物，该衍生物的结构式如下：
其中，R、R1为氢原子或CnH2n+1或杂原子取代的烃基。
2.权利要求1所述的苯并咪唑喹啉衍生物，具体为2-(4-N,N-二取代苯乙烯基)-8-(1H-苯并咪唑)喹啉，具体结构式如下：
3.权利要求1所述的苯并咪唑喹啉衍生物的制备方法，其特征在于，包括如步骤：
(1)2-甲基喹啉-8-羧酸和邻苯二胺，多聚磷酸混合后，搅拌回流反应4小时以上，经分离、纯化后，得到中间体(1)，即，2-甲基-8-(1H-苯并咪唑)喹啉；
(2)将中间体I和取代醛溶于极性溶剂中，加入哌啶和催化剂，隔绝空气，搅拌回流5小时以上，固体析出，抽滤，甲醇水溶液重结晶，抽滤得到苯并咪唑喹啉衍生物；具体的反应式如下：
4.权利要求3所述的苯并咪唑喹啉衍生物的制备方法，其特征在于，步骤(1)中，2-甲基喹啉-8-羧酸和邻苯二胺的摩尔比为1:0.5～2，优选摩尔比为1:1.1；步骤(2)中中间体I和取代醛的摩尔比为1:0.8～1.5，优选摩尔比为1:1，所述的极性溶剂为甲醇、乙醇、丙醇或丁醇。
5.权利要求3所述的苯并咪唑喹啉衍生物的制备方法，其特征在于，步骤(1)中，搅拌回流反应6小时；
所述的分离步骤是将反应液加入到盛有大量水的容器中，用碱调pH为中性，搅拌，固体析出后抽滤即可完成分离步骤，其中碱为氨水；
所述的纯化步骤是将分离后的固体在二氯甲烷与石油醚的洗脱液中洗脱。
6.权利要求5所述的苯并咪唑喹啉衍生物的制备方法，其特征在于，二氯甲烷与石油醚的体积比为0-1：3-100；所述的洗脱液还可以为乙酸乙酯与石油醚的混合液，其中，乙酸乙酯与石油醚的体积比为0-1：3-100。
7.权利要求5所述的苯并咪唑喹啉衍生物的制备方法，其特征在于，所述的纯化
步骤还可以为将分离后的固体用醇的水溶液重结晶，醇的水溶液为体积浓度为20-80％的乙醇水溶液。
8.权利要求3所述的苯并咪唑喹啉衍生物的制备方法，其特征在于，所述的取代醛为氨基、伯胺基或位仲胺基取代的苯甲醛，结构式为R、R1为氢原子或CnH2n+1或杂原子取代的烃基。
9.权利要求3所述的苯并咪唑喹啉衍生物的制备方法，其特征在于，所述的步骤(2)中，哌啶还包括吡啶或N,N-二甲基吡啶的有机碱或碳酸钠、碳酸钾的无机碱；所述的催化剂包括乙酸、乙酸酐或硫酸。
10.权利要求1-9任一项所述的苯并咪唑喹啉衍生物在铜离子Cu2+显色指示剂上的应用。
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