CN111548362B - 一种樟脑耦合苯并噻唑基烯腈型次氯酸荧光探针及其制备方法和应用 - Google Patents
一种樟脑耦合苯并噻唑基烯腈型次氯酸荧光探针及其制备方法和应用 Download PDFInfo
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- 241000723346 Cinnamomum camphora Species 0.000 title claims abstract description 14
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Abstract
本发明公开了一种樟脑耦合苯并噻唑基烯腈型次氯酸荧光探针及其制备方法与应用。本发明利用樟脑衍生物2‑羟基‑5‑(樟脑‑3‑甲烯基)苯甲醛为原料,与4‑溴甲基苯硼酸频哪酯进行取代反应,得到2‑(4‑(4,4,5,5‑四甲基‑1,3,2‑二噁硼烷‑2‑基)苯甲氧基)‑5‑(樟脑‑3‑甲烯基)苯甲醛;2‑(4‑(4,4,5,5‑四甲基‑1,3,2‑二噁硼烷‑2‑基)苯甲氧基)‑5‑(樟脑‑3‑甲烯基)苯甲醛与2‑氰甲基苯并噻唑进行缩合反应,得到2‑(2‑苯并噻唑基)‑3‑(2‑(4‑(4,4,5,5‑四甲基‑1,3,2‑二噁硼烷‑2‑基)苯甲氧基)‑5‑(樟脑‑3‑甲烯基)苯基)丙烯腈。该化合物能特异性识别次氯酸,可作为定性和定量检测次氯酸的荧光探针,具有良好的应用前景。
Description
技术领域
本发明属精细有机合成技术领域,涉及樟脑耦合苯并噻唑基烯腈型次氯酸荧光探针及其合成方法和应用。
背景技术
次氯酸(OCl-)是一种重要的活性氧,是家用漂白剂、游泳池消毒剂的主要成分,在人们的日常生活中有着广泛的应用。此外,次氯酸也是生命系统中最重要的活性氧(ROS)之一,在各种生理过程中起着关键的作用。内源性OCl-是由氯离子(Cl-)与过氧化氢(H2O2)在髓过氧化物酶(MPO)作用下产生,在免疫系统中可抵御侵入性的细菌和病原体,但是,过量的ClO-会通过氯化或氧化作用导致组织损伤和许多疾病,包括心血管疾病、类风湿性关节炎、哮喘、动脉粥样硬化和癌症等。
近年来,报道了许多用于检测ClO-的荧光探针,这些荧光探针主要由香豆素、罗丹明、氟硼二吡咯、1,8-萘酰亚胺、荧光素等传统的荧光团设计合成。这些荧光探针的检测效果不仅容易受到竞争性离子、反应时间、pH范围等外界因素的干扰,且都是单一的检测模式,对不同浓度次氯酸不能进行定量检测。因此,设计开发一种可高灵敏性地、高选择性地、定量快速地检测ClO-的荧光探针具有十分重要的意义。
发明内容
发明目的:针对现有技术中存在的不足,本发明的目的在于提供一种樟脑耦合苯并噻唑基烯腈型化合物,满足使用需求。本发明的另一目的是提供一种上述樟脑耦合苯并噻唑基烯腈型化合物的合成方法。本发明还有一目的是提供该化合物的应用。
技术方案:为实现上述发明目的,本发明采用的技术方案为:
樟脑耦合苯并噻唑基烯腈型化合物,为2-(2-苯并噻唑基)-3-(2-(4-(4,4,5,5-四甲基-1,3,2-二噁硼烷-2-基)苯甲氧基)-5-(樟脑-3-甲烯基)苯基)丙烯腈,其结构式为:
所述的樟脑耦合苯并噻唑基烯腈型化合物合成方法,包括如下工艺步骤:
1)2-羟基-5-(樟脑-3-甲烯基)苯甲醛与4-溴甲基苯硼酸频哪酯进行取代反应,得到2-(4-(4,4,5,5-四甲基-1,3,2-二噁硼烷-2-基)苯甲氧基)-5-(樟脑-3-甲烯基)苯甲醛。
2)2-(4-(4,4,5,5-四甲基-1,3,2-二噁硼烷-2-基)苯甲氧基)-5-(樟脑-3-甲烯基)苯甲醛与2-氰甲基苯并噻唑进行缩合反应,得到2-(2-苯并噻唑基)-3-(2-(4-(4,4,5,5-四甲基-1,3,2-二噁硼烷-2-基)苯甲氧基)-5-(樟脑-3-甲烯基)苯基)丙烯腈。
步骤1)中,2-羟基-5-(樟脑-3-甲烯基)苯甲醛与4-溴甲基苯硼酸频哪酯进行取代反应,得到2-(4-(4,4,5,5-四甲基-1,3,2-二噁硼烷-2-基)苯甲氧基)-5-(樟脑-3-甲烯基)苯甲醛,具体的制备方法包括:
(1)将0.5mmol 2-羟基-5-(樟脑-3-甲烯基)苯甲醛、0.6mmol 4-溴甲基苯硼酸频哪酯、0.6mmol碳酸钾和8mL N,N-二甲基甲酰胺依次加入15mL干燥的三口烧瓶中,回流反应20h,用TLC法跟踪监测,至反应完全后停止反应。
(2)反应液经减压蒸馏除去N,N-二甲基甲酰胺后再加入乙酸乙酯,用饱和食盐水进行洗涤至中性,有机相再经无水硫酸钠干燥、过滤、浓缩后得到2-(4-(4,4,5,5-四甲基-1,3,2-二噁硼烷-2-基)苯甲氧基)-5-(樟脑-3-甲烯基)苯甲醛粗产物。
(3)2-(4-(4,4,5,5-四甲基-1,3,2-二噁硼烷-2-基)苯甲氧基)-5-(樟脑-3-甲烯基)苯甲醛粗产物经硅胶柱分离(乙酸乙酯/石油醚=1/2),得到2-(4-(4,4,5,5-四甲基-1,3,2-二噁硼烷-2-基)苯甲氧基)-5-(樟脑-3-甲烯基)苯甲醛纯品。
步骤2)中,2-(4-(4,4,5,5-四甲基-1,3,2-二噁硼烷-2-基)苯甲氧基)-5-(樟脑-3-甲烯基)苯甲醛与2-氰甲基苯并噻唑进行缩合,得到2-(2-苯并噻唑基)-3-(2-(4-(4,4,5,5-四甲基-1,3,2-二噁硼烷-2-基)苯甲氧基)-5-(樟脑-3-甲烯基)苯基)丙烯腈,具体的制备方法包括:
(1)将0.5mmol 2-(4-(4,4,5,5-四甲基-1,3,2-二噁硼烷-2-基)苯甲氧基)-5-(樟脑-3-甲烯基)苯甲醛、0.6mmol 2-氰甲基苯并噻唑、0.6mmol哌啶、8mL无水乙醇依次加入15mL干燥的三口烧瓶中,在氮气保护下加热回流反应10h。
(2)反应液冷却至室温后,析出的固体经抽滤、并用少量的无水乙醇洗涤,得到2-(2-苯并噻唑基)-3-(2-(4-(4,4,5,5-四甲基-1,3,2-二噁硼烷-2-基)苯甲氧基)-5-(樟脑-3-甲烯基)苯基)丙烯腈纯品。
所述的2-(2-苯并噻唑基)-3-(2-(4-(4,4,5,5-四甲基-1,3,2-二噁硼烷-2-基)苯甲氧基)-5-(樟脑-3-甲烯基)苯基)丙烯腈在检测次氯酸中的应用。
所述的2-(2-苯并噻唑基)-3-(2-(4-(4,4,5,5-四甲基-1,3,2-二噁硼烷-2-基)苯甲氧基)-5-(樟脑-3-甲烯基)苯基)丙烯腈在制备荧光探针中的应用。
所述的2-(2-苯并噻唑基)-3-(2-(4-(4,4,5,5-四甲基-1,3,2-二噁硼烷-2-基)苯甲氧基)-5-(樟脑-3-甲烯基)苯基)丙烯腈作为荧光探针在检测次氯酸中的应用。
本发明利用2-羟基-5-(樟脑-3-甲烯基)苯甲醛为原料,与4-溴甲基苯硼酸频哪酯进行取代反应,得到2-(4-(4,4,5,5-四甲基-1,3,2-二噁硼烷-2-基)苯甲氧基)-5-(樟脑-3-甲烯基)苯甲醛;2-(4-(4,4,5,5-四甲基-1,3,2-二噁硼烷-2-基)苯甲氧基)-5-(樟脑-3-甲烯基)苯甲醛与2-氰甲基苯并噻唑进行缩合反应,得到2-(2-苯并噻唑基)-3-(2-(4-(4,4,5,5-四甲基-1,3,2-二噁硼烷-2-基)苯甲氧基)-5-(樟脑-3-甲烯基)苯基)丙烯腈;发现该化合物能特异性识别次氯酸,可作为检测次氯酸的荧光探针。
有益效果:与现有技术相比,本发明利用2-羟基-5-(樟脑-3-甲烯基)苯甲醛为原料制得的樟脑耦合苯并噻唑基烯腈型化合物能特异性识别次氯酸,可作为定性和定量检测次氯酸的荧光探针,具有很好的实用价值。
附图说明
图1是2-(2-苯并噻唑基)-3-(2-(4-(4,4,5,5-四甲基-1,3,2-二噁硼烷-2-基)苯甲氧基)-5-(樟脑-3-甲烯基)苯基)丙烯腈与0-45μM浓度范围次氯酸作用的荧光强度结果图;
图2是2-(2-苯并噻唑基)-3-(2-(4-(4,4,5,5-四甲基-1,3,2-二噁硼烷-2-基)苯甲氧基)-5-(樟脑-3-甲烯基)苯基)丙烯腈与45-80μM浓度范围次氯酸作用的荧光强度结果图;
图3是2-(2-苯并噻唑基)-3-(2-(4-(4,4,5,5-四甲基-1,3,2-二噁硼烷-2-基)苯甲氧基)-5-(樟脑-3-甲烯基)苯基)丙烯腈与不同离子作用的荧光强度结果图。
具体实施方式
下面结合具体实施例对本发明做进一步的说明。
实施例1
樟脑耦合苯并噻唑基烯腈型化合物的合成,反应式为:
具体步骤如下:
1)2-(4-(4,4,5,5-四甲基-1,3,2-二噁硼烷-2-基)苯甲氧基)-5-(樟脑-3-甲烯基)苯甲醛的制备:
将0.5mmol 2-羟基-5-(樟脑-3-甲烯基)苯甲醛、0.6mmol 4-溴甲基苯硼酸频哪酯、0.6mmol碳酸钾和8mLN,N-二甲基甲酰胺依次加入15mL干燥的三口烧瓶中,回流反应20h,用TLC法跟踪监测,至反应完全。反应液经减压蒸馏除去N,N-二甲基甲酰胺后再加入乙酸乙酯,用饱和食盐水进行洗涤至中性,有机相再经无水硫酸钠干燥、过滤、浓缩后得到2-(4-(4,4,5,5-四甲基-1,3,2-二噁硼烷-2-基)苯甲氧基)-5-(樟脑-3-甲烯基)苯甲醛粗产物。经硅胶柱层析(乙酸乙酯/石油醚=1/2),得到白色粉末状2-(4-(4,4,5,5-四甲基-1,3,2-二噁硼烷-2-基)苯甲氧基)-5-(樟脑-3-甲烯基)苯甲醛,得率为58.2%,纯度为98.5%;1H NMR(400MHz,CDCl3)δ:10.57(s,1H),8.00(d,J=4Hz,1H),7.85(d,J=8Hz,2H),7.60(d,J=8Hz,1H),7.44(d,J=8Hz,2H),7.16(s,1H),7.04(d,J=8Hz,1H),5.26(s,2H),3.09(d,J=4Hz,1H),2.17-2.24(m,1H),1.75-1.82(m,1H),1.47-1.60(m,2H),1.35(s,12H),1.02(s,3H),1.00(s,3H),0.79(s,3H);13C NMR(100MHz,CDCl3)δ:208.07,189.24,160.92,141.81,138.73,137.48,135.25,129.15,128.77,126.38,125.83,125.19,113.45,83.96,77.36,77.04,76.72,70.60,57.08,49.08,46.75,30.72,25.89,24.87,20.58,18.29,9.28;HRMS(ESI+):m/z calculated for C31H37BO5[M+H]+501.2812,found 501.2823。
2)2-(2-苯并噻唑基)-3-(2-(4-(4,4,5,5-四甲基-1,3,2-二噁硼烷-2-基)苯甲氧基)-5-(樟脑-3-甲烯基)苯基)丙烯腈的制备:
将0.5mmol 2-(4-(4,4,5,5-四甲基-1,3,2-二噁硼烷-2-基)苯甲氧基)-5-(樟脑-3-甲烯基)苯甲醛、0.6mmol 2-氰甲基苯并噻唑、0.6mmol哌啶、8mL无水乙醇依次加入15mL干燥的三口烧瓶中,在氮气保护下加热回流反应10h。反应液冷却至室温后,析出的固体经抽滤、并用少量的无水乙醇洗涤,得淡黄色的2-(2-苯并噻唑基)-3-(2-(4-(4,4,5,5-四甲基-1,3,2-二噁硼烷-2-基)苯甲氧基)-5-(樟脑-3-甲烯基)苯基)丙烯腈纯品,得率84.8%,纯度为98.6%;1H NMR(400MHz,CDCl3)δ:8.66(s,1H),8.47(s,1H),8.11(d,J=8Hz,1H),7.91(d,J=8Hz,1H),7.86(d,J=8Hz,2H),7.49-7.55(m,2H),7.42-7.47(m,3H),7.18(s,1H),7.01(d,J=8Hz,1H),5.28(s,2H),3.33(d,J=4Hz,1H),2.22-2.30(m,1H),1.75-1.81(m,1H),1.59-1.65(m,1H),1.48-1.54(m,1H),1.35(s,12H),1.03(s,3H),1.02(s,3H),0.82(s,3H);13C NMR(100MHz,CDCl3)δ:208.40,163.24,157.77,153.67,142.04,141.46,138.93,136.21,135.26,134.83,129.07,128.75,126.84,126.12,126.10,125.71,123.88,122.39,121.62,116.25,112.97,106.72,83.96,70.76,57.21,49.01,46.78,30.80,26.20,24.89,20.65,18.23,9.35;HRMS(ESI+):m/z calculated for C40H41BN2O4S[M+H]+657.2958,found 657.2968。
实施例2
将2-(2-苯并噻唑基)-3-(2-(4-(4,4,5,5-四甲基-1,3,2-二噁硼烷-2-基)苯甲氧基)-5-(樟脑-3-甲烯基)苯基)丙烯腈溶解于PBS/THF(v/v=6/4)缓冲液中配制成1×10-5M浓度的探针溶液,将次氯酸溶于PBS/THF(v/v=6/4)缓冲液中配成浓度为0,2.5,5.0,7.5,10.0,12.5,15.0,17.5,20.0,22.5,25.0,27.5,30.0,32.5,35.0,37.5,40.0,42.5,45.0,47.5,50.0,52.5,55.0,57.5,60.0,62.5,65.0,67.5,70.0,72.5,75.0,77.5,80.0μM的溶液。采用标准滴定法在荧光分光光度计下测得不同浓度的次氯酸对2-(2-苯并噻唑基)-3-(2-(4-(4,4,5,5-四甲基-1,3,2-二噁硼烷-2-基)苯甲氧基)-5-(樟脑-3-甲烯基)苯基)丙烯腈的荧光发射光谱,如图1、图2所示。结果表明,在0-45μM浓度范围内(图1),随着体系中次氯酸浓度的不断增加,溶液从无色变为绿色荧光,在45-80μM浓度范围内(图2),溶液的绿色荧光逐渐减弱而红色荧光逐渐增强,由此说明,该探针可以灵敏地、定量地检测次氯酸。
实施例3
将2-(2-苯并噻唑基)-3-(2-(4-(4,4,5,5-四甲基-1,3,2-二噁硼烷-2-基)苯甲氧基)-5-(樟脑-3-甲烯基)苯基)丙烯腈溶解于PBS/THF(v/v=6/4)缓冲液中配制成1×10-5M浓度的探针溶液,将各种离子溶解于PBS/THF(v/v=6/4)缓冲液中配制成5×10-4M浓度的溶液,次氯酸配制成8.5×10-5M浓度的溶液。采用标准滴定法在荧光分光光度计下测得不同的离子对2-(2-苯并噻唑基)-3-(2-(4-(4,4,5,5-四甲基-1,3,2-二噁硼烷-2-基)苯甲氧基)-5-(樟脑-3-甲烯基)苯基)丙烯腈的荧光发射光谱,如图3所示。结果表明,在探针溶液中加入次氯酸后荧光发生明显变化,而加入其他离子如Al3+,Zn2+,Ca2+,Fe2+,Fe3+,Cu2+,Mg2+,F-,I-,HCO3 -,CO3 2-,HSO3 -,SO3 2-,SO4 2-,NO2 -,NO3 -,HPO4 2-,Cys,Hcy,GSH,H2O2,BPO,TBHP,AMP,ADP,ATP等,溶液的荧光光谱没有发生明显的变化,由此说明,该探针可专一性地识别次氯酸。
Claims (5)
2.权利要求1所述的樟脑耦合苯并噻唑基烯腈型次氯酸荧光探针的合成方法,其特征在于,包括如下步骤:
1)2-羟基-5-(樟脑-3-甲烯基)苯甲醛与4-溴甲基苯硼酸频哪酯进行取代反应,得到2-(4-(4,4,5,5-四甲基-1,3,2-二噁硼烷-2-基)苯甲氧基)-5-(樟脑-3-甲烯基)苯甲醛;
2)2-(4-(4,4,5,5-四甲基-1,3,2-二噁硼烷-2-基)苯甲氧基)-5-(樟脑-3-甲烯基)苯甲醛与2-氰甲基苯并噻唑进行缩合反应,得到2-(2-苯并噻唑基)-3-(2-(4-(4,4,5,5-四甲基-1,3,2-二噁硼烷-2-基)苯甲氧基)-5-(樟脑-3-甲烯基)苯基)丙烯腈。
3.根据权利要求2所述的樟脑耦合苯并噻唑基烯腈型次氯酸荧光探针的合成方法,其特征在于,步骤1)的制备方法包括:
(1)将0.5mmol 2-羟基-5-(樟脑-3-甲烯基)苯甲醛、0.6mmol 4-溴甲基苯硼酸频哪酯、0.6mmol碳酸钾和8mLN,N-二甲基甲酰胺依次加入15mL干燥的三口烧瓶中,回流反应20h,用TLC法跟踪监测,至反应完全后停止反应;
(2)反应液经减压蒸馏除去N,N-二甲基甲酰胺后再加入乙酸乙酯,用饱和食盐水进行洗涤至中性,有机相再经无水硫酸钠干燥、过滤、浓缩后得到2-(4-(4,4,5,5-四甲基-1,3,2-二噁硼烷-2-基)苯甲氧基)-5-(樟脑-3-甲烯基)苯甲醛粗产物;
(3)2-(4-(4,4,5,5-四甲基-1,3,2-二噁硼烷-2-基)苯甲氧基)-5-(樟脑-3-甲烯基)苯甲醛粗产物经硅胶柱分离,得到2-(4-(4,4,5,5-四甲基-1,3,2-二噁硼烷-2-基)苯甲氧基)-5-(樟脑-3-甲烯基)苯甲醛纯品。
4.根据权利要求2所述的樟脑耦合苯并噻唑基烯腈型次氯酸荧光探针的合成方法,其特征在于,步骤2)的制备方法包括:
(1)将0.5mmol 2-(4-(4,4,5,5-四甲基-1,3,2-二噁硼烷-2-基)苯甲氧基)-5-(樟脑-3-甲烯基)苯甲醛、0.6mmol2-氰甲基苯并噻唑、0.6mmol哌啶、8mL无水乙醇依次加入15mL干燥的三口烧瓶中,在氮气保护下加热回流反应10h;
(2)反应液冷却至室温后,析出的固体经抽滤、并用少量的无水乙醇洗涤,得到2-(2-苯并噻唑基)-3-(2-(4-(4,4,5,5-四甲基-1,3,2-二噁硼烷-2-基)苯甲氧基)-5-(樟脑-3-甲烯基)苯基)丙烯腈固体产物。
5.权利要求1所述的2-(2-苯并噻唑基)-3-(2-(4-(4,4,5,5-四甲基-1,3,2-二噁硼烷-2-基)苯甲氧基)-5-(樟脑-3-甲烯基)苯基)丙烯腈在制备用于检测次氯酸的荧光探针中的应用。
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