CN111675657B - 脱氢枞酸基2,4-二芳基苯并咪唑类三价铁离子、汞离子荧光探针及其制备方法和应用 - Google Patents
脱氢枞酸基2,4-二芳基苯并咪唑类三价铁离子、汞离子荧光探针及其制备方法和应用 Download PDFInfo
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Abstract
本发明公开了脱氢枞酸基2,4‑二芳基苯并咪唑类三价铁离子、汞离子荧光探针及其制备方法和应用。脱氢枞酸经过酰氯化和甲酯化合成脱氢枞酸甲酯,然后与NBS生成,产物经过双硝化合成12‑溴‑13,14‑二硝基脱氢枞酸甲酯,继续与3,4,5‑三甲氧基苯硼酸反应生成12‑(3,4,5‑三甲氧基苯基)‑13,14‑二硝基脱氢枞酸甲酯,再经Fe/HCl还原反应生成12‑(3,4,5‑三甲氧基苯基)‑13,14‑双氨基脱氢枞酸甲酯,产物再与2‑羟基‑1‑萘甲醛缩合生成该化合物。该化合物能选择性地与Fe3+、Hg2+生成络合物,形成络合物后蓝色荧光猝灭,可作为Fe3+或Hg2+浓度检测用荧光探针。
Description
技术领域
本发明属于精细有机合成技术领域,具体涉及脱氢枞酸基2,4-二芳基苯并咪唑类三价铁离子、汞离子荧光探针及其制备方法和应用。
背景技术
Fe3+是人体所必需的微量元素之一,铁在生物和病理过程中起着至关重要的作用,参与氧化反应以及酶反应。铁离子的过量或缺乏会引起不同的疾病,如癌症、贫血、阿尔茨海默病、帕金森等。汞是一种有毒的元素,它的所有形式都有潜在的健康危害,因为它可能积聚在大脑和肾脏等重要器官,并导致无法治疗的疾病。目前虽然有很多金属离子的检测方法,如原子吸收法、分光光度法、循环伏安法等,但是这些方法存在检测环境严格,样品标准要求高,操作专业性高等问题,而荧光探针法具有检测速度快,检测环境广,灵敏度高等优点已被应用于铁离子,汞离子等金属离子的检测中。近年来,人们研究了很多有机荧光探针用于金属离子的检测,如罗丹明类荧光探针检测三价铁离子,萘酰胺基荧光探针检测三价铁离子,香豆素类荧光探针检测铁离子,汞离子等,但是还没有合成脱氢枞酸基2,4-二芳基苯并咪唑类荧光探针检测铁离子,汞离子的相关报道。
发明内容
针对现有技术中存在的问题,本发明要解决的一个技术问题在于提供脱氢枞酸基2,4- 二芳基苯并咪唑类三价铁离子、汞离子荧光探针,与Fe3+、Hg2+络合并在波长365nm紫外灯照射下蓝色光发生猝灭,用于检测Fe3+、Hg2+浓度。本发明要解决的另一个技术问题在于提供上述脱氢枞酸基2,4-二芳基苯并咪唑类三价铁离子、汞离子荧光探针的制备方法,利用从天然可再生资源歧化松香中提取到的脱氢枞酸为原料,经过一系列化学反应制得,原料来源广泛,为大批量生产奠定基础。本发明要解决的技术问题还有一个在于提供上述脱氢枞酸基2,4-二芳基苯并咪唑类三价铁离子、汞离子荧光探针的应用,该化合物能选择性的与Hg2+、Fe3+络合,蓝色荧光猝灭,可作为荧光探针用于检测Hg2+、Fe3+离子。
为了解决上述问题,本发明所采用的技术方案如下:
脱氢枞酸基2,4-二芳基苯并咪唑类三价铁离子、汞离子荧光探针,该化合物名称为: 2-(2-羟基萘-1-基)-6,9a-二甲基-11-(3,4,5-甲氧基苯基-4,5,5a,6,7,8,9,9a-八氢-3H-菲罗[1,2-d] 咪唑-6-甲酯,结构式为:
上述脱氢枞酸基2,4-二芳基苯并咪唑类三价铁离子、汞离子荧光探针的制备方法,包括以下步骤:
1)脱氢枞酸经过甲酯化、溴代和双硝化反应,制得12-溴-13,14-二硝基脱氢枞酸甲酯;
2)12-溴-13,14-二硝基脱氢枞酸甲酯与3,4,5-三甲氧基苯硼酸反应生成12-(3,4,5-三甲氧基苯基)-13,14-二硝基脱氢枞酸甲酯;
3)12-(3,4,5-三甲氧基苯基)-13,14-二硝基脱氢枞酸甲酯经过Fe/HCl还原,制得12-(3,4,5-三甲氧基苯基)-13,14-二氨基脱异丙基脱氢枞酸甲酯;
4)12-(3,4,5-三甲氧基苯基)-13,14-二氨基脱异丙基脱氢枞酸甲酯与2-羟基-1-萘甲醛反应生成2-(2-羟基萘-1-基)-6,9a-二甲基-11-(3,4,5-甲氧基苯基-4,5,5a,6,7,8,9,9a-八氢-3H-菲罗 [1,2-d]咪唑-6-甲酯。
所述脱氢枞酸基2,4-二芳基苯并咪唑类三价铁离子、汞离子荧光探针的制备方法,12- 溴-13,14-二硝基脱氢枞酸甲酯的制备:
(1)向脱氢枞酸甲苯溶液中加入二氯亚砜进行反应,反应结束后真空旋干,加入甲醇进行甲酯化反应,反应结束后旋干,加入乙醇溶解结晶,得到脱氢枞酸甲酯;所述脱氢枞酸甲苯溶液的浓度为0.2~0.8g/mL,脱氢枞酸与二氯亚砜的用量比为1g:0.3~0.4mL,脱氢枞酸与甲醇的用量比为1g:1~3mL;所述脱氢枞酸与二氯亚砜的反应温度为75~80℃,反应时间为2~4h;所述甲酯化反应温度为75~80℃,反应时间为2~4h;
(2)向脱氢枞酸甲酯的乙腈溶液中加入N-溴代丁二酰亚胺,避光常温反应,反应结束后旋蒸,二氯甲烷洗涤两次,甲醇溶解结晶,得到12-溴代脱氢枞酸甲酯;所述脱氢枞酸甲酯乙腈溶液的浓度为0.15~0.20g/mL,反应时间为20~24h;所述氢枞酸甲酯与N-溴代丁二酰亚胺的质量比为1.0:1~1.5:1;
(3)将12-溴代脱氢枞酸甲酯加入发烟硝酸和浓硫酸中进行双硝化反应,反应结束后倒入冰水中,用乙酸乙酯萃取三次,水洗三次,饱和碳酸氢钠水溶液洗一次,饱和食盐水洗一次,无水硫酸钠干燥除水,用石油醚:乙酸乙酯=500:1-200:1过柱提纯,得到淡黄色的12-溴-13,14-二硝基脱氢枞酸甲酯;所述12-溴代脱氢枞酸甲酯与发烟硝酸的用量比为1g:6~7mL,所述12-溴代脱氢枞酸甲酯与浓硫酸的用量比为1~3g:1mL,所述硝化反应在冰浴条件下反应0.5~1.5h。
所述脱氢枞酸基2,4-二芳基苯并咪唑类三价铁离子、汞离子荧光探针的制备方法, 12-(3,4,5-三甲氧基苯基)-13,14-二硝基脱氢枞酸甲酯的制备:将12-溴-13,14-二硝基脱氢枞酸甲酯溶于甲苯和乙醇中,然后加入3,4,5-三甲氧基苯硼酸、K2CO3溶液、pd(pph3)4(四(三苯基膦)钯)在氮气保护下80~100℃回流12h;反应结束后,用乙酸乙酯萃取三次,水洗三次,饱和碳酸氢钠水溶液洗一次,饱和食盐水洗一次,无水硫酸钠干燥除水,用石油醚:乙酸乙酯=100:1-50:1过柱提纯,得到黄色油状固体12-(3,4,5-三甲氧基苯基)-13,14-二硝基脱氢枞酸甲酯。
所述脱氢枞酸基2,4-二芳基苯并咪唑类三价铁离子、汞离子荧光探针的制备方法,所述12-溴-13,14-二硝基脱氢枞酸甲酯与3,4,5-三甲氧基苯硼酸的用量比为1.3:1~1.4:1;所述 12-溴-13,14-二硝基脱氢枞酸甲酯与pd(pph3)4的用量比为7:1~8:1。
所述脱氢枞酸基2,4-二芳基苯并咪唑类三价铁离子、汞离子荧光探针的制备方法, 12-(3,4,5-三甲氧基苯基)-13,14-二氨基脱氢枞酸甲酯的制备:将12-(3,4,5-三甲氧基苯基)-13,14-二硝基脱氢枞酸甲酯溶于HFIP(六氟异丙醇)中,然后加入铁粉、蒸馏水、盐酸进行还原反应,反应结束后用乙酸乙酯萃取三次,水洗三次,饱和碳酸氢钠水溶液洗一次,饱和食盐水洗一次,无水硫酸钠干燥除水,旋干得到油状的粗品12-(3,4,5-三甲氧基苯基)-13,14-双氨基脱氢枞酸甲酯。
所述脱氢枞酸基2,4-二芳基苯并咪唑类三价铁离子、汞离子荧光探针的制备方法,所述12-(3,4,5-三甲氧基苯基)-13,14-二硝基脱氢枞酸甲酯与HFIP的用量比为1g:4~5mL,所述12-(3,4,5-三甲氧基苯基)-13,14-二硝基脱氢枞酸甲酯与铁粉的用量比为1:1~1:1.1, 12-(3,4,5-三甲氧基苯基)-13,14-二硝基脱氢枞酸甲酯与盐酸的用量比为0.1~0.12g:1mL;所述Fe/HCl还原温度为40~50℃,反应时间为2~3h。
所述脱氢枞酸基2,4-二芳基苯并咪唑类三价铁离子、汞离子荧光探针的制备方法,将 12-(3,4,5-三甲氧基苯基)-13,14-二氨基脱氢枞酸甲酯溶于无水乙醇中,加入2-羟基-1-萘甲醛和对甲苯磺酸,氮气保护,80~90℃下回流反应12h;反应结束后,旋蒸干,用水洗三遍,饱和碳酸钠溶液萃取一次,饱和食盐水萃取一次,无水硫酸钠干燥除水,用石油醚:乙酸乙酯=100:1-20:1过柱提纯,得到纯的2-(2-羟基萘-1-基)-6,9a-二甲基-11-(3,4,5-甲氧基苯基-4,5,5a,6,7,8,9,9a-八氢-3H-菲罗[1,2-d]咪唑-6-甲酯。
所述脱氢枞酸基2,4-二芳基苯并咪唑类三价铁离子、汞离子荧光探针的制备方法,所述12-(3,4,5-三甲氧基苯基)-13,14-二氨基脱氢枞酸甲酯、2-羟基-1-萘甲醛和对甲苯磺酸的质量比为1:1.2~1.2:0.1~0.11。
上述脱氢枞酸基2,4-二芳基苯并咪唑类三价铁离子、汞离子荧光探针在检测三价铁离子、汞离子中的应用。
本发明利用从天然可再生资源歧化松香中提取的脱氢枞酸为原料,脱氢枞酸经过酰氯化和甲醇合成脱氢枞酸甲酯,脱氢枞酸甲酯与NBS(N-溴代丁二酰亚胺)生成,12-溴代脱氢枞酸甲酯与浓硫酸和发烟硝酸合成12-溴-13,14-二硝基脱氢枞酸甲酯,12-溴-13,14-二硝基脱氢枞酸甲酯与3,4,5-三甲氧基苯硼酸生成12-(3,4,5-三甲氧基苯基)-13,14-二硝基脱氢枞酸甲酯,12-(3,4,5-三甲氧基苯基)-13,14-二硝基脱氢枞酸甲酯在盐酸的作用下还原成 12-(3,4,5-三甲氧基苯基)-13,14-双氨基脱氢枞酸甲酯。12-(3,4,5-三甲氧基苯基)-13,14-二氨基脱氢枞酸甲酯与2-羟基-1-萘甲醛缩合生成2-(2-羟基萘-1-基)-6,9a-二甲基-11-(3,4,5-甲氧基苯基-4,5,5a,6,7,8,9,9a-八氢-3H-菲罗[1,2-d]咪唑-6-甲酯;该化合物能识别Hg2+、Fe3+,可作为检测Hg2+、Fe3+的探针。
有益效果:与现有的技术相比,本发明的优点包括:
本发明利用从天然可再生资源歧化松香中提取的脱氢枞酸为原料制备的脱氢枞酸基 2,4-二芳基苯并咪唑类化合物,能选择性的与Hg2+、Fe3+络合,蓝色荧光猝灭,该化合物可作为荧光探针用于检测Hg2+、Fe3+离子。
附图说明
图1为2-(2-羟基萘-1-基)-6,9a-二甲基-11-(3,4,5-甲氧基苯基-4,5,5a,6,7,8,9,9a-八氢-3H- 菲罗[1,2-d]咪唑-6-甲酯与铁离子、汞离子络合的荧光吸收光谱效果图,其中图1a为加入铁离子的荧光吸收光谱图,图1b为加入汞离子的荧光吸收光谱图;
图2为2-(2-羟基萘-1-基)-6,9a-二甲基-11-(3,4,5-甲氧基苯基-4,5,5a,6,7,8,9,9a-八氢-3H- 菲罗[1,2-d]咪唑-6-甲酯在日照及365nm紫外光下与铁离子、汞离子络合前后的结果图,其中图2a为日照下化合物加入Fe3+、Hg2+离子前后的照片,图2b为365nm紫外灯下化合物加入Fe3+、Hg2+离子前后照片;
图3为2-(2-羟基萘-1-基)-6,9a-二甲基-11-(3,4,5-甲氧基苯基-4,5,5a,6,7,8,9,9a-八氢-3H- 菲罗[1,2-d]咪唑-6-甲酯与不同金属离子作用的荧光吸收光谱效果图。
具体实施方式
为使本发明的上述目的、特征和优点能够更加明显易懂,下面结合具体实施例对本发明的具体实施方式做详细的说明。
实施例1
脱氢枞酸基2,4-二芳基苯并咪唑类化合物的合成方法,合成过程为:
具体步骤如下:
1)12-溴-13,14-二硝基脱氢枞酸甲酯的制备:脱氢枞酸经过甲酯化、溴代和双硝化反应制得,具体过程如下:
称取30g脱氢枞酸溶于60mL的甲苯中,加入11mL的二氯亚砜在78-80℃中反应3h,真空旋干,加入60mL甲醇,在78-80℃下反应3h,旋干加入30mL乙醇溶解结晶,得到脱氢枞酸甲酯;
准确称取5g脱氢枞酸甲酯,溶于30mL乙腈中,加入4g N-溴代丁二酰亚胺,避光常温反应24h,旋蒸,二氯甲烷洗涤两次,100mL甲醇溶解结晶,得到12-溴代脱氢枞酸甲酯;
准确称取3g 12-溴代脱氢枞酸甲酯溶于19mL发烟硝酸和1.5mL的浓硫酸中,在冰浴条件下反应1h,反应结束后倒入冰水中,用乙酸乙酯萃取三次,水洗三次,饱和碳酸氢钠水溶液洗一次,饱和食盐水洗一次,无水硫酸钠干燥除水,用石油醚:乙酸乙酯=500:1-200:1过柱提纯,得到淡黄色的12-溴-13,14-二硝基脱氢枞酸甲酯,得率为88.2%。
2)12-(3,4,5-三甲氧基苯基)-13,14-二硝基脱氢枞酸甲酯的制备
准确称取0.88g 12-溴-13,14-二硝基脱氢枞酸甲酯溶于30mL甲苯和15mL乙醇中,加入0.64g 3,4,5-三甲氧基苯硼酸,2mol/L的K2CO3溶液12mL,pd(pph3)4 0.115g,在氮气保护下90℃回流12h。反应结束后,用乙酸乙酯萃取三次,水洗三次,饱和碳酸氢钠水溶液洗一次,饱和食盐水洗一次,无水硫酸钠干燥除水,用石油醚:乙酸乙酯=100:1-50:1 过柱提纯,得到黄色油状固体12-(3,4,5-三甲氧基苯基)-13,14-二硝基脱氢枞酸甲酯。得率为85.4%。
3)12-(3,4,5-三甲氧基苯基)-13,14-二氨基脱氢枞酸甲酯的制备
准确称取0.53g 12-(3,4,5-三甲氧基苯基)-13,14-二硝基脱氢枞酸甲酯溶于2.5mL HFIP(六氟异丙醇)中,加入铁粉0.56g,蒸馏水30mL,盐酸5mL,45℃下搅拌反应2.5h,反应结束后用乙酸乙酯萃取三次,水洗三次,饱和碳酸氢钠水溶液洗一次,饱和食盐水洗一次,无水硫酸钠干燥除水,旋干得到粗的油状的12-(3,4,5-三甲氧基苯基)-13,14-二氨基脱氢枞酸甲酯,用乙醇重结晶,得率为81.8%。
4)2-(2-羟基萘-1-基)-6,9a-二甲基-11-(3,4,5-甲氧基苯基-4,5,5a,6,7,8,9,9a-八氢-3H-菲罗 [1,2-d]咪唑-6-甲酯的制备
准确称取上一步得到的0.468g 12-(3,4,5-三甲氧基苯基)-13,14-二氨基脱氢枞酸甲酯溶于30mL无水乙醇中,加入0.6g 2-羟基-1-萘甲醛,对甲苯磺酸50mg,氮气保护,85℃下回流反应12h;反应结束后,旋蒸干,用水洗三遍,饱和碳酸钠溶液萃取一次,饱和食盐水萃取一次,无水硫酸钠干燥除水,用石油醚:乙酸乙酯=100:1-20:1过柱提纯,得到黄色纯的2-(2-羟基萘-1-基)-6,9a-二甲基-11-(3,4,5-甲氧基苯基)-4,5,5a,6,7,8,9,9a-八氢-3H-菲罗 [1,2-d]咪唑-6-甲酯,得率为74.5%。
产物表征数据为:M.p 171.9~172.8℃;IR(KBr,cm-1):732,820,973,1006,1127,1245, 1464,1577,1623,1723,2833,2937,3305,3446;1H NMR(CDCl3,600MHz):δ1.33(s,3H), 1.36(s,3H),1.57~1.85(m,6H),1.98(m,1H),2.39(d,J=11.9Hz,1H),2.49(d,J=12.5Hz, 1H),3.13(m,1H),3.24(m,1H),3.67(s,3H),3.91(s,3H),3.98(s,6H),7.06(brs,2H),7.28(d,J =8.8Hz,1H),7.35(t,J=7.4Hz,1H),7.37(s,1H),7.52(t,J=7.6Hz,1H),7.77(d,J=8.9Hz, 1H),7.81(d,J=8.0Hz,1H),8.30(d,J=8.5Hz,1H);13C NMR(CDCl3,150MHz):δ16.57, 18.69,21.11,25.44,25.48,36.70,37.56,38.51,45.32,47.80,52.09,56.31,61.02,105.27,119.08, 119.72,120.83,121.72,123.33,126.23,126.58,128.15,128.62,129.71,130.88,132.50,134.39, 137.64,140.27,145.14,148.15,150.67,153.67,158.46,179.18;ESI-MS:m/z[M+H]+calcd for C38H41N2O6 621.2958,found621.2958.
实施例2
将2-(2-羟基萘-1-基)-6,9a-二甲基-11-(3,4,5-甲氧基苯基-4,5,5a,6,7,8,9,9a-八氢-3H-菲罗 [1,2-d]咪唑-6-甲酯溶于乙醇水溶液(乙醇:水=1:1)中(1×10-5M),加入(0-1)×10-4M的Fe3+、 Hg2+测得不同浓度Fe3+、Hg2+对2-(2-羟基萘-1-基)-6,9a-二甲基-11-(3,4,5-甲氧基苯基-4,5,5a,6,7,8,9,9a-八氢-3H-菲罗[1,2-d]咪唑-6-甲酯的荧光吸收光谱,如图1所示1a:加入铁离子的荧光吸收光谱图;1b:加入汞离子的荧光吸收光谱图,该化合物的荧光吸收明显减弱,直至猝灭,说明化合物能与Fe3+、Hg2+络合。
实施例3
准确称取62mg 2-(2-羟基萘-1-基)-6,9a-二甲基-11-(3,4,5-甲氧基苯基-4,5,5a,6,7,8,9,9a- 八氢-3H-菲罗[1,2-d]咪唑-6-甲酯溶于10mL无水乙醇中,配制成1×10-3M的溶液,取100 μM原液用乙醇水溶液(乙醇:水=1:1)稀释成10mL浓度为1×10-5M的溶液,每次加入5μL 的Fe3+(1×10-2M),Hg2+(1×10-2M),随着Fe3+的加入溶液变为淡黄色,随着Hg2+的加入溶液颜色无变化。在365nm紫外灯下观察,如图2所示,2a:日照下化合物加入Fe3+、 Hg2+离子前后的照片;2b:365nm紫外灯下化合物加入Fe3+、Hg2+离子前后照片,加入 Hg2+、Fe3+离子的溶液的蓝色荧光猝灭,说明该化合物与Hg2+、Fe3+络合,然后加入Hg2+或Fe3+后在365nm紫外光下蓝色荧光猝灭,检出三价铁离子,汞离子。通过加入等摩尔量的Na+,Zn2+,Ca2+,Cu2+,Fe2+,Mn2+,Mg2+,Co2+,Cs2+,Cd2+,K+,Sn2+,Ni2+,La3+, Cr3+等金属离子,通过荧光分光光度计测量,谱图显示不会导致化合物荧光的猝灭,如图3 所示。说明该化合物可以作为一种有效识Fe3+、Hg2+离子的荧光探针。
Claims (10)
2.权利要求1所述脱氢枞酸基2,4-二芳基苯并咪唑类三价铁离子、汞离子荧光探针的制备方法,其特征在于,包括以下步骤:
1)脱氢枞酸经过甲酯化、溴代和双硝化反应,制得12-溴-13,14-二硝基脱氢枞酸甲酯;
2)12-溴-13,14-二硝基脱氢枞酸甲酯与3,4,5-三甲氧基苯硼酸反应生成12-(3,4,5-三甲氧基苯基)-13,14-二硝基脱氢枞酸甲酯;
3)12-(3,4,5-三甲氧基苯基)-13,14-二硝基脱氢枞酸甲酯经过Fe/HCl还原,制得12-(3,4,5-三甲氧基苯基)-13,14-二氨基脱异丙基脱氢枞酸甲酯;
4)12-(3,4,5-三甲氧基苯基)-13,14-二氨基脱异丙基脱氢枞酸甲酯与2-羟基-1-萘甲醛反应生成2-(2-羟基萘-1-基)-6,9a-二甲基-11-(3,4,5-甲氧基苯基-4,5,5a,6,7,8,9,9a-八氢-3H-菲罗[1,2-d]咪唑-6-甲酯。
3.根据权利要求2所述脱氢枞酸基2,4-二芳基苯并咪唑类三价铁离子、汞离子荧光探针的制备方法,其特征在于,12-溴-13,14-二硝基脱氢枞酸甲酯的制备:
(1)向脱氢枞酸甲苯溶液中加入二氯亚砜进行反应,反应结束后真空旋干,加入甲醇进行甲酯化反应,反应结束后旋干,加入乙醇溶解结晶,得到脱氢枞酸甲酯;所述脱氢枞酸甲苯溶液的浓度为0.2~0.8g/mL,脱氢枞酸与二氯亚砜的用量比为1g:0.3~0.4mL,脱氢枞酸与甲醇的用量比为1g:1~3mL;所述脱氢枞酸与二氯亚砜的反应温度为75~80℃,反应时间为2~4h;所述甲酯化反应温度为75~80℃,反应时间为2~4h;
(2)向脱氢枞酸甲酯的乙腈溶液中加入N-溴代丁二酰亚胺,避光常温反应,反应结束后旋蒸,二氯甲烷洗涤两次,甲醇溶解结晶,得到12-溴代脱氢枞酸甲酯;所述脱氢枞酸甲酯乙腈溶液的浓度为0.15~0.20g/mL,反应时间为20~24h;所述氢枞酸甲酯与N-溴代丁二酰亚胺的质量比为1.0:1~1.5:1;
(3)将12-溴代脱氢枞酸甲酯加入发烟硝酸和浓硫酸中进行双硝化反应,反应结束后倒入冰水中,用乙酸乙酯萃取三次,水洗三次,饱和碳酸氢钠水溶液洗一次,饱和食盐水洗一次,无水硫酸钠干燥除水,用石油醚:乙酸乙酯=500:1-200:1过柱提纯,得到淡黄色的12-溴-13,14-二硝基脱氢枞酸甲酯;所述12-溴代脱氢枞酸甲酯与发烟硝酸的用量比为1g:6~7mL,所述12-溴代脱氢枞酸甲酯与浓硫酸的用量比为1~3g:1mL,所述硝化反应在冰浴条件下反应0.5~1.5h。
4.根据权利要求2所述脱氢枞酸基2,4-二芳基苯并咪唑类三价铁离子、汞离子荧光探针的制备方法,其特征在于,12-(3,4,5-三甲氧基苯基)-13,14-二硝基脱氢枞酸甲酯的制备:将12-溴-13,14-二硝基脱氢枞酸甲酯溶于甲苯和乙醇中,然后加入3,4,5-三甲氧基苯硼酸、K2CO3溶液、pd(pph3)4,在氮气保护下80~100℃回流12h;反应结束后,用乙酸乙酯萃取三次,水洗三次,饱和碳酸氢钠水溶液洗一次,饱和食盐水洗一次,无水硫酸钠干燥除水,用石油醚:乙酸乙酯=100:1-50:1过柱提纯,得到黄色油状固体12-(3,4,5-三甲氧基苯基)-13,14-二硝基脱氢枞酸甲酯。
5.根据权利要求4所述脱氢枞酸基2,4-二芳基苯并咪唑类三价铁离子、汞离子荧光探针的制备方法,其特征在于,所述12-溴-13,14-二硝基脱氢枞酸甲酯与3,4,5-三甲氧基苯硼酸的用量比为1.3:1~1.4:1;所述12-溴-13,14-二硝基脱氢枞酸甲酯与pd(pph3)4的用量比为7:1~8:1。
6.根据权利要求2所述脱氢枞酸基2,4-二芳基苯并咪唑类三价铁离子、汞离子荧光探针的制备方法,其特征在于,12-(3,4,5-三甲氧基苯基)-13,14-二氨基脱氢枞酸甲酯的制备:将12-(3,4,5-三甲氧基苯基)-13,14-二硝基脱氢枞酸甲酯溶于HFIP中,然后加入铁粉、蒸馏水、盐酸进行还原反应,反应结束后用乙酸乙酯萃取三次,水洗三次,饱和碳酸氢钠水溶液洗一次,饱和食盐水洗一次,无水硫酸钠干燥除水,旋干得到油状的粗品12-(3,4,5-三甲氧基苯基)-13,14-双氨基脱氢枞酸甲酯。
7.根据权利要求6所述脱氢枞酸基2,4-二芳基苯并咪唑类三价铁离子、汞离子荧光探针的制备方法,其特征在于,所述12-(3,4,5-三甲氧基苯基)-13,14-二硝基脱氢枞酸甲酯与HFIP的用量比为1g:4~5mL,所述12-(3,4,5-三甲氧基苯基)-13,14-二硝基脱氢枞酸甲酯与铁粉的用量比为1:1~1:1.1,12-(3,4,5-三甲氧基苯基)-13,14-二硝基脱氢枞酸甲酯与盐酸的用量比为0.1~0.12g:1mL;所述Fe/HCl还原温度为40~50℃,反应时间为2~3h。
8.根据权利要求2所述脱氢枞酸基2,4-二芳基苯并咪唑类三价铁离子、汞离子荧光探针的制备方法,其特征在于,将12-(3,4,5-三甲氧基苯基)-13,14-二氨基脱氢枞酸甲酯溶于无水乙醇中,加入2-羟基-1-萘甲醛和对甲苯磺酸,氮气保护,80~90℃下回流反应12h;反应结束后,旋蒸干,用水洗三遍,饱和碳酸钠溶液萃取一次,饱和食盐水萃取一次,无水硫酸钠干燥除水,用石油醚:乙酸乙酯=100:1-20:1过柱提纯,得到纯的2-(2-羟基萘-1-基)-6,9a-二甲基-11-(3,4,5-甲氧基苯基-4,5,5a,6,7,8,9,9a-八氢-3H-菲罗[1,2-d]咪唑-6-甲酯。
9.根据权利要求8所述脱氢枞酸基2,4-二芳基苯并咪唑类三价铁离子、汞离子荧光探针的制备方法,其特征在于,所述12-(3,4,5-三甲氧基苯基)-13,14-二氨基脱氢枞酸甲酯、2-羟基-1-萘甲醛和对甲苯磺酸的质量比为1:1.2~1.2:0.1~0.11。
10.权利要求1所述脱氢枞酸基2,4-二芳基苯并咪唑类三价铁离子、汞离子荧光探针在检测三价铁离子、汞离子中的应用。
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