CN113087731B - 一种对三乙胺响应的双氟硼荧光染料的制备方法及应用 - Google Patents
一种对三乙胺响应的双氟硼荧光染料的制备方法及应用 Download PDFInfo
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Abstract
本发明公开了一种对碱响应的双氟硼结构的荧光染料的制备方法及应用,在室温下向反应瓶中加入七元氟硼化合物1,二氯甲烷,搅拌溶解,然后再加入水杨醛、对甲苯磺酸,加热回流反应得到反应液1,加热回流反应温度为35‑40℃,回流2‑18h;再加入二氯甲烷,三乙胺,缓慢的滴加三氟化硼乙醚络合物,加热回流反应得到反应液2,加热回流反应温度为35‑40℃,回流2‑18h得到双氟硼结构荧光染料化合物。通过不同荧光强度区分三乙胺的摩尔量,可以检测DCM液体环境中三乙胺的摩尔量的变化,染料对三乙胺的检测限的摩尔比为1:1‑25000,可检测DCM中三乙胺的摩尔量范围较大,并且在酸性和中性溶液不显色,即在荧光光谱稳定。
Description
技术领域
本发明公开了一种对三乙胺响应的双氟硼结构的荧光染料的制备方法及应用,具体的说涉及一种能通过不同荧光强度区分三乙胺的摩尔量的荧光染料,可以检测DCM液体环境中三乙胺的摩尔量的变化。
背景技术
三乙胺是一种挥发性有机胺,为中等毒性化合物,而且如果吸入可能会引起呼吸器官以及血液循环系统,包括有中枢系统以及身体的肝脏等机体出现有失常的症状出现,同时可能还会使口腔腐蚀甚至出现有肺水肿以及导致化学性的灼伤。对于女性患者如果吸入三乙胺的成分,还会出现有不孕不育的情况。
三乙胺在生产中常作为缚酸剂,最后形成废水排出,废水中三乙胺的浓度高达500g/L,经处理后废水中的三乙胺浓度可以降到几个ppm,快速测定三乙胺是废水深度处理的前提。目前测定水中三乙胺含量的方法有分光光度法和气相色谱法等,分光光度法常用于废水中。
国内外现有的利用不同荧光探针实现对三乙胺检测的方法大多数存在操作方法复杂、反应时间长、灵敏度不高等缺陷。因此,需要一种操作简单、检测快速且能对三乙胺高灵敏识别的检测方法。
发明内容
本发明的一个目的是解决上述问题,提供一种可在二氯甲烷中检测三乙胺的摩尔量的双氟硼结构的荧光染料及其制备方法,该染料制备简单、易得,并且结构稳定,其本身的荧光强度很强,但在碱性条件下,可产生荧光更弱的物质,该染料对三乙胺的检测具有灵敏度高,选择性好,快捷等优势,并可以探测浓度较高的三乙胺液体环境。
本发明所述的一种对三乙胺响应的双氟硼结构的荧光染料,分子式为C23H19B2F4N3O,结构式如下所示:
本发明所提供的荧光染料是通过以下合成步骤制备得到的:
(1)在室温下向反应瓶中加入七元氟硼化合物1,二氯甲烷,搅拌溶解,然后再加入水杨醛、对甲苯磺酸,加热回流反应得到反应液1,加热回流反应温度为35-40℃,回流2-18h;
(2)将步骤(1)中的反应液1旋蒸,再经硅胶柱层析分离得到橙色固体化合物3;
(3)分别向步骤(2)中的化合物3加入二氯甲烷,三乙胺,缓慢的滴加三氟化硼乙醚络合物,加热回流反应得到反应液2,加热回流反应温度为35-40℃,回流2-18h(优选为升温至 35℃搅拌回流反应0.5-8h);
(4)将步骤(3)中的反应液2分别水洗、萃取、干燥,柱层析,旋干后得到金黄色固体化合物I。
所述步骤(1)中七元氟硼化合物1、水杨醛、对甲苯磺酸的投料摩尔比为1:1-10:0.01-1。对甲苯磺酸的添加量对化合物3的产率影响较大。所述步骤(3)化合物3、三乙胺与三氟化硼乙醚络合物的投料摩尔比为1:1-25:1-25,投料的顺序为化合物3,二氯甲烷,三乙胺,三氟化硼乙醚。
本发明有益效果如下:
(1)本发明将所述的双氟硼结构荧光染料化合物,通过不同荧光强度区分三乙胺的摩尔量,可以检测DCM液体环境中三乙胺的摩尔量的变化,染料对三乙胺的检测限的摩尔比为 1:1-25000,可检测DCM中三乙胺的摩尔量范围较大,并且在酸性和中性溶液不显色,即在荧光光谱稳定。
(2)本发明将所述的双氟硼结构荧光染料化合物对三乙胺的检测操作简单、检测快速,在三乙胺加入后的30秒,荧光强度可降到最低,峰值变化趋于稳定。
附图说明
图1是化合物I的氢谱图。
图2是化合物I的质谱图。
图3是化合物I的滴定的荧光光谱图。
图4是化合物I的滴定的荧光与时间关系的光谱图。
具体实施方式
下面结合实施例来进一步说明本发明,但本发明要求保护的范围并不局限于实施例表述的范围。
实施例1实施例1探针分子的合成
实施例1-1
取化合物1(598mg,2mmol);水杨醛(1.96ml,2mmol),TsOH(34.2,mg,0.2mmol)溶于DCM(60ml)中,35℃搅拌12h,点板监测反应至原料完全反应,加碱中和,将产物水洗,萃取,干燥,旋蒸,过滤纯化得到化合物3(216mg,产率为26.7%)。取上述化合物3 (202mg,0.5mmol),加入20ml二氯甲烷溶液,1.00ml三乙胺,在电磁搅拌下,慢慢滴加三氟化硼乙醚溶液(1.00ml),升高温度至35℃,回流30min,TLC点板检测,将产物水洗,萃取,干燥,旋蒸,过滤纯化得到金黄色固体化合物I,(194mg,产率为86%)。
实施例1-2
取化合物1(598mg,2mmol);水杨醛(1.96ml,2mmol),TsOH(17.1,mg,0.1mmol)溶于DCM(60ml)中,35℃搅拌12h,点板监测反应至原料完全反应,加碱中和,将产物水洗,萃取,干燥,旋蒸,过滤纯化得到化合物3(299mg,产率为37%)。取上述化合物3 (202mg,0.5mmol),加入20ml二氯甲烷溶液,1.00ml三乙胺,在电磁搅拌下,慢慢滴加三氟化硼乙醚溶液(1.00ml),升高温度至35℃,回流30min,TLC点板检测,将产物水洗,萃取,干燥,旋蒸,过滤纯化得到金黄色固体化合物I,(198.4mg,产率为88%)。相对于实施例1-1,对甲苯磺酸的量减少一半,化合物3的产率提高了10.3%。
实施例1-3
取化合物1(598mg,2mmol);水杨醛(1.96ml,2mmol);TsOH(8.55,mg,0.05mmol)溶于 DCM(60ml)中,35℃搅拌12h,点板监测反应至原料完全反应,加碱中和,将产物水洗,萃取,干燥,旋蒸,过滤纯化得到化合物3(346mg,产率为42.8%)。取上述化合物3 (202mg,0.5mmol),加入20ml二氯甲烷溶液,1.00ml三乙胺,在电磁搅拌下,慢慢滴加三氟化硼乙醚溶液(1.00ml),升高温度至35℃,回流30min,TLC点板检测,将产物水洗,萃取,干燥,旋蒸,过滤纯化得到金黄色固体化合物I(196.2mg,产率为87%)。相对于实施例1-2,对甲苯磺酸的量减少一半,化合物3的产率提高了5.8%。
实施例1-4
取化合物1(598mg,2mmol);水杨醛(1.96ml,2mmol);TsOH(1.72,mg,0.01mmol)溶于DCM(60ml)中,35℃搅拌12h,点板监测反应至原料完全反应,加碱中和,将产物水洗,萃取,干燥,旋蒸,过滤纯化得到化合物3(435mg,产率为53.8%)。取上述化合物3 (202mg,0.5mmol),加入20ml二氯甲烷溶液,1.00ml三乙胺,在电磁搅拌下,慢慢滴加三氟化硼乙醚溶液(1.00ml),升高温度至35℃,回流30min,TLC点板检测,将产物水洗,萃取,干燥,旋蒸,过滤纯化得到金黄色固体化合物I(198.4mg,产率为88%)。相对于实施例1-2,对甲苯磺酸的量减少5倍,化合物3的产率提高了11%。
实施例1-5
取化合物1(598mg,2mmol);水杨醛(1.96ml,2mmol;TsOH(1.72,mg,0.01mmol)溶于DCM(60ml)中,35℃搅拌12h,点板监测反应至原料完全反应,加碱中和,将产物水洗,萃取,干燥,旋蒸,过滤纯化得到化合物3(435mg,产率为53.8%)。取上述化合物3 (202mg,0.5mmol),加入20ml二氯甲烷溶液,1.00ml三氟化硼乙醚溶液,在电磁搅拌下,慢慢滴加1.00ml三乙胺,升高温度至35℃,回流30min,TLC点板检测,将产物水洗,萃取,干燥,旋蒸,过滤纯化得到少量金黄色固体化合物I(51.9mg,产率为23%)。相当于实施例I-4,三乙胺与三氟化硼乙醚溶液的添加顺序改变时,化合物I的产率明显下降。
实施例2化合物I对三乙胺的检测
称取化合物I(4.51mg,0.01mmol),加入1mLDCM,溶解配成0.01mol/L的母液,然后取3μL母液分别溶入3ml蒸馏水、乙醇、乙腈、二甲基亚砜中,配成10μmol/L的待测溶液,再取3μL 7.18mol/L的三乙胺溶液分别加入其中,分别检测其荧光光谱的变化。观察到荧光光谱无明显变化,化合物I在其它溶剂中对三乙胺无响应。
称取化合物I(4.51mg,0.01mmol),加入1mLDCM,溶解配成0.01mol/L的母液,然后再取2次3μL母液溶入3ml DCM中,配成2份10μmol/L的待测溶液。分别取3 μL 3.37mol/L的三氟乙酸、3μL 5mol/L的醋酸溶液分别加入其中,分别检测其荧光光谱的变化。观察到在酸性溶液中,荧光光谱无明显变化,化合物I对酸无响应。
称取化合物I(4.51mg,0.01mmol),取1mLDCM溶解配成0.01mol/L的母液,然后再取3μL母液溶入3ml DCM中,配成10μmol/L的待测溶液。前五次分别取3μL 7.18mol/L的三乙胺溶液,其后六次分别取6μL 7.18mol/L的三乙胺溶液,最后八次分别取 10μL7.18mol/L的三乙胺溶液,逐次滴加到待测溶液中,检测其荧光光谱的变化,得到图3 (图3中的曲线从上到下依次为0μmmol,21.58μmmol,43.17μmmol,64.8μmmol, 129.6μmmol,172.8μmmol,216μmmol,259.2μmmol,302.4μmmol,345.6μmmol, 388.8μmmol,460.8μmmol,532.8μmmol,604.8μmmol,676.8μmmol,748.8μmmol, 820.8μmmol,892.8μmmol,964.8μmmol)。可以观察到随着碱的量增加,荧光光谱中, 541nm的峰逐步降低趋向于0;当三乙胺的实际加入量到104μL即748μmol时,峰值变化趋于稳定。
实施例3化合物I对三乙胺的检测
称取化合物I(4.51mg,0.01mmol),取1mLDCM溶解配成0.01mol/L的母液,然后再取3 μL母液溶入3ml DCM中,配成10μmol/L的待测溶液。然后再取104μL三乙胺快速滴加到待测溶液中,在加入三乙胺后0min、0.5min、1min时检测其荧光光谱的变化,得到图 4。可以观察到在三乙胺加入后的30秒,荧光强度可降到最低,0.5min至1min后峰值变化趋于稳定。
上述的实施例仅为本发明的优选技术方案,而不应视为对于本发明的限制,本申请中的实施例及实施例中的特征在不冲突的情况下,可以相互任意组合。本发明的保护范围应以权利要求记载的技术方案,包括权利要求记载的技术方案中技术特征的等同替换方案为保护范围。即在此范围内的等同替换改进,也在本发明的保护范围之内。
Claims (7)
3.根据权利要求2所述的双氟硼结构荧光染料化合物的制备方法,其特征在于:所述步骤(1)中七元氟硼化合物1、水杨醛、对甲苯磺酸的投料摩尔比为1:1-10:0.01-1。
4.根据权利要求2所述的双氟硼结构荧光染料化合物的制备方法,其特征在于:所述的步骤(1)及步骤(3)中加热回流反应温度为35-40℃,回流2-18h。
5.根据权利要求2所述的双氟硼结构荧光染料化合物的制备方法,其特征在于:所述步骤(3)化合物3、三乙胺与三氟化硼乙醚络合物的投料摩尔比为1:1:1-100。
6.根据权利要求2所述的双氟硼结构荧光染料化合物的制备方法,其特征在于:所述步骤(3)中,投料的顺序为化合物3,二氯甲烷,三乙胺,三氟化硼乙醚。
7.根据权利要求1所述的双氟硼结构荧光染料化合物在检测DCM液体环境中三乙胺上的应用。
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