CN109975254B - 一种蒽醌衍生物的制备方法 - Google Patents
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Abstract
本发明公开了一种蒽醌衍生物的用途，属于荧光检测领域。该方法是通过化合物Ⅰ在氧化剂的作用下进行氧化反应，制备得到化合物Ⅱ；在酸性环境下，化合物Ⅱ与乙醇进行酯化反应，得到化合物Ⅲ；在加热回流的条件下，化合物Ⅲ与水合肼进行反应，得到化合物Ⅳ；在惰性气体保护的环境下，化合物Ⅳ与异硫氰酸苯酯进行反应，得到化合物Ⅴ。本发明所提供的制备方法简单，易于工业化生产。且制备得到的多信号探针对汞离子的检出限低且选择性高。
Description
本申请是申请日为：2017-12-27、申请号为：2017114392079、名称为：一种蒽醌衍生物及合成方法和应用的发明专利的分案申请。
技术领域
本发明涉及荧光检测领域，具体涉及一种蒽醌衍生物的用途。
背景技术
工业污染导致Hg2+在环境中的污染已经变得十分普遍。Hg2+是具有严重生理毒性的过渡金属离子之一，一旦进入到海洋中，无机的Hg2+会在细菌的作用下转变为危害更大的甲基汞并进入到食物链中，甲基汞对人体的危害十分显著，它能轻易的被人体吸收并突破人体的血脑屏障，然后直接作用于我们的中枢神经系统，对人体造成巨大伤害。因此，开发和研究新型的汞离子及汞化合物检测方法有着重要的意义。
发明内容
本发明的目的可以通过以下技术方案实现：
一种蒽醌衍生物，该衍生物的结构式如下所示：
一种上述的蒽醌衍生物的制备方法，该方法反应路线如下：
上述制备方法包括以下步骤：
1)化合物Ⅰ在氧化剂的作用下进行氧化反应，制备得到化合物Ⅱ；
2)在酸性环境下，化合物Ⅱ与乙醇进行酯化反应，得到化合物Ⅲ；
3)在加热回流的条件下，化合物Ⅲ与水合肼进行反应，得到化合物Ⅳ；
4)在惰性气体保护的环境下，化合物Ⅳ与异硫氰酸苯酯进行反应，得到化合物Ⅴ。
本发明技术方案中：步骤1)中所述的氧化即为三氧化铬、高锰酸钾或次氯酸钠；氧化反应所用的溶剂为乙醇或冰醋酸。
本发明技术方案中：步骤2)中酸性环境所用的酸性试剂为为硫酸、磷酸或者硼酸，酯化反应的温度为加热回流温度。
本发明技术方案中：步骤3)反应所用的溶剂为甲醇、乙醇或乙腈。
本发明技术方案中：步骤4)反应的温度为0～100℃，反应所用的溶剂为甲醇、乙醇、乙腈或二氯甲烷。
本发明技术方案中：所述的蒽醌衍生物作为检测汞离子的应用。
本发明技术方案中：所述的蒽醌衍生物在环境中作为检测汞离子的应用。
本发明的有益效果：
本发明所提供的制备方法简单，易于工业化生产。且制备得到的多信号探针对汞离子的检出限低且选择性高。
附图说明
图1是探针分子ddpb对Hg2+的选择性吸收光谱识别。
图2为Hg2+对探针分子ddpb的吸收光谱滴定图。
图3是探针分子ddpb对Hg2+的选择性荧光光谱识别。
图4为Hg2+对探针分子ddpb的荧光光谱滴定图。
图5为Hg2+与探针分子ddpb反应时间对溶液荧光强度的影响图。
图6为当溶液中有其它共存金属离子时对探针ddpb选择性识别Hg2+的影响图。
图7为Hg2+浓度与荧光强度的线性关系图。
具体实施方式
下面结合实施例对本发明做进一步说明，但本发明的保护范围不限于此：
实施例1
在100mL冰醋酸中加入1,4-二甲基蒽醌(10mmol，2.36g)和三氧化铬(100mmol，10g)，在搅拌的条件下加热回流10小时。反应结束后冷却至室温，抽滤，将所得固体产物溶于10％的热氢氧化钠溶液中，趁热过滤，所得滤液冷却后用浓盐酸调节溶液pH值到 2左右，抽滤，所得固体用丙酮洗涤，真空干燥，得淡黄色化合物Ⅱ2.77g，产率：93.6％，纯度：99.54％。
元素分析：(％)for C16H8O6:计算值：C 64.87；H 2.72，实测值：C 65.18；H 2.85。
IR(KBr),ν,cm-1:3088,1780,1693,1674,1588,1373,1286,1257,1203,897,814,747,683。
1H NMR(500MHz,CDCl3,TMS):δ＝7.81(d,J＝6.8,2H),8.34(d,J＝6.8,2H),8.19(s,2H), 12.97(s,2H)ppm.
在100mL无水乙醇中加入化合物Ⅱ(10mmol，2.96g)和5mL浓硫酸，加热回流6 小时。反应结束后，旋转蒸干乙醇，所得固体依次用5％的碳酸钠溶液、水洗至中性，再用丙酮洗，真空干燥，得黄色化合物Ⅲ3.37g，产率：95.6％，纯度：99.28％。
元素分析：(％)for C20H16O6:计算值：C 68.18；H 4.58，实测值：C 68.73；H4.37。
IR(KBr),ν,cm-1:3072,1732,1691,1578,1532,1497,1217,1138,961,819,767。
1H NMR(500MHz,CDCl3,TMS):δ＝1.33(t,J＝7.0,6H),4.36(q,J＝7.0,4H),7.83(d,J＝6.8,2H), 8.32(d,J＝6.8,2H),8.57(s,2H).
在100mL无水乙醇中加入化合物Ⅲ(10mmol，3.52g)，在加热回流的条件下用恒压漏斗缓慢的滴加10mL水合肼，滴加完成后继续反应6小时。反应结束后冷却至室温，将反应液倒入100mL的水中，然后用乙酸乙酯萃取(50mL×3)，合并有机相，无水硫酸镁干燥过夜，过滤，旋转蒸干溶剂后得黄色化合物Ⅳ3.07g，产率：94.7％，纯度：99.19％。元素分析：(％)for C16H12N4O4:计算值：C 59.26；H 3.73；N 17.28，实测值：C 59.17；H 3.41； N 17.46。
IR(KBr),ν,cm-1:3378,3284,3068,1697,1688,1642,1516,1482,1286,1329,1157,932,827,715,674 1H NMR(500MHz,CDCl3,TMS):δ＝3.87(d,J＝7.2,4H),7.71(d,J＝7.0,2H),8.12(d,J＝6.8,2H), 8.38(d,J＝6.8,2H),10.51(br,2H).
在通入N2保护的条件下，在100mL无水乙腈中加入化合物Ⅳ(10mmol，3.24g)和异硫氰酸苯酯(22mmol，2.97g)，在室温下反应24小时。反应结束后旋转蒸干溶剂，将所得固体产物过硅胶柱(乙酸乙酯:己烷＝1:3)，旋转蒸除溶剂的橘黄色化合物Ⅴ(ddpb) 5.53g，产率：93.1％，纯度：99.47％。
元素分析：(％)for C30H22N6O4S2:计算值：C 60.59；H 3.73；N 14.13，实测值：C61.13；H 3.84；N 13.91。
IR(KBr),ν,cm-1:3267,3216,3011,1721,1683,1632,1421,1207,1189,1157,878,704,682。
1H NMR(500MHz,CDCl3,TMS):δ＝3.67-3.71(m,4H),4.38(s,2H),6.95-7.03(m,6H),7.16(d, J＝6.8,4H),7.82(d,J＝6.8,2H),8.03(d,J＝6.8,2H),8.33(d,J＝6.8,2H).
实施例2
在100mL50％的乙醇溶液中加入1,4-二甲基蒽醌(10mmol，2.36g)和高锰酸钾(100mmol，15.8g)，在搅拌的条件下加热回流12小时。反应结束后冷却至室温，抽滤，将所得固体产物溶于10％的热氢氧化钠溶液中，趁热过滤，所得滤液冷却后用浓盐酸调节溶液pH值到2左右，抽滤，所得固体用丙酮洗涤，真空干燥，得淡黄色化合物Ⅱ2.64g，产率：89.1％，纯度：99.17％。
在100mL无水乙醇中加入化合物Ⅱ(10mmol，2.96g)和5mL磷酸，加热回流8小时。反应结束后，旋转蒸干乙醇，所得固体依次用5％的碳酸钠溶液、水洗至中性，再用丙酮洗，真空干燥，得黄色化合物Ⅲ3.24g，产率：92.1％，纯度：98.17％。
在100mL无水甲醇中加入化合物Ⅲ(10mmol，3.52g)，在加热回流的条件下用恒压漏斗缓慢的滴加15mL水合肼，滴加完成后继续反应8小时。反应结束后冷却至室温，将反应液倒入100mL的水中，然后用乙酸乙酯萃取(50mL×3)，合并有机相，无水硫酸镁干燥过夜，过滤，旋转蒸干溶剂后得黄色化合物Ⅳ3.01g，产率：92.8％，纯度：99.17％。
在通入N2保护的条件下，在100mL无水乙醇中加入化合物Ⅳ(10mmol，3.24g)和异硫氰酸苯酯(25mmol，3.38g)，在室温下反应30小时。反应结束后旋转蒸干溶剂，将所得固体产物过硅胶柱(乙酸乙酯:己烷＝1:3)，旋转蒸除溶剂的橘黄色化合物Ⅴ(ddpb) 5.37g，产率：90.3％，纯度：98.16％。
实施例3
在100mL50％的乙醇溶液中加入1,4-二甲基蒽醌(10mmol，2.36g)，加热回流搅拌。然后用恒压漏斗缓慢滴加300mL 10％的次氯酸钠溶液。溶液滴加完成后继续在搅拌的条件下加热回流15小时。反应结束后冷却至室温，用浓盐酸调节溶液pH值到2左右，抽滤，所得固体用丙酮洗涤，真空干燥，得淡黄色化合物Ⅱ2.51g，产率：84.7％，纯度： 98.12％。
在100mL无水乙醇中加入化合物Ⅱ(10mmol，2.96g)和5mL硼酸，加热回流10小时。反应结束后，旋转蒸干乙醇，所得固体依次用5％的碳酸钠溶液、水洗至中性，再用丙酮洗，真空干燥，得黄色化合物Ⅲ3.15g，产率：89.4％，纯度：99.26％。
在100mL无水乙腈中加入化合物Ⅲ(10mmol，3.52g)，在加热回流的条件下用恒压漏斗缓慢的滴加20mL水合肼，滴加完成后继续反应10小时。反应结束后冷却至室温，将反应液倒入100mL的水中，然后用乙酸乙酯萃取(50mL×3)，合并有机相，无水硫酸镁干燥过夜，过滤，旋转蒸干溶剂后得黄色化合物Ⅳ2.94g，产率：90.6％，纯度：99.09％。
在通入N2保护的条件下，在100mL二氯甲烷中加入化合物Ⅳ(10mmol，3.24g)和异硫氰酸苯酯(30mmol，4.06g)，在室温下反应48小时。反应结束后旋转蒸干溶剂，将所得固体产物过硅胶柱(乙酸乙酯:己烷＝1:3)，旋转蒸除溶剂的橘黄色化合物Ⅴ(ddpb) 5.29g，产率：89.0％，纯度：98.16％。
性质部分
1、吸收光谱实验
蒽醌衍生物ddpb对Hg2+的吸收光谱识别
图1是探针分子ddpb对Hg2+的选择性吸收光谱识别。在10mL浓度为0.1mmol/L探针分子ddpb溶液中分别加入10μL浓度为0.2mol/L(2倍摩尔量)的金属离子溶液(Al3+、 Ag+、Na+、Ca2+、Cd2+、Hg2+、Mg2+、Co2+、K+、Cu2+、Ni2+、Pb2+、Zn2+)。实验中所使用的溶液体系均为乙腈/水(1:1，v:v)的混合溶液，吸收光谱在岛津UV-2450型紫外分光光度计上测定。
由图1可以看出探针分子在乙腈/水(1:1，v:v)的混合溶液中自身的吸收在510nm左右，当我们向探针分子溶液中加入过量的金属离子后，我们发现只有在加入Hg2+后，溶液的吸收蓝移至465nm左右，溶液的颜色也由紫色变为黄色，而当在探针分子溶液中加入其它金属离子时，则没有这一现象的发生，这说明该探针分子的吸收光谱对Hg2+有着独特的响应。
图2为Hg2+对探针分子ddpb的吸收光谱滴定图。在10mL浓度为0.1mmol/L探针FcL溶液中依次加入0.2、0.4、0.6、0.8、1.0、1.2、1.4、1.6、1.8、2.0、2.5、3.0倍摩尔量的 Hg2+。实验中所使用的溶液体系均为乙腈/水(1:1，v:v)的混合溶液，吸收光谱在岛津 UV-2450型紫外分光光度计上测定。由图2可以看出，随着Hg2+的加入，溶液的吸收波长逐渐由510nm蓝移至465nm，当Hg2+加入量达到探针分子2倍摩尔量后，溶液的吸收波长不再移动，且峰的强度基本不变。这说明探针分子ddpb与Hg2+是1:2配位的。
2、荧光光谱实验
蒽醌衍生物ddpb对Hg2+的荧光识别
图3是探针分子ddpb对Hg2+的选择性荧光光谱识别。将探针分子ddpb溶于乙腈/水(1:1，v:v)的混合溶液中，配制成浓度为10μmol/L的溶液，在此溶液中分别加入2倍摩尔量的金属离子(Al3+、Ag+、Na+、Ca2+、Cd2+、Hg2+、Mg2+、Co2+、K+、Cu2+、Ni2+、 Pb2+、Zn2+)。激发波长为470nm，测定溶液的荧光光谱。从图3中可以看出，探针分子溶液在525nm处有一个弱荧光发射峰，在加入Hg2+后，溶液在525nm处弱荧光发射峰消失，而在582nm处出现一个很强的荧光发射峰，而加入其它金属离子则没有这一现象，这说明该探针分子对Hg2+表现出非常强的荧光选择识别性。实验中所使用的溶液体系均为乙腈 /水(1:1，v:v)的混合溶液，荧光光谱在AMINCO Bowman Series 2荧光光谱仪上测得。
图4为Hg2+对探针分子ddpb的荧光光谱滴定图。在10μmol/L的探针分子ddpb的乙腈/ 水(1:1，v:v)的混合溶液中，分别加入0.2、0.4、0.6、0.8、1.0、1.2、1.4、1.6、1.8、 2.0、2.5、3.0倍摩尔量的Hg2+。在470nm处激发，测量溶液的发射光谱，如图所示随着 Hg2+的浓度增加，525nm处弱荧光发射峰逐渐减弱最终消失，而在582nm处出现一个新的荧光发射峰，并且在Hg2+加入量达到2倍摩尔量后582nm处的发射峰强度基本不再增加。
图5为Hg2+与探针分子ddpb反应时间对溶液荧光强度的影响图。在10μmol/L的探针分子ddpb的乙腈/水(1:1，v:v)的混合溶液中，加入2倍摩尔量的Hg2+。在激发波长470nm，发射波长525nm处，分别在0、1、2、3、4、5、6、7、8分钟时记录溶液的荧光强度。如图所示，在探针分子ddpb溶液中加入Hg2+5分钟后，荧光强度达到最大值，且随着时间延长基本保持不变。
图6为当溶液中有其它共存金属离子时对探针ddpb选择性识别Hg2+的影响图。在10μmol/L的探针分子ddpb的乙腈/水(1:1，v:v)的混合溶液中，分别加入溶有10倍摩尔量的金属离子(Al3+、Ag+、Na+、Ca2+、Cd2+、Hg2+、Mg2+、Co2+、K+、Cu2+、Ni2+、Pb2+、 Zn2+)，在激发波长470nm，发射波长525nm处，测量溶液的荧光强度，然后再在上述溶液中加入10倍摩尔量的Hg2+，在激发波长470nm，发射波长525nm处，测量溶液的荧光强度，从图6中可以看出，当溶液中大量存在其他金属离子时，探针分子ddpb对Hg2+的选择性识别并不受影响。
图7为Hg2+浓度与荧光强度的线性关系图。在1μmol/L的探针分子ddpb的乙腈/水(1:1， v:v)的混合溶液中，分别加入0.1、0.2、0.3、0.4、0.5、0.6、0.7、0.8倍摩尔量的Hg2+在激发波长470nm，发射波长525nm处，测量溶液的荧光强度。从图中可以看出当Hg2+浓度在0.1-0.8μmol/L范围内呈现出良好的线性关系(R2＝0.9963)，使用3σIUPAC标准计算所得的检测限为2.45×10-8mol/L。
Claims (1)
1.一种式V所示的蒽醌衍生物的制备方法，其特征在于：所述的制备方法如下：
1)化合物Ⅰ在氧化剂的作用下进行氧化反应，制备得到化合物Ⅱ；所述的氧化剂为三氧化铬、高锰酸钾或次氯酸钠；氧化反应所用的溶剂为乙醇或冰醋酸；
2)在酸性环境下，化合物Ⅱ与乙醇进行酯化反应，得到化合物Ⅲ；所述的酸性环境所用的酸性试剂为硫酸、磷酸或者硼酸，酯化反应的温度为加热回流温度；
3)在加热回流的条件下，化合物Ⅲ与水合肼进行反应，得到化合物Ⅳ；本步骤中反应所用的溶剂为甲醇、乙醇或乙腈；
4)在惰性气体保护的环境下，化合物Ⅳ与异硫氰酸苯酯进行反应，得到化合物Ⅴ；本步骤中反应的温度为0～100℃，反应所用的溶剂为乙醇、乙腈或二氯甲烷。
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102675164A (zh) * | 2011-03-09 | 2012-09-19 | 同济大学 | 齐聚磺化氨基蒽醌超敏铅离子荧光探针及其制备与应用 |
| KR20140078465A (ko) * | 2012-12-17 | 2014-06-25 | 경북대학교 산학협력단 | 1,2-디아미노안트라퀴논을 이용하여 수은 이온을 검출하는 방법 |
| CN106045878A (zh) * | 2016-05-12 | 2016-10-26 | 山西大学 | 一种蒽醌衍生物及其合成方法和在检测Cu2+中的应用 |
| CN108164448B (zh) * | 2017-12-27 | 2018-10-09 | 南京晓庄学院 | 一种蒽醌衍生物及合成方法和应用 |
Non-Patent Citations (1)
| Title |
|---|
| 一种新型耐尔蓝衍生物的合成及其对Hg2+识别研究;徐鉴;《化学试剂》;20150228;第37卷(第2期);全文 * |
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| Publication number | Publication date |
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| CN109975254A (zh) | 2019-07-05 |
| CN108164448B (zh) | 2018-10-09 |
| CN108164448A (zh) | 2018-06-15 |
| CN109096166A (zh) | 2018-12-28 |
| CN109096166B (zh) | 2020-02-14 |
| CN108912025A (zh) | 2018-11-30 |
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