CN111718245B - 一种光催化脱羧转化制备氘代化学品的方法 - Google Patents

一种光催化脱羧转化制备氘代化学品的方法 Download PDF

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CN111718245B
CN111718245B CN202010712960.6A CN202010712960A CN111718245B CN 111718245 B CN111718245 B CN 111718245B CN 202010712960 A CN202010712960 A CN 202010712960A CN 111718245 B CN111718245 B CN 111718245B
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王心晨
郑梅芳
施佳乐
袁涛
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Abstract

本发明公开了一种光催化脱羧转化制备氘代化学品的方法，包括以下步骤：羧酸类化合物在光源、催化剂共同催化作用下，与氘源进行脱羧加氘反应，得到氘代化学品；其中所述氘源为氘水、氘代醇类化合物中的一种或多种。本发明以环保、廉价的氘水或氘代试剂替代传统的氘气或复杂含氘有机物作为氘源，反应条件温和，以可见光为驱动能，整个过程绿色、简洁、高效；在光催化的作用下实现在温和的条件下对羧酸类化合物的定位氘化反应。本方法较传统的氘化反应具有更高的选择性、更温和的反应条件以及更经济适用性。

Description

一种光催化脱羧转化制备氘代化学品的方法
技术领域
本发明属于光催化有机合成技术领域，具体涉及一种光催化脱羧反应制备氘代化学品的方法。
背景技术
氘代化学品是一种关键的诊断工具，在药物分析，药理研究，医疗诊断及残留分析等研究中提供药物代谢的重要信息。此外，氘代化学品在化学的机理研究以及动力学研究等领域也有着重要应用。因此，寻找和发展绿色地制备氘代化合物的新方法一直是科研工作者的研究热点。该方法面临的巨大挑战在于氘代的选择性控制以及官能团的普适性。传统方法涉及高温、高压(氘气为氘源)、强酸、强碱或昂贵的金属催化剂。然而，由于加氘反应(或氘解反应)需要用到氘气或者其它复杂的氘代有机试剂，以及高温、高压和贵金属催化剂，大大限制了加氘反应的适用范围。该发明以简单廉价的羧酸化合物为底物，以非金属基半导体为光催化剂实现脱羧加氘反应，具有更普适的官能团兼容性和更高的化学选择性，实现合成定点氘化产物，可作为较理想的制备含氘化合物的策略。
因此，现有技术还有待于改进和发展。
发明内容
为了解决以上现有技术的缺点和不足之处，本发明的目的在于提供一种通过非金属基半导体光催化脱羧加氢制备氘代化学品的方法。
本发明目的通过以下技术方案实现，包括以下步骤：
1、光催化剂硼氮碳的合成：硼氮碳化学式为h-BCN，类石墨结构，比表面积为300-400 m2/g，吸收带边在400-600 nm，包括以下步骤：
（1）将前驱体葡萄糖、尿素以及硼酸研磨混合均匀；
（2）将步骤（1）得到的固体粉末在氨气气氛下1000~1200℃煅烧，得到硼氮碳光催化剂。
2、氘代化学品的制备：在反应器中，加入羧酸类化合物为底物，六方相硼氮碳为光催化剂，加入氘源、溶剂以及碱，通入氮气保护，在室温下可见光光照条件下搅拌反应48 h，合成氘代化学品。反应结束后用乙酸乙酯萃取，合并有机相干燥，过滤，减压浓缩得最终产物，其反应方程式如下：
Figure 270428DEST_PATH_IMAGE002
其中芳基为苯环或吡啶环。优选地，所述的光催化剂为六方硼氮碳；光催化剂的加入量与底物的质量比为0.2:1；所述的氘源为氘代水或氘代甲醇；碱的加入量与底物的摩尔比为0.2:1；所述的溶剂为乙腈、二氯乙烷或无需溶剂；所述的碱为碳酸钾或碳酸钠；碱的加入量为调控初始反应液pH值为8-10。
本发明的原理为：在可见光光照下，羧酸类化合物脱羧得到碳自由基，再攫取氘源中的氘定位高选择性得到氘代产物。
本发明的制备方法具有如下优点及有益效果：
（1）本发明的合成方法避免了贵重金属以及其它有机氘源的使用，减少了其所带来的副产物，方法简单易行，条件温和，操作安全；
（2）本发明的合成方法无需加热，在室温可见光照下就能得到较高的收率，收率可达87%，节能环保；
（3）本发明的合成方法步骤经济性高，无需分离提纯，反应条件温和，具有良好的工业应用前景。
（4）催化剂简单易得，且可重复使用。
附图说明
图1为本发明的羧酸化合物的光催化脱羧反应方程式；
图2为本发明制得的六方硼氮碳光催化剂的比表面积图（A）和紫外-可见吸收光谱图（B）。
具体实施方式
下面结合实施例及附图对本发明作进一步详细的描述，但本发明的实施方式不限于此。
光催化剂硼氮碳的合成：六方相硼氮碳化学式为h-BCN，类石墨结构，比表面积为339 m2/g（如图2A所示），吸收带边在400-600nm（如图2B所示），包括以下步骤：
（1）将前驱体葡萄糖、尿素以及硼酸按质量比1:2:1研磨混合均匀；
（2）将步骤（1）得到的固体粉末在氨气气氛下1200℃煅烧，得到硼氮碳光催化剂。
实施例1
在反应器中，加入0.2 mmol 1,3-二甲氧基苯甲酸，30 mg上述制备的硼氮碳光催化剂，6 mL 氘代甲醇，及0.2当量的碳酸钾（调控初始反应液pH值为9），在氮气氛围中室温下光照搅拌反应48 h，反应结束后用乙酸乙酯萃取，合并有机相干燥，过滤，减压浓缩得目标产物，氘代收率50%。
产物：
Figure 656410DEST_PATH_IMAGE004
3,5-Dimethoxybenzene-d (2a-D)
14 mg, 50% yield. 1H NMR (400 MHz, CDCl3) δ = 7.20 (t, J=8.2, 0.08H),6.60 – 6.44 (m, 3H), 3.80 (s, 6H). 13C NMR (101 MHz, CDCl3) δ = 160.90,129.86, 106.10, 100.50, 55.27. MS (m/z, EI): 53, 79, 110,139 (100).
实施例2
在反应器中，加入0.2 mmol 3,4,5-二甲氧基苯乙酸，30 mg上述制备的硼氮碳光催化剂，6 mL 氘代甲醇，及0.2当量的碳酸钾（调控初始反应液pH值为9），在氮气氛围中室温下光照搅拌反应48 h，反应结束后用乙酸乙酯萃取，合并有机相干燥，过滤，减压浓缩得目标产物，氘代收率87%。
产物：
Figure 170568DEST_PATH_IMAGE006
1,2,3-Trimethoxy-5-(methyl-d)benzene (2b-D)
32 mg, 87% yield. 1H NMR (400 MHz, CDCl3) δ = 6.39 (s, 2H), 3.83 (s,6H), 3.81 (s, 3H), 2.29 (s, 2.02H). 13C NMR (101 MHz, CDCl3) δ = 153.02,135.82, 133.54, 105.98, 60.86, 56.01, 21.75, 21.56, 21.36. MS (m/z, EI): 54,108, 140, 168, 183 (100).
实施例3
在反应器中，加入0.2 mmol 2,3-二苯基丙酸，30 mg上述制备的硼氮碳光催化剂，6 mL 氘代甲醇，及0.2当量的碳酸钾（调控初始反应液pH值为9），在氮气氛围中室温下光照搅拌反应48 h，反应结束后用乙酸乙酯萃取，合并有机相干燥，过滤，减压浓缩得目标产物，氘代收率60%。
产物：
Figure 34619DEST_PATH_IMAGE008
(Ethane-1,2-diyl-1-d)dibenzene (2c-D)[14]
21.9 mg, 60% yield. 1H NMR (400 MHz, CDCl3) δ = 7.33 – 7.17 (m, 10H),2.93 (s, 3.02H). 13C NMR (101 MHz, CDCl3) δ = 141.80, 128.47, 128.35, 125.93,37.89. MS (m/z, EI): 65, 92 (100), 116, 166, 183.
实施例4
在反应器中，加入0.2 mmol 5-(甲氧羰基)-2-吡啶羧酸，30 mg上述制备的硼氮碳光催化剂，6 mL 氘代甲醇，及0.2当量的碳酸钾（调控初始反应液pH值为9），在氮气氛围中室温下光照搅拌反应48 h，反应结束后用乙酸乙酯萃取，合并有机相干燥，过滤，减压浓缩得目标产物，氘代收率60%。
产物：
Figure 521095DEST_PATH_IMAGE010
3-Pyridine-6-d-carboxylic acid, methyl ester (2d-D)
16.6 mg, 60% yield. 1H NMR (400 MHz, CDCl3) δ = 9.19 (s, 1H), 8.75 (s,0.14H), 8.31 – 8.24 (m, 1H), 7.37 (d, J=7.7, 1H), 3.93 (s, 3H). 13C NMR (101MHz, CDCl3) δ = 165.74, 153.37, 150.87, 137.09, 126.08, 123.17, 52.41. MS (m/z, EI): 51, 79, 107 (100), 138.
以上所述仅为本发明的较佳实施例，凡依本发明申请专利范围所做的均等变化与修饰，皆应属本发明的涵盖范围。

Claims (6)

1.一种光催化脱羧转化制备氘代化学品的方法，其特征在于：包括以下步骤：以羧酸类化合物为底物，六方相硼氮碳为光催化剂，加入氘源以及碱，通入氮气保护，在室温下可见光光照条件下搅拌反应48 h，合成氘代化学品；
所述六方相硼氮碳为类石墨结构，比表面积为300-400 m2/g，吸收带边在400-600nm；所述六方相硼氮碳的制备方法包括以下步骤：
（1）将前驱体葡萄糖、尿素以及硼酸按质量比1:2:1研磨混合均匀；
（2）将步骤（1）得到的固体粉末在氨气气氛下1000~1200℃煅烧，得到六方相硼氮碳。
2.根据权利要求1所述的制备方法，其特征在于：所述氘源为氘水、氘代醇类化合物中的一种或多种。
3.根据权利要求1所述的制备方法，其特征在于：还加入了非质子性溶剂。
4.根据权利要求1所述的制备方法，其特征在于：所述碱为碳酸钾或碳酸钠；碱的加入量为调控初始反应液pH值为8-10。
5.根据权利要求1所述的制备方法，其特征在于：六方相硼氮碳的加入量与羧酸类化合物的质量比为0.2:1。
6.根据权利要求1所述的制备方法，其特征在于：反应步骤还包括，反应结束后用乙酸乙酯萃取，合并有机相干燥，过滤，减压浓缩得氘代化合物，无需柱层析分离提纯。
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