CN108546233B - 一种通过半导体光催化c-h活化制备芳基胺的方法 - Google Patents
一种通过半导体光催化c-h活化制备芳基胺的方法 Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/02—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of hydrogen atoms by amino groups
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
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Abstract
该方法通过半导体光催化C‑H活化制备芳基胺,以芳香类化合物为底物,硼氮碳为光催化剂,加入胺基源、溶剂以及碱,在氧气氛围中室温下可见光光照条件下搅拌反应48h,合成芳基胺化合物。硼氮碳(h‑BCN)是一种可见光响应的不含金属元素的半导体聚合物光催化剂,具有廉价易得、化学稳定性好、无毒无害以及合适的禁带宽度和能带位置等优点。将该催化剂用于合成芳基胺类化合物,反应过程操作简单,在可见光下进行,条件温和,催化效果好,对于目标产物的产率可达72%。本发明工艺简单,成本低,符合实际生产需要,具有较大的应用潜力。
Description
技术领域
本发明属于光催化有机合成技术领域,具体涉及一种硼氮碳光催化C-H活化合成芳基胺类化合物的方法。
背景技术
芳香胺类化合物在工业中发挥重要作用,例如,作为用于药物或农业化学产品的试剂或中间体,并在精细化学和电子化学领域的多种应用中发挥重要作用。寻找和发展绿色地制备芳基胺的新方法一直是科研工作者的研究热点。传统合成芳基胺的方法主要通过硝基的还原,Buchwald胺化、Ullman偶联以及Chan-Lam偶联制备。但往往使用芳基卤代物为底物、添加强氧化剂和以贵重金属为催化剂,存在着原子经济性以及合成成本的问题。通过C-H活化合成胺类化合物有着重要意义。而利用光催化技术实现C-H胺化更符合绿色合成化学的要求。吴骊珠课题组报道了光催化的C-H胺化反应,以吖啶盐为光催化剂,以氨气为胺源,合成了一系列芳基胺类化合物(J. Am. Chem. Soc.2016, 138, 10080)。因此,在芳基胺合成上需要一种催化剂简单易得,反应操作简便,反应条件温和以及成本低廉等的创新方法。
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半导体光催化C-H活化制备芳基胺的方法。
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10-200 m2/g,吸收带边在400-600nm,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、芳基胺化合物的制备:在反应器中,加入芳香类化合物为底物,硼氮碳光催化剂,胺基源、溶剂、氧化剂及碱,室温下用可见光光照搅拌反应48h,反应结束后用乙酸乙酯萃取,合并有机相干燥,过滤,减压浓缩得粗产物,经柱层析提纯得目标化合物,其反应方程式如下:
其中芳基为萘或者苯,胺源为氯化铵。优选地,所述的光催化剂为硼氮碳;光催化剂的加入量与底物的质量比为0.2:1;所述的氧化剂为双氧水、氧气或者过硫酸钠;碱的加入量与底物的摩尔比为1.2:1;所述的溶剂为乙腈、二氯乙烷或二甲亚砜;所述的碱为碳酸钾或氟化铯;碱的加入量为调控初始反应液pH值为8-10;所述的柱层析提纯是以石油醚与乙酸乙酯的体积比为(5~20):1的混合溶剂为洗脱液的柱层析提纯。
本发明的原理为:在可见光照下,以芳香类化合物以及铵盐为原料,在光催化剂和氧化剂的共同作用下,经历两分子氧化脱氢偶联过程一锅法合成萘胺。
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强氧化剂以及贵重金属的使用,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72%,节能环保;
(3)本发明的合成方法原子经济性高,水为唯一副产物,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为本发明的芳基胺化合物的反应方程式;
图2为本发明制得的硼氮碳光催化剂的XRD图。
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:硼氮碳化学式为h-BCN,类石墨结构(如图2所示),比表面积为10-200 m2/g,吸收带边在400-600nm,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,得到硼氮碳光催化剂。
实施例1
在反应器中,加入100 mg萘,20 mg硼氮碳光催化剂,100 mg 氯化铵为胺基源,3ml的乙腈及1.2当量的碳酸钾(调控初始反应液pH值为8-10),在氧气氛围中室温下光照搅拌反应48h,反应结束后用乙酸乙酯萃取,合并有机相干燥,过滤,减压浓缩得粗产物,所用的柱层析洗脱液为体积比为20:1的石油醚:乙酸乙酯混合溶剂,产率53%。
产物:
Naphthalen-1-amine
Colorless oil, 15.2 mg, 53% yield. 1H NMR (400 MHz, CDCl3) δ = 7.83(s, 2H), 7.48 (s, 2H), 7.30 (dd, J=17.9, 10.2, 2H), 6.80 (d, J=6.2, 1H), 4.06(s, 2H). 13C NMR (101 MHz, CDCl3) δ = 142.08, 134.39, 128.58, 126.37, 125.89,124.90, 123.65, 120.82, 119.01, 109.72. MS: 143.
实施例2
在反应器中,加入100 mg苯甲醚,20 mg硼氮碳光催化剂,100 mg 氯化铵为胺基源,3ml的二氯乙烷及1.2当量的氟化铯(调控初始反应液pH值为8-10),在氧气氛围中室温下光照搅拌反应48h,反应结束后用乙酸乙酯萃取,合并有机相干燥,过滤,减压浓缩得粗产物,所用的柱层析洗脱液为体积比为20:1的石油醚:乙酸乙酯混合溶剂,产率41%。
产物:
4-Methoxyaniline and 2-methoxyaniline
Colorless oil, 10.1 mg, 41% yield. 1H NMR (400 MHz, CDCl3) δ = 6.82 –6.71 (m, 2H), 6.66 (d, J=8.2, 2H), 3.85 (s, 1H), 3.45 (N-H, 2H). 1H NMR (400MHz, CDCl3)δ = 6.82 – 6.71 (m, 2H), 6.66 (d, J=8.2, 2H), 3.75 (s, 3H), 3.45(N-H, 2H). 13C NMR (101 MHz, CDCl3) δ = 152.79, 147.32, 139.92, 136.14,121.07, 118.50, 116.44, 115.03, 114.79, 110.40, 55.75, 55.43.
实施例3
在反应器中,加入100 mg 1,3,5-三甲氧基苯,20 mg硼氮碳光催化剂,100 mg 氯化铵为胺基源,3ml的二甲亚砜及1.2当量的氟化铯(调控初始反应液pH值为8-10),在氧气氛围中室温下光照搅拌反应48h,反应结束后用乙酸乙酯萃取,合并有机相干燥,过滤,减压浓缩得粗产物,所用的柱层析洗脱液为体积比为10:1的石油醚:乙酸乙酯混合溶剂,产率41%。
产物:
2,4,6-Trimethoxyaniline
Colorless oil, 15.0 mg, 41% yield.1H NMR (400 MHz, CDCl3) δ 6.18 (d, J= 1.7 Hz, 2H), 3.83 (s, 6H), 3.76 (s, 3H), 3.27 (s, 2H). 13C NMR (101 MHz,CDCl3) δ = 152.58, 148.08, 118.97, 91.48, 55.86.
实施例4
在反应器中,加入100 mg 2-甲氧基萘,20 mg硼氮碳光催化剂,100 mg 氯化铵为胺基源,3ml的乙腈及1.2当量的碳酸钾(调控初始反应液pH值为8-10),在氧气氛围中室温下光照搅拌反应48h,反应结束后用乙酸乙酯萃取,合并有机相干燥,过滤,减压浓缩得粗产物,所用的柱层析洗脱液为体积比为20:1的石油醚:乙酸乙酯混合溶剂,产率72%。
产物:
2-Methoxynaphthalen-1-amine
Yellow oil, 24.9 mg, 72% yield. 1H NMR (400 MHz, CDCl3) δ 7.79 (d, J =7.6 Hz, 2H), 7.45 (d, J = 5.2 Hz, 1H), 7.31 (dd, J = 36.3, 6.0 Hz, 3H), 4.20(d, J = 17.0 Hz, 1H), 4.00 (d, J = 2.2 Hz, 3H). 13C NMR (101 MHz, CDCl3) δ =142.59, 129.58, 128.41, 125.02, 123.99, 123.59, 120.33, 118.48, 113.63,56.76.
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 (8)
1.一种通过半导体光催化C-H活化制备芳基胺的方法,其特征在于:包括以下步骤:以芳香类化合物为底物,硼氮碳为光催化剂,加入胺基源、溶剂、氧化剂以及碱,在室温下可见光光照条件下搅拌反应48h,合成芳基胺化合物,其中芳基为苯环或萘环;
所述的硼氮碳化学式为h-BCN,类石墨结构,比表面积为10-200 m2/g,吸收带边在400-600nm;
所述硼氮碳光催化剂的制备方法,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,得到硼氮碳光催化剂。
2.根据权利要求1所述的制备方法,其特征在于:所述的氧化剂为双氧水、氧气、空气或过硫酸钠。
3.根据权利要求1所述的制备方法,其特征在于:所述的溶剂为乙腈、二氯乙烷或二甲亚砜。
4.根据权利要求1所述的制备方法,其特征在于:所述的碱为碳酸钾或氟化铯;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:所述的胺基源为氯化铵。
6.根据权利要求1所述的制备方法,其特征在于:硼氮碳的加入量与底物的质量比为0.2:1。
7.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,减压浓缩得粗产物,经柱层析提纯得到芳基胺化合物。
8.根据权利要求7所述的制备方法,其特征在于:所述的柱层析提纯是以石油醚与乙酸乙酯按体积比5~50:1的混合溶剂作为洗脱液的柱层析提纯。
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