CN115232013A - 一种芳香胺类化合物的制备方法 - Google Patents
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- 238000000034 method Methods 0.000 claims abstract description 19
- 238000006722 reduction reaction Methods 0.000 claims abstract description 13
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- VBXDEEVJTYBRJJ-UHFFFAOYSA-N diboronic acid Chemical group OBOBO VBXDEEVJTYBRJJ-UHFFFAOYSA-N 0.000 claims abstract description 7
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- 229910052799 carbon Inorganic materials 0.000 claims abstract description 3
- 125000005245 nitryl group Chemical group [N+](=O)([O-])* 0.000 claims abstract description 3
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- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
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- BMIBJCFFZPYJHF-UHFFFAOYSA-N 2-methoxy-5-methyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine Chemical compound COC1=NC=C(C)C=C1B1OC(C)(C)C(C)(C)O1 BMIBJCFFZPYJHF-UHFFFAOYSA-N 0.000 description 1
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- 229910052736 halogen Inorganic materials 0.000 description 1
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- 150000002431 hydrogen Chemical class 0.000 description 1
- QLNAVQRIWDRPHA-UHFFFAOYSA-N iminophosphane Chemical compound P=N QLNAVQRIWDRPHA-UHFFFAOYSA-N 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
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- 238000004519 manufacturing process Methods 0.000 description 1
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- 150000003141 primary amines Chemical class 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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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
- C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
- C07C209/42—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitrogen-to-nitrogen bonds
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- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B43/00—Formation or introduction of functional groups containing nitrogen
- C07B43/04—Formation or introduction of functional groups containing nitrogen of amino groups
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- 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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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C221/00—Preparation of compounds containing amino groups and doubly-bound oxygen atoms bound to the same carbon skeleton
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/04—Formation of amino groups in compounds containing carboxyl groups
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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- C07C259/04—Compounds containing carboxyl groups, an oxygen atom of a carboxyl group being replaced by a nitrogen atom, this nitrogen atom being further bound to an oxygen atom and not being part of nitro or nitroso groups without replacement of the other oxygen atom of the carboxyl group, e.g. hydroxamic acids
- C07C259/10—Compounds containing carboxyl groups, an oxygen atom of a carboxyl group being replaced by a nitrogen atom, this nitrogen atom being further bound to an oxygen atom and not being part of nitro or nitroso groups without replacement of the other oxygen atom of the carboxyl group, e.g. hydroxamic acids having carbon atoms of hydroxamic groups bound to carbon atoms of six-membered aromatic rings
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- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/72—Nitrogen atoms
- C07D213/73—Unsubstituted amino or imino radicals
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- C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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- C07D295/16—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms
- C07D295/18—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms by radicals derived from carboxylic acids, or sulfur or nitrogen analogues thereof
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Abstract
本发明提供了一种芳香胺类化合物的制备方法，属于有机合成技术领域。本发明的芳香胺类化合物的制备方法，包括以下步骤：将式(1)所示的芳香基叠氮类化合物在铜盐催化剂和还原剂存在的条件下于溶剂中进行还原反应，生成式(2)所示的芳香胺类化合物；
式(1)和式(2)中，R1、R2各自独立地选自H、烷基、卤代基、醚类基团、胺基、硝基、氰基、羧基、酯基、酰胺基、芳香基中的一种，X选自碳或氮；所述还原剂为联硼酸和/或联硼酸酯。本发明采用联硼酸和/或联硼酸酯作为还原剂，通过铜盐催化剂进行催化，无需贵重金属，反应条件温和，且反应效率高、时间短，有利于工业推广应用。
Description
技术领域
本发明属于有机合成技术领域，具体涉及一种芳香胺类化合物的制备方法。
背景技术
芳香胺类化合物具有多种化学药物，例如具有解热镇痛功能的扑热息痛，治疗前列腺癌的比卡鲁胺，有麻醉作用的苯佐卡因等。并且芳香胺类化合物作为一类重要的有机化学品，也被广泛应用于染料、农药、阻燃剂、聚合物等科研生产领域。
目前芳香胺类化合物可采用芳基叠氮类化合物进行选择性还原制备，现有技术中将芳基叠氮类化合物还原为芳香胺类化合物的方法有很多，常见的有以下几种：
(1)Staudinger还原叠氮基的反应，主要利用三取代膦试剂与叠氮基生成叠氮膦，释放氮气得到亚氨基膦中间体，而后水解得到伯胺。此方法条件温和，操作简便，但是会生成大量膦氧化副产物，不利于胺产物的分离纯化。
(2)催化氢化还原叠氮基，包括金属催化加氢和催化氢转移还原两种体系。催化氢化效率高，但是反应选择性较差，对一些分子中含卤素的底物，在还原时容易发生脱卤副反应。
(3)低价金属参与的叠氮基还原，包括金属铟参与的还原体系，水合硫酸铁还原体系。此体系条件温和，但是需要超当量的金属试剂加入，氨水的使用也在一定程度上限制了其应用范围。
(4)硼氢化物还原叠氮基的反应，有NaBH4/Ni(AcO)2体系，Zn(BH4)2体系等都可实现叠氮的还原，但其催化剂使用量较大，反应效率低。
因此，已有的将芳基叠氮类化合物还原为芳香胺类化合物的方法，针对不同的底物，反应效率低、时间长；在有些金属催化加氢反应中，需要用到贵金属催化剂、易燃易爆气体和高温高压装置，对反应条件要求较高，不利于降低成本。
发明内容
本发明的目的在于提供一种芳香胺类化合物的制备方法，具有反应效率高、条件要求低、成本低的优点。
本发明的芳香胺类化合物的制备方法，所采用的方案如下：
一种芳香胺类化合物的制备方法，包括以下步骤：将式(1)所示的芳香基叠氮类化合物在铜盐催化剂和还原剂存在的条件下于溶剂中进行还原反应，生成式(2)所示的芳香胺类化合物；
式(1)和式(2)中，R1、R2各自独立地选自H、烷基、卤代基、醚类基团、胺基、硝基、氰基、羧基、酯基、酰胺基、芳香基中的一种，X选自碳或氮；所述还原剂为联硼酸和/或联硼酸酯。
本发明的芳香胺类化合物的制备方法采用联硼酸(B2(OH)4，即
)和/或联硼酸酯作为还原剂，通过铜盐催化剂进行催化，无需贵重金属，反应条件温和，且反应效率高、时间短，有利于工业推广应用。
优选地，所述联硼酸酯为联硼酸频哪醇酯(B2pin2)，结构如下式a所示。
优选地，所述卤代基选自-F、-Cl、-Br、-I中的一种。
优选地，所述芳香胺类化合物包括以下2a～2y所示的芳香胺类化合物。
优选地，所述铜盐催化剂选自醋酸铜、硫酸铜、溴化铜的一种或任意组合。采用价廉、易得的铜盐催化剂，催化芳香基叠氮类化合物还原为芳香胺类化合物，有利于进一步降低成本。
优选地，所述铜盐催化剂的摩尔量为芳香基叠氮类化合物摩尔量的1～10％。
优选地，所述溶剂为醇类水溶液，醇类选自甲醇、乙醇、丙醇中的一种或任意组合。本发明将芳基叠氮类化合物溶解在醇类水溶液中反应，无需有机溶剂，有利于反应产物从反应体系中的分离，使反应产物达到较高的纯度，无需柱层析处理纯度即可达到＞90％。
优选地，所述醇类水溶液中醇与水的体积比为(1～10):1，例如醇与水的体积比为5:1。
优选地，所述还原反应的温度为20～50℃，反应时间为10～60min。
进一步地，所述反应温度为30～50℃，例如为40℃。
优选地，所述还原剂的摩尔量为芳香基叠氮类化合物摩尔量的1～3倍。
优选地，反应结束后，还包括将反应体系除酸后采用有机溶剂进行萃取，然后纯化。
优选地，所述除酸为向反应体系中加入碱性溶液。
进一步地，所述碱性溶液为碱金属氢氧化物的水溶液，例如氢氧化钠溶液。
优选地，所述萃取用有机溶剂为酯类溶剂，例如乙酸乙酯。
优选地，萃取后还包括将得到的有机萃取相采用饱和食盐水进行洗涤。
优选地，所述纯化为将有机萃取相进行干燥、浓缩。
进一步地，所述干燥为向有机萃取相中加入干燥剂，所述干燥剂为无水硫酸镁。
具体实施方式
下面结合具体实施例对本发明的实施方式作进一步说明。以下实施例或对比例涉及的原料均为常规市售产品。
实施例1
本实施例的芳香胺类化合物的制备方法，用于制备4-溴苯胺，反应流程如下：
包括以下步骤：
将1-叠氮基-4-溴苯(1.0mmol)、联硼酸(B2(OH)4)(1.5mmol)和醋酸铜(1mol％)，依次加入到带有磁子的20mL玻璃封管反应器中。然后，向反应器中加入3mL的甲醇/水(体积比为5:1)，用四氟塞密封后，将反应器直接置于40℃油浴中加热，反应在10min内结束。然后，将反应液移出油浴，冷至室温，加入2mL氢氧化钠水溶液(1N)，搅拌5min，用乙酸乙酯(10mL*2)萃取，合并有机相，采用饱和食盐水进行洗涤。然后向有机相中加入无水硫酸镁干燥，浓缩，所得到的苯胺化合物，收率为92％，纯度为99％。
实施例2
本实施例的芳香胺类化合物的制备方法，用于制备4-溴苯胺，反应流程如下：
包括以下步骤：
将1-叠氮基-4-溴苯(1.0mmol)、联硼酯(B2pin2)(1.3mmol)和醋酸铜(1mol％)，依次加入到带有磁子的20mL玻璃封管反应器中。然后，加入3mL的甲醇/水(体积比为5:1)，用四氟塞密封后，将反应器直接置于40℃油浴中加热，反应在10min内结束。然后，将反应液移出油浴，冷至室温，加入2mL氢氧化钠水溶液(1N)，搅拌5min，用乙酸乙酯(10mL*2)萃取，合并有机相，采用饱和食盐水进行洗涤。无水硫酸镁干燥，浓缩，所得到的苯胺化合物，纯度为99％。
实施例3～26
实施例3～26的芳香胺类化合物的制备方法，与实施例1相比，仅改变了芳基叠氮底物和还原剂，制备工艺和相关实验结果如表1所示。
表1 实施例3～26的芳香胺类化合物的制备工艺与相关实验结果
实施例1～26的实验结果显示，在本发明的反应体系中联硼酸(B2(OH)4)或者联硼酯(B2pin2)作为还原剂，都能实现芳基叠氮类化合物快速还原为芳香胺类化合物。并且，本发明的芳香胺类化合物的制备方法，反应效率高、时间短，能够得到收率和纯度均较高的芳香胺类化合物，收率可达93％，纯度最高达到99％，反应条件温和、绿色环保，成本低，官能团容忍性好，底物中含有H、烷基、卤代基、醚类基团、胺基、硝基、氰基、羧基、酯基、酰胺基、芳香基等基团均不会对反应产生影响，具有极高的工业应用价值。
Claims (9)
1.一种芳香胺类化合物的制备方法，其特征在于：包括以下步骤：将式(1)所示的芳香基叠氮类化合物在铜盐催化剂和还原剂存在的条件下于溶剂中进行还原反应，生成式(2)所示的芳香胺类化合物；
式(1)和式(2)中，R1、R2各自独立地选自H、烷基、卤代基、醚类基团、胺基、硝基、氰基、羧基、酯基、酰胺基、芳香基中的一种，X选自碳或氮；所述还原剂为联硼酸和/或联硼酸酯。
2.如权利要求1所述的芳香胺类化合物的制备方法，其特征在于：所述铜盐催化剂选自醋酸铜、硫酸铜、溴化铜的一种或任意组合。
3.如权利要求1或2所述的芳香胺类化合物的制备方法，其特征在于：所述铜盐催化剂的摩尔量为芳香基叠氮类化合物摩尔量的1～10％。
4.如权利要求1所述的芳香胺类化合物的制备方法，其特征在于：所述溶剂为醇类水溶液，醇类选自甲醇、乙醇、丙醇中的一种或任意组合。
5.如权利要求4所述的芳香胺类化合物的制备方法，其特征在于：所述醇类水溶液中醇与水的体积比为(1～10):1。
6.如权利要求1所述的芳香胺类化合物的制备方法，其特征在于：所述还原反应的温度为20～50℃，反应时间为10～60min。
7.如权利要求1所述的芳香胺类化合物的制备方法，其特征在于：所述还原剂的摩尔量为芳香基叠氮类化合物摩尔量的1～3倍。
8.如权利要求1所述的芳香胺类化合物的制备方法，其特征在于：反应结束后，还包括将反应体系除酸后采用有机溶剂进行萃取，然后纯化。
9.如权利要求8所述的芳香胺类化合物的制备方法，其特征在于：所述萃取用有机溶剂为酯类溶剂。
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