WO2020087233A1 - 离子型铁（iii）配合物作为催化剂在制备苄基胺类化合物中的应用 - Google Patents

离子型铁（iii）配合物作为催化剂在制备苄基胺类化合物中的应用 Download PDF

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WO2020087233A1
WO2020087233A1 PCT/CN2018/112510 CN2018112510W WO2020087233A1 WO 2020087233 A1 WO2020087233 A1 WO 2020087233A1 CN 2018112510 W CN2018112510 W CN 2018112510W WO 2020087233 A1 WO2020087233 A1 WO 2020087233A1
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ionic iron
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孙宏枚
李瑞鹏
王丹
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南通纺织丝绸产业技术研究院
苏州大学
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Priority to PCT/CN2018/112510 priority Critical patent/WO2020087233A1/zh
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Priority to US17/239,496 priority patent/US11890602B2/en

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Definitions

  • the invention belongs to the technical field of preparation of organic compounds, and specifically relates to the application of an ionic iron (III) complex as a catalyst in the preparation of benzylamine compounds.
  • benzylamine compounds widely exist in natural products, pesticides, polymers and drug molecules.
  • Traditional synthesis of such compounds requires the use of pre-functionalized substrates, such as halogenated hydrocarbons, through the Buchwald-Hartwig (Buchwald – Hartwig) cross-coupling reaction (see: JF Hartwig, Acc. Chem . Res. , 2008 , 41 , 1534).
  • This method has the disadvantages of poor atomic economy and emission of halides that cause serious pollution to the environment. Therefore, the development of new methods for the synthesis of benzylamine compounds is of great practical value.
  • iron-based catalysts have been rapidly developed due to their advantages such as cheap availability, low toxicity or non-toxicity, and good biocompatibility, but so far, no benzyl sites involving iron-based catalysts Literature reports on the oxidation of carbon-hydrogen bonds. Therefore, the development of high-efficiency iron-based catalysts and the construction of benzylamine compounds through the reaction of benzene compounds and aromatic amines are in line with the development requirements of green chemistry, and are also highly innovative and valuable in application.
  • the purpose of the present invention is to provide ionic iron (III) complex as a catalyst in the preparation of benzylamine compounds, is a new method for the synthesis of benzylamine compounds, that is, the molecular formula is [( t BuNCHCHN t Bu ) CH] [FeBr 4 ]
  • Ionic iron (III) complex containing 1,3-di-tert-butylimidazole cation as catalyst using di-tert-butyl peroxide as oxidant, through toluene / ethylbenzene compounds and aromatic Amine reaction to synthesize benzylamine compounds.
  • [( t BuNCHCHN t Bu) CH] [FeBr 4 ] is an iron (III) complex with a clear structure that is simple, easy to obtain, and stable in air.
  • the preparation of the benzylamine compound takes the benzene compound and the aromatic amine as raw materials in the presence of an oxidizing agent.
  • the oxidant is di-tert-butyl peroxide.
  • the method for preparing a benzylamine compound includes the following steps: mixing a catalyst, an aromatic amine, an oxidizing agent, and a benzene compound, and reacting to obtain a benzylamine compound.
  • the benzene compound is a liquid and can be used as a reaction raw material and a solvent.
  • the temperature of the reaction is 80-150 ° C, and the time is 15-60 hours.
  • the reaction solution is cooled to room temperature, and then purified by column chromatography to obtain a benzylamine compound.
  • a mixed solvent of ethyl acetate / petroleum ether with a volume ratio of 1:50 is used as a developing agent.
  • the amount of oxidant is 1 to 1.6 times that of aromatic amine, and the amount of catalyst is 5 to 20% of aromatic amine.
  • the amount of oxidant is 1.5 times that of aromatic amine, and the amount of catalyst is 10% of aromatic amine.
  • the aromatic amine is expressed by the following chemical structural formula:
  • R is hydrogen or methyl; R 1 is cyano, nitro, trifluoromethyl or acetyl.
  • benzene compounds are expressed by the following chemical structural formulas:
  • R 2 is hydrogen or methyl
  • Ar is phenyl, p-tert-butylphenyl, o-methylphenyl, mesitylphenyl, p-chlorophenyl, o-chlorophenyl, naphthyl, thienyl One kind.
  • reaction process for preparing benzylamine compounds of the present invention can be expressed as follows:
  • the present invention has the following advantages compared with the prior art:
  • the present invention uses an iron (III) complex as a single-component catalyst to realize the reaction of toluene / ethylbenzene compounds and aromatic amines, and provides a new method for synthesizing benzylamine compounds.
  • the iron (III) complex used in the present invention is a solid compound with a clear structure and air stability, which has the characteristics of low cost, easy synthesis, greenness, and environmental friendliness, and is beneficial to large-scale industrial synthesis applications.
  • the preparation method disclosed in the present invention has a wide range of applications, not only for toluene compounds containing primary carbon-hydrogen bonds in the benzyl position, but also for ethylbenzene compounds containing secondary carbon-hydrogen bonds in the benzyl position.
  • the applicability of the substrate is improved; in particular, it solves that the existing method can only be applied to the compound containing the secondary carbon-hydrogen bond in the benzylic position, and is not applicable to the compound containing the primary carbon-hydrogen bond in the benzine position. problem.
  • Example 1 Synthesis of ionic iron complex containing 1,3-di-tert-butylimidazole cation (molecular formula [( t BuNCHCHN t Bu) CH] [FeBr 4 ])
  • 1,3-Di-tert-butylimidazole bromide (0.26 g, 1.0 mmol) was added to a solution of ferric tribromide (0.27 g, 0.9 mmol) in tetrahydrofuran, and the reaction was carried out at 60 ° C for 24 hours.
  • the solvent was washed with hexane, pumped dry, extracted with tetrahydrofuran, centrifuged to transfer the supernatant, recrystallized by adding hexane to the supernatant, and red-brown crystals were precipitated at room temperature with a yield of 89%.
  • the cationic part of the complex [( t BuNCHCHN t Bu) CH] + was characterized by mass spectrometry and found to have a molecular ion peak at 181.1699. In theory, the molecular ion peak is at 181.1699, and the measured results are consistent with the theory.
  • the yield is only 8%: when the oxidant is tert-butyl hydroperoxide (1.5 times), the yield is only 22%.
  • Example 8 [( t BuNCHCHN t Bu) CH] [FeBr 4 ] catalyzed reaction of p-cyanoaniline with 1-methylnaphthalene
  • Example 10 [( t BuNCHCHN t Bu) CH] [FeBr 4 ] catalyzed reaction of p-trifluoromethylaniline with toluene
  • Example 15 [( t BuNCHCHN t Bu) CH] [FeBr 4 ] catalyzed reaction of N-methyl p-cyanoaniline with toluene

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Abstract

本发明公开了离子型铁（III）配合物作为催化剂在制备苄基胺类化合物中的应用，即以分子式为[(RNCHCHNR)CH][FeBr 4]（R为叔丁基）的含1,3-二叔丁基咪唑阳离子的离子型铁（III）配合物为催化剂、以过氧化二叔丁基为氧化剂，通过甲苯/乙苯类化合物与芳胺的氧化反应来合成苄基胺类化合物。本发明适用范围广，不仅适用于含苄位伯碳-氢键的甲苯类化合物，也适用于含苄位仲碳-氢键的乙苯类化合物。这是由铁系催化剂实现的经甲苯/乙苯类化合物和芳胺的氧化反应来制备苄基胺类化合物的第一例。

Description

离子型铁（III）配合物作为催化剂在制备苄基胺类化合物中的应用 技术领域
本发明属于有机化合物的制备技术领域，具体涉及到离子型铁（III）配合物作为催化剂在制备苄基胺类化合物中的应用。
 背景技术
苄基胺类化合物作为一种关键的骨架结构广泛存在于天然产物、农药、聚合物和药物分子中。传统合成这类化合物时需要使用预先功能化的底物，如卤代烃，通过布赫瓦尔德-哈特维希(Buchwald –Hartwig）交叉偶联反应来合成（参见：J. F. Hartwig, Acc. Chem. Res., 2008, 41, 1534）。此种方法具有原子经济性差、排放出对环境有严重污染的卤化物等缺点。因此，开发合成苄基胺类化合物的新方法是有很强的实际应用价值的。
近年来，通过过渡金属催化的碳-氢键的氧化反应来构建碳-氮键成为了合成胺类化合物的一个新方法，该方法避免了卤代烃的使用，具有更好的原子经济性和环境友好性。但是涉及苄位碳-氢键氧化反应的报道极少，公开的铜催化体系也仅适用于含苄位仲碳-氢键的底物。
在过去十年里，铁系催化剂因具有廉价易得、低毒或者无毒、生物相容性好等优点而得到了快速发展，但到目前为止，还未见涉及铁系催化剂催化的苄位碳-氢键的氧化反应的文献报道。因此，开发高效的铁系催化剂，通过苯类化合物与芳胺的反应来构建苄基胺类化合物是符合绿色化学的发展要求的，也是极具创新性和应用价值的。
 技术问题
本发明的目的是提供离子型铁（III）配合物作为催化剂在制备苄基胺类化合物中的应用，是一种合成苄基胺类化合物的新方法，即以分子式为[( tBuNCHCHN tBu)CH][FeBr 4]的含1,3-二叔丁基咪唑阳离子的离子型铁（III）配合物为催化剂、以过氧化二叔丁基为氧化剂、通过甲苯/乙苯类化合物与芳胺的反应来合成苄基胺类化合物。[( tBuNCHCHN tBu)CH][FeBr 4]是一种简单易得的、并且在空气中稳定的、具有明确结构的铁(III)配合物。
技术解决方案
为达到上述发明目的，本发明采用的技术方案是:
离子型铁（III）配合物作为催化剂在制备苄基胺类化合物中的应用；所述离子型铁（III）配合物的化学结构式如下：
Figure 682715dest_path_image001
。
上述技术方案中，制备苄基胺类化合物时以苯类化合物和芳胺为原料，在氧化剂存在下进行。
上述技术方案中，所述氧化剂为过氧化二叔丁基。
上述技术方案中，制备苄基胺类化合物的方法，包括以下步骤，混合催化剂、芳胺、氧化剂、苯类化合物，反应得到苄基胺类化合物。
上述技术方案中，苯类化合物为液体，可以作为反应原料与溶剂。
上述技术方案中，所述反应的温度为80～150 °C，时间为15～60小时。
上述技术方案中，反应结束后，反应液冷却至室温，再通过柱层析进行提纯，得到苄基胺类化合物。优选的，柱层析提纯时以体积比为1∶50的乙酸乙酯/石油醚混合溶剂为展开剂。
上述技术方案中，以物质的量计，氧化剂的用量为芳胺的1～1.6倍，催化剂的用量为芳胺的5～20%。
优选的技术方案中，以物质的量计，氧化剂的用量为芳胺的1.5倍，催化剂用量为芳胺的10 %。
本发明中，芳胺由下列化学结构式表达：
Figure 472817dest_path_image002
R为氢或者甲基；R 1为氰基、硝基、三氟甲基或者乙酰基。
本发明中，苯类化合物由下列化学结构式表达：
Figure 961567dest_path_image003
R 2为氢或者甲基；Ar 为苯基、对叔丁基苯基、邻甲基苯基、均三甲基苯基、对氯苯基、邻氯苯基、萘基、噻吩基中的一种。
本发明制备苄基胺类化合物的反应过程可如下表示：
Figure 26475dest_path_image004
。
有益效果
由于上述技术方案运用，本发明与现有技术相比具有以下优点：
本发明首次以铁(III)配合物为单组份催化剂，实现了甲苯/乙苯类化合物与芳胺的反应，为合成苄基胺类化合物提供了一种新方法。本发明所用的铁(III)配合物是具有结构明确和空气稳定性的固体状化合物，具有价廉易合成、绿色、环境友好的特点，有利于大规模的工业合成应用。
本发明公开的制备方法适用范围广，不仅适用于含苄位伯碳-氢键的甲苯类化合物，也适用于含苄位仲碳-氢键的乙苯类化合物。在很大程度上提高了底物的适用性；尤其是解决了现有方法仅能适用于含苄位仲碳-氢键的化合物，对于含苄位伯碳-氢键的化合物是不适用的问题。
 本发明的实施方式
下面结合实施例对本发明作进一步描述：
实施例一：含1,3-二叔丁基咪唑阳离子（分子式为[( tBuNCHCHN tBu)CH][FeBr 4]）的离子型铁配合物的合成
将1,3-二叔丁基咪唑溴盐（0.26克，1.0毫摩尔）加入到三溴化铁（0.27克，0.9毫摩尔）的四氢呋喃溶液中，60 °C下反应24小时，真空抽去溶剂，己烷洗涤，抽干，用四氢呋喃萃取，离心清液转移，在清液中加入己烷重结晶，室温下析出红棕色晶体，产率89%。
 产物进行元素分析，结果如下所示：
元素分析
  C：（%） H：（%） N：（%）
理论值 23.73 3.80 5.03
实际值 23.88 3.89 5.14
此配合物[( tBuNCHCHN tBu)CH][FeBr 4]是以离子对的形式存在的，其中[FeBr 4] -通过拉曼光谱进行了表征，发现其在204 cm -1处有特征峰。
配合物的阳离子部分[( tBuNCHCHN tBu)CH] +通过质谱进行了表征，发现其在181.1699处有一个分子离子峰，理论上此分子离子峰在181.1699，实测与理论一致。
证明所得化合物为目标化合物，化学结构式如下：
Figure 284281dest_path_image005
。
实施例二：[( tBuNCHCHN tBu)CH][FeBr 4]催化的对氰基苯胺与甲苯的反应
在反应瓶中依次加入对氰基苯胺（59毫克，0.5毫摩尔），催化剂（28毫克，0.05毫摩尔），过氧化二叔丁基（138微升，0.75毫摩尔），甲苯（7毫升）在120℃下反应24小时，反应结束后冷却至室温，产物用柱层析提纯，（以乙酸乙酯/石油醚体积比为1∶50的混合溶剂为展开剂），产率为88%。
当催化剂为溴化铁（10mol %）时，收率只有8%：当氧化剂为叔丁基过氧化氢（1.5 倍）时，收率只有22%。
将产物溶于CDCl 3中（约0.4 mL），封管，室温下于Unity Inova-400型NMR仪上测定表征： 1H NMR (400 MHz, CDCl 3, TMS): 7.38-7.28 (m, 7H), 6.58-6.55 (m, 2H), 4.73 (s, 1H), 4.35 (s, 2H) ppm。
实施例三：[( tBuNCHCHN tBu)CH][FeBr 4]催化的对氰基苯胺与对叔丁基甲苯的反应
在反应瓶中依次加入对氰基苯胺（59毫克，0.5毫摩尔），催化剂（14毫克，0.025毫摩尔），过氧化二叔丁基（138微升，0.75毫摩尔），对叔丁基甲苯（7毫升）在80℃下反应60小时，反应结束后冷却至室温，产物用柱层析提纯，（以乙酸乙酯/石油醚体积比为1∶50的混合溶剂为展开剂），产率为86%。
将产物溶于CDCl 3中（约0.4 mL），封管，室温下于Unity Inova-400型NMR仪上测定表征： 1H NMR (400 MHz, CDCl3, TMS): 7.45 (m, 4H), 7.32 (d, J = 7.9 Hz, 2H), 6.69-6.60 (m, 2H), 4.65 (s, 1H), 4.39 (s, 2H), 1.38 (s, 9H) ppm。
实施例四：[( tBuNCHCHN tBu)CH][FeBr 4]催化的对氰基苯胺与邻二甲苯的反应
在反应瓶中依次加入对氰基苯胺（59毫克，0.5毫摩尔），催化剂（14毫克，0.025毫摩尔），过氧化二叔丁基（138微升，0.75毫摩尔），邻二甲苯（7毫升）在90℃下反应52小时，反应结束后冷却至室温，产物用柱层析提纯，（以乙酸乙酯/石油醚体积比为1∶30的混合溶剂为展开剂），产率为83%。
将产物溶于CDCl 3中（约0.4 mL），封管，室温下于Unity Inova-400型NMR仪上测定表征： 1H NMR (400 MHz, CDCl 3, TMS): 7.50-7.45 (m, 2H), 7.35-7.21 (m, 4H), 6.68-6.61 (m, 2H), 4.57 (s, 1H), 4.37 (d, J = 4.7 Hz, 2H), 2.42 (s, 3H) ppm。
实施例五：[( tBuNCHCHN tBu)CH][FeBr 4]催化的对氰基苯胺与均三甲苯的反应
在反应瓶中依次加入对氰基苯胺（59毫克，0.5毫摩尔），催化剂（28毫克，0.05毫摩尔），过氧化二叔丁基（92微升，0.5毫摩尔），均三甲苯（7毫升）在100℃下反应40小时，反应结束后冷却至室温，产物用柱层析提纯，（以乙酸乙酯/石油醚体积比为1∶10的混合溶剂为展开剂），产率为84%。
将产物溶于CDCl 3中（约0.4 mL），封管，室温下于Unity Inova-400型NMR仪上测定表征： 1H NMR (400 MHz, CDCl3, TMS): 7.52-7.39 (m, 2H), 7.01 (s, 3H), 6.74-6.58 (m, 2H), 4.75 (s, 1H), 4.35 (d, J = 5.1 Hz, 2H), 2.38 (s, 6H) ppm。
实施例六：[( tBuNCH 2CH 2N tBu)CH][FeBr 4]催化的对氰基苯胺与对氯甲苯的反应
在反应瓶中依次加入对氰基苯胺（59毫克，0.5毫摩尔），催化剂（42毫克，0.075毫摩尔），过氧化二叔丁基（138微升，0.75毫摩尔），对氯甲苯（7毫升）在110℃下反应32小时，反应结束后冷却至室温，产物用柱层析提纯，（以乙酸乙酯/石油醚体积比为1∶50的混合溶剂为展开剂），产率为80%。
将产物溶于CDCl 3中（约0.4 mL），封管，室温下于Unity Inova-400型NMR仪上测定表征： 1H NMR (400 MHz, CDCl 3, TMS):7.51-7.46 (m, 2H), 7.43-7.39 (m, 2H), 7.22 (d, J = 8.4 Hz, 2H), 6.61-6.56 (m, 2H), 4.77 (s, 1H), 4.36 (s, 2H) ppm。
实施例七：[( tBuNCHCHN tBu)CH][FeBr 4]催化的对氰基苯胺与邻氯甲苯的反应
在反应瓶中依次加入对氰基苯胺（59毫克，0.5毫摩尔），催化剂（28毫克，0.05毫摩尔），过氧化二叔丁基（138微升，0.75毫摩尔），邻氯甲苯（7毫升）在120℃下反应24小时，反应结束后冷却至室温，产物用柱层析提纯，（以乙酸乙酯/石油醚体积比为1∶10的混合溶剂为展开剂），产率为82%。
将产物溶于CDCl 3中（约0.4 mL），封管，室温下于Unity Inova-400型NMR仪上测定表征： 1H NMR (400 MHz, CDCl 3, TMS): 7.47-7.42 (m, 3H), 7.37 (d, J = 4.2 Hz, 1H), 7.34-7.24 (m, 2H), 6.63 (d, J = 8.8 Hz, 2H), 4.94 (s, 1H), 4.52 (d, J = 5.9 Hz, 2H) ppm。
实施例八：[( tBuNCHCHN tBu)CH][FeBr 4]催化的对氰基苯胺与1-甲基萘的反应
在反应瓶中依次加入对氰基苯胺（59毫克，0.5毫摩尔），催化剂（56毫克，0.1毫摩尔），过氧化二叔丁基（138微升，0.75毫摩尔），1-甲基萘（7毫升）在130℃下反应18小时，反应结束后冷却至室温，产物用柱层析提纯，（以乙酸乙酯/石 体积比为1∶10的混合溶剂为展开剂），产率为82%。
将产物溶于CDCl 3中（约0.4 mL），封管，室温下于Unity Inova-400型NMR仪上测定表征： 1H NMR (400 MHz, CDCl 3, TMS): 8.03 (dd, J = 7.8, 1.9 Hz, 1H), 8.01-7.94 (m, 1H), 7.90 (d, J = 7.6 Hz, 1H), 7.65-7.57 (m, 2H), 7.50 (dd, J = 8.8, 5.4, 1.8 Hz, 4H), 6.73-6.62 (m, 2H), 4.81 (d, J = 5.1 Hz, 2H), 4.68 (s, 1H) ppm。
实施例九：[( tBuNCHCHN tBu)CH][FeBr 4]催化的对氰基苯胺与2-甲基噻吩的反应
在反应瓶中依次加入对氰基苯胺（59毫克，0.5毫摩尔），催化剂（56毫克，0.1毫摩尔），过氧化二叔丁基（138微升，0.75毫摩尔），2-甲基噻吩（7毫升）在130℃下反应38小时，反应结束后冷却至室温，产物用柱层析提纯，（以乙酸乙酯/石油醚体积比为1∶10的混合溶剂为展开剂），产率为83%。
将产物溶于CDCl 3中（约0.4 mL），封管，室温下于Unity Inova-400型NMR仪上测定表征： 1H NMR (400 MHz, CDCl 3, TMS):7.47 (d, J = 8.8 Hz, 2H), 7.29 (dd, J = 5.0, 1.2 Hz, 1H), 7.06 (d, J = 0.7 Hz, 1H), 7.04 (d, J = 5.0 Hz, 1H), 6.68 (d, J = 8.8 Hz, 2H), 4.77 (s, 1H), 4.60 (d, J = 5.5 Hz, 2H) ppm。
实施例十：[( tBuNCHCHN tBu)CH][FeBr 4]催化的对三氟甲基苯胺与甲苯的反应
在反应瓶中依次加入对三氟甲基苯胺（64微升，0.5毫摩尔），催化剂（28毫克，0.05毫摩尔），过氧化二叔丁基（147微升，0.8毫摩尔），甲苯（7毫升）在140℃下反应16小时，反应结束后冷却至室温，产物用柱层析提纯，（以乙酸乙酯/石油醚体积比为1∶50的混合溶剂为展开剂），产率为75%。
将产物溶于CDCl 3中（约0.4 mL），封管，室温下于Unity Inova-400型NMR仪上测定表征： 1H NMR (400 MHz, CDCl 3, TMS): 7.38-7.26 (m, 7H), 6.58 (d, J = 8.8 Hz, 2H), 4.31 (s, 3H) ppm。
实施例十一：[( tBuNCHCHN tBu)CH][FeBr 4]催化的对乙酰基苯胺与甲苯的反应
在反应瓶中依次加入对乙酰基苯胺（68毫克，0.5毫摩尔），催化剂（28毫克，0.05毫摩尔），过氧化二叔丁基（138微升，0.75毫摩尔），甲苯（7毫升）在150℃下反应15小时，反应结束后冷却至室温，产物用柱层析提纯，（以乙酸乙酯/石油醚体积比为1∶100的混合溶剂为展开剂），产率为74%。
将产物溶于CDCl 3中（约0.4 mL），封管，室温下于Unity Inova-400型NMR仪上测定表征： 1H NMR (400 MHz, CDCl 3, TMS): 7.82-7.79 (m, 2H), 7.36-7.27 (m, 5H), 6.60-6.57 (m, 2H), 4.69 (s, 1H), 4.39 (d, J = 4.8 Hz, 2H), 2.47 (s, 3H) ppm。
实施例十二：[( tBuNCHCHN tBu)CH][FeBr 4]催化的对氰基苯胺与乙苯的反应
在反应瓶中依次加入对氰基苯胺（59毫克，0.5毫摩尔），催化剂（28毫克，0.05毫摩尔），过氧化二叔丁基（147微升，0.8毫摩尔），乙苯（7毫升）在130℃下反应18小时，反应结束后冷却至室温，产物用柱层析提纯，（以乙酸乙酯/石油醚体积比为1∶5的混合溶剂为展开剂），产率为81%。
将产物溶于CDCl 3中（约0.4 mL），封管，室温下于Unity Inova-400型NMR仪上测定表征：： 1H NMR (400 MHz, CDCl 3, TMS):7.34-7.28 (m, 6H), 7.26-7.21 (m, 1H), 6.48-6.45 (m, 2H), 4.70 (s, 1H), 4.51 (q, J = 6.7 Hz, 1H), 1.53 (d, J = 6.7 Hz, 3H) ppm。
实施例十三：[( tBuNCHCHN tBu)CH][FeBr 4]催化的对硝基苯胺与乙苯的反应
在反应瓶中依次加入对硝基苯胺（69毫克，0.5毫摩尔），催化剂（28毫克，0.05毫摩尔），过氧化二叔丁基（138微升，0.75毫摩尔），乙苯（7毫升）在140℃下反应16小时，反应结束后冷却至室温，产物用柱层析提纯，（以乙酸乙酯/石油醚体积比为1∶20的混合溶剂为展开剂），产率为80%。
将产物溶于CDCl 3中（约0.4 mL），封管，室温下于Unity Inova-400型NMR仪上测定表征： 1H NMR (400 MHz, CDCl 3, TMS): 7.98-7.97 (m, 2H), 7.37-7.30 (m, 4H), 7.27-7.23 (m, 1H), 6.47-6.43 (m, 2H), 4.95 (d, J = 4.8 Hz, 1H), 4.58 (q, J = 6.4 Hz, 1H), 1.57 (d, J = 6.8 Hz, 3H) ppm。
实施例十四：[( tBuNCHCHN tBu)CH][FeBr 4]催化的N-甲基对硝基苯胺与甲苯的反应
在反应瓶中依次加入N-甲基对硝基苯胺（76毫克，0.5毫摩尔），催化剂（42毫克，0.075毫摩尔），过氧化二叔丁基（138微升，0.75毫摩尔），甲苯（7毫升）在140℃下反应16小时，反应结束后冷却至室温，产物用柱层析提纯，（以乙酸乙酯/石油醚体积比为1∶10的混合溶剂为展开剂），产率为68%。
将产物溶于CDCl 3中（约0.4 mL），封管，室温下于Unity Inova-400型NMR仪上测定表征： 1H NMR (400 MHz, CDCl 3, TMS): 8.14 (d, J = 9.4 Hz, 2H), 7.39 (d, J = 7.6 Hz, 3H), 7.22 (d, J = 7.1 Hz, 2H), 6.71 (d, J = 9.4 Hz, 2H), 4.73 (s, 2H), 3.24 (s, 3H) ppm。
实施例十五：[( tBuNCHCHN tBu)CH][FeBr 4]催化的N-甲基对氰基苯胺与甲苯的反应
在反应瓶中依次加入N-甲基对氰基苯胺（66毫克，0.5毫摩尔），催化剂（56毫克，0.1毫摩尔），过氧化二叔丁基（138微升，0.75毫摩尔），甲苯（7毫升）在130℃下反应18小时，反应结束后冷却至室温，产物用柱层析提纯，（以乙酸乙酯/石油醚体积比为1∶10的混合溶剂为展开剂），产率为75%。
将产物溶于CDCl 3中（约0.4 mL），封管，室温下于Unity Inova-400型NMR仪上测定表征： 1H NMR (400 MHz, CDCl 3, TMS): 7.52-7.46 (m, 2H), 7.37 (dd, J = 25.5, 3.8 Hz, 3H), 7.22 (d, J = 7.3 Hz, 2H), 6.77-6.71 (m, 2H), 4.67 (s, 2H), 3.18 (s, 3H) ppm。

Claims (10)

  1. 离子型铁（III）配合物作为催化剂在制备苄基胺类化合物中的应用；所述离子型铁（III）配合物的化学结构式如下：
    Figure 76528dest_path_image001
    。
  2. 根据权利要求1所述离子型铁（III）配合物作为催化剂在制备苄基胺类化合物中的应用，其特征在于，制备苄基胺类化合物时以苯类化合物和芳胺为原料，在氧化剂存在下进行。
  3. 根据权利要求2所述离子型铁（III）配合物作为催化剂在制备苄基胺类化合物中的应用，其特征在于，所述氧化剂为过氧化二叔丁基；苯类化合物为液体。
  4. 根据权利要求2所述离子型铁（III）配合物作为催化剂在制备苄基胺类化合物中的应用，其特征在于，制备苄基胺类化合物的方法，包括以下步骤，混合催化剂、芳胺、氧化剂、苯类化合物，反应得到苄基胺类化合物。
  5. 根据权利要求4所述离子型铁（III）配合物作为催化剂在制备苄基胺类化合物中的应用，其特征在于，所述反应的温度为80～150℃，时间为15～60小时。
  6. 根据权利要求4所述离子型铁（III）配合物作为催化剂在制备苄基胺类化合物中的应用，其特征在于，反应结束后，反应液冷却至室温，再通过柱层析进行提纯，得到苄基胺类化合物。
  7. 根据权利要求2所述离子型铁（III）配合物作为催化剂在制备苄基胺类化合物中的应用，其特征在于，以物质的量计，氧化剂的用量为芳胺的1～1.6倍，催化剂的用量为芳胺的5～20%。
  8. 根据权利要求7所述离子型铁（III）配合物作为催化剂在制备苄基胺类化合物中的应用，其特征在于，以物质的量计，氧化剂的用量为芳胺的1.5倍，催化剂用量为芳胺的10 %。
  9. 根据权利要求2所述离子型铁（III）配合物作为催化剂在制备苄基胺类化合物中的应用，其特征在于，芳胺由下列化学结构式表达：
    Figure 140299dest_path_image002
    R为氢或者甲基；R 1为氰基、硝基、三氟甲基或者乙酰基；
    苯类化合物由下列化学结构式表达：
    Figure 73620dest_path_image003
    R 2为氢或者甲基；Ar 为苯基、对叔丁基苯基、邻甲基苯基、均三甲基苯基、对氯苯基、邻氯苯基、萘基、噻吩基中的一种。
  10. 根据权利要求1所述离子型铁（III）配合物作为催化剂在制备苄基胺类化合物中的应用，其特征在于，催化剂的制备方法为，将1,3-二叔丁基咪唑溴盐加入到三溴化铁的四氢呋喃溶液中，60℃下反应24小时；反应结束后真空抽去溶剂，反应液经过己烷洗涤、抽干、用四氢呋喃萃取、离心清液转移后，在清液中加入己烷重结晶，室温下析出红棕色晶体，为催化剂。
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112694375A (zh) * 2021-01-22 2021-04-23 苏州大学 含1,3-二叔丁基咪唑阳离子的铁（iii）配合物在合成芳基苄基醚类化合物中的应用
WO2022155936A1 (zh) * 2021-01-22 2022-07-28 苏州大学 一种合成芳基苄基醚类化合物的方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103408433A (zh) * 2013-07-16 2013-11-27 湖南大学 一种炔丙胺类化合物的合成方法
CN105481695A (zh) * 2015-12-30 2016-04-13 苏州大学 一种制备羧酸酯类化合物的方法
CN107311890A (zh) * 2017-05-17 2017-11-03 苏州大学 一种合成羧酸氰甲基酯的方法
CN107935860A (zh) * 2017-12-08 2018-04-20 苏州大学 一种制备烯丙基胺类化合物的方法
CN109232265A (zh) * 2018-10-22 2019-01-18 苏州大学 一种制备苄基胺类化合物的方法
CN109320434A (zh) * 2018-10-22 2019-02-12 苏州大学 离子型铁（iii）配合物作为催化剂在制备苄基胺类化合物中的应用

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103408433A (zh) * 2013-07-16 2013-11-27 湖南大学 一种炔丙胺类化合物的合成方法
CN105481695A (zh) * 2015-12-30 2016-04-13 苏州大学 一种制备羧酸酯类化合物的方法
CN107311890A (zh) * 2017-05-17 2017-11-03 苏州大学 一种合成羧酸氰甲基酯的方法
CN107935860A (zh) * 2017-12-08 2018-04-20 苏州大学 一种制备烯丙基胺类化合物的方法
CN109232265A (zh) * 2018-10-22 2019-01-18 苏州大学 一种制备苄基胺类化合物的方法
CN109320434A (zh) * 2018-10-22 2019-02-12 苏州大学 离子型铁（iii）配合物作为催化剂在制备苄基胺类化合物中的应用

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112694375A (zh) * 2021-01-22 2021-04-23 苏州大学 含1,3-二叔丁基咪唑阳离子的铁（iii）配合物在合成芳基苄基醚类化合物中的应用
WO2022155936A1 (zh) * 2021-01-22 2022-07-28 苏州大学 一种合成芳基苄基醚类化合物的方法
CN112694375B (zh) * 2021-01-22 2023-02-24 苏州大学 含1,3-二叔丁基咪唑阳离子的铁（iii）配合物在合成芳基苄基醚类化合物中的应用

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