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CN116239779A - A two-dimensional halogen-bonded organic framework material for iodination reagents, its preparation method and application - Google Patents

A two-dimensional halogen-bonded organic framework material for iodination reagents, its preparation method and application Download PDF

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CN116239779A
CN116239779A CN202211096325.5A CN202211096325A CN116239779A CN 116239779 A CN116239779 A CN 116239779A CN 202211096325 A CN202211096325 A CN 202211096325A CN 116239779 A CN116239779 A CN 116239779A
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陈世贵
夏宁
王璐
韩继新
王继科
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Abstract

The invention relates to the technical field of organic frame materials, in particular to a two-dimensional halogen bond organic frame material for iodination reagent, a preparation method and application thereof, and the structural formula is as follows
Figure DDA0003834804450000011
Or (b)
Figure DDA0003834804450000012
The two-dimensional halogen bond organic framework material of the invention has a two-dimensional network structure [ N.I. ] and is + ···N]The linked halogen-bonded organic framework material has a stable I + The preparation method has the advantages of simple steps and convenient operation, and the preparation method exists in a rigid framework, and has better crystallinity and thermal stability. The two-dimensional halogen bond organic framework material is used as an iodination reagent in the iodination reaction of aryl boric acid, so that the reaction can obtain good yield under the mild condition without a catalyst.

Description

一种用于碘化试剂的二维卤键有机框架材料、其制备方法及 应用A two-dimensional halogen bond organic framework material for iodination reagent, preparation method and application thereof

技术领域Technical Field

本发明涉及有机框架材料的技术领域，具体涉及一种用于碘化试剂的二维卤键有机框架材料、其制备方法及应用。The present invention relates to the technical field of organic framework materials, and in particular to a two-dimensional halogen bond organic framework material for an iodination reagent, a preparation method and application thereof.

背景技术Background Art

芳基硼酸是一种易得、易处理的化合物，近年来在Suzuki偶联反应中作为芳基供体成为有机合成中的重要底物。卤代烃是一种有价值的合成中间体，其制备方法多种多样。虽然亲电芳香卤化法用于制备氯代芳烃和溴代芳烃的效果很好，但芳烃与碘的直接碘化通常是不可行的。因此，许多用于制备碘代芳烃的不同方法已经被开发出来。这些方法包括：(a)使用强氧化试剂来活化卤素；(b)使用具有高反应性和毒性的芳香汞和铊化合物的方法；(c)Sandmeyer反应，在酸性条件下通过芳基重氮离子对氯、溴和碘进行区域选择性引入。这些方法必须使用昂贵的有毒金属催化剂或在苛刻的反应条件下完成制备。Arylboronic acids are readily available and easy to handle compounds that have become important substrates in organic synthesis in recent years as aromatic donors in Suzuki coupling reactions. Halogenated hydrocarbons are valuable synthetic intermediates and can be prepared by a variety of methods. Although electrophilic aromatic halogenation works well for the preparation of chloroaromatic hydrocarbons and bromoaromatic hydrocarbons, direct iodination of aromatic hydrocarbons with iodine is generally not feasible. Therefore, many different methods for the preparation of iodoaromatic hydrocarbons have been developed. These methods include: (a) the use of strong oxidizing agents to activate the halogen; (b) methods using highly reactive and toxic aromatic mercury and thallium compounds; and (c) Sandmeyer reactions, which regioselectively introduce chlorine, bromine, and iodine through aromatic diazonium ions under acidic conditions. These methods must use expensive toxic metal catalysts or perform the preparation under harsh reaction conditions.

已经有部分工作使用N-卤代琥珀酰亚胺或Baluenga试剂作为亲电卤素的来源与芳基硼酸反应制备碘代芳烃，可适用于必须避免苛刻的反应条件的底物。当使用硼酸官能团作为卤代烃的保护基团时，在温和的条件下，通过与亲电卤素试剂反应，很容易使卤代烃再生。然而，目前常用的亲电碘化试剂N-卤代琥珀酰亚胺或Baluenga试剂具有较差的热稳定性，这两类商品化试剂的储存环境一般为2-8℃，储存过程中易分解，不利于稳定的长期储存。Some studies have used N-halosuccinimide or Baluenga reagent as a source of electrophilic halogen to react with arylboronic acid to prepare iodinated aromatic hydrocarbons, which can be applied to substrates that must avoid harsh reaction conditions. When the boronic acid functional group is used as a protecting group for the halogenated hydrocarbon, the halogenated hydrocarbon can be easily regenerated by reacting with the electrophilic halogen reagent under mild conditions. However, the commonly used electrophilic iodination reagents N-halosuccinimide or Baluenga reagent have poor thermal stability. The storage environment of these two types of commercial reagents is generally 2-8°C, and they are easy to decompose during storage, which is not conducive to stable long-term storage.

[N···I+···N]连接的卤键有机框架是一种新型的框架材料，这种材料具有良好的结晶度和热稳定性，且在固体状态及溶液状态都能够稳定存在。因此，[N···I+···N]连接的卤键有机框架可以提供稳定的I+用于化学反应。鉴于以上优点，[N···I+···N]连接的卤键有机框架是一种充满潜力的材料，目前还没有关于卤键有机框架用于作碘化反应的亲电碘化试剂的方法被报道。[N···I + ···N]-linked halogen-bonded organic framework is a new type of framework material, which has good crystallinity and thermal stability and can exist stably in both solid and solution states. Therefore, [N···I + ···N]-linked halogen-bonded organic framework can provide stable I + for chemical reactions. In view of the above advantages, [N···I + ···N]-linked halogen-bonded organic framework is a material full of potential. At present, no method for using halogen-bonded organic framework as electrophilic iodination reagent for iodination reaction has been reported.

发明内容Summary of the invention

本发明的目的之一在于提供一种用于碘化试剂的二维卤键有机框架材料，结晶性和热稳定性较好。One of the purposes of the present invention is to provide a two-dimensional halogen bond organic framework material for iodination reagent, which has good crystallinity and thermal stability.

本发明的目的之二在于提供一种用于碘化试剂的二维卤键有机框架材料的制备方法，制备工艺简便，易于调节。The second object of the present invention is to provide a method for preparing a two-dimensional halogen bond organic framework material for an iodination reagent, which has a simple preparation process and is easy to adjust.

本发明的目的之三在于提供一种用于碘化试剂的二维卤键有机框架材料的应用，用于芳基硼酸的碘化反应中的碘化试剂，能使反应在无需催化剂且温和的条件下得到良好的产率。The third object of the present invention is to provide an application of a two-dimensional halogen bond organic framework material for an iodination reagent, which is used as an iodination reagent in the iodination reaction of an aromatic boronic acid, and can enable the reaction to obtain a good yield under mild conditions without the need for a catalyst.

本发明实现目的之一所采用的方案是：一种用于碘化试剂的二维卤键有机框架材料，结构式为The solution adopted by the present invention to achieve one of the purposes is: a two-dimensional halogen bond organic framework material for iodination reagent, the structural formula is

Figure BDA0003834804430000021
Figure BDA0003834804430000021

本发明实现目的之二所采用的方案是：一种所述的用于碘化试剂的二维卤键有机框架材料的制备方法，其包括以下步骤：The solution adopted by the present invention to achieve the second purpose is: a method for preparing the two-dimensional halogen bond organic framework material for iodination reagent, which comprises the following steps:

A1、将配体L溶于有机溶剂I中，得到配体溶液；A1, dissolving the ligand L in the organic solvent I to obtain a ligand solution;

A2、将四氟硼酸银溶于有机溶剂II后滴加入步骤A1获得的配体溶液中，室温下搅拌至反应完全，得到混合溶液；A2, dissolving silver tetrafluoroborate in organic solvent II and then adding dropwise to the ligand solution obtained in step A1, stirring at room temperature until the reaction is complete, to obtain a mixed solution;

A3、将碘溶于有机溶剂III后滴加入步骤A2获得的混合溶液中，室温下搅拌至反应完全，将沉淀分离、洗涤并干燥；A3, dissolving iodine in organic solvent III and then adding dropwise to the mixed solution obtained in step A2, stirring at room temperature until the reaction is complete, separating, washing and drying the precipitate;

A4、将步骤A3获得的沉淀加入有机溶剂IV中，在40-200℃下保持0.1-2h后缓慢降温，分离出沉淀、洗涤并干燥，即得到所述用于碘化试剂的二维卤键有机框架材料。A4. Add the precipitate obtained in step A3 into an organic solvent IV, maintain it at 40-200° C. for 0.1-2 h, then slowly cool it down, separate the precipitate, wash it, and dry it to obtain the two-dimensional halogen bond organic framework material for the iodination reagent.

优选地，所述步骤A1中，配体L的结构式为

Figure BDA0003834804430000031
Preferably, in step A1, the structural formula of ligand L is
Figure BDA0003834804430000031

优选地，所述配体L、四氟硼酸银和单质碘的摩尔比为1:1.5:1.5。Preferably, the molar ratio of the ligand L, silver tetrafluoroborate and elemental iodine is 1:1.5:1.5.

优选地，有机溶剂I为三氯甲烷和/或甲醇组成的溶剂，其中甲醇的体积占比范围为0％-100％，有机溶剂II为甲醇，有机溶剂III为三氯甲烷，有机溶剂IV为甲醇或N,N-二甲基甲酰胺。Preferably, organic solvent I is a solvent composed of chloroform and/or methanol, wherein the volume proportion of methanol ranges from 0% to 100%, organic solvent II is methanol, organic solvent III is chloroform, and organic solvent IV is methanol or N,N-dimethylformamide.

步骤A3中，反应完后，将反应体系抽滤，分离沉淀，使用二氯甲烷洗涤沉淀，步骤A4中，将反应完全后的体系抽滤，分离沉淀，使用二氯甲烷洗涤沉淀。In step A3, after the reaction is completed, the reaction system is filtered, the precipitate is separated, and the precipitate is washed with dichloromethane. In step A4, after the reaction is completed, the system is filtered, the precipitate is separated, and the precipitate is washed with dichloromethane.

本发明实现目的之三所采用的方案是：一种所述的用于碘化试剂的二维卤键有机框架材料的应用，采用所述的二维卤键有机框架材料与芳基硼酸化合物合成碘代芳基化合物。The solution adopted by the present invention to achieve the third purpose is: an application of the two-dimensional halogen bond organic framework material for iodination reagent, using the two-dimensional halogen bond organic framework material and an aromatic boronic acid compound to synthesize an iodinated aromatic compound.

优选地，包括以下步骤：将二维卤键有机框架材料和芳基硼酸化合物溶于溶剂V中，在0-100℃、惰性气氛下反应至完全，冷却后过滤、浓缩、纯化、干燥后得到所述碘代芳基化合物。Preferably, the method comprises the following steps: dissolving a two-dimensional halogen bond organic framework material and an aromatic boronic acid compound in a solvent V, reacting to completion at 0-100° C. in an inert atmosphere, cooling, filtering, concentrating, purifying and drying to obtain the iodinated aromatic compound.

优选地，所述芳基硼酸化合物为以下化合物中的任意一种：Preferably, the aryl boronic acid compound is any one of the following compounds:

Figure BDA0003834804430000032
Figure BDA0003834804430000032

优选地，所述二维卤键有机框架材料与芳基硼酸化合物的摩尔比为1.0-2.0：1。Preferably, the molar ratio of the two-dimensional halogen bond organic framework material to the aryl boronic acid compound is 1.0-2.0:1.

优选地，所述溶剂V为乙腈、甲醇、四氢呋喃、甲苯、氯仿、N,N-二甲基甲酰胺中的一种或多种溶剂的混合溶液。Preferably, the solvent V is a mixed solution of one or more solvents selected from the group consisting of acetonitrile, methanol, tetrahydrofuran, toluene, chloroform and N,N-dimethylformamide.

采用柱层析法(PE：EA＝40:3-5)对混合物进行纯化。The mixture was purified by column chromatography (PE:EA=40:3-5).

本发明具有以下优点和有益效果：The present invention has the following advantages and beneficial effects:

本发明的二维卤键有机框架材料为二维网络结构，[N···I+···N]连接的卤键有机框架材料具有稳定的I+存在于刚性骨架中，结晶性和热稳定性较好。The two-dimensional halogen bond organic framework material of the present invention is a two-dimensional network structure. The [N···I + ···N]-connected halogen bond organic framework material has stable I + existing in the rigid skeleton and has good crystallinity and thermal stability.

本发明的二维卤键有机框架材料的制备步骤简单，操作方便。The preparation steps of the two-dimensional halogen bond organic framework material of the present invention are simple and easy to operate.

将本发明的二维卤键有机框架材料用于芳基硼酸的碘化反应中的碘化试剂，能使反应在无需催化剂且温和的条件下得到良好的产率。The two-dimensional halogen bond organic framework material of the present invention is used as an iodination reagent in the iodination reaction of aromatic boronic acid, so that the reaction can obtain a good yield under mild conditions without the need for a catalyst.

附图说明BRIEF DESCRIPTION OF THE DRAWINGS

图1是本发明实施例1、2得到的卤键有机框架的X射线光电子能谱图；FIG1 is an X-ray photoelectron spectrum of the halogen bond organic framework obtained in Examples 1 and 2 of the present invention;

图2是本发明实施例1、2得到的卤键有机框架的粉末X射线衍射图；FIG2 is a powder X-ray diffraction pattern of the halogen bond organic framework obtained in Examples 1 and 2 of the present invention;

图3为本发明实施例1、2得到的卤键有机框架的热稳定曲线。FIG3 is a thermal stability curve of the halogen bond organic framework obtained in Examples 1 and 2 of the present invention.

具体实施方式DETAILED DESCRIPTION

为更好的理解本发明，下面的实施例是对本发明的进一步说明，但本发明的内容不仅仅局限于下面的实施例。For a better understanding of the present invention, the following examples are provided to further illustrate the present invention, but the present invention is not limited to the following examples.

实施例1Example 1

1)将185mg配体

Figure BDA0003834804430000041
溶于60ml CHCl3/MeOH(v/v＝4:1)(单一种类的甲醇和三氯甲烷或者两者任意比例混合都可以作溶剂，本实施例中优选CHCl3/MeOH(v/v＝4:1))混合溶液。1) 185 mg of ligand
Figure BDA0003834804430000041
Dissolved in 60 ml CHCl 3 /MeOH (v/v=4:1) (methanol and chloroform alone or a mixture of the two in any ratio can be used as the solvent, and CHCl 3 /MeOH (v/v=4:1) is preferred in this embodiment) mixed solution.

2)将175mg AgBF4溶于9ml甲醇，在搅拌过程中逐滴加入到1)中溶液，在室温下搅拌1小时。2) Dissolve 175 mg of AgBF4 in 9 ml of methanol, add dropwise to the solution in 1) while stirring, and stir at room temperature for 1 hour.

3)将229mg碘溶于36ml氯仿，逐滴加入2)中溶液，室温下搅拌1小时。3) Dissolve 229 mg of iodine in 36 ml of chloroform, add dropwise to the solution in 2), and stir at room temperature for 1 hour.

4)将3)中得到的反应体系抽滤，干燥得到淡黄色固体。4) The reaction system obtained in 3) was filtered and dried to obtain a light yellow solid.

5)固体在N,N-二甲基甲酰胺中160℃(一般反应温度为40-200℃，本实施例中优选160℃)搅拌1小时(一般反应时间为0.1-2h，本实施例优选1h)后缓慢降温。5) The solid is stirred in N,N-dimethylformamide at 160° C. (general reaction temperature is 40-200° C., preferably 160° C. in this embodiment) for 1 hour (general reaction time is 0.1-2 hours, preferably 1 hour in this embodiment) and then slowly cooled.

6)将5)中沉淀过滤，使用二氯甲烷洗涤，真空干燥得到卤键有机框架XOF-TPy。6) Filter the precipitate in 5), wash with dichloromethane, and vacuum dry to obtain the halogen bond organic framework XOF-TPy.

本实施例制备的二维卤键有机框架材料的X射线光电子能谱图如图1所示；数据在ESCALAB 250Xi型光电子能谱仪上完成采集；从图中可以看出：XOF-TPy的谱图中，621.0和632.4eV处的谱峰可以分别归属于I+的I 3d3/2和I 3d5/2轨道，619.6和631.0eV处的谱峰可以分别归属于I-的I 3d3/2和I 3d5/2轨道，这些结果均表明了框架材料中I+的存在。The X-ray photoelectron spectrum of the two-dimensional halogen-bonded organic framework material prepared in this embodiment is shown in Figure 1; the data was collected on an ESCALAB 250Xi photoelectron spectrometer; it can be seen from the figure that in the spectrum of XOF-TPy, the peaks at 621.0 and 632.4 eV can be attributed to the I 3d 3/2 and I 3d 5/2 orbitals of I +, respectively, and the peaks at 619.6 and 631.0 eV can be attributed to the I 3d 3/2 and I 3d 5/2 orbitals of I -, respectively, and these results all indicate the presence of I + in the framework material.

本实施例制备的二维卤键有机框架材料的粉末X射线衍射图如图2所示，数据在日本Rigaku SmartLab SE型X射线衍射仪采集。从图中可以看出，本实施例制备的二维卤键有机框架材料的结晶性较好。The powder X-ray diffraction pattern of the two-dimensional halogen-bonded organic framework material prepared in this embodiment is shown in Figure 2, and the data was collected by a Japanese Rigaku SmartLab SE X-ray diffractometer. It can be seen from the figure that the two-dimensional halogen-bonded organic framework material prepared in this embodiment has good crystallinity.

本实施例制备的二维卤键有机框架材料的热稳定曲线如图3所示；数据在瑞士Mettler Toledo的TGA/DSC1型同步热分析仪采集。从图中可以看出，本实施例制备的卤键有机框架至少从200℃开始失重，表明它们良好的热稳定性。The thermal stability curve of the two-dimensional halogen-bonded organic framework material prepared in this embodiment is shown in Figure 3; the data was collected by a TGA/DSC1 type synchronous thermal analyzer of Mettler Toledo, Switzerland. It can be seen from the figure that the halogen-bonded organic framework prepared in this embodiment starts to lose weight at least from 200°C, indicating that they have good thermal stability.

实施例2Example 2

1)将388mg配体

Figure BDA0003834804430000051
溶于50ml CHCl3/MeOH(v/v＝4:1)(单一种类的甲醇和三氯甲烷或者两者任意比例混合都可以作溶剂，本实施例中优选CHCl3/MeOH(v/v＝4:1))混合溶液。1) 388 mg of ligand
Figure BDA0003834804430000051
Dissolved in 50 ml CHCl 3 /MeOH (v/v=4:1) (methanol and chloroform alone or a mixture of the two in any ratio can be used as the solvent, and CHCl 3 /MeOH (v/v=4:1) is preferred in this embodiment) mixed solution.

2)将292mg AgBF4溶于15ml甲醇，在搅拌过程中逐滴加入到1)中溶液，在室温下搅拌1小时。2) Dissolve 292 mg of AgBF4 in 15 ml of methanol, add dropwise to the solution in 1) while stirring, and stir at room temperature for 1 hour.

3)将381mg碘溶于60ml氯仿，逐滴加入2)中溶液，室温下搅拌1小时。3) Dissolve 381 mg of iodine in 60 ml of chloroform, add dropwise to the solution in 2), and stir at room temperature for 1 hour.

4)将3)中得到的反应体系抽滤，干燥得到淡黄色固体。4) The reaction system obtained in 3) was filtered and dried to obtain a light yellow solid.

5)固体在甲醇中160℃(一般反应温度为40-200℃，本实施例中优选160℃)搅拌2小时(一般反应时间为0.1-2h，本实施例优选2h)后缓慢降温。5) The solid is stirred in methanol at 160° C. (general reaction temperature is 40-200° C., preferably 160° C. in this embodiment) for 2 hours (general reaction time is 0.1-2 hours, preferably 2 hours in this embodiment) and then slowly cooled.

6)将5)中沉淀过滤，使用二氯甲烷洗涤，真空干燥得到卤键有机框架XOF-TPEB。6) Filter the precipitate in 5), wash with dichloromethane, and vacuum dry to obtain the halogen bond organic framework XOF-TPEB.

本实施例制备的二维卤键有机框架材料的X射线光电子能谱图如图1所示；数据在ESCALAB 250Xi型光电子能谱仪上完成采集；从图中可以看出：XOF-TPEB的谱图中，620.5和632.0eV处的谱峰可以分别归属于I+的I 3d3/2和I 3d5/2轨道，618.4和630.0eV处的谱峰可以分别归属于I-的I 3d3/2和I 3d5/2轨道，这些结果均表明了框架材料中I+的存在。The X-ray photoelectron spectrum of the two-dimensional halogen-bonded organic framework material prepared in this embodiment is shown in Figure 1; the data was collected on an ESCALAB 250Xi photoelectron spectrometer; it can be seen from the figure that in the spectrum of XOF-TPEB, the peaks at 620.5 and 632.0 eV can be attributed to the I 3d 3/2 and I 3d 5/2 orbitals of I +, respectively, and the peaks at 618.4 and 630.0 eV can be attributed to the I 3d 3/2 and I 3d 5/2 orbitals of I -, respectively, and these results all indicate the presence of I + in the framework material.

本实施例制备的二维卤键有机框架材料的粉末X射线衍射图如图2所示，数据在日本Rigaku SmartLab SE型X射线衍射仪采集。从图中可以看出，本实施例制备的二维卤键有机框架材料的结晶性较好。The powder X-ray diffraction pattern of the two-dimensional halogen-bonded organic framework material prepared in this embodiment is shown in Figure 2, and the data was collected by a Japanese Rigaku SmartLab SE X-ray diffractometer. It can be seen from the figure that the two-dimensional halogen-bonded organic framework material prepared in this embodiment has good crystallinity.

本实施例制备的二维卤键有机框架材料的热稳定曲线如图3所示；数据在瑞士Mettler Toledo的TGA/DSC1型同步热分析仪采集。从图中可以看出，本实施例制备的卤键有机框架至少从200℃开始失重，表明它们良好的热稳定性。The thermal stability curve of the two-dimensional halogen-bonded organic framework material prepared in this embodiment is shown in Figure 3; the data was collected by a TGA/DSC1 type synchronous thermal analyzer of Mettler Toledo, Switzerland. It can be seen from the figure that the halogen-bonded organic framework prepared in this embodiment starts to lose weight at least from 200°C, indicating that they have good thermal stability.

实施例3Example 3

将18mg

Figure BDA0003834804430000061
102mg卤键有机框架XOF-TPEB和1.5ml无水乙腈加入反应管中，在氩气保护下，81℃(一般反应温度为0-100℃，本实施例优选81℃)下搅拌14h。然后将反应体系过滤，通过旋转蒸发浓缩。用柱层析法(PE：EA＝40:3)对混合物进行纯化。真空干燥得到相应的碘化产物，产率为78％，见表1。18mg
Figure BDA0003834804430000061
102 mg of halogen bond organic framework XOF-TPEB and 1.5 ml of anhydrous acetonitrile were added to the reaction tube and stirred at 81°C (generally the reaction temperature is 0-100°C, and 81°C is preferred in this embodiment) for 14 h under argon protection. The reaction system was then filtered and concentrated by rotary evaporation. The mixture was purified by column chromatography (PE:EA=40:3). The corresponding iodinated product was obtained by vacuum drying with a yield of 78%, as shown in Table 1.

实施例4Example 4

将17mg

Figure BDA0003834804430000062
102mg卤键有机框架XOF-TPEB和1.5ml无水乙腈加入反应管中，在氩气保护下，81℃(一般反应温度为0-100℃，本实施例优选81℃)下搅拌14h。然后将反应体系过滤，通过旋转蒸发浓缩。用柱层析法(PE：EA＝8:1)对混合物进行纯化。真空干燥得到相应的碘化产物，产率为73％，见表1。17mg
Figure BDA0003834804430000062
102 mg of halogen bond organic framework XOF-TPEB and 1.5 ml of anhydrous acetonitrile were added to the reaction tube and stirred at 81°C (generally the reaction temperature is 0-100°C, and 81°C is preferred in this embodiment) for 14 h under argon protection. The reaction system was then filtered and concentrated by rotary evaporation. The mixture was purified by column chromatography (PE:EA=8:1). The corresponding iodinated product was obtained by vacuum drying with a yield of 73%, as shown in Table 1.

实施例5Example 5

将24mg

Figure BDA0003834804430000063
102mg卤键有机框架XOF-TPEB和1.5ml无水乙腈加入反应管中，在氩气保护下，81℃(一般反应温度为0-100℃，本实施例优选81℃)下搅拌14h。然后将反应体系过滤，通过旋转蒸发浓缩。用柱层析法(PE：EA＝8:1)对混合物进行纯化。真空干燥得到相应的碘化产物，产率为95％，见表1。24mg
Figure BDA0003834804430000063
102 mg of halogen bond organic framework XOF-TPEB and 1.5 ml of anhydrous acetonitrile were added to the reaction tube and stirred at 81°C (generally the reaction temperature is 0-100°C, and 81°C is preferred in this embodiment) for 14 h under argon protection. The reaction system was then filtered and concentrated by rotary evaporation. The mixture was purified by column chromatography (PE:EA=8:1). The corresponding iodinated product was obtained by vacuum drying with a yield of 95%, as shown in Table 1.

实施例6Example 6

将18mg

Figure BDA0003834804430000064
102mg卤键有机框架XOF-TPEB和1.5ml无水乙腈加入反应管中，在氩气保护下，81℃(一般反应温度为0-100℃，本实施例优选81℃)下搅拌14h。然后将反应体系过滤，通过旋转蒸发浓缩。用柱层析法(PE：EA＝10:1)对混合物进行纯化。真空干燥得到相应的碘化产物，产率为68％，见表1。18mg
Figure BDA0003834804430000064
102 mg of halogen bond organic framework XOF-TPEB and 1.5 ml of anhydrous acetonitrile were added to the reaction tube and stirred at 81°C (generally the reaction temperature is 0-100°C, and 81°C is preferred in this embodiment) for 14 h under argon protection. The reaction system was then filtered and concentrated by rotary evaporation. The mixture was purified by column chromatography (PE:EA=10:1). The corresponding iodinated product was obtained by vacuum drying with a yield of 68%, as shown in Table 1.

实施例7Example 7

将24mg

Figure BDA0003834804430000065
102mg卤键有机框架XOF-TPEB和1.5ml无水乙腈加入反应管中，在氩气保护下，81℃(一般反应温度为0-100℃，本实施例优选81℃)下搅拌14h。然后将反应体系过滤，通过旋转蒸发浓缩。用柱层析法(PE：EA＝10:1)对混合物进行纯化。真空干燥得到相应的碘化产物，产率为71％，见表1。24mg
Figure BDA0003834804430000065
102 mg of halogen bond organic framework XOF-TPEB and 1.5 ml of anhydrous acetonitrile were added to the reaction tube and stirred at 81°C (generally the reaction temperature is 0-100°C, and 81°C is preferred in this embodiment) for 14 h under argon protection. The reaction system was then filtered and concentrated by rotary evaporation. The mixture was purified by column chromatography (PE:EA=10:1). The corresponding iodinated product was obtained by vacuum drying with a yield of 71%, as shown in Table 1.

实施例8Example 8

将22mg

Figure BDA0003834804430000071
102mg卤键有机框架XOF-TPEB和1.5ml无水乙腈加入反应管中，在氩气保护下，81℃(一般反应温度为0-100℃，本实施例优选81℃)下搅拌20h。然后将反应体系过滤，通过旋转蒸发浓缩。用柱层析法(PE：EA＝40:3)对混合物进行纯化。真空干燥得到相应的碘化产物，产率为76％，见表1。22mg
Figure BDA0003834804430000071
102 mg of halogen bond organic framework XOF-TPEB and 1.5 ml of anhydrous acetonitrile were added to the reaction tube and stirred at 81°C (generally the reaction temperature is 0-100°C, and 81°C is preferred in this embodiment) for 20 h under argon protection. The reaction system was then filtered and concentrated by rotary evaporation. The mixture was purified by column chromatography (PE:EA=40:3). The corresponding iodinated product was obtained by vacuum drying with a yield of 76%, as shown in Table 1.

实施例9Example 9

将23mg

Figure BDA0003834804430000072
127mg卤键有机框架XOF-TPEB和1.5ml无水乙腈加入反应管中，在氩气保护下，81℃(一般反应温度为0-100℃，本实施例优选81℃)下搅拌20h。然后将反应体系过滤，通过旋转蒸发浓缩。用柱层析法(PE：EA＝40:3)对混合物进行纯化。真空干燥得到相应的碘化产物，产率为72％，见表1。23mg
Figure BDA0003834804430000072
127 mg of halogen bond organic framework XOF-TPEB and 1.5 ml of anhydrous acetonitrile were added to the reaction tube and stirred at 81°C (generally the reaction temperature is 0-100°C, and 81°C is preferred in this embodiment) for 20 h under argon protection. The reaction system was then filtered and concentrated by rotary evaporation. The mixture was purified by column chromatography (PE:EA=40:3). The corresponding iodinated product was obtained by vacuum drying with a yield of 72%, as shown in Table 1.

实施例10Example 10

将22mg

Figure BDA0003834804430000073
102mg卤键有机框架XOF-TPEB和1.5ml无水乙腈加入反应管中，在氩气保护下，81℃(一般反应温度为0-100℃，本实施例优选81℃)下搅拌18h。然后将反应体系过滤，通过旋转蒸发浓缩。用柱层析法(PE：EA＝8:1)对混合物进行纯化。真空干燥得到相应的碘化产物，产率为92％，见表1。22mg
Figure BDA0003834804430000073
102 mg of halogen bond organic framework XOF-TPEB and 1.5 ml of anhydrous acetonitrile were added to the reaction tube and stirred at 81°C (generally the reaction temperature is 0-100°C, and 81°C is preferred in this embodiment) for 18 h under argon protection. The reaction system was then filtered and concentrated by rotary evaporation. The mixture was purified by column chromatography (PE:EA=8:1). The corresponding iodinated product was obtained by vacuum drying with a yield of 92%, as shown in Table 1.

实施例11Embodiment 11

将18mg

Figure BDA0003834804430000074
94mg卤键有机框架XOF-TPy和3ml无水乙腈加入反应管中，在氩气保护下，81℃(一般反应温度为0-100℃，本实施例优选81℃)下搅拌14h。然后将反应体系过滤，通过旋转蒸发浓缩。用柱层析法(PE：EA＝40:3)对混合物进行纯化。真空干燥得到相应的碘化产物，产率为77％，见表1。18mg
Figure BDA0003834804430000074
94 mg of halogen bond organic framework XOF-TPy and 3 ml of anhydrous acetonitrile were added to a reaction tube and stirred at 81°C (generally the reaction temperature is 0-100°C, and 81°C is preferred in this embodiment) for 14 h under argon protection. The reaction system was then filtered and concentrated by rotary evaporation. The mixture was purified by column chromatography (PE:EA=40:3). The corresponding iodinated product was obtained by vacuum drying with a yield of 77%, as shown in Table 1.

实施例12Example 12

将17mg

Figure BDA0003834804430000081
94mg卤键有机框架XOF-TPy和1.5ml无水乙腈加入反应管中，在氩气保护下，81℃(一般反应温度为0-100℃，本实施例优选81℃)下搅拌14h。然后将反应体系过滤，通过旋转蒸发浓缩。用柱层析法(PE：EA＝8:1)对混合物进行纯化。真空干燥得到相应的碘化产物，产率为47％，见表1。17mg
Figure BDA0003834804430000081
94 mg of halogen bond organic framework XOF-TPy and 1.5 ml of anhydrous acetonitrile were added to the reaction tube and stirred at 81°C (generally the reaction temperature is 0-100°C, and 81°C is preferred in this embodiment) for 14 h under argon protection. The reaction system was then filtered and concentrated by rotary evaporation. The mixture was purified by column chromatography (PE:EA=8:1). The corresponding iodinated product was obtained by vacuum drying with a yield of 47%, as shown in Table 1.

实施例13Example 13

将24mg

Figure BDA0003834804430000082
94mg卤键有机框架XOF-TPy和1.5ml无水乙腈加入反应管中，在氩气保护下，81℃(一般反应温度为0-100℃，本实施例优选81℃)下搅拌14h。然后将反应体系过滤，通过旋转蒸发浓缩。用柱层析法(PE：EA＝8:1)对混合物进行纯化。真空干燥得到相应的碘化产物，产率为81％，见表1。24mg
Figure BDA0003834804430000082
94 mg of halogen bond organic framework XOF-TPy and 1.5 ml of anhydrous acetonitrile were added to the reaction tube and stirred at 81°C (generally the reaction temperature is 0-100°C, and 81°C is preferred in this embodiment) for 14 h under argon protection. The reaction system was then filtered and concentrated by rotary evaporation. The mixture was purified by column chromatography (PE:EA=8:1). The corresponding iodinated product was obtained by vacuum drying with a yield of 81%, as shown in Table 1.

实施例14Embodiment 14

将18mg

Figure BDA0003834804430000083
118mg卤键有机框架XOF-TPy和1.5ml无水乙腈加入反应管中，在氩气保护下，81℃(一般反应温度为0-100℃，本实施例优选81℃)下搅拌14h。然后将反应体系过滤，通过旋转蒸发浓缩。用柱层析法(PE：EA＝10:1)对混合物进行纯化。真空干燥得到相应的碘化产物，产率为40％，见表1。18mg
Figure BDA0003834804430000083
118 mg of halogen bond organic framework XOF-TPy and 1.5 ml of anhydrous acetonitrile were added to the reaction tube and stirred at 81°C (generally the reaction temperature is 0-100°C, and 81°C is preferred in this embodiment) for 14 h under argon protection. The reaction system was then filtered and concentrated by rotary evaporation. The mixture was purified by column chromatography (PE:EA=10:1). The corresponding iodinated product was obtained by vacuum drying with a yield of 40%, as shown in Table 1.

实施例15Embodiment 15

将24mg

Figure BDA0003834804430000084
118mg卤键有机框架XOF-TPy和1.5ml无水乙腈加入反应管中，在氩气保护下，81℃(一般反应温度为0-100℃，本实施例优选81℃)下搅拌14h。然后将反应体系过滤，通过旋转蒸发浓缩。用柱层析法(PE：EA＝10:1)对混合物进行纯化。真空干燥得到相应的碘化产物，产率为39％，见表1。24mg
Figure BDA0003834804430000084
118 mg of halogen bond organic framework XOF-TPy and 1.5 ml of anhydrous acetonitrile were added to the reaction tube and stirred at 81°C (generally the reaction temperature is 0-100°C, and 81°C is preferred in this embodiment) for 14 h under argon protection. The reaction system was then filtered and concentrated by rotary evaporation. The mixture was purified by column chromatography (PE:EA=10:1). The corresponding iodinated product was obtained by vacuum drying with a yield of 39%, as shown in Table 1.

实施例16Example 16

将22mg

Figure BDA0003834804430000085
94mg卤键有机框架XOF-TPy和1.5ml无水乙腈加入反应管中，在氩气保护下，81℃(一般反应温度为0-100℃，本实施例优选81℃)下搅拌20h。然后将反应体系过滤，通过旋转蒸发浓缩。用柱层析法(PE：EA＝40:3)对混合物进行纯化。真空干燥得到相应的碘化产物，产率为60％，见表1。22mg
Figure BDA0003834804430000085
94 mg of halogen bond organic framework XOF-TPy and 1.5 ml of anhydrous acetonitrile were added to the reaction tube and stirred at 81°C (generally the reaction temperature is 0-100°C, and 81°C is preferred in this embodiment) for 20 h under argon protection. The reaction system was then filtered and concentrated by rotary evaporation. The mixture was purified by column chromatography (PE:EA=40:3). The corresponding iodinated product was obtained by vacuum drying with a yield of 60%, as shown in Table 1.

实施例17Embodiment 17

将23mg

Figure BDA0003834804430000091
94mg卤键有机框架XOF-TPy和1.5ml无水乙腈加入反应管中，在氩气保护下，81℃(一般反应温度为0-100℃，本实施例优选81℃)下搅拌20h。然后将反应体系过滤，通过旋转蒸发浓缩。用柱层析法(PE：EA＝40:3)对混合物进行纯化。真空干燥得到相应的碘化产物，产率为43％，见表1。23mg
Figure BDA0003834804430000091
94 mg of halogen bond organic framework XOF-TPy and 1.5 ml of anhydrous acetonitrile were added to the reaction tube and stirred at 81°C (generally the reaction temperature is 0-100°C, and 81°C is preferred in this embodiment) for 20 h under argon protection. The reaction system was then filtered and concentrated by rotary evaporation. The mixture was purified by column chromatography (PE:EA=40:3). The corresponding iodinated product was obtained by vacuum drying with a yield of 43%, as shown in Table 1.

实施例18Embodiment 18

将22mg

Figure BDA0003834804430000092
94mg卤键有机框架XOF-TPy和1.5ml无水乙腈加入反应管中，在氩气保护下，81℃(一般反应温度为0-100℃，本实施例优选81℃)下搅拌18h。然后将反应体系过滤，通过旋转蒸发浓缩。用柱层析法(PE：EA＝8:1)对混合物进行纯化。真空干燥得到相应的碘化产物，产率为62％，见表1。22mg
Figure BDA0003834804430000092
94 mg of halogen bond organic framework XOF-TPy and 1.5 ml of anhydrous acetonitrile were added to the reaction tube and stirred at 81°C (generally the reaction temperature is 0-100°C, and 81°C is preferred in this embodiment) for 18 hours under argon protection. The reaction system was then filtered and concentrated by rotary evaporation. The mixture was purified by column chromatography (PE:EA=8:1). The corresponding iodinated product was obtained by vacuum drying with a yield of 62%, as shown in Table 1.

实施例19Embodiment 19

将18mg

Figure BDA0003834804430000093
78mg卤键有机框架XOF-TPy和1.5ml无水乙腈加入反应管中，在氩气保护下，81℃(一般反应温度为0-100℃，本实施例优选81℃)下搅拌14h。然后将反应体系过滤，通过旋转蒸发浓缩。用柱层析法(PE：EA＝40:3)对混合物进行纯化。真空干燥得到相应的碘化产物，产率为60％，见表1。18mg
Figure BDA0003834804430000093
78 mg of halogen bond organic framework XOF-TPy and 1.5 ml of anhydrous acetonitrile were added to the reaction tube and stirred at 81°C (generally the reaction temperature is 0-100°C, and 81°C is preferred in this embodiment) for 14 h under argon protection. The reaction system was then filtered and concentrated by rotary evaporation. The mixture was purified by column chromatography (PE:EA=40:3). The corresponding iodinated product was obtained by vacuum drying with a yield of 60%, as shown in Table 1.

实施例20Embodiment 20

将18mg

Figure BDA0003834804430000094
157mg卤键有机框架XOF-TPy和1.5ml无水乙腈加入反应管中，在氩气保护下，81℃(一般反应温度为0-100℃，本实施例优选81℃)下搅拌14h。然后将反应体系过滤，通过旋转蒸发浓缩。用柱层析法(PE：EA＝40:3)对混合物进行纯化。真空干燥得到相应的碘化产物，产率为85％，见表1。18mg
Figure BDA0003834804430000094
157 mg of halogen bond organic framework XOF-TPy and 1.5 ml of anhydrous acetonitrile were added to the reaction tube and stirred at 81°C (generally the reaction temperature is 0-100°C, and 81°C is preferred in this embodiment) for 14 h under argon protection. The reaction system was then filtered and concentrated by rotary evaporation. The mixture was purified by column chromatography (PE:EA=40:3). The corresponding iodinated product was obtained by vacuum drying with a yield of 85%, as shown in Table 1.

表1实施例3-18反应的产率汇总Table 1 Summary of the yields of the reactions of Examples 3-18

Figure BDA0003834804430000101
Figure BDA0003834804430000101

Figure BDA0003834804430000111
Figure BDA0003834804430000111

以上所述是本发明的优选实施方式而已，当然不能以此来限定本发明之权利范围，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和变动，这些改进和变动也视为本发明的保护范围。The above is only a preferred embodiment of the present invention, which certainly cannot be used to limit the scope of rights of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and changes can be made without departing from the principle of the present invention, and these improvements and changes are also regarded as the protection scope of the present invention.

Claims (10)

1.一种用于碘化试剂的二维卤键有机框架材料，其特征在于：结构式为1. A two-dimensional halogen bond organic framework material for iodination reagent, characterized in that: the structural formula is
Figure FDA0003834804420000011
Figure FDA0003834804420000011
 2.一种如权利要求1所述的用于碘化试剂的二维卤键有机框架材料的制备方法，其特征在于，包括以下步骤：2. a preparation method for the two-dimensional halogen bond organic framework material of iodination reagent as claimed in claim 1, is characterized in that, comprises the following steps: A1、将配体L溶于有机溶剂I中，得到配体溶液；A1, dissolving the ligand L in the organic solvent I to obtain a ligand solution; A2、将四氟硼酸银溶于有机溶剂II后滴加入步骤A1获得的配体溶液中，室温下搅拌至反应完全，得到混合溶液；A2. Dissolving silver tetrafluoroborate in the organic solvent II is added dropwise to the ligand solution obtained in step A1, and stirred at room temperature until the reaction is complete to obtain a mixed solution; A3、将碘溶于有机溶剂III后滴加入步骤A2获得的混合溶液中，室温下搅拌至反应完全，将沉淀分离、洗涤并干燥；A3. Dissolve iodine in organic solvent III and add dropwise to the mixed solution obtained in step A2, stir at room temperature until the reaction is complete, separate, wash and dry the precipitate; A4、将步骤A3获得的沉淀加入有机溶剂IV中，在40-200℃下保持0.1-2h后缓慢降温，分离出沉淀、洗涤并干燥，即得到所述用于碘化试剂的二维卤键有机框架材料。A4. Add the precipitate obtained in step A3 into the organic solvent IV, keep it at 40-200°C for 0.1-2h, then slowly lower the temperature, separate the precipitate, wash and dry, and obtain the two-dimensional halogen bond for iodination reagent Organic framework materials. 3.根据权利要求2所述的用于碘化试剂的二维卤键有机框架材料的制备方法，其特征在于：所述步骤A1中，配体L的结构式为
Figure FDA0003834804420000021
3. the preparation method of the two-dimensional halogen bond organic framework material that is used for iodinating reagent according to claim 2, is characterized in that: in described step A1, the structural formula of ligand L is
Figure FDA0003834804420000021
 4.根据权利要求2所述的用于碘化试剂的二维卤键有机框架材料的制备方法，其特征在于：所述配体L、四氟硼酸银和单质碘的摩尔比为1:1.5:1.5。4. the preparation method of the two-dimensional halogen bond organic framework material that is used for iodination reagent according to claim 2, is characterized in that: the mol ratio of described ligand L, silver tetrafluoroborate and elemental iodine is 1:1.5 :1.5. 5.根据权利要求2所述的用于碘化试剂的二维卤键有机框架材料的制备方法，其特征在于：有机溶剂I为三氯甲烷和/或甲醇组成的溶剂，其中甲醇的体积占比范围为0％-100％，有机溶剂II为甲醇，有机溶剂III为三氯甲烷，有机溶剂IV为甲醇或N,N-二甲基甲酰胺。5. the preparation method of the two-dimensional halogen bond organic framework material that is used for iodinating reagent according to claim 2, is characterized in that: organic solvent I is the solvent that chloroform and/or methyl alcohol form, and wherein the volume of methyl alcohol accounts for The ratio ranges from 0% to 100%, the organic solvent II is methanol, the organic solvent III is chloroform, and the organic solvent IV is methanol or N,N-dimethylformamide. 6.一种权利要求1所述的用于碘化试剂的二维卤键有机框架材料或者权利要求2-4中任一项所述的制备方法制备的用于碘化试剂的二维卤键有机框架材料的应用，其特征在于：采用所述的二维卤键有机框架材料与芳基硼酸化合物合成碘代芳基化合物。6. A two-dimensional halogen bond organic framework material for iodination reagent according to claim 1 or the two-dimensional halogen bond for iodination reagent prepared by the preparation method described in any one of claims 2-4 The application of the organic framework material is characterized in that: the iodoaryl compound is synthesized by using the two-dimensional halogen bond organic framework material and the arylboronic acid compound. 7.根据权利要求6所述的应用，其特征在于，包括以下步骤：将二维卤键有机框架材料和芳基硼酸化合物溶于溶剂V中，在0-100℃、惰性气氛下反应至完全，冷却后过滤、浓缩、纯化、干燥后得到所述碘代芳基化合物。7. The application according to claim 6, characterized in that it comprises the following steps: dissolving the two-dimensional halogen-bonded organic framework material and the arylboronic acid compound in solvent V, and reacting to complete at 0-100°C under an inert atmosphere , after cooling, filter, concentrate, purify and dry to obtain the iodoaryl compound. 8.根据权利要求6或7所述的应用，其特征在于：所述芳基硼酸化合物为以下化合物中的任意一种：8. The application according to claim 6 or 7, characterized in that: the aryl boronic acid compound is any one of the following compounds:
Figure FDA0003834804420000022
Figure FDA0003834804420000022
 9.根据权利要求6或7所述的应用，其特征在于：所述二维卤键有机框架材料与芳基硼酸化合物的摩尔比为1.0-2.0：1。9. The application according to claim 6 or 7, characterized in that the molar ratio of the two-dimensional halogen-bonded organic framework material to the arylboronic acid compound is 1.0-2.0:1. 10.根据权利要求7所述的应用，其特征在于：所述溶剂V为乙腈、甲醇、四氢呋喃、甲苯、氯仿、N,N-二甲基甲酰胺中的一种或多种溶剂的混合溶液。10. The application according to claim 7, characterized in that: the solvent V is a mixed solution of one or more solvents in acetonitrile, methanol, tetrahydrofuran, toluene, chloroform, N,N-dimethylformamide .
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