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Organic ligand and Pd/Pb-based bi-metal organic framework as well as synthetic method and application thereof

A technology of organic framework and organic ligand, which is applied in the field of catalyst preparation, can solve the problems of excessive phosphine ligand usage, non-recyclable catalyst, and air sensitivity, and achieve the effects of less catalyst usage, easy recycling, and mild reaction temperature

Inactive Publication Date: 2016-02-24
SHANDONG NORMAL UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
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Problems solved by technology

At present, transition metal-catalyzed coupling reactions involving benzyne are mostly homogeneous reactions. Although the efficiency is high, the catalyst is not recyclable and the cost is high.
At the same time, most of the reaction catalytic ligands are organophosphine ligands. In the field of catalysis, organophosphine ligands assist transition metals as catalysts are widely used. Organic phosphine ligands can stabilize low-valent metal centers and pass The dissociation of the ligand provides a coordination site but because the phosphorus-carbon bond is easy to break during the reaction, the amount of the phosphine ligand generally needs to be greatly excessive, and the organophosphine ligand generally has the following disadvantages: (1) low toxicity, (2) poor stability, (3) sensitive to air, (4) expensive, so chemists have been looking for a suitable ligand (such as TV-heterocyclic ligand) to replace the phosphine ligand for Catalytic reaction
Since nitrogen-heterocyclic carbene ligands can coordinate both transition metals and main group metals, and the nitrogen-heterocyclic carbene ligands have stronger electron-donating ability and stereoselectivity than phosphine ligands. The body has the above-mentioned advantages, nitrogen-heterocyclic carbene metal compounds are widely used in organic catalysis, and carbene ligands assist transition metal-catalyzed benzyne coupling reactions are rarely reported

Method used

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  • Organic ligand and Pd/Pb-based bi-metal organic framework as well as synthetic method and application thereof
  • Organic ligand and Pd/Pb-based bi-metal organic framework as well as synthetic method and application thereof
  • Organic ligand and Pd/Pb-based bi-metal organic framework as well as synthetic method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0055] Embodiment 1: Preparation of Pd carbene metal organic ligand L

[0056] Concrete preparation steps are as follows:

[0057] (1)N 2 Under protection, methyl 4-bromobenzoate (4.3g, 20mmol), imidazole (2.04g, 30mmol), cesium carbonate (19.6, 60mmol), cuprous iodide (0.19g, 1mmol) were added to a three-necked flask, Add dry 100mL DMF, stir and heat to 130°C. After the reaction is monitored by TLC, pour it into 200mL saturated saline, extract with 200mL×3 dichloromethane, combine the organic phases, and wash with saturated saline three times, and wash the organic phase with anhydrous sulfuric acid Dry over magnesium, filter, remove the solvent under reduced pressure, and separate and purify by column chromatography to obtain 3.15 g of white solid with a yield of 78.00%.

[0058]

[0059] (2) Intermediate A (5 mmol, 1.01 g) was placed in a 100 ml single-necked bottle, 10 ml of dibromomethane was added, and heated to reflux overnight. According to TLC tracking, after the...

Embodiment 2

[0064] Embodiment 2: the synthesis of Pd / Pb-MOF

[0065] The organic ligand L (6.80 mg, 0.01 mmol) prepared in Example 1, lead nitrate (0.04 mmol, 13.3 mg), oxalic acid (1 mmg, 0.01 mmol) were dissolved in 2 mL of ethanol: water = 1:3 mixed solvent, Put it in a 5ml small test tube, keep the temperature at 150°C for 72 hours, and cool it down to room temperature after 50 hours, to obtain colorless blocky crystal {[Pb 4 (C 42 h 28 N 8 o 8 Pd)(C 2 o 4 )Br 4 ]}, yield 4.2 mg, yield 20% (based on L).

[0066] We characterized the compound by IR, TGA, the results are shown in Figure 5 with Image 6 , the single crystal structure of Pd / Pb-MOF is shown in figure 1 As shown, the three-dimensional structure of Pd / Pb-MOF is as follows figure 2 shown.

experiment example 3

[0067] Experimental example 3: Pd / Pb-MOF catalyzes the self-coupling of benzyne to generate 9,10-triphenylene. The reaction equation is as follows:

[0068]

[0069] 2-(Trimethylsilyl)phenyltrifluoromethanesulfonate (0.5mmol, 121 μL), cesium fluoride (1.5mmol, 228mg), 2ml of acetonitrile were added to a 25ml single-necked round bottom flask, and then 12mg of catalyst compound was added, Stir, heat to 60°C, monitor the reaction progress by TLC, after two hours the reaction is over, centrifuge quickly to recover the catalyst, the product is extracted with dichloromethane, separated by column chromatography, the calculated yield is 72%.

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Abstract

The invention discloses an organic ligand and a Pd / Pb-based bi-metal organic framework as well as a synthetic method and application of the organic ligand and the Pd / Pb metal organic framework. A structural formula of the Pd / Pb-based bi-metal organic framework (Pd / Pb-MOF) is [Pb4(C42H28N8O8Pd)(C2O4)Br4]n, wherein n is a nonzero natural number. The Pd / Pb-based bi-metal organic framework (Pd / Pb-MOF) is used as a catalyst to be applied to catalyzing benzyne homocoupling and catalyzing three-component coupling reaction of benzyne, boracic acid and allyl halohydrocarbon. The MOF catalyst with active sites can be used for replacing some heavy metals to achieve a catalytic effect, so that the harm of the heavy metals to the environment is reduced. The MOF catalyst with the active sites is used for catalysis, so that heterocatalysis is realized; additionally, the bi-metal organic framework catalyst can be recycled for more than four times, and the catalyst is easy to recycle, so that the utilization rate of the catalyst is increased, and the cost is reduced.

Description

technical field [0001] The invention relates to an organic ligand, a Pd / Pb bimetallic organic framework, a synthesis method and application thereof, and belongs to the technical field of catalyst preparation. Background technique [0002] Metal-organic framework (Metal-organic Framework, MOF) is a research hotspot in recent years. Compared with traditional porous materials, MOF has porosity, larger specific surface area and pore volume in the framework. As a porous functional material in Applications in catalysis present great advantages. [0003] As an important reaction intermediate, benzyne has very active reactivity, so benzyne can be seen in many organic reactions, and has an irreplaceable position in synthesis. According to the different bonding methods, the reactions in which benzyne participates can be divided into the following categories: Diels-Alder reactions, cycloaddition reactions participating as double dipoles, and insertion reactions. In addition, reactions...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F15/00C07F19/00B01J31/22C07C1/32C07C15/38
CPCY02P20/584C07F15/006B01J31/1691B01J2231/4205C07B2200/13C07C1/32C07C2531/22C07C15/38
Inventor 董育斌董英李悦马建平
Owner SHANDONG NORMAL UNIV
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