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Three-dimensional N-heterocyclic carbene metal coordination polymer, preparation method and application thereof

A nitrogen-heterocyclic carbene and metal coordination technology, which is applied in the direction of organic compound/hydride/coordination complex catalysts, chemical instruments and methods, catalytic reactions, etc. Stability and other issues, to achieve the effect of good stability, high catalytic activity, efficient recovery and reuse

Active Publication Date: 2017-12-22
FUDAN UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

But summing up all the reactions, we found that homogeneous catalysts are efficient, but unstable to air and water, and cause loss of precious metals; heterogeneous catalysis realizes catalyst recycling, but the reaction conditions are harsh and the number of cycles is limited

Method used

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  • Three-dimensional N-heterocyclic carbene metal coordination polymer, preparation method and application thereof
  • Three-dimensional N-heterocyclic carbene metal coordination polymer, preparation method and application thereof
  • Three-dimensional N-heterocyclic carbene metal coordination polymer, preparation method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0062] Example 1, the preparation of tetraphenylmethane tetraimidazolium salt 5a (a nitrogen heterocyclic carbene precursor)

[0063]

[0064] At room temperature, add triphenylmethane chloride 1 (5 g) and aniline (4.4 mL) to a 50 mL round-bottom flask in sequence. Heat to 190°C for 15 minutes. Cool to room temperature, add dilute hydrochloric acid (2M, 20 mL) and methanol (30 mL), heat to 80°C and stir for 30 minutes. Cool to room temperature, filter, wash with water, and dry. Suspend the dried solid in N,N-dimethylformamide (50 mL), cool to -15 °C, add concentrated sulfuric acid (5.5 mL), isoamyl nitrite (4 mL), stir for 1 hour, then Hypophosphorous acid (25 mL) was added dropwise. Slowly raise the temperature to 50°C and stir for 5 hours. Filtration and washing gave tetraphenylmethane 2 (5.2 g, 90%). Add liquid bromine (12 mL) into a 50 mL round bottom flask, add tetraphenylmethane 2 (4 g) in batches, stir at room temperature for 20 minutes, and cool to -78 ℃ , add...

Embodiment 2

[0068] Example 2, preparation of novel three-dimensional nitrogen heterocyclic carbene metal coordination assembly supported catalyst 6a:

[0069]

[0070] Under the protection of nitrogen atmosphere, rigid tetradentate imidazolium salt (azacyclic carbene precursor) 5a (0.58 g), [Ir(COD)Cl] 2(0.33 g), DMF (5 mL), tetrahydrofuran solution of LiHMDS (1M, 2 mL), stirred evenly and heated to reflux for 12 hours, a large amount of yellow solid precipitated, stop heating and cool the reaction system to room temperature. After adding 10 mL of distilled water to the reaction system, it was filtered, the solid was washed with distilled water, and dried in vacuo to obtain a brownish-yellow solid, which was the three-dimensional azacyclic carbene metal coordination-assembled catalyst 6a, with a yield of 0.70 g, 94%. The IR spectrum of product characterization is as attached Figure 4 shown.

[0071] IR (KBr pellet) ν 617.24, 682.62, 823.55, 1246.19, 1363.81, 1476.16, 1507.57, 155...

Embodiment 3

[0072] Example 3, preparation of novel three-dimensional nitrogen heterocyclic carbene metal coordination assembly supported catalyst 6b:

[0073]

[0074] Under the protection of nitrogen atmosphere, rigid tetradentate imidazolium salt (azacyclic carbene precursor) 5a (0.58 g), [Ir(CO) 2 (acac)] (0.35 g), DMF (5 mL), tetrahydrofuran solution of LiHMDS (1M, 2 mL), stirred evenly and heated to reflux for 12 hours, a large amount of brown-yellow solid precipitated, stop heating and cool the reaction system to room temperature . After adding 10 mL of distilled water to the reaction system, it was filtered, the solid was washed with distilled water, and dried in vacuo to obtain a brownish-yellow solid, which was the three-dimensional azacyclic carbene metal coordination-assembled supported catalyst 6b, with a yield of 0.68 g, 97%. The IR spectrum of product characterization is as attached Figure 5 shown.

[0075] IR (KBr pellet) ν 1363.72, 1477.25, 1507.74, 1544.43, 1559....

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Abstract

Belonging to the technical field of heterogeneous catalysts, the invention specifically relates to a three-dimensional N-heterocyclic carbene metal coordination polymer, a preparation method and application thereof. The three-dimensional N-heterocyclic carbene metal coordination polymer provided by the invention can utilize a tetradentate imidazole salt to react with a metal precursor under an alkaline condition, and coordination assembly is conducted to obtain the three-dimensional N-heterocyclic carbene metal coordination polymer. The three-dimensional N-heterocyclic carbene metal coordination polymer can be used for catalyzing the hydrogenation cyclization reaction of biomass levulinic acid and levulinic acid derivative to prepare gamma-valerolactone and derivatives thereof efficiently. The three-dimensional self-loaded catalytic system combines the advantages of homogeneous catalysis and non-homogeneous catalysis, and can realize efficient, high selectivity and mass conversion of biomass keto acid raw material under very mild condition, also the catalyst has the advantages of high efficiency recovery and repeated recycle, and has very good application prospect in preparation of gamma-valerolactone in an industrial catalysis way.

Description

technical field [0001] The invention belongs to the technical field of heterogeneous catalysts, and in particular relates to a three-dimensional azacyclic carbene metal coordination polymer and its preparation method and application. Background technique [0002] Levulinic acid is considered a platform molecule because it is inexpensive and a readily available starting material. Levulinic acid can be effectively obtained through simple hydrolysis of biomass sugars (cellulose, sugar or starch), which is an industrial raw material produced in large quantities. With the deepening of research, γ-valerolactone, a value-added derivative of levulinic acid, has been paid more and more attention. γ-valerolactone is a very valuable compound, which has a wide range of applications in industry, such as coatings, adhesives, pesticides, food additives, etc. And it is a potential biofuel that has the potential to replace ethanol in gasoline-ethanol blends. In addition, γ-valerolactone h...

Claims

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Application Information

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IPC IPC(8): C08G83/00B01J31/22C07D307/33C07D309/30C07D307/88
CPCY02P20/55C08G83/008B01J31/1691B01J2231/641B01J2531/0233B01J2531/827C07D307/33C07D307/88C07D309/30
Inventor 涂涛刘尧旗
Owner FUDAN UNIV
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