Bidentate phosphine [2Fe2S] diiron complex as well as preparation method and application thereof

A technology of iron complexes and bidentate phosphine, which is applied in the field of applied research of catalyzing benzene to phenol, can solve the problems of long reaction time, low atom utilization rate, unfavorable large-scale utilization, etc.

Active Publication Date: 2020-07-07
QILU UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0007] In summary, the synthesis cycle of molecular sieve catalysts is long and the cost is high, which is not conducive to large-scale utilization in the future; the yield of phenol under the action of heteropolyacid catalysts is low , the reaction time is too long, and the utilization rate of atoms is low; the catalytic reaction temperature of metal oxide catalysts is too high, and the selectivity and yield of phenol are not high

Method used

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  • Bidentate phosphine [2Fe2S] diiron complex as well as preparation method and application thereof
  • Bidentate phosphine [2Fe2S] diiron complex as well as preparation method and application thereof
  • Bidentate phosphine [2Fe2S] diiron complex as well as preparation method and application thereof

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0040] Embodiment 1, (μ-dmedt) [Fe 2 (CO) 6 ]Synthesis

[0041] Under nitrogen atmosphere, add toluene (55mL), Fe(CO) 5 (13.4g, 68.6mmol) and 2,3-butanedithiol (2.77g, 22.7mmol), stirred and refluxed for 29h. After cooling to room temperature, the solvent was distilled off under reduced pressure at 140°C. The reaction solvent was dried under vacuum. Then it was separated and purified by silica gel column, eluted and purified with n-hexane as the eluent, and the product with the first band was collected to obtain red solid complex 1 (3.439 g, 37.9%).

[0042] Analysis of Complex 1: 1 H NMR (CDCl 3 ); δ=2.21(m, 2H, SCH), 1.33(d, 6H, CH 3 C). Elemental analysis; measured value; C, 30.07; H, 2.12. Theoretical value (C 10 h 8 o 6 Fe 2 S 2 ); C, 30.03; H, 2.02. Mass spectrum; measured value 401.2; theoretical value 400.7. 1 H NMR (CDCl 3 ); δ=2.21(m, 2H, SCH), 1.33(d, 6H, CH 3 C).

Embodiment 2

[0043] Embodiment 2, catalyst (μ-dmedt) [Fe 2 (CO) 6 ](PMe 3 ) 2 Synthesis

[0044] Under nitrogen protection, the PMe 3 (0.46mmol, 31.2mg), (μ-dmedt)[Fe 2 (CO) 6 ] (0.23mmol, 90mg) and Me 3 NO (46mg, 0.46mmol) was added to a 50mL round-bottomed Schleck flask, and 20mL of toluene solution was added under the condition of maintaining nitrogen atmosphere after anhydrous and oxygen-free operation (nitrogen was replaced three times). Then keep stirring and reacting under nitrogen atmosphere at toluene reflux temperature (110° C.) for 12 hours, the color of the solution turns dark red, stop the reaction and evaporate the solvent to dryness. The obtained red solid was separated and purified by silica gel column chromatography, using dichloromethane solution as the eluent, wherein the first band was unreacted (μ-dmedt)[Fe 2 (CO) 6 ] band and a single substitution product band, wherein the second band is the product band. After rotary evaporation of the product, 54.02 mg of ...

Embodiment 3

[0049] The synthesis of embodiment 3, phenol

[0050] At normal temperature and pressure, 3.0 mL of CH 3 CN was added to a 25mL single-necked flask with magnetic stirring, followed by adding 0.05mmol catalyst, 1mmol benzene, 6mmol hydrogen peroxide (H 2 o 2 ) and stirred evenly to fully dissolve the catalyst in the reaction solvent, and control the temperature of the reaction system to be 60°C. React for 2 hours. After the reaction was completed, the reaction liquid was naturally cooled to room temperature, centrifuged for 5 minutes (8000r / min), and the catalyst was separated from the system. The sample was analyzed by gas chromatography. The yield of phenol was 13.6%, and the selectivity was 100%.

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Abstract

The invention relates to a bidentate phosphine [2Fe2S] diiron complex as well as a preparation method and application thereof. In a nitrogen atmosphere, a reactant (mu-dmedt) [Fe2(CO)6] and trimethylphosphine PMe3 are mixed, an organic solvent is injected, stirring reaction is performed, then trimethylamine oxide is added, stirring reaction continues to be performed at the same temperature, a reaction product is separated, and the bidentate phosphine chelated [2Fe2S] diiron complex is obtained. According to the method, the bidentate phosphine chelated [2Fe2S] diiron complex (mu-dmedt) [Fe2(CO)6](PMe3)2 is used as a catalyst, acetonitrile is used as a solvent, hydrogen peroxide is used as a hydroxylation reagent, benzene is hydroxylated to prepare phenol by a one-step method, the catalyticyield can reach 18.6%, only the product phenol is obtained, the selectivity is 100%, and no by-product is generated.

Description

technical field [0001] The invention relates to the field of metalloenzyme biomimetic synthesis chemistry and catalysis application, in particular to a preparation method of a metal complex catalyst containing P ligand and its application research on direct one-step catalysis of benzophenol under mild conditions. Background technique [0002] Phenol is a colorless needle-like crystal with a special smell. As an industrial raw material, it is widely used in the synthesis of rubber, plastics, synthetic fibers, pesticide emulsification, medicine, additives, spices, paints, dyes, oil refining and other fine chemicals. There are many ways to synthesize p-phenol, and now the main methods for industrial production of phenol are cumene method, sulfonation method and toluene benzoic acid method. Among the three methods, the cumene method is the most promising and widely used method, and the conversion of benzene and propylene into phenol with more industrial production and applicatio...

Claims

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Application Information

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IPC IPC(8): C07F15/02B01J31/24B01J31/20B01J31/22C07C37/60C07C39/04
CPCC07F15/02B01J31/24B01J31/20B01J31/226C07C37/60C07C39/04B01J2531/842B01J2531/0238B01J2231/70Y02P20/52
Inventor 张夏肖加奇
Owner QILU UNIV OF TECH
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