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Ionized iron (III) coordination compound containing phenol-bridged imidazolium and application thereof

A biimidazolium salt and ionic technology is applied in the field of ionic iron complexes containing phenol bridged biimidazolium salts to achieve the effects of deepening understanding, strong electron donating ability and high catalytic activity

Active Publication Date: 2012-07-25
优标易站(苏州)电子商务有限公司
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0007] So far, in the application of iron-based catalytic systems with imidazolium salts as auxiliary ligands in the cross-coupling reaction between aryl Grignard reagents and β-H-containing alkyl halides, the imidazolium salts used They are all monoimidazole ring systems, and there are no reports of iron-based catalysts containing bis-imidazole ring systems, that is, phenol-bridged bis-imidazole salts.

Method used

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  • Ionized iron (III) coordination compound containing phenol-bridged imidazolium and application thereof
  • Ionized iron (III) coordination compound containing phenol-bridged imidazolium and application thereof
  • Ionized iron (III) coordination compound containing phenol-bridged imidazolium and application thereof

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0038] [O-4-C(CH 3 ) 3 -C 6 h 2 -2,6-di-{CH 2 [CH(NCHCHNR)]}]FeX 4 (R is isopropyl, X=Cl) synthesis.

[0039] Under anhydrous and oxygen-free conditions, in an argon atmosphere, a tetrahydrofuran (THF) solution of ferric chloride (0.1622g, 1mmol) was added to a THF suspension of phenol bridged imidazolium salt (0.4675g, 1mmol), Stir at room temperature for 1 hour, the solid in the reaction system gradually disappeared, and the color of the solution was yellowish brown. Remove the solvent in vacuo, extract the residue with THF, centrifuge, drain the solvent, add THF and hexane solvent in turn, and precipitate at 0-5 °C The crystal is the above-mentioned ionic iron (III) complex containing phenol bridged imidazolium salt, and the yield is 75%.

[0040] We carried out elemental analysis, melting point determination, Raman spectrum characterization and crystal structure determination of the product.

[0041] The elemental analysis and melting point determination results of ...

Embodiment 2

[0083] [O-4-C(CH 3 ) 3 -C 6 h 2 -2,6-di-{CH 2 [CH(NCHCHNR)]}]FeX 4 (For isopropyl, X=Br) synthesis.

[0084] Under anhydrous and oxygen-free conditions, in an argon atmosphere, a tetrahydrofuran solution of iron tribromide (0.2957g, 1mmol) and anhydrous and oxygen-treated sodium bromide (0.6585g, 6.4mmol) were sequentially added to the phenol bridge Biimidazole salt (0.4675g, 1mmol) in tetrahydrofuran suspension, stirred at room temperature for 2 hours, the solid in the reaction system gradually disappeared, the solution color was yellowish brown, the solvent was removed in vacuo, the residue was extracted with THF, centrifuged, and drained As a solvent, add THF and hexane solvent in sequence, and crystals are precipitated at 0-5° C., which is the above-mentioned ionic iron (III) complex containing phenol-bridged imidazolium salt, with a yield of 70%.

[0085] The product was characterized by elemental analysis, melting point determination and Raman spectroscopy.

[008...

Embodiment 3

[0090] [O-4-C(CH 3 ) 3 -C 6 h 2 -2,6-di-{CH 2 [CH(NCHCHNR)]}]FeX 4 (R is methyl, X=Cl) synthesis.

[0091] Under anhydrous and oxygen-free conditions, in an argon atmosphere, a tetrahydrofuran solution of ferric chloride (0.1622g, 1mmol) was added to a THF suspension of phenol bridged imidazolium salt (0.4955g, 1mmol), and stirred at room temperature After 1 hour, the solid in the reaction system gradually disappeared, and the color was yellowish brown. Remove the solvent in vacuo, extract the residue with THF, centrifuge, drain the solvent, add THF and hexane solvent successively, and precipitate crystals at 0-5 °C, which is The yield of the above-mentioned ionic iron (III) complex containing phenol bridged imidazolium salt is 76%.

[0092] The product was characterized by elemental analysis and Raman spectroscopy.

[0093] The elemental analysis results of the product are shown in the table below:

[0094] C:(%)

[0095] The complex was characterized by...

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Abstract

The invention discloses an ionized iron (III) coordination compound containing phenol-bridged imidazolium. The ionized iron (III) coordination compound containing the phenol-bridged imidazolium is characterized by having a chemical general formula as follows: [O-4-C(CH3)3-C6H2-2,6-di-{CH2[CH(NCHCHNR)]}FeX4, wherein R is selected from one of benzyl, 2,6-diisopropyl phenyl, mesityl and saturated alkyl from C1 to C4; and X is chlorine or bromine. Aryloxy-bridged bis(N-heterocyclic carbine) synthesized in situ in the catalysis process of the ionized iron (III) coordination compound containing the phenol-bridged imidazolium disclosed by the invention is not only beneficial to the generation of a low-valence-state iron catalytic active center, but also capable of more effectively stabilizing the low-valence-state iron catalytic active center, so that the ionized iron (III) coordination compound disclosed by the invention has extremely high catalytic activity for the cross-coupling reaction between an aryl grignard reagent and alkyl halohydrocarbon containing b-H and novel efficient catalysts are developed.

Description

technical field [0001] The invention belongs to the field of ligands and complexes, in particular to an ionic iron (III) complex containing phenol bridged imidazolium salt and its application. Background technique [0002] The transition metal-catalyzed cross-coupling reaction between nucleophilic carbon atoms and halogenated hydrocarbons is an important reaction type for the formation of C-C bonds. It has become an indispensable means in organic synthesis and is widely used in biology, medicine, pesticides, fine The synthesis of chemicals and advanced materials, etc., has brought significant economic benefits to society (see: de Meijere, A.; Diederich, F.; Eds. Metal-Catalyzed Cross-Coupling Reactions, 2nd ed.; Wiley-VCH : Weinheim, 2004). In the past 30 years, a large number of transition metal catalysts have been developed, the most effective of which are the palladium and nickel-based catalysts, which not only provide the most abundant and efficient catalytic performanc...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F15/02B01J31/22C07B49/00C07C13/28C07C1/32
Inventor 孙宏枚夏莹朱凡张晓娟沈琪
Owner 优标易站(苏州)电子商务有限公司
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