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Ionic iron (III) complex containing bisphenol functional imidazoline salt and application thereof

An imidazoline salt, ionic technology, applied in cross-coupling reactions, in the field of ionic iron complexes, can solve the problems of dehalogenation and low yield of target products, and achieve easy product, simple reaction and easy operation , high yield effect

Inactive Publication Date: 2013-01-23
SUZHOU UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, among the iron-based catalysts developed above, there are very few successful examples of cross-coupling reactions involving b-H-containing alkyl chlorinated hydrocarbons. During the coupling reaction, alkyl chlorinated hydrocarbons are prone to side effects such as dehalogenation. reaction, the yield of the target product is generally low

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0043] [(ArNCH 2 CH 2 NAr)CH]FeX 4 (Ar = 3,5-di-C(CH 3 ) 3 -2-(OH)-C 6 h 2 , X = Cl) synthesis.

[0044] For the synthesis of ligands see: Charles, R.; Lydia, B.; Stephane, B. L.; Samuel, D. Organometallics, 2010, 29, 1191.

[0045] [(ArNCH 2 CH 2 NAr)CH]Cl (0.52 g, 1.0 mmol) was added to a tetrahydrofuran solution of ferric chloride (0.16 g, 1.0 mmol), reacted at 30°C for 2 hours, removed the solvent in vacuo, washed with hexane, and dried , extracted with tetrahydrofuran, centrifuged to transfer the supernatant, and added hexane to the supernatant for recrystallization, and yellow-brown crystals were precipitated at room temperature with a yield of 88%.

[0046] Carry out elemental analysis to product, test melting point, the result is as follows:

[0047] Elemental analysis and melting point

[0048] C：（%） H：（%） N：（%） theoretical value 54.97 6.99 4.14 actual value 54.55 7.19 3.91

[0049] Since the iron complex is paramagnetic, i...

Embodiment 2

[0054] [(ArNCH 2 CH 2 NAr)CH]FeX 4 (Ar = 3,5-di-C(CH 3 ) 3 -2-(OH)-C 6 h 2 , X = Br) synthesis.

[0055] In turn [(ArNCH 2 CH 2 NAr)CH]Cl (0.52 g, 1.0 mmol) and NaBr (0.32 g, 3.0 mmol) were added to a tetrahydrofuran solution of iron tribromide (0.29 g, 1.0 mmol), reacted at 60°C for 12 hours, and vacuum Remove the solvent, wash with hexane, drain, extract with tetrahydrofuran, transfer the supernatant by centrifugation, add hexane to the supernatant for recrystallization, and precipitate red-brown crystals at room temperature with a yield of 80%.

[0056] Carry out elemental analysis to product, test melting point, the result is as follows:

[0057] Elemental analysis and melting point

[0058] C：（%） H：（%） N：（%） theoretical value 43.54 5.54 3.28 actual value 44.05 5.95 3.25

[0059] Since the iron complex is paramagnetic, it was not characterized by NMR.

[0060] This complex [(ArNCH 2 CH 2 NAr)CH]FeBr 4 Exists in the form of io...

Embodiment 3

[0064] [(ArNCH 2 CH 2 NAr)CH]FeX 4 (Ar = 5-C(CH 3 ) 3 -2-(OH)-C 6 h 3 , X = Cl) for the synthesis of

[0065] (For the synthesis of ligands see: David, R. W.; Nilay, H.; Jay, A. L.; John, E. B. Organometallics, 2010, 29, 1).

[0066] [(ArNCH 2 CH 2NAr)CH]Cl (0.40 g, 1.0 mmol) was added to a tetrahydrofuran solution of ferric chloride (0.16 g, 1.0 mmol), reacted at 30°C for 2 hours, removed the solvent in vacuo, washed with hexane, and dried , extracted with tetrahydrofuran, centrifuged to transfer the supernatant, added hexane to the supernatant for recrystallization, and brown crystals were precipitated at room temperature with a yield of 84%.

[0067] Carry out elemental analysis to product, the result is as follows:

[0068] Elemental analysis

[0069] C：（%） H：（%） N：（%） theoretical value 48.88 5.53 4.96 actual value 49.22 5.61 4.90

[0070] Since the iron complex is paramagnetic, it was not characterized by NMR.

[0071] This co...

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Abstract

The invention discloses an ionic iron (III) complex containing bisphenol functional imidazoline salt, which is expressed by the following chemical structural formula shown in the specification, wherein R1 and R2 are respectively one of hydrogen atom, methyl and tert-butyl; and X is one of chlorine or bromine. According to the ionic iron (III) complex containing bisphenol functional imidazoline salt, such structural unit as imidazoline is first introduced into the design and synthesis of a ligand; meanwhile, the flexible and variable regulation and control on the steric hindrance and electronic effect of the corresponding iron (III) complex is realized by introducing a structure-variable phenoxy modification radical onto the imidazoline ring, thus developing a novel efficient iron-based catalyst; and the cross coupling reaction of alkyl primary / secondary bromohydrocarbon and alkyl primary / secondary chlorohydrocarbon can be effectively catalyzed.

Description

technical field [0001] The invention relates to a metal complex, in particular to an ionic iron (Ⅲ) complex containing bisphenol functionalized imidazolinium salt and its use as a single-component catalyst in the presence of aryl Grignard reagents and b-H-containing alkyl halides Applications in cross-coupling reactions between substituted hydrocarbons. Background technique [0002] Kumada cross-coupling reactions catalyzed by transition metal complexes are one of the most important methods for constructing carbon-carbon bonds in organic synthesis (see: de Meijere, A.; Diederich, F., Eds.; Metal-Catalyzed Cross-Coupling Reactions , 2nd ed.; Wiley-VCH, Weinheim, 2004), the development of efficient new catalysts has been the core driving force for the development of this field. In this reaction, traditional high-efficiency catalysts are mostly palladium-based or nickel-based complexes. In the past ten years, with the deepening of people's understanding of the sustainable dev...

Claims

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Application Information

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IPC IPC(8): C07F15/02B01J31/22C07C13/28C07C15/107C07C15/02C07C1/32
Inventor 孙宏枚夏崇亮解存飞沈琪
Owner SUZHOU UNIV
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