Preparation method and application of 2, 9-diaryl-substituted phenanthroline and 2, 9-diaryl-substituted phenanthroline iron complex

A technology of o-phenanthroline and phenanthroline, applied in the field of o-phenanthroline iron complexes, can solve the problems of large substrate limitations, less iron catalysts, and low catalyst activity

Active Publication Date: 2018-01-16
NANKAI UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, there are few types of iron catalysts that can successfully catalyze the hydrosilation of olefins in the literature, and there are problems such as generally low catalyst activity, large substrate limitations, poor functional group tolerance, and difficulty in catalyst synthesis.

Method used

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  • Preparation method and application of 2, 9-diaryl-substituted phenanthroline and 2, 9-diaryl-substituted phenanthroline iron complex
  • Preparation method and application of 2, 9-diaryl-substituted phenanthroline and 2, 9-diaryl-substituted phenanthroline iron complex
  • Preparation method and application of 2, 9-diaryl-substituted phenanthroline and 2, 9-diaryl-substituted phenanthroline iron complex

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0070] Example 1: Preparation of 2,9-diaryl substituted o-phenanthroline 2a-2c

[0071]

[0072]Reactant 1 (747 mg, 3 mmol), 2,4,6-triethylphenylboronic acid (1.86 g, 9 mmol), Ba( Oh) 2 ·8H 2 O (4.74g, 15mmol), PdCl 2 (dPpf) (329mg, 0.45mmol), replace the system with nitrogen atmosphere on the vacuum line, add degassed toluene (100mL) and water (5mL) under nitrogen flow, start stirring, and heat the oil bath to 110°C. After heating and stirring for 15 h, TLC confirmed that the reactant was completely consumed, and the heating was stopped and cooled to room temperature. Remove the insoluble matter by filtration, wash the residue with 40mL DCM, and remove the filtrate under vacuum, dissolve the residual brown-black solid with 100mL DCM, transfer to a separatory funnel, wash with saturated saline, dry over anhydrous sodium sulfate, and remove the organic phase under vacuum Post-dry loading column chromatography (PE / EA=5:1 as eluent) to obtain the target product 2,9-bis-2,4...

Embodiment 2

[0080] Example 2: Preparation of 2,9-diaryl substituted o-phenanthroline 2d, 2e

[0081]

[0082] Into a 250mL two-necked bottle equipped with a reflux condenser, an air extraction head, and a rubber stopper, the reactant 1 (498mg, 2mmol), 2,4,6-triisopropylphenylboronic acid (596mg, 2.4mmol), K 3 PO 4 ·3H 2 O (2.66g, 10mmol), Pd (PPh 3 ) 4 (346 mg, 0.3 mmol), the system was replaced by nitrogen atmosphere on the vacuum line, degassed DME (70 mL) and water (2.5 mL) were added under nitrogen flow, stirring was started, and the temperature of the oil bath was raised to 95 °C. After heating and stirring for 15 h, TLC confirmed that the reactant was completely consumed, and the heating was stopped and cooled to room temperature. Remove the insoluble matter by filtration, wash the residue with 20mL DCM, vacuum precipitation, dissolve the residue with 50mL DCM and transfer to a separatory funnel, wash with saturated saline, dry over anhydrous sodium sulfate, dry the organic p...

Embodiment 3

[0087] Example 3: Preparation of 2,9-diaryl substituted o-phenanthroline iron complexes

[0088]

[0089] In a glove box, weigh 2,9-bis-2,4,6-triisopropylphenyl-1,10-phenanthroline (2a) (1.001 g, 2 mmol) and FeCl into a 25 mL reaction vial 2 (253.5mg, 2mmol), add 20mL tetrahydrofuran, react at room temperature for 24 hours, vacuum pump to remove part of tetrahydrofuran (about 5mL remaining in the system), add 15mL n-hexane, orange-red solid precipitates, filter, and use n-hexane (3× 5mL) to wash the filter cake, the resulting solids were collected, and the high vacuum pump was drained to obtain the target product 2,9-bis-2,6-diethylphenyl-1,10-phenanthroline ferrous chloride (3a), Orange powder, yield 83%, decomposition temperature 282-286 ℃. 1 HNMR (400MHz, CDCl 3 )δ53.85(s, 2H), 27.88(s, 2H), 3.76(s, 2H), 1.87(s, 2H), 1.10(s, 4H), 0.27(s, 6H), -3.58(s, 12H), -10.77(s, 4H), -12.86(s, 4H), -16.74(s, 2H).IR(neat): 3555m, 3481s, 3416s, 3237w, 2967w, 2933, 2033w, 1639m, 161...

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Abstract

The present invention relates to a preparation method and application of 2, 9-diaryl-substituted phenanthroline and a 2, 9-diaryl-substituted phenanthroline iron complex. Specifically, the substitutedphenanthroline is prepared by Suzuki coupling reaction of 2, 9-diaryl-dichloro-phenanthroline and arylboronic acid, and the 2, 9-diaryl-substituted phenanthroline iron complex is prepared by complexation reaction of the substituted phenanthroline and an iron salt. The phenanthroline iron complex can catalyze hydrosilation reaction of various olefins or alkynes with silane in the presence of additives, shows very high activity and selectivity especially for the hydrosilation reaction of styrene derivatives, 1-arylbutadiene and 1-alkyl-1-arylbutadiene, shows excellent 1,2-disubstituted ethylenebenzyl-site selectivity, and has a good application prospect.

Description

technical field [0001] The invention relates to a preparation method and application of a novel 2,9-diaryl substituted o-phenanthroline and its iron complex. Specifically, the substituted o-phenanthroline is prepared by Suzuki coupling reaction of 2,9-dichloro-phenanthroline and arylboronic acid, and it is complexed with iron salt to prepare the o-phenanthroline iron complex. compound. In the presence of additives, the o-phenanthroline iron complex can catalyze the hydrosilylation reaction of various alkenes or alkynes with silanes, showing high activity and selectivity, especially for styrene derivatives, 1-aryl Hydrosilylation of 1-alkyl-1-aryl-butadiene, 1-alkyl-1-aryl-butadiene, gives a different selectivity for Markov addition than known iron catalysts, and exhibits excellent selectivity for 1,2-disubstituted ethylene Benzyl selectivity has good application prospects. Background technique [0002] Organosilicon compounds are widely used in various fields such as indu...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D471/04C07F15/02B01J31/22C07F7/08
Inventor 朱守非胡梦阳贺荞王立新
Owner NANKAI UNIV
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