Method for catalyzing cyanosilicification reaction of ketone by using deprotonated phenyl bridged beta-ketimine lithium complex

A technology for catalyzing ketone cyanosilicone and lithium ketimine, which is applied in catalytic reactions, organic compound/hydride/coordination complex catalysts, chemical instruments and methods, etc., can solve the problem of long time and high catalyst consumption of cyanosilication reaction , Catalyst preparation complex and other issues, to achieve the effect of efficient reduction

Inactive Publication Date: 2020-11-10
SUZHOU UNIV
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  • Summary
  • Abstract
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Problems solved by technology

[0003] In the prior art, n-butyllithium, ketone, and silane are mixed for cyanosilification reaction, which has a good catalytic effect on ketones and a wide range of substrates for trial use. However, n-butyllithium uses a higher catalyst dosage to catalyze ketones. Long cyanosilation reaction time
In the prior art, Mg-Al hydrotalcite laminates are first prepared; a series of polyacid intercalated hydrotalcite catalytic materials are prepared by intercalating polyacids into hydrotalcite laminates by exfoliation and recombination method, and the prepared polyacid intercalated water The talc catalytic material not only avoids the problem of equal impurities in the traditional multi-acid intercalation hydrotalcite process, but also has high catalytic activity for the addition reaction of aliphatic aldehydes, aromatic aldehydes and ketones, but the preparation process is complicated.
In the prior art, the metal-organic framework Ni-MOF-1 is synthesized by the organic ligand L, and then the crystal of Ni-MOF-1 is heated at 100°C for 4-6 hours to prepare Ni-MOF-2, and finally, the Ni -MOF-2 was immersed in the gas phase atmosphere of iodine for 24 hours to obtain a new type of iodine-supported catalyst Ni-MOF-3, which can effectively catalyze the silicocyanation reaction of benzaldehyde, does not require solvent reaction, and reduces the harm of toxic solvents to the environment; but Catalyst preparation is complex

Method used

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  • Method for catalyzing cyanosilicification reaction of ketone by using deprotonated phenyl bridged beta-ketimine lithium complex
  • Method for catalyzing cyanosilicification reaction of ketone by using deprotonated phenyl bridged beta-ketimine lithium complex
  • Method for catalyzing cyanosilicification reaction of ketone by using deprotonated phenyl bridged beta-ketimine lithium complex

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0026] Embodiment one: [L ph’ Li 4 (THF) 4 ] 2 Catalytic Reduction of Acetophenone and TMSCN

[0027] Under nitrogen atmosphere, add catalyst 0.6 mg (0.0005 mmol, 0.05%) to the reaction flask after dehydration and deoxygenation treatment, add acetophenone (116.6 μL, 1.0 mmol), TMSCN (137.6 μL, 1.1 mmol), after reacting at room temperature for 15 min, draw a drop into the NMR tube with a dropper, add CDCl 3 Dubbed into a solution. Calculated 1 H spectrum yield was 99%. NMR data of the product: 1 H NMR (400 MHz, CDCl 3 ) δ 7.49-7.46 (m, 2H, Ar H ),7.33-7.24 (m, 3H, Ar H ), 1.77 (s, 3H, C Me ), 0.11 (s, 9H, Si(C H 3 ) 3 ), the spectrum see figure 1 .

Embodiment 2

[0028] Embodiment two: [L ph’ Li 4 (THF) 4 ] 2 Catalytic Reduction of p-Methylacetophenone and TMSCN

[0029] Under a nitrogen atmosphere, add 0.6 mg (0.0005 mmol) of the catalyst to the reaction flask after dehydration and deoxygenation, and then add p-methylacetophenone (133.5 μL, 1.0 mmol), TMSCN (137.6 μL, 1.1 mmol), after reacting at room temperature for 15 min, draw a drop into the NMR tube with a dropper, add CDCl 3 Dubbed into a solution. Calculated 1 H spectrum yield was 99%. NMR data of the product: 1 H NMR (400 MHz, CDCl 3 ) δ 7.46 (d, 3 J H-H = 8.3 Hz, 2H, Ar H ),7.22 (d, 3 J H-H = 8.0 Hz, 2H, Ar H ), 2.38 (s, 3H, Ar-C H 3 ), 1.86 (s, 3H, C Me ),0.19 (s, 9H, Si(C H 3 ) 3 ).

Embodiment 3

[0030] Embodiment three: [L ph’ Li 4 (THF) 4 ] 2 Catalyzed reduction reaction of o-fluoroacetophenone and TMSCN

[0031] Under a nitrogen atmosphere, add 0.6 mg (0.0005 mmol) of the catalyst to the reaction flask after dehydration and deoxygenation, and then add o-fluoroacetophenone (124.1 μL, 1.0 mmol), TMSCN (137.6 μL, 1.1 mmol) with a pipette gun ), after reacting at room temperature for 15 min, draw a drop into the NMR tube with a dropper, add CDCl 3 Dubbed into a solution. Calculated 1 H spectrum yield was 99%. NMR data of the product: 1 H NMR (400 MHz, CDCl 3 ) δ 7.54-7.50 (m, 1H, Ar H ), 7.30-7.25(m, 1H, Ar H ), 7.13-7.09 (m, 1H, Ar H ), 7.04-6.99 (m, 1H, Ar H ), 1.87 (s, 3H,C Me ), 0.19 (s, 9H, Si(C H 3 ) 3 ).

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Abstract

The invention discloses a method for catalyzing a ketone cyanosilicification reaction by using a deprotonated phenyl bridged beta ketimine lithium complex. The method comprises the following step: with the deprotonated phenyl bridged beta ketimine lithium complex as a catalyst and ketone and silane as raw materials, conducting reacting at room temperature for 15 minutes to complete the cyanosilicification reaction, wherein in the complex, each beta-ketimine unit is double anions, and since a double-anion beta-ketimino group is a group with high activity, efficient reduction of ketone and TMSCNcan be realized within a short reaction time at a reaction temperature of room temperature when the complex is applied to the cyanosilicification reaction of ketone.

Description

technical field [0001] The invention relates to a lithium complex and its application in the field of organic synthesis, in particular to a deprotonated β-ketimine lithium complex, its preparation method and its application in the cyanosilication reaction of ketones. Background technique [0002] β-ketoimine, as an important class of non-cene-based ligands, is easy to synthesize, its charge and steric effect can be easily adjusted by changing the substituents at the α-position and β-position, and it can be combined with metals through a variety of coordination methods. Coordination, thus forming the characteristics of metal complexes with structural diversity. However, compared with the research on β-diimine anionic ligands in organometallic chemistry, the application research of β-ketoimine anionic ligands is less. Existing reports focus on complexes with single anion β-ketimine as the backbone. There is no report about the complexes of dianions-ketimine ligands so far. ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F7/18B01J31/22
CPCB01J31/2243B01J2231/342B01J2531/11C07F7/188
Inventor 薛明强徐晓娟康子晗周帅陈素芳郑煜
Owner SUZHOU UNIV
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