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Asymmetric beta-diimine monovalent magnesium compound, preparation method and application thereof in aldehyde-ketone-boron hydrogenation reaction

A magnesium compound, asymmetric technology, applied in the preparation of amino compounds, the preparation of organic compounds, organic compound/hydride/coordination complex catalysts, etc., can solve problems such as the hydroboration reaction of borane and carbonyl compounds that have not yet been developed, Achieve the effect of simple and controllable reaction, easy synthesis and simple structure

Active Publication Date: 2018-01-09
NANJING UNIVERSITY OF TRADITIONAL CHINESE MEDICINE +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

So far, no monovalent magnesium compound has been reported to catalyze the hydroboration reaction of borane with carbonyl compounds

Method used

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  • Asymmetric beta-diimine monovalent magnesium compound, preparation method and application thereof in aldehyde-ketone-boron hydrogenation reaction
  • Asymmetric beta-diimine monovalent magnesium compound, preparation method and application thereof in aldehyde-ketone-boron hydrogenation reaction
  • Asymmetric beta-diimine monovalent magnesium compound, preparation method and application thereof in aldehyde-ketone-boron hydrogenation reaction

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0040] 1) Asymmetric β-diimine ligand ( DipMes Preparation of Nacnac(H)

[0041]Under the protection of argon, add 120mL of toluene to a 250mL round bottom flask, then add 145.8mmol of 2,6-diisopropylaniline, 145.8mmol of acetylacetone and 1.7mmol of p-toluenesulfonic acid, in the Dean-Stark apparatus Reflux at 160°C for 8h. After the reaction, drain and add 145.8mmol of 2,4,6-trimethylaniline and 145.8mmol of p-toluenesulfonic acid in 120mL of toluene solvent and reflux at 160°C for 24h . Drain, wash with dichloromethane and saturated NaHCO 3 Extracted three times, the organic phase was extracted with anhydrous MgSO 4 After drying and sucking to dryness, the obtained solid is the asymmetric β-diimine ligand with a yield of 64%. NMR data of the product: 1 H NMR (CDCl 3 ,600MHz):δ12.27(s,1H,NH),7.13(s,3H,Ar-H),6.89(s,2H,Ar-H),4.89(s,1H,=CH),3.08(sept , 3 J HH =6.6Hz,2H,CH(CH 3 ) 2 ),2.28(s,3H,CH 3 ),2.16(s,6H,CH 3 ),1.73(s,3H,NCCH 3 ),1.72(s,3H,NCCH 3 ),1.24(d, ...

Embodiment 2

[0045] 1) unsymmetrical β-diimine monovalent magnesium compound [{( DipXyl Nacnac)Mg} 2 ] preparation

[0046] Under anhydrous and oxygen-free conditions, under argon protection, in a single-port reaction tube, 8.29 mmol of methylmagnesium iodide was slowly added dropwise to the asymmetric β-diimine ligand ( DipXyl NacnacH) 8.29mmol ether solution, stirred overnight at room temperature, stood and filtered to obtain magnesium iodide. Then 2.48mmol of magnesium iodide was dissolved in 30mL of toluene, placed in a sodium mirror made of excess sodium 21mmol, reacted for 4 days, filtered, and the filtrate was concentrated to obtain a large number of crystals, which were asymmetric β-dimethoxy Amine monovalent magnesium compound[{( DipXyl Nacnac)Mg} 2 ], the yield was 60%. NMR data of the product: 1 H NMR (C 6 D. 6 ,600MHz):δ7.10–7.00(m,12H,Ar-H),4.84(s,2H,=CH),2.96(sept, 3 J HH =6.6Hz,4H,CH(CH 3 ) 2 ),1.96(s,12H,Ar-CH 3 ),1.57(s,6H,NCCH 3 ),1.48(s,6H,NCCH 3 ),1.10(d,...

Embodiment 3

[0047] Example 3: [{( DipMes Nacnac)Mg} 2 ] Catalyzed synthesis of boronate from benzaldehyde and pinacol borane

[0048] Under anhydrous and oxygen-free conditions, under nitrogen protection, in a glove box, the catalyst [{( DipMes Nacnac)Mg} 2 ]0.0003mmol was added to about 0.5mL of C 6 D. 6 Then add 0.3 mmol of pinacol borane with a pipette gun and mix evenly, and finally add 0.3 mmol of benzaldehyde, react at room temperature for 10 minutes, and measure NMR. Calculated 1 H spectrum yield was 99%. NMR data of the product: 1 HNMR (C 6 D. 6 ,600MHz):7.06-7.27(m,5H,Ar-H),4.92(s,2H,Ar-CH 2 ),1.08(s,12H,C(CH 3 ) 2 ).

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Abstract

The invention discloses an unsymmetrical β-diimine monovalent magnesium compound, a preparation method thereof and an application in aldehyde and ketone hydroboration reactions. Its preparation method is as follows: first condense acetylacetone with different kinds of aromatic amines respectively to generate asymmetric β-diimine ligands, then react it with an equal amount of methylmagnesium iodide to generate magnesium iodide, and finally use excess The sodium reduction of unsymmetrical β-diimine monovalent magnesium compound. The preparation method of the invention is simple, and the synthesized asymmetric β-diimine monovalent magnesium compound has a remarkable effect in the hydroboration reaction of aldehydes and ketones, and the catalyst consumption is only 0.1%, the reaction speed is fast, the yield is very high, and it is highly in line with green Chemistry concept.

Description

technical field [0001] The invention relates to the technical field of catalytic reactions of magnesium metal compounds, in particular to an asymmetric β-diimine monovalent magnesium compound, its preparation method and its application in the hydroboration reaction of aldehydes and ketones. Background technique [0002] Boron is a non-toxic, pollution-free inactive element, which has good flame-retardant, anti-wear and flame-retardant properties. Borate esters can be regarded as derivatives after the hydrogen in boric acid is replaced by organic groups, so it also has the characteristics of non-toxic, odorless, and good environmental adaptability. Therefore, borates are often used in flame retardants, surfactants, coupling agents, lubricating oil additives, automotive brake fluids, etc. The addition reaction of carbonyl compound and borane is an important method for borate synthesis. This reaction is non-toxic and harmless, has no other side reactions, and has good selectiv...

Claims

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Application Information

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IPC IPC(8): C07C209/00C07C211/53B01J31/22C07F5/04
Inventor 姚薇薇马猛涛沈兴超李佳
Owner NANJING UNIVERSITY OF TRADITIONAL CHINESE MEDICINE
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