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Asymmetric beta-diimine univalent magnesium complex as well as preparation method and application thereof in hydroboration of nitrile

An asymmetric and diimine technology, applied in the field of asymmetric beta-diimine monovalent magnesium complex and its preparation, can solve problems such as yet, and achieve the effects of fast reaction speed, mild reaction conditions and non-toxic catalyst

Inactive Publication Date: 2018-01-19
NANJING FORESTRY UNIV +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

These reactions prove that monovalent magnesium metal compounds have high activity for organic nitrile compounds. Up to now, there has been no report on the hydroboration reaction of borane and organic nitrile compounds catalyzed by monovalent magnesium compounds.

Method used

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  • Asymmetric beta-diimine univalent magnesium complex as well as preparation method and application thereof in hydroboration of nitrile
  • Asymmetric beta-diimine univalent magnesium complex as well as preparation method and application thereof in hydroboration of nitrile
  • Asymmetric beta-diimine univalent magnesium complex as well as preparation method and application thereof in hydroboration of nitrile

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0033] (1) Asymmetric β-diimine ligand ( DipMes Preparation of Nacnac(H)

[0034] Under argon protection, add 120mL of toluene to a 250mL round bottom flask, then add 147mmol of 2,6-diisopropylaniline, 147mmol of acetylacetone and 1.8mmol of p-toluenesulfonic acid. Reflux for 9 hours, after the reaction is completed, pump dry, then add 147mmol of 2,4,6-trimethylaniline and 147mmol p-toluenesulfonic acid in 120mL of toluene solvent, reflux at 160°C for 24h under the Dean-Stark apparatus, pump dry, use Dichloromethane and saturated NaHCO 3 Extracted three times, the organic phase was extracted with anhydrous MgSO 4 After drying, the obtained solid is exactly the asymmetric β-diimine ligand ( DipMes NacnacH), the yield was 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, 3 J ...

Embodiment 2

[0037] Example 2: [{( DipMes Nacnac)Mg} 2 ] Catalyzed hydroboration reaction of benzonitrile and pinacol borane

[0038] Under anhydrous and oxygen-free conditions, in the glove box, [{( DipMes Nacnac)Mg} 2 ]0.006mmol was added to about 0.5mL of C 6 D. 6 Then add 1.2mmol of pinacol borane with a pipette gun and mix well, and finally add 0.6mmol of benzonitrile, react at 60°C for 8h, and measure the NMR. Calculated 1 H spectrum yield was 98%. NMR data of the product: 1 H NMR (C 6 D. 6 ,600MHz):7.58(m,2H,Ar-H),7.25(m,2H,Ar-H),7.11(m,1H,Ar-H),4.61(s,2H,Ar-CH 2 ),1.03(s,24H,C(CH 3 ) 2 ).

Embodiment 3

[0039] Example 3: [{( DipMes Nacnac)Mg} 2 ] Catalytic hydroboration of 4-methoxybenzonitrile and pinacol borane

[0040] Under anhydrous and oxygen-free conditions, in the glove box, [{( DipMes Nacnac)Mg} 2 ]0.006mmol was added to about 0.5mL of C 6 D. 6 Then add 1.2mmol of pinacol borane with a pipette gun and mix well, and finally add 0.6mmol of 4-methoxybenzonitrile, react at 60°C for 24h, and measure NMR. Calculated 1 H spectrum yield was 83%. NMR data of the product: 1 HNMR (C 6 D. 6 ,600MHz):7.56(d, 3 J HH =8.4Hz, 2H, Ar-H), 6.87(d, 3 J HH =8.4Hz,2H,Ar-H),4.58(s,2H,Ar-CH 2 ),3.34(s,3H,OCH 3 ),1.05(s,24H,C(CH 3 ) 2 ).

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Abstract

The invention discloses an asymmetric beta-diimine univalent magnesium complex as well as a preparation method and an application thereof in a hydroboration reaction of nitrile. The preparation methodcomprises the steps as follows: firstly, acetylacetone and 2,6-diisopropyl aniline are condensed and then react with 2,4,6-trimethylaniline to produce an asymmetric beta-diimine ligand, then the asymmetric beta-diimine ligand reacts with the same amount of methylmagnesium iodide to produce magnesium iodide, finally, the magnesium iodide is reduced with excessive sodium, and the asymmetric beta-diimine univalent magnesium complex is obtained. The preparation method is simple, the synthesized asymmetric beta-diimine univalent magnesium complex has the high yield and has significant effects in the hydroboration reaction of nitrile, the reaction condition is mild, the reaction speed is high, the yield can reach 90% or above, and a catalyst has very high activity.

Description

technical field [0001] The invention belongs to the technical field of synthesis and catalytic reaction of magnesium metal complexes, and specifically relates to an unsymmetrical β-diimine monovalent magnesium complex, a preparation method thereof and an application in nitrile hydroboration reaction. Background technique [0002] Since primary amines play a key role in the chemical industry as reaction intermediates, how to efficiently and multifunctionally synthesize these primary amines has become one of the focuses of current research [S.A.Lawrence, In Amines: Synthesis, Properties, and Application, Cambridge University, Cambridge, 2004.]. The reduction of organic nitriles to primary amines is one of the important ways to synthesize primary amines in many industries, and the catalytic hydrogenation of nitriles can be realized under heterogeneous conditions. However, these methods are often poorly selective and also lead to the formation of unwanted imine and secondary am...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F3/02B01J31/22C07F5/02
Inventor 马猛涛沈兴超李佳姚薇薇
Owner NANJING FORESTRY UNIV
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