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Unsymmetrical β-diimine monovalent magnesium compound and its preparation method and application

A technology of magnesium compounds and diimine, which is applied in the preparation of imino compounds, magnesium organic compounds, chemical instruments and methods, etc., can solve the problems such as the lack of alkaline earth metal compounds, and achieve simple structure, easy synthesis and high catalytic activity. Effect

Inactive Publication Date: 2019-11-05
NANJING FORESTRY UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

So far, no alkaline earth metal compounds have been reported to catalyze the hydroboration of boranes and alkynes

Method used

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  • Unsymmetrical β-diimine monovalent magnesium compound and its preparation method and application
  • Unsymmetrical β-diimine monovalent magnesium compound and its preparation method and application
  • Unsymmetrical β-diimine monovalent magnesium compound and its preparation method and application

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0033] (1) Preparation of asymmetric β-diimine ligands

[0034] Under argon protection, add 140mL of toluene to a 250mL round bottom flask, then add 132mmol of 2,6-diisopropylaniline, 132mmol of acetylacetone and 1.6mmol of p-toluenesulfonic acid. Reflux for 8 hours, after the reaction is completed, pump dry, then add 132 mmol of 2,6-dimethylaniline and 132 mmol of p-toluenesulfonic acid, reflux for 21 hours at 150°C in a Dean-Stark apparatus in 130 mL of toluene solvent, pump dry, and use two Methyl chloride and saturated NaHCO 3 Extracted three times, the organic phase was extracted with anhydrous MgSO 4 After drying and drying, the obtained solid is an asymmetric β-diimine ligand, referred to as DipXyl NacnacH, 71% yield.

[0035] Characterize the product, NMR data: 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...

Embodiment 2

[0039] Example 2: [{( DipXyl Nacnac)Mg} 2 ] Catalyzed Hydroboration of Phenylacetylene and Pinacacol Borane

[0040] Under anhydrous and oxygen-free conditions, in the glove box, [{( DipXyl Nacnac)Mg} 2 ]0.006mmol was added to about 0.5mL of toluene-d 8 Then add 0.18 mmol of pinacol borane with a pipette gun and mix evenly, and finally add 0.12 mmol of phenylacetylene, react at 110°C for 6 hours, and measure NMR. Calculated 1 H spectrum yield was 99%.

[0041] NMR data of the product: 1 H NMR (600MHz, tol-d 8 ):δ7.63(d, 3 J HH =18.6Hz,2H),7.30(d, 3 J HH =7.2Hz,2H),7.06(d, 3 J HH =7.2Hz,2H),6.35(d, 3 J HH =18.6Hz,2H),1.16(s,12H). 13 C{ 1 H}NMR (151MHz, tol-d 8 ): δ149.7, 137.1, 128.5, 128.3, 127.0, 116.2, 82.7, 24.5. 11 B NMR (193MHz, tol-d 8 ): δ30.37.

Embodiment 3

[0042] Example 3: [{( DipXyl Nacnac)Mg} 2 ]Catalyzed hydroboration reaction of p-methoxyphenylacetylene with pinacol borane

[0043] Under anhydrous and oxygen-free conditions, in the glove box, [{( DipXyl Nacnac)Mg} 2 ]0.006mmol was added to about 0.5mL of toluene-d 8 Then add 0.18mmol of pinacol borane with a pipette gun and mix evenly, and finally add 0.12mmol of p-methoxyphenylacetylene, react at 110°C for 10h, and measure NMR. Calculated 1 H spectrum yield was 98%.

[0044] NMR data of the product: 1 H NMR (600MHz, tol-d 8 ):δ7.62(d, 3 J HH =18.6Hz,2H),7.23(d, 3 J HH =8.4Hz,2H),6.60(d, 3 J HH =8.4Hz,2H),6.22(d, 3 J HH =18.6Hz,2H),3.26(s,3H).1.16(s,12H). 13 C{ 1 H}NMR (151MHz, tol-d 8 ): δ160.8, 149.8, 137.5, 131.0, 114.25, 83.0, 25.0. 11 BNMR (193MHz, tol-d 8 ): δ31.0.

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Abstract

The invention discloses an unsymmetrical β-diimine monovalent magnesium compound as well as its preparation method and application. 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 asymmetric β-diimine monovalent magnesium compound prepared by the invention has a remarkable catalytic effect in the hydroboration reaction of alkynes, the reaction conditions are mild, the reaction speed is fast, the yield can reach more than 90%, and the catalyst has high activity. , which is the first case of using an alkaline earth metal compound to catalyze this type of reaction, which has good practicability.

Description

technical field [0001] The invention relates to the technical field of catalytic reactions of magnesium metal compounds, in particular to an asymmetric monovalent magnesium compound, its preparation method and its application in alkyne hydroboration reaction. Background technique [0002] Boronic acid esters are a key class of organic reagents in synthetic chemistry because organoborates are considered stable, easy-to-handle, and versatile, and thus they can serve as building blocks for various cross-coupling transformations [Boronic Acids, ed. D.G. Hall, Wiley-VCH, 2011]. Hydroboration of alkynes provides a straightforward and efficient method for the preparation of organoborate compounds. Metal-catalyzed hydroboration of alkynes has been shown to be an atom-economical and selective route to alkenyl boronic esters, and thus the development of efficient metal catalysts for regio- and stereoselectivity has attracted considerable attention. Many groups have investigated tran...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07F3/02C07C249/02C07C251/12C07F5/02B01J31/22
CPCB01J31/1805B01J2531/0241B01J2531/22C07C249/02C07C251/12C07F3/003C07F5/025
Inventor 马猛涛华海明沈兴超李佳
Owner NANJING FORESTRY UNIV
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