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Two-oxazoline contained chiral dinuclear ligand with benzo cinnoline maternal skeleton, and synthesis method thereof

A technology of benzocinnoline and synthesis method, which is applied in the field of chiral dinuclear ligand containing two oxazolines and its synthesis, and can solve the problems of limited chiral catalytic reaction, small atomic radius, limited oxygen coordination ability, etc. , to achieve the effect of good application prospects

Inactive Publication Date: 2012-05-23
SHANGHAI JIAO TONG UNIV +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, the coordination ability of oxygen is limited and the atomic radius is small, which not only requires the selected metal to have higher Lewis acidity, but also requires the distance between the two metals in the catalyst to be very close, thus limiting the application of the catalyst. Types of Chiral Catalytic Reactions

Method used

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  • Two-oxazoline contained chiral dinuclear ligand with benzo cinnoline maternal skeleton, and synthesis method thereof
  • Two-oxazoline contained chiral dinuclear ligand with benzo cinnoline maternal skeleton, and synthesis method thereof
  • Two-oxazoline contained chiral dinuclear ligand with benzo cinnoline maternal skeleton, and synthesis method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0043] (1) prepare 2-nitro-3-iodobenzoic acid methyl ester from 3-iodobenzoic acid:

[0044] Put 6.0mL of fuming nitric acid in a 25mL two-necked bottle, drop to -10°C, slowly add 5.0g (20mmol) of m-iodobenzoic acid, react at -10°C for 3 hours, suction filter with a sand core funnel, wash with water, transfer the solid to The one-necked bottle was vacuum pumped dry. 4.28 g of a light yellow powder solid mixture was obtained.

[0045] 4.28g (14.6mmol) of the obtained light yellow powder solid mixture was dissolved in 11.6mL (146mmol) of methanol, 2mL of concentrated sulfuric acid was added dropwise, heated to 70°C, and the reaction was completed in 24 hours. Add 40 mL each of water and ethyl acetate dropwise, separate the layers, dry the organic phase with anhydrous sodium sulfate, spin dry, and separate through a column. The product 2-nitro-3-iodobenzoic acid methyl ester was obtained as 2.06 g of white crystals, and the yield was 33.5%.

[0046] 1H NMR (400MHz, CDCl 3 )δ=...

Embodiment 2

[0063] (1) Preparation of compound 2-nitro-3-iodobenzoic acid methyl ester from 3-iodobenzoic acid:

[0064] Put 10.0mL of fuming nitric acid in a 25mL two-necked bottle, drop to -10°C, slowly add 5.0g (20mmol) of m-iodobenzoic acid, react at -5°C for 100 hours, filter with a sand core funnel, wash with water, transfer the solid to The one-necked bottle was vacuum pumped dry. 4.5 g of a light yellow powder solid mixture was obtained.

[0065] 4.28g (14.6mmol) of the obtained light yellow powder solid mixture was dissolved in 0.85mL (14.6mmol) of methanol, 2mL of concentrated sulfuric acid was added dropwise, heated to 65°C, and the reaction was completed in 100 hours. Add 40 mL each of water and ethyl acetate dropwise, separate the layers, dry the organic phase with anhydrous sodium sulfate, spin dry, and separate through a column. The product 2-nitro-3-iodobenzoic acid methyl ester was obtained as 1.5 g of white crystals, and the yield was 24.4%.

[0066] 1H NMR (400MHz, C...

Embodiment 3

[0082] Starting from substituted m-iodobenzoic acid II, dinuclear ligand I is prepared via compounds III, IV, V, VI, VII:

[0083] (1) prepare 2-nitro-3-iodobenzoic acid methyl ester from 3-iodobenzoic acid:

[0084] Put 16.0mL of fuming nitric acid in a 25mL two-necked bottle, drop to -10°C, slowly add 5.0g (20mmol) of m-iodobenzoic acid, react at 10°C for 1 hour, filter with a sand core funnel, wash with water, and transfer the solid into a single-port Vacuum pump the bottle dry. 4.1 g of a light yellow powder solid mixture was obtained.

[0085] 4.28 g (14.6 mmol) of the obtained light yellow powder solid mixture was dissolved in 85 mL (1460 mmol) of methanol, 2 mL of concentrated sulfuric acid was added dropwise, and the reaction was carried out at 20° C. for 1 hour. Add 40 mL each of water and ethyl acetate dropwise, separate the layers, dry the organic phase with anhydrous sodium sulfate, spin dry, and separate through a column. The product 2-nitro-3-iodobenzoic acid ...

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PUM

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Abstract

The invention relates to a two-oxazoline contained chiral dinuclear ligand with a benzo cinnoline maternal skeleton, and a synthesis method thereof, which belong to the field of chemical technology. The structural formula of the chiral dinuclear ligand I is shown in a formula I. A nitrogen-nitrogen double bond is used as a connection functional group to be connected with bi-metal to be designed into a series of novel chiral dinuclear ligands which can be used for screening more transition metals and applied to more asymmetric catalytic reactions. The synthesis method provided by the invention is simple and has higher yield, the prepared ligand can be coordinated with copper, palladium, silver, rhodium, ruthenium and zinc to form monometallic and bimetallic catalysts applied to many catalytic reactions, and the ligand has a good application prospect.

Description

technical field [0001] The invention relates to a ligand in the technical field of chemical synthesis and a preparation method thereof, in particular to a chiral dinuclear ligand containing two oxazolines with benzocinnoline as a parent skeleton and a synthesis method thereof. Background technique [0002] The key to asymmetric catalytic synthesis is how to design and synthesize chiral catalysts with high selectivity and high catalytic activity, in which chiral ligands are the source of chirality induction and control of chiral catalysts, and metal ions act as active centers of catalytic reactions. effect. Chiral oxazoline ligands are widely used in various reactions catalyzed by metals, such as cyclopropanation, Micheal Addition reactions, Diels-Alder reactions, etc. After nearly two decades of development, a large number of chiral oxazoline ligands have emerged. In addition, chiral bimetallic catalysts have gradually gained the attention of chemists. Among them, the chi...

Claims

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Application Information

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IPC IPC(8): C07D413/14
Inventor 张万斌杨国强张亮
Owner SHANGHAI JIAO TONG UNIV
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