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NN ligand, NN ligand iron complex, crystals, preparation method and applications thereof

A technology of iron complexes and ligands, applied in the preparation of carbon-based compounds, the preparation of organic compounds, iron-organic compounds, etc., can solve the problems of low reaction yield, high production cost, poor stereoselectivity, etc.

Inactive Publication Date: 2015-11-25
SHANGHAI INST OF ORGANIC CHEMISTRY - CHINESE ACAD OF SCI
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  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0004] The technical problem to be solved by the present invention is in order to overcome the preparation method report of secondary allyl borate in the prior art is less, the applicable substrate range of reaction is narrow, the stereoselectivity of reaction is poor, regioselectivity is poor, reaction yield is low , cumbersome steps, high production cost, not suitable for industrial production and other defects, and provides NN ligand, NN ligand iron complex, crystal, preparation method and application

Method used

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  • NN ligand, NN ligand iron complex, crystals, preparation method and applications thereof
  • NN ligand, NN ligand iron complex, crystals, preparation method and applications thereof
  • NN ligand, NN ligand iron complex, crystals, preparation method and applications thereof

Examples

Experimental program
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Effect test

Embodiment 1

[0156] Embodiment 1: prepare NN ligand 6 of the present invention

[0157]

[0158] Add 2-acetyl-6-methylpyridine (2.5g, 18.5mmol, 1.0equiv), 2,6-diisopropylaniline (2.5g, 15.3mmol, 0.77equiv) and p-toluene to a 100ml single-necked bottle successively Sulfonic acid (141.0mg, 741μmol, 4mol%), toluene (30mL), then reflux for 48h and remove the water formed by the reaction through a water separator. After the reaction, the solvent was removed under reduced pressure, the sample was dry-loaded, and separated by column chromatography (v / v, ethyl acetate:n-hexane=1:100) to obtain yellow oil 6a, 3.6g, with a yield of 81%.

[0159] 1 HNMR (400MHz, CDCl 3 )δ=8.16-8.14(d, J=7.6Hz, 1H, Ar-H), 7.70-7.66(t, J=7.6Hz, 1H, Ar-H), 7.24-7.22(m, 1H, Ar-H ),7.16-7.15(m,2H,Ar-H),7.10-7.06(m,1H,Ar-H),2.79-2.72(m,2H,Ar(CH(CH 3 ) 2 ) 2 ),2.619(s,3H,ArCH 3 ),2.21(s,3H,NCCH 3 ), 1.15-1.13(d, J=7.2, 12H, Ar(CH(CH 3 ) 2 ) 2 ). 13 CNMR (101MHz, CDCl 3 )δ=167.50, 157.49, 156.06, 146.75, 136....

Embodiment 2

[0161] Embodiment 2: prepare the NN ligand 6 of the present invention

[0162]

[0163] Add 2-acetylpyridine (3.6g, 30.0mmol, 1.0equiv), 2,6-diethylaniline (3.7g, 25mmol, 0.83equiv), p-toluenesulfonic acid (285.0mg, 1.5 mmol, 5mol%), toluene (40mL), then reflux for 48h and remove the water generated by the reaction through a water separator. After the reaction was completed, the solvent was removed under reduced pressure, the sample was dry-loaded, and column chromatography (v / v, ethyl acetate:n-hexane=1:100) was obtained to obtain NN ligand 6e5.5g in a yellow oil with a yield of 88% .

[0164] 1 HNMR (400MHz, CDCl 3 )δ=8.68-8.66(m,1H,Ar-H),8.38-8.36(m,1H,Ar-H),7.82-7.78(td,J=8.0Hz,1.6Hz,1H,Ar-H), 7.39-7.36(m,1H,Ar-H),7.12-7.10(d,J=7.6Hz,2H,Ar-H),7.05-7.01(m,1H,Ar-H),2.46-2.29(m, 4H,Ar(CH 2 CH 3 ) 2 ),2.02(s,3H,NCCH 3 ), 1.15-1.12(t, J=7.6Hz, 6H, Ar(CH 2 CH 3 ) 2 ). 13 CNMR (101MHz, CDCl 3 )δ=167.01, 156.54, 148.68, 147.84, 136.57, 131.26, 126.02, 124.92, 123....

Embodiment 3

[0177] Embodiment 3: prepare NN ligand iron complex 7 of the present invention

[0178]

[0179] In a nitrogen glove box, the FeCl 2 (133mg, 1.0mmol, 1.0equiv) and THF (35mL) were added to a 50mL round bottom Schlenk bottle, and the FeCl 2 After complete dissolution, a THF solution (10 mL) of 6a ligand (324 mg, 1.1 mmol, 1.05 equiv) was added dropwise to the above solution, the color gradually turned blue-brown, and the reaction was stirred at room temperature for 24 h. After the reaction is completed, filter with dried diatomaceous earth in the glove box. After the filtrate is concentrated to 1-2 mL, add about 10 mL of n-hexane to it, and a large amount of red solid will be precipitated; then filter the obtained solid with a fine sand core And washed with n-hexane, the solvent was removed under reduced pressure to obtain blue powder 7j. Complex 7j is dissolved in CH 2 Cl 2 / n-hexane mixed solvent (volume ratio 1:7), slowly volatilized to obtain a single crystal, and it...

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Abstract

The invention discloses a NN ligand, a NN ligand iron complex, crystals, a preparation method and applications thereof. The invention provides a NN ligand 6, a NN ligand iron complex, crystals of NN ligand iron complexes 7j, 7k and 7h, preparation methods of the crystals, and applications of the NN ligand iron complex 7 in catalysis of diolefin boron hydrogenation reactions. The method has the advantages of environmental protection, high atomic economy, mild reaction condition, high stereoselectivity, high regioselectivity, high conversion rate, high yield, simple post-processing operation, wide range of suitable substrates, good compatibility, low production cost and application of industrial production.

Description

technical field [0001] The invention relates to NN ligand, NN ligand iron complex, crystal, preparation method and application. Background technique [0002] Allyl borate is an important class of organic synthesis intermediates. This type of compound is widely used in the allylation reaction of carbonyl, in which the stereo configuration of the carbon-carbon double bond of the allyl group can be preserved. In addition, primary and secondary allyl boron compounds are also used in palladium-catalyzed allyl substitution reactions, and the generated alkyl aromatics are an important class of substituted aromatic compounds. Methods for the synthesis of primary allyl borates have been extensively developed, but methods for the synthesis of secondary allyl borates are relatively rare. The classic synthesis method of secondary allyl borate is to react organolithium reagent or Grignard reagent with borate. Recently, Aggarwal et al. reported a lithiated borylation method to obtain c...

Claims

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Application Information

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IPC IPC(8): C07D213/53C07F9/58C07F15/03B01J31/22B01J31/24C07F5/04C07C43/215C07C41/30C07C15/52C07C1/32C07C49/796C07C45/68C07D317/50C07D317/54C07D317/52C07C49/813C07C43/225
Inventor 黄正曹艳春张延路
Owner SHANGHAI INST OF ORGANIC CHEMISTRY - CHINESE ACAD OF SCI
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