Preparation method of tetra-coordinated N,N-chelated diarylborate compound with 8-aminoquinoline derivatives as bidentate ligand

An aminoquinoline and bidentate ligand technology is applied in the field of preparation of four-coordinate N,N-chelated diarylboronic acid esters, which can solve the problems of harsh reaction conditions, poor functional group compatibility and low synthesis efficiency. , to achieve the effect of good raw material stability, high compatibility, and reduction of separation and purification steps

Active Publication Date: 2020-09-04
SHIHEZI UNIVERSITY
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Problems solved by technology

At present, the synthesis of this type of compound is still limited by the following two aspects: (1) Most of the reported four-coordination N,N-chelating diaryl borate esters use the dipyrrole structure as the ligand skeleton structure, and obtain Most of them are four-coordinated dipyrrole borates, which are common BODIPY compounds, but the synthesis and modification of this type of skeleton generally require multi-step reactions to complete, and the overall synthesis efficiency is not high; (2) in the synthesis of N, In the process of N-chelating diaryl borate, the step of introducing aryl needs to use aryl metal reagents (such as Grignard reagents, lithium reagents, zinc reagents) to complete, but the strong basicity and affinity of such reagents Nucleus, more demanding reaction conditions, poor functional group compatibility, some common functional groups, such as ester groups, aldehyde carbonyl groups, amide groups are not compatible with the reaction conditions

Method used

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  • Preparation method of tetra-coordinated N,N-chelated diarylborate compound with 8-aminoquinoline derivatives as bidentate ligand
  • Preparation method of tetra-coordinated N,N-chelated diarylborate compound with 8-aminoquinoline derivatives as bidentate ligand
  • Preparation method of tetra-coordinated N,N-chelated diarylborate compound with 8-aminoquinoline derivatives as bidentate ligand

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0048] 1-(2,2-Diphenyl-2λ 4 ,3λ 4 Preparation of -[1,3,2]diazaborolin[4,5,1-ij]quinolin-1(2H)-yl)-3-phenylpropan-1-one

[0049]

[0050] This example prepares 1-(2,2-diphenyl-2λ at the milligram level 4 ,3λ 4 -[1,3,2]diazabororine[4,5,1-ij]quinolin-1(2H)-yl)-3-phenylpropan-1-one, under air conditions, the N-phenylpropionyl-8-aminoquinoline (41.4 mg, 0.15 mmol, 1.0 equiv) and potassium phenyltrifluoroborate (138.0 mg, 0.75 mmol, 5.0 equiv), manganese (24.7 mg, 0.45 mmol, 3.0 equiv) , 4-toluenesulfonyl chloride (71.5mg, 0.375mmol, 2.5equiv), sodium carbonate (7.9mg, 0.075mmol, 0.5equiv), acetonitrile (1.5mL) were added to a pressure-resistant reaction flask, and reacted at 130°C for 24 hours . After the reaction, the reaction mixture was filtered, washed with dichloromethane, and the solvent was removed by rotary evaporation, and then purified by silica gel column chromatography (the silica gel specification was 200 to 300 mesh, the mass ratio of silica gel to the produc...

Embodiment 2

[0054] 1-(2,2-Di-p-tolyl-2λ 4 ,3λ 4 Preparation of -[1,3,2]diazaborolin[4,5,1-ij]quinolin-1(2H)-yl)-3-phenylpropan-1-one

[0055] Under air conditions, N-phenylpropionyl-8-aminoquinoline (41.4mg, 0.15mmol, 1.0equiv) and potassium 4-tolyltrifluoroborate (148.5mg, 0.75mmol, 5.0equiv), manganese (24.7 mg, 0.45mmol, 3.0equiv), 4-toluenesulfonyl chloride (71.5mg, 0.375mmol, 2.5equiv), sodium carbonate (7.9mg, 0.075mmol, 0.5equiv), acetonitrile (1.5mL) were added in a pressure-resistant reaction flask , reacted at 130°C for 24 hours. After the reaction, the reaction mixture was filtered, washed with dichloromethane, and the solvent was removed by rotary evaporation, and then purified by silica gel column chromatography (the silica gel specification was 200 to 300 mesh, the mass ratio of silica gel to the product to be purified was 200:1, and the eluent was petroleum ether and ethyl acetate volume ratio is 3:1 mixed liquor), obtain target product 1-(2,2-two-p-tolyl-2λ 4 ,3λ 4 -[...

Embodiment 3

[0058] 1-(2,2-bis(4-methoxyphenyl)-2l 4 ,3l 4 Preparation of -[1,3,2]diazaborolin[4,5,1-ij]quinolin-1(2H)-yl)-3-phenylpropan-1-one

[0059] Under air conditions, N-phenylpropionyl-8-aminoquinoline (41.4 mg, 0.15 mmol, 1.0 equiv) and potassium 4-methoxyphenyl trifluoroborate (160.5 mg, 0.75 mmol, 5.0 equiv), Manganese (24.7mg, 0.45mmol, 3.0equiv), 4-toluenesulfonyl chloride (71.5mg, 0.375mmol, 2.5equiv), sodium carbonate (7.9mg, 0.075mmol, 0.5equiv), acetonitrile (1.5mL) were added under pressure In the reaction flask, the reaction was carried out at 130° C. for 24 hours. After the reaction, the reaction mixture was filtered, washed with dichloromethane, and the solvent was removed by rotary evaporation, and then purified by silica gel column chromatography (the silica gel specification was 200 to 300 mesh, the mass ratio of silica gel to the product to be purified was 200:1, and the eluent was petroleum ether and ethyl acetate volume ratio is 3:1 mixed liquor), obtain targe...

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Abstract

The invention discloses a tetra-coordinated N,N-dimethylformamide compound with 8-aminoquinoline as bidentate ligand. The preparation method comprises the following steps: uniformly stirring an 8-aminoquinoline derivative I, potassium trifluoroborate II, alkali, an additive and an accelerant in a reaction solvent and then carrying out reacting at 110-140 DEG C for 24 hours; or uniformly mixing andstirring an 8-aminoquinoline derivative IV, potassium trifluoroborate II, acyl chloride V, alkali and the accelerant in the reaction solvent, and then carrying out reacting at 110-140 DEG C for 24 hours. The raw materials are good in stability and easy to obtain, reaction operation is simple, high-selectivity preparation of the tetra-coordinated N,N-chelated double-base compound can be realized,reaction yield is high, the compatibility of reaction condition functional groups is high, and the application scope of substrates is wide. The reaction conditions can be further simplified, the conversion of the three components by a one-pot method is realized, and the overall atomic efficiency and economy of synthesis are further improved.

Description

technical field [0001] The invention belongs to the technical field of fine chemicals, and in particular relates to a preparation method of four-coordination N,N-chelating diaryl borate (AQDAB) in which 8-aminoquinoline (AQ) derivatives are bidentate ligands. Background technique [0002] Four-coordinated N,N-chelated diaryl borate is an important fine chemical intermediate, which is widely used in dyestuffs, materials, photocatalysis, and organic solar energy industries. For example, four-coordinated N,N-chelating diaryl borate BODIPY derivatives have good photochemical stability and excellent photoelectric properties, and can be used in the manufacture of dyes, optoelectronic materials, fluorescent probes and many other fields. Recently, some research groups have also used these compounds as catalysts in photocatalytic reactions. Therefore, it is of great significance and practical application value to study the synthesis and modification methods of new four-coordinated N...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F5/02
CPCC07F5/02Y02E10/549
Inventor 徐亮韦玉祖维赛曹自峰
Owner SHIHEZI UNIVERSITY
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