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Method for preparing alcohol compound by using aromatic carboxylic acid based on n-butyllithium

A technology of aromatic carboxylic acid and n-butyllithium, which is applied in the direction of carboxylate preparation, organic compound preparation, and compounds containing elements of group 3/13 of the periodic table, etc., which can solve the problems of difficult catalysts, high safety risks, and cost Advanced problems, to achieve the effect of high reaction yield, simple post-treatment, and short reaction time

Active Publication Date: 2019-03-15
SUZHOU UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0003] Existing hydroboration methods have significant disadvantages: LiAlH 4 and NaBH 4 The system security risk is very high, SmI 2 -H 2 O-Et 3 The N system needs a lot of reagents in excess, and the transition metal complex system needs to be carried out under high temperature and high pressure. On the one hand, it needs to use a catalyst that is difficult to synthesize, and the cost is high; on the other hand, the catalytic reaction requires 60 o The reaction temperature of C and the reaction time of 24 hours
On the one hand, the existing method needs to use a catalyst that is difficult to synthesize, and the cost is high; on the other hand, the catalytic reaction requires 60 o The reaction temperature of C and the reaction time of 24 hours

Method used

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  • Method for preparing alcohol compound by using aromatic carboxylic acid based on n-butyllithium
  • Method for preparing alcohol compound by using aromatic carboxylic acid based on n-butyllithium

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0024] Embodiment one: N-butyllithium catalyzes the hydroboration reaction of benzoic acid and pinacol borane

[0025] Under an inert gas atmosphere, add benzoic acid (61.1 mg, 0.5 mmol) to the reaction flask after dehydration and deoxygenation, add pinacol borane (289 μL, 2 mmol) with a pipette gun, and finally add 25 μL Tetrahydrofuran solution (0.1M) of n-butyllithium (0.5 mol% dosage, the same below), reacted at room temperature for 45 minutes, exposed the reaction solution to air, removed the solvent, and obtained the product borate, sampled, and equipped with nuclear magnetic Trimethoxybenzene (84.15 mg, 0.5 mmol) was used as internal standard, and CDCl 3 Dissolve and stir for 10 minutes. Calculated 1 The yield of H is 99%; if n-butyl lithium is replaced by triaryl oxide rare earth catalyst Nd(OAr) 3 (THF) 2 , no product is obtained. NMR data of the product: 1 H NMR (400 MHz, CDCl 3 ) : δ 7.22– 7.32 (m,5H, ArH), 4.92 (s, 2H, CH 2 ), 1.26 (s, 36H, CH 3 ).

[002...

Embodiment 2

[0031] Embodiment 2: n-butyllithium catalyzes the hydroboration reaction of 4-fluorobenzoic acid and pinacol borane

[0032] Under an inert gas atmosphere, add 4-fluorobenzoic acid (70.8 mg, 0.5 mmol) to the reaction flask after dehydration and deoxygenation treatment, add pinacol borane (290 μL, 2 mmol) with a pipette gun, and finally add The tetrahydrofuran solution of n-butyllithium (0.5 mol% dosage) was reacted at room temperature for 45 minutes, the reaction solution was exposed to air, and the solvent was removed to obtain the product borate, which was sampled, and NMR was calculated. 1 H yield was 90%. NMR data of the product: 1 H NMR (400 MHz, CDCl 3 ): δ7.21 (br s, 2H, ArCH), 6.91 (t, 2H, ArCH), 4.75 (s, 2H, OCH 2 ), 1.15 (s, 36H, CH 3). Add 1 g of silica gel and 3 mL of methanol to the system in which the solvent was removed after the hydroboration reaction, and react at 50 ° C for 2 h. After the reaction, extract three times with ethyl acetate, combine the orga...

Embodiment 3

[0033] Embodiment three: n-butyllithium catalyzes the hydroboration reaction of 4-bromobenzoic acid and pinacol borane

[0034] Under an inert gas atmosphere, add 4-bromobenzoic acid (100 mg, 0.5 mmol) to the reaction flask after dehydration and deoxygenation treatment, add pinacol borane (289 μL, 2 mmol) with a pipette gun, and finally add The tetrahydrofuran solution of n-butyllithium (0.5 mol% dosage) was reacted at room temperature for 45 minutes, the reaction solution was exposed to air, and the solvent was removed to obtain the product borate, which was sampled and NMR was prepared. Calculated 1 H yield was 95%. NMR data of the product: 1 H NMR (400 MHz, CDCl 3 ): δ 7.40 (brs, 2H, ArCH), 7.17 (t, 2H, ArCH), 4.81 (s, 2H, OCH 2 ), 1.20 (s, 36H, CH 3 ). Add 1 g of silica gel and 3 mL of methanol to the system in which the solvent was removed after the hydroboration reaction, and react at 50 ° C for 2 h. After the reaction, extract three times with ethyl acetate, combi...

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Abstract

The invention relates to the application of n-butyllithium, in particular to a method for preparing an alcohol compound by using aromatic carboxylic acid based on the n-butyllithium. The method comprises the following steps: uniformly stirring and mixing a catalyst, borane and carboxylic acid for reaction, then exposing the mixture to air to terminate the reaction; removing a solvent from a reaction liquid at a reduced pressure, and adding silica gel methanol for hydrolysis to obtain the alcohol compound. The n-butyllithium disclosed in the invention can catalyze, with high activity, the hydroboration of carboxylic acid and borane at a room temperature, and the use amount of the catalyst is only 0.5 mol percent of the molar amount of the carboxylic acid; compared with an existing catalyticsystem, the method has the advantages that a commercial reagent n-butyllithium is used, the reaction conditions are mild, and the yields of boric acid esters with different substituents under definedconditions can be up to 90 percent or above.

Description

technical field [0001] The invention relates to the application of the commercial reagent n-butyllithium, in particular to the application of n-butyllithium to catalyze the synthesis of carboxylic acid and borane to prepare alcohol compounds. Background technique [0002] Alcohol compounds are common organic compounds with many uses and clear effects. There are various methods for preparing alcohol compounds, among which organic borates can be regarded as orthoboric acid B(OH) 3 It is an effective method for the synthesis of alcohol compounds. [0003] Existing hydroboration methods have significant disadvantages: LiAlH 4 and NaBH 4 The system security risk is very high, SmI 2 -H 2 O-Et 3 The N system needs a lot of reagents in excess, and the transition metal complex system needs to be carried out under high temperature and high pressure. On the one hand, it needs to use a catalyst that is difficult to synthesize, and the cost is high; on the other hand, the catalytic ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C33/22C07C33/46C07C33/18C07C33/24C07C29/132C07C43/23C07C41/26C07F5/04C07D209/12C07C65/01C07C51/367
CPCC07C33/18C07C33/22C07C33/24C07C33/46C07C43/23C07C65/01C07D209/12C07F5/04
Inventor 薛明强徐晓娟颜丹丹朱章野郑煜沈琪
Owner SUZHOU UNIV
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