Looking for breakthrough ideas for innovation challenges? Try Patsnap Eureka!

Method for preparing alcohol compound from 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 difficult catalysts, high cost, and safety risks Large and other problems, to achieve the effect of high reaction yield, short reaction time and simple post-treatment

Active Publication Date: 2021-11-09
SUZHOU UNIV
View PDF3 Cites 0 Cited by
  • 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

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
View more

Image

Smart Image Click on the blue labels to locate them in the text.
Viewing Examples
Smart Image
  • Method for preparing alcohol compound from aromatic carboxylic acid based on n-butyllithium
  • Method for preparing alcohol compound from 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 dehydrated and deoxygenated reaction flask, 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 ).

[0026] Add 1...

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 n- The tetrahydrofuran solution of 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 equipped with NMR. Calculated 1 H yield was 95%. NMR data of the product: 1 H NMR (400 MHz, CDCl 3 ): δ7.40 (br s, 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, comb...

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
Login to View More

PUM

No PUM Login to View More

Abstract

The present invention relates to the application of n-butyllithium, in particular to a method for preparing alcohol compounds based on n-butyllithium aromatic carboxylic acid, in which the catalyst, borane and carboxylic acid are stirred and mixed in sequence, and after the reaction, they are exposed to the air to terminate the reaction. The solvent was removed from the reaction solution under reduced pressure, and then silica gel was added for methanol hydrolysis to obtain the alcohol compound. The n-butyllithium disclosed by the present invention can catalyze the hydroboration reaction of carboxylic acid and borane with high activity at room temperature, and the amount of catalyst is only 0.5mol% of the molar weight of carboxylic acid. Compared with the existing catalytic system, the use of The commercial reagent n-butyllithium was discovered, the reaction conditions were mild, and the yield of borate esters with different substituents could reach more than 90% under limited conditions.

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

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
Login to View More

Application Information

Patent Timeline
no application Login to View More
Patent Type & Authority Patents(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
Who we serve
  • R&D Engineer
  • R&D Manager
  • IP Professional
Why Patsnap Eureka
  • Industry Leading Data Capabilities
  • Powerful AI technology
  • Patent DNA Extraction
Social media
Patsnap Eureka Blog
Learn More
PatSnap group products

Browse by: Latest US Patents, China's latest patents, Technical Efficacy Thesaurus, Application Domain, Technology Topic, Popular Technical Reports.

© 2024 PatSnap. All rights reserved.Legal|Privacy policy|Modern Slavery Act Transparency Statement|Sitemap|About US| Contact US: help@patsnap.com