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

Method for preparing alcoholic compound from anilino lithium compound as catalyst

A technology of lithium anilide and alcohol compound is applied in the application field of synthesis to prepare alcohol compound, which can solve the problems of high cost, difficult catalyst, high safety risk and the like, and achieves short reaction time, high reaction yield and simple post-processing. Effect

Active Publication Date: 2019-02-22
SUZHOU UNIV
View PDF1 Cites 1 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

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 alcoholic compound from anilino lithium compound as catalyst
  • Method for preparing alcoholic compound from anilino lithium compound as catalyst

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0024] Example 1: Lithium anilide catalyzed hydroboration of benzoic acid and pinacol borane

[0025] Under inert gas atmosphere, benzoic acid (61.1 mg, 0.5 mmol) was added to the reaction flask after dehydration and deoxygenation treatment, pinacol borane (289 μL, 2 mmol) was added with a pipette, and finally 40 μL was added The tetrahydrofuran solution (0.1M) of lithium anilide (0.8 mol% consumption, the same below) was reacted at room temperature for 75 minutes, the reaction solution was contacted with air, and the solvent was removed to obtain the product boronate ester, sampled, matched with nuclear magnetic resonance, with mesitylene Oxybenzene (84.15 mg, 0.5 mmol) was used as internal standard, and CDCl was used 3 Dissolve and stir for 10 minutes. Calculated 1 The yield of H is 99%; if the anilide lithium compound is replaced by the triaryloxy rare earth catalyst Nd(OAr) 3 (THF) 2 , the product is not obtained. NMR data of the product: 1 H NMR (400 MHz, CDCl 3 ) ...

Embodiment 2

[0031] Example 2: Lithium anilide catalyzed hydroboration of 4-fluorobenzoic acid and pinacol borane

[0032] Under inert gas atmosphere, 4-fluorobenzoic acid (70.8 mg, 0.5 mmol) was added to the reaction flask after dehydration and deoxygenation treatment, pinacol borane (290 μL, 2 mmol) was added with a pipette, and finally The tetrahydrofuran solution of the lithium anilide compound (0.8 mol% dosage) was reacted at room temperature for 75 minutes, the reaction solution was contacted with air, and the solvent was removed to obtain the product boronate ester, sampled, matched with NMR, and calculated by 1 The 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). 1 g of silica gel and 3 mL of methanol were added to the system from which the solvent was removed after the hydroboration reaction, and the reaction was carried out at 50° C. for 135 minutes. After the reaction...

Embodiment 3

[0033] Example 3: Lithium p-toluidine catalyzed hydroboration of 4-bromobenzoic acid and pinacol borane

[0034] Under inert gas atmosphere, 4-bromobenzoic acid (100 mg, 0.5 mmol) was added to the reaction flask after dehydration and deoxygenation treatment, pinacol borane (289 μL, 2 mmol) was added with a pipette, and finally The tetrahydrofuran solution of p-toluidine lithium (0.8 mol%) was reacted at room temperature for 75 minutes, the reaction solution was contacted with air, and the solvent was removed to obtain the product boronate ester, which was sampled and matched with nuclear magnetic resonance. Calculated 1 The H yield was 92%. 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 ). 1 g of silica gel and 3 mL of methanol were added to the system from which the solvent was removed after the hydroboration reaction, and the reaction was carried out at 50° C. for 135 minutes. Aft...

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 invention relates to an application of an anilino lithium compound, in particular to a method for preparing an alcoholic compound from the anilino lithium compound as a catalyst. The catalyst, borane and carboxylic acid are stirred and mixed uniformly, subjected to a reaction and exposed to air to terminate the reaction, a reacted liquid is subjected to reduced-pressure treatment for solvent removal, silica gel and methanol are added, and the alcoholic compound is obtained by hydrolysis. The anilino lithium compound can perform high-activity catalysis on the reaction between carboxylic acid and borane at room temperature, dose of the catalyst is only 0.8mol% of the mole ratio of carboxylic acid, compared with the conventional catalysis system, the commercial reagent anilino lithium compound is used, reaction conditions are mild, and yield of borate with different substituents under limit conditions can reach 90% or higher.

Description

technical field [0001] The application of the commercial reagent anilide lithium compound involved in the present invention specifically relates to the application of the anilide lithium compound to catalyze the synthesis of carboxylic acid and borane to prepare alcohol compound. 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 borate esters 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 obvious disadvantages: LiAlH 4 and NaBH 4 System security risks are very high, SmI 2 -H 2 O-Et 3 The N system needs a lot of excess reagents, the transition metal complex system needs to be carried out at high temperature and high pressure, and on the one hand, it needs to use a catalyst that is difficult to synthesize, and the cost is high; o...

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
IPC IPC(8): C07F5/04C07C29/12C07C33/22B01J31/02
CPCB01J31/0252C07C29/12C07F5/04C07C33/22
Inventor 薛明强徐晓娟颜丹丹陈素芳蔡玲霞沈琪
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