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

A kind of synthetic method of 2-ethoxybenzoic acid compound

A technology of ethoxybenzoic acid and synthesis method, applied in organic chemistry, amide preparation, etc., can solve problems such as difficulty in detaching product-directing groups, harsh reaction conditions, etc., achieve good substrate universality, simple reaction system, The effect of high yield

Active Publication Date: 2016-07-06
ZHENGZHOU UNIV
View PDF1 Cites 0 Cited by
  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0003] The technical problem to be solved by the present invention is to provide a kind of 2-ethoxybenzoic acid for the direct functionalization of C-H bond to synthesize 2-ethoxybenzoic acid with harsh reaction conditions and problems such as the product directing group is difficult to detach from after the reaction. The synthetic method of formic acid compound, this method uses cheap metal as catalyst and is simple and efficient

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

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0020] The synthetic method step of the 2-ethoxybenzoic acid of the present embodiment is as follows:

[0021] (1) Preparation of 2-ethoxybenzamidopyridine-1-oxide: benzamidopyridine-1-oxide (0.2mmol, 42.8mg), anhydrous CuCl (0.2mmol, 19.6mg) , into a high-pressure sealed tube, then inject 0.75mL ethanol and 0.75mL pyridine, stir at room temperature for 30 minutes, and add K after precipitation of the complex 2 CO 3 (0.1mmol, 13.8mg), the reaction system was heated to 130°C for 12h. After the reaction, dilute hydrochloric acid (5mL, 2N) was added to quench the reaction, and then the reaction solution was washed with CH 2 Cl 2 (10×3mL) extracted, dried over anhydrous sodium sulfate, separated by thin layer chromatography (CH 2 Cl 2 / acetone) to obtain 43mg of 2-ethoxyamide products, with a yield of 84% and a melting point of 140-141°C. 1 HNMR (400MHz, CDCl 3 )δ12.30(s,1H),8.73(d,J=8.4Hz,1H),8.31-8.28(m,2H),7.55-7.51(m,1H),7.38-7.34(m,1H),7.13 -7.09(m,1H),7.07(d,J=8.4Hz,1...

Embodiment 2

[0024] The synthetic method of the 4-methylbenzoic acid of the present embodiment is as follows:

[0025] (1) Preparation of 2-(4-methyl-2-ethoxybenzamido)pyridine-1-oxide: according to the method described in Example 1, the difference is that the substrates and reagents used are: 2 -(4-Methyl-benzamido)pyridine-1-oxide (0.2mmol, 45.6mg), CuCl (0.2mmol, 19.6mg), K 2 CO 3 (0.1mmol, 13.8mg), EtOH 0.75mL, pyridine 0.75mL, react at 130°C for 12h to obtain 46mg of 2-(4-methyl-2-ethoxybenzamido)pyridine-1-oxide, Solid, 85% yield. The melting point is 162-163°C. 1 HNMR (400MHz, CDCl 3 )δ12.16(s,1H),8.66(d,J=8.4Hz,1H),8.20-8.18(m,1H),8.09-8.07(d,J=8.0Hz,1H),7.26-7.23(m ,1H),6.91-6.88(m,1H),6.83(d,J=8.0Hz,1H),6.77(s,1H),4.24(q,J=7.0Hz,2H),2.32(s,3H) ,1.63(t,J=7.0Hz,3H). 13 CNMR (100MHz, CDCl 3 )δ164.0, 157.4, 145.5, 137.4, 132.5, 127.9, 122.0, 118.3, 117.8, 115.7, 113.0, 65.2, 21.9, 14.8. HRMS (ESI) Calcd.ForC 15 h 17 N 2 o3 :[M+H] + ,273.1239,Found:273.1234;

[0026] (2) ...

Embodiment 3

[0028] The preparation method of the 4-tert-butylbenzoic acid of the present embodiment is as follows:

[0029] (1) Preparation of 2-(4-tert-butyl-2-ethoxybenzamido)pyridine-1-oxide: according to the method described in step (1) of Example 1, the difference is the substrate used And the reagents are: 2-(4-tert-butyl-benzamido)pyridine-1-oxide (0.2mmol, 54.0mg), CuCl (0.2mmol, 19.6mg), K 2 CO 3 (0.1mmol, 13.8mg), EtOH 0.75mL, pyridine 0.75mL, react at 130°C for 12h to obtain 52mg of 2-(4-tert-butyl-2-ethoxybenzamido)pyridine-1-oxide , solid, yield 83%. The melting point is 127-128°C. 1 HNMR (400MHz, CDCl 3 )δ12.27(s,1H),8.75(dd,J=8.5Hz,J=1.7Hz,1H),8.29(dd,J=6.5Hz,J=1.0Hz,1H),8.20(d,J= 8.3Hz,1H),7.37-7.33(m,1H),7.14(dd,J=8.4Hz,J=1.7Hz,1H),7.05(d,J=1.6Hz,1H),7.00-6.96(m, 1H),4.37(q,J=7.0Hz,2H),1.73(t,J=7.0Hz,3H).1.36(s,9H). 13 CNMR (100MHz, CDCl 3 )δ164.0, 158.6, 157.3, 145.5, 137.3, 132.3, 127.8, 118.4, 118.3, 117.8, 115.8, 109.4, 65.1, 35.4, 31.1, 14.8. HRMS (ESI) Calcd...

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 discloses a synthesis method of a 2-ethoxybenzoic acid compound. The synthesis method comprises the following steps of orderly adding aromatic acylaminopyridine-1-oxide, cuprous chloride and an organic solvent into a reactor, stirring the mixture at a room temperature for 25-35min, adding potassium carbonate into the mixture after complex precipitates are produced, heating the reaction system to a temperature of 125-135 DEG C to cause a reaction lasting for 10-15h, after the reaction, carrying out extraction, drying, condensation and chromatographic separation to obtain an ethoxylated product, and carrying out alkaline hydrolysis and acidification to obtain the 2-ethoxybenzoic acid compound. The synthesis method has the advantages of easy acquisition of raw materials, cheap catalyst, mild reaction system, operation simpleness, high yield and substrate universality. The synthesis method has the yield of 87% and can realize guide base removal under mild conditions.

Description

technical field [0001] This paper relates to a kind of synthetic method of 2-ethoxybenzoic acid compound. The method uses benzoic acid as the starting material to introduce an N-O bidentate guiding group, and efficiently obtains 2-ethoxy compounds under the catalysis of cuprous chloride, and finally removes the guiding group to obtain 2-ethoxybenzoic acids compound. Background technique [0002] 2-Ethoxybenzoic acid compounds are an important class of medical materials, which have analgesic and anti-inflammatory effects in medical experiments, and are widely used in the synthesis of antagonists of sildenafil and arginine antidiuretic hormone receptors V1A and V2 Among them, the efficient synthesis of 2-ethoxybenzoic acid compounds has attracted widespread attention. Since the direct functionalization of the C-H bond does not require pre-functionalization of the raw materials, the synthesis steps are short, environmentally friendly, and has many advantages such as high atom...

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): C07C65/21C07C65/24C07C51/06
CPCC07C51/06C07D213/89C07C65/21C07C65/24
Inventor 牛俊龙张林宝张守坤郝新奇任保增宋毛平
Owner ZHENGZHOU 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