Preparation method of 2-(4-hydroxyphenyl)-5,7-dimethoxy benzofuran

A technology of dimethoxybenzene and dimethoxyphenyl, which is applied in the field of preparation of 2--5,7-dimethoxybenzofuran, can solve the problems of poor substrate adaptability, complex catalytic system, Harsh reaction conditions and other issues, to achieve the effects of easy large-scale preparation, simple post-treatment process, and no need for noble metal catalysis

Active Publication Date: 2013-10-30
GUANGZHOU CHEM CO LTD CHINESE ACADEMY OF SCI
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AI Technical Summary

Problems solved by technology

However, the reaction conditions of the above-mentioned preparation method are relatively harsh, requiring higher reaction temperature and longer reaction time; strong acid, strong base, expensive heavy metal catalyst and ligand need to be used; and the raw materials are not easy to obtain, and the substrate adaptability is not good. Wide range, complex catalytic system, low yield
Moreover, for 2-(4-hydroxyphenyl)-5,7-dimethoxybenzofuran (Formula 1), there is no report on its preparation method

Method used

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  • Preparation method of 2-(4-hydroxyphenyl)-5,7-dimethoxy benzofuran
  • Preparation method of 2-(4-hydroxyphenyl)-5,7-dimethoxy benzofuran

Examples

Experimental program
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Effect test

Embodiment 1

[0033] Embodiment 1: the preparation of 2-bromo-3,5-dimethoxyphenylacetic acid (formula 2)

[0034] In a 150mL reaction flask, add 3,5-dimethoxyphenylacetic acid (9.80g, 50mmol) and 100mL of chloroform, respectively, stir and heat, and when the temperature rises to 40°C, slowly add dibromohydantoin (DBDMH , 7.15g, 25mmol), after the addition, continue to react for 15h, pour the reaction solution into ice water, stir for 1.5h, filter with suction, collect the filtrate and wash 3 times with saturated sodium bisulfite, 30mL / time, concentrate under reduced pressure, Recrystallized with distilled water to obtain 11.46 g of 2-bromo-3,5-dimethoxyphenylacetic acid, yield: 83.3%. m.p.122-124°C. 1 H NMR (400MHz, DMSO-d 6 ):δ12.44(s,1H),6.61(d,J=2.8Hz,1H),6.58(d,J=2.8Hz,1H),3.81(s,3H),3.90(s,3H),3.77 (s,2H); MS(EI):m / z=276[M+2] + ,274[M] + ,195[M-Br] + ,180[M-COOCH 3 ] + ,77[C 6h 5 ] + .

Embodiment 2

[0035] Example 2: Preparation of 2-(2-bromo-3,5-dimethoxyphenyl)-3-(4-hydroxyphenyl)acrylic acid (Formula 3)

[0036] In a 150ml reaction flask, add 2-bromo-3,5-dimethoxyphenylacetic acid (6.88g, 25mmol), p-hydroxybenzaldehyde (3.05g, 25mmol), triethylamine (7.0ml, 50mmol) 1. 15ml of acetic anhydride, stirred and heated to 110°C, and maintained at this temperature for 8h. After the reaction was completed, the reaction system was slowly poured into 50ml of ice-water solution, stirred, left overnight, suction filtered, washed with water, and the filter cake was purified by column chromatography (ethyl acetate:petroleum ether=2:1) ​​to obtain 2-(2 -Bromo-3,5-dimethoxyphenyl)-3-(4-hydroxyphenyl)acrylic acid 8.47g, yield: 89.4%. m.p.110-112°C. 1 HNMR (400MHz, DMSO-d 6 ):δ10.36(s,1H),7.18(dd,J 1 =8.00,J 2 =1.74Hz,1H),6.89(d,J=1.74Hz,1H),6.75(d,J=8.00Hz,1H),5.30(s,1H),3.96(s,2H),3.74(s,3H ),3.65(s,3H); MS(EI):m / z=239[M] + ,208[M-OCH 3 ] + ,180[M-COOCH 3 ] + ,77[C 6 h 5 ]...

Embodiment 3

[0037] Example 3: Preparation of 2-(4-hydroxyphenyl)-5,7-dimethoxybenzofuran-3-carboxylic acid (formula 4)

[0038] In a 150ml normal-pressure stainless steel reaction flask, add 2-(2-bromo-3,5-dimethoxyphenyl)-3-(4-hydroxyphenyl)acrylic acid (3.79g, 10mmol), anhydrous Copper sulfate (4.8g, 30mmol), the mass fraction is 10% sodium hydroxide solution (NaOH solid 4.0g, 100mmol, add 36ml water to dissolve), warm up to 120°C, reflux for 72h, stop the reaction. Cool to 25°C, remove insoluble matter by suction filtration, slowly add dilute hydrochloric acid with a mass fraction of 5% to the filtrate and adjust the pH to 4-5, let it stand, and precipitate a large amount of black gray solid, and use ethyl acetate-petroleum ether (1: 2) The mixed solvent was recrystallized to obtain a light yellow solid, 2-(4-hydroxyphenyl)-5,7-dimethoxybenzofuran-3-carboxylic acid, weight: 1.48g, yield: 76.8%. m.p.212-214°C. 1 H NMR (400MHz, DMSO-d 6 ):δ12.75(s,COOH),10.05(s,OH),7.81(d,J=8.8Hz,2H),...

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Abstract

The invention discloses a synthetic method of 2-(4-hydroxyphenyl)-5,7-dimethoxy benzofuran. The synthetic method comprises the following steps of: firstly, performing bromination reaction and Perkin reaction on 3,5-dimethoxy phenylacetic acid and parahydroxyben-zaldehyde which are used as raw materials to obtain 2-(2-bromo-3,5-dimethoxy phenyl)-3-(4-hydroxyphenyl) acroleic acid; then performing series-wound hydroxylation/intramolecular cyclization/dehydrogenation reaction to obtain 2-(4-hydroxyphenyl)-5,7-dimethoxy benzofuran-3-carboxylic acid; and finally, performing decarboxylic reaction to prepare the 2-(4-hydroxyphenyl)-5,7-dimethoxy benzofuran. According to the method, raw materials are low in price and easy to obtain, the synthetic route is simple, quick and efficient, a noble metal and a ligand are not needed for catalysis, and the method is simple and convenient to operate and good in atom economy.

Description

technical field [0001] The invention relates to the field of chemical industry, in particular to a preparation method of 2-(4-hydroxyphenyl)-5,7-dimethoxybenzofuran. Background technique [0002] 2-arylbenzofuran natural product Livistone C (chemical name: 2-(4-hydroxyphenyl)-5,7-dimethoxybenzofuran, structure shown in formula 1) was first developed by Yue et al. A natural product with novel structure extracted and isolated from Hainan palmetto (J.Asian Nat.Prod.Res.,2009,3,243). [0003] [0004] 2-Arylbenzofuran compounds have a wide range of biological activities, such as antifungal activity, anti-inflammatory activity, anti-tumor activity, antioxidant activity, anti-rheumatic activity, calcium inhibition activity, anti-platelet activity and promotion of plant development, etc. Function (Phytochemistry.2004, 65, 3113). In addition to the field of medicine, 2-arylbenzofuran compounds are also expected to be used in organic light-emitting diodes (OLED) (Org. J.Org.Che...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D307/86
Inventor 邹永徐田龙黄琦魏文张恩生黄桐堃何树杰
Owner GUANGZHOU CHEM CO LTD CHINESE ACADEMY OF SCI
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