CN101717386A - Method for synthesizing 7-hydroxy-4-methylcoumarin in presence of compound solid superacid catalyst - Google Patents

Method for synthesizing 7-hydroxy-4-methylcoumarin in presence of compound solid superacid catalyst Download PDF

Info

Publication number
CN101717386A
CN101717386A CN200910218786A CN200910218786A CN101717386A CN 101717386 A CN101717386 A CN 101717386A CN 200910218786 A CN200910218786 A CN 200910218786A CN 200910218786 A CN200910218786 A CN 200910218786A CN 101717386 A CN101717386 A CN 101717386A
Authority
CN
China
Prior art keywords
reaction
methylcoumarin
hydroxy
solid superacid
compound solid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN200910218786A
Other languages
Chinese (zh)
Inventor
宋晓平
王小蕊
付明哲
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Northwest A&F University
Original Assignee
Northwest A&F University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Northwest A&F University filed Critical Northwest A&F University
Priority to CN200910218786A priority Critical patent/CN101717386A/en
Publication of CN101717386A publication Critical patent/CN101717386A/en
Pending legal-status Critical Current

Links

Classifications

    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Landscapes

  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention relates to a method for synthesizing 7-hydroxy-4-methylcoumarin in the presence of a compound solid superacid catalyst, which has the advantages that: the reaction yield is high; and the used compound solid superacid catalyst avoids corroding equipment and polluting environment and can be used repeatedly. The invention adopts a technical scheme that: resorcinol and ethyl acetoacetate are sequentially added into a reactor in a molar ratio of 1:0.7-2.0 and heated to a reaction temperature between 100 and 170 DEG C; then the compound solid superacid catalyst SO42-/ZroO2-TiO2 is added into the reactor in an amount which is 0.6 to 5 percent of the mass of the reaction raw materials; after the material addition is finished, a water distributor connected with a condenser is arranged; the mixture is heated at a controlled temperature to undergo a reaction for 1.5 to 2.5 hours; after the reaction is finished, the resulting product is cooled slightly, and a small amount of absolute ethanol is added , and the mixture is heated to 70 DEG C to dissolve the resulting product; the catalyst is reclaimed by vacuum filtration; the hot filtrate is poured into water with crushed ice to precipitate a flocculent precipitate; the solution is subjected to vacuum filtration; and a filter cake of a coarse product is recrystallized by using ethanol solution, and the crystals are dried to obtain the 7-hydroxy-4-methylcoumarin.

Description

The method of the synthetic 7-hydroxy-4-methylcoumarin of a kind of presence of compound solid superacid catalyst
Technical field
The present invention relates to a kind of chemical synthesis process of compound, especially the method that relates to the synthetic 7-hydroxy-4-methylcoumarin of a kind of presence of compound solid superacid catalyst, its for a kind of be raw material with Resorcinol and methyl aceto acetate, complex solid superacid is the method for the synthetic 7-hydroxy-4-methylcoumarin of catalyst or solvent.
Background technology
7-hydroxy-4-methylcoumarin (having another name called Hymecromone) belongs to heterocyclic aromatic compound, is the important intermediate of synthetic medicine, agricultural chemicals and fluorescent material, is widely used in the laser dyes, also can be used as the logical bulk drug of choleretic-courage.Have in recent years this compound of research report have significant kill full active [beans pass Na. oriental wormwood kills the separation and purification and the structure that expire activeconstituents and identifies. Xibei Univ. of Agricultural ﹠ Forest Science ﹠ Technology's master thesis, Yang Ling, 2007].
The traditional synthetic method of 7-hydroxy-4-methylcoumarin is to be catalyzer with the vitriol oil, the Pechmann reaction method of Resorcinol and methyl aceto acetate one step condensation.One of key of this synthetic method is the use of acid catalyst.So far, though extensive work has been carried out in the research of this catalysts both at home and abroad, be catalyzer with the vitriol oil in the synthetic 7-hydroxy-4-methylcoumarin method of tradition, side reaction easily takes place in long reaction time, the aftertreatment complexity.In addition, vitriol oil corrosive equipment can not reclaim repeated use, and produces a large amount of waste liquids and contaminate environment.
Summary of the invention
The present invention is in order to solve the weak point in the above-mentioned background technology, the method of the synthetic 7-hydroxy-4-methylcoumarin of a kind of presence of compound solid superacid catalyst is provided, its reaction yield height, and the presence of compound solid superacid catalyst agent of using is etching apparatus, free from environmental pollution, reusable not, really realized green synthesizing, be convenient to industrial production and promote.
For achieving the above object, the technical solution used in the present invention is:
The method of the synthetic 7-hydroxy-4-methylcoumarin of a kind of presence of compound solid superacid catalyst, it is characterized in that: under condition of no solvent, add Resorcinol and methyl aceto acetate 1: 0.7 in molar ratio～2.0 in the reactor successively, after being warming up to 100 ℃～170 ℃ of temperature of reaction, add the complex solid superacid SO that accounts for reaction raw materials massfraction 0.6%～5% again 4 2-/ ZrO 2-TiO 2, reinforced finishing adds the water trap that is fitted with prolong, the temperature control heating, the reaction times is 1h～4h, reaction finishes and cools off slightly, add a small amount of dehydrated alcohol, 70 ℃ of following heating for dissolving products, suction filtration reclaims catalyzer, in hot filtrate impouring trash ice water, separate out flocks, suction filtration is with thick product filter cake ethanolic soln recrystallization, drying promptly gets purified 7-hydroxy-4-methylcoumarin.
The preferred molar ratio of preferred Resorcinol and methyl aceto acetate is 1: 1.3～2.0.
Preferred presence of compound solid superacid catalyst agent SO 4 2-/ ZrO 2-TiO 2The preferred mass mark that accounts for reaction raw materials is 2%～3%.
Preferable reaction temperature is 150 ℃～170 ℃, and the preferred reaction time is 1.5h～2.5h.
Concentration of ethanol is 67% in the ethanolic soln recrystallization.
Compared with prior art, the advantage and the effect that have of the present invention is as follows:
(1) the present invention adopts complex solid superacid as the synthetic 7-hydroxy-4-methylcoumarin of catalyst, etching apparatus, reaction solution and product are not easy to separate, shortcomings such as reaction mixture difficult treatment, the environmental pollution that is brought in can avoiding producing is serious, improve economic benefit and the social benefit in the production process, met green synthetic theory.
(2) this synthetic method is easy and simple to handle, and presence of compound solid superacid catalyst is active high, reusable, the meaning that has industry to apply.
Embodiment
The synthetic method of present embodiment is: under condition of no solvent, with Resorcinol and methyl aceto acetate in molar ratio 1: (0.7～2.0), add in the reactor successively, after being warming up to 100 ℃～170 ℃ of certain temperature of reaction, add again that to account for the reaction raw materials massfraction be 0.6%～5% complex solid superacid SO 4 2-/ ZrO 2-TiO 2Reinforced finishing adds the water trap that is fitted with prolong, the temperature control heating, reaction times is 1h～4h, and reaction finishes and cools off slightly, adds a small amount of dehydrated alcohol, 70 ℃ of following heating for dissolving products, suction filtration reclaims catalyzer, in hot filtrate impouring trash ice water, separates out flocks, suction filtration, with 67% ethanolic soln recrystallization, drying promptly gets purified 7-hydroxy-4-methylcoumarin with thick product filter cake.
The product outward appearance of the inventive method preparation is a white needle-like crystals, and recording fusing point is 186 ℃～189 ℃, FT-IR υ Max KBr(cm -1): 3154 (Ar-H), 1677 (C=O), 1388 (CH 3), 1066 (C-O), 844,582; 1H NMR (400MHz, d 6-DMSO) δ: 10.51 (1H, s, OH), 2.50 (3H, s, CH 3), 6.13 (1H, s, H-3), 7.59 (1H, d, J=8.8Hz, H-5), 6.80 (1H, dd, J=8.8Hz, J=2.4Hz, H-6), 6.70 (s, 1H, H-8); EI-MS m/z:[M+H] +: 177.22.
Following examples help to understand the present invention, but are not limited to content of the present invention.
Embodiment one:
In the 500mL there-necked flask that 0 ℃～200 ℃ of range thermometers are housed, add Resorcinol 11.01g, magnetic agitation, slowly drip methyl aceto acetate 19.14mL under the oil bath heat temperature raising situation, wait to dropwise, be warming up to 150 ℃ and add complex solid superacid SO down 4 2-/ ZrO 2-TiO 20.6g, install water trap and prolong additional, stop heating behind the reaction 1.5h, after question response liquid cools off slightly, adding a small amount of dehydrated alcohol (dissolves product fully, as follows), 70 ℃ of following heating for dissolving products, suction filtration reclaims catalyzer, with crystallization in the hot filtrate impouring trash ice water, separate out flocks, suction filtration is with 67% ethanol 300mL recrystallization.Drying promptly gets white needle-like crystals, and yield is 88.0%.
Embodiment two:
In the 500mL there-necked flask that 0 ℃～200 ℃ of range thermometers are housed, add Resorcinol 11.01g, magnetic agitation, slowly drip methyl aceto acetate 19.14mL under the oil bath heat temperature raising situation, wait to dropwise, be warming up to 150 ℃ and add complex solid superacid SO down 4 2-/ ZrO 2-TiO 20.8g, install water trap and prolong additional, stop heating behind the reaction 1.5h, after question response liquid cools off slightly, add a small amount of dehydrated alcohol, 70 ℃ of following heating for dissolving products, suction filtration reclaims catalyzer, with crystallization in the hot filtrate impouring trash ice water, separate out flocks, suction filtration is with 67% ethanol 300mL recrystallization.Drying promptly gets white needle-like crystals, and yield is 85.3%.
Embodiment three:
In the 500mL there-necked flask that 0 ℃～200 ℃ of range thermometers are housed, add Resorcinol 11.01g, magnetic agitation, slowly drip methyl aceto acetate 19.14mL under the oil bath heat temperature raising situation, wait to dropwise, be warming up to 160 ℃ and add complex solid superacid SO down 4 2-/ ZrO 2-TiO 20.6g, install water trap and prolong additional, stop heating behind the reaction 1.5h, after question response liquid cools off slightly, add a small amount of dehydrated alcohol, 70 ℃ of following heating for dissolving products, suction filtration reclaims catalyzer, with crystallization in the hot filtrate impouring trash ice water, separate out flocks, suction filtration is with 67% ethanol 300mL recrystallization.Drying promptly gets white needle-like crystals.Yield 87.7%.
Embodiment four:
In the 500mL there-necked flask that 0 ℃～200 ℃ of range thermometers are housed, add Resorcinol 11.01g, magnetic agitation, slowly drip methyl aceto acetate 22.97mL under the oil bath heat temperature raising situation, wait to dropwise, be warming up to 150 ℃ and add complex solid superacid SO down 4 2-/ ZrO 2-TiO 20.6g, install water trap and prolong additional, stop heating behind the reaction 1.5h, after question response liquid cools off slightly, add a small amount of dehydrated alcohol, 70 ℃ of following heating for dissolving products, suction filtration reclaims catalyzer, with crystallization in the hot filtrate impouring trash ice water, separate out flocks, suction filtration is with 67% ethanol 300mL recrystallization.Drying promptly gets white needle-like crystals.Yield 87.2%.
Embodiment five:
In the 500mL there-necked flask that 0 ℃～200 ℃ of range thermometers are housed, add Resorcinol 11.01g, magnetic agitation, slowly drip methyl aceto acetate 19.14mL under the oil bath heat temperature raising situation, wait to dropwise, be warming up to 150 ℃ and add complex solid superacid SO down 4 2-/ ZrO 2-TiO 20.6g, install water trap and prolong additional, stop heating behind the reaction 2h, after question response liquid cools off slightly, add 70 ℃ of heating for dissolving products of a small amount of dehydrated alcohol, suction filtration reclaims catalyzer, with crystallization in the hot filtrate impouring trash ice water, separate out flocks, suction filtration is with 67% ethanol 300mL recrystallization.Drying promptly gets white needle-like crystals, and yield is 87.3%.

Claims (4)

1. the method for the synthetic 7-hydroxy-4-methylcoumarin of a presence of compound solid superacid catalyst, it is characterized in that: under condition of no solvent, add Resorcinol and methyl aceto acetate 1: 0.7 in molar ratio～2.0 in the reactor successively, after being warming up to 100 ℃～170 ℃ of temperature of reaction, add the complex solid superacid SO that accounts for reaction raw materials massfraction 0.6%～5% again 4 2-/ ZrO 2-TiO 2, reinforced finishing adds the water trap that is fitted with prolong, the temperature control heating, the reaction times is 1h～4h, reaction finishes and cools off slightly, add a small amount of dehydrated alcohol, 70 ℃ of following heating for dissolving products, suction filtration reclaims catalyzer, in hot filtrate impouring trash ice water, separate out flocks, suction filtration is with thick product filter cake ethanolic soln recrystallization, drying promptly gets purified 7-hydroxy-4-methylcoumarin.
2. the method for the synthetic 7-hydroxy-4-methylcoumarin of a kind of presence of compound solid superacid catalyst according to claim 1, it is characterized in that: the mol ratio of Resorcinol and methyl aceto acetate is 1: 1.3～2.0.
3. the method for the synthetic 7-hydroxy-4-methylcoumarin of a kind of presence of compound solid superacid catalyst according to claim 1 is characterized in that: presence of compound solid superacid catalyst agent SO 4 2-/ ZrO 2-TiO 2The massfraction that accounts for reaction raw materials is 2%～3%.
4. the method for the synthetic 7-hydroxy-4-methylcoumarin of a kind of presence of compound solid superacid catalyst according to claim 1, it is characterized in that: temperature of reaction is 150 ℃～170 ℃, and the reaction times is 1.5h～2.5h.
CN200910218786A 2009-11-03 2009-11-03 Method for synthesizing 7-hydroxy-4-methylcoumarin in presence of compound solid superacid catalyst Pending CN101717386A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN200910218786A CN101717386A (en) 2009-11-03 2009-11-03 Method for synthesizing 7-hydroxy-4-methylcoumarin in presence of compound solid superacid catalyst

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN200910218786A CN101717386A (en) 2009-11-03 2009-11-03 Method for synthesizing 7-hydroxy-4-methylcoumarin in presence of compound solid superacid catalyst

Publications (1)

Publication Number Publication Date
CN101717386A true CN101717386A (en) 2010-06-02

Family

ID=42432030

Family Applications (1)

Application Number Title Priority Date Filing Date
CN200910218786A Pending CN101717386A (en) 2009-11-03 2009-11-03 Method for synthesizing 7-hydroxy-4-methylcoumarin in presence of compound solid superacid catalyst

Country Status (1)

Country Link
CN (1) CN101717386A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102503920A (en) * 2011-11-21 2012-06-20 苏州诚和医药化学有限公司 Method for preparing 7-hydroxyl-4-methyl coumarin
CN112142705A (en) * 2020-09-10 2020-12-29 浙江工业大学 Method for synthesizing cromolyn sodium key intermediate 7-hydroxy-4-methylcoumarin

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102503920A (en) * 2011-11-21 2012-06-20 苏州诚和医药化学有限公司 Method for preparing 7-hydroxyl-4-methyl coumarin
CN112142705A (en) * 2020-09-10 2020-12-29 浙江工业大学 Method for synthesizing cromolyn sodium key intermediate 7-hydroxy-4-methylcoumarin

Similar Documents

Publication Publication Date Title
CN111484499B (en) Method for preparing drug intermediate chromene pyrimido indazolone derivative through catalysis
CN102816062A (en) Method for preparing gallic acid by hydrochloric acid catalytic hydrolysis of tannin containing biomass in high temperature liquid water
CN102307859A (en) Process for the synthesis of cleistanthin
CN101717386A (en) Method for synthesizing 7-hydroxy-4-methylcoumarin in presence of compound solid superacid catalyst
CN111187206A (en) Method for synthesizing 2-amino-5-bromopyridine under catalysis of microwave and ionic liquid
CN101723925B (en) Preparation method of 7-hydroxy-4-methylcoumarin
CN109180628A (en) A kind of preparation method of apiolin
CN110698335A (en) Synthesis method of terbutaline intermediate
CN101531634B (en) High-purity blonanserin and preparation method thereof
CN107325055A (en) A kind of synthetic method of olaparib compound
CN103539728A (en) Synthesis method of lansoprazole drug intermediate chloromethyl pyridine derivative
CN107936045A (en) A kind of preparation method of high-purity Flurbiprofen known impurities
JPH0390080A (en) Method for preparation of pure guanine improved in coloration
CN112341433A (en) Preparation method of loratadine
CN112125889A (en) Preparation method of 7-bromo-2- (1-methyl-1H-pyrazol-4-yl) quinoxaline
CN102206185B (en) Process for refining bendazac lysine and analogs thereof
CN105130972A (en) Emtricitabine benzoate, preparation method thereof, and method of preparing emtricitabine from emtricitabine benzoate
CN109574847A (en) A kind of green synthesis process of 11 ester of preservative nipalgin
CN113200880B (en) Precursor compound containing beta-aminoketone with conjugated structure and preparation method thereof
CN115784894B (en) Refining method of ultra-high purity sodium p-nitrophenolate
CN115626893B (en) Synthesis method of 2-hydroxy-5-hydroxymethylpyridine
CN113416188B (en) Synthetic method of [1,2,4] triazolo [1,5-A ] pyridine compound
CN113214197B (en) Preparation method of vitamin C ethyl ether
CN113801089B (en) Preparation method of clenbuterol intermediate
CN105906646A (en) Method for preparing pyrano [4,3-b] pyran derivatives by basic ionic liquid catalysis

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C02 Deemed withdrawal of patent application after publication (patent law 2001)
WD01 Invention patent application deemed withdrawn after publication

Open date: 20100602