CN101676253B - Method for synthesizing 3,4-dihydroxy benzaldehyde by using air catalytic oxidation - Google Patents
Method for synthesizing 3,4-dihydroxy benzaldehyde by using air catalytic oxidation Download PDFInfo
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- CN101676253B CN101676253B CN2008102223899A CN200810222389A CN101676253B CN 101676253 B CN101676253 B CN 101676253B CN 2008102223899 A CN2008102223899 A CN 2008102223899A CN 200810222389 A CN200810222389 A CN 200810222389A CN 101676253 B CN101676253 B CN 101676253B
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- 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
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The invention relates to a method for synthesizing 3,4-dihydroxy benzaldehyde by using air catalytic oxidation, comprising the following steps: carrying out condensation reaction on pyrocatechin and glyoxylic acid at alkali condition to obtain 3,4-dihydroxymandelic acid, separating the 3,4-dihydroxymandelic acid to obtain a pure product, weighing the pure product accurately after drying, dissolving the pure product into water, adjusting the pH value to alkalescence by alkaline aqueous solution, adding catalyzer, introducing air and carrying out oxidation reaction under the condition of heating and stirring to obtain the 3,4-dihydroxy benzaldehyde, wherein, the catalyzer is composite type metallic oxide with multicomponents, the mole ratio of the catalyzer and the 3,4-dihydroxymandelic acid is 0.02-0.05, the temperature is 85-95 DEG C, the air flow is 80-110L/h, the yield of the 3,4-dihydroxy benzaldehyde is 72.3-90.7%, and the catalyzer is easy to be recycled and reused and is suitable for large scale production of 3,4-dihydroxy benzaldehyde.
Description
Technical field:
The present invention relates to a kind of 3,4-dihydroxyl racemic melic acid that generates with pyrocatechol and oxoethanoic acid generation condensation reaction is raw material, synthesizes 3 through the air catalytic oxidation decarboxylic reaction, the method for 4-Dihydroxy benzaldehyde.
Background technology:
3; The 4-Dihydroxy benzaldehyde is a kind of important organic synthesis raw material and medicine intermediate; Be the activeconstituents that extraction separation obtains from Chinese medicines such as the holly plant SIJIQING and the salvia red sage root at first; Being used for synthetic multiple microbiotic and antiphlogistic drug, is the critical materials of antiphlogistic drug Anoretic and verivate thereof, new cephalosporin microbiotic Cephalosporin and semisynthetic antibiotics Ant iarone-F.Can also be used for synthetic antishock vasoactive drug dopamine hydrochloride, suprarenal gland and noradrenaline hormone.
According to bibliographical information, 3, in 4-Dihydroxy benzaldehyde synthetic main adopt pyrocatechol be raw material through above reaction of two steps synthesis of vanillin, and then hydrolysis is synthetic 3, the 4-Dihydroxy benzaldehyde.This route exists and designs problem unreasonable and complex process, needs the new preparation process of design.People such as Zhang Hao, Song Guoqiang delivered in " 3; the synthesis technique of 4-Dihydroxy benzaldehyde " in 2002 2 phases " Speciality Petrochemicals ", was main raw material with PARA HYDROXY BENZALDEHYDE, bromine, through bromo, hydrolysis preparation 3; The 4-Dihydroxy benzaldehyde, product yield reaches 53%.Wang Junhua carries out condensation reaction generation 3 with pyrocatechol and oxoethanoic acid under the sodium hydroxide effect in " 3, the production technique of 4-Dihydroxy benzaldehyde (CN02158203) "; 4-dihydroxyl racemic melic acid, will generate then 3,4-dihydroxyl racemic melic acid and compound mantoquita carry out oxidative decarboxylation reaction and have generated 3; The 4-Dihydroxy benzaldehyde; Oxidative decarboxylation step of reaction in this course uses compound mantoquita as oxygenant separately, and its consumption is very big; And reclaim difficulty, make production cost increase considerably.
Summary of the invention:
The objective of the invention is with the polycomponent composite type metallic oxide is catalyzer, as oxygenant, 3,4-dihydroxyl racemic melic acid is oxidized to the method for 3,4-Dihydroxy benzaldehyde with air.
The technical scheme that realizes above-mentioned purpose of the present invention is:
Condensation reaction is taken place in pyrocatechol and oxoethanoic acid obtain 3,4-dihydroxyl racemic melic acid under alkaline condition, after separating, obtain pure article; The accurately weighing of dry back is dissolved in the water, uses alkaline aqueous solution to regulate the pH value and is weakly alkaline; Add catalyzer; Oxidizing reaction takes place and obtains 3,4-Dihydroxy benzaldehyde in bubbling air under condition of heating and stirring.
Chemical equation of the present invention is:
Alkali involved in the present invention can be one or more mixtures in sodium hydroxide, Pottasium Hydroxide, yellow soda ash, the salt of wormwood, and related oxygenant is an air, its skeleton symbol of related catalyzer with form as follows:
(Al)a·(Cu)b·(Mo)c·(Mn)d·(Fe)e·(Zn)f·(Na)g·(O)h·(S)i
A, b, c, d, e, f, g are the molfraction of each element in the catalyzer in the formula, wherein:
The a value is that 0.001～0.4 b value is that 0.002～0.3 c value is 0.001～0.25
The d value is that 0.001～0.4 e value is that 0.001～0.35 f value is 0.015～0.4
The g value is that 0.001～0.3 h value is that 0.001～0.4 i value is 0.001～0.4
The Preparation of catalysts method is:
Proportionally, Sodium orthomolybdate and the vitriol that contains other element are dissolved in the water simultaneously, dissolving was stirred 30 minutes, and decompression steams moisture then, in the empty baking oven of vacuum, after the oven dry, put into high speed ball mill subsequently and ground 1 hour, promptly obtained required catalyzer.
The mol ratio of catalyzer and 3,4-dihydroxyl racemic melic acid is 0.02～0.05; Temperature is 85～95 ℃; Air flow quantity 80～110L/h.
Compare with existing method, present method can significantly reduce production costs, and 3, the yield of 4-Dihydroxy benzaldehyde is 72.3～90.7%, the catalyzer easy recovery is reused, and is fit to the scale operation of 3,4-Dihydroxy benzaldehyde.
Embodiment:
Combine embodiment that the present invention is described in detail as follows at present:
Following embodiment is to be used for the present invention is further described, but also non exhaustive, the present invention is not done any restriction.
Embodiment 1
3,4-dihydroxyl racemic melic acid adding of accurate weighing is equipped with in the reactor drum of whisking appliance, TM, reflux, stirs and drip 30% aqueous sodium hydroxide solution down; Make that the pH value of solution is a weakly alkaline; Add catalyzer (mol ratio of catalyzer and 3,4-dihydroxyl racemic melic acid is 0.02) again, be warming up to 90 ℃; Bubbling air reacts 7h with this understanding.Reaction finishes back sampling analysis 3, the yield of 4-Dihydroxy benzaldehyde, and test-results is seen attached list.
Embodiment 2
According to the operation steps of embodiment 1, adopt respectively to add catalyzer and 3, the mol ratio of 4-dihydroxyl racemic melic acid is 0.03,0.04,0.05, and all the other processing condition remain unchanged with embodiment 1, and test-results is seen attached list.
Embodiment 3
According to the operation steps of embodiment 1, except that changing the reaction times, all the other processing condition are identical with embodiment 1, and test-results is the face subordinate list as follows.
Embodiment 4
According to the operation steps of embodiment 1, except that changing temperature of reaction, all the other processing condition are identical with embodiment 1, and test-results is the face subordinate list as follows.
Embodiment 5
According to the operation steps of embodiment 1, except that changing air flow quantity, all the other processing condition are identical with embodiment 1, and test-results is the face subordinate list as follows.
Subordinate list: main technique condition and the result of each embodiment
Claims (2)
1. an air catalytic oxidation is synthetic 3, and the method for 4-Dihydroxy benzaldehyde is characterized in that: condensation reaction is taken place under alkaline condition for pyrocatechol and oxoethanoic acid obtain 3; 4-dihydroxyl racemic melic acid obtains pure article after separating, the accurately weighing of dry back; Be dissolved in the water, use alkaline aqueous solution to regulate the pH value and be weakly alkaline, add catalyzer; Oxidizing reaction takes place and obtains 3,4-Dihydroxy benzaldehyde in bubbling air under condition of heating and stirring;
Catalyzer is the polycomponent composite type metallic oxide, and its element and molfraction formula are:
(Al)a·(Cu)b·(Mo)c·(Mn)d·(Fe)e·(Zn)·f·(Na)g·(O)h·(S)i；
In the formula: a, b, c, d, e, f, g, h, i are respectively the molfraction of A1, Cu, Mo, Mn, Fe, Zn, Na, O, S, and a is 0.001～0.4, and b is 0.002～0.3, and c is 0.001～0.25; D is 0.001～0.4, and e is 0.001～0.35, and f is 0.015～0.4, and g is 0.001～0.3, and h is 0.001～0.4, and i is 0.001～0.4;
The mol ratio of catalyzer and 3,4-dihydroxyl racemic melic acid is 0.02～0.05; Temperature is 85～95 ℃; Air flow quantity 80～110L/h.
2. air catalytic oxidation according to claim 1 is synthetic 3, and the method for 4-Dihydroxy benzaldehyde is characterized in that: used alkali is one or more the mixture in sodium hydroxide, Pottasium Hydroxide, yellow soda ash, the salt of wormwood.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2008102223899A CN101676253B (en) | 2008-09-18 | 2008-09-18 | Method for synthesizing 3,4-dihydroxy benzaldehyde by using air catalytic oxidation |
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| CN2008102223899A CN101676253B (en) | 2008-09-18 | 2008-09-18 | Method for synthesizing 3,4-dihydroxy benzaldehyde by using air catalytic oxidation |
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| CN101676253A CN101676253A (en) | 2010-03-24 |
| CN101676253B true CN101676253B (en) | 2012-07-18 |
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| CN103012091A (en) * | 2011-09-22 | 2013-04-03 | 中国石油天然气股份有限公司 | Method for preparing 3,4-dihydroxy benzaldehyde through copper oxide lattice oxygen oxidation |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4165341A (en) * | 1977-02-04 | 1979-08-21 | Ube Industries, Ltd. | Process for preparing protocatechualdehyde and its derivatives |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4165341A (en) * | 1977-02-04 | 1979-08-21 | Ube Industries, Ltd. | Process for preparing protocatechualdehyde and its derivatives |
Non-Patent Citations (2)
| Title |
|---|
| JP昭54-66639A 1979.05.29 |
| JP昭55-22614A 1980.02.18 |
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