CN100526281C - Method of synthesizing 3-methoxy-4-dydroxymandelic acid or 3-ethoxy-4-dydroxymandelic acid by acetaldehyde acid method - Google Patents
Method of synthesizing 3-methoxy-4-dydroxymandelic acid or 3-ethoxy-4-dydroxymandelic acid by acetaldehyde acid method Download PDFInfo
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- CN100526281C CN100526281C CNB2007100552990A CN200710055299A CN100526281C CN 100526281 C CN100526281 C CN 100526281C CN B2007100552990 A CNB2007100552990 A CN B2007100552990A CN 200710055299 A CN200710055299 A CN 200710055299A CN 100526281 C CN100526281 C CN 100526281C
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Abstract
The invention discloses a making method of 3-methoxy (or 3-ethoxy)-4-hydroxy amygdalic acid, which comprises the following steps: adopting methyl guaiacol or ethyl guaiacol and glyoxylic acid as raw material; setting the molar rate of methyl guaiacol or ethyl guaiacol and sodium hydroxide at 1:1.1:2.2-1:1.2:2.3; using 0.5-5% quaternary amine compound as catalyst under 28+-1 deg.c; stirring; dripping methyl guaiacol or ethyl guaiacol, glyoxylic acid and residual sodium hydroxide in the alkaline solution of catalyst; finishing dripping course within 3h; reacting for 0.5-2h; selecting catalyst from at least one of tetramethyl ammonium hydroxide, tetramethyl ammonium chloride, tetraethyl ammonium chloride or tetramethyl ammonium bromide; improving product receiving rate to 81.28-86.25%.
Description
Technical field
The present invention relates to a kind of is raw material with methyl catechol or ethylguaiacol and oxoethanoic acid, carries out condensation reaction in containing the basic solution of catalyzer, prepares the method for 3 methoxy 4 hydroxymandelic acid or 3-oxyethyl group-4-hydroxymandelic acid.
Background technology
3 methoxy 4 hydroxymandelic acid (3-methoxy-4-hydroxyphenyle-thanol acid) and 3-oxyethyl group-4-hydroxymandelic acid (3-oxyethyl group-4-hydroxymandelic acid) are the important intermediate of synthesis of vanillin and vanirone, vanillin food grade,1000.000000ine mesh or vanirone are universal spices, can be used as fixative, seasonings and spoiled dose; Remove this, still synthetic medical important intermediate, as: 3 methoxy 4 hydroxymandelic acid is a preparation Trimpex 3,4, the important intermediate of 5-trimethoxy-pyrimidine TMP.
According to the literature, at present, adopt the synthetic 3 methoxy 4 hydroxymandelic acid of acetaldehyde acid system and 3-oxyethyl group-4-hydroxymandelic acid, operational path is simple, easy to operate, but have deficiencies such as long reaction time, temperature of reaction height, selectivity and product yield are low, as: the research for preparing vanillin food grade,1000.000000ine mesh with methyl catechol and oxoethanoic acid, Li Jiansheng etc. (Tianjin chemical research institute), the Jiangsu chemical industry, the 21st the 3rd phase of volume, the 13rd～16 page, 1993, announced that with methyl catechol and oxoethanoic acid be raw material, carry out condensation reaction under 70 ℃, product yield is 54%～78%.Oxoethanoic acid prepares the optimization of vanillin food grade,1000.000000ine mesh processing condition, swim good brave etc., food and the 24th the 4th phase of volume of biotechnology journal, the 97th～99 page, publish in July, 2005, announced oxoethanoic acid and methyl catechol are carried out condensation reaction under 75 ℃, the methyl catechol transformation efficiency is 84%, and product yield is up to 85%.3 methoxy 4 hydroxymandelic acid synthetic, Zhao Yuan, Chengde Petroleum Higher Junior College's journal, the 2nd the 1st phase of volume, the 31st～34 page, published in 2000 years, disclosing in temperature of reaction is that 33～35 ℃, reaction times are under 7～8h optimal conditions, and product yield is 76%.
Vanillin food grade,1000.000000ine mesh and vanirone are a kind of fine chemicals of high additive value.For many years, the experts and scholars of some enterprise and institutions and institution of higher learning the yield that improves vanillin food grade,1000.000000ine mesh and vanirone, all study as an important problem, but yield are still not ideal enough.The method of present disclosed acetaldehyde acid system synthesis of vanillin and vanirone, subject matter is that yield is low.It is reported that the vanillin food grade,1000.000000ine mesh yield of India is 76%; As above-mentioned, domestic general level is 76～78%.
Summary of the invention
The object of the present invention is to provide a kind of is raw material with methyl catechol or ethylguaiacol and oxoethanoic acid, in the presence of catalyzer, in basic solution, carry out condensation reaction, the method of synthetic 3 methoxy 4 hydroxymandelic acid or 3-oxyethyl group-4-hydroxymandelic acid is to shorten the reaction times, reduce temperature of reaction, to improve the reaction product yield.
The mechanism of action of the present invention is expressed as follows with chemical equation:
With methyl catechol and oxoethanoic acid is raw material, in containing the basic solution of catalyzer, as follows through the reaction equation of the synthetic 3 methoxy 4 hydroxymandelic acid of condensation reaction:
Main reaction:
Side reaction:
With ethylguaiacol and oxoethanoic acid is raw material, in containing the basic solution of catalyzer, as follows through the reaction equation of the synthetic 3-oxyethyl group of condensation reaction-4-hydroxymandelic acid:
Main reaction:
Side reaction:
The technical scheme that realizes above-mentioned purpose of the present invention is:
A kind of method for preparing 3 methoxy 4 hydroxymandelic acid or 3-oxyethyl group-4-hydroxymandelic acid, with methyl catechol or ethylguaiacol and oxoethanoic acid is raw material, oxoethanoic acid, methyl catechol or ethylguaiacol, the mol ratio of sodium hydroxide is 1: 1.1: 2.2～1: 1.2: 2.3, with the quaternary ammonium salt compound is catalyzer, its consumption is 0.5～5% of methyl catechol or an ethylguaiacol quality, the control setting-up point is 28 ± 1 ℃, stir down in the basic solution of described catalyzer, drip methyl catechol or ethylguaiacol respectively simultaneously, oxoethanoic acid and remaining sodium hydroxide solution, 3h drips, and continues reaction 0.5～2h then under above-mentioned condition.Reaction is reduced to room temperature with temperature of reaction after finishing, and sampling analysis amygdalic acid content also calculates product yield.
Above-described method, its described quaternary ammonium salt compound catalyzer is selected from Tetramethylammonium hydroxide A (CH
3)
4NOH, tetramethyl ammonium chloride B (CH
3)
4NCl, 4 bromide C (CH
3)
4NBr, etamon chloride D (C
2H
5)
4NCl or tetraethylammonium bromide E (C
2H
5)
4At least a among the NBr.
The present invention compared with prior art has a significant effect: this technology with quaternary ammonium salt compound as catalyzer, change feed way, with methyl catechol or ethylguaiacol, glyoxylic acid solution and remaining alkaline solution, splash into simultaneously respectively in the basic solution of catalyzer and carry out condensation reaction, reaction milder and stable, setting-up point is reduced to 28 ± 1 ℃, reaction times is 3.5～5h, thereby reduced the generation of by product, condensation reaction products 3 methoxy 4 hydroxymandelic acid, 3-oxyethyl group-4-hydroxymandelic acid yield have been brought up to 81.28～86.25%.
Embodiment
Now the present invention is described in detail as follows in conjunction with embodiment:
Embodiment 1
(1) takes by weighing the 37g oxoethanoic acid and be added in the 57g water, stir evenly standby.
(2) take by weighing 18.8g sodium hydroxide and add 140g water, it is standby to be mixed with sodium hydroxide solution.
(3) taking by weighing the 27g mass content is that 99.4% methyl catechol is standby.
Taking by weighing 110g water is added in the condensation still that water bath with thermostatic control, agitator, thermometer are housed, start stirring, be warming up to 28 ℃, add 0.5g catalyst A (Tetramethylammonium hydroxide), add the aqueous sodium hydroxide solution that 17g above-mentioned (2) prepares again, behind the temperature-stable, drip glyoxylic acid solution, (2) remaining aqueous sodium hydroxide solution and (3) methyl catechol that above-mentioned (1) prepares respectively simultaneously through three pipelines, 3h drips off, and continues stirring reaction 1h more with this understanding.Reaction finishes back sampling analysis 3 methoxy 4 hydroxymandelic acid content, and test-results is seen attached list.
Embodiment 2
Operation steps according to embodiment 1, adopt catalyst B (tetramethyl ammonium chloride), catalyzer C (4 bromide), catalyst A to add B (in mass respectively, 1), catalyst A adds C (in mass A: B=1:, A: C=1: 1), catalyst B and C (in mass, 1), catalyst A adds B and add C (in mass B: C=1:, A: B: C=1: 2: 2), 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
(1) takes by weighing the 40g oxoethanoic acid and be added in the 61.6g water, stir evenly standby.
(2) take by weighing 21g sodium hydroxide and add 156g water, it is standby to be mixed with sodium hydroxide solution.
(3) taking by weighing the 31.56g mass content is that 99.4% methyl catechol is standby.
Taking by weighing 119g water is added in the condensation still that water bath with thermostatic control, agitator, thermometer are housed, start stirring, be warming up to 28 ℃, add 1.58g catalyst B (tetramethyl ammonium chloride), add the aqueous sodium hydroxide solution that 18g above-mentioned (2) prepares again, behind the temperature-stable, drip glyoxylic acid solution, (2) remaining aqueous sodium hydroxide solution and (3) methyl catechol that above-mentioned (1) prepares respectively simultaneously through three pipelines, 3h drips off, and continues stirring reaction 1h more with this understanding.Reaction finishes back sampling analysis 3 methoxy 4 hydroxymandelic acid content, and test-results is seen attached list.
Embodiment 6
According to the operation steps of embodiment 5, remove change catalyzer add-on, other processing condition are with embodiment 5, and test-results is seen attached list.
Comparative example 1 (according to the method for document 1)
(1) taking by weighing the 37g mass content is that 36.1% oxoethanoic acid is added in the 57g water, stirs evenly standby.
(2) take by weighing 16.25g sodium hydroxide and add 140g water, it is standby to be mixed with sodium hydroxide solution.
Take by weighing 110g water and be added in the condensation still that water bath with thermostatic control, agitator, thermometer are housed, start stirring, adding 36.4g mass content is 99.4% methyl catechol, is warming up to 70 ℃, adds above-mentioned (2) prepared sodium hydroxide solution again.Behind the temperature-stable, drip the glyoxylic acid solution that above-mentioned (1) prepares, 1.5h drips, and continues stirring reaction 0.5h again under this temperature.Reaction finishes to stop to stir afterreaction thing surface tangible oily by product.Test-results: oxoethanoic acid transformation efficiency 95.38%, 3 methoxy 4 hydroxymandelic acid yield 70.80%.
Comparative example 2 (on the basis of document 1, adding the used catalyzer of the present invention)
(1) taking by weighing the 37g mass content is that 36.1% oxoethanoic acid is added in the 57g water, stirs evenly standby.
(2) take by weighing 16.25g sodium hydroxide and add 140g water, it is standby to be mixed with sodium hydroxide solution.
Taking by weighing 110g water is added in the condensation still that water bath with thermostatic control, agitator, thermometer are housed, add catalyst B (tetramethyl ammonium chloride) 0.7g, start stirring, adding 36.4g mass content is 99.4% methyl catechol, be warming up to 70 ℃, add above-mentioned (2) prepared sodium hydroxide solution again.Behind the temperature-stable, drip the glyoxylic acid solution that above-mentioned (1) prepares, 1.5h drips, and continues stirring reaction 0.5h again under this temperature.Reaction finishes to stop to stir afterreaction thing surface tangible oily by product.Test-results: oxoethanoic acid transformation efficiency 95.38%, 3 methoxy 4 hydroxymandelic acid yield 76.54%.
Comparative example 3 (according to the method for document 2)
(1) taking by weighing the 37g mass content is that 36.1% oxoethanoic acid is added in the 57g water, stirs evenly standby.
(2) take by weighing 18.74g sodium hydroxide and add 140g water, it is standby to be mixed with sodium hydroxide solution.
Take by weighing 110g water and be added in the condensation still that water bath with thermostatic control, agitator, thermometer are housed, start stirring, add the glyoxylic acid solution that above-mentioned (1) prepares, be warming up to 75 ℃.Behind the temperature-stable, dripping above-mentioned (2) prepared sodium hydroxide solution and 27g mass content respectively through two pipelines is 99.4% methyl catechol, drips in the 2h, continues stirring reaction 1h again under this temperature.Reaction finishes back sampling analysis 3 methoxy 4 hydroxymandelic acid content.Test-results: oxoethanoic acid transformation efficiency 91.19%, 3 methoxy 4 hydroxymandelic acid yield 72.73%.
Embodiment 7
(1) takes by weighing the 37g oxoethanoic acid and be added in the 57g water, stir evenly standby.
(2) take by weighing 18.8g sodium hydroxide and add 140g water, it is standby to be mixed with sodium hydroxide solution.
(3) taking by weighing the 30g mass content is that 99.8% ethylguaiacol is standby.
Taking by weighing 110g water is added in the condensation still that water bath with thermostatic control, agitator, thermometer are housed, start stirring, be warming up to 28 ℃, add 0.5g catalyzer D (etamon chloride), add the aqueous sodium hydroxide solution that 17g above-mentioned (2) prepares again, behind the temperature-stable, drip glyoxylic acid solution, (3) ethylguaiacol and (2) remaining aqueous sodium hydroxide solution that above-mentioned (1) prepares respectively simultaneously through three pipelines, 3h drips off, and continues stirring reaction 1h again under this temperature.Reaction finishes back sampling analysis 3-oxyethyl group-4-hydroxymandelic acid content.Test-results: oxoethanoic acid transformation efficiency 97.8%, 3-oxyethyl group-4-hydroxymandelic acid yield 85.41% (for details see attached table).
Embodiment 8
(1) takes by weighing the 37g oxoethanoic acid and be added in the 57g water, stir evenly standby.
(2) take by weighing 18.8g sodium hydroxide and add 140g water, it is standby to be mixed with sodium hydroxide solution.
(3) taking by weighing the 30g mass content is that 99.8% ethylguaiacol is standby.
Taking by weighing 110g water is added in the condensation still that water bath with thermostatic control, agitator, thermometer are housed, start stirring, be warming up to 28 ℃, add 0.5g catalyzer E (tetraethylammonium bromide), add the aqueous sodium hydroxide solution that 17g above-mentioned (2) prepares again, behind the temperature-stable, drip glyoxylic acid solution, (3) ethylguaiacol and (2) remaining aqueous sodium hydroxide solution that above-mentioned (1) prepares respectively simultaneously through three pipelines, 3h drips off, and continues stirring reaction 1h again under this temperature.Reaction finishes back sampling analysis 3-oxyethyl group-4-hydroxymandelic acid content.Oxoethanoic acid transformation efficiency 98.23%, 3-oxyethyl group-4-hydroxymandelic acid yield 84.38% (test-results sees following subordinate list for details).
Subordinate list. main technique condition and the result of each embodiment
Claims (2)
1, a kind of method for preparing 3 methoxy 4 hydroxymandelic acid or 3-oxyethyl group-4-hydroxymandelic acid, with methyl catechol or ethylguaiacol and oxoethanoic acid is raw material, oxoethanoic acid, methyl catechol or ethylguaiacol, the mol ratio of sodium hydroxide is 1: 1.1: 2.2～1: 1.2: 2.3, setting-up point is 28 ± 1 ℃, with the quaternary ammonium salt compound is catalyzer, its consumption is 0.5～5% of methyl catechol or an ethylguaiacol quality, the control setting-up point is 28 ± 1 ℃, stirring down to pH is in the basic solution of 9～13 described catalyzer, drip methyl catechol or ethylguaiacol respectively simultaneously, oxoethanoic acid and remaining sodium hydroxide solution, 3h drips, and continues reaction 0.5～2h under above-mentioned condition.
2, method according to claim 1, described quaternary ammonium salt compound catalyzer is selected from Tetramethylammonium hydroxide (CH
3)
4NOH, tetramethyl ammonium chloride (CH
3)
4NCl, 4 bromide (CH
3)
4NBr, etamon chloride (C
2H
5)
4NCl or tetraethylammonium bromide (C
2H
5)
4At least a among the NBr.
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| CNB2007100552990A CN100526281C (en) | 2007-02-02 | 2007-02-02 | Method of synthesizing 3-methoxy-4-dydroxymandelic acid or 3-ethoxy-4-dydroxymandelic acid by acetaldehyde acid method |
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| CNB2007100552990A CN100526281C (en) | 2007-02-02 | 2007-02-02 | Method of synthesizing 3-methoxy-4-dydroxymandelic acid or 3-ethoxy-4-dydroxymandelic acid by acetaldehyde acid method |
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| CN100526281C true CN100526281C (en) | 2009-08-12 |
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| CN102086151B (en) * | 2009-12-04 | 2013-10-16 | 中国石油天然气股份有限公司 | Method for preparing 3-methoxy-4-hydroxy mandelic acid |
| CN105862070B (en) * | 2016-04-11 | 2018-02-23 | 广州大有精细化工厂 | The method that the hydroxymandelic acid of 3 methoxyl group 4 or the hydroxymandelic acid of 3 ethyoxyl 4 are prepared using bipolar membrane electrodialysis |
| CN109956858B (en) * | 2017-12-26 | 2022-02-15 | 万华化学集团股份有限公司 | Method for preparing 3-methoxy-4-hydroxymandelic acid |
| CN114082449B (en) * | 2021-12-01 | 2023-10-17 | 万华化学集团股份有限公司 | Preparation method and application of aluminum ligand catalyst |
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Non-Patent Citations (4)
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| 3-甲氧基-4-羟基扁桃酸的合成. 赵元.承德石油高等专科学校学报，第2卷第1期. 2000 |
| 3-甲氧基-4-羟基扁桃酸的合成. 赵元.承德石油高等专科学校学报，第2卷第1期. 2000 * |
| 乙基香兰素合成方法及研究新进展. 张德善，项文彦，尹秀清等.化工科技，第13卷第5期. 2005 |
| 乙基香兰素合成方法及研究新进展. 张德善，项文彦，尹秀清等.化工科技，第13卷第5期. 2005 * |
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