CN101486630A - Catalytic synthesizing process of 3-methoxy-4-phenol methanol - Google Patents
Catalytic synthesizing process of 3-methoxy-4-phenol methanol Download PDFInfo
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- CN101486630A CN101486630A CNA2009100465972A CN200910046597A CN101486630A CN 101486630 A CN101486630 A CN 101486630A CN A2009100465972 A CNA2009100465972 A CN A2009100465972A CN 200910046597 A CN200910046597 A CN 200910046597A CN 101486630 A CN101486630 A CN 101486630A
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- methoxyl group
- salicylic alcohol
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Abstract
The invention relates to a catalytic synthesis method of 3-methoxyl-4-hydroxybenzyl alcohol. The method takes guaiacol and formaldehyde as raw materials, adopts inorganic base or one or the mixture of a plurality of inorganic bases as a catalyst and takes aqueous solution or the mixture of water and organic solvent as a solvent, the reaction lasts for 30 minutes to 300 minutes, the reaction temperature is 5 DEG C to 60 DEG C and such side reactions as product polymerization, dismutation and the like caused by high temperature are avoided. The method not only has cheap raw materials which are easy to obtain, but also has simple technique, low energy consumption and fairly high industrial practicability and is environmentally friendly.
Description
Technical field
The present invention relates to the process for catalytic synthesis of a kind of 3-methoxyl group-4-salicylic alcohol (being commonly called as vanillic alcohol).More specifically, refer in particular to methyl catechol and formaldehyde method through hydroxyalkylation prepared in reaction 3-methoxyl group-4-salicylic alcohol.
Background technology
Calendar year 2001, B.P.Bandgar etc. reduce vanillin food grade,1000.000000ine mesh with the hydrogen exchange resin of sulfation boron (SBER) and obtain vanillic alcohol, this method temperature of reaction low (normal temperature), productive rate height (80%), but the reaction times reach 35 hours.Lei Shi in 2004 etc. are catalyzer with Ni, are that solvent can obtain 54% vanillic alcohol with the vanillin food grade,1000.000000ine mesh reduction with THF.Yuhan Zhou in 2008 etc. are with NaBH
4/ Me
2SO
4/ B (OMe)
3For reducing vanillinated, catalyzer obtains high yield vanillic alcohol (98%), only 1.5 hours reaction times.Above synthetic method all belongs to reduction method, and this method product is pure, convenient separation, and technology is simple, but vanillic alcohol major industry application is a synthesis of vanillin, so this method can only can not be adopted by suitability for industrialized production as a kind of laboratory synthetic method.
In the process of methyl catechol and the synthetic 3-methoxyl group of formaldehyde method-4-salicylic alcohol, because hydroxyl is the adjacency pair bit substituent, generating product not only has the 3-methoxyl group-4-salicylic alcohol of para-orientation, 3-methoxyl group-2-salicylic alcohol of also following the ortho position to replace simultaneously, therefore control the attack point of formaldehyde, improve the contraposition product, be one of focus of studying of scientific research personnel always.
The main method of present industrial synthesis of vanillin is the nitrosification method.The first step methyl catechol and formaldehyde (or urotropine) are that catalyst reaction gets vanillic alcohol with hydrochloric acid.Again by vanillic alcohol and NDMA (by N, N one xylidine and nitrite reaction make) oxidizing reaction and vanillin food grade,1000.000000ine mesh.In order to increase the yield of vanillin food grade,1000.000000ine mesh, in reaction process, make catalyzer with copper and cuprous chloride.But this method norm quota of consumption (in methyl catechol) can reach 1.32, and reaction efficiency is low, particularly environmental pollution is serious.
European patent EP 0485613A1 has described phenol, especially methyl catechol to hydroxymethylation, by methyl catechol and formaldehyde, in alcohol organic solvent, exist at sodium hydroxide and quaternary ammonium compound (as Tetramethylammonium hydroxide) and to react.But in reaction process, successively need two step underpressure distillation to remove unnecessary solvent, thereby cause operational path loaded down with trivial details.In addition, it is higher that this method also has temperature of reaction, the shortcoming that the reaction times is long.
U.S. Pat 005811587A has described the hydroxyalkylation method of carbocyclic ring aromatic oxide.Carbocyclic ring aromatic oxide and carbonyl compound react under there is situation in catalyzer, it is characterized in that hydroxyalkylation reaction is to carry out existing under the significant quantity zeolite situation.It is relatively stricter that but this method requires zeolite, must be the hydrophobic mordenite with high silicon aluminum ratio of macropore, and mordenite with high silicon aluminum ratio has certain degree of difficulty on synthetic technology, cause cost higher.Late nineteen eighties, Japan repeatedly delivers the selection synthetic article about p-Hydroxybenzylalcohol.Beta-cyclodextrin and the effect of derivative in this reaction thereof discussed in detail in article.This method is a raw material with phenol and formaldehyde, is catalyzer with sodium hydroxide and beta-cyclodextrin, reacts under aqueous conditions.But sodium hydroxide that this reaction needed is a large amount of and beta-cyclodextrin and speed of response are very slow, therefore are difficult to industrialization.
Summary of the invention
The object of the present invention is to provide that a kind of technology is simple, energy consumption is low, eco-friendly 3-methoxyl group-4-salicylic alcohol synthetic method.
Primary and foremost purpose of the present invention is to provide the preparation method of a kind of 3-methoxyl group-4-salicylic alcohol, and the feature of this compound is to carry out the hydroxyalkylation reaction in the contraposition of methyl catechol.With methyl catechol and formaldehyde is raw material, carries out in the liquid phase environment under the basic catalyst condition.
Compared with prior art, the present invention has the following advantages:
1) temperature of reaction of the present invention is carried out under 5-60 ℃, has avoided side reactions such as product polymerization that high temperature causes and disproportionation, thereby has improved product selectivity.
2) one-step synthesis 3-methoxyl group of the present invention-4-salicylic alcohol, methyl catechol, formaldehyde and triethylamine source are abundant.Possesses very high industrial applicibility.
3) technology of the present invention is simple, energy consumption is low, environmental friendliness.
(1) catalyzer
The method according to this invention, hydroxyalkylation are carried out in alkaline environment.Required catalyzer is a sodium hydroxide, potassium hydroxide, yellow soda ash, salt of wormwood, sodium bicarbonate, ammoniacal liquor, thanomin, diethanolamine, trolamine, methylamine, Trimethylamine 99, one or several mixtures in the basic cpds such as triethylamine and Bian amine.Preferred C
1-8Organic amine.
(2) solvent
Hydroxyalkylation is reflected in the aqueous solution and carries out.
(3) reaction conditions
According to the present invention, reduce temperature and help improving the selectivity of contraposition, but transformation efficiency can reduce simultaneously.Therefore, in order to guarantee enough activity, temperature of reaction should be between 0-100 ℃, preferred 5-60 ℃.
Described reaction is finished within the 15-480 after all reactants mix minute usually, preferably finishes within 30-300 minute.
Described reaction is all carried out under normal pressure.
According to the present invention, the ratio of methyl catechol and formaldehyde generally is controlled between the 0.01-10, between the preferred 0.5-9.
According to the present invention, the mol ratio of required catalyzer and methyl catechol is between 0.01-6, between the preferred 0.1-4.
The embodiment that provides below is in order to further specify the present invention, but never is limitation of the present invention.
Embodiment 1
Be equipped with at 100ml and add methyl catechol 0.01mol, triethylamine 2ml, Paraformaldehyde 96 0.04mol, water 10ml in the there-necked flask of mechanical stirring device.Adopt thermostatic bath to be heated to 30 ℃ reaction mixture, keep constant.After the homo(io)thermism, controlling reaction time is 4h, efficient liquid phase chromatographic analysis.Triethylamine is carried out recycling.
The productive rate of 3-methoxyl group-4-salicylic alcohol is: 18.9%; The selectivity of 3-methoxyl group-4-salicylic alcohol is: 27.3%; The transformation efficiency of methyl catechol is: 69.2%.
Embodiment 2
Be equipped with at 100ml and add methyl catechol 0.01mol, triethylamine 1ml, Paraformaldehyde 96 0.04mol, water 25ml in the there-necked flask of mechanical stirring device.Adopt thermostatic bath to be heated to 25 ℃ reaction mixture, keep constant.After the homo(io)thermism, controlling reaction time is 2.5h, efficient liquid phase chromatographic analysis.Triethylamine is carried out recycling.
The productive rate of 3-methoxyl group-4-salicylic alcohol is: 12.3%; The selectivity of 3-methoxyl group-4-salicylic alcohol is: 37.1%; The transformation efficiency of methyl catechol is: 33.2%.
Embodiment 3
Be equipped with at 100ml and add methyl catechol 0.01mol, triethylamine 1.5ml, Paraformaldehyde 96 0.03mol, water 25ml in the there-necked flask of mechanical stirring device.Adopt thermostatic bath to be heated to 30 ℃ reaction mixture, keep constant.After the homo(io)thermism, controlling reaction time is 3.5h, efficient liquid phase chromatographic analysis.Triethylamine is carried out recycling.
The productive rate of 3-methoxyl group-4-salicylic alcohol is: 17.2%; The selectivity of 3-methoxyl group-4-salicylic alcohol is: 30.8%; The transformation efficiency of methyl catechol is: 55.8%.
Embodiment 4
Be equipped with at 100ml and add methyl catechol 0.01mol, sodium hydroxide 0.03mol, Paraformaldehyde 96 0.09mol, water 25ml in the there-necked flask of mechanical stirring device.Adopt thermostatic bath to be heated to 28 ℃ reaction mixture, keep constant.After the homo(io)thermism, controlling reaction time is 4h, efficient liquid phase chromatographic analysis.
The productive rate of 3-methoxyl group-4-salicylic alcohol is: 31.4%; The selectivity of 3-methoxyl group-4-salicylic alcohol is: 44.1%; The transformation efficiency of methyl catechol is: 71.1%.
Embodiment 5
Be equipped with at 100ml and add methyl catechol 0.01mol, potassium hydroxide 0.03mol, Paraformaldehyde 96 0.05mol, water 20ml in the there-necked flask of mechanical stirring device.Adopt thermostatic bath to be heated to 28 ℃ reaction mixture, keep constant.After the homo(io)thermism, controlling reaction time is 4h, efficient liquid phase chromatographic analysis.
The productive rate of 3-methoxyl group-4-salicylic alcohol is: 16.7%; The selectivity of 3-methoxyl group-4-salicylic alcohol is: 52.7%; The transformation efficiency of methyl catechol is: 32.0%.
Embodiment 6
Be equipped with at 100ml and add methyl catechol 0.01mol, sodium hydroxide 0.03mol, Paraformaldehyde 96 0.09mol, water 20ml in the there-necked flask of mechanical stirring device.Adopt thermostatic bath to be heated to 28 ℃ reaction mixture, keep constant.After the homo(io)thermism, controlling reaction time is 2h, efficient liquid phase chromatographic analysis.
The productive rate of 3-methoxyl group-4-salicylic alcohol is: 21.9%; The selectivity of 3-methoxyl group-4-salicylic alcohol is: 45.0%; The transformation efficiency of methyl catechol is: 48.7%.
Claims (8)
1. the present invention relates to the process for catalytic synthesis of a kind of 3-methoxyl group-4-salicylic alcohol, it is characterized in that 3-methoxyl group-4-salicylic alcohol is to be carried out catalysis in the liquid phase environment in the presence of catalyzer to synthesize by methyl catechol and formaldehyde.
2. according to the process for catalytic synthesis of the described 3-methoxyl group of claim 1-4-salicylic alcohol, it is characterized in that required catalyzer is a sodium hydroxide, potassium hydroxide, yellow soda ash, salt of wormwood, sodium bicarbonate, ammoniacal liquor, thanomin, diethanolamine, trolamine, methylamine, Trimethylamine 99, one or several mixtures in the basic cpds such as triethylamine and Bian amine, preferred C
1-8Organic amine.
3. according to the process for catalytic synthesis of each described 3-methoxyl group-4-salicylic alcohol of claim 1-2, it is characterized in that required solvent is the aqueous solution.
4. according to the process for catalytic synthesis of each described 3-methoxyl group-4-salicylic alcohol of claim 1-3, the temperature that it is characterized in that carrying out the hydroxyalkylation reaction between 0-100 ℃, preferred 5-60 ℃.
5. according to the process for catalytic synthesis of each described 3-methoxyl group-4-salicylic alcohol of claim 1-4, the mol ratio that it is characterized in that required catalyzer and methyl catechol is between 0.01-6, between the preferred 0.1-4.
6. according to the process for catalytic synthesis of each described 3-methoxyl group-4-salicylic alcohol of claim 1-5, it is characterized in that the mol ratio of methyl catechol and formaldehyde generally is controlled between the 0.01-10, between the preferred 0.5-9.
7. according to the process for catalytic synthesis of each described 3-methoxyl group-4-salicylic alcohol of claim 1-6, it is characterized in that the reaction times generally between 15-480 minute, preferred 30-300 minute.
8. according to the process for catalytic synthesis of each described 3-methoxyl group-4 salicylic alcohol of claim 1-7, it is characterized in that being reflected under the normal pressure and carry out.
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| CN 200910046597 CN101486630B (en) | 2009-02-25 | 2009-02-25 | Catalytic synthesizing process of 3-methoxy-4-phenol methanol |
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| CN 200910046597 CN101486630B (en) | 2009-02-25 | 2009-02-25 | Catalytic synthesizing process of 3-methoxy-4-phenol methanol |
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| CN101486630B CN101486630B (en) | 2013-06-12 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108264454A (en) * | 2016-12-30 | 2018-07-10 | 上海医药工业研究院 | A kind of preparation method of phloroglucin analog derivative and intermediate |
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| WO1991018858A1 (en) * | 1990-05-25 | 1991-12-12 | Mitsubishi Petrochemical Company Limited | Process for para-methylolating phenolic compound |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108264454A (en) * | 2016-12-30 | 2018-07-10 | 上海医药工业研究院 | A kind of preparation method of phloroglucin analog derivative and intermediate |
| CN108264454B (en) * | 2016-12-30 | 2021-05-28 | 上海医药工业研究院 | Preparation method of phloroglucinol derivative and intermediate |
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