CN1097575C - Process for preparing 4-methyl catechol - Google Patents
Process for preparing 4-methyl catechol Download PDFInfo
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- CN1097575C CN1097575C CN99125464A CN99125464A CN1097575C CN 1097575 C CN1097575 C CN 1097575C CN 99125464 A CN99125464 A CN 99125464A CN 99125464 A CN99125464 A CN 99125464A CN 1097575 C CN1097575 C CN 1097575C
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- Prior art keywords
- hydrogen peroxide
- cresols
- methyl
- methyl pyrocatechol
- reaction
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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
- 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
- Y02P20/582—Recycling of unreacted starting or intermediate materials
Abstract
The present invention relates to a method of preparing 4-methylpyrocatechol using hydrogen peroxide solution through hydroxylation. The method uses a titanium silicon molecular sieve as a catalyst and uses low concentration hydrogen peroxide solution to proceed the hydroxylation of 4-cresol. The present invention has the advantages of low reaction temperature, high selectivity, high single pass yield and no pollution.
Description
The present invention relates to the preparation method of 4-methyl pyrocatechol, particularly relate to a kind of method for preparing the 4-methyl pyrocatechol with the superoxol hydroxylation.
The 4-methyl pyrocatechol is a kind of purposes organic compound more widely, can be used as the important intermediate of many chemical such as spices, medicine, agricultural chemicals, dyestuff, oxidation inhibitor.German patent DE-PS 20 64 497 discloses a kind ofly to be had under the condition that strong acid exists, the nuclear hydroxylating technology of aromatic hydroxy compound, the particularly phenol that carries out with hydrogen peroxide.When the reaction beginning, the content of water is no more than 20% (weight) in the reaction medium, is preferably 10% (weight), more preferably below 1% (weight); The pH value of strong acid is below 0.1.Therefore, above-mentioned strong acid preferably sulfuric acid or perchloric acid.Yet the applicant of DE-PS 20 64 497 patents has done negative evaluation to own above-mentioned technical scheme in the specification sheets of its later patents DE-PS 26 58 545.They point out that when using strong acid and metal complex component such as phosphoric acid at the same time, also only below 30%, in fact transformation efficiency only is 4～10% to the yield of hydroxylation product (calculating with the aromatic hydroxy compound that transforms).Thereby the raw material of quite a lot of volume need recycle, and the corrosion of strong acid also can not be ignored.
So for improving aforesaid method, in German patent DE-PS 26 58 545, except the catalyzer and stablizer that are proposed, also aromatic aldehydes is added in suggestion in addition, as phenyl aldehyde etc.Promptly in strong acid, metal complex component and add in addition under the condition of aromatic aldehyde, phenol and substituted phenol are carried out hydroxylating with hydrogen peroxide.Become three components owing to influence two components of reaction at this moment, these components all are difficult to reclaim, but must separate from reaction mixture again, and aromatic aldehyde is entered the danger in the finished product in addition by hydrogen peroxide oxidation generation impurity.If phenol: the proportioning of hydrogen peroxide reaches 20: 1, adds hydrogen peroxide and is about at 85% o'clock, can reach about 70～76% yield.There is the yield of two embodiment can reach 80%,, still must reclaims big content of starting materials even if in this case.
At German patent DE-PS 33 08 737, DE-PS 33 08 769, also disclose the method that prepare 4-methyl pyrocatechol different with above-mentioned technology among DE-PS 33 08 763 and the DE-PS33 08 726.This method is under the condition that has sulfurous gas or tin anhydride to exist, and carries out hydroxylating with the organic solvent of phenol or derivatives thereof by hydrogen peroxide, and this is undoubtedly a significant improvement to preceding method.Although can not produce the corrosion of introducing in the method by strong acid, but it also need add aldehyde cpd or the complex compound component is strengthened this process, and need almost water-free hydrogen peroxide solution in this method, the content that is water can not be greater than 1% (weight), and preferably water content will be lower than 0.5 (weight) %.Yet the use of anhydrous hydrogen peroxide can bring the problems of secure context.
Introduce a kind of inorganic or organic compound of arsenic or antimony that uses among the clear 58-39633 of day disclosure special permission communique and made catalyzer, carried out the method for the hydroxylating of phenol or derivatives thereof with aqueous hydrogen peroxide solution.Requiring hydrogen peroxide in this method is 30%～90% (weight), and temperature of reaction is preferably in 70～130 ℃ of scopes at 50～150 ℃.Hydrogen peroxide is below 0.3, to be preferably in below 0.15 with the ratio of aromatics.But this method yield is lower, and yield is with H among the embodiment
2O
2Calculating is about 46% (mole), only is 3.5% with 4-cresols calculated yield; And still have a large amount of raw materials to need reuse.
German patent DE-PS 36 43 206 discloses a kind of in the presence of sulfurous gas or tin anhydride catalyzer, and phenol or derivatives thereof and aqueous hydrogen peroxide solution carry out the method for hydroxylating.The aqueous hydrogen peroxide solution concentration that this hydroxylating adopts is 30～85% (wt), is preferably 70～85% (wt); The mol ratio of its substituted phenol and hydrogen peroxide is 5 to 25: 1, is preferably 10 to 16: 1.But still there are many safety problems in the aqueous hydrogen peroxide solution of high density, and this method once through yield is too low, also has a large amount of raw materials to need to recycle.
This shows, in the prior art of preparation 4-methyl pyrocatechol method, the problem that big content of starting materials need reclaim or recycle, safety problem that strong acid corrosive problem, use high-strength hydrogen peroxide bring or the like is the Root of Clark Clematis of this technical development of puzzlement.
Purpose of the present invention is exactly in order to overcome the shortcoming and defect of above-mentioned prior art, to provide a kind of temperature of reaction low, the selectivity height, and the once through yield height, free of contamination, use the lower concentration hydrogen peroxide to prepare the method for 4-methyl pyrocatechol.
Preparation 4-methyl pyrocatechol method of the present invention is achieved in that
4-methyl pyrocatechol of the present invention is to be raw material with 4-cresols and hydrogen peroxide,, reacts in inert solvent as catalyzer with HTS, and temperature of reaction is 40～100 ℃.
When concrete enforcement was of the present invention, the weight percent of above-mentioned hydrogen peroxide can be 10～50%, preferred 20～30%; On the consumption of titanium-silicon molecular sieve catalyst can be 1～20% of 4-cresols, preferred 5～12%; Count in molar ratio, the mol ratio of above-mentioned hydrogen peroxide and 4-cresols is 0.1～1, is preferably 0.2～0.5.Above-mentioned inert solvent is selected from one of following material or its mixture: water, methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, the trimethyl carbinol, acetone, butanone, propione, pimelinketone, benzene,toluene,xylene, trichloromethane, tetracol phenixin.
Can be during concrete operations with a certain amount of 4-cresols, HTS and appropriate solvent add and have stirring, condenser, temperature and take into account in the four-hole bottle of tear drop mouth.HTS is 1～20% (weight) of 4-cresols, is preferably 5～12% (weight); 4-cresols generally is to be dissolved in the suitable inert solvent, as acetone, in the solution such as ethanol/water or water.Reaction adopts normal pressure to stir, under agitation with mixture heating up to certain temperature, generally be at 50～100 ℃.Beginning to drip aqueous hydrogen peroxide solution then reacts.Aqueous hydrogen peroxide solution concentration is 10～50% (weight), is preferably 20～30% (weight), and the mol ratio of hydrogen peroxide and 4-cresols is 0.1～1, is preferably 0.2～0.5.Be incubated for some time again after dropwising, make that the hydroxylating of 4-cresols and hydrogen peroxide is complete.Respectively reaction product, catalyzer, the intact 4-cresols of unreacted are separated from solvent behind the sufficient reacting, promptly obtained reaction product 4-methyl pyrocatechol.The 4-cresols that reclaims according to method of the present invention need not carry out special processing and just can recycle.
Reaction product 4-methyl pyrocatechol of the present invention is analyzed with gas-chromatography.
In sum, the method for the 4-of preparation methyl pyrocatechol of the present invention is with the different of prior art: that prior art adopts is hydrogen peroxide organic solution or high concentration solution, the danger of blast is arranged, poor stability.And one aspect of the present invention is the low concentration hydrogen peroxide aqueous solution owing to what adopt, so technology is simple, and the reaction conditions gentleness is safe; On the other hand owing to used HTS to make catalyzer, the etching problem that has separation difficulty and generation when having avoided adopting strong acid catalyst, also eliminated the environmental issue that causes the waste water saliferous to bring because of the acid neutralization, simultaneously, make catalyzer with HTS, catalyst separating is easy, can repeatedly use repeatedly after manipulation of regeneration.
In a word, the method temperature of reaction for preparing the 4-methyl pyrocatechol of the present invention is low, the selectivity height, and the once through yield height, pollution-free, be a kind of good method of using the lower concentration hydrogen peroxide to prepare the 4-methyl pyrocatechol.
Below, the invention will be further described for the example by the inventive method.Protection scope of the present invention is not subjected to the restriction of following embodiment.The data of experimental result are measured with gas-liquid chromatograph (GLC) method.
Embodiment 1
250ml, have stirring, condenser, temperature and take into account in the four-hole bottle of tear drop mouth, add 86g (0.8ml) 4-cresols, add titanium-silicon molecular sieve catalyst 6.9g, add 34ml acetone and 52ml water as solvent again.With after the above-mentioned mixture heating up to 80 ℃, begin to drip the H of 30% (weight) concentration
2O
2, add-on 27g, in 150 minutes, add.Temperature of reaction is controlled at 80-85 ℃.Add H
2O
2Follow-up continuation of insurance temperature 90 minutes.As a result, the transformation efficiency of 4-cresols is 18%, and 4-methyl pyrocatechol, its selectivity of generating in the 4-cresols that transforms are 70%, and promptly the yield of 4-methyl pyrocatechol is 12.6%.
Embodiment 2
With 86 (0.8mol) 4-cresols, titanium-silicon molecular sieve catalyst 6.9g, 34m acetone and 52ml water add
With 86 (0.8mol) 4-cresols, titanium-silicon molecular sieve catalyst 6.9g in 34m acetone and the four-hole bottle of 52ml water adding with embodiment 1, is heated to 80 ℃, begins to drip the H of 30% (wt)
2O
2, add-on 45g adds in 120mins.Other conditions are with example 1.As a result, the transformation efficiency of 4-cresols is 28%, and selectivity is 49%, and 4-methyl pyrocatechol yield is 13.7%.
Embodiment 3
With 42.5ml ethanol and 42.5ml water as solvent, all the other conditions are with example 1, and dripping concentration is the H of 20% (wt)
2O
2240 minutes, 4-cresols transformation efficiency was 13%, and selectivity is 60%.
Embodiment 4
4-cresols adds 86g (0.8ml), H
2O
2With the mol ratio of 4-cresols be 0.2, all the other conditions are with the H of example 1,20% (wt)
2O
2Dripped off at 180 minutes, 4-cresols transformation efficiency is 13%, and selectivity is 87%.
Embodiment 5
The catalyzer dosage is 6% (wt) of 4-cresols, and all the other are with example 1, H
2O
2Dripped off in 270 minutes, 4-cresols transformation efficiency is 22%, and selectivity is 74%.
Embodiment 6
The catalyzer dosage is 12% (wt) of 4-cresols, and all the other are with example 1, H
2O
2Concentration is 20%, H
2O
2Dripped off in 150 minutes, 4-cresols transformation efficiency is 24%, and selectivity is 67%.
Embodiment 7
4-cresols adds 86g (0.8ml), H
2O
2Concentration is 20%, H
2O
2With the mol ratio of 4-cresols be 0.75, all the other are with example 1,4-cresols transformation efficiency is 32%, selectivity is 34%.
Claims (8)
1.4-the preparation method of methyl pyrocatechol is characterized in that: described 4-methyl pyrocatechol is to be raw material with 4-cresols and hydrogen peroxide,, reacts in inert solvent as catalyzer with HTS, and temperature of reaction is 40～100 ℃.
2. by the method for claim 1, it is characterized in that: the weight percent of described hydrogen peroxide is 10～50%.
3. by the method for claim 1, it is characterized in that: the weight percent of described hydrogen peroxide is 20～30%.
4. by the method for claim 1, it is characterized in that: by weight percentage, the consumption of described titanium-silicon molecular sieve catalyst is 1～20% of a 4-cresols.
5. by the method for claim 1, it is characterized in that: by weight percentage, the consumption of described titanium-silicon molecular sieve catalyst is 5～12% of a 4-cresols.
6. by the method for claim 1, it is characterized in that: the mol ratio of hydrogen peroxide and 4-cresols is 0.1～1.
7. by the method for claim 1, it is characterized in that: the mol ratio of hydrogen peroxide and 4-cresols is 0.2～0.5.
8. by the method for claim 1, it is characterized in that: described inert solvent is selected from one of following material or its mixture: water, methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, the trimethyl carbinol, acetone, butanone, propione, pimelinketone, benzene,toluene,xylene, trichloromethane, tetracol phenixin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99125464A CN1097575C (en) | 1999-12-09 | 1999-12-09 | Process for preparing 4-methyl catechol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99125464A CN1097575C (en) | 1999-12-09 | 1999-12-09 | Process for preparing 4-methyl catechol |
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| Publication Number | Publication Date |
|---|---|
| CN1298857A CN1298857A (en) | 2001-06-13 |
| CN1097575C true CN1097575C (en) | 2003-01-01 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN99125464A Expired - Fee Related CN1097575C (en) | 1999-12-09 | 1999-12-09 | Process for preparing 4-methyl catechol |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115974662A (en) * | 2022-12-01 | 2023-04-18 | 兄弟科技股份有限公司 | Synthetic method of bio-based vanillin or ethyl vanillin |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4701428A (en) * | 1985-04-23 | 1987-10-20 | Enichem Sintesi S.P.A. | Catalyst of silicon and titanium having high mechanical strength and a process for its preparation. |
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1999
- 1999-12-09 CN CN99125464A patent/CN1097575C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4701428A (en) * | 1985-04-23 | 1987-10-20 | Enichem Sintesi S.P.A. | Catalyst of silicon and titanium having high mechanical strength and a process for its preparation. |
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| CN1298857A (en) | 2001-06-13 |
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