CN103864578A - Synthesis method of 4-methylcatechol - Google Patents
Synthesis method of 4-methylcatechol Download PDFInfo
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- CN103864578A CN103864578A CN201410106368.6A CN201410106368A CN103864578A CN 103864578 A CN103864578 A CN 103864578A CN 201410106368 A CN201410106368 A CN 201410106368A CN 103864578 A CN103864578 A CN 103864578A
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- CRJHSGYHUOYXKP-UHFFFAOYSA-N CC(C=C1OC)=CCC1O Chemical compound CC(C=C1OC)=CCC1O CRJHSGYHUOYXKP-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/01—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis
- C07C37/055—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis the substituted group being bound to oxygen, e.g. ether group
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Abstract
The invention discloses a synthesis method of 4-methylcatechol. The synthesis method comprises the following steps: in the presence of hydrobromic acid and sodium sulfite, performing one-step demethylation with 2-methoxyl-4-methylphenol serving as a raw material; in a dark place and under protection of inert gas, continuously introducing hydrogen bromide gas into a reaction system, and heating reflux for reacting for 4-6 hours; after reaction, adding sodium carbonate so as to adjust the system pH to a weak-acid level; extracting by a cyclohexane-methylbenzene mixed solvent as an extracting agent so as to obtain an upper layer oil phase; washing the extract by a NaCl solution, distilling under protection of inert gas to remove the extracting agent, and cooling to separate out crystals; and finally under the condition of low temperature, performing centrifugal rejection filtration so as to obtain white crystalline 4-methylcatechol. Since the target product is synthesized from the natural green raw material via a one-step process, the problem of chemical material residue is not caused and the synthesis technology is safe and environmental-friendly; and the products are high in yield and purity.
Description
Technical field
The invention belongs to organic chemical synthesis technical field, particularly, relate to a kind of synthetic method of 4-methyl pyrocatechol.
Background technology
4-methyl pyrocatechol has another name called homopyrocatechol, acacatechin, and molecular formula is C7H8O2.4-methyl pyrocatechol is important fine-chemical intermediate, can be applicable to the synthetic of apple shape spices, watermelon ketone, medicine (antiseptic-germicide), agricultural chemicals, as important industrial chemicals, for stablizer, the oxidation inhibitor etc. of photographic developer, anthraquinone dye, synthetic ammonia solubility promoter, rubber antioxidant, coating and essence.
The early stage method of preparing 4-methyl pyrocatechol is mainly strong acid method, is made under strong acid, metal complex and aromatic aldehyde exist by 4-cresols by high-strength hydrogen peroxide aqueous solution chlorination.But the shortcoming that this method exists is: strong acid has stronger corrodibility to equipment, has a lot of safety problems, and yield is lower, and impurity is more.
Afterwards, along with the exploitation of exploitation, improvement and arsenic or the antimony compounds catalyzer of sulfurous gas or tin anhydride catalysis synthesizing technology, this technique is also improved, but still needs to use the aqueous hydrogen peroxide solution of anhydrous hydrogen peroxide or high density.But due to the use of hydrogen peroxide, make preparation technology still have many safety problems, and the problem that the equal once through yield of synthesis technique is too low, impurity is many is resolved not yet.
In the recent period, along with the research and development of molecular sieve catalyst, TS-1 type catalyzer is applied to the synthetic of 4-methyl pyrocatechol gradually.This type of reaction can catalyze and synthesize under the aqueous hydrogen peroxide solution condition of low concentration.Solve to a certain extent safety problem, but because catalyzer cost is higher, still cannot carry out suitability for industrialized production, and the low problem of yield cannot be resolved always.
Summary of the invention
In order to overcome prior art above shortcomings, the object of the present invention is to provide a kind of synthetic method of 4-methyl pyrocatechol.The method solved the security that existing synthesis technique exists low, pollute problem high, that income is poor, impurity in products is many, finally obtained the product of green safety environmental protection.
In order to realize above-mentioned purpose of the present invention, the invention provides following technical scheme:
The method of 4-methyl pyrocatechol shown in a kind of composite structure formula (I), take the 2-methoxyl group-4-methylphenol shown in the structural formula (II) extracting in bio oil as raw material, under Hydrogen bromide and S-WAT existence, demethylating reaction is carried out in heating, again by regulating pH, extraction, washing, distillation, centrifugal rejection filter to obtain 4-methyl pyrocatechol shown in structural formula (I)
According to described synthetic method, the bio oil that wherein said bio oil obtains through fast pyrogenation for biomass.
According to described synthetic method, wherein said Hydrogen bromide is that massfraction is 40～60% solution, and S-WAT is pressed powder.
According to described synthetic method; wherein said demethylating reaction is in lucifuge; under protection of inert gas; be heated to 100～120 ℃ of backflows; and constantly in reaction system, supplement bromize hydrogen gas, the reaction times is 4～6 hours, after reaction finishes; be cooled to room temperature, in reaction system, add soda ash to regulate pH to 3～5.
According to described synthetic method, the extraction liquid that wherein said extraction is used is the mixed solvent of hexanaphthene and toluene, and its volume ratio is 5～10:1, extracts 5～8 times.
According to described synthetic method, wherein said washing is that extraction liquid is washed 3～10 times in NaCl solution, and NaCl liquid quality fraction is 20～27%.
According to described synthetic method, wherein said distillation is that normal pressure steams extraction liquid under protection of inert gas, is cooled to-10～10 ℃, crystallization.
According to described synthetic method, wherein said centrifugal rejection filter is under protection of inert gas, will distill the centrifugal rejection filter of gained crystallization to absence of liquid and flow out, and takes out.
The present invention further provides concrete synthetic method: in reactor, adding purity is 2-methoxyl group-4-methylphenol of 80～99%, add again 40～60% hydrobromic acid solutions and S-WAT, in lucifuge, under nitrogen protection condition, constantly in reaction system, pass into bromize hydrogen gas, heated and stirred simultaneously, temperature of reaction is controlled at 100 ℃～120 ℃, 4-6 hour is carried out in reaction, after reaction finishes, reaction system is naturally cooled to room temperature, again soda ash is added, regulating reaction solution pH is 3～5, use hexanaphthene and toluene the solvent mixture extractive reaction liquid, extract 3 times, use 20～27%NaCl solution washing extraction liquid 3 times again, extraction liquid is merged, steam most of solvent under air distillation condition, be cooled to 15 ℃ of crystallize outs, then, under 25 ℃ of conditions, centrifugal rejection filter, obtains white to off-white color crystal 4-methyl pyrocatechol.
The present invention is synthetic 4-methyl pyrocatechol take 2-methoxyl group-4-methylphenol as raw material, and uses hydrogen bromide as demethylation reagent.In lucifuge, under the condition of protection of inert gas, first there is bromination demethylation in 2-methoxyl group-4-methylphenol, then is shifted and obtained 4-methyl pyrocatechol by bromine.In reaction process, need constantly to pass into bromize hydrogen gas.Reaction proceeds to 4 hours, adds alkali that the major part acid in reaction system is removed.Again by solvent extraction, the method for salts solution washing, by product and complete raw material and the separation of by-products of unreacted.Under protection of inert gas, extraction agent is removed in air distillation, cooling crystallize out.Finally obtain by centrifugal rejection filter the 4-methyl pyrocatechol that purity is higher.
The invention has the beneficial effects as follows: the invention provides a kind of synthetic method of 4-methyl pyrocatechol, solved the security that existing synthesis technique exists low, pollute problem high, that income is poor, impurity in products is many, finally obtained the product of green safety environmental protection.
Embodiment
Further illustrate essentiality content of the present invention with embodiments of the invention below, but do not limit the present invention with this.
Embodiment 1:
The chemical equation of the inventive method is:
In reactor, adding 140g purity is 2-methoxyl group-4-methylphenol of 99%, then adds hydrobromic acid solution (46%) and the 1g S-WAT of 100ml.Under the condition of lucifuge, nitrogen protection, constantly in reaction system, pass into bromize hydrogen gas, heated and stirred simultaneously, temperature of reaction is controlled at 100 ℃ of left and right, and reaction is carried out approximately 4 hours.After reaction finishes, reaction system is naturally cooled to room temperature, then soda ash is added, regulate reaction solution pH ≈ 4 left and right.Use 90ml hexanaphthene and 10ml toluene the solvent mixture extractive reaction liquid, extract 3 times.Use again the 20%NaCl solution washing extraction liquid 3 times of 100ml.Extraction liquid is merged, under air distillation condition, steam most of solvent, be cooled to 15 ℃ of crystallize outs.Under 25 ℃ of conditions, centrifugal rejection filter, obtains white to off-white color crystal 4-methyl pyrocatechol 110g, and productive rate is 87.6%.
Embodiment 2:
In reactor, adding 70g purity is 2-methoxyl group-4-methylphenol of 98%, then adds hydrobromic acid solution (40%) and the 0.6g S-WAT of 60ml.Under the condition of lucifuge, nitrogen protection, constantly in reaction system, pass into bromize hydrogen gas, heated and stirred simultaneously, temperature of reaction is controlled at 110 ℃ of left and right, and reaction is carried out approximately 5 hours.After reaction finishes, reaction system is naturally cooled to room temperature, then soda ash is added, regulate reaction solution pH ≈ 4 left and right.Use 60ml hexanaphthene and 20ml toluene the solvent mixture extractive reaction liquid, extract 5 times.Use again the 25%NaCl solution washing extraction liquid 3 times of 70ml.Extraction liquid is merged, under air distillation condition, steam most of solvent, be cooled to 10 ℃ of crystallize outs.Under 20 ℃ of conditions, centrifugal rejection filter, obtains white to off-white color crystal 4-methyl pyrocatechol 53g, and productive rate is 84.4%.
Claims (9)
1. the method for 4-methyl pyrocatechol shown in a composite structure formula (I), it is characterized in that: take the 2-methoxyl group-4-methylphenol shown in the structural formula (II) extracting in bio oil as raw material, under Hydrogen bromide and S-WAT existence, demethylating reaction is carried out in heating, again by regulating pH, extraction, washing, distillation, centrifugal rejection filter to obtain 4-methyl pyrocatechol shown in structural formula (I)
2. synthetic method according to claim 1, is characterized in that: the bio oil that described bio oil obtains through fast pyrogenation for biomass.
3. synthetic method according to claim 1, is characterized in that: described Hydrogen bromide is that massfraction is 40～60% solution, and S-WAT is pressed powder.
4. synthetic method according to claim 1; it is characterized in that: described demethylating reaction is in lucifuge; under protection of inert gas; be heated to 100～120 ℃ of backflows; and constantly in reaction system, supplement bromize hydrogen gas, the reaction times is 4～6 hours, after reaction finishes; be cooled to room temperature, in reaction system, add soda ash to regulate pH to 3～5.
5. synthetic method according to claim 1, is characterized in that: the extraction liquid that described extraction is used is the mixed solvent of hexanaphthene and toluene, and its volume ratio is 5～10:1, extracts 5～8 times.
6. synthetic method according to claim 1, is characterized in that: described washing is that extraction liquid is washed 3～10 times in NaCl solution, and NaCl liquid quality fraction is 20～27%.
7. synthetic method according to claim 1, is characterized in that: described distillation is that normal pressure steams extraction liquid under protection of inert gas, is cooled to-10～10 ℃, crystallization.
8. synthetic method according to claim 1, is characterized in that: described centrifugal rejection filter is under protection of inert gas, will distill the centrifugal rejection filter of gained crystallization to absence of liquid and flow out, and takes out.
9. synthetic method according to claim 1, it is characterized in that: in reactor, adding purity is 2-methoxyl group-4-methylphenol of 80～99%, add again 40～60% hydrobromic acid solutions and S-WAT, in lucifuge, under nitrogen protection condition, constantly in reaction system, pass into bromize hydrogen gas, heated and stirred simultaneously, temperature of reaction is controlled at 100 ℃～120 ℃, reaction is carried out 4～6 hours, after reaction finishes, reaction system is naturally cooled to room temperature, again soda ash is added, regulating reaction solution pH is 3～5, use hexanaphthene and toluene the solvent mixture extractive reaction liquid, extract 3 times, use 20～27%NaCl solution washing extraction liquid 3 times again, extraction liquid is merged, steam most of solvent under air distillation condition, be cooled to 15 ℃ of crystallize outs, then, under 25 ℃ of conditions, centrifugal rejection filter, obtains white to off-white color crystal 4-methyl pyrocatechol.
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| CN201410106368.6A CN103864578A (en) | 2014-03-19 | 2014-03-19 | Synthesis method of 4-methylcatechol |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108658730A (en) * | 2018-05-11 | 2018-10-16 | 常州大学 | A kind of preparation method of p-fluorophenol |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1986002634A1 (en) * | 1984-10-22 | 1986-05-09 | Chemical Dynamics Development Ab | A method for dealkylation of alkyl-aryl ethers |
| CN103570507A (en) * | 2013-11-13 | 2014-02-12 | 浙江理工大学 | Preparation method of 4-methylcatechol |
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2014
- 2014-03-19 CN CN201410106368.6A patent/CN103864578A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1986002634A1 (en) * | 1984-10-22 | 1986-05-09 | Chemical Dynamics Development Ab | A method for dealkylation of alkyl-aryl ethers |
| CN103570507A (en) * | 2013-11-13 | 2014-02-12 | 浙江理工大学 | Preparation method of 4-methylcatechol |
Non-Patent Citations (2)
| Title |
|---|
| 何建玲等: "《有机化学基础教程》", 28 February 2011, article "第8.3节醚", pages: 197 - 3 * |
| 王积涛等: "《有机化学 第三版 上册》", 31 December 2009, article "第10.4节醚的化学性质", pages: 337 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108658730A (en) * | 2018-05-11 | 2018-10-16 | 常州大学 | A kind of preparation method of p-fluorophenol |
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Application publication date: 20140618 |