CN102557903B - Preparation method of 4-hydroxyl-2-methoxybenzaldehyde - Google Patents
Preparation method of 4-hydroxyl-2-methoxybenzaldehyde Download PDFInfo
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- CN102557903B CN102557903B CN201210009874.4A CN201210009874A CN102557903B CN 102557903 B CN102557903 B CN 102557903B CN 201210009874 A CN201210009874 A CN 201210009874A CN 102557903 B CN102557903 B CN 102557903B
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Abstract
The invention relates to a new preparation method of 4-hydroxyl-2-methoxybenzaldehyde as a medical intermediate, belonging to the technical field of chemical preparation. The new preparation method comprises the following steps of: (1) carrying out esterification reaction by adopting m-hydroxybenzoic ether, acetic anhydride and an ion liquid catalyst, as materials, and after the esterification reaction is finished, carrying out reduced-pressure distillation and separation to obtain 3-acetoxyl anisole; (2) introducing aldehyde groups to the obtained 3-acetoxyl anisole, N, N-dimethylformamide and phosphorus oxychloride by Vilsmeier reaction and generating reaction liquid; dripping the reaction liquid into water, stirring fully after the dripping is finished, and generating 2-methoxyl-4-acetoxybenzaldehyde; rising the temperature continuously, stirring to remove acetyls, generating a target product, standing for layering to obtain an organic layer, washing the organic layer with water, distilling to remove the water content of the organic layer, and obtaining the 4-hydroxyl-2-methoxybenzaldehyde. The new preparation method has the advantages that the reaction condition in the whole process is mild, the product quality is good, the yield is high, and the implementation is easy.
Description
Technical field
The novel preparation method that the present invention relates to a kind of medicine intermediate 4-hydroxyl-2-methoxybenzaldehyde, belongs to chemical preparation technical field.
Background technology
4-hydroxyl-2-methoxybenzaldehyde is medicine intermediate, also can be used for solid phase protein synthesis aspect, for acid-sensitive type resin link.
4-hydroxyl-2-methoxybenzaldehyde (4-Hydroxy-2-methoxybenzaldehyde),
No. CAS: 18278-34-7
Molecular formula: C
8h
8o
3
Molecular weight: 152.15
Structural formula:
For white crystal, fusing point 158-159 ℃, dissolves in the organic solvents such as ether and ethyl acetate.
The present invention is a synthetic route of this compound, has no document and records.
Summary of the invention
The invention provides a kind of preparation method of 4-hydroxyl-2-methoxybenzaldehyde, this preparation method's reaction conditions is gentle, and product quality is good, yield is high, is easy to realize.
For achieving the above object, the technical solution adopted in the present invention is:
A preparation method for 4-hydroxyl-2-methoxybenzaldehyde, comprises the steps:
(1) take m-hydroxy methyl-phenate (having another name called: 3-hydroxyanisol, 3-methoxyphenol, meta-methoxy phenol) is main raw material, m-hydroxy methyl-phenate is dissolved in anhydrous acetic acid, add ionic-liquid catalyst to carry out esterification, the separated 3-acetoxyl group methyl-phenoxide that obtains of underpressure distillation after esterification completes; Wherein, each material weight ratio that feeds intake is: m-hydroxy methyl-phenate: anhydrous acetic acid: ionic-liquid catalyst=1:0.90 ~ 1.21:0.08 ~ 0.1;
(2) above-mentioned gained 3-acetoxyl group methyl-phenoxide is reacted to (Vilsmeier reaction) with DMF (DMF), phosphorus oxychloride through Wei Er David Smail and introduce aldehyde radical formation reaction liquid; Wherein, each material weight ratio that feeds intake is: 3-acetoxyl group methyl-phenoxide: N, dinethylformamide: phosphorus oxychloride=1:1.02 ~ 1.16:1.10 ~ 1.20, gained reaction solution is slowly splashed in the water of triplication, after dropwising, fully stir again, generate 2-methoxyl group-4-acetoxyl group phenyl aldehyde; Continue to heat up, stir and remove that ethanoyl generates target product, stratification obtains organic layer, washing organic layer, distillation remove organic layer moisture and obtain 4-hydroxyl-2-methoxybenzaldehyde (purity 99.6%), and molar yield is more than 90%.
In described step (1), temperature during esterification is 50 ~ 80 ℃.
In described step (2), the temperature during reaction of Wei Er David Smail is-8 ~-2 ℃, and the reaction times is 1 hour.
In described step (2), while gained reaction solution slowly being splashed in the water of triplication, control water temperature and be no more than 20 ℃, and after dropwising, carry out again fully stirring 30 minutes, generate 2-methoxyl group-4-acetoxyl group phenyl aldehyde.
In described step (2), the 2-methoxyl group-4-acetoxyl group phenyl aldehyde generating continues to be warming up to 50 ~ 55 ℃, and carries out fully stirring and within 1 hour, remove ethanoyl and generate target product.
Described ionic-liquid catalyst is any one in 1-butyl-3-Methylimidazole acetate, 1-butyl-3-Methylimidazole bromine salt.
It is esterifying catalyst that the present invention has adopted nontoxic ionic liquid in the first step, reaction process produces without the three wastes substantially, in reaction, unique generation by product is water, ionic liquid, unreacted acetic acid can be applied mechanically, in m-hydroxy methyl-phenate product 3-acetoxyl group methyl-phenoxide yield 97%, purity 99.7%.Traditional esterification adopts inorganic acid to make esterifying catalyst and equipment is produced to deep-etching and spent acid processes difficultly, and does catalyst prod yield low (generally below 80%) with solid super-strong acid etc.
Second step reaction utilizes the space steric effect of acetoxyl group, through Wei Er David Smail reaction (Vilsmeier reaction), introduces aldehyde radical well at the ortho position of methoxyl group, through many experiments result, shows, the by product that other positions do not detected produces; The strong acidic condition that utilizes dexterously the hydrolytic process after the reaction of Wei Er David Smail finishes to produce, the temperature condition of controlling well removes ethanoyl, obtains target compound purity and reaches 99.6% simultaneously.
The whole technological process reaction conditions of the present invention is gentle, and product quality is good, yield is high, be easy to realize, and be the good method of a suitability for industrialized production 4-hydroxyl-2-methoxybenzaldehyde.
The m-hydroxy methyl-phenate 99%min that above-mentioned m-hydroxy methyl-phenate selects Beijing Heng Yezhongyuan Chemical Co., Ltd. to produce; 1-butyl-3-Methylimidazole acetate select Chinese Academy of Sciences Lanzhou chemistry 1-butyl-3-Methylimidazole acetate 98%min; 1-butyl-3-Methylimidazole bromine salt select Chinese Academy of Sciences Lanzhou chemistry 1-butyl-3-Methylimidazole bromine salt 98%min.
Embodiment
The preparation method of a kind of 4-hydroxyl-2-methoxybenzaldehyde of the present invention comprises the steps:
The first step: hydroxyl protection
The m-hydroxy methyl-phenate (having another name called: 3-hydroxyanisol, 3-methoxyphenol, meta-methoxy phenol) of take is main raw material, m-hydroxy methyl-phenate is dissolved in anhydrous acetic acid, add ionic-liquid catalyst to carry out esterification, temperature during esterification is 50 ~ 80 ℃, the separated 3-acetoxyl group methyl-phenoxide (purity 99.7%, yield 97%) that obtains of underpressure distillation after esterification completes; Wherein, each material weight ratio that feeds intake is: m-hydroxy methyl-phenate: anhydrous acetic acid: ionic-liquid catalyst=1:0.90 ~ 1.21:0.08 ~ 0.1.Ionic-liquid catalyst is any one in 1-butyl-3-Methylimidazole acetate, 1-butyl-3-Methylimidazole bromine salt.
Second step: introduce aldehyde radical in methoxyl group ortho-orientation, remove ethanoyl again and obtain target product
Above-mentioned gained 3-acetoxyl group methyl-phenoxide is reacted and introduces aldehyde radical formation reaction liquid through Wei Er David Smail with DMF, phosphorus oxychloride, and the temperature during reaction of Wei Er David Smail is-8 ~-2 ℃, and the reaction times is 1 hour; Wherein, each material weight ratio that feeds intake is: 3-acetoxyl group methyl-phenoxide: DMF: phosphorus oxychloride=1:1.02 ~ 1.16:1.10 ~ 1.20; Gained reaction solution is slowly splashed in the water of triplication, control water temperature and be no more than 20 ℃, and after dropwising, carry out again fully stirring 30 minutes, generate 2-methoxyl group-4-acetoxyl group phenyl aldehyde; 2-methoxyl group-4-acetoxyl group the phenyl aldehyde generating continues to be warming up to 50 ~ 55 ℃; and carry out fully stirring and within 1 hour, remove that ethanoyl generates target product, stratification obtains organic layer; washing organic layer, distillation remove organic layer moisture and obtain 4-hydroxyl-2-methoxybenzaldehyde (purity 99.6%), and molar yield is more than 90%.
Following concrete example gives an actual example:
Embodiment 1:
The first step: add stock yard hydroxyanisol 124g, anhydrous acetic acid 120g, ionic liquid 1-butyl-3-methyl imidazolium acetate ([Bmim] OAc) 6.2g in the reactor with thermometer, agitator and heating jacket, open stirring, heating for dissolving, interior temperature keeps 55 ℃, reacts 2 hours.The separated 3-acetoxyl group methyl-phenoxide 145.6g(purity 99.77% that obtains of underpressure distillation) molar yield: 87.7%.
Second step: add 3-acetoxyl group methyl-phenoxide 83g, N in the reactor with thermometer, agitator and cryostat device, dinethylformamide 83g, open stirring, open low-temperature receiver, to temperature in reactor at-7 ℃, start to drip 92g phosphorus oxychloride, in keeping, temperature, at-7 ℃, dropwises, and fully stirring reaction is 1 hour.Reaction solution is slowly splashed in the 800ml water under agitation condition, control all the time water temperature at 10 ~ 18 ℃, dropwise abundant stirring 30 minutes, generate 2-methoxyl group-4-acetoxyl group phenyl aldehyde.After continuing to be warming up to 50 ℃, fully stir and within 1 hour, remove ethanoyl generation target product, stratification obtains organic layer, and washing organic layer, distillation remove organic layer moisture and obtain 4-hydroxyl-2-methoxybenzaldehyde 68.5g(purity 99.6%), molar yield 90.1%.
Embodiment 2:
The first step: add stock yard hydroxyanisol 124g, anhydrous acetic acid 135g, ionic liquid 1-butyl-3-methyl imidazolium acetate ([Bmim] OAc) 12.4g in the reactor with thermometer, agitator and heating jacket, open stirring, heating for dissolving, interior temperature keeps 55 ℃, reacts 2 hours.The separated 3-acetoxyl group methyl-phenoxide 159.3g(purity 99.78% that obtains of underpressure distillation) molar yield: 96.0%.
Second step: add 3-acetoxyl group methyl-phenoxide 83g, N in the reactor with thermometer, agitator and cryostat device, dinethylformamide 90g opens stirring, opens low-temperature receiver, to temperature in reactor at-7 ℃, start to drip 92g phosphorus oxychloride, in keeping, temperature is at-7 ℃, dropwise, fully stirring reaction is 1 hour.Reaction solution is slowly splashed in the 800ml water under agitation condition, control all the time 8 ~ 15 ℃ of water temperatures, dropwise abundant stirring 30 minutes, generate 2-methoxyl group-4-acetoxyl group phenyl aldehyde.After continuing to be warming up to 50 ℃, fully stir and within 1 hour, remove ethanoyl generation target product, stratification obtains organic layer, and washing organic layer, distillation remove organic layer moisture and obtain 4-hydroxyl-2-methoxybenzaldehyde 68.8g(purity 99.7%), molar yield 90.5%.
Embodiment 3:
The first step: add stock yard hydroxyanisol 124g, anhydrous acetic acid 150g, ionic liquid 1-butyl-3-methyl imidazolium acetate ([Bmim] OAc) 12.4g in the reactor with thermometer, agitator and heating jacket, open stirring, heating for dissolving, interior temperature keeps 60 ℃, reacts 2 hours.The separated 3-acetoxyl group methyl-phenoxide 159.6g(purity 99.78% that obtains of underpressure distillation) molar yield: 96.1%.
Second step: add 3-acetoxyl group methyl-phenoxide 83g, N in the reactor with thermometer, agitator and cryostat device, dinethylformamide 96g opens stirring, opens low-temperature receiver, to temperature in reactor at-5 ℃, start to drip 100g phosphorus oxychloride, in keeping, temperature is at-5 ℃, dropwise, fully stirring reaction is 1 hour.Reaction solution is slowly splashed in the 800ml water under agitation condition, control all the time 12 ~ 18 ℃ of water temperatures, dropwise abundant stirring 30 minutes, generate 2-methoxyl group-4-acetoxyl group phenyl aldehyde.After continuing to be warming up to 55 ℃, fully stir and within 1 hour, remove ethanoyl generation target product, stratification obtains organic layer, and washing organic layer, distillation remove organic layer moisture and obtain 4-hydroxyl-2-methoxybenzaldehyde 68.8g(purity 99.7%), molar yield 90.5%.
Embodiment 4:
The first step: add stock yard hydroxyanisol 124g, anhydrous acetic acid 120g, ionic liquid 1-butyl-3-methyl imidazolium bromine salt ([Bmim] OBr) 6.2g in the reactor with thermometer, agitator and heating jacket, open stirring, heating for dissolving, interior temperature keeps 50 ℃, reacts 2 hours.The separated 3-acetoxyl group methyl-phenoxide 117.1g(purity 99.75% that obtains of underpressure distillation) molar yield: 70.5%.
Second step: add 3-acetoxyl group methyl-phenoxide 83g, N in the reactor with thermometer, agitator and cryostat device, dinethylformamide 83g opens stirring, opens low-temperature receiver, to temperature in reactor at-8 ℃, start to drip 92g phosphorus oxychloride, in keeping, temperature is at-8 ℃, dropwise, fully stirring reaction is 1 hour.Reaction solution is slowly splashed in the 800ml water under agitation condition, control all the time 15 ~ 20 ℃ of water temperatures, dropwise abundant stirring 30 minutes, generate 2-methoxyl group-4-acetoxyl group phenyl aldehyde.After continuing to be warming up to 52 ℃, fully stir and within 1 hour, remove ethanoyl generation target product, stratification obtains organic layer, and washing organic layer, distillation remove organic layer moisture and obtain 4-hydroxyl-2-methoxybenzaldehyde 68.5g(purity 99.6%), molar yield 90.1%.
Embodiment 5:
The first step: add stock yard hydroxyanisol 124g, anhydrous acetic acid 135g, ionic liquid 1-butyl-3-methyl imidazolium bromine salt ([Bmim] OBr) 12.4g in the reactor with thermometer, agitator and heating jacket, open stirring, heating for dissolving, interior temperature keeps 80 ℃, reacts 2 hours.The separated 3-acetoxyl group methyl-phenoxide 144.4g(purity 99.81% that obtains of underpressure distillation) molar yield: 87.0%.
Second step: add 3-acetoxyl group methyl-phenoxide 83g, N in the reactor with thermometer, agitator and cryostat device, dinethylformamide 90g opens stirring, opens low-temperature receiver, to temperature in reactor at-2 ℃, start to drip 92g phosphorus oxychloride, in keeping, temperature is at-2 ℃, dropwise, fully stirring reaction is 1 hour.Reaction solution is slowly splashed in the 800ml water under agitation condition, control all the time 10 ~ 16 ℃ of water temperatures, dropwise abundant stirring 30 minutes, generate 2-methoxyl group-4-acetoxyl group phenyl aldehyde.After continuing to be warming up to 53 ℃, fully stir and within 1 hour, remove ethanoyl generation target product, stratification obtains organic layer, and washing organic layer, distillation remove organic layer moisture and obtain 4-hydroxyl-2-methoxybenzaldehyde 68.8g(purity 99.7%), molar yield 90.5%.
Embodiment 6:
The first step: add stock yard hydroxyanisol 124g, anhydrous acetic acid 150g, ionic liquid 1-butyl-3-methyl imidazolium bromine salt ([Bmim] OBr) 12.4g in the reactor with thermometer, agitator and heating jacket, open stirring, heating for dissolving, interior temperature keeps 70 ℃, reacts 2 hours.The separated 3-acetoxyl group methyl-phenoxide 144.4g(purity 99.81% that obtains of underpressure distillation) molar yield: 87.0%.
Second step: add 3-acetoxyl group methyl-phenoxide 83g, N in the reactor with thermometer, agitator and cryostat device, dinethylformamide 96g opens stirring, opens low-temperature receiver, to temperature in reactor at-6 ℃, start to drip 100g phosphorus oxychloride, in keeping, temperature is at-6 ℃, dropwise, fully stirring reaction is 1 hour.Reaction solution is slowly splashed in the 800ml water under agitation condition, control all the time 15 ~ 20 ℃ of water temperatures, dropwise abundant stirring 30 minutes, generate 2-methoxyl group-4-acetoxyl group phenyl aldehyde.After continuing to be warming up to 50 ℃, fully stir and within 1 hour, remove ethanoyl generation target product, stratification obtains organic layer, and washing organic layer, distillation remove organic layer moisture and obtain 4-hydroxyl-2-methoxybenzaldehyde 68.8g(purity 99.7%), molar yield 90.5%.
The preparation method of a kind of 4-hydroxyl-2-methoxybenzaldehyde of the present invention, operational path is reasonable, and reaction conditions is gentle, and yield is high.Particularly in the first step esterification, we adopt nontoxic ionic liquid to replace the vitriol oil, solid super-strong acid etc. of severe corrosive is esterifying catalyst, and reaction conditions is gentle, almost without the three wastes, produce, and product purity, yield all meets the requirements.This operational path, whole condition is not harsh, be easy to realize, and can be applicable to suitability for industrialized production, for market provides highly purified product, obtains good economic benefit.
Above-described embodiment is only for the inventive concept of the present invention of explaining, but not restriction to rights protection of the present invention, allly utilizes this design to carry out the change of unsubstantiality to the present invention, all should fall into protection scope of the present invention.
Claims (5)
1. a preparation method for 4-hydroxyl-2-methoxybenzaldehyde, is characterized in that comprising the steps:
(1) take m-hydroxy methyl-phenate as main raw material, m-hydroxy methyl-phenate is dissolved in anhydrous acetic acid, add ionic-liquid catalyst to carry out esterification, the separated 3-acetoxyl group methyl-phenoxide that obtains of underpressure distillation after esterification completes; Wherein, each material weight ratio that feeds intake is: m-hydroxy methyl-phenate: anhydrous acetic acid: ionic-liquid catalyst=1:0.90～1.21:0.08～0.1;
(2) above-mentioned gained 3-acetoxyl group methyl-phenoxide is reacted and introduces aldehyde radical formation reaction liquid through Wei Er David Smail with DMF, phosphorus oxychloride; Wherein, each material weight ratio that feeds intake is: 3-acetoxyl group methyl-phenoxide: N, dinethylformamide: phosphorus oxychloride=1:1.02～1.16:1.10～1.20, gained reaction solution is slowly splashed in the water of triplication, after dropwising, fully stir again, generate 2-methoxyl group-4-acetoxyl group phenyl aldehyde; Continue to heat up, stir and remove that ethanoyl generates target product, stratification obtains organic layer, washing organic layer, distillation remove organic layer moisture and obtain 4-hydroxyl-2-methoxybenzaldehyde;
Described ionic-liquid catalyst is any one in 1-butyl-3-Methylimidazole acetate, 1-butyl-3-Methylimidazole bromine salt.
2. the preparation method of a kind of 4-hydroxyl-2-methoxybenzaldehyde as claimed in claim 1, is characterized in that: in described step (1), temperature during esterification is 50～80 ℃.
3. the preparation method of a kind of 4-hydroxyl-2-methoxybenzaldehyde as claimed in claim 1, is characterized in that: in described step (2), the temperature during reaction of Wei Er David Smail is-8～-2 ℃, and the reaction times is 1 hour.
4. the preparation method of a kind of 4-hydroxyl-2-methoxybenzaldehyde as claimed in claim 1, it is characterized in that: in described step (2), while gained reaction solution slowly being splashed in the water of triplication, control water temperature and be no more than 20 ℃, and after dropwising, carry out again fully stirring 30 minutes, generate 2-methoxyl group-4-acetoxyl group phenyl aldehyde.
5. the preparation method of a kind of 4-hydroxyl-2-methoxybenzaldehyde as claimed in claim 1; it is characterized in that: in described step (2); 2-methoxyl group-4-acetoxyl group the phenyl aldehyde generating continues to be warming up to 50～55 ℃, and carries out fully stirring and within 1 hour, remove ethanoyl and generate target product.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4089606A (en) * | 1975-04-17 | 1978-05-16 | Kabushiki Kaisha Hayashibara Seibutsu Kagaku Kenkyujo | Echinatin glycosides |
| US6844346B2 (en) * | 1997-10-27 | 2005-01-18 | Ibbex, Inc. | Chromogenic substrates of sialidase and methods of making and using the same |
| EP1124836B1 (en) * | 1998-10-27 | 2005-12-14 | IBBEX, Inc. c/o Gryphus Diagnostics, L.L.C. | Chromogenic substrates of sialidase and methods of making and using the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH05105643A (en) * | 1991-10-15 | 1993-04-27 | Kao Corp | Cinnamic acid derivative and skin-beautifying cosmetic containing the derivative as active component |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4089606A (en) * | 1975-04-17 | 1978-05-16 | Kabushiki Kaisha Hayashibara Seibutsu Kagaku Kenkyujo | Echinatin glycosides |
| US6844346B2 (en) * | 1997-10-27 | 2005-01-18 | Ibbex, Inc. | Chromogenic substrates of sialidase and methods of making and using the same |
| EP1124836B1 (en) * | 1998-10-27 | 2005-12-14 | IBBEX, Inc. c/o Gryphus Diagnostics, L.L.C. | Chromogenic substrates of sialidase and methods of making and using the same |
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| Title |
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| JP特开平5-105643A 1993.04.27 |
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