CN101337868A - Method for preparing 3-phenoxy-benzaldehyde - Google Patents
Method for preparing 3-phenoxy-benzaldehyde Download PDFInfo
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- CN101337868A CN101337868A CNA2008101246681A CN200810124668A CN101337868A CN 101337868 A CN101337868 A CN 101337868A CN A2008101246681 A CNA2008101246681 A CN A2008101246681A CN 200810124668 A CN200810124668 A CN 200810124668A CN 101337868 A CN101337868 A CN 101337868A
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- bromobenzaldehyde
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Abstract
The invention belongs to the chemical pharmaceutical field, and particularly relates to a preparation method of m-phenoxy benzaldehyde. The preparation method comprises the following steps: condensation, etherification and hydrolysis. Compared with other methods, the preparation method has the advantages of brief route, low operation cost, less emission of the three wastes, etc.; and has reduced cost and has the effect of inhibiting side reactions due to the small amount of the adopted catalyst.
Description
Technical field
The present invention relates to a kind of preparation method of 3-phenoxy-benzaldehyde, belong to chemical pharmacy field.
Background technology
3-phenoxy-benzaldehyde (being called for short ether aldehyde or MPA) has in organic synthesis more widely to be used. and be the important intermediate of synthetic pesticide, disinfectant etc.Particularly the application aspect the synthetic pyrethroid agricultural chemicals is very extensive.Pyrethroid is all to attach great importance to both at home and abroad the present age and mass production use and the third generation agricultural chemicals of continually developing research.The development of producing along with the rise of pyrethroid pesticide research and promoting the use of in large area will be more and more important as its cost of 3-phenoxy-benzaldehyde and the quality of key intermediate, directly influence the use and the plant protection of this class agricultural chemicals.So the meaning of the Study of synthesis method that it is new is outstanding day by day.
Domestic present production ether aldehyde mainly contains following 4 kinds of methods: (1) 3-bromobenzaldehyde method; (2) m-cresol method; (3) m-chloro benzyl alcohol oxidation method; (4) m-chlorotoluene oxidation style.Be subjected to the restriction of yield, raw material and processing condition, preceding two kinds of methods are mainly adopted in industrialization at present.Many and the product purification difficult of method (2) impurity and seldom adopting wherein.Method (1) also exists such as expensive, high energy consumption, complicated operation, defective such as pollution is big, the industrialization effect is undesirable.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of 3-phenoxy-benzaldehyde, this preparation method can overcome defectives such as original technology is expensive, high energy consumption, complicated operation, pollution is big, the industrialization effect is undesirable, thereby can realize the purpose of low-cost suitability for industrialized production.
Technical solution of the present invention is that this preparation method may further comprise the steps: condensation → etherificate → hydrolysis, and its synthetic route is:
Wherein M represents alkali metal lithium, sodium or potassium; R
1, R
2Being the aldehyde radical protecting group, is CH
3-, CH
3CH
2-, CH
3CH
2CH
2-, (CH
3)
2CH-,-CH
2CH
2-in a class, R
1, R
2Identical or inequality; Catalyzer can be copper and mantoquita or their mixture, is that active copper powder, Red copper oxide, cuprous chloride, neutralized verdigris or two (triphenylphosphines) close a kind of in the cupric chloride (I).
Among the preparation method of a kind of 3-phenoxy-benzaldehyde of the present invention, condensation reaction:
Wherein, R represents R above-mentioned
1, R
2, molar ratio is 3-bromobenzaldehyde: ROH=1: 1.2-4, and temperature of reaction is 60-140 ℃, and the reaction times is 6-12h.
Among the preparation method of a kind of 3-phenoxy-benzaldehyde of the present invention, etherification reaction:
Principal reaction condition when feeds intake:
3-bromobenzaldehyde second two acetals: phenol: MOH: catalyzer=1: 1.1～2.5: 1.2～2.5: 0.01～0.15 (mol ratio)
Etherification reaction temperature: 120～190 ℃, the reaction times: 2～8h.
Among the preparation method of a kind of 3-phenoxy-benzaldehyde of the present invention, hydrolysis reaction:
Principal reaction condition when feeds intake:
3-bromobenzaldehyde second two acetals: concentrated hydrochloric acid=1: 0.5～2.0 (mol ratio)
Temperature of reaction: 50～100 ℃, the reaction times: 8～15h.
The present invention has following beneficial effect:
(1) preparation technology compares with other method, and it is brief to have a route, advantage such as process cost is low, three waste discharge is few.
(2) adopt catalyst consumption seldom, saved cost, side reaction is had certain restraining effect.
Embodiment
Embodiment 1:
Condensation reaction:
3-bromobenzaldehyde 92.5g (0.5mol), ethylene glycol 46.5g (0.75mol), toluene 100ml and tosic acid 0.5g are once dropped into the reactor of being with division box, be heated to 110 ℃ of reflux water-dividings.Tosic acid is the catalyzer of condensation reaction.Do not observe in the water trap begin when moisture goes out the sampling, material content is below 0.5% behind the 10h.Change vacuum distillation plant after the cooling into, remove toluene and ethylene glycol.Product at the bottom of the still is directly used and next step reaction.
Etherification reaction:
With sodium hydroxide 30.0g (0.75mol), phenol 61.1g (0.65mol), toluene once drops into the reactor that has division box, and reflux is divided water.Guarantee to reflux obviously.Treated that a large amount of white sodium phenylate solids occur, and do not had moisture to go out in the observation water trap, when two-phase interface is clear, steamed most toluene.Be cooled to the violent back of backflow slightly and add N, dinethylformamide, reheat heats up, and steams and removes toluene 150 ℃ of temperature at the bottom of the still.Be cooled to below 60 ℃.Stir to drop into successively down and go up 3-bromobenzaldehyde second two acetals that the step makes, the cuprous 1.44g of catalyst oxidation (0.01mol).Etherification reaction temperature is controlled at 140 ℃ of reactions.3h begins the tracking sampling analysis, stops less than 0.5% to raw material.Reaction changes vacuum distillation plant into after finishing, and steams most of N, dinethylformamide, and raffinate directly is hydrolyzed.
Hydrolysis reaction:
In etherificate precipitation liquid, add toluene 100ml, water 200ml, concentrated hydrochloric acid 50ml (0.5mol), stir, heat up, be controlled at 70 ℃ of reactions.About 8h begins sampling analysis, and extremely main content about 95% stops.Tell the toluene phase, distillation is purified, and gets light yellow transparent liquid 87.4g.
Embodiment 2:
Condensation reaction:
3-bromobenzaldehyde 185g (1.0mol), ethylene glycol 102.3g (1.65mol), toluene 200ml and tosic acid 0.8g are once dropped into the reactor of being with division box, be heated to 115 ℃ of reflux water-dividings.Do not observe in the water trap begin when moisture goes out the sampling, material content is below 0.5% behind the 12h.Change vacuum distillation plant after the cooling into, remove toluene and ethylene glycol.Product at the bottom of the still is directly used and next step reaction.
Etherification reaction:
With sodium hydroxide 60.0g (1.5mol), phenol 141g (1.5mol), toluene once drops into the reactor that has division box, and reflux is divided water.Guarantee to reflux obviously.Treated that a large amount of white sodium phenylate solids occur, and do not had moisture to go out in the observation water trap, when two-phase interface is clear, steamed most toluene.Be cooled to the violent back of backflow slightly and add N, dinethylformamide, reheat heats up, and steams and removes toluene 150 ℃ of temperature at the bottom of the still.Be cooled to below 60 ℃.Stir to drop into successively down and go up 3-bromobenzaldehyde second two acetals that the step makes, catalyzer cuprous chloride 5g (0.05mol).Etherification reaction temperature is controlled at 160 ℃ of reactions.Beginning tracking sampling analysis behind the 5h stops less than 0.5% to raw material.Reaction changes vacuum distillation plant into after finishing, and steams most of N, dinethylformamide, and raffinate directly is hydrolyzed.
Hydrolysis reaction:
In etherificate precipitation liquid, add toluene 200ml, water 400ml, concentrated hydrochloric acid 150ml (1.5mol), stir, heat up, be controlled at 80 ℃ of reactions.10h begins sampling analysis, and extremely main content about 95% stops.Tell the toluene phase, distillation is purified, and gets light yellow transparent liquid 150g.
Embodiment 3:
Condensation reaction:
3-bromobenzaldehyde 92.5g (0.5mol), ethylene glycol 62g (1.0mol), toluene 150ml and tosic acid 0.6g are once dropped into the reactor of being with division box, be heated to 120 ℃ of reflux water-dividings.Do not observe in the water trap begin when moisture goes out the sampling, material content is below 0.5% behind the 6h.Change vacuum distillation plant after the cooling into, remove toluene and ethylene glycol.Product at the bottom of the still is directly used and next step reaction.
Etherification reaction:
With potassium hydroxide 42g (0.75mol), phenol 61.1g (0.65mol), toluene once drops into the reactor that has division box, and reflux is divided water.Guarantee to reflux obviously.Treated that a large amount of white sodium phenylate solids occur, and do not had moisture to go out in the observation water trap, when two-phase interface is clear, steamed most toluene.Be cooled to the violent back of backflow slightly and add N, dinethylformamide, reheat heats up, and steams and removes toluene 150 ℃ of temperature at the bottom of the still.Be cooled to below 60 ℃.Stir to drop into successively down and go up 3-bromobenzaldehyde second two acetals that the step makes, catalyst activity copper powder 0.64g (0.01mol).Etherification reaction temperature is controlled at 120 ℃ of reactions.4h begins the tracking sampling analysis, stops less than 0.5% to raw material.Reaction changes vacuum distillation plant into after finishing, and steams most of N, dinethylformamide, and raffinate directly is hydrolyzed.
Hydrolysis reaction:
In etherificate precipitation liquid, add toluene 100ml, water 200ml, concentrated hydrochloric acid 100ml (1.0mol), stir, heat up, be controlled at 60 ℃ of reactions.Begin sampling analysis behind the 10h, extremely main content about 95% stops.Tell the toluene phase, distillation is purified, and gets light yellow transparent liquid 85g.
The invention is not restricted to these disclosed embodiment; the present invention is with the described scope of soverlay technique scheme; and the various distortion of claim scope and equivalence variation; under the prerequisite that does not depart from technical solution of the present invention, any modification or improvement that those skilled in the art that the present invention did are realized easily all belong to the present invention's scope required for protection.
Claims (4)
1. the preparation method of a 3-phenoxy-benzaldehyde is characterized in that this preparation method may further comprise the steps: condensation → etherificate → hydrolysis, and its synthetic route is:
Wherein M represents alkali metal lithium, sodium or potassium; R
1, R
2Being the aldehyde radical protecting group, is CH
3-, CH
3CH
2-, CH
3CH
2CH
2-, (CH
3)
2CH-,-CH
2CH
2-in a class, R
1, R
2Identical or inequality; Catalyzer can be copper and mantoquita or their mixture, is that active copper powder, Red copper oxide, cuprous chloride, neutralized verdigris or two (triphenylphosphines) close a kind of in the cupric chloride (I).
2, the preparation method of a kind of 3-phenoxy-benzaldehyde according to claim 1 is characterized in that condensation reaction:
Wherein, R represents R above-mentioned
1, R
2, molar ratio is 3-bromobenzaldehyde: ROH=1: 1.2-4, and temperature of reaction is 60～140 ℃, and the reaction times is 6～12h.
3, the preparation method of a kind of 3-phenoxy-benzaldehyde according to claim 1 is characterized in that etherification reaction:
Principal reaction condition when feeds intake:
3-bromobenzaldehyde second two acetals: phenol: MOH: catalyzer=1: 1.1～2.5: 1.2～2.5: 0.01～0.15 (mol ratio)
Etherification reaction temperature: 120～190 ℃, the reaction times: 2～8h.
4, the preparation method of a kind of 3-phenoxy-benzaldehyde according to claim 1 is characterized in that hydrolysis reaction:
Principal reaction condition when feeds intake:
3-bromobenzaldehyde second two acetals: concentrated hydrochloric acid=1: 0.5～2.0 (mol ratio)
Temperature of reaction: 50～100 ℃, the reaction times: 8～15h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008101246681A CN101337868A (en) | 2008-08-29 | 2008-08-29 | Method for preparing 3-phenoxy-benzaldehyde |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008101246681A CN101337868A (en) | 2008-08-29 | 2008-08-29 | Method for preparing 3-phenoxy-benzaldehyde |
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| CN101337868A true CN101337868A (en) | 2009-01-07 |
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|---|---|---|---|
| CNA2008101246681A Pending CN101337868A (en) | 2008-08-29 | 2008-08-29 | Method for preparing 3-phenoxy-benzaldehyde |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104230688A (en) * | 2013-06-24 | 2014-12-24 | 淄博职业学院 | Catalyzed synthesis method for m-phenoxy benzaldehyde |
| CN104926633A (en) * | 2015-05-06 | 2015-09-23 | 江西力田维康科技有限公司 | Preparation method for 3-alkoxybenzaldehyde |
| CN110256285A (en) * | 2019-07-09 | 2019-09-20 | 上海出入境检验检疫局动植物与食品检验检疫技术中心 | A kind of synthetic method of stable isotope labeling pyrethroid |
-
2008
- 2008-08-29 CN CNA2008101246681A patent/CN101337868A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104230688A (en) * | 2013-06-24 | 2014-12-24 | 淄博职业学院 | Catalyzed synthesis method for m-phenoxy benzaldehyde |
| CN104926633A (en) * | 2015-05-06 | 2015-09-23 | 江西力田维康科技有限公司 | Preparation method for 3-alkoxybenzaldehyde |
| CN110256285A (en) * | 2019-07-09 | 2019-09-20 | 上海出入境检验检疫局动植物与食品检验检疫技术中心 | A kind of synthetic method of stable isotope labeling pyrethroid |
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Open date: 20090107 |