CN107778167A - The preparation method of the methoxy benzoic acid of 2 methyl 3 - Google Patents
The preparation method of the methoxy benzoic acid of 2 methyl 3 Download PDFInfo
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- CN107778167A CN107778167A CN201610772409.4A CN201610772409A CN107778167A CN 107778167 A CN107778167 A CN 107778167A CN 201610772409 A CN201610772409 A CN 201610772409A CN 107778167 A CN107778167 A CN 107778167A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
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Abstract
The present invention relates to a kind of preparation method of the methoxy benzoic acid of 2 methyl 3, specific steps include：A. appropriate sodium methoxide solution, 2 are added in a kettle, and 6 dichlorotoleune, dimethylformamide and cuprous salt stirring heating, temperature control are reacted at 80 DEG C~150 DEG C, obtain the chloroanisole of 2 methyl 3；B. added appropriate tetrahydrofuran and magnesium in another reactor, temperature control adds the mixed liquor of bromoethane and the chloroanisole of 2 methyl 3 at 30 DEG C~60 DEG C, after reacting 20min~40min, the chloroanisole of 2 methyl 3 is added dropwise at 40 DEG C~60 DEG C in temperature control, rear insulation reaction 1.5h~2.5h is added dropwise, it is subsequently cooled to 15 DEG C~5 DEG C, dry ice is added by batch, temperature control is in 0 DEG C~20 DEG C insulation reaction 2h~4h, then tetrahydrofuran is reclaimed, it is the methoxy benzoic acid of 2 methyl 3 that adjustment ph values, which separate out white powder,.The preparation method route of the methoxy benzoic acid of 2 methyl 3 of the present invention is succinct and yield is high.
Description
Technical field
The present invention relates to a kind of preparation method of compound, especially a kind of preparation of 2- methyl -3- methoxy benzoic acids
Method.
Background technology
2- methyl -3- methoxy benzoic acids are organic synthesis intermediates important in agricultural chemicals, medical industry, especially efficiently
The important intermediate of low-toxin farm chemicals methoxyfenozide.The synthetic method of 2- methyl -3- methoxy benzoic acids have it is a variety of, wherein applying
Relatively broad one kind is using 3- nitro -2- methyl benzoic acids as raw material, through reduction, diazotising, methoxylation, obtains 2- first
Base -3- methoxy benzoic acids.But using 3- nitro -2- methyl benzoic acids as raw material, the raw material sources are difficult, price, industry
It is melted into this height.Another method is using 2,6-DCT as raw material, and etherified, cyaniding, hydrolysis obtain 2- methyl -3- methoxies
Yl benzoic acid.Because the cyanide using severe toxicity is as catalyst, more problem be present, and there are the more three wastes, therefore also not
Suitable industrialized production.
How to provide a kind of preparation method for the 2- methyl -3- methoxy benzoic acids that route is succinct and yield is high is this area
Technical staff's technical issues that need to address.
The content of the invention
2- methyl -3- methoxybenzene the first succinct and high yield the technical problem to be solved in the present invention is to provide a kind of route
The preparation method of acid.
The present invention is to solve a kind of technical scheme that above-mentioned technical problem proposes to be：A kind of 2- methyl -3- methoxybenzene first
The preparation method of acid, specific steps include：
A. appropriate sodium methoxide solution, 2,6- dichlorotoleune, dimethylformamide and cuprous salt stirring is added in a kettle to rise
Temperature, temperature control are reacted at 80 DEG C~150 DEG C, and room temperature is cooled to after reaction completely, are filtered off except mantoquita, filtrate decompression essence
Dimethylformamide is reclaimed after evaporating, obtains 2- methyl -3- chloroanisoles；
B. added in another reactor and appropriate tetrahydrofuran and magnesium, temperature control are added into bromoethane at 30 DEG C~60 DEG C
With the mixed liquor of 2- methyl -3- chloroanisoles, after reacting 20min~40min, 2- is added dropwise at 40 DEG C~60 DEG C in temperature control
Methyl -3- chloroanisoles, rear insulation reaction 1.5h~2.5h is added dropwise, is subsequently cooled to -15 DEG C~-5 DEG C, it is dry by batch addition
Then ice, temperature control are poured into reaction solution in frozen water in 0 DEG C~20 DEG C insulation reaction 2h~4h, acid adding adjusts ph values to 1,
Tetrahydrofuran is reclaimed after layering in organic layer, then adds alkali to adjust ph values to 12 in residue, is decolourized, filtered with activated carbon
Liquid acid adding adjusts ph values to 1, and it is 2- methyl -3- methoxy benzoic acids to separate out white powder.
In the step B, the parts by weight of tetrahydrofuran are 700~900, and the parts by weight of magnesium are 30~50, the weight of dry ice
Part is 70~80, and the parts by weight of bromoethane are 2~4；2- first in the mixed liquor of bromoethane and 2- the methyl -3- chloroanisoles
The parts by weight of base -3- chloroanisoles are 1~2, and the parts by weight for the 2- methyl -3- chloroanisoles being added dropwise are 248~249.
The cuprous salt is stannous chloride or cuprous cyanide.
The concentration of the sodium methoxide solution is 30%.
The acid that ph values are adjusted in the step B is the hydrochloric acid solution that concentration is 10%.
The alkali that ph values are adjusted in the step B is the sodium hydroxide solution that concentration is 5%.
White powder is separated out in the step B and obtains finished product after centrifuge dripping is dried.
The mol ratio of the 2,6- dichlorotoleune and sodium methoxide is the ︰ 0.9 of 1 ︰ 1.35~1.
The quality of the cuprous salt is the 0.2%~0.5% of 2,6- dichlorotoleune and sodium methoxide gross mass.
The quality of the dimethylformamide is 60%~100% to 2,6- dichlorotoleune and sodium methoxide gross mass.
The present invention has positive effect：The preparation method of the 2- methyl -3- methoxy benzoic acids of the present invention is with sodium methoxide
It is that raw material route is succinct with 2,6-DCT, reaction process is short, and dimethylformamide is easily recycled as solvent, can be repeatedly
Recycle, and yield can be effectively improved, advantageously reduce cost.The system of the 2- methyl -3- methoxy benzoic acids of the present invention
Preparation Method is suitable to industrial mass production.
Brief description of the drawings
Fig. 1 is the reaction equation in the embodiment of the present invention（1）.
Fig. 2 is the reaction equation in the embodiment of the present invention（2）.
Embodiment
Embodiment 1
The specific steps of the preparation method of the 2- methyl -3- methoxy benzoic acids of the present embodiment include：
A. sodium methoxide solution 180kg, 2,6- dichlorotoleune 161kg, dimethylformamide that concentration is 30% are added in a kettle
161kg and stannous chloride 0.5kg, stirring heating, temperature control are reacted at 100 DEG C, and room temperature, mistake are cooled to after reacting 16h
Elimination removes mantoquita, reclaims dimethylformamide after filtrate decompression rectifying, obtains the 2- methyl -3- chloroanisole liquid of water white transparency
Body.Step A reaction equation（1）It is as follows：
B. in another reactor add tetrahydrofuran 400kg and magnesium 20kg, temperature control 40 DEG C add 1kg bromoethanes and
The mixed liquor of 0.5kg 2- methyl -3- chloroanisoles, after reacting 30min, 2- methyl -3- chlorine is added dropwise at 50 DEG C for temperature control
Methyl phenyl ethers anisole 124.5kg, rear insulation reaction 2h is added dropwise, is subsequently cooled to -10 DEG C, dry ice 35kg, temperature control are added by batch
In 10 DEG C of insulation reaction 3h, then reaction solution is poured into frozen water, adds the hydrochloric acid solution that concentration is 10% to adjust ph values to 1, is layered
Tetrahydrofuran is reclaimed in organic layer afterwards, then adds the sodium hydroxide solution that concentration is 5% to adjust ph values to 12 in residue, is used
Activated carbon is decolourized, and filtrate adds the hydrochloric acid solution that concentration is 10% to adjust ph values to 1, separates out white powder, centrifuge dripping, does
Finished product 2- methyl -3- methoxy benzoic acids are obtained after dry, measure actual content as 98.8%.Step B reaction equation（2）It is as follows：
Embodiment 2
The specific steps of the preparation method of the 2- methyl -3- methoxy benzoic acids of the present embodiment include：
A. sodium methoxide solution 270kg, 2,6- dichlorotoleune 161kg, dimethylformamide that concentration is 30% are added in a kettle
200kg and stannous chloride 0.5kg, stirring heating, temperature control are reacted at 120 DEG C, and room temperature, mistake are cooled to after reacting 15h
Elimination removes mantoquita, reclaims dimethylformamide after filtrate decompression rectifying, obtains the 2- methyl -3- chloroanisole liquid of water white transparency
Body.
B. tetrahydrofuran 400kg and magnesium 20kg is added in another reactor, temperature control adds 1kg bromine second at 45 DEG C
The mixed liquor of alkane and 0.5kg 2- methyl -3- chloroanisoles, react 40min after, temperature control be added dropwise at 55 DEG C 2- methyl -
3- chloroanisole 124.5kg, rear insulation reaction 2.5h is added dropwise, is subsequently cooled to -10 DEG C, dry ice 40kg, temperature are added by batch
Degree is controlled in 20 DEG C of insulation reaction 2.5h, is then poured into reaction solution in frozen water, adds the hydrochloric acid solution that concentration is 10% to adjust ph values
To 1, tetrahydrofuran is reclaimed after layering in organic layer, then add the sodium hydroxide solution that concentration is 5% to adjust ph values in residue
To 12, decolourized with activated carbon, filtrate adds the hydrochloric acid solution that concentration is 10% to adjust ph values to 1, separates out white powder, centrifugation
Dry, finished product 2- methyl -3- methoxy benzoic acids are obtained after drying, measure actual content as 98.3%.
Embodiment 3
The specific steps of the preparation method of the 2- methyl -3- methoxy benzoic acids of the present embodiment include：
A. sodium methoxide solution 240kg, 2,6- dichlorotoleune 161kg, dimethylformamide that concentration is 30% are added in a kettle
180kg and cuprous cyanide 0.5kg, stirring heating, temperature control are reacted at 110 DEG C, and room temperature, mistake are cooled to after reaction completely
Elimination removes mantoquita, reclaims dimethylformamide after filtrate decompression rectifying, obtains the 2- methyl -3- chloroanisole liquid of water white transparency
Body.
B. tetrahydrofuran 400kg and magnesium 20kg is added in another reactor, temperature control adds 1kg bromine second at 40 DEG C
The mixed liquor of alkane and 0.5kg 2- methyl -3- chloroanisoles, react 40min after, temperature control be added dropwise at 45 DEG C 2- methyl -
3- chloroanisole 124.5kg, rear insulation reaction 2.5h is added dropwise, is subsequently cooled to -10 DEG C, dry ice 35kg, temperature are added by batch
Degree is controlled in 10 DEG C of insulation reaction 3h, is then poured into reaction solution in frozen water, adds the hydrochloric acid solution that concentration is 10% to adjust ph values extremely
1, tetrahydrofuran is reclaimed after layering in organic layer, then add the sodium hydroxide solution that concentration is 5% to adjust ph values extremely in residue
12, decolourized with activated carbon, filtrate adds the hydrochloric acid solution that concentration is 10% to adjust ph values to 1, separates out white powder, centrifugal drying
It is dry, finished product 2- methyl -3- methoxy benzoic acids are obtained after drying, measure actual content as 99.1%.
Raw materials used in the present invention is bought-in article unless otherwise specified, and concentration is that chemistry is pure.
Obviously, above-described embodiment is only intended to clearly illustrate example of the present invention, and is not to the present invention
The restriction of embodiment.For those of ordinary skill in the field, it can also be made on the basis of the above description
Its various forms of changes or variation.There is no necessity and possibility to exhaust all the enbodiments.And these belong to this hair
Among the obvious changes or variations that bright spirit is extended out is still in protection scope of the present invention.
Claims (10)
1. a kind of preparation method of 2- methyl -3- methoxy benzoic acids, it is characterised in that specific steps include：
A. appropriate sodium methoxide solution, 2,6- dichlorotoleune, dimethylformamide and cuprous salt stirring is added in a kettle to rise
Temperature, temperature control are reacted at 80 DEG C~150 DEG C, and room temperature is cooled to after reaction completely, are filtered off except mantoquita, filtrate decompression essence
Dimethylformamide is reclaimed after evaporating, obtains 2- methyl -3- chloroanisoles；
B. added in another reactor and appropriate tetrahydrofuran and magnesium, temperature control are added into bromoethane at 30 DEG C~60 DEG C
With the mixed liquor of 2- methyl -3- chloroanisoles, after reacting 20min~40min, 2- is added dropwise at 40 DEG C~60 DEG C in temperature control
Methyl -3- chloroanisoles, rear insulation reaction 1.5h~2.5h is added dropwise, is subsequently cooled to -15 DEG C~-5 DEG C, it is dry by batch addition
Then ice, temperature control are poured into reaction solution in frozen water in 0 DEG C~20 DEG C insulation reaction 2h~4h, acid adding adjusts ph values to 1,
Tetrahydrofuran is reclaimed after layering in organic layer, then adds alkali to adjust ph values to 12 in residue, is decolourized, filtered with activated carbon
Liquid acid adding adjusts ph values to 1, and it is 2- methyl -3- methoxy benzoic acids to separate out white powder.
2. the preparation method of 2- methyl -3- methoxy benzoic acids according to claim 1, it is characterised in that：The step B
In, the parts by weight of tetrahydrofuran are 700~900, and the parts by weight of magnesium are 30~50, and the parts by weight of dry ice are 70~80, bromoethane
Parts by weight be 2~4；The weight of 2- methyl -3- chloroanisoles in the mixed liquor of bromoethane and 2- the methyl -3- chloroanisoles
It is 1~2 to measure part, and the parts by weight for the 2- methyl -3- chloroanisoles being added dropwise are 248~249.
3. the preparation method of 2- methyl -3- methoxy benzoic acids according to claim 2, it is characterised in that：It is described cuprous
Salt is stannous chloride or cuprous cyanide.
4. the preparation method of 2- methyl -3- methoxy benzoic acids according to claim 1, it is characterised in that：The methanol
The concentration of sodium solution is 30%.
5. the preparation method of 2- methyl -3- methoxy benzoic acids according to claim 1, it is characterised in that：The step B
The acid of middle adjustment ph values is the hydrochloric acid solution that concentration is 10%.
6. the preparation method of 2- methyl -3- methoxy benzoic acids according to claim 1, it is characterised in that：The step B
The alkali of middle adjustment ph values is the sodium hydroxide solution that concentration is 5%.
7. the preparation method of 2- methyl -3- methoxy benzoic acids according to claim 1, it is characterised in that：The step B
Middle precipitation white powder obtains finished product after centrifuge dripping is dried.
8. the preparation method of 2- methyl -3- methoxy benzoic acids according to any one of claim 1 to 7, its feature exist
In：The mol ratio of the 2,6- dichlorotoleune and sodium methoxide is the ︰ 0.9 of 1 ︰ 1.35~1.
9. the preparation method of 2- methyl -3- methoxy benzoic acids according to any one of claim 1 to 7, its feature exist
In：The quality of the cuprous salt is the 0.2%~0.5% of 2,6- dichlorotoleune and sodium methoxide gross mass.
10. the preparation method of 4- phenoxy benzenemethanols according to any one of claim 1 to 7, it is characterised in that：It is described
The quality of dimethylformamide is 60%~100% to 2,6- dichlorotoleune and sodium methoxide gross mass.
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| CN201610772409.4A CN107778167A (en) | 2016-08-31 | 2016-08-31 | The preparation method of the methoxy benzoic acid of 2 methyl 3 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1188107A (en) * | 1996-09-24 | 1998-07-22 | 罗姆和哈斯公司 | Process for synthesizing benzoic acids |
| CN1232018A (en) * | 1998-03-09 | 1999-10-20 | 罗姆和哈斯公司 | Process for synthesizing benzoic acids |
| EP1044980A1 (en) * | 1997-12-09 | 2000-10-18 | Ihara Chemical Industry Co., Ltd. | Process for producing toluene derivatives |
-
2016
- 2016-08-31 CN CN201610772409.4A patent/CN107778167A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1188107A (en) * | 1996-09-24 | 1998-07-22 | 罗姆和哈斯公司 | Process for synthesizing benzoic acids |
| EP1044980A1 (en) * | 1997-12-09 | 2000-10-18 | Ihara Chemical Industry Co., Ltd. | Process for producing toluene derivatives |
| CN1232018A (en) * | 1998-03-09 | 1999-10-20 | 罗姆和哈斯公司 | Process for synthesizing benzoic acids |
Non-Patent Citations (1)
| Title |
|---|
| 崔茹平: "3-甲氧基-2-甲基苯甲酸的合成研究", 《广东化工》 * |
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Application publication date: 20180309 |