CN103012124A - Preparation method of 3,6-dichloro-2-hydroxybenzoic acid - Google Patents
Preparation method of 3,6-dichloro-2-hydroxybenzoic acid Download PDFInfo
- Publication number
- CN103012124A CN103012124A CN2012105762021A CN201210576202A CN103012124A CN 103012124 A CN103012124 A CN 103012124A CN 2012105762021 A CN2012105762021 A CN 2012105762021A CN 201210576202 A CN201210576202 A CN 201210576202A CN 103012124 A CN103012124 A CN 103012124A
- Authority
- CN
- China
- Prior art keywords
- chloro
- reaction
- acid
- gac
- chlorophenesic acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of 3,6-dichloro-2-hydroxybenzoic acid, which sequentially comprises the following steps: 1) salifying 2,5-dichlorophenol; 2) carboxylation: transferring the 2,5-dichlorophenate solution into a high-pressure reaction kettle, adding a cocatalyst, and introducing CO2 to carry out high-pressure carboxylation reaction to obtain the reaction product containing 3,6-dichloro-2-hydroxybenzoate, wherein the cocatalyst is composed of potassium carbonate and activated carbon; 3) refinement: after cooling the reaction product containing 3,6-dichloro-2-hydroxybenzoate obtained in the step 2) to room temperature, adding an alkali solution, regulating the pH value to 11-13, uniformly stirring, filtering to recover activated carbon, stratifying the filtrate, and taking the water phase; and adding an acid solution into the water phase, regulating the pH value to 1-3, carrying out vapor distillation to recover the 2,5-dichlorophenol, cooling to crystallize, carrying out vacuum filtration, and drying to obtain the 3,6-dichloro-2-hydroxybenzoic acid.
Description
Technical field
The invention belongs to dicamba 98 intermediate production technique, relate to a kind of 3, the synthetic method of 6-two chloro-2 hydroxybenzoic acids.
Background technology
3,6-, two chloro-2 hydroxybenzoic acids, 3, the 6-dichlorosalicylic acid, English name 3,6-Dichlorosallicylic Acid, structural formula:
3,6-, two chloro-2 hydroxybenzoic acids are intermediates of preparation pesticide herbicide dicamba 98 (3,6-, two chloro-O-Anisic Acids).Dicamba 98 is a kind of M-nitro benzoic acid serial herbicide that is at first developed by former U.S. west Bel chemical company.Forbidding and restriction grand along with chlorine sulphur and the metsulfuronmethyl preparation are used, and the demand of dicamba 98 is with increasing, and market outlook are good.At present, the global sales of dicamba 98 is about 1.5 ten thousand t/, and it produces the BASF AG mainly concentrate on Germany and the Sandoz company of Switzerland, domesticly mainly is Zhejiang Shenghua Biok Biology Co., Ltd. and raises agricultural chemical industry.
The technique of at present synthetic 3,6-, two chloro-2 hydroxybenzoic acids generally is solvent high pressure carboxylation method, i.e. klobe-schmitt reaction.Namely under alkaline condition, 2,5-chlorophenesic acid forms phenates, then in organic solvent, adds catalyzer, passes into CO
2Carry out carboxylation reaction, generate 3,6-, two chloro-2 hydroxybenzoic acid salt, after at last reaction mixture being added water stratification, the water product adds acid and carries out acidifying, wet distillation Separation and Recovery unreacted 2, it is pure 3 that 5-chlorophenesic acid, suction filtration oven dry then obtain, 6-two chloro-2 hydroxybenzoic acid solids.It was three steps that reaction is divided into:
In kolbe-schmitt reaction, undertaken often using salt of wormwood in the reaction of high pressure carboxylation by phenates or yellow soda ash is used as catalyzer.And for 2,5-dichlorobenzene phenates is well more a lot of than the effect with yellow soda ash as catalyzer with salt of wormwood.Therefore, at present in kolbe-schmitt reaction industry production 3, in the 6-two chloro-2 hydroxybenzoic acids, come the catalysis carboxylation reaction with salt of wormwood as catalyzer.
Although existing technology is improved the production technique of 3,6-, two chloro-2 hydroxybenzoic acids from different aspects, wherein mainly be to concentrate on the yield and reduction reaction cost two aspects that improve reaction to carry out.In existing technology, the yield of this reaction will improve yield very high to the requirement of technology production, industrial very difficult realization about 45%.In this reaction, unreacted raw material can wet distillation reclaim, and other raw material is all relatively cheap, so the consumption of catalyzer carbonic acid potassium has accounted for very large a part of ratio in the cost of this reaction.Therefore, if reduce the consumption of salt of wormwood, just can reduce the cost of this reaction, thereby reduce the production cost of herbicide dicamba.But, according to prior art, if reduce the consumption of salt of wormwood, can cause occurring the bad result that reaction yield reduces.
Summary of the invention
The technical problem to be solved in the present invention provide a kind of with low cost, yield is higher 3, the preparation method of 6-two chloro-2 hydroxybenzoic acids.
In order to solve the problems of the technologies described above, the invention provides a kind ofly 3, the preparation method of 6-two chloro-2 hydroxybenzoic acids may further comprise the steps successively:
1), 2,5-chlorophenesic acid salify:
2,5-chlorophenesic acid is dissolved in carries out salt-forming reaction in the alkaline solution, then add organic solvent and mix, get mixed solution; Mixed solution is carried out processed, obtain 2,5-chlorophenesic acid salts solution; The mol ratio of 2,5-chlorophenesic acid and alkali is 1:0.9 ~ 1.1;
2), carboxylation:
2,5-chlorophenesic acid salts solution is transferred in the autoclave, adds co-catalyst, then pass into CO
2Carry out the high pressure carboxylation reaction, must contain the reaction product of 3,6-, two chloro-2 hydroxybenzoic acid salt; Temperature of reaction is 140 ~ 160 ℃, and reaction pressure is 6 ~ 8Mpa, and the reaction times is 6 ~ 12h; Co-catalyst is comprised of salt of wormwood and gac, and the mass ratio of salt of wormwood and 2,5-chlorophenesic acid is that 0.01 ~ 0.2:1(is preferably 0.04 ~ 0.1:1); The mass ratio of gac and 2,5-chlorophenesic acid is that 0.01 ~ 0.2:1(is preferably 0.04 ~ 0.2:1);
3), refining:
With step 2) after the reaction product that contains 3,6-, two chloro-2 hydroxybenzoic acid salt of gained is cooled to room temperature (referring generally to 10 ~ 25 ℃), add alkaline solution, regulating pH to 11 ~ 13(is preferably about pH12), stir filtered and recycled gac, the phase of fetching water after the filtrate layering; At aqueous phase adding acid solution, regulate pH to 1 ~ 3, after steam distillation reclaims 2,5-chlorophenesic acid (wet distillation steams until no longer include 2,5-chlorophenesic acid), spontaneous nucleation, suction filtration drying get 3,6-, two chloro-2 hydroxybenzoic acids after the cooling.
As of the present invention 3, the preparation method's of 6-two chloro-2 hydroxybenzoic acids improvement: in the step 1): mixed solution is heated to 140 ~ 145 ℃, thereby realizes azeotropic dehydration, until steam without moisture, dehydration finishes; Obtain 2,5-chlorophenesic acid salts solution.
As of the present invention 3, the preparation method's of 6-two chloro-2 hydroxybenzoic acids further improvement: in the step 1): organic solvent is high boiling solvent;
High boiling solvent is toluene, dimethylbenzene, dimethyl sulfoxide (DMSO), DMF, n-Octanol.More preferably dimethylbenzene.
As of the present invention 3, the preparation method's of 6-two chloro-2 hydroxybenzoic acids further improvement: in the step 1): alkali is sodium hydroxide or potassium hydroxide.Be preferably potassium hydroxide.
In step 3) of the present invention, the alkaline solution that is used for adjusting pH is sodium hydroxide solution, and acid solution is hydrochloric acid soln (for example being concentrated hydrochloric acid).
Step 2 of the present invention) operation of the concrete technology of carboxylation reaction and control condition are specially in: 2,5-chlorophenesic acid salts solution is transferred in the autoclave, then adds co-catalyst, open intake valve and pass into CO
2Get rid of air in the still, with the reactor heat temperature raising, open simultaneously and stir, and in still, pass into a certain amount of CO after exhaust is complete
2, make temperature in the kettle and pressure be stabilized in respectively 140 ~ 160 ℃ and 6 ~ 8Mpa, under this state, react 6-12h.
The present invention is to provide a kind of at salt of wormwood (K
2CO
3), gac is altogether under the catalysis, 2,5-dichlorobenzene phenates and CO
2Technology by klobe-schmitt reaction preparation 3,6-two chloro-2 hydroxybenzoic acids.In the present invention, the gac that reclaims in the step 3) can be recycled.
The remarks explanation: in exquisite step, owing to need adding alkaline solution and acid solution to regulate accordingly pH, so salt of wormwood can't be recycled.
Provided by the invention 3,6-two chloro-2 hydroxybenzoic acid preparation methods have following characteristics:
1, the salt of wormwood that uses in replacing producing at present with the salt of wormwood of small amount and gac, the consumption of salt of wormwood be use in producing at present salt of wormwood 1/5, thereby reduce production costs.
2, the gac in the co-catalyst can recycle.
In sum, the present invention is with K
2CO
3, the co-catalyst catalysis kolbe-schmitt carboxylation reaction that forms of gac, replace using the larger salt of wormwood of amount ratio in the traditional mode of production, thereby reduce production costs.With K
2CO
3, synthetic 3,6-, the two chloro-2 hydroxybenzoic acids of gac co-catalyst method have no bibliographical information.
Embodiment
The below will be by embodiment to further instruction of the present invention.
The percentage ratio that below the present invention relates to is mass percent.
Embodiment 1, a kind of 3, the preparation method of 6-two chloro-2 hydroxybenzoic acids, carry out following steps successively:
1), in the there-necked flask of 1000ml, take by weighing 146g(0.83 mol) 2,5-chlorophenesic acid (95% purity) is dissolved in the aqueous solution (mass concentration 48% of 98gKOH, the KOH that contains 0.84mol) in, add again 640ml dimethylbenzene even as solvent, 142 ~ 145 ℃ of heating heat up, until steamed in substantially anhydrous minute, get 2,5-chlorophenesic acid potassium solution with water trap dehydration.
2), with above-mentioned steps 1) gained 2,5-chlorophenesic acid potassium solution is transferred to autoclave, then adds 12gK
2CO
3With the 14g gac as co-catalyst, in autoclave, fill CO
2To 3Mpa, emptying after stable, consecutive identical operation 3 times, thus fully replace air in the still; Then fill CO
2To 5Mpa, and heating; At last, the control temperature of reaction is 145 ℃, and reaction pressure is 6Mpa, carries out carboxylation reaction, and the reaction times is 12h.After reaction finishes, must contain the reaction product of 3,6-, two chloro-2 hydroxybenzoic acid potassium.
3), after the above-mentioned reaction product that contains 3,6-, two chloro-2 hydroxybenzoic acid potassium is cooled to room temperature, add the aqueous solution and the 350ml water of the NaOH of 155ml 40%, this moment, pH was about 12, filtered after fully stirring, and got filter cake and filtrate; Namely get the gac of recovery behind the filtration cakes torrefaction, heavy 13.8g can be recycled.Be positioned at the organic phase and the water that is positioned at lower floor on upper strata filtrate being divided into, then the phase of fetching water is the pH to 1 that 36% concentrated hydrochloric acid is regulated water, then steam distillation (regulating temperature is 140 ℃) with massfraction, until the clarification of water that steams, no longer exist 2,5-chlorophenesic acid and steam, be cooled to spontaneous nucleation after the room temperature, the gained crystal is after suction filtration and oven dry (drying to constant weight in 60 ℃), obtain 3,6-, two chloro-2 hydroxybenzoic acid solid 80.4g(0.388mol), calculated yield is 46.6%.The cut of wet distillation obtains 3,5-chlorophenesic acid solid 72.5g(0.434mol after the drying after filtration), the rate of recovery of raw material is 52.3%.Calculating raw material and the total yield of product is 98.9%.
Embodiment 2
Gac 14g among the embodiment 1 is reclaimed instead gac 13.8g(embodiment 1 gained that obtains)+the 0.2g gac, all the other are with embodiment 1.The result is:
Recovery obtains gac 13.9g, reclaims to obtain 3,5-chlorophenesic acid 73g(0.437mol), calculate recovery rate is 52.7%.Obtain 3,6-, two chloro-2 hydroxybenzoic acid solid 80g(0.386mol), calculated yield is 46.5%.Calculating raw material and the total yield of product is 99.2%.
Embodiment 3
Gac 14g among the embodiment 1 is reclaimed instead gac 13.9g(embodiment 2 gained that obtain)+the 0.1g gac, all the other are with embodiment 1.The result is:
Recovery obtains gac 13.9g, reclaims to obtain 3,5-chlorophenesic acid 72.1g(0.432mol), calculate recovery rate is 52.0%.Obtain 3,6-, two chloro-2 hydroxybenzoic acid solid 80.8g(0.390mol), calculated yield is 47.0%.Calculating raw material and the total yield of product is 99.0%.
Embodiment 4
Gac 14g among the embodiment 1 is reclaimed instead gac 13.9g(embodiment 3 gained that obtain)+the 0.1g gac, all the other are with embodiment 1.The result is:
Recovery obtains gac 13.7g, reclaims to obtain 3,5-chlorophenesic acid 74g(0.443mol), calculate recovery rate is 53.4%.Obtain 3,6-, two chloro-2 hydroxybenzoic acid solid 78.9g(0.381mol), calculated yield is 45.9%.Calculating raw material and the total yield of product is 99.3%.
Comparative Examples 1,
With the 12gK as co-catalyst among the embodiment 1
2CO
3Make 60g salt of wormwood into the 14g gac, corresponding step 3) in " filter after fully stirring, get filter cake and filtrate; Namely get the gac of recovery behind the filtration cakes torrefaction, heavy 13.8g can be recycled; Be positioned at the organic phase on upper strata filtrate being divided into and be positioned at the water of lower floor " become " after fully stirring, self-assembling formation is positioned at the organic phase on upper strata and is positioned at the water of lower floor ".All the other are with embodiment 1.Obtain at last 3,6-dimethyl-2 hydroxybenzoic acid solid 80.4g(0.388mol), calculated yield is 46.6%.3 of recovery, 5-chlorophenesic acid solid is 72.1g(0.432mol), the rate of recovery is 52.0%.Calculating raw material and the total yield of product is 98.6%.
Comparative Examples 2,
The 12gK as co-catalyst among the cancellation embodiment 1
2CO
3" filtering after fully stirring, getting filter cake and filtrate with the use of 14g gac, corresponding step 3); Namely get the gac of recovery behind the filtration cakes torrefaction, heavy 13.8g can be recycled; Be positioned at the organic phase on upper strata filtrate being divided into and be positioned at the water of lower floor " become " after fully stirring, self-assembling formation is positioned at the organic phase on upper strata and is positioned at the water of lower floor ".All the other are with embodiment 1.Obtain at last 3,6-, two chloro-2 hydroxybenzoic acid solid 58.2g(0.281mol), calculated yield is 33.9%.3 of recovery, 5-chlorophenesic acid solid is 88.2g(0.426mol), the rate of recovery is 63.6%.Calculating raw material and the total yield of product is 97.5%
Comparative Examples 3,
The use of the 14g gac among the cancellation embodiment 1 is namely only with 12gK
2CO
3" filtering after fully stirring, getting filter cake and filtrate as catalyzer, corresponding step 3); Namely get the gac of recovery behind the filtration cakes torrefaction, heavy 13.8g can be recycled; Be positioned at the organic phase on upper strata filtrate being divided into and be positioned at the water of lower floor " become " after fully stirring, self-assembling formation is positioned at the organic phase on upper strata and is positioned at the water of lower floor ".All the other are with embodiment 1.Obtain at last 3,6-, two chloro-, 2 hydroxy-benzoic acid solid 68.7g(0.332mol), calculated yield is 40%.3 of recovery, 5-chlorophenesic acid solid is 81.4g(0.487), the rate of recovery is 58.7%.Calculating raw material and the total yield of product is 98.7%.
Comparative Examples 4,
The use of the 14g gac among the cancellation embodiment 1 is with K
2CO
3Weight make 26g into by 12g, corresponding step 3) in " filter after fully stirring, get filter cake and filtrate; Namely get the gac of recovery behind the filtration cakes torrefaction, heavy 13.8g can be recycled; Be positioned at the organic phase on upper strata filtrate being divided into and be positioned at the water of lower floor " become " after fully stirring, self-assembling formation is positioned at the organic phase on upper strata and is positioned at the water of lower floor ".All the other are with embodiment 1.Obtain at last 3,6-, two chloro-, 2 hydroxy-benzoic acid solid 72.1g(0.348mol), calculated yield is 42%.3 of recovery, 5-chlorophenesic acid solid is 74.3g(0.445mol), the rate of recovery is 53.6%.Calculating raw material and the total yield of product is 95.6%.
Comparative Examples 5,
With the 12gK as co-catalyst among the embodiment 1
2CO
3Make 12gK into the 14g gac
2CO
3With the 28g gac, all the other are with embodiment 1.Recovery obtains gac 27.6g.Obtain 3,6-, two chloro-2 hydroxybenzoic acid solid 78.9g(0.381mol), calculated yield is 45.9%.Recovery obtains 3,5-chlorophenesic acid 72.1g(0.432mol), calculate recovery rate is 52.0%.Calculating raw material and the total yield of product is 97.9%.
Comparative Examples 6,
With the 12gK as co-catalyst among the embodiment 1
2CO
3Make 12gK into the 14g gac
2CO
3With the 7g gac, all the other are with embodiment 1.Recovery obtains gac 6.9g.Obtain 3,6-, two chloro-2 hydroxybenzoic acid solid 73.7g(0.356mol), calculated yield is 42.9%.Recovery obtains 3,5-chlorophenesic acid 76.3g(0.457mol), calculate recovery rate is 55.1%.Calculating raw material and the total yield of product is 98.0%.
Comparative Examples 7,
With the 12gK as co-catalyst among the embodiment 1
2CO
3Make 6gK into the 14g gac
2CO
3With the 14g gac, all the other are with embodiment 1.Recovery obtains gac 13.8g.Obtain 3,6-, two chloro-2 hydroxybenzoic acid solid 74g(0.357mol), calculated yield is 43.1%.Recovery obtains 3,5-chlorophenesic acid 75.4g(0.451mol), calculate recovery rate is 54.4%.Calculating raw material and the total yield of product is 97.5%.
At last, it is also to be noted that, what more than enumerate only is several specific embodiments of the present invention.Obviously, the invention is not restricted to above embodiment, many distortion can also be arranged.All distortion that those of ordinary skill in the art can directly derive or associate from content disclosed by the invention all should be thought protection scope of the present invention.
Claims (4)
1.3 the preparation method of 6-two chloro-2 hydroxybenzoic acids is characterized in that may further comprise the steps successively:
1), 2,5-chlorophenesic acid salify:
2,5-chlorophenesic acid is dissolved in carries out salt-forming reaction in the alkaline solution, then add organic solvent and mix, get mixed solution; Mixed solution is carried out processed, obtain 2,5-chlorophenesic acid salts solution; Described 2, the mol ratio of 5-chlorophenesic acid and alkali is 1:0.9 ~ 1.1;
2), carboxylation:
2,5-chlorophenesic acid salts solution is transferred in the autoclave, adds co-catalyst, then pass into CO
2Carry out the high pressure carboxylation reaction, must contain the reaction product of 3,6-, two chloro-2 hydroxybenzoic acid salt; Temperature of reaction is 140 ~ 160 ℃, and reaction pressure is 6 ~ 8Mpa, and the reaction times is 6 ~ 12h; Described co-catalyst is comprised of salt of wormwood and gac, and the mass ratio of described salt of wormwood and 2,5-chlorophenesic acid is 0.01 ~ 0.2:1; The mass ratio of described gac and 2,5-chlorophenesic acid is 0.01 ~ 0.2:1;
3), refining:
With step 2) after the reaction product that contains 3,6-, two chloro-2 hydroxybenzoic acid salt of gained is cooled to room temperature, add alkaline solution, regulate pH to 11 ~ 13, stir filtered and recycled gac, the phase of fetching water after the filtrate layering; Add acid solution at aqueous phase, regulate pH to 1 ~ 3, after steam distillation reclaimed 2,5-chlorophenesic acid, crystallisation by cooling, suction filtration drying got 3,6-, two chloro-2 hydroxybenzoic acids.
2. according to claim 13, the preparation method of 6-two chloro-2 hydroxybenzoic acids is characterized in that in the step 1): mixed solution is heated to 140 ~ 145 ℃, thereby realizes azeotropic dehydration, until steam without moisture, dehydration finishes; Obtain 2,5-chlorophenesic acid salts solution.
3. according to claim 1 and 23, the preparation method of 6-two chloro-2 hydroxybenzoic acids is characterized in that in the step 1): described organic solvent is high boiling solvent;
Described high boiling solvent is toluene, dimethylbenzene, dimethyl sulfoxide (DMSO), DMF, n-Octanol.
4. according to claim 33, the preparation method of 6-two chloro-2 hydroxybenzoic acids is characterized in that in the step 1): alkali is sodium hydroxide or potassium hydroxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210576202.1A CN103012124B (en) | 2012-12-26 | 2012-12-26 | Preparation method of 3,6-dichloro-2-hydroxybenzoic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210576202.1A CN103012124B (en) | 2012-12-26 | 2012-12-26 | Preparation method of 3,6-dichloro-2-hydroxybenzoic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103012124A true CN103012124A (en) | 2013-04-03 |
| CN103012124B CN103012124B (en) | 2015-03-25 |
Family
ID=47961290
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210576202.1A Expired - Fee Related CN103012124B (en) | 2012-12-26 | 2012-12-26 | Preparation method of 3,6-dichloro-2-hydroxybenzoic acid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103012124B (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102838482A (en) * | 2012-09-20 | 2012-12-26 | 山东潍坊润丰化工有限公司 | Preparation method of 3,6-dichlorosalicylic acid |
| CN104086411A (en) * | 2014-07-18 | 2014-10-08 | 甘肃省化工研究院 | Method for synthesizing 3,5-di-tert-butyl-2-hydroxybenzoic acid |
| CN104086393A (en) * | 2014-07-23 | 2014-10-08 | 山东潍坊润丰化工股份有限公司 | Improved preparation method of 3,6-dichloro salicylic acid |
| CN105481685A (en) * | 2014-10-09 | 2016-04-13 | 中国石油化工股份有限公司 | One-step method for synthesizing salicylic acid with phenol and supercritical carbon dioxide |
| CN106167453A (en) * | 2016-08-04 | 2016-11-30 | 山东省化工研究院 | A kind of preparation method of 2,4 dichlorphenoxyacetic acid methyl ester |
| CN106242971A (en) * | 2016-08-04 | 2016-12-21 | 山东省化工研究院 | A kind of chloracetate synthesis in water technology and the new method of preparation 2,4 D esters thereof |
| CN106278862A (en) * | 2016-08-04 | 2017-01-04 | 山东省化工研究院 | A kind of new technique for synthesizing of 2,4 dichlorphenoxyacetic acids |
| CN106478400A (en) * | 2015-09-02 | 2017-03-08 | 江苏优士化学有限公司 | A kind of method of the continuous Carboxylation salicylate of high pressure |
| WO2018106564A1 (en) | 2016-12-07 | 2018-06-14 | Monsanto Technology Llc | Processes for purification, recovery, and conversion of chlorophenol salts and preparation and recovery of products prepared therefrom |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4508920A (en) * | 1982-03-23 | 1985-04-02 | Bayer Aktiengesellschaft | Process for the preparation of aromatic hydroxycarboxylic acids |
| EP0478197A1 (en) * | 1990-09-17 | 1992-04-01 | MITSUI TOATSU CHEMICALS, Inc. | Control process of isomer ratio of aromatic hydroxycarboxylic acid |
| US6392090B1 (en) * | 1996-10-02 | 2002-05-21 | Mitsui Chemicals, Inc. | Process for preparing hydroxybenzoic acids |
| CN1684935A (en) * | 2002-10-01 | 2005-10-19 | 株式会社上野制药应用研究所 | Process for production of hydroxybenzoic acids |
| CN1784373A (en) * | 2003-03-04 | 2006-06-07 | 株式会社上野制药应用研究所 | Process for production of hydroxybenzoic acids |
| CN102211995A (en) * | 2011-05-09 | 2011-10-12 | 杭州方迪科技有限公司 | Preparation method of 2,6-dihydroxybenzoic acid |
-
2012
- 2012-12-26 CN CN201210576202.1A patent/CN103012124B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4508920A (en) * | 1982-03-23 | 1985-04-02 | Bayer Aktiengesellschaft | Process for the preparation of aromatic hydroxycarboxylic acids |
| EP0478197A1 (en) * | 1990-09-17 | 1992-04-01 | MITSUI TOATSU CHEMICALS, Inc. | Control process of isomer ratio of aromatic hydroxycarboxylic acid |
| US6392090B1 (en) * | 1996-10-02 | 2002-05-21 | Mitsui Chemicals, Inc. | Process for preparing hydroxybenzoic acids |
| CN1684935A (en) * | 2002-10-01 | 2005-10-19 | 株式会社上野制药应用研究所 | Process for production of hydroxybenzoic acids |
| CN1784373A (en) * | 2003-03-04 | 2006-06-07 | 株式会社上野制药应用研究所 | Process for production of hydroxybenzoic acids |
| CN102211995A (en) * | 2011-05-09 | 2011-10-12 | 杭州方迪科技有限公司 | Preparation method of 2,6-dihydroxybenzoic acid |
Non-Patent Citations (3)
| Title |
|---|
| IIJIMA, TAKAYUKI ET AL: "Efficient regioselective carboxylation of phenol to salicylic acid with supercritical CO2 in the presence of aluminum bromide", 《JOURNAL OF MOLECULAR CATALYSIS A: CHEMICAL》, vol. 295, no. 12, 12 November 2008 (2008-11-12), pages 52 - 56, XP025574317, DOI: doi:10.1016/j.molcata.2008.07.017 * |
| 严招春: "3,6-二氯水杨酸的合成研究", 《化工生产与技术》, vol. 10, no. 2, 31 December 2003 (2003-12-31), pages 8 - 9 * |
| 孟明扬等: "溶剂法碳酸化合成芳羟基羧酸新技术", 《燃料与染色》, vol. 41, no. 6, 31 December 2004 (2004-12-31), pages 373 - 375 * |
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102838482B (en) * | 2012-09-20 | 2015-02-04 | 山东潍坊润丰化工股份有限公司 | Preparation method of 3,6-dichlorosalicylic acid |
| CN102838482A (en) * | 2012-09-20 | 2012-12-26 | 山东潍坊润丰化工有限公司 | Preparation method of 3,6-dichlorosalicylic acid |
| CN104086411A (en) * | 2014-07-18 | 2014-10-08 | 甘肃省化工研究院 | Method for synthesizing 3,5-di-tert-butyl-2-hydroxybenzoic acid |
| CN104086393A (en) * | 2014-07-23 | 2014-10-08 | 山东潍坊润丰化工股份有限公司 | Improved preparation method of 3,6-dichloro salicylic acid |
| CN104086393B (en) * | 2014-07-23 | 2016-09-14 | 山东潍坊润丰化工股份有限公司 | A kind of preparation method of the 3,6-dichlorosalicylic acid of improvement |
| CN105481685A (en) * | 2014-10-09 | 2016-04-13 | 中国石油化工股份有限公司 | One-step method for synthesizing salicylic acid with phenol and supercritical carbon dioxide |
| CN105481685B (en) * | 2014-10-09 | 2018-03-23 | 中国石油化工股份有限公司 | By phenol and the salicylic method of supercritical carbon dioxide one-step synthesis |
| CN106478400A (en) * | 2015-09-02 | 2017-03-08 | 江苏优士化学有限公司 | A kind of method of the continuous Carboxylation salicylate of high pressure |
| CN106478400B (en) * | 2015-09-02 | 2019-10-15 | 江苏优士化学有限公司 | A kind of method of the continuous Carboxylation salicylate of high pressure |
| CN106278862A (en) * | 2016-08-04 | 2017-01-04 | 山东省化工研究院 | A kind of new technique for synthesizing of 2,4 dichlorphenoxyacetic acids |
| CN106242971A (en) * | 2016-08-04 | 2016-12-21 | 山东省化工研究院 | A kind of chloracetate synthesis in water technology and the new method of preparation 2,4 D esters thereof |
| CN106167453B (en) * | 2016-08-04 | 2019-06-21 | 山东省化工研究院 | A kind of preparation method of 2,4 dichlorophenoxyacetic acid methyl esters |
| CN106167453A (en) * | 2016-08-04 | 2016-11-30 | 山东省化工研究院 | A kind of preparation method of 2,4 dichlorphenoxyacetic acid methyl ester |
| WO2018106564A1 (en) | 2016-12-07 | 2018-06-14 | Monsanto Technology Llc | Processes for purification, recovery, and conversion of chlorophenol salts and preparation and recovery of products prepared therefrom |
| CN110248919A (en) * | 2016-12-07 | 2019-09-17 | 孟山都技术公司 | The technique of purifying, recycling and conversion chlorophenate and preparation and the recycling product as made from chlorophenate |
| US10913701B2 (en) | 2016-12-07 | 2021-02-09 | Monsanto Technology Llc | Processes for purification, recovery, and conversion of chlorophenol salts and preparation and recovery of products prepared therefrom |
| JP2022050607A (en) * | 2016-12-07 | 2022-03-30 | モンサント テクノロジー エルエルシー | Method for purification, recovery and conversion of chlorophenol salt as well as method of preparation and recovery of product prepared therefrom |
| US11629114B2 (en) | 2016-12-07 | 2023-04-18 | Monsanto Technology Llc | Processes for purification, recovery, and conversion of chlorophenol salts and preparation and recovery of products prepared therefrom |
| CN110248919B (en) * | 2016-12-07 | 2023-07-14 | 孟山都技术公司 | Process for purifying, recovering and converting chlorophenolates and for preparing and recovering products made from chlorophenolates |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103012124B (en) | 2015-03-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103012124B (en) | Preparation method of 3,6-dichloro-2-hydroxybenzoic acid | |
| CN103012123B (en) | Synthetic method for 3,6-dichloro-2-hydroxybenzoic acid | |
| CN108840854A (en) | A kind of method of one pot process 5- chlorothiophene -2- carboxylic acid | |
| CN103224451A (en) | Method for synthesizing 3,5-dichlorobenzoic acid | |
| CN105198710B (en) | The synthetic method of one inter-species tert-butyl phenol | |
| CN108440409B (en) | Green and efficient preparation method of rebamipide | |
| CN101778824B (en) | Process for producing toluidine compound | |
| CN102701954B (en) | Preparation method of alpha-ketovaline calcium | |
| CN104892371A (en) | Method for producing glycol dimethyl ether | |
| CN102408329B (en) | Preparation method of 2,4-dihydroxy benzoic acid | |
| CN103992241B (en) | The preparation method of N-substituted-phenyl glycine | |
| CN102295552A (en) | Method for increasing yield of 3,6-dichloro-2-hydroxybenzoic acid | |
| CN101307019B (en) | Method for preparing N-amino-3-azabicyclo[3,3,0]octane hydrochloride | |
| CN112047897A (en) | Preparation method of 3-aminoisoxazole | |
| CN101676276B (en) | Method for preparing N-tert-butyloxycarbonylpiperazine acetic acid hydrochloride | |
| CN103755577B (en) | A kind of method reclaiming Transbroncho alkali from Ambroxol HCl refinement mother liquor | |
| CN112174798A (en) | Synthesis method of Sacubitril valsartan sodium LCZ696 | |
| CN107652195A (en) | A kind of preparation method of 1 amino cyclopropanecarboxylic acid | |
| WO2009079861A1 (en) | Method for preparing iminodiacetic acid by using raw material of hydroxy acetonitrile | |
| CN105801378A (en) | Preparation method of 3,6-dichlorosalicylic acid | |
| CN111269084A (en) | Method for removing methyl formate and/or dimethyl carbonate in methanol | |
| CN109503561A (en) | A kind of preparation method of thiamine tetrahydrofuryl disfulfide | |
| CN101704771B (en) | Improved process for producing asulam | |
| CN104744352A (en) | Method for preparing 4-substituted oxyphenol compound | |
| CN115536548B (en) | Environment-friendly synthesis method of intermediate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150325 Termination date: 20151226 |
|
| EXPY | Termination of patent right or utility model |