CN101274889A - Preparation for 3-(2-Chloro-alpha,alpha,alpha-trifluoro-p-tolyoxy) benzoic acid - Google Patents
Preparation for 3-(2-Chloro-alpha,alpha,alpha-trifluoro-p-tolyoxy) benzoic acid Download PDFInfo
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- CN101274889A CN101274889A CNA2008100159934A CN200810015993A CN101274889A CN 101274889 A CN101274889 A CN 101274889A CN A2008100159934 A CNA2008100159934 A CN A2008100159934A CN 200810015993 A CN200810015993 A CN 200810015993A CN 101274889 A CN101274889 A CN 101274889A
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Abstract
The invention relates to a method for preparing 3-(2-Chloro-4-trifluoro-p-tolyoxy) benzoic acid, which pertains to the technique filed of fluoride diphenyl ether pesticides. The technical points are that: m-hydroxybenzoic acid and potassium hydroxide first generate salt in a solvent; condensation reaction is carried out by adding anhydrous potassium carbonate, 3, 4-dichlorotrifluormethyl benzene and a copper-based catalyst and after the condensation reaction is finished, the etherate, 3-(2-Chloro-4-trifluoro-p-tolyoxy) benzoic acid with high content is obtained after desolvation, water-adding, acidification, air pump filtration, centrifugation and drying. The 3-(2-Chloro-4-trifluoro-p-tolyoxy) benzoic acid of the invention has high content which is more than or equal to 93 percent and high yield, thus shortening the reaction time, and the raw material is cheap and easy to be obtained and is easy to be realized in industry.
Description
Technical field
The invention belongs to fluorine-containing diphenyl ether technical field of pesticide, be specifically related to a kind of 3-[2-chloro-4-(trifluoromethyl) phenoxy group] benzoic method for making.
Background technology
Fomesafen (fomesafen) has another name called prowers, removes the beans green bristlegrass; chemical name is 5-[2-chloro-4-(trifluoromethyl) phenoxy group]-N-methylsulfonyl-2-nitrobenzamide; belonging to fluorine-containing diphenyl ether herbicide, is proporphyrinogen oxidase inhibitor, is a kind of efficient, low toxicity, wide spectrum dry land herbicide; for after tagging property weedicide touches the target plant cauline leaf; can enter cell interior rapidly, destroy cytolemma, entocyte is overflowed; plant tissue produces the physical property injury, finally causes death.Fomesafen is mainly used in soybean field, fruit tree, rubber plantation, leguminous crop, prevents and kill off annual and perennial broadleaf weed, as piemarker, Siberian cocklebur, Tender Catchweed Bedstraw Herb, black nightshade, Herba Commelinae, artemisia, amaranth grass, knotweed, thorn apple, lead a cow, sesbania etc.Present domestic 4 manufacturers that have of the former medicine of fomesafen, annual production is about 600 tons.3-[2-chloro-4-(trifluoromethyl) phenoxy group] phenylformic acid is the important intermediate of the former medicine of fomesafen in synthetic, its quality directly affects the quality of the former medicine of fomesafen.Therefore produce high-load 3-[2-chloro-4-(trifluoromethyl) phenoxy group] phenylformic acid become the problem of domestic enterprise's research.
" the former medicine of high-content fomesafen is synthetic " (Jiang Chengyan " agricultural chemicals " the 45th volume the 2nd phase P99-101 February in 2006) discloses the synthetic method of the former medicine of a kind of high-content fomesafen, its 3-[2-chloro-4-(trifluoromethyl) phenoxy group] phenylformic acid is synthetic comprises the steps: to add in condensation reactor quantitative solvent methyl-sulphoxide, m-Salicylic acid, potassium hydroxide, catalyzer, stirring is warming up to 110 ℃, and insulation 3h makes its abundant salify.Be cooled to below 90 ℃ the back and add quantitatively 3,4-two chlorobenzotrifluorides are warming up to 130-150 ℃ again, insulation 8h, and decompression subsequently removes and desolvates, and adds the solid that certain water gaging is separated out with dissolving.Feed liquid is cooled to below 50 ℃, slowly is added dropwise to 30% hydrochloric acid, reach between the 1-2, more after filtration, washing, oven dry promptly get the intermediate condenses until material liquid PH value.Condenses is to 3, and 4-two chlorobenzotrifluoride yields reach more than 90%.Dry product content is greater than 90%.
Summary of the invention
The object of the present invention is to provide the former medicine intermediate of a kind of fomesafen---3-[2-chloro-4-(trifluoromethyl) phenoxy group] benzoic method for making, in building-up process, improved the yield of target product, shorten the reaction times.
Synthetic route of the present invention is: m-Salicylic acid and potassium hydroxide is salify in solvent earlier, add Anhydrous potassium carbonate, 3 again, 4-two chlorobenzotrifluorides and catalyzer carry out condensation reaction, precipitation after condensation reaction is finished, add water, acidifying, suction filtration, centrifugal, obtain high-content etherate 3-[2-chloro-4-(trifluoromethyl) phenoxy group after the drying] phenylformic acid.
The concrete technical scheme that the present invention adopts is:
A kind of 3-[2-chloro-4-(trifluoromethyl) phenoxy group] benzoic method for making, it is characterized in that, comprise the following steps:
1) salify: methyl-sulphoxide is put into reactor, adds potassium hydroxide and m-Salicylic acid while stirring, is carried out to reactant salt in 2 hours 90～110 ℃ of insulations, and after salt-forming reaction was finished, water and partial solvent that reaction generates were deviate from underpressure distillation;
Its reaction equation is:
2) condensation: cooling, in still, add catalyzer, Anhydrous potassium carbonate and 3,4-two chlorobenzotrifluorides, reacting by heating is warming up to 148～152 ℃ of insulations and carries out condensation reaction, soaking time 6～8 hours, after reaction finishes, be cooled to below 130 ℃, the solvent methyl-sulphoxide is deviate from underpressure distillation, and the methyl-sulphoxide that steams recycles;
Its reaction equation is:
3) after underpressure distillation was finished, the remaining solids behind the precipitation that is dissolved in water in the still dripped concentrated hydrochloric acid in the solution and carries out acidifying, and regulating the pH value is 1～2, separates out a large amount of solids at this moment; After acidifying finished, centrifugation promptly got 3-[2-chloro-4-(trifluoromethyl) phenoxy group with filtration cakes torrefaction] phenylformic acid;
Its reaction equation is:
The reaction mass mol ratio is: 3, and 4-two chlorobenzotrifluorides: m-Salicylic acid: potassium hydroxide: salt of wormwood: methyl-sulphoxide=1.0: 1.06: 2.4: 0.35: 7;
Described catalyzer is a Cu-series catalyst, and the add-on of described catalyzer is 2 ‰ of m-Salicylic acid weight～5 ‰.
Described catalyzer is a kind of in copper powder, cupric oxide, Red copper oxide, cupric chloride, the cuprous chloride.
Described 3-[2-chloro-4-(trifluoromethyl) phenoxy group] benzoic content 〉=93%, yield is with 3,4-two chlorobenzotrifluoride meter 〉=93%.
Key point of the present invention is that condensation reaction has added Cu-series catalyst.This step condensation reaction is a bimolecular nucleophilic substitution, and its principle is that example illustrates with the basic hydrolysis of haloalkane (R-Cl): as nucleophilic reagent OH
-During carbon atom in the attack haloalkane, because halogen atom had the part negative charge originally, therefore electronegative nucleophilic reagent is general always from the backside attack carbon atom of halogen atom, near the carbon atom process, partly form the C-O key gradually, the C-Cl key is owing to be subjected to OH simultaneously
-The influence of attack and extend gradually and die down, the electron pair that makes the halogen atom band original Cheng Jian leaves carbon atom gradually.In carrying out nucleophilic substitution reaction, the halogen in the haloalkane is a leavings group, and its tendency of leaving away is big more, and substitution reaction is carried out with regard to easy more.And the copper atom in the copper catalyst series has a unoccupied orbital that does not fill up, and has increased the tendency of leaving away of halogen in the haloalkane, thereby has accelerated speed of response, has shortened the reaction times.
All raw materials that the present invention adopts all are commercially available Industrial products.
The invention has the advantages that:
(1) the former medicine intermediate of fomesafen etherate 3-[2-chlorine 4--(trifluoromethyl) phenoxy group of the present invention's preparation] benzoic acid content height (〉=93%), yield height, total recovery 〉=93% (with 3,4-two chlorobenzotrifluoride meters).
(2) use of catalyzer has promoted the generation of target product, has shortened the reaction times, has reduced the generation of by product, has improved former medicine content, and raw material is cheap and easy to get, industrial easy realization.
Embodiment
Embodiment 1
(1) salify: in the reactor of 100L, add 38.60Kg methyl-sulphoxide (99%, 490mol) put into reactor after metering, add 10.20Kg potassium hydroxide (92% while stirring, 168mol) and the 10.45Kg m-Salicylic acid (98%, 74.2mol), be warming up to about 100 ℃ insulation and be carried out to reactant salt in 2 hours, after salt-forming reaction was finished, water and the partial solvent that reaction generates deviate from distillation under reduced pressure.
(2) condensation: cooling, in still, add the 3.45Kg Anhydrous potassium carbonate (98%, 24.5mol), 15.28Kg 3,4-two chlorobenzotrifluorides (98.5%, 70mol) with the 0.04Kg cupric oxide, reacting by heating is warming up to 148～152 ℃ and carries out condensation reaction, through HPLC assaying reaction terminal point, finished in 6 hours, reaction is cooled to below 130 ℃ after finishing, and the solvent methyl-sulphoxide is deviate from underpressure distillation.
(3) acidifying: after distillation is finished, remaining solids behind the interior precipitation of the still that is dissolved in water, drip concentrated hydrochloric acid in the solution and carry out acidifying, regulating the pH value is 1～2, acidifying is carried out centrifugation after finishing, and obtains 23.65Kg 3-[2-chloro-4-(trifluoromethyl) phenoxy group after the product drying that will wet] phenylformic acid, content is 93.1%, and yield is 93.7%.
Embodiment 2
(1) salify: in the reactor of 100L, add 38.60Kg methyl-sulphoxide (99%, 490mol) put into reactor after metering, add 10.20Kg potassium hydroxide (92% while stirring, 168mol) and the 10.45Kg m-Salicylic acid (98%, 74.2mol), be warming up to about 100 ℃ insulation and be carried out to reactant salt in 2 hours, after salt-forming reaction was finished, water and the partial solvent that reaction generates deviate from distillation under reduced pressure.
(2) condensation: cooling, in still, add the 3.45Kg Anhydrous potassium carbonate (98%, 24.5mol), 15.28Kg 3,4-two chlorobenzotrifluorides (98.5%, 70mol) with 0.04Kg Red copper oxide, reacting by heating is warming up to 148～152 ℃ and carries out condensation reaction, through HPLC assaying reaction terminal point, finished in 7 hours, reaction is cooled to below 130 ℃ after finishing, and the solvent methyl-sulphoxide is deviate from underpressure distillation.
(3) acidifying: after distillation is finished, remaining solids behind the interior precipitation of the still that is dissolved in water, drip concentrated hydrochloric acid in the solution and carry out acidifying, regulating the pH value is 1～2, acidifying is carried out centrifugation after finishing, and obtains 23.4Kg 3-[2-chloro-4-(trifluoromethyl) phenoxy group after the product drying that will wet] phenylformic acid, content is 93.5%, and yield is 93.1%.
Embodiment 3
Repeat embodiment 1 by described identical step, but in step (2) condensation reaction, add the 0.04Kg cupric chloride, through HPLC assaying reaction terminal point, condensation reaction was finished in 6.5 hours, finally obtain 23.35Kg 3-[2-chloro-4-(trifluoromethyl) phenoxy group] phenylformic acid, content is 93.7%, and yield is 93.1%.
All the other are with embodiment 1.
Embodiment 4
Repeat embodiment 1 by described identical step, but in step (2) condensation reaction, add the 0.04Kg cuprous chloride, through HPLC assaying reaction terminal point, condensation reaction was finished in 7 hours, finally obtain 23.6Kg 3-[2-chloro-4-(trifluoromethyl) phenoxy group] phenylformic acid, content is 93.2%, and yield is 93.6%.
All the other are with embodiment 1.
Claims (3)
1. a 3-[2-chloro-4-(trifluoromethyl) phenoxy group] benzoic method for making, it is characterized in that, comprise the following steps:
1) salify: methyl-sulphoxide is put into reactor, adds potassium hydroxide and m-Salicylic acid while stirring, is carried out to reactant salt in 2 hours 90～110 ℃ of insulations, and after salt-forming reaction was finished, water and partial solvent that reaction generates were deviate from underpressure distillation;
2) condensation: cooling, in still, add catalyzer, Anhydrous potassium carbonate and 3,4-two chlorobenzotrifluorides, reacting by heating is warming up to 148～152 ℃ of insulations and carries out condensation reaction, soaking time 6～8 hours, after reaction finishes, cooling is below 130 ℃, and the solvent methyl-sulphoxide is deviate from underpressure distillation, and the methyl-sulphoxide that steams recycles;
3) after underpressure distillation was finished, the remaining solids behind the precipitation that is dissolved in water in the still dripped concentrated hydrochloric acid in the solution and carries out acidifying, and regulating the pH value is 1～2, separates out a large amount of solids at this moment; After acidifying finished, centrifugation promptly got 3-[2-chloro-4-(trifluoromethyl) phenoxy group with filtration cakes torrefaction] phenylformic acid;
The reaction mass mol ratio is: 3, and 4-two chlorobenzotrifluorides: m-Salicylic acid: potassium hydroxide: salt of wormwood: methyl-sulphoxide=1.0: 1.06: 2.4: 0.35: 7;
Described catalyzer is the copper catalyst series, and the add-on of described catalyzer is 2 ‰ of m-Salicylic acid weight～5 ‰.
2. 3-[2-chloro-4-according to claim 1 (trifluoromethyl) phenoxy group] benzoic method for making, it is characterized in that described catalyzer is a kind of in copper powder, cupric oxide, Red copper oxide, cupric chloride, the cuprous chloride.
3. 3-[2-chloro-4-according to claim 1 (trifluoromethyl) phenoxy group] benzoic method for making, it is characterized in that described 3-[2-chloro-4-(trifluoromethyl) phenoxy group] benzoic content 〉=93%, yield is with 3,4-two chlorobenzotrifluoride meter 〉=93%.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102399152A (en) * | 2011-09-16 | 2012-04-04 | 华东理工大学 | A New Synthetic Process of 2,4-Bis(2-Chloro-4-trifluoromethylphenoxy)-Nitrobenzene |
| CN102766043A (en) * | 2012-07-27 | 2012-11-07 | 京博农化科技股份有限公司 | Preparation method for 3- (2-chloro-4- (trifluoromethyl) phenoxy) -benzoic acid |
| CN103012126A (en) * | 2012-12-25 | 2013-04-03 | 江苏联化科技有限公司 | Preparation method of benzoic acid derivative |
| CN107032979A (en) * | 2017-06-12 | 2017-08-11 | 青岛瀚生生物科技股份有限公司 | The preparation method of 3 (trifluoromethyl of 2 chlorine 4) phenoxy benzoic acids |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100393692C (en) * | 2005-01-19 | 2008-06-11 | 江苏长青农化股份有限公司 | A method for synthesizing 3-(2-chloro-a, а, а-trifluoro-p-tolyloxy)-benzoic acid |
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- 2008-05-14 CN CN2008100159934A patent/CN101274889B/en active Active
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102399152A (en) * | 2011-09-16 | 2012-04-04 | 华东理工大学 | A New Synthetic Process of 2,4-Bis(2-Chloro-4-trifluoromethylphenoxy)-Nitrobenzene |
| CN102399152B (en) * | 2011-09-16 | 2014-02-12 | 华东理工大学 | Synthesis of 2,4-bis(2-chloro-4-trifluoromethylphenoxy)-nitrobenzene |
| CN102766043A (en) * | 2012-07-27 | 2012-11-07 | 京博农化科技股份有限公司 | Preparation method for 3- (2-chloro-4- (trifluoromethyl) phenoxy) -benzoic acid |
| CN102766043B (en) * | 2012-07-27 | 2014-12-17 | 京博农化科技股份有限公司 | Preparation method for 3- (2-chloro-4- (trifluoromethyl) phenoxy) -benzoic acid |
| CN103012126A (en) * | 2012-12-25 | 2013-04-03 | 江苏联化科技有限公司 | Preparation method of benzoic acid derivative |
| CN103012126B (en) * | 2012-12-25 | 2014-12-03 | 江苏联化科技有限公司 | Preparation method of benzoic acid derivative |
| CN107032979A (en) * | 2017-06-12 | 2017-08-11 | 青岛瀚生生物科技股份有限公司 | The preparation method of 3 (trifluoromethyl of 2 chlorine 4) phenoxy benzoic acids |
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