CN101274889B - 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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- CN101274889B CN101274889B CN2008100159934A CN200810015993A CN101274889B CN 101274889 B CN101274889 B CN 101274889B CN 2008100159934 A CN2008100159934 A CN 2008100159934A CN 200810015993 A CN200810015993 A CN 200810015993A CN 101274889 B CN101274889 B CN 101274889B
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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 the benzoic method for making of a kind of 3-[2-chloro-4-(trifluoromethyl) phenoxy].
Background technology
Fomesafen (fomesafen) has another name called prowers, removes the beans green bristlegrass, and chemical name is 5-[2-chloro-4-(trifluoromethyl) phenoxy]-N-methylsulfonyl-2-nitrobenzamide, belongs to fluorine-containing diphenyl ether herbicide; Being 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 get into 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, like 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, YO is about 600 tons.3-[2-chloro-4-(trifluoromethyl) phenoxy] phenylformic acid is the important intermediate during the former medicine of fomesafen synthesizes, and its quality directly affects the quality of the former medicine of fomesafen.Therefore produce the problem that high-load 3-[2-chloro-4-(trifluoromethyl) phenoxy] phenylformic acid has become domestic enterprise to study.
" 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 compound method of the former medicine of a kind of high-content fomesafen; Its 3-[2-chloro-4-(trifluoromethyl) phenoxy] phenylformic acid is synthetic to comprise the steps: in condensation reactor, to add quantitative solvent methyl-sulphoxide, m-Salicylic acid, Pottasium 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.Be cooled to feed liquid below 50 ℃, slowly be added dropwise to 30% hydrochloric acid, reach between the 1-2, promptly get the midbody condenses through filtering, wash, drying again 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 midbody of a kind of fomesafen---the benzoic method for making of 3-[2-chloro-4-(trifluoromethyl) phenoxy], in building-up process, improved the yield of title product, shorten the reaction times.
Synthetic route of the present invention is: m-Salicylic acid and Pottasium Hydroxide is salify in solvent earlier, adds Anhydrous potassium carbonate, 3 again, and 4-two chlorobenzotrifluorides and catalyzer carry out condensation reaction; Precipitation after condensation reaction is accomplished; Add water, acidifying, suction filtration; Centrifugal, obtain high-content etherate 3-[2-chloro-4-(trifluoromethyl) phenoxy] phenylformic acid after the drying.
The concrete technical scheme that the present invention adopts is:
The benzoic method for making of a kind of 3-[2-chloro-4-(trifluoromethyl) phenoxy] is characterized in that, comprises the following steps:
1) salify: methyl-sulphoxide is put into reaction kettle, adds Pottasium 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 accomplished, water and partial solvent that reaction generates were deviate from underpressure distillation;
Its reaction equation is:
2) condensation: cooling adds catalyzer, Anhydrous potassium carbonate and 3,4-two chlorobenzotrifluorides in still; 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 accomplished, remaining solids behind the precipitation in the still that is dissolved in water 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, spinning promptly got 3-[2-chloro-4-(trifluoromethyl) phenoxy] phenylformic acid with filtration cakes torrefaction;
Its reaction equation is:
The reaction mass mol ratio is: 3, and 4-two chlorobenzotrifluorides: m-Salicylic acid: Pottasium 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 said 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] 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 is explained 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 receive 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 just carried out more easily.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 midbody of fomesafen etherate 3-[2-chloro-4--(trifluoromethyl) phenoxy] benzoic acid content high (>=93%) of the present invention's preparation, yield is high, total recovery >=93% (with 3,4-two chlorobenzotrifluoride meters).
(2) use of catalyzer has promoted the generation of title product, has shortened the reaction times, has reduced the generation of by product, has improved former medicine content, and low in raw material cost is easy to get, and realizes easily in the industry.
Embodiment
Embodiment 1
(1) salify: in the reaction kettle of 100L, adding 38.60Kg methyl-sulphoxide (99%, 490mol) put into reaction kettle after metering; Add 10.20Kg Pottasium Hydroxide (92% while stirring; 168mol) with 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 accomplished, 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; Be warming up to 148～152 ℃ and carry out condensation reaction,, accomplished in 6 hours through HPLC assaying reaction terminal point; Reaction is cooled to below 130 ℃ after finishing, and the solvent methyl-sulphoxide is deviate from underpressure distillation.
(3) acidifying: after distillation is accomplished, remaining solids behind the precipitation in the still that is dissolved in water, the dropping concentrated hydrochloric acid carries out acidifying in the solution; Regulating the pH value is 1～2; Acidifying is carried out spinning after finishing, and obtains 23.65Kg 3-[2-chloro-4-(trifluoromethyl) phenoxy] phenylformic acid after the article drying that will wet; Content is 93.1%, and yield is 93.7%.
Embodiment 2
(1) salify: in the reaction kettle of 100L, adding 38.60Kg methyl-sulphoxide (99%, 490mol) put into reaction kettle after metering; Add 10.20Kg Pottasium Hydroxide (92% while stirring; 168mol) with 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 accomplished, 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; Be warming up to 148～152 ℃ and carry out condensation reaction,, accomplished in 7 hours through HPLC assaying reaction terminal point; Reaction is cooled to below 130 ℃ after finishing, and the solvent methyl-sulphoxide is deviate from underpressure distillation.
(3) acidifying: after distillation is accomplished, remaining solids behind the precipitation in the still that is dissolved in water, the dropping concentrated hydrochloric acid carries out acidifying in the solution; Regulating the pH value is 1～2; Acidifying is carried out spinning after finishing, and obtains 23.4Kg 3-[2-chlorine 4-(trifluoromethyl) phenoxy] phenylformic acid after the article drying that will wet; 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 accomplished in 6.5 hours, finally obtained 23.35Kg 3-[2-chloro-4-(trifluoromethyl) phenoxy] 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 accomplished in 7 hours, finally obtained 23.6Kg 3-[2-chloro-4-(trifluoromethyl) phenoxy] phenylformic acid; Content is 93.2%, and yield is 93.6%.
All the other are with embodiment 1.
Claims (1)
1. the benzoic method for making of a 3-[2-chloro-4-(trifluoromethyl) phenoxy] is characterized in that, comprises the following steps:
1) salify: methyl-sulphoxide is put into reaction kettle, adds Pottasium 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 accomplished, water and partial solvent that reaction generates were deviate from underpressure distillation;
2) condensation: cooling adds catalyzer, Anhydrous potassium carbonate and 3,4-two chlorobenzotrifluorides in still; 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 accomplished, remaining solids behind the precipitation in the still that is dissolved in water 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, spinning promptly got 3-[2-chloro-4-(trifluoromethyl) phenoxy] phenylformic acid with filtration cakes torrefaction;
The reaction mass mol ratio is: 3, and 4-two chlorobenzotrifluorides: m-Salicylic acid: Pottasium 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 said catalyzer is 2 ‰ of m-Salicylic acid weight～5 ‰;
Described copper catalyst series is a kind of in copper powder, cupric oxide, Red copper oxide, cupric chloride, the cuprous chloride;
Described 3-[2-chloro-4-(trifluoromethyl) phenoxy] benzoic content >=93%, yield is with 3,4-two chlorobenzotrifluoride meter >=93%.
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| CN102399152B (en) * | 2011-09-16 | 2014-02-12 | 华东理工大学 | Synthesis process for 2,4-bis(2-chloro-4-trifluoromethylphenoxy)-nitrobenzene |
| 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 |
| 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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| CN1680265A (en) * | 2005-01-19 | 2005-10-12 | 江苏长青农化股份有限公司 | Synthesis of 3-(2-Cl-a,a,a,-trifluoro-p-toloxy)-benzene carbonic acid |
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| CN1680265A (en) * | 2005-01-19 | 2005-10-12 | 江苏长青农化股份有限公司 | Synthesis of 3-(2-Cl-a,a,a,-trifluoro-p-toloxy)-benzene carbonic acid |
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