CN101362698B - Loctofen preparation method - Google Patents
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Abstract
The invention relates to a preparation method of Lactofen technical product of pesticides, belonging to the technical field of fluorine-containing diphenyl ether pesticide. 3,4-dichloro (trifluoromethyl) benzene and m-hydroxybenzoic acid are used as starting materials. After salification, condensation, acidification and nitrification processes, acifluorfen-sodium that is the intermediate product is produced. Acifluorfen-sodium and ethyl 2-chloropropionate are condensed into Lactofen technical product of pesticides under the action of catalyzer. The invention is characterized in that the catalyzer is quaternary ammonium salt and the dosage is within the range 5 permil to 10 permil. The method of the invention has the advantages of high yield, high content of technical product of pesticides, cheap and available raw material and easy realization in industry.
Description
Technical field
The invention belongs to fluorine-containing diphenyl ether technical field of pesticide, be specifically related to a kind of method for making of Loctofen.
Background technology
Lactofen (lactofen) has another name called the wealthy pleasure of gram; chemical name is O-[5-(2-chloro-4-4-trifluoromethylphenopendant)-2-nitro benzoyl-DL ethyl lactate; 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.Lactofen is mainly used in various crop fields such as soybean, peanut, cotton, paddy rice, grape, is used to prevent and kill off annual broadleaf weed such as Siberian cocklebur, black nightshade, artemisiifolia, thorn apple, purslane, Herba Acalyphae etc.China starts from nineteen nineties to the research of lactofen, and late nineteen nineties begins to drop into industrial production, present domestic 4 manufacturers that have, and annual production is about 600 tons.But the former medicine ubiquity of domestic production content is lower, and generally 75～80%, and state's exogenesis medicine content is more than 85%.
" chemosynthesis of lactofen " (Sun Ke, Lv Liangzhong, Qu Shude, Zhao Jing, Yu Rongzhen " agricultural chemicals " the 35th roll up the 17th～18 page of the 2nd phase) discloses a kind of method of lactofen chemosynthesis, and its disclosed content quotation is in this.
The lactofen of prior art is synthetic to adopt 3,4-two chlorobenzotrifluorides and m-Salicylic acid are starting raw material, obtain the intermediate product acifluorfen through salify, condensation, acidifying, after nitrated, condensation obtains Loctofen to acifluorfen with the 2-chloropropionate again.This synthetic route gained lactofen is more because of impurity at present, content is on the low side, its major cause is: in acifluorfen and the 2-chloropropionate condensation course, under the reaction conditions of prior art, a large amount of side reactions take place, generate a large amount of by products, thereby influence the content of Loctofen.
Summary of the invention
The invention provides a kind of method for making of Loctofen, solved and suppressed the problem that side reaction produces in the Loctofen building-up process, improved the target product generation.
Synthetic route of the present invention is: with 3, to be starting raw material obtain the intermediate product acifluorfen through salify, condensation, acidifying, after nitrated for 4-dichloro (trifluoromethyl) benzene and m-Salicylic acid, and acifluorfen and 2-chloropropionate are condensed into Loctofen under catalyst action.
The concrete technical scheme that the present invention adopts is:
A kind of method for making of Loctofen, with 3, to be starting raw material obtain the intermediate product acifluorfen through salify, condensation, acidifying, after nitrated for 4-dichloro (trifluoromethyl) benzene and m-Salicylic acid, acifluorfen and 2-chloropropionate are condensed into Loctofen under catalyst action, it is characterized in that described catalyzer is the quaternary ammonium salt catalyzer.
Described catalyzer is a kind of in benzyltriethylammoinium chloride, benzyl trimethyl ammonium chloride, benzyl triethyl ammonium bromide, tetramethyl ammonium chloride, 4-propyl bromide, Tetrabutyl amonium bromide, the dodecyl benzyl dimethyl ammonium chloride; The add-on of described catalyzer is 5 ‰ of acifluorfen weight～10 ‰.
The method for making of described Loctofen is characterized in that, comprises the following steps:
(1) 3-[2-chloro-4-(trifluoromethyl) phenoxy group] preparation of phenylformic acid (first intermediate)
Methyl-sulphoxide is put into reactor after metering, adds potassium hydroxide and m-Salicylic acid through metering while stirring, is warming up to 110 ℃ and is carried out to reactant salt, and insulation is 3 hours under this temperature, under reduced pressure deviates from water and the partial solvent that reaction generates.Add Anhydrous potassium carbonate and 3 then in still, 4-dichloro (trifluoromethyl) benzene continues to be warming up to 152-158 ℃, carries out condensation reaction, and insulation is 20-22 hour under this temperature, deviates from the solvent methyl-sulphoxide, and the methyl-sulphoxide that steams recycles.The remaining solid thing in the still that is dissolved in water drips concentrated hydrochloric acid in the solution and carries out acidifying, and pH is controlled at 1-2, after the acidifying end, carries out centrifugation, and centrifugal material is drying to obtain 3-[2-chloro-4-(trifluoromethyl) phenoxy group] phenylformic acid.
3-[2-chloro-4--(trifluoromethyl) phenoxy group] benzoic acid content 〉=85%.
The raw materials used mol ratio of step 1) is: 3, and 4-dichloro (trifluoromethyl) benzene: m-Salicylic acid: potassium hydroxide: salt of wormwood: methyl-sulphoxide=1.0: 1.06: 2.4: 0.35: 7.
Its reaction equation is:
2) 5-[2-chloro-4-(trifluoromethyl) phenoxy group]-preparation of 2-nitrobenzoic acid (second intermediate)
The vitriol oil is put into nitration mixture configuration still after metering, stirs and slowly put into the concentrated nitric acid through metering; Join in the nitrating pot after the methylene dichloride metering, under agitation add the exsiccant condenses, controlled temperature is 20～25 ℃, slowly add nitration mixture, after nitration mixture drips and finishes, back flow reaction, reaction end adopts high performance liquid phase (HPLC) control, and sampling records 3-[2-chloro-4-(trifluoromethyl) phenoxy group in the material] benzoic acid content≤0.5% is qualified, and qualified back keeps little standing demix that boils, lower floor's spent acid removes to handle device, the upper strata dichloromethane solution is put into the precipitation still, steams methylene dichloride, the decompression of precipitation later stage, solid materials washing behind the precipitation, suction filtration gets thick itrated compound acifluorfen; Its chemical name is 5-[2-chloro-4-(trifluoromethyl) phenoxy group]-the 2-nitrobenzoic acid.
Step 2) raw materials used mol ratio is: 3-[2-chloro-4--(trifluoromethyl) phenoxy group] phenylformic acid: nitric acid: sulfuric acid=1: 1.4: 2.9
5-[2-chloro-4-(trifluoromethyl) phenoxy group]-2-nitrobenzoyl acid content 〉=75%.
Its reaction equation is:
3) Loctofen is synthetic
With acifluorfen and 2-chloropropionate thermosol, under 80～85 ℃, be added dropwise in 2-chloropropionate and the salt of wormwood mixed solution, drip the back and add catalyzer down at 90～95 ℃, then 90～95 ℃ of insulations 6-8 hour, through HPLC assaying reaction terminal point, to filter, filtrate adds water and is washed to neutrality, branch vibration layer, oil reservoir are deviate from excessive 2-chloropropionate and are promptly obtained Loctofen.
Its reaction equation is:
Side reaction:
The lactofen content of the present invention's preparation is 86%～88%, total molar yield 〉=and more than 68% (with 3,4-dichloro (trifluoromethyl) benzene meter).
The principle that catalyzer of the present invention is selected is to be that example illustrates with the replacement(metathesis)reaction of inorganic anion (CN-) in haloalkane in the organic phase (R-Br) and the water item under catalyzer (quaternary ammonium salt) acts on: positive ion of catalyzer (Q+) and CN-negative ion are combined into ion pair, transfer in the organic phase then, react with the haloalkane in the organic phase, generate prussiate, and the positive ion of catalyzer and halogen ion carry out association reaction, generate quaternary ammonium salt again and transfer in the water item.Phase-transfer catalyst can be used for aspects such as nucleophilic substitution, condensation reaction, addition reaction, ring expansion, high molecular weight reactive, organometallics reaction, asymmetric synthesis.
This reaction condensation operation is by water-soluble material salt of wormwood and the reaction of ester dissolubility raw material fellowship, has therefore selected such catalyzer for use.
All raw materials that the present invention adopts all are commercially available Industrial products.
Beneficial effect of the present invention is:
(1) the Loctofen content height (86%～88%) of the present invention's preparation, yield height (with 3,4-dichloro (trifluoromethyl) benzene meter), total molar yield 〉=68%.
(2) use of catalyzer has promoted the generation of target product, 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) 3-[2-chloro-4-(trifluoromethyl) phenoxy group] benzoic preparation
In the reactor of 100L, add 38.60Kg methyl-sulphoxide (99%, 490mol) put into reactor after metering, add 10.10Kg potassium hydroxide (93% while stirring, 168mol) and the 10.45Kg m-Salicylic acid (98%, 74.2mol), be warming up to 110 ℃ and be carried out to reactant salt, 3 hours time, under reduced pressure deviate from water and the partial solvent that reaction generates.In still, add then the 3.45Kg Anhydrous potassium carbonate (98%, 24.5mol) and 15.28Kg 3.4-two chlorobenzotrifluorides (98.5%, 70mol), continue to be warming up to 152-158 ℃, carry out condensation reaction, condensation reaction 20-22 hour, deviate from the solvent methyl-sulphoxide.The remaining solid thing in the still that is dissolved in water drips concentrated hydrochloric acid in the solution and carries out acidifying and make PH=1-2, after the acidifying end, carry out centrifugation, obtain 22.65Kg 3-[2-chloro-4-(trifluoromethyl) phenoxy group after the product drying that will wet] phenylformic acid, content is 85.6%, yield is 87.5%.
2) 5-[2-chloro-4-(trifluoromethyl) phenoxy group]-preparation of 2-nitrobenzoic acid
With the 17.4Kg vitriol oil (98%, 174mol) put into 50L nitration mixture configuration still, stir and slowly put into the 5.4Kg concentrated nitric acid (98%, 84mol); In the 150L reactor, add the 80L methylene dichloride, under agitation add 22.18Kg exsiccant 3-[2-chloro-4-(trifluoromethyl) phenoxy group] phenylformic acid (85.6%, 60mol), under 20～25 ℃, slowly add nitration mixture, after nitration mixture drips and finishes, 18～20 ℃ of insulation reaction 2 hours, reaction end adopted high performance liquid phase (HPLC) control, and qualified back keeps little standing demix that boils, lower floor's spent acid removes to handle device, the upper strata dichloromethane solution is put into the precipitation still, steams methylene dichloride, the decompression of precipitation later stage, solid materials washing behind the precipitation, suction filtration, filtration cakes torrefaction is got 20.38Kg5-[2-chloro-4-(trifluoromethyl) phenoxy group]-the 2-nitrobenzoic acid, content 91.2%, yield 85.7%.
3) preparation of lactofen
In the 100L reactor, add 73.25 Kg2-chloropropionates (99%, 530mol), under agitation add 19.82Kg5-[2-chloro-4-(trifluoromethyl) phenoxy group]-2-nitrobenzoic acid (91.2%, 50mol), be warming up to 80～85 ℃ and get solution A, in the 150L reactor, add 43.95Kg 2-chloropropionate (99%, 320mol) and 9.15Kg salt of wormwood (99%, 65mol), stirring heats up 80～85 ℃ gets solution B, at 80～85 ℃ A solution is splashed in the solution B, be warming up to 90～95 ℃ after dripping and add the 0.2Kg benzyltriethylammoinium chloride down, then 90～95 ℃ of insulations 6-8 hour, through HPLC assaying reaction terminal point, filter, filtrate adds water and is washed to neutrality, branch vibration layer, oil reservoir is deviate from excessive 2-chloropropionate and is obtained the 24.5Kg Loctofen, content 87.2%, yield 92.6% is in 3.4-two chlorobenzotrifluoride total recoverys 69.4%.
The raw material that adopts in the preparation is the commercially available prod.
Embodiment 2
1) 3-[2-chloro-4-(trifluoromethyl) phenoxy group] benzoic preparation
In the reactor of 100L, add 38.60Kg methyl-sulphoxide (99%, 490mol) put into reactor after metering, add 10.10Kg potassium hydroxide (93% while stirring, 168mol) and the 10.45Kg m-Salicylic acid (98%, 74.2mol), be warming up to 110 ℃ and be carried out to reactant salt, 3 hours time, under reduced pressure deviate from water and the partial solvent that reaction generates.In still, add then the 3.45Kg Anhydrous potassium carbonate (98%, 24.5mol) and 15.28Kg 3.4-two chlorobenzotrifluorides (98.5%, 70mol), continue to be warming up to 152-158 ℃, carry out condensation reaction, condensation reaction 20-22 hour, deviate from the solvent methyl-sulphoxide.The remaining solid thing in the still that is dissolved in water drips concentrated hydrochloric acid in the solution and carries out acidifying and make PH=1-2, after the acidifying end, carry out centrifugation, biscuit is obtained 22.58Kg 3-[2-chloro-4-(trifluoromethyl) phenoxy group after dry] phenylformic acid, content is 85.8%, yield is 87.4%.
2) 5-[2-chloro-4-(trifluoromethyl) phenoxy group]-preparation of 2-nitrobenzoic acid
With the 17.4Kg vitriol oil (98%, 174mol) put into 50L nitration mixture configuration still, stir and slowly put into the 5.4Kg concentrated nitric acid (98%, 84mol); In the 150L reactor, add the 80L methylene dichloride, under agitation add 22.13Kg exsiccant 3-[2-chloro-4-(trifluoromethyl) phenoxy group] phenylformic acid (85.8%, 60mol), under 20～25 ℃, slowly add nitration mixture, after nitration mixture drips and finishes, 18～20 ℃ of insulation reaction 2 hours, reaction end adopted high performance liquid phase (HPLC) control, and qualified back keeps little standing demix that boils, lower floor's spent acid removes to handle device, the upper strata dichloromethane solution is put into the precipitation still, steams methylene dichloride, the decompression of precipitation later stage, solid materials washing behind the precipitation, suction filtration, filtration cakes torrefaction is got 20.42Kg5-[2-chloro-4-(trifluoromethyl) phenoxy group]-the 2-nitrobenzoic acid, content 91.6%, yield 86.2%.
3) preparation of lactofen
In the 100L reactor, add 73.25 Kg2-chloropropionates (99%, 530mol), under agitation add 19.73Kg5-[2-chloro-4-(trifluoromethyl) phenoxy group]-2-nitrobenzoic acid (91.6%, 50mol), be warming up to 80～85 ℃ and get solution A, in the 150L reactor, add 43.95Kg 2-chloropropionate (99%, 320mol) and 9.15Kg salt of wormwood (99%, 65mol), stirring heats up 80～85 ℃ gets solution B, at 80～85 ℃ A solution is splashed in the solution B, be warming up to 90～95 ℃ after dripping and add the 0.2Kg benzyl trimethyl ammonium chloride down, then 90～95 ℃ of insulations 6-8 hour, through HPLC assaying reaction terminal point, filter, filtrate adds water and is washed to neutrality, branch vibration layer, oil reservoir is deviate from excessive 2-chloropropionate and is obtained the 24.3Kg Loctofen, content 87.4%, yield 92.1% is in 3.4-two chlorobenzotrifluoride total recoverys 69.3%.
The raw material that adopts in the preparation is the commercially available prod.
Embodiment 3
Repeat embodiment 1 by described identical step, but from step 3): the preparation of lactofen: the 100L reactor, add 73.25Kg2-chloropropionate (99%, 530mol), under agitation add 19.86Kg 5-[2-chloro-4-(trifluoromethyl) phenoxy group]-2-nitrobenzoic acid (91.0%, 50mol), be warming up to 80～85 ℃ and get solution A, in the 150L reactor, add 43.95Kg 2-chloropropionate (99%, 320mol) with 9.15Kg salt of wormwood (99%, 65mol), stirring heats up 80～85 ℃ gets solution B, at 80～85 ℃ A solution is splashed in the solution B, be warming up to 90～95 ℃ after dripping and add the 0.2Kg Tetrabutyl amonium bromide down, 90～95 ℃ of insulations 6-8 hour,, filter then through HPLC assaying reaction terminal point, filtrate adds water and is washed to neutrality, branch vibration layer, oil reservoir are deviate from excessive 2-chloropropionate and are obtained the 24.4Kg Loctofen, content 87.3%, yield 92.3% is in 3.4-two chlorobenzotrifluoride total recoverys 68.9%.
All the other are with embodiment 1.
Embodiment 4
Repeat embodiment 1 by described identical step, but from step (3): the preparation of lactofen: the 100L reactor, add 73.25Kg2-chloropropionate (99%, 530mol), under agitation add 19.84Kg 5-[2-chloro-4-(trifluoromethyl) phenoxy group]-2-nitrobenzoic acid (91.1%, 50mol), be warming up to 80～85 ℃ and get solution A, in the 150L reactor, add 43.95Kg 2-chloropropionate (99%, 320mol) with 9.15Kg salt of wormwood (99%, 65mol), stirring heats up 80～85 ℃ gets solution B, at 80～85 ℃ A solution is splashed in the solution B, be warming up to 90～95 ℃ after dripping and add the 0.2Kg dodecyl benzyl dimethyl ammonium chloride down, 90～95 ℃ of insulations 6-8 hour,, filter then through HPLC assaying reaction terminal point, filtrate adds water and is washed to neutrality, branch vibration layer, oil reservoir are deviate from excessive 2-chloropropionate and are obtained the 24.2Kg Loctofen, content 87.4%, yield 91.6% is in 3.4-two chlorobenzotrifluoride total recoverys 68.5%.
All the other are with embodiment 1.
Comparative Examples
Repeat embodiment 1 by described identical step, but from step (3): the preparation process of lactofen: do not add catalyzer, it is 80.2% that condensation reaction obtains lactofen content, and yield 85.6% is in 3.4-two chlorobenzotrifluoride total recoverys 61.3%.
All the other are with embodiment 1.
Claims (1)
1. the method for making of a Loctofen is characterized in that, comprises the steps:
1) 3-[2-chloro-4-(trifluoromethyl) phenoxy group] benzoic preparation
Earlier methyl-sulphoxide is added in the reactor, add potassium hydroxide and m-Salicylic acid successively under stirring, be warming up to 110 ℃ and be carried out to reactant salt, and be incubated 3 hours down at 110 ℃; The water of partial solvent and reaction generation is deviate from underpressure distillation, control precipitation temperature is no more than 95 ℃, in still, add Anhydrous potassium carbonate and 3 then, 4-dichloro (trifluoromethyl) benzene, continue to be warming up to 152-158 ℃, carry out condensation reaction, condensation reaction soaking time 20-22 hour, insulation finishes, and the solvent methyl-sulphoxide is deviate from underpressure distillation; The remaining solid thing in the still that is dissolved in water drips concentrated hydrochloric acid in the solution and carries out acidifying, and acidifying is carried out centrifugation after finishing, and drying must 3-[2-chloro-4-(trifluoromethyl) phenoxy group] phenylformic acid;
The raw materials used mol ratio of step 1) is: 3, and 4-dichloro (trifluoromethyl) benzene: m-Salicylic acid: potassium hydroxide: Anhydrous potassium carbonate: methyl-sulphoxide=1.0: 1.06: 2.4: 0.35: 7;
2) 5-[2-chloro-4-(trifluoromethyl) phenoxy group]-preparation of 2-nitrobenzoic acid
The vitriol oil adds in the nitration mixture configuration still after metering, stirs and the slow concentrated nitric acid that adds through metering; Join in the nitrating pot after the methylene dichloride metering, under agitation add exsiccant 3-[2-chloro-4-(trifluoromethyl) phenoxy group] phenylformic acid, controlled temperature is 20～25 ℃, slowly be added dropwise to nitration mixture, after nitration mixture drips and finishes, back flow reaction, reaction end adopt high performance liquid phase control, and sampling records 3-[2-chloro-4-(trifluoromethyl) phenoxy group in the material] benzoic acid content≤0.5% be qualified, qualified back keeps little standing demix that boils, lower floor's spent acid removes to handle device, and the upper strata dichloromethane solution is put into the precipitation still, steams methylene dichloride, after observation solvent receiving amount reaches 80%～85%, the decompression precipitation, the solid materials washing behind the precipitation, suction filtration gets acifluorfen;
Step 2) raw materials used mol ratio is: 3-[2-chloro-4-(trifluoromethyl) phenoxy group] phenylformic acid: concentrated nitric acid: the vitriol oil=1: 1.4: 2.9;
3) Loctofen is synthetic
With acifluorfen and 2-chloropropionate thermosol, under 80～85 ℃, be added dropwise in 2-chloropropionate and the salt of wormwood mixed solution, drip the back and add catalyzer down at 90～95 ℃, catalyzer is a benzyltriethylammoinium chloride, benzyl trimethyl ammonium chloride, benzyl triethyl ammonium bromide, tetramethyl ammonium chloride, 4-propyl bromide, Tetrabutyl amonium bromide, a kind of in the dodecyl benzyl dimethyl ammonium chloride, catalyst consumption is 5 ‰ of acifluorfen weight～10 ‰, then 90～95 ℃ of insulations 6-8 hour, acifluorfen content was reaction end less than 0.5% o'clock in HPLC mensuration material, filter, filtrate adds water and is washed to neutrality, branch vibration layer, oil reservoir are deviate from excessive 2-chloropropionate and are promptly obtained Loctofen.
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| 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 |
| CN103694123B (en) * | 2014-01-07 | 2016-03-23 | 上虞颖泰精细化工有限公司 | A kind of preparation method of lactofen |
| CN104285950A (en) * | 2014-09-26 | 2015-01-21 | 青岛康和食品有限公司 | Pre-emergence herbicide mixture applied to peanut field |
| CN112279790A (en) * | 2019-07-23 | 2021-01-29 | 佳木斯市恺乐农药有限公司 | Preparation method of fomesafen original drug |
| CN111732511A (en) * | 2020-07-27 | 2020-10-02 | 西安思科赛实业有限公司 | Preparation process of acifluorfen |
| CN113548969A (en) * | 2021-08-17 | 2021-10-26 | 西安思科赛实业有限公司 | Preparation method of fluoroglycofen-ethyl |
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