CN101386578A - Method for making high content lactofen original drug - Google Patents
Method for making high content lactofen original drug Download PDFInfo
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- CN101386578A CN101386578A CNA2007101128197A CN200710112819A CN101386578A CN 101386578 A CN101386578 A CN 101386578A CN A2007101128197 A CNA2007101128197 A CN A2007101128197A CN 200710112819 A CN200710112819 A CN 200710112819A CN 101386578 A CN101386578 A CN 101386578A
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Abstract
The present invention discloses a method for preparing a high content lactofen raw pesticide, which belongs to the technical field of fluoride bearing diphenyl oxide pesticide.3,4-dichloro benzotrifluoride and m-hydroxybenzoic acid which are adopted as the initial raw materials are subjected to salification, condensation, acidification and nitration to obtain an intermediate product that is acifluorfen. The acifluorfen and 2-chloropropionic acid ethyl ester are condensed into the lactofen raw pesticide in the presence of a catalyst. The method is characterized in that the catalyst is a quaternaries catalyst and the dosage is between 5 and 10 per mille. The method has the advantages of high yield, high content of raw pesticide, inexpensive material, easy obtaining of the material, and easy industrial realization.
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 high content lactofen original drug.
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 soybean, peanut Tanaka, 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%.Therefore produce the problem that high-load lactofen has become domestic enterprise to study.
Domestic lactofen synthetic employing 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." chemosynthesis of lactofen " (" agricultural chemicals " such as Sun Ke, Lv Liangzhong were rolled up the 17th, 18 pages of the 2nd phases in 1996 the 35th) discloses a kind of chemical synthesis process of lactofen, its total recovery is 60%, former medicine content is 80.5%, and its disclosed content quotation is in this.
This synthetic route gained lactofen is more because of impurity at present, and content is on the low side, and its major cause is: in acifluorfen and the 2-chloropropionate condensation course, under this reaction conditions, there are a large amount of side reactions to take place, generate a large amount of by products, thereby influence the content of Loctofen.
Summary of the invention
The object of the present invention is to provide a kind of method for making of high content lactofen original drug, solved and improved the target product generation in the Loctofen building-up process, suppressed the problem that side reaction produces.
Synthetic route of the present invention is: with 3,4-two chlorobenzotrifluorides and m-Salicylic acid, for starting raw material obtains the intermediate product acifluorfen through salify, condensation, acidifying, after nitrated, acifluorfen and 2-chloropropionate are condensed into Loctofen under catalyst action.
The concrete technical scheme that the present invention adopts is: the method for making of high content lactofen original drug, its feature 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, 3 hours time, under reduced pressure deviates from water and the partial solvent that reaction generates.In still, add Anhydrous potassium carbonate and 3.4-two chlorobenzotrifluorides then, continue to be warming up to 152-158 ℃, carry out condensation reaction, condensation reaction 20-22 hour, deviate from the solvent methyl-sulphoxide, 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, after the acidifying end, carries out centrifugation, and cake is drying to obtain 3-[2-chloro-4-(trifluoromethyl) phenoxy group] phenylformic acid.3-[2-chloro-4--(trifluoromethyl) phenoxy group] benzoic acid content 〉=85%.
This 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.
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, the control certain temperature, slowly add nitration mixture, after nitration mixture drips and finishes, back flow reaction, reaction end adopts high performance liquid phase (HPLC) control, qualified back keeps little standing demix that boils, and lower floor's spent acid removes to handle device, and the upper strata dichloromethane solution is put into the precipitation still, steam methylene dichloride, the decompression of precipitation later stage, the solid materials washing behind the precipitation, suction filtration get thick itrated compound; Be intermediate 5-[2-chloro-4-(trifluoromethyl) phenoxy group]-the 2-nitrobenzoic acid.
Reaction conditions:
Material proportion (mol ratio) is an etherate: nitric acid: sulfuric acid=1:1.4:2.9
The dropping temperature of nitration mixture: 20～25 ℃
Holding temperature: 18～20 ℃
5-[2-chloro-4-(trifluoromethyl) phenoxy group]-2-nitrobenzoyl acid content 〉=75%.
Its reaction equation is:
Synthesizing of Loctofen
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:
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, and add-on is 5 ‰～10 ‰.
The lactofen content of the present invention's preparation is 86%～88%, total molar yield 〉=and more than 68% (with 3,4-two chlorobenzotrifluoride meters).
Key point of the present invention is selection of catalysts.Its principle is 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) effect: 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.
The invention has the advantages that:
(1) the Loctofen content height (86%～88%) of the present invention's preparation, yield height (with 3,4-two chlorobenzotrifluoride meters), 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 15.28Kg3.4-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 22.65Kg3-[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 73.25Kg2-chloropropionate (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 the 43.95Kg2-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 15.28Kg3.4-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 22.58Kg3-[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 73.25Kg2-chloropropionate (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 the 43.95Kg2-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 19.86Kg5-[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 43.95Kg2-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 19.84Kg5-[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 43.95Kg2-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 (3)
1. the method for making of a high content lactofen original drug, with 3, to be starting raw material obtain the intermediate product acifluorfen through salify, condensation, acidifying, after nitrated for 4-two chlorobenzotrifluorides and m-Salicylic acid, acifluorfen and 2-chloropropionate are condensed into Loctofen under catalyst action, feature is that described catalyzer is the quaternary ammonium salt catalyzer.
2. the method for making of high content lactofen original drug according to claim 1, it is characterized in that 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.
3. the method for making of high content lactofen original drug according to claim 1 is characterized in that, described catalyst consumption is 5 ‰～10 ‰.
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| CNA2007101128197A CN101386578A (en) | 2007-09-10 | 2007-09-10 | Method for making high content lactofen original drug |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103694123A (en) * | 2014-01-07 | 2014-04-02 | 上虞颖泰精细化工有限公司 | 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 |
| CN105766998A (en) * | 2016-04-15 | 2016-07-20 | 佛山市聚成生化技术研发有限公司 | Preparation method of biodegradable corn field herbicide and prepared biodegradable corn field herbicide |
| CN111732511A (en) * | 2020-07-27 | 2020-10-02 | 西安思科赛实业有限公司 | Preparation process of acifluorfen |
-
2007
- 2007-09-10 CN CNA2007101128197A patent/CN101386578A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103694123A (en) * | 2014-01-07 | 2014-04-02 | 上虞颖泰精细化工有限公司 | Preparation method of lactofen |
| 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 |
| CN105766998A (en) * | 2016-04-15 | 2016-07-20 | 佛山市聚成生化技术研发有限公司 | Preparation method of biodegradable corn field herbicide and prepared biodegradable corn field herbicide |
| CN105766998B (en) * | 2016-04-15 | 2018-07-17 | 佛山市聚成生化技术研发有限公司 | A kind of preparation method of degradable corn field herbicidal and prepared degradable corn field herbicidal |
| CN111732511A (en) * | 2020-07-27 | 2020-10-02 | 西安思科赛实业有限公司 | Preparation process of acifluorfen |
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