CN102757363A - Preparation method of efficient cypermethrin - Google Patents
Preparation method of efficient cypermethrin Download PDFInfo
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- CN102757363A CN102757363A CN2012102677173A CN201210267717A CN102757363A CN 102757363 A CN102757363 A CN 102757363A CN 2012102677173 A CN2012102677173 A CN 2012102677173A CN 201210267717 A CN201210267717 A CN 201210267717A CN 102757363 A CN102757363 A CN 102757363A
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Abstract
The invention discloses a preparation method of efficient cypermethrin. The method comprises the following steps of: dissolving cypermethrin crude oil into alkane, slowly heating to 40-50 DEG C, and fully mixing to form a uniform phase; filtering undissolved substances out, and cooling to the room temperature; adding a guanidine compound while stirring at the temperature of 14-16 DEG C, adding a small amount of efficient cypermethrin solid crystal, reacting at the same temperature for 18-30 hours, gradually cooling to 12-14 DEG C, and preserving heat for reacting for 18-30 hours; cooling to 10-20 DEG C, and preserving heat for 38-58 hours; adding an alkane solvent, cooling to 4-6 DEG C, and preserving heat for 20-28 hours; and sampling and analyzing to determine that the transformation rate of epimerization is 95 percent, slowly adding the acid water of which the pH is 1-2 into a material which is subjected to epimerization while stirring, testing whether the pH is less than 4, removing a water layer, washing to neutral, stirring, and standing for delaminating to obtain an efficient mother liquid. Due to the adoption of the preparation method, inactive isomers in cypermethrin crude oil can be transformed into high-activity isomers, the transformation rate is up 95 percent, and the displacement yield is over 98 percent.
Description
Technical field
The present invention relates to a kind of preparation method of agricultural insecticide, is a kind of preparation method of beta_cypermethrin specifically.
Background technology
General synthetic agricultural chemicals usually is suitable, trans isomer or the left and right mixture that revolves body, needs usually that epimerization through cis-trans-isomer separates, the physico-chemical processes of left dextrorotatory form splits or orientation is synthesized and prepared high-efficient solid isomery agricultural chemicals.Because epimerization mechanism is identical with the isomery mechanism of optics (and how much) isomer under alkalescence or an acidic catalyst effect of organic cpds; Under suitably the alkali of intensity (or acid) acts on; Substituted ethylene basic ring propane carboxylic acid esters is because the carbon atom that the alcohol position upward links to each other with cyanic acid is more active; Change of configuration just easily takes place, and comparatively speaking, the unsymmetrical carbon on the Trimetylene is under attack earlier and racemization takes place.Cis-configuration molecule after the racemization just dissolves in the solvent, and only contain irrotationality photoactive raceme in the solution this moment.As long as reaction conditions control is proper, this configuration racemization just occurs over just on the unsymmetrical carbon of alcohol moiety, and the unsymmetrical carbon on the ring does not then have effect.Raceme carries out protonated in reaction system thereupon, and then causes soluble part to form the ester of 2 diastereomers ［ S and R ］ alcohol of equimolecular ratio.
Cypermethrin crude oil is eight kinds of mixture of isomers; Be 1RcisR/1ScisS or 1RtransR/1StransS (suitable, the anti-body of poor efficiency); 1RcisS/1ScisR or 1RtransS ∕ 1StransR (efficiently suitable, anti-body); Wherein efficient isomer has only two kinds, comprises that its enantiomorph only accounts for the 35%-45% of total ester, all the other then relative poor efficiency or nearly unavailables.These poor efficiencys or invalid element be prevention and elimination of disease and pests effectively not only, and has improved the usage quantity of medicament, contaminate environment, the drug residue of increase agricultural-food.Therefore, mutual conversion and reaction thereof between the research isomer obtain effective steric isomer in industry, be very important problem.
Summary of the invention
The preparation method who the purpose of this invention is to provide the beta_cypermethrin that a kind of technical process is simple and feasible, transformation efficiency is high.
The preparation method of a kind of beta_cypermethrin provided by the invention is dissolved in cypermethrin crude oil in the alkane, slowly is heated to 40～50 ℃, and thorough mixing makes it to become homogeneous phase; Remove by filter insolubles, again cool to room temperature; Under 14～16 ℃, stir the adding guanidine compound, and add a little beta_cypermethrin solid crystal seed, after reacting 18～30 h under this temperature, cool to 12～14 ℃ gradually, insulation reaction 18～30 h; Reduce to 10～12 ℃ again, insulation 38～58 h; And then the adding alkane solvent is cooled to 4～6 ℃, insulation 20～28h; The transformation efficiency of sampling analysis epimerization is 95%, is 1～2 sour water with preparing pH, under agitation above-mentioned sour water is slowly added in the material of having accomplished epimerization; Survey pH < 4; Branch vibration layer is washed to neutrality again, stirs static layering, obtains the active isomer mother liquor; Wherein the feed ratio of cypermethrin crude oil, alkane, guanidine compound and crystal seed is 90～110g:90～110 ml:0.1～5g:0.3～0.5g, and the alkane that is used to dissolve cypermethrin crude oil accounts for 75～85% of its total consumption.
Catalyzer is selected guanidine compound, is because it had both had good katalysis, has both the dual nature of organic bases, mineral alkali again simultaneously.
Guanidine compound is one type of strong organic bases, in general physiological environment, is in complete proton state, and can in the pH of broad scope, keep positive polarity, and this is for the bonding negatively charged ion and promote catalytic performance and obviously be superior to mineral alkali and other organic alkali catalyst.The catalytic mechanism of guanidine compound mainly is: form the zwitter-ion hydrogen bond through the negatively charged ion transition state; The electric charge that disperses transition state with the form of resonance; Reach stable transition state, the purpose of reduction reaction activity; Guanidine compound after modifying then can be used for asymmetry catalysis, and catalysis efficiency is excellent.
In the present invention, guanidine compound is Guanidinium carbonate, methylguanidine, tetramethyl guanidine, bicyclo guanidine or MTBD.
Select alkane solvent; The consistency of it and active isomer is not high; Than old technology with Virahol as solvent, transposition finishes and contains a large amount of Virahols in the water that aftertreatment branches away, and need carry out the recycling of Virahol to waste water; Treating processes will adopt the high tower fractionation could reclaim the above Virahol of 98% content; Virahol volatilization a large amount of losses not only can occur and also can pollute to environment in removal process, also can produce waste water in the treating processes, also environment is polluted in the time of waste water resource.Make solvent with alkane and directly can prepare the mother liquor product, just do not use the rectifying tower purification and reclaim, reached the purpose of energy-saving and emission-reduction consumption reductions.
Because selected alkanes organic solvent is bigger to the solvency action that molecule had of ［ R ］ configuration, oppose that mutually ［ S ］ configuration is then less, so the ester of ［ S ］ configuration is constantly separated out with crystallized form from the solution center; And the excellent asymmetric catalyst effect of guanidine compound performance usefulness makes the ester of ［ R ］ configuration that the racemization transposition constantly take place.So; As long as the ester of continual making ［ S ］ configuration from reaction system in a continuous manner crystallization separate out, break the balance of original reaction system, make reaction all the time to the right direction carry out; The racemization transposition is carried out thoroughly, to make the beta_cypermethrin isomer.
In the present invention, alkane is pentane, hexane, hexanaphthene, heptane, suberane, octane or nonane.
In above-mentioned, the acid in the sour water is hydrochloric acid, sulfuric acid or Glacial acetic acid min. 99.5.
The present invention is starting raw material with the cypermethrin crude oil; With the guanidine compound is catalyzer; Adopt alkane solvent to substitute alcohols and prepare beta_cypermethrin, the isomer of non-activity in the cypermethrin crude oil is changed into highly active isomer, experiment shows; Transformation efficiency reaches 95%, and transposition yield is up to more than 98%.Technical process of the present invention is simple and feasible, reaches energy-saving and cost-reducing purpose simultaneously.
Embodiment
Embodiment: get the 100g total ester content and be not less than 93% cypermethrin crude oil and be dissolved in the 80 ml normal hexanes, slowly be heated to 45 ℃, stir, make it to become homogeneous phase; Remove by filter insolubles, again cool to room temperature; Under 15 ℃, stir adding 2g Guanidinium carbonate, and add beta_cypermethrin solid crystal seed 0.4g, cooling to 13 ℃ gradually, insulation reaction 24 h behind reaction 24 h under this temperature; Reduce to 11 ℃ again, be incubated 48 h; Be incubated, added 20 ml alkane solvents and be cooled to 5 ℃, insulation 24h; Get middle control, transformation efficiency is up to 95%, is that 1 sour water under agitation slowly adds in the good material of transposition with the pH that uses Glacial acetic acid min. 99.5 to prepare, and < 4, branch vibration layer is washed to neutrality again, stirs static layering, obtains the active isomer mother liquor to survey pH.
Normal hexane and Guanidinium carbonate in above-mentioned are analytical pure.
Claims (5)
1. the preparation method of a beta_cypermethrin is characterized in that, cypermethrin crude oil is dissolved in the alkane, slowly is heated to 40～50 ℃, and thorough mixing makes it to become homogeneous phase; Remove by filter insolubles, again cool to room temperature; Under 14～16 ℃, stir the adding guanidine compound, and add a little beta_cypermethrin solid crystal seed, after reacting 18～30 h under this temperature, cool to 12～14 ℃ gradually, insulation reaction 18～30 h; Reduce to 10～12 ℃ again, insulation 38～58 h; And then the adding alkane solvent is cooled to 4～6 ℃, insulation 20～28h; The transformation efficiency of sampling analysis epimerization is 95%, is 1～2 sour water with preparing pH, under agitation above-mentioned sour water is slowly added in the material of having accomplished epimerization; Survey pH < 4; Branch vibration layer is washed to neutrality again, stirs static layering, obtains the active isomer mother liquor; Wherein the feed ratio of cypermethrin crude oil, alkane, guanidine compound and crystal seed is 90～110g:90～110 ml:0.1～5g:0.3～0.5g, and the alkane that is used to dissolve cypermethrin crude oil accounts for 75～85% of its total consumption.
2. the preparation method of a kind of beta_cypermethrin according to claim 1 is characterized in that, alkane is pentane, hexane, hexanaphthene, heptane, suberane, octane or nonane.
3. the preparation method of a kind of beta_cypermethrin according to claim 1 is characterized in that, guanidine compound is Guanidinium carbonate, methylguanidine, tetramethyl guanidine, bicyclo guanidine or MTBD.
4. the preparation method of a kind of beta_cypermethrin according to claim 1 is characterized in that, the acid in the sour water is hydrochloric acid, sulfuric acid or Glacial acetic acid min. 99.5.
5. the preparation method of a kind of beta_cypermethrin according to claim 1 is characterized in that, total ester content is not less than 93% in the cypermethrin crude oil.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106818847A (en) * | 2017-03-15 | 2017-06-13 | 合肥华创现代农业科技有限公司 | A kind of starch sustained-release micro-spheres comprising effective cypermethrin and preparation method thereof |
| CN106942265A (en) * | 2017-03-15 | 2017-07-14 | 合肥华创现代农业科技有限公司 | A kind of plant oil base micro emulsion oil comprising effective cypermethrin and preparation method thereof |
| CN106942264A (en) * | 2017-03-15 | 2017-07-14 | 合肥华创现代农业科技有限公司 | A kind of aqueous emulsion of phosphate compounding comprising effective cypermethrin and preparation method thereof |
| CN106957194A (en) * | 2017-03-15 | 2017-07-18 | 合肥华创现代农业科技有限公司 | A kind of composite fertilizer with pesticide particle comprising effective cypermethrin and preparation method thereof |
| CN106962392A (en) * | 2017-03-15 | 2017-07-21 | 合肥华创现代农业科技有限公司 | A kind of biomass carbon particle for loading effective cypermethrin and preparation method thereof |
| CN114982776A (en) * | 2022-05-17 | 2022-09-02 | 中研瑞科科技(北京)有限公司 | Fullerene functional liquid for preventing and treating root knot nematode disease of crops and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2075011A (en) * | 1980-04-23 | 1981-11-11 | Shell Int Research | Process for Preparing Cyclopropane Carboxylic Acid Ester Derivatives |
| CN1042348A (en) * | 1989-11-01 | 1990-05-23 | 南开大学 | The improvement of method for producing high efficiency cis-and trans-cypermethrin |
| US5128497A (en) * | 1990-01-03 | 1992-07-07 | Fmc Corporation | Conversion of pyrethroid isomers to more active species |
| CN1068933A (en) * | 1991-07-27 | 1993-02-17 | 张曾如 | Manufacturing method for high active chloro-cyanogen pyrethrin pesticide |
-
2012
- 2012-07-31 CN CN2012102677173A patent/CN102757363A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2075011A (en) * | 1980-04-23 | 1981-11-11 | Shell Int Research | Process for Preparing Cyclopropane Carboxylic Acid Ester Derivatives |
| CN1042348A (en) * | 1989-11-01 | 1990-05-23 | 南开大学 | The improvement of method for producing high efficiency cis-and trans-cypermethrin |
| US5128497A (en) * | 1990-01-03 | 1992-07-07 | Fmc Corporation | Conversion of pyrethroid isomers to more active species |
| CN1068933A (en) * | 1991-07-27 | 1993-02-17 | 张曾如 | Manufacturing method for high active chloro-cyanogen pyrethrin pesticide |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106818847A (en) * | 2017-03-15 | 2017-06-13 | 合肥华创现代农业科技有限公司 | A kind of starch sustained-release micro-spheres comprising effective cypermethrin and preparation method thereof |
| CN106942265A (en) * | 2017-03-15 | 2017-07-14 | 合肥华创现代农业科技有限公司 | A kind of plant oil base micro emulsion oil comprising effective cypermethrin and preparation method thereof |
| CN106942264A (en) * | 2017-03-15 | 2017-07-14 | 合肥华创现代农业科技有限公司 | A kind of aqueous emulsion of phosphate compounding comprising effective cypermethrin and preparation method thereof |
| CN106957194A (en) * | 2017-03-15 | 2017-07-18 | 合肥华创现代农业科技有限公司 | A kind of composite fertilizer with pesticide particle comprising effective cypermethrin and preparation method thereof |
| CN106962392A (en) * | 2017-03-15 | 2017-07-21 | 合肥华创现代农业科技有限公司 | A kind of biomass carbon particle for loading effective cypermethrin and preparation method thereof |
| CN114982776A (en) * | 2022-05-17 | 2022-09-02 | 中研瑞科科技(北京)有限公司 | Fullerene functional liquid for preventing and treating root knot nematode disease of crops and preparation method thereof |
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Application publication date: 20121031 |