CN106632463A - Preparation method and use of phenthoate stereoisomer - Google Patents
Preparation method and use of phenthoate stereoisomer Download PDFInfo
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- CN106632463A CN106632463A CN201611218224.5A CN201611218224A CN106632463A CN 106632463 A CN106632463 A CN 106632463A CN 201611218224 A CN201611218224 A CN 201611218224A CN 106632463 A CN106632463 A CN 106632463A
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- phenthoate dimephenthoate
- dimephenthoate cidial
- phenthoate
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- XAMUDJHXFNRLCY-UHFFFAOYSA-N phenthoate Chemical class CCOC(=O)C(SP(=S)(OC)OC)C1=CC=CC=C1 XAMUDJHXFNRLCY-UHFFFAOYSA-N 0.000 title claims abstract description 170
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000000706 filtrate Substances 0.000 claims abstract description 3
- 239000007787 solid Substances 0.000 claims abstract description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 20
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 238000012986 modification Methods 0.000 claims description 15
- 230000004048 modification Effects 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000004088 simulation Methods 0.000 claims description 10
- -1 phenthoate dimephenthoate cidial stereoisomer Chemical class 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 8
- 239000003480 eluent Substances 0.000 claims description 8
- 239000001913 cellulose Substances 0.000 claims description 7
- 229920002678 cellulose Polymers 0.000 claims description 7
- 239000002917 insecticide Substances 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- 230000000844 anti-bacterial effect Effects 0.000 claims description 6
- 239000003899 bactericide agent Substances 0.000 claims description 6
- 238000002347 injection Methods 0.000 claims description 6
- 239000007924 injection Substances 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 6
- 239000000945 filler Substances 0.000 claims description 5
- 239000011343 solid material Substances 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 238000003795 desorption Methods 0.000 claims description 4
- 238000005070 sampling Methods 0.000 claims description 4
- 238000001179 sorption measurement Methods 0.000 claims description 4
- KPCOLEDDUNYSQA-UHFFFAOYSA-N (3,5-dimethylphenyl)carbamic acid Chemical class CC1=CC(C)=CC(NC(O)=O)=C1 KPCOLEDDUNYSQA-UHFFFAOYSA-N 0.000 claims description 3
- 235000007164 Oryza sativa Nutrition 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 150000007530 organic bases Chemical class 0.000 claims description 3
- 235000009566 rice Nutrition 0.000 claims description 3
- CVXBEEMKQHEXEN-UHFFFAOYSA-N carbaryl Chemical compound C1=CC=C2C(OC(=O)NC)=CC=CC2=C1 CVXBEEMKQHEXEN-UHFFFAOYSA-N 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 238000004321 preservation Methods 0.000 claims 1
- 239000000575 pesticide Substances 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 7
- 238000004587 chromatography analysis Methods 0.000 abstract description 3
- 230000001954 sterilising effect Effects 0.000 abstract description 2
- 238000004659 sterilization and disinfection Methods 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract 2
- 230000002349 favourable effect Effects 0.000 abstract 1
- 238000001953 recrystallisation Methods 0.000 abstract 1
- 230000017105 transposition Effects 0.000 abstract 1
- 239000003905 agrochemical Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 230000000749 insecticidal effect Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000523 sample Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 241000238578 Daphnia Species 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 231100000419 toxicity Toxicity 0.000 description 3
- 230000001988 toxicity Effects 0.000 description 3
- HBAQYPYDRFILMT-UHFFFAOYSA-N 8-[3-(1-cyclopropylpyrazol-4-yl)-1H-pyrazolo[4,3-d]pyrimidin-5-yl]-3-methyl-3,8-diazabicyclo[3.2.1]octan-2-one Chemical class C1(CC1)N1N=CC(=C1)C1=NNC2=C1N=C(N=C2)N1C2C(N(CC1CC2)C)=O HBAQYPYDRFILMT-UHFFFAOYSA-N 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 241000607479 Yersinia pestis Species 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000000857 drug effect Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 241001530056 Athelia rolfsii Species 0.000 description 1
- 241001494246 Daphnia magna Species 0.000 description 1
- 230000005526 G1 to G0 transition Effects 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- QTNSTIREPWXBLE-UHFFFAOYSA-N anilino carbamate Chemical compound NC(=O)ONC1=CC=CC=C1 QTNSTIREPWXBLE-UHFFFAOYSA-N 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 231100000820 toxicity test Toxicity 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000001018 virulence Effects 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/16—Esters of thiophosphoric acids or thiophosphorous acids
- C07F9/165—Esters of thiophosphoric acids
- C07F9/1653—Esters of thiophosphoric acids with arylalkanols
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
- A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
- A01N43/14—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings
- A01N43/16—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings with oxygen as the ring hetero atom
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
- A01N47/22—O-Aryl or S-Aryl esters thereof
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
- A01N57/10—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds
- A01N57/14—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds containing aromatic radicals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/07—Optical isomers
Landscapes
- Life Sciences & Earth Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Health & Medical Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
- Chemical & Material Sciences (AREA)
- Plant Pathology (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Organic Chemistry (AREA)
- Biochemistry (AREA)
- Molecular Biology (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention relates to a preparation method and use of a phenthoate stereoisomer. The preparation method comprises the following steps: dissolving an ordinary phenthoate raw pesticide containing S-phenthoate and R-phenthoate into a mobile phase, and performing industrial separation to obtain solids rich in the S-phenthoate and filtrate rich in the R-phenthoate by adopting simulated moving bed chromatography; performing low-temperature desolventizing and recrystallization to obtain an S-phenthoate raw pesticide and an R-phenthoate raw pesticide. The phenthoate stereoisomer has better sterilization effects, and is more ecological and environment-friendly, efficient successful separation of the enantiomer R-phenthoate and transposition reutilization of the S-phenthoate are more favorable for popularization and application, and the using amount of a pesticide is reduced.
Description
Technical field
The present invention relates to preparation technique of pesticide field, and in particular to the preparation method and its use of phenthoate dimephenthoate cidial stereoisomer
On the way.
Background technology
Phenthoate dimephenthoate cidial is a kind of agricultural chemicals to insect pest with good prevention effect, and it is a kind of replacement high-toxic organic phosphorus agricultural chemicals
The biodegradable pesticide kind of low toxicity, has desinsection, biocidal efficacies concurrently, is there is good prevention effect to rice grub
Meanwhile, to prevent and treat rice green smut, banded sclerotial blight, black kernel have it is certain it is simultaneous control effect, and to pest natural enemy and to feeding
Newborn animal has preferable security.Since developing from Italian Meng Tekadini companies sixties, production in the market and
The phenthoate dimephenthoate cidial product of sale is mainly the mixture of its racemic modification.
There is an asymmetric carbon atom, Jing biological activity tests, R- phenthoate dimephenthoate cidial insecticidal activity is better than S- in phenthoate dimephenthoate cidial molecule
Phenthoate dimephenthoate cidial, its biologically active differs 2-5 times, and both chemical structural formulas are as follows：
Wang Ping, Zhou Zhiqiang, Ye Guibiao, wait that (" high performance liquid chromatography Cellulose based CSP is to racemic phenthoate dimephenthoate cidial
Split ",《Agricultural chemicals》, 2004,43 (12)：The CDMPC chiral stationary phases of its synthesis 542-546) be have studied to phenthoate dimephenthoate cidial racemic
Body has and preferably split ability, but its emphasis also rests on microseparation conceptual phase.
The preparation of industrialization of phenthoate dimephenthoate cidial stereoisomer and purposes are temporarily without concrete report.
To sum up, there is a need in the art for one kind can economical and efficiently split phenthoate dimephenthoate cidial racemic modification, have more to obtain
The R- phenthoate dimephenthoate cidial enantiomters of excellent insecticidal activity can industrialized production technology of preparing, so as to reduce Pesticide use amount, drop
Low cost, improves insecticidal effect, and to more environment-friendly.
The content of the invention
For achieving the above object, inventor after research and testing, having obtained being capable of efficient separating phenthoate dimephenthoate cidial racemic modification
The method of mixture, specifically, the method that present invention employs Simulation moving bed carrys out resolving chiral compound phenthoate dimephenthoate cidial mapping
Isomers.
Simulation moving bed is the mass transfer apparatus that a kind of utilization absorption principle carries out liquid lock out operation.It is continuous with adverse current
Mode of operation, by the material import and export position for converting fixed bed absorption equipment, generation is continuously moved down equivalent to adsorbent,
And the effect that material is continuously moved up.The production capacity and separative efficiency of this equipment is higher than fixed adsorption bed, can avoid again
Channel between moving bed adsorption abrasion, fragment or dust occluding device or pipeline and solid particle seam.
The simulated moving bed process of resolving chiral compound phenthoate dimephenthoate cidial enantiomter of the present invention, is characterized in that using simulation
Mobile bed chromatic system, filler be cellulose 3,5- dimethylphenylcarbamates, with n-hexane and isopropanol (V:V)=5:
1 is mobile phase, and highly purified R- phenthoate dimephenthoate cidial and S- phenthoate dimephenthoate cidial are split out from the racemic modification of phenthoate dimephenthoate cidial.The present invention is with regard to simulation
The breakthrough of moving bed technology of preparing, for environment friendly agricultural industrialized production is instructed, with high activity enantiomer racemic agricultural chemicals is replaced,
The usage amount of agricultural chemicals is reduced, it is all significant in terms of reducing environmental pressure and increasing Pesticide use security.
One aspect of the present invention provides a kind of preparation method of phenthoate dimephenthoate cidial stereoisomer, and the preparation method is adopted
Simulation moving bed splits to phenthoate dimephenthoate cidial racemic modification, and comprises the following steps：
(1) by phenthoate dimephenthoate cidial racemic modification flowing phased soln, the concentration after dissolving is 1～100mg/ml, and by sampling pump
Into the chromatographic system of Simulation moving bed, filler is cellulose 3,5- dimethylphenylcarbamates or cellulose iii phenylamino
Carbamate,
Chromatographic system is divided into four areas, wherein an area is located between eluent entrance and extracting liquid outlet, realizes in this area
The desorption of S- phenthoate dimephenthoate cidial；2nd area be located between extracting liquid outlet and injection port, this area make S- phenthoate dimephenthoate cidial repeatedly Adsorption and desorption,
Concentration；3rd area are located between injection port and raffinate outlet, and in this area R- phenthoate dimephenthoate cidial is obtained；4th area are located at raffinate and export and wash
On the one hand between de- liquid entrance, the eluent in 3rd area enters into area's reusable edible, another aspect Jiang Sanqu and one separate from
R- phenthoate dimephenthoate cidial in opening to prevent raffinate enters into an area；
(2) the R- phenthoate dimephenthoate cidial and S- phenthoate dimephenthoate cidial of acquisition are carried out into concentration to refine, obtains the product that purity is more than 97%.
Further, mobile phase described in step (1) is the mixture of n-hexane and any proportioning of isopropanol, i.e. both bodies
Product proportioning (V:V) it is n-hexane:Isopropanol=(0-100):(0-100), further preferred n-hexane:Isopropanol (V:V)=5:
1。
Further, the concentration in step (1) after phenthoate dimephenthoate cidial racemic modification flowing phased soln is 40-80mg/ml, enters one
Step is preferably 60-70mg/ml.
Further, the operation temperature of the chromatographic system of described Simulation moving bed is 0-50 DEG C, more preferably 25-
45℃。
Further, the preparation method also includes：To dissolve after the gained removing mobile phase of the filtrate rich in S- phenthoate dimephenthoate cidial
In methyl alcohol or ethanol, it is subsequently adding appropriate organic base and adjusts pH value to 6.2, be heated to 45 DEG C, is incubated 24h so that about 50%
Enantiomer conversion；Then methyl alcohol or ethanol are sloughed, solid material is obtained, the solid material is returned as the common active compound of phenthoate dimephenthoate cidial
With.
Further, the weight ratio of S- phenthoate dimephenthoate cidial and R- phenthoate dimephenthoate cidial is (46-50) in the solid material：(50-54).
Further, the R- phenthoate dimephenthoate cidial for being obtained is positioned over into the low poles such as isopropanol, acetone, dichloromethane, n-hexane
Preserve in solvent.R- phenthoate dimephenthoate cidial is stable in above-mentioned solvent, without enantiomer Transformation Phenomenon, is conducive to long term storage, will not reduce
Drug effect.
Another aspect of the present invention provides phenthoate dimephenthoate cidial stereoisomer R- phenthoate dimephenthoate cidial, and the R- phenthoate dimephenthoate cidial is by this
The preparation method of bright phenthoate dimephenthoate cidial stereoisomer is obtained.
Another aspect of the invention provides phenthoate dimephenthoate cidial stereoisomer R- phenthoate dimephenthoate cidial as insecticide and bactericide
Using.
Another aspect of the invention provides a kind of insecticide and bactericide, and the insecticide and bactericide include above-mentioned
R- phenthoate dimephenthoate cidial stereoisomer and mixed thing, the mixed thing includes at least one in sevin and kasugarnycin.
Present invention achieves phenthoate dimephenthoate cidial efficient insecticide sterilization isomers R- phenthoate dimephenthoate cidial be successfully separated and can volume production industrialization；
It is raw to survey insecticidal bactericide drug effect height, dosage province that result is shown R- phenthoate dimephenthoate cidial and obtained by mixture, to crop and environment
It is ecological safer；, the market competitiveness low with respect to cost accounting is strong, meets the direction of current Agrochemicals.
Specific embodiment
Technical solution of the present invention is described further below by embodiment.It will be appreciated that following examples are only used for
Bright technical solution of the present invention, but it is not limited to the scope of the present invention.
Embodiment 1
1st, equipment and condition are selected
Using simulated moving bed chromatography system include wash-out pump, sampling pump, extraction pump, chromatographic column, magnetic valve, thermostat
With the part such as system controller and computer.Sample solution and eluent are respectively from sample liquid entrance and eluent entrance injection system
System, two enantiomers of phenthoate dimephenthoate cidial flow out respectively from two outlets of raffinate and extract.At regular intervals often, sample liquid
Export with eluent entrance, extract and raffinate and switch to next chromatographic column along the direction of mobile phase flowing.
2nd, chromatographic column filler and mobile phase solvent are selected
Fillers selection Cellulose trisphenylcarbamate, with n-hexane and isopropanol (V:V)=5:1 is mobile phase.
3rd, separating step
(1) sample flowing phased soln, concentration is 60mg/ml after dissolving, and by sampling pump chromatographic system, sample introduction concentration are injected
Increase be conducive to improving yield, but its concentration limited by phenthoate dimephenthoate cidial solubility.Chromatographic system prepares post group by 4～24
Into, it is divided into 4 areas, the more separating effects of chromatographic column number are better, but the complexity and system pressure of system are higher, optimal
It is 8～12.By the controller of simulated moving bed chromatography system, periodically the opening and closing of control magnetic valve, makes injection port, extract
Outlet and residual solution outlet are periodically converted along the direction of mobile phase, make two enantiomers of phenthoate dimephenthoate cidial from extract and raffinate two
Individual outlet outflow system.
(2) it is the product solution for obtaining is refined through concentration, obtain the qualified products of purity 97.8%.
Embodiment 2
The phenthoate dimephenthoate cidial raceme crude oil of 100g purity >=92% is dissolved in n-hexane/isopropanol double solvents, is tied again
Crystalline substance obtains phenthoate dimephenthoate cidial raceme active compound 70g (mother liquid recycle is to improve refined yield) of purity >=96%.By purity >=96%
Phenthoate dimephenthoate cidial raceme active compound is dissolved into mobile phase (n-hexane and isopropanol (V by 7g/L:V)=5:1) in, adjust into sample liquid, extraction
Liquid, eluent flow rate are taken, is automatically separated in 15 DEG C of conditions of column temperature, collected extract and raffinate is distinguished low temperature desolventizing and recrystallized
S- phenthoate dimephenthoate cidial and R- phenthoate dimephenthoate cidial, S- phenthoate dimephenthoate cidial purity 98.0%, R- phenthoate dimephenthoate cidial purity 98.2%.
Embodiment 3
Toxicity test adopts iso standard method, first drafts 5 concentration, a blank according to the preliminary data that trial test draws
Control, each concentration is parallel 4 groups, and in each beaker (50ml) 5 same type Daphnia magnas are put.20 DEG C of water temperature, does not change solution difference
Draw 48h-LC50Value.
Jing determines the toxicity of phenthoate dimephenthoate cidial racemic modification and its enantiomer：R- phenthoate dimephenthoate cidial insecticidal toxicities are significantly better than racemic modification
Phenthoate dimephenthoate cidial.LC of the R- phenthoate dimephenthoate cidial to Daphnia magna50It is worth for 0.73mg/L, LC of the racemic modification phenthoate dimephenthoate cidial to Daphnia magna50It is worth and is
1.77mg/L, the two toxicity differs 2.42 times；LC of the S- phenthoate dimephenthoate cidial to Daphnia magna50It is worth for 4.12mg/L, the virulence of R- phenthoate dimephenthoate cidial
It is stronger than S- phenthoate dimephenthoate cidial 5.64 times.
Embodiment 4
50g S- phenthoate dimephenthoate cidial active compounds are dissolved in 100ml methyl alcohol or ethanol solution, appropriate organic base are subsequently adding and are adjusted
PH value is warming up to 45 DEG C to 6.2, detects after insulation 24h, S- and R- enantiomers about respectively account for 50%, and poorly efficient body is capable of achieving indexing,
Active compound continues on for the fractionation of effective body after precipitation.
Although the present invention is described in detail above to have used general explanation and specific embodiment, at this
On the basis of invention, it can be made some modifications or improvements, this will be apparent to those skilled in the art.Therefore,
Without departing from theon the basis of the spirit of the present invention these modifications or improvements, belong to the scope of protection of present invention.
Claims (10)
1. a kind of preparation method of phenthoate dimephenthoate cidial stereoisomer, it is characterised in that the preparation method adopts Simulation moving bed pair
Phenthoate dimephenthoate cidial racemic modification is split, and is comprised the following steps：
(1) by phenthoate dimephenthoate cidial racemic modification flowing phased soln, the concentration after dissolving is 1～100mg/ml, and by sampling pump
Into the chromatographic system of the Simulation moving bed, filler is cellulose 3,5- dimethylphenylcarbamates or cellulose triphen
Aminocarbamic acid ester,
Chromatographic system is divided into into four areas, wherein an area is located between eluent entrance and extracting liquid outlet, in this area S- is realized
The desorption of phenthoate dimephenthoate cidial；2nd area are located between extracting liquid outlet and injection port, and in this area S- phenthoate dimephenthoate cidial Adsorption and desorption, dense repeatedly is made
Contracting；3rd area are located between injection port and raffinate outlet, and in this area R- phenthoate dimephenthoate cidial is obtained；4th area are located at raffinate and export and wash-out
Between liquid entrance, on the one hand the eluent in 3rd area enters into area's reusable edible, and another aspect Jiang Sanqu is separated with one and left
R- phenthoate dimephenthoate cidial in prevent raffinate enters into an area；
(2) the R- phenthoate dimephenthoate cidial and S- phenthoate dimephenthoate cidial of acquisition are carried out into concentration to refine, obtains the product that purity is more than 97%.
2. preparation method as claimed in claim 1, it is characterised in that the mobile phase is the mixing of n-hexane and isopropanol
Thing.
3. preparation method as claimed in claim 1, it is characterised in that the phenthoate dimephenthoate cidial racemic modification is with after flowing phased soln
Concentration is 40-80mg/ml.
4. preparation method as claimed in claim 1, it is characterised in that the operation temperature of the chromatographic system of the Simulation moving bed
For 0-50 DEG C.
5. the preparation method as any one of claim 1-4, it is characterised in that the preparation method also includes：By institute
Must be rich in after the filtrate of S- phenthoate dimephenthoate cidial removing mobile phase and be dissolved in methyl alcohol or ethanol, be subsequently adding appropriate organic base and adjust pH value
To 6.2,45 DEG C are heated to, are incubated 24h so that 50% enantiomer conversion；Then methyl alcohol or ethanol are sloughed, solids is obtained
Material, the solid material is used as the common active compound reuse of phenthoate dimephenthoate cidial.
6. preparation method as claimed in claim 5, it is characterised in that S- phenthoate dimephenthoate cidial and R- phenthoate dimephenthoate cidial in the solid material
Weight ratio is (46-50)：(50-54).
7. preparation method as claimed in claim 6, it is characterised in that the preparation method also includes：By the R- rice for being obtained
Rich dissipating is positioned over preservation in isopropanol, acetone, dichloromethane or n-hexane solvent.
8. such as R- phenthoate dimephenthoate cidial stereoisomers that any one of claim 1-7 preparation method is obtained.
9. the R- phenthoate dimephenthoate cidial stereoisomer for being obtained such as any one of claim 1-7 preparation method is used as insecticide and sterilized
The purposes of agent.
10. a kind of insecticide and bactericide, it is characterised in that the insecticide and bactericide include as claimed in claim 8
R- phenthoate dimephenthoate cidial stereoisomer and mixed thing, the mixed thing includes at least one in sevin and kasugarnycin.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101309583A (en) * | 2003-12-22 | 2008-11-19 | 巴斯福股份公司 | Composition for the impregnation of fibers, fabrics and nettings imparting a protective activity against pests |
-
2016
- 2016-12-26 CN CN201611218224.5A patent/CN106632463A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101309583A (en) * | 2003-12-22 | 2008-11-19 | 巴斯福股份公司 | Composition for the impregnation of fibers, fabrics and nettings imparting a protective activity against pests |
Non-Patent Citations (3)
| Title |
|---|
| 吕裕斌: "模拟移动床分离天然产物的研究", 《中古优秀博硕士学位论文全文数据库（博士）工程科技I辑》 * |
| 屠云杰: "稻丰散和三氯杀虫酯的环境毒理及归趋研究", 《中国优秀硕士学位论文全文数据库工程科技I辑》 * |
| 柳春辉: "模拟移动床色谱分离制备手性药物雷诺嗪的研究", 《中国化学会第二十四届学术年会论文摘要集》 * |
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