CN85105604A - Insecticidal esters - Google Patents
Insecticidal esters Download PDFInfo
- Publication number
- CN85105604A CN85105604A CN85105604.0A CN85105604A CN85105604A CN 85105604 A CN85105604 A CN 85105604A CN 85105604 A CN85105604 A CN 85105604A CN 85105604 A CN85105604 A CN 85105604A
- Authority
- CN
- China
- Prior art keywords
- alkene
- alpha
- chloro
- fluoro
- cyano
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- 230000000749 insecticidal effect Effects 0.000 title claims abstract description 5
- 150000002148 esters Chemical class 0.000 title description 4
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- -1 alpha-cyano-4-fluoro-3-benzyloxy phenoxy Chemical group 0.000 claims description 55
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- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
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- 239000004575 stone Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000012747 synergistic agent Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 125000005207 tetraalkylammonium group Chemical group 0.000 description 1
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 description 1
- RXMRGBVLCSYIBO-UHFFFAOYSA-M tetramethylazanium;iodide Chemical compound [I-].C[N+](C)(C)C RXMRGBVLCSYIBO-UHFFFAOYSA-M 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 description 1
Abstract
A pair of -alpha-cyano-4-fluoro-3-phenoxybenzyl (1R, cis) -3- (z-2-chloro-3, 3, 3-trifluoroprop-1-en-1-yl) -2, 2-dimethylcyclopropane carboxylic acid esters and the preparation of the enantiomers thereof are described. The para-isomer is converted to a more effective insecticidal compound in solution by base-catalyzed epimerization, represented by (S) - α -cyano-4-fluoro-3-phenoxybenzyl (1R, cis) -3- (z-2-chloro-3, 3, 3-trifluoroprop-1-en-1-yl) -2, 2-dimethylcyclopropanecarboxylate and its enantiomer, and crystallized from solution.
Description
The invention relates to a kind of new-type effective desinsection product, it is made up of the racemic mixture of two kinds of isomer.
Compound (±)-d-cyano group-4-fluoro-3-benzyloxy phenoxy base (±)-suitable/anti--3-(2-chloro-3,3,3-trifluoropropyl-1-alkene-1-yl)-2, the method for making of 2-dimethyl cyclopropane carboxylic acid ester is announced in No. 0008340 at european patent application and is mentioned, but the mixture to this compound cis and trans-isomer(ide) is not described in detail, and it may be eight cis-isomerides and eight trans-isomer(ide)s.
The present invention proposes a kind of novel insect-killing product that comprises just two kinds of isomer that exist with racemic object form, this racemoid is by (S)-alpha-cyano-4-fluoro-3-phenoxy benzyl (1R, suitable)-3-(Z-2-chloro-3,3,3-trifluoropropyl-1-alkene-1-yl)-2,2-dimethyl cyclopropane carboxylic acid ester and its enantiomorph (R)-alpha-cyano-4-fluoro-3-benzyloxy phenoxy base (1S, suitable)-3-(Z-2-fluoro-3,3,3-trifluoropropyl-1-alkene-1-yl)-2,2-dimethyl cyclopropane carboxylic acid ester forms, and has removed other isomer of same compound in fact, and below will claim it to be " racemoid ".
Can from the mixture of foreign body object, obtain racemoid with chromatography, for example: can be from (1RS, suitable)-3-(Z-2-chloro-3,3,3-trifluoropropyl-1-alkene-1-yl)-2, obtain it in four kinds of isomer that 2-dimethyl cyclopropane carboxylic acid and (RS)-4-fluoro-esterification of 3-phenoxy benzonitrile aldehyde hydrogen alcohol obtains.Alkali metal cyanide, water are arranged, when phase-transfer catalyst (for example: resemble the salt the halogenation tetraalkyl ammonium) and organic solvent exist arbitrarily, this product can be made by 4-fluoro-3-phenoxy benzonitrile aldehyde and hydrochloric acid reaction easily.This only by at 2-chloro-3,3, have the product that four cis-isomerides of Z-configuration form on the 3-trifluoro-propenyl and formerly do not obtain describing, so it has also constituted a part of the present invention, and will claim that below this product is " initiator ".It is compared with the effectiveness of trans-isomer(ide) mixture with previously described cis, and the latter is a kind of more effective sterilant.In any case this racemoid of discussing previously of being made up of two kinds of individual isomer is a kind of more effective desinsection product.
Here usefulness " removing in fact " means, and the weight of other isomer that contains the same compound of product of racemoid is not more than 10%.
Utilize high efficiency liquid chromatography, can finish the chromatographic separation of racemoid, with alkane (as normal hexane) with have than the silicon post of high polarity material (, resembling ethyl acetate) mixture wash-out and preferentially select for use as ester.
Use crystallization technique can obtain the racemoid crystal equally.
This technology provides a kind of method that obtains crystalline material (below will claim this crystalline material to be ' product '), crystalline material is in fact by being expressed as (S)-alpha-cyano-3-benzyloxy phenoxy base (1R, suitable)-3-(Z-2-chloro-3,3,3-trifluoropropyl-1-alkene-1-yl)-2,2-dimethyl cyclopropane carboxylic acid ester and (R)-alpha-cyano-3-fluoro (1S, suitable)-3-(Z-2-chloro-3,3,3-trifluoropropyl-1-alkene-1-yl)-2,2-dimethyl cyclopropane carboxylic acid ester is formed in the isomer of a pair of enantiomorph of racemize ratio, removed alpha-cyano-4-fluoro-3-benzyloxy phenoxy base-3-(Z-chloro-3,3,3-trifluoropropyl-1-alkene-1-yl)-2 in fact, any other the isomer of 2-dimethyl cyclopropane carboxylic acid ester, the preparation method comprises the steps:
(a) prepare the strong solution of initiator with organic solvent, organic solvent is to select initiator weight in the said solution from containing up to the alkanol of 6 carbon atoms and containing up to the liquid alkane of 8 carbon atoms: the weight of solvent is approximately from 1: 2 to 1: 4,
(b) temperature of regulator solution makes temperature in 17 ℃ to 20 ℃ scope, adds the crystal of a pair of enantiomer of some amount in solution, and keeps the crystal of adding later on to be in the non-dissolved state of solid,
(c) in time enough, the temperature that keeps solution in said scope so that allow crystalline substance from solution, to be precipitated out,
(d) from solution, separate sedimentary crystalline material; And
(e) can optionally make crystalline material carry out recrystallization if desired.
" remove in fact " and mean, other any mixture of isomers weight is no more than 10% of product weight.
The alkanol solvent of preferentially selecting for use is ethanol, Virahol, 1-butanols, 2-butanols, 1-amylalcohol and Virahol/uncle-butanols (1: 1), Virahol/1,2-di-alcohol (2: 1), and what wherein especially preferentially select for use is Virahol.The liquid alkane solvent of preferentially selecting for use is normal hexane, normal heptane.
Said strong solution is meant preferentially selects initiator weight for use: weight of solvent is for from 1: 2 to 1: 4, and override selects for use is 1: 3.
Employed initiator may mix in this method has weight up to 10% corresponding trans-isomer(ide) and (E) isomer, and preferably selecting purity is initiator more than at least 95%, because high yield, highly purified product can be provided like this.
Utilize the crystal that adds a certain amount of a pair of enantiomer to realize this process.For product is precipitated out from solution, these well as if absolute demand.Resemble and from other existing isomer, isolate a pair of enantiomer that needs previously described, initiator is separated through high efficiency liquid chromatography can obtain a certain amount of enough pure a pair of enantiomer that will add.
If necessary, this method is preferably carried out like this, utilizes mild heat to prepare this solution, cools off this solution then and makes its temperature in 17 ℃～20 ℃ scope.During this period of time, will there be an amount of product to crystallize out.In improving one's methods, strong solution slowly joins to be had in the mixture that does not dissolve crystal and a small amount of solvent, and the speed control of adding is equating with speed that product is separated out.The volume of the time that adds according to adding solution can change from several hours by several days.
Product crystallizes out in critical temperature, being lower than under 17 ℃ the situation, comprises unwanted isomer in the precipitation; Be higher than and do not have the precipitation appearance in 20 ℃ of then used strong solutions.
For from may with other isomer of this product generation co-precipitation isolate this product, always need recrystallization, the realization of recrystallization is to utilize any suitable recrystallization solvent, for example: be effective in this process for obtaining the solvent that product preferentially selects for use in front.
If in the top method at least step (c) be under the condition that alkali exists, to carry out, in fact the output of product can increase.The increase of output is the result of a pair of enantiomer difference to the stereoisomerism transformation, this is expressed as (R)-alpha-cyano-4-fluoro-3-benzyloxy phenoxy base (1R to enantiomer, suitable)-3-(Z-2-chloro-3,3,3-trifluoropropyl-1-alkene-1-yl)-dimethyl cyclopropane carboxylic acid's ester and (S)-alpha-cyano-4-fluoro-3-benzyloxy phenoxy base (IS, suitable)-3-(Z-2-chloro-3,3,3-trifluoropropyl-1-alkene-yl)-2,2-dimethyl cyclopropane carboxylic acid ester, a pair of enantiomer that this enantiomer forms in solution is (S)-alpha-cyano-4-fluoro-3-benzyloxy phenoxy base (IS, suitable)-3-(Z-2-chloro-3,3,3-trifluoropropyl-1-alkene-1-yl)-2,2-dimethyl cyclopropane carboxylic acid ester and (R)-alpha-cyano-4-fluoro-3-benzyloxy phenoxy base (IS, suitable)-3-(Z-2-chloro-3,3,3-trifluoropropyl-2,2-dimethyl cyclopropane carboxylic acid ester.The latter separates out from solution as product.
With its simplest form, the invention provides an alpha-cyano-4-fluoro-3-benzyloxy phenoxy base-3-(Z-2-chloro-3,3,3-trifluoropropyl-1-alkene-1-yl)-2, be expressed as corresponding of 2-dimethyl cyclopropane carboxylic acid ester (S)-alpha-cyano-4-fluoro-3-benzyloxy phenoxy base (IR with it, suitable)-3-(Z-2-chloro-3,3,3-trifluoropropyl-1-alkene-1-yl)-2,2-dimethyl cyclopropane carboxylic acid ester and (R)-alpha-cyano-4-fluoro-3-benzyloxy phenoxy base (IS, suitable)-3-(Z-2-chloro-3,3,3-trifluoropropyl-1-alkene-1-yl)-2,2-dimethyl cyclopropane carboxylic acid ester-to the relative concentration method of enantiomer, it makes and contains a pair of enantiomer for (R)-2-cyano group-4-fluoro-3-benzyloxy phenoxy base (IR, suitable)-3-(Z-2-chloro-3,3,3-trifluoropropyl-1-alkene-1-yl)-2,2-dimethyl cyclopropane carboxylic acid ester and (S)-alpha-cyano-4-fluoro-3-benzyloxy phenoxy base (IS, suitable)-3-(Z-2-chloro-3,3,3-trifluoropropyl-1-alkene-1-yl)-2, the solution of 2-dimethyl cyclopropane carboxylic acid ester is done in order to produce epimerization with alkali.
For the suitable solvent of this method is the specified alcohol in front.What especially preferentially select for use is Virahol.Alkali can be any organic or inorganic alkali of locating steady state under reaction conditions.Organic amine, particularly secondary amine and amine and heterocyclic alkali are useful.For example: triethylamine, diisopropylamine, dibutylamine and 2,2,6,6-tetramethyl--N-acylpiperidine.In this method, for the restriction initiator be decomposed into bottom line the time, preferentially select for use diisopropylamine to produce the height epimerization.Occur decomposing mainly is because contain the transesterification of the base catalysis of spirit solvent.Another kind of useful alkali is 1H-1,5, and 9-three azabicyclics (4,4,0)-last of the ten Heavenly stems-9-alkene.
Mineral alkali also is useful, as: an alkali metal salt that the weak organic acid reaction alkali, alkaline earth metal hydroxides, carbonate and the acetate generates.Especially preferentially select Anhydrous potassium carbonate and Potassium ethanoate for use.Therefore, in the concrete grammar of a preferred first usefulness, initiator solution will be by containing the tower of Anhydrous potassium carbonate, to finish epimerization.
Use technology described above, it is effective especially finishing the concentrated of generation crystallized product mother liquor with this.Concentrate and crystallization phases bonded method by using, in fact the initiator of all existence can reflect the right form of body with desirable mapping and obtain.
Therefore, further, the invention provides and be used to obtain improving one's methods of product, this method comprises following several steps:
(a) prepare the strong solution of initiator with organic solvent, organic solvent is to select initiator weight in the said solution from containing up to the alkanol of 6 carbon atoms and containing the liquid alkane of 5～8 carbon atoms: weight of solvent is 1: 2 to 1: 4;
(b) temperature of regulator solution makes temperature in 17 ℃ to 20 ℃ scope, add the crystallization of a pair of enantiomer of some amount in solution, and the crystal that adds after keeping is in the non-dissolved state of solid;
(c) in time enough, the temperature that keeps solution is in said scope, so that allow crystalline substance to be precipitated out from solution;
(d) from solution, separate sedimentary crystalline material; And
(e) if desired, can optionally make crystalline material carry out recrystallization.
Because the change of this method has contained alkali initiator solution and can slowly add in the mixture with kind a small amount of solvent that is stirring.
Product is a kind of typical molten white crystal in 60-67 ℃ scope.For this racemoid, purity is 66.5-67 ℃ at the molten point of the product more than 99%.
This racemoid can be used to go out and remove and control spreading of insect pest, also can be used for for example such invertebrate pests of worm simultaneously.Insect pest and the evil that can use racemoid to go out and remove and control, it comprises the storage with the associated agricultural of insect (agricultural comprises growth, gardening, the animal rearing of food crop and fibre crops), forestry, greengrocery here, for example: fruit, cereal, timber.Racemoid also can be used for controlling and eliminating the insect that those infect the humans and animals disease.
For using racemoid to murder worm, people press the formulated resulting mixture with the effective constituent of sterilant and with inert diluent, solid support material and/or tensio-active agent that its adapts to usually.This mixture also can contain another kind of insecticidal materials, for example: it can be another kind of sterilant, agent extremely, sterilant, insecticide synergist, this synergistic agent can be dodecyl imidazoles, 4-(3,4-methylene dioxy phenyl)-and 5-methyl-two a alkane or 3,4-(methylenedioxy) phenmethyl butoxide.
The mixture that contains racemoid also can powder shape form exist, and this racemoid mixes mutually with solid-state attenuant or carrier, for example: kaolin, wilkinite, diatomite or talcum; Perhaps they also can clever particle shape formula exist, and racemoid is absorbed by the porous particulate material, for example: float stone, a gypsum or corn core material.Material is effective especially for the insect that kills based on soil, for example: the root worm, cutworm class, the threadworms that belong to the Diabrotica class, the weight that a material of preferentially selecting for use contains racemoid is from 1% to 2.5%, this racemoid is to be adsorbed on the particle, for example: will be ejected on this particle with volatile solvent dissolved racemoid, then solvent volatilizees from particle surface, solution also can contain other composition, for example: add a kind of resin and control the speed that racemoid is overflowed from particle, prevent that perhaps the grain husk grain from changing in quality prematurely.Can select for use one of following method that particle is used among the soil, use particle in two row crops or in the furrow between sowing seeds, if desired can be a little with it and mixing with soil; Perhaps when being a farmer, they are used in the furrow in crops oneself, generally, be benchmark with the racemoid that uses, use particulate quantity from 5-25 pound/acre (approaching 5-25 kilogram/hectare), it is enough for the control insect pest, and the scope of preferentially selecting for use is 8-15 pound/acre (approaching 8-15 kilogram/hectare).
When being used for spraying and immersion, the mixture of selection can be mixed with liquid state.It is the emulsion of water dispersion or racemoid normally, and have one or more wetting agents of having known, dispersion agent or emulsifying agent (tensio-active agent) to participate in.
Wetting agent, dispersion agent and emulsifying agent can be positively charged ion, negatively charged ion or non-ionic type.For example: the quaternary ammonium compound cetyl trimethylammonium bromide can be suitable cationics.Suitable anionic agent, for example: soap; Various sulfuric acid aliphatic mono class salt as Sodium Lauryl Sulphate BP/USP; The salt of the aromatic hydrocarbons compounds of group as sodium laurylsulfonate; The mixture of sodium, calcium, ammonium lignin sulfonate or butyl naphthalene sulfonate(BNS), di-isopropyl sodium and triisopropyl sulfonate.The nonionics that is fit to, for example: the condensable product of oxyethane or propylene oxide has the such fatty alcohol of tame oleyl alcohol or hexadecanol, or tame octyl phenol, nonylphenol and the such alkylphenol of octyl group cresylol is arranged in the product.Other nonionics is that the condensed product of said ester has oxyethane, propylene oxide and Yelkin TTS from longer chain fatty acid and deutero-ester the sugar alcohol acid anhydride.
Racemoid is dissolved in the suitable solvent can makes this mixture, for example: the ketone solvent resemble the diacetone, perhaps aromatic solvent resemble the Three methyl Benzene.But also Xiang Shuizhong add that acquired one or more are moistening, the mixture of dispersion or emulsifying agent.Other appropriate organic solvent is dimethyl formamide, titanium dioxide ethene, Virahol, different two pure and mild other dibasic alcohol, Pyranton, toluene, kerosene light oil, methylnaphthalene, dimethylbenzene and trieline, N-methyl-Z-pyrrolidone and tetrahydrofurfuryl alcohol.
When mixture was used to spray, it can be mixed with aerosol and be loaded in the pressurized vessel, and this pressure is to be propelling agent with (one) fluoro trichloromethane and Refrigerant 12.
When using this mixture with water dispersion and emulsion form, it normally uses with the conc forms that contains a high proportion of racemoid.Said enriched material diluted with in the past used water.These enriched materials often need experience long storage, and after the storage, it can also form water preparation by dilute with water.This water preparation matter that remains unchanged in long-time is so that use them with the spraying plant of using always.This enriched material can contain heavy 1～85% racemoid.When it becomes water preparation when dilution, can contain the active composition of different amounts in the water preparation.For using on agricultural and gardening, the racemoid water preparation that contains heavy 0.001%-0.1% is effective especially.
During use, this mixture can be used in insect, and the place of insect is arranged, and the method for any use insecticide mixtures of knowing can be used at this in the place that recurrent place of insect or insect are easy to grow.For example: dusting or spraying.
Mixture of the present invention all has very big toxicity for various insects and other invertebrate pests in very wide scope.For example comprise following:
Aphis fabae (aphid)
Megoura viceae (aphid)
Aeaes aegypti (mosquito)
Dysdercus fasciatus (educating stinkbug)
Musca domestica (housefly)
Pieris brassicae (white butterfly, larva)
Plutella maculipennis (diamond-back moth, larva)
Phaedon cochleariae (leaf mustard beetle)
Tetranychas cinnabrainus (cochineal look)
Trialeuroiaes class (twill burglar moth)
Blattella germanioa (cockroach)
Spodoptera littoralis (clothing pretty young woman)
Ohortiocstes terminufera (locust)
Diabrotioa class (rootworm)
Agrotis class (cutworm)
Compound of the present invention and the mixture that has provided are effective especially for the lepidoptera pest of controlling cotton.For example: Spodoptera class and Heliothis class.The character of this compound can make it go out except that the insect among the soil, for example: the Heliothis class.Remove outstanding obstinate insect such as fly for going out, they also can optionally use with other sterilant together.They remove the worm and the evil that produce for going out in domestic animal be effective especially, for example: Lucilia sericata and flat
, for example Boophius class, Ixodes class, Amblyomma class, Phipicephalas class and Permaceutor class.They all are sensitive and durable effective for the insect of going out except that adult, larva and vegetative period.And it can also local, oral, external treatment be used in large quantities of animals of growth insect.
The present invention describes by the following example.
Embodiment 1:
Present embodiment is used for illustrating (RS)-alpha-cyano-4-fluoro-3-benzyloxy phenoxy base (IRS, suitable)-3-(Z-2-chloro-3,3,3-trifluoropropyl-1-alkene-1-yl)-2, the preparation method that the 2-dimethyl cyclopropane carboxylic acid sees.
(IRS, suitable)-1-chlorine carboxyl-3-(Z-2-chloro-3,3,3-trifluoropropyl-1-alkene-1-yl)-2,2-dimethylcyclopropane (0.52g), 4-fluoro-3-phenoxy benzaldehyde (0.43g), sodium cyanide (98mg), normal hexane (5.0cm
3), water (2.0cm
3) and the mixture of tetramethylammonium iodide (10mg) stirred 16 hours in room temperature (about 25 ℃).Dilute behind this mixture with the saturated sodium bicarbonate solution washing with ethyl acetate, use the salt solution washed twice again.Isolate organic phase, dry on anhydrous magnesium sulfate, filtration, and with the filtrate vapourisation under reduced pressure, solvent concentrates.Residual oil is purified with preparative column chromatography (the silicon post is with containing 5% volume normal hexane and 10% volumes of acetic acid ethyl ester wash-out continuously).Differentiate the cut that contains product by gas chromatographic analysis (225 ℃ of column temperatures).Cut increases, and under reduced pressure removes solvent by evaporation, obtains a kind of incrystallizable oily product, and this oil product is for having the mixture of four possible cis-isomerides of Z-conformation at chlorine trifluoro propene group.It respectively is 29% (S)-alpha-cyano-4-fluoro-3-benzyloxy phenoxy base (IS that four isomer contain on weight, suitable)-3-(Z-2-chloro-3,3,3-trifluoropropyl-1-alkene-1-yl)-2,2-dimethyl cyclopropane carboxylic acid ester and enantiomorph thereof: (R)-alpha-cyano-4-fluoro-3-benzyloxy phenoxy base (IR, suitable)-3-(Z-2-chloro-3,3,3-trifluoropropyl-1-alkene-1-yl)-2,2-dimethyl cyclopropane carboxylic acid ester, respectively be (S)-alpha-cyano-4-fluoro-3-benzyloxy phenoxy base (IR of 18%, suitable)-3-(Z-2-chloro-3,3,3-trifluoropropyl-1-alkene-1-yl)-2,2-dimethyl cyclopropane carboxylic acid ester and enantiomorph thereof: (R)-alpha-cyano-4-fluoro-3-benzyloxy phenoxy base (IS, suitable)-3-(Z-2-chloro-3,3,3-trifluoropropyl-1-alkene-1-yl)-2,2-dimethyl cyclopropane carboxylic acid ester, remaining 6% is impurity and residual solvent.
1H nucleus magnetic resonance (CDCl
3) displacement δ: 1.19-1.32
(complex body, 6H); 200 (d, J=9H
21H);
228(bdd，J＝9，9.1H)；6.22，6.33
(S，1H)，6.72-7.50(m，10H)。
19F nucleus magnetic resonance (CDCl
3) displacement δ :-127.75 (td=7.28 6.28,
1F)；-69.32(S，3F)。
Infrared (whiteruss): 1740,1650,1592,1510,
1490，1465，1370，1295，
1270，1120，750Cm
-1
Embodiment 2:
Present embodiment is used for illustrating the separation of two pairs of racemic isomers that exist in embodiment 1 product,
(i) the silico analysis post of a long 5Cm is with containing the normal hexane of 4% (body) ethyl acetate with 1cm
3The speed wash-out of/min, the small amount of sample of embodiment 1 product be process high performance liquid chromatography separating treatment on above-mentioned silico analysis post.In retention time is to observe two peaks in 6.39 minutes and 7.66 minutes, and its relative area is 4: 1.Isomer corresponding with it is to being (S)-alpha-cyano-4-fluoro-3-benzyloxy phenoxy base (IS respectively, suitable)-3-(Z-2-chloro-3,3,3-trifluoropropyl-1-alkene-1-yl)-2,2-dimethyl cyclopropane carboxylic acid ester and its enantiomorph: (R)-alpha-cyano-4-fluoro-3-benzyloxy phenoxy base (IR, suitable)-3-(Z-2-chloro-3,3,3-trifluoropropyl-1-alkene-1-yl)-2,2-dimethyl cyclopropane carboxylic acid ester (claiming " racemoid " hereinafter) reaches (S)-alpha-cyano-4-fluoro-3-benzyloxy phenoxy base (IR, suitable)-3-(Z-2-chloro-3,3,3-trifluoropropyl-1-alkene-1-yl)-2,2-dimethyl cyclopropane carboxylic acid ester and its enantiomorph: (R)-alpha-cyano-4-fluoro-3-benzyloxy phenoxy base (1S, suitable)-3-(Z-2-chloro-3,3,3-trifluoropropyl-1-alkene-yl)-2,2-dimethyl cyclopropane carboxylic acid ester (claiming " racemoid B " hereinafter).
(ii) with one and half preparation high efficiency liquid chromatography instrument, operational condition is with reference to leading portion, product in the example 1 is divided into equal several parts (every part of 2.5mg) one by one, and obtaining summation is the racemoid A (the racemoid B that comprises 6% (weight)) of 50mg and the racemoid B (the racemoid A that comprises 7% (weight)) of 15mg.
(iii) with a preparation high efficiency liquid chromatography instrument (Gi1son), product 500mg among the embodiment 1 is separated, operational condition obtains the miscellany (63mg) of pure racemoid A (218mg) and racemoid A (20% (weight)) and racemoid B (80% (weight)) with top (i).
Two pairs of racemic isomers are composed with proton magnetic resonance and are distinguished that main difference point is as follows:
Nucleus magnetic resonance (CDCl
3) displacement δ:
Racemoid A; 1.32 (S, 6H); 6.I8 (S, 1H);
Racemoid B; 1.19 (S, 3H);
1.32(S，3H)；6.33(S，1H)。
Embodiment 3:
Present embodiment has illustrated (RS)-alpha-cyano-4-fluoro-3-benzyloxy phenoxy base (1RS, suitable)-3-(Z-2-chloro-3,3,3-trifluoropropyl-1-alkene-1-yl)-2, the preparation of 2-dimethyl cyclopropane carboxylic acid ester.
At stirring at room (IRS, suitable)-3-(Z-2-chloro-3,3,3-trifluoropropyl-1-alkene-1-yl)-2,2-dimethyl cyclopropane carboxylic acid (90.94g) and toluene (225cm
3) miscellany, and in this mixture, add and contain dimethyl formamide (0.5cm
3) thionyl chloride (90cm
3), the mixture with aforesaid combination stirred more than 16 hours then, afterwards, under reduced pressure removed volatile part by evaporation.Surplus oil shows that with infrared measurement it mainly is by (IRS, suitable)-1-chlorine carboxyl-3-(Z-2-chloro-3,3,3-trifluoropropyl-1-alkene-1-yl)-2, and the 2-dimethylcyclopropane is formed.Mix with 4-fluoro-3-phenoxy benzaldehyde (76.92g) with it, and this mixture is joined sodium cyanide (22.0g) that stirred and the water (71cm that contains 1% (weight) wetting agent (Synperonic) NX (registered trademark)
3) and toluene (32cm
3) mixture in go, temperature keeps 35 ℃, the time is more than 1 hour.Reaction mixture was cooled to after the room temperature continuously stirring 4 hours, with ether (300cm
3) extraction.Ethereal extract saturated sodium bicarbonate solution (10cm
3) and salt solution (2 * 100cm
3) washing, and vapourisation under reduced pressure is concentrated, obtains (RS)-alpha-cyano-4-fluoro-3-benzyloxy phenoxy base (IRS, the suitable)-3-(Z-2-chloro-3,3,3-trifluoropropyl-1-alkene-1-yl)-2 of colorless oil, 2-dimethyl cyclopropane carboxylic acid ester (147g).Gas chromatographic analysis shows by 93% pure products and is made up of the cis-isomeride that four kinds of isostatic embodiment 1 point out.
Embodiment 4:
Present embodiment has illustrated the method that obtains racemic product by crystallization and concentrated mother liquor.
Stirring contains (R)-alpha-cyano-4-fluoro-3-benzyloxy phenoxy base (IS, suitable)-3-(Z-alpha-chloro-3,3,3-trifluoropropyl-1-alkene-1-yl)-2,2-dimethylcyclopropane and (S)-alpha-cyano-4-fluoro-3-benzyloxy phenoxy base (IR, suitable)-3-(Z-2-chloro-3,3,3-trifluoropropyl-1-alkene-1-yl)-2, the fluorine third-1-alkene-1-yl of 2-dimethylcyclopropane)-2, the 2-dimethylcyclopropane is in the solid crystal thing (1.0g) and dried Virahol (5.0Cm of racemize ratio
3) mixture, keeping its temperature is 17.5 ℃, is added dropwise to diisopropylamine (3.5Cm then with the time more than 7 days in said mixture
3) (RS)-alpha-cyano-4-fluoro-3-benzyloxy phenoxy base (IRS, suitable)-3-(Z-2-chloro-3,3,3-trifluoropropyl-1-alkene-1-yl)-2, the dried Virahol (141Cm of 2-dimethyl cyclopropane carboxylic acid ester (47.0g, the method preparation of pressing embodiment 2)
3) solution.After being added dropwise to complete, stir the mixture more than 24 hours.Solid collected by filtration precipitation, on strainer with dried Virahol (5.0Cm
3Be cooled to 0 ℃) washing, dry, obtain crystallized product (19.0g in the racemize ratio, nuclear resonance analytical pure 99%, fusing point: 66.5～67.0 ℃), this product is by (R)-alpha-cyano-4-fluoro-3-benzyloxy phenoxy base (IS, suitable)-3-(Z-2-chloro-3,3,3-trifluoropropyl-1-alkene-yl)-2,2-dimethyl cyclopropane carboxylic acid ester and (S)-alpha-cyano-4-fluoro-3-benzyloxy phenoxy base (IR, suitable)-3-(Z-2-chloro-3,3,3-trifluoropropyl-1-alkene-1-yl)-2,2-dimethyl cyclopropane carboxylic acid ester is formed.
1H nuclear resonance (CDCl
3) displacement δ: 1.19 (S, 3H);
1.32(S，3H)；2.0(d，J＝9H
a，1H)
2.28(dd，J＝9，9Ha，1H)；6.33
(S，1H)；6.72-7.50(m.10H)。
19F nuclear resonance (CDCl
3) displacement δ :-127.75 (td=7.28,
(84.26 megahertz) 6.28,1F)
-69.32(S，3F)
Infrared (KB
r): 1745,1652,1592,1513
1495，1421，1305，1300，
1275，1197，1137，1129，
1085，820，?805，?752Cm
-1
Reduce pressure following evaporating solvent with concentrated mother liquor, the residuum acetic acid ethyl dissolution.Solution with water, salt solution is also dry on anhydrous magnesium sulfate, and the vapourisation under reduced pressure solvent concentrates then, obtains four kinds of ratios and is approximately 1: 1: 1: 1 cis mixtures of isomers, with regard to racemoid, just indicated the concentration process of whole mother liquors in this method like this.
Embodiment 5:
Present embodiment is used for illustrating the modified activity that product of the present invention is compared with known insecticides.The LC of product
50Value depends on that bollworm drafts a document the control experiment of green larva (tobacco budworm-kind of important cotton-plant pest-insects), promptly by larva being placed on containing on the leaf that the composition product spraying that is expressed as various ppm concentration (ratio) handled, and when various different ratios, observe mortality ratio, determine LC by calculating then
50Value (50% desired concn kills off the insect pests), following form is not only with LC
50The form of value but also list the result with regard to the reactivity coefficient of Cyhalothin (known sterilant) can find out that the reactivity coefficient of invention product is more much bigger than known insecticides reactivity coefficient from table, shown that invention its lytic activity degree is higher.
| Product LC 50FACTOR P Pm v.cyhalothrin |
| Cyhalothrin (known product) *3.4 1.0 Cyfluthrin (known product)+4.8 0.71 embodiment, 1 product, 0.9 3.78 racemoid B 0.44 2.73 |
*Cyhalothrin is (±)-alpha-cyano-3-benzyloxy phenoxy base-(±)-suitable-(Z-2-chloro-3,3,3-trifluoropropyl-1-alkene-1-yl)-2,2-dimethyl cyclopropane carboxylic acid ester.
+ Cyfluthrin is (±)-alpha-cyano-4-fluoro-3-benzyloxy phenoxy base (±)-suitable/anti--3-(2, the 2-dichloroethylene)-2,2-dimethyl cyclopropane carboxylic acid ester.
Claims (12)
1. concentrated alpha-cyano-4-fluoro-3-benzyloxy phenoxy base-3-(Z-2-chloro-3,3,3-trifluoropropyl-1-alkene-1-base-2,2-dimethyl cyclopropane carboxylic acid ester and corresponding being expressed as (S)-alpha-cyano-4-fluoro-3-benzyloxy phenoxy base (IR, suitable)-3-(Z-alpha-chloro-3,3,3-trifluoropropyl-1-alkene-1-yl)-2,2-dimethyl cyclopropane carboxylic acid ester and (R)-alpha-cyano-4-fluoro-3-benzyloxy phenoxy base (IS, suitable)-3-(Z-2-chloro-3,3,3-trifluoropropyl-1-alkene-1-yl)-2, the method of 2-dimethyl cyclopropane carboxylic acid ester solution, this method comprises making and contains enantiomer for (R)-alpha-cyano-4-fluoro-3-benzyloxy phenoxy base (IR, suitable)-3-(Z-2-chloro-3,3,3-trifluoropropyl-1-alkene-1-yl)-2,2-dimethyl cyclopropane carboxylic acid ester and (S)-alpha-cyano-4-fluoro-3-benzyloxy phenoxy base (IS, suitable)-3-(Z-2-chloro-3,3,3-trifluoropropyl-1-alkene-1-yl)-2,2-dimethyl cyclopropane carboxylic acid ester solution is done in order to implement epimerization with alkali in organic solvent.
2. according to the method for claim 1, said organic solvent is the low-level chain triacontanol that contains up to 6 carbon atoms.
3. according to the method for claim α, said low-level chain triacontanol is a Virahol.
4. according to the method for claim 1, said alkali is secondary amine or tertiary amine or heterocyclic alkali.
5. according to the method for claim 4, said alkali is diisopropylamine, 2,2,6, and 6-tetramethyl--N-acylpiperidine or 1H-1,5,9-three azabicyclics (4,4,0)-last of the ten Heavenly stems-9-alkene.
6. volume increase method that obtains crystalline material, said crystalline material is by being expressed as (S)-alpha-cyano-4-fluoro-3-benzyloxy phenoxy base (IR basically, suitable)-3-(Z-2-chloro-3,3,3-trifluoropropyl-1-alkene-1-yl)-2,2-dimethyl cyclopropane carboxylic acid ester and (R)-alpha-cyano-4-fluoro-3-benzyloxy phenoxy base (IS, suitable)-3-(Z-2-chloro-3,3,3-trifluoropropyl-1-alkene-1-yl)-2,2-dimethyl cyclopropane carboxylic acid ester is formed in a pair of enantiomer of racemize ratio, exempted alpha-cyano-4-fluoro-3-benzyloxy phenoxy base-3-(2-chloro-3,3,3-trifluoropropyl-1-alkene-1-yl)-2 in fact, any other isomer of 2-dimethyl cyclopropane carboxylic acid ester, this method comprises the steps:
(a) form (RS)-alpha-cyano-3-benzyloxy phenoxy base (IRS, suitable)-3-(Z-2-chloro-3,3,3-trifluoropropyl-1-alkene-1-yl)-2 with containing the organic solvent of in 6 carbon atom low-level chain triacontanols, selecting, the concentrated solution of Z-dimethyl cyclopropane carboxylic acid ester,
(b) temperature of regulator solution is controlled in 17 ℃ to the 20 ℃ scopes temperature, adds the crystal of the one-tenth enantiomer of some amount in solution, and after this, the crystal that keeps adding is in the undissolved solid state,
(c) temperature of control solution is in said temperature range, and with time enough crystallisate is precipitated out from solution,
(d) sedimentary crystalline material in the solution is separated, and
(e) if desired, can optionally crystalline material be carried out recrystallization,
It is characterized in that: alkali exists in the method for step (C) at least, thereby has a certain proportion of being expressed as (R)-alpha-cyano-4-fluoro-3-benzyloxy phenoxy base (IR at least, suitable)-3-(ZR, suitable)-3-(Z-2-chloro-3,3,3-difluoro third-1-alkene-1-yl)-2,2-dimethyl cyclopropane carboxylic acid ester, (S)-alpha-cyano-4-fluoro-3-benzyloxy phenoxy base (IR, suitable)-3-(Z-2-chloro-3,3,3-trifluoropropyl-1-alkene-1-yl)-2, the a pair of enantiomer of 2-dimethyl cyclopropane carboxylic acid ester is transformed into (S)-alpha-cyano-4-fluoro-3-benzyloxy phenoxy base (IR, suitable)-3-(Z-2-chloro-3,3,3-trifluoropropyl-1-alkene-1-yl)-2,2-dimethyl cyclopropane carboxylic acid ester and (R)-alpha-cyano-4-fluoro-3-benzyloxy phenoxy base (IS, suitable)-3-(Z-2-chloro-3,3,3-trifluoropropyl-1-alkene-1-yl)-2, a pair of enantiomer of 2-dimethyl cyclopropane carboxylic acid ester.
7. according to the method for claim 6, different is the mixture that adds a pair of undissolved enantiomer crystal and organic solvent in the solution that also contains alkali lentamente, keeps organic solvent temperature in 17 ℃～20 ℃ scopes.
8. by (R)-alpha-cyano-4-fluoro-3-benzyloxy phenoxy base (IS, suitable)-3-(Z-2-chloro-3,3,3-trifluoropropyl-1-alkene-1-yl)-2,2-dimethyl cyclopropane carboxylic acid ester and (S)-alpha-cyano-4-fluoro-3-benzyloxy phenoxy base (IR, suitable)-3-(Z-2-chloro-3,3,3-trifluoropropyl-1-alkene-1-yl)-2, the enantiomer that 2-dimethyl cyclopropane carboxylic acid ester is formed in the racemize ratio, and exempt alpha-cyano-4-fluoro-3-benzyloxy phenoxy base-3-(Z-chloro-3,3 in fact, 3-trifluoropropyl-1-alkene-1-yl)-2, other any isomer of 2-dimethyl cyclopropane carboxylic acid ester.
9. according to Claim 8, be in the enantiomorph of the isomer of crystalline solid state, its molten o'clock in 60 ℃～70 ℃ scopes.
10. according to Claim 8, pesticide compound contains an amount of enantiomer that insecticidal action is arranged, exempted alpha-cyano-4-fluoro-3-benzyloxy phenoxy base-3-(2-chloro-3 in fact, 3,3-trifluoropropyl-1-alkene-1-yl)-2, any other isomer of 2-dimethyl cyclopropane carboxylic acid ester, it is satisfied that the inert diluent of sterilant or carrier combine with agricultural and gardening.
11. according to claim 10, the on-site method of a kind of Pest Control is included in the mixture that use in the insect location insecticidal action in right amount.
12. (RS)-alpha-fluoro-3-benzyloxy phenoxy base (IRS, suitable)-3-(Z-2-chloro-3,3,3-trifluoropropyl-1-alkene-1-yl)-2,2-dimethyl cyclopropane carboxylic acid ester has been removed any trans-isomer(ide) or (E) formula mixture of isomers in fact.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 85105604 CN1015362B (en) | 1984-07-18 | 1985-07-23 | Insecticidal composition containing trifluoropropenyl-substituted phenoxyfluorobenzyl cyclopropanecarboxylate derivative |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB848418331A GB8418331D0 (en) | 1984-07-18 | 1984-07-18 | Insecticidal ester |
| CN 85105604 CN1015362B (en) | 1984-07-18 | 1985-07-23 | Insecticidal composition containing trifluoropropenyl-substituted phenoxyfluorobenzyl cyclopropanecarboxylate derivative |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN85105604A true CN85105604A (en) | 1987-01-28 |
| CN1015362B CN1015362B (en) | 1992-02-05 |
Family
ID=25741890
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 85105604 Expired CN1015362B (en) | 1984-07-18 | 1985-07-23 | Insecticidal composition containing trifluoropropenyl-substituted phenoxyfluorobenzyl cyclopropanecarboxylate derivative |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1015362B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104649933A (en) * | 2013-11-18 | 2015-05-27 | 江苏扬农化工股份有限公司 | Pyrethroid compound having specific spatial configuration, preparation method and application thereof |
-
1985
- 1985-07-23 CN CN 85105604 patent/CN1015362B/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104649933A (en) * | 2013-11-18 | 2015-05-27 | 江苏扬农化工股份有限公司 | Pyrethroid compound having specific spatial configuration, preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1015362B (en) | 1992-02-05 |
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