CN86101380A

CN86101380A - Pyrethroid composition containing multiple active components

Info

Publication number: CN86101380A
Application number: CN86101380.8A
Authority: CN
Inventors: 拉斯洛·帕普; 吉奥吉·黑达希; 桑多尔·佐尔坦; 伊斯特万·塞克利; 比拉·伯托克; 鲁多夫·索斯; 埃塞比特·拉德瓦尼·尼·赫格杜斯; 拉约斯·纳吉; 安塔尔·加扎里; 埃瓦·索姆法; 阿格尼斯·赫格杜斯; 桑多尔·伯塔尔; 塔马斯·萨伯尔克希
Original assignee: Chinoin Gyogyszer es Vegyeszeti Termekek Gyara Zrt
Current assignee: Chinoin Private Co Ltd
Priority date: 1986-01-08
Filing date: 1986-03-07
Publication date: 1987-07-15
Anticipated expiration: 2001-03-07
Also published as: PL149799B1; CN1015709B; TR22867A; IL77624A; HUT41962A; EG18336A; EG18452A; PL267524A1; PL153005B1; CS48086A2; PL150680B1; CN1031972C; PL269466A1; PL151661B1; TR22871A; CN86101357A; AR244504A1; CS254994B2; CN1050810A; PL257782A1

Abstract

An insecticidal composition comprises multiple active components, and contains synthetic pyrethroid active component 0.001-99 wt%. That is, a mixture of enantiomer pairs Ia: Ib of 55: 45 to 25: 75 out of 8 possible isomeric forms is at least 95%, wherein Ia is 1R cis S +1S cis R and Ib is 1R trans S +1S trans R. If desired, various additives may be incorporated as described in the specification.

Description

The composition that contains the pyrethroid of various active component

The present invention relates to Pesticidal combination that contains multiple pyrethroid active component and uses thereof.Also relate to this active component and preparation process thereof.

In this manual, relevant with the asymmetric carbon atom of " α " expression substituent spatial configuration uses " S " and " R " to characterize respectively.The title of " cis " and " trans " indicates the substituent position that links to each other with the carbon atom " 3 " of cyclopropane ring respectively.The carbon atom of cyclopropane ring " 3 " is relevant with the substituent spatial configuration of carbon atom " 1 ".The absolute steric configuration that links to each other with carbon atom " 1 " is used prefix " 1R " and " 1S " expression respectively.

In this manual, various enantiomer and enantiomer are to representing with following abbreviation:

The mixture of I a:1R cis S and 1S cis R

The mixture of trans S of I b:1R and the trans R of 1S

The mixture of I c:1R cis R and 1S cis S

The mixture of trans R of I d:1R and the trans S of 1S

I f:1R cis S

The trans S of I g:1R

I h:1S cis R

The trans R of I i:1S

Compound by general formula (I):

Can obtain following commercial compound:

" Fenvalerate " of-general formula (II) contains all isomrs;

" the α Mi Silin " of-general formula (II) only contains 1R cis S and 1S cis R isomr;

" the δ Mi Silin " of-fraction (III) only contains 1R cis S isomr.

Selecting possible isomr is to be benchmark with the insecticidal effect, (particularly according on housefly class insect, carried out test) carried out according to the result of test, some their toxicity on some insect of homogeneous isomer proof is high and remarkable, and trend towards significantly throwing in the strongest homogeneous isomer of vitality, trend towards the synthetic the strongest homogeneous isomer of this vitality equally significantly to market.〔Pest.Sci./7，273-（1976）〕

As everyone knows, the pyrethroid of general formula (II) (its class is called " Fenvalerate ") belongs to the important class family of synthetic pyrethroid, and it is as insecticide useful (hungarian patent No.170,866).This compound can have under the situation of alkali, forms (Pst.Sci.6,537-by m-phenoxy group-benzaldehyde cyanhydrin and the reaction of cyclopropane-carboxylic acid chloride ... (1975)).The product that obtains like this is made up of 8 kinds of stereoisomerses, promptly is made up of a kind of 4 right mixtures of enantiomer.If what use is that a kind of trans and ratio cis is 60: 40 the muriatic mixture of cyclopropane-carboxylic acid, so this mixture comprises that 18～19% enantiomer is to I a, 22% enantiomer is to I c, 26～27% enantiomer to I b and 33～34% enantiomers to I d.

According to prior art, the stereoisomers of " Fenvalerate " shows different biologically actives.It has been generally acknowledged that the molecular activity that contains the cis cyclopropane-carboxylic acid is compared with the molecular activity of corresponding antiderivative be eager to excel (Pest.Sci.7,273(1976)).

In the contrast biologic test of various pyrethroids (Pest.Sci.9,112～116(1978)), once cis and trans the stereoisomers stereoisomers of Fenvalerate (comprise to) were carried out commentary.

Comparative test be the L in housefly belong to and Phaedon cochleariae in the Fab genus carry out.We notice the chlorine derivative that derives from trans homogeneous isomer, have found the trans S(I of 1R g) and the activity data of the trans R of 1R.Above-mentioned data show (although the homogeneous isomer of the trans S of 1R has very strong activity), the trans R homogeneous isomer of 1R is wanted much weak (show according to test, the activity of the anti-resmethrin of dextrorotation (100) on housefly is 1400 and 81, is 2200 and 110 on Phaeto cochleariae).We have disclosed two seed ginsengs afterwards, and to add the activity of mixture of homogeneous isomer of test lower than calculated value.Thereby a kind of antagonism rather than desired synergistic effect appear in this homogeneous isomer.Its efficient that disappears is respectively 1.42 and 1.46 on housefly and mustard beetle.

Because above-mentioned test and some publications make the biological interest of trans homogeneous isomer and composition thereof be tending towards dim, research is focused on active cis derivative and composition thereof.This has just caused the development of α Mi Silin (mixture of chlorine derivative 1R cis S and 1S cis R(I homogeneous isomer a)), and has caused the development of Mi Silin in the last of the ten Heavenly stems (only comprising br-derivatives 1R cis S homogeneous isomer (I f)).

For this reason, we have known that the mixture of several homogeneous isomers from known Fenvalerate class extracts the preparation process of mixture of cis homogeneous isomer.

A content of the present invention is exactly that a kind of Pesticidal combination that contains the various active component will be provided.If need, can also in intermixture, mix activator and/or mix adjuvant, its value can reach 100%; It is better to mix antioxidant, stabilizing agent, wetting agent, emulsifier, dispersant, antifoaming agent, thinner, carrier and/or filler or the like.This Pesticidal combination is comprising the such active component of synthetic pyrethroid of general formula (I), and its shared weight ratio is that X represents chlorine or bromine in 0.001～99%(general formula (I)).That is, except the 8 kinds of isomerism beyond the region of objective existences that can deposit, enantiomer is that 55: 45 to 25: 75 mixture accounts for 95% at least to I a: I b, and wherein, I a is 1R cis S+1S cis R, and I b is the trans R of the trans S+1S of 1R.

The present invention has found precious and the favourable biological nature of having of isomerism mixture I a+ I b.Although carried out extensive studies work and published a large amount of documents and monograph in the field of the pyrethroid of general formula (I), above-mentioned characteristic still makes the people be shocked and is novel.

Just can know that later on the mixture that extracts can produce (C.A.95,1981 with the method for crystallization from the solution that contains other homogeneous isomer in the cis homogeneous isomer; Publication number: 57755/81).The mixture that a kind of purity is roughly 1: 1 1R cis S and 1S cis R homogeneous isomer also can be separated (british patent document number: 2,064,528) by suitable solution from contain other cis homogeneous isomer.This piece file says, this isomerism mixture I a ten minutes is active.Particularly, study intensively out what is called " high cis-position " synthetic method in order to produce the cis cyclopropane-carboxylic acid intermediate that contains the cis homogeneous isomer that surpasses a certain limit (about 50%), however appropriate litigation fees height (Angew.Chem.Ie, 24 of these methods, (11), 996(1985)).

The present invention finds: when most active trans homogeneous isomer in the compound of the trans S homogeneous isomer I g(general formula (II) with 1R) and the trans R homogeneous isomer of 1S I i(come in the homogeneous isomer of owing to enliven of seven kinds of remaining homogeneous isomers) synthetic the time, find that early stage disclosed homogeneous isomer is not to there being antagonism.

Moreover, when with this synthetic, outside the additive effect of pure I g and I i homogeneous isomer synergy has appearred again.

In order to develop a kind of new active component type, then can from synthetic pyrethroid, select a kind of novel active component from above discovery with outstanding characteristic.Above-mentioned novel active component is showed and is better than hitherto known homogeneous isomer selection:

-be low toxicity for homoiothermy class animal and human class.

-production process more economically.

-minimizing is to the infringement of useful parasite and honeybee.

The new compound of this homogeneous isomer mixture is described and required to contain to (sequence number is 158/85) in claim in the patent that we apply for the same period.

The present invention further finds, the biology of the physiologically active that special homogeneous isomer is observed in advance continue order and describe the right known rule of homogeneous isomer for other homogeneous isomer to there not being necessary relation.

Thereby we compare with other homogeneous isomer as possible, and have tested the trans R enantiomer of the trans S+1S of 1R simultaneously I b(is found that by our test I b is active).Comparison shows that, be I g and I i to I b(at enantiomer) joint between viewed synergistic effect not appear at corresponding cis enantiomer be I f and I h to I a() joint between.

The present invention further finds, simultaneously from 1R cis S(I f) and the trans S(I of 1R g) homogeneous isomer, normally more active I f homogeneous isomer, enantiomer proves opposite to the physiologically active of I a and I b on some kind.

Because aforesaid result, we have obtained surprising discovery finally: when using enantiomer to I a and I b simultaneously, will observe synergy, that is to say, when using this synthetic, synthetic effect will surpass a kind of additive effect of two kinds of enantiomer centerings.

The biological effect that has found that the synergy of I a+ I b mixture is not limited to such mixture, and in mixture, I b is more active than I a.Thereby, go up these two kinds of enantiomers of use to having caused a kind of effective synergistic effect Colorado colorado potato beetle (Lepti-notersa decemlineata).The above results is at length announced in an embodiment.

Based on above-mentioned discovery, we have carried out new screening from the mixture of known homogeneous isomer, and it has caused the appearance of new compound of the present invention.

Except synergy, compound of the present invention also has a large amount of better advantages, and therefore, it is a kind of good quality production.Significantly, compound of the present invention is little to hitherto known toxicity of compound with effect for mammal.This point is proved undoubtedly by so-called selectivity index (being respectively 517 and 747).Selectivity index is near the merchant of the median lethal dose measured on mouse P.O (be respectively 280 and 355mg/kg) and near the merchant of the median lethal dose of local measurement on housefly (be respectively 0.54 and 0.48mg/kg).The selectivity index of above-mentioned I a equals 50/0.45=111.

Synergy also can be at last observing (seeing biological Examples 19), thereby this compound also is effective as killing agent.The toxicity that compound of the present invention shows for the honeybee class is very low, and it does not endanger the parasite (biological Examples 25 and 26) of useful insect.Above-mentioned superior characteristic is the repelling effect of active component due to, better persistence and suitable peculiar activity.

Above characteristic the right mixture of enantiomer of the present invention can be applied in the integrated complex of resist technology (IMP=pest control association).

The economic interests of the present composition are the same with biologicak efficiency at least important.Prepare the forfeiture that pure cis enantiomer needs the high synthetic method of price to I a or cause the trans composition that generates in reactant mixture.On the other hand, the present invention makes all the components of I a and I b generate (efficient depends on used special synthetic method certainly and depends on mixture I a and I b components in proportions) from the mixture of reaction with most economical synthetic method.

The homogeneous isomer that is mixed with additives known of comprising provided by the invention can be with being suitable for direct occupation mode preparation to the Pesticidal combination of I a and I b.

Composition provided by the invention can be ultralow volume (ULV) composition, and it can be sprayed, and can make dispersible fine powder and shot-like particle, and it is wettable and can makes the fine powder of other type and stable emulsion or the like.Above-mentioned composition is suitable for the desinsection of vegetable plot, vineyard, orchard, cropland and other extensive plantation to be handled.Because low toxicity, composition provided by the invention be particularly suitable for resisting winged insect and be suitable for the pasture treatment hide be in and the insect among the horse Stables or the like.

The content of further referring to according to the present invention provides the using method of above-mentioned Pesticidal combination.In the condition afield, preferably use above-mentioned composition with the ratio of per hectare 52～59 active components.

Pesticidal combination provided by the invention can comprise except that enantiomer to activator and synergist the I a+ I b, for example: piperonyl butoxide.The increase of above-mentioned additive does not have to increase the toxicity to homoiothermy class animal, but has strengthened the efficient of active component.

The concrete scheme of preferentially selecting for use according to the present invention provides to calculate by weight to comprise 1～99% active component, and the suitable additive that mixes with it is calculated by weight and then contained 99%～1.The anion and/or the non-ionic surface active agent that can operating weight account for 0.1-1% as adjuvant.For example, the alkali metal salt and the formaldehyde of alkarylsulphonic acid alkali metal salt, alkarylsulphonic acid concentrate, alkaryl polyglycol ether, sulfuration long-chain alcohol, PEO, sulfurized fatty family alcohol, fatty acid polyglycol glycol ether and various other commercially available surfactant.

Pesticidal combination provided by the invention can be 5～50% active component with preferably containing weight ratio also, and the weight ratio of additive is that the mode of 50～95 concentrate is prepared.When the condensed emulsified liquid of emulsification in water or when mixing water in condensed emulsified liquid, additive can make stable emulsion generate.

As additive, can operating weight than being that 1～20% surfactant and/or weight ratio are 0.1～5% stabilizing agent, mixture preferably converts 100% with organic solution.

As surfactant, preferably use anion and non-ionic surface active agent.Preferably use surfactant down: the calcium salt of alkyl sulfonic acid, the two lipids of mono phosphoric acid ester, nonyl and three fourth phenol polyglycol ethers, the adduct of fatty alcohol and oxirane, fatty acid polyglycol glycol ether, oxirane-1.2 propylene oxide block copolymer or the like.

As solvent, and the most handy aromatic hydrocarbon mixture (for example: dimethylbenzene), ring ethanol, butanols, MEK, isopropyl alcohol or the like.

The composition that the present invention proposes also may comprise the synergist that can reduce active component quantity.For this reason, preferably use piperonyl butoxide.

The content of further referring to according to the present invention provides a kind of preparation process of insecticidal active ingredient.This insecticidal active ingredient comprises 8 kinds of possible homogeneous isomers (X represents chlorine or bromine in the formula) of the synthetic pyrethroid that self-drifting (I) provides.In fact only comprise enantiomer and be 55: 45～25: 75 mixture (wherein I a is 1R cis S and 1S cis R, and I b is trans S of 1R and the trans R of 1S) to I a: I b.This preparation process comprises:

A) from a kind of mixture, produce.This mixture is except comprising homogeneous isomer I a+ I b, also comprise the homogeneous isomer that other is possible, and/or comprising homogeneous isomer to I a+ I b with the ideal value of a kind of ratio rather than saturated solution, this saturated solution is the non-proton organic solvent inert of a kind of proton or polarity.The seed crystal of the mixture of I a and I b being made of a kind of 55: 45～25: 75 enantiomers put into solution, separate out precipitation in the temperature between 30 ℃～-30 ℃.

B) between 10 °～60 ℃ of temperature, the finger crystal seed is put into a kind of dissolving liquid of mixture, this mixture also comprises other homogeneous isomer except containing homogeneous isomer to the I a+ I b, and/or comprises homogeneous isomer I a+ I b with a kind of ratio rather than ideal value.Seed crystal by enantiomer to I a: I b=55: 45～25: 75 mixture is formed.Allow crystallization in the temperature of solution between 30 ℃～-10 ℃.Vacation is between-10 ℃～-20 ℃ in temperature then if required, and the mixture that obtains like this is suspended in proton or the nonpolarity non-proton inert organic solvents crystalline solid of separating out precipitation.

C) fused solution of a kind of solution of increase or a kind of mixture.The fused solution of this mixture is except comprising homogeneous isomer I a+ I b, also comprise other homogeneous isomer, and/or with a kind of ratio rather than a kind ofly specifically the ideal value of I a or I b is being comprised homogeneous isomer I a+ I b, enantiomer is with such value to I a or I b, that is: solution or fused solution should comprise homogeneous isomer with 55: 45～25: 75 ratio.Vacation if required, then can by a) or b) shown in method carry out crystallization.

D) with desirable ratio mix enantiomer to I a and I b(if wish to add proton and nonpolarity non-proton organic solution), make mixture homogenization, and carry out crystallization (vacation then can be undertaken by the step of putting into behind seed crystal a) if required).

A kind of best processing procedure that a) provides among the present invention is C _1-12Hydrocarbon, C _1-6Chlorinated hydrocabon, C _1-5=hydrocarbyl ether or C _1-10Alcohol is as organic solvent.Above-mentioned organic solvent can be straight chain also can be side chain, can be the ring, also can be alicyclic ring.

The method of preferentially selecting for use is when adding antioxidant, puts into a kind of seed crystal (particularly, tert-butyl group hydroxy-methylbenzene or 2,2,4-trimethylquinoline), and as solvent, what choosing was selected for use earlier is ethanol, isopropyl alcohol benzinum or hexane.

Processing procedure is preferably by slowly finishing crystallization under the cooling.

According to the mode of preferentially finishing process provided by the invention, the mixture of 60% trans Fenvalerate and 40% cis Fenvalerate (18.2% I a, 26.8% I b, 21.8% I c and 33.2% I d; It thinks I e in the time of earlier) be taken as raw material and use.Said mixture is dissolved in the isopropyl alcohol, be placed in the solution by I a and I b and add 0.01% 2,2, the seed crystal that the mixture of 4-trimethylquinoline or tert-butyl group hydroxy-methylbenzene is formed.We have obtained crystalline goods with 35～40% absolute yield, this crystalline goods fusing point is 63.5～65 ℃, containing enantiomer is 40: 60 to the ratio of I a and I b, and comprises that value is 5% enantiomer I c and I d(I c and I d are existed as impurity).Like this goods of Huo Deing can resemble above-mentioned method be recrystallized.Like this, enantiomer just can be made the mixture of I a and I b and surpass 99% purity.

When the mixture to other suitable/inverse ratio was recrystallized, we had obtained same result.

Being used as the mixture esterification method of the cyclopropane-carboxylic acid that Fenvalerate that raw material use can be by making suitably suitable/inverse ratio produces.

In following table, provided various suitable/fusing point of the mixture of inverse ratio.

Ⅰa/Ⅰb 25∶75 30∶70 40∶60 50∶50 55∶45

Fusing point: ℃ 67～71.5 65～78 63.5～65 60.5～62 61.5～64

On the desirable direction of crystallisation step, practical feasibility depends on the purity of former Fenvalerate mixture consumingly.If the content of active component is lower than 95%, so, yield will reduce, even tarry impurity can suppress crystallization.

Enantiomer also can carry out under solvent-free situation according to the present invention the crystallization of I a and I b mixture.Like this, can to put into Fenvalerate compounds I e just precipitable in a week at the mixture of refrigerator I a and I b with containing I a and I b crystal.The acquisition of this crystal is to separate out and leach crystal in the mixture by the ethanol that is cooled to-20 ℃ is added to.

Enantiomer to the mixture of I a and I b also can be according to the present invention by mixing and/or the method for crystallization I a and I b or inhomogeneous I a and I b is produced, perhaps by mixing and/or the method for the calculated value of crystallization I a and I b or I b is produced.

The biologically active of goods is to do overtesting on various insects according to the present invention.In the method for experiment, we have also found to be used as effect reference standard and produce the stereoisomers of (for example with chromatography or use the chromatography of the Fenvalerate of producing) from chiral acid with known method.

Pesticidal combination environmentally safe of the present invention is specially adapted to resist in hiding being in and winged insect and insect among the horse Stables, also is applicable to the control of pasture insect.

In following chemistry and biology example, further set forth the present invention, but protection scope of the present invention is not limited only to this.

Chemistry embodiment:

Embodiment 1

Temperature is 45.0 ℃, under constantly stirring, the Fenvalerate of 100g is (according to gas chromatography by a kind of 18.2% I a, 21.8% I c, the mixture of 26.8% I b and 33.2% I d is formed), 0.29 2,6-di-t-butyl-4-sylvan will be dissolved in the isopropyl alcohol of 2000ml.This solution is cooled to 30 ℃ lentamente, in 30 ℃, clarifies, filter with active carbon.This colourless solution is put into the crystallization that the I a by 60% I b and 40% forms, and mixture stirred 24 hours in-10 ℃.The product of filtering-depositing is cleaned with isopropyl alcohol, is placed in the vacuum dry.So just obtained the snow-white crystalline product of 36.02g, its temperature is 62～65 ℃ (non-correction values).According to gas chromatography and thin-layer chromatography analysis, product contains 37% I a and 58% I b homogeneous isomer, and yield is that 76%(is relevant with the content of the I a+ I b homogeneous isomer of raw material Fenvalerate).The Rf=0.25 of I a homogeneous isomer, the Rf=0.20 of I b homogeneous isomer.Behind the recrystallization, as gathering in the crops for the first time, we have obtained the product of 32g from isopropyl alcohol, and its fusing point is 63.5～65.0 ℃; Product is made up of 39.5% I a and 59.5% I b.Infrared spectrum (KBr) ν c=0: 1730,1735cm ^-1

Nuclear magnetic resonnance (CDCl ₃) δ (1,000,000/):

1.05～2.45m（8H）;5.6，d，J＝8Hz

(the trans 0.6H of=CH); 6.14, d, J=8Hz

(=CH cis 0.4H); 6.35, d(1H);

6.85～7.60m，（9H）

Embodiment 2

Temperature is in 45 ℃, constantly stirs 100g Fenvalerate (27.8%, I a, 21.8% I b, 32.1% I e and 18.2% I d), 0.2g potassium hydroxide and 0.2g2, and 6-di-t-butyl-4-sylvan will be dissolved in the isopropyl alcohol of 2000ml.In 30 ℃ with the active carbon settled solution and filter it.The seed crystal of being made up of 20% I b and 80% I a is put into this colourless solution, in-10 ℃, stirred 36 hours.The goods of filtering-depositing are cleaned also dry in a vacuum with isopropyl alcohol.We have obtained the snow-white crystalline goods of 30g like this, and its fusing point is 66～73 ℃.According to gc analysis, this goods contain 77% I a+19% I b, and purity is the 96%(thin-layer chromatography, sees embodiment 1).Behind the recrystallization, as generating for the first time, we have obtained the snow-white crystalline goods of 26.5g from isopropyl alcohol, and its fusing point is 70～73 ℃.Goods are by 81.5% I a+18% I b(gc analysis).Infrared spectrum (KBr) ν c=0: 1730cm ^-1

Nuclear magnetic resonnance (CDCl ₃) δ (one of percentage):

1.05～2.45m（8H）;5.60d，J＝8Hz，

(the trans 0.2H of=CH); 6.14d J=8Hz

(=CH cis 0.8H); 6.35d(ArCH 1H)

6.85～7.60m（9H）。

Embodiment 3:

The seed crystal of being made up of 60% I b and 40% I a is put into the water white oily Fenvalerate of 100g, allow solution one week of crystallization in 7 ℃.This mixture is suspended in the mixed solution of 100ml isopropyl alcohol and Di Iso Propyl Ether, filters it in-15 ℃.Crystal is cleaned with isopropyl alcohol, and is dry in a vacuum.We have obtained the snow-white crystalline goods of 40.1g like this.This goods contain 37% I a and 59% I b, and its fusing point is 62.5～65 ℃, and its yield is 86%.Behind recrystallization from isopropyl alcohol, as generating first, we have obtained the snow-white crystalline goods of 36g, and its fusing point is 63.5～65 ℃, and it is by 40% I a and 60% I b(gc analysis).What provide among infrared spectrum and nuclear magnetic resonnance and the embodiment 1 is identical.

Embodiment 4:

In 0 ℃ of the temperature under constantly stirring, 100g Fenvalerate (18.2% I a, 21.8% I c, 26.8% I b, 33.2% I d) and 0.05g2,6-di-t-butyl-4-sylvan just is dissolved in the Di Iso Propyl Ether of 100ml, clarifies this solution with the active carbon of 2g.Filtering solution is also put into solution to the seed crystal of being made up of 60% I b and 40% I a in-15 ℃.Allow crystalline mixture 72 hours, leach crystal, clean with the Di Iso Propyl Ether and the third different alcohol, and dry.We obtain the snow-white crystalline goods of 38g like this, and its fusing point is 62～65 ℃, and it comprises 37.5% I a and 58% I b, and yield is 80.6%.Behind the isopropyl alcohol recrystallization, as generating for the first time, we obtain the snow-white crystalline goods of 35g, and its fusing point is 63.5～65 ℃, and the ratio of I a and I b homogeneous isomer is 40: 60.What provide among its physical quantity and the embodiment 1 is identical.

Embodiment 5:

The 10g sample product (ratio of I a and I b homogeneous isomer is 4: 1) that is obtained according to example 2 respectively with 4.60g, 6g, 10g, 16.67g and the pure I b seed crystal of 22 22.09g is blended together, like this as described in the mixing image embodiment 1 of Huo Deing every kind all from 10 times isopropyl alcohol, be recrystallized.The composition of the goods of Huo Deing and fusing point are shown in the table like this.

I a: I b fusing point: (℃)

55∶45 61.5～64

5∶5 60.5～62

4∶6 63.5～65

3∶7 65～68

25∶75 67～71.5

Embodiment 6:

10g be crystalline pure homogeneous isomer to the sample of I a respectively with 8.20g, 10.00g and 15.00g are crystalline pure homogeneous isomer I b are blended together, and this mixture is stirred well.Contained I a of crystalline mixture of Huo Deing and the material of I b like this) be respectively 55: 45,50: 50 and 40: 60, fusing point was respectively 61.5～64 ℃, 60.5～62 ℃ and 63.5～65 ℃.

Embodiment 7:

10g is in crystalline pure homogeneous isomer is dissolved in 10 times to the sample of I a the isopropyl alcohol, and the crystalline pure homogeneous isomer I b of 23.34g is added in each sample.Solution is through recrystallization.The ratio that the white crystalline goods (solubility is respectively 65～68 ℃ and 67～71.5 ℃) of precipitation contain I a and I b homogeneous isomer respectively is 30: 70 and 25: 75.The goods of the Huo Deing prescription that can be used as plant protection product uses like this, and it is a kind of useful insecticidal active ingredient.

Allotment embodiment

Embodiment 8

The synthetic silicic acid of 0.8g (silicic acid 300) is being added in the perlite (dmax=120 μ m) of 166.2g in the fluidisation agitator fast.The 20g enantiomer to I a: I b=4: 6 Fenvalerate mixture and 2g fatty alcohol polyglycol ether are also added it, so that mixture is by homogenizing equably.This pulverulent mixture at first grinds in machinery stone roller machine, grinds in air-flow stone roller machine then.In flash mixer, 5g octyl phenol polyglycol ether (EO=20) and 2g sulfuration succinate are added thereon, the wettable pulverulent mixture (WP) of Huo Deing has carried out suspending stabilized degree test like this.Wetting time=23 second; The WHO method of floatability=89%(standard).

Embodiment 9

In the equipment of homogenizing, the 3g enantiomer to I a: I b=3: the mixture of 7 Fenvalerate and 0.3g fatty alcohol polyglycol ether are applied in the talcum (dmax=15 μ m), with 0.8g synthetic silicic acid (Aerosil 200) and 193.9g potassium phosphate and the such buffer of sodium phosphate, the pH value is adjusted to 6.5.1g=octyl group sulfuration succinate and 1g fatty alcohol polyglycol ether sulfonated ester, under agitation be added in this mixture, it is 20 μ m that mixture is ground particle mean size.We have just obtained a kind of fine and flowable fine powder mixture like this.

Embodiment 10

Stir lentamente and make the 5g enantiomer to I a: I b=55: the mixture of 45 Fenvalerate is dissolved in the mixed solution of 25g=toluene and 42.5gn-propyl alcohol.The 4g ethyoxyl alkyl phenol+calcium salt admixture of straight chain alkaryl sulfuration ester and the alkali metal salt of 6g ethoxylated amine+straight chain alkaryl sulfonated ester, under agitation be added in this solution, till all materials dissolve fully.21.25g water is added in the above-mentioned mixed solution.We have obtained a kind of transparent solution like this.In the temperature of this solution between 0 ℃ and 50 ℃, its characteristic can be kept long time.This solution can be the emulsion product of 0.8～1.5 μ m in droplet size, with the random dilute with water of arbitrary proportion.

Embodiment 11

The 5g enantiomer to I a: I b=25: the mixture of 75 Fenvalerate is dissolved in the mixed solution of the fat oil that contains 75g=toluene and 10g.Under stirring slowly, with the mixture (7.5g) of ethyoxyl alkyl phenol+straight chain alkaryl sulfonated ester calcium salt, the mixture (2.5g) with ethoxylated fatty acid+straight chain alkyl aryl sulfonate (salt) is added in the above-mentioned solution simultaneously.When measuring according to the CIPAC method, emulsion concentrate proof was still stable after 170 hours.

Embodiment 12

Is the enantiomer of Fenvalerate 50: 50 mixture to the ratio of I a and I b, in mechanical granulating machine with the poly-carboxylate alkali metal salt of 150g, the 500g neopelex, 500g sucrose and 7200g China potter's clay mix.The water of powder compound and 8300ml is mixed with the big agitator of shearing strength (v=10m/ second), carry out atomized drying then.Size distribution is as follows: 0.1～0.4mm accounts for 95%, and the floatability value is that 98%(is according to the WHO method).

Embodiment 13

Produce emulsifiable concentrate (EC) with the method for mixing following ingredients:

10 EC

Become score value, kg/kg

Homogeneous isomer is to I a: I b=40: 60 0.105

Ring ethanol 0.290

This (Atlox) 3386B 0.020 of Aunar Roc

This (Atlox) 3400B 0.045 of Aunar Roc

Tasteless mineral oil 0.540

5 EC

Become score value, kg/kg

Homogeneous isomer is to I a: I b=40: 60 0.050

Ring ethanol 0.290

Atlox 3386B 0.020

Atlox 3400B 0.045

Tasteless mineral oil 0.595

Biology embodiment

Embodiment 14

The activity of the stereoisomers of various Fenvalerates on housefly (Musca domestica) is shown in Table 1.

Test is carried out as follows:

It is in 1: 2 the mixture that active component is dissolved in oil and the ratio of acetone; Filter paper is full of corresponding stereoisomers solution and enantiomer respectively to solution.Allow acetone evaporated, insect is placed on the filter paper of Petri dish.Contrast three times, every kind of dosage and 15 insects are put into each Petri dish, after 24 hours, measure the percentage of lethality.Calculate the lethality percentage of revising with Alpert (Abbot) formula.

Table 1

Fenvalerate dosage (every filter paper of mg/)

Stereoisomers 0.04 0.11 0.33 1.00 3.00

(24 hours lethality (%)

Ⅰf 68 93 100 100 100

Ⅰa 44 84 100 100 100

Ⅰg 48 68 83 100 100

Ⅰb 32 62 95 100 100

Ⅰa∶Ⅰb＝40∶60 41 81 100 100 100

According to test, the activity of the mixture of I a+ I b is equivalent to the activity of pure I a homogeneous isomer.

Embodiment 15

As can be seen from Table 2, the increase activity that is shown in embodiment 14 is because the synergy of trans homogeneous isomer causes.

Table 2

Dosage (every filter paper of mg/)

Active component 0.11 0.33 1.00 3.00

24 hours, lethality %

1S cis R(I h) 0 38 80 100

1R cis S(I f) 80 100 100 100

Ⅰa 22 65 94 100

The trans R(I of 1S i) 00 71 90

The trans S(I of 1R g) 70 92 100 100

Ⅰb 64 89 100 100

Ⅰa∶Ⅰb＝40∶60 61 89 100 100

In embodiment 18, demonstrate on more insects, enantiomer provided by the invention is to the specific activity I a height of I b.The activity proof that increases it oneself is not only at 24 hours lethality height, and shows rapidlyer on toxic effect.

Embodiment 16

On flour beetle (Tribolium confusum), the enantiomer of various ratios is shown in the table 3 insecticidal effect of the mixture of I a and I b.Test method provides in embodiment 14.

Table 3

Dosage (every filter paper of mg/)

Ⅰa∶Ⅰb 0.02 0.06 0.25 1.00

24 hours lethality %

10∶0 0 14 54 100

5∶5 0 43 100 100

4∶6 14 53 100 100

3∶7 20 81 100 100

0∶10 8 46 100 100

Top data have clearly illustrated that at enantiomer the synergistic effect between I a and the I b.

Embodiment 17

According to further discovery of the present invention, when enantiomer during to the synergist chemical combination of the mixture of I a and I b and common pyrethroid (for example: piperonyl butoxide, NIA 16388 etc.), the value big (seeing embodiment 16) that the specific activity of increase is common.

Activity on the colorado potato beetle of Colorado is shown in Table 4.

The method of experiment is as follows:

Test material is dissolved in the cellosolvo (Cellosolve).The solution of one 0.3 μ m is applied on the target of adult belly.Contrast three times, and every kind of dosage has the mode of 10 worms to handle.Measure lethality after 48 hours.

Table 4

Dosage (every beetle of mg/)

Active component 0.05 0.10 0.20 0.40

24 hours lethality %

Ⅰa 50 55 75 80

Ⅰb 0 25 75 85

Ⅰa∶Ⅰb＝4∶6 45 60 70 80

Ⅰa∶Ⅰb＝3∶7 45 65 75 85

δ rice department woods 45 60 75 85

Fenvalerate 0 20 45 75

Although on the colorado potato beetle of Colorado, the specific activity I b of I a is big, synergistic effect occurred between enantiomer is to I a and I b.Enantiomer is just the same to the activity of the activity of the mixture of I a and I b performance and δ Mi Silin.

Embodiment 18

We go up I a, I b and a kind of I a: I b=40 bean weevil (Acanthoscelides obtectus), flour beetle (Tribolium confusum), housefly (Musca domestica) and sheep maggot fly (Lucillia sericata): 60 mixture compares test.Test method is embodiment 14 employed methods.Its result is summarized in the table 5.

Table 5

Dosage (every filter paper of mg/)

The kind enantiomer is to 0.02 0.07 0.22 0.67 2.0 6.0

Lethality %

Bean weevil I a 10 37 63 95 100 100

(adult) I b 32 55 87 100 100 100

Ⅰa∶Ⅰb＝4∶6 30 55 90 100 100 100

Flour beetle I a 0 18 51 100 100 100

(adult) I b 14 73 100 100 100 100

Ⅰa∶Ⅰb＝4∶6 16 80 100 100 100 100

Housefly I a 36 63 88 100 100 100

(adult) I b 0 18 67 100 100 100

Ⅰa∶Ⅰb＝4∶6 25 45 85 100 100 100

Sheep maggot fly I a 0 30 29 57 60 65

(adult) I b 22 55 70 75 100 100

Ⅰa∶Ⅰb＝4∶6 18 50 60 75 100 100

Embodiment 19

The right activity of Fenvalerate stereoisomers is the function of time on flour beetle.

The adult of flour beetle (Tribolium confusum) is placed in the Petri dish according to the method that embodiment 14 describes.For every kind of dosage, contrast three times.Each comparative trial is all put 15 adults.On each time point, calculate the insect lie on the back, the results are shown in the table 6 of its percentage.

Table 6

Stereoisomers is to putting into dosage (every filter paper of mg/)

With enantiomer to the time 0.11 0.33 1.00 3.00

The percentage % of poisoning situation appears in (branch) insect

Ⅰb 30 0 0 0 0

60 0 0 0 8

120 0 0 0 67

180 0 0 0 88

Ⅰf 30 0 0 48 64

60 0 5 84 100

120 0 40 100 100

180 39 61 100 100

Ⅰa 30 0 0 0 33

60 0 0 16 88

120 0 14 66 100

180 10 49 100 100

Ⅰi 30 0 0 0 15

60 0 0 0 70

120 0 0 0 100

180 0 0 0 100

Ⅰg 30 0 0 15 68

60 18 34 98 100

120 30 70 100 100

180 34 84 100 100

Ⅰb 30 0 0 47 61

60 0 21 82 100

120 28 100 100 100

180 56 100 100 100

Ⅰa∶Ⅰb＝ 30 0 0 50 55

4∶6 60 15 85 85 100

120 30 100 100 100

180 55 100 100 100

Embodiment 20

Dispose the adult of flour beetle (Triboliumconfusum) with embodiment 14 similar methods.Is dosage that the piperonyl butoxide of every filter paper of 0.5mg/ uses as synergist.

Table 7

Dosage (every filter paper of mg/)

Fenvalerate 0.4 0.2 0.1 0.05 0.025

24 hours lethality % of stereoisomers

Ⅰa 96 53 12 0 0

Ⅰa+FBO 100 58 16 0 0

Ⅰa+Ⅰb 100 90 57 18 0

Ⅰa+Ⅰb+FBO 100 95 75 43 7

As can be seen, enantiomer to the scope of the producible synergistic effect of mixture of I a and I b than scope big (the I a: I b=4: 6) of enantiomer to I a.

Embodiment 21

Solubilization of active ingredient in cellosolvo, and is added in L with the drop of 0.2 μ l volume with this drips of solution ₇～L ₈The back of the worm that is caught in stage (Hyphantria cunea) larva.Worm after the disposal is placed on strawberry (strawberry) leaf in the Petri dish.Use a kind of dosage, the secondary contrast is tested with the method that each dosage is put 10 insects.Calculate the worm amount of killing after 24 hours, calculate the percentage lethality.Its result is summarized in the table 8.

Table 8

Dosage (every larva of μ g/)

0.023 0.047 0.094 0.188 0.375

24 hours lethality % of active component

Ⅰa 40 60 65 80 90

Ⅰb 10 15 30 70 80

Ⅰa∶Ⅰb＝4∶6 40 50 55 65 75

Fenvalerate 0 10 25 50 75

Embodiment 22

Leaf spray medicine to having been invaded and harassed under baud tower (Potter Tower) by acarid (Tetranychus urticae).After 24 hours, compare at epiphyllous lethality and the tester handled.

Table 9

Active component is near median lethal dose (1,000,000/)

Ⅰa 0.056

Ⅰb 0.340

Ⅰa∶Ⅰb＝4∶6 0.060

Fenvalerate 0.120

δ rice department woods 0.185

Embodiment 23

The 5EC prescription of producing according to embodiment 12 dilutes with the water of 50 times, 100 times, 200 times, 400 times, 800 times and 1600 times.0.5ml dosage is sprayed on the glass plate.After the drying, put 10 beetles (decemlineata) adult on the every glass plate, and build with Petri dish.Test is to contrast three times with 6 kinds of dosage and every kind of dosage.Calculate the worm amount of killing after 48 hours.It the results are shown in the table 10.

Table 10

Dilution factor

1600 times 800 times 400 times 200 times 100 times 50 times

The 5EC lethality of filling a prescription

Ⅰa 0 27 53 63 87 97

Ⅰa∶Ⅰb＝4∶6 0 33 53 73 80 93

δ rice department woods 7 35 53 67 83 100

Fenvalerate 0 17 53 50 67 83

Embodiment 24

With 5EC prescription spraying glass plate, the method for spraying is similar to embodiment 23.The 5EC prescription is according to embodiment 13 preparations.After doing spray, put 10 bean weevils (Acemthoscelides obtectus) adult on the every glass plate, and build with Petri dish.Calculate the worm amount of killing after 24 hours.Test is with 6 kinds of dosage, and the method that adopts every kind of dosage to contrast three times is carried out.Its result is summarized in the table 11.

Table 11

Dilution factor

1600 times 800 times 400 times 200 times 100 times 50 times of 5EC prescriptions

Lethality %

Ⅰa 0 13 27 33 50 70

Ⅰa∶Ⅰb＝4∶6 10 17 30 37 53 70

δ rice department woods 7 13 20 37 57 75

Fenvalerate 03 10 20 45 60

Embodiment 25

Catch the 15 strain pulses leguminous plantss of leaf lice (Myzus persical) in 6 days time, a basin is planted in a strain.In 12 day time, chose and infect heavy and plant uniformly, use fresh emulsion to spray according to the formulated of embodiment 13.With three kinds of dosage (active component is 2.5/1000000ths, 5 and 10) and contrast (each basin) four times.After processing second day, the 4th day and the 8th day swept on the blank sheet of paper from plant with thin brush handle aphid, calculates the quantity of the worm that lives.It the results are shown in the table 12.

Table 12

The mean of the every basin aphid of concentration

Fate after the 5EC prescription is handled

(1,000,000/) 248

Ⅰa 2.5 44 83 245

5.0 22 29 90

10.0 8 17 30

Ⅰa∶Ⅰb＝4∶6 2.5 38 71 251

5.0 21 32 82

10.0 10 11 21

δ rice department woods 2.5 26 47 137

5.0 13 19 29

10.0 6 11 23

Amount to 1,850 2,780 4120

Embodiment 26

In advance tomato class plant cultivating in basin, with the spraying of a kind of suspension of active component.The suspension of this active component is that the mixed solution by acetone and water forms.Plant after the processing is put in the cage, and uses L ₃The larva of the colorado potato beetle in stage (Leptinotarsa decemlineara) infects.Measure the paralysis that falls from plant after 6 hours the percentage of larva.It the results are shown in the table 13.

Table 13

Ⅰa Ⅰa∶Ⅰb＝4∶6

The percentage % of concentration (1,000,000/) paralysis larva

1000 100 100

200 100 100

40 46 75

8 18 60

Embodiment 27

Processing to Colorado colorado potato beetle on the severe infections flies to carry out in the territory at 25 square metres.Each zone marks 10 strains with additional character.On each zone, calculate the quantity of Colorado colorado potato beetle in advance and (when estimating that insect is counted, only consider the adult of second procreation in summer.Because when experiment, L ₃And L ₄The larva in stage can be ignored.On 25 square metres zone, handle with the dosage of per hectare 10g active component.Active component is the watery suspension according to the formulated of embodiment 10, contrasts three times.Test is estimated with the method for calculating the worm that lives on the plant that marks.The mean value of three comparative trials is shown in Table 14.

Table 14

Worm mean alive/10 strains

The 5ME prescription (elapsed time after handling (my god)

0 1 3 9

Ⅰa 171 11 9 25

Ⅰa∶Ⅰb＝4∶6 213 8 4 22

δ rice department woods 181 7 10 19

Tester 211 206 179 183

Embodiment 28

The aftereffect contact test of on the adult of Aphidinus matricarial, carrying out.The adult of Am matricarial is placed in and newly is applied on the residue that forms the active component on the glass plate that shrouds, and calculates survivor's quantity then.

Handle: experiment goods (test product(s)) with the tester of water treatment.

Same test: at least three times, area size (grid): 1 shrouds.

Use the known life-span parasite of (24 hours).

Is concentration that the product of 5.1ppm is applied on the every glass plate.

The female worm of 10 A.matricariae is put into during each shrouds, and feeds with honeybee.The quantity of the female worm that independent operational measure is survived after 1 hour, 5 hours and 24 hours.Each is shrouded statistics survivor's sum.It the results are shown in the table 15.

Table 15

Concentration

5,000,000/1000000ths/

1 hour 1 hour 5 hours 24 hours

Lethality %

Ⅰa 100 100 100 96

Ⅰa∶Ⅰb＝4∶6 100 50 90 63

δ rice department woods 100 20 100 85

Embodiment 29

On the pupa of A.matricarial, carried out direct contact test.

The active component that the ripe pupa contact of A.matricarial on the red pepper leaf that allows at Petri dish is directly sprayed.Use when before the red pepper that parasitic pupa is arranged grows young leaves 2 days or 3 days.Leaf is placed on the filter paper that bedews in the plastics Petri dish.

The application of handling: see embodiment 28.

Leaf after several processing is moved to the bottom of clean Petri dish.It is that 20 ℃, relative moisture are 70% that culture dish is stored in a temperature, is in 16～8 hours the greenhouse after 2～3 days with the daily cycle, and the pupa of survival begins hatching.Calculate the quantity of hatching and the quantity of dead pupa.It the results are shown in the table 16.

Table 16

Concentration

5,000,000/10,000,000/30,000,000/1000000ths/

Lethality %

Ⅰb∶Ⅰa＝6∶4 14.3 0 0 0

δ rice department woods 75.0 33.0 00

Ⅰa 77.0 12.5 0 0

Comparison 0000

Claims

1, the Pesticidal combination that contains the various active component is characterized in that comprising the such active component of synthetic pyrethroid of a kind of general formula (1), and its shared weight ratio is 0.001～99%.(X represents chlorine or bromine in the general formula (1)).-promptly come from the right of 8 kinds of possible homogeneous isomers

Reflect body to Ia: Ib=55: 45～25: 75 mixture accounts for 95% at least, wherein Ia is 1R cis S+1S cis R, Ib be the trans R-vacation of the trans S+1S of 1R if required, can also in mixture, mix a kind of activator, and/or mix a kind of adjuvant, value is to 100%; It is better to mix a kind of antioxidant, stabilizing agent, wetting agent, emulsifier, dispersant, antifoaming agent, carrier and/or filler.

2,, wherein comprise the I a that uses as active component: I b=40: 60 mixture according to the Pesticidal combination of claim 1.

3,, wherein comprise the I a that uses as active component: I b=30: 70 mixture according to the Pesticidal combination of claim 1.

4,, wherein comprise the I a that uses as active component: I b=50: 50 mixture according to the Pesticidal combination of claim 1.

5, insecticidal active ingredient comprises 8 kinds of possible homogeneous isomers (X represents chlorine or bromine in the general formula (1)) of the synthetic pyrethroid that self-drifting (1) provides.In fact only comprise enantiomer to I a: I b=55: 45～25: 75 mixture (wherein I a is 1R cis S and 1S cis R, and I b is trans S of 1R and the trans R of 1S).The preparation method of this insecticidal active ingredient comprises:

A) from mixture, produce.This mixture also comprises other possible homogeneous isomer except comprising homogeneous isomer to the I a+ I b.And/or comprise homogeneous isomer to I a+ I b with the ideal value of a kind of ratio rather than saturated solution.This saturated solution is proton or nonpolarity non-proton inert organic solvent.By enantiomer to I a: I b=55: the seed crystal that 45～25: 75 mixture is formed, put into solution, the crystalline solid of separating out precipitation in the temperature between 30 ℃～-30 ℃.

B) in the temperature between 10 ℃～60 ℃, seed crystal is put into a kind of molten mixture.This mixture also comprises other homogeneous isomer except comprising homogeneous isomer to the I a+ I b, and/or is that ideal value comprises homogeneous isomer I a+ I b with a kind of ratio percentage.Seed crystal by enantiomer to I a: I b=55: 45～25: 75 mixture is formed.Allow crystallization in the temperature of solution between 30 ℃～-10 ℃.Vacation then in the temperature between-10 ℃～-20 ℃, is suspended in proton or the nonpolarity non-proton inert organic solvents crystalline solid of separating out precipitation to the mixture that obtains so if required.

C) add a kind of solution or a kind of molten mixture.Mixture also comprises other homogeneous isomer except comprising homogeneous isomer to the I a+ I b.And/or with a kind of ratio rather than a kind of enantiomer the ideal value of I a or I b to be comprised homogeneous isomer be such value to I a+ I b enantiomer to I a or I b, that is, solution or fused mass should comprise homogeneous isomer with 55: 45～25: 75 ratio.Vacation if required, then can by a) or b) carry out crystallization.

D) mix enantiomer if required with desirable ratio, then add proton or nonpolarity non-proton organic solution I a and I b(vacation), make mixture homogenization, and carry out crystallization (then can be undertaken vacation if required) by the step of putting into behind seed crystal a).

6, according to the process of producing a) in the claim 5, comprise C _1-12Hydrocarbon, C _1-6Chlorinated hydrocabon, C _2-6Dialkyl ethers or C _1-10Alcohol uses as organic solution.Above-mentioned solvent can be straight chain also can be side chain, can be the ring also can be alicyclic ring.

7, according to claim 5 a), c) or d) described preparation method, be included under the situation that anti-antioxidant participates in, put into seed crystal.

8, according to the preparation method of claim 7, comprise tert-butyl group hydroxy-methylbenzene or 2,2, the 4-trimethylquinoline uses as antioxidant.

9, according to each preparation method in claim 7 and 8, wherein ethanol, benzinum or ethane are used as solvent.

10, Pesticidal combination according to claim 1 can be prevented and treated hexapeopoda pest with the dosage of the active component of per hectare 2.0～25g.