CN1015709B - Insecticidal compositions comprising more than one active ingredients - Google Patents
Insecticidal compositions comprising more than one active ingredientsInfo
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- CN1015709B CN1015709B CN86101357A CN86101357A CN1015709B CN 1015709 B CN1015709 B CN 1015709B CN 86101357 A CN86101357 A CN 86101357A CN 86101357 A CN86101357 A CN 86101357A CN 1015709 B CN1015709 B CN 1015709B
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- isomer
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- 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
- A01N53/00—Biocides, pest repellants or attractants, or plant growth regulators containing cyclopropane carboxylic acids or derivatives thereof
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
- A01P7/00—Arthropodicides
- A01P7/04—Insecticides
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- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Environmental Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Engineering & Computer Science (AREA)
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- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Dentistry (AREA)
- Agronomy & Crop Science (AREA)
- Insects & Arthropods (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a combined insert killer containing more than one active component; the utility model is innocuous to environment and comprises a molecular type (one) combined pyrethrum ester of 0.001-99 percent (weight). In eight isomers, the invention contains only enantiomorph (one b) of 1R transform S and 1S transform R, mixes with one or a plurality of activator and additive with a content of 100 percent (weight). The invention relates to a compound one b and relevant production method.
Description
The present invention relates to contain insect-killing composition and the using method thereof of more than one molecular formula, active ingredient and preparation method thereof for the pyrethroid active ingredient of (I).
In patent specification, when relating to the substituent space structure of chiral carbon atom of usefulness " α " expression, use respectively " S " and " R ".The position characteristic of replacement relevant with the substituent space structure of carbon atom " 1 ", that be connected with carbon atom " 3 " on the cyclopropane ring uses " cis " and " trans " to represent respectively.The substituent absolute space structure that is connected with carbon atom " 1 " is used prefix " 1R " and " 1S " expression respectively.
In patent specification, various enantiomorphs and enantiomorph are to representing with following abbreviation respectively:
The mixture of Ia 1R cis S and 1S cis R
The mixture of trans S of Ib 1R and the trans R of 1S
The mixture of Ic 1R cis R and 1S cis S
The mixture of trans R of Id 1R and the trans S of 1S
If 1R cis S
The trans S of Ig 1R
Ih 1S cis R
The trans R of Ii 1S
Known pyrethroid with molecule formula I (is commonly called as Sai Bomisilin-Cypermethrine) and belongs to the most useful gang in the synthetic pyrethroid, can be used as sterilant (No. 170,866, hungarian patent).The preparation method of these compounds is as follows: in the presence of alkali, between using-phenoxy group-benzaldehyde cyanhydrin and the corresponding reaction of cyclopropane-carboxylic acid muriate [Pestic.Sci.6,537-... (1975)].The product that obtains in this way contains 8 kinds of steric isomers, that is: four kinds of mixtures that enantiomorph is right.When the trans and muriatic ratio of cis cyclopropane-carboxylic acid corresponding in the mixture is 60: 40, contain the 18-19% enantiomorph in the product mixture to Ia, the 21-22% enantiomorph is to Ic, and the 26-27% enantiomorph is to Ib, and the 33-34% enantiomorph is to Id.
According to prior art, the different steric isomers of Sai Bomisilin demonstrate different biological activitys.Usually can think: the activity of cis cyclopropane carboxylic acid acid molecule is higher than the activity (Pest.Sci.7,273(1976)) of corresponding antiderivative molecule.
In the contrast biological test of various pyrethroids [Pest.Sci.9,112-116(1978)] to cis and trans-stereoisomer-comprise Sai Bomisi stand in great numbers the body isomer right-estimate jointly.
Carried out simultaneous test with housefly L and beans snail shape daikon leaf beetle.About the chlorine derivative of trans-isomer(ide), the trans S(Ig of IR is disclosed) and the activity data of the trans R of 1R.These data show: the trans S isomer of 1R has very strong activity, and the trans R isomer of 1R has only very low activity.[according to test, corresponding to 100 parts of biological Li Simisi woodss (bioresmethrine), above-mentioned two kinds of isomer are respectively 1400 and 81 to the activity of housefly, and the activity of snail shape daikon leaf beetle is respectively 2200 and 110].Subsequently, it is lower than calculated value also to disclose the activity of these two kinds of underproof isomer mixtures.This be because the antagonistic action that shows of isomer greater than the cause of the synergy of being expected.Mixture is respectively 1.42 and 1.46 to the antagonistic action rate of housefly and mustard beetle.
The result who delivers of this experiment and trans-isomer(ide) and composition thereof has promoted people to study the interest of biological this situation of active group, and research work is focused on cis reactive derivative and composition thereof aspect.This causes the exploitation of a Mi Silin [the 1R cis S and the 1S cis R isomer mixture (Ia) that contain chlorine derivative] and Mi Silin in the last of the ten Heavenly stems [the 1R cis S isomer (If) that contains br-derivatives].
The similar data of having announced that contains br-derivatives in addition, it is 1.48 to the antagonistic action rate of mustard beetle.
One aspect of the present invention provides and contains synergistic complexing insect killing composition more than one active ingredients, environmental sound.It is characterized in that containing synthetic pyrethroid 0.001 to the 99%(weight of molecular formula for (I))-promptly in 8 kinds of possible isomer, the enantiomorph that in fact only contains trans S of 1R and the trans R of 1S arrives 100%(weight to (Ib)-randomly at most with content) a kind of or several activators and auxiliary, oxidation inhibitor particularly, stablizer, wetting agent, emulsifying agent, dispersion agent, antifoams, thinner and/or weighting agent fusion.
In the embodiment of this recommendation on the one hand of the present invention, provide a kind of insect-killing composition that purity is not less than 95% isomer mixture that contains.
This isomer mixture is a kind of new crystalline material, and its physical-chemical data openly in an embodiment of the present invention.
The present invention have effectively with isomer mixture (Ib) and easily these admitted facts of biological property be foundation.Even consider molecular formula has been finished a large amount of cut-and-try works for the pyrethroid of (I), and announced many relevant patents and patent specification, this point is still beat all.
Moreover the present invention is a foundation with the following fact of generally acknowledging also.Promptly, using the trans S isomer of 1R Ig(is that molecular formula is a highest active trans-isomer(ide) in the compound of (I)) and the trans R isomer of 1S Ii(be the minimum isomer of activity in 7 kinds of isomers that are left) composition, do not observe the right antagonistic action of isomer of previous announcement.
Moreover when using composition, find the additive effect of synergistic effect greater than pure Ig and Ii isomer.
The above-mentioned generally acknowledged fact helps to pick out the novel active ingredient with obvious characteristic from those have the pyrethroid ester isomer of synergy.This novel active component is compared with the isomer that uses so far always, shows various advantages:
-to warm-blooded animal kind and human hypotoxicity
-both economical production method
-little to the injury of useful zooparasite and honeybee
Obvious and the conclusive advantage of isomer mixture Ib provided by the invention is not cause allergy and tetter.And this is to use and generally sees when having similar active corresponding cis Sai Bomisilin isomer.
The synergism activity of isomer mixture Ib composition is more unexpected, because similar synergy does not take place isomer mixture Ia composition.
It is right that another aspect of the present invention provides through the isomer of selecting, and contains the right insect-killing composition of this isomer, and preparation method thereof and using method.
Another aspect of the present invention provides the right preparation method of this novel isomer.The aspect of a particularly important of the present invention provides the preparation method of Sai Bomisilin isomer to Ib.This method is a kind of method for preparing active ingredient of high economic benefit.Activity with the activity of the active ingredient of this method preparation and those the pure single cis-isomeride active ingredients that up to the present can only could produce with the isolation process of costliness is identical.
Another aspect of the present invention provides and contains synergistic complexing insect killing composition more than one active ingredients, environmental sound, it is characterized in that, contain synthetic pyrethroid 0.001 to the 99%(weight of molecular formula for (I))-promptly in 8 kinds of possible isomer, the enantiomorph that in fact only contains trans S of 1R and the trans R of 1S is up to 100%(weight to (Ib)-randomly with content) a kind of or several activators and auxiliary, oxidation inhibitor particularly, stablizer, wetting agent, emulsifying agent, dispersion agent, antifoams, thinner and/or weighting agent fusion.
Another aspect of the present invention provides purity and is not less than 95% the molecular formula isomer mixture Ib that the trans S of 1R and the trans R of 1S is made of enantiomorph for (I).
The right physical constant of this enantiomorph is as follows:
C=0=1735 centimetre of infrared spectra (Potassium Bromide) γ
-1;
Nucleus magnetic resonance
(CDCl
3) δ (ppm)=1.22,1.27CMe
2; 1.69d 1HCl; 2.32m 1HCl '; 5.6, d.1HCl '; 6.39S1H α proton.
This pure enantiomorph is right, as far as our knowledge goes, is a kind of white crystals of never describing in the prior art.The fusing point of 1: 1 mixture of isomer is 81.0-81.5 ℃.According to another report, the Ig of isomer centering and Ii composition itself is not crystalloid.Therefore, except biology and favourable condition economic aspect, the present composition is also simplified production process, preparation, storage and facture.
From the side effect aspect, isomer of the present invention also is better than known composition to Ib.New isomer of the present invention is right, and honeybee is had low-down toxicity, does not injure useful insect and zooparasite (seeing biological Examples 4 and 5).This is because the repellent effect of active ingredient, good persistence and suitable intrinsic activity determined.Owing to have above-mentioned these superior character, insect-killing composition of the present invention can be used for " comprehensive plant protection technology " (IPM=integrated disease scolite reason)
The present invention is also based on the following generally acknowledged fact: insecticidal activity that enantiomorph of the present invention is right and enantiomorph are basic identical to the insecticidal activity of Ia, and the warm-blooded animal kind is had significantly lower toxicity.This point can very clearly be proved with selectivity coefficient.Selection index (7800) is the merchant of the approximate medium lethal dose (LD50,5000 milligrams/kilogram) of mouse divided by approximate medium lethal dose (0.64 milligram/kilogram) gained of housefly.Enantiomorph is 50/0.45=111 to this selectivity coefficient of Ia.
With isomer Ia is compared, isomer has lower toxicity to Ib to zooparasite, this point particularly important.Owing to this reason, use insect-killing composition of the present invention safer.At the edge that sprays the district, (i.e. the zone of handling) after treatment with the active ingredient of lower concentration, zooparasite and honeybee are not injured.Isomer is also good highlightedly to the repellent effect of Ib.
With of the present invention, contain insect-killing composition and the known additives fusion of isomer to Ib, can be mixed with and be suitable for the medicine type that directly uses.
Composition of the present invention can be the ultra-low volume composition, spray liquid, but dispersion powder, particle, wettable powder, other pulvis or stable emulsion.Above-mentioned composition is applicable to the deinsectization processing of vegetable garden, orchard, cereal farmland and other extensive raise crop.Because composition of the present invention has hypotoxicity, so the winged insect in be specially adapted to unpeople dwelling house and the corral and with the insect of concealed manner life.The deinsectization that also is applicable to domestic animal bathing and pasture is handled.
Another aspect of the present invention provides the using method of this insect-killing composition.The using method of the said composition of recommending is: under the condition of farmland, the active ingredient consumption in per hectare farmland is the 2-25 gram.
Insect-killing composition of the present invention also comprises the activator Ib added to isomer and other synergist.For example: piperonyl butoxide.Above-mentioned additive can be strengthened the efficient of active ingredient, does not increase the toxicity to warm-blooded animal.
In the embodiment that the present invention recommends, provide and use 1-99%(weight) active ingredient and 99-1%(weight) discrete particles that suitable additive is blended into, can use 0.1-1%(weight as auxiliary) anionic and/or nonionic surface active agent.For example: the basic metal alkylaryl sulphonate, the an alkali metal salt of alkyl aryl sulphonic acid and formaldehyde condensation products, alkylaryl polyglycol ether, the sodium salt of sulfonated long chain alcohol, polyethylene oxide, the sodium salt of sulfonated aliphatic alcohol, fatty acid polyglycol ester and other various tensio-active agents as commodity selling.
Insect-killing composition of the present invention also can be mixed with enriched material.The enriched material 5-50%(weight of recommending) active ingredient and 50-95%(weight) the additive fusion of formation stable emulsion forms.
Can also use an anti-additive [consumption is 1-20%(weight)] and/or the stablizer [consumption is 0.1-5%(weight)] opened.The most handy organic solvent complements to 100% with mixture.
The anti-additive of recommending to use of opening is anionic or the non-ionic type anti-mixture of opening additive of hydrophile-lipophile balance value (HLB value) as 8-14.Preferably use the following anti-additive of opening: alkyl aryl sulphonic acid calcium, phosphoric acid one ester or phosphodiester, nonyl and tributyl phenol polyglycol ether, Fatty Alcohol(C12-C14 and C12-C18) and ethylene oxide adduct, fatty acid polyglycol ester, oxyethane one propylene oxide bulk copolymerization thing etc.
The solvent of recommending to use is aromatic hydrocarbons mixture (for example, dimethylbenzene), hexalin, butanols, butanone, Virahol etc.
Composition of the present invention also can contain other synergist, and the latter can reduce the consumption of active ingredient.For this purpose, recommend to use piperonyl butoxide.
Another aspect of the present invention provide from other mixture of isomers that contains other composition the preparation molecular formula for (I), in 8 kinds of possible isomer, in fact only contain the method for the enantiomorph of trans S of 1R and the trans R of 1S to the product of (Ib).
All mention in several parts of patent specifications: enrichment may have the Sai Bomisilin mixture of greater activity in isomer.[CA95 rolls up (1981) according to patent specification, Japan's publication 57755/81], crystalline, contain 86.9%Ic, the Sai Bomisilin isomer mixture of 9.5%Ia and 5.6%Ib+Id can be produced in the mixture of 38.7%Ia and 7.8%Ib+Id with seeding from containing 53.5%Ic.In the case, can expect that the biological activity of staying the compound in female alkali lye will improve.
The target of other currently known methods also be the preparation cis-isomeride to or the material of cis-isomeride centering enrichment.According to known technology, adopt asymmetric method for transformation, make Ia and Ic enantiomorph stand epimerization, can be the Ic enantiomorph is right to changing into the Ia enantiomorph by asymmetric conversion, with make respectively known α Mi Silin and the last of the ten Heavenly stems Mi Silin.[Chem.and Ind., March 19,1985,199-204; GB Patent Application No. 8013308; EP NO.0067461; HOII P 888431 is seen Derwent 79766D].
Prior art is not mentioned the preparation method of trans-isomer(ide).
Another aspect of the present invention provides also the method for in fact only by enantiomorph the trans S of 1R and the trans R-of 1S promptly being had only the two kinds-isomer mixture Ib that forms from molecular formula for preparation other mixture of isomers of (I) in molecular formula may isomer for (I) 8 kinds in fact.This method comprises:
A) adopt protonic solvent or nonpolar proton-inert organic solvent, will contain required isomer and be mixed with in addition that possible mixture of isomers is mixed with saturated solution.With containing the crystal seed of enantiomorph solution is carried out seeding to trans S of 1R and the trans R of 1S.The settled crystallization of in+30 ℃ to-30 ℃ temperature range, emanating out.
B) will contain required isomer and be mixed with in addition that possible mixture of isomers dissolves.In 10 ℃ to 60 ℃ temperature range, usefulness contains the trans S of 1R and the right crystal seed of the trans R enantiomorph of 1S carries out seeding to melt.In 30 ℃ to-10 ℃ temperature range, generate crystal.If desired, in-10 ℃ to-20 ℃ temperature range, the mixture that generates in this way is suspended in protonic solvent or the nonpolar proton-inert organic solvent the separated crystallization of emanating out.
C) will contain required isomer to Ib and be mixed with in addition that possible mixture of isomers is dissolved in the organic solvent, the silica gel by recommendation is housed or the chromatographic column of diatomite adsorbant are separated.
D) the trans-isomer(ide) mixture of molecular formula for the compound of (I) is dissolved in protonic solvent or the nonpolar aprotic solvent.With containing enantiomorph to trans S of 1R and the trans R(Ib of 1S) crystal seed solution is carried out seeding.Settled crystallized product Ib emanates out.After this, if desired, female alkali lye that will contain the Ib+Id mixture carries out epimerization with organic or inorganic alkali to be handled.If desired, can repeat aforesaid operations and/or crystallization operation.
E) the trans-isomer(ide) mixture is dissolved in the secondary amine or tertiary amine organic bases that contains 4-9 carbon atom-adds the solution of a kind of optional organic solvent-will obtain in this way, carry out seeding with the crystal seed that contains trans S of 1R and the trans R isomer of 1S.Then, the settled crystallization of emanating out.
According to the present invention, such scheme a) and e) in, preferably with an organic solvent: C
1-12Hydrocarbon, C
1-6Chlorinated hydrocarbon, C
1-5Dialkyl ether, or C
1-10Alcohol goes ahead.Above-mentioned solvent can be respectively a straight chain, side chain, cyclic or alicyclic.
Carrying out seeding when handling, the seeding process of recommendation should be carried out under 4-trimethylquinoline-existence at the tertiary butyl hydroxytoluene or 2,2 of oxidation inhibitor-particularly.Should use ethanol simultaneously, Virahol, sherwood oil or hexane are made solvent.
According to the inventive method, at such scheme d) in, the solvent of recommending to use is: C
4-10Alkane, C
5-10Naphthenic hydrocarbon, C
1-8Alkyl alcohol and/or C
5-8Cycloalkanol or its mixture.Solvent is especially easily: hexane, sherwood oil, hexanaphthene, methyl alcohol, ethanol or Virahol.
When carrying out the epimerization processing, ammonia, secondary amine, tertiary amine or Cycloalkyl amine can use as alkaline matter.The alkaline matter of recommending to use has: triethylamine, diethylamine, morpholine, tetramethyleneimine, piperidines, Diisopropylamine, ephedrine, triethylenediamine, benzylamine, n-Butyl Amine 99, sec-butylamine, tetrabutylammonium hydroxide, sodium hydroxide, potassium tert.-butoxide, sodium isopropylate or contain the ion exchange resin of quaternary ammonium compound or be equivalent to the high molecular weight amines of catalyst levels.
The solvent of recommending to use has: methyl alcohol, ethanol, Virahol, sherwood oil or hexane.
If include molecular formula in total production line for the preparation of isomer (I), different with Ib during with application, above-mentioned reaction scheme can be used very economically.
If synthetic Sai Bomisilin process adopts such scheme, and the major objective of invention is to adopt certain esterification techniques only to produce trans Sai Bomisilin mixture, so, the described such scheme e of the inventive method) be exactly a kind of most economical method of isomer that be particularly suitable for producing to Ib.According to such scheme e), exactly whole trans mixtures are changed into required enantiomorph to Ib.
According to scheme e), the organic amine bases of recommending to use has: triethylamine, drench tetramethyleneimine, piperidines, Diisopropylamine, ephedrine or sec-butylamine.
Scheme e) prerequisite of feasibility with amorphous pure isomer Ii and Id make purity greater than 95%, be higher than 80 ℃ of highly purified crystal seeds of following fused.Be beneficial to realize this target of asymmetric conversion.
In addition, further going on doing is preferably in organic solvent and exists down mixture is dissolved in the amine, for realizing this purpose, and the solvent that available solutions is enumerated in a).
According to scheme a), going ahead is with trans Sai Bomisilin isomer mixture-contain the trans S of 1R, the trans R of 1S, the trans S isomer of trans R of 1R and 1S-be dissolved in the triethylamine.Crystalline raw material is dissolved down at 40 ℃ to 70 ℃.Filter gained solution.Buttery Sai Bomisilin mixture at room temperature also can dissolve.The right crystallization of the trans R isomer of trans S of 1R and 1S can at room temperature be used solution is carried out the realization of seeding method.Crystal seed is trans S of 1: 1 1R and the trans R mixture of isomers of 1S (purity 99.8% of recommendation).Then, with the mixture that obtains in this way, 0 ℃ under 20 ℃, under stirring or not stirring, carry out crystallization treatment.The crystallization that is settled out is separated with filtration or centrifugal method.Stick to female alkali lye on the crystal surface with hydrocarbon (solvent of recommendation is naphthenic hydrocarbon, particularly sherwood oil) flush away.Merge female alkali lye, fully concentrate.Above-mentioned crystallization operation can repeat.Asymmetric conversion process is preferably in the exsiccant rare gas element (preferably nitrogen) carries out.
Can make the trans S of 1R and the trans R mixture of isomers of 1S of purity about 95% according to the method described above, one-pass yield can reach 80%.Use alcohol, particularly Virahol carries out recrystallization, can make purity bring up to 99-99.5%.
Also can make solvent with alkali.Recommend the water content of the amine alkali of use should be not more than 0.2-0.4%.Trans Sai Bomisilin mixture as raw material will descend as be infected with productive rate by sequence isomer.
Insect-killing composition environmental sound of the present invention, the winged insect in be specially adapted to unpeople dwelling house and the corral and with the insect of concealed manner life is applicable to that also the bathing of domestic animal and the deinsectization in pasture handle.
Details of the present invention will be introduced in following chemical embodiment and biological Examples.But, these embodiment do not limit protection scope of the present invention.
Chemistry embodiment
Embodiment 1
10 grams are contained 18.2%Ia, and 21.8%Ic, the Sai Bomisilin mixture of 26.8%Ib and 33.2%Id are dissolved in 50 milliliters of normal hexanes and tetrahydrofuran compound of 95: 5.Solution is poured in the chromatographic column that 500 gram silica gel G are housed.Do the eluent elution with 95: 5 normal hexanes and tetrahydrofuran compound and go out 25 milliliters of fractions.Collection Rf value is 0.2 fraction (thin-layer chromatography moving phase is 95: 5 normal hexane and tetrahydrofuran compound).With this fraction vacuum-evaporation.The residue that will obtain in this way (2.9 gram) under 45 ℃, is dissolved in 29 milliliters of ethanol again.Under 0 ℃, carry out crystallization.Leach throw out.With water-cooled alcohol flushing secondary, 10 milliliters of each consumptions.Vacuum-drying can obtain 2.6 gram white crystals.80.2 ℃ of fusing points.
Representational analytical data is as follows:
R
f=0.2(diatomite G post is 95: 5 normal hexane and a tetrahydrofuran compound)
C=0=1735 centimetre of infrared (Potassium Bromide) γ
-1
Nucleus magnetic resonance (CDCl
3) δ (ppm) 1.22,1.27, CMe
2; 1.69, d, 1HCl; 2.32, m1HC3; 5.6, d, 1HCl; 6.39, S, 1H, Ca proton.
Embodiment 2
In the trans Sai Bomisilin mixture of 10 gram crystalline (, containing trans S isomer of the trans R+1S of 53.9%1R and 43.3%Ib isomer), add 15 milliliters of anhydrous triethylamines by the gas chromatographic analysis data.Mixture under continuously stirring, heat temperature raising to 60 ℃ in nitrogen gas stream.Solution is filtered fast, be cooled to 30 ℃.The cleaning colourless solution that this method obtains was with 1: 1 Ib isomer mixture crystal seed seeding.Be cooled to room temperature.Placed one day, and made its crystallization.With the mixture cold filtration.Product is at room temperature dry.Obtain the snow-white crystallization of 8.4 grams like this, fusing point is 79.5-80.5 ℃.Gas chromatographic analysis shows that product contains the Ib isomer mixture of 95%1: 1 expection.With female spent liquor evaporation.Repeat aforesaid operations, obtain second batch 1.05 gram white crystals product, fusing point 79-80 ℃.
After the product merging, carry out recrystallization with 50 milliliters of Virahols.As firstling, obtain the snow-white crystalline product of 8.5 grams, 80.5 ℃ of fusing points, active component content 98%.Carry out recrystallization once more, obtain 7.5 gram crystalline products, 81.5 ℃ of fusing points, active component content is higher than 99.5%.
C=0=1735 centimetre of infrared (Potassium Bromide) γ
-1;
Nucleus magnetic resonance (CDCl
3) δ (ppm)=1.22,1.27CMe
2; 1.69, d, 1HCl; 2.32, m, 1HCl; 5.6, d, 1HCl '; 6.39, S, 1H, Ca proton.
Embodiment 3
Thick (purity 95%) the trans Sai Bomisilin mixture of 100 gram oilies is (by the gas chromatographic analysis data, contain the trans S isomer of trans R of 48%1R and 1S, the 47%Ib isomer), under agitation, be dissolved in 150 milliliters of anhydrous triethylamine solution that contain 0.2 gram tertiary butyl hydroxytoluene.Solution is filtered fast seeding.According to the method for embodiment 2, secondary crystal and recrystallization.Like this, obtain snow-white knot product 82 grams of isomer to Ib, fusing point 80-80.5 ℃, active component content 97.5%.
Embodiment 4
The 10 gram trans Sai Bomisilin mixtures of oily (containing trans S isomer of the trans R+1S of 85% 1R and 14%Ib isomer) under room temperature, stirring, are dissolved in 15 milliliters of anhydrous triethylamines.Subsequently, press embodiment 2 methods, solution is filtered and crystallization.Obtain snow-white crystallization 8 grams of isomer mixture Ib like this, fusing point 79-80.5 ℃.
Embodiment 5
10 gram crystalline trans Sai Bomisilin (contain trans S isomer of the trans R+1S of 52% 1R and 47%Ib isomer to) under 50 ℃, are dissolved in 15 milliliters of Tri-n-Propylamines.Solution filters.Be cooled to 30 ℃.Ib isomer mixture crystal seed seeding with 1: 1.Make mixture at 48 hours intercrystallines.Can obtain snow-white crystallization 8.2 grams, fusing point 78-80 ℃, purity 95%(is by the gas chromatographic analysis data).
Embodiment 6
It is identical with embodiment 5 to carry out method.Just do alkali with 15 milliliters of Tributylamines.Like this, obtain the right snow-white crystallization of Ib isomer 7.5 grams, fusing point 77-79 ℃, purity 93%.
Embodiment 7
It is identical with embodiment 5 to carry out method.Just do alkali with 15 milliliters of tri-isopropyl amines.Like this, obtain the right snow-white crystallization of Ib isomer 7.5 grams, fusing point 78-80 ℃, purity 95.5%.
Embodiment 8
It is identical with embodiment 5 to carry out method.Just do alkali with 15 milliliters of Diisopropylamines.Like this, obtain the right snow-white crystallization of Ib isomer 8.0 grams, fusing point 78-80 ℃, purity 95.5%.
Embodiment 9
The 10 trans Sai Bomisilin of gram (contain trans R isomer of the trans S+1S of 48%1R and 49%Id isomer to), stir and heating under, be dissolved in 50 milliliters of Virahols.Subsequently, add 2 milliliters of ammonium hydroxide aqueous solutions (proportion is 0.880 grams per milliliter).Solution 20 ℃, stir under, with Ib isomer solvate seeding 24 hours.Be cooled to 0 ℃-5 ℃, under this temperature, continue to stir.With suspension filtered.Product is also dry with Virahol and petroleum ether.Like this, obtain Ib(1: 1) right white crystals 6 grams of isomer, fusing point 78-79 ℃, purity 92%(stratographic analysis).From female alkali lye,, obtain white crystals product 1.5 grams, fusing point 78-79 ℃ as second batch of product.The composition of second batch of product is identical with the crystalline composition of first generation.
Embodiment 10
The trans Sai Bomisilin of 10 grams (contain the trans R isomer of 1S of the trans S of 54%1R and 45%Id isomer to) is dissolved in 100 milliliters of sherwood oils.(the sherwood oil boiling point is 60-80 ℃).Add 1 milliliter of 0.5 molar sodium carbonate solution and 1 subsequently: the water 1(volume) and methyl alcohol (containing 10 weight/volume bromination tetrabutylammoniums) mixture.The solution crystal seed seeding of embodiment 2.Crystallization 4 days.Filter.With petroleum ether and dry.Like this, obtain the right white crystals of Ib isomer 6.8 grams, fusing point 78-80 ℃, purity 95%(gas chromatographic analysis).
Embodiment 11
The 10 gram trans Sai Bomisilin of crystalline (containing trans R isomer of the trans S+1S of 52%1R and the trans S isomer of the trans R+1S of 47%1R) under 50-60 ℃, are dissolved in 100 milliliters of sherwood oils.In solution, add 0.02 gram, 2.6 di-t-butyls, 4 methylphenols.After the filtration, filtrate is under 30 ℃, with 1: 1Ib isomer mixture seeding.Carry out crystallization with top disclosed method.Like this, obtain Ib(1: 1) right snow-white crystallization 3.8 grams of isomer, fusing point 77-79 ℃, purity 93%.Carry out recrystallization with sherwood oil, fusing point can rise to 80.5 ℃.The female alkali lye of crystallization carries out epimerization in independent step.
Embodiment 12
The 10 gram trans Sai Bomisilin of crystalline (containing trans R isomer of the trans S+1S of 45%1R and the trans S isomer of the trans R+1S of 53%1R) under 50-60 ℃, are dissolved in 75 milliliters of Virahols.Solution is handled by embodiment 11 methods, like this, obtains the right snow-white crystallization of Ib isomer 3.6 grams.According to gas chromatographic analysis, mixture content can reach 94% in pure 1: 1,80 ℃ of fusing points.Press embodiment 2 method recrystallizations.Like this, make and contain the product of active ingredient more than 99%.The female alkali lye of crystallization carries out epimerization through independent step.
Embodiment 13
In the equipment that whipping appts is arranged, add the female alkali lye (solution of enrichment Id isomer) that obtains by embodiment 11 methods.Adding the 1 gram trade mark then is the base ion exchange resin in Dowex type 2 * 4 holes (ion-exchange cellulose).Heterogeneous suspension stirred 12 hours at 40 ℃.Filter, use the washed with isopropyl alcohol secondary, 2 milliliters of each consumptions.According to gas chromatographic analysis, contain in the solution 41%Ib isomer to the 46%Id isomer.Press embodiment 11 methods with solution evaporation and crystallization.
Embodiment 14
It is identical with embodiment 13 to carry out method.Just make solvent with sherwood oil.According to gas chromatographic analysis, contain the trans S isomer of the trans R+1S of 39%Ib isomer and 56%1R in the solution.
Embodiment 15
10 gram colorless oil Sai Bomisilin (containing 30%Ib), 31%Id, 18%Ia and 21%Ic) with 1: 1Ib isomer mixture seeding.Under 7 ℃, one week of crystallization.The oily thickness crystallisate that obtains-15 ℃ of down coolings, is suspended in the mixture of 10 milliliters of 1: 1 Virahols and diisopropyl ether and is cooled to-15 ℃, carries out cold filtration then.The crystallization that obtains like this has 5 milliliters of ice-cold washed with isopropyl alcohol, and is at room temperature dry then.Like this, obtain white Ib crystallized product 2 grams, fusing point 78-80 ℃, purity 96%(gas chromatographic analysis).With 13 milliliters of hexane recrystallizations, obtain snow-white crystallized product 2.25 grams, fusing point 80-81 ℃, active component content 99%.
Embodiment 16
10 Ke Saibomisilin (containing 30%Ib, 31%Id, 18%Ia and 21%Ic) are dissolved in 100 milliliters of hot Virahols.Add 0.02 gram, 2.5 di-t-butyls, 4 methylphenols subsequently.Solution is clarified with 0.2 gram charcoal.Heat filtering.Filtrate is with 1: 1 Ib isomer mixture crystal seed, under 30 ℃, and seeding.Mixture is 10 ℃ of following crystallizations 24 hours, 0 ℃ of following crystallization 48 hours, at last-5 ℃ of following crystallizations 24 hours (should avoid isolating the oily product during crystallization).Washed with isopropyl alcohol is used in the cold filtration of crystallization, and is at room temperature dry.Like this, obtain snow-white crystallization 2.6 grams of Ib isomer to (1: 1), fusing point 78-80 ℃, purity 95%.Use the hexane recrystallization, obtain snow-white crystallized product 2.3 grams, fusing point 80-81 ℃, active component content 99%.
Preparation embodiment
Embodiment 17
Emulsification enriched material (Ec) can be produced by the fusion following ingredients.
10Ec
The component content kg/kg
Isomer is to Ib 0.105
Hexalin 0.290
Atlox3386B 0.020
Atlox3400B 0.045
Odorlessness mineral oil 0.540
5Ec
The component content kg/kg
Isomer is to Ib 0.050
Hexalin 0.290
Atlox3386B 0.020
Atlox3400B 0.045
Odorlessness mineral oil 0.595
When the dosage of 5Ec composition is per hectare 20 gram active ingredients,, be equivalent to have same composition but the preparation (α Mi Silin composition) that comprises the Ia isomer to preventing the effect of Colorado beetle insect pest.
Embodiment 18
Contain 1.5 gram Ib isomer to the solution of 1.5 gram fatty alcohol polyglycol ethers, in the pulvis homogenizer, with the 30 gram trades mark be the synthetic silicic acid of WessalonS, 60 gram talcums (pH value is 7.1), 5 gram sucrose and 3.35 restrain the Witco 1298 Soft Acid homogenizing.Like this, make thin mobile pulvis.
Embodiment 19
20 gram Ib isomer are right, with 2 gram alcohol dilutions.In the pulvis homogenizer, with solution and 5 gram wooden calcium sulfonates, 5 gram nonyl phenyl polyglycol ethers (Eo=20) and 70 gram lime carbonate fusion.With the product that obtains like this in Alpine100 type grinding machine for grinding.Press CIPAC, the amount of swimming reaches 81%, and wetting time is 18 seconds.
Biological Examples
Embodiment 20
To beans weevil (ACanthoscelides obtectus), the comparison activity test of fluorescence beetle (Tribolium confusum) and sheep maggot fly (Lucilia sericata) shows: enantiomorph is higher than the activity of enantiomorph to Ia to the activity of Ib to enantiomorph to Ia and Ib.
Test-results is summarized in table 1.
It is as follows that method is carried out in test:
Steric isomer is dissolved in 1: 2 the mineral oil and acetone mixture.With the activity component impregnation of filter paper disk (Whatman No1,9 centimetres of diameters), acetone evaporated is fallen with corresponding dosage.Insect is placed on the filter paper disk in the Petri dish, so that test.Every kind of dosage parallel test three times.Put 15 animals on every Petri dish.Measure mortality ratio after 24 hours.The correct mortality ratio that causes rate % data usefulness Abbot formula calculation correction.
Embodiment 21
There is synergy between the steric isomer of digital proof enantiomorph to Ib of table 2.Test is carried out with the fluorescence beetle.Adopt various active ingredient dosage " method of tagging ", obtain table 2 result:
Test is undertaken by the method for embodiment 20.
Embodiment 22
Table 3 discloses the right medium lethal dose (LD of Ig and Ii isomer and Ib isomer
50) value.
Data are typical measuring result (seeing Table 3).
Above-mentioned digital proof:, all have synergy between the trans-isomer(ide) to two kinds of insects.
It is as follows that method is carried out in test:
A) housefly
Active ingredient is dissolved in the cellosolvo (cellosolve), again 0.3 microlitre drips of solution is added on the back side epidermis of 3-5 days female housefly of birth.With 10 animals, every kind of dosage parallel test secondary.In field of activity 0% to 100% interval, carry out the test of 5 kinds of dosage levels.After 24 hours, measure mortality ratio.Data change log10 dose and probit mortality ratio into.Medium lethal dose and fiducial interval value are calculated with the linear regression analysis method of " logarithm-probability " data.The expected value that needs when calculating synergy is asked for the harmonic mean method.
The synergism factor is the merchant of expected value divided by the observed value gained.
B) fluorescence beetle
Active ingredient is dissolved in the cellosolvo, 0.3 microlitre drips of solution is added in the belly of the adult in birth 1-2 week.In field of activity 0%-100% interval, carry out 5 kinds of dosage level tests.Every kind of dosage uses 20 animals, parallel test secondary.Adopt method evaluation and the definite medium lethal dose value and the synergism factor described in the embodiment 21.
Embodiment 23
To the residue of aphid parent adult the test of tagging.
Aphid parent adult is exposed to newly is applied on the glass dish, form in the active ingredient in imprisonment district, calculate survivor's number then.
Handle: water Processing Test product and contrast.
Repeated experiments: at least 3 times.1 imprisonment district of experimental scale (only).
The zooparasitic life-span of using is 24 hours.
In every glass dish, test products concentration is 1-5ppm.
In each imprisonment district, place 10 female aphid parents, and feeding honey.Through 1 hour, 5 hours and 24 hours, measure the female parent number of surviving respectively.Calculate the sum of survivor in each imprisonment district.
Test-results is summarized in table 4.
Embodiment 24
The test of directly tagging to the aphid pupa.
Place Petri dish directly to spray the sophisticated aphid pupa that is attached on the red pepper leaf with active ingredient.
Select the red pepper leaf and the parasitic pupa of sprout wings the first two or three days for use.Leaf is placed on the filter paper of plastics Petri dish.Filter paper is moist.
Test method is seen embodiment 23.
After the test, blade is moved into the Petri dish bottom of cleaning.To test pallet and put into climatic test cabinet.Keep 20 ℃ of temperature, relative temperature 70% and diurnal cycle 16-8 hour.The pupa of surviving is through the number of hatching and pupa death after two to three days.The result is as shown in table 5.
Embodiment 25
With solubilization of active ingredient in cellosolvo.0.3 microlitre drips of solution is added on the web of colorado potato bug adult.Test divides two groups, parallel carrying out.Every kind of dosage uses 10 insects.After the test, insect is placed Petri dish, after 48 hours, measure its mortality ratio.Test-results is shown in following table 6.
Embodiment 26
The confused flour beetle adult is tested by embodiment 20 methods.Measure mortality ratio percentage ratio after 24 hours.Piperonyl butoxide (hereinafter to be referred as " PBO ") consumption is 0.5 a milligram/dish.Test result publication is in table 7.As can be seen, enantiomorph to the synergy of Ib greater than isomer to Ia.
Embodiment 27
Active ingredient is dissolved in the cellosolvo.0.2 microlitre drips of solution is added in is in L
7-L
8On the back of the web spinner of larval stage.With will testing on the careless mould leaf that caterpillar places Petri dish of being attached to.Use 5 kinds of various dose during test.Every kind of dosage is got 10 insects, carries out two groups of parallel tests.Calculate the caterpillar number and the mortality ratio percentage ratio of being tagged after 24 hours.
Test-results is summarized in table 8.
Embodiment 28
To be made into 50-according to the 5EC enriched material dilute with water of embodiment 17 methods preparation, 100-, 200-, 400-, 800-, 1600-dilute emulsion doubly.0.5 milliliter of emulsion is sprayed on the glass dish, carries out drying subsequently.Then, in every glass dish, place 10 Colorado beetle adults.Cover glass cover, fasten insect.6 kinds of dosage are used in test.Every kind of dosage carries out three groups of parallel tests.After 48 hours, calculate the insect number and the mortality ratio percentage ratio of being tagged.Test-results is as shown in table 9.
Embodiment 29
Carry out insect killing effect test with the bean weevil adult.After 24 hours, calculate the insect number and the mortality ratio percentage ratio of being tagged.Test-results is as shown in table 10.
Table 1
To dosage (milligram/dish)
Reflect
Species body 0.02 0.07 0.22 0.67 2.0 6.0
To mortality ratio %
Beans weevil Ia 10 37 63 100 100 100
(adult) Ib 32 55 87 100 100 100
Fluorescence beetle Ia 0 18 51 100 100 100
(adult) Ib 14 73 100 100 100 100
Sheep maggot fly Ia 0 30 29 57 60 65
(adult) Ib 22 55 70 75 100 100
Table 2
Dosage (milligram/dish) 0.11 0.33 1.00 3.00
Mortality ratio %
The trans R Ii 00 71 90 of 1S
The trans S Ig 80 94 100 100 of 1R
The Ib enantiomorph is to 90 100 100 100
Table 3
LD
50(nanogram/insect) LD
50(nanogram/insect)
Sai Bomisilin
Fluorescence beetle housefly
Steric isomer
The observed value mathematical expectation synergism factor observed value mathematical expectation synergism factor
The trans S 73.6--13.4 of Ig 1R--
The trans R 1291.8--141.9 of Ii 1S--
Ib 51.9 139.3 2.68 12.8 24.5 1.92
Table 4
Concentration
5ppm 1ppm
1 hour 1 hour 5 hours 24 hours
Mortality ratio %
Ia 100 100 100 96
Ib 100 0 75 88
Contrast 000 1.5
Table 5
Concentration (ppm)
30 10 5 1
Mortality ratio %
Ib 61.0 0 0 0
δ rice department woods 75.0 33.0 00
Contrast 0000
Table 6
Dosage (microgram/insect)
Sai Bomisilin
0.05 0.10 0.20 0.40
Enantiomer
24 hours mortality ratio %
Ib 0 25 75 85
Sai Bomisilin 0 20 45 75
Table 7
Dosage (milligram/dish)
Active ingredient 0.4 0.2 0.1 0.05 0.025
24 hours mortality ratio %
Ia 96 53 12 0 0
Ia+PBO 100 58 16 0 0
Ib 100 85 51 10 0
Ib+PBO 100 91 68 39 9
Table 8
Dosage (microgram/larva)
Sai Bomisilin
0.023 0.047 0.094 0.188 0.375
Steric isomer
24 hours mortality ratio %
Ib 10 15 30 70 80
Sai Bomisilin 00 25 50 75
Table 9
Extent of dilution
1600 times 800 times 400 times 200 times 100 times 50 times in 5EC preparation
Mortality ratio %
Sai Bomisilin 0 17 33 50 67 83
Ib 0 13 37 57 87 100
Table 10
Extent of dilution
1600 times 800 times 400 times 200 times 100 times 50 times in 5EC preparation
Mortality ratio %
Sai Bomisilin 03 10 20 43 60
Ib 3 10 20 37 53 67
Claims (1)
1, the desinsection group parting that contains more than one active ingredients, environmental sound and have synergy is characterized by said composition and contains the synthetic pyrethroid of 0.01 to 99% (weight) molecular formula for (I),
--the enantiomorph that promptly has only trans S of 1R in its 8 kinds of possible isomer and the trans R of 1S in fact is to (I b) and optional one or more activators and auxiliary, particularly oxidation inhibitor, stablizer, wetting agent, emulsifying agent, dispersion agent, antifoams, thinner and/or weighting agent.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| HU8674A HU198373B (en) | 1986-01-08 | 1986-01-08 | Artropodicide composition containing trans-cipermetrin isomeres and process for producing the active components |
| HU74/85 | 1986-01-08 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN86101357A CN86101357A (en) | 1987-07-15 |
| CN1015709B true CN1015709B (en) | 1992-03-04 |
Family
ID=10947772
Family Applications (3)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN86101380A Expired - Lifetime CN1031996C (en) | 1986-01-08 | 1986-03-07 | Pyrethroid compound containing many kinds of active components |
| CN86101357A Expired CN1015709B (en) | 1986-01-08 | 1986-03-07 | Insecticidal compositions comprising more than one active ingredients |
| CN90109426A Expired - Lifetime CN1031972C (en) | 1986-01-08 | 1986-03-07 | Pyrethroid composition containing activatet components |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN86101380A Expired - Lifetime CN1031996C (en) | 1986-01-08 | 1986-03-07 | Pyrethroid compound containing many kinds of active components |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN90109426A Expired - Lifetime CN1031972C (en) | 1986-01-08 | 1986-03-07 | Pyrethroid composition containing activatet components |
Country Status (10)
| Country | Link |
|---|---|
| CN (3) | CN1031996C (en) |
| AP (2) | AP14A (en) |
| AR (1) | AR244504A1 (en) |
| CA (1) | CA1317220C (en) |
| CS (2) | CS254994B2 (en) |
| EG (2) | EG18452A (en) |
| HU (1) | HU198373B (en) |
| IL (1) | IL77624A (en) |
| PL (4) | PL150680B1 (en) |
| TR (2) | TR22871A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1301304C (en) * | 2004-02-26 | 2007-02-21 | 深圳市展辰达化工有限公司 | Nitro termite-proof insect-protected enclosed priming paint |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103819363A (en) * | 2014-03-21 | 2014-05-28 | 中国农科院植保所廊坊农药中试厂 | Method of improving transposition synthetic yield of beta-cypermethrin |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IE41614B1 (en) * | 1973-08-15 | 1980-02-13 | Nat Res Dev | Substituted 2,2-dimethyl cylopropane carboxylic acid estersprocess for their preperation and their use as insecticides |
| FR2375161A1 (en) * | 1976-04-23 | 1978-07-21 | Roussel Uclaf | PROCESS FOR TRANSFORMATION OF AN OPTICALLY ACTIVE A-CYANE SECONDARY ALCOHOL CHIRAL ACID ESTER OF STRUCTURE (R) INTO A-CYANE SECONDARY ALCOHOL CHIRAL ACID ESTER OF STRUCTURE (S) |
| US4261921A (en) * | 1979-06-06 | 1981-04-14 | Fmc Corporation | Process for preparation of a crystalline insecticidal pyrethroid enantiomer pair |
| EP0107296B1 (en) * | 1982-10-18 | 1987-07-15 | Imperial Chemical Industries Plc | Insecticidal product and preparation thereof |
-
1986
- 1986-01-08 HU HU8674A patent/HU198373B/en not_active IP Right Cessation
- 1986-01-16 IL IL77624A patent/IL77624A/en not_active IP Right Cessation
- 1986-01-22 CS CS86481A patent/CS254994B2/en not_active IP Right Cessation
- 1986-01-22 CS CS86480A patent/CS254993B2/en not_active IP Right Cessation
- 1986-02-02 EG EG50/86A patent/EG18452A/en active
- 1986-02-03 PL PL1986269466A patent/PL150680B1/en unknown
- 1986-02-03 PL PL1986257772A patent/PL151661B1/en unknown
- 1986-02-04 EG EG55/86A patent/EG18336A/en active
- 1986-02-04 PL PL1986267524A patent/PL149799B1/en unknown
- 1986-02-04 PL PL1986257782A patent/PL153005B1/en unknown
- 1986-02-26 AP APAP/P/1986/000024A patent/AP14A/en active
- 1986-02-26 AP APAP/P/1986/000023A patent/AP13A/en active
- 1986-03-07 CN CN86101380A patent/CN1031996C/en not_active Expired - Lifetime
- 1986-03-07 CN CN86101357A patent/CN1015709B/en not_active Expired
- 1986-03-07 CN CN90109426A patent/CN1031972C/en not_active Expired - Lifetime
- 1986-05-05 TR TR227/86A patent/TR22871A/en unknown
- 1986-05-05 TR TR24355A patent/TR22867A/en unknown
- 1986-11-05 CA CA000522189A patent/CA1317220C/en not_active Expired - Fee Related
-
1988
- 1988-02-27 AR AR88303240A patent/AR244504A1/en active
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1301304C (en) * | 2004-02-26 | 2007-02-21 | 深圳市展辰达化工有限公司 | Nitro termite-proof insect-protected enclosed priming paint |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1031972C (en) | 1996-06-12 |
| CS254993B2 (en) | 1988-02-15 |
| AR244504A1 (en) | 1993-11-30 |
| PL153005B1 (en) | 1991-02-28 |
| AP8600023A0 (en) | 1986-02-01 |
| CA1317220C (en) | 1993-05-04 |
| TR22871A (en) | 1988-09-23 |
| TR22867A (en) | 1988-09-19 |
| CN86101357A (en) | 1987-07-15 |
| CN86101380A (en) | 1987-07-15 |
| PL151661B1 (en) | 1990-09-28 |
| EG18452A (en) | 1993-04-30 |
| CS48086A2 (en) | 1987-06-11 |
| AP14A (en) | 1988-03-08 |
| PL150680B1 (en) | 1990-06-30 |
| CS254994B2 (en) | 1988-02-15 |
| PL257782A1 (en) | 1988-01-07 |
| AP8600024A0 (en) | 1986-02-01 |
| PL149799B1 (en) | 1990-03-31 |
| HUT41962A (en) | 1987-06-29 |
| PL257772A1 (en) | 1988-04-28 |
| PL269466A1 (en) | 1988-12-22 |
| EG18336A (en) | 1993-06-30 |
| AP13A (en) | 1988-03-08 |
| PL267524A1 (en) | 1988-05-26 |
| CN1031996C (en) | 1996-06-12 |
| CN1050810A (en) | 1991-04-24 |
| IL77624A (en) | 1990-12-23 |
| HU198373B (en) | 1989-10-30 |
| CS48186A2 (en) | 1987-06-11 |
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