DK159802B

DK159802B - ACARICID PREPARATION

Info

Publication number: DK159802B
Application number: DK328383A
Authority: DK
Inventors: John Clifford Felton; John Stewart Badmin; Roland Stephen Twydell
Original assignee: Shell Int Research
Priority date: 1977-02-09
Filing date: 1983-07-15
Publication date: 1990-12-10
Also published as: DK328383D0; DK328383A; DK159802C

Description

DK 159802 BDK 159802 B

Den foreliggende opfindelse angår et acaricidpræparat, især et præparat, som indeholder en repræsentant for de såkaldte syntetiske pyrethroider og et formamidin.The present invention relates to an acaricide composition, in particular a composition containing a representative of the so-called synthetic pyrethroids and a formamidine.

Det har vist sig, at et sådant præparat har synergistisk virk-5 ning, hvad angår acaride skadelige organismer, dvs., at aktiviteten af kombinationen af de to pesticider bliver en mere end additiv pesticid virkning.It has been found that such a preparation has a synergistic effect on acaride harmful organisms, that is, the activity of the combination of the two pesticides becomes more than additive pesticide action.

Den foreliggende opfindelse angår et acaricidpræparat, som indeholder: 10 a) N,N-dimethyl-N'-(2-methyl-4-chlorphenyl)formamidin (i det følgende benævnt "chlorphenamidin"), ogThe present invention relates to an acaricide composition comprising: a) N, N-dimethyl-N '- (2-methyl-4-chlorophenyl) formamidine (hereinafter referred to as "chlorophenamidine"), and

b) et pyrethroidinsecticid med den almene formel A - COO - CH_7/ \V Wb) a pyrethroid insecticide of the general formula A - COO - CH_7 / \ V W

15 hvor A er 2-(2,2-dichlorvinyl)-3,3-dimethylcyclopropyl, 2-(2,2-di-bromvinyl)-3,3-dimethylcyclopropyl eller a-isopropyl-4-chlorbenzyl.Wherein A is 2- (2,2-dichlorovinyl) -3,3-dimethylcyclopropyl, 2- (2,2-dibromovinyl) -3,3-dimethylcyclopropyl or α-isopropyl-4-chlorobenzyl.

Forbindelsen med den almene formel I kan være til stede i en hvilken som helst af sine optiske isomere, cis-transisomere og andre slags geometriske isomere. Der kan ligeledes være racemater og blandinger 20 af isomere af én eller flere forbindelser med den almene formel I til stede.The compound of general formula I may be present in any of its optical isomers, cis-transisomers and other kinds of geometric isomers. Also, racemates and mixtures of isomers of one or more compounds of general formula I may be present.

De mest foretrukne pyrethroider til anvendelse i de acaricide præparater ifølge den foreliggende opfindelse er de forbindelser, der er betegnet forbindelserne X og Y i eksemplerne.The most preferred pyrethroids for use in the acaricidal compositions of the present invention are the compounds designated compounds X and Y in the Examples.

25 Blandingen af chlorphenamidin og pyrethroidinsecticidet giver ikke blot et pesticid med et væsentligt bredere virkningsspektrum, menThe mixture of the chlorphenamidine and the pyrethroid insecticide not only provides a pesticide with a significantly wider spectrum of action, but

DK 159802 BDK 159802 B

2 giver også en overraskende synergis tisk virkning, især hvad angår acarider, fx Tetranychus urticae.2 also gives a surprising synergistic effect, especially with regard to acarides, for example Tetranychus urticae.

Vægtforholdet mellem pyrethiroidinsecticidet og methomyl eller chlor-phenamidin kan være i området 5:1-1:50, fortrinsvis i området 5 1:1-1:25.The weight ratio of the pyrethiroid insecticide to methomyl or chlorophenamidine may be in the range 5: 1-1: 50, preferably in the range 5 1: 1-1: 25.

De aktive bestanddele i præparatet ifølge den foreliggende opfindelse udgør normalt 1-50 vægtprocent af præparatet; den resterende del af præparatet udgøres af en bærer eller et overfladeaktivt middel eller begge dele. Der kan således i det pesticide præparat ifølge den 10 foreliggende opfindelse også anvendes en bærer, et overfladeaktivt middel eller både en bærer og et overfladeaktivt middel til at lette påførslen af præparatet på den skadelige organisme eller dens tilholdssted med de ønskede doseringsniveauer.The active ingredients in the composition of the present invention usually constitute 1-50% by weight of the composition; the remaining portion of the composition is a carrier or surfactant or both. Thus, in the pesticidal composition of the present invention, a carrier, a surfactant or both a carrier and a surfactant may also be used to facilitate application of the composition to the harmful organism or its site at the desired dosage levels.

Udtrykket "bærer” betegner her et fast eller flydende materiale, som 15 kan være uorganisk eller organisk og af syntetisk eller naturlig oprindelse.The term "carrier" here refers to a solid or liquid material which may be inorganic or organic and of synthetic or natural origin.

Typiske faste bærere er fx naturlige eller syntetiske lerarter og silicater, fx naturlige silicajordarter såsom diatoméjord og alumini-umsilicater, fx kaoliniter, montmorilloniter og glimmer. Typiske 20 flydende bærere er ketoner, fx methylcyclohexanon, aromatiske carbon-hydrider, fx methylnaphthalener, jordoliefraktioner såsom, fx, jord-oliexylener og lette mineralolier, og chlorerede carbonhydrider, fx carbontetrachlorid. Blandinger af væsker er ofte hensigtsmæssige.Typical solid carriers are, for example, natural or synthetic clays and silicates, for example, natural silica soils such as diatomaceous earth and aluminosilicates, e.g., kaolinites, montmorillonites and mica. Typical liquid carriers are ketones, e.g., methylcyclohexanone, aromatic hydrocarbons, e.g., methylnaphthalenes, petroleum fractions such as, for example, petroleum xylenes and light mineral oils, and chlorinated hydrocarbons, e.g., carbon tetrachloride. Mixtures of liquids are often appropriate.

Der kan indeholdes ét eller flere overfladeaktive midler og/eller 25 klæbemidler i formuleringen. Det overfladeaktive middel kan være et emulgeringsmiddel eller et dispergeringsmiddel eller et befugtnings-middel; det kan være ikke-ionisk eller ionisk. Der kan anvendes et hvilket som helst af de overfladeaktive midler, som sædvanligvis anvendes ved formulering af herbicider eller insecticider. Eksempler 30 på egnede overfladeaktive midler er natrium- eller calciumsaltene af polyacrylsyrer og ligninsulfonsyrer; kondensationsprodukterne af fedtsyrer eller aliphatiske aminer eller amider med mindst 12 car-bonatomer i molekylet med ethylenoxid og/eller propylenoxid; fedtsy-One or more surfactants and / or 25 adhesives may be included in the formulation. The surfactant may be an emulsifier or dispersant or wetting agent; it can be non-ionic or ionic. Any of the surfactants commonly used in the formulation of herbicides or insecticides can be used. Examples of suitable surfactants are the sodium or calcium salts of polyacrylic acids and lignin sulfonic acids; the condensation products of fatty acids or aliphatic amines or amides having at least 12 carbon atoms in the molecule with ethylene oxide and / or propylene oxide; fatty

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3 reestere af glycerol, sorbitan, saccharose eller pentaerythritol, og kondensater af disse med ethylenoxid og/eller propylenoxid, kondensationsprodukter af fedtalkoholer eller alkylphenoler, fx p-octyl-phenol eller p-octylcresol, med ethylenoxid og/eller propylenoxid, 5 sulfater eller sulfonater af disse kondensationsprodukter, alkali-eller jordalkalimetalsalte, fortrinsvis natriumsalte, af svovlsyreeller sulfonsyreestere med mindst 10 carbonatomer i molekylet, fx natriumlaurylsulfat, natriumsek.alkylsulfater, natriumsalte, af sulfoneret ricinusolie og natriumalkylarylsulfonater såsom natrium-10 dodecylbenzensulfonat; og polymere af ethylenoxid og copolymere af ethylenoxid og propylenoxid.3 residues of glycerol, sorbitan, sucrose or pentaerythritol, and their condensates with ethylene oxide and / or propylene oxide, condensation products of fatty alcohols or alkyl phenols, eg p-octylphenol or p-octylcresol, with ethylene oxide and / or propylene oxide or 5 of these condensation products, alkali or alkaline earth metal salts, preferably sodium salts, of sulfuric acid or sulfonic acid esters having at least 10 carbon atoms in the molecule, for example sodium lauryl sulfate, sodium silk sulphates, sodium salts, of sulphonated castor oil and sodium alkyl aryl sulphonate sulfate and polymers of ethylene oxide and copolymers of ethylene oxide and propylene oxide.

Den foreliggende opfindelse angår også vandige dispersioner og emulsioner, fx præparater fremstillet ved fortynding af et befugteligt pulver eller et koncentrat ifølge den foreliggende opfindelse med 15 vand. Disse emulsioner kan være af vand-i-olie eller af olie-i-vand-typen, og de kan have en tyk "mayonnaise"-agtig konsistens.The present invention also relates to aqueous dispersions and emulsions, e.g., compositions prepared by diluting a wettable powder or concentrate of the present invention with 15 water. These emulsions may be water-in-oil or oil-in-water type and may have a thick mayonnaise-like consistency.

Den foreliggende opfindelse angår også en fremgangsmåde til at bekæmpe skadelige organismer, hvilken fremgangsmåde omfatter påføring til den skadelige organisme eller dens levested af en pesticidt 20 effektiv mængde af præparatet ifølge den foreliggende opfindelse.The present invention also relates to a method for controlling harmful organisms which comprises applying to the harmful organism or its habitat a pesticide effective amount of the composition of the present invention.

Den foreliggende opfindelse belyses nærmere ved følgende eksempler, hvori den forenede virkning af to pesticider analyseres ifølge metoden efter Yun-Pei Sun og E.R. Johnson, Journal of Economic Entomology, 1960, bind 53, nr. 5, side 887-892.The present invention is further illustrated by the following examples in which the combined action of two pesticides is analyzed according to the method of Yun-Pei Sun and E.R. Johnson, Journal of Economic Entomology, 1960, Volume 53, No. 5, pages 887-892.

25 Den forenede virkning af to pesticider analyseres således ved at bestemme de faktiske toxicitetsindekser af komponenterne og af blandingerne af forbindelserne under anvendelse af dosis-mortalitetskurver. Blandingens teoretiske toxicitet er lig med summen af toxici-tetsindekserne beregnet ud fra procentdelen af hver komponent multi-30 pliceret med dens toxicitetsindeks. Den forenede toxicitet eller blandingens co-toxicitetskoefficient er derfor lig med blandingens faktiske toxicitetsindeks _ x 100 blandingens teoretiske toxicitetsindeksThus, the combined effect of two pesticides is analyzed by determining the actual toxicity indices of the components and of the mixtures of the compounds using dose-mortality curves. The theoretical toxicity of the mixture is equal to the sum of the toxicity indices calculated from the percentage of each component multiplied by its toxicity index. Therefore, the combined toxicity or co-toxicity coefficient of the mixture is equal to the actual toxicity index of the mixture - x 100 mixture theoretical toxicity index

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44

En blandingskoefficient nær 100 indicerer sandsynlighed for en lignende virkning af de to pesticider; uafhængig virkning giver sædvanligvis en koefficient på mindre end 100, mens en koefficient signifikant større end 100 stærkt indicerer synergisme.A mixing coefficient near 100 indicates the probability of a similar effect of the two pesticides; independent effect usually gives a coefficient of less than 100, while a coefficient significantly greater than 100 strongly indicates synergism.

5 De testede forbindelser i eksemplerne er de nedenfor viste.The compounds tested in the Examples are those shown below.

Forbindelse X.Compound X.

\ /H=ccl’. q_/~\ '/*sT CN _/ \-/ CH3 / \ CO. 0. CH -i \ CH3' h\ / H = ccl '. q_ / ~ \ '/ * sT CN _ / \ - / CH3 / \ CO. 0. CH -i \ CH3 'h

Forbindelse Ύ.Connection Ύ.

10 =¾ /CH3 0^\ ^ CH ^ CN _/ \-/ ci _^ ^-~ch-co .o-chH^ y10 = ¾ / CH3 0 ^ \ ^ CH ^ CN _ / \ - / ci _ ^^ - ~ ch-co .o-chH ^ y

EKSEMPELEXAMPLE

Virkning af pyrethroid/chlorphenamidinblanding mod Tetranychus ur-ticae.Effect of pyrethroid / chlorophenamidine mixture on Tetranychus ur-ticae.

15 Den acaricide virkning af forbindelserae X og Y og blandinger deraf med chlorphenamidin bestemmes på følgende måde.The acaricidal effect of compounds X and Y and mixtures thereof with chlorophenamidine is determined as follows.

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'J'J

Forbindelserne og blandingerne formuleres som opløsninger eller suspensioner i vand indeholdende 20 vægtprocent acetone og 0,05 vægtprocent Triton X-100 som befugtningsmiddel. Formuleringen indeholder 0,4 vægtprocent af den forbindelse eller blanding, der skal 5 testes, og fortyndes for at fremstille formuleringer med forskellige koncentrationer. Bladplader skåret fra franske bønneplanter sprøjtes med formuleringerne og lades tørre i 1/2-1 time. Hver bladplade podes med 10 Tetranychus urticae, og mortalitetstællinger foretages 24 timer efter podningen. Ud fra disse resultater kan LD50-værdierne 10 (den letale dosis i mikrogram aktivt materiale, der skal til for at dræbe 50% af midepopulationen) beregnes.The compounds and mixtures are formulated as solutions or suspensions in water containing 20% by weight acetone and 0.05% by weight Triton X-100 as wetting agent. The formulation contains 0.4% by weight of the compound or mixture to be tested and diluted to prepare formulations of various concentrations. Leaves cut from French bean plants are sprayed with the formulations and allowed to dry for 1/2 hour. Each leaf plate is seeded with 10 Tetranychus urticae and mortality counts are made 24 hours after inoculation. From these results, the LD50 values 10 (the lethal dose in micrograms of active material needed to kill 50% of the mid-population) can be calculated.

Toxicitetsindeks for forbindelser og blandinger beregnes ved hjælp af følgende formel: LD^o af standardinsecticid (parathion) 15 _Toxicity index of compounds and mixtures is calculated by the following formula: LD 50 of standard insecticide (parathion) 15

Toxicitetsindeks = LD5O af forbindelse eller blandingToxicity index = LD50 of compound or mixture

Co-toxicitetskoefficienten beregnes derpå på den ovenfor beskrevne måde. Resultaterne er anført i nedenstående tabel.The co-toxicity coefficient is then calculated in the manner described above. The results are given in the table below.

Claims

6 DK 159802 B TABLE Effect of pyrethroid mixtures on Tetranychus urticae Treatment LD50 Coefficient of toxicity Experiment No. Experiment No. 5 12 12 Chlorophenamidine 0.42 0.23 Compound Y 0.25 0.17 10 Compound X 0.28 0.17 Parathion 0.0070 0.0058 Chlorophenamidine + Compound Y (2: 1) 0.17 0.075 204 277 15 Chlorphenamidine + Compound X (2: 1) 0.15 0.075 243 277 The table shows that the co-toxicity coefficient is well above 20 100 for mixtures according to the invention, which clearly shows the synergistic effect produced by these mixtures against Tetranychus urticae.

An acaricidal composition, characterized in that it contains a) N, N-dime thyl-Ν '- (2-methyl-4-chlorophenyl) formamidine (hereinafter referred to as "chlorophenamidine") and DK 159802 B b) a pyrethroid insecticide with wherein A is 2- (2,2-dichlorovinyl) -3,3-dimethylcyclopropyl, 2- (2,2-di-bromovinyl) -3,3- dimethylcyclopropyl or α-isopropyl-4-chlorobenzyl.

Composition according to claim 1, characterized in that the weight ratio of the pyrethroid insecticide to chlorophenamidine is in the range of 5: 1 to 1:50.

Composition according to claim 1 or 2, 10, characterized in that the active constituents of the composition comprise 1-50% by weight of the composition and the remainder is a carrier or a surfactant or both a carrier and a surfactant.