CS227687B2 - Insecticide and acaricide - Google Patents

Abstract

Pesticidal agents containing a combination of a compound of the formula I <IMAGE> in which R represents identical or different radicals from the group comprising halogen, (C1-C3)-alkyl, NO2, OCH3, R1, R2 and R3 represent (C1-C3)-alkyl, X represents O, S and n represents an integer from 1 - 3, and of a compound of the formula II <IMAGE> in which Y represents an optionally substituted aralkyl, cyclopropyl or arylamino group , R represents hydrogen, cyano or ethynyl, X represents halogen or aryloxy which is optionally substituted by halogen, and n represents an integer from 1 - 5, the ratio between the components of the formulae I and II being 500 : 1 to 1 : 100, their use for controlling insects and mites, and methods for their application.

Description

SUMMARY OF THE INVENTION The present invention provides an insecticidal and acaricidal composition which comprises a compound of formula I as an active ingredient.

_CH3 CHq \ ^3/3

/AND/

Г in which

R is chlorine or (C1-C3) -alkyl,

And R ₂ denote methyl or ethyl, n represents an integer I or 2 in combination with a compound of formula II

O R

II I

Y-C-O-CH wherein

Y represents a group of the formula

! 1

or a group of the formula wherein

Ra and Rb

Ha

Rb

h denotes a methyl group or represents hydrogen and represents dichlorvinyl, dibromvinyl, tetrachloroethyl, tetrbromomethyl, dichlorodiomethyl, and represents cyano or hydrogen, its optical isomers or geometric isomers or mixtures thereof, the ratio of the components of formulas I being: II is 200: 1 to 1:50.

Preferred compounds of formula I are, for example, the following compounds:

la S- ^{/ 2} 1J- 2-lee ^tn У ^1E, another ¹ / N POoroρylkarbeIloylmet ^{l h} y 1 ^J IO ethylrnmeh ^ d ^ ^ HWF OSL ^mounted,

Ib S-pb [5-dichloro-phenyl] - (1-chloro-pyrrolidin-1-yl)] - [1,1-dimethyl] methylthiophene],

Ic S-n-4-chlorophenyl / N-isopropyylcarbonylbenzoyl-ethyl-methylmethyldithirrate

1d S - [- 33-Methylphenyl] -1S-isopropylkirberyylmethyl-1-ethene / methyldithrifrontone,

Ie ~ ^{S [/} - / ^e 41me h enyl ^{HN1 /} - / 1 ^{and rn} srprr ^pn lkrrireo meth ^{e n} yl ester -Oo1e ^thn meehanni THW ^{1-bisphosphonic} acid ^é

If S - [N-isorrorpin-N-1/2-isopropyl-l-l / kaibaeryl-ethyl] -O-methyl-thiophenone.

Preferred compounds of formula II are, for example, the following compounds:

(IIa) 3 '- (1-methoxybenzyl-3 - [, 1 - dichloro-vinyl] - (1') - dimethylcyclopropyanecarboxlate,

IIb (1 ', 1', 3'-phenoxybenzyl), 1b (1 '), 2-dimethylbenzene, 1,2-dimethylcyclopropanecarbonyl (II) (II) (1'r) fr (4'-oxyl) -benzyl] -benzene (1') IЗ // 1: ί-S1l · ^, //, 2-diirrmvinnll- /, 2 · 1dimettylcyk / rproprnkrrir1 xylate,

Γ Id. (S) -1a-chloro-11'-methoxybenzyl] -1,1-3-tetrahydro-free-1 (1) ₍ 1-ethene) acyclopropylpropylario xylate,

IIe (S) β-ω-ω-311-glycolynin (1R) (c1S131), (ilichloril, 2 'idibromeethy) - (f) idylthiylpropylproxycarboxylate a.

The alpha-knan-3-enyloxybenzyl (ether) - [4-chlorophenyl] -1'-methylethylic acid (1-alkyl1) -aryl) caramino-methylthiololithonium or the idithiophene (I), their preparation and their pesticidal activity are known, for example, from: DOS 2,617,736. These compounds have good activity against mite pests / Acaainna. However, their effect against some insect species is not co-rotating, especially at lower applied insects.

A group of insecticidally active compounds of the formula II known as piyrethroidn is described, for example, in Chem. Soc. Roar. £ / 1978 / 473,150 '. These compounds have excellent activity against various insect species, but their activity against spider mites is undesirable in many cases. . .

SUMMARY OF THE INVENTION It is therefore an object of the present invention to provide a composition which is pesticidally active against both insects and mites. It has now surprisingly been found that the combined use of compounds of formula I with compounds of formula II exhibits a synergistic effect in controlling insects and mites.

The ratio of the components of the formula I and the formula II can vary within wide limits and ranges between 200: 1 to 1:50, in particular between 125: 1 and even 1:31.

The insecticidal and acaricidal compositions of the present invention exhibit excellent synergistic effects against a wide range of pests, such as various spider mites such as spider mite (Panonychus ulmi), spider mite (Panonychus citri), and spider mite (Tetranychus utricae), further harmful absorbent and biting insects, beetles such as Epilachna varivestis, Colorado potato beetle (Leptinotarsa decemlinnett), Phyllotreta spec., Coennorhinus gmanmans, Anthonomus grandis (Anthonomus grandis), Agriotes spee./ furthermore, flower, such as moss beetle Pegomya betae /, the propeller / Ceeatis capitata / and cockroaches such as the Russian blatta / Blatta germbtLncа / and the cockroach / Blatta orientalis / as well as the mucus, such as the poppy moth / Dooalis fahae /, the peach aphid / Myzus pe ^i ^ e / a Onnoopetus fasciatus and Dyndercus spec.

Efficacy extends to all, as well as to individual developmental stages, both of the normal species and of the resistant species of the listed pests.

The combinations according to the invention, on the other hand, are characterized by good tolerability by a large number of crop plants.

SiMe active substances according to the invention can be used in the conventional form of preparations, such as e] ooUznícУ konccenrátů, solutions / ULV i.e. highly concentrated solutions /, dispersions, smOáitelných powders, dusts or ^R1 rtnuSátů. / Content of active agent in the market běžnýchna it is generally about 0.1 to 95% hrodenootic, preferably between 10 and 80% of the otototin active ingredient. In addition, these formulations contain the usual adhesives, emulsifiers, suspensions, dispersants, fillers, carriers and solvents.

The active compound combinations according to the invention can be applied in the form of salts prepared in a reservoir immediately before use, whereby the individual active ingredients in the form of preparations are mixed just prior to application or can be applied in the form of ready-to-use preparations.

Finished mixture. in the form of absorbable powders, emulsifiable concentrates, dispersions, dusts, granulates or sprayable solutions, they contain the customary auxiliaries which are used in such formulations as self-lubricating, non-lubricating, adhesives, dispersible, solid or liquid or solid or liquid or , auxiliary agents to facilitate the dissolution and dissolution of the solvent.

The wettable powders are present in water uniformly dispersible preparations which contain, in addition to the active ingredient and in addition to diluents, carriers or inert substances, mixtures of, for example, polyoxyethylated nitro-alcohol, polyoxyethylated fixed alcohols, alkyl or alkylphenyl-ulphonates, and isisoprotal. for example, ligninsufoonic acid calcium, 2,2'-sodium-methanesulfonic acid, sodium di-lysine, sodium salt of di-sulfonate-sulfonic acid. or also olelolbeeУyltausios sodium.

Embossed concentrates are prepared, for example, by dissolving the active ingredient in an organic solvent, for example butanol, cyclohexene, dibetylforbid, xylene, or else in high-boiling, hydrocarbon or hydrocarbons, with the addition of at least one explosive.

The following may be used as emulsifiers: calcium salts of alpha-1-sulfonyl sulfonic acid, such as calcium salts of dodecyl benzene sulphonic acid, non-ionic e-agents such as polyglycoesters of matic acids, glycol glycol ethers, polyglucols, fatty alcohol alcohols.

start with propylene oxide and ethylene oxide products, fatty alcohol products, propylene oxide and ethylene oxide products, alkyl polyethers, sorbitan fatty acid esters, polyoxethylene sorbitan fatty acid esters, sorbitol polyoxyethylene sorters, condensation products of arylalkanes with propylene oxide and ethylene oxide.

Dusts are obtained, for example, by grinding the active compound with finely divided, solids, for example talc, natural clays such as kaolin, bentonite, pyrophilite or diatomaceous earth.

Granules can be prepared, for example, by spraying the active ingredient solution onto an adsorptive, granulated inert material, or by applying active ingredient concentrates with adhesives such as polyvitylalcohol, sodium acrylic acid or also mineral oils to the surface of carriers such as Suitable active substances can also be granulated in the manner customary for the production of granulated fertilizers, optionally in admixture with a fertilizer.

Concentrations of active substances in preparations customary on the market may vary with pesticide formulations.

For wettable powders, for example, the total active compound concentration can range from about 10 to 80%, the remainder to 100% by weight of the above-mentioned ingredients in the compositions.

The concentration of the active ingredient can also be about 10% to 80% in the case of eucuggable concatenates.

Powder formulations generally comprise from 5 to 20% by weight of active ingredient, the extensible solutions contain from about 2 to 20% by weight of active ingredient.

In the case of granules, the active substance content depends in part on whether the active compound is present in solid or liquid form and which granulating auxiliaries, fillers, etc. are used. This content is generally about 0.5 to 30% by weight.

For application, the commercially available concetrates are optionally diluted in the customary manner, for example in the case of readable powders and emulsifiable concentrates with water. Powdered and granular preparations as well as redox solutions are generally not further diluted with other inert substances prior to application. The applied concentrations of the active compound combinations according to the invention in the suspensions vary as usual according to external conditions, such as the method of application, the climatic conditions, in particular temperature and humidity, and, if appropriate, depending on the type of crop plant or its crop. w ^ I ^ -Li ^ s ^ s ^ zl. These concentrations can be concen- trated in wide oats and are about 0.005 to 0.1% w / w, preferably 0.005 to 0.05% w / w, of the active ingredients in spray suspensions. Higher concentrations of active ingredients can also be used, but only minor technical or economic benefits can be expected.

When applied to agricultural soil, for example, the applied properties of the active compounds according to the invention are about 0.3 to 31 kg / ha, preferably 1 to 11 kg / ha.

The active compound combinations according to the invention can also be applied together with other pest control agents, such as insecticides, fungicides or herbicides, either in the form of a soybean or also sequentially. Combination application with fertilizer is also possible.

The following examples illustrate the invention in more detail, without limiting its scope in any way. '

Examples illustrating composition of compositions;

Example 1

An emulsifiable concentrate is obtained from parts hmoVncvtníeh active ingredient mixture sestávaiíeí from compounds azvreů I t II Parts hmoVtnvtníeh eyklvhextnvni t ^{parts h} motnnstn ^{te h} VXE ^ ylpatn ^ v nvnylfenv ^ Li / 10 Ае0 / ⁺ ^ ^{+ /} pvčet AEO = number e ^Thy lenvxidc> ^above-h jedttte ^{to the} residual e i ^ l ^ iytoletheru.

Example d 2

A highly dispersible wettable powder is obtained by mixing

2 part ^{5 of} motncstníe ^{h and h} of the Prior nnýe ^{M A k +} te ^/ Assembly of IEI ^ ¹ t slvučieni.n azvreů II hmotncstníeh parts quartz tbsahulíeíht kaolin parts Ηοο ^ ^^ ο ο! Li-oninsulfonic acid calcium salt t part of the salt salt t t mixture to be used in the binder mill.

^{+ //} used independently inne ^ ^ ¹ t azvreů area ^{11 b} may YT TT in ^{Ké f} VRM šnýeh ^{of VHI-P, PR} and aa ^ ^ing straight rtaeny ktždá Zalas t until t pvtom mixed with spvlečně rtzemelt1. .

he said a d 3

Poprtš is obtained by mixing ^d i ^ SM ⁰ I ^ ^l innýeh AT: e ^{k +} / ^ consist of slv1čet azvreů ⁱ n ¹ t ¹¹ t bridge parts hmotncstníeh získtná mixture rvzeuele in kltdivovéu mill.

řříkltd4

The Grandate is obtained by mixing a mixture of up to 15 parts by weight of the active ingredient consisting of compounds and mixtures of up to 85 parts of inert inert acetals, such as silica, silica, and silica.

^{+ /} Unity-two ^{of the} active ^la t ^ky melting ^L V1 en ^{No. L} ^ t ^ c ^ ^o. In the first step, the t-part can be prepared separately, ^{and the} third time it is mixed with the rvzeuelv.

B. Examples illustrating the biocidal activity:

řříkltd I

In order to determine the bituminous content of the individual substances, the starting point is based on the LC values determined by the individual pests. The pure modified active ingredient ^1c, if desired, mixes the active ingredients in the suspension in a spray suspension, if necessary in a controlled release formulation, which is required to provide 1% of the active substance test. with 50% effect. Hcdnoty pvtřebté previously tettt purpose dfítalí ^d with each of the diг ^] ^ i ^ O1 znázorrш1ícíht závislvst effect nt Dave PV plot zjištěnýeh hvdnot modalities pv t construct the regression line. The efficacy of the mummies consists of a crowd of tears, determined by a method that describes Yun-Pei Sun t ER Jvnsnsvn. Ec ^. Еп ^ то ^, 1960, Vol. 5, 5; 887 to 892.

The first purpose is to calculate the coefficient of kotoxicity may be as follows following the actual index of the mixture tetretic index x 100

A coefficient of kotoxicity of the mixture close to 100 indicates a combined effect of both substances · a coefficient less than 100 indicates antagonism and a coefficient greater than 100 indicates synergism.

Bean plants which are heavily infected with the spider mite (Tetranychus urticae) are sprayed with the preparations obtained from the emulsion concentrates of the individual active substances or the active substance combination (WS) listed in Table I by dilution with water by the dilution method until dripping begins The spray layers were placed in a greenhouse at 20 ° C to 3 ° C. The mortality of warbill mites is determined 8 days after treatment. From the values obtained it is found always Lc _5Q / WS% in the spray slurry and / cotoxicity coefficient is calculated for the mixture according to the method described by Yun-Pei Sun and others. The test results are summarized in Table I.

Table I

Active substances ^{+ /} * ^1c 50 (wt% WS). kotoxicity coefficient compound Ic 0.00044 compound If 0.0006 5 compound IIc 0.00950 of Ic + IIc 0.00030 269 weight ratio 1: 1 of Ic + IIc 0.00500 207 1:31 weight ratio of compound If + che 0.00070 176 weight ratio 1: 1 of compound If + che 0.00400 167 1:31 weight ratio

+ / Compound les S- [N- (4-chlorophenyl) -N-isopropylcarbamoylmethyl] -O-ethylmethyldithiophosphonate Compound If with S- [N-isopropyl-N- (2-isopropylphenyl) carbamoylmethyl] -O-methylmethyldithiophosphonate

Compound IIc: (S) -α-cyano-3-phenoxybenzyl (1R) -cis-3- (2,2-dibromvinyl) -2,2-dimethylcyclopropanecarboxylate.

It can be seen from the last column of Table I that the kotoxicity coefficients of the mixtures are well above 100, i.e. they are synergistic.

Example II

Bean plants (Vicia faba) heavily attacked by aphids (Aphis craccivora) are treated with aqueous suspensions prepared from wettable powders of the individual active substances or combinations of active substances (WS) listed in Table II in the dilution series until the drop dripping stage and after drying the layers were placed in a greenhouse at 20 and 3 ° C. Determination of aphid mortality is performed 3 days after treatment. The LC _5q (x% WS) values in the spray suspension / and the kotoxicity coefficients for the mixtures are determined analogously to Example I. The results are summarized in Table II below.

Table II

Effective L ^and T ^{+ ky} / ^LC S0 /% УmrI ^ n ^ rt ^: i WS ................ k ^ e ^ eicient kotoxicity compound If 0,0016 compound IIc 0.000005 compound lid 0.0000075 of compound If + che ’0.00024 338 weight ratio 63: 1 If + ld compounds 0.00009 135 УльШп ^ п! 16: 1 ratio

¹ Compounds If and cf. Table I;

Compound IId: (S) -affa-cyano-3-phenoxybenzyl (1R) -cS (3- (tetrabromoethyl) -2,2-dimethylcyclopropanecarbboyyite).

As can be seen from the last column of Table II, the co-toxicity coefficients of the compositions are clearly greater than 100, except that synergisms occur with these compositions. Example III

1 ml of acetonic solutions of the individual active substances or the combination of active substances (WS) listed in Table III in the dilution series are pipetted on the inside of the lid and the bottom of the Petri dishes, and the lids or dishes are left open in the air until complete evaporation of acetone. Then, 10 eyes of the house fly (Musea doimesica) are placed in the dishes and the lids are closed. After 3 hours, the mortality of the individual housefly eyemmulators was determined. Determination of LC ^ / =% WS values in concrete samples / coefficients. The toxicity of the salts is analogous to Example I. The results are summarized in Table III below.

Table III

Effective 1 ^^ + / LC50 /% Уortortort koeeicient WS / kotoxic.ity compound If 0.015 compound IIc ^; 0.00001 compound lid 0,0013 of compound If + che 0.0005 229 the 125: 1 molar ratio of If + people had a mortar ratio of 3.2: 1 0,0033 150

cf. Tables I and II

As can be seen from the last column of Table III, it exceeds ϊϊ Ι otox

SALES value of 100, in that they have a Si-sous. Example 1 a d IV -

In an analogous manner to that of Example III, the active compounds or the active ingredient combinations listed in Table IV in the form of acetic solutions in dilution series are applied to the inside of the lid and bottom of the Petri dishes, and the solutions are then not drained. Then, 10 specimens of Blatella germanica in the fourth larval stage are placed in each dish, and the plates are sealed with lids after 72 hours, and the degree of percent morrthity is determined. Determination of LC values of $ ₀ (=% WS in acetonic solution) and coefficients of toxicity for smmsi is performed analogously to Example I. The results are summarized in Table IV.

Table IV

6činn ^{é á} l ⁺ area ^/ /% hmornnrtnS WS / koeeicient-toxicity compounds If Compound IIc-IIc compounds If hmornirtní ratio 32: 1

0.013

0.000042

0.00095

131 ⁺ cf. Table I.

As can be seen from the last column of Table IV, the observed kotoxicity coefficient clearly exceeds 100, i.e. there is synergism in the mixture.

Example V

1 ml of the acetic acid solution of the individual active substances or the active compound combinations (WS) listed in Table V in the dilution rows are pipetted onto the filter paper discs by pipette, and the thus dripped paper discs are placed on the outer side of the bottom of the Petri dish. and acetone was evaporated. Ten larvae (3rd larval stage) (Tenebrio mooltor) are then added to each filter dish on filter paper and the dishes are closed with lids. The% mortality rate is determined after 48 hours. Determination of values _5Q LC / WS =% acetone solution and / koeeicientů cotoxicity the mixture is carried out in an analogous manner as described in Example I. The results are listed in summary form in Table successors · V

Ta bulka V

Effectively ^{E! and} TK ^{+ y} / / 4 · hmmrnnrtní

WS / coefficient of kotoxicity compound If compound face of compound If + face ^ !ί ^ ο ^ η! arm 2: 1

0.0044

0.001

0.00085

253 cf. Table I.

As can be seen from the last column of Table V, the observed thioefficient is well above 100, i.e. synergy is found in the boldness.

EXAMPLE VI

The active compound (s) / WS (s) mentioned in Table VI are added dropwise in a dilution series in a manner analogous to that described in Example V, and the acetone is allowed to evaporate. Then, 10 µg of black pimpered louse (S / S granarius) was placed in each Petri filter paper dish and sealed with the appropriate lids. The determination of тоШШу in% is performed after 48 hours. Determining the _5Q LC / WS% acetonic solution and / Co-toxicity coefficients of the sites is performed in a manner analogous to that described in Example I. The test results are listed in summary form in Table VI. .

Tib Street VI

^Star active substances ^{// + LC} 50 (% TANO WS). coefficient of kotoxicity compound If 0,0225 Λ compound IIc 0.00038 compound lid 0,00042 ' - of compound If + che 0.004 201 mass 31: 1 If + ld compounds 0.0046 118 mass ratio 16: 1

+ / cf.

Table II.

As can be seen from the last column of iotoxiaity for the mixtures, the value of 100, Table VI, significantly exceeds the observed coefficient values, i.e. there is synergism in these mixtures.

Claims (1)

An insecticidal and acaricidal composition comprising, as an active ingredient, a compound of formula (I) CH I " N-C-CH ₂ -S- _P> o S »llx« ^R2 _»7-OR3 wherein R is chloro or C1 -C3 alkyl, R @ 2 and R @ 2 are methyl or ethyl, and n is 1 or 2, in combination with a compound of formula II wherein: Y represents a group of the formula CH (CH ₃ ) CH ”or where Ra and Rb are methyl or Ra is hydrogen and Rb is dichlorovinyl, dibromvinylovou group, tetrachloroethyl Groups should ^л pin, tetrabromefcbylovou group dichlordibromethylovou group, and, R is cyano or hydrogen, its optical isomers or geometric isomers or mixtures thereof /, wherein the ratio of the components of formulas I: II to each other is between 200: 1 and 1;