DD295525A5 - SHEEP LABORATORY II - Google Patents

Abstract

The invention relates to pesticides that are able to break existing resistance in pest populations and their application in agriculture and forestry, in the protection of stored products, in the household and in the hygiene sector. According to the invention, pesticides are used which contain as active constituents a) an insecticide from the group of the thio- or dithiophosphoric acid esters of the general formula I and b) an N-arylamino acid 2-ethylhexyl ester of the general formula II. A, B, C, D and R correspond to the substituents given in the description of the invention. Formula (I) and (II) {pesticides; N-Arylaminosäure 2-ethylhexyl; thiophosphoric; dithiophosphoric; Resistance; Agriculture; Forestry; Stock protection; Household; Hygiene sector}

Description

i \ -NH-CH-CO-OClL ₁ -CIi-C ₄ H ₉ (n) (H)

in which for

R is hydrogen, C ₁ ^ - unbranched / branched alkyl or phenyl.

2. pesticides according to claim 1, characterized in that they contain as active ingredients 0.0-dimethyl-S- / N-methylcarbamoylmethyl / dithiophosphate (dimethoate) and a N-arylamino acid 2-ethylhexylester of the formula II.

3. pest control agent according to claim 1, characterized in that they contain as active ingredients 0.0-dimethyl-0-4-nitrophenylphosphorothioate (parathion-methyl) and an N-arylamino acid 2-ethylhexylesterder formula II.

4. pest control agent according to claim 1-3, characterized in that it contains as active ingredients a thio- or di-thiophosphorsäureester of formula I and a N-aryl amino acid 2-ethylhexylester of formula II in a ratio of 5: 1 to 1:10 Parts by weight in addition to conventional pesticide auxiliaries, diluents, modifiers or conditioners.

5. pesticides according to claim 1-4, characterized in that they are used for controlling animal pests in field crops of agricultural crops, for the protection of crop products, in animal husbandry facilities and in sanitary facilities.

Field of application of the invention

The present invention relates to pesticides containing as active ingredients an insecticide from the group of thio or Dithiophosphorsäureester and a N-Arylaminosäure-2-ethyl ester and their application in agriculture and forestry, in the protection of stored products, in the household and in the hygiene sector ,

Characteristic of the known technical solutions

Thio- and dithiophosphoric acid esters are distinguished by a relatively rapid knock-down action against pests and mites occurring in agriculture and in the household, and in some cases with relatively high warm-blood toxicity. The said insecticides therefore have the disadvantage that their applicability in practice,

This disadvantage is of considerable economic and toxicological importance, since, moreover, the repeated use of commercial preparations leads to marked resistance and thus to the necessity of increasing the required amount of active ingredient in order to guarantee a sufficient combatting effect can

From the literature it is known that widespread in agriculture and forestry and in the hygiene sector to the occurrence of resistance in various pests and Lastlingen against insecticides and acaricidal thio- and Dithiophosphorsaureesters comes

Klunker (Day Ber Akad Landw Wiss DDR ₁ BIn [1974] 126, 133-50) and Pilz et al (Arch Phytopathol u Pflanzensch Bin [1978] 6,383-391) report resistance phenomena in spider mite populations (Tetranychus urticae KOCH) to dimethoate plutheroetal (J Econ Entomol 74 [6], 1981, 736-740) describe resistance effects on malathion in Drosophila melanogaster Resistance to aphids (Myzus persicae Sulz) in relation to dimethoate is described inter alia by Devonshire (Pestle Sei 4 [1973], 521-529) and Otto ( Arch Phytopatol u Pflanzensch Bin 16 (1980), 283-285) reported pronounced resistance to various thio and especially Dithiophosphorsaureestern in populations of Musca domestica L is described inter alia by Sawicki (Pestle Sei 1973,4, 501-512) and Rupes et al (Int Pest Control 25 [4] 1983, 106-108) as well as Rupes et al. (Acta Entom Bohem. 79 [1982], 412-421). Malathion resistance was finally confirmed by, inter alia, Wool et al. (Appl. Appl ], 1 Further, from the literature some N-phenyl alanine esters have become known which have been used as intermediates in the synthesis of DL-N-aryl-N-acyl-alanine esters (eg CH 609,964, GB 1,164,160) Preparation of the corresponding insecticides are the subject of numerous applications for industrial property rights (eg US Pat. No. 2,494,283, DBP 814,142). In the literature, however, there is hitherto no indication that combinations of thio- and dithiophosphoric esters and N-arylamino acid-2-ethylhexyl esters have a more than additive insecticidal effect Furthermore, hitherto it has not been known that such combinations can break a resistance or cross resistance caused by thio- or dithiophosphorusorganics

Object of the invention

The object of the invention is the development of new pesticides with improved efficacy which at the same time can break a resistance caused by insecticides from the group of thio- or Dithiophosphorsaureester in pest populations

Explanation of the essence of the invention

The invention has for its object to develop new pest control agents that increase their economic effectiveness while reducing their Warmblutertizizitat by reducing the drug cost of known pesticides and at the same time break existing resistance in pest populations inventions The object is achieved by the fact that pesticides, which as active ingredients

a) an insecticide from the class of thio or Dithiophosphorsaureester the general formula I.

A S

p ' (D.

/ \ B C-D

in which A and B is a C 1-4 -alkoxy, C is oxygen or sulfur, and for D / 4 '- (O-dialkyl-thionophosphoryloxy) -phenyl-thiophenyl /, 4-bromo-2,5-dihalophenyl З-АІкуІ- 4-nitrophenyl 4-Nitrophenyl 2,6-Dialkylpyrmidin-4-yl N-alkylcarbamoylalkyl 1,2-Bis (alkoxycarbonyl) alkyl (6-halo-2,3-dihydro-2-oxobenzoxazol-3-yl) -alkyl (3 , 4-dihydro-4-oxobenzo / d / - / 1,2,3 / triazin-3-yl) alkyl or alkylthioalkyl and

b) a N-arylamino acid-2-ethylexylester of the general formula II

/ 'CNH-CH-CO-OCH -CH _{0-C 71} H _0, ч ^(II)

⁴ "~ ' ^C 2 ^H 5

in which for

R is hydrogen, C 1-8 straight-chain / branched alkyl or phenyl, which are capable of simultaneously breaking existing resistance in pest populations

Particularly preferred are the following compounds:

thiophosphoric

Compound 1 4,4-bis- (0,0-dimethyl-thionophosphoryloxy) -diphenyl-sulfide (Abate)

Compound 2 0- (4-bromo-2,5-dichlorophenyl-0,0-dimethyl-monothiophosphate) (Bromophos)

Compound 3 O, O-dimethyl-O- (3-methyl-4-nitrophenyl) -monothiophosphate (fenitrothion)

Compound 4 0,0-dimethyl-O- (4-nitrophenyl) -monothiophosphate (parathion-methyl)

Compound 5 O.O-diethyl-O-isopropyl-e-methylpyrimidine ^ -yl phosphorothioate (diazinon)

dithiophosphoric

Compound 6 O.O-dimethyl-SiN-methylcarbamoyl-methyl-dithiophosphate (dimethoate)

Compound 7 S-i ^ -BislethoxycarbonyOethyl-OjO-dimethylphosphorodithionate (malathion)

Compound 8 Б-б-СЫого-г.З-гііИугіго-г-охоЬепгохагоІ-З-уІ methyl-0,0-diethylphosphorodithioate (phosalone)

Compound 9 S- (3,4-dihydro-4-oxobenzo / d / - / 1,2,3-triazin-3-ylmethyl) -0,0-dimethylphosphorodithionate (azinphos-methyl)

Compound 0.0-diethyl-S-ethylthiomethyl-phosphorodithionate (Phorate) The N-arylamino acid 2-ethylhexyl esters of general formula II show a surprising synergistic effect on the insecticidal activity of the thio- and dithiophosphoric acid esters (formula I). Surprisingly, the pesticides according to the invention also at the same time also existing resistance or cross-resistance in pest populations, especially in Diptera, z. B. Musca domestica, to break.

This is significant in that a significant shortcoming in the permanent or periodic use of insecticides from the group of thio and dithiophosphoric acid esters in pest populations is the rapid population genetic accumulation of resistant mutants within the gene pool of the treated population. This unwanted and unwanted selection of a resistance strain inevitably leads to the need to use higher amounts of insecticide to decimate the population, which appears problematic from a toxicological as well as an economic point of view.

The pesticides according to the invention are therefore of considerable use in the fields of agriculture and forestry including the protection of stored products, in the household and in the hygiene sector, as they provide opportunities for breaking existing resistance in pest populations and ways to reduce the cost of active ingredients in the control of normal sensitive strains miscellaneous Result in pests.

The novel pesticides according to the present invention may comprise the usual pesticide auxiliaries, diluents, modifiers or conditioners for providing preparations in the form of solutions, emulsions, dispersions, powders, dusts, granules, etc.

The amount of active ingredient in the preparations of the invention varies depending on the mode of application of the preparation and is usually between about 0.05 to 95% by weight of the total preparation. Usually the amount of active ingredient is below 30%. The term "active ingredient" as used herein means at least one N-arylamino acid 2-ethylhexyl ester of the general formula II and combinations thereof and at least one compound from the group of the thio or dithiophosphoric acid esters of the general formula I and combinations thereof.

The ratio of synergist of general formula II to insecticide does not appear to be critical. Usually the two major components, i. Synergist and insecticide in the preparation in a ratio of about 1: 5 to 10: 1 parts by weight of synergist (II) to insecticide present, wherein "insecticide" refers to a compound from the group of thio or Dithiophosphorsäureester and combinations thereof.

The novel pesticides can be used according to the invention, for example as a wettable powder, as a microcapsule, as dust,

be formulated as granules, as a solution, as an emulsifiable concentrate, as an emulsion, as a suspension concentration or as an aerosol. They can have defined "release" properties and can also be used as bait.

The new pesticides of the invention may also contain other ingredients, e.g. B. one or

several compounds with pesticidal, especially herbicidal or f ugic properties or attractants, eg. B.

Pheromones or food ingredients for use as baits or for formulations for insect traps. The invention also includes a method for controlling pests, which is characterized in that the Pesticides according to the invention against pests in field crops of agricultural crops,

for the protection of harvested products and in livestock systems and in sanitary facilities are applied.

As preferred compounds of general formula II may be mentioned:

/ \ -NH-CH-CO-O-

CH ₀ -CH-C ₄ H ₉ Cn) ^(II)

Verb no. -R Kp ( ⁰ C) 140 11 -H Kpo, is 138-140 12 -CH ₃ Kpo, 3 130 13 -C ₂ H ₅ kpo * 145 14 -C ₃ H ₇ (n) Kpo.i 143 15 -C ₃ H ₇ (J) Kpo.i (Bzl / hexane [1: 1I) 16 -C ₆ H ₅ Fp ₆₆ -?

The proof of the insecticidal synergistic effect of the pesticides according to the invention was carried out on Laboratory strains of the housefly Musca domestica (see exemplary embodiment). The following examples illustrate the invention in more detail, but are not intended to limit its scope in any way. embodiment

1. Synergistic effects of combinations of compounds of the general formula I with compounds of the general

Formula II on the housefly (Musca domestica L.) based on the decision concentration:

Female houseflies from a PO-resistant laboratory strain (trichlorfon: LD ₅₀ = 200 pg / 2) are treated topically with 1 μM of the respective test solution. The method of application follows the method proposed by the "FAO-working party of Experts on Resistance of Pests to Pesticides, 1969" for monitoring the resistance of animal pests (FAO Plant Protection Bull. 17.76 [1969]).

A synergistic effect is obtained if the effect (mortality) of the active substance-synergist mixture differs significantly from the action of the insecticidal active substance alone. The significance test used was the X ² test shown in Weber (Plan of Biological Statistics, Stuttgart, 1972) the four-error table (see also L. Cavalli-Sforca: Biometry, Jena, 1972). The measured mortality values were corrected before the calculation according to the correction equation of Abbott (1925) (see also FA01969 and WHO report in: Hlth. Org. Techn. Rep. Ser. 1970,443):

w ... · ·, ",. % Mort test .-% control Mort. " _Лл

Corr. Mortality (% = rr-r ^ 7, n ~ n * 100

100% control mortality%

Table 1 shows the respective increase in activity (W) as the quotient of the effect of the insecticide alone and the effect of the mixture. The respective statistical quality of the calculated significances is symbolized for an error probability of Pi = 1% with [++] or P ₁ = 5% with [+].

Table 1 Measured increase in the activity of compounds of the formula I after addition of compounds of the formula II

links links effect the formula I the formula Il increase [W] 4 14 2.2 6 11 1.8 6 12 2.2 6 13 1.6 6 14 4.9 6 16 4.5

The sensitivity of the strain used (RKT) was approximately ₅₀ times higher than the dimethoate sensitivity of a PO-sensitive control strain with LD ₅₀ = 0.135pg dimethoate / 2 (LDs ₀ [SRS] = 0.01 μg / 9). Thus, for the PO-resistant strain (RKT) used, there is cross resistance to these dithiophosphoric acid esters with a resistance index of approximately R ₁ = 4.35.

The amounts used in the mixtures and alone amounted to Dimethoat at 0,005 € / 0 (0 mortality: 8,9%) Parathion-methyl at 0.5 pg / 9 (0 mortality: 16.5%) The mixing ratio of both synergistic components used was 1: 1 parts by weight.

2. Synergistic or resistance-breaking action of combinations of compounds of the general

Formula I and compounds of the general formula II on the spider mite (Tetranychus urticae KOCH)

Female adult individuals of the spider mite (Tetranychus urticae KOCH) of a dimethoate-resistant laboratory strain are planted on bush bean leaves previously treated with the aqueous active ingredient emulsion. The mortality control takes place after 3 days of keeping under standard conditions.

The active ingredient dimethoate was used with the synergists, each in the ratio 1: 1 parts by weight. The use of dimethoate was carried out in a commercial formulation (Bi58EC *) at a concentration of 0.5% preparation in the dipping solution.

Table 2

Measured increase in the activity of compounds of general formula I by addition of compounds of general formula II to spider mites (Tetranychus urticae KOCH)

Connection of Connection of achieved effect Formula I Formula Il Mortality (%) increase (W) 6 _ 17.6 _ 6 12 97.3 5.5 6 13 97.2 5.5 6 14 98.6 5.6

Claims (3)

1,2-bis- (alkoxycarbonyl) alkyl (6-halo-2,3-dihydro-2-oxobenzoxazol-3-yl) alkyl 1. pesticides, characterized in that they contain as active ingredients a) a thio- or Dithiophosphorsäureester the general formula I. P (I) / 'ч B C-U in which for A and B is a C ₁ ^ -alkoxy group, C means oxygen or sulfur and for D 4- (0,0-dialkyl-thionophosphoryloxy) -phenylthiophenyl .4-bromo-2,5-dihalophenyl З-АІкуІ-4-nitrophenyl 4-nitrophenyl 2,6-Dialkylpyrimidin-4-yl N -alkylcarbamoylalkyl (3,4-dihydro-4-oxobenzo / d / - / 1,2,3 / triazin-3-yl) alkyl or alkylthioalkyl and
b) an N-arylamino acid 2-ethylhexyl ester of the general formula II