DD295527A5 - SCHAEDLINGSBEKAEMPFUNGSMITTEL V - Google Patents

Abstract

The invention relates to pesticides. It is the object of the invention to develop such new pesticides, which increase their economic effectiveness by reducing the drug cost of known insecticides and at the same time able to break existing resistance or cross-resistance in pest populations. According to the invention, pesticides are used which contain as active constituents a) a carboxylic acid derivative of the general formula I and b) an N-phenylalanine ester of the general formula III. Both A and B as R to R exp 3 correspond to the substituents given in the description of the invention. Formula (I) and (III) {Pesticides; Active compound application; Insecticides; Effectiveness; Resistance; Cross-resistance; Pest population; Carboxylic acid derivatives}

Description

NH - CH - COOR

in which

R, R ¹ and R ² independently of one another are hydrogen, C _1-4 -alkyl, halogen or C _1-4 -alkoxy, and

R ^{3 is} Ci-12 un / branched alkyl, Ca ^ -cycloalkyl, Cs-g-alkenyl, C ₂ _4-haloalkyl, C ₃ _e-alkoxyalkyl, C / ^ - dialkylaminoalkyl, an optionally substituted phenyl, benzyl or phenethyl

is included.

2. Pesticides according to item 1, characterized in that they contain as active ingredients fenvalerate and an N-phenyl-alanine ester of the formula III.

3. Pesticides according to item 1, characterized in that they contain as active ingredients permethrin and an N-Phenylalaninester of formula III.

4. Pesticides according to item 1, characterized in that they contain active ingredients Cypermethrin and an N-Phenylalaninester.

5. Pesticides according to item 1 to 4, characterized in that they contain as active ingredients a carboxylic acid derivative of the formula I and an N-phenyl-alanine ester of the formula III in a ratio of 5: 1 to 1: 10 parts by weight in addition to contain the usual pesticide auxiliary, diluting, modifying or conditioning agents.

6. Pesticides according to item 1 to 4, characterized in that they are used for controlling animal pests in field crops of agricultural crops, for the protection of harvested 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 a pyrethroid insecticide and an N-phenyl alanine ester and their application in agriculture and forestry, in the protection of stored products, in the household and in the hygiene sector.

-2- 295 527 Characteristic of the known technical solutions

Synthetic pyrethroids are insecticides with low toxicity to warm-blooded horses, characterized by a rapid knock-down effect against insect pests found in agriculture and households. However, the synthetic pyrethroids have the disadvantage that their knock-down effect against pest insects is much lower when they are processed alone and in particular as aerosol spray.

Furthermore, it is reported in the literature (PA Chapman et al., Brit. Crop. Prot. Conf. Pests Dis., Brighton, Nov. 16-19, 1981) that increased use of commercial pyrethroid preparations has led to an increase in the Resistance has occurred in insect populations, which is an effective control of animal pests in low-cost funds used is at risk. Furthermore, it also appears questionable from a toxicological and population genetic point of view to protect the fight against agricultural pests and hygiene pests by increasing the drug expenditure.

Furthermore, the use of natural and synthetic pyrethroids in combination with synergists, e.g. Tributyl trithiophosphate (LT Jao et al., Pest Biochem Physiol 4,465-472 (1974)), piperonyl butoxide, safroxan and sulfoxide (Asada, S., et al., Botyo-Kagaku 36, 179-183 (1971)), 3,4- Dihydro-2- (2-propynylisoquinolinone- (1) (US 4,349,676), N-benzyltriazoles (EP 7589) and benzyl-2-propynyl ethers (US 3,880,999), however, these combinations have the disadvantage that they do not exacerbate existing resistance in pest populations to be able to break.

Further, some N-phenylalanine esters have become known from the literature which find utility as intermediates in the synthesis of DL-N-aryl-N-acyl-alanine esters (e.g., CH 609,964, GB 1,164,160).

It has not previously been known from the literature that N-phenylalanine esters can break a resistance or cross-resistance caused by pesticides in pest populations.

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 existing pyrethroid resistance in pest populations.

Explanation of the essence of the invention

The invention has for its object to provide new pesticides, which increase their economic effectiveness by reducing the drug cost of known insecticides and at the same time able to break existing resistance in pest populations.

According to the invention, this object is achieved by the fact that pesticides containing as active constituents a) a carboxylic acid derivative of the general formula I:

OA-C-O-B (I)

in which A is optionally substituted aralkyl, alkyl, cycloalkyl or arylaminoalkyl and B is a group of formula II:

in which R is hydrogen, cyano or ethynyl and X is alkyl, alkenyl, aralkyl or aryloxy and η is 1 to 5, or B is 5-benzyl-3-furylmethyl or 3,4,5,6-tetrahydrophthalimidomethyl, and b) an N-phenylalanine ester of general formula III:

CH ₃

-NH-CH-CO-OR ³

(III)

in which

R, R ¹ and R ² are independently hydrogen, C ₁ ^ ₄ - alkyl, halogen or C _1-4 -alkoxy, and R ³ is Cl ₁₂ un / branched alkyl, C ₃ - $ - cycloalkyl, Cj-e- alkenyl, C ₂ -4-haloalkyl, C _l _ _e alkoxyalkyl, C "stands _6- dialkylaminoalkyl, optionally substituted phenyl, benzyl or phenethyl,

and that can develop a more than additive insecticidal effect on animal pests and at the same time break existing resistance in pest populations.

It should be noted that optical isomers, cis-trans isomers and other types of geometric isomers of compounds of general formula I and general formula III are also included in this invention, as are racemates and mixtures of isomers of one or more compounds of the formula I and Formula III.

The compounds of the general formula I are a group of carboxylic acid derivatives which are grouped by their origin under the name "pyrethroid insecticides." The preparation of these compounds is the content of numerous patent applications, for example GB 1,413,941, OE 2,231,312; Some of the compounds of the general formula III have become known as intermediates in the synthesis of N-Arvl-N-acyl-alanine esters and can be prepared by known processes, for example J. Org by reaction of un / substituted anilines with α-halocarboxylic acid esters (eg CH 609,964) or by esterification of un / substituted N-phenylalanine (eg GB 1,164,160) The other compounds of general formula III can be prepared by analogous methods.

The N-phenyl-alanine esters of the general formula III show a surprising synergistic effect on the insecticidal activity of the carboxylic acid derivatives of the formula I with respect to animal pathogens.

Surprisingly, the pesticides according to the invention are also capable of existing resistance in pest populations, especially in dipterans, eg. B. Musca domestica, 2U break.

This is significant in that a major shortcoming in the permanent or periodic use of pyrethroid insecticides 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 according to the invention varies depending on the method of application of the preparation and is usually between about 0.05 to 95% by mass of the total preparation. Usually the amount of active ingredient is below 10%. The term "active ingredient" used herein means at least one N-phenylalanine ester of the general formula III and combinations thereof and at least one compound from the group of the pyrethroid insecticides of the general formula I and combinations thereof.

The ratio of synergist N-phenylalanine ester to insecticide does not appear to be critical. Usually the two major components, i. Synergist and insecticide present in the preparation in a ratio of about 1: 5 to 10: 1 parts by weight of N-phenylalanine ester to insecticide, wherein "insecticide" refers to a compound from the group of pyrethroid insecticides and combinations thereof.

According to the invention, the novel pesticides can be formulated, for example, as a wettable powder, as a microcapsule, as a dust, as granules, as a solution, as an emulsifiable concentrate, as an emulsion, as a suspension concentrate or as an aerosol. They may have defined "release" properties and may also be used as baits The novel pesticides according to the invention may also contain other constituents, for example one or more compounds having pesticidal, in particular herbicidal or fungicidal properties or attractants, for example pheromones or food constituents The invention also includes a method of controlling pests, characterized in that the pesticides according to the invention are controlled against pests in field crops of agricultural crops, for the protection of harvested products and in livestock farming facilities, as well as for use as baits or insect traps may be applied in sanitary facilities.

Compound 1 fenvalerate

Compound 2 Fluvalinates

Compound 3 phenothrin

Compound 4 permethrin

Compound 5 Cypermethrin

Compound 6 decamethrin

Compound 7 fenpropathrin

Compound 8 tetramethrin

Compound 9 resmethrin

Compound 10 Bromethrin

Compound 11 bioethanomethrin

Compound 12 kadethrin

Compound 13 deltamethrin

Compound 14 Tralomethrin

Compound 15 tralocythrin

Compound 16 Cyhalothrin

Compound 17 Cyfluthrin

As preferred Verbindugnen the general formula III may be mentioned:

CH, I

NH - CH - CO - OR ³ (""

R R ¹ R ² R ³ -4- Kp ro 295 527 Ser. -H -H -H -CH _{3 132/6} FP (X) 18 -H -H -H -C ₂ Ha 124 / _s 40-41 19 -H -H -H -C ₃ H ₇ (n) 124-125 / ,, ₂ 20 -H -H -H -C ₃ H ₇ (I) 150-152 / ₃ , 6 45 21 -H -H -H -C ₄ H ₉ (n) _{114/0, 2} 37-38 22 -H -H -H -C ₄ H ₈ (I) _140/2 23 -H -H -H -C ₆ H ₁₃ (n) 153-154 / ₃ 24 -H -H -H -C ₈ H ₁₇ In) 147-148Λ.5 25 -H -H -H -C ₁₂ H ₂₅ (n) 215-217 / ₂ 26 -H -H -H -C ₅ H ₁ (C) 149-15V ₃ 27 -H -H -H -C ₆ H ₁₁ (C) 144-145 / ₂₆ 28 -H -H -H -CH ₂ -CH = CH ₂ 109.5 to 110 / 29 -H -H -H - (CH ₂ I ₂ -CI 156 / j 30 -H -H -H - (CH ₂ JrOCH ₃ 169-171 / ₄ 31 -H -H -H - (CH ₂ I ₂ -OC ₂ H ₅ 153-155Λ 32 -H -H -H - (CH ₂ ) ₂ -N (CH ₃ ) ₂ 175/4 33 -H -H -H -C _e H ₅ 135 / 0.1 34 -H -H -H -CH ₂ -CiHs 35 -Η -H -H - (CHj) ₂ -C ₆ H ₆ 160-162 / o.ra 64.5 to 66 36 -H -H -H -CH (CH ₃ JC ₆ H ₆ 181-Ί83Λ 42-43 37 2-CH -H -H -CH _{3 132/6} 44-45 38 -H -H 3-CH ₃ -CH ₃ 124-125 / 2 39 -H -H 4-CH ₃ -CH ₃ 124-i25 / ₃ 40 2-CI -H -H -CH ₃ 111-112 / 47-48 41 -H -H 3-CI -CH ₃ 114-115A.2 42 -H -H 4-CI -CH ₃ 145-i46 / ₄ . _8th 25-26 43 2-OCH ₃ -H -H -CH ₃ 133-134 / 2 36-37 44 -H -H 3-OCH ₃ -CH ₃ 147-i48 / ₄ .s 45 -H -H 4-OCH ₃ -CH ₃ 143 / ,, β 46 2-CH ₃ -H 3-CH ₃ -CH ₃ 118-i20 / ,, 5 47 2-CH ₃ -H 4-CH ₃ -CH ₃ 108-109 / 0.2 48 2-CH ₃ 5-CH ₃ -H -CH ₃ 112 to 113.5 / z 49 2-CH ₃ 6-CH ₃ -H -CH _{3 108/2} 50 3-CH ₃ -H 4-CH ₃ -CH ₃ 140 / 4.5 51 3-CH ₃ 5-CH ₃ -H -CH ₃ 126 / _{0th 6} 52 2-CI -H 3-CI -CH ₃ 150-151 / 3.6 53 2-CI -H 4-CI -CH ₃ 147-148 / ₆₈ 54 2-CI 5-CI -H -CH ₃ 129-130Λ * 35.5 55 2-CI 6-Cl -H -CHJ 120 / 0.7 56 3-CI -H 4-CI -CH ₃ 152Λ. _8th 57 3-CI 5-CI -H -CH ₃ 137-138 / 42.5 to 43 58 2-CH ₃ -H 3-CI -CH ₃ 170 / J.E. 59 2-CH ₃ -H 4-CI -CH ₃ 193 / 4.5 60 2-CH ₃ 5-CI -H -CH ₃ 138-140 / ₂₆ 61 3-CI -H 4-CH ₃ -CH _{3 160/3} 63.5 to 65 62 2-C ₂ H ₆ 6-CH ₃ -H -CH ₃ 107-108 / ₂ 63 2-C ₂ H ₆ 6-C ₂ H ₈ -H -CH ₃ 100 / e ,. 64 2-CH ₃ 6-CH ₃ 4-CH ₃ -CH _{3 137/3. 6} 65 2-CI 6-Cl 4-CI -CH _{3 135/01} 66 2-C ₃ H ₇ 6-C ₃ H ₇ -H -CH ₃ 121 / m 67

example 1

Synergistic effects on Musca domestica L.

The application method used was the one from the FAO-working party of Experts on Resistance of Pests to Pesticides (FAO, 1969).

and the WHO (1963, 1970) used topical application method recommended for monitoring resistance events in animal pathogens.

The test for possible self-toxicity of the compounds of general formula III was carried out by running parallel to the test mixture control concentrations of these compounds.

The mortality values determined in the test were corrected according to Abbott (1925) (see also FAO 1969, WHO 1970) the following relationship:

Corr. Mortality (%)

% Test Mort. -% ControHomort. 100% - control mortality%

χ 100

The statistical assurance of the measurement results was carried out on the basis of (at E.Weber plan view of the biological statistics, Stuttgart, 19721 described κ'-test means of the fourfold table. The Sigifikanz (κ ²⁾ of Formula

(/ abb c / - 1 / 2n) ² (a + b) (a + c) (b + d) (c + (

"2 =.

calculated. See also L. Cavalli-Sforza, Biometrie Jena, 1972, p.57ff

 Here, a, b, c, d and η are the absolute frequencies of the 2 x 2 panel:

aba + bc ei c + d

a + c b + d n = a + b + c + d

Synergism is then present with 1% or 5% error probability if the calculated κ ^{2 is} greater than a value tabulated for each of these error probabilities and the mortality value of the mixture is greater than that of the insecticide. CO ₂ anesthetized female flies are treated by means of a microdosing device (Microdosing device of the company Instrumentation Specialties & Co., Lincoln, Nebraska, U SA) with 1 μΙ each of the appropriately dosed test substance. The acetone solution of the test substance is applied to the ventral side of the flies and kept (in each case 15 animals per test concentration) for 24 hours in glass containers. Subsequently, the counting of the dead animals. From these data, the mortality rate (%) per test concentration is determined and determined by means of the K ² test described above, the synergistic effect of the pesticidal composition over the drug control. As test animals flies of a trichlorfon-resistant breeding strain of Musca domestica L. were used, which has a weak cross-resistance with the factor 1.82 compared to decamethrin. In the test, the average percentage mortality of the pyrethroid insecticides alone and a mixture with the respective synergist in the ratio 2: 1 is measured. Table 2 shows, in addition to the statistical evaluation (K ² test), the respective factor (W) of the increase in activity compared with the insecticidal activity, which is calculated as the quotient of the two measured effects, is determined for each mixture alone.

For the pyrethroid active ingredients selected in the exemplary embodiment, the following concentration ratios were determined for the test animal strain used:

Table 1

LD5o values, used dosages and measured mortalities

Pyrethroid LDso levels dosage alone average

and in the mixture mortality

Fenvalerate 0.1 0.05 31.0

Permethrin 0.06 0.06 59.9

Cypermethrin 0.004 O ₁ OT 17.8

In the mixture, these agents were used in the same high dosage.

Claims (1)

1. Pesticides, characterized in that they contain as active ingredients a) a carboxylic acid derivative of the formula I: A-C-O-B (I) in which A is optionally substituted aralkyl, alkyl, cycloalkyl or arylaminoalkyl and B is a group of formula II in which R is hydrogen, cyano or ethynyl and X is alkyl, alkenyl, aralkyl or aryloxy and η is 1 to 5, or B is 5-benzyl-3-furylmethyl or 3,4,5,6-tetrahydrophthalimidomethyl, and
b) an N-phenylalanine ester of formula III