DE2541512A1 - SOIL INSECTICIDES - Google Patents

Description

The present invention relates to the use of 2,4-disubstituted ones 3-Oxo-5 (2H) -pyridazinyl esters of phosphoric or thiophosphoric acid as insecticidal agents against those living in the soil Pests.

So far, pesticidally effective pyridazonyl-5-esters have been reported in the literature of organophosphoric acids of the general formula I known:

(D

-R.

In this formula, R ₁ and R ″ denote identical or different, saturated or unsaturated hydrocarbon radicals having 1 to 4 carbon atoms, an alkoxy or alkyl mercapto group, one optionally with a halogen atom or with an alkyl or amino group of the general formula II

609816/1046

^E 4

(II)

where R ₄ and Rj- V / hydrogen atoms, identical or different, saturated or unsaturated aliphatic or cyclic hydrocarbon radicals with 1 to 6 carbon atoms, optionally substituted by halogen atoms or cyano groups, which radicals together with the nitrogen atom form a heterocyclic ring which still has another Can have hetero atom, can form substituted aryl radical; R 1 denotes a hydrogen atom, a saturated or unsaturated aliphatic or cyclic hydrocarbon radical having 1 to 12 carbon atoms, optionally substituted by a halogen atom, an alkyl or nitro group; R also denotes an aryl radical, optionally substituted with a halogen atom, with an alkyl or nitro group, an aralkyl, alkoxymethyl, aryloxymethyl, dialkylaminomethyl, alkylthiomethyl, alkylsulfinylmethyl or alkylsulfonylmethyl group; X represents a halogen atom and X ₁ , X “and X represent an oxygen or sulfur atom.

Furthermore, pyridazonyl-4-esters are insecticidally and acaricidally effective Organophosphoric acids of the general formula III

R ^(III)

^R 4

known. In this formula, R ₁ and R _? Halogen atoms, identical or different hydrocarbon radicals with 1 to 5 carbon atoms or together a free or substituted amino group; R, denotes a saturated or unsaturated hydrocarbon radical having 1 to 5 carbon atoms, a phenyl radical, which optionally

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substituted with a halogen atom or with a methyl or nitro group can be; furthermore, R denotes a group of the general formula IV

R ₆ -X ₄ - CH ₂ - CH ₂ -

(IV)

wherein R, a hydrocarbon radical with 1 to 4 carbon atoms, a phenyl radical, optionally with a halogen atom or with may be substituted by a methyl or nitro group;

R. means a hydrocarbon radical with 1 to 6 carbon-4

atoms, a benzyl group, which optionally with a halogen atom, may be substituted with a nitro or methyl group, a phenyl radical, optionally with a halogen atom with a methyl or nitro group and X., X «, X,

and X. represent oxygen or sulfur atoms. 4th

The preparation and properties of the compounds of the general Formulas I and III are described in Czechoslovak Patent Nos. 133 * 589 and 141 * 951. You are for example accessible by reacting organophosphoric acid chlorides with a 2,4-disubstituted 3-oxo-5-hydroxypyridazine.

Up to now, none of the compounds has been as generalized as above Formulas describe the insecticidal effectiveness against the pests living in the soil.

It has now been found that pyridazinyl-5-ester of phosphorus or Thiophosphoric acid of the general formula V

- R.

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where R., R _? and R, an alkyl radical with 1 to 4 carbon atoms, R. an alkyl radical with 1 to 6 carbon atoms, an alkenyl radical with 2 to 6 carbon atoms, a cyclohexyl, phenyl or benzyl radical and X., X _? and Y denotes an oxygen or sulfur atom, display a high degree of insecticidal activity against pests living in the soil, in particular against the pests of the order Coleoptera, Diptera and Lepidoptera. The effectiveness of the compounds mentioned against the click beetle larvae (family Elateridae), in particular against the strains Agriotes and Corymbites, such as A. obscurus (L.), A. ustulatus (Sch.), A. lineatus (L.), is economically significant. C. aeneus (L.), C. latus (Fabr.) And also the effectiveness against the grubs of the family Scarabeidae and Chrysomelidae, the larvae of the two-winged insect of the family Anthomydae, Bibionidae, Psilidae and caterpillars of the family Hoctuidae.

The active compounds according to the invention can be used for application Process solutions, emulsions, suspensions, scatter powders, pastes and granulates. These can be produced in different ways be, for example with auxiliaries, such as with liquid Solvents or solids, optionally using surface-active substances such as emulsifiers or dispersants. If water is used as the solvent, an organic, so-called liquid solvent, can be used as an auxiliary solvent. are used .. Mainly aromatics such as xylene and toluene, chlorinated aromatics such as chlorobenzene and some crude oil fractions, also methanol and butanol. In addition, strongly polar solvents, such as dimethylformamide and dimethylsulfoxide, and also water used.

For example, kaolin, aluminum oxide, chalk, Talc and silicates are used. Both nonionic and ionic types can be used as emulsifiers, for example polyoxyesters of fatty alcohols, alkylaryl polyglycol ethers, alkyl and aryl sulfonates. Waste sulphite liquors, for example, can be used as dispersants and methyl cellulose in question.

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The most advantageous form for application is in the ground The granules are. As a rule, it is by spraying the active ingredient in an amount of 1 to 25 wt .- ^ i on the granulated Carrier material with a grain size of 0.2 Ms 3> 0 "im (according to Art of the plant), if necessary with the use of auxiliaries, such as stabilizers and the like. As a granulated carrier, kaolin, atapulgite, diatomite, silica gel are used etc. used. The amount of active ingredient injected depends on the absorption capacity of the granulated carrier.

The 2,4-disubstituted 3-Ox ° -5 (2H) -pyridazinyl esters used according to the invention the phosphoric and thiophosphoric acids possess when used to fight against stages of the harmful ones living in the soil Insects have several advantages compared to insecticidal agents based on O-ethyl-S-phenylethyldithiophosphonate, 0,0-diethyl-S- (ethylthiomethyl) -dithiophosphate, 0,0-diethyl-0- (4-nitrophenyl) -thiophosphate, 2,3-dihydro-2,2-diethyl-0- (3,5,6-trichloro-2-pyridyl) -thiophosphate etc., which are used in practice to combat soil pests.

They have advantageous physicochemical properties, they are practically odorless, they are sufficiently stable in the ground; they are not phytotoxic and can be easily degraded with alkalis detoxify. Above all, they have a very advantageous residual effectiveness.

The following examples are intended to illustrate the invention in more detail. without limiting them in any way.

example 1

The effectiveness of the compounds that can be used according to the invention on the larvae of the click beetle (Elateridae) was determined by the following method »

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The earth, which is used to create the experiment, is first dried, sifted and processed to the desired structure. The soil prepared in this way becomes 200 g each for a tested concentration weighed in. The weighed-in soil is put into a 2 liter powder jar with the exactly weighed-in agent. The powder jar is closed and shaken on a shaker for 5 minutes. The mixture of the earth and the agent prepared in this way is poured into cylinders (height 12 cm, diameter 5 cm), which are stiffened inside with a PVC polie; the lower part the film is attached to the cylinder by means of a polyamide fabric and a rubber band. The cylinder prepared in this way is placed on a Petri dish with the polyamide fabric facing down. 5 click beetle larvae are placed in each cylinder and the surface is poured with 10 ml of water. To prevent cannibalism among the individual larvae, three are placed in each cylinder Corn kernels. Then the cylinders are in a room with a tem perature of 22 - 2 C and with a corresponding relative humidity given. Each concentration is repeated six times. Every other day, each cylinder is poured with 10 ml of water. After 14 days the experiment was evaluated in such a way that the dead click beetle larvae were counted. Three reps became the middle one Percentage calculated.

The residual effectiveness after 14 days was determined in the same way, The only difference is that the click beetle larvae were not inserted into the cylinders until 14 days after the experiment was started after mixing the soil with the agent and pouring it into the cylinders. The evaluation was also carried out after 14 days. The results are shown in Tables 1 and 2.

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Table 1

Determination of the insecticidal effect on click beetle larvae (Elateridae) under laboratory conditions using the cylinder method

Name of the connection
or the active ingredient concentration
in ppm At first
effect Effect after
14 days 0,0-diethyl-0- (4-nitrophenyl)
-monothiophosphate, parathion-
NIRAN-G (standard) 12th
6th
3 100
100
100 100
100
100 O-ethyl-S-phenylethyl-di-
thiophosphonate
Phonophos-DYPONATE (standard) 12th
6th
3 100
100
100 100
100
100 0,0-Diethyl-S- (ethylthio-
methyl) dithiophosphate
Phora.t-THII.1ET (standard) 12th
6th
3 100
100
100 100
100
100 0,0-diethyl-S- (3-thiopentyl)
-dithiophosphate
Disulfoton-DISYSTON (standard) 12th
6th
3 100
100
100 100
100
100 O-ethyl-0-isopropyl-0- (2- ^
methyl-3-oxo-4-methoxy-5 / .2H / -
pyridazinyl) thiophosphate 12th
6th
3 100
100
86 100
95
87 O-ethyl-0-isopropyl-0- (2-
phenyl-3-oxo-4-ethoxy-5j [2H / -
pyridazinyl) thiophosphate 12th
6th
3 100
100
100 100
100
100 0-ethyl-0-isopropyl-0- (2-
phenyl-3-oxo-4-methoxy-5-
£ 2Η7 pyridazinyl) thiophosphate 12th
6th
3 100
100
100 100
100
100 0-ethyl-S-isopropyl-0- (2-
methyl-3-oxo-4-methoxy-5-
^ 2H7pyridaziny1) thi phosphate 12th
6th
5 46
53
55 100
95
100 0-ethyl-0-isopropyl-0- (2-
benzyl-3-oxo-4-methoxy-5-
/ -2Hj pyri daziny 1) thi ophosphate 12th
6th
3 86
75
15th - 0,0-dipropyl-0- (2-raethyl-
-3-oxo-4-methoxy-5 / 2H ^ pyri
dazinyl) thiophosphate 12th
6th
3 86
40
15th 100
100
100

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Table 2

Determination of the insecticidal effect on click beetle larvae (Elateridae) under laboratory conditions with the cylinder method

Name of the compound concentration
or of the active ingredient in ppm 12th At first
effect 1. O-ethyl-O-isopropyl- ^ CY 2-hexyl-
^ -oxo - ^ - niethoxy- 5 / 2iJpyri-
dazinyl) thiophosphate 12th 96 2. 0-Ethyl-0-i3opropyl-0 - (^ cyclo
hexyl-3-oxo-4-methoxy-5 / 2H / -
pyridazinyl) thiophosphate 12th 99 3. 0-ethyl-0-isopropyl-0 _z (2-allyl-
-3-oxo-4-methoxy-5 / 2H / pyri
dazinyl) thiophosphate 12th 100 4 · 0-methyl-0-isobutyl-0- (2-methyl-
-3-oxo-4-methoxy-5 / _2H7 pyrida
zinyl) thiophosphate 12th 87 5. 0-ethyl-0-isopropyl-0- (2-methyl-
-3-oxo-4-methylthio-5Z2Il7-pyri
dazinyl) thiophosphate 12th 100 6. 0-ethyl-0-isopropyl-0- (2-methyl-
^ -oxo ^ -propoxy ^ Z ^ Hjpyrida-
zinyl) thiophosphate 12th 100 7. 0-ethyl-0-isopropyl _r 0- (2-phenyl-
-3-oxo-4-methoxy-5 / 2Il7pyrida-
.zinyl) thiophosphate 12th 91 8. O-ethyl-3-phenyl-ethyl-dithio-
phosphonate Phonophös-Dyfonate
(Default) 100

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Example 2

The effect of the compounds proposed according to the invention on the click beetle larvae (Elateridae) was found in combined soil? tests followed by the following procedure:

In the case of the combined soil tests, the agents were applied directly into the soil on a field and the soil samples were taken at regular time intervals. The soil was then worked up as in Example 1, and the testing as in Experiment 1 was continued in the same way. Mortality was evaluated after 14 and 50 days.
The results are given in Table 3.

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Table 5

Combined soil test. Determination of the insecticidal effect on click beetle larvae (Elateridae) under laboratory conditions with the cylinder method

Name of the connection

I. Evaluation
Active ingredient / ha
Mortality. $
4 kg / h 3 kg / ha

II. Evaluation

Active ingredient / ha mortality% 4 kg / ha 3 kg / ha

0-ethyl-0- (2,4,5-trichlorophenyl)

-ethyl monothiophosphonate trichloronate AGRITOX

42.1

33.3

37.5

2,3-dihydro-2,2-dimethylbenzo-
furan-7-yl-1J-methyl carbamate
C arbofuran-Puradan - 94, 7th - 92, 3 O-ethyl-S-phenylethyldithio-
phosphonate Phonophos-DYFONATE 26.3 5, 5 12.2 0 -Zyanbenzylidenaminodiethyl-
phosphorothionate '
Phoxim-VALEXOH 15.7 11 1 37.5 0 O, O-diethyl-O- (3,5,6-trichloro-
-2-pyridyl) htonothiophosphate
ChI orphyrophos-DURSBAEF 52.6 0 12.5 0 0, O-diethyl-S- (ethylthiomethyl) -
dithiophosphate
Phorate THIMET 21.0 16, 6th 18.7 46, 1 Methyl-N'ijJf'-dimethyl-H-Cmethyl-
carbamoyl) oxy1-1-thioaxaminidate
Oxamyl VYDATE 21.0 5, 5 25.0 0 8 <$> HCH-I somer
Lindane LIDENAL 47.3 0 25.0 9, 2 1,2-dichiorethane
Ethylene dichloride NEMACÜR 36.8 22 2 75.0 0 S-chloromethy1-0,0-diethylphosphoro-
thiolothionate
Chlormephos-BÖTAJT 94.7 88 8th 68.7 0 O-ethyl-SjS-dipropyldithiophosphate
Ethoprop MOCAP 100.0 16, 6th 31.2 0 0,0-Dxäthyl-0- (4-nitropheny1) -
monothiophosphate
Paration-NIRM-G 42.1 11 » 1 6.2 0 0-ethyl-0-isopropy3-0- (2-methyl-
-3-oxo-4-methoxy-5t2H / pyridazinyl)
thiophosphate 100.0 100, 0 47.0 29 4th

60 98 1 6 / T 0 4.6

Claims (6)

Claim Use of 2,4-disubstituted 3-O ^x ° -5 (2H) pyridazinyl esters the phosphoric or thiophosphoric acid of the general formula R-O wherein R ₁ , R "and R, an alkyl radical with 1 to 4 carbon atoms, R. an alkyl radical with 1 to 6 carbon atoms, an alkenyl radical with 2 to 6 carbon atoms, a cyclohexyl, phenyl or benzyl radical and X ₁ , X" and Y mean oxygen or sulfur atoms, as insecticidal agents against pests living in the soil, 6 0 9816/1046