DE2352141A1 - NEW ESTERS - Google Patents

Description

CIBA-GEIGYAG. CH-4002 Basel

A-GBGY

Dr..F. Zumstein sen. - Dr. Ms. Acsr.iann Dr. R. Koenigsberger Dip !, l'isyo. R. Holzhauer

Dr. F. Zumstein jun. Potent Attorneys

8 Munich 2, Bräuhausstraße 4 / III

Case 5-8481 / 1 + 2 / = Germany

New esters

The present invention relates to triazolyl phosphorus compounds, Process for their production and their use for pest control. The triazolyl phosphorus compounds correspond to

formula

^SR 1

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wherein R _{1 is} C ₁ -C ₃ -AllCyI and 40 0 Z

η are the numbers 0 to 2.

The alkyl groups for R ₁ can be branched or straight-chain. Examples of such groups are: methyl, ethyl, propyl, isopropyl.

Because of their action, compounds of the formula I in which R ₁ denotes n-propyl and η denotes the numbers 0 to 2 are preferred.

The compounds of the formula I can be prepared by methods known per se, for example as follows:

Hal-P <r

NQTJ

(II) "* ' (IH)

N W "/ ^OC 2 ^H 5

Civ) ^> ^0Me _(III) ^SR i

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In the formulas II, III and IV, R ₁ and η have the meaning given for the formula I, Hal stands for halogen, such as fluorine, chlorine, bromine or iodine and Me stands for a monovalent metal, in particular an alkali metal.

The following bases, for example, can be used as acid-binding agents: tertiary amines, such as triethylamine, dimethylaniline, Pyridine, inorganic bases such as hydroxides and carbonates of alkali and alkaline earth metals, preferably sodium and potassium carbonate.

The reactions can preferably be carried out in solvents or diluents which are inert towards the reactants. For this purpose, the following are suitable, for example: aromatic hydrocarbons such as benzene, toluene, gasoline ₉ halohydrocarbons, chlorobenzene, polychlorobenzenes, bromobenzene _s chlorinated alkanes having 1 to 3 carbon atoms, ethers such as dioxane, tetrahydrofuran; Esters, such as ethyl acetate ; Ketones such as acetone, methyl _{ethyl ketone 3} diethy! Ketone, nitriles e.g. acetonitrile etc.

Some of the starting materials of the formulas II and IV are known compounds which, for example, are analogous to that in Chem. Ber "56 B, 2276-83 (1923) described method can be produced.

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The compounds of the formula I have a broad biocidal action and can be used to control various plant and animal pests. But they have in particular insecticidal and acaricidal properties and can be used against all stages of development such as eggs, larvae pupae, nymphs and adults of insects and representatives of the Akarina order, such as against family insects; Tettigonidae, Gryllidae, Gryllotalpidae, Blattidae, Reduvidae, Phyrrhocoridae, Cimicidae, Belphaeidae, Aphididae, Diaspididae, Pseudococcidae, Scarabaeidae, Dermestidae, Coccinellidae, Tenebrionidae, Chrysomelidae, Bruchidae, Tineidae, Noctuidae ₉ Lymatriidae ₉ Pyralidae, Culcidae, Tripulidae, Stomoxydae, Trypetidae _s Muscidae, Galliphoridae and Fulicidae ₃ as well as acarids of the families Ixodidae, Argasidae _s Tetranychidae and Dermanyssidae. The insecticidal or acaricidal effect can be significantly broadened and adapted to given circumstances by adding other insecticides and / or acaricides.

organic phosphorus compounds, derivatives of nitrophenols !! _D.

Urea _s carbamates and / or chlorinated hydrocarbons

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The active ingredients of the formula I are also suitable for combating representatives of the Thallophyta department such as viruses, Bacteria and fungi. They have fungicidal properties against phytopathogenic fungi on various crops, such as grain, corn, rice, vegetables, ornamental plants, fruit trees, vines, field crops etc. With the new active ingredients, fungi that appear on fruits, trees, leaves, stalks, tubers and roots can be removed can be contained or destroyed, with later overgrown parts of plants being spared from such fungi stay. The active ingredients of the formula I are particularly effective against the following classes of phytopathogenic fungi effective: Oomycetes, Zygomycetes, Ascomycetes, Basidiomycetes, Denterömycetes.

Furthermore, the new active ingredients are also used to treat seeds, fruits, tubers, etc., to protect against fungal infections, for example from _{smut fungi of all kinds 9,} such as ugilaginales, and to combat phytopathogenic nematodes.

The compounds of the formula I can be used alone or together with suitable carriers and / or additives can be used. Suitable carriers and additives can be solid or liquid and correspond to those in the Substances commonly used in formulation technology such as natural or regenerated substances, solvents, dispersants, wetting agents, Adhesives, thickeners, binders and / or fertilizers. For application, the compounds of the formula I can be used Dusts, emulsion concentrates, granules, dispersions, sprays, to solutions or slurries in the usual way Formulation used in application technology for General knowledge should be processed. Furthermore, "cattle dips", i.e. cattle baths, and "spray races", i.e. Mention should be made of spray courses in which aqueous preparations are used.

The agents according to the invention are produced in an known manner by intimate mixing and / or grinding of active ingredients of the formula I with the appropriate ones Carrier substances, possibly with the addition of opposite dispersants or solvents that are inert to the active ingredients. The active ingredients can be used in the following working-up forms are available and applied;

-Ir

Forms of processing: dust, grit,

Granules, coating granules, impregnation granules and Homogeneous granules

Liquid

Forms of processing:

a) dispersible in water
Active ingredient concentrates: wettable powders

Pastes, emulsions;

b) Solutions

The content of active substance in the above described compositions is between ₉ I O to 95%, is to be noted -that ₉ during application, from the aircraft or other suitable application equipment concentrations of up to 99.5% or even pure active substance to be used can"

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The active ingredients of the formula I can, for example, be formulated as follows:

Dust: To produce a) 5% and b) 27o dust, the following substances are used:

a) 5 parts of active ingredient
95 parts of talc;

b) 2 parts of active ingredient

1 part of highly disperse silica, 97 parts of talc

The active ingredients x ^ ground mixed with the carriers and marry.

Granules: The following substances are used to produce 5% granules:

5 parts of active ingredient

0.25 part of epichlorohydrin, 0.25 part of cetyl polyglycol ether,

3.50 parts of polyethylene glycol 91 parts of kaolin (grain size O ₉ 3-0.8 mm). The active substance is mixed with epichlorohydrin and dissolved with 6 parts of acetone. Polyethylene glycol ether and Ce'cy! Polyglycol ether are then added. The solution thus obtained is sprayed onto kaolin and then the

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Acetone evaporated in vacuo.

Wettable powders: For the preparation of a a) 407 _o by weight, b) and c) 257oigen d) 107 _o wettable powder following constituents are used:

a) 40 parts of active ingredient

5 parts of lignin sulfonic acid sodium salt,

1 part dibutylnaphthalenesulfonic acid sodium salt,

54 'parts of silica;

b) 25 parts of active ingredient

4.5 parts calcium ligin sulfonate,

1.9 parts of champagne chalk / hydroxyethyl cellulose mixture (1: 1),

1.5 parts of sodium dibutyl naphthalene sulfonate, 19.5 parts silica, 19.5 parts Champagne chalk, 28.1 parts of kaolin;

c) 25 parts of active ingredient

2.5 parts of isooctylphenoxy-polyoxyethylene-ethanol, 1.7 parts of champagne chalk / hydroxyethyl cellulose

Mixture (1: 1), 8.3 parts of sodium aluminum silicate,

16.5 parts of kieselguhr, parts of kaolin;

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d) 10 parts of active ingredient

3 parts Geraisch of the sodium salts of saturated

Fatty alcohol sulfates,
5 parts of naphthalenesulfonic acid / formaldehyde condensate,

82 parts of kaolin.

The active ingredients are mixed with the additives in suitable mixers intimately mixed and ground on appropriate mills and rollers. One receives wettable powder that can be diluted with water to form suspensions of any desired concentration.

Emulsifiable concentrates: The following substances are used to produce a) 10% and b) 25% emulsifiable concentrate:

a) IO parts active ingredient

3.4 parts epoxidized vegetable oil,

13.4 parts of a combination emulsifier, consisting of fatty alcohol polyglycol and alkylarylsulfonate calcium salt,

40 parts of dimethylformamide,

43.2 parts of xylene;

b) 25 parts of active ingredient

2.5 parts epoxidized vegetable oil,

10 parts of an alkylarylsulfonate / fatty alcohol polyglycol ether mixture,

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5. Parts dimethylformamide,
57.5 parts of xylene.

Such concentrates can be made by diluting with water Emulsions of any desired concentration can be prepared.

Spray: The following ingredients are used to produce a 5% spray:

5 parts active ingredient,

1 part epichlorohydrin,
94 parts gasoline (boiling limits 160 - 190 ⁰ C)

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example 1

Production of O-ethyl-S- (n) -propyl-0- [1-phenyl-1,2,4-triazolyl- (3)] - dithiophosphate

For 24 g of 1-phenyl-3-hydroxy-1,2,4-triazole and 32.8 g O-ethyl-S-n-propyl-dithiophosphoric acid chloride in 500 ml Acetone, 16.7 g of triethylamine are slowly added dropwise. The mixture is refluxed for 6 hours. After this After cooling, the precipitated triethylamine hydrochloride is filtered off. The filtrate is concentrated in vacuo and the Residue taken up in ether. The ether phase is with Water washed. The water phase is separated off and the ether phase is dried with sodium sulfate. After this Filtering off the drying agent, the ether is distilled off in vacuo "

The residue is over silica gel with chloroform as Eluent purified by chromatography »After evaporation of the solvent, the compound of the formula is obtained

■ 1

lefraktioa from

as folass yellow

-i- · _ J. ο

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The following connections are also established in the same way:

-N

n _D ²⁰ = 1.5849

Cl

• KF K

Cl

C ₃ H ₇ (Ii)

n _D ²⁰ . 1.5880

-sr

n _D ²⁰ »1.5736

Cl

Ο *

f p

L "ζ ⁰¹

C ₂ H

(η)

Ν—

-N

C "Η.

Ό · "· κ

ClCl

ö ^ ci _(Β)

N N

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Example 3

A) insecticides milling s fit ft-action clothes 2352141

Cotton plants and potato plants were sprayed with: an 0.057% aqueous active ingredient emulsion (obtained from a 10% emulsifiable concentrate). After the covering had dried on, the cotton plants were each populated with Spodoptera littoralis or Heliothio virescens larvae Lo and the potato thaws with Colorado beetle larvae (Leptinotarsa decemlineata). The experiment was carried out at 24 ⁰ G and. 60% relative humidity carried out.

The compounds according to Examples 1 and 2 show in the above reading a good insecticidal food poison effect against Spodoptera-j Hellothis and Leptinotarsa decemlineata larvae.

B) System laugh insecticidal effect.

To determine the systemic action rooted -Bohnenpflanzen '(Vicia faba) were placed in a 0 ₈ 01% aqueous solution of active substance (obtained from a 107 _o emulsifiable concentrate) set. After 24 hours, aphids (Aphie fabae) were placed on the above-ground parts of the plant. The animals were protected from contact and gas effects by a special device. The experiment was carried out at 24 ^@ G and 70% relative speed ο

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The compounds according to Example 1 acted in 2352141 above test systemically against Aphis fabae.

Example 4

Effect ge, q; en Chllo ßup presnnlls.

6 rice plants of the Caloro variety were placed in plaotic pots, which had an upper diameter of 17 cm, transplanted and raised to a height of approx. 60 cm. Infestation with Chllo cupprescalia Larvae (L .; 3-4 mm long) took place 2 days after the addition of the active ingredient in granulate form (application rate 8 kg Active ingredient per hectare) in dao Paddy-Waooer. The evaluation of the insecticidal effect is carried out 10 days after the addition of the Granulateo.

The compounds according to Example 1 were effective against Chilo suppressalis in the above test.

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■ - 17 -

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Example 5 Effect against soil insects

Sterilized compost soil is mixed homogeneously with a wettable powder containing 25% active ingredient, so that a concentration of 16 ppm, respectively. of 8, 4, 2, 1 ppm arises. In the soil treated in this way, young courgette and cabbage plants are placed and immediately with 5 larvae of Aulacophora femoralis (age: 15 d / 25 ° C) resp. 15 eggs of Chortophil'a brassicae (cabbage flies) infected; a third corresponding earth pattern is provided with apple wedges as fodder and planted with 5 larvae of Pachnoda savignyi (20 d / 25 ° C). Mortality is rated 10 days after application and infestation. The screening test with groundworms (Agrotis Y-L2) proceeds analogously, with the difference that the concentrations are 40, 20, 10 ppm. Mälven leaves are used as food.

The compounds according to Example 1 showed activity against Aulacophora femoralis-, Chortophila brassicae, Pachnoda savignyi and Agrotis larvae.

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Example 6

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Effect against ticks '

A) R hipice phalus bursa

5 adult ticks or 50 tick larvae were each in one Glass tubes counted and for 1 to 3 2 minutes in 2 ml one .aqueous emulsion from a dilution series of 100 each, 10, 1 or 0.1 ppm tea substance immersed. The tube was then verochloc3en with a standardized wadding hole and divided on the head so that the active ingredient emulsion could be absorbed by the wadding. The evaluation of the adults took place after 2 weeks and in the larvae after 2 days. Two repetitions were run for each attempt.

B) Boophilus microplus (larvae)

With an analogous dilution series as in test A, 20 sensitive reap. OP-resistant larvae Tests carried out. (The resistance relates to

the tolerance of Diazinon)

The compounds according to Example 1 were active in these tests against adults and larvae of Rhipicephalus bursa and sensitive resp. OP-resistant larvae of

Boophilus microplus.

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Acaricidal effect . ■

Phaqeolus vulgaria (plants) vrarden 12 hours before dew Teot for acaricidal effect with an invested leaf DtUck from a box cultivation of Tetranychus urticae. The overflowing mobile stages were anaesthetized with the emulsified tea preparations from a chromatography cerealer so that the spray liquor did not run off. After two bio 7 days, larvae, adults and eggs are evaluated under the binocular for living and dead individuals and the result is printed out in prosents. During the "hold time ¹¹ dio behandltcn plants stood in Gewächchauskabinen at 25 ⁰ C.

The compounds according to Example 1 were active in the above test against adults ₉ larvae and eggs of Tetranychus urticae "

Example 10
Effect; gen ge

To check the effect against Bodennew.atoden vmrden dio Active substances in the JGWeilo ßngebonen concentration in infected by VJurselsGllen nematodes (Meloidogyna arenaria) Earth given and intimately mixed «In the ao prepared earth were immediately in a Veroucha series after that torr.atensetslinga planted and in another Test series neeh 8 days waiting time tomatoes elngoaät.

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To assess the nematocidal effect, 28 days * after planting bzxtf. after the seed, those at the roots existing galls are counted.

In this test, the active ingredients according to Example 1 showed a good action against Meloidogyne arenaria.

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Claims (1)

2352H1 Claims compounds, of the formula ι S wherein IL is C -, - C, -alkyl and η mean the numbers 0 to 2. 2. Compounds according to claim 1, in which R-, n-propyl and η denote the numbers 0-2. 3. Compound according to claim 2 of the formula 409817/1186 4. Compound according to claim 1 of the formula 00 H SCH 5. A compound according to claim 2 of the formula -N 6. A compound according to claim 2 of the formula Cl T ^s Il I '/ OC ₀ H ₁ , Cl k "/ 7. Process for the preparation of compounds according to Claims 1 to 6, characterized in that one a compound of the formula II / OC ₉ H ₁ ^X SR 409817/1186 2352H1 with a compound of the formula ~ * 'Cci), in the presence of an acid-binding agent or with a Compound of formula -N
OMe converts _s where R ₁ and η have the meaning given in claim 1 and Hal is a halogen atom and Me is a monovalent metal, 8ο pesticides that are considered active Component a compound according to claims 1 to 6 and suitable carriers and / or other additives contains. ·, ·· .. ·· .. 9 ο Use of compounds according to the claims 1 to 6 for combating various animal and vegetable pests. 409817/1186 INSPECTED 2352U1 10. Use according to claim 9 for combating Insects and representatives of the order Akarina. 11. Use according to claim 9 for combating phytopathogenic nematodes. 409817/1186