DE2405189A1 - PICOLYLDITHIOPHOSPHORIC ACID ESTERS, METHOD FOR THEIR MANUFACTURING AND USE - Google Patents

Description

CSBA-GEIGY

CLBA-GEIGY AG, CH-4002 Basel

Dr. F. To the tein sen. - Dr. E. Assmann Dr.R.Kosni-3i / -.r.-er - D ^ i.F ^ .ys.R. Koizbauer

ti. F. Ζο:., -: η pn.

P α ί θ η 5 α η ν / α I t β

8 Munich 2, Bräuhausstraße 4 / III

Case 5-8637 / 1 + 2 / =
Germany

"PicolylditMophösphor acid ester, process for their preparation and their use "

The present invention relates to picolyldithiophosphorus acid esters, process for their preparation and their use in pest control. The picolyldithiophosphoric acid esters have the formula

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wherein R, C-j-C ^ -alkyl,

^R 2 C, -C ₁ -alkyl or propargyl,

X hydrogen or chlorine and

η denote the numbers 1 to 4.

The alkyl groups to be considered for R 1 and R 1 can be straight-chain or branched. Examples of such groups are: methyl, ethyl, propyl, isopropyl, n-, i-, sec., tert., butyl, n-pentyl and its isomers.

Because of their action, compounds of the formula I are preferred,

where R, ethyl,

R ^ C, -C _1. -Alkyl or propargyl, X is hydrogen or chlorine and η denotes the numbers 1 or 2.

The compounds of the formula I can be prepared analogously to known methods, for example as follows:

O

¹ > I + MeHnI

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where R- ,, R ₉₅ X and η have the meaning given for the formula I and Hal is a halogen atom such as fluorine, chlorine, bromine or iodine, in particular chlorine or bromine and Me is an alkali metal, in particular sodium or potassium.

The reaction is conducted at normal pressure, a temperature between O - 100 ⁰ C and carried out in inert towards the reaction participants solvents or diluents - 15O ° C, in particular between 20th Examples of such inert solvents or diluents include: aromatic hydrocarbons such as benzene, toluene, halogenated hydrocarbons, chlorobenzene, polychlorobenzenes, bromobenzene, 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, diethyl ketone, nitriles such as acetonitrile, etc. Some of the starting materials of the formula II are known or can be prepared analogously to known methods. The compounds of the formula I have a broad biocidal action and can be used for combating various types of plant and animal pests and as plant regulators.

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In particular, they are suitable for combating insects of the families: Acrididae, Blattidae, Gryllidae, Gryllotalpidae, Tettigoniidae, Cimicidae, Phyrrhocoridae, Reduviidae, Aphididae, Delphacidae, Diaspididae, Pseudococcidae, Scaridae, Coccinellidae
Dermestidae, Tenebrionidae, Curculionidae, Tineidae,
Noctuidae, Lymantriidae, Pyralidae, Galleridae, Culicidae, • Tipulidae, Stomoxydae, Muscidae, Calliphoridae, Trypetidae, Pulicidae and acarids of the families: Ixodidae,
Argasidae, Tetranychidae, Dermanyssidae.
The insecticidal or acaricidal effect can be through
Substantially broaden the addition of other insecticides and / or acaricides and adapt to the given circumstances. The following active ingredients are suitable as additives:

organic phosphorus compounds;
Nitrophenols and their derivatives;
Formamidine; ! Carbamates; Ureas and chlorinated hydrocarbons.

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In addition to the properties mentioned above, the compounds of the formula I also have a microbicidal activity on. Some of these compounds show bactericidal activity. But they are mostly against fungi, in particular effective against the following classes of phytopathogenic fungi: Oomycetes, Zygomycetes, Ascomycetes, Basidiomycetes, Denteromycetes.

Compounds of the formula I also show a fungitoxic effect on fungi that remove the plants from the soil to attack. The new active ingredients are also suitable for treating seeds, fruits, tubers, etc. to protect against fungal infections. Compounds of the formula I are also suitable for combating phytopathogens Nematodes.

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™ D ■ "

The compounds of formula I can be used alone or together with suitable carriers and / or additives can be used. Suitable carriers and aggregates can be solid or liquid and correspond to 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 added to dusts, emulsion concentrates, granules, dispersions, Sprays, solutions or slurries'in more common Formulations that are part of general knowledge in application technology can be processed. Furthermore are "cattle dips", i.e. cattle baths, and "spray races", i.e. spray courses in which aqueous preparations are used be to mention.

The agents according to the invention are produced in an known way by intimately mixing and / or grinding active ingredients of the formula I with the appropriate ones Carriers, optionally with the addition of dispersants or solvents which are inert towards the active ingredients. The active ingredients can be present and used in the following working-up forms;

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Festivals

Forms of processing: dust, grit,

Granules, coating granules, iTiipr'dgnierungsgranulate and Homogeneous granules

Liquid
Forms of processing:

a) dispersible in water
Active ingredient concentrates: wettable powders

Pastes, emulsions;

b) Solutions

The content of active ingredient in the agents described above is between 0.1 and 95%, it should be mentioned that When applying from an aircraft or using other suitable application devices, concentrations of up to 99.5% or even pure active ingredient can be used.

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

StHubemitte !: The following substances are used to produce a) 5% and b) 2 / CJgen dust:

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 substances are mixed with the carrier substances and ground.

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 0.3-0.8 mm). The active ingredient is mixed with epichlorohydrin and dissolved with 6 parts of acetone, then polyethylene glycol and cetyl polyglycol ether are added. The thus obtained Solution is sprayed onto kaolin and then the

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Acetone evaporated in vacuo.

Spray powder : To produce a) 407, b) and c) 25% 3gcn d) 307o spray powder, the following ingredients are used:

a) AO parts active ingredient

5 parts of lignosulfonic acid sodium salt,

1 part dibutylnaphthalene sulphonic acid sodium salt,

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 of silica, 19.5 parts of Champagne chalk, 28.1 parts of kaolin;

c) 25 parts of active ingredient

2.5 parts of isooctylphenoxy-polyoxy'äthylen-'äthanol, 1.7 parts Champagne chalk / Hydroxy'a thy! 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 mixture of the sodium salts of saturated

Fatty alcohol sulfates,
5 parts naphthalenesulfonic acid / formaldehyde condensate

sat,

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 ether 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 alkylary] sulfonate / fatty alcohol polyglycol cither mixture,

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5 parts of 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 of epichlorohydrin, 94 parts petrol (boiling limits 160-190 ⁰ C);

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example 1

Production of O-ethyl-S-n-propyl-S ^ o-dichloropicolyl-3-phosphorothiolate

14 g of 2,6-dichloropicolyl-3-chloride is dissolved in 150 ml of acetonitrile. 16.9 g of potassium O-ethyl-Sn-propyldithiophosphate are added in portions to this solution. That
The reaction mixture is stirred for 16 hours at room temperature. After the solvent has been distilled off, the residue is mixed with ether, washed with water and dried over anhydrous sodium sulfate.
After evaporation of the ether, the compound of the formula is obtained

II / OCJL-

C ₁ An _n A ₀₁ ; ^x sc ₃ H ₇ (n)

with a refraction of n ": 1.5740.

The following connections are also established in the same way:

n ^ ⁴ : 1/5617

C II (r.)

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2 5 n _D ⁺ : 1.5

5CH

O

Il / OC _? H

24 \ s _N /> - ^ SO ₅ H ₇ (η) ⁿ D ^:

= 1.5995

H / OC ₀ H ₅

.H,

* ⁵ 20

-rtuL-pxT η _Ώ = 1.5691

C1 ^{/ XN} N ^{/ N} C1 ° CMH ₃ D

^C 2

JC ₀ H ,.

/ \ 0

i Y "/ ° ^CH 20

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Example 2

A) T nsc'ktri aim ¹ fra sst'i ff effect

Bauinwol ipfJ angcn and card) f Γ (. · 1 staue! Cn were with a 0.05% of aq 1OXigen emulsifiable concentrate) sprayed. After the covering had dried on, the cotton plants became each with Spodoptera littoralis or Heliothis virescens larvae Lo and the potato plants with Colorado beetle larvae (Leptinotarsa decemlineata) occupied. The experiment was carried out at 24 ° C and 60% relative humidity carried out.

The compounds according to Example 1 showed in the above test a good insecticidal milling poison effect against Spodoptera, Heliothis and Leptinotarsa decemlineata larvae.

B) Systemic insecticidal action To determine the systemic action, rooted bean plants (Vicia faba) were placed in a 0.01% strength aqueous active ingredient solution (obtained from a 10% strength emulsifiable concentrate). After 24 hours, aphids (Aphis fabae) were placed on the above-ground parts of the plant. The animals were slit in front of the contact and gas effects by a special device. The experiment was carried out at 24 ° C. and 70% relative humidity.

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Compounds according to Example 1 acted systemically against Aphis fabae in the above test.

Example 3 Effect against Chilo suppressalis

6 rice plants of the Caloro variety were placed in plastic pots with an upper diameter of 17 cm, transplanted and raised to a height of approx. 60 cm. The infestation with Chilo suppressalis 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 substance per hectare) in the paddy water. The evaluation for insecticidal effect is carried out for 10 days after adding the granules.

Compounds according to Example 1 acted against Chilo suppressalis in the above test.

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Example 4 Effect against ticks

A) Rhipicephalus bnrsa

5 adult ticks or 50 tick larvae were counted in a glass tube and for 1 to 2 minutes in 2 ml one aqueous emulsion from a dilution series with 100 each, 10, 1 or 0.1 ppm test substance immersed. The tube was then closed with a standardized cotton ball and turned upside down 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 resp. OP-resistant larvae Tests carried out. (The resistance relates to the tolerance of Diazinon)

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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Example 5 Acaricidal effect

Phaseolus vulgaris (plants) were covered with an infested piece of leaf from a mass cultivation of Tetranychus urticae 12 hours before the test for acaricidal activity. The overflowing mobile stages were dusted with the emulsified test preparations from a chromatography atomizer so that the spray mixture did not run off. After two to 7 days, larvae, adults and eggs were evaluated under the binocular for living and dead individuals and the result was printed out as a percentage. During the "hold time" were the behandlten plants in greenhouse compartments at 25 ⁰ C.

Compounds according to Example 1 worked in the above test against adults, larvae and eggs of Tetranychus urticae.

Example 6 Effect against soil nematodes

To test the effect against soil nematodes, the Active ingredients in the concentration indicated in each case in infected by root cell nematodes (Meloidogyne arenaria) Earth given and intimately mixed. In the soil prepared in this way, a series of experiments was carried out directly then tomato seedlings were planted and, in another test series, tomatoes were sown after a waiting period of 8 days.

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The nematocidal effect was assessed for 28 days after planting or after sowing, the galls present on the roots are counted.

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

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Claims (15)

CLBA-GEIGY AG - 19 - Patent Claims 1. Compounds of the formula Il / OR _n η vx "/ c X ₀₁₁ ^ wherein R, C, -C _1. -alkyl, R ₂ C ₁ -C ^ alkyl or propargyl, X hydrogen or chlorine and η denote the numbers 1 to 4. 2. Compounds according to claim 1, where R, ethyl, R ₂ C ^ -C alkyl or propargyl, X hydrogen or chlorine and η denote the numbers 1 or 2. 409832/1096 CIBA-GEIGY AG - 20 - 3. Compound according to claim 2 of the formula 0
/ \ Il / OCJI ₁ . {' jrcH.-sp <^c; niA \ | Am '' "HC-JI ,. (π) 4. A compound according to claim 2 of the formula II / OC H _r , H "(n) 5. A compound according to claim 2 of the formula 6. A compound according to claim 2 of the formula II / OC ^N N 409832/1 096 CIBA-GElGY AG - 21 - 7. A compound according to claim 2 of the formula C ₀ IL. fC ₃ H ₇ Cn) 8. A compound according to claim 2 of the formula > v II / OC ₂ H Cl / ^ N 'Xl 9. A compound according to claim 2 of the formula / \ ! I / OC ₉ tbsp / y V-CH - s - P \ - ^ ₀ I ² ^ ^X SC ₃ H ₇ (i) 10. A compound according to claim 2 of the formula Il / OC H CH _? -SP <f ^ ^X S-CH-CH. 4C9832 / 1096 11. Process for the preparation of compounds according to claims 1 to 10, characterized in that one a compound of the formula with a compound of the formula wherein R ₁ , R ", Ro, X and η have the meaning given in the claim and Hal stands for a halogen atom and Me for an alkali metal. 12. Pesticides, which as the active component a compound according to claims 1 to 10 and suitable carriers and / or other additives included. 13. Use of compounds according to the claims 1 to 10 for the control of various plant and animal pests and as plant regulators. A C9832 / 1096 CLBA-GEIGY AG - 23 - 14. Use according to claim 13 for combating Insects and representatives of the order Akarina. 15. Use according to claim 13 for combating phytopathogenic nematodes. 4C9832 / 1 096