DE2349746A1 - THIOPHOSPHORIC ACID ESTERS OF OXAZOLOPYRIDINE COMPOUNDS AND ANIMAL REPRODUCTIONS CONTAINING THESE - Google Patents

Description

CIBA-GEIGYAG. CH-4002 Basel

CIBA-GEIGY

Dr. F. Zumstein Sr. - Dr. E. Assmann Λ <) / ΠΤ / f> Dr.R.Koenigsberger - Dipl.Phys.R. Holzbauer Z-JH <3 / hQ Dr. F. Zumstein jun. Patent attorneys

8 Munich 2, Bräuhausstraße 4 / III

Case 5-8450 / 1 + 2 / U

a uo Hoforccylon

The present invention relates to dithiophosphates, processes for their preparation and their use in of pest control. The dithiophosphates have the formula

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R ₁ hydrogen, halogen or nitro, 2349745

2 C ₁ C ₅
R ₃ C ₁ -C alkyl, C ₃ -C alkenyl,

C ₁ -C ₅ alkoxy-C ₁ -C alkyl or Cj ^ -C

C ^ C ^ alkyl,
X represent oxygen or sulfur.

Halogen is to be understood as meaning fluorine, chlorine, bromine and / or iodine. The one for R _? and R ₃ eligible Cj-Cc-alkyl-, CjC ^ -alkenyl-C ₃ -C ₅ -alkynyl-, C - ^ - C ^ alkoxy-C ^ C ^ alkyl- and C ^ C ^ alkylthio-Cj- Cc-alkyl groups can be straight-chain or branched. Examples of such groups include: methyl, methoxy, methoxymethyl, ethyl, ethoxyethyl, ethylthioethyl, propyl, isopropyl, η-butyl, i-, sec-, tert-butyl, n-pentyl, isopentyl, allyl, Meth allyl, propargyl, isobutinyl.

_{Compounds of the formula I 9} are preferred because of their action

R ₁ hydrogen or chlorine,

R2 methyl or ethyl,

R ₃ n-propyl, iso-propyl, iso-butyl, methoxyethyl or

Ethoxy'äthyl and
X mean oxygen.

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

^a) B ₁ ^ V ⁰ V, χ ", J / ™ ²

(ID

^ sr _{5 means}

(II) CH ₂ -Cl ()

In the formulas II, III and IV, R 1 to R 1 and X have the meaning given for the formula I and Me stands for a monovalent metal, in particular an alkali metal such as sodium or potassium. As acid-binding agents come into question; tertiary amines _9, for example TrI · alkylamines ₉ pyridine, dialkylanilines; inorganic bases ₃ such as hydroxides; Carbonates and bicarbonates of Alka! I- ₉ alkaline earth metals. It is with the implementations. sometimes it is necessary to use catalysts such as copper or copper chloride.

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Reactions a and b are carried out at a temperature of 0-120 C, preferably between 10 and 70 ° C., under normal pressure and in solvents or diluents which are inert towards the reactants carried out. Suitable solvents or diluents are e.g. ethers and ether-like compounds, such as Diethyl ether, dipropyla'ther, dioxane, dimethoxyethane, tetrahydrofuran; Amides such as Ν, Ν-di-alkylated carboxamides; aliphatic, aromatic and halogenated hydrocarbons, in particular Benzene, toluene, xylenes, chloroform, chlorobenzene; Nitriles such as acetonitrile; DMSO, ketones such as acetone, methyl ethyl ketone or mixtures Such solvents with water, The starting materials of the formulas II, III and IV are known and can be prepared analogously to known methods.

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The compounds of the formula I have a broad biocidal effect and are therefore suitable for combating various plant and animal pests. But you have in particular insecticidal and acaricidal properties and can be used against all stages of development such as eggs, larvae, pupae, Nymphs and adults are used by insects and representatives of the order Akarina, e.g. against insects of the families: Tettigoniidae, Gryllidae, Gryllotalpidae, Blattidae, Reduviidae, Phyrrhocoridae, Cimicidae, Delphacidae, Aphididae, Diaspididae, Pseudococcidae, Scarabacidae, Dermestidae, Coccinellidae, Tenebrionidae, Chrysomelidae, Bruchidae, Tineidae, Noctuidae, Lymatriidae, Pyralidae, Culcidae, Tripulidae, Stomoxydae, Trypetidae, Muscidae, Calliphoridae and Pulicidae, as well as acarids of the families Ixodidae, Argasidae, Tetranychidae and Dermanyssidae. The insecticidal or acaricidal effect can be reduced by adding from other insecticides and / or acaricides widen significantly and adapt to the given circumstances. Suitable additives are, for example:

organic phosphorus compounds

Derivatives of nitrophenols

Formamidine

Ureas

Carbamates and

chlorinated hydrocarbons.

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The active ingredients of the formula I are also suitable for combating representatives of the Thallophyta x ^ ie, viruses, bacteria and pilsenic department. They have fungicidal properties against phytopathogenic fungi on various types of crops, such as grain, maize, rice, vegetables, ornamental plants, fruit trees, vines, fields, etc. With the new active ingredients, fungi that occur on fruits, flowers, foliage, stems, tubers and roots can be contained or destroyed, in which case parts of plants that grow later are spared from such fungi. The active ingredients of the formula I are particularly effective against the following classes of phytopathogenic fungi belonging to: Oomycetes, Zj'gomycetes ₃ Ascomycetes, Basidiomycetes, Denteromycetes.

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

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CIBA-GEIGYAG _t _ =. 7 -

The compounds of the formula I can be used alone or together with suitable carriers and / or additives. Suitable .Träger and additives can be solid or liquid and correspond to the substances common in formulation practice, such as natural or regenerated substances, solvents, dispersants _S sharpening, adhesives, thickeners, binders and / or fertilizers. For application, the compounds of the formula I can be processed into dusts, emulsion concentrates, granules, dispersions, sprays, into solutions or slurries in customary formulations which are part of general knowledge in application technology. Further, "cattle dips", ie cattle baths, and d _s "spray races' ^1, h. Sprühgänge in which aqueous preparations used werdenj be mentioned.

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 Carriers, optionally 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 available and applied?

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Forms of processing: dust, grit,

Granules, coating granules, impregnation granules and Homogeneous granules

Liquid

Processing forms:

a) dispersible in water
Active ingredient concentrates: wettable powders

pastes, emulsions j

b) Solutions «

The content of active ingredient in the agents described above is usually O ₃ I up to 95%. It should be noted that v up to 5 J 99j, or .sogar pure active compound used in the application from the aircraft or other means of application devices gsaignater concentrations' to earth ground /

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

Dusting agent: To produce a) 5% and b) 2% dusting agent, 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 are mixed and ground with the carrier substances.

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 substance is mixed with epichlorohydrin and dissolved with 6 parts of acetone, then polyethylene glycol is added and cetyl polyglycol ether added. The solution obtained in this way is sprayed onto kaolin and then the

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CIBA-GEIGYAG - \ 10 -

Acetone evaporated in vacuo.

Spray powder: To produce a) 40%, b) and c) 25% d) 107o spray powder, the following ingredients are used:

a) 40 parts of Xt active ingredient

5 parts of lignin sulfonic acid sodium salt,

1 part dibutylnaphthalenesulfonic 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-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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CIBA-GEfGYAG JI

«2) 10 parts of active ingredient

- 3 parts mixture of the sodium salts of saturated

Fatty alcohol sulfates ₂
5 parts of naphthalenesulfonic acid / formaldehyde condensate,

82 parts of kaolin.

The active ingredients are intimately mixed with the additives in suitable mixers and ground on appropriate mills and rollers. This gives wettable powders ₃ which can be diluted with water to form suspensions of any desired concentration.

Emulsifiable concentrates; The following substances are used to produce a) 107o and b) 25% emulsifiable concentrate:
a) IO parts active ingredient

3 _S 4 parts of epoxidised vegetable oil ₉ 13.4 parts of a combination consisting of _s Fettalkoholpolyglykoiather and alkylarylsulfonate Caleium salt,
Parts of dimethylformamide ₉
2 parts of xylene;
25 parts of active ingredient

2 _S 5 parts epoxidized vegetable oil _s

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

11/111

ciBA-GEiGYAG - - · ■ 12 -

5 parts of dimethylformamide, 57.5 parts of xylene.

Emulsions of any desired concentration can be prepared from such concentrates by dilution with water will.

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

5 parts active ingredient,

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

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Preparation of Q »S — Dimethyl-S- [6-chloro-oxazolo (4 _? 5-b) pyridine-

2 (3H) -on-3-yl-methyl] dithiophosphate

22 g of 3-chloromethyl-6-chloro-oxazolo (4 _s 5-b) -pyridin-2 (3B) -one, 24 g of the potassium salt of O, S-dimethyl-dithiophosphoric acid and 50 ml of methanol are heated to 65 ° C. for 5 minutes . The methanol is then distilled off, 100 ml of water are added to the residue and the oil which has separated out is isolated by ethereal extraction. You get the connection

the formula "

0 ii

/ C _n

"PS-CH ₂ -If P

as a pale brown oil that cannot be distilled.

Calc .: C 31.7 H 3.0 N 8.2 P 9.1 S 18.8 Cl 10.4% C 31.4 H 3.1 N 7.8 P 8.8 S 18.7 Cl 10 , 7 %.

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The following compounds are also produced in an analogous manner;

R ₁ R ₂ ^R 3 X Microanalyses e H CH3 (Ti) -C ₃ H ₇ - 0 a) HC ₂ H ₅ C ₂ H ₅ - 0 b) HC ₂ H ₅ (Ti) -C ₃ H ₇ - 0 c) HC ₉ H ₁ ; (XSo) -C ₃ H ₇ - 0 d) HC ₂ H ₅ Cn) -C ₄ H ₉ - 0 e) HC ₂ H ₅ (ISO) -C ₄ H ₉ - 0 f) HC ₂ H ₅ CH ₃ OC ₂ H ₄ - 0 G) HC ₂ H ₅ C ₂ H ₅ OC ₂ H ₄ - 0 H) HC ₉ H ₁ - CH ₂ = CH-CH ₂ - 0 i) Cl CH ₃ (Ti) -C ₃ H ₇ 0 J) Cl C ₂ H ₅ C ₂ H ₅ - 0 k) Cl C ₂ H ₅ Cn) -C ₃ H ₇ - 0 D. Cl C ₂ H ₅ (ISo) -C ₃ H ₇ - 0 m) Ci C ₂ H ₅ CrO-C ₄ H ₉ - 0 n) CiSO) -C ₄ H ₉ ^ O
ij 0)

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^R l R ₂ R ₃ X Microanalysis Cl C ₂ H ₅ CH ₃ OC ₂ H ₄ - O M.p. 69-71 ° C Cl C ₂ H ₅ C ₂ H ₅ OC ₂ H ₄ - O P) Cl C ₂ H ₅ CH ₂ = CH-CH ₂ - O q)

Microanalysis

but. C 39.5 H 4.5 N 8.4 P 9.3 S 19.2% Found 39.2 4.7 8.0 9.4 19.5%

b) Ber. C 39.5 H 4.5 N 8.4 P .9.3 S 19.2% found 39.5 4.6 8.3 9.2 19.0 %

c) Ber. C 41.3 H 4.9 N 8.0 P 8.9 S 18.4 % found 41.0 5.1 8 _s 0 8 ₃ 9 18.2%

d) Ber. C 41.3 H 4.9 N 8.0 P 8.9 S 18.4% found 41.3 5.1 8.1 8.8 18.1 %

e) Ber. C 43.1 H 5.3 N 7.7 P 8.6 S 17.7 % found 42.8 5.3 7.7 8.6 17.3 %

f) Ber. C 43.1 H 5.3 N 7.7 P 8.6 S 17.7 % found 43.0 5.3 7.7 8 ₃ 7 17.6 %

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g) Ber. C 39.6 H 4.7 N 7.7 P 8.5 S 17.6 %
Found 39.5 4.9 7.5 8.6 17.6%

h) Ber. C 41.2 H 5.1 N 7.4 P 8.2 S 17.0 %
Found 41.1 5.1 7.3 8.3 16.7%

i) Ber. C 41.6 H 4.4 N 8.1 P 9.0 S 18.5%
Found 41.4 4.5 8.1 9.0 18.4 %

j) Ber. C 35.8 H 3.8 Cl 9.6 N 7.6 P 8.4 S 17.4% Found 35.9 4.0 9.8 7.3 8.5 17.4%

k) Ber. C 35.8 H 3.8 Cl 9.6 N 7.6 P 8.4 S 17.4% Found 36.0 3.8 10.0 7.9 8.1 17.0%

1) Ber. C 37.6 H 4.2 N 7 _S 3 P 8.1 S 16.7 Cl 9.3%

Found, 37.6 4.1 7.4 7 _S 8 16.4 9.6 %

^m 2 _Ber , C 37.6 H 4.2 Cl 9 ₃ 3 N 7.3 P 8.1 S 16.7%

Found 37.4 4.1 9 ₅ 5 7 _S 5 7.9 16.5%

n) Ber. C 39.4 H 4.6 Cl 8.9 N 7.1 P 7.8 S 16.2%

Found 39.1 4.5 9.3 6.8 7.7 16.5%

o) Ber. C 39.4 H 4 ₃ 6 Cl 8.9 N 7 _S 1 P 7.8 S 16.2%

Found, 39.1 4.6 9 ₃ 2 7.2 7.7 16.0 %

p) Ber. C 37.8 E 4.4 Cl 8.6 N 6.8 P 7.5 S 15.5%

Found 38.0 4.3 8.9 6.8 7.4 15.1%

q) Ber. C 37.9 H 3.7 Cl 9.3 N 7.4 P 8.2 S 16.8 %

Found 3S ₃ I 3.8 9 _S 6 7.6 8.1 16.5%

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CIBA-GEIOYAQ Example 2

A) Insecticidal milling poison effect

Cotton plants and potato plants were with a 0.05% aqueous active substance emulsion (obtained from a 10% emulsifiable concentrate) sprayed. After the covering had dried on, the cotton plants became each with Spodoptera littoralis or Heliothis virescens larvae L ~ and the potato plants with Colorado beetle larvae (Leptinotarsa decemlineata) occupied. The experiment was carried out at 24 ° G and 60% relative humidity carried out.

In the above test, the compounds according to Example 1 showed a good insecticidal feed poison action against Spodoptera, Heliothis and Leptinotarsa decemlineata larvae.

B) Systemic insecticidal action To determine the systemic effects were rooted bean plants (Vicia faba) in a 0,017 _o aqueous solution of active substance (obtained from a 10% emulsifiable concentrate) set. 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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CIBA-GEIGY AG

- 13 -

The compounds according to Example 1 worked in the above Test eystemic against Aphis fabae.

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.

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

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CIBA-GEIQYAQ - Example 4 Effect against ticks

A) Rhipicephalus bursa

5 adult ticks or 50 tick larvae were counted in a glass tube and immersed for 1 to 2 minutes in 2 ml of an aqueous emulsion from a dilution series with 100, 10, 1 or 0.1 ppm test substance. The tube was then covered with a standardized cotton ball "could be closed and thus _s upside drug emulsion of the cotton added the evaluation was carried out at the adults was made after 2 weeks and in the larvae after two days" for any attempt ran two repetitions.

B) Boophilus microplus (larvae)

With an analog dilution series as in Test A were 20 sensitive respectively ₀ OP = resists £ s larvae tests performed (The resistance refers "sieh'auf the compatibility of Dia ^ inon) The compounds gemMss Example 1 acted in these tests against adults and larvae of Rhlpieephalus bursa and sensitive resp _o OP-resistant larvae of Boophilus microplus.

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CSBA-GEIGY AG

Example 5
Acaricidal effect

Phaqeolus vulgaris (plants) were covered with an infected leaf piece from a mass cultivation of Tetranychus urticae 12 hours before the test for acaricidal activity For 7 days, larvae, adults and eggs were evaluated under the binocular for living and dead individuals and the result was expressed as a percentage. During the "holding time", the treated plants were in greenhouse cabins at 25 ⁰ G,

The compounds according to Example 1 worked in the above test against adults, larvae and eggs of Tetrenychus urticae.

BeJ. 3y

Effect against soil nematodes

To test the effect against soil nema'coden, the Active ingredients in the specified concentration in infected by root cell nematodes (Meloidogyne arenaria) Earth given and intimately mixed. In the so prepared soil were in a test series directly then planted tomato seedlings and put them in another Test series sown tomatoes after a waiting period of 3 days.

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CIBA-GEiGYAG _ 21 -

To assess the nematocidal effect, those on the roots were carried out 28 days after planting or after sowing existing galls are counted.

In this test, the active ingredients were shown in Example 1 a good effect against Meloidogyne arenaria.

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Claims (17)

Claims 1. Compounds of the formula R, hydrogen, halogen or nitro, R ₂ C ₁ -C ₅ AlCyI, ^R 3 C ₁ -C ₅ AlCyI, C ₃ -C ₅ alkenyl, C ₃ -C ₅ ^C l " ^C 5" ^AlkoXy " ^C l" ^C 5 " ^{alkyl or} CjC ₅ -alkylthio ^C l ~ ^C 5 ~ ^alkyl} X signify oxygen or sulfur. 409815/1180 2. Compounds according to claim wherein R, hydrogen or chlorine, R «methyl or ethyl _s R ~ n = propyl ₉ iso-propyl, iso-butyl, methoxymethyl or ethoxy methyl and X is oxygen; 3. Compound according to claim 2 of the formula • N ^x 0 C H Ox II / Cv D ( 4. A compound according to claim 2 of the formula y- 5. A compound according to claim 2 of the formula 0 Il CH Ov Il χ C _x ^D > PS-CH ^ -E 0 409815/1180 6. A compound according to claim 2 of the formula 0 !! CHO _x / > 7. A compound according to claim 2 of the formula 0 0 H 8. A compound according to claim 2 of the formula 0 H CH ₃ Ov Ii / C _x (n) C ₃ H ₇ S / ² 9. A compound according to claim 2 of the formula 0 H CHCKII / C _x ⁰ > P - & - CH -N Cn) CJi S /
⁵ ' 409815/1180 10. A compound according to claim 2 of the formula 0 0 II 11. A compound according to claim 2 of the formula 0 0 Il CH-OC ₀ Hf
3 2 4 12 ο compound according to claim 2 of the formula 13. A compound according to claim 2 of the formula 0 0 II J (iso JC ^ EC 815/1180 14. Process for the preparation of compounds according to Hss Claims 1 to 13, characterized in that a compound of the formula c = x with a compound of the formula II X) R ₂ in the presence of a sludge binding agent or with a Compound of formula 0 measurement converts, in which R 1 to Ro and X are those specified in claim 1 Have meaning and Me stands for a monovalent metal. 409815/1180 15. Pesticides which contain a compound according to claims 1 to 13 as the active component and contain suitable carriers and / or other additives. 16. Use of compounds according to the claims 1 to 13 for combating various animal and vegetable pests. 17. Use according to claim 16 for combating insects and representatives of the order Akarina. 80