DE2643476A1 - SCHAEDLING INHIBITOR - Google Patents

Description

Pesticides

D. The present invention relates to -3-N-phenyl- -carbamoyl- ^ hydroxy-l ^ - (benzo) pyrone derivatives, the one Have action against insects, processes for their production, as well as insecticides. which this Containing derivatives as active ingredients and methods for controlling insects using the new Active ingredients.

The 3-N-phenyl-carbamoyl-4-hydroxy-1, 2- (benzo) pyrone- derivatives have the formula I. I.

C-NH-R ₃

(D

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R 1 denotes a methyl group and R "denotes a hydrogen atom or R, and R "together form a condensed .benzene nucleus

form and
Pure . optionally substituted one, two or three times by halogen, methyl, ethyl, i-propyl, trifluoromethyl, nitro and / or cyano. Pheny! Group represents

where, when R ₁ and R 2 together form a fused benzene nucleus, "not a phenyl", 4-nitrophenyl, 3-trifluoromethylphenyl or halogen-substituted phenyl group. ·

The term "halogen" means chlorine, fluorine, bromine and iodine.

The compounds of the formula are of particular importance because of their insecticidal action

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Ia and especially the formula Ib

R ₉ V ₅ X ^ - CO-NH ^{1 R} 5

(Ib)

'- Il I XJ /. "5

R ₁ and R "have the meanings already given under formula I."

have and
R, and Rc independently of one another for a hydrogen or halogen atom, or. a: methyl or trifluoromethyl group.

The compounds of the formula I are obtained according to methods known per se by e.g.

a) an ester of the formula II

OH

^ -C00R.

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with an aniline of the formula III

with an isocyanate of the formula V

implements;

b) a compound of the formula IV. OH '

. (IV)

R, -N = C = O (V)

lets react; or that one

c) a compound of the above formula IV with an azide of formula VI

• · R ₃ -CO-N ₃ (VI)

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treated; where in the formulas II to VI R. to R ₃ have the meanings already given under formula I and R ₆ stands for a C 1 -C 4 -alkyl radical.

Processes (a) and (c) are preferably carried out at a reaction temperature between 100 ° and 200 ° C and the Process (b) carried out at a reaction temperature between 0 ° and 200 ° C. The reactions can be normal or elevated pressure, if appropriate in a solvent or diluent which is inert towards the reactants and optionally carried out in the presence of a base.

Suitable solvents or diluents for these reactions are, for example, ethers and ethereal compounds, such as dipropyl ether, dioxane, dimethoxyethane and tetrahydrofuran: amides such as N, N-di-alkylated carboxamides; aliphatic aromatic and halogenated hydrocarbons, in particular toluene, xylenes and chlorobenzene; Nitriles such as acetonitrile; DMSO and ketones such as acetone and methyl ethyl ketone. Particularly suitable bases are tertiary amines, such as triethylamine, dimethylaniline, pyridine, picolines and lutidines, and also hydroxides, oxides, carbonates and bicarbonates of alkali and alkaline earth metals and alkali metal alcoholates such as potassium t, butoxide and sodium methylate.

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Compounds of the formula

OH

7th

mean an alkyl or aryl radical and a hydrogen atom or

Ry-j. and Rq together an optionally 'by * halogen, Form hydroxyl and / or alkyl substituted, fused phenyl radical and, in which

R is Cj, -C · ^ -alkyl-, C ^ -C-. 2 ~ alkenyl, aralkyl or optionally aryl radical substituted by halogen, hydroxyl or acyloxy and R-iq is a hydrogen atom mean or

Rq and R. < _n together with the nitrogen atom to which they are attached form a piperidinyl, pyrrolidinyl or morpholinyl ring,

have already been mentioned in British Patent No. 919,807 and are known as fungicides and bactericides.

According to the present invention, surprisingly found that the compounds of formula I, which are in part covered by this British patent, a excellent good. .Effect against insects. In particular, the compounds of the formula I have a very beneficial action against insects which are harmful to plants and animals

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and can, for example, according to the invention for combating insects of the families: Acrididae, Blattidae, Gryllidae, Gryllotalpidae, Tettigoniidae, Cimicidae, Pyrrhocoridae, Reduvüdae, Aphididae, Delphacidae, Diaspididae, Pseudococcidae, Chrysomelidae, Coccinellidae, Bruchidae, Scarabaeidae, Dermestididae, Tenebrionidae, Curculionidae, 'Tineidae, Noctuidae, Lymantriidae, Pyralidae, Galleridae, Culicidae, Tipulidae, Stomoxydae, Muscidae, Calliphoridae, Trypetridae and Pucilidae can be used. Above all, however, compounds of the formula I are suitable for combating plants damaging to plants Insects in particular of the order Coleoptera, such as Leptinotarsa decemlineata and Anthonomus grandis, in e.g. vegetable and cotton crops. For this purpose, individual compounds of the formula I have an excellent action against ectoparasitic insects such as Lucilia sericata and against Insects that are harmful in the areas of hygiene and stock protection, such as Musca domestica, Aedes aegypti and Sitophilus granarius, on.

The insecticidal effect can be reduced by adding others Substantially widen insecticides and / or acaricides and adapt them to the given circumstances.

Suitable additives are, for example:

org. Phosphorus compounds; Nitrophenols and their derivatives; Formamidine;

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-UB-

pyrethrin-like compounds;

Carbamates and chlorinated hydrocarbons.

The compounds of the formula I can be used alone or together with suitable carriers and / or additives will. Suitable carriers and additives can be solid or liquid and correspond to those used in formulation technology common substances 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 common Formulations that are part of general knowledge in application technology can be processed.

The agents according to the invention are produced in and of themselves in a known manner by intimately mixing and / or grinding active ingredients of the formula I with the suitable carriers, optionally with the addition of dispersants or solvents which are inert towards the active ingredients. The active ingredients can "be in the following working-up forms and be applied;

Fixed forms of processing: dust, grit,

Granules, (coating granules, impregnation granules and Homogeneous granules);

Liquid processing forms:

a) water-dispersible active ingredient concentration rates:

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Wettable powder

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 during the application Higher concentrations can also be used from the aircraft or by means of other suitable application devices can.

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

Dust: The following substances are used to produce a) 5% and b) 2% 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 ingredients are mixed with the carrier materials and marry.

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

5 parts active ingredient,
0.25 part of epichlorohydrin,
0.25 parts 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 and Cetyl polyglycol ether added. The solution thus obtained

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is sprayed onto kaolin and then the acetone im Vacuum evaporates.

Spray powder : To produce a) 40%, b) and c) 25% d) 10% spray powder, the following ingredients are used:

a) 40 parts of active ingredient,

5 parts of lignin sulfonic acid sodium salt, 1 part of dibutylnaphthalene sulfonic acid sodium salt, Parts of silica;

b) 25 parts of active ingredient,

4.5 parts of calcium lignosulfonate, 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-polyethylene-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;

d) 10 parts of active ingredient,

3 parts mixture of the sodium salts of saturated

Fatty alcohol sulfates,

5 parts of naphthalenesulfonic acid / formaldehyde condensate, Share kaolin.

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The active ingredients are mixed with the additives in suitable mixers intimately mixed and ground on appropriate mills and rollers. A wettable powder which can be mixed with water is obtained allow to dilute to suspensions of the desired concentration.

Emulsifiable concentrates : The following substances are used to produce an a) lOXy emulsifiable concentrate:

a) IO parts active ingredient,

3.4 parts of epoxidized vegetable oil, 3.4 parts of a combination emulsifier, consisting of fatty alcohol polyglycol ether and alkylarylsulfonate calcium salt,
40 parts of dimethylformamide, 43.2 parts of xylene.

Such a concentrate can be diluted with water to produce emulsions of the desired concentration. Spray powder : The following ingredients are used to produce a) 5% and b) 95% spray:

a) 5 parts of active ingredient

1 part epichlorohydrin,
94 parts of gasoline (boiling point 160-190 ° C);

b) 95 parts of active ingredient,

5 parts of epichlorohydrin.

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nt

The following examples serve to explain the invention in more detail.

example 1

Preparation of: 3-N- (4-Trifluoromethylphenyl) -carbamoyl-4- -hydroxy-coumarin.

To a solution of 16.2 g of 4-hydroxycoumarin in 150 ml of dimethyl sulfoxide are added at room temperature and with stirring 10.1 g of triethylamine, and then 18.6 g of 4-trifluoromethylphenyl isocyanate added dropwise. The reaction mixture obtained is stirred for a further 4 hours at room temperature and the reaction mixture is then poured into a solution of 15 ml of concentrated hydrochloric acid in 300 ml of water. The resulting Precipitate is filtered off with suction. After recrystallization from dioxane, the product of the formula is obtained

3 »(connection no. 1)

with a m.p. of 258-260 ° C

The following compounds of the formula lc and Id were also prepared in an analogous manner:

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1) Compounds of the formula Ic

OH

(Ic)

Verb.
No. ^R 3 - ^R 4 ^R 5 Physical
data 249 - 254 0 1 C. - C. 2 3-Cl 4-CF ₃ H M.p. 185 - 187 ° C. 3 3-CF ₃ H 5-CF ₃ M.p. 175 - 177 ° C. 4th ³ ~ ^CH 3 H H M.p. 194 - 197 ° C. 5 3-Cl 4-CH ₃ H M.p. 203 - 205 " C. 6th ■ 2-CH ₃ 4-Cl ' E. Stnp. 247 - 251 ° C. 7th 3 ~ CN H H M.p. 288 - 29O ° C 8th 2-CH ₃ 4-NO ₂ H M.p. 285 - 287 " 9 2-Cl 4-NO ₂ H M.p. 256 - 259 ° C 10 2-NO ₂ ■■ 4-Cl H M.p. 214 - 216 ° C 11 3-CF ₃ 4-Cl H M.p. 222 -.225 ° C 12th 2-Cl, H 5-CF ₃ M.p. 260 - 262 ° C 13th H 4-CN H M.p. 280 - 283 ° C 14th 2-CN 4-Cl - H M.p.

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/ J

TI) compounds of the formula Id

(Id)

Verb.
No. R ₃ ^R 4 • ^R 5 Physical
data 185 - 188 O C. 15th 3-Cl 4-Cl H M.p. 105 - 110 O C. 16 ' 3-CF ₃ H 5-CF ₃ M.p. 213 ° C. 17 " 3-Cl 4-CF ₃ H M.p. 177 - 179 (1 C. 18 · 3-Cl 4-CH ₃ H M.p. 215 - 216 O C. ■ 19,: 2-CH ₃ 4-Cl H M.p. 198 - 200 O C. .2O ₁ ..., - 2-Cl H 6-Cl M.p. 250 - 252 O C. 21. 2-Cl 4-Cl H M.p. 226 - 228 O C. , 22 2-Cl 4-Cl 5-Cl M.p. 246 - 248 O C. 23 2-CH ₃ 4-NO ₂ H M.p. 246 - 248 ° c 24 ^! 2-Cl 4-NO ₉ H Smp » 217 - 221 ° c ; 25 ' 2-NO ₂ 4-Cl H M.p.

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to

Verb.
No. R ₃ ^R A ^R 5 Physical ·
data 174 - 177 ° C 26 ο 3-CF ₃ A-Cl H M.p. 178 - 179 ° C 27 i 2-Cl H 5-CF ₃ M.p. 250 - 253 ° C 28 2-CN 4-Cl H M.p. 210 - 212 ° C 29 " H' 4-y H M.p. 201 - 2O4 ° C 30th 2-Cl H 5-Cl M.p. 155 - 157 ° C 31 ',; ' H H H M.p. 219 - 22O ^Q C 32 H 4-Br H M.p. 146 - 147 ° C 33; , H 3-Cl H M.p.

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Example 2

Action against Leptinotarsa decemlineata I

Potato plants were made with a 0.05% aqueous Active ingredient emulsion (obtained from a 10% emulsifiable Concentrate). After the topping had dried on, the potato plants were covered with Leptinotarsa decemlineata larvae (L3) occupied.

The destruction achieved was evaluated after 2, 4, 8, 24 and 48 hours. The experiment was carried out at 24 ^° C. and 60% relative humidity.

Compounds according to Example 1 showed in the above experiment a good action against Leptinotarsa decemlineata larvae. Compounds 1, 2, 6, 15, 16, 17, 21, 26, 29, 32 and 33 were particularly effective.

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Example 3

Action against Leptinotarsa decemlineata II

Two 15 cm high potato plants were mixed with 25 ml of an acetone / water mixture containing 0.05% test substance (1: 1) injected.

• After the topping had dried on, the potato plants were populated with 10 larvae each of the species Leptinotarsa decem-, lineata (L3 stage). Then a 'Plastic cylinder over the plant = -placed around a possible Prevent larval migration. A copper gauze lid served as a finish. After 2 days the feeding damage certainly.

'Compounds according to Example 1 showed in the above experiment a positive anti-feeding effect. Because of their particularly good effect (only slight damage caused by eating) the connections 1, 4, 6, 7, 10 to 12, 14, 19, 21, 23, 26, 28, 29, 32 and 33 are to be emphasized.

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Example 4

Action against Spodoptera littoralis

Two 15 cm high cotton plants were with 25 ml of a Solution containing 0.1% test substance (acetone / water 1: 1). After drying were per plant 5 larvae of the species Spodoptera littoralis (L3 stage) are attached. A plastic cylinder was over the plant everted and closed with a copper gauze lid. The damage caused by eating was determined after 2 days.

Compounds according to Example 1 showed a good anti-eating effect in the above experiment. Because of her Compounds 1, 4, 6 and 29 are particularly effective (only slight damage caused by eating) to highlight.

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Example 5

Effect against Lucilia. sericata

_{2 ml of an aqueous solution containing O 5} IX test substance are added to 2 ml of a culture medium. About 30 freshly hatched Lucilia sericata larvae are then added to the culture medium and the insecticidal effect is determined after 96 hours by determining the mortality rate. Compounds according to Example 1, in particular compounds 1, 3, 11, 12, 14, 21, 22, 26, 27 and 32, showed a good action against Lucilia sericata larvae in the above test.

Example 6. .

Effect against Musca domestica

50 g each of CSMA maggot substrate were weighed into beakers. From a 17 _o strength acetone solution was pipetted to 50 ml gr. Made of substrate per active substance 2.5 times each. After the treated substrate has been thoroughly mixed, the solvent is allowed to evaporate. 25 1-, 2-, and 3-day maggots and approx. 50 fly eggs were then used for each active ingredient. After pupation was complete, the pupae were flushed out and counted. After 10 days, the number of hatched flies was determined and thus a possible influence on the metamorphosis was determined.

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Compounds according to Example 1 showed a good effect against Musca dornestica in the above experiment. Because of their effect compound 1 is particularly suitable.

Example 7

Action against Aedes aegypti larvae

In a beaker containing a solution of the active substance (Concentration 5 ppm) Approximately 20 2-day larvae of the yellow fever mosquito (Aödes aegypti) were grown. The cup was then covered with a sieve lid. After the control animals had completed their adult moult, they were killed Test animals examined and the percentage of normal adults compared to the control determined. In this test, compounds according to Example 1 showed a good action against Aödes aegypti larvae. Because of her special compound 1 is to be emphasized for its good effect.

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Example 8

See effect against supplies ? cfli nge

Wheat was pickled with the active ingredient (10 ppm) and each with 25 adult beetles loaded. After 3 months of exposure, the number of test animals compared to the untreated Control determined.

Compounds according to the preceding examples showed a very good action against Trogoderma granarium, Sitophilius granarius, Rhyzoperta dominica, Tribolium castaneum and Oryzaephilus surinamensis. "

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Claims (12)

CSEiA-CEiGYAG .- 3 «? .. claims 1. / Compounds of the formula I wor in R, means a: methyl group and R _{9 represents} a hydrogen atom or R and R ₂ together represent a fused-on benzene nucleus form and
R. "represents a phenyl group optionally substituted one, two or three times by halogen, methyl, ethyl, i-propyl, trifluoromethyl, nitro and / or cyano, where, if R, and Ro condensed one on together Benzene nucleus form R "- not a" phenyl, 4-nitrophenyl, 3-trifluoromethylphenyl or exclusively by halogen substituted phenyl group ': may. · '-. 70 * 814/1100 ORIGINAL fNSPECTED 2. Compounds according to claim 1 of the formula Ia ^R 2Y "V ^CO - ^NH -V i) there) R, -Nr-S 5
in which. . R ₁ and R have the meanings already given in claim 1 and R, and Rc independently of one another for a hydrogen or halogen atom,. or a methyl or trifluoromethyl group. 3. Compounds according to claim 1 of the formula Ib ^R 2 wherein R ₁ and R _{2 have} the meanings already given in claim 1 and R, and R_ independently of one another for a hydrogen or Halogen atom or v7. a methyl or trifluoromethyl group stand. 7Ü98UM100 4. 3-N- (4-trifluoromethylphenyl) -carba.Kioyl-4-hydroxy- -coumarin according to claim 5. 3-N- (3-methylphenyl) -carbamoyl-4-hydroxy-coumarin according to claim 3. 6. 3-N- (4-chloro-2-methy! Phenyl) -carbamoyl-4-hydroxy- -coumarin according to claim 7. Process for the preparation of compounds of the formula I according to claim 1, characterized in that man a) an ester of the formula II OH with an aniline of the formula III II ⁶ . dl) H ^R 3 " ^N \ _H - (HD implements; 709814/1100 b) a compound of the formula IV OH . (IV) with an isocyanate of the formula V R ₃ -NCO '(V) lets react; or that one c) a compound of the above formula IV with an azide of formula VI • R ₃ -CO-N ₃ (VI) treated ; where in the formulas II to VI R 1 to R "have the meanings already given in claim 1 and R ₆ represents a C 1-4 alkyl radical. 7093ΗΠ 1 OQ 8. Insecticidal agent, characterized in that it contains a compound according to claim 1 as active ingredient., 9 .. Use of a compound according to claim 1 for combating insects. 10. Use of a compound according to claim 1 for Control of plant-damaging insects. 11. Use of a compound according to claim 1 for combating plant-damaging insects in Gemtise- or cotton crops. 12. Use of a compound according to claim 1 for combating ectoparisitarian insects. 7098U / 11