CA1088079A - Insecticidally active 3-n-phenyl-carbamoyl-4-hydroxy- 1,2-(benzo)-pyrone-derivatives - Google Patents

Abstract

Abstract The present invention relates to the compound 3-N-(4-trifluoro-methylphenyl)-carbomoyl-4-hydroxy-coumarin of the formula I

Description

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The present invention relates to the compound 3-N-(4-trifluoromethylphenyl)-carbamoyl-4-hydroxy-coumarin of the formula I
O
.\ /.~ /C-NH-.~ ~--CF3 (I) ~./ \o/ ~0 ' a process for the manufacture thereof, insecticidal com-positions which contain this compound as active component, and a method of controlling insects, which comprises the use of the new compound.
The compound of the formula I may be obtained by methods which are known per se, for example by reacting (a) an ester of the formula II
OH
~ ~COOR6 y (II) ~./ \0/-~0 wherein R6 represents a Cl-C4-alkyl group, with 4-trifluoromethylaniline;
(b) a compound of the formula III
OH

i (III) ~.~ \o/ ~0 with 4-trifluoromethylphenylisocyanate;
or (c) a compound of the above formula III with an azide of the formula IV
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=--F C~ --C0-N3 (IV) --Preferably the processes (a) and (c) are carried out at a reaction temperature between 100 and 200C and process (b) at a reaction temperature between 0 and 200C.
The reactions can be carried out at normal or elevated pressure, optionally in a solvent or diluent which isinert to the reactants and, if appropriate, in the presence of a base.

Solvents and diluents which are suitable for these reactions are for example: ethers and ethereal compounds, such as dipropyl ether, dioxan, dimethoxyethane and tetra-hydrofurane; amides, such as N,N-dialkylated carboxamides;
aliphatic, aromatic and halogenated hydrocarbons, in par- -ticular benzene, toluene, xylenes, and chlorobenzene;
nitriles, such as acetonitrile; dimethyl sulphoxide; and ketones, such as acetone and methyl ethyl ketone.

Suitable bases are tertiary amines, such as tri-ethylamine, dimethyl aniline, pyridine, picolines and lutidines, hydroxides, oxides, carbonates and bicarbonates of alkali metals and alkaline earth metals, for example potassium tert.butylate and sodium methylate.

In accordance, with the present invention it has now been found that the compound of the formula I has an exceptionally good action on insects. In particular, the compound of the formula I is very effective against insects that are harmful to plants and animals and can be used for example to control insects of the families:

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Acrididae, Blattidae, Gryllidae, Gryllotalpidae, Tettigoni-idae, Cimicidae, Pyrrhocoridae, Reduviidae, Aphididae, Delphacidae, Diaspididae, Pseudococcidae, Chrysomelisae, Coccinellidae, Bruchidae, Scarabaeidae, Dermestidae, Tene-brionidae, Curculionidae, Tineidae, Noctuidae, Lymantri-idae, Pyralidae, Galleridae, Culicidae, Tipulidae, Stomoxy-dae, Muscidae, Calliphoridae, Trypetidae, and Pulicidae.

However, the compound of the formula I is chiefly suitable for controlling plant-injurious insects, especial-ly those of the order Coleoptera, for example Leptinotarsa decemlineata and Anthonomous grandis, for example in veget-able crops and cotton plantations. In addition the compound of the formula I is outstandingly effective against ecto-parasitic insects, for example Lucilia sericata, and against insects which are harmful in the spheres of hygiene and storage, for example Musca domestica and Aëdes aegypti.

The insecticidal action of the subject compound can be substantially broadened and adapted to prevailing cir-cumstances by the addition of other insecticides and/or acaricides. Examples of suitable additives are: organic phosphorus compounds, nitrophenols and derivatives thereof, formamidines, ureas, pyrethroids, carbamates, and chlorin-ated hydrocarbons.

The compound of the formula I may be used as pure active substance or together with suitable carriers and/or additives. Suitable carriers and additives can be solid or liquid and correspond to the substances conventionally used in the art of formulation, for example natural or regenerated substances, solvents, dispersants, wetting agents, tackifiers, thickeners, binders and/or fertilisers.

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For application, the compound of the formula I may be processed to dusts, emulsion concentrates, granules, dispersions, sprays, to solutions or suspensions, in the conventional formulation which is commonly employed in application technology.

The compositions according to the invention are obtained in known manner by intimately mixing and/or grinding the compound of the formula I with the suitable carriers, with or without the addition of dispersants or solvents which are inert to the active substances.

The compositions according to the invention may take, and be used in, the following forms:
Solid forms:
Dusts, tracking agents, granules, coated granules, impregnated granules and homogeneous granules.
Liquid forms:
a) active substance concentrates which are dis-persible in water: wettable powders, pastes, emulsions;
b) solutions.

The content of the compound of the formula I in the above described compositions is between 0.1% and 95%, in which connection it must be mentioned that higher concen-trations can also be used if the compositions are applied from an aircraft or other appropriate application devices.

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

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Dusts The following substances are used to obtain a) a 5%
and b) a 2% dust:
a) 5 parts of the compound of the formula I, 95 parts of talcum;
b) 2 parts of the compound of the formula I, 1 part of highly disperse silicic acid, 97 parts of talcum.

The compound of the formula I is mixed with the carriers and ground.

Granules The following substances are used to produce 5%
granules:
parts of the compound of the formula I, 0.25 parts of epichlorohydrin, 0.25 parts of cetyl polyglycol ether, 3.50 parts of polyethylene glycol, 91 parts of kaolin (particle size 0.3-0.8 mm).

The compound of the formula I is mixed with epichlor-ohydrin and dissolved with 6 parts of aceton; the poly-ethylene glycol and cetyl polyglycol ether are then added.
The resultant solution is sprayed on kaolin, and the acetone is subsequently evaporated in vacuo.

Wettable powder:
The following constituents are used for the prepar-ation of a) a 40%, b) and c) a 25~, and d) a 10% wettable powder:
B

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b) 54 parts of silicic acid, parts of the compound of the formula I, , 4.5 parts of calcium lignin sulphonate, 1.9 parts of Champagne chalk/hydroxyethyl cellulose mixture (1:1), 1.5 parts of sodium dibutyl naphthalene sulphonate, 19.5 parts of silicic acid, 19.5 parts of Champagne chalk, 28.1 parts of kaolin.
c) 25 parts of the compound of the formula I,

2.5 parts of isooctylphenoxy-polyoxyethylene-ethanol, 1.7 parts of Champagne chalk/hydroxyethyl cellulose mixture (1:1), 8.3 parts of sodium aluminium silicate, 16.5 parts of kieselgur, 46 parts of kaolin.
d) 10 parts of the compound of the formula I,

3 parts of a mixture of the sodium salts of saturated fatty alcohol sulphates, parts of naphthalenesulphonic acid/formaldehyde condensate, 82 parts of kaolin.

The active compound of the formula I is intimately mixed, in suitable mixers, with the additives, the mixture being then ground in appropriate mills and rollers to yield wettable powders, which can be diluted with water to give suspensions of the desired concentration .

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Emulsifiable concentrate:

The following substances are used to produce a 10%
emulsifiable concentrate:
parts of the compound of the formula I, 3.4 parts of epoxidised vegetable oil, 3.4 parts of a combination emulsifier consisting of fatty alcohol polyglycol ether and alkyl-aryl sulphonate calcium salt, parts of dimethylformamide, 43.2 parts of xylene.

By diluting such a concentrate with water it is possible to manufacture emulsions of the desired concen-tration.

Spray:

The following constituents are used to prepare a) a 5% and b) a 95% spray:
a) 5 parts of the compound of the formula I, 1 part of epichlorohydrin, 94 parts of benzene (boiling limits 160C-190C.) b) 95 parts of the compound of the formula I, 5 parts of epichlorohydrin.

The following Examples illustrate the invention in more detail.

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Example 1: Preparatlon of 3-N-(4-trifluoromethylphenyl)-carbamoyl-4-hydroxy-coumarin With stirring, 10.1 g of triethylamine and then 18.6 g of 4-trifluoromethylphenylisocyanate are added drop-wise at room temperature to a solution of 16.2 g of

4-hydroxycoumarin in 150 ml of dimethyl sulphoxide. The reaction mixture is stirred for a further 4 hours at room temperature and then poured into a solution of 15 ml of concentrated hydrochloric acid in 300 ml of water. The precipitate which has formed is collected by suction fil-tration. Recrystallisation from dioxane gives the product of the formula OH .=.
CO-NH--~ ~--CF3 il ~-/-\0/-~0 with a melting point of 258-260C.

Example 2: Action on Leptinotarsa decemlineata I

Potato plants were sprayed with a 0.05% aqueous emulsion of the compound of the formula I (obtained from a 10% emulsifiable concentrate).

After the spray coating had dried, the plants were populated with larvae of Leptinotarsa decemlineata in the L3-stage. Evaluation of the mortality achieved took place after 2, 4, 8, 24 and 48 hours. The test was carried out at 24C and 60% relative humidity.

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In the above te~t, the co~pound of the formula I
exhLbited good insecticidal stomach poison on Leptinotarsa decemlineata larvae.

Example 3: Action on Leptinotarsa decemlineata II , Two potato plants (15 cm in height) were sprayed with 25 ml of an acetone/water mixture (1:1) containing 0.05% of the compound of the formula I.

After the spray coating had dried, each of the potato plants were each populated with 10 larvae of the species Leptinotarsa decemlineata (L3-stage). A plastic cylinder was then slipped over each plant to prevent the larvae from migrating. A copper gauze top was used to seal the cylinder. The damage caused by eating was determined 2 days later.

In the above test, the compound of the formula I
effectively inhibited damage from eating (only minor damage observed).

Example 4: Action on Spodoptera littoralis Two cotton plants (15 cm in height) were sprayed with 25 ml of a solution of acetone/water (1:1) containing 0.1% of the compound of the formula I. After the spray coating had dried, each plant was populated with 5 larvae of the species Spodoptera littoralis (L3-stage). A plastic cylinder was slipped over each plant and sealed with a copper gauze top. The damage caused by eating was deter-mined 2 days later.

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In the above test, the compound of the formula I
effectively inhibited damage caused by eating (only minor damage observed).

Example 5: Action on Lucilia sericata An aqueous solution containing 0.1% of the compound ofthe formula I (2 ml) was added to2 ml ofa culture medium.
Approx. 30 freshly hatched-out larvae of Lucilia sericata were then added to the culture medium and the insecticidal action was determined after 96 hours by evaluating the mortality rate.

In this test, the compound of the formula I was particularly effective against larvae of Lucilia sericata.

Example 6: Action on Musca domestica 50 g of freshly prepared CSMA nutrient substrate for maggots were charged into beakers. A specific amount of a 1% acetonic solution of the compound of the formula I
was pipetted onto the nutrient substrate present in the beakers. The substrate was then thoroughly mixed and the acetone subsequently allowed to evaporate over a period of at least 20 hours.

Then 25 one day-old maggots of Musca domestica were put into each of the beakers containing the treatednutrient substrate for testing at each of its given concentrations.
After the maggots had pupated, the pupae were separated from the substrate by flushing them out with water and then deposited in containers closed with a perforated top.
B

--Each batch of flushed out pupae was counted to determine the toxic effect of the active substance on the maggot development. The number of flies which had hatched out of the pupae was then counted after 10 days and any influence on the metamorphosis thereby determined.

In the above test, the compound of the formula I
was very effective against Musca domestica.

Example 7: Action on the larvae of Aëdes aegypti Approx. 20 two day-old larvae of the yellow fever fly (Aëdes aegypti) were put into a beaker containing a solution of the compound of the formula I (concentration=

5 ppm). The beaker was then covered with a perforated top.
After the controls had shed and emerged fully to the adult stage, the test subjects were examined and the percentage of normal adults in comparison with the controls wasdeter-mined. In this test, the compound of the formula I wasvery effective against larvae of Aëdes aegypti.

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Claims

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PRIVILEGE OR PROPERTY ARE CLAIMED ARE DEFINED AS FOLLOWS:

1. The compound 3-N-(4-trifluoromethylphenyl)-carbamoyl--4-hydroxy-coumarin of the formula I

(I) .

2. Process for the production of the compound of the formula I as defined in claim 1, which process comprises a) reacting an ester of the formula II

(II) where R6 represents a C1-C4-alkyl group, with 4-tri-fluoromethylaniline;
b) reacting a compound of the formula III

(III) with 4-trifluoromethylphenyl-isocyanate; or c) reacting a compound of the formula III above with an azide of the formula IV

( IV) 3. A method of controlling insect pests at a locus which method comprises applying to said locus an insect-icidally effective amount of the compound 3-N-(4-trifluoro-methylphenyl)-carbamoyl-4-hydroxy-coumarin as claimed in

claim 1.