DE3627161A1 - Novel oxadiazines, their preparation, and pesticides containing these compounds - Google Patents

Abstract

Novel N-phenyl-1,3,5-oxadiazine-2,4-diones of the formula I <IMAGE> in which R1 denotes fluorine or chlorine and R2 denotes hydrogen, fluorine, chlorine or methoxy, their preparation, their use in pest control, and pesticides which contain these oxadiazines as active substance are disclosed. The preferred field of application is the control of pests on animals and plants.

Description

The present invention relates to new N-phenyl-1,3,5-oxadiazine 2,4-dione, their manufacture, their use in pest control as well as pesticides which these oxadiazines contain.

From DE-OS 29 05 687 N-phenyl-1,3,5-oxadiazine-2,4-dione as Insecticidal active ingredients known in which the N-phenyl is not simultaneously in the 2.5 position by Cl and in the 4 position by 1,1,2,3,3,3- Hexafluoropropoxy is substituted.

The oxadiazines according to the invention correspond to formula I. wherein
R ₁ fluorine or chlorine and
R _{2 is} hydrogen, fluorine, chlorine or methoxy
mean.

Preferred compounds of the formula I are those in which R ₁ and R _{2 are} identical and are fluorine or chlorine.

Examples of compounds of formula I are thus

The compounds according to the invention can be produced by processes known in principle. Such methods are described in DE-OS 27 32 115 and 29 05 687, among others. So the compounds of formula I z. B. can be obtained by using a benzoyl isocyanate of formula II with the isocyanate of formula III implements. To carry out the process, the two reaction components are heated, if appropriate in the presence of a solvent or diluent, to a temperature in the range from 50 to 150 ° C. for 30 minutes to 30 hours, preferably to a temperature in the range from 80 to 120 for 5 to 15 hours ° C. Suitable solvents or diluents are above all polar aprotic solvents such as. B. dimethyl sulfoxide, dimethylformamide or N, N-dimethylacetamide.

The compounds of the invention can also be prepared by other methods, e.g. B. by
a) a halocarbonylbenzamide of the formula IV with the isocyanate of formula III, or
b) a benzoyl isocyanate of the formula II with a carbamic acid ester of the formula V condensed. In the formulas II, IV and V, the radicals R ₁ and R _{2 have} the meaning given for formula I, while X is halogen, preferably chlorine, and R is an alkyl radical, preferably a lower alkyl radical having 1 to 4 carbon atoms.

The compounds of the formula II to V are known or can be according to known methods are produced. So can the benzoyl isocyanates of formula II by implementation of the appropriately substituted Benzamides made with oxalyl chloride and the isocyanate Formula III from the correspondingly substituted aniline Implementation can be obtained with phosgene.  

The compounds according to the invention surprisingly have compared to the compounds known from DE-OS 29 05 687 superior activity against Heliothis virescens and Spodoptera littoralis on. In general, they are cheap with warm-blooded animals and plant tolerance valuable active ingredients in pest control. So are the compounds of formula I z. B. for Control of pests on animals and plants. Such pests mainly belong to the tribe of arthropods, in particular Insects of the orders Lepidoptera, Coleoptera, Homoptera, Heteroptera, Diptera, Thysanoptera, Orthoptera, Anoplura, Siphonaptera, Mallophaga, Thysanura, Isoptera, Psocoptera or Hymenoptera and Arachnids of the order Acarina, such as B. mites and ticks. Here any stage of pest development can be controlled, d. H. both adults, dolls and nymphs, and especially the Larvae and eggs. So especially larvae and eggs from phytopathogenic Insect pests and mites in ornamental and useful plants, such as e.g. B. in fruit and vegetable crops, and especially in cotton crops, be combated effectively. Will connections of the Formula I absorbed by adults, so their effect can be in show immediate killing of the pests or in reduced Egg laying and / or hatching rate. The latter phenomenon can especially in coleopteras. When fighting of animal parasitic pests, especially on domestic and farm animals, come mainly ectoparasites, such as. B. mites and ticks and Dipteras such as B. Lucilia sericata.

The good pesticidal activity of the compounds according to the invention corresponds to a mortality rate of at least 50-60% of the pests mentioned.

The effect of the compounds according to the invention or of them containing agents can be added by adding other insecticides and / or acaricides significantly widen and given circumstances to adjust. As such additives come e.g. B. organic phosphorus compounds,  Nitrophenols and derivatives, formamidines, ureas, carbamates, Pyrethroids, chlorinated hydrocarbons and Bacillus thuringiensis preparations.

The compounds of the formula I can also be used with particular advantage combine with substances that reinforce a pesticide Exert effect. Examples of such connections include. a. Piperonyl butoxide, Propynyl ether, popynyl oxime, propynyl carbamate and Propynyl phosphonates, 2- (3,4-methylenedioxyphenoxy) -3,6,9-trioxaundecane or S, S, S-tributylphosphorotrithioate.

The compounds of formula I are in unchanged form or preferably together with those customary in formulation technology Tools used and are therefore z. B. emulsion concentrates, directly sprayable or dilutable solutions, diluted Emulsions, wettable powders, soluble powders, dusts, Granules or encapsulations in e.g. B. polymeric substances in processed in a known manner. The application methods, such as spraying, Misting, dusting, scattering or pouring are also possible like the means the intended goals and the given circumstances chosen accordingly.

The formulations, i.e. H. which are an active ingredient of the formula I or Combinations of these active substances with other insecticides or Acaricides, and optionally a solid or liquid additive containing agents, preparations or compositions, are manufactured in a known manner, for. B. by intimate mixing and / or grinding the active ingredients with extenders, such as. B. with Solvents, solid carriers and optionally surface-active compounds (surfactants).

Possible solvents are: Aromatic hydrocarbons, preferably fractions C ₈ to C ₁₂ , such as. B. xylene mixtures or substituted naphthalenes, phthalic esters such as dibutyl or dioctyl phthalate, aliphatic hydrocarbons such as cyclohexane, paraffins, alcohols and glycols and their ethers and esters such as ethanol, ethylene glycol, ethylene glycol monomethyl or ethyl ether, ketones, such as cyclo Solvents, such as N-methyl-2-pyrrolidone, dimethyl sulfoxide or dimethylformamide, and optionally epoxidized vegetable oils, such as epoxidized coconut oil or soybean oil, or water.

As solid carriers, e.g. B. for dusts and dispersible Powders, like natural rock flours, are usually used Calcite, talc, kaolin, montmorillonite or attapulgite. For improvement the physical properties can also be highly disperse Silicas or highly disperse absorbent polymers added will.

Porous types such as are used as granular, absorptive granulate carriers e.g. B. pumice, broken brick, sepiolite or bentonite, as not sorptive carrier materials e.g. B. calcite or sand, in question. In addition, a variety of pre-granulated materials inorganic or organic nature, such as especially dolomite or shredded plant residues can be used.

Depending on the nature of the surface active compounds formulating active ingredient of formula I or the combination thereof Active ingredients with other insecticides or non-ionic acaricides, cationic and / or anionic surfactants with good emulsifying, dispersing and network properties. Among surfactants are also Understand surfactant mixtures.

Suitable anionic surfactants can be both water-soluble Soaps as well as water-soluble synthetic surface-active Connections.

As soaps are the Akali, alkaline earth or optionally substituted ammonium salts of higher fatty acids (C ₁₀ -C ₂₂ ), such as. B. the Na or K salts of oleic or stearic acid, or of natural fatty acid mixtures which, for. B. can be obtained from coconut or tall oil. The fatty acid methyl taurine salts should also be mentioned.

However, so-called synthetic surfactants are used more often, especially fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or alkylarylsulfonates.

The fatty sulfonates or sulfates are usually alkali, Alkaline earth or optionally substituted ammonium salts before and generally have an alkyl radical with 8 to 22 carbon atoms, where alkyl also includes the alkyl portion of acyl groups, e.g. B. that Na or Ca salt of lignin sulfonic acid, the dodecylsulfuric acid ester or one made from natural fatty acids Fatty alcohol sulfate mixture. The salts of Sulfuric acid esters and sulfonic acids from fatty alcohol-ethylene oxide adducts. The sulfonated benzimidazole derivatives preferably contain 2 Sulfonic acid groups and a fatty acid residue with about 8-22 carbon atoms. Arylalkyl sulfonates are e.g. B. the Na, Ca or triethanolamine salts dodecylbenzosulfonic acid, dibutylnaphthalenesulfonic acid or a naphthalenesulfonic acid-formaldehyde condensation product. Corresponding phosphates, such as, for. B. salts of Phosphoric acid ester of a p-nonylphenol- (4-14) -ethalenoxide adduct in question.

The primary nonionic surfactants are polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, saturated or unsaturated fatty acids and alkylphenols in Question, the 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon radical and 6 to 18 carbon atoms may contain in the alkyl radical of the alkylphenols. Farther suitable nonionic surfactants are the water-soluble 20 to 250 Ethylene glycol ether groups and 10 to 100 propylene glycol ether groups containing polyethylene oxide adducts with polypropylene glycol, Ethylene diaminopolypropylene glycol and alkyl polypropylene glycol with 1 to  10 carbon atoms in the alkyl chain. The connections mentioned usually contain 1 to 5 per propylene glycol unit Ethylene glycol units.

Examples of nonionic surfactants are nonylphenol polyethoxyethanols, Castor oil polyglycol ether, polypropylene-polyethylene oxide Adducts, tributylphenoxypolyäthoxyäthanol, polyethylene glycol and Octylphenoxypolyäthoxyäthanol mentioned. There are also fatty acid esters of polyoxyethylene sorbitan, such as the polyoxyethylene sorbitan trioleate, into consideration.

The cationic surfactants are primarily quaternary Ammonium salts, which as N-substituents at least one Contain alkyl radicals with 8 to 22 carbon atoms and as further substituents low, optionally halogenated alkyl, benzyl or have low hydroxyalkyl radicals. The salts are preferably as halides, methyl sulfates or ethyl sulfates, e.g. B. that Stearyltrimethylammonium chloride or the benzyl-di- (2-chloroethyl) - ethyl ammonium bromide.

The surfactants commonly used in formulation technology are u. a. in described in the following publications:

"Mc Cutcheon's Detergents and Emulsifiers Annual" MC Publishing Corp., Ridgewood, New Jersey, 1981; Dr. Helmut Stache "surfactant Paperback ", Carl Hanser Verlag Munich / Vienna 1981.

The pesticidal preparations usually contain 0.1 to 99%, in particular 0.1 to 95%, active ingredient of the formula I or combinations of these agents with other insecticides or acaricides, 1 to 99.9% of a solid or liquid additive and 0 to 25%, in particular 0.1 to 20% of a surfactant. While as a commodity rather concentrated means are preferred, the end user uses usually diluted preparations that are essential have lower drug concentrations.  

The agents can also contain other additives, such as stabilizers, defoamers, Viscosity regulators, binders, adhesives and Fertilizers or other active ingredients to achieve special effects contain.

Example 1:

a) Preparation of 2,5-dichloro-4- (1,1,2,3,3,3-hexafluoropropoxy- phenyl isocyanate

16.4 g of 2,5-dichloro-4- (1,1,2,3,3,3-hexafluoropropoxy) aniline are dissolved in 94.5 ml of toluene and added dropwise with stirring at 22 ° C. to a solution consisting of 90 g of toluene containing 20% by weight of phosgene, 100 ml of dioxane and 300 ml of chlorobenzene were added. The reaction mixture is then stirred for an hour at room temperature, 50 ° C and 80 ° C. The mixture is then concentrated under a water jet vacuum and distilled under a high vacuum. The title compound of the formula is obtained as a colorless oil. Bp 95 ° C / 2.5 mbar.

b) Preparation of 3- [2,5-dichloro-4- (1,1,2,3,3,3-hexafluoropropoxy) - phenyl] -6- (2,6-difluorophenyl) -3,4-dihydro-2H-1,3,5-oxadiazine 2,4-dione

With exclusion of moisture, 5.49 g of 2,6-difluorobenzoyl isocyanate are added to 10 g of 2,5-dichloro-4- (1,1,2,3,3,3-hexafluoropropoxy) phenyl isocyanate with stirring. The temperature is kept at 120 ° C. for 14 hours, stirring until the reaction mixture begins to solidify. When the resulting crystal slurry has cooled to room temperature, it is ground with hexane and then suction filtered. The residue is recrystallized from toluene. The title compound of the formula is obtained with a mp. of 189-191 ° C.

The following connections are made in an analogous manner:

Example 2: Formulation examples for active compounds of the formula I. according to production example 1

From such concentrates, emulsions can be diluted with water any desired concentration.

2.2 solutions

The solutions are suitable for use in the form of tiny drops.

2.3 granules

The active ingredient is dissolved in methylene chloride on the carrier sprayed on and then the solvent in vacuo evaporated.

2.4 dusts

By intimately mixing the carriers with the active ingredient ready-to-use dusts.  

2.5 wettable powder

The active ingredient is mixed well with the additives and ground well in a suitable mill. Spray powder is obtained which can be diluted with water to form suspensions of any desired concentration.
2.6 Extruder granules
Active ingredient according to production example 1 10%
Na lignin sulfonate 2%
Carboxymethyl cellulose 1%
Kaolin 87%

The active ingredient is mixed with the additives, ground and moistened with water. This mixture is extruded and then dried in an air stream.
2.7 coating granules
Active ingredient according to production example 1 3%
Polyethylene glycol (MG 200) 3%
Kaolin 94%

The finely ground active ingredient is applied evenly in a mixer to the kaolin moistened with polyethylene glycol. In this way, dust-free coating granules are obtained.
2.8 Suspension concentrate
Active ingredient according to production example 1 40%
Ethylene glycol 10%
Nonylphenol polyethylene glycol ether (15 mol AeO) 6%
Na lignin sulfonate 10%
Carboxymethyl cellulose 1%
37% aqueous formaldehyde solution 0.2%
Silicone oil in the form of a 75% aqueous emulsion 0.8%
Water 32%

The finely ground active ingredient becomes intimate with the additives mixed. A suspension concentrate is thus obtained, from which by diluting with water suspensions of any desired concentration can be produced.

Example 3: Biological examples Example 3.1: Action against Musca domestica

50 g freshly prepared CSMA nutrient substrate for maggots are in weighed a mug. From a 1% by weight acetone solution of the active ingredient are 5 ml on the nutrient substrate in the cup pipetted. After mixing the substrate, leave evaporate the acetone for at least 20 hours.

Then 25 one-day maggots of Musca domestica are born given treated nutrient substrate containing cups. After yourself If the maggots have pupated, the pupae formed will be through Flush with water separated from the substrate and in one with a vessel sealed with a sieve lid.  

The washed out dolls are counted (toxic influence of Active ingredient on maggot development). Then after 10 days the Number of flies hatched from the dolls determined.

Compounds according to Example 1 show good activity in the above test.

Example 3.2: Action against Lucilia sericata

1 ml of a 0.5% active substance is added to 9 ml of growth medium at 50 ° C containing aqueous preparation. Now about 30 added freshly hatched Lucilia sericata larvae to the culture medium. After 48 and 96 hours, the insecticidal effect is determined the kill rate found.

Compounds according to Example 1 show good activity in this test against Lucilia sericata.

Example 3.3: Effect against Aedes aegypti

On the surface of 150 ml of water, which is in a container is so much of a 0.1% acetone solution of the The active ingredient pipettes that a concentration of 12.5 ppm is obtained. After the acetone has evaporated, the container with 30-40 2-day Aedes larvae are fed. After 2 and 7 days the Mortality checked.

Compounds according to Example 1 show good activity in this test.

Example 3.4: Insecticidal feeding poison effect

Cotton plants (approx. 20 cm high) are washed with an aqueous Active ingredient emulsion (obtained from a 10% emulsifiable concentrate) sprayed, the active ingredient emulsion 100 ppm of the test Contains connection.

After the covering has dried on, the cotton plants are included Spodoptera littoralis and Heliothis virescens larvae in the third larval stage occupied. The test becomes more relative at 24 ° C and 60%  Humidity carried out. At intervals of each 24 hours are mortality, developmental and molting disorders of the attached larvae.

Compounds according to Example 1 show good activity in this test.

Example 3.5: Effect on Spodoptera Littoralis and Heliothis virescens (larvae and eggs)

Three cotton plants, about 15-20 cm high, grown in pots are treated with a sprayable liquid preparation of the active substance to be tested. After the spray coating has dried on, the potted plants are placed in a tin container of about 20 liters, which is covered with a glass plate. The moisture inside the covered vessel is regulated so that no condensed water forms. Direct light falling on the plants is avoided. Then the three plants are infested, with a total of:
a) 50 larvae of Spodoptera Littoralis or Heliothis virescens of the first larval stage;
b) 20 larvae of Spodoptera littoralis or Heliothis virescens of the third larval stage;
c) two ice levels of Spodoptera littoralis or Heliothis virescens (2 leaves of a plant are enclosed in a plexiglass cylinder closed on both sides with gauze); two ice levels from Spodoptera or part of a cotton leaf with eggs from Heliothis placed thereon are added to the enclosed leaves.

After 4 and 5 days, the evaluation compared to untreated controls takes into account the following criteria:
a) number of larvae still alive,
b) larval inhibition of development and molting,
c) damage caused by eating (scraping and pitting),
d) hatching rate (number of larvae hatched from the eggs).

Compounds according to Example 1 show in a concentration of 400 ppm good overall effectiveness in the above test.

Example 3.6: Ovicidal effect on Spodoptera littoralis

Spodoptera littoralis eggs deposited on filter paper are released cut out of the paper and in a 0.05% by weight solution of the Active ingredient immersed in an acetone / water mixture (1: 1). The so treated egg layers are then removed from this mixture and at 28 ° C and 60% relative humidity in plastic trays deposited.

After 5 days, the hatching rate, i.e. H. the number of larvae that develop developed from the treated eggs.

Compounds according to Example 1 show good activity in the above test.

Example 3.7: Effect on Laspeyresia pomonella (eggs)

Laid eggs of Laspeyresia pomonella that are not older than 24 hours are on filter paper for 1 minute in a acetone-aqueous solution containing 400 ppm of the test Active ingredient, immersed. After the solution dries, it will Filter paper with the eggs laid out in a petri dish and at left at a temperature of 28 ° C. After 6 days the percentage Hatching from the treated eggs was rated.

Compounds according to Example 1 show good activity in the above test.

Example 3.8: Reproductive influence on Anthonomus grandis

Adult Anthonomus grandis, which after hatching is not older than 24 hours are in groups of 25 beetles each in cages transferred with lattice walls. The cages with the beetles are then placed in an acetone solution for 5 to 10 seconds, containing 0.1% by weight of the active ingredient to be tested, immersed.  

When the beetles are dry again, they become copulations and Egg laying in covered trays containing food. Laying eggs are made two to three times a week with flowing Water washed out, counted, by two to three hours Put in an aqueous disinfectant and then disinfect deposited in trays containing a suitable larval diet. To Seven days are examined to determine whether larvae are present in the deposited eggs have developed.

To determine the duration of the influence on reproduction The egg laying of the beetles becomes an effect of the active substances to be tested checked over a period of about four weeks. The Rating is based on the reduction in the number of filed Eggs and the daruas hatched larvae compared to untreated Controls.

Connections according to Example 1 show a good reduction in production Effect in the above test.

Example 3.9: Activity against Anthonomus grandis (adults)

Two potted cotton plants in the 6-leaf stage are with containing aqueous wettable emulsion preparations 100 ppm of the active ingredient to be tested, sprayed. After drying of the spray coating (about 1.5 hours), each plant is 10 adult beetles (Anthonomus grandis) populated. Plastic cylinder, whose upper openings are covered with gauze, are then over the treated plants populated with the test animals to prevent the beetles from migrating. The treated plants are kept at 25 ° C and about 60% relative humidity. The evaluation takes place after 2, 3, 4 and 5 days on the basis the percentage mortality of the test animals used (% supine) as well as the antifeedant effect compared to untreated Control approaches.

Compounds according to Example 1 show good effects in this test.

Claims (13)

1. Compounds of formula I. wherein
R ₁ fluorine or chlorine and
R _{2 is} hydrogen, fluorine, chlorine or methoxy
mean. 2. Compounds according to claim 1, wherein R _{1 is} fluorine or chlorine and R _{2 is} hydrogen, fluorine or chlorine. 3. Compounds according to claim 2, wherein R ₁ and R ₂ each represent fluorine or chlorine. 4. A compound according to claim 3 of the formula 5. A compound according to claim 3 of the formula 6. A compound according to claim 1 of the formula 7. Connection according to claim 2 of the formula 8. A compound according to claim 2 of the formula 9. Process for the preparation of a compound of formula I. wherein
R ₁ fluorine or chlorine and
R _{2 is} hydrogen, fluorine, chlorine or methoxy
mean, characterized in that a benzoyl isocyanate of the formula II with the isocyanate of formula III implemented in a known manner, wherein in the formula II the symbols R ₁ and R _{2 have} the meaning given for formula I. 10. pesticide, which is a compound of formula I as the active component contains what
R ₁ fluorine or chlorine and
R _{2 is} hydrogen, fluorine, chlorine or methoxy
mean together with suitable carriers and / or additives. 11. pesticide according to claim 10, which contains as active component a compound of formula I in which R _{1 is} fluorine or chlorine and R _{2 is} hydrogen, fluorine or chlorine. 12. Use of a compound of formula I. wherein
R ₁ fluorine or chlorine and
R _{2 is} hydrogen, fluorine, chlorine or methoxy
mean to control pests on animals and plants. 13. Use according to claim 5 for combating arthropods, especially insects and arachnids harmful to plants.