DE3704100A1 - Acylaminonitriles, their preparation and their use as biocides - Google Patents

Abstract

Novel acylaminonitriles of the general formula <IMAGE> in which R has the meaning given in the description, and their preparation are described. The compounds according to the invention display a broad biocidal activity, in particular an insecticidal, acaricidal and herbicidal activity.

Description

The invention relates to new acylaminonitriles, their preparation and their use as biocides with insecticidal, acaricidal and herbicidal effects.

The compounds according to the invention differ in their chemical structure from all previously known biocides Active ingredients. They represent a completely new biocide Substance class and thus enrich the stand of the technique.

It has been found that acylaminonitriles of the general Formula I.

in the

R is hydrogen, a C _1-12 alkyl, C _1-12 alkyl, C _1-12 optionally substituted one or more times, identically or differently, by halogen, C _1-4 alkoxy, C _1-4 alkylthio, C _1-4 dialkylamino Alkenyl or C _1-12 alkynyl radical, a C _3-8 cycloalkyl radical, one optionally one or more times, identically or differently, with halogen, C _1-4 alkyl, C _1-4 alkoxy, C _1-4 - Alkylthio, C _1-4 -dialkylamino, C _1-6 -alkoxycarbonyl, carboxy, trifluoromethyl, trifluoromethoxy, difluoromethoxy, nitro, cyano-substituted phenyl, naphthyl, pyridyl, thienyl, furyl, phenyl-C _1-4 - alkyl, phenylvinyl, phenoxy-C _1-4 -alkyl, phenylthio-C _1-4 -alkyl, phenylamino-C _1-4 -alkyl or phenoxy, one or more, optionally, the same or different with halogen , C _1-4 alkoxy, C _1-4 alkylthio substituted C _1-12 dialkylamino, C _1-12 alkoxy, C _1-12 alkenoxy, C _1-12 alkynyloxy, C _3-8 -Cycloalkoxy- or C _1-12 -Alkylthiorest means, show a broad biocidal effect and especially one in Secticidal, acaricidal and herbicidal activity.

The compounds of general formula I according to the invention can also be used as a spectroscopic analysis cyclic E / Z isomers are present, as described by the following Formula I ′

being represented.

The invention thus relates to both the compounds of formula I as well as the cyclic isomers of formula I ' and their mixtures with one another.

The expressions C _1-4 alkyl or C _1-12 alkyl used in formula I are derived from straight-chain and branched-chain alkyl groups. Examples include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl and undecyl.

Unsaturated alkyl groups with up to 12 carbon atoms, such as alkenyl or alkynyl, can also be straight or branched be and more than one C = C double bond or C ≡ C triple bond exhibit. Examples include vinyl, allyl, Ethynyl and l-propynyl.

Halogen is to be understood as fluorine, chlorine, bromine or iodine.

The compounds according to the invention can be prepared by that a 4,4-bis (trifluoromethyl) -1-oxa-3-azabuta- 1,3-diene of formula II  

wherein

R has the meaning given in formula I,

either

• (A) reacted with trimethylsilyl cyanide and then the 4,4-bis (trifluoromethyl) -2-oxazoline-5-trimethylsilylimine of the formula III obtained as an intermediate whereinR has the meaning given in formula I, hydrolyzed or
• (B) implemented directly with hydrogen cyanide or
• (C) with alkali metal salts of hydrocyanic acid implemented and then hydrolyzed.

Process variant (A) is preferably carried out in such a way that with the starting material of formula II Trimethylsilyl cyanide between -20 ° C and 100 ° C with or without a solvent, usually at normal pressure Brings reaction. The following are suitable as solvents inert solvents such as, for example, the reactants Toluene, xylene, hexane, ether and tetrahydrofuran.

The trimethylsilyl cyanide is in a molar ratio of 1: 1 to 1: 3 based on the starting material of formula II used. The reaction time is about 0.5 to 40 hours.

The reaction mixture is mixed with dilute aqueous mineral acids, such as hydrochloric acid, then added neutralized with aqueous sodium bicarbonate solution and with an organic solvent such as diethyl ether, extracted.

The crude products can be obtained in the usual way by recrystallization, Vacuum distillation or column chromatography clean.

Process variant (B) is expediently carried out in such a way that that directly the starting material of formula II with hydrogen cyanide in a temperature range of -20 ° C to 120 ° C with or without a solvent at elevated Pressure or at normal pressure. The hydrogen cyanide is in a molar ratio of 1: 1 to 1:20, based on the starting material of formula II used. The reaction time is 0.5-60 hours.

The product is worked up by evaporating off the excess Hydrogen cyanide and optionally the solvent. The crude products can be obtained in the usual way by recrystallization, Clean vacuum distillation or column chromatography.  

Process variant (C) is expediently so carried out that the starting material of formula II with a salt of hydrocyanic acid, such as. B. Potassium cyanide or sodium cyanide, and then acidic worked up.

The reaction of the starting material of formula II with a Cyanide occurs in a temperature range between -20 ° C and 100 ° C in an inert to the reactants Solvents usually at normal pressure. As a solvent are suitable, for example, toluene, xylene, hexane, Ether and tetrahydrofuran.

The cyanide is in a molar ratio of 1: 1 to 1: 5 based on the starting material of formula II used. The response time is 0.5 to 200 hours.

The reaction mixture is worked up by Hydrolysis with dilute aqueous mineral acids, such as. B. Hydrochloric acid, followed by neutralization with aqueous Sodium bicarbonate solution and extraction with an organic Solvents such as B. Diethyl ether.

The crude products can be obtained in the usual way by recrystallization, Vacuum distillation or column chromatography clean.

The starting products for the production of the invention Connections are known per se or can be per se known methods can be produced.

The compounds of the invention are generally colorless and odorless crystalline or viscous substances which is sparingly soluble in water and in organic solvents are more or less soluble.  

The compounds according to the invention are notable for a good insecticidal and also acaricidal action against important harmful organisms from the order of the Coleoptera, Lepidoptera, Diptera, Homoptera, Heteroptera and Acarina out.

You can use it both in crop protection and on the Hygiene, storage protection and veterinary area as a pesticide be used.

The use of the compounds according to the invention can be found in Concentrations from 0.0005 to 5%, preferably from 0.001 to 0.1% depending on the area of application.

The compounds of the invention can either be used alone, in a mixture with one another or with other insecticidal active ingredients be applied. If necessary, others can Plant protection or pesticides, such as Example acaricides or fungicides, depending on the desired Purpose to be added.

The compounds of the invention are further distinguished from a general herbicidal effect. In higher application rates (<5 kg / ha) they are suitable for total weed control. However, their use in application quantities is more interesting from approx. 0.1 to 5.0 kg / ha as selective post-emergence herbicides in cultures. They inhibit or prevent the emergence of monocotyledonous and dicotyledonous weeds.

The compounds of the invention can e.g. B. against species from the following plant species:

Dicotyledon weeds of the genera: Abutilon, Chrysanthemum, Brassica, Helianthus, Mentha, Sinapis, Lepidium, Galium, Stellaria, Anthemis, Chenopodium, Atriplex, Senecio,  Portulaca, Ipomoea, Matricaria, Galinsoga, Urtica, Amaranthus, Convolvulus, Polygonum, Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solanum, Rorippa, Lamium, Veronica, Datura, Viola, Centaurea and Galeopsis.

Monocot weeds of the genera: Avena, Alopecurus, Echinochloa, Setaria, Panicum, Digitaria, Poa, Eleusine, Brachiaria, Lolium, Bromus, Cyperus, Agropyron, Sagittaria, Cynodon, Monochoria, Fimbristylis, Eleocharis, Ischaemum and apera.

The compounds can be found in main agricultural crops such as cotton, soy, rice, corn, wheat, barley, Oats, rye, sorghum and sugar cane are applied.

However, the use of the compounds according to the invention is not only on the weed genera and Cultivated plants limited, but extends in the same Also in other plants.

The compounds of the invention are suitable depending from concentration to total weed control, e.g. B. on industrial and track systems and on paths and squares.

Weed control compounds can also be used in Permanent crops, e.g. B. forest, ornamental trees, fruit, wine, Citrus, nut, banana, coffee, tea, rubber, oil palm, Cocoa, berry fruit and hop plants can be used.

In addition, the compounds of the invention have growth regulatory in correspondingly low application rates Properties in crops by intervene regulating the plant's own metabolism, without killing the plants so that they can e.g. B. used  can be used for general control and inhibition of unwanted vegetative growth and to prevent the Storage.

The application rates used in practice can be in fluctuate over a larger area. They essentially hang depends on the type of effect you want. Generally lie the application rates between 0.01 and 5 kg of active ingredient per Hectares of soil, preferably between 0.1 and 0.5 kg per hectare

Depending on the goal, the application can be pre- and post-emergence respectively. The connections can also be worked into the soil will.

If a broadening of the spectrum of activity or Other people may want to increase effectiveness Herbicides can be added. For example, are suitable as herbicidally active mixture partner active ingredients which in Weed Abstracts, Vol .: 34, No. 3, 1985, under the title "List of common names and abbreviations employed for currently used herbicides and plant growth regulators in Weed Abstracts ".

Are the active ingredients for post-emergence use for certain Crop plants less tolerable, can by certain Application techniques (post-directed, lay-by) full tolerance can be achieved in which the leaves of the Crop plants should not be hit while the active ingredients on the leaves below weeds growing or get onto the uncovered floor area.  

Some of the new active ingredients are also suitable for Desiccation and defoliation.

In addition, non-phytotoxic agents can also be added with herbicides and / or growth regulators result in a synergistic increase in effectiveness can, such as wetting agents, emulsifiers, solvents and oily additives.

Phospholipids can also be used as mixing partners such as those from the group phosphatidylcholine, the hydrogenated phosphatidylcholines, phosphatidylethanolamine, the N-acyl-phosphatidylethanolamines, Phosphatidylinositol, Phosphatidylserine, Lysolecithin and Phosphatidylglycerol.

The active compounds according to the invention are expediently in the form of preparations such as powders, sprinkling agents, granules or solutions with the addition of liquid and / or solid carriers or diluents and if necessary, wetting agents and / or adhesives are used.

Suitable liquid carriers are, for example, water, Methanol, ethanol, dimethylformamide or dimethyl sulfoxide. Mineral soils such as are suitable as solid carriers Example Tonsil, silica gel, talc or kaolin.

The following can be mentioned for surface-active substances: cationic, anionic and non-ionic surfactants such as Calcium lignin sulfonate, polyethylene alkylphenyl ether, Naphthalenesulfonic acids and their salts, formaldehyde condensates, Fatty alcohol sulfates and substituted benzenesulfonic acids and their salts.  

The proportion of the active ingredient (s) in the different Preparations can vary within wide limits. For example the agents contain about 10 to 90 percent by weight Active ingredients, about 90 to 10 percent by weight liquid or solid carriers and optionally up to 40 percent by weight surfactants.

The funds can be spent in the usual way, for example with water as a carrier in spray liquor quantities of about 100 to 1000 l / ha.

An application of the funds in so-called "low-volume" or "Ultra-low-volume processes" is just as possible as theirs Application in the form of so-called microgranules.

The preparation of these preparations can be done in a manner known per se Way, for example by grinding or mixing processes, be performed. If desired, the Individual components are only mixed shortly before they are used like, for example, in the so-called tank mix process is carried out in practice.

For the preparation of the preparations, for example Components used in the following amount:

A. wettable powder

a)

40% by weight of active ingredient 25% by weight of clay minerals 20 weight percent powdered silica 10% by weight calcium salt of lignin sulfonic acid 5 weight percent surfactants the base of a mixture of the calcium salt Lignin sulfonic acid with alkylphenol polyglycol ethers

b)

80 percent by weight of active ingredient 15% by weight kaolin 5 weight percent surfactants on the Base of the sodium salt of N- Methyl-N-oleyl taurins and des Calcium salt of lignin sulfonic acid

c)

25 percent by weight of active ingredient 60% by weight kaolin 10 weight percent powdered silica 5 weight percent surfactants on the Base of the sodium salt of N-methyl N-oleyl-taurine and the calcium salt lignin sulfonic acid

B. Paste

45% by weight of active ingredient 5% by weight sodium aluminum silicate 15 percent by weight cetyl polyglycol ether with 8 moles Ethylene oxide 2% by weight spindle oil 10% by weight polyethylene glycol 23 parts of water

C. Emulsion concentrate

25 percent by weight of active ingredient 15% by weight cyclohexanone 55% by weight xylene 5% by weight mixture of nonylphenyl polyoxyethylene or calcium dodecylbenzenesulfonate

The following examples explain the production of the compounds of the invention.

Example 1 (process variant A 3,4-dichlorobenzoic acid- (1-cyano-2,2,2-trifluoro-1-trifluoromethylethyl) - amid

83 mmol of 3,4-dichlorobenzoic acid (2,2,2-trifluoro-1- trifluoromethylethylidene) -amide in 30 ml of toluene and added then with 9.4 g (100 mmol) of trimethylsilyl cyanide. It is stirred for 12 hours at 80 ° C. Then the fleeting Components distilled off. The residue is dissolved in 300 ml of ether taken up and shaken with 180 ml of 0.05N hydrochloric acid for 1 hour. It is neutralized with sodium hydrogen carbonate Solution. The organic phase is separated off with water washed and dried with magnesium sulfate. After distilling off the volatile components are made from chloroform / Recrystallized hexane.

Yield: 19.5 g = 64% (of theory) Mp: 121-122oC

Example 2 (process variant B) Benzoic acid- (1-cyano-2,2,2-trifluoro-1-trifluoromethylethyl) - amid

2.69 g (10 mmol) benzoic acid- (2,2,2-trifluoro-1-trifluoromethylethylidene) - amide with 4.05 g (150 mmol) of hydrogen cyanide 6 hours at room temperature in the containment tube implemented. The excess hydrocyanic acid is distilled off and the residue was recrystallized from chloroform / hexane.

Yield: 2.72 g = 92% (of theory) Mp: 104-106 ° C  

Example 3 (process variant C) 4-chlorobenzoic acid- (1-cyano-2,2,2-trifluoro-1-trifluoromethylethyl) - amid

5.8 g (0.089 mol) of potassium cyanide are suspended in 40 ml of ether and then dropwise 20 g (0.066 mol) of 4-chlorobenzoic acid (2,2,2-trifluoro-1-trifluoromethylethylidene) amide slowly. The mixture is stirred at room temperature for 5 hours and then shaken 1 hour with 50 ml of 2N hydrochloric acid. You neutralize with Sodium bicarbonate solution, separates the organic phase and shake the aqueous phase three times with 50 ml of ether.

The combined organic phases are washed with water and dried with magnesium sulfate. After distilling off the solvent is recrystallized from chloroform / hexane.

Yield: 16.9 g = 77% (of theory) Mp .: 129-130 ° C.

The following compounds are analogous to Example 1 produced:

The following examples serve to explain the possible applications of the compounds of the invention in the form of the above-mentioned preparations.

Application example I Killing cockroach (Plutella xylostella)

The compounds of the invention were as aqueous Suspension with an active ingredient concentration of 0.0064% used. With this preparation, cauliflower leaves were (Brassica oleracea var. Botrytis) in polystyrene petri dishes sprayed with 4 mg spray liquor / cm². After drying the spray pads were in each petri dish 10 cabbage cockroaches (Plutella xylostella) counted and for 2 days in the closed petri dishes exposed feed exposed. Criterion for the impact assessment was the caterpillar mortality in% after 2 days. It was found that the compounds according to the examples in the specified experimental setup 1, 3, 11, 13, 14, 20, 24, 25, 39 and 45-47 have a 90-100% mortality effect showed.

Application example II Killing effect on larvae (L 3) of the Mexican Bean beetle (Epilachna varivestis)

The compounds of the invention were as aqueous Suspension with the active ingredient concentration of 0.0064% used. Bush bean plants were used in this preparation (Phaseolus vulgaris) immersed in the primary leaf stage. Per  A total of two plant stems were used in the test four primary leaves in plastic cups filled with water adjusted and caged in plexiglass cylinders. Then five larvae of the Mexican bean beetle were born (Epilachna varivestis) in the third larval stage counted in the plexiglass cylinder and for three days held in it. Criterion for the impact assessment was the mortality of the larvae after 3 days.

The test arrangement showed that the connections according to Examples 1, 3, 11, 13, 14, 20, 24, 25, 34, 37, 39 and 45-47 showed a 90-100% mortality effect.

Application example III

In the greenhouse, those listed in the table were Plants with both before and after emergence Compounds according to the invention in an application rate of 3.0 kg of active ingredient / ha treated. The connections were too this purpose as suspensions or emulsions with 500 l Water / ha evenly on Brassica sp. and Solanum sp. as Sprayed test plant. 3 weeks after treatment the treatment result is rated according to the following scheme:

0 = no effect
1 = little effect or weak inhibition of plant growth
2 = medium effect or inhibition of plant growth
3 = total growth inhibition
4 = total destruction of the plants

As can be seen from the table, was usually the test plants were destroyed.

Claims (7)

1. Acylaminonitriles of the general formula I in which R is hydrogen, a C _1-12 alkyl, C _1-12 optionally substituted one or more times, identically or differently, by halogen, C _1-4 alkoxy, C _1-4 alkylthio, C _1-4 dialkylamino -Alkenyl or C _1-12 alkynyl radical, a C _3-8 cycloalkyl radical, one optionally one or more times, identically or differently, with halogen, C _1-4 alkyl, C _1-4 alkoxy, C _1-4 -Alkylthio, C _1-4 -dialkylamino, C _1-6 -alkoxycarbonyl, carboxy, trifluoromethyl, trifluoromethoxy, difluoromethoxy, nitro, cyano-substituted phenyl, naphthyl, pyridyl, thienyl, furyl, phenyl-C _1-4 -alkyl-, phenylvinyl-, phenoxy-C _1-4 -alkyl-, phenylthio-C _1-4 -alkyl-, phenylamino-C _1-4 -alkyl- or phenoxy, one or more, optionally the same or different with Halogen, C _1-4 alkoxy, C _1-4 alkylthio substituted C _1-12 dialkylamino, C _1-12 alkoxy, C _1-12 alkenoxy, C _1-12 alkynyloxy, C _{3- 8 means} cycloalkoxy or C _1-12 alkylthio. 2. A process for the preparation of compounds of the general formula I, characterized in that a 4,4-bis (trifluoromethyl) -1-oxa-3-azabuta-1,3-diene of the formula II whereinR has the meaning given in formula I, either

• (A) reacted with trimethylsilyl cyanide and then the 4,4-bis (trifluoromethyl) -2-oxazoline-5-trimethylsilylimine of the formula III obtained as an intermediate whereinR has the meaning given in formula I, hydrolyzed or
• (B) directly reacted with hydrogen cyanide or
• (C) reacted with alkali metal salts of hydrocyanic acid and then hydrolyzed.

3. Biocidal agent, characterized by a content of at least one compound according to claim 1. 4. Biocidal agents according to claim 3 with herbicidal activity. 5. Biocidal agents according to claim 3 with insecticidal activity. 6. Biocidal agents according to claim 3 with acaricidal activity. 7. Composition according to claims 3-6 in admixture with carrier and / or auxiliary substances.