DD267414A5 - AKARICIDAL AGENTS - Google Patents

Abstract

The invention relates to acaricidal agents containing as active ingredient azomethines of 2,3-Diaminomaleinsaeurenitrils. The object of the invention is to provide new agents which have an acaricidal action. According to the invention, the object is achieved by providing means which contain azomethines of 2,3-diaminomaleic acid nitrile of the formula (I), wherein the substituents which have the meaning given in the description, besides conventional extenders and / or surface-active agents. Formula (I)

Description

Field of application of the invention

The invention relates to acaricidal agents based on partially known azomethines (= Schiff bases) of 2,3-Diaminomaleinsäurenitrils.

The invention further relates to novel azomethines (= Schiff bases) of 2,3-Diaminomaleinsäurenitrils and a process for their preparation.

Characteristic of the known state of the art

It is already known that azomethines of 2,3-diaminomalic acid nitrile have bactericidal, viricidal and germicidal activities, such as the amino-toluylidene aminomalonic acid nitrile (see, for example, JP 51151525).

Furthermore, from the publication by R. W.Gabland et al. J.Org.Chem.39, no. 16 (1974), p.2341 ff. Azomethine of 2,3-Diaminomaleinsäurenitrils known which contain certain chloro-substituted phenyl groups (amino-2-chlorotoluylidenamino-maleinsäurenitril and Amino ^ e-Dichlortoluyltdenaminomaleinsäurenitril).

However, to date, nothing has become known about the effectiveness of the aforementioned class of compounds against animal pests, in particular against spider mites.

Object of the invention

With the invention acaricidal agents are provided which contain as active ingredient azomethines of 2,3-Diaminomaleinsäurenitrils. Such an effect has not yet become known from the class of these azomethines.

Explanation of the essence of the invention

The object of the invention is to provide new agents which have an acaricidal action.

It has now been found that the partially known azomethines of 2,3-diamino-maleic acid nitrile of the formula

(D,

in which

X is halogen, haloalkyl or CN, R ¹ , R ² , R ³ and R ^{4 may be the} same or different

is hydrogen, optionally substituted alkyl, optionally substituted alkoxy, halogen, CN, NO ₂ , optionally substituted dialkylamino, alkoxycarbonyl, optionally substituted alkylthio, optionally substituted alkylthionyl, optionally substituted alkylsulfonyl, OH, SH, NH ₂ , have very strong acaricidal properties ,

The partially known azomethines of 2,3-diaminomaleonitrile of the formula (I)

NC NH ₂

in which

X is halogen, haloalkyl or CN, R ¹ , R ² , R ³ and R ^{4 may be the} same or different

is hydrogen, optionally substituted alkyl, optionally substituted alkoxy, halogen, CN, NO ₂ , optionally substituted dialkylamino, alkoxycarbonyl, optionally substituted alkylthio, optionally substituted alkylthionyl, optionally substituted alkylsulfonyl, OH, SH, NH ₂ , obtained when

2,3-diamino-maleic acid nitrile ("DAMN") of the formula

NC _m NH ₂

NC NH ₂

in molar amounts in a suitable diluent with an aldehyde of the formula

• ЧЗ- С г

С-C > -R ² (III) _f

R ⁴ R ³

in which X, R ¹ , R ² , R ³ and R ^{4 have} the abovementioned meaning, is reacted.

Surprisingly, the partially known azomethines of the formula (I) have an acaricidal activity. Such an effect has not yet become known from the class of azomethines Diaminomaleinsäurenitrils. The use of the compounds of the formula (I) as acaricides thus represents an enrichment of the prior art. The compounds of the general formula (I) may be present in the stereoisomeric cis and / or trans forms, e.g. B.

NC NH ₂ H ₂ N CN

R ¹ or (IXR ¹

NC N = CH-C VP ^{2 NC N =}

I · I "

Preferably, however, the compounds are in the cis form (G).

The azomethines are generally defined by the formula (I).

In the formula (I), X is preferably fluorine, chlorine, bromine, iodine, CF ₃ or CN.

In the radicals R ¹ , R ² , R ³ and R ⁴ as substituents for alkyl, alkoxy, dialkylamino, alkylthio, alkylthionyl, alkylsulfonyl are preferably: halogen, in particular fluorine, chlorine and bromine and OH, NH ₂ .

Preference is given to using compounds of the formula (I) in which X and R "may be identical or different and represent fluorine, chlorine, bromine, iodine, CF 3 or CN, R ¹ , R ² and R ^{3 may be} identical or different and denote Hydrogen, AlkyKd-Ci), haloalkyKCi-CJ, AlkOXy (Ci-C ₄ ), haloalkoxy (C, -C ₄ ), halogen, CN, NO ₂ , DialkyKCi-CJamino, alkoxy (C, -C ") carbonyl, alkyl are _(Cr-C4) thio alkyl (C, -C ₄₎ thionyl, dihaloalkyl _(Ci-C4) amino, AlkyK ^ -CJsulfonyl, OH, SH, NH _2.

Particular preference is given to using compounds of the formula la NC NH ₂

NC N = C

in which X 'and R ^{1 may be} identical or different and are fluorine, chlorine, bromine, iodine or CF ₃ and R "is hydrogen, chlorine, bromine, iodine, cyano, nitro, methyl, ethyl, η and Propyl, n-, i-, s- and t-butyl, methoxy, ethoxy, methoxycarbonyl, ethoxycarbonyl, trifluoromethyl, trichloromethyl, pentafluoroethyl, trifluoroethyl, trifluoromethylsulfone, trifluoromethoxy, trichloromethoxy, pentafluoroethoxy, dimethylamino, diethylamino, di-.beta.-chloroethylamino, di -β-hydroxyethylamino.

Very particular preference is given to using compounds of the formula I b

NC NH ₂

NC N = CH

(Ib)

in which X "and R ^{1 may be} identical or different and are chlorine or bromine and R"'is chlorine, bromine, iodine, hydrogen, cyano, nitro, methyl, ethyl, η- and i-propyl, methoxy, ethoxy, Methoxycarbonyl, ethoxycarbonyl, trifluoromethyl, trichloromethyl, dimethylamino, diethylamino, trifluoromethylsulfone.

Very particular preference is given to using compounds of the formula Ic

NC

NC

NH

N = CH

in which X "'and R ^{1 may be} identical or different and represent chlorine or bromine, and R""is hydrogen, chlorine, bromine, methyl, cyano, trichloromethyl, trifluoromethyl, methoxy, trifluoromethoxy, trichloromethoxy or trifluoromethylsulfone.

Exceptionally preferred compounds of the general formula Id

NC NH ₂

NC N = CH

(Id)

in which R ¹ "is chlorine or bromine and R""is hydrogen, chlorine, methyl, trichloromethyl, methoxy, trichloromethoxy, trifluoromethoxy.

Exceptionally preferred is the compound of formula

NC NH ₂

NC N = CH

listed.

Specifically, in addition to the compounds mentioned in the preparation examples, the following azomethines of the general formula (I) may be mentioned:

NC

NH

N = CH '

R ¹

(I)

R ⁴

br H H H br Cl CH ₃ H H Cl Cl C ₂ H ₅ H H CH ₃ Cl CH ₃ H H CH ₃ br H br H H br H H br H Cl H H H br Cl H C ₂ H ₅ H CH ₃ Cl H H H C ₂ H ₆ CF ₃ H H H Cl CF ₃ H H H CF ₃ Cl H F H Cl

The present invention also relates to novel azomethines of 2,3-diaminomalic acid nitrile of the formula NC NH ₂

NC

X * R ¹ '

in which

X * is halogen, haloalkyl or CN, R ", R ^r , R ³ 'and R ⁴ ' may be the same or different and is hydrogen, optionally substituted alkyl, optionally substituted alkoxy, halogen, CN, NO ₂ , optionally substituted Dialkylamino, alkoxycarbonyl, optionally substituted alkylthio, optionally substituted alkylthionyl, optionally substituted alkylsulfonyl, OH, SH, NH ₂ , with the remainder

may not stand for 2-chlorophenyl and not for 2,6-dichlorophenyl. The new compounds of the formula

NC NH ₂

X * R ^]

NC N = C

З ¹

wherein X *, R ^1, R ² ', R ³ and R ⁴ have the abovementioned meaning, are obtained when 2,3-diaminomaleic acid nitrile ( "DAMN") of the formula

NC NH ₂

NC NH ₂

in molar amounts in a suitable diluent with an aldehyde of the formula

in which X *, R ¹ , R ² , R ³ and R ⁴ 'have the abovementioned meaning, is reacted.

Preference is given to compounds of the formula (Γ)

in which

X * represents chlorine, fluorine, bromine, iodine, CF ₃ or CN,

R ⁴ 'is hydrogen, chlorine, fluorine, bromine, iodine, CF ₃ or CN,

R ¹ ', R ² and R ^{3 may be the} same or different and represent hydrogen, alkyl (Ci-C ₄ ), haloalkyl (

Haloalkoxy (C, -C _4), halogen, CN, NO _2, dialkyl (C ₁ -C ₄₎ amino, alkoxy (Ci-C ₄₎ carbonyl, alkyl _(Ci-C4) thio, alkyl ( Ci-C ₄ ) thionyl, dihaloalkyl (C ₁ -C ₄ ) amino, AlkyKCi-CJsulfonyl, OH, SH, NH ₂ , where the rest

may not stand for 2,6-dichlorophenyl and 2-chlorophenyl.

If, for example, 2,3-diaminomaleonitrile (DAMN) and 2,4-dichlorobenzaldehyde are used as starting materials, the preparation process according to the invention can be represented as follows:

NH-NH-

NC NH ₂

NC

N = C

The aldehydes required for carrying out the process for the preparation of the compounds (I) or (II) starting materials are generally defined by the formulas (III) and (IH '), respectively.

O. Bayer, in Houben-Weyl, Vol. VII / 1, pp. 16-36 (1954).

The further starting compound 2,3-Diaminomaleinsäurenitril (II) is also known from the literature and commercially available.

As diluents for carrying out the process for the preparation of compounds (I) or (Γ) are preferably polar organic solvents in question, such as. As alcohols (especially methanol, ethanol, propanol [n and i]).

Dimethylformamide (DMF), dimethyl sulfoxide (DMSO), hexemethylphosphoric triamide (HMPT), acetonitrile.

The reaction temperature is generally in the range between about 0 ° C to a maximum of the boiling point of the respective

Solvent, in particular, the reaction at temperatures of about 20 to about 100 ⁰ C is performed.

The reaction is preferably carried out at atmospheric pressure.

For carrying out the process for the preparation of the compounds (I) or (Γ), preferably equimolar amounts of the reactants (II) and (III) or (ΙΙΓ) are reacted with one another. But it can also be a slight excess of either

Reactants are used.

In a preferred embodiment, the two reactants are added at room temperature in the diluent

together and then heated to reflux.

The workup is carried out by conventional methods, after cooling, the reaction product is preferably filtered off with suction and worked up by methods known per se.

The active ingredients are suitable for good plant tolerance and favorable toxicity to warm-blooded animals for controlling animal pests, in particular mites (acarina), which occur in agriculture, in forests, in the protection of stored products and in the hygiene sector. They are against normally sensitive and resistant species as well as against all or individual

Development stages effective. The above mentioned pests include:

From the order of Acarina z. Acarus siro, Argas spp., Ornithodoros spp., Dermanyssus gallinae, Eriophyes ribis,

Phyllocoptruta oleivora, Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalomma spp., Ixodes spp., Psoroptes spp., Chorioptes spp., Sarcoptes spp., Tarsonemus spp., Bryobia praetiosa, Panonychus spp., Tetranychus spp.

The active ingredients (I) and (Γ) not only act against plant, hygiene and storage pests, but also on the

Veterinary sector against animal parasites (ectoparasites) such as ticks, leather ticks, mange mites,

Mites.

They are effective against normal-sensitive and resistant species and strains, as well as against all parasitic and non-parasitic stages of ectoparasite development.

The active compounds (I) or (ff) are distinguished by a high acaricidal activity. They can be used with particularly good success against plant-damaging mites, such as against the common spider mite (Tetranychus urticae).

In addition, the compounds of formulas (I) and (Γ) still have a fungicidal activity.

The active compounds can be converted into the customary formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, active substance-impregnated natural and synthetic substances, microencapsulations in polymeric substances and in seed coating compositions, furthermore in formulations with fuel assemblies, such as smoking cartridges, doses, spirals, etc., as well as ULV KaIt and warm mist formulations.

These formulations are prepared in a known manner, for. Example, by mixing the active compounds with extenders, that is liquid solvents, liquefied gases under pressure and / or solid carriers, optionally with the use of surfactants, emulsifiers and / or dispersants and / or foam-forming agents. In the case of using water as an extender z. As well as organic solvents can be used as auxiliary solvent. Suitable liquid solvents are essentially: aromatics such as xylene, Toluol'oder alkylnaphthalenes, chlorinated aromatic or chlorinated aliphatic hydrocarbons such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffins, eg. For example, petroleum fractions, alcohols such as butanol or glycol and their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, and water; with liquefied gaseous extenders or carriers are meant liquids which are gaseous at normal temperature and under normal pressure, eg. B. aerosol propellants, such as halogenated hydrocarbons as well as butane, propane, nitrogen and carbon dioxide; As solid carriers are suitable: z. Natural minerals such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals such as fumed silica, alumina and silicates; As solid carriers for granules are: z. B. crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules of inorganic and organic flours and granules of organic material such as sawdust, coconut shells, corncobs and tobacco stalks; as emulsifier and / or foaming agent are: z. Nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. B. Alkylarylpolyglykol ethers, alkylsulfonates, alkyl sulfates, arylsulfonates and protein hydrolysates; suitable dispersants are: e.g. Lignin-sulphite liquors and methylcellulose.

Adhesives such as carboxymethyl cellulose, natural and synthetic powdery, granular or latex polymers may be used in the formulations, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, as well as natural phospholipids such as cephalins and lecithins, and synthetic phospholipids. Other additives may be mineral and vegetable oils.

It can dyes such as inorganic pigments, eg. For example, iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azo and Metallphthalocyaninfarbstoffe and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc can be used.

The formulations generally contain between 0.1 and 95% by weight of active compound, preferably between 0.5 and 90%. The active compounds (I) or (I'J may be present in their commercially available formulations and in the formulations prepared from these formulations in admixture with other active ingredients, such as insecticides, attractants, sterilants, acaricides, nematicides or fungicides, insecticides, for example, include phosphoric acid esters , Carbamates, carboxylic acid esters, chlorinated hydrocarbons, phenylureas, substances produced by microorganisms, etc.

The active compounds (I) or (II) can furthermore be present in their commercial formulations and in the formulations prepared from these formulations in admixture with synergists. Synergists are compounds which increase the effect of the active ingredients without the added synergist itself having to be active.

The active substance content of the application forms prepared from the commercial formulations can vary within wide ranges. The active ingredient concentration of the application forms may be from 0.0000001 to 95% by weight of active ingredient, preferably between 0.0001 and 1% by weight. The application is done in a custom forms adapted to the application.

The active substances which can be used according to the invention are also suitable for controlling mites, ticks, etc., in the field of livestock and livestock breeding, wherein better control of the pests results, e.g. Higher milk yields, higher weight, better animal coat, longer life etc. can be achieved.

The use of the active ingredients according to the invention is carried out in this field in a known manner such as by oral administration in the form of, for example, tablets, capsules, potions, granules, by dermal or external application in the form of, for example, diving (dipping), spraying (spraying), pouring (pour-on and spot-on) and powdering, as well as by parenteral application in the form of, for example, injection, and further by the feed-through procedure. In addition, an application as a shaped body (collar, ear tag) is possible.

EXAMPLES Production Examples Example 1 (new compound)

NC NH

10.8 g of 2,3-diamino-maleinsäurenitrii be heated in 100 ml of ethanol with 17.5g of 2,4-dichlorobenzaldehyde to reflux. To

The solution is allowed to cool for 3 hours and the precipitate is filtered off. This gives 25.7 g (= 97% of theory) of the compound described above. Melting point: 228 ^° C. (with decomposition)

Example 2

NC

NC

(Substance without indication of a biological activity known from J. Org. Chem. 39, No. 16, 2344 [1974].) In 10OmI acetonitrile is brought to a mixture of 10.8 g of 2,3-Diaminomaleinsäurenitril and 17.5 g of 2.6 Dichlorobenzaldehyde to boiling. Thin-layer chromatography indicates the end of the reaction after 4 hours. After cooling, 24.2 g (91% of theory) of the title compound are filtered off with suction. The substance (yellow-green needles) melts at 191 ^° C. In analogy to the abovementioned examples, the following new compounds were obtained:

NC NH ₂

NC HC

Hal R ¹

Ex. shark R ¹ R ² R ³ R ⁴ melting point No. Cl H CF ₃ H H oderlR data 3 Cl H H H H 189 4 Cl H Cl H Cl 190 (dec.) 5 Cl Cl CF ₃ H Cl 234 (dec.) 6 gl H COOCH ₃ H CL 198 (dec.) 7 Cl CF ₃ Cl H H 179 8th br H br H br 113 9 Cl H br H Cl 304 10 Cl H Cl H br 3400/3300 (NH ₂ ) 11 Cl H CF ₃ H Cl 2280/2230 (CN) 12 Cl H OCF ₃ H Cl 2300/2240 (CN) 13 Cl H OCCI ₃ H Cl 3430/3310 (NH ₂ ) 14 Cl H OCF ₃ H H 3420/3300 (NH ₂ ) 15 Cl H OCCI ₃ H H 2250/2210 (CN) 16 Cl H OCH ₃ H Cl 1605 (C = C) 17 Cl H OCH ₃ H H 3430/3300 (NH ₂ ) 18 Cl H SCF ₃ H Cl 2240/2200 (CN) 19 Cl H SO ₂ CF ₃ H Cl 2250/2210 (CN) 20 Cl H SCF ₃ H H 1320 (-SO ₂ -) 21 Cl H SO ₂ CF ₃ H H 3400/3300 (NH ₂ ) 22 Cl H H H CH ₃ 1315 (-SO ₂ -) 23 Cl H CF ₃ H CH ₃ 1370 (CH ₃ ) 24 Cl H OCF ₃ H CH ₃ 1375 (CH ₃ ) 25 Cl H SO ₂ CF ₃ H CH ₃ 1380 (CH ₃ ) 26 Cl H SCF ₃ H CH ₃ 1375 (CH ₃ ) 27 Cl H H H CN 1375 (CH ₃ ) 28 Cl H CN H Cl 2210/2250/2200 (CN) 29 Cl H H NO ₂ H 2220/2240/2250 (CN) 30 F F F F F 266 31 Cl H H H F 198 32 CF ₃ H H H CF ₃ 184 33 F H H H F 190 34 F CF ₃ F F F 217 35 Cl H Cl OCF ₃ Cl 152 36 163

Example A

Tetranychus test (resistant) Solvent: 7 parts by weight Dimethylformamide Emulsifier: 1 part by weight Alkylaryl polyglycol ether To prepare a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent and the stated amount of emulsifier and the concentrate is diluted with water to the desired concentration.

Bean plants (Phaseolus vulgaris) that are heavily infested with all stages of development of the common spider mite or bean spider mite (Tetranychus urticae) are treated by being dipped into the preparation of active compound of the desired concentration.

After the desired time the kill is determined in%. 100% means that all spider mites have been killed; 0% means that no spider mites have been killed.

In this test, z. For example, the following compounds of Preparation Examples have an excellent activity against Tetranychus urticae (2).

table

(plant-damaging mites)

Tetranychus test

Degree of killing active ingredients Wirkstoffkonz. in% after7 days in%

NC NH ₂

Cl

0.1

Claims (10)

claims: 1. Acaricidal agent, characterized by a content of at least one azomethine of the 2,3-diamino-maleinsäurenitrils the general formula (D in which X is halogen, haloalkyl or CN, R ¹ , R ² , R ³ and R ^{4 may be the} same or different is hydrogen, optionally substituted alkyl, optionally substituted alkoxy, halogen, CN, NO ₂ , optionally substituted dialkylamino, alkoxycarbonyl, optionally substituted alkylthio, optionally substituted alkylthionyl, optionally substituted alkylsulfonyl, OH, SH, NH ₂ , in addition to extenders and / or surface-active means. 2. Acaricidal compositions according to claim 1, characterized in that they contain at least one azomethine of 2,3-Diaminomaleinsäurenitrils of formula (I) in which X and R ^{4 may be the} same or different and for fluorine, chlorine, bromine, iodine, CF ₃ or CN, R ¹ , R ² and R ^{3 may be the} same or different for hydrogen, alkyl (C 1 -C ₄ ), nano-3-coco-butyl-C_H), haloalkoxy (C 1 -C ₄ ), halogen, CN, NO ₂ , dialkyKCT-C-amino, alkoxy-C 1 -C -carbonyl, alkyl (C 1 -C ₄ ) C ₄ ) thio, AlkyKCi-CJthionyl, DihalogenalkyKCr-O-amino, AlkyK ^ -CSulfonyl, OH, SH, NH ₂ stand. 3. Acaricidal agent according to claim 1, characterized by a content of at least one azomethine of 2,3-Diaminomaleinsäurenitrils of the formula (La) in the X 'and R' may be the same or different and are fluorine, chlorine, bromine, iodine or CF ₃ R "is hydrogen, chlorine, bromine, iodine, cyano, nitro, methyl, ethyl, η- and i-propyl, n-, i-, s- and t-butyl, methoxy, ethoxy, methoxycarbonyl, ethoxycarbonyl, trifluoromethyl, trichloromethyl , Pentafluoroethyl, trifluoroethyl, trifluoromethylsulfonyl, trifluoromethoxy, trichloromethoxy, pentafluoroethoxy, dimethylamino, diethylamino, di-.beta.-chloroethylamino, di-.beta.-hydroxyethylamino stands. 4. Acaricidal agent according to claim 1, characterized by a content of at least one azomethine of 2,3-Diaminomaleinsäurenitrils the formula ДІ * (Ib) in the X "and R ¹ 'may be identical or different and represent chlorine or bromine and R ¹¹ ' is chlorine, bromine, iodine, hydrogen, cyano, nitro, methyl, ethyl, η- and i-propyl, methoxy, ethoxy, Methoxycarbonyl, ethoxycarbonyl, trifluoromethyl, trichloromethyl, dimethylamino, diethylamino, trifluoromethylsulfonyl. 5. Acaricidal composition according to claim 1, characterized by a content of at least one azomethine of 2,3-Diaminomaleinsäurenitrils the formula II " (Ic) NC in the X "'and R ^{r may be the} same or different and represent chlorine or bromine, and R "" represents hydrogen, chlorine, bromine, methyl, cyano, trichloromethyl, trifluoromethyl, methoxy, trifluoromethoxy, trichloromethoxy or trifluoromethylsulfonyl. 6. Acaricidal composition according to claim 1, characterized by a content of at least one azomethine of 2,3-Diaminomaleinsäurenitrils the formula (Id) in which R ^{1 is} chlorine or bromine R "'" represents hydrogen, chlorine, methyl, trifluoromethyl, trichloromethyl, methoxy, trichloromethoxy, Trifluoromethoxy stands. 7. Acaricidal agent according to claim 1, characterized by a content of the compound of formula Cl 8. A process for the preparation of acaricidal agents, characterized in that mixing Azomethine of 2,3-Diaminomaleinsäurenitrils of formula (I) with extenders and / or surface-active agents. 9. A method for combating mites (Acarina), characterized in that azomethines of 2,3-Diaminomaleinsäurenitrils of formula (I) is allowed to act on mites and / or their habitat. 10. Use of azomethines of 2,3-Diaminomaleinsäurenitrils of formula (I), characterized in that they are used for controlling mites (Acarina).