DE4304006A1 - Pyrimidylhydrazones - Google Patents

Abstract

Novel pyrimidylhydrazones of the formula <IMAGE> in which R<1> represents hydrogen, methyl, ethyl, n-propyl, isopropyl, fluorine, chlorine, bromine or trifluoromethyl, R<2> represents hydrogen, methyl, ethyl, n-propyl, isopropyl, fluorine, chlorine, bromine or trifluoromethyl, R<3> represents alkyl having 2 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, cycloalkyl having 3 to 8 carbon atoms, phenyl which is substituted by halogen, alkyl having 1 to 6 carbon atoms and/or haloalkyl having 1 to 6 carbon atoms and 1 to 7 halogen atoms, or represents phenylalkyl having 1 to 4 carbon atoms in the alkyl moiety and which is optionally substituted by halogen, alkyl having 1 to 6 carbon atoms and/or haloalkyl having 1 to 6 carbon atoms and 1 to 7 halogen atoms, or represents pyridyl which is substituted by halogen, alkyl having 1 to 6 carbon atoms and/or haloalkyl having 1 to 6 carbon atoms and 1 to 7 halogen atoms, R<4> represents hydrogen or alkyl, R<5> represents hydrogen, alkyl, alkynyl, alkoxy, alkylthio, cycloalkyl or halogen, R<6> represents hydrogen, alkyl, alkoxy, alkylthio, cycloalkyl or halogen, R<7> represents hydrogen, alkyl, alkynyl, alkoxy, alkylthio, cycloalkyl or halogen, and their acid addition salts and metal salt complexes, a process for the preparation of the novel substances, and their use as pesticides.

Description

The present invention relates to new pyrimidylhydra zone, a process for their manufacture and their ver Use as a pesticide.

It has already become known that numerous pyridyl and Pyrimidylhydrazone possess fungicidal properties (see J. Pestic. Sci. 14, 295-300 (1989), BE-PS 561 091, DE-OS 27 44 385 and EP-OS 0 019 450). So can be Example the connections of the formulas

and

use to control phytopathogenic fungi. The Effect of these substances is good, but leaves at low In some cases, application rates leave something to be desired.

There have now been new pyrimidyl hydrazones of the formula

in which,
R ^{1 represents} hydrogen, methyl, ethyl, n-propyl, isopropyl, fluorine, chlorine, bromine or trifluoromethyl,
R ^{2 represents} hydrogen, methyl, ethyl, n-propyl, isopropyl, fluorine, chlorine, bromine or trifluoromethyl,
R ^{3 represents} alkyl having 2 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, cycloalkyl having 3 to 8 carbon atoms, phenyl substituted by halogen, alkyl having 1 to 6 carbon atoms and / or haloalkyl having 1 to 6 carbon atoms and 1 to 7 halogen atoms, for phenols optionally substituted by halogen, alkyl having 1 to 6 carbon atoms and / or haloalkyl having 1 to 6 carbon atoms and 1 to 7 halogen atoms, or substituted by halogen, alkyl having 1 to 6 carbon atoms and / or haloalkyl pyridyl substituted with 1 to 6 carbon atoms and 1 to 7 halogen atoms,
R ^{4 represents} hydrogen or alkyl,
R ^{5 represents} hydrogen, alkyl, alkynyl, alkoxy, alkylthio, cycloalkyl or halogen,
R ^{6 represents} hydrogen, alkyl, alkoxy, alkylthio, cycloalkyl or halogen and
R ^{7 represents} hydrogen, alkyl, alkynyl, alkoxy, alkylthio, cycloalkyl or halogen,
as well as their acid addition salts and metal salt complexes.

The pyrimidyl hydrazones of the formula (I) can depend on the position of the substituents at the C = N- Double bond in the form of geometric isomers (syn / anti). The present invention thus relates probably the individual isomers as well as their mixtures.

Furthermore, it was found that the pyrimidyl hydrazones Formula (I) and their acid addition salts and metal salt complexes when 2-pyridyl ketones of For mel

in which,
R ¹ , R ² and R ^{3 have} the meanings given above, with pyrimidylhydrazines of the formula

in which,
R ⁴ , R ⁵ , R ⁶ and R ^{7 have} the meanings given above,
in the presence of a diluent and, if appropriate, in the presence of a catalyst, and if appropriate adding an acid or a metal salt to the compounds of the formula (I) thus obtained.

Finally it was found that the new Pyrimidylhy drazone of formula (I) and their acid addition salts and metal salt complexes very well as pest control care agents are suitable. They prefer to be as fungicides for combating phytopathogenic fungi and as insecticides in crop protection.

Surprisingly, the fabrics of the invention better fungicidal properties than the comparative substances of the formulas (A) to (I), which constitutes nell similar, known active ingredients of the same we direction.

Formula (I) provides a general definition of the pyrimidyl hydrazones according to the invention.
R ¹ preferably represents hydrogen, methyl, ethyl, n-propyl, isopropyl, fluorine, chlorine, bromine or trifluoromethyl.
R ² preferably represents hydrogen, methyl, ethyl, n-propyl, isopropyl, fluorine, chlorine, bromine or trifluoromethyl.
R ³ preferably represents straight-chain or branched alkyl having 2 to 18 carbon atoms, straight-chain or branched alkenyl having 2 to 18 carbon atoms, cycloalkyl having 3 to 7 carbon atoms, for phenyl which is monosubstituted to trisubstituted in the same manner or differently by fluorine, chlorine, bromine, alkyl having 1 to 4 carbon atoms and / or haloalkyl having 1 to 4 carbon atoms, such as fluorine, chlorine and bromine, and in addition,
R ³ preferably for phenylalkyl having 1 or 2 carbon atoms in the alkyl part, where the phenyl radical can be substituted one to three times, in the same way or differently, by fluorine, chlorine, bromine, alkyl having 1 to 4 carbon atoms and / or halo genalkyl having 1 to 4 Carbon atoms and 1 to 5 halogen atoms, such as fluorine, chlorine and bromine, and furthermore,
R ³ preferably for pyridyl, which is monosubstituted to trisubstituted, identical or different, by fluorine, chlorine, bromine, alkyl having 1 to 4 carbon atoms and / or haloalkyl having 1 to 4 carbon atoms and 1 to 5 halogen atoms, such as fluorine, chlorine and bromine.
R ⁴ preferably represents hydrogen or straight-chain or branched alkyl having 1 to 4 carbon atoms.
R ⁵ preferably represents hydrogen, straight-chain or branched alkyl having 1 to 6 carbon atoms, straight-chain or branched alkynyl having 2 to 6 carbon atoms, straight-chain or branched alkoxy having 1 to 6 carbon atoms, straight-chain or branched alkylthio having 1 to 4 carbon atoms, Cycloalkyl with 3 to 7 carbon atoms, fluorine, chlorine or bromine.
R ⁶ preferably represents hydrogen, straight-chain or branched alkyl having 1 to 6 carbon atoms, straight-chain or branched alkoxy having 1 to 6 carbon atoms, straight-chain or branched alkylthio having 1 to 4 carbon atoms, cycloalkyl having 3 to 7 carbon atoms, fluorine, chlorine or Bromine.
R ⁷ preferably represents hydrogen, straight-chain or branched alkyl having 1 to 6 carbon atoms, straight-chain or branched alkynyl having 2 to 6 carbon atoms, straight-chain or branched alkoxy having 1 to 6 carbon atoms, straight-chain or branched alkylthio having 1 to 4 carbon atoms, Cycloalkyl with 3 to 7 carbon atoms, fluorine, chlorine or bromine.
R ¹ particularly preferably represents hydrogen, methyl, ethyl, n-propyl, isopropyl, fluorine, chlorine, bromine or trifluoromethyl.
R ² particularly preferably represents hydrogen, methyl, ethyl, n-propyl, isopropyl, fluorine, chlorine, bromine or trifluoromethyl.
R ³ particularly preferably represents straight-chain or branched alkyl having 2 to 8, 10, 12, 16 or 18 carbon atoms, straight-chain or branched alkenyl having 2 to 16 carbon atoms, cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, for phenyl which is simple to triple is identical or differently substituted by fluorine, chlorine, bromine, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl and / or haloalkyl having 1 or 2 carbon atoms and 1 to 3 fluorine, chlorine and / or bromine atoms, and furthermore,
R ^{3 is} particularly preferably for phenylalkyl having 1 or 2 carbon atoms in the alkyl part, where the phenyl radical can be substituted once to three times, in the same way or differently, by fluorine, chlorine, bromine, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert. Butyl and / or haloalkyl having 1 or 2 carbon atoms and 1 to 3 fluorine, chlorine and / or bromine atoms, and furthermore,
R ^{3 is} particularly preferably for pyrid-2-yl, pyrid-3-yl and pyrid-4-yl, where each of these radicals is monosubstituted to trisubstituted, identically or differently, by fluorine, chlorine, bromine, methyl, ethyl, n-propyl , Isopropyl, n-butyl, tert-butyl and / or haloalkyl with 1 or 2 carbon atoms and 1 to 3 fluorine, chlorine and / or bromine atoms.
R ⁴ particularly preferably represents hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl or tert-butyl,
R ⁵ particularly preferably represents hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, propargyl, methoxy, ethoxy, methylthio, ethylthio, cyclopropyl, cyclohexyl, cyclopentyl, fluorine, chlorine or bromine.
R ⁶ particularly preferably represents hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, methoxy, ethoxy, methylthio, ethylthio, cyclopropyl, cyclopentyl, cyclohexyl, fluorine, chlorine or bromine.
R ⁷ particularly preferably represents hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, propargyl, methoxy, ethoxy, methylthio, ethylthio, cyclopropyl, cyclohexyl, cyclopentyl, fluorine, chlorine or bromine.

Preferred substances according to the invention are also addition products of acids and those pyrimidylhydrazones of the formula (I) in which R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ^{7 have} the meanings given as preferred.

Acids that can be added include: preferably hydrohalic acids, such as. B. the chlorine hydrochloric acid and hydrobromic acid, in particular hydrochloric acid, also phosphoric acid,  Nitric acid, sulfuric acid, mono- and bifunctional Carboxylic acids and hydroxycarboxylic acids, such as. B. Vinegar acid, maleic acid, succinic acid, fumaric acid, wine acid, citric acid, salicylic acid, sorbic acid and Lactic acid and sulfonic acids, such as. B. p-toluenesul fonic, 1,5-naphthalenedisulfonic acid or camphersul fonic acid, saccharin and thiosaccharin.

In addition, preferred compounds according to the invention are addition products from salts of metals of the II. To IV. Main and of I. and II. And IV. To VIII. In addition to group of the periodic table of the elements and those pyrimidylhydrazones of the formula (I) in which R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ^{7 have} the meanings indicated as preferred.

Here are salts of copper, zinc, manganese, magne sium, tin, iron and nickel especially before moves. Anions of these salts are those in Be that derive from such acids that to lead physiologically compatible addition products. Particularly preferred such acids are in this Connection the hydrohalic acids, such as. B. the Hydrochloric acid and hydrobromic acid, also phosphoric acid, nitric acid and sulfuric acid.

As examples of pyrimidyl hydrazones of the formula (I) are the substances listed in Table 1 below called.  

If (pyrid-2-yl) propyl ketone and (pyrimid-2- yl) hydrazine as starting materials, the course of the method according to the invention by the following formula scheme are illustrated:

Formula (II) provides a general definition of the 2-pyridyl-ketones required as starting materials in the process according to the invention. The radicals R ¹ , R ² and R ³ preferably have those meanings which have already been mentioned as preferred for these substituents in connection with the description of the pyrimidylhydrazones of the formula (I) according to the invention.

The 2-pyridyl ketones of the formula (II) are known or can be manufactured according to known methods len (see BE-PS 561 091 and DE-OS 27 44 385). So get you get 2-pyridyl-ketones of formula (II), if you have 2-cyano pyridines of the formula

in which,
R ¹ and R ^{2 have} the meanings given above, with organometallic compounds of the formula

R ³ -Me (V)

in which,
R ^{3 has} the meaning given above and
Me stands for lithium or MgX, where
X represents chlorine, bromine or iodine,
in the presence of an inert, organic diluent, such as, for example, diethyl ether, at temperatures between -20 ° C. and + 25 ° C. and the intermediate 2-pyridyl-ketimines of the formula

in which,
R ¹ , R ² , R ³ and Me have the meanings given above,
in the presence of an inert, organic diluent, such as, for example, diethyl ether, successively with an aqueous buffer system, such as, for example, an aqueous ammonium chloride solution, and with acid, such as, for example, aqueous hydrochloric acid, at temperatures between -10 ° C. and + 20 ° C implements. The 2-pyridyl-ketones of the formula (II) can be isolated from the resulting mixture by customary methods. In general, the procedure is such that the reaction mixture is extracted with an organic solvent which is not very miscible with water and the solution obtained is distilled, if necessary after drying.

The in the preparation of the 2-pyridyl ketones of the formula (II) according to the above method as reaction components required substances of the formulas (IV) and (V) are known or can be produced using generally known methods put.

Formula (III) provides a general definition of the pyrimidylhydrazines which are further required as starting materials in the process according to the invention. The radicals R ⁴ , R ⁵ , R ⁶ and R ⁷ preferably have those meanings which have already been mentioned as preferred for these substituents in connection with the description of the pyrimidylhydrazones of the formula (I) according to the invention.

The pyrimidylhydrazines of the formula (III) are known or can be done according to generally known methods produce.

As a diluent when performing the the inventive method all the usual inert organic solvents. Preferably alcohols such as methanol, ethanol, n- Propanol, isopropanol, n-butanol and tert-butanol, also nitriles, such as acetonitrile, also aromatic Hydrocarbons such as benzene, toluene and xylene and also halogenated aliphatic hydrocarbons substances such as methylene chloride, chloroform and tetrachlor carbon.

As catalysts come in the implementation of the inventive method all for such implementations gene usual reaction accelerator in question. Preferential Acids such as acetic acid and aqueous are usable Hydrochloric acid.

The reaction temperatures can be carried out of the method according to the invention in a larger Be be varied widely. Generally one works at Temperatures between 0 ° C and 140 ° C, preferably between between 20 ° C and 120 ° C.

When carrying out the method according to the invention one generally works under normal pressure. It is but also possible, with increased or decreased Pressure to work.  

When carrying out the method according to the invention 1 mol of 2-pyridyl ketone of the formula (II) generally 0.8 to 1.2 moles of pyrimidylhydrazine Formula (III) and optionally a small amount a reaction accelerator. The workup takes place according to usual methods. Generally you go in such a way that the reaction mixture is concentrated, the remaining residue with a little with water miscible organic solvent takes up the resulting Clean solution by filtration, then concentrate and den Residue recrystallized or distilled.

The pyrimidyl hydrazones of the formula (I) according to the invention can in acid addition salts or metal salt complexes be transferred.

For the production of acid addition salts of the compounds Those acids are preferred for the formula (I) in question already in connection with the description exercise of the acid addition salts according to the invention as preferred acids were mentioned.

The acid addition salts of the compounds of formula (I) can in a simple manner according to usual salt formation methods, e.g. B. by dissolving a compound of formula (I) in a suitable inert solvent and adding the acid, e.g. B. hydrochloric acid can be obtained and in a known manner, e.g. B. by filtering, iso liert and optionally by washing with an inert organic solvents can be cleaned.  

For the production of metal salt complexes of the compounds The salts of the formula (I) are preferably those of metals in question that are already related the description of the metal salt com plexes were mentioned as preferred metal salts.

The metal salt complexes of the compounds of the formula (I) can be done in a simple manner using customary procedures will hold so z. B. by dissolving the metal salt in Alcohol, e.g. B. ethanol and adding to compounds of Formula (I). One can know metal salt complexes in known Way, e.g. B. by filtering, isolating and given if clean by recrystallization.

The active compounds according to the invention are very suitable as a pesticide. You are preferred as fungicides for combating phytopathogenic fungi and can also be used as insecticides in crop protection.

Fungicides are used in crop protection for fighting Plasmodiophoromycetes, Oomycetes, Chytri diomycetes, zygomycetes, ascomycetes, basidiomycetes, Deuteromycetes.

Some pathogens are exemplary but not limiting of fungal and bacterial diseases that under the generic terms listed above fall, called:

Xanthomonas species, such as Xanthomonas oryzae;
Pseudomonas species, such as Pseudomonas lachrymans,
Erwinia species, such as Erwinia amylovora;
Pythium species, such as Pythium ultimum;
Phytophthora species, such as Phytophthora infestans;
Pseudoperonospora species, such as Pseudoperonospora humuli or Pseudoperonospora cubensis;
Plasmopara species, such as Plasmopara viticola;
Peronospora species, such as Peronospora pisi or P. brassicae;
Erysiphe species, such as Erysiphe graminis;
Sphaerotheca species, such as Sphaerotheca fuliginea;
Podosphaera species, such as Podosphaera leucotricha;
Venturia species, such as Venturia inaequalis;
Pyrenophora species, such as Pyrenophora teres or P. graminea;
(Conidial form: Drechslera, Syn: Helminthosporium);
Cochliobolus species, such as Cochliobolus sativus;
(Conidial form: Drechslera, Syn: Helminthosporium);
Uromyces species, such as Uromyces appendiculatus;
Puccinia species, such as Puccinia recondita;
Tilletia species, such as Tilletia caries;
Ustilago species, such as Ustilago nuda or Ustilago avenae;
Pellicularia species, such as Pellicularia sasakii;
Pyricularia species, such as Pyricularia oryzae;
Fusarium species, such as Fusarium culmorum;
Botrytis species, such as Botrytis cinerea;
Septoria species, such as Septoria nodorum;
Leptosphaeria species, such as Leptosphaeria nodorum;
Cercospora species, such as Cercospora canescens;
Alternaria species, such as Alternaria brassicae;
Pseudocercosporella species, such as Pseudocercosporella herpotrichoides.

The good plant tolerance of the active ingredients in the necessary to combat plant diseases Kon centers allows treatment from above ground Parts of plants, of seedlings and soil.

The active compounds according to the invention are particularly suitable to combat Pyricularia oryzae and Pellicu laria sasakii on rice and to control cereals diseases such as Leptosphaeria nodorum, Cochliobolus sativus, Pyrenophora teres, Pseudocercosporella herpotrichoides, Erysiphe and Fusarium species. Furthermore the substances according to the invention show a very good one Action against Venturia, Sphaerotheca and Botrytis.

The active compounds according to the invention also have a favorable warm-blooded toxicity and are suitable for loading control of animal pests, preferably crops z-damaging arthropods and nematodes. You are against normally sensitive and resistant species as well as against all or individual stages of development. To the above Pests include:

From the order of the Isopoda z. B. Oniscus asellus, Arma dillidium vulgare, Porcellio scaber.

From the order of the Diplopoda z. B. Blaniulus guttulatus.

From the order of the Chilopoda z. B. Geophilus carpopha gus, Scutigera spec.

From the order of the Symphyla z. B. Scutigerella immacu lata.

From the order of the Thysanura z. B. Lepisma saccharina.  

From the order of the Collembola z. B. Onychiurus armatus. From the order of Orthoptera z. B. Blatta orientalis, Periplaneta americana, Leucophaea maderae, Blattella germanica, Acheta domesticus, Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus differentialis, Schistocerca gregaria.

From the order of the Dermaptera z. B. Auricular Forficula ria.

From the order of the Isoptera z. B. Reticulitermes spp. From the order of the Anoplura z. B. Phylloxera vastatrix, Pemphigus spp., Pediculus humanus corporis, Hsematopinus spp., Linognathus spp.

From the order of the Mallophaga z. B. Trichodectes spp., Damalinea spp.

From the order of the Thysanoptera z. B. Hercinothrips femoralis, thrips tabaci.

From the order of Heteroptera z. B. Eurygaster spp., Dysdercus intermedius, Piesma quadrata, Cimex lectula rius, Rhodnius prolixus, Triatoma spp.

From the order of Homoptera z. B. Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Aphis fabae, Doralis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Macrosiphum avenae, Myzus spp., Phorodon humuli, Rhopalosiphum padi, Empoasca spp., Euscelis bilobatus, Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcuu spp. Psylla spp.  

From the order of the Lepidoptera z. B. Pectinophora gossy piella, Bupalus piniarius, Cheimatobia brumata, Litho colletis blancardella, hyponomeuta padella, plutella maculipennis, Malacosoma neustria, Euproctis chrysorr hoea, Lymantria spp. Bucculatrix thurberiella, Phylloc nistis citrella, Agrotis spp., Euxoa spp., Feltia spp., Earias insulana, Heliothis spp., Spodoptera exigua, Mamestra brassicae, Panolis flammea, Prodenia litura, Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella, Pieris spp., Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Galleria mellonella, Tineola bisselliella, Tinea pellionella, Hofmannophila pseudospretella, Cacoecia podana, Capua reticulana, Choristoneura fumiferana, Clysia ambiguella, Homona magnanima, Tortrix viridana.

From the order of the Coleoptera z. B. Anobium punctatum, Rhizopertha dominica, Acanthoscelides obtectus, Acan thoscelides obtectus, Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedon cochleariae, Diabrotica spp., Psylliodes chrysocephala, Epilachna varivestis, Atomaria spp., Oryzaephilus surinamensis, Anthonomus spp., Sitophilus spp., Otiorrhynchus sul catus, Cosmopolites sordidus, Ceuthorrhynchus assimilis, Hypera postica, Dermestes spp., Trogoderma spp., Anthre nus spp., Attagenus spp., Lyctus spp., Meligethes aeneus, Ptinus spp., Niptus hololeucus, Gibbium psylloi des, Tribolium spp., Tenebrio molitor, Agriotes spp., Conoderus spp., Melolontha melolontha, Amphimallon solstitialis, Costelytra zealandica.  

From the order of the Hymenoptera z. B. Diprion spp., Hop locampa spp., Lasius spp., Monomorium pharaonis, Vespa spp.

From the order of the Oiptera z. B. Aedes spp., Anopheles spp., Culex spp., Simulium spp., Drosophila melano gaster, Musca spp., fannia spp., Calliphora erythro cephala, Lucilia spp., Lyperiosa spp., Chrysomyia spp., Cuterebra spp., Gastrophilus spp., Hyppobosca spp., Stomoxys spp., Melophagus spp., Oestrus spp., Hypoderma spp., Dermatobia, Tabanus spp., Tannia spp., Bibio hortulanus, Oscinella frit, Phorbia spp., Pegomyia hyoscyami, ceratitis capitata, dacus oleae, tipula paludosa.

From the order of the Siphonaptera z. B. Xenopsylla cheo pis, Ceratophyllus spp.

From the order of the Arachnida z. B. Scorpio maurus, Latrodectus mactans.

From the order of Acarina z. B. Acarus siro, Argas spp., Otobius spec., Ornithodoros spp., Dermanyssus gallinae, Bdellonyssus spp., Eriophyes ribis, Phyllocop truta oleivora, Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalomma spp., Ixodes spp., Haemaphy salis spp., Dermacentor spp., Psoroptes spp., Chorioptes spp., Sarcoptes spp., Demodex spp., Psorergates spp., Myobia spp., Myocoptee spp., Notoedres spp., Octodectes spp., Varroa spp., Tarsonemus spp., Bryobia praetiosa, Panonychus spp., Tetranychus spp.  

Plant parasitic nemathodes include praty lenchus spp., Radopholus similis, Ditylenchus dipsaci, Tylenchulus semipenetrans, Heterodera spp., Meloidogyne spp., Aphelenchoides spp., Longidorus spp., Xiphinema spp., Trichodorus spp.

The active compounds according to the invention are particularly notable characterized by excellent insecticidal activity. They show when used against leaf and ground insects strong effect for example against horseradish leaf beetle larvae (Phaedon cochleariae), caterpillars of the cabbage cockroach (Plutella maculipennis) and against caterpillars of the American tobacco owl (Heliothis virescens).

The substances according to the invention can be in the usual Formulations are transferred, such as solutions, emulsions NEN, suspensions, powders, foams, pastes, granules, Aerosols, very fine encapsulations in polymeric substances and in coating compositions for seeds, as well as ULV formulations.

These formulations are produced in a known manner provides, e.g. B. by mixing the active ingredients with stretch agents, i.e. liquid solvents, are under pressure liquefied gases and / or solid carrier fen, if necessary using surfaces active agents, i.e. emulsifiers and / or dispersers yawing and / or foaming agents. In the event of the use of water as an extender can, for. B. also organic solvents as auxiliary solvents be used. As liquid solvents come in  essential in question: aromatics, such as xylene, toluene, or Alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, Chlorethylene or methylene chloride, aliphatic carbons Hydrogen, such as cyclohexane or paraffins, e.g. B. petroleum fractions, alcohols, the butanol or glycol as well their ethers and esters, ketones, such as acetone, methylethyl ketone, methyl isobutyl ketone or cyclohexanone, strong polar solvents such as dimethylformamide and dimethyl sulfoxide and water; with liquefied gaseous Excipients or carriers are such liquids keiten meant, which at normal temperature and below Normal pressure are gaseous, e.g. B. aerosol propellants, such as Butane, propane, nitrogen and carbon dioxide; as fixed Carriers come into question: z. B. natural rock flours, such as kaolins, clays, talc, chalk, quartz, Attapulgite, montmorillonite or diatomaceous earth and syn thetic rock powder, such as highly disperse silica, Alumina and silicates; as solid carriers for Granules are possible: B. broken and fractio nated natural rocks such as calcite, marble, pumice, Sepiolite, dolomite and synthetic granules inorganic and organic flours and granules organic material such as sawdust, coconut shells, Corn cobs and tobacco stalks; as an emulsifier and / or Foaming agents are possible: B. not ionogenic and anionic emulsifiers, such as polyoxyethylene Fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. B. Alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates,  Aryl sulfonates and protein hydrolyzates; as a disperser middle come into question: z. B. lignin sulfite and Methyl cellulose.

Adhesives such as carboxy can be used in the formulations methylcelluloee, natural and synthetic powdery, granular or latex-shaped polymers can be used, such as Gum arabic, polyvinyl alcohol, polyvinyl acetate, as well natural phospholipids, such as cephalins and lecithins, and synthetic phospholipids. Other additives can mineral and vegetable oils.

Dyes such as inorganic pigments, e.g. B. Iron oxide, titanium oxide, ferrocyan blue and organic color substances such as alizarin, azo and metal phthalocyanine color substances and trace nutrients such as salts of iron, manganese, Boron, copper, cobalt, molybdenum and zinc are used the.

The formulations generally contain between 0.1 and 95 percent by weight of active ingredient, preferably between 0.5 and 90%.

The active compounds according to the invention can be found in the formulation stances in a mixture with other known active ingredients such as fungicides, insecticides, acaricides and Her bicidal and in mixtures with fertilizers and wax regulators.  

The active ingredients as such, in the form of their formu lations or the application forms prepared from them such as ready-to-use solutions, emulsifiable concentrates, Emulsions, foams, suspensions, wettable powders, pastes, soluble powders, dusts and granules become. The application is done in the usual way, e.g. B. by pouring, spraying, spraying, scattering, ver dusting, foaming, brushing, etc. It is further possible, the active ingredients according to the ultra-low-volume ver drive or apply the drug preparation or inject the active ingredient into the soil yourself. It can also the seeds of the plants are treated.

When using the substances according to the invention, the on wall quantity depending on the type of application in a larger Range can be varied. This is how the active ingredient concentrations are trations in the treatment of parts of plants in the Application forms generally between 1 and 0.0001 % By weight, preferably between 0.5 and 0.001%. In the Seed treatment are generally active ingredient amounts from 0.001 to 50 g per kg of seed, preferably 0.01 to 10 g needed. When treating the soil are effective substance concentrations from 0.00001 to 0.1% by weight preferably from 0.0001 to 0.02%, required at the site of action such.

The production and use of the invention Fabrics are shown in the following examples.

Manufacturing examples example 1

Under a nitrogen atmosphere, a mixture of 2.54 g (0.017 mol) (pyrid-2-yl) -n-propyl-ketone, 80 ml of ethanol, 1.87 g (0.017 mol) of (pyrimid-2-yl) hydrazine and 2 drops Glacial acetic acid heated under reflux for 60 hours. After that the reaction mixture is cooled to room temperature and by stripping off the solvent under reduced pressure Pressure reduced. You take the remaining residue in chloroform, filtered through a mixture of active coal and silica gel and concentrated again. The residue is recrystallized from petroleum ether. You get on this way 3.61 g (88% of theory) of (pyrid-2-yl) -n- propyl-keto- (pyrimid-2-yl) hydrazone in the form of a solid substance from melting point 82 to 89 ° C.

Preparation of the starting substance of the formula

Under a nitrogen atmosphere and with stirring Mixture of 61.7 g (0.6 mol) of n-propyl magnesium chloride in 100 ml of diethyl ether at 0 ° C dropwise with a Solution of 59.44 g (0.57 mol) of 2-cyano-pyridine in 100 ml Diethyl ether added. After the exothermic has subsided The reaction is stirred for a further 3 hours at 25 ° C., then Chilled to 0 ° C and dropwise with 142 ml of one 30% aqueous ammonium chloride solution added. On finally, while stirring, 223 ml of 6 N hydrochloric acid dripped in. After standing at room temperature for 12 hours The reaction mixture is ratur by adding ver thinner, aqueous sodium hydroxide solution made slightly basic and then extracted six times with 200 ml of diethyl ether. The combined organic solutions are over potassium carbonate dried and concentrated under reduced pressure tight. The remaining residue is distilled. Man receives 71.5 g (84% of theory) in this way (Pyrid-2-yl) -n-propyl-ketone in the form of a colorless Oil. 39 to 44 ° C / 0.06 Torr.

According to the previously specified method, the in the following table 2 substances specified in formulas produced.  

According to the method given in Example 1 the substances listed in Table 3 below Formula (II) prepared.

Table 3

Table 3

In the following usage examples, the Compounds of the formula listed below as Comparative substances used:

and

Example A Erysiphe test (barley) / protective

Solvent: 14.8 parts by weight of dimethylformamide,
Emulsifier: 1.2 parts by weight of alkylaryl polyglycol ether.

For the preparation of a suitable preparation of active ingredient mix 1 part by weight of active ingredient with the specified quantities of solvent and emulsifier and dilute that Concentrate with water to the desired concentration.

To test for protective effectiveness, spray jun plants with the active ingredient preparation in the specified level of application. After the spray coating has dried on the plants are covered with spores of Erysiphe graminis f.sp. hordei pollinated.

The plants are grown in a greenhouse at a tem temperature of approx. 20 ° C and a relative humidity 80% to ensure the development of Favor mildew pustules.

Evaluation is carried out 7 days after the inoculation.

In this test, the compound according to the invention shows (I-5) at a rate of 200 g / ha a we efficiency of over 70%, while the efficiency of the Comparative substances (A) to (G) between 0% and 50% lies.  

Example B Leptosphaeria nodorum test (wheat) / protective

Solvent: 14.8 parts by weight of dimethylformamide,
Emulsifier: 1.2 parts by weight of alkylaryl polyglycol ether.

For the preparation of a suitable preparation of active ingredient mix 1 part by weight of active ingredient with the specified quantities of solvent and emulsifier and dilute that Concentrate with water to the desired concentration.

To test for protective effectiveness, young people are sprayed Plants with the active ingredient preparation in the specified Application rate. After the spray coating has dried on the plants with a spore suspension of Leptosphaeria sprayed nodorum. The plants remain for 48 hours 20 ° C and 100% relative humidity in one ink station cabin.

The plants are grown in a greenhouse at a tem temperature of approx. 15 ° C and a relative humidity of approximately 80%.

Evaluation is carried out 10 days after the inoculation.

In this test, the compounds according to the invention show (I-9), (I-17) - (I-19), (I-21), (I-24) and (I-26) in one Application rate of 200 g / ha an efficiency of over 70%, while the efficiency of the comparison substances (A) to (H) is 45% or less.  

Example C Cochliobolus sativus test (barley) / curative

Solvent: 12.4 parts by weight of dimethylformamide,
Emulsifier: 0.6 part by weight of alkylaryl polyglycol ether.

For the preparation of a suitable preparation of active ingredient mix 1 part by weight of active ingredient with the specified quantities of solvent and emulsifier and dilute that Concentrate with water to the desired concentration.

Young plants are used to test curative effectiveness zen with a conidia suspension of Cochliobolus sativus sprayed. The plants remain at 20 ° C and 48 hours 100% rel. Humidity in an incubation cabin. The plants are then sprayed with the active ingredient preparation in the specified application rate.

The plants are grown in a greenhouse at a tem temperature of approx. 20 ° C and a relative humidity of approximately 80%.

Evaluation is carried out 7 days after the inoculation.

In this test, the compound according to the invention shows (I-2) at a rate of 400 g / ha a we degree, while the reference substance has no effect having.  

Example D Pyrenophora teres test (barley) / protective

Solvent: 34 parts by weight of dimethylformamide,
Emulsifier: 6 parts by weight of alkylaryl polyglycol ether.

For the preparation of a suitable preparation of active ingredient mix 1 part by weight of active ingredient with the specified quantities of solvent and emulsifier and dilute that Concentrate with water to the desired concentration.

To test for protective effectiveness, spray jun plants with the active ingredient preparation in the specified level of application. After the spray coating has dried on plants with a conidia suspension of Sprayed Pyrenophora teres. The plants remain 48 Hours at 20 ° C and 100% relative humidity in an incubation cabin.

The plants are grown in a greenhouse at a tem temperature of approx. 20 ° C and a relative humidity of approximately 80%.

Evaluation is carried out 7 days after the inoculation.

In this test, the compounds according to the invention show (I-3), (I-9), (I-17) - (I-19) and (I-26) at one expense amount of 40 g / ha an efficiency of 70% during the efficiency of the reference substance (J) be only 33% wearing.  

Example E Venturia test (apple) / protective

Solvent: 4.7 parts by weight of dimethylformamide,
Emulsifier: 0.3 part by weight of alkylaryl polyglycol ether.

For the preparation of a suitable preparation of active ingredient mix 1 part by weight of active ingredient with the specified quantities of solvent and emulsifier and dilute that Concentrate with water to the desired concentration.

To test for protective efficacy one splashes young plants with the active ingredient preparation up to Dripping wet. After the spray coating has dried on, the Plants with an aqueous conidia suspension of Apple scab pathogen (Venturia inaequalis) inoculated and then remain at 20 ° C and 100% relative air for 1 day humidity in an incubation cabin.

The plants are grown in a greenhouse at 20 ° C and a relative humidity of approx. 70% poses.

Evaluation is carried out 12 days after the inoculation.

In this test, the compounds according to the invention show (I-11) and (I-17) at a concentration of 10 ppm in the spray liquid has an efficiency of over 80%, while the efficiency the comparative substance (C) weni is less than 30%.  

Example F Pyricularia test (rice) / protective

Solvent: 12.5 parts by weight of acetone,
Emulsifier: 0.3 part by weight of alkylaryl polyglycol ether.

For the preparation of a suitable preparation of active ingredient mix 1 part by weight of active ingredient with the specified quantities of solvent and emulsifier and dilute that Concentrate with water to the desired concentration.

To test for protective efficacy one splashes young plants with the active ingredient preparation up to Dripping wet. After the spray coating has dried off the plants with an aqueous spore suspension of Pyricularia oryzae inoculated. Then the Plant in a greenhouse at 100% rel. Humidity activity and 25 ° C.

The evaluation of the Disease.

In this test, the compounds according to the invention show (I-1), (I-2), (I-8), (I-9), (I-11), (I-17) and (I-27) at a concentration of 0.025% in the spray liquid an efficiency of 90% or more during the we degree of comparison substances (A), (B) and (D) only Is 30% or less.  

Example G Plutella test

Solvent: 7 parts by weight of dimethylformamide,
Emulsifier: 1 part by weight of alkylaryl polyglycol ether.

For the preparation of a suitable preparation of active ingredient mix 1 part by weight of active ingredient with the specified quantities of solvent and emulsifier and dilute that Concentrate with water to the desired concentration.

Cabbage leaves (Brassica oleracea) are dipped in the active ingredient preparation of the desired concentration treated and with caterpillars caterpillars (Plutella maculipennis) as long as the leaves are still moist are.

After the desired time, the efficiency in% certainly. 100% means that all caterpillars are killed were; 0% means that no caterpillars have been killed.

In this test, the compounds according to the invention show (I-1), (I-2), (I-11) and (I-13) with an active ingredient con concentration of 0.1% in the active ingredient preparation 100% efficiency.  

Example H Phaedon larval test

Solvent: 7 parts by weight of dimethylformamide,
Emulsifier: 1 part by weight of alkylaryl polyglycol ether.

For the preparation of a suitable preparation of active ingredient mix 1 part by weight of active ingredient with the specified quantities of solvent and emulsifier and dilute that Concentrate with water to the desired concentration.

Cabbage leaves (Brassica oleracea) are dipped in the active ingredient preparation of the desired concentration treated and with horseradish leaf beetle larvae (Phaedon cochleariae) occupied while the leaves are still moist are.

After the desired time, the efficiency in% certainly. 100% means that all beetle larvae were killed; 0% means that no beetle larvae were killed.

In this test, the compounds according to the invention showed (I-1), (I-2) and (I-11) at an active ingredient concentration an efficiency of 0.1% in the active ingredient preparation of 100%.  

Example I Heliothis virescens test

Solvent: 7 parts by weight of dimethylformamide,
Emulsifier: 1 part by weight of alkylaryl polyglycol ether.

For the preparation of a suitable preparation of active ingredient mix 1 part by weight of active ingredient with the specified quantities of solvent and emulsifier and dilute that Concentrate with water to the desired concentration.

Soybean shoots (Glycine max) are obtained by diving into the Active ingredient preparation of the desired concentration treated and with the tobacco bud caterpillar (Heliothis virescens) as long as the leaves are still moist are.

After the desired time, the efficiency in% certainly. 100% means that all caterpillars are killed were; 0% means that no caterpillars have been killed.

In this test, the compound according to the invention shows (I-2) at an active ingredient concentration of 0.1% in the Active ingredient preparation an efficiency of 100%.

Claims (7)

1. Pyrimidyl hydrazones of the formula in which,
R ^{1 represents} hydrogen, methyl, ethyl, n-propyl, isopropyl, fluorine, chlorine, bromine or trifluoromethyl,
R ^{2 represents} hydrogen, methyl, ethyl, n-propyl, isopropyl, fluorine, chlorine, bromine or trifluoromethyl,
R ^{3 represents} alkyl with 2 to 20 carbon atoms, alkenyl with 2 to 20 carbon atoms, cycloalkyl with 3 to 8 carbon atoms, phenyl substituted by halogen, alkyl with 1 to 6 carbon atoms and / or haloalkyl with 1 to 6 carbon atoms and 1 to 7 halogen atoms , for optionally substituted by halogen, alkyl with 1 to 6 carbon atoms and / or haloalkyl with 1 to 6 carbon atoms and 1 to 7 halogen atoms, phenylalkyl with 1 to 4 carbon atoms in the alkyl part or for halogen, alkyl with 1 to 6 carbon atoms and / or Haloalkyl with 1 to 6 carbon atoms and 1 to 7 halogen atoms substituted pyridyl,
R ^{4 represents} hydrogen or alkyl,
R ^{5 represents} hydrogen, alkyl, alkynyl, alkoxy, alkyl thio, cycloalkyl or halogen,
R ^{6 represents} hydrogen, alkyl, alkoxy, alkylthio, cycloalkyl or halogen and
R ^{7 represents} hydrogen, alkyl, alkynyl, alkoxy, alkyl thio, cycloalkyl or halogen,
as well as their acid addition salts and metal salt complexes. 2. pyrimidyl hydrazones of the formula (I) according to claim 1, in which,
R ^{1 represents} hydrogen, methyl, ethyl, n-propyl, isopropyl, fluorine, chlorine, bromine or trifluoromethyl,
R ^{2 represents} hydrogen, methyl, ethyl, n-propyl, isopropyl, fluorine, chlorine, bromine or trifluoromethyl,
R ^{3 represents} straight-chain or branched alkyl having 2 to 18 carbon atoms, straight-chain or branched alkenyl having 2 to 18 carbon atoms, cycloalkyl having 3 to 7 carbon atoms, or phenyl which is mono- to triple, identical or differently substituted by fluorine , Chlorine, bromine, alkyl having 1 to 4 carbon atoms and / or haloalkyl having 1 to 4 carbon atoms, and moreover,
R ^{3 represents} phenylalkyl having 1 or 2 carbon atoms in the alkyl part, where the phenyl radical can be substituted one to three times, in the same way or differently, by fluorine, chlorine, bromine, alkyl having 1 to 4 carbon atoms and / or haloalkyl having 1 to 4 carbon atoms and 1 to 5 halogen atoms, and further,
R ³ stands for pyridyl which is monosubstituted to trisubstituted, identical or different, by fluorine, chlorine, bromine, alkyl having 1 to 4 carbon atoms and / or haloalkyl having 1 to 4 carbon atoms and 1 to 5 halogen atoms,
R ^{4 represents} hydrogen or straight-chain or branched alkyl having 1 to 4 carbon atoms,
R ^{5 represents} hydrogen, straight-chain or branched alkyl having 1 to 6 carbon atoms, straight-chain or branched alkynyl having 2 to 6 carbon atoms, straight-chain or branched alkoxy having 1 to 6 carbon atoms, straight-chain or branched alkylthio having 1 to 4 carbon atoms, cycloalkyl with 3 to 7 carbon atoms, fluorine, chlorine or bromine,
R ^{6 represents} hydrogen, straight-chain or branched alkyl having 1 to 6 carbon atoms, straight-chain or branched alkoxy having 1 to 6 carbon atoms, straight-chain or branched alkylthio having 1 to 4 carbon atoms, cycloalkyl having 3 to 7 carbon atoms, fluorine, chlorine or bromine stands and
R ^{7 represents} hydrogen, straight-chain or branched alkyl having 1 to 6 carbon atoms, straight-chain or branched alkynyl having 2 to 6 carbon atoms, straight-chain or branched alkoxy having 1 to 6 carbon atoms, straight-chain or branched alkylthio having 1 to 4 carbon atoms, cycloalkyl 3 to 7 carbon atoms, fluorine, chlorine or bromine. 3. Process for the preparation of pyrimidylhydrazones of the formula in which
R ^{1 represents} hydrogen, methyl, ethyl, n-propyl, isopropyl, fluorine, chlorine, bromine or trifluoromethyl,
R ^{2 represents} hydrogen, methyl, ethyl, n-propyl, isopropyl, fluorine, chlorine, bromine or trifluoromethyl,
R ^{3 represents} alkyl with 2 to 20 carbon atoms, alkenyl with 2 to 20 carbon atoms, cycloalkyl with 3 to 8 carbon atoms, phenyl substituted by halogen, alkyl with 1 to 6 carbon atoms and / or haloalkyl with 1 to 6 carbon atoms and 1 to 7 halogen atoms , for optionally substituted by halogen, alkyl with 1 to 6 carbon atoms and / or haloalkyl with 1 to 6 carbon atoms and 1 to 7 halogen atoms, phenylalkyl with 1 to 4 carbon atoms in the alkyl part or for halogen, alkyl with 1 to 6 carbon atoms and / or haloalkyl having 1 to 6 carbon atoms and 1 to 7 halogen atoms substituted pyridyl,
R ^{4 represents} hydrogen or alkyl,
R ^{5 represents} hydrogen, alkyl, alkynyl, alkoxy, alkyl thio, cycloalkyl or halogen,
R ^{6 represents} hydrogen, alkyl, alkoxy, alkylthio, cycloalkyl or halogen and
R ^{7 represents} hydrogen, alkyl, alkynyl, alkoxy, alkyl thio, cycloalkyl or halogen,
as well as their acid addition salts and metal salt complexes, characterized in that 2-pyridyl ketones of the formula in which
R ¹ , R ² and R ^{3 have} the meanings given above,
with pyrimidylhydrazines of the formula in which,
R ⁴ , R ⁵ , R ⁶ and R ^{7 have} the meanings given above,
in the presence of a diluent and, if appropriate, in the presence of a catalyst, and optionally then adding an acid or a metal salt to the compounds of the formula (I) thus obtained. 4. Pest control, characterized by contains at least one pyrimidylhydrazone of formula (I) according to claim 1 or on an acid addition salt or metal salt complex of a pyrimi dylhydrazone of formula (I). 5. Use of pyrimidylhydrazones of the formula (I) according to claim 1 or their acid addition Salts and metal salt complexes to combat Pests. 6. Method of combating pests, thereby characterized in that pyrimidyl hydrazones of For mel (I) according to claim 1 or its acid addition Salts or metal salt complexes on the pests and / or their habitat. 7. Process for the manufacture of pest control means, characterized in that pyrimidyl hydrazones of formula (I) according to claim 1 or their Acid addition salts or metal salt complexes with Extenders and / or surfactants mixed.