JP3100150B2 - Nitrated nitrogen-containing heterocyclic compounds - Google Patents

Description

The present invention relates to novel nitrated nitrogen-containing heterocyclic compounds, to a process for their preparation and to their use in pesticides, in particular as insecticides. Things.

Certain pyrimidino-thiazines, such as 7-ethyl-9-nitro-3,4,7,8-tetrahydro- (2H, 6H) -pyrimidino- [4,3-b] -1,3-thiazine, It is already known to have insecticidal properties (US Pat. No. 4,031,
087).

Formula (I) Wherein A represents a straight-chain alkanediyl, Het represents an unsubstituted or substituted pyridyl or an unsubstituted or substituted thiazolyl, and Z represents a linear or branched or represents alkanediyl, or a group -Y -, - Y-a ¹ - or -Y-a ² -Y- represents, wherein Y is unsubstituted or alkyl - represents a substituted cycloalkanediyl A ¹ represents a straight-chain or branched alkanediyl and A ² represents a direct bond or oxygen, sulfur, —NH— or a straight-chain or branched alkanediyl Or group A novel nitrated nitrogen-containing heterocyclic compound of the formula and acid addition salts thereof have now been found.

Further, nitrated nitrogen-containing heterocyclic compounds of formula (I) and acid addition salts thereof can be prepared by reacting with a compound of formula (II) Wherein A and Het have the above-mentioned meaning. The nitromethylene derivatives of formula (I) are optionally reacted with an acid catalyzed, in the presence of at least 2 times the amount of formaldehyde (per mole of compound of formula (II)). In the presence and, optionally, in the presence of a diluent, with a diamine of the formula (III) H ₂ N—Z—NH ₂ (III), wherein Z has the meaning given above, and optionally forming It was also found that the compound was obtained by adding an acid to the compound.

Surprisingly, the nitrated nitrogen-containing heterocyclic compounds of the formula (I) according to the invention are distinguished by excellent activity as insecticides and ectoparasiticides.

The alkanediyl in the definition of A preferably has 2 carbon atoms.
Represents, in particular, 2 or 3 linear alkanediyls, in the definition of A ¹ and A ² alkanediyl preferably has 1 to 4 carbon atoms and in particular 1 or 2 carbon atoms. Represents a straight-chain or branched alkanediyl, and in the definition of Z, it preferably has 1 carbon atom
-18, especially 1-14 and especially 1-12 straight-chain or branched alkanediyl. The following alkanediyls are suitable examples: methanediyl, ethane-1,1- and -1,2-diyl, propane-1,
1-, -1,2-, -2,2- and -1,3-diyl, butane-
1,3-diyl, pentane-1,5-diyl, hexane-1,6
-Diyl, heptane-1,7-diyl, octane-1,8-diyl, nonane-1,9-diyl, decane-1,10-diyl,
Undecane-1,11-diyl, dodecane-1,12-diyl,
Tridecane-1,15-diyl and tetradecane-1,14-
Diyl and their structural isomers.

Cycloalkanediyl has 3 to 7 carbon atoms, especially 4 carbon atoms.
-6 and especially 5 or 6 cycloalkanediyl. Cycloalkanediyl groups are one or more identical or different alkyl groups, preferably having 1 to 4 carbon atoms, such as methyl, ethyl, n- and i-propyl and n-, i-, s- and t-butyl. , May be substituted by

Halogen represents fluorine, chlorine, bromine or iodine, especially chlorine.

In the present invention, A preferably represents a straight-chain alkanediyl having 2 to 4 carbon atoms, and Het represents an unsubstituted or halogen-substituted pyridyl or an unsubstituted or halogen-substituted thiazolyl. , and Z represents a straight-chain or branched alkanediyl having 1 to 18 carbon atoms, or a group ^{-Y -, - Y-a 1} - or -Y-a ² -Y- represents, here Wherein Y represents an unsubstituted or C1-C4 alkyl-substituted cycloalkanediyl having 3-7 carbon atoms, and A ¹ represents a linear or branched C1-C4 alkyl group; A represents an alkanediyl and A ² represents a direct bond, or oxygen, sulfur, —NH— or a straight-chain or branched alkanediyl having 1 to 4 carbon atoms, or a group And compounds of the formula (I) and their acid addition salts.

Particularly preferred compounds of formula (I) are those wherein A represents a straight-chain alkanediyl having 2 to 4 carbon atoms, and Het is And Z represents a straight-chain or branched alkanediyl having 1 to 18 carbon atoms, or a group Wherein R ¹ , R ² , R ³ and R ⁴ independently represent hydrogen,
Or a straight-chain or branched alkyl having ¹ to 4 carbon atoms, A ¹ represents a straight-chain or branched alkanediyl having 1 to 4 carbon atoms, and A ² represents a direct bond. Represents oxygen, sulfur, -NH- or a linear or branched alkanediyl having 1 to 4 carbon atoms, or represents a group Represents

Particularly preferred compounds of formula (I) are those in which A represents ethane-1,2-diyl or propane-1,3-diyl and Het is And Z is methanediyl, ethane-1,2-diyl, propane-
1,3-diyl, propane 1,2-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8 -Jill,
Represents nonane-1,9-diyl, decane-1,10-diyl, undecane-1,11-diyl, dodecane-1,12-diyl, tridecane-1,13-diyl or tetradecane-1,14-diyl Or group Wherein R ¹ , R ² , R ³ and R ⁴ independently represent hydrogen, methyl or ethyl, and A ¹ has methanediyl, ethane-1,1-diyl, ethane-1,2 -Diyl, propane-1,3-diyl or propane-2,2-diyl and A ² represents a direct bond, or oxygen, sulfur, methanediyl, ethane-1,2-diyl or propane-2, Represents 2-diyl or a radical Represents

Addition products of a nitrated nitrogen-containing heterocyclic compound of formula (I) with an acid wherein A, Het and Z have the meanings listed above as being suitable for these substituents are also described in the present invention. Are suitable compounds.

The acids which can be added are preferably hydrohalic acids such as hydrochloric and hydrobromic acids, especially hydrochloric acid, and phosphoric, sulfuric, nitric, acetic, oxalic, malonic, succinic, malic, tartaric acids , Maleic acid, fumaric acid, methanesulfonic acid, benzoic acid, substituted benzoic acids, formic acid, chloroacetic acid, toluenesulfonic acid, benzenesulfonic acid, trichloroacetic acid, phthalic acid, naphthalenesulfonic acid, nicotinic acid, citric acid and ascorbic acid Acids are included.

For example, when 3- (2-chloro-pyridin-5-yl-methyl) -2-nitromethylene-imidazolidine, n-octane-1,8-diamine and formaldehyde are used as starting materials for the process according to the invention. Can be represented by the following reaction formula: Formula (II) provides a general definition of the nitromethylene derivatives used as starting materials in the process according to the invention. In this formula (II), A and Het preferably represent groups which have already been mentioned as suitable for A and Het with regard to the definition of the substances of the formula (I) according to the invention.

The compounds of the formula (II) are known and / or known in the art, for example, German Published Specification 2,514,402, European Published Specification 136,636, European Published Specification 154,178.
And European published specification 163,855.

Formula (III) provides a general definition of nitromethylene derivatives which are also used as starting materials in the process according to the invention. In this formula (III), Z preferably represents a group which has already been mentioned as suitable for this substituent with respect to the definition of the substance of the formula (I) according to the invention.

The diamines of the formula (III) are generally known organic chemical compounds.

The process according to the invention for the preparation of the novel compounds of the formula (I) is preferably carried out using a diluent. Diluents which can be used here are water and organic solvents which are inert in the reaction. These are preferably aliphatic and aromatic, optionally halogenated hydrocarbons such as pentane, hexane, heptane, cyclohexane, petroleum ether, benzene, ligroin, benzene, toluene, xylene, chloride Methylene, ethylene chloride, chloroform, carbon tetrachloride, chlorobenzene and o-dichlorobenzene, ethers such as diethyl ether, dibutyl-ether, glycol dimethyl ether, diglycol dimethyl ether, tetrahydrofuran and dioxane, and alcohols such as methanol, ethanol, n -Propanol and isopropanol. Mixtures of alcohols and water are preferably used.

Optionally, the process according to the invention is carried out in the presence of an acidic, non-oxidizing catalyst. Hydrohalic acids such as hydrochloric acid and hydrobromic acid, phosphoric acid and lower carboxylic acids such as acetic acid and propionic acid have proven to be particularly suitable.

The reaction temperatures when carrying out the process according to the invention can be varied within a substantial range. Generally, the reaction is -20
It is carried out at a temperature between 0C and + 120C, preferably at a temperature between 0C and + 80C.

The method according to the invention is generally performed at atmospheric pressure. However, the method can also be carried out under elevated or reduced pressure.

To carry out the process according to the invention, one mole of formula (II)
0.5 to 0.75 mol, preferably 0.5 to 0.6 mol, of the diamines of the formula (III) and 2 to 2
4 mol, preferably 2-3 mol, of formaldehyde are used.

If appropriate, the diamines of the formula (III) can also be used in the form of an aqueous solution. If gaseous diamines of the formula (III) are used, these compounds can be passed through a mixture of a diluent, a compound of the formula (II) and formaldehyde. The process according to the invention uses formaldehyde in aqueous solution. The reaction is generally carried out in a suitable diluent, and the reaction mixture is stirred at the specified required temperature for 5 or 6 hours. The processing of the method according to the invention takes place in each case in a general manner.

The acid addition salts of the compounds of the formula (I) can be prepared in a simple manner by customary salt-forming procedures, for example by dissolving the compound of the formula (I) in a suitable inert solvent and converting an acid such as, for example, hydrochloric acid. By addition, they can be obtained and they can be isolated in a known manner, for example by filtration, and can be purified by washing, if appropriate with an inert organic solvent.

 Physiologically acceptable acid addition salts are preferred.

The active compounds of the general formula (I) are suitable for controlling animal pests, especially insects and nematodes, which are encountered in the protection of agriculture, forestry, stored products and materials and in the field of hygiene, and It has good plant resistance and favorable low toxicity to warm-blooded animals. They are active against normally sensitive and resistant species and all or some stages of development.

The above-mentioned pests include: those of the order Isopoda, such as Oniscus ascers (O.
niscus asellus), Omadan bug (Armadillidium)
vulgare) and Porcellio scaba (Porcellio sc)
abar); those of Diplopoda, for example, Blaniulus guttulatus; those of the order Chilopoda, for example, Geophilus carpohagus and Scutigera spp .; Symphyl
a), such as Scachigerella imakiyurata (Scuti
gerella immaculata); from the order of Thysanura
For example, Lepisma saccharin
a); from the order of the Collembola, such as Onychiurus armatus; from the order of the Orthoptera, such as Blatta orientalis, Periplan
eta americana), Leucopha
ea maderae), Cockroaches (Blattella germ)
anica), Acheta domesticus (Acheta domesticu)
s), Kera (Gryllotalpa spp.), Tonosabata (Lo)
custa migratoria migratorioides), Melanoplus differential diis (Melanoplus differentialis)
And Schistocerca gregaria
aria); from the order of the Dermaptere, for example, Forficula auricular
ia); from the order of the Isoptera, for example, Reticulitermes spp .;
lura), such as Filoxera Bastarsk (Ph
ylloxera vastatrix), Penhuigus (Pemphigus sp)
p.) and human lice (Pediculus humanus corpori)
s), Lice lice (Haematopinus spp.) and L. lice (Linognathus spp.);
ophaga), such as the psyllid lice (Trichodectes)
spp.) and Damalinea spp .; from the order of the Thysanoptera, such as Hercinothrips femoralis and Thrips tabaci; from the order of the Heteroptera, such as Eurygaster. spp.), Dysdercus intermedi
us), Piesma quadrata, Bedbugs (Cimex lectularius), Rhodnius prolixus and Triatma (Tria)
toma spp.); of the order Homoptera, for example, Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, and evicon aphid brica ), Cryptomyzus ribis, Doraris huabae (Dora)
lis fabae), Doralis pomi, Eriosoma lanigerum, Homolopterus arundinis, Macrosiphum avenae, Mop aphid
yzus spp.), Phorodon humu
li), wheat beetle (Rhopalosiphum pad)
i), leafhopper (Empoasca spp.), Euscelis bilobatus, Nephotettix cincticeps, leaf beetle (Lecanium corni), olive beetle (Saissetia oleae), Lambertus phax (Laodelphix)
striatellus, brown planthopper (Nilaparvata luge)
ns), Red-eyed scale insect (Aonidiella auranti)
i), white scale insects (Aspidiotus hederae),
Pseudodococcus spp. And Psylla spp .; Lepidoptera,
For example, cotton beetle (Pectinophora gossypiell
a), Bupalus piniariu
s), Cheimatobia brumat
a) Lithocolletis blanc caldera
blancardella), Hyponomeut
a padella), Japanese moth (Plutella maculipennis), plum beetle (Malacosoma neustria), mulberry beetle (Euproctis chrysorrhoea), Gypsy moth (Lyman-tr)
ia spp.), Butucaratricus sliveriella (Bucc)
ulatrix thurberiella, mandarin leaf moth (Phylloc)
nistis citrella), Noctuid (Agrotis spp.), Yuxoa (Euxoa spp.), Fuercia (Feltia spp.),
Earias insulana, Heliothis (Heliothis spp.), Japanese squirrel (Laphy)
gma exigua), armyworm (Mamestra brassicae),
Panolis flammea, Spodoptera litura, Spodoptera
spp.) Trichoplusia ni, Carpocapsa pomonella, Carabocasa (Pieris spp.), Chimes sp.
p.), Pyrausta nubilalis, Ephestia kuehniella, Galleria mellonella, Tineola bisselliella, Tinea perionella (T
inea pellionella, Hofmannophila pseudospretella, Cacoecia podana, Capua reticulana, Cristoneura fumiferana, Crysia ambiguera Homona
magnanima) and Tortrix bildana (Tortrix)
viridana); of the order Coleoptera, for example, Anobium punctatum, Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus, Hirorupesj , Agelastica alni (Agelastica alni), Leptinotarsa decemlineata (Leptinotarsa decemlineata),
Phedon cochleariae,
Diabrotica (Diabrotica spp.), Psylliodes chrysocephala, Papilionas chrysocephala, Epilachna varivestis, Atomaria (Atomaria spp.), Sawtooth beetle (Oryzae)
philus surinamensis, weevil (Anthonomus)
spp.), Sitophilus spp., Otiorrhychus sulcatus, Cosmopolites sordidus, Ceuthorrhynchus assimilli
s), Hypera postica, Dermestes spp., Trogoderm
a spp.), Anthrenus (Anthrenus spp.), Attagenus (Attagenus spp.), Flycatcher beetle (Lyctus
spp.), Meligethes aeneus
us), giant beetle (Ptinus spp.), Niptus hololeucus, Gibbium psylloides,
bolium spp.), Tenebrion beetle (Tene
brio molitor), click beetle (Agriotes spp.),
Conoderus spp., Melolontha melolontha, Amphimallon solstitialis and Costelytra zealandic
a); from the order Hymenoptera, for example, pine wasp (Diprion spp.), hoplocampa (Hoplocampa sp.)
p.), Lasius (Lasius spp.), and Himeari (Mono)
morium pharaonis and wasp (Vespa sp)
p.); of the order Diptera, for example, Aedes (Aedes)
spp.), Anopheles spp., Culex (C)
ulex spp.), Drosophila
melanogaster), Housefly (Musca spp.), Musca domestica (Fannia spp.), Blowfly Erythrocephala (Cal)
liphoro erythrocephala, flies (Lucilia sp.)
p.), lobster fly (Chrysomya spp.), terebra (Cuterebra spp.), horsefly (Gastrophilus sp.)
p.), Hyppobosca spp., Stomflies (Stomoxys spp.), Sheep flies (Oestrus spp.),
Bullflies (Hypoderma spp.), Tabby (Tabanus sp.)
p.), Tania (Tannia spp.), Fly (Bibio hortu)
lanus), Oscinella frit, Oscinella frit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Daeva oleae
eae) and gagbo paludos (Tipula paludos)
a); from the order of Siphonaptera, such as Xenopsylla cheopis and Nagano flea (C
eratopyllus spp.); those of the spider web (Arachnida), such as Scorpio maurus and Latrodectus mactans
s).

The active compounds of the formula (I) according to the invention are characterized by a pronounced insecticidal activity. Especially when used as foliar insecticides, they exhibit significant activity against scarab beetle larvae, such as Phadhon cochleariae.

The active compounds of the formula (I) according to the invention furthermore exhibit root-penetrating activity against aphids, such as, for example, Aphis fabae.

The active compounds according to the invention can also be used for extracorporeal parasites such as larvae of Lusilia cuprina and Sitophilus granarius.
It is also very suitable for pest control.

The novel compounds are particularly suitable for use in controlling leaf insects and ectoparasites.

The active compounds can be prepared in the customary formulations, for example solutions, emulsions,
Suspensions, powders, foams, pastes, granules, aetosols, natural and synthetic substances impregnated with active compounds, microcapsules in polymeric substances, coating compositions for seeds and burning equipment such as fumigation cartridges, fumigation Formulations used with cans and fumigation coils can be converted to ULV cold and hot mist formulations.

These formulations may be prepared in a known manner, for example by extending the active compound with a liquid or liquefied gaseous or solid diluent or carrier, and optionally with a surfactant, ie emulsifier and / or dispersant and / or foaming agent. And can be produced by mixing. When water is used as the extender, for example, an organic solvent can be used as an auxiliary solvent. As liquid diluent or carrier, especially as solvent, mainly aromatics, such as xylene, toluene or alkylnaphthalene, chlorinated aromatic or aliphatic hydrocarbons, such as chlorobenzene, chloroethylene, ethylene chloride, aliphatic hydrocarbon Such as cyclohexane, or paraffins such as mineral oil fractions, alcohols such as butanol or glycol and their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strong polar solvents such as Dimethylformamide and dimethylsulfoxide and water are suitable. By liquefied gaseous diluent or carrier is meant a liquid that is gaseous at normal temperature and pressure, such as halogenated hydrocarbons and butane, propane,
Aerosol propellants such as nitrogen and carbon dioxide. Suitable as solid carriers are, for example, ground natural minerals, such as kaolin, clay, talc, chiyoke, quartz, attapulgite, montmorillonite or diatomaceous earth, and synthetic minerals, such as highly dispersed silicic acid, alumina and silicates. I have. As solid carriers for granules, ground and fractionated natural stones, such as calcite, marble, pumice, sepiolite and dolomite, as well as inorganic and organic finely-divided granules and granules of organic substances, such as sawdust, coconut, corn Cobs and tobacco stems are suitable. As emulsifiers and / or foaming agents, nonionic and anionic emulsifiers such as polyoxyethylene-fatty acid esters, polyoxyethylene fatty alcohol ethers such as alkylaryl polyglycol ethers, alkylsulfonates, alkylsulfates, arylsulphonates and Albumin hydrolysis products are suitable. Suitable dispersants are, for example, lignin sulphite waste liquors and methylcellulose.

Adhesives such as carboxymethylcellulose and natural and synthetic polymers in powder, granular or latex form such as gum arabic, polyvinyl alcohol and polyvinyl acetate, and natural phospholipids such as cephalins and lecithins, and synthetic phospholipids. It can be used in compositions. Mineral and vegetable oils can also be used as other additives.

Use colorants, such as inorganic pigments, such as iron oxide, titanium oxide and Prussian blue, and organic dyes, such as alizarin dye, and trace nutrients, such as salts of iron, manganese, boron, copper, cobalt, molybdenum, and zinc. be able to.

The formulations generally comprise between 0.1 and 95% by weight, preferably between 0.5 and 90%.
% By weight of active compound.

The active compounds according to the invention can be used in the formulations of their commercially available types and in the use forms prepared from these formulations in the form of other active compounds, such as insecticides, attractants, sterilants, It can also be present as a mixture with acaricides, nematicides, fungicides, growth regulators or herbicides. Insecticides include, for example, phosphates, carbamimates, carboxylates, chlorinated carbohydrates, phenylureas, and substances produced by microorganisms.

The active compounds can also be present as mixtures with synergists in their commercially available preparations and in the use forms prepared from these preparations.
Synergists are compounds which increase the activity of the active compound, although the synergist added need not be active itself.

The active compound content of the use forms prepared from the commercially available types of preparations can be varied over a wide range. The active compound content in the use form is 0.
0000001-95% by weight, preferably 0.0001-1% by weight
Of the active compound.

 Application can be carried out in a customary manner appropriate for the use form.

When used against sanitary pests or stored product pests, the active compounds have excellent residual activity on wood and soil, and good stability against alkali on lime-treated substances Is characteristic of having

The active compounds which can be used according to the invention are also suitable for controlling insects, small insects, mosquitoes and the like in the field of animal and cattle breeding, for example by controlling the pests for higher milk production, Good results such as heavy weight, more attractive animal fur, and longer lifespan are obtained.

Especially when used as ectoparasitic agents, they show excellent activity against larvae of blowfly and mosquito fly, such as Lutilia cuprina.

The application of the active compounds according to the invention is carried out in a manner known in the art, for example by in-vitro application in the form of dipping, spraying, pouring, dripping and dusting.

The biological activity of the compounds according to the invention is illustrated with reference to the following examples.

Manufacturing Example Example 1 1.5 ml (0.02 mol) of 37% strength formaldehyde aqueous solution was added to 90 ml of ethanol to 2.54 g (0.01 mol) of 3-
(2-chloropyridin-5-yl-methyl) -2-nitromethylene-imidazolidine and 0.72 g (0.005 mol)
Of n-octane-1,8-diamine at room temperature and the mixture was heated under reflux for 12 hours. After cooling to room temperature, the solvent was removed in vacuo, acetone was added to the residue and the product was filtered off with suction.

2.1 g (% of theory) of 1,8-bis- [6,7-dihydro-8-nitro- (5H) -3- (2
-Chloropyridin-5-yl-methyl) -imidazolidino- (2,3-f) -pyrimidin-6-yl] -n-octane was obtained.

In a manner analogous to Example 1 and in accordance with the invention, the compounds of formula (I) shown in Table 1 below could be prepared.

Use Examples In the following use examples, the following compounds were used as comparative substances: 7-ethyl-9-nitro-3,4,7,8-tetrahydro- (2H, 6H) -pyrimidino- from U.S. Pat. No. 4,031,087
[4,3-b] -1,3-thiazine.

Example A Phaedon larval test Solvent: 7 parts by weight of dimethylformamide Emulsifier: 1 part by weight of alkylaryl polyglycol ether To prepare a suitable formulation of the active compound, 1 part by weight of the active compound is added in the above amount. And the above amount of emulsifier, and the concentrate was diluted with water to the desired concentration.

Treating cabbage (Brassica oleracea) leaves by immersing them in the desired concentration of active compound formulation;
The larvae of the mustard beetle (Phaedon cochleariae) were infected while the leaves were as moist as possible.

After a certain time, the degree of death (%) was measured. 100%
Means the killing of all beetle larvae. 0% means that no beetle larvae were killed.

In this test, for example, the compounds from the following preparation examples showed 100% higher activity than the prior art compound (A): 2, 30, 10, 8, 4, 3, 6, 11, 37, 38, 1, 1
7, 23, 5, 31, 7, 12, 14, 19, 21, 25, 20, 13, 1
6, 43, 18, 45, 22, 24, 26, 49, 9, 35, 41, 40, 4
2, 44, 48, 50 and 52.

Example B Aphis test (osmotic activity) Test insect: Phaedon cochle
ariae) Larvae Solvent: 7 parts by weight of dimethylformamide Emulsifier: 1 part by weight of alkylaryl polyglycol ether To prepare a suitable formulation of the active compound, 1 part by weight of the active compound is mixed with the above amount of solvent, The above amount of emulsifier was added and the concentrate was diluted with water to the desired concentration.

A black bean aphid (Aphis fabae) infected bean plants (Vicia faba) each containing 20 ml of the desired concentration of the active compound formulation in each of the active compound formulations Is sprayed in such a way that it penetrates into the soil without wetting the branches.The active compound is absorbed by the roots and sent to the branches.

After a certain time, the degree of death (%) was measured. 100%
Means the death of all Affidos. 0% means that no affid was killed.

In this test, for example, the compounds from the following preparation examples showed 100% higher activity than the prior art compound (A): 10, 8, 6, 17, 7, 19, 21, 25, 35, 41, 40, 4
2, 44, 48, 50 and 52.

Example C Test with Lucilia cuprina resistant larvae Emulsifier: 35 parts by weight of ethylene polyglycol monomethyl ether 35 parts by weight of nonylphenol polyglycol ether To prepare a suitable formulation of the active compound, 3 parts by weight Parts of the active compound were mixed with 7 parts by weight of the above mixture, and the concentrate thus obtained was diluted with water to the desired concentration.

It was placed into a test tube containing about twenty Lucilia Kupurina (Lucilia cuprina) active compound formulation horse meat of a resistant larvae approximately 1 cm ³ and 0.5 ml. After 24 hours, the extent of death was measured.

In this test, for example, the compounds from the following preparation examples showed 100% higher activity than the prior art compound (A): 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 1
3, 14, 1, 16, 17, 18, 19, 21, 22, 23, 24, 25, 2
6, 29, 30, 31, 37, 38, 39, 42, 43, 44, 45, 47, 4
9, 51 and 52.

Example D Sitophilus granarius
2. Test using a circular filter paper (φ9 cm, Schleicher und Schul BF) in a plastic dish was impregnated with 2 ml in each case of the desired concentration of the test substance.

After drying of the filters, the dishes were capped and 24 hours after insertion, in each case 10 CO ₂ -anesthetized Sitophilus granarius were added.

Specific time after addition of S. filarius (5-360 minutes or 1 after addition of S. filarius)
-7 days).

The so-called unpowered state of the test arthropod (no signs of survival)
Was used as a measure of activity onset.

100% means the death of all Citophilus granarius. 0% means that Sitophilus granarius was not killed at all.

In this test, for example, the compounds from the following preparation examples showed a degree of killing of 100% at an exemplary concentration of 100 ppm: 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, 13, 1
4, 1, 16, 17, 18, 21, 22, 24, 25, 26, 29, 30, 3
5, 37, 38, 39, 40, 41, 42, 43, 44, 45, 47, 49, 5
0, 51 and 52.

The main features and aspects of the present invention are as follows.

1. Formula (I) Wherein A represents a straight-chain alkanediyl, Het represents an unsubstituted or substituted pyridyl or an unsubstituted or substituted thiazolyl, and Z represents a linear or branched or represents alkanediyl, or a group -Y -, - Y-a ¹ - or -Y-a ² -Y- represents, wherein Y is unsubstituted or alkyl - represents a substituted cycloalkanediyl A ¹ represents a straight-chain or branched alkanediyl, and A ² represents a direct bond or oxygen, sulfur, -NH-
Or a linear or branched alkanediyl, or a group And a nitrogen-containing heterocyclic compound and an acid addition salt thereof.

2. A represents a straight-chain alkanediyl having 2 to 4 carbon atoms, Het represents an unsubstituted or halogen-substituted pyridyl or an unsubstituted or halogen-substituted thiazolyl, and Z represents a carbon atom. whether the number represents straight-chain or branched alkanediyl having from 1 to 18, or a group ^{-Y -, - Y-a 1} - or -Y-a ² -Y- represents, wherein Y is unsubstituted Or a cycloalkanediyl having 3 to 7 carbon atoms substituted by an alkyl having 1 to 4 carbon atoms, and A ¹ represents a linear or branched alkanediyl having 1 to 4 carbon atoms, And A ² represents a direct bond, or oxygen, sulfur, —NH—, or a linear or branched alkanediyl having 1 to 4 carbon atoms, or a group A compound of the above formula (I) and acid addition salts thereof.

3. A represents a straight-chain alkanediyl having 2 to 4 carbon atoms, and Het represents And Z represents a straight-chain or branched alkanediyl having 1 to 18 carbon atoms, or a group Wherein R ¹ , R ² , R ³ and R ⁴ independently represent hydrogen,
Or a straight-chain or branched alkyl having ¹ to 4 carbon atoms, A ¹ represents a straight-chain or branched alkanediyl having 1 to 4 carbon atoms, and A ² represents a direct bond. Represents oxygen, sulfur, -NH- or a linear or branched alkanediyl having 1 to 4 carbon atoms, or represents a group A compound of formula (I) according to 1 above,

4.A represents ethane-1,2-diyl or propane-1,3-diyl, and Het is And Z is methanediyl, ethane-1,2-diyl, propane-
1,3-diyl, propane 1,2-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8 -Jill,
Represents nonane-1,9-diyl, decane-1,10-diyl, undecane-1,11-diyl, dodecane-1,12-diyl, tridecane-1,13-diyl or tetradecane-1,14-diyl Or group Wherein R ¹ , R ² , R ³ and R ⁴ independently represent hydrogen, methyl or ethyl, and A ¹ has methanediyl, ethane-1,1-diyl, ethane-1,2 -Diyl, propane-1,3-diyl or propane-2,2-diyl and A ² represents a direct bond, or oxygen, sulfur, methanediyl, ethane-1,2-diyl or propane-2, Represents 2-diyl or a radical A compound of formula (I) according to 1 above,

5. Formula (I) Wherein A represents a straight-chain alkanediyl, Het represents an unsubstituted or substituted pyridyl or an unsubstituted or substituted thiazolyl, and Z represents a linear or branched or represents alkanediyl, or a group -Y -, - Y-a ¹ - or -Y-a ² -Y- represents, wherein Y is unsubstituted or alkyl - represents a substituted cycloalkanediyl A ¹ represents a straight-chain or branched alkanediyl, and A ² represents a direct bond or oxygen, sulfur, -NH-
Or a linear or branched alkanediyl, or a group And a method for producing a nitrogen-containing heterocyclic compound of the formula (II) and an acid addition salt thereof. Wherein A and Het have the above-mentioned meaning. The nitromethylene derivatives of formula (I) are optionally reacted with an acid catalyzed, in the presence of at least 2 times the amount of formaldehyde (per mole of compound of formula (II)). In the presence and, optionally, in the presence of a diluent, with a diamine of the formula (III) H ₂ N—Z—NH ₂ (III), wherein Z has the meaning given above, and optionally forming A method comprising adding an acid to the compound obtained.

6. A pesticidal composition comprising at least one nitrogen-containing heterocyclic compound of the formula (I) of the above formulas (1) to (5).

7. Formulas (I) of the above 1 to 5 for controlling pests
Use of a nitrogen-containing heterocyclic compound of formula (I).

8. A method for controlling pests, which comprises causing the nitrogen-containing heterocyclic compound of the formula (I) of the above 1 to 5 to act on pests and / or their environment.

9. A method for producing a pesticidal composition, which comprises mixing the nitrogen-containing heterocyclic compound of the formula (I) of the above 1 to 5 with an extender and / or a surfactant.

────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Bilhelm Schüttendel, Germany Day 5600 Butzpertal 1, Inden Birken 55 (56) References JP-A-1-160981 (JP, A) JP-A-1-153690 ( JP, A) JP-A-62-292765 (JP, A) JP-A-50-69098 (JP, A) JP-A-50-77397 (JP, A) JP-B-48-25200 (JP, B1) (58 ) Fields studied (Int. Cl. ⁷ , DB name) C07D 519/00 C07D 487/04 A01N 43/90 105 CA (STN) REGISTRY (STN)

Claims (4)

(57) [Claims] (1) Formula (I) Wherein A represents a straight-chain alkanediyl, Het represents an unsubstituted or substituted pyridyl or an unsubstituted or substituted thiazolyl, and Z represents a linear or branched or represents alkanediyl, or a group -Y -, - Y-a ¹ - or -Y-a ² -Y- represents, wherein Y is unsubstituted or alkyl - represents a substituted cycloalkanediyl A ¹ represents a straight-chain or branched alkanediyl, and A ² represents a direct bond or oxygen, sulfur, -NH-
Or a linear or branched alkanediyl, or a group And a nitrogen-containing heterocyclic compound and an acid addition salt thereof. 2. Formula (I) Wherein A represents a straight-chain alkanediyl, Het represents an unsubstituted or substituted pyridyl or an unsubstituted or substituted thiazolyl, and Z represents a linear or branched or represents alkanediyl, or a group -Y -, - Y-a ¹ - or -Y-a ² -Y- represents, wherein Y is unsubstituted or alkyl - represents a substituted cycloalkanediyl A ¹ represents a straight-chain or branched alkanediyl, and A ² represents a direct bond or oxygen, sulfur, -NH-
Or a linear or branched alkanediyl, or a group And a method for producing a nitrogen-containing heterocyclic compound of the formula (II) and an acid addition salt thereof. Wherein A and Het have the above-mentioned meaning. The nitromethylene derivatives of formula (I) are optionally reacted with an acid catalyzed, in the presence of at least 2 times the amount of formaldehyde (per mole of compound of formula (II)). In the presence and, optionally, in the presence of a diluent, with a diamine of the formula (III) H ₂ N—Z—NH ₂ (III), wherein Z has the meaning given above, and optionally forming A method comprising adding an acid to the compound obtained. 3. A pesticidal composition comprising at least one nitrogen-containing heterocyclic compound of the formula (I) according to claims 1 and 2. 4. The method according to claim 1, wherein the nitrogen-containing heterocyclic compound of the formula (I) acts on pests and / or their environment.
Pest control method.