DE4217864A1 - Substituted pyrazolines - Google Patents

Abstract

Described are substituted pyrazolines of the formula given in the description, as well as several methods of preparing them and their use as pest-control agents.

Description

The invention relates to new, substituted pyrazolines, several processes for their manufacture and their use as a pesticide.

It is known that certain substituted pyrazolines possess insecticidal properties (cf. e.g. DE-A 27 00 258; DE-A 25 29 689; US-A 4,174,393).

The level of effectiveness or duration of this known Connections is, however, especially with certain Insects or at low application concentrations not completely satisfied in all areas of application posed.

There were new substituted pyrazolines of the general Formula (I) found

in which the substituents R ¹ , R ² , R ³ and R ⁴ each have the following combinations of meanings

Furthermore, it was found that the new substi tuated pyrazolines of the general formula (I)

in which the substituents R ¹ , R ² , R ³ and R ^{4 have} the meaning given above, if unsubstituted pyrazolines of the formula (II)

in which
R ¹ , R ² and R ^{3 have} the meaning given above,
either

• a) with isocyanates of the formula (III), R ⁴ -N = C = O (III) in which
  R ^{4 has} the meaning given above,
  or
• b) with carbamic acid chlorides of the formula (IV) in which
  R ^{4 has} the meaning given above,
  if appropriate in the presence of a diluent and if appropriate in the presence of a reaction auxiliary.

Finally it was found that the new ones were substituted Pyrazolines of the general formula (I) have good activity against animal pests.

Surprisingly, the substi according to the invention did pyrazolines of the general formula (I) significantly better insecticidal efficacy compared to the chemically known from the prior art and / or connections which are obviously effective.

In particular, refer to the manufacturing examples referred connections referred.

For example, if 3- (4-fluorophenyl) -4- (2- acetylamino-4,5-dihydropyrazole and 4-trifluoromethyl phenyl isocyanate as a starting material, so the Reaction sequence of the process (a) according to the invention represented by the following formula:

For example, if 3- (4-chlorophenyl) -4- (cyclo propyl-carbonylamino) -4,5-dihydropyrazole and 4-fluorine phenyl-carbamic acid chloride as starting materials, can be the course of the reaction of process (b) according to the invention represent the following formula scheme:

Formula (II) provides a general definition of the pyrazolines which are unsubstituted in the 1-position and are required as starting materials for carrying out process (a) and (b) according to the invention. In this formula (II) R ¹ , R ² and R ^{3 represent} those radicals which have already been mentioned in connection with the description of the compounds of the formula (I) according to the invention.

The pyrazolines of the formula which are unsubstituted in the 1-position (II) are not yet known. You get it for example wise if phenacylamine derivatives of the formula (V)

in which
R ¹ , R ² and R ^{3 have} the meaning given above,
with dimethylmethyleneimmonium chloride of the formula (VI)

optionally in the presence of a diluent such as for example acetonitrile at temperatures between  30 ° C and 80 ° C and then in a second stage the phenacyldiamine derivatives of the formula obtainable in this way (VII)

in which
R ¹ , R ² and R ^{3 have} the meaning given above,
with hydrazine hydrate if appropriate in the presence of a diluent such as acetonitrile at temperatures between 30 ° C and 80 ° C.

It is also possible and, if necessary, from before Part g the implementation of the phenacylamine derivatives of the formula (V) with dimethylmethyleneimmonium chloride of the formula (VI) and the subsequent implementation of the so available Phenacyldiamine derivatives of the formula (VII) with hydrazinhy drat in one reaction step in a so-called To carry out "one-pot process".

The pyrazolines of the formula (II)  can alternatively also be obtained by phenacylamine vate of formula (Va)

in which
R ¹ , R ² and R ^{3 have} the meaning given above,
first in a first stage with formaldehyde, if appropriate in the presence of a diluent such as, for example, ethanol at temperatures between 30 ° C. and 80 ° C. and then the phen acyl-enamine derivatives of the formula (VIII) thus obtainable

in which
R ¹ , R ² and R ^{3 have} the meaning given above,
with hydrazine hydrate, if appropriate in the presence of a diluent such as ethanol, at temperatures between 30 ° C. and 80 ° C.

It is also possible and, if necessary, from before part, the implementation of the phenacylamine derivatives of the formula (Va) with formaldehyde and the subsequent implementation of the thus obtainable phenacyl enamine derivatives of the formula (VIII) with hydrazine hydrate in one reaction step in to carry out a so-called "one-pot process".

Phenacylamine derivatives of the formulas (V) and (Va) are be known or available in analogy to known methods (see e.g. Che ;. Ber. 122, 295-300 [1989]; J. Med. Chem. 29, 333-341 [1986]; J. Amer. Chem. Soc. 98, 3621-3627 [1976]; Tetrahedron 31, 2145-2149 [1975]; Zh. Org. Khim. 10, 2429-2436 [1974]; J. Org. Chem. 55, 3658-3660 [1990]; Chem. Ind. 1975, 177; Synthesis 1990, 520).

Dimethylmethyleneimmonium chloride of the formula (VI) is be knows (see, for example, J. Org. Chem. 47, 2940-2944 [1982]; Bull. Soc. Chim. 1970, 2707-2711).

Phenacyldiamine derivatives of the formula (VII) are partial known (see, for example, US 2980674 [1957] or CA 56: 3419 [1962]).

Phenacyl enamine derivatives of the formula (VIII) are known or available in analogy to known processes (cf. e.g. B. Chem. Ber. 93, 387-391 [1960]; Sankyo Kenkyusho Nempo 15, 36 (1963) or Chem. Abstr. 60: 11876d [1964]; 3. Med. Chem. 30, 1497-1502 [1987]; JP 61-053239; US 4277420; Chem. Abstr. 87: 67928y; Khim. Farm. Zh. 9, 21-24 [1975] and CA 83: 58351v; Collect. Czech.  Commun. 19, 317-328 (1954); Ann. Chim. 46, 267-269 [1956]; J.Chem. Soc. 1953, 4066-4073; Zh. Obshch. Khim. 30, 3714 [1960]; Pharm. Chem. J. 9, 301-304 [1975]).

Formula (III) provides a general definition of the isocyanates required as starting materials for carrying out process (a) according to the invention. In this formula (III), R ⁴ preferably represents those radicals which have already been mentioned in connection with the description of the compounds of the formula (I) according to the invention. The isocyanates of the formula (III) are generally known compounds of organic chemistry.

Formula (IV) provides a general definition of the carbamic acid chlorides required as starting materials for carrying out process (b) according to the invention. In this formula (IV), R ^{4 represents} those radicals which have already been mentioned for these substituents in connection with the description of the substances of the formula (I) according to the invention.

The carbamic acid chlorides of formula (IV) are general known or obtainable using known methods (see, for example, JP 57-108057 or Chem. Abstr. 98: 53440y; JP-A 50-089344 or Chem. Abstr. 83: 205987n; DE-A 24 29 523; AU-A 491880 or Chem. Abstr. 89: 163572q).

As a diluent for performing the fiction Processes (a) and (b) use inert organic solvents means in question. This includes in particular alipha tables, alicyclic or aromatic, optionally  halogenated hydrocarbons such as Ben zin, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, Petroleum ether, hexane, cyclohexane, dichloromethane, chloro form or carbon tetrachloride; Ethers such as diethyl ether, Diisopropyl ether, dioxane, tetrahydrofuran or ethylene glycol dimethyl or diethyl ether; Ketones such as acetone or butanone or methyl isobutyl ketone; Nitriles like Acetonitrile, propionitrile or benzonitrile; Amides like N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl formanilide, N-methylpyrrolidone or hexamethylphosphorus acid triamide, esters such as methyl acetate or Es ethyl acetate or sulfoxides such as dimethyl sulfoxide.

Processes (a) and (b) according to the invention can be carried out before preferably in the presence of a suitable reaction aid be carried out by means. As such, all come over Lichen inorganic or organic bases in question. These include, for example, alkaline earth or alkali metals tall hydroxides such as sodium hydroxide, calcium hydroxide, Ka lium hydroxide or ammonium hydroxide, alkali metal carbonates such as sodium carbonate, potassium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate or ammonium carbonate, alkali or alkaline earth metal acetates such as natri umacetate, potassium acetate, calcium acetate or ammonium ace tat and tertiary amines such as trimethylamine, triethyl amine, tributylamine, N, N-dimethylaniline, pyridine, pipe ridine, N-methylpiperidine, N, N-dimethylaminopyridine, Di azabicyclooctane (DABCO), diazabicyclonones (DBN) or Diazabicycloundecene (DBU).  

The reaction temperatures can be carried out of processes (a) and (b) in one larger range can be varied. Generally ar one works at temperatures between 0 ° C and 120 ° C, preferably at temperatures between 20 ° C and 80 ° C.

Processes (a) and (b) according to the invention are carried out Licher carried out under normal pressure. It is ever but also possible under increased or reduced pressure to work.

To carry out process (a) according to the invention is used per mole of Py unsubstituted in the 1-position razoline of the formula (II) in general 1.0 to 2.5 mol, preferably 1.0 to 1.5 mol of isocyanate of the formula (III) and optionally 0.01 to 2.0 mol, preferably 0.1 to 1.2 moles of used as reaction aids Base one.

The implementation of the reaction, workup and isolation the reaction products are carried out according to generally customary methods Methods (see the manufacturing examples).

To carry out process (b) according to the invention is used per mole of Py unsubstituted in the 1-position razoline of the formula (II) in general 1.0 to 2.5 mol, preferably 1.0 to 1.5 moles of carbamic acid chloride Formula (IV) and optionally 0.01 to 2.0 moles preferably 0.1 to 1.2 mol of as a reaction aid base used.

The implementation of the reaction, workup and isolation the reaction products are carried out according to generally customary methods Methods.  

The active substances are suitable for controlling animal pests, preferably arthropods and nematodes, in particular insects and arachnids, which occur in agriculture, in forests, in the protection of stored goods and materials and in the hygiene sector. They are effective against normally sensitive and resistant species as well as against all or individual stages of development. The pests mentioned above 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 guttula tus;
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. Forficula auricula 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, Haematopinus 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 the Heteroptera z. B. Eurygaster spp., Dysdercus intermedius, Piesma guadrata, Cimex lectula rius, Rhodnius prolixus, Triatoma spp;
from the order of Homoptera z. B. Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossy pii, Brevicoryne brassicae, Cryptomyzus ribis, Aphis fabae, Doralis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Macrosiphum avenae, Myzus spp., Phoropaliphasum. Euscelis bilobatus, Nephotettix cincticeps, Lecanium corni, Sais setia oleae, Laodelphax striatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus 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., Trichoplocapsia n ., Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Galleria mellonella, Tineola bisselliella, Tinea pellionella, Hofmannophila pseudospretella, Ca coecia podana, Capua reticulana, Choristoneura fumi ferana, Clysia ambiguella, Torona viridana, Homona magnanana
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 chrysoyzapharia, syllable, spp. Sitophilus spp., Otiorrhynchus sul catus, Cosmopolites sordidus, Ceuthorrhynchus assimilis, Hypera postica, Dermestes spp., Trogoderma spp., Anthre nus spp., Attagenus spp., Lyctus spp., Meligethes aene us, Ptinusium spp., Ptinusium spp psylloides, Tribolium spp., Tenebrio molitor, Agriotes spp., Cono derus spp., Melolontha melolontha, Amphimallon solsti tialis, 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 Diptera z. B. Aedes spp., Anopheles spp., Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphora erythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp., Gastrophilus spp., Hyp pobosca spp., Stomoxys spp., Oestrus spp., Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus, Os cinella frit, Phorbia spp., Pegomyia hyoscyami, Cerati tis 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., Ornithodoros spp., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora, Boophilus spp., Rhipice phalus spp., Amblyomma spp., Hyalomma spp., Ixodes spp., Psororioptes spp. , Sarcoptes spp., Tarso nemus spp., Bryobia praetiosa, Panonychus spp., Tetra nychus spp.

Plant parasitic nematodes include pratyls chus 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 can also be used particularly good success in combating plant damage insects such as against the larvae the horseradish leaf beetle (Phaedon cochleariae) or ge towards the caterpillars' caterpillars (Plutella maculipennis) deploy.

The active ingredients can depend on their respective physical and / or chemical properties usual formulations are transferred, such as solutions, Emulsions, suspensions, powders, foams, pastes, gra nulates, aerosols, active ingredient-impregnated natural and syn synthetic materials, fine encapsulation in polymers Fabrics and in coating compositions for seeds, also in form burnings with fuel sets, such as smoking cartridges, cans, spirals and the like, as well as ULV cold and warm fog formulations stanchions.  

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, optionally using surface ac tive agents, so emulsifiers and / or dispersants agents and or foaming agents. In case of Use of water as an extender can e.g. Belly Use organic solvents as auxiliary solvents be det. Essentially come as liquid solvents lichen in question: aromatics such as xylene, toluene, or Al kylnaphthalenes, chlorinated aromatics or chlorinated ali phatic hydrocarbons, such as chlorobenzenes, chlorine ethylene or methylene chloride, aliphatic coal water serstoffe, such as cyclohexane or paraffins, e.g. B. petroleum fractions, alcohols, such as butanol or glycol, and their ethers and esters, ketones, such as acetone, methylethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly po lare solvents such as dimethylformamide and dimethyl sulfoxide and water; with liquefied gaseous Extenders or carriers are such liquids ten meant, which at normal temperature and below Normal pressure are gaseous, e.g. B. aerosol propellants, such as Halogenated hydrocarbons as well as butane, propane, stick fabric and carbon dioxide; come as solid carriers in question: e.g. B. natural stone powder, such as kaolins, Clay, talc, chalk, quartz, attapulgite, Montmoril lonite or diatomaceous earth and synthetic rock powder, such as finely divided silica, aluminum oxide and silica Kate; come in as solid carriers for granules Question: e.g. B. broken and fractionated natural Ge  stones like calcite, marble, pumice, sepiolite, dolomite such as synthetic granules from inorganic and orga flours and granules made from organic material such as sawdust, coconut shells, corn cobs and tobacco stem; as an emulsifier and / or foam-generating agent come into question: z. B. non-ionic and anionic emuls gators, such as polyoxyethylene fatty acid esters, polyoxy ethylene-fatty alcohol ether, e.g. B. alkylaryl polyglycol Ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and Protein hydrolyzates; as dispersants are: e.g. B. lignin sulfite and methyl cellulose.

Adhesives such as carboxy can be used in the formulations methylcellulose, 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 ingredients can be in their commercially available form as well as in those prepared from these formulations Application forms in a mixture with other active ingredients, such as insecticides, attractants, sterilants, acaricides, Nematicides, fungicides, growth regulators or herbicides. Insecticides include for example phosphoric acid esters, carbamates, carbon acid esters, chlorinated hydrocarbons, phenyl urine substances, substances produced by microorganisms u. a.

The active ingredients can also be in their commercially available Formulations as well as in from these formulations prepared application forms in mixture with synergists available. Synergists are connections through which the Effect of the active ingredients is increased without the synergist must be actively active itself.

The active ingredient content of the from the commercial formu Formulations prepared use can be widely used range vary. The drug concentration of the users Forms of application can be from 0.0000001 to 95% by weight of active ingredient substance, preferably between 0.0001 and 1 wt .-% lie gene.

The application takes place in one of the application forms adapted usual way.

When used against hygiene and storage pests the active ingredients are characterized by an excellent Residual effect on wood and clay as well as by a good Alkali stability on limed substrates.  

The production and use of the invention Active ingredients can be found in the following examples emerged:

Manufacturing examples Example 1 (Method (a))

To 1.8 g (0.073 mol) of 3- (4-fluorophenyl) -4- (cyclopropyl carbonylamino) -4,5-dihydropyrazole in 50 ml dichloromethane are added dropwise at room temperature with stirring 1.23 g (0.008 mol) of 4-chlorophenyl isocyanate and heated for one hour at reflux temperature.

For working up, the reaction mixture is cooled, suctioned off precipitated solid and dried.

1.9 g (65% of theory) are obtained 3- (4-fluorophenyl) -4- (cyclopropylcarbonylamino) -1 - ((4- chlorphenyl) aminocarbonyl) -3,5-dihydroxypyrazole from Melting point <200 ° C. In a corresponding manner and in accordance with the general information on the manufacture gives the the following pyrazolines of the general formula (I):

Preparation of the starting compounds Example II-1

Similarly, the following are obtained in 1- Position of unsubstituted pyrazolines of the general formula (II):

Examples of use

The following was used in the following application examples listed compound as a reference substance set:

O- (4-methylthiophenyl) -O-ethyl-S- (n-propyl) thionophos phosphoric acid ester (known from DE 21 11 414).  

Example A 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 active ingredient preparation mix 1 part by weight of active ingredient with the specified amount of solvent and the specified amount of emul gator and dilute the concentrate with water to the ge wanted concentration.

Cabbage leaves (Brassica oleracea) are made by diving 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 kill in% Right. 100% means that all beetle larvae are off were killed; 0% means that no beetle larvae were killed.

In this test, e.g. B. the following compounds of the manufacturing examples superior effectiveness against about the state of the art.  

Example B Plutella test

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

For the preparation of a suitable active ingredient preparation mix 1 part by weight of active ingredient with the specified amount of solvent and the specified amount of emul gator and dilute the concentrate with water to the ge wanted concentration.

Cabbage leaves (Brassica oleracea) are made by diving in the active ingredient preparation of the desired concentration treated and with caterpillars caterpillars (Plutella macu lipennis) occupied while the leaves are still moist are.

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

In this test, e.g. B. the following compounds of the manufacturing examples superior effectiveness against about the state of the art.

Claims (7)

1. Substituted pyrazolines of the general formula (I) in which the substituents R ¹ , R ² , R ³ and R ⁴ each have the following combinations of meanings: 2. Process for the preparation of substituted pyrazoles of the general formula (I) in which the substituents R ¹ , R ² , R ³ and R ^{4 can have} the meaning combinations listed in claim 1,
characterized in that un-substituted pyrazolines of the formula (II) in which
R ¹ , R ² and R ^{3 have} the meaning given above, either

• a) with isocyanates of the formula (III), R ⁴ -N = C = O (III) in which
  R ^{4 has} the meaning given above, or
• b) with carbamic acid chlorides of the formula (IV)

in which R ^{4 has} the meaning given above,
if appropriate in the presence of a diluent and if appropriate in the presence of a reaction auxiliary. 3. Pest control, characterized by a content of at least one substituted Pyrazoline of formula (I). 4. Procedure for controlling animal pests gene, characterized in that one substituted Pyrazolines of formula (I) on animal pests and-or let their living space take effect. 5. Use of substituted pyrazolines Formula (I) for combating animal damage succeed. 6. Process for the preparation of pest control agents, characterized in that one substituted pyrazolines of formula (I) with stretch agents and / or surface active agents mixes.