WO2000034257A1

WO2000034257A1 - Substituted 2-imino-thiazolines and their use as herbicides

Info

Publication number: WO2000034257A1
Application number: PCT/EP1999/009281
Authority: WO
Inventors: Klaus-Helmut Müller; Mark Wilhelm Drewes; Dieter Feucht; Rolf Pontzen; Ingo Wetcholowsky
Original assignee: Bayer Aktiengesellschaft
Priority date: 1998-12-10
Filing date: 1999-11-30
Publication date: 2000-06-15
Also published as: DE19856966A1; AU1557800A

Abstract

The invention relates to novel substituted 2-imino-thiazolines of general formula (I), wherein A represents a simple bond or optionally substituted alkanediyl (alkylene), R1 represents nitro, cyano, thiocarbamoyl, nitroalkyl, cyanoalkyl, thiocarbamoyl alkyl or formylalkyl, R2 represents hydrogen, cyano, carboxy, carbamoyl, thiocarbamoyl, halogen, or optionally substituted alkyl or optionally substituted alkoxycarbonyl, R3 represents hydrogen, cyano, carboxy, carbamoyl, thiocarbamoyl, halogen, or optionally substituted alkyl or optionally substituted alkoxycarbonyl, and R4 represents hydrogen, cyano, halogen or alkoxy, or optionally substituted cycloalkyl, optionally substituted aryl or optionally substituted heterocyclyl, including the possible E- and Z-isomers of these compounds. The invention also relates to methods for producing the inventive substituted 2-imino-thiazolines and to their use as herbicides.

Description

SUBSTITUTED 2-IMINO-THIAZOLINE AND THEIR USE AS HERBICIDES

The invention relates to new substituted 2-imino-thiazolines, processes for their preparation and their use as herbicides.

It is known that certain substituted 2-imino-thiazolines have herbicidal properties (cf. EP-A-446802, EP-A-529481, EP-A-529482, EP-A-531970). However, these connections have so far not gained any particular importance.

New substituted 2-imino-3-thiazolines of the general formula (I)

in which

A represents a single bond or optionally substituted alkanediyl (alkylene),

R ^{1 represents} nitro, cyano, thiocarbamoyl, nitroalkyl, cyanoalkyl, thiocarbamoylalkyl or formylalkyl,

R ^{2 represents} hydrogen, cyano, carboxy, carbamoyl, thiocarbamoyl, halogen, or optionally substituted alkyl or alkoxycarbonyl,

R ^{3 represents} hydrogen, cyano, carboxy, carbamoyl, thiocarbamoyl, halogen, or each optionally substituted alkyl or alkoxycarbonyl, and R ^{4 represents} hydrogen, cyano, halogen or alkoxy, or optionally substituted cycloalkyl, aryl or heterocyclyl,

including the possible E and Z isomers of the compounds of formula (I) found.

In the definitions, the hydrocarbon chains, such as alkyl or alkanediyl - also in combination with heteroatoms, such as in alkoxy - are each straight-chain or branched.

Preferred substituents of the radicals shown in the above formula and the formulas below are explained below.

A preferably represents a single bond or, optionally, by

Cyano, halogen or C, -C ₄ alkoxy substituted alkanediyl (alkylene) having 1 to 4 carbon atoms.

R ¹ preferably represents nitro, cyano, thiocarbamoyl or nitroalkyl, cyanoalkyl, thiocarbamoylalkyl or formylalkyl, each having up to 6 carbon atoms.

R ² preferably represents hydrogen, cyano, carboxy, carbamoyl, thiocarbamoyl, halogen, or alkyl or alkoxycarbonyl, each optionally substituted by cyano, halogen or C _r C ₄ alkoxy, each having up to 4 carbon atoms.

R ³ preferably represents hydrogen, cyano, carboxy, carbamoyl, thiocarbamoyl, halogen, or represents in each case optionally substituted by cyano, halogen, or C _j ^ -C alkyl alkoxy or alkoxycarbonyl each having up to 4

Carbon atoms. R ⁴ preferably represents hydrogen, cyano, halogen, alkoxy having 1 to 6 carbon atoms, cycloalkyl having 3 to 6 carbon atoms optionally substituted by cyano, halogen or C 1 -C ₄ -alkyl, optionally by nitro, cyano, Halogen, C, -C ₄ alkyl, C, -C ₄ haloalkyl,

C, -C ₄ -alkoxy, C, -C ₄ -haloalkoxy, C, -C ₄ -alkylthio, C, -C ₄ -haloalkyl-thio, C, -C ₄ -alkylsulfonyl, C, -C ₄ -haloalkylsulfonyl, C, -C ₄ alkylsulfonyl, C, -C ₄ haloalkylsulfonyl, C, -C ₂ alkylene dioxy or C, -C ₂ haloalkylenedioxy substituted aryl having 6 or 10 carbon atoms, or for each optionally substituted by cyano, halogen, C, -C ₄ alkyl, C, -C ₄ halo-alkyl, C, -C ₄ alkoxy, C, -C ₄ haloalkoxy, C, _-C4 alkylthio, C, -C ₄ halo- alkylthio, C, -C ₄ alkylsulfonyl, C, -C ₄ haloalkylsulfonyl, C, -C ₄ alkylsulfonyl or C _r C ₄ haloalkylsulfonyl substituted, monocyclic or bicyclic heterocyclyl having 1 to 9 carbon atoms, 1 to 4 nitrogen - atoms and / or 1 or 2 oxygen or sulfur atoms.

A particularly preferably represents a single bond or methylene (CH ₂ ) or dimethylene (ethane-1,2-diyl, CH ₂ CH ₂ ) or trimethylene (propane-1,3-) which is optionally substituted by cyano, fluorine and / or chlorine. diyl, CH ₂ CH ₂ CH ₂ ).

R ¹ particularly preferably represents nitro, cyano, thiocarbamoyl, nitromethyl, nitroethyl, nitropropyl, cyanomethyl, cyanoethyl or cyanopropyl.

R ² particularly preferably represents hydrogen, cyano, carboxy, carbamoyl,

Thiocarbamoyl, fluorine, chlorine, bromine, or for methyl, ethyl, n- or i-propyl, methoxy carbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl, each optionally substituted by cyano, fluorine, chlorine, methoxy or ethoxy.

R ³ particularly preferably represents hydrogen, cyano, carboxy, carbamoyl,

Thiocarbamoyl, fluorine, chlorine, bromine, or for each optionally by Cyano, fluorine, chlorine, methoxy or ethoxy substituted methyl, ethyl, n- or i-propyl, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl.

R ⁴ particularly preferably represents hydrogen, cyano, fluorine, chlorine, bromine, methoxy, ethoxy, n- or i-propoxy, in each case optionally by cyano,

Fluoropropyl, chlorine, methyl or ethyl substituted cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl, for optionally by nitro, cyano, fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, n-, i-, s- or t -Butyl, trifluoromethyl, methoxy, ethoxy, n- or i-propoxy, difluoromethoxy, trifluoromethoxy, methylthio, ethylthio, n- or i-propylthio, difluoromethylthio, trifluoromethylthio, methylsulfmyl, ethyl sulfonyl, trifluoromethylsulfyl, methyl Ethylsulfonyl, trifluoromethylsulfonyl, methylenedioxy, ethylenedioxy, difluoromethylenedioxy, trifluoroethylenedioxy or tetrafluoroethylenedioxy or phenyl which is substituted by cyano, fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-

Butyl, trifluoromethyl, methoxy, ethoxy, n- or i-propoxy, difluoromethoxy, trifluoromethoxy, methylthio, ethylthio, n- or i-propylthio, difluoromethylthio, trifluoromethylsulfonyl, trifluoromethylsulfonyl, methylsulfonyl or methylsulfonyl the series furyl, thienyl, pyridinyl or pyrimidinyl.

A very particularly preferably represents a single bond or methylene (CH ₂ ).

R ¹ very particularly preferably represents nitro or cyano (in particular cyano).

R ² very particularly preferably represents chlorine, bromine, methyl or ethyl.

R ³ very particularly preferably represents hydrogen or methyl. R ⁴ very particularly preferably represents optionally by nitro, cyano, fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, trifluoromethyl, methoxy, ethoxy , n- or i-propoxy, difluoromethoxy, trifluoromethoxy, methylthio, ethylthio, n- or i-propylthio, difluoromethylthio, trifluoromethylthio, methylsulfmyl, ethylsulfinyl, trifluoromethylsulfmyl,

Methylsulfonyl, ethylsulfonyl, trifluoromethylsulfonyl, methylenedioxy, ethylenedioxy, difluoromethylenedioxy, trifluoroethylenedioxy or tetrafluoroethylenedioxy or phenyl substituted by cyano, fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, n-, i-, i-, i- s- or t-butyl, trifluoromethyl, methoxy, ethoxy, n- or i-propoxy, difluoromethoxy,

Trifluoromethoxy, methylthio, ethylthio, n- or i-propylthio, difluoromethylthio, trifluoromethylthio, methylsulfmyl, ethylsulfinyl, trifluoromethylsulfinyl, methylsulfonyl, ethylsulfonyl or trifluoromethylsulfonyl substituted pyridinyl or pyrimidinyl.

According to the invention, preference is given to the compounds of the formula (I) in which there is a combination of the meanings listed above as preferred.

According to the invention, particular preference is given to the compounds of the formula (I) in which a combination of those listed as particularly preferred above

Meanings exist.

According to the invention, very particular preference is given to the compounds of the formula (I) in which there is a combination of the meanings listed above as being particularly preferred.

Furthermore, those compounds of formula (I) are particularly emphasized in which A for each optionally substituted by cyano, fluorine and / or chlorine

Methylene (CH ₂ ) or dimethylene (ethane-1,2-diyl, CH ₂ CH ₂ ) or trimethylene (propane-1,3-diyl, CH ₂ CH ₂ CH ₂ ),

R ^{1 represents} nitro or cyano (especially cyano),

R ^{2 represents} chlorine, bromine, methyl or ethyl,

R ^{3 represents} hydrogen or methyl, and

R ^{4 represents} hydrogen, cyano, fluorine, chlorine, methoxy, ethoxy, n- or i-propoxy, or represents cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl which is optionally substituted by cyano, fluorine, chlorine, methyl or ethyl.

The general or preferred radical definitions listed above apply both to the end products of the formula (I) and correspondingly to the starting or intermediate products required in each case for the preparation. These radical definitions can be combined with one another, that is to say also between the specified preferred ranges.

The new substituted 2-imino-thiazolines of the general formula (I) have interesting biological properties. They are particularly characterized by strong herbicidal - and to a certain extent also by insecticidal - effectiveness.

The new substituted 2-imino-thiazolines of the general formula (I) are obtained if 2-imino-thiazolines of the general formula (II)

in which

A, R ² , R ³ and R ^{4 have} the meaning given above,

- or acid adducts of compounds of the general formula (II) -

with alkylating or acylating agents of the general formula (III)

XR ¹ (III)

in which

R ^{1 has} the meaning given above and

X represents halogen or the grouping -O-CO-alkyl,

if appropriate in the presence of a reaction auxiliary and if appropriate in the presence of a diluent,

and, if appropriate, subsequently carries out substitution reactions in the customary manner as part of the definition of substituents.

In the event that in formula (I) R ^{1 is} nitro, the corresponding

Compounds can be prepared by reacting compounds of the formula (II) with customary nitrating agents, such as, for example, nitric acid - optionally in a mixture with sulfuric acid or acetic acid - by customary methods. In principle, the compounds of the general formula (I) can also be synthesized as shown schematically below:

Isomerization of 5-alkylidene-2-imino-thiazolidines of the general formula (IV) - where A, R ¹ , R ³ and R ^{4 have} the meaning given above and R ^{2 "1 is} hydrogen or alkyl - at elevated temperature:

(IV) (la)

If, for example, 5-ethyl-2-imino-3- (3-trifluoromethyl-phenyl) thiazoline and chloroacetonitrile are used as starting materials, the course of the reaction in the process according to the invention can be outlined using the following formula:

Formula (II) provides a general definition of the 2-imino-thiazolines to be used as starting materials in the process according to the invention for the preparation of compounds of the general formula (I). In the general formula (II), A, R ² , R ³ and R ⁴ preferably have those meanings which have already been mentioned above in connection with the description of the compounds of the invention Formula (I) has been given as preferred, particularly preferred or very particularly preferred for A, R ² , R ³ and R ⁴ .

The starting materials of the general formula (II) are known and / or can be prepared by processes known per se (cf. US-A-5459277, EP-A-545431).

Formula (III) provides a general definition of the alkylating or acylating agents to be used as starting materials in the process according to the invention. In the general formula (III), R ¹ preferably has the meaning which have already been given above in connection with the description of the compounds of the general formula (I) according to the invention as preferred, particularly preferred or very particularly preferred for R ¹ ; X preferably represents fluorine, chlorine, bromine, iodine or the grouping -O-CO- (C, -C ₄ - alkyl), in particular chlorine, bromine, iodine or -O-CO-CH ₃ .

The starting materials of the general formula (III) are known synthetic chemicals.

The process according to the invention for the preparation of compounds of the general formula (I) is optionally carried out using a reaction auxiliary. The usual inorganic or organic bases or acid acceptors are generally suitable as reaction aids for the process according to the invention. These preferably include alkali metal or alkaline earth metal acetates, amides, carbonates, bicarbonates, hydrides, hydroxides or alkanolates, such as sodium, potassium or calcium acetate, lithium,

Sodium, potassium or calcium amide, sodium, potassium or calcium carbonate, sodium, potassium or calcium hydrogen carbonate, lithium, sodium, potassium or calcium hydride, lithium, sodium, potassium or Calcium hydroxide, sodium or potassium methoxide, ethanolate, n- or -i-propanolate, -n-, -i-, -s- or -t-butanolate; also basic organic nitrogen compounds, such as trimethylamine, triethylamine, tripropylamine, tributylamine, ethyldiisopropyl amine, N, N-dimethyl-cyclohexylamine, dicyclohexylamine, ethyl-dicyclohexylamine, N, N-dimethyl-aniline, N, N-dimethyl-benzylamine, pyridine, 2-methyl, 3-methyl, 4-methyl, 2 , 4-dimethyl-, 2,6-dimethyl-, 3,4-dimethyl- and 3,5-dimethyl-pyridine, 5-ethyl-2-methyl-pyridine, 4-dimethylamino-pyridine, N-methyl-piperidine, 1,4-diazabicyclo [2,2,2] octane (DABCO), 1,5-diazabicyclo [4,3,0] non-5-ene (DBN), or

1,8-diazabicyclo [5,4,0] -undec-7-ene (DBU).

Phase transfer catalysts are also suitable as further reaction aids for the process according to the invention. Examples of such catalysts are:

Tetrabutylammonium bromide, tetrabutylammonium chloride, tetraoctylammonium chloride, tetrabutylammonium hydrogen sulfate, methyl trioctylammonium chloride, hexadecyl-trimethylammonium chloride, hexadecyl-trimethylammonium-bromide, benzylchloride, benzyl methylammonium hydroxide, benzyl triethylammonium hydroxide, benzyl tributyl ammonium chloride, benzyl tributylammonium bromide, tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tributyl hexadecylphosphonium bromide, butyl triphenyl Tetraphenylphosphonium bromide.

The process according to the invention for the preparation of the compounds of the general formula (I) is preferably carried out using diluents. In addition to water, suitable diluents for carrying out the process according to the invention are, above all, inert organic solvents.

These include in particular aliphatic, alicyclic or aromatic, optionally halogenated hydrocarbons, such as, for example, gasoline, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, chloroform, carbon tetrachloride; Ethers such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran or ethylene glycol dimethyl or diethyl ether; Ketones, such as acetone, butanone or methyl isobutyl ketone; Nitriles, such as acetonitrile, propio nitrile or butyronitrile; Amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoric acid triamide; Esters such as methyl acetate or ethyl acetate, sulfoxides such as dimethyl sulfoxide, alcohols such as methanol, ethanol, n- or i-propanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, their mixtures with water or pure water.

The reaction temperatures can be varied within a substantial range when carrying out the process according to the invention. In general, temperatures between 0 ° C and 150 ° C, preferably between 10 ° C and 120 ° C.

The process according to the invention is generally carried out under normal pressure. However, it is also possible to carry out the process according to the invention under elevated or reduced pressure - generally between 0.1 bar and 10 bar.

To carry out the process according to the invention, the starting materials are generally used in approximately equimolar amounts. However, it is also possible to use one of the components in a larger excess. The reaction is generally carried out in a suitable diluent in the presence of a reaction auxiliary and the reaction mixture is generally stirred at the required temperature for several hours. The work-up is carried out using customary methods (cf. the manufacturing examples).

The active compounds according to the invention can be used as defoliants, desiccants, haulm killers and in particular as weed killers. Weeds in the broadest sense are understood to mean all plants that grow in places grow where they are undesirable. Whether the substances according to the invention act as total or selective herbicides depends essentially on the amount used.

The active compounds according to the invention can e.g. can be used in the following plants:

Dicotyledon weeds of the genera: Sinapis, Lepidium, Galium, Stellaria, Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsium, Carduippum, Sonuanum , Rotala, Lindernia, Lamium, Veronica,

Abutilon, Emex, Datura, Viola, Galeopsis, Papaver, Centaurea, Trifolium, Ranunculus, Taraxacum.

Dicotyledon cultures of the genera: Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis,

Brassica, lactuca, cucumis, cucurbita.

Monocotyledonous weeds of the genera: Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleocharis,

Scirpus, Paspalum, Ischaemum, Sphenoclea, Dactyloctenium, Agrostis, Alopecurus, Apera, Aegilops, Phalaris.

Monocot cultures of the genera: Oryza, Zea, Triticum, Hordeum, Avena, Seeale, Sorghum, Panicum, Saccharum, Pineapple, Asparagus, Allium.

However, the use of the active compounds according to the invention is by no means restricted to these genera, but extends in the same way to other plants. Depending on the concentration, the active compounds according to the invention are suitable for combating total weeds, for example on industrial and rail tracks and on paths and squares with and without tree growth. The active compounds according to the invention for combating weeds in permanent crops, for example forest, ornamental wood, fruit, wine, citrus, nut, banana, coffee, tea, rubber, oil palm,

Cocoa, berry fruit and hop plants, on ornamental and sports turf and pasture land as well as for selective weed control in annual crops.

The compounds of formula (I) according to the invention show strong herbicidal activity and a broad spectrum of activity when used on the soil and on above-ground parts of plants. To a certain extent, they are also suitable for the selective control of monocotyledon and dicotyledon weeds in monocotyledon and decotyledon crops, both in the pre-emergence and in the post-emergence process.

The active compounds can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusts, pastes, soluble powders, granules, suspension emulsion concentrates, active substance-impregnated natural and synthetic substances and very fine encapsulations in polymeric substances.

These formulations are prepared in a known manner, e.g. B. by mixing the active ingredients with extenders, ie liquid solvents and / or solid carriers, optionally using surface-active agents, ie emulsifiers and / or dispersants and / or foam-generating agents.

If water is used as an extender, e.g. also organic

Solvents are used as auxiliary solvents. The following are essentially suitable as liquid solvents: aromatics, such as xylene, toluene, or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as Chlorobenzenes, chlorethylenes or methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffins, for example petroleum fractions, mineral and vegetable oils, alcohols such as butanol or glycol and their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, and water.

Possible solid carriers are: e.g. Ammonium salts and natural rock powders such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powders such as highly disperse silica, aluminum oxide and silicates are suitable as solid carriers for granules: e.g. broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules from inorganic and organic flours and granules from organic material such as sawdust, coconut shells, corn cobs and tobacco stems; as emulsifying and / or foam-generating agents are possible: e.g. non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. Alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates; Possible dispersants are: e.g. Lignin sulfite liquor and methyl cellulose.

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

Dyes such as inorganic pigments, for example iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc can be used. The formulations generally contain between 0.1 and 95 percent by weight of active compound, preferably between 0.5 and 90%.

The active compounds according to the invention, as such or in their formulations, can also be used for combating weeds, in a mixture with known herbicides, finished formulations or tank mixes being possible.

Known herbicides are suitable for the mixtures, for example acetochlor, acifluorfen (sodium), aclonifen, alachlor, alloxydim (sodium), ametryne, amidochlor, amidosulfuron, anilofos, asulam, atrazine, azafenidin,

Azimsulfuron, Benazolin (-ethyl), Benfuresate, Bensulfuron (-methyl), Bentazon, Benzofenap, Benzoylprop (-ethyl), Bialaphos, Bifenox, Bispyribac (-sodium), Bromobutide, Bromofenoxim, Bromoxynil, Butachlor, Butroxydim, Butylate, Cafenstrole, Caloxydim, Carbetamide, Carfentrazone (-ethyl), Chlomethoxyfen, Chloramben, Chloridazon, Chlorimuron (-ethyl), Chlornitrofen, Chlorsulfuron, Chlortoluron, Cinidone (-ethyl), Cinmethylin, Cinosulfuron, Clethodim, Clpropargylop Clomazone, Clomeprop, Clopyralid, Clopyrasulfuron (-methyl), Cloransulam (- methyl), Cumyluron, Cyanazine, Cybutryne, Cycloate, Cyclosulfamuron, Cycloxydim, Cyhalofop (-butyl), 2,4-D, 2,4-DB, 2,4-DP, Desmedipham, Diallate, Dicamba, Diclofop (-mefhyl), Diclosulam, Diethatyl (-ethyl), Difenzoquat, Diflufenican, Difluefenzopyr, Dimefuron, Dimepiperate, Dimethachlor, Dimethametryn, Dimethenamid, Dimexramine Diphen Diquat, Dithiopyr, Diuron, Dymron, Epoprodan, EPTC, Esprocarb, Ethalfluralin, Ethametsulfuron (- methyl), ethofumesate, ethoxyfen, ethoxysulfuron, etobenzanide, fenoxaprop (-P-ethyl), flamprop (-isopropyl), flamprop (-isopropyl-L), flamprop (-methyl), flazasulfuron, fluazifop (-P-butyl) , Fluazolate, Flucarbazone, Flufenacet, Flumetsulam, Flumiclorac (-pentyl), Flumioxazin, Flumipropyn, Flumetsulam, Fluometuron, Fluorochloridone, Fluoroglycofen (-ethyl), Flupoxam, Flupropacil, Flurpyrsulfuron (-), Methyl, ), Fluridone, Fluroxypyr (-meptyl), Flurprimidol, Flurtamone, Fluothiacet (-methyl), Fluthiamide, Fomesafen, Glufosinate (-ammonium), Glyphosate (- isopropylammonium), Halosafen, Haloxyfop (-ethoxyethyl), Haloxyfop (-Haloxyfop ( -methyl), Hexazinone, imazamethabenz (-methyl), imazamethapyr propalin, imazamox, imazapic, imazapyr, imazaquin, imazethapyr, imazosulfuron, iodosulfuron, ioxynil, iso-, isoproturon, isouron, isoxaben, Isoxachlortole, isoxaflutole, isoxapyrifop, lactofen, lenacil, linuron, MCPA, MCPP, Mefenacet, Mesotrione, Metamitron, Metazachlor, Mefhabenzthiazuron, Metobenzuron, Metobromuron, (alpha-) Metolochlor, Metosulam, Metoxuron, Metribuzin, Metsulfuron (-methyl), Molinate, Monolinuron, Naproanulfuron, Naproanulfuron, Norflurazon, orben-carb, oryzalin, oxadiargyl, oxadiazon, oxasulfuron, oxaziclomefone, oxyfluorfen, paraquat, pelargonic acid, pendimethalin, pentoxazone, phenmedipham, piperophos, pretilachlor, primisulfuron (-methyl), propetrizil, propetrynil, propetrynil, propetrynil, propetrynan, propetrynil, propetrynil, propetrynil, propetrynil Propyzamides, prosulfocarb, prosulfuron, pyraflufen (-ethyl), pyrazolates, pyrazosulfuron (-ethyl), pyrazoxyfen, pyribenzoxime, pyributicarb, pyridates, pyriminobac (-methyl), pyrithiobac (-sodium), Q uinchlorac, Quinmerac, Quinoclamine, Quizalofop (-P-ethyl), Quizalofop (-P-tefuryl), Rimsulfuron, Sethoxydim, Simazine, Simetryn, Sulcotrione, Sulfentrazone, Sulfometuron (-methyl),

Sulfosate, Sulfosulfuron, Tebutam, Tebuthiuron, Tepraloxydim, Terbuthylazine, Terbutryn, Thenylchlor, Thiafluamide, Thiazopyr, Thidiazimin, Thifensulfuron (- methyl), Thiobencarb, Tiocarbazil, Tralkoxydim, Triallate, Tri-sulfonuronuron- tri-sulfonuron-tri-sulfate- Tridiphane, trifluralin and triflusulfuron.

A mixture with other known active compounds, such as fungicides, insecticides, acaricides, nematicides, bird repellants, plant nutrients and agents which improve soil structure, is also possible.

The active compounds can be used as such, in the form of their formulations or in the use forms prepared therefrom by further dilution, such as ready-to-use solutions, suspensions, emulsions, powders, pastes and granules. They are used in the customary manner, for example by watering, spraying, spraying or scattering. The active compounds according to the invention can be applied both before and after emergence of the plants. They can also be worked into the soil before sowing.

The amount of active ingredient used can vary over a wide range. It essentially depends on the type of effect desired. In general, the application rates are between 1 g and 10 kg of active ingredient per hectare of soil, preferably between 5 g and 5 kg per ha.

The preparation and use of the active compounds according to the invention can be seen from the examples below.

Preparation Examples:

example 1

0.6 g (5 mmol) of cyanogen bromide are stirred at room temperature (20 ° C. to 25 ° C.) to a mixture of 1.5 g (5 mmol) of 2-imino-5-methyl-3- (3-trifluoromethyl- phenyl) thiazoline hydrochloride, 1.1 g (10 mmol) of triethylamine and 60 ml of ethyl acetate and the reaction mixture is stirred for 30 minutes at room temperature. Then it is washed with 1N hydrochloric acid, dried with sodium sulfate and filtered. The filtrate is concentrated in a water jet vacuum, the residue is digested with diisopropyl ether and the crystalline product is isolated by suction.

1.2 g (84% of theory) of 2-cyanimino-5-methyl-3- (3-trifluoromethylphenyl) thiazoline with a melting point of 153 ° C. are obtained.

Analogously to Example 1 and in accordance with the general description of the production process according to the invention, it is also possible, for example, to prepare the compounds of the general formula (I) listed in Table 1 below.

Table 1: Examples of the compounds of the formula (I)

Examples of use:

Example A

Pre-emergence test

Solvent: 5 parts by weight of acetone

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.

Seeds of the test plants are sown in normal soil. After about 24 hours, the soil is sprayed with the active ingredient preparation in such a way that the desired amount of active ingredient is applied per unit area. The concentration of the spray liquor is chosen so that the desired amount of active compound is applied in 1000 liters of water per hectare.

After three weeks, the degree of damage to the plants is rated in% damage compared to the development of the untreated control.

It means: 0% = no effect (like untreated control)

100% = total annihilation

In this test, for example, the compounds according to Preparation Examples 1 and 8, with good tolerance to crop plants, such as, for example, cotton and barley, show a strong action against weeds. Example B

Post emergence test

Solvent: 5 parts by weight of acetone

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

Test plants which have a height of 5 to 15 cm are sprayed with the active compound preparation in such a way that the desired amounts of active compound are applied per unit area. The concentration of the spray liquor is chosen so that in

1000 1 water / ha the desired amounts of active ingredient are applied.

It means:

0% = no effect (like untreated control)

100% = total annihilation

In this test, the compounds according to Preparation Examples 1 and 8, for example, show good tolerance to crop plants, such as e.g. Wheat, effective against weeds.

Claims

claims

1. Substituted 2-imino-3-fhiazolines of the general formula (I)

in which

A represents a single bond or optionally substituted alkanediyl (alkylene),

R ² for hydrogen, cyano, carboxy, carbamoyl, thiocarbamoyl,

Halogen, or for each optionally substituted alkyl or

Is alkoxycarbonyl,

R ³ for hydrogen, cyano, carboxy, carbamoyl, thiocarbamoyl,

Halogen, or represents in each case optionally substituted alkyl or alkoxycarbonyl, and

R ^{4 represents} hydrogen, cyano, halogen or alkoxy, or optionally substituted cycloalkyl, aryl or heterocyclyl,

including the possible E and Z isomers of these compounds. Substituted 2-imino-3-thiazolines according to Claim 1, characterized in that

A represents a single bond or alkanediyl (alkylene) having 1 to 4 carbon atoms which is optionally substituted by cyano, halogen or C 1 -C ₄ -alkoxy,

R ^{1 represents} nitro, cyano, thiocarbamoyl, or nitroalkyl, cyanoalkyl, thiocarbamoylalkyl or formylalkyl, each with up to 6 carbon atoms,

R ^{2 represents} hydrogen, cyano, carboxy, carbamoyl, thiocarbamoyl, halogen, or alkyl or alkoxycarbonyl, each optionally substituted by cyano, halogen or C, -C ₄ -alkoxy, each having up to 4 carbon atoms,

R ^{3 stands} for hydrogen, cyano, carboxy, carbamyl, thiocarbamoyl, halogen, or for alkyl or alkoxycarbonyl, each optionally substituted by cyano, halogen or C _] -C ₄ -alkoxy, each having up to 4 carbon atoms, and

R ⁴ for hydrogen, cyano, halogen, for alkoxy with 1 to 6 carbon atoms, for cycloalkyl with 3 to 6 carbon atoms optionally substituted by cyano, halogen or C 1 -C ₄ -alkyl, for optionally with nitro, cyano, halogen, C, -C ₄ alkyl, C _r C ₄ -

Haloalkyl, C _r C ₄ -alkoxy, C _r C ₄ -haloalkoxy, C _r C ₄ -alkylthio, C, -C ₄ -haloalkylthio, C _r C ₄ -alkylsulfmyl, C, -C ₄ -haloalkyl-sulfinyl, C _r C ₄ alkylsulfonyl, C, -C ₄ haloalkylsulfonyl, C, -C ₂ alkylene dioxy or C _r C ₂ haloalkylenedioxy substituted aryl having 6 or 10 carbon atoms, or for each optionally substituted by

Cyano, halogen, C, -C ₄ alkyl, C _] -C ₄ haloalkyl, C, -C ₄ alkoxy, C _r C ₄ haloalkoxy, C, _-C4 alkylthio, C, -C ₄ haloalkylthio, C, -C ₄ - alkylsulfinyl, C, -C ₄ haloalkylsulfinyl, C, -C ₄ alkylsulfonyl or C _r C ₄ - Haloalkylsulfonyl-substituted, monocyclic or bicyclic heterocyclyl having 1 to 9 carbon atoms, 1 to 4 nitrogen atoms and / or 1 or 2 oxygen or sulfur atoms.

3. Substituted 2-imino-3-thiazolines according to claim 1, characterized in that

A for a single bond or for each optionally by cyano,

Fluorine and / or chlorine substituted methylene (CH ₂ ) or dimethylene (ethane-1,2-diyl, CH ₂ CH ₂ ) or trimethylene (propane-1,3-diyl, CH ₂ CH ₂ CH ₂ ),

R ^{1 represents} nitro, cyano, thiocarbamoyl, nitromethyl, nitroethyl, nitro-propyl, cyanomethyl, cyanoethyl or cyanopropyl,

R ² for hydrogen, cyano, carboxy, carbamoyl, thiocarbamoyl, fluorine,

Chlorine, bromine, or for methyl, ethyl, n- or i-, each optionally substituted by cyano, fluorine, chlorine, methoxy or ethoxy

Propyl, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl,

R ^{3 represents} hydrogen, cyano, carboxy, carbamoyl, thiocarbamoyl, fluorine, chlorine, bromine, or each optionally by cyano, fluorine,

Chlorine, methoxy or ethoxy substituted methyl, ethyl, n- or i-propyl, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl, and

R ⁴ for hydrogen, cyano, fluorine, chlorine, bromine, methoxy, ethoxy, n- or i-propoxy, for each optionally by cyano, fluorine, chlorine, Methyl or ethyl substituted cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl, for optionally by nitro, cyano, fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl , Trifluoromethyl, methoxy, ethoxy, n- or i-propoxy, difluoromethoxy, trifluoromethoxy, methylthio, ethylthio, n- or i-propylthio, difluoromethylthio, trifluoromethylthio, methylsulfmyl, ethylsulfinyl, trifluoromethylsulfinyl, methylsulfonylmethylsulfonyl, methylsulfonyl , Ethylenedioxy, difluoromethylene, tri-fluoroethylenedioxy or tetrafluoroethylenedioxy substituted phenyl, or for each optionally substituted by cyano, fluorine, chlorine, bromine,

Methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, trifluoromethyl, methoxy, ethoxy, n- or i-propoxy, difluoromethoxy, trifluoromethoxy, methylthio, ethylthio, n- or i- Propylthio, difluoromethylthio, trifluoromethylthio, methylsulfmyl, ethylsulfinyl, trifluoromethylsulfmyl, methylsulfonyl, ethylsulfonyl or trifluoromethylsulfonyl substituted heterocyclyl from the series furyl, thienyl, pyridinyl or pyrimidinyl.

4. Substituted 2-imino-3-thiazolines according to claim 1, characterized in that

A represents a single bond or methylene (CH ₂ ),

R ^! represents nitro or cyano (in particular cyano),

R ^{2 represents} chlorine, bromine, methyl or ethyl,

R ^{3 represents} hydrogen or methyl, and

R ⁴ for optionally by nitro, cyano, fluorine, chlorine, bromine, methyl,

Ethyl, n- or i-propyl, n-, i-, s- or t-butyl, trifluoromethyl, Methoxy, ethoxy, n- or i-propoxy, difluoromethoxy, trifluoromethoxy, methylthio, ethylthio, n- or i-propylthio, difluoromethylthio, trifluoromethylthio, methylsulfmyl, ethylsulfinyl, trifluoromethylsulfinyl, methylsulfonyl, trifluoromethylsulfonyl, trifluoromethyl Methylenedioxy, ethylenedioxy, difluoromethylenedioxy, trifluoro-ethylenedioxy or tetrafluoroethylenedioxy, or phenyl substituted for, in each case optionally by cyano, fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl , Trifluoromethyl, methoxy, ethoxy, n- or i-propoxy, difluoromethoxy, trifluoromethoxy, methylthio, ethylthio, n- or i-propylthio, difluoromethylthio, trifluoromethylthio, methylsulfmyl, ethylsulfinyl, trifluoromethylsulfyl, methylsulfyl, methylsulfyl, methylsulfyl, methylsulfyl, methylsulfyl, methylsulfyl, methylsulfonyl substituted pyridinyl or pyrimidinyl.

Substituted 2-imino-3-thiazolines according to Claim 1, characterized in that

A represents optionally cyano-, fluorine and / or chlorine-substituted methylene _(CH2) or dimethylene (ethane-l, 2-diyl, CH ₂ CH ₂₎ or trimethyl len (propane- 1, 3 -diyl, CH ₂ CH ₂ CH ₂ )

R ^{1 represents} nitro or cyano,

R ^{2 represents} chlorine, bromine, methyl or ethyl,

R ^{3 represents} hydrogen or methyl, and

R ⁴ for hydrogen, cyano, fluorine, chlorine, methoxy, ethoxy, n- or i-

Propoxy, or for cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl optionally substituted by cyano, fluorine, chlorine, methyl or ethyl.

6. Substituted 2-imino-3-thiazolines according to one of claims 1 to 5, characterized in that R ^{1 is} cyano.

7. Substituted 2-imino-3-thiazolines according to one of claims 1 to 6, characterized in that R ^{4 represents} phenyl or pyridinyl substituted by trifluoromethyl and / or fluorine or chlorine.

8. A process for the preparation of substituted 2-imino-3-thiazolines according to any one of claims 1 to 7, characterized in that 2-imino-thiazolines of the general formula (II)

in which

A, R ² , R ³ and R ^{4 have} the meaning given in one of claims 1 to 7,

- or acid adducts of compounds of the general formula (II) -

with alkylating or acylating agents of the general formula (III)

XR ¹ (III)

in which

R ^{1 has} the meaning given in one of claims 1 to 6 and X represents halogen or the grouping -O-CO-alkyl,

9. Use of at least one substituted 2-imino-3-thiazoline according to one of claims 1 to 7 for controlling unwanted plants and / or animal pests, in particular insects.

10. Plant treatment agent, characterized by the content of at least one substituted 2-imino-3-thiazoline according to one of claims 1 to 7 and conventional extenders.