EP1202981A1

EP1202981A1 - Substituted heteroaryloxyacetanilides and their use as herbicides

Info

Publication number: EP1202981A1
Application number: EP00949287A
Authority: EP
Inventors: Klaus-Helmut Müller; Lothar Rohe; Joachim Kluth; Mark Wilhelm Drewes; Peter Dahmen; Dieter Feucht; Rolf Pontzen
Original assignee: Bayer AG
Current assignee: Bayer CropScience AG
Priority date: 1999-07-20
Filing date: 2000-07-07
Publication date: 2002-05-08
Also published as: PL359366A1; KR20020012614A; MXPA02000679A; BR0012563A; US6544931B1; CA2379562A1; CN1361772A; JP2003505381A; DE19933936A1; HK1048315A1; AU6270300A; WO2001005777A1

Abstract

The invention relates to compounds of formula (I), wherein Xn represents a hydrogen or defined substituents, R represents s-butyl, t-butyl, 1-ethyl-propyl, 2-propinyl, 1-methyl-2-propinyl, 1-ethyl-2-propinyl, 2-butinyl, 1-methyl-2-butinyl or 1-ethyl-2-butinyl, and Z represents heteroaryl that is optionally substituted and that is chosen from the group of oxazolyl, benzoxazolyl, thiazolyl, benzthiazolyl, oxadiazolyl, thiadiazolyl. The inventive substances are characterized by their herbicidal properties.

Description

SUBSTITUTED HETEROARYLOXYACETANILIDES AND THEIR USE AS HERBICIDES

The invention relates to new substituted heteroaryloxyacetanihde, a process and intermediates for their preparation and their use as herbicides.

It is already known that certain substituted heteroaryloxyacetanihde have herbicidal properties (cf. EP-A-037524, cf. also EP-A-005501, EP-A-18497, EP-A-37526, EP-A-37527, EP- A-94541, EP-A-100044, EP-A-148501, EP-A-300344, EP-A-348734, EP-A-348737, US-A-4509971, US-A-4585471, US-A- 4645525, US-A-4708731, US-A-4968342, US-A-4988380). However, the action of these previously known compounds, especially at low application rates and concentrations, is not completely satisfactory in all areas of application.

New substituted heteroaryloxyacetanihde of the general formula (I)

in which

n represents the numbers 0, 1, 2 or 3,

R for s-butyl, t-butyl, l-ethyl-propyl, 2-propynyl, l-methyl-2-propynyl, 1-

Ethyl 2-propynyl, 2-butynyl, 1-methyl-2-butynyl or 1-ethyl-2-butynyl,

X for nitro, cyano, fluorine, chlorine, bromine or for methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl which is optionally substituted by cyano, fluorine, chlorine, methoxy or ethoxy, Methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, n- or i-propylthio, methylsulfinyl, ethylsulfinyl, n- or i-propylsulfinyl, methylsulfonyl, ethylsulfonyl, n- or i-propylsulfonyl, and Z for each optionally by nitro, cyano, carbamoyl, thiocarbamoyl,

Fluorine, chlorine, bromine, or by (in each case optionally substituted by cyano, fluorine, chlorine, methoxy or ethoxy) methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy , n- or i-propoxy, n-, i-, s- or t-

Butoxy, methylthio, ethylthio, n- or i-propylthio, n-, i-, s- or t-butylthio, methylsulfinyl, ethylsulfinyl, n- or i-propylsulfinyl, methylsulfonyl, ethylsulfonyl, n- or i-propylsulfonyl substituted Heteroaryl from the series oxazolyl, benzoxazolyl, thiazolyl, benzthiazolyl, oxadiazolyl, thiadiazoyl,

found.

Preferred substituents or ranges of the radicals present in the formulas listed above and below are described below.

n preferably represents the numbers 0, 1 or 2.

R preferably represents s-butyl, t-butyl, l-ethyl-propyl, 2-propynyl or 1-methyl-2-propynyl.

X preferably represents nitro, cyano, fluorine, chlorine, bromine or methyl, ethyl, n- or i-propyl, methoxy, ethoxy, methylthio, ethylthio, methylsulfinyl, ethylsulfinyl, which are each optionally substituted by cyano, fluorine, chlorine, methoxy or ethoxy , Methylsulfonyl or ethylsulfonyl.

Z preferably represents in each case optionally by nitro, cyano, carbamoyl,

Thiocarbamoyl, fluorine, chlorine, bromine, or by (in each case if necessary by

Cyano, fluorine, chlorine, methoxy or ethoxy substituted) methyl, ethyl, n- or i-propyl, methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, n- or i-propylthio, methylsulfinyl, ethylsulfinyl, n- or i-propylsulfinyl, Methylsulfonyl, ethylsulfonyl, n- or i-propylsulfonyl substituted heteroaryl from the series oxazolyl, benzoxazolyl, thiazolyl, benzthiazolyl, 1,2,4-oxadiazolyl, 1,3,4-oxadiazolyl, 1,2,4-thiadiazoyl, 1,3 , 4-thiadiazoyl.

n particularly preferably represents the numbers 0, 1 or 2.

R particularly preferably represents s-butyl, t-butyl, l-ethyl-propyl, 2-propynyl or l-methyl-2-propynyl.

X particularly preferably represents nitro, cyano, fluorine, chlorine, bromine or methyl, ethyl, n- or i-propyl, methoxy, ethoxy, methylthio, ethylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl or each optionally substituted by fluorine and / or chlorine ethylsulfonyl.

Z particularly preferably represents in each case optionally through nitro, cyano,

Carbamoyl, thiocarbamoyl, fluorine, chlorine, bromine, or by (in each case optionally substituted by fluorine and / or chlorine) methyl, ethyl, n- or i-propyl, methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, n - or i- Propylthio, methylsulfinyl, ethylsulfinyl, n- or i-propylsulfinyl, methylsulfonyl, ethylsulfonyl, n- or i-propylsulfonyl substituted heteroai'yl from the series oxazolyl, benzoxazolyl, thiazolyl, benzthiazolyl, 1, 2,4- Oxadiazolyl, 1,2,4-thiadiazolyl, 1,3,4-thiadiazolyl.

very particularly preferably stands for the numbers 0 or 1.

R very particularly preferably represents t-butyl, l-ethyl-propyl or 2-propynyl.

X very particularly preferably represents cyano, fluorine, chlorine, methyl, ethyl, trifluoromethyl, methoxy or trifluoromethoxy. Z very particularly preferably represents in each case optionally by nitro, fluorine,

Chlorine, bromine, methyl, ethyl, n- or i-propyl, difluoromethyl, trifluoromethyl, difluorochloromethyl, fluorodichloromethyl, dichloromethyl, trichloromethyl, methylthio, ethylthio, n- or i-propylthio-substituted heteroaryl from the series oxazolyl, benzoxylylylolol, thiazole 1, 2,4-oxadiazolyl,

1,2,4-thiadiazolyl, 1,3,4-thiadiazolyl.

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. This

Residual definitions can be combined with one another, that is, also between the specified preferred ranges.

Preferred compounds according to the invention are those 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 those compounds of the formula (I) in which there is a combination of the meanings listed above as being particularly preferred.

Those compounds of the formula (I) which have a combination of the meanings given above as being very particularly preferred are very particularly preferred according to the invention.

Optionally substituted radicals can be mono- or polysubstituted, whereby in the case of multiple substitution the substituents can be the same or different.

A very particularly preferred group are those compounds of the

Formula (I) in which n represents the numbers 0 or 1,

R represents t-butyl,

X represents cyano, fluorine, chlorine, methyl, ethyl, trifluoromethyl, methoxy or trifluoromethoxy, and

Z for each optionally substituted by fluorine, chlorine, bromine, methyl, ethyl, difluoromethyl, trifluoromethyl, dichloromethyl or trichloromethyl

Heteroaryl from the series oxazolyl, benzoxazolyl, thiazolyl, benzthiazolyl, 1,2,4-thiadiazolyl, 1, 3,4-thiadiazolyl.

Another very particularly preferred group are those compounds of the formula (I) in which

n represents the numbers 0 or 1,

R represents 2-propynyl,

Heteroaryl from the series oxazolyl, benzoxazolyl, thiazolyl, benzthiazolyl, 1,2,4-thiadiazolyl, 1,3,4-thiadiazolyl.

The new substituted heteroaryloxyacetanihde of general Fonnel (I) have interesting biological properties. They are particularly characterized by their strong and selective herbicidal activity. The new substituted heteroaryloxyacetanihde of the general formula (I) are obtained if

Heteroarenes of the general formula (II)

ZX ¹ (II) in which

Z has the meaning given above and

X represents fluorine, chlorine, bromine, methylthio, methylsulfinyl or methylsulfonyl,

with hydroxyacetanilides of the general formula (III)

in which

n, R and X have the meaning given above,

if appropriate in the presence of an acid binder and if appropriate in the presence of a diluent.

If, for example, 2-chloro-benzoxazole and N- (t-butyl) -N- (3-fluorophenyl) -2-hydroxyacetamide 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 heteroarenes 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), Z preferably or in particular has the meaning which have already been mentioned above in connection with the description of the compounds of the general formula (I) according to the invention preferably or as being particularly preferred for Z; X ¹ preferably represents chlorine or methylsulfonyl.

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

Formula (III) provides a general definition of the hydroxyacetanilides 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 (III), n, R and X preferably or in particular have those meanings which have already been mentioned above in connection with the description of the compounds of the general formula (I) according to the invention preferably or as particularly preferred for n, R and X. have been.

The starting materials of the general formula (III) with the exception of the compounds N- (s-butyl) -N- (4-ethoxyphenyl) -2-hydroxy-acetamide, N- (s-butyl) -N- (4-methyl - phenyl) -2-hydroxy-acetamide, N- (t-butyl) -N-phenyl-2-hydroxy-acetamide, N-phenyl-N- (2-propynyl) -2-hydroxy-acetamide and N-phenyl- N- (l-methyl-2-propynyl) -2-hydroxy-acetamide (see DE-A-2160380, DE-A-2201432, DE-A-3038608, EP-A-753507, US-A-3954827) are not yet known from the literature. With the exception of the compounds N- (s-butyl) -N- (4-ethoxy-phenyl) -2-hydroxy-acetamide, N- (s-butyl) -N- (4-methyl-phenyl) -2- hydroxyacetamide, N- (t-butyl) -N-phenyl-2- Hydroxy-acetamide, N-phenyl-N- (2-propynyl) -2-hydroxy-acetamide and N-phenyl-N- (l-methyl-2-propynyl) -2-hydroxy-acetamide as new substances are also the subject of the present Registration.

The hydroxyacetanilides of the general formula (III) are obtained if haloacetanilides of the general formula (IV)

in which

R and X have the meaning given above and

X 'represents fluorine, chlorine or bromine (especially chlorine),

with alkali metal acetates, e.g. Sodium acetate or potassium acetate, optionally in the presence of reaction auxiliaries, such as e.g. Potassium carbonate and triethylamine, and optionally in the presence of diluents such as e.g. N, N-dimethylformamide or N, N-dimethyl acetamide, at temperatures between 50 ° C and 150 ° C and the acetoxyacetanihde of the general formula (V) formed

in which

n, R and X have the meaning given above, - if necessary after intermediate insulation or also “in situ” - with methanol, if appropriate in the presence of an acid acceptor, such as sodium methylate, at temperatures between 20 ° C. and 100 ° C. and worked up by customary methods (cf. the preparation examples).

The haloacetanihde of the general formula (IV) required as precursors are known and / or can be prepared by processes known per se (cf. DE-A-2362743, DE-A-2633159, US-A-3345151).

The haloacetanihde of the general formula (IV) are obtained if N-substituted anilines of the general formula (VI)

in which

n, R and X have the meaning given above,

with haloacetyl halides of the general formula (VII)

in which

X ^" and X ³ each represent fluorine, chlorine or bromine (especially chlorine),

if appropriate in the presence of a reaction auxiliary, such as pyridine, and, if appropriate, in the presence of a diluent, such as toluene, at temperatures between 0 ° C. and 100 ° C. (cf. the preparation examples). Suitable diluents for carrying out the process according to the invention for the preparation of the compounds of the general formula (I) are, in addition to water, 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, propionitrile or butyronitrile;

Amides such as N, N-dimethylfonτιamid, N, N-dimethylacetamide, N-methyl-formanilide, N-methyl-pyπOlidon 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.

In general, the customary inorganic or organic bases or acid acceptors are suitable as acid binders 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 - - methanolate, -ethanolate, -n- or -i-propanolate, -n-, -i-, -s- or -t-butanolate; basic organic nitrogen compounds such as trimethylamine, triethylamine, tripropylamine, tributylamine, ethyl-diisopropylamine, N, N-dimethylcyclohexylamine, 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).

The reaction temperatures can be carried out when carrying out the process according to the invention

Process can be varied over a wide range. In general, temperatures between -20 ° C and 100 ° C, preferably between 0 ° C and 60 ° 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 an acid binder and the reaction mixture is generally stirred at the required temperature for several hours. Working up is carried out according to customary methods (cf. the production 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 all plants that grow in places 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 be used, for example, in the following plants: Dicotyledon weeds of the genera: Abutilon, Amaranthus, Ambrosia, Anoda, Anthemis, Aphanes, Atriplex, Bellis, Bidens, Capsella, Carduus, Cassia, Centaurea, Chenopodium, Cirsium, Convolvulus, Datura, Desmodium, Emex, Erysimum, Gupopsisia, Euphorbia , Galium, Hibiscus, Ipomoea, Kochia, Lamium, Lepidium, Lindernia, Matricaria, Mentha, Mercurialis, Mullugo, Myosotis, Papaver,

Pharbitis, Plantago, Polygonum, Portulaca, Ranunculus, Raphanus, Rorippa, Rotala, Rumex, Salsola, Senecio, Sesbania, Sida, Sinapis, Solanum, Sonchus, Sphenoclea, Stellaria, Taraxacum, Thlaspi, Trifolium, Urtica, Veronica, Viola, Xanth.

Dicotyledon cultures of the genera: Arachis, Beta, Brassica, Cucumis, Cucurbita,

Helianthus, Daucus, Glycine, Gossypium, Ipomoea, Lactuca, Linum, Lycopersicon, Nicotiana, Phaseolus, Pisum, Solanum, Vicia.

Monocotyledonous weeds of the genera: Aegilops, Agropyron, Agrostis, Alopecurus, Apera, Avena, Brachiaria, Bromus, Cenchrus, Commelina, Cynodon, Cyperus,

Dactyloctenium, Digitaria, Echinochloa, Eleocharis, Eleusine, Eragrostis, Eriochloa, Festuca, Fimbristylis, Heteranthera, Imperata, Ischaemum, Leptochloa, Lolium, Monochoria, Panicum, Paspalum, Phalaris, Phleum, Poa, Sagaria, Setaria, Setaria.

Monocot cultures of the genera: Allium, pineapple, asparagus, Avena, Hordeum, Oryza, Panicum, Saccharum, Seeale, Sorghum, Triticale, Triticum, Zea.

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 others

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 weed control 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 areas and for selective weed control in annual cultures are used.

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 dicotyledon crops, both in the pre-emergence and in the post-emergence process.

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

Substances.

These formulations are produced 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

Agents, ie emulsifiers and / or dispersants and / or foam-generating agents.

If water is used as an extender, organic solvents can, for example, also be 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 as well as synthetic granules from inorganic and organic flours as well as granules from organic material such as sawdust,

Coconut shells, corn cobs and tobacco stems; as emulsifying and / or foaming 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 waste liquor and

Methylcellulose.

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

Dyes such as inorganic pigments, e.g. 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 the form of their formulations, can also be used in a mixture with known herbicides for combating weeds, 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) Benzobicyclone, Benzofenap, Benzoylprop (-ethyl), Bialaphos, Bifenox, Bispyribac (- sodium), Bromobutide, Bromofenoxim, Bromoxynil, Butachlor, Butroxydim,

Butylates, cafenstrole, caloxydim, carbetamides, carfentrazone (-ethyl), chloromethoxyfen, chloramben, chloridazon, chlorimuron (-ethyl), chloronitrofen, chlorosulfonone, chlorotoluron, cinidon (-ethyl), cinmethylin, cinosulfuron, clefoxydim, clethod Clodinafop (-propargyl), Clomazone, Clomeprop, Clopyralid, Clopyra-sulfuron (-methyl), Cloransulam (-methyl), Cumyluron, Cyanazine, Cybutryne,

Cycloate, Cyclosulfamuron, Cycloxydim, Cyhalofop (-butyl), 2,4-D, 2,4-DB, 2,4-DP, Desmedipham, Diallate, Dicamba, Diclofop (-methyl), Diclosulam, Diethatyl (-ethyl), Difenzoquat, Diflufenican, Diflufenzopyr, Dimefuron, Dimepiperate, Dimethachlor, Dimethametryn, Dimethenamid, Dimexyflam, Dinitramine, Diphenamid, Diquat, Diethiopyr, Diuron, Dymron, Epropodan, EPTC, Esprocon, Ethamulfate- Ethoxyfen, Ethoxysulfuron, Etobenzanid, Fenoxaprop- (-P-ethyl), Fentrazamide, Flamprop (-isopropyl), Flamprop (-isopropyl-L), Flamprop (- methyl), Flazasulfuron, Florasulam, Fluazifop (-P-butyl), Fluazolate , Flucarbazone, Flufenacet, Flumetsulam, Flumiclorac (-pentyl), Flumioxazin, Flumipropyn, Flumet- sulam, Fluometuron, Fluorochloridone, Fluoroglycofen (-ethyl), Flupoxam, Fluprop-acil, Fluφyrsulfuron (-methyluren -sodium ), Fluridone, Fluroxypyr (- meptyl), Fluφrimidol, Flurtamone, Fluthiacet (-methyl), Fluthiamide, Fomesafen, Glufosinate (-ammonium), G Phyphosate (-isopropylammonium), Halosafen, Haloxyfop- (-ethoxyethyl), Haloxyfop (-P-methyl), Hexazinone, Imazamethabenz (-methyl), Imazamethapyr, Imazamox, Imazapic, Imazapyr, Imazaquin, Imazethapyr, Iodosulfuron methyl, sodium), ioxynil, isopropalin, isoproturon, isouron, Isoxaben, Isoxachlortole, Isoxaflutole, Isoxapyrifop, Lactofen, Lenacil, Linuron, MCPA, MCPP, Mefenacet, Mesotrione, Metamitron, Metazachlor, Methabenzthiazuron, Metobenzuron, Metobromuron, (alpha-) Metolachloruronuron, Metobromuron, Metolachloronuron, Metobromuron ), Molinate, Monolinuron, Naproanilide, Napropamide, Neburon, Nicosulfuron, Norflurazon, Orbencarb, Oryzalin, Oxadiargyl, Oxadiazon, Oxasulfuron, Oxaziclomefone, Oxyfluorfen, Paraquat, Pelargonic acid, Pendimedhaloxin, Pendraliperine, Pendraliperine Pretilachlor, Primisulfuron (-methyl), Prometryn, Propachlor, Propanil, Propaquizafop, Propisochlor, Propyzamide, Prosulfocarb, Prosulfuron, Pyraflufen (-ethyl), Pyrazolate, Pyrazosulfuron (-efhyl), Pyrazoxyfen, Pyribenzoxarb, Pyributoxox, Pyributoxim, Pyributox Pyriminobac (- methyl), Pyrithiobac (-sodium), Quinchlorac, Quinmerac, Quinoclamine, Quizalofop- (-P-ethyl), Quizalofop (-P-tefuryl), Rimsulfuron, Sethoxydim, Simazine, Simetryn, Sulcotrione, Sulfentrazone, Sulfome turon (-methyl), sulfosate, sulfosulfuron, tebutam, tebuthiuron, tepraloxydim, terbuthylazine, terbutryn, thenylchlor, thifluamamide, thiazopyr, thidiazimin, thifensulfuron (-methyl), thiobencarb, tiocarb- aulf, trallonuron, tralkonydur, tralkoxydib, tralkoxydur -methyl), triclopyr, tri-diphane, 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 usual way, e.g. by pouring, spraying, spraying, sprinkling.

The active compounds according to the invention can be applied both before and after the plants emerge. 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

A mixture of 5.0 g (21 mmol) of N- (t-butyl) -N- (4-chlorophenyl) -2-hydroxy-acetamide, 4.9 g (21 mmol) of 2-methylsulfonyl-5 -trifluoromethyl-l, 3,4-thiadiazole and 50 ml acetone is cooled to -15 ° C. and a solution of 1.4 g (35 mmol) sodium hydroxide in 7 ml water is added dropwise at this temperature while stirring. The reaction mixture is stirred for 3 hours at -15 ° C, then adjusted to pH 5 with acetic acid and then poured onto 500 ml of ice water. The solvent is removed by decanting, the remaining oily product is crystallized by digesting with petroleum ether and then isolated by suction.

6.5 g (79% of theory) of N- (t-butyl) -N- (4-chlorophenyl) -2- (5-trifluoromethyl-l, 3,4-thiadiazol-2-yl are obtained -oxy) -acetamide with a melting point of 82 ° C.

Example 2

2.1 g (10 mmol) of 2,6-dichlorobenzthiazole become at room temperature (approx. 20 ° C) with stirring to a mixture of 2.1 g (10 mmol) of N- (4-fluorophenyl) -N - (2-propynyl) -2-hydroxy-acetamide, 0.15 g (12.5 mmol) of sodium hydroxide, 2 ml of water and 30 ml of acetone are added and the reaction mixture is stirred for 15 hours at room temperature. temperature stirred. Then it is shaken well with 150 ml of methylene chloride, the organic phase is separated off, washed with water, 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.

2.0 g (97% of theory) of N- (4-fluorophenyl) -N- (2-propynyl) -2- (6-chlorobenzthiazol-2-yl-oxy) acetamide with a melting point of 126 are obtained ° C.

Analogously to Examples 1 and 2 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)

The logP values given in Table 1 were determined in accordance with EEC Directive 79/831 Annex V.A8 by HPLC (High Performance Liquid Chromatography) on a phase reversal column (C 18). Temperature: 43 ° C.

(a) Eluents for determination in the acidic range: 0.1% aqueous phosphoric acid, acetonitrile; linear gradient from 10% acetonitrile to 90% acetonitrile - corresponding measurement results are marked in Table 1 with ^a ).

(b) eluents for determination in the neutral range: 0.01 molar aqueous phosphate buffer solution, acetonitrile; linear gradient from 10% acetonitrile to 90% acetonitrile - corresponding measurement results are marked in Table 1 with ^D ).

The calibration was carried out with unbranched alkan-2-ones (with 3 to 16 carbon atoms) whose logP values are known (determination of the logP values on the basis of the retention times by linear interpolation between two successive alkanones).

The lambda max values were determined on the basis of the UV spectra from 200 nm to 400 nm in the maxima of the chromatographic signals. Starting materials of the formula (III): Example (III- 1)

A mixture of 22 g (85 mmol) of N- (t-butyl) -N- (4-chlorophenyl) -2-chloroacetamide, 3.3 g of potassium carbonate and 0.3 g of triethylamine is brought to 120 ° C heated and with stirring, 10.5 g of sodium acetate are added in portions to this mixture within 2 hours. The mixture is then stirred for a further 2 hours at 120 ° C. and then cooled to 50 ° C. Then 200 ml of methanol are added and the mixture is heated under reflux for 4 hours. After concentration in a water jet vacuum, the residue is shaken with 300 ml of water / 300 ml of methylene chloride, the organic phase is separated off, washed with water, 1N hydrochloric acid and then again with water, dried with sodium sulfate and filtered. The solvent is carefully distilled off from the filtrate under reduced pressure.

20.8 g (100% of theory) of N- (t-butyl) -N- (4-chlorophenyl) -2-hydroxyacetamide are obtained. logP (at pH = 2.3): 2.54.

Example (II1-2)

A mixture of 20 g (80 mmol) of N- (4-fluorophenyl) -N- (2-propynyl) -2-acetoxy-acetamide, 0.22 g (4 mmol) of potassium hydroxide and 200 ml of methanol is added for 4 hours Reflux heated and then concentrated in a water jet vacuum. The The residue is shaken with methylene chloride / water, the organic phase is separated off, dried with sodium sulfate and filtered. The solvent is carefully distilled off from the filtrate under reduced pressure.

14.9 g (90% of theory) of N- (4-fluorophenyl) -N- (2-propynyl) -2-hydroxyacetamide with a melting point of 57 ° C. are obtained.

Analogously to Examples (III-1) and (III-2), it is also possible, for example, to prepare the compounds of the general formula (III) shown in Table 2 below.

Table 2: Examples of the compounds of the formula (III)

Intermediates of formula (V):

Example (V-1)

A mixture of 20 g (88.5 mmol) of N- (4-fluorophenyl) -N- (2-propynyl) -2-chloroacetamide, 8.7 g (106 mmol) of sodium acetate, 1 g of benzyltriethylammonium chloride and 200 ml of toluene is heated under reflux for 7 hours. After cooling to room temperature, the mixture is washed with 1N hydrochloric acid and then with water, dried with sodium sulfate and filtered. The solvent is carefully distilled off from the filtrate under reduced pressure.

21.3 g (96% of theory) of N- (4-fluorophenyl) -N- (2-propynyl) -2-acetoxyacetamide are obtained.

Analogously to example (V-1), for example the compounds of the general formula (V) shown in Table 3 below can also be prepared.

Table 3: Examples of the compounds of the formula (V)

Products of formula (IV):

Example (IV- 1)

A mixture of 18.4 g (100 mmol) of N- (t-butyl) -N- (4-chlorophenyl) amine, 6.2 g (55 mmol) of chloroacetyl chloride and 50 ml of toluene is heated under reflux until a clear solution has been formed. Then another 6.2 g (55 mmol) of chloroacetyl chloride are added and the mixture is further heated under reflux until the evolution of gas (HG) has ended. The mixture is then concentrated in a water jet vacuum and the residue is distilled under reduced pressure.

22 g (89% of theory) of N- (t-butyl) -N- (4-chlorophenyl) -2-chloroacetamide are obtained. logP (at pH = 2.5): 3.34.

Example (IV-2)

A solution of 1 1, 3 g (0.1 mol) of chloroacetyl chloride in 30 ml of toluene is added dropwise at room temperature (about 20 ° C) with stirring to a mixture of 15 g (0.1 mol) of N- (4-fluorine -phenyl) -N- (2-propynyl) amine, 8.4 g of pyridine and 200 ml of toluene are added and the reaction mixture is stirred for 15 hours at room temperature. It is then washed with saturated aqueous sodium chloride solution and with water, dried with sodium sulfate and filtered. The filtrate is concentrated in vacuo, the residue digested with diisopropyl ether and the crystalline product isolated by suction.

20.5 g (90% of theory) of N- (4-fluorophenyl) -N- (2-propynyl) -2-chloroacetamide of melting point 1 15 ° C. are obtained.

Analogously to Examples (IV-1) and (IV-2), it is also possible, for example, to prepare the compounds of the general formula (I) listed in Table 4 below.

Table 4: Examples of the compounds of the formula (IV) X ^" here stand for Cl

Application examples: 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 specified amount is given

Amount of emulsifier and dilute the concentrate with water to the desired concentration.

Seeds of the test plants are sown in nomial 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 destruction

In this test, for example, the compounds according to Preparation Examples 1, 3, 4, 6, 7, 9 and 11 with strong tolerance to cultivated plants, such as cotton, corn, wheat and sugar beets, show a strong action against weeds.

Table A2: Pre emergence-Tcst / greenhouse

Table A3: Pre emergence-Tcst / greenhouse

Table A4: Pre emergence test / greenhouse

Table A5: Pre emergence test / greenhouse

Table A6: Pre emergence test / greenhouse

Table A7: Pre emergence test / greenhouse

Example B

Post-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 level

Concentration.

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.

After three weeks, the damage π-ad of the plants is rated in% damage in comparison 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 Example 1, 2, 3, 4, 6, 7 and 9 show a strong action against weeds. 4

Table B2: Post emergence test / greenhouse

Claims

claims

1. Compounds of the general formula (I),

5 a by g

for 2-propinyl, 1-methyl-2-propiny 10 l-ethyl-2-butinyl or l-ethyl- but

for or for each optionally substituted by oxy or ethoxy

15 Me -, i-, s- or t-butyl, methoxy,

Eth hio, ethylthio, n- or i-propylthi - or i-propylsulfinyl, methyl sul pylsulfonyl stands, and

20 Z for each optionally by nitro, cyano, carbamoyl, thio

2. Compounds according to Anspmch 1, characterized in that

n represents the numbers 0, 1 or 2,

R represents s-butyl, t-butyl, l-ethyl-propyl, 2-propynyl or l-methyl-2-propynyl,

X for nitro, cyano, fluorine, chlorine, bromine or for methyl, ethyl, n- or i-propyl, methoxy, ethoxy, methylthio, ethylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl, optionally substituted by cyano, fluorine, chlorine, methoxy or ethoxy or ethylsulfonyl, and

Z for in each case optionally by nitro, cyano, carbamoyl, thiocarbamoyl, fluorine, chlorine, bromine or by (in each case optionally substituted by cyano, fluorine, chlorine, methoxy or ethoxy) methyl, ethyl, n- or i-propyl, methoxy , Ethoxy, n- or i-propoxy, methylthio, ethylthio, n- or i-propylthio, methylsulfinyl, ethylsulfinyl, n- or i-propylsulfinyl, methylsulfonyl, ethylsulfonyl, n- or i-propylsulfonyl substituted heteroaryl from the series

Oxazolyl, benzoxazolyl, thiazolyl, benzthiazolyl, 1,2,4-oxadiazolyl, 1,3,4-oxadiazolyl, 1,2,4-thiadiazoyl, 1, 3,4-thiadiazoyl,

3. Compounds according to Anspmch 1 or 2, characterized in that

n represents the numbers 0, 1 or 2,

R represents s-butyl, t-butyl, l-ethyl-propyl, 2-propynyl or l-methyl-2-propynyl, X represents nitro, cyano, fluorine, chlorine, bromine or represents methyl, ethyl, n- or i-propyl, methoxy, ethoxy, methylthio, ethylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl or ethylsulfonyl, each optionally substituted by fluorine and / or chlorine, and

Z for each optionally by nitro, cyano, carbamoyl, thiocarbamoyl, fluorine, chlorine, bromine, or by (in each case optionally substituted by fluorine and / or chlorine) methyl, ethyl, n- or i-propyl, methoxy, ethoxy, n- or i-Propoxy, methylthio, ethylthio, n- or i-propylthio, methylsulfinyl, ethylsulfinyl, n- or i-propylsulfinyl, methylsulfonyl, ethylsulfonyl, n- or i-propylsulfonyl-substituted heteroaryl from the series oxazolyl, benzoxazolyl, thiazolyl, 1 , 2,4-oxadiazolyl, 1,2,4-thiadiazolyl, 1,3,4-thiadiazolyl.

4. Compounds according to one of claims 1 to 3, characterized in that

n represents the numbers 0 or 1,

R represents t-butyl, l-ethyl-propyl or 2-propynyl,

X for cyano, fluorine, chlorine, methyl, ethyl, trifluoromethyl, methoxy or

Trifluoromethoxy stands, and

Z for each optionally by nitro, fluorine, chlorine, bromine, methyl,

Ethyl, n- or i-propyl, difluoromethyl, trifluoromethyl, difluorochloromethyl, fluorodichloromethyl, dichloromethyl, trichloromethyl, methylthio, ethylthio, n- or i-propylthio substituted heteroaryl from the series oxazolyl, benzoxazolyl, thiazolyl, benzyl thiazolyl, 1, 2,4-oxadiazolyl, 1,2,4-thiadiazolyl, 1,3,4-thiadiazolyl.

5. Compounds according to one of claims 1 to 4, characterized in that

n represents the numbers 0 or 1,

R represents t-butyl, 1-ethylpropyl or 2-propinyl,

Z for each optionally by fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, difluoromethyl, trifluoromethyl, dichloromethyl,

Difluorochloromethyl, fluorodichloromethyl, trichloromethyl, methylthio, ethylthio, n- or i-propylthio substituted heteroaryl from the series oxazolyl, benzoxazolyl, thiazolyl, benzthiazolyl, 1, 2,4-oxadiazolyl, 1,2,4-thiadiazolyl, 1, 3,4 -Thiadiazolyl stands.

6. A method for producing the compounds according to any one of claims 1 to 5, characterized in that

Heteroarenes of the general formula (II)

ZX ¹ (II)

in which

Z has the meaning given in one of claims 1 to 5 and X ^{1 represents} fluorine, chlorine, bromine, methylthio, methylsulfinyl or methylsulfonyl,

with hydroxyacetanilides of the general formula (III)

in which

n, R and X have the meaning given in one of claims 1 to 5,

optionally in the presence of an acid binder and optionally in the presence of a diluent.

7. Compounds of the general formula (III),

characterized in that

n, R and X have the meaning given in one of claims 1 to 5,

except for the compounds N- (s-butyl) -N- (4-ethoxy-phenyl) -2-hydroxy-acetamide, N- (s-butyl) -N- (4-methyl-phenyl) -2-hydroxy -acetamide, N- (t-butyl) -N-phenyl-2-hydroxy-acetamide, N-phenyl-N- (2-propynyl) -2-hydroxy-acetamide and N-phenyl-N- (l-methyl- 2-propynyl) -2-hydroxy-acetamide.

8. A method for controlling unwanted vegetation, characterized in that at least one compound according to one of the sayings 1 to 5 can affect unwanted plants and / or their habitat.

9. Use of at least one compound according to one of claims 1 to 5 for controlling unwanted plants.

10. Herbicidal agent, characterized by a content of a compound according to one of claims 1 to 5 and conventional extenders and / or surface-active agents.

INTERNATIONAL SEARCH REPORT International application No. PCT / EP 00/06461

A. CLASSIFICATION OF SUBJECT MATTER

IPC 7 C07D285 / 13 C07D277 / 68 C07D263 / 58 C07D285 / 08 C07D271 / 07

C07D277 / 34 A01N43 / 74 A01N43 / 80 C07C235 / 16 According to International Patent Classification (IPC) or to both national classification and IPC

B. FIELDS SEARCHED

Mmimum documentation searched (classification System followed by classification Symbols) IPC 7 C07D A01N C07C

Documentation searched other than minimum documentation to the extent that such documents are included in the fields searched EPO-Internal, WPI Data, BEILSTEIN Data, CHEM ABS Data

Electronic data base consulted during the international search (name of data base and, where practical, search terms used)

C. DOCUMENTS CONSIDERED TO BE RELEVANT

Category * Citation of document, with indication, where appropriate, of the relevant passages Relevant to claim No.

X DE 30 38 608 A (BAYER AG) 1-10

19 May 1982 (19.05.82) the whole document, in particular page22, example 4

X DE 22 01 432 A (BADISCHE ANILIN-UND SODA-FABRIK AG)

19 July 1973 (7/19/73) cited in the application page 5, 17 to 25 compound, the abstract with page 7, equation b

X EP 0 010 673 A (BAYER AKTIENGESELLSCHAFT)

14 May 1980 (14.05.80) the whole document, in particular claim 2, process d and page 32, 2.

Formula scheme, the abstract with examples 11, 12, 15, 17, 18, 25, 26, 34, and

38-40

ÖFurther documents are sted in the continuation of box C. Patent family members are listed in annex.

* Special categories of cited documents "T" later document published after the international filing date or pπoπty date and not in conflict with the application but cited to

"A" document defining the general State of the art which is not resistance the pπnciple or theory underlying the mvention considered to be of particular relevance

"X" document of particular relevance, the claimed prevention cannot be

"E" earher document but published on or after the international filmg considered novel or cannot be considered to involve an inventive date step when the document is taken alone

"L" document which may thro doubts on pπoπty claιm (s) or which "Y" document of particular relevance, the claimed mvention cannot be cited to establish the pubhcation date of another citation or considered to involve an inventive step when the document is other Special reason (as specified) combined with one or more other such documents, such combination bemg obvious to a person skilled in the art

"O" document referring to an oral disclosure, use, exhibition or other means "&" document member of the same patent family

"P" document published pπor to the international fihng date but Iater than the pπoπty date claimed

Date of the actual completion of the international search Date of maihng of the international search report 1 November 2000 (01.11.00) 16 November 2000 (16.1 1.00)

Name and mailing address of the Authorized officer ISA EP Telephone No.

Form PCT / ISA / 210 (second sheet) (July 1992) C (Coπtlπuatlon) DOCUMENTS CONSIDERED TO BE RELEVANT

Category ^• Citation of document, with in Scation.whθre appropriate, of the relevant passagβs Relevant to claim No.

EP 0005501 A (BAYER AKTIENGESELLSCHAFT) 1-10 November 28, 1979 (1979-11-28) cited in the application the whole document

EP 0018497 A (BAYER AG) 1-10 November 12, 1980 (1980-11-12) cited in the application the whole document

EP 0094541 A (BAYER AG) 1-10 23 November 1983 (1983-11-23) cited in the application the whole document

EP 0100044 A (BAYER AG) 1-10 8 February 1984 (1984-02-08) cited in the application the whole document

EP 0148501 A (BAYER AG) 1-10 17 July 1985 (1985-07-17) cited in the application the whole document

EP 0300344 A (BAYER AG) 1-10 25 January 1989 (1989-01-25) cited in the application the whole document

Form PCTΛSA / 210 (contkiuatlon of ββcond ehest) (July 1992) PCT / EP 00/06461

Patent document Publicatjon Patent family Publicatjon cited in search report date member (3) date

DE 3038608 A 19-05-1982 JP 1578045 C 13-09-1990

JP 2003789 B 24-01-1990

JP 57095973 A 15-06-1982

JP 2138270 A 28-05-1990

DE 2201432 A 19-07-1973 AR 195814 A 09-11-1973

AT 322276 B 12-05-1975

AU 472352 B 20-05-1976

AU 5080073 A 11-07-1974

BE 794013 A 12-07-1973

BG 22788 A 20-04-1977

CA 1001642 A 14-12-1976

CH 575712 A 31-05-1976 es 192459 B 31-08-1979

DD 104171 A 05-03-1974

DK 134042 B 06-09-1976

FR 2168009 A 24-08-1973

GB 1407114 A 24-09-1975

HU 165488 B 28-09-1974

IL 41216 A 29-02-1976

IT 976809 B 10-09-1974

JP 1092085 C 16-04-1982

JP 48080727 A 29-10-1973

JP 56035162 B 15-08-1981

NL 7300422 A 17-07-1973

0A 4316 A 15-01-1980

SU 708977 A 05-01-1980

TR 17278 A 24-03-1975

US 3870740 A 11-03-1975

US 3929454 A 30-12-1975

US 3954827 A 04-05-1976

US 3919282 A 11-11-1975

US 3925439 A 09-12-1975

ZA 7300264 A 28-11-1973

EP 10673 A 14-05-1980 DE 2847287 A 14-05-1980

DE 2927461 A 08-01-1981

AR 225156 A 26-02-1982

AT 613 T 15-02-1982

AU 5231479 A 12-06-1980

BR 7907029 A 15-07-1980 es 208791 B 15-09-1981

DD 147903 A 29-04-1981

DE 2961993 D 11-03-1982

DK 458579 A 01-05-1980

ES 485541 A 16-05-1980

HU 179412 B 28-10-1982

IE 49101 B 24-07-1985

JP 55064555 A 15-05-1980

NZ 191947 A 24-04-1981

PL 219330 A 15-12-1980

PT 70360 A 01-11-1979

RO 78638 A 12-04-1982

ZA 7905815 A 26-11-1980

EP 5501 A 28-11-1979 DE 2822155 A 22-11-1979

DE 2903966 A 07-08-1980

BR 7903094 A 11-12-1979

Form PCT ISA 210 (patent family artnex) (July 1992) ι it

i