HU218299B - Substituted aromatic thiocarboxylic acid amides, preparation and use thereof as herbicides - Google Patents

Abstract

FIELD OF THE INVENTION The present invention relates to novel substituted aromatic di-carboxylic acids of formula (I) wherein R1 is hydrogen or halogen, R2 is hydrogen, hydroxy, amino, cyano, nitro, halogen, or alkoxy, alkenyloxy optionally substituted by halogen. alkynyloxy, (C 1 -C 4) alkoxy (C 1-4 alkoxy), (C 1 -C 4) alkoxy (C 1 -C 4) alkoxy (1-4Calkoxy), alkylsulfonylamino an amino group substituted with an alkylsulfonyl and / or alkyl group; R3 represents a hydrogen atom, Z is a saturated or partially saturated or partially saturated 5 or 6 membered heterocyclyl group, optionally substituted with one or two CO or CS groups, optionally substituted with one or two CO or CS groups; R6 and R7 are amino, nitro, cyano, halogen, cycloalkyl, haloalkyl, alkylamino, dialkylamino, and optionally 2 adjacent R6 and R6 or R7 and R7 or R6 and R7 together it forms a C3-C5 alkylene chain. ŕ

Description

The present invention relates to novel substituted aromatic thiocarbamic acid amides, their preparation and their use as herbicides.

Certain aromatic carbothioamides, such as 2,6-dichlorobenzothioamide (chlorothiamide), are known to have herbicidal properties (see GB-PS 987253). However, the effect of this known compound is not fully satisfactory in all applications, especially at low application rates and concentrations.

The present invention provides novel substituted aromatic thiocarboxylic amides of formula (I) wherein R ¹ is hydrogen or halogen,

R ² is hydrogen, hydroxy, amino, cyano, nitro, halogen, or optionally substituted C 1 -C 6 alkoxy, C 2 -C 6 alkenyloxy, C 2 -C 6 alkynyloxy, (1) C 1-4 -alkoxy) - (C 1-4 -alkoxy) - (C 1-4 -alkoxy) - (C 1-4 -alkoxy) - (C 1-6 -alkyl) sulfonyl- amino, C 1-6 alkylsulfonyl and / or C 1-4 alkyl substituted amino;

R ³ is hydrogen,

Z represents

R ^r

(Z *) (z ² )

(Z ' ⁴ ) (z ") (Z °)

R ¹

NQ ^{1 H} '- </> - NN (z' ^T )

NQ ¹ / \

N -

n-q R ⁵ (2 ") (z ¹³ ) Q ² K. w // -N N-N (Z ² ')

Q ¹ is -CO-, -CS-;

Q ² is -CO-, -CS-;

R ⁶ and R ⁷ are amino, nitro, cyano, halogen, preferably fluoro, chloro or bromo, C 1-6 alkyl, preferably methyl, ethyl, n or isopropyl, C 3-6 cycloalkyl; preferably cyclopropyl, C 1-6 haloalkyl, preferably difluoromethyl, trifluoromethyl, chlorodifluoromethyl, C 1-6 alkylamino, preferably methylamino, ethylamino, n- or isopropylamino, dimethylamino, diethylamino, and wherein optionally 2 adjacent R ⁶ and R ⁶ or R ⁷ and R ⁷ or R ⁶ and R ⁷ together are C 3 -C 5 forms an alkylene chain.

The novel substituted aromatic thiocarboxylic acid amides of formula (I) are prepared by substituting a substituted aromatic nitrile of formula (II) wherein R ¹ , R ² , R ³ and Z are as defined above,

GB 218,299 Β where hydrogen sulfide (H ₂ S acid) or with thioacetamide, catalysts and optionally in the presence of a diluent.

The novel substituted aromatic thiocarboxylic acid amides of formula (I) are highly selective.

In the definitions, saturated or unsaturated hydrocarbon chains, such as alkyl, alkylene, alkenyl or alkynyl, or linked to heteroatoms, such as alkoxy or alkylamino, may be straight or branched.

The halogen may generally be fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine, especially fluorine or chlorine.

The present invention preferably relates to compounds of formula I wherein:

R ¹ is hydrogen, fluorine, chlorine or bromine,

R ² is hydrogen, hydroxy, amino, cyano, nitro, halogen, or optionally substituted with halo in the alkyl group

C 1 -C 6 alkoxy, C 2 -C 6 alkenyloxy, C 2 -C 6 alkynyloxy, (C 1 -C 4 alkoxy) - (C 1 -C 4 alkoxy) -, (C 1 -C 4 alkoxy) - (1). (C4-C4) alkoxy (C1-C4) -alkoxy, (C1-C6-alkyl) sulfonylamino, (C1-C6) alkylsulfonyl, and / or C1-C4-alkyl substituted amino;

R ³ is hydrogen and Z is

R j.

Ν '(Z')

Λ (z ² )

The t

y-c?

R ^T · N

<Z ">

(Z ⁴ ) Q ² ' ^Q ' nK

R ^s R ³ (z ' ⁴ ) (Z' °) • Q, ι X

(Z ' ⁵ ) ⁵ X \

N-Q

K \ // N-N

NQ ^{1 r5} X \ n—

N-Q ¹ <Z ")

(z ' ⁹ ) (Z' ^T )

Η Rs ^/ w // n-n k 1 ' (Z * ·) (z ²⁵ )

Q ¹ is -CO-, -CS-;

Q ² is -CO-, -CS-;

R ⁶ and R ⁷ is amino, nitro, cyano, halogen, preferably fluorine, chlorine or bromine, Me-60 butyl, ethyl, n- or i-propyl, cyclopropyl, difluoromethyl, trifluoromethyl, , chlorodifluoromethyl, methylamino, ethylamino, n- or isopropylamino, diethylamino,

And wherein optionally 2 adjacent R ⁶ and R ⁶ or R ⁷ and R ⁷ or R ⁶ and R ⁷ together form a C 3 -C 5 alkylene chain.

More particularly, the present invention relates to compounds of formula I wherein R ¹ is hydrogen, fluoro or chloro;

R ² is hydrogen, hydroxy, amino, cyano, nitro, fluoro, chloro or bromo, or optionally fluoro, chloro, substituted methoxy, ethoxy, n or isopropoxy, η, iso- , bis or tert-butoxy, η, iso-, chair- or tert-pentyloxy, propenyloxy, butenylyl, propynyloxy, butynyloxy,

R ³ is hydrogen and Z is

-n ' ^Q ' n <Z ¹ ) q ^! ' ^Q -n> = «' {rt

, .Q '

Ν '> = <R * R'

C2 ^{, Z} )

R ^T

N-Q

R ² (z ^{, a} )

R ¹

NQ ^{1 RS} ~ {\) NQ ^{1 rS} X nn-q '

<Z *>

(z ¹⁹ ) (2 ¹⁸ )

N-N

(z ²⁵ ) (z ²⁵ )

Q ¹ is -CO-, -CS-;

Q ² is -CO-, -CS-; 50

R ⁶ and R ⁷ are amino, nitro, cyano, fluoro, chloro or bromo, methyl, ethyl, n- or isopropyl, cyclopropyl, difluoromethyl, trifluoromethyl, chlorodifluoromethyl, methyl -amino, ethylamino, n- or isopropylamino, dimethylamino, diethylamino, and wherein optionally 2 are adjacent to R ⁶ and R ⁶ or R ⁷ and R ⁷ or R ⁶ and R ⁷ together form a C 3 -C 5 alkylene chain.

The general or preferred group definitions given above include the final products of formula (I) and the corresponding starting materials and intermediates. These group definitions may be combined with each other and within the stated range of preferred compounds.

Examples of compounds of the present invention represented by formula (I) are listed below.

Group 1 Compounds of formula IA-1 R ¹ , R ² and R ³ are as defined in the following list:

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Example- song R ¹ R ² R ³ First H F H Second H cl H 4th cl F H 5th F F H 11th F -NHC ₂ H ₅ H 13th F -N (CH ₃ ) SO ₂ C ₂ H ₅ H 14th cl -N (CH ₃ ) SO ₂ C ₂ H ₅ H 17th F OH H 18th cl OH H 20th F -nh-so ₂ ch ₃ H 28th F -oc ₂ h ₅ H 29th F -N (C ₂ H ₅ ) SO ₂ C ₂ H ₅ H 30th F -N (SO ₂ CH ₃ ) 2 H 35th F -O CH 1 CH 2) - C = CH H 37th F -o-ch ₂ ch ₂ -och ₃ H 38th F ~ O (CH ₂ CH ₂ O) ₂ CH ₃ H 39th F -o-ch ₂ ch = ch ₂ H 40th F -O-CH ₂ CsCH H 45th F -O-CH ₂ -CF ₃ H 46th F O-CH (CH ₂ F) ₂ H 49th F -NH-SO ₂ C ₂ H ₅ H 50th cl NH SO ₂ C ₂ H ₅ H 52nd F -NH-SO ₂ CH (CH ₃ ) ₂ H 53rd F -nh-so ₂ c ₄ h ₉ H 86th F OCH ₂ CH (C 1) = CH ₂ H 88th F -o-chf ₂ H 103rd F -NCH (CH ₃ ) ₂ SO ₂ C ₂ H ₅ H 104th F -N (CH ₃ ) SO ₂ CH (CH ₃ ) ₂ H 106th cl -N (CH ₃ ) SO ₂ C ₄ H ₉ H 107th F -N (CH ₃ ) SO ₂ C ₂ H ₅ H 108th F -N (CH ₃ ) SO ₂ CH ₃ H 109th F -N (SO ₂ C ₂ H ₅ ) ₂ H 110th F N (SO, CH,) SO, C ₂ H ₅ H 112th F -N (CH ₃ ) ₂ H 113th F NH, H

Pclda- song R ¹ R ² R ³ 114th cl -NH ₂ H 115th cl -O-CH (CH ₃ ) ₂ H 116th F O CH (CH 3), H

Group 2 Compounds of Formula IA-2

R ^1, R ² and R ³ are as defined in group 1.

Group 3 Compounds of formula IA-3

R ^1, R ² and R ³ are as defined in group 1.

Group 4 Compounds of Formula IA-4

R ^1, R ² and R ³ are as defined in group 1.

Group 5 Compounds of Formula IA-5

R ^1, R ² and R ³ are as defined in group 1.

Group 7 compounds of formula IA-7

R ^1, R ² and R ³ are as defined in group 1.

Group 8 compounds of formula IA-8

R ^1, R ² and R ³ are as defined in group 1.

Group 9 compounds of formula IA-9

R ^1, R ² and R ³ are as defined in group 1.

Group 15 compounds of formula IA-15

R ^1, R ² and R ³ are as defined in group 1.

Group 16 is a compound of formula IA-16

R ^1, R ² and R ³ are as defined in group 1. Group 22 Compounds of formula IA-22

R ^1, R ² and R ³ are as defined in group 1. Group 28 is a compound of formula IA-28

R ^1, R ² and R ³ are as defined in group 1.

Group 31 Compounds of formula IA-31

R ^1, R ² and R ³ are as defined in group 1.

Group 32 Compounds of formula IA-32

R ^1, R ² and R ³ are as defined in group 1. Group 36 Compounds of formula IA-36

R 1, R ² and R ³ are as defined in Group 1.

Group 39 Compounds of formula IA-39

R ^1, R ² and R ³ are as defined in group 1.

Group 40 compounds of formula IA-40

R ^1, R ² and R ³ are as defined in group 1.

Group 41 Compounds of formula IA-41

R ^1, R ² and R ³ are as defined in group 1.

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Group 43 Compounds of formula IA-43

R ^1, R ² and R ³ are as defined in group 1.

Group 49 Compounds of formula IA-49

R ^1, R ² and R ³ are as defined in group 1.

Group 50 is a compound of formula IA-50

R ^1, R ² and R ³ are as defined in group 1.

Group 55 Compounds of formula IA-55

R ^1, R ² and R ³ are as defined in group 1.

Group 60 Compounds of formula IA-60

R ^1, R ² and R ³ are as defined in group 1.

Group 62 is a compound of formula IA-62

R ^1, R ² and R ³ are as defined in group 1.

Group 63 Compounds of formula IA-63

R ^1, R ² and R ³ are as defined in group 1.

Group 64 Compounds of formula IA-64

R ^1, R ² and R ³ are as defined in group 1.

Group 65 is a compound of formula IA-65

R ^1, R ² and R ³ are as defined in group 1.

Group 66 Compounds of formula IA-66

R ^1, R ² and R ³ are as defined in group 1.

Group 67 Compounds of formula IA-67

R ^1, R ² and R ³ are as defined in group 1.

Group 68 Compounds of formula IA-68

R ^1, R ² and R ³ are as defined in group 1.

Group 69 Compounds of formula IA-69

R ^1, R ² and R ³ are as defined in group 1.

Group 72 is a compound of formula IA-72

R ^1, R ² and R ³ are as defined in group 1.

Group 77 Compounds of formula IA-77

R ^1, R ² and R ³ are as defined in group 1.

Group 81 is a compound of formula IA-81

R ^1, R ² and R ³ are as defined in group 1.

For example, if 2- (2-fluoro-4-cyano-5-methoxyphenyl) -4-methyl-5- (difluoromethyl) -2,4-dihydro-3H-1,2,4-triazol-3-one and using hydrogen as a starting material, the reaction scheme of the present invention can be illustrated by the following Scheme 1.

In the process of the invention, substituted aromatic nitriles of formula (II) are also used to prepare compounds of formula (I). Preferred values for R ¹ , R ² , R ³ and Z in formula II are given with respect to compounds of formula I. The starting materials of the formula (II) are known and / or can be prepared by known methods, see the literature (EP-A 370332; DE-A 4238125; DE-A 4303376; US-P 5084084) and the preparation examples.

Suitable diluents for the process of the invention are all customary organic solvents. These include in particular aliphatic, alicyclic or aromatic, optionally halogenated hydrocarbons such as gasoline, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, chloroform, tetrachloromethane, ethers, e.g. 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 benzonitrile, amides such as N, N-dimethylformamide , Ν, Ν-dimethylacetamide, N-methyl formanilide, N-methylpyrrolidone or hexamethylphosphoric triamide, esters such as methyl acetic acid or ethyl acetic acid, sulfoxides such as dimethyl sulfoxide, azines such as pyridine, alcohols such as methanyl, ethanol, n- or isopropanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether or the like with water. or pure water.

The process of the invention is preferably carried out in the presence of a suitable catalyst. As the boiler, conventional inorganic or organic bases may be used. These include, for example, alkali metal or alkaline earth metal hydrides, hydroxides, amides, alcoholates, acetates, carbonates or bicarbonates, such as sodium hydride, sodium amide, sodium methylate, sodium ethylate, butylate), sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium acetate, potassium acetate, calcium acetate, ammonium acetate, sodium carbonate, potassium carbonate, potassium bicarbonate, sodium bicarbonate or carbonate as well as basic organic nitrogen compounds such as trimethylamine, triethylamine, tributylamine, Ν, Ν-dimethylaniline, pyridine, N-methylpiperidine, Ν, Ν-dimethylaminopyridine, diazabicyclooctane (DABCO), diazabicyclo-nonane (DBN) or diazabicyclo-undecene (DBU).

The reaction temperature of the process according to the invention can be varied within a wide range, generally from 0 to 100 ° C, preferably from 10 to 80 ° C.

The process of the present invention may generally be carried out at atmospheric pressure, but may also be carried out at elevated or reduced pressure, for example between 0.1 and 10 bar.

The starting materials of formula (II) for the process of the invention are generally used in a suitable diluent and in the presence of a catalyst, and hydrogen sulfide or thioacetamide is added slowly. Preferably, a large excess of hydrogen sulfide or thioacetamide is used. The reaction mixture was stirred for several hours at the required temperature. Work-up is carried out in a manner known in the process of the present invention (see Preparation Examples).

The compounds of the present invention have an effect on plant growth and, therefore, as a deciduous agent, a germinating agent, a ter

They may be used as an agent to kill parts of plants, in particular as an active ingredient in a herbicide. Weeds in the broadest sense are those plants that grow where they are undesirable. Whether the agents of the present invention act as total or selective agents depends essentially on the amount employed.

The active compounds of the present invention can be used to control the following dicotyledonous weeds: mustard (Sinapis), cress (Lepidium), gala (Galium), starch (Stellaria), medical chair (Matricaria), Roman chair (Anthemis), mushroom (Galinsoga), goatop (Chenopodium), nettle (Urtica), carob (Senecio), porcupine (Amaranthus), cornflower (Portulaca), sea buckthorn (Xanthium), watercress (Convolvulus), dawn (Ipomoea) bitter grass (Polygonum), Sesbania parsley (Cirsium), Thistle (Carduus), Rhubarb (Sonchus), Lucerne (Solanum), Austrian Yarrow (Rorippa), Rotala, Sage Grass (Lindemia), Orchid (Lamium), Veronica (Veronica), Abutilon, Emex, Masquerade (Datura) , violet (Viola), hemp (Galeopsis), poppy (Papaver), imola (Centaurea), here (Trifolium), buttercup (Ranunculus), dandelion (Taraxacum).

The novel compounds can be used, for example, in the following dicot cultures: cotton (Gossypium), soybean (Glycine), beet (Beta), carrot (Daucus), bean (Phaseolus), pea (Pisum), potato (Solanum), flax (Linum), dawn (Ipomoea), bean (Vicia), tobacco (Nicotiana), tomato (Lycopersicon), peanut (Arachis), cabbage (Brassica), lettuce (Lactuca), cucumber (Cucumis), pumpkin (Cucurbita).

Among the monocotyledonous weeds, the following may be killed by the agents of the present invention: Cocksfoot (Echinochloa), Muhar (Setaria), Millet (Panicum), Fescue (Festuca), Drought (Eleusine), Brachiaria, Fescue (Digitaria), Komochin (Peony) (Poa), Fescue (Festuca), Eleusine, Brachiaria, vadoc (Lolium), Rozen (Bromus), Oat (Avena), Palatine (Cyperus), Sorghum, Tarack (Agropyron), Bermuda (Cynodon), Monochoria, Fimbrisylis, Arrowgrass (Sagittaria), Chard (Eleocharis), Chard (Scirpus), Paspalum, Ischaemum, Sphenoclea, Dactyloctenium, Tipan (Agrostis), Brush Lawn (Alopecurus), Heather Beet (Apera).

The novel compounds can be used, for example, in the following monocot cultures: rice (Oryza), maize (Zea), wheat (Triticum), barley (Hordeum), oat (Avena), rye (Secale), sorghum (Sorghum), millet (Panicum), sugar cane (Saccharum), pineapple (Ananas), asparagus (Asparagus), onion (Allium).

However, the applicability of the agents of the present invention is not limited to the above crops but also extends to other plants.

Depending on their concentration of active ingredient, the agents of the present invention can be used as total herbicides, for example, to kill weeds growing in industrial areas, along railway tracks, on roads and in squares. The products are also used in forests, shrubs, fruit, grapes, citrus, walnuts, bananas, coffee, tea, rubber, olive, cocoa and hops, ornamental and sports lawns and field surfaces, and non-perennial can be used as a selective herbicide in cultures.

Particularly in monocotyledonous and dicotyledonous cultures, the compounds of the present invention can be used for the selective control of monocotyledonous and dicotyledonous weeds by pre- and postemergence.

They also exhibit some degree of fingicidal activity against the compounds of formula I, e.g., in rice against Pyricularia oryzae.

The active compounds of the present invention can be formulated into standard formulations such as solutions, emulsions, spray powders, suspensions, powders, soluble powders, pastes, granules, suspension emulsion concentrates, fines, and fines impregnated with natural active ingredients.

The compositions are prepared in a manner known per se by mixing the active ingredients with excipients, i.e. liquid solvents and / or solid carriers, optionally with surfactants, i.e. emulsifiers and / or dispersants and / or foaming agents. If water is used as a carrier, an organic cosolvent may be added.

When water is used as a liquid carrier, organic solvents, for example, may also be used as co-solvents. Suitable liquid solvents are essentially aromatic compounds such as benzene, toluene, xylene or alkylnaphthalenes, chlorinated aromatic or chlorinated aliphatic hydrocarbons such as chlorobenzene, chloroethylene or methylene chloride, aliphatic hydrocarbons such as cyclohexane or fractions, alcohols such as butanol or glycol as well as their esters and ethers, ketones such as acetone, methyl ethyl ketone, methyl isobut ketone or cyclohexanone, highly polar solvents such as dimethylformamide, dimethyl sulfoxide and water.

Solid carriers include ammonium salts and natural rock flour such as kaolin, chalk, clay earth, talc, quartz, attapulgite, montmorillonite and diatomaceous earth, or synthetic rock flour such as high dispersion silica, alumina and silica. The granules include solid and fractionated natural rocks such as chelate, marble, pumice, sepiolite, dolomite as solid carriers, and synthetic granules from inorganic or organic flours, and granules from organic materials such as wood flour, coconut shells, corn cob.

Non-ionic and anionic emulsifiers such as polyoxyethylene fatty acid ester, polyoxyethylene fatty alcohol ether such as alkylaryl polyglycol ether, alkylsulfonates, arylsulfonates as emulsifiers and / or foaming agents. egg white hydrolyzate, such as lignin sulphite lye and methylcellulose.

Dispersing agents include, for example, lignin sulphite waste liquors and methylcellulose.

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Carboxymethylcellulose, natural and synthetic polymers in powder, granular or latex form, for example, gum arabic, polyvinyl alcohol, polyvinyl acetate and natural phospholipids such as cephalin and lecithin, and synthetic phospholipids. Other additives may include mineral and vegetable oils.

Dyes such as inorganic pigments such as iron oxide, titanium oxide, ferrocyan, organic dyes and printing elements such as iron, manganese, leather, copper, cobalt, molybdenum and zinc salts may be used.

The formulations generally contain from 0.1 to 95% by weight of the active ingredient, preferably from 0.5 to 90% by weight of the active ingredient.

The active compounds of the present invention may also be mixed with other known herbicides either in ready-made formulations or in tank mixing.

For example, the following herbicides may be used in the mixtures: anilides such as diflufenican or propanyl; arylcarboxylic acids such as dichloro-picolinic acid, dicamba and picloram; aryloxyalkanoic acids such as 2,4-D, 2,4-DB, 2,4-DP, fluroxypyr, MCPA, MCPP and triclopyr, aryloxy-phenoxy-alkanoic acid esters such as diclofop-methyl, fenoxaprop-ethyl, fluazifop-butyl, haloxyfop-methyl and quizalofop-ethyl; azions such as chlorideazone and norflurazone; carbamates such as chlorpropham, desmedipham, phenmedipham and profam; chloroacetanilides such as alachlor, acetochlor, butachlor, metazachlor, metolachlor, pretilachlor and propachlor; dinitroanilines such as orizaline, pendimethalin and trifluralin; diphenyl ethers such as acifluorfen, bifenox, fluoroglycofen, fomesafen, halosafen, lactofen and oxifluorfen; ureas such as chlorotoluron, diuron, fluometuron, isoproturon, linuron and metabenzthiuron; hydroxylamines such as alloxidim, clletodim, cycloxidim, setoxidim and tralkoxydim; imidazolinones such as imazetapir, imazamethabenz, imazapir and imazaquin; nitriles such as bromoxynil, diclobenyl and ioxynil; oxyacetamides such as mefenacet; sulfonylureas such as amidosulfuron, bensulfuron-methyl, chlorimuron-ethyl, chlorosulfuron, cinosulfuron, methulfuron-methyl, nicosulfuron, primisulfuron, pyrazosulfuron-ethyl, thifensulfuron-methyl, triazulfuron and tribenzuron; thiolcarbamates, such as butylates, cycloate, dialiate, EPTC, esprocarb, molinate, prosulfocarb, thiobencarb and triallate; triazines such as atrazine, cyanazine, simazine, symmetrine, terbutryn and terbuthylazine; triazinones such as hexazinone, metamitron and metribuzin; others such as aminothiazole, benfurezate, bentazone, cinmethylline, clomazone, clopiralid, difenzoquat, dithiopyr, ethofumesate, fluorochloridone, glufosinate, glyphosate, isoxaben, pyridate, quinchlorac, quinmerac, sulfosate and tridifane.

It can also be combined with other known active ingredients, such as fungicides, insecticides, acaricides, nematocides, bird food preservatives, plant nutrients, soil improvers.

The active compounds may be formulated or formulated as further dilutions in ready-to-use solutions, emulsions, suspensions, powders, pastes, granules. The application is carried out in the usual manner, for example by spraying, spraying, dusting, irrigation, spraying.

In particular, the compositions may be applied before and after emergence of the plants.

The preparations can be incorporated into the soil before sowing.

The amount of active ingredient used will vary over a wide range and will essentially depend on the desired effect. Generally, 10 g to 10 kg active ingredient / ha, preferably 50 g to 5 kg active ingredient / ha, are applied.

The following examples illustrate the preparation and use of the active compounds of the invention.

Production examples

Example 1 Compound of Formula (1)

5.5 g of 15 mmol of 2- (4-cyano-2-fluoro-5- (ethylsulfonylamino) -phenyl) -5,6,7,8-tetrahydro-1,2,4-triazole [4,3-a] of pyridin-3- (2H) -one, 5 ml of triethylamine and 50 ml of pyridine are heated to 50-60 ° C until saturated hydrogen sulfide is added and the mixture is stirred at 60 ° C for 30 minutes. The reaction mixture was concentrated in vacuo and the residue was stirred with 2N hydrochloric acid and filtered. The solid product was recrystallized from isopropanol. 4.8 g of 80% 2- (2-fluoro-5- / ethylsulfonylamino / -4-thiocarbamoyl-phenyl) -5,6,7,8-tetrahydro-1,24-triazolo [4,3-a] pyridine-3 ( 2H) -one, m.p. 220 ° C.

Example 2 Compound 2

6.3 g of 0.02 mol of 2- (2-fluoro-4-cyano-5-aminophenyl) -4-ethyl-5- (trifluoromethyl) -2,4-dihydro-3H-1,2,4- triazol-3one in 100 ml of acetone was added 4.04 g of 0.04 mole of triethylamine. At 23 ° C, hydrogen sulfide is introduced slowly while the internal temperature rises to 33 ° C. After 1 hour, the reaction was complete. The solution was evaporated on a rotary evaporator, the residue was recrystallized from isopropanol and 2.9 g of 42% 2- (2-fluoro-4-thiocarbamoyl-5-phenyl) -4-ethyl-5- (trifluoromethyl) -2,4- of dihydro-3H1,2,4-triazol-3-one, m.p. 161 ° C.

Example 3 Compound 3 g 0.0276 moles of 2- (2-fluoro-4-cyano-5-ethylsulfonylamino-phenyl) -4-methyl-5- (difluoromethyl) -2,4-dihydro-3H -1,2,4-Triazole-3-thione is stirred in 100 ml of pyridine under anhydrous hydrogen sulfide for 4.5 hours at 70 ° C. The solution was evaporated on a rotary evaporator, the residue was stirred with water, acidified with concentrated hydrochloric acid, filtered off, washed with water and recrystallized from isopropanol. 9 g 77% 2- (2-Fluoro-4-thiocarbamoyl-5- (ethylsulfonylamino) -phenyl) -4-methyl-5- (difluoromethyl) -2,4-dihydro-3H-1,2,4-triazole -3-thione is obtained, m.p. 183 ° C.

By analogy to Preparation Examples 1, 2 and 3 and the general description of the preparation process of the invention, for example, the compounds of formula I listed in Table 1 below can be prepared.

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Example R 'R ² r' z number

Melting point (* C)

Table 1 Compounds of formula (I)

F -NH-SO ₂ -C ₂ H ₅

-O-CH = CH-C

I

CH

F -NH-SO2-C2H5

F -NH-SO2-C2H5

F -NH-SO2-C2H5

F F

F -OC ₂ H ₅

H SHE A-N Λ = ν PJC 110 H 0 Λ = ν F, C ^Z 143 H s hUC \ χ *** * N N f, ch ' 162 H 0 Π, ΜΠ ^ ^ Α H, C ' 237 / triethyl- ammonium salt/ H S H, C _X. Λ / NN 220 F, CH ^Z H 0 · * νΑ, Α F, CH ^Z 218 H N (CHJ, / 1 = Ν 185 H 0 υ = ^ 218 H 0 ^ 'An' ' U = N 202

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Table 1 (continued)

Example R ¹ R ^J R ³ Z number

Melting point (* C)

F -NH-SO2-C2H5H

210

F

NH-SO2-C2H5

203

F

F

-N-SOJ-CJH,

CH

F

-OCH (CH ₃ ) 2

F

OH

F

-Ν-δΟ, -Ο, Η,

CH

F

NH-SO2-C2H5

F

NH-SO2-C2H5

185

170

206

250

208

HU 218 299 Β

Table 1 (continued)

R ³

Example R ¹

R ^J

Z

Melting point ( ^e C)

NH-SO2-C2H5

NH-SO2-C2H5

-N-CH-SOJ,

CH

(amorphous)

183

167

-NH-SO 2 -CH 3 H

-NH-SO 2 -CH 3 H

SHE

130

243

199

-NH-SO 2 -C 2 H 5 H

202

-NH-SO 2 -CH 3 H

-NH-SO 2 -CH (CH ₃ ) 2 H

200

204

HU 218 299 Β

Table 1 (continued)

Example R ¹ R ² R ³ Z number

Melting point (* C)

F -NH-SO ₂ -C ₂ H ₅

195

-N

-O-CH = CH-C

I

CH »tj

122

N

-O-CH = CH-C

FIC

190

F · 'NH-SO2-CH3 / 1 = Ν

F, C ^Z

S

178

-N

F -NH-SO2-C3H7

203

F -NH-SO2-C2H5

F, C '(CH ₃₎ CH _t>

-N

X

I • N

199

F -NH-SO2-C2 ^h 5

153

F -NH-SO2-C2H5

206

F -NH-SO2-C2H5 (CH,> _a CH. _XN X _N /

167

HU 218 299 Β

Table 1 (continued)

Example No. R ¹ R ^J

R ³ Z

Melting point ('C)

F F

F -OCH ₂ CF ₃

F -OC2H4OCH3

F -OC ₂ H ₅

F -OC3H7

cl

130

173

148

155

130

F F H

131

F -001 {0¾¼

F -OC ₂ H ₅

F -NH-SO ₂ -C ₂ H ₅

H-NH-SO ₂ -C ₂ H ₅

N = N

202

185

111

118

HU 218 299 Β

Table 1 (continued)

R '

R ³ Z

Melting point ( ^e C)

Example R number

NH-SO2-C3H7. _n

-OC2H4OC2H4OCH3

NH-SO2-C3H7. _n

-NH-SO 2 -C ₃ H ₇ . _n

-NH-SO2 C3H7.Í

-NH-SO2 C3H7.Í

-NH-SO2-C3H74

-NH-SO2-C3H74

-NH-SO2-C3H74

FjCK

143

168 (amorphous)

232

226

187

236

252

109

HU 218 299 Β

Table 1 (continued)

Example R ¹ R ² R ³ Z number

Melting point ( ^e C)

F -NH-SO2-C3H7.I

SHE

207

F -NH-SO2-C3H7.I

F is -N (CH 3) -SO 2 C 2 H 5

215

102

F -NH-SO2-C2H5H

185

Cl-NH-SO 2 -C 2 H 5 H

F F H

F -NH-SO2-C ₂ H _S H

F-OH H

O «Λ Λ /

N N

FjCH

121

157

195

193 (Z.) DBU salt

Preparation of starting materials

II 1st example

6.3 g, 0.034 mol of 4-methyl-3- (trifluoromethyl) -1,2,4-triazolin-5-one (see, for example, U.S. Patent 3,780,052); and 5.4 g, 0.034 mol. To a solution of 4,5-trifluorobenzonitrile (see, for example, European Patent Application No. 191181) in 150 ml of dimethyl sulfoxide was added 5.8 g (0.042 mol) of potassium carbonate at room temperature and the mixture was heated at 100 ° C for 14 hours. For working-up, the cooled reaction mixture is taken up in water, acidified to pH 2 with dilute hydrochloric acid and extracted several times with dichloromethane. The combined organic layers were dried over sodium sulfate and dried

Evaporate under vacuum. The residue was chromatographed on silica gel (eluent: dichloromethane). 6.2 g (60%) of 1- (4-cyano-2,5-difluorophenyl) -4-methyl-3- (trifluoromethyl) -1,2,4-triazolin-5-one, m.p. 74 ° C. .

II 2nd EXAMPLE 5 Compound 5

1- (4-Cyano-2,5-difluorophenyl) -4-methyl-3- (trifluoromethyl) -1,2,4-triazolin-5-one (1.52 g, 0.005 mol) and 0.005 g (0.005 g) To a stirred mixture of methanesulfonic acid amide (50 moles) in dimethyl sulfoxide (50 mL) was added potassium carbonate (0.83 g, 0.006 moles) at room temperature and heated at 120 for 12 hours. For working-up, the cooled reaction mixture is taken up in water, acidified to pH 2 with dilute hydrochloric acid and extracted several times with dichloromethane. The combined organic phases were dried over sodium sulfate, concentrated in vacuo and the residue chromatographed on silica gel. The eluent was dichloromethane: methanol (20: 1, v / v). 0.55 g of 28% 1- (4-cyano-2-fluoro-5- (methylsulfonylamino) phenyl) -4-methyl-3- (trifluoromethyl) -1,2,4-triazoline-5- m.p. 67 ° C.

II, 3rd EXAMPLE 6 Compound 6

A solution of 3-amino-4,4,4-trifluorocrotonic acid ethyl ester (1.8 g, 10 mmol) in dimethylformamide (30 mL) and toluene (2 mL) was treated with sodium hydride (0.3 g, 10 mmol) at 0-5 ° C. 80%). The mixture was stirred for 30 minutes at 0-5 ° C. After cooling, a solution of 4-cyano-2,5-difluorophenyl isocyanate (0.9 g, 5 mmol) in toluene (10 mL) was added at -70 ° C, and the mixture was stirred at -60 ° C-70 ° C for 150 minutes. -you. After removal of the cooling bath, acetic acid (2 ml) was added and the mixture was diluted to 2X with water and extracted with ethyl acetate. The organic phase is evaporated and the residue is crystallized with diisopropyl ether. 1.1 g (69%) of 1- (4-cyano-2,5-difluorophenyl) -3,6-dihydro-2,6-dioxo-4- (trifluoromethyl) -1- (2H) -pyrimidine are obtained, m.p. 194 ° C.

II-fourth EXAMPLE 7 Compound 7

0.83 g, 3 mmol 1- (4-cyano-2,5-difluorophenyl) -3,6-dihydro-2,6-dioxo-3,4-dimethyl-1 (2H) -pyrimidine 0.32 g, A mixture of 3 mmol of methanesulfonamide, 0.6 g of potassium carbonate and 10 ml of dimethyl sulfoxide was heated at 120 ° C for 10 hours. After cooling, the reaction mixture was poured into ice-water, acidified with 2N hydrochloric acid, extracted with ethyl acetate, and the organic phase was washed with water, dried over sodium sulfate and filtered. The solvent was thoroughly distilled off from the filtrate using a water jet vacuum pump. 0.8 g of 76% 1- (4-cyano-2-fluoro-5- (methylsulfonylamino) phenyl) -3,6-dihydro-2,6-dioxo-3,4-dimethyl (2H) -pyrimidine crystalline residue, m.p. 250 ° C.

Application examples

The example

Preemergent test

Solvent: 5 parts by weight of acetone

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

A suitable formulation is prepared by mixing the active ingredient in an amount of 1 part by weight with the above amount of carrier and emulsifier, and diluting the resulting emulsifiable concentrate with water to the desired concentration.

Seeds of the test plants are seeded in normal soil and watered with the active compound formulation after 24 hours. Meanwhile, the amount of water per unit area is preferably kept constant. The concentration of the active ingredient does not play a role in the formulation, only the amount of active ingredient per unit surface area is decisive. After 3 weeks, evaluate the plants for damage! is expressed as a percentage relative to the development of untreated control.

0% = no effect (untreated control)

100% = total eradication

The table

Preemergent test / greenhouse

agent (Synthesis- Example No.) Application quantity (G / ha) Barley Maize Amaranthus (Pigweed) Chenopo- palladium (Goosefoot) Matricaria (medical chamomile) Portulaca (At flowers) Solanum (nightshade) Third 125 0 0 100 100 100 100 100 5th 125 0 0 100 100 90 90 100 6th 125 0 30 100 100 95 100 100 7th 125 30 0 100 100 95 100 95

Table B

Preemergent test / greenhouse

agent (Szintczis- Example No.) USES SUPPLY quantity (G / ha) Wheat Maize Abuthilon (silk- mallow) Amaranthus (pig- grass on) Cheno- podium (Goosefoot) Matricaria (medical chamomile) Portulaca (at- flower) Solanum (nightshade) 19th 60 10 0 100 95 100 100 100 100 20th 60 20 0 100 100 100 100 100 100

HU 218 299 Β

Table B (continued)

agent (Synthesis- Example No.) USES SUPPLY quantity (G / ha) Wheat Maize Abuthilon (silk- mallow) Amaranthus (pig- grass on) Cheno- podium (Goosefoot) Matricaria (medical chamomile) Portulaca (at- flower) Solanum (nightshade) 21st 60 0 0 100 100 100 100 100 100 22nd 250 0 20 100 100 100 100 95 100 23rd 60 0 0 95 70 95 100 95 70 24th 30 0 20 100 95 100 100 100 100 25th 30 0 0 100 100 90 100 100 100 26th 60 0 0 100 80 100 100 100 90 4th 250 0 10 80 50 70 95 90 70 5th 125 0 0 10 100 100 70 90 100 Third 60 0 0 100 100 100 100 100 100 6th 60 20 30 100 100 100 100 100 95 7th 125 50 0 95 100 100 95 100 95 8th 60 40 0 100 100 100 95 95 100 9th 60 0 0 100 100 100 95 90 100 First 125 0 0 100 100 100 95 100 100 12th 60 20 0 70 70 100 95 95 70 13th 60 0 0 100 100 100 70 90 100 16th 60 10 0 95 20 100 90 80 80 17th 30 0 0 100 100 100 100 100 100 28th 60 0 20 100 100 100 100 100 100 29th 60 0 0 100 100 100 100 100 100 30th 60 0 0 100 100 100 90 100 100 31st 60 0 0 100 100 100 100 100 100 32nd 30 10 0 - 100 100 100 95 100 33rd 30 10 10 95 95 100 100 100 100 34th 60 0 0 100 100 100 100 100 100 35th 60 0 0 100 100 100 90 95 100 40th 250 20 0 30 40 100 95 100 80 41st 60 20 30 100 100 100 100 100 100 45th 125 0 0 95 100 100 100 90 95 46th 60 0 70 100 100 100 100 100 100 47th 30 0 0 100 95 100 100 100 100 48th 60 0 0 100 100 100 100 100 100 51st 30 0 20 100 - 100 95 100 100

Example B

Post-Emergency Test Solvent: 5 parts by weight of acetone

Emulsifier: 1 part by weight of alkylaryl polyglycol ether 55 A suitable preparation is made by mixing the active ingredient in 1 part by weight with the above-mentioned carrier and emulsifying agent and diluting the emulsifiable concentrate to the desired concentration with water. 60

The active compound formulation is sprayed on test plants at a height of 5 to 15 cm to deliver the desired amount of active ingredient per unit area. After 3 weeks, the degree of damage to the plants is evaluated against the development of untreated control and expressed as a percentage.

0% = no effect (as in untreated control) 100% = total effect

HU 218 299 Β

Table C

Post-emergence effect / greenhouse

agent (Synthesis- pcldaszám) Application quantity (G / ha) Wheat Maize Abuthilon (silk- mallow) Amaranthus (Pigweed) Chenopodium (Goosefoot) Solanum (nightshade) Veronica (speedwell) 19th 4 5 20 95 95 95 100 100 20th 4 0 15 100 95 95 100 95 21st 4 5 60 90 100 70 100 100 22nd 30 15 0 100 100 40 100 20 23rd 30 0 50 95 - 90 100 100 24th 30 15 70 100 100 100 100 100 25th 15 0 50 100 100 100 100 100 26th 15 0 30 50 90 50 50 100 5th 15 10 20 100 100 100 100 100 Third 30 10 30 100 100 100 100 100 6th 8 30 50 100 100 100 100 95 7th 60 10 50 100 100 95 100 95 8th 60 10 30 100 100 100 100 100 9th 60 10 30 100 100 100 100 100 First 15 10 50 100 95 95 100 100 12th 8 10 30 100 100 95 100 100 13th 15 0 30 95 100 80 100 90 16th 60 20 60 95 100 100 100 100 17th 8 10 10 100 100 95 100 100 28th 30 0 30 100 100 90 100 100 29th 8 5 0 70 100 90 100 95 30th 8 0 50 100 100 95 100 70 31st 8 0 70 100 100 90 100 100 32nd 4 15 30 100 100 95 100 100 33rd 4 20 60 100 100 100 100 100 34th 15 0 30 100 100 100 100 100 35th 30 0 25 100 100 90 100 95 40th 125 10 5 50 70 100 100 90 41st 15 20 50 100 80 90 100 95 43rd 15 0 50 100 95 100 100 100 44th 8 0 15 100 100 100 95 100 45th 8 10 40 95 95 95 100 - 46th 8 15 20 100 100 95 100 100 47th 8 10 10 100 100 95 100 100 48th 8 5 60 100 100 80 100 100 49th 8 0 60 60 100 10 100 100 50th 15 5 70 100 95 80 100 95 51st 15 15 60 100 100 70 100 100

Claims (8)

PATENT CLAIMS Substituted aromatic thiocarboxylic amides of formula (I), wherein R ¹ is hydrogen or halo; R ² is hydrogen, hydroxy, amino, cyano, nitro, halogen, or C 1 -C 6 alkoxy optionally substituted with halo; C 2 -C 6 alkenyloxy, C 2 -C 6 alkynyloxy, (C 1 -C 4 alkoxy) - (C 1 -C 4 alkoxy), (C 1 -C 4 alkoxy) (C 1 -C 4 alkoxy) - (C 1 -C 4 alkoxy), (C 1 -C 6 alkyl) sulfonylamino, (C 1 -C 6 alkyl) sulfonyl and / or (C 1 -C 4) alkyl substituted amino; R ³ is hydrogen, Z is <zb r ^Q Q ² N \ = n R ⁷ <z '°) (Z ⁴ ) {z'b ^Q l q' (Z °) R ¹ n-q ' ^r5_ {\) - NN (Z ^{, s} ) (Z' ^T ) (2 ^{, e} ) (Z ¹⁹ ) (Z ²¹ ) (z ²⁴ ) Ν —N N (2 ²⁵ ) (Z ²⁸ ) Q ¹ is -CO-, -CS-; Q ² is -CO-, -CS-; R ⁶ and R ⁷ are amino, nitro, cyano, halogen, preferably fluoro, chloro or bromo, C 1-6 alkyl, preferably methyl, ethyl, n or isopropyl, C 3-6 cycloalkyl, preferably cyclopropyl, C 1-6 haloalkyl, preferably difluoromethyl, trifluoromethyl, chlorodifluoromethyl, C 1-6 alkylamino, preferably methylamino, ethylamino-. , n- or isopropylamino, dimethylamino, diethylamino, and wherein optionally two adjacent R ⁶ and R ⁶ or R ⁷ and R ⁷ or R ⁶ and R ⁷ together form a C 3-5 alkylene chain. Substituted aromatic thiocarboxylic amides of the formula I according to claim 1, wherein R ¹ is hydrogen, fluorine, chlorine or bromine, R ² is hydrogen, hydroxy, amino, cyano, nitro, halogen, or (C 1 -C 6) alkoxy, (C 2 -C 6) alkenyloxy or alkynyloxy, (C 1 -C 4) alkoxy optionally substituted by halogen; ) - (C 1 -C 4) Alkoxy), (C 1 -C 4) alkoxy (C 1 -C 4) alkoxy (C 1 -C 4) alkoxy, (C 1 -C 6) alkylsulfonylamino, (1- Amino substituted with C 6 alkyl) sulfonyl and / or C 1-4 allele; R ³ is hydrogen, and Z is' Ν N '^ = N <z') (Z'b R ^r {z'b R ¹ NQ ^{1 R} 'X \) NN (Z ^J ) (2 ”) ez ¹³ ) <z * b <z * bwu Ν-N <Z *) (z ²⁵ ) Q ¹ is -CO-, -CS-; Q ² is -CO-, -CS-; R ⁶ and R ⁷ is amino, nitro, cyano, fluorine, chlorine, bromine, methyl, ethyl, n- or i-45 isopropylidene propyl, cyclopropyl, difluoromethyl, trifluoromethyl, chloro-difluoromethyl, methylamino, ethylamino, n-or isopropylamino, dimethylamino, diethylamino, and optionally having 2 adjacent R ⁶ and R ⁶ or 50 R ⁷ and R ⁷ or R ⁶ and R ⁷ together form a C 3 -C 5 alkylene chain. Substituted aromatic thiocarboxylic acid amides of formula I according to claim 1, wherein R ¹ is hydrogen, fluorine or chlorine, R ² is hydrogen, hydroxy, amino, cyano, nitro, fluoro, chloro or bromo, or optionally substituted with fluoro, chloro, methoxy, ethoxy, n or isopropoxy, η, iso-, a chair or tert-butoxy, η, iso-, chair- or tert-pentyloxy, propenyloxy, butenyloxy, propynyloxy, butenyloxy group, R ³ is hydrogen, and Z represents HU 218 299 Β (z ²⁴ ) (Z ²⁵ ) Q ¹ is -CO-, - CS; Q ² is -CO-, -CS-; R ⁶ and R ⁷ are amino, nitro, cyano, fluoro, chloro or bromo, methyl, ethyl, n- or isopropyl, cyclopropyl, difluoromethyl, trifluoromethyl, chloro-difluoro methyl, methylamino, ethylamino, n or isopropylamino, dimethylamino, diethylamino, and wherein optionally 2 adjacent R ⁶ and R ⁶ or R ⁷ and R ⁷ or R ⁶ and R ⁷ together form a C 3 -C 5 alkylene chain. A process for the preparation of the substituted aromatic thiocarboxylic acid amides of the formula I according to claim 1, wherein R ¹ , R ² , R ³ and Z are as defined in claim 1, characterized in that a substituted aromatic nitrile of the formula II wherein R ¹ , R ² , R ³ and Z are as defined above, with hydrogen sulfide or thioacetamide, optionally in the presence of a catalyst and optionally a diluent. 30 5. A method for controlling undesirable plants, comprising the steps of: 1-3. Substituted aromatic thiocarboxylic acid amide according to any one of claims 1 to 10, applied to the unwanted plants and / or their habitat in a composition of 10 g to 10 kg / ha. 6. Use of substituted aromatic thiocarboxylic acid amides of formula (I) according to any one of claims 1 to 3, against undesirable plants. A process for the preparation of a herbicidal composition, comprising the steps of: 1-3. A substituted aromatic thiocarboxylic acid amide of the formula I as claimed in any one of claims 1 to 6 with adjuvants and / or surfactants. 8. A herbicidal composition comprising at least one of claims 1-3. A substituted aromatic thiocarboxylic acid amide according to any one of claims 1 to 3 in an effective amount.