WO1993004050A1

WO1993004050A1 - Substituted triazolinones with herbicide properties

Info

Publication number: WO1993004050A1
Application number: PCT/EP1992/001829
Authority: WO
Inventors: Aktiengesellschaft Bayer
Original assignee: Kuhnt, Dietmar; Müller, Klaus-Helmut; Findeisen, Kurt; König, Klaus; Lürssen, Klaus; Santel, Hans-Joachim; Schmidt, Robert, R.
Priority date: 1991-08-23
Filing date: 1992-08-11
Publication date: 1993-03-04
Also published as: DE4128029A1; AU2409192A

Abstract

L'invention concerne de nouvelles triazolinones substituées ayant la formule générale (I) dans laquelle R1 désigne un alkyle ou un cycloalkyle; R2 désigne un cycloalkyle, un aryle ou un hétérocyclyle, chacun d'eux portant éventuellement des substituants; A désigne un reste ayant la formule (a); (b); (c) ou (d); X désigne un oxygène ou un soufre, et Y désigne un oxygène ou un soufre, R3 représentant un hydrogène, un cyano ou un alkyle, et R4, R5 et R6 représentant respectivement, indépendamment l'un de l'autre, un hydrogène ou un alkyle, ou R3 et R4 formant un reste deux fois lié de formule -(CH2)p; Q désigne un oxygène, un soufre, un groupe sulfinyle, un groupe sulfonyle ou un reste de formule >N-R7; R7 désigne un hydrogène, un alkyle, hydroxyalkyle, alcoxyalkyle, cyanalkyle ou alcanoyle; m est égal à 0, 1 ou 2; n est égal à 0, 1 ou 2, et p est égal à 2, 3, 4, 5 ou 6; ainsi que plusieurs procédés de fabrication de ces composés et leur utilisation comme herbicides et comme nouveaux produits intermédiaires.The invention relates to new substituted triazolinones having the general formula (I) in which R1 denotes an alkyl or a cycloalkyl; R2 denotes a cycloalkyl, an aryl or a heterocyclyl, each of which optionally carries substituents; A denotes a residue having the formula (a); (b); (c) or (d); X denotes an oxygen or a sulfur, and Y denotes an oxygen or a sulfur, R3 representing a hydrogen, a cyano or an alkyl, and R4, R5 and R6 representing respectively, independently of one another, a hydrogen or a alkyl, or R3 and R4 forming a twice-linked residue of formula - (CH2) p; Q denotes an oxygen, a sulfur, a sulfinyl group, a sulfonyl group or a residue of formula> N-R7; R7 denotes hydrogen, alkyl, hydroxyalkyl, alkoxyalkyl, cyanalkyl or alkanoyl; m is 0, 1 or 2; n is 0, 1 or 2, and p is 2, 3, 4, 5 or 6; as well as several processes for the manufacture of these compounds and their use as herbicides and as new intermediate products.

Description

Substituted TrϊazoHnone with herbicidal properties

_____________________________________ The invention relates to new substituted triazolinones, several processes for their preparation and their use as herbicides.

It is known that certain substituted triazolinones such as, for example, the compound 1- (4-phenyl-2-butylaminocarbonyl) -3-methyl-4-amino-1,2,4-triazolin-5-one or the compound 1- (1-cyclohexyl-1-ethylaminocarbonyl) -3-methyl-4-amino-1,2,4-triazolin-5-one or the compound 1- (3-phenyl-2-methyl-2-propylaminocarbonyl) -3- have ethyl-4-amino-1,2,4-triazolin-5-one herbicidal properties (compare, for example, DE-OS 37 19 575),

However, the herbicidal activity of these previously known compounds against problem weeds, like their tolerance to important crop plants, is not entirely satisfactory in all fields of application. New substituted triazolinones of the general formula (I)

(I)

in which R ^{1 represents} alkyl or cycloalkyl,

R ^{2 represents} in each case optionally substituted cycloalkyl, aryl or heterocyclyl, A represents a radical of the formula or

(CH ₂ ) _m -Q- (CH ₂ ) _n -

represents oxygen or sulfur and represents oxygen or sulfur, where R ^{3 represents} either hydrogen, cyano or alkyl and

R ⁴ , R ⁵ and R ⁶ each independently represent hydrogen or alkyl or R ³ and R ⁴ together represent a doubly linked radical of the formula - (CH ₂ ) _p -,

Q represents oxygen, sulfur, a sulfinyl group, a sulfonyl group or a radical of the formula) NR ⁷ ,

R ^{7 represents} hydrogen, alkyl, hydroxyalkyl, alkoxyalkyl, cyanoalkyl or alkanoyl, m represents a number 0, 1 or 2, n represents a number 0, 1 or 2 and p represents a number 2, 3, 4, 5 or 6 is found.

Depending on the nature of the substituents R ¹ , R ² and A, the compounds of the formula (I) may optionally be present as geometric and / or optical isomers or isomer mixtures of different compositions. Both the pure isomers and the isomeric strain are claimed according to the invention. Furthermore, it was found that the new substituted triazolinones of the general formula (I)

(I)

in which R ^{1 represents} alkyl or cycloalkyl,

(CH ₂ ) _m -Q- (CH ₂ ) _n -

X stands for oxygen or sulfur and Y stands for oxygen or sulfur, where R ^{3 represents} either hydrogen, cyano or alkyl and

R ⁴ , R ⁵ and R ⁶ each independently represent hydrogen or alkyl or

R ³ and R ⁴ together represent a doubly linked radical of the formula - (CH ₂ ) _p -,

Q represents oxygen, sulfur, a sulfinyl group, a sulfonyl group or a radical of the formula> NR ⁷ ,

R ^{7 represents} hydrogen, alkyl, hydroxyalkyl, alkoxyalkyl, cyanoalkyl or alkanoyl, m represents a number 0, 1 or 2, n represents a number 0, 1 or 2 and p represents a number 2, 3, 4, 5 or 6 is obtained if a) hydrazones of the formula (II),

in which

R ¹ , R ² , A, X and Y have the meaning given above and

R ⁸ and R ⁹ each independently represent hydrogen, alkyl, aralkyl or aryl, if appropriate with an acid in the presence of a diluent, or if 1H-triazolinones of the formula (III),

(III)

in which

R ¹ and X have the meaning given above, with iso (thio) cyanates of the formula (IV),

R ² -AN = C = Y (IV) in which

R ² , A and Y have the meaning given above, if appropriate in the presence of a diluent and if appropriate in the presence of a reaction auxiliary.

Finally, it was found that the new substituted triazolinones of the general formula (I) have herbicidal properties.

Surprisingly, the substituted triazolinones of the general formula (I) according to the invention show a considerably better herbicidal activity against problem weeds and, at the same time, a comparatively good tolerance to important crop plants in comparison to the substituted triazole inones known from the prior art, such as, for example, the compound 1- ( 4-phenyl-2-butylarainocarbonyl) -3-methyl-4-amino-1,2,4-triazolin-5-one or the compound 1- (1-cyclohexyl-1-ethylaminocarbonyl) -3-methyl-4 -amino-1,2,4-triazolin-5-one or the compound 1- (3-phenyl-2-methyl-2-propylaminocarbonyl) -3-ethyl-4-amino-1,2,4-triazolin-5 -on, which are chemically and functionally obvious compounds.

The substituted triazolinones according to the invention are generally defined by the formula (I). Compounds of formula (I) are preferred in which

R ¹ for straight-chain or branched alkyl with 1 to

6 carbon atoms or for cycloalkyl with 3 to

7 carbon atoms, R ^{2 represents} optionally mono- or polysubstituted, identically or differently substituted cycloalkyl having 3 to 7 carbon atoms, the following being suitable as substituents:

Halogen, cyano, in each case straight-chain or branched alkyl having 1 to 4 carbon atoms and in each case straight-chain or branched haloalkyl each having 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms;

in addition stands for aryl with 6 or 10 carbon atoms or heteroaryl with 2 to 9 carbon atoms and 1 to 4 identical or different heteroatoms - in particular nitrogen, oxygen and / or sulfur - which is optionally mono- or polysubstituted by identical or different substituents - in particular nitrogen, oxygen and / or sulfur, the substituents being in each case:

Halogen, cyano, nitro, each straight-chain or branched alkyl, alkoxy or alkylthio, each having 1 to 4 carbon atoms; each straight-chain or branched haloalkyl, haloalkoxy or haloalkylthio each having 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms; doubly linked, straight-chain or branched, optionally mono- to quadruple, identical or different, halogen-substituted dioxyalkylene having 1 to 3 carbon atoms;

Dialkylamino, N-alkanoylamino, alkoxycarbonyl or alkoximinoalkyl each having 1 to 4 carbon atoms in the individual straight-chain or branched alkyl parts, and in each case if appropriate Aryl or aryloxy with 6 or 10 carbon atoms, substituted one or more times, identically or differently, by halogen and / or straight-chain or branched alkyl having 1 to 4 carbon atoms, A for a radical of the formula or

(CH ₂ ) _m -Q- (CH ₂ ) _n -

X represents oxygen or sulfur and

Y represents oxygen or sulfur, where

R ^{3 represents} either hydrogen, cyano or straight-chain or branched alkyl having 1 to 8 carbon atoms and

R ⁴ , R ⁵ and R ⁶ each independently represent hydrogen or straight-chain or branched alkyl having 1 to 6 carbon atoms or

R ³ and R ⁴ together represent a doubly linked radical of the formula - (CH ₂ ) _p -, Q represents oxygen, sulfur, a sulfinyl group, a sulfonyl group or a radical of the formula> NR,

R ^{7 represents} hydrogen or straight-chain or branched alkyl, hydroxyalkyl, alkoxyalkyl, cyanoalkyl or alkanoyl each having 1 to 8 carbon atoms in the individual alkyl parts, m represents a number 0, 1 or 2, n represents a number 0, 1 or 2 stands for and p stands for a number 4, 5 or 6.

Compounds of the formula (I) in which

R ^{1 represents} methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl,

R ² for in each case one to five times,

the same or different substituted cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl, where the following are suitable as substituents:

Fluorine, chlorine, bromine, cyano, methyl, ethyl, n- or i-propyl, chloromethyl, dichloromethyl, trichloromethyl, difluoromethyl or trifluoromethyl; in addition, in each case optionally mono- to trisubstituted, identically or differently substituted

Phenyl, α-naphthyl, β-naphthyl, pyridyl, pyrimidyl, triazinyl, pyridazinyl, pyrazolyl, imidazolyl, triazolyl, thiazolyl, isothiazolyl, benzothiazolyl, oxazolyl, isoxazolyl, benzoxazolyl, pyrrolyl,

Furanyl, thienyl, indolyl, benzopyranyl or

Quinolyl is available, the following being suitable as substituents:

Fluorine, chlorine, bromine, cyano, nitro, 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, difluoromethyl, trifluoromethyl, difluoromethoxy, trifluoromethoxy, difluoromethylthio, trifluoromethylthio, dimethylamino, diethylamino, N-acetamido, dioxymethylene, difluorodioxymethylene, dioxydioxyethylene, methoxydioxyloxy, oxyoxyoxy, methoxydioxyethylene, methoxydioxyethylene, methoxydioxyethylene, trifluorodioxyethylene, methoxydioxyethylene, trifluorodioxyethylene, methoxydioxyethylene, methoxydioxyethylene, trifluorodioxyethylene, Methoximinoethyl, ethoximinomethyl, ethoximinoethyl or in each case optionally substituted one to three times, identically or differently, by fluorine, chlorine, bromine, methyl, ethyl, methoxy and / or ethoxy

Phenyl, phenoxy, α-naphthyl or β-naphthyl, for a radical of the formula

(CH ₂ ) _m -Q- (CH ₂ ) _n -

X represents oxygen or sulfur and

Y represents oxygen or sulfur, where

R ^{3 represents} either hydrogen, cyano or straight-chain or branched alkyl having 1 to 6 carbon atoms and

R ³ and R ⁴ together represent a radical of the formula - (CH ₂ ) ₅ -,

Q represents oxygen, sulfur or a radical of the formula> NR ⁷ ,

R ^{7 represents} hydrogen or represents straight-chain or branched alkyl, hydroxyalkyl, alkoxyalkyl, cyanoalkyl or alkanoyl each having 1 to 4 carbon atoms in the individual alkyl parts, m stands for a number 0 or 1 and n stands for a number 0 or 1. Compounds of the formula (I) in which

R ^{1 represents} methyl, ethyl, n- or i-propyl or cyclopropyl, R ^{2 represents} phenyl which is optionally mono- to trisubstituted by identical or different substituents, the following being suitable in each case:

Fluorine, chlorine, bromine, cyano, nitro, 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, difluoromethyl, trifluoromethyl, difluoromethoxy, trifluoromethoxy, difluoromethylthio, trifluoromethylthio, dimethylamino, diethylamino, N-acetamido, dioxymethylene, difluorodioxomethylene, dioxyethylene, trifluorodoxymethyloxyoxy, ethoxydioxyethyloxoxy, methoxydoxymethyloxyoxy, ethoxylated, methoxydoxymethyloxyoxy, ethylenedioxydoxymethyloxyoxy, ethylenedoxydoxymethyloxyoxy, ethylenedoxydoxymethyloxoxy, oxydoxymethyloxoxy, oxydoxymethyloxoxy, , Ethoximinoethyl or in each case optionally substituted one to three times, identically or differently, by fluorine, chlorine, bromine, methyl, ethyl, methoxy and / or ethoxy

Phenyl, phenoxy, α-naphthyl or β-naphthyl,

A for a radical of the formula or

(CH ₂ ) _m -Q- (CH ₂ ) _n -

X stands for oxygen and

Y represents oxygen, where

R ^{3 represents} either hydrogen, cyano or straight-chain or branched alkyl having 1 to 4 carbon atoms and

R ⁴ , R ⁵ and R ⁶ each independently represent hydrogen or straight-chain or branched alkyl having 1 to 3 carbon atoms or

R ³ and R ⁴ together represent a radical of the formula - (CH ₂ ) ₅ -,

Q represents oxygen, sulfur or a radical of the formula> NR ⁷ ,

R ^{7 stands} for hydrogen or for straight-chain or branched alkyl, hydroxyalkyl, alkoxyalkyl, cyanoalkyl or alkanoyl each having 1 to 3 carbon atoms in the individual alkyl parts, m stands for a number 0 or 1 and n stands for a number 0 or 1. The compounds listed in the preparation examples may be mentioned in detail.

If, for example, 1- {N- [4- (4-chlorophenoxy) -2-methyl-but-2-yl] carbamoyl} -4-isopropylidenimino-3-methyl-1,2,4-triazolin-5-one is used as the starting compound, the course of the reaction of process (a) according to the invention can be represented by the following formula:

If, for example, 4-amino-3-methyl-1,2,4- (1H) -triazole in-5-one and 3-methyl-4-phenoxy-but-2-yl-isocyanate are used as starting materials, then the course of the reaction of process (b) according to the invention is represented by the following formula:

Formula (II) provides a general definition of the hydrazones required as starting materials for carrying out process (a) according to the invention. In this formula (II), R ¹ , R ² , A, X and Y preferably represent those radicals which have already been mentioned as preferred for these substituents in connection with the description of the compounds of the formula (I) according to the invention.

R ⁸ and R ⁹ preferably each independently represent hydrogen, straight-chain or branched alkyl having 1 to 4 carbon atoms, phenyl or benzyl.

The hydrazones of the formula (II) are not yet known. They are also the subject of the present invention. They are obtained in analogy to known processes (compare, for example, DE-OS 38 03 523 or Acta Pol. Pharm. 38, 153-162 [1981] or CA 95: 203841), for example if 1H-triazole inones are used Formula (III),

(III)

in which

R ¹ and X have the meaning given above, with aldehydes or ketones of the formula (V),

(V)

in which R ⁸ and R ^{9 have} the meaning given above, optionally in the presence of a diluent such as dichloromethane or toluene and optionally in the presence of a reaction auxiliary such as p-toluenesulfonic acid at temperatures between 40 ° C and 120 ° C and the 1 unsubstituted triazole inone hydrazones of the formula (VI),

(VI)

in which

R ¹ , R ⁸ , R ⁹ and X have the meaning given above, either in a subsequent second stage with iso (thio) cyanates of the formula (IV),

R ² -AN = C = Y (IV) in which

R ² , A and Y have the meaning given above, optionally in the presence of a diluent such as dichloromethane or dioxane and optionally in the presence of a reaction auxiliary such as triethylamine at temperatures between 0 ° C and 150 ° C or alternatively in a subsequent 2nd Stage with (thio) chloroformate esters of the formula (VII),

(VII)

in which

R ^{10 represents} alkyl, aralkyl or aryl and

Y has the meaning given above, or with (thio) phosgene optionally in the presence of a diluent such as chloroform, dichloromethane or tetrahydrofuran and optionally in the presence of a reaction auxiliary such as triethylamine, sodium hydride or potassium tert-butylate at temperatures between -20 ° C and + 100 ° C and the triazole inone derivatives of the formula (VIII) thus obtainable, (VIII)

in which

Z represents a radical -OR ¹⁰ or chlorine and

R ¹ , R ⁸ , R ⁹ , X and Y have the meaning given above

have in a subsequent 3rd stage with amines of the formula (IX), R ² -A-NH ₂ (IX) in which

R ² and A have the meaning given above, optionally in the presence of a diluent such as tetrahydrofuran and optionally in the presence of a reaction auxiliary such as sodium hydroxide or potassium hydroxide at temperatures between 20 ° C and 50 ° C.

Alternatively, triazolinone derivatives of the formula (VIII) can also be obtained if triazolinones of the formula (X) (X)

in which R ¹ , X and Y have the meaning given above and R ^{10 represents} alkyl, aralkyl or aryl, with aldehydes or ketones of the formula (V),

(V)

in which R ⁸ and R ^{9 have} the meaning given above, optionally in the presence of a diluent such as dichloromethane or toluene and optionally in the presence of a reaction auxiliary such as p-toluene sulphonic acid at temperatures between 40 ° C and 120 ° C implemented.

The 1H-triazole inones required as starting materials for carrying out process (b) according to the invention and for synthesizing the precursors of the formula (II) are indicated by

Formula (III) generally defined. In this formula (III), R ¹ and X preferably represent those radicals which have already been mentioned as preferred for these substituents in connection with the description of the substances of the formula (I) according to the invention. The 1H-triazolinones of the formula (III) are known or can be obtained in analogy to known processes (compare, for example, J. Heterocycl. Chem. 16, 403 [1979]; J,

Heterocycl. Chem. 17, 1691, [1980]; Europ. J. Med. Chem. 18, 215 [1983]; Chem. Ber, 98, 3025 [1965]; Liebigs Ann. Chem, 637, 135 [1960]; DE-OS 37 19 575; DE-OS

38 03 523).

Formula (IV) provides a general definition of the iso (thio) cyanates required for carrying out process (b) according to the invention and for synthesizing the precursors of the formula (II) as starting materials. In this formula (IV), R ² , A and Y preferably represent those radicals which have already been mentioned as preferred for these substituents in connection with the description of the substances of the formula (I) according to the invention. The iso (thio) cyanates of the formula (IV) are known in some cases (compare, for example, JJ med. Chem. 30, 1767-1773

[1987]; J. org. Chem. 35, 47-52 [1970]; Be. Pharm. 51, 379 [1983]; Synthesis 1984, 315; Synthesis 1990, 803; Appl. Chem. 98, 1111 [1986]; Nouv. J. Chim. 1, 243-254 [1977] or CA 87: 151614a) or obtainable in analogy to known processes (compare, for example, Synthesis 1977, 756; Org. Syntheses Coll. Vol. IV, 521 [1963] or

"Organikum" VEB Deutecher Verlag der Wissenschaften Berlin 1981, p. 703). For example, they are obtained by amines of the formula (IX), R ² -A-NH ₂ (IX) in which R ² and A have the meaning given above, with phosgene or thiophosgene optionally in the presence of a diluent such as chloroform, toluene, chlorobenzene or tetrahydrofuran and optionally in the presence of a reaction auxiliary such as triethylamine, sodium hydroxide or potassium hydroxide at temperatures between -20 ° C. and + 150 ° C.

The amines of the formula (IX) are known or can be obtained in analogy to known processes (see, for example,

EP 273 328; Ind. J. Chem, Sect. B, 24B, 940-947 [1985]; Acta Pharm. Suec, 20, 349-364 [1983] and CA100: 174345; On. Quim. 73, 1177-1183 [1977] and CA89: 129148; Bull, Soc, Chim, Belg. 85, 421-425 [1976]; Tetrahedron Lett. 1976, 2289-2290; Bull. Chem, Soc, Jpn, 60, 609-612

[1987]).

The triazolinones of the formula (X) are known or can be obtained by analogy with known processes (compare, for example, DE-OS 37 19 575; DE-OS 38 03 523),

Aldehydes and ketones of the formula (V) are generally known compounds of organic chemistry. (Thio) chloroformic acid esters of the formula (VII) are also generally known compounds of organic chemistry.

Suitable diluents for carrying out process (a) according to the invention are all customary organic or inorganic solvents. Polar water-miscible organic solvents, in particular alcohols, such as methanol, ethanol, propanol or butanol, the mixtures of which are preferably used

Water or pure water as a solvent. The reaction temperatures can be varied within a substantial range when carrying out process (a) according to the invention. In general, temperatures between + 20 ° C and + 150 ° C, preferably at temperatures between + 50 ° C and + 120 ° C.

Process (a) according to the invention is usually carried out under normal pressure or under reduced pressure. If you work under reduced pressure, pressure ranges between 20 and 400 mbar, preferably between 100 and 200 mbar.

To carry out process (a) according to the invention, 1.0 to 50.0 mol, preferably 1.0 to 25 mol, of acid are generally employed per mol of hydrazone of the formula (II). The hydrazone of formula (II) is dissolved in a suitable amount of diluent, then the required amount of acid is added and the mixture is slowly concentrated under reduced pressure over several hours.

In a special embodiment, it is also possible to carry out process (a) according to the invention and the preparation of the precursors of the formula (II) required therefor in one reaction step in a so-called "one-pot process". Here's how that either the starting compounds are selected from the triazolinone derivatives of the formula (VIII) and these are reacted in succession in a "one-pot process" with amines of the formula (IX) and then with acid in accordance with process (a) according to the invention, or alternatively that the first compounds are unsubstituted triazoline hydrazones of the formula (VI) are selected and these are reacted in succession in a "one-pot process" with Ieo (thio) cyanates of the formula (IV) and then with acid in accordance with process (a) according to the invention.

The reaction is carried out, worked up and isolated by known processes (see, for example, DE-OS 38 03 523 or the preparation examples),

Inert organic solvents are suitable as diluents for carrying out process (b) according to the invention. 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 benzonitrile; 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 or sulfoxides such as dimethyl sulfoxide. If appropriate, process (b) according to the invention can be carried out in the presence of a suitable reaction auxiliary. All conventional inorganic or organic bases are suitable as such. It is preferred to use tertiary amines, such as trimethylamine, triethylamine, tributylamine, N, N-dimethylaniline, pyridine, piperidine, N-methylpiperidine, N, N-dimethylaminopyridine, diazabicyclooctane (DABCO), diazabicyclonones (DBN) or diazabicycloundecenes (DBU)

The reaction temperatures can be increased when carrying out process (b) according to the invention

Range can be varied. In general, temperatures between 0 ° C and + 150 ° C, preferably at temperatures between + 10 ° C and + 100 ° C. To carry out process (b) according to the invention, 1.0 to 2.0 mol, preferably 1.0 to 1.5 mol, of iso (thio) cyanate of the formula are generally employed per mol of 1H-triazole inone of the formula (III) (IV) and optionally 0.001 to 2.0 mol, preferably 0.001 to 1.0 mol, of reaction auxiliary.

The reaction is carried out, worked up and isolated using known processes (see, for example, DE-OS 38 03 523 or the preparation examples).

The end products of the formula (I) are purified using customary methods, for example by column chromatography or by recrystallization. The characterization is carried out using the melting point or, in the case of non-crystalline compounds, using proton nuclear magnetic resonance spectroscopy ( ¹ H-NMR).

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 which grow up 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 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, Polygonuro, Sesbania, Ambrosia, Cirsium, Carduippum, Sonuanum , Rotala, Linderniai 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. Monocotyledon weeds of the genera: Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis, Sagittaria, Iochasumirumum, Scalumumum, Scalumumum , Sphenoclea, Dactyloctenium, Agrostis, Alopecurus, Apera,

Monocot cultures of the genera: Oryza, Zea, Triticum, Hordeum, Avena, Secale, 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 compounds are suitable for total weed control, e.g. on industrial and track systems and on paths and squares with and without tree cover. Likewise, the compounds for weed control in permanent crops, e.g. 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 and for selective purposes Weed control can be used in annual crops.

The active compounds according to the invention can be used particularly successfully to control monocotyledon and dicotyledon weeds in monocotyledon and dicotyledon crops such as, for example, wheat, corn or sugar beet. 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 polymeric substances,

These formulations are prepared in a known manner, for example by mixing the active ingredients with

Extenders, that is liquid solvents, pressurized liquefied gases and / or solid carriers, optionally using surface-active agents, that is to say emulsifiers

and / or dispersing agents and / or foaming agents.

If water is used as an extender, e.g. organic solvents can also be used as auxiliary solvents. The following are essentially suitable as liquid solvents: aromatics such as xylene, toluene or alkylnaphthalene, chlorinated aromatics and chlorinated aliphatic hydrocarbons such as chlorobenzenes, chlorethylenes or methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffins, e.g. 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,

The following are suitable as solid carriers:

e.g. Ammonium salts and natural stone powder such as

Kaolins, clays, talc, chalk, quartz, attapulgite, Montmorillonite or diatomaceous earth and synthetic stone powder such as highly disperse silica, aluminum oxide and silicates; Solid carriers for granules are possible: for example broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules from inorganic and organic flours as well as granules from organic material such as sawdust, coconut shells, corn cobs and tobacco stalks; suitable emulsifiers and / or foam-generating agents are: for example nonionic and anionic emulsifiers such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates; Possible dispersing agents are, for example, lignin sulfite waste liquor and methyl cellulose.

Adhesives such as carboxymethylcellulose, 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 dyestuffs 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 anilides, such as, for example, diflufenican and propanil; Aryl carboxylic acids, such as, for example, dichloropicol acid, dicamba and picloram; Aryloxyalkanoic acids, such as, for example, 2.4 D, 2.4 DB, 2.4 DP, fluroxypyr, MCPA, MCPP and triclopyr; Aryloxy-phenoxy-alkanoic acid esters, such as, for example, diclofop-methyl, fenoxaprop-ethyl, fluazifop-butyl, haloxyfop-methyl and quizalofop-ethyl; Azinones such as chloridazon and norflurazon; Carbamates such as chlorpropham, desmedipham, phenmedipham and propham; Chloroacetanilides such as alachlor, acetochlor, butachlor, metazachlor, metolachlor, pretilachlor and propachlor; Dinitroaniline such as Oryzalin, Pendimethal in and Trifluralin; Diphenyl ethers such as acifluorfen, bifenox, fluoroglycofen, fomesafen, halosafen, lactofen and oxyfluorfen; Ureas such as chlorotoluron, diuron, fluometuron, isoproturon, linuron and methabenzthiazuron; Hydroxylamines, such as, for example, alloxydim, clethodim, cycloxydim, setoxydim and tralkoxydim; Imidazolinones such as imazethapyr, imazamethabenz, imazapyr and imazaquin; Nitriles such as bromoxynil, dichlobenil and ioxynil; Oxyacetamides such as mefenacet; Sulfonylureas, such as amidosulfuron, bensulfuron-methyl, chlorimuron-ethyl, chlorosulfuron, cinosul furon, metsulfuron-methyl, nicosulfuron, primisulfuron, pyrazosulfuron-ethyl, thifensulfuron-methyl, triasulfuron and tribenuron-methyl; Thiol carbamates such as butylates, cycloates, dialallates, EPTC, esprocarb, molinates, prosulfocarb, thiobencarb and triallates; Triazines such as atrazine, cyanazine, simazin, simetryne, terbutryne and terbutylazine; Triazinones such as hexazinone, metamitron and metribuzin; Others such as aminotriazole, benfuresate, bentazone, cinmethylin, clomazone, clopyralid, difenzoquat, dithiopyr, ethofumesate, fluorochloridone, glufosinate, glyphosate, isoxaben, pyridate, quinchlorac, quinmerac, sulphosate and tridiphane. 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. Active substances can never 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 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 the desired effect. In general, the application rates are between 10 g and 10 kg of active ingredient per hectare of soil, preferably between 50 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:

[Method (a) - "One-pot variant"]

To 3.9 g (0.02 mol) of 4- (4-methylpent-2-ylidene-imino) -3-methyl-1,2,4-triazolin-5-one in 100 ml of dichloromethane is added in succession 0.1 g of diazabicycloundecene (DBU) and 3.7 g (0.02 mol) of 3-methyl-1-phenyl-but-1-yn-3-yl isocyanate and stirred for 18 hours at 20 ° C. Then the solvent removed in vacuo, the residue taken up in 100 ml of ethanol, mixed with 20 ml of water and 5 ml of concentrated hydrochloric acid and stirred for 3 hours at 60 ° C. and 200 mbar. For working up, the solvent is distilled off in vacuo, the residue is taken up in dichloromethane, washed with saturated aqueous sodium hydrogen carbonate solution, dried over sodium sulfate and concentrated in vacuo. The residue is crystallized by trituration with petroleum ether, filtered off and dried.

1.2 g (20% of theory) of 4-amino-3-methyl-1- (3-methyl-1-phenyl-but-1-yn-3-yl-aminocarbonyl) -1,2,4- triazolin-5-one with a melting point of 100 ° C. Establishing the output connection:

Example IV-1:

A solution of 159 g (1.0 mol) of 3,3-dimethyl-1-phenyl-propynylamine in 1 is added dropwise to 150 g (1.5 mol) of phosgene in 2.5 l of chlorobenzene at 15 ° C. with stirring, 0 1 chlorobenzene, the temperature of the reaction mixture rising to 25 ° C. When the addition is complete, the mixture is heated to 70 ° C. and with stirring and further introduction of

Phosgene (approx. 50 g / hour) slowly heated to the reflux temperature and stirred at this temperature for a further 30 minutes. For working up, about 1 liter of chlorobenzene is distilled off together with excess phosgene, the residue is concentrated in a water jet vacuum and distilled in a high vacuum.

106 g (57% of theory) of 3-methyl-1-phenylbut-1-yn-3-yl isocyanate are obtained, with a boiling point of 80 ° C. at 0.5 mbar and a refractive index = 1.5258.

Example IX-1

To 78.51 g (0.5 mol) of bromobenzene and 45.7 g (0.55 mol) of 3-amino-3,3-dimethyl-1-propyne in 500 ml of triethylamine are added 7.0 g (0.01 Mol) palladium (II) bis-triphenylphosphine dichloride, 7.6 g (0.04 mol) copper (I) iodide and 21.0 g (0.4 mol) triphenylphosphine, heated for 24 hours to reflux temperature, then filtered and the filtrate concentrated in a water jet vacuum. The residue is partitioned between dichloromethane (approx. 300 ml) and water (approx. 300 ml), the organic phase is separated off, dried over sodium sulfate and filtered. The filtrate is concentrated in a water jet vacuum and distilled in a high vacuum.

74.1 g (75% of theory) of 3-amino-3,3-dimethyl-1-phenyl-1-propyne of the refractive index are obtained

= 1.5443,

Example VI-1:

A mixture of 114 g (1.0 mol) of 4-amino-3-methyl-1,2,4-triazolin-5-one (see, for example, DE-OS 38 03 523), 2 g of p-toluenesulfonic acid and 500 ml of 4th -Methylpentan-2-one is refluxed for 4 hours over a water separator. For working up, the mixture is concentrated in vacuo. The residue is stirred with petroleum ether, filtered off and dried.

187 g (95% of theory) of 4- (4-methylpent-2-ylidene-imino) -3-methyl-1,2,4-triazolin-5-one are obtained

Melting point 91 ° C,

The following substituted triazolinones of the general formula (I) are obtained in a corresponding manner and in accordance with the general information on the preparation:

(I)

*) The ¹ H-NMR spectra were in deuterochloroform

(CDCl ₃ ) or hexadeuterodimethyl sulfoxide (DMSO-d ₆ ) with tetramethyl silane (TMS) added as the internal standard. The chemical shift is given as a δ value in ppm.

Examples of use:

In the following application examples, the compounds listed below were used as comparison substances:

1- (4-phenyl-2-butylaminocarbonyl) -3-methyl-4-amino-

1,2,4-triazolin-5-one

1- (3-phenyl-2-methyl-2-propylaminocarbonyl) -3-ethyl-4-amino-1,2,4-triazolin-5-one

1- (1-cyclohexyl-1-ethylaminocarbonyl) -3-methyl-4-amino-1,2,4-triazolin-5-one (all known from DE-OS 37 19 575) 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 and watered with the active ingredient preparation after 24 hours. The amount of water per unit area is expediently kept constant. The concentration of active substance in the preparation is irrelevant, the decisive factor is only the amount of active substance applied per unit area. 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, the compounds according to preparation examples 10 and 11, for example, show a clear superiority in effectiveness as well as in crop selectivity compared to the prior art. The compounds according to the production examples 10 and 11 show, for example, at an application rate of 1,000 to 2,000 g per hectare in the pre-emergence test, a 70 to 100% activity against problem weeds such as amaranthus, cassia, portulaca and viola with excellent tolerance to useful plants such as wheat , Corn and sugar beet. In contrast, the comparison compound A shows only little effects on problem weeds at an application rate of 2,000 g per hectare.

At game 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 5-15 cm are sprayed with the active substance preparation in such a way that the desired amounts of active substance are applied per unit area. 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, 11, 12, 13 and 19 show a clear superiority in effectiveness as well as in crop selectivity compared to the prior art. Compounds according to the production examples 1, 3, 11, 12, 13 and 19 show, for example, at application rates between 125 and 500 g per hectare in the post-run test, an 80 to 100% activity against problem weeds such as Amaranthus, Galium, Matricaria, Solanum and Viola with excellent crop selectivity, especially with respect to wheat and corn. The comparison compounds B and C, however, have only a low herbicidal activity.

Claims

1. Substituted triazolinones of the general formula (I),

(I) V

in which R ^{1 represents} alkyl or cycloalkyl R ^{2 represents} in each case optionally substituted cycloalkyl, aryl or heterocyclyl,

A for a residue of the formula

or

R

stands,

R ⁴ , R ⁵ and R ⁶ each independently represent hydrogen or alkyl, or R ³ and R ⁴ together represent a double bond

Rest of the formula - (CH ₂ ) _p - stand,

R ^{7 represents} hydrogen, alkyl, hydroxyalkyl, alkoxyalkyl, cyanoalkyl or alkanoyl, m represents a number 0, 1 or 2, n represents a number 0, 1 or 2 and p represents a number 2, 3, 4, 5 or 6 stands.

2. Herbicidal agents, characterized in that they contain at least one substituted triazolinone

Formula (I) according to claim 1.

3. A method for controlling unwanted plants, characterized in that substituted triazolinones of the formula (I) according to Claim 1 are allowed to act on undesired plants and / or their habitat.

4. Use of substituted triazole inones

Formula (I) according to claim 1 for combating undesirable plants,

5. Substituted hydrazones of the formula (II),

(II) V

in which

R ^{1 represents} alkyl or cycloalkyl,

R ² for each optionally substituted

Cycloalkyl, aryl or heterocyclyl, A represents a radical of the formula

X stands for oxygen or sulfur and Y stands for oxygen or sulfur, where

R ^{3 is} either hydrogen, cyano or alkyl

is and R ⁴ , R ⁵ and R ⁶ are each independently

Are hydrogen or alkyl or

R ³ and R ⁴ together for a double linked

Rest of the formula - (CH ₂ ) _p - stand,

Q represents oxygen, sulfur, a sulfinyl group, a sulfonyl group or a radical of the formula> NR ⁷ , R ^{7 represents} hydrogen, alkyl, hydroxyalkyl,

Alkoxyalkyl, cyanoalkyl or alkanoyl, m stands for a number 0, 1 or 2, n stands for a number 0, 1 or 2 and p stands for a number 2, 3, 4, 5 or 6, and

R ⁸ and R ⁹ each independently represent hydrogen, alkyl, aralkyl or aryl.