SK279720B6 - Substituted triazolinones, method and intermediates for their preparation, use thereof, and herbicidal agent them containing - Google Patents

Abstract

Novel compounds of the general formula (I), wherein R1 is hydrogen, C1-8-alkyl, C3-7-cycloalkyl, halogen-C1-4-alkyl or optionally substituted C6-10-aryl, R2 is C1-18-alkyl, C2-8- -alkenyl, C2-8-alkinyl, halogen-C1-8-alkyl, halogen-C2-8- -alkenyl, cyano-C1-8-alkyl, C1-6-alkoxy-C1-6-alkyl, C1-6-alkoxycarbonyl-C1-6-alkyl, C1-6-alkoxycarbonyl-C2-6- -alkenyl, C1-6-alkylamino-C1-6-al-kyl, di-C1-6-alkylamino-C1-6- -alkyl, optionally substituted C1-6-cycloalkyl or C3-12- -cycloalkyl-C1-6-alkyl, optionally substituted C6-10-aryl-C1-8- -alkyl or C6-10-aryl, X and Y denote-independently from each other an oxygen or sulphur atom. There is further described a herbicidal agent which contains at least one compound of the general formula (I), as its active ingredient, wherein R1 is C1-4-alkyl or C1-4-halogenalkyl, R2 is C1-10-al-kyl, C1-6- -halogenalkyl, optionally substituted C3-12-cycloalkyl, C2-8-alkinyl, optionally substituted C3-8-cycloalkyl-C1-4-alkyl, X and Y denote an oxygen atom. There is also disclosed a method for the preparation of compounds of formula (I) and novel intermediates used during the process of said preparation.

Description

Technical field

The present invention relates to novel substituted triazolinones, to several methods for their preparation and to their use as herbicides. Furthermore, the invention relates to novel intermediates which are used in the production of said novel substituted triazolinones.

BACKGROUND OF THE INVENTION

It is known that certain heterocyclic compounds containing nitrogen as a heteroatom such as 4-amino-3-methyl-6-phenyl-1,2,4-triazin-5-one or N-isobutyl-2-oximidazolidine-1-carboxamide ( DEOS 23 64 474 and R. Wegler Chemie der Pflanzenschutz- und Schädlingsbekämpfungsmittel, Vol. 5, 219 (1977) have herbicidal properties.

The herbicidal activity of these first known compounds against weeds, which can be controlled very difficultly, is not entirely satisfactory in all fields of use, as is their tolerance to important crop plants.

Furthermore, certain substituted triazolinones are known, such as 1- (N, N-dimethylcarbamoyl) -3-phenyl-4-amino-1,2,4-triazolin-5-one (cf. J. Heterocycl. Chem 17, 1691 - 1696 (1980), Org Mass Spectrom 14, 369-378 (1979)).

However, nothing has been known about the efficacy of these first known triazolinones as herbicides.

SUMMARY OF THE INVENTION

New substituted triazolinones of formula (I) have now been found.

in which

R ¹ represents a hydrogen atom, a straight or branched alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 7 carbon atoms in the cycloalkyl moiety, optionally at least once, as well as a different halogen atom substituted with 6-10 carbon atoms or haloalkyl a group having 1 to 4 carbon atoms and up to 9 of the same or different halogen atoms,

R ² is straight or branched alkyl group having 1 to 18 carbon atoms, alkenyl of 2-8 carbon atoms, alkynyl of 2-8 carbon atoms, haloalkyl of 1 to 8 carbon atoms and 1 to 17 identical or different halogen atoms , C 2 -C 8 haloalkenyl and C 1 -C 15 identical or different, C 1 -C 8 cyanoalkyl, C 1 -C 6 alkoxyalkyl and C 1 -C 6 alkoxyalkyl, C 1 -C 6 alkoxycarbonylalkyl carbon atoms in the alkoxy and alkyl moieties, alkoxycarbonylalkenyl of 1 to 6 carbon atoms in the alkoxy moiety with 2 to 6 carbon atoms in the alkenyl moiety, alkylaminoalkyl of 1 to 6 carbon atoms in the alkyl moieties, a dialkylaminoalkyl group of 1 to 6 carbon atoms in the alkyl moieties or in each case at least once the same or different sub a C 3 -C 12 cycloalkyl or cycloalkylalkyl radical having from 1 to 6 carbon atoms in the straight or branched chain alkyl moiety, the substituents being halogen, straight or branched (C 1 -C 4) alkyl groups , (C 1 -C 4) haloalkyl, (C 1 -C 4) haloalkyl, (C 1 -C 9) or different halogen or straight-chained or branched (C 4 -C 4) haloalkenyl, with 1 to 5 identical or different halogen atoms, furthermore R ² represents an optionally at least one, same or different, substituted aralkyl, or an aryl group having 6 to 10 carbon atoms in the aryl lo Vej part and optionally from 1 to 8 carbon atoms in a straight or branched alkyl, wherein the substituents of the alkyl group where appropriate, and halogen atoms and as aryl substituents are halogen, straight or branched (C1-C6) alkyl or (C1-C6) alkoxy,

X is O or S and Y is O or S.

In particular, the present invention relates to substituted triazolinones of the general formula (I) in which: is H, straight or branched alkyl of 1 to 8 carbon atoms, cycloalkyl having 3 to 7 carbon atoms and optionally at least one, same or different halogen substituted aryl of 6 to 10 carbon atoms, R ² is straight or branched (C až-C) alkyl, (C až-C alk) alkenyl, (C až-C 8) alkynyl, (C až-C as) haloalkyl, (C alebo-C až), C 1-C hal hal) 8 to about 15 identical or different halogen atoms, a cyanoalkyl group having 1 to 8 carbon atoms, an alkoxyalkyl group having 1 to 6 carbon atoms in the alkoxy and alkyl moieties or an alkoxycarbonylalkyl group having 1 to 6 carbon atoms in both the alkoxy and alkyl moieties C 1 -C 6 dialkylaminoalkyl; or in each case at least once the same or differently substituted cycloalkyl or cycloalkylalkyl group each having from 3 to 8 carbon atoms in the cycloalkyl moiety and from 1 to 6 carbon atoms in the straight or branched chain alkyl moiety, the substituents being halogen, straight or a branched alkyl group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms and having 1 to 9 same or different halogen atoms or a haloalkenyl group having up to 4 carbon atoms in a straight or branched chain having 1 to 5 identical or different halogen atoms R ² is optionally at least one, same or differently substituted aralkyl or aryl group having 6 to 10 carbon atoms in the aryl moiety and optionally having 1 to 8 carbon atoms in the straight or branched alkyl moiety, optionally as alkyl substituents consideration at halogen atoms and aryl substituents are halogen, straight or branched (C 1 -C 6) alkyl or (C 1 -C 6) alkoxy,

X is oxygen or sulfur; and

Y represents an oxygen atom or a sulfur atom.

The compounds of formula (I) may optionally be present, depending on the nature of the substituents R ¹ and R ² as geometric and / or optical isomers or isomer mixtures of different composition. Both pure isomers and mixtures of isomers are within the scope of the present invention.

The present invention further provides a process for the preparation of the novel substituted triazolinones of formula (I)

in which

R ¹ is hydrogen, straight or branched alkyl of 1 to 8 carbon atoms, cycloalkyl having 3 to 7 carbon atoms in the cycloalkyl, optionally, at least one, same or different halogen substituted aryl of 6 to 10 carbon atoms or haloalkyl a group having 1 to 4 carbon atoms and up to 9 of the same or different halogen atoms,

R ² is straight or branched alkyl group having 1 to 18 carbon atoms, alkenyl of 2-8 carbon atoms, alkynyl of 2-8 carbon atoms, haloalkyl of 1 to 8 carbon atoms and 1 to 17 identical or different halogen atoms , C 2 -C 8 haloalkenyl of up to 15 identical or different halogen atoms, C 1 -C 8 cyanoalkyl, C 1 -C 6 alkoxyalkyl, C 1 -C 6 alkoxycarbonylalkyl in both alkoxy and alkyl moieties, C 1 -C 6 alkoxycarbonylalkenyl in the C 2 alkoxy moiety, C 1 -C 6 alkylaluminoalkyl, C 1 -C 6 dialkylaminoalkyl in the alkyl moieties or in each case at least once the same or different subst an ituated cycloalkyl or cycloalkylalkyl group having from 3 to 12 carbon atoms in the cycloalkyl moiety and from 1 to 6 carbon atoms in the straight or branched chain alkyl moiety, the substituents being halogen, straight or branched alkyl of 1 to 4 atoms C 1 -C 4 haloalkyl, C 1 -C 4 haloalkyl, C 1 -C 9 haloalkyl or C 1 -C 4 haloalkenyl of 1 to 5 identical or different atoms R ² is optionally at least one, same or differently substituted aralkyl, or aryl of 6 to 10 carbon atoms in the aryl moiety and optionally of 1 to 8 carbon atoms in the straight or branched alkyl moiety, wherein as alkyl substituents where appropriate, etc We halogen, and substituents of the aryl group are, for halogen, straight or branched alkyl group having 1 to 6 carbon atoms or alkoxy of 1 to 6 carbon atoms,

X is oxygen or sulfur; and

Y stands for an oxygen atom or a sulfur atom which consists of:

(a) reacting the hydrazones of formula (II)

in which

R ¹ , R ² , X and Y are as defined above and

R ³ and R ⁴ are each independently hydrogen, alkyl, aralkyl or aryl, with an acid, optionally in the presence of a diluent, or

b) reacting 1 H-triazolinones of general formula (H1)

in which

R ¹ and X are as defined above, with a iso (thio) cyanates of formula (IV)

R ² -N = C = Y (IV) wherein

R ² and Y are as defined above, optionally in the presence of a diluent and optionally in the presence of a reaction auxiliary, or

c) reacting the triazolinones of general formula (V)

in which

R ^1, X and Y are defined as above, and

R ⁵ represents an alkyl group, an aryl group or an arylalkyl group, with amines of general formula (VI)

R ² -NH ² (VI) wherein

R ² has the stated meaning, optionally in the presence of a diluent and optionally in the presence of a reaction auxiliary.

Finally, it has been found that the novel substituted triazolinones of formula (I) have herbicidal properties.

Surprisingly, the substituted triazolinones of the general formula (I) according to the invention have a considerably higher herbicidal activity against weeds which can be controlled only with difficulty compared to the nitrogen-containing heterocyclic compounds known in the art, such as 4-amino-3-methyl -6-phenyl-1,2,4-triazin-5-one, and which are the closest related compounds in terms of chemical and activity.

The substituted triazolinones of the invention are generally defined by formula (I). Preferred are those compounds of formula (I) in which

R ¹ is H, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, n-hexyl , isohexyl, cyclopentyl, cyclohexyl, cyclopropyl or, optionally, one to three times the same or differently substituted phenyl group, the substituents being fluorine, chlorine and bromine,

R ² is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl, in each case straight-chain or branched pentyl, hexyl, heptyl, octyl , nonyl, decyl, dodecyl, allyl, straight or branched butenyl, pentenyl or hexenyl, propargyl, straight or branched butynyl, pentinyl or hexinyl, straight or branched halogeno 8 carbon atoms and 1 to 9 identical or different halogen atoms, in particular fluorine, chlorine or bromine, in each case a straight or branched haloalkenyl or haloalkynyl group each having from 3 to 8 carbon atoms of about 3 halogen atoms, in particular fluorine or chlorine, in each case straight or branched; branched cyano C 1-6 alkyl, alkoxyalkyl, alkoxycarbonylalkyl, dialkylaminoalkyl of up to 4 carbon atoms in the individual alkyl or alkenyl moieties, or in each case optionally one to three times, the same or differently substituted cyclopropyl, cyclopropylmethyl , cyclopropylethyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclohexylmethyl, cyclohexylethyl, each substituent being fluorine, chlorine, bromine, methyl, ethyl, n-propyl, n-propyl n-butyl, isobutyl, sec-butyl, or tert-butyl or dichloroallyl,

R &^lt; ² > furthermore optionally represents one or three times the same or differently substituted benzyl, phenethyl, phenylpropyl, phenylbutyl, phenylpentyl, phenylhexyl, phenylheptyl, phenyl or naphthyl groups, fluorine substituents being in each case fluorine , chloro, bromo, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, methoxy and ethoxy,

X is oxygen or sulfur; and

Y represents an oxygen atom or a sulfur atom

Very particularly preferred are compounds of formula (I) wherein:

R ¹ represents a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group,

R ² is hydrogen, in each case optionally mono- to trisubstituted by fluorine and / or chlorine-substituted methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl , allyl, propargyl, in each case straight or branched pentyl, hexyl, heptyl, octyl, butenyl, pentenyl, hexenyl, butynyl, pentinyl or hexinyl;

moreover, in each case, one to three times the same or differently represents fluorine, chlorine, methyl, ethyl-substituted cyclopropyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclopropylethyl, cyclohexylmethyl, cyclohexylethyl or cycloheptyl and cycloheptyl , a phenylethyl group or a phenyl group,

X is oxygen or sulfur; and

Y represents an oxygen atom or a sulfur atom.

The following substituted triazolinones of general formula (I) may be individually mentioned in addition to the compounds given in the examples.

0o oo

0s ss ss □ o

R ¹

B ²

CH ₃ -CE-COOC ₃ H ₃ ch ₃

CH2-CH2-CH2-CH2-CH- (CH2-J-CH-j)

CH 2 CH 3 ^ca 3

-GH

(ch ₂ ) ₂ -ck ₃

(ck ₂ ) ₂ -cb ₃

(CHjJj -CH

CE-CH

R-configuration ³ 'xCH-CH

R ²

S · configuration

CH

-CH-CH, -OCH, I ² 3

CH

CH

CH

· CH.

- (^ CHP -CH

- (CH-CHgJj

-ÍCHgJj-C ^

I ⁵ «3

Sc so so so

Accordingly, a further object of the present invention is a herbicidal composition which comprises as an active ingredient at least one substituted triazolinone of formula (I) in which:

R ¹ is C 1 -C 4 alkyl or C 1 -C 4 haloalkyl of up to 9 same or different halogen atoms, R ² is C 1 -C 10 alkyl, C 1 -C 6 haloalkyl and s C 1 -C 13 halogen, C 3 -C 12 cycloalkyl optionally substituted with C 1 -C 4 alkyl or C 1 -C 4 haloalkyl; C 2 -C 8 alkynyl, C 3 -C 8 cycloalkylalkyl having 1 to 4 carbon atoms in the alkyl moiety, the cycloalkylalkyl group being optionally substituted in the cycloalkyl moiety with C 1 -C 4 alkyl; a halogen atom, or a (C 1 -C 4) alkoxyalkyl group in the alkoxy and alkyl moieties, X is an oxygen atom, and

Y represents an oxygen atom.

The present invention also relates to the use of these substituted triazolinones for weed control, as well as to a process for preparing herbicidal compositions which comprises mixing the substituted triazolinone defined with a carrier and / or a surfactant.

The preparation of the compounds of formula (I) as well as the intermediates required for this process will be described in more detail below.

If, for example, 1- (N-isobutylcarbamoyl) -4-isopropylidenimino-3-methyl-1,2,4-triazolin-5-one is used as starting material in the process according to the invention, the reaction according to variant a) of the process according to the invention can be carried out as shown in the following reaction scheme:

7 '/ o K ₉ -CH ₂ -CH (CH.p ₂

H-CH ₂ -CE (CH ₃ ) ₂

If, for example, 4-amino-3-methyl-1,2,4- (1H) -triazolin-5-one and tert-butylisocyanate are used as starting materials, the reaction according to variant b) of the process according to the invention can be illustrated by the following reaction scheme:

If, for example, 1-ethoxycarbonyl-4-amino-3-methyl-1,2,4-triazolin-5-one and N, N-diethyl-propane-1,3-diamine are used as starting materials, then the course may be Reactions according to variant c) of the process according to the invention are represented by the following reaction scheme:

SK 279720-6

ABOUT . C-OCjKj

The hydrazones required as starting materials in carrying out the process of the invention (variant a) are generally defined by formula (II). In this formula, R ¹ , R ² , X and Y preferably have the meanings already indicated for these substituents as preferred in connection with the description of the compounds of formula (I).

The substituents R ³ and R ⁴ preferably each independently represent a hydrogen atom, a straight or branched alkyl group having 1 to 4 carbon atoms, or a phenyl group or a benzyl group.

The hydrazones of formula (II) have not been known hitherto. These novel intermediates are also an object of the present invention.

Compounds of formula (II) are prepared analogously to known procedures (cf. e.g. Acta Pol. Pharm. 38, 153-162 (1981) or CA 95, 203841j), for example by reacting 1-unsubstituted 4-ammotriazolinones of formula (III)

H in which

R ¹ and X are as defined above, with aldehydes or ketones of general formula (VII)

(VII) in which:

R ³ and R ⁴ are as defined above, optionally in the presence of a diluent such as dichloromethane or toluene and optionally in the presence of a catalyst such as p-toluenesulfonic acid at temperatures between 40 ° C and 120 ° C, whereupon the I-unsubstituted thus obtained triazolinone hydrazones of general formula (VIII)

M in which

R ¹ , R ³ , R ⁴ and X are as defined above, either reacted with iso (thio) cyanates of formula (IV) in the next second step

^R2 - N = C = Y (IV) wherein

R ² and Y are as defined above, optionally in the presence of a diluent, such as dichloromethane or dioxane and optionally in the presence With it, a reagent, such as triethylamine, at temperatures between 50 and 150, or, alternatively, in a subsequent second step, the p (thio) chloroformic acid esters of general formula (IX)

Y _c H

R 5 -O-C-Cl (IX) wherein

R ⁵ represents an alkyl group, an aryl group or an arylalkyl group and

Y is as hereinbefore defined, optionally in the presence of a diluent such as tettahydrofuran and optionally in the presence of an auxiliary reagent such as sodium hydride or potassium tert-butoxide at temperatures between -20 ° C and +40 ° C, and the triazolinones thus obtained X)

r = coR ⁵ in which

R ¹ , R ³ , R ⁴ , R ³ , X and Y are as defined above, and are reacted with amines of formula (VI) in the next step

R ² -NH ₂ (VI) wherein

R ² has the stated meaning, optionally in the presence of a diluent, such as napríkladtetrahydroturánu, and optionally in the presence of a base such as sodium or potassium hydroxide, at temperatures between 20 ° C and 50 ° C.

Reaction of the 1-unsubstituted triazolinone hydrazones of formula (VIII) with (thio) chloroformic acid esters of formula (IX) and the subsequent reaction of the triazolinones of formula (X) thus obtained with amines of formula (VI) in the same a single reaction step (i.e., the reaction is carried out in a single reaction vessel) (cf. Example 3).

The 1-unsubstituted 4-aminotriazolinones of formula (ΠΙ) are known compounds or can be obtained analogously to known procedures (cf., for example, J. Heterocycl. Chem. 16, 403 (1979), J. Heterocycl. Chem. 17, 1961 (1980), Europe). J. Med. Chem., 18, 215 (1983), Chem Ber., 98, 3025 (1965 or Liebigs Ann. Chem. 637, 135 (1960)).

The aldehydes or ketones of formula (VII) are generally known organic chemistry compounds.

The 1-unsubstituted triazolinone hydrazones of formula (VHI) are largely known compounds (cf., for example, J. Heterocycl. Chem. 20, 77-80 (1983); J. Heterocycl. Chem. 16, 403-407 (1979), Chim. Acta Turc., 7, 269-290 (1979), J. Chem. Soc., Parkin Trans. II, 1973, 9-11, J. Org. Chem., 36, 2190-2192 (1971).

The (thio) chloroformic acid esters of formula (IX) are generally known organic chemistry compounds.

The triazolinones of formula (X), referred to as intermediates, are partially known compounds (cf., for example, Acta Pol. Pharm. 38, 153-162 (1981) and C.A. 95, 203841j).

The triazolinones of formula (X) that are new are defined by formula (Xa)

^ X (Xa)

X «C - 0 - r5 in which

¹ R ^'1 is alkyl, and

R ³ , R ⁴ , R ⁵ , X and Y are as defined above

Preferred are compounds of formula (Xa) in which

¹ R ^'1 is preferably a straight or branched alkyl of 1 to 4 carbon atoms, especially of 1 to 3 carbon atoms, very particularly ¹ then R' ¹ is methyl,

R ³ and R ⁴ are each independently hydrogen, straight or branched (C 1 -C 4) alkyl or phenyl, or benzyl,

R ⁵ is preferably a straight-chain or branched alkyl having 1 to 4 carbon atoms, or optionally mono- to trisubstituted by identical or different substituted phenyl or benzyl, wherein the substituents are, for a halogen atom, cyano, nitro, in each case linear or branched, alkyl, alkoxy or alkylthio, in each case having from 1 to 4 carbon atoms or in each case straight-chain or branched haloalkyl, haloalkoxy or haloalkylthio, in each case having from 1 to 4 carbon atoms and from 1 to 9 identical or different halogen atoms,

R ⁵ is especially methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl, or optionally once or twice, as well or differently substituted phenyl or benzyl and, in each case, fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert- butyl, methoxy, ctoxy, n-propoxy, isopropoxy, methylthio, trifluoromethyl, trifluoromethoxy or trifluoromethylthio,

X and Y are each independently O or S, preferably O.

The 1 H-triazolinones required as starting materials in carrying out the process of variant b) are generally defined by formula (III). In this formula (ΠΙ), R ¹ and X are preferably those that have been shown to be advantageous for these symbols in the context of the description of the compounds of formula (I) of the invention.

The 1 H-triazolinones of the formula (ΠΙ) are known or obtained analogously to known procedures (cf., for example, J. Heterocycl. Chem. 16, 403 (1979), J. Heterocycl. Chem. 17, 1691 (1980), Europe. J. Med. Chem., 18, 215 (1983), Chem Ber, 98, 3025 (1965), Liebigs Ann. Chem., 637, 135 (1960).

The iso (thio) cyanates that are further required as starting materials in carrying out the process of variant b) are generally defined by formula (IV). In this formula (IV) R ² represents a substituent, and Y preferably represent those radicals which have already been mentioned as preferred in connection with the description of the compounds of formula (I) of the invention for these substituents.

The iso (thio) cyanates of formula (IV) are mostly known organic chemistry compounds. However, 2, 1,2-trifluoroisopropyl cyanate and 2,2,2-trifluoro-1,1-dimethylethyl cyanate have not been known. However, these compounds can be prepared according to known methods. Thus, iso (thio) cyanates are obtained, for example, by reacting the corresponding amines with phosgene, optionally in the presence of a base such as triethylamine (cf., for example, DE-OS 28 04 082, DE-OS 25 12 514, U.S. Pat. No. 028, U.S. Pat. No. 27,0673, U.S. Pat. No. 3,311,654, JP 50/29599, Synthesis 1985, page 682 or J. Am Chem. Soc., 77, 1901-1902 (1955).

The triazolinones required as starting materials in carrying out the process of variant c) are generally defined by formula (V). In this formula (V), the substituents R ¹ , X and Y preferably have the meanings already mentioned as preferred in connection with the description of the compounds of the general formula (I), while

R ⁵ is preferably a straight-chain or branched alkyl having 1 to 4 carbon atoms or optionally mono- to trisubstituted by identical or different substituted phenyl or benzyl, wherein the substituents are, for a halogen atom, cyano, nitro, in each case straight-chain or branched alkyl a (C1 -C4) alkoxy or alkylthio group, in each case a straight or branched haloalkyl, (C1 -C4) haloalkoxy or haloalkylthio radical having from 1 to 9 the same or different halogen atoms,

R ⁵ is especially methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl or optionally once or twice, as well or differently substituted phenyl or benzyl wherein, in each case, fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl are suitable substituents , methoxy, ethoxy, n-propoxy, isopropoxy, methylthio, trifluoromethyl, trifluoromethoxy or trifluoromethylthio

The triazolinones of formula (V) are partially known compounds (cf., for example, J. Heterocycl. Chem. 17, 1691-1666 (1980)).

The triazolinones of formula (Va) are still unknown

in which

SK 279720-6

R ¹ 'represents an alkyl group, preferably a straight or branched alkyl group having 1 to 4 carbon atoms, in particular 1 to 3 carbon atoms, very particularly preferably a methyl group,

R ⁵ , X and Y are as defined above.

These compounds are obtained in an analogous manner to the preparation of the known compounds of formula (V) by reacting the 1H-triazolinones of formula (IHa).

in which

R ¹ 'and X ¹ are as defined above, with esters of (thio) chlóimravčej of formula (IX) R 5 -O-C-Cl (IX),

Y in which

R ⁵ and Y have the meanings indicated, optionally in the presence of a diluent such as tetrahydrofuran and optionally in the presence of an auxiliary reagent such as potassium tert-butoxide or sodium hydride at temperatures between -20 ° C and +40 ° C (see also examples embodiment).

The ΙΗ-triazolinones of the formula (IIIa) are known or obtained analogously to known methods (cf., for example, J. Heterocycl. Chem. 16, 403 (1979), J. Heterocycl. Chem. 17, 1691 (1980), Europe. J. Chem., 18, 215 (1983), Chem Ber, 98, 3025 (1965), Liebigs Ann. Chem., 637, 135 (1960).

Suitable acids for carrying out the process according to the invention (variant a) are all the inorganic and organic acids which are usable in general for the cleavage of hydrazone. Inorganic mineral acids such as hydrochloric acid, sulfuric acid or phosphoric acid are preferably used.

Suitable diluents for carrying out the process according to the invention (variant a) are all customary organic or inorganic solvents. Preference is given to using water-miscible organic solvents, in particular alcohols such as methanol, ethanol, propanol or butanol, mixtures thereof with water or pure water.

The reaction temperatures can be varied within a wide range when carrying out the process according to the invention (variant a). In general, the reaction is carried out at temperatures between 20 ° C and 150 ° C, preferably at temperatures between 50 ° C and 120 ° C.

Process variant a) is usually carried out at atmospheric pressure or under reduced pressure. When operating under reduced pressure, pressures in the range of between 2,000 and 40,000 Pa, preferably between 1,000 and 20,000 Pa are suitable.

In carrying out the process according to variant a), 1 to 50 mol, preferably 1 to 20 mol, of acid is generally used per 1 mol of hydrazone of the formula (Π). The hydrazone of the formula (TI) is dissolved in a suitable amount of diluent, the acid is then added to the solution obtained and the mixture is concentrated under reduced pressure for several hours.

In a particular embodiment, it is also possible to carry out the process according to variant a) to produce the intermediates necessary for this purpose of formula (II) in a single reaction step, i. j. in a single reaction vessel.

It is possible to select triazolinones of the formula (X) as starting materials and to react them successively in a single reaction vessel with amines of the formula (VI) and then with the acid according to the invention (variant a) (cf. triazoline hydrazones of formula (VHI) and these are reacted sequentially in a single reaction vessel with (thio) chloroformic acid esters of formula (IX), then with amines of formula (VI) and finally with the acid according to process a).

As diluents for carrying out the process according to the variant

(b) all inert organic solvents are suitable. These include, in particular, aliphatic, alicyclic or aromatic or halogenated hydrocarbons such as, for example, benzene, benzene, toluene, xylene, chlorobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, chloroform, carbon tetrachloride, ethers such as diethyl ether, dioxane, tetrahydrofuran or ethylene glycol. ethylene glycol diethyl ether, nitriles such as acetonitrile or propionitrile, smears such as dimethylformamide, dimethylacetamide, N-methylformanilide, N-methylpyrrolidine or hexamethylphosphoric triamide, or esters such as ethyl acetate.

Optionally, the process of variant b) is carried out in the presence of a suitable auxiliary reagent. All conventional inorganic or organic bases are themselves suitable. These include, for example, tertiary amines, such as triethylamine, Ν, Ν-dimethylaniline, N, N-diethylbenzylamine, Ν, Ν-dimethylcyclohexylamine or dibutyleindilaurate, pyridine, N, N-dimethylaminopyridine, diazabicyclooctane, diazabicyclonicene or diazabicyclonicene.

The reaction temperatures may be varied within a wide range in carrying out the process of variant b). In general, the reaction is carried out at temperatures between 0 ° C and 150 ° C, preferably at temperatures between 20 ° C and 100 ° C.

In order to carry out the process according to the invention, generally 1.0 to 2.0 mol, preferably 1.0 to 1.5 mol, of iso (thio) cyanate of formula (IV) and optionally 0.001 to 1.0 mol are used per mole of 1H-triazolinone of the formula (III). 2.0 mol, preferably 0.001 to 1.0 mol, of the auxiliary reagent.

Carrying out the reaction, working up the reaction mixture and isolating the reaction products are carried out according to the usual methods.

As diluents for carrying out the process according to the variant

(c) inert organic solvents are suitable. These include, in particular, aliphatic, alicyclic or aromatic or halogenated hydrocarbons, such as, for example, benzene, benzene, toluene, xylene, chlorobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, chloroform, carbon tetrachloride, ethers such as diethyl ether, dioxane, tetrahydrofuran or ethylene glycol ether. , nitriles such as acetonitrile or propionitrile, amides such as dimethylformamide, dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoric triamide, or esters such as ethyl acetate or sulfoxides such as dimethyl sulfoxide.

The process of variant c) may be carried out in the presence of a suitable auxiliary reagent. Suitable such reagents are all conventional inorganic or organic bases. These include, for example, alkali metal hydroxides such as sodium hydroxide or potassium hydroxide, alkali metal carbonates such as sodium carbonate, potassium carbonate or sodium bicarbonate, as well as tertiary amines such as triethylamine, N, N-dimethylaniline, pyridine, Ν, dim-dimethylaminopyridine , diazabicyclooctane, diazabicyclononene or diazabicycloundecene.

The reaction temperatures may be varied within a wide range in carrying out the process of variant c). In general, the reaction is carried out at temperatures between 0 ° C and 120 ° C, preferably at temperatures between 20 ° C and 50 ° C.

In order to carry out the process according to variant c), 1.0 to 5.0 mol, preferably 1.0 to 2.5 mol of the amine of the formula (VI) and optionally 1.0 to 2, are used per mole of triazolinone of formula (V), 0 mole, preferably 1.0 to 1.2 mole of auxiliary reagent.

The reaction, processing of the reaction mixture and isolation of the reaction products are carried out according to generally conventional methods.

In a particular embodiment of process (c), the production of the intermediates of formula (V) required for this process can be carried out in a single reaction step, i. j. in a single reaction vessel.

Starting from 1H-triazolinones of formula (III), these compounds are reacted sequentially in a single reaction vessel first with (thio) chloroformic acid esters of formula (IX) and then with amines of formula (VI) according to variant c).

Another method for obtaining compounds of formula (I) is to react the oxadiazolinones of formula (XI).

R ¹ yr

A < ^rz > ϊ ⁰ / A?

in which

R ¹ , R ² and Y are as defined above, with hydrazine hydrate in the presence of a suitable diluent such as methanol and ethanol at temperatures between 20 ° C and 100 ° C and the carbazidic acid derivatives of formula (XII) thus obtained

OO, ¹¹¹¹

R1-C-NH-C-NH-C-NH 2

I, (W,

Y-C-NH-R 2 in which

R ¹ , R ² and Y are as defined above, in the presence of a suitable diluent such as toluene, chlorobenzene or dichlorobenzene at temperatures between 80 ° C and 200 ° C, cyclized by heat treatment.

Oxadiazolinones of the formula (XI) are known compounds (cf., for example, FR 14 15 605 and CA 64, P51O5g as well as NL 6 510 645 and CA 65, P2274d-f, respectively) or are obtained according to generally known procedures, e.g. -oxadiazolinones with iso (thio) cyanates of formula (IV) analogously to the synthesis used to produce starting materials of formula (II).

The purification of the reaction products of formula (I) is carried out by conventional means, for example by column chromatography or recrystallization. Compounds are characterized by melting point and, for non-crystallising compounds, by proton magnetic resonance spectra.

The active compounds according to the invention can be used as defoliating agents, desiccants, weed control agents and in particular as weed control agents. Weed, in the broadest sense, means all plants that grow in places where they are undesirable. Whether the active compounds according to the invention act as total or selective herbicides depends essentially on the amount used.

For example, the active compounds according to the invention can be used in the following plants: dicotyledonous weeds of the genera: mustard (Sinapis), cress (Lepidium), grayling (Gallium), starfish (Stellaria), camomile (Matricaria), ruman (Anthemis), galinsoga (Galinsoga) , Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania , ragweed (Ambrosia), thistle (Cirsium), thistle (Carduus), milk (Sonchus), oily (Solanum), roripa (Rorippa), Rotala, Lindemia, deadnet (Lamium), veronica (Veronica), abutilon (Abutilon), Bmex, durman (Datura), violet (Viola), hemp (Galeopsis), poppy (Papaver), neva (Centaurea) and Mercurialis, dicotyledonous plants of the genera:

cotton (Gossypium), soybean (Glycine), beets (Beta), carrots (Daucus), beans (Phaseolus), peas (Pisum), potatoes (Solanum), flax (Linum), tunicate (Ipomoea), vetch (Wolf), tobacco (Nicotiana), tomatoes (Lycopersicon), groundnut (Arachis), tusk (Brassica), lettuce (Lactuca), cucumber (Cucumis), pumpkin (Cucurbita).

monocotyledonous weeds: hedgehog (Echinochlora), bar (Setaria), millet (Panicum), ring finger (Digitaria), timothy (Phleum), meadowgrass (Poa), fescue (Festuca), eleusine (Eleusine), Brachiaria, mätoooh (Lolium) , sewer (Bromus), oat (Avena), chess (Cyperus), sorghum (Sorghum), wheatgrass (Agropyron), hawk (Cynodon), Monochoria, Fimbristylis, rosehip (Segittaria), Eleocharis, Scirpus, Paspalum, Ischaemum, Sphenoclea Dactyloctenium, distemper (Agrostis), psiarka (Alopecurus), whisk (Apera).

monocotyledons of the genera:

rice (Oryza), maize (Zea), wheat (Triticum), barley (Hordeum), oats (Avena), rye (Secale), sorghum (Sorghum), millet (Panicum), sugar cane (Saccharum), pineapple (Pineapple) , asparagus (Asparagus), garlic (Allium).

However, the use of the active compounds according to the invention is by no means restricted to these genera but also to other plants in the same way.

The compounds according to the invention are suitable, depending on the concentration, for total weed control, for example on industrial areas and railways, as well as on roads and squares, possibly with tree growth. The compounds of the invention may also be used for weed control in long-term crops such as forest crops, ornamental tree crops, fruit trees, vineyards, citrus, nut, banana, coffee, tea, rubber, coconut, cocoa, cocoa, berry and hop plants and selective weed control in annual crops.

The active compounds according to the invention can be used with particular success for the control of monocotyledonous and dicotyledonous weeds, in particular in dicotyledonous crops such as sugar beet.

It is also worth mentioning the excellent effectiveness against Pheasant (Mercurialis), which is a problematic weed that is difficult to eradicate.

The active substances can be converted into conventional formulations such as solutions, emulsions, wettable powders, suspensions, powders, dusts, pastes, soluble powders, granules, concentrates based on suspensions and emulsions, natural and synthetic substances impregnated with active substances, as well as encapsulated formulations in polymeric substances.

These compositions are prepared in a known manner, for example by mixing the active ingredients with fillers, e.g. j. with liquid solvents and / or solid carriers, optionally using surfactants, i. j. emulsifiers and / or dispersants, and / or foaming agents.

If water is used as a carrier, for example, organic solvents can also be used as co-solvents. Basically suitable liquid solvents are: aromatic hydrocarbons, such as xylene, toluene or alkyl naphthalenes, chlorinated aromatic hydrocarbons or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chlorethylene or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffinic petroleum, e.g. oils, alcohols such as butanol or glycol, as well as 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 as well as water.

Suitable solid carriers are, for example, natural stone meal, such as kaolins, alumina, talc, chalk, quartz, atapulgite, montmorillonite or diatomaceous earth, and synthetic stone meal, such as highly disperse silica, alumina and silicates. Suitable solid carriers for the preparation of granulates are, for example, crushed and fractionated stone materials such as limestone, marble, pumice, sepiolite and dolomite, as well as synthetic granules of organic material such as sawdust, coconut shells, corn sticks and tobacco stems. Suitable emulsifiers and / or foaming agents are, for example, non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, fatty alcohol polyoxyethylene ethers, e.g.

The compositions of the invention may include adhesives such as carboxymethylcellulose, natural and synthetic, powdered, granular or latex polymers such as gum arabic, polyvinyl alcohol and polyvinyl acetate, as well as natural phospholipids such as ketalines and lecithins and synthetic phospholipids. Other additives may be mineral and vegetable oils.

In addition, these compositions may contain coloring agents such as inorganic pigments, for example iron oxide, titanium dioxide and ferrocyanide, and organic dyes such as alizarin dyes, azo dyes and metal niocyanine dyes, as well as trace elements such as iron, manganese, boron, copper, cobalt, molybdenum and zinc.

The compositions generally contain between 0.1 and 95% by weight of active ingredient, preferably between 0.5 and 90% by weight of active ingredient.

The active compounds according to the invention can also be used as such or in the form of their compositions also in admixture with known herbicides used for weed control, this addition being also possible to the finished compositions or immediately before application by addition to a storage tank.

Known herbicides, such as 1-amino-6-ethylthio-3- (2,2-dimethylpropyl) -1,3,5-triazine-2,4 (1H, 3H) dione or N- ( 2-benzothiazolyl) -N, N'-dimethylurea for weed control in cereal crops; 4-amino-3-methyl-6-phenyl-1,2,4-triazin-5 (4H) -one for weed control in sugar beet and 4-amino-6- (1,1-dimethyl-ethyl) -3 -methylthio-1,2,4-triazin-5 (4H) -one for soybean weed control. Mixtures with 5- (2-chloro-4-trifluoromethylphenoxy) -2-nitrobenzoic acid, N- (methoxymethyl) -2,6-diethylanilide chloroacetic acid, methyl-6,6-dimethyl-2,4- dioxo-3- [1- (2-propenyloxyamino) butylidene] -cyclohexanecarboxylic acid, methyl 5- (2,4-dichlorophenoxy) -2-nitrobenzate, 5-amino-4-chloro-2-phenyl-2, 3-dihydro-3-oxy-pyridazine, ethyl 2 - [[(4-chloro-6-methoxy-2-pyrimidinyl) -aminocarbonyl] aminosulfonil] benzoate, exo-1-methyl-4- (1-methyl) -ethyl) -2- (2-methylphenylmethoxy) -7-oxabicyclo [2.2.1] heptane, ethyl-2 - [[(4-chloro-6-methoxy-2-pyridinyl) aminocarbonyl] aminosulfonyl] benzoate, 3,6-dichloro-2-pyridine-carboxylic acid, N, S-diethyl-N-cyclohexylthiolcarbamate, 3- (methoxycarbonylamino-phenyl) -N-methylcarbamate, 2- [4- (2,4-dichlorophenoxy) phenoxy propionic acid, its methyl or ethyl esters, 4-amino-6-tert-butyl-3-ethylthio-1,2,4-triazin-5- (4H) -one, 2- / 4 - ((6-chloro- 2-benzoxazolyl) oxy] phenoxy / propanoic acid, its methyl ester or its ethyl ester rom, 2- (4- (3,5-dichloropyrid-2-yloxy) phenoxy) propionic acid trimethylsilylmethyl ester, 5- (2-chloro-4-trifluoromethylphenoxy) -N-methylsulfonyl-2-nitrobenzamide, 2- / 4 - ((3-chloro-5-trifluoromethyl) -2-pyridinyl) oxy]: enoxy / propanoic acid or ethyl ester thereof, 2- (4- (2,4-dichlorophenoxy) phenoxy) propionic acid methyl ester, 2- [5-methyl-5- (1-methyl-ethyl) -4-oxo-2-imidazolin-2-yl] -3-quinolinecarboxylic acid, 1-isobutylaminocarbonyl-2-imidazolidinone, 3-cyclohexyl -5,6-trimethylene-uiacil, N-methyl-2- (1,3-benzothiazol-2-yloxy) acetanilide, 2-chloro-N- (2,6-dimethylphenyl) -N - [(1 H) pyrazole- 1-ylmethyl-acetamide, 2-ethyl-6-methyl-N- (1-methyl-2-methoxyethyl) chloroacetanilide, 3- (ethoxycarbonylaminophenyl) -N- (3'-methylphenyl) carbamatoin, 2- [1- (ethoxyamino) butylidene] -5- (2-ethylthiopropyl) -1,3-cyclohexadione, N, N-diisopropyl-S- (2,3,3-trichloroallyl) thiolcarbamate or 2,6-dinitro-4-trifluoromethyl-N, N-dipropylaniline. Surprisingly, some mixtures also have a synergistic effect.

Mixing with other known active substances such as fungicides, insecticides, acaricides, nematicides, bird tartar, plant nutrients and soil improvers is also possible.

The active compounds can be used per se, in the form of concentrates or as dosage forms prepared from these concentrates by further dilution such as ready-to-use solutions, suspensions, emulsions, powders, pastes and granules. The application is carried out in the usual manner, for example by watering, spraying, spreading and the like.

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

The active substances can also be incorporated before the sowing of the plants.

The application rate of the active ingredient varies widely. This amount depends essentially on the type of effect desired. In general, the application rates are between 0.01 and 10 kg of active substance per hectare of soil area, preferably between 0.05 and 5 kg of active substance per hectare of soil area.

The following examples illustrate the preparation of the active compounds according to the invention and their use. However, these examples do not limit the invention in any way.

DETAILED DESCRIPTION OF THE INVENTION

EXAMPLES EXAMPLE 1 Production Method of Active Substances Example 1

Procedure a)

To 11.1 g (0.04 mol) of 1- (N-isobutylcarbamoyl) -4-iso-propylidene-imino-3-methyl-1,2,4-triazolin-5-one in 100 ml of ethanol is added 20 ml of of concentrated hydrochloric acid and the reaction solution are concentrated at 60 ° C and at a pressure of about 20,000 Pa for 5 hours on a rotary evaporator. The residue is triturated with a 1: 1 mixture of ethanol and diethyl ether to crystallize and air dried. 4.3 g (50% of theory) of 4-amino-1- (N-isobutylcarbamoyl) -3-methyltriazolin-5-one are obtained.

Example 2

Procedure b)

To 3.42 g (0.03 mol) of 4-amino-3-methyl-1,2,4- (1H) -triazolin-5-one in 80 ml of absolute acetonitrile is added 3.6 g (0.036 mol) of tert-butylamine. butylisocyanate and 0.05 g to 0.1 g diazabicycloundecene, stirred for 2 hours at 20 ° C, then concentrated under reduced pressure, the residue taken up in dichloromethane, washed with water, dried over sodium sulfate, concentrated under reduced pressure and the residue crystallizes on trituration with diethyl ether.

5.0 g (78.3% of theory) of 4-amino-1- (N-tert-butylcarbamoyl) -3-methyl-1,2,4-triazolin-5-one are obtained. .

Example 3

Procedure a) - variant in a single reaction step

To 8.2 g (0.03 mol) of 4-isopropylidenenimino-3-methyl-1-phenoxycarbonyl-1,2,4-triazolin-5-one in 50 ml of absolute tetrahydrofuran is added 4.2 g (0, 0 mol). (2,2-dichlorocyclopropylpropyl) methylamine, the mixture is then stirred for 12 hours at 20 ° C, concentrated under reduced pressure, the residue is taken up in 100 ml of ethanol, 3 ml of concentrated hydrochloric acid are added and the mixture is stirred for 3 to 3 hours. The reaction mixture is concentrated under reduced pressure, the residue is taken up in dichloromethane, the dichloromethane solution is washed three times with saturated aqueous sodium hydrogen carbonate solution, dried over sodium sulphate and concentrated under reduced pressure. The residue is triturated by trituration with diethyl ether.

4.4 g (52% of theory) of 4-amino-1- [N- (2,2-dichlorocyclopropylmethyl) carbamoyl] -3-methyl-1,2,4-triazolin-5-one are obtained. mp 149 ° C.

Example 4

C-NH ---- C- (CK ₂ ) ₂ -CH ₃

Procedure (c)

To 3.2 g (0.0137 mol) of 4-amino-3-methyl-1-phenoxycarbonyl-1,2,4-triazolin-5-one in a mixture consisting of 25 ml of tetrahydrofuran and 10 ml of dioxane is added 8.9 g (0.088 mol) of 1,1-dimethylbutylamine, the reaction mixture is heated under reflux for 24 hours, then concentrated under reduced pressure, the residue is taken up in dichloromethane, the dichloromethane solution is washed with 2% sodium hydroxide solution and water, dried over sulphate The solvent was removed under reduced pressure and the residue crystallized upon trituration with diethyl ether.

1.9 g (61% of theory) of 4-amino-1- [N- (1,1-dimethylbutyl) carbamoyl] -3-methyl-1,2,4-triazolin-5-one are obtained, m.p. C.

The following substituted triazolinones of general formula (I) are obtained in an analogous manner and according to the general process-related data:

Z ° \,

I ^X HH-R ^Z

R1 R2 (D,

Example number

r.2 X Y physical properties

X Y physical properties

ch ₃

^B - configuration

1.5 (a) ^Cll 3 ch ₃ • c-ch ₃ mp 100 ° C

ABOUT

ABOUT

1.5 (d) o

about

mp $ 13 ° C

(Roslclad)

mp 106 ° C

mp 135 ®C

^s -configuration

-ch <ch ₃ )

- (ch ₂ ) ₅ -ch ₂ ci

-ch (c ₂ h ₅ ) ₂

-CH-CHICHE.)

H -CCHg _{3 5} -Ca ₂ Cl to mp 131 ° C

24 ck ₃ -CH-CH-CKG 25 CH ₃ 0 -ch ₂ -c-oc ₂ h ₅

CK-Cl

I

CH. -C-CH

I

CH 2 Cl 2 O m.p. 92 ° C

O O m.p. 127 [deg.] C

OO n * ² 1.5055

CH,

I

CH, -C-CKCl ₂ i

O o t, t. 176 ° c

O O hi-NMB * '

4.4; 7.95

CIUT 1 29 cb ₃ -c-cb ₃ Cl 2 CH ₃ F 30 OjH · -C-4JH. 1 CH ₂ ?

O O m.p. 13 ° C

O O m.p. 10-40 ° C

SK 279720-6

Example R ¹ Number

X Y physical properties

P-IMM

Salo

R2 physical properties

«3 CH C-cjk; ^0B 3 0 0 m.p. 99 ’c ch ₃ -CK- _(CH3) j -CH (CB _{3) 2} ^C * 3 oo ¹ H KMK ^') 4.40; 7, SL

O O

0,35-0.6; 0.93

36 CH - (CH-CHjIj 37 ch ₃ CH ₃ 38 CH - (CH ₂ ) ₂ -CK ₃

0 m.p. 108-109 ° C

O m.p. 160-170 ° C

O O m.p. 134-136 ° C

O O m.p. 10 ° C (hydrochloride)

CK i

-CB

O O m.p. 135 ° C

O O m.p. 200-203 ° C

CSJ

O O m.p. 119 “C

OT tt 175-178 ^e C

CH ₃

CK ₃ CB ₃

-CB-CK I ^e 3

CSJ

O O m.p. 122 “C

O O m.p. 141 ° C

O C mp, 176 ° C

o O m.p. 113 “c

O O mp, 109 ° C

O O m.p. 14 ° C

62 ^Ca 3 -CH- (CS) .- CB. 1 ^CH 3 63 ca ₃ -CK-CH-OCH, 1 CH ₃

CH 3 - (ca ₂ > ₂ -0CE ₃

O O m.p. 67 O

O O m.p. 120 “c

O O m.p. 114 ° C

Cl,

O O m.p. 64 ° C (hydrochloride)

O S m.p. 147 ° C

Example number

R '

R ² XY physical properties

Example number _______ r2 x y physical properties

CX ₃ cb ₃ -C 6

O S m.p. 205 ° C

CH ₃

O O m.p. 134 ° C

OC tt 164 ° C ^ CH ₂ CL ch, -c ³ V ^ ch-ch ₂ o 0 tt 120 ° C

CH, and 01 - 50 «J -c - CH-CB-C 0 0 n ²⁰ 1.3840 1 1 ^ -Cl = ¾ %

O 0 m.p. 1-8 ° C

76 CH -CK-ca or Ci ₃ | 78 CH ₃ -C- <CS _a > ₃ -M ₃ ch ₃ 79 ch ₃ -CB-tCB.b-CX, 1 ™ 3

0 m.p. 147 ° C

1.4891 ”D

O 0 1.4920

BO

CH ₃ CH ₃

O O m.p. 140 [deg.] C

O O m.p. 115 ° C

Example NUMBER

X Y physical properties

Example R ¹ was

X Y physical properties

CH 2 -CH 2 -CH-C 1 H 6 CH ₃ O 0 106 ° C

O m.p. 104 ° C

O O 1.1. 120 ° C (decomposition)

100

o O 1.1. 108 ’c

101

102

103

104

O O t.l. 114 ° C

O O Drawbar 1.4572

105 'Ä

CK ₃ -C-C ₃ H ₃ C _and H,

O O 1.1. 128 [deg.] C

105

107

CH

-CK- (CK i> 2-CB

108

oBJ

CKj ^CK 3

OO mp, 73 DEG C. _ / ^c, and

CB ₃ -C ₍ CH ₃₎ -X

O O »3 ° 1.5815

CH 3 - (CH 3 H-K \ CH 3

O O m.p. 210 ° C (hydrochloride)

110

111

112 “CH-CEj-CK

113

IhydrDchloríd)

114

115

116

CH

CH

CH

CH

1.5150

D (hydrochloride)

mp 145 ° C

T. L. 108 ° 0

Drawbar ⁰ 1.5100 (hydrochloride)

1.4830

mp 81 ° C

1.1. Mp 123 ° C

I ^e A

CH

- (CH ₄ -CH

1.1. 93 ° C

109

A

X Y physical properties Example R ¹ R ^ľ X Y fyzMlne Dalu features and ΰ mp us »c 141 c ₂ K ₅ _A C 0 mp 104 ^c C 142 ° A CH (CB _{3) 2} Q 0 mp 89 ° C 0 0 tt 123 ^and C T * ³ (Tado-foras) I 143 ^C 2 «5 CH-CKjCl 0 0 1 ^ -1.4919 0 0 mp 131 ° c 144 CJH. CH-CjBj 0 0 »^ 1.4955 (Exo Forum ·) IN 0 0 mp 14 ° C 145 "3 -X 0 0 mp 146 ^e C <4 CH 0 0 mp 117 ° C 145 <In » C-CHjCl 0 0 mp Ío; C ch ₃ 147 ca ₃ - (CH-CSj.jj 0 0 mp Mp 110 ° C 0 0 149 ™ 3 - (C ₁₅ H ₁₅ -C 8 ₎ D 0 mp 9 ° C

149

1.45 (»)

7.04-7.43 (a)

150

151

152

153

154

155

156

157

CJK - £ (ch ₃ ) ₃ y ⁵ 0 0 m.p. 15 ° C ^C A C 1 -C 8 CB 1 -CB 0 0 m.p. Mp 119 ° C

15B

159 (CH 2 J-CH

C-CCHPj-PURPOSE

mp 195 ° C

Example of violet rl R! X Y physicah features 160 08. 0 0 m.p. 137 ° C 3 ./V ³ 0¾ ch ₃ 161 ca ₃ ^c8 3 X ~ 7 ci \ X ci 0 0 m.p. Mp 162 ° C 162 ®3 -e 0 Q tt 172 ^D C 163 ° A D 0 0 m.p. 11 ° c 154 (0¾) ₃ C- - (082) 5-0¾ 0 0 n | ° -1.4980 ¾ ³ 165 C ^ -tCHj> ₂ - -C-CH 2 CH 3 0 0 m.p. 106 ° c 0¾

Example R1 alo

173 C ₂ K ₅

179 C ₂ K ₅

166 (0¾) ^ 08-c-csca m.p. 90 ®C

167 CHj

O m.p. 90 °

130 CjKj iai (CHjjjC132 < ^CH3 ? J ^c -

183 _{(CH3> 3} C

184 C ₂ H ₃

169 CHyíCH ^ j170 (CK i ^ C171 CH-C ₂ R ÍCHjJj173

174 CEJ-CCH ^ ·

17 «0¾

from\ 0 Λ 0 FROM\ 0 ABOUT C 0 0 CH, | ^J -C-C ^ F 0 ^CH 3 -0-0¾ Cl 1 C CH, CH, 1 " -C-C ^ l 0 to Cl l> r Q "3

O m.p. 133 ° c

O m.p. 9 ° C

O m.p. 156 [deg.] C

O m.p. 100 ®C

0, ^n- 1, 516B

O m.p. 137 ° C

O ηζ ^υ · 1 ₍ 5β90

0 ° -1.565 °

O m.p. 105 ’C

186

187

X Y physically vlirtnoile

08.01 r ² C-8, 1 cBjCi 0 P -O-CH 2 Cl 1 CH 3 0

O nj ^and -1, 5149

O m.p. Mp 123 ° C

-0- (0¾¾ ^ ¾o

CH

-o O

0 ' "3 CH-CH _{(CH3) 2} 0

-c (ca ₃ ) ₃

(S-Tortoise) j

190 (CKjljC-

(R-Conflfluric ·)

0¾ 191 —C — CH 3 O 1 ^cr 3 192 (CH ₃ ) ₃ C- -CC = CC 1 ^CC 3

193

O nj »1, 4926 (H-XJGt):

O 1.44 (93)

4.43 (2 H) ^{1H-KMR e):}

O 1.44 (9H),

4.53 (28)

O m.p. 142 ° C

C, m.p. 93 ° C

O O m.p. 112 [deg.] C

O O m.p. 103 ° C

mp 151 ° o

O O m.p. 133 ’C

O O m.p. 148 [deg.] C

Hive, 1 ³ (OljJjO- -0- (0¾ ^. ^ ° 5) 0 0 η * ° · 1.4β44

Γ 194 -08-08 (0¾) _a

O D m.p. 135 ®C

mp Mp 172 ° C

1.1. 109 ° c

mp 177 ’C (CHj

mp 83 ° C i ⁰ , 4801

mp 124 ’C (CKjJ ^ CK — CH (CHj) g (CH (CH

CCH ₃ J 2 CH (CH ₃ ) ₂ CH-

CH, ^c '3

C

CH-CH (CH) j

In physical Example pure R1 R 2 X Y physical properties 0 m.p. ltl ° c 212 ^C A (WITH) / \ í \ / "3 0 0 ^ B * KNR) 1.29 (t, 3H) i, 53 (a, 3i ·) 0 m.p. 208 ° C 213 C, E _S ^ Jj -CHCHjCHÍ ^TA 3 0 0 (amorphous product) 0.15-1.5S10 21+ c ₂ s ₅ 0 0 (amorphous product) 215 «2 * 5 ^ ^ -CHtCHj CHCCH 0 0 (amorphous product)

np ° = l 'e60

mp 136 ° C

221

222

223

22+

22?

1.1. 1 ° C

1.1, no

- (J-CHjkCH

(amorphous product)

Note to table:

*) H-NMR spectra have been performed in deuterochloroform (CDCl _a) using tctrametylsilánu as internal standard. The chemical shift is given as the value of two ppm.

Production of starting materials

Example II-1

Example R1 r2 ref

physical vtastnosf

o nh-ch ₂ -ch (ch ₃ ; ₂

6 g (0.04 mol) of 4-isopropylidenenimino-3-methyl-1H-triazolin-5-one and 4 g (0.04 mol) of triethylamine in 20 ml of dioxane are added dropwise at 20 [deg.] C. while stirring. 0.12 mol) of isobutyl isocyanate and the mixture is stirred at 100 ° C for 3 hours after the addition is complete. To work up, the reaction mixture is concentrated under reduced pressure, the residue is taken up in 100 ml of dichloromethane, washed several times with 100 ml of water each time, dried over sodium sulfate and freed from the solvent under reduced pressure.

11.2 g (100% of theory) of 1- (N-isobutylcarbamoyl) -4-isopropylidenemin-3-methyl-1,2,4-triazolin-5-one are obtained as an oil.

@ 1 H-NMR (CDCl3): d = 0.85 (d, 6H) ppm.

The following intermediates of the general formula (Π) are obtained accordingly and according to the general data relating to the manufacturing process.

¾ ³

11-9 CH ₃ -C-C 1 Cl 2

CK i

C (CK _{3> 2 t. T.} O _O • _{B a} C (CH _{3) 2} 1.1. JJ9 C

-C _(CH3) j ₀₁ j • CÍCHj> ₂ t, t, 10J ° _C • CtCHjij t, i. gj = ctCH _{3 and} tt 121-122 ⁶ C

Table 2

Example Rt2

• CK-CH _{(CH3) 2}

3.9

II-4 C _Hj 1 ⁵ CH ₃ -C (CH ₃ ) ₂ 1.1. 86 ° C 1-5 Ch ₃ -CH (CH ₃ > ₂ C (ch ₃ ) ₂ 1.1. 107 ° c I-6 ch ₃ -CH (C ₂ H ₅ ) ₂ C (CH ₃ ) ₂ t, t. 5 ° C II-7 ^CE J -CH-CH (CH3) ₂ -C _{(CH3) 2} 0.54 (s, CH) ir-e ^ca 3 - ^C 2 2 Ύ K) ¹ -C (CH ₃ ) ₂ T. L. 115 ° C

)

Example III-1

H

11.4 g (0.1 mol) of 4-amino-3-methyl-1,2,4- (1H) -triazolin-5-one (cf. J. Med. Chem., Chim. Ther. 18, 215-220 (1983) and 0.1 g of toluenesulfonic acid in 100 ml (79.06 g, 1.36 mol) of acetone were stirred at 70 ° C for 40 hours and then concentrated in vacuo to give 15.4 g. (100% of theory) 4-isopropyridinimino-3-methyl-1,2,4- (1H) -triazolin-5-one, m.p. 140-144 ° C.

Example V-1

To 2.3 g (0.02 mol) of 4-amino-3-methyl-1,2,4- (1H) triazolin-5-one in 25 ml of absolute tetrahydrofuran is added 2.7 g (0.024 mol) of tert- of potassium butoxide, the reaction mixture is stirred at 20 ° C for 1 hour, then 3.1 g (0.02 mol) of chloroformic acid phenyl ester is added dropwise with stirring, the reaction mixture is stirred at room temperature for 12 hours, then glacial. the acetic acid is adjusted to pH 5, concentrated under reduced pressure, the residue taken up in chloroform, washed with water, dried over sodium sulphate, concentrated under reduced pressure and the residue crystallized by trituration with ether.

1.1 g (23.5% of theory) of 4-amino-3-methyl-1-thenoxycarbonyl-1,2,4-triazolin-5-one of melting point 175 DEG C. is obtained.

Example VIII-1

11.4 g (0.1 mol) of 4-amino-3-methyl-1,2,4- (1H) -triazolin-5-one (cf. J. Med. Chem. Chim. Ther. 18, 215) 220 (1983)) and 0.1 g of p-toluenesulfonic acid in 100 ml (79.06 g, 1.36 mol) of acetone are stirred for 40 hours at 70 ° C and then the reaction mixture is concentrated under reduced pressure. 15.4 g (100% of theory) of 4-isopropylideneimino-3-methyl-1,2,4- (1H) -triazolin-5-one, m.p. 140 DEG-144 DEG C., are obtained.

To 15.4 g (0.1 mol) of 4-isopropylidenenimino-3-methyl-1,2,4- (1H) -triazolin-5-one in 100 ml of absolute tetrahydrofuran is added first at room temperature 13.4 g ( Potassium tert-butoxide (0.12 mol), the reaction mixture is stirred at room temperature for one hour, then added

15.5 g (0.1 mol) of chloroformic acid phenyl ester are added and the mixture is stirred for a further 12 hours at 20 ° C.

To work up, the reaction mixture was acidified with glacial acetic acid, concentrated under reduced pressure, the residue taken up in chloroform, washed with water, dried over sodium sulfate, concentrated again under reduced pressure and recrystallized from acetone.

10 g (36% of theory) of 4-isopropylideneimino-3-methyl-1-phenoxycarbonyl-1,2,4-triazolin-5-one of melting point 162 DEG C. are obtained.

Example X-2

7.7 g (0.05 mol) of 4-isopropylidenenimino-3-methyl-1,2,4- (1H) -triazolin-5-one in 50 ml of absolute tetrahydrofuran are added at 20 ° C to 1.5 g ( Of sodium hydride (0.05 mol), the reaction mixture is stirred for 1 hour at room temperature, then 5.4 g (0.05 mol) of ethyl chloroformate are added dropwise with stirring, and after the addition the reaction mixture is stirred for a further 12 hours at room temperature. temperature 20 ° C.

To work up, the reaction mixture is acidified with glacial acetic acid, then concentrated under reduced pressure, the residue is taken up in dichloromethane, the dichloromethane solution is washed with water, dried over sodium sulfate, concentrated again under reduced pressure and recrystallized from isopropanol.

5.0 g (44% of theory) of 1-ethoxycarbonyl-4-iso-propylideneimino-3-methyl-1,2,4-triazolin-5-one of melting point 91 DEG C. is obtained.

Examples illustrating biological activity

In the following examples, the following compounds are used as reference (standards):

about

U)

Compound A:

4-amino-3-methyl-6-phenyl-1,2,4-triazin-5-ol (a compound known from DE-OS 23 64 474, Example 1-22),

o mt - ch (oh ₃ ) ₂ (B)

Compound B:

N-isobutyl-2-oximidazolidine-1-carboxamide (compound known from R. Wegler Chemie der Pflanzenschutz- und Schädlingsbekämpfiingsmittel, Vol. 5, p. 219 (1977)).

Example A

Preemergence test Solvent: 5 parts by weight of acetone Emulsifier: 1 part by weight of alkyl aryl polyglycol ether

To prepare a suitable active ingredient, 1 part by weight of active ingredient is mixed with the indicated amount of solvent, the said amount of emulsifier is added, and the concentrate is diluted with water to the desired concentration.

The seeds of the test plants are sown in normal soil and, after 24 hours, watered with the active compound preparation. The amount of water per unit area is expediently kept constant. The concentration of the active ingredient in the formulation is of no importance, only the amount of active ingredient used per unit area is critical. After three weeks, the degree of damage to the plants is evaluated in% of damage compared to the development of untreated control plants. It means:

% no effect (as in the untreated control plants)

100% complete destruction (death) of plants.

In this test, for example, the compounds of Examples 2, 14, 23, 32, 41, 45, 48, and 57 have a significantly better herbicidal activity against weeds and a significantly better selectivity in crop plants, for example in sugar beet than Comparative B. for example, the compounds of Examples 7 and 175 significantly improved herbicidal activity and good barley selectivity.

The results of these tests are summarized in Tables A and A-1 below.

Tafeulkt A tmmwMntii HM (flux w · «Urtku) <£ vd using Atapran Amanntiui DMn Stellarta uweutait nrwiMw beet <94f (B) 200030 (« (· ί>

(2) 20000 (14! 20090 (23) 20000 (32) 20000 (41) 20000 (49) 2000 ($) 2000C ($ 7) 2000C

TO o «o

9β 100100

Í0 100100

100100

100100

100100

1OO9J

BO 100100 ep60 loo 100100

100 K100

100 100100

100 100100

100100

100 100100

100loo

100 looloo (0) 2OW>

(tHUI <2) tOCO (14) 2M0 (23) 20Co (32) 20C (4D2000 (49) 2000 (46) 2000

())> 2000 (78) 2000

0100 ese

0100

10100

0100

10loo

090

10100

10loo

100

Loo

100

100 (fines in Mtenik)

(71) 500 (19) 1000 (34) 10000 (3) 1000O (U) 1000O (138) JOO0 (175) JOO10 loo

100 i 00

LOO

100

iCO

LOO

106 iOO

Example B

Postemergence test Solvent: 5 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether To prepare a suitable active preparation, 1 part of the active ingredient is mixed with the indicated amount of solvent, the said amount of emulsifier is added and the concentrate diluted with water to the desired concentration.

Experimental plants having a height of 5 to 15 cm are sprayed with the active preparation in such a way that the required amount of active substance is always applied per unit area. The concentration of the spray suspension is chosen such that the required amount of active ingredient is always applied in 2000 liters of water per ha. After three weeks, the degree of damage to the plants is evaluated in% of damage compared to the development of untreated control plants.

It means:

% = no effect (same as for untreated control plants)

100% = complete destruction (death) of plants.

In this test, for example, the compounds of Examples 1 and 48, the Examples 2, 14, 23, 32, 41, 45, 48, 57, 78 and the Examples 7, 15, 34, 3, 63, 138 and 175 in controlling monocotyledonous and dicotyledonous weeds a significantly better herbicidal effect than comparative substance A or B.

The results of these tests are summarized in Tables B-1, B-2 and B-3 below:

TMuk e-l.poMnwrfMinýiMi (pcKu ^ v> * J «r * u)

Claims (12)

PATENT CLAIMS 1. Substituted triazolinones of general formula (I) T (I) in which R ¹ is hydrogen, straight or branched alkyl of 1 to 8 carbon atoms, cycloalkyl having 3 to 7 carbon atoms in the cycloalkyl, optionally at least one, same or different halogen substituted aryl of 6 to 10 carbon atoms or haloalkyl a group having 1 to 4 carbon atoms and up to 9 of the same or different halogen atoms, R ² is straight or branched alkyl group having 1 to 18 carbon atoms, alkenyl of 2-8 carbon atoms, alkynyl of 2-8 carbon atoms, haloalkyl of 1 to 8 carbon atoms and 1 to 17 identical or different halogen atoms , (C 2 -C 8) haloalkenyl of up to 15 identical or different halogen atoms, (C 1 -C 8) cyanoalkyl, (C 1 -C 6) alkoxyalkyl, (C 1 -C 6) alkoxycarbonylalkyl carbon in the alkoxy and alkyl moieties, alkoxycarbonylalkenyl of 1 to 6 carbon atoms in the alkoxy moiety with 2 to 6 carbon atoms in the alkenyl moiety, alkylaminoalkyl of 1 to 6 atoms23 C1-C6-dialkylaminoalkyl or C1-C6-cycloalkyl or C1-C6-cycloalkylalkyl optionally in each case at least once or at least once or differently substituted cycloalkyl or cycloalkylalkyl; in a straight or branched chain alkyl moiety, the substituents being halogen, straight or branched alkyl of 1 to 4 carbon atoms, haloalkyl of 1 to 4 carbon atoms, haloalkyl of 1 to 4 carbon atoms and 1 to 4 carbon atoms 9 identical or different halogen atoms or haloalkenyl having up to 4 carbon atoms in a straight or branched chain and 1 to 5 identical or different halogen atoms, furthermore R ² represents an optionally at least one, same or different, substituted aralkyl, or an aryl group having 6 to 10 atoms in the aryl moiety and optionally with 1 to 8 carbon atoms in the straight or branched alkyl moiety, wherein, optionally, halogen atoms are suitable as alkyl substituents, and halogen, straight or branched alkyl groups containing 1-6 carbon atoms are suitable substituents for the aryl group. up to 6 carbon atoms or alkoxy of 1 to 6 carbon atoms, X is oxygen or sulfur; and Y represents an oxygen atom or a sulfur atom. Substituted triazolinones of general formula (I) according to claim 1, in which R ^{@ 1} represents a hydrogen atom, a straight or branched alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 7 carbon atoms or optionally at least once, the same or a different halogen atom substituted with an alkyl group having 6 to 10 carbon atoms, R ² is straight or branched alkyl group having 1 to 18 carbon atoms, alkenyl of 2-8 carbon atoms, alkynyl of 2-8 carbon atoms, haloalkyl of 1 to 8 carbon atoms and 1 to 17 identical or different halogen atoms , C 2 -C 8 haloalkenyl, C 1 -C 15 identical or different, C 1 -C 8 cyanoalkyl, C 1 -C 6 alkoxyalkyl or C 1 -C 6 alkoxycarbonylalkyl carbon atoms in the alkoxy and alkyl moieties, dialkylaminoalkyl of 1 to 6 carbon atoms in the alkyl moieties or in each case optionally at least once the same or differently substituted cycloalkyl or cycloalkylalkyl radical of 3 to 8 carbon atoms in the cycloalkyl moiety and 1 to 6 carbon atoms in a straight or branched chain alkyl moiety, e.g. wherein the substituents are halogen, straight or branched (C 1 -C 4) alkyl, (C 1 -C 4) haloalkyl and (C 1 -C 9) identical or different, or straight-chain or haloalkenyl (C 4 -C 4); branched chain and 1 to 5 identical or different halogen atoms, furthermore R ² is optionally, at least one, same or different, substituted aralkyl or aryl group having 6 to 10 carbon atoms in the aryl moiety and optionally with 1 to 8 carbon atoms in a straight or branched an alkyl moiety wherein, optionally, halogen atoms are suitable substituents for the alkyl group, and a halogen atom, a straight or branched alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms are suitable substituents for the aryl group, X is oxygen or sulfur; and Y represents an oxygen atom or a sulfur atom. Substituted triazolinones of general formula (I) according to claim 1, in which R ¹ is C 1 -C 4 alkyl or C 1 -C 4 haloalkyl of up to 9 same or different halogen atoms, R ² is C 1 -C 10 alkyl, C 1 -C 6 haloalkyl and s C 1 -C 13 halo, C 3 -C 3 cycloalkyl C 12 optionally substituted by C 1 -C 4 alkyl or C 1 -C 4 haloalkyl; C 2 -C 8 alkynyl, C 3 -C 8 cycloalkylalkyl having 1 to 4 carbon atoms in the alkyl moiety, the cycloalkylalkyl group being optionally substituted in the cyclic moiety with a C 1 -C 4 alkyl group; or a halogen atom, or a (C 1 -C 4) alkoxyalkyl group in the alkoxy and alkyl moieties, X represents an oxygen atom and Y represents an oxygen atom. Substituted triazolinones of general formula (I) according to claim 1, in which R ¹ represents an alkyl group having 1 to 4 carbon atoms, R ² is alkyl having 1 to 10 carbon atoms, haloalkyl group having 1 to 6 carbon atoms and 1 to C 1 -C 4 -alkyl, C 3 -C 8 -cycloalkyl optionally substituted by C 1 -C 4 alkyl or C 1 -C 4 haloalkyl; C 2 -C 8 alkynyl, C 3 -C 8 cycloalkylalkyl having 1 to 4 carbon atoms in the alkyl moiety optionally substituted in the cyclic moiety with C 1 -C 4 alkyl; a halogen atom; or is (C 1 -C 4) alkoxyalkyl, and X is O and Y represents an oxygen atom. A process for the manufacture of substituted triazolinones of formula (I) according to claim 1 wherein R ¹ is hydrogen, straight or branched alkyl of 1 to 8 carbon atoms, cycloalkyl having 3 to 7 carbon atoms in the cycloalkyl, optionally, at least one, same or different halogen substituted aryl of 6 to 10 carbon atoms or haloalkyl a group having 1 to 4 carbon atoms and up to 9 of the same or different halogen atoms, R ² is straight or branched alkyl group having 1 to 18 carbon atoms, alkenyl of 2-8 carbon atoms, alkynyl of 2-8 carbon atoms, haloalkyl of 1 to 8 carbon atoms and 1 to 17 identical or different halogen atoms . C 2 -C 8 haloalkenyl of up to 15 identical or different halogen atoms, C 1 -C 8 cyanoalkyl, C 1 -C 6 alkoxyalkyl, C 1 -C 6 alkoxyalkyl and C 1 -C 6 alkoxyalkyl carbon atoms in the alkoxy and alkyl moieties, alkoxycarbonylalkenyl of 1 to 6 carbon atoms in the alkoxy moiety with 2 to 6 carbon atoms in the alkenyl moiety, alkylaminoalkyl of 1 to 6 carbon atoms in the alkyl moieties, a dialkylaminoalkyl group of 1 to 6 carbon atoms in the alkyl moieties or in each case at least once the same or a differently substituted cycloalkyl or cycloalkylalkyl radical having from 3 to 12 carbon atoms in the cycloalkyl moiety and from 1 to 6 carbon atoms in the straight or branched chain alkyl moiety, the substituents being halogen , direct or branched (C 1 -C 4) alkyl, (C 1 -C 4) haloalkyl, (C 1 -C 4) haloalkyl (C 1 -C 9) halogen or straight or branched (C 4 -C 4) haloalkenyl; 1 to 5 same or different halogen atoms, furthermore R ² represents an optionally, at least one, same or different substituted aralkyl group or an aryl group having 6 to 10 carbon atoms in the aryl moiety and optionally with 1 to 8 carbon atoms in a straight or branched alkyl wherein, as the substituents of the alkyl group, halogen atoms are suitable and as the substituents of the aryl group, a halogen atom, a straight or branched alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms are suitable, X is an oxygen or sulfur atom and Y is an oxygen or sulfur atom, characterized in that (a) the hydrazones of formula (II) are reacted c) reacting the triazolinones of general formula (V) in which: R ¹ , X and Y are as defined in claim 1 a R ⁵ represents an alkyl group, an aryl group or an arylalkyl group, with amines of general formula (XT) R ² -NH ₂ (VI) wherein R ² is as defined in Claim 1, optionally in the presence of a diluent and optionally in the presence of a reaction auxiliary. A process according to claim 5 for the production of a compound of the formula characterized in that the compound of the formula I '' Nh - s * in which: R ¹ , R ² , X and Y are as defined in claim 1 a R ³ and R ⁴ are each independently hydrogen, alkyl, aralkyl or aryl, with an acid, optionally in the presence of a diluent, or b) reacting the 1H-triazolinones of the formula III with an acid, optionally in the presence of a diluent, or reacting the compound of the formula with a compound of the formula R ¹ and X are as defined in Claim 1, with a iso (thio) cyanates of formula (IV) R ² -N = C = Y (IV) wherein R ² and Y are as defined in Claim 1, optionally in the presence of a diluent and optionally in the presence of a reaction auxiliary, or (CH ₂₎ optionally in the presence of a diluent and optionally in the presence of a reaction auxiliary. An intermediate for the preparation of compounds of formula (I) according to any one of claims 1 to 4 which are hydrazones of formula (II) in which: R ¹ is hydrogen, straight or branched alkyl of 1 to 8 carbon atoms, cycloalkyl having 3 to 7 carbon atoms in the cycloalkyl, optionally, at least one, same or different halogen substituted aryl of 6 to 10 carbon atoms or haloalkyl a group having 1 to 4 carbon atoms and up to 9 of the same or different halogen atoms, R ² is straight or branched alkyl group having 1 to 18 carbon atoms, alkenyl of 2-8 carbon atoms, alkynyl of 2-8 carbon atoms, haloalkyl of 1 to 8 carbon atoms and 1 to 17 identical or different halogen atoms , C 2 -C 8 haloalkenyl of up to 15 identical or different halogen atoms, C 1 -C 8 cyanoalkyl, C 1 -C 6 alkoxyalkyl, C 1 -C 6 alkoxycarbonylalkyl in both alkoxy and alkyl moieties, C 1 -C 6 alkoxycarbonylalkenyl having 2 to 6 carbon atoms in the alkenyl moiety, C 1 -C 6 alkylaminoalkyl, C 1 -C 6 dialkylaminoalkyl in the alkyl moieties or in each case at least once the same or different substit a cycloalkyl or cycloalkylalkyl group having from 3 to 12 carbon atoms in the cycloalkyl moiety and from 1 to 6 carbon atoms in the straight-chain or branched alkyl moiety, the substituents being halogen, straight or branched alkyl of 1 to 4 atoms; C 1 -C 4 haloalkyl, C 1 -C 4 haloalkyl and C 1 -C 9 identical or different halogen atoms, or straight-chained or branched haloalkenyl C 1 -C 4, with 1 to 5 identical or different halogen atoms R ² is optionally at least one, same or differently substituted aralkyl or aryl group having 6 to 10 carbon atoms in the aryl moiety and optionally having 1 to 8 carbon atoms in the straight or branched alkyl moiety, optionally substituted as alkyl groups atoms halogen and aryl substituents are halogen, straight or branched (C1-C6) alkyl or (C1-C6) alkoxy, R ³ and R ⁴ are independently hydrogen, alkyl of 1 to 4 carbon atoms, phenyl or benzyl, X is oxygen or sulfur; and Y represents an oxygen atom or a sulfur atom. An intermediate for the preparation of compounds of formula (I) according to any one of claims 1 to 4, which are triazolinones of formula (Va) in which: R ¹¹ represents a C 1 -C 4 alkyl group, R ⁵ represents a C 1 -C 4 alkyl group or a phenyl group or a benzyl group optionally substituted one to three times, the substituents being in each case a halogen atom, a cyano group, a nitro group, an alkyl group, an alkoxy group or an alkylthio group having from 1 to 4 atoms each carbon, haloalkyl, haloDalkoxy or haloalkylthio having in each case 1 to 4 carbon atoms, and X and Y are each independently O or S. An intermediate for the preparation of compounds of formula (I) according to any one of claims 1 to 4, which are triazolinones of formula (Xa) ¹ R ^'1 is alkyl having 1 to 4 carbon atoms, R ³ and R ⁴ are each independently hydrogen, C 1 -C 4 alkyl, phenyl or benzyl, R @ ⁵ represents a C1 -C4 alkyl group, optionally substituted one to three times a phenyl or benzyl group, with halogen, cyano, nitro, alkyl, alkoxy or alkylthio having 1 to 4 carbon atoms in each case as substituents, haloalkyl, haloalkoxy or haloalkylthio having in each case 1 to 4 carbon atoms, and X and Y are each independently O or S. A herbicidal composition, characterized in that it contains at least one substituted triazolinone of the formula (I) according to claim 3 or 4 as the active ingredient. The herbicidal composition according to claim 10, characterized in that it comprises carriers and / or surfactants. Use of substituted triazolinones of general formula (I) according to claims 3 or 4 for weed control.