SK400788A3 - Substituted triazolinones, method and intermediate products for manufacturing thereof, their use and herbicidal agent containing same - Google Patents

Abstract

Novel substituted triazolinones of the formula (I) <IMAGE> in which R<1> represents hydrogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, alkoxyalkyl, cycloalkyl, cycloalkylalkyl, tetrahydrofuranyl, tetrahydrofuranylalkyl, or in each case optionally substituted aralkyl or aryl, R<2> represents hydrogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, cyanoalkyl, hydroxyalkyl, alkoxyalkyl, alkoxycarbonylalkyl, alkoxycarbonylalkenyl, alkylaminoalkyl, dialkylaminoalkyl or in each case optionally substituted cycloalkyl, cycloalkylalkyl, cycloalkenyl or cycloalkenylalkyl, or in each case optionally substituted heterocyclylalkyl, or in each case optionally substituted aralkyl, aroyl, aryl, aralkyloxy or aryloxy, or represents alkoxy, alkenyloxy or alkynyloxy, X represents oxygen or sulphur and Y represents oxygen or sulphur, a process for the preparation of these compounds, and their use as herbicides.

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 ( cf., for example, 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), 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 the formula I have now been found

RNH.

N (I) in which

R1 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 substituted aryl group having 6 to 10 carbon atoms or a haloalkyl group (C 1 -C 4) and up to 9 identical or different halogen atoms; R ² represents a straight or branched (C 1 -C 18) alkyl, (C 2 -C 8) alkenyl, (C 2 -C 8) alkynyl, haloalkyl of 1 to 8 carbon atoms and 1 to 17 identical or different halogen atoms, haloalkenyl of 2 to 8 carbon atoms and 1 to 15 identical or different halogen atoms, C1-C8alkylalkyl, alkoxyalkyl of 1 to 8 carbon atoms 6 carbon atoms in the alkoxy and alkyl moieties, alkoxycarbonylalkyl moiety in each case having 1 to 6 carbon atoms in the alkoxy and alkyl moieties, alkoxycarbonyialkenyl having 1 to 6 carbon atoms in the alkoxy moiety and 2 to 6 carbon atoms in the alkenyl moiety, an alkylaminoalkyl group having 1 to 6 carbon atoms in the alkyl moieties, a dialkylaminoalkyl group having 1 up to 6 carbon atoms in the alkyl moieties or in each case at least one or the same or 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; halogen, straight or branched (C 1 -C 4) alkyl, (C 1 -C 4) haloalkyl, (C 1 -C 4) haloalkyl (C 1 -C 9) or different halogen or haloalkenyl (C 4 -C 4) in direct or ro branched chain and with 1 to 5 same or different halogen atoms; optionally represents 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 halogen atoms and aryl substituents are halogen, straight or branched (C 1 -C 6) alkyl or (C 1 -C 6) alkoxy,

X represents an oxygen atom or a sulfur atom, and

Y represents an oxygen atom or a sulfur atom.

In particular, the present invention relates to substituted triazolinones of the formula I in which:

R ^{@ 1} represents a hydrogen atom, a straight or branched alkyl group of up to 8 carbon atoms, a cycloalkyl group of 3 to 7 carbon atoms or, optionally, at least once, the same or different halogen substituted aryl group of 6 to 10 carbon atoms,

R ² is straight or branched alkyl group having 1 to 18 carbon atoms, aikenylovú having 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 cyanalkyl, C 1 -C 6 alkoxyalkyl or C 1 -C 6 alkoxyalkyl or C 1 -C 6 alkoxyalkyl; to carbon atoms in the alkoxy and alkyl moieties, w

a (C 1 -C 6) dialkylaminoalkyl group or in each case at least one or the same or differently substituted C 3 -C 8 cycloalkyl or cycloalkylalkyl group having from 1 to 6 carbon atoms in the straight or branched chain alkyl moiety; suitable substituents are halogen, straight or branched (C 1 -C 4) alkyl, (C 1 -C 4) haloalkyl and (C 1 -C 9) identical or different halogen or straight or branched (C 4 -C 4) haloalkenyl. and having 1 to 5 identical or different halogen atoms, further R ² represents optionally at least one, equally 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 a straight or branched alkyl parts, pr where, optionally, halogen atoms are suitable as alkyl substituents and halogen, straight or branched (C 1 -C 6) alkyl or (C 1 -C 6) alkoxy are suitable substituents for aryl,

X represents an oxygen atom or a sulfur atom, and

Y represents an oxygen atom or a sulfur atom.

The compounds I may be optionally 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)

of ^c \,

T ^X NH-R wherein

R ¹ is hydrogen, straight or branched alkyl having up 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 having 1 to 4 carbon atoms and up to 9 identical 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, C 1 -C 15 same or different, C 1 -C 8 cyanalkyl, C 1 -C 6 alkoxyalkyl, C 1 -C 6 alkoxyalkyl, C 1 -C 6 alkoxycarbonylalkyl (C alko-C v alko), C 1-C alko alko (C až-C 2) alkoxycarbonylalkenyl, (C až-C 6 alky) alkylaluminoalkyl, (C až až-C dial) dialkylaminoalkyl in the alkyl moieties or in each case at least once the same or different s a 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, straight or branched alkyl having 1 to 4 carbon atoms , (C 1 -C 4) haloalkyl, (C 1 -C 4) haloalkyl (C 1 -C 9) halogen or straight-chained or branched (C 1 -C 5) haloalkenyl, C 1 -C 5 haloalkenyl, 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 the substituents of the alkyl group are, where appropriate, the consideration at halogen atoms and aryl substituents are halogen, straight or branched (C 1 -C 6) alkyl or (C 1 -C 6) alkoxy,

X represents an oxygen atom or a sulfur atom, and

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

a) reacting the hydrazones of the general formula II (II)

R ³

R ^{@ 1} N = C

R ⁴ 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 the 1 H-triazolinones of formula III with a group,

(III) in which:

R ¹ and X are as defined above, with the iso (thio) cyanates of formula IV r 2. _N = _c = γ (iv) in which

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

c) reacting the triazolinones of formula V

N _{/ H} H ₂ (A),

Y ^x 0 in which

R ¹ , X and Y are as defined above and r 5 is an alkyl, aryl or arylalkyl group with amines of formula VI

R ² - NH ₂ (VI), wherein

R ² is defined as above, 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 the formula I have herbicidal properties.

Surprisingly, the substituted triazolinones of the formula I according to the invention show 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 wherein:

R 1 is H, methyl, ethyl, npropylovú, isopropyl, n-butyl, isobutyl, sec -butyl group _x, t sec-butyl, n-pentyl, isopentyl, n-hexyl, an isohexyl group, a cyclopentyl group, a cyclohexyl group, a cyclopropyl group or in each case 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 _Å -butyl group or t and r-butyl, in each case straight-chain or branched pentyl, hexyl, heptyiovú, octyl nonyl, decyl, dodecyl, allyl, straight or branched butenyl, pentenyl or hexenyl, propargyl, straight or branched butynyl, pentinyl or hexinyl, straight or branched halogeno; up to 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 having from 3 to 8 carbon atoms each having from 1 to 3 halogen atoms, in particular fluorine or chlorine straight or branched to C 1 -C 6 -alkylalkyl, alkoxyalkyl, alkoxycarbonylalkyl, dialkylaminoalkyl of up to 4 carbon atoms in each alkyl or alkenyl moiety or in each case optionally one to three times, as well as differently substituted cyclopropyl, cyclopropylmethyl , cyclopropylethyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclohexylmethyl, cyclohexylethyl, each substituent being fluorine, chlorine, bromine, methyl, ethyl, n-propyl, n-propyl, n-propyl, n-butyl, isobutyl, sec, -butyl or tert -butyl or dichloroallyl,

R @ 2 is furthermore optionally one to three times the same or differently substituted benzyl, phenethyl, phenylpropyl, phenyibutyl, phenylpentyl, phenylhexyl, phenylheptyl, phenyl or naphthyl groups, the substituents of the phenyl radical in each case being fluorine, chloro, bromo, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, i.e., 4 '

sec-butyl, tert-butyl, methoxy and ethoxy,

X represents an oxygen atom or a sulfur atom, and

Y represents an oxygen atom or a sulfur atom,

Particularly particularly preferred are compounds of formula I in which

R ¹ is H, methyl, ethyl, npropylovú, isopropyl,

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, SefY-butyl, sec-butyl tert allyl, propargyl, 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 represents an oxygen atom or a sulfur atom, and

Y represents an oxygen atom or a sulfur atom.

The following substituted triazolinones of the formula I can be mentioned individually in addition to the compounds mentioned in the examples

NH, tx>,

X »-, *

R '

X Y

S - configuration

H -C (CH ₃ ) ₃ 0 0

H -C (CH ₃ ) ₃

H (CH _{3) 3}

CH

CH ₃

CH

CH

C-CH ₂ OCH ₃

CH.

-CH = CH ·

-c-ch ₂

R ¹

R ¹

CH

ch-c ₂ h ₅

CH, CH,

CHCH-

C-Chg-CH

CHCH,

CH, -CH-COOC, C OO _C

J | 2 5

CH ₃ t

CH ₃ -CH-CH ₂ -CH ₂ -CH- (CH ₂ ) ₂ -CH ₃ oo

CH ₃ CH ₃ (CH ₂ ) ₂ -ch ₃

CH, CH OO (CH _{2) 2} CH ₃

Cl

CH ₃

ΟΗβ

R ¹

R ²

CH

CH.

-ch- (ch ₂ ) ₃ -ch ₃ ^C 2 ^H 5

CH-CH- (CH ₂ ) ₂ -CH ₃ c ₂ h ₅ ch.

CH _{(CH2) 3-CH}

CH23

CH

CH

CH

CH

CH,

1 ^3. ^ CH-CH.

CH-CHCH-ch ₂ -ch

Both all.

CH.

CH-C-CH.

CN CH-

CH

-C-CH

CH '

X Y

CH.

CHCHCH.

R - configuration

S - configuration ₃

CH-CH

CH 2 CH ³

-ch-ch ₂ -och ₃

CH _{(CH2) 2 -CH3}

CH

CHCH25

CH

CH

CH

CH-C.H.

CH

CH

- (ch ₂ ) ₂ -ch ₃

- (CH ₂ ) ₃ -CH ₃ • CH.

CH

-CH ₂ -CH

CHCH

-ch-c ₂ h ₅

O S

O S

O S

O S

S o s o s o s o

CH.

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

R ¹ represents an alkyl group having 1 to 4 carbon atoms or a haloalkyl group having 1 to 4 carbon atoms and up to 9 identical or different halogen atoms,

R 2 is C 1 -C 10 alkyl, C 1 -C 6 haloalkyl, C 1 -C 13 halogen, C 3 -C 12 cycloalkyl optionally substituted with C 1 -C 4 alkyl or haloalkyl C 1 -C 4; 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 represents 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 as defined above 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-isopropylideneimino-3-methyl-1,2,4-triazoline is used as starting material in the process of the invention27

5-one, the reaction sequence according to variant a) of the process according to the invention can then be illustrated by the following reaction scheme:

CH.

H ^ C.

CHs, A

H ₂ O / H (CC ₃ ) ₂ CC .z * NH-CH ₅ -CH (CH 3) 2 3 α

H ₃ C, NH

SA

0 ^ \ H-CH ₂ -CH (CH _{3) 2}

If, for example, 4-amino-3-methyl-1,2,4 (1H) -triazolin-5-one) (and tert-butyl isocyanate) 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:

H (CH ₃ ) ₃ CN = C = O

If, for example, 1-ethoxycarbonyl-4-amino-3-methyl-1,2,4-triazolin-5-one ([alpha], [beta] -diethylpropane-1,3-diamine) is used as the starting material, then the reaction may proceed according to variant c) of the process according to the invention represented by the following reaction scheme:

CH

NH,

C _O H_?

H ₂ N-CH ₂ -CH ₂ -CH ₂ -N 4 ->

^ H0-C-C-O-C ₂ C ₅

C ₂ H ₅ -OH ^c -x_zin N

N? X í

n u

· Λ. ·

0 = C-NH-CH ₂ -CH ₂ CH ₂ N c ^c 2 ~ 5

Hydrazones, which are required as starting substances for the process according to the invention (variant a). \ ^Of a general definition of 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 @ 1 and R @ 1 are each independently hydrogen, straight or branched (C1 -C4) alkyl or phenyl or benzyl.

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-aminotriazolinones of formula III ir x in which

R ¹ and X are as defined above, with aldehydes or ketones of formula VII c = o (VII), wherein 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 1-unsubstituted triazolinone hydrazones of formula VIII thus obtained

H in which

R ¹ , R ⁴ and X are as defined above, either reacted with iso (thio) cyanates of formula IV r 2 in the next second step. n = C = Y (IV) in which

R2aY are as defined above, optionally in the presence of a diluent such as dichloromethane or dioxane and optionally in the presence of an auxiliary reagent such as triethylamine at temperatures between 50 and 150 ° C or alternatively reacted with esters (thio of chloroformic acid of formula IX

Y _C R 5 II-a-Cl (IX) in which

R ⁵ represents an alkyl group, an aryl group or an arylalkyl group, and Y is as defined above, optionally in the presence of a diluent such as tetrahydrofuran 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 of formula X (X) thus obtained,

Y = C-O-R 'in which

R 1, R ³ , R 4, R ⁵ , 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 is defined as above, optionally in the presence of a diluent, for example tetrahydrofuran, 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 subsequent reaction of the triazolinones of formula (X) thus obtained with amines of formula (VI) in a single reaction step (i.e. (in Example 3).

The 1-unsubstituted 4-aminotriazolinones of formula III 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), 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 VIII are largely known compounds (cf., for example, J. Heterocycl. Chem. 20, 77 80 (1983), J. Heterocycl. Chem. 16, 403-407 (1979), Chim. Acta). 7, 269, 290 (1979), J. Chem. Soc., Parkin Trans., 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 which are new are defined by formula Xa

ϊ = C - Ο - R ⁵ in which

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

R ¹ ' ¹ is preferably a straight or branched alkyl group having 1 to 4 carbon atoms, in particular 1 to 3 carbon atoms, very particularly especially R 11' is a methyl group,

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 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, sephyl-butyl or tert-butyl or optionally once or twice, the same or differently substituted phenyl or benzyl group wherein the substituents are, for each of F, Cl, Br, cyano, nitro, methyl, ethyl, npropylová, isopropyl, n-butyl, isobutyl, cuts-butyl, tert -butyl _x a group, methoxy, ethoxy, n-propoxy, isopropoxy, methylthio, trifluoromethyl, trifluoromethoxy or trifluoromethylthio,

X and Y are independently oxygen or sulfur, preferably oxygen.

The H-triazolinones required as starting materials in carrying out the process of variant b) are generally defined by Formula III. In this formula III, R @ 1 and X are preferably those which have been shown to be preferred for the compounds of the formula I according to the invention.

The H-triazolinones of the formula III 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. med. Chem. Chem., 18, 215 (1983), Ber., 98, 3025 (1965), Liebigs Ann, Chem., 637, 135 (1960).

The iso (thio) cyanates which are further required as starting materials in carrying out the process of variant b) are generally defined by formula IV. In 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 are the following substituents.

Thezo (thio) cyanates of formula IV are mostly known organic chemistry compounds. However, 2,2,2-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, DEOS 28 04 082, DE-OS 25 12 514, U.S. Pat. U.S. Patent No. 27,065,753, U.S. Patent No. 33,165,654, JP 50/29599, Synthesis 1985, p. 682 or J. Am. Chem. Soc., 77, 1901-1922 (1955).

The triazolinones required as starting materials for carrying out the process of variant c) are generally defined by formula V. In this formula V, R 1, X and Y preferably have the meanings already indicated as being advantageous in relation to the description of compounds of formula I,

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 fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n36 propyl, isopropyl, n-butyl, isobutyl, sephylbutyl, tert -butyl and the like. a group, 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, 1691-1686 (1980)).

The triazolinones of the formula Va are still unknown

Y = C-O-R ⁵ (Ve) in which an alkyl group, preferably a straight or branched alkyl group having 1 to 4 carbon atoms, in particular 1 to 3 carbon atoms, is 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 the formula V by reacting the 1H-triazolinones of the formula IIIa.

R ¹ ' ¹ \

nh ₂ (Hla) in which

R ¹¹ and X are as defined above, with (thio) chloroformic acid esters of formula IX

R 5 -O-C-CI (IX)

Wherein Y 5 and Y are defined above, optionally in the presence of a diluent, such as tetrahydrofuran, and optionally in the presence of a reaction auxiliary, such as tert _x potassium t-butoxide or sodium hydride, at temperatures between -20 ° C and + 40 ° C (cf. also examples).

The H-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. med. Chem. Chem., 18, 215 (1983), Ber., 98, 3025 (1965), Liebigs Ann, Chem., 637, 135 (1960).

Suitable acids for carrying out the process according to the invention (variant a) X are all 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 polar, 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), generally 1 to 50 mol, preferably 1 to 20 mol, of acid are used per 1 mol of hydrazone of the formula II. The hydrazone of formula II is dissolved in a suitable amount of diluent, the solution is then treated with the required amount of acid and concentrated under reduced pressure for several hours.

In a particular embodiment, it is also possible to carry out the process of variant a) to produce the intermediates necessary for this purpose of formula II in a single reaction step, i. 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) X (cf. also examples) or alternatively select triazoline hydrazones of the formula VIII and reacting them successively 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).

Suitable diluents for carrying out the process according to variant b) are all inert organic solvents. 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-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. As such, all conventional inorganic or organic bases are suitable. These include, for example, tertiary amines such as triethylamine, Ν, Ν-dimethylaniline, N, N-diethylbenzylamine, N, N-dimethylcyclohexylamine or dibutyltin dilaurate, pyridine, N, N-dimethylaminopyridine, diazabicyclooctane, diazabicycicononene or diazabicycyclononene.

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, 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 2.0 mol, preferably 0.001 to 2.0 mol, are used per mole of 1H-triazolinone of the formula III. 0.001 to 1.0 mole of auxiliary reagent.

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

Suitable diluents for carrying out the process according to variant c) are inert organic solvents. 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, diazabicyclooctoctane , 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 2.0 mol, preferably 1.0 to 5.0 mol, are used per mole of triazolinone of the formula V 1.0 to 1.2 moles 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. in a single reaction vessel.

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

Another method for obtaining compounds of formula I is by reacting oxadiazolinones of formula XI

Ο

Ο

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

O, II ii

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

Y = C-NH-R 2 (XH) wherein

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

Oxadiazolinones of the formula XI are known compounds (cf., for example, FR 14 15 605 and CA 64, P5105g as well as NL 6 510 645 and CA 65, P2274d-f, respectively) or are obtained according to generally known procedures, for example by reaction of the corresponding 4H-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 the formula I is carried out by conventional methods, 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 genera:

mustard (Sinapis), cress (Lepidium), rhododendron (Gallium), starfish (Stellaria), camomile (Matricaria), ruman (Anthemis), galinsoga (Galinsoga), carrot (Chenopodium), ragwort (Urtica), ragwort (Senecio), Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsium, Cardus Milk (Sonchus), Solanum, Rorippa, Rotala, Lindernia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, 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), warbler (ipomoea), vetch (Vicia), tobacco (Nicotiana), tomatoes (Lycopersicon), peanut (Arachis), tusk (Brassica), lettuce (Lactuca), cucumber (Cucumis), pumpkin (Cucurbíta).

monocotyledonous weeds of genera:

hedgehog (Echinochlora), bar (Setaria), millet (Panicum), fingergrass (Digitaria), timothy (Phleum), grayling (Poa), fescue (Festuca), eleusine (Eleusine), Brachiaria, Buttercup (Lolium), Barn (Bromus) ), oats (Avena), chess (Cyperus), sorghum (Sorghum), wheatgrass (Agropyron), hawk (Cynodon), Monochoria, Fimbristylis, rosehip (Segittaria), Eleocharis, Scirpus, Paspalum, Ischaemum, Sphenoclea, Dactyloctenium 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 preparations 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, i. with liquid solvents and / or solid carriers, optionally using surfactants, i. 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 cephalins and lecithins and synthetic phospholipids. Other additives may be mineral and vegetable oils.

In addition, these compositions may contain colorants such as inorganic pigments, for example iron oxide, titanium dioxide and ferrocyanide blue, and organic colorants such as alizarin dyes, azo dyes and metal phthalocyanine 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 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) are suitable for this mixing. -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 to kill weeds in soybean. 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-nitrobenzoate, 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-546 (4H) -one, 2- [4 - [(6-chloro-2-benzoxazolyl) oxy] phenoxy] propanoic acid, is j methyl or ethyl ester thereof, 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] phenoxy] propanoic acid or ethyl ester thereof, 2- (4- (2,4-dichlorophenoxy) phenoxy] propionic acid methyl ester, 2- [5] - methyl -5- (1-methylethyl) -4-oxo-2-imidazolin-2-yl] -3-quinolinecarboxylic acid, 1-isobutyl-aminocarbonyl-2-imidazolidinone, 3-cyclohexyl-5,6-trimethylene-uracil, N methyl-2- (1,3-benzothiazol-2-yloxy) acetanilide, 2-chloro-N- (2,6-dimethylphenyl) -N - [(1H) pyrazol-1-ylmethyl] acetamide, 2 -ethyl 6-methyl-N- (1-methyl-2-methoxyethyl) chloroacetanilide, 3 (ethoxycarbonylaminophenyl-N-1'-methylphenyl) carbamate, 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 exhibit a synergistic effect.

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

The active compounds can be used as such, 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 illustrating the method of production of active ingredients:

Example 1

/ ^C \

0 ^ NH-CH ₂ -CH (CH _{3) 2}

Procedure a)

To 11.1 g (0.04 mol) of 1- (N-isobutylcarbamoyl) -4-isopropyl-propylene-imino-3-methyl-1,2,4-triazolin-5-one in 100 ml of ethanol is added 20 ml of concentrated acid 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- (Nizobutylcarbamoyl) -3-methyltriazolin-5-one of melting point 183 DEG C. are thus obtained.

Example 2 ^H 3 ^C \

nh _{2 0} A

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) tert-butyl isocyanate and 0.05 g to 0.1 g of diazabicycloundecene, stirred for 2 hours at 20 ° C, then concentrated under reduced pressure, the residue is taken up in dichloromethane, washed with water, dried over sodium sulfate, concentrated by evaporation under reduced pressure, under reduced pressure and the residue crystallized upon 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 of melting point 132 DEG C. are obtained.

Example 3 - 3 °

Procedure a) - variant in a single reaction step

To 8.2 g (0.03 mol) of 4-isopropylidenenimino-3-methyl-1-phenoxycarbonyl-1H-triazolin-S-one in 50 ml of absolute tetrahydrofuran is added 4.2 g (0.03 mol) ( 2,2-dichlorocyclopropyl) 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 3-4 hours. at 60 ° C at 20,000 Pa. For working-up, 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 sulfate and concentrated under reduced pressure. The residue is crystallized 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 ^H 3 ° \

NH,

CH0-C - C-NH - _(CH? CH ₇

I cr

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 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 at 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 sodium sulfate, 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. .

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

(I),

S-configuration

-1 0 0 n-N * £ K '

1.5 (d) c ₂ h ₅ ~ 0

1.1. 139

CH ₃ -CH (CH ₃ ) ₂

CH 2 - (CH ₂ ) ₅ -CH ₂ Cl

CH ₃ -CH-C ₂ H ₅

O tt 161 ^c

O O m.p. High: 63 ° C

OO ¹ Η-ΚΜΗ ^χ) >

1.45 (m, 4H)

O O

CH

0.95 (t, 3H)

CH ₃ -CH (C ₂ H ₅ ) ₂

CH ₃ -CH-CH (CH ₃ ) ₂

O O m.p. 103 ° C

O O m.p. 103 ° C

CH

O O m.p. 105 ° c

O O m.p. 135 ° C

CH ₃ -ch- _2- c-ch ₃

O O m.p. 106 ° C

CH ₃ (decomposition)

R2 X Y physical properties

Example number

R ¹

CHch ₃

I

-C-CHCHH - (CH ₂ ) ₅ -CH ₂ Cl

SO mp 100 ° C ⁰ mp 131 ° c

Example R ¹ Number

R ² XY physical properties

CH24

CH25

CH

-c-ch ₂ ci

CH-CH ₂ CH = CH ₂ CH ₂ CH ₃ -C-OC ₂ H ₅ CH ₂ C

CH-C-CH ₂ Cl

H CH _{3 I-c-2}

CHCHC ₂ H ₅ -CH ₂ -C-CH ₃

CH0 0 m.p. 118 ° C

0 1.1. 92 ° C

O O 1.1. 127 [deg.] C

0 n “1.5055

O O m.p. 176 [deg.] C

4.4; 7.95

Example R 6 number

R ² XY physical properties ch ₃ ^C 2 ^H 5

CH _? F

I

-c-ch ₃

I _CH2 F _CH2 access ^and

- ^C - ^Objective 3

0 1.1. 133 ° c

0 mt 30-40 ^c C

0 ¹ Η-ΝΜΗ ^ϊ)

4.36; 8.23

CHch ₃ -cc ₂ h ₅

0 1.1. 99 ° c

CHCl ₃ -CH (CH _{2) 3} -CH _{(CH3) 2}

0 ¹ H-NMR ^x)

4.40; 7.61

CH

R1

Example number

CH,

CH

J CH-CH, CH ₃ - (CH _{2) 2} CH ₃

CHCH, -CH-C-CHch ₃ ch ₃

CH,

CHCH,

CH,

I

C-CF.

CH

X Y physical properties

0 m.p. Mp 198 ° C

0 m.p. 108-109 ° C

O 1.1. Mp 168-170 ° C

0 m.p. Mp 134-136 ° C

Q m.p. m'c

0 m.p. 149-151 [deg.] C

O O m.p. Mp 93-94 ° C

O O m.p. 175-178 [deg.] C

CH ₂ CH ₂ CN

Example R ** number

R ² XY physical properties

CH h ₃ -ch ₂ -ch- (ch ₂ ) ₃ -ch ₃

Mp 91-92 ° C ^C 2 ^H 5

CH ₂ h ₅

-cc ₂ h ₅

0 1.1. 102-103 ° C

CHCH:

CH ₃ · -C-CH ₂ -F

0 m.p. 178 ° C

CH

0 1.1. 113 ° C

0 m.p. 109 ° C

0 m.p. 148 [deg.] C

CH ₃ -C ₂ H ₅

O O m.p. 185 ° C

CH

-ch ₂

CH:

-c-ch ₂

CH

-C-CH «C

Cl

O O m.p. 198 ° C (hydrochloride)

OO mp 135 ° c ch ₃

Cl

CH 2 -CH-CH ₂ -C 1

O O m.p. 136 ° C

O O m.p. 122 [deg.] C

-ch-cf ₃

O O m.p. 141 ° C

C-CN

CH

O O m.p. 176 [deg.] C

X Y physical properties

R ¹ R 2

Example number

CH ₃ -CH- (CH ₂ ) ₄ -CH ₃ ch ₃

CH. CH-N.-QCH.

^{3 and 2 3} ch ₃

CH ₃ - (CH ₂ ) ₂ -OCH ₃

O O m.p. 67 C

O O m.p. 120 [deg.] C

G3, -CH-CH ₂ -N '

CH

c ₂ h ₅ c ₂ h ₅

O O m.p. 114 ° C

O .0 m.p. 84 ° C (hydrochloride)

O S m.p. 147 ° C

O S m.p. 195 ° C

O S m.p. 205 ° C

ies

O S m.p. Mp 212 ° C

CH

CH, -CH-CH-Cl

I I

CH ₃ CH ₃

Mp 114 ° C ch ₃ -CH-CH = C

CH

Cl

Cl

CH, C1 ²

CH, -CH

CH = CH ₂ CH ₃

Cl o 0 ηβ 1,5328

O O m.p. 120 [deg.] C

C-CH-CH = C 11

CH ₃ CH ₃

1.3840

Cl

Example R1 number

R2 X Y physical properties

CH, -CH

CH78 _{CH2 CH2} C C _CH2-CH-CH2 C

Cl

-ch-ch ₂ or c ₂ h ₅

CH,

O 0 1.1. 158 ^U C (3: 1) ch ₃ -c- (ch ₂ ) ₃ -ch ₃

CHCH,

-CH- (CH ₂ ) ₅ -CH ₃

CHCH.

CH, -CH-CH 2, -C-CH,

II

CH, CH,

CH,

-ch ₂ -ch

C H. X 2?

^C 2 ^H 5

O 0 m.p. 147 C

O n ²²¹ ' ⁴⁸⁹¹

O n ²⁰ 1.4920

OO tt 140 ^U C o tt 115 c

R ² XY physical properties

Example number

0 1.1. 144 ° C

Example number

X Y physical properties • 90

ABOUT

2.33

0 m.p. 152 [deg.] C

S m.p. 178 ° C

0 m.p. 156 [deg.] C

M.p.167 ° C

0 m.p. 113 ° C

° C

_{CH3 -CH2-C 2} H ₅ CH ₃ H mp of 106 DEG C.

CH ₃ - (CH ₂ ) ₂ -CH (CH ₃ ) ₂

O O m.p. 104 ° C

Cl Cl

100 ch ₃ -ch ₂ CH

101

102

0 m.p. 151 ° c

O O m.p. 151 ° c

-C-CH

CH

O O m.p. 134 ° C

CH

103

R1

R ²

X Y

Example Physical Property Number

104 ch ₃ -ch- (ch ₂ ) ₂ -ch ₃

CH, n ° ° 1.4972

105

CH106

CH107

108 ^C 2 ^H 5

-cc ₂ h ₅ c ₂ h ₅

CH ₃ -ch- (CH ₂ ) ₂ -ch _{/ C} h ₃

CHCHCH ^C 2 ^H 5

0 m.p. 128 C

0 1.1. 101 C

0 m.p. 73 C

- ( ^CH ₂ ) ₃ -n ^C 2 ^H 5

0 np ° 1.5815 (hydrochloride)

CH ₃ - (CH ₂ ) ₃ -n

CHo 0 m.p. 210 ° C (hydrochloride)

109

R1

R 2

X Y physical properties

Example number no ch ₃ -ch-ch ₂ -cn

0 m.p. 145 ° c

111 CH c ₂ h ₅ i -CH-CH ₂ -CH-C ₂ H ₅

OO Hp ° 1.4890 ^C 2 ^H 5 ^CH 3

CH112 ch ₃ -ch-ch ₂ -ch

O? N? ° 1.4858

CH113 CHCH,

O O m.p. 108 ° C (hydrochloride)

114 ch ₃ - (ch ₂ ) ₄ -ch ₃

OT tt 81 ^U C

115 CH,

-CH- (CH ₂ ) ₃ -N

CH,

-ch-ch ₂ -ni, ^C 2 ^H 5

CH,

CH,

C ₂ H ₅

O O Πρ ° 1,5100 (hydrochloride)

O O Πρ ° ^ 515 ° (hydrochloride)

116 CH,

R ^ X Y physical properties

Example number

R1

117

118

119

O O m.p. 157 ° C

O O m.p. Mp 116 ° C

O O m.p. 145 ° C

120

121

CH ₃ -C 1 -CH ₂ -O 4 H ₃

O O m.p. Mp 123 ° C

O O m.p. 213 ° C

122

R1

R ² XY physical properties

Example number

123

CH

0 m.p. 93 ° c

125

* 126

127

128 h ₃ c.

Cl

CH, -CH

CHCH-CH = C

Cl

0 H ^ Ni ^ £ 3 ^*

1.58 (dd);

1.77 (t); 2.76 (t), CH ² / \

CH (CH ₂ ) ₉

O 0 m.p. 142 ° C

O O m.p. 123 ° C (endo-forms)

O O m.p. 131 ° C (ex-form)

R1

R 2

Example number

X Y physical properties

O O 1.1. 133 ° c

0 m.p. 117 ° C

132

CH

1.45 (s), 7.04-7.43 (m)

133

O 0 m.p. 118 ° C

R ² XY physical properties

Example number

135

136

137

138

139

140

R1

CH ₃ - CH - C - ch ₃ c ₂ h ₅ ch ₃

O 0 m.p. 157 ° c

^C 2 ^H 5

Mp 95 ° ^C 2 ^H 5

-C _{(CH3) 3}

O m.p. 158 ° C

I.

-C-C-CH

CH,

O m.p. Mp 119 ° C

Example R ¹ number r 2 XY physical properties

141

142 ^C 2 ^H 5 ^C 2 ^H 5

143 C ₂ H ₅

144 C ₂ H ₅

145 CH ₃

146 C ₂ H ₅

147 CH ₃

148 CH ₃

149 CH ₃

-ΖΛ 0 0 mp 106 ° C CH _{(CH3) 2} 0 0 mp 89 ° c CH. I-CH ³ CHgCl 0 0 ^ n '= l, 4929 CH 1-CH-C ₂ H ₅ 0 0 n | SL, 4955 P: h ₃ CH ₃ -CC 1 Cl 2 0 0 0 0 mp 146 ° C mp 105 ° C 1 CH ₃ - (0¾) ^ ¾ 0 0 mp Mp 110 ° C • ^(OH 2> 15 ^CH 3 0 0 mp 98 ° C 3 0 mp 104 ° C

Example R1 number

R ^ X Y physical properties

150 CH-

Y CH-CH j

-CH-, O O 1.1. 118 ° C

151 CH - <H - CH (CH ₃ ) ₂ OO 1.1. 129 [deg.] C

152 CH-

OO tt 112 ^UC

153 CH ₃

C (CH ₃ ) ₃ O mp 193 C

154 CH.

c ₂ h ₅

O O m.p. 125 ° C

155 C ₂ H ₅

-C (CH _{2) 3} CH ₃

0404, 4896

CH156 CH • CHg — ClO O 1.1.

185 ° C

Example R ¹ Number

R ² XY physical properties

157 CH-

0 m.p. 158 ° C

CH158 CH-C-CH _{(CH3) 2}

0 tt 132 ^C c

CN? 2 ^H 5

159 CH ₃

O O m.p. 98 ° C

160 CH ₃

161 CH ₃

_C-CH3

O O m.p. 137 ° C

O O m.p. Mp 162 ° C

162 CH ₃

O O m.p. 172 ° C

R ² XY physical properties

Example number

R1

163

164 _{(CH3) 3} C165

166 _{(CH3) 2 CH3} ch167

- (CH 2) ₅ -CH ₃

CH _? (

C-nosed

I

CH ₃

CH, i

C-C »CH

I

CH ₃

- (0¾) ej 'CH ₃

168 (ch ₃ ) ₂ ch169 ch ₃ - (0¾) ₂ "

170 (CH _{3) 3} C-

O Mp = 104 ° C

0.104-1.480 °

O O m.p. 106 ° C

O O m.p. 90 ° C

O O m.p. 90 ° C

O O m.p. 133 ° C

O O m.p. 98 ° C

Mp 158 ° C

R ² XY physical properties

Example number

173 C ₂ H ₅

-c-ch ₂ f

0 m.p. 137 ° c

174 CH ₃ - (CH ₂ ) ₂ i

Cl-C-Cl

0 n £ = 1.5830

175 (CH ₃ ) ₂ CH-C-CH ₂ Cl

0 nj = 1.5650

Cl F

176 CH ₃

CH

0 m.p. 105 ° C

178 C ₂ H ₅ ch ₂ Cl

I

-C-CH-, i

Cl Cl

O O nj «1.5149

179 C ₂ H ₅

-C-CH ₂ C1

O O m.p. 128 [deg.] C

CH

180 ^C 2 ^H 5 * 1.4928

181 (ch ₃ ) ₃ cC- (CH ₂ ) ₂ -CH ₃

182 <ch ₃ ) ₃ c-

O 0 1.44 (9H), 4.53 (2H)

R1

R ² XY physical properties

Example number

183

184

185

186

187

188

189 (ch ₃ ) ₃ c-c (ch ₃ ) ₃ ^C 2 ^H 5

CH.

CH-CH _{(CH3) 2}

CH ₃ - (CH ₂ ) ₂ -C (CH ₃ ) ₃ (CH ₃ ) ₂ CH- ^c (CH ₃ ) ₃

O O m.p. 142 ° C

O O m.p. 93 C

mp 203 DEG C. o. 112 DEG C. o. 108 ° C

O O m.p. 151 ° c

-C (CH ₃ ) ₃

(S-configuration,)

Example R ¹ Number

R ² XY physical properties

190 (OHp-jC-

(R-configuration) n l 1.511

CH191 (CH _{3) 3} CC-CH? Cl

I

CH,

mp 133 C

CH.

192 (CH ₃ ) ₃ -C-CH 2 CH

O O m.p. 148

CH,

CH193 (CH _{3) 3} CC (CH 2) ₃ CH ₃

O n ° -1, 4844

CH,

CH.

194 (CH ₃ ) ₃ C-CH-CH (CH ₃ ) ₂

O O m.p. 135 ° C

R1

R2 X Y

Example number

CH.

195 _{(CH3) 3} C F ^ CTT

196 (CH) ₇ C 3 ^S

CH197 _{(CH3) 3} C198 _{(CH3) 3} C199 (CH _{3) 2} CH

ch

200 (ch ₃ ) ₂ ch-ch-c ₂ h ₅

CH.

201 (CH ₃ ) ₂ CH-CC ₂ H ₅ physical properties

1.1. 141 ° C

mp 203 ° C n ° 1.555 °

mp Mp 172 ° C

mp 109 ° C

1.1. 83 [deg.] C. n-1, 4801

CH.

Example number

X Y physical properties

202

203

204

O m.p. 177 ° C

0 m.p. 107 ° C

0 m.p. 124 ° C

205 ch ₂ ci

I (0 ') CH--C-CH i

CH ₂ C1

0 1.34 (6H),

4.40 (2H), 3.12 (1H)

206

207 (ch ₃ ) ₂ ch-c-i ₂

I

CH ₃ (CH ₃₎ CH ₂ CH (CH _{3) 2} 0 mp of 121 DEG C.

0 m.p. 124 ° c

208 (ch ₃ .j. ₂ chCH

C-iCHG) ₂ CH ₃

° C, 4874

CH

R ¹

R2 X Y physical properties

Example number

209

- 210

211

212

213

214

(CH ₃ ) ₂ CH- Qlk I ^J -c- (ch ₂ ) ₃ -ch ₃ o CK ₃ 0 n ° = l £, 4847 CH ₃ | (CH ₃ ) ₂ CH- 1 -CH-CH (CH ₃ ) ₂ O 0 n ^ ° = l, 486O CH ₃ i ^C 2 ^H 5 I -C-CN ⁰ I 0 1.1. 13 ° C CH ₃ Λ “- * \ And NMR *) c ₂ h ₅ S-ΖΛ, 0 1.29 (t, 3H) I \ - / 1.58 (d, 3H) oh ₃ -CHCH, CH (CH3), O 0 (amorphous ^c 2 ^h 5 i ² product) CH ₃ C- ^H 5 -CH (CH 2) ₉ CH (CH ₂ ) ₂ o 0 (amorphous t y | fc c J ohj product) ^C 2 ^H 5 -CH (CH 2) ₃ CH (CH ₃ ) ₂ O 0 (amorphous product)

CH ₃

215

218 C ₂ H ₅

0 m.p. 105 ° C

219 ^C 2 ^H 5

220 C ₂ H ₅

221 CH ₃

222 CH 2

Cl

Cl

CH

O O m.p. 114 C

0 (amorphous product)

0 m.p. 128 [deg.] C

O O m.p. 118 ° C

Example R1 number

X Y physical properties

223 CH ₃

mp 112 ° C. 224 C ₂ H ₅

mp 90 ° C

225 C ₂ H ₅

mp 108 ° C

Note to table:

1 H-NMR spectra were performed in deuterochloroform (CDCl 3) using tetramethylsilane as an internal standard. The chemical shift is given as the value of d in ppm.

Production of starting materials Example 11-1

^ ^G \

NH-CH ₂ -CH (CH ₂ ) 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. with stirring. (0.12 mol) of isobutyl isocyanate and the mixture was stirred at 100 ° C for 3 hours after the addition was complete. For working-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, dried over sodium sulfate and freed from the solvent under reduced pressure.

11.2 g (100% of theory) of 1- (N-isobutylcarbamoyl) -4-isopropylideneimino-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 formula (II) are obtained in a corresponding manner and according to the general process data

N-C

R ³ \ _B 4

NH-R

(II) physical properties

Table 2

Example R1 R2 number

R3

R4

η-4 ch ₃ -ce-c ₂ h ₅ = c (ch ₃ ) ₂ ch ₃

ΞΣ-5 CK ₃ -CH (CH ₃ ) ₂ = C (CH ₃ ) ₂ :: - 6 ck ₃ -ch (c ₂ h ₅ ) ₂ = c (ch ₃ ) ₂

ZI-7 CE ₃ -CH-CH (CH ₃ ) ₂ = C (CH ₃ ) ₂

II-8

mp 87 ° Art

mp 107 ° c

mp 68 ° C

0.54 (d, TA ₃₎

mp 115 ° C

Example number

R 2

R3

physical properties

CH.

II-9

II-10 ch ₃ -c-ch ₂ ci = c (ch ₃ ) ₂

CH

mp 88 ° C

mp 139 [deg.] C

ΙΣ-11

11-12

11-13

CH ₃ -CH ₂ -COOC ₂ H ₅ = C (CH ₃ ) ₂

CH ₃ -CH ₂ -CH = CH ₂ = C (CH ₃ ) ₂ oil

mp 108 ° C

mp 86 ° C

Example R1 r2 number

physical properties

CH

11-17

-CH ₂ -C-CH ₃ = C (CH ₃ ) ₂ mp 121-122 ° C

CH

Example 111-1

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 toluenesulfonic acid in 100 ml (79.06 g, 1.36 mol) of acetone are stirred for 40 hours at 70 ° C and then the mixture is concentrated in vacuo to give 15, 4 g (100% of theory) of 4-isopropylideneimino-3-methyl-1,2,4- (1H) -triazolin-5-one, m.p. 140-144 ° C.

Example V-1

= C - 0

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 was added 2.7 g (0.024 mol) of tert-butylamine. 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, glacial acetic acid was adjusted to pH 5, concentrated under reduced pressure, the residue taken up in chloroform, washed with water, dried over sodium sulfate, concentrated under reduced pressure, and crystallized by trituration with ether.

1.1 g (23.5% of theory) of 4-amino-3-methyl-1-phenoxycarbonyl-1,2,4-triazolin-5-one are 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 are obtained, m.p. 140-144 ° C. Example X-1 .CH.

H ₃ C

CH.

= C - 0

To 15.4 g (0.1 mol) of 4-isopropylidenemimino-3-methyl-1,2,4- (1H) -triazolin-5-one in 100 ml of absolute tetrahydrofuran is added at room temperature first 13.4 g (0 , 12 mol) tert. of potassium butoxide, the reaction mixture is stirred for one hour at room temperature, then 15.5 g (0.1 mol) of phenyl chloroformate are added and the mixture is stirred for a further 12 hours at 20 ° C.

For working 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

0 = 0-0- C ₂ H ₅

7.7 g (0.05 mol) of 4-isopropylideneimino-3-methyl-1,2,4- (1H) -triazolin-5-one in 50 ml of absolute tetrahydrofuran are added at 20 DEG C. to 1.5 g. (0.05 mol) of sodium hydride, 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 20 ° C.

For working 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 sulphate, concentrated again under reduced pressure and recrystallized from isopropanol.

5.0 g (44% of theory) of 1-ethoxycarbonyl-4-isopropylideneimino-3-methyl-1,2,4-triazolin-5-one are obtained.

Examples illustrating biological activity:

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

4-amino-3-methyl-6-phenyl- _1,2,4 -triazin-5-one (a compound known from DE-OS 23 64 474, Example I-22),

C - NH - CH (CH ₃ ) ₂ (B)

Compound B:

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

Example A

Preemergence test

Solvent: 5 parts by weight of acetone

Emulsifier: 1 part by weight of alkylaryl 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 show 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 assays are summarized in Tables A and A-1 below.

.2

Έ υ

0) o

o rH .2

JS

W to 'o.

(0 c

w

CO Q

O) (0

C <0

E <

ABOUT ABOUT about ABOUT Q ABOUT ABOUT about about WHAT ABOUT ABOUT ABOUT ABOUT about about H H i-l H r4 (-1 H

ABOUT about o o ABOUT about about about ABOUT 00 about about about about about about r4 r4 rh r4 r-i r4 r4

O '

0 O O O Q

O O O CO O ir \ o cr> O rH

Table A; preemergence test (greenhouse experiments) to υ

about.

o <

'OS>

p

U (Q

Q.

Φ o

'WHAT

o tO O m m cr> co σ »oo

ABOUT

CO o o

CO CO

about 8 about ABOUT ABOUT 2 o 2 o o o 8 about about about about 8 about 8 about ABOUT about about CM CM CM CM CM CM CM CM CM

ΌΒ

B

XB c

CQ H

CM

CM m

co 'à cin

ΌO)

Table A -1: pre-emergence test (greenhouse experiments)

E □

c ro o

w ω

CL

CO c

0 (0 o

_TO

C3 c

about

ĽL .2

E co

E □

-a o

Q.

ABOUT

C ω

r

O »c cu

E> o

CO ‘CD

WHAT

¼

O) »N □

ABOUT

Q.

'WHAT

o o ca O

O ir \ o σ>

rh

O o o r-1 ι — I m

c— l “í

ABOUT)

Table A-2: pre-emergence test (greenhouse experiment) o

>

ro o

ro

ΣΙ c

ABOUT

Q.

ro ω

E o

Q.

E □

T3

ABOUT

Q.

ABOUT

C ω

JC

O ω

□ c

ro

L_ ro. E <

ro o

* c □

□

O tn

ABOUT

Q.

• ro

CO u_ o

σ>

o c \ í m

E ω

z — z \ o-z

Example B

Post-emergence test

Solvent: 5 parts by weight of acetone

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To prepare a suitable active ingredient, 1 part of the 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.

with

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 so that the required amount of active substance 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 untreated control plants)

100% - complete destruction (death) of plants

In this test, for example, the compounds according to Examples 1 and 48, the compounds according to Examples 2, 14, 23, 32, 41, 45, 48, 57, 78, and the compounds from 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 assays are summarized in Tables B-1, B-2 and below

B-3:

him

Table B-1: post-emergence test (greenhouse experiments) f

□ e

<u

Ro ‘Ro ro ω

and

C

m

Q.

> u · □

OT (δ · o o o co

IPi σ *

O O

CO O

H o

do i

Q

O ε

about

Q.

o c

Q) x:

ABOUT

Έ □

TD

ABOUT

Q.

O o

R-I

ABOUT

cifs

0 \

I

Φ

M

WHAT

ch

Table B - 2: post-emergence test (greenhouse experiments)

w

Q.

(0 c

ω

TO ω

E o

Q.

O O o

O-O-I-I-I

>

-X

ABOUT

TO i— □

TO

ABOUT

O O O o o r-1 (—1 rH § 8 § 8 8 c

n □

c ra

E <

'TO la * £ υ

about

CL

O c ~ o

CM o

ΙΛ

O o

o o

rH §O ir \ O Q

O σ 'O O

ABOUT ABOUT about o o about ABOUT ABOUT about about 0> about about about about ABOUT about rh rh rh rh rh rh rh

o o o rH

0 o rH rH

about about about 8 ABOUT ABOUT ABOUT ABOUT 8 ABOUT ABOUT about about about about about about 8 8 ABOUT ABOUT about about ABOUT 8 CM CM CM CM CM CM CM CM CM CM

.w '5.

n c

w

O σ »o

c8 rH (Q ω

E o

Q.

(Π

O) o

V) c

n

ABOUT

WITH?

O o ia q m O o

O what σ \ o σ> o o * * rd rd rd

About IA O O O O O

O ca ia n o o

H rd

O O Q O o O o

O O O O CA O O 'Ί ι-d rd rd rd rd ca ca

o o

rd

ABOUT

O rd ia O <A O rd

Table B - 3: post-emergence test (greenhouse experiments)

W □

C n

E <

o o

rH o

o o

rd

C

V> «

Q.

o o o rd o

from

M> N

O = (B ^{E E} E><DO) Xi JC '3 ~

ABOUT

Q.

ABOUT ABOUT ABOUT about o o about about ABOUT about about about about about IA about about about about IA IA rd rh rh rh

(D 'JS' CD

C c

iô> □ ia rd

Π \ O

CD n

rd

IA rrd

Table B - 4: post-emergence test (greenhouse experiments)

Claims (12)

PATENT CLAIMS Substituted triazolinones of general formula I (I), in which R 1 represents a hydrogen atom, a straight or branched alkyl group with s C 1 -C 8 -cycloalkyl having 3 to 7 carbon atoms in the cycloalkyl moiety, optionally at least once, likewise, or Λ a halogen-substituted aryl group having 6 to 10 carbon atoms or a haloalkyl group having 1 to 4 carbon atoms and having up to 9 identical 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 1 to 15 identical or different halogen atoms, C 1 -C 8 -alkylalkyl, C 1 -C 6 alkoxyalkyl, C 1 -C 6 alkoxyalkyl and C 1 -C 6 alkoxycarbonylalkyl 102 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, dialkylaminoalkyl of 1 to 6 carbon atoms in the alkyl moieties or in each case at least once the same or 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, halogen being a substituent; straight 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 re and R ² is optionally at least one, equally or differently substituted aralkyl or aryl having 6 to 10 carbon atoms in the aryl moiety and optionally having 1 to 8 carbon atoms in a straight or branched chain. 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 represents an oxygen atom or a sulfur atom, 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 with s C 1 -C 8 -cycloalkyl having 3 to 7 atoms Or optionally substituted aryl of 6 to 10 carbon atoms at least once, the same or different halogen atom, 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 , a haloalkenyl group having 2 to 8 carbon atoms and having 1 to 15 identical or different k atoms to k. C 1 -C 8 cyanalkyl, C 1 -C 6 alkoxyalkyl, C 1 -C 6 alkoxyalkyl or C 1 -C 6 alkoxycarbonylalkyl, C 1 -C 6 dialkylaminoalkyl in the alkyl moieties or in each case at least once the same or differently substituted cycloalkyl or cycloalkylalkyl radical 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, halogen being a substituent; straight or branched (C 1 -C 4) alkyl, (C 1 -C 4) haloalkyl (C 1 -C 9) or different halogen atom or C 4 -C 4 haloalkenyl (C 1 -C 5) carbon atom or different halogen, furthermore R ² represents an 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 alkyl, wherein the substituents of the alkyl group are, if considered halogen atoms and as substituents of an aryl group are suitable 104 halogen, straight or branched (C1-C6) alkyl or (C1-C6) alkoxy, X represents an oxygen atom or a sulfur atom, 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 an alkyl group having 1 to 4 carbon atoms or a haloalkyl group having 1 to 4 carbon atoms and up to 9 identical or different halogen atoms, R ² is alkyl having 1 to 10 carbon atoms, haloalkyl group having 1 to 6 carbon atoms and 1 to 13 halogen atoms, a cycloalkyl group having 3 to 12 carbon atoms, optionally substituted with C 1 -C 4 -alkyl or C C 1 -C 4; 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 formula I according to claim 1, in which R1 is C1-C4alkyl, R ² is C 1 -C 10 alkyl, C 1 -C 6 haloalkyl, C 1 -C 13 haloalkyl, C 3 -C 8 cycloalkyl optionally substituted with C 1 -C 4 alkyl 105 carbon atoms or haloalkyl having 1 to 4 carbon atoms; 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 (C1-C4) alkoxyalkyl in the alkoxy and alkyl moieties, and X represents an oxygen atom and Y represents an oxygen atom. A process for the preparation of substituted triazolinones of formula I according to claim 1 wherein R 1 represents a hydrogen atom, a straight or branched alkyl group having from 1 to 2 carbon atoms; C 8 -C 7 -cycloalkyl, C 3 -C 7 -cycloalkyl, optionally at least once, same or different halogen substituted C 6 -C 10 aryl or C 1 -C 4 haloalkyl of up to 9 identical or different atoms halogen, in 750 / 93H-1.3.1998 106 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 -alkyl, 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 carbon atoms in the alkyl moieties, dialkylaminoalkyl of 1 to 6 carbon atoms in the alkyl moieties parts, or in each case at least once the same or different substances bold cycloalkyl or cycloalkylalkyl 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 carbon atoms , (C 1 -C 4) haloalkyl, (C 1 -C 4) haloalkyl (C 1 -C 9) halogen or straight-chained or branched (C 1 -C 5) haloalkenyl, C 1 -C 5 haloalkenyl, 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 the substituents of the alkyl group are, where appropriate, the considerations of atoms 107 halogen and a substituent for an aryl group is 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, X represents an oxygen atom or a sulfur atom, and Y represents an oxygen atom or a sulfur atom, characterized in that: (a) reacting the hydrazones of formula (II) 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 1 H-triazolinones of formula III 108 in which R * and X are as defined in claim 1, with iso (thio) cyanates of formula IV r2. _N = c = Y (IV) in which 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 c) reacting the triazolinones of formula V (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 formula VI R ² - NH ₂ (VI), 109 in which 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 preparation of a compound of formula characterized in that the compound of formula ( ^OH ) 3 is reacted CHCH. 0 = C - NH - CH (CH ₂ ) ₉ CH ₂ is treated with an acid, optionally in the presence of a diluent, or reacted with a compound of formula 110 HC ΝΗ _? ^3κ - with a compound of the formula optionally in the presence of a diluent and optionally in the presence of an auxiliary reagent. 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 750 / 93H-1.3.1998 111 in which R ^{@ 1} represents a hydrogen atom, a straight or branched alkyl group s C 1 -C 8 -cycloalkyl, C 3 -C 7 -cycloalkyl, optionally at least once, same or different halogen substituted C 6 -C 10 aryl or C 1 -C 4 haloalkyl and up to 9 identical 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 , a haloalkenyl group having 2 to 8 carbon atoms and 1 to 15 identical or different atoms Halogen, cyanalkyl having 1 to 8 carbon atoms, alkoxyalkyl having 1 to 6 carbon atoms in the alkoxy and alkyl moieties, alkoxycarbonylalkyl having 1 to 6 carbon atoms in both the alkoxy and alkyl moieties, alkoxycarbonylalkenyl (C 1 -C 6) alkoxy and (C 2 -C 6) alkenyl, (C 1 -C 6) alkylaminoalkyl, (C 1 -C 6) dialkylamino (C 1 -C 6) alkyl group or in each case optionally at least once the same; or a differently substituted 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 (C 1 -C 4) alkyl group carbon, a (C 1 -C 4) haloalkyl group or (C 1 -C 4) -alkyl, (C 1 -C 4) -haloalkyl, (C 1 -C 9) or different (C 1 -C 4) haloalkenyl; R @ ² denotes optionally at least one, equally 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 chain of 1 to 5 identical or different halogen atoms; in a branched alkyl moiety, wherein optionally halogen atoms are suitable as alkyl substituents, and halogen, straight or branched (C 1 -C 6) alkyl or (C 1 -C 6) alkoxy are suitable as aryl substituents, R 3 and R 4 are each independently hydrogen, C 1 -C 4 alkyl, phenyl or benzyl, X represents an oxygen atom or a sulfur atom, 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: Y = C - O - R ⁵ (Va), _R 1 - represents an alkyl group having 1 to 4 carbon atoms. R @ 5 represents a C1 -C4 alkyl group or a phenyl or benzyl group optionally substituted one to three times, in each case halogen, cyano, nitro, alkyl, alkoxy or alkylthio, in each case C1 -C4 substituents which may be mentioned as substituents , haloalkyl in 750 / 93H-1.3.1998 113, haloalkoxy or haloalkylthio having in each case 1 to 11 carboxylic acids 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 in which _R 1-1 represents an alkyl group 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 or a phenyl or benzyl group optionally substituted one to three times, with halogen, cyano, nitro, alkyl, alkoxy or C1 -C4 alkylthio, haloalkyl being suitable as substituents. haloalkoxy or haloalkylthio having in each case 1 to 4 carbon atoms, and X and Y are each independently O or S. in 750 / 93H-1.3.1998 114 A herbicidal composition, characterized in that it contains, as active ingredient, at least one substituted triazolinone of the formula I according to claim 3 or 4, The herbicidal composition according to claim 10, characterized in that it contains carriers and / or surfactants. Use of substituted triazolinones of the general formula I according to claims 3 or 4 for weed control.