DD284581A5 - HERBICIDE MEDIUM - Google Patents

Abstract

The invention relates to herbicidal compositions which contain, in addition to extenders and / or surface-active agents, at least one triazolinone of the formula I. The novel agents can z. B. be used to combat monocot and dikotyler weeders. Depending on the concentration, they are suitable for total weed control and for weed control in permanent crops. {Herbicides; active ingredient; triazolinones; Method; Use; combating}

Description

Herbicidal agent application area, the JSrrindung

The invention relates to herbicidal compositions containing as active ingredient at least one substituted triazolinone of formula 1.

Cha characteristics of the known prior art

It is known that certain nitrogen heterocycles, such as, for example, 4-amino-3-methyl-6-phenyl-1,2,4-triazin-5-one or N-isobutyl-2-oximidazoliain-i-carboxamide (cf. For example, DE-OS 2 j64 W and E. Regulator "Ghemie the Crop Protection and 'pesticides Volume 5, 219 (1977)) herbicidal properties ousitzen.

The herbicidal activity of these prior art compounds against problem weeds, however, is not completely satisfactory in all fields of application as well as their compatibility with important crops.

"Also known are certain substituted" iriazolinones, such as, for example, 2- (N, H-dimethylcarbamoyl) -3-phenyl-4-amino-1,2, -triazolin-5-one (cf. Hetorocycl Chem 17, 1591 - 1S96 / 1980 / j Org. Mass. Spectram 14, 369-373 / 1979 /).

The effectiveness of these previously known riazolinones as herbicides is hitherto unknown.

- 2 objective of the invention

The substituted triazolinones used according to the invention exhibit a considerably higher herbicidal potency over problem weeds than the compounds known from the prior art.

Explanation of the reading of the invention

The object of the invention is to provide new herbicidal gowns.

Ss were new substituted triazolinones of the general formula (I),

(D

Ш - H ²

in v / elcher

3 ¹ represents hydrogen, alkyl, alkenyl, alkynyl, haloalkyl, vinylalkenyl, haloalkynyl, alkoxyalkyl, cycloalkyl, cycloalkylalkyl, or for each of the optionally substituted aralkyl or aryl,

ρ H for .. 'assersrof, alkyl, alkenyl, alkynyl, zlalogenalkyl, haloalkeny-1, haloalkynyl, cyanoalkyl, hydroxyalkyl, alkoxyalkyl, alkoxycarbonylalkyl, Alkf o: cycarbonylalkenyl, alkylaminoalkyl, dialkylaminoalkyl, each optionally substituted cycloalkyl, Cyc1oalkylalk _v 1,

Cycloalkenyl or cycloalkenylalkyl, optionally substituted heterocyclylalkyl, in each case optionally substituted aralkyl, aroyl, aryl, aralkyloxy or aryloxy, represents alkoxy, alkenyloxy or alkynyloxy,

X is oxygen or sulfur and Y is oxygen or sulfur,

found

 15

Depending on the nature of the substituents R ¹ and R ^{1, the} compounds of the formula (I) may optionally be present as geometric and / or optical isomers or mixtures of isomers of different composition. Both the pure isomers and the isomer mixtures are claimed according to the invention.

Furthermore, it has been found that the new substituted triazolinones of the general formula (I), 25

(I)

in which

R ^{1 is} hydrogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, alkoxyalkyl,

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Cycloalkyl, cycloalkylalkyl, tetrahydrofuranyl, tetrahydrofuranylalkyl or each optionally substituted aralkyl or aryl,

R ^{2 represents} hydrogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, cyanoalkyl, hydroxyalkyl, alkoxyalkyl, alkoxycarbonylalkyl, alkoxycarbonylalkenyl, alkylaminoalkyl, dialkylaminoalkyl, in each case optionally substituted cycloalkyl, cycloalkylalkyl, cycloalkenyl or cycloalkenylalkyl, for example as appropriate substituted heterocyclylalkyl, in each case optionally substituted aralkyl, aroyl, aryl, aralkyloxy or aryloxy, or represents alkoxy, alkenyloxy or alkynyloxy,

X is oxygen or sulfur and У is oxygen or sulfur,

gets when you 25

(a) hydrazones of formula (II), R ¹ ^ ₁ № "N = C

⁴

N ^ N ^ x (II)

in which 35

NH

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

R ³ and R ⁴ independently of each other for

Hydrogen, alkyl, aralkyl or aryl

stand, 10

with an acid, if appropriate in the presence of a diluent,

or if you are 15

(b) 1H-triazolinones of the formula (III),

(III)

I

in which

R ¹ and X have the abovementioned meaning,

with iso (thio) cyanates of the formula (IV),

R ² -N = C = Y (IV)

in which

R ² and Y have the abovementioned meaning, 35

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if appropriate in the presence of a diluent and if appropriate in the presence of a reaction auxiliary,

or if you are

(c) triazolinones of formula (V), R ¹ ^ ₁ N- "NH _?

^ _X (V)

in which

R, X and Y are as defined above, 20

and R ^{5 is} alkyl, aryl or arylalkyl, with amines of the formula (VI),

R ² -NH ₂ (VI)

in which 30 F ^{u has} the meaning given above,

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if appropriate in the presence of a diluent and if appropriate in the presence of a reaction auxiliary.

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

Surprisingly, the substituted triazolinones of the general formula (I) according to the invention exhibit a considerably higher herbicidal potency over problem weeds than the nitrogen heterocycles known from the prior art, such as, for example, the 4-amino-3-methyl-6-phenyl-1,2,4-diene. triazin-5-one, which are chemically and functionally obvious compounds.

The substituted triazolinones of the invention are generally defined by the formula (I). Preference is given to compounds of the formula (I) in which

R * is hydrogen, in each case straight-chain or branched alkyl having 1 to 8 carbon atoms, alkenyl having 2 to 8 carbon atoms, alkynyl having 2 to 8 carbon atoms, haloalkyl having 1 to 8 carbon atoms and 1 to 17 identical or different halogen atoms, haloalkenyl having 2 to 8 carbon atoms and 1 to 15 identical or different halogen atoms, halogenoalkynyl having 2 to 8 carbon atoms and 1 to 13 identical or different halogen atoms, alkoxyalkyl having 1 to 6

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Carbon atoms in the individual alkyl moieties, for cycloalkyl or cycloalkylalkyl with 3 to

7 carbon atoms in Cycloalkyltei1 and optionally 1 to 6 carbon atoms in the straight-chain or branched alkyl moiety, for tetrahydrofuranyl or tetrahydrofuranylalkyl having optionally 1 to 4 carbon atoms in the straight-chain or branched alkyl moiety or for each optionally mono- or polysubstituted by identical or different aralkyl or aryl each having 6 to 10 carbon atoms in the aryl moiety and optionally 1 to 6 carbon atoms in the straight-chain or branched alkyl moiety, suitable as aryl substituents in each case: halogen, cyano, nitro and in each case straight-chain or branched alkyl, alkoxy, alkylthio, haloalkyl, haloalkoxy or haloalkylthio each having 1 to 4 carbon atoms and optionally

1 to 9 identical or different halogen atoms,

R ^{6 is} hydrogen, in each case straight-chain or branched alkyl having 1 to 18 carbon atoms, alkenyl having 2 to 8 carbon atoms, alkynyl having

2 to 8 carbon atoms, haloalkyl with 1 to

8 carbon atoms and 1 to 17 identical or different halogen atoms, haloalkenyl or haloalkynyl having in each case 2 to 8 carbon atoms and 1 to 15 or 13 identical or different halogen atoms, cyanoalkyl having 1 to 8 carbon atoms, hydroxyalkyl having 1 to 8 carbon atoms

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atoms and 1 to 6 hydroxy groups, alkoxyalkyl, alkoxycarbonylalkyl or alkoxycarbonylalkenyl each having up to 6 carbon atoms in the individual alkyl or alkenyl moieties, alkylaminoalkyl or dialkylaminoalkyl each having 1 to 6 carbon atoms in the individual alkyl moieties, cycloalkyl having 11 carbon atoms or each optionally monosubstituted or polysubstituted by identical or different substituents cycloalkyl, cycloalkylalkyl, cycloalkenyl or cycloalkenylalkyl having in each case 3 to 8 carbon atoms in the cycloalkyl or

¹ S cycloalkenyl and optionally 1 to 6 carbon atoms in the alkyl moiety, where as substituents in question: halogen, cyano and in each case straight-chain or branched alkyl or halogenoalkyl each having 1 to 4 carbon atoms and optionally 1 to 9 identical or different halogen atoms or straight-chain or branched Haloalkenyl having up to 4 carbon atoms and 1 to 5 identical or different halogen atoms or each doubly linked alkanediyl, or alkenediyl having in each case up to 4 carbon atoms JR ^ also for in the heterocyclyl optionally mono- or polysubstituted by identical or different substituted heterocyclylalkyl having 1 to 6 carbon atoms in the straight-chain or branched alkyl part and 1 to 9 carbon atoms and 1 to 3 heteroatoms - in particular nitrogen, oxygen and / or sulfur - in Heterocyclyltei1, where as substituents come into question: halogen, cyano, nitro, and in each case straight-chain s or branched alkyl, alkoxy, alkylthio, haloalkyl, haloalkoxy, haloalkyl

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thio or alkoxycarbonyl each having 1 to 5 carbon atoms and optionally 1 to 9 identical or different halogen atoms; R ^{2 is} in each case also in each case straight-chain or branched alkoxy having 1 to 8 carbon atoms "alkenyloxy having 2 to 8 carbon atoms or alkynyloxy having 2 to 8 carbon atoms

¹ ^ lenstoffatomen and finally each optionally optionally mono- or polysubstituted, identically or differently substituted aralkyl, aroyl, aryl, aralkyloxy or aryloxy, each having 6 to 10 carbon atoms in the aryl moiety and optionally 1 to 8 carbon atoms in the straight-chain or branched alkyl moiety, where as alkyl substituents optionally halogen and cyano come into question and being suitable as aryl substituents in each case: halogen, cyano, nitro, hydroxy, in each case straight-chain or branched alkyl, alkoxy, alkylthio, haloalkyl, haloalkoxy, haloalkylthio, alkylsulfinyl, alkylsulfonyl, haloalkylsulfinyl, haloalkylsulfonyl, alkanoyl or alkoxycarbonyl each having 1 to 6 carbon atoms in the alkyl portion and optionally 1 to 9 same or different halogen atoms, cycloalkyl of 3 to 6 carbon atoms and phenoxy; or R ^{2 is} benzyl with -O-CH 2 -O- group fused in the phenyl moiety,

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

Particular preference is given to compounds of the formula (I) in which

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R ^{1 is} hydrogen, methyl, ethyl, η- or i-propyl, n-, i-, s- or t-butyl, n- or i-pentyl, n- or i-hexyl, allyl, propargyl, straight-chain or branched haloalkyl having 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms, in particular fluorine, chlorine or bromine, for methoxymethyl, ethoxymethyl, propoxymethyl, cyclopentyl, cyclohexyl, cyclopropyl, cyclopropylmethyl, cyclohexylmethyl, cyclohexylethyl, tetrahydrofuranyl, tetrahydrofuranylmethyl or for each optionally monosubstituted to trisubstituted by identical or different substituents benzyl or phenyl, wherein suitable substituents are: fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, η- or i-propyl, η-, i-, s- or t Butyl, methoxy, ethoxy, methylthio, trifluoromethyl, trifluoromethoxy or trifluoromethylthio,

R ^{2 is} hydrogen, methyl, ethyl, η- or i-propyl, η-, i-, s- or t-butyl, in each case straight-chain or branched pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, for allyl, in each case straight-chain or branched butenyl, pentenyl or hexenyl, propargyl, in each case straight-chain or branched butynyl, pentinyl or hexynyl, for straight-chain or branched haloalkyl having 1 to 8 carbon atoms and 1 to 9 identical or different halogen atoms, in particular fluorine, chlorine or bromine, in each case straight-chain or branched haloalkenyl or haloalkynyl each having 3 to 8

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Carbon atoms and 1 to 3 halogen atoms, in particular fluorine or chlorine, in each case straight-chain or branched cyanoalkyl having 1 to 6 carbon atoms in the alkyl moiety, hydroxyalkyl having 1 to 6 carbon atoms and 1 to 3 hydroxy groups, alkoxyalkyl, alkoxycarbonylalkyl or alkoxycarbonylalkenyl, alkylaminoalkyl or dialkylaminoalkyl with in each case to to 4 carbon atoms in the individual alkyl or alkenyl or for each optionally mono- to trisubstituted by identical or different substituted cyclopropyl, cyclopropylmethyl , cyclopropylethyl , cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclohexylmethyl, cyclohexylethyl, cyclohexenyl or cyclohexenylmethyl, where as substituents in each case: fluorine, chlorine, bromine, methyl, ethyl, η- or i-propyl, n-, i-, s- or t-butyl, cyano, methanediyl, ethanediyl, butanediyl or butadienediyl or DichloralIyIweiterhin for in heterocyclyl optionally - up to three times, the same or different subst ithiertes heterocyclylmethyl, heterocyclylpropyl or heterocyclylethyl, where as heterocycles each come into question:

N_4-N, -M *

ILJi "J)

-N

-N

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-la

-О

-NO or -NNH

where Z is in each case oxygen or sulfur and in each case the following are suitable as substituents:

Fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, methylthio, trifluoromethyl, trifluoromethoxy or trifluoromethylthio;

R 1 additionally being in each case straight-chain or branched alkoxy having 1 to 6 carbon atoms, alkenyloxy having 3 to 6 carbon atoms or alkynyloxy having 3 to 6 carbon atoms or benzyl, phenylethyl, optionally substituted once to three times, identically or differently, optionally straight-chain or branched Phenylpropyl, phenylbutyl, phenylpentyl, phenylhexyl, phenylheptyl, phenylcyanmethyl, phenylcyanoethyl, phenylcyanopropyl, benzyloxy, phenylethyloxy, phenoxy, benzoyl, phenyl or naphthyl, in each case being suitable as phenyl substituents: fluorine, chlorine, bromine, hydroxyl, cyano, nitro, methyl, Ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, methylthio, trifluoromethyl, trifluoromethoxy, trifluoromethylthio, trifluoromethylsulfinyl, trifluoromethylsulfonyl, methylsulfinyl, methyl-

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sulfonyl, acetyl, propionyl, methoxycarbonyl, ethoxycarbonyl, cyclohexyl or phenoxy,

X is oxygen or sulfur and Y is oxygen or sulfur.

Very particular preference is given to compounds of the formula (I) in which

R ^{1 is} hydrogen, methyl, ethyl, η- or i-propyl, methoxymethyl, ethoxymethyl or propoxymethyl,

R ² represents hydrogen, represents in each case optionally mono- to trisubstituted by ² ^ fluorine and / or chlorine-substituted methyl, ethyl, η- or i-propyl, n-, i-, s- or t-butyl, allyl, propargyl, in each case straight or branched pentyl, hexyl, heptyl, octyl, butenyl; Pentenyl, hexenyl, butynyl,

² ^ is pentynyl or hexynyl; furthermore in each case optionally monosubstituted to trisubstituted by identical or different fluorine, chlorine, methyl, ethyl and / or cyano, cyclopropyl, cyclopentyl, cyclohexyl, cyclohexenyl, cyclopropylmethyl, cyclopropylethyl, cyclohexylmethyl, cyclohexylethyl or cycloheptyl, and finally benzyl, phenylethyl or phenyl stands,

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X is oxygen or sulfur and 5

Y is oxygen or sulfur.

Specifically, in addition to the compounds mentioned in the preparation examples, the following substituted triazolinones of the general formula (I) may be mentioned:

  - (i,

i-p2

_R l _R 2

CH ₃ - <H

CH ₃

CH ₃

CH ₃ CH ₃

CH ₃ -C (CH ₃ ) ₃

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R ¹

^C 2 ^H 5 ^С 2 ^Н 5

C ₂ H ₅

CoH

₂ H ₅

C _{(CH3) 3} H

-С (СН ₃ ) ₃ -C (CH ₃ J ₃ -С (СН ₃ ) ₃

C ₂ H ₅ -s_ / CH ₃ ^С 2 ^Н ₅ - ^cH 4D S configuration ion H -C (CH ₃ J ₃ H - <H>

0 0 S

0 s

0 0

0 S 0

0 0

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10 15 20 25 30

H H H

CH,

CH-

CH ₃

I ³

-C-CH ₂ -OCHo CH ₃

-CH-CH ^

I CH ₃

CH ₃

CH ₃ CH ₃

-C-CH ₂ -N CHo

-CKl CH-CoHc

II ²

CH ₃ CH ₃

0 S 0

S 0 S

35

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10

15

CH-

CH-

CH-

-С

CH-

СН-

-C

CH-

- 18 -

OCH

CH-

2 ^Н 5

20

25

CH-

CH-

30

CH,

CH-

-с-сн <

CH-

CH-

CH-CH-

CH-

-C

35

CH-

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R ¹ R ²

CH ₃

CHo-CH-CoHc

! ₍ 2

CH ₃

CH ₃ -С-СН ₂ -СН <

20 CH ₃ CH ₃ 25 сн ₃

CH ₃

CH ₃ CHO CH ₃

CHo-C C-CH

||

CH ₃ CH ₃ CHo

I ³ -C-CH ₂

CH ₃ -CH-COOCoH

I сн ₃

CH ₃ -CH <

(CH ₂ ) 2 "C ₂ H ₅

CHo -C-CHo, ₍

^С 2 ^Н 5

CH-CH ₂ -CH ₂ -CH- (СН ₂ ) ₂ -СН ₃ О CH ₃ CH ₃ (CH ₂ ) ₂ -NH ₃

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10

CH:

Cl

CFr

-CH ₂ -CH ₂

35

CH -: - CH ₂ -CH ₂

15

CH: OCH

-CH ₂ -CH ₂ - (^ у} - OCH

20

ochr

25

CHr

CHRCHR

Cl

30

CHr

CHrCl "Cl

Cl ⁵ Cl

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35

Cl

10 CH.

15

CH.CH.

CH.

20

CH.

CH.CH.

CH.

-CH- /

CH.

25

CH. CH- (CHo) o-CHo ^С 2 ^Н 5

CH. сн- (сн ₂ ) ₂ -сн ₃ ^С 2 ^Н 5

30

СИ- ~ (СН ₂ ) ₃ -СН '

CH

CH-

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CH-;

CH.

CH-

CH-

CH-

- 22 -

CH-

CH-CHR

-CH <

CH-CHO

I

CH ₃

-CH-CH ₂ -N CH ₃

-sn ₂ -sn <

ochr

ochr

CHr

-CH-C-CH ₃ CN CH ₃

CHr

-CH-CH ^ -C

сн _:

-CH ₂ CH ₃

I ^э

-C-C CHo

CH ₃ R configuration

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10

15

20

CH-

CH,

CH,

CH,

CH-

CH,

CH,

CH ₃ S configuration

-CH-CH <

CH,

CH,

-CH-CH ₂ -OCH ₃

- (CH ₂ J ₂ -CH ₃

CH,

CH,

CH ₂ -CH <

CH-

CH-

-CH-C ₂ H ₅ CHo

25

30

35

CH,

CH-

CH-

CH,

CH-

CH, (CH ₂ ) ₂ -CH ₃ (CHO 'o. -CH ₃

-CH ₂ -CH <

CH-

CH-

-CH-C ₂ H ₅

S S

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If, for example, 1- (N-isobutylcarbamoyl) -4-isopropylidenimino-3-methyl-l, 2,4-lriazolin-5-one is used as starting compound, the course of the reaction of process (a) according to the invention can be represented by the following equation:

^ CH ₃

H ₂ O / H

- (сн ₃ ) ₂ со

NH-CH ₂ -CH (CH ₃ ) 2

NH-CH ₂ -CH (CH ₃ ) 2

If, for example, 4-amino-3-methyl-l, 2,4- (IH) -triazolin-5-one and t-butyl isocyanate are used as starting materials, the course of the reaction of process (b) according to the invention may be represented by the following equation:

(CH ₃ J ₃ CN = C = O

O = C-NH-C (CH ₃ J

₃ J ₃

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If, for example, 1-ethoxycarbonyl-4-amino-3-methyl-l, 2,4-triazol-5-o-o and Ν, Ν-diethyl-1,3-propanediol are used as starting materials, the reaction sequence of the process according to the invention can be ( c) represent by the following formula scheme:

C ₂ H ₅

Π J + H ₂ N-CH ₂ -CH ₂ -CH ₂ -N *

N ^ N ^ CoHc

j -40 2 5

O = C-OC ₂ H ₅ 15

- C ₂ H ₅ -OH

O = C-NH-CH ₂ -CH ₂ -CH ₂ -N ^

^C 2 ^H 5

The for carrying out the method according to the invention

(a) Hydrazones required as starting materials are generally defined by the formula (II). In this formula (II), R, R, X and У are preferably those

Residues already described in connection with the description 25

the substances of the formula (I) according to the invention have been mentioned as being preferred for these substituents.

R 1 and R 3 are preferably each independently of one another hydrogen, straight-chain or 30

branched alkyl having 1 to 4 carbon atoms or for phenyl or benzyl.

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The hydrazones of the formula (II) are not yet known, but are also the subject of the present invention, but they are obtained in analogy to known processes (cf., for example, Acta Pol. Pharm, 38, 153-162 C1981] or CA. 9J5: 20384Ij), for example if 1-unsubstituted 4-amino-triazolinones of the formula (III)

(Ill) н

in which R and X have the abovementioned meaning,

with aldehydes or ketones of the formula (VII),

R ³ >.

^ C = O (VII)

^R

in which

R ³ and B 1 have the abovementioned meaning,

if appropriate in the presence of a diluent such as, for example, dichloromethane or toluene and

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if appropriate in the presence of a catalyst such as p-toluenesulfonic acid at temperatures between 40 ° C and 120 ⁰ C and the thus available 1 unsubstituted triazolinone hydrazones of the formula (VIII),

.

R ⁴ (VIII)

H in which

R 1, R ⁴ , R ⁴ and X have the abovementioned meaning,

either in a subsequent 2 stage with iso (thio) cyanates of the formula (IV),

R ² -N = C = Y (IV)

in which 25

R ² and Y have the abovementioned meaning,

optionally in the presence of a diluent such as oichloromethane or dioxane and optionally in the presence of a reaction auxiliary such as triethylamine at temperatures between 50 ⁰ C and 150 ⁰ C;

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or alternatively in a subsequent second stage with (thio) chloroformates of the formula (IX),

₅ II

R ⁵ -OC-C1 (IX) in which

R ^{5 is} alkyl, aryl or arylalkyl and

Y has the meaning given above, 15

reacting 20 ⁰ C and + 40 ° C, and the thus obtained union triazolinones of the formula (X), - optionally in the presence of a diluent such as tetrahydrofuran and optionally in the presence of a reaction auxiliary such as sodium hydride or Kaiium t-butylate at temperatures between

in which

R ¹ , R ³ , R ⁴ , R ⁵ , X and Y are as defined above

to have,

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in a subsequent third stage with amines of the formula (VI),

R ² -NH ₂ (VI)

in which 10

R ^ has the meaning given above,

optionally in the presence of a diluent such as tetrahydrofuran and optionally in the presence of a base such as sodium hydroxide or potassium hydroxide at temperatures between 20 ⁰ C and 50 ⁰ C reacted.

It is also possible and optionally advantageous to react the 1-unsubstituted triazolinone hydrazones of the formula (VIII) with (thio) chloroformates of the formula (IX) and then reacting the thus obtained triazolinones (X) with amines of the formula (VI ) in a reaction step in a so-called one-pot process (see Example 3).

The 1-unsubstituted 4-amino-triazolinones of the formula (III) are known or obtainable in analogy to known processes (cf. for example J. Heterocycl Chem 16 403 [1979];.... J. Heterocycl Chem 1691 Y7_ _t [.. 19803; Europ, J. Med. Chem. G8, 215 [1983]; Chem. Ber. 9j5, 3025 [1965] or Liebigs Ann. Chem. 637, 135 [I960]).

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

The 1-unsubstituted triazolinone hydrazones of the formula (VIII) are known in large part (cf., for example, J. Heterocycl Chem 2J3, 77-80 [19833, J. Heterocycl Chem 16.] 403-407 [1979]. Chim. Acta., Tur., 7, 269-290 [1979]; J. Chem. Soc.j Perkin Trans II, 1973. 9-11; J. Org. Chem., 36, 2190-2192 [1971]. ).

The (thio) chloroformates of the formula (IX) are * * ** generally known compounds of organic chemistry.

The triazolinones of the formula (X) mentioned as intermediates are known in some cases (cf., for example, Acta.

Pharm. 38, 153-162 [1981] and CA. 95: 20384Ij). 20

Not yet known and also the subject of the present application are triazolinones of the formula (Xa)

Y = COR ⁵

in which R ¹ " ^{1 is} alkyl and

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

to have. 35

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R ¹ " ¹ preferably represents straight-chain or branched alkyl having 1 to 4, in particular 1 to

3 carbon atoms; very particularly preferably R ¹ " ^{1 is} methyl,

R ³ and R ⁴ are preferably each independently hydrogen, straight or

branched alkyl having 1 to 4 carbon atoms or for phenyl or benzyl »

It preferably represents straight-chain or branched alkyl having 1 to 4 carbon atoms or optionally mono- to trisubstituted by identical or different substituents phenyl or benzyl, where as substituents in question: halogen, cyano, nitro, in each case straight-chain or branched alkyl, alkoxy or Alkylthio with .ieweils 1 to 4 carbon atoms or in each case straight-chain or branched haloalkyl, haloalkoxy or halogenoalkylthio each having 1 to

4 carbon atoms and 1 to 9 same or different halogen atoms;

R ^ is in particular methyl, ethyl, η- or i-propyl, n-, i-, s- or t-butyl or optionally mono- to disubstituted by identical or different substituents phenyl or benzyl, which are each suitable as substituents : Fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, η- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy,

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η- or i-propoxy, methylthio, trifluoromethyl, trifluoromethoxy or Trifluormethylthioj

X and Y are each independently oxygen and sulfur, preferably

oxygen

 10

The 1H-triazolinones required as starting materials for carrying out the process (b) according to the invention are generally defined by the formula (III). In this formula (III), R and X preferably represent those radicals which have already been mentioned in connection with the description of the substances of the formula (I) according to the invention as being preferred for these substituents.

The 1H-triazolinones of the formula (III) are known or obtainable in analogy to known processes (cf., for example, J. Heterocycl, Chem., JJ, 403 [1979]; J. Heterocycl., Chem., 17, 1691 [19803, Europ. J. Med. Chem. 18, 215 [1983], Chem. Ber. 98., 3025 [1965]; Liebigs Ann. Chem. 637 .

[I960])

 25

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

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The iso (thio) cyanates of the formula (IV) are largely known compounds of organic chemistry. The compounds 2,2,2-trifluoroisopropylcyanate and 2,2,2-trifluoro-1,1-dimethylethylcyanate are not yet known, but can be prepared by known methods. For example, iso (thio) cyanates are obtained by reacting the corresponding amines with phosgene, if appropriate in the presence of a base such as, for example, triethylamine (cf., for example, DE-OS 28 04 082, DE-OS 25 12 514, US-P 35 84 028 , US Pat. No. 2,706,753, US Pat. No. 3,311,654, JP 50/29599, Synthesis 1985, page 682 or J. Am. Chem. Soc. ZZ 1901-1902 (1955)).

The triazolinones required as starting materials for carrying out the process (c) according to the invention are generally defined by the formula (V). In this formula (V), R *, X and Y preferably represent those radicals which have already been mentioned in connection with the description of the substances of the formula (I) according to the invention as being preferred for these substituents.

R ° preferably represents straight-chain or branched alkyl having 1 to 4 carbon atoms or represents optionally mono- to trisubstituted by identical or different substituents phenyl or benzyl,

where as substituents each request come:

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

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R *> is in particular methyl, ethyl, η- or i-propyl, η-, i-, s- or t-butyl or optionally mono- to disubstituted by identical or different substituents phenyl or benzyl, where as substituents in each case fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, η- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, methylthio, trifluoromethyl , Trifluoromethoxy or trifluoromethylthio.

The triazolinones of formula (V) are known in part (see, e.g., J. Heterocycl Chem IZ, 1691-1696 [1980]).

Not yet known and also subject matter of the present application are triazolinones of the formula (Va),

Il I -

(Va)

in which

R is alkyl, preferably straight-chain or branched alkyl having 1 to 4, in particular having 1 to 3 carbon atoms, very particularly preferably methyl and

R ^, X and Y are as defined above.

They are obtained in analogy to the preparation of the known compounds of formula (V), if lH-triazolinones of the formula (IIIa),

Le A 25 302-foreign countries

I (Ilia)

in which 10

R ¹ " ¹ and X have the meaning given above»

with (thio) chloroformates of the formula (IX),

R ⁵ -OC-C1 (IX)

Il

in which

R 'and Y have the meaning given above,

optionally in the presence of a diluent such as tetrahydrofuran and optionally in the presence of a reaction auxiliary such as potassium t-butoxide or sodium hydride at temperatures between - 20 ° C and + 40 ° C (see also the Preparation Examples).

The 1H-triazole inones of the formula (IIIa) are known or obtainable in analogy to ЪекаппЬеп processes (cf., for example, J. Heterocycl, Chem., JJb, 403 [1979], J. Heterocycl., Chem., 1791, [1980]; .. J. Chem med IJ _- 215 [1983]; Chem, 9JS, 3025 [1965]; Liebigs Ann Chem 637 135 [I960]).....

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Suitable acids for carrying out process (a) according to the invention are all inorganic and organic acids which can usually be used for hydrazone cleavings. Preferably used inorganic mineral acids such as hydrochloric acid, sulfuric acid or phosphoric acid.

Suitable diluents for carrying out the process (a) according to the invention 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 as diluent

The reaction temperatures can be carried out

of the process (a) according to the invention can be varied within a substantial range. In general, one works at temperatures between 20 ° C and 150 ⁰ C, preferably at temperatures between 50 ° C and 120 ⁰ C.

The process (a) according to the invention is usually carried out at atmospheric pressure or under reduced pressure. Working under reduced pressure, so come pressure ranges between 20 and 400 mbar, preferably between 100 and 200 mbar in question.

To carry out process (a) according to the invention, in general from 1 to 50 mol, preferably from 1 to 20 mol, of acid are employed per mole of hydrazone of the formula (II)

Le A 25 302-foreign countries

on. In this case, the hydrazone of the formula (II) is dissolved in a suitable amount of diluent, then the required amount of acid is added and the mixture is concentrated slowly under reduced pressure for several hours.

In a particular embodiment, it is also possible to carry out the process (a) according to the invention and the preparation of the required precursors of the formula (II) in a reaction step in a so-called one-pot process. 15

It is possible to choose as starting compounds the triazolinones of the formula (X) and to react them one after the other in a one-pot process with amines of the formula (VI) and then with acid according to the process (a) according to the invention (compare also the preparation examples) or Alternatively, to choose as starting compounds, the triazoline hydrazones of the formula (VIII) and these successively in a one-pot process with (thio) chloroformates of the formula (IX), then with

Amines of the formula (VI) and then reacted with acid according to the inventive method (a).

Suitable diluents for carrying out process (b) according to the invention are inert organic solvents. These include in particular aliphatic, alicyclic or aromatic, optionally 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,

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Tetrahydrofuran or ethylene glycol dimethyl or diethyl 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.

The process (b) according to the invention is optionally carried out in the presence of a suitable reaction auxiliary. As such, all customary inorganic or organic bases are suitable. These include, for example, tertiary amines, such as triethylamine, Ν, Ν-dimethylaniline, Ν, Ν-diethylbenzylamine, N, N-dimethylcyclohexylamine or dibutyltin dilaureate, pyridine, N, N-dimethylaminopyridine, diazabicyclooctane (DABCO), diazabicyclononene (DBN) or diazabicycloundecene (DBU ).

The reaction temperatures can be varied within a substantial range when carrying out process (b) according to the invention. In general, one works at temperatures between ^{0 0} C and 150 ⁰ C, preferably at

Temperatures between 20 ⁰ C and 100 ⁰ C. 25

For carrying out the process (b) according to the invention, 1.0 to 2.0 mol, preferably 1.0 to 1.5 mol, of I iso (thio) cyanoate of the formula (IV) and optionally 0.001 to 2.0 are generally employed per mole of 1H-triazolinone of the formula (III) Mol, preferably 0.001 to 1.0 mol of reaction auxiliary.

The reaction procedure, work-up and isolation of the reaction products is carried out according to generally customary

methods

 35

Le A 25 302-foreign countries

Suitable diluents for carrying out the process (c) according to the invention are inert organic solvents. These include in particular aliphatic, alicyclic or aromatic, optionally halogenated hydrocarbons, such as, for example, benzene, benzene, toluene, xylene, chlorobenzene, petroleum ether,

¹ ^ hexane, cyclohexane, dichloromethane, chloroform, carbon tetrachloride, ethers such as diethyl ether, dioxane, tetrahydrofuran or ethylene glycol dimethyl or diethyl 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.

If appropriate, the process (c) according to the invention can be carried out in the presence of a suitable reaction auxiliary. As such, all customary inorganic or organic bases are suitable. These include, for example, alkali metal hydroxides such as sodium hydroxide or potassium hydroxide, Alkalimetal1 carbonates such as sodium carbonate, potassium carbonate or sodium bicarbonate, and tertiary amines such as triethylamine, N, N-Dimethylani1 in, pyridine, N, N-dimethylaminopyridine, diazabicyclooctane (DABCO), diazabicy-

clonons (DBN) or diazabicycloundecene (DBU). 30

The reaction temperatures can in carrying out the process (c) in a larger

Le A 25 302-foreign countries

Range can be varied. In general, one works at temperatures between ^{0 0} C and 120 ⁰ C, preferably at temperatures between 20 ⁰ C and 50 ⁰ C.

For carrying out the process (c) according to the invention, in each case, in each case, per mole of triazolinone of the formula (V)

Ю common 1.0 to 5.0 moles, preferably 1.0 to 2.5 moles of amine of formula (VI) and optionally 1.0 to mol, preferably 1.0 to 1.2 moles of reaction auxiliary

 The Reaktionsdurchfuhrung, workup and isolation of the reaction products by commonly used methods.

In a particular embodiment, it is also possible to carry out the process (c) according to the invention and the preparation of the required precursors of the formula (V) in a reaction step in a so-called one-pot process.

It starts from lH-triazolinones of the formula (III) and reacts them one after the other in a one-pot process first with (thio) chloroformates of the formula (IX) and then with amines of the formula (VI) according to the process (c) according to the invention.

A further method of obtaining compounds of the formula (I) according to the invention is that oxadiazolinones of the formula (XI)

Le A 25 302-foreign countries

R ¹ '

in which 10

R ¹ , R ² and Y have the abovementioned meaning,

reacted with hydrazine hydrate in the presence of a suitable diluent such as methanol or ethanol at temperatures between 20 ⁰ C and 100 ⁰ C and the thus obtained carbazic acid derivatives of the formula (XII),

0 0

R ^ C-NH-N-C-NH-NH? (XII)

¹ 2

Y = C-NH-R ²

in which

₁ -

R, R ^Ä and Y have the abovementioned meaning,

in the presence of a suitable diluent such as toluene, chlorobenzene or dichlorobenzene

at temperatures between 80 ⁰ C and 200 ⁰ C thermally 30

cyclized.

Oxadiazolinones of the formula (XI) are known (cf., for example, FR 14 15 605 and CA 6_4ί P5105g and NL 6 510 645

Le A 25 302-foreign countries

or CA. £ 5 .: P2274d-f) or obtainable according to generally known processes, for example by reacting the corresponding 4H-oxadiazolinones with iso (thio) cyanates of the formula (IV) in analogy to carrying out the process (b) according to the invention or for the synthesis of the precursors of the formula (II)

 10

The purification of the end products of the formula (I) is carried out by means of customary processes, for example by column chromatography or by recrystallization.

They are characterized with the aid of Schmelzpunk- * * * tes or non-crystallizing compounds with the aid of proton nuclear magnetic resonance spectrum.

The active compounds according to the invention can be used as defoliants, desiccants, herbicide and in particular as weed killers. Weeds in the broadest sense are understood to mean all plants that grow up in places where they are undesirable. Whether the substances according to the invention act as total or selective herbicides essentially depends on the amount used.

The active compounds of the invention may e.g. used in the following plants:

Dikotvle weeds of the genera: Sinapis, Lepidium, Galium »Stellaria, Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia,

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Cirsium, Carduus, Sonchus, Solanum, Rorippa, Rotala, Linderia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis, Papaver, Centaurea and Mercurial is.

Dikotvle cultures of the genera; Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, ^ Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, Cucumis, Cucurbita.

Monocotyledonous weeds of the genera; Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, ** Brachiaria, Loium, Bromus, Avena, Cyperus, Sorghum, Agropyrone, Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleocharis, Scirpus, Paspalum, Ishaemum, Sphenoclea, Dactyloctenium, Agrostis, Alopecurus, Apera.

Monocot cultures of the genera; Oryza, Zea, Triticum, Hordeum, Avena, Seeale, Sorghum, Panicum, Saccharum, Pineapple, Asparagus, Allium.

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

The compounds are useful depending on the concentration for total weed control e.g. on industrial and railway tracks and on paths and squares with and without tree cover. Similarly, the compounds for weed control in permanent crops, e.g. Forst, ornamental

Le A 25 302-foreign countries

wood, fruit, wine, citrus, nut, banana, coffee, tea, gum, oil palm, cocoa, berry fruit and hop plants and used for selective weed control in annual crops.

In this case, the active compounds according to the invention can be used with particularly good success for combating monocotyledonous and dicotyledonous weeds, in particular in dicotyledonous crops such as, for example, sugar beets.

Of particular note is the excellent effectiveness against the hard-to-control problem weed broom (Mercurial is).

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

These formulations are prepared in a known manner, for. B. by mixing the active compounds with extenders, that is, liquid solvents and / or solid carriers, optionally with the use of surfactants, emulsifiers and / or dispersants and / or foam-forming agents.

In the case of using water as an extender, e.g. also organic solvents as auxiliary

Le A 25 302-foreign countries

be used. Suitable liquid solvents * are essentially: aromatics, such as xylene, toluene, or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, Ю e.g. Petroleum fractions, mineral and vegetable oils, alcohols, such as butanol or glycol, and their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents,

such as dimethylformamide and dimethyl sulfoxide, as well as water. 15

Suitable solid carriers are:

For example, Ammonium salts and ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite,

Montmorillonite or diatomaceous earth and ground synthetic minerals, such as finely divided silica, alumina and silicates, as solid carriers for granules are suitable: e.g. Cracked and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules of inorganic and organic flours and granules of organic material such as sawdust, coconut shells, corn cobs and tobacco stalks. Suitable emulsifiers and / or foam formers are: eg nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. Alkylaryl polyglycol ethers, alkylsulfonates, alkyl sulfates, arylsulfonates and protein hydrolysates; suitable dispersants are: e.g. Lignin-sulfonic

sludge and methylcellulose

 35

Le A 25 302-foreign countries

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

Dyes such as inorganic pigments, e.g. Iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.

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

The active compounds according to the invention can be used as such or in their formulations also in a mixture with known herbicides for weed control, ready-to-use formulations or tank mixes being possible.

For the mixtures, known herbicides such as e.g. 1-amino-6-ethylthio-3- (2,2-dimethylpropyl) -1,3,5-triazine-2,4 (1H, 3H) -dione or N- (2-benzthiazolyl) -N, N'- dimethylurea for weed control in cereals; 4-amino-3-

Le A 25 302-foreign countries

Methyl 6-phenyl-l, 2,4-triazine-5 (4H) -one for weed control in sugar beet and 4-amino-6- (1,1-dimethylethyl) -3-methylthio-l, 2,4-triazine -5 (4H) -one for weed control in soybeans. Also, mixtures with 5- (2-chloro-4-trifluoromethyl-phenoxy) -2-nitro-benzoic acid, chloroacetic acid-N- (methoxymethyl) -2,6-diethy1-anilide; Methyl 6,6-dimethyl-2H-dioxo-S-C1- (2-propenyloxyamino) -butylidene-1-cyclohexanecarboxylic acid; Methy1-5- (2,4-dichlorophenoxy) -2-nitrobenzoate; 5-Amino-4-chloro-2 -phenyl-2,3-dihydro-3-oxy-pyridazine-ethyl-2- {C (4-chloro-6-methoxy-2-pyrimidinyl) -aminocarbonyl] -aminosulfonyl} -benzoate; exo-1-methyl-4- (1-methylethyl) -2- (2-methylphenylmethoxy) -7-oxabicyclo (2,2, l) -heptane J ethyl 2- {C (4-chloro-6-methoxy-2-pyridinyl) -aminocarbonyl] -aminosulfonyl} benzoate 3,6-dichloro-2-pyridinecarboxylic acid; N, S-diethyl-N-cyclohexyl-thiocarbamate J 3- (methoxycarbonyl)

^ O aminophenyl) -N-phenyl-carbamate 2-C4- (2,4-dichlorophenoxy) phenoxy] -propionic acid, its methyl or ethyl ester J 4-amino-6-t-butyl-3-ethylthio-1, 2,4-triazine-5 (4H) -oneJ 2- {4-C (6-chloro-2-benzoxazolyl) -oxy! -Phenoxy} -propanoic acid, its methyl or ethyl ester; 2- [4-5 (3,5-dichloropyrid-2-yloxy) -phenoxy] -propionic acid (trimethylsilyl ethyl ester); 5- (2-chloro-4-trifluoromethylphenoxy) -N-methylsulfonyl-2-nitrobenzamide; 2 - {- 4 - [(3-chloro-5- (trifluoromethyl) -2-pyridinyl> -oxy-3-phenoxy} -propanoic acid or -propanoic acid ethyl ester; 2-C4- (2,4-dichlorophenoxy) -phenoxy-3-propionic acid methyl ester; 2-C5-methyl-5- (1-methylethyl) -4-OXO-2-imidazolin-2-yl] -3-quinolinecarboxylic acid: 1-isobutylaminocarbonyl-2-imidazolidinone-3-cyclohexyl-5-6 trimethylene uracil; N-methyl-2- (1,3-

Le A 25 302-foreign countries

benzthiazol-2-yloxy) -acetanilide-2-chloro-N- (2,6-dimethylphenyl) -N - [(IH) -pyrazol-1-yl-methyl-3-acetamide; 2-Ethyl-6-methyl-N- (1-methyl-2-methoxyethyl) -chloroacetanilide-3- (ethoxycarbonylaminophenyl) -N- (3'-methylphenyl) -carbamate-2-Cl- (ethoxamino) butylidene 3-5- ( 2-ethylthiopropyl) -l, 3-cyclohexadione; N, N-diisoproyl-S- (2,3,3-trichloroallyl) -thiolcarbamate or 2, fe-dinitroM-trifluoromethyl-N, N-dipropylaniline are possible. Surprisingly, some mixtures also show a synergistic effect

** Mixtures with other known active substances, such as fungicides, insecticides, acaricides, nematicides, bird repellents, plant nutrients and soil conditioners, are also possible.

The active compounds can be used as such, in the form of their formulations or the use forms prepared therefrom by further dilution, such as ready-to-use solutions, suspensions, emulsions, powders, pastes and granules. The application is done in the usual way, e.g. by pouring, spraying, spraying, spreading.

The active compounds according to the invention can be used both before and

be applied after emergence of the plants. 30

They can also be incorporated into the soil before sowing.

Le A 25 302-foreign countries

- 49 -

The amount of active ingredient used can vary over a larger range »It depends essentially on the nature of the desired effect. In general, the application rates are between 0.01 and 10 kg of active ingredient per hectare of soil, preferably between 0.05 and 5 kg per hectare.

The preparation and the use of the active compounds according to the invention are evident from the following examples.

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Embodiments Preparation Examples: 1 3eispiel

-CH ₂ -GH (CH ₃ ) ₂ (method a)

To 11.1 g (0.04 l) of 1- (H-isobutylcarbamoyl) -4-isopropylidenimino-3-methyl-1,2,4-triazolin-5-one in 100 ml of ethanol is added 20 ml of concentrated hydrochloric acid and the solution is concentrated at 60 ⁰ G and 200 mba r in the course of 3 hours on! rotary evaporator. The meat is brought to crystallization by trituration with ethanol / diethyl ether (1: 1) and dried э η dei air. LIan receives 4.3 g (50% of theory) of Ц- iimino-i- (11-isobutylcarbauoyl) -3-methyl-triazolin-5-one of melting point 183 ⁰ G.

example

(Method b)

- 51 -

CH ₃ ^ ₇₇ N-IiH ₂

/ CH ₃ = C-NH-C-CH.

To 3.42 g (0.03 mol) of 4-amino-3-methyl-l, 2,4- (IH) -triazolin-5-one in 80 ml of absolute acetonitrile are added 3.6 g (0.036 mol) of t-butyl isocyanate and 0 , 05 g to 0.1 g of diazabicycloundecene (DBU), stirred for 2 hours at 20 ⁰ C, concentrated in vacuo, the residue is taken up in dichloromethane, washed with water, dried over sodium sulfate, concentrated in vacuo and the residue is crystallized Trituration with diethyl ether.

One obtains 5.0 g (78.3% of theory) of 4-amino-l- (N-tbutylcarbamoyl) -3-methyl-l, 2,4-triazolin-5-one of melting point 132 ⁰ C.

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Example 3 5

O = C-NH-CHo ² "

(Method a-Stuff Variant)

To 8.2 g (0.03 mol) of isopropylidenimino-S-methyl-1-phenoxycarbonyl-1,2,4-tria2olin-5-one in 50 ml of absolute tetrahydrofuran are added 4.2 g (0.03 mol) (2 , 2-dichlorocyclopropyl) methylamine, then stirred for 12 hours at 20 ⁰ C, concentrated in vacuo, the residue is taken up in 100 ml of ethanol, added to 3 ml of concentrated hydrochloric acid and _ft

Stirred for 3 to 4 hours at 60 ⁰ C and 200 mbar. For workup, the mixture is concentrated in vacuo, the residue taken up in dichloromethane, washed three times with saturated aqueous sodium bicarbonate solution, dried over sodium sulfate and concentrated in vacuo. The residue is crystallized by trituration with diethyl ether.

This gives 4.4 g (52 V, theory) of 4-amino-1- [N- (2,2-dichlorocyclopropylmethyl) carbamoyl] -3-methyl-1,2,4- _n

triazolin-5-one of melting point 149 ^Q c.

Le A 25 302-foreign countries At game 4

| 3

O = C-NH С- (СНо) о-СНо

ίο у * ^{Δ J}

CH ₃ (method с)

To 3.2 g (0.0137 mol) of 4-amino-3-methyl-1-phenoxy-5-yl-1,2,4-triazolin-5-one in a mixture of 25 ml of tetrahydrofuran and 10 ml of dioxane are added 8 , 9 g (0.088 mol) of 1,1-dimethylbutylamine, heated 24 hours at reflux temperature, concentrated in vacuo, the residue is taken up in dichloromethane, wash with zweiprozen- ² ^ tiger sodium hydroxide solution and water, dried over sodium sulfate, the solvent is removed in Vacuum and crystallize the residue by trituration with diethyl ether.

One receives 1.9 g (61 x /. Of the theory) of 4-amino-l- [N- (1,1-dimethylbutyl) carbamoyl] -3-methyl-l, 2,4-triazolin-5-one of melting point 110 ^° C.

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- 54 -

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

(I)

ίο J, " ^л

i-r2

15 table 1 R ¹ R ² X С : н ₃ Y Physical Properties Example no. CH ₃ R-Configuration 0 ¹ H-NMR * ^} 1.5 (d) 5 С-С 20 CH ₃ -С 0 ¹ H-NMR * ^} 1.5 (d) 6 ^C 2 ^H 5 .H ₃ с 3-configuration 0 Mp 139 ⁰ C 25 7 H ^ 0

Le A 25 302-foreign countries Table 1 - continued

Eg No. physical X Y properties

10

11

CH

CH

CH

CH (CH ₃ ) ₂ - (CH ₂ ) ₅ -CH ₂ Cl

O O

O O

O O

O O

CH mp. 161 ⁰ C

Mp 63 ⁰ C

¹ H NMR * ⁰ 1.45 (m, 4H)

¹ H NMR * ⁵ 0.95 (t, 3H)

12

13 14

CH-

CH,

CHr

-CH-

-CH (C ₂ H ₅ ) ₂ -CH-CH (CH ₃ ) ₂ CHo

OO mp. 133 ⁰ C

OO Fp. 103 ⁰ C

OO mp 103 ° C

15

CH-

OO Mp. 105 ⁰ C

16

CH ₃ -CHO ^- CH ₂

OO Mp. 135 ⁰ C

17

CH

CH-

~ C ~ CH

CH

О О Mp. 106 ⁰ C

(Dec.)

Le A 25 302-foreign countries Table 1 - continued

Ex. No physical X Y properties

18

20

CH ₃ -CH- (CH ₂ ) ₂ "- C } 0 0

19 CH,

CH-

CH-

CH ₃ -C-CH ₃

S 0

1.5496

Mp 128 ⁰ C

SO Fp 10O ⁰ C

21 H - (CH ₂ ) ₅ -CH ₂ Cl OO mp 131 ⁰ C

CoH

22 CHo - < H V-CH, OO mp 153 ⁰ C

25 23 CH ₃ -C-CH ₂ Cl

24

25

CH ₃

CH ₃ -CH ₂ -CH = CH ₂

CH ₃ -CH ₂ -C-OC ₂ H ₅

OO mp 118 ° C

OO mp 92 ° C

O O

Mp 127 ⁰ C

Le A 25 302-foreign countries Table 1 - continued

Eg No. physical X Y properties

26

27

28

29

30

31

CHoCl

I ²

CHo -C-CH ₃

.

CH ₂ Cl CHo

I ³

CHo -C-CHCl-

CHr

CH,

C ₂ H ₅ -CH ₂ -C-CH ₃ I CHoF I CH ₃ I -C-CHo I CH ₂ F CH ₃ CH ₂ F -C-CH ₃ CH ₂ F ^C 2 ^H 5

CH,

CHo -C

CHr

OO n £ ² 1.5055

O O

O O

O O

O O

O O

Mp 176 ⁰ C

¹ H-NMR * ⁾ : 4.4; 7.95

Mp 133 ⁰ C

Fp30-40 ° C

¹ H-NMR * ⁵ :

4.36;

8.23

Le A 25 302-Aus1 and

Table 1 - continued

Ex. No physical X Y properties

10 32

^CH

CUr 0

Fp 99 ° C

33 CH ₃ -CH- (CH ₂ ) ₃ -CH (CH ₃ ) 2 O 0

34 CH ₃ - (H> -CF ₃ OO

¹ H-NMR * ⁰ :

4.40;

7.61

Mp 162 ⁰ C

CH

CH

O O

O O

Mp 198 ⁰ C

Mp 108-109 ⁰ C

CH 0

²⁵ 38 CH ₃ - (CH ₂ J ₂ -CH ₃ 0 0

Mp 168-170 ⁰ C

Fd 134-136 ⁰ C

CH,

-CH C-CH-

CH ₃ CH ₃ OO

Mp 149 ⁰ C

Le A 25 302-foreign countries Table 1 - continued

Ex. No physical X Y properties

41 42 43

44

CH,

CH

CH-

40 CH ₃ -C-CF ₃

CHO

-C

CH ₃ -CH ₂ -CH ₂ -CNO 0

0 0

0 0

₃ -CH ₂ -CH- (CH ₂ ) ₃ -CH ₃ 0 0

CH-

CH

^C 2 ^H 5

OHC

² OO

Fp is: 149 L ⁰ C 91- ⁰ C Fp 94 93- ⁰ C Mp 175 178 ⁰ C Mp 92

Fp 102-103 ⁰ C

45

-C-CHO-F

I

CHO O O

Fo 178 ⁰ C

46

47

JCH

H У- С-

^C 2 ^H 5 OO

O O

Fp 113 ⁰ C

Mp 109 ⁰ C

Le A 25 302-foreign countries Table 1 - Continued

Example

 No.

physical X У properties

48 CH:

O O

Mp 148 ⁰ C

49

CHo -CH

CH-OO

¹ H NMR * ^} : 0.35-0.65 0.93

50 CH- CH-

O O

Mp 175 ⁰ C

51 CH-

CH-

CH-OO

Mp 211 ⁰ C (Hydrochloric!)

52 CH ₃ -CH ₂ -C

25 53

CH-

CH, OO

O O

Mp 152 ⁰ C

Mp 185 ⁰ C

54 CH,

55

CH-

CH-

CH-

CH,

CH ₃ -C-CH = C <

I Cl O O

Mp 198 ° C (Hydrochloric!)

Mp 135 ° C

Le A 25 302-foreign countries

Table 1 - Continued

Example

 No.

physical X У properties

CH.

(CH ₃ ) ₃ 0 0

CH, mp 200-203 ⁰ C

CH-

о о

Mp 119 ⁰ C

58

CH ₃ -CH-CH ₂ -Cl 0 0 Fp 136 ⁰ C

CH,

59

СИ- CH ₃ , 3, 3

-C-CHo-C-CH, ²

CH ₃ CH ₃

CH "-CH-CF

0

0

Mp 122 ⁰ C

Mp 141 ⁰ C

61

CH-

CH,

CH ₃ -C-CN

CH, 0

Mp 176 ⁰ C

62

CH ₃ -CH- (CH ₂ ) ₄ -CH ₃ OO Fp 67 ⁰ C

CH-

CHo-CH-CHO

O O

Fd 120 ° C

CH,

Le A 25 302-foreign countries Table 1 - continued

Ex. No physical X Y properties

66 67

68 69

70

71

72

CH ₃ - (CH ₂ ) ₂ -OCH ₃

65 CH ₃ -CH-CH ₂ -N <

CH

CH.

CH-

CH.

CH-

^C 2 ^H 5

UW ₃ (CHo) q- (

fat W

-CH

-сн- / ~ Л

CH

-CH CH-Cl

I i

CH ₃ CH ₃

-CH-CH = C (

Cl

Cl

O O fp 114 "C 147 ⁰ C O O Mp 84 ⁰ C (Hydro- chloride) 195 ⁰ C O S fp 205 ⁰ C. O S fp 212 ⁰ C. O S fp 139 ⁰ C O S fp O O fd

O O

O O

Fo 114 ⁰ C

n | ^ö 1.5328

73

CH <

CH ₂ Cl

CH = CH-OO

Fd 120 ⁰ C

Le A 25 302-foreign countries Table 1 - continued

Example no. R ¹ R ² X Y Physical Properties 74 CH ₃ CHq I ei -C CH-CH = C <II ei CH ₃ CH ₃ O O n% ° 1.3840 75 CH ₃ CH ₂ Cl -CH <and CH ₂ Cl O O Mp 158 ⁰ C -CH ₂ -CH-CH ₂ Cl Cl (3: 1) 76 CH ₃ -CH-CHoCl I O O Mp 147 ⁰ C C ₂ H ₅

77

79

80

CH

CH-

-CH-CH ₂ -NO 0 0

-CH ₃ -СН- (СН ₂ ) ₅ -СН ₃ 0 О

CH-

CH-

CH ₃ CH ₃

n ² , ² 1.4995 (hydrochloride)

-C- (CH ₂ ) ₃ -CH ₃ OO n ² , ² 1.4891

n | ° 1.4920

-CH-CH ₂ -C-CH ₃ 0 0 Fp 140 ⁰ C

Le A 25 302-foreign countries

Table 1 - Continuation

Example, no.

physical X Y properties

81

CH ₃ -CH ₂ -CH <

C ₂ H ₅ ^C 2 ^H 5

0 0 Fp 115 C

82 CH-0 0

Mp 134 ⁰ C

83 CH-

CH ₃ H

CH-0 0 Fp 164 ⁰ C

84

CH-

CHo (ice) 0 0 Fp 144 ⁰ C

85 CH,

η L -CH 0 0

Fd 121 ° C

86 CH,

CoH

^C 2 ^H 5 0 0

2:33

87

CH ₃ -CH ₂ -CF ₃ 0 0

Fd 152 ° C

88 CH-OS mp 178 ° C

Le A 25 302-foreign countries Table 1 - continued

Example

No,

physical X Y properties

Cl

10 89 CH

0 0 Fp 156 ⁰ C

90 CH-

0 0 Fp 167 ⁰ C

15 91 CH-

0 0 Fp 113 ⁰ C

92 CH,

CH-

93 CH

0 0 Fp 133 ⁰ C

(CH ₂ ); Fd 98 ⁰ C

CH ₃ - (CH ₂ ) ₂ - < P

CH ₃ O

0 0 Fp 156 ⁰ C

95 CH ₃ - (CH ₂ ) ₂ - <^ ^) - OCH ₃ 0 0 Mp 210 ⁰ C

96 CH

-CH

XT mp 175 ⁰ C

Le A 25 302-foreign countries Table 1 - continued

Eg No. physical X Y properties

97

CH ₃ -CH ₂ -CH-C ₂ H ₅ 0 0 Fp 106 ⁰ C

CH-

98

CH ₃ - (CH ₂ ) ₂ -CH (CH ₃ ) ₂ 0 0 Fp 104 ⁰ C

99 CHo -CH- /.

ΟΡFp 120 ⁰ C

(Dec.)

100 CH ₃ -CH ₂ .

⁰ X ¹ .CH ₃ O 0

Mp 108 ⁰ C

CH ₃ Cl

101 CH ₃ -CH ₂ - ( У- ei о о

CH-Fp 151 ⁰ C

102

CH ₃ - (CH ₂ ) ₂ - \ P 0 0 Fp 151 ⁰ C

CH-

103 CH ₃ -C-CH ₂

CH-

0 mp 134 ⁰ C

CH-

104

CH ₃ -CH- (CH ₂ ) ₂ -CH ₃ 0 0 ng ⁰ 1.4972

CH-

Le A 25 302-foreign countries Table 1 - continued

Ex. No, physical X Y properties

105 CH ₃ -CC ₂ H ₅

0 mp 128 ⁰ C

^C 2 ^H 5

106 CH-

0 mp 101 ⁰ C

CH ₃ 107 CH ₃ -CH- (CH ₂ ) ₂ -CH <0 0

Fd 73 ⁰ C

CH-

C ₂ H ₅ 20 108 CH ₃ - (CH ₂ ) ₃ -N <0 0

^C 2 ^H 5

nS ° 1.5815 (hydrochloride)

109 CH ₃ - (CH ₂ ) ₃ -N <0 0

Mp 210 ⁰ C (hydrochloride)

110 CH ₃ -CH-CH ₂ -CN

0 mp 145 ⁰ C

^C 2 ^H 5

111 CH ₃ -CH-CH ₂ -CH-C ₂ H ₅ 0 0 n | ° 1.4890

C ₂ H ₅ CH ₃

CH ₃ 112 CH ₃ -CH-CH ₂ -CH <0 0

CH-n | ° 1.4858

Le A 25 302-Off 1 and

35

Table 1 - continued

Eg, no physical XY properties

10

113

114 -CH-CHo-N

O O

Mp 108 ⁰ C (Hydrochloric!)

CH ₃ - (CH ₂ J ₄ -CH ₃ OO Fp 81 ⁰ C

15

115

CH-C ₂ H ₅

CH- (CH ₂ ) ₃ -N <OOC ₂ H ₅

n | ° 1.5100 (hydrochloride)

116

CH-CH-

CH-

о о

n ° ° 1.5150 (hydrochloride)

20

117

CH-

0

Mp 157 ⁰ C

25

118

119

CH-

CH-

^2H 5

CH

0

0

Mp 116 ⁰ C

Mp 145 ° C

30

120

CH-0

Mp 118 ⁰ C

Le A 25 302-foreign countries

Table 1 - continued

Eg no physical X Y properties

121 122

CH ₃ -CH ₂ -CH ₂ -OC ₂ H ₅ 0 0

CH,

0

Mp 123 ⁰ C mp 213 ⁰ C

123 124

125

CH,

CH,

j CH ₃

.CH = C <О О

CH,

0

О О

Cl

Mp 93 ⁰ C

Mp 93 ⁰ C

IH-NMR *>: 1.58 (dd); 1.77 (t); 2.76 (t)

126

CHo -CH

О О

Mp 142 ⁰ C

127

128

сн

CH,

О О

О О

Mp 123 ⁰ C (endo form)

Mp 131 ⁰ C

(Exo-form)

129

CH,

-CH-CH.

О О

Mp 133 ⁰ C

130 CH ₃ -CH ₂ о о

Mp 125 ⁰ C

Le А 25 302-foreign countries

Table 1 - continued

Ex.

No. R ¹ R '

physical X Y properties

131

-CH- (H

ΟΠ

CH-

132 CH ₀ . C- <

O O

Mp 117 ⁰ C

¹ H-NMR * ⁾ : 1.45 (s); 7.04-7.43 (m)

133 CH3 -CH ₂ -CH ₂ -C. > -F 0 0 Fp 168 ⁰ C

134 CH ₃ -CH- (H

135

0 mp 118 ⁰ C

^C 2 ^H 5

CH-

-CH C-CH-

C ₂ H ₅ CH ₃

0 Fp 157 ⁰ C

136 CHo-CHo-C

137 CH-

0 mp 180 ° C

OO Fp 188 ° C

138

-CH-

CH-

Mp 95 ⁰ C

Le A 25 302-foreign countries

The ¹ H-NMR SPeKtTeHi were taken up in deuterochloroform (CDCl ₃ ) with tetramethylsilane (TMS) as the internal standard. The chemical shift is given as the δ value in ppm.

Preparation of the starting compounds

Example II- 15

NH-CH ₂ -CH (CH ₃ ) ₂ 20

To 6 g (0.04 mol) of 4-Isopropylidenimino-3-methyl-lH-triazolin-5-one and 4 g (0.04 mol) of triethylamine in 20 ml of dioxane are added dropwise at 20 ° C with stirring 12 g ( 0.12 mol) isobutyl isocyanate and stirred for 3 hours at 100 ⁰ C for workup. The reaction mixture is concentrated in vacuo, the residue taken up in 100 ml of dichloromethane, washed several times with 100 ml of water, dried over sodium sulfate and in vacuo Solvent freed.

One obtains 11.2 g (100 V. of theory) of 1- (N-isobutylcarbamoyl) -4-isopropylidenimino-3-methyl-1,2,4-triazolin-5-one as an oil

¹ H-NMR (CDCl _3): δ = 0.85 (d, 6H) ppm.

Le A 25 302-foreign countries

In a corresponding manner and in accordance with the general information on the preparation, the following precursors of the general formula (II) are obtained:

tl

ΝΜΪ ·

(II)

table

Example, NR:

R ¹ R ²

physical X Y properties

II-2

CH-

= C (CH ₃ ) ₂ 0 0 mp 125 ° C

II-3

II-4

II-5 II-6

7-II

CH,

CH

CH-

= СН-СН (СНо) о О О ¹ H-NMR * ⁵ : ² 3.9

= C (CH ₃ ) ₂ OO Fp 87 ⁰ C

CH ₃ -CH (CH ₃ ) ₂ = C (CH ₃ ) 2 OO Fp 107 ⁰ C CH ₃ -CH (C ₂ Hg) ₂ = C (CH ₃ ) ₂ 0 0 Fp 68 ⁰ C

CH ₃ -CH-CH (CH ₃ ) ₂ = C (CH ₃ ) ₂ 0 0 ¹ H-NMR * ⁰ :

0.54 (d, CH ₃ )

Le A 25 302-foreign countries Table 2 - Continued

Example

 No.

R ¹ R ²

= C

physical XY properties

11-8 CH ₃ -CH ₂ - (H) = C (CH ₃ ) 2 0 0 Mp 115 ⁰ C

II-9

11-12 11-13

CHO

I ³

CH ₃ -C-CH ₂ Cl = C (CH ₃ ) ₂ OO Fp 88 ⁰ C

CH ₃

II-10 CH,

= C (CH ₃ ) ₂ OO Fp 139 ⁰ C

CH

CoH

11-11 CH-

H ₃ = C (CH ₃ ) ₂ OO

CoH

2 ⁿ 5

CH ₃ -CH ₂ -COOC ₂ H ₅ = C (CH ₃ ) ₂ 0 0 CH ₃ -CH ₂ -CH = CH ₂ = C (CH ₃ ) ₂ 0 0

oil

Mp 108 ⁰ C mp 86 ⁰ C

11-14 CH ₃ - ^ /) = C (CH ₃ ) ₂ OO Fp 158 ⁰ C

11-15 CH-

CF ₃ = C (CHO) ₂ OO Fp 218 ⁰ C

11-16 CH-

1 = C (CH ₃ ) ₂ OO mp 185 ° C

Le A 25 302-foreign countries

Table 2 - continued 5

/ R ³ physical

Ex. R ¹ R ² = C XY properties

No. ^ ⁴

₃ I

11-17 CH ₃ -CH ₂ -C-CH ₃ = C (CH ₃ ) ₂ 0 0 mp 121-122 ⁰ C

CH ₃

Example III-1

/ CH ₃ ^H 3 ^C > N ^ N «C ^

Il I CH ₃

11.4 g (0.1 mol) of 4-amino-3-methyl-1,2, A- (IH) -triazolin-5-one (see European Union 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 concentrated under reduced pressure 15.4 g (100 Ά of theory) of 4-Isopropylidenimino-3-methyl-l, 2,4- (IH) -triazolin-5-one of melting point 140-144 ⁰ C.

Le A 25 302-Off 1 and

Example VI 5

To 2.3 g (0.02 mol) of 4-amino-3-methyl-l, 2,4- (IH) -triazolin-5-one in 25 ml of absolute tetrahydrofuran are added 2.7 g (0.024 mol) of potassium tert-butoxide, stirred for 1 hour at 20 ⁰ C, then added dropwise with stirring 3.1 g (0.02 mol) of phenyl chloroformate, stirred for hours at room temperature, then adjusted with glacial acetic acid to pH 5, concentrated in vacuo, takes Backlog in

Ζ® chloroform, washed with water, dried over sodium sulfate, concentrated in vacuo and the residue is crystallized by trituration with ether.

This gives 1.1 g (23.5% of theory) of 4-amino-3-methyl-1-phenoxycarbonyl-1,2,4-triazolin-5-one of melting point 175 ⁰ C.

Le A 25 302-foreign countries

Example XI 5

To 15.4 g (0.1 mol) of 4-Isopropylidenimino-3-methyl-l, 2,4- (lH) -triazolin-5-one in 100 ml of absolute tetrahydrofuran is added at room temperature initially 13.4 g (0.12 mol) Kaiium t-butylate, stirred for one hour at room temperature, then 15.5 g (0.1 mol) of phenyl chloroformate and stirred for a further 12 hours at 20 ⁰ C. For workup is acidified with glacial acetic acid, concentrated in vacuo, the residue taken up in chloroform , washed with water, dried over sodium sulfate, concentrated again in vacuo and recrystallized from acetone.

One obtains 10 g (36.5% of theory) of 4-Isopropylidenimino-3-methyl-1-phenoxyсarbonyl 1,2,4-triazolin-5-one of melting point 162 ⁰ C.

Le A 25 302-foreign countries

Example X-2 5

O = C-O-CH

2 ⁿ 5

To 7.7 g (0.05 mol) of 4-Isopropylidenimino-3-methyl-l, 2,4- (IH) -triazolin-5-αη in 50 ml of absolute tetrahydrofuran are added at 20 ⁰ C 1.5 g ( 0.05 mol) of sodium hydride, stirred for one hour at room temperature, then added dropwise with stirring 5.4 g (0.05 mol) of ethyl chloroformate and stirred after the addition of additional hours at 20 ⁰ C.

For workup is acidified with glacial acetic acid, concentrated in vacuo, the residue taken up in dichloromethane, washed with water, dried over sodium sulfate, concentrated again in vacuo and recrystallized from isopropanol.

This gives 5.0 g (44 V. of theory) of 1-ethoxycarbonyl-4-isopropylidenimino-3-methyl-l, 2,4-triazolin-5-one of melting point 91 ⁰ C.

Le A 25 302-foreign countries

- 78 -

Application example:

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

(A)

N ^ N ^ * \ CH ₃ 15

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

I II

¹ Ho) о (B)

Il

N-Isobutyl-2-oximidazolidine-1-carboxamide (known from R. Wegler "Chemie der Pflanzenschutz- und Schädlingsbekungsmittel" Bd, 5, page 219 (1977))

Le A 25 302-foreign countries Example A

Prе-emergence test

Solvent: 5 parts by weight of acetone emulsifier: 1 part by weight of alkylaryl polyglycol ether

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

Seeds of the test plants are sown in normal soil and watered after 24 hours with the preparation of active ingredient. It is advisable to keep the amount of water per unit area expediently constant. The Wirkstoffkonzentrat ion in the preparation does not matter, only the application rate of the active ingredient per unit area is crucial. After three weeks, the degree of damage of the plants is rated in % damage compared to the development

the untreated control. It means:

0 % = no effect (as untreated control) 100 V. = total destruction

In this test, for example, the compounds according to Preparation Examples 2, 14, 23, 32, 41, 45, 48 and 57 show a significantly better herbicidal activity against weeds as well as a significantly better selectivity in crops such as sugar beet than the reference substance (B).

Le A 25 302-foreign countries

Example В 5

Post-emergence test

Solvent: 5 parts by weight of acetone emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent, the indicated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.

With the preparation of the active compound, test plants which have a height of 5-15 cm are injected in such a way that the respective desired amounts of active ingredient per unit area are expelled.

be brought. The concentration of Spntzbruhe is chosen so that in 2000 1 water / ha, the respective desired amounts of active ingredient are applied. After three weeks, the degree of damage of the plants is scored in Y. damage in comparison to the development of the untreated control.

It means:

0 V, = no effect (like untreated control) 100 '/. = total annihilation

In this test, e.g. the compounds according to Examples 1 and 48 and 1, 2, 3, 14, 23, 32, 41, 45, 48, 57 and 78 in the control of mono- and dicotyledonous weeds a significantly better herbicidal activity than the comparison substance (A) or, (B).

Le A 25 302-foreign countries

Claims (5)

Please contact Pa tent in which R ^{1 is} hydrogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, alkoxyalkyl, cycloalkyl, cycloalkylalkyl, tetrahydrofuranyl, 1-tetrahydrofuranylalky 1 or each optionally substituted aralkyl or aryl, H far is hydrogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, cyanoalkyl, hydroxyalkyl, alkoxyalkyl, alkoxycarbonylalkyl, alkoxycarbonylalkenyl _t alkylaminoalkyl, dialkylaminoalkyl, fir jev / Eils optionally substituted cycloalkyl, Cyclpalkylal ^ yl, cycloalkenyl or cycloalkenylalkyl, stituiertes optionally suku Heterocyclylalkyl, in each case optionally substituted aralkyl, aroyl, -aryl, aralkyloxy or aryloxy, or alkoxy, alkenyloxy or aynyloxy, X is oxygen or sulfur and Y is oxygen or sulfur in addition to extenders and / or surface-active agents. 2
Halogen atoms; E furthermore each straight-chain or branched alkoxy having 1 to 8 carbon atoms, alkenyloxy having 2 to 8 carbon atoms or alkynyloxy having 2 to 8 carbon atoms and finally each optionally mono- or polysubstituted by identical or different substituents aralkyl, aroyl, aryl, aralkyloxy or aryloxy, each having 6 to 10 carbon atoms in the aryl moiety and optionally 1 to 8 carbon atoms in the alkyl moiety, where as alkyl substituents optionally halogen and cyano come into question and where as aryl substituents in question: halogen, cyano, I ¹ Titro, hydroxy, in each case straight-chain or branched Alkyl, alkoxy, alkylthio, haloalkyl, haloalkoxy, haloalkylthio, alkylsulfinyl, Лікуіsulfonyl, haloalkylsulfinyl, haloalkylsulfonyl, alkanoyl or alkoxycarbonyl each having 1 to о carbon atoms in the alkyl moiety and optionally 1 to 9 identical or different halogen atoms, cycloalkyl having 3 to 6 carbon atoms men and phenoxy, IC for sour s s off or sulfur st lord l for oxygen or Iclr.vefal stands, neoen extenders and / or surface-active .JLtöeln included. 2. Mitic herbicidal composition according to claim 1, characterized in that it is an active ingredient at least one substituted triazolinone of the formula I, in which R is hydrogen, for each straight-chain or branched Alky 1 having 1 to 8 carbon atoms, alkenyl having 2 to 8 carbon atoms, alkynyl having 2 to 8 carbon atoms, haloalkyl having 1 to 8 carbon atoms and 1 to 17 identical or different halogen atoms, Halog enalkenyl with From 2 to 8 carbon atoms and from 1 to 15 identical or different halogen atoms, haloalkynyl of 2 to 8 carbon atoms and 1 to 13 identical or different halogen atoms, alkoxyalkyl of 1 to 6 carbon atoms in the individual alkyl moieties, or cycloalkyl or cycloalkylalkyl of 3 to 7 each Carbon atoms in the cycloalkyl moiety and optionally 1 uis δ carbon atoms in the straight-chain or branched Alky lteil, fdr x'etraaydrofuranyl or f л? i3traaydrofuranylalkyl with, where appropriate, 1 or 4 carbon atoms in the straight-chain or branched alkyl moiety or for each зз ^ эЬ mono- or polysubstituted, identically or differently substituted aralkyl or aryl, in each case 6 to 10 carbon atoms in the aryl part and optionally 1 to 6 carbon atoms in the straight-chain or branched alkyl part; where as aryl substituents in question: halogen, cyano, nitro and in each case straight-chain or branched alkyl, alkoxy, alkylthio, haloalkyl, haloalkoxy or haloalkylthio having in each case 1 to 4 carbon atoms and optionally 1 to 9 ** same or different halogen atoms, R ^ is hydrogen, in each case straight-chain or branched alkyl having 1 to 18 carbon atoms, alkenyl having 2 to 8 carbon atoms * Q atoms, alkynyl of 2 to 8 carbon atoms, Haloalkyl having 1 to 8 carbon atoms and 1 to 17 identical or different halogen atoms, haloalkenyl or haloalkynyl each having 2 to 8 carbon atoms and 1 to 15 or 13 identical or different halo genatomen, cyanoalkyl having 1 to 8 carbon atoms, hydroxyalkyl having 1 to 8 carbon atoms and 1 to 6 hydroxy groups, alkoxyalkyl, alkoxycarbonylalkyl or alkoxycarbonylalkenyl each having up to 6 carbon atoms in the individual alkyl or alkenyl moieties, alkylaminoalkyl or dialkylaminoalkyl Le A 25 302-foreign countries each having 1 to 6 carbon atoms in the individual alkyl moieties, for cycloalkyl with 11 carbon atoms or for each optionally mono- or polysubstituted or differently substituted cycloalkyl, cycloalkylalkyl, cycloalkenyl or cycloalkenylalkyl having in each case 3 to 8 carbon atoms in the cycloalkyl or cycloalkenyl moiety and optionally 1 to 6 carbon atoms in the straight-chain or branched alkyl moiety, suitable substituents being in each case: halogen, cyano and in each case straight-chain tiger or branched alkyl or haloalkyl having in each case 1 to 4 carbon atoms and optionally 1 to 9 identical or different halogen atoms or straight-chain or branched haloalkenyl having up to 4 carbon atoms atoms and 1 to 5 identical or different halogen atoms or each doubly linked alkanediyl or alkenediyl having in each case up to 4 carbon atoms; R ^ may also be simple in the heterocyclyl moiety or multiply, identically or differently substituted heterocyclylalkyl having 1 to 6 carbon atoms in the straight-chain or branched alkyl part and 1 to 9 carbon atoms and ι to 3 heteratoms - in particular stick substance, oxygen and / or sulfur - in the heterocyclyl radical 1, suitable substituents being: halogen, cyano, nitro, and in each case straight-chain or branched alkyl, alkoxy, alkylthio, haloalkyl, halogeno koxy, haloalkylthio or alkoxycarbonyl with Le A 25 302-Au sland in each case 1 to 5 carbon atoms and. optionally 1 to 9 identical or different 3 · Process for the preparation of herbicidal LIittein, characterized in that substituted triazolinones of the formula (I) according to claim 1 or 2 are mixed with extenders and / or surface-active Sudstanzen. 4. A method for controlling weeds, characterized in da3 substituted triazolinones of the formula (I) according to claim 1 or 2 to act on the weeds and / or their habitat. Use of substituted triazolinones of the general formula I according to claim 1 or 2, characterized in that they are used for controlling weeds.