DD298393A5 - SUBSTITUTED TRIAZOLINONE - Google Patents

Abstract

The invention relates to novel substituted triazolinones of the general formula in which R 1 is alkyl having 3 to 4 carbon atoms or cyclopropyl and R 2 is hydrogen, alkyl, alkenyl, alynyl, haloalkyl, haloalkenyl, haloalkynyl, cyanoalkyl, hydroalkyl, alkoxyalkyl, alkoxycarbonylalkyl, alkoxycarbonylalkenyl , Alkylaminoalkyl, dialkylaminoalkyl, in each case optionally substituted cycloalkyl, cycloalkylalkyl, cycloalkenyl or cycloalkenylalkyl, optionally substituted heterocyclylalkyl, in each case optionally substituted aralkyl, aroyl, aryl, aralkyloxy or aryloxy, alkoxy, alkenyloxy or alkynyloxy, a plurality of processes and novel intermediates their preparation and their use as herbicides. Formula (I)

Description

The invention relates to novel substituted triazolinones, mehrt "> process for their preparation and their use as

Herbicides.

It is known that certain substituted triazolinones such as the compound 4-amino-1 - (N-isopropylcarbamoyl) -

3-methylthio (1H, 4H) -1 ₍ 2,4-triazolin-5-one or the compound 4-amino-1 - (N-propylcarbamoyl-S-methylthio-U H, 4H) -1,2, 4-triazolin-5-one or the compound 4-amino-1- (N-butylcarbamoyl) -3-methylthio (1H, 4H) -1,2,4-triazolin-5-one or the

Compound 4-amino-1- ^{(N-cyclohexylcarbamoyl):} 3-methylthio (1H, 4H) -1,2,4-triazolin-5-one (vgl.zB JP 52/125168) have herbicidal Own properties. However, the herbicidal activity of these prior art compounds against problem weeds is as well as theirs Compatibility with important crops is not completely satisfactory in all fields of application. Furthermore, certain substituted triazolinones, such as the 1- (N, N-dimethylcarbanioyl) -3-phenyl-4-amino

1,2,4-triazolin-5-one is known (compare J. Heterocycl Chem.17: 691-1696 [1980], Org. Mass. Spectrom 14, 369-378 [1979]).

About an activity of these prior art triazolinones as herbicides is not yet known. There have been new substituted triazolinones of the general formula (I),

-N-NH ₂

il) I

O, NH-R ²

in which

R 'is alkyl of 3 to 4 carbon atoms or cyclopropyl and

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

found.

The precursors of the formula (I) may optionally be used as a function of the nature of the substituents R 'and R ²

geometric and / or optical isomers or isomer mixtures of different composition are present. Both an isomer and the isomer mixtures are claimed according to the invention.

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

N-NH ₂

O NH-R ²

in which

R 'is alkyl of 3 to 4 carbon atoms or cyclopropyl and

R ² is hydrogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, cyanoalkyl, hydroxyalkyl, alkoxyalkyl, alkoxycarbonylalkyl, alkoxycarbonylalkenyl, alkylaminoalkyl, dialkylaminoalkyl / ^f or respectively optionally substituted cycloalkyl, cycloalkylalkyl, cycloalkenyl or cycloalkenylalkyl, optionally substituted heterocyclylalkyl, for each optionally substituted aralkyl, aroyl, aryl, aralkyloxy or aryloxy, is alkoxy, alkenyloxy or alkynyloxy,

if you get

(a) hydrazones of the formula (II),

-N-N = C

O "NH-R ²

in which

R ¹ and R ^{2 have} the abovementioned meaning 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 if

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

N-NiI ₂ ^ O ' ^(III)

in which

R ^{1 has} the abovementioned meaning, with isocyanates of the formula (IV),

RJ-N = C = O (IV)

in which

R ^{2 has} the abovementioned meaning, if appropriate in the presence of a diluent and optionally in Reacting the presence of a reaction auxiliary,

or that one

(c) triazolinones of the formula (V),

N-NH ₇

O 0-R ⁵

in which

R ^{1 has} the abovementioned meaning, and R ^{5 is} alkyl, aryl or »arylalkyl, with amines of the formula (VI),

R ² -NH ₂ (VI)

in which

R ^{2 has} the abovementioned meaning, if appropriate in the presence of a diluent and optionally in

Reacting the presence of a reaction auxiliary, or when (d) 1 H-triazolinones of the formula (III),

in which

R ^{1 has} the abovementioned meaning, with urethanes of the formula (VII),

OR ⁵ -OC-NH-R ² (VII)

in which

R ^{2 has} the meaning given above and R ^{5 is} alkyl, aryl or arylalkyl, optionally in the presence of a diluent and optionally in Reacting the presence of a reaction auxiliary.

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

Surprisingly, the substituted triazolinones of the general formula (I) according to the invention have a considerably higher herbicidal potency over problem weeds than the substituted triazolinones known from the prior art, for example 4-amino-1- (N-i-propylcarbamoyl) -3-methylthio ( 1H, 4H) -1,2,4-triazolin-5-one or the compound 4-amino-1- (N-propylcarbamoyl) -3-methylthio (1H, 4H) -1,2,4-triazoline-6 or the compound 4-amino-1- (N-butylcarbamoyl) -3-methylthio (1H, 4H) -1,2,4-triazolin-5-one or the compound 4-amino-1- (N- cyclohexylcarbarrnyl) -3-methylthio (1H, 4H) -1,2,4-triazolin-5-one, which are chemically and operatively 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 ^{1 is} n-propyl, i-propyl, η-butyl,! -Butyl, s-butyl, t-butyl or cyclopropyl and

R ^{2 is} hydrogen, each being straight or branched alkyl of 1 to 18 carbon atoms, alkenyl of 2 to 8 carbon atoms, alkynyl of 2 to 8 carbon atoms, haloalkyl of 1 to 8 carbon atoms and 1 to 17 identical or different halogen atoms, haloalkenyl or haloalkynyl 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 and 1 to 6 hydroxy groups, alkoxyalkyl, alkoxycarbonylalkyl or alkoxycarbonylalkenyl having in each case up to 6 carbon atoms in the individual Alkyl or alkenyl, alkylaminoalkyl or dialkylaminoalkyl having in each case 1 to 6 carbon atoms in the individual alkyl moieties, for cycloalkyl having 11 carbon atoms or for each optionally mono- or polysubstituted or differently substituted cycloalkyl, Cycloalkylnlkyl, cycloalkenyl or Cycloalkenylalkyl each having 3 to 8 Carbon atoms in the cycloalkyl or cycloalkenyl moiety and optionally 1 to 6 carbon atoms in the alkyl moiety, where as substituents in question are: 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 same 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 in each case doubly linked alkanediyl or alkenediyl having in each case up to 4 carbon atoms; R ² furthermore in the heterocyclyl part optionally mono- or polysubstituted, 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 1 to 3 heteroatoms - in particular nitrogen, oxygen and / or sulfur - in the heterocyc./ Iteil is, where possible substituents: halogen, cyano, nitro, and in each case straight-chain or branched alkyl, alkoxy, alkylthio, haloalkyl, haloalkoxy, haloalkylthio or alkoxycarbonyl having in each case 1 to 5 carbon atoms and optionally 1 to 9 identical or different halogen atoms; R ^{2 is} 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 and finally each optionally mono- or polysubstituted by identical or different substituents aralkyl, A'oyl, aryl, aralkyloxy or aryloxy having in each case 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 where as aryl substituents in question: halogen, cyano, nitro, hydroxy , in each case straight-chain or branched alkyl, alkoxy, alkylthio, haloalkyl, haloalkoxy, haloalkylthio, alkylsulfinyl, alkylsulfonyl, haloalkylsulfinyl, haloalkylsulfonyl, alkanoyl or alkoxycarbonyl having in each case 1 to β carbon atoms in the alkyl moiety and optionally 1 to 9 identical or different halogen atoms, cycloalkyl with 3 to β carbon atoms and phenoxy; or R ^{2 is} benzyl with O-CHj-O group fused in the phenyl moiety.

Particular preference is given to compounds of the formula (I) in which R 'is n-propyl, isopropyl, isobutyl, s-butyl, t-butyl or cyclopropyl and

R ^{2 is} hydrogen, methyl, ethyl, η- or i-propyl, n-, 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 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 of 1 to 6 carbon atoms and 1 to 3 hydroxy groups, alkoxyalkyl, alkoxycarbonylalkyl or alkoxycarbonylalkenyl, alkylaminoalkyl or dialkylaminoalkyl each having up to

4 carbon atoms in the individual alkyl or alkenyl moieties or in each case optionally mono- to trisubstituted by identical or differently substituted cyclopropyl, cyclopropylmethyl, cyclopropylethyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclohexylmethyl, cyclohexylethyl, cyclohexenyl or cyclohexenylmethyl, where as substituents in each case in question: fluorine, chlorine, bromine, methyl, ethyl, η- or i-propyl, n-, i-, s- or t-butyl, cyano-, methanediyl, ethanediyl, butanediyl or butadienediyl or Dichlorallyl;

R ² furthermore represents heterocyclylmothyl, heterocyclylpropyl or heterocyclylethyl which is optionally monosubstituted to trisubstituted by identical or different substituents in the heterocyclyl moiety, in each case being suitable as heterocycles:

Μ-μ-Ν r-μ-Ν / 1 / \

if JJ τ ίι -ν J -O

or -N

-7- 29 »

where Z is in each case oxygen or sulfur and in each case being suitable as substituents:

Fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, η- or i-propyl, η-, i-, s- or t-butyl, methoxy, ethoxy, methyltoluio, Trifluoromethyl, trifluoromethoxy or trifluoromethylthio; R ² furthermore for 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 each optionally optionally mono- to trisubstituted by identical or different, optionally straight-chain or branched benzyl, phenylethyl, phenylpropyl, phenylbutyl, phenylpentyl, phenylhexyl, phenylheptyl, phenylcyanmethyl, phenylcyanoethyl, phenylcyanopropyl, benzyloxy, phenylethyloxy , Phenoxy, benzoyl, phenyl or naphthyl, where as Phenylsubstituer.ten in question: fluorine, chlorine, bromine, hydroxyl, cyano, nitro, methyl, ethyl, η- or i-propyl, η-, i-, s or t-butyl, methoxy, ethoxy, methylthio, trifluoromethyl, trifluoromethoxy, trifluoromethylthio, trifluoromethylsulfinyl, trifluoromethylsulfonyl, methylsulfinyl, methylsulfonyl, acetyl, propionyl, methoxycarbonyl, ethoxycarbonyl, cyclohexyl or phenoxy.

Very particular preference is given to compounds of the formula (I) in which R ^{1 is} isopropyl, cyclopropyl or s-butyl and

R ^{2 is} in each case optionally mono- to trisubstituted by fluorine and / or chlorine, methyl, ethyl, η- or i-propyl, n-, i-, sodert-butyl, allyl, propargyl, in each case straight-chain or branched pentyl, hoxyl, heptyl, Octyl, butenyl, pentenyl, hexenyl, butynyl, pentynyl or hexynyl; in addition, in each case optionally monosubstituted to trisubstituted by identical or different fluorine, chlorine, methyl, ethyl and / or cyano, cyclopropyl, cyclopentyl, cyclohexyl, cyclohexenyl, cyctopropylmethyl, cyclopropylethyl, cyclohexylmethyl, cyclohexylethyl or cycloheptyl and finally represents benzyl or phenylethyl.

Specifically, the following substituted trlazolinones of the general formula (I) may be mentioned:

^RJ

-N-NH '

"nh-r ²

(CH ₃ ) ₂ CH-

(CH ₃ J ₂ CH- (CH ₃ J ₂ CH- (CH ₃ J ₂ CH- (CH ₃ J ₂ CH-

-CH I

^C 2 ^H 5

(CH ₃ J ₂ CH- (CH ₃ J ₂ CH- (CH ₃ J ₂ CH- (CH ₃ J ₂ CH-

CH.

* ~ CHo * ~ CH

~ / CHoF

(CH ₃ J ₂ CH- CH

^CH 3

(CH ₃ J ₂ CH- -C-CH = CH ₇

CH ₃

I (CH ₃ ) ₂ CH- -C-CH ₂ -CH = CH ₂

CH ₃ CHO

I ³

(CH ₃ ) ₂ CH- -C -CH ₂ F

CH ₃ CHO

I ³

(CH ₃ ) ₂ CH- -C-CH ₂ Cl

CH ₃ CHoF

I ²

(CH ₃ J ₂ CH- -C-CH ₃

CH ₂ F (CH ₃ J ₂ CH- CH ₂ CH ₂ Cl

CH ₃

CHoCl

I ²

(CH ₃ J ₂ CH- -C-CH ₃

CH ₂ Cl

CH ₃ (CH ₃ J ₂ CH- -C-CHCl ₂

CH ₃ (CH ₃ J ₂ CH-CH-CH ₂ -CH (CH ₃ J ₂

CH ₃

(CH ₃ J ₂ CH (CH ₃ J ₂ CH

CH- (CH ₂ J ₂ -CH (CH ₃ J ₂

(CH ₃ J ₂ CH-

(CH ₃ J ₂ CH- (CH ₃ J ₂ CH- (CH ₃ J ₂ CH- (CH ₃ J ₂ CH-

(CH ₃ J ₂ CH- (CH ₃ ) ₂ CH- (CH ₃ ) ₂ CH-

(CH ₃ J ₂ CH-

(CH ₃ J ₂ CH-

(CH ₃ J ₂ CH-

CH

CH- (CH ₂ J ₃ -CH (CH ₃ J ₂ CH ₃

CH

-C-CF ₃ CH ₃

- (CH ₂ J ₂ ^- CH ₃

- (CH ₂ Jq ^- CH ₃ --CH (CH ₃ J ₂

CH-C ₂ H ₅ CH ₃

CH-CH (CH ₃ J ₂ CH ₃

-CH

CH,

-CH

^C 2 ^H 5 CHO

-C

CHr

CH.

-C-C = CH

CH-

CH-

CH

(CH ₃ ) ₂ CH-

CH-

C- (CH ₂ ) ₂ -CH ₃

(CH ₃ ) ₂ CH- (CH ₃ ) ₂ CH-

H ₂ C 1 CH-I CH-I CH-

H ₂ C 1 CH-I CH-

I I-

H ₂ C \ I CH-I CH-C ^

C \ I CH-

I CH-

C- (CH ₂ ) ₃ -CH ₃

CH-

-C (CH ₃ ) ₃

/ CH ₂ -CH I

H ₃ C

^C 2 ^H 5

-CH-

-CH ₂ -CH ₂ - / V-Cl

-CH

CH

-C-CH = CHo

CHO

R ²

CH ₃ H ₂ C \ I

CH-C-CH ₂ -CH = CH ₂

CH ₃

CH ₃ H ₂ C \ I

CH - C - CH ₂ F

H ₂ Cl

CH ₃

CH ₃ H ₂ C \ I

CH-C-CH ₂ Cl

C I

CH ₂ FI

CH- -C-CH

CH ₂ F

CH-CH-CH ₂ -Cl

C / "I

CH ₃

CH ₂ Cl

CH- -C-CH ₃

CH ₂ Cl CH ₃

CH-C-CHCl

CH ₃

CH-CH-CHo-CH (CHO)

^ I ²

CH ₃

CH- CH- (CH ₂ ) ₂ -CH (CH ₃ ) ₂

^H 2 ^C ί

CH ₃

CH - CH - (CH ₇ ) o - CH (CHO) o

C ^! 2332

CH ₃

CH ₃ I

H ₂ C \ I

CH- -C-CF

CH ₃

H ₂ C \ I

CH-

H ₂ C \ I

CH-

H ₂ C \ I

CH-

CH-

CH-

CH-

H ₂ C \ I

CH-

- (CH ₂ ) ₂ -CH ₃ - (CH ₂ J ₃ -CH ₃ -CH (CH ₃ ) ₂

-CH-CoHc CH ₃

-CH-CH (CH ₃ ) ₂ CHo

-CH

CH

^C 2 ^H 5 9 ^H 3

CH

CH I

-C-C = CH

CH-

9 \ CH-

CH-

CH ₃

CH ₃

I -C (CH ₂ ) ₂ -CH ₃

I CH ₃

CH ₃

I -C (CH ₂ ) ₃ -CH ₃

I CH ₃

I CH-

C ₂ H ₅ -CH-CM ₃

C ₂ H ₅ -CH-

-C (CH ₃ ) ₃

C ₂ H ₅ -CH-CH ₃

CH

-CH I

H ₃ C

^C 2 ^H 5

^C 2 ^H 5 "9 ^H " CHo

^C 2 ^H 5 "9 ^H CHo

CoHc CH ^- 2 5 j

CHO

CoHc ₁ -CH-2 5, CHo

CoHc-CH-2 5 j

CH ₃

-CH-

/ -CH ₂ F CH

^C 2 ^H 5 "9 ^H CH ₃

-C-CH = CHo

CH ₃

CHO

I ³

C ₂ H ₅ -CH- -C-CH ₂ -CH = CH ₂

CH ₃ CH ₃

CHO

I ³

CoHc ^- Cr * ~C ~ CHoF

CH ₃ CH ₃

CH ~

I °

CoHe-CH- -C-CHoCl

²⁵ II

CH ₃ CH ₃

chof

I ²

CoH ₅ -CH- -C-CIIo

²⁵ II

CH ₃ CH ₂ F

CoHc-CH- -CH-CHo-Cl

²⁵ II

CH ₃ CH ₃

CHoCl

I ²

CoHc-CH- -C-CHo

I

CH ₃ CK ₂ Cl

CHO

I ³

CoH ₅ -CH- -C-CHClO

5,!

CH ₃ CH ₃

C ₂ H ₅ -CH- -CH-CH ₂ -CH (CH ₃ J ₂

CH ₃ CHO

C ₂ H ₅ -CH- -CH- (CH ₂ ) ₂ -CH (CH ₃ ) ₂

CH ₃ CH ₃

C ₂ H ₅ -CH- -CH- (CH ₂ ) ₃ -CH (CH ₃ ) ₂

CHO

I ³

C-Cfo

I

CH ₃

CH ₃

CH ₃

CoHc-CH "5,

CH ₃

C ₂ H ₅ -CH-CH ₃

^C 2 ^H 5 "9 ^H " CHo

CoHc-CH-5 j

CHO

C ₂ H ₅ -CH-CHr

^C 2 ^H 5 ~ 9 ^H ~ CHo

^C 2 ^H 5 "9 ^H " CH ₃

* ~ CH ~

C ₂ H ₅ -CH-CH ₃

C ₂ H ₅ -CH-

~ (CH

-CH (CH ₃ ) O ₁

CH-C ₂ H ₅ CHo

-CH-CH (CH ₃ ) ₂ CH ₃

-CH ^ ^NX CH-

-CH

^C 2 ^H 5 CHO

-C

CHr

CH-

-C-C = CH

CH-

CHr

? " ^C 2 ^H 5 CHo

CHO

I ³

-C- (CH ₂ ) ₂ -CH ₃ CH ₃

CHQ

I ³

-C- (CH ₂ J ₃ -CH ₃

CH ₃ -C (CH ₃ J ₃

If, for example, HN-isobutylcarbamoylH-isopropylidenimino-S-isopropylM-triazoline-S-on is used as the starting compound, the course of the reaction of process (a) according to the invention can be represented by the following formula scheme:

/ CH ₃

H ₂ O / Η®

- (CH ₃ J ₂ CO NH-CH ₂ -CH (CH ₃ J ₂

^ ₂ -CHn ₁ -r ^m 2

O NH-CH ₂ -CH (CH ₃ ) ₂

If, for example, 4-amino-3-cyclopropyl-1,2,4- (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 can be represented by the following formula scheme:

N-NHo

^£ + (CH₃J₃C-N = C = O

O = C-NH-C (CH ₃ ) ₃

If, for example, i-phenoxycarbonylM-amino-SS-butylM ^^ -triazolin-B-on and N, N-oiethylpropane-1,3-diamine are used as starting materials, the course of the reaction of process (c) according to the invention can be described by the following equation represent:

CHO

I ³

-N-NH ₂

+ H ₂ N-CH ₂ -CH ₂ -CH ₂ -N

O = C-OC ₆ H ₅

? ^H 3

- C ₆ H ₅ -OH

J ₇ Hc; -CrT ^, N-NHo

T ⁰

O = C-NH-CH ₂ -CH ₂ -CH ₂ -N

If, for example, 4-amino-3-isopropyl-1,2,4- (1H) -triazolin-5-one and N-isopropyl-phenylcarbamate are used as starting materials, the course of the reaction of process (d) according to the invention can be determined by the following equation represent:

Τι ι

-NH-

N-NH ₂

-C ₆ H ₅ OH "

> ₀

I / CH ₃

O = C-NH-CH

The hydrazones required as starting materials for carrying out the process (a) according to the invention are generally defined by the formula (II). In this formula (II) R 'and R ² , preferably those radicals which have already been mentioned in connection with the description of the compounds of the formula (I) according to the invention as being preferred for these substituents. R ³ and R ⁴ are each independently hydrogen, straight or branched alkyl of 1 to 4 carbon atoms or phenyl or benzyl.

The hydrazones of the formula (II) are not yet known. They are also the subject of the present invention. However, they are obtained in analogy to known processes (cf., for example, Acta Pol. Pharm, 38, 153-162 [1981] or CA 95, 203841 j), for example when 1-unsubstituted 4-amino-triazolinones of the formula (III) .

(III)

in which

R 'has the meaning given above,

with aldehydes or ketones of the formula (VIII),

C = O (VIII)

in which R ³ and R ^{4 have} the abovementioned meaning, if appropriate 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 ⁰ C and 12O ⁰ C reacted and the thus obtainable 1 - unsubstituted triazolinone hydrazones of the formula (IX),

-N-N = C

in which

R ¹ , R ³ and R ^{4 have} the abovementioned meaning, either in a subsequent second stage with isocyanates of the formula (IV),

Ri-N = C = O (IV)

in which

R ^{2 has} the meaning given above, optionally in the presence of a diluent, such as Dichloromethane or dioxane and gegebenenfclls in the presence of a reaction auxiliary, such as ^Be: game as triethylamine at Temperatures between 50 ⁰ C and 15O ⁰ C converts;

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

OR ⁵ -OC-CI (X)

in which

R ^{5 is} alkyl, aryl or arylalkyl, optionally in the presence of a diluent such as tetrahydrofuran and optionally in the presence of a reaction auxiliary, such as sodium hydride or potassium t-butoxide at temperatures between -2O ⁰ C and + 40 ⁰ C and the like available triazolinones of the formula (XI),

(XI)

in which

R ', R ³ , R ⁴ and R ^{5 have} the abovementioned meaning, in a subsequent third stage with amines of the formula (VI),

R ² -NH ₂ (VI)

in which

R ^{2 has} the abovementioned meaning, if appropriate in the presence of a diluent such as tetrahydrofuran and optionally in the presence of a base such as sodium hydroxide, potassium hydroxide or diazabicycloundecene (DBU) at temperatures between 2O ⁰ C and 50 ⁰ C.

It is also possible and optionally advantageous to react the 1 -unsubstituted triazoline hydrazones of the formula (IX) with chloroformates of the formula (X) and then reacting the triazolinones (XI) thus obtainable with amines of the formula (VI) in to carry out a reaction step in a so-called one-pot process.

The 1-unsubstituted 4-amino-triazolinones of the formula (III) are known in some cases and can be obtained in analogy to known processes (cf., for example, J. Heterocycl, Chem., 16, 403 (1979); J. Heterocycl, Chem., 17,1691 [1980 Chem. 18,215 [1983]; Chem. Ber 98,3025 [1965]; Liebigs Ann. Chem. 637,135 [19601; J. Heterocycl Chem 21,1769-1774 [1984]; Chim. Acta Door, 7, 269-290 [1979] or CA 106 (17): 138338β [1986]).

The aldehydes or ketones of the formula (VIII) are generally known compounds of organic chemistry. The 1-unsubstituted triazolinone hydrazones of the formula (IX) are known in some cases (see, for example, Chim, Acta, Türe, 7, 269-290 [1979]).

The chloroformic acid ethers of formula (X) are generally known compounds of organic chemistry.

The mentioned as intermediates triazolinones of the formula (Xl) are not yet known and also the subject of the invention.

R 'preferably represents those radicals which have already been described in connection with the description of

Substances of the formula (I) according to the invention have been mentioned as being preferred for this substituent.

R ³ and R ⁴ are each independently hydrogen, straight or branched alkyl of 1 to 4 carbon atoms, or phenyl or benzyl, and

R ⁵ preferably represents straight-chain or branched alkyl having 1 to 4 carbon atoms or optionally

one to three, identically or differently substituted phenyl or benzyl, suitable substituents being in each case: 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.halogenoalkoxy or haloalkylthio each having 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms;

R ° stands in particular for methyl, ethyl, η or i-propyl, n-, i-, s- or t-butyl or, if desired, one to two times,

identical or differently substituted phenyl or benzyl, with sub-substituents being in each case: fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, η- or i-propyl, η-, i-, s- or t-butyl, Methoxy, ethoxy, n- or i-propoxy, methylthio, trifluoromethyl, trifluoromethoxy or trifluoromethylthio.

The 1 H-triazolinones required as starting materials for carrying out the processes (b) and (d) according to the invention are generally defined by the formula (III). In this formula (III), R 'preferably represents 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 this substituent.

The 1 H-triazolinones of the formula (III) are either known or obtainable in analogy to known processes (cf.

J. Heterocycl. Chem. 16,403 [1979]; J. Heterocycl. Chem. 17,1691 [1980]; Europ. J. med. Chem. 18,215 [1983]; Chem. Ber. 98, 302511965]; Liebigs Ann Chem. 637,135 [196O]; J. Heterocycl. Chem. 21, 1769-1774 [1984]; Chim. Acta door. 7,269-270 [1979]; CA 106 (17): 138338 e [1986]).

Not yet known and also the subject of the invention are 1-unsubstituted 4-aminotriazolinones of the formula (III a),

^{1 1} N-NH ₂

in which

R ¹ ' ^{1 is} η-butyl, i-butyl, s-butyl or cyclopropyl, in particular s-butyl or cyclopropyl.

They are obtained in analogy to known processes (cf., for example, J. Heterocycl Chem 21,1769 [1984] and Chem. Ber 98,3025 [1965]), for example, when hydrazine hydrate is reacted with diphenyl carbonate in a conventional manner and the carbonic acid hydrazide obtainable with carboxylic acid derivatives of the formula (XII)

R '-'-COOR "(XII)

in which

R ¹ '' has the meaning given above, and R * represents hydrogen or straight-chain or branched alkyl of up to 4 carbon atoms,

also in the usual way at temperatures of between 15O ⁰ C and 250 ° C is cyclized (see. also the preparation examples). Carboxylic acid derivatives of the formula (XII) are generally known compounds of organic chemistry. The isocyanates 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 form (IV), R ² preferably represents 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 this substituent. The isocyanates of the formula (IV) are generally 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.

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 ¹ preferably represents 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 this substituent. R ⁶ 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 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;

R ⁶ in particular represents 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, where as substituents in question come: fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, η odor i-propyl, η-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, methylthio, trifluoromethyl , Trifluoromethoxy or trifluoromethylthio

 The triazolinones of the formula (V) are not yet known

 They are obtained in analogy to known processes, if 1H-triazolinones of the formula (III),

(III)

I ~

in which

R ^{1 has} the abovementioned meaning, with chloroformates of the formula (X),

OR ⁵ -OC-CI (X)

in which

R ^{6 has} 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 Ίβί teratures between -2O ⁰ C and + 4O ⁰ C (see also the preparation examples). For carrying out the process (d) further required as starting materials urethanes are characterized by the Formula (VII) generally defined. In this formula (VII), R ² preferably represents those radicals which are already related

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

R ⁵ preferably represents those radicals which have already been used in connection with the description of the precursors of the forms! (V)

have been mentioned as preferred or particularly preferred for this substituent.

The urethanes of formula (VII) are generally known compounds of organic chemistry or can be obtained by means of general

known method.

As acids for carrying out the process (a) according to the invention, all are usually used for hydrazone cleavage

usable inorganic and organic acids in question. Preferably, inorganic mineral acids such as hydrochloric acid, sulfuric acid or phosphoric acid are used.

Suitable diluents for carrying out the process (a) according to the invention are all customary organic or

inorganic solvents in question. Preference is given to using polar mi: 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 in the implementation of the inventive method (a) in a wider range

be varied. In general, one works at temperatures between 2O ⁰ C and 15O ⁰ C, preferably at temperatures between 5O ⁰ C and 12O ⁰ C.

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

200mbar in question.

For carrying out the process (a) according to the invention, in general 1 to 1 are used per mole of hydrazines of the formula (II)

50 moles, preferably 1 to 20 moles of acid. In this case, the hydrazone of the formula (II) is dissolved in a suitable amount

Diluent, then adds the required amount of acid and the mixture is concentrated under reduced pressure over

slowly for several hours.

In a particular embodiment, it is also possible, the inventive method (a) and the preparation of the

required precursors of formula (II) in a reaction step in a so-called one-pot process to perform.

There is the possibility to choose as starting compounds the triazolinones of the formula (XI) and these successively in the One-pot process with amines of the formula (VI) and then with acid according to the process (a) according to the invention

(see also the preparation examples) or alternatively, as starting compounds, the triazoline hydrazones of

To select formula (IX) and this successively in a one-pot process with chloroformates of formula (X), then with Amines of formula (Vl) 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 Question. These include in particular aliphatic, aicyclic or aromatic, optionally halogenated Hydrocarbons, such as, for example, benzene, benzene, toluene, xylene, chlorobenzene, petroleum ether, hexane, cyclohexane, Diciilormethan, 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. If appropriate, the process (b) according to the invention is 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, N, N-dimethylaniline, N, N-diethylbenzylamine, Ν, Ν-dimethylcyclohexylamine or dibutyltin dilaureate, Pyridine, Ν, Ν-dimethylaminopyridine, diazabicyclooctane (DABCO), diazabicyclononene (DBN) or diazabicycloundecene (DBU). The reaction temperatures can in carrying out the process (b) in a wider range

be varied. In general, one works at temperatures between 0 ° C and 150 ⁰ C, preferably at temperatures between 2O ⁰ C and 100 ⁰ C.

To carry out the process (b) according to the invention, in general, 1 mol of 1H-triazolinone of the formula (III) is employed

1.0 to 2.0 moles, preferably 1.0 to 1.5 moles of isocyanate of formula (IV) and optionally 0.001 to 2.0 moles, preferably 0.001 to 1.0 mole of reaction auxiliary.

The reaction is carried out, workup and isolation of the reaction products by generally customary methods. Suitable diluents for carrying out the processes (c) and (d) according to the invention are inert organic compounds Solvent in question. These include in particular aliphatic, aicyclic 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, 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 Essigsäureeth \! Aster, or sulfoxides, such as dimethyl sulfoxide. If appropriate, the processes (c) and (d) according to the invention can be carried out in the presence of a suitable reaction auxiliary

be performed. As such, all customary inorganic or organic bases are suitable. 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, and also tertiary amines, such as triethylamine, Ν, Ν-dimethylaniline, pyridine,

Ν, Ν-dimethylaminopyridine, diazabicyclooctane (DABCO), diazabicyclononene (DBN) or diazabicycloundecene (DBU).

The reaction temperatures can in carrying out the process according to the invention (c) and (d) in a larger Bareich be varied. In general, one works at temperatures between 0 ° C and 12O ⁰ C, preferably at Temperatures between 20 ° C and 5O ⁰ C. In order to carry out process (c) according to the invention, in general 1.0 is added per mole of triazolinone of the formula (V)

to 5.0 moles, preferably 1.0 to 2.5 moles of amine formula (VI) and optionally 1.0 to 2.0 moles, preferably 1.0 to 1.2 moles of reaction auxiliary.

The reaction is carried out, workup and isolation of the reaction products by generally customary methods. In a particular embodiment, it is also possible, the inventive method (c) and the preparation of the

to carry out necessary precursors of the formula (V) in a reaction step in a so-called one-pot process.

It is based on 1 H-triazolinones of the formula (III) and sets them one after the other in a one-pot process first Chioroic acid esters of the formula (X) and then with amines of the formula (VI) according to the invention Method (c) um. To carry out the process (d) according to the invention, in general, 1 mol of 1H-triazolinone of the formula (III) is employed

1.0 to 5.0 moles, preferably 1.0 to 2.5 moles, of urethane of formula (VII) and optionally 1.0 to 5.0 moles, preferably 1.0 to 2.5 moles, of reaction auxiliaries.

The reaction is carried out, workup and isolation of the reaction products by generally customary methods. A further method of obtaining compounds according to the invention of formula (I) is that oxadiazolinones of the Formula (XIII),

(XIII)

NH-R ²

in which

R * and R ^{2 have} the abovementioned meaning, with hydrazine hydrotreated in the presence of a suitable diluent such as methanol or ethanol at temperatures between 20 ° C and 100 ⁰ C and the thus available carbazic acid derivatives of the formula (XIV),

R'-C-NH-N-C-NH-NHa (XIV)

O = C-NH-R ²

in which

R 'and R ^{2 have} the abovementioned meaning, in the presence of a suitable diluent such as Toluene, chlorobenzene or dichlorobenzene thermally cyclized at temperatures between 8O ⁰ C and 200 ⁰ C. Oxadiazolinones of the formula (XIII) are known (see, for example, FR 1415605 and CA 64: P5105g and NL6G10645 and CA 65, respectively: P2274d-f) or obtainable according to well-known ancestors, for example by reaction of the corresponding

4 H-oxadiazolinones with isocyanates 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).

The purification of the end products of the formula (I) is carried out by conventional methods, for example by column chromatography

or by recrystallization.

The characterization is carried out by means of the melting point or by 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, haulm killers and in particular as Weed killers are used. By weeds in the broadest sense are meant all plants in places

grow up where they are unwanted.

Whether the substances according to the invention act as total or selective herbicides depends essentially on the one used

Amount off.

The active compounds according to the invention can, for. B. be used in the following plants.

Dlkotyle weeds of the genera: Sinapis, Lepidium, Galium, Stellaria, Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solanum, Rorippa , Rotala, Lindernia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis, Papaver, Centaurea, and Mercurialis.

Dicotyledonous 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, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum , Sphenoclea, Dactyloctenium, Agrostis, Alopecurus, Apera.

Monocotyledonous cultures of the genera: Oryza, Zea, Triticum, Hordeum, Avena, Seeale, Sorghum, Panicum, Saccharum, Pineapple, Asparagus, Allium. However, the use of the active substance according to the invention is by no means restricted to these genera but extends

in the same way to other plants.

The compounds are suitable depending on the concentration for total weed control z. B. on industrial and Railway tracks and on paths and squares with and without tree cover. Likewise, the connections to the Weed control in permanent crops, e.g. Forestry, ornamental, fruit, wine, citrus, nut, banana, coffee, tea, rubber, Oil palm, cocoa, berry fruit and hop plants and used for selective weed control in annual crops

become.

In this case, the active compounds according to the invention can be mono- and dikotyler with particularly good success to combat Weeds in monocotyledonous and dicotyledonous crops such as sugar beets, corn, wheat and barley. 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 substance impregnated nature and synthetic materials as well as Feinstverkapselungen in polymeric materials.

These formulations are prepared in a known manner, for. B. by mixing the active ingredients with extenders, ie

liquid solvents and / or solid Träger'.offen, optionally with the use of surfactants, emulsifiers and / or dispersants and / or foam-forming agents.

In the case of using water as an extender z. As well as organic solvents used as auxiliary solvents

become. Suitable liquid solvents are essentially: aromatics, such as xylene, toluene, or Alky! Naphthalenes, chlorinated aromatic and chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for. Petroleum fractions, mineral and vegetable oils,

Alcohols such as butanol or glycol and their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or Cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethyl sulfoxide, and water. Suitable solid carriers are: For example, ammonium salts and natural flours, such as kaolins, clays, talc, chalk, quartz, attapulgite, Montmorillonite or diatomaceous earth and ground synthetic minerals, such as fumed silica, alumina and Silicates, as solid carriers for granules come into question: z. Broken and fractionated natural rocks such as calcite, Marble, pumice, sepiolite, dolomite and synthetic granules of inorganic and organic flours and granules

made of organic material such as sawdust, coconut shells, corn cobs and tobacco stalks; as emulsifying and / or foam-producing agents are in question: z. Nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid

Esters, polyoxyethylene fatty alcohol ethers, e.g. B. alkylaryl polyglycol ether, alkyl sulfonates, Alky! Sulfate, arylsulfonates and protein hydrolysates; suitable dispersants are: e.g. Lignin-sulphite liquors and methylcellulose. Ee can be used in the formulations adhesives such as carboxymethylcellulose, natural and synthetic powdery, granular or

latex-shaped polymers are used, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, as well as natural

Phospholipids, such as cephalins and lecithins, and synthetic phospholipids. Other additives can be mineral and

be vegetable oils.

It can dyes such as inorganic pigments, eg. For example, iron oxide, titanium oxide, Ferrocyanblau 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 are used. 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 admixture with known herbicides for controlling weeds, ready-to-use formulations or tank mixes possibly being suitable. 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 (AMETHYDIONE) or N- (2-benzthiazolyl) -N, N'-dimethylurea (METABENZTHIAZURONE) for weed control in cereals; 4-Amino-3-methyl-6-phenyl-1,2,4-triazine-5 (4H) -one (METAMITRON) for controlling weeds in sugar beets and 4-arro-ino-6 (1,1-dimethylethyl) - 3-methylthio-1,2,4-triazine-5 (4H) -one (METRIBUZINE) for weed control in soybeans. Also, mixtures with 2,4-dichlorophenoxyacetic acid (2,4-D); 4- (2,4-dichlorophenoxy) -butyric acid (2,4-DB); 2,4-dichlorophenoxypropionic acid (2,4-DP); Chloroacetic acid N- (methoxymethyl) -2,6-diethylanilide (ALACHLOR); 2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine (ATRAZIN); Methyl 5- (2,4-dichlorophenoxy) -2-nitrobenzoate (BIFENOX); 3,5-dibromo-4-hydroxybenzonitrile * Z ', O,' -. 69S_BM & lMM.M {((4-methoxy-6-methyl-1,3,5-triazin-2-yl) -amino] -carbonyl} N, N-dimethyl-N '- (3-chloro-4-methylphenyl) -urea (CHLORTOLURON); 2-chloro-4-ethylamino-6- (3-cyanopropylamino) -1,3-benzene sulfonamide (CHLOROSULFURON); 5-triazine (CYANAZINE); 2- (4- (2,4-Dichlorophenoxy) -phenoxyl-propionic acid, its methyl or ethyl ester (DICLOFOP); 3,6-dichloro-2-pyridinecarboxylic acid (CLOPYRALID); NN-Di N-propyl-thiocarbamic acid S-ethyl ester (EPTAME); 4-Amino-6-t-butyl-3-ethylthio-1,2,4-triazine-5 (4H) -one (ETHIOZIN); 2- {4 - ((6-chloro-2-benzoxazolyl) -oxy] -phenoxy} -propanoic acid, its methyl or ethyl ester (FENOXAPROP); | (4-amino-3,5-dichloro-6-fluoro-2-pyridinyl) -oxy] -acetic acid or its 1-methylheptyl ester (FLUROXYPYR); methyl 2- (4,5-dihydro-4-methyl-4- (1-methylethyl) -5-oxo-1H-imidazol-2-yl 'j-4 (5) -methylbenzoate (IMAZAMETHZENZ); 3,5-diiodo-4-hydroxybenzonitrile (1OXYNIL); N, N-dimethyl-N' - (4-isopropylphenyl) urea (ISOPROTURON); (2-methyl -4-c chlorophenoxy) acetic acid (MCPA); (4-chloro-2-methylphenoxy) -propionic acid (MCPP); N-methyl-2- (1,3-benzthiazol-2-yloxy) -acetanilide (MEFENACET); 2-ethyl-6-methyl-N- (1-methyl-2-methoxyethyl) -chloroacetanilide (METOLACHLOR); 2 - {[l ((4-methoxy-6-methyl-1,3,5-triazin-2-yl) amino) carbonyl] amino) sulfonyl} benzoic acid or its methyl ester (METSULFURON); (2-Chloro-4-trifluoromethyl-phenyl) - (3-ethoxy-4-nitro-phenyl) -ether (OXYFLUORFEN); N- (1-tylpropyl) -3,4-dimethyl-2,6-dinitroaniline (PENDIMETHALIN); 2-chloro-N-isopropylacetanilide (PROPACHLOR); O- (6-Chloro-3-phenyl-pyridazine-butyl-S-octyl-thiocarbonate-PYRIATECHI-chloMe-bis-tethylamino J-ISB-triazine (SIMAZIN); 4-ethylamino-2-t-butylamino-e-methylthio s-triazine (TERBUTRYNE); 3-l ([((4-methoxy-6-methyl-1,3,5-triazin-2-yl) amino] carbonyl] amino] sulfonyl] thiophene-2 methyl N-carboxylate (THIAMETURON); N, N-diisopropyl S- (2,3,3-trichloroallyl) thiolcarbamate (TRIALLATE) and 2,6-dinitro-4-trifluoromethyl-N, N-dipropylaniline (TRIFLURALIN) Surprisingly, some mixtures also show a synergistic effect.

It is also possible to mix it with other known active substances, such as fungicides, insecticides, acaricidone, nematicides, bird repellants, plant nutrients and soil conditioners.

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, for. B. by pouring, spraying, spraying, Stre ien. The active compounds according to the invention can be applied both before and after emergence of the plants. They can also be incorporated into the soil before sowing.

The amount of active ingredient used can vary within a substantial range. It depends essentially on th ^e type of effect desired. In general, the application rates are between 0.01 and 10 kg of active ingredient per HeKd bottom surface, preferably between 0.05 and 5 kg per ha

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

Preparation Examples

Beispiol 1

N-NH ₂

(Method Ib])

To 7.1 g (0.05 mol) of 4-amino-3-isopropyl- (1H) -1,2,4-triazolin-5-one in 100 ml of absolute acetonitrile is added 6.1 g (0.055 mol) Cyclopentyl isocyanate and a small amount of diazabicycloundecene (DBU), stirred for 12 hours at room temperature, then concentrated in Vacuum, the residue is taken up in dichloromethane, washed with water until neutral, dried over magnesium sulfate, concentrated

and the residue is crystallized by trituration with diethyl ether.

This gives 10.0 g (78% of theory) of 4-amino-1- (N-cyclopentylcarbamoyl) -3-isopropyl-1,2,4-triazolin-5-one of melting point Example 2

N-NH ₂

HIN ^ N ' ^X ^ ₀

i Γ ³

O, NH-C-C = CH

CH ₃

(Method (a) - stoving variant)

To 11.1 g (0.05 mol) of 4- (4-methylpent-2-ylidenimino) -3-cyclopropyl-1,2,4- (1H) -triazolin-5-one in 150 ml of absolute acetonitrile

5.5 g (0.05 mol) of 3-methyl-3-butynyl isocyanate and a dodecabicycloundecene (DBU), stirring for 12 hours at 20 ° C, then concentrated in vacuo, the residue is taken up in aqueous ethanol, 2 Concentrated hydrochloric acid, concentrated at 60 ° C slowly under reduced pressure, the residue is taken up in dichloromethane, washed with saturated

Sodium bicarbonate solution, dried over magnesium sulfate, concentrated and the residue is crystallized by trituration with Diethyl ether. This gives 10.4 g (84% of theory) of α-amino-α-cyclopropyl-1-N-O-methyl-S-butyne-1-carbamoyl-1-yl atriazolin-o-one from Melting point 160 ^° C. In a corresponding manner and according to the general information on the preparation, the following substituted Triazolinones of the general formula (I):

(I)

Ex, -No.

NH-R '

3 (CH ₃ J ₃ C-

4 CH ₃ - (CH ₂ J ₂ -

(CH ₃ ) ₂ CH-

- (CH ₂ ) ₅ -CH ₃

CH-

-C-C = CH

CH-

CH,

-C-C = CH

phys ikali see constant

n ²⁰ : 1.4980

Mp 106 ⁰ C

Mp 90 ^° C

(CH ₃ ) ₂ CH-

-CH

Mp 133 ⁰ C

CHo "* (CHo) o ~ *

Mp 98 ⁰ C

(CH ₃ ) ₃ C-

CHo "* (CHo

(CH ₃ J ₂ CH-

Mp. 158 ⁰ C mp. 100 C ⁰

n ²⁰ : 1.5168 D

Example, no.

^RJ

physico-chemical constant

CH ₃ - (CH ₂ J ₂ -

(CH ₃ J ₂ CH-

(CH ₃ J ₃ C-

14 (CH ₃ J ₃ C- 15 (CH ₃ J ₃ C- 16 (CH ₃ J ₃ C- 17 CH ₃ - (CH ₂ J ₂ 18 (CH ₃ JoCH- Ct 19 HoC-v I CH- H ₂ C--

CH-

~ C ~ CH ₂ C1

CH-

CH,

-C-CH ₂ Cl

CH

-C (CH ₃ J ₃

-C (CH ₃ J ₃ -C (CH ₃ J ₃

-C (CH ₃ J ₃ n ²⁰ : 1.5890

n ²⁰ : 1.5650

¹ H-NMR * ⁾ : 1.44 (9H), 4.48 (2H)

¹ H NMR * ^} : 1.44 (9H), 4.53 (2H)

Mp 142 ⁰ C mp 203 ⁰ C

Mp. 112 ⁰ C mp. 108 C ⁰

Mp 151 ⁰ C

(CH ₃ J ₃ C-

(CH ₃ J ₃ C-

-CH- *

(S-J config.

CHo -CH (R + J config.

n ²⁰ : 1.5171

D,

n ²⁰ : 1.5411

Eg no.

^RJ

physical constant

22 (CH ₃ ) ₃ C-C-CH ₂ -Cl mp 133 ° C

23 (CH ₃ ) ₃ C-

27 (CH ₃ J ₃ C-

28 (CH ₃ J ₃ C-

(CH ₃ J ₃ C- (CH ₃ J ₂ CH-

CH-

CH,

CHr

CH,

CH

-CH-C ₂ H ₅ CH ₃ Fp. 148 ⁰ C

(CH ₃ J ₃ C- -C- (CH ₂ J ₃ -CH ₃ η ²⁰ : D 1, 4844 (CH ₃ J ₃ C- -CH-CH (CH ₃ J ₂ I Mp. 135 ⁰ C CH ₃ CHO (CH ₃ J ₃ C- -C-CH ₂ F Mp. 141 ⁰ C

Mp 208 ⁰ C

n ²⁰ : 1.5520 mp. 172 ⁰ C

Mp 83 ⁰ C

Eg no.

phys ikali see constant

31 (CHg) ₂ CH-

I CH-C ^

C \ I CH-

^C " ^C 2 ^H 5 CHo

n ²⁰ : 1.4801

Mp 177 ⁰ C

Mp 107 ⁰ C

34 (CHg) ₂ CH-

35 (CHg) ₂ CH-

(CH ₂ ) ₂ CH- (CH ₂ ) ₂ CH- (CH ₂ ) ₂ CH-

C-CH ₉ FI 3 I CH ₂ ci CH I CH ₃ I C- I ₂ ci I CH 3 CH T CHCl I C-

CH

-CH (CHg) ₂

CH

-C- (CH ₂ J ₃ -CH ₃ Fp. 124 ⁰ C

¹ H NMR * ⁵ : 1.34 (6H), 3.12 (IH), 4.40 (2H)

Mp 121 ⁰ C

Mp 124 ⁰ C

n ²⁰ : 1.4874

CH,

39 (CH _{3) 2} CH- -C- (CH _{2) 3} -Chg

CHo n ²⁰ : 1.4847

Example no.

40 (CH ₃ J ₂ CH-

41 (CH ₃ J ₂ CH-

42 (CH ₃ J ₂ CH-

CH-CH (CH ₃ J ₂

CHr

* -CH

phys ical constant

n ²⁰ : 1.4860

n ²⁰ : 1.5308

CH ₃ (S -) - Config

CH-

-C

CHr

n ²⁰ : 1.5355

43 (CH ₃ J ₂ CH-

n ²⁰ : 1.5011 D

I CH-

CH,

-C-CHoCl

I ²

CHO

Mp 94 ⁰ C

H ₂ C \ I CH-

CHr

-C-chof

I ²

CHO

Mp 138 ⁰ C

* The 'H NMR spectra were recorded in duuterochloroform (CDCI ₃ ) with totramethylsilane (TMS) as the internal standard. Given is the chemical advance as δ value in ppm.

Preparation of Starting Variants Example III-1

N-NHo

To 884g (17.68 moles) of hydrazine hydrate are added with stirring and ice-cooling portions 1892g (8.84 mol) of diphenyl carbonate, so that the temperature of the reaction mixture does not exceed 3O ⁰ C. After completion of the addition, the mixture is stirred for about 3 hours at 80 ° C, water of reaction removed in vacuo, then 760g (8.84 mol) Cyclopropancnrbonräure to, then heated under inert gas in the course of β hours to 200 ° C and distilled - early release of water of reaction. After completion of the reaction, it is concentrated to dryness in vacuo, the residue is extracted with 3,000 ml of boiling ethanol, filtered, cooled and the precipitated crystalline precipitate is filtered off with suction and dried. 420g (34% of theory) of 4-amino-3-cyclopropyl-1,2,4- (1H) -triazolin-5-one of melting point 181 ⁰ C. In a corresponding manner one obtains:

Example 111-2CHo

CoHc-Clfv, N-NH ₇

2 5 γ ~

H Melting point 16Q ⁰ C Delsplel III-3 / pn \ ρπ \ jr Ny H Schrp ':. Zpunkt168 ° C Example III-4 CH ₃ \ CH ₃ ^ ^H 2N C ² N-NHo I I

H Example 111-5CH ₃ - (CH ₂ )

II

H Example {111-6}

(CH ₃ ) ^ CV ₁ N-NH ₂

-V

tl

H melting point 261 ⁰ C

Example VIII-I

H ₂ C \ _ / H / CH ₃

\ CH ₂ -CH (CH ₃ ) ₂

142g (1.0 mol) of 4-amino-3-cyclopropyl-1,2,4- (iH) -triazolin-5-one are dissolved in 1000mL of methyl isobutyl ketone with 100mg addition

p-toluenesulfonic acid while heated under reflux over a water until no more reaction water

is released. For workup, the mixture is concentrated in vacuo and the residue by trituration with petroleum ether for

Crystallization brought.

This gives 66 g (30% of theory) of 4- (4-Mbthylpent-2-ylidenimino) -3-cyclopropyl-1,2,4- (1 H) -triazolin-5-one of the melting point

-29- 298 393 Application belsplele

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

-N-NH ₂

(A) O = C-NH-CH (CH ₃ J ₂

4-Amino-1- (N-isopropylcarbamoyl) -3-methylthio (1H, 4H) -1,2,4-triazolin-5-one CH ₃ S ^ N-NH ₂

N ^ -N '^ Q (B)

O = C-NH- (CH ₂ J ₂ -CH ₃

4-amino-1- (N-propylcarbamoy!) - 3-methylthio (1H, 4H) -1,2,4-triazolin-5-one _l3 Sv ^ -N-NH ₂

(O

O = C-NH- (CH ₂ J ₃ -CH ₃

4-Amino-1- (N-butylcarbamoyl) -3-methylthio (1H, 4H) -1,2,4-triazolin-5-one N-NHo

, Ο,

NH-

4-Amino-1- (N-cyclohexylcarbamoyl) -3-methylthio (1H, 4H) -1,2,4-triazolin-5-one all known from JP 52/125168.

Example A Pre-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 concentration of active ingredient in the preparation does not matter, only the application rate of the active ingredient per unit area is decisive. After three weeks, the degree of damage of the plants is rated in% damage compared to the development of the untreated control. It means:

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

A clear superiority in the effectiveness of comparable crop selectivity over the prior art show in this test z. B. the compounds according to the following preparation examples: (1), (10), (18), (30), (31), (34), (37) and (40).

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 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 active compound is injected test plants, which have a height of 5-1 Scm so that the particular desired amounts of active ingredient per unit area are applied. The concentration of the spray mixture is chosen so that in 2000I water / ha, the respective desired amounts of active ingredient are applied. After three weeks, the degree of damage of the plants is rated in% damage in comparison to the development of the untreated control

 It means:

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

A clear superiority in the effectiveness of comparable crop selectivity over the prior art show in this test z. B. the compounds according to the following Horstellungsbeispiele: (12), (18), (19), (30), (34), (36), (37), (38), (39) and (40).

Claims (8)

claims: 1. Substituted triazolinones of the general formula (I)
N-NH ₂ ¹¹ 1 2
O NH-FT in which R ^{1 is} alkyl of 3 to 4 carbon atoms or cyclopropyl and R ^{2 is} hydrogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, cyanoalkyl, hydroxyalkyl, alkoxyalkyl, alkoxycarbonylalkyl, alkoxycarbonylalkenyl, alkylaminoalkyl, dialkylaminoalkyl, each optionally substituted cycloalkyl , Cycloalkylalkyl, cycloalkenyl or cycloalkenylalkyl, optionally substituted heterocyclylalkyl, each optionally substituted aralkyl, aroyl, aryl, aralkyloxy or aryloxy, alkoxy, alkenyloxy or alkynyloxy. 2. Substituted triazolinones of the formula (I) according to claim 1, in which R ^{1 is} n-propyl, i-propyl, η-butyl, i-butyl, s-butyl, t-butyl or cyclopropyl; and R ^{2 is} hydrogen, in each case straight-chain or branched alkyl having 1 to 18 carbon atoms, alkenyl having 2 to 8 carbon atoms, alkynyl of 2 to 8 carbon atoms, haloalkyl of 1 to 8 carbon atoms and 1 to 17 identical or different halogen atoms, haloalkenyl or haloalkynyl mt each 2 to 8 carbon atoms and 1 to 15 or 13 identical or different halogen atoms, cyanoalkyl with 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 each having from 1 to 6 carbon atoms in the individual alkyl moieties, for Cycloalkyl having 11 carbon atoms or for each optionally mono- or polysubstituted or different substituie rtes 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 alkyl moiety, where as substituents in question are: halogen, cyano and in each case straight-chain or branched alkyl or haloalkyl 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 and 1 to 5 identical or different halogen atoms or in each case doubly linked alkanediyl or alkenediyl having in each case up to 4 carbon atoms; R ^{2 is} also in the heterocyclyl optionally single or polysubstituted, 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 1 to 3 heteroatoms in particular nitrogen, oxygen and / or sulfur - in the heterocyclyl, wherein suitable substituents are: halogen, cyano, nitro, and in each case straight-chain or branched alkyl, alkoxy, alkylthio, haloalkyl, haloalkoxy, haloalkylthio or aikoxycarbonyl having in each case 1 to 5 carbon atoms and optionally 1 to 9 identical or different halogen atoms; R ² furthermore represents in each case straight-chain or branched alkoxy having 1 to 8 carbon atoms, alkeniyloxy having 2 to 8 carbon atoms or alkynyloxy having 2 to 8 carbon atoms and finally in each case optionally monosubstituted or polysubstituted by identical or different substituents Aralkyl, aroyl, aryl, aralkyloxy or aryloxy , in each case having 6 to 10 carbon atoms in the aryl part and optionally 1 to 8 carbon atoms in the straight-chain or branched alkyl part, suitable alkyl substituents being halogen and cyano and wc being suitable as aryl substituents in each case: halogen, cyano, nitro, hydroxy, in each case straight-chain or branched alkyl, alkoxy, alkylthio, haloalkyl, haloalkoxy, Halogtr.alkylthio, alkylsulfinyl, alkylsulfonyl, haloalkylsulfinyl, haloalkylsulfonyl, alkanoyl or Aikoxycarbonyl each having 1 to 6 carbon atoms in the alkyl moiety and optionally 1 to 9 identical or different halogen atoms, cycloalkyl with 3 to 6 carbon atoms and phenoxy; or R ^{2 is} benzyl with -0-CH ₂ -O-GrUpPe fused in the phenyl moiety. 3. A process for the preparation of new substituted triazolinones of the general formula (I), ¹ N-NH ₂ ^ O NH-R ² in which R ^{1 is} alkyl of 3 to 4 carbon atoms or cyclopropyl and R ^{2 is} hydrogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, cyanoalkyl, hydroxyalkyl, alkoxyalkyl, alkoxycarbonylalkyl, alkoxycarbonylalkenyl, alkylaminoalkyl, dialkylaminoalkyl, each optionally substituted cycloalkyl , Cycloalkylalkyl, cycloalkenyl or cycloalkenylalkyl, optionally substituted heterocyclylalkyl, in each case optionally substituted aralkyl, aroyl, aryl, aralkyloxy or aryloxy, represents alkoxy, alkenyloxy or alkynyloxy, characterized in that la) hydrazones of the mold UH), N-N = C ι - O NH-R ² in which R ¹ and R ^{2 have} the abovementioned meaning and R ³ and R ⁴ independently of one another each represent hydrogen, alkyl, aralkyl or aryl, with an acid, if appropriate in the presence of a diluent, or in that (b) 1 H-triazolinone of the formula (III) N-NH ₂ in which R ^{1 has} the abovementioned meaning, with isocyanates of the formula (IV), R ² -N = C = 0 (IV) in which R ^{2 has} the abovementioned meaning, if appropriate in the presence of a diluent and if appropriate in the presence of a reaction auxiliary, or that one (c) triazolinones of the formula (V), ¹ · ^, N I i -NHo O 0-R ⁵ in which R ^{1 has} the abovementioned meaning, and R ^{5 represents} alkyl, aryl or arylalkyl, with amines of the formula (VI), R ² -NH ₂ (VI) in which R ^{2 has} the abovementioned meaning, if appropriate in the presence of a diluent and if appropriate in the presence of a reaction auxiliary, or that one (d) 1 H-triazolinone of the formula (III), N-NH ₂ (III) I ~ H in which R ^{1 has} the abovementioned meaning, with urethanes of the formula (VII), R ⁵ -OC-NH ~ F (VII) in which R ^{2 has} the meaning given above and R ^{B is} alkyl, aryl or arylalkyl, if appropriate in the presence of a diluent and if appropriate in the presence of a reaction auxiliary. 4. A herbicidal composition, characterized by a content of at least one substituted triazolinone of the formula (I) according to claims 1 to 3. 5. A method for combating weeds, characterized in that one allows substituted triazolinones of the formula (I) according to claims 1 to 3 to act on the weeds and / or their habitat. 6. Use of substituted triazolinones of the formula (I) according to claims 1 to 3 for controlling weeds. 7. Process for the preparation of herbicidal agents, characterized in that substituted triazolinones of the formula (I) according to Claims 1 to 3 are mixed with extenders and / or surface-active agents. 8. Hydrazones of the formula (II), / -R ^{3 1} NN = C θ """NH-R ² in which R ^{1 is} alkyl of ^{3 to} 4 carbon atoms or cyclopropyl and R ^{2 is} hydrogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, Cyanoalkyl, hydroxyalkyl, alkoxyalkyl, alkoxycarbonylalkyl, alkoxycarbonylalkenyl, alkylaminoalkyl, dialkylaminoalkyl, each optionally substituted cycloalkyl, cycloalkylalkyl, cycloalkenyl or cycloalkenylalkyl, optionally substituted heterocycloalkyl, each optionally substituted aralkyl, aroyl, aryl, aralkyloxy or aryloxy, alkoxy, alkenyloxy or Alkynyloxy is and R ³ and R ⁴ are each independently hydrogen, alkyl, aralkyl or aryl. 9. 1-unsubstituted 4-aminotriazolinones of the formula (IIIa) in which . R ¹ ' ^{1 is} n-butyl, i-butyl, s-butyl or cyclopropyl, in particular s-butyl or cyclopropyl. 10. Triazolinones of the formula (XI) R ¹ N NN = C / R ³ O = COR ⁵ in which R ^{1 is} alkyl of 3 to 4 carbon atoms or cyclopropyl, R ³ and R ^{4 are} independently hydrogen, alkyl, aralkyl or aryl and R ^{5 is} alkyl, aryl or arylalkyl.