AU655019B2 - 2-amido-1,2,4-triazolinone derivatives - Google Patents

Description

7" OPI DATE 30/12/92 A0JP DATE 11/02/93 APPLN. ID 16800/92'DiiI filI111li 11 I 111Ili PCT NUMBER PCT/EP92/00968 hl11111 liIli ii11111 li11111111 liii11111111111111111 AU921 6800

DIE

OCT)

(51) Internationalepatentkassifikation 5 (11) Internationale Veroffentlichungsnummer: WO 92/ 20663 C07D 249/14, 405/04, 403/04 Al (43) Internationales AOlN 43/653 Verbffentlichungsdatum: 26. November 1992 (26.11.92) (21) Internationales Aktenzeichen: PCT/EP92/00968 (74) Genicinsamer Vertreter: BAYER AKTIENGESELL- SCHAFT; Bayerwerk, D-5090 Leverkusen (DE).

(22) Internationales Anmeldedatum: 4. Mai 1992 (04.05.92) (81) Bestimmungsstaaten: AT (europdisches Patent), AU, BE Prioritaitsdaten: (europqisches Patent), BR, CA, CH (europ~isches Pa- P 41 16 115.7 17. Mai 1991 (17.05.9 1) DE tent), CS, DE (europdisches Patent), DK (europaisches Patent), ES (europaisches Patent), FR (europiiisches Pa- (71) Anmelder (fair alle Bestimmungsstaaten ausser US): BAYER tent), GB (europ~isches Patent), GR (europ~isches Pa- AKTIENGESELLSCHAFT [DE/DE]; Bayerwerk, D- tent), HU, IT (europ~isches Patent), JP, KR, LU (euro- 5090 Leverkusen paisches Patent), WIC (europiiisches Patent), NL (europaisches Patent), RU, SE (europdisches Patent), US.

(72) Erfinder; und Erfinder/Anmielder (hurflir US) FINDEISEN, Kurt [DE/ Veroffentlicht DE]; Duenfelder Strasse 28, D-5090 Leverkusen Mil internationalem Recherchenberich.

KUHNT, Dietmar [qE/DE]; Koernerstrasse 5, D-5090 Leverkusen MULLER, Klaus-Helmut [AT/DEl; Bockhackstrasse 55, D-4000 Duesseldorf 13 KO- NIG, Klaus [DE/DE]; Zumn Hahnenberg 40, D-5068 Odenthal L{YRSSEN, Klaus [DE/DE]; August-Kierspel-Strasse 145, D-5060 Bergisch Gladbach 2 'V 0J SANTEL, Hans-Joachim [DE/DE]; Gruenstrasse 9a, D- 5090 Leverkusen SCHMIDT, Robert. R. [DE/ DE]; Im Waldwinkel 1 10, D-5060 Bergisch Gladbach 2

(DE).

(54) Title: SUBSTITUTED TRIAZOLINONES (54) Bezeichnung: SUBSTITUIERTE TRIAZOLINONE (57) Abstract R 1K R 2 The invention relates to novel substituted triazolinones n -HR of general formula in which: RI and R 2 are mutually in- 11 dependently alkyl, alkenyl, alkinyl, halogen alkyl, halogen X alkenyl, halogen alkinyl, cyanalkyl, alkoxyalkyl, alkoxy, cycloalkyl, cycloalkyalkyl, possibly substituted aryl, aralkyl or heteroaryl or, together with the nitrogen atom to which they are bonded, a possible substituted heterocycle; R 3 is alkyl or cycloalkyl; R 4 is alkyl, alkenyl, alkinyl, halogen alkyl, halogen alkenyl, halogen alkinyl, cyanalkyl, hydroxyalkyl, alkoxyalkyl, aryloxyalkyl, arylthioalkyl, arylsuiphinylalkyl, arylsulphonylalkyl, arylaminoalkyl, N-alkyl-arylaminoalkyl, arylazoal kyl, alkoxycarbonylalkyl, alkoxycarbonylalkenyl, alkylaminoalkyl, dialkylaminoalkyl, possibly substituted cycloalkyl, cycloalkylalkyl, cycloalkenyl or cycloalkenylalkyl, possibly substituted heterocyclyalkyl, possibly substituted aralkyl, arylalkenyl, arylalkinyl, aroyl, aryl, aralkyloxy or aryloxy, alkoxy, alkenyloxy or alkinyloxy; and X is oxygen or sulphur; several processes for their production and their use as herbicides.

(57) Zusammnenfagsung Die Erfindung betrifft neue substituierte Triazolinone der allgemeinen Formel in welcher R 1 und R 2 unabhatngig vonej,nander jeweils fdr Alkyl, Alkenyl, Alkinyl, Halogenalkyl, Halogenalkenyl, Halogenalkinyl, Cyanalkyl, Alkoxyalkyl, Alkoxy, Cycloalkyl, Cycloalkylalkyl, f~r jeweils gegebenenfalls substituiertes Aryl, Aralkyl oder H-eteroaryl stehen oder gemeinsamn mit demn Stickstoffatom, an welches sic gebunden sind, f~r einen gegebenenfalls substituierten Heterocyclus stehen, R 3 ffir Alkyl oder Cycloalkyl steht, R 4 for Alkyl, Alkenyl, Alkinyl, Halogenalkyl, Halogenalkenyl, Halogenalkinyl, Cyanalkyl, Hydroxyalkyl, Alkoxyalkyl, Aryloxyalkyl, Arylthioalkyl, Arylsulfinylalkyl, Arylsulfonylalkyl, Arylaminoalkyl, N-Alkyl-arylaminoalkyl, Arylazoalkyl, Alkoxycarbonylalkyl, Alkoxycarbonylalkenyl, Alkylaminoalkyl, Dialkylaminoalkyl, f~jr jeweils gegebenenfalls substituiertes Cycloalkyl, Cycloalkylalkyl, Cycloalkenyl oder Cycloalkenylalkyl, f~r gegebenenfalls substituiertes Heterocyclylalkyl, fir jeweils gegebenenfalls substituiertes Aralkyl, Aiylalkenyl, Arylalkinyl, Aroyl, Aryl, Aralkyloxy oder Aryloxy, ffir Alkoxy, Alkenyloxy oder Alkinyloxy steht, und X ftir Sauerstoff oder Schwefel steht, mehrere Verfahren zur ihrer Herstellung und ihre Verwendung als Herbizide.

k:"i wo 92/20663 PCT/EP92/00968 Substituted triazolinones The invention relates to new substitutnd triazolinones, to a plurality of processes for their preparation, and to their uses as herbicides.

Certain substituted triazolinones, such as, for example, 2-phenylaminocarbonyl-5-morpholino-1,2-dihydro-3H-l,2,4triazol-3-one have already been disclosed (cf. DE-OS [German Published Specification] 2,042,660). However, the properties of these known compounds, for example their herbicidal activity, which is only poor, do not meet the demands of practical use, for example in agriculture.

New substituted triazolinones of the general formula (I) R 2

N

R 3

C-

X

NH-R4 in which

II~~

t.$

R

1 and R 2 independently of one another in each case represent alkyl, alkenyl, alkinyl, halogenoalkyl, halogenoalkenyl, halogenoalkinyl, cyanoalkyl, alkoxyalkyl, alkoxy, cycloalkyl, cycloalkylalkyl, Le A 28 424 ZZF 4 in each case optionally substituted aryl, aralkyl or heteroaryl, or, together with the nitrogen atom to which they are bonded, an optionally substituted heterocycle,

R

3 represents alkyl or cycloalkyl,

R

4 represents alkyl, alkenyl, alkinyl, halogenoalkyl, halogenoalkenyl, halogenoalkinyl, cyanoalkyl, hydroxyalkyl, alkoxyalkyl, aryloxyalkyl, arylthioalkyl, arylsulphinylalkyl, arylsulphonylalkyl, arylaminoalkyl, N-alkyl-arylaminoalkyl, arylazoalkyl, alkoxycarbonylalkyl, alkoxycarbonylalkenyl, alkylaminoalkyl, dialkylaminoalkyl, in each case optionally substituted cycloalkyl, cycloalkylalkyl, cycloalkenyl or cycloalkenylalkyl, or represents optionally substituted heterocyclylalkyl, in each case optionally substituted aralkyl, arylalkenyl, arylalkinyl, aroyl, aryl, aralkyloxy or aryloxy, or represents alkoxy, alkenyloxy or alkinyloxy, and X represents oxygen or sulphur, have now been found.

Where appropriate, the compounds of the formula can be present in the form of geometric and/or optical isomers or isomer mixtures of varying composition, depending on the nature of the substituents R 1

R

2

R

3 and

R

4 The invention relates to the pure isomers and to the SLe A 28 424 -2z -4l

I

r It

I

mixtures of isomers.

Furthermore, it has been found that the new substituted triazolinones of the general formula are obtained when a) triazolinones of the general formula (II) 1

R

2

R

3

H

(II)

in which

R

1

R

2 and R 3 have the abovementioned meaning, and/or tautomers of these compounds, that is to say the corresponding hydroxytriazoles, are reacted with iso(thio)cyanates of the general formula (III)

R

4

-N=C=X

(III)

in which

R

4 and X have the abovementioned meaning, i ::a i Le A 28 424 3 ii ;i i

I;

if appropriate, in the presence of a reaction auxiliary and, if appropriate, in the presence of a diluent, or when b) chlorocarbonyl-triazolinones of the general formula

(IV)

R

2 N -N N R3N--N C(IV)

R

3 C-C1 I I in which

R

1

R

2 and R 3 have the abovementioned meaning, are reacted with amines of the general formula (V) H2N-R 4

(V)

in which

R

4 has the abovementioned meaning, if appropriate, in the presence of an acid-binding agent and, if appropriate, the presence of a diluent.

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

4 Surprisingly, the new substituted triazolinones of the general formula display considerably more powerful activity against weeds than the known compound 2-phenylaminocarbonyl-5-morpholino-l,2-dihydro-3H-l,2,4-triazol-3one, which has a similar structure, while simultaneously being well tolerated by important crop plants.

In the general formulae, halogen denotes fluorine, chlorine, bromine and iodine, preferably fluorine, chlorine or bromine, in particular fluorine or chlorine.

Optionally substituted aryl groups, such as, for example, aryl, aralkyl or aryloxy, can have one or more, preferably 1 to 5, in particular 1 to 3, and particularly preferably 1 or 2, identical or different substituents.

In aryl-containing radicals, aryl preferably represents phenyl or naphthyl.

1 2 In the event that the radicals R and R2 form a heterocycle together with the nitrogen atom to which they are bonded, they preferably represent a heterocycle of the formula N 0 H N '00 -N NH -N -N -N 0 0 0 28 421 "Ii7L A 28 424 5 -N -N

-N

or which is optionally monosubstituted, disubstituted or trisubstituted by identical or different substituents, the following being selected as substituents: halogen and in each case straight-chain or branched alkyl or halogenoalkyl, each of which has 1 to 4 carbon atoms and, if appropriate, 1 to 9, preferably 1 to 5, in particular 1 to 3, identical or different halogen atoms.

Methyl, ethyl, n- or i-propyl, chlorine and trifluoromethyl are particularly preferably selected substituents.

The radical heterocycle in the meaning of heterocyclylalkyl for R 4 preferably represents the following heterocycles: SN N I N4-N N -NJ N-7-N -N 0 -N NH 0--7 or Z in each case representing oxygen or sulphur.

Le A 28 424 6 I.S$ V 'fri

C

2 p A

S

V~

i Alkyl in the meaning of heterocyclylalkyl represents, for example, methyl, ethyl, n- or iso-propyl, iso-, sec.

or tert.-butyl.

The heterocycle in the meaning of heterocyclylalkyl can be monosubstituted or polysubstituted, preferably monosubstituted to trisubstituted, in particular monosubstituted or disubstituted, by identical or different substituents from the series consisting of in each case straight-chain or branched alkyl or halogenoalkyl having 1 to 4, preferably 1 or 2, carbon atoms and 1 to 9, preferably 1-to 5, in particular 1 to 3 identical or different halogen atoms, or in each case divalent alkanediyl or alkenediyl having up to 4 carbon atoms.

Radicals which are selected as substituents are, in particular, methyl and ethyl.

Preferred compounds of the formula are those in which

R

1 and R 2 ii 4 ~49 independently of one another represent in each case straight-chain or branched alkyl having 1 to 8 carbon atoms, alkenyl having 2 to 8 carbon atoms, alkinyl having 2 to 8 carbon atoms, halogenoalkyl having 1 to 8 carbon atoms and 1 to 17 identical or different halogen atoms, halogenoalkenyl or haiogenoalkinyl, each of which has 2 to 8 carbon atoms and 1 to 15, or 1 to 13, identical or different halogen atoms, cyanoalkyl, alkoxyalkyl or alkoxy, each of which has 1 to 6 carbon atoms in the individual e A 28 424 /1Q zEN 7 1 i

I-

alkyl moieties, cycloalkyl having 3 to 7 carbon atoms cycloalkylalkyl having 3 to 7 carbon atoms in the cycloalkyl moiety and 1 to 6 carbon atoms in the alkyl moiety, or represent aralkyl having 6 to 10 carbon atoms in the aryl moiety and 1 to 6 carbon atoms in the alkyl moiety, aryl having 6 to 10 carbon atoms or heteroaryl having 2 to 9 carbon atoms and 1 to 3 hetero atoms, in particular nitrogen, oxygen and/or sulphur, each of these radicals optionally being monosubstituted or polysubstituted by identical or different substituents, suitable substituents in each case being: halogen, cyano, nitro and in each case straight-chain or branched alkyl, alkoxy, alkylthio, halogenoalkyl, halogenoalkoxy or halogenoalkylthio, each of which has 1 to 4 carbon atoms and, if appropriate, 1 to 9 identical or different halogen atoms, or

I

4A

UUT

R

1 and R 2 together with the nitrogen atom to which they are bonded represent a five- to ten-membered heterocycle which can, if appropriate, contain 1 to 2 further hetero atoms, in particular nitrogen, oxygen and/or sulphur, and which is optionally 2- monosubstituted or polysubstituted by identical or different substituents, suitable substituents being: halogen and in each case straight-chain or branched alkyl or halogenoalkyl, each of which has 1 to 4 carbon atoms and, if appropriate, 1 to 9 identical Le A 28 424

I-,

-Q

0Xo~ 8 or different halogen atoms, and also 1 to 2 oxo or thiono groups, R represents straight-chain or branched alkyl having 1 to 8 carbon atoms or cycloalkyl having 3 to 8 carbon atoms,

R

4 represents in each case straight-chain or branched alkyl having 1 to 18 carbon atoms, alkenyl having 2 to 8 carbon atoms, alkinyl having 2 to 8 carbon atoms, halogenoalkyl having 1 to 8 carbon atoms and 1 to 17 identical or different halogen atoms, halogenoalkenyl or halogenoalkinyl, each having 2 to 8 carbon atoms and 1 and 15, or 1 to 13, identical or different halogen atoms, cyanoalkyl having 1 to 8 carbon atoms, hydroxyalkyl having 1 to 8 carbon atoms and 1 to 6 hydroxyl groups, or represents phenoxyalkyl, phenylthioalkyl, phenylsulphinylalkyl, phenylsulphonylalkyl, phenylaminoalkyl, N- (C-C 4 -alkyl) -phenylaminoalkyl or phenylazoalkyl, each of which has 1 to 4 carbon atoms in the alkyl moiety, or represents alkoxyalkyl, alkoxycarbonylalkyl or alkoxycarbonylalkenyl, each of which has up to 6 carbon atoms in the individual alkyl or alkenyl moieties, or represents alkylaminoalkyl or dialkylaminoalkyl, each of which has 1 to 6 carbon atoms in the individual alkyl moieties, or represents cycloalkyl, cycloalkylalkyl, cycloalkenyl or cycloalkenylalkyl, each of which has 3 to 8 carbon atoms in the cycloalkyl or cycloalkenyl a oi i 251 o crbn tos n heinivdul lki oitis,.

Le A 28 424 9 d:

;:D

lb.

D" "I' At ii ii,

I::

L~

Oh'

.I

Ie, moiety and, if appropriate, 1 to 6 carbon atoms in the alkyl moiety and is optionally monosubstituted to trisubstituted by identical or different substituents, suitable substituents in each case being: halogen, cyano, phenyl and in each case straight-chain or branched alkyl or halogenoalkyl, each of which has 1 to 4 carbon atoms and, if appropriate, 1 to 9 identical or different halogen atoms, and straight-chain or branched halogenoalkenyl having 1 to 4 carbon atoms and 1 to 5 identical or different halogen atoms, or in each case divalent alkanediyl, or alkenediyl, each of which has up to 4 carbon atoms; R 4 further represents heterocyclylalkyl which has 1 to 6 carbon atoms in the straight-chain or branched alkyl moiety and 2 to 9 carbon atoms and 1 to 3 hetero atoms in particular nitrogen, oxygen and/or sulphur in the heterocyclyl moiety and which is optionally monosubstituted or polysubstituted in the heterocyclyl moiety by identical or different substituents, suitable substituents being: halogen, cyano, nitro, and in each case straight-chain or branched alkyl, alkoxy, alkylthio, halogenoalkyl, halogenoalkoxy, halogenoalkylthio or alkoxycarbonyl, each of which has 1 to 5 carbon atoms and, if appropriate, 1 to 9 identical or different halogen atoms;

R

4 furthermore represents in each case straightchain or branched alkoy having 1 to 8 carbon atoms, alkenyloxy having 2 to 8 carbon atoms or alkinyloxy having 2 to 8 carbon atoms, or aralkyl, arylalkenyl, arylalkinyl, aroyl, aryl, aralkyloxy or aryloxy, Le A 28 424 k.7 10 i for and on behalf of the applicant(s).

each of which has 6 to 10 carbon atoms in the aryl moiety and, if appropriate, 1 to 8 carbon atoms in the straight-chain or branched alkyl moiety or 2 to 8 carbon atoms in the straight-chain or branched alkenyl moiety or alkinyl moiety, it being possible for the hydrogen atoms of the a-carbon atom to be replaced by ethane-1,2-diyl, propane-1,3-diyl, butane-1,4-diyl or penr.ane-1,5-diyl, each of the abov° radicals being optionally monosubstituted to trisubstituted by identical or different substituents, suitable alkyl substituents being, if appropriate, halogen and cyano, and suitable aryl substituents in each case being: halogen, cyano, nitro, amino, hydroxyl, in each case straight-chain or branched alkyl, alkoxy, alkylthio, halogenoalkyl, halogenoalkoxy, halogenoalkylthio, alkylsulphinyl, alkylsulphonyl, halogenoalkylsulphinyl, halogenoalkylsulphonyl, alkanoyl or alkoxycarbonyl, each of which has 1 to 6 carbon atoms in the alkyl moiety and, if appropriate, 1 to 9 identical or different halogen atoms, cycloalkyl having 3 to 6 carbon atoms, oxaalkanediyl having up to 5 carbon atoms and phenoxy; or R 4 represents benzyl with a -O-CH 2 group fused to the phenyl moiety, and X represents oxygen or sulphur.

Particularly preferred compounds of the formula are those in which S '4 e A 28 424 -11 E e 8 2 i L; fa 7 heteroaryl, or, together with the nitrogen atom to which they are bonded, an optionally substituted heterocycle,

R

3 represents alkyl or cycloalkyl, /2 L. ICI I ii i- :i iY i Ii,

C;

IL S 1 L II I. Mqi k iW

R

1 and R 2 independently of one another in each case represent methyl, ethyl, n- or i-propyl, sor t-butyl, n- or i-pentyl, allyl, propargyl, in each case straight-chain or branched halogenoalkyl having 1 to 4 carbon atoms, halogenoalkenyl having 3 to 6 carbon atoms or halogenalkinyl having 3 to 6 carbon atoms and in each case 1 to 9 identical or different halogen atoms, or represent cyanoethyl, methoyymethyl, methoxyethyl, methoxy, ethoxy, cyclopropyl, cyclopropylmethyl, cyclopentyl, cyclohexyl, cyclohexylmethyl, cyclohexylethyl, cyclopentylmethyl, or represent benzyl, phenylethyl or phenyl, each of which is optionally monosubstituted to trisubstituted by identical or different substituents, suitable substituents being: fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, nor i-propyl, s- or t-butyl, methoxy, ethoxy, methylthio, trifluoromethyl, trifluoromethoxy or trifluoromethylthio, or

R

1 and R 2 together with the are bonded represent a nitrogen atom to which they heterocycle of the formula -N -ND -N 0

\-I

0 O A4 -N NH

O-

-N

0

-N

0~ .r Le A 28 424 12 i -b \1

L-~

-r 'I 0

-N

-N 1 or -N I each of which is optionally monosubstituted to trisubstituted by identical or different substituents, suitable substituents being: methyl, ethyl, n- or i-propyl, chlorine or trifluoromethyl,

R

3 represents methyl, ethyl, propyl, isopropyl, i-, s- or t-butyl, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl,

R

4 represents methyl, ethyl, n- or i-propyl, sor t-butyl, in each case straight-chain or branched pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, or represents allyl, in each case straight-chain or branched butenyl, pentenyl or hexenyl, propargyl, in each case straight-chain or branched butinyl, pentinyl or hexinyl, straight-chain or branched halogenoalkyl having 1 to 8 carbon atoms and 1 to 9 identical or different halogen atoms, in particular fluorine, chlorine or bromine, in each case straightchain or branched halogenoalkenyl or halogenoalkinyl, each of which has 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 having 1 to 6 carbon atoms and 1 to 3 hydroxyl groups, alkoxyalkyl, alkoxycarbonylalkyl or alkoxycarbonylalkenyl, alkylaminoalkyl or _4 in I Le A 28 424 13 dialkylaminoalkyl, each of which has up to 4 carbon atoms in the individual alkyl or alkenyl moieties, or represents cyclopropyl, cyclopropylmethyl, cyclopropylethyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclohexylmethyl, cyclohexylethyl, cyclohexenyl or cyclohexenylmethyl, each of which is optionally monosubstituted to trisubstituted by identical or different substituents, suitable substituents in each case being: fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, sor t-butyl, cyano, methanediyl, ethanediyl, butanediyl or butadienediyl or dichloroallyl;

R

4 furthermore represents heterocyclylmethyl, heterocyclylpropyl or heterocyclylethyl, each of which is optionally monosubstituted to trisubstituted in the heterocyclyl moiety by identical or different substituents, suitable heterocycles in each case being: i N O Cr -N -N 0 or -N NH 0 ii is 14 L~Y--~lr :1L-i- i~ Le A 28 424 1

I

K Z in each case representing oxygen or sulphur and suitable substituents in each case being: fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n- or i-propyl, s- or t-butyl, methoxy, ethoxy, methylthio, trifluoromethyl, trifluoromethoxy, or trifluoromethylthio; R furthermore represents in each case straight-chain or branched alkoxy having 1 to 6 carbon atoms, alkenyloxy having 3 to 6 carbon atoms or alkinyloxy having 3 to 6 carbon atoms, or represents optionally straight-chain or branched benzyl, phenylethyl, phenylpropyl, phenylpropenyl, phenylpropinyl, phenylbutyl, phenylbutenyl, phenylbutinyl, phenylpentyl, phenylpentenyl, phenylpentinyl, phenylhexyl, phenylhexenyl, phenylhexinyl, phenylheptyl, phenylheptenyl, phenylheptinyl, phenyloctyl, phenyloctenyl, phenyloctinyl, phenylcyanomethyl, phenylcyanoethyl, phenylcyanopropyl, benzyloxy, phenylethyloxy, phenoxy, phenoxyethyl, phenoxypropyl, phqnoxy-i-propyli, phenoxyisobutyl, phenoxy-tertbutyl, phenylthioisobutyl, phenylthio-tert-butyl, phenylthioethyl, phenylthiopropyl, pihenylthio-ipropyl, benzoyl or naphthyl, each of these radicals being optionally monosubstituted to trisubstituted by identical or different substituents, suitable phenyl substituents in each case being: fluorine, chlorine, bromine, hydroxyl, cyano, nitro, methyl, ethyl, nor i-propyl, s- or t-butyl, methoxy, ethoxy, methylthio, difluoromethyl, trifluoromethyl, i V:i i; A 28 424 15 i %is

I

i Le A 28 424 2

I

i7~f i'difluoromethoxy, trifluoromethoxy, trifluoromethylthio, trifluoromethylsulphinyl, trifluoromethylsulphonyl, methylsulphinyl, methylsulphonyl, acetyl, propionyl, methoxycarbonyl, ethoxycarbonyl, n- or ipropoxycarbonyl, cyclohexyl or phenoxy, and X represents oxygen or sulphur.

Very particularly preferred compounds of the formula (I) are those in which

R

1 represents methyl, ethyl, n- or i-propyl, sor t-butyl, n- or i-pentyl, cyclopropyl, cyclopentyl or cyclohexyl,

R

2 represents methyl, ethyl, n- or i-propyl, sor t-butyl, n- or i-pentyl, or

R

1 and R 2 together with the nitrogen atom to which they are bonded represent a heterocycle of the formula -N -ND.

-01 -N 0 or

CH

3 -N O

CH

3

R

3 represents methyl, ethyl, propyl or isopropyl, in particular methyl, 16 Le A 28 424-3 3 0 :1

I-,

R

4 represents l-rethyl-3-phenyl-propyl, l-ethyl-3phenyl-propyl, l-propyl-3 henyl-propyl, 1isopropyl-3-phenyl-propyl, 2-m6 .yl- 3-phenyl-propyl, 1, 1-dixethyl-3-phenyl-propyl, l-methyl-l-ethyl-3phenyl-propyl, 1, l-diethyl-3-phenyl-propyl, 1methyl-l-propyl-3-phenyl-propyl, l-methyl-3-phenyl- 2-propenyl, 1 -ethyl- 3-phenyl 2-propenyl, 1-propyl-3phenyl-2-propenyl, l-isopropyl-3-phenyl-2-propenyl, 1, l-dime thyl-3--phenyl-2-propenyl, 1-methyl-i-ethyl- 3-phenyl-2-propenyl, 1, l,-diethyl-3-phenyl-2propenyl, 1-methyl-l-propyl-3-phenyl-2-propenyl, 1methyl-37phenyl-2-propinyl, l-ethyl-3-phenyl-2propinyl, 1-propyl-3-phenyl-2-propinyl, 1-isopropyl- 3-phenyl-2-propinyl, 1, l-dimethyl-3-phenyl-2propinyl, 1 -methyl- 1-ethyl 3-phenyl 2-propinyl, 1,1diethyl-3-phenyl-2-propinyl, 1-methyl-l-propyl-3phenyl-2-propinyl, 1, 2-dimethyl-3-phenyl-propyl, 2ethyl-l-methyl-3-phenyl-propyl, 1, 2,2-trimnethyl-3phenyl-propyl, 1,3, 3-trimethyl-3-phenyl-propyl or 1, 1,2,2-tetrainethyl-3-phenyl-propyl, each of which is optionally monosubstituted to trisubstituted by identical or different substituents, suitable phenyl.

substituents in each case being: fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, sor t-butyl, trifluoromethyl, phenyl, mnethoxy, ethoxy, propoxy, isopropoxy, difluoromethoxy, trifluoromethoxy, difluoromethyl, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, cyano, methylthio, ethylthio, propylthio, isopropylthio, difluoromethylthio, trifluoromethylthio, methylsulphinyl,

I

*1 f Le A 28 424 17 4- Em r methylsuiphonyl furthermore and trifluoromethylsulphonyl, X represents oxygen.

If, for example, 5-dimethylaxnino-l-methyl-l, 2-dihydro-3H- 1,2 ,4-triazol- -one and 3-methyl-4-phenyl-2-butyl isocyanate are used as starting compounds, the course of the reaction of process according to the invention can be represented by the following equation: C CH 3 2

N

H

3 C H

CH

3

O=C=N-CHCH-CH

2

CR'

3

(CH

3 2 N

CH

3

H-

3 C C-NH-CH-CH&CH 2 il 0 Lk' 3 If, for example, 1,2-dihydro-3H1--,2,4-triazol-3-one and -4 chlorophenyl)-3-aminobutane are used as starting compounds, the course of the reaction of process (b) according to the invention can be represented by the following equation: Le N 28 424 18 1)

I

N

N N H3C C-C1 1 1

H

2

N-CHCHH

2

-CH

2 /1

CH

3

-HC

-HC1

SN

N-N

H

3 C C-NH-CH-CH 2

-CH

2

/-C

0

CH

3 In the intermediates and precursors, the radicals (R 1

R

2 X etc.) which have been defined in the active compounds of the formula also have the meanings given for all ranges of definitions in the case of the compounds of the formula The same applies analogously to the radicals which are mentioned several times in the precursors and intermediates.

The starting compounds of the formula (II) or the corresponding tautomeric hydroxytriazoles have been disclosed and/or can be prepared by processes known per se (cf. DE-OS [German Published Specification] 2,042,660, DE-OS [German Published Specification] 2,330,089, DE-OS [German Published Specification] 2,428,204, DE-OS [German Published Specification] 2,537,973).

Le A 28 424 19 Le A 28 424 6 The triazolinones of the formula (II) are obtained, for example, when cyanamides of the formula (VI) FR2-C

(VI)

in which

R

1 and R 2 have the abovementioned meaning, are reacted with chloroformic esters of the formula (VII) Cl-COOR (VII) in which R represents methyl, ethyl or phenyl, preferably phenyl, at temperatures between 20"C and 150 0 C, and the resulting chloroformamidine derivatives of the formula (VIII) R22 ,N-C=N-COOR

R

2

I

(VIII)

in which R, R 1 and R 2 have the abovementioned meaning, are reacted, if appropriate after isolation by

SI

Le A 28 424 20 ui: ii ::i i i.: S eA 28 424 Q' 7 ,-i i:i

I

(y ::j771 *17 4i:~ distillation in vacuo or by other customary methods, with alkylhydrazines of the formula (IX)

R

3

-NH-NH

2

(IX)

in which

R

3 has the abovementioned meaning, at temperatures between 0°C and 100'C, if appropriate in the presence of diluents, such as, for example, methylene chloride, dioxane and/or diethyl ether, and the product is worked up by customary methods (cf. the preparation examples).

The starting compounds of the formula (III) are known organic synthesis chemicals (cf. for example, Nouv.

J. Chim. 1 (1977), 243-254 cited in Chem. Abstracts 87: 151614a; Liebigs Ann. Chem. 562 (1949), 75-136; Synthesis 1990, 803-815; Preparation examples).

The starting compounds of the formula (IV) have not hitherto been disclosed in the literature, but are the subject-matter of an earlier, non-prior-published Patent Application (cf.

German Patent Specification 3,939,952/LeA 27,343).

The chlorocarbonyl-triazolinones of the formula (IV) are obtained when triazolinones of the formula (II) ~i i- 1' Le A 28 424 21 .cC j U@ Le A 28 424 8

R(II

R

2

-N

R

3 in which R, R 2 and R 3 have the abovementioned meaning, are reacted with phosgene at temperatures between 0 C and 150 0 C, if appropriate in the presence of an acid-binding agent, such as, for example, triethylamine, and, if appropriate, in the presence of a diluent, such as, for example, toluene or acetonitrile.

The starting compounds of the formula are known and/or can be prepared by processes known per se (cf. J.

Med. Chem. 25 (1982), 1363-1370; Tetrahedron Lett. 29 (1988), 223-224; Chem. Ber. 117 (1984), 856-858; DE-OS [German Published Specification] 3,426,919; EP-A 237,305; J. Am. Chem. Soc. 71 (1949), 3482-3485; Tetrahedron Lett.

27 (1986), 3957-3960; Bull. Soc. Chim. France 1974 (3-4, Pt. 615-622; Tetrahedron Lett. 31 (1990), 2661-2664; J. Med. Chem. 13 (1970), 1249-1250; Preparation examples).

The process according to the invention for the preparation of the new substituted triazolinones of the formula is preferably carried out using diluents.

Diluents which are suitable for this purpose are virtually all inert organic solvents.

Le A 28 424 22 ,ft h'9 9 These preferably include aliphatic and aromatic, optionally halogenated hydrocarbons, such as pentane, hexane, heptane, cyclohexane, petroleum ether, benzine, ligroine, benzene, toluene, xylene, methylene chloride, ethylene chloride, chloroform, carbon tetrachloride, chlorobenzene and o-dichlorobenzene, ethers, such as diethyl ether, dibutyl ether, glycol dimethyl ether and diglycol dimethyl ether, tetrahydrofuran and dioxane, ketones, such as acetone, methyl ethyl ketone, methyl isopropyl ketone and methyl isobutyl ketone, esters, such as methyl acetate and ethyl acetate, nitriles, such as, for example, acetonitrile and propionitrile, amides, such as, for example, dimethylformamide, dimethylacetamide and N-methyl-pyrrolidone, and also dimethyl sulphoxide, tetramethylene sulphone and hexamethylphosphoric triamide.

If appropriate, process according to the invention can be carried out in the presence of a basic reaction auxiliary. Suitable basic reaction auxiliaries are all customary inorganic and organic bases. The following are preferably used: tertiary amines, such as triethylamine, N,N-dimethylaniline, pyridine, N,N-dimethylaminopyridine, diazabicyclooctane (DABCO), diazabicyclononene (DBN) or diazabicycloundecene (DBU).

However, the addition of such catalysts is not essential.

When carrying out the process according to the invention, the reaction temperatures can be varied within S- Le A 28 424 23 ~ru-r~~rxn ~nrm'l~.T~.~m~i+Nil~RI~C~Str~ 1 Le A 2 8 4 24 10 Ji A6, a substantial range. In general, the process is carried out at temperatureE between 0 0 C and +150 0 C, preferably at temperatures between +40 0 C and +1200C.

Process according to the invention is conventionally cazried out under atmospheric pressure. However, the process can also be carried out under elevated pressure, in particular when the starting compounds are in gaseous form.

To carry out process according to the invention, 1 to mol, preferably 1 to 2.5 mol, of iso(thio)cyanate of the formula (III) and, if appropriate, 1 to 2.5 mol of reaction auxiliary are generally employed per mole of triazolinone of the formula The reaction is carried out and the reaction products are worked up and isolated analogously to generally known processes (cf. the preparation examples).

Suitable diluents for carrying out process are also inert organic solvents. Diluents which are preferably used are those mentioned in process If appropriate, process according to the invention is carried out in the presence of a suitable acid-binding agent. Suitable acid-binding agents are all customary inorganic or organic bases. These include, for example, alkali metal hydroxides, such as sodium hydroxide or potassium hydroxide, alkali metal cabonates*, such as sodium carbonate, potassium carbonate or sodium hydrogen carbonate, and also tertiary amines, such as 4 2gi--L Al 424 -2 24 /fle A 28 424 "w 11 I ~I 1 i Ir -r triethylamine, N,N-dimethylaniline, pyridine, N,N-dimethylaminopyridine, diazabicyclooctane (DABCO), diazabicyclononene (DBN) or diazabicycloundecene (DBU).

The amine of the formula which is used as reactant, can also be employed in a suitable excess to act simultaneously as acid-binding agent.

When carrying out process according to the invention, the reaction temperatures can be varied .:ithin a substantial range. In general, the process is carried out at temperatures between 0°C and +150°C, preferably at temperatures between +10°C and Process according to the invention is conventionally carried out under atmospheric pressure. However, it can also be carried out under elevated pressure.

To carry out process according to the invention, 1 to mol, preferably 1 to 2.5 mol, of amine of the formula and, if appropriate, 1 to 2.5 mol, of acid-binding agent are generally employed per mole of chlorocarbonyltriazolinone of the formula The reaction is carried out and the reaction products are worked up and isolated analogously to generally known processes (cf. the preparation examples).

The active compounds according to the invention can be used as defoliants, desiccants, agents for destroying broad-leaved plants and, especially, as weed-killers. By 1

L.

L1

I-;

Le A 28 424 25

'L

M

I

Le A 28 424 12 i ~s *1- V. V.a weeds, in the broadest sense, there are to be understood all plants which grow in locations where they are undesired. Whether the compounds according to the invention act as total or selective herbicides depends essentially on the amount used.

The active compounds according to the invention can be used, for example, for the following plants: Dicotyledon weeds of the genera: Sinapis, Lepidium, Galium, Stel-laria, 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, Trifolium, Ranunculus and Taraxacum.

Dicotyledon cultures of the genera: Gossypium, Glycine, Beta, Daucus, Phaseo3us, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, Cucumis and Cucurbita.

Monocotyledon weeds of the genera: Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum, Sphenoclea, Dactyloctenium, Agrostis, Alopecurus and Apera.

4 pj Le A 28 424 cc 26 I ~h

-L

12 Monocotyledon cultures of the genera: Oryza, Zea, Triticum, Hordeum, Avena, Secale, Sorghum, Panicum, Saccharum, Ananas, Asparagus and Plium.

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

The compounds are suitable, depending )n the concentration, for the total combating of weeds, for example on industrial terrain and rail tracks, and on paths and squares with or without tree plantings. Equally, the compounds can be employed for combating weeds in perennial cultures, for example forests, decorative tree plantings, orchards, vineyards, citrus groves, nut orchards, banana plantations, coffee plantations, tea plantations, rubber plantation,, oil palm plantations, cocoa plantations, soft fruit plantings and hopfields, in lawns, turf and pasture-land, and for the selective combating of weeds in annual cultures.

The compounds of the formula according to the invention are particularly suitable for selectively combating monocotyledon and dicotyledon weeds in monocotyledon and dicotyledon cultures by the pre- and post-emergence methods.

To a certain extent, they can also be used as defoliants 25 in cotton or as foliar insecticides.

I

A

v 27 c J 1 i L- 14 -I p.- Seepage of the compounds of the formula in the soil is extremely slow; contamination of the ground-water can therefore be virtually excluded.

The active compounds can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusting agents, pastes, soluble powders, granules, suspension-emulsion concentrates, natural and synthetic materials impregnated with active compound, and very fine capsules in polymeric substances.

These formulations are produced in a known manner, for example by mixing the active compounds with extenders, that is liquid solvents and/or solid carriers, optionally with the use of surface-active agents, that is emulsifying agents and/or dispersing agents and/or foamforming agents.

In the case of the use of water as an extender, organic solvents can, for example, also be used as auxiliary solvents. As liquid solvents, there are suitable in the main: 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, for example petroleum t fractions, mineral and vegetable oils, alcohols, such as butanol or glycol as well as their ethers and esters, a* ketones, such as acetone, methyl ethyl ketone, methyl <S 1^ 1' Le A 28 424 28 1, Le A 28 424 r^0/

'-W

7 p~~ 15 ;1 ii ri t i i L i"

I

111-7

I

f' ii I~ I isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethyl sulphoxide, as well as water.

As solid carriers there are suitable: 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 highly disperse silica, alumina and silicates, as solid carriers for granules there are suitable: for example crushed and fractionated natural rocks -such as calcite, marble, pumice, sepiolite and dolomite, as well as synthetic granules of inorganic and organic meals, and granules of organic material such as sawdust, coconut shells, maize cobs and tobacco stalks; as emulsifying and/or foam-forming agents there are suitable: for example non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonates as wall as albumen hydrolysis products; as dispersing agents there are suitable: for example lignin-sulphite waste liquors and methylcellulose.

Adhesives such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or latexes, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, as well as natural phospholipids, such as cephalins and lecithins, and synthetic phospholipids, al-.

I

Le A 28 424 29 ,d h e A 28 424- 16can be used in the formulations. Further additives can be mineral and vegetable oils.

It is possible to use colorants such as inorganic pigments, for example iron oxide, titanium oxide and Prussian Blue, and organic dyestuffs, such as alizarin dyestuffs, azo dyestuffs and metal phthalocyanine dyestuffs, and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.

The formulations in general contain between 0.1 and per cent by weight of active compound, preferably between and For combating weeds, the active compounds according to the invention, as such or in the form of their formulations, can also be used as mixtures with known herbicides, finished formulations or tank mixes being possible.

Suitable herbicides for the mixtures are known herbicides, such as, for example, l-amino-6-ethylthio-3- (2,2-dimethylpropyl)-l,3,5-triazine-2,4(1H,3H)-dione (AMETHYDIONE) or N-(2-benzothiazolyl)-N,N'-dimethylurea (METABENZTHIAZURON) for combating weeds in cereals; 4amino-3-methyl-6-phenyl-1,2,4-triazin-5(4H)-one (METAMITRON) for combating weeds in sugar beet and 4amino-6-(1,1-dimethylethyl)-3-methylthio-1,2,4-triazin- 5(4H)-one (METRIBUZIN) for combating weeds in soya beans; furthermore also 2,4-dichlorophenoxyacetic acid S Le A 28 424 -30 I .J j -Ij Le A 28 424 -117

I

4-(2,4-dichlorophenoxy)-butyric acid 2,4dichiorophenoxyprop ionic acid (2 ,4-DP) 5-(2-chloro-4trifluoromethyl-phenoxy) -2-nitro-benzoic acid (ACIFLUJORFEN); 2,6-diethyl-N-methoxy-methylchloroacetanilide (ALACHLOR); methyl-6, 6-diiethyl-2,4-dioxo-3- (2 -propenyloxyanino) -butylidene] -cyclohexanecarboxylic acid (ALLOXYDIM); methyl 4-amino-benzenesulfonylcarbamate (ASULAM); 2-chloro-4-ethylanino-6-isopropyamino-1,3,5-triazine (ATRAZINE); methyl dimethoxypyrimidin-2-yl)amino]-carbonyl]-amilo]sulphonyl] -methyl] -benzoate (BENSULFURON); 3-isopropyl- 2, 1,3-benzoth-iadiazin-4-one 2,2-dioxide (BENTAZONE); methyl 5-(2,4-dichlorophenoxy)-2-nitrobenzoate (BIFENOX); 3, 5-dibromo-4-hydroxy--benzonitrile (BROMOXYNIL); N- (butoxymethyl) -2-chloro-N-(2, 6-diethylphenyl)-acetamide (BUTACHLOR); 5-amino-4-chloro-2-phenyl-2,3-dihydro-3oxypyridazine (CHLORIDAZON); ethyl [(4-chloro-6methoxy-2-pyrimidinyl) -aminocarbonyl] -axinosulphonyl}benzoate (CHLORIMTJRON); N- (3-chlorophenyl) -isopropyl carbalmate (CHLORPROPHAM); 2-chloro-N-{ [(4-methoxy-6methyl-1,3,5-triazin-2-yl)-amino]-carbonyl-belzelesulphonamide (CHLORSULFURON); N,N-dimethyl-N'- (3-chloro- 4-methylphenyl) -urea (CHLORTOLURON); exo-1-methyl-4-(1methylethyl) (2-methylphenyl-methoxy) -7-oxabicyclo- (2,2,1)-heptane (CINMETHYLIN); 3,6-dichloro-2-pyridinecarboxylic acid (CLOPYRALID) 2-chloro-4-ethylamilo-6- (3cyanopropylamino) 3,5-triazine (CYANAZINE); N,Sdiethyl-N-cyclohexylthiocarbanate (CYCLOATE); 2-[1- (ethoximino) -butyl ]-3-hiydroxy-5- [tetrahydro- (2H) thiopyran-3-yl]-2-cyclohexen-l-one(CYCLOXYDIM);

A

1 p

I

Le A 28 424 31 Le X 28 424 -118 X~'Z

A

II.

\4:1Jc3' 1 L ~k.

f;i~ ,4-dichlorophenoxy)-phenoxy]-propionic acid, its methyl ester or its ethyl ester (DICLOFOP); 2-[(2-chlorophenyl) -methyl 4-dimethylisoxazolidin-3-one (DIMETHAZONE); S-ethyl N,N-di-n-propyl-thiocarbamate (EPTAME); 4-axino-6-t-butyl-3-ethylthio-1,2,4-triazin- 5(4H)-one (ETHIOZIN); 2-{4-[(6-chloro-2-benzoxazolyl)oxy]-phenoxy} -propanoic acid, its methyl ester or its ethyl ester (FENOXAPROP); 2-[4-(5-trifluoromethyl-2pyridyloxy)-phenoxy]-propanoic acid or its butyl ester (FLUAZIFOP); N,N-dimethyl-N' (3-trifluoromethylphenyl) urea (FLUOMETURON) l-methyl-3-phenyl-5- (3-trifluoromethylphenyl) -4-pyridone (FLURIDONE); [(4-aznino-3, dichloro-6-fluoro-2-pyridinyl)-oxy] -acetic acid or its 1methylheptyl ester (FLUROXYPYR); 5- (2-chloro-4-trifluoromethyl-phenoxy)-N-methylsulphonyl-2-nitrobenzamide (FOMESAFEN); 2-{4-[(3-chloro-5-(trifluoromethyl)-2pyridinyl)-oxy]-phenoxy}-propanoic acid or its ethyl ester (IALOXYFOP); 3-Cyclohexyl-6-dirnethylamino-1-methyl- 1,3,5-triazine-2,4-dione (HEXAZINONE); methyl 2-[14,5dihydro-4-methyl-4-(l-methylethyl)-5-oxo-lH-imidazol-2- (I'AZAMETHABENZ); 2-[5-methyl-5- (l-methylethyl) -4-oxo-2-imidazolin-2-yl]-3-,quinoliiecarboxylic acid (IMAZAQtJIN); 2-[4,5-dihydro-4-methyl-4- 1H) -imidazol-2-yl] -5-ethaylpyridine-3carboxylic acid (IMAZETHAPYR) 3,5-diiodo-4-hydroxybenzonitril (IOXYNIL); N,N-dimethyl-N'-(4-isopropylphenyl)urea, (ISOPROTURON) (2-ethoxy-l-methyl-2-oxo-ethyl)-5-[2chloro-4-(trifluoromethyl) -phenoxy]-2-nitrobenzoate (LACTOFEN); (2-methyl-4-chlorophenoxy) -acetic acid (MCPA); (4-chloro-2-methylphenoxy) -propionic acid (MCPP)

I

Le A 2 8 4 24 32 *Le A28 424 -9 N-methyl-2- 3-benzothiazol-2-yloxy) -acetanilide (MEFENACET); 2-chloro-N-(2,6-diinethylphenyl)-N-[ (lH) pyrazol-1-yl-methyl]--acetanide (METAZACHLOR); 2-ethyi-6methyl-N- (l-methyl-2-inethoxyethyl) -chioroacetanilide (IETOLACHLOR); (4-Iethoxy-6-methyl-1,3,5-triazin-2yl)-aznino)-carbonyl]-amino]- iulphonyl}-benzoic acid or its methyl ester (METSULFURON); S-.ethyl N,N-hexainethylenethiolcarbamate, (MOLINATE); 1- (3-trifluoromethylphenyl)-4-methylamino-5-chloro-6-pyridazone (NORFLURAZON); 4-(di-n-propylamino)-3 suiphonamide (ORYZALIN) 2-chloro-4-trif luoromethylphenyl 3-ethoxy-4-nitro-pheny. ether (OXYFIAJORFEN); N-(l-ethylpropyl) 4-dimethyl-2 ,6-di-nitroaniline (PENDIMETHALIN); 3-(ethoxycarbonylaminophenyl) -methyiphenyl)cLrbalnate (PHENMEDIPHAM); a-chloro-2',6'-diethyl-N-(2propoxyethyl) -acetanilide (PRETILACHLOR) 2-chloro-Nisopropylacetanilide (PROPACHILOR); isopropyl N-phenylcarbamate (PROPHAM); 0- (6-chloro-3-phenyl-pyridazin-4-yl) S-octyl thiocarbonate (PYRIDATE); ethyl 2-[4-(6-chloroquinoxalin-2-.yl-oxy) -phenoxy] -propionate (QUIZALOFOP- ETHYL); 2-[l-(ethoxamino)-butylidene]-5-(2-ethylthiopropyl)-1,3-cyclohexadione (SETHOXYDIM); 2-chloro-4,6bis-(ethylamino)-1,3,5-triazine (SIMAZINE) 2,4-bis-[Nethylamino]-6--methylthio-1,3,5-triazine (SIMETRYN); 4 ethylamino-2-t-butylamino- 6-methylthio-s-triazine (TERBUTRYNE); methyl 3-[[[[(4-methoxy-6-methyl-1,3,5triazin-2-yl)-amino]-carbonyl]-amino]-sulphonyl]thiophene-2-carboxylate (THIAIAETURON); (4-chiorophenyl)-methyl] N,N-diethylthiocarbamate (THIOBENCARB); 3,3-trichloroallyl) N, N-d i is opropy thio carbamate Ie Le A 28 424 -33- ~u

I.

S/ 2Le 20 -42 2 show a synergistic action.

Mixtures with other known active compounds, such as fungicides, insecticides, acaricides, nematicides, bird repellants, plant nutrients and agents which improve soil structure, are also possible.

The active compounds can be used as such, in the form of their formulations or in the use forms prepared therefrom by further dilution, such as ready-to-use solutions, suspensions, emulsions, powders, pastes and granules.

They are used in the customary manner, for example by watering, spraying, atomizing or scattering.

The active compounds according to the invention can be applied either before or after emergence of the plants.

They can also be incorporated into the soil before sowing.

The amount of active compound used can vary within a substantial range. It depends essentially on the nature of the desired effect. In general, the amounts used are between 1 g and 10 kg of active compound per hectare of soil surface, preferably between 5 g and 5 kg per ha.

The preparation and use of the active compounds according to the invention can be seen from the following examples.

:LeA242 34 TLe A 28 424 -34 u e wateing spryin, aomizng r sctteing Th aciecmoud codngt h nenincnb 15 ppled ithr bfor oraftr eergnceof he lans.

Theycan lsobe icororatd ito te sil bfor sowing.

Th' e amon of activ copudusdcnvrywti subtania rage Iti deed senilyo tentr Le A 28 424 -2 21 Preparation ExaMples: Example 1

C

2

H

j

H

3

C

NH-CH-CH

2

-CH

2

H

3

CH

3 (process 18.9 g (0.1 mol) of 1-(4-methylphenyl-3-butyl isocyanate are added to 15. 6 g 1 mol) of amino- 1, 2-dihydro- 3H- 1,2, 4-triazol- 3-one and 250 ml of acetonitrile and, after 5 drops of 1,8-diazabicyclo- [5.4.0]-undec-7-ene (DBU) have been added, the reaction mixture is stirred for 2 hours at room temperature. The solution is concentrated under a water pump vacuum, and the residue is chromatographed over silica gel (eluant: cyclohexane/ethyl acetate 1:1).

28 g (81% of theory) of 2-[4-(4-methyl-phenyl)-but-2ylaminocarbonyl -methyl-5-ethyl-methylamino- 1,2dihydro-3H-1,2,4-triazol-3-one are obtained as an oil.

1 H-NMR (CDCl 3 /TMS): 8 1.20-1.23; 1.24-1.30; 2.30; 2.56-2.66; 3.10; 3.30; 7.05; 8.05-8.07 ppm Le A 28 424 35 SLe A 28 424- 22 A 22 A-4tMOWN I III Example 2 (C H 3 2 N H5C2 1-~ 5 c 2 0 C NH-CH-CH 2 2 o~css-e-c2-CH2-

CH

CH3 (process A mixture of 4.4 g (25 mmol) of l-(4-ethylphenyl-3butylamine and 2.6 g (25 mmol) of triethylamine is added dropwise to a mixture of 5.5 g (25 mmol) of 2-chlorocarbonyl-5-dimethylamino-l-ethyl-1,2-dihydro-3H-1,2,4triazol-3-one and 150 ml of acetonitrile. During this process, the temperature of the reaction mixture rises to 33"C. The mixture is stirred for 2 hours at room temperature and then filtered. The filtrate is evaporated under a water pump vacuum, the residue is extracted using methylene chloride/water, the organic phase is dried using sodium sulphate and filtered, and the solvent is removed by distillation under a water pump vacuum. The residue is chromatographed over silica gel (eluant: cyclohexane/ethyl acetate 1:1).

4.9 (55% of theory) of 2-[4-(4-ethylphenyl)-but-2-ylaminocarbonyl]-l-ethyl-5-dimethylamino-1, 2-dihydro-3H- 1,2,4-triazol-3-one are obtained as an oil.

"H-NMR (CDC1 3 /TMS): 8 1.00-.05, 1.20-1.26; 2.60-2.70;

I

Le A 28 424 -36 V I i: I Le A 28 424 23

NUNN

y 3.18; 3.82-3.90; 3.90-4.00; '7.10; 8.12-8-16 ppm Other examples of the compounds of the formula which can be prepared analogously to Examples 1 and 2 and following the general description of the preparation processes according to the invention are those listed in Table 1 below.

RI I

R

2 Le A 28 424 -3 37

I

.1r Table 1: Examples of the compounds of the formula (I) Ex. No.

"E 1 N- E 2 X Physical Properties -NC CH 3 2 -N OH 3 2 -CH4 3

-CH

3

-NCH-

3 2 -NC CH 3 2

_-N(CH

3 2

-N(CH

3 2

-CH

3

-CH

3

CH-

3

CH

3

-C(CH

3 2

-CH

2

-CH

2

-CH

2

-CHI-CH

2

C(CH

3 3

CH

3

-CH-CH

2

-CH

2 C 4

H

9 n -CH-CH 2 -_CH 2

CH

3 U1H 3 -CH-CH 2 -CF1 2

IC

CH 3 0 91-92,C 0 98-1001C

'H-NMR;

2.60-2.75; 3. 15; 3.35; 3.90-4 1, 20-1 2.30; 2,55- 2.70; 3.15 1

H-NMR:

1 .22-1 .27; 2.60-2.*70; 3.15; 8.05 1

H-NMR:

0.87-0.92; 2.60-2.70; 3.15; 3.35

-CH-CH

2

-CH

2 Cl

C;H

2

-C-[(CH

3 2 Table 1 Ex. No.

Continuation

RN

2 X Physical Properties -N C CH 3 2

-CH

3 -NC CH 3 2

-NCCH

3 2

-CH

3

-CH-

3

-CH-CH-CF[

2 0

I

CH

3

-CH-CH

2 -0 Cl

CH

3 2 2 8- 2 .3 8 3.15; 3.35; 8.20-8

'H-NMR:

1,.25-1 .28; 2.60-2.73; 3.15; 3.35 0 129-131 0

C

-N(CH

3 2 -N (CCM 3 2

-CH

3

CM

3

CM

3 C H 3

-C-H

2

-C

CM 3

CH

3 C I

-C(CHM

3 2 -C F1 2

C

2 H C1 C 1

-CC(CH

3 2 -CM1 2 -C4 2 1 .05-1 1.30; 1.38; 3.15 1 H- NR: 1.42; 2.03- 2.08; 3.18; 3.32 0 99-1011C 2' -e Table 1 Ex. No.

Continuation X Physical Properties -N (CI 3 2

-C(CH-

3 2 -Cl] 2 -CH 2 /Cl

-CH

3 0 95-97 0

C

-N (Cl] 3 2

-N(CH

3 2 -Cl] 3

-CH

3 Cl] 3 -C-Cl] 2

<D/

I -C-Cl] 2 -0 Cu- 2 Cl(Cl] 3 2 0 Mn.P., 104-10511C 0 120-122 0

C

-N (CH 3 2 C 215 -CH- CI- 2

-CH

2 CD/ C1 CI-I-CH CH 14 C1 1 I Cl] 3 U11- 3 I H- NMR: 1. 00- 1 2.60-2.70; 3.18; 3.80- 3 1l]-NMR: 0.83-0 3. 18-3,*35; 8.15-8.23 CH13 1!.

4

FBI

Table 1 Continuation Ex. No.

,R

I

N-

R

X Physical Properties

-N(CH

3 2

CH

3

-CH

3

-N(CH

3 2

-N(CH

3 2

-N(CH

3 2

CH

3 2

-CH

3

-CR

3

-CH

3

-CH

3

C

2

H

-C C3 -H-CI-1 2

CH

2

C

2 C I -C(CH -CIHI 2

-CH

2

CX/CR

-C (CfH 3 2

CH

2

-CH

2

F

C1H 3

C

2 1- -C (CF1 3 2

-CFH

2 -C1 2 Cl 0 93-94O C o m. 108- 109 0

C

o 140-141 0

C

o 105-107 0

C

o 93-950 C 0 97 0

C

Table 1 Ex. No.

Continuation

-N

2 X Physical Properties -N 2

-CH

3 -CH- CH-C I 1

CH

3

C

2

H

5 -N (CH 3 2

-CH

3 I -NMR: 1 20- 1.25; 3 .18; 6,90-7. 00; 8.15-8.23 1 H-NMR: 0.88-1 .00; 3. 7 .10-7 8 .15-8 .23

'H-NMR:

1 .20-1 2.30; 2.55; 3.18; 3.35

-CH

3 -N (CH 3 2 -N (CR 3 2 -C3

-CH

3 -CH-C (CH 3 2

-CFH

2

/CR

3 CI3 -C(C4 3 2 CH 2 -CH-CH 2 -C14 2 CE1 3 ClI

-C(CH

3 2 -N=N Cl 0 xn.p.: 116-118 0

C

'H-NMR:

1,'80- 1.90; 3 .15 3 7.10-7.35 1

Y-NMR:

1.75; 3.18; 3.35; 7,40- 7.45; 9.40 -N (CY1 3 2

-CH

3 ~1i S

I

I1~ 1' Table 1 Continuation Ex. No.

1 R 2 X Physical Properties -N (CH 3 2

-N(CH

3 2

-N(CH

3 2

CE

3

-CH

3

-CH

3

-CR

3

-CH

3 C N H 3

C;F

2

-CH(CH

3 )2

-CR-CR

2 0 OCR4 3

CR

3

CN

C -CH 2 -SC 1) CI

CR

3

-CH--CFH

2 -O

CR

3 CR4 3 OCR4 3 -CR4 2 -CR4 2 /OCY1 3 OCR1 3 0 145- 1470 C O 114-116 0

C

O Mn.P.: 182-184 0

C

1

R-NMR:

1.35-1 2. 26; 3, 4.22-4.35

RH-NMR:

2, 90-2. 3.20; 3.40; 3.82; 3.85; 6.48

L

1) 'Ii

A

t 4

(D

CC)

Table 1 Ex. No.

Continuation

R

2 X Physical Properties

CO

-NCH

3 2

-CH

3

-CH-CH-

2 00 a CRl- 3 N I H- NMR: 1.30; 2.70- 2.77; 3.15; 6.63-6.70 ~1H-NMR: 20-1.*25; 3.15; 7.05- 7.13; 8.20- 8

-N(CH

3 )2

-CH

3

-CH

2

-CH-CH

2

CH(CH

3 2

CR

3 1 39 -N(CH 3 2

CR

3

-NC(CH

3 2 -NC CH 3 2

-CR

3

-CH

3

CH

3 2 -0

C,

CH

3 CI H 3

-CH-CH

2 CH 3

CH

3 -CI--CI-1 2 -0 C14 3 0 124-125'C 1

H]NMR:

2. 18; 2.22; 3.15; 8.25- 8.32 1

H-NMR:

1.35-1.40; 2.30; 3.15; 4.*23-4.35; 8.30-8.35 I

I

Table 1 Ex. No.

Continuation X Physical Properties 43 CH- C1 2 -H CI 2

CH

3 -N C CH 3 2 -N(C

H

3 2

CH

3

-CH

3 C 11 Cl-I 3

CH

3 -CHCF-CHq 2

CH

3

CH

3

CI-I

3 C1

-CH-CH-CH

2

CH

3 CH 3

CH

3

-CH

2

-CH

2 C11 2 -01-

'H-NMR:

1 .2 7-1I- 32; 3.15; 4.00- 4 .12; 8.15- 8 1

H-NMR:

1, 20-1 2.30; 3.18; 7.15-7.20 1

H-NMR;

0. 82-0.90; 1.20-1 3.15; 7.10 1HNMR: 1.,20-1.25; 3.15; 3,35; 7.15-7.20; 8. 15-8.*20 1

H-NMR:

2.30; 3,15; 3.32; 7.08- 7.13; 8, 17- 8 .23

(D

K)

-N(C H 3 2 -NC CH 3 2

CH

3

-CH

3

I

(D

00:, Table 1 Ex. No.

Continuation "R

I

X Physical Properties

-N(CH

3 2

-CH

3 ~cH 2 cH 2 Ir

C

2 I-Is 0 134 -135 0

C

-NC CH 3 2 -N (CH 3 2 -N (CH 3 2 -NC CH 3 2

-CH

3

-CH

2

-CH

2 -CHi( 2 0 163-164 0

C

-CH

3

CH-

3

C

-C-CH

2

-CH

2 UCH7 3

CI

-CH

3

-CI----CH-CH

2 I I

CH

3

CH

3 0C 4

H

9

-CH-CH

2

-CFH

2

/C

2

H

5

CIH

IF1-NI4R: 1,45; 2.00- 2.05; 3.15; 3.33; 8.20 1 1-1-NMR?: 0. 95-1 00; 1 .70-1 3.15; 7.10- 7 1 H- NMR: 1 .20-1,30; 2,56-2.70; 3.15; 7.10; 8.05-8.*10

-CH

3

I

(D

t, Table 1 Continuation Ex. No.

R

I

X Physical Properties -N (CH 3 2

-C

2

HS

-N (CH 3 2 -0 2

H

5

CM

3

-CM-CM-CM

2 I I

CM

3 CF1 3

-CH-CH-CH

2 -Cl I I

CH

3 C1-I 3

-CH

2

-CH-CH

2 Cl

-CH-CH

2 -0 OCFM 3

LC-C

2 113/ 11 3 Ij

IH--NMR:

0 198-1 2.80-2,.90; 3.15; 3,30- 3,40; 7,10- 7,.30 1

H-NMR:

1. .00- 1 3.18; 3.80; 3.90; 7.05- 7 1 H- NMR: 0.90-0.93; 3.15; 3.35; 7.05-7.30; 8.25-8.30

-N(CM

3 2

-N(CH

3 2

-C

2

M

5

-C

2

M

5 0 125-127 0

C

0 99-101 0

C

1

I

'F

II

(D

00 Table 1 Continuation Ex. No.

1- X Physical Properties

-N(CH

3 2 C2 CH C1 2 -CH 2

C

C1A -NC CH 3 2

C

2 I5I

-CFI

2

-CH-CH

2 CH (CH 3 2

-CH-CH

2 -CHq 2

/CH

3 3 1 H-NMR 1, 15-1,.20; 2 6 0-2 70 3.15; 3.85- 3,90; 8,10- 8.15 1 H-NMR: 0.90-0.95; 3.15; 3.82- 3.90; 7.08- 7.16; 8.30- 8 1 H-NMR.

1 .0 0 -1 1 .25-1 .28; 3.85-3.90; 7.06; 8.00- 8.15

IHNMR:

1 .35-1 2.35; 3,18; 3.90-4 8.35-8.40

-C

2

HS

-N(CH

3 2

-C

2

H

5 C1H 3

-CH-CH

2 -O Cl CR 3

I

j ~f.

!~4 03

MP

Table 1 Continuation Ex. No.

I-R 1 FR2 X Physical Properties -NC CH 3 2

-CH

3

,,CH

3

,,CH

3 C2H C H 3

-CH

3 C H- C-CH 2 CH 2 D 4 0 3

CH

3 -C (CfH 3 2- 2 -CH 2 -0

-CH

2

-CHI-CH

2

C(CH

3 3

C;H

3

-CH-CH-CH

2 I I CFk! 3

C;F!-

3

-CHI-CF

2

-CH

2 Cl CF1 0 83-850 C 1

H-NMR:

1 23 -1 26; 1.70-1 .88; 3 .15; 3.80; 6.80-6 .83

-CF!

3

-CH

3 1

H-NMR:

0 .9 3- 0 .9 6 1.30; 3.13; 3.32; 8.23- 8 .26

IH-NMH:

0.83-0.90; 2.*80-2.*90; 3.12; 3.50- 3,60; 8.20- 8 1H-NMRI: 1. 23-1.30; 1. 70-1,90; 3,12; 3.32; 8.05-8.10

C

2

H

5 Ut fI~ 77 b

J

I'

Table 1 Continuation Ex. No. IR !R2.

X Physical Properties C

H

CZH

5 C 2

H

5 F3

CH

3

-C--CH

2

-CI

2 Cl

C;H

2 -CH(CfH 3 2 -CH-CH -CFI\ C 2H2 1 H-NMR 1 .25-1 2.6 0- 2 .70 3.13; 3 3.50-3 1

H-NMR:

1 25 -1 1 p75-1 3.10; 3,30; 3.-90-4 00; 8.05-8.10 C 2

H

,-CH

3 C2H

-CH

3

-CH-CH

2 /Cl C H 3

CH

3 I -C'H-CH2C<

H

2

-C

CH

3 C14 3 0) 111-1131C

-CH

3 I H-NMR: 1 .0 5-1I 1.35; 3.10; 3.20; 3.85- 3.95; 7.15- 7 ,,CH3

C

2

H

-C (CH 3 2 -C14 2 -CH 2 C

-CH

3 0 88-90 0

C

CDf N3

I'

Table 1 Continuation Ex. NO. RR3 X Physical Properties

,CH

3

C

2

H

C H 3

C

2

H

5 CH3 C2H C 1 -C (C1 3 2

-CH

2 -I -CH 2 1 C

-CH

3 1 1 -NIR 1 .25-1 1.40; 2.00- 2.08; 2.57- 2.62; 3.10; 3

-CH

3

-C(CH

3 2 -CH 2

-CH

2

D

0 Mf.P.: 123-124 0

C

-CH

3 C13 21 5

CH

3 -CH-CH-CH-- C CI CIT1 3 CI*1 3 1 H-NMR 3,15; 3.35; 3.50-3.57; 7

IH-NMR:

0.85-0.90; 1,.20- 1.25; 3. 10; 3,50- 3.55; 7.05- 7,15; 8.15- 8

I

9 Table 1 Ex. No.

Continuation X Physical Properties

,CH

3

C

2

H

C

2

H

C

2

H

5

H

3

C

2

H

-CH

3

-CH

3

-CH

3

CH

3

-C(C

2

H

5 2

-CH

2

-CH

2

-C(CH

3 2 -CH1 2 -CH 2 /CH 3

IH-NMR:

1.25-1 00- 2. 2.55-2.60; 3.10; 3.50- 3.55; 8.00 1

H-NMR.'

1.25-1.30; 1.40; 2.60- 2.65; 3.10; 3.50-3,55; S. 1

HNMR:

1.40; 2.56- 2.62; 3.10; 3.50-3 7.05-7.20 0 t.P

CO

Tab Ex.

-C(CH

3 2

-CH

2

-CH

2

CI

-C(CI-

3 2

-CH

2

-CH

2 V 0 84-86 0

C

C H 3

C

2

H

5 I H-NMR: 0 .9 0 1.25-1.30; 60-2.* 3. 10; 3,50- 3.55; 0. -Tv 1-

I

Table 1 Continuation Ex. No. -R 1- X Physical Properties

AU

Q Ir Ar 1C .Tab' Ex.

N,-C 4

,-CH

3 C143

-CH

3 -C (CH 3 2

CH

2

H

2 -Q cI -CHq-CH-CH 2

-<D/F

CH-C14- C H 2 /C1 1 1

CH

3

C

2 14 5 0 Ml.P.: 64 0

C

C

2

H

5

-CH

3 I H-NMR: 0. 80 1 .25-1 3.15; 3.50- 3.60; 8.20- 8 1H-NNR; 1. .15 -1 1 .70- 1.80; 3.12; 3.95- 4.10; 3.15- 8 .22 1

H-NMR:

1.20-1.25; 2.30; 2.53; 3.12; 3.50- 3.58; 7.00- 7.10 1 HNMR: 0 .85-0. 1 1 3.10; 3,50- 3,58; 8.20- 8 C 2 F1 5 -0143 -CF--CH-CH 2 CH3 CF1 3 Cl-I 3

C

2 14 5

-CH

3

-CEH-CH-CH

2 \Q 01-13 CI-1 3 00C31-17 Table 1 Ex. No.

Continuation X Physical Properties Tab' Ex.

-N(C

2

H

5 2

I

,-CH

2

-CH

2

-CH

3

C

2

H

5

-CH

3 -C3

CI

3

-CH-CF-CH

2 Cl

CH

3

CH

3 -CH-CH-CII\ Cl

CH

3

CH

3

-CM--CM-CM

2 I I

CH

3 CH4 3

-CH-CH

2 -O C7/ Cl

UM

3

H-NMR:

0 0.85-0.90; 1.20-1 3.30; 3.45- 3.55; 8.18- 8 11- NMR; 0 2.25-2.35; 2,70-2.83; 3.30; 3.45- 3.55; 8.20- 8 1

H-NMR:

0 1.65-1.75; 3.30; 3,35- 3.40; 3.45- 3.55; 8,20- 8 1H-NMP:.

o 1.25-1.30; 1.35-1.40; 3.30; 3.45- 3.55; 8.30- 8

H

2

-CM

2

-CH

3

C

2

H

5 ,C H 2

-CM

2 -C H 3

C

2

H

5

I

J I Table 1 Continuation Ex. No.

X Physical Properties

,,CH

2

-CH

2

-CH

3

CH

3

,,CH

2

-CH

2

-CH

3

CH

3

,,CH

2

-CH

2

-CH

3

CH

3

-CH

3

-CH

3 -C (C1 3 2

-CH

2

-CH

2

\O

-CH-CH-CFH

2 /Cl CHt 2 -CH k Uil 3 2

-CH-CH

2

-CH

2 Cl

-CH-CH-CH-

2 Cl CF1 3

CH

3 0 1.45; 1.65- 1.75; 2.60- 2.67; 3 .12; 3 .42-3 .48; 8 1H-NMR: 0 0 .9 0- 0 .9 1.65-1.85; 3.13; 3.32; 7.*10-7 1 H--NIIP: 0 0 .95-1 .00; 1 22- 1 2. 60-2. 3.is 3.32; 8.05-8,10 11H-NMR: 0 1.20-1.25; 1.65-1.75; 3.12; 3.40- 3.50; 8.18- 8

-CH

3

-CH

3

I-.

Table 1 Continuation Ex.- No.

I.

X Physical ,,CH2-CH2- CH 3

CH

3

,,CH

2 -CH2- CH 3

CH

3

-NCCH(CH

3 2 2

,,CH(CH

3 2

,,CH(CCH

3 2

CH

3

-CH

3

CH

3

-CH

3 -CH--CH-CH 2

UH

3

CH

3

-CH

3 F3 -C (CH 3 2 -CH-CH4 2

CH

3 -C (C1 3 2

-CH

2 -C1 2 1 ifiNMR: 0 1 .23-1 .26; 2.60-2.70; 3,13; 3.-50- 3.58; 7.05 1

H-NMR:

o 1.20-1.25; 3.13; 3.40- 3.50; 7.15- 7.30; 8.20- 8 0 Mf.P.: 113-115 0

C

1 H-NMR: 0 1. 25-1.28; 1.45; 2.60- 2,68; 2.98; 7,13-7.30

IH-NMR:

0 0. 90-0. 1. 25 -1.30; 2.60-2.75; 3.00; 3.32; 7.15-7 8. 00-8.*05

-CH

3

-CH--CH

2 -CI4 2

C;

4

H

9 Table 1 Continuation Ex. No.

1~ X Physical

(D

m

.P.

tM Properties .,CH C CH 3 2 98

CH

3 ,,CH CH 3 2 99

CH-

3 -CH-CH 2

CH

2 ClI

CH

2

-GH(CH'

3 2

-CH

3 100 101 102 ,,CH (CH 3 2

CH

3 ,,CH (CH 3 2

CH

3 ,,CH (CH 3 2

CH

3

CH

3

-CH

3

-CH

3

C(CH

3 2

-CH

2

-CH

2 H 3 -C H--C H C H 2 /1 1 1

CH

3

CH

3

-CH-CH

2 -CH 2 0 1,23- 1.30; 1 .70- 1 2. 60 70 2.96; 3.30; 8.05-8.10 '11--NMR: o 1.25-1.30; 2.60-2.70; 3.00-3.32; 7.10-7 1 Hl-NMR: o 1.25-1.28; 1.45; 2.06; 2.30; 2.95; 3.30; 8.2-0 IH-N4R: 0 0.85-0.90; 1. 85- 2. 00; 2.98; 3 .23; 4.35-4

'H-NMR'.

0 1,20-1,27; 2,30; 2.55- 2,70; 2.9J5; 3.30; 7

I

LL~

p,.

Table 1 Continuation Tah Ex.

Ex. No.

2N X Physical Properties 103 104 .CH C CH 3 2

CH

3 n C 4 H H 9 3

CFH

3

-CH

3

CH

3

-CH

3 0C 3 1- 7 0 1 1 C14 3

CH

3

-C(CH

3 2

-CH

2

-CH

2

-CF--CH-CH

2 ClI

CH

3

CH

3

-CH-CI-

2

-CH

2 CH1 3

CIH

1 Hq-NMR: 0 1 .00-1 1.20-1.30; 3.00; 3.30; 3 .85-3 8.20-8.25 1

H-NMR:

o 1.45; 2-00- 2.08; 3.10; 3.43-3.50; 8.20 1 H-NMR: o 0.85-0.90; 0. 95 -1 00; 3.15; 3.45- 3 .50; 8.18- 8.23 1 1--NMR: 0 0 .9 5 -1,.00; 1 .22- 1.26; 2 .60-2 3.12; 3.45- 3 .50; 7 105 106

,,C

4

H

9

CH

3 .,nC 4

H

9

CH

3 a

I

(D

Table 1 Continuation Ex. No.

AR'

-N~

2 X Physical Properties 108

C

7 H15

CH

3 -N 0 -N -N 0

-CH

3 109 CH 3 -C (CH 3 2 -CH1 2

-CH

2

-CH

2

-CH-CH

2

C(CH

3 3

CH

3

-CH-CH

2

-_CH

2

C;

4

H

9

-CH-CH

2

-CH

2

CH

3

I

CH

3

CA

0 110-112 0

C

0 1 4 8 1 5 0 o C I H-NMR: 2 2.60-2.70; 3.12; 3.45- 3.50; 8.20 110 111 112

-CH

3 0 94-96c C '-N0 -N 0 0 118-120 0

C

CH13 1 Hl-NM-R: 0. 85-0.90; 3.25; 3.60; 3.68; 8.15- 8.20

I

f

(D

Table 1 Continuation Ex. No. N..

X Physical Properties Tabi Ex. 7 113 114 -N 0.

-N 0

-CR

3

-CH-

3 115 116 -N 0 -N 0

-CR

3

-CH

3

-CIH-CH

2

-CH

2 /Cl

CI-

2 -CH (C4- 3 2

-CH-CH

2 -CH 2

CR

3 -CH _CH 2

-C(CR)

2

C

CR

3

-CH-CHR-CR

2 3 Cl I I Ct- 3 C-i 3 1 1-1-NM13: 0,90-0,95; 2,60-2.70; 3.35 3,65- 3.70; 7.10- 7.*20 1 H-NMR: 1. 25-1.-20; 1 .75-1 2.60-2.75; 3.35; 3.85- 3 0 170.-172 0

C

1

H-NMR:

1 .05-1 I 1,30; 1.40; 3.20; 3-60- 3.65; 7.60- 7 117 -N 0 -CR 3 0 a. p. 1320 C Table 1 Continuation Ex. No. "R' X Physical X Properties 118 119 120 -N0 -N \-j0 -N 0 -ND0

-ND

-CH

3

-CH

3

-CH

3

-CH

3

-CH

3 -C(CI1-1 3 2 -C 1 2 -C 11 2 <D H C- 3 C H -C-1 2

F

I I

CH

3

CI-I

3 -H-CI-1 2

-CH

2

CH

3

CH

3

-C(CH

3 2

-CH

2

-CH

2

-CHI-CH

2

-CH

2

H

3 C 1 0 119-121 0

C

0 125-126 0

C

0 mn.p.: 99-101 0

C

o m.p. 1o2 0 c 121 122 1

H-NMR:

1 .70; 2.30; 2.60-2.70; 3,30; 3,55; 7.05; 8.05- 8.10 1FH-NMR: I 22-1.* 26; 1,70; 2.60- 2.70; 3.30; 3.55; 7.15- 7.*30 123

-ND

-CH

3 -CH-CI1 2 -CH4 2 0

CH

3 j

A

0-

CIE

(D

OD

.P.

-P-

I

Table 1 Ex. No.

Continuation X Physical Properties -ND cl- 3

-CH-CH

2 -O Cl C H 3 -CH-CH-CHq 2 Cl

CH

3 C11 3 0 119-121 0

C

125 -ND -CH 3 126 127 128 -ND -CH 3

-C(CH

3 2

-CH

2 -CHq 2

/CH

3 1 1-I-NMR: 0.85-0 1.20-1.25; 1.70; 3.30; 3.55; 8.20- 8 14NMHW 1.40; 1.70; 2.00-2.05; 2.30; 3 3.55; 8.23

'H-NMR:

1 .20-1 1,70; 2-60- 2.70; 3.30; 3.55; 8.05- 8.10 -ND -CH 3

-CH-CH

2

-CH

2 Cl -C (CH 3 2

-CH-

2 -CiH 2

-C

-NJ] CH3 0 110 0

C

-Ti -77 Table 1 Continuation ~y.

Ex. No.

"R

I

R 2 X Physical Properties

-NJ

~NJ

-CH

3

-CH

3 -C (CH 3 2

-CH

2

CH

2

.<D/CH

3

-CH--CH-CH

2 1 1 1

CH

3

CH

3 130 1-I 1

H-NMR:

0 1 .40; 2 .00; 2.30; 2.55- 2.60; 3.35; 7 .05-7. 1 1--NMR: 0 1 .15 -1 2.0; 3.35- 3.60; 7.05- 7 1 H- NMR: 0 1.45; 2.00- 2.05; 3.00; 7,.10-7 5.,23 1 H-NMR.

0 1.20-1.25; 1.*65-1.*75; 2.30., 3.10; 3.40(J-3.* 8,*14-8 -C (CH 3 2

-CH

2 -CH 2 132 ,,C2_

C

H

2

C-

3

CH

3

CH

3 C1H 3 -CH-CH-CH 2 1 1 Ck- 3 UH 3 ~-1NV4~ 4 Table 1 Continuation Ex. No.

-pR 1 N- NR 2 X Physical Properties Tab Ex.

133 134 135 136 137 ,cC (Ci 3 2 CiA 3

CH

3

-N(CH

3 2 -14(CH 3 2 ,C 2

H

5

CH

3

-CH

3

CH

3

-CH

3

CH

3 -CH-CH-CF1 2 1C H -CH-CH-CH 2 I I L; 3 UC1i4 3 -C(AC3-C-Ci 2 /0

CH

3 CI1 3 -CH-CH4 2 -O C H 3 1 1

NMR:

1,20-1 2.30; 2.95; 3.30; 6.95- 7.20; 8.20- 8.*25 1 -NMR: 0. 80-0.90; 2.30; 3.12; 3.50-3.60; 8,15-8.*23 1

H-NMR:

2.30; 3.15; 3.85-3.90; 6.90-7,20; 8.25-8.30 0 142-144 0

C

-CH

3 'iA-NMR: 1. 25-1.30; 2.30; 3.10; 3.50-3.55; 8.30-8.35 t7

(D

:r rU, Table 1 Continuation Ex. No.

R

R

2 X Physical Properties 138

,,C

2

H

5

CH

3

CH-

3 139 -N (CH 3 2 -CH-CH 2 -C -1 2 -C C 1 C 3 C t 3 CH--CH- CH 2

:/CH

3 I I

CH

3

CH

3

-CH--CHI

2

-CH

2

OC

2

H-

5

-CH-CH

2

-CH

2

F

CF'

3 1 H-NtIR: 1 .20-1 2 .5 5 -2 65 3.10; 3.75; 8.05-8.10 1 H-NI-R; I 20- 1. 2,20; 3.15; 6 .8 5 -7 8.18-8.23 1

FH-NMR:

1.23-1 1.70-1,.90; 3.15; 3.95- 4.03; 8.05- 8.10

IHNMR:

1.25-1 .27; 2. 60 70 3.18; 3.90- 4 .00; 8 8.10 140 -N (CH 3 2

-CH

3

CF

3 -1

I

Al- Table 1 Continuation Ex. No. TablE Ex. b~ X Physical Properties 142

,C

2

H

5 C H 3 143 144 145 146 ,C 2

H

5

CH

3

,C

2 H5 -NC CH 3 2

-CH

3

-CR--CH-CIT

2 1 1 CR1 3 CR 3

CR

3

-CH

3

-CH-CH

2

-CR-

2 0C 2

H

5

-CR

3 -CH _CH 2 -O /0 CHR 3 C1H 0 117-119 0

C

1 H-NMR: 0.85-0.90; 2.80-2.90; 3.12; 3.50- 3.60; 7.10; 8 .20-8 1

H-NMR:

1.20-1.30; 1.70-1.90; 5 3.10; 8.05- 8.10

-CR

3

CR-

3 -C (CR 3 2 -C C C1

C(CH

3 2

-C

5 C 0 129 0

C

0 Mn.P.: 127 0

C

I

4

I

It

'I

Table 1 Ex. No.

Continuation R1 Physical Properties Tabi Ex.

147 -N (CH 3 2 -N (CH 3 2 148

-CH

3

-CR

3

-CH

3

-CH

3

-CH

3

CEC

H

149 150 151 -N (CH 3 2 0 121 0

C

C1H 3

CH

2 -CH(CH 3 )2

-C(CH

3 2 -C(CH 3 2 -N=N 1

H-NMR:

0.85; 0,90; 1,75; 3,15; 3,33; 7.80- 7.*83 0 113-115 0

C

0 136-137 0

C

0 93-95 0

C

,C 2

H

5

CH

3 Table 1 Continuation Ex. No.

X Physical Properties 152 -N 0 -C3 -C (CH 3 2 -N=N

-CH-CH

2

-CH

2 OCR 3 C H 3 C 145-147 0

C

153 154 -N CH 3 2 -C2H5

-CR-CH

2 -0

CH

3 CI'1 3 I H-NMR: 1 .00-1 .03; 2 ,5 8- 2.-6 3.15; 3.75; 8,10-8.15 1H NM Rh 0.98-1 .03j; 2.30; 3.15; 4.23-4.33; 8.35-8.40 1 H-NMR 1.25-1 1 70-1 3.13; 3.32; 3.50-3.58 1

H-NMR:

1 .25 -1 .28; 1 .36 -1 2.98; 3.30; 6 .80-6 155 156 ,C 2

H

5

CH

3

-CR

3

-CH-CH

2 -CF1 2

-F

CH

3

-CI-I-CH

2 -0

OCR

3 j

CH

3

,-CH(CH

3 2

CH

3 -C3 f

[I

Table 1 Continuation Ex. No.

"R1 X Physical Properties Tabb Ex. I 157 158 159 160 161

-N(CH

3 2 -NC CH 3 2

-N(CH

3 2

.,C

4

H

9 n

.CH

3

-ND

-CH

3

-CH-

3

CH

3

CH

3

CYH

3 -C(CF1 3 2

-CH-

2 2 C CN

CH

3 0 145-147'C 1H-NMP: 1.33; 1.88- 1.95; 3.15; 3.28; 7.96- 8.02

CH

3

-C-CH

2 -S0 2 Cl

CN

-CH

2 _0

-CH

2 _0 0 Mf.P.: 163 0

C

(decoup.)

H.NMR:

0 1.30-1.40; 1,.60-1 3.10; 3.30; 4.47-4.50 0 107 0

C

~Ij Table 1 Ex. No.

Continuation Table Ex. N( X Physical Properties 162 163 N3

CH

3

-CH

2 _,CH (CH 3 2 CH3-

-,C

3

H

7 n

CR

3

-,C

6

H

1 3 n

CH

3 C1H 3

CH

3 -Cl-1 2

-CR

2 -0

-CR

2 0 1.,90-2, 00; 3 .40 4 .47 4.50; 8.55- 8.60 o 119-i21 0

C

1 1--NMR: o 1.6 3 73; 3.13; 3.33; 4.48-5,03 1 H-NMR: o 1.,2 5-1.3 3,13; 3.32; 3,40-3,50; 4 .47-5 .00 165 CFH 3 Table 1 Continuation Ex. No.

N-R

TablE Ex. DS X Physical Properties -NC CH 3 2 -N (CR 3 2

-N(CH

3 )2 -N (CH 3 2

CR

3

-CH-CH

2 -S5< 1" 1

H-NMR:

1.30-1.35; 3.15; 3.30; 8 15-08 C H 3 H 0 181-183'C

CR

3 H -O 0 mn.p.: 125 0

C

CR

3 CI--C H 2 -C H 2

C

IR

1

R-NMR:

1 .25-1 .28; 2,70-2.78; 3.10; 3.35;, 3.90-4 .02; 100 101 If Table 1 Ex. No.

Continuation X Physical X Properties Tabl( Ex. I 170 -NC CIA1 3 2

CH

3 -CH-CH F C1A 3

F

-NC CH 3 2

CHI

3 cl-1 3

C

0 1

H-NMR:

1.25-1.28; 2 62-2 .70 3.18; 3 3 88-4 00; 0 1 IA-N'R: 1.36- 1.-38; 3.15 3 3,90-4 4 .25-4 0 1H-NMR: 0 9 0- 0.9 6 1 24- 1 .27; 3.15; 3.35; 7.-10; 103 104 172 -NC CH 3 2 CH 3

-CH-CH

2

-CA

2

-C

3

H

7

IA

105 106

I

2~r4i Table 1 \Continuation Ex. No.

R

X Physical Properties Table Ex. N 173 -N (C CU 3 2 -NC CH 3 2

-N(CH

3 2

CH

3

CH

3 cl- 3

CU-

3

CH

3 -CH- C-CH 2 -O F

CH

3 Gil 3 -CH-CF1 2 -O F I -Q

CU

3

F

-CH--CH

2

-CH

2

F

CI-

3

F

CI 2 CIH 2 -CI 120 Ii 1-WiIR 1 .05 1.-12; 1 .18-1 .22; 3.15; 3.32; 4 .00-4 1.37-1.4 3,17; 3,35; 4 .22-4 .32; 1 H-NMR: 1 .22-1.-25; 1 .72- 1,85; 2. 60-2. 68; 3.15; 3.35; (Syrup) 107 108 109 175 176 The 1

H

as the 110 I11 112 NMR spectra were recorded in deuterochioroforn (CDCl 3 with tetramethylsilane (TMS) internal standard. The chemical shift is stated as the 8 value in ppm.

;ij i.

0 0) Ei Le A 28 424 60 /1 B j 9 d:i Startina compounds of the formula (II): Example (II-1)

(CH

3 2

N

H

3

C

-N

N-N

Step 1:

(CH

3 2 N-C=N-C-O A mixture of 35 g (0.5 mol) of dimethyl cyanamide and 156 g (1.0 mol) of phenyl chloroformate is stirred for 16 hours at 100°C. More readily volatile components are then removed by distillation under a water pump vacuum (bath temperature: 80°C), and the oily residue is distilled under an oil-pump vacuum.

61.4 g (54% of theory) of N,N-dimethyl-N'-phenoxycarbonyl-chloroformamidine of boiling range 158°C- 165°C/0.5 mbar 0.8 mbar are obtained.

41 2 l- Step 2:

(CH

3 2

N

H N--N

H

3 C "H A solution of 6.9 g (0.15 mol) of methylhydrazine in Le A 28 424 74 i^I -I (9 x CO '-4 UIN \Le A 28 424 A 61 i: i

~I

I'i" i ;i ~a; 100 ml of dioxane is added dropwise with stirring at to 30°C (cooling required!) to a mixture of 17.0 g (0.075 mol) of N,N-dimethyl-N'-phenoxycarbonyl-chloroformamidine and 100 ml of methylene chloride. The reaction mixture is stirred for 4 hours at 20 0 C and then filtered. The solvent is removed from the filtrate by distillation under a water pump vacuum, and the freed phenol is removed by distillation under an oil-pump vacuum.

9.8 g (92% of theory) of 5-dimethylamino-l-methyl-l,2dihydro-3H-1,2,4-triazol-3-one are obtained as an oily residue.

'H-NMR (DMSO-d6, 8, ppm): 3.20; 3.45.

The product can be brought to crystallisation by boiling with acetonitrile; melting point: 222°C.

Example (II-2)

(CH

3 2

N

(CH3C

-N

(CH3 2 CH

H

Step 1:

C-N

I

(CH

3 )2CH-N-NH-COOC 2

H

73 g (0.5 mol) of ethyl 2-isopropylhydrazinecarboxylate and 42 g (0.5 mol) of sodium hydrogen carbonate are Le A 28 424 75 (a x E-i w Le A 28 424 62 i "i._li i i r r r:~i?.7~Psp si~- ~X i i i ii~l r ji ri::c

I

introduced into 200 ml of methylene chloride and 400 ml of water. 55 g (0.52 mol) of cyanogen bromide are introduced with stirring at room temperature (cooling required). The evolution of CO 2 ceases after further stirring for three hours. The organic phase is separated using a separating funnel, dried over sodium sulphate and concentrated in vacuo.

73 g (85.4% of theory) of ethyl 2-isopropyl 2-cyanohydrazinecarboxylate are obtained as the residue in the form of a pale oil.

1 H NMR: (CDC1 3 8, ppm) 1.25-1.30; 1.30-1.35; 3.5-3.65; 4.20-4.30.

Step 2: (CH3)2N CH3 2CHN -N(CH3)2CH

(CM

3

CH

g (0.2 mol) of ethyl 2-isopropyl-2-cyanohydrazinecarboxylate are added dropwise to a solution of 100 ml 33% dimethylamine in absolute ethanol. The solution is stirred first for 8 hours at room temperature and then for 1.5 hours at reflux temperature. After concentration in vacuo, an oily residue, which crystallises slowly upon standing, remains. Recrystallisation from cyclohexane/ethyl acetate (4:1 by volume) gives 30 g (88% of theory) of 5-dimethylamino-l-isopropyl-l,2-dihydro-3H- 4 ~dL1I~W \Le A 28 424 76 63 3.

1,2,4-triazol-3-one of melting point 111 0

C.

Compounds of the formula (II) which can be prepared analogously are, f or example, those in Table 2 below:

R

2 .N

FR

3 II Table Examples of the starting compounds of the formula (II) Ex. No. R1 R R 2 R5 Melting point (0 0

C)

11-3 11-4 11-5 11-6 11-7 Il-8 11-9

C

2

H

5

CAH

-CH

2

CH

2

-O-CH

2

CH

2

CH

3

CH

3

CH

3

CH

3

CH

3

CH

3

C

2

HS

89 183 (amorphous) (amorphous) 119 (amorphous) CH (CH 3 2

CH

3

CH

3 CHi(CH- 3 2

C

2 11 5

CH

3 Startina compounds of thp formula (III)

CH

3

H

5

C

2 00C H 2

-CH

2

-C-N=O=

CH

3 150 g (1.5 mol) of phosgene are introduced at 15'C into 77

S.,

1 of chlorobenzene, and a solution of 235 g (1.0 mol) of 1,l-dimethyl-3-(4-ethoxycarbonyl-phenyl)-propylamine in 1.0 1 of chlorobenzene is metered dropwise into this solution, while stirring, during which process the internal temperature rises to approximately 25 0 C. The reaction mixture is then heated to approximately 70 0 C and slowly heated to reflux (approximately 127 0 C) while stirring and passing in more phosgene (approximately g/h) and, after 30 minutes, treated with phosgene under reflux. Approximately 1 1 of chlorobenzene together with excess phosgene is removed from the clear solution by distillation. Finally, the mixture is evaporated under a water pump vacuum, and the residue is distilled under an oil-pump vacuum.

253 g (97% of theory) of 1,1-dimethyl-3-(4-ethoxycarbonyl-phenyl)-propyl isocyanate of boiling range 125 0 C-130OC/0.1 mbar are obtained.

Le A 28 424 78 other examples of compounds of the formula (III) which can be prepared analogously to Example (III-1) are those listed in Table 3 below: R 4

-N=C=X

(III)

3: Examples of the compounds of the formula (III) Ex. No. R 4 X Physical Data

CH

3 111-2

H

5

C

2 00C CH 3

CH

3 111-3 H 7

C

3 00C H 2

-CH

2

CH

3

CH

3 111-4 NC H 2

-CH

2

CH

3 O) 110-113C at 0.08 mnbar o) 110*C at 0.1- 0.2 mnbar

CH

3 111-5 0 H 2

-CH

2

-C-

CH

3 111-6 H 2

-CH

2

-CH-

CH1 3 4 0 0

I

I

yLe A 28 424 79

I,

Table 3 Continuation Ex. No. R 4 X Physical D E L a

CH

3 111-7 Cl <7 -H 2

-CR

2

-C-

CH

3 111-8 R 3 C H 2

-CH

2 -CW4-

C"

3 94*. at 0.2 mbar 111-9

CH

3

H

2

-CH

2

-CL;

1 CR 3

CR

3 III- 10 H 2

-CH

2

-C-

Cl CRI -4

CR

3

I

I II- 11

R

3 C CR 3

CR

3 111-12 R 2

-CH

2

-CU-

CR

3

CR

3

CH

3 111-13 H 2

-CH

2 CN

CR'-

3 9

K

80

IT

J

Starting compounds of the formula (IV) Example (Tv-i)_

(CH

3 2

,SN-N.

F

3 C c-cl 11 0 A mixture of 71 g (0.5 mol) of 1,2-dihydro-3H-1,2,4-triazol-3-one and 800 ml of acetonitrile is heated to ref lux point while passing in phosgene and treated with phosgene until the evolution of hydrogen chloride has ceased. Nitrogen is subsequently blown through the mixture, and the solvent is then carefully distilled off. The residue is recrystallised from ethyl acetate.

88 g (86% of theory) of 2 -c hloroc arbonyl 5-dinethyl amino 1-methyl-l,2-dihydro-3H-1,2,4-triazol-3-one of melting point 98-100 0 C are obtained,, 'H-NMR (CDCl 3 /TMS): 8 3.20; 3.28 ppm.

4 81 i* "St I .i i t; I: gL~ l.W C

B;

Starting compounds of the formula Example (V-l)

CH

3

C-C-NH

2 C1 CH 3 li 96.7 g (0.50 mol) of 1-bromo-2-chloro-benzene and 45.7 g (0.55 mol) of 3-amino-3,3-dimethyl-l-propine are introduced into 500 ml of triethylamine. 7.0 g (0.01 mol) of palladium(II)-bis(triphenylphosphine) dichloride, 7.6 g (0.04 mol) of copper(I) iodide and 21.0 g (0.4 mol) of triphenylphosphine are added, and the reaction mixture is then refluxed for 24 hours. The mixture is then filtered, and the filtrate is evaporated under a water pump vacuum. The residue is extracted using methylene chloride/water (approximately 300 ml/300 ml), and the organic phase is separated off, dried using sodium sulphate and filtered-. The solvent is removed from the filtrate by distillation under a water pump vacuum, and the crude product which remains is purified by distillation under an oil-pump vacuum.

74.1 g (75% of theory) of 3-amino-3,3-dimethyl-l-(2chloro-phenyl)-l-propine of refractive index 20 n D 1.5799 are obtained.

\Le A 28 424 82 sj ji t N dA r i in' Example (V-2)

CH

3 Cl

H=CH-C-NH

2

I

CH

3 In a Parr hydrogenation apparatus, 96.8 g (0.50 mol) of 3-amino-3,3-dimethyl-l-(4-chloro-phenyl)-1-propine are mixed with 400 ml of tetrahydrofuran, and 13.0 g of Lindlar catalyst palladium on calcium carbonate, doped with lead) are added. The mixture is then shaken under a hydrogen pressure of 3 bar at a temperature which rises gradually from 25 0 C to 50 0 C, until the calculated hydrogen uptake (1 mole equivalent after approximately 15 hours) has ended. The mixture is then filtered, the filtrate is evaporated under a water pump vacuum, and the crude product which remains is purified by distillation under an oil-pump vacuum.

67.5 g (69% of theory) of 3-amino-3,3-dimethyl-l-(4chloro-phenyl)-l-propene of refractive index n 1.5528 are obtained.

Example (V-3)

CH

3 S/ H 2

-CH

2

-C-NH

2 Cl

CH

3 In a stirred autoclave, 40.6 g (0.21 mol) of 3-amino-3,3- Ij4 Le A 28 424 83 N1

I

dimethyl-l-(2-chloro-phenyl)-l-propine are mixed with 250 ml of tetrahydrofuran, and 10 g of Raney nickel are added. Hydrogen is then metered in up to a pressure of bar, and the mixture is gradually heated from 25 0 C to 40°C, while stirring. Every time the hydrogen pressure drops to 40 bar, it is readjusted to 50 bar until the pressure remains constant. The mixture is subsequently filtered, the filtrate is evaporated under a water pump vacuum, and the crude product which remains is distilled under an oil-pump vacuum.

31.8 g (77% -of theory) of 3-amino-3,3-dimethyl-l-(2chloro-phenyl)-propane of refractive index n 1 1.4817 are obtained.

Use Examples: In the Use Examples which follow, the compound shown below is used as comparison substance: O N

(A)

H C-NH-

I

o 2-phenylaminocarbonyl-5-morpholino-l,2-dihydro-3H-1,2,4triazol-4-one (disclosed in DE-OS [German Published Specification] 2,042,660, Example .bd~ld

I

Le A 28 424 84 j i' i- i

I

:t i -'vss^ Example A Post-emergence test Solvent: Emulsifier: 5 parts by weight of acetone 1 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.

Test plants which have a height of 5 15 cm are sprayed with the preparation of the active compound in such a way as to apply the particular amounts of active compound desired per unit area. The concentration of the spray liquor is so chosen that the particular amounts of active compound desired are applied in 1,000 1 of water/ha.

After three weeks, the degree of damage to the plants is rated in damage in comparison to the development of the untreated control. The figures denote: 0% no action (like untreated control) 100% total destruction Used at an application rate of 500 g/ha, an activity of up to 100% against Panicum, Setaria, Abutilon, Datura, Galium and Polygonum, combined with an outstanding 2 i 85

V

i 1 I- j i: 7; i r i

I

tolerance in wheat, maize and soya beans, is shown by the compounds of Preparation Examples: 1, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 15, 18, 20, 22, 23, 26, 27, 30, 63, 64, 65, 67, 69, 74, 77, 81, 91, 92, 96, 98, 101, 110, 111, 112; 114, 116, 119, 122, 123, 125 and 127. No activity against the abovementioned weeds is shown by comparison compound Example B Pre-emergence test Solvent: 5 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.

Seeds of the test plants are sown in normal soil and, after 24 hours, watered with the preparation of the active compound. It is expedient to keep constant the amount of water per unit area. The concentration of the active compound in the preparation is of no importance, only the amount of active compound applied per unit area being decisive. After three weeks, the degree of damage to the plants is rated in damage in comparison to the development of the untreated control. The figures denote: ",Le A 28 424 86 L- i r.l r 0% no action (like untreated control) 100% total destruction Used at an application rate of 1000 g/ha, an activity of up to 100% against Amaranthus, Impomoea, Matricaria and Portulaca, combined with an outstanding tolerance in barley, maize and soya beans, is shown by the compounds of the following Preparation Examples: 7, 9, 12, 65 and 67. The comparison compound only shows an activity against Ipomoea and Portulaca The formulae of the compounds of the general formula (I) according to the invention which have been used for the use examples are listed individually hereinbelow and provided with the number of the preparation examples ("Example

,N

H

3 C N

H

3 C C -NH-CH-CH 2 CH2-- /-CH 3

II

(CH

3 )2N 0

CH

3 CH3

H

3

C

-s

C-NH-C-CH

2

-CH

2 I CH o

CH

3 87 -I i o \Le A 28 424

S/

t 'e^

(C

3 2

N

-N

(4) j

H

3 C C-NH-CH -CH-CH 2

(CR

3 o CH 3

-N

H

3 C C-NH-CH-CH 2

-CR

2 o C 4 Hqn

(CH

3 2

N

-N

(6)

H

3 C ,NNC-NH-CR--CH 2

-CH

2

>-H

3 0

CH

3

(CR

3 2

N

N-N,

R

3 C C-NH-CH-CH 2

-CH

2 1 o

CR

3

(CR

3 )2 (8)

H

3 c C- NH CH CH 2 -CH 2 1 0 C4Hqn Le A 28 424 -8 88

(CH

3 21

H

-N NI

H

3 C C-NH-CR-CH-CH 2 o CH 3

CH

3 2

N

l1 3 c C-NR-CH-CH 2

-CH

2 I I I o

CR

3

(CR

3 2

H

3

C

(CR

3 2

H

3

C

N

C-NH-CH-CH

2 -a 1 o CH 3

N

rN= CR 3 (12)

C-NR-CH-CH

2 -C 1 0 CR 3

CR

3 2 IN N(13) 2 ~CH3

H

3 C CNCR-R 0 CH- 3

C

4 eA 28 424 89 (CHM 2 7 CH 3 14CC-NH--C-CH 2

-CH

2 0 CH 3 C 1

(CH

3 2

N

-N

(18)

M

5 C 2

C-NH-CM-CH

2

-CM

0 CH 3

(CM

3 2 N -N =C 2 0

I

H

3 C C-NH-C-CM 2

-CH

2 0 C 2

H

(CM

3 2

N

CH

3 (22)

H

3 C C-NH-C-CH 2

-CH-

2 0 CH 3 Cl

(CH

3 2

N

S CH 3 (23) 0. CM 3 3 2

N\-

>=oCM 3 (26) H C C-NH-CM-CM-CM 2 H F I. 0 CM 3 90

(CH

3 2N

C

2 HS (27)

H

3 C C-NH- CH-CH- C- 1 0

CH

3

(CH

3 2)

H-

3 C C-NI--CH-CH 2

-CH

2 0 CH 3 cl

.H

5 c 2

H

3 C H3C C-NH-CH 2

CH-CH

2 CC CH 3 3

H

5

C

2

H

3

N

CH 3 (64)

H

3 C c -NH CH CH- CH 2 0 CH 3

H

5

C

2

H

3 C -N

H

3 C C- NH C H-C H 2 -C H 2 -0 I I II

CH

3 <A 28 424 -91-

-NI

H

5 c 2

H-

3 C -N

=D

H

3 C C-NH-CH--CH 2 CH 2

H

3 C N =CH

H

3 C C-NH--CH-CH 2 -C <Dr/ 3I I II

I

o uH 3

CH

3

H

3 C T-N

=CH

H

3 C C-NH-CH-CH -C H 2 o

CH

3 H3

CH

3 H 3 C C-NH-C-CH 2

-CH

2 Ii 1 0 CH 3 Cl (67) (69) (74) (77)

H

3 C

H

H

3 C C-NH-CH-CH--CH 2

F

I I I 0

CH

3 (81)

I

y Le A _8 4 92 79

H

7

C

H

3 C N -N =o(1

H

3 C C-NH-CH-CH 2

-CH

2 D H7C3**.

H

3 C -N

CH

3 (92)

H

3 C C-NM-CM-CH -C c 1 -o

CM

3

(CH

3

)C

H

3 C

CM

3 (96)

I

H

3 C C-NH-C-CM 2

-CM

2 O M 3

(CM

3 2 H3 C (98)

H

3 C C-NH-CH-CH 2

-CH

2 C1 (CM3

H

3 CH -N

CH

3 (101)

H

3 C C-NM-CM-CM-CM 2

-<D

0 CM 3 Le A 28 424 -93- 80

I,

0 N

CH

3

H

3 C C-NM-CuM2- CH 2 C HC 3 0 N

,N-N,

H

3 C C- ~C H- CH 2 -CH 1 o N

CH

3 H C C-NH-CH-CH-CH 2 0I N

-NN=

11 N 0 N

H

3 C C-NH-CH-CH 2

-CH

2 o t' CH 3 (110) (1il1) (112) (114) (116)

I

V

Le A 28 424 94 N1N 0 N

CH

3 (119)

H

3 C C-NH-CH-CH-CH 2

F

o

CH

3

CN

7 >==o(122)

H-

3 C ,NNC-NH-CH-CH 2

-CH

2 <7 H 3 -0

CH

3

CN

(123)

H

3 C C-NH--CH-CH 2

-CH

2 o Cl- 3

CN

CH

3 (125)

H

3 C C-NH-CH-CH CH-1 1 0 UM3 cN

-N

(127) .41. H3C C-NH-CH-CH -CH 2 1 0 CH 3 SA28 424 -95

LV

Claims (5)

1. 4. Patent Claims 1. Substituted triazolinones of the general formula (I) R 1 /-N I =o (I) 3N--N R 3 C-NH-R 4 iX X in which R 1 and R 2 independently of one another in each case represent alkyl, alkenyl, alkinyl, halogenoalkyl, halogenoalkenyl, halogeno- alkinyl, cyanoalkyl, alkoxyalkyl, alkoxy, cycloalkyl, cycloalkylalkyl, in each case optionally substituted aryl, aralkyl or heteroaryl, or, together with the nitrogen atom to which they are bonded, an optionally substituted heterocycle, R 3 represents alkyl or cycloalkyl, 41 R 4 represents alkyl, alkenyl, alkinyl, halogeno- alkyl, halogenoalkenyl, halogenoalkinyl, cyano- alkyl, hydroxyalkyl, alkoxyalkyl, aryloxyalkyl, arylthioalkyl, arylsulphinylalkyl, aryl- sulphonylalkyl, arylaminoalkyl, N-alkyl-aryl- .I i I *i\Le A 28 424 96 Le A 28 424 83 0IS L fti i ;iI I F c aminoalkyl, arylazoalkyl, alkoxycarbonylalkyl, alkoxycarbonylalkenyl, alkylaminoalkyl, di- alkylaminoalkyl, in each case optionally substituted cycloalkyl, cycloalkylalkyl, cyclo- alkenyl or cycloalkenylalkyl, or represents optionally substituted heterocyclylalkyl, in each case optionally substituted aralkyl, arylalkenyl, arylalkinyl, aroyl, aryl, aralkyloxy or aryloxy, or represents alkoxy, alkenyloxy or alkinyloxy, and X represents oxygen or sulphur 2. Substituted triazolinones of the general formula according to Claim 1, in which R 1 and R 2 independently of one another represent in each case straight-chain or branched alkyl having 1 to 8 carbon atoms, alkenyl having 2 to 8 carbon atoms, alkinyl having 2 to 8 carbon atoms, halogenoalkyl having 1 to 8 carbon atoms and 1 to 17 identical or different halogen atoms, halogenoalkenyl or halogenoalkinyl, each of which has 2 to 8 carbon atoms and 1 to or 1 to 13, identical or different halogen atoms, cyanoalkyl, alkoxyalkyl or alkoxy, each of which has 1 to 6 carbon atoms in the individual alkyl moieties, cycloalkyl having 3 I' "f l'Le A 28 424 97 Vj Le A 28424 84 to 7 carbon atoms, cycloalkylalkyl having 3 to 7 carbon atoms in the cycloalkyl moiety and 1 to 6 carbon atoms in the alkyl moiety, or represent aralkyl having 6 to 10 carbon atoms in the aryl moiety and 1 to 6 carbon atoms in the alkyl moiety, aryl having 6 to 10 carbon atoms or heteroaryl having 2 to 9 carbon atoms and 1 to 3 hetero atoms, in particular nitrogen, oxygen and/or sulphur, each of these radicals optionally being monosubstituted or polysubstituted by identical or different subtituents, suitable substituents in each case being: halogen, cyano, nitro and in each case straight-chain or branched alkyl, alkoxy, alkylthio, halogenoalkyl, halogenoalkoxy or halogenoalkylthio, each of which has 1 to 4 carbon atoms and, if appropriate, 1 to 9 identical or different halogen atoms, or R1 and R 2 together with the nitrogen atom to which they are bonded represent a five- to ten- membered heterocycle which can, if appropriate, contain 1 to 2 further hetero atoms, in particular nitrogen, oxygen and/or sulphur, and which is optionally monosubstituted or poly- substituted by identical or different substituents, suitable substituents being: halogen and in each case straight-chain or branched alkyl or halogenoalkyl, each of which has 1 to 4 carbon atoms and, if appropriate, 1 L/ e A 28 424 98 2 s b; i c o susiuetsutbe usitet big halogen~~~i an nec aesrih-hi r: r( j 2 Al'e A 28 424 vA;~ ;i V4? i Ii, to 9 identical or different halogen a also 1 to 2 oxo or thiono groups, ns, and R 3 represents straight-chain or branched alkyl having 1 to 8 carbon atoms or cycloalkyl having 3 to 8 carbon atoms, R 4 represents in each case straight-chain or branched alkyl having 1 to 18 carbon atoms, alkenyl having 2 to 8 carbon atoms, alkinyl having 2 to 8 carbon atoms, halogenoalkyl having 1 to 8 carbon atoms and 1 to 17 identical or different halogen atoms, halogenoalkenyl or halogenoalkinyl, each having 2 to 8 carbon atoms and 1 and or 1 to 13, identical or different halogen atoms, cyanoalkyl having 1 to 8 carbon atoms, hydroxyalkyl having 1 to 8 carbon atoms and 1 to 6 hydroxyl groups, or represents phenoxy- alkyl, phenylthioalkyl, phenylsulphinylalkyl, phenylsulphonylalkyl, phenylaminoalkyl, N-(C 1 C 4 -alkyl)-phenylaminoalkyl or phenylazoalkyl, each of which has 1 to 4 carbon atoms in the alkyl moiety, or represents alkoxyalkyl, alkoxycarbonylalkyl or alkoxycarbonylalkenyl, each of which has up to 6 carbon atoms in the individual alkyl or alkenyl moieties, or represents alkylaminoalkyl or dialkylamino- alkyl, each of which has 1 to 6 carbon atoms in the individual alkyl moieties, or represents Il 1<~ B, :Le A 28 424 Sj( A' &j*<f f^4 4 99 -L 86 I d t;a~: I cycloalkyl, cycloalkylalkyl, cycloalkenyl or cycloalkenylalkyl, each of which has 3 to 8 carbon atoms in the cycloalkyl or cyclo- alkenyl moiety and, if appropriate, 1 to 6 carbon atoms in the alkyl moiety and is optionally monosubstituted to trisubstituted by identical or different substituents, suitable substituents in each case being: halogen, cyano, phenyl and in each case straight-chain or branched alkyl or halogenoalkyl, each of which has 1 to 4 carbon atoms and, if appropriate, 1 to 9 identical or different halogen atoms, and straight-chain or branched halogenoalkenyl having 1 to 4 carbon atoms and 1 to 5 identical or different halogen atoms, or in each case divalent alkanediyl, or alkene- diyl, each of which has up to 4 carbon atoms; R 4 further represents heterocyclylalkyl which has 1 to 6 carbon atoms in the straight-chain or branched alkyl moiety and 2 to 9 carbon atoms and 1 to 3 hetero atoms in particular nitrogen, oxygen and/or sulphur in the heterocyclyl moiety and which is optionally monosubstituted or polysubstituted in the heterocyclyl moiety by identical or different substituents, suitable substitu- ents being: halogen, cyano, nitro, and in each case straight-chain or branched alkyl, alkoxy, alkylthio, halogenoalkyl, halogenoalkoxy, halo- genoalkylthio or alkoxycarbonyl, each of which has 1 to 5 carbon atoms and, if appropriate, 1 I-V ct t jl j' C; I i k~l Le A 28 424 100 1 i 87 to 9 identical or different halogen atoms; R 4 furthermore represents in each case straight- chain or branched alkoxy having 1 to 8 carbon atoms, alkenyloxy having 2 to 8 carbon atoms or alkinyloxy having 2 to 8 carbon atoms, or aralkyl, arylalkenyl, arylalkinyl, aroyl, aryl, aralkyloxy or aryloxy, each of which has 6 to carbon atoms in the aryl moiety and, if appropriate, 1 to 8 carbon atoms in the straight-chain or branched alkyl moiety or 2 to 8 carbon atoms in the straight-chain or branched alkenyl moiety or alkinyl moiety, it being possible for the hydrogen atoms of the a- carbon atom to be replaced by ethane-l,2-diyl, propane-, 3-diyl, butane-l,4-diyl or pentane- each of the above radicals being optionally monosubstituted to trisubstituted by identical or different substituents, suitable alkyl substituents being, if appropriate, halogen and cyano, and-suitable aryl substituents in each case being: halogen, cyano, nitro, amino, hydroxyl, in each case straight-chain or branched alkyl, alkoxy, alkylthio, halogeno- alkyl, halogenoalkoxy, halogenoalkylthio, alkylsulphinyl, alkylsulphonyl, halogenoalkyl- sulphinyl, halogenoalkylsulphonyl, alkanoyl or alkoxycarbonyl, each of which has 1 to 6 carbon atoms in the alkyl moiety and, if appropriate, 1 to 9 identical or different halogen atoms, S 30 cycloalkyl having 3 to 6 carbon atoms, oxa- Le A 28 424 101 Le A 28 424 88 :7Li 'Y" iii~~ 'c alkanediyl having up to 5 carbon atom and phenoxy; or R 4 represents benzyl with a -O-CH 2 O- group fused to the phenyl moiety, and X represents oxygen or sulphur. 3. Substituted triazolinones of the general formula (I) according to Claim 1, in which R 1 and R 2 independently of one another in each case represent methyl, ethyl, n- or i-propyl, i, s- or t-butyl, n- or i-pentyl, allyl, .0 propargyl, in each case straight-chain or branched halogenoalkyl having 1 to 4 carbon atoms, halogenoalkenyl having 3 to 6 carbon atoms or halogenalkinyl having 3 to 6 carbon atoms and in each case 1 to 9 identical or different halogen atoms, or represent cyano- ethyl, methoxymethyl, methoxyethyl, methoxy, ethoxy, cyclopropyl, cyclopropylmethyl, cyclo- pentyl, cyclohexyl, cyclohexylmethyl, cyclo- hexylethyl, cyclopentylmethyl, or represent benzyl, phenylethyl or phenyl, each of which is optionally monosubstituted to trisubstituted by identical or different substituents, suitable substituents being: fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n- or i- propyl, s- or t-butyl, methoxy, ethoxy, methylthio, trifluoromethyl, trifluoromethoxy or trifluoromethylthio, or 4 2a I l l 102 i I u- i~ :I-1 1~ 1 i e A 28 424 89 K.- a I II r R 1 and R 2 together with the nitrogen atom to which they are bonded represent a heterocycle of the formula -N -N -N 0O NH -N NH -N 0 -N 0 0 0 0 -N 0 or each of which is optionally monosubstituted to trisubstituted by identical or different substituents, suitable substituents being: methyl, ethyl, n- or i-propyl, chlorine or trifluoromethyl, R 3 represents methyl, ethyl, propyl, isopropyl, s- or t-butyl, cyclopropyl, cyclo- butyl, cyclopentyl or cyclohexyl, R 4 represents methyl, ethyl, n- or i-propyl, n-, s- or t-butyl, in each case straight-chain or branched pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, or represents allyl, in each case straight-chain or branched butenyl, pentenyl or hexenyl, propargyl, in each case straight-chain or branched butinyl, pentinyl or I, 2J Le A 28 424 103 M'~ ii1 1 \Le A 28 424 NIk 90 .1 xr I.. s f* hexinyl, straight-chain or branched halogeno- alkyl 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 halogeno- alkenyl or halogenoalkinyl, each of which has 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 having 1 to 6 carbon atoms and 1 to 3 hydroxyl groups, alkoxyalkyl, alkoxy- carbonylalkyl or alkoxycarbonylalkenyl, alkyl- aminoalkyl or dialkylaminoalkyl, each of which has up to 4 carbon atoms in the individual alkyl or alkenyl moieties, or represents cyclopropyl, cyclopropylmethyl, cyclopropyl- ethyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclohexylmethyl, cyclohexylethyl, cyclohexenyl or cyclohexenylmethyl, each of which is optionally monosubstituted to trisubstituted by identical or different substituents, suitable substituents in each case being: fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, s- or t- butyl, cyano, methanediyl, ethanediyl, butanediyl or butadienediyl or dichloroallyl; R 4 furthermore represents heterocyclylmethyl, heterocyclylpropyl or heterocyclylethyl, each of which is optionally monosubstituted to 104 91 i r i i-; i i.;n Ez trisubstituted in the heterocyclyl moiety by identical or different substituents, suitable heterocycles in each case being: 6 7 F, Z ;N N-4-N N -J kZI NZ I -N, Cj j -N 0 or -N NH Z in each case representing oxygen or sulphur and suitable substituents in each case being: fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n- or i-propyl, s- or t- butyl, methoxy, ethoxy, methylthio, trifluoro- methyl, trifluoromethoxy, or trifluoromethyl- thio; I~ R 4 furthermore represents in each case straight- chain or branched alkoxy having 1 to 6 carbon atoms, alkenyloxy having 3 to 6 carbon atoms or alkinyloxy having 3 to 6 carbon atoms, or represents optionally straight-chain or branched benzyl, phenylethyl, phenylpropyl, Le A 28 424 ,f ot/ j- '4 .v i, 2/c. 105 Le A 28 424 -9 92 I p&-:nylpropenyl, phenvipropinyl, peybtl phenylbutenyl, phenylbutinyl, phenylpentyl, phenylpentenyl, phenylpentinyl, phenylhexyl, phenyihexenyl, phenyihexinyl, phenyiheptyl, phenyliheptenyl, phenyiheptinyl, phenyloctyl, pbh nyioctenyl, phenyloctinyl, phenylcyano- me thyl, phenylcyanoethyl, phenylcyanopropyl, benzyloxy, phenylethyloxy, phenoxy, phenoxy- ethyl, phenoxypropyl, phenoxy-i-propyl, phenoxyisobutyl, phenoxy-tert-butyl, phenyl- thioisobutyl, phenylthio-tert-butyl, phenyl- thiQethyl, phenyithiopropyl, phenylthio-i-. propyl, benzoyl or naphthyl, each of these radicals beinfg optionally monosubstituted to trisubstituted by identical or different substituents, suitable phenyl substituents in each case being: fluorine, chlorine, bromine, hydroxyl cyano, nitro, methyl, ethyl, n- or i-propyl, i-, s- or t-butyl, methoxy, ethoxy, methylthio, difluoromethyl, trifluoromethyl, difluoro- methoxy, trif luoromethoxy, trif luoromethylthio, trifluoromethylsulphinyl, trifluorornethyl- sulphonyl, methylsulphinyl, methylsulphonyl, acetyl, propionyl, methoxycarbonyl, ethoxy- carbonyl, ni- or i-propoxycarbonyl, cyclohexyl or phenoxy, and I X represents oxygen or sulphur. 4. Substituted triazolinones of the generai formuJ.a (I) L~e A 28 424 10 106 I' according to Claim 1, in which 1~ K~. R1 represents methyl, ethyl, n- or i-propyl, n-, s- or t-butyl, n- or i-pentyl, cyclopropyl, cyclopentyl or cyclohexyl, R 2 represents methyl, ethyl, n- or i-propyl, n-, s- or t-butyl, n- or i-pentyl, or R' and R 2 together with the nitrogen atom to which they are bonded represent a heterocycle of the formula -NJ -ND _Cj; -N 0 CR 3 -N 0 CH 3 R 3 represents methyl, ethyl, propyl or isopropyl, in particular methyl, R 4 represents l-methyl-3-phenyl-propyl, l-et:,yl-3- phenyl-propyl, 1-propyl- 3-phenyl-propyl, 1- isopropyl-3-phenyl-propyl, 2-methyl-3-phenyl- propyl, 1, l-diinethyl-3-phenyl-propyl, 1-methyl- 1-ethyl- 3-phenyl-propyl, 1, 1-diethyl- 3-phenyl- propyl, l-methyl-l-propyl-3-phenyl-propyl, I- methyl-3-phenyl-2-propenyl, 1-ethyl-3-phenyl-2- Ai'~ Le A 28 424 107 p A 28 424 94 4' propenyl, 1-propyil-3-phenyl-2-propenyl, 1- isopropyl-3-phenyl-2-propenyl, 1, 1-diinethyl-3- phenyl-2-propenyl, l-methyl-l-ethyl-3-phenyl-2- propenyl, 1,1, -diethyl-3-phenyl-2-propenyl, 1- met-hyl- 1-propyl- 3-phenyl- 2-propenyl, 1-methyl- 3-phenyl-2-propinyl, 1-ethyl-3-phenyl-2- propinyl, l-propyl-3-phenyl-2-propinyl, 1- isopropyl-3-phenyl-2-propinyl, 1, l-dimethyl-3- phenyl-2-propinyl, l-methyl-l-ethyl-3-phenyl-2- propinyl, -diethyl-3-phenyl-2-propinyl, 1- meth'yl-l-propyl-3-phenyl-2-propinyl, 1,2- dimethyl-3-phenyl-propyl, 2-ethyl-1-methyl-3- phenyl-propyl, 1,2 ,2-trimethyl-3-phenyl-propyl, 1,31 3-trimethyl-3-phenyl-propyl or 1,1,2,2- tetramethyl-3-phenyl-propyl, each of which is optionally monosubstituted to trisubstituted by identi-cal or different substituents, suitable pheny. substituents in each case being: fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, s- or t-butyl, trifluoro- methyl, phenyl, methoxy, ethoxy, propoxy, isopropoxy, difluoromethoxy, trifluoromethoxy, difluoromethyl, methoxycarbonyl, ethoxy- carbonyl, propoxycarbonyl, cyano, methylthio, ethylthio, propylthio, isopropylthio, dif luoro- methylthio, trifluoromethylthio, methyl- suiphinyl, methylsulphonyl and trif luoromethyl- sulphonyl, furthermore X represents oxygen. *\Le A 2 8 4 24 108 "v eA 2 8 4 2 4 -9 95 4i 'I 2 I'- Process for the preparation of substituted triazolinones of the general formula according to Claim 1, R R 3 C-NH-R 4 in which RI- and R 2 independently of one another in each case represent alkyl, alkenyl, alkinyl, halogeno- alkyl, halogenoalkentyl, halogenoalkinyl, cyano- alkyl, alkoxyalkyl, alkoxy, cycloalkyl, cyclo- alkylalkyl, in each case optionally substituted aryl, aralkyl or heteroaryl, or, together with the nitrogen atom to which they are bonded, an optionally substituted heterocycle, represents alkyl or cycloaikyl, I <I. 4 R4 represents alkyl, alkenyl, alkinyl, halogeno- alkyl, halo genoalkenyl, halogenoalkinyl, cyano- alkyl, hydroxyalkyl, alkoxyalkyl, aryloxyalkyl, arylthioalkyl, arylsulphinylalkyl, aryl- sulphonylalkyl, arylaminoalkyl, N-alkyl-aryl- aininoalkyl, arylazoalkyl, alkoxycarbonylalkyl, alkoxycarbonylalkenyl, alkylaminoalkyl, .Le A 28 424 aN,~ J i 109 Le A 28 424 l' f f 4 ALk. IA1 /P .4 0 96 QI i :4 i! 1 41 y I -Y ?^La I-I- 1 i ii- L p dialkylaminoalkyl, in each case optionally substituted cycloalkyl, cycloalkylalkyl, cyclo- alkenyl or cycloalkenylalkyl, or represents optionally substituted heterocyclylalkyl, in each case optionally substituted aralkyl, arylalkenyl, arylalkinyl, aroyl, aryl, aralkyloxy or aryloxy, or represents alkoxy, alkenyloxy or alkinyloxy, and X represents oxygen or sulphur, characterised in that a) triazolinones of the general formula (II) 1 RI -N RZ\ 2 N R3 N H (II) in which R 1 R 2 and R 3 have the abovementioned meaning, and/or tautomers of these compounds, that is to say the corresponding hydroxytriazoles, 4i are reacted with iso(thio)cyanates general formula (III) of the ,i Le A 28 424 0/W 110 'Le A-28 424 ,46/4' 97 f Si. d" r d L. ;i- R4-N=C=X (III) in which R 4 and X have the abovementioned meaning, if appropriate, in the presence of a reaction auxiliary and, if appropriate, in the presence of a diluent, or in that b) chlorocarbonyl-triazolinones of the general formula (IV) P 1 N P 3 ~C-C1 I I 0 (IV) in which R 1 R 2 and R 3 have the abovementioned meaning, are reacted with amines of the general formula (V) 4m H 2 N-R 4 in which R 4 has the abovementioned meaning, 4- 111 A 28 42 '1 i:ii 4 Le A 28 424 ^1 fI n 0.' 98 I8 I: i :i i. E I i if appropriate, in the presence of an acid-binding agent and, if appropriate, in the presence of a diluent
2. 6. Herbicidal agents, characterised in that they contain at least one substituted triazolinone of the formula according to Claim 1 in association with one or more agriculturally acceptable carriers.
3. 7. Method of combating undesired plants, characterised in that substituted .0 triazolinones of the formula according to Claim 1 are allowed to act on undesired plants and/or their environment.
4. 8. Substituted triazolinones of the general formula according to Claim 1, process for their preparation, herbicidal agents containing them and method of combatting 15 undesired plants involving them, substantially as herein described with reference to the examples. o o O 1 O, 0 0 o a o0 .o o o a «0 a o o 0 d <«ri 610 a aO 00 6 9 (L DATED this 4th day of October, 1994. ID~~~ BAYER AKTIENGESELLSCHAFT By Its Patent Attorneys DAVIES COLLISON CAVE tr I* 4 COi~ '4 I Le A 28 424 i 9 99 I I i: :i .1 i iiii* ~1 -3: -I; i:- ;r Substituted triazolinones Abstract The invention relates to new substituted triazolinones of general formula (I) R 2 N-N R 3 C-NH-R4 1I in which R 1 and R 2 independently of one another in each case represent alkyl, alkenyl, alkinyl, halogeno- alkyl, halogenoalkenyl, halogenoalkinyl, cyanoalkyl, alkoxyalkyl, alkoxy, cycloalkyl, cycloalkylalkyl, in each case optionally substituted aryl, aralkyl or heteroaryl, or, together with the nitrogen atom to which they are bonded, an optionally substituted heterocycle, R 3 represents alkyl or cycloalkyl, R 4 represents alkyl, alkenyl, alkinyl, halogenoalkyl, halogenoalkenyl, halogenoalkinyl, cyanoalkyl, hydroxy- alkyl, alkoxyalkyl, aryloxyalkyl, arylthioalkyl, 4 I I, 'V PCT i I b. r Le A 28 424 100 N-% arylsulphinylalkyl, arylsulphonylalkyl, arylamino- alkyl, N-alkyl-arylaminoalkyl, arylazoalkyl, alkoxycarbonylalkyl, alkoxycarbonylalkenyl, alkylaminoalkyl, dialkylaminoalkyl, in each case optionally substituted cycloalkyl, cycloalkylalkyl, cycloalkenyl or cycloalkenylalkyl, or represents optionally substituted heterocyclylalkyl, in each case optionally substituted aralkyl, arylalkenyl, arylalkinyl, aroyl, aryl, aralkyloxy or aryloxy, or represents alkoxy, alkenyloxy or alkinyloxy, and X represents oxygen or sulphur, to a plurality of processes for their preparation, and to their use as herbicides. ,9 eA 28 424 PCT h Ii Le A 28 424 101 0^ A \'wus i r h i i INTERNATIONAL SEARCH REPORT International application No. PCT/EP92/00968 A. CLASSIFICATION OF SUBJECT MATTER C07D 249/14; C07D 405/04; C07D 403/04; A01N 43/653 According to International Patent Classification (IPC) or to both national classification and IPC B. FIELDS SEARCHED Minimum documentation searched (classification system followed by classification symbols) C07D Documentation searched other than minimum documentation to the extent that such documents are included in the fields searched Electronic data base consulted during the international search (name of data base and, where practicable, search terms used) C. DOCUMENTS CONSIDERED TO BE RELEVANT Category* Citation of document, with indication, where appropriate, of the relevant passages Relevant to claim No. A EP, A,0 283 876 (BAYER) 28 September 1988 1-8 see the whole document A EP, A,0 305 844 (BAYER) 8 March 1989 1-8 see the whole document A EP, A,0 398 096 (BAYER) 22 November 1990 1-8 see the whole document A DE, A,2 042 660 (BAYER) 2 March 1972 1-8 cited in the application see the whole.document see page 10- page 12; example P,X EP, A,0 431 390 (BAYER) 12 June 1991 1-8 see the whole document S Further documents are listed in the continuation of Box C. O See patent family annex. S Special categories of cited documents: later document published after the international filingdateorpriority document defining the general state of the art which is not considered date ad not in conflict with the application but cited to understand to be of particular relevance the principle or theory underlying the invention earlier document but published on or after the international filing date document of particular relevance; the claimed invention cannot be considered novel or cannot be considered to involve an inventive document which may throw doubts on priority claim(s) or which is step when the document is taken alone cited to establish the publication date of another citation or other special reason (as specified) document of particular relevance; the claimed invention cannot be document referring to an oral disclosure, use, exhibition or other considered to involve an inventive step when the document is means combined with oneormore othersuch documents, such combination being obvious to a person skilled in the art P" document published prior to the international filing date but later than the priority date claimed document member of the same patent family Date of the actual completion of the international search Date of mailing of the international search report 21 July 1992 (21.07.92) 31 July 1992 (31.07.92) Name and mailing address of the ISA/ Authorized officer European Patent Office Facsimile No. Telephone No. Form PCT/ISA/210 (second sheet) (July 1992) 1'I i ,r d II t I i ;i; ANNEX TO THE INTERNATIONAL SEARCH REPORT ON INTERNATIONAL PATENT APPLICATION No. EP SA 9200968 59235 Tis annex lists the patent family members relating to the patent documents cited in the above-mentioned international mearch report. The members are as contained in the European Patent Office EDE~ file on T'he European Patent Office is in no way liable for these particulars which are meely given for the purpose of information. 21/07/92 I I For more details about this annex me Official Journal of the Europeah Patent Offce No. 12/82 Le A 28 424-10 103 INTERNATIONALER RECHERCHENBERICHT PC EP 2/06 L LASSlMIMTON DES ANNMUJ3UNGSGEGEUMNS "hlm~v xeduvrei id a#l a=ml)' Nachde iv Iose"ami Pasudmsuffiksttue MPC) a uch der aftiouma Kewiludm Nw der [c Int.MK. 5 C070249/14; C07D405/ 04; C07D403/04; ADIN43/653 U. REOIDERUTE SACIGET~E Igackbalta, Mhaiatiprlgtaff 7 Int.K1. 5 C07D Rachrchlerte uicht Mlfdestprifstolf &skbrods Vuffdiclespa sont dim UL KINSOIAGIGE VEROFFENTUCHNGEN'I AMD lKsouchumg eaiv vsfmchung t1 ,w mIa oflhm a te Alas. der adalichee TolleU Dat8. Aaspracb Nr~u A EP,A,O 283 876 (BAYER) 28. September 1988 1-8 *Insgesamt* A EPA, 305 844 (BAYER) 8. Mirz 1989 1-8 *Insgesamt* A EP,A,0 398 096 (BAYER) 22. Novemb er 1990 1-8 *Insgesamt* A DE,A2 042 660 (BAYER, 2. Narz 1972 1-8 in der Annieldung erwlhnt *Insgesamt* slehe Seite 10 Selte 12; Beispiel PX EP,A,0 431 390 (BAYERN, 12. JunI 1991 1-8 *Insgesamt* Verdficadichan, die dam afivecie Stuid der Tedhalk Tr 5,miv Vs fiatI die mach deinsimum An- daiert, &lW cht mis bmaes bedurn stmsem it maddtu d iatttumu vamecftllht warin ditam Daksmemt 1 in sduch wit so iN ac dern istena- is md Enit der Anusin zq mlt hnlidiet, scaev nor mu ticesles Aarn.Medaturn V.WWALffk4jt W0914 il Vvsztwis do der Fri g xegoidiqtAmi rup ILI Ve~feibg di s, m aiede iv bs nmadelisjdrn Thud.e aeabs lit zweielbft mbsiove~ b, da urthdir-.2w vraf'dowhinww w leivun. die h6.Uapwb- fesllchaegusarn day mim in Racwhh'lcbt go to Whiling hams vidb hi mse o de set orndtsh Titg it"m v lfatlchn hdqt nrdw Smal Oda die mas alucs Wit basked hurachiit werdm aim bmmedvim Grand amqbem it (wi. susigsuhat) *Y Vaulifuddug WS bessdwvr 3luu qIs~nu "O Valffotichung dlih desaim *uldlicb Offmmbusnn to ErfadMag hamihi mIS sale= flmi slue 3muaumg, sims Aaatdta mdw madue Mllubum Mgni huleht gad. is Vadama gubmacht *rd mad dine Veridmg flit *r V~atllcubun ai vw dern isteraiauon" Anmideds- slam Fmchmaa Mabldiin it turn, inky ach i. bmaspeclti Priw'ltatsdatum rn uffumt- W a dwug dl. Mitigid idhem Patiamills kIt lidht wudem ist IV. NESOIEIIGUNG Defts. do Aiscldwus dw intumwlse Racbye AbseadldS* des iastlmmalM Rechuchabwicht
5. 21.JULI 1992 3 0.7.92 lotmomal. Rhechoborde Umnhltdo bevlrnadhtlgtm DalamitWe EUROPAISCHES PATENTAMT LUTEN H.W. Musgt IPCT/h/IsM44148 2) 4.mu I". ii 2! Le A 28 424-14 104 mliii. I ANHANG ZUM INTERNATIONALEN RECHERCHENBERICHT O)BER DIE INTERNATIONALE PATENTANMELDUNG NR. EP 9200968 SA 59235 In diesm Anhang mand die Mditgleder der Patmatfamilen der im obea~tcm uatemnadnale Recbdmrcbt anpfiihaten Pawmdokwmente angegben. Die Angaben fiber die Faznil eumitglieder etsprecben dim Stand der Datei des FEumpiischen Patmnt am Diem Angaben dicennu mar i Unterrictang und erfolhen obne Gewfihr. 21/07/92 Im Rechecdaibiricbt Datm der Mltglied(er) der Datb= dir anef~lrtes Patentiolaimt Verdffuatlikung Patamdufaii Vurffenldinung EP-A-0283876 28-09-88 DE-A- 3709574 06-10-88 AU-B- 605566 17-01-91 AU-A- 1359788 22-09-80 JP-A- 63255271 21-10-88 US-A- 5061311 29-10-91 EP-A-0305844 08-03-89 DE-A- 3729070 09-03-89 AU-A- 2169288 02-03-89 JP-A- 1071861 16-03-89 US-A- 4931084 05-06-90 EP-A-0398096 22-11-90 DE-A- 3916208 22-11-90 JP-A- 3017070 25-01-91 DE-A-2042660 02-03-72 Kelne EP-A-0431390 12-06-91 DE-A- 3939952 06-06-91 JP-A- 3181472 07-08-9 1 F* miba-c Ejaulbektm =dime= Ambafh iii. AmbIautdi. Fiwiiade Patamts, Mr.12/12