SULPHONYL AMINO(THIO)CARBONYL-1,2,4-TRIAZOLIN(THI)ONE DERIVATIVES, THE PRODUCTION THEREOF AND THE USE THEREOF AS HERBICIDES

DERIVES SULFONYLAMINO(THIO)CARBONYL-1,2,4-TRIAZOLINE(THI)ONES, LEUR PREPARATION ET LEUR UTILISATION COMME HERBICIDES

English Abstract

The invention relates to sulphonylamino(thio)carbonyl-triazolin(ethi)ones of
the general
formula (I)

(see formula I)

in which
Q1 represents oxygen or sulphur,
Q2 represents oxygen or sulphur,
R1 represents hydrogen, hydroxyl, amino, alkylideneamino or a respectively
optionally substituted radical from the group consisting of alkyl, alkenyl,
alkinyl, alkoxy, alkenyloxy, alkylamino, dialkylamino, alkanoylamino,
cycloalkyl, cycloalkylamino, cycloalkylalkyl, aryl and arylalkyl,

R2 represents hydrogen, hydroxyl, mercapto, amino, halogen or a respectively
optionally substituted radical from the group consisting of alkyl, alkenyl,
alkinyl, alkoxy, alkenyloxy, alkinyloxy, alkylthio, alkenylthio, alkinylthio,
alkylamino, alkenylamino, alkinylamino, dialkylamino, alkanoylamino,
aziridino,
pyrrolidino, piperidino, morpholino, cycloalkyl, cycloalkenyl, cycloalkyloxy,
cycloalkylthio, cycloalkylamino, cycloalkylalkyl, cycloalkylalkoxy,
cycloalkylalkylthio, cycloalkylalkylamino, aryl, arylalkyl, aryloxy,
arylalkoxy,



arylthio, arylalkylthio, arylamino and arylalkylamino, or
R1 and R2 together represent optionally branched alkanediyl, and
R3 represents respectively optionally substituted aryl, arylalkyl or
heteroaryl,
- with the proviso that either Q1 or Q2'- represents sulphur or both represent
sulphur -,
and to salts of the compounds of the formula (I), furthermore to a plurality
of processes
for preparing the novel compounds of the formula (I) and the salts thereof and
to the
use of these compounds as herbicides.

French Abstract

L'invention concerne des sulfonylamino(thio) carbonyl-triazoline(thi)ones de la formule (I) dans laquelle Q<1> désigne oxygène ou soufre, Q<2> désigne oxygène ou soufre, R<1> désigne hydrogène, hydroxy, amino, alkylidène-amino ou un reste éventuellement substitué du groupe alkyle, alcényle, alkinyle, alcoxy, alcényloxy, dialkylamino, alcanoyle-amino, cycloalkyle, cycloalkylamino, cycloalkylalkyle, aryle, arylalkyle, R<2> désigne hydrogène, hydroxy, mercapto, amino, halogène ou un reste éventuellement substitué du groupe alkyle, alcényle, alkinyle, alcoxy, alcényloxy, alkinyloxy, alkylthio, alcénylthio, alkinylthio, alkylamino, alcénylamino, alkinylamino, dialkylamino, alcanoyle-amino, aziridino, pyrrolidino, pipéridino, morpholino, cycloalkyle, cycloalcényle, cycloalkyloxy, cycloalkylthio, cycloalkylamino, cycloalkylalkyle, cycloalkylalcoxy, cycloalkylalkylthio, cycloalkylalkylamino, aryle, arylalkyle, aryloxy, arylalcoxy, arylthio, arylalkylthio, arylamino, arylalkylamino, ou R<1> et R<2> désignent conjointement alcanediyle éventuellement ramifié, et R<3> désigne aryle, arylalkyle ou hétéroalkyle éventuellement substitués, sous réserve que Q<1> ou Q<2> désigne soufre ou ou que les deux désignent soufre. L'invention concerne également des sels des composés de la formule (I), et des procédés de préparation des nouveaux composés de la formule (I) et de leur sels, et l'utilisation de ces composés comme herbicides. L'invention concerne en outre leurs composés intermédiaires de la formule (IV) dans laquelle Z désigne halogène, alcoxy, aryloxy ou arylalcoxy.

Claims

-68-

CLAIMS:

1. A compound of the general formula (I) or a salt
thereof:
Image
wherein:
R1 represents: (i) H, hydroxyl, amino, C2-C10-
alkylideneamino, C3-C6-alkenyloxy or di- (C1-C4-alkyl) -amino,
(ii) optionally F-, Cl-, Br-, cyano-, C1-C4-alkoxy-, C1-C4-
alkyl-carbonyl- or C1-C4-alkoxy-carbonyl-substituted C1-C6-
alkyl, (iii) optionally F-, Cl-, Br- or a combination
thereof-substituted C2-C6-alkenyl or C2-C6-alkinyl, (iv)
optionally F-, Cl-, cyano-, C1-C4-alkoxy- or C1-C4-alkoxy-
carbonyl-substituted C1-C6-alkoxy, C1-C6-alkyl amino or C1-C6-
alkanoylamino, (v) optionally F-, Cl-, Br-, cyano-, C1-C4-
alkyl- or a combination thereof-substituted C3-C6-cycloalkyl,
C3-C6-cycloalkylamino or C3-C6-cycloalkyl-C1-C4-alkyl, or (vi)
optionally F-, Cl-, Br-, cyano-, nitro-, C1-C4-alkyl-,
trifluoromethyl-, C1-C4-alkoxy- or a combination thereof-
substituted phenyl or phenyl-C1-C4-alkyl;
R2 represents: (i) H, hydroxyl, mercapto, amino, F,
Cl, Br, I, C3-C6-alkenyloxy, C3-C6-alkinyloxy, C3-C6-
alkenylthio, C3-C6-alkinylthio, C3-C6-alkenylamino, C3-C6-
alkinylamino or di-(C1-C4-alkyl)-amino, (ii) as defined for
R1, (iii) as defined for R1, (iv) optionally F-, Cl-, cyano-,
C1-C4-alkoxy- or C1-C4-alkoxy-carbonyl-substituted C1-C6-
alkoxy, C1-C6-alkylthio, C1-C6-alkylamino or C1-C6-
alkanoylamino, (v) optionally methyl-, ethyl- or a
combination thereof-substituted aziridino, pyrrolidino,


-69-

piperidino or morpholino, (vi) optionally F-, Cl-, Br-,
cyano-, C1-C4-alkyl- or a combination thereof-substituted
C3-C6-cycloalkyl, C5-C6-cycloalkenyl, C3-C6-cycloalkyloxy,
C3-C6-cycloalkylthio, C3-C6-cycloalkylamino, C3-C6-cycloalkyl-
C1-C4-alkyl, C3-C6-cycloalkyl-C1-C4-alkoxy, C3-C6-cycloalkyl-
C1-C4-alkylthio or C3-C6-cycloalkyl-C1-C4-alkylamino, or (vii)
optionally F-, Cl-, Br-, cyano-, nitro-, C1-C4-alkyl-,
trifluoromethyl-, C1-C4-alkoxy- or a combination thereof-
substituted phenyl, phenyl-C1-C4-alkyl, phenoxy, phenyl-C1-C4-
alkoxy, phenylthio, phenyl-C1-C4-alkylthio, phenylamino or
phenyl-C1-C4-alkyl amino; or
R1 and R2 together represent optionally branched
alkanediyl having 3 to 11 carbon atoms; and
R3 represents:
Image
wherein:
R4 and R5 are identical or different and each
represent: (i) H, F, Cl, Br, I, nitro, C3-C6-alkinyloxy,
C3-C6-alkinylthio, phenyl, phenoxy, C1-C4-alkyl-carbonylamino,
C1-C4-alkoxy-carbonylamino, C1-C4-alkylamino-carbonyl-amino,
di-(C1-C4-alkyl)-amino-carbonylamino, trimethylsilyl,
thiazolinyl, C1-C4-alkyl-sulphonyloxy or di- (C1-C4-alkyl) -
aminosulphonylamino, (ii) optionally F-, Cl-, Br-, cyano-,
carboxyl-, C1-C4-alkoxycarbonyl-, C1-C4-alkylamino-carbonyl-,
di- (C1-C4-alkyl) -amino-carbonyl-, hydroxyl-, C1-C4-alkoxy-,
formyloxy-, C1-C4-alkyl-carbonyloxy-, C1-C4-alkoxy-
carbonyloxy-, C1-C4-alkylamino-carbonyloxy-, C1-C4-alkylthio-,
C1-C4-alkylsulphinyl-, C1-C4-alkylsulphonyl-, di- (C1-C4-
alkyl)-aminosulphonyl-, C3-C6-cycloalkyl- or phenyl-


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substituted, C1-C6-alkyl, (iii) optionally F-, Cl-, Br-,
cyano-, C1-C4-alkoxy-carbonyl-, carboxyl- or phenyl-
substituted C2-C6-alkenyl or C2-C6-alkinyl, (iv) optionally
F-, Cl-, Br, cyano-, carboxyl-, C1-C4-alkoxy-carbonyl-, C1-C4-
alkoxy-, C1-C4-alkylthio-, C1-C4-alkylsulphinyl- or C1-C4-
alkylsulphonyl-substituted C1-C4-alkoxy, (v) optionally F-,
Cl-, Br, cyano-, carboxyl-, C1-C4-alkoxy-carbonyl-, C1-C4-
alkylthio-, C1-C4-alkylsulphinyl- or C1-C4-alkylsulphonyl-
substituted C1-C4-alkylthio, (vi) optionally F-, Cl-, Br-,
cyano- or C1-C4-alkoxy-carbonyl-substituted C2-C6-alkenyloxy,
(vii) optionally F-, Cl-, Br-, cyano-, nitro-, C1-C3-
alkylthio- or C1-C4-alkoxy-carbonyl-substituted C2-C6-
alkenylthio, or (viii) -S(O)p-R6, -CO-R8 or -CH=N-R9, wherein:
p represents 1 or 2,
R6 represents: (i) optionally F-, Cl-, Br-, cyano-
or C1-C4-alkoxy-carbonyl-substituted C1-C4-alkyl, (ii) C3-C6-
alkenyl, C3-C6-alkinyl, C1-C4-alkoxy, C1-C4-alkoxy-C1-C4-
alkylamino, C1-C4-alkyl amino, di-(C1-C4-alkyl)-amino or
phenyl, or (iii) -NHOR7, wherein:
R7 represents: (i) optionally F-, Cl-, cyano-,
C1-C4-alkoxy-, C1-C4-alkylthio-, C1-C4-alkylsulphinyl-, C1-C4-
alkylsulphonyl-, C1-C4-alkyl-carbonyl-, C1-C4-alkoxy-
carbonyl-, C1-C4-alkylamino-carbonyl- or di-(C1-C4-alkyl)-
amino-carbonyl-substituted C1-C12-alkyl, (ii) optionally F-,
Cl- or Br-substituted C3-C6-alkenyl, (iii) optionally F-,
Cl-, nitro-, cyano-, C1-C4-alkyl-, C1-C4-alkoxy- or C1-C4-
alkoxy-carbonyl-substituted C3-C6-alkinyl, C3-C6-cycloalkyl,
C3-C6-cycloalkyl-C1-C2-alkyl or phenyl-C1-C2-alkyl, (iv)
benzhydryl, or (v) optionally F-, C1-, nitro-, cyano-, C1-C4-
alkyl-, trifluoromethyl-, C1-C4-alkoxy-, C1-C2-fluoroalkoxy-,
C1-C4-alkylthio-, trifluoromethylthio- or C1-C4-alkoxy-
carbonyl-substituted phenyl,



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R8 represents: (i) H, or (ii) optionally F-, Cl- or
a combination thereof-substituted, C1-C6-alkyl, C3-C6-
cycloalkyl, C1-C6-alkoxy, C3-C6-cycloalkoxy, C3-C6-alkenyloxy,
C1-C4-alkylthio, C1-C4-alkyl amino, C1-C4-alkoxyamino, C1-C4-
alkoxy-C1-C4-alkyl-amino or di- (C1-C4-alkyl) -amino, and
R9 represents: (i) optionally F-, Cl-, cyano-,
carboxyl-, C1-C4-alkoxy-, C1-C4-alkylthio-, C1-C4-
alkylsulphinyl- or C1-C4-alkylsulphonyl-substituted C1-C6-
alkyl, (ii) optionally F- or Cl-substituted benzyl, C3-C6-
alkenyl or C3-C6-alkinyl, (iii) optionally F-, Cl-, Br-,
C1-C4-alkyl-, C1-C4-alkoxy-, trifluoromethyl-,
trifluoromethoxy- or trifluoromethylthio-substituted phenyl,
(iv) optionally F-, Cl- or a combination thereof-substituted
C1-C6-alkoxy, C3-C6-alkenyloxy, C3-C6-alkinyloxy or benzyloxy,
(v) amino, C1-C4-alkylamino, di-(C1-C4-alkyl)-amino,
phenylamino, C1-C4-alkyl-carbonyl-amino, C1-C4-alkoxy-
carbonylamino or C1-C4-alkyl-sulphonylamino, or (vi)
optionally F-, Cl-, Br- or methyl-substituted
phenylsulphonylamino;
Image
wherein:
R10 represents H or C1-C4-alkyl, and
R11 and R12 are identical or different and each
represent: (i) H, F, Cl, Br, nitro, cyano, carboxyl, C1-C4-
alkoxy-carbonyl, dimethylaminocarbonyl, C1-C4-alkylsulphonyl
or di-(C1-C4-alkyl)-aminosulphonyl, or (ii) optionally F-,
Cl- or a combination thereof-substituted C1-C4-alkyl or C1-C4-
alkoxy;



-72-

Image
wherein:
R13 and R19 are identical or different and each
represent: (i) H, F, Cl, Br, nitro or cyano, or (ii) as
defined for R11 and R12;
Image
wherein:
R15 and R16 are identical or different and each
represent: (i) H, F, Cl, Br, nitro, cyano, aminosulphonyl,
mono-(C1-C4-alkyl)-aminosulphonyl, di-(C1-C4-alkyl)-
aminosulphonyl, C1-C4-alkoxy-carbonyl or
dimethylaminocarbonyl, or (ii) optionally F-, Cl- or a
combination thereof-substituted C1-C4-alkyl, C1-C4-alkoxy,
C1-C4-alkylthio, C1-C4-alkylsulphinyl or C1-C4-alkylsulphonyl;
Image
wherein:
R17 and R18 are identical or different and each
represent: (i) H, F, Cl, Br or di-(C1-C4-alkyl)-
aminosulphonyl, or (ii) as defined for R15 and R16
Image
wherein:
R19 and R20 are identical or different and each
represent: (i) H, F, Cl, Br, cyano, nitro, di-(C1-C4-alkyl)-


-73-

amino-sulphonyl, C1-C4-alkoxy-carbonyl or
dimethylaminocarbonyl, or (ii) as defined for R15 and R16, and
A represents O, S or N-Z1, wherein:
Z1 represents: (i) H, C1-C4-alkyl-carbonyl, C1-C4-
alkoxy-carbonyl or di-(C1-C4-alkyl)-amino-carbonyl, (ii)
optionally F-, Cl-, Br or cyano-substituted C1-C4-alkyl, or
(iii) optionally F-, Cl-, Br- or nitro-substituted C3-C6-
cycloalkyl, benzyl or phenyl;
Image
wherein:
R21 and R22 are identical or different and each
represent H, C1-C4-alkyl, a halogen atom, C1-C4-alkoxy-
carbonyl, C1-C4-alkoxy or C1-C4-halogenoalkoxy, and
Y1 represents S or N-R23, wherein R23 represents H
or C1-C4-alkyl;
Image
wherein:
R24 represents H, C1-C4-alkyl, benzyl, pyridyl,
quinolinyl or phenyl,
R25 represents: (i) H, a halogen atom, cyano,
nitro, dioxolanyl or C1-C4-alkoxy-carbonyl, or (ii) as
defined for R11 and R12, and
R26 represents H, a halogen atom or C1-C4-alkyl; or



-74-

Image

2. A compound of the general formula (I) according to
claim 1, wherein the salt is the sodium, potassium,
magnesium, calcium, ammonium, C1-C4-alkyl-ammonium, di- (C1-C4-
alkyl)-ammonium, tri-(C1-C4-alkyl)-ammonium, tetra- (C1-C4-
alkyl)-ammonium, tri-(C1-C4-alkyl)-sulphonium, C5- or C6-
cycloalkyl-ammonium or di-(C1-C2-alkyl) -benzyl-ammonium salt
thereof.

3. A compound of the general formula (I) or a salt
thereof according to claim 1 or 2, wherein:
R1 represents: (i) H, hydroxyl, amino, C3-C8-
alkylideneamino, propenyloxy, butenyloxy, dimethylamino or
diethylamino, (ii) optionally F-, Cl-, cyano-, methoxy- or
ethoxy-substituted methyl, ethyl, n- or i-propyl, or n-, i-,
s- or t-butyl, (iii) optionally F-, Cl- or Br-substituted
propenyl, butenyl, propinyl or butinyl, (iv) optionally F-,
Cl-, cyano-, methoxy- or ethoxy-substituted methoxy, ethoxy,
n- or i-propoxy, n-, i-, s- or t-butoxy, methylamino,
ethylamino, n- or i-propylamino, or n-, i-, s- or
t-butylamino, (v) optionally F-, Cl-, methyl-, ethyl- or a
combination thereof-substituted cyclopropyl, cyclobutyl,
cyclopentyl, cyclohexyl, cyclopropylamino, cyclobutylamino,
cyclopentylamino, cyclohexylamino, cyclopropylmethyl,
cyclobutylmethyl, cyclopentylmethyl or cyclohexylmethyl, or
(vi) optionally F-, Cl-, methyl-, trifluoromethyl-, methoxy-
or a combination thereof-substituted phenyl or benzyl;



-75-

R2 represents: (i) H, hydroxyl, mercapto, amino, F,
Cl, Br, propenyloxy, butenyloxy, propinyloxy, butinyloxy,
propenylthio, butenylthio, propinylthio, butinylthio,
propenylamino, butenylamino, propinylamino, butinylamino,
dimethylamino, diethylamino or dipropylamino, (ii)
optionally F-, Cl-, cyano-, methoxy- or ethoxy-substituted
methyl, ethyl, n- or i-propyl, or n-, i-, s- or t-butyl,
(iii) optionally F-, Cl- or Br-substituted propenyl,
butenyl, propinyl or butinyl, (iv) optionally F-, Cl-,
cyano-, methoxy- or ethoxy-substituted methoxy, ethoxy, n-
or i-propoxy, n-, i-, s- or t-butoxy, methylthio, ethylthio,
n- or i-propylthio, n-, i-, s- or t-butylthio, methylamino,
ethylamino, n- or i-propylamino, or n-, i-, s- or
t-butylamino, (vi) optionally F-, Cl-, methyl-, ethyl- or a
combination thereof-substituted cyclopropyl, cyclobutyl,
cyclopentyl, cyclohexyl, cyclopentenyl, cyclohexenyl,
cyclopropyloxy, cyclobutyloxy, cyclopentyloxy,
cyclohexyloxy, cyclopropylthio, cyclobutylthio,
cyclopentylthio, cyclohexylthio, cyclopropylamino,
cyclobutylamino, cyclopentylamino, cyclohexylamino,
cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl,
cyclohexylmethyl, cyclopropylmethoxy, cyclobutylmethoxy,
cyclopentylmethoxy, cyclohexylmethoxy,
cyclopropylmethylthio, cyclobutylmethylthio,
cyclopentylmethylthio, cyclohexylmethylthio,
cyclopropylmethylamino, cyclobutylmethylamino,
cyclopentylmethylamino or cyclohexylmethylamino, or (vii)
optionally F-, Cl-, methyl-, trifluoromethyl-, methoxy- or a
combination thereof-substituted phenyl, benzyl, phenoxy,
benzyloxy, phenylthio, benzylthio, phenylamino or
benzylamino; or
R1 and R2 together are as defined in claim 1; and
R3 represents:



-76-

Image
wherein:
R4 represents: (i) F, Cl or Br, (ii) optionally F-,
Cl- or a combination thereof-substituted methyl, ethyl, or
n- or i-propyl, (iii) optionally F-, Cl-, methoxy- or
ethoxy-substituted methoxy, ethoxy, n- or i-propoxy,
methylthio, ethylthio, n- or i-propylthio, methylsulphinyl,
ethylsulphinyl, n- or i-propylsulphinyl, methylsulphonyl,
ethylsulphonyl, n- or i-propylsulphonyl,
dimethylaminosulphonyl, diethylaminosulphonyl, N-methoxy-N-
methylaminosulphonyl, methoxyaminosulphonyl, phenyl or
phenoxy, or (iv) optionally F-, Cl-, methoxy- or ethoxy-
substituted methoxycarbonyl, ethoxycarbonyl, or n- or
i-propoxycarbonyl, and
R5 represents H, methyl, ethyl, F, Cl or Br;
Image
wherein:
R10 and R12 represent H, and
R11 represents F, Cl, Br, methyl, trifluoromethyl,
methoxy, difluoromethoxy, trifluoromethoxy, ethoxy, methoxy-
carbonyl, ethoxycarbonyl, methylsulphonyl or dimethylamino-
sulphonyl;
Image



-77-

wherein R represents methyl, ethyl, n- or i-propyl; or
Image
wherein:
R29 represents methyl, ethyl, n- or i-propyl,
phenyl or pyridyl,
R25 represents H, F, Cl or Br, and
R26 represents F, Cl, Br, methoxycarbonyl or
ethoxycarbonyl.

4. A process for preparing a compound of the general
formula (I) and a salt thereof according to any one of
claims 1 to 3, comprising
(a) reacting, optionally in the presence of a
reaction auxiliary and optionally in the presence of a
diluent, a compound of the general formula (II):
Image
wherein R1 and R2 are each as defined in claim 1 or 3, with a
compound of the general formula (III):
R3-SO2-N=C=S (III)
wherein R3 is as defined in claim 1 or 3; or



-78-

(b) reacting, optionally in the presence of an
acid acceptor and optionally in the presence of a diluent, a
compound of the general formula (IV):
Image
wherein R1 and R2 are each as defined in claim 1 or 3, and Z
represents a halogen atom, alkoxy, aryloxy or arylalkoxy,
with a sulphonamide of the general formula (V):
R3-SO2-NH2 (V)
wherein R3 is as defined in claim 1 or 3; or
(c) reacting, optionally in the presence of an
acid acceptor and optionally in the presence of a diluent, a
compound of the general formula (II) as defined in step (a)
with a compound of the general formula (VI):
R3-SO2-NH-CS-Z (VI)
wherein R3 is as defined in claim 1 or 3, and Z is as defined
in step (b); or
(d) reacting, optionally in the presence of a
reaction auxiliary and optionally in the presence of a
diluent, a compound of the general formula (II) as defined
in step (a) with a sulphonyl halide of the general
formula (VII):
R3-SO2-X (VII)
wherein R3 is as defined in claim 1 or 3, and X represents a
halogen atom, and a compound of the general formula (VIII):



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MS-CN (VIII)
wherein M represents an alkali metal or an alkaline earth
metal equivalent; and
optionally converting a compound of the general
formula (I) obtained by processes (a), (b), (c) or (d) into
a salt thereof.

5. A herbicidal composition, comprising at least one
compound of the general formula (I) or a salt thereof as
defined in any one of claims 1 to 3, and an extender, a
surface-active agent or a mixture thereof.

6. Use of a compound of the general formula (I) or a
salt thereof as defined in any one of claims 1 to 3, or a
composition as defined in claim 5, for controlling undesired
plant growth.

7. A method for controlling weeds, wherein a compound
of the general formula (I) or a salt thereof as defined in
any one of claims 1 to 3, or a composition as defined in
claim 5, is allowed to act on the weeds or their habitat.

8. A method of preparing a herbicidal composition,
wherein a compound of the general formula (I) or a salt
thereof as defined in any one of claims 1 to 3 is mixed with
an extender, a surface-active agent or a mixture thereof.

9. A compound of the general formula (IV):
Image
wherein:



-80-

R1 is as defined in claim 1, excluding amino,
C3-C8-alkylideneamino, di-(C1-C4-alkyl)-amino and (vi) as
defined for R1 in claim 1;
R2 is as defined in claim 1, excluding amino,
di-(C1-C4-alkyl) -amino and (vi) as defined for R1 in claim 1;
or
R1 and R2 together are as defined in claim 1; and
Z is as defined in claim 4.

Description

CA 02211411 1997-07-24
E. r~ s .. r
Le A 30 882-Foreign countries / Bi/Kr/S-P
-1-
.n ~,. eon [~ per~ ~~ t
T-~' TRA,~a~LbTtQM
Sulphonylamino(thio)ca~onyl-triazoli~ethi)ones
The invention relates to sulphonylamino(thio)carbonyl-triazolin(ethi)ones
containing at
least one thiocarbonyl group [-C(=S)-J, to a plurality of processes for their
preparation,
and to their use as herbicides.
It is known that certain sulphonylaminocarbonyltriazolinones have herbicidal
properties
(cf. EP-A 341489, EP-A 422469, EP-A 425948, EP-A 431291). However,
sulphonylamino(thio)carbonyl-triazolin(ethi)ones having at least one
thiocarbonyl group
have hitherto not been disclosed.
This invention, then, provides the novel sulphonylamino(thio)carbonyl-
triazolin(ethi)ones of the general formula (I)
Q,
R
l ~ ~ , R~
SOz,NH N
N
Rz
in which
Q' represents oxygen or sulphur,
QZ represents oxygen or sulphur,
R' represents hydrogen, hydroxyl, amino, alkylideneamino or a respectively
optionally substituted radical from the group consisting of alkyl, alkenyl,
alkinyl, alkoxy, alkenyloxy, alkylamino, dialkylamino, alkanoylamino,
cycloalkyl, cycloalkylamino, cycloalkylalkyl, aryl and arylalkyl,

CA 02211411 1997-07-24
yt
.. -
M
. ' Le A 30 882-Foreign countries / BilKr/S-P
-2-
R'- represents hydrogen, hydroxyl, mercapto, amino, halogen or a respectively
optionally substituted radical from the group consisting of alkyl, ,alkenyl,
alkinyl, alkoxy, alkenyloxy, alkinyloxy, alkylthio, alkenylthio, alkinylthio,
alkylamino, alkenylamino, alkinylamino, dialkylamino, alkanoylamino,
aziridino,
pyrrolidino, piperidino, morpholino, cycloalkyl, cycloalkenyl, cycloalkyloxy,
cycloalkylthio, cycloalkylamino, cycloalkylalkyl, cycloalkylalkoxy,
cycloalkylalkylthio, cycloalkylalkylamino, aryl, arylalkyl, aryloxy,
arylalkoxy,
arylthio, arylalkylthio, arylamino and arylalkylamino, or
R' and Rz together represent optionally branched alkanediyl, and
R3 represents respectively optionally substituted aryl, arylalkyl or
heteroaryl,
- with the proviso that either Q' or Qz represents sulphur or both represent
sulphur -,
and salts of the compounds of the formula (I).
The novel sulphonylamino(thio)carbonyl-triazolin(ethi)ones of the general
formula (I)
are obtained when
(a) triazolin(ethi)ones of the general formula (II)
Q,
H~N~N~R'
N
Rz
in which
Q', R' and RZ are each as described above,
are reacted with sulphonyl iso(thio)cyanates of the general formula (III)

CA 02211411 1997-07-24
Le A 30 882-Foreign countries
-3-
R3-SOZ N=C=Q'- (III)
in which
Q'- and R3 are each as described above,
if appropriate in the presence of a reaction auxiliary and if appropriate in
the
presence of a diluent,
or
(b) triazolin(ethi)one derivatives of the general formula (IV)
Qz Q'
R'
~N~N
(IV)
N
Rz
in which
Q', QZ, R' and RZ are each as described above and
Z represents halogen, alkoxy, aryloxy or arylalkoxy,
are reacted with sulphonamides of the general formula (V)
R3-SOZ-NHS (V)
in which
R3 is as described above,

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~ Le A 30 882-Foreign countries
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if appropriate in the presence of an acid acceptor and if appropriate in the
presence of a diluent,
or
(c) triazolin(ethi)ones of the general formula (II)
Q,
H~N~N~R'
v (i1)
N
R2
in which
Q', R' and RZ are each as described above,
are reacted with sulphonamide derivatives of the general formula (VI)
R3-SOZ NH-CQZ-Z (VI)
in which
QZ and R3 are each as described above and
Z represents halogen, alkoxy, aryloxy or arylalkoxy,
" if appropriate in the presence of an acid acceptor and if appropriate in the
presence of a diluent,
or
(d) triazolin(ethi)ones of the general formula (II)

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Q,
H,N~N,R'
N =C
R2
in which
Q', Rl and RZ are each as described above,
are reacted with sulphonyl halides of the general formula (VII)
R3-SOZ-X (VII)
in which
R3 is as described above and
X represents halogen,
and metal (thio)cyanates of the general formula (VIII)
MQZCN (VIII)
in which
QZ is as described above and
M represents an alkali metal or an alkaline earth metal equivalent,
if appropriate in the presence of a reaction auxiliary and if appropriate in
the
presence of a diluent,

s
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-6-
and the compounds of the formula (I) obtained by processes (a), (b), (c) or
(d) are, if
desired, converted into salts by customary methods.
The mover su~p~onylainirio(thio)carbonyl=triazolin(ethi)ories of-the general
formula (I)
have strong herbicidal action.
The invention preferably relates to compounds of the formula (I) in which
Q' represents oxygen or sulphur,
Q' represents oxygen or sulphur,
R' represents hydrogen, hydroxyl or amino, or represents Cz-C,o
alkylideneamino
or represents optionally fluorine-, chlorine-, bromine-, cyano-, C,-C4 alkoxy-
,
C,-C4 alkyl-carbonyl- or C,-C4 alkoxy-carbonyl-substituted C,-C6 alkyl, or
represents respectively optionally fluorine-, chlorine- and/or bromine-
substituted
CZ C6 alkenyl or CZ C6-alkinyl, or represents respectively optionally fluorine-
,
chlorine-, cyano-, C,-C4 alkoxy- or C,-C4-alkoxy-carbonyl-substituted C,-C6-
alkoxy, C,-C6-alkylamino or C1-C6-alkanoylamino, or represents C3-C6-
alkenyloxy, or represents di-(C,-C4-alkyl)-amino, or represents respectively
optionally fluorine-, chlorine-, bromine-, cyano- and/or C1-C4 alkyl-
substituted
C3-C6 cycloalkyl, C3-C6-cycloalkylamino or C3-C6-cycloalkyl-C,-C4 alkyl, or
represents respectively optionally fluorine-, chlorine-, bromine-, cyano-,
nitro-,
CI-C4-alkyl-, trifluoromethyl- and/or CI-C4 alkoxy-substituted phenyl or
phenyl-
C,-C4-alkyl,
RZ represents hydrogen, hydroxyl, mercapto, amino, fluorine, chlorine, bromine
or
iodine, or represents optionally fluorine-, chlorine-, bromine-, cyano-, C,-C4-

alkoxy-, C,-C4-alkyl-carbonyl- or C,-C4-alkoxy-carbonyl-substituted C,-C6-
alkyl,
or represents respectively optionally fluorine-, chlorine- and/or bromine-
substituted CZ-C6-alkenyl or CZ C6-alkinyl, or represents respectively
optionally
fluorine-, chlorine-, cyano-, C1-C4-alkoxy- or C1-C4-alkoxy-carbonyl-
substituted


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CI-C6-alkoxy, C,-C6-alkylthio, C,-C6-alkylamino or C,-C6-alkanoylamino, or
represents C3-C6-alkenyloxy, C3-C6 alkinyloxy, C;-C6-alkenylthio, C3-C6-
alkinylthio, C3-C6-alkenylamino or C3-C6-alkinylamino, or represents di-(C,-C4-

alkyl)-amino, or represents respectively optionally methyl- and/or ethyl-
substituted aziridino, pyrrolidino, piperidino or morpholino, or represents
respectively optionally fluorine-, chlorine-, bromine-, cyano- and/or C,-C4
alkyl-
substituted C3-C6-cycloalkyl, CS-C6-cycloalkenyl, C3-C6-cycloalkyloxy, C3-C6
cycloalkylthio, C3-C6-cycloalkylamino, C3-C6-cycloalkyl-C1-C4-alkyl, C3-C6
cycloalkyl-C,-C4-alkoxy, C3-C6-cycloalkyl-CI-C4-alkylthio or C3-C6-cycloalkyl-
C,-C4-alkylamino, or represents respectively optionally fluorine-, chlorine-,
bromine-, cyano-, vitro-, C~-C4-alkyl-, trifluoromethyl- and/or C,-C4-alkoxy-
substituted phenyl, phenyl-C,-C4-alkyl, phenoxy, phenyl-C,-C4-alkoxy,
phenylthio, phenyl-C,-C4-alkylthio, phenylamino or phenyl-C,-C4-alkylamino, or
R' and R' together represent optionally branched alkanediyl having 3 to 11
carbon
atoms, and
Rs
R3 represents the grouping \ /
Ra
in which
R4 and RS are identical or different and each represent hydrogen, fluorine,
chlorine, bromine, iodine, vitro, C,-C6-alkyl (which is optionally
substituted by fluorine, chlorine, bromine, cyano, carboxyl, C,-C4-
alkoxycarbonyl, CI-C4-alkylamino-carbonyl, di-(C,-C4-alkyl)-amino-
carbonyl, hydroxyl, C,-C4-alkoxy, formyloxy, C,-C4-alkyl-carbonyloxy,
C,-C4 alkoxy-carbonyloxy, C,-C4 alkylamino-carbonyloxy, C,-C4

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_g_
alkylthio, C,-C4 alkylsulphinyl, C,-C4 alkylsulphonyl, di-(C,-C4-alkyl)-
aminosulphonyl, C3-C6-cycloalkyl or phenyl), or represent C~-C6-alkenyl
(which is optionally substituted by fluorine, chlorine, bromine, cyano,
CI-C4-alkoxy-carbonyl, carboxyl or phenyl), or represent CZ C6-alkinyl
(which is optionally substituted by fluorine, chlorine, bromine, cyano,
C,-C4-alkoxy-carbonyl, carboxyl or phenyl), or represent C,-C4-alkoxy
(which is optionally substituted by fluorine, chlorine, bromine, cyano,
carboxyl, C,-C4 alkoxy-carbonyl, C,-C4-alkoxy, C,-C4-alkylthio, CI-C4-
alkylsulphinyl or C,-C4-alkylsulphonyl), or represent C,-C4 alkylthio
(which is optionally .substituted by fluorine, chlorine, bromine, cyano,
carboxyl, C1-C4 alkoxy-carbonyl, C~-C4-alkylthio, C,-C4-alkylsulphinyl
or C,-C4 alkylsulphonyl), or represent CZ-C6-alkenyloxy (which is
optionally substituted by fluorine, chlorine, bromine, cyano or C1-C4
alkoxy-carbonyl), or represent CZ-C6 alkenylthio (which is optionally
substituted by fluorine, chlorine, bromine, cyano, vitro, C,-C3-alkylthio
or C~-C4 alkoxy-carbonyl), C3-C6-alkinyloxy, C3-C6-alkinylthio, or
represent the radical -S(O)P R6 in which
p represents the numbers 1 or 2 and
R6 represents C1-C4 alkyl (which is optionally substituted by
fluorine, chlorine, bromine, cyano or C,-C4-alkoxy-carbonyl), C3-
C6-alkenyl, C3-C6-alkinyl, Ci-C4-alkoxy, C,-C4-alkoxy-C,-C4
alkylamino, C1-C4 alkylamino, di-(CI-C4-alkyl)-a.>nino or phenyl,
or represent the radical -NHOR' in which
R' represents C,-C,2-alkyl (which is optionally substituted by
fluorine, chlorine, cyano, C,-C4-alkoxy, C~-C4-alkylthio,
C,-C4-alkylsulphinyl, C1-C4 alkylsulphonyl, C~-C4-alkyl-
carbonyl, C~-C4 alkoxy-carbonyl, C,-C4 alkylamino-
carbonyl . or di-(C I-C4-alkyl)-amino-carbonyl), or
represents C3-C6-alkenyl (which is optionally substituted

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by fluorine, chlorine or bromine), C;-C6 alkinyl, C3-C6
cycloalkyl, C3-C6-cycloalkyl-C,-C,-alkyl or phenyl-C,-Cz-
alkyl (which is optionally substituted by fluorine,
chlorine, vitro, cyano, C,-C4-alkyl, C,-C4-alkoxy or
C,-C4-alkoxy-carbonyl), or represents benzhydryl or
represents phenyl (which is optionally substituted by
fluorine, chlorine, vitro, cyano, C,-C4-alkyl,
trifluoromethyl, C,-C4-alkoxy, C,-C,-fluoroalkoxy, C,-C4
alkylthio, trifluoromethylthio or C,-C4-alkoxy-carbonyl),
R4 and RS further represent phenyl or phenoxy, or represent C,-C4 alkyl-
carbonylamino, C,-C4 alkoxy-carbonylamino,C,-C4 alkylamino-carbonyl-
amino or di-(C,-C4 alkyl)-amino-carbonylamino, or represent the radical
-CO-Rg in which
Rg represents hydrogen, C,-C6-alkyl, C3-C6-cycloalkyl, C,-C6-alkoxy,
C3-C6-cycloalkoxy, C3-C6-alkenyloxy, C,-C4-alkylthio, C,-C4-
alkylamino, C,-C4-alkoxyamino, C,-C4 alkoxy-C,-C4-alkyl-amino
or di-(C,-C4 alkyl)-amino (each of which is optionally substituted
by fluorine and/or chlorine),
R4 and/or RS further represent trimethylsilyl, thiazolinyl, C,-C4 alkyl
sulphonyloxy or di-(C,-C4-alkyl)-aminosulphonylamino, or represent the
radical -CH=N-R9 in which
R9 represents optionally fluorine-, chlorine-, cyano-, carboxyl-,
C,-C4-alkoxy-, C,-C4-alkylthio-, C,-C4 alkylsulphinyl- or C,-C4-
alkylsulphonyl-substituted C,-C6-alkyl, or represents optionally
fluorine- or chlorine-substituted benzyl, or represents optionally
fluorine- or chlorine-substituted C3-C6-alkenyl or C3-C6-alkinyl,
or represents optionally fluorine-, chlorine-, bromine-, C,-C4
alkyl-, C,-C4-alkoxy-, trifluoromethyl-, trifluoromethoxy- or

a
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trifluoromethylthio-substituted phenyl, or represents optionally
fluorine- and/or chlorine-substituted C,-C6-alkoxy, C3-C6-
alkenyloxy, C3-C6-alkinyloxy or benzyloxy, or represents amino,
C,-C4-alkylamino, di-(C,-C4-alkyl)-amino, phenylamino, C,-C4-
alkyl-carbonyl-amino, CI-C4-alkoxy-carbonylamino or C,-C4-
alkyl-sulphonylamino, or represents optionally fluorine-,
chlorine-, bromine- or methyl-substituted phenylsulphonylamino,
furthermore,
R, o
D, 2
R3 represents the radical -CH
\ /
R"
in which
R'° represents hydrogen or C,-C4-alkyl,
R" and R'2 are identical or different and each represent hydrogen, fluorine,
chlorine,
bromine, vitro, cyano, CI-C4-alkyl (which is optionally substituted by
fluorine
and/or chlorine), C,-C4-alkoxy (which is optionally substituted by fluorine
and/or chlorine), carboxyl, C,-C4-alkoxy-carbonyl, dimethylaminocarbonyl,
C,-C4-alkylsulphonyl or di-(CI-C4 alkyl)-aminosulphonyl;
furthermore,
R3 represents the radical R,3

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in which
R'3 and R'4 are identical or different and each represent hydrogen, fluorine,
chlorine, bromine, vitro, cyatlo, C~-C4-alkyl (which is optionally
substituted by fluorine and/or chlorine) or C,-C4-alkoxy (which is
optionally substituted by fluorine and/or chlorine);
furthermore,
R~s
R3 represents the radical
w
N R~s
in which
R'S and R'6 are identical or different and each represent hydrogen, fluorine,
chlorine, bromine, vitro, cyano, C,-C4-alkyl (which is optionally
substituted by fluorine and/or chlorine), C,-C4-alkoxy (which is
optionally substituted by fluorine and/or chlorine), or represent C,-C4-
alkylthio, C,-C4-alkylsulphinyl or C,-C4-alkylsulphonyl (each of which
is optionally substituted by fluorine and/or chlorine), or represent
aminosulphonyl or mono-(C,-C4-alkyl)-aminosulphonyl, or represent di-
(C,-C4 alkyl)-aminosulphonyl or C,-C4-alkoxy-carbonyl or dimethyl-
aminocarbonyl;
furthermore,

r
a
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R3 represents the radical R'~ ~ ~ R'8
N
in which
R" and R'8 are identical or different and each represent hydrogen, fluorine,
chlorine, bromine, CI-C4-alkyl (which is optionally substituted by
fluorine and/or bromine), C,-C4 alkoxy (which is optionally substituted
by fluorine and/or chlorine), or represent C1-C4-alkylthio, C,-C4-
alkylsulphinyl or C,-C4-alkylsulphonyl (each of which is optionally
substituted by fluorine and/or chlorine), or represent di-(C,-C4 alkyl)-
aminosulphonyl;
furthermore,
R'9
R3 represents the radical ~ ~ Rzo
A
in which
R'9 and RZ° are identical or different and each represent hydrogen,
fluorine,
chlorine, bromine, cyano, nitro, C,-C4-alkyl (which is optionally
substituted by fluorine and/or chlorine), C,-C4 alkoxy (which is
optionally substituted by fluorine and/or chlorine), C,-C4-alkylthio,
C,-C4-alkylsulphinyl or C,-C4 alkylsulphonyl (each of which is
optionally substituted by fluorine and/or chlorine), di-(C,-C4-alkyl)-
amino-sulphonyl, C,-C4-alkoxy-carbonyl or dimethylaminocarbonyl, and

CA 02211411 1997-07-24
r
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A represents oxygen, sulphur or the grouping N-Z' in which
Z' represents hydrogen, C1-C4 alkyl (which is optionally substituted
by fluorine, chlorine, bromine or cyano), C3-C6-cycloalkyl,
benzyl, phenyl (which is optionally substituted by fluorine,
chlorine, bromine or nitro), C,-C4-alkyl-carbonyl, C1-C4 alkoxy-
carbonyl or di-(C1-C4 alkyl)-amino-carbonyl;
furthermore,
Rz~
R3 represents the radical ~ ~ R22
Y'
in which
RZ' and RZZ are identical or different and each represent hydrogen, C,-C4-
alkyl,
halogen, C,-C4-alkoxy-carbonyl, C,-C4-alkoxy or C~-C4 halogenoalkoxy,
Y' represents sulphur or the grouping N-R23 in which
R23 represents hydrogen or C1-C4-alkyl;
furthermore,
Rzs
R3 represents the radical NI ' ~R25
~N
Rza

,;
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in which
R'4 represents hydrogen, C,-C4 alkyl, benzyl, pyridyl, quinolinyl or phenyl,
R'-5 represents hydrogen, halogen, cyano, nitro, CI-C4-alkyl (which is
optionally substituted by fluorine and/or chlorine), CI-C4-alkoxy (which
is optionally substituted by fluorine and/or chlorine), dioxolanyl or
C,-C4 alkoxy-carbonyl, and
R26 represents hydrogen, halogen or C,-C4 alkyl,
and furthermore,
R3 represents one of the groupings listed below
H3C0 / H3C
~ ~ ~N' N~
O
~SOZ C4H9 . ~g OCH2CF3 .
O
- with the proviso that either Q' or QZ represents sulphur or that both
represent sulphur.
The invention further preferably relates to the sodium, potassium, magnesium,
calcium,
ammonium, C,-C4-alkyl-ammonium, di-(C,-C4-alkyl)-ammonium, tri-(C,-C4-alkyl)-
ammonium, tetra-(CI-C4-alkyl)-ammonium, tri-(C1-C4 alkyl)-sulphonium, CS- or
C6
cycloalkyl-ammonium and di-(C,-Cz alkyl)-benzyl-ammonium salts of compounds of
the formula (I) in which Q', Q2; R', Rz and R3 are preferably as defined
above.
The invention in particular relates to compounds of the formula (I) in which
Q1 represents oxygen or sulphur,

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QZ represents oxygen or sulphur,
R' represents hydrogen, hydroxyl or amino, or represents C3-C$-alkylideneamino
or
represents respectively optionally fluorine-, chlorine-, cyano-, methoxy- or
ethoxy-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, or
represents
respectively optionally fluorine-, chlorine- or bromine-substituted propenyl,
butenyl, propinyl or butinyl, or represents respectively optionally fluorine-,
chlorine-, cyano-, methoxy- or ethoxy-substituted methoxy, ethoxy, n- or
i-propoxy, n-, i-, s- or t-butoxy, methylamino, ethylamino, n- or i-
propylamino,
n-, i-, s- or t-butylamino, or represents propenyloxy or butenyloxy, or
represents
dimethylamino or diethylamino, or represents respectively optionally fluorine-
,
chlorine-, methyl- and/or ethyl-substituted cyclopropyl, cyclobutyl,
cyclopentyl,
cyclohexyl, cyclopropylamino, cyclobutylamino, cyclopentylamino, cyclohexyl
amino, cyclopropylmethyl; cyclobutylmethyl, cyclopentylmethyl or
cyclohexylmethyl, or represents respectively optionally fluorine-, chlorine-,
methyl-, trifluoromethyl- and/or methoxy-substituted phenyl or benzyl,
RZ represents hydrogen, hydroxyl, mercapto, amino, fluorine, chlorine' or
bromine,
or represents respectively optionally fluorine-, chlorine-, cyano-, methoxy-or
ethoxy-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, or
represents
respectively optionally fluorine-, chlorine- or bromine-substituted propenyl,
butenyl, propinyl or butinyl, or represents respectively optionally fluorine-,
chlorine-, cyano-, methoxy- or ethoxy-substituted methoxy, ethoxy, n- or
i-propoxy, n-, i-, s- or t-butoxy, methylthio, ethylthio, n- or i-propylthio,
n-, i-,
s- or t-butylthio, methylamino, ethylamino, n- or i-propylamino, n-, i-, s- or
t-butylamino, or represents propenyloxy, butenyloxy, propinyloxy, butinyloxy,
propenylthio, butenylthio, propinylthio, butinylthio, propenylamino,
butenylamino, propinylamino or butinylamino, or represents dimethylamino,
diethylamino or dipropylamino, or represents respectively optionally fluorine-
,
chlorine-, methyl- and/or ethyl-substituted cyclopropyl, cyclobutyl,
cyclopentyl,
cyclohexyl, cyclopentenyl, cyclohexenyl, cyclopropyloxy, cyclobutyloxy,
cyclopentyloxy, cyclohexyloxy, cyclopropylthio, cyclobutylthio,
cyclopentylthio,

,a
.6
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cyclohexylthio, cyclopropylamino, cyclobutylamino, cyclopentylamino,
cyclohexylamino, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl,
cyclohexylmethyl, cyclopropylmethoxy, cyclobutylmethoxy,
cyclopentylmethoxy, cyclohexylmethoxy, cyclopropylmethylthio,
cyclobutylmethylthio, cyclopentylmethylthio, cyclohexylmethylthio,
cyclopropylmethylamino, cyclobutylmethylamino, cyclopentylmethylamino or
cyclohexylmethylamino, or represents respectively optionally fluorine-,
chlorine-, methyl-, trifluoromethyl- and/or methoxy-substituted phenyl,
benzyl,
phenoxy, benzyloxy, phenylthio, benzylthio, phenylamino or benzylamino, or
R' and RZ together represent optionally branched alkanediyl having 3 to 11
carbon
atoms, and
- R5
R3 represents the radical \ /
R4
in which
R4 represents fluorine, chlorine or bromine, or represents respectively
optionally fluorine- and/or chlorine-substituted methyl, ethyl, n- or
i-propyl, or represents respectively optionally fluorine-, chlorine-,
methoxy- or ethoxy-substituted methoxy, ethoxy, n- or i-propoxy,
methylthio, ethylthio, n- or i-propylthio, methylsulphinyl, ethylsulphinyl,
n- or i-propylsulphinyl, methylsulphonyl, ethylsulphonyl, n- or
i-prcpyls;:'.phcnyl, dimethylGrr:inosulphor_yl, diethylaminosulphonya,
N-methoxy-N-methylaminosulphonyl, methoxyaminosulphonyl, phenyl
or phenoxy, or represents respectively optionally fluorine-, chlorine-,
methoxy- or ethoxy-substituted methoxycarbonyl, ethoxycarbonyl, n- or
i-propoxycarbonyl, and

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,
t Le A 30 882-Foreign countries
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RS represents hydrogen, methyl, ethyl, fluorine, chlorine or bromine;
furthermore,
R"
R3 represents the radical - R~z
-cH
Rio
in which
Rl° represents hydrogen,
R" represents fluorine, chlorine, bromine, methyl, trifluoromethyl, methoxy,
difluoromethoxy, trifluoromethoxy, ethoxy, methoxycarbonyl,
ethoxycarbonyl, methylsulphonyl or dimethylaminosulphonyl, and
R'z represents hydrogen;
furthermore,
R3 represents the radical Ro-c I s
0
in which
R represents methyl, ethyl, n- or i-propyl,

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or
Rzs Rzs
R3 represents the radical
N
Rza
in which
R24 represents methyl, ethyl, n- or i-propyl, phenyl or pyridyl,
S R25 represents hydrogen, fluorine, chlorine or bromine,
R26 represents fluorine, chlorine, bromine, methoxycarbonyl or
ethoxycarbonyl,
- with the proviso that either Q' or QZ represents sulphur or that both
represent sulphur.
The radical definitions listed above, whether general or in ranges of
preference, apply
not only to the end products of the formula (I) but also, correspondingly, to
the starting
materials and/or intermediates required in each case for the preparation.
These radical
definitions can be combined with one another as desired, thus including
combinations
between the preferred ranges indicated.
In the definitions of the radicals, hydrocarbon radicals such as alkyl,
alkenyl or alkinyl,
are, even in combination with heteroatoms, such as in alkoxy, alkylthio or
alkylamino,
even if this is not explicitly stated, straight-chain or branched.
Halogen generally represents fluorine, chlorine, bromine or iodine, preferably
fluorine,
chlorine or bromine, in particular fluorine or chlorine.

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Examples of the meaning of the radicals R', R'- and R3 in the compounds of the
formula (I) according to the invention are listed in the groups below.
Group 1
S O
R
SOz,NH N N~R (IA)
N
R2
R1 has, for example, the meanings listed below:
amino, n- or i-propylideneamino, methyl, ethyl, n- or i-propyl, n-, i-, s- or
t-butyl,
dichloropropyl, dibromopropyl, methoxypropyl, propenyl, butenyl, propinyl,
butinyl,
methoxy, ethoxy, n- or i-propoxy, methylamino, ethylamino, n- or i-
propylamino,
propenyloxy, dimethylamino, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl,
methyl
cyclopropyl or cyclopropylmethyl.
R'- has, for example, the meanings listed below:
hydrogen, chlorine, bromine, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-
butyl,
trifluoromethyl, methoxymethyl, ethoxymethyl, propenyl, butenyl, propinyl,
butinyl,
methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, methylthio,
ethylthio, n- or
i-propylthio, n-, i-, s- or t-butylthio, fluoromethylthio, chloromethylthio,
fluoroethylthio,
chloroethylthio, difluoroethylthio, trifluoroethylthio, trifluoropropylthio,
methylamino,
ethylamino, n- or i-propylamino, n-, i-, s- or t-butylamino, propenyloxy,
butenyloxy,
propinyloxy, butinyloxy, propenylthio, butenylthio~, propenylamino,
butenylamino,
propinylamino, butinylamino, dimethylamino, diethylamino, N-methyl-ethylamino,
N-methyl-propylamino, N-ethyl-propylamino, cyclopropyl, cyclopropyloxy,
cyclopropylamino, cyclopropylmethyl, cyclopropylmethoxy,
cyclopropylmethylthio,
phenyl, phenoxy, phenylthio, phenylamino, phenylmethyl, phenylmethoxy,
phenylmethylthio or phenylmethylamino.

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Additionally, R' and R'- together have, for example, the following meanings:
propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, heptane-
1,7-diyl
and undecane-l,ll-diyl.
R3 has, for example, the meanings listed below:
2-fluoro-phenyl, 2-chloro-phenyl, 2-bromo-phenyl, 2,6-difluoro-phenyl, 2,6-
dichloro-
phenyl, 2-methyl-phenyl, 2-chloro-6-methyl-phenyl, 2-trifluoromethyl-phenyl,
2-(2-fluoro-ethyl)-phenyl, 2-(2-chloro-ethyl)-phenyl, 2-(3-fluoro-propyl)-
phenyl,
2-(3-chloro-propyl)-phenyl, 2-(3,3,3-trifluoro-propyl)-phenyl, 2-(3,3,3-
trifluoro-1-
propenyl)-phenyl, 2-methoxy-phenyl, 2-ethoxy-phenyl, 2-difluoromethoxy-phenyl,
2-trifluoromethoxy-phenyl, 2-(2-fluoro-ethoxy)-phenyl, 2-(2-chloro-ethoxy)-
phenyl,
2-(2-methoxy-ethoxy)-phenyl, 2-methylthio-phenyl, 2-ethylthio-phenyl,
2-methylsulphinyl-phenyl, 2-ethylsulphinyl-phenyl, 2-methylsulphonyl-phenyl,
2-ethylsulphonyl-phenyl, 2-dimethylaminosulphonyl-phenyl, 2-phenyl-phenyl,
2-methoxycarbonyl-phenyl, 2-ethoxycarbonyl-phenyl, 2-chloro-phenylmethyl,
2,6-dichloro-phenylmethyl, 2-difluoromethoxy-phenylmethyl, 2-trifluoromethoxy-
phenylmethyl, 2-methoxycarbonyl-phenylmethyl, 2-ethoxycarbonyl-phenylmethyl,
2-methoxycarbonyl-3-thienyl, 2-ethoxycarbonyl-3-thienyl, 4-methoxycarbonyl-1-
methyl-
5-pyrazolyl, 4-ethoxycarbonyl-1-methyl-5-pyrazolyl, 3-chloro-4-methoxycarbonyl-
1-
methyl-5-pyrazolyl, 3-chloro-4-ethoxycarbonyl-1-methyl-5-pyrazolyl,
3-methoxycarbonyl-2-pyridyl, 3-ethoxycarbonyl-2-pyridyl, 3-
dimethylaminocarbonyl-2-
pyridyl, 3-methylsulphonyl-2-pyridyl or 3-ethylsulphonyl-2-pyridyl.
Group 2
O S
R
R~
SOZ_NH N ~ (1B)
N
Rz

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R', RZ and R3 have, for example, the meanings listed above in group 1 under
formula
(IA).
Group 3
S
R
R~
SOZ _ NH N ~ (IC)
N
RZ
R', RZ and R3 have, for example, the meanings listed above in group 1 under
formula
(IA).
Using, for example, 2,6-difluoro-phenyl isocyanate and 5-ethyl-4-methoxy-2,4-
dihydro-
3H-1,2,4-triazole-3-thione as starting materials, the course of reaction in
the process (a)
according to the invention can be illustrated by the following equation:
s
F F
I + H~N N,OCH3 ~ I O S
, w SOZ N_C_O N~ ~ ~ SO2' ~N~N~OCH3
N
F C2H5 F NH
C2Hs
Using, for example, 2-methylthio-benzenesulphonamide and 2-chlorocarbonyl-4-
dimethylamino-5-methyl-2,4-dihydro-3H-1,2,4-triazole-3-thion~s starting
materials, the
course of reaction in the process (b) according to the invention can be
illustrated by the
following equation:
s
SCH O ~ SCH
,N(CH3)2 3 O
I + CI N N ~ I
~ S02 NHZ N=C -HCI ~ SOZ' ~N N~N(CH3)2
CH3 NH
N
CH3

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Using, for example, N-methoxythiocarbonyl-2-methoxy-benzenesulphonamide and S-
ethoxy-4-methyl-2,4-dihydro-3H-1,2,4-triazol-3-one as starting materials, the
course of
reaction in the process (c) according to the invention can be illustrated by
the following
eq'~zation:-
S
OCH3 ~ OCH3
H~N N,CH3 I O S
S \ SOz N=C - HOCH3 ~ gOz\ ~N~N~CH3
OCzHs NH ~
H~N~OCH3 N OC H
zs
S
Using, for example, 4-ethyl-S-ethylthio-2,4-dihydro-3H-1,2,4-triazole-3-thione
and 2-
bromo-benzenesulphonyl chloride and potassium thiocyanate as starting
materials, the
course of reaction in the process (d) according to the invention can be
illustrated by the
following equation:
Br S
SOZCI H ~ N ~ N' CzHs
N
SC2Hs
S S
+ KSCN
---~ SOz ~ N ~ N' CzHs
KCI N
N
H SCzHs
A general definition of the triazolin(ethi)ones to be used as starting
materials in the
processes (a), (c) and (d) according to the invention for preparing compounds
of the
formula (I) is given by the formula (II).
In the formula (II), Q', R' and Rz each preferably or in particular have that
meaning
1 S which has already been indicated above, in connection with the description
of the
compounds of the formula (I) according to the invention, as being preferable
or
Br

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particularly preferable for Q', R'- and R2.
The triazolin(ethi)ones of the general formula (II) are known and/or can be
prepared by
methods known per se (cf. Arch. Pharm. 301 (1968), 827; loc. cit. 307 (1974),
889;
Bull. Soc. Chim. France 1962, 1365; loc. cit. 1975, 1191; Chem. Ber. 90
(1957), 909-
921; loc. cit. 98 (1965), 3025-3099; loc. cit. 102 (1969), 755; J. Heterocycl.
Chem. 15
(1978), 237-240; J. Indian Chem. Soc. 6 (1929), 565; Liebigs Ann. Chem. 637
(1960),
135; Monatshefte Chemie 123 (1992), 257; Tetrahedron 32 (1976), 2347-2352;
Helv.
Chim. Acta 63 (1980), 841-859; J. Chem. Soc. C 1967, 746-751; loc. cit. 1970,
26-34;
J. Chem. Soc. Perkin I 1973, 2644; Fen Fak. Derg., Seri A (Ege Univ.) 7
(1984), 1-6 -
quoted in Chem. Abstracts 101:90846m; EP-A 283876; EP-A 294666; EP-A 298371;
EP-A 301946; EP-A 305844; EP-A 341489; EP-A 362633; EP-A 370293; EP-A
391187; EP-A 398096; EP-A 398097; EP-A 399294; EP-A 415196; EP-A 422469;
EP-A 425948; EP-A 431291; EP-A 477646; EP-A 502307; EP-A 503437; EP-A
505819; EP-A 511569; EP-A 513621; DE-A 2336827; DE-A 3839206; DE-A 3916208;
DE-A 3916930; DD-P 64970; WO-A 93/04050; Preparation Examples).
A general definition of the sulphonyl iso(thio)cyanates also to be used as
starting
materials in the process (a) according to the invention for preparing
compounds of the
formula (I) is given by the formula (III).
In the formula (III), QZ and R3 each preferably or in particular have that
meaning which
has already been indicated above, in connection with the description of the
compounds
of the formula (I) according to the invention as being preferable or
particularly
preferable for QZ and R3.
The starting materials of the formula (III) are known and/or can be prepared
by
methods known per se (cf. US-P 4127405, US-P 4169719, US-P 4371391, EP-A 7687,
EP-A 13480, EP-A 21641, EP-A 23141, EP-A 23422, EP-A 30139, EP-A 35893, EP-A
44808, EP-A 44809, EP-A 48143, EP-A 51466, EP-A 64322, EP-A 70041, EP-A
173312).

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A general definition of the triazolin(ethi)one derivatives to be used as
starting materials
in the process (b) according to the invention for preparing compounds of the
general
formula (I) is given by the formula (IV). In the formula (IV), Q', Q'-, R' and
R'- each
preferably or in particular have that meaning which has already been indicated
above,
in connection with the description of the compounds of the formula (I), as
being
preferable or particularly preferable for Q', Q2, R' and RZ; Z preferably
represents
fluorine, chlorine, bromine, methoxy, ethoxy, benzyloxy, phenoxy, halogeno- or
nitro-
phenoxy, and in particular represents methoxy, phenoxy or 4-nitro-phenoxy.
The starting materials of the formula (IV) have not been disclosed in the
literature; as
novel substances, they are also part of the subject matter of the present
application.
The novel compounds of the general formula (IV) are obtained when
triazolin(ethi)ones
of the general formula (II)
O
H~N~N,R II
( )~
Rz
in which
Q', R' and R'- are each as defined above,
are reacted with (thio)carbonic acid derivatives of the general formula (IX)
Z-CQz-Z' (IX)
in which
Z and QZ are each as defined above and
Z' , represents halogen, alkoxy, aralkoxy or aryloxy,

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if appropriate in the presence of an acid acceptor, such as, for example,
sodium
hydroxide or potassium hydroxide, sodium t-butoxide or potassium t-butoxide,
and if
appropriate in the presence of a diluent, such as, for example, methylene
chloride,
tetrahydrofuran or dimethoxyethane and/or water, at temperatures between
0°C and
100°C.
A general definition of the sulphonamides also to be used as starting
materials in the
process (b) according to the invention for preparing compounds of the general
formula
(I) is given by the formula (V). In the formula (V), R3 preferably or in
particular has
that meaning which has already been indicated above, in connection with the
description of the compounds of the formula (I), as being preferable or
particularly
preferable for R3.
The starting materials of the formula (V) are known and/or can be prepared by
methods
known per se (cf. US-P 4127405, US-P 4169719, US-P 4371391, EP-A 7687, EP-A
13480, EP-A 21641, EP-A 23141, EP-A 23422, EP-A 30139, EP-A 35893, EP-A
44808, EP-A 44809, EP-A 48143, EP-A 51466, EP-A 64322, EP-A 70041, EP-A
173312).
A general definition of the sulphonamide'derivatives to be used as starting
materials in
the process (c) according to the invention for preparing compounds of the
general
formula (I) is given by the formula (VI). In the formula (VI), QZ and R3 each
preferably or in particular have that meaning which has already been indicated
above,
in connection with the description of the compounds of the formula (I), as
being
preferable or particularly preferable for QZ and R3; Z preferably represents
fluorine,
chlorine, bromine, methoxy, ethoxy; benzyloxy or phenoxy, and in particular
represents
methoxy or phenoxy.
The starting materials of the formula (VI) are known and/or can be prepared by
methods known per se.
A general definition of the sulphonyl halides to be used as starting materials
in the

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process (d) according to the invention for preparing compounds of the formula
(I) is
given by the formula (VII). In the formula (VII), R3 preferably or in
particular has that
meaning which has already been indicated above, in connection with the
description of
the compounds of the formula (I), as being preferable. or particularly
preferable for R3;
X preferably represents fluorine, chlorine or bromine, and in particular
represents
chlorine.
The starting materials of the formula (VII) are known and/or can be prepared
by
methods known per se.
The processes (a), (b), (c) and (d) according to the invention for the
preparation of the
novel compounds of the formula (I) are preferably carried out using diluents.
Suitable
diluents in this context are virtually all inert organic solvents. These
include, preferably,
aliphatic and aromatic, optionally halogenated hydrocarbons such as pentane,
hexane,
heptane, cyclohexane, petroleum ether, benzine, ligroin, benzene, toluene,
xylene,
methylene chloride, ethylene chloride, chloroform, tetrachloromethane,
chlorobenzene
and o-dichlorobenzene; ethers such as diethyl ether and 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, for example
acetonitrile and
propionitrile; amides, for example dimethylformamide, dimethylacetamide and
N-methylpyrrolidone, and also dimethyl sulphoxide, tetramethylene sulphone and
hexamethylphosphoric triamide.
As reaction auxiliaries and/or as acid acceptors in the processes (a), (b),
(c) and (d)
according to the invention it is possible to employ all acid-binding agents
which can.
customarily be used for such reactions. Preference is given to alkali metal
hydroxides,
for example sodium hydroxide and potassium hydroxide, alkaline earth metal
hydroxides, for example calcium hydroxide, alkali metal carbonates and
alkoxides, such
as sodium carbonate and potassium carbonate, sodium tent-butoxide and
potassium tert-
butoxide, and also basic nitrogen compounds, such as trimethylamine,
triethylamine,
tripropylamine, tributylamine, diisobutylamine, dicyclohexylamine,

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ethyldiisopropylamine, ethyldicyclohexylamine, N,N-dimethylbenzylamine,
N,N-dimethyl-aniline, pyridine, 2-methyl-, 3-methyl-, 4-methyl-, 2,4-dimethyl-
,
2,6-dimethyl-, 2-ethyl-, 4-ethyl- and 5-ethyl-2-methyl-pyridine, 1,5-
diazabicyclo[4.3.0]-
non-5-ene (DBN), 1,8-diazabicyclo[5.4.0]-undec-7-ene (DBU) and 1,4-
diazabicyclo-
[2.2.2]-octane (DABCO).
The reaction temperatures in the processes (a), (b), (c) and (d) according to
the
invention can be varied within a relatively wide range. The reactions are in
general
carried out at temperatures of between -20°C and +150°C,
preferably at temperatures
between 0°C and +100°C.
The processes (a), (b), (c) and (d) according to the invention are generally
carned out
under atmospheric pressure. However, it is also possible to operate under
elevated or
reduced pressure.
For carrying out processes (a), (b), (c)' and (d) according to the invention,
the starting
materials required in each case are in general employed in approximately
equimolar
quantities. However, it is also possible to use one of the components employed
in each
case in a relatively large excess. The reactions are in general carned out in
a suitable
diluent in the presence of an acid acceptor, and the reaction mixture is
stirred for a
number of hours at the particular temperature required. Work-up in the case of
the
processes (a), (b), (c) and (d) according to the invention is in each case
carried out by
customary methds (cf. the Preparation Examples).
Salts of the compounds of the general formula (I) according to the invention
can be
prepared if desired. Such salts are obtained in a simple manner by customary
methods
of forming salts, for example by dissolving or dispersing a compound of the
formula
(I) in an appropriate solvent, for example methylene chloride, acetone, tert-
butyl methyl
ether or toluene, and adding an appropriate base. The salts can then - if
desired after
prolonged stirring - be isolated by concentration or filtration with suction.
The active compounds according to the invention can be used as defoliants,
desiccants,

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a.
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-28-
haulm killers and, especially, as weed-killers. By weeds, in the broadest
sense, there are
to be understood all plants which grow in locations where they are not wanted.
Whether the substances 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, in
connection with the following plants:
Dicotyledonous weeds of the enera: Sinapis, Lepidium, Galium, Stellaria,
Matricaria,
Anthemis, Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca,
Xanthium,
Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsium, Carduus,
Sonchus,
Solanum, Rorippa, Rotala, Lindernia, Lamium, Veronica, Abutilon, Emex, Datura,
Viola, Galeopsis, Papaver, Centaurea, Trifolium, Ranunculus and Taraxacum.
Dicotyledonous crops of the enera~ Gossypium, Glycine, Beta, Daucus,
Phaseolus,
Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis,
Brassica,
Lactuca, Cucumis and Cucurbita.
Monocotyledonous weeds of the enera~ 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.
Monocotyledonous crops of the general Oryza, Zea, Triticum, Hordeum, Avena,
Secale, Sorghum, Panicum, Saccharum, Ananas, Asparagus and Allium.
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 on the concentration, for the total
control of
" 25 weeds, for example on industrial terrain and rail tracks, and on paths
and squares with

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or without tree plantings. Equally, the compounds can be employed for
controlling
weeds in perennial crops, for example afforestations, decorative tree
plantings, orchards,
vineyards, citrus groves, nut orchards, banana plantations, coffee
plantations, tea
plantations, rubber plantations, oil palm plantations, cocoa plantations, soft
fruit
plantings and hopfields, in lawns, turf and pasture-land, and for the
selective control of
weeds in annual crops.
The compounds of the formula (I) according to the invention are preferably
suitable for
the selective control of monocotyledonous and dicotyledonous weeds in
monocotyledonous and dicotyledonous crops, both pre-emergence and post-
emergence.
The active compounds can be converted into the customary formulations, such as
solutions, emulsions, wettable powders, suspensions, powders, dusting agents,
pastes,
soluble powders, granules, suspo-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 foam-forming agents.
In the case of the use of water as an extender, organic solvents can, for
example, also
be used as auxiliary solvents. Suitable liquid solvents are 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
fractions,
mineral and vegetable oils, alcohols, such as butanol or glycol as well as
their ethers
and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl
ketone or
cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethyl
sulphoxide, as well as water.

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Suitable solid carriers are:
for example ammonium salts and ground natural minerals, such as kaolins,
clays, talc,
chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground
synthetic
minerals, such as finely divided silica, alumina and silicates, suitable solid
carriers for
granules are: 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; suitable emulsifying and/or foam-forming agents are: 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 well as protein
hydrolysates;
suitable dispersing agents are: for example lignin-sulphite waste liquors and
methylcellulose.
Adhesives such as carboxymethylcellulose and natural and synthetic polymers in
the
form of powders, granules or latices, such as gum arabic, polyvinyl alcohol
and
polyvinyl acetate, as well as natural phospholipids, such as cephalins and
lecithins, and
synthetic phospholipids, can 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 dyes, such as alizarin dyes, azo
dyes and
metal phthalocyanine dyes, and trace nutrients such as salts of iron,
manganese, boron,
copper, cobalt, molybdenum and zinc.
The formulations in general contain between 0.1 and 95 per cent by weight of
active
compound, preferably between 0.5 and 90%.
For controlling 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,
ready-to-use formulations or tank mixes being possible.

1
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Possible components for the mixtures are known herbicides, for example
anilides, such
as diflufenican and propanil; arylcarboxylic acids, such as dichloropicolinic
acid,
dicamba and picloram; aryloxyalkanoic acids, such as 2,4-D, 2,4-DB, 2,4-DP,
fluroxypyr, MCPA, MCPP and triclopyr; aryloxy-phenoxy-alkanoic esters, such as
diclofop-methyl, fenoxaprop-ethyl, fluazifop-butyl, haloxyfop-methyl and
quizalofop-
ethyl; azinones, such as chloridazon and norflurazon; carbamates, such as
chlorpropham, desmedipharr~, phenmedipham and propham; chloroacetanilides,
such as
alachlor, acetochlor, butachlor, metazachlor, metolachlor, pretilachlor and
propachlor;
dinitroanilines, such as oryzalin, pendimethalin and trifluralin; diphenyl
ethers, such as
acifluorfen, bifenox, fluoroglycofen, fomesafen, halosafen, lactofen and
oxyfluorfen;
areas, such as chlorotoluron, diuron, fluometuron, isproturon, linuron and
methabenzthiazuron; hydroxylamines, such as alloxydim, clethodim, cycloxydim,
sethoxydim and tralkoxydim; imidazolinones, such as imazethapyr,
imazamethabenz,
imazapyr and imazaquin; nitrites, such as bromoxynil, dichlobenil and ioxynil;
oxyacetamides, such as mefenacet; sulphonyl-areas, such as amidosulfuron,
bensulfuron-methyl, chlorimuron-ethyl, chlorsulfuron, cinosulfuron,
inetsulfuron-methyl,
nicosulfuron, primisulfuron, pyrazosulfuron-ethyl, thifensulfuron-methyl,
triasulfuron
and tribenuron-methyl; thiocarbamates, such as butylate, cycloate, diallate,
EPTC,
esprocarb, molinate, prosulfocarb, thiobencarb and triallate; triazines, such
as atrazine,
cyanazine, simazine, simetryne, terbutryne and terbutylazine; triazinones,
such as
hexazinone, metamitron and metribuzin; others, such as aminotriazole,
benfuresate,
bentazone, cinmethylin, clomazone, clopyralid, defenzoquat, dithiopyr,
ethofumesate,
fluorochloridone, glufosinate, glyphosate, isoxaben, pyridate, quinchlorac,
quinmerac,
sulphosate and tridiphane.
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

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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 10
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.

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_ ~3 _
Preparation Examples
Example 1
O
S
CI \
S02,NH N N~CH3
N
SCH3
(by process (a))
A mixture of 3.0 g (20.7 mmol) of 4-methyl-5-methylthio-2,4-dihydro-3H-1,2,4-
triazol-
3-one, 4.8 g (20.7 mmol) of 3-chloro-phenylsulphonyl isothiocyanate, 0.3 g of
triethylamine and 60 ml of acetonitrile is heated under reflux for 12 hours
and then
concentrated under, water pump vacuum. The residue is stirred with diethyl
ether and
the crystalline product is isolated by filtration under suction.
2.1 g (27% of theory) of 2-(3-chloro-phenylsulphonyl-aminothiocarbonyl)-4-
methyl-5-
methylthio-2,4-dihydro-3H-1,2,4-triazol-3-one of melting point 141 °C
are obtained.
Example 2
OCF3
S O
S02, ~N~N~CH3
NH
N
OCH3
(by process (b))
A mixture of 3.2 g (12 mmol) of 5-methoxy-4-methyl-2-phenoxythiocarbonyl-2,4-
dihydro-3H-1,2,4-triazol-3-one, 2.9 g (12 mmol) of 2-trifluoromethoxy-benzene-

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sulphonamide, 1.9 g (12.5 mmol) of 1,8-diazabicyclo-[5.4.0]-undec-7-ene (DBU)
and
30 ml. of dioxane is stirred at 20°C for 12 hours. The mixture is then
diluted with
methylene chloride and water and the pH is adjusted to 3 using 2N hydrochloric
acid.
The organic phase is then separated off, dried with sodium sulphate and
filtered. The
filtrate is concentrated under a water pump vacuum, the residue is
crystallized by
digestion with diethyl ether and the product is isolated by filtration under
suction.
3.1 g (63% of theory) of 5-methoxy-4-methyl-2-(2-trifluoromethoxy-
phenylsulphonyl-
aminothiocarbonyl)-2,4-dihydro-3H-1,2,4-triazol-3-one of melting point
139°C are
obtained.
Example 3
CF3
S O
S02,NH N N~CH3
N=-C
SCH3
(by process (b))
At 20°C, 28.1 g (0.125 mol) of 2-trifluoromethyl-benzenesulphonamide
and a solution
of 19 g of 1,8-diazabicyclo-[5.4.0]-undec-7-ene (DBU) in 50 ml of acetonitrile
are
added in succession to a solution of 28.1 g (0.10 mol) of 4-methyl-5-
methylthio-2-
phenoxythiocarbonyl-2,4-dihydro-3H-1,2,4-triazol-3-one in 300 ml of
acetonitrile. The
reaction mixture is stirred at 20°C until a clear solution is obtained.
The solution is
then concentrated under water pump vacuum and the residue is admixed with
water and
methylene chloride (300 mI each) and acidified with 2N hydrochloric acid. The
organic
phase is separated off, the aqueous phase is extracted once more with 100 ml
of
methylene chloride and the combined organic phases are dried with magnesium
sulphate and filtered. The filtrate is concentrated under a water pump vacuum
and the
residue is crystallized from isopropanol.

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29.6 g (72% of theory) of 4-methyl-5-methylthio-2-(2-trifluoromethyl-
phenylsulphonyl-
aminothiocarbonyl)-2,4-dihydro-3H-1,2,4-triazol-3-one of melting point
154°C are
obtained.
By the methods of Examples 1, 2 and 3 and in accordance with the general
description
of the preparation processes according to the invention, it is also possible
to prepare,
for example, the compounds of the formula (I) listed in Table 1 below.
Q,
R ~ ~ R~
S02,NH N N' (I)
N=C
R2

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Table 1: Examples of compounds of the formula (I)
Ex. Q' Q'- R' R'- R3 Melti
No.
point
4 O S CH3 OC3H, ~ OCF3 94
5 S O CH3 C~HS / C F3 126
6 O S CH3 SCH3 CI 142
i
7 O S CH3 SCH3 F 186
i
8 O S CH3 SCH3 CI 174
i
9 O S CH3 SCH3 196
/ \
COOCZHS
10 O S CH3 SCH3 ~ cF3 194
I
11 O S CH3 SCH3 g~ 143
i
12 O S CH3 SCH3 159
i

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Table l: (continued)
Ex. Q' Q'- R' R'- R3 Melting
No. point (°C)
13 O S CH3 SCH3 CH 156
3
14 O S CH3 SCH3 OCHF 139
O S CH3 SCH3 OCF 151
~ 3
16 O S CH3 SCH3 ~ cF3 125
17 O S CH3 SCH3 F 164
i
w
F
18 O S CH3 SCH3 CI 149
i
CI
10 19 O S CH3 SCH3 CH3 156
i
CI

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- Table l: (continued)
Ex. Q' QZ R' R' R3 Melting
No. point (°C)
20 O S CH3 SCH3 sc H 157
zs
21 O S CH3 SCH3 ~ soZc2H5 171
I
22 O S CH3 SCH3 OCH 134
3
23 O S CH3 SCH3 oC2H5 139
i
24 O S CH3 SCH3 c1 134
i
CHz
CI
25 O S CH3 SCH3 OCF3 140
i
CHZ
26 O S CH3 SCH3 OCHF 125
2
CH2
27 O S CH3 C2H5 ~ CF3 126
\
28 O S CH3 OCZHS CF 152
3

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Table l: (continued)
Ex. Q' Q'- R' RZ R3 Melting
No. point (°C)
29 O S CH3 CZHS ~ CH3 128
30 O S CH3 C~HS OCF3 103
i
31 O S CH3 C2H5 ~ cF, 92
32 O S CH3 CZHS ~ ~ cF3 111
33 O S CH3 CZHS ~ CI 141
w
G
34 O S CH3 OCzHS CH 142
3
35 O S CH3 OCZHS OCF3 133
i
36 O S CH3 OCZHS ~ cF3 110
\ I
37 O S CH3 OCZHS ~ ~ cF, 131
\ I

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Table l: (continued)
Ex. Q' QZ R' RZ R3 Melting
No. point (°C)
38 O S CH3 OCZHS CI 156
i
\
CI
39 O S CH3 OCZHS F 141
i
F
40 O S CH3 OCZHS CH3 160
i
CI
41 O S CH3 OCZHS C H 155
ss
42 O S CH3 OCZHS ~ sC2H5 123
43 O S CH3 OCZHS ~ OCH3 127
\
44 O S CH3 OCH3 CF 155
3
45 O S -(CHZ)5- ~ OCF3 128
i

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' Table 1: (continued)
Ex. Q' QZ R' R'- R3 Melting
No. point (°C)
46 O S CH3 OOHS ~ OCHFZ 147
47 O S OCzHS OCZHS CF3 114
i
48 O S OCZHS OC2H5 OCF3 113
i
49 O S N(CH3)~ C3H,-n CF3 113
50 O S N(CH3), C3H., n , OCF3 114
w
51 O S ~ OC3H~ i CF 74
3
52 O S ~ OC3H~ i OCF3 119
i
I
53 O S ~ N(CH3)~ ~ CF3 131
54 O S ~ N(CH3)Z ~ OCF3 132

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Table 1: (continued)
Ex. Q' Q'- R' R'- R' Melting
No. point (°C)
55 O S
CF3 114
56 O S ~ ~ OCF3 124
57 O S ~ SC,HS CF 123
3
58 O S ~ SC,HS ~ OCF3 125
59 O S OCH3 SCH3 CF 110
3
60 O S OCH3 SCH3 OCF 127
3
\
61 O S OCH3 SCzHs CF 121
3
62 O S OCH3 SC,HS OCF 122
3
63 O S CH3 CH3 CF 119
~ \ 3
\

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' Table 1: (continued)
Ex. Q' QZ R' R'- R3 Melting
No. point (°C)
64 O S CH3 CH; OCF3 122
i
65 O S CH3 CH3 ~ OCHFz 113
I
66 O S CH3 C2H5 / OCHFZ 118
67 O S CH3 C3H~ n CF3 112
i
\
68 O S CH3 C3H~ n ~ OCHFZ 112
I
w
69 O S CH3 C3H; i CF3 119
i
\
70 O S CH3 C3H; i OCF 101
3
71 O S CH3 C3H~ i ~ OCHFz 118
72 O S CH3 CHZOCH3 CF 124
3
73 O S CH3 CHZOCH3 OCF 108
3
\

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' Table 1: (continued)
Ex. Q' Q'- R' R'- R3 Melting
No. point (°C)
74 O S CH3 CHZOCH3 OCHFz 106
/v
I
75 O S CH; SCZHS CF 129
3
76 O S CH3 SCZHS OCF3 131
i
77 O S CH3 SC~HS ~ OCHFZ 135
78 O S CH3 OCH3 ~ OCHFz 131
\
79 O S CZHS OOHS CF3 128
i
80 O S CZHS OCZHS OCHFz 85
I
81 O S CH3 OC3H~ n CF 108
3
82 O S CH3 OC3H, n CF3 122
j
\

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- 45 -
- Table 1: (continued)
Ex. Q' Q'- R' R'- R' Melting
No. point (°C)
83 O S CH; OC3H~ i OCF3 119
i
84 O S CH3 OC3H~-i OCHF 130
2
85 O S CZHS OCH3 cF3 123
i
\
86 O S CZHS OCH3 ~ OCHFz 132
\
87 O S OCzHs CZHS OCF3 109
i
88 O S OCZHS CzHs ~ OCHFZ 105
89 O S CH3 Br ~F3 126
i
\
90 O S CH3 Br OCF 115
3
91 O S CH3 Br ~ oCHFz 113
\

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Table 1: (continued)


Ex. Q' Q'- R' R' R3 Melting


No. point
(C)



92 O S ~ Br oF3 113
i
w


93 O S ~ Br oCF3 107
i
I


94 O S ~ Br ocHFz 103
I


95 O S ~ OOHS cF3 117


96 O S ~ OCZHS ocF3 105
w


97 O S ~ OCZHS ~ OCHFZ 90


98 O S ~ CHZOCH3 cF3 106
w


99 O S ~ CHZOCH3 oCF3 119
i


100 O S ~ CHZOCH3 ~ OCHFZ 110



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Table 1: (continued)
Ex. Q' QZ R' R'- R3 Melting
No. point (°C)
101 O S CH3 C,HS , SOZN(CH3)z 119
102 O S CH3 CZHS sc H 126
Zs
w
103 O S CH3 C2H5 ~ soZc2H5 122
104 O S CH3 CZHS ocH3 127
i ,
105 O S CH3 CZHS oczHS 129
i
106 O S CH3 OOHS / So2N(CH~)z 137
\I
107 O S CH3 OC,HS so2c2H5 127
108 O S CH3 OCZHS OCZHS 151
w
109 O S CH3 C~HS F 141
i
I
F

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- 48 -
Table 1: (continued)
Ex. Q' QZ R' R'- R3 Melting
No. point (°C)
110 O S CH3 CZHS CH 143
3
111 O S CH3 SCH3 130
I
112 O S CH3 C,HS F 128 -
i
w
113 O S CH3 CZHS ci 115
/
\
114. O S CH3 CZHS ci 108
I
115 O S CH3 CZHS g~ 129
/
I
116 O S CH3 CZHS 128
/
117 O S CH3 OCzHS F 130
/

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- Table 1: (continued)
Ex. Q' Q'- R' R' R3 Melting
No. point (°C)
118 O S CH3 OC,HS ~~ 135
i
119 O S CH3 OCZHS ci 145
i
120 O S CH3 OCZHS g,. 128
i
I
121 O S CH3 OCZHS 121
i
122 O S CH3 CZHS CF 92
3
CH2
123 O S CH3 CzHS ocF3 115
i
CH2-
124 O S CH3 OCZHS CF3 147
i
CHZ-
125 O S CH3 OCZHS ocF3 132
i
I
CHZ

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Table 1: (continued)
Ex. Q' QZ R' R'- R3 Melting
No. point (°C)
126 O S CH3 SCH3 cF3 138
i
I
CHZ
127 O S ~ OCZHS cH3 137
\
128 O S ~ OCZHS scH3 105
\
129 O S ~ OC,HS off 122
i
\
130 O S OCZHS CZHS CF3 102
i
I
\
131 O S OCZHS CZHS off 97
i
\
132 O S ~ Br scH3 132
i
\
133 O S OCZHS C2H5 cH
3
134 O S OCZHS CzHS scH3 11~
i

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Table l: (continued)
' Ex. Q' QZ R' RZ R3 Melting
No. point (°C)
135 O S ~ Br cH3 118
i
\
136 O S CH3 CHZOCH3 ~ scH3 100
\
137 O S ~ Br
i
\
138 O S CH3 CHZOCH3 cH
3
139 O S CH3 OCHZCF3 cF 73
3
140 O S CH3 OCHZCF3 ocF3 107
\
141 O S CH3 OCHzCF3 OCHF 116
2
\ I
142 O S CH3 OC3H,-n ocHF2
i

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Table 1: (continued) '
Ex. Q' Q'- R' R'- R3 Melting
No. point (°C)
143 O S OCH,HS CZHS OCF3
i
w
144 O S CH3 OCZHS CI
i
w
CH,-
Ci
145 O S CZHS OCH3 OCF 143
3
146 O S OCH3 C3H; n OCF 98
3
147 O S CH3 SCH3 sc2H5 208
I
(Na salt)
148 O S CH3 SCH3 CF 237
(Na salt)
I
149 O S CH3 OCH3 CF 2I0
(Na salt)
I
150 O S CH3 OCH3 oCF 216
3 (Na salt)
I
I' I O S CH3 OCZHs , oCHFz 21 I
(Na salt)

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Table 1: (continued)
Ex. Q' Q'- R' R'- R3 Melting
No. point (°C)
152 O S CH3 OC3H~ n OCF 217
(Na salt)
153 O S CH3 CZHS CI 40
i
CHZ-
CI
154 O S -CHZCH=CHZ OCZHS CH 130
3
155 O S -CHZCH=CHZ OCZHS oCF 84
3
156 O S -CHZCH=CHI OCZHS CF 85
3
157 O S OCZHS ~ OCHF2 205
~ (Na salt)
158 O S
Br OCHFZ 212
(Na salt)
w
159 O S
Br OCF3 220
(Na salt)

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Table l: (continued)


Ex. Q' Q'- R' R'- R3 Melting


No. point (C)


160 O S -a Br ~ 150
CF3


I (Na salt)


161 O S CH3 -CH20CH3 oCF 205


(Na salt)


162 O S CH3 -CHZOCH3 CF 165


(Na salt)
w


163 O S ~ OCZHS ~ osoZcH3 128


164 O S OCZHS C2H5 ~ oso2cH3 120



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Starting materials of the formula (II):
Example (II-1)
O
H~N~N~O-C2H5
N=-C
S-CH3
A mixture of 4.0 g (20 mmol) of the potassium salt of 4-ethoxy-5-mercapto-2,4-
S dihydro-3H-1,2,4-triazol-3-one, 4.3 g (30 mmol) of methyl iodide and 50 ml
of
methanol is stirred at 20°C for 16 hours and then concentrated. The
residue is
extracted with methylene chloride/water and the organic phase is separated
off, dried
with magnesium sulphate and filtered. The filtrate is concentrated, the
residue is
digested with diethyl ether and the crystalline product is isolated by
filtration under
suction.
1.8 g (51%6+1 of theory) of 4-ethoxy-5-methylthio-2,4-dihydro-3H-1,2,4-triazol-
3-one
of melting point 99°C are obtained.
By the methods of Example (II-1) and/or by other known methods (cf. the
publications
mentioned above), it is also possible to prepare, for example, the compounds
of the
formula (II) below:
4-methyl-, 4,5-dimethyl-, 4-methyl-5-ethyl-, 4-methyl-5-n-propyl-, 4-methyl-5-
i-propyl-,
4-methyl-5-n-butyl-, 4-methyl-5-phenoxy-, 4-methyl-5-methylthio-, 4-methyl-5-
ethylthio-, 4-methyl-5-n-propylthio-, 4-methyl-5-i-propylthio-, 4-methyl-5-
allylthio-,
4-methyl-5-propargylthio-, 4-methyl-5-cyclopropyl-, 4-methyl-5-chloro-, 4-
methyl-5-
bromo-, 4-methyl-5-methoxy-, 4-methyl-5-ethoxy-, 4-methyl-5-n-propoxy-, 4-
methyl-5-
i-propoxy-, 4-methyl-5-n-butoxy-, 4-methyl-5-cyclopropylmethoxy-, 4-methyl-5-
cyclopropylthio-, 4-methyl-5-trifluoroethoxy-,4-methyl-5-dimethylamino-and 4-
methyl-
5-methylamino- -2,4-dihydro-3H-1,2,4-triazol-3-one and -2,4-dihydro-3H-1,2,4-
triazole-3-thione;

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4-ethyl-, 4,5-diethyl-, 4-ethyl-5-methyl-, 4-ethyl-S-n-propyl-, 4-ethyl-5-i-
propyl-,
4-ethyl-5-n-butyl-, 4-ethyl-5-phenoxy-, 4-ethyl-5-methylthio-, 4-ethyl-5-
ethylthio-,
4-ethyl-5-n-propylthio-, 4-ethyl-5-i-propylthio-, 4-ethyl-S-allylthio-, 4-
ethyl-5-
propargylthio-, 4-ethyl-5-cyclopropyl-, 4-ethyl-5-chloro-, 4-ethyl-5-bromo-, 4-
ethyl-5-
methoxy-, 4-ethyl-5-ethoxy-, 4-ethyl-5-n-propoxy-, 4-ethyl-5-i-propoxy-, 4-
ethyl-5-n-
butoxy-, 4-ethyl-5-cyclopropylmethoxy-, 4-ethyl-5-cyclopropylthio-, 4-ethyl-5-
trifluoroethoxy-,4-ethyl-5-dimethylamino-and 4-ethyl-5-methylamino--2,4-
dihydro-3H-
1,2,4-triazol-3-one and -2,4-dihydro-3H-1,2,4-triazole-3-thione;
4-cyclopropyl-5-methyl-, 4-cyclopropyl-5-ethyl-, 4-cyclopropyl-5-n-propyl-,
4-cyclopropyl-5-i-propyl-, 4-cyclopropyl-5-n-butyl-, 4-cyclopropyl-5-phenoxy ,
4-cyclopropyl-5-methylthio-, 4-cyclopropyl-5-ethylthio-, 4-cyclopropyl-5-n-
propylthio-,
4-cyclopropyl-5-i-propylthio-,4-cyclopropyl-5-allylthio-,4-cyclopropyl-5-
propargylthio-,
4-cyclopropyl-5-cyclopropyl-, 4-cyclopropyl-5-chloro-, 4-cyclopropyl-5-bromo-,
4-cyclopropyl-5-methoxy-, 4-cyclopropyl-5-ethoxy-, 4-cyclopropyl-5-n-propoxy-,
4-cyclopropyl-S-i-propoxy-, 4-cyclopropyl-5-n-butoxy-, 4-cyclopropyl-5-
cyclopropylmethoxy-, 4-cyclopropyl-5-cyclopropylthio-, 4-cyclopropyl-S-
trifluoroethoxy-, 4-cyclopropyl-5-dimethylamino- and 4-cyclopropyl-5-
methylamino-
-2,4-dihydro-3H-1,2,4-triazol-3-one and -2,4-dihydro-3H-1,2,4-triazole-3-
thione;
4-methoxy-, 4,5-dimethoxy-, 4-methoxy-5-methyl-, 4-methoxy-5-ethyl-, 4-methoxy-
5-n
propyl-, 4-methoxy-5-i-propyl-, 4-methoxy-5-n-butyl-, 4-methoxy-5-phenoxy-,
4-methoxy-5-methylthio-, 4-methoxy-5-ethylthio-, 4-methoxy-5-n-propylthio-,
4-methoxy-5-i-propylthio-, 4-methoxy-5-allylthio-, 4-methoxy-5-propargylthio-,
4-methoxy-5-cyclopropyl-, 4-methoxy-5-chloro-, 4-methoxy-5-bromo-, 4-methoxy-5
ethoxy-, 4-methoxy-5-n-propoxy-, 4-methoxy-5-i-propoxy-, 4-methoxy-5-n-butoxy-
,
4-methoxy-5-cyclopropylmethoxy-, 4-methoxy-5-cyclopropylthio-, 4-methoxy-5-
trifluoroethoxy-, 4-methoxy-5-dimethylamino- and 4-methoxy-5-methylamino-
2,4-dihydro-3H-1,2,4-triazol-3-one and -2;4-dihydro-3H-1,2,4-triazole-3-
thione;
4-ethoxy-, 4,5-diethoxy-, 4-ethoxy-5-methyl-, 4-ethoxy-5-ethyl-, 4-ethoxy-5-n-
propyl-,
4-ethoxy-5-i-propyl-, 4-ethoxy-5-n-butyl-, 4-ethoxy-5-phenoxy-, 4-ethoxy-5-
methylthio-,
4-ethoxy-5-ethylthio-, 4-ethoxy-5-n-propylthio-, 4-ethoxy-5-i-propylthio-, 4-
ethoxy-5-
allylthio-, 4-ethoxy-5-propargylthio-, 4-ethoxy-5-cyclopropyl-, 4-ethoxy-5-
chloro-,
4-ethoxy-5-bromo-, 4-ethoxy-5-methoxy-, 4-ethoxy-5-n-propoxy-, 4-ethoxy-5-i-

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propoxy-, 4-ethoxy-5-n-butoxy-, 4-ethoxy-5-cyclopropylmethoxy-, 4-ethoxy-S-
cyclopropylthio-, 4-ethoxy-5-trifluoroethoxy-, 4-ethoxy-5-dimethylamino- and 4-
ethoxy-
5-methylamino- -2,4-dihydro-3H-1,2,4-triazol-3-one and -2,4-dihydro-3H-1,2,4-
triazole-3-thione;
4-amino-, 4-amino-S-methyl-, 4-amino-5-ethyl-, 4-amino-5-n-propyl-, 4-amino-5-
i-
propyl-, 4-amino-5-n-butyl-, 4-amino-5-phenoxy-, 4-amino-5-methylthio-, 4-
amino-5-
ethylthio-, 4-amino-5-n-propylthio-, 4-amino-S-i-propylthio-, 4-amino-5-
allylthio-,
4-amino-5-propargylthio-, 4-amino-5-cyclopropyl-, 4-amino-5-chloro-, 4-amino-5-

bromo-, 4-amino-5-methoxy-, 4-amino-5-ethoxy-, 4-amino-5-n-propoxy-, 4-amino-5-
i-
propoxy-, 4-amino-5-n-butoxy-, 4-amino-5-cyclopropylmetlloxy-, 4-amino-5-cyclo-

propylthio-, 4-amino-5-trifluoroethoxy-, 4-amino-5-dimethylamino- and 4-amino-
5-
methylamino- -2,4-dihydro-3H-1,2,4-triazol-3-one and -2,4-dihydro-3H-1,2,4-
triazole-
3-thione;
4-methylamino-, 4-methylamino-5-methyl-,4-methylamino-5-ethyl-,4-methylamino-5-
n
propyl-, 4-methylamino-5-i-propyl-, 4-methylamino-5-n-butyl-, 4-methylamino-5
phenoxy-, 4-methylamino-5-methylthio-, 4-methylamino-5-ethylthio-, 4-
methylamino-5
n-propylthio-, 4-methylamino-S-i-propylthio-, 4-methylamino-S-allylthio-,
4-methylamino-S-propargylthio-, 4-methylamino-5-cyclopropyl-, 4-methylamino-5
chloro-, 4-methylamino-5-bromo-, 4-methylamino-5-methoxy-, 4-methylamino-5
ethoxy-, 4-methylamino-5-n-propoxy-,4-methylamino-5-i-propoxy-,4-methylamino-5-
n-
butoxy-, 4-methylamino-5-cyclopropylmethoxy-, 4-methylamino-5-cyclopropylthio-
,
4-methylamino-5-trifluoroethoxy-, 4-methylamino-5-dimethylamino- and
4-methylamino-5-methylamino- -2,4-dihydro-3H-1,2,4-triazol-3-one and
-2,4-dihydro-3 H-1,2,4-triazole-3-thione;
4-dimethylamino-, 4-dimethylamino-5-methyl-, 4-dimethylamino-5-ethyl-,
4-dimethylamino-5-n-propyl-,4-dimethylamino-5-i-propyl-,4-dimethylamino-5-n-
butyl-,
4-dimethylamino-5-phenoxy-, 4-dimethylamino-5-methylthio-, 4-dimethylamino-5-
ethylthio-, 4-dimethylamino-5-n-propylthio-, 4-dimethylamino-5-i-propylthio-,
4-dimethylamino-5-allylthio-, 4-dimethylamino-5-propargylthio-, 4-
dimethylamino-5-
cyclopropyl-, 4-dimethylamino-5-chloro-,4-dimethylamino-5-bromo-,4-
dimethylamino-
5-methoxy-, 4-dimethylamino-5-ethoxy-, 4-dimethylamino-5-n-propoxy-,
4-dimethylamino-5-i-propoxy-, 4-dimethylamino-5-n-butoxy-, 4-dimethylamino-5-

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cyclopropylmethoxy-, 4-dimethylamino-5-cyclopropylthio-, 4-dimethylamino-5-
trifluoroethoxy-, 4-dimethylamino-5-dimethylamino- and 4-dimethylamino-5-
methylamino- -2,4-dihydro-3H-1,2,4-triazol-3-one and 2,4-dihydro-3H-1,2,4-
triazole-3-
thione.
Starting materials of the formula (IV)'
Example (IV-1)
S O
W ~N~N~CH3
O
N
SCH3
At 20°C, a solution of 15.0 g (103 mmol) of 4-methyl-S-methylthio-2,4-
dihydro-3H-
1,2,4-triazol-3-one in 120 ml of methylene chloride is admixed with a solution
of 4.6 g
of sodium hydroxide and 0.5 g of tetrabutylammonium bromide in 120 ml of
water. A
solution of 19.6 g (114 mmol) of O-phenyl chlorothioformate in 100 ml of
methylene
chloride is then added dropwise to this mixture at 20°C, and the
reaction mixture is
stirred at 20°C for a further 12 hours. The crystalline product is
isolated by filtration
under suction.
25.6 g (88% of theory) of 4-methyl-5-methylthio-2-phenoxythiocarbonyl-2,4-
dihydro-
3H-1,2,4-triazol-3-one of melting point 242°C are obtained.
Example (IV-2)
t S O
w ~N~N~CH3
O
N
OCZHS
At 20°C, a solution of 29.6 g (206 mmol) of 4-methyl-5-ethoxy-2,4-
dihydro-3H-1,2,4-

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triazol-3-one in 240 ml of methylene chloride is admixed with a solution of
9.2 g of
sodium hydroxide and 1 g of tetrabutylammonium bromide in 240 ml of water. A
solution of 39.2 g (228 mmol) of O-phenyl chlorothioformate in 200 ml of
methylene
chloride is then added dropwise to this mixture at 20°C, and the
reaction mixture is
stirred at 20°C for a further 12 hours. The organic phase is then
separated off and the
aqueous phase is extracted once more with 100 ml of methylene chloride. The
combined organic phases are washed with 200 m1 of water, dried with magnesium
sulphate and filtered. The filtrate is concentrated under water pump vacuum,
the residue
is stirred with diethyl ether and the crystalline product is isolated by
filtration under
suction.
44.3 g (77% of theory) of 4-methyl-5-ethoxy-2-phenoxythiocarbonyl-2,4-dihydro-
3H-
1,2,4-triazol-3-one of melting point 123°C are obtained.
By the methods of Examples (IV-1) and (IV-2), it is also possible to prepare,
for
example, the compounds of the formula (IV) listed in Table 2 below.

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Q2 Q1
~


_ 1
~N
N~R


IV
N ()



Tabl'.e a (IV)
2: Examples
of the
compounds
of the
formul


Ex., Q' QZ R' RZ Z Melting


No. point (C)



IV-~3 O S CH3 C,HS OC6H5 136


IV-~I O S NHZ CH3 OC6H5 177


IV-5 O S NHz N(CH3)z OC6H5 161


IV-6 O S / ~~CgH9 n N(CH3)2 OC6H5 92


CH3


IV-7 O S NHZ OCH3. OC6H5 158


IV-8 O S CH3 OC3H~ n OC6H5 90


IV-9 O S CH3 OCH3 OC6H5 186


IV-10 O S -(CH2)5- OC6H5 153



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Table 2: (continued)
Ex. Q ' QZ R' R'- Z Melting
No. point (°C)
IV-11 O S ~ OCzHS OC6H5 148
S IV-12 O S CH3 CH3 OC6H5 139


IV-13 O S OCZHS OCZHS OC6H5 98


IV-14 O S OCH3 SCH3 OC6H5 180


IV-15 O S OCH3 SCZHS OC6H5 100


IV-16 O S N(CH3)2 C3H~-n OC6H5 58


~


IV-17 O S OC3H~ i OC6H5 89


IV-18 O S ~ N(CH3)z OC6H5 154

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Table 2: (continued)
Ex.- Q' QZ R' R.'- Z Melting
No. point (°C)
IV-19 O S ~ ~ OC6H5 144
IV-20 O S ~ S-CZHS OC6H5 124
IV-21 O S CH3 OC3H,-i OC6H5 108


IV-22 O S CZHS OCH3 OC6H5 122


IV-23 O S OCZHS CZHS OC6H5 95


IV-24 , O S CH3 Br OC6H5 211


IV-25 O S CH3 OCHZCF3 OC6H5 122


IV-26 O S OCH3 C3H, n OC6H5 oil



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Table 2: (continued)
Ex.- Q' Q'- R' RZ Z Melting
No. point (°C)
IV-27 O S ~ Br OC6H5 172
IV-28 O S ~ CHZOCH3 OC6H5 74
IV-29 O S CzHs OCZHS OC6H5 89


IV-30 O S CH3 SOZCH3 OC6HS 196


IV-31 O S CH3 C3H~-n OC6H5 67


IV-32 O S CH3 C3H~ i OC6H5 96


IV-33 O S CH3 CHZOCH3 OC6H5 98


IV-34 O S CH3 SCZHS OC6H5 130


IV-35 O S CHZ CH=CHZ OCZHS OC6H5


IV-36 S O CH3 H OC6H5 172



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Use Examples:
Example A
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. After 24 hours, the soil is
watered
with the preparation of the active compound. It is advantageous 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:
0% = no action (like untreated control)
100% = total destruction
In this test, the compounds according to Preparation Examples 3, 23, 27 and
28, for
example, exhibit a very strong action against weeds, while some of them are
very well
tolerated by crops, such as cotton.

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Table A: Pre-emergence testlgreenhouse
Appli-CottonEchinoPoa SetariaPortu-Sola-


Active compound cation chloa laca num


rate


(glha)


CF3
S O


~CH ~0 0 95 95 90 95 95
S02,
a
N


~
NH
N


SCH3


(3)


OCzHs
S O


soz, N ~ N ~CH3 60 0 80 95 90 70 90


NH
N


SCH3


(23)


CF3
S O


sot, N~N--~H3 60 0 95 95 95 90 90
~


N
~
N=


C2Hs


(27)


CF3
S O


sot, N ~ N,~H3 60 0 95 95 95 95 95


NH
N


OC2H5


(28)



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Example B
Post-emergence test
Solvent: 5 parts by weight of acetone
Emulsifier: 1 part by weight of alkylaryl polyglycol ether
To produce a suitable preparation of active compound, 1 part by weight of
active
compound is mixed with the stated amount of solvent, the 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 chosen so that
the
particular amounts of active compound desired are employed in 1000 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
In this test, the compounds of Preparation Examples 3, 15 and 28, for example,
exhibit
a very strong action against weeds, while being well tolerated by crops, such
as wheat.

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Table B: Post-emergence test/greenhouse
Appli- Wheat Amaran- Helia Sola- Xanthium
Active compound cation thus nthus num
rate
(g/ha)
CF3
S O
so2,N ~N~N~CHa 60 5 95 100 90 95
N
SCH3
(3)
OCF3
S O
sot, N~N~oH3 60 0 85 95 85 70
Nf~ ~
AI~I
~V
SCH3
(15)
CF3
S O
sot, N~N~cH3 60 10 95 100 99 90
NH
N
OCzHS
(28)

Representative Drawing