SULPHONYLAMINO(THIO)CARBONYLTRIAZOLIN(THI)ONES WITH ARYLOXY OR ARYLTHIO SUBSTITUENTS

COMPOSES SULFONYLAMINO(THIO)CARBONYLTRIAZOLINE(THI)ONES A SUBSTITUANTS ARYLOXY OU ARYLTHIO UTILISES COMME HERBICIDES

English Abstract

The invention concerns sulphonylamino(thio)carbonyltriaxolin(thi)ones of
formula (I) in which Q1 is oxygen or sulphur, Q2 is oxygen or sulphur, Q3 is
oxygen or sulphur, R1 is hydrogen, hydroxy, amino, alkylidenamino or an
optionally substituted group from the series alkyl, alkenyl, alkinyl, alkoxy,
alkylamino, dialkylamino, alkanoylamino, cycloalkyl, cycloalkylalkyl,
cycloalkylamino, aryl and arylalkyl, R2 is substituted aryl when Q3 is oxygen
and R2 is optionally substituted aryl when Q3 is sulphur, and R3 is an
optionally substituted group from the series alkyl, arylalkyl, aryl and
heteroaryl, plus salts of such compounds. The invention also concerns methods
of preparing compounds of formula (I), intermediates for use in their
preparation and the use of the compounds as herbicides.

French Abstract

L'invention concerne de nouvelles sulfonylamino(thio)carbonyltriazoline(thi)ones de formule (I), dans laquelle Q?1¿ désigne un oxygène ou un soufre, Q?2¿ désigne un oxygène ou un soufre, Q?3¿ désigne un oxygène ou un soufre, R?1¿ désigne un hydrogène, un hydroxy, amino, alkylidène-amino ou un reste, éventuellement substitué, choisi dans la série alkyle, alkényle, alkinyle, alkoxy, alkylamino, dialkylamino, alkanoylamino, cycloalkyle, cycloalkylalkyle, cycloalkylamino, aryle, arylalkyle, R?2¿ désigne un aryle substitué, dans le cas où Q?3¿ est un oxygène et, dans le cas où Q?3¿ est un soufre, un aryle éventuellement substitué, et R?3¿ désigne un reste éventuellement substitué, choisi dans la série alkyle, aralkyle, aryle, hétéroaryle, ainsi que des sels des composés de formule (I). L'invention concerne également des procédés et de nouveaux produits intermédiaires pour la fabrication des composés de formule (I), ainsi que leur utilisation comme herbicides.

Claims

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claims
1. Sulfonylamino(thio)carbonyltriazolin(ethi)one having aryloxy or arylthio
substituents of the general formula(I)



Image (I)



in which

Q1 represents oxygen or sulfur,

Q2 represents oxygen or sulfur,

Q3 represents oxygen or sulfur,

R1 represents hydrogen, hydroxyl, amino, alkylidenamino or represents a
respectively optionally substituted radical from the group consisting of
alkyl, alkenyl, alkinyl, alkoxy, alkylamino, dialkylamino, alkanoylamino,
cycloalkyl, cycloalkylalkyl, cycloalkylamino, aryl and arylalkyl,


R2 represents substituted aryl when Q3 represents oxygen and represents
optionally substituted aryl when Q3 represents sulfur and

R3 represents a respectively optionally substituted radical from the group
consisting of alkyl, aralkyl, aryl and heteroaryl,
and salts of compounds of the formula (I).

2. Compounds of the formula (I) according to claim 1, characterized in that


- 78 -
Q1 represents oxygen or sulfur,

Q2 represents oxygen or sulfur,

Q3 represents oxygen or sulfur,

R1 represents hydrogen, hydroxyl, amino, C1-C6-alkylidenamino, optionally
fluorine-, chlorine-, bromine-, cyano-, C1-C4-alkoxy-, C1-C4-alkyl-carbonyl-
or C1-C4-alkoxy-carbonyl-substituted C1-C6-alkyl, represents respectively
optionally fluorine-, chlorine- and/or bromine-substituted C2-C6-alkenyl or
C2-C6-alkinyl, represents respectively optionally fluorine- and/or
chlorine-substituted C1-C6-alkoxy, C1-C6-alkylamino, di-(C1-C4-alkyl)-amino or
C1-C4-alkanoylamino, represents respectively optionally fluorine-, chlorine-,
bromine- and/or C1-C4-alkyl-substituted C3-C6-cycloalkyl or C3-C6-
cycloalkyl-C1-C4-alkyl, or represents respectively optionally fluorine-,
chlorine-, bromine-, cyano-, nitro-, C1-C4-alkyl-, trifluoromethyl-, C1-C4-
alkoxy- and/or C1-C4-alkoxycarbonyl-substituted phenyl or phenyl-C1-C4-
alkyl,

R2, in the case where Q3 represents oxygen, represents phenyl or naphthyl, each
of which is substituted by cyano, carboxy, halogen, by C1-C4-alkyl (which
is optionally substituted by cyano, halogen or C1-C4-alkoxy), by C1-C4-
alkoxy, C1-C4-alkyl-carbonyl, C1-C4-alkoxy-carbonyl or C1-C4-alkylthio
(each of which is optionally substituted by cyano or halogen), by C3-C6-
cycloalkyl, phenyl or phenyl-C1-C4-alkyl (each of which is optionally
substituted by cyano, halogen, C1-C4-alkyl, C1-C4-halogenoalkyl, C1-C4-
alkoxy and/or C1-C4-halogenoalkoxy), and, in the case where Q3 represents
sulfur, represents phenyl or naphthyl, each of which is optionally
substituted by cyano, carboxy, halogen, by C1-C4-alkyl (which is optionally
substituted by cyano, halogen or C1-C4-alkoxy), by C1-C4-alkoxy, C1-C4-
alkyl-carbonyl, C1-C4-alkoxy-carbonyl or C1-C4-alkylthio (each of which is
optionally substituted by cyano or halogen), by C3-C6-cycloalkyl, phenyl or



- 79 -
phenyl-C1-C4-alkyl (each of which is optionally substituted by cyano,
halogen, C1-C4-alkyl, C1-C4-halogenoalkyl, C1-C4-alkoxy and/or C1-C4-
halogenoalkoxy),


R3 represents the grouping Image



in which

R4 and R5 are identical or different and each represent hydrogen, fluorine,
chlorine, bromine, iodine, nitro, C1-C6-alkyl (which is optionally
substituted by fluorine, chlorine, bromine, cyano, carboxy, C1-C4-alkoxy-
carbonyl, 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-alkylsulfinyl, C1-C4-alkylsulfonyl, di-(C1-C4-alkyl)-aminosulfonyl,
C3-C6-cycloalkyl or phenyl), represents C2-C6-alkenyl (which is
optionally substituted by fluorine, chlorine, bromine, cyano, C1-C4-
alkoxy-carbonyl, carboxy or phenyl), represents C2-C6-alkinyl (which is
optionally substituted by fluorine, chlorine, bromine, cyano, C1-C4-
alkoxy-carbonyl, carboxy or phenyl), represents C1-C4-alkoxy (which is
optionally substituted by fluorine, chlorine, bromine, cyano, carboxy,
C1-C4-alkoxy-carbonyl,C1-C4-alkoxy, C1-C4-alkylthio, C1-C4-alkylsulfinyl
or C1-C4-alkylsulfonyl), represents C1-C4-alkylthio (which is optionally
substituted by fluorine, chlorine, bromine, cyano, carboxy, C1-C4-alkoxy-
carbonyl, C1-C4-alkylthio, C1-C4-alkylsulfinyl or C1-C4-alkylsulfonyl),
represents C2-C6-alkenyloxy (which is optionally substituted by fluorine,
chlorine, bromine, cyano or C1-C4-alkoxy-carbonyl), represents C2-C6-
alkenylthio (which is optionally substituted by fluorine, chlorine,





- 80-
bromine, cyano, nitro, C1-C3-alkylthio or C1-C4-alkoxycarbonyl), C3-C6-
alkinyloxy, C3-C6-alkinylthio or represents the radical -S(O)p-R6 where,

p represents the numbers 1 or 2 and

R6 represents C1-C4-alkyl (which is optionally substituted by
fluorine, chlorine, bromine, cyano or C1-C4-alkoxy-carbonyl),
C3-C6-alkenyl, C3-C6-alkinyl, C1-C4-alkoxy, C1-C4-alkoxy-C1-C4-
alkylamino, C1-C4-alkylamino, di-(C1-C4-alkyl)-amino, phenyl or
represents the radical -NHOR7 where

R7 represents C1-C12-alkyl (which is optionally substituted by
fluorine, chlorine, cyano, C1-C4-alkoxy, C1-C4-alkylthio,
C1-C4-alkylsulfinyl, C1-C4-alkylsulfonyl, C1-C4-alkyl-
carbonyl, C1-C4-alkoxy-carbonyl, C1-C4-alkylamino-
carbonyl or di-(C1-C4-alkyl)-amino-carbonyl), represents
C3-C6-alkenyl (which is optionally substituted by fluorine,
chlorine or bromine), C3-C6-alkinyl, C3-C6-cycloalkyl,
C3-C6-cycloalkyl-C1-C2-alkyl, phenyl-C1-C2-alkyl (which is
optionally substituted by fluorine, chlorine, nitro, cyano,
C1-C4-alkyl, C1-C4-alkoxy or C1-C4-alkoxy-carbonyl),
represents benzhydrol or represents phenyl (which is
optionally substituted by fluorine, chlorine, nitro, cyano,
C1-C4-alkyl, trifluoromethyl, C1-C4-alkoxy, C1-C2-
fluoroalkoxy, C1-C4-alkylthio, trifluoromethylthio or C1-C4-
alkoxy-carbonyl),

R4 and/or R5 furthermore represent phenyl or phenoxy, represent C1-C4-
alkyl-carbonylamino, C1-C4-alkoxy-carbonylamino, C1-C4-alkylamino-
carbonyl-amino, di-(C1-C4-alkyl)-amino-carbonylamino, or represent
the radical -CO-R8 where



- 81 -
R8 represents hydrogen, C1-C6-alkyl, C3-C6-cycloalkyl, C1-C6-alkoxy,C3-C6-cycloalkoxy, C3-C6-alkenyloxy, C1-C4-alkylthio, C1-C4-
alkylamino, C1-C4-alkoxyamino, C1-C4-alkoxy-C1-C4-alkylamino
or di-(C1-C4-alkyl)-amino (each of which are optionally
substituted by fluorine and/or chlorine),

R4 and/or R5 furthermore represent trimethylsilyl, thiazolinyl, C1-C4-
alkyl-sulfonyloxy, di-(C1-C4-alkyl)-aminosulfonylamino or represent
the radical

-CH=N-R9 where

R9 represents optionally fluorine-, chlorine-, cyano-, carboxy-,
C1-C4-alkoxy-, C1-C4-alkylthio-, C1-C4-alkylsulfinyl-, or C1-C4-
alkylsulfonyl-substituted C1-C6-alkyl, represents optionally
fluorine- or chlorine-substituted benzyl, represents optionally
fluorine- or chlorine-substituted C3-C6-alkenyl or C3-C6-alkinyl,
represents optionally fluorine-, chlorine-, bromine-, C1-C4-alkyl-,
C1-C4-alkoxy-, trifluoromethyl-, trifluoromethoxy- or
trifluoromethylthio-substituted phenyl, represents optionally
fluorine- and/or chlorine-substituted C1-C6-alkoxy, C3-C6-
alkenyloxy, C3-C6-alkinyloxy or benzyloxy, represents amino,
C1-C4-alkylamino, di-(C1-C4-alkyl)-amino, phenylamino, C1-C4-
alkyl-carbonyl-amino, C1-C4-alkoxy-carbonylamino, C1-C4-alkyl-
sulfonylamino or represents optionally fluorine-, chlorine-,
bromine- or methyl-substituted phenylsulfonylamino,

furthermore


- 82 -



R3 represents the radical Image




in which

R10 represents hydrogen or C1-C4-alkyl,

R11 and R12 are identical or different and each represent hydrogen, fluorine,
chlorine, bromine, nitro, cyano, C1-C4-alkyl (which is optionally substituted
by fluorine and/or chlorine), C1-C4-alkoxy (which is optionally substituted
by fluorine and/or chlorine), carboxy, C1-C4-alkoxy-carbonyl,
dimethylaminocarbonyl, C1-C4-alkylsulfonyl or di-(C1-C4-alkyl)-
aminosulfonyl;

furthermore


R3 represents the radical Image



in which

R13 and R14 are identical or different and each represent hydrogen, fluorine,
chlorine, bromine, nitro, cyano, C1-C4-alkyl (which is optionally
substituted by fluorine and/or chlorine) or C1-C4-alkoxy (which is
optionally substituted by fluorine and/or chlorine);

- 83 -
furthermore


R3 represents the radical Image




in which

R15 and R16 are identical or different and each represent hydrogen, fluorine,
chlorine, bromine, nitro, cyano, C1-C4-alkyl (which is optionally
substituted by fluorine and/or chlorine), C1-C4-alkoxy (which is
optionally substituted by fluorine and/or chlorine), represents C1-C4-
alkylthio, C1-C4-alkylsulfinyl or C1-C4-alkylsulfonyl (each of which is
optionally substituted by fluorine and/or chlorine), represent
aminosulfonyl, mono-(C1-C4-alkyl)-aminosulfonyl, represent di-(C1-C4-
alkyl)-aminosulfonyl or C1-C4-alkoxy-carbonyl or
dimethylaminocarbonyl;

furthermore


R3 represents the radical Image



in which

R17 and R18 are identical or different and each represent hydrogen, fluorine,
chlorine, bromine, C1-C4-alkyl (which is optionally substituted by


- 84 -
fluorine and/or bromine), C1-C4-alkoxy (which is optionally substituted
by fluorine and/or chlorine), represents C1-C4-alkylthio, C1-C4-
alkylsulfinyl or C1-C4-alkylsulfonyl (which are optionally substituted by
fluorine and/or chlorine), or represent di-(C1-C4-alkyl)-aminosulfonyl;

furthermore


R3 represents the radical Image



in which

R19 and R20 are identical or different and each represent hydrogen, fluorine,
chlorine, bromine, cyano, nitro, C1-C4-alkyl (which is optionally
substituted by fluorine and/or chlorine), C1-C4-alkoxy (which is
optionally substituted by fluorine and/or chlorine), C1-C4-alkylthio, C1-
C4-alkylsulfinyl or C1-C4-alkylsulfonyl (each of which are optionally
substituted by fluorine and/or chlorine), di-(C1-C4-alkyl)-amino-sulfonyl,
C1-C4-alkoxy-carbonyl or dimethylaminocarbonyl, and

A represents oxygen, sulfur or the grouping N-Z1 where

Z1 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), C1-C4-alkyl-carbonyl, C1-C4-alkoxy-
carbonyl or di(C1-C4-alkyl)-aminocarbonyl;

furthermore


- 85 -

R3 represents the radical Image



in which

R21 and R22 are identical or different and each represent hydrogen, C1-C4-
alkyl, halogen, C1-C4-alkoxy-carbonyl, C1-C4-alkoxy or C1-C4-
halogenoalkoxy,

Y1 represents sulfur or the grouping N-R23 where

R23 represents hydrogen or C1-C4-alkyl;

furthermore


R3 represents the radical
Image



in which

R24 represents hydrogen, C1-C4-alkyl, benzyl, pyridyl, quinolinyl or
phenyl,

R25 represents hydrogen, halogen, cyano, nitro, C1-C4-alkyl (which is
optionally substituted by fluorine and/or chlorine), C1-C4-alkoxy
(which is optionally substituted by fluorine and/or chlorine),


- 86 -

dioxolanyl or C1-C4-alkoxy-carbonyl and

R26 represents hydrogen, halogen or C1-C4-alkyl,

and also 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)-sulfonium, C5- or C6-cycloalkyl-
ammonium and di-(C1-C2-alkyl)-benzyl-ammonium salts thereof.

3. Compounds of the formula (I) according to claim 1, characterized in that

Q1 represents oxygen or sulfur,

Q2 represents oxygen or sulfur,

Q3 represents oxygen or sulfur,

R1 represents respectively optionally fluorine-, chlorine-, cyano-, methoxy- or
ethoxy-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl,
represents respectively optionally fluorine-, chlorine- or bromine-substituted
propenyl, butenyl, propinyl or butinyl, represents methoxy, ethoxy, n- or
i-propoxy, n-, i-, s- or t-butoxy, methylamino, ethylamino, n- or
i-propylamino, n-, i-, s- or t-butylamino, dimethylamino or diethylamino,
represents respectively optionally fluorine-, chlorine-, bromine-, methyl- or
ethyl-substituted cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl,
cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl or
cyclohexylmethyl, or represents respectively optionally fluorine-, chlorine-,
bromine-, cyano-, methyl-, trifluoromethyl- or methoxy-substituted benzyl
or phenyl,

R2, in the case where Q3 represents oxygen, represents cyano-, carboxy-,
fluorine-, chlorine-, bromine-, methyl-, ethyl-, n- or i-propyl, n-, i-, s- or


- 87 -
t-butyl-, trifluoromethyl-, methoxy-, ethoxy-, n- or i-propoxy-, n-, i-, s- or
t-butyloxy-, difluoromethoxy-, trifluoromethoxy-, chlorodifluoromethoxy-,
acetyl-, propionyl-, methoxycarbonyl-, ethoxycarbonyl-, methylthio-,
ethylthio-, cyclopentyl-, cyclohexyl-, phenyl- or benzyl-substituted phenyl,
and, in the case where Q3 represents sulfur, represents optionally cyano-,
carboxy-, fluorine-, chlorine-, bromine-, methyl-, ethyl-, n- or i-propyl-, n-,
i-, s- or t-butyl-, trifluoromethyl-, methoxy-, ethoxy-, n- or i-propoxy-, n-,
i-, s- or t-butyloxy-, difluoromethoxy-, trifluoromethoxy-,
chlorodifluoromethoxy-, acetyl-, propionyl-, methoxycarbonyl-,
ethoxycarbonyl-, methylthio-, ethylthio-, cyclopentyl-, cyclohexyl-, phenyl-
or benzyl-substituted phenyl,

R3 represents the radical Image


in which

R4 represents fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl,
trifluoromethyl, methoxy, ethoxy, n- or i-propoxy, n or i-butoxy,
difluoromethoxy, trifluoromethoxy, 2-chloro-ethoxy, 2,2,2-trifluoro-ethoxy,
1,1,2,2-tetrafluoro-ethoxy, 1,1,2,2,2-pentafluoro-ethoxy, 2-
methoxy-ethoxy, methylthio, ethylthio, n- or i-propylthio, n- or
i-butylthio, 2-fluoro-ethylthio, allyloxy, propargyloxy, methylsulfinyl,
ethylsulfonyl, methylsulfonyl, ethylsulfonyl, dimethylaminosulfonyl,
diethylaminosulfonyl, N-methoxy-N-methylaminosulfonyl, phenyl,
phenoxy, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl,
and

R5 represents hydrogen, fluorine, chlorine, bromine, methyl, ethyl or


- 88 -
trifluoromethyl;

furthermore


R3 represents the radical Image


in which

R10 represents hydrogen,

R11" represents fluorine, chlorine, bromine, methyl, methoxy,
difluoromethoxy, trifluoromethoxy, ethoxy, methoxycarbonyl,
ethoxycarbonyl, methylsulfonyl or dimethylaminosulfonyl and

R12 represents hydrogen;

furthermore



R3 represents the radical Image




in which


- 89 -
R represents methyl, ethyl, n- or i-propyl, or

R3 represents the radical Image

in which

R24 represents methyl, ethyl, n- or i-propyl, phenyl or pyridyl,

R25 represents hydrogen, fluorine, chlorine or bromine,

R26 represents fluorine, chlorine, bromine, methoxycarbonyl or
ethoxycarbonyl.

4. Process for preparing compounds of the formula (I) according to claim 1 and
salts thereof, characterized in that

(a) triazolin(ethi)ones of the general formula (II)
Image (II)

in which

Q1, Q3, R1 and R2 are each as defined in claim 1


- 90 -
are reacted with sulfonyl iso(thio)cyanates of the general formula (III)

R3-SO2-N=C=Q2 (III)

in which

Q2 and R3 are each as defined in claim 1,

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)
Image (IV)
in which

Q1, Q2, Q3, R1 and R2 are each as defined above and

Z represents halogen, alkoxy, aralkoxy or aryloxy

are reacted with sulfonamides of the general formula (V)

R3SO2-NH2 (V)

in which


- 91 -
R3 is as defined above,

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)

Image (II)


in which

Q1, Q3, R1 and R2 are each as defined above

are reacted with sulfonamide derivatives of the general formula (VI)

R3-SO2-NH-CQ2-Z (VI)

in which

Q2 and R3 are each as defined above and

Z represents halogen, alkoxy, aralkoxy or aryloxy,

if appropriate in the presence of an acid acceptor and if appropriate in the
presence of a diluent,

or





- 92 -
(d) triazolin(ethi)ones of the general formula (II)
Image (II)
in which

Q1, Q3, R1 and R2 are each as defined above

are reacted with sulfonyl halides of the general formula (VII)

R3-SO2-X (VII)

in which

R3 is as defined above and

X represents halogen,

and metal (thio)cyanates of the general formula (VIII)

MQ2CN (VIII)

in which

Q2 is as defined 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,


- 93 -
and the compounds of the formula (I) obtained by process (a), (b), (c) or
(d) are, if required, converted into salts by customary methods.

5. Herbicidal compositions, characterized by a content of at least one compound
of the formula (I) or a salt thereof according to claim 1.

6. Use of compounds of the general formula (I) or of salts thereof according to
claim l for controlling undesirable vegetation.

7. Method for controlling weeds, characterized in that compounds of the general
formula (I) or salts thereof according to claim 1 are allowed to act on the weeds
or their habitat.

8. Process for preparing herbicidal compositions, characterized in that compounds
of the general formula (I) or salts thereof according to claim 1 are mixed with
extenders and/or surfactants.

9. Triazolin(ethi)one derivatives of the general formula (IV)

Image (IV)

in which

Q1 represents oxygen or sulfur,

Q2 represents oxygen or sulfur,

Q3 represents oxygen or sulfur,

R1 represents hydrogen, hydroxyl, amino, alkylidenamino or represents a

- 94 -
respectively optionally substituted radical from the group consisting of
alkyl, alkenyl, alkinyl, alkoxy, alkylamino, dialkylamino, alkanoylamino,
cycloalkyl, cycloalkylalkyl, cycloalkylamino, aryl and arylalkyl,

R2 represents substituted aryl when Q3 represents oxygen and represents
optionally substituted aryl when Q3 represents sulfur and

Z represents halogen, alkoxy, aralkoxy or aryloxy.

Description

CA 02220494 1997-11-07
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.

- 1
Sulfonylamino(thio)ca~bonyll~iazolin(ethi)ones having aryloxy or arylthio substituen~

The invention relates to novel sulfonylamino(thio)carbonyltriazolin(ethi)ones having
aryloxy or arylthio substituents, to a plurality of processes for their plepal~tion and to
their use as herbicides.

5 Certain sulfonylaminocarbonyltriazolinones are already known to have herbicidal
p~ ellies (cf. EP-A 341489, EP-A 422469, EP-A 425948, EP-A 431291, EP-A
507171). However, the activity of these compounds is not satisfactory in all aspects.

This invention, accordingly, provides the novel
sulfonylamino(thio)carbonyltriazolin(ethi)ones having aryloxy or arylthio substituents
10 of the general formula (I)


R3 Q2 Q

S~2--NH N, ~N--R
Q3 R2 (I~

in which

Q' represents oxygen or sulfur,

Q2 represents oxygen or sulfur,

Q3 represents oxygen or sulfur,

15 R' represents hydrogen, hydroxyl, amino, alkyli~ien~mino or represents a
respectively optionally substituted radical from the group con~i~ting of alkyl,
alkenyl, alkinyl, alkoxy, alkylamino, dialkylamino, alkanoylamino, cycloalkyl,
cycloalkylalkyl, cycloalkylamino, aryl and arylalkyl,

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- 2 -
R2 represents substituted aryl when Q3 represents oxygen and represents optionally
substituted aryl when Q3 represents sulfur and

R3 represents a respectively optionally substituted radical from the group con~ ting
of alkyl, aralkyl, aryl and heteroaryl,

S and salts of compounds of the forrnula (I).

The novel sulfonylamino(thio)carbonyltriazolin(ethi)ones having aryloxy or arylthio
substituents of the general formula (I) are obtained when

(a) triazolin(ethi)ones of the general formula (II)

,1~
H--N N--R

=( 3 2
Q-R

in which

Q', Q3, R' and R2 are each as defined above,

are reacted with sulfonyl iso(thio)cyanates of the general formula (III)

R3-So2-N=C=QZ (III)

in which

Q2 and R3 are each as defined above,

if approl)liate in the presence of a reaction auxiliary and if apl)lop~iate in the
presence of a diluent,

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3 -
or

(b) triazolin(ethi)one derivatives of the general formula (IV)

Q2 Q
Z~--N N~
N =~
Q3 R2 (~
in which

Ql, Q2, Q3, Rl and R2 are each as defined above and

S Z represents halogen, alkoxy, aralkoxy or aryloxy

are reacted with sulfonamides of the general formula (V)

R3So2-NH2 (V)

in which

R3 is as defined above,

if appropl;ate in the presence of an acid acceptor and if appropriate in the
presence of a diluent,

or

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- 4 -
(c) triazolin(ethi)ones of the general forrnula (II)
Q'
H J~ ~R
N N
~3 R2 (Ll)




in which

Q~, Q3, Rl and R2 are each as defined above

are reacted with sulfonarnide derivatives of the general formula (VI)

R3-So2-NH-CQ'-Z (VI)

in which

Q2 and R3 are each as defined above and

Z represents halogen, alkoxy, aralkoxy or aryloxy,

if ~pr~liate in the presence of an acid acceptor and if appropriate in the
presence of a diluent,

or

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- 5
(d) triazolin(ethi)ones of the general formula (II)
Q1

~l~NJ~N~
=(' 3 2
Q-R ~II)



in which

Ql, Q3, Rl and R2 are each as defined above

are reacted with sulfonyl halides of the general formula (VII)

R3-So2-X (VII)

in which

R3 is as defined above and

X represents halogen,

and metal (thio)cyanates of the general formula (VIII)

l 0 MQ2CN (VIII)

in which

Q2 is as defined above and

M represents an alkali metal or an alkaline earth metal equivalent,

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-- 6 --
if appropl;ate in the presence of a reaction auxiliary and if a~plopliate in thepresence of a diluent,

and the compounds of the formula (I) obtained by process (a), (b), (c) or (d)
are, if required, converted into salts by customary methods.

The novel sulfonylamino(thio)carbonyltriazolin(ethi)ones having aryloxy or arylthio
substituents of the general forrnula (I) have strong herbicidal activities.

The invention preferably provides compounds of the formula (I) in which

Q' represents oxygen or sulfur,

Q2 represents oxygen or sulfur,

10 Q3 represents oxygen or sulfur,

Rl represents hydrogen, hydroxyl, amino, Cl-C6-alkyliclen~mino, optionally
fluorine-, chlorine-, bromine-, cyano-, C,-C4-alkoxy-, Cl-C4-alkyl-carbonyl- or
Cl-C4-alkoxy-carbonyl-substituted Cl-C6-alkyl, represents respectively optionally
fluorine-, chlorine- and/or bromine-substituted C2-C6-alkenyl or C2-C6-alkinyl,
represents respectively optionally fluorine- and/or chlorine-substituted Cl-C6-
alkoxy, Cl-C6-alkylarnino, di-(Cl-C4-alkyl)-amino or Cl-C4-alkanoylamino,
represents respectively optionally fluorine-, chlorine-, bromine- and/or Cl-C4-
alkyl-substituted C3-C6-cycloalkyl or C3-C6-cycloalkyl-Cl-C4-alkyl, or represents
respectively optionally fluorine-, chlorine-, bromine-, cyano-, nitro-, Cl-C4-
alkyl-, trifluoromethyl-, Cl-C4-alkoxy- and/or Cl-C4-alkoxycarbonyl-substituted
phenyl or phenyl-Cl-C4-alkyl,

R2, in the case where Q3 represents oxygen, represents phenyl or naphthyl, each of
which is substituted by cyano, carboxy, halogen, by Cl-C4-alkyl (which is
optionally substituted by cyano, halogen or Cl-C4-alkoxy), by Cl-C4-alkoxy,

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.
- 7 -
C,-C4-alkyl-carbonyl, C,-C4-alkoxy-carbonyl or C,-C4-alkylthio (each of which
is optionally substituted by cyano or halogen), by C3-C6-cycloalkyl, phenyl or
phenyl-C,-C4-alkyl (each of which is optionally substituted by cyano, halogen,
C,-C4-alkyl, C,-C4-halogenoalkyl, C,-C4-alkoxy and/or C,-C4-halogenoalkoxy),
and, in the case where Q3 represents sulfur, represents phenyl or naphthyl, eachof which is optionally substituted by cyano, carboxy, halogen, by C,-C4-alkyl
(which is optionally substituted by cyano, halogen or C,-C4-alkoxy), by C,-C4-
alkoxy, C,-C4-alkyl-carbonyl, C,-C4-alkoxy-carbonyl or C,-C4-alkylthio (each of
which is optionally substituted by cyano or halogen), by C3-C6-cycloalkyl,
phenyl or phenyl-C~-C4-alkyl (each of which is optionally substituted by cyano,
halogen, C~-C4-alkyl, C,-C4-halogenoalkyl, C,-C4-alkoxy and/or C~-C4-
halogenoalkoxy),


R3 represents the grouping ~R5




in which

R4 and R5 are identical or different and each represent hydrogen, fluorine,
chlorine, bromine, iodine, nitro, C,-C6-alkyl (which is optionally substituted
by fluorine, chlorine, bromine, cyano, carboxy, Cl-C4-alkoxy-carbonyl,
C,-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-alkylthio, C,-C4-
alkylsulfinyl, C,-C4-alkylsulfonyl, di-(C,-C4-alkyl)-arninosulfonyl, C3-C6-
cycloalkyl or phenyl), represents C2-C6-alkenyl (which is optionally
substituted by fluorine, chlorine, bromine, cyano, C,-C4-alkoxy-carbonyl,
carboxy or phenyl), represents C2-C6-alkinyl (which is optionally substituted

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- 8 -
by fluorine, chlorine? bromine, cyano, Cl-C4-alkoxy-carbonyl, carboxy or
phenyl), represents Cl-C4-alkoxy (which is optionally substituted by
fluorine, chlorine, bromine, cyano, carboxy, Cl-C4-alkoxy-carbonyl, Cl-C4-
alkoxy, Cl-C4-alkylthio, Cl-C4-alkylsulfinyl or Cl-C4-alkylsulfonyl),
represents Cl-C4-alkylthio (which is optionally substituted by fluorine,
chlorine, bromine, cyano, carboxy, Cl-C4-alkoxy-carbonyl, Cl-C4-alkylthio,
Cl-C4-alkylsulfinyl or Cl-C4-alkylsulfonyl), represents C2-C6-alkenyloxy
(which is optionally substituted by fluorine, chlorine, bromine, cyano or
Cl-C4-alkoxy-carbonyl), represents C2-C6-alkenylthio (which is optionally
substituted by fluorine, chlorine, bromine, cyano, nitro, Cl-C3-alkylthio or
Cl-C4-alkoxycarbonyl), C3-C6-alkinyloxy, C3-C6-alkinylthio or represents the
radical -S(O)p-R6 where,

p represents the numbers 1 or 2 and

R6 represents Cl-C4-alkyl (which is optionally substituted by fluorine,
chlorine, bromine, cyano or Cl-C4-alkoxy-carbonyl), C3-C6-alkenyl,
C3-C6-alkinyl, Cl-C4-alkoxy, Cl-C4-alkoxy-C,-C4-alkylamino, Cl-C4-
alkylamino, di-(C,-C4-alkyl)-amino, phenyl or represents the radical
-NHoR7 where

R7 represents Cl-Cl2-alkyl (which is optionally substituted by
fluorine, chlorine, cyano, Cl-C4-alkoxy, Cl-C4-alkylthio, Cl-C4-
alkylsulfinyl, Cl-C4-alkylsulfonyl, Cl-C4-alkyl-carbonyl, Cl-C4-
alkoxy-carbonyl, Cl-C4-alkylamino-carbonyl or di-(CI-C4-alkyl)-
amino-carbonyl), represents C3-C6-alkenyl (which is optionally
substituted by fluorine, chlorine or bromine), C3-C6-alkinyl,
C3-C6-cycloalkyl, C3-C6-cycloalkyl-CI-C2-alkyl, phenyl-CI-C2-
alkyl (which is optionally substituted by fluorine, chlorine, nitro,
cyano, Cl-C4-alkyl, Cl-C4-alkoxy or Cl-C4-alkoxy-carbonyl),
represents benzhydryl or represents phenyl (which is optionally
substituted by fluorine, chlorine, nitro, cyano, Cl-C4-alkyl,

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trifluoromethyl, C~-C4-alkoxy, C~-C2-fluoroalkoxy, C~-C4-
alkylthio, trifluoromethylthio or C,-C4-alkoxy-carbonyl),

R4 and/or R5 furthermore represent phenyl or phenoxy, represent C~-C4-
alkyl-carbonylamino, C,-C4-alkoxy-carbonylamino, C,-C4-alkylamino-
carbonyl-amino, di-(C,-C4-alkyl)-amino-carbonylamino, or represent the
radical -Co-R5 where

R3 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-alkylamino
or di-(C,-C4-alkyl)-amino (each of which are optionally
substituted by fluorine and/or chlorine),

R4 and/or R5 furthermore represent trimethylsilyl, thiazolinyl, C,-C4-alkyl-
sulfonyloxy, di-(C,-C4-alkyl)-aminosulfonylamino or represent the radical

-CH=N-R9 where

R9 represents optionally fluorine-, chlorine-, cyano-, carboxy-, C,-C4-
alkoxy-, C,-C4-alkylthio-, C,-C4-alkylsulfinyl-, or C,-C4-
alkylsulfonyl-substituted C,-C6-alkyl, represents optionally fluorine- or
chlorine- substituted benzyl, represents optionally fluorine- or
chlorine-substituted C3-C6-alkenyl or C3-C6-alkinyl, represents
optionally fluorine-, chlorine-, bromine-, C,-C4-alkyl-, C,-C4-alkoxy-,
trifluoromethyl-, trifluoromethoxy- or trifluoromethylthio-substituted
phenyl, represents optionally fluorine- and/or chlorine-substituted
C,-C6-alkoxy, C3-C6-alkenyloxy, C3-C6-alkinyloxy or benzyloxy,
represents amino, C,-C4-alkylamino, di-(C,-C4-alkyl)-amino,
phenylamino, C,-C4-alkyl-carbonyl-amino, C,-C4-alkoxy-
carbonylamino, C,-C4-alkyl-sulfonylamino or represents optionally
fluorine-, chlorine-, bromine- or methyl-substituted

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- 10 -
phenylsulfonylamino,

furthermore


R'~ 12
R3 represents the radical I H~R

. R"


in which

R'~ represents hydrogen or C,-C4-alkyl,

R~ and Rl2 are identical or different and each represent hydrogen, fluorine,
chlorine, bromine, nitro, cyano, C,-C4-alkyl (which is optionally substituted
by fluorine and/or chlorine), Cl-C4-alkoxy (which is optionally substituted
by fluorine and/or chlorine), carboxy, C,-C4-alkoxy-carbonyl,
dimethylaminocarbonyl, C~-C4-alkylsulfonyl or di-(C~-C4-alkyl)-
aminosulfonyl;

furthermore


R3 represents the radical R'3~3R14



in which

lS R'3 and R'4 are identical or different and each represent hydrogen, fluorine,

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.

chlorine, bromine, nitro, cyano, 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



S R3 represents the radical [~
N R16



in which

R'5 and Rl6 are identical or different and each represent hydrogen, fluorine,
chlorine, bromine, nitro, cyano, Cl-C4-alkyl (which is optionally substituted
by fluorine and/or chlorine), C,-C4-alkoxy (which is optionally substituted
by fluorine and/or chlorine), represents Cl-C4-alkylthio, Cl-C4-alkylsulfinyl
or Cl-C4-alkylsulfonyl (each of which is optionally substituted by fluorine
and/or chlorine), represent aminosulfonyl, mono-(C ,-C4-alkyl)-
aminosulfonyl, represent di-(C,-C4-alkyl)-aminosulfonyl or C,-C4-alkoxy-
carbonyl or dimethylaminocarbonyl;

1 5 furthermore


R3 represents the radical R'7~3R'~



in which

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R~7 and Rl3 are identical or different and each represent hydrogen, fluorine,
chlorine, bromine, C,-C4-alkyl (which is optionally substituted by fluorine
and/or bromine), C,-C4-alkoxy (which is optionally substituted by fluorine
and/or chlorine), represents C,-C4-alkylthio, C~-C4-alkylsulfinyl or C~-C4-
alkylsulfonyl (which are optionally substituted by fluorine and/or chlorine),
or represent di-(C,-C4-alkyl)-aminosulfonyl;

furthermore


R
R3 represents the radical {~R2o



in which

R'9 and R20 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), Cl-C4-alkoxy (which is optionally substituted
by fluorine and/or chlorine), Cl-C4-alkylthio, Cl-C4-alkylsulfinyl or C~-C4-
alkylsulfonyl (each of which are optionally substituted by fluorine and/or
chlorine), di-(CI-C4-alkyl)-amino-sulfonyl, Cl-C4-alkoxy-carbonyl or
dimethylaminocarbonyl, and

A represents oxygen, sulfur or the grouping N-ZI where

Z~ replesents hydrogen, C~-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), Cl-C4-alkyl-carbonyl, Cl-C4-alkoxy-carbonyl or di(CI-C4-alkyl)-
aminocarbonyl;

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furtherrnore


R2l
R3 represents the radical {~L~R22
y1


in which

R2~ and R22 are identical or different and each represent hydrogen, C,-C4-
S alkyl, halogen, C,-C4-alkoxy-carbonyl, C~-C4-alkoxy or C,-C4-
halogenoalkoxy,

Y' represents sulfur or the grouping N-R23 where

R23 represents hydrogen or C,-C4-alkyl;

fiurthermore


R26
10 R3 represents the radical ~R25

R24



in which

R24 represents hydrogen, C,-C4-alkyl, benzyl, pyridyl, quinolinyl or phenyl,

R25 represents hydrogen, halogen, cyano, nitro, C,-C4-alkyl (which is

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.
~ - 14 -
optionally substituted by fluorine and/or chlorine), C,-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.

Furtherrnore, the invention preferably provides sodium, potassium, magnesiurn, calcium,
ammoniurn, C,-C4-alkyl-ammonium, di-(C,-C4-alkyl)-ammonium, tri-(C,-C4-alkyl)-
ammonium, tetra-(C,-C4-alkyl)-ammonium, tri-(C,-C4-alkyl)-sulfonium, C5- or C6-
cycloalkyl-ammoniurn and di-(C,-C2-alkyl)-benzyl-ammonium salts of the compoundsof the formula (I) in which Ql, Q2, Q3, R', R2 and R3 each have the preferred meanings
given above.

The invention in particular provides compounds of the forrnula (I) in which

Ql represents oxygen or sulfur,

Q2 represents oxygen or sulfur,

Q3 represents oxygen or sulfur,

15 R' represents respectively optionally fluorine-, chlorine-, cyano-, methoxy- or
ethoxy-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, represents
respectively optionally fluorine-, chlorine- or bromine-substituted propenyl,
butenyl, propinyl or butinyl, represents methoxy, ethoxy, n- or i-propoxy, n-, i-,
s- or t-butoxy, methylamino, ethylarnino, n- or i-propylamino, n-, i-, s- or
t-butylarnino, dimethylamino or diethylarnino, represents respectively optionally
fluorine-, chlorine-, bromine-, methyl- or ethyl-substituted cyclopropyl,
cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclobutylmethyl,
cyclopentylmethyl or cyclohexylmethyl, or represents respectively optionally
fluorine-, chlorine-, bromine-, cyano-, methyl-, trifluoromethyl- or methoxy-
substituted benzyl or phenyl,

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R2, in the case where Q3 r~rese~ oxygen, represents cyano-, carboxy-, fluorine-,
chlorine-, bromine-, methyl-, ethyl-, n- or i-propyl, n-, i-, s- or t-butyl-,
trifluoromethyl-, methoxy-, ethoxy-, n- or i-propoxy-, n-, i-, s- or t-butyloxy-,
difluoromethoxy-, trifluoromethoxy-, chlorodifluoromethoxy-, acetyl-,
propionyl-, methoxycarbonyl-, ethoxycarbonyl-, methylthio-, ethylthio-,
cyclopentyl-, cyclohexyl-, phenyl- or benzyl-substituted phenyl, and, in the case
where Q3 represents sulfur, represents optionally cyano-, carboxy-, fluorine-,
chlorine-, bromine-, methyl-, ethyl-, n- or i-propyl-, n-, i-, s- or t-butyl-,
trifluoromethyl-, methoxy-, ethoxy-, n- or i-propoxy-, n-, i-, s- or t-butyloxy-,
difluoromethoxy-, trifluoromethoxy-, chlorodifluoromethoxy-, acetyl-, proponyl-,methoxycarbonyl-, ethoxycarbonyl-, methylthio-, - ethylthio-, cyclopentyl-,
cyclohexyl-, phenyl- or benzyl-substituted phenyl,

~R5
R3 represents the radical ~
~,~4



in which

R4 represents fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl,
trifluoromethyl, methoxy, ethoxy, n- or i-propoxy, n or i-butoxy,
difluoromethoxy, trifluoromethoxy, 2-chloro-ethoxy, 2,2,2-trifluoro-ethoxy,
1,1,2,2-tetrafluoro-ethoxy, 1,1,2,2,2-pentafluoro-ethoxy, 2-methoxy-ethoxy,
methylthio, ethylthio, n- or i-propylthio, n- or i-butylthio, 2-fluoro-ethylthio,
allyloxy, propargyloxy, methylsulfinyl, ethylsulfinyl, methylsulfonyl,
ethylsulfonyl, dimethylaminosulfonyl, diethylaminosulfonyl, N-methoxy-N-
methylaminosulfonyl, phenyl, phenoxy, methoxycarbonyl, ethoxycarbonyl,
n- or i-propoxycarbonyl, and

R5 represents hydrogen, fluorine, chlorine, bromine, methyl, ethyl or

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- 16 -
trifluoromethyl;

furthermore



R3 represents the radical CH ~5




in which

Rl~ represents hydrogen,

Rll represents fluorine, chlorine, bromine, methyl, methoxy, difluoromethoxy,
trifluoromethoxy, ethoxy, methoxycarbonyl, ethoxycarbonyl, methylsulfonyl
or dimethylaminosulfonyl and

Rl2 represents hydrogen;

1 0 furthermore


R3 represents the radical Ro~




in which

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- 17 -
R replcsell~s methyl, ethyl, n- or i-propyl, or


R26 RX
R3 represents the radical J~ I

R24



in which

R24 represents methyl, ethyl, n- or i-propyl, phenyl or pyridyl,

R25 represents hydrogen, fluorine, chlorine or bromine,

R26 represents fluorine, chlorine, bromine, methoxycarbonyl or ethoxycarbonyl.

The abovementioned general or preferred radical definitions apply both to the end
products of the formula (I) and, correspondingly, to the precursors or intermediates
required in each case for the plepaldtion. These radical definitions can be combined
10 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 straight-chain or branched, even in combination with hetero atoms, as in alkoxy,
alkylthio or alkylamino, even if this is not explicitly stated.

15 Halogen generally represents fluorine, chlorine, bromine or iodine, preferably fluorine,
chlorine or bromine, in particular fluorine or chlorine.

Using, for example, 2-trifluoromethoxy-phenylsulfonyl isocyanate and 4-ethyl-5-(2-
fluoro-phenoxy)-2,4-dihydro-3H-1,2,4-triazol-3-one as starting materials, the course of

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- 18 -
the reaction in the process (a) according to the invention can be illustrated by the
following scheme:

o ,~ O-CF3

[~ ' ~ H_N)~N--C2Hs ~SO c NJ~N c2Hs
~F~l C~



Using, for example, 2-ethylthio-benzenesulfonamide and 2-chlorothio-carbonyl-4-
cyclopropyl-5-(4-cyano-phenoxy)-2,4-dihydro-3H-1,2,4-triazol-3-one as starting5 materials, the course of the reaction in the process (b) according to the invention can
be illustrated by the following scheme:



~50 Cl ~ [~SO, NH N~ ~


~CN (~CN

Using, for example, N-methoxycarbonyl-2-methoxy-benezenesulfonamide and 4-methyl-
5-phenylthio-2,4-dihydro-3H-1,2,4-triazol-3-one as starting materials, the course of the
reaction in the process (c) according to the invention can be illustrated by the following
10 scheme:


[~ N=~ 3 NH =
SO2-NH-COOCH3 C6Hs S--CsH5

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19
Using, for example, 2-chloro-6-methyl-ben7~n~sulfonyl chloride, 4-allyl-5-(4-chloro-
phenylthio)-2,4,-dihydro-3H-1,2,4-triazol-3-one and sodium cyanate as starting
materials, the course of the reaction in the process (d) according to the invention can
be illustrated by the following scheme:


~ H_NJ~N--CH2-cH=cH2 ~0 J~--NJ~N--CH2-CH=CH2
Cl ~3~C NaCI S~C


5 A general definition of the tri~olin(ethi)ones to be used as starting materials in the
processes (a), (c) and (d) according to the invention for plt;pa~ g compounds of the
formula (I) is given by the formula (II).

In the formula (II), Q', Q3, R' and R2 each preferably or in particular have those
meanings which have already been indicated above, in connection with the description
10 of the compounds of the formula (I) according to the invention, as preferred or
particularly preferred for Q', Q3, R' and R2.

The triazolin(ethi)ones of the general formula (II) are known and/or can be prepared by
processes known per se (cf. EP 507171, DE 3924571, US 4098896, J. Org. Chem. 50
(1985), 1295-1298).

lS The triazolin(ethi)ones of the formula (II) are obtained when (thio)carbazates of the
general formula (IX)
Q1
1~
NH O
NH2 R2 (L~

in which

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- 20 -
Q' is as defined above and

R27 represents alkyl (preferably methyl or ethyl)

are reacted with imino(di/thio)carbonic diesters of the general formula (X)


2 R2
~ a3 ~Q3 / (X)

S in which

Q3, Rl and R2 are each as defined above,

if appropriate in the presence of a diluent such as, for example, N,N-dimethyl-
forrnamide, and if a~lopliate in the presence of a reaction auxiliary such as, for
- example, hydrochloric acid or pivalic acid, at temperatures between 0~C and 100~C,
10 and the resulting compounds of the general formula (XI)



N O
N~NH
Q ~
R (X~)



in which

Q', Q3, R', R2 and R~7 are each as defined above

are cyclocondensed - if a~ropliate after interrnediate isolation - if appropriate in the

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- - 21 -
presence of a diluent such as, for example, toluene, and if a~ o~liate in the presence
of a reaction auxiliary such as, for example, sodium hydroxide or sodium methoxide,
at temperatures between 20~C and 150~C (cf. the Plel)ald~ion Examples).

The triazolin(ethi)ones of the general formula (II) can also be obtained by reacting
5 triazolin(ethi)ones of the general formula (IIa)



Q3 R2 ~a)


in which

Ql, Q3 and R2 are each as defined above

with alkylating agents of the general formula (XII)

X'-R' (XII)

10 in which

R' is as defined above and

X' represents halogen or the grouping -O-SO2-R',

if applopliate in the presence of an acid acceptor such as, for example, potassium
carbonate, and if a~propliate in the presence of a diluent such as, for example,15 acetonitrile, at tempelalules between 0~C and 100~C (cf. the preparation examples).

Furthermore, the triazolin(ethi)ones of the general formula (II) can also be obtained by
reacting triazolin(ethi)ones of the general formula (IIb)

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- 22 -


H--N ~N_R
~ 3(~) M


in which

Q~, Q3 and Rl are each as defined above - however Q3 preferably represents sulfur -
and

M represents a metal equivalent, preferably sodium or potassium,

5 with diazonium salts of the general formula (XIII)

N2-R2~ XO (~I)

in which

R2 and X are each as defined above,

in the presence of a catalyst such as, for example, copper(II) chloride and in the
presence of water and, if appropriate, an organic diluent such as, for example,
10 methylene chloride, at tempeld~ul~s between 0~C and 50~C (cf. the Ple~ ion
Examples).

A general definition of the sulfonyl iso(thio)cyanates further to be used as starting
materials in the process (a) according to the invention for p~e~ g compounds of the
formula (I) is given by the formula (III).

15 In the formula (III), Q2 and R3 each preferably or in particular have those me~ning~
which have already been indicated above, in connection with the description of the

-
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- 23 -
compounds of the formula (I) according to the invention, as preferred or particularly
- preferred for Q2 and R3.

The starting materials of the formula (III) are known and/or can be prepared by
processes 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 triazolin(ethi)one derivatives to be used as starting materials
in the process (b) according to the invention for prepaling compounds of the general
formula (I) is given by the formula (IV). In the formula (IV), Q~, Q2, Q3, R~ and R2
each preferably or in particular have those meanings which have already been indicated
above, in connection with the description of the compounds of the formula (I), as
preferred or as particularly preferred for Q', Q2, Q3, R' and R2; here, Z preferably
represents fluorine, chlorine, bromine, methoxy, ethoxy, benzyloxy, phenoxy, halogeno-
or nitro-phenoxy, in particular methoxy, phenoxy or 4-nitro-phenoxy.

The starting materials of the formula (IV) have not been disclosed in the literature; as
novel compounds, they also form part of the subject matter of the present application.

The novel compounds of the formula (IV) are obtained when triazolin(ethi)ones of the
general formula (II)
Q'
N N
N =(
Q3 R2 (II)

20 in which

Q', Q3, R' and R2 are each as defined above

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-

- - 24 -
are reacted with carbonic acid derivatives of the general formula (XIV)
Z CQ2ZI ~V)




in which

Q2 and Z are each as defined above and
S Z' represents halogen (in particular chlorine), alkoxy (in particular methoxy),
aralkoxy (in particular benzyloxy) or aryloxy (in particular phenoxy),

if applol,liate in the presence of an acid acceptor such as, for example, sodium hydride
or potassium hydride, sodium hydroxide or potassiurn hydroxide, sodium t-butoxide or
potassium t-butoxide, and if appropliate in the presence of a diluent such as, for
example, tetrahydrofuran or dimethoxyethane, or in a two-phase system of water and
an organic solvent such as, for example, methylene chloride or chloroform at
temperatures between 0~C and 100~C.

A general definition of the sulphonamides further to be used as starting materials in the
process (b) according to the invention for ple~ g compounds of the general formula
(I) is given by the formula (V). In the formula (V), R3 preferably or in particular has
those meanings which have 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 plepa~ g compounds of the formula (I)

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.
- - 25 -
is given by the formula (VI). In the formula (VI), Q2 and R3 each preferably or in
particular have those me~ning~ which have already been indicated above, in connection
with the description of the compounds of the formula (I), as being preferable orparticularly preferable for Q2 and R3; here, Z preferably represents fluorine, chlorine,
5 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
10 process (d) according to the invention for plep~illg compounds of the formula (I) is
given by the formula (VII). In the formula (VII), R3 preferably or in particular has
those meanings which have 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 in15 particular represents chlorine.

The starting materials of the formula (VII) are known and/or can be prepared by
methods known per se. This also applies to the starting materials and intermediates of
the formulae (VIII) to (XIV).

The processes (a), (b), (c) and (d) according to the invention for the plepa alion of the
20 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
25 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

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propionitrile; arnides, for example dimethylformamide, dimethyl~cet~mide and
N-methylpyrrolidone, and also dimethyl sulfoxide, tetramethylene sulfone and
hexamethylphosphoric triamide.

As reaction auxiliaries and/or as acid acceptors in the processes (a), (b), (c) and (d)
5 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 tert-butoxide and potassium tert-
10 butoxide, and also basic nitrogen compounds, such as trimethylamine, triethylamine,tripropylamine, tributylamine, diisobutylamine, dicyclohexylamine,
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-di~z~bicyclo-[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 +100~C, preferably at temperatures
20 between 0~C and +80~C.

The processes (a), (b), (c) and (d) according to the invention are generally carried out
under atmospheric ples~ule. 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
25 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 carried out in a suitable
diluent in the presence of an acid acceptor, and the reaction mixture is stirred for a

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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 methods (cf. the Preparation Examples).

Salts of the compounds of the general formula (I) according to the invention can be
5 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 app,opliate solvent, for example methylene chloride, acetone, tert-butyl methyl
ether or toluene, and adding an al~plopliate base. The salts can then - if desired after
prolonged stirring - be isolated by concentration or filtration with suction.

10 The active compounds according to the invention can be used as defoliants, desiccants,
haulm killers and, especially, as weed-killers. By weeds, in the broadest sense, 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.

15 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,
20 Solanum, Rorippa, Rotala, T in~1erni~, Lamium, Veronica, Abutilon, Emex, Datura,
Viola, Galeopsis, Papaver, Centaurea, Trifolium, Ranunculus and Taraxacum.

Dicotyledonous crops of the genera: Gossypium, Glycine, Beta, Daucus, Phaseolus,Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica,
Lactuca, Cucumis and Cucurbita.

25 Monocotyledonous weeds of the ~enera: Echinochloa, Setaria, Panicum, Digitaria,
Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus, Avena, Cyperus,

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Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleocharis,
Scirpus, Paspalum, Ischaemum, Sphenoclea, Dactyloctenium, Agrostis, Alopecurus and
Apera.

Monocot,vledonous crops of the ~enera: Oryza, Zea, Triticum, Hordeum, Avena,
5 Secale, Sorghum, Panicum, Saccharum, Ananas, Asparagus and Allium.

However, the use of the active compounds according to the invention is in no wayrestricted 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
weeds, for example on industrial terrain and rail tracks, and on paths and squares with
10 or without tree pl~ntin~ Equally, the compounds can be employed for controlling
weeds in perennial crops, for example forests, decorative tree plantings, orchards,
vineyards, citrus groves, nut orchards, banana plantations, coffee plantations, tea
plantations, rubber plantations, oil palm plantations, cocoa plantations, soft fruit
pl~nting~ and hopfields, in lawns, turf and pasture-land, and for the selective control of
15 weeds in annual crops.

The compounds of the formula (I) according to the invention are particularly suitable
for the selective control of monocotyledonous and dicotyledonous weeds in
monocotyledonous and dicotyledonous crops, both pre-emergence and post-emergence.

To a certain extent, the compounds of the formula (I) also have fungicidal activity, for
20 example against Pyricularia oryzae in rice.

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.

25 These formulations are produced in a known manner, for example by mixing the active

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compounds with extenders, that is liquid solvents and/or solid carriers, optionally with
the use of surf~ct~ntc, 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
5 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 pekoleum fractions,
mineral and vegetable oils, alcohols, such as butanol or glycol as well as their ethers
10 and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or
cyclohexanone, skongly polar solvents, such as dimethylformamide and dimethyl
sulfoxide, as well as water.

Suitable solid carriers are:

for example ammonium salts and ground natural minerals, such as kaolins, clays, talc,
15 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
20 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,
alkylsulfonates, alkyl sulfates, arylsulfonates as well as protein hydrolysates; suitable
dispersing agents are: for example lignin-sulfite waste liquors and methylcellulose.

25 Tackifiers 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

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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, m~ng~nese, boron,
S copper, cobalt, molybdenum and zinc.

The formulations in general comprise between 0. l and 9S per cent by weight of active
compound, preferably between O.S 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,
lO ready-to-use formulations or tank mixes being possible.

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
15 diclofop-methyl, fenoxaprop-ethyl, fluazifop-butyl, haloxyfop-me~.hyl and qui_alofop-
ethyl; a_inones, such as chloridazon and norflurazon; carbamates, such as
chlorpropham, desmedipham, phenmedipham and propham; chloroacetanilides, such asalachlor, acetochlor, butachlor, met~7~cll10r, metolachlor, pretilachlor and propachlor;
dinitro~nilin~s, such as oryzalin, pendimethalin and trifluralin; diphenyl ethers, such as
20 acifluorfen, bifenox, fluoroglycofen, fomesafen, halosafen, lactofen and oxyfluorfen;
ureas, such as chlorotoluron, diuron, fluometuron, isoproturon, linuron and
methaben7thi~711ron; hydroxyl~min~s, such as alloxydim, clethodim, cycloxydim,
sethoxydim and tralkoxydim; imidazolinones, such as ima_ethapyr, im~7~methabenz,im~7~pyr and ima_aquin; nitriles, such as bromoxynil, dichlobenil and ioxynil;
25 oxyacetamides, such as mefenacet; sulfonyl-ureas, such as amidosulfuron, bensulfuron-
methyl, chlorimuron-ethyl, chlorsulfuron, cinosulfuron, metsulfuron-methyl,
nicosulfuron, primisulfuron, pyrazosulfuron-ethyl, thifensulfuron-methyl, triasulfuron
and tribenuron-methyl; thiocarb~m~tes, such as butylate, cycloate, ~ te, EPTC,

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esprocarb, molinate, prosulfocarb, thiobencarb and triallate; triazines, such as atrazine,
cyanazine, ~im~7ine, simetryne, terbutryne and terbutylazine; triazinones, such as
hexazinone, metamitron and metribuzin; others, such as aminotriazole, benfuresate,
bentazone, cinmethylin, clomazone, clopyralid, defenzoquat, dithiopyr, ethofumesate,
S fluorochloridone, glufosinate, glyphosate, isoxaben, pyridate, quinchlorac, quinmerac,
sulphosate and tridiphane.

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

10 The active compounds can be used as such, in the form of théir 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
15 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 S g
and 2 kg per ha.

20 The p~ lion and use of the active compounds according to the invention can be seen from the examples below.

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Plcp~dlion examples:

Example 1



2 - NH ~OCH
0~


(Process (b))

1.8 g (5 mmol) of 2-phenoxythiocarbonyl-4-methyl-5-(2-methoxy-phenoxy)-2,4-dihydro-
3H-1,2,4-triazol-3-one are added to a mixture of 1.1 g (5 mmol) of 2-trifluoromethyl-
benzenesulfonamide, 0.8 g (5 mmol) of 1,8-diazabicyclo-5.4.0]-undec-7-ene (DBU) and
50 ml of acetonitrile, and the reaction mixture is stirred at about 20~C for about
15 hours. The mixture is then concentrated using water pump vacuum and the residue
is taken up in methylene chloride, washed with lN hydrochloric acid, dried with
sodium sulfate and filtered. The filtrate is concentrated using water pump vacuum, the
residue is digested with diethyl ether and the resulting crystalline product is isolated by
filtration with suction.

1.3 g (53 % of theory) of 2-(2-trifluoromethyl-phenylsulfonyl-aminothiocarbonyl)-4-
methyl-5-(2-methoxy-phenoxy)-2,4-dihydro-3H- 1 ,2,4-triazol-3-one of melting point
143~C are obtained.

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Example 2


S~~ - NH N N
N =~ OCH3
o~3




(Process (d))

A mixture of 2.2 g (10 mmol) of 4-methyl-5-(2-methoxy-phenoxy)-2,4,-dihydro-3H-
1,2,4-triazol-3-one, 2.6 g (10 mmol) of 2-trifluoromethoxy-benzenesulfochloride, 1.3 g
5 (20 mmol) of sodium cyanate and S0 ml of acetonitrile is heated at reflux for 15 hours.
The mixture is then concentrated using water pump vacuum and the residue is taken up
in methylene chloride, washed with lN hydrochloric acid, dried with sodium sulfate
and filtered. The solvent is carefully distilled off from the filtrate using water pump
vacuum.

2.7 g (56 % of theory) of 2-(2-trifluoromethoxy-phenylsulfonyl-aminocarbonyl)-4-methyl-5-(2-methoxy-phenoxy)-2,4-dihydro-3H-1,2,4-triazol-3-one are obtained as a
crystalline residue of melting point 154~C.

By the methods of Examples 1 and 2 and in accordance with the general description of
the preparation processes according to the invention, it is also possible to prepare, for
15 example, the compounds of the formula (I) listed in Table 1 below.

Q2 Q'

S~2 - NH , N

N=(
Q3 R2 (I)

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Table 1: Examples of compounds of the formula (I)

Ex. Ql Q2 Q3 Rl R2 R3 Melting
No point (~C)
3 O O O CH3 ~cl ~cooc~, 175

4 O O O CH3 ~CI ~cOOcH, 130

O O O CH3 ~ [~cooa1, 164

6 O o O CH3 ~cl ~OCHF2 147

7 0 0 0 CH3 "Q ~OCHf2 143

8 O O O CH3 ~cl [~OCHF2 172

9 O O O CH3 ~CI ~CH3 130


0 o O CH3 ~ [~CH3 150

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Table 1: (Continued)

Ex. Ql Q2 Q3 Rl R2 R3 Melting
No. point (~C)
11 0 0 0 CH3 ~cl [~CH3 140


12 O O O CH3 ~cl ~CF3 205

3 ~ ~ ~ CH3 ~ CF3 210

14 O o o CH3 ~cl [~CF3 210

O O O CH3 COOCH3 ~OCHF2 150


16 O ~ ~ CH3 COOCH3 ~CH3 158


17 O ~ ~ CH3 COOCH3 [~CF3 185

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Table 1: (Continued)
Ex. Ql Q2 Q3 Rl R2 R3 Melting
No. point (~C)
18 O O O CH3 ~ [~OCHF2 142


\~SCH, ~

O O O CH3 ~ ~CF3 180

21 O o o CH3 ~OCH3 ~COOCH, 140


22 O ~ ~ C2H5 COOCH3 ~Br 132


23 O ~ ~ C2H5 ~g3OCH3 ~CF3 130


24 O ~ ~ C2H5 COOCH3 coOCH3 134


O O O C2H5 ~cl ~Br 145

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Table 1: (Continued)

Ex Ql Q2 Q3 Rl R2 R3 Melting
No. point (~C)
26 O O O C2H5 ~,cl ~Br 100

27 O o o CH3 ~c~ ~COOCH, 128

28 O O O CH3 ~ ~ ~COOCH~ 154

29 O o o CH3 ~cc~, I~COOCH, 153

O O O CH3 '13~ ~cOOCH, 120

31 O ~ ~ CH3 ~a1, ~CF3 145

O O O CH3 ~OC2H~ ~CF3 125

33 O O O CH3 '13~ 0~CF3 I go

34 O O O CH3 ~cl ~F 185

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Table 1: (Continued)
Ex. Q 1 Q2 Q3 R I R2 R3 Melting
No. point (~C)
3 5 0 0 0 CH3 ~1 ~COOCH, 150


36 O O O CH3 ~3 ~CF, ~06


37 O O O CH3 cl CH3 142


38 o O O CH3~[~lOCH3 C~ Cl 160


39 O O O C2H5cl ~cOOc,H, 145


O o O C2H5'13~ ~cooc~ 117

41 0 0 0 CH3 ~ CF3 180


42 o O O C2Hs~CI ~CooC,H, 133

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Table 1: (Continued)

Ex. Q I Q2 Q3 R I R2 R3 Melting
No. point (oC~
43 O O O C2H5 ~3~ ~coocy, 145

44 O O O C2Hs ~CI ~cOOc,H, 142

O O O C2Hs ~,cl ~CF3 130

46 0 0 0 ~0~ CF3 136


~ O C2E~5 ~ ~CF~ 162


48 0 ~ ~ CH3 COOCH,SC2H5 125


49 o O O CH3 c~SC2H~ 152
\~ ~

O o O CH3 ~ [~SC7Hs 128

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Table 1: (Continued)
Ex. Ql Q2 Q3 Rl R2 R3 Melting
No. point (~C)
51 O ~ ~ CH3 cl ~cooc~, 199


CH3

52 0 0 0 C83 ~[~ ~CF3 182


CH3
53 O O O CH3 cl ~ F 192
'1~1 ~

CH3

54 0 0 0 C2H5 Cl @~COOclH, 130


CH3
55 0 0 0 C~85 ~[~ r 150


CH3

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Table 1: (Continued)

No. Q2 Q3 Rl R2 R3 M It
56 0 0 0 ~ ~ ~CH3 200

CH3 Cl

5~ ~ ~ ~ ~'~ ~ 0~cH, 165


CH3
S8 O O o f~ Cl [~cooc2H~ 168


CH3
59 0 0 0 ~ ~ ~CF3 170


CH3
0 0 0 ~ Cl ~COOCH, 180


CH,

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Table 1: (Continuecl)

Ex. Ql Q2 Q3 Rl R2 R3 Melting
No. point (~C)
61 0 0 0 ~ ~ [~CH3 14~


6~ 0 0 0 ~ ~[~3 [~C~SI~ 137


63 0 0 0 ~ ~ CF3 190


64 0 0 0 ~ CH3 177


65 0 0 0 ~ Cl ~CO~ 172


66 0 0 0 ~ F~CF3 120


67 0 0 0 ~ OCH3 ~COOCH, 150

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Table 1: (Continued)

Ex. Ql Q2 Q3 Rl R2 R3 Melting
No. point (~C)
68 O ~ ~ CH3 OCH3 ~COOCH, 1 78


69 O ~ ~ CH3 ~C2H5 ~COOCH~ 147
\~ ,

O O O CH3 ~[~Hs ~CF~ 175


71 0 0 0 CH3~H3 0~CF3 196


72 O O O CHOCH3 [~CH3 180


73 O O O CH3~Hs ~CH3 152


74 ~ O O C2H5 OCH3 146
~C~H,

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Table 1: (Continued)

Ex. Ql Q2 Q3 Rl R2 R3 Melting
No. point (~C)
O O O C2H5 ~[~H3 ~C~3 12


O O O C2H5 ~3H3 ~Br 126


~ ~ ~ C2HS ~H5 - ~Br 125


O O C2Hs ~3H3 ~COOCH,


79 0 0 0 ~,~ ~lH3 ~COOC,H, 135
~,

0 0 0 ~ ~H5 0~c~

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Table 1: (Continued)

No. Q2 Q3 Rl R2 R3 Melting
81 o o o ~ ~5 ~coocH, 141


82 o o o C2Hs~[~Hs ~COOCH~ 1 s8


83 0 0 0 ~OCH3 ~CH3 102


84 0 0 0 ~~Hs @~CH, 106


8~ O o O ~ ~


86 0 0 0 ~ ~H5 [~CH3 146

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Table 1: (Continued)
Ex. Ql Q2 Q3 Rl R2 R3 Melting
No point (~C)
87 O ~ ~ CH3 OCH3 ~SC2Hs 1 34


O O CH3 ~[~H5 ~SC,H,


89 o o o CH3 ~H~ ~F 150


O O O CH3 ~Hs ~F 145


~ COOCH3 ~OCHF2 127


92 O O O ~ COOCH, 0~r 135


93 ~ ~ O ~ COOCH3 0~CF3 1 40

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Table 1: (Continued)
Ex. Ql Q2 Q3 Rl R2 R3 Melting
No. point (~C)
O O O ~,~ ~,~H3 ~OCHF2


o o o ~ ~ ~OC11F,


96 0 0 0 ~ ~Hs ~OCHF2 132


97 o O O C2H5 ~ ~ 162


CH3

98 O O O ~ Cl [~CH3 180

(Na salt)
CH3

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Table 1: (Continued)
Ex. Ql Q2 Q3 Rl R2 R3 Melting
No. point (~C)
99 ~ O O ~ ~ ~Br 155


CH3

100 0 0 0 ~ CF3 180

(Na salt)


101 O O O CH3 p ~ 3 198
~3

102 O o O ~ ~ 0~CF3 140


103 o O O ~ ~ ~ ~Br 168

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Table 1: (Continll~cl)

Ex. Q I Q2 Q3 R I R2 R3 Melting
No point (~C)
104 O O O ~ ~ ~co~ 140


105 O O O CH3 ~ ~COOCH, 150
~.


106 O O O CH3 p [~OCF3 155
~3

107 O o o CH3 p ~cH3 133
~3 Cl




108 O o o CH3 p [~SC2H5 164
~1

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Table 1: (Continued)

Ex. Q I Q2 Q3 R I R2 R3 Melting
No point (~C)
109 O o O CH3 p ~ 215
~3

110 O O O C2H5 ~ ~ooc~ 157
~3


~1

112 O O O ~ ~cH, [~CF3 145


113 O O O ~ ~CH, [~OCHFz 50

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.
- 51 -
Table 1: (Continued)

Ex. Ql Q2 Q3 Rl R2 R3 Melting
No. point (~C)
114 O O O ~ ~ ' ~c~ 168

115 O O O CH3 OCH3 ~COOCH, 130

~ (Na salt)

116 O O O CH3 ~Hs ~c~ 130

~ (Na salt)

7 O O O CH3 ~Hs [~CF3 180

(Na salt)

118 O O O C H OCH3 [~coocH, 125

~J (Na salt)

119 0 0 0 ~ OCH3 ~COOC,H, 173

(Na salt)

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Table 1: (Continued)

Ex. Q I Q2 Q3 R I R2 R3 Melting
No. point (~C)
120 O O O ~,~ ~H5 ~cooc 135

1~ (Na salt)

121 O O O ~ ~Hs ~COOCH,

~ (Na salt)

122 O O O C2H5 ~H5 ~COOCH,

l~ (Na salt)

123 O O O ~ \~CH, [~CF3 170

(Na salt)
124 O O O CH3 ~a

125 O O O C2H5 ~a [~

126 O o o CH3 ~CH~ [~F 203

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Table 1: (Continued)

Ex. Ql Q2 Q3 Rl R2 R3 Melting
No. point (~C)
127 O O O ~ ~ [~


128 O O O ~ F ~OCHF2 136




~3
130 o O O ~ F [~CH3 145


131 O O O C2H5 ~ ~ 13 8


132 O O O ~ F ~CF3 142

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Table 1: (Continued)

Ex. Ql Q2 Q3 Rl R2 R3 Melting
No. point (~C~
133 0 0 0 ~ ~ ~OCHF,


~ O O CH3 ~ ~ 150




~ F

136 0 0 0 ~ ~ [~CH3 124


137 0 0 0 ~ ~ ~ 90

~F
13 8 0 0 0

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Table 1: (Continued)

Ex. Q I Q2 Q3 R I R2 R3 Melting
No point (~C)
139 0 0 0 ~ F ~CH3 116



~ F ~ccoyl, 122


141 0 0 0 ~,~ ~3~ ~ 147


142 0 0 0 ~ F ~CF3 154


143 O O O ~ F ~COOCH, 168


144 O O O ~ ~ [~ 150

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Table 1: (Continl-e-l)

Ex. Ql Q2 Q3 Rl R2 R3 Melting
No. point (~C)


~er

~ ~ O CH3 ~ (~CF~ ~4



147 0 0 0 H ~3H, [~CF3 92


8 O O O CH3 ~H3 ~cooc,HT 120


O O O CH3 ~H3 ~CH3 174


O H3 @~cooc~ 122

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Table 1: (Continued)

Ex Q I Q2 Q3 R I R2 R3 Melting
No. point (~C)
I S 1 O S ~ CH3 ~W ~


152 o S ~ CH3 OCH3 ~OCHF2 142
W




153 o o S CH3 COOCH3. COOCH3 218


154 O o S CH3 COOCH3COOCH3 1 60
~3 (Isopropyl-
salt)

155 O O S f~ COOCH3~OCH3 114


156 O O S CH3 ~3 3 ~ 3 156

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Table 1: (Continued)

Ex. Ql Q2 Q3 Rl R2 R3 Melting
No. point (~C)
157 O O S CH3 COOCH3 [~CF3 200


158 O O S CH3 COOCH3 [~OCF3 198


159 O O S CH3 COOCH3 ~OCHF2 1 89


160 O O S CH3 COOCH3 [~3~ 3 180


161 O O S CH3 COOCH3 ~OCH3 1 80


162 O O S CH3 COOCH3 ~OC2H, 192


163 O O S CH3 COOCH3 ~SC2H5 204

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Table 1: (Continued)

Ex. Q I Q2 Q3 R I R2 R3 Melting
No. point (~C)
164 O O S CH3 ~ ~'~~


165 O O CH ~ ~oc~, 179


166 O O O CH3 ~H~ ~ 190


O C~3 ~H~ ~OCHF,


168 O O S ~ ~ ~cooo~ 176


169 O O S ~ ~ ~~CHF2 141


170 O o S CH3 ~ ~cooo~ 154

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Table 1: (Continued)

Ex. Q 1 Q2 Q3 R I R2 R3 Melting
No. point (~C)
171 o o S CH3 ~3 [~OCHF2
172 0 0 S CH3 ~3 ~OCF3 148


173 0 0 S CH3 ~ CH3 1 80

174 0 ~ S CH3 \~3 [~ 3 1 65

O O S CH3 ~3 ~OCH3 141


176 0 0 S CH3 \ 3 0~CH3 92

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Table 1: (Continued)

Ex. Q I Q2 Q3 R I R2 R3 Melting
No. point (~C)
177 0 O S CH3 ~0 ~OC2Hs 119


178 o o S CH3 ~3 ~sc2H5 136


179 0 O S CH3 ~3 ~ 124


180 O O S ~ COOCH3 [~CH3 133

OC3H,-n

181 0 0 0 CH3 ~3 OCH3


O O CH3 ~3H3 [~OCH,

OC,H,~

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Sta~ matenals of the folmula (II):

Example (II-1)


H--N N_CH3
N~
0 ~

Cl ~-1)

At 20~C, a solution of 105 g (0.69 mol) of phenyl - calba~e in 175 ml of
dimethylformamide is added dropwise with stirring to a mixture of 205 g (0.69 mol) of
5 bis-(4-chloro-phenyl) methyliminocarbonate and 250 ml of dimethylformamide. The
reaction mixture is stirred at 20~C for 16 hours and then, using water pump vacuum
(about 15 mbar), slowly heated to about 100~C to distill off most of the
dimethylformamide. The remainder of the volatile components is then removed at about
150~C using oil pump vacuum (about 1 mbar). At about 0.1 mbar/200~C, the residueaffords 25 g of a sublimate which yields, after digestion with isopropanol, 15 g (10 %
of theory) of 5-(4-chloro-phenoxy)-4-methyl-2,4-dihydro-3H-1,2,4-triazol-3-one of
melting point 196~C.

Example (II-2)


H_NJ~N--CH3
N = ( l CH3




~-[~
(II-2)


9.7 g (77 mrnol) of dimethyl sulfate are added dropwise with stirring to a mixture of
15.4 g(70 mmol) of 5-(2-methoxy-phenoxy)-2,4-dihydro-3H-1,2,4-triazol-3-one,10.6 g

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(77 mmol) of potassium carbonate and 100 ml of acetonitrile which has been heated to
50~C. The reaction ~ e is stirred at 50~C for 15 hours and then cooled to room
temperature (about 20~C) and filtered off with suction. The filtrate is evaporated to
dryness using water pump vacuum, and the residue is digested with diethyl ether. The
5 resulting crystalline product is isolated by filtration with suction.

13 g (84 % oftheory) of 5-(2-methoxy-phenoxy)-4-methyl-2,4-dihydro-3H- 1,2,4-tri~ol-
3-one of melting point 105~C are obtained.

Example (II-3)


H--N N_CH3
N=~


--[~coOCH3 (II-3)

30.2 g (0.20 mol) of methyl 4-amino-benzoate are suspended in 100 ml of water and
treated with 50 g of 37 % strength hydrochloric acid (0.5 mol of HCI). At 0~C to-10~C, a solution of 14.1 g (0.20 mol) of sodium nitrite in 30 ml of water is added
dropwise with vigorous stirring and cooling. At about 10~C, the resulting di~onium
salt solution is added dropwise to a solution of 34 g (0.20 mol) of the potassium salt
of 5-mercapto-4-methyl-2,4-dihydro-3H-1,2,4-tri~ol-3-one24.6 g (0.30 mol) of sodium
acetate and 100 mg of copper(II) chloride in 250 ml of water, causing the reaction to
foam with nitrogen being released. Subsequently, the reaction is admixed with 300 ml
of methylene chloride and the mixture is stirred at 20~C for a further 12 hours. The
white solid that has formed is isolated by filtration with suction and washed
successively with water, isopropanol and diethyl ether. A second product fraction is
20 obtained by drying and conce~ hlg (water pump vacuum) the methylene chloride
phase, stirring the residue with isopropanol and filtration with suction.

Total yields: 27.9 g (52.5 % of theory) of 5-(4-methoxycarbonyl-phenylthio)-4-methyl-


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2,4-dihydro-3H-1,2,4-triazol-3-one of melting point 196~C.

By the methods of Examples (II-1) to (II-3), it is also possible to prepare, for example,
the compounds of the formula (II) listed in Table 2 below.

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H_NJ~N_R'

Q3 R2 (II)


Table 2: Examples of compounds of the forrnula (II)

Ex. - Ql Q3 Rl R2 Melting point
No. (~C)

II~ O S CH3 COOCH3 188



II-S O S CH3 COOH 252



II-6 O S CH3 ~COOCH3 137


II-7 O S CH3 ~COOH 182


II-8 O S CH3 ~ 293
COOH

II-9 o S "~ COOCH3 175
~3 '

II- 10 0 0 H OCH3 207

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Table 2: (Continued)
Ex. Ql Q3 R R2 Meltingpoint
No. (~C)


II- 1 1 O S ~ \~31


II-12 O S CH3 ~3


II-13 O O CH


II-14 O O CH3 ~CI


II-l 5 O o CH3 ~3~CI


II-16 O O CH3 ~

SCH3

II-17 O O CH3 ~CH3
SCH3

II-18 O O CH3


CH3

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Table 2: (Continued)
Ex. Ql Q3 R R2 Meltingpoint
No. (~C)


~I- 19 0 ~ CH3
~3

II-20 O O CH3 \~CH3
Cl
II-2 1 O ~ CH3 F

\[~F

II-22 O ~ CH3 F


F

II-23 O O ~
~3

II-24 0 0 ~ ~CH3
Cl

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Startin~ materials of the formula (IV):

Example (IV-l)

s ~
HsC6_ ~--N N-- 3
N =( OCH3
0~
11




(IV-I)

A solution of 5.7 g (33 mmol) of phenyl chlorothioformate in 30 ml of methylene
chloride is added dropwise with stirring to a mixture of 6.6 g (30 mmol) of 5-(2-
methoxy-phenoxy)-4-methyl-2,4-dihydro-3H-1,2,4-triazol-3-one, 30 ml of water, 1.3 g
(33 mmol) of sodium hydroxide and a spatula tip of triethylbutylammonium chloride
(TEBA), and the reaction mixture is sitrred at 20~C for 15 hours. The organic phase is
then separated off, dried with sodium sulfate and filtered. The filtrate is concentrated,
the residue is digested with diethyl ether and the resulting crystalline product is isolated
by filtration with suction.

7 g (65 % of theory) of 5-(2-methoxy-phenoxy)-4-methyl-2-phenoxythiocarbonyl-2,4-
dihydro-3H-1,2,4-triazol-3-one of melting point 138~C are obtained.

By the method of Example (IV-1), it is possible to prepare, for example, the
compounds of the formula (IV) listed in Table 3 below.

Q2 Q'
--N J~ N--R

Q3 R2 (~

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Table 3: Examples of compounds of the fo~nula (IV)
Ex. Q Q2 Q3 Rl R2 z Melting point
No. (~C)


IV-2 O O ~ CH3 ~3OCH3 H C O


IV-3 O O O CH3 ~ HsC6O


IV 1 0 0 O CH3 ~ H5C6O


IV-5 O O O CH3 ~ HSC6O

IV-6 O O S CH3 ~3 H5C6O


IV-7 O O O ~ ~3~cl HsC6O


IV-8 o O S ~ ~3 H5C6O


IV-9 O O O ~ HsC6O
'~3

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Table 3: Examples of compounds of the formula (IV)
Ex. Ql Q2 Q3 Rl R2 z Melting point
No. (~C)

IV- 10 O ~ ~ CH3 HsC6O


IV-I I O ~ ~ CH3 H3CO
~, ,.

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Application 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 l"ep~dlion of active compound, 1 part by weight of active
compound is mixed with the stated amount of the solvent, the stated amount of
emulsifiers is added and the concentrate is diluted with water to the desired
concentration.

Seeds of the test plants are sown in normal soil. After about 24 hours, the soil is
watered or sprayed with the active compound preparation. It is advantageous to keep
the amount of water per unit area constant. The concentration of active compound in
the prepaldlion is of no importance, only the amount of active compound per unit area
being decisive.

After three weeks, the degree of damage to the plants is rated in % damage in
comparison with the development of the untreated control. The figures denote:

0 % = No effect (like untreated control)
100 % = Total destruction

In this test, the compounds of P~e~alalion Examples 9, 15, 16, 17, 21, 23, 24, 66, 129,
131, 132, 135, 137 and 140, for example, exhibit strong activity against weeds.


Table A: Pre-emergence test/greenhouse r

-
Compound of Application Alo- Bromus PoaSetaria Cheno- Portu- Sina- Sola- ~
preparation rate(g/ha) pecurus podium laca pisexample No. rq

9 500 80 - 70 80 70 80 100 80 c

1 5 125 80 - 95 90 70 90 9S 9S ~ ~
16 125 9S 95 95 95 95 100 loo 95
17 125 95 95 95 95 80 9S loO 95 ~ ~
2 1 1 25 95 95 95 95 9S 9S 95 95 O
~.23 250 90 9S 95 9S 9S 9S 90 9S
24 . 250 95 95 95 95 9~ 95 90 9S
66 125 80 9S 90 90 9S 95 80 95
129 125 90 95 80 90 95 95 95 95
13 1 125 90 90 90 90 100 90 80 9S



Table A: (Continued)

x
Compoundof Application Alo- Bromus PoaSetaria Cheno- Po~ Sina- Sola- ~
preparation rate (g/ha)pecun~s podium laca pis num
exampleNo. ~,

132 125 - 95 95 95 95 9S 9S 9S ~D O
135 12S 90 90 80 80 80 80 80 90
137 125 95 95 95 70 80 95 90 95
140 125 9S 9S 9S 80 70 80 80 95

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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

S To produce a suitable prepalation of active compound, 1 part by weight of active
compound is mixed with the stated amount of the solvent, the stated amount of
emulsifiers 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 active compound
10 ple~ ion 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 applied in 1000 l of water/ha.
After three weeks, the degree of damage to the plants is rated in % damage in
comparison with the development of the untreated control.

15 The figures denote:

0 % = No effect (like untreated control)
100 % = Total destruction

In this test, the compounds of Plel)a~lion Examples 4, 5, 13, 15, 16, 17, 21, 23, 24,
66, 128, 129, 131 and 137, for example, exhibit strong activity against weeds.

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o ~ ~ ~ ~ O~ O~ ~ O~ ~ O o


p~ o 't' ~ o~ ~ O~ o

4 ~' ~' _ ~ o O o O

,= , , o -O~ ~ ~ ~ ~ v' O


~ o o O~ o O ~ ~ o o


o O~ ~ ~ ~ ~ O~ o o o

u~
o ~ Ov~ o o o ~ o o o o

r
o
._ ~

c .5 ~ o ~O ,,,

04
' ~0
~o ~ o Z

E o ' x

m




Table B: fContinued)


CompoundofApplication Alo- Bromus Setaria Ama- Datura Poly- Sola- ~pq
preparationrate (g/ha) pecurus ranthus gonum num o
example No. ~. D

128 250 95 60 - 100 - 95 loo
129 125 60 50 70 100 - 9S 100 ~ r

131 30 90 70 70 - 9S 50 90 l '
137 125 70 80 - 90 70 95 9S

Representative Drawing