Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
~~~r~~.3
The invention relates to new sulphonylamino-
carbonyltriazolinones having substituents which are
bonded via sulphur, to a variety of processes for their
preparation, and to their use as herbicides.
It is known that certain substituted amino-
carbonyliruidazolinones, such as, for example, 1-isobutyl-
aminocarbonyl-2-imidazolidinone (isocarbamid), have
herbicidal properties (cf. R. Wegler, Chemie der
Pflanzenschutz-and and Schadlingsbekampfungsmittel
[Chemistry of Plant Protection Agents and Pesticides],
Volume 5, p. 219, Springer-Verlag, Berlin-Heidelberg-New
York, 197?). However, the action of this compound is not
satisfactory in all resgects.
The new sulphonylaminocarbonyl-triazolinones
having substituents which are bonded via sulphur, of the
formula (I) '
0
R3-S02-NI-i-CO-N~N-R1 ( I )
~S(0)n-R2
in which
n represents the numbers 0, 1 or 2,
Rx represents hydrogen, hydroxyl or amino, or repre
seats an optionally substituted radical from the
series comprising alkyl, alkenyl, alkinyl, cyclo
alkyl, aralkyl, aryl, alkoxy, alkenyloxy, al 1
ky -
Le A 27 156 - I -
~~?~13?
amino, cycloalkylamino and dialkylamino,
RZ represents an optionally substituted radical from
the series comprising alkyl, alkenyl, alkinyl,
cycloalkyl, cycloalkenyl, aralkyl and aryl, and
R3 represents an optionally substituted radical from
the series comprising alkyl, aralkyl, aryl and
heteroaryl,
as well as salts of compounds of the formula ( I ) , have
now been found.
The new sulphonylaminocarbonyltriazolinones
having substituents which are bonded via sulphur, of the
general formula (I), are obtained when
a) triazolinones of the general formula (II)
0
~ (II)
HN~N-R1
~S(O)n-R2
in which
n, R~ and RZ have the abovementioned meanings,
are reacted with sulphonyl isocyanates of the
general formula (III)
R3-S02-N~~=p (III)
in which
R3 has the abovementioned meaning,
if appropriate in the presence of a diluent, or when
b) triazolinone derivatives of the general formula (IV)
Le A 27 156 _ z
Z-CO-N~N-R1 (zv)
~S(OJn-R2
in which
n, Rl and RZ have the abovementioned meanings and
Z represents halogen, alkoxy, aralkoxy or aryloxy,
are reacted with sulphonamides of the general
formula (V)
R3-S02-NHZ (V)
in which
R3 has trxe abovementioned meaning,
if appropriate in the presence of an acid acceptor
and if appropriate in the presence of a diluent, or
when
c) triazolinones of the general formula (II)
O
u II
HN~N-R1 ( )
~S(0)n-R2
in which
nr R~ and RZ have the abovementioned meanings,
are reacted with sulphonamide derivatives of the
Le A 27 156
general formula (VI)
R3-S02-NH-C0-Z (vI)
in which
R~ has the abovementioned meaning 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,
and, if desired, salts are formed by customary
methods from the compounds of the formula (I)
prepared by process (a), (b) or (c).
The new sulphonylaminocarbonyltriazolinones
having substituents which are bonded via sulphur, of the
general formula (I), and their salts are distinguished by
a powerful herbicidal activity.
Surprisingly, the new compounds of the
formula (I) have a considerably better herbicidal action
than the herbicide 1-isobutylaminocarbonyl-2-imidazol-
idinone (isocarbamid), which is known and has a similar
structure.
The invention preferably relates to compounds of
the formula (I) in which
n represents the numbers 0, 1 or 2,
R1 represents hydrogen, hydroxyl or amino, or repre
sents C1-C6-alkyl which is optionally substituted by
fluorine, chlorine, bromine, cyano, C~-C4-alkoxy,
Ca-Ca-alkylcarbonyl or C1-C4-alkoxy-carbonyl, or
represents C3-C6-alkenyl or C3-Cs-alkinyl, each of
which is optionally substituted by fluorine, chlor-
Le ~, 27 156 _ q,
ine and/or bromine, or represents C3-Cs-cycloalkyl
which is optionally substituted by fluorine, chlor-
ine, bromine and/or C1-C4-alkyl, or represents
phenyl-C1-C3-alkyl which is optionally substituted by
fluorine, chlorine, bromine, cyano, vitro, Cl-C4-
alkyl, trifluoromethyl, C1-Cb-alkoxy and/or C1-C4-
alkoxy-carbonyl, or represents phenyl which is
optionally substituted by fluorine, chlorine,
bromine, cyano, vitro, C,-C4-alkyl, trifluoromethyl,
C1-C4-alkoxy, fluorine- and/or chlorine-substituted
C1-C3-alkoxy, C1-C4-alkylthio, fluorine- and/or
chlorine-substituted C1-C3-alkylthio, Cl-C4-alkylsul-
phinyl, Cl-C4-alkylsulghonyl and/or Cl-C4-alkoxy-
carbonyl, or represents C1-Cfi-alkoxy which is option-
ally substituted by fluorine, chlorine, cyano,
phenyl, C1-C4-alkoxy or C~-C4-alkoxy-carbonyl, or
represents C3-C,;-alkenyloxy, ar represents Cl-C4-
alkylamino which is optionally substituted by
f luorine, cyano, C1-C4-alkoxy or C~-Ca-alkoxy-
carbonyl, ar represents C3-C6-cycloalkylamino or di-
( Cl-C4-alkyl ) -amino,
R2 represents Cl-Cfi-alkyl which is optionally substi-
tuted by fluorine, chlorine, bromine, cyano, C3-C6-
cycloalkyl, C1-C4-alkoxy or C1-C4-alkoxycarbonyl, or
represents C3-C6-alkenyl or C3-C6-alkinyl, each of
which is optionally substituted by fluorine, chlor-
ine and/or bromine, or represents C3-C6-cycloalkyl
which is optionally substituted by fluorine, chlor-
ine, bromine and/or C1-C4-alkyl, or represents
cyclohexenyl, or represents phenyl-C~-C3-alkyl which
Le A 27 156 - 5 -
is optionally substituted by fluorine, chlorine,
bromine, cyano, vitro, C1-C4-alkyl, trifluoromethyl,
C1-C4-alkoxy and/or C1-C,,-alkoxycarbonyl, or repre-
sents phenyl which is optionally substituted by
fluorine, chlorine, bromine, cyano, vitro, C
alkyl, trifluoromethyl, C1-C4-alkoxy, fluorine-
and/or chlorine-substituted C1-C3-alkoxy, C1-C4-
alkylthio, fluorine- and/or chlorine-substituted
C1-C3-alkylthio, C1-G4-alkyl-sulphinyl, Cl-C4-alkyl-
sulphonyl and/or C1-C4-alkoxy-carbonyl, and
R5
R3 represents the group ~ ~ where
R9
R4 and RS are identical or different and represent
hydrogen, fluorine, chlorine, bromine, iodine,
vitro, C1-C6-alkyl (which is optionally substituted
by fluorine, chlorine, bromine, cyano, carboxyl,
C1-C4-alkoxycarbonyl, C1-C4-alkylamino-carbonyl, di-
( C1-C,,-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-C,,-alkylsulphonyl,
di- ( C1-C4-alkyl ) -aminosulphonyl , C3-Cs-cycloalkyl or
phenyl ) , or represent CZ-Cs-alkenyl (which is option-
ally substituted by fluorine, chlorine, bromine,
cyano, Cl-C4-alkoxy-carbonyl, carboxyl or phenyl ) , or
represent Cy-C6-alkinyl (which is optionally substi-
tuted by fluorine, chlorine, broanine, cyano, C1-C4-
alkoxy-carbonyl, carboxyl or phenyl), or represent
Le A 27 156 - S -
~p~~~~?
C1-C4-alkoxy (which is optionally substituted by
fluorine, chlorine, bromine, cyano, carboxyl, C~-C~-
alkoxy-carbonyl, C~-C4-alkoxy, C~-C4-alkylthio, C1-C4-
alkylsulphinyl or C1-C4-alkylsulphonyl ) , or represent
Cl-C4-alkylthio (which is optionally substituted by
fluorine, chlorine, bromine, cyano, carboxyl, C1-C4-
alkoxy-carbonyl, C1-C4-alkylthio, C1-C4-alkylsulphinyl
or Cl-C4-alkylsulphonyl ) , or represent C3-C6-alkenyl-
oxy (which is optionally substituted by fluorine,
chlorine, bromine, cyano or C1-C,~-alkoxy-carbonyl},
or represent C2-Cs-alkenylthio (which is optionally
substituted by fluorine, chlorine, bromine, cyano,
nitro, C1-C3-alkylthio or Gl-C,,-alkoxycarbonyl ) ,
C3-G6-alkinyloxy or C3-C6-alkinylthio, or represent
the radical -S(O)p-R6 where
p represents the numbers 1 or 2 and
R6 represents C1-C,,-alkyl (which is optionally
substituted by fluorine, chlorine, bromine,
cyano ar C1-C4-alkoxy-carbonyl ) , C3-C6-alkenyl,
C3-Cs-a7.kinyl, C1-C4-alkoxy, C1-C4-alkoxy-C1-C4-
alkylamino, Cl-C,,-alkylamino, di- ( Cl-C4-alkyl ) -
amino or phenyl, or represents the radical
-NHOR' where
R' represents C1-C1z-alkyl (which is optionally
substituted by fluorine, chlorine, cyano,
C1-C,,-alkoxy, C1-C4-alkylthio, C1-C~,-alkylsul
phinyl, Cl-C4-alkylsulphonyl, Cl-C4-alkyl
carbonyl, Cl-C~-alkoxycarbonyl, C1-C4-alkyl
amino-carbonyl or di-(Cl-C4-alkyl}-amino
carbonyl), or represents C3-C6-alkenyl (which
Le A 27 156 - 7 -
~~~~~~~
is optionally substituted by fluorine,
chlorine or bromine ) , C3-Cs-alkinyl, C3-Cs-
cycloalkyl, C3-Cs-cycloalkyl-C1-CZ-alkyl,
phenyl-C1-CZ-alkyl (which is optionally
substituted by fluorine, chlorine, vitro,
cyano, C1-Ca-alkyl, Cl-C4-alkoxy or C1-C4-
alkoxy-carbonyl), or represents benzhydryl,
or represents phenyl (which is optionally
substituted by fluorine, chlorine, vitro,
cyano, Ci-C4-alkyl, trifluoromethyl, C1-C,,-
alkoxy, C1-C2-fluoroalkoxy, Cl-C4-alkylthio,
trifluoromethylthio or C~-C4-alkoxycarbonyl),
R4 and/or RS furthermore represent phenyl or phenoxy,
ar represent Cl-C4-alkylcarbonylamino, C1-C4
alkoxycarbonyiamino, C1-C~-alkylamino-carbonyl
amino or di-(C1-C4-alkyl)-amino-carbonylamina, or
represent the radical -CO-RB where
Rs represents C1-Cs-alkyl, Cl-Cs-alkoxy, C3-Cs
cycloalkoxy, C3-Cs-alkenyloxy, Cl-C4 alkylthio,
C1-C4-alkylamino, Cl-C4-alkoxyamino, Cl-C,,_
alkoxy-Cl-C4-alkyl-amino or di- ( Cl-Ck-alkyl ) -
amino (each of which is optionally substi-
tuted by fluorine and/or chlorine),
R" and/or RS furthermore represent trimethylsilyl,
thiazolinyl, C1-C4-alkylsulphonyloxy or di-(Ci-C4
alkyl)-aminosulphonylamino, or represent the
radical -CH=N-R9 where
R9 represents C~-Cs-alkyl which is optionally
substituted by fluorine, chlorine, cyano,
carboacyl, C1-C~-alkoxy, C1-C4-alkylthio, Ci-C4
Le A 27 156 -- 8
alkylsulphinyl or C1-Ca-alkylsulphonyl, or
represents benzyl which is optionally sub-
stituted by fluorine or chlorine, or repre-
sents C3-Cs-alkenyl or C3-Cs-alkinyl, each of
which is optionally substituted by fluorine
or chlorine, or represents phenyl which is
optionally substituted by fluorine, chlorine,
bromine, C1-C4-alkyl, C1-C4-alkoxy, trifluoro-
methyl, trifluoromethoxy or trifluoromethyl-
thic, or represents C,-Cs-alkoxy, G3-Cs-alken-
oxy, C3-Cs-alkinoxy or benzyloxy, each of
which is optionally substituted by fluorine
and/or chlorine, or represents amino, C1-C4-
alkylamino, di-(C1-C4-alkyl)-amino, phenyl-
amino, C1-C4-alkyl-carbonyl-amino, C1-C4--
alkoxy-carbonylamino or C1-C4-alkyl-sulphonyl-
amino, or represents phenylsulphonylamino
which is optionally substituted by fluorine,
chlorine, bromine or methyl,
furthermore
R12
-CH '
R3 represents the radical R10 Rii ~ where
R1° represents hydrogen or C1-C~-alkyl,
Rli and Rlz are identical or different and represent
hydrogen, fluorine, chlorine, bromine, vitro,
cyano, C1-C4-alkyl (which is optionally substi
tuted by fluorine and/or chlorine), Ca-Ca-alkaxy
(which is optionally substituted by fluorine
and/or chlorine), carboxyl, Cl-C4-alkoxy-carbonyl,
Le A 27 156 ~ g -
dimethylaminocarbonyl, C1-C4-alkylsulphonyl or di-
(Ca-C4-alkyl)-aminosulphonyl; furthermore
R3 represents the radical R13 ~ f ~ R14 where
Rl3and R1" are identical or different and represent
hydxogen, fluorine, chlorine, bromine, vitro, cyano,
C1-C~-alkyl (which is optionally substituted by
fluorine and/or chlorine) or Ci-C4-alkoxy (which is
optionally substituted by fluorine and/or chlorine);
furthermore R15
R3 represents the radical / ~ where
R16
R15 and R16 are identical or different and represent
hydrogen, fluorine, chlorine, bromine, vitro,
cyano, C1-C4-alkyl {which is optionally
substituted by fluorine and/or chlorine), C~-C~-
alkoxy (which is optionally substituted by
fluorine and/or chlorine), or represents C1-C4-
alkylthio, C1-C4-alkylsulphinyl or C1-C4-alkyl-
sulphonyl (each of which is optionally substi-
tuted by fluorine and/or chlorine) , or represents
ami.nosulphonyl, mono-(Cl-C4-alkyl)-aminosulphonyl,
or represents di-{C1-Cs-alkyl)-aminosulphonyl or
C1-C4-alkoxycarbonyl or dimethylaminocarbonyl;
furthermore
R3 represents the radical R17 ~ ( ~Rlg where
w N'
Le A 27 156 _ 10
Rl' and RI8 are identical or different and represent
hydrogen, fluorine, chlorine, bromine, C1-C4-alkyl
(which is optionally substituted by fluorine and/or
bromine), Cl-C4-alkoxy (which is optionally substi-
toted by fluorine and/or chlorine), or represent
C1-C4-alkylthio, C1-C,,-alkylsulphinyl or Cl-Ca-alkyl-
sulphonyl (which is optionally substituted by
fluorine and/or chlorine), or represent di-(C1-C4-
alkyl)-aminosulphonyl;
furthermore
R29
R3 represents the radical _~2o where
R1~ and RZ° are identical or different and represent
hydrogen, fluorine, chlorine, bromine, cyano,
vitro, C,-C4-alkyl (which is optionally substi-
I5 toted by fluorine and/or chlorine}, Cl-C4-alkoxy
(which is optionally substituted by fluorine
and/or chlorine), C1-C,,-alkylthio, C~-C4-alkylsul-
phinyl or C1-C4-alkylsulphonyl (which is option-
ally substituted by fluorine and/or chlorine),
di- ( Ci-C,,-alkyl ) -amino-sulphonyl, C1-C,,-alkoxy-car-
bonyl or dimethylaminocarbonyl, and
A represents oxygen, sulphur or the group N-Z1 where
Z1 represents hydrogen, Cl-C4-alkyl (which is
optionally substituted by fluorine, chlorine,
bromine or cyano), C3-C6-cycloalkyl, ben~yl,
phenyl (which is optionally substituted by
L~e A 2 7 15 6 - 11
~~~~1~°~
fluorine, chlorine, bromine or nitro), C1-Ca-
alkylcarbonyl, C1-Ca-alkoxy-carbonyl or di-
( CmCa-alkyl ) -aminocarbonyl;
furthermore
R22
R3 represents the radical ~22 where
Z
R21 and R22 are identical or different and represent
hydrogen, C,-Ca-alkyl, halogen, C1-Ca-alkoxycar-
bonyl, Cl-Ca-alkoxy or Cl-Ca-halogenoalkoaty,
Y1 represents sulphur or the group N-R2a where
Ras represents hydrogen or C~-Ca-alkyl;
furthermore
R26
R3 represents the radical '~, where
N~N~ 2 5
R
X24
RZa represents hydrogen, Ci-Ca-alkyl, benzyl, pyri-
dyl, quinolinyl or phenyl,
R25 represents hydrogen, halogen, cyano, nitro,
C1-Ca-alkyl (which is optionally substituted by
fluorine and/or chlorine), C1-Ca-alkoxy (which is
optionally substituted by fluorine and/or
chlorine), dioxolanyl or C1-Ca-alkoxy-carbonyl
and
RZS represents hydrogen, halogen or C1-Ca-alkyl;
furthermore
Le A 27 156 - 12 -
R3 represents one of the groups listed below,
H3C0 ~~ ' H3C
S~'N-C~H9 ; NHS CH2GF3
02
0
0
The invention furthermore preferably relates to
sodium salts, potassium salts, magnesium salts, calcium
salts, ammonium salts, C1-C4-alkyl-ammonium salts,
di-(C1-C4-alkyl)-ammonium salts, tri-(C1-C4-alkyl)-ammonium
salts, CS- or Cs-cycloalkyl-ammonium salts and di-(Cl-CZ-
alkyl)-benzyl-ammonium salts of compounds of the
formula ( I ) in which n, R1, RZ and R3 have the meanings
indicated above as being preferred.
In particular, the invention relates to compounds
of the formula (I) in which
n represents the numbers 0, 1 or 2,
R1 represents hydrogen ar amino, or represents CI-C4
alkyl which is optionally substituted by fluorine,
cyano, methoxy or ethoxy, or represents allyl, or
represents C3-C6-cycloalkyl, or represents benzyl, or
represents phenyl, or represents Cl-C4-alkoxy, or
represents C3-C~-alkenyloxy, or represents C1-C3
alkylamino, C3-C6-cycloalkylamina, or represents di
2 0 ( C1-C3-alkyl ) -amino,
Le A 27 156 - 13 -
~~~~~c~"t~
Rz represents hydrogen, or represents C1-G4-alkyl which
is optionally substituted by fluorine and/or chlor-
ine, methoxy or ethoxy, or represents C3-C4-alkenyl
which is optionally substituted by fluorine and/or
chlorine, or represents C3-C6-cycloalkyl, or repre-
sents benzyl which is optionally substituted by
fluorine, chlorine and/or methyl, and
RS
R3 represents the group ~ where
R'1
R° represents fluorine, chlorine, bromine, methyl,
trifluoromethyl, methoxy, difluoromethoxy,
trifluoromethoxy, 2-chloro-ethoxy, 2-methoxy-
ethoxy, C1-C3-alkylthio, C1-C3-alkylsulphinyl,
C1-C3-alkylsulphonyl, dimethylaminosulphonyl,
diethylaminosulphonyl, N-methoxy-N-methylamino-
sulphonyl, methoxyaminosulphonyl, phenyl, phenoxy
or C1-C3-alkoxy-carbonyl, and
RS represents hydrogen, fluorine, chlorine or
bromine
furthermore
R12
~--~ R12
2d R3 represents the radical -CH~ where
~1 ~0
R1° represents hydrogen,
R11 represents fluorine, chlorine, bromine, methyl,
Le A 27 156 _ 14 -
~~~~~.3~ .
methoxy, difluoromethoxy, trifluoromethoxy,
ethoxy, methoxycarbonyl, ethoxycarbonyl, methyl-
sulphonyl or dimethylaminosulphonyl, and
R12 represents hydrogen;
furthermore
R3 represents the radical ~ I
RO-C S
0
where R represents C1-C4-alkyl, or
0
represents the radical RO-CI
N~N
I
where R represents Cl-C4-alkyl. CH3
Examples of the compounds according to the
invention are listed in Table 1 below - cf. also the
Preparation Examples.
0
R3-S02-NH-CO-N~N-R1
(I)
S(0)n-R2
Le .A 2? 15s - 15 -
Table to Examples of the compounds of the formula (T)
R~ R~ R3 n
F
CH3 /-\ 0
C1
CH3 /~\ 0
COOC2H5
CH3 C2N5 /'\ 0
OCHF'2
CH3 CH2-CH=CHI -\ 0
S02N(CH372
CHO CH3 -\
COOCH3
CH3 CH3 /~\ H2- 0
COOC2H5
CHO C2H5 ~ ~ 0
NON
CH3
Le A 27 156 - 16 -
.
Table 1: (Continuation)
R~ R2 R~ n
CH3 C2H5 ' ~ 0
S OOCH3
CH3 C2H5 / \ 0
J \
C2H5 C2H5 /-\ 0
/ i \
CF3
C2H5 C3H7 0
OCFO
CH3 /~\ H2- 0
OCH2CHZC1
C2H5 /-\. 0
CH(CH312 ~ ~ CON(CH3)2 0
Le A 27 156 - 17 -
Table (Continuation)
1:
R1 R2 R3 n
S02NH2
s
CH3 CH(CH312 ~ 0
SCH(CH312
~
CH3 CHZ-CH=CH2 ~~ 1
S02CH3
C2H5 CH3 ~ 2
~
F
C2H5 C~HS ~-~ 0
Si(CH313
CH3 C2H5 ~ 0
~
-
OCF3
/
C2H5 C3H7 ~\ 0
H2-
CON(CH312
CH3 C2H5 0
~1
~e .~ 27 156 _ lg
~fl~~~:l.~
Tabie 1: (Continuation)
R1 R2 R3 n
Br
CH2 /-\ CH3 / \ 0
OCH2CH2-0CH3
C2H5 \ 0
/
-
r
CHI L I o
NON
CH3
S02N(CH3)2
C2H5 \ 0
/
_
OCHF~
C3H7-n \ H2- 0
/
-
COOCH(CH3)2
\
CH3 C2H5 0
C1
Le A 27 156 - 19 -
~~~~~J~
Table 1: (Continuation)
R1 R2 R3 n
C00C2H5
CHO CH3 \ 0
F2CH0
CH3 C2H5 p
/ ~ \
CH3 -CH2-C=CH / \ p
S
N
0-CH2-CF3
/ \
CH3 C2H5 0
COOCH3
C2H5 I ( 0
NON
i I
0
v
COOCH3
CH3 N'N ~ 0
N~ w
i
Le A 27 156 - 20 -
Table 1: (Continuation)
R1 R2 R3
n
C1
CH3 CHO ~ ~
0
NHS
CON(CHO)Z
CHO COH7 _ \ 0
~
HOC
C2H5 C2Hg ~ 0
~
S OOCHO
COOCHO
~
~
CH2-CH=CH2 C2HS ~
H2-
0
CH2-CH=CH2 CHO ~ f
0
NON
CHO
COOCHO
~
\
OCHO CHO ~
0
S02NCH0(0CH0)
OC2H5 C2H5 0
Le A 27 156 _ 21 _
~~?'~~.~~
Table 1: (Continuation)
R2 R2 R3 n
CH3
OC3Hp CH?-CH=CH2 /~\ 0
OCH3
CH3 CHO /-\ 0
C1
C2H5 / \
CH3
Br
C2H5 / \ 0
CHO
C1
C2H5 C2H5 ~ ~ 0
N'~N
CH3
CH3 CZHS /-\ 0
S02 /-\
Le A 27 156 - 22 -
>~~~
Table 1: (Continuation)
R1 R2 R3 n
OCHF2
CH3 C~H7 f~~ H2- 0
OCH3 CH3 ~ ' 0
S COOCH3
OCH3
OCZHS CH3 f~~ 0
OCH2CH~-C1
OC2H5 C2H5 f'~ 0
F
0-CH2-CH=CH2 C2H5 f-~ 0
CH3 CzHS ~ 0
r CF3
CH3 CH3 0
~'N
Le A27 156 w 23 -
Table 1: (Continuation)
gl g2 g3
n
N(CH31Z CH3 w
I
r
0
S02NH2
CH3 C2H5 0
~N
SOZNH2
OCH3 C2H5 0
CH ~
3 I
S02NH2
0
CH3 C2H5 I I 0
S
0-CF2-CF2C1
OCH2CH2-C1
N(CH312 CH3 0
Ze A 27 156 - 24 -
If, for example, 2,6-difluoro-phenyl isocyanate
and 5-ethyl.thio-4-methoxy-2,4-dihydro-3H-1,2,4-triazol-
3-one are used as starting substances, the course of the
reaction in grocess (a) according to the invention can be
outlined by the following equation:
F 0
S02-N=C=0 + H~N~NiOCHS >
F ~SC2HS
F 0
S02-NH-CO~N~Ni0CH3
F ~SC2H5
If, for example, 2-methylthio-benzenesulphonamide
and 2-chlorocarbonyl-4-dimethylamino-5-propylthio-2,4-
dihydro-3H-1,2,4-triazol-3-one are used as starting
substances, the course of the reaction in process (b)
according to the invention can be outlined by the follow-
ing equation:
SCH3 0
(. ,r°S02-NH2 + C 1-CO~N~N~N ( CH3 ) 2 -°->
'~% (~~ - HC 1
~SC3H7
SCHS 0
~S02-NH-CO~N~N~'N ( CH3 ) 2
~SG3H7
Le A 27 156 - 25 -
If, for example, N-methoxycarbonyl-2-methoxy-
benzenesulphonamide and 5-methylsulphonyl-4-difluoro-
methyl-2,4-dihydro-~H-1,2,4-triazol-3-one are used as
starting substances, the course of the reaction in
process (c) according to the invention can be outlined by
the following equation:
0
OCH3
~ f~t~N~N~'CHF 2
~S02-NH-COOCH3 + ~--~~[
~S02CH3
OCH3 0
-'> ~-S02-NH-CO~N~N~'CHFz
-HOCH3
~S02CH3
Formula (IIj provides a general definition of the
triazolinones to be used as starting substances in
processes (a) and (cj according to the invention for the
preparation of compounds of the formula (Ij.
In Formula ( II ) , n, R1 and RZ preferably, or in
particular, have those meanings which have already been
mentioned above in connection with the description of the
Le A 27 156 - 2~
~~~~~~.3
compounds of the formula (I) according to the invention
as being preferred, or particularly preferred, for n, R1
and R2.
Examples of the starting substances of the
formula (II) are listed in Table 2 below.
0
HN~N~R1
~- ' (II)
~S(0)n-g2
Table 2s Examples of the starting substances of the
formula (II)
R2
n
H CHg 0
CH3 CH3 0
C2H5 CH3 0
C3H7 CH3 0
CH(CHS12 CH
3 0
C9H9 CH3 0
Le A 27 156 _ 27
- ~~8~~~~~
TaL~le 2: (Continuation
R1 R2 n
CH3 0
CH3 C2H5 0
CH3 C3H~ 0
CH3 CH(CH312 0
CH3 CH2-CH=CH2 0
CH3 CH2 ~y~ 0
CH3 CH2-G=CH p
C2H5 G2H5 0
C3H7 G2H5 0
C2H5 , 0
CH2-GH=CH2 C2H5 0
CH2-CHBr-CH2Br G2H~ p
C3H7 0
CH2-CH=CH2 0
Le A 27 156 - 28 -
~fl~~~.3~
Table 2: (Continuation
R1 R2 n
CH(CH3)2 0
C2H5 CH(CH3)2 0
C3H~ CH(CH3)Z 0
CH2-CH=CH2 C3H~ 0
C2H5 C3H7 0
C2H5 -CH2-C=CH 0
CgH7 C3H~ 0
OCH3 CH3 0
OCH3 C2H5 0
Le A 27 156 - 29 -
CA 02029132 2000-09-20
The starting substances of the formula ~II~ are
known and/or can be prepared by processes known per se
(cf. J. Heterocycl. Chem. 15 (1978), pp. 377-384; DE-OS
(German Published Specification) 2,250,572; DE-OS (German
Published Specification) 2,527,676; DE-OS (German
Published Specification) 3,709,574; US Patent 4,098,896;
US Patent 4,110 X32; JP-A-52-125 168).
Formula (III) provides a general definition of
the sulphonyl isocyanates also to be used as starting
substances in process (a) according to the invention for
the preparation of compounds of the formula (I).
In formula ( III ) , R3 preferably, or in particular,
has the meaning which has already been mentioned above in
connection with the description of the compounds of the
formula (I) according to the invention as being pre-
ferred, or particularly preferred, for R3.
Examples of the starting substances of the
formula (III) which may be mentioned are:
2-fluoro-, 2-chloro-, 2-bromo-, 2-methyl-, 2-methoxy-, 2
trifluoromethyl-, 2-difluoromethoxy-, 2-trifluorometh
oxy-, 2-methylthio-, 2-ethylthio-, 2-propylthio-, 2
methylsulphinyl-,2-methylsulphonyl-,2-dimethylaminosul
phonyl-, 2-diethylaminosulphonyl-, 2-(N-methoxy-N
methyl)-aminosulphonyl-, 2-phenyl-, 2-phenoxy-, 2-meth
oxycarbonyl-, 2-ethoxycarbonyl-, 2-propoxycarbonyl- and
2-isopropoxycarbonyl-phenylsulphonyl isocyanate, 2-
fluoro-, 2-chloro-, 2-difluoromethoxy-, 2-trifluorometh-
oxy-, 2-methoxycarbonyl- and 2-ethoxycarbonyl-benzylsul-
phonyl isocyanate, 2-methoxycarbonyl-3-thienyl-sulphonyl
isocyanate, 4-methoxycarbonyl- and 4-ethoxycarbonyl-1-
Le A 27 156 - 30 -
methyl-pyrazol-5-yl-sulphonylisocyanate.
The sulphonyl isocyanates of the formula (ITI)
are known and/'or can be prepared by processes known per
se (cf. US Patent 4,127,405, 4,169,719, 4,3?1,391;
EP-A 7,687, 13,480, 21,641, 23,141, 23,422, 30,139,
35,893, 44,808, 44,809, 48,143, 51,466, 64,322, 70,041,
173,312).
Process (a) according to the invention for the
preparation of the new compounds of the formula ( I ) is
preferably carried out using diluents. Suitable diluents
for this purpose are virtually all inert organic sol-
vents. These preferably include aliphatic and aramatic,
optionally halogenated hydrocarbons, such as pentane,
hexane, heptane, cyclohexane, petroleum ether, benzine,
ligroin, benzene, toluene, xylene, methylene chloride,
ethylene chloride, chloroform, carbon tetrachloride,
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, such as,
for example, acetonitrile and propionitrile, amides, such
as, for example, dimethylformamide, dimethylacetamide and
N-methyl-pyrrolidone, and also dimethyl sulphoxide,
tetramethylene sulphone and hexamethylphosphoric tri-
amide.
In process (a) according to 'the invention, the
reaction temperatures can be varied within a substantial
range. In general, the process is carried out at
he A 27 156 - 31 -
~~~~~.~a
temperatures between 0°C and 150°C, preferably at temper-
atures between 10°C and 00°C.
Process (a) according to the invention is gener-
ally carried out under atmospheric pressure.
For carrying out process (a) according to the
invention, between 1 and 3 moles, preferably between 1
and 2 moles, of sulphonyl isocyanate of the formula (III)
are generally employed per mole of triazolinone of the
formula (II).
The reactants can be combined in any desired
sequence. The reaction mixture is stirred until the
reaction is complete, and the product is isolated by
filtration with suction. In another work-up variant, the
mixture is concentrated, and the crude product which
remains in the residue is crystallized with a suitable
solvent, such as, for example, diethyl ether. The product
of the formula (I), which in this process is obtained in
crystalline form, is isolated by filtration with suction.
Formula (IV) provides a general definition of the
triazolinone derivatives to be used as starting sub
stances in process (b) according to the invention for the
preparation of compounds of the formula (I).
In formula (IV), n, R1 and R2 preferably, or in
particular, have those meanings which have already been
mentioned above in connection with the description of the
compounds of the formula (I) according to the invention
as being preferred, or particularly preferred, for n, R1
and RZ, and
Z preferably represents chlorine, C1-C4-alkoxy, benzyl-
oxy or phenoxy, in particular methoxy or phenoxy.
he A 27 156 - 32 -
r~a
Possible examples of the starting substances of
formula (IV) are the compounds of the formula (IV) to be
prepared from the compounds of the formula (II) listed in
Table 2 and phosgene, methyl chloroformate, benzyl
chloroformate, phenyl chloroformate or dipheny.l
carbonate.
The starting substances of the formula (IV) were
hitherto unknown.
The new triazolinone derivatives of the
formula (IV) are obtained when triazolinones of the
general formula (I2)
0
HN~NiRj (II)
~StO)n-Ft2
in which
n, R1 and RZ have the abovementioned meanings,
are reacted with carbonic acid derivatives of the general
formula (XI)
z-co-zI (xz)
in which
Z has the abovementioned meaning and
Z1 represents a leaving group, such as chlorine,
methoxy, benzyloxy or phenoxy,
if appropriate in the presence of a diluent, such as, far
Le A 2Z 156 _ 33 _
~ ')
~a~~~ ~p~
example, tetrahydrofuran, and if appropriate in the
presence of an acid acceptor, such as, for example,
sodium hydride or potassium tent-butylate, at temper
atures between -20°C and +100°C (cf. also the Preparation
Examples).
Formula (V) provides a general definition of the
sulphonamides also to be used as starting substances in
process (b) according to the invention far the prepar-
ation of compounds of the formula (I).
ZO In formula (V), R3 preferably, or in particular,
has the meaning which has already been mentioned above in
connection with the description of the compounds of the
formula (I) according to the invention as being pre-
ferred, or particularly preferred, for R3.
Examples of the starting substances of the
formula (V) which may be mentioned are:
2-fluoro-, 2-chloro-, 2-bromo-, 2-methyl-, 2-methoxy-, 2-
trifluoromethyl-, 2-difluoromethoxy-, 2-trifluorometh-
oxy-, 2-methylthio-, 2-ethylthio-, 2-propylthio-, 2-
methylsulphinyl-,2-methylsulphonyl-,2-dimethylaminosul-
phonyl-, 2-diethylaminosulphonyl-, 2-(N-methoxy-N-
methyl)-aminosulphonyl-, 2-phenyl-, 2-phenoxy-, 2-meth-
oxycarbonyl-, 2-ethoxycarbonyl-, 2-propoxycarbonyl- and
2-isopropoxycarbonyl-benzenesulphonamide, 2-fluoro-, 2-
chloro-, 2-.difluoromethoxy-, 2-trifluoromethoxy-, 2-
methoxycarbonyl- and 2-ethoxycarbonyl-phenylmethanesul-
phonamide, 2-methoxycarbonyl-3-thioghenesulphonamide, 4-
methoxycarbonyl- and 4-ethoxycarbonyl-1-methyl-pyrazol-
5-sulphonamide.
The sulphonamides of the formula (V) are known
Le A 27 156 - 34 -
and/or can be prepared by processes known per se (cf.US
Patents 4,127,405, 4,169,719, 4,371,391; EP-A 7,687,
13,480, 21,641, 23,141, 23,422, 30,139, 35,893, 44,808,
44,809, 48,143, 51,466, 64,322, 70,041, 173,312).
In process (b) according to the invention, prepar-
ation of the new compounds of the formula (I) is prefer-
ably carried out using diluents. Diluents which are
suitable for this purpose are virtually all inert organic
solvents, for example those which have been indicated
above for process (a) according to the invention.
Acid acceptors which can be employed in pro-
cess (b) according to the invention are all acid-binding
agents which can customarily be used for reactions of
this type. The following are preferably suitable: alkali
metal hydroxides, such as, for example, sodium hydroxide
and potassium hydroxide, alkaline earth metal hydroxides,
such as, for example, calcium hydroxide, alkali metal
carbonates and alkali metal alcoholates, such as sodium
carbonate, potassium carbonate, sodium tert-butylate and
potassium tert-butylate, furthermore aliphatic, aromatic
or heterocyclic amines, for example triethylamine,
trimethylamine, dimethylaniline, dimethylbenzylamine,
pyridine, 1,5-diazabicyclo-[4,3,0]-non-5-ene (DBN), 1,8-
diazabicyclo-[5,4,0]-undec-7-ene (DBU) and 1,4-diazabi-
cyclo[2,2,2]-octane (DABCO).
In process (b) according to the invention, the
reaction temperatures can be varied within a substantial
range. In general, the process is carried out at temper
atures between 0°C and 100°C, preferably at temperatures
between 10°C and 60°C.
Z,e A 27 156 - 35
Cb fx ~ ~
.J
In general, process (b) according to the
invention is carried out under atmospheric pressure.
However, it is also possible to carry out the process
under increased or reduced pressure.
For carrying out process (b) according to the
invention, the specifically required starting substances
are generally employed in approximately equimolar
amounts. However, it is also possible to use one of the
two components employed in each case in a substantial
excess . In general, the reactions are carried out in a
suitable diluent in the presence of an acid acceptor, and
the reaction mixture is stirred for several hours at the
specifically required temperature. In process (b) accord-
ing to the invention, working-up is carried out in each
case by customary methods.
The triazolinones of the formula (TI) to be used
as starting substances in process (c) according to the
invention for the preparation of compounds of the
formula (I) have already been described as starting
substances for process (a) according to the invention.
Formula (VI) provides a general definition of the
sulphonamide derivatives also to be used as starting
substances in process (c) according to the invention far
the preparation of compounds of the formula (I).
In formula (VI), R3 and Z preferably, or in
particular, have those meanings which have already been
mentioned above in connection with the description of the
compounds of the formula (I), or (IV), according to the
invention as being preferred, or particularly preferred,
for R3 and Z .
Le A 27 156 - 36 -
~,~,.~~
Process (c) according to the invention is
preferably carried out using diluents. The same organic
solvents which have been mentioned above in connection
with the description of process (a) according to the
invention are suitable for this purpose.
If appropriate, process (c) is carried out in the
presence of an acid acceptor. The same acid-binding
agents which have been mentioned above in connection with
the description of process (b) according to the invention
are suitable for this purpose.
In process (c) according to the invention, the
reaction temperatures can be varied within a substantial
range. In general, the process is carried out at temper
atures between 0°C and 100°C, preferably at temperatures
between 10°C and 60°C.
In general, process (c) according to the inven-
tion is carried out under atmospheric pressure. However,
it is also gossible to carry out the process under
increased or reduced pressure.
For carrying out process (c) according to the
invention, the specifically required starting substances
are generally employed in approximately equi.molar
amounts. However, it is also possible to use one of the
two specifically employed components in a substantial
excess . In general, the reactions are carried out in a
suitable diluent in the presence of an acid acceptor, and
the reaction mixture is stirred for several hours at the
specifically required temperature. In process (c) accord-
ing to the invention, working-up is carried out in each
case by customary methods.
Le A 27 156 - 37 -
S
y 1 ~ ~ ~ ~,~ :/J
Y ) k .:
For converting the compounds of the formula (I)
into salts, they are stirred with suitable salt formers,
such as, fox example, sodium hydroxide, sodium methylate,
sodium ethylate, potassium hydroxide, potassium methylate
or potassium ethylate, ammonia, isopropylamine, dibutyl-
amine or triethylamine, in suitable diluents, such as,
for example, water, methanol or ethanol. The salts can be
isolated as crystalline products - then if appropriate
after concentration.
The active compounds according to the invention
can be used as defoliants, desiccants, agents for de-
stroying broad-leaved plants 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 undesired. 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 follow
ing plants:
Dicotyledon weeds of the genera: Sinapis,
Lepidium, Galium, Stellaria, Matricaria, Anthernis,
Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus,
Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum,
Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solanum,
Rorippa, Rotala, Lindernia, Lamium, Veronica, Abutilon,
Emex, Datura, Viola, Galeopsis, Papaver, Centaurea,
Trifolium, Ranunculus and Taraxacum.
Dicotyledon cultures of the Genera: Gossypium,
Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum,
Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis,
Le A 27 256 - 38 -
I r~ ~~ ~ oh. ~ ;i~
r l1 a a ~. cy r~
Brassica, Lactuca, Cucumis and Cucurbita.
Monocotyledon weeds of the genera: Echinochloa,
Setaria, Panicum, Digitaria, Phleum, Poa, Festuca,
Eleusine, Brachiaria, holium, Bromus, Avena, Cyperus,
Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis,
Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum,
Sphenoclea, Dactyloctenium, Agrostis, Alopecurus and
Apera.
Monocotyledon cultures of the genera: 0ryza,
ZO Zea, Triticum, Hordeum, Avena, Secale, Sorghum, Panicum,
Saccharum, Ananas, Asparagus and Allium.
However, the use of the active compounds accord
ing 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 combating of weeds, for
example on industrial terrain and rail tracks, and on
paths and squares with or without tree plantings.
Equally, the compounds can be employed for combating
weeds in perennial cultures, for example afforestations,
decorative tree plantings, orchards, vineyards, citrus
groves, nut orchards, banana plantations, coffee plant a-
tions, tea plantations, rubber plantations, oil palm
plantations, cocoa plantations, soft fruit plantings and
hop-fields, on lawn, turf and pasture-land, and for the
selective combating of weeds in annual cultures.
In particular, the compounds of the formula (I)
according to the invention are suitable for selectively
combating monocotyledon and dicotyledon weeds in mono
Le A 27 156 - 39 -
t'~ rig ;x -~. ~ '!~
~~ ~e7 .c c~ .;4. e9 .-,r
cotyledon crops, either using the pre-emergence or the
post-emergence method. They are markedly more effective
than, fox example, isocarbamid.
To a certain extent, the compounds according to
the invention also show fungicidal action, for example
against Pyricularia on 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, suspension-emulsion
concentrates, natural and synthetic materials impregnated
with active compound, and very fine capsules in polymeric
substances.
These formulations are produced in a known
manner, fox examgle 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 andlor 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. As liquid solvents, there are suit-
able in the main: aromatics, such as xylene, toluene or
alkylnaphthalenes, chlorinated aromatics and chlorinated
aliphatic hydrocarbons, such as chlorobenzenes, chloro-
ethylenes 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
Le A 27 156 - 40 -
isobutyl ketone or cyclohexanone, strongly polar sol-
vents, such as dimethylformamide and dimethyl sulphoxide,
as well as water.
As solid carriers there are suitable: for example
ammonium salts and ground natural minerals, such as
kaolins, clays, talc, chalk, quartz, attapulgite, mont
morillonite or diatomaceous earth, and ground synthetic
minerals, such as highly-disperse silica, alumina and
silicates, as solid carriers for granules there are
suitable: fox example crushed and fractionated natural
rocks such as calcite, marble, pumice, sepiolite and
dolomite, as well as synthetic granules of inorganic and
organic meals, and granules of organic material such as
sawdust, coconut shells, maize cobs and tobacco stalks
as emulsifying and/or foam-forming agents there are
suitable: for example non-ionic and anionic emulsifiers,
such as polyoxyethylene fatty acid esters, polyoxyethyl-
ene fatty alcohol ethers, for example alkylaryl poly-
glycol ethers, alkylsulphonates, alkyl sulphates, aryl-
sulphonates as well as albumen hydrolysis products; as
dispersing agents there are suitable: for example lignin-
sulphite waste liquors and methylcellulose.
Adhesives such as carboxymethylcellulose and
natural and synthetic polymers in the form of powders,
granules or latexes, such as gum arabic, polyvinyl
alcohol and polyvinyl acetate, as well as natural phos-
pholipids, such as cephalins and lecithins, and synthetic
phospholipids, can be used in the formulations. Further
additives can be mineral and vegetable oils.
39 It is possible to use colorants such as inorganic
Le A 27 156 - 41 -
~~ ~3 ; ~ t~
pigments, for example iron oxide, titanium oxide and
Prussian Blue, and organic dyestuffs, such as alizarin
dyestuffs, azo dyestuffs and metal phthalocyanine dye-
stuffs, 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 combating weeds, the active compounds accord
ing to the invention, as such or in the form of their
formulations, can also be used as mixtures with known
herbicides, finished formulations or tank mixes being
possible.
Suitable herbicides for the mixtures are known
herbicides, such as, for example, 1-amino-6-ethylthio-3
(2,2-dimethylpropyl)-1,3,5-triazine-2,4-(1H,3H)-dione
(AMETHYDIONE) or N-(2-benzothiazolyl)-N, N'-dimethylurea
(METABENZTHIAZURON) for combating weeds in cereals; 4
amino-3-methyl-6-phenyl-1,2,4-triazin-5(4H)-one
(METAMITRON) for combating weeds in sugar beet, and 4-
amino-6-(1,1-dimethylethyl)-3-methylthio-1,2,4-triazin-
5(4H)-one (METRIBUZIN) for combating weeds in soya beans;
furthermore also 2,4-dichlrophenoxyacetic acid (2,4-D);
4-(2,4-dichlorophenoxy)-butyric acid (2,4-DB); 2,4-di-
chlorophenoxypropionic acid (2,4-DP}; 3-isopropyl-2,1,3-
benzothiadiazin-4-one 2,2-dioxide (BENTAZONE); methyl 5-
(2,4-dichlorophenoxy)-2-nitrobenzoate (BIFENOX); 3,5-
dibromo-4-hydroxy-benzonitrile (BROMOXYNIL); 2-chloro-
N~[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-amino]-car-
bonyl~benzenesulphonamide (CHLORSULFURON}; N,N-di.methyl-
Le A 2? 156 - 42 -
J 1 J i.,l ;. E.Y :.1
N'-(3-chloro-4-methylphenyl)-urea (CHLORTOLURON); 2-[4-
(2,4-dichlorophenoxy)-phenoxy]-propionic acid, its methyl
ester or its ethyl ester (DICLOFOP); 4-amino-6-t-butyl-
3-ethylthio-1,2,4-triazin-5(4H)-one(ETHIOZIN);2-~4-[(6-
chloro-2-benzoxazolyl)-oxy)-phenoxy}-propanoic acid, its
methyl ester or its ethyl ester (FENOXAPROP); [(4-amino-
3,5-dichloro-6-fluoro-2-pyridin-yl)-oxy]-acetic acid or
its 1-methylheptyl ester (FLUROXYPYR); N-phosphonomethyl-
glycin (GLYPHOSATE); methyl 2-[4,5-dihydro-4-methyl-4-(1-
methylethyl)-5-oxo-1H-imidazol-2-yl]-4(5)-methylbenzoate
(IMAZAMETHABENZ); 3,5-diiodo-4-hydroxybenzonitrile
(IOXYNIL); N,N-dimethyl-N'-(4-isopropylphenyl)-urea
(ISOPROTURON); (2-methyl-4-chlorophenoxy)-acetic acid
(MCPA); (4-chloro-2-methylphenoxy)-propionic acid (MCPP);
N-methyl-2-(i,3-benzothiazol-2-yloxy)-acetanilide
(MEFENACET);2-~[[((4-methoxy-6-methyl-1,3,5-triazin-2-
yl)amino)-carbonyl]-amino]-sulphonyl}-benzoic acid or its
methyl ester (METSULFURON); N-(1-ethylpropyl)-3,4-di-
methyl-2,6-dinitroaniline (PENDIMETHALIN); 0-(6-chloro-
3-phenyl-pyridazin-4-yl)-S-octyl thiocarbamate
(PYRIDATE); 4-ethylamino-2-t-butylamino-6-methylthio-s-
triazine (TERBUTRYNE) and methyl 3-[[[[(4-methoxy-6-
methyl-1,3,5-triazin-2-yl)-amino]-carbonyl]-amino]-
sulphonyl]-thiophene-2-carboxylate (THIAMETURON). Sur-
prisingly, some mixtures also show synergistic action.
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.
The active compounds can be used as such, in the
Le A 27 156 - 43 -
form of their formulations or in the use forms prepared
therefrom by further dilution, such as ready-to-use
solutions, suspensions, emulsions, powders, pastes and
granules. They are used in the customary manner, for
example by watering, spraying, atomizing or scattering.
The active compounds according to the invention
can be applied either before ox 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 0.01 and 15 kg of active compound per
hectare of soil surface, preferably between 0.05 and
10 kg per ha.
The preparation and use of the active compounds
according to the invention can be seen from the following
examples.
Preparation Examples
Example 1
COOCHS 0
S02-NH-CO-N~N-CH3
~S-CH3
(Process (a))
3.0 g (20.? mmol) of 4-methyl-5-methylthio-2,4-
dihydro-3H-1,2,4-triazol-3-one are dissolved in 60 ml of
7Ge A 2? 156 _ 44 _
acetonitrile, and 7.0 g (29 mmol) of 2-methoxycarbonyl-
phenylsulphonyl-isocyanate, dissolved in 20 ml of
acetonitrile, are added to this solution with stirring.
The reaction mixture is stirred at 20°C for 6 hours. The
product which is obtained in crystalline form is then
isolated by filtration with suction.
This gives 6.0 g (75 ~ of theory) of 4-methyl-5
methylthio-2-(2-methoxycarbonyl-phenylsulphonyl-amino
carbonyl)-2,4-dihydro-3H-1,2,4 -triazol-3-one of melting
point 184°C.
Example 2
OCF3 0
502-NH-CO-N~N-NH2
~S-CH3
(Process (b))
1.7 g (11.2 mmol) of 1,8-diazabicyclo-(5,4,0]
undec-7-ene (DBU) and 2.7 g (11.2 mmol) of 2-trifluoro
methoxybenzenesulphonamide are added to a solution of
3.0 g (11.3 mmol) of 4-amino-5-methylthio-2-phenoxy-
carbonyl-2,4-dihydro-3H-1,2,4-triazol-3-one in 60 ml of
methylene chloride. The reaction mixture is stirred for
4 hours at 20°C, then washed twice with 1 ~ strength
hydrochloric acid and three times with water, dried with
sodimn sulphate, and filtered. The filtrate is concen-
trated, the residue is stirred with diethyl ether, and
the product which is obtained in crystalline form is
Le A 27 156 - 45 -
isolated by filtration with suction.
This gives 2.1 g (45 ~ of theory) of
4-amino-5-methylthio-2-(2-trifluoromethoxy-phenylsul
phonyl-aminocarbonyl)-2,4-dihydro-3H-1,2,4-triazol-3-one
of melting point 136°C.
For example, the compounds of the formula (I)
listed in Table 3 below can also be prepared analogously
to Examples 1 and 2 and following the general description
of the preparation processes according to the invention.
o
R3-S02-NH-CO~N~N~RZ (I)
~S(O1n-R2
Le A 27 156 - 46 -
1 4
Table 3: compounds
Preparation of
ExampJ.es the
of
the
foxznula
(
I
)
Ex. Rl R2 R3 n Melting
NO. point (C)
COOCH3
~
3 CH3 C2H5 ~ 0 I49
~
C00CH3
4 CH3 CH(CH3)2 ~ ~ 0 161
COOCH3
~
5 CH3 CH2CH=CH2 ~ 0 I40
~
COOCH3
6 C2H5 C2H5 ~ ~ 0 128
COOCH3
7 C2H5 CH3 0 167
C00CH3
8 C2H5 CH2C6H5 ~ 0 285
Le ~ z~ ass - 4~ -
Table 3: (Continuation)
Ex. R' RZ R3 n Melting
No. point (°C)
COOCH3
CH3 CH2C6H5 \ ~ 0 143
COOCH3
20 CH2C6H5 CH3 \ ~ 0 134 '
COOCH3
11 CH(CH3>2 CH3 \ ~ 0 142
C00CH3
I2 ~ \
-\ CH3 ~ 0 205
Ci
COOCH3
13 CH3 C3H7 / \
o I4z
COOCH3
I4 C2H5 -CH2CH=CH2 ~- \ 0
I11
Le A 27 156 _ 4g _
~,
Table 3: (Continuation)
Esc. R1 RZ R3 n Melting
No. point (°C)
COOCH3
7
15 C2H5 C3H7 ~~ 0 125
COOCH3
16 C2H5 CH(CH3)2 ~- ~ 0 131
OCF3
17 CH3 CH3 ~~ 0 150
COOCH3
18 C3H7 -CH2CH=CH2 ~- ~ 0 128
COOCH3
19 C3H7 C3H~ ~ 0 137
COOCH3
20 C3H7 CH(CH3)2 7a~ 0 221
OCF3
21 CH3 C2H5 ~-~ 0 133
Le ~. 27 156 _ 4g _
C
Table 3: (Continuation)
Ex. R1 R2 R3 n Melting
No. point ('C)
COOCH3
22 ~ -CH2CH=CH2 ~ 0 151
~
-
COOCH3
23 ~ C3H7 ~ 0 199
~
_
COOCH3
24 ~ CH(CH ~ 0 163
) ~
3 _~
2
COOCH3
~
25 C3H7 CH3 _~ 0 144
C00CH3
~
26 C3H7 C2H5 -~ 0 130
COOCH3
27 ~ C2H5 ~ 0 173
'
COOCH3
28 ~ CH ~ 0 173
~
3 -
Le A 27 z56 - 50 -
~?:~ ~
Table
3:
(Continuation)
Ex. R1 Rz R3 n Melting
No. point (C)
C00CH3
/
29 -CH2-CH=CH2 CH3 '~ 0 137
COOCH3
~
30 -CH2-CH=CH2 C2H5 _~ 0 128
OCF3
31 ~ CH3 ~ 0 182
~
-
OCF3
32 ~ C ~ 0 152
H ~
2 -
5
COOCH3
~
33 CH3 CH3 -~ 2 176
C1
34 CH3 C2H5 / ~ 0 138
CH3
Le A 27 156 - 51 -
Table
3:
(Continuation)
Ex. R1 RZ R3 n Melting
No. point (C)
C1 '
35 CH3 CH3 ~ ~ 0 175
CH3
COOCH3
~
~
36 ~ 0 101
-CHZ-CH=CH2 -CH2-CH=CH2
C1
37 ~ CH3 ~ ~ 0 190
CH3
Ci
3g ~ C2H5 ~ ~ 0 163
CH3
OCF3
~
39 -CH2-CH=CH2 CH3 -~ 0 163
OCF3
~
-CHZ-CH=CH2 C2H5 ~~ 0 133
35
Le A 27 156 - 52 -
Table 3: (Continuation)
E~ . R1 RZ R3 n Melting
No. point (°C)
OCF3
41 CH3 C3H7 7-~ 0 133
OCF3
92 C2H5 -CH2-CH=CH2 ~-~ 0 107
OCF 3
43 ~ C3H7 /~~ 0 121
COOCH3
44 -CH2-CH=CH2 C3H7 /-~ 0 124
COOCH3
45 -CH2-CH=CH2 CH(CH3)2 /-~ 0 94
C1
4o CH3 CH(CH3)2 / ~ 0 142
CH3
Le A 27 156 - 53 -
,
Table
3:
(Continuation)
Ex. R1 RZ R3 n Melting ,
No. point (C)
C1
47 -CH2-CH=CH2 CH3 ~ ~ 0 165
CH3
C1
48 -CH2-CH=CH2 C2H5 ~ ~ 0 140
CH3
~ C1
49 ~ CH(CH3)2 ~ ~ 0 131
CH3
C1
50 C
H \
3 0 138
7
CH3
C1
51 C2H5 CH3 0 168
CH3
C1
52 C2H5 C2H5 ~ ~ 0 129
CN3
Le 27 156 - 54 -
A
t~~~ ~~.~~
Table (Continuation)
3:
Ex. R' RZ R3 n Melting
No. point (C)
CZ
53 CH3 C3H~ ~ ~ 0 146
CH3
C1
54 CH3 -CH2-CH=CH2 ~ ~ 0 125
CH3
C1
55 ~ -CH2-CH=CH2 ~ ~ 0 141
CH3
C1
~
56 C2H5 C3H7 ~ 0 122
CH3
C1
57 C2H5 -CH2-CH=CH2 ~-.\ 0 96
CH3
C1
58 -CH2-CH=CH2 -CH2-CH=CH2 113
/ ~ 0
CH3
Le A 27 156 - 55 -
~~~~~~~
Table
3:
(Continuation)
Ex R1 R3 n Melting
. RZ
No. point ('C)
C1
59 -CH2-CH=CH2 ~ ~ 0 102
C3H7
CH3
C1
60 -CH2-CH=CH2 ~ ~ 0 122
CH(CH3)2
CH3
OCF3
/
61 CH3 -_\ 0 106
CH(CH3)2
OCF 3
~
62 CH3 _~ 0 125
-CH2-CH=CH2
OCF 3
63 ~ /-~ 0 12S
-CH2-CH=CH2
OCF3
64 ~ CH(CH ~ 0 127
) ~
3 ~
2
Le A 27 156 - 56 °
Table 3: (Continuation]
Ex. R1 RZ R3 n Melting
NO. point ('Cj
OCF3
~
65 C2H5 CH3 -~ 0 171
OCF3
~
66 C2H5 C2H5 -~ 0 238
OCF3
~
~
67 -CH2-CH=CH2C3H7 - 89
0
OCF 3
~
68 C2H5 C3H7 ~ 0 ? 27
-
OCF 3
~
69 -CH2-CH=CH2CH(CH3)2-~ 0 117
OCF3
~
~
70 -CH2-CH=CH2-CH2-CH=CH2 79
-
0
Le A 27 156 - 57 -
~~~~.~,~
r r
~ lF J
Table 3: (Continuation)
Ex. R1 RZ R3 n Melting
No. point (°C)
i0
C1
71 C2H5 CH(CH3)2 ~ ~ 0 137
CH3
72 CH3 CH3 ~ ~ 0 193-194
S~COOCH3
73 CH3 C2H5 ~ ~ 0 176-177
S~COOCH3
74 ~ CH3 ~ ~ 0' 175-177
S COOCH3
75 ~ C2H5 ~ ~ 0 153-155
COOCH3
Le A 27 156 - 58 -
~~~.'~'
Table 3: (Continuation)
Ex. R1 RZ R3 n Melting
No. point (°C)
COOCH3
76 N(CH3)2 GH3 -~ 0 178-179
COOCH3
77 N(CH3)2 C2H5 7~~ 0 139-136
COOC2H5
78 ~ CH3 ~ ( 0 188-191
I~I~N
CH3
Br
79 CH3 CH3 ~-~ 0- 176- 179
Br
80 CH3 C2H5 ~~~ 0 , 154-156
I,e A 27 X56 - 59 -
Table 3: (Continuation)
Ex. R1 RZ R3 n Melting
No. point (°C)
Br
81 ~ CH3 /~\ 0 192-195
$r
82 ~ C2H5 7-\ 0 151-154
CH3
7
83 CH3 CH3 -\ 0 157
C Y. 3
CH3
89 ~ 7
0 168
CH3
7
\
85 CH3 C2H5 -
0 132
Le A 27 156 - 60 -
5
Table 3: (Continuation)
Ex. R' RZ R3 n Melting
No. point (°C)
ZO
CH3
86 ~ C2H5 ~-~ 0 137
C00CH3
87-CH2-CH=CH2 -CH2-C=CH ~_~ 0 95
COOCH3
r
88 ~ -CH2-C=CH ~ 0 128-131
Z5 COOCH3
89 CH3 -CH2-C=CH ~~~ 0 143-144
CH3
90 CH3 -CH(CH3)2 /-~ 0 107-109
Br
91 CH3 - CH ( CH3 ) 2 ~-~~ 0 103- 104
Le A 27 156 - 61 --
Table 3: (Continuation)
Ex. R' RZ R3 n Melting
No. point ('C)
CF3
92 CH3 -CH(CH3)2 /~~ 0 lI9-117
CF3
93 ~ CH3 ~ 0 199-195
/
,
~
CF3
94 C2H5 '~ 0 150-152 '.
CF3
95 CH3 C2H5 /-~ - 0 146-148
35
Le A 27 156 - 62 -
Starting substances of the formula ~ II )
Examgle (-,II-11
0
H-N~N-CH3
~S-CH3
Step 1
S
CH3-NH-C-NH-NH-COOC2H5
A solution of 175 g (2.4 mol) of methyl isothio-
cyanate in 300 ml of diethyl ether is added to a solution
of 250 g (2.4 mol) of ethyl hydrazinoformate, with stir-
ring. The reaction mixture is stirred for 12 hours at
20°C and then cooled to about 10°C, and the product which
is obtained in crystalline form is isolated by filtration
with suction. This gives 404 g (95 ~ of theory) of
4-methyl-1-ethoxycarbonylthiosemicarbazide of melting
point I30°C.
The following are obtained analogously:
4-ethyl-1-methoxycarbonyl-thiosemicarbazide
I5 (melting points 142°C);
4-propyl-1-methoxycarbonyl-thiosemicarbazide
(melting point: 117°C
4-cyclopropyl-1-methoxycarbonyl-thiosemicarbazide
(melting point: 148°C);
4-allyl-1-methoxycarbonyl-thiosemicarbazide
(melting point: 151°C);
4-dimethylamino-1-methoxycarbonyl-thiosemicarbazide
(melting point: 144oC).
Le A 27 156 - 63 -
Step 2
C
H-N~N-CH3
~SeKe
A mixture of lO.Og (56.5 mmol) of 4-methyl-1-
ethoxycarbonyl-thiosemicarbazide (cf. Step 1), 4.0 g
(29 mmol) of potassium carbonate and 80 ml of ethanol is
refluxed until the evolution of gas has ceased (about 3
hours). When the mixture is cold, it is concentrated, the
residua is stirred with 50 ml of methylene chloride, and
the product, which has remained undissolved, is isolated
by filtration with suction.
This gives 9.2 g (96 ~ of 'theory) of the potas-
sium salt of 5-mercapto-4-methyl-2,4-dihydro-3H-1,2,4-
triazol-3-one (melting point >230°C).
The potassium salts of
5-mercapto-4-ethyl-2,4-dihydro-3H-1,2,4-triazol-3-one,
5-mercapto-4-propyl-2,4-dihydro-3H-1,2,4-triazol-3-one,
5-mercapto-4-cyclopropyl-2,4-dihydro-3H-1,2,4-triazol-3-
one,and 5-mercapto-4-allyl~2,4-dihydro-3H-1,2,4-triazol-
3-one, and 5-mercapto-4-dimethylamino-2,4-dihydro-3H-
1,2,4-triazol-3-one, all of which melt above 230 oC,
are obtained analogously.
Le A 27 156 - 64 -
G ~ ~~ ~A ~.9~ '~
lJ ~ ~nl N7 ~ .~.1
Step 3
0
H-N~N-CH3
~S-CH3
A mixture of 4.0 g (23.'7 mmol) of the potassium
salt of 5-mercapto-4-methyl-2,4-dihydro-3H-1,2,4-triazol-
3-one (cf. Step 2), 4.1 g (28.9 mmol) of methyl iodide
and 80 ml of methanol is stirred for 12 hours at 20°C.
The mixture is then concentrated, the residue is stirred
with methylene chloride, and the potassium iodide, which
has remained undissolved, is separated off by filtration.
The filtrate is concentrated, the residue is stirred with
500 ml of diethyl ether/petroleum ether (lel by vol.),
and the product which has been obtained in crystalline
from is isolated by filtration with suction.
This gives 3.4 g (99 ~ of theory) of 4-methyl-5
methylthio-2,4-dihydro-3H-1,2,4-triazol-3-one o~ melting
point 97°C.
For example the compounds of the formula (II)
listed in Table 4 below can also be prepared analogously
to Example (II-1).
0
(II}
H-N~N-R~
~S(0)n-R2
Le A 2? 156 - 65 -
Table 4 Preparation Examples of the compounds of the
formula (II)
Ex. R1 RZ n m>p. C)
(
No. (Refra ctive
index)
--
II-2 CH3 C2H5 0 97
II-3 CH3 C3H7 0 50
II-9 CH3 CH(CH3)2 0 91
II-5 CH3 -CH2CH=CH2 0 58 '
II-6 CH3 -CH2C6H5 0
II-7 C2H5 CH3 0 95
II-8 C2H5 C2H5 0 87
II-9 C2H5 C3H7 0 73
II-i0 C2H5 CH(CH3)2 0 42
II-i1 C2H5 -CH2CH=CH2 0 (nD: 1,5400)
~5 II-12 C2H5 -CH2C6H5 0
II-13 C3N7 CN3 0 78
II-14 C3H7 C2H5 0 (nD; 1,5215)
II-15 C3H7 C3H7 0 56
II-16 C3H7 CH(CH3)2 0 55
II-17 C3H7 -CH2CH=CH2 0 (nD: 1,5350)
II-18 CH(CH3)2 CH3 0
II-19 --a CH3 0 160
II-20 -~ C2H5 0 119
Le A 27 156 - 66 -
~~~~~ 3~ ._
Table 4 (Continuation)
Ex. R1 RZ n m.p. ( °C)
No. (Refractive
index)
II-21 --a C3H7 0 94
II-22 --~ CH(CH3)2 0 94
II-23 --a -CH2CH=CH2 0 105
II-24 -CH2C6H5 CH3 0 135
II-25 -CH2CH=CH2 CH3 0 70
II-26 -CH2CH=CH2 C2H5 0 55
II-27 CH3 CH3 2 166
II-28 -CH2-CH=CH2 -CH2-CH=CH2 0 (amorphous)*
II-29 _CH2_CH=CH2 CH(CH3)2 0 57
II-30 -CH2-CH=CH2 C3H7 0 45
II-31 -Id(CH3)2 CH3 0 168-169
I I-32-J~I(CH3)2 C2H5 0 146
II-33 CH3 -CH2-C=CH 0 153
II-34 --~a -CH2-C=CH 0 153-154
II-35 -CH2-CH=CH2 -CH2--C=CH 0 102-103
* 1H -1~17~fR (D6-DI~5S0,360 I~Hz ) 3, 66 S-CH2-) ;
: 8 = (d,
4, 17 (m, 1y-CH2-);4,95-5,28 2CH2=);
(m,
5, 75-5,99 (m, ppm.
2CH=); 12,0
(13H)
Le A 27 156 - 67 -
.,
Startincr substances of the formula (IVJv:
Example Iy-1)_
0
0-CO-N~N-NH2
~S-CH3
22.1 g (0.141 mol) of phenyl chloroformate are
added to a mixture of 20.Og (0.137 mol) of 4-amino-5-
methylthio-2,4-dihydro-3H-1,2,4-triazol-3-one, 5.6 g
(0.141 mol) of sodium hydroxide, 0.2 g of tetrabutylam-
monium bromide and 200 ml of methylene chloride/water
(1:1, by vol.), with vigorous stirring. The reaction
mixture is stirred for 12 hours at 20°C, and the product
which is obtained in crystalline form is isolated by
filtration with suction. This gives 34.8 g (95 ~ of
theory) of 4-amino-5-methylthio-2-phenoxycarbonyl-2,4-
dihydro-3H-1,2,4-triazol-3-one of melting point 211°C.
For example the compounds of the formula (IV)
listed in Table 5 below can also be prepared analogously
to Example (IV-1).
0
Z-CO-N~N-R1. (IV)
~S(0)n-R2
Le A 2? 156 - 68 -
/~: ~ s'~ -t
f~ui lj ~~
Table 5 Preparation of the compounds of the
Examples
formula (IV)
Ex . R1 Rz n Z Melting
No. point (C)
~
~
IV-2 CH3 CH3 0 166
-
~
\
IV-3 CH3 C2H5 0 112
-
IV-9 C2H5 C2H5 0
IV-5 CH3 C3H~ 0 C1
IV-6 CH3 CH2-CH=CH2 0 /- \
IV-7 ~ CH3 0 /-\ 193
IV-8 ~ C2H5 0 ~~~ 89
IV-9 ~ C3H7 0
Le A 27 156 - 69
Table 5 (Continuation)
Ex. R1 RZ n Z Melting
No. point (C)
IV-10 ~ CH2-CH=CH2 0
IV-11 OCH3 CH3 0
IV-12 OC2H5 C2H5 0
IV-13 OCH2-CH=CH2 0
C2H5
IV-14 ~ CH(CH3)2 0 C1
IV-15 C2H5 CH3 0 C1
IV-16 C2H5 C3H~ 0 ~~~
IV-17 NH-CH3 CH3 0
IV-18 NH-CH3 C2H5 0 ~~~
Le A 27 15~ ~ 70 -
Table 5 (Continuation)
Ex. R1 R2 n Z Melting
No. point (C)
IV-19 N(CH3)2 C2H5 0
IV-20 NH-CH3 C3H7 0 /-~
IV-21 NH-CH3 CH(CH3)2 0 ~ ' ~
IV-22 NH-CH3 CH2-CH=CH2
0
IV-23 CH2-CH=CH2 C2H5 0
Le A 27 156 - 71 -
~~~~~.3~~'
Use Examples:
In the Use Examples which follow, the known
herbicide isocarbamid, of the formula (A) below, is used
as comparison substance:
n
I-i~-CO-NH-CH2CH(CH3)2
~0
(disclosed in, for example, DE-1,795,117).
In the text below, the formulae of the compounds
according to the invention used for the Use Examples are
listed individually, the numbers being those of the
Preparation Examples:
COOCH3 0
502-NH-CO~N~N~CH3 (1)
~S-CH3
COOCH3 0
S02-NH-CO~N~N~CH3 (3)
~S-C2H5
COOCH3 0
S02-NH-CO~N~N~CH3 (9)
~S-CH(CH3)2
Le A 27 156 - 72 -
COOCH3
~ S02-NH-CO~N~N~CH3 (5)
~S-CH2CH=CH2
COOCH3 0
\ ~ S02-1QH-CO~N~NiC2H5 ( 6 )
N°~SC2H5
COOCH3 O
~ ~ S02-l~H-C0~1J~N~C2H5 ( 7 )
~S-CH3
COOCH3 O
~ ~ S02-NH-CO~Id~~?~l~Ci':g ( 9 )
?~S-CH2C6H5
COOCH3 0
502-?'?H-C0~?I~?J~CH3 ( 13 )
;~~5-C3H~-n
COOCH3 O
~ S02-NH-CO~ld~N~'C2H5 ( 14 )
~S-CH2CH=CH2
COOCH3 0
~ S02-NH-CO~I~~?~I~C2H5 ( 15 )
~S-C3H7-n
Le A 27 156 a 73
~~a ,~y ~
Y~,7 ~Y YHI y~ .~- 0:d rJ
COOCH3 O
_ ~
~ S02-1~H-CO~l~~N~C2H5 ( 16 )
~S-CH(CH3)2
OCF3 0
~ S02-l~tH-COT N~CH3 ( 17 )
I~S-CH3
COOCH3 0
~ ~ S02-NN-CO~N~1~~C3H~-n (20)
N-~S-CH(CH3)2
OCF3 O
~'~ S02-NH-CO~I~~N~CH3 ( 2? )
I~S-C2H5
COOCH3 0
~ S02-NH-C0~1~~N ( 22 )
[
I~S-CH2CH=CH2
COOCH3 0
~ S02-NH-CO~N~N (23)
1~S-C3H7-n
COOCH3 0
~ S02-NH-CO~N~N (29)
~S-CH(CH3)2
Le A 27 156 - 74 -
COOCH3
_
~ S02-NH-CO~N~NiC3H7-n (25)
~S-CH3
OCF3 O
~ S02-NH-CO~l~~la~C3H7-n ( 26 )
~S_C2H5
COOCH3 0
~ 7 S02-IJH-CO~I~~N ( 27 )
~S-C2H5
OCF3 0
~~ ~ S02-NH-CO~N~Iv' ( 28 )
N~S-CH3
COOCH3 0
S02-IJH-CO~I~I~I,;~CH2-CH=CH2 ( 29 )
~~~
~S-CH3
COOCH3 0
~502-NH-CO~N~N~CH2-CH=CH2 (30)
I
~S-C2H5
OCF3 0
S02-1v'H-CO~N~N~ ( 31 )
I~S-~CN3
Le A 27 156 - 75 -
i
OCF3 0
/~
~ S02-NH-C0~I4~N~ ( 32 )
1~S -~CJ2H 5
C1 0
~ S02-NH-CO~IJ~N~CH3 ( 34 )
CH3 ~S-C2H5
C1 0
~~~ S02-I~H-CO~Id~I~i~'CH3 ( 35 )
CH3 l~S-CH3
C1 0
~ ~ S02-1~H-CO~N~L1~ ( 37 )
CH3 1~S °~C133
C1 0
502-1QH-CO~N~LT ( 3g )
j
CH3 I'T~~S'CZHS
0CF 3 0
~ S02-IQH-C0~13~N~CH2-CH=CH2 ( 4 0 )
N-~S-C2H5
Le A 27 156 ~ 70 -
~~~,~,~ ~;~
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
and, after 24 hours, watered with the preparation of the
active compound. It is expedient to keep the amount of
water per unit area constant. 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, a clearly superior activity com-
pared with the prior art is shown, for example, by the
compounds of Preparation Examples:
l, 3, 4, 5, 6, 7, 13, 17, 21, 22, 23, 24, 25, 26, 27,
28, 29, 30, 31, 32, 34, 35, 37.
Le A 27 156 - 77 -
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 so chosen that the particular amounts of
active compound desired are applied in 1,000 1 of
water/ha. After three weeks, the degree of damage to the
plants is rated in ~ damage in comparison to the develop-
ment of the untreated control. The figures denote:
0~ = no action (like untreated control)
100 _ total destruction
In this test, a clearly superior activity com-
pared with the prior art is shown, for example, by the
compounds of Preparation Examples:
1, 3, 4, 5, 6, 7, 13, 14, 16, 17, 20, 21, 22, 23, 24,
25, 26, 27, 28, 29, 30, 31, 32, 34, 35, 37, 38, 40.
Le A 27 156 - 78 -
~~'~~~~?~
Example C
Pyricularia test (rice) / protective
Solvent: 12,5 parts by weight of acetone
Emulsifier: 0,3 parts by weight of alkylarylpolyglycol ether
To produce a suitable preparation of active compound,
1 part by weight of active compound is mixed with the
stated amount of solvent, and the concentrate is diluted
with water and the stated amount of emulsifier, to the
desired concentration.
To test for protective activity, young rice plants are
sprayed with the preparation of active compound until
dripping wet. After the spray coating has dried off, the
plants are inoculated with an aqueous spore suspension of
Pyricularia orycae. The plants are then placed in
a greenhouse at 100 o relative atmospheric humidity and
25°C.
Evaluation of the disease infestation is carried out 4 days
after the inoculation.
Tn this test, a clearly superior activity compared with the
prior art is shown, for example, by the compounds according
to the following preparation examples:
1, 3, 4, 5, 7, 9.
Le A 27 156 - ?9 -
Example D
Pyricularia test (rice) / systemic
Solvent . 12,5 parts by weight of acetone
Emulsifier: 0,3 parts by weight of alkylarylpolyglycol ether
To produce a suitable preparation of active compound,
1 part by weight of active compound is mixed with the
stated amount of solvent, and the concentrate is diluted
with water and the stated amount of emulsifier, to the
desired concentration.
To test for systemic properties, standard soil in which
young rice plants have been grown is watered with 90 ml
of the preparation of active compound. 7 days after the
treatment, the plants are inoculated with an aaueous spore
suspension of Pyricularia oryzae.
Thereafter, the plants remain in a greenhouse at a tempera-
ture of 25° and a relative atmospheric humidity of 100
until they are evaluated.
Evaluation of the disease infestation is carried out 4 days
after the inocualtion.
In this test, a clearly superior activity compared with
the prior art is shown, for example, by the compounds
according to the following preparation examples:
l, 3, 4, 5, 7, 15, 17, 21, 22, 25.
I~e A 27 156 - 80
