Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
The invention relates to new halogenated sul-
phonylaminocarbonyltriazolinones, to several processes
for their preparation, and to their use as herbicides.
It is known that certain substituted aminocarbon
ylimidazolinones, such as, for example, 1-isobutylamino
carbonyl-2-imidazolidinone (isocarbamid), have herbicidal
properties (cf. R. Wegler, Chemie der Pflanzenschutz- and
5chadlingsbekampfungsmittel [Chemistry of Plant Protec
tion Agents and Pesticides], Vol. 5, p. 219, Springer
Verlag, Berlin-Heidelberg-New York, 1977). However, the
action of this compound is not satisfactory in all
respects.
The new halogenated sulphonylaminocarbonyl-
triazolinones of the general formula (I)
0
R3-SOZ-NH-CO-Nr\N-R1 (I)
~R2
in which
R1 represents hydrogen, hydroxyl or amino, or repre-
sents an optionally substituted radical from the
series comprising alkyl, alkenyl, alkinyl, cyclo-
alkyl, aralkyl, aryl, alkoxy, alkenyloxy, al 1
amino, cycloalkylamino and dialkylamino,
R2 represents halogen and
R3 represents an optionally substituted radical from
the series comprising alkyl, aralkyl, aryl and
Le A 27 155 _ 1
heteroaryl,
as well as salts of compounds of the formula (I) have now
been found.
The new halogenated sulphonylaminocarbonyltri-
azolinones of the general formula (I) are obtained when
a) halogenated triazolinones of the general formula
(II)
0
HN~N-R1 (II)
in which
R' and RZ have the abovementioned meanings
are reacted with sulphonyl isocyanates of the
general formula (III)
R3-SOZ-N=C=0 ( I I I )
in which
I5 R3 has the abovementioned meaning,
if appropriate in the presence of a diluent, or when
b) halogenated triazolinone derivatives of the general
formula (IV)
0
Z-CO-N~N-R1 (IV)
~R2
Le A 27 155
in which
Rr and Rz h ve the abovementioned meanings and
Z represents halogen, alkoxy, aralkoxy or aryloxy
are reacted with sulphonamides of the general
formula (V)
R3-S~z-~z f V)
in which
R3 has the abovementioned meaning,
if ,appropriate in the presence of an acid acceptor
ld and if appropriate in the presence of a diluent, or
when
c) halogenated triazolinones of the general formula
(II)
O
HN~N-R1 (II)
~R2
in which
R' and Rz have the abovementioned meanings
are reacted with sulphonamide derivatives of the
general formula (VI)
R3-sot-rrx-c~-z ~ vI ~
2a in which
R3 has the abovementioned meaning and
Z represents halogen, alkoxy, aralkoxy or
Le A 27 155 - 3
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 halogenated sulphonylaminocarbonyltri-
azolinones 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
known herbicide 1-isobutylaminocarbonyl-2-imidazolidinone
(isocarbamid), which has a similar structure.
The invention preferably relates to compounds of
the formula (I) in which
R1 represents hydrogen, hydroxyl or amino, or repre-
sents C1-C6-alkyl which is optionally substituted by
fluorine, chlorine, bromine, cyano, C1-Ca-alkoxy,
C1-Ca-alkylcarbonyl or C1-Ca-alkoxy-carbonyl, or
represents C3-Cs-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-Ca-alkyl, or represents
phenyl-Cl-C3-alkyl which is optionally substituted by
fluorine, chlorine, bromine, cyano, nitro, C1-Ca-
alkyl, trifluoromethyl, C1-Ca-alkoxy and/or C1-Ca-
alkoxy-carbonyl, or represents phenyl which is
optionally substituted by fluorine, chlorine,
bromine, cyano, nitro, C~-Ca-alkyl, trifluoromethyl,
he A 27 155
C1-C4-alkoxy, fluorine- and/or chlorine-substituted
C1-C3-alkoxy, C~-C4-alkylthio, fluorine- and/or
chlorine-substituted C1-C3-alkylthio, Cl-C4-alkylsul-
phinyl, C1-C4-alkylsulghonyl and/or Cl-C,,-alkoxy-
carbonyl, or represents C1-Cs-alkoxy which is option-
ally substituted by fluorine, chlorine, cyano, C1-C4-
alkoxy or Cl-C,,-alkoxy-c _rbonyl, or represents C~-C4-
alkenyloxy, or represents fluorine-, cyano-,
phenyl-, C1-Ca-alkoxy- or C1-C4-alkoxy-carbonyl-
ZO substituted Cl-C4-alkylamino, C3-C6-cycloalkylamino,
or represents di- ( C1-C,,-alkyl ) -amino,
RZ represents fluorine, chlorine, bromine or iodine and
R5
R3 represents the group ~ , where
R4
R° and RS are identical or different and represent
hydrogen, fluorine, chlorine, bromine, iodine,
nitro, C1-C6-alkyl (which is optionally substi-
tuted by fluorine, chlorine, bromine, cyano,
carboxyl, C1-C4-alkoxycarbonyl, C1-C4-alkyl-
amino-carbonyl, di-(Cl-C4-alkyl)amino-carbonyl,
hydroxyl, C1-C,,-alkoxy, formyloxy, C,-Cw-alkyl-
carbonyloxy, C1-C4-alkoxy-carbonyloxy, C~-C4-
alkylamino-carbonyloxy, C1-C4-alkylthio, C1-C4_
alkylsulphinyl, Cl-C4-alkylsulphonyl, di- ( C1-C,,-
alkyl)-aminosulphonyl, C3-C6-cycloalkyl or
phenyl), or represent CZ-Cs-alkenyl (which is
optionally substituted by fluorine, chlorine,
bromine, cyano, C1-C4-alkoxy-carbonyl, carboxyl
or phenyl ) , or represent C2-C6-alkinyl (which is
Le A 27 155 - 5 -
~~2~~~~
optionally substituted by fluorine, chlorine,
bromine, cyano, C1-C,,-alkoxy-carbonyl, carboxyl
or phenyl), or represent C1-C4-alkoxy (which
is
optionally substituted by fluorine, chloxine,
bromine, cyano, carboxyl, C1-C4-alkoxy-carbonyl,
G1-C4-alkoxy, Cl-C~-alkylthio, C1-G4-alkyl-
sulphinyl or C1-C4-alkylsulphonyl ) , or represent
C1-C4-alkylthio (which is optionally substituted
by fluorine, chlorine, bromine, cyano, car-
boxyl, C1-C4-alkoxy-carbonyl, C1-C4-alkylthio,
C1-C4-alkylsulphinyl or C1-C4-alkylsulphanyl
) , ar
represent C~-Cs-alkenyloxy (which is optionally
substituted by fluorine, chlorine, bromine,
cyano or C1-C4-alkoxy-carbonyl), or represent
CZ-Cs-alkenylthio (which is optionally sub-
stituted by fluorine, chlorine, bromine, cyano,
nitro, Ci-C3-alkylthio or C1-C,,-alkoxycarbonyl
) ,
C~-Cs-alkinyloxy, C3-Cs-alkinylthio ar the
radical -~ ( O ) p-Rs, where
p represents the numbers 1 or 2 and
Rs represents C1-C4-alkyl (which is optionally
substituted by fluorine, chlorine, brom-
ine, cyano or C1-C4-alkoxy-carbonyl ) , C3-Cs-
alkenyl, C3-Cs~alkinyl, C1-C4-alkoxy, C1-C4-
alkoxy-C1-Cw-alkylamino, Cl-C4-alkylamino,
di-(C1-CH-alkyl)-amino and phenyl, ar
represents the radical -IdHOR', where
R' represents C1-C12-alkyl (which is
optionally substituted by fluorine,
chlorine, cyano, C1-C4-alkaxy, C1-C4-
Le A 27 155 - 6 -
alkylthio, C1-C4-alkylsulphinyl, Cl-C4_
alkylsulphonyl, C1-Ca-alkyl-carbonyl,
Cl-Ca-alkoxycarbonyl, Cl-Ca-alkylamino-
carbonyl or di-(C1-Ca-alkyl)-amino-
carbonyl ) , or represents C3-Cs-alkenyl
(which is optionally substituted by
fluorine, chlorine or bromine ) , C3-Cs-
alkinyl, C3-Cs-cycloalkyl, C3-Cs-
cycloalkyl-C1-CZ-alkyl, phenyl-Cl-CZ_
alkyl (which is optionally substitu
,, ted by fluorine, chlorine, vitro,
cyano, C1-Ca-alkyl, C1-Ca-alkoxy or
C1-Ca-alkoxy-carbonyl ) , or represents
benzhydryl, or represents phenyl
(which is optionally substituted by
fluorine, chlorine, vitro, cyano,
C1-Ca-alkyl, trifluoromethyl, C1-Ca-
alkoxy, C1-C2-fluoroalkoxy, C1-Ca-
alkylthio, trifluoromethylthio or
C1-Ca-alkoxycarbonyl ) ,
Ra and/or RS furthermore represent phenyl or phenoxy,
or represent C1-Ca-alkylcarbonylamino, Cl-Ca-
alkoxy-carbonylamino, Cl-Ca-alkylamino-carbonyl-
amino and di-(C1-Ca-alkyl)-amino-carbonylamino
or represent the radical -CO-Red where
Rs represents C1-Cs-alkyl, C1-Cs-alkoxy, C3-Cs-
cycloalkoxy, C3-Cs-alkenyloxy, Cl-ca-alkyl-
thio, Cx-Ca-alkylamino, Cl-Ca-alkoxyamino,
C1-Ca-alkoxy-C1-Ca-allyl-amino or di- ( C1-Ca_
alkyl)-amino (which are optionally
Le A 27 155 - 7
~~2~:~
substituted by fluorine and/or chlorine),
R'' and/or RS furthermore represent trimethylsilyl,
thiazolinyl, C1-C,,-alkylsulphonyloxy or di
(C1-C4-alkyl)-aminosulphonylamino or represent
the radical -CH=N-R9, where
R9 is C1-C6-alkyl which is optionally substi-
tuted by fluorine, chlorine, cyano,
carboxyl, Cl-C4-alkoxy, C1-C~-alkylthio,
Cl-C,,-alkylsulphinyl or C1-C4-alkylsul-
phonyl, or represents benzyl which is
optionally substituted by fluorine or
chlorine, or represents C3-C6-alkenyl or
G3-C6-alkinyl, each of which is optionally
substituted by fluorine or chlorine, or
represents phenyl which is optionally
substituted by fluorine, chlorine, brow-
ine, C~-C4-alkyl, C1-C4-alkoxy, trifluoro-
methyl, trifluoromethoxy or trifluoro-
methylthio, or represent C1-Cs-alkoxy,
C3-C6-alkenoxy, 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, phenylamino, C1-C4-alkyl-carbonyl-
amino, C1-C4-alkoxy-carbonyl-amino or C1-C4-
alkyl-sulphonylamino, or represents
phenylsulphonylamino which is optionally
substituted by fluorine, chlorine, bromine
or methyl,
furthermore
Le A 27 155
- R12
R3 represents the radical '~H ~ _ where
R10 ~I1
Rz° represents hydrogen or C1-Ca-alkyl,
R11 and R12 are identical or different and represent
hydrogen, fluorine, chlorine, bromine, vitro,
cyano, C1-Ca-alkyl (which is optionally sub
stituted by fluorine and/or chlorine), C1-Ca-
alkoxy (which is optionally substituted by
fluorine and/or chlorine), carboxyl, C1-Ca-
alkoxy-carbonyl, dimethylaminocarbonyl, C~-Ca-
" alkylsulphonyl or di-(C1-Ca-alkyl)-amino-
sulphonyl
furthermore
R3 represents the radical R13 ~ ~~ s R14 where
Y
R13 and R'a are identical or different and represent
hydrogen, fluorine, chlorine, bromine, vitro,
cyano, C1-Ca-alkyl (which is optionally substi-
tuted by fluorine and/or chlorine) or C1-Ca-
alkoxy (which is optionally substituted by
fluorine and/or chlorine);
furthermore
R15
R3 represents the radical ~ ~ where
~N
fib
R15 and R16 are identical or different and represent
hydrogen, fluorine, chlorine, bromine, vitro,
cyano, C~-Ca-alkyl (which is optionally substi
tuted by fluorine and/or chlorine) , C1-Ga-alkoxy
Le A 27 155 - 9 -
(which is optionally substituted by fluorine
and/or chlorine), or represent C1-C4-alkylthio,
Cz-C4-alkylsulphinyl or C1-C4-alkylsulphonyl
(which are optionally substituted by fluorine
and/or chlorine), ar represent aminosulphonyl,
mono- ( C1-C4-alkyl ) -aminosulphonyl, di- ( C1-Ck-
alkyl)-aminosulphonyl or C1-C~-alkoxy-carbonyl
or dimethylaminocarbonyl;
furthermore
R3 rep,,resents the radical R1 ~ ~) ~~R1 a
Rl' and Rl8 are identical or different and represent
hydrogen, fluorine, chlorine, bromine, C1-C4-
alkyl (which is optionally substituted by
fluarine and/or bromine), C1-C4-alkoxy (which is
optionally substituted by fluorine and/or
chlorine ) , or represent C1-C4-alkylthio, C1-C4
alkylsulphinyl or C1-C,,-alkylsulphonyl (which
are optionally substituted by fluorine and/or
chlorine), or represent di-(C1-C4-alkyl)-amino
sulphonyl;
furthermore
Rz~
R3 represents the radical -~R20 where
A
R19 and Rz° are identical or different and represent
hydrogen, fluorine, chlorine, bromine, cyano,
nitro, C1-C4-alkyl (which is optionally sub-
stituted by fluorine and/or chlorine), Cl-CA-
Le .~. 27 ? 55 - 10 -
~~~J ~.~~
alkoxy (which is optionally substituted by
fluorine and/or chlorine), C1-Ca-alkylthio,
C1-Cu-alkylsulphinyl or C,-C4-alkylsulphonyl
(which is optionally substituted by fluorine
and/or chlorine), di-(C1-C,,-alkyl}-amino-
sulphonyl, C1-C4-alkoxy-carbonyl or dimethyl-
aminocarbonyl, and
A represents oxygen, sulphur or the group N-Z'',
where
IO Z1 represents hydrogen, C1-Ca-alkyl (which is
optionally substituted by fluorine,
chlorine, bromine or cyano), C3-Cs-cyclo-
alkyl, benzyl, phenyl (which is optionally
substituted by fluorine, chlorine, bromine
or vitro), C1-C6-alkylcarbonyl, Cl-C4-
alkoxy-carbonyl or di- ( C1-C4-alkyl ) -amino-
carbonyl;
furthermore
R21
~-~- N
R3 represents the radical ~-~-f-R2z where
Y~
R21 and R22 are identical or different and represent
hydrogen, C1-C4-alkyl, halogen, C1-C4-alkoxycar-
bonyl, C1-C,,-alkoxy or C1-C4-halogenoalkoxy,
Y1 represents sulphur or the group N-Rz3, where
R23 represents hydrogen or C1-C~-alkyl;
furthermore
R26
R3 represents the radical ( where
Id~N~
R25
R2~1
Le A 2? 155 - 11 -
Rz4 represents hydrogen, C1-C4-alkyl , benzyl ,
pyridyl, quinolinyl or phenyl,
Rz5 represents hydrogen, halogen, cyano, vitro,
C1-Ca-alkyl (which is optionally substituted by
fluorine and/or chlorine), C1-C4-alkoxy (which
is optionally substituted by fluorine and/or
chlorine) , dioxolanyl or C1-C4-alkoxy-carbonyl
and
Rzs represents hydrogen, halogen or C1-C,~-alkyl;
furthermore
R3 represents one of the groups listed below:
H3C0 ~ H3C I I
S-'N-C4H9 ; N~~ CHZCF3
I 02
Il o
0
The invention also 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- ( C1-Cz-alkyl )
benzyl-ammonium salts of compounds of the formula (I) in
which R1, Rz and R3 have the meanings indicated above as
being preferred.
The invention particularly relates to compaunds
of the formula (I) in which
Le A 27 155 - 12 -
R1 represents hydrogen, or represents C,-C4-alkyl which
is optionally substituted by fluorine, cyano,
methoxy or ethoxy, or represents allyl, or repre-
sents C3-C6-cycloalkyl, or represents phenyl, or
represents C1-C,,-alkoxy, C3-C4-alkenyloxy, or repre-
sents C1-C3-alkyl amino, C3-C6-cycloalkylamino, or
represents di-(C~-C3-alkyl)-amino,
RZ represents chlorine or bromine, and
R5
R3 represents the group -~j where
~ , RR
R° represents fluorine, chlorine, bromine, methyl,
trifluoromethyl, methoxy, difluoromethoxy,
trifluoromethoxy, 2-chloro-ethoxy, 2-methoxy-
ethoxy, Cl-C~-alkylthio, Cz-C3-alkylsulphinyl,
C1-C3-alkylsulphonyl, dimethylaminosulphonyl,
diethylaminosulphonyl, N-methoxy-N-methylamino-
sulphonyl, N-methoxyaminosulphonyl, phenyl,
phenoxy or C1-G3-alkoxy-carbonyl, and
RS represents hydrogen, fluorine, chlorine or
bromine;
furthermore
R11
_ R12
R3 represents the radical -cH ~ ~ where
y o
Ri° represents hydrogen,
R'1 represents fluorine, chlorine, bromine, methyl,
methoxy, difluoromethoxy, trifluoromethoxy,
ethoxy, methoxycarbonyl, ethoxycarbonyl,
methylsulphonyl or dimethylaminosulphonyl, and
Le A 27 155 - 13 -
R12 represents hydrogen;
furthermore
R3 represents the radical Ro-c'~S
0
where R represents C~-Ca-alkyl, or p
Ro-c ~
represents the radical
~N~'N
where R represents Cl-C4-alkyl. ~E
3
Examples of the compounds according to the
invention are listed in fable 1 below - cf. also the
Preparation Examples.
Le A 27 X55 - 14
O
R3-SOZ-NH-CO-N~N-R1
N~R2
Table 1: Examples the compounds o the ormula (I)
o
R1 R2 R3
F
Br
C1
C1
\ _
/
_
COOCH3
CH3 F
OCHF2
CH3 C1 /
\
-
OCF~
Br
CH
3
SCH~
F
C
H
2
OCH2CH~C1
CHICH=CH2 C1
Le A 27 155 ° 15 r
Table 1: (continuation)
~a R3
COOC2H5
C1 ~
~
~
~COOCH
S 3
~ COOGH3
C 2 ( ?--C H
-
Z
OCHF2
~
'
CH3 Br -
~ CH2- .
COOCH3
/
'
CH3 Br -
~ CH2-
OCF3
C2H5 C1 ~CH~-
COOCH3
OCH C1
3
SO~CH3
O-CHI-CH=GH2 C1
Le A z7 ls5 - is -
~~2~:~~~
Table 1: (continuation)
Ri R2 Rs
F
CHI C1
S02-N(CH3)2
CH3 Br
SO'NHOCH~
CH3 C1
COOC2H5
C2H5 C1
CHF20
C1
C3Hy C1
N~N~
CH3
--rCOOCH3
C ~~ ~~1
N~N~
N\~~
~COOC~HS
CH3 C1
NON
CH3
Le ~ 27 1.55 _ 17 _
_ ~a'~,'~~.~
Table 1: (continuation)
N(CH3)Z C1 ~ ~
S COOCH3
o CF3
N(CH3>Z F
\N~
CON(CH3)2
CH3 ~ C2 ~ ~~
/~
S02NH2
CH3 C1
N~
C2H5 C1 ~CON(CH3)2
'
H3C
~~~
OCH2-CHZ-OCH3
Br
O-CHZ-CH2-C1
C1 /
\
--
Br
F J
\
~
CH3
C1
Le A 27 155 - 18 -
Table 1: (continuation)
Ri Rz Rs
0CH3
CH2-~ Br /
C1
S02 /-\
CH3 Br / \
/ \
CH3 C1 /!\ _
0 /-\
F
NlCH3)2 C1 /
CH3
CH3 C1 / \
C1
CH3
CHI Br / \
Br
Le A 27 155 - 19 -
Table 1: (continuation)
~2 ~3
C1
CH3 F' CH3"~
CH3
CH2 ~-~ C1 ~~'~ CHL_
.. OC2H5
CH3 C1
CH N-
B
3 0--
r S
Si(CH3)~
C1
'I CON(CH3)z
Br
~COOCH3
C I! ,I
1
wtd~
i
w
r
CH2-CH=CH2 Br
N>N~
CH3
Le .~ 27 i55 _ 2p
~,~2~~.~~
Table is (continuation)
Ri Ra Rs
OCHF2
CH2-CHBr-CH2-8r Br f-\ CH -
Z
SCH3
CH3 C1
S02NCH3(OCH3)
CH3 Br /-\
Sp2CH3
CH3 C1 ~ '
N02
CN3 F ~ '
CZ
C2H5 C1 ~ ' CH2_
C1
OCHF2
C2H5 Br \
OCHF2
OCF3
C3H~-n Br
Le A 27 155 - 21 -
Table 1: (continuation)
R1 RZ R3
C1
CH3 C1
SCH(CH3)2
CH3 Br /-~
If, for example, 2,6-difluoro-phenylsulphonyl isocyanate
and 5-bromo-4-ethyl-2,4-dihydro-3H-1,2,4-triazol-3-one
are used as starting substances, the course of the
reaction in process (a) according to the invention can be
outlined by the following equation:
0
F ~,
H-N~N-C2H5
S02-N=C=0 +
N'~B r
F
F O
'~ S02-NH-CO~N~N-C2H5
F ~Br
Le A 27 155 - 22 -
If, for example, 2-methoxy-benzenesulphonamide
and 5-chloro-2-chlorocarbonyl-4-methoxy-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 following equation:
0
OCH3 ll
C1-CO-N~N-OCH3
502-NH2 + f
~C1
.. OCH3 O
/-_\ ~
---~ S02-NH-CO~N~N-OCH3
-HC1
~C 1
If, for example, 5-bromo-4-dimethylamino-2,4-
dihydro-3H-1,2,4-triazol-3-one and N-methoxycarbonyl-2-
trifluoromethyl-benzenesulphonamide are used as starting
substances, the course of the reaction in process (c)
according to the invention can be outlined by the follow-
ing equation:
0
CF3 ~
\ H-N~N-N(CH3)2
~S02-NH-COOCH3 + ~
~Br
CF3 0
-°'° ~-~ S02-NH-CO~N~N-N(CN3)2
-HOCH3 ~
~Br
Le A 27 155 - 2~ -
Formula (II) provides a general definition of the
halogenated triazolinones to be used as starting substan-
ces in processes (a) and (e) according to the invention
for the preparation of compounds of the formula (I).
In formula (II), R1 and RZ preferably, or in
particular, have those meanings which have already been
given above in connection with the description of the
compounds of the formula (I) according to the invention
as being preferred, or particularly preferred, for R1 and
RZ .
~:Yamples of the starting substances of the
formula (II) are listed in Table 2 below.
0
HN~N~R1
N--~R2 ( I I )
Table 2: Examples of the starting substances of the
formula (II):
~z
H Br
CH3 Br
C2H5 Br
C3H7 Br
CH(CH3)2 C1
C4H9 C1
CH3 C1
C2H5 C1
Bs
CH2-CH=CHI gs
Le A 27 155 _ 2~ -
Table 2: (continuation)
Ra Rz
CH(CH3)2 F
CH3 F
C3H~ CI
C2H5 F
/~\
Br
N(CH3)2 Br
N(CH3)2 CI
NH-CH3 Br
OCH3 Br
OCH3 C1
C2H5 F
C3H~ F
C1
F
OOHS Br
OCZHS C1
CH2-C I Br
CH2~ C1
C(CH3)3 Br
CH2-CH(CH3)2 Br
CH2-CH(CH3)2 C1
CH2~ Br
0-CBH~-n Br
Le .A 27 155 _ 25
Table 2: (continuation)
CH2 Br
~' C 1
C1
CZHS I
CqHg Br
iH-C2H5 Br
CH3
~H-CZHS~ C1
CH3
CH(CH3)2 C1
CHZ-CHBr-CH2Br Br
CHZ-CHBr-CHZBr C1
Br
CN3
C1
CH3
F
C1
Br
Le A a~ i5s _ 2s
Table 2: (continuation)
Ri RZ
Br
C1
Br
C1
OC3N~ C1
The starting substances of the formula (II) are
known andlor can be prepared by processes known per se
(cf. Chem. Ber. 102 (1969), 755-766 and the Preparation
Examples).
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 ( I II ) , 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
preferred, or particularly preferred, for R3.
The following may be mentioned as examples of the
starting substances of the formula (III): 2-fluoro-, 2-
Le A 27 155 .. 27
~~~~s~3
chloro-, 2-bromo-, 2-methyl-, 2-methoxy-, 2-trifluoro-
methyl-, 2-difluoro-methoxy-, 2-trifluoromethoxy-, 2-
methylthio-, 2-ethylthio-, 2-propylthio-, 2-methyl-
sulphinyl-, 2-methylsulphonyl-, 2-dimethylaminosulpho-
nyl-, 2-diethylaminosulphanyl-, 2-(N-methoxy-N-methyl)-
aminosulphonyl-, 2-phenyl-, 2-phenoxy-, 2-methoxy-
carbonyl-, 2-ethoxycarbonyl-, 2-propoxycarbonyl- and 2-
isopropoxycarbonyl-phenylsulphonyl isocyanate,2-fluoro-,
2-chloro-, 2-difluoromethoxy-, 2-trifluoromethoxy-, 2-
methoxycarbonyl- and 2-ethoxycarbonyl-benzylsulphonyl
isocyanate, 2-methoxycarbonyl-3-thienyl-sulphonyl iso-
cyanate, 4-methoxycarbonyl- and 4-ethoxycarbonyl-1-
methyl-pyrazol-5-yl-sulphonyl isocyanate.
The sulphonyl isocyanates of the formula (TII)
are known and/or can be prepared by processes known per
se (cf. US Patent 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, 1?3,312).
Process (a) according to the invention for the
preparation of 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 aromatic,
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, tetrahydrafuran and dioxane,
Le A 27 155 - 28 _
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 propionitxile, amides, such
as, for example, dimethylformamide, dimethylacetamide and
N-methyl-pyrrolidone, and also dimethyl sulphoxide,
tetramethylene sulphone and hexamethylphosphoric
triamide.
When carrying out process (a) according to the
invention, the reaction temperatures can be varied within
a substantial range. In general, the process is carried
out at temperatures between 0°C and 150°C, preferably at
temperatures between 10°C and 80°C.
Process (a) according to the invention is gener-
ally carried out under atmospheric pressure.
Far 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, concentrated, and the crude product
which remains in the xesidue is crystallized using a
suitable solvent, such as, for example, diethyl ether.
The product of the formula (I) which is obtained as
crystals is isolated by filtration with suction.
Formula (IV) provides a general definition of the
triazolinone derivatives to be used as starting substan
ces in process (b) according to the invention for the
Le A 27 155 - 2g _
~~~~=~~.~3.~
preparation of compounds of the formula (I).
In formula (IV), R1 and Rz 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 R1 and
R2, and
Z preferably represents chlorine, C1-C4-alkoxy,
benzyloxy or phenoxy, in particular methoxy or
phenoxy.
:..xamples which may be given for the starting
substances of the 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
25 chloroformate, benzyl chloro~~rmate, phenyl chloroformate
or diphenyl carbonate.
The starting substances of the formula (IV) were
hitherto unknown.
The new halogenated triazolinone derivatives of
ZO the formula (IV) are obtained when triazolinones of the
general formula (II)
0
HN~N~R1 (II)
N~R 2
in which
R1 and Rz have the abovementioned meanings,
25 are reacted with carbonic acid derivatives of the general
Le A 27 Z55 -. 30
formula (XI)
z-CO-Z1 (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, fox
example, tetrahydrofuran, and if appropriate in the
presence of an acid acceptor, such as, for example,
sodium hydride or potassium tert-butylate, at tempera-
tures between -20°C and +100°C (cf. also the Preparation
Examples).
Formula (V) grovides a general definition of the
sulphonamides also to be used as starting substances in
35 process (b) according to the invention for the prepara
tion of compounds of the formula (I). _
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 prefer-
red, or particularly preferred, for R3.
The following may be mentioned as examples of the
starting substances of the formula (V): 2-fluaro-, 2-
chloro-, 2-bromo-, 2-methyl-, 2-methoxy-, 2-trifluoro-
methyl-, 2-difluoro-methoxy-, 2-trifluoromethoxy-, 2-
methylthio-, 2-ethylthio-, 2-propylthio-, 2-methyl-
sulphinyl-,2-methylsulphonyl-,2-dimethylaminosulphonyl-
2-diethylaminosulphonyl-, 2-(R1-methoxy-N-methyi)
aminosulphonyl-, 2-phenyl-, 2-phenoxy-, 2-methoxy_
carbonyl-, 2-ethoxycarbonyl-, 2-propoxycarbonyl- and 2
I~e .A 2 7 15 5 _ 31 _
~~~3 ~. ~~
isopropoxycarbonyl-benzenesulphonamide, 2-fluoro-, 2-
chloro-, 2-difluoromethoxy-, 2-trifluoromethoxy-, 2-
methoxycarbonyl- and 2-ethoxycarbonyl-phenylmethane-
sulphonamide, 2-methoxycarbonyl-3-thiophenesulphonamide,
4-methoxycarbonyl- and 4-ethoxycarbonyl-1-methyl-
pyrazole-5-sulphonamide.
The sulphonamides of the formula (V) are known
andlor can be prepared by processes known per se (ef. US
Patent 4,12?,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).
Process (b) according to the invention prepara-
tion of the new compounds of the formula (I) is prefera
bly carried out using diluents. Suitable diluents for
this purpose are virtually all inert organic solvents,
for example those which are indicated above for process
(a) according to the invention.
Acid acceptors which can be employed in process
(b) according to the invention are all acid-binding
agents which can customarily be employed 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 tart-butylate and
potassium tart-butylate, furthermore aliphatic, aromatic
or heterocyclic amines, for example triethylamine,
trimethylamine, dimethylaniline, dimethylbenzylamine,
pyridine, 1,5-diazabicyclo-[4.3.0]-non-5-ene (DEN), 1,8-
he A 27 155 - 32
~~2~~.0~
diazabicyclo-[5.4.0]-undec-7-ene (DBU) and 1,4-diaza-
bicyclo-[2.2.2]-octane (DABCO).
When carrying out process (b) according to the
invention, the reaction temperatures can be varied within
a substantial range. In general, the process is carried
out at temperatures between 0°C and 100°C, preferably at
temperatures between 10°C and 60°C.
Process (b) according to the invention is gener
ally 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 specifically employed components in a substantial
excess. The reactions are generally carried out in a
suitable diluent in the presence of an acid acceptor, and
the reaction mixture is stirred for several hours at the
ZO specifically required temperature. Working-up in process
(b) according to the invention is carried out in each
case by customary methods.
The halogenated triazolinones of the formula (II)
to be used as starting substances in process (c) accord
ing 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 for
Le A 27 155 - 33 -
~~U~~~.~~
the preparation of compounds of the formula (I}.
In formula (VI), R3 and Z preferably, or in
particular, have those meanings which have already peen
indicated 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,
f or R3 and Z .
Process (c) according to the invention is prefer-
ably carried out using diluents. Suitable diluents for
this purpose are the same organic solvents which have
been mentioned above in connection with the description
of process (a) according to the invention.
If appropriate, process (c) is carried out in the
presence of an acid acceptor. Suitable acid-binding
agents for this purpose are the same which have been
mentioned above in connection with the description of
process (b) according to the invention.
When carrying out process (c) according to the
invention, the reaction temperatures can be varied within
a substantial range. In general, the process is carried
out at temperatures between 0°C and 100°C, preferably at
temperatures between 10°C and 60°C.
Process (c) according to the invention is gener
ally carried aut under atmospheric pressure. However, it
is also possible 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 equimolar
amounts. However, it is also possible to use one of the
Le A 27 155 - 3~ -
two specifically employed components in a substantial
excess. The reactions are generally 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 recyuired temperature. Working-up in process
(c) according to the invention is carried out in each
case by customary methods.
To convert the compounds of the formula ( I ) to
salts, they are stirred with suitable salt formers, such
as, for 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
then be isolated as crystalline products, if necessary
after concentration.
The active compounds according to the invention
can be used as defoliants, desiccants, agents for des-
troying 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 aenera° Sinapis,
Lepidium, Galium, Stellaria, Matricaria, Anthemis,
Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus,
Le ~ 27 155 _ 35 _
Portulaca, Xanthium, Canvolvulus, Ipomoea, Polygonum,
Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solarium,
Rorippa, Rotala, Lindernia, Lamium, Veronica, Abutilon,
Emex, Datura, Viola, Galeopsis, Papaver, Centaurea,
Trifolium, Ranunculus and Taraxacum.
Dicotvledon cultures of the genera~ Gossypium,
Glycine, Beta, Daueus, Phaseolus, Pisum, Solarium, Linum,
Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Bras-
sica, Lactuca, Cucumis and Cucurbita.
Monocotyledon weeds of the genera~ Echinochloa,
Setaria, Panicum, Digitaria, Phleum, Poa, Festuca,
Eleusine, Brachiaria, Lolium, Bromus, Avena, Cyperus,
Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis,
Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum,
Sphenoclea, Dactyloctenium, Agrastis, Alopecurus and
Apera.
Monocotyledon cultures of the genera_ Oryza,
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, far 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 planta-
tions, tea plantations, rubber plantations, oil palm
Le A 27 155 - 3s -
plantations, cocoa plantations, soft fruit plantings arid
hopfields, in ornamental lawns, sports fields and grazing
land, and for the selective combating of weeds in annual
cultures.
The compounds of the formula (I) according to the
invention are particularly suitable for selectively
combating monocotyledon and dicotyledon weeds in mono
cotyledon crops, using the pre-emergence or the post
emergence method. They are markedly more effective than,
for example, isocarbamid.
To a certain extent, the compounds according to
the invention also have a fungicidal action, for example
against powdery mildew on vines arid against Pyricularia
oryzae 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, for example by mixing the active compounds with
extenders, that is liquid solvents and/or solid carriers,
optionally with the use of surface-active agents, that is
emulsifying agents and/or dispersing agents and/or foam-
forming agents.
In the case of the use of water as an extender,
organic solvents can, for example, also be used as
auxiliary solvents. As liquid solvents, there are
Le A 27 155 - 37
suitable in the main: aromatics, such as xylene, toluene,
ox alkylnaphthalenes, chlorinated aromatics and chlorina-
ted aliphatic hydrocarbons, such as chlorobenzenes,
chloroethylenes or methylene chloride, aliphatic hydro-
carbons, such as cyclohexane or paraffins, for example
petroleum fractions, mineral and vegetable oils,
alcohols, such as butanol or glycol as well as their
ethers and esters, ketones, such as acetone, methyl ethyl
ketone, methyl isobutyl ketone or cyclohexanone, strongly
polar solvents, such as dimethylformamide and dimethyl
sulphoxide, as well as water.
As solid carriers there are suitable: for example
ammonium salts and ground natural minerals, such as
kaolins, clays, talc, chalk, quartz, attapulgite, mon~tmo-
rillonite or diatomaceous earth, and ground synthetic
minerals, such as highly disperse silica, alumina and
silicates, as solid carriers for granules there are
suitable: for example crushed and fractionated natural
rocks such as calcite, marble, pumice, sepiolite and
dolomite, as well as synthetic granules of inorganic and
organic meals, and granules of organic material such as
sawdust, coconut shells, maize cobs and tobacco stalks;
as emulsifying and/or foamforming agents there are
suitable: for example non-ionic and anionic emulsifiers,
such as polyoxyethylene fatty acid esters, polyoxyethy-
lene fatty alcohol ethers, for example alkylaryl polygly-
col ethers, alkylsulphonates, alkyl sulphates, arylsul-
phonates as well as albumen hydrolysis products; as
dispersing agents there are suitable: for example lignin-
sulphite waste liquors and methylcellulose.
he A 27 155 - 3g _
~~~~~a~
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.
It is possible to use colorants such as inorganic
pigments, far example iron oxide, titanium oxide and
Prussian Hlue, 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
(AMETFIYDIONE) or N-(2-benzothiazolyl)-N, N'-dimethylurea
(3KETABENZTAIAZURON) for combating weeds in cereals; 4-
amino-3-methyl-6-phenyl-1,2,4-triazin-5(4~I)-one
{I~IETAMITRON) for combating weeds in sugar beet, and 4-
amino-6-(1,1-di.methylethyl)-3-methylthio-1,2,4-triazi.n-
5(4H)-.one (PiETRIBUZIN) for combating weeds i.n soya beans;
Le A 27 155 - 3g -
furthermore also 2,4-dichlorophenoxyacetic acid (2,4-D);
4-(2,4-dichlorophenoxyj-butyric acid (2,4-DBj; 2,4-
dichlorophenoxypropionic 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 (BROI~IOXYNIL); 2-
chloro-N~[(4ametlnoxy-6-methyl-1,3,5-triazin-2-yl)-amino]-
carbonyl}-benzenesulphonamide (CHLORSULFURON); N,N-di-
methyl-N'-(3-chloro-4-methylphenyl)-urea (CHLORTOLURON);
4-amino-6-t-butyl-3-ethylthio-1,2,4-triazin-5(4H)-one
(ETHIOZIN); [(4-amino-3,5-dichloro-6-fluoro-2-pyridinyl)-
oxy]-acetic acid or its 1-methylheptyl ester
(FLUROXYPYR);methyl2-[4,5-dihydro-4-methyl -4-(1-methyl-
ethyl)-5-oxo-1H-imidazol-2-yl]-4(5)-methylbenzoate
(IMAZAMETHABENZ); 3,5-diiodo-4-hydroxybenzonitrile
(IOXYNIL); N,N-dimethyl-N'-(4-isopropylphenyl)-urea
(ISOPROTURONj; (2-methyl-4-chlorophenoxy)-acetic acid
(MCPA); (4-chloro-2-methylphenoxy)-propionic acid (MCPP);
N-methyl-2-(1,3-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); O-(6-chloro
3-phenyl-pyridazin-4-yl) S-octyl thiocarbonate
(PYRIDATE);
4-ethylamino-2-t-butylamino-6-methylthio-s-triazine
(TERBUTRYNE); methyl 3-[[[[(4-methoxy-6-methyl-1,3,5-
triazin-2-yl)-amino]-carbonyl]-amino]-sulphonyl]-
thiophene-2-carboxylate (THTAMETURON) and 5-(2,3,3-
trichloroallyl) N,N-diisopropylthiocarbamate (TRI-
Le A 27 155 - 40 -
ALLATE). Surprisingly, 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
foran of their formulations or in the use forans prepared
therefrom by further dilution, such as ready-to-use
solutions, suspensions, emulsions, powders, pastes and
granules. They are used in the customary manner, for
example by watering, spraying, atomizing or scattering.
The active compounds according to the invention
can be applied either before or after emergence of the
plants.
They can also be incorporated into the soil
bafore 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.
Le A 27 155 _ 41
Preparation Examples
Example 1
COOCH3 0
~ S02-NH-CO-N~N-N(CH3?2
~1
(Process (a))
P2.8 g (I7.2 mmol) of 5-chloro-4-dimethylam._no-
2,4-dihydro-3H-I,2,4-triazol-3-one are dissolved in 6~ ml
of acetonitrile and 6.6 g (27.4 mmol) of 2-meth~xy-
carbonyl-phenylsulphonyl isocyanate, dissolved in 2? ml
of acetonitrile, are added to this solution ~~ith
stirring. The reaction mixture is stirred for 6 hour: at
20°C and then concentrated. The residue which remains is
stirred with diethyl ether, and the product obtaine<in
crystalline form is isolated by filtration with suct._on.
6 . 9 g ( 99 ~ of theory) of 5-chloro-4-dimet:iyl
amino-2-(2-methoxycarbonyl-phenylsulphonyl-am_no
carbonyl)-2,4-dihydro-3H-1,2,4-triazol-3-one of mel~:ing
point 145°C are obtained.
Example 2
C1 0
S02-NH-CO-N~N-N(CH3?2
CH 3 N~'~B r
Le A 27 155 - 42 -
~(~~~~ ~~
(Process (b))
1.9 g (12.5 mmol) of 1,8-diazabicyclo-[5.4.0]-
undec-7-ene (DBU) and 2.6 g (12.6 mmol) of 2-chloro-6-
methyl-benzenesulphonamide are added to a solution of
4.0 g (12.2 mmol) of 5-bromo-4-dimethylamino-2-phenoxy-
carbonyl-2,4-dihydro-3H-1,2,4-triazol-3-one in 60 ml of
acetonitrile. The reaction mixture is stirred for 3 hours
at 20°C, then poured into approximately twice the volume
of ice-water and then brought to a pH of approximately 2
by adding 2~1 hydrochloric acid. The mixture is subse-
quentlyP extracted using methylene chloride, and the
organic phase is washed with water, dried with sodium
sulphate and filtered. The filtrate is concentrated, the
residue is stirred with diethyl ether, and the product
which is obtained in crystalline form is isolated by
filtration with suction.
1.0 g (19 $ of theory) of 5-bromo-4-dimethyl
amino-2-(2-chloro-6-methyl-phenylsulphonyl-amino
carbonyl)-2,4-dihydro-3H-1,2,4-triazol-3-one of melting
point 163°C is obtained.
Other examples of the compounds which can be
prepared analogously to Examples 1 and 2 and following
the general description of the preparation processes
according to the invention are those which are listed in
2S Table 3 below.
0
R3-S02-NH-CO-N~N-RI
N~ ----.~R 2
Le A 27 155 - 43
Table 3:
Preparation examples of the compounds of the formula (I)
Ex. R1 R2 R3 Melting point
No. ('~)
COOCH3
~
3 CH3 C1 -~ 170
COOCH3
~
4 CH3 Br -~ 173
COOCH3
N(CH3)2 Br ~ _~ 139
COOCH3
6 -a Br ~-~ I55
COOCH3
7 ~ C1 ~-~ 148
COOCH3
~
8 C3H7 Br -~ 120
COOCH3
~
9 C3H7 C1 -~ lI9
Le A ~7 155 - 44 -
fable 3: (continuation)
Ex. Melting point
Duo R~ R2 R3 ( C )
.
C1
CH3 C1 ~ ~ 191
CH3
to C1
11 CH3 Br ~ 159
CH3
C1
12 --a Br ~ 168
CH3
CI
13 "'q C1 ~ ~ 162
CH3
COOCH3
19 C2H5 Hr !-~ 197
COOCH3
15 C2H5 C1 ~-' 161
C1
16 C2H5 Hr ~ 161
CH3
Le A 27 155
~; ,(~ a
Wi~Ed~.l.~v
Table 3: (continuation)
Ex. Melting point
No. R1 R2 R3 (C>
C1
17 C2H5 C1 ~ 156
CH3
IO OGF3
18 ""~ C 1 ~
14 2
OCF3
19 -~ Br ~ 134
OCF3
CH3 C1 ~-~ 144
20
OCF3
21 CH3 Br
I69
OCF3
22 C2H5 C1 ~ 122
OCF3
23 C2H5 Br ~ 133
24 --~ C1 ~ ' 174
COOCH3
La A 27 155 - 46
r~~~~~~
Startin4 substances of the formula (II~~
Example r( II-1~,
H-N~N~N(CH3)2
~Br
Stage 1:
0
H-N~N~N(CH3>2
H
856 g (4.0 mol) of diphenyl carbonate are dis-
solved in 5B8 g of ethylene chloride. With water-cooling,
245 g (4.0 mol) of dimethylhydrazine (98 ~) are added
dropwise, the mixture is then warmed slowly, and, after
4 hours, stirring is continued at 60°C.
After the mixture has cooled to 20°C, 200 g
(4.0 mol) of hydrazine hydrate are added dropwise and
stirring is continued for 12 hours. The mixture is warmed
to 70-80°C, and, after approximately 1 hour, stirred
again. When cold, the solution is distilled in vacuo,
during which process ethylene chloride and water are
removed (bottom temperature in the end 100°C). The above
phenolic dimethyl carbodihydrazide solution is added
dropwise in the course of 90 minutes at reflux tempera-
ture (approximately 102°C) to 424 g (4.0 mol) of tri-
methyl orthoformate. After the methanol which has formed
has been removed by distillation, phenol is distilled off
in vacuo, and at a head temperature of 85-105°C, 282 g of
Le A 27 155
_ 97
~U2U~.~3~
product mixture are subsequently obtained. This mixture
is boiled with 600 ml of acetone and, after filtration at
boiling temperature, the filtrate is cooled. The product
which is obtained during this process in crystalline form
is isolated by filtration with suction.
71 g (14 ~ of theory) of 4-dimethylamino-2,4-
dihydro-3H-1,2,4-triazol-3-one of melting point 127°C are
obtained.
Sta_c~e 2:
0
H-N~N~'N(CH3)2
Br
18.8 g (0.117 mol) of bromine are added with ice-
caoling in the course of 2 hours to a stirred mixture of
15.0 g (0.117 mol) of 4-dimethylamino-2,4-dihydro-3H-
1,2,4-triazol-3-one, 4.7 g (O.lI7 mol) of sodium hydr-
oxide and 150 ml of water. The product which is obtained
in crystalline form is subsequently isolated by filtra-
tion with suction.
19.6 g (81 ~ of theory) of 5-bromo-4-dimethyl
amino-2,4-dihydro-3H-I,2,4-triazol-3-one of melting 163°C
are obtained.
Le .A 27 155
- 48 -
Example ~( I I-2 J,
O ,
H-N~N~N(CH3>2
~C1
A mixture of 6.0 g (0.029 molj of 5-bromo-4-
dimethylamino-2,4-dihydro-3H-1,2,4-triazol-3-one and
200 ml of concentrated hydrochloric acid is refluxed for
3 hours. The mixture is then concentrated, the residue is
taken up in a little water, the mixture is rendered
neutral using sodium hydrogen carbonate, and the product
which is obtained in crystalline form is isolated by
filtration with suction. The filtrate is extracted using
ethyl acetate, the crystalline product which has previ-
ously been isolated is added to the organic phase, and
the latter is dried with sodium sulphate and filtered.
The filtrate is concentrated, the residue is triturated
with diethyl ether, and the product which is obtained in
crystalline form during this process is isolated by
filtration with suction.
3.1 g (66 ~ of theory) of 5-chloro-4-dimethyl
amino-2,4-dihydro-3H-1,2,4-triazol-3-one of melting point
158°C are obtained.
Other exaanples of compounds of the formula (IIj
which can be prepared analogously to Examples (II-lj and
(II-2j are those listed in Table 4 below.
Le A 27 155
- 49 -
0
HN~N~R1 (II)
~R2
Table 4: Preparation examples of the compounds of the
formula (II)
Example R1 R2 Melting point
No. (°C)
II-3 -~ Br 137
lI-4 C3H7 Br X18
II-5 --~ C1 121
II-6 C3H7 C1 yl
II-7 C2H5 Br 142
II-8 C2H5 C1 112
II-9 CH2~ Br
II-10 CH2-~ CI
Le ~ 27 155
- 50 -
~L~~~fl~
Starting substances of the formula ~IV)~
Example ~j IV-11
O
~ 0-CO-N~N-N(CH3>2
NAB r
7.0 g (33.8 mmol) of 5-bromo-4-dimethylamino-2,4-
da_hydro-3H-1,2,4-triazol-3-one are taken up in 100 ml of
water and 100 ml of methylene chloride, and 0.2 g of
tetrabutylammonium bromide and 1.5 g (37.5 mmol) of
sodium hydroxide are added. 5.9 g (37.7 mmol) of phenyl
chloroformate are then added dropwise at 20°C with
vigorous stirring, and the reaction mixture is stirred
for a further 12 hours at 20°C. The organic phase is
separated off, washed with water, dried with sodium
sulphate and filtered. The filtrate is concentrated, the
residue is stirred with diethyl ether, and the product
which is abtai.ned in crystalline form in this process is
isolated by filtration with suction.
8.7 g (79 ~ of theory) of 5-bromo-4-dimethyl-
amino-2-phenoxycarbonyl-2,4-dihydro-3H-1,2,4-tri.azol-3-
one of melting point 136°C are obtained.
Use Examples:
In the following Use Examples, the known her-
bicide isocarbamid of formula (A) below is used as
comparison substances
Le A 27 155
- 51 -
~~2~:~.~~
n (A,
HN~-CO-NH-CH2CH(CH3)2
0
(disclosed in EE 737,449; DE 1,795,117).
T~e A 27 155
- 52 -
Example A
Pre-emergence test
Solvent: 5 parts :oy weight of acetone
Emulsifier: 1 part by weight of alkylaryl polyglycol
ether
To produce a suitable preparation of active
compound, 1 part by weight of active compound is mixed
with the stated amount of solvent, the stated amount of
emulsifier is added and the concentrate is diluted with
water to the desired concentration.
Seeds of the test plants are sown in normal soil
and, after 24 hours, watered with the preparation of the
active compound. It is expedient to keep constant the
amount of water per unit area. The con;:entration 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 da~r~age
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
Tn this test, for example the compounds of Pre~_ar-
ation Example 3 , 6 and 7 show a clearly superior activity com-
pared with the prior art.
Le A 27 155
- 53 -
' ~~~~'~.fl
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 2,000 1 of
water/ha. After three weeks, the degree of damage to the
plants is rated in ~ damage in comparison to the
development of the untreated control. The figures denote:
0~ = no action (like untreated control)
100 = total destruction
In this test, for example the compounds of Pre~ar-
ation Example 3 , 6 and 7 show a clearly sur~erior acti~ritv_ 'com-
pared with the prior art.
he A 27 155
- 54 -
