Note: Descriptions are shown in the official language in which they were submitted.
3 iJ
The invention relates to new sulphonylamino-
carbonyltriazolinones, to several processes for their
preparation, and to their use as herbicide~.
It is known that certain substituted amino-
carbonylimidazolinones, such as, fox example, 1-isobutyl~
aminocarbonyl-2-imidazolidinone (isocarbamide), have
herbicidal properties (cf. R~ Wegler, Chemie der
Pflan~enschutz-undSchadlingsbekampfungsmittel[Chemistry
of Plant Protection 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 sulphonylamino-
carbonyl-t~iazolinones of the general formula (I)
R3-So2-NH-Co-N ~ N-R1 (I)
N=~R 2
in which~5 R1 repres~nts hydrogen, hydroxyl or amino, or repre-
sents an optionally substituted radical from the
series comprising alkyl, alkenyl, alkinyl, cyclo-
alk~l, aralkyl, aryl, alkoxy, alkenyloxy, alkylamino
and dialkylamino,~0 R2 represents hydrogen, hydro~yl, mercapto or amino, or
represents an optionally substituted radical from
the series comprising alkyl, cycloalkyl,
Le A 27 154 - 1 -
cycloalkenyl, aralkyl, aryl, alkoxy, alkylamino and
dialXylamino, and
R3 represents an optionally substituted radi~al 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 of
the general formula (I) are obtained when
a) triazolinones of the general formula (II)
Hl ~ N-R1 (II)
N~R2
in which
R1 and R2 have the abovementioned meanings,
are reacted with sulphonyl isocyanates of the
qeneral formula (III)
R3-So2-N=C=o (III)
in which
R3 has the abovementioned ~n; ~g,
if appropriate in the presence of a diluent, or when
b) triazolinone derivatives of the general formula (IV)
Le A 27 154 - 2 -
3 ~
o
Z-CO-N ~ N-R1 (IV)
~R2
in which
Rl and R2 have the abovementioned meanings and
Z represents halogen, alkoxy, aralkoxy or aryloxy,
are reacted with sulphon~mides of ~he general
S formula (V)
R3-So2-NH2 (V)
in which
R3 has the 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
HN ~ N-R
~R2
in which
R1 and R2 have the abovementioned meanings
Le A 27 154 _ 3 _
~ ~3 2 ~
are reacted with sulphonamide derivatives of the
general formula (VI)
R3-So2-NH-Co-Z ~VI)
in which
R3 has the abo~. ?ntioned -~n i ng and
Z represents halogen, alkoxy, aralkoxy or aryloxy,
if appropriate in the pre~ence of an acid acceptor
and if appropriate in the presence of a diluent,
and, if appropriate, salt~ are formed by customary
methods from the compounds of the formula (I)
prepared by process ~a), tb) or (c).
The new sulphonylaminocarbonyltriazolinones of
the general formula (I) and their salts are distinguished
by a powerful herbicidal activity. Surprisingly, the new
compounds of the formula (I) show a considerably better
herbicidal action than the known herbicide l-isobutyl-
aminocarbonyl-2-imidazolidinone (isocarbamide), which has
a similar structure.
The invention preferably relates tG compounds of
the formula (I) in which
R1 represents hydxogen, hydroxyl or amino, or repre-
sents C1-C6-alkyl which is optionally substituted by
fluorine, chlorine, bromine, cyano, C1-C4-alkoxy,
C1-C4-alkylcarbonyl or Cl-C4-alkoxy-carbonyl, 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 i~ optionally substituted by fluorine,
Le A 27 154 - 4 -
chlorine, bl~- inQ and/or C1-C4-alkyl, or represents
phenyl-Cl-C3-alkyl which is optionally substituted by
fluorine, chlorine, bl~ ; ne~ cyano, nitro, C1-C4-
alkyl, trifluoromethyl, Cl-C4-alkoxy and~or Cl-C4-
alkoxy-carbonyl, or represents phenyl which is
optionally substituted by fluorine, chlorine,
bL~ in~ cyano, nitro, Cl-C4-alkyl, trifluoromethyl,
Cl-C4-alkoxy, fluorine- and/or chlorine-substituted
Cl-C3-alkoxy, Cl-C4-alkylthio, fluorine and/or
chlorine-substituted Cl-C3-alkylthio, Cl-C4-alkylsul-
phinyl~ Cl-C4-alkylsulphonyl and/or Cl-C4-alkoxy-
carbonyl, or represents C1-C~-alkoxy which is option-
ally substituted by fluorine, chlorine, cyano,
phenyl, Cl-C4-alkoxy or Cl-C4-alkoxy-carbonyl, or
rep.resents C3-C4-alkenyloxy, or represents Cl-C4-
alkylamino which is optionally substituted by
fluorine, cyano, Cl-C4-alkoxy or Cl-C4-alkoxy-car~
bonyl, or represents di-(Cl-C4-alkyl)-amino,
R~ represents hydrogen, hydroxyl, mercapto or amino, ox
represents Cl-C6-alkyl which is optionally ~ubstitut-
ed by fluorine, chlorine, bromine, cyano, C3-C6-
cycloalkyl, C1-C4-alkoxy or C1-C4-alkoxy-carbonyl, or
xepresents C3-C6-cycloalkyl which is optionally
substituted by fluorine, chlorine, bromine and/or
Cl-C4-alkyl, or represents cyclohexenyl, or repre-
sents phenyl-Cl-C3-alkyl which is optionally substi-
tuted by fluorine, chlorine, bromine, cyano, nitro,
Cl-C4-alkyl, trifluoromethyl, Cl-C4-alkoxy and/or
C1-C4-alkoxy carbonyl, or represents phenyl which is
optionally substituted by fluorine, chlorine,
Le A 27 154 - 5 -
2 ~ ~
bromine, cyano, nitro, Cl-C4-alkyl, trifluoromethyll
Cl-C4-alkoxy, fluorine- and/or chlorine-substituted
Cl-C3~alkoxy, Cl-C4-alkylthio, fluorine- and/or
chlorine-substituted Cl-C3-alkylthio, Cl-C4-alkyl-
sulphinyl, Cl-C4-alkylsulphonyl and/or Cl-C4-alko~y-
carbonyl, or represents Cl-C8-alkoxy which is option-
ally substituted by fluorine, chlorine, cyano, Cl-C4-
alkoxy or Cl-C4-alkoxy-carbonyl, or represents Cl-C4-
alkylamino or di-(Cl-C4-alkyl)-amino, and
R3 represents the group ~ R5 , where
~4 and R5 are identical or different and represent
hydrogen, fluorine, chlorine, bromine, iodine,
nitro, Cl-C6-alkyl (which is optionally substituted
by fluorine, chlorine, bromine, cyano, carboxyl,
Cl-C4-alkoxycarbonyl, Cl-C4-alkylamino~carbonyl, di-
(Cl-C4-alkyl)amino-carbonyl, hydroxyl, Cl-C4-alkoxy,
formyloxy, Cl-C4-alkyl-carbonyloxy, Cl-C4-alkoxy-
carbonyloxy, Cl-C4-alkylamino-carbonyloxy, Cl-C4-
alkylthio, Cl-C4-alkylsulphinyl, Cl-C4-alkylsulphonyl,
di-(Cl-C4-alkyl)-aminosulphonyl, C3-C6-cycloalkyl or
phenyl), or represent C2-C6-alkenyl (which is option-
ally substituted by fluorine, chlorine, bromine,
cyano, Cl-C4 alkoxy-carbonyl, carboxyl or phenyl), or
represent C2 C6-alkinyl ~which is optionally substi-
tuted by fluorine, chlorine, bromine, cyano, Cl-C4-
alkoxy-carbonyl, carboxyl or phenyl), or represent
Le A 27 154 - 6 -
~ ~q ~ i J ~J ~3
C1-C4-alkoxy (which is optionally substituted by
fluorine, chlorine, bl~- ine~ cyano, carboxyl, Cl-C~-
alkoxy-carbonyl, Cl-C4-alkoxy, C1-C4-alkylthio, Cl-C4-
alkylsulphinyl or C1-C4-alkylsulphonyl), or represent
C1-C4-alkylthio (which is optionally substituted by
fluorine, chlorine, b~l ine, cyano, carboxyl, Cl-C4-
alkoxy-carbonyl, Cl-C4-alkylthio, Cl-C4-alkylsulphinyl
or Cl-C4-alkylsulphonyl), or represent C3-C6~alkenyl-
oxy (which is optionally substituted by fluorine,
chlorine, bromine, cyano or C1-C4-alkoxy-carbonyl),
or represent C2-C6-alkenylthio (which is optionally
substituted by fluorine, chlorine, b~l- ine, cyano,
nitro, C1-C3-alkylthio or C1-C4-alkoxycarbonyl),
C3-C6-alkinyloxy, C3-C6-alkinylthio, or represent the
radical -S(O)p-R6 where
p represents the numbers 1 or 2 and
R6 represents Cl-C4-alkyl (which is optionally
substituted by ~luorine, chlorine, bl~- ine, cyano
or Cl-C4-alkoxy-carbonyl)~ C3-C6-alkenyl, C3-C6-
alkinyl, Cl-C4~alkoxy, Cl-C4-alkoxy-Cl-C4-alkyl-
amino, Cl-C4-alkylamino, di-(Cl-C4-alkyl)-amino or
phenyl~ or represents the radical -NHoR7 where
R7 represents C1-C12-alkyl (which is optionally
substituted by fluorine, chlorine, cyano,
Cl-C4-alkoxy, Cl-C4-alkylthio, Cl-C4-alkylsul-
phinyl, Cl-C4-alkylsulphonyl, Cl-C4 alkyl-
carbonyl, C1-C4-alkoxycarbonyl, C1-C4-alkyl-
amino-carbonyl or di-(Cl-C4 alkyl)-amino-
carbonyl), or represents C3-C6-alkenyl (which
is option lly substituted by fluorine,
Le A 27 154 - 7 -
2~
chlorine or bromine), C3-C6-alkinyl, C3-C6-
cycloalkyl, C3-C6-cycloalkyl-Cl-C2-alkyl,
phenyl-C1-C2-alkyl (which is optionally substi-
tuked by fluorine, chlorine, nitro, cyano,
Cl-C4-alkyl, Cl-C4-alkoxy or Cl-C4-alkoxy car-
bonyl), or represents benzohydryl, or repre-
sents phenyl (which is optionally substituted
by fluorine, chlorine, nitro, cyano, C1~C4-
alkyl, trifluoromethyl, Cl-C4-alkoxy, Cl-C2-
fluoroalkoxy, Cl-C4-alkylthio, trifluol~.. eLhyl-
thio or Cl-C4-alkoxycarbonyl),
R4 and/or R5 furt.he. -re represent phenyl or phenoxy,
or represent Cl-C4-alkylcarbonylamino, Cl-C4-
alkoxycarbonylamino, Cl-C4-alkylamino-carbonyl-
amino, di-(Cl-C4-alkyl)amino-caxbonylamino, or
repre~ent the radical -CO-R8, where
R~ represents Cl-C6-alkyl, C1-C6 alkoxy, C3-C6-
cycloalkoxy, C3-C6-alkenyloxy, Cl-C4 alkylthio,
Cl-C4-alkylamino, Cl-C4-alkoxyamino, Cl-C4-
alkoxy-C1-C4-alkyl-amino or di-(C1-C4-alkyl~-
amino (each of which is optionally substituted
by fluorine and/or chlorine),
R4 and/or Rs furthe ~re represent trimethylsilyl,
thiazolinyl, Cl-C4-alkylsulphonyloxy, di-(Cl-C4-
alkyl)-aminosulphonylamino, or represent the
radical -CH=N-R9, where
R9 represents Cl-C6-alkyl which is optionally
substituted by fluorine, chlorine, cyano,
carboxyl, Cl-C4-alkoxy, C1-C4-alkylthio~ C1-C4
alkylsulphinyl or Cl-C4-alkylsulphonyl, or
Le A 27 154 - 8 -
~ ~ 2 7 J ~3 ç~
represents ben~yl which is optionally substi-
tuted by fluorine or chlorine, or xepresents
C3-C6-alkenyl or C3-C6-alkinyl, each of which is
optionally substituted by fluorine or chlox-
ine, or represents phenyl which is optionally
substituted by fluorine, chlorine, bromine,
Cl-C4-alkyl, Cl-C4-alkoxy, trifluoromethyl,
trifluoromethoxy or trifluoromethylthio, or
represents Cl-C6-alkoxy, C3-C6-alkenoxy, C3-C6-
Alkinoxy or benzyloxy, each of which is
optionally substituted by fluorine and/or
chlorine, or represents amino, C~-C4-alkyl-
amino, di-(Cl-C4-alkyl)-amino, phenylamino,
Cl-C"-alkyl-carbonyl-amino, C,-C4-alkoxy-car-
bonylamino or C,-C4-alkyl-sulphonylamino, or
represents phenylsulphonylamino which is
optionally substituted by fluorin~, chlorine,
bromine or methyl,
furthe -re
R3 represents the radical -I ~ , where
R10 R11
Rl~ represents hydrogen or Cl-C4-al~yl,
R'1 and R12 are identical or different and represent
hydro~en, fluorine, chlorine, bromine, nitro,
cyano, C,-C4-alkyl (which is optionally ~ubstitut-
ed by ftuorine and/or chlorine), Cl~C4-alko~y
(which is optionally substituted by fluorine
and~orchlorine), carboxyl, C1-C4-alkoxy-carbonyl,
1e A 27 154 ~ 9 -
~ ~ ~;J ~ fJ 13 .3
dimethylaminocarbonyl,Cl-C4-alkylsulphonyl or di-
( C1-C4-a1kY1 )-aminosulphonyl;
furthermore
R3 represents the radical R13 ~ R14, where
Rl3 and Rl4 are identical or different and represent
hydrogen, fluorine, chlorine, bromine, nitro,
cyano, Cl-C4-alkyl (which is optionally substitut-
ed by fluorine and/or chlorine) or C~-C4-alkoxy
(which is optionally substituted by fluorine
and/or chlorine);
furthermore
R15
R3 represents the radical ~ , where
R16
Rl5 and Rl~ are identical or different and represent
hydrogen, fluorine, chlorine, bromine, nitro,
cyano, Cl C4-alkyl (which is optionally substitut~
ed by fluorine and/or chlorine~/ C~-C4-alkoxy
(which is optionally substitu~ed hy fluorine
and/or chlorine), or represent Cl-C4-alkylthio,
Cl-C4-alkylsulphinyl or Cl-C4-alkylsulphonyl teach
of which is optionally subs~ituted by fluorine
and/or chlorine), or r~present di-(Cl-C4-alkyl)-
aminosulphonyl or Cl-C4-alko~y-carbonyl or ~i-
methyl~minocarbonyl;
Le A 27 154 - 10 -
~ 33 2 ~ ~ J li
furthermore
R3 represents the radical R17 ~ R1~ , where
R17 and R18 are identical or different and represent
hydrogen, fluorine, chlorine, bL~ ine, Cl-C4-alkyl
(which is op~ionally substituted by fluorine and/or
bromine), Cl-C4-alkoxy ~which is optionally substi~
tuted by fluorine and/or chlorine), or repre~ent
Cl-C4-alkylthio, Cl-C4-alkylsulphinyl or Cl C~-alkyl-
sulphonyl (each of which is optionally substituted
lQ by fluorine and/or rhlorine), or represent di-(Cl-C4-
alkyl)-aminosulphonyl;
furthermore
R19
R3 represents the radical ~ R20 ' where
A
Rl9 and R20 ar~ identical or different and represent
hydrogen, fluorine, chlorine, bromine, cyano,
nitro, Cl-C4-alkyl (which is optionally substitut-
ed by fluorine and/or chlorine), Cl-C4-alko~y
(which is optionally substituted by fluorine
and/or chlorine), Cl-C4-alkylthio, C1-C4-alkylsul-
phinyl or C~-C4-alkylsulphonyl (which is optional-
ly substituted by fluorine and/or chlorine), di-
(Cl-C4-alkyl)-~mino-sulphonyl, C1-C4-aIkoxy-car-
bonyl or dimethylaminocarbonyl, and
A repr~sents oxygen, sulphur or the group N-2~,
Le A 27 154
'3 ~
where
Z1 represents hydrogen, C1-C4-alkyl (which is
optionally s~bstituted by fluorine, chlorine,
bLr ine or cyano), C3-C~-cycloalkyl, ben~yl,
phenyl (which is optionally substituted by
fluorine, chlorine, bromine or nitro), C1-C4-
alkylcarbonyl, Cl-C4-alko~y-carbonyl or di-
(C1-C4-alkyl)-aminocarbonyl;
furthermore
R3 represents the radical ~ R22 ' where
R21 and R22 are identical or different and represent
hydrogen, Cl-C4-alkyl, halogen, Cl-C4-alkoxy-
carbonyl, Cl-C4-alkoxy or Cl-C4-halogenoalkoxy,
Y~ represents sulphur or the group N-R23, where
R23 represents hydrogen or Cl-C4-alkyl;
furtherrore
R26
R3 represents the radical ~ , where
N' ¦ R2 5
R29
R24 represents hydrogen, C1-C4-alkyl, benzyl,
quinolinyl or phenyl,
R25 represents hydrogen, halogen, cyano, nitro,
Cl-C4-al~yl (which is optionally substituted by
Le A 27 154 - 12 -
~ ~r~ r,
fluorine and/or chlorine), C1-C4-alkoxy (which
is optionally substituted by fluorine and/or
chlorine), dioxol~nyl or Cl-C4-alkoxy-carbonyl,
and
R26 represents hydrogen, halogen or C1-C4-alkyl;
furthermore
R3 represents one of th~ groups listed below,
H3CO~ H3C~
S'N- C4H9 ; N~S~OCH2CF3
~2
~0
The invencion furthermore preferably relates to
the sodium, potassium, magnesium, calcium, ammonium,
Cl-C4-alkylammonium, di-tC1-C4-alkyl)-~mmonium, tri-(Cl-C4-
al~yl~-ammonium, Cs~ or C6-cycloalkyl-ammonium and di-
(Cl-C2-alkyl)-benzyl-ammonium salts of compounds of the
formula (I~ in which R1, R2 and R3 have the meanings
mentioned above as being preferred.
In particular, the invention relates to compounds
of the formula (I) in which
Rl represents hydrogen, or represents Cl-C~-alkyl which
is optionally substituted by fluorine, chlorine,
bromine, cyano, methoxy or e~hoxy, or represents
allyl, or represents C3-C6-cycloalkyl, or repre-
~e A 27 154 - 13 -
sents phenyl, or represents benzyl, or represents
Cl-C3-alkoxy, or represents Cl-C3-alkylamino, or
represents di-(Cl-C2-alkyl)-amino.
R2 represents hydrogen, or represents Cl-C4-alkyl which
is optionally substituted by fluorine and/or chlor-
ine or by methoxy or ethoxy, or represents C3-C6-
cycloalkyl, or represents phenyl, or represents
Cl-C3-alkoxy, or represents Cl-C3-alkylamino, or
represents di-(Cl-C2-alkyl)-amino, and
R3 represents the group ~ R5 ' where
R4 represents fluorine, chlorine, bromine, methyl,
trifluoromethyl, methoxy, difluoromethoxy,
trifluoromethoxy, 2-chloro-ethoxy, 2-methoxy-
ethoxy, Cl-C3-alkylthio, Cl-C3-alkylsulphinyl,
Cl-C3-alkylsulphonyl, dimethylaminosulphonyl,
diethylaminosulphonyl, N-methoxy-N-methylamino-
sulphonyl, phenyl, phenoxy or C~-C3-alkoxy-car-
bonyl, and
R5 represents hydrogen, fluorine, chlorine or
bromine;
furthermore
Rl 1
R3 represents the radical -cH ~ R12 ' where
R10 repre~ents hydrogen,
Le A 27 154 - 14
3 ;3
-
represents fluorine, chlorine, bromine, methyl,
methoxy, difluoromethoxy, trifluoromethoxy,
ethoxy, methoxycarbonyl, ethoxycarbonyl,
methylsulphonyl or dimethylaminosulphonyl, and
R12 represents hydrogen;
furthermore
R3 represents the radical
F~O- C S
o
where R represents Cl-C4-alkyl, or
represents the radical RO
-C~
N~M
CH3
where R represents C,-C4-alkyl.
Examples of the compounds according to the
invention are listed in Table 1 below - cf. also the
Preparation Examples.
Le A 27 154 - 15 -
~ '~ 2 ~ 2 ~) ,
R3-So2-NH-CO-NJ~N-Rl
I~R2 ( I )
Table 1: Examples of the colr.pounds oî the formula ~ I )
R1 R2 R3
H
~\ H <~
OC~3
CH2-CH=CH2 C2H5 <~H2
OCHF2
OCH ~ C3H7 ~Hz-
~\ ~
O-C~2-CH=CH2 S OOCH3
COOC2H5
C2H5 C4Hg-n ~
I,e A 27 154 ~ 16
Table 1 - continuation
R 1 R2 R3
So2NwocH3
~H3 C3H7 ~
p C3H7 ~ ZN(CH3~2
CH3 C2H5 Cl
Br
C2H5 C3H7 ~
CH3
COOCH2-CH2 -C 1
OC2H5 e~
OC3H7 CH3 ~ COOCH3
CH3
CH3 C3H7 ~COOCH3
COOCH
N(CH3~2 CH2 <~CH23
Le A ~7 154 - 17 -
i) 2 r~ ~
Table 1 - continuation
R1 R2 R3
COOCH3
NH-CH3 ~ H2_
COOC2H5
CH3 C3H
~zCHO
OCF3
OCH3 ~
OCHF2
C~L OCzH5
CH2~> CH2~
~ OCF3
CH2 C3H
C3H7 ~ N ~
COOCH3
CH3 C H5 CH30 ~ S~N-C4~s
Le A 27 154 - 18 -
~, ~,.
Table 1 - continuation
R 1 R2 E~3
~CON(CH3)2
CH3 C4H9 ~
~CON(CH3)2
C3~7
CH3 C3H7 ~3
C2~5 C2H5
C3H7 5~2~
OCH;2 ~ CH2 - C 1
C2}15 C2H5 ~
OCH3
~<
CH3 C3H7~n <~
OC 2H5
C3H7~
Le A 27 154 - 19 -
~27~1J 3)~
Table 1 - continuation
R1 R2 R3
CF3
CH3 (~
oc~3
CH3 C4Hg ~CH2-
CH3 ~ ~2-
C2H5 ~ ~2
CF3
C3H7 C3H7 ~ Hz-
CN
CH3 CH(CH3)2 ~ H2_
~COOC2H5
~\ N'N--
CH3
Nl~
Le A 27 lS4 - 20 -
2 ~3 ,C~
Table 1 - continuation
R 1 R2 R3
~COOC2H5
N'7
OCH3 C2H5 G~N
COOCH ( CH3 ) 2
~C2~5 C2H5 Cl
~CF3
CH3 CH3 I~NJ~
l~r
CH3 C2H5 N~N~
CH3
H3COOC
/\ /~ ~ ,N~H3
Cl
~CON(CH3)2
CH3 CH3 H3C--
OCF3
CH3 CH(CH~)2 ~ H2
Le A 27 154 - 21 -
Table l - continuation
Rl R2 R3 Br
OCH2-CH=CH2 C2H5 CH3~
,CH3
S~2 ~ N~
OCH3 C2H5 ~ OCH3
Br
CH3 CH ( CH3 ) 2 ~
SCH3
CH3 CH2-CH=CH2 <~
502CH 3
CH3 CH2-O-CH3 ~
SCHtCH3)2
CH3 CH2-O-c2H5 ~
C2H5 C2H4-0-CH3 ~
~ CON~CH3)2
CH~ - CH = CH2 H ~J~
Le A 27 154 - 22 -
f~ I
~able 1 - continuation
Rl R2 R3
OCHF2
CH2-CH=CH2 CH~ ~
~ r
CH2-CH=CH2 C2H5 N~N~
c~3
~ [~
~2H5 S~A~COOCH3
COOC2H5
CH3 C3H? ~
CH3
NH-CH3 C2~5 Cl
COOCH3
NH-CH3 ~ H2_
Si(CH3~3
CH3 C3H7 ~
ON(CH3)2
C2H5 Cl
Le A 27 154 - 23
~3~ ~f~,~J~
q~able 1 - continuation
E~ 1 RZ E~
~CON ( CH 3 ) 2
C2H5 C4H9 S
CH3~
CH3 C3H7 N'S~OCH2-CF3
~\ ~0
C 2H s N~7~
CH3
CH3 ~ N S3
~3
C2H5 ~
CH3
OCH3 CH ( CH3 ) 2 ~CH2-
C2H5
~C2HS C2H5 ~
~CF3
CH3 H
LP A 27 154 - 24 -
~J ~ J ~ ~
Table 1 - continuation
R1 RZ R3
CHZ-CH2-0-CH3
CH3 C2H5 e~
O SOzCH3
CH3 C3H
OCH3 ~ ~
SO~CH3
OCH3 H ~
CH3
c~3 C2H5 ~~
Br
OCHF2
CH2-CH=CH2 CH2-0-CH3
~e A 27 154 - 25 -
Table 1 - continuation
Rl R2 R3
OCH2C112 - C 1
N(C113)2 N(CH3)2 ~
If, for example, 2,6-difluorophenyl isocyanate
and 5-ethyl-4-methoxy-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:
o
~S ~2 - N = C = O t H~NJ~U~CH 3 >
F 2H5
O
~S02 - NH - CO~NJ~N'OCH3
F U=~C2~5
If, for example, 2-methylthio-benzenesulphonamide and 2-
chlorocarbonyl-4-dimethylamino-2,4-dihydro 3H-1,2,4-
triazol-3-one are used as starting subst2nces, the course
lQ of the reaction in process tb) according to the invention
Le A 27 154 - 26 -
7 ,.' ~ ~
can be outlined by the following equation:
SCH o
2 NH2 Cl -CO~NIJ~N~N ~ CH3 ) 2 -HCl
H
SCH3 ~
~502-NH-co~NlJ~N~N ( CH3 12
N==L--H
If, for example, N-methoxycarbonyl-2-methoxy-benzenesul-
phonamide and 5-diethylamino-4-difluoromethyl-2,4-di-
hydro-3H-1,2,4-triazol-3-one are used as starting sub- .
stances, the course of the reaction in process (c)
according to the invention can be outlined by the -follow-
ing ~quation:
OCH3 Ll
l~=< H~N~N~CHF2
~S02-NH-COOCH3 ~ l l
N~N(C2H5 )2
OCH3 ~
-HOCH3 e~S02-NH-CO~NJ~N'CHF2
N(C2H5 ~2
Formula (II) provides a general definition of the triazo-
Le A 27 154 - 27 -
linones to be used as starting substances in processes
(a) and (c) according to the invention for the prepara-
tion of compounds of the formula (I).
In formula (II), Rl 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 R1 and
R2 .
Examples of the starting substances of the
formula (II) are listed in Table 2 belowO
HN ~ NfRl (II)
N=I~R2
Table 2: Examples of the starting substances of the
formula (II)
Rl R2
H H
CH3 H
C2H5 H
C3~7 H
Le A 27 154 - 28 -
~ ~ 7 i3 n
Table 2 - continuation
Rl R2
CH(CH3)2 H
CqHg H
CH2CH(CH3)2 H
C(CH3)3 H
H CH3
C2H5
H C3H7
H CH~CH3)2
H C4H9
H CH2CH(CH3)2
H CtCH3)3
C~F2 H
CH2CH2CN H
CH2CH20CH3 H
H CF3
H CH20CH3
H CH20C2H5
CH2C~20CH3
c~3 CH3
Le A 27 154 - 29 ~
7i~jlSi
Table 2 - continuation
R1 R2
CH3 C2H5
CH3 C3H7
CH3 CH~CH3~2
CH3 c4~9
CH3 CH2CH(C~3)2
CH3 C(CH3~3
C2H5 CH3
C3H7 CH3
CH(CH3)2 CH~
C4H9 CH3
CH2CH(CH3)2 CH3
C2H5 C2~5,
C3H7 C3H7
CHF2 C3H7
CHF2 CH3
CHF2 C2H5
~3 C~3
C2H5 CF~
C~2CHF2 c~3
C2H5 C3H7
~e A 27 1~4 - 30 -
2 ~ J
Table 2 - continuation
Rl R2
C2H5 CqH9
C6H5 CH3
~CH2
-CH I CH3
~CH2
~CH2
CH~3 - CH
~CH2
CH3
CH3
CH3 N(CH3)2
C2H5 N ~ CH3 ) 2
C2H5
C3H7
OCH ~
2HS
C3}17
-
Le A 27 154 - 31 -
f'~ ~3 f~ 3 r~
Table 2 - continuation
Rl R2
CH3
2 5
C3H7
~ C3H7
CH3
CH3
NH2 CH3
CH3 NHCH3
NHCH3 CH3
NHCH3 C2~5
NHCH3 C3H7
N(CH3)2 CH3
N(CH3)2 Cz~g5
NtC~3)2 C3~7
Le A 27 154 - ~2 -
. ~ .
: '
Table 2 - continuation
Rl R2
OCH3 CH3
OCH3 C2H5
~C2H5 CH3
~C2H5 C2H5
/\
CHz-O-C2H5
/~
N ( CH3 ) 2
O-C3H7 C3H7
{~
o - CH2 - cH= CHz CH3
O-CH2-CH=CH2 C2H5
O-CH2-CH=CH~ C3H7
~~C112~CH-CH2-Br c3~7
Br
OCH3
Le A 27 154 - 33 -
~ ~ 2 ~ ~ ,
Table 2 ~ continuation
R1 R2
OCH3
OCH3 ~
OCH3 ~>
OCH3 CH2
OCH3 N ( CH3 ) 2
O-CH2-COOCH3 C3H7
N~CH3)2
N(CH3)2 ~1
N(CH3)z {~
OC 2H 5 C 3H 7
OC 2H5
Le A 27 154 _ 3d, w
~J ~ ;) S~ ,~3 ~3J, ~
Table 2 - continuation
Rl R2
~\ ~3
~ C2H5
NH-CH3 ~H2-0-CH ~
/ \ CH2-0-CH~
CH3 CH2-0-CH3
Le A ~7 154 - 35 -
~J '~!ç~ 4
The starting substances of the formula (II~ are known
and/or can be prepared by processes known per se (cf.
Chem. ser. 90 (1957), 909-921; loc.cit. 98 (1965), 3025-
3099; J. Heterocycl. Chem. 15 (1978), 237-240; Tetra-
5 hedron 32 (1976), 2347-2352; Helv. Chim. Acta 63 51980),
841-859; J. Chem. Soc. C 1967, 746-751; EP-A 283,876;
EP-A 294,666; EP-A 301,946; EP-A 298,371;
DE-P 3,839,206/LeA 26,538 dated 19.11 1988,
DE-P 3,916,207/LeA 26,849 dated 18.05.1989;
~E-P 3,916,208/Le~ 26,850 dated 18.05.1989; J. Chem. Soc.
C 1970, 26-34; DE-P 3,916,930/LeA 26,886 dated
24.05.1989).
For example, the triazolinones of the
formula (II) are obt~ine~ when
~) oxadiazolinones of the general formula (VII)
H~NJ~O ( Y I I )
N=~R2
in which
R2 has the abovementioned meaning
are reacted with amino compounds of the general
formula (VIII)
H2N-R1 (VIII)
in which
R1 has the abovemen~ioned meaning,
Le A 27 154 - 36 -
at temperatures between 20~C and 120~C and, if
appropriate, in the presence of a diluent, such as,
for example, water, and the hydrazine derivatives
formed ~y this process, of the general formula (IX)
H~ ,,C O - NH - R 1
,N~ ( I X )
H CO-R2
in which
R1 and R2 have the abov.- -ntioned meanings,
are isolated by customary methods (cf. the
Preparation Examples) and - or if appropriate even
without inte~ ate isolation - the compounds of
the formula (IX) are condensed at temperatures
between 20~C and 120~C and, if appropriateg in the
presence of a basic condensation auxiliary, such as,
for example, sodium hydroxide, and, if appropriate,
in the presence of a diluent, such as, for example,
water, to give the compounds of the formula (II)
(cf. EP-A 301,946, DE-OS (German Published
Specification~ 3,743,493/LeA 25,759 and the
Preparation Examples),
or when
~) amino compounds of the general fo~mula (VIII)
~2N-R1 (VIII~
Le A 27 154 - 37 -
in which
Rl has the abo~ementioned meaning,
are reacted with carbonic acid derivatives, such as,
for example, diphenyl carbonate, then with hydrazine
or hydrazine hydrate and eventually with a car-
boxylic acid derivative or carbonic acid derivative
of the general formula (X)
(RO)3C-R2 (X)
in wh.ich
R2 has the abo~ -ntioned meaning and
R represents lower alkyl,
at temperatures between 0~C and 150~C and, if
appropriate, in the presence of a diluent, such as,
for example, ethylene chloride (cf.
DE-P 3,920,270/LeA 26l937 dated 21.06.1989,
DE-P 3,928,662/LeA 27,137 dated 30.08.1989, and the
Preparation Examples).
The triazolinones of the general formula (IIa)
HNJ~N~A 1 ( I I a )
I~A 2
in which
A represents in each case optionally substituted
alkyl, alkenyl~ cycloalkyl, alkoxy or dialkyl-
amino and
A represents hydrogen, or represents in each case
optionally substituted alkyl, cycloalkyl, aralkyl,
aryl or alkoxy,
Le A 27 154 - 38 -
~2 ~f'J~J
provided that both Al and A2 do not simultaneously re-
present alkyl,
are new and a subject of the present invention.
The new triazolinones of the formula (IIa) are
obtained either when oxadiazolinones of the general
formula (VIIa)
H''NJ~ (VIla)
~A2
in which
A2 has the abovementioned meaning,
are reacted with amino compounds of the general
formula (VIIIa)
H2N-A1 (VIlIa)
in which
Al has the abovementioned meaning,
analogously to the process described above under (~), or
when
amino compounds of the ~eneral formula (VIIIa)
H2N-A1 (VIII3~
are reacted with carbonic acid derivatives, then with
hydrazine or hydrazine hydrate and eventually with a
carboxylic acid derivative or carbonic acid derivative of
Le A 27 154 - 39 -
~. ~3 ,~ ~ J~g
the general formula (xa)
( RO ) 3C-A2 ( Xa )
in which
A2 and R have the abovementioned meanings,
analogously to the process described above under (~)
(also see the Preparation Examples).
In the general formul~ (IIa),
Al preferably represents Cl-C6-alkyl. C3-C5-alkenyl
or C3-C6-cycloalkyl, or represents Cl-C6-alkoxy
which is optionally substituted by fluorine, chlo-
rine, bromine, cyano, Cl-C4-alkoxy or Cl-C4-alk-
oxy-carbonyl, in particular methyl, ethyl, allyl,
cyclopropyl, methoxy, ethoxy, propoxy or isoprop-
oxy, or represents di-(Cl-C4-alkyl)-a~ino, in par-
ticular dimethyla~ino or diethylamino, and
A2 preferaLbly represents hydrogen, or represents Cl-C6-
alkyl which is optionally substituted by fluorine,
chlorine, bromine, cyano, Cl-C4-alkoxy, Cl-C4-alkyl-
carbonyl or Cl-C4-alkoxy-carbonyl, or represents
C3-C6-cycloalkyl which is optionally substituted by
fluorine, chlorine, bromine and/or Cl-C4-alkyl, or
represents phenyl-Cl-C3-alkyl which is optionally
substituted by iluorine/ chlorine, bromine, cyano,
nitro, Cl-C4-alkyl, trifluoromethyl, C~C4-alkoxy
and~or Cl-C4-alXoxycarbonyl, or represents phenyl
which i8 optionally substituted by fluorine, chlor-
ine, bromine, cyano, nitro, Cl-C4~alkyl, trifluoro-
methyl, Cl-C4-alkoxy, fluorin~- and~or chlorine-
substituted Cl-C3-alkoxy, Cl-C4-alkylthio, fluorine-
and/or chlorine-substituted Cl-C3-alkylthio~ Cl-C4-
alkylsulphinyl, Cl-C4-alkylsulphonyl and/or Cl-C4-
Le A 27 154 _ 40 ~
alkoxy-carbonyl, or represents C1-C4-alkoxy, in
particular hydrogen, Cl-C4-alkyl ~hich is option-
ally substituted by fluorine and/or chlorine,
methoxy or ethoxy, or represents C3-C6-cycloalkyl,
S or represents methoxy ~r ethoxy,
provided that both Al and A2 do not simultaneously re~
present Cl-C6-alkyl.
The ~ompounds of the formulae (VII), (VIIa~,
(VIII), (VIIIa) and (X) or (Xa) which are to be us~d as
starting substances for the preparation of the triazolin-
ones of the formulae (II) or (IIa) are known (cf. He~v.
Chim. Acta 55 ~1972), 1174; EP-A 301,946; DE-OS (Ge ~n
Published Specification) 3,743,493).
Formula (III) provides a general definition of
the sulphonyl isocyanates further to be used as starting
substances in process (a) accoxding to the invention for
the preparation of compounds of the foxmula (I).
In formula (III), R3 prPferably, 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.
Examples of the starting substances of the
formula (III) which may be mentioned are:
2-flucro-, 2-chloro-, 2-bromo-, 2-methyl-, 2-methoxy-, 2-
trifluoromethyl-, 2-difluoro-methoxy-, 2-trifluorometh-
oxy-, 2-methylthio-, 2-ethylthio-, 2-propylthio-l 2-
methylsulphinyl-, 2-methylsulphonyl-, 2-dimethylamino-
sulphonyl-, 2-diethylaminosulphonyl-, 2-(N-methoxy-N-
methyl)-aminosulphonyl-, 2-phenyl-, 2-phenoxy-, 2-meth-
oxycarbonyl-, 2-ethoxycarbonyl-, 2-propo~ycarbonyl- and
2-isopropoxycarbonyl-phenylsulphonyl isocyanate, 2-
fluoro-, 2-chloro-, 2-difluoromethoxy , 2-trifluorometh~
Le A 27 154 41 -
2-methoxycarbonyl- and 2-ethoxycarbonyl-benzylsulphonyl
isocy~nate,2-methoxycarbon~1-3-thienyl-sulphonylisocya-
nate, 4-metho~ycarbonyl- and 4-ethoxycarbonyl-1-methyl-
pyrazol-5-yl-sulphonyl isocyanate.
The sulphonyl isocyanates of th~ formula (III)
are known and/ox can be prepared by processes known per
8e (cf. US-P 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, 173,31~).
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
in this context are virtually all inert organic solvents.
These preferably include aliphatic and aromatic, option-
ally halogenated hydrocarbons, such as pentane, h~ne,
heptane, cycloh~Y~ne, 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 di-
methyl 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 ex-
ample, acetonitrile and propionitrile, amides, such as,
for example, dimethylformamidet dimethylacetamide and N-
methyl-pyrrolidone, and also dLmethyl sulphoxide, te$ra-
methylene sulphone and hexamethylphosphoric triamide.
In process (a) according to the invention, the
reaction temperatures can be varied within a substantial
Le A 27 154 - 42 -
range. In general, the process is carried out at temper-
atures between 0~C and 150~C, preferably at temperatures
between 10~C and 80~C.
Process (a) accoxding 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 concentrated, and the crude
product which r~m~ i n~ in the residue is crystallized
using a suitable solvent, such as, for example, diethyl
ether. The product of the formula (I) which has been
obt~ine~ in crystalline form is isolated by filtration
with suction.
Formula (IV) provides a general definition of the
triazolinone derivatives to be used as starting substanc-
es in process (b) according to the invention for the
preparation of compounds of the formula (I).
In formula (IV), 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 R1 and
R2, and
Z preferably represents chlorine, C1-C4-alkoxy,
benzyloxy or phenoxy, in particular methoxy or
Le A 27 154 - 43 -
J ~ 3
phenoxy.
Examples of the starting substances of the
formula (IV) which are possible are the compounds of the
formula tIV) to be prepared from the compounds of the
formula (II) listed in Table 2 and phosgene, methyl
chloroformate, benzyl chloroformate, phenyl chloroformate
or diphenyl carbonate.
The starting substances of the formula (IV) are
known and/or can be prepared by processes known per ~e
(cf. EP-A 283,876; EP-A 294,666; EP-A 298,371.
The triazolinone derivatives of the formula (IV)
are obtained for example when triazolinon~s of the
general formula lII)
HNJ~N~Rl ( I I )
~L~R2
in which
R1 and RZ have the abov.~ -~tioned me~nings,
are reacted with carbonic acid derivatives of the general
formula (XI)
z co-z1 (XI~
in which
~ has the abov. -ntioned --n i ~g and
L~ A 27 154 - 44 -
b~
Z1 represents a leaving group, such as chlorine,
methoxy, benzyloxy or phenoxy,
at temperatures between -20~C and +100~C, if appropriate
in the presence of a diluent, such as, for example r
tetrahydrofuran, and, if appropriate, in the presence of
an acid acceptor, Ruch as, for example, sodium hydride or
potassium tert-butylate (cf. the Preparation Examples).
Formula (V) provides a general definition of the
sulpho~ides further to be used as starting ~ubstances
in process (b) according to the in~ention for the prepar-
ation of compounds of the formula (I).
In formula (V), R3 preferably, or in particular,
has the --n;ng which has already been mentioned above in
connection with the description of the compounds of th~
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-difluoro-methoxy-, 2-trifluorometh-
oxy-, 2-methylthio-, 2-ethylthio-, 2-propylthio-, 2-
methylsulphinyl-, 2-methylsulphonyl-, 2-dimethylamino-
sulphonyl-, 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-
phon~m ide, 2-methoxycar~onyl-3-thiophenesulphonamide, 4-
methoxycarbonyl- and 4-ethoxycarbonyl-1-methyl pyrazol-
Le A 27 154 - 45 -
5-sulphonamide.
The sulphonamides of the formula (V) axe known
and/or can be prepared by processes known pex se (cf.
US-P 4,127,405, 4,169,719, 4,371,391; EP-A 7,687, 13,480,
21,641, 23,141, 23,422, 30,422, 30,139, 35,893, 44,808,
44,809, 48,143, 51,466, 64,322, 70,041, 173,312).
Process (b) according to the invention for the
preparation of the new compounds of the formula ~I) is
preferably carried out using diluents. Suitable diluents
in this context are virtually all inert organic solvents,
for example those which have been indicated above in the
case of process (a) according to the invention.
Acid acceptors which can be employed in
process (b) according to the invention are all aaid-bind-
ing 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, dimethylben~ylamine,
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-t2,2,2J-octane (DABCO).
When carrying out process (b) according to the
invention, the reaction temperatures can be ~aried within
a substantial range. In general, the process i5 carried
Le A 27 154 ~ 46 -
out at temperatures between 0~C and lOODC, preferably at
temperatures between 10~C and 60~C.
In general, process (b) according to the inven-
tion 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 ~tarting 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. 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. Working-up in
process (b) according to the invention is carried out in
each case by customary methods.
The triazolinones of the formula (II) which are
to be used as starting substances in process (c) accord-
ing to the invention for the preparation of compounds ofthe 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 further to be u~ed as starting
substances in process ~c) according to the invention for
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
Le A 27 154 - 47 ~
~J 3.,~ r.) ~
invention as bein~ preferred, or particularly preferred,
for R3 and Z.
Process (c) according to the invention is prefer-
ably carried out using diluents. Suitable diluents in
this context are the same organic solvents as 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 in this context are the same as have been men-
tioned 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 i5 carried
out at temperatures between 0~C and 100~CI preferably at
temperatures between 10~C and 60~C.
In general, process (c) according to the inYen-
tion 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 ~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
two specifically employed components in a substantial
excess. In general, the reactions are carried out in a
6uitable diluent in the presence of an acid acceptor, and
the reaction mixture is st~rred for several hours at ~he
~pecifically required temperature. Working-up in
Le A 27 154 - 48 -
~,t~ //J~)3
process (c) according to the invention is carried out in
each case by customary methods.
To convert the compounds of the formula (I) into
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, using suitable diluents, such as,
for example, water, methanol or ethanol. The salts can be
isolated as crystalline products - then if appropriate
after concentrating the mi~ture.
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 broadèst sense, there axe 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 usedt for example, in connec~ion with the follow-
ing plants:
DicotYledon weeds of the qenera: Sinapis,
Lepidium, Galium, Stellaria, Matricaria, Anthemis,
Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus,
Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum,
Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solanum,
Rorippa, Rotala, Lindernia, Lamium, Veronica, Abutilon,
Emex, Datura, Viola, Galeopsis, Papaver,Centaurea,Tnfolium,
3 0 Ranunculus a n d Taraxacum.
DicotYledon cultures of the qenera Gossypium,
Le A 27 154 - 49 -
~J s'~ f~
Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum,
Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis,
Brassica, Lactuca, Cuc~mis and Cucurbita.
Monocotyledon weeds of the qenera: Echinochloa,
Setaria, Panicum, Digitaria/ Phleum, Poa, Pestuca,
Eleusine, Brachiaria, Lolium, Bromus, A~ena, Cyperus,
Sorghum, AyLo~Lon~ Cynodon, Monochoria, Fimbristylis,
Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum,
Sphenoclea, Dactyloctenium, Agrostis, Alopecurus and
Apera.
Monocotyledon cultures of the genera: Oryza,
Zea, Triticum, Hordeum, Avena, Secale, Sorghum, Panicum,
Saccharum, An~n~5 ~ 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 tre~ plantings. Equal-
ly, the compounds can be employed for combating weeds in
perennial cultures, for example afforestations, decor-
ative tree plantings, orchards, vineyards, citrus groves,
nut orchards, banana plantations, coffee plantations, tea
plantations, rubber plantations, oil palm plantations,
cocoa plantations, soft fruit plantings and hopfields,
inlawns,~,meadowsandpas~es,
and for the selective combating of weeds in annual
cultures.
The compounds of the formula ~I) according to the
Le A 27 154 _ 50
invention are suitable for combating monocotyledon and
dicotyledon weeds both in the prc i -rgence and the
post-emergence method. They are markedly more effective
than, for ~xample, isocarh~mi~e.
To a certain extent, the compounds according to
the invention also show a fungicidal action, for example
against powdery mildews and against apple scab, and also
against Pyricularia oryzae on rice.
The active compounds can be converted into the
customary formulations, such as ~olutions, emulsions,
wettable powders, suspensions, powders, dusting agents,
pastes, soluble powders, granules, ~uspension-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 a~ents, that is
emulsifying agents and/or dispersing agents andtor 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 cyclohe~ne or paraffins, for example petrole~m
fractions, mineral and vegetable oils, alcohols, such as
~e A 27 154 - 51 -
butanol or glycol as well as their ethers and esters,
ketones, such as acetone, methyl ethyl ketone, methyl
isobutyl ketone or cyclohe~Anone, strongly polar
solvents, such as dimethylformamide and dimethyl
sulphoxide, as well as water.
As solid carriers there are suitable: for ~xample
ammonium 8alts and ground natural minerals, such as
kaolins, clays, talc, chalk, quartz, attapulgite,
montmorillonite or diatomaceous earth, and ground
synthetic minerals, ~uch as highly disper~e ~ilica,
alumina and silicates, as solid carriers for granules
there are suitable: for example crushed and fractionated
natural rocks such as calcite, marble, pumice, sepiolite
and dolomite, as well as synthetic granules of inorganic
and organic meals, and granules of organic material such
as sawdust, coconut shells, maize cobs and tobacco
stalks; as emulsifying and/or foam-forming agents there
are ~uitable: for example non-ionic and anionic
emulsifiers, such as polyoxyethylene fatty acid esters,
polyoxyethylene fatty alcohol ethers, for example
alkylaryl polyglycol ethers, alkylsulphonates, alkyl
sulphates, arylsulphonates as well as 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 latices, such as gum arabic, polyvinyl
alcohol and polyvinyl acetate, as well as natural
phospholipids, ~uch as cephalins and lecithins, and
Le A 27 154 - 52 -
?~ J J
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
pi~ments, for example iron oxide, titanium oxide and
Prussian Blue, and organic dyestuffs, such as alizarin
dyestuffs, azo dyestuffs and metal phthalocyanine
dyestuffs, and trace nutrients such as salts of iron,
mangane~e, 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
according to the invention, as such or in the form of
their formulations, can also be used as mixtures with
known herbicides, finished formulations or tank mixes
being possible.
Suitable herbicides for the mixtures are known
her~icides, 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'-dLmethylurea
(METABENZ~HIAZURON) 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;
furthP -re also mixtures with 2,4-dichlorophsnoxyacetic
acid (2,4-D); 4-(2,4-dichlorophenoxy)-butric acid ~2,4-
DB); 2,4-dichlorophenoxypropionic acid ~2,4-DP); 5-(2-
chloro-4-trifluoromethyl-phenoxy)-2-nitrobenzoic acid
(ACIF~UORFEN); 2-chloro-2',6'-diethyl N-methoxy-methyl-
he A 27 154 - 53 -
h .~S ~ J ~
acetanilide (AT~Ac~T~QR); 2-chloro-4-ethylamino- 6 iso-
propylamino-1,3,5-triazine (ATRAZINE); methyl 2-
[[[t[(4,6-dimethoxypyrimidin-2-yl)-amino]carbonyl]-
amino]-sulphonyl]-methyl]-benzoate (BENSULFURON); 3-
isopropyl-2,1,3-benzothiadiazin-4-one 2,2-dioxide
(BENTAZONE); methyl 5-(2,4-dichlorophenoxy)-2-nitro-
benzoate (BIFENOX); 3,5-dibromo-4-hydroxy-benzonitrile;
(BROMOXYNIL); N-~butoxymethyl)-2-chloro-N-(2,6-diethyl-
phenyl)-acetamide (~U~CFT~OR); ethyl 2-~[(4--chloro-6-
lQ methoxy-2-pyrimidinyl)-aminocarbonyll-aminosulphonyl}-
benzoate( CHLORIMURON);2 -chloro-N-{[(4-methoxy-6-m2thyl-
1,3,5-txiazin-2-yl)-amino]-carbonyl}-benzenesulphonamide
(CHLORSULFURON); N,N-dimethyl-N'-(3-chloro-4-methyl-
phenyl)-urea(CHLORTOLURON); 2-chloro~4-ethylamino-6-(3-
cyanopropylamino)-1,3,5-triazine~CYANAZINE);2,6-dichlo-
robenzonitrile(DICRT.O~P.~IL);2-[4-(2,4-dichlorophenoxy)-
phenoxy]-propionic acid, its methyl ester or its ethyl
ester ( DICLOFOP); 2-[(2-chlorophenyl)-methyl]-4,4-di-
methylisoxa~olidin-3-one (DIMETHAZONE); ~-amino-6-t-
butyl-3-ethylthio-1,2,4-triazin-5(4H)-on2 (ETHIOZIN); 2-
{4-[6-chloro-2-benzoxazolyl)-oxy~-phenoxy}-propanoic
acid, its methyl ester or its ethyl ester (FENOXAPROP);
2-[4-(5-trifluoromethyl-2-pyridyloxy)-phenoxy]-propanoic
acid or its butyl ester (FLUAZIFOP); NIN-dimethyl-N'-(3-
trifluoromethylphenyl)-urea (FLUOMETURON); l-m~thyl-3-
phenyl-5-(3-trifluoromethylphenyl)-4-pyridone
(FLURIDONE 3; 5-(2-chloro-4-trifluoromethyl~phenoxy)-N-
methylsulphonyl-2-nitrobenzamide (F~M~.SAFEN); N-phos-
phonomethyl-glycine ( GLYPHOSATE);
methyl 2-[4,5-dihydro-4-methyl-4~ methylethyl)-5-oxo
Le A 27 154 - 54 -
lH-imidazol-2-yl]-4(5)-methylbenzoate (IMAZA~ETHABENZ);
2-(4,5-dihydro-4-methyl-4-is~propyl-5-oxo-lH-Lmidazol-2-
yl)-pyridine-3-carboxylic acid (IMAZAPYR); 2-[5-methyl-
5-(1--me~hylethyl)-4-oxo-2-imidazolin-2-yl]-3-~uinolin-
carboxylic acid (TM~7~QuIN); 2-[4,5-dihydro-4-methyl-4-
isopropyl-5-oxo-(lH)-imidazol-2-yl]-5-ethylpyridin-3-
carboxylic acid ~IMA~E~HAPYR); 3,5-diiodo-4-hydroxy-
benzonitrile ( IOXYNIL); N,N-dimethyl-N'-(4-iso-
propylphenyl)-urea (ISOPROTURON); (2-methyl-4-chloro-
phenoxy)-acetic acid (MCPA); (4-chloro-2-methylphenoxy)-
propionic acid (MCPP); N-methyl-2-(1,3-benzothiazol-2-
yloxy)-acetanilide (MEFENACET); 2-chloro-N-(2,6-dimethyl-
phenyi)-N-[(lH)-pyrazol-l-yl-methyl]-acetamide
(ME~A7.~CR~OR); 2-ethyl-6-methyl-N~(1-methyl-2-metho~
xyethyl)-chloroacetanilide (METOLACXLOR); 2-~[((4-
methoxy-6-methyl-1,3,5-triazin-2-yl)-amino)-carbonyl]-
amino]-sulphonyl}-benzoic aicd or its methyl ester
(METSULFURON); 1-(3-trifluoromethyl-phenyl)-4-methyl-
amino-5-chloro-6-pyridazone (NORFLURAZON); N-(l-ethyl-
propyl)-3,4-dimethyl-2,6-dinitroaniline (PENDIMETHALIN);
0-(6-chloro-3-phenyl-pyridazin-4-yl) S-octyl thio-
carbamate (PYRIDATE); ethyl 2-[4-(6-chloro-quinoxalin-2-
yl-oxy)-phenoxy]-propionate (QUIZALOFOP-ETHYL); 2-[1-
(ethoxamino)-butylidene~-5-(2-ethylthiopropyl)-1,3-
cyclohex~ione (SETHOXYDIM); methyl 2-{[(4,6-dimethyl-2-
pyrimidinyl)-aminocarbonyl]-aminosulphonyl}-benzoate
(SULFOMETURON); 4-ethylamino-2-t-butyl~mino-6-methylthio-
s-triazine (TERBUTRYNE); methyl 3-[[[[(4-methoxy-6-
methyl-1,3~5~triazin-2-yl)-amino]-carbonyl3-aminol-
sulphonyl]-thiophene-2-carboxyla~e (THIAMETURON); S-
Le A 27 154 - 55 -
~2,3,3-trichloroallyl~-N~N-diisopropylthiocarbamate
t TRI -ALLATE ), 2,6-dinitro-4-trifluoromethyl-N,N-dipro-
pylaniline (TRIFLURALIN). Suprisingly ,some mixtures also
show a ~ynergistic effect.
Mixtures with other known active compounds, such
as fungicides, insecticides, acaricides, nematicides,
bird repellants, plant nutrients and agents which improve
soil structure, are also possible.
The active compounds can be used as such, in the
form of their formulations or in the use forms prepared
therefrom by further dilution, such as ready-to-use
solutions ~ suspensions, emulsions, powders, pastes and
granules. They are used in the customary manner, for
example by watering, spraying, atomizing or scattering.
The active compounds according to the invention
can be applied either before or after emergence of the
plants.
They can also be incorporated into the ~oil
before sowing.
The amount of active compound used can vary
within a sub~tantial 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.
~e A 27 154 - 56 -
~Jlj2
Preparation Examples:
EXamD1e 1
CC)OCH3 O ~
~S ~2 ~ NH - CO~N N,L_1
H3
(Process (a))
3.0 g (17.95 mmol) of 4-cyclopentyl-5-methyl-2,4-
5dihydro 3H-1,2,4-triazol-3-one are dissolved in 60 ml of
acetonitrile, and 6.9 g ~28.6 mmol) of 2-methoxycarbonyl-
phenylsulphonyl isocyanate, dissolved in 20 ml of aceto~
nitrile, are added to this ~olution with s~irxing. The
reaction mixture is stirred for 6 hours at 20~C and then
10concentrated. The residue which ~ i n~ is stirred with
diethyl ether, and the product which has been obtained in
cry~t~lline form is isolated by filtration with suction.
. This gives 6.6 g (90 ~ of theory) of 4-cyclo-
pentyl-5-methyl~2-(2-methoxycarbonyl-phenylsulphonyl-
15aminocarbonyl)-2,4-dihydro-3H-1,2,4-triazol-3-one of
melting point 146 DC .
Le A 27 154 - 57 -
~"/,i7J 7 ~
Exampl~ 2
Cl O
~2 -NH - CO~NJ~N~CH3
CH 2H5
(Process (b) )
1,8 g (11.8 mmol) of 1,8-diazabicyclo-~5,4,0]-
undec-7~ene (DBU) are added to a stirred mixture of 3.0 g
(12.1 mmol) of 5-ethyl-4~methyl-2-phenoxycarbonyl-2,4-
dihydro-3H-1,2,4-triazol-3-one, 2.5 g (12.2 mmol) of 2-
chloro-6-methyl-benzenesulphonamide and 60 ml of aceto-
nitrile. The reaction mixture is stirred for 2 hours at
20~C, then poured into about twice the volume of
ice-water, and a pH of about 2 is established by dropwise
addition of concentrated hydrochloric acid. The product
which has been obt~ined during this process in crystal-
line form is isolated by ~iltration with ~uction.
This gives 3.2 g (73.5 % of theory) of 5-ethyl-
4-methyl-2-(2-chloro-6-methyl-phenyl3ulphonyl-amino-
carbonyl)-2,4-dihydro-3H-1,2,4-triazol 3-one of melting
point 176~C.
For example the compounds of the formula (I)
listed in Table 3 below can al80 be prepared analogously
to Examples 1 and 2 and ~ollowing the general instruc-
tions of the preparation processes according to the
invention.
Le A 27 154 _ 5~ _
J ~
R3-So2-NH-Co~NJ~N~Rl ( I )
Table 3: Preparation Examples of the compounds of the
formula (l) (m.p. = melting point)-
~x. Rl R2 R3 m~p. (~C)
No.
COOC~3
3 C6H5 CH~ ~ 1s8
OCHF2
4 CH3 C2H5 ~ 15 9
OCHF2
C~H5 C2Hs ~ 115
OCHF2
6 CH3 C3~7 ~ 1 4 3
Cl
7 C2H5 C2H5 ~$ 139
~H3
~e A 27 154 - 59 -
Table 3: - continuation
Ex. R1 R2 R3 m.p. (~C)
No.
Cl
8 CH3 C3H7 ~ 141
~H3
COOCH3
g OCH3 CH~ ~ 121
So2N(cH3)2
OCH3 CH3 ~ ~ 1 BO
11 OC~3 CH3 CH3 149
COOCH3
12 QCH3 C2H5 ~ 144
COOCH3
~--(
13 OCH3 C3H7 ~ 128
5O2N(CH3)2
14 CH3 C2H5 ~ 173
Le A 27 154 - 60 -
~JJ ~P ~ J~ i,J ~
Table 3: - continuation
Ex. R1 R2 R3 m.p. (~C~
No .
5O2N(CH3)2
C~3 C3H7 ~ 133
COOCH3
16 C2H5 ~ 154
COOCH3
17 OCH3 CH(CH3)2 ~ 137
SO2N~CH~2
/\ ~< '
18 C2H5 ~ 174
COOCH3
19 C3H7 ~ 97
COOCH3
CH3 N(CH3)z ~ 168
COOCH3
21 OCH2C6H5 CH3 ~ 174
Cl
22 C2H5 C3H7 ~ 136
CH3
Le A 27 154 - 61 -
~ 3 ~ ~ r~J ~i~3
Table 3: - continuation
Ex. Rl R2 R3 m.p. ( C)
No .
COOCH3
23 N(CH3)2 C2H5 ~ 139
COOCH3
24 N(CH332 H ~ 197
COOCH3
N(CH3)2 CH(CH3)2 ~ 148
GOOCH3
26 ~C2HS C2H5 ~ . 153
COOCH3
27 ~C2H5 C3H7 ~ 155
COOCH~
~ ~C
28 CH(CH3)2 ~ 186
Cl
29 C3H7 ~ 146
CH3
COOCH3
N(CH332 C3H7 ~ llo
Le A 27 154 - 62 -
~ ~J 1~ t,3 ~J
Table 3: - continuation
Ex. Rl R2 R3 m.p. ( qC)
No .
C OOCH 3
~\ ~<
31 N(CH3)2 <~ 131
COOC~3
32 C2H5 C4H9 ~ 98
COOC~13
33 CH3 C4H9 ~ 113
COOCH3
34 C3H7 C4H9 e~ 88
COOCH3
3s C~Hg ~ 117
COOCH 3
36 O~H3 C4H9 ~ 117
COOCH3
37 CH3 ~ 141
COOCH3
38 C2H5 ~ 130
Le A 27 154 - 63 -
~J~ J~
.
Table 3: - continuation
Ex . Rl R2 R3 m . p . ( C )
No .
COOCH3
39 C3H7 ~ 139
COOCH
~ ~\ ~e~ 3
~ 151
COOCH3
41 {~ CH3 ~ lSl
COOCH3
42 CH(C113)2 NHCH(CH3)2 ~ 135
C OOCH 3
43 N~CH3)2 N~C113)2 ~ 171
OCF3
44 CH3 C3H7 ~ 168
COOCH3
~5 C2~5 N(CH3)2 ~ 134
OCF3
4 6 CH3 C2HS ~ 16 7
Le A 27 154 64 -
Table 3: - continuation
Ex. R1 R2 R3 m.p. (~C)
No.
OCF3
47 NH2 C3H7 ~ 120
COOCH3
48 ~ NH ~ ~ 120
COOCH3
49 H ~ 195
COOCH3
-CH2CH=CHz C2H5 ~ 108
COOCH3
51 -CH2CH=CH2 H ~ 158
OCF3
52 OCH3 C3H7 ~ 110 - 111
COOCH3
53 CHz ~ H ~ 212 - 214
COOCH3
54 C3H7 H ~ 1~8 - 169
Le A 27 154 - 65 -
Table 3: - continuation
Ex. Rl ~2 R3 m.p. (~C)
No.
OCF3
C3H7 ~ 103 - 105
OCF3
56 C2H5 ~ 127
OCF3
57 OCH3 C2H5 ~ 111 - 113
COOC~3
/\ ~
58 -OCH3 ~ 139
OCF3
59 -1~HCH3 C3H7~n ~ 196
F
CH3 C3H7 n ~ 178
COOCH3
61 ~ H ~ 177
Le A 27 154 - 66 -
~ ~ f. . .~ - 3 ~ ~
;
Table 3: - continuation
Ex. Rl R2 R3 m.p. ~C)
No.
COOCH3
62 -CH2CH(CH3)2 C2H5 ~ 123
COOCH3
63 -CH2-CH=~H2 C3H7 n ~ (amorphous)
COOCH3
64 CH2 ~ C2H5 ~ 157
COOCH3
~ C2H5 ~ 117
COOCH3
66 -C~CH3)3 C2H5 ~ 182
COOCH3
67 ~ C2H5 ~ 133
COOCH3
68 ~ C2H5 ~ 162
COOCH3
6~ -CH2-CH-CH2 CH3 ~ 120
L~ A 27 154 _ ~7 -
~ ~ ~', ?, ? ~
Table 3: - c~ntinuation
Ex. Rl- R R3 m.p. (~C)
NoO
COOCH3
~ C2H5 ~ 183
COOCH3
71 C2H5 H ~ 196
COOC~3
72 ~ CH3 ~ 153
OCF3
73 -OCH3 ~ 138
COOCH3
74 CH(CH3)2 H ~ 191
COOCH3
~ H ~ 191
COOCH3
76 ~ H ~ lq2
COOCH3
77 -C~CH3)3 H ~ 211
Le A 27 154 - 68 -
~,l$j,,~"~
Table 3: - continuation
Ex. R1 R2 R3 m.p. ~ DC)
No.
COOC~3
78 -CHz-CH-CH2Br CH3 ~ 110
Br
COOCH3
79 CH3 -CH20CH3 ~ 152
CH3 C2H5 ~ 174
COOCH3
81 CH3 -CH20C2H5 ~ F3 123
82 -OCH3 C3H7~n ~ (amorphous)
~\ ,~CON(CH3)2
83 C2H5 ~ 124
OCF3
84 -CH20CH3 ~ 102
COOCH3
-CH20CH3 ~ 155
Le A 27 154 - 69 -
~ ~ ~ r~1
Table 3: - continuation
Ex. Rl R2 R3 m.p. (~C)
No.
86 -CH20C2H5 ~ OCH3 123
OCF3
87 -CH20C2H5 ~
88 -N(CH3)2 ~ 189
Cl3
89 -OCH3 C2H5 ~ 15S
CH3
C2H5 ~ 133
CH3
91 -OCH3 C3H7~n ~ 125
CH3
92 C~H5 ~ 138
5 OOCH~
Le A 27 154 ~ 70 -
r'
Table 3. - continuation
Ex . R1 R2 R3 m . p . ( C )
No .
OCF3
93 -OC2H5 C2H5 ~ 132
OCF3
94 -0C2Hs C3H7~n ~ 107
OCF3
-OCH3 CH(CH3)2 ~ 128
OCF3
g6 OCH3 CH3 ~ 119
97 C3H7 n ~ COOCH3 100
OCF3
~ 140
98 ~
COOCH3
99 -N(CH3)2 ~ 163
CH3
100 -N(CH3)2 ~ 182
Le A 27 154 - 71 -
~ !3
Table 3: - continuation
Ex. R1 R2 R3 m.p. t~C)
No.
101 CH3 -N(CH3)2 ~ 181
CH3
COOCH3
102 CH3 -OCH3 ~ 1 150
103 C2H5 ~ 147
CH3
104 -CH2-CH=CH2 CH3 ~ 132
C 1
105 -CH2-CH=CH2 C2H5 ~ 109
CH3
106 -CH2-CH=CH2 C3H7~n ~ 104
CH3
Le A 27 154 72 -
Table 3: - continuation
EX. Rl RZ R3 m.p. ~ C)
No.
107 -OC2H5 C2H5 ~ 147
Cl3
108 -~C2H5 C3H7 n ~ 136
CH3
109 -~CH3 CH(CH3)2 ~ H3 126
Cl
110 CH3 CH3 ~ 146
CH3
111 CH3 ~ 175
CH3
112 CH3 CH(CH3)2 ~ 124
CH3
Le A 27 154 _ 73 _
Table 3: - continuation
Ex. R~ R2 R3 m.p. (~C)
No.
113 CH~ ~ 171
CH3
114 CH(CH3)2 ~ 132
115 ~ 167
CH3
CH3
116 CH3 C~3 ~ 155
CH3
117 CH3 CZH5 ~ 147
CH3
118 CH3 C3H7 n ~ 16
~e A 27 154 - 74 -
~able 3: - continuation
Ex . R1 R2 R3 m . p . ~ C )
No .
119 OCH3 C2H5, ~COOCH3
Cx COOCH3
120 --CH2 C2H5 ~ 132
Le A 27 154 _ 75 _
Startinq substances of the formula (II):
Exa~pl~ (II-1)
o
H7J~N~OC 2H5
2H5
steP 1:
H-N-co-NH-oc2H5 ( IX- 1 )
H-N-CO-C2H5
A mixture of 68.5 g (0.60 mol) of 5-methyl-lr3,4-
oxadiazolin-2-one, 45.8 g (0.75 mol) of 0-ethyl-hydroxyl-
amine and 400 ml of water is refluxed for 12 hours and
then concentrated. The residue is taken up in ethanol and
reconcentrated. The residue which is obtained in this
process is stirred with diethyl ether, and the product
which has been obtained in crys~alline form is isolated
by filtration with suction.
This gives 77.5 g (74 % of theory) of 1-ethoxy-
aminocarbonyl-2-propionyl-hydrazine of m~lting point
122~C.
Le A 27 154 - 76 -
Ste~ 2:
H7 ~ N~OC2H5 (II-l)
NC~C 2 H 5
A mixture of 75c5 g (0.43 mol) of l-ethoxyamino-
carbonyl-2-propionyl-hydrazine, 17.5 g (0.44 mol) of
sodium hydroxide and 300 ml of water is refluxed for 12
hours. When the mixture is cold, a ph of between 3 and 4
is established by adding concentrated hydrochloric acid,
and the mixture is concentrated. The residue is stirred
with ethyl acetate, and the sodium chloride which has
r~;ned undissolved is separated off by filtration with
suction. The filtrate is concentrated, the residue i5
stirred with diethyl ether, and the product which has
been obtained in crystalline form is isolated by filtra-
tion with suction.
This gives 37 g (55 % of theory) of 4~ethoxy-5-
ethyl-2,4-dihydro-3H-1,2,4-triazol-3-one of melting point
93~C.
Example (II-2)
H7J~N~CH3 ( I 1-2 )
N=l~C 3H 7
mixture of 40 g (0.31 mol) of 5-propyl-1,3,4-
~e A 27 154 - 77 -
oxadiazolin-2-one, 109 g of aqueous methylamine solution
(32 % strength, 1.125 mol of CH3NH2) and 500 ml of water
is refluxed for 12 hours and then concentrated. The
residue is taken up in ethanol and reconcentrated. The
residue obtained in this process is stirred with diethyl
ether, and the product which has been obtained in crys-
talline form is isolated by filtration with suction.
This gives 31.7 g (72 % of theory) of 4-methyl-
5-propyl-2,4-dihydro-3H-1,2,4-triazol-3-one of melting
point 86~C.
Example (II-3)
O
HN ~ N~N(CH3)2
856 g (4.0 mol) of diphenyl carbonate are dis-
solved in 588 g of ethylene chloride. 245 g (4.0 mol) of
dimethylhydrazine (98 % pure) are added dropwise with
lS water-cooling, and the mixture is heated slowly and,
for 4 hours, stirred at 60~C.
After the mixture has cooled to 20~C, 200 g
(4.0 mol) of hydrazine hydrate are added dropwise, and
the mixture is then stirxed for 12 hours. It is warmed to
70-80~C and, for about 1 hour, stirring is continued.
When cold, the solution is dis~illed in vacuo, during
which pro ess ethylene chloride and water are removed
(final bottom t~mrPrature 100~C~. The abo~e phenolic
Le A 27 154 - 78 ~ -
dimethyl carbodihydrazide solution is added dropwise in
the course of 90 minutes at reflux temperature (about
102~C) to 424 g (4.0 mol) of trimethyl orthoformate.
After the methanol which has formed is removed by distil-
lation, phenol is distilled off in vacuo, after which282 g of product mixture are obtained at a head temper-
ature of 85-105CC. This mixture is boiled with ~00 ml of
acetone, and filtered at boiling point, and the filtrate
is then cooled. The product which has been obtained in
this process in crystalline form is isolated by filtra-
tion with suction.
This gives 71 g (14 % of theory) of 4-dimethyl-
amino-2,4-dihydro-3H-1,2,4-triazol-3-one of melting point
127~C
For example the compounds of the formulae (II)
and (IIa) listed in Table 4 below can also be prepared
analogously to Examples (II-l) to (II-3).
HNJ~N--Rl ( I I )
N R
Le A 27 154 - 79
,3 f i
~able 4: Preparation examples of the compounds of the
formula (II)
~x. R1 R2 m.p. (~C)
No.
II-4 C3H7 CH3 48
II-S CH(CH3)2 CH3 118
11-6 CH3 CH3 139
II-7 C2H5 C2H5 117
I1-8 C3H7 C2H5 42 - 45
II-9 CH(CH3)2 C2H5 102
II-10 C~H5 C3H7 97
I1-11 C3H7 C3H7 (amorphous)
II-12 CH(CH3)2 C3H7 91
II-13 CH3 CH~CH3)2 9Z
II 14 C2H5 CH(CH3)2(amorphous)
II-15 c3~7 CH(CH3)2(amorphous)
II-16 CH(CH3)2 CH(CH3)2 168
II-17 C2H5 CH3 134
/\
II-18 CH3 159
I1-19 OCH3 c~3 178
II-20 OCH3 C2H5 140
II-21 OCH3 c3~7 127
Le A 27 154 - 80 -
,7 !iJ ~ I Ir~
Table 4 - continuation
~x. ~1 R2 m.p. (~C)
No.
II-22 OCH3 CH(CH3)2 130
Il-23 ~CH2c6H5 CH3 106
~\
II-24 C2H5 150
11-25 C3H7 130
11-26 ~C2H5 C3H7 72
~\
II-27 CHtCH3)2 12~
II-28 CH3 C4H9 50
II-29 C2H5 C4H~ 76
Il-30 C3H7 C4H9(amorphous)
II-31 OCH3 C4H9 100
.~
II-32 C4H9 66
II-33 CH3 68
II-34 C2H5 130
I I - 35 C3H7 6 8
II-36 154
Le A 27 154 - 81 -
3 ~
Table 4 - continuation
Ex. R1 R2 m.p. (~C)
No.
II-37 N(CH3)2 CH3 153
II-38 N~CH3)2 C2H5 114
II-3s N(CH3)2 C3H7 108
Il-40 N(CH3)2 CH(CH3)2 100
II-41 CH3 N(CH3)2 80
~\
II-42 N~CH3)2 134
II-4~ CHtCH3)2 NHCH(CH3)z205
II-44 N~CH3)2 NtCH3)2 93
II-45 C2H5 N(CH3)2 50
II-46 n CH3 145
II-47 ~ CH3 163
II-48 H 102
II-49 ~CH3 136 - 137
II-50 CH3 C6H5
II-51 NH2 H 19?
II-52 NH~ CH3 230
I I-5:3 NH2 C~3 163
Le A 27 154 - 82 -
~ f;,~?~lJ~
Tabl~ 4 continuation
EX. Rl ~2m.p. ( ~C)
No.
II-54 NHCH~ CH(CH3~2 105
/~
II-55 NHCH3 95
II-56 ~H2 C2H5 170
II-57 NH2 C3H7 147
II-58 NHCH3 NHCH3 137
II-59 CH2C6H5 C2H5 125
II-60 NHCH3 H 133
II-61 NHCH3 N~CH3)2 129
II-62 NHCH3 C3H7 76
II-63 NH2 ~ 1 248
II-64 NH2 -CHC2H5 176
C~3
II-65 NH2 183
II-66 NH2 ~ 210
CF3
11-67 NHCH3 C2H5 101
II-6R NH~ N(C2H5)2 196
Le A 27 l54 - 83 - I
~ 3~.J
Table 4 - continuation
Ex~ Rl R2 m.p. ~ C)
No.
II-69 NH2 C N- 233
II-70 NH2 CHtCH3~2 172
II-71 N~2 C(CH3~3 261
II-72 NH2 CH2CH2~CH3 98
II-73 NH2 C(CH3)2C2H5213
II-74 NH2 NHC2H5 220
II-75 NH2 OCH3 (amorphous)
lI-76 NH2 CH20CH3 134
II-77 NH2 CH20C2H5 104
II-78 NtCH3)2 CH3 153
II-79 CH2 ~ ~ C1 C2H5 103
II-80 -CH2CHtCH3)2 C2~5 105
II-81 C6H5 H 183
II-82 N(CH3)2 CHtCH3~2(amorphous)
II-83 NHCH3 CH3 114
II-84 NH2 CH2C6H5 168
II-85 NH2 N(CH3~2 207
II-86 NH2 C6H5 2 O
Le A 27 154 - 84 -
Table 4 - continuation
Ex. R1 R2m.p. ( ~C)
No .
II-87 NH2 ~ 223
II-88 NH2 NHcH(cH3)2152
II-89 NHCH3 NHCH(C~3~2120
11-90 ~ NH ~ 254
II-91 N(CH3~2
II-92 CH2C6H5 H 111
II-93 C3H? H 48
Il-94 C6H5 C2H5 124
Il-95 C(CH3~3 C2H5 158
II-96 CH3 H 157
II-97 ~ C2~5 108
II-98 I C2H5 132
Il-99 -CH2CH=CH2 CH3 108
II-100 C6H5 CiY3 150
II-101 ~ CH~ 116
II-102 ~ C~H5 146
II-103 C2H5 H 68
II-104 CH(CH3)2 H 105
Le A 27 154 - 85 -
~::
Table 4 - continuation
Ex. R1 R2 m.p. ( C)
No.
II-105 ~ H 79
II-106 ~ H 162
II-107C(CH3)3 H 194
II-108-CH2-CH-CH2Br CH3 111
Br
II-109CH3 -C~20CH3 104
II-110CH3 -CH20C~H5 102
II-lI1 ~ -CH20CH3 102
II-112 ~ -CH20C2H5 119
II-113 ~ -N(CH3)2 130
~CH3
II-114NH2 -N 186
'C2H5
,CH3
II-115NHz -N 165
C3H7 n
~C2H5
II-116NH2 -N 186
~C3H7-n
'I-117NH2 -N 0 267
II-118CH3 -OCH3 144
Le A 27 154 - 86 -
The compound of Example (II-118) disclosed in Table 4
(above) can be prepared as follows:
o
HN ~ N~CH~ 118)
C~
50.2 g (0.33 mol) of hydrazino-formic acid phenyl es~er
(= l-phenoxycarbonyl-hydrazine) and 36.~ g (0.33 mol;
90 % purity) of 0,0,~-trimethyl-iminocarbonate are mixed
at 40 ~C with 100 ml of 1,2-dichlorobenzene, and this
mixture is then stirred for two hours at 60 ~C. There-
after the mixture is heated further up to 120 ~C,
while methanol (formed during the reaction) is being
distilled off. Then the reaction mixture is cooled and
heated again in vacuo (0.01 mbar) to a temperature of
120 ~C in order to remove any remaining volatile com-
pounds (me~hanol, phenol and 1,2-dichlorobenzene) from
the reaction mixture. At a temperature above 120 ~C the
reaction product is distilled roughly and then crystal
lized from toluene.
This gives 7.5 g (18 % of theory) of 5-methoxy-4-methyl-
2,4-dihydro-3H-1,2,4-triazol-one as colorless crystals
of melting point 144 ~C.
Le A 27 154 - 87 -
i
~ .
~ J~
Examples of hydrazine derivatives of the
formula (IX) which can be obtained analogously to Ex-
~ ample (II-1), ~tep 1, are li~ted in Table 5 below.
H-N-CO-NH-Rl
I (IX)
H-N-CO-R2
Table 5: Examples of the hydrazine derivatives of the
formula (IX)
Ex, R1 R2 m.p. (~C)
No.
IX-2 OCH3 CzH5 120
~X-3 OCH3 C3H7 125
IX-4 OCH3 CH~CH3)2 127
IX-5 ~CH2c6H5 CH3 lOO
~\
IX-6 C2~5 174
~\
IX-7 C3H7 180
IX-8 ~C2H5 C3H7 119
~\
IX-9 CH(CH3)2 ISO
IX-10 OCH3 C4H9 134
IX-11 C4H9 159
Le A 27 154 - 88 -
Table 5 - continuation
Ex. R1 R~ m.p. ( ~C)
No .
~ /\
IX-12 188
/\
IX- 13 OCH3 140
IX-14 CH2-CH=CH2 C~H7 134
/\
IX-15 -CH20C2H5 9?
Le A 27 154 - 89 -
f;~ ~J~ ~
Startin~ sub6tances of the formula ~IV):
Example (IV-l)
~ J~
~ -CO'N N~CH3
N=L~C 2H 5
6.4 g (0.05 mol) of 5-ethyl-4-methyl-2,4-dihydro-
3H-1,2l4-triazol-3-one are dissolved in 80 ml of tetra-
5 hydrofur~n, and 1.8 g ~0.06 mol) of sodi~m hydride (8~ %
of substance) are added under nitrogen. After the mixture
has been stirred for one hour at 20~C, 7.9 g (0~05 mol)
of phenyl chloroformate are added dropwise, and the
reaction mixture is stirred at 20~C for a further 20
hours. After the mixture has been concentrated, the
residue is taken up in methylene chloride, and the
mixture is washed with water, dried with sodium sulphate
and filtered. The filtrate is concentrated, the residue
is triturated with diethyl ether, and the product which
has been obtained in crystalline form is isolated by
filtration with suction.
This gives 4.5 g (36 % of theory) of 5-ethyl-4-
methyl~2-phenoxycarbonyl-2,4-dihydro-3H-1,2,4-triazol-3-
one of melting point 141~C.
For example the compounds of the formula (IY)
listed in Table 6 beIow can also be prepared analogously
to Example (IV-1).
~e A 27 154 _ go -
.
h ~ ~J
Z - CO'N~N'Rl t I V )
~=L~R2
Table 6: Examples of the compounds of the formula ( IV)
Ex. ~ 2 z m.p. ( ~C)
No .
lV-2 C3H7 C3H7 C6~5 88
IV-3 OCH3 C3~7 C6H5 82
IV-4 CH3 C3H7 C6H5 84
IV-5 NH2 C3H7 C6H5 133
IV-6 NH2 CH3 C6H5 82
~\ .
IV-7 C2H5 C6H5 152
IV-8 ~C2H5 C2H5 C6H5
IV-s OCH2CH=CH2 CH3 C6~5
IV- I O ~ C4H9 Cl,H5
IV-ll c~3 C6H5
IV-~2 NHCH3 C?H5 C6H5
Le A 27 154 - 91 -
Table 6 - continuation
Ex. R1 R2 z m.p. (~C)
No.
IV-13 CH3 CH2C6H5 C6H5
IV-14 CH3 NHCH(CH3)2 C6H5
IV-15 MtCH3)2 N(CH3)2 C6H5
IV-16 C6H5
IV-17 ~C2H5 C6H5
IV- 18 OC3H7 C2H5 C6H5
IV- 19 C2H5 C4H9 C6H5
IV-20 CH(CH3)Z CH(CH3)2 C6H5
IV-21 OCH ~ C2H5 C6H5 89
IV-2Z C3H7 n C6H5 104
Le A 27 154 - 92
use Examples:
In the following use examples,the known herbicide
isocarbamide, of formula (A) below, is used as comparison
substance:
r~
~N~N - CO-NH- CH2CH ( CH3 ~ 2 ( A )
The formulae of ~he compounds according to the
invention used in the Vse Examples are listed indi~idual-
ly below in conjunction with the number of the
Preparation Examples:
OCHF2 0
~502-NH-CO~N N~CH3 (4
2H5
OCHF2 0
~S02-NH-CO'NJ~N'C2H5 ~ 5
N----C2H5
OCHF2 0
_< 11
<~so2-NH-co'N~N~cH3 ( 6 )
3H7
Cl O
~502-NH-CO'NJ~N~CH3 ( 2 )
CH3 ~C2H5
Le A 27154 - 9~ -
~ ~ ,~f J , ~
ClO
2 NH-C0~7 ~ N~C2~5 t7
C~3 ~ C2H5
(~1 0
SO2-NH-CO~N ~ N'CH3 t8)
CH3 ~ 3H7
COOC~3 O
5o2-N~-co~ ~ 'OCH3 (12)
C2H5
COOCH3 O
5o2-NH-co~ ~ OC~3 (1~)
3H7
N(CH3)2 o
~ SO2-NH-co~ ~ CH3 (14
~ 2~15
5o2N(cH3)2 o
SO2-NH-CO~N ~ N~CH3 (15)
~ C3~7
COOCH3 O
SO2-NH-CO ~ ~ (16)
2~5
COO~ O
SO2-NH-CO~ ~ OCH3 (17
}l~cl~l3)2
Le A 27 154 - 94 -
J ~ ~3
5o2N~cH3~2 o
~SO2-N~_co~ ~\ ( 18
C2H5
~SO2-NH-CO~N--I~h ~\ ~19 )
N=J~C 3H7
COOCH3 ~
~2 -NH- CO~N~N~C~3 ( 2a )
N ( CH3 ) 2
COOCH3 O
~SO2-NH-CO~Oc2H5 ( 26 )
zH5
~SO2-NH-CO~c2H ( 27 )
3H7
COOCH3 ~
~S02-NH-CO~N~ ~\ ~ 28 )
CH(C~3 J2
~S ~ 2 - NH - C O~N~N ~\ ~ 2 9 J
CH 3 N=C~C3H~
~502-NI~-CO~NJ~N~N (CH ) ( 3D )
3)~7
Le A 27 154
- 95 ~
:
,~
~5~ 3: ~
COOCH3 0
S02-NH-CO'N ~ N'C2H5 (32)
4H9
COOCH3 0
5~2 NH-C0~7 ~ N~CH3 (33
4Hg
COOCH3 0
S02-NH-CO~N ~ N'C3H7 (34)
~ C4H9
COOCH3 0
2 NH-C0'7 ~ ~ ~35
N ~ C4H9
COOCH3 0
S02-NH-CO'N ~ N'CH3 (37)
COOCH3 0
S02 NH CO~7 ~ 1~C3H7 (39)
<~502-NH-C0~7~ ~ (401
Le A 27 154 - g6 -
~ 3
COOCH3 O
502-NH-CO~y ~ N~OCH3 (9)
h ~H3
COOCH3 O
S02-NH-CO~N ~ N'N(C 3)2 (~
COOCH3 N ~ N
SO2-NH-CO' ~OCH3 (36)
C4Hg
Le A 27 154 - 97 -
~ ~ f; i I J ~
ExamPle A
Prc ~ -rgence test
Solvent: 5 parts by weight of acetone
~mulsifiero 1 part by weight of alkylaryl polyglycol
ether
To prepare 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 o~
active compound. It is expedient here to keep constant
the amount of water per unit area. ~he concentration of
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
of the plants is rated in % damage in comparison with 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 2, 6, 8, 12J 13, 16,
17, 18, 19, 20, ~5, 27, 28, 29, 34, 37, 39 and 40.
Le A 27 154 - 98 -
Example B
Post-emergence test
Solvent: 5 parts by weight of acetone
Emulsifier: 1 part by weight o~ alkylaryl polyglycol
ether
To prepare a suitable preparation o~ 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 having a height of 5 - 15 cm are
sprayed with the preparation of active compound in such
a way that the specifically desired amounts of active
compound per unit area are applied. The concentration of
the spray liquor is chosen in such a way that the speci-
fically desired amounts of active substance are applied
in lO00 1 of water/ha. After three weeks, the degree of
damage of the plan~s is rated in ~ damage in comparison
with the development of the untreated control. The
fi~ures denote:
0 % = no action (like unkreat~d control)
lO0 % = total destruction
In this test a clearly superior activity com-
pared with the prior ~rt i6 shown, for example, by the
compounds of Preparation Examples 2, 4, 5, 6, 7, R, 12,
13, l~, 15, ~6, 17, 18, 19, 20, 2~, ~7, ~8, 29, 30, 32,
33, 34, 35, 37, 39 and 40.
Le A 27 154 - 99 _
Example C
Pyricularia test (rice) / protective
Solvent: l2,5 parts by weight of acetone
~ 5jf;~r 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 ~oncentrate is ailuted
with water and the stated 2mount 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 % relative atmospheric humidity and
25~C
Evaluation of the disease infestation is carried out 4 days
after the inoculation.
In this test, a very good activity is sho~n, for
example, by the compounds according to the following
preparation examples:
9, 12, 13, 20~ 30, 31, 32, 33, 34, 35, 36, 37.
Le A 27 l54 - 100 -
i~ ~ ( r ;~ ~ IJ ~
Example D
Pyricularia Test (rice) / systemic
Solvent : 12,5 parts by weight of acetone
Emulsifier: 0,3 parts by weight of alkylaryl-poly-
glycol 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 plants have been grown is watered with 40
ml of the preparation of active compound. 7 days
after the treatment, the plants are inoculated with
an aqueous spore suspension of Pyricularia oryzae.
Thereafter, the plants remain in a greenhouse at a
temperature 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 inoculation.
In this test, an excellent activity is shown, for
example, by the compounds according to the following
preparation examples:
9, 12, 13, 20, 30, 31, 32, 33, 34, 35, 36, 37.
Le A 27 1~4 - 101 -
