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23189-7150E
A Process For Preparing 5-Methoxy-4
Methyl-2,4-DihydrD-3H-1,2,4-Triazol-3-one
The present divisional application is divided out of
parent application Serial No. 2,189,698 which is a divisional
application of application Serial No. 2,027,206 filed on
October 10, 1990.
The invention of the parent application relates to
new sulphonylaminocarbonyl-triazolinones of the formula I, to
several processes for their preparation, and to their use as
herbicides.
The invention of the present divisional application
relates to a process for preparing 5-methoxy-4-methyl-2,4-
dihydro-3H-1,2,4-triazol-3-one described in more detail here-
inunder. However, the expression "the invention" or the like
encompasses the subject matter of both the parent and the
divisional.
It is known that certain substituted aminocarbonyl-
imadazolinones, such as, for example, 1-isobutylaminocarbonyl-
2-imidazolidinone (isocarbamide), have herbicidal properties
(cf. R. Wegler, Chemie der Pflanzenschutz-and
Schadlingsbekampfungsmittel [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
sulphonylaminocarbonyl-triazolinones are a subgroup of the
broad class of compounds of the general formula (I)
O
R3 S02 NH CO- N N R1 (I)
~~ 2
R
in which R1 represents hydrogen, hydroxyl or amino, or
represents an
- 1 -
CA 02302058 2000-03-29
optionally substituted radical from the series
comprising alkyl, alkenyl, alkinyl, cycloalkyl, aralkyl,
aryl, alkoxy, alkenyloxy, alkylamino and dialkylamino,
R2 represents hydrogen, hydroxyl, mercapto or amino, or
represents an optionally substituted radical from the
series comprising alkyl, cycloalkyl, cycloalkenyl,
aralkyl, aryl, alkoxy, alkylamino and dialkylamino, and
R3 represents an optionally substituted radical from the
series comprising alkyl, aralkyl, aryl and heteroaryl,
as well as salts of compounds of the formula (I),
have now been found.
The sulphonylaminocarbonyl-triazolinones of the
general formula (I) are obtained when
a) triazolinones of the general formula (II)
O
HN~N_Rt
W )
R2
in which
R1 and R2 have the abovementioned meanings, are reacted
with sulphonyl isocyanates of the general formula (III)
3
R -S02-N=C=O (III)
in which
R3 has the abovementioned meanings, if appropriate in
the presence of a diluent, or when
b) triazolinone derivatives of the general formula (IV)
- 2 -
23189-7150D
' CA 02302058 2000-03-29
~.. ~ ,
~,
O
Z-CO-N~N-R1 (IY)
~R2
in which
R1 and RZ have the abovementioned meanings and
Z represents halogen, alkoxy, aralkoxy or aryloxy,
are reacted with sulphonamides of the general
formula (V)
R3-502-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-R1 (II)
~N---.~ 2
R
in which
Rl and RZ have the abovementioned meanings
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CA 02302058 2003-05-20
30517-181E
are reacted with-sulphonamide derivatives of the genera 1
formula (VI)
R3- 50,7 NH-CO-Z (VI )
._
in which R3 has the abovvernentioned meaning and Z represents
halogen, alkoxy, aralkoxy or aryloxy, if appropriate in the
presence of an acid acc~:=ptor and if appropriate in the presence
of a diluent, s.nd, if ap~~ropriate salts are formed by customary
methods from the compouz-~cs of the formula (I) prepared by
process (a), (b) oa-~ (c) .
The :resent iu~~ention provides a process for prepar-
ing 5-methoxy-~4-methyy-.:,-~_-d:~hyc~ro--3H-i,~,4-triazol-3-one of
the formula (I_:-118 )
L
~1
(II-118)
~;1~ N-CH3
OCI~.~
which process comprise: reacting hydrazino-fcrmic acid pher~wi
1~- ester with an <about~ eq~::i::~ac>lar amount of O,N,2.T-trimethyliminc-
carbonate at elevated t :m~.~r~rature, in t~~: presence of a diluent.
The :zew sulpl~.or.-e ar~5.nocarbonz-1-triazclinones of the
general formula (I arc' f..aE:~.r salt:r are dl stirgui.shed by a
powerful herbi~zidal act:-iv~.ty . Surprisingly, the new compounds
of the formula (I) show a considerably better herbicida 1 action
than the known herbicic:ve i-isobutylaminocarbonyl-2-imidazoli-
dinone (isoca:rbamide), which has a similar structure.
The new comprunds of the present parent application
are those compounds of the formula (I) in which R1 represents
hydrogen, hydroxyl or amino, or represents C1-C6-alkyl which is
optionally substituted by fluorine, chlorine, bromine, cyano,
C1-C4-alkoxy, C1-C4-alk;ylcarbonyl or Cl-C4-alkoxycarbonyl, or
repzesents C3-C6-alken~rl or C3-C8-alkinyl, each of which is
optionally substituted by fluorine, chlorine and/or bromine,
or represents C3-C6-cyc:-loalkyl which is optionally substituted
by fluorine,
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CA 02302058 2000-03-29
chlorine, bromine and or Cl-C4-alkyl, or represents
phenyl-C1-C3-alkyl which ~is optionally substituted by
fluorine, chlorine, bromine, cyano, vitro, C1-C~-
alkyl, trifluoromethyl, C1-C4-alkoxy and/or (:1-C~-
alkoxy-carbonyl, or represents phenyl which is
optionally substituted by fluorine, chlorine,
bromine, cyano, vitro, C1-C~-alkyl, trifluoromethyl,
Cl-C~-alkoxy, fluorine- and/or chlorine-substituted
Cl-C3-alkoxy, C1-C4-alkylthio, f luorine- and/or
chlorine-substituted C1-C3-alkylthio, Ca-C4-alkylsul-
phinyl, C1-C,-alkylsulphonyl and/or C1-C4-alkoxy-
carbonyl, or represents C1-Cg-alkoxy which is option-
ally substituted by fluorine, chlorine, cyano,
phenyl, C1-C4-alkoxy or Cl-Cy-alkoxy-carbonyl, or
represents C3-C,-alkenyloxy, or represents C1-C4-
alkylamino which is optionally substituted by
fluorine, cyano, C1-C4-alkoxy or C1-C4-alkoxy-car-
bonyl, or represents di-(C1-C~-alkyl)-amino,
R2 represents hydrogen, hydroxyl, mercapto or amino, or
represents C1-CB-alkyl which is optionally substitut
ed by fluorine, chlorine, bromine, cyano, C3-CB
cycloalkyl, C1-Cy-alkoxy or C1-Cw-alkoxy-carbonyl, or
represents C3-CB-cycloal.kyl which is optionally
substituted by fluorine, chlorine, bromine and/or
C1-C,-alkyl, or represents cyclohexenyl, or repre-
sents phenyl-C1-C3-alkyl which is optionally substi-
tuted by fluorine, chlorine, bromine, cyano, vitro,
C1-C4-alkyl, trifluoromethyl, C,-C4-alkoxy and/or
C1-C,-alkoxy-carbonyl, or represents phenyl which is
optionally substituted by fluorine, chlorine,
,f
r
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bromine, cyano, vitro, C1-C,-alkyl, trifluoromethyl.
C1-C~-alkoxy, fluorine- and/or chmrm~s-aunstituced
C1-C3-alkoxy, C~-C'-alkylthio, fluorine- and/or
chlorine-substituted Cl-C3-alkylthio, C,-C,,-alkyl-
sulphinyl, Cl-C~-alkylsulphonyl and/or C1-c:,-alkoxy-
carbonyl, or represents C1-C6-alkoxy which is option-
ally substituted by fluorine, chlorine, cyano, C,-C,-
alkoxy or Ci-C,-alkoxy-carbonyl, or represents C1-C~-
alkylamino or di-(C1-C~-alkyl)-amino, and
R3 represents the group R5 , where
R4
R4 and Rs are identical or different and represent
hydrogen, fluorine, chlorine, bromine, iodine,
vitro, C1-C6-alkyl (which is optionally substituted
by fluorine, chlorine, bromine, cyano, carboxyl,
C1-C~-alkoxycarbonyl, Cl-C,-alkyl amino-carbonyl, di-
( C1-C4-alkyl ) amino-carbonyl, hydroxyl, C1-C~-alkoxy,
formyloxy, C1-C~-alkyl-carbonyloxy, Cl-C,-alkoxy-
carbonyloxy, C1-C,-alkyl amino-carbonyloxy, C1-C4_
alkylthio, C~-C4-alkylsulphinyl, C1-C,-alkylsulphonyl,
di-(Cl-Cw-alkyl)-aminosulphonyl, C3-C6-cycloalkyl or
phenyl ) , or represent CZ-C6-alkenyl (which is option-
ally substituted by fluorine, chlorine, bromine,
cyano, C1-C~-alkoxy-carbonyl, carboxyl or phenyl ) , or
represent CZ-Cfi-alkinyl (which is optionally s'ubsti-
tuted by fluorine, chlorine, bromine, cyano, C1-C4-
alkoxy-carbonyl, carboxyl or phenyl), or represent
Le A 27 154 _
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C1-C~-alkoxy (which is optionally substituted by
fluorine, chlorine, bromine, cyano, carboxyl, C1-C~-
alkoxy-carbonyl, C1-C4-alkoxy, C~-C~-alkylthio, C1-C~-
alkylsulphinyl or Ci-C~-alkylsulphonyl ) , or represent
C1-C~-alkylthio (which is optionally substituted by
fluorine, chlorine, bromine, cyano, carboxyl, C1-Cy-
alkoxy-carbonyl, C1-C,-alkylthio, C1-C~-alkylsulphinyl
or C1-C,-alkylsulphonyl ) , or represent C3-C6-alkenyl-
oxy (which is optionally substituted by fluorine,
chlorine, bromine, cyano or C1-C~-alkoxy-carbonyl),
ar represent C2-C6-alkenylthio (which is optionally
substituted by fluorine, chlorine, bromine, cyano,
vitro, C1-C3-alkylthio or C~-C,,-alkoxycarbonyl ) ,
C3-C6-alkinyloxy, C3-C6-alkinylthio, or represent the
radical -S ( O ) p-RB where
p represents the numbers 1 or 2 and
R6 represents C1-C4-alkyl (which is optionally
substituted by fluorine, chlorine, bromine, cyano
or Cl-C4-alkoxy-carbonyl ) , C3-C6-alkenyl, C3-C6-
alkinyl, C1-C~-alkoxy, C1-C4-alkoxy-Cl-C~-alkyl-
amino, Cl-Cy-alkylamino, di- ( C~-C~-alkyl ) -amino or
phenyl, or represents the radical -NHOR' where
R' represents C,-C,2-alkyl (which is optionally
substituted by fluorine, chlorine, cyano,
C1-C4-alkoxy, C1-C4-alkylthio, C1-C4-alkylsul
phinyl, l C1-C4-alkylsulphonyl, C1-C4-alkyl
carbonyl, Cl-C~-alkoxycarbonyl, C1-C,-alkyl
amino-carbonyl or di-(Cl-C~-alkyl)-amino
carbonyl), or represents C3-C6-alkenyl (which
is optionally substituted by fluorine,
be A 27 154 - 7 -
CA 02302058 2000-03-29
chlorine or bromine), C3-C6-alkinyl, C3-CB-
cycloalkyl, C3-Cs-cycloalkyl-C1-CZ-alkyl,
phenyl-C,-C2-alkyl (which is optionally substi-
tuted by fluorine, chlorine, vitro, cyano,
C1-C~-alkyl, C1-C,-alkoxy or C~-C,-alkoxy-car-
bonyl), or represents benzohydryl, or repre-
sents phenyl (which is optionally substituted
by fluorine, chlorine, vitro, cyano, Cl-C4-
alkyl, trifluoromethyl, C1-C4-alkoxy, C1-C2-
fluoroalkoxy, C1-C~-alkylthio, trifluoromethyl-
thio or C,-C~-alkoxycarbonyl),
R~ and/or Rs furthermore represent phenyl or phenoxy,
or represent Ci-C~-alkylcarbonylamino, Cl-Cw-
alkoxycarbonylamino, C1-C4-alkylamino-carbonyl-
amino, di-(Cl-C~-alkyl)amino-carbonylamino, or
represent the radical -CO-Re, where
Re represents C1-CB-alkyl, C1-C6-alkoxy, C3-C8-
cycloalkoxy, C3-C6-alkenyloxy, Cl-C' alkylthio,
C1-C4-alkylamino, C1-C~-alkoxyamino, C1-Cd-
alkoxy-C1-Ca-alkyl-amino or di- ( Cl-C~-alkyl ) -
amino (each of which is optionally substituted
by fluorine and/or chlorine),
R4 and/or RS furthermore represent trimethylsilyl,
thiazolinyl, Cl-C~-alkylsulphonyloxy, di-(Cl-C~
alkyl)-aminosulphonylamino, or represent the
radical -CH=N-Re, where
Re represents C1-C6-alkyl which is optionally
substituted by fluorine, chlorine, ~cyano,
carboxyl, C~-C~-alkoxy, C1-C~-alkylthio, C1-C~-
alkylsulphinyl or Cl-C~-alkylsulphonyl, or
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represents benzyl which is optionally substi-
tuted by fluorine or chlorine, or represents
C3-CB-alkenyl or C3-CB-alkinyl, each of which is
optionally substituted by fluorine or chlor-
ine, or represents phenyl which is optionally
substituted by fluorine, chlorine, bromine,
C1-C~-alkyl, C1-C~-alkoxy, trifluoromethyl,
trifluoromethoxy or trifluoromethylthio, or
represents C~-CB-alkoxy, C3-C6-alkenoxy, C3-Cs-
alkinoxy or benzyloxy, each of which is
optionally substituted by fluorine and/or
chlorine, or represents amino, C1-C~-alkyl-
amino, di-(C1-Cy-alkyl)-amino, phenylamino,
C1-C,-alkyl-carbonyl-amino, C1-C4-alkoxy-car-
bonylamino or C1-C~-alkyl-sulphonylamino, or
represents phenylsulphonylamino which is
optionally substituted by fluorine, chlorine,
bromine or methyl,
furthermore
R12
R3 represents the radical -~ , where
R10 Ril
Rl° represents hydrogen or C,-C,-alkyl,
Rll and R'2 are identical or different and represent
hydrogen, fluorine, chlorine, bromine, nitro,
cyano, C~-C,-alkyl (which is optionally substitut-
ed by fluorine and/or chlorine), C1-C,-alkoxy
{which is optionally substituted by fluorine
and/or chlorine) , carboxyl,~Cl-C,-alkoxy-carbonyl,
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dimethylaminocarbonyl, C1-C~-alkylsulphonyl or di-
( C1-C,-alkyl ) -aminosulphonyl;
furthermore
R' represents the radical R13 ' ~ ~ R14, where
R13 and R14 are identical or different and represent
hydrogen, fluorine, chlorine, bromine, vitro,
cyano, C1-C,-alkyl (which is optionally substitut
ed by fluorine and/or chlorine) or C1-c:~-atxoxy
(which is optionally substituted by fluorine
and/or chlorine);
furthermore
R15
R3 represents the radical
where
R16
R15 and Rl° are identical or different and represent
hydrogen, fluorine, chlorine, bromine, vitro,
cyano, Cl-C4-alkyl (which is optionally substitut-
ed by fluorine and/or chlorine), C1-C~-alkoxy
(which is optionally substituted by fluorine
and/or chlorine , or represent C,-C~-alkylthio,
C1-C~-alkylsulphinyl or Cl-C4-alkylsulphonyl (each
of which is optionally substituted by fluorine
and/or chlorine), or represent di-(C,-C~-alkyl)-
aminosulphonyl or C1-C~-alkoxy-carbonyl or di-
methylaminocarbonyl;
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' furthermore
R' represents the radical R1~ ~ ~ ~R18 , where
y
R1' and R'° are identical or different and represent
hydrogen, fluorine, chlorine, bromine, C1-C,-alkyl
(which is optionally substituted by fluorine and/or
bromine), Cl-C,-alkoxy (which is optionally substi-
tuted by fluorine and/or chlorine), or represent
C1-C,-alkylthio, C1-C,-alkylsulphinyl or C,-C,-alkyl-
sulphonyl (each of which is optionally substituted
by fluorine .and/or chlorine), or represent di-(C1-C,-
alkyl)-aminosulphonyl;
furthermore
R' represents the radical R19
where
A
Rte and RZ° are identical or different and represent
hydrogen, fluorine, chlorine, bromine, cyano,
vitro, Cl-C,-alkyl (which is optionally substitut-
ed by fluorine ~ and/or chlorine ) , Cl-C,-alkoxy
(which is optionally substituted by fluorine
and/or chlorine), C1-C,-alkylthio, C1-C,-alkylsul-
phinyl or C1-C,-alkylsulphonyl (which is optional-
ly substituted by fluorine. and/or chlorine), di-
( C1-C,-alkyl ) -amino-sulphonyl, (:1-C,-alkoxy-car-
bonyl or dimethylaminocarbonyl, and
A represents oxygen, sulphur or the group N-Zl,
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I !
' CA 02302058 2000-03-29
where
Z' represents hydrogen, C1-C'-alkyl (which is
optionally substituted by fluorine, chlorine,
bromine or cyano), C3-C6-cycloalkyl, benzyl,
phenyl (which is optionally substituted by
fluorine, chlorine, bromine or vitro), C1-C'-
alkylcarbonyl, C1-C~-alkoxy-carbonyl or di-
(C,-C,-alkyl)-aminocarbonyl;
furthermore
R21
R' represents the radical
'~R22 , where
1J1
Rz' and Rzz are identical or different and represent
hydrogen, C1-C'-alkyl, halogen, C1-C'-alkoxy-
carbonyl, C1-C'-alkoxy or C1-C'-halogenoalkoxy,
Y1 represents sulphur or the group N-Rz', where
Rz3 represents hydrogen or C~-C'-alkyl;
furthermore
R26
R3 represents the radical
' l where
tJ~N~
R25
124
R
Rz' represents hydrogen, C,-C'-alkyl, benzyl,
quinolinyl or phenyl, .
2g Rzs represents hydrogen, halogen, cyano, vitro,
C1-C'-alkyl (which is optionally substituted by
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i i,
CA 02302058 2000-03-29
fluorine and/or chlorine), Cl-C4-alkoxy (which is
optionally substituted by fluorine and/or
chlorine), dioxolanyl or Cl-C4-alkoxy-carbonyl, and
R26 represents hydrogen, halogen or Cl-C4-alkyl=
furthermore
R3 represents one of the groups listed below,
H3C0 / H3C
\ ~ ~N-C~9 ' N~
S ~~z~'3
2
\ O
O
The invention furthermore preferably relates to the
sodium, potassium, magnesium, calcium, ammonium, Cl-C4-
alkylammonium, di-(Cl-C4-alkyl)-ammonium, tri-(Cl-C4-alkyl)-
ammonium, CS- or C6-cycloalkyl-ammonium and di-(Cl-C2-alkyl)-
benzyl-ammonium salts of compounds of the formula (I) in
which Rl, R2 and R3 have the meanings mentioned above as
being preferred.
In particular, the invention of the parent
application relates to compounds of the formula (I) in which
R1 represents hydrogen, or represents Cl-C4-alkyl which is
optionally substituted by fluorine, chlorine, bromine,
cyano, methoxy or ethoxy, or represents allyl, or
represents C3-C6-cycloalkyl, or repre-
- 13 -
23189-7150D
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sents phenyl, or represents benzyl, or represents
C1-C3-alkoxy, or represents C1-C3-alkylamino, or
represents di-(C1-C2-alkyl)-amino,
R2 represents hydrogen, or represents C1-C~-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
C1-C3-alkoxy, or represents C1-C3-alkylamino, or
rEpresents di-(Ci-C2-alkyl)-amino, and
R3 represents the group , R5 , where
RQ
R" represents fluorine, chlorine, bromine, methyl,
trifluoromethyl, methoxy, difluoromethoxy,
trifluoromethoxy, 2-chloro-ethoxy, 2-methoxy-
ethoxy, Cl-C3-alkylthio, C1-C3-alkylsulphinyl,
C1-C3-alkylsulphonyl, dimethylaminosulphonyl,
diethylaminosulphonyl, N-methoxy-N-methylamino-
sulphonyl, phenyl, phenoxy or C1-C3-alkoxy-car-
bonyl, and
Rs represents hydrogen, fluorine, chlorine or
bromine;
furthermore
R»
R12
R3 represents the radical _CH~ , where
R10
R1° represents hydrogen,
r'
Le A 27 154 - 14 -
i
CA 02302058 2000-03-29
R11 represents fluorine, chlorine, bromine, methyl,
methoxy, dif luoromethoxy, t rif luoromethoxy, ethoxy,
methoxycarbonyl, ethoxycarbonyl, methylsulphonyl or
dimethylaminosulphonyl, and
R12 represents hydrogen,
furthermore
R3 represents the radical
IJ
RO-C S '
I
O
where R represents Cl-C4-alkyl, or
represents the radical
O
I I
RO-C
I ~ IN
N
I
~3
where R represents Cl-C4-alkyl.
Examples of the compounds are listed in Table 1
below - cf. also the Preparation Examples.
- 15 -
23189-7150D
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O '
R3-S02-NH-CO-N~N-~l
(I)
R
Table 1: Examples of the compounds of the formula (I)
Rl R2 R3
F
H
C1
H
OCF3
CHZ-CH=CHZ C2H5 ~H2_
OCHF2
OCH3 C3Hy ~H2-
O-CH2-CH=CH2 S OOCH3
COOCZHS
C2H5 C4H9 n
Le A 27 154 - 16 -
~ CA 02302058 2000-03-29
~ablg 1 - coptinuation
R1 R2 R3
S02NHOCH3
CH3 03H'
SOZN(CH3)2
C3H~
C1
GH3 C2H5 C 1~
e~r
C2H5 C3H7
CH3
COOCH2-CH2-C1
OC2H5
COOCH3
OC3H~ CH3 NON
CH3
CH3 C3H~ S OOCH3
COOCH3
1V ( CH3 ) 2 CH2~ ~H2_
Le A 27 154 _ 17 _
i
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Table 1 - continuation
Ri R2 R3
COOCH3
NH-CH3 ~ _
~H2
COOC2H5
CH3 C3H~
F~CHO
OCF3
OCH3
OCHFZ
OC2H5
F
C H 2-(. ,) C H 2
OCF3
CH2
C3H7
~N-
C3H7 ~N
'COOCH3
CH30
CH C~HS ~ SAN-C4H9
3
02
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Table 1 - continuation
R1 R2 ~3
CON(CH3)2
CH3 CqH9
CON(CH3)2
C3H7
CH3 C3H~
CZHS C2H5
- /
C3H~ /~'~
S02
OCHZ-CH2-C1
C2H5 C2H5
OCH3
CH3 C3H~-n
OC2H5
C3H? n
Le A 27 154 - 19 -
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aT ble 1 - continuation
RI R2 R3
H CF3
C~3
OCH3
CH3 C4H~ H2_
C1
v
CH3 ( HZ_
~C Cl
C2H5 / H2_
C1
CF3
C3H7 C3H7 ~H2_
CN
CH3 CH(CH3)2 ~CH2_
COOC2H5
-~ NON I
CH3
N~ I
Le A 27 154 - 20 -
i ,
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Table 1~- continuation
R1 R2 R3
COOC2H5
NON
OCH3 C2H5 ' ~N
i
COOCH(CH3)2
OC2H5 CZHS
Cl
CH3 CH3 ' I CF'3
r
CH3 CZHS
CH3
H3COOC
,N-C H 3
C1
CON(CH3)2
CH3 CH3 H3C
OCF3
CH3 CH(CH3)2 ~H2-
Le A 27 1~4 - 21 -
I,
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Table 1 - continuation
R 1 R2 1~3
Br
OCHZ-CH=CHZ C2H5 CH3
~CHS
S02-N~
OCH3
OCH3 C2H5
Br
CH3 CH(CH3)2
SCH3
CH3 CH2-CH=CHZ
S02CH3
CH3 CHZ-O-CH3
SCH(CH3)2
CH3 CH2-O-C2H5 /
F
C2H5 CZH4 O CH3 /
F
CH2-CH=CH2 H ~ I CON(CH3)2
Le A 27 154 - 22 -
I 1
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Tab - continuation
R1 R2 R3
OCHF2
CH2-CH=CH2 CH3
r
CH2-CH=CHZ CZHS ~/~N
CH3
C2H5 S OOCH3
COOC2H5
CH3 C3H
CH3
NH-CH3 CZHS
Cl
COOCH3
NH-GH3
'CHZ -
Si(CH3~3
CH3 C3H~
i ~ CON(CH3)2
C2H5 Cl
Le A 27 154 - 23 -
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Table 1 - continuation
f~c ~
CON(CH3)2
C2H5 C4H9 S
CH3
CH3 C3H~ N~S CHZ-CF3
-O
C2H5
CH3
CH
3 S
CH3
C2H5
CH3
OCH3 CH(CH3)2 ~ H2-
C2H5
OC2H5 C2H5
. i ( CF3
CH3 H
I~e A 27 154 - 24 -
i i
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fable 1 - continuation
R1 R2 R3
CH2-CHZ-0-CH3
CH3 CZHS
O-S02CH3
CH3 C3H~
' i 1
OCH3 C3H~ ~ II O
O
S02CH3
OCH3 H
CH3
CH3 C2H5 /
Br
OCHF2
CH2-CH=CHZ CHZ-O-CH3
Le A 27 154 - 25 -
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Table 1 - continuation
Rt R2 R3
~2~2'~
N(~3~ N(~3h
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) can be outlined by the following equation:
F O
H.N~N~O(:H3
NaC'O +
N C2Hs
F
F
_ O
SO2 NH CO~N~N~OC:H3
I
F N-~-~
~C H
2 S
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 substances, the course of the
reaction in process (b) can be outlined by the following
equation:
- 26 -
23189-7150D
CA 02302058 2000-03-29
scH3 0
~-CO~N~N~N~~3~2
-HCl
H
SCH3
_ O
NH-CO~N~N'N(CH3~
N--~
H
If, for example, N-methoxycarbonyl-2-methoxy-benzenesul-
phonamide and 5-diethylamino-4-difluoromethyl-2,4-dihydro-3H-
1,2,4-triazol-3-one are used as starting substances, the
course of the reaction in process (c) can be outlined by the
following equation:
OCH3 O
H.N~N'CH~'2
S02 NH COOCH3 I
N N(CZHsh
~3
O
-HOCH3 ~ ~ SOa NH CO~N~N'CHFZ
I
N--~
~N C H .
( 2 s~2
Formula (II) provides a general definition of the triazo-
linonea to be used as starting substances in processes (a)
and (c) for the preparation of compounds of the formula (I).
In formula (II), Rl and R2 preferably, or in
particular, have those meanings which have already been
- 27 _
23189-7150D
CA 02302058 2000-03-29
mentioned above in connection with the description of the
compounds of the formula (I) as being preferred, or
particularly preferred, for R1 and R2.
Examples of the starting substances of the formula
(II) are listed in Table 2 below.
O
HN~N_R1
I~ (B)
N R2
Table 2: Examples of the starting substances of the formula
(II)
R1 R2
H H
CH3 H
C2H5 H
C3H~ H
- 28 -
23189-7150D
i
CA 02302058 2000-03-29
Table 2 - continuation
~2
CH(CH3)2 H
C4H9 H
CH2CH(CH3)2 H
C(CH3)3 H
H CH3
H C2H5
H C3H?
H CH(CN3)2
H C4H9
H CH2CH(CH3)2
H C(CH3)3
CHF2 H
CH2CH2CN
CHZCHZOCH3 H
H CF3
H ' CH20CH3
H CH20C2H5
H CHZCHZOCH3
CH3 CH3
Le A 2? 154 _ 29 _
CA 02302058 2000-03-29
..
Table 2 - continuation
R1 R2
CH3 G2H5
CH3 C3H'
CH3 CH(CH3)2
CH3 C4H9
CH3 CHZCH(CH3)Z
CH3 C(CH3)3
C2H5 CH3
C3H7 CH3
CH(CH3)2 CH3
C4H9 CH3
CH2CH(CH3)2 CH3
C2H5 C2H5
C3H7 C3H7
CHF2 C3H~
CHF2 CH3
CHF2 C2H5
CH3 CF3
C2H5 CF3
CF2CHF2 CH
3
C2H5 C3H~
Le A 27 X54 - 30 -
CA 02302058 2000-03-29
Table 2 - continuation
f31 R 2
C2H5 C9H9
C6H5
/CHZ
C~CH CH 3
2
/CH2
CH3 -CH
~H2
CH3
CH3
CH3 N(CH3)2
C2H5 N(CH3)2
C2H5
C3H~
OCH3
C2H5
C3H7
Le A 27 154 - 31 -
CA 02302058 2000-03-29
Table 2 - continuation
R1 R2
CH3
CZH
C3H?
C3H?
CH3
CH3
NH2 CH3
CH3 NHCH3
NHCH3 CH
3
NHCH3 C H
2 5
NHCH3 C H
3 ?
NLCH3)2 CH
3
N(CH3)2 C H
2 5
N(CH3)2 C H
3 ?
Le A 27 154 - 32 -
i , !
CA 02302058 2000-03-29
Table 2 - continuation
R1 H2
OCH3 CHI
OCH3 C~H~
OCZHS GHQ
OCZHS ~~HS
CH2_O-C2H5
NtCHg~2
O_C3H7 C3H7
O-CH2-CH=CHZ CH3
O-CH2-CH=CH2 C2H5
O-CH2-CH=CHZ C3H~
O-CH2-iH-CHZ-Br C3H~
Br
OCH3
Le A 27 154 - 33 -
CA 02302058 2000-03-29
Table 2 - continuation
R~ N2
OCH3 I
OCH3
OCH3
OCH3
OCH3 N(CH3)2
O-CH2-COOCH3 C3H?
N(CH3)2
N(CH3)2
N(CH3>2
OC2H5 C3H7
OC2H5
Le A 27 154 - 34 -
i
t CA 02302058 2000-03-29
fable 2 - continuation
C~H
NH-CH3 CNZ-4-CH3
Cli2-O-CH3
CH3 CNZ-0-CH3
Le A 27 154 - 35 -
CA 02302058 2000-03-29
The starting substances of the formula (II) are known
and/or can be prepared by processes known per se (cf.
Chem. Her. 90 (1957)i 909-921; loc.cit. 98 (1965), 3025-
3099; J. Heterocycl. Chem. 15 (1978), 237-240; Tetra-
hedron 32 (1976), 23#7-2352; Hely. Chim. Acta 63 (1980),
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;
DE-P 3,916,208/LeA 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 obtained when
a) oxadiazolinones of the general formula (VII)
0
H~N~ (VII)
N~R2
in which
R2 has the abovementioned meaning
are reacted with amino compounds of the general
formula (VIII)
HZN'Ri (YIII)
in which
R1 has the abovementioned meaning,
Le A 27 154 - 36 -
CA 02302058 2000-03-29
at temperatures between 20°C and 120°C and, if
appropriate, in the presence of a diluent, such as,
for example, water, end the hxdrazine derivatives
fonued by this proce~a, o~ t#~~ general formula (IX)
H~ NCO-NH-Ri
H
(IX)
~N~
H CO-R2
in which
R' and RZ have the abovementioned meanings,
are isolated by customary methods (cf. the
Preparation Examples) and - or if appropriate even
without intermediate isolation - the compounds of
the formula (IX) are condensed at temperatures
between 20°C and 120°C and, if appropriate, 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) 3,7~3,493/LeA 25,759 and the
Preparation Examples),
or when
p) amino compounds of the general formula (VIII)
H2N-R~ (VIII)
Le A 27 154 - 37
i i
CA 02302058 2000-03-29
in which
R1 has the abovementioned meaning, are reacted with
carbonic acid derivatives, such as, for example, diphenyl
carbonate, then with hydrazine or hydrazine hydrate and
eventually with a carboxylic acid derivative or carbonic acid
derivative of the general formula (X)
(RO)3C_R2 (X)
in which
R2 has the abovementioned meaning and
R represents lower alkyl,
at temperature 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 26,937 dated 21.06.1989, DE-
P 3,928,662/LeA 27,137 dated 30.08.1989, and the Preparation
Examples).
Some of the compounds of formula II are novel.
According to one aspect of the invention of the
present divisional application there is provided a
triazolinone of the general formula (IIa)
O
1
~~N~A
W )
Az
in which either
(1) A1 represents di-(C1-C4-alkyl)-amino and
A2 represents hydrogen, or represents C1-C6-alkyl
which is optionally substituted by fluorine,
- 38 -
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i
CA 02302058 2000-03-29
chlorine, bromine, cyano, Cl-C4-alkoxy, C1-C4-
alkyl-carbonyl or C1-C4-alkoxy-carbonyl, or
represents C3-C6-cycloalkyl which is
optionally substituted by fluorine, chlorine,
bromine andlor C1-C4-alkyl, or represents
C1-C4-alkoxy;
or in which
( 2 ) A1 representsand A2 repres~ts
~3 ~3
OCH 3 C2Hs
OCH 3 C3H~
OC2Hs C2Hs
~3 ~(~3~2
OCHZC6Hs CH3
~2Hs C3H~
~3 C4H9
- 39 -
23189-7150D
i
' CA 02302058 2000-03-29
~3
~2Hs
~3H7 C3H7
~2'~-~2 ~3
acH2-cH-ci-~2 c2Hs
O-CHZ-CH-CH2 C~.H7
O-CH2- ~t,'H-CH-B!C3H7
~3
~3
OCH3 H
~3 ~2
O-CH2-COOC'H 3 C3H~
OCZHs
C3H~
~~~ 3~1
C4Hg
~3
CZHs
C~i~
H
- 39a -
23189-7150D
i I.
CA 02302058 2000-03-29
NH2 OCH3
C2Hs
-~2~'~2 CHg
CH3
~3 -CH20CH 3
'~2~ 3
'~2~2H5
-N~~3h
The new triazolinones of the formula (IIa) are
obtained either when oxadiazolinones of the general formula
(VIIa)
O
H~N~O
A2
in which
A2 has the abovementioned meaning,
are reacted with amino compounds of the general formula
(VIIIa)
HZN-A1 (VIIIa)
in which
A1 has the abovementioned meaning,
analogously to the process described above under (a), or when
amino compounds of the general formula (VIIIa)
H2N-A1 (VIIIa)
- 39b -
23189-7150D
i
I CA 02302058 2000-03-29
are reacted with carbonic acid derivatives, then with
hydrazine or hydrazine hydrate and eventually with a
carboxylic acid derivative or carbonic acid derivative of
- 39c -
23189-7150D
CA 02302058 2000-03-29
the general formula (Xa)
(RO)3C-AZ (Xa)
in which
A2 and R have the abovementio~ed meanings,
analogously to the process described above under (~)
(also see the Preparation Examples).
In the general formula (IIa),
A1 preferably represents C1-C6-alkyl, C3-C5-alkenyl
or C3-Cb-cycloalkyl, or represents C1-C6-alkoxy
Which is optionally substituted by fluorine, chlo-
rine, bromine, cyano, C1-C4-alkoxy or C1-C4-alk-
oxy-carbonyl, in particular methyl, ethyl, allyl,
cyclopropyl, methoxy, ethoxy, propoxy or isoprop-
oxy; or represents di-(C1-C4-alkyl)-amino, in par-
titular dimethylamino or diethylamino, and
A2 preferably represents hydrogen, or represents C~-C6-
alkyl which is optionally substituted by fluorine,
chlorine, bromine, cyano, C1-C~-alkoxy, C1-C~-alkyl-
carbonyl or Cl-C~-alkoxy-carbonyl, or represents
C3-C6-cycloalkyl which is optionally substituted by
fluorine, chlorine, bromine and/or Cl-C,,-alkyl, or
represents phenyl-C1-C3-alkyl which is optionally
substituted by fluorine, chlorine, bromine, cyano,
vitro, C1-C~-alkyl, trifluoromethyl, Cl-Cw-alkoxy
and/or C1-Cw-alkoxycarbonyl, or represents phenyl
which is optionally substituted by fluorine, chlor-
ine, bromine, cyano, vitro, Cl-C~-alkyl, trifluoro-
methyl, C,-C,-alkoxy, fluorine- and/or chlorine-
substituted C~-C3-alkoxy, C~-C4-alkylthio, fluorine-
and/or chlorine-substituted C1-C3-alkylthio, C1-C~-
alkylsulphinyl, C1-C,-alkylsulphonyl and/or C1-C,-
Le A 27 154 - 40 -
CA 02302058 2000-03-29
alkoxy-carbonyl, or represents C1-C4-alkoxy, in
particular hydrogen, Cl-C4-alkyl which is optionally
substituted by fluorine and/or chlorine, methoxy or
ethoxy, or represents C3-C6-cycloalkyl, or represents
methoxy or ethoxy,
provided that both Al and A2 do not simultaneously represent
Cl-C6-alkyl.
The compounds of the formulae (VII), (VIIa),
(VIII), (VIIIa) and (X) or (Xa) which are to be used as
starting substances for the preparation of the triazolinones
of the formulae (II) or (IIa) are known (cf. Helv. Chim. Acta
55(1972), 1174; EP-A 301,946; DE-OS (German 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) for the preparation of compounds of
the formula (I).
In formula (III), R3 preferably, or in particular,
has the meaning which has already been mentioned above in
connection with the description of the compounds of the
formula (I) as being preferred, or particularly preferred,
for R3.
Examples of the starting substances of the formula
(III) which may be mentioned are:
2-fluoro-, 2-chloro-, 2-bromo-, 2-methyl-, 2-methoxy-,
2-trifluoromethyl-, 2-difluoro-methoxy-, 2-trifluoromethoxy-,
2-methylthio-, 2-ethylthio-, 2-propylthio-, 2-methyl-
sulphinyl-, 2-methylsulphonyl-, 2-dimethylaminosulphonyl-,
- 41 -
23189-7150D
CA 02302058 2000-03-29
2-diethylaminosulphonyl-, 2-(N-methoxy-N-methyl)-
aminosulphonyl-, 2-phenyl-, 2-phenoxy-, 2-methoxycarbonyl-,
2-ethoxycarbonyl, 2-propoxycarbonyl- and 2-isopropoxy-
carbonyl-phenylsulphonyl isocyanate, 2-fluoro-, 2-chloro-,
2-difluoromethoxy-, 2-trifluorometh-2-methoxycarbonyl- and
2-ethoxycarbonyl-benzylsulphonyl isocyanate, 2-methoxy-
carbonyl-3-thienyl-sulphonyl isocyanate, 4-methoxycarbonyl-
and 4-ethoxycarbonyl-1-methylpyrazol-5-yl-sulphonyl
isocyanate.
The sulphonyl isocyanates of the formula (III) are
known and/or can be prepared by processes known per 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, 30,139, 35,893, 44,808, 44,809,
48,143, 51,466, 64,322, 70,041, 173,312).
Process (a) 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, optionally halogenated hydrocarbons,
such as pentane, hexane, heptane, cyclohexane, petroleum
ether, benzine, ligroin, benzene, toluene, xylene, methylene
chloride, ethylene chloride, chloroform, carbon
tetrachloride, chlorobenzene and o-dichlorobenzene, ethers,
such as diethyl ether and dibutyl ether, glycol dimethyl
ether and diglycol dimethyl ether, tetrahydrofuran and
dioxane, ketones, such as acetone, methyl ethyl ketone,
methyl isopropyl ketone and methyl isobutyl ketone, esters,
such as methyl acetate and ethyl acetate, nitriles, such as,
- 42 -
23189-7150D
CA 02302058 2000-03-29
for example, acetonitrile and propionitrile, amides, such as,
for example, dimethylformamide, dimethylacetamide and
N-methyl-pyrrolidone, and also dimethyl sulphoxide, tetra-
methylene sulphone and hexamethylphosphoric t riamide.
In process (a), 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) is generally carried out under
atmospheric pressure.
For carrying out process (a), 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
remains in the residue is crystallized using a suitable
solvent, such as, for example, diethyl ether. The product of
the formula (I) which has been obtained in crystalline form
is iso lat ed by f 1 It rat ion with suct ion .
Formula (IV) provides a general definition of the
triazolinone derivatives to be used as starting substances in
process (b) 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
- 43 -
23189-7150D
CA 02302058 2000-03-29
compounds of the formula t1) 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
- 43a -
23189-7150D
CA 02302058 2000-03-29
phenoxy.
Examples of the starting substances of the
formula (IV) which are possible are the compounds of the
formula (IV) to be prepared from the compounds of the
formula (II) listed in Tablp 2 Wand 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 se
(cf. EP-A 283,876; EP-A 294,666; EP-A 298,371.
The triazolit~one derivatives of the formula (IV)
are obtained for e~campl~ Whec~ triazolinones of the
general formula (II)
0
HN~N~R1 (II)
~R2
in which
R1 and R2 have the abovementioned meanings,
are reacted with carbonic acid derivatives of the general
formula (XI)
Z-CO-Z1 (XI)
in which
Z has the abovementioned meaning and
Le A 27 154 _ 44 _
CA 02302058 2000-03-29
Z1 represents a leaving 4roup, 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,
tetrahydrofuran, and, if appropriate, in the presence of an
acid acceptor, such as, for example, sodium hydride or
potassium tert-butylate (cf. the Preparation Examples).
Formula (V) provides a general definition of the
sulphonamides further to be used as starting substances in
process (b) for the preparation 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) as being preferred, 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-,
ZO 2-trifluoromethyl-, 2-difluoro-methoxy-, 2-trifluoromethoxy-,
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-methoxycarbonyl-,
2-ethoxycarbonyl-, 2-propoxycarbonyl- and 2-isopropoxy-
carbonyl-benzenesulphonamide, 2-fluoro-, 2-chloro-,
2-difluoromethoxy-, 2-trifluoromethoxy-, 2-methoxycarbonyl-
- 45 -
23189-7150D
CA 02302058 2000-03-29
and 2-ethoxycarbonyl-phenylmethanesulphonamide, 2-methoxy-
carbonyl-3-thiophenesulphonamide, 4-methoxycarbonyl- and
4-ethoxycarbonyl-1-methyl-pyrazol-5-sulphonamide.
The sulphonamides of the formula (V) are known
and/or can be prepared by processes known per se (cf. US-P
4,127,405, 4,169,719, 4,371,391f 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) 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).
Acid acceptors which can be employed in process (b)
are all acid-binding agents which can customarily be used for
reactions of this type. The following are preferably
suitable: alkali metal hydroxides, such as, for example,
sodium hydroxide and potassium hydroxide, alkaline earth
metal hydroxides, such as, for example, calcium hydroxide,
alkali metal carbonates and alkali metal alcoholates, such as
sodium carbonate, potassium carbonate, sodium tert-butylate
and potassium tent-butylate, furthermore aliphatic, aromatic
or heterocyclic amines, for example triethylamine,
trimethylamine, dimethylaniline, dimethylbenzylamine,
pyridine, 1-5-diazabicyclo-[4.3.0]-non-5-ene (DBN), 1-8-
diazabicyclo-[5.4.0]-undec-7-ene (DHU) and 1,4-diazabicyclo-
[2,2,2]-octane (DAHCO).
When carrying out process (b), the reaction
- 46 -
23189-7150D
I I'
CA 02302058 2000-03-29
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.
In general, process (b) 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), 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 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) 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) for the
preparation of compounds of the formula (I) have already been
described as starting substances for process (a).
Formula (VI) provides a general definition of the
sulphonamide derivatives further to be used as starting
substances in process (c) for the preparation of compounds of
the formula (I).
In formula (UI), R3 and Z preferably, or in
particular, have those meanings which have already been
mentioned above in connection with the description of the
- 47 -
23189-7150D
CA 02302058 2000-03-29
t
compounds of toe formula (I) or (IV) as being preferred, or
particularly preferred, for R3 and Z.
Process (c) is preferably 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).
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 mentioned above in
connection with the description of process (b).
When carrying out process (c) 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.
In general, process (c) 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), 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 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 (c) is carried out in
each case by customary methods.
- 48 -
23189-7150D
CA 02302058 2000-03-29
To convert the compounds of the formula (T) 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, dibutylamine 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 mixture.
The active compounds can be used as defoliants,
desiccants, agents for destroying 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
act as total or selective herbicides depends essentially on
the amount used.
The active compounds can be used, for example, in
connection with the following plants:
Dicotyledon weeds of the genera: Sinapis,
Lepidium, .Galium, Stellaria, Matricaria, Anthemis, Galinsoga,
Chenopodium, Urtica, Senecio, Amaranthus, Portulaca,
Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania,
Ambrosia, Cirsium, Carduus, Sonchus, Solanum, Rorippa,
Rotala, Lindernia, Lamium, Veronica, Abutilon, Emex, Datura,
Viola, Galeopsis, Papaver, Centaurea, Trifolium, Ranunculus
and Taraxacum.
Dicotvledon cultures of the genera: Gossypium,
Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum,
- 49 -
23189-7150D
CA 02302058 2000-03-29
r
Ipornoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica,
Lactuca, Cucumis and Cucurbita.
Monocotyledon weeds of the ctenera: Echinochloa,
Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine,
Branchiaria, Lolium, Bromus, Avena, Cyperus, Sorghum,
Agropyron, 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, Ananas, Asparagus and Allium.
However, the use of the active compounds is in no
way restricted to these genera, but also extends in the same
manner to other plants.
The compounds are suitable, depending on the
concentration, for the total combating of weeds, for example
on industrial terrain and rail tracks, and on paths and
squares with or without tree plantings. Equally, the
compounds can be employed for combating weeds in perennial
cultures, for example afforestations, decorative tree
plantings, orchards, vineyards, citrus groves, nut orchards,
banana plantations, coffee plantations, tea plantations,
rubber plantations, oil palm plantations, cocoa plantations,
soft fruit plantings and hopfields, in lawns, turf, meadows
and pastures, and for the selective combating of weeds in
annual cultures.
The compounds of the formula (I) are suitable for
combating monocotyledon and dicotyledon weeds both in the
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23189-7150D
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t
pre-emergence and the post-emergence method. They are
markedly more effective than, far example, isocarbamide.
To a certain extent, the compounds 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 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 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 suitable in the
main: aromatics, such as xylene, toluene, or
alkylnaphthalenes, chlorinated aromatics and chlorinated
aliphatic hydrocarbons, such as chlorobenzenes,
chloroethylenes or methylene chloride, aliphatic
hydrocarbons, such as cyclohexane or paraffins, for example
petroleum fractions, mineral and vegetable oils, alcohols,
such as
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23189-7150D
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t
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,
montmorillonite 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 foam-forming agents there
are suitable: 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, such as cephalins and lecithins, and
Le A 27 154 - 52 -
CA 02302058 2000-03-29
synthetic phospholipids, can be used in the formulations.
Further additives can be mineral and vegetable oils.
It is possible to use colorants such as inorganic
pigments, for example iron oxide, titanium oxide and Prussian
Blue, and organic dyestuffs, such as alizarin dyestuffs, azo
dyestuffs and metal phthalocyanine dyestuffs, and trace
nutrients such as salts of ion, 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 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-5-ethylthio-3-(2,2-
dimethylpropyl)-1,3,5-triazine-2,4(1H,3H)-dione (AMETHYDIONE)
or N-(2-benzothiazolyl)-N, N'-dimethylurea (METABENZTHIAZURON)
for combating weeds in cereals= 4-amino-3-methyl-6-phenyl-
1,2,4-triazin-5(4H)-one (METAMITRON) for combating weeds in
sugar beet and 4-amino-6-(1,1-dimethylethyl)-3-methylthio-
1,2,4-triazin-5(4H)-one (METRIBUZIN) for combating weeds in
Soya beanss furthermore also mixtures with 2,4-
dichlorophenoxyacetic acid (2,4-D)i
4-(2,4-dichlorophenoxy)-butric acid (2,4-DB)= 2,4-
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23189-7150D
CA 02302058 2000-03-29
dichlorophenoxypropionic acid (2,4-DP); 5-(2-chloro-4-
trifluoromethyl-phenoxy)-2-nitrobenzoic acid (ACIFLUORFEN);
2-chloro-2',6'-diethyl-N-methoxy-methyl-
- 53a -
23189-7150D
CA 02302058 2000-03-29
f 1
acetanilide (ALACHLOR); 2-chloro-4-ethylamino-6-iso-
propylamino-1,3,5-triazine (ATRAZINE); methyl 2-
[[[[[(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 (HUTACHLOR); ethyl 2-t[(4-chloro-6-
methoxy-2-pyrimidinyl)-aminocarbonyl]-aminosulphonyl}-
benzoate(CHLORIMURON);2-chloro-N-~[(4-methoxy-6-methyl-
1,3,5-triazin-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(DICHLOBENIL);2-[4-(2,4-dichlorophenoxy)-
phenoxy]-propionic acid, its methyl ester or its ethyl
ester (DICLOFOP); 2-[(2-chlorophenyl)-methyl]-4,4-di-
methylisoxazolidin-3-one (DIMETHAZONE); 4-amino-6-t-
butyl-3-ethylthio-1,2,4-triazin-5(9H)-one (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); N,N-dimethyl-N'-(3-
trifluoromethylphenyl)-urea (FLUOMETURON); 1-methyl-3-
phenyl-5-(3-trifluoromethylphenyl)-4-pyridone
(FLURIDONE); 5-(2-chloro-4-trifluoromethyl-phenoxy)-N-
methylsulphonyl-2-nitrobenzamide (FOMESAFEN); N-phos-
phonomethyl-glycine (GLYPHOSATE);
methyl 2-[4,5-dihydro-4-methyl-4-(1-methylethyl)-5-oxo-
Le A 27 154 - 54 -
CA 02302058 2000-03-29
. , r ,
1H-imidazol-2-yl]-4(5)-methylbenzoate (IMAZAMETHABENZ);
2-(4,5-dihydro-4-methyl-4-isopropyl-5-oxo-1H-imidazol-2-
yl)-pyridine-3-carboxylic acid (IMAZAPYR); 2-[5-methyl-
5-(1-methylethyl)-4-oxo-2-imidazolin-2-yl]-3-quinolin-
carboxylic acid (IMAZAQUIN); 2-[4,5-dihydro-4-methyl-4-
isopropyl-5-oxo-(1H)-imidazol-2-yl]-5-ethylpyridin-3-
carboxylic acid (IMAZETHAPYR); 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-di.methyl-
phenyl)-N-[(1H)-pyrazol-1-yl-methyl]-acetamide
(METAZACHLOR); 2-ethyl-6-methyl-N-(1-methyl-2-metho-
xyethyl)-chloroacetanilide (METOLACHLOR); 2-~[[((4-
methoxy-6-methyl-1,3,5-triazin-2-yl)-amino)-carbonyl]-
amino]-sulphonyl}-benzoic aicd or its methyl ester
(METSUI~FURON); 1-(3-trifluoromethyl-phenyl)-4-methyl-
amino-5-chloro-6-pyridazone (NORFLURAZON); N-(1-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-
cyclohexadione (SETHOXYDIM); methyl 2-{[(4,6-dimethyl-2-
pyrimidinyl)-aminocarbonyl]-aminosulphonyl}-benzoate
(SULFOMETURON); 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 (THIAMETURON); S-
Le A 27 154 - 55 -
CA 02302058 2000-03-29
(2,3,3-trichloroallyl)-N,N-diisopropylthiocarbamate (TRI-
ALLATE), 2,6-dinitro-4-trifluoromethyl-N,N-dipropylaniline
(TRIFLURALIN). Surprisingly, some mixtures also show a
synergistic 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 can be applied either before
or after emergence of the plants.
They can also be incorporated into the soil before
sowing.
The amount of active compound used can vary within
a substantial range. It depends essentially on the nature of
the desired effect. In general, the amounts used are between
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 can
be seen from the following examples.
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23189-7150D
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. .
Preparation Examples:
Example 1
COOCH3 O
~--S O2 - NH - C O~N~N
H3
(Process (a))
3.0 g (17.95 mmol) of 4-cyclopentyl-5-methyl-2,4-
dihydro-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 solution with stirring. The
reaction mixture is stirred for 6 hours at 20°C and then
concentrated. The residue which remains is stirred with
diethyl ether, and the product which has been obtained in
crystalline 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
aminocarbonyl)-2~4-dihydro-3H-1,2,4-triazol-3-one of
melting point 146°C.
Le A 27 154 - 57 -
CA 02302058 2000-03-29
f
Example 2
CI
O
SO2 NH CO~N~ ~CH3
N
I
N~C H
2 5
(Process (b))
1.8 g (11.8 mmol) of 1,8-diazabicyclo-[5,4,0]-
under-7-ene (DBU) are added to a stirred mixture of 3.0 g
(~2.1 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
acetonitrile. 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
obtained during this process in crystalline form is isolated
by f 1 It rat ion wit h suet ion .
This gives 3.2 g 973.5 ~ of theory) of 5-ethyl-4-
methyl-2-(2-chloro-6-methyl-phenylsulphonyl-aminocarbonyl)-
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 also be prepared analogously to Examples
1 and 2 and following the general instructions of the
preparation processes
- 58 -
23189-7150D
CA 02302058 2000-03-29
O
R3-SOZ-NH-CO~N~N~1 II)
2
R
Table 3: Preparation Examples of the compounds of the
formula (1j (m.p, - melting
point):
EX. R1 RZ R3 m.p. ( 'C)
No.
COOCH3
3 C6H5 CH3 158
OCHFZ
4 CH3 C2H5 159
OCHF2
5 CZHS C2H5 115
OCHFZ
6 CH3 C3H~ 143
Cl
7 C2H5 C2H5 ~ 139
CH3
Le A 27 154 _ 5g _
I CA 02302058 2000-03-29
1
i ~
Table 3s - continuation
EX. R1 R2 A9 m.p. ( °C)
No.
c1
8 CH3- C3H~ ~ 141
CN3
COOCH3
9 OCH3 CH3 121
Sb2N(CH3)2
OCH3 CH3 180
C1
11 OCH3 CH3 ~ 149
CH3
COOCH3
12 OCH3 C2H5 ~ 144
COOCH3
13 OCH3 C3H7 ~ 128
SOZN(CH3)2
14 CH3 C2H5 ~ 173
Le A 27 154 - 60 -
CA 02302058 2000-03-29
z
Table 3: - continuatiop
EX. R1 Ra ~t9 m.p. ( °C)
No.
SO~N(CH3)2
15 CH3 C3H7 ~ 133
CooCH~
16 C2H5 ~" 154
COOCH3
17 OCH3 CH(CH3)2 ~ 137
S02N<CH3)2
18 C2H5 ~/ '- 174
COOCH3
19 C3H7 97
COOCH3
20 CH3 N(CH3)2 168
COOCH3
21 OCH2C6H5 CH3 174
C1
22 C2H5 C3H7 ~ . 136
CH3
Le A 27 154 - 61 -
CA 02302058 2000-03-29
fable 3~ - continuation
Ex. R1 R2 R9 m.p. ( ~C)
No.
COOCH3
23 N(CH3)2 C2H5 139
COOCH3
24 N(CH3)2 H 197
COOCH3
25 N(CH3)2 CH(CH3)2 ~ 148
COOCH3
26 OC2H5 C2H5 153
COOCH3
27 OC2H5 C3H7 ~ 155
COOCH3
28 CHICH3)2 186
C1
29 C3H7 ~ 146
CH3
COOCH3
30 N ( CH3 ) C3H7 ~ 1-10
2
Le A 27 154 - 62 -
CA 02302058 2000-03-29
r
Table 3: - continuation
Ex. R1 R2 ~i3 m~P~
No.
COOCH3
31 N(CH3)2
131
COOCH3
32 C2H5 C4ti~ ~~ 98
COOCH3
33 CH3 C4H9 ~ 113
COOCH3
34 C3H7 C4H9 ~/ 88
COOCH3
C4H9 / 117
COOCH3
36 OCH3 C4H9 ~ 117
COOCH3
37 CH3
141
COOCH3
38 C2H5 130
Le A 27 154 - 63 -
' CA 02302058 2000-03-29
Table 3: - continuation
Ex. R1 R2 g' m.p. ( ~C)
No.
COOCH3
39 C3H7
139
COOCH3
151
COOCH3
41 ~ CH3
/ 151
COOCH3
42 CH(CH3)Z NHCI~(CH3)2 ~ 135
COOCH3
43 N(CH3)2 N(CH3)2 ~ 171
OCF3
44 CH3 C3H? ~ 168
COOCH3
CZHS N(CH3)2 ~ 134
OCF3
46 CH3 CZHS ~ 167
~e A 27 154 - 64 -
CA 02302058 2000-03-29
Table 3: - continuation
Ex. R1 Rz R3 m.p. ( °C)
No.
ocF3
47 NH2 C3H' 120
COOCH3
4e -O NH~ 120
COOCH3
49 H
195
COOCH3
50 -CH2CH=CH2 C2H5 108
COOCH3
51 -CH2CH=CH2 H 158
OCF3
52 OCH3 C3H7 ~ 110 - 111
COOCH3
53 CH2~ H 212 - 214
COOCH3
54 C3H7 N 168 - 169
Le A 27 154 - 65 -
CA 02302058 2000-03-29
Table 3: - continuation
EX. R1 R2 R3 m~P~ ('C)
No.
OCF3
55 C3H7 ~ 103 - 105
OCF3
56 C2H5 127
OCF3
57 OCH3 C2H5 ~ 111 - 113
COOCH3
58 -OCH3 139
OCF3
59 -~~HCH3 C3H7-n ~ 196
F
6D CH3 C3H7-n ~ 178
COOCH3
61 ~ H ~ 177
Le A 27 154 - 66 -
CA 02302058 2000-03-29
Table 3: - continuation
Ex. R' R2 R3 m.p. ( C)
No.
COOCN3
62 -CH2CH(CN3) 2 C2H5 ~ 123
COOCH3
63 -CH2-CH=CH2 C3H7-n ~ (amorphous)
COOCH3
64 CH C2H5 157
-t )
2 ~
COOCH3
65 ~ C2H8 ~ 117
~
__
COOCH3
66 -C(CH3)3 C2H5 ~ 182
COOCH3
67 ~ C2H5 , ~ ~ 133
c_
COOCH3
~ ~
68 C2H5 162
COOCH3
69 -CH2-CH=CH2 CH3 ~ 120
Le A 27 154 - 6? -
CA 02302058 2000-03-29
r'
Table 3: - continuation
Ex. R1 R2 R3 m.p. ( 'C)
No.
COOC1~3
~ ~
70 C2H5 183
COOCH3
71 C2H5 H 1 196
COOCH3
72 CH3 153
OCF3
~
73 -OCH3 ~ 138
COOCH3
79 CH(CH3)2 H ~ 191
COOCH3
75 ~ H ~ 191
COOCH3
76 ~ H ~ 192
COOCH3
77 -C(CH3)3 H ~ 211
Le A 27 154 _ 6g -
CA 02302058 2000-03-29
a,
Table 3: - continuation
EX. R1 R2 R~ m.p. ('C)
No.
,,
COOCH3
78 -CH2-iH-CH2Br CH3 ' 110
Br
COOCH3
79 CH3 -CH20CH3 ~ 152
F
80 CH3 C2H5 ~ 174
COOCH3
81 CH3 -CH20C2H5 ~ 123
CF3
~
82 -OCH3 C3H7-n (amorphous)
CON(CH3)2
83 C2H5 ' ~ 124
OCF3
~ ~
84 -CH20CH3 -~ 102
COOCH3
~
85 -CH20CH3 ~ 155
Le A 27 154 - 69 -
CA 02302058 2000-03-29
r
Table 3: - cor~tinuatfon
Ex. R1 R2 R3 m.p. ('C)
No.
COOC~3
~
86 -CH20C2H5 123
OC~'3
8? -CH20C2H5 ' 99
C1
88 -N(CH3)2 ~ 189
CH3
C1
89 -OCH3 C2H5 ~ 155
CH3
C1
9D C2H5 ~ 133
CH3
C1
91 -OCH3 C3H7-n ~ 125
CH3
~
92 C2H5 ~ 138
~
~~
OOCH
S
3
Le A 27 154 - ?p _
CA 02302058 2000-03-29
r
Table 3: - continuation
Ex. R' R2 R3 m.p. ('C)
No.
OCF3
93 -OC2H5 C2H5 \ 132
OCF3
94 -OC2H5 C3H7-n \ 107
OCF3
95 -OCN3 CHtCH3)2 ~ 128
OCF3
96 OCH3 CH3 119
97 C3H7-n ~ 100
~
COOCH3
OCF3
98 \ 140
~
COOCH3
99 -N(CH3)2 ~ 163
CH3
100 -N(CH3)2 ~ 182
Le A 27 154 _ 71 _
CA 02302058 2000-03-29
Table 3: - continuation
EX. R1 R2 R~ m.p. ( C)
No.
C1
101 CH3 -N(CH3)2 1 181
CH3
COOCH3
102 CH3 -OCH3 ~ 150
C1
103 C2H5 ~ 197
CH3
C1
109 -CH2-CH=CH2 CH3 ~ 132
CH3
C1
105 -CH2-CH=CH2 C2H5 ~ 109
CH3
C1
106 -CH2-CH=CH2 C3H7-n ~ 104
CH3
Le A 27 154 - 72 -
CA 02302058 2000-03-29
Table 3: - continuation
EX. R1 RZ R3 m.p. ( C)
No.
C1
107 -OC2H5 C2H5 \ 147
CH3
C1
108 -OC2H5 C3H~-n \ 136
CH3
C1
109 -OCH3 CH(CH3)2 ~ \ 126
CH3
Cl
110 CH3 CH3 \ 146
CH3
C1
111 CH3 175
CN3
C1
112 CH3 CH(CH3)2 \ 124
CH3
Le A 27 159 _ 73 _
CA 02302058 2000-03-29
Table 3: - continuation
EX. R1 RZ Rg m.p. ( °C)
No.
C1
113 CH3 ~ 171
CH3
C1
114 CN~CN3)2 ~ 132
CH3
C1
115 167
CH3
CH3
115 CH3 CH3 ~ ~ 155
CH3
117 CH3 C2H5 ~ ~ 197
CH3
118 CH3 C3H7-n ~ 169
Le A 27 154 - 74 _
CA 02302058 2000-03-29
Table 3: - continuation
Ex. R1 RZ R3 m.p. ('C)
No.
119 OCH3 C2H5 ~
BROOCH
3
C~ COOCH3
120 CH2 -C2H5 132
r
1.e A 2? 154 - ?5 -
CA 02302058 2000-03-29
r'
~tartinq substances of the formula (I,
example (II-1)
O
HN~N~OC2H5
~2H5
to
H-i-CO-NH-OC2H~
(IX-1)
H-N-CO-C2H5
A mixture of 6B . 5 g ( 0. 60 mol ) of 5-methyl-1, 3, 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 crystalline form is isolated
by filtration with suction.
This gives 77.5 g (74 % of theor~,r) of 1-ethoxy-
aminocarbonyl-2-propionyl-hydrazine of melting point
122°C.
I,e A 27 154 - 76 -
CA 02302058 2000-03-29
m
step 2s
O
riN~N~OC2H5 ( I I -1 >
n ''r2H5
A mixture of 75.5 g (0.43 mol) of 1-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
remained undissolved is separated off by filtration with
suction. The filtrate is concentrated, the residue is
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-1,24-triazol-3-one of melting point
93°C.
Example (II-21
0
HN~N~CH3 (II-2)
-"3H7
A mixture of 40 g (0.31 mol) of 5-propyl-1,3,4-
Le A 27 154 - 77 -
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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
res idue 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-1,24-tri~zol-3-one of melting
point 86°C.
example (II-31_
O
HN~N~NtCH3)2
~H
856 g ( 4 . 0 mol ) of Biphenyl carbonate are dis-
solved in 588 g of ethylene chloride. 245 g (4.0 mol) of
dimethylhydrazine (98 % pure) are added dropwise with
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 stirred for 12 hours. It is warmed to
70-80°C and, far about 1 hour, stirring is continued.
When cold, the solution is distilled in vacuo, during
which process ethylene chloride and water are removed
(final bottom temperature 100'C). The above phenolic
Le A 27 154 - 78 _
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r
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-
s lation, phenol is distilled off in vacuo, after which
282 g of product mixture are obtained at a head temper-
ature of 85-105°C. This mixture is boiled with 600 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 9 below can also be prepared
analogously to Examples (II-1) to (II-3).
O
HN~N~R1 (II)
N~R 2
Le A 27 154 - 79 -
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. r
Table 4: Preparation example$ of the compounds of the
formula (II)
Ex. A' R2 m.p. ( C)
No.
II-4 C3H7 CH3 _ 48
II-5 CH(CH3)2 CH3 118
II-6 C~13 CH3 139
II-7 CZHS C2H5 117
II-8 ~ C3H7 C2H5 42 - 45
II-9 CHtCH3)2 C~HS 102
II-10 C2H5 C3H7 97
II-11 C3H7 C3H7 (amorphous)
I1-12 CHtCH3)2 C3H7 91
II-13 CH3 CH(CH3)2 92
II-14 C2H5 CH(CH3)2 (amorphous)
II-15 C3H7 ~ CH(CH3)2 (amorphous)
II-16 CH(CH3)2 CH(CH3)2 168
II-17 C2H5 CH3 134
II-18 CH3 159
II-19 OCH3 CH3 178
II-20 OCH3 C2H5 140
II-21 OCH3 C3H7 127
Le A 27 154 - 80 -
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t
fable 4 - continuation
hx. R' RZ m.p. ( C)
No.
II-22 OCH3 GHtCi'13I2 130
II-23 OCl~2C6HS CHI 106
II-24 C2H5 150
II-25 C3H7 130
II-26 OC2H5 C3H7 72
II-27 CN(CH3)2 121
II-28 CH3 C4H9 50
II-29 C2H5 C4Hy 76
II-30 C3H7 C4H9 (amorphous)
II-31 OCH3 CQH9 100
II-32 CqH9 66
II-33 CH3 68
II-34 C2H5 130
II-35 C3H7 68
II-36 154
Le A 27 154 _ g1 _
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~~ble 4 - continuation
Ex. R1 RZ m.p. ( C)
No.
II-37 N(CH3)2 CH3 153
II-38 N(CH3)2 C2H$ 114
II-39 N(CH3)2 C3H7 108
II-40 N(CH3)2 CH(CN3)2 100
II-41 CH3 N(CH3)2 80
II-42 N(CH3)2 134
II-43 CH(CH3)2 NHCH(CH3)2 205
II-44 N(CH3)2 N(CH3)2 93
II-45 C2H5 N(CH3)2 50
II-46 CH3 145
II-47 ~ CH3 163
II-48 H 102
II-49 OCH3 136 - 137
II-50 CH3 C6H5
II-51 NH2 H 192
II-52 NH2 CH3 230
II-53 ' CF3 163
NH2
Le A 27 154 - 82 -
CA 02302058 2000-03-29
t,
fable 4 - continuation
Ex. R' Rz m.p. ('C)
Ho.
II-54 NHCH3 CHICH3)2 105
II-55 NHCH3 ~ 95
II-56 NH2
CZHS i70
II-57 NH2 C3H7 147
II-58 NHCH3 NHCH3 137
II-59 CH2CbH5 C2H5 125
II-60 NHCH3 H 133
II-61 NHCH3 N(CH3)2 129
II-62 NHCH3 C3H7 76
II-63 NH2 1 2
~ 48
II-64 NH2 -iHC2H5 176
CH3
II-65 NH2 ~ 183
II-66 NH2 210
CF'3
II-67 NHCH3 C2H5 101
II-68 NH2 N(C2H5)2 196
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,.
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Table 4 - continuation
EX. R1 #ta m.p. ( C)
No.
II-69 NH2 ' .N- 233
II-70 NH2 CN(CH3)2 172
II-?1 NN2 C(CH3)~ 261
I I -72 NH2 CH2CH20C~i3 98
II-73 NH2 C(CH3)2C~H5 213
II-74 NH2 NHC2H5 220
II-75 NH OCH
~ 2 3 (amorphous)
II-76 TiH2 ~ CH~OCH3 134
II-77 NH2 CH20C2H5 104
II-78 N(CH3)2 CH3 153
II-79 -CH2 Cl C2H5 103
Cl
I I -80 -CH2Cti ( CH3 ) C2H5 105
2
II-81 C6H5 H 183
II-82 N(CH3)2 CH(CH3)2 (amorphous)
II-83 NHCH3 CH3 114
II-84 NH2 CH2C6H5 168
II-85 NH2 N(CH3)2 207
II-86 NH2 C6H5 230
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i
T b1 - cpntinuation
Ex. R' Rz m.p. ( C)
No.
II-87 NH2 223
II-88 NH2 NHCH(CH3)2 152
II-89 NHCH3 NHCH(CH3)2 120
II-90 ~ NH~ 254
II-91 N(CH3)2
II-92 CH2C6H5 H 111
II-93 C3H7 H 48
II-94 C6H5 C2H5 , 124
II-95 C(CH3)3 C2H5 158
II-96 CH3 #~ 157
II-97
C 108
H
2
5
C
II-98 ~ C H
2 5 132
II-99 -CH2CH=CH2 CH3 108
II-100 C6H5 CH3 150
II-101 ~ CH3 116
II-102 ~ C2H5 196
II-103 C2H5 H 68
II-104 CH(CH3)2 H 105
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' r'
Table 4 - continuation
Ex. Al Ri m.p. ('C)
No.
II-105 ~ H 7g
II-106 ~ H 162
II-107 C(CH3)3 H 194
II-108 -CH2-iH-CH28r CH3 111
6 c-
II-109 CH3 -CH20CH3 104
II-110 CH3 -CH20C2H5 102
II-111 --Q -CH20CH3 102
I I -1 ---a -CH20C2H5 1 19
12
II-113 --~ -N(CH3)2 130
~CH3
II-114 NH2 -N 186
'C2H5
~H3
II-115 NH2 -N 165
~C3H7-n
2H5
I I -116NH2 -N~ 186
C3H7_n
II-117 NH2 -NCO 267
II-118 CH3 -OCH3 144
Le A 27 154 _ g6 _
CA 02302058 2000-03-29
The compound of Example (II-118) disclosed in Table 4
(above) can be prepared as follows;
O
HN~N~CH3 (II-118)
~CH3
50.2 g (0.33 mol) of hydrazino-formic acid phenyl ester
(= 1-phenoxycarbonyl-hydrazine) and 36.6 g (0.33 mol;
90 % purity) of O,O,N-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 (methanol, 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 x 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 - 8? -
i
CA 02302058 2000-03-29
a
Examples of hydrazine
derivatives of the
formula (IX) which can be obtained analogously to Ex-
ample (II-1), isted in Table 5 below,
step 1, are
l
H-N-CO-NH-R1
( IX)
H-N-CO-R2
fable 5: Examples #hydrazinederivatives of the
of the
fonaula ( IX)
EX. R1 Ra m.p. ( C)
No.
IX-2 OCH3 C2H5 120
IX-3 OCH3 C3H? 125
IX-4 OCH3 CH(CH3)2 127
IX-5 OCH2C6H5 CH3 100
IX-6 C2H5 174
IX-7 C~H~ 180
IX-8 OCZHS C3H~ 119
IX-9 CH(CH3)2 150
IX-10 OCH3 C4H9 134
IX-11 C4H9 159
Le A 27 154 - 8B -
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r.
Table - continuation '
Ex. Rl RZ m.p. ('C)
No.
IX-12 ' 188
IX-13 OCH3 140
IX-14 CH2-CH=CH2 C3H7 134
IX-15 -CHZOC2H5 97
Le A 27 154 _ 89
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' . r,
~ta__rti~~ substances of the formula ~IV~s
Example ( IV-11
O
-CO~N~N~CHg
~2H5
6.4 g (0.05 mol) of 5-ethyl-4-methyl-2,4-dihydro-
3H-1,2,4-triazol-3-one are dissolved in 80 ml of tetra-
s hydrofuran, and 1.B g (0.06 mol) of sodium hydride (80 %
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 etherr 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 (IV)
listed in Table 6 below can also be prepared analogously
to Example (IV-1).
Le A 27 154 _ g0 -
CA 02302058 2000-03-29 '.
.. , s
O
Z-CO~N~iRl (IV)
2
R
Table 6: Examples of the compounds of the formula (IV)
EX. R1 R2 Z m.p. ('C)
No.
IV-2 C3H~ C3H? . C6H5 88
IV-3 OCH3 C3H~ C6H5 82
IV-4 CH3 C3H~ C6H5 84
IV-5 NH2 C3H~ C6H5 133
IY-6 NH2 CH3 C6H5 82
IV-7 , C2H5 C6H5 152
IV-8 OC2H5 C2H5 C6H5
IV-9 OCH2CH=CH2 CH3 C6H5
IY-10 CQH9 C6H5
IV-li CH3 C6H5
IV-12 NHCH3 C2H5 CbHs
Le A 27 154 _ g1 _
CA 02302058 2000-03-29
c
Table - continuation
Ex. RI R2 2 m.p. (~C~
No.
IY-13 CH3 CH2C6H5 CbHs
I V-14 CH3 NHCH ( Cl~l3 C6H5
) 2
IY-15 N(CH~)2 N(CH3)~ C6H5
IV-16 C6H~
IV-17 OC2H~ C6H5
IV-18 OC3H7 C2H5 CbHS
IY-19 C2H5 C4H9 C6H5
IV-20 CH(CH3)2 CHtCH3)2 C6H5
IV-21 OCH3 C2H5 C6H5 89
IV-22 C3H7-n C6H8 104
Le A 27 154 _ 92 _
CA 02302058 2000-03-29
Use Examples:
In the following use examples, the known herbicide
isocarbamide, of formula (A) below, is used as comparison
substance:
HN~~N-CO-NH-CHZCH(CH3~ ( A )
O
The formulae of the compounds used in the Use
Examples are listed individually below in conjunction with
the number of the Preparation Examples=
~~~ 2
_ O
/ SOZ NH-CO~N~N~CH3 ( 4 )
1
N--~
'C Hs
2
OCHF2
_ O
SOZ NH-CO~N~N~C2H3 ( 3 )
N--~
~C H
2 s
2
O
SOZ NH CO~N~N'CH3 ( 6 )
I
N--~
~C i
3F ~
C1
0
SO2 NH CO~N~N~CH3 ( z )
I
CH 3 N--~
~C H
2 s
- 93 -
23189-7150D
CA 02302058 2000-03-29
Cl O
~
N~C2H5 (7)
502-NH-CO'N
~C
H
2
CH3 i
Cl O
' t8)
~
~
CH3
N
S02-NH-CO
N
~
H
CH3
3
7
COOCH3 O
~
N~OCH3 t12)
~S02-NH-CO'N
-'C
H
N
2
5
COOCH3 O
~
NiOCH3 t13)
S02-NH-CO'N
H
~3
7
S02N(CH3)2 O
~
N~CH3 t14)
S02-NH-CO'N
~
H
5
2
S02N(CH3)2 O
~
N~'CH3 t 15
S02-NH-CO'N )
~C
H
3
~
COOCH3 O
S0 t16)
-NH-CO'N~
,
2
H
~
5
2
COOCH3
S02-NH-CO'N N~OCH3 (17)
~
HtCH3)2
..-
Le A 27 154 - 94 -
CA 02302058 2000-03-29
S02N(CH3)2 O
(s ,t-S02-NH-CO~N~N~ (18)
-"2H5
COOCH3 O
S02-NH-CO~N~ (19)
N'~C 3 H 7
COOCH3 O
("j-S02-NH-CO~N~N~CH3 (20)
~N(CH3)2
COOCN3 O
(A ,j--S02-NH-CO~N~N~OC2H5 ( 26
" -"2H5
COOCH3 O
~S02-NH-CO~N~N~OC2H5 (27)
-"3H7
COOCH3 O
("J--S02-NH-CO~N~N~ ( 28
~H(CH3)2
C1 O
S02-NH-CO~N~ (29)
CH3 ~3H7
COOCH3 O
("j-S02-NH-CO~N~N~'N I CH3 ) 2 ( 30 )
~3H7
r
Le A 7 154 - 95 -
CA 02302058 2000-03-29
COOCH3 O
,)-S0
-NH-CO~N~N~C
H
(32)
2 2
5
~
4H9
COOCH3 0
S0 CO~N~N~CH
-NH- (33)
2 3
H
4
9
COOCH3 O
502-NH- CO~N~N~C
H
(34)
3
'
~
4H9
COOCH3 O
~S0 CO~
-NH- ~
~
2 N
N
(35)
~
H
4
COOCH3 O
S02-NH- CO~N~N~CH
(37)
3
COOCH3 O
502-NH-CO~N~N~C3H7 (39)
N
COOCH3 O
("r-S02-NH-CO~N~ (40)
Le A 27 154 - 96 -
CA 02302058 2000-03-29
COOCH3 0
~SOZ-NH-CO~N~N~OCH~ (9)
~CH 3 .
COOCH3
4 ,?-S02-NH-CO~N N~N(CH3)2 (31)
~J
COOCH3 O
502-NH-CO~N~N~OCH3 (36)
~4N9
Le A 27 154 - 9~ -
CA 02302058 2000-03-29
Example A
Pre-emergence test
Solvent: 5 parts by weight of acetone
Emulsifier; 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 of
active compound. It is expedient here to keep constant
the amount of water per unit area. The 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, 12, 13, 16,
17, 18, 19, 20, 26, 27, 28, 29, 34, 37, 39 and 40.
Le A 27 154 - 9g -
CA 02302058 2000-03-29
, . ~
~Xample B
Post-emergence test
Solvent: 5 parts by weight of acetone
Emulsifier: 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.
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 1000 1 of water/ha. 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, 4, 5, 6, 7, 8, 12,
13, 14, 15, 16, 17, 18, 19, 20, 26, 27, 28, 29, 30, 32,
33, 34, 35, 37, 39 and 4p.
Le A 27 154 - 99 -
CA 02302058 2000-03-29
,.
Example
Pyricularia test (rice) / protective
Solvent: 12,5 parts by weight of acetone
Emulsifier: 0, 3 parts by weight of alkylarylpolyglycol ether
To produce a suitable preparation of active compound,
1 part by weight of active compound is mixed with the
stated amount of solvent, and~the concentrate is diluted
with water and the stated amount of emulsifier to the
desired concentration.
To test for protective activity, young rice plants are
sprayed with the preparation of active compound until
dripping wet. After the spray coating has dried off, the
plants are inoculated with an aqueous spore suspension of
Pyricularia, orycae. The plants are then placed in
a greenhouse at 100 $ 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 shown, for
example, by the compounds according to the following
preparation examples:
9, 12, 13, 20, 30, 31, 32, 33, 34, 35, 36, 37.
~e A 27 154 - 100 -
CA 02302058 2000-03-29
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 90
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 27 154 - 101 -
