Note: Descriptions are shown in the official language in which they were submitted.
CA 02420329 2003-03-13
30517-181F
Substituted 1,2,3-Triazol-3-ones.
The present divisional application is divided out
of parent application Serial No. 2,189,698, which was itself
divided out 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 divisional application Serial No.
2,189,698 relates to novel intermediates of formula IIa and
processes for preparing the intermediates. Compounds of the
formula IIa are useful in the preparation of compounds of
formula I.
The invention of the present divisional
application relates to novel intermediates of formula IIa
which are structurally different than those of application
Serial No. 2,189,698. The intermediates of the present
divisional application are useful in the preparation of
compounds of formula I, illustrated below.
It is known that certain substituted amino-
carbonylimadazolinones, such as, for example, 1-isobutyl-
aminocarbonyl-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
- 1 -
CA 02420329 2003-03-13
30517-181F
are a subgroup of the broad class of compounds of the
a general formula (T)
0
1
R SOZ NH CO N N --- R
N----
Rz
in which R'' represents hydrogen, hydroxyl or amino, or
represents an
- la -
CA 02420329 2003-03-13
opt ionally subst ituted radical f rom 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-R~
N (ll)
R2
in which
R1 and R2 have the abovementioned meanings, are reacted
with sulphonyl isocyanates of the general formula (III)
R3 802-N C-~ (III)
in which
2Q R3 has the abovementioned meanings, if appropriate in
the presence of a diluent, or when
b) triazolinone derivatives of the general formula (IV)
CA 02420329 2003-03-13
0
Z-CO-N~N-R1 (IV)
~R2
in which
R' and R2 have the abovementioned meanings and
Z represents halogen, alkoxy, aralkoxy or aryloxy,
axe reacted with sulphonamides of the general
formula (V)
R3'S~2'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) triazoli.t~ones of the general formala (II)
O
1-iN~N-R1 ( I I )
~~-----1~ 2
R
in which
R1 and RZ have the abovementianed meanings
- 3 -
CA 02420329 2003-03-13
are reacted with sulphonamide derivatives of the general
_ formula (VI)
R3-S02-NH-CO-Z (~z)
i. n wh 1 ch
R3 has the abovementioned meaning and
Z represents halogen, alkoxy, aralkoxy or aryloxy, if
appropriate in the presence of an acid acceptor and if
appropriate in the presence of a diluent, and, if
appropriate, salts are formed by customary methods from
ZO the compounds of the formula (T) prepared by process
(a), (b) or (c).
The new sulphonylaminocarbonyl-tria2olinones 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 1-isobutyl-
aminocarbonyl-2-imidazolidinone (isocarbamide), which has a
similar structure.
The new compounds of the present' parent application
20 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, Cl-Cg-alkoxy, Cl-C4-
alkylcarbonyl or C1-C4-alkoxy-carbonyl, or represents
C3-C6-alkenyl or C3-C6-alkinyl, each of which is
- 4 -
CA 02420329 2003-03-13 ,
optionally substituted by fluorine, chlorine and/or
bromine, or represents C3-C6-cyGloalkyl which~is
opt ional 1y subst ituted: by f luori.ne,
- 4a -
CA 02420329 2003-03-13
d chlorine, bromine and or.Cr-C4-alkyl, or represents
phenyl-C1-C3-alkyl which ~is optionally substituted by
fluorine, chlorine, bromine, cyano, vitro, C~-C4-
alkyl, trifluoromethyl, Cr-C~-alkoxy and/or Lr-C4-
alkoxy-carbonyl, or represents phenyl which is
optionally substituted by fluorine, chlorine,
bromine, cyano, vitro, C1-C4-alkyl, trifluoromethyl,
C1-C~-alkoxy, fluorine- and/or chlorine-substituted
Ci-C3-alkoxy, Cl-C,,-alkylthi~, fluorine- and/or
chlorine-substituted C1-C3-alkyltluio, C~-C,,-alkylsul-
phinyl, C,-C~-alkylsulphonyl and/or C,-C4-alkoxy-
carbonyl, or represents Cr-C6-alkoxy which is option-
ally substituted by fluorine, chlorine, cyano,
phenyl, C1-C4-alkoxy or C1-C4-alkoxy-carbonyl., or
represents C3-C4-alkenyloxy, or represents Cl-C4-
alkylamino which is optionally substituted by
fluorine, cyano, C1-C4-alkoxy or Cr-C4-alkoxy-car-
bonyl, or represents di-(C,-Cy-alkyl)-amino,
R2 represents hydrogen, hydroxyl, mercapto or amino, or
represents Cr-C6-alkyl which is optionally substitut
ed by fluorine, chlorine, brornine, cyano, C3-C6
cycloalkyl, C,-C,,-alkoxy or C1-C,,-alkoxy-carbonyl., or
represents C3-C6-cycloal.kyl which is optionally
substituted by fluorine, chlorine, bromine and/or.
Cl-C~-alkyl, or represents cyclohexenyl, or repre-
sents phenyl-Cr-C3-alkyl which is optionally substi-
tuted by fluorine, chlorine, bromine, cyano, vitro,
Cr-C,,-alkyl, trifluoromethyl, Cr-C4-alkoxy and/or
Cl-Cy-alkoxy-carbonyls or represents phenyl which is~
34 optionally substituted by fluorine, chlorine,
- 5 -
CA 02420329 2003-03-13
bromine, cyano, vitro, Cl-Cy-alkyl, trifluoromethyl.
Cl-C~-alkoxy, fluorine- and/or chiora.ne~-sunst~.tured
C1-C3-alkoxy, Cl-C4-alkylthio, f luorine- and/or
chlorine-substituted C1-C3-alkylthio, Cl-C;-alkyl-
sulphinyl, C1-C~-alkylsulphonyl and/or C1-c:5-alkoxy
carbonyl, or represents C1-C6-alkoxy which is option
. ally substituted by fluorine, chlorine, cyano, C,-C,,
alkoxy or C1-C4-alkoxy-carbonyl, or represents C1-C4-
alkylamino or di-(C1-C~-alkyl)-amino, and
R3 represents the group R5 , where
R4
R° and RS are identical or different and represent ,
hydrogen, fluorine, chlorine, bromine, iodine,
vitro, CI-C6-alkyl.(which is optionally substituted
by fluorine, chlorine, bromine, cyano, carboxyl,
C~-C'-alkoxycarbonyl, Cl-C~-alkylamino-carbonyl, .di-
(C~-C,,-alkyl)amino-carbonyl, hydroxyl, Ci-C,-alkoxy,
formyloxy, C1-C,,-alkyl-carbonyloxy, Cl-C,,-alkoxy-
carbonyloxy, C1-C,-alkylamino-carbonyloxy, Cl-C4-
alkylthio, C~-C,~-alkylsulphinyl, C~-C~-alkylsulphonyl,
di-(C1-C4-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 C2-C6-alkinyl (which is optionally s'ubsti-.
tuted by fluorine, chlorine, bromine, cyano, Cl-C4-
alkoxy-carbonyl, carboxyl or phenyl), or represent
- s --
CA 02420329 2003-03-13
" C1-C4-alkoxy (which is optionally substituted by
fluorine, chlorine, bromine, cyano, carboxyl, C1-Cy-
alkoxy-carbonyl, C1-C4-alkoxy, C1-C~-alkylthio, C1-C~-
alkylsulphinyl or C1-C4-alkylsulphonyl ) , or represent
C1-C4-alkylthio (which is optionally substituted by
fluorine, chlorine, bromine, cyano, carboxyl, C1-C,,-
alkoxy-carbonyl, C1-C4-alkylthio, Ci-C4-alkyl.sulphinyl
or C1-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, bromine, cyano,
vitro, C1-C3-alkylthio or Cl-C4-al.koxycarbonyl ) ,
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 C1-C4-alkyl (which is optionally
substituted by fluorine, chlorine, bromine, cyano
or Cl-C4-alkoxy-carbonyl ) , C3-C6-alkenyl ~ C3-C6-
alkinyl, Ci-C4-alkoxy, Cl--C~-alkoxy-C1-C4-alkyl-
amino, C1-C4-alkylamino, di- ( C,-C4-alkyl ) -amino or
phenyl, or represents the radical -NHOR' where
R'_ represents C1-C12-alkyl (which is optionally
substituted by fluorine, chlorine, cyano,
C,-C$-alkoxy, C1-C4-alkylthio, C1-C4-alkylsul
phinyl, l C,-C4-alkylsulphonyl, Cl-C4-alkyl
carbonyl, C1-Cy-alkoxycarbonyl, C1-C,-alkyl
amino-carbonyl or di-(C1-C4-alkyl)-amino
carbonyl), or represents C3-G6-alkenyl (which
is optionally substituted by fluorine,
_ 7 _
CA 02420329 2003-03-13
_ chlorine or bromine) , C3-C6-alkinyl, C~-C6-
cyclaalkyl, C3-C6-cycloalkyl-C1-C2-alkyl,
phenyl-C1-C2-alkyl (which is optionally substi-
tuted by fluorine, chlorine, nitro, cyano,
Cl-C4-alkyl, C1-C4-alkoxy ar C1-C,-alkoxy-car-
bonyl), or represents benzohydryl, or repre-
sents phenyl (which is optionally substituted
by f luorine, chlorine, nitro, cyano, C1-C,,--
alkyl-, trifluoromethyl, C~-C,,-alkaxy, C~-C2-
fluoroalkoxy, C1-C4-alkyl.thio, trifluoromethyl-
thio or C,-C~-alkoxycarbonyl ) ,
R° and/or Rs furthermore represent phenyl or phenoxy,
or represent C1-C~-alkylcarbonylamino, C~-C4-
alkoxycarbonylamino, C1-C4~-alkylamino-carbonyl-
amino, di-(C1-C4-alkyl)amino-carbonylamino, or
represent the radical -CO-R8, where
RB represents C1-C6-alkyl, C1-C6-alkoxy, C3-C6-
cycloalkoxy, C3-C6-alkenyloxy, C1-C4 alkylthio,
C1-C4-alkylamino, C1-Cy-alkoxyamino, C1-C4-
alkoxy-C~-C4-alkyl-amino or di- ( C1-C4-alkyl ) -
amino ( each of which is optionally substituted
by fluorine and/or chlorine),
R' and/or Rs furthermore represent tr.i.methylsilyl,
thiazolinyl, C1-C,-alkylsulphonylox.y, di-(C1-C~
alkyl)-aminosulphonylamino, or represent the
radical -CH=N-R9, where
Rs represents Cl-C~-alkyl which is optionally
substituted by fluorine, chlorine, .cyano,
. carboxyl, Ci-C~-alkoxy, C1-C4-alkylthio, C1-C~
alkylsulpl~inyl or C1-(:4-alkyl sulphonyl, or
- 8 -
CA 02420329 2003-03-13
represents benzyl which is optionally substi-
- tuted by fluorine or chlorine, or represents
C3-CB-alkenyl or C3-C6-alkinyl, each of which is
optionally substituted by fluorine or chlor
ine, or represents phenyl which is optionally
substituted by fluorine, chlorine, bromine,
C1-C4-alkyl, Cl-C~-alkoxy, trifluoromethyl,
trifluoromethoxy or trifluoromethylthio, or
represents C~-C6-alkoxy, C3-C6-alkenoxy, C3-C6-
alkinoxy or benzyloxy, each of which is
optionally substituted by fluorine and/or
chlorine, or represents amino, Cl-C~-alkyl-
amino, di-{Cl-C4-alkyl)-amino, phenylamino,
C1-C4-alkyl-carbonyl-amino, C1-C,-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 -iH , where
R10 R11
Rl° represents hydrogen or Ci-C~-alkyl,
R'1 and R12 are identical or different and represent
hydrogen, fluorine, chlorine, bromine, vitro,
cyano, C~-C,-alkyl (which is optionally substitut-
ed by fluorine and/or chlorine), C~-C~-alkoxy
(which is optionally substituted by fluorine
and/or chlorine), carboxyl,'Cl-C,-alkoxy-carbonyl,
f
- ~ r
CA 02420329 2003-03-13
dimethylaminocarbonyl, C1-C~-alkylsulphonyl or di-
(C1-C,-alkyl)-aminosulphonyl;
furthermore
14
R3 represents the radical R13 ~ R , where
R'3 and R'~ 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~-~,,-alxoxy
(which is optionally substituted by fluorine
and/or chlorine);
furthermore
R15
R' represents the radical ~ ~ , where
. . ~N
ftib
R'S and R'6 are identical or different and represent
hydrogen, fluorine, chlorine, bromine, nitro,
cyano, C~-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,-C4-alky l.thio,
C1-Cy-alkylsulphinyl or C1-C4-alkylsulphonyl (each
of which is optionally substituted by fluorine
and/or chlorine), or represent di-(Cl-C~-alkyl)-
aminosulphonyl or C1-C~-alkoxy-carbonyl or di-
methylaminocarbonyl;
- to -
CA 02420329 2003-03-13
furthermore
R3 represents the radical R1~ ~ ~ ~ Rla , where
~J
R" and RlB are identical or different and represent
hydrogen, fluorine, chlorine, bromine, C~-C,-alkyl
(which is optionally substituted by fluorine and/or
bromine), Cg-C~-alkoxy (which is optionally substi-
tuted by fluorine and/or chlorine), or represent
C1-C~-alkylthio, Cl-C4-alkylsulphinyl or C1-C,-alkyl-
sulphonyl (each of which is optionally substituted
by fluorine and/or chlorine) ~ or represent di-(C1-C4-
alkyl)-aminosulphonyl;
furthermore
R19
R3 represents the radical , where
~' ~R20
Rte and RZ°.are identical or different and represent
hydrogen, fluorine, chlorine, bromine, cyano,
vitro, C1-C~-alkyl (which is optionally substitut-
ed by fluorine and/or chlorine), C1-C,-alkoxy
(which is optionally substituted by fluorine
and/or chlorine) , C~-C4-alkylthio, C1-C~-ahkylsul-
phinyl or Cl-C4-alkylsulphonyl (which is optional-
ly substituted by fluorine. and/or chlorine), di-
(C1-C4-alkyl)-amino-sulphonyl, C:l-C4-alkoxy-car-
bonyl or di.methylaminocarbonyl, and.
A represents oxygen, sulphur or the group N-Z',
_ 11
CA 02420329 2003-03-13
where
- Z' represents hydrogen, Cl-C4-alkyl (which is
optionally substituted by fluorine, chlorine,
bromine or cyano), C3-C6-cycloalkyl, benzyl,
phenyl (which is optionally substituted by
f luorine, chlorine, bromine or vitro ) , C1-C4-
alkylcarbonyl, C1-C,-alkoxy-carbonyl or di-
(C,-C~-alkyl)-aminocarbonyl;
furthermore
R21
R3 represents the radical .~~R22 r where
1 ,
R21 and R22 are identical or different and represent
hydrogen, C1-Cy-alkyl, halogen, Ci-Ca-alkoxy-
carbonyl, Ci-C~-alkoxy or C1-C4-halogenoalkoxy,
Y1 represents sulphur or the group N-R23, where
Rz3 represents hydrogen or C1-Cu-alkyl g
furthermore
R26
R3 represents the radical ( , where
tJ~N
R25
~24
R
R24 represents hydrogen, C,-C~-alkyl, benzyl,
quinolinyl or phenyl,
RZS represents hydrogen, halogen, cyano, vitro,
C1-C~-alkyl (which is optionally substituted by
- 12 -
CA 02420329 2003-03-13
fluorine and/or chlorine); Cl-C4-alkoxy (which is
optionally substituted by fluorine and/or
chlorine), dioxolanyl or Cl-C4-alkoxy-carbonyl, and
Rz6 represents hydrogen, halogen or C1-C4-alky l
furthermore
R3 represents one of the groups listed below,
H3C0 / H3C
\ ~ ~ N'_Ca~9 ' N ~
~S S ~'OCHZCP3
O2
'~ 1
\ o
0
The invention furthermore preferably relates to the
sodium, potassium, magnesium, calcium, ammonium, C1-C4-
alkylammonium, di-(Cl-C~-alkyl)-ammonium, tri-(Cl-C4-alkyl)-
ammonium, C5- or C~-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 C1-C~-alkyl which is
optionally substituted by fluorine, chlorine, bromine,
cyano, methoxy or ethoxy, or represents allyl, or
represents C3-C6-cycloalkyl, or repre-
- 13 -
CA 02420329 2003-03-13
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 Ci-C"-alkyl which
is optionally substituted by fluorine and/or chlor
ine or by methoxy or ethoxy, or represents C3
cycloalkyl, or represents phenyl, or represents
C1-C3-alkoxy, or represents C1-C3-alkylamino, or
represents di-(C1-C2-alkyl)-amino, and
R3 represents the group , R~ , where
R4
R4 represents fluorine, chlorine, bromine,, methyl,
trifluoromethyl, methoxy, difluoromethoxy,
trifluoromethoxy, 2-chloro-ethoxy, 2-methoxy-
ethoxy, C1-C3-alkylthio, C~-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
R11
R12
R9 represents the radical _~1~~ , where
R10
R'° represents hydrogen,
- 14 -
CA 02420329 2003-03-13
' , R11 represents fluorine, chlorine, bromine, methyl,
methoxy, difluoromethoxy, trifluoromethoxy, ethoxy,
methoxycarbonyl, ethoxycarbonyl, methylsulphonyl or
dimethylaminosulphonyl, and
R~'2 represents hydrogen,
furthermore
R~ represents the radical
~J
RO-C S '
IJ
O
where R represents Cl-C4-alkyl, or
represents the radical
O
I I
RO-C
I ,IN
N
1
~3
where R represents C1-C4-alkyl.
Examples of the compounds are listed in Table 1
below -- cf. also the Preparation Examples.
- 15 -
CA 02420329 2003-03-13
R3-S02-N!-~-CO-H~N-~i
(I)
R
Table 1: Examples of the compounds of the formula (I)
R1 R2 ~3
F
H
C1
H
OCF3
CH2-CH=CHI C2HS
OCHF2
OCH3 C3H7 ~H2_
O-CH2-CH=CH2 S COOCH3
COOC2H5
C2H5 C9H9_n
- is -
CA 02420329 2003-03-13
Table 1 - cont~.nuation
R1 R2 R3
S02NHOCH3
CH3 C3H?
S02N(CH3)2
C3H~
C1
GH3 CzHS C 1_~
~/
Br
C2H5 C3H7
CHI
COOCH2-CH2-C1
OC2H5
~~COOCH3
OC3H~ CH3 'NI~N~
CH3
CH3 C3H7 S~COO.CH3
COOCH3
N(CH3)2 CHZ ~H2_
- 17 -
CA 02420329 2003-03-13
- Table 1 - continuation
R1 R2 R3
COOCH3
NH-CH3 ~H
COOCZHS
CH3 C3Hy r/
F~CHO
OCF3
OCH3
OCHF2
OCZHS
F
CH~~ CH2~ /
OCF3
CHZ C3H' ~/
~ .N~
C3H~ ~N
COOCH~
CH~O
CH3 C2H5 ~ SAN-C4H9
02
- 18 -
CA 02420329 2003-03-13
Table 1 - continuation
R1 R2 R3
,~ CONtCH312
CH3 CqH9
CON(CHal2
C3H7
CH3 C3H~ i
C2H5 C2H5
C3H~ /~
SO2
OCH2-CH2-C1
C2H5 C2H5
OCH3
CH3 C3H~-n
OC2H5
C3H7-n
- 19 -
CA 02420329 2003-03-13
Tabs _ continuation
R1 R2 R3
CF'3
CH3
OCH3
CH3 C4H~ HZ'
C1
CH3 ~ v
H2_
Cl
C2H5 / H2,
C1
CFA
C3H7 C3H7 H
2
CN
CH3 CH(CH3)2 H
~~~COOCZHS
CH3 I
N,
~. ~
- 20 -
CA 02420329 2003-03-13
Table 1~- continuation
R1 R2 R3
~COOC2H5
N N
OCH3 CaHS ~N
i
COOCH(CH3)2
OGZHS C2H5 /
ca
CH3 CH3 ..' ! CF3
r
CH3 C2H5 N
CH3
N3COOC
~N--C H 3
C 1.
CON(CH372
CH3 CH3 H3C' N
OCF3
CH3 CH(CH3)2 H2
- 21 -
CA 02420329 2003-03-13
Table 1 - continuation
R1 R2 ~3
Br
OCH2-C~-i=CH2 C2H5 CH3
~CH3
S02-N.,
OCH3
OCH3 C2Hg /
Br
CH3 CH(CH3~2
SCH3
CH3 CHZ-CH=C~2
SO~CH3
CH3 CH2-O-CH3
SCH(CH3)2
CH3 CH2-O-C2H5
F
C2H5 C2H4-O-CH3
F
.~~ CON(CH3)2
CH2-CH=CH2 H
- 22 -
CA 02420329 2003-03-13
s
Table 1 - continuation
Ri R2 H3
OCHFZ
CH2-GH=CN2 CH3
r
CH2-CH=CHZ G~HS ~N'N
CH3
C2Hg S OOCH3
COOC2H5
CH3 C3H'
CH3
NH-CH3 CZHS /
C1
COOCH3
NH-GH3
~~__~ H 2 _
Si(CH3)3
CH3 C3H7
i I CON(CH3)~
C2~i5 C~
- 23 -
CA 02420329 2003-03-13
Table 1 - continuation
f~ 1 R2 N3
CON<CH3)2
C2H$ C4H9 S
CH3
CH3 C3H? , NHS CH2-CF3
'O
C 2H 5 NwN/'r.
GH3
CH3 S
CH3
C2H5
CH3
OCH3 CH(CH3)2 / H2~
C2H5
OC2H5 C2HS /
. i CF'3
CHI H
- 29 -
CA 02420329 2003-03-13
Table 1 - continuation
Ri R2 ~3
CHZ-CH2-O-CH3
CHI C2H5
O-SOZCH3
CHI, C3H~ f
OCH3 C3H? \ 1) O .
O
SOZCH~
OCH3 H
CH3
CH3 CZHS /
Bc
OCHF'2
CHZ-CH~GH2 CH2-O-CH3
- 25 -
CA 02420329 2003-03-13
Table 1 - continuation
Rt R2 R3
OCH2CH~-C1
N(CH 3~. N(CH 3~
If, for example, 2-6-difluoraphenyl 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:
O
H.N~N~OGH3
_. N=C~O + !
N
P
SOZ NH-CO~ ~ ~OCH3
N N
N
~C 1H
2s
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 -
CA 02420329 2003-03-13
SCH3 ~
r Cl-CO~N~N~N(CH3)2 _
\ , S02-NHZ + N -HCl
H
SCHg
O
\~/ SOZ-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 ()
+ H.N~N..CHFa
\ ~ SOz~~ ~~~ ~ I
N(C~,Hs~
OCH3
O
-H c \ / ~°2~~ co,N~..,N'CHF2
3 I
N rt(C2H~)a .
'Formula (II) provides a general definition of the triazo-
linones to be used as starting substances in processes (a)
and (c) for the preparation of compounds of the formula (I).
In formula (II), R1 and R2 preferably, or in
particular, have those meanings which have already been
- 27
CA 02420329 2003-03-13
mentioned above in connection with the description of the
- compounds of the formula (I) as being preferred, or
f part icularly preferred, far R1 and Rz .
Examples of the starting substances of the formula
(II) are listed in Table 2 below.
O
~~~~R1
N (II)
R2
Table 2: Examples of the starting substances of the formula
(II)
R1 R2
H H
CH3 H
C2H5 H
C3H~ H
- 2H -
CA 02420329 2003-03-13
Table 2 - continuation
R 1 H2
CH(CH3)2 ~
CqH9 ' H
CH2CH(CH~)2 H
C(CH3)3
H CH3
H C~HS
H CgH~
H cHccNs)2
H C~H9
H CH~CH(CH3)2
H CICH3)3
CHF'2 H
CH2CH2CN H
CH2CHZOCH3 H
H CF3
H ' CH20CH3
H CH20CZH~
H CH2CHZOCH3
CHI CH3
- 29 -
CA 02420329 2003-03-13
Table 2 - continuation
R1 R2
CHa GZHS
CH3 C~H~
CH3 CHtCH3)2
CH3 C~~9
CH3 CH2C~i t CH3 ) 2
CH3 C(C~~~3
CZHS C~3 ,
C3H7 CH3.
CH(CH3)2 C~3
C4H9 CH3
CH2CHtCH3)2 CH3
CZHS C2H5
C3H7 C3H~
CHF2 C3H7
CHFZ CH3
CHF2 CZHS
CH3 CF3
C2H5 CR3
CFZCHFZ CH
3
C2H5 C3H7
- 30
CA 02420329 2003-03-13
,, v . . ..:,,i
i
Table 2 , continuation
H1 H2
C2H5 C'~Hg
C6H5 t:H3
/t:H 2
_C~CH CH3
2
/CH2
cH3 ~ ~G~cH
2
CHI
GH3 NtCH~)~
C2H~ N(CH~)
~,
CzHS
C3H~
OCH3
C2H5
C~H~
_ 31 -
CA 02420329 2003-03-13
<~ Table 2 - continuation .
R1 R2
CH3
~2H5
C3H~
C3HT
CH3
CH3
NH2 CH3
CH3 NHCH~
NHCH~ CH3
NHCH3 C2H5
NHCH~ C~H'
N(CH3)2 CHI
N(CH3)2 C2H5
N(CH3)2 C3H7
- 32 -
CA 02420329 2003-03-13
a , Table 2 continua~tiox~
.. R~ ~~
OCN3 C~l~
OCH3 C~H~
OCZHS CHI
~C2H5 G2H~
..:.~
CH2'O-C~1-i5
N(CH~>~,
O-C3H7 C3H?
O-CH2-CH=CH2 CH~-
O-CHZ-CH=CH2 C~HS
O-CH~-CH=CH2 C3H7
O-CHI-~H-CH2-Br C~H7 ;
Hr
OCH3
- 33 -
CA 02420329 2003-03-13
Table 2 - continuation
OC H.3
OCH
3
OCH3
OCH3 CHx
OCH3 NtCN3)2
O-CH2-COOCH3 C3H~
NtCH3)2
NtCH~)2
NtCH3)2
OC2HS Cgkl7
OC 2H 5
- 34 -
CA 02420329 2003-03-13
Table 2 - continuation
.. R1
NH-CH3 . C~2-p-CHI
.__L.~ CN2_O_CH3
CH3 Ctl2-p-CH3
- ~5 -
CA 02420329 2003-03-13
', The starting substances of the formula (II) are known
w and/or can be prepared by processes known per se (cf.
Chem. Ber. 90 (1957) 909-921 loc.cit. 98 (1965), 3025
3099; J. Heterocycl. Chem. 15 (1978), 237-240; Tetra
hedron 32 (1976), 237-2352; Hely. Chim. Acta 63 (1980),
841-859; J. Chem. Soc. C 196?, 746-751; EP-A 283,876;
EP-A 294,666; EP-A 301946; EP-A 298,371;
DE-P 3,839,206/LeA 26,538 dated 19.11.1988;
DE-P 3,916,20?/LeA 26,849 dated 18.05.1989;
DE-P 3,916,208/LeA 26,850 dated 18.05.1989;.7. Chem. Soc.
C 1970, 26-34; DE-P 3,916,930/LeA 26,886 dated
24.05.1989).
For example, the triazoli.nones of the
formula (II) are obtained when
«) oxadiazolinones of the general formula (V)T)
~N~ t Y I I )
N~R2
in which
R2 has the abovementioned meaning
are reacted with amino compounds of the general
formula (VIII)
HZN-Ri (VIII)
in which
R' has the abovementioned meaning,
- 36 -
CA 02420329 2003-03-13
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 by this process, q~ t~~ general formula (IX)
H~ ~.CO-N~-R~
H
(IX)
.-Nw
H CO-R2
in which
Rl and R2 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) 3,743,493/LeA 25,759 and the
Preparation Examples ),
or when
p) amino compounds of the general formula (VIII)
H2N'RI (YIII)
- - 37 -
CA 02420329 2003-03-13
30517-181F
in which
Rl has the abovementioned meaning, are reacted with
carbonic acid derivatives, such as, for example, Biphenyl
carbonate, then with hydrazine or hydrazine hydrate and
eventually with a carboxylic acid derivative or carbonic
acid derivative of the general formula (X)
~ Rp~ 30
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
divisional application Serial No. 2,189,698, there is
provided a triazolinone of the general formula (IIa)
0
A1
HN N~ (IIa)
N
A
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 -
CA 02420329 2003-03-13
chlorine, bromine, cyano, C1-C4-alkoxy, Cl-C4
alkyl-carbonyl or C1-C4-alkoxy-carbonyl, or
represents C3-C6-cycloalkyl which is
optionally substituted by fluorine, chlorine,
bromine and/or C1-C4-alkyl, or represents
C1-C~-alkoxy;
or in which
( 2 ) A1 represents and A2 represents
OCIi3 CH3
OCH3 C2H5
OCH 3 C3H7
C2H5
OCH 3 ~(~ 3)2
OGH2C6Iis CH3
OG2Hs C~.H~
OCH 3 C,~.H9
- 39 -
CA 02420329 2003-03-13
a
OCH3
OC2H3 CH3
OC~H~ C3H~.
OCHZ-CHCH2 ~3
O-CHZ-CHCH2 ~-2H5
O-CH2-CHCH2 C3H7
O-CH2-CH-CH-Hr C~.H~
Br
~3
~3
OCH3 H
OCH3 CH2
O-CH~_COOCH 3 C3H7
OG2H5
C3H~
CH(CH 3)~
C4H9
CH3
C2H5
C~~
H
- 39a -
CA 02420329 2003-03-13
30517-181F
NHz OCH3
o CzHs
-CHZCH=CHz CH3
CH3
CH3 -CHzOCH3
-CH20CH3
-CHZOC2Hs
~ -N ( CH3 )
z .
According to one aspect of the present divisional
invention, there is provided a triazolinone of the formula
0
HN N~ (IIa)
I
N Rz
wherein R1 is Cl-C6-alkoxy (which is optionally substituted
by fluorine, chlorine, bromine, cyano, phenyl, Cl-C4-alkoxy
or C1-C4-alkoxycarbonyl) or is C3-C4-alkenyloxy and Rz is
hydrogen, or represents Cl-C6-alkyl which is optionally
substituted by fluorine, chlorine, bromine, cyano,
C1-C4-alkoxy or Cl-C4-alkylcarbonyl or C1-C4-alkoxy-carbonyl,
or represents C3-C6-cycloalkyl which is optionally
substituted by fluorine, chlorine, bromine and/or
C1-C4-alkyl, or represents phenyl-C1-C3-alkyl which is
optionally substituted by fluorine, chlorine, bromine,
cyano, vitro, C1-C4-alkyl, trifluoromethyl, Cl-C4-alkoxy
and/or Cl-C4-alkoxycarbonyl, or represents phenyl which is
optionally substituted by fluorine, chlorine, bromine,
cyano, vitro, C1-C4-alkyl, trifluoromethyl, methyl,
C1-C4-alkoxy, fluorine- and/or chlorine-substituted
- 39b -
CA 02420329 2003-03-13
30517-181F
C1-C3-alkoxy, C1-C4-alkylthio, fluorine- and/or
chlorine-substituted C1-C3-alkylthio, C1-C4-alkylsulphinyl,
Cl-C4-alkylsulphonyl and/or Cl-C4-alkoxy-carbonyl.
According to another aspect of the present
divisional invention, there is provided a triazolinone as
described herein, wherein R'' is methoxy, ethoxy, propoxy or
isopropoxy, and RZ is hydrogen, C2-C4-alkyl which is
optionally substituted by fluorine and/or chlorine, methoxy
or ethoxy, or represents C3-C6-cycloalkyl.
According to still another aspect of the present
divisional invention, there is provided a triazolinone as
described herein, selected from the group consisting of
those wherein
- 39c -
CA 02420329 2003-03-13
30517-181F
R1 represents and Rz represents
OCH3 CH3
OCH3 CzHs
OCH3 C3H~
OCZHS
CzHs
OCH3 CH ( CH3 ) z
OCH2C6H5 CH3
OCzHs C3H~
OCH3 C4H9
OCH3
OCZHS CH3
OC3H~ C3H~
O-CHz-CH=CHz CH3
O-CHz-CH=CHz Calls
O-CHz-CH=CHz C3H~
0- C H 2 -C H-C H z-B r C3H~
Br
OCH3
OCH3
OCH3
H
OCH3
CHz
O-CHz_COOCH3 C3H~
OCZH5
The new triazolinones of the formula (IIa) are
obtained either when oxadiazolinones of the general
formula (VIIa)
- 3 9d -
CA 02420329 2003-03-13
30517-181F
0
N 0 (VIIa)
N-
Az
in which
A2 has the abovementioned meaning, are reacted with
amino compounds of the general formula (VIIIa)
H2N 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)
HzN A1 (VIIIa)
are reacted with carbonic acid derivatives, then with
hydrazine or hydrazine hydrate and eventually with a
carboxylic acid derivative or carbonic acid derivative of
- 39e -
CA 02420329 2003-03-13
the general formula (Xa)
tR0)3C-A2 (Xa)
in which
A2 and R have the aboyementio~ed meanings,
analogouslx to tile process described above under (,e)
(also see the Preparation Examples).
In the general formula (IIa),
Al preferably represents C1-C5-alkyl, C3-CS-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)-amino, in par-
ticular dimethylamino or diethylamino, and
A2 preferabhy represents hydrogen, or represents C~-C6-
alkyl which is optionally substituted by fluorine,
chlorine, bromine, cyano, C1-C4-alkoxy, C1-C~-alkyl-
carbonyl or C~-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-C4-alkoxy
and/or Cl-C~-alkoxycarbonyl, or represents phenyl
which is optionallx substituted by fluorine, chlor-
ine, bromine, cyano, vitro, C1-C4-alkyl, trifluoro-
methyl, Cl-Cw-alkoxy, fluorine- and/or chlorine-
substituted C1-C3-alkoxy, C1-C~-alkylthio, fluorine-
and/or chlorine-substituted C1-C3-alkylthio, Cl-C4-
alkylsulphinyl, C1-C,,-alkylsulphonyl and/or C1-C~-
- 40 _
CA 02420329 2003-03-13
alkoxy-carbonyl, or represents C1-C4-alkoxy, in
particular hydrogen, C1-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
C1-C6-alkyl.
The compounds of the formulae (VII), (VIIa);
(VTII), (VIIIa) and (X) or (Xa) which are to be used as
starting substances for the preparation of the triaxolinones
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 ( IIT ) , R3 preferably, or in part icular,
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 -
- CA 02420329 2003-03-13
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-difluoramethoxy-, 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;.EF-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
ail inert organic solvents. These preferably include
aliphatic and aromatic, optionally haiogenated 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 -
CA 02420329 2003-03-13
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 triamide.
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) 1s 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
seguence. 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 (T) which has been obtained in crystalline form
is isolated by filtration with suction.
Formula (IV) provides a general definition of the
triazolinone derivatives to be used as starting substances in
process (b) for the preparation of compounds of the formula
(I).
In formula (IU), R1 and R2, preferably, or in
particular, have those meanings which have already been
mentioned above in connection with the description of the
- 43 -
CA 02420329 2003-03-13
compounds of the formula ( T ) as being preferred, or
particularly preferred; for R1 and R2, and
Z preferably represents chlorine, Cl-C4-alkoxy, benzylaxy
or phenoxy, in particular methoxy or
- 43a -
CA 02420329 2003-03-13
- 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 Table 2 Wand phosgene, methyl
chloroformate, benzyl chloroformate, phenyl chloroformate
or Biphenyl 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 triazolinone derivatives of the formula (IV)
are obtained for example When ~.riazolinanes of the
general formula (II)
0
NN~N~R1 tII>
I RZ
in which
R1 and R2 have the abovementioned meanings,
are reacted with carbonic said derivatives of the general
formula (XIj
z-co-z~
in which
Z has the abovementioned meaning and
_ 44 _
CA 02420329 2003-03-13
Z1 represents a leaving croup, 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 tent-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
(T). .
In formula ( V ) , R3 preferably, or in part icular,
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-t rif luoromethyi- , 2-dif luoro-methoxy- , 2-t rif luoromethoxy- ,
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-methoxycarbonyJ.-
- 45 -
CA 02420329 2003-03-13
and 2-ethaxycarbonyl-phenylmethanesulphanamide, 2-methoxy-
carbonyl-3-thiaphenesu7_phonamide, 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, 4,371,391; 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) for the preparation of the new
compounds of the formula (I) is preferably carried out using
diluents. Suj.table 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 tert-butylate, furthermore aliphatic, aromatic
or heteracyclic amines, for example triethylamine,
trimethylamine, dimethylaniline, dimethylbenzylamine,
pyridine, 1-5-diazabicyclo-(4.3.0]-non-5-ene (DBN), 1-8-
diazabicyclo-[5.4.U)-undec-7-ene (DHU) and 1,4-diazabicyclo-
[2,2,2]-octane (DABCO).
When carrying out process (b), the reaction
- 46 -
CA 02420329 2003-03-13
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 (VI), R3 and Z preferably, or in
particular, have those meanings which have already been
ment ioned above in connect ion with 'the descript ion of the
_ 47
CA 02420329 2003-03-13
V 1
compounds of the 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 -
CA 02420329 2003-03-13
To convert tlne 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, 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, Tpornoea, Polygonum, Sesbania,
Ambrosia, Cirsium, Carduus, Sonchus; Solanum, Rorippa,
Rotala, Lindernia, Lamium, Veronica, Abutilon, );mex, Datura,
Viola, Galeopsis; Papaver, Centaurea, Trifolium, Ranunculus
and Taraxacum.
Dicotyledon cultures of the genera~ Gossypium,
Glycine, Heta, Daucus, Phaseolus, Pj.sum, Solanum, Linum,
49 -
CA 02420329 2003-03-13
Ipoznaea, Vicia, Nicoti_aIla, Lyropersleon, Arachis, E3rassica,
Lar_tuca, Cucumis and Cucurbita.
Monacotyledon weeds of the Genera: Echinochloa,
Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine,
Branchiaria, Lolium, Bramus, Avena, Cyperus, Sorghum,
Agropyron, Cynodon, Monochoria, Fimbristylis, Sagittaria,
Eleocharis, Scirpus, Paspalum, Ischaemum, Sphenoclea,
Dactylactenium, Agrastis, Alopecurus and Apera.
Monocot~edon 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 cornbating of weeds in
annual cultures.
The compounds of the formula (I) are suitable for
combating monocotyledon and dicotyledon weeds both 'in the
- 50 -
CA 02420329 2003-03-13
pre-emergence and the post-emergence method. They are
- markedly more effective than, for example, isocarbamide.
To a certain extent, the compounds also Shaw a
fungicidal action, far example against powdery mildews and
against apple scab, and also against Pyricularia oryzae on
rice.
The active campounds ca.n 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-act ive 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
- 51 -
~ CA 02420329 2003-03-13
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 dixnethyl
sulphoxide, as well as water.
As solid carriers there ~:re 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 fox 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 cephalir~s and lecithins, and
- 52 -
CA 02420329 2003-03-13
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-6-ethylthio-3~(2,2-
dimethylpropy'1)-1,3,5-triazine-2,4(1H,3H)-dione (AMETHYDIONE)
or N-(2-benzothiazolyl)-N, N'-dimethylurea (METABENZTHIAZURONj
for combating weeds in cereals 4-amino-3-methyl-6-phenyl-
1,2,4-t_riazin-5(4H)-one (METAMITRON) for combating weeds in
sugar beet and 4-amino=6-(l,1-dimethylethyl)-3-methylthio-
1,2,4-triazin-5(4H)-one (METRIHUZIN) for combating weeds in
soya beans= furthermore also mixtures with 2,4-
dichlorophenoxyacetic acid (2,4-D);
4-(2,4-dichlorophenoxy)-butric acid (2,4-DH); 2,4-
- 53 -
CA 02420329 2003-03-13
dichlorophenoxypropionic acid (2,4-DP); 5-(2-chloro-4-
trifluoromethyl-phenoxy)-2-nitrobenzoic acid (ACIFLUORFEN);
2-chloro-2',6'-diethyl-N-methoxy-methyl-
- 53a -
CA 02420329 2003-03-13
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 (BTFENOX); 3,5-dibromo-4-hydroxy-benzonitrile;
(BROMOXYNIL); N-(butoxymethyl)-2-chloro-N-(2,6-diethyl-
phenyl)-acetamide (BUTACHLOR); ethyl 2-{[(4-chloro-6-
methoxy-2-pyrimidinyl)-aminocarbonyl]-aminosulphonyl}-
benzoate(CHT.ORIMURON);2-chloro-N-i[(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-chlaro-4-ethylamino-6-(3-
cyanopropylamino)-1,3,5-triazine(CYANAZINE);2,6-dichlo-
robenzonitrile(DICHLOBENIL);2-[4-(2,4-dichlorophenoxy)-
phenoxy]-propianic acid, its methyl ester or its ethyl
ester (DICLOFOP); 2-[(2-chlorophenyl)-methyl]-4,4-di-
methylisoxazolidin-3-one (DIMET~iAZONE); 4-amino-6-t-
butyl-3-ethylthio-1,2,4-triazin-5(9H)-one (ETHIOZIN); 2-
~4-[6-chloro-2-benzoxazolyl)-oxy]-phenoxy}-propanaic
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-
trifluoromethyl.phenyl)-urea {FLUOMETURON); 1-methyl-3-
phenyl-5-(3-triflnoromethylphenyl)-4-pyridone
(FLURIDONE); 5-(2-chloro-4-trifluoromethyl-phenoxy)-N-
mett~ylsulphonyl-2-nitrobenzamide (FOMESAFEN); N-phos-
phonomethyl-glycine (GLYPHOSATE);
methyl 2-[4,5-dihydro-4-methyl-4-(1-methylethyl)~5-oxo-
- 54 -
CA 02420329 2003-03-13
0 1H-imidazol-2-yl]-9(5)-methylbenzoate (IMAZAMETHABENZ);
- 2-(4,5-dihydro-9-methyl-9-isopropyl-5-oxo-1H-imidazol-2-
yl)-pyridine-3-carboxylic acid (IMAZ,APYR); 2-[5-methyl
5-(1-methylethyl)-4-oxo-2-imidazolin-2-yl]-3-quinoli_n
carboxylic acid (TMAZAQUIN); 2-[4,5-dihydro-4-methyl-4
isopropyl-5-oxo-(1H)-imidazol-2-yl]-5-ethylpyridin-3-
carboxylic acid (IMAZETIiAPYR); 3,5-diiodo-4-hydroxy-
benzonitrile (IOXYNIL); N,N-dimethyl-N'-(4-iso-
propylphenyl)-urea (ISOPROTURON); (2-methyl-4-chloro-
phenoxy)-acetic acid {MCPA); (9-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-.{[j((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-(1-ethyl-
propyl)-3_,4-dimethyl-2,6-dinitroaniline (PENDIMETHALIN);
0-{6-chloro-3-phenyl-pyridazin-9-yl) S-octyl thio-
carbamate (PYRIDATE); ethyl 2-[4-(6-chloro-quinoxalin-2-
yl-oxy)-phenoxy]-propionate (QUIZALOFOP-ETH'YL); 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-
- 55 -
CA 02420329 2003-03-13
(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, 1I18eCtiCideS, 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 he 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.
- 56 -
2
CA 02420329 2003-03-13
a Prega~ation~Xamples:
- Examgle 1
COOCH3 O
(A ,j--S02-NH-CO~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-3~.-~,2i4-triazol-3-one of
melting point 146°C.
- 5? -
CA 02420329 2003-03-13
Example 2
CI
_ O
S02 NH-CO~N"~N~CH3
1
N---~
'C H
2 l
(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
(y2.1 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. l It rat ion with 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 -
CA 02420329 2003-03-13
R3-S02-NH-CO~N~N~1 (I)
~R2
Table 3~ Preparation Examples of the compounds of the
formula (1y (w. - melting point):
p,
Ex . R1 R2 R3
No.
COOCH3
3 CbNS CH3 158
ocHF2
4 CH3 C2H5 159
OCNFZ
5 C2H5 CZHS 115
c~.._r
OCHF'2
6 CH3 C3H~ ~ 143
C1
7 C2H5 C2H5 ~ 139
CH3
_ 59 _
CA 02420329 2003-03-13
r
Table 3: continuation
-
EX. R1 R2 R9 m.p. (
"C)
No.
CI
8 CH3 C3H~ ~ 141
CN3
COOCH3
9 OCH3 CH3 , 121
SOZN(CH3)2
l0 OCH3 CH3 180
C1
11 OCH3 CH3 ~ 149
CH3
COOCH3
12 OCH3 C2H5 ~ 144
COOCH3
13 OCH3 C3H~ 128
S02NtCH3)2
14 CH3 C2HS ~ i73
- 60 -
CA 02420329 2003-03-13
Table 3r - conti~uatiorl
EX. R1 R2 R9 m.p. ( °C)
No.
SO~NtCH3)2
15 CH3 C3H7 133
COOCH3
~,
16 C2H5 ~ 154
COOCH3
17 OCH3 CH(CH3)2 137
~i
S02N(CH3)2
18 C2H5 ~ 174
COOCH3
19 C3H7 ~ 97
COOCN3
20 CH3 NtCH3)2 168
COOCH3
21 OCH2C6H5 CH3 174
Cl
22 C2H5 C3H7 ~ 136
C~3
- b1 -
CA 02420329 2003-03-13
Table 3s - continuation
Ex. Ri R2 R3 m.p. ( C)
No.
COOCH3
23 N(CH3)2 C2H5 ~ a39
COOCH3
24 N(CH3)2 H 197
COOCH3
25 NtCH3)2 CH(CH3)z ~- 148
COOCH3
26 OC2N5 C2H5 ~ 153
COOCH3
T
27 OC2H5 C3H7 ~ 155
COOCH3
28 CH(CH3)2 186
r J~
C1
29 C3H~ ~ 146
CH3
COOCH3
30 N ( CHa C3H7 / 1_1 G
) 2
- 62 -
CA 02420329 2003-03-13
Table 3: - continuation
Ex. R1 RZ #i$ m.p. ( °C)
No.
COOCt~3
31 N(CH3a2 ~~ 131
COOCH3
32 C2H5 C,~H~ ~ 98
COOCH3
33 CH3 C4H9 ~ 113
COOCH3
34 C3H7 C4H9 ~ 88
COOCH3
35 C4Hg ~ 117
COOCH3
36 OCH3 C4H9 ~ 117
COOCH3
37 CH3 141
GOOCH3
38 C2H5 ~ 130
- 63 -
CA 02420329 2003-03-13
Table 3s -
continuation
Ex. R1 RZ ~i$ m.p. ( C~
No.
COOCH3
39 C3H7 ~ -- 139
COOCH3
9 0 lsl
COOCH3
41 ~ CH3 ~ 151
.
COOCH3
92 CH(CH3)2 NHCt-1(CH3)2~ ~ 13s
COOCH3
93 N(CH3)2 N(CH~)2 ~ 171
OCF3
A4 CH3 C3H~ r 1b8
COOCH3
45 C2H5 N(CH3)2 i34
OC~'3
46 CH3 C2H5 ~ 167
- 64 -
CA 02420329 2003-03-13
Table 3: - continuation
fix. R1 R2 R3 m.p. ( °C)
No.
pC~3
47 NH2 C3H~ / 120
COOCH3
4s --~ NH~ 120
coocH~
49 H 195
COOCH3 '
50 -CH2GH=CH2 G2H5 108
COOCH3
51 -CH2CH=CH2 H ~~ 158
OCF3
52 OCH3 C3H7 110 - 111
COOC~3
3 CH2--(") H / , 212 - 214
COOCH3
54 C3H7 ~d 168 - 169
- 65 -
CA 02420329 2003-03-13
Table 3: - continuation
- Ex. R1 R2 R3 m.p. ('C)
No.
OCF3
55 C3H7 ~ ~ 103 - 105
OC~'3
56 C2H5 127
OCF3
57 OCH3 C2H5 ~ ~ 111 - 113
COOCH3
58 -OCH3 139
OCF3
~
59 -I~HCH3 C3H7-n ~ 196
F -
60 CN3 C3H7-n ~ ~ i78
COOCH3
61 ~ H ~ 177
- 66 -
CA 02420329 2003-03-13
Table 3:
- continuation
Ex. R1 R2 R3 mP ~ ~0)
No.
COOC#i3
/
62 -CH2CH(CH3)2 C2H5 \ 123
COOCH3
63 -CH2-CH=CH2 C3N7-n (amorphous)
COOCH3
6A CH C ~ 157
/ H
~
2 2 /
- 5
COOCH3
b5 / CZHS / 117
\ \
__ ~_
COOCH3
7
bb -C(CH3)3 C2H5 -~ 182
COOCH3
67 ~ C2H5 / \
133
COOCH3
68 ~ C2H5
62
COOCH3
69 -CH2-CH=CH2 CH3 120
- 6? -
CA 02420329 2003-03-13
Table 3:
- continuation
- EX. R~ R2
No.
GOOCH3
70 H C ~- 183
HS
2
C00CH3
71 C2H5 H 1 196
COOCH3
72 CH
3 153
OCF3
~
73 -OCH3 ~ 138
COOCH3
~
79 CH(CH3)2 H ~ 191
C00CH3
75 ~ H
91
COOCH3
76 ~ H ~ 192
COOCH3
77 -C(CH3)3 H ~ ~ 211
6D _
CA 02420329 2003-03-13
Table 3: - continuation
Ex. R' R2 R3 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 ' ~ 129
OCF3
84 -CH20CN3 /'\
102
COOCH3
85 -CH20CH3 / \ 155
I _ 6g _
CA 02420329 2003-03-13
Table 3: - continuation
- EX. R1 RZ R3 m.p~ ( '~.')
No.
COOC~-13
~
~
86 -CH20C2H5 123
OC~'3
87 -CH20C2H5 ~ 99
C~
88 -NiCH3)2 ~ 189
CH3
C1
89 -OCH3 C2H5 ~ 155
CH3
C1
90 C2H5 7 133
~
CH3
Ci
91 -OCH3 C3H7-n ~ 125
~
CH3
92 C2H5 ~ 138
~
S
QOCH3
- 7d -
CA 02420329 2003-03-13
Table 3: - continuation
EX. R1 R2 R3 m.p. ( 'C)
No.
OCF3
93 -OC2H5 C2H5 \ 132
OCF3
~
94 -OC2H5 C3H~-n \ 107
OCF3
95 -OCH3 CH(CH3)~ ~ 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
- 71 -
CA 02420329 2003-03-13
Table 3: - continuation
Ex. R' RZ R3 m.p. ( 'C)
No.
C1
101 CH3 -N(CH3)z ~~ 181
CH3
Co0CH3
102 CH3 -OCH3 ~ 150
CI
103 CZHS ~ ~ 147
CH3
C1
104 -CH2-CH=CH2 CH3 ~ 132
CH3
C1
105 -CH2-CH=CH2 C2H5 ~ ~ 109
CH3
C1
106 -CH2-CH=CH2 C3H7-n ~ lpq
CH2
_ 72 _
CA 02420329 2003-03-13
Table 3: - continuation
EX. R1 RZ R3 m.p. ( ~C)
No.
C1
107 -OC2H5 C2N5 , ~ 197
CH3
C1
108 -OC2H5 C3H7-n r ' 136
C ~i 3
Cl
109 -OCH3 CH(CH3)2 / ~ 126
CH3
C1
110 CH3 CH3 ~ ~ 146
CH3
C1
111 CH3 ~ ~ 175
CH3
C1
112 CH3 CH(CH3)2 ~ ~ 124
CH3
- 73 -
CA 02420329 2003-03-13
Table 3: - continuation
EX. R~ RZ R3 m.p. ( 'C)
No.
C1
113 CH3 , ~ 171
C~3
C1
114 CHICH3)2 / \ 132
CH3
C1
115 ~ ~ 167
CH3
CH3
1I6 CH3 CH3
155
CH3
117 CN3 C2H5 ~ ~ 147
CH3
118 CH3. C3H7-n ~ 169
- 74 _
CA 02420329 2003-03-13
Table 3: - continuation
° E x . R1 R2 R3 m . p . ( ' C )
No.
119 OCH3 C2H5
OOCH3
G~ COOCH3
120 -CH2 _C~HS - 132
- ?5 -
CA 02420329 2003-03-13
tartan substances of the formul II s
Example (II-11
0
HN~N-'O C 2 H 5
~2H5
Step 1:
H-i-CO-NH-OC2H5
(zX-1)
N-N-CO-C2H5
A mixture of 68.5 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 theory) of 1-ethoxy-
aminocarbonyl-2-propionyl-hydrazine of melting point
122°C.
_ 76 _
CA 02420329 2003-03-13
Step 2:
O
NN~NipC2H~ (II-11
~2H5
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 chlaride 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-2,9-dihydro-3II-1,24-triazol-3-one of melting paint
93°C.
Example (II-2~
0
HN~N~CH3 (II-2)
~C3H7
A mixture of 90 g (0.3i molj of 5-propyl-1,3,4-
- 77 -
CA 02420329 2003-03-13
oxadiazolin-2-one, 109 g of aqueous methylamine solution
. (32 $ strength, 1.125 mol of CN3NHz) and 500 ml of water
is refluxed for 12 hours and then concentrated. The
residue is taken up in ethanol and~reconcentrated. The
residua 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.
Thi$ gives 31.7 g (72 % of theory) of 9-methyl-
5-propyl-2,4-dihydro-3H-1,24-triazol-3-one of melting
point 86°C.
Example( I I-3 ~,
O
HN~N~'N(CH3)2
~H
856 g ( 4 . 0 mol ) of Biphenyl carbonate are dis-
solved in 588 g of ethylene chloride. 295 g (9.0 mol)~of
dimethylhydrazine (98 $ pure) are added dropwise with
15, 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, for about 1 hour, stirring is continued.
When cold, the solution is distilled in vacuo, during
which process ethylene chloride aid water are removed
(final bottom temperature 100°C). The above phenolic
- 78 -
CA 02420329 2003-03-13
~ dimethyl carbodihydrazide solution is added dropwise in
the course of 90 minutes at reflux temperature (about
102°C) to g24 g (4.0 mol) of trimethyl orthoformate.
After the methanol which has farmed is removed by distil-
s lation, phenol is distilled off in vacua, 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 4 below can also be prepared
analogously to Examples (II-1) to (II-3).
0
HN~NiRl (II)
- 79 -
CA 02420329 2003-03-13
Table 4: Preparation examples of ~~e compounds of the
formula (TI) -
Ex. R' R2 m.p. ( C)
No.
II-4 C3H? CN3 . 48
II-S CH(CH3)2 CH3 11B
II-6 C)-I3 CH3 ~ 139
II-7 C2H5 C2H5 117
II-8 C3H~ C2HS 42 - 45
II-9 CH(CH3)2 C2H5 102
II-10 C2H$ C3H~ 97
II-il C3H~ C3H~ (amorphous)
I1-12 CH(CH3)2 C3H~ 91
II-13 CH3 CH(CH3)2 92
II-14 C2H5 CH(CH3)2 (amorphous)
II-1S C3H~ ~ CH(CH3)2 (amorphous)
II-16 CH(CH3)2 CH(CH3)2 1b8
II-17 C2H5 GH3 134
II-18 CH3 159
II-19 OCH3 CH3 178
II-20 OCH3 C2HS 140
I1-21 OCH3 C3H~ 127
- 80 --
CA 02420329 2003-03-13
Table 4 - continuation
I;x. R' R2 m.p. (Cj
No.
II-22 OCH3 GH(~H3)2 130
II-23 OCH2CbH~ CHI lOb
II-24 C2H5 150
II-25 C3H7 130
II-26 OC2H5 C3H7 72
II-27 C~3tCH3)2 121
II-28 CH3 C4H9 50
II-29 C2H5 C4H9 76
II-30 C3H7 C4H9 (amorphous)
II-31 OCH3 C4H9 100
II-32
C4H9 6b
II-33 CH3 68
II-34 C2H5 130
II-35 C3H7 ~ 68
II-36 154
- ai -
CA 02420329 2003-03-13
,
Table 4 -
cQ~~inuation
Ex. R1 R2 m.p ('C)
No.
II-37 NtCH3)2 CH3 153
II-38 N(CH3)2 C2H~ 114
II-39 N(CH3)2 C3H7 108
II-40 N(CH3)2 CH(CH3)2 100
II-41 CH3 N(CH3)2 80
II-42 N(CH3)2 134
II-43 CHtCH3)2 NHCH(Ctl3)2 205
II-44 N(CN3)2 N(CH3)2 93
II-45 CZHS NtCH3~2 50
II-46 CN3 145
II-47 ~ CH3 163
II-98 H 102
I1-49 OCH3 136 - 137
II-50 CH3 C6H5
II-51 NH2 H 192
II-52 NH2 CH3 230
II-53 ' CF'3 163
NH2
- 82 -
CA 02420329 2003-03-13
t
~ Table 4 - continuation
Ex. Ri R~ m.p. ( C)
No.
II-54 NHCH3 CHiCH3)2 105
II-55 NHCH3 ~ 95
II-56 NHZ C2H5 170
II-57 NHZ C3H7 147
iI-58 NHCH3 NHCH3 137
II-59 CH2C6H5 C2H5 125
II-60 NHCH3 H 133
II.-61 NHCH3 N(Ct~3)2 129
II-62 NHCH3 C3H7
II-63 NH2 ~ I 248
II-64 NH2 -~HC2H5 176
CH3
II-65 NH2 183
II-66 NH2 210
CF3
II-67 NHCH3 C2H5 101
II-68 NH2 N(C2H5)2 196
- g3 _
CA 02420329 2003-03-13
Table 4 - continuation
Ex. R1 R2 mP ( oC)
No.
II-69 NH2 ~N- 233
II-70 NH2 CH(CN3D2 172
II-71 NH2 C(CH3)3 261
II-72 NH2 CH2CH20CH3 98
II-73 NH2 C(CH3)2C~H5 213
II-74 NH2 ~lHC2H5 220
II-75 . NH2 OCH3 (amorphous)
II-76 HH~ ~ CH20GH3 134
II-77 NH2 CH20C2H5 104
II-78 N(CH3)2 GH3 153
II-79 -CH2 C1 C2H5 103
C1
II-80 -CH2CH(CH3)2 C2H5 105
II-81 C6H5 H 183
II-82 N(CH3)2 CH(CH3)2 (amorphous)
II-83 NHCH3 CH3 114
II-84 NH2 CH2CbH5 168
II-85 NH2 N(CH3)2 207
II-86 NH2 CbHS 230
- 84 -
CA
02420329
2003-03-13
Table 4 - continuation
Ex. R1 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(C~3)2
II-92 GH2C6H5 H ill
II-93 C3H7 y~ 48
II-94 C6H5 C2H5 , 124
II-95 C(CH3)3 C2~j5 158
II-96 CH3 ~ 157
II-97
C 108
H
2
5
II-98 ~ C H
2 5 132
iI-99 -CH2CH=CH2 CH3 108
II-100 C6H5 CH3 I50
II-101 ~ CH3 116
II-102 ~ C2H5 146
II-103 C2H5 H 68
II-104 CH(CH3)2 H 105
- 85 -
CA 02420329 2003-03-13
Table 9 - continuation
- Ex. R' RZ m.p. ( C)
No.
II-105 ~ H 79
II-106 ~ H 162
II-107 C(CH3)3 H 194
II-108 -CN2-iH-CH2Br CH3 111
W
II-109 CH3 -CH20CH3 104
II-1.10 _ CH3 -CH20C2H5 102
II-111 --Q -CH20CH3 102
II-112 ~ -CH20C2H5 119
II-113 -~ -N(CH3)2 130
iCH3
II-114 NN2 -N 186
\C2H5
~.CN3
II-115 NH2 -N 165
~C3H7-n
~2H5
II-l1b NH2 -N 186
.
,.C3H7_n
II-117 NH2 -N O 2b7
U
II-118 CH3 -OCH3 144
_ 86 _
CA 02420329 2003-03-13
k The compound of Example (II-118) disclosed in Table 4
(above) can be prepared as follows;
O
HN~N~CH3 tII-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 Ia 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 ~ of theory) of 5-methoxy-4-methyl-
2,4-dihydro-3l~-1,2,4-triazol-one as colorless crystals
of melting point 144°C.
~- S 3
CA 02420329 2003-03-13
Examples of hydrazine derivatives of the
formula (IX) which can be obtained analogously to Ex-
ample {II-1), step listed in Table 5 below,
1, are
H-N-CO-NH-Ri
tIX)
H-N-CO-R2
Table 5: Examples o~ the hxdr~~ine derivatives
of the
formula (IX)
Ex. R1 RZ m.p. ( C)
No.
IX-2 OCH3 C2H5 120
IX-3 OCH3 C3H7 125
IX-4 OCH3 CHtCH3)2 127
IX-5 OCH2C6H5 CH3 1D0
IX-6 C2H~ 17Q
IX-7 C~H7 180
IX-8 OOHS C3H~ 119
IX-9 CH t t:j~3 ) 150
2
IX-10 OCH3 CgH9 134
IX-11 CQH9 159
- 8B -
CA 02420329 2003-03-13
Table 5 - continuation
EX. R1 ~t2 m~p~ ( '~')
No.
IX-I2 ~ 188
IX-13 OCH3 140
IX-19 CH2-CH=CH2 C3H7 134
_~
IX-15 ~ -CH20C2H5 97
- 89 -
CA 02420329 2003-03-13
Startin substances of the formula IV
- Example (IV-1~
O
- C O'~N~N~C H 3
°' '''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 BO m1 of tetra-
s hydrofuran, and 1.8 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 ethers 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).
- 90 -
CA 02420329 2003-03-13
Z - C O~N~N~Fi 1 ( I V )
2
R
Table 6: Examples of the compounds of the formula {IV)
Ex. R1 RZ Z m.p. ('C)
No.
I V-2 C3?~~ C3H~ . C6H5 88
IV-3 OCH3 C3H~ CbHS 82
IV-4 CH3 C3N~ C6H5 84
IV-5 NH2 C3Hy GbHS 133
IV-6 NH2 CH3 C6?~5 82
IV-7 C2H5 C6H5 152
iV-8 OC2H5 C2H5 CbHS
IV-9 OCH2CH=CH2 CH3 C6H5
IV-10 CQH9 C6H5
IV-I1 CH3 C6H5
IV-12 NHCH3 C2H5 C6H5
CA 02420329 2003-03-13 _
a
_ Table 6 - continuation
EX. R~ R2 Z m.p. ('C)
No.
IV-13 CH3 CH2CbH5 C6H5
IY-14 CH3 NHCH(CH3)2 C6H5
IV-15 N(CHa)2 N(CN3)~ C6H5
IV-16 C6H5
IV-17 OC2H5 C6HS
IV-18 0C3H7 CZHS C6H5
IV-19 C2H5 CqH9 C6H5
IV-2Q CHfCH3)2 CH(CH3)2 CbE~5
iv-21 OcH3 C2H5 C6H5 89
IV-22 C3H7-r~ C6H5 109
- 92 -
Use Examples:
CA 02420329 2003-03-13
In the following us-e examples, the known herbicide
isocarbamide, of formula (A) below, is used as comparison
substance:
HN~~ N-CO-NH--CI~zCH(CIi3~ ( 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:
OC~H~2
C
SOZ-NH-CU~N~N~CH3 ( 4
I
N---~
'C H
2. 5
OCHFZ
O
~~/ -S02-NH-CO~N~~~CxHs ( 5 )
I
N ~C2H5
OCHF2
0
SOz NH-CO~N~ ~CH3 ( 6
N
I
N C
C1
O
SO2 Nii CO~N~ ~CH3 ( 2 )
N
I
CH3 N----~
~C ~I
2 s
- 93
CA 02420329 2003-03-13
Cl O
~ S02-1JH-CO~N~PJ~'C2H5 ( 7 )
CH 3 TT"-"1C 2H 5
Cl O
~ SOZ-NH-CO~N~N-'CH3 ( g )
CHI 1~3H~
COOCH3 O
("J-S02-NH-CO~N~N~OCH3 (12)
~C2H5
COOCtf3 O
502-NH-CO~N~N~'OCI~i3 ( 1 3 )
-"3H7
S02N(CH3)2 O
~SOZ-NH-CO~N~N~CH3 (1A)
~.~%
. ~2H5
S02N(CH3)2 O
~ SO~-NH-CO'~N~1J~CH3 ( 15
~c 3 ti ~
COOCH3 O
~S02-NH-CO~N~ , (16D
~2ti5
COOCH3 O
S02-NH-CO''~N~N~OCH3 t 1 7 )
~H(CH~)2
r'
- 94 -
CA 02420329 2003-03-13
so2N ( cl-i3
) 2 0
~S0
-NH-CO'~
~
-~
2 N ( 1
N 8
~ D
C2H5
COOCH3 O
S0
-Nl~-CO~N~
~ t 1
2 N--~c 9
y )
i ~
3
COOCH3 O
50 ( 20
-NH-CO~N~N~'CH )
2 3
I-~_~~~~
I~NtCH
)
3
2
COOCHS O
50 (26)
-NH-CO'~N~N~OC
H
2 Z
S
-"2H5
COOCH3 O
~S0
-1JH-CO~N~
~
2 OC2tl5 t 27
N )
~I~ ~
~
3H7
COOCH~ O
50
-Nti-CO~1J~~
~
2 N ( 28
~H )
tCH3)2
C1 p
S0
-NH-CO~N~
2 1 t29)
CH
3
COOCJi3 O
S0
-NH-CO~N~
'
~ N- t aO
2 N ( CH ) )
3 2
~
~N~
- 95 -
CA 02420329 2003-03-13
w COOCH~ 0
- ~'SOZ'NH-CO~N~N~'G2H5 ( 32
~4H9
COOCH3 O
S02-NH-CO~N~N~'CH3 ( 33
COOCH3 O
502-NH-CO~N~N~C3H~ (3q
l
N'~4H9
COOCH3 O
S02-NH-CO~N~ (3S
4H9
COOCH3 O
S02-NH-CO~N~N~'CH3 ( 3y
GOOCH3 O
to ,l--S02-NH-CO'~N~N~'C3H~ ( 39
-I
COOCH3 O
S02-NH-CO~N~ (40)
- 96 -
CA 02420329 2003-03-13
COOCH3 O
502-NH-CO'N~N~'OC1-~~ ( 9 )
~CH3
COOCH3
S02-NH-CO'i I~N(CH3)2 (31)
COOCH3 O
S02-NH-CO'IJ~N~OC~-I3 ( 36
- 97
CA 02420329 2003-03-13
t
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 denotes
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, 1B, 19, 20, 26, 2?, 28, 29, 34, 3?, 39 and 40.
- 98 -
CA 02420329 2003-03-13
i
~' Example H
Post-emergence test
Solvent: 5 parts by weight of acetone
Emulsifiers 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, 1B, 19, 20, 26, 27, 28, 29, 30, 32,
33, 34, 35, 37, 39 and 4p.
- 99 -
CA 02420329 2003-03-13
Example G
Pyricularia test (rice) / protective
Solvent: 12,5 parts by weight of acetone
ET:rulsifier: 0,3 parts by weight of alkylaxylpolyglycol 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 arc 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, 3Q, 31, 32, 33, 34, 35, 36 ,37.
- i00 -
CA 02420329 2003-03-13
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 compoun d. 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 evaluatedo
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, 3b, 37.
- l
