Note: Descriptions are shown in the official language in which they were submitted.
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BILE, P~td-tit T~il~~~~-B
'F~#~ TRANSLATION
Substituted 2-aryl-1,2,4-triazine-3,5-di(tbi)ones
The invention relates to novel substituted 2-aryl-1,2,4-triazine-3,5-
di(thi)ones, to
processes for their preparation and to their use as herbicides.
S
EP 11693, EP 271170, WO 86/00072, US 4755217, US 4878941, US 4956004, US
5262390, and US 5344812 disclose that certain substituted 2-aryl-1,2,4-
triazine-
(thi)ones have herbicidal properties. However, the compounds described therein
have
not attained any major importance.
This invention, accordingly, provides the novel substituted 2-aryl-1,2,4-
triazine-3,5-
di(thi)ones of the general formula (I),
Rs Q1 R9
Ra ~ N Qz (I)
'N
Rs Rz
in which
Q1 represents oxygen or sulphur,
Q2 represents oxygen or sulphur,
R1 represents hydrogen, cyano, amino, or represents respectively option-
ally substitutued alkyl, alkoxy, alkylamino, dialkylamino, alkylcarbonyl,
alkoxycarbonyl, alkenyl, alkenylcarbonyl, alkenyloxycarbonyl, alkinyl,
alkinylcarbonyl, alkinyloxycarbonyl, cycloalkyl or cycloalkylalkyl,
R2 represents hydrogen, halogen, nitro, carboxyl, cyano, thiocarbamoyl,
amino, or represents respectively optionally substituted alkyl, alkoxy,
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alkylthio, alkylamino, dialkylamino, alkenyl, alkenyloxy, alkenylthio,
alkinyl, alkinyloxy, alkinylthio, cycloalkyl or cycloalkylalkyl,
R3 represents halogen,
R4 represents cyano or thiocarbamoyl and
RS represents the grouping below,
-Al-A2-A3
in which
A1 represents a single bond, represents oxygen, sulphur, -SO-,
-S02-, -CO- or the grouping -N-A4-, where A4 represents
hydrogen, hydroxyl, alkyl, alkenyl, alkinyl, alkoxy, aryl,
alkylcarbonyl, arylcarbonyl, alkylsulphonyl or arylsulphonyl,
A1 furthermore represents respectively optionally halogen
substituted alkanediyl, alkenediyl, azaalkenediyl, alkinediyl,
cycloalkanediyl, cycloalkenediyl or phenylene,
A2 represents a single bond, represents oxygen, sulphur, -SO-,
-S02-, -CO- or the grouping -N-AS-, where AS represents
hydrogen, hydroxyl, alkyl, alkoxy, aryl, alkylsulphonyl or
arylsulphonyl,
A2 furthermore represertt5 respectively optionally halogen-
substituted alkanediyl, alkenediyl, azaalkenediyl, alkinediyl,
cycloalkanediyl, cycloalkenediyl or phenylene,
A3 represents hydrogen with the proviso that in this case A1 and/or
A2 do not represent a single bond
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-3-
A3 furthermore represents hydroxyl, mercapto, amino, cyano, iso-
cyano, thiocyanato, nitro, carboxyl, carbamoyl, thiocarbamoyl,
sulpho, chlorosulphonyl, halogen, represents respectively
optionally halogen- or alkoxy-substituted alkyl, alkoxy, alkyl-
thio, alkylsulphinyl, alkylsulphonyl, alkylamino, dialkylamino,
alkoxycarbonyl or dialkoxy(thio)phosphoryl, represents re-
spectively optionally halogen-substituted alkenyl, alkenyloxy,
alkenylthio, alkenylamino, alkylideneamino, alkenyloxycarbon-
y1; alkinyl, alkinyloxy, alkinylthio, alkinylamino or alkinyl-
oxycarbonyl, represents respectively optionally halogen-,
cyano-, carboxyl-, alkyl- and/or alkoxy-carbonyl-substituted
cycloalkyl; cycloalkyloxy, cycloalkylalkyl, cycloalkylalkoxy,
cycloalkylideneamino, cycloalkyloxy-carbonyl or cycloalkyl
alkoxycarbonyl, or represents respectively optionally nitro-,
cyano- carboxyl-, halogen-, alkyl-, halogenalkyl-, alkyloxy-,
halogenalkyloxy- and/or alkoxy-carbonyl-substituted aryl, aryl
oxy; aralkyl, arylalkoxy, aryloxycarbonyl or arylalkoxycarbonyl,
A3 furthermore represents respectively optionally fully or partially
hydrogenated pyrrolyl, pyrazolyl, imidazolyl, triazolyl, furyl,
oxiranyl, oxetanyl, dioxolanyl, thienyl, oxazolyl, isoxazolyl,
thiazolyl, isothiazolyl, oxadiazolyl, thiadiazolyl, pyridinyl,
pyrimidinyl, triazinyl, pyrazolylalkyl, furylalkyl, thienylalkyl, a
oxazolylalkyl, isoxazolylalkyl, thiazolylalkyl, pyridinylalkyl,
pyrimidinylalkyl, pyrazolylalkoxy, furylalkoxy, represents per-
hydropyranylalkoxy or pyridylalkoxy.
The novel substituted 2-aryl-I,2,4-triazine-3,5-di(thi)ones of the general
formula (I),
are obtained when
(a) 1,2,4-triazine-3,5-di(thi)ones of the general formula (I1 j,
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k
-4-
R~
Q ~
-- N
H - N Q2 (II)
'N =
R2
in which
Q1, Q2, Ri and R2 are each as defined above,
are reacted with halogenobenzene derivatives of the general formula (III),
R3
R4 ~ ~ X1 (III)
Rs
in which
R3, R4 and RS are each as defined above and
Xl represents halogen,
if appropriate in the presence of a diluent and if appropriate in the presence
of
a reaction auxiliary,
or when
(b) 2-aryl-1,2,4-triazine-3,5-di(thi)ones of the general formula (Ia),
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R3 Q~ H
i
R4 ~ N Qa _ (Ia)
~N
R~ Rz
in which
Q1~ Q2~ R2~ R3~ R4 ~d RS are each as defined above
are reacted with alkylating agents of the general formula (IV),
Rl-XZ fIVI
in which
Rl is as defined above and
X2 represents halogen or the grouping -O-S02-O-Rl,
if appropriate in the presence of a diluent and if appropriate in the presence
of
a reaction auxiliary,
or when
(c) arylhydrazones of the general formula (V),
R3
CH3
R4 ~ ~ N H N
CH3
Rs
in which
R3, R4 and RS are each as defined above
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are reacted with alkali metal (thio)cyanates of the general formula (VI),
M-Q 1-CN Cue)
in which
Q 1 is as defined above and
M represents an alkali metal atom,
if appropriate in the presence of a diluent and if appropriate in the presence
of
a reaction auxiliary and the resulting 2-aryl-1,2,4-triazolidine-3-(thi)ones
of
the general formula (VII),
R3 0\'1 H
Ra N~N~
CHs
N
Rs / CHs
H (VII)
in which
Q 1 ~ R3, R4 and RS are each as defined above
are reacted with ketocarboxylic acids of the general formula (VIII),
O
2~OH
~''(R
O (VIII)
in which
R2 is as defined above
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if appropriate in the presence of a diluent and if appropriate in the presence
of
a reaction auxiliary,
or when
(d) aryl-amines of the general formula (IX),
R3
R4 ~ ~ NHz
R5
in which
R3, R4 and RS are each as defined above
are diazotized and subsequently reacted with a cyanoacetylcarbamic acid ester
of the general formula (X),
R~
NC~N~O~C H
z s
O O
in which
R1 is as defined above,
if appropriate in the presence of a diluent and if appropriate in the presence
of
a reaction auxiliary,
and the resulting compounds of the general formula (XI),
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L
O~O~
R
C2Hs
N-R~ _
R ~ ~ NH O
'N
RS CN
in which
RI, R3, R4 and RS are each as defined above
are cyclized if appropriate in the presence of a diluent and if appropriate in
the
presence of a reaction auxiliary,
or when
(e) arylhydrazines of the general formula (XII)
R3
R'' ~ ~ NH-NHz (
Rs
in which
R3, R4 and RS are each as defined above
are reacted with ketocarboxylic acid derivatives of the general formula
(XIII),
O
II O. R
R
O (XIII)
in which
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R2 is as defined above and
R represents hydrogen or alkyl,
if appropriate in the presence of a diluent and if appropriate in the presence
of
a reaction auxiliary, and the resulting compounds of the general formula (XIV'
R3 R
O
R4 ~ ~ N H O (
'N -
Rs R2
in which
R2, R3, R4 and RS are each as defined above and
R represents hydrogen or alkyl,
are reacted with iso(thio)cyanates of the general formula (~~,
Rl-N-C-Q1 (
in which
Q1 and Rl are each as defined above,
if appropriate in the presence of a diluent and if appropriate in the presence
of
a reaction auxiliary
and the resulting compounds of the general formula (XVI),
i..
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R'
R~ Q~ ~ , R
_ ~-NHO
R4 ~ ~ N O (XVI)
N-
Rs Rz
in which
Q1, Rl, R2, R3, R4 and RS are each as defined above and
R represents hydrogen or alkyl,
are cyclized, if appropriate in the presence of a diluent and if appropriate
in the
presence of a reaction auxiliary,
or when
(f) 2-aryl-1,2,4-triazine-3,5-dione-6-carboxylic acids of the general formula
(
R3 O H
N
R4 ~ O
,N -
R$ COOH
in which
R3, R4 and RS are each as defined above are obtained,
if aryl-amines of the general formula (IX),
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R3
R4 ~ ~ NHZ - (IX)
R5
in which
R3, R4 and R$ are each as defined above
are diazotized and subsequently reacted with the malonyldiurethane of the
formula (XVII),
CHZ(CO-NH-COOC2H5)2 (XVII)
if appropriate in the presence of a diluent and if appropriate in the presence
of
a reaction auxiliary and subsequently cyclized.
It is also possible to convert the compounds of the general formula (I)
according to
further customary methods into other compounds of the general formula (I)
according
to the definition above, for example by nucleophilic substitution (for example
R5: F
~ OH, SH, NH2, OCH3, OCH2CH=CH2, NHS02CH3); or by further functional
group conversions (for example R2: COOH ~ H, COOH --~ COCI, COOCH3, COCI
~CONH2, CN -~ CSNH2; R4: CN ~ CSNH2; R5: N02 ~ NH2, NH2 -a F, Cl,
Br, CN, NHS02CH3, S02C1) or by oxidation or sulphurization (for example Q1,
Q2:
O ~ S, or S ~ O), cf. also the Preparation Examples.
The novel substituted 2-aryl-1,2,4-triazine-3,5-di(thi)ones of the general
formula (I)
have strong and selective herbicidal activity.
In the definition, the saturated or unsaturated hydrocarbon chains, such as
alkyl,
alkenyl or alkinyl, are in each case straight-chain or branched.
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Halogen generally represents fluorine, chlorine, bromine or iodine, preferably
fluorine,
chlorine or bromine, in particular fluorine or chlorine.
The invention preferably provides compounds of the formula (I) in which
Q1 represents oxygen or sulphur,
Q2 represents oxygen or sulphur,
Rl represents hydrogen, cyano, amino, represents respectively optionally
cyano- fluorine-, chlorine-, C1-Cq.-alkoxy- or Cl-Cq.-alkylthio-
substituted alkyl, alkoxy, alkylamino, dialkylamino, alkylcarbonyl or
alkoxycarbonyl having in each case 1 to 6 carbon atoms in the alkyl
groups, represents respectively optionally fluorine-, chlorine- or
bromine-substituted alkenyl, alkenylcarbonyl, alkenyloxycarbonyl,
alkinyl, alkinylcarbonyl or alkinyloxycarbonyl having in each case 2 to
6 carbon atoms in the alkenyl or alkinyl groups, or represents
respectively optionally cyano-, fluorine-, chlorine-, bromine- or C1-Cq.-
alkyl-substituted cycloalkyl or cycloalkylalkyl having in each case 3 to
6 carbon atoms in the cycloalkyl groups and optionally 1 to 4 carbon
atoms in the alkyl moiety,
R2 represents hydrogen, halogen, nitro, carboxyl, cyano, thiocarbamoyl,
amino, represents respectively optionally cyano-, fluorine-, chlorine-,
C1-Cq.-alkoxy- or C1-Cq-alkylthio-substituted alkyl, alkoxy, alkylthio,
alkylamino or dialkylamino having in each case 1 to 6 carbon atoms in
the alkyl groups, represents respectively optionally fluorine-, chloririe-
or bromine-substituted alkenyl, alkenyloxy, alkenylthio, alkinyl,
alkinyloxy or alkinylthio having in each case 2 to 6 carbon atoms in the
alkenyl- or alkinyl-groups, or represents respectively optionally cyano-,
fluorine-, chlorine-, bromine- or Cl-Cq.-alkyl-substituted cycloalkyl or
cycloalkylalkyl having in each case 3 to 6 carbon atoms in the
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cycloalkyl groups and optionally 1 to 6 carbon atoms in the alkyl
moiety,
R3 represents fluorine, chlorine or bromine,
R4 represents cyano or thiocarbamoyl and
RS represents the grouping -Al-A2-A3 ,
in which
A1 represents a single bond, represents oxygen, , sulphur, ~S0-,
-S02-, -CO- or the grouping -N-A4-, where A4 represents
hydrogen, hydroxyl, Cl-Cq-alkyl, Cg-Cq-alkenyl, C3-Cq-
alkinyl, Cl-Cq-alkoxy, phenyl, Cl-Cq-alkylsulphonyl or
phenylsulphonyl,
A1 furthermore represents respectively optionally fluorine-,
chlorine- or bromine-substituted Cl-C6-alkanediyl, C?-C6-
alkenediyl, C2-C6-azaalkenediyl, C2-C6-alkinediyl, C3-C6-
cycloalkanediyl, C3-C6-cycloalkenediyl or phenylene,
A2 represents a single bond, represents oxygen, sulphur; -SO-,
-S02-, -CO- or the grouping -N-A3-, where AS represents
hydrogen, hydroxyl, Cl-Cq-alkyl; Cl-Cq-alkoxy, phenyl, Cl-
Cq-alkylsulphonyl or phenylsulphonyl,
A2 furthermore represents respectively optionally fluorine-,
chlorine- or bromine-substituted Ct-C6-alkanediyl, C~
alkenediyl, C2-C6-azaalkenediyl, C2-C6-alkinediyl, C3-C6-
cycloalkanediyl, C3-C6-cycloalkenediyl or phenylene,
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A3 represents hydrogen, with the proviso that in this case A1
and/or A2 do not represent a single bond,
A3 furthermore represents hydroxyl, amino, cyano, isocyano,
thiocyanato, vitro, carboxyl, carbamoyl, thiocarbamoyl, sulpho,
chlorosulphonyl, fluorine, chlorine, bromine, represents
respectively optionally fluorine-, chlorine- or C 1-C4-alkoxy-
substituted alkyl, alkoxy, alkylthio, alkylsulphinyl, alkyl-
sulphonyl, alkylamino, dialkylamino, alkoxycarbonyl or
dialkoxy-(thio)phosphoryl having in each case 1 to 6 carbon
atoms in the alkyl groups, represents respectively optionally
fluorine- or chlorine-substituted alkenyl, alkenyloxy, alkenyl-
amino, alkylideneamino, alkenyloxycarbonyl, alkinyl, alkinyl-
oxy, alkinylamino or alkinyloxycarbonyl having in each case 2
to 6 carbon atoms in the alkenyl, alkylidene or alkinyl groups,
represents respectively optionally fluorine-, chlorine-, cyano-,
carboxyl-, C1-C4-alkyl- and/or C1-C4-alkoxy-carbonyl-sub-
stituted cycloalkyl, cycloalkyloxy, cycloalkylalkyl, cycloalkyl-
alkoxy, cycloalkylideneamino, cycloalkyloxycarbonyl or cyclo-
alkylalkoxycarbonyl having in each case 3 to 6 carbon atoms in
the cycloalkyl groups and optionally 1 to 4 carbon atoms in the
alkyl groups, or represents respectively optionally vitro- cyano-,
carboxyl-, fluorine-, chlorine-, bromine-, C1-C4-alkyl-, C1-C4-
halogenoalkyl-, C1-C4-alkyloxy-, C1-C4-halogenoalkyloxy-
and/or C1-C4-alkoxy-carbonyl-substituted phenyl, phenyloxy,
phenyl-C 1-C4-alkyl, phenyl-C 1-C4-alkoxy, phenyloxycarbonyl
or phenyl-Cl-C4-alkoxycarbonyl,
A3 furthermore represents respectively optionally fully or partially
hydrogenated pyrrolyl, pyrazolyl, imidazolyl, triazolyl, furyl,
oxiranyl, oxetanyl, dioxolanyl, thienyl, oxazolyl, isoxazolyl,
thiazolyl, isothiazolyl, oxadiazolyl, thiadiazolyl, pyridinyl,
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pyrimidinyl, triazinyl, pyrazolyl-C1-Cq-alkyl, furyl-C1-Cq.-alkyl,
thienyl-C1-Cq.-alkyl, oxazolyl-Cl-Cq.-alkyl, isoxazolyl-Cl-Cq.
alkyl, thiazolyl-C 1-Cq.-alkyl, pyridinyl-C 1-C4-alkyl, pyrimidi
nyl-C1-Cq.-alkyl, pyrazolylmethoxy, furylmethoxy, represents
s perhydropyranylmethoxy or pyridylmethoxy.
The invention in particular relates to compounds of the formula (~, in which
Q1 represents oxygen or sulphur,
Q2 represents oxygen or sulphur,
Rl represents hydrogen, cyano, amino, represents respectively optionally
cyano-, fluorine-, chlorine-, methoxy- or ethoxy-substituted methyl,
1 s ethyl, n- or i-propyl, n-, i- s- or t-butyl, methoxy, ethoxy, n- or i-
propoxy, n-, i-, s- or t-butoxy, methylamino, ethylamino, n- or i-
propylamino, n-, i-, s- or t-butylamino, dimethylamino, diethylamino,
acetyl, propionyl, n- or i-butyroyl, methoxycarbonyl, ethoxycarbonyl,
n- or i-propoxycarbonyl, represents respectively optionally fluorine-,
chlorine- or bromine-substituted propenyl, butenyl, propenylcarbonyl,
butenylcarbonyl, propenyloxycarbonyl, butenyloxycarbonyl, represents
propinyl, butinyl, propinylcarbonyl, butinylcarbonyl, propinyloxy-
carbonyl or butinyloxycarbonyl, or represents respectively optionally
cyano-, fluorine-, chlorine-, bromine-, methyl- or ethyl-substituted
2s cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylmethyl,
cyclobutylmethyl, cyclopentylmethyl or cyclohexyhnethyl,
R2 represents hydrogen, halogen, nitro, carboxyl, cyano, thiocarbamoyl,
amino, represents respectively optionally cyano-, fluorine-, chlorine-,
methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, n-, i- s-'or
t-butyl, methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy,
methylthio, ethylthio, n- or i-propylthio, n-, i-, s- or t-butylthio,
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methylamino, ethylamino, n- or i-propylamino, n-, i-, s- or t-
butylamino, dimethylamino or diethylamino, represents respectively
optionally fluorine-, chlorine- or - bromine-substituted propenyl,
propenyloxy, propenylthio, butenyl, butenyloxy or butenylthio,
represents propinyl, propinyloxy, propinylthio, butinyl, butinyloxy or
butinylthio, or represents respectively optionally cyano-, fluorine-,
chlorine-, bromine-, methyl- or ethyl-substituted cyclopropyl, cyclo-
butyl, cyclopemyl, cyclohexyl, cyclopropylmethyl, cyclobutylmethyl,
cyclopentylmethyl or cyclohexylmethyl,
f0
R3 represents fluorine or chlorine,
R4 represents cyano or thiocarbamoyl and
RS represents the grouping -A1-A2-A3 ,
in which
A~ represents a single bond, represents oxygen, sulphur, -SO-,
-S02-, -CO- or the grouping -N-A4- , where A4 represents
hydrogen, hydroxyl, methyl, ethyl, n- or i-propyl, methoxy,
ethoxy, n- or i-propoxy, methylsulphonyl or ethylsulphonyl,
Al furthermore represents methylene, ethane-l;l-diyl, ethane-l,2-
diyl, propane-l,l-diyl, propane-1,2-diyl, propane-1;3-diyl,
ethene-1,2-diyl, propene-1,2-diyl, propene-1,3-diyl, ethine-1,2-
diyl or propine-1,3-diyl,
A2 represents a single bond, represents oxygen, sulphur, -SO-;
-S02-, -CO- or the grouping -N-AS- , where A5 represents
hydrogen, hydroxyl, methyl, ethyl, n- or i-propyl, methoxy,
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ethoxy, n- or i-propoxy, methylsulphonyl, ethylsulphonyl, n- or
i-propylsulphonyl or phenylsulphonyl,
A2 furthermore represents methylene, ethane-l, l-diyl, ethane-1,2-
diyl, propane-l,l-diyl, propane-1,2-diyl, propane-1,3-diyl,
ethene-1,2-diyl, propene-1,2-diyl, propene-1,3-diyl, ethine-1,2-
diyl or propine-1,3-diyl,
A3 represents hydrogen, with the proviso that in this case A1
and/or A2 do not represent a single bond,
A3 furthermore represents hydroxyl, amino, cyano, nitro, carboxy,
carbamoyl, sulpho, fluorine, chlorine, bromine, represents
respectively optionally fluorine-, chlorine-, methoxy- or ethoxy-
substituted methyl, ethyl, n- or i-propyi, n- , i-, s- or t-butyl, n-,
i-, s- or t-pentyl, methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or
t-butoxy, n-, i-, s- or t-pentyloxy, methylthio, ethylthio, n- or i-
propylthio, n-, i-, s- or t-butylthio, methylsulphinyl, ethyl-
sulphinyl, n- or i-propylsulphinyl, methylsulphonyl, ethyl-
sulphonyl, n- or i-propylsulphonyl, methylamino, ethylamino, n-
or i-propylamino, n-, i-, s- or t-butylamino, dimethylamino,
diethylamino, methoxycarbonyl, ethoxycarbonyl, n- or i-
propoxycarbonyl, dimethoxyphosphoryl, diethoxyphosphoryl or
dipropoxyphosphoryl, diisopropoxyphosphoryl, represents
respectively optionally fluorine- or chlorine-substituted pro-
penyl, butenyl, propenyloxy, butenyloxy, propenylamino,
butenylamino, propylideneamino, butylideneamino, propenyl-
oxycarbonyl, butenyloxycarbonyl, propinyl, butinyl, pro-
pinyloxy, butinyloxy, propinylamino, butinylamino, propinyl-
oxycarbonyl or butinyloxycarbonyl, represents respectively
optionally fluorine-, chlorine-, cyano-, carboxyl-, methyl-,
ethyl-, n- or i-propyl-, methoxycarbonyl- or ethoxycarbonyl-
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substituted cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl,
cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy,
cyclopropylmethyl, cyclobutylinethyl, cyclopentylmethyl, cyclo-
hexylmethyl, cyclo-propylmethoxy, cyclobutylmethoxy, cyclo-
pentylmethoxy, cyclohexylmethoxy, cyclopentylideneamino,
cyclohexyl-ideneamino, cyclopentyloxycarbonyl, cyclohexyl-
oxycarbonyl, cyclopentylmethoxycarbonyl or cyclohexyl-
methoxycarbonyl, or represents respectively optionally nitro-,
cyano-, carboxyl-, fluorine-, chlorine-, bromine-, methyl-,
, ethyl-, n- or i-propyl-, trifluoromethyl-, methoxy-, ethoxy-, n-
or i-propoxy-, difluoromethoxy-, trifluoromethoxy-, methoxy-
carbonyl- and/or ethoxycarbonyl-substituted phenyl, phenyloxy,
benzyl, phenylethyl, benzyloxy, phenyloxycarbonyl, benzyloxy-
carbonyl,
A3 furthermore represents (in each case optionally fully or partially
hydrogenated) pyrrolyl, pyrazolyl, imidazolyl, triazolyl, furyl,
thienyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, oxadiazolyl,
thiadiazolyl, pyridinyl, pyrimidinyl, triazinyl, pyrazolylmethyl,
furylmethyl, thienylmethyl, oxazolylmethyl, isoxazolylmethyl,
thiazolylmethyl, pyridinylmethyl, pyrimidinylmethyl, pyrazolyl-
methoxy, furylmethoxy or pyridylmethoxy.
The general or preferred radical definitions listed above apply both to the
end
products of the formula (I) and, in a corresponding manner, also to the
starting
materials or intermediates which are required in each case for the
preparation. These
radical definitions can be combined with each other at will, i.e. combinations
between
the given preferred ranges are also possible.
Examples of the compounds of the formula (I) according to the invention are
listed in
the groups below.
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Cnroup 1
O / CH3
~- N
Ar- N O (IA-I)
~N -
H
Ar has in this case for example the meanings given below:
2-fluoro-S-chloro-4-cyano-phenyl, 2,5-dichloro-4-cyano-phenyl, 2-chloro-5-
fluoro-4-
cyano-phenyl, 2-chloro-4,5-dicyano-phenyl, 2,5-difluoro-4-cyano-phenyl, 2-
chloro-4-
cyano-5-methyl-phenyl, 2-fluoro-4-cyano-5-methyl-phenyl, 2-chloro-4-cyano-5-
tri-
fluoromethyl-phenyl, 2-fluoro-4-cyano-5-trifluoro-methyl-phenyl, 2,5-difluoro-
4-thio-
carbamoyl-phenyl, 2-fluoro-4-cyano-S-methoxy-phenyl, 2-fluoro-4-cyano-5-i-
propoxy-phenyl, 2-chloro-4-cyano-5-(2-propinyloxy)-phenyl, 2-fluoro-4-cyano-5-
(1-
methyl-2-propinyloxy)-phenyl, 2-chloro-4-thiocarbamoyl-5-i-propoxy-phenyl, 2-
fluoro-4-cyano-5-(2-propenyloxy)-phenyl, 2-chloro-4-cyano-5-methylsulphonyl-
amino-phenyl, 2-fluoro-4-cyano-S-ethylsulphonylamino-phenyl, 2-fluoro-4-thio-
carbamoyl-5-methylsulphonyl-phenyl, 2-chloro-4-cyano-5-ethylsulphonylamino-
I S phenyl, 2-fluoro-4-cyano-5-cyclopropylsulphonylamino-phenyl, 2-fluoro-4-
cyano-5-i-
propylsulphonylamino-phenyl, 2-chloro-4-thiocarbamoyl-5-ethylsulphonylamino-
phenyl, 2-chloro-4-cyano-5-cyano-amino-phenyl, 2-fluoro-4-cyano-5-
trifluormethyl-
sulphonylamino-phenyl, 2-fluoro-4-cyano-5-(2,2-difluorethylsulphonylamino)-
phenyl,
2-fluoro-4-cyano-5-phenylsulphonyl-amino-phenyl, 2-fluoro-4-cyano-5-t-butyl-
sulphonylamino-phenyl, 2-chloro-4-cyano-5-methoxycarbonyl-phenyl, 2-fluoro-4-
cyano-5-ethoxycarbonyl-phenyl, 2-fluoro-4-thio-carbamoyl-S-methoxycarbonyl-
phenyl, 2-chloro-4-cyano-5-(N-cyclopropyl-ethyl-sulphonylamino)-phenyl, 2-
fluoro-
4-cyano-5-(I-methyl-2-propinylthio)-phenyl, 2-fluoro-4-cyano-5-methylamino-
phenyl,
2-chloro-4-thiocarbamoyl-5-methoxycarbonylmethyl-phenyl, 2-chloro-4-cyano-5-(N-
methyl-ethylsulphonylamino)-phenyl, 2-chloro-4-cyano-5-i-propoxycarbonyl-
phenyl,
2-fluoro-4-cyano-5-(bis-ethylsulphonyl-amino)-phenyl, 2-fluoro-4-cyano-5-(N-
methylsulphonyl-ethylsulphonylamino)-phenyl, 2-fluoro-4-cyano-5-(1-methoxy-
carbonyl-ethoxy)-phenyl, 2-fluoro-4-cyano-5-cyclo-propyloxy-phenyl, 2-chloro-4-
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cyano-5-dimethylamino-phenyl, 2-fluoro-4-cyano-5-tetrahydrofurylmethoxy-
phenyl,
2-fluoro-4-cyano-5-amino-phenyl, 2-fluoro-4-cyano-5-methylaminocarbonyl-
phenyl,
2-fluoro-4-cyano-5-methylsulphonyloxy-phenyl, ' 2-chloro-4-cyano-5-difluoro-
methoxy-phenyl, 2-fluoro-4-cyano-5-ethoxycarbonylmethoxy-phenyl, 2-fluoro-4-
cyano-5-dimethylaminocarbonyl-phenyl, 2-fluoro-4-cyano-5-cyanomethoxy-phenyl,
2-
fluoro-4-cyano-5-(2-chloro-2-propenyloxy)-phenyl, 2-fluoro-4-cyano-5-hydroxy-
phenyl, 2-fluoro-4-cyano-S-vitro-phenyl, 2-fluoro-4-cyano-5-diethoxyphosphoryl-
amino-phenyl, 2-fluoro-4-cyano-5-chlorosulphonyl-phenyl, 2-fluoro-4-cyano-5-
formylamino-phenyl, 2-chloro-4-cyano-5-ethoxycarbonyloxy-phenyl, 2-fluoro-4-
cyano-5-diethoxyphosphorylmethoxy-phenyl, 2-chloro-4-cyano-5-hydroxy-phenyl, 2-
fluoro-4-cyano-5-(N,N-diacetyl-amino)-phenyl, 2-fluoro-4-cyano-5-acetylamino-
phenyl, 2-chloro-4-cyano-5-thiocyanato-phenyl, 2-fluoro-4-cyano-5-diethyl-
amino-
oxy-phenyl, 2-fluoro-4-cyano-5-tetrahydrofuryloxy-phenyl, 2-fluoro-4-cyano-5-
ureido-phenyl, 2-fluoro-4-cyano-5-dimethoxymethyleneamino-phenyl, 2-chloro-4-
cyano-5-ethoxymethyleneamino-phenyl, 2-fluoro-4-cyano-5-(2-chloro-ethoxy-
carbonyl-oxy)-phenyl, 2-chloro-4-cyano-5-dimethylaminomethyleneamino-phenyl, 2-
chloro-4-cyano-5-(perhydropyran-4-yloxy)-phenyl, 2-fluoro-4-cyano-5-(2-methoxy-
carbonyl-ethyl)-phenyl, 2-chloro-4-cyano-5-(2-carboxy-2-chloro-ethyl)-phenyl,
2-
fluoro-4-cyano-5-(2-chloro-2-methoxycarbonyl-ethyl)-phenyl, 2-fluoro-4-cyano-5-
(2-
chloro-2-s-butoxycarbonyl)-phenyl, 2-fluoro-4-cyano-5-(2-chloro-2-carbamoyl-
ethyl)-phenyl, 2-fluoro-4-cyano-5-(2-chloro-2-methoxycarbonyl-1-methyl-ethyl)-
phenyl, 2-fluoro-4-cyano-5-(1,2-dibromo-2-methoxycarbonyl-ethyl)-phenyl, 2-
chloro-
4-cyano-5-(2-chloro-2-i-propoxy-carbonyl-ethyl)-phenyl, 2-fluoro-4-cyano-5-(2-
carboxy-2-chloro-ethyl)-phenyl, 2-fluoro-4-cyano-5-(2-chloro-2-
ethylaminocarbonyl-
ethyl)-phenyl, 2-fluoro-4-cyano-5-(2-allylaminocarbonyl-2-chloro-ethyl)-
phenyl, 2-
fluoro-4-cyano-5-(2-ethoxycarbonyl-ethenyl)-phenyl, 2-fluoro-4-cyano-S-(2-
chloro-2-
cyclopropylaminocarbonyl-ethyl)-phenyl, 2-fluoro-4-cyano-5-(2-chloro-2-
dimethyl-
aminocarbonyl-ethyl)-phenyl, 2-chloro-4-cyano-5-(2-chloro-2-
ethylsulphonylamino-
carbonyl-ethyl)-phenyl, 2-fluoro-4-thiocarbamoyl-5-(2-ethylaminocarbonyl-
ethenyl)-
phenyl, 2-fluoro-4-cyano-5-(1-ethoxycarbonyl-ethyl)-phenyl, 2-chloro-4-cyano-5-
(1-
ethoxycarbonylethyl)-phenyl, 2-chloro-4-cyano-S-carboxy-phenyl, 2-fluoro-4-
cyano-
5-1-butoxy-phenyl, 2-chloro-4-cyano-5-1-butoxy-phenyl, 2-chloro-4-cyano-5-(2-
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methoxy-ethoxy)-phenyl, 2-fluoro-4-cyano-5-(2-oxetanyloxy)-phenyl, 2-fluoro-4-
cyano-5-(2-oxetanyloxycarbonylmethoxy)-phenyl, 2-fluoro-4-cyano-5-(2-oxetanyl-
oxy)-phenyl.
Group 2
N
C2H5
Ar - N O (IA-2)
~N -
H
Ar has in this case the meanings listed above in Group 1.
Group 3
O nCsH7
N (IA-3 )
Ar- N O
~N -
H
Ar has in this case the meanings listed above in Group 1.
Group 4
O / iC3H~
-- N
Ar- N O (IA-4)
N
H
Ar has in this case the meanings listed above in Group I .
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Group 5
O / C(CH3)3
-N
Ar - N O (IA-5)
N-
H
Ar has in this case the meanings listed above in Group 1.
Group 6
O H
-- N~
Ar - N O (IA-6)
N-
H
Ar has in this case the meanings listed above in Group 1.
Group 7
S CHs
N
Ar- N O (Ip,_~)
N-
H
Ar has in this case the meanings listed above in Group 1.
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Group 8
/ CH3
~-- N
Ar- N S (IA-8)
v
N-
H
Ar has in this case the meanings listed above in Group 1.
Group 9
/ CH3
O N
Ar - N\ S (IA-9)
N-
H
Ar has in this case the meanings listed above in Group 1.
Grog 10
O
~N
Ar- N O (IA-10)
N-
H
Ar has in this case the meanings listed above in Crroup 1.
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Group 11
O ~ CN
~- N
Ar- N O (IA-11)
N-
H
Ar has in this case the meanings listed above in Group 1.
Group 12
O / NHZ
~- N
Ar- N O (IA-12)
v
N-
H
Ar has in this case the meanings listed above in Group 1.
Group 13
O / NHCH3
-- N
Ar- N O (IA-13)
N-
H
Ar has in this case the meanings listed above in Group 1.
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Group 14
N(cH3)2
N (IA-14)
Ar-N O
v
N-
H
Ar has in this case the meanings listed above in Group 1.
Group 15
O
N (IA-15)
Ar-N O
N-
H
Ar has in this case the meanings listed above in Group 1.
Group 16
O
-- N
Ar- N O (IA-16)
N-
H
Ar has in this case the meanings listed above in Group 1.
i
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Group 17
/- CN
N
Ar- N O (IA-17)
N-
H
Ar has in this case the meanings listed above in Group 1.
Group 18
/- OCH3
N
Ar- N' O (IA-18)
N-
H
Ar has in this case the meanings listed above in Group 1.
Group 19
~- SCH3
N
Ar- N O (IA-19)
N-
H
Ar has in this case the meanings listed above in Group 1.
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Group 20
F
O
N (IA-20)
Ar-N O
N-
H
Ar has in this case the meanings listed above in Group 1.
Group 21
O
~-- N~ F
Ar- N O (IA-21)
N-
H
Ar has in this case the meanings listed above in Group 1.
Group 22
O CI-IFZ
N
Ar - N O (IA-22)
N-
H
Ar has in this case the meanings listed above in Group 1.
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Group 23
O CHF2
N
Ar- N O (IA-23)
N-
H
Ar has in this case the meanings listed above in Group 1.
Group 24
O / COOCH3
N
Ar - N O (IA-24)
N-
H
Ar has in this case the meanings listed above in Group 1.
Group 25
O / COOC2H$
~N
Ar- N\ O (IA-25)
N-
H
Ar has in this case the meanings listed above in Group 1.
i
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Group 26
O / COCH3
-- N
Ar- N O (IA-26)
N-
H
Ar has in this case the meanings listed above in Group I .
Group 27
COCF3
N (IA-27)
Ar-N O
N-
H
Ar has in this case the meanings listed above in Group 1.
Group 28
~- CFs
N
Ar - N O (IA-28)
N-
H
Ar has in this case the meanings listed above in Group 1.
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Group 29
O ~ C2F$
-N
Ar - N O (IA-29)
v
N-
H
Ar has in this case the meanings listed above in Group 1.
Group 3 0
O CHs
N
Ar- N O (IA-30)
N-
CH3
Ar has in this case the meanings listed above in Group 1.
Group 31
O / CzHs
~- N
Ar - N' O (IA-31 )
N-
CH3
Ar has in this case the meanings listed above in Group 1.
i
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Group 3 2
O / iC3H~
~N
Ar- N O (IA-32)
N-
CH3
Ar has in this case the meanings listed above in Group 1.
Group 3 3
~ CH3
~- N
Ar- N O (IA-33)
N-
CH3
Ar has in this case the meanings listed above in Group I .
Group 34
O CHs
i
N
Ar- N' S (IA-34)
N-
CH3
Ar has in this case the meanings listed above in Group 1.
_ CA 02246678 1998-08-19
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_32_
Group 3 5
S CHs
N/
Ar- N S (IA-35)
N-
CH3
Ar has in this case the meanings listed above in Group 1.
Group 3 6
O
N
Ar- N~ ~ (IA-36)
N-
CH3
Ar has in this case the meanings listed above in Group 1.
Group 3 7
a
p CN
i
N
Ar- N' O (IA-37)
N-
CH3
Ar has in this case the meanings listed above in Group 1.
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Group 3 8
NH2
N/
Ar- N O (IA-38)
v
N-
CHs
Ar has in this case the meanings listed above in Group 1.
Group 3 9
O NHCHs
~N/
Ar-N O (IA-39)
N-
CHs
Ar has in this case the meanings listed above in Group 1.
Group 40
O / N(CHs)2
~N
Ar - N O (IA-40)
N-
CHs
Ar has in this case the meanings listed above in Group 1.
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Group 41
O
~-- N
Ar-N O
N-
CH3 (IA-41)
Ar has m this case the meanings fisted above m Group 1.
Group 42
O
-- N
Ar- N O (IA-42)
N-
CH3
Ar has in this case the meanings listed above in Group 1.
Group 43
~- CN
N
Ar- N O (IA-43)
N-
CH3
Ar has in this case the meanings listed above in Group 1.
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Crroup 44
~-OCH3
N
Ar - N O (IA-44)
v
N-
CH3
S Ar has in this case the meanings listed above in Group I .
Group 45
O ~ SCH3
N
Ar- N O (IA-45)
N-
CH3
Ar has in this case the meanings listed above in Group 1.
Group 4G
F
O
N
Ar - N O (IA-46)
N-
CH3
Ar has in this case the meanings listed above in Group 1.
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Group 47
O ~
~- N~ F
Ar- N O
N-
CH3 (IA-47)
Ar has in this case the meanings listed above in Group 1.
Group 48
O / CHFZ
~- N
Ar - N O (IA-48)
N-
CH3
Ar has in this case the meanings listed above in Group 1.
Group 49
O / CH2F
-- N
Ar- N O (IA-49)
N-
CH3
Ar has in this case the meanings listed above in Group 1.
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Group 50
O / COOCH3
~- N
Ar- N O
(IA-50)
N -
CH3
Ar has in this case the meanings listed above in Group 1.
Group 51
O / COOC2H5
~N
Ar- N O (IA-51)
N-
CH3
Ar has in this case the meanings listed above in Group 1.
Group 52
O COCH3
N
Ar- N O (IA-52)
N-
CH3
Ar has in this case the meanings listed above in Group 1.
i
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Group 53
O COCF3
i
N
Ar- N O (IA-53)
N-
CH3
Ar has in this case the meanings listed above in Group 1.
Group 54
O ~- CF3
-N
Ar- N O
(IA-54)
N-
CH3
Ar has in this case the meanings listed above in Group 1.
Group 55
O ~ ZFs
~-- N
Ar-N O (IA-55)
N-
CH3
Ar has in this case the meanings listed above in Group I.
i
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Group 56
O H
~N ''
Ar- N O (1A_56)
N-
CF3
Ar has in this case the meanings listed above in Group 1.
o Group 57
O CHs
N~
Ar-N O
v
N-
CF3 (IA-57)
Ar has in this case the meanings listed above in Group 1.
Group 5 8
~ CzHs
N
Ar- N O
N - (IA-58)
CF3
Ar has in this case the meanings listed above in Group 1.
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Group 59
0 / IC3H7
~- N
Ar- N O (IA-59)
N-
CF3
Ar has in this case the meanings listed above in Group 1.
Group 60
O
~N
Ar - N O (TA-60)
N-
CF3
Ar has in this case the meanings listed above in Group 1.
Group 61
S CHs
i
N
Ar - N O (IA-61 )
N-
CF3
Ar has in this case the meanings listed above in Group 1.
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Crroup 62
~- N
Ar- N O (IA-62)
v
N-
CF3
Ar has in this case the meanings listed above in Group 1.
Group 63
CN
~- N
Ar- N O (IA-63)
N-
CF3
Ar has in this case the meanings listed above in Group 1.
Group 64
O CN
N
Ar- N O
(IA-64)
N-
CF3
Ar has in this case the meanings listed above in Group 1.
i
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Group 65
O NHS
N
Ar- N O (IA-65)
N-
CF3
Ar has in this case the meanings listed above in Group 1.
Group 67
O ~ N(CH3)2
-- N
Ar - N O (IA-67)
v
N-
CF3
Ar has in this case the meanings listed above in Group 1.
Group 68
O
-N
Ar- N O (IA-68)
N-
CF3
Ar has in this case the meanings listed above in Group 1.
i
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Group 69
O
~- N
Ar- N O (IA-69)
N-
CF3
Ar has in this case the meanings listed above in Group I.
Group 70
O /- OCH3
N
Ar - N~ O (IA-70)
N-
CF3
Ar has in this case the meanings listed above in Group 1.
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Group 71
O ~ SCH3 . _
-N
Ar- N O (IA-71)
N-
CF3
Ar has in this case the meanings listed above in Group 1.
Group 72
O ~-- CN
~- N
Ar- N ~ (IA-72)
N-
CF3
Ar has in this case the meanings listed above in Group 1.
Group 73
O F
~- N~
Ar- N O (IA-73)
v
N-
CF3
Ar has in this case the meanings listed above in Group I .
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Group 74
O ~--~
~- N F
Ar- N O (IA-74)
N-
CF3
Ar has in this case the meanings listed above in Group 1.
Group 75
O COOCH3
N/
Ar - N O (IA-75)
N-
CF3
Ar has in this case the meanings listed above in Group I .
Grou 76
COOC2H5
O
-- N
Ar - N O (IA-76)
N-
CF3
Ar has in this case the meanings listed above in Group 1.
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Group 77
O COCH3
N
Ar - N ~ (IA-77)
N-
CF3
Ar has in this case the meanings listed above in Group 1.
Group 78
O CHs
N
Ar- N O (IA-78)
N-
CZHS
Ar has in this case the meanings listed above in Group 1.
Group 79
O CH3
~- N/
Ar - N O (IA-79)
N-
-
Ar has in this case the meanings listed above in Group 1.
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Group 80
O CH3
~-- N~
Ar - N O (IA-80)
N-
iC3H~
Ar has in this case the meanings listed above in Group I .
Group 81
O ~ H3
-N
Ar- N O
v (IA-81 )
N-
Ar has in this case the meanings listed above in Group 1.
Group 82
O CHs
~N
Ar- N O (IA-82)
N-
CI
Ar has in this case the meanings listed above in Group 1.
i...
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Group 83
p /
CH3
~- N
Ar- N O (IA-83)
N-
Br
Ar has in this case the meanings listed above in Group 1.
Group 84
O CHs
~- N/
Ar- N O (IA-84)
N -
F
Ar has in this case the meanings listed above in Group 1.
Group 85
O CHs
N
Ar- N O (IA-85)
N-
COOH
Ar has in this case the meanings listed above in Group 1.
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Group 86
O CH3
~- N/
Ar- N O (IA-86)
N-
CN
Ar has in this case the meanings listed above in Crroup 1.
Group 87
O CHs
N
Ar - N O (IA-87)
N-
CSNHZ
Ar has in this case the meanings listed above in Group 1.
Group 88
O
~N F
Ar- N O (IA-88)
N-
CN
Ar has in this case the meanings listed above in Group 1.
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Group 89
O ~
~- N F
Ar- N ~ (IA-89)
N-
CSNH2
Ar has in this case the meanings listed above in Group 1.
Group 90
O CHs
~N
Ar - N O (IA-90)
N-
NOZ
Ar has in this case the meanings listed above in Group 1.
Group 9I
O CHs
N
Ar- N O (IA-91)
N-
NHZ
Ar has in this case the meanings listed above in Group 1.
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Group 92
O /CH3
-- N
Ar- N O (IA-92)
N-
NHCH3
Ar has in this case the meanings listed above in Group 1.
Group 93
O CH3
N
Ar- N' -O (IA-93)
N-
N(CH3)2
Ar has in this case the meanings listed above in Group 1.
Group 94
O /CH3
~N
Ar- N! O (IA-94)
v
N-
OCH3
Ar has in this case the meanings listed above in Group I .
_ CA 02246678 1998-08-19
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Group 95
O CH3
~- N/
Ar- N O (IA-95)
v
N- S
Ar has in this case the meanings listed above in Group 1.
Group 96
O CH3
~N/
Ar- N O (IA-96)
N-
O
Ar has in this case the meanings listed above in Group 1.
Group 97
O CHs
-- N~
Ar- N O (IA-97)
N-
OCH3
Ar has in this case the meanings listed above in Group 1.
i
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Groun 98
/ CH3
~-- N
Ar-N O (IA-98)
N - ,
CN
Ar has in this case the meanings listed above in Group 1.
Using, for example, 4,6-diethyl-1,2,4-triazine-3,5(2H,4H)-dione and 2,4,5-
trifluoro-
benzonitrile as starting materials, the course of the reaction in the process
(a)
according to the invention can be illustrated by the following equation:
F CZHs C2Hs
O
F O F N
/ N ~ _. I
N~N
z s
NC \ I + ~N N~ H / ~' II \C H
H ~ CzHs \ O
F O NC
F
Using, for example, 2-(4-cyano-S-ethoxy-2-fluoro-phenyl)-6-trifluoromethyl-
1,2,4
triazine-3,5(2H,4H)-dione and ethylbromide as starting materials, the course
of the
reaction in the process (b) according to the invention can be illustrated by
the
following equation:
CF3 CF3
O O
F N~ +C H-Br F N
/ ~N N\ ~ / N N~
H - HBr \ ~ ~ C2Hs
NC NC
OC~Hs OC2Hs
i
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Using, for example, acetone N-(5-chloro-4-cyano-2-fluoro-phenyl)-hydrazone and
potassium thiocyanate and, in the subsequent step, pyruvic acid as starting
materials,
the course of the reaction in the process (c) according to the invention can
be
illustrated by the following equation:
CH ' CH3
F N ~ CH3 F NON
NH + KSCN N ~C
/ I ~ / I S
NC
NC
CI CI CH3
O.
F N
+CH3C0-CO-OH / iN~N~H
NC
CI
Using, for example, 4-amino-3-fluoro-2-methylthio-benzonitrile and ethyl cyano
acetylcarbamate as starting materials, the course of the reaction in the
process (d)
according to the invention can be illustrated by the following equation:
CN
F O
NHZ H F N
I
+ N O~ --1 / NH ~N~
NC NC ~ ~ CZHS I H
SCH3 O O NC ~ OC2H5
SCH3
CN
O
F N
I N
- HOC~H$ /
H
NC ~ I O
SCH3
_ CA 02246678 1998-08-19
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Using, for example, 2-chloro-4-cyano-5-methyl-phenylhydrazine and methyl
pyruvate
and, in the subsequent step, ethyl isothiocyanate as starting materials, the
course of
the reaction in the process (e) according to the invention can be illustrated
by the
following equation:
CH3
CI NH2
NH CI N
/ ~ + CH3 CO-CO-OCH3 / I
NH ~CH3
NC \
CH3 NC
CH3
CH3 CH3
O
CI N ~O CI N
+ S=C=N-CZHs ( OCH3 N N
/ N _,
~T NH - H H / ~ ~ \ CZHs
NC \ S ~ 3NC ~ S
CH3 CZHs CH3
Using, for example, 4-amino-2,5-dichloro-benzonitrile and sodium
nitrite/hydrochloric
acid and, in the subsequent step, malonyldiethylurethane as starting
materials, the
course of the reaction in the process (f) according to the invention can be
illustrated
by the following equation:
CI CI
/ NHZ NaNOz/HCI / Nz+CI
NC ~ NC \ H
CI
CI CI N ~O
+ CH2(CO-NH-COOCZHS)2 / i N ~ N w H
\ l O
NC
CI
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The formula (II) provides a general definition of the 1,2,4-triazine-3,5-
di(thi)ones to
be employed as starting materials in the process (a) according to the
invention for
preparing compounds of the formula (I). In the formula (II), Q1, Q2, R1 and R2
each
preferably or in particular have those meanings which have already been
indicated
above, in connection with the description of the compounds of the formula (I)
according to the invention, as being preferred or particularly preferred for
Ql, Q2, Rl
and R2.
The starting materials of the formula (II) are known and/or can be prepared by
known
methods (cf.. J. Am. Chem. Soc. 80 (1958), 976; J. Heterocycl. Chem. 16
(1979),
1649; J. Org. Chem. 23 (1958), 1951-1953).
The formula (IIl~ provides a general definition of the halogenobenzene
derivatives
furthermore to be used as starting materials in the process (a) according to
the
invention. In the formula (III), R3, R4 and RS each preferably or in
particular have
those meanings which have already been indicated above, in connection with the
description of the compounds of the formula (I) according to the invention, as
being
preferred or particularly preferred for R3, R4 and R5; X1 preferably
represents
fluorine, chlorine or bromine, in particular fluorine.
The starting materials of the formula (III) are known and/or can be prepared
by
processes known per se (cf. EP 191181, EP 370332, EP 431373, EP 441004).
The formula (Ia) provides a general definition of the 2-aryl-1,2,4-triazine-
3,5-di(thi)-
ones to be employed as starting materials in the process (b) according to the
invention. In the formula (Ia), Q1, Q2, R2 , R3, R4 and RS each preferably or
in
particular have those meanings which have already been indicated above, in
connection with the description of the compounds of the formula (I) according
to the
invention, as being preferred or particularly preferred for Q1, Q2, R2 , R3,
R4 and
R5.
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The starting materials of the formula (Ia) are novel compounds according to
the
invention; they can be prepared by the processes (a) and (c) to (f) according
to the
invention.
The formula (IV) provides a general definition of the alkylating agents
furthermore to
be employed as starting materials in the process (b) according to the
invention. In the
formula (IV), Rl preferably or in particular has those meanings which have
already
been indicated above, in connection with the description of the compounds of
the
formula (I) according to the invention, as being preferred or particularly
preferred for
Ri; X2 preferably represents fluorine, chlorine, bromine, iodine,
methoxysulphonyloxy
or ethoxysulphonyloxy, in particular chlorine or bromine.
The starting materials of the formula (IV) are known organic chemicals for
synthesis.
The formula (V) provides a general definition of the arylhydrazones to be
employed ~as
starting materials in the process (c) according to the invention for preparing
compounds of the formula (I). In the formula (V), R3, R4 and RS each
preferably or
in particular have those meanings which have already been indicated above, in
connection with the description of the compounds of the formula (I) according
to the
invention, as being preferred or particularly preferred for R3, R4 and R5.
The starting materials of the formula (V) are known and/or can be prepared by
known
processes (cf. WO 86/00072, US 4956004).
The formula (VI) provides a general definition of the alkali metal
(thio)cyanates
furthermore to be employed as starting materials in the process (c) according
to the
invention. In the formula (VI), Q 1 preferably or in particular has those
meanings
which have already been indicated above, in connection with the description of
the
compounds of the formula (I) according to the invention, as being preferred or
particularly preferred for Q 1 ~ M preferably represents lithium, sodium,
potassium,
rubidium or caesium, in particular sodium or potassium.
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The starting materials of the formula (VI) are known chemicals for synthesis.
The formula (VIII) provides a general definition of the ketocarboxylic acids
furthermore to be employed as starting materials in the process (c) according
to the
invention. In the formula (VIII, R2 preferably or in particular has those
meanings
which have already been indicated above, in connection with the description of
the
compounds of the formula (I) according to the invention, as being preferred or
particularly preferred for R2.
The starting materials of the formula (VIII are known organic chemicals for
synthesis.
The formula (IX) provides a general definition of the aryl amines to be
employed as
starting materials in the processes (d) and (fj according to the invention for
preparing
compounds of the formula (I). In the formula (IX), R3, R4 and RS each
preferably or
in particular have those meanings which have been indicated above, in
connection
with the description of the compounds of the formula (I) according to the
invention,
as being preferred or particularly preferred for R3, R4 and R5.
The starting materials of the formula (IX) are known and/or can be prepared by
known processes (cf. EP 224001, EP 303573, DE 3835168, EP 40389I).
The formula (X) provides a general definition of the cyanoacetylcarbamic acid
esters
furthermore to be employed as starting materials in the process (d) according
to the
invention. In the formula (X), Rl preferably or in particular has those
meanings which
have already been indicated above, in connection with the description of the
compounds of the formula (I) according to the invention, as being preferred or
particularly preferred for Rl.
The starting materials of the formula (X) are known organic chemicals for
synthesis.
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The formula (XII) provides a general definition of the arylhydrazines to be
employed
as starting materials in the process (e) according to the invention for
preparing
compounds of the formula (I). In the formula (XII), R3, R4 and RS each
preferably or
in particular have those meanings which have already been indicated above, in
connection with the description of the formula (I) according to the invention,
as being
preferred or particularly preferred for R3, R4 and R5.
The starting materials of the formula (XII) are known and/or can be prepared
by
known processes (cf. EP 370332).
The formula (XIII) provides a general definition of the ketocarboxylic acid
derivatives
furthermore to be employed as starting materials in the process (e) according
to the
invention. In the formula (XIII), R2 preferably or in particular has those
meanings
which have already been indicated above, in connection with the description of
the
compounds of the formula (I) according to the invention, as being preferred or
particularly preferred for R2~ R preferably represents hydrogen or Cl-Cq.-
alkyl, in
particular hydrogen, methyl or ethyl.
The starting materials of the formula (XIII) are known organic chemicals for
synthesis.
The formula (X~ provides a general definition of the iso(thio)cyanates
furthermore
to be employed as starting materials in the process (e) according to the
invention. In
the formula (X~, Q1 and R1 preferably or in particular have those meanings
which
have already been indicated above, in connection with the description of the
compounds of the formula (I) according to the invention, as being preferred or
particularly preferred for Q 1 and R1.
The starting materials of the formula (X~ are known chemicals for synthesis
The malonyldiurethane of the formula (XVII) to be employed as starting
material in
the process according to the invention is a known chemical for synthesis.
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Suitable diluents for carrying out the processes (a) to (f) according to the
invention
are in particular inert organic solvents. These include in particular
aliphatic, alicyclic
or aromatic, optionally halogenated hydrocarbons, such as, for example,
benzine,
benzene, toluene, xylene, chlorobenzene, dichlorobenzene, petroleum ether,
hexane,
cyclohexane, dichloromethane, chloroform, carbon tetrachloride; ethers, such
as
diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran or ethylene glycol
dimethyl
ether or ethylene glycol diethyl ether; ketones, such as acetone, butanone or
methyl
isobutyl ketone; nitrites, such as acetonitrile, propionitrile or
butyronitrile; amides,
such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-formanilide, N
methyl-pyrrolidone or hexamethylphosphoric triamide; esters such as methyl
acetate
or ethyl acetate, sulphoxides, such as dimethyl sulphoxide, alcohols, such as
methanol,
ethanol, n- or i-propanol, ethylene glycol monomethyl ether, ethylene glycol
monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol
monoethyl
ether, mixtures thereof with water or pure water.
Suitable reaction auxiliaries for the processes (a) to (f) are generally the
customary
inorganic or organic bases or acid accepters. These preferably include alkali
metal or
alkaline earth metal acetates, amides, carbonates, bicarbonates, hydrides,
hydroxides
or alkoxides, such as, for example, sodium acetate, potassium acetate or
calcium
acetate, lithium amide, sodium amide, potassium amide or calcium amide, sodium
carbonate, potassium carbonate or calcium carbonate, sodium bicarbonate,
potassium
bicarbonate or calcium bicarbonate, lithium hydride, sodium hydride, potassium
hydride or calcium hydride, lithium hydroxide, sodium hydroxide, potassium
hydroxide or calcium hydroxide, sodium methoxide or potassium methoxide,
sodium
ethoxide or potassium ethoxide, sodium n- or i-propoxide or potassium n- or i-
propoxide, sodium n-, or i-, s- or t-butoxide or potassium n-, i-, s- or t-
butoxide;
furthermore also basic organic nitrogen compounds, such as, for example,
trimethylamine, triethylamine, tripropylamine, tributylamine, ethyl-
diisopropylamine,
N,N-dimethyl-cyclohexylamine, dicyclohexylamine, ethyl-dicyclohexylamine, N,N-
di-
methyl-aniline, N,N-dimethyl-benzylamine, pyridine, 2-methyl-, 3-methyl-, 4-
methyl-,
2,4-dimethyl-, 2,6-dimethyl-, 3,4-dimethyl- and 3,5-dimethyl-pyridine, 5-ethyl-
2-
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methyl-pyridine, 4-dimethylamino-pyridine, N-methyl-piperidine, 1,4-
diazabicyclo-
[2,2,2]-octane (DABCO), 1,5-diazabicyclo[4,3,0]-non-5-ene (DBN), or 1,8-diaza-
bicyclo[5,4,0]-undec-7-ene (DBU).
S When carrying out the processes (a) to (f) according to the invention, the
reaction
temperatures can be varied within a relatively wide range. In general,
temperatures of
between -20°C and +150°C, preferably between 0°C and
+120°C, are employed.
The processes (a) to (f) according to the invention are generally carried out
under
atmospheric pressure. However, it is also possible to carry out the processes
according to the invention under elevated or reduced pressure - in general
beween 0,1
bar and 10 bar.
In the practice of the processes (a) to (f) according to the invention, the
starting
materials are generally employed in approximately equimolar amounts. However,
it is
also possible to use in each case one of the components in a relatively large
exess. The
reaction is generally carried out in a suitable diluent in the presence of a
reaction
auxiliary, and the reaction mixture is generally stirred for a number of hours
at the
temperature required. Work-up is carried out by customary methods (cf. the
Preparation Examples).
The active compounds according to the invention can be used as defoliants,
desiccants, haulm killers and, especially as weed killers. By weeds in the
broadelst
sense, there are to be understood all plants which grow in locations where
they are
undesirable. Whether the substances according to the invention act as total or
selective herbicides depends essentially on the amount used.
The active compounds according to the invention can be used, for example, in
connection with the following plants:
Dicotyledonous weeds of the eg nera: Sinapis, Lepidium, Galium, Stellaria,
Matricaria,
Anthemis, Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca,
_ i
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Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsium,
Carduus, Sonchus, Solarium, Rorippa, Rotala, Lindernia, Lamium, Veronica,
Abutilon, Emex, Datura, Viola, Galeopsis, Papaver, Centaurea, Trifolium,
Ranunculus
and Taraxacum.
Dicotyledonous crops of the eg nera: Gossypium, Glycine, Beta, Daucus,
Phaseolus,
Pisum, Solarium, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis,
Brassica,
Lactuca, Cucumis and Cucurbita.
Monocotyledonous weeds of the genera: Echinochloa, Setaria, Panicum,
Digitaria,
Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus, Avena, Cyperus,
Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleocharis,
Scirpus, Paspalum, Ischaemum, Sphenoclea, Dactyloctenium, Agrostic, Alopecurus
and Apera. ,
Monocotyledonous crops of the genera: Oryza, Zea, Triticum, Hordeum, Avena,
Secale, Sorghum, Panicum, Saccharum, Ananas, Asparagus and Allium.
However, the use of the active compounds according to the invention is in no
way
restricted to these genera, but also extends in the same manner to other
plants.
The compounds are suitable, depending on the concentration, for the total
control of
weeds, for example on industrial terrain and railway tracks, and on paths and
squares
with or without tree plantings. Equally, the compounds can be employed for
controlling weeds in perennial cultures, for example forests, 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, on lawns, turf and pasture-
land, and for
the selective control of weeds in annual cultures.
The compounds of the formula (I) according to the invention are suitable in
particular
for selectively controlling monocotyledonous and dicotyledonous weeds in
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monocotyledonous and docotyledonous crops, both pre-emergence and post-
emergence.
The active compounds can be converted into the customary formulations, such as
solutions, emulsions, wettable powders, suspensions, powders, dusting agents,
pastes,
soluble powders, granules, suspo-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 surfactants, that is emulsifiers and/or dispersing
agents
and/or foam-forming agents.
If the extender used is water, it is also possible to employ for example
organic
solvents as auxiliary solvents. Essentially, suitable liquid solvents are:
aromatics, such
as xylene, toluene or alkylnaphthalenes, chlorinated aromatics and chlorinated
aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methyleme
chloride, aliphatic hydrocarbons, such as cyclohexane or paraffns, for example
petroleum fractions, mineral and vegetable oils, alcohols, such as butanol or
glycol
and their ethers and esters, ketones, such as acetone, methyl ethyl ketone,
methyl
isobutyl Icetone or cyclohexanone, strongly polar solvents, such as
dimethylformamide
and dimethyl sulphoxide and water.
Suitable solid carriers are: for example ammonium salts and ground natural
minerals,
such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or
diato-
maceous earth, and ground synthetic minerals, such as finely divided silica,
alumima
and silicates, suitable solid carriers for granules are: for example crushed
arid
fractionated natural rocks such as calcite, marble, pumise, 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;
suitable
emulsifiers and/or foam-forming agents are: for example nonionic and anionic
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emulsifers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty
alcohol
ethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkyl
sulphates,
arylsulphonates as well as protein hydrolysates; suitable dispersing agents
are: for
example lignin-sulphite waste liquors and methylcellulose.
Tackifiers such as carboxymethylcellulose and natural synthetic polymers in
the form
of powders, granules or latexes, such as gum arabic, polyvinyl alcohol and
polyvinyl
acetate, as well as natural phospholipids, such as cephalins and lecithins,
and synthetic
phospholipids, can be used in the formulations. Further additives can be
mineral and
vegetable oils.
i
It is possible to use colorants such as inorganic pigments, for example iron
oxide,
titanium oxide and Prussian Blue, and organic dyes, such as alizarin dyes, azo
dyes
and metal phthalocyanine dyes, and trace nutrients such as salts of iron,
manganese,
boron, copper, cobalt, molybdenum and zinc.
The formulations in general contain between 0.1 and 95 per cent by weight of
active
compound, preferably between 0.5 and 90%.
For controlling weeds, the active compounds according to the invention, as
such or in
the form of their formulations, can also be used as mixtures with known
herbicides,
finished formulations or tank mixes being possible.
Possible components for the mixtures are known herbicides, for example
anilides,
such as diflufenican and propanil; arylcarboxylic acids, such as
dichloropicolinic acid,
dicamba and picloram; aryloxyalkanoic acids, such as 2,4-D, 2,4-DB, 2,4-DP,
fluroxypyr, MCPA, MCPP and triclopyr; aryloxy-phenoxy-alkanoic esters, such as
diclofop-methyl, fenoxaprop-ethyl, fluazifop-butyl, haloxyfop-methyl and
quizalofop-
ethyl; azinones, such as chloridazon and norflurazon; carbamates, such ~as
chlorpropham, desmedipham, phenmedipham and propham; chloroacetanilides, such
as alachlor, acetochlor, butachlor, metazachlor, metolachlor, pretilachlor and
propachlor; dinitroanilines, such as oryzalin, pendimethalin and trifluralin;
diphenyl
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ethers, such as acifluorfen, bifenox, fluoroglycofen, fomesafen, halosafen,
lactofen and
oxyfluorfen; ureas such as chlorotoluron, diuron, fluometuron, isoproturon,
linuron
and methabenzthiazuron; hydroxylamines, such as alloxydim, clethodim,
cycloxydim,
sethoxydim and tralkoxydim; imidazolinones, such as imazethapyr,
imazamethabenz,
imazapyr and imazaquin; nitrites, such as bromoxynil, dichlobenil and ioxynil;
oxyacetamides, such as mefenacet; sulphonylureas, such as amidosulfuron,
bensulfuron-methyl, chlorimuron-ethyl, chlorsulfuron, cinosulfuron,
metsulfuron-
methyl, nicosulfuron, primisulfuron, pyrazosulfuron-ethyl, thifensulfuron-
methyl,
triasulfitron and tribenuron-methyl; thiocarbamates, such as butylate,
cycloate,
diallate, EPTC, esprocarb, molinate, prosulfocarb, thiobencarb and triallate;
triazines,
such as atrazine, cyanazine, simazine, simetryne, terbutryne and
terbutylazine;
triazinones, such as hexazinone, metamitron and metribuzin; and others, such
as
aminotriazole, benfuresate, bentazone, cinmethylin, clomazone, clopyralid,
difenzo-
quat, dithiopyr, ethofumesate, fluorochloridone, glufosinate, glyphosate,
isoxaben,
pyridate, quinchlorac, quinmerac, sulfosate and tridiphane.
Mixtures with other known active compounds, such as fungicides, insecticides,
acaricides, nematicides, bird repellants, plant nutrients and agents which
improve soil
structure, are also possible.
The active compounds can be used as such, in the form of their formulations or
in the
use forms prepared therefrom by further dilution, such as ready-to-use
solutions,
suspensions, emulsions, powders, pastes and granules. They are used in the
customary
manner, for example by watering, spraying, atomizing or scattering.
The active compounds according to the invention can be applied either before
or after
emergence of the plants. They can also be incorporated into the soil before
sowing.
The amount of active compound used can vary within a substantial range. It
depends
essentially on the nature of the desired ef~'ect. In general, the amounts used
are
between 1 g and 10 kg of active compound per hectare of soil surface,
preferably
between 5 g and 5 kg per ha.
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The preparation and use of the active compounds according to the invention can
be
seen from the Examples below.
Preparation Examples:
Example 1:
F O ~ NHz
-- N
NC ~ ~ N O
N-
F CHs
At 70°C, 7.1 g (50 mMol) of 4-amino-6-methyl-1,2,4-triazine-3,5(2H,4H)-
dione,
6.9 g (50 mMol) of potassium carbonate and 7.9 g (50 mMol) of 2,4,5-Trifluoro-
benzonitrile in 100 ml of dimethyl sulphoxide axe stirred for 4 hours, the
mixture is
subsequently cooled to room temperature and stirred into ice-water and
precipitated
product is filtered oil with suction, dried and recrystallized from ethanol.
2.9 g (20 % of theory) of 2-(2,4-difluoro-4-cyano-phenyl)-4-amino-4-methyl-
1,2,4-
triazine-3,5(2H,4H)-dione of melting point 125°C are obtained.
Example 2:
F O H
N
NC ~ ~ N O
N-
F
CHs
At 120°C, 2.54 g (20 mMol) of 6-methyl-1,2,4-triazine-3,5(2H,4H)-dione
in 50 ml of
dimethyl sulphoxide are stirred with 2.8 g (20 mMol) of potassium carbonate
and
3.14 g (20 mol) of 2,4,5-trifluoro-benzonitrile for 12 hours, the mixture is
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subsequently cooled to room temperature and stirred with water, the pH is
adjusted to
using hydrochloric acid and precipitated product is filtered off with suction,
stirred
with water and dried.
5 4.6 g (87% of theory) of 2-(2,4-difluoro-4-cyano-phenyl)-6-methyl-1,2,4-
triazine-
3,5(2H,4H)-dione of melting point 214°C are obtained.
Example 3:
H
F O
-- N
NC ~ ~ N O
N-
O
CH3
5.2 g {20 mMol) of 2-(2,4-difluoro-4-cyano-phenyl)-6-methyl-1,2,4-triazine-
3,5(2H,4H)-dione are initially charged in 50 ml of acetonitrile with 2.8 g (40
mMol)
of 3-butin-2-ol, and at room tempeature (about 20°C), the mixture is
mixed a little at
a time with 1.15 g (40 mMol) of sodium hydride (80% strength in paraffin) and
the
mixture is stirred at room temperature for 12 hours. The mixture is
concentrated
under reduced pressure, the residue is stirred with water, the pH is adjusted
to 5 using
concentrated hydrochloric acid and the precipitated product is isolated by
filtration.
5.8 g (92 % of theory) of 2-(2-fluoro-4-cyano-5-but-1-in-3-yl-oxy-phenyl)-6-
methyl-
1,2,4-triazine-3,5(2H,4H)-dione of melting point 153°C (decomp.) are
obtained.
Example 4:
F O ~ C'2H5
~- N
NC ~ ~ N O
N-
O
CH3
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At room temperature (about 20°C), 1.6 g (5 mMol) of 2-(2-fluoro-4-cyano-
5-but-1-
in-3-yl-oxy-phenyl)-6-methyl-1,2,4-triazine-3,5(2H,4H)-dione in 50 ml of
dimetliyl
sulphoxide are stirred with 1.38 g (10 mMol) of potassium carbonate and 1.56 g
(10 mMol) of ethyl iodide for 12 hours. The mixture is concentrated under
reduced
pressure, the residue is stirred with water, the pH is adjusted to 5 using
concentrated
hydrochloric acid and the precipitated product is isolated by filtration.
1.6 g (93.5% of theory) of 2-(2-fluoro-4-cyano-5-but-1-in-3-yl-oxy-phenyl)-4-
ethyl-
6-methyl-1,2,4-triazine-3,5(2H,4H)-dione of melting point 139°C are
obtained.
Similar to Preparation Examples 1 to 4 and in accordance with the general
description
of the preparation processes according to the invention, it is also possible,
for
example, to prepare the compounds of the formula (I) listed in Table 1 below.
R3 Q~ R~
N/
R4 ~ Qz
v
N-
Rs Rz (I)
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'Fable 1: Examples of compounds of the general formula (I)
Ex.R1 R~ Q1 Q R' R'* R' Physical
No. 2 Data
NH2 C(CH3)3O O F CN F Mp.:120C
6 H H O O F CN F Mp.: >250C
a
7 H CH3 O O F CN F Mp.:130C
8 CH3 CH3 O O F CN OCH(CH3)C---CHMp.:102C
9 H H O O F CN OCH(CH3)C=CH Mp.:202C
CH3 H O O F CN OCH(CH3)C---CHMp.:129C
11 H H O O F CN NHS02C2H5 Mp.:121C
(Decomp.)
i
12 H H O O F CN OCH2-C---CH Mp.:175C
13 CH3 H O O F CN OCH2-C=CH Mp.: 137C
14 CH3 H O O F CN NHS02C2H5 Mp.:187C
[contains
about
30%-N(CH3)-]
CH3 H O O F CN OCH2CH=CH2 Mp.:139C
16 CH(CH3)2 CH3 O O F CN OCH(CH3)C=CH Mp.:112C
17 C2H5 H O O F CN OC2H5 Mp.:142C
18 C2H5 H O O F CN OCH2-C=CH 1H NMR:
19 C2H5 H O O F CN OCH(CH3)C---CHMp.:132C
CH(CH3)2 H O O F CN OCH(CH3)C---CHMp.:70C
21 H H O O F CN OC2H5 Mp.:150C
22 H H O O F CN OH Mp.:220C
23 CH2CH2F H O O F CN OCH(CH3)C=CH
24 (CH2)3F H O O F CN OCH(CH3)C---CH
CH2-C---CHH O O F CN OCH(CH3)C---CHMp.:132C
26 CH2CH2F CH3 O O F CN OCH(CH3)C---CHMp.:119C
27 (Cl-I2)3F CH3 O O F CN OCH(CH3)C---CHMp.:115C
28 Cl-I3 CH3 O O F CN NHS02C2H5 Mp.:129C
29 CH2CH=CH2 H O O F CN OCH(CH3)C---CHMp.:84C
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Ex.R 1 R~ Q Q R~ Ry' R~ Physical
No. 1 2 Data.
30 CH3 CH3 O O F CN NHS02CH3 Mp.:115C
I
31 (CH2)3F H O O F CN F Mp.:85C
32 H CH3 O O F CN NHS02CH3 Mp.:140
33 (CH2)3F CH3 O O F CN NHS02CH3 Mp.: 108C
34 CH3 H O S F CN OCH(CH3)C---CH(amorphous)
35 CH2CH2F H O O F CN OCH2C=CH Mp.:135C
36 (cH2)2cF=cF2H O O F CN OCH2C=CH (amorphous)
37 (CH2)3F H O O F CN OCH2C~CH Mp.:126C
38 (cH2)zcF-cF2H O O F CN NHS02C2H5 Mp.:88C
39 (CH2)3F CH3 O O F CSNH2 NHS02CH3 Mp.: >210C
40 C2H5 H O O F CN N(C2H5)S02C2H5Mp.: 154C
41 CH3 H O O F CN N(CH3)S02C2H5Mp.:91C
42 H H O O F CN N(S02C2H5)2 Mp.: >250C
43 CH3 H O O F CN N(S02C2H5)2 Mp.:164C
44 CH3 H O O F CN NHS02C2H5 Mp.:233C
,
45 CH2CH2F H O O F CN NHS02C2H5 Mp.:190C
46 (CH2)3F H O O F CN NHS02C2H5 Mp.:98C
47 (CH2)3F H O O F CN NHS02CH3 Mp.:186C
48 CH2CH2F H O O F CN NHS02CH3 Mp.:178C
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Use examples:
Examnte A
Pre-emergence Test
Solvent: 5 parts by weight of acetone
Emulsifier: 1 part by weight of alkylaryl polyglycol ether
To produce a suitable preparation of active compound, 1 part by weight of
active
compound is mixed with the stated amount of solvent, the stated amount of
emulsifier
is added and the concentrate is diluted with water to the desired
concentration.
Seeds of the test plants are sown in normal soil. After about 24 hours, the
soil is
watered with the preparation of the active compound. Advantageously, the
amount of
water per unit area is kept constant. The active compound concentration in the
preparation is not important, only the active compound application rate per
unit area
matters.
After three weeks, the degree of damage to the plants is rated in % damage in
comparison with the development of the untreated control.
The figures denote:
0 % - no effect (like untreated control)
100 % - total destruction
In this test, for example, the compounds of Preparation Example 7, 8, 10, 17,
18 and
19 exhibit, at an application rate between 60 and 125 g/ha, very strong
activity against
weeds such as Alopecurus (70 to 100 %), Digitaria (70 to 100 %), Sorghum (70
to
100 %), Amaranthus (100 %), Chenopodium (100 %) and Solanum (100 %), and
they are tolerated well by crops, such as, for example, wheat (up to 20 %),
barley (0
to 10 %), Maize (0 %), Soya (10 to 20 %) and cotton (0 to 30 %).
i
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Example B
Post-emergence Test
Solvent: 5 parts by weight of acetone
Emulsifier: 1 part by weight of alkylaryl polyglycol ether
To produce a suitable preparation of active compound, 1 part by weight of
active
compound is mixed with the stated amount of solvent, the stated amount of
emulsifier
is added and the concentrate is diluted with water to the desired
concentration.
Test plants which have a height of 5-l5cm are sprayed with the preparation of
the
active compound in such a way as to apply the particular amounts of active
compound
desired per unit area. The concentration of the spray liquor is chosen so that
the
particular amounts of active compound desired are applied in 10001 of
water/ha.
After three weeks, the degree of damage to the plants is rated in % damage ~in
comparison with the development of the untreated control.
The figures denote:
0 % = no effect (like untreated control)
100 % = total destruction
In this test, for example, the compounds of Preparation Example 7, 8 and 10
exhibit,
at outwall rates between 60 and 125 g/ha, very strong activity against weeds
such 'as
Digitaria (70 to 95 %), Echinochloa (80 to 100 %), Setaria (70 to 100 %),
Datura
(100 %), Solanum (100 %) and Viola (100 %), and they are well tolerated by
crops,
such as, for example, wheat (0 to 10%) and barley (0%).
