Note: Descriptions are shown in the official language in which they were submitted.
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Substituted 1,3-diaza-2-(thi)oxo-cycloalkanes
The invention relates to new substituted 1,3-diaza-2-(thi)oxo-cycloalkanes, to
processes for their preparation and to their use as herbicides.
Some substituted 1,3-diaza-2-(thi)oxo-cycloalkanes are already known from the
literature (cf. J. Chem. Eng. Data 13 (1968), 582-585 - cited in Chem.
Abstracts
69:106613). However, nothing has been disclosed about the biological
properties of
these compounds.
There have now been found the new substituted 1,3-diaza-2-(thi)oxo-
cycloalkanes of
the general formula (I)
Q
' ~ Rz
RAN N~ (I)
~(CHZ)~
in which
n represents I, 2 or 3,
Q represents oxygen or sulphur,
RI represents hydrogen, formyl or in each case optionally substituted alkyl,
alkoxy, alkylamino, dialkylamino, alkenyl, alkinyl, cycloalkyl or cycloalkyl-
alkyl, and
R2 represents an optionally substituted monocyclic or bicyclic aromatic group
which is optionally fused to a heterocycle.
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-2-
In the definitions, the hydrocarbon chains such as alkyl - also in connection
with
hetero atoms such as in alkoxy - are in each case straight-chain or branched.
n preferably represents 1, 2 or 3;
Q preferably represents oxygen or sulphur;
RI preferably represents hydrogen, formyl, or represents alkyl, alkoxy,
alkylamino, dialkylamino, each of which has 1 to 6 carbon atoms in the alkyl
groups and each of which is optionally substituted by cyano, halogen, Cl-C4-
alkoxy, Cl-C4-alkyl-carbonyl, Cl-C4-alkoxy-carbonyl or morpholinyl, or
represents alkenyl or alkinyl, each of which has 2 to 6 carbon atoms, and each
of which is optionally substituted by cyano, halogen or C1-C4-alkoxy-
carbonyl, or represents cycloalkyl or cycloalkylalkyl, each of which has 3 to
6
carbon atoms in the cycloalkyl groups and, if appropriate, 1 to 4 carbon atoms
in the alkyl moiety and each of which is optionally substituted by cyano,
halogen or C 1-C4-alkyl;
R2 preferably represents the aromatic group defined hereinbelow
R~ / Rs
Rs \ ~ Ra
R5
where
2~ R3 represents hydrogen, vitro, amino, cyano, formylamino, halogen, or
represents alkyl, alkoxy, alkylcarbonylamino, alkoxycarbonylamino,
alkylaminocarbonylamino, each of which has 1 to 6 carbon atoms in
the alkyl groups and each of which is optionally substituted by cyano,
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halogen or C1-C4-alkoxy, or represents cycloalkylcarbonylamino
which has 3 to 6 carbon atoms in the cycloalkyl moiety and which is
optionally substituted by cyano, halogen, C 1-C4-alkyl or C 1-C4-
halogenoalkyl, or represents phenylcarbonylamino which is optionally
substituted by cyano, nitro, C 1-C4-alkyl, C 1-C4-halogenoalkyl, C 1-
C4-alkoxy or C1-C4-halogenoalkoxy;
R4 represents hydrogen, nitro, cyano, fluorine, chlorine or bromine;
RS represents nitro, cyano, carboxyl, carbamoyl, thiocarbamoyl, hydroxyl,
fluorine, chlorine, bromine, or represents alkyl, alkoxy, alkylcarbonyl
or alkoxycarbonyl, each of which has up to 4 carbon atoms and each
of which is optionally substituted by fluorine and/or chlorine;
R~ represents the group hereinbelow:
_A 1 _A2_~,3
in which
Al represents a single bond, or represents oxygen, sulphur, -SO-, -S02-,
-CO- or the group -N-A4- where A4 represents hydrogen, hydroxyl,
C 1-C4-alkyl, C3-C4-alkenyl, C3-C4-alkinyl, C 1-C4-alkoxy, phenyl,
C 1-C4-alkyl-carbonyl, phenylcarbonyl, C 1-C4-alkyl-sulphonyl or
phenylsulphonyl,
Al furthermore represents Cl-C~-alkanediyl, C2-C~-alkenediyl, C2-Cb-
azaalkenediyl, C2-C~-alkinediyl, C3-C6-cycloalkanediyl, C3-C6-
cycloalkenediyl or phenylene, each of which is optionally substituted
by fluorine, chlorine or bromine,
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A2 represents a single bond, or represents oxygen, sulphur, -SO-, -S02-,
-CO- or the group -N-A4- where A4 represents hydrogen, hydroxyl,
C1-C4-alkyl, C1-C4-alkoxy, phenyl, C1-C4-alkylsulphonyl or phenyl-
sulphonyl,
A2 furthermore represents C1-C6-alkanediyl, C2-C6-alkenediyl, C2-C6-
azaalkenediyl, C2-C6-alkinediyl, C3-C6-cycloalkanediyl, C3-G~-
cycloalkenediyl or phenylene, each of which is optionally substituted
by fluorine, chlorine or bromine,
A3 represents hydrogen, hydroxyl, mercapto, amino, cyano, isocyano,
thiocyanato, nitro, carboxyl, carbamoyl, thiocarbamoyl, sulpho,
chlorosulphonyl, fluorine, chlorine, bromine, or represents alkyl,
alkoxy, alkylthio, alkylsulphinyl, alkylsulphonyl, alkylamino, dialkyl-
I S amino, alkoxycarbonyl or dialkoxy(thio)phosphoryl, each of which has
1 to 6 carbon atoms in the alkyl groups and each of which is optionally
substituted by fluorine, chlorine or C1-C4-alkoxy, or represents
alkenyl, alkenyloxy, alkenylamino, alkylideneamino, alkenyloxy-
carbonyl, alkinyl, alkinyloxy, alkinylamino or alkinyloxycarbonyl,
each of which has 2 to 6 carbon atoms in the alkenyl, alkylidene or
alkinyl groups and each of which is optionally substituted by fluorine
or chlorine, or represents cycloalkyl, cycloalkyloxy, cycloalkylalkyl,
cycloalkylalkoxy, cycloalkylideneamino, cycloalkyloxycarbonyl or
cycloalkylalkoxycarbonyl, each of which has 3 to 6 carbon atoms in
the cycloalkyl groups and, if appropriate, I to 4 carbon atoms in the
alkyl groups and each of which is optionally substituted by fluorine,
chlorine, cyano, carboxyl, CI-C4-alkyl and/or CI-C4-alkoxy-
carbonyl, or represents phenyl, phenoxy, phenyl-CI-C4-alkyl, phenyl-
C I -C4-alkoxy, phenoxycarbonyl or phenyl-C 1-C,1-alkoxycarbonyl,
each of which is optionally substituted by nitro, cyano, carboxyl,
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fluorine, chlorine, bromine, Cl-C4-alkyl, C1-C4-halogenoalkyl, C1-
C4-alkyloxy, C1-C4-halogenoalkyloxy and/or C1-C4-alkoxy-carbonyl,
A3 furthermore represents (in each case optionally fully or partially
S hydrogenated) pyrrolyl, pyrazolyl, imidazolyl, triazolyl, furyl,
oxiranyl, oxetanyl, dioxolanyl, thienyl, oxazolyl, isoxazolyl, thiazolyl,
isothiazolyl, oxadiazolyl, thiadiazolyl, pyridinyl, pyrimidinyl, triazinyl,
pyrazolyl-C 1-C4-alkyl, furyl-C 1-C4-alkyl, thienyl-C 1-C4-alkyl,
oxazolyl-Cl-C4-alkyl, isoxazol-C1-C4-alkyl, thiazol-C1-C4-alkyl,
pyridinyl-C1-C4-alkyl, pyrimidinyl-C1-C4-alkyl, pyrazolylmethoxy,
furylmethoxy, perhydropyranylmethoxy or pyridylmethoxy,
R~ represents hydrogen, fluorine or chlorine,
or in each case two adjacent radicals - R3 and R4, R4 and R5, RS and Rb or R6
and
R~ - together represent one of the following groups
-Q3-CQ4-> -Q3-CQ4-QS-> -Q3-C(Rg>R9)-QS-> -C(Rg>R9)-CQ4->
-C(Rg~R9)-Q3-CQ4-> -Q3-C(R$>R9)-C(Rg>R9)->
-Q3-C(Rg,R~)-C(Rg,R9)-QS-, -C(Rg,R9)-C(Rg,R9)-CQ4-,
-Q3-C(Rg)-C(Rg)-~ -C(Rg)-C(Rg)-CQ4-> -Q3-C(Rg>R9)-CQ4->
_N(R10)_C(R8~R9)_CQ4_, _C(R8)-N_, _Q3_CQ4-C(R8~R9)->
-Q3-CQ4_N(R10)_, -Q3_C(R8~R9)-CQ4_N(R10)-
_C(R8,R9)_Q3_CQ4-N(R10)-~ -C(R8,R9)_C(R8,R9)-N(R10)-
_C(R8>R9)_C(R8>R9)_CQ4_N(R10)_> _C(R8)-C(R8)-N(R10)_>
-C(R8)_C(R8)_CQ4-N(R10)_, -C(R8,R9)_CQ4-N(R10)-,
_N(R10~_C~R8;R9~_CQ4_N~R10~-> _C(R8~-N_N~R10)_,
_Q3-CQ4_C(RS.R9)_N(R10~_, Q3_C(R8>R9~_C(R8>R9)_CQ4-N(R10)_
where
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Q3~ Q4 ~d QS ~-a identical or different and represent in each case oxygen or
sulphur,
Rg and R9 are identical or different and individually represent hydrogen,
fluorine,
chlorine, bromine or Cl-C4-alkyl or together represent C2-CS-alkanediyl, and
R10 represents hydrogen, hydroxyl or represents alkyl, alkylcarbonyl, alkoxy-
carbonyl or alkylsulphonyl, each of which has 1 to 6 carbon atoms in the alkyl
groups and each of which is optionally substituted by cyano, fluorine,
chlorine, C 1-C4-alkoxy, C 1-C4-alkyl-carbonyl or C 1-C4-alkoxy-carbonyl, or
represents alkenyl or alkinyl, each of which has 2 to 6 carbon atoms and each
of which is optionally substituted by fluorine, chlorine or bromine, or
represents cycloalkyl or cycloalkylalkyl, each of which has 3 to 6 carbon
atoms in the cycloalkyl groups and, if appropriate, 1 to 3 atoms in the alkyl
moiety and each of which is optionally substituted by fluorine, chlorine,
bromine or Cl-C4-alkyl, or represents alkoxy or alkenyloxy, each of which
has up to 6 carbon atoms and each of which is optionally substituted by
fluorine and/or chlorine, or represents benzyl or benzyloxy, each of which is
optionally substituted by cyano, fluorine, chlorine, Cl-C4-alkyl, C1-C4-
halogenoalkyl, C 1-C4-alkoxy or C 1-C4-halogenoalkoxy.
n especially preferably represents 1, 2 or 3;
Q especially preferably represents oxygen or sulphur;
R 1 especially preferably represents hydrogen, formyl, or represents methyl,
ethyl,
n- or i-propyl, n-, i-, s- or t-butyl, each of which is optionally substituted
by
cyano, fluorine, chlorine, methoxy or ethoxy, or represents propenyl, butenyl,
propinyl or butinyl, each of which is optionally substituted by fluorine or
chlorine, or represents cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl,
cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl or cyclohexyl-
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methyl, each of which is optionally substituted by cyano, fluorine, chlorine,
methyl or ethyl;
R3 preferably represents hydrogen, nitro, amino, cyano, formylamino, fluorine,
chlorine, or represents methyl, trifluoromethyl, acetylamino, propionylamino,
butyroylamino, i-butyroylamino, trifluoroacetylamino, methoxycarbonyl-
amino, ethoxycarbonylamino, methylaminocarbonylamino, ethylamino-
carbonylamino, cyclopropylcarbonylamino or phenylcarbonylamino (benzoyl-
amino);
R4 preferably represents hydrogen, fluorine or chlorine;
RS preferably represents cyano, thiocarbamoyl, chlorine, bromine, methyl,
trifluoromethyl, methoxy, difluoromethoxy or trifluoromethoxy;
R~ especially preferably represents the group hereinbelow:
-A1-A2_A3
in which
A1 represents a single bond, or represents oxygen, sulphur, -SO-, -S02-,
-CO- or the group -N-A4- where A4 represents hydrogen, hydroxyl,
methyl, ethyl, n- or i-propyl, methoxy, ethoxy, n- or i-propoxy,
methylsulphonyl or ethylsulphonyl,
A 1 furthermore represents methylene, ethane- I ,1-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, propinc-1,2-diyl or
propinc-1,3-diyl,
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_g_
A2 represents a single bond, or represents oxygen, sulphur, -SO-, -S02-,
-CO- or the group -N-A4- where A4 represents hydrogen, hydroxyl,
methyl, ethyl, n- or i-propyl, methoxy, ethoxy, n- or i-propoxy,
methylsulphonyl, ethylsulphonyl, n- or i-propylsulphonyl or
phenylsulphonyl,
A2 furthermore represents methylene, ethane-1,1-diyl, ethane-1,2-diyl,
propane-1,1-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, propine-1,2-diyl or
propine-1,3-diyl,
A3 represents hydrogen, hydroxyl, amino, cyano, nitro, carboxyl,
carbamoyl, sulpho, fluorine, chlorine, bromine, or represents methyl,
ethyl, n- or i-propyl, 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, ethylsulphinyl, n- or i-propylsulphinyl,
methylsulphonyl, ethylsulphonyl, n- or i-propylsulphonyl, methyl-
amino, ethylamino, n- or i-propylamino, n-, i-, s- or t-butylamino,
dimethylamino, diethylamino, methoxycarbonyl, ethoxycarbonyl, n- or
i-propoxycarbonyl, dimethoxyphosphoryl, diethoxyphosphoryl or
dipropoxyphosphoryl, diisopropoxyphosphoryl, each of which is
optionally substituted by fluorine, chlorine, methoxy or ethoxy, or
represents propenyl, butenyl, propenyloxy, butenyloxy, propenyl-
amino, butenylamino, propylideneamino, butylideneamino,
propenyloxycarbonyl, butenyloxycarbonyl, propinyl, butinyl,
propinyloxy, butinyloxy, propinylamino, butinylamino, propinyloxy-
carbonyl or butinyloxycarbonyl, each of which is optionally
substituted by fluorine or chlorine, or represents cyclopropyl, cyclo-
3O butyl, cyclopcntyl, cyclohexyl, cyclopropyloxy, cyclobutyloxy, cyclo-
pentyloxy, cyclohexyloxy, cyclopropylmethyl, cyclobutylmethyl,
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cyclopentylmethyl, cyclohexylmethyl, cyclopropylmethoxy, cyclo-
butylmethoxy, cyclopentylmethoxy, cyclohexylmethoxy, cyclo-
pentylideneamino, cyclohexylideneamino, cyclopentyloxycarbonyl,
cyclohexyloxycarbonyl, cyclopentylmethoxycarbonyl or cyclo-
hexylmethoxycarbonyl, each of which is optionally substituted by
fluorine, chlorine, cyano, carboxyl, methyl, ethyl, n- or i-propyl,
methoxycarbonyl or ethoxycarbonyl, or represents phenyl, phenyloxy,
benzyl, phenylethyl, benzyloxy, phenyloxycarbonyl, benzyloxy-
carbonyl, each of which is optionally substituted by nitro, cyano,
carboxyl, fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, tri-
fluoromethyl, methoxy, ethoxy, n- or i-propoxy, difluoromethoxy, tri-
fluoromethoxy, methoxycarbonyl and/or ethoxycarbonyl,
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, thienyl-
methyl, oxazolylmethyl, isoxazolmethyl, thiazolmethyl, pyridinyl
methyl, pyrimidinylmethyl, pyrazolylmethoxy, furylmethoxy or
pyridylmethoxy;
R~ preferably represents hydrogen, fluorine or chlorine.
Two adjacent radicals - R3 and R4, R4 and R5, RS and Rb or R6 and R~ -
together
preferably represent one of the following groups:
-Q3-CQ4-~ -Q3-CQ4-QS-~ -Q3-C(Rg>R9)-QS-, -C(Rg~R9)-CQ4-,
-C(R8,R9~-Q3_CQ4_, _Q3_C~R8,R9~_C(R8,R9~_,
-Q3_C~R8,R9)_C(R8,R9)_QS_, _C(R8,R9)_C(R8>R9)-CQ4_,
-Q3-C(Rg)=C(Rg)-, _C(R8~-C(R8~_CQ4_, -Q3-C~R8,R9~_CQ4-,
-N~R10~_C(R8~R9~_CQ4_, _C(R8~-N_, _Q3_CQ4_C(R8,R9~_>
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-Q3_CQ4_N(R10)_~ _Q3_C(R8~R9)-CQ4_N(R10)-
_C(R8~R9)_Q3_CQ4_N~R10)-~ _C(R8~R9)-C~R8~R9)-N(R10)_
_C(R8~R9)-C~R8~R9)-CQ4_N(R10)_~ _C(R8)=C(R8)_N(R10)-
_C(R8)-C(R8)_CQ4_N~R10)-~ _C(R8~R9)-CQ4-N(R10)-
_N(R10)_C(R8~R9)_CQ4_N(R10)_~ _C(R8)-N_N(R10)_~
-Q3_CQ4_C(R8~R9)-N(R10)_~ Q3_C(R8~R9)-C(R8~R9)-CQ4_N(R10)_
where
Q3, Q4 and QS are identical or different and in each case represent oxygen or
sulphur,
R8 and R9 are identical or different and individually represent hydrogen,
fluorine,
chlorine, methyl or ethyl or together represent ethane-1,2-diyl (dimethylene),
and
R 10 represents hydrogen, hydroxyl, or represents methyl, ethyl, n- or i-
propyl, n-,
i-,s or t-butyl, each of which is optionally substituted by cyano, fluorine,
chlorine, methoxy, ethoxy, acetyl, propionyl, methoxycarbonyl or ethoxy-
carbonyl, or represents propenyl, butenyl, propinyl or butinyl, each of which
is optionally substituted by fluorine, chlorine or bromine, or represents
cyclo-
propyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclobutyl-
methyl, cyclopentylmethyl or cyclohexylmethyl, each of which is optionally
substituted by fluorine, chlorine, bromine, methyl or ethyl, or represents
methoxy, ethoxy, n- or i-propoxy, n-, i- or s-butoxy, propenyloxy or butenyl-
oxy, each of which is optionally substituted by fluorine and/or chlorine, or
represents benzyl or benzyloxy, each of which is optionally substituted by
cyano, fluorine, chlorine, methyl, ethyl, trifluoromethyl, methoxy, ethoxy,
difluoromethoxy or trifluoromethoxy;
n very especially preferably represents 1 or 2;
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Q very especially preferably represents oxygen or sulphur;
R1 very especially preferably represents methyl, ethyl, n- or i-propyl, each
of
S which is optionally substituted by cyano, fluorine, chlorine, methoxy or
ethoxy;
R3 especially preferably represents hydrogen, fluorine or chlorine;
R4 especially preferably represents hydrogen;
RS especially preferably represents cyano, thiocarbamoyl, chlorine, bromine,
methyl or trifluoromethyl;
Rf especially preferably represents the group hereinbelow:
_A 1 _A2_A3
in which
A 1 represents a single bond,
A2 represents a single bond,
2~ A3 represents hydroxyl, amino, cyano, nitro, carboxyl, carbamoyl, sulpho,
fluorine, chlorine, bromine, or represents methyl, ethyl, n- or i-propyl,
n-, i-, s- or t-butyl, n-, i-, s- or t-pentyl, methoxy, ethoxy, n- or i-prop-
oxy, n-, i-, s- or t-butoxy, n-, i-, s- or t-pentyloxy, methylthio, ethyl-
thio, n- or i-propylthio, n-, i-, s- or t-butylthio, methylsulphinyl,
cthylsulphinyl, n- or i-propylsulphinyl, methylsulphonyl,
ethylsulphonyl, n- or i-propylsulphonyl, methylamino, ethylamino, n-
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or i-propylamino, n-, i-, s- or t-butylamino, dimethylamino, diethyl-
amino, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl,
each of which is optionally substituted by fluorine, chlorine, methoxy
or ethoxy, or represents propenyl, butenyl, propenyloxy, butenyloxy,
propenylamino, butenylamino, propylideneamino, butylideneamino,
propenyloxycarbonyl, butenyloxycarbonyl, propinyl, butinyl, propinyl-
oxy, butinyloxy, propinylamino, butinylamino, propinyloxycarbonyl or
butinyloxycarbonyl, each of which is optionally substituted by fluorine
or chlorine, or represents cyclopropyloxy, cyclobutyloxy, cyclopentyl-
oxy, cyclohexyloxy, cyclopropylmethoxy, cyclobutylmethoxy, cyclo-
pentylmethoxy, cyclohexylmethoxy, cyclopentyloxycarbonyl, cyclo-
hexyloxycarbonyl, cyclopentylmethoxycarbonyl or cyclohexyl-
methoxycarbonyl, each of which is optionally substituted by fluorine,
chlorine, cyano, carboxyl, methyl, ethyl, n- or i-propyl, methoxy-
carbonyl or ethoxycarbonyl, or represents phenoxy, benzyloxy,
phenyloxycarbonyl or benzyloxycarbonyl, each of which is optionally
substituted by nitro, cyano, carboxyl, fluorine, chlorine, bromine,
methyl, ethyl, n- or i-propyl, trifluoromethyl, methoxy, ethoxy, n- or i-
propoxy, difluoromethoxy, trifluoromethoxy, methoxycarbonyl and/or
ethoxycarbonyl;
R~ especially preferably represents hydrogen.
Preferred in accordance with the invention are the compounds of the formula
(I)
which contain a combination of the meanings mentioned above as being
preferred.
Especially preferred in accordance with the invention are the compounds of the
formula (I) which contain a combination of the meanings mentioned above as
being
especially preferred.
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Very especially preferred in accordance with the invention are the compounds
of the
formula (I) which contain a combination of the meanings mentioned above as
being
especially preferred.
A very especially preferred group are those compounds of the formula (I) in
which
n represents 1 or 2,
Q represents oxygen or sulphur,
R1 represents methyl, ethyl, n- or i-propyl, each of which is optionally
substituted
by cyano, fluorine, chlorine, methoxy or ethoxy and
R2 represents the aromatic group defined hereinbelow
R~ / Rs
Rs \ ~ R4
Rs
where
R3 represents hydrogen, fluorine or chlorine,
R4 represents hydrogen,
RS represents cyano, thiocarbamoyl, chlorine, bromine, methyl or
trifluoromethyl,
R~' rrpresents the group hereinbclow
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_A 1 _A2_A3
in which
A 1 represents the group -N-A4- where A4 represents hydrogen,
methylsulphonyl or ethylsulphonyl,
A2 represents a single bond or -CO-,
A3 represents hydrogen, or represents 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, methylsulphonyl, ethylsulphonyl, n- or i-propyl-
sulphonyl, each of which is optionally substituted by fluorine,
chlorine, methoxy or ethoxy, or represents cyclopropyl, cyclo-
butyl, cyclopentyl, cyclohexyl, cyclopropyloxy, cyclobutyloxy,
cyclopentyloxy, cyclohexyloxy, cyclopropylmethyl, cyclobutyl-
methyl, cyclopentylmethyl, cyclohexylmethyl, cyclopropyl-
methoxy, cyclobutylmethoxy, cyclopentylmethoxy, cyclohexyl-
methoxy, each of which is optionally substituted by fluorine,
chlorine, cyano, carboxyl, methyl, ethyl, n- or i-propyl,
methoxycarbonyl or ethoxycarbonyl, or represents phenyl,
phenoxy, benzyl or benzyloxy, each of which is optionally
substituted by vitro, cyano, carboxyl, fluorine, chlorine,
bromine, methyl, ethyl, n- or i-propyl, trifluoromethyl, meth-
oxy, ethoxy, n- or i-propoxy, difluoromethoxy, tri-
fluoromethoxy, methoxycarbonyl and/or ethoxycarbonyl, and
R~ represents hydrogen.
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A further very especially preferred group are those compounds of the formula
(I) in
which
n represents 1 or 2,
Q represents oxygen or sulphur,
R1 represents methyl, ethyl, n- or i-propyl, each of which is optionally
substituted
by cyano, fluorine, chlorine, methoxy or ethoxy, and
R2 represents the aromatic group defined hereinbelow
R~ / Rs
Rs \ ~ R4
Rs
where
R3 represents hydrogen, fluorine or chlorine,
R4 represents hydrogen,
R5 represents cyano, thiocarbamoyl, chlorine, bromine, methyl or
tri fluoromethyl,
Rb represents the group hereinbelow
-A 1-A2-A3
in which
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A1 represents the group -N-A4- where A4 represents hydrogen,
methylsulphonyl or ethylsulphonyl,
A2 represents -S02-,
A3 represents methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, each
of which is optionally substituted by fluorine, chlorine,
methoxy or ethoxy, or represents cyclopropyl, cyclobutyl,
cyclopentyl or cyclohexyl, each of which is optionally
substituted by fluorine, chlorine, cyano or methyl, or represents
phenyl or benzyl, each of which is optionally substituted by
nitro, cyano, fluorine, chlorine, bromine, methyl, ethyl, tri-
fluoromethyl, methoxy, ethoxy, difluoromethoxy, trifluoro-
methoxy, methoxycarbonyl or ethoxycarbonyl, and
R~ represents hydrogen.
The definitions of radicals mentioned above in general terms or in preferred
ranges
apply not only to the end products of the formula (I), but also accordingly to
the
starting materials or intermediates required in each case for the preparation.
These
definitions of radicals can be combined with each other as desired, that is to
say
combinations between the stated ranges of preferred compounds are also
possible.
The new substituted 1,3-diaza-2-(thi)oxo-cycloalkanes of the general formula
(I) are
distinguished by a potent and selective herbicidal activity.
The new substituted 1,3-diaza-2-(thi)oxo-cycloalkanes of the general formula
(I) are
obtained when
3t)
1,3-diaza-2-(thi)oxo-cycloalkanes of the general formula (II)
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Q
R~N~N~H (II)
~(CHz)~
in which
n, Q and R1 are as defined above
are reacted with halogen compounds of the general formula (III)
X 1-R2 (III)
in which
R2 is as defined above and
X 1 represents halogen,
if appropriate in the presence of a reaction auxiliary and if appropriate in
the presence
of a diluent, and, if appropriate, electrophilic or nucleophilic substitution
reactions
are subsequently carried out in the customary manner within the definition of
the
substituents.
In principle, the compounds of the general formula (I) can also be synthesized
as
shown schematically hereinbelow:
Reaction of diamines of the general formula (IV) with (thio)carbonic acid
derivatives
of the general formula (V)
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R ~ Rz + Q
(I)
(CH2)n
(N) (V)
where
S
n, Q, R1 and R2 are as defined above and
Y1 and Y2 are identical or different and in each case represent halogen (in
particular
chlorine), alkoxy (in particular methoxy or ethoxy), alkoxyalkoxy (in
particular (methoxyethoxy or ethoxyethoxy), phenoxy or imidazolyl,
if appropriate in the presence of a reaction auxiliary such as, for example,
pyridine
and if appropriate in the presence of a diluent such as, for example, toluene.
1 S Reaction of 1,3-diaza-2-(thi)oxo-cycloalkanes of the general formula (VI)
with
halogen compounds of the general formula (VII)
Q
2
H\N~N~R + R~ z
(I)
-(CHZ)~ X --
(VI) (VII)
where
n, Q, R 1 and R2 are as defined above and
2S ~-' represents halogen (in particular chlorine, bromine or iodine),
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if appropriate in the presence of a reaction auxiliary such as, for example,
ethyl-diiso-
propylamine and if appropriate in the presence of a diluent such as, for
example,
acetonitrile.
Reaction of (thio)ureas of the general formula (VIII) with a,w-disubstituted
alkanes
of the general formula (IX)
Q
Ei
R\H H/R + E2~(CH2)~ --~ (I)
( V III) (IX)
where
n, Q, R1 and R2 are as defined above, and
E1 and E2 represent leaving groups which can be substituted by a nucleophile,
such
as halogen (in particular chlorine or bromine or alkylsulphonyloxy (in
particular methylsulphonyloxy),
if appropriate in the presence of a reaction auxiliary such as, for example,
potassium
carbonate and if appropriate in the presence of a diluent such as, for
example,
acetone.
If, for example, 1-methyl-imidazolidin-2-one and 2,4,5-trifluorobenzonitrile
are used
as starting materials, the course of the reaction in the process according to
the
?5 invention can be outlined by the following formulaic scheme:
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F
O
II CN
HsC.N~N.H + O / I
-' ~ \
- HF H3C~N~N
L--J F
Formula (II) provides a general definition of the 1,3-diaza-2-(thi)oxo-
cycloalkanes to
be used as starting materials in the process according to the invention for
the
preparation of compounds of the formula (I). In formula (II), n, Q and RI
preferably,
or in particular, have those meanings which have already been stated above in
connection with the description of the compounds of the formula (I) according
to the
invention as being preferred, or particularly prefered, for n, Q and R I .
The starting materials of the general formula (II) are known and/or can be
prepared
by processes known per se (cf. J. Am. Chem. Soc. 80 (1958), 6409-6412; J.
Chem.
Soc. Perkin Trans. 1, 1981, 2499-2503; J. Org. Chem. 22 (1957), 1581; J. Org.
Chem. 28 ( 1992), 7339-7342; Synth. Commun. 27 (1997), 3565-3571 ).
Formula (III) provides a general definition of the halogen compounds
furthermore to
be used as starting materials in the process according to the invention. In
formula
(III), R2 preferably, or in particular, has that meaning which has already
been stated
above in connection with the description of the compounds of the formula (I)
according to the invention as being preferred, especially preferred or very
especially
preferred for R2; X2 preferably represents fluorine or chlorine, in particular
fluorine.
The starting materials of the general formula (III) are known and/or can be
prepared
by processes known per se (cf EP-A-191181, EP-A-370332, EP-A-431373,
EP-A-441004, EP-A-597360).
The process according to the invention for the preparation of the compounds of
the
general formula (I) is preferably carried out using a diluent. Suitable
dilucnts are,
above all, inert organic solvents. These include, in particular, aliphatic,
alicyclic or
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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
S 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 hexamethyl phosphoric tr-iamide; esters such as methyl
acetate or ethyl acetate, sulphoxides such as dimethyl sulphoxide.
The process according to the invention for the preparation of the compounds of
the
general formula (I) is preferably carried out using a reaction auxiliary.
Suitable
reaction auxiliaries are generally the customary inorganic or organic bases or
acid
acceptors. These preferably include the acetates, amides, carbonates,
1 S hydrogencarbonates, hydrides, hydroxides or alkoxides of alkali metals or
alkaline
earth metals 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 hydrogencarbonate,
potassium hydrogencarbonate or calcium hydrogencarbonate, 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-, -i-, -s- or -t-
butoxide, or
potassium n-, -i-, -s- or -t-butoxide; furthermore also basic organic nitrogen
2S compounds such as, for example, tr-imethylamine, triethylamine,
tripropylamine, tri-
butylamine, ethyl-diisopropylamine, N,N-dimethyl-cyclohexylamine, dicyclo-
hexylamine, ethyl-dicyclohexylamine, N,N-dimethyl-aniline, N,N-dimethyl-
benzylamine, pyridine, 2-methyl-, 3-methyl-, 4-methyl-, 2,4-dimethyl-, 2,6-
dimethyl-,
3,4-dimethyl- and 3,S-dimethyl-pyridine, S-ethyl-2-methyl-pyridine, 4-dimethyl-
amino-pyridine, N-methyl-piperidine, 1,4-diazabicyclo[2,2,2Joctane (DABCO),
l,S-
diazabicyclo[4,3,OJnon-S-ene (DBN), or 1,8-diazabicyclo[S,4,OJundec-7-ene
(DBU).
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When carrying out the process according to the invention, the reaction
temperatures
can be varied within a substantial range. In general, the process is carried
out at
temperatures between 0°C and 1 SO°C, preferably between
20°C and 120°C.
S
The process according to the invention is generally earned out under
atmospheric
pressure. However, it is also possible for the process according to the
invention to be
carried out under elevated or reduced pressure, in general between 0.1 bar and
10 bar.
To carry out the process according to the invention, the starting materials
are
generally employed in approximately equimolar amounts. However, it is also
possible to use one of the components in a larger excess. 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 several hours at the temperature
required.
1 S 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 weedkillers. By weeds, in the
broadest
sense, there are to be understood all plants which grow in locations where
they are
undesired. Whether the substances according to the invention act as total or
selective
herbicides depends essentially on the amount used.
The active compounds according to the invention can be used, for example, in
connection with the following plants:
Dicotyledonous weeds of the genera: Sinapis, Lepidium, Galium, Stellaria,
Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus,
Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia,
Cirsium, Carduus, Sonchus, Solanum, Rorippa, Rotala, Lindernia, Lamium,
Veronica, Abutilon, Emex, Datura, Viola, Galeopsis, Papaver, Centaurea,
Trifolium,
Ranunculus and Taraxacum.
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Dicotyledonous crops of the genera: Gossypium, Glycine, Beta, Daucus,
Phaseolus,
Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis,
Brassica, Lactuca, Cucumis and Cucurbita.
S
Monocotyledonous weeds of the enera: 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, Agrostis, 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.
Depending on the concentration, the compounds are suitable for total weed
control,
for example on industrial terrain and rail tracks, and on paths and areas with
or
without tree stands. Equally, the compounds can be employed for controlling
weeds
in perennial crops, for example forests, ornamental 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 and pastures, and for selective weed
control in
annual crops.
The compounds of the formula (I) according to the invention arc particularly
suitable
for the selective control of monocotyledonous and dicotyledonous weeds in
monocotyledonous crops, both pre- and post-emergence.
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The active compounds can be converted into the customary formulations, such as
solutions, emulsions, wettable powders, suspensions, powders, dusts, pastes,
soluble
powders, granules, suspoemulsion concentrates, natural and synthetic materials
impregnated with active compound, and microencapsulations in polymeric
S 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 dispersants
and/or
foam formers.
If water is used as an extender, organic solvents can, for example, also be
used as
cosolvents. Liquid solvents which are mainly suitable are: aromatics such as
xylene,
toluene or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic
I S 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 butanol or glycol as
well as
their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl
isobutyl
ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and
dimethyl sulphoxide, and water.
Suitable solid carriers are: 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; suitable solid carriers for granules are: for example
crushed
and fractionated natural rocks such as calcite, marble, pumice, sepiolite and
dolomite,
or else 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 formers are: for example non-ionic and anionic
emulsifiers,
such as polyoxyethylenc fatty acid esters, polyoxyethylene fatty alcohol
ethers, for
example alkylaryl polyglycol ethers, alkylsulphonates, alkyl sulphates,
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arylsulphonates and protein hydrolysates; suitable dispersants are: for
example
lignin-sulphite waste liquors and methylcellulose.
Adhesives such as carboxymethylcellulose and natural and synthetic polymers in
the
form of powders, granules or latexes such as gum arabic, polyvinyl alcohol and
polyvinyl acetate, or else natural phospholipids such as cephalins and
lecithins, and
synthetic phospholipids can be used in the formulations. Further additives can
be
mineral and vegetable oils.
It is possible to use colourants 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
iron, manganese, boron, copper, cobalt, molybdenum and zinc.
The formulations generally comprise between 0.1 and 95 per cent by weight of
active
compound, preferably between 0.5 and 90%.
The active compounds according to the invention, as such or in their
formulations,
can also be used for controlling weeds as a mixture with known herbicides,
ready-
mixes or tank mixes being possible.
Herbicides which are suitable for the mixtures are known herbicides, for
example
acetochlor, acifluorfen(-sodium), aclonifen, alachlor, alloxydim(-sodium),
ametryne,
amidochlor, amidosulfuron, anilofos, asulam, atrazine, azafenidin,
azimsulfuron,
benazolin(-ethyl), benfuresate, bensulfuron(-methyl), bentazone, benzofenap,
benzoylprop(-ethyl), bialaphos, bifenox, bispyribac(-sodium), bromobutide,
bromo-
fenoxim, bromoxynil, butachlor, butroxydim, butylate, cafenstrole, caloxydim,
carbetamide, carfentrazone(-ethyl), chlomethoxyfen, chloramben, chloridazon,
chlor-
imuron(-ethyl), chlornitrofen, chlorsulfuron, chlortoluron, cinmethylin,
cinosulfuron,
clethodim, clodinafop(-propargyl), clomazone, clomeprop, clopyralid,
clopyrasulf=
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uron(-methyl), cloransulam(-methyl), cumyluron, cyanazine, cycloate,
cyclosulfam-
uron, cycloxydim, cyhalofop(-butyl), 2,4-D, 2,4-DB, 2,4-DP, desmedipham, di-
allate,
dicamba, diclofop(-methyl), diclosulam, diethatyl(-ethyl), difenzoquat,
diflufenican,
diflufenzopyr, dimefuron, dimepiperate, dimethachlor, dimethametryn, dimethen-
S amid, dimexyflam, dinitramine, diphenamid, diquat, dithiopyr, diuron,
dymron, epo-
prodan, EPTC, esprocarb, ethalfluralin, ethametsulfuron(-methyl),
ethofumesate,
ethoxyfen, ethoxysulfuron, etobenzanid, fenoxaprop-(-P-ethyl), flamprop(-
isopropyl),
flamprop(-isopropyl-L), flamprop(-methyl), flazasulfuron, florasulam, fluazi-
fop(-P-butyl), flumetsulam, flumiclorac(-pentyl), flumioxazin, flumipropyn,
flumet-
sulam, fluometuron, fluorochloridone, fluoroglycofen(-ethyl), flupoxam,
flupropacil,
flurpyrsulfuron(-methyl, -sodium), flurenol(-butyl), fluridone, fluroxypyr(-
meptyl),
flurprimidol, flurtamone, fluthiacet(-methyl), fluthiamide, fomesafen,
glufosinate(-
ammonium), glyphosate(-isopropylammonium), halosafen, haloxyfop(-ethoxyethyl),
haloxyfop(-P-methyl), hexazinone, imazamethabenz(-methyl), imazamethapyr,
imazamox, imazapyr, imazaquin, imazethapyr, imazosulfuron, ioxynil,
isopropalin,
isoproturon, isouron, isoxaben, isoxaflutole, isoxapyrifop, lactofen, lenacil,
linuron,
MCPA, MCPP, mefenacet, metamitron, metazachlor, methabenzthiazuron, meto-
benzuron, metobromuron, (alpha-)metolachlor, metosulam, metoxuron, metribuzin,
metsulfuron(-methyl), molinate, monolinuron, naproanilide, napropamide,
neburon,
nicosulfuron, norflurazon, orbencarb, oryzalin, oxadiargyl, oxadiazon,
oxasulfuron,
oxaziclomefone, oxyfluorfen, paraquat, pelargonic acid, pendimethalin,
pentoxazone,
phenmedipham, piperophos, pretilachlor, primisulfuron(-methyl), prometryn,
propa-
chlor, propanil, propaquizafop, propisochlor, propyzamide, prosulfocarb,
prosulf
uron, pyraflufen(-ethyl), pyrazolate, pyrazosulfuron(-ethyl), pyrazoxyfen,
pyribenz-
oxim, pyributicarb, pyridate, pyriminobac(-methyl), pyrithiobac(-sodium), quin-
chlorac, quinmerac, quinoclamine, quizalofop(-P-ethyl), quizalofop(-P-
tefuryl), rim-
sulfuron, sethoxydim, simazine, simetryn, sulcotrione, sulfentrazone, sulfo-
meturon(-methyl), sulfosate, sulfosulfuron, tebutam, tebuthiuron,
terbuthylazine, ter-
butryn, thenylchlor, thiafluamide, thiazopyr, thidiazimin, thifensulfuron(-
methyl),
3(1 thiobencarb, tiocarbazil, tralkoxydim, tri-allate, triasulfuron,
tribenuron(-methyl), tri-
clopyr, tridiphane, trifluralin and triflusulfuron.
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Mixtures with other known active compounds such as fungicides, insecticides,
acaricides, nematicides, bird repellants, plant nutrients and soil
conditioners, 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 spreading.
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
1 S essentially on the nature of the desired effect. 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 S kg per ha.
The preparation and use of the active compounds according to the invention can
be
seen from the examples which follow.
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Preparation Examples:
Example 1
F
CN
H3C~N~N \
F
A mixture of 5.8 g (50 mmol) of 1-methyl-imidazolidine-2-thione, 8.6 g (SS
mmol)
of 2,4,5-trifluoro-benzonitrile, 7.6 g (SS mmol) of potassium carbonate and 50
ml of
dimethyl sulphoxide is stirred for 16 hours at 80°C. When cold, the
mixture is poured
into a stirred mixture of approximately equal volumes of methylene chloride
and
water and acidified with 2N hydrochloric acid. The organic phase is separated
off,
washed with water, dried with sodium sulphate and filtered. The filtrate is
concentrated in a water pump vacuum, the residue is digested with diethyl
ether, and
the product which is obtained as crystals is isolated by filtration with
suction.
This gives 9.5 g (75% of theory) of 1-methyl-3-(4-cyano-2,5-difluoro-phenyl)-
imida-
zolidine-2-thione of melting point 143°C.
Example 2
C2Hs
HN~SO2
CN
H3C~N~N \
F
(subsequent reaction)
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A mixture of 2.0 g (8 mmol) of 1-methyl-3-(4-cyano-2,5-difluoro-phenyl)-imida-
zolidine-2-thione, 1.8 g (16 mmol) of ethanesulphonamide, 2.2 g (16 mmol) of
potassium carbonate and 50 ml of dimethyl sulphoxide is stirred for 16 hours
at
100°C. When cold, the mixture is poured into a stirred mixture of
approximately
equal volumes of methylene chloride and water and acidified with 2N
hydrochloric
acid. The organic phase is separated off, washed with water, dried with sodium
sulphate and filtered. The filtrate is concentrated in a water pump vacuum,
the
residue is digested with isopropanol, and the product which is obtained as
crystals is
isolated by filtration with suction.
This gives 1.9 g (68% of theory) of 1-methyl-3-(4-cyano-2-fluoro-5-
ethylsulphonyl-
amino-phenyl)-imidazolidine-2-thione of melting point 174°C.
Other examles of compounds of the formula (I) which can be prepared
analogously to
the Preparation Examples 1 to 2 and in accordance with the general description
of the
preparation processes according to the invention are those listed in Table 1
below.
Q
Rz
RU-N~ (I)
(CHz)~
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Table 1: Examples of the compounds of the formula (I)
Ex. Melting
No. n Q R1 R2 point (°C)
3 1 S CH3 F NH2 227
~O
F
4 1 S CH3 OCH3 222
CN
/
F
5 1 O CH3 F 103
CN
F
6 1 O CH3 ~ CI 98
N02
7 1 S CH3 ~ CI 166
N02
8 1 S CH3 213
O
CN
/
F
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Ex. Melting
No. n Q R1 R2 point (°C)
9 1 S CH3 ~ 164
O CH3
CN
/
F
10 1 O CH3 ~ 2Hs 188
HN'S02
CN
F
11 1 O CH3 203
O
CN
/
F
12 1 O CH3 112
O CH3
CN
/
F
13 1 S CH3 ~ C~ 105
H~N~O
''Of~CH3
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Ex. Melting
No. n Q R1 R2 point (°C)
14 1 S CH3 ~ CI 187
H~N~O
'N~HCH3
15 1 S CH3 ~ ~I 142
H~N~(O
'C~H(CH3)2
16 1 S CH3 ~ CI 1 SO
H~N O
17 1 S CH3 ~ CI
H~N~O
'C~s H s
18 1 S CH3 ~ CI 162
H~N~O
C~F3
19 1 O CHI ~ CI 127
H~N~O
'C~f~F3
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Ex. Melting
No. n Q R1 R2 point (°C)
20 1 O CH3 ~ C~ 144
/
H~N~O
'C~H(CH3)2
21 1 O CH3 ~ C~ 149
H~N~O
'C~sHs
22 1 O CH3 ~ C~ 220
H~N~O
'N~HCH3
23 1 S CH3 ~ C~ 1 gg
H~N~O
'~H
24 1 S CH3 C~ 150
CN
25 1 S CHFz F 143
CN
/
F
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Ex. Melting
No. n Q R1 R2 point (°C)
26 1 S CHFZ ~ 2H5 90
HN'S02
\ CN
/
F
27 1 O ~N~ F 165
O ~ \ CN
F
28 I O CHFz F loge = 2.23
CN b>
F
29 1 S CHFZ C3H~-i 138
HN'SOZ
\ CN
/
F
30 1 S CHFz ~ H3 130
HN'SOz
\ CN
/
F
31 1 S C~HS F 117
\ CN
/
F
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Ex. Melting
No. n Q R1 R2 point (°C)
32 1 O CHO F loge = 1.42
CN b>
F
33 1 O H F 19S
CN
/
F
34 1 S H ~zHs 1S7
HN'S02
\ CN
F
The loge values stated in Table 1 were determined by HPLC (high performance
liquid chromatography) on a reversed phase column (C 18) in accordance with
EEC
Directive 79/831 Annex V.AB. Temperature: 43°C.
S
(a) Eluents for the determination in the acidic range: 0.1 % aqueous
phosphoric
acid, acetonitrile; linear gradient from 10% acetonitrile to 90% acetonitrile -
the relevant readings are marked with a) in Table 1.
(b) Eluents for the determination in the neutral range: 0.01 molar aqueous
phosphate buffer solution, acetonitrile; linear gradient from 10% acetonitrile
to 90% acetonitrile - the relevant readings arc marked with b) in Table 1.
Standardization was done with unbranched alkan-2-ones (with 3 to 16 carbon
atoms)
1 S whose loge values are known (determination of the loge values with the aid
of the
retention times by linear interpolation between two subsequent alkanones).
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The lambda-max values were determined with the aid of the I1V spectra from
200 nm to 400 nm in the maxima of the chromatographic signals.
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Use Examples:
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 active compound preparation, 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 approx. 24 hours, the
soil is
sprayed with the active compound preparation in such a way that the amounts of
active compound desired in each case are applied per unit area. The
concentration of
the spray mixture is chosen in such a way that the amounts of active compound
desired in each case are applied in 1000 1 of water/ha.
After three weeks, the degree of damage to the plants is scored 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 potent action against weeds combined in some cases with good
tolerance by crop plants such as, for example, maize is shown, for example, by
the
compounds of Preparation Example 2, S, 8, 9, 10, 1 1 and 12.
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Example B
Post-emergence test
S Solvent: S parts by weight of acetone
Emulsifier: 1 part by weight of alkylaryl polyglycol ether
To prepare a suitable active compound preparation, 1 part by weight of active
compound is mixed with the stated amount of solvent, the stated amount of
emulsifier is added, and the concentrate is diluted' with water to the desired
concentration.
Test plants which have a height of 5 - 15 cm are sprayed with the active
compound
preparation in such a way that the amounts of active compound desired in each
case
are applied per unit area. The concentration of the spray mixture is chosen in
such a
way that the amounts of active compound desired in each case are applied in
1000 1
of water/ha.
After three weeks, the degree of damage to the plants is scored 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 potent action against weeds combined in some cases with good
tolerance by crop plants such as, for example, barley is shown, for example,
by the
compounds of Preparation Example 2, 8, 9, 10 and 12.
