U.S. patent application number 10/353455 was filed with the patent office on 2003-11-06 for substituted n-aryl nitrogen-containing heterocyclic compounds.
Invention is credited to Dollinger, Markus, Findeisen, Kurt, Goto, Toshio, Lender, Andreas, Linker, Karl-Heinz, Santel, Hans-Joachim, Schallner, Otto, Yanagi, Akihiko.
Application Number | 20030208073 10/353455 |
Document ID | / |
Family ID | 25942887 |
Filed Date | 2003-11-06 |
United States Patent
Application |
20030208073 |
Kind Code |
A1 |
Linker, Karl-Heinz ; et
al. |
November 6, 2003 |
Substituted N-aryl nitrogen-containing heterocyclic compounds
Abstract
The invention relates to novel substituted N-aryl
nitrogen-containing heterocyclic compounds of the general formula
(I) 1 and to the compounds isomeric to the substituted N-aryl
nitrogen-containing heterocyclic compounds of the formula (I), of
the formulae (Ia) and (Ib) 2 in which Q.sup.1, Q.sup.2, R.sup.1,
R.sup.2 and Ar have the meanings given in the description,
processes for their preparation and their use as herbicides.
Inventors: |
Linker, Karl-Heinz;
(Leverkusen, DE) ; Findeisen, Kurt; (Leverkusen,
DE) ; Schallner, Otto; (Monheim, DE) ; Lender,
Andreas; (Wuppertal, DE) ; Santel, Hans-Joachim;
(Leverkusen, DE) ; Dollinger, Markus; (Leverkusen,
DE) ; Yanagi, Akihiko; (Oyamashi, JP) ; Goto,
Toshio; (Kokubunji-machi, JP) |
Correspondence
Address: |
KURT BRISCOE
NORRIS, MCLAUGHLIN & MARCUS, P.A.
220 EAST 42ND STREET, 30TH FLOOR
NEW YORK
NY
10017
US
|
Family ID: |
25942887 |
Appl. No.: |
10/353455 |
Filed: |
January 29, 2003 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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10353455 |
Jan 29, 2003 |
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10138011 |
May 2, 2002 |
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10138011 |
May 2, 2002 |
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09667392 |
Sep 20, 2000 |
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6426318 |
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09667392 |
Sep 20, 2000 |
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09245818 |
Feb 5, 1999 |
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6162765 |
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09245818 |
Feb 5, 1999 |
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08849966 |
Jun 6, 1997 |
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08849966 |
Jun 6, 1997 |
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PCT/EP95/04759 |
Dec 4, 1995 |
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Current U.S.
Class: |
544/333 ;
544/209; 546/204; 546/272.4; 548/136; 548/143; 548/206; 548/247;
548/263.4 |
Current CPC
Class: |
C07D 249/12 20130101;
C07D 405/04 20130101; A01N 43/653 20130101; C07D 413/04 20130101;
A01N 43/84 20130101 |
Class at
Publication: |
544/333 ;
546/272.4; 546/204; 548/206; 548/136; 548/143; 548/247; 548/263.4;
544/209 |
International
Class: |
C07D 417/02; C07D
413/02; C07D 43/02 |
Foreign Application Data
Date |
Code |
Application Number |
Dec 15, 1994 |
DE |
P 44 44 741.8 |
Aug 24, 1995 |
DE |
195 31 152.3 |
Claims
1. A substituted N-aryl nitrogen-containing heterocyclic compound
of the general formula (I) 217in which Q.sup.1 represents oxygen or
sulfur, Q.sup.2 represents oxygen or sulfur, R.sup.1 represents
hydrogen, cyano or formyl or represents alkyl which is optionally
substituted by halogen, cyano, carboxyl, alkoxy, alkenyloxy,
alkinyloxy, alkylthio, alkenylthio, alkinylthio, alkoxycarbonyl,
alkenyl-oxycarbonyl or alkinyloxycarbonyl, R.sup.1 furthermore
represents alkenyl or alkinyl, in each case optionally substituted
by halogen, R.sup.1 furthermore represents alkylcarbonyl,
alkenylcarbonyl, alkinylcarbonyl, alkoxycarbonyl,
alkenyloxycarbonyl or alkinyloxycarbonyl, in each case optionally
substituted by halogen, R.sup.1 furthermore represents cycloalkyl
or cycloalkylcarbonyl, in each case optionally substituted by
halogen, cyano or carboxyl, R.sup.2 represents hydrogen, cyano or
formyl, or represents alkyl which is optionally substituted by
halogen, cyano, carboxyl, alkoxy, alkenyloxy, alkinyloxy,
alkylthio, alkenylthio, alkinylthio, alkoxycarbonyl,
alkenyloxycarbonyl or alkinyloxycarbonyl, R.sup.2 furthermore
represents alkenyl or alkinyl, in each case optionally substituted
by halogen, R.sup.2 furthermore represents alkylcarbonyl,
alkenylcarbonyl, alkinylcarbonyl, alkoxycarbonyl,
alkenyloxycarbonyl or alkinyloxycarbonyl, in each case optionally
substituted by halogen, R.sup.2 furthermore represents cycloalkyl
or cycloalkylcarbonyl, in each case optionally substituted by
halogen, cyano or carboxyl, and Ar represents the substituted
monocyclic or bicyclic aryl or heteroaryl grouping defined below.
218 in which R.sup.3 represents hydrogen or halogen, R.sup.4
represents hydrogen or halogen, R.sup.5 represents cyano, carboxyl,
chlorocarbonyl, carbamoyl, thiocarbamoyl, hydroxyl or halogen, or
represents alkyl, alkoxy or alkoxycarbonyl, in each case optionally
substituted by halogen, R.sup.6 represents the following
grouping--A.sup.1--A.sup.2--A.sup.3 in which A.sup.1 represents a
single bond, or represents oxygen, sulfur, --SO--, --SO.sub.2--,
--CO-- or the grouping --N--A.sup.4--, in which A.sup.4 represents
hydrogen, hydroxyl, alkyl, alkenyl, alkinyl, alkoxy, aryl,
alkylcarbonyl, arylcarbonyl, alkylsulfonyl or arylsulfonyl, A.sup.1
furthermore represents alkanediyl, alkenediyl, azaalkenediyl,
alkanediyl, cycloalkanediyl, cycloalkenediyl or phenylene, in each
case optionally substituted by halogen, A.sup.2 represents a single
bond, or represents oxygen, sulfur, --SO--, --SO.sub.2--, --CO-- or
the grouping --N--A.sup.4--, in which A.sup.4 represents hydrogen,
hydroxyl, alkyl, alkoxy, aryl, alkylsulfonyl or arylsulfonyl,
A.sup.2 furthermore represents alkanediyl, alkenediyl,
azaalkenediyl, alkinediyl, cycloalkanediyl, cycloalkenediyl or
phenylene, in each case optionally substituted by halogen, A.sup.3
represents hydrogen, with the proviso that in this case A.sup.1
and/or A.sup.2 do(es) not represent any single bond, A.sup.3
furthermore represents hydroxyl, mercapto, amino, cyano, isocyano,
thiocyanato, nitro, carboxyl, carbamoyl, thiocarbamoyl, sulfo,
chlorosulfonyl or halogen, or represents alkyl, alkoxy, alkylthio,
alkylsulfinyl, alkylsulfonyl, alkylamino, dialkylamino,
alkoxycarbonyl or dialkoxy(thio)-phosphoryl, in each case
optionally substituted by halogen or alkoxy, A.sup.3 furthermore
represents alkenyl, alkenyloxy, alkenylthio, alkenylamino,
alkylidenamino, alkenyloxycarbonyl, alkinyl, alkinyloxy,
alkinylthio, alkynylamino or alkinyloxycarbonyl, in each case
optionally substituted by halogen A.sup.3 furthermore represents
cycloalkyl, cycloalkyloxy, cycloalkylalkyl, cycloalkylalkoxy,
cycloalkylidenamino, cycloalkyloxycarbonyl or
cycloalkylalkoxycarbonyl, in each case optionally substituted by
halogen, cyano, carboxyl. alkyl and/or alkoxy carbonyl, A.sup.3
furthermore represents aryl, aryloxy, aralkyl, arylalkoxy,
aryloxycarbonyl or arylalkoxycarbonyl, in each case optionally
substituted by nitro, cyano, carboxyl, halogen, alkyl,
halogenalkyl, allyloxy, halogenalkyloxy and/or alkoxy-carbonyl,
A.sup.3 furthermore represents in each case optionally completely
or partly hydrogenated pyrrolyl, pyrazolyl, imidazolyl, triazolyl,
furyl, oxiranyl, oxetanyl, dioxolanyl, thienyl, oxazolyl,
isoxazolyl, thiazolyl, isothiazolyl, oxadiazolyl, thiadiazolyl,
pyridinyl, pyrimidinyl, triazinyl, pyrazolylalkyl, furylalkyl,
thienylalkyl, oxazolylalkyl, isoxazolylalkyl, thiazolylalkyl,
pyridinylalkyl, pyrimidinylalkyl, pyrazolylalkoxy or furylalkoxy,
or represents perhydropyranylalkoxy or pyridylalkoxy, and R.sup.7
represents hydrogen or halogen, or in each case two adjacent
radicals--R.sup.3 and R.sup.4, R.sup.4 and R.sup.5, R.sup.5 and
R.sup.6 or R.sup.6 and R.sup.7--together represent one of the
following groupings --Q.sup.3--CQ.sup.4--,
--Q.sup.3--CQ.sup.4--Q.sup.5--- ,
--Q.sup.3--C(R.sup.8,R.sup.9)--Q.sup.5--,
--C(R.sup.8,R.sup.9)--CQ.sup.4- --,
--C(R.sup.8,R.sup.9)--Q.sup.3--CQ.sup.4--,
--Q.sup.3--C(R.sup.8,R.sup.- 9)--C(R.sup.8,R.sup.9)--,
--Q.sup.3--C(R.sup.8,R.sup.9)--C(R.sup.8,R.sup.9- )--Q.sup.5--,
--C(R.sup.8,R.sup.9)--C(R.sup.8,R.sup.9)--CQ.sup.4--,
--Q.sup.3--C(R.sup.8).dbd.C(R.sup.8)--,
--C(R.sup.8).dbd.C(R.sup.8)--CQ.s- up.4--,
--Q.sup.3--C(R.sup.8,R.sup.9)--CQ.sup.4--, --N(R.sup.10)--C(R.sup.-
8,R.sup.9)--CQ.sup.4--, --C(R.sup.8).dbd.N--,
--Q--CQ.sup.4--C(R.sup.8,R.s- up.9)--,
--Q.sup.3--CQ.sup.4--N(R.sup.10)--, --Q.sup.3--C(R.sup.8,R.sup.9)-
--CQ.sup.4--N--(R.sup.10)--,
--C(R.sup.8,R.sup.9)--Q.sup.3--CQ.sup.4--N(R.- sup.10)--,
--C(R.sup.8,R.sup.9)--C(R.sup.8,R.sup.9)--N(R.sup.10)--,
--C(R.sup.8,R.sup.9)--C(R.sup.8,R.sup.9)--CQ.sup.4--N(R.sup.10)--,
--C(R.sup.8).dbd.C(R.sup.8)--N(R.sup.10)--,
--C(R.sup.8).dbd.C(R.sup.8)--- CQ.sup.4--N(R.sup.10)--,
--C(R.sup.8,R.sup.9)--CQ.sup.4--N(R.sup.10)--N(R.-
sup.10)--C(R.sup.8,R.sup.9)--CQ.sup.4--N(R.sup.10)--,
--C(R.sup.8).dbd.N--N(R.sup.10)--,
--Q.sup.3--CQ.sup.4--C(R.sup.8,R.sup.9- )--N(R.sup.10)--,
Q.sup.3--C(R.sup.8,R.sup.9)--C(R.sup.8,R.sup.9)--CQ.sup.-
4--N(R.sup.10)-- in which Q.sup.3, Q.sup.4, and Q.sup.5 are
identical or different and in each case represent oxygen or sulfur,
R.sup.8 and R.sup.9 are identical or different and individually
represent hydrogen, halogen or alkyl or together represent
alkanediyl, and R.sup.10 represents hydrogen or hydroxyl, or
represents alkyl, alkylcarbonyl, alkoxycarbonyl or alkylsulfonyl
which are optionally substituted by cyano, halogen, alkoxy,
alkyl-carbonyl or alkoxy-carbonyl, or represents alkenyl or
alkinyl, in each case optionally substituted by halogen, or
represents cycloalkyl or cycloalkylalkyl, in each case optionally
substituted by halogen or alkyl, or represents alkoxy or
alkenyloxy, in each case optionally substituted by halogen, or
represents arylalkyl or arylalkoxy, in each case optionally
substituted by cyano, halogen, allyl, halogenoalkyl, alkoxy or
halogenoalkoxy, excluding the compounds
4-(3,4-dichlorophenyl)-1,2-dimethyl-5-thioxo-1,2,4-triazolidin-3-one
and
4-(4-chloro-3-trifluoromethylphenyl)-1,2-dimethyl-5-thioxo-1,2,4-triazoli-
din-3-one.
2. A substitute N-aryl nitrogen-containing heterocyclic compound of
the general formula (Ia) 219in which Q.sup.1, Q.sup.2, R.sup.1,
R.sup.2 and Ar have the meanings given in claim 1.
3. A substituted N-aryl nitrogen-containing heterocyclic compound
of the general formula (Ib) 220in which Q.sup.1, Q.sup.2, R.sup.1,
R.sup.2 and Ar have the meanings given in claim 1.
4. A process for the preparation of a substituted N-aryl
nitrogen-containing heterocyclic compound of the general formula
(I) or of a compound of the formula (Ia) or (Ib) as claimed in
claims 1 to 3, which comprises a procedure in which (a) a
(thio)semicarbazide derivative of the general formula (II) 221 in
which Q.sup.1, Q.sup.2, R.sup.1, R.sup.2 and Ar have the meanings
given in claim 1 and R represents alkyl, is subjected to a
cyclizing condensation reaction, if appropriate in the presence of
a reaction auxiliary and if appropriate in the presence of a
diluent, and thereafter, if appropriate, electrophilic or
nucleophilic substitution reactions are carried out in the
customary manner in the context of the definition of the
substituents, or in wich (b) an aryliminoheterocyclic compound of
the general formula (III) 222 in which Q.sup.1, Q.sup.2, R.sup.1,
R.sup.2 and Ar have the abovementioned meanings, -- or a compound
of the formula (Ia) or (Ib)--above--is isomerized thermally
("pyrolytically"), if appropriate in the presence of a reaction
auxiliary and if appropriate in the presence of a diluent.
5. A substituted N-aryl nitrogen-containing heterocyclic compound
of the general formula (I), (Ia) or (Ib) as claimed in claims 1 to
3, in which Q.sup.1 represents oxygen or sulfur, Q.sup.2 represents
oxygen or sulfur, R.sup.1 represents hydrogen, cyano or formyl, or
represents C.sub.1-C.sub.6-alkyl, in each case optionally
substituted by fluorine, chlorine, cyano, carboxyl,
C.sub.1-C.sub.4-alkoxy, C.sub.3-C.sub.4-alkenyloxy,
C.sub.3-C.sub.4-alkyloxy, C.sub.1-C.sub.4-alkylthio,
C.sub.3-C.sub.4-alkenylthio, C.sub.3-C.sub.4-alkylthio,
C.sub.1-C.sub.4-alkoxy carbonyl,
C.sub.3-C.sub.4-alkenyloxy-carbonyl or C.sub.3-C.sub.4-alkinyloxy
carbonyl, R.sup.1 furthermore represents C.sub.3-C.sub.6-alkenyl or
C.sub.3-C.sub.6-alkinyl, in each case optionally substituted by
fluorine or chlorine, R.sup.1 furthermore represents
C.sub.1-C.sub.6-alkyl-carbony- l, C.sub.3-C.sub.6-alkenyl-carbonyl,
C.sub.3-C.sub.6-alkinylcarbonyl, C.sub.1-C.sub.6-alkoxy-carbonyl,
C.sub.3-C.sub.6-alkenyloxy-carbonyl or
C.sub.3-C.sub.6-alkinyloxy-carbonyl, in each case optionally
substituted by fluorine or chlorine, R.sup.1 furthermore represents
C.sub.3-C.sub.6-cycloalkyl or C.sub.3-C.sub.6-cycloalkyl-carbonyl,
in each case optionally substituted by fluorine, chlorine, bromine,
cyano or carboxyl, R.sup.2 represents hydrogen, cyano or formyl, or
represents C.sub.1-C.sub.6-alkyl, in each case optionally
substituted by fluorine, chlorine, cyano, carboxyl,
C.sub.1-C.sub.4-alkoxy, C.sub.3-C.sub.4-alkenyloxy,
C.sub.3-C.sub.4-alkinyloxy, C.sub.1-C.sub.4-alkylthio,
C.sub.3-C.sub.4-alkenylthio, C.sub.3-C.sub.4-adylthio,
C.sub.1-C.sub.4-alkoxy-carbonyl,
C.sub.3-C.sub.4-alkenyloxy-carbonyl or
C.sub.3-C.sub.4-alkinyloxy-carbony- l, R.sup.2 furthermore
represents C.sub.3-C.sub.6-alkenyl or C.sub.3-C.sub.6-alkinyl, in
each case optionally substituted by fluorine or chlorine, R.sup.2
furthermore represents C.sup.1-C.sub.6-alkyl-carbony- l,
C.sub.3-C.sub.6-alkenyl-carbonyl, C.sub.3-C.sub.6-alkinyl-carbonyl,
C.sub.1-C.sub.6-alkoxy-carbonyl,
C.sub.3-C.sub.6-alkenyloxy-carbonyl or C.sub.3-C.sub.6-alkinyloxy
carbonyl, in each case optionally substituted by fluorine or
chlorine, R.sup.2 furthermore represents C.sub.3-C.sub.6-cycloalkyl
or C.sub.3-C.sub.6-cycloalkyl-carbonyl, in each case optionally
substituted by fluorine, chlorine, bromine, cyano or carboxyl, and
Ar represents the, substituted monocyclic or bicyclic aryl or
heteroaryl grouping defined below 223 in which R.sup.3 represents
hydrogen, fluorine, chlorine or bromine, R.sup.4 represents
hydrogen, fluorine, chlorine or bromine, R.sup.5 represents cyano,
carboxyl, chlorocarbonyl, carbamoyl, thiocarbamoyl, hydroxyl,
fluorine, chlorine, bromine or represents alkyl, alkoxy or
alkoxycarbonyl having in each case up to 4 carbon atoms and in each
case optionally substituted by fluorine and/or chlorine, R.sup.6
represents the following grouping--A.sup.1--A.su- p.2--A.sup.3 in
which A.sup.1 represents a single bond, or represents oxygen,
sulfur, --SO--, --SO.sub.2--, --CO-- or the grouping --NA.sup.4--,
in which A.sup.4 represents hydrogen, hydroxyl,
C.sub.1-C.sub.4-alkyl, C.sub.3-C.sub.4-alkenyl,
C.sub.3-C.sub.4-alkinyl, C.sub.1-C.sub.4-alkoxy, phenyl,
C.sub.1-C.sub.4-alkyl carbonyl, phenyl-carbonyl,
C.sub.1-C.sub.4-alkyl-sulfonyl or phenylsulfonyl, A.sup.1
furthermore represents C.sub.1-C.sub.6-alkanediyl,
C.sub.2-C.sub.6-alkenediyl, C.sub.2-C.sub.6-azaalkenediyl,
C.sub.2-C.sub.6-alkenediyl, C.sub.3-C.sub.6-cycloalkanediyl,
C.sub.3-C.sub.6-cycloalkenediyl or phenylene, in each case
optionally substituted by fluorine, chlorine or bromine, A.sup.2
represents a single bond, or represents oxygen, sulfur, --SO--,
--SO.sub.2--, --CO-- or the grouping --N--A.sup.4--, in which
A.sup.4 represents hydrogen, hydroxyl, C.sub.1-C.sub.4-alkyl,
C.sub.1-C.sub.4-alkoxy, phenyl, C.sub.1-C.sub.4-alkylsulfonyl or
phenylsulfonyl, A.sup.2 furthermore represents
C.sub.1-C.sub.6-alkenediyl, C.sub.2-C.sub.6-alkenediyl,
C.sub.2-C.sub.6-azaakenediyl, C.sub.2-C.sub.6-alkinediyl,
C.sub.3-C.sub.6-cloallediyl, C.sub.3-C.sub.6-cycloalkenediyl or
phenylene, in each case optionally substituted by fluorine,
chlorine or bromine, A.sup.3 represents hydrogen, with the proviso
that in this case A.sup.1 and/or A.sup.2 do(es) not represent a
single bond, A.sup.3 furthermore represents hydroxyl, mercapto,
amino, cyano, isocyano, thiocyanato, nitro, carboxyl, carbamoyl,
thiocarbamoyl, sulfo, chlorosulfonyl, fluorine, chlorine or
bromine, A.sup.3 furthermore represents alkyl, alkoxy, alkylthio,
alkylsulfinyl, alkylsulfonyl, alkylamino, dialkylamino,
alkoxycarbonyl or dialkoxy(thio)phosphoryl having in each case 1 to
6 carbon atoms in the alkyl groups and in each case optionally
substituted by fluorine, chlorine or C.sub.1-C.sub.4-alkoxy,
A.sup.3 furthermore represents alkenyl, alkenyloxy, alkenylamino,
alkylidenamino, alkenyloxycarbonyl, alkinyl, alkinyloxy,
alkinylamino or alkinyloxycarbonyl having in each case 2 to 6
carbon atoms in the alkenyl, alkylidene or alkinyl groups and in
each case optionally substituted by fluorine or chlorine, A.sup.3
furthermore represents cycloalkyl, cycloalkyloxy, cycloalkylalkyl,
cycloalkylalkoxy, cycloalkylidenamino, cycloalkyloxycarbonyl or
cycloalkylalkoxycarbonyl having in each case 3 to 6 carbon atoms in
the cycloalkyl groups and where appropriate 1 to 4 carbon atoms in
the alkyl groups and in each case optionally substituted by
fluorine, chlorine, cyano, carboxyl, C.sub.1-C.sub.4-alkyl and/or
C.sub.1-C.sub.4-alkoxy-carbonyl, A.sup.3 furthermore represents
phenyl, phenyloxy, phenyl-C.sub.1-C.sub.4-alkyl,
phenyl-C.sub.1-C.sub.4-alkoxy, pentyloxycarbonyl or
phenyl-C.sub.1-C.sub.4-alkoxycarbonyl, in each case optionally
substituted by nitro, cyano, carboxyl, fluorine, chlorine, bromine,
C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-halogenalkyl,
C.sub.1-C.sub.4-alkyloxy, C.sub.1-C.sub.4-halogenalkyloxy and/or
C.sub.1-C.sub.4-alkoxycarbonyl, A.sup.3 furthermore represents in
each case optionally completely or partly hydrogenated pyrrolyl,
pyrazolyl, imidazolyl, triazolyl, furyl, oxiranyl, oxetanyl,
dioxolanyl, thienyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl,
oxadiazolyl, thiadiazolyl, pyridinyl, pyrimidinyl, triazinyl,
pyrazolyl-C.sub.1-C.sub.4-alkyl, furyl-C.sub.1-C.sub.4-alkyl,
thienyl-C.sub.1-C.sub.4-alkyl, oxalolyl-C.sub.1-C.sub.4-alkyl,
isoxazolyl-C.sub.1-C.sub.4-alkyl, thiazolyl-C.sub.1-C.sub.4-alkyl,
pyridinyl-C.sub.1-C.sub.4-alkyl, pyridinyl-C.sub.1-C.sub.4-alkyl,
pyrazolylmethoxy or furthermore, or represents
perhydropyranylmethoxy or pyridylmethoxy, and R.sup.7 represents
hydrogen, fluorine or chlorine or in each case two adjacent
radicals--R.sup.3 and R.sup.4, R.sup.4 and R.sup.5, R.sup.5 and
R.sup.6 or R.sup.6 and R.sup.7--together represent one of the
following groupings --Q.sup.3--CQ.sup.4--,
--Q.sup.3--CQ.sup.4--Q.sup.5--,
--Q.sup.3--C(R.sup.8,R.sup.9)--Q.sup.5--,
--C(R.sup.8,R.sup.9)--CQ.sup.4-- -,
--C(R.sup.8,R.sup.9)--Q.sup.3--CQ.sup.4--,
--Q.sup.3--C(R.sup.8,R.sup.9- )--C(R.sup.8,R.sup.9)--,
Q.sup.3--C(R.sup.8,R.sup.9)--C(R.sup.8,R.sup.9)--- Q.sup.5--,
--C(R.sup.8,R.sup.9)--C(R.sup.8,R.sup.9)--CQ.sup.4--,
--Q.sup.3--C(R.sup.8).dbd.C(R.sup.8)--,
--C(R.sup.8).dbd.C(R.sup.8)--CQ.s- up.4--,
--Q.sup.3--C(R.sup.8,R.sup.9)--CQ.sup.4--, --N(R.sup.10)--C(R.sup.-
8,R.sup.9)--CQ.sup.4--, --C(R.sup.8).dbd.N--,
--Q.sup.3--CQ.sup.4--C(R.sup- .8,R.sup.9)--,
--Q.sup.3--CQ.sup.4--N(R.sup.10)--, --Q.sup.3--C(R.sup.8,R.-
sup.9)--C(R.sup.8,R.sup.9)--N(R.sup.10)--,
--C(R.sup.8,R.sup.9)--C(R.sup.8- ,R.sup.9)--,
CQ.sup.4--N(R.sup.10)--, --C(R.sup.8).dbd.C(R.sup.8)--N(R.sup-
.10)--, --C(R.sup.8).dbd.C(R.sup.8)--CQ.sup.4--N(R.sup.10)--,
--C(R.sup.8,R.sup.9)--, --CQ.sup.4--N(R.sup.10)--,
--C(R.sup.8,R.sup.9)--Q.sup.3--CQ.sup.4--N(R.sup.10)--,
--C(R.sup.8,R.sup.9)--CQ.sup.4--N(R.sup.10)--,
--N(R.sup.10)--C(R.sup.8,R- .sup.9)--CQ.sup.4--N(R.sup.10)--,
--C(R.sup.8).dbd.N--N(R.sup.10)--,
--Q.sup.3--CQ.sup.4--C(R.sup.8,R.sup.9)--N(R.sup.10)--,
Q.sup.3--C(R.sup.8,R.sup.9)--C(R.sup.8,R.sup.9)--CQ.sup.4--N(R.sup.10)--,
in which Q.sup.3, Q.sup.4 and Q.sup.5 are identical or different
and in each case represent oxygen or sulfur, R.sup.8 and R.sup.9
are identical or different and individually represent oxygen,
fluorine, chlorine, bromine or C.sub.1-C.sub.4-alkyl or together
represent C.sub.2-C.sub.5-alkanediyl, and R.sup.10 represents
hydrogen or hydroxyl, or represents alkyl, alkylcarbonyl,
alkoxycarbonyl or alkylsulfonyl having in each case 1 to 6 carbon
atoms in the alkyl groups and in each case optionally substituted
by cyano, fluorine, chlorine, C.sub.1-C.sub.4-alkoxy,
C.sub.1-C.sub.4-alkyl carbonyl or C.sub.1-C.sub.4-alkoxy-carbonyl,
R.sup.10 furthermore represents alkenyl or alkinyl having in each
case 2 to 6 carbon atoms and in each case optionally substituted by
fluorine, chlorine or bromine, R.sup.10 furthermore represents
cycloalkyl or cycloalkylalkyl having in each case 3 to 6 carbon
atoms in the cycloalkyl groups and where appropriate 1 to 3 atoms
in the alkyl group and in each case optionally substituted by
fluorine, chlorine, bromine or C.sub.1-C.sub.4-alkyl, R.sub.10
furthermore represents alkoxy or alkenyloxy having in each case up
to 6 carbon atoms and in each case optionally substituted by
fluorene and/or chlorine, and R.sup.10 furthermore represents
benzyl or benzyloxy, in each case optionally substituted by cyano,
fluorene, chlorine, C.sub.1-C.sub.4-alkyl,
C.sub.1-C.sub.4-halogenoalkyl, C.sub.1-C.sub.4-alkoxy or
C.sub.1-C.sub.4-halogenoalkoxy, excluding the compounds
4-(3,4-dichloro-phenyl)-1,2-dimethyl-5-thioxo-1,2,4-tiazolidin--
3-one and
4-(4-chloro-3-trifluoromethyl-phenyl)-1,2-dimethyl-5-thioxo-1,2,-
4-triazolidin-3-one.
6. A substituted N-aryl nitrogen-containing heterocyclic compound
of the general formula (I), (Ia) or (Ib) as claimed in claims 1 to
3, in which Q.sup.1 represents oxygen or sulfur, Q.sup.2 represents
oxygen or sulfur, R.sup.1 represents hydrogen, cyano or formyl, or
represents methyl, ethyl, n- or i-propyl or n-, i-, s- or t-butyl,
in each case optionally substituted by fluorine, chlorine, cyano,
carboxyl, methoxy or ethoxy, R.sup.1 furthermore represents
propenyl, butenyl, propinyl or butinyl, in each case optionally
substituted by fluorine or chlorine, R.sup.1 furthermore represents
acetyl, propionyl, methoxycarbonyl or ethoxy-carbonyl, in each case
optionally substituted by fluorine or chlorine, R.sup.1 furthermore
represents cyclopropyl which is optionally substituted by fluorine
or chlorine, R.sup.2 represents hydrogen, cyano or formyl, or
represents methyl, ethyl, n- or i-propyl or n-, i-, s- or t-butyl,
in each case optionally substituted by fluorine, chlorine, cyano,
carboxyl, methoxy or ethoxy, R.sup.2 furthermore represents
propenyl, butenyl, propinyl or butinyl, in each case optionally
substituted by fluorine or chlorine, R.sup.2 furthermore represents
acetyl, propionyl, methoxycarbonyl or ethoxy-carbonyl, in each case
optionally substituted by fluorine or chlorine, R.sup.2 furthermore
represents cyclopropyl which is optionally substituted by fluorine
or chlorine, and Ar represents the substituted monocyclic or
bicyclic aryl or heteroaryl grouping defined below 224 in which
R.sup.3 represents hydrogen, fluorine or chlorine, R.sup.4
represents hydrogen, fluorine or chlorine, R.sup.5 represents
cyano, thiocarbamoyl, chlorine, bromine, methyl, trifluoromethyl,
methoxy, difluoromethoxy or trifluoro-methoxy, R.sup.6 represents
the following grouping--A.sup.1--A.sup.2--A.sup.3 in which A.sup.1
represents a single bond, or represents oxygen, sulfur, --SO--,
--SO.sub.2--, --CO--0 or the grouping --N--A.sup.4--, in which
A.sup.4 represents hydrogen, hydroxyl, methyl, ethyl, n- or
i-propyl, methoxy, ethoxy, n- or i-propoxy, methylsulfonyl or
ethylsulfonyl, A.sup.1 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,
propane-1,2-diyl, propane-1,3-diyl, ethine-1,2-diyl,
propine-1,2-diyl or propine-1,3-diyl, A.sup.2 represents a single
bond, or represents oxygen, sulfur, --SO--, --SO.sub.2--, --CO-- or
the grouping --N--A.sup.4--, in which A.sup.4 represents oxygen,
hydroxyl, methyl, ethyl, n- or i-propyl, methoxy, ethoxy, n- or
i-propoxy, methylsulfonyl, ethylsulfonyl, n- or i-propylsulfonyl or
phenylsulfonyl, A.sup.2 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,
propane-1,2-diyl, propane-1,3-diyl, ethine-1,2-diyl,
propine-1,2-diyl or propine-1,3-diyl, A.sup.3 represents hydrogen,
with the proviso that in this case A.sup.1 and/or A.sup.2 do(es)
not represent a single bond, A.sup.3 furthermore represents
hydroxyl, amino, cyano, nitro, carboxyl, carbamoyl, sulfo,
fluorine, chlorine or bromine, A.sup.3 furthermore 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, methylsulfinyl,
ethylsulfinyl, n- or i-propylsulfinyl, methylsulfonyl,
ethylsulfonyl, n- or i-propylsulfonyl, methylamino, ethylamino, n-
or i-propylamino, n-, i-, s- or t-butylamino, dimethylamino,
diethylamino, methoxycarbonyl, ethoxycarbonyl, n- or
i-propoxycarbonyl, dimethoxyphosphoryl, diethoxyphosphoryl,
dipropoxyphosphoryl or diisopropoxyphosphoryl, in each case
optionally substituted by fluorine, chlorine, methoxy or ethoxy,
A.sup.3 furthermore represents propenyl, butenyl, propenyloxy,
butenyloxy, propenylamino, butenylamino, propylidenamino,
butylidenamino, propenyloxycarbonyl, butenyloxycarbonyl, propinyl,
butinyl, propinyloxy, butinyloxy, propinylamino, butinylamino,
propinyloxycarbonyl or butinyloxycarbonyl, in each case optionally
substituted by fluorine or chlorine, A.sup.3 furthermore represents
cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropyloxy,
cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, cyclopropylmethyl,
cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl,
cyclopropylmethoxy, cyclobutylmethoxy, cyclopentylmethoxy,
cyclohexylmethoxy, cyclopentylidenamino, cyclobexylidenamino,
cyclopentyloxycarbonyl, cyclohexyloxycarbonyl,
cyclopentylmethoxycarbonyl or cyclohexylmethoxycarbonyl, in each
case optionally substituted by fluorine, chlorine, cyano, carboxyl,
methyl, ethyl, n- or i-propyl, methoxycarbonyl or ethoxycarbonyl,
A.sup.3 furthermore represents phenyl, phenyloxy, benzyl,
phenylethyl, benzyloxy, phenyloxycarbonyl or benzyloxycarbonyl, in
each case optionally substituted by 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, A.sup.3
furthermore represents in each case optionally completely or partly
hydrogenated pyrrolyl, pyrazolyl, imidazolyl, triazolyl, furyl,
thienyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl,
oxadiazolyl, thiadiazolyl, pyridinyl, pyrimidinyl, triazinyl,
pyrazolylmethyl, furylmethyl, thienylmethyl, oxazolylmethyl,
isoxazolylmethyl, thiazolylmethyl, pyridinylmethyl,
pyrimidinylmethyl, pyrazolylmethoxy, furylmethoxy or
pyridylmethoxy, R.sup.7 represents hydrogen, fluorine or chlorine,
or in each case two adjacent radicals--R.sup.3 and R.sup.4, R.sup.4
and R.sup.5, R.sup.5 and R.sup.6 or R.sup.6 and R.sup.7--together
represent one of the following groupings --Q.sup.3--CQ.sup.4--,
--Q.sup.3--CQ.sup.4--Q.sup.5--,
--Q.sup.3--C(R.sup.8,R.sup.9)--Q.sup.5--,
--C(R.sup.8,R.sup.9)--CQ.sup.4-- -,
--C(R.sup.8,R.sup.9)--Q.sup.3--CQ.sup.4--,
--Q.sup.3--C(R.sup.8,R.sup.9- )--C(R.sup.8,R.sup.9),
--Q--C(R.sup.8,R.sup.9)--C(R.sup.8,R.sup.9)--Q.sup.- 5--,
--C(R.sup.8,R.sup.9)--C(R.sup.8,R.sup.9)--CQ.sup.4--,
--Q.sup.3--(R.sup.8).dbd.C(R.sup.8)--,
--C(R.sup.8).dbd.C(R.sup.8)--CQ.su- p.4--,
--Q.sup.3--C(R.sup.8,R.sup.9)--CQ.sup.4--,
--N(R.sup.10)--C(R.sup.8- ,R.sup.9)--CQ.sup.4--,
--C(R.sup.8).dbd.N--, --Q.sup.3--CQ.sup.4--C(R.sup.- 8,R.sup.9)--,
--Q.sup.3--CQ.sup.4--N(R.sup.10)--, --Q.sup.3--CR(R.sup.8,R.-
sup.9)--CQ.sup.4--N--(R.sup.10)--,
--C(R.sup.8,R.sup.9)--Q.sup.3--CQ.sup.4- --N(R.sup.10)--,
--C(R.sup.8,R.sup.9)--C(R.sup.8,R.sup.9)--N(R.sup.10)--,
--C(R.sup.8,R.sup.9)--C(R.sup.8,R.sup.9)--CQ.sup.4--N(R.sup.10)--,
--C(R.sup.8).dbd.C(R.sup.8)--N(R.sup.10)--,
--C(R.sup.8).dbd.C(R.sup.8)--- CQ.sup.4--N(R.sup.10)--,
--C(R.sup.8).dbd.C(R.sup.8)--N(R.sup.10)--,
--C(R.sup.8).dbd.C(R.sup.8)--CQ.sup.4--N(R.sup.10)--,
--C(R.sup.8,R.sup.9)--CQ.sup.4--N(R.sup.10)--,
--N(R.sup.10)--C(R.sup.8,R- .sup.9)--CQ.sup.4--N(R.sup.10)--,
--C(R.sup.8).dbd.N--N(R.sup.10)--,
--Q.sup.3--CQ.sup.4--C(R.sup.8,R.sup.9)--N(R.sup.10)--,
Q.sup.3--C(R.sup.8,R.sup.9)--C(R.sup.8,R.sup.9)--CQ.sup.4--N(R.sup.10)--,
in which Q.sup.3, Q.sup.4 and Q.sup.5 are identical or different
and in each case represent oxygen or sulfur, R.sup.8 and R.sup.9
are identical or different and individually represent hydrogen,
fluorine, chlorine, methyl or ethyl or together represent
ethane-1,2-diyl(dimethylene), and R.sup.10 represents hydrogen or
hydroxyl, or represents methyl, ethyl, n- or i-propyl or n-, i-, s-
or t-butyl which are optionally substituted by cyano, fluorine,
chlorine, methoxy, ethoxy, acetyl, propionyl, methoxycarbonyl or
ethoxycarbonyl, R.sup.10 furthermore represents propenyl, butenyl,
propinyl or butinyl, in each case optionally substituted by
fluorine, chlorine or bromine, R.sup.10 furthermore represents
cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl,
cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl or
cyclohexylmethyl, in each case optionally substituted by fluorine,
chlorine, bromine, methyl or ethyl, R.sup.10 furthermore represents
methoxy, ethoxy, n- or i-propoxy, n-, i- or s-butoxy, propenyloxy
or butenyloxy, in each case optionally substituted by fluorine
and/or chlorine, and R.sup.10 furthermore represents benzyl or
benzyloxy, in each case optionally substituted by cyano, fluorine,
chlorine, methyl, ethyl, trifluoromethyl, methoxy, ethoxy,
difluoromethyl or trifluoromethoxy, excluding the compounds
4-(3,4-dichloro-phenyl)-1,2-dim-
ethyl-5-thioxo-1,2,-triazolidin-3-one and
4-(4-chloro-3-trifluoromethyl-ph-
enyl)1,2-diethyl-5-thioxo-1,2,4-triazolidin-3-one.
7. A herbicidal composition which has a content of at least one
N-aryl nitrogen-containing heterocyclic compound of the general
formula (I), (Ia) or (Ib) as claimed in claims 1 to 6.
8. A method of combating undesirable plants which comprises
allowing an N-aryl nitrogen-containing heterocyclic compound of the
general formula (I), (Ia) or (Ib) as claimed in claims 1 to 6 to
act on undesirable plants and/or their environment.
9. The use of an N-aryl nitrogen-containing heterocyclic compound
of the general formula (I), (Ia) or (Ib) as claimed in claims 1 to
6 for combating undesirable plants.
10. A process for the preparation of a herbicidal composition,
which comprises mixing an N-aryl nitrogen-containing heterocyclic
compound of the general formula (I), (Ia) or (Ib) as claimed in
claims 1 to 6 with extenders and/or surface-active substances.
Description
[0001] The invention relates to novel substituted N-aryl
nitrogen-containing heterocyclic compounds, processes for their
preparation and their use as herbicides.
[0002] It is known that certain N-aryl nitrogen-containing
heterocyclic compounds have herbicidal properties (cf. EP 11693, DE
2952685, DE 3026739, U.S. Pat. Nos. 4,276,420, and 4,326,878, WO
94/14817). However, the compounds known from the patent
applications mentioned have not acquired noteworthy importance.
[0003] The novel substituted N-aryl nitrogen-containing
heterocyclic compounds of the general formula (I) 3
[0004] in which
[0005] Q.sup.1 represents oxygen or sulfur,
[0006] Q.sup.2 represents oxygen or sulfur,
[0007] R.sup.1 represents hydrogen, cyano or formyl or represents
alkyl which is optionally substituted by halogen, cyano, carboxyl,
alkoxy, alkenyloxy, alkinyloxy, alkylthio, alkenylthio,
alkinylthio, alkoxycarbonyl, alkenyloxycarbonyl or
alkinyloxycarbonyl,
[0008] R.sup.1 furthermore represents alkenyl or alkinyl, in each
case optionally substituted by halogen,
[0009] R.sup.1 furthermore represents alkylcarbonyl,
alkenylcarbonyl, alkinylcarbonyl, alkoxycarbonyl,
alkenyloxycarbonyl or alkinyloxycarbonyl, in each case optionally
substituted by halogen,
[0010] R.sup.1 furthermore represents cycloalkyl or
cycloalkylcarbonyl, in each case optionally substituted by halogen,
cyano or carboxyl,
[0011] R.sup.2 represents hydrogen, cyano or formyl, or represents
alkyl which is optionally substituted by halogen, cyano, carboxyl,
alkoxy, alkenyloxy, alkinyloxy, alkilthio, alkenylthio,
alkinylthio, alkoxycarbonyl, alkenyloxycarbonyl or
alkinyloxycarbonyl,
[0012] R.sup.2 furthermore represents alkenyl or alkinyl, in each
case optionally substituted by halogen,
[0013] R.sup.2 furthermore represents alkylcarbonyl,
alkenylcarbonyl, alkinylcarbonyl, alkoxycarbonyl,
alkenyloxycarbonyl or alkinyloxycarbonyl, in each case optionally
substituted by halogen,
[0014] R.sup.2 furthermore represents cycloalkyl or
cycloalkylcarbonyl, in each case optionally substituted by halogen,
cyano or carboxyl, and
[0015] Ar represents the substituted monocyclic or bicyclic aryl or
heteroaryl grouping defined below. 4
[0016] in which
[0017] R.sup.3 represents hydrogen or halogen,
[0018] R.sup.4 represents hydrogen or halogen,
[0019] R.sup.5 represents cyano, carboxyl, chlorocarbonyl,
carbamoyl, thiocarbamoyl, hydroxyl or halogen, or represents alkyl,
alkoxy or alkoxycarbonyl, in each case optionally substituted by
halogen,
[0020] R.sup.6 represents the following grouping
--A.sup.1--A.sup.2--A.sup.3
[0021] in Which
[0022] A.sup.1 represents a single bond, or represents oxygen,
sulfur, --SO--, --SO.sub.2--, --CO-- or the grouping
--N--A.sup.4--, in which A.sup.4 represents hydrogen, hydroxyl,
alkyl, alkenyl, alkinyl, alkoxy, aryl, alkylcarbonyl, arylcarbonyl,
alkylsulfonyl or arylsulfonyl,
[0023] A.sup.1 furthermore represents alkanediyl, alkanediyl,
azaalkenediyl, alkinediyl, cycloalkanediyl, cycloalkenediyl or
phenylene, in each case optionally substituted by halogen,
[0024] A.sup.2 represents a single bond, or represents oxygen,
sulfur, --SO--, --SO.sub.2--, --CO-- or the grouping
--N--A.sup.4--, in which A.sup.4 represents hydrogen, hydroxyl,
alkyl, alkoxy, aryl, alkylsulfonyl or arylsulfonyl,
[0025] A.sup.2 furthermore represents alkanediyl, alkanediyl,
azaalkenediyl, alkinediyl, cycloalkanediyl, cycloalkenediyl or
phenylene, in each case optionally substituted by halogen,
[0026] A.sup.3 represents hydrogen, with the proviso that in this
case A.sup.1 and/or A.sup.2 do(es) not represent any single
bond,
[0027] A.sup.3 furthermore represents hydroxyl, mercapto, amino,
cyano, isocyano, thiocyanato, nitro, carboxyl, carbamoyl,
thiocarbamoyl, sulfo, chloro-sulfonyl or halogen, or represents
alkyl, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, alkylamino,
dialkylamino, alkoxycarbonyl or dialkoxy(thio)-phosphoryl, in each
case optionally substituted by halogen or alkoxy,
[0028] A.sup.3 furthermore represents alkenyl, alkenyloxy,
alkenylthio, alkenylamino, alkylidenamino, alkenyloxycarbonyl,
alkinyl, alkinyloxy, alkinylthio, alkinylamino or
alkinyloxycarbonyl, in each case optionally substituted by
halogen,
[0029] A.sup.3 furthermore represents cycloalkyl, cycloalkyloxy,
cycloalkylalkyl, cycloalkylalkoxy, cycloalkylidenamino,
cycloalkyloxycarbonyl or cycloalkylalkoxycarbonyl, in each case
optionally substituted by halogen cyano, carboxyl, alkyl and/or
alkoxy-carbonyl,
[0030] A.sup.3 furthermore represents aryl, aryloxy, aralkyl,
arylalkoxy, aryloxycarbonyl or arylalkoxycarbonyl, in each case
optionally substituted by nitro, cyano, carboxyl, halogen alkyl,
halogenalkyl, alkyloxy, halogenalkyloxy and/or alkoxy-carbonyl,
[0031] A.sup.3 furthermore represents in each case optionally
completely or partly hydrogenated pyrrolyl, pyrazolyl, imidazolyl,
triazolyl, furyl, oxiranyl, oxetanyl, dioxolanyl, thienyl,
oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, oxadiazolyl,
thiadiazolyl, pyridinyl, pyrimidinyl, triazinyl, pyrazolylalkenyl,
furylalkyl, thienylalkyl, oxazolylalkyl, isoxazolylalkyl,
thiazolylalkyl, pyridinylalkyl, pyrimidinylalkyl, pyrazolylalkoxy
or furylalkyl, or represents perhydropyranylalkoxy or
pyridylalkoxy, and
[0032] R.sup.7 represents hydrogen or halogen,
[0033] or in each case two adjacent radicals--R.sup.3 and R.sup.4,
R.sup.4 and R.sup.5, R.sup.5 and R.sup.6 or R.sup.6 and
R.sup.7--together represent one of the following groupings
[0034] --Q.sup.3--CQ.sup.4--, --Q.sup.3--CQ.sup.4--Q.sup.5--,
--Q.sup.3--C(R.sup.8,R.sup.9)--Q.sup.5--,
--C(R.sup.8,R.sup.9)--CQ.sup.4-- -,
--C(R.sup.8,R.sup.9)--Q.sup.3--CQ.sup.4--,
--Q.sup.3--C(R.sup.8,R.sup.9- )--C(R.sup.8,R.sup.9)--,
--Q.sup.3--C(R.sup.8,R.sup.9)--C(R.sup.8,R.sup.9)- --Q.sup.5--,
--C(R.sup.8,R.sup.9)--CQ.sup.4--, --Q.sup.3--C(R.sup.8).dbd.C-
(R.sup.8)--, --C(R.sup.8).dbd.C(R.sup.8)--CQ.sup.4--,
--Q.sup.3--C(R.sup.8,R.sup.9)--CQ.sup.4--,
--N(R.sup.10)--C(R.sup.8,R.sup- .9)--CQ.sup.4--,
--C(R.sup.8).dbd.N--, --Q.sup.3--CQ.sup.4--C(R.sup.8,R.su- p.9)--,
--Q.sup.3--CQ.sup.4--N(R.sup.10)--, --Q.sup.3--C(R.sup.8,R.sup.9)--
-CQ.sup.4--N(R.sup.10)--,
--C(R.sup.8,R.sup.9)--CQ.sup.3--CQ.sup.4--N(R.su- p.10)--,
--C(R.sup.8,R.sup.9)--C(R.sup.8,R.sup.9)--N(R.sup.10)--,
--C(R.sup.8,R.sup.9) --C(R.sup.8,R.sup.9)--CQ.sup.4--N(R.sup.10)--,
--C(R.sup.8).dbd.C(R.sup.8)--N(R.sup.10)--,
--C(R.sup.8).dbd.C(R.sup.8)--- CQ.sup.4--N(R.sup.10)--,
--C(R.sup.8,R.sup.9)--CQ.sup.4--N(R.sup.10)--,
--N(R.sup.10)--C(R.sup.8,R.sup.9)--CQ.sup.4--N(R.sup.10)--,
--C(R.sup.8).dbd.N--N(R.sup.10)--,
--Q.sup.3--C--Q.sup.4--C(R.sup.8,R.sup- .9)--N(R.sup.10)--,
--Q.sup.3--C(R.sup.8,R.sup.9)--(R.sup.8,R.sup.9)--CQ.s-
up.4--N(R.sup.10)--
[0035] in which
[0036] Q.sup.3, Q.sup.4 and Q.sup.5 are identical or different and
in each case represent oxygen or sulfur,
[0037] R.sup.8 and R.sup.9 are identical or different and
individually represent hydrogen, halogen or alkyl or together
represent alkanediyl, and
[0038] R.sup.10 represents hydrogen or hydroxyl, or represents
alkyl, alkylcarbonyl, alkoxycarbonyl or alkylsulfonyl Which are
optionally substituted by cyano, halogen, alkoxy, alkyl-carbonyl or
alkoxy-carbonyl, or represents alkenyl or alkinyl, in each case
optionally substituted by halogen, or represents cycloalkyl or
cycloalkylalkyl, in each case optionally substituted by halogen or
alkyl, or represents alkoxy or alkenyloxy, in each case optionally
substituted by halogen or represents arylalkyl or arylalkoxy, in
each case optionally substituted by cyano, halogen, alkyl,
halogenoalkyl, alkoxy or halogenoalkoxy,
[0039] have now been found, the already known compounds
4-(3,4-dichlorophenyl)-1,2-dimethyl-5-thioxo-1,2,4-triazolidin-3-one
and
4-(4-chloro-3-trifluoromethylphenyl)-1,2-dimethyl-5-thioxo-1,2,4-triazoli-
din-3-one (cf. DE 2952685 and DE 3026739) being excluded by
disclaimer.
[0040] The compounds isomeric to the substituted N-aryl
nitrogen-containing heterocyclic compounds of the formula (I), of
the formulae (Ia) and (Ib) 5
[0041] in which
[0042] Q.sup.1, Q.sup.2, R.sup.1, R.sup.2 and Ar have the
abovementioned meanings, have furthermore also been found.
[0043] The novel substituted N-aryl nitrogen-containing
heterocyclic compounds of the general formula (I) and, where
appropriate, the compounds of the formulae (Ia) or (Ib) are
obtained when
[0044] (a) (thio)semicarbazide derivatives of the general formula
(II) 6
[0045] in which
[0046] Q.sup.1, Q.sup.2, R.sup.1, R.sup.2 and Ar have the
abovementioned meanings and
[0047] R represents alkyl.
[0048] are subjected to a cyclizing condensation reaction, if
appropriate in the presence of a reaction auxiliary and if
appropriate in the presence of a diluent, and thereafter, if
appropriate, electrophilic or nucleophilic substitution reactions
are carried out in the customary manner in the context of the
definition of the substituents.
[0049] or when
[0050] (b) aryliminoheterocyclic compounds of the general formula
(III) 7
[0051] in which
[0052] Q.sup.1, Q.sup.2, R.sup.1, R.sup.2 and Ar have the
abovementioned meanings, --or compounds of the formula (Ia) or
(Ib)--above--
[0053] are isomerized thermally ("pyrolytically"), if appropriate
in the presence of a reaction auxiliary and if appropriate in the
presence of a diluent
[0054] The compounds of the formula (I) can in principle also be
synthesized as shown schematically below:
[0055] (c) reaction of aryl iso(thio)cyanates of the formula (IV)
with hydrazines of the formula (V) to give aryl(thio)semicarbazides
of the formula (VI) and reaction thereof with (thio)phosgene: 8
[0056] (d) reaction of aryl iso(thio)cyanates of the formula (IV)
with S-alkyldithio-carbazates of the formula (VII) and subsequent
cyclizing condensation: 9
[0057] (e) reaction of N,N-bis-chlorocarbonyl- or
N,N-bis-phenoxycarbonyl-- arylamines of the formula (VIII)--Y:Cl or
OC.sub.6H.sub.5--with hydrazines of the formula (V): 10
[0058] (f) reaction of arylamines of the formula (IX) with
hydrazinedicarboxylic acid esters of the formula (X): 11
[0059] The compounds of the general formula (I) can also be
converted into other compounds of the general formula (I) according
to the above definition by further customary methods, for example
by customary, conversions of carboxylic acid groupings or
derivatives thereof (for example R.sup.5: COOH.fwdarw.COCl,
COOH.fwdarw.COOCH.sub.3, COCl.fwdarw.CONH.sub.2,
COOCH.sub.3.fwdarw.CONH.sub.2, CONH.sub.2 .fwdarw.CN,
CN.fwdarw.CSNH.sub.2), by alkylation reactions (for example
R.sup.1: H.fwdarw.CH.sub.3 or CHF.sub.2) or by oxidation or
sulfurization (for example Q.sup.1: O.fwdarw.S or S.fwdarw.O)--cf.
also the preparation examples.
[0060] The novel substituted N-aryl nitrogen-containing
heterocyclic compounds of the general formula (I) are distinguished
by a potent herbicidal activity.
[0061] In the definitions, the saturated or unsaturated hydrocarbon
chains, such as alkyl, alkenyl or alkinyl, are in each case
straight-chain or branched.
[0062] Halogen in general represents fluorine, chlorine, bromine or
iodine, preferably fluorine, chlorine or bromine, in particular
fluorine or chlorine.
[0063] The invention preferably relates to compounds of the
formulae (I), (Ia) and (Ib) in which
[0064] Q.sup.1 represents oxygen or sulfur,
[0065] Q.sup.2 represents oxygen or sulfur,
[0066] R.sup.1 represents hydrogen, cyano or formyl, or represents
C.sub.1-C.sub.6-alkyl, in each case optionally substituted by
fluorine, chlorine, cyano, carboxyl, C.sub.1-C.sub.4-alkoxy,
C.sub.3-C.sub.4-alkenyloxy, C.sub.3-C.sub.4-alkinyloxy,
C.sub.1-C.sub.4-alkylthio, C.sub.3-C.sub.4-alkenylthio,
C.sub.3-C.sub.4-alkinylthio, C.sub.1-C.sub.4-alkoxy-carbonyl,
C.sub.3-C.sub.4-alkenyloxy-carbonyl or
C.sub.3-C.sub.4-alkinyloxy-carbony- l,
[0067] R.sup.1 furthermore represents C.sub.3-C.sub.6-alkenyl or
C.sub.3-C.sub.6-alkinyl, in each case optionally substituted by
fluorine or chlorine.
[0068] R.sup.1 furthermore represents
C.sub.1-C.sub.6-alkyl-carbonyl, C.sub.3-C.sub.6-alkenyl-carbonyl,
C.sub.3-C.sub.6-alkinyl-carbonyl, C.sub.1-C.sub.6-alkoxy-carbonyl,
C.sub.3-C.sub.6-alkenyloxy-carbonyl or
C.sub.3-C.sub.6-alkinyloxy-carbonyl, in each case optionally
substituted by fluorine or chlorine,
[0069] R.sup.1 furthermore represents C.sub.3-C.sub.6-cycloalkyl or
C.sub.3-C.sub.6-cycloalkyl-carbonyl, in each case optionally
substituted by fluorine, chlorine, bromine, cyano or carboxyl,
[0070] R.sup.2 represents hydrogen, cyano or formyl, or represents
C.sub.1-C.sub.6-alkyl in each case optionally substituted by
fluorine, chlorine, cyano, carboxyl, C.sub.1-C.sub.4-alkoxy,
C.sub.3-C.sub.4-alkenyloxy, C.sub.3-C.sub.4-alkinyloxy,
C.sub.1-C.sub.4-alkylthio, C.sub.3-C.sub.4-alkenylthio,
C.sub.3-C.sub.4-alkylthio, C.sub.1-C.sub.4-alkoxy-carbonyl,
C.sub.3-C.sub.4-alkenyloxy-carbonyl or C.sub.3-C.sub.4-alkinyloxy
carbonyl,
[0071] R.sup.2 furthermore represents C.sub.3-C.sub.6-alkenyl or
C.sub.3-C.sub.6-alkinyl, in each case optionally substituted by
fluorine or chlorine.
[0072] R.sup.2 furthermore represents
C.sub.1-C.sub.6-alkyl-carbonyl, C.sub.3-C.sub.6-alkenyl carbonyl,
C.sub.3-C.sub.6-alkylcarbonyl, C.sub.1-C.sub.6-alkoxy carbonyl,
C.sub.3-C.sub.6-alkenyloxy carbonyl or
C.sub.3-C.sub.6-alkinyloxy-carbonyl, in each case optionally
substituted by fluorine or chlorine,
[0073] R.sup.2 furthermore represents C.sub.3-C.sub.6-cycloalkyl or
C.sub.3-C.sub.6-cycloalkyl-carbonyl, in each case optionally
substituted by fluorine, chlorine, bromine, cyano or carboxyl,
and
[0074] Ar represents the substituted monocyclic or bicyclic aryl or
heteroaryl grouping defined below 12
[0075] in which
[0076] R.sup.3 represents hydrogen, fluorine, chlorine or
bromine,
[0077] R.sup.4 represents hydrogen, fluorine, chlorine or
bromine,
[0078] R.sup.5 represents cyano, carboxyl, chlorocarbonyl,
carbamoyl, thiocarbamoyl, hydroxyl, fluorine, chlorine, bromine or
represents alkyl, alkoxy or alkoxycarbonyl having in each case up
to 4 carbon atoms and in each case optionally substituted by
fluorine and/or chlorine,
[0079] R.sup.6 represents the following grouping
--A.sup.1--A.sup.2--A.sup.3
[0080] in which
[0081] A.sup.1 represents a single bond, or represents oxygen,
sulfur, --SO--, --SO.sub.2--, --CO-- or the grouping
--N--A.sup.4--, in which A.sub.4 represents hydrogen, hydroxyl,
C.sub.1-C.sub.4-alkyl, C.sub.3-C.sub.4-alkenyl,
C.sub.3-C.sub.4-alkinyl, C.sub.1-C.sub.4-alkoxy, phenyl,
C.sub.1-C.sub.4-alkyl-carbonyl, phenylcarbonyl,
C.sub.1-C.sub.4-alkyl-sulfonyl or phenylsulfonyl,
[0082] A.sup.1 furthermore represents C.sub.1-C.sub.6-alkanediyl,
C.sub.2-C.sub.6-alkanediyl, C.sub.2-C.sub.6-azaalkenediyl,
C.sub.2-C.sub.6-aeinediyl, C.sub.3-C.sub.6-cycloalkanediyl,
C.sub.3-C.sub.6-cycloalkenediyl or phenylene, in each case
optionally substituted by fluorine, chlorine or bromine,
[0083] A.sup.2 represents a single bond, or represents oxygen,
sulfur, --SO--, --SO.sub.2--, --CO-- or the grouping
--N--A.sup.4--, in which A.sup.4 represents hydrogen, hydroxyl,
C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-alkoxy, phenyl,
C.sub.1-C.sub.4-alkylsulfonyl or phenylsulfonyl,
[0084] A.sup.2 furthermore represents C.sub.1-C.sub.6-alkanediyl,
C.sub.2-C.sub.6-alkanediyl, C.sub.2-C.sub.6-azaalkenediyl,
C.sub.2-C.sub.6-alkenyl, C.sub.3-C.sub.6-cycloalkanediyl,
C.sub.3-C.sub.6-cycloalkenediyl or phenylene, in each case
optionally substituted by fluorine, chlorine or bromine,
[0085] A.sup.3 represents hydrogen with the proviso that in this
case A.sup.1 and/or A.sup.2 do(es) not represent a single bond
[0086] A.sup.3 furthermore represents hydroxyl, mercapto, amino,
cyano, isocyano, thiocyanato, nitro, carboxyl, carbamoyl,
thiocarbamoyl, sulfo, chlorosulfonyl, fluorine, chlorine or
bromine.
[0087] A.sup.3 furthermore represents alkyl, alkoxy, alkylthio,
alkylsulfinyl, alkylsulfonyl, alkylamino, dialkylamino,
alkoxycarbonyl or dialkoxy(thio)phosphoryl having in each case 1 to
6 carbon atoms in the alkyl groups and in each case optionally
substituted by fluorine, chlorine or C.sub.1-C.sub.4-alkoxy,
[0088] A.sup.3 furthermore represents alkenyl, alkenyloxy,
alkenylamino, alkylidenamino, alkenyloxycarbonyl, alkinyl,
alkinyloxy, alkinylamino or alkinyloxycarbonyl having in each case
2 to 6 carbon atoms in the alkenyl, alkylidene or alkinyl groups
and in each case optionally substituted by fluorine or
chlorine,
[0089] A.sup.3 furthermore represents cycloalkyl, cycloalkyloxy,
cycloalkylalkyl, cycloalkylalkoxy, cycloalkylidenamino,
cycloalkyloxycarbonyl or cycloalkylalkoxycarbonyl having in each
case 3 to 6 carbon atoms in the cycloalkyl groups and where
appropriate 1 to 4 carbon atoms in the alkyl groups and in each
case optionally substituted by fluorine, chlorine, cyano, carboxyl,
C.sub.1-C.sub.4-alkyl and/or C.sub.1-C.sub.4-alkoxy carbonyl,
[0090] A.sup.3 furthermore represents phenyl, phenyloxy,
phenyl-C.sub.1-C.sub.4-alkyl, phenyl-C.sub.1-C.sub.4-alkoxy,
phenyloxycarbonyl or phenyl-C.sub.1-C.sub.4-alkoxycarbonyl, in each
case optionally substituted by nitro, cyano, carboxyl, fluorine,
chlorine, bromine, C.sub.1-C.sub.4-alkyl,
C.sub.1-C.sub.4-halogenalkyl, C.sub.1-C.sub.4-alkyloxy,
C.sub.1-C.sub.4-halogenalkyloxy and/or
C.sub.1-C.sub.4-alkoxy-carbonyl,
[0091] A.sup.3 furthermore represents in each case optionally
completely or partly hydrogenated pyrrolyl, pyrazolyl, imidazolyl,
triazolyl, furyl, oxiranyl, oxetanyl, dioxolanyl, thienyl,
oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, oxadiazolyl,
thiadiazolyl, pyridinyl, pyrimidinyl, triazinyl,
pyrazolyl-C.sub.1-C.sub.4-alkyl, furyl-C.sub.1-C.sub.4-alkyl,
thienyl-C.sub.1-C.sub.4-alkyl, oxazolyl-C.sub.1-C.sub.4-alkyl,
isoxazolyl-C.sub.1-C.sub.4-alkyl, thiazolyl-C.sub.1-C.sub.4-alkyl,
pyridinyl-C.sub.1-C.sub.4-alkyl, pyrimidinyl-C.sub.1-C.sub.4-alkyl,
pyrazolylmethoxy or furylmethoxy, or represents
perhydropyranylmethoxy or pyridylmethoxy, and
[0092] R.sup.7 represents hydrogen, fluorine or chlorine,
[0093] or in each case two adjacent radicals--R.sup.3 and R.sup.4,
R.sup.4 and R.sup.5, R.sup.5 and R.sup.6 or R.sup.6 and R.sup.7
--together represent one of the following groupings
[0094] --Q.sup.3--CQ.sup.4--, --Q.sup.3--CQ.sup.4--Q.sup.5--,
--Q.sup.3--C(R.sup.8,R.sup.9)--Q.sup.5,
--C(R.sup.8,R.sup.9)--CQ.sup.4--,
--C(R.sup.8,R.sup.9)--Q.sup.3--CQ.sup.4--,
--Q--C(R.sup.8,R.sup.9)--C(R.s- up.8,R.sup.9)--,
--Q.sup.3--C(R.sup.8,R.sup.9)--C(R.sup.8,R.sup.9)--Q.sup.- 5--,
--C(R.sup.8,R.sup.9)--C(R.sup.8,R.sup.9)--CQ.sup.4--,
--Q.sup.3--C(R.sup.8).dbd.C(R.sup.8)--,
--C(R.sup.8).dbd.C(R.sup.8)--CQ.s- up.4--,
--Q.sup.3--C(R.sup.8,R.sup.9)--CQ.sup.4--, --N(R.sup.10)--C(R.sup.-
8,R.sup.9)--CQ.sup.4--, --C(R.sup.8).dbd.N--,
--Q.sup.3--CQ.sup.4--C(R.sup- .8,R.sup.9)--,
--Q.sup.3--CQ.sup.4--N(R.sup.10)--, --Q.sup.3--(R.sup.8,R.s-
up.9)--CQ.sup.4--N(R.sup.10)--,
--C(R.sup.8,R.sup.9)--Q.sup.3--CQ.sup.4--N- (R.sup.10)--,
--C(R.sup.8,R.sup.9)--C(R.sup.8,R.sup.9)--N(R.sup.10)--,
--C(R.sup.8,R.sup.9)--C(R.sup.8,R.sup.9)--CQ.sup.4--N(R.sup.10)--,
--C(R.sup.8).dbd.C(R.sup.8)--N(R.sup.10)--,
C(R.sup.8).dbd.C(R.sup.8)--CQ- .sup.4--N(R.sup.10)--,
--C(R.sup.8,R.sup.9)--CQ.sup.4--N(R.sup.10)--,
N(R.sup.10)--C(R.sup.8,R.sup.9)--CQ.sup.4--N(R.sup.10)--,
--C(R.sup.8).dbd.N--N(R.sup.10)--,
--Q.sup.3--CQ.sup.4--C(R.sup.8,R.sup.9- )--N(R.sup.10)--,
Q.sup.3--C(R.sup.8,R.sup.9)--C(R.sup.8,R.sup.9)--CQ.sup.-
4--N(R.sup.10)
[0095] in which
[0096] Q.sup.3, Q.sup.4 and Q.sup.5 are identical or different and
in each case represent oxygen or sulfur,
[0097] R.sup.8 and R.sup.9 are identical or different and
individually represent oxygen, fluorine, chlorine, bromine or
C.sub.1-C.sub.4-alkyl or together represent
C.sub.2-C.sub.5-alkanediyl, and
[0098] R.sup.10 represents hydrogen or hydroxyl, or represents
alkyl, alkylcarbonyl, alkoxycarbonyl or alkylsulfonyl having in
each case 1 to 6 carbon atoms in the alkyl groups and in each case
optionally substituted by cyano, fluorine, chlorine,
C.sub.1-C.sub.4-alkoxy, C.sub.1-C.sub.4-alkyl carbonyl or
C.sub.1-C.sub.4-alkoxy-carbonyl,
[0099] R.sup.10 furthermore represents alkenyl or alkinyl having in
each case 2 to 6 carbon atoms and in each case optionally
substituted by fluorine, chlorine or bromine,
[0100] R.sup.10 furthermore represents cycloalkyl or
cycloalkylalkyl having in each case 3 to 6 carbon atoms in the
cycloalkyl groups and were appropriate 1 to 3 atoms in the alkyl
group and in each case optionally substituted by fluorine,
chlorine, bromine or C.sub.1-C.sub.4-alkyl,
[0101] R.sup.10 furthermore represents alkoxy or alkenyloxy having
in each case up to 6 carbon atoms and in each case optionally
substituted by fluorine and/or chlorine, and
[0102] R.sup.10 furthermore represents benzyl or benzyloxy, in each
case optionally substituted by cyano, fluorine, chlorine,
C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-halogenoalkyl,
C.sub.1-C.sub.4-alkoxy or C.sub.1-C.sub.4-halogenoalkoxy,
[0103] the already known compounds
4-(3,4-dichloro-phenyl)-1,2-dimethyl-5--
thioxo-1,2,4-triazolidin-3-one and
4-(4-chloro-3-trifluoromethyl-phenyl)-1-
,2-dimethyl-5-thioxo-1,2,4-triazolidin-3-one (cf. DE 2952685 and DE
3026739) being excluded by disclaimer.
[0104] The invention particularly relates to compounds of the
formulae (I), (Ia) and (Ib) in which
[0105] Q.sup.1 represents oxygen or sulfur,
[0106] Q.sup.2 represents oxygen or sulfur,
[0107] R.sup.1 represents hydrogen, cyano or formyl or represents
methyl, ethyl, n- or i-propyl or n-, i-, s- or t-butyl, in each
case optionally substituted by fluorine, chlorine, cyano, carboxyl,
methoxy or ethoxy,
[0108] R.sup.1 furthermore represents propenyl, butenyl, propinyl
or butinyl, in each case optionally substituted by fluorine or
chlorine,
[0109] R.sup.1 furthermore represents acetyl, propionyl,
methoxycarbonyl or ethoxycarbonyl, in each case optionally
substituted by fluorine or chlorine.
[0110] R.sup.1 furthermore represents cyclopropyl which is
optionally substituted by fluorine or chlorine,
[0111] R.sup.2represents hydrogen, cyano or formyl, or represents
methyl, ethyl, n- or i-propyl or n-, i-, s- or t-butyl, in each
case optionally substituted by fluorine, chlorine, cyano, carboxyl,
methoxy or ethoxy,
[0112] R.sup.2 furthermore represents propenyl, butenyl, propinyl
or butinyl, in each case optionally substituted by fluorine or
chlorine,
[0113] R.sup.2 furthermore represents acetyl, propionyl,
methoxycarbonyl or ethoxycarbonyl, in each case optionally
substituted by fluorine or chlorine,
[0114] R.sup.2 furthermore represents cyclopropyl which is
optionally substituted by fluorine or chlorine, and
[0115] A.sup.1 represents the substituted monocyclic or bicyclic
aryl or heteroaryl grouping defined below 13
[0116] in which
[0117] P.sup.3 represents hydrogen fluorine or chlorine.
[0118] R.sup.4 represents hydrogen, fluorine or chlorine.
[0119] R.sup.5 represents cyano thiocarbamoyl, chlorine, bromine
methyl, trifluoromethyl. methoxy, difluoromethoxy or
trifluoromethoxy,
[0120] R.sup.6 represents the following grouping
--A.sup.1--A.sup.2--A.sup.3
[0121] in which
[0122] A.sup.1 represents a single bond, or represents oxygen,
sulfur, --SO--, --SO.sub.2--, --CO-- or the grouping
--N--A.sup.4--, in which A.sup.4 represents hydrogen, hydroxyl,
methyl, ethyl, n- or i-propyl, methoxy, ethoxy, n- or i-propoxy,
methylsulfonyl or ethylsulfonyl,
[0123] A.sup.1 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,
[0124] A.sup.2 represents a single bond, or represents oxygen
sulfur, --SO--, --SO.sub.2--, --CO-- or the grouping
--N--A.sup.4--, in which A.sup.4 represents oxygen, hydroxyl,
methyl, ethyl, n- or i-propyl, methoxy, ethoxy, n- or i-propoxy,
methylsulfonyl, ethylsulfonyl, n- or i-propylsulfonyl or
phenylsulfonyl,
[0125] A.sup.2 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,
[0126] A.sup.3 represents hydrogen, with the proviso that in this
case A.sup.1 and/or A.sup.2 do(es) not represent a single bond,
[0127] A.sup.3 furthermore represents hydroxyl, amino, cyano,
nitro, carboxyl, carbamoyl, sulfo, fluorine, chlorine or
bromine.
[0128] A.sup.3 furthermore 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 methylsulfinyl, ethylsulfinyl, n- or
i-propylsulfinyl, methylsulfonyl, ethylsulfonyl, n- or
i-propylsulfonyl, methylamino. ethylamino, n- or i-propyl amino,
n-, i-, s- or t-butylamino, dimethylamino, diethylamino,
methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl,
dimethoxyphosphoryl, diethoxyphosphoryl, dipropoxyphosphoryl or
diisopropoxyphosphoryl, in each case optionally substituted by
fluorine, chlorine, methoxy or ethoxy,
[0129] A.sup.3 furthermore represents propenyl, butenyl,
propenyloxy, butenyloxy, propenylamino, butenylamino,
propylidenamino, butylidenamino, propenyloxycarbonyl,
butenyloxycarbonyl, propinyl, butinyl, propinyloxy, butinyloxy,
propinylamino, butinylamino, propinyloxycarbonyl or
butinyloxycarbonyl, in each case optionally substituted by fluorine
or chlorine,
[0130] A.sup.3 furthermore represents cyclopropyl, cyclobutyl,
cyclopentyl, cyclohexyl, cyclopropyloxy, cyclobutyloxy,
cyclopentyloxy, cyclohexyloxy, cyclopropylmethyl, cyclobutylmethyl,
cyclopentylmethyl, cyclohexylmethyl, cyclopropylmethoxy,
cyclo-butylmethoxy, cyclopentylmethoxy, cyclohexylmethoxy,
cyclopentylidenamino, cyclohexylidenamino, cyclopentyloxy-carbonyl,
cyclohexyloxycarbonyl, cyclopentylmethoxycarbonyl or
cyclohexylmethoxycarbonyl, in each case optionally substituted by
fluorine, chlorine, cyano, carboxyl, methyl, ethyl, n- or i-propyl,
methoxycarbonyl or ethoxycarbonyl,
[0131] A.sup.3 furthermore represents phenyl, phenyloxy, benzyl,
phenylethyl, benzyloxy, phenyloxycarbonyl or benzyloxycarbonyl, in
each case 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,
[0132] A.sup.3 furthermore represents in each case optionally
completely or partly hydrogenated pyrrolyl, pyrazolyl, imidazolyl,
triazolyl, furyl, thienyl, oxazolyl, isoxazoly, thiazolyl,
isothiazolyl, oxadiazolyl, thiadiazolyl, pyridinyl, pyrimidinyl,
triazinyl, pyrazolylmethyl, furylmethyl, thienylmethyl,
oxazolylmethyl, isoxazolylmethyl, thiazolylmethyl,pyridinylmethyl,
pyrimidinylmethyl, pyrazolylmethoxy, furylmethoxy or
pyridylmethoxy,
[0133] R.sup.7 represents hydrogen, fluorine or chlorine,
[0134] or in each case two adjacent radicals--R.sup.3 and R.sup.4,
R.sup.4 and R.sup.5, R.sup.5 and R.sup.6 or R.sup.6 and
R.sup.7--together represent one of the following groupings
[0135] --Q.sup.3--CQ.sup.4--, --Q.sup.3--CQ.sup.4--Q.sup.5--,
--Q.sup.3--C(R.sup.8,R.sup.9)--Q.sup.5--,
--C(R.sup.8,R.sup.9)--CQ.sup.4-- -,
--C(R.sup.8,R.sup.9)--Q.sup.3--CQ.sup.4--,
--Q.sup.3--C(R.sup.8,R.sup.9- )--C(R.sup.8,R.sup.9)--,
--Q.sup.3--C(R.sup.8,R.sup.9)--C(R.sup.8,R.sup.9)- --Q.sup.5--,
--C(R.sup.8,R.sup.9)--C(R.sup.8,R.sup.9)--CQ.sup.4--,
--Q.sup.3--C(R.sup.8).dbd.C(R.sup.8)--,
--C(R.sup.8).dbd.C(R.sup.8)--CQ.s- up.4--,
--Q.sup.3--C(R.sup.8,R.sup.9)--CQ.sup.4--, --N(R.sup.10)--C(R.sup.-
8,R.sup.9)--CQ.sup.4--, --C(R.sup.8).dbd.N--,
--Q.sup.3--CQ.sup.4--C(R.sup- .8,R.sup.9)--,
--Q.sup.3--CQ.sup.4--N(R.sup.10)--, --Q.sup.3--C(R.sup.8,R.-
sup.9)--CQ.sup.4--N(R.sup.10)--,
--C(R.sup.8,R.sup.9)--Q.sup.3--CQ.sup.4--- N(R.sup.10)--,
--C(R.sup.8,R.sup.9)--C(R.sup.8,R.sup.9)--N(R.sup.10)--,
--C(R.sup.8,R.sup.9)--C(R.sup.8,R.sup.9)--CQ.sup.4--N(R.sup.10)--,
--C(R.sup.8).dbd.C(R.sup.8)--N(R.sup.10)--,
--C(R.sup.8).dbd.C(R.sup.8)--- CQ.sup.4--N(R.sup.10)--,
--C(R.sup.8,R.sup.9)--CQ.sup.4--N(R.sup.10)--,
--N(R.sup.10)--C(R.sup.8,R.sup.9)--CQ.sup.4--N(R.sup.10)--,
--C(R.sup.8).dbd.N--N(R.sup.10)--,
--Q.sup.3--CQ.sup.4--C(R.sup.8,R.sup.9- )--N(R.sup.10)--,
Q.sup.3--C(R.sup.8,R.sup.9)--CQ.sup.4--N(R.sup.10)--,
[0136] in wich
[0137] Q.sup.3, Q.sup.4 and Q.sup.5 are identical or different and
in each case represent oxygen or sulfur.
[0138] R.sup.8 and R.sup.9 are identical or different and
individually represent hydrogen fluorine, chlorine, methyl or
ethyl, or together represent ethane-1,2-diyl (dimethylene), and
[0139] R.sup.10 represents hydrogen or hydroxyl, or represents
methyl, ethyl, n- or i-propyl or n-, i-, s- or t-butyl which are
optionally substituted by cyano, fluorine chlorine, methoxy ethoxy,
acetyl, propionyl, methoxycarbonyl or ethoxy-carbonyl,
[0140] R.sup.10 furthermore represents propenyl, butenyl, propinyl
or butinyl, in each case optionally substituted by fluorine,
chlorine or bromine,
[0141] R.sup.10 furthermore represents cyclopropyl, cyclobutyl,
cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclobutylmethyl,
cyclopentylmethyl or cyclohexylmethyl, in each case optionally
substitute by fluorine, chlorine, bromine, methyl or ethyl,
[0142] R.sup.10 furthermore represents methoxy, ethoxy, n- or
i-propoxy, n-, i- or s-butoxy, propenyloxy or butenyloxy, in each
case optionally substituted by fluorine and/or chlorine, and
[0143] R.sup.10 furthermore represents benzyl or benzyloxy, in each
case optionally substituted by cyano, fluorine, chlorine, methyl,
ethyl, trifluoromethyl, methoxy, ethoxy, difluoromethyl or
trifluoromethoxy,
[0144] the already known compounds
4-(3,4-dichloro-phenyl)-1,2-dimethyl-5--
thioxo-1,2,4-triazolidin-3-one and
4-(4-chloro-3-trifluoromethyl-phenyl)-1-
,2-dimethyl-5-thioxo-1,2,4-triazolidin-3-one (cf. DE 2952685 and DE
3026739) being excluded by disclaimer.
[0145] The above mentioned definitions of radicals given generally
or in preferred ranges apply both to the end products of the
formula (I) and also correspondingly to the staring substances or
intermediate products in each case required for the preparation.
These definitions of radicals can be combined with one another as
desired, that is to say also between the stated ranges of preferred
compounds.
[0146] Examples of the compounds of the formula (I) according to
the invention are given in the following groups.
Group 1
[0147] 14
[0148] Ar here has, for example, the meanings listed below:
[0149] 2,4-dichloro-phenyl, 3-chloro-4-fluoro-phenyl,
2-chloro-4-cyano-phenyl, 2-fluoro-4-cyano-phenyl,
4,5-difluoro-phenyl, 2,4,5-trichloro-phenyl,
2,4-dichloro-5-fluoro-phenyl, 2-chloro-4,5-difluoro-phenyl,
4chloro-2,5-di-fluoro-phenyl, 5-chloro-2,4-difluoro-phenyl,
2-fluoro-5-chloro-4-cyano-phenyl, 2,4,5-trifluoro-phenyl,
2,5-dichloro-4-cyano-phenyl, 2-chloro-5-fluoro-4-cyano-phenyl,
2-chloro-4,5-dicyano-phenyl, 2-chloro-4-fluoro-5-cyano-phenyl,
2,5-difluoro-4-cyano-phenyl, 4-cyano-3-methyl-phenyl,
2-chloro-4-cyano-5-methyl-phenyl, 2,4-dichloro-5-methoxy-phenyl,
2,4-dichloro-5-ethoxy-phenyl,
2,4-dichloro-5-n-propoxy-phenyl,2,4-dichloro-5-i-propoxy-phenyl,
4-chloro-2-fluoro-5-methoxy-phenyl,
4-chloro-2-fluoro-5-ethoxy-phenyl,
4-chloro-2-fluoro-5-n-propoxy-phenyl,
4-chloro-2-fluoro-5-i-propoxy-pheny- l,
2-fluoro-4-cyano-5-methyl-phenyl, 2,4-dichloro-5-methyl-phenyl,
2-chloro-4-cyano-5-trifluoromethyl-phenyl,
4-fluoro-3-trifluoromethyl-phe- nyl,
2-fluoro-4-cyano-5-trifluoromethyl-phenyl,
2-chloro-4-methyl-5-triflu- oromethyl-phenyl,
2-chloro-5-fluoro-4-methoxy-phenyl,
2-fluoro-4-methoxy-5-methyl-phenyl,
2,5-difluoro-4-thicarbamoyl-phenyl,
2-chloro-4-fluoro-5-i-propoxy-phenyl,
2-fluoro-4-cyano-5-methoxy-phenyl,
2-fluoro-4-cyano-5-i-propoxy-phenyl,
2-chloro-4-cyano-5-(2-propinyloxy)-p- henyl,
2-fluoro-4-cyano-5-(1-methyl-2-propinyloxy)-phenyl,
2-fluoro-4-chloro-5-(1-methyl-2-propinyloxy)-phenyl,
2-chloro-4-thio-carbamoyl-5-i-propoxy-phenyl,
2-fluoro-4-cyano-5-(2-prope- nyloxy)-phenyl,
2-fluoro-4-chloro-5-(2-propenyloxy)-phenyl,2-chloro-4-cyan-
o-5-methyl-sulfonylamino-phenyl,
2-fluoro-4-cyano-5-ethylsulfonylamino-phe- nyl,
2-fluoro-4-thiocarbamoyl-5-methylsulfonylamino-phenyl,
2-fluoro-4-cyano-5-ethylsulfonylamino-phenyl,
2-fluoro-4-cyano-5cyclpropy- lsulfonylamino-phenyl,
2-fluoro-4-cyano-5-i-propylsulfonylamino-phenyl,
2-chloro-4-thiocarbamoyl-5-ethylsulfonylamino-phenyl,
2-chloro-4-cyano-5-cyanamino-phenyl,
2-fluoro-4-cyano-5-(2,2-difluoroethy- lsulfonylamino)-phenyl,
2-fluoro-4-cyano-5-phenyl-sulfonylamino-phenyl,
2-fluoro-4-cyano-5-t-butylsulfonylamino-phenyl,
2-chloro-4-cyano-5-methox- ycarbonyl-phenyl,
2-fluoro-4-cyano-5-ethoxycarbonyl-phenyl,
2-fluoro-4-chloro-5-ethoxycarbonyl-phenyl,
2-fluoro-4-thiocarbamoyl-5-met- hoxy-carbonyl-phenyl,
2-chloro-4-cyano-5-(N-cyclopropyl-ethylsulfonylamino- )-phenyl,
2-fluoro-cyano-5-(1-methyl-2-propinylthio)-phenyl,
2fluoro-4-cyano-5-methylamino-phenyl,
2-chloro-4-thiocarbamoyl-5-methoxyc- arbonylmethyl-phenyl,
2-chloro-4-cyano-5-(N-methyl-ethylsulfonylamino)-phe- nyl,
2-fluoro-4-cyano-5-i-propoxycarbonyl-phenyl,
2-fluoro-4-chloro-5-i-pr- opoxycarbonyl-phenyl,
2-fluoro-4-cyano-5-(bis-ethylsulfonyl-amino)-phenyl,
2-fluoro-4-cyano-5-(N-methylsulfonyl-ethylsulfonylamino)-phenyl,
2-fluoro-4-cyano-5-(1-methoxycarbonyl-ethoxy)-phenyl,
2-fluoro-4-cyano-5-(1-ethoxycarbonyl-ethoxy)-phenyl,
2-fluoro-4-chloro-5-(1-methoxycarbonyl-ethoxy)-phenyl,
2-fluoro-4-chloro-5-(1-ethoxycarbonyl-ethoxy)-phenyl,
2-fluoro-4-cyano-5-cyclopropyloxy-phenyl,
2-chloro-4-cyano-5-dimethylamin- o-phenyl,
2-fluoro-4-cyano5-tetrahydrofurylmethoxy-phenyl,
4-chloro-2-fluoro-5-tetrahydrofurylmethoxy-phenyl,
2-fluoro-4-cyano-5-amino-phenyl,
2-fluoro-4-cyano-5-methylaminocarbonyl-p- henyl,
2-fluoro-4-cyano-5-methysulfonyloxy-phenyl,
2-chloro-4-cyano-5-difl- uoromethoxy-phenyl,
2-fluoro-4-chloro-5-methoxycarbonylmethoxy-phenyl,
2-fluoro-4-chloro-5-ethoxycarbonyl-methoxy-phenyl,
2-fluoro-4-cyano-5-methoxycarbonylmethoxy-phenyl,
2-fluoro-4-cyano-5-etho- xycarbonylmethoxy-y-phenyl,
4-cyano-3-(1-methyl-2-propinyloxy)-phenyl,
2-fluoro-4-cyano-5-dimethyl-aminocarbonyl-phenyl,
2-fluoro-4-cyano-5-cyan- omethoxy-phenyl,
2-fluoro-4-cyano-5-(2-chloro-2-propenyloxy)-phenyl,
2-fluoro-4-cyano-5-hydroxy-phenyl, 2-fluoro-4-cyano-5-nitro-phenyl,
2-fluoro-4-cyano-5-diethoxyphosphorylamino-phenyl,
2-fluoro-4-cyano-5-cholorosulfonyl-phenyl,
2-fluoro-4-cyano-5-formylamino- -phenyl,
2-chloro-4-cyano-5-ethoxycarbonyloxy-phenyl,
2-fluoro-4-cyano-5-diethoxy-phosphorylmethoxy-phenyl,
4-chioro-2-fluoro-5-diethoxy-phosphorylmethoxy-phenyl,
2-fluoro-4-cyano-5-(1-diethoxyphosphoryl-ethoxy)-phenyl,
4-chloro-2-fluoro-5(1-diethoxyphosphoryl-ethoxy)-phenyl, 2-chloro
-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-phen-
yl, 2-fluoro-4-cyano-5-diethylaminooxy-phenyl,
2-fluoro-4-cyano-5-tetrahyd- rofuryloxy-phenyl,
2-fluoro-4-cyano-5-ureido-phenyl,
2-fluoro-4-cyano-5-dimethoxymethylenamino-phenyl,
2-chloro-4-cyano-5-etho-
xymethylenamino-phenyl,2-fluoro-4-cyano-5-(2-chloro-ethoxycarbonyl-oxy)-ph-
enyl, 2-chloro-4-cyano-5-dimethylaminomethylenamino-phenyl,
2-chloro-4-cyano-5-(perhydropyran-4-yloxy)-phenyl,
2-fluoro-4-cyano-5-(2-methoxycarbonyl-ethyl)-phenyl,
4-chloro-2-fluoro-5-(2-methoxycarbonyl-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-c-
hloro-5-(2-chloro-2-methoxycarbonyl-ethyl)-phenyl,
2-fluoro-4-cyano-5-(2-c- hloro-2-ethoxycarbonyl-ethyl)-phenyl,
2-fluoro-4-chloro-5-(2-chloro-2-etho- xycarbonyl-ethyl)-phenyl,
2-fluoro-4-cyano-5-(2-bromo-2-methoxycarbonyl-et- hyl)-phenyl,
2-fluoro-4-chloro-5-(2-bromo-2-methoxycarbonyl-ethyl)-phenyl,
2-fluoro-4-cyano-5-(2-bromo-2-ethoxycarbonyl-ethyl)-phenyl,
2-fluoro-4-chloro-5-(2-bromo-2-ethoxycarbonyl-ethyl)-phenyl,
2-fluoro-4-cayno-5-(2-bromo-2-ethoxycarbonyl-ethyl)-phenyl,
2-fluoro-4-cyano-5-(2,3-dibromo-2-methoxycarbonyl-ethyl)-phenyl,
2-fluoro-4-chloro-5-(2,3-dibromo-2-methoxycarbonyl-ethyl)-phenyl,
2-fluoro-4-cyano-5-(2,3-dibromo-2-ethoxycarbonyl-ethyl)-phenyl,
2-fluoro-4-chloro-5-(2,3-dibromo-2-ethoxycarbonyl-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,
2,4-dichloro-5-(2-methoxy-carbonyl-ethyl)-phenyl,2-fluoro-4-cyano-5-(2-ca-
rboxy-2-chloro-ethyl)-phenyl,
2-fluoro-4-cyano-5-(2-chloro-2-ethylamino-ca- rbonyl-ethyl)-phenyl,
2-fluoro-4-cyano-5-(2-allylaminocarbonyl-2-chloro-et- hyl)-phenyl,
2-fluoro-4-cyano-5-(2-methoxycarbonyl-ethenyl)-phenyl,
2-fluoro-4-chloro-5-(2-methoxycarbonyl-ethenyl)-phenyl,
2-fluoro-4-cyano-5-(2-ethoxycarbonyl-ethenyl)-phenyl,
2-fluoro-4-chloro-5-(2-ethoxycarbonyl-ethenyl)-phenyl,
2-fluoro-4-cyano-5-(2-chloro-2-methylaminocarbonyl-ethyl)-phenyl,
2-fluoro-4-cyano-5-(2-chloro-2-ethylaminocarbonyl-ethyl)-phenyl,
2-fluoro-4-cyano-5-(2-chloro-2-cyclopropylamino-carbonyl-ethyl)-phenyl,
2-fluoro-4-chloro-5-(2-chloro-2-methylaminocarbonyl-ethyl)-phenyl,
2-fluoro-4-chloro-5-(2-chloro-2-ethylaminocarbonyl-ethyl)-phenyl,
2-fluoro-4-chloro-5-(2-chloro-2-cyclopropylaminocarbonyl-ethyl)-phenyl,
2-fluoro-4-cyano-5(2-chloro-2-dimethylaminocarbonyl-ethyl)-phenyl,
2-fluoro-4-cyano-5-(2-chloro-2-ethylsulfonylaminocarbonyl-ethyl)-phenyl,
2-fluoro-4-chloro-5-(2-chloro-2-ethylsulfonylaminocarbonyl-ethyl)-phenyl,
2-fluoro-4-chloro-5-(2-carboxy-ethenyl)-phenyl,
2-fluoro-4-thiocarbamoyl-- 5-(2-ethylaminocarbonyl-ethenyl)-phenyl,
2,6-difluoro-4-cyano-5-i-propoxy-- phenyl,
2-chloro-4-cyano-6-fluoro-3-i-propoxy-phenyl,
2-chloro-6-fluoro-3-i-propoxy-4-trifluoromethyl-phenyl,
2,6-di-chloro-4-cyano-3-fluoro-phenyl,
2-fluoro-4-cyano-5-(1-ethoxycarbon- yl-ethyl)-phenyl,
2-chloro-4-cyano-5-(1-ethoxycarbonyl-ethyl)-phenyl,
2-chloro-4-cyano-5carboxy-phenyl
2-fluoro-4-chloro-5-(1-ethoxycarbonyl-et- hyl)-phenyl,
2-fluoro-4-chloro-5-(1-i-propoxycarbonyl-ethyl)-phenyl,
2-fluoro-4-cyano-5-i-butoxy-phenyl),
2-chloro-4-cyano-5-i-butoxy-phenyl,
2-chloro-4-cyano-5-(2-methoxy-ethoxy)-phenyl,2-fluoro-4-chloro-5-(2-metho-
xy-ethoxy)-phenyl,2-fluoro-4-chloro-5-i-butoxy-phenyl,
4-hydroxy-4-ethoxycarbonyl-phenyl,
2-fluoro-4-cyano-5-i-propoxycarbonyl-p- henyl,
2-fluoro-4-hydroxy-5-i-propoxycarbonyl-phenyl,
2-fluoro-4-cyano-5-(2-oxetanyloxy)-phenyl,
2-fluoro-4-cyano-5-(2-oxetanyl- oxy-carbonylmethoxy)-phenyl,
2-fluoro-4-cyano-5-(2-oxetanyloxy)-phenyl,
2-fluoro-4-cyano-5-(2-chloro-2-propenyloxy)-phenyl,
4-chloro-2-fluoro-5-(2-chloro-2-propenyloxy)-phenyl,
2-fluoro-4-chloro-5-methoxycarbonylmethylthio-phenyl,
2-fluoro-4-chloro-5-ethoxycarbonylmethylthio-phenyl,
2-fluoro-4-cyano-5-methoxycarbonylmethylthio-phenyl,
2-fluoro-4-cyano-5-ethoxycarbonylmethylthio-phenyl,
2-fluoro-4-chloro-5-(1-methoxycarbonyl-ethylthio)-phenyl,
2-fluoro-4-chloro-5(1-ethoxycarbonyl-ethylthio)-phenyl,
2-fluoro-4-cyano-5-(1-methoxycarbonyl-ethylthio)-phenyl,
2-fluoro-4-cyano-5-(1-ethoxycarbonyl-ethylthio)-phenyl,
15161718
[0150] R here represents, for example, hydrogen, hydroxyl, methyl,
ethyl, n- or i-propyl, i- or s-butyl, allyl, propargyl, methoxy,
ethoxy, n- or i-propoxy, cyanomethyl, carboxymethyl, methoxymethyl,
ethoxymethyl, methoxycarbonylmethyl, ethoxycarbonylmethyl, acetyl,
propionyl, methoxycarbonyl, ethoxycarbonyl, methylsulfonyl or
ethylsulfonyl.
Group 2
[0151] 19
[0152] Ar here has, for example, the meanings listed above in Group
1.
Group 3
[0153] 20
[0154] Ar here has, for example, the meanings listed above in Group
1.
Group 4
[0155] 21
[0156] Ar here has, for example, the meanings listed above in Group
1.
Group 5
[0157] 22
[0158] Ar here has, for example, the meanings listed above in Group
1.
Group 6
[0159] 23
[0160] Ar here has, for example, the meanings listed above in Group
1.
Group 7
[0161] 24
[0162] Ar here has, for example, the meanings listed above in Group
1.
Group8
[0163] 25
[0164] Ar here has, for example, the meanings listed above in Group
1.
Group 9
[0165] 26
[0166] Ar here has, for example, the meanings listed above in Group
1.
Group 10
[0167] 27
[0168] Ar here has, for example, the meanings listed above in Group
1.
Group 11
[0169] 28
[0170] Ar here has, for example, the meanings listed above in Group
1.
Group 12
[0171] 29
[0172] Ar here has, for example, the meanings listed above in Group
1.
Group 13
[0173] 30
[0174] Ar here has, for example, the meanings listed above in Group
1.
Group 14
[0175] 31
[0176] Ar here has, for example, the meanings listed above in Group
1.
Group 15
[0177] 32
[0178] Ar here has, for example, the meanings listed above in Group
1.
Group 16
[0179] 33
[0180] Ar here has, for example, the meanings listed above in Group
1.
Group 17
[0181] 34
[0182] Ar here has, for example, the meanings listed above in Group
1.
Group 18
[0183] 35
[0184] Ar here has, for example, the meanings listed above in Group
1.
Group 19
[0185] 36
[0186] Ar here has, for example, the meanings listed above in Group
1.
Group 20
[0187] 37
[0188] Ar here has, for example, the meanings listed above in Group
1.
Group 21
[0189] 38
[0190] Ar here has, for example, the meanings listed above in Group
1.
Group 22
[0191] 39
[0192] Ar here has, for example, the meanings listed above in Group
1.
Group 23
[0193] 40
[0194] Ar here has, for example, the meanings listed above in Group
1.
Group 24
[0195] 41
[0196] Ar here has, for example, the meanings listed above in Group
1.
Group 25
[0197] 42
[0198] Ar here has, for example, the meanings listed above in Group
1.
Group 26
[0199] 43
[0200] Ar here has, for example, the meanings listed above in Group
1.
Group 27
[0201] 44
[0202] Ar here has, for example, the meanings listed above in Group
1.
Group 28
[0203] 45
[0204] Ar here has, for example, the meanings listed above in Group
1.
Group 29
[0205] 46
[0206] Ar here has, for example, the meanings listed above in Group
1.
Group 30
[0207] 47
[0208] Ar here has, for example, the meanings listed above in Group
1.
Group 31
[0209] 48
[0210] Ar here has, for example, the meanings listed above in Group
1.
Group 32
[0211] 49
[0212] Ar here has, for example, the meanings listed above in Group
1.
Group 33
[0213] 50
[0214] Ar here has, for example, the meanings listed above in Group
1.
Group 34
[0215] 51
[0216] Ar here has, for example, the meanings listed above in Group
1.
Group 35
[0217] 52
[0218] Ar here has, for example, the meanings listed above in Group
1.
Group 36
[0219] 53
[0220] Ar here has, for example, the meanings listed above in Group
1.
Group 37
[0221] 54
[0222] Ar here has, for example, the meanings listed above in Group
1.
Group 38
[0223] 55
[0224] Ar here has, for example, the meanings listed above in Group
1.
Group 39
[0225] 56
[0226] Ar here has, for example, the meanings listed above in Group
1.
Group 40
[0227] 57
[0228] Ar here has, for example, the meanings listed above in Group
1.
Group 41
[0229] 58
[0230] Ar here has, for example, the meanings listed above in Group
1.
Group 42
[0231] 59
[0232] Ar here has, for example, the meanings listed above in Group
1.
Group 43
[0233] 60
[0234] Ar here has, for example, the meanings listed above in Group
1.
Group 44
[0235] 61
[0236] Ar here has, for example, the meanings listed above in Group
1.
Group 45
[0237] 62
[0238] Ar here has, for example, the meanings listed above in Group
1.
Group 46
[0239] 63
[0240] Ar here has, for example, the meanings listed above in Group
1.
Group 47
[0241] 64
[0242] Ar here has, for example, the meanings listed above in Group
1.
Group 48
[0243] 65
[0244] Ar here has, for example, the meanings listed above in Group
1.
Group 49
[0245] 66
[0246] Ar here has, for example, the meanings listed above in Group
1.
Group 50
[0247] 67
[0248] Ar here has, for example, the meanings listed above in Group
1.
Group 51
[0249] 68
[0250] Ar here has, for example, the meanings listed above in Group
1.
Group 52
[0251] 69
[0252] Ar here has, for example, the meanings listed above in Group
1.
Group 53
[0253] 70
[0254] Ar here has, for example, the meanings listed above in Group
1.
Group 54
[0255] 71
[0256] Ar here has, for example the meanings listed above in Group
1.
Group 55
[0257] 72
[0258] Ar here has, for example, the meanings listed above in Group
1.
Group 56
[0259] 73
[0260] Ar here has, for example, the meanings listed above in Group
1.
Group 57
[0261] 74
[0262] Ar here has, for example, the meanings listed above in Group
1.
Group 58
[0263] 75
[0264] Ar here has, for example, the meanings listed above in Group
1.
Group 59
[0265] 76
[0266] Ar here has, for example, the meanings listed above in Group
1.
Group 60
[0267] 77
[0268] Ar here has, for example, the meanings listed above in Group
1.
Group 61
[0269] 78
[0270] Ar here has, for example, the meanings listed above in Group
1.
Group 62
[0271] 79
[0272] Ar here has, for example, the meanings listed above in Group
1.
Group 63
[0273] 80
[0274] Ar here has, for example, the meanings listed above in Group
1.
Group 64
[0275] 81
[0276] Ar here has, for example, the meanings listed above in Group
1.
Group 65
[0277] 82
[0278] Ar here has, for example, the meanings listed above in Group
1.
Group 66
[0279] 83
[0280] Ar here has, for example, the meanings listed above in Group
1.
Group 67
[0281] 84
[0282] Ar here has, for example, the meanings listed above in Group
1.
Group 68
[0283] 85
[0284] Ar here has, for example, the meanings listed above in Group
1.
Group 69
[0285] 86
[0286] Ar here has, for example, the meanings listed above in Group
1.
Group 70
[0287] 87
[0288] Ar here has, for example, the meanings listed above in Group
1.
Group 71
[0289] 88
[0290] Ar here has, for example, the meanings listed above in Group
1.
Group 72
[0291] 89
[0292] Ar here has, for example, the meanings listed above in Group
1.
Group 73
[0293] 90
[0294] Ar here has, for example, the meanings listed above in Group
1.
Group 74
[0295] 91
[0296] Ar here has, for example, the meaning listed above in Group
1.
Group 75
[0297] 92
[0298] Ar here has, for example, the meanings listed above in Group
1.
[0299] If, for example,
4-(4-cyano-2,5-difluoro-phenyl)-1-methoxycarbonylt-
hiosemicarbazide is used as the starting substance, the course of
the reaction in process (a) according to the invention can be
represented by the following equation: 93
[0300] If, for example,
2-(4-chloro-2-fluoro-5-methoxy-phenylimino)-3,4-di-
methyl-3,4-dihydro-5-oxo-1,3,4-thiadiazole is used as the starting
substance, the course of the reaction in process (b) according to
the invention can be outlined by the following equation: 94
[0301] Formula (II) provides a general definition of the
(thio)semicarbazide derivatives to be used as starling substances
in process (a) according to the invention for the preparation of
the compounds of the general formula (I). In formula (II), Q.sup.1,
Q.sup.2, R.sup.1, R.sup.2 and Ar preferably or in particular have
those meanings which have already been mentioned above as preferred
or as particularly preferred for Q.sup.1, Q.sup.2, R.sup.1, R.sup.2
and Ar in connection with the description of the compounds of the
formula (I); preferably represents alkyl having 1-4 carbon atoms,
in particular methyl or ethyl.
[0302] The starting substances of the formula (II) are known and/or
can be prepared by known processes (cf. Synthesis 1982, 159-160; DE
1200824, DE 2952685 and DE 3026739).
[0303] The (thio)semicarbazide derivatives of the formula (II) are
obtained when
[0304] (.alpha.) aryl iso(thio)cyanates of the general formula
(IV)
Ar--N.dbd.C.dbd.Q.sup.1 (IV)
[0305] in which
[0306] Ar and Q.sup.1 have the abovementioned meanings,
[0307] are reacted with carbazates of the general formula (XI)
RO--CQ.sup.2--N(R.sup.2)--NH--R.sup.1 (XI)
[0308] in which
[0309] Q.sup.2, R.sup.1 and R.sup.2 have the abovementioned
meanings and
[0310] R represents alkyl, and preferably represents
C.sub.1-C.sub.6-alkyl, and particularly preferably represents
methyl or ethyl,
[0311] if appropriate in the presence of a diluent, such as, for
example, toluene, at temperatures of between 0.degree. C. and
150.degree. C. (cf. the preparation examples),
[0312] or when
[0313] (.beta.) arylamines of the general formula (XII)
Ar--NH.sub.2 (XII)
[0314] in which
[0315] Ar has the abovementioned meaning,
[0316] are reacted with (thio)carbonyl-diimidazole of the formula
(XIII)
Im--CQ.sup.1--Im (XIII)
[0317] in which
[0318] Q.sup.1 has the abovementioned meaning and
[0319] Im represents imidazolyl, and with carbazates of the general
formula (XI)
RO--CQ.sup.2--N(R.sup.2)--NH--R.sup.1 (XI)
[0320] in which
[0321] Q.sup.2, R.sup.1 and R.sup.2 have the abovementioned
meanings and
[0322] R represents alkyl, and preferably represents
C.sub.1-C.sub.6-alkyl, and particularly preferably represents
methyl or ethyl,
[0323] if appropriate in the presence of a reaction auxiliary, such
as, for example, potassium hydroxide, and if appropriate in the
presence of a diluent, such as, for example, methanol, ethanol
and/or water, at temperatures of between 0.degree. C. and
100.degree. C.
[0324] The aryl iso(thio)cyanates of the formula (IV) required as
precursors are known and/or can be prepared by known processes (cf.
DE 4327743, DE 4335438 and DE 4343451).
[0325] The carbazates of the formula (VIII) furthermore required as
precursors are known organic chemicals.
[0326] Process (a) according to the invention is preferably carried
out in the presence of a suitable reaction auxiliary. Possible
reaction auxiliaries are all the customary organic or inorganic
bases. These include, for example, alkali metal or alkaline earth
metal hydrides, hydroxides, amides, alcoholates, acetates,
carbonates or hydrogencarbonates, such as, for example, lithium,
sodium, potassium or calcium hydride, lithium, sodium or potassium
amide, sodium or potassium methylate, sodium or potassium ethylate,
sodium or potassium propylate, aluminum isopropylate, sodium or
potassiun tert-butylate, sodium or potassium hydroxide, ammonium
hydroxide, sodium, potassium or calcium acetate, ammonium acetate,
sodium, potassium, rubidium, cesium, magnesium or calcium
carbonate, ammonium carbonate and sodium or potassium
hydrogencarbonate, and basic organic nitrogen compounds, such as
trimethylamine, triethylamine, tripropylamine, tributylamine,
ethyl-diisopropylamine, N,N-dimethylcyclohexylamine,
dicyclohexylamine, ethyl-dicyclohexylamine, N,N-dimethylaniline,
N,N-dimethyl-benzylamine, pyridine, 2-methyl-, 3-methyl- and
4-methyl-pyridine, 2,4-dimethyl-, 2,6-dimethyl-, 3,4-dimethyl- and
3,5-dimethyl-pyridine, 5-ethyl-2-methyl-pyridine,
N-methylpiperidine, N,N-dimethylaminopyridine, diazabicyclooctane,
(DABCO), diazabicyclononene (DBN) or diazabicycloundecene
(DBU).
[0327] Possible diluents for carrying out process (a) according to
the invention are the customary organic solvents. These include, in
particular, aliphatic, alicyclic or aromatic, optionally
halogenated hydrocarbons, such as, for example, pentane, hexane,
heptane, petroleum ether, ligroin, benzine, benzene, toluene,
xylene, chlorobenzene, dichlorobenzene, cyclohexane,
methylcyclohexane, methylene chloride, chloroform or carbon
tetrachloride; ethers, such as diethyl ether, diisopropyl ether,
t-butyl methyl ether, t-pentyl methyl ether, dioxane,
tetrahydrofuran, ethylene glycol dimethyl or diethyl ether or
diethylene glycol dimethyl or diethyl ether, ketones, such as
acetone, butanone or methyl isobutyl ketone; nitriles, such as
acetonitrile, propionitrile, butyronitrile or benzonitrile; amides,
such as N,N-dimethylformamide, N,N-dimethylacetamide,
N-methylformanilide, N-methyl-pyrrolidone or hexamethylphosphoric
acid triamide; esters, such as methyl, ethyl, n- or i-propyl or n-,
i- or s-butyl acetate; sulfoxides, such as dimethyl sulfoxide;
alcohols, such as methanol, ethanol, n- or i-propanol, n-, i-, s-
or t-butanol, ethylene glycol monomethyl or monoethyl, ether,
diethylene glycol monomethyl ether or diethylene glycol monoethyl
ether; and mixtures thereof with water or pure water.
[0328] The reaction temperatures can be varied within a substantial
range when carrying out process (a) according to the invention. The
process is in general carried out at temperatures of between
0.degree. C. and +150.degree. C., preferably at temperatures
between 10.degree. C. and 120.degree. C.
[0329] Process (a) according to the invention is in general carried
out under normal pressure. However, it is also possible to carry
out the process under increased or reduced pressure--in general
between 0.1 bar and 10 bar.
[0330] For carrying out process (a) according to the invention, the
starting substances of formula (II) are in general initially
introduced into the reaction vessel in a suitable diluent and--if
appropriate after addition of a reaction auxiliary--are stirred at
the required temperate until the reaction has ended. Working up can
be carried out in the customary manner (cf. the preparation
examples).
[0331] Formula (III) provides a general definition of the
aryliminoheterocyclic compounds to be used as starting substances
in process (b) according to the invention for the preparation of
the compounds of the general formula (I). In formula (III),
Q.sup.1, Q.sup.2, R.sup.1, R.sup.2 and Ar preferably or in
particular have those meanings which have already been mentioned
above as preferred or as particularly preferred for Q.sup.1,
Q.sup.2, R.sup.1, R.sup.2 and Ar in connection with the description
of the compounds of the formula (I).
[0332] The starting substances of the formula (III) are not yet
known from the literature; however, they are the subject of a prior
application which has not previously been published (cf. DE
4424787).
[0333] The aryliminoheterocyclic compounds of the formula (III) are
obtained when aryl(thio)semicarbazides of the general formula (VI)
are reacted with reactive carbonic acid derivatives, such as, for
example, phosgene or thiophosgene, if appropriate in the presence
of diluents, such as, for example, toluene and/or methylene
chloride, at temperatures of between 0.degree. and 100.degree.
C.
[0334] Formulae (Ia) and (Ib) provide general definitions of the
compounds to be used, if appropriate, as starting substances, in
process (b) according to the invention for the preparation of the
compounds of the general formula (I). In formulae (Ia) and (Ib),
Q.sup.1, Q.sup.2, R.sup.1, R.sup.2 and Ar preferably or in
particular have those meanings which have already been mentioned
above as preferred or as particularly preferred for Q.sup.1,
Q.sup.2, R.sup.1, R.sup.2 and Ar in connection with the description
of the compounds of the formula (I).
[0335] The compounds of the formula (Ia) or (Ib) are obtained when
N-aryl nitrogen-containing heterocyclic compounds of the general
formula (I) in which at least one of the groups R.sup.1 or R.sup.2
represents hydrogen are reacted with alkylating or acylating agents
of the formulae (IXa or (IXb)
X--R.sup.1 (XIVa)
X--R.sup.2 (XIVb)
[0336] in which
[0337] R.sup.1 and R.sup.2 have the abovementioned meanings, with
the exception of hydrogen, and
[0338] X represents halogen--preferably chlorine, bromine or
iodine--or one of the groupings --O--SO.sub.2--O--R.sup.1 or
--O--SO.sub.2--O--R.sup- .2,
[0339] if appropriate in the presence of a diluent and if
appropriate in the presence of a reaction auxiliary at tempt of
between 0.degree. C. and 80.degree. C. (cf. the preparation
examples).
[0340] The same diluents and reaction auxiliaries as in process (a)
according to the invention are preferably possible here.
[0341] If appropriate, process (b) according to the invention is
carried out in the presence of a reaction auxiliary. The same
reaction auxiliaries as in process (a) according to the invention,
but furthermore in addition also alkali metal sulfides, such as,
for example, sodium sulfide or potassium sulfide, are possible
here.
[0342] Process (b) according to the invention is preferably carried
out using a diluent. The same diluents as in process (a) according
to the invention are possible here.
[0343] The reaction temperatures can be varied within a substantial
range when carrying out process (b) according to the invention. The
process is in general carried out at temperatures of between
0.degree. C. and +250.degree. C., preferably at temperatures of
between 20.degree. C. and 150.degree. C.
[0344] Process (b) according to the invention is in general carried
out under normal pressure. However, it is also possible to carry
out the process under increased or reduced pressure--in general
between 0.1 bar and 10 bar.
[0345] For carrying out process (b) according to the invention, the
starting substances of the formula (III) or of the formulae (Ia) or
(Ib)--are in general initially introduced into the reaction vessel
in a suitable diluent and are stirred at the required temperature
until the reaction has ended Working up can be carried out in the
customary manner.
[0346] The active compounds according to the invention can be used
as defoliants, desiccants, agents for destroying broad-leaved
plants and, especially, as weed-killers. By weeds, in the broadest
sense, there are to be understood all plants which grow in
locations where they are undesired Whether the substances according
to the invention act as total or selective herbicides depends
essentially on the amount used.
[0347] The active compounds according to the invention can be used,
for example, in connection with the following plants:
[0348] Dicotyledon weeds of the genera: Sinapis, Lepidiunm, 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,
Taraxacum.
[0349] Dicotyledon cultures of the genera: Gossypium, Glycine,
Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia,
Nicotiana, Lycopersicor, Arachis, Brassica, Lactucae, Cucumis and
Cucurbita.
[0350] Monocotyledon 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, Agrostis,
Alopecurus and Apera.
[0351] Monocotyledon cults of the genera: Oryza, Zea, Triticum,
Hordeum, Avena, Secale, Sorghum, Panicum, Saccharum, Ananas,
Asparagus and Allium.
[0352] 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.
[0353] The compounds are suitable, depending on the concentration,
for the total combating of weeds, for example on industrial terrain
and rail tracks, and on paths and squares with or without tree
plantings. Equally, the compounds can be employed for combating
weeds in perennial cultures, for example afforestations, decorative
tree plantings, orchards, vineyards, citrus groves, nut orchards,
banana plantations, coffee plantations, tea plantations, rubber
plantations, oil palm plantations, cocoa plantations, soft fruit
plantings and hopfields, in lawns, turf and pasture-land, and-for
the selective combating of weeds in annual cultures.
[0354] The compounds of the formula (I) according to the invention
are particularly suitable for selectively combating monocotyledon
and dicotyledon weeds in monocotyledon cultures both by the
pre-emergence and by the post-emergence method.
[0355] The active compounds can be convened into the customary
formulations, such as solutions, emulsions, wettable powders,
suspensions, powders, dusting agents, pates, soluble powders,
granules, suspension-emulsion concentrates, natural and synthetic
materials impregnated with active compound, and very fine capsules
in polymeric substances.
[0356] These formulations are produced in a known manner, for
example by mixing the active compounds with extenders, that is
liquid solvents and/or solid carriers, optionally with the use of
surface-active agents, that is emulsifying agents and/or dispersing
agents and/or foam-forming agents.
[0357] In the case of the use of water as an extender, organic
solvents cm, for example, also be used as auxiliary solvents. As
liquid solvents, there are suitable in the main: aromatics, such as
xylene, toluene or alkylnaphthalenes, chlorinated aromatics and
chlorinated aliphatic hydrocarbons, such as chlorobenzenes,
chloroethylenes or methylene chloride, aliphatic hydrocarbons, such
as cyclohexane or paraffins, for example petroleum fractions,
mineral and vegetable oils, alcohols, such as 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 sulfoxide,
as well as water.
[0358] As solid carriers there are suitable: for example ammonium
salts and ground natural minerals, such as kaolins, clays, talc,
chalk, quartz, attapulgite, montmorillonite or diatomaceous earth,
and ground synthetic minerals, such as highly disperse silica,
alumina and silicates, as solid carriers for granules there are
suitable: for example crushed and fractionated natural rocks such
as calcite, marble, pumice, sepiolite and dolomite, as well as
synthetic granules of inorganic and organic meals, and granules of
organic material such as sawdust, coconut shells, maize cobs and
tobacco stalks; as emulsifying and/or foam-forming agents there are
suitable: for example non-ionic and anionic emulsifiers, such as
polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol
ethers, for example alkylaryl polyglycol ethers, alkylsulfonates,
alkyl sulfates, arylsulfonates as well as albumen hydrolysis
products; as dispersing agents there are suitable: for example
lignin-sulfite waste liquors and methylcellulose.
[0359] 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, 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.
[0360] It is possible to use colorants such as inorganic pigments,
for example iron oxide, titanium oxide and Prussian Blue, and
organic dyestuffs such as alizarin dyestuffs, azo dyestuff and
metal phthalocyanine dyestuffs, and trace nutrients such as salts
of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
[0361] The formulations in general contain between 0.1 and 95
percent by weight of active compound, preferably between 0.5 and
90%.
[0362] For controlling weeds, the active compounds according to the
invention, as such or in the form of their formulations, can also
be used as mixture with known herbicides, finished formulations or
tank mixes being possible.
[0363] Suitable herbicides for the mixtures are known herbicides,
for example anilides such as, for example, diflufenican and
propanil; arylcarboxylic acids such as, for example,
dichloropicolinic acid, dicamba and picloram; aryloxyalkanoic acids
such as, for example, 2,4 D, 2,4 DB, 2,4 DP, fluroxypyr, MCPA, MCPP
and triclopyr; aryloxy-phenoxy-alkanoic esters such as, for
example, diclofop-methyl, fenoxaprop-ethyl, fluazifop-butyl,
haloxyfop-methyl and quizalofop-ethyl; azinones such as, for
example, chloridazon and norflurazon; carbamates such as, for
example, chlorpropham, desmedipham phenmedipham and propham;
chloroacetanilides such as, for example, alachlor, acetochlor,
butachlor, metazachlor, metolachlor, pretilachior and propachlor,
dinitroanilines such as, for example, oryzalin, pendimethalin and
trifluralin; diphenyl ethers such as, for example, acifluorfen,
bifenox, fluoroglycofen, fomesafen, halosafen, lactofen and
oxyfluorfen; ureas such as, for example, chlortoluron, diuron,
fluometuron, isoproturon, linuron and methabenzthiazuron;
hydroxylamines such as, for example, alloxydim, clethodim,
cycloxydim sethoxydim and tralkoxydim; imidazolinones such as, for
example, imazethapyr, imazamethabenz, imazapyr and imazaquin;
nitriles such as, for example, bromoxynil, dichlobenil and ioxynil;
oxyacetamides such as, for example, mefenacet; sulfonylureas such
as, for example, amidosulfuron, bensulfuron-methyl,
chlorimuron-ethyl, chlorsulfuron, cinosufuron, metsulfuron-methyl,
nicosulfuron, primisulfuron, pyrazosulfuron-ethyl,
thifensulfuron-methyl and tribenuron-methyl; thiocarbamates such
as, for example, butylate, cycloate, di-allate, EPTC, esprocarb,
molinate, prosulfocarb, thiobencarb and tri-allate; triazines such
as, for example, atrazine, cyanazine, simazine, simetryne,
terbutryne and terbutylazine; triazinones such as, for example,
hexazinone, metamitron and metribuzin; others such as, for example,
aminotriazole, benfuresate, bentazone, cinmethylin, clomazone,
clopyralid, difenzoquat, dithiopyr, ethofumesate, fluorochloridone,
glufosinate, glyphosate, isoxaben, pyridate, quinchlorac,
quinmerac, sulphosate and tridiphane.
[0364] A mixture with other known active compounds, such as
fungicides, insecticides, acaricides, nematicides, bird repellants,
plant nutrients and agents for improving soil structure is also
possible.
[0365] 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.
[0366] 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.
[0367] The amount of active compound used can vary within a
substantial range. It depends essentially on the nature of the
desired effect. In general, the amounts used are between 1 g and 10
kg of active compound per hectare of soil surface, preferably
between 5 g and 5 kg per ha.
[0368] The preparation and use of the active compounds according to
the invention can be seen from the following examples.
PREPARATION EXAMPLES
Example 1
[0369] 95
[0370] 20.2 g (75 mmol) of
4-(4-cyano-2,5-difluoro-phenyl)-1-ethoxycarbony- l-semicarbazide
are stirred in 50 ml of 25% strength aqueous potassium hydroxide
solution at 80.degree. C. for 2 hours. After the mixture has been
cooled to 20.degree. C., it is brought to pH=4 with concentrated
hydrochloric acid and the product obtained as crystals is isolated
by filtration.
[0371] 16.0 g (90% of theory) of
4-(4-carboxy-2,5-difluorophenyl)-1,2,4-tr- iazoline-2,5-dione of
melting point >250.degree. C. are obtained.
Example 2
[0372] 96
[0373] A mixture of 3.90 g (10 mmol) of
4-(4-cyano-2-fluoro-5-methylsulfon-
ylaminophenyl)-2-methyl-1-ethoxycarbonyl-thiosemicarbazide,8.10 g
(80 mmol) of triethylamine and 100 ml of acetonitrile is stirred at
the reflux temperature for 12 hours. The solvent is removed in
vacuo, the residue is stirred with water, the mixture is acidified
with concentrated hydrochloric acid and the product obtained as
crystals is isolated by filtration.
[0374] 1.20 g (35% of theory) of
4-cyano-2-fluoro-5-methylsulfonylaminophe-
nyl)-1-methyl-5-thioxo-1,2,4-triazolin-3-one of melting point
>250.degree. C. are obtained.
Example 3
[0375] 97
[0376] A mixture of 5.2 g (15 mmol) of
4-(4-chloro-2-fluoro-5-i-propoxycar-
bonyl-phenyl)-1-methyl-5-thioxo-1,2,4-triazolin-3-one, 5.2 g (37.5
mmol) of potassium carbonate and 50 ml of acetonitrile is stirred
at 60.degree. C. for 60 minutes; Frigen (CHClF.sub.2) is then
passed in at 60.degree. C. for 6 hours. The mixture is subsequently
concentrated under reduced pressure, the residue is taken up in
water, the mixture is acidified with concentrated hydrochloric acid
and exited with methylene chloride, and the organic phase is dried
over sodium sulfate and filtered The filtrate is concentrated and
the crude product obtained in the residue is purified by column
chromatography (silica gel, hexane/ethyl acetate, Vol.: 7:1).
[0377] 0.7 g (12% of theory) of
4-(4-chloro-2-fluoro-5-i-propoxycarbonyl-p-
henyl)1-methyl-2-difluoromethyl-5-thioxo-1,2,4-triazolin-3-one of
melting point 51.degree. C. is obtained.
Example 4
[0378] 98
[0379] A mixture of 7.6 g (23 mmol) of
2-(7-fluoro-3,4-dihydro-3-oxo-4-pro-
pargyl-(2H)-1,4-bezoxazin-6-yl-imino-3-methyl-3,4-dihydro-5-oxo-(4H)-1,3,4-
-thiadiazole and 20 ml of dimethyl sulfoxide is heated at
50.degree. C. for 2 hours, at 70.degree. C. for a further 2 hours
and at 80.degree. C. for a further 2 hours. It is then concentrated
under reduced pressure, the residue is stirred with water and the
product obtained as crystals is isolated by filtration.
[0380] 6.6 g (85% of theory) of
4-(7-fluoro-3,4-dihydro-3-oxo-4-propargyl--
(2H)-1,4-benzoxazin-6-yl)-1-methyl-5-thioxo-1,2,4-triazolin-3-one
of melting point 190.degree. C. are obtained.
[0381] The compounds of the formula (I) listed in the following
Table 1, for example, can also be prepared analogously to Examples
1 to 4 and in accordance with the general description of the
preparation processes according to the invention.
1TABLE 1 Examples of the compounds of the formula (I) (I) 99
Example Physical No. Q.sup.1 Q.sup.2 R.sup.1 R.sup.2 Ar data 5 O O
H CH.sub.3 100 M.p.: 234.degree. C. 6 S O CH.sub.3 H 101 M.p.:
224.degree. C. 7 S O CH.sub.3 CHO 102 M.p.: 95.degree. C. 8 O S H
CH.sub.3 103 M.p.: 172.degree. C. 9 S O CH.sub.3 CHF.sub.2 104
M.p.: 183.degree. C. 10 S O CH.sub.3 CH.sub.3 105 M.p.: 118.degree.
C. 11 S O CH.sub.3 H 106 M.p.: 139.degree. C. 12 S O CH.sub.3
CH.sub.3 107 M.p.: 227.degree. C. 13 S S CH.sub.3 CH.sub.3 108
M.p.: 175.degree. C. 14 S O CH.sub.3 CHF.sub.2 109 M.p.:
122.degree. C. 15 S O CH.sub.3 CHF.sub.2 110 M.p.: 64.degree. C. 16
S S CH.sub.3 CH.sub.3 111 M.p.: 155.degree. C. 17 S S CH.sub.3
CH.sub.3 112 M.p.: 70.degree. C. 18 S S CH.sub.3 CH.sub.3 113 M.p.:
198.degree. C. 19 S S CH.sub.3 CH.sub.3 114 20 S S C.sub.2H.sub.5
C.sub.2H.sub.5 115 M.p.: 120.degree. C. 21 S S CH.sub.3 CH.sub.3
116 M.p.: 228.degree. C. 22 S S CH.sub.3 CH.sub.3 117 M.p.:
146.degree. C. 23 S S C.sub.2H.sub.5 C.sub.2H.sub.5 118 M.p.:
142.degree. C. 24 S S CH.sub.3 CH.sub.3 119 M.p.: 192.degree. C. 25
S S C.sub.2H.sub.5 C.sub.2H.sub.5 120 M.p.: 149.degree. C. 26 S S
C.sub.2H.sub.5 C.sub.2H.sub.5 121 M.p.: 195.degree. C. 27 S S
C.sub.2H.sub.5 C.sub.2H.sub.5 122 M.p.: 148.degree. C. 28 S S
C.sub.2H.sub.5 C.sub.2H.sub.5 123 M.p.: 133.degree. C. 29 S S
C.sub.2H.sub.5 C.sub.2H.sub.5 124 30 S S CH.sub.3 CH.sub.3 125 31 S
S C.sub.2H.sub.5 C.sub.2H.sub.5 126 M.p.: 197.degree. C. 32 S S
CH.sub.3 CH.sub.3 127 M.p.: 229.degree. C. 33 S S CH.sub.3 CH.sub.3
128 M.p.: 174.degree. C. 34 S S C.sub.2H.sub.5 C.sub.2H.sub.5 129
M.p.: 103.degree. C. 35 S S CH.sub.3 CH.sub.3 130 M.p.: 259.degree.
C. 36 S S C.sub.2H.sub.5 C.sub.2H.sub.5 131 M.p.: 248.degree. C. 37
S S CH.sub.3 CH.sub.3 132 M.p.: 251.degree. C. 38 O S H CH.sub.3
133 M.p.: 201.degree. C. 39 O S CHO CH.sub.3 134 M.p.: 75.degree.
C. 40 O O CHF.sub.2 CH.sub.3 135 M.p.: 70.degree. C. 41 O S
CH.sub.3 CH.sub.3 136 M.p.: 157.degree. C. 42 O S CH.sub.3 CH.sub.3
137 M.p.: 250.degree. C. 43 O S CHF.sub.2 CH.sub.3 138 M.p.:
127.degree. C. 44 O S CH.sub.3 CH.sub.3 139 M.p.: 58.degree. C. 45
O S CH.sub.3 CH.sub.3 140 M.p.: 138.degree. C. 46 O S CH.sub.3
CH.sub.3 141 M.p.: 236.degree. C. 47 O S 142 CH.sub.3 143 M.p.:
122.degree. C. 48 O S 144 CH.sub.3 145 49 O S --CH.sub.2CF.sub.3
CH.sub.3 146 M.p.: 135.degree. C. 50 O S 147 CH.sub.3 148 M.p.:
42.degree. C. 51 O S CH.sub.3 CH.sub.3 149 M.p.: 163.degree. C. 52
O S CHF.sub.2 CH.sub.3 150 M.p.: 176.degree. C. 53 O S CH.sub.3
CH.sub.3 151 M.p.: 150.degree. C. 54 O S H CH.sub.3 152 M.p.:
67.degree. C. 55 O S H H 153 M.p.: 250.degree. C. 56 O S H CH.sub.3
154 57 O O 155 156 157 n.sub.d.sup.20 = 1.5442 58 O O 158 159 160
n.sub.d.sup.20 = 1.5349 59 O O 161 CH.sub.3 162 n.sub.d.sup.20 =
1.5600 60 O O 163 164 165 61 O O H CH.sub.3 166 M.p.: 215.degree.
C. 62 O O H CH.sub.3 167 M.p.: 250.degree. C. 63 O O H CH.sub.3 168
M.p.: 156.degree. C. 64 O O H CH.sub.3 169 .sup.1H-NMR
(CDCl.sub.3): 3.25, 4.40-4.46, 7.22-7.24 ppm 65 O S H CH.sub.3 170
M.p.: 210.degree. C. 66 O O H CH.sub.3 171 M.p.: 163.degree. C. 67
O S H CH.sub.3 172 M.p.: 143.degree. C. 68 O S H CH.sub.3 173 M.p.:
158.degree. C. 69 O S H CH.sub.3 174 M.p.: 75.degree. C. 70 O S
CH.sub.3 CH.sub.3 175 .sup.1H-NMR (CDCl.sub.3): 3.45, 3.73,
7.30-7.40 ppm 71 O S CH.sub.3 CH.sub.3 176 M.p.: 146.degree. C. 72
O S CH.sub.3 CH.sub.3 177 M.p.: 208.degree. C. 73 O S CH.sub.3
CH.sub.3 178 M.p.: 195.degree. C. 74 O O H CH.sub.3 179 (amorphous)
75 O O H H 180 M.p.: 150.degree. C. 76 O O CH.sub.3 CH.sub.3 181
M.p.: 101.degree. C. 77 O S 182 CH.sub.3 183 M.p.: 172.degree. C.
78 O S 184 CH.sub.3 185 M.p.: 199.degree. C. 79 O S H CH.sub.3 186
amorphous 80 S S CH.sub.3 CH.sub.3 187 M.p.: 160.degree. C. 81 O S
H CH.sub.3 188 amorphous 82 O S CHF.sub.2 CH.sub.3 189 M.p.:
99.degree. C. 83 O S CH.sub.3 CH.sub.3 190 84 S S CH.sub.3 CH.sub.3
191 M.p.: 131.degree. C. 85 O S CHF.sub.2 CH.sub.3 192 86 O S
C.sub.2H.sub.5 CH.sub.3 193
[0382] The compound listed as Example 13 in Table 1 can be
prepared, for example, as follows: 194
[0383] A mixture of 1.0 g (0.3 mmol) of
2-(4-cyano-2-fluoro-4-i-propoxy-ph-
enylimino)-3,4-dihydro-3,4-methyl-5-thioxo(4H)-1,3,4-thiadiazole,
0.1 g (0.1 mmol) of sodium sulfide and 20 ml of ethanol is heated
under reflux for about 20 hours. It is then concentrated, the
residue is taken up in methylene chloride and the mixture is washed
with water, dried with sodium sulfate and filtered The filtrate is
concentrated, the residue is digested with diethyl ether and the
product obtained as crystals is isolated by filtration.
[0384] 0.25 g (25% of theory) of
4-(4-cyano-2-fluoro-5-i-propoxy-phenyl)1,-
2-dimethyl-1,2,4-triazoline-2,5-dithione of melting point
175.degree. C. is obtained.
[0385] The compound listed as Example 21 in Table 1 can be
prepared, for example, as follows: 195
[0386] Hydrogen sulfide is passed into a mixture of 0.9 g (2.6
mmol) of
4-(4-cyano-2-fluoro-5-i-propoxy-phenyl)-1,2-dimethyl-1,2,4-triazoline-2,5-
-dithione, 2 ml (14 mmol) of triethylamine and 20 ml of pyridine at
90.degree. C. for 9 hours. After the mixture has been cooled, the
solvent is stripped off on a rotary evaporator and the residue is
stirred with 2 normal hydrochloric acid. The crude product is
filtered off with suction, washed with water, dried and purified by
column chromatography (mobile phase: hexane/ethyl acetate 4:1).
[0387] 0.42 g (43% of theory) of
4-(2-fluoro-5-i-propoxy-thiocarbamoylphen-
yl)-1,2-dimethyl-1,2,4-triazoline-2,5-dithione of melting point
228.degree. C. is obtained.
[0388] The compound listed as Example 46 in Table 1 can be
prepared, for example, as follows: 196
[0389] A solution of 2.1 g (6 mmol) of
4-7-fluoro-3,4-dihydro-3-oxo-4-prop-
argyl-(2H)-1,4-benzoxazin-6-yl)-1-methyl-5-methylthio-1,2,4-triazolin-3-on-
e in 20 ml of dimethylformamide is heated under reflux for 16
hours. It is then concentrated under a water pump vacuum and the
residue is purified by column chromatography.
[0390] 0.9 g (43% of theory) of
4-(7-fluoro-3,4-dihydro-3-oxo-4-propargyl--
(2H)-1,4-benzoxazin-6-yl)-1,2-dimethyl-5-thioxo-1,2,4-triazolin-3-one
of melting point 236.degree. C. is obtained.
[0391] The compound listed as Example 61 in Table 1 can be
prepared, for example, as follows: 197
[0392] 44.7 g (0.15 mol) of
4-(4-cyano-2,5-difluoro-phenyl)-1-ethoxycarbon-
yl-2-methyl-semicarbazide are stirred in 200 ml of 4 molar aqueous
potassium hydroxide solution at 80.degree. C. for 30 minutes. After
the mixture has been cooled to 20.degree. C., it is brought to pH=4
with concentrated hydrochloric acid and the product obtained as
crystals is isolated by filtration.
[0393] 36 g (95% of theory) of
4-(4-carboxy-2,5-difluoro-phenyl)-1-methyl--
1,2,4-triazoline-3,5-dione of melting point 215.degree. C. are
obtained.
[0394] The compound listed as Example 62 in Table 1 can be
prepared, for example, as follows: 198
[0395] 27.1 g (0.1 mol) of
4-(4-carboxy-2,5-difluoro-phenyl)-1-methyl-1,2,-
4-triazole-3,5-dione are heated to 80.degree. C. in 200 ml of
toluene, 14.3 g (0.12 mol) of thionyl chloride are added dropwise
at this tense in the course of 30 minutes, and the mixture is
heated to the reflux temperature and stirred for about 2 hours
until the evolution of gas has ended. After the mixture has been
cooled to 20.degree. C., the product obtained as crystals is
isolated by filtration.
[0396] 7.2 g (25% of theory) of
4-(4-chlorocarbonyl-2,5-difluoro-phenyl)-1-
-methyl-1,2,4-triazole-3,5-dione of melting point >250.degree.
C. are obtained.
[0397] The compound listed as Example 63 in Table 1 can be
prepared, for example, as follows: 199
[0398] 6.5 g (0.024 mol) of
4-(4-carboxy-2,5-difluoro-phenyl)-1-methyl-1,2-
,4-triazole-3,5-dione are stirred at the reflux temperature with
200 ml of methanol and two drops of sulfuric acid for 8 hours.
After the mixture has been cooled to 200.degree. C., it is
concentrated under a water pump vacuum the residue is dissolved in
methylene chloride, the solution is washed with water and the
organic phase is dried over sodium sulfate and freed thoroughly
from the solvent under a water pump vacuum.
[0399] 4.2 g (62% of theory) of
4-(4-methoxycarbonyl-2,5-difluoro-phenyl)--
1-methyl-1,2,4-triazole-3,5-dione of melting point 156.degree. C.
are obtained
[0400] The compound listed as Example 69 in Table 1 can be
prepared, for example, as follows: 200
[0401] 29.3 g (0.096 mol) of
4-(4-chloro-2-fluoro-phenyl)-2-methyl-1-ethox-
ycarbonyl-thiosemicarbazide are stirred at the reflux temperature
in 400 ml of acetonitrile with 78 g (0.77 mol) of triethylamine for
8 hours and, after the minute has been cooled, it is concentrated
under a water pump vacuum. Water is added to the residue, the
mixture is brought to pH=4 with concentrated hydrochloric acid and
extracted with methylene chloride, and the organic phase is
separated off, dried over sodium sulfate and concentrated under a
water pump vacuum
[0402] 22 g (88% of theory) of
4-(4-chloro-2-fluoro-phenyl)-1-methyl-5-thi-
oxo-1,2,4-triazol-3-one of melting point 75.degree. C. are
obtained.
[0403] The compound listed as Example 70 in Table 1 can be
prepared, for example, as follows: 201
[0404] 7.1 g (0.026 mol) of the meso ionic compound according to
Example (Ia-5)--below--are stirred under reflux in 100 ml of
dimethylformamide for 18 hours and, after the mixture has been
cooled, it is concentrated under a water pump vacuum.
[0405] 5.9 g (83% of theory) of
4-(4-chloro-2-fluorophenyl)-1,2-dimethyl-5-
-thioxo-1,2,4-triazol-3-one are obtained.
[0406] .sup.1H-NMR (CDCl.sub.3): 3.45; 3.73; 7.30-7.40 ppm.
[0407] The compound listed as Example 71 in Table 1 can be prepared
for example, as follows: 202
[0408] 4.65 g (0.017 mol) of
4-(4-chloro-2-fluoro-phenyl)-1,2-dimethyl-5-t-
hioxo-1,2,4-triazol-3-one are initially introduced into the
reaction vessel in 30 ml of concentrated sulfuric acid, and 3 ml of
98% strength nitric acid are added dropwise at 0.degree. C. The
mixture is subsequently stirred at room temperate for 8 hours and
stirred with ice water and the product which has precipitated out
is filtered off.
[0409] 2.9 g (54% of theory) of
4-(4-chloro-2-fluoro-5-nitro-phenyl)-1,2-d-
imethyl-5-thioxo-1,2,4-triazol-3-one of melting point 146.degree.
C. are obtained.
[0410] The compound listed as Example 72 in Table 1 can be
prepared, for example, as follows: 203
[0411] 2.6 g (0.008 mol) of
4-(4-chloro-2-fluoro-5-nitro-phenyl)-1,2-dimet-
hyl-5-thioxo-1,2,4-triazol-3-one are initially introduced into the
reaction vessel in 20 ml of acetic acid with 10 ml of water and 10
ml of ethyl acetate, and 4.6 g (0.0082 mol) of iron powder are
added in portions, the temple being kept at maximum of 45.degree.
C. using an ice-bath. When the addition has ended, the m is
subsequently stirred at 23.degree. C. for 2 hours and filtered with
suction and. the residue is washed with water. The filtrate is
extracted with ethyl acetate and the organic phase is washed with
sodium hydrogencarbonate solution, dried over sodium sulfate and
concentrated under a water pump vacuum.
[0412] 1.5 g (65% of theory) of
4-(4-chloro-2-fluoro-5-amino-phenyl-1,2-di-
methyl-5-thioxo-1,2,4-triazol-3-one of melting point 208.degree. C.
are obtained.
[0413] The compound listed as Example 73 in Table 1 can be
prepared, for example, as follows: 204
[0414] 1.8 g (0.018 mol) of triethylamine and then 2.3 g (0.018
mol) of ethanesulfonyl chloride are added to 1.3 g (0.0045 mol) of
4-(4-chloro-2-fluoro-5-amino-phenyl)-1,2-dimethyl-5-thioxo-1,2,4-triazol--
3-one in 50 ml of methylene chloride at -10.degree. C., the mixture
is stirred at room temperature for 3 hours, water is added and the
organic phase is separated off, dried over sodium sulfate and
concentrated under a water pump vacuum.
[0415] 2.0 g (94% of theory) of
4-[4-chloro-2-fluoro-5-diethylsulfonyl)-am-
ino-phenyl]-1,2-dimethyl-5-thioxo-1,2,4-triazol-3-one of melting
point 195.degree. C. (decomposition) are obtained.
Compounds of the Formulae (Ia) or (Ib)
Example (Ia-1)
[0416] 205
[0417] A mixture of 4.2 g (12 mmol) of
4-(4-chloro-2-fluoro-5-i-propoxycar-
bonyl-phenyl)-1-methyl-5-thioxo-1,2,4-triazolin-3-one, 3.5 g (25
mmol) of potassium carbonate, 2.2 g (15 mmol) of methyl iodide and
60 ml of acetonitrile is stirred at 40.degree. C. for 12 hours. It
is then concentrated, the residue is taken up in water, the mixture
is acidified with concentrated hydrochloric acid and extracted with
methylene chloride and the organic phase is dried with sodium
sulfate and filtered. The filtrate is concentrated and the crude
product obtained as the residue is purified by column
chromatography (silica gel, methylene chloride/methanol, volume:
40:1).
[0418] 1.0 g (24% of theory) of the compound of the structural
formula given above of melting point 159.degree. C. is
obtained.
[0419] The compounds of the formula (Ia) listed in the following
Table 2, for example, can also be prepared analogously. 206
2TABLE 2 Examples of the compounds of the formula (Ia) Ex- am- ple
Physical No. Q.sup.1 Q.sup.2 R.sup.1 R.sup.2 Ar data Ia-2 S O
CH.sub.3 CH.sub.3 207 M.p.: 237.degree. C. Ia-3 S O CH.sub.3
CH.sub.3 208 M.p.: 168.degree. C. Ia-4 S O CH.sub.3 CH.sub.3 209
M.p.: 185.degree. C. Ia-5 S O CH.sub.3 CH.sub.3 210 M.p.:
182.degree. C.
[0420] The compound listed as Example (Ia-5) in Table 2 can be
prepared, for example, as follows 211
[0421] 20.7 g(0.08 mol) of
4-(4-chloro-2-fluoro-phenyl)-1-methyl-5-thioxo--
1,2,4-triazol-3-one are initially introduced into the reaction
vessel with 150 ml of dimethyl sulfoxide and 22 g (0.16 mol) of
potassium carbonate, 23 g (0.16 mol) of methyl iodide are then
added dropwise at 0.degree. C. in the course of 30 minutes. The
mixture is subsequently. stirred at 23.degree. C. for 4 hours and
then concentrated. The residue is stirred with water, the mixture
is acidified with concentrated hydrochloric acid and extracted with
methylene chloride, and the organic phase is dried over sodium
sulfate and concentrated under a water pump vacuum. After the
residue has been stirred with isopropanol, the product obtained as
crystals is isolated by filtration.
[0422] 7.8 g (36% of theory) of the mesoionic compound of the
structure given above are obtained.
Starting Substances of the Formula (II)
Example (II-1)
[0423] 212
[0424] 18.0 g (0.10 mol) of 4-cyano-2,5-difluoro-phenyl isocyanate
are added to a solution of 10.4 g (0.10 mol) of ethyl carbazate in
100 ml of toluene at 10.degree. C. and the mixture is stirred at
20.degree. C. for 2 hours and then at the reflux temperature for a
further 2 hours. The product obtained as crystals after cooling is
isolated by filtration.
[0425] 24.2 g (90% of theory) of
4-(4-cyano-2,5-difluoro-phenyl)-1-ethoxy-- carbonyl-semicarbazide
of melting point 245.degree. C. are obtained.
Example (II-2)
[0426] 213
[0427] 18.8 g (0.1 mol) of 4-chloro-2-fluoro-phenyl isothiocyanate
are stirred at the reflux temperature in 200 ml of acetonitrile
with 11.8 g (0.1 mol) of 2-methyl-1-ethoxy-carbonyl-hydrazine and
9.24 g (0.11 mol) of sodium hydrogencarbonate for 8 hours. After
the mixture has been cooled, it is concentrated under a water pump
vacuum, the residue is stirred with water, the mixture is extracted
with methylene chloride and the organic phase is separated of;
dried over sodium sulfate and concentrated under a water pump
vacuum.
[0428] 29 g (95% of theory) of
4-(4-chloro-2-fluoro-phenyl)-2-methyl-1-eth-
oxy-carbonyl-thiosemicarbazide of melting point 151.degree. C. are
obtained.
Starting Substances of the Formula (III)
Example (III-1)
[0429] 214
[0430] 6 g (12 mmol) of a 20% strength solution of phosgene in
toluene are added to a suspension of 3.1 g (10 mmol) of
2-methyl-4-(7-fluoro-3,4-dihy-
dro-3-oxo-4-propargyl-(2H)-1,4-benzoxazin-6-yl)-thiosemicarbazide
in 50 ml of methylene chloride at about 20.degree. C. The reaction
mixture is heated at 40.degree. C. for about 15 hours, the solvent
is removed in vacuo and the residue is taken up in water. The
mixture is neutralized with sodium bicarbonate solution and the
solid is filtered off, washed with water and dried in vacuo at
40-50.degree. C.
[0431] 2.8 g (84% of theory) of
2-(7-fluoro-3,4-dihydro-3-oxo-4-propargyl--
(2H)-1,4-benzoxazin-6-yl-imino)-3-methyl-3,4-dihydro-5-oxo-(4H)-1,3,4-thia-
diazole are obtained.
[0432] Melting point: 214.degree. C.
Example (III-2)
[0433] 215
[0434] 0.66 g (5.7 mmol) of thiophosgene is added to a solution of
1.7 g (5.7 mmol) of
4-(4-cyano-2-fluoro-5-i-propoxy-phenyl)-1,2-dimethylthiosem-
icarbazide in 30 ml of dry methylene chloride. The reaction is
slightly exothermic. The reaction mixture is stirred at the reflux
temperature for 4 hours, the solvent is removed in vacuo and the
residue is stirred with saturated sodium carbonate solution. The
solid which forms is filtered off washed with water and pressed off
on clay.
[0435] 1.5 g (78% of theory) of
2-(4-cyano-2-fluoro-5-i-propoxy-phenylimin-
o)-3,4-dimethyl-5-thio-1,3,4-thiadiazole of melting point
117.degree. are obtained.
Starting Substances of the Formula (IV)
Example (IV-1)
[0436] 216
[0437] 129 g (1.12 mol) of thiophosgene are added to 81 g (0.56
mol) of 4-chloro-2-fluoro-aniline in 500 ml of chlorobenzene at
80.degree. C. to 90.degree. C. in the course of 1 hour and the sure
is then stirred at the reflux temperature for 2 hours until the
evolution of gas has ended The clear solution is concentrated to
dryness under a water pump vacuum.
[0438] 102 g (97% of theory) of 4-chloro-2-fluoro-phenyl
isothiocyanate are obtained
[0439] .sup.1H-NMR (CDCl.sub.3): 7.10-7.20 ppm; GC-MS: (M=187)
98.4%.
[0440] Use examples:
[0441] Example A
[0442] Pre-emergence test
[0443] Solvent: 5 parts by weight of acetone
[0444] Emulsifier: 1 part by weight of alkylaryl polyglycol
ether
[0445] 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.
[0446] Seeds of the test plants are sown in normal soil and, after
24 hours, watered with the preparation of the active compound. It
is expedient to keep constant the amount of water per unit area.
The concentration of the active compound in the preparation is of
no importance, only the amount of active compound applied per unit
area being decisive. After three weeks, the degree of damage to the
plants is rated in % damage in comparison to the development of the
untreated control, The figures denote:
[0447] 0%=no action (like untreated control)
[0448] 100%=total destruction
[0449] In this test, for example, the compounds according to
preparation examples 3, 9, 10, 12, 13, 14 and 15, when applied in
amounts of 60 g/ha, show in some cases a good tolerability toward
crop plants, such as, for example, barley and corn (10-70%) and a
very potent action against weeds, such as Alopecurus (90-100%),
Cynodon (95-100%), Setaria (70-100%), Amaranthus (90-100%),
Chenopodium (100%), Matricaria (95-100%), Polygonum (80-100%),
Portulaca (95-100%) and Viola (90-100%).
[0450] Example B
[0451] Post-emergence test
[0452] Solvent: 5 parts by weight of acetone
[0453] Emulsifier: 1 part by weight of alkylaryl polyglycol
ether
[0454] 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.
[0455] Test plants which have a height of 5-15 cm 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
After three weeks, the degree of damage to the plants is rated in %
damage in comparison to the development of the untreated control,
The figures denote:
[0456] 0%=no action (like untreated control)
[0457] 100%=total destruction
[0458] In this test, for example, the compounds according to
preparation examples 3, 4, 9, 10, 12, 13, 14 and 15 and Ia-1 and
Ia-2, when applied in amounts of between 15 and 250 g/ha, show a
potent action against weeds, such as Amaranthus (60-100 %),
Chenopodium (90-100%), Datura (80-100%), Galium (90-100%) and
Veronica (50-100%).
* * * * *