U.S. patent application number 09/895649 was filed with the patent office on 2002-06-13 for novel substituted phenylketoenols.
Invention is credited to Andersch, Wolfram, Bretschneider, Thomas, Dahmen, Peter, Dollinger, Markus, Erdelen, Christoph, Fischer, Reiner, Graff, Alan, Hagemann, Hermann, Wachendorff-Neumann, Ulrike.
Application Number | 20020072617 09/895649 |
Document ID | / |
Family ID | 26032141 |
Filed Date | 2002-06-13 |
United States Patent
Application |
20020072617 |
Kind Code |
A1 |
Hagemann, Hermann ; et
al. |
June 13, 2002 |
Novel substituted phenylketoenols
Abstract
The invention relates to novel phenyl-substituted cyclic
ketoenols of the formula (I) 1 in which Het represents one of the
groups 2 and G, V, W, X, Y and Z are each as defined in the
description, to processes and intermediates for their preparation
and to their use as pesticides and herbicides.
Inventors: |
Hagemann, Hermann;
(Leverkusen, DE) ; Fischer, Reiner; (Monheim,
DE) ; Bretschneider, Thomas; (Lohmar, DE) ;
Erdelen, Christoph; (Leichlingen, DE) ;
Wachendorff-Neumann, Ulrike; (Neuwied, DE) ; Dahmen,
Peter; (Neuss, DE) ; Dollinger, Markus;
(Overland Park, KS) ; Graff, Alan; (Leverkusen,
DE) ; Andersch, Wolfram; (Leverkusen, DE) |
Correspondence
Address: |
BAYER CORPORATION
PATENT DEPARTMENT
100 BAYER ROAD
PITTSBURGH
PA
15205
US
|
Family ID: |
26032141 |
Appl. No.: |
09/895649 |
Filed: |
June 29, 2001 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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09895649 |
Jun 29, 2001 |
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09319489 |
Jun 4, 1999 |
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6288102 |
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Current U.S.
Class: |
548/541 ;
546/290 |
Current CPC
Class: |
C07D 491/10 20130101;
C07D 495/10 20130101; C07D 309/10 20130101; A01N 43/90 20130101;
C07D 309/08 20130101; C07D 405/12 20130101; C07F 9/6561 20130101;
C07D 309/14 20130101; C07D 493/10 20130101 |
Class at
Publication: |
548/541 ;
546/290 |
International
Class: |
C07D 27/12; C07D 213/30;
C07D 213/32 |
Foreign Application Data
Date |
Code |
Application Number |
Dec 12, 1996 |
DE |
196 51 686.2 |
Claims
1. Compounds of the fornula (I) 85in which V represents hydrogen,
halogen, alkyl or alkoxy, W represents hydrogen, cyano, nitro,
halogen, alkyl, alkenyl, alkinyl, alkoxy, halogenoalkyl,
halogenoalkoxy, in each case optionally substituted phenyl,
phenoxy, phenylthio, phenylalkoxy or phenylalkylthio, X represents
halogen, alkyl, alkenyl, alkinyl, alkoxy, halogenoalkyl,
halogenoalkoxy, cyano, nitro, in each case optionally substituted
phenyl, phenoxy, phenylthio, phenylalkyloxy or phenylalkylthio, Y
represents hydrogen, halogen, alkyl, alkoxy, halogenoalkyl,
halogenoalkoxy, cyano or nitro, Z represents hydrogen, halogen,
alkyl, alkoxy, halogenoalkyl, halogenoalkoxy, hydroxyl, cyano,
nitro or in each case optionally substituted phenoxy, phenylthio,
5- or 6-membered hetaryloxy, 5- or 6-membered hetarylthio,
phenylalkyloxy or phenylalkylthio, or Y and Z together with the
linking carbon atoms represent an optionally substituted cycle
which is optionally interrupted by one or more heteroatoms, or W
and Z together with the linking carbon atoms represent an
optionally substituted cycle which is optionally interrupted by one
or more heteroatoms, Het represents one of the groups 86wherein G
represents hydrogen (a) or represents one of the groups 87wherein E
represents a metal ion equivalent or an ammonium ion, L represents
oxygen or sulphur, M represents oxygen or sulphur, R.sup.1
represents in each case optionally halogen- or cyano-substituted
alkyl, alkenyl, alkoxyalkyl, alkylthioalkyl or polyalkoxyalkyl or
represents in each case optionally halogen-, alkyl- or
alkoxy-substituted cycloalkyl or heterocyclyl or represents in each
case optionally substituted phenyl, phenylalkyl, hetaryl,
phenoxyalkyl or hetaryloxyalkyl, R.sup.2 represents in each case
optionally halogen- or cyano-substituted alkyl, alkenyl,
alkoxyalkyl or polyalkoxyalkyl or represents in each case
optionally substituted cycloalkyl, phenyl or benzyl, R.sup.3,
R.sup.4 and R.sup.5 independently of one another each represent in
each case optionally halogen-substituted alkyl, alkoxy, alkylamino,
dialkylamino, alkylthio, alkenylthio or cycloalkylthio or represent
in each case optionally substituted phenyl, benzyl, phenoxy or
phenylthio, R.sup.6 and R.sup.7 independently of one another each
represent hydrogen, represent in each case optionally halogen- or
cyano-substituted alkyl, cycloalkyl, alkenyl, alkoxy, alkoxyalkyl,
represent in each case optionally substituted phenyl or benzyl, or
together with the linking N atom form an optionally oxygen- or
sulphur-containing and optionally substituted cycle.
2. Compounds of the formula (I) according to claim 1, in which V
represents hydrogen, halogen, C.sub.1-C.sub.6-alkyl or
C.sub.1-C.sub.6-alkoxy, W represents hydrogen, nitro, cyano,
halogen, C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkenyl,
C.sub.2-C.sub.6-alkinyl, C.sub.1-C.sub.6-alkoxy,
C.sub.1-C.sub.4-halogenoalkyl, C.sub.1-C.sub.4-halogenoalkoxy or
represents in each case optionally halogen-, C
.sub.1-C.sub.6-alkyl-, C.sub.1-C.sub.6-alkoxy-,
C.sub.1-C.sub.4-halogenoalkyl-, C.sub.1-C.sub.4-halogenoalkoxy-,
nitro- or cyano-substituted phenyl, phenoxy, phenylthio,
phenyl-C.sub.1-C.sub.4-- alkoxy or
phenyl-C.sub.1-C.sub.4-alkylthio, X represents halogen,
C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkenyl,
C.sub.2-C.sub.6-alkinyl, C.sub.1-C.sub.6-alkoxy,
C.sub.1-C.sub.4-halogenoalkyl, C.sub.1-C.sub.4-halogenoalkoxy,
cyano, nitro or represents in each case optionally halogen-,
C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-alkoxy,
C.sub.1-C.sub.4-halogenoalkyl, C.sub.1-C.sub.4-halogenoalkoxy,
nitro- or cyano-substituted phenyl, phenoxy, phenylthio,
phenyl-C.sub.1-C.sub.4-alk- oxy or
phenyl-C.sub.1-C.sub.4-alkylthio, Y represents hydrogen, halogen,
C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-alkoxy,
C.sub.1-C.sub.4-halogenoal- kyl, C.sub.1-C.sub.4-halogenoalkoxy,
cyano or nitro, Z represents hydrogen, halogen,
C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-alkoxy,
C.sub.1-C.sub.4-halogenoalkyl, C.sub.1-C.sub.4-halogenoalkoxy,
hydroxyl, cyano, nitro or represents in each case optionally
halogen-, C.sub.1-C.sub.4-alkyl-, C.sub.1-C.sub.4-alkoxy-,
C.sub.1-C.sub.4-halogeno- alkyl-, C.sub.1-C.sub.4-halogenoalkoxy-,
nitro- or cyano-substituted phenoxy, phenylthio, thiazolyloxy,
pyridinyloxy, pyrimidyloxy, pyrazolyloxy,
phenyl-C.sub.1-C.sub.4-alkyloxy or phenyl-C.sub.1-C.sub.4-a-
lkylthio or Y and Z together with the linking carbon atoms
represent in each case optionally halogen-, C.sub.1-C.sub.6-alkyl-,
C.sub.1-C.sub.6-alkoxy- or
C.sub.1-C.sub.4-halogenoalkyl-substituted
C.sub.3-C.sub.5-alkanediyl or C.sub.3-C.sub.5-alkenediyl in which
optionally one to three members may be replaced independently of
one another by oxygen, sulphur, nitrogen or a carbonyl group, or W
and Z together with the linking carbon atoms represent in each case
optionally halogen-, C.sub.1-C.sub.6-alkyl-,
C.sub.1-C.sub.6-alkoxy- or
C.sub.1-C.sub.4-halogenoalkyl-substituted
C.sub.3-C.sub.5-alkanediyl or C.sub.3-C.sub.5-alkenediyl in which
one to three members may be replaced independently of one another
by oxygen, sulphur, nitrogen or a carbonyl group, Het represents
one of the groups 88G represents hydrogen (a) or represents one of
the groups 89in which E represents a metal ion equivalent or an
ammonium ion, L represents oxygen or sulphur and M repersents
oxygen or sulphur. R.sup.1 represents in each case optionally
halogen- or cyano-substituted C.sub.1-C.sub.20-alkyl,
C.sub.2-C.sub.20-alkenyl,
C.sub.1-C.sub.8-alkoxy-C.sub.1-C.sub.8-alkyl,
C.sub.1-C.sub.8-alkylthio-C.sub.1-C.sub.8-alkyl or
poly-C.sub.1-C.sub.8-alkoxy-C.sub.1-C.sub.8-alkyl or represents
optionally halogen-, C.sub.1-C.sub.6-alkyl- or
C.sub.1-C.sub.6-alkoxy-sub- stituted C.sub.3-C.sub.8-cycloalkyl in
which optionally one or two not directly adjacent methylene groups
are replaced by oxygen and/or sulphur, represents optionally
halogen-, cyano-, nitro-, C.sub.1-C.sub.6-alkyl-,
C.sub.1-C.sub.6-alkoxy-, C.sub.1-C.sub.6-halogenoalkyl-,
C.sub.1-C.sub.6-halogenoalkoxy-, C.sub.1-C.sub.6-alkylthio-or
C.sub.1-C.sub.6-alkylsulfonyl-substituted phenyl, represents
optionally halogen-, nitro-, cyano-, C.sub.1-C.sub.6-alkyl-,
C.sub.1-C.sub.6-alkoxy-- , C.sub.1-C.sub.6-halogenoalkyl- or
C.sub.1-C.sub.6-halogenoalkoxy-substit- uted
phenyl-C.sub.1-C.sub.6-alkyl, represents optionally halogen- or
C.sub.1-C.sub.6-alkyl-substituted 5- or 6-membered hetaryl having
one or two heteroatoms from the group consisting of oxygen, sulphur
and nitrogen, represents optionally halogen- or
C.sub.1-C.sub.6-alkyl-substit- uted phenoxy-C.sub.1-C.sub.6-alkyl
or represents optionally halogen-, amino- or
C.sub.1-C.sub.6-alkyl-substituted 5-or 6-membered
hetaryloxy-C.sub.1-C.sub.6-alkyl having one or two heteroatoms from
the group consisting of oxygen, sulphur and nitrogen, R.sup.2
represents in each case optionally halogen- or cyano-substituted
C.sub.1-C.sub.20-alkyl, C.sub.2-C.sub.20-alkenyl,
C.sub.1-C.sub.8-alkoxy-- C.sub.2-C.sub.8-alkyl or
poly-C.sub.1-C.sub.8-alkoxy-C.sub.2-C.sub.8-alkyl- , represents
optionally halogen-, C.sub.1-C.sub.6-alkyl- or
C.sub.1-C.sub.6-alkoxy-substituted C.sub.3-C.sub.8-cycloalkyl or
represents in each case optionally halogen-, cyano-, nitro-,
C.sub.1-C.sub.6-alkyl-, C.sub.1-C.sub.6-alkoxy-,
C.sub.1-C.sub.6-halogeno- alkyl- or
C.sub.1-C.sub.6-halogenoalkoxy-substituted phenyl or benzyl,
R.sup.3 represents optionally halogen-substituted
C.sub.1-C.sub.8-alkyl or represents in each case optionally
halogen-, C.sub.1-C.sub.6-alkyl-, C.sub.1-C.sub.6-alkoxy-,
C.sub.1-C.sub.4-halogenoalkyl-, C.sub.1-C.sub.4-halogenoalkoxy-,
cyano- or nitro-substituted phenyl or benzyl, R.sup.4 and R.sup.5
independently of one another each represent in each case optionally
halogen-substituted C.sub.1-C.sub.8-alkyl, C.sub.1-C.sub.8-alkoxy,
C.sub.1-C.sub.8-alkylamino, di-(C.sub.1-C.sub.8-alkyl)amino,
C.sub.1-C.sub.8-alkylthio or C.sub.3-C.sub.8-alkenylthio or
represent in each case optionally halogen-, nitro-, cyano-,
C.sub.1-C.sub.4-alkoxy-, C.sub.1-C.sub.4-halogenoalkoxy-,
C.sub.1-C.sub.4-alkylthio-, C.sub.1-C.sub.4-halogenoalkylthio-,
C.sub.1-C.sub.4-alkyl- or C.sub.1-C.sub.4-halogenoalkyl-substituted
phenyl, phenoxy or phenylthio and R.sup.6 and R.sup.7 independently
of one another each represent hydrogen, represent in each case
optionally halogen- or cyano-substituted C.sub.1-C.sub.8-alkyl,
C.sub.3-C.sub.8-cycloalkyl, C.sub.1-C.sub.8-alkoxy,
C.sub.3-C.sub.8-alkenyl or
C.sub.1-C.sub.8-alkoxy-C.sub.2-C.sub.8-alkyl, represent in each
case optionally halogen-, C.sub.1-C.sub.8-alkyl-,
C.sub.1-C.sub.8-halogenoalky- l- or
C.sub.1-C.sub.8-alkoxy-substituted phenyl or benzyl or together
represent an optionally C.sub.1-C.sub.6-alkyl-substituted
C.sub.3-C.sub.6-alkylene radical in which optionally one methylene
group is replaced by oxygen or sulphur.
3. Compounds of the formula (I) according to claim 1, in which V
represents hydrogen, fluorine, chlorine, bromine,
C.sub.1-C.sub.4-alkyl or C.sub.1-C.sub.4-alkoxy, W represents
hydrogen, nitro, cyano, fluorine, chlorine, bromine,
C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-alkoxy,
C.sub.1-C.sub.2-halogenoalkyl, C.sub.1-C.sub.2-halogenoalkoxy or
represents in each case optionally fluorine-, chlorine-, bromine-,
C.sub.1-C.sub.4-alkyl-, C.sub.1-C.sub.4-alkoxy-,
C.sub.1-C.sub.2-halogeno- alkyl-, C.sub.1-C.sub.2-halogenoalkoxy-,
nitro- or cyano-substituted phenyl, phenoxy or benzyloxy, X
represents fluorine, chlorine, bromine, C.sub.1-C.sub.4-alkyl,
C.sub.1-C.sub.4-alkoxy, C.sub.1-C.sub.2-halogenoal- kyl,
C.sub.1-C.sub.2-halogenoalkoxy, cyano, nitro or represents in each
case optionally fluorine-, chlorine-, bromine-,
C.sub.1-C.sub.4-alkyl-, C.sub.1-C.sub.4-alkoxy-,
C.sub.1-C.sub.2-halogenoalkyl-, C.sub.1-C.sub.2-halogenoalkoxy-,
nitro- or cyano-substituted phenyl, phenoxy or benzyloxy, Y
represents hydrogen, fluorine, chlorine, bromine,
C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-alkoxy,
C.sub.1-C.sub.2-halogenoal- kyl, C.sub.1-C.sub.2-halogenoalkoxy,
cyano or nitro, Z represents hydrogen, fluorine, chlorine, bromine,
C.sub.1-C.sub.4-alkyl-, C.sub.1-C.sub.4-alkoxy-,
C.sub.1-C.sub.2-halogenoalkyl, C.sub.1-C.sub.2-halogenoalkoxy,
hydroxyl, cyano, nitro or represents in each case optionally
fluorine-, chlorine-, bromine-, C.sub.1-C.sub.4-alkyl-,
C.sub.1-C.sub.4-alkoxy-, C.sub.1-C.sub.2-halogeno- alkyl-,
C.sub.1-C.sub.2-halogenoalkoxy-, nitro- or cyano-substituted
phenoxy or benzyloxy or Y and Z together with the linking carbon
atoms represent in each case optionally fluorine-, chlorine-,
bromine-, C.sub.1-C.sub.4-alkyl-, C.sub.1-C.sub.4-alkoxy-or
C.sub.1-C.sub.2-halogen- oalkyl-substituted
C.sub.3-C.sub.4-alkanediyl or C.sub.3-C.sub.4-alkenediy- l in which
optionally one or two not directly adjacent members may be replaced
independently of one another by oxygen, sulphur or nitrogen, or W
and Z together with the linking carbon atoms represent in each case
optionally fluorine-, chlorine-, bromine-, C.sub.1-C.sub.4-alkyl-,
C.sub.1-C.sub.4-alkoxy-or C.sub.1-C.sub.2-halogenoalkyl-substituted
C.sub.3-C.sub.4-alkanediyl or C.sub.3-C.sub.4-alkenediyl in which
one or two not directly adjacent members may be replaced
independently of one another by oxygen, sulphur or nitrogen, Het
represents one of the groups 90G represents hydrogen (a) or
represents one of the groups 91in which E represents a metal ion
equivalent or an ammonium ion, L represents oxygen or sulphur and M
represents oxygen or sulphur, R.sup.1 represents in each case
optionally fluorine- or chlorine-substituted
C.sub.1-C.sub.16-alkyl, C.sub.2-C.sub.16-alkenyl,
C.sub.1-C.sub.6-alkoxy-C.sub.1-C.sub.6-alkyl,
C.sub.1-C.sub.6-alkylthio-C.sub.1-C.sub.6-alkyl or
poly-C.sub.1-C.sub.6-alkoxy-C.sub.1-C.sub.6-alkyl or represents
optionally fluorine-, chlorine-, C.sub.1-C.sub.5-alkyl- or
C.sub.1-C.sub.5-alkoxy-substituted C.sub.3-C.sub.7-cycloalkyl in
which optionally one or two not directly adjacent methylene groups
are replaced by oxgyen and/or sulphur, represents optionally
fluorine-, chlorine-, bromine-, cyano-, nitro-, C
.sub.1-C.sub.4-alkyl-, C.sub.1-C.sub.4-alkoxy-,
C.sub.1-C.sub.3-halogenoalkyl-, C.sub.1-C.sub.3-halogenoalkoxy-,
C.sub.1-C.sub.4-alkylthio- or
C.sub.1-C.sub.4-alkylsulphonyl-substituted phenyl, represents
optionally fluorine-, chlorine-, bromine-, C.sub.1-C.sub.4-alkyl-,
C.sub.1-C.sub.4-alkoxy-, C.sub.1-C.sub.3-halogenoalkyl- or
C.sub.1-C.sub.3-halogenoalkoxy-substituted
phenyl-C.sub.1-C.sub.4-alkyl, represents in each case optionally
fluorine-, chlorine-, bromine- or C.sub.1-C.sub.4-alkyl-substituted
pyrazolyl, thiazolyl, pyridyl, pyrimidyl, furanyl or thienyl,
represents optionally fluorine-, chlorine-, bromine- or
C.sub.1-C.sub.4-alkyl-substituted phenoxy-C.sub.1-C.sub.5-alkyl or
represents in each case optionally fluorine-, chlorine-,
bromine-amino-or C.sub.1-C.sub.4-alkyl-substituted
pyridyloxy-C.sub.1-C.sub.5-alkyl,
pyrimidyloxy-C.sub.1-C.sub.5-alkyl or
thiazolyloxy-C.sub.1-C.sub.5-alkyl, R.sup.2 represents in each case
optionally fluorine- or chlorine-substituted
C.sub.1-C.sub.16-alkyl, C.sub.2-C.sub.16-alkenyl,
C.sub.1-C.sub.6-alkoxy-C.sub.2-C.sub.6-alkyl or
poly-C.sub.1-C.sub.6-alkoxy-C.sub.2-C.sub.6-alkyl, represents
optionally fluorine-, chlorine-, C.sub.1-C.sub.4-alkyl- or
C.sub.1-C.sub.4-alkoxy-su- bstituted C.sub.3-C.sub.7-cycloalkyl or
represents in each case optionally fluorine-, chlorine-, bromine-,
cyano-, nitro-, C.sub.1-C.sub.4-alkyl-, C.sub.1-C.sub.3-alkoxy-,
C.sub.1-C.sub.3-halogenoalkyl- or
C.sub.1-C.sub.3-halogenoalkoxy-substituted phenyl or benzyl,
R.sup.3 represents optionally fluorine- or chlorine-substituted
C.sub.1-C.sub.6-alkyl or represents in each case optionally
fluorine-, chlorine-, bromine-, C.sub.1-C.sub.4-alkyl-,
C.sub.1-C.sub.4-alkoxy-, C.sub.1-C.sub.2-halogenoalkoxy-,
C.sub.1-C.sub.2-halogenoalkyl-, cyano- or nitro-substituted phenyl
or benzyl, R.sup.4 and R.sup.5 independently of one another each
represent in each case optionally fluorine- or chlorine-substituted
C.sub.1-C.sub.6-alkyl-, C.sub.1-C.sub.6-alkoxy-,
C.sub.1-C.sub.6-alkylamino-, di-(C.sub.1-C.sub.6-alkyl)amino,
C.sub.1-C.sub.6-alkylthio or C.sub.3-C.sub.4-alkenylthio or
represent in each case optionally fluorine-, chlorine-, bromine-,
nitro-, cyano-, C.sub.1-C.sub.3-alkoxy-,
C.sub.1-C.sub.3-halogenoalkoxy-, C.sub.1-C.sub.3-alkylthio-,
C.sub.1-C.sub.3-halogenoalkylthio-, C.sub.1-C.sub.3-alkyl or
C.sub.1-C.sub.3-halogenoalkyl-substituted phenyl, phenoxy or
phenylthio and R.sup.6 and R.sup.7 independently of one another
each represent hydrogen, represent in each case optionally
fluorine- or chlorine-substituted C.sub.1-C.sub.6-alkyl,
C.sub.3-C.sub.6-cycloalkyl, C.sub.1-C.sub.6-alkoxy,
C.sub.3-C.sub.6-alkenyl or
C.sub.1-C.sub.6-alkoxy-C.sub.2-C.sub.6-alkyl, represent in each
case optionally fluorine-, chlorine-, bromine-,
C.sub.1-C.sub.5-halogenoalkyl-, C.sub.1-C.sub.5-alkyl- or
C.sub.1-C.sub.5-alkoxy-substituted phenyl or benzyl, or together
represent an optionally C.sub.1-C.sub.4-alkyl-substituted
C.sub.3-C.sub.6-alkylene radical in which optionally one methylene
group is replaced by oxygen or sulphur.
4. Compounds of the formula (I) according to claim 1, in which V
represents hydrogen, fluorine, chlorine, bromine, methyl, ethyl,
propyl, iso-propyl, tert-butyl, methoxy, ethoxy, propoxy or
iso-propoxy, W represents hydrogen, nitro, cyano, fluorine,
chlorine, bromine, methyl, ethyl, propyl, n-butyl, iso-propyl,
iso-butyl, methoxy, ethoxy, propoxy, iso-propoxy, trifluoromethyl,
difluoromethoxy, trifluoromethoxy, phenyl or benzyloxy X represents
fluorine, chlorine, bromine, methyl, ethyl, propyl, butyl,
iso-butyl, iso-propyl, methoxy, ethoxy, propoxy, iso-propoxy,
trifluoromethyl, trifluoromethoxy, difluoromethoxy, cyano, nitro,
phenyl or benzyloxy, Y represents hydrogen, fluorine, chlorine,
bromine, methyl, ethyl, propyl, iso-propyl, n-butyl, iso-butyl,
tert-butyl, methoxy, ethoxy, propoxy, iso-propoxy, trifluoromethyl,
trifluoromethoxy, difluoromethoxy, cyano or nitro, Z represents
hydrogen, fluorine, chlorine, bromine, methyl, ethyl, propyl,
butyl, iso-butyl, iso-propyl, tert-butyl, methoxy, ethoxy, propoxy,
iso-propoxy, trifluoromethyl, trifluoromethoxy, difluoromethoxy,
cyano or nitro or Y and Z together with the linking carbon atoms
represent optionally fluorine-, chlorine-, methyl-, ethyl- propyl-,
iso-propyl-, methoxy-, ethoxy-, propoxy-, iso-propoxy- or
trifluoromethyl-substituted C.sub.3-C.sub.4-alkanediyl in which
optionally two not directly adjacent members are replaced by oxygen
or W and Z together with the linking carbon atoms represent
optionally fluorine-, chlorine-, methyl-, ethyl-, propyl-,
iso-propyl-, methoxy-, ethoxy-, propoxy-, iso-propoxy- or
trifluoromethyl-substituted C.sub.3-C.sub.4-alkanediyl in which
optionally two not directly adjacent members are replaced by
oxygen, Het represents one of the groups 92G represents hydrogen
(a) or represents one of the groups 93in which E represents a metal
ion equivalent or an ammonium ion, L represents oxygen or sulphur
and M represents oxygen or sulphur, R.sup.1 represents in each case
optionally chlorine- or fluorine-substituted
C.sub.1-C.sub.14-alkyl, C.sub.2-C.sub.14-alkenyl,
C.sub.1-C.sub.4-alkoxy-C.sub.1-C.sub.6-alkyl,
C.sub.1-C.sub.4-alkylthio-C- .sub.1-C.sub.6-alkyl,
poly-C.sub.1-C.sub.4-alkoxy-C.sub.1-C.sub.4-alkyl or represents
optionally fluorine-, chlorine-, methyl-, ethyl-, n-propyl-,
i-propyl-, n-butyl-, i-butyl-, tert-butyl-, methoxy-, ethoxy-,
n-propoxy- or iso-propoxy-substituted C.sub.3-C.sub.6-cycloalkyl in
which optionally one or two not directly adjacent methylene groups
are replaced by oxygen and/or sulphur, represents optionally
fluorine-, chlorine-, bromine-, cyano-, nitro-, methyl-, ethyl-,
n-propyl-, i-propyl-, methoxy-, ethoxy-, trifluoromethyl-,
trifluoromethoxy-, methylthio-, ethylthio-, methylsulphonyl- or
ethylsulphonyl-substituted phenyl, represents optionally fluorine-,
chlorine-, bromine-, methyl-, ethyl-, n-propyl-, i-propyl-,
methoxy-, ethoxy-, trifluoromethyl- or trifluoromethoxy-substi-
tuted benzyl, represents in each case optionally fluorine-,
chlorine-, bromine-, methyl- or ethyl-substituted furanyl, thienyl
or pyridyl, represents optionally fluorine-, chlorine-, methyl- or
ethyl-substituted phenoxy-C.sub.1-C.sub.4-alkyl or represents in
each case optionally fluorine-, chlorine-, amino-, methyl-or
ethyl-substituted pyridyloxy-C.sub.1-C.sub.4-alkyl,
pyrimidyloxy-C.sub.1-C.sub.4-alkyl or
thiazolyloxy-C.sub.1-C.sub.4-alkyl, R.sup.2 represents in each case
optionally fluorine- or chlorine-substituted
C.sub.1-C.sub.14-alkyl, C.sub.2-C.sub.14-alkenyl,
C.sub.1-C.sub.4-alkoxy-C.sub.2-C.sub.6-alkyl or
poly-C.sub.1-C.sub.4-alkoxy-C.sub.2-C.sub.6-alkyl, represents
optionally fluorine-, chlorine-, methyl-, ethyl-, n-propyl,
iso-propyl- or methoxy-substituted C.sub.3-C.sub.6-cycloalkyl, or
represents in each case optionally fluorine-, chlorine-, cyano-,
nitro-, methyl-, ethyl-, n-propyl-, i-propyl-, methoxy-, ethoxy-,
trifluoromethyl- or trifluoromethoxy-substituted phenyl or benzyl,
R.sup.3 represents in each case optionally fluorine- or
chlorine-substituted methyl, ethyl, propyl, iso-propyl, n-butyl,
tert-butyl, or represents in each case optionally fluorine-,
chlorine-, bromine-, methyl-, ethyl-, iso-propyl-, tert-butyl-,
methoxy-, ethoxy-, iso-propoxy-, trifluoromethyl-,
trifluoromethoxy-, cyano- or nitro-substituted phenyl or benzyl,
R.sup.4 and R.sup.5 independently of one another each represent in
each case optionally fluorine- or chlorine-substituted
C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-alkoxy,
C.sub.1-C.sub.4-alkylamino, di-(C.sub.1-C.sub.4-alkyl)amino or
C.sub.1-C.sub.4-alkylthio or represent in each case optionally
fluorine-, chlorine-, bromine-, nitro-, cyano-, methyl-, methoxy-,
trifluoromethyl- or trifluoromethoxy-substituted phenyl, phenoxy or
phenylthio and R.sup.6 and R.sup.7 independently of one another
represent hydrogen, represent in each case optionally fluorine- or
chlorine-substituted C.sub.1-C.sub.4-alkyl,
C.sub.3-C.sub.6-cycloalkyl, C.sub.1-C.sub.4-alkoxy,
C.sub.3-C.sub.4-alkenyl or
C.sub.1-C.sub.4-alkoxy-C.sub.2-C.sub.4-alkyl, represent in each
case optionally fluorine-, chlorine-, bromine-, methyl-, methoxy-
or trifluoromethyl-substituted phenyl or benzyl, or together
represent an optionally methyl- or ethyl-substituted
C.sub.5-C.sub.6-alkylene radical in which optionally one methylene
group is replaced by oxygen or sulphur.
5. Process for preparing compounds of the formula (1) according to
claim 1, characterized in that (A) Compounds of the formula (I-1-a)
94in which V, W, X, Y and Z are each as defined in claim 1 are
obtained when compounds of the formula (II) 95in which V, W, X, Y
and Z are each as defined above and R.sup.8 represents alkyl are
intramolecularly condensed in the presence of a diluent and in the
presence of a base, (B) Compounds of the formula (I-2-a) 96in which
V, W, X, Y and Z are each as defined above are obtained when
compounds of the formula (III) 97in which V, W, X, Y, Z and R.sup.8
are each as defined above are intramolecularly condensed in the
presence of a diluent and in the presence of a base, (C) Compounds
of the formula (I-3-a) 98in which V, W, X, Y and Z are each as
defined above are obtained when compounds of the formula (IV) 99in
which V, W, X, Y, Z and R.sup.8 are each as defined above and T
represents hydrogen, halogen, alkyl or alkoxy are intramolecularly
cyclized, if appropriate in the presence of a diluent and in the
presence of an acid, and the resulting compounds of the formulae
(I-1-a) to (I-3-a) shown above in which V, W, X, Y and Z are each
as defined above are subsequently, if appropriate, in each case (D)
.alpha.) reacted with acyl halides of the formula (V) 100in which
R.sup.1 is as defined in claim 1 and Hal represents halogen or
.beta.) with carboxylic anhydrides of the formula
(VI)R.sup.1--CO--O--CO--R.sup.1 (VI)in which R.sup.1 is as defined
above, if appropriate in the presence of a diluent and if
appropriate in the presence of an acid binder; or (E) reacted with
chloroformic esters or chloroformic thioesters of the formula
(VII)R.sup.2--M--CO--Cl (VII)in which R.sup.2 and M are each as
defined above, if appropriate in the presence of a diluent and if
appropriate in the presence of an acid binder; (F) reacted with
chloromonothioformic esters or chlorodithioformic esters of the
formula (VIII) 101in which M and R.sup.2 are each as defined in
claim 1, if appropriate in the presence of a diluent and if
appropriate in the presence of an acid binder, or (G) reacted with
sulphonyl chlorides of the formula (IX)R.sup.3--SO.sub.2--Cl (IX)in
which R.sup.3 is as defined in claim 1, if appropriate in the
presence of a diluent and if appropriate in the presence of an acid
binder; or (H) reacted with phosphorous compounds of the formula
(X) 102in which L, R.sup.4 and R.sup.5 are each as defined in claim
1 and Hal represents halogen, if appropriate in the presence of a
diluent and if appropriate in the presence of an acid binder; or
(I) reacted with metal compounds or amines of the formulae (XI) or
(XII) Me(OR.sup.10), (XI) 103in which Me represents a mono- or
divalent metal t represents the number 1 or 2 and R.sup.10,
R.sup.11, R.sup.12 independently of one another each represent
hydrogen or alkyl, if appropriate in the presence of a diluent, or
(J) .alpha.) reacted with isocyanates or isothiocyanates of the
formula (XIII)R.sup.6--N.dbd.C.dbd.- L (XIII)in which R.sup.6 and L
are each as defined in claim 1, if appropriate in the presence of a
diluent and if appropriate in the presence of a catalyst or .beta.)
reacted with carbamoyl chlorides or thiocarbamoyl chlorides of the
formula (XIV) 104in which L, R.sup.6 and R.sup.7 are each as
defined in claim 1, if appropriate in the presence of a diluent and
if appropriate in the presence of an acid binder.
6. Compounds of the formula (II) 105in which V, W, X, Y and Z are
each as defined in claim 1 and R.sup.8 represents alkyl.
7. Compounds of the formula (XVII) 106in which V, W, X, Y and Z are
each as defined in claim 1.
8. Compounds of the formula (XXV) 107in which V, W, X, Y and Z are
each as defined in claim 1.
9. Compounds of the formula (III) 108in which V, W, X, Y and Z are
each as defined above and R.sup.8 represents alkyl.
10. Compounds of the formula (XXVI) 109in which R.sup.8 represents
alkyl.
11. Compounds of the formula (IV) 110in which T, V, W, X, Y and Z
are each as defined above and R.sup.8 represents alkyl.
12. Compounds of the formula (XXVII) 111in which T represents
hydrogen, halogen, alkyl or alkoxy and Hal represents halogen.
13. Compounds of the formula (XXIV) 112
14. Compounds of the formula 113in which R.sup.8 represents
alkyl.
15. Compounds of the formula 114
16. Pesticides or herbicides, characterized in that they contain a
compound of the formula (I) according to claim 1.
17. Use of compounds of the formula (I) according to claim 1 for
controlling pests and weeds.
18. Method for controlling pests and weeds, characterized in that
compounds of the formula (I) according to claim 1 are allowed to
act on pests or weeds and/or their habitat.
19. Process for preparing pesticides and herbicides, characterized
in that compounds of the formula (I) according to claim 1 are mixed
with extenders and/or surfactants.
Description
[0001] The invention relates to novel phenyl-substituted cyclic
ketoenols, to a plurality of processes and intermediates for their
preparation and to their use as pesticides and herbicides.
[0002] It is already known that certain phenyl-substituted cyclic
ketoenols are active as insecticides, acaricides and/or
herbicides.
[0003] 1H-arylpyrrolidine-dione derivatives (EP-A-456 063, EP-A-521
334, EP-A-596 298, EP-A-613 884, EP-A-613 885, DE 44 40 594, WO
94/01 997, WO 95/01 358, WO 95/20 572, EP-A-668 267, WO 95/26 954,
WO 96/25395 and WO 96/35 664) having insecticidal, acaricidal and
in some cases herbicidal activity are known.
[0004] It is known that certain substituted
.DELTA..sup.3-dihydrofuran-2-o- ne-derivatives have herbicidal
properties (cf. DE-A-4 014 420). The synthesis of the tetronic acid
derivatives (such as, for example,
3-(2-methyl-phenyl)-4-hydroxy-5-(4-fluorophenyl)-.DELTA..sup.3-dihydrofur-
an-(2)-one) used as starting materials is also described in DE-A-4
014 420. Compounds of a similar structure are known from the
publication Campbell et al., J. Chem. Soc., Perkin Trans. 1, 1985,
(8) 1567-76, without an insecticidal and/or acaricidal activity
being mentioned. Furthermore, 3-aryl-.DELTA..sup.3-dihydrofuranone
derivatives having herbicidal, acaricidal and insecticidal
properties are known from EP-A-528 156, EP-A-0 647 637, WO
96/25395, WO 96/20196 and the abovementioned hitherto undisclosed
patent application. 3-aryl-.DELTA..sup.3-dihydrothiophene-one
derivatives are also known (WO 95/26 345, WO 96/25395 and WO
96/35664).
[0005] However, the acaricidal and insecticidal activity and/or
spectrum of activity and/or plant tolerance of these compounds, in
particular with respect to crop plants, is not always
satisfactory.
[0006] The invention, accordingly, provides novel compounds of the
formula (I) 3
[0007] in which
[0008] V represents hydrogen, halogen, alkyl or alkoxy,
[0009] W represents hydrogen, cyano, nitro, halogen, alkyl,
alkenyl, alkinyl, alkoxy, halogenoalkyl, halogenoalkoxy or in each
case optionally substituted phenyl, phenoxy, phenylthio,
phenylalkoxy or phenylalkylthio,
[0010] X represents halogen, alkyl, alkenyl, alkinyl, alkoxy,
halogenoalkyl, halogenoalkoxy, cyano, nitro or in each case
optionally substituted phenyl, phenoxy, phenylthio, phenylalkyloxy
or phenylalkylthio,
[0011] Y represents hydrogen, halogen, alkyl, alkoxy,
halogenoalkyl, halogenoalkoxy, cyano or nitro,
[0012] Z represents hydrogen, halogen, alkyl, alkoxy,
halogenoalkyl, halogenoalkoxy, hydroxyl, cyano, nitro or in each
case optionally substituted phenoxy, phenylthio, 5- or 6-membered
hetaryloxy, 5- or 6-membered hetarylthio, phenylalkyloxy or
phenylalkylthio, or
[0013] Y and Z together with the linking carbon atoms represent an
optionally substituted cycle which is optionally interrupted by one
or more heteroatoms, or
[0014] W and Z together with the linking carbon atoms represent an
optionally substituted cycle which is optionally interrupted by one
or more heteroatoms,
[0015] Het represents one of the groups 4
[0016] in which
[0017] G represents hydrogen (a) or represents one of the groups
5
[0018] in which
[0019] E represents a metal ion equivalent or an ammonium ion,
[0020] L represents oxygen or sulphur,
[0021] M represents oxygen or sulphur,
[0022] R.sup.1 represents in each case optionally halogen- or
cyano-substituted alkyl, alkenyl, alkoxyalkyl, alkylthioalkyl or
polyalkoxyalkyl or represents in each case optionally halogen-,
alkyl- or alkoxy-substituted cycloalkyl or heterocyclyl or
represents in each case optionally substituted phenyl, phenylalkyl,
hetaryl, phenoxyalkyl or hetaryloxyalkyl,
[0023] R.sup.2 represents in each case optionally halogen- or
cyano-substituted alkyl, alkenyl, alkoxyalkyl or polyalkoxyalkyl or
represents in each case optionally substituted cycloalkyl, phenyl
or benzyl,
[0024] R.sup.3, R.sup.4 and R.sup.5 independently of one another
each represent in each case optionally halogen-substituted alkyl,
alkoxy, alkylamino, dialkylamino, alkylthio, alkenylthio or
cycloalkylthio or represent in each case optionally substituted
phenyl, benzyl, phenoxy or phenylthio,
[0025] R.sup.6 and R.sup.7 independently of one another each
represent hydrogen, represent in each case optionally halogen- or
cyano-substituted alkyl, cycloalkyl, alkenyl, alkoxy, alkoxyalkyl
or represent in each case optionally substituted phenyl or benzyl,
or together with the linking N atom form an optionally oxygen- or
sulphur-containing and optionally substituted cycle.
[0026] The compounds of the formula (I) can be present, depending,
inter alia, on the nature of the substituents, as optical isomers
or isomer mixtures of differing composition which, if appropriate,
can be separated in a customary manner. Both the pure isomers and
the isomer mixtures, their preparation and use, and compositions
comprising them are part of the subject matter of the present
invention. In the following, for simplicity, however, compounds of
the formula (I) are always referred to, although pure compounds
and, if appropriate, mixtures having different proportions of
isomeric compounds are intended.
[0027] Including the meanings (1) to (3) of the group Het, the
following principal structures (I-1) to (I-3) result: 6
[0028] in which
[0029] G, V, W, X, Y and Z are each as defined above.
[0030] Including the various meanings (a), (b), (c), (d), (e), (f)
and (g) of the group G, the following principal structures (I-1-a)
to (I-1-g) result if Het represents the group (1) 7
[0031] in which
[0032] E, L, M, V, W, X, Y, Z, R.sup.1, R.sup.2, R.sup.3, R.sup.4,
R.sup.5, R.sup.6 and R.sup.7 are each as defined above.
[0033] Including the various meanings (a), (b), (c), (d), (e), (f)
and (g) of the group G, the following principal structures (I-2-a)
to (I-2-g) result if Het represents the group (2) 8
[0034] in which
[0035] E, L, M, V, W, X, Y, Z, R.sup.1, R.sup.2, R.sup.3, R.sup.4,
R.sup.5, R.sup.6 and R.sup.7 are each as defined above.
[0036] Including the various meanings (a), (b), (c), (d), (e), (f)
and (g) of the group G, the following principal structures (I-3-a)
to (I-3-g) result if Het represents the group (3) 9
[0037] in which
[0038] E, L, M, V, W, X, Y, Z, R .sup.1, R.sup.2, R.sup.3, R.sup.4,
R.sup.5, R.sup.6 and R.sup.7 are each as defined above.
[0039] Furthermore, it has been found that the novel compounds of
the formula (I) are obtained by the processes described below:
[0040] (A) compounds of the formula (I-1-a) 10
[0041] in which
[0042] V, W, X, Y and Z are as defined above
[0043] are obtained when
[0044] compounds of the formula (II) 11
[0045] in which
[0046] V, W, X, Y and Z are each as defined above
[0047] and
[0048] R.sup.8 represents alkyl (preferably
C.sub.1-C.sub.6-alkyl)
[0049] are intramolecularly condensed in the presence of a diluent
and in the presence of a base.
[0050] (B) Moreover, it has been found that compounds of the
formula (I-2-a) 12
[0051] in which
[0052] V, W, X, Y and Z are each as defined above
[0053] are obtained when
[0054] compounds of the formula (III) 13
[0055] in which
[0056] V, W, X, Y, Z and R.sup.8 are each as defined above
[0057] are intramolecularly condensed in the presence of a diluent
and in the presence of a base.
[0058] (C) Furthermore, it has been found that compounds of the
formula (I-3-a) 14
[0059] in which
[0060] V, W, X, Y and Z are each as defined above
[0061] are obtained when
[0062] compounds of the formula (IV) 15
[0063] in which
[0064] V, W, X, Y, Z and R.sup.8 are each as defined above and
[0065] T represents hydrogen, halogen, alkyl (preferably
C.sub.1-C.sub.6-alkyl) or alkoxy (preferably
C.sub.1-C.sub.8-alkoxy)
[0066] are intramolecularly cyclized, if appropriate in the
presence of a diluent and in the presence of an acid.
[0067] Moreover, it has been found
[0068] (D) that the compounds of the formulae (I-1-b) to (I-3-b)
shown above in which R.sup.1, V, W, X, Y and Z are each as defined
above are obtained when compounds of the formulae (I-1-a) to
(I-3-a) shown above in which V, W, X, Y and Z are each as defined
above are in each case reacted
[0069] .alpha.) with acyl halides of the formula (V) 16
[0070] in which
[0071] R.sup.1 is as defined above and
[0072] Hal represents halogen (in particular chlorine or
bromine)
[0073] or
[0074] .beta.) with carboxylic anhydrides of the formula (VI)
R.sup.1--CO--O--CO--R.sup.1 (VI)
[0075] in which
[0076] R.sup.1 is as defined above,
[0077] if appropriate in the presence of a diluent and if
appropriate in the presence of an acid binder;
[0078] (E) that the compounds of the formulae (I-1-c) to (I-3-c)
shown above in which R.sup.2, V, W, M, X, Y and Z are each as
defined above and L represents oxygen are obtained when compounds
of the formulae (I-1-a) to (I-3-a) shown above in which V, W, X, Y
and Z are each as defined above are in each case reacted
[0079] with chloroformic esters or chloroformic thioesters of the
formula (VII)
R.sup.2--M--CO--Cl (VII)
[0080] in which
[0081] R.sup.2 and M are each as defined above,
[0082] if appropriate in the presence of a diluent and if
appropriate in the presence of an acid binder;
[0083] (F) that compounds of the formulae (I-1-c) to (I-3-c) shown
above in which R.sup.2, V, W, M, X, Y and Z are each as defined
above and L represents sulphur are obtained when compounds of the
formulae (I-1-a) to (I-3-a) shown above in which V, W, X, Y and Z
are each as defined above are in each case reacted
[0084] with chloromonothioformic esters or chlorodithioformic
esters of the formula (VIII) 17
[0085] in which
[0086] M and R.sup.2 are each as defined above,
[0087] if appropriate in the presence of a diluent and if
appropriate in the presence of an acid binder,
[0088] (G) that compounds of the formulae (I-1-d) to (I-3-d) shown
above in which R.sup.3, V, W, X, Y and Z are each as defined above
are obtained when compounds of the formulae (I-1-a) to (I-3-a)
shown above in which V, W, X, Y and Z are each as defined above are
in each case reacted
[0089] with sulphonyl chlorides of the formula (IX)
R.sup.3--SO.sub.2--Cl (IX)
[0090] in which
[0091] R.sup.3 is as defined above,
[0092] if appropriate in the presence of a diluent and if
appropriate in the presence of an acid binder,
[0093] (H) that compounds of the formulae (I-1-e) to (I-3-e) shown
above in which L, R.sup.4, R.sup.5, V, W, X, Y and Z are each as
defined above are obtained when compounds of the formulae (I-1-a)
to (I-3-a) shown above in which V, W, X, Y and Z are each as
defined above are in each case reacted
[0094] with phosphorus compounds of the formula (X) 18
[0095] in which
[0096] L, R.sup.4 and R.sup.5 are each as defined above and
[0097] Hal represents halogen (in particular chlorine or
bromine),
[0098] if appropriate in the presence of a diluent and if
appropriate in the presence of an acid binder,
[0099] (I) that compounds of the formulae (I-1-f) to (I-3-f) shown
above in which E, V, W, X, Y and Z are each as defined above are
obtained when compounds of the formulae (I-1-a) to (I-3-a) in which
V, W, X, Y and Z are each as defined above are in each case
reacted
[0100] with metal compounds or amines of the formuale (XI) or (XII)
19
[0101] in which
[0102] Me represents a mono- or divalent metal (preferably an
alkali metal or alkaline earth metal, such as lithium, sodium,
potassium, magnesium or calcium),
[0103] t represents the number 1 or 2 and
[0104] R.sup.10, R.sup.11, R.sup.12 independently of one another
each represent hydrogen or alkyl (preferably
C.sub.1-C.sub.8-alkyl),
[0105] if appropriate in the presence of a diluent,
[0106] (J) that compounds of the formulae (I-1-g) to (I-3-g) shown
above in which L, R.sup.6, R.sup.7, V, W, X, Y and Z are each as
defined above are obtained when compounds of the formulae (I-1-a)
to (I-3-a) shown above in which V, W, X, Y and Z are each as
defined above are in each case reacted
[0107] .alpha.) with isocyanates or isothiocyanates of the formula
(XIII)
R.sup.6--N.dbd.C.dbd.L (XIII)
[0108] in which
[0109] R.sup.6 and L are each as defined above,
[0110] if appropriate in the presence of a diluent and if
appropriate in the presence of a catalyst or
[0111] .beta.) with carbamoyl chlorides or thiocarbamoyl chlorides
of the formula (XIV) 20
[0112] in which
[0113] L, R.sup.6 and R.sup.7 are each as defined above,
[0114] if appropriate in the presence of a diluent and if
appropriate in the presence of an acid binder.
[0115] Furthermore, it has been found that the novel compounds of
the formula (I) have very good activity as pesticides, preferably
as insecticides, acaricides and herbicides, and that they are
additionally frequently very well tolerated by plants, in
particular by crop plants.
[0116] The formula (I) provides a general definition of the
compounds according to the invention. Preferred substituents and/or
ranges of the radicals listed in the formulae mentioned herein
above and herein below are illustrated below:
[0117] V preferably represents hydrogen, halogen,
C.sub.1-C.sub.6-alkyl or C.sub.1-C.sub.6-alkoxy,
[0118] W preferably represents hydrogen, nitro, cyano, halogen,
C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkenyl,
C.sub.2-C.sub.6-alkinyl, C.sub.1-C.sub.6-alkoxy,
C.sub.1-C.sub.4-halogenoalkyl, C.sub.1-C.sub.4-halogenoalkoxy or
preferably represents in each case optionally halogen-,
C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-alkoxy,
C.sub.1-C.sub.4-halogenoalkyl, C.sub.1-C.sub.4-halogenoalkoxy,
nitro- or cyano-substituted phenyl, phenoxy, phenylthio,
phenyl-C.sub.1-C.sub.4-alk- oxy or
phenyl-C.sub.1-C.sub.4-alkylthio,
[0119] X preferably represents halogen, C.sub.1-C.sub.6-alkyl,
C.sub.2-C.sub.6-alkenyl, C.sub.2-C.sub.6-alkinyl,
C.sub.1-C.sub.6-alkoxy, C.sub.1-C.sub.4-halogenoalkyl,
C.sub.1-C.sub.4-halogenoalkoxy, cyano, nitro or preferably
represents in each case optionally halogen, C.sub.1-C.sub.6-alkyl,
C.sub.1-C.sub.6-alkoxy, C.sub.1-C.sub.4-halogenoal- kyl,
C.sub.1-C.sub.4-halogenoalkoxy, nitro- or cyano-substituted phenyl,
phenoxy, phenylthio, phenyl-C.sub.1-C.sub.4-alkoxy or
phenyl-C.sub.1-C.sub.4-alkylthio.
[0120] Y preferably represents hydrogen, halogen,
C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-alkoxy,
C.sub.1-C.sub.4-halogenoalkyl, C.sub.1-C.sub.4-halogenoalkoxy,
cyano or nitro.
[0121] Z preferably represents hydrogen, halogen,
C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-alkoxy,
C.sub.1-C.sub.4-halogenoalkyl, C.sub.1-C.sub.4-halogenoalkoxy,
hydroxy, cyano, nitro or preferably represents in each case
optionally halogen, C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-alkoxy,
C.sub.1-C.sub.4-halogenoalkyl, C.sub.1-C.sub.4-halogenoalkoxy,
nitro- or cyano-substituted phenoxy, phenylthio, thiazolyloxy,
pyridinyloxy, pyrimidyloxy, pyrazolyloxy,
phenyl-C.sub.1-C.sub.4-alkyloxy or phenyl-C.sub.1-C.sub.4-alkylthio
or
[0122] Y and Z together with the linking carbon atoms preferably
represent in each case optionally halogen-, C.sub.1-C.sub.6-alkyl-,
C.sub.1-C.sub.6-alkoxy- or
C.sub.1-C.sub.4-halogenoalkyl-substituted
C.sub.3-C.sub.5-alkanediyl or C.sub.3-C.sub.5-alkenediyl in which
optionally one to three members may be replaced independently of
one another by oxygen, sulphur, nitrogen or a carbonyl group,
or
[0123] W and Z together with the linking carbon atoms preferably
represent in each case optionally halogen-, C.sub.1-C.sub.6-alkyl-,
C.sub.1-C.sub.6-alkoxy- or
C.sub.1-C.sub.4-halogenoalkyl-substituted
C.sub.3-C.sub.5-alkanediyl or C.sub.3-C.sub.5-alkenediyl in which
one to three members may be replaced independently of one another
by oxygen, sulphur, nitrogen or a carbonyl group.
[0124] Het preferably represents one of the groups 21
[0125] G preferably represents hydrogen (a) or preferably
represents one of the groups 22
[0126] (in particular represents (a), (b) or (c))
[0127] in which
[0128] E represents a metal ion equivalent or an ammonium ion,
[0129] L represents oxygen or sulphur and
[0130] M represents oxygen or sulphur.
[0131] R.sup.1 preferably represents in each case optionally
halogen- or cyano-substituted C.sub.1-C.sub.20-alkyl,
C.sub.2-C.sub.20-alkenyl,
C.sub.1-C.sub.8-alkoxy-C.sub.1-C.sub.8-alkyl,
C.sub.1-C.sub.8-alkylthio-C- .sub.1-C.sub.8-alkyl or
poly-C.sub.1-C.sub.8-alkoxy-C.sub.1-C.sub.8-alkyl or preferably
represents optionally halogen-, C.sub.1-C.sub.6-alkyl- or
C.sub.1-C.sub.6-alkoxy-substituted C.sub.3-C.sub.8-cycloalkyl in
which optionally one or two not directly adjacent methylene groups
are replaced by oxygen and/or sulphur,
[0132] preferably represents optionally halogen-, cyano-, nitro-,
C.sub.1-C.sub.6-alkyl-, C.sub.1-C.sub.6-alkoxy-,
C.sub.1-C.sub.6-halogeno- alkyl-, C.sub.1-C.sub.6-halogenoalkoxy-,
C.sub.1-C.sub.6-alkylthio-or
C.sub.1-C.sub.6-alkylsulfonyl-substituted phenyl,
[0133] preferably represents optionally halogen-, nitro-, cyano-,
C.sub.1-C.sub.6-alkyl-, C.sub.1-C.sub.6-alkoxy-,
C.sub.1-C.sub.6-halogeno- alkyl- or
C.sub.1-C.sub.6-halogenoalkoxy-substituted
phenyl-C.sub.1-C.sub.6-alkyl,
[0134] represents optionally halogen- or
C.sub.1-C.sub.6-alkyl-substituted 5- or 6-membered hetaryl having
one or two heteroatoms from the group consisting of oxygen, sulphur
and nitrogen, for example pyrazolyl, thiazolyl, pyridyl, primidyl,
furamyl or thienyl,
[0135] preferably represents optionally halogen- or
C.sub.1-C.sub.6-alkyl-substituted phenoxy-C.sub.1-C.sub.6-alkyl
or
[0136] preferably represents optionally halogen-, amino- or
C.sub.1-C.sub.6-alkyl-substituted 5-or 6-membered
hetaryloxy-C.sub.1-C.su- b.6-alkyl having one or two heteroatoms
from the group consisting of oxygen, sulphur and nitrogen, for
example pyridyloxy-C.sub.1-C.sub.6-alky- l,
pyrimidyl-C.sub.1-C.sub.6-alkyl or
thiazolyloxy-C.sub.1-C.sub.6-alkyl).
[0137] R.sup.2 preferably represents in each case optionally
halogen- or cyano-substituted C.sub.1-C.sub.20-alkyl,
C.sub.2-C.sub.20-alkenyl,
C.sub.1-C.sub.8-alkoxy-C.sub.2-C.sub.8-alkyl or
poly-C.sub.1-C.sub.8-alko- xy-C.sub.2-C.sub.8-alkyl,
[0138] preferably represents optionally halogen-,
C.sub.1-C.sub.6-alkyl- or C.sub.1-C.sub.6-alkoxy-substituted
C.sub.3-C.sub.8-cycloalkyl or
[0139] preferably represents in each case optionally halogen-,
cyano-, nitro-, C.sub.1-C.sub.6-alkyl-, C.sub.1-C.sub.6-alkoxy-,
C.sub.1-C.sub.6-halogenoalkyl- or
C.sub.1-C.sub.6-halogenoalkoxy-substitu- ted phenyl or benzyl.
[0140] R.sup.3 preferably represents optionally halogen-substituted
C.sub.1-C.sub.8-alkyl or preferably represents in each case
optionally halogen-, C.sub.1-C.sub.6-alkyl-,
C.sub.1-C.sub.6-alkoxy-, C.sub.1-C.sub.4-halogenoalkyl-,
C.sub.1-C.sub.4-halogenoalkoxy-, cyano- or nitro-substituted phenyl
or benzyl.
[0141] R.sup.4 and R.sup.5 independently of one another each
preferably represent in each case optionally halogen-substituted
C.sub.1-C.sub.8-alkyl, C.sub.1-C.sub.8-alkoxy,
C.sub.1-C.sub.8-alkylamino- , di-(C.sub.1-C.sub.8-alkyl)amino,
C.sub.1-C.sub.8-alkylthio or C.sub.3-C.sub.8-alkenylthio or
preferably represent in each case optionally halogen-, nitro-,
cyano-, C.sub.1-C.sub.4-alkoxy-, C.sub.1-C.sub.4-halogenoalkoxy-,
C.sub.1-C.sub.4-alkylthio-, C.sub.1-C.sub.4-halogenoalkylthio-,
C.sub.1-C.sub.4-alkyl- or C.sub.1-C.sub.4-halogenoalkyl-substituted
phenyl, phenoxy or phenylthio.
[0142] R.sup.6 and R.sup.7 independently of one another each
preferably represent hydrogen, preferably represent in each case
optionally halogen- or cyano-substituted C.sub.1-C.sub.8-alkyl,
C.sub.3-C.sub.8-cycloalkyl, C.sub.1-C.sub.8-alkoxy,
C.sub.3-C.sub.8-alkenyl or
C.sub.1-C.sub.8-alkoxy-C.sub.2-C.sub.8-alkyl, preferably represent
in each case optionally halogen-, C.sub.1-C.sub.8-alkyl-,
C.sub.1-C.sub.8-halogenoalkyl or C.sub.1-C.sub.8-alkoxy-substituted
phenyl or benzyl or together preferably represent an optionally
C.sub.1-C.sub.6-alkyl-substituted C.sub.3-C.sub.6-alkylene radical
in which optionally one methylene group is replaced by oxygen or
sulphur.
[0143] V particularly preferably represents hydrogen, fluorine,
chlorine, bromine, C.sub.1-C.sub.4-alkyl or
C.sub.1-C.sub.4-alkoxy.
[0144] W particularly preferably represents hydrogen, nitro, cyano,
fluorine, chlorine, bromine, C.sub.1-C.sub.4-alkyl,
C.sub.1-C.sub.4-alkoxy, C.sub.1-C.sub.2-halogenoalkyl,
C.sub.1-C.sub.2-halogenoalkoxy or particularly preferably
represents in each case optionally fluorine-, chlorine-, bromine-,
C.sub.1-C.sub.4-alkyl-, C.sub.1-C.sub.4-alkoxy-,
C.sub.1-C.sub.2-halogeno- alkyl-, C.sub.1-C.sub.2-halogenoalkoxy-,
nitro- or cyano-substituted phenyl, phenoxy or benzyloxy.
[0145] X particularly preferably represents fluorine, chlorine,
bromine, C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-alkoxy,
C.sub.1-C.sub.2-halogenoal- kyl, C.sub.1-C.sub.2-halogenoalkoxy,
cyano, nitro or particularly preferably represents in each case
optionally fluorine-, chlorine-, bromine-, C.sub.1-C.sub.4-alkyl-,
C.sub.1-C.sub.4-alkoxy-, C.sub.1-C.sub.2-halogenoalkyl-,
C.sub.1-C.sub.2-halogenoalkoxy-, nitro- or cyano-substituted
phenyl, phenoxy or benzyloxy.
[0146] Y particularly preferably represents hydrogen, fluorine,
chlorine, bromine, C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-alkoxy,
C.sub.1-C.sub.2-halogenoalkyl, C.sub.1-C.sub.2-halogenoalkoxy,
cyano or nitro.
[0147] Z particularly preferably represents hydrogen, fluorine,
chlorine, bromine, C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-alkoxy,
C.sub.1-C.sub.2-halogenoalkyl, C.sub.1-C.sub.2-halogenoalkoxy,
hydroxyl, cyano, nitro or particularly preferably represents in
each case optionally fluorine-, chlorine-, bromine-,
C.sub.1-C.sub.4-alkyl-, C.sub.1-C.sub.4-alkoxy-,
C.sub.1-C.sub.2-halogenoalkyl-, C.sub.1-C.sub.2-halogenoalkoxy-,
nitro- or cyano-substituted phenoxy or benzyloxy or
[0148] Y and Z together with the linking carbon atoms particularly
preferably represent in each case optionally fluorine-, chlorine-,
bromine-, C.sub.1-C.sub.4-alkyl-, C.sub.1-C.sub.4-alkoxy-or
C.sub.1-C.sub.2-halogenoalkyl-substituted
C.sub.3-C.sub.4-alkanediyl or C.sub.3-C.sub.4-alkenediyl in which
optionally one or two not directly adjacent members may be replaced
independently of one another by oxygen, sulphur or nitrogen, or
[0149] W and Z together with the linking carbon atoms particularly
preferably represent in each case optionally fluorine-, chlorine-,
bromine-, C.sub.1-C.sub.4-alkyl-, C.sub.1-C.sub.4-alkoxy-or
C.sub.1-C.sub.2-halogenoalkyl-substituted
C.sub.3-C.sub.4-alkanediyl or C.sub.3-C.sub.4-alkenediyl in which
one or two not directly adjacent members may be replaced
independently of one another by oxygen, sulphur or nitrogen.
[0150] Het particularly preferably represents one of the groups
23
[0151] G particularly preferably represents hydrogen (a) or
particularly preferably represents one of the groups 24
[0152] (in particular represents (a), (b) or (c))
[0153] in which
[0154] E represents a metal ion equivalent or an ammonium ion,
[0155] L represents oxygen or sulphur and
[0156] M represents oxygen or sulphur.
[0157] R.sup.1 particularly preferably represents in each case
optionally fluorine- or chlorine-substituted
C.sub.1-C.sub.16-alkyl, C.sub.2-C.sub.16-alkenyl,
C.sub.1-C.sub.6-alkoxy-C.sub.1-C.sub.6-alkyl,
C.sub.1-C.sub.6-alkylthio-C.sub.1-C.sub.6-alkyl or
poly-C.sub.1-C.sub.6-alkoxy-C.sub.1-C.sub.6-alkyl or particularly
preferably represents optionally fluorine-, chlorine-,
C.sub.1-C.sub.5-alkyl- or C.sub.1-C.sub.5-alkoxy-substituted
C.sub.3-C.sub.7-cycloalkyl in which optionally one or two not
directly adjacent methylene groups are replaced by oxgyen and/or
sulphur,
[0158] particularly preferably represents optionally fluorine-,
chlorine-, bromine-, cyano-, nitro-, C.sub.1-C.sub.4-alkyl-,
C.sub.1-C.sub.4-alkoxy-- , C.sub.1-C.sub.3-halogenoalkyl-,
C.sub.1-C.sub.3-halogenoalkoxy-, C.sub.1-C.sub.4-alkylthio- or
C.sub.1-C.sub.4-alkylsulphonyl-substituted phenyl,
[0159] particularly preferably represents optionally fluorine-,
chlorine-, bromine-, C.sub.1-C.sub.4-alkyl-,
C.sub.1-C.sub.4-alkoxy-, C.sub.1-C.sub.3-halogenoalkyl- or
C.sub.1-C.sub.3-halogenoalkoxy-substitu- ted
phenyl-C.sub.1-C.sub.4-alkyl,
[0160] particularly preferably represents in each case optionally
fluorine-, chlorine-, bromine- or C.sub.1-C.sub.4-alkyl-substituted
pyrazolyl, thiazolyl, pyridyl, pyrimidyl, furanyl or thienyl,
[0161] particularly preferably represents optionally fluorine-,
chlorine-, bromine- or C.sub.1-C.sub.4-alkyl-substituted
phenoxy-C.sub.1-C.sub.5-alk- yl or
[0162] particularly preferably represents in each case optionally
fluorine-, chlorine-, bromine-, amino- or
C.sub.1-C.sub.4-alkyl-substitut- ed
pyridyloxy-C.sub.1-C.sub.5-alkyl,
pyrimidyloxy-C.sub.1-C.sub.5-alkyl or
thiazolyloxy-C.sub.1-C.sub.5-alkyl.
[0163] R.sup.2 particularly preferably represents in each case
optionally fluorine- or chlorine-substituted
C.sub.1-C.sub.16-alkyl, C.sub.2-C.sub.16-alkenyl,
C.sub.1-C.sub.6-alkoxy-C.sub.2-C.sub.6-alkyl or
poly-C.sub.1-C.sub.6-alkoxy-C.sub.2-C.sub.6-alkyl,
[0164] particularly preferably represents optionally fluorine-,
chlorine-, C.sub.1-C.sub.4-alkyl-or
C.sub.1-C.sub.4-alkoxy-substituted C.sub.3-C.sub.7-cycloalkyl
or
[0165] particularly preferably represents in each case optionally
fluorine-, chlorine-, bromine-, cyano-, nitro-,
C.sub.1-C.sub.4-alkyl-, C.sub.1-C.sub.3-alkoxy-,
C.sub.1-C.sub.3-halogenoalkyl-or
C.sub.1-C.sub.3-halogenoalkoxy-substituted phenyl or benzyl.
[0166] R.sup.3 particularly preferably represents optionally
fluorine- or chlorine-substituted C.sub.1-C.sub.6-alkyl or
particularly preferably represents in each case optionally
fluorine-, chlorine-, bromine-, C.sub.1-C.sub.4-alkyl-,
C.sub.1-C.sub.4-alkoxy-, C.sub.1-C.sub.2-halogeno- alkoxy-,
C.sub.1-C.sub.2-halogenoalkyl-, cyano- or nitro-substituted phenyl
or benzyl.
[0167] R.sup.4 and R.sup.5 independently of one another each
particularly preferably represent in each case optionally fluorine-
or chlorine-substituted C.sub.1-C.sub.6-alkyl,
C.sub.1-C.sub.6-alkoxy, C.sub.1-C.sub.6-alkylamino,
di-(C.sub.1-C.sub.6-alkyl)amino, C.sub.1-C.sub.6-alkylthio or
C.sub.3-C.sub.4-alkenylthio or particularly preferably represent in
each case optionally fluorine-, chlorine-, bromine-, nitro-,
cyano-, C.sub.1-C.sub.3-alkoxy-, C.sub.1-C.sub.3-halogenoalkoxy-,
C.sub.1-C.sub.3-alkylthio-, C.sub.1-C.sub.3-halogenoalkylthio-,
C.sub.1-C.sub.3-alkyl or C.sub.1-C.sub.3-halogenoalkyl-substituted
phenyl, phenoxy or phenylthio.
[0168] R.sup.6 and R.sup.7 independently of one another each
particularly preferably represent hydrogen, particularly preferably
represent in each case optionally fluorine-, or
chlorine-substituted C.sub.1-C.sub.6-alkyl,
C.sub.3-C.sub.6-cycloalkyl, C.sub.1-C.sub.6-alkoxy,
C.sub.3-C.sub.6-alkenyl or
C.sub.1-C.sub.6-alkoxy-C.sub.2-C.sub.6-alkyl, particularly
preferably represent in each case optionally fluorine-, chlorine-,
bromine-, C.sub.1-C.sub.5-halogenoalkyl-, C.sub.1-C.sub.5-alkyl- or
C.sub.1-C.sub.5-alkoxy-substituted phenyl or benzyl, or together
particularly preferably represent an optionally
C.sub.1-C.sub.4-alkyl-substituted C.sub.3-C.sub.6-alkylene radical
in which optionally one methylene group is replaced by oxygen or
sulphur.
[0169] V very particularly preferably represents hydrogen,
fluorine, chlorine, bromine, methyl, ethyl, propyl, iso-propyl,
tert-butyl, methoxy, ethoxy, propoxy or isopropoxy.
[0170] W very particularly preferably represents hydrogen, nitro,
cyano, fluorine, chlorine, bromine, methyl, ethyl, propyl, n-butyl,
iso-propyl, iso-butyl, methoxy, ethoxy, propoxy, iso-propoxy,
trifluoromethyl, difluoromethoxy, trifluoromethoxy, phenyl or
benzyloxy.
[0171] X very particularly preferably represents fluorine,
chlorine, bromine, methyl, ethyl, propyl, butyl, iso-butyl,
iso-propyl, methoxy, ethoxy, propoxy, isopropoxy, trifluoromethyl,
trifluoromethoxy, difluoromethoxy, cyano, nitro, phenyl or
benzyloxy.
[0172] Y very particularly preferably represents hydrogen,
fluorine, chlorine, bromine, methyl, ethyl, propyl, iso-propyl,
n-butyl, iso-butyl, tert-butyl, methoxy, ethoxy, propoxy,
iso-propoxy, trifluoromethyl, trifluoromethoxy, difluoromethoxy,
cyano or nitro.
[0173] Z very particularly preferably represents hydrogen,
fluorine, chlorine, bromine, methyl, ethyl, propyl, butyl,
iso-butyl, iso-propyl, tert-butyl, methoxy, ethoxy, propoxy,
iso-propoxy, trifluoromethyl, trifluoromethoxy, difluoromethoxy,
cyano or nitro or
[0174] Y and Z together with the linking carbon atoms very
particularly preferably represent optionally fluorine-, chlorine-,
methyl-, ethyl-, propyl-, iso-propyl-, methoxy-, ethoxy-, propoxy-,
iso-propoxy- or trifluoromethyl-substituted
C.sub.3-C.sub.4-alkanediyl in which optionally two not directly
adjacent members are replaced by oxygen or
[0175] W and Z together with the linking carbon atoms very
particularly preferably represent optionally fluorine-, chlorine-,
methyl-, ethyl-, propyl-, iso-propyl-, methoxy-, ethoxy-, propoxy-,
iso-propoxy- or trifluoromethyl-substituted
C.sub.3-C.sub.4-alkanediyl in which optionally two not directly
adjacent members are replaced by oxygen.
[0176] Het very particularly preferably represents one of the
groups 25
[0177] G very particularly preferably represents hydrogen (a) or
very particularly preferably represents one of the groups 26
[0178] (in particular represents (a), (b) or (c))
[0179] in which
[0180] E represents a metal ion equivalent or an ammonium ion,
[0181] L represents oxygen or sulphur and
[0182] M represents oxygen or sulphur.
[0183] R.sup.1 very particularly preferably represents in each case
optionally chlorine- or fluorine-substituted
C.sub.1-C.sub.14-alkyl, C.sub.2-C.sub.14-alkenyl,
C.sub.1-C.sub.4-alkoxy-C.sub.1-C.sub.6-alkyl,
C.sub.1-C.sub.4-alkylthio-C.sub.1-C.sub.6-alkyl,
poly-C.sub.1-C.sub.4-alk- oxy-C.sub.1-C.sub.4-alkyl or very
particularly preferably represents optionally fluorine-, chlorine-,
methyl-, ethyl-, n-propyl-, i-propyl-, n-butyl-, i-butyl-,
tert-butyl-, methoxy-, ethoxy-, n-propoxy- or
iso-propoxy-substituted C.sub.3-C.sub.6-cycloalkyl, in which
optionally one or two not directly adjacent methylene groups are
replaced by oxygen and/or sulphur, <very particularly preferably
represents optionally fluorine-, chlorine-, bromine-, cyano-,
nitro-, methyl-, ethyl-, n-propyl-, i-propyl-, methoxy-, ethoxy-,
trifluoromethyl-, trifluoromethoxy-, methylthio-, ethylthio-,
methylsulphonyl- or ethylsulphonyl-substituted phenyl,
[0184] very particularly preferably represents optionally
fluorine-, chlorine-, bromine-, methyl-, ethyl-, n-propyl-,
i-propyl-, methoxy-, ethoxy-, trifluoromethyl- or
trifluoromethoxy-substituted benzyl,
[0185] very particularly preferably represents in each case
optionally fluorine-, chlorine-, bromine-, methyl- or
ethyl-substituted furanyl, thienyl or pyridyl,
[0186] very particularly preferably represents optionally
fluorine-, chlorine-, methyl-or ethyl-substituted
phenoxy-C.sub.1-C.sub.4-alkyl or
[0187] very particularly preferably represents in each case
optionally fluorine-, chlorine-, amino-, methyl- or
ethyl-substituted pyridyloxy-C.sub.1-C.sub.4-alkyl,
pyrimidyloxy-C.sub.1-C.sub.4-alkyl or
thiazolyloxy-C.sub.1-C.sub.4-alkyl.
[0188] R.sup.2 very particularly preferably represents in each case
optionally fluorine- or chlorine-substituted
C.sub.1-C.sub.14-alkyl, C.sub.2-C.sub.14-alkenyl,
C.sub.1-C.sub.4-alkoxy-C.sub.2-C.sub.6-alkyl or
poly-C.sub.1-C.sub.4-alkoxy-C.sub.2-C.sub.6-alkyl,
[0189] very particularly preferably represents optionally
fluorine-, chlorine-, methyl-, ethyl-, n-propyl, iso-propyl- or
methoxy-substituted C.sub.3-C.sub.6-cycloalkyl,
[0190] or very particularly preferably represents in each case
optionally fluorine-, chlorine-, cyano-, nitro-, methyl-, ethyl-,
n-propyl-, i-propyl-, methoxy-, ethoxy-, trifluoromethyl- or
trifluoromethoxy-substi- tuted phenyl or benzyl.
[0191] R.sup.3 very particularly preferably represents in each case
optionally fluorine- or chlorine-substituted methyl, ethyl, propyl,
iso-propyl, n-butyl, tert-butyl, or very particularly preferably
represents in each case optionally fluorine-, chlorine-, bromine-,
methyl-, ethyl-, iso-propyl-, tert-butyl-, methoxy-, ethoxy-,
iso-propoxy-, trifluoromethyl-, trifluoromethoxy-, cyano- or
nitro-substituted phenyl or benzyl.
[0192] R.sup.4 and R.sup.5 independently of one another each very
particularly preferably represent in each case optionally fluorine-
or chlorine-substituted C.sub.1-C.sub.4-alkyl,
C.sub.1-C.sub.4-alkoxy, C.sub.1-C.sub.4-alkylamino,
di-(C.sub.1-C.sub.4-alkyl)amino or C.sub.1-C.sub.4-alkylthio or
very particularly preferably represent in each case optionally
fluorine-, chlorine-, bromine-, nitro-, cyano-, methyl-, methoxy-,
trifluoromethyl- or trifluoromethoxy-substituted phenyl, phenoxy or
phenylthio.
[0193] R.sup.6 and R.sup.7 independently of one another very
particularly preferably represent hydrogen, very particularly
preferably represent in each case optionally fluorine- or
chlorine-substituted C.sub.1-C.sub.4-alkyl,
C.sub.3-C.sub.6-cycloalkyl, C.sub.1-C.sub.4-alkoxy,
C.sub.3-C.sub.4-alkenyl or
C.sub.1-C.sub.4-alkoxy-C.sub.2-C.sub.4-alkyl, very particularly
preferably represent in each case optionally fluorine-, chlorine-,
bromine-, methyl-, methoxy- or trifluoromethyl-substituted phenyl
or benzyl, or together
[0194] very particularly preferably represent an optionally methyl-
or ethyl-substituted C.sub.5-C.sub.6-alkylene radical in which
optionally one methylene group is replaced by oxygen or
sulphur.
[0195] The abovementioned general or preferred definitions of
radicals or illustrations can be combined with each other as
desired, that is to say combinations between the ranges and
preferred ranges in question are also possible. They apply both to
the end products and, correspondingly, to the starting materials
and intermediates.
[0196] Preference according to the invention is given to those
compounds of the formula (I) which contain a combination of the
definitions given above as being preferred (preferable).
[0197] Particular preference according to the invention is given to
those compounds of the formula (I) which contain a combination of
the definitions given above as being particularly preferred.
[0198] Very particular preference according to the invention is
given to those compounds of the formula (I) which contain a
combination of the definitions given above as being very
particularly preferred.
[0199] Saturated or unsaturated hydrocarbon radicals, such as alkyl
or alkenyl, may be, also in combination with heteroatoms such as,
for example, in alkoxy, in each case straight-chain or branched as
far as is possible.
[0200] Optionally substituted radicals may be mono- or
polysubstituted, it being possible for the substituents in the case
of polysubstitutions to be identical or different.
[0201] In addition to the compounds mentioned in the Preparation
Examples, the following compounds of the formula (I-1-a) may be
mentioned specifically:
1TABLE 1 (I-1-a) 27 V X W Y Z H Br H Cl H H Cl H Br H H Cl H Cl H H
Cl H F H H F H Cl H H Cl H OCH.sub.3 H H Cl H CH.sub.3 H H
OCH.sub.3 H Cl H H OCH.sub.3 H OCH.sub.3 H H CH.sub.3 H Cl H H
CH.sub.3 H F H H CH.sub.3 H OCH.sub.3 H H CH.sub.3 H
t-C.sub.4H.sub.9 H H CH.sub.3 H CH.sub.3 H H Cl Cl H H H Cl F H H H
Cl OCH.sub.3 H H H Cl CH.sub.3 H H H Cl OC.sub.2H.sub.5 H H H
OCH.sub.3 OCH.sub.3 H H H CH.sub.3 CH.sub.3 H H H Br CH.sub.3 Br H
H Cl Cl CH.sub.3 H H CH.sub.3 Br CH.sub.3 H H CH.sub.3 Cl CH.sub.3
H H CH.sub.3 OCHF.sub.2 CH.sub.3 H H CH.sub.3 OCH.sub.2CF.sub.3
CH.sub.3 H H CH.sub.3 OC.sub.2H.sub.5 CH.sub.3 H H CH.sub.3
OCH.sub.3 CH.sub.3 H H CH.sub.3 CH.sub.3 CH.sub.3 H H Br Br
CH.sub.3 H H Cl Cl CH.sub.3 H H C.sub.2H.sub.5 C.sub.2H.sub.5 Br H
H CH.sub.3 CH.sub.3 Br H H CH.sub.3 CH.sub.3 OCH.sub.3 H H Br Cl
CH.sub.3 H H Br CH.sub.3 Cl H H Cl CH.sub.3 Br H H C.sub.2H.sub.5
Br CH.sub.3 H H CH.sub.3 O--C.sub.3H.sub.7 CH.sub.3 H H CH.sub.3
O--Bz* CH.sub.3 H H CH.sub.3 CH.sub.3 Cl H H CH.sub.3 Ph* CH.sub.3
H H Cl H Cl Cl H CH.sub.3 H CH.sub.3 CH.sub.3 H CH.sub.3 H Cl
CH.sub.3 H Br H Cl CH.sub.3 H Br H CH.sub.3 CH.sub.3 H Cl H Br
CH.sub.3 H Cl H Cl CH.sub.3 H CH.sub.3 H Br CH.sub.3 H Cl H Cl F H
Cl H --O--CF.sub.2--O-- H Br H --(CH.sub.3).sub.3-- H Cl H CH.sub.3
Cl H CH.sub.3 H H H H Cl H H H H Br H H H H O--Bz H H H H CF.sub.3
H H H H OCH.sub.3 H H H H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3
CH.sub.3 CH.sub.3 H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H
CH.sub.3 H Br Br --(CH.sub.2).sub.3-- H CH.sub.3 CH.sub.3 CH.sub.3
F H CH.sub.3 CH.sub.3 CH.sub.3 Cl H CH.sub.3 CH.sub.3 CH.sub.3 Br H
CH.sub.3 CH.sub.3 H Cl H CH.sub.3 CH.sub.3 H Br H Cl Cl H Br
CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 *Bz = benzyl; Ph =
phenyl
[0202] In addition to the compounds mentioned in the Preparation
Examples, the following compounds of the formula (I-2-a) may be
mentioned specifically.
2TABLE 2 (I-2-a) 28
[0203] in which
[0204] V, W, X, Y and Z are each as defined in Table 1.
[0205] In addition to the compounds mentioned in the Preparation
Examples, the following compounds of the formula (I-3-a) may be
mentioned specifically.
3TABLE 3 (I-3-a) 29
[0206] in which
[0207] V, W, X, Y and Z are each as defined in Table 1.
[0208] Using according to process (A)
N-[(4-chloro-2,6-dimethyl)-phenylace-
tyl]-3-amino-3-carboxyethyl-tetrahydropyran as starting material,
the course of the process according to the invention can be
represented by the following equation: 30
[0209] Using according to process (B)
O-[(2-chloro-6-methyl)-phenylacetyl]-
-3-hydroxy-3-carboxyethyl-tetrahydropyran as starting material, the
course of the process according to the invention can be represented
by the following equation: 31
[0210] Using according to process (c) ethyl
2-[(2-chloro-4,6-dimethyl)-phe-
nyl]-4-(4-methoxy)-benzylmercapto-4,4-methyleneoxypropyl-3-oxo-valerate,
the course of the process according to the invention can be
represented by the following equation: 32
[0211] Using according to process (D.alpha.)
3-[(2-chloro-4-methyl)-phenyl-
]-5,5-methyleneoxypropyl-pyrrolidine-2,4-dione and pivaloyl
chloride as starting materials, the course of the process according
to the invention can be represented by the following equation:
33
[0212] Using according to process (D) (Variant .beta.)
3-[(2,4-dichloro)-phenyl]-4-hydroxy-5,5-methyleneoxypropyl-.DELTA..sup.3--
dihydrofuran-2-one and acetic anhydride as starting materials, the
course of the process according to the invention can be represented
by the following equation: 34
[0213] Using according to process (E)
8-[(2,4-dichloro)-phenyl]-5,5-methyl-
eneoxypropyl-pyrrolidine-2,4-dione and ethoxyethyl chloroformate as
starting materials, the course of the process according to the
invention can be represented by the following equation: 35
[0214] Using according to process (F)
3-[(2,6-dibromo-4-methyl)-phenyl]-4--
hydroxy-5,5-methyleneoxypropyl-.DELTA..sup.3-dihydrofuran-2-one and
methyl chloromonothioformate as starting materials, the course of
the reaction can be represented as follows: 36
[0215] Using according to process (G)
2-[(2,4,6-trimethyl)-phenyl]-5,5-met-
hyleneoxypropyl-pyrrolidine-2,4-dione and methanesulphonyl chloride
as starting material, the course of the reaction can be represented
by the following equation: 37
[0216] Using according to process (H)
2-[(4-bromo-2-chloro-6-methyl)-pheny-
l]-4-hydroxy-5,5-methyleneoxypropyl-.DELTA..sup.3-dihydrofuran-2-one
and (2,2,2-trifluoroethyl) methanethio-phosphonyl chloride as
starting materials, the course of the reaction can be represented
by the following equation: 38
[0217] Using according to process (I)
3-[(2,4-dichloro)-6-methylphenyl]-5,-
5-methyleneoxypropyl-pyrrolidine-2,4-dione and NaOH as components,
the course of the process according to the invention can be
represented by the following equation: 39
[0218] Using according to process (J) (variant .alpha.)
3-[(2-chloro-4-bromo-5-methyl)-phenyl]-4-hydroxy-5,5-methyleneoxypropyl-.-
DELTA..sup.3-dihydrofuran-2-one and ethylisocyanate as starting
materials, the course of the reaction can be represented by the
following equation: 40
[0219] Using according to process (J) (variant .beta.)
3-[(2-chloro-4,6-dimethyl)-phenyl]-5,5-methyleneoxypropyl-pyrrolidine-2,4-
-dione and dimethylcarbamidoyl chloride as starting materials, the
course of the reaction can be represented by the following
equation: 41
[0220] The compounds of the formula (II) required as starting
materials in the process (A) according to the invention 42
[0221] in which
[0222] V, W, X, Y, Z and R.sup.8 are each as defined above are
novel.
[0223] The acylamino acid esters of the formula (II) are obtained,
for example, when amino acid derivatives of the formula (XV) 43
[0224] in which
[0225] R.sup.8 is as defined above
[0226] are acylated with substituted phenylacetyl halides of the
formula (XVI) 44
[0227] in which
[0228] V, W, X, Y and Z are each as defined above and
[0229] Hal represents chlorine or bromine (Chem. Reviews 52,
237-416 (1953); Bhattacharya, Indian J. Chem. 6, 341-5, 1968),
[0230] or when acylamino acids of the formula (XVII) 45
[0231] in which
[0232] V, W, X, Y and Z are each as defined above are esterified
(Chem. Ind. (London) 1568 (1968)).
[0233] The compounds of the formula (XVII) 46
[0234] in which
[0235] V, W, X, Y and Z are each as defined above are novel.
[0236] Compounds of the formula (XVII) are obtained, for example,
when 3-amino-tetrahydropyran-3-carboxylic acid of the formula
(XVIII) 47
[0237] is acylated according to Schotten-Baumann (Organikum, VEB
Deutscher Verlag der Wissenschaften, Berlin 1977, p. 505) with
substituted phenylacetyl halides of the formula (XVI) 48
[0238] in which
[0239] V, W, X, Y and Z are each as defined above and
[0240] Hal represents chlorine or bromine.
[0241] Some of the compounds of the formula (XVI) are novel and can
be prepared by known processes (cf., for example, WO 97/02 243, WO
97/01 535 and DE-196 13 171).
[0242] The compounds of the formula (XVI) are obtained, for
example, by reacting substituted phenylacetic acids of the formula
(XIX) 49
[0243] in which
[0244] V, W, X, Y and Z are each as defined above
[0245] with halogenating agents (for example thionyl chloride,
thionyl bromide, oxalyl chloride, phosgene, phosphorus trichloride,
phosphorus tribromide or phosphorus pentachloride), if appropriate
in the presence of a diluent (for example optionally chlorinated
aliphatic or aromatic hydrocarbons such as toluene or methylene
chloride) at temperatures of from -20.degree. C. to 150.degree. C.,
preferably of from -10.degree. C. to 100.degree. C.
[0246] Some of the compounds of the formula (XIX) are novel, they
can be prepared by processes known from the literature (Organikum
15th edition, p. 533, VEB Deutscher Verlag der Wissenschaften,
Berlin 1977, cf., for example, WO 97/02 243, WO 07/01 535 and
DE-196 13 171). The compounds of the formula (XIX) are obtained,
for example, by hydrolyzing substituted phenylacetic acids of the
formula (XX) 50
[0247] in which
[0248] V, W, X, Y, Z and R.sup.8are each as defined above
[0249] in the presence of an acid (for example an inorganic acid
such as hydrochloric acid) or a base (for example an alkali metal
hydroxide such as sodium hydroxide or potassium hydroxide) and, if
appropriate, a diluent (for example an aqueous alcohol such as
methanol or ethanol) at temperatures between 0.degree. C. and
150.degree. C., preferably between 20.degree. C. and 100.degree.
C.
[0250] Some of the compounds of the formula (XX) are novel, they
can be prepared by processes known in principle.
[0251] The compounds of the formula (XX) are obtained, for example,
by reacting substituted 1,1,1-trichloro-2-phenylethanes of the
formula (XXI) 51
[0252] in which
[0253] V, W, X, Y and Z are each as defined above
[0254] initially with alkoxides (for example alkali metal alkoxides
such as sodium methoxide or sodium ethoxide) in the presence of a
diluent (for example of the alcohol derived from the alkoxide) at
temperatures between 0.degree. C. and 150.degree. C., preferably
between 20.degree. C. and 120.degree. C. and subsequently reacting
with an acid (preferably an inorganic acid, such as, for example,
sulphuric acid) at temperatures between -20.degree. C. and
150.degree. C., preferably between 0.degree. C. and 100.degree. C.,
(cf. DE-3 314 249).
[0255] Some of the compounds of the formula (XXI) are novel, they
can be prepared by processes known in principle.
[0256] The compounds of the formula (XXI) are obtained, for
example, when anilines of the formula (XXII) 52
[0257] in which
[0258] V, W, X, Y and Z are each as defined above
[0259] are reacted in the presence of an alkyl nitrite of the
formula (XXIII)
R.sup.13--ONO (XXIII)
[0260] in which
[0261] R.sup.13 represents alkyl, preferably
C.sub.1-C.sub.6-alkyl,
[0262] in the presence of copper (II) chloride and if appropriate
in the presence of a diluent (for example an aliphatic nitrile such
as acetonitrile) at a temperature of from -20.degree. C. to
80.degree. C., preferably from 0.degree. C. to 60.degree. C., with
vinylidene chloride (CH.sub.2.dbd.CCl.sub.2).
[0263] Some of the compounds of the formula (XXII) are known.
However, they can be prepared by processes known from the
literature, for example by reducing the corresponding nitro
compounds or by halogenating the anilines or acetanilines, followed
by recleavage.
[0264] The compounds of the formula (XXIII) are known compounds of
organic chemistry. Copper(II) chloride and vinylidene chloride have
been known for a long time and are commercially available.
[0265] The compounds of the formula (XV) and (XVIII) are novel.
They can be prepared by known processes (see, for example
Compagnon, Ann. Chim. (Paris) [14] 5, p. 11-22, 23-27 (1970), L.
Munday, J. Chem. Soc. 4372 (1961); J. T. Eward, C. Jitrangeri, Can.
J. Chem. 53, 3339 (1975).
[0266] Furthermore, the starting materials of the formula (II)
53
[0267] in which
[0268] V, W, X, Y, Z and R.sup.8 are each as defined above
[0269] used in the process (A) can be prepared when
3-amino-tetrahydropyran-3-carbonitrile of the formula (XXIV) 54
[0270] is reacted with substituted phenylacetiyl halides of the
formula (XVI) 55
[0271] in which
[0272] V, W, X, Y, Z and Hal are each as defined above
[0273] to give compounds of the formula (XXV) 56
[0274] in which
[0275] V, W, X, Y and Z are each as defined above
[0276] and these are subsequently subjected to acid
alcoholysis.
[0277] The compounds of the formula (XXV) are also novel. The
compounds of the formula (XXIV) are also novel (see Preparation
Example).
[0278] The compounds of the formula (III) 57
[0279] in which
[0280] V, W, X, Y, Z and R.sup.8 are each as defined above
[0281] required as starting materials in the process (B) according
to the invention are novel. They can be prepared in a simple manner
by methods known in principle.
[0282] The compounds of the formula (III) are obtained, for
example, when 3-hydroxy-tetrahydropyran-3-carboxylic esters of the
formula (XXVI) 58
[0283] in which
[0284] R.sup.8 is as defined above
[0285] are acylated with substituted phenylacetyl halides of the
formula (XVI) 59
[0286] in which
[0287] V, W, X, Y, Z and Hal are each as defined above
[0288] (Chem. Reviews 52, 237-416 (1953)).
[0289] The 3-hydroxy-tetrahydropyran-3-carboxylic esters of the
formula (XXVI) are novel. They are obtained, for example, by
alcoholizing 3-hydroxy-tetrahydropyran-3-carbonitrile of the
formula (XXVI-a) in the presence of acids, for example according to
Pinner (see Preparation Example). The cyanohydrin is obtained, for
example, by reacting tetrahydropyran-3-one with hydrocyanic
acid.
[0290] The compounds of the formula (IV) 60
[0291] in which
[0292] T, V, W, X, Y, Z and R.sup.8 are each as defined above
[0293] required as starting materials in the above process (C) are
novel.
[0294] They can be prepared by methods known in principle.
[0295] The compounds of the formula (IV) are obtained, for example,
when substituted phenylacetic esters of the formula (XX) 61
[0296] in which
[0297] V, W, X, Y, R.sup.8 and Z are each as defined above
[0298] are acylated with 2-benzylthio-carbonyl halides of the
formula (XXVII) 62
[0299] in which
[0300] T is as defined above and
[0301] Hal represents halogen (in particular chlorine or
bromine)
[0302] in the presence of strong bases (see, for example, M. S.
Chambers, E. J. Thomas, D. J. Williams, J. Chem. Soc. Chem.
Commun., (1987), 1228).
[0303] The benzylthio-carbonyl halides of the formula (XXVII) are
novel. They can be prepared by known processes (J. Antibiotics
(1983), 26, 1589).
[0304] The acyl halides of the formula (V), carboxylic anhydrides
of the formula (VI), chloroformic esters or chloroformic thioesters
of the formula (VII), chloromonothioformic esters or
chlorodithioformic esters of the formula (VIII), sulphonyl
chlorides of the formula (IX), phosphorus compounds of the formula
(X) and metal hydroxides, metal alkoxides or amines of the formula
(XI) and (XII) and isocyanates of the formula (XIII) and carbamoyl
chlorides of the formula (XIV) furthermore required as starting
materials for carrying out the processes (D), (E), (F), (G), (H),
(I) and (J) according to the invention are generally known
compounds of organic or inorganic chemistry.
[0305] The compounds of the formulae (XVI), (XIX), (XX), (XXI) and
(XXII) are furthermore known from the patent applications cited at
the outset and/or can be prepared by methods given therein (cf.
also WO 96/35 664, WO 97/01 535, WO 97/02 243 and DE-196 13
171).
[0306] The process (A) is characterized in that compounds of the
formula (II) in which V, W, X, Y, Z and R.sup.8 are each as defined
above are subjected to an intramolecular condensation in the
presence of a diluent and in the presence of a base.
[0307] Suitable diluents for use in the process (A) according to
the invention are all organic solvents which are inert towards the
reactants. Preference is given to using hydrocarbons, such as
toluene and xylene, furthermore ethers, such as dibutyl ether,
tetrahydrofuran, dioxane, glycol dimethyl ether and diglycol
dimethyl ether, moreover polar solvents, such as dimethyl
sulphoxide, sulpholane, dimethylformamide and N-methyl-pyrrolidone,
and also alcohols such as methanol, ethanol, propanol,
iso-propanol, butanol, iso-butanol and tert-butanol.
[0308] Suitable bases (deprotonating agents) for use in the
practice of the process (A) according to the invention are all
customary proton acceptors. Preference is given to using alkali
metal and alkaline earth metal oxides, hydroxides and carbonates,
such as sodium hydroxide, potassium hydroxide, magnesium oxide,
calcium oxide, sodium carbonate, potassium carbonate and calcium
carbonate, which may also be used in the presence of phase-transfer
catalysts, such as, for example, triethylbenzylammonium chloride,
tetrabutylammonium bromide, Adogen 464
(.dbd.methyltrialkyl(C.sub.8-C.sub.10)ammonium chloride) or TDA 1
(.dbd.tris-(methoxyethoxyethyl)-amine). It is also possible to use
alkali metals such as sodium or potassium. Furthermore, it is
possible to use alkali metal and alkaline earth metal amides and
hydrides, such as sodium amide, sodium hydride and calcium hydride,
and moreover also alkali metal alkoxides, such as sodium methoxide,
sodium ethoxide and potassium tert-butoxide.
[0309] When carrying out the process (A) according to the
invention, the reaction temperature can be varied within a
relatively wide range. In general, the reaction is carried out at
temperatures between -75.degree. C. and 200.degree. C., preferably
between -50.degree. C. and 150.degree. C.
[0310] The process (A) according to the invention is generally
carried out under atmospheric pressure.
[0311] When carrying out the process (A) according to the
invention, the reaction component of the formula (II) and the
deprotonating base are generally employed in equimolar to about
doubly-equimolar amounts. However, it is also possible to use one
component or the other in a relatively large excess (upto 3
mol).
[0312] The process (B) is characterized in that compounds of the
formula (III) in which V, W, X, Y, Z and R.sup.8 are each as
defined above are intramolecularly condensed in the presence of a
diluent and in the presence of a base.
[0313] Suitable diluents for use in the process (B) according to
the invention are all solvents which are inert towards the
reactants. Preference is given to using hydrocarbons, such as
toluene and xylene, furthermore ethers, such as dibutyl ether,
tetrahydrofuran, dioxane, glycol dimethyl ether and diglycol
dimethyl ether, moreover polar solvents, such as dimethyl
sulphoxide, sulpholane, dimethylformamide and N-methylpyrrolidone.
Furthermore, it is possible to use alcohols such as methanol,
ethanol, propanol, iso-propanol, butanol, iso-butanol and
tert-butanol.
[0314] Suitable bases (deprotonating agents) for use in the
practice of the process (B) according to the invention are all
customary proton acceptors. Preference is given to using alkali
metal and alkaline earth metal oxides, hydroxides and carbonates,
such as sodium hydroxide, potassium hydroxide, magnesium oxide,
calcium oxide, sodium carbonate, potassium carbonate and calcium
carbonate, which may also be used in the presence of phase-transfer
catalysts, such as, for example, triethylbenzylammonium chloride,
tetrabutylammonium bromide, Adogen 464
(.dbd.methyltrialkyl(C.sub.8-C.sub.10)ammonium chloride) or TDA 1
(.dbd.tris-(methoxyethoxyethyl)-amine). It is also possible to use
alkali metals such as sodium or potassium. Furthermore, it is
possible to use alkali metal and alkaline earth metal amides and
hydrides, such as sodium amide, sodium hydride and calcium hydride,
and moreover also alkali metal alkoxides, such as sodium methoxide,
sodium ethoxide and potassium tert-butoxide.
[0315] When carrying out the process (B) according to the
invention, the reaction temperature can be varied within a
relatively wide range. In general, the reaction is carried out at
temperatures between -75.degree. C. and 200.degree. C., preferably
between -50.degree. C. and 150.degree. C.
[0316] The process (B) according to the invention is generally
carried out under atmospheric pressure.
[0317] When carrying out the process (B) according to the
invention, the reaction components of the formula (III) and the
deprotonating bases are generally employed in approximately
equimolar amounts. However, it is also possible to use one
component or the other in a relatively large excess (upto 3
mol).
[0318] Process (C) is characterized in that compounds of the
formula (IV) in which T, V, W, X, Y, Z and R.sup.8 are each as
defined above are intramolecularly cyclized in the presence of an
acid and, if appropriate, in the presence of a diluent.
[0319] Suitable diluents for use in the process (C) according to
the invention are all organic solvents which are inert towards the
reactants. Preference is given to using hydrocarbons, such as
toluene and xylene, furthermore halogenated hydrocarbons, such as
dichloromethane, chloroform, ethylene chloride, chlorobenzene,
dichlorobenzene, moreover polar solvents, such as dimethyl
sulphoxide, sulpholane, dimethylformaide and N-methyl-pyrrolidone.
Furthermore, it is also possible to use alcohols such as, methanol,
ethanol, propanol, iso-propanol, butanol, iso-butanol,
tert-butanol.
[0320] If appropriate, the acid used can also serve as diluent.
[0321] Suitable acids for use in the process (C) according to the
invention are all customary inorganic and organic acids, such as,
for example, hydrohalic acids, sulphuric acid, alkyl-, aryl-, and
haloalkylsulphonic acids, and use is made in particular of
halogenated alkylcarboxylic acids, such as, for example,
trifluoroacetic acid.
[0322] When carrying out the process (C) according to the
invention, the reaction temperature can be varied within a
relatively wide range. In general, the reaction is carried out at
temperatures between 0.degree. C. and 250.degree. C., preferably
between 50.degree. C. and 150.degree. C.
[0323] The process (C) according to the invention is generally
carried out under atmospheric pressure.
[0324] When carrying out the process (C) according to the
invention, the reaction components of the formula (IV) and the acid
are employed, for example, in equimolar amounts. However, it is
also possible, if appropriate, to use catalytic amounts of the
acid.
[0325] The process (D.alpha.) is characterized in that compounds of
the formulae (I-1-a) to (I-3-a) are in each case reacted with
carbonyl halides of the formula (V), if appropriate in the presence
of a diluent and if appropriate in the presence of an acid
binder.
[0326] Suitable diluents for use in the process (D.alpha.)
according to the invention are all solvents which are inert towards
the acyl halides. Preference is given to using hydrocarbons, such
as benzine, benzene, toluene, xylene and tetraline, furthermore
halogenated hydrocarbons, such as methylene chloride, chloroform,
carbon tetrachloride, chlorobenzene and o-dichlorobenzene, moreover
ketones, such as acetone and methyl isopropyl ketone, furthermore
ethers, such as diethyl ether, tetrahydrofuran and dioxane,
additionally carboxylic esters, such as ethyl acetate, and also
strongly polar solvents, such as dimethylformamide, dimethyl
sulphoxide and sulpholane. The hydrolytic stability of the acyl
halide permitting, the reaction can also be carried out in the
presence of water.
[0327] Suitable acid binders for the reaction according to process
(D.alpha.) according to the invention are all customary acid
acceptors. Preference is given to using tertiary amines, such as
triethylamine, pyridine, diazabicyclooctane (DABCO),
diazabicycloundecene (DBU), diazabicyclononene (DBN), Hunig base
and N,N-dimethyl-aniline, furthermore alkaline earth metal oxides,
such as magnesium oxide and calcium oxide, and also alkali metal
and alkaline earth metal carbonates, such as sodium carbonate,
potassium carbonate and calcium carbonate and also alkalie metal
hydroxides such as sodium hydroxide and potassium hydroxide.
[0328] The reaction temperature of the process (D.alpha.) according
to the invention can be varied within a relatively wide range. In
general, the reaction is carried out at temperatures between
-20.degree. C. and +150.degree. C., preferably between 0.degree. C.
and 100.degree. C.
[0329] When carrying out the process (D.alpha.) according to the
invention, the starting materials of the formulae (I-1-a) to
(I-3-a) and the carbonyl halide of the formula (V) are generally
each employed in approximately equivalent amounts. However, it is
also possible to employ a relatively large excess (upto 5 mol) of
the carbonyl halide. Work-up is carried out by customary
methods.
[0330] The process (D.beta.) is characterized in that compounds of
the formulae (I-1-a) to (I-3-a) are each reacted with carboxylic
anhydrides of the formula (VI), if appropriate in the presence of a
diluent and if appropriate in the presence of an acid binder.
[0331] Suitable diluents for use in the process (D.beta.) according
to the invention are preferably those diluents which are also
preferred when acyl halides are used. Additionally, a carboxylic
anhydride employed in excess can also simultaneously act as
diluent.
[0332] The acid binders which are, if appropriated added in the
process (D.beta.) are preferably those acid binders which are also
preferred when acyl halides are used.
[0333] The reaction temperature in the process (D.beta.) according
to the invention can be varied within a relatively wide range. In
general, the reaction is carried out at temperatures between
-20.degree. C. and +150.degree. C., preferably between 0.degree. C.
and 100.degree. C.
[0334] When carrying out the process (D.beta.) according to the
invention, the starting materials of the formulae (I-1-a) to
(I-3-a) and the carboxylic anhydride of the formula (VI) are
generally each employed in approximately equivalent amounts.
However, it is also possible to employ a relatively large excess
(upto 5 mol) of carboxylic anhydride. Work-up is carried out by
customary methods.
[0335] In general, diluent and excess carboxylic anhydride and also
the carboxylic acid formed are removed by distillation or by
washing with an organic solvent or with water.
[0336] The process (E) is characterized in that compounds of the
formulae (I-1-a) to (I-3-a) are in each case reacted with
chloroformic esters or chloroformic thiol esters of the formula
(VII), if appropriate in the presence of a diluent and if
appropriate in the presence of an acid binder.
[0337] Acid binders which are suitable for the process (E)
according to the invention are all customary acid acceptors.
Preference is given to using tertiary amines, such as
triethylamine, pyridine, DABCO, DBU, DBN, Hunig base and
N,N-dimethyl-aniline, furthermore alkaline earth metal oxides, such
as magnesium oxide and calcium oxide, moreover alkali metal and
alkaline earth metal carbonates, such as sodium carbonate,
potassium carbonate and calcium carbonate, and also alkali metal
hydroxides such as sodium hydroxide and potassium hydroxide.
[0338] Suitable diluents for use in the process (E) according to
the invention are all solvents which are inert towards the
chloroformic esters or chloroformic thio esters. Preference is
given to using hydrocarbons, such as benzine, benzene, toluene,
xylene and tetralin, furthermore, halogenated hydrocarbons, such as
methylene chloride, chloroform, carbon tetrachloride, chlorobenzene
and o-dichlorobenzene, moreover ketones, such as acetone and methyl
ispropyl ketone, furthermore ethers, such as diethyl ether,
tetrahydrofuran and dioxane, additionally carboxylic esters, such
as ethyl acetate, moreover nitrites such as acetonitrile and also
strongly polar solvents, such as dimethylformamide, dimethyl
sulphoxide and sulpholane.
[0339] When carrying out the process (E) according to the
invention, the reaction temperature can be varied within a
relatively wide range. In general, the reaction temperature is
between -20.degree. C. and +100.degree. C., preferably between
0.degree. C. and 50.degree. C.
[0340] The process (E) according to the invention is generally
carried out under atmospheric pressure.
[0341] When carrying out the process (E) according to the
invention, the starting materials of the formulae (I-1-a) to
(I-3-a) and the appropriate chloroformic ester or chloroformic
thiol ester of the formula (VII) are generally each employed in
approximately equivalent amounts. However, it is also possible to
employ one component or the other in a relatively large excess (up
to 2 mol). Work-up is carried out by customary methods. In general,
precipitated salts are removed and the reaction mixture which
remains is concentrated by removing the diluent under reduced
pressure.
[0342] The process (F) according to the invention is characterized
in that compounds of the formulae (I-1-a) to (I-3-a) are in each
case reacted with compounds of the formula (VIII) in the presence
of a diluent and, if appropriate, in the presence of an acid
binder.
[0343] In the preparation process (F), approximately 1 mol of
chloromonothioformic ester or chlorodithioformic ester of formula
(VIII) per mole of starting material of the formulae (I-1-a) to
(I-3-a) is reacted at 0 to 120.degree. C., preferably at 20 to
60.degree. C.
[0344] Diluents which may be added, if appropriate, are all inert
polar organic solvents, such as ethers, amides, sulphones,
sulphoxides, and also halogenoalkanes.
[0345] Preference is given to using dimethyl sulphoxide,
tetrahydrofuran, dimethylformamide, ethyl acetate or methylene
chloride.
[0346] If, in a preferred embodiment, the enolate salt of the
compounds (I-1-a) to (I-3-a) is prepared by addition of strong
deprotonating agents such as, for example, sodium hydride or
potassium tert-butoxide, the addition of acid binders can be
dispensed with.
[0347] Suitable bases for use in the process (F) are all customary
proton acceptors. Preference is given to using alkali metal
hydrides, alkali metal alkoxides, alkali metal or alkaline earth
metal carbonates or bicarbonates or nitrogen bases. Examples
include sodium hydride, sodium methoxide, sodium hydroxide, calcium
hydroxide, potassium carbonate, sodium bicarbonate, triethylamine,
dibenzylamine, diisopropylamine, pyridine, quinoline,
diazabicyclooctane (DABCO), diazabicyclononene (DBN) and
diazabicycloundecene (DBU).
[0348] The reaction can be carried out under atmospheric pressure
or under elevated pressure and is preferably carried out under
atmospheric pressure. Work-up is carried out by customary
methods.
[0349] The process (G) according to the invention is characterized
in that compounds of the formulae (I-1-a) to (I-3-a) are in each
case reacted with sulphonyl chlorides of the formula (IX), if
appropriate in the presence of a diluent and if appropriate in the
presence of an acid binder.
[0350] In the preparation process (G), approximately 1 mol of
sulphonyl chloride of the formula (IX) per mole of starting
material of the formula (I-1-a) to (I-3-a) is reacted at -20 to
150.degree. C., preferably at 0 to 70.degree. C.
[0351] The process (G) is preferably carried out in the presence of
a diluent.
[0352] Suitable diluents are all inert polar organic solvents such
as ethers, amides, ketones, carboxylic esters, nitrites, sulphones,
sulphoxides or halogenated hydrocarbons such as methylene
chloride.
[0353] Preference is given to using dimethyl sulphoxide,
tetrahydrofuran, dimethylformamide, ethyl acetate, methylene
chloride.
[0354] If, in a preferred embodiment, the enolate salt of the
compounds (I-1-a) to (I-3-a) is prepared by addition of strong
deprotonating agents (such as, for example, sodium hydride or
potassium tert-butoxide), the addition of acid binders can be
dispensed with.
[0355] If acid binders are used, then customary inorganic or
organic bases are suitable, examples being sodium hydroxide, sodium
carbonate, potassium carbonate, pyridine and triethylamine.
[0356] The reaction can be carried out under atmospheric pressure
or under elevated pressure and is preferably carried out under
atmospheric pressure. Work-up is carried out by customary
methods.
[0357] The process (H) according to the invention is characterized
in that compounds of the formulae (I-1-a) to (I-3-a) are in each
case reacted with phosphorus compounds of the formula (X), if
appropriate in the presence of a diluent and if appropriate in the
presence of an acid binder.
[0358] In the preparation process (H), 1 to 2, preferably 1 to 1.3,
mol of the phosphorus compound of the formula (X) are reacted per
mole of the compounds (I-I-a) to (I-3-a), at temperatures between
-40.degree. C. and 150.degree. C., preferably between -10 and
110.degree. C., to obtain compounds of the formulae (I-1-e) to
(I-3-e).
[0359] The process (H) is preferably carried out in the presence of
a diluent.
[0360] Suitable diluents are all inert, polar organic solvents such
as ethers, carboxylic esters, halogenated hydrocarbons, ketones,
amides, nitrites, sulphones, sulphoxides, etc.
[0361] Preference is given to using acetonitrile, dimethyl
sulphoxide, tetrahydrofuran, dimethylformamide, methylene
chloride.
[0362] Acid binders which are added, if appropriate, are customary
inorganic or organic bases, such as hydroxides, carbonates or
amines. Examples include sodium hydroxide, sodium carbonate,
potassium carbonate, pyridine and triethylamine.
[0363] The reaction can be carried out under atmospheric pressure
or under elevated pressure and is preferably carried out under
atmospheric pressure. Work-up is carried out according to customary
methods of organic chemistry. The end products are preferably
purified by crystallization, chromatographic purification or by
so-called "encipient distillation", i.e. removal of the volatile
components under reduced pressure.
[0364] The process (I) is characterized in that compounds of the
formulae (I-1-a) to (I-3-a) are in each case reacted with metal
hydroxides or metal alkoxides of the formula (XI) or amines of the
formula (XII), if appropriate in the presence of a diluent.
[0365] Diluents which are preferred for use in the process (I)
according to the invention are ethers such as tetrahydrofuran,
dioxane, diethyl ether, or else alcohols such as methanol, ethanol,
isopropanol, but also water. The process (I) according to the
invention is generally carried out under atmospheric pressure. The
reaction temperature is generally between -20.degree. C. and
100.degree. C., preferably between 0.degree. C. and 50.degree.
C.
[0366] The process (J) according to the invention is characterized
in that compounds of the formulae (I-1-a) to (I-3-a) are in each
case reacted with (J.alpha.) compounds of the formula (XIII), if
appropriate in the presence of a diluent and if appropriate in the
presence of a catalyst, or (J.beta.) with compounds of the formula
(XIV), if appropriate in the presence of a diluent and if
appropriate in the presence of an acid binder.
[0367] In the preparation process (J.alpha.), approximately 1 mol
of isocyanate of the formula (XIII) is reacted per mole of starting
material of the formulae (I-1-a) to (I-3-a) at 0 to 100.degree. C.,
preferably at 20 to 50.degree. C.
[0368] The process (J.alpha.) is preferably carried out in the
presence of a diluent.
[0369] Suitable diluents are all inert organic solvents, such as
aromatic hydrocarbons, halogenated hydrocarbons, ethers, amides,
nitrites, sulphones or sulphoxides.
[0370] If appropriate, catalysts may be added to accelerate the
reaction. Catalysts which can be employed very advantageously are
organotin compounds, such as, for example, dibutyltin
dilaurate.
[0371] The process is preferably carried out under atmospheric
pressure.
[0372] In the preparation process (J.beta.), approximately 1 mol of
carbamoyl chloride of the formula (XIV) is reacted per mole of
starting material of the formulae (I-1-a) to (I-3-a) at 0 to
150.degree. C., preferably at 20 to 70.degree. C.
[0373] Diluents which may be added, if appropriate, are all inert
polar organic solvents such as ethers, carboxylic esters, nitrites,
ketones, amides, sulphones, sulphoxides or halogenated
hydrocarbons.
[0374] Preference is given to using dimethyl sulphoxide,
tetrahydrofuran, dimethylformamide or methylene chloride.
[0375] If, in a preferred embodiment, the enolate salt of the
compound (I-1-a) to (I-3-a) is prepared by addition of strong
deprotonating agents (such as, for example, sodium hydride or
potassium tert-butoxide), the addition of acid binders can be
dispensed with.
[0376] If acid binders are employed, then customary inorganic or
organic bases are suitable, examples including sodium hydroxide,
sodium carbonate, potassium carbonate, triethylamine or
pyridine.
[0377] The reaction can be carried out under atmospheric pressure
or under elevated pressure and is preferably carried out under
atmospheric pressure. Work-up is carried out by customary
methods.
[0378] The active compounds are suitable for controlling animal
pests, preferably arthropods and nematodes, in particular insects
and arachnida, which are encountered in agriculture, in forestry,
in the protection of stored products and of materials, and in the
hygiene field. They are active against normally sensitive and
resistant species and against all or some stages of development.
The abovementioned pests include:
[0379] From the order of Isopoda, for example, Oniscus asellus,
Armadillidium vulgare and Porcellio scaber.
[0380] From the order of the Diplopoda, for example, Blaniulus
guttulatus.
[0381] From the order of the Chilopoda, for example, Geophilus
carpophagus and Scutigera spec.
[0382] From the order of the Symphyla, for example, Scutigerella
immaculata.
[0383] From the order of the Thysanura, for example, Lepisma
saccharina.
[0384] From the order of the Collembola, for example, Onychiurus
armatus.
[0385] From the order of the Orthoptera, for example, Blatta
orientalis, Periplaneta americana, Leucophaea maderae, Blatella
germanica, Acheta domesticus, Gryllotalpa spp., Locusta migratoria
migratorioides, Melanoplus differentialis and Schistocerca
gregaria.
[0386] From the order of the Dermaptera, for example, Forficula
auricularia.
[0387] From the order of the Isoptera, for example, Reticulitermes
spp.
[0388] From the order of the Anoplura, for example, Phylloxera
vastatrix, Pemphigus spp., Pediculus humanus corporis, Haematopinus
spp. and Linognathus spp.
[0389] From the order of the Mallophaga, for example, Trichodectes
spp. and Damalinea From the order of the Thysanoptera, for example,
Frankliniella occidentalis, Hercinothrips femoralis, Thrips palmi
and Thrips tabaci.
[0390] From the order of the Heteroptera, for example, Eurygaster
spp., Dysdercus intermedius, Piesma quadrata, Cimex lectularius,
Rhodnius prolixus and Triatoma spp.
[0391] From the order of the Homoptera, for example, Aleurodes
brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis
gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Aphis fabae,
Doralis porni, Eriosoma lanigerum, Hyalopterus arundinis,
Macrosiphum avenae, Myzus spp., Phorodon humuli, Rhopalosiphum
padi. Empoasca spp., Euscelis bilobatus, Nephotettix cincticeps,
Lecanium comi, Saissetia oleae, Laodelphax striatellus, Nilaparvata
lugens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp.
and Psylla spp.
[0392] From the order of the Lepidoptera, for example, Pectinophora
gossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocoletis
blancardella, Hyponomeuta padella, Plutella maculipennis,
Malacosoma neustria, Euproctis chrysorrhoea, Lymantria spp,
Bucculatrix thurberiella, Phyllocnistis citrella, Agrotis spp.,
Buxoa spp., Feltia spp., Earias insulana, Heliothis spp.,
Spodoptera exigua, Mamestra brassicae, Panolis flammea, Prodenia
litura, Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella,
Pieris spp., Chilo spp., Pyrausta nubilalis, Ephestia kuehniella,
Galleria mellonella, Tineola bisselliella, Tinea pellionella,
Hofmannophila pseudospretella, Cacoecia podana, Capua reticulana,
Choristoneura fumiferana, Clysia ambiguella, Homona magnanima and
Tortrix viridana.
[0393] From the order of the Coleoptera, for example, Anobium
punctatum, Rhizopertha dominica, Acanthoscelides obtectus,
Acanthoscelides obtectus, Hylotrupes bajulus, Agelastica alni,
Leptinotarsa decemlineata, Phaedon cochleariae, Diabrotica spp.,
Psylliodes chrysocephala, Epilachna varive stis, Atomaria spp.,
Oryzaephilus surinamensis, Antho nomus spp., Sitophilus spp.,
Otiorrhynchus sulcatus,
[0394] Cosmopolites sordidus, Ceuthorrhynchus assimilis, Hypera
postica, Dermestes spp., Trogoderma spp., Anthrenus spp., Attagenus
spp., Lyctus spp., Meligethes aeneus, Ptinus spp., Niptus
hololeucus, Gibbium psylloides, Tribolium spp., Tenebrio molitor,
Agriotes spp., Cono derus spp., Melolontha melolontha, Amphimallon
solsti tialis and Costelytra zealandica.
[0395] From the order of the Hymenoptera, for example, Diprion
spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis and Vespa
spp.
[0396] From the order of the Diptera, for example, Aedes spp.,
Anopheles spp., Culex spp., Drosophila melanogaster, Musca spp.,
Fannia spp., Calliphora erythrocephala, Lucilia spp., Chrysomyia
spp., Cuterebra spp., Gastrophilus spp., Hyppobosca spp., Liriomyza
spp., Stomoxys spp., Oestrus spp., Hypoderma spp., Tabanus spp.,
Tannia spp., Bibio hortulanus, Oscinella frit, Phorbia spp.,
Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae and Tipula
paludosa.
[0397] From the order of the Siphonaptera, for example, Xenopsylla
cheopis and Ceratophyllus spp.
[0398] From the order of the Arachnida, for example, Scorpio maurus
and Latrodectus mactans.
[0399] From the order of the Acarina, for example, Acarus siro,
Argas spp., Ornithodoros spp., Dermanyssus gallinae, Eriophyes
ribis, Phyllocoptruta oleivora, Boophilus spp., Rhipicephalus spp.,
Amblyomma spp., Hyalomma spp., Ixodes spp., Psoroptes spp.,
Chorioptes spp., Sarcoptes spp., Tarsonemus spp., Bryobia
praetiosa, Panonychus spp. and Tetranychus spp.
[0400] The active compounds according to the invention have a high
insecticidal and acaricidal activity.
[0401] They can be used to particularly good effect for controlling
insects which are injurious to plants, such as, for example,
against the larvae of the mustard beetle (Phaedon cochleariae), or
against the larvae of the green rice leaf hopper (Nephotettix
cincticeps) and against the caterpillars of the cabbage moth
(Plutella maculipennis).
[0402] The active compounds according to the invention can
furthermore be used as defoliants, desiccants, haulm killers and,
especially, as weedkillers. By weeds, in the broadest sense, there
are to be understood all plants which grow in locations where they
are not wanted. Whether the substances according to the invention
act as total or selective herbicides depends essentially on the
amount used.
[0403] The doses of the active compounds according to the invention
necessary to control weeds are between 0.001 and 10 kg/ha,
preferably between 0.005 and 5 kg/ha.
[0404] The active compounds according to the invention can be used,
for example, in connection with the following plants:
[0405] Dicotyledonous weeds of the genera: Sinapis, Lepidium,
Galium, Stellaria, Matricaria, Anthemis, Galinsoga, Chenopodium,
Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus,
Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsium, Carduus, Sonchus,
Solanum, Rorippa, Rotola, Lindernia, Lamium, Veronica, Abutilon,
Emex, Datura, Viola, Galeopsis, Papaver, Centaurea, Trifolium,
Ranunculus and Taraxacum.
[0406] Dicotyledonous crops of the genera: Gossypium, Glycine,
Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia,
Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, Cucumis and
Cucurbita.
[0407] Monocotyledonous weeds of the genera: Echinochloa, Setaria,
Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria,
Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Cycnodon,
Monochoria, Fimbristylis, Sagittaria, Eleocharis, Scirpus,
Paspalum, Ischaemum, Sphenoclea, Dactyloctenium, Agrostis,
Alopecurus and Apera.
[0408] Monocotyledonous crops of the genera: Oryza, Zea, Triticum,
Hordeum, Avena, Secale, Sorghum, Panicum, Saccharum, Ananas,
Asparagus and Allium.
[0409] 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.
[0410] The compounds are suitable, depending on the concentration,
for the total control of weeds, for example on industrial terrain
and rail tracks, and on paths and squares with and without tree
plantings. Equally, the compounds can be employed for controlling
weeds in perennial crops, for example forests, decorative tree
plantings, orchards, vineyards, citrus groves, nut orchards, banana
plantations, coffee plantations, tea plantations, rubber
plantations, oil palm plantations, cocoa plantations, soft fruit
plantings and hopfields, in lawns, turf and pasture-land and for
the selective control of weeds in annual crops.
[0411] The active compounds according to the invention are
particularly suitable for the selective control of monocotyledonous
weeds in dicotyledonous crops, both pre-emergence and
post-emergence. In cotton and sugar beet, for example, they can be
employed very successfully for controlling weed grasses.
[0412] The active compounds can be converted into the customary
formulations, such as solutions, emulsions, wettable powders,
suspensions, powders, dusting agents, pastes, soluble powders,
granules, suspo-emulsion concentrates, natural and synthetic
materials impregnated with active compound, and very fine capsules
in polymeric substances.
[0413] These formulations are produced in a known manner, for
example by mixing the active compounds with extenders, that is
liquid solvents and/or solid carriers, optionally with the use of
surfactants, that is emulsifying agents and/or dispersing agents
and/or foam-forming agents.
[0414] If the extender used is water, it is also possible to use,
for example, organic solvents as auxiliary solvents. Essentially,
suitable liquid solvents include: aromatics, such as xylene,
toluene or alkylnaphthalenes, chlorinated aromatics and chlorinated
aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes of
methylene chloride, aliphatic hydrocarbons, such as cyclohexane or
paraffins, for example petroleum fractions, mineral and vegetable
oils, alcohols, such as butanol or glycol, and also their ethers
and esters, ketones, such as acetone, methyl ethyl ketone, methyl
isobutyl ketone or cyclohexanone, strongly polar solvents, such as
dimethylformamide and dimethyl sulphoxide, and also water.
[0415] Suitable solid carriers are:
[0416] for example ammonium salts and ground natural minerals, such
as kaolins, clays, talc, chalk, quartz, attapulgite,
montmorillonite or diatomaceous earth, and ground synthetic
minerals, such as highly disperse silica, alumina and silicates,
suitable solid carriers for granules are: for example crushed and
fractionated natural rocks such as calcite, marble, pumice,
sepiolite and dolomite, and also synthetic granules of inorganic
and organic meals, and granules of organic material such as
sawdust, coconut shells, maize cobs and tobacco stalks; suitable
emulsifying and/or foam-forming agents are: for example non-ionic
and anionic emulsifiers, such as polyoxyethylene fatty acid esters,
polyoxyethylene fatty alcohol ethers, for example alkylaryl
polyglycol ethers, alkylsulphonates, alkylsulphates,
arylsulphonates and also protein hydrolysates; suitable dispersing
agents are: for example lignin-sulphite waste liquors and
methylcellulose.
[0417] Tackifiers such as carboxymethylcellulose and natural and
synthetic polymers in the form of powders, granules or latices,
such as gum arabic, polyvinyl alcohol and polyvinyl acetate, as
well as natural phospholipids such as cephalins and lecithins, and
synthetic phospholipids, can be used in the formulations. Other
possible additives are mineral and vegetable oils.
[0418] It is possible to use colorants such as inorganic pigments,
for example iron oxide, titanium oxide and Prussian Blue, and
organic dyestuffs, such as alizarin dyestuffs, azo dyestuffs and
metal phthalocyanine dyestuffs, and trace nutrients such as salts
of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
[0419] The formulations in general contain between 0.1 and 95 per
cent by weight of active compound, preferably between 0.5 and 90%,
and additionally preferably extenders and surfactants.
[0420] The active compound according to the invention can be
present in its commercially available formulations and in the use
forms prepared from these formulations, as a mixture with other
active compounds, such as insecticides, attractants, sterilizing
agents, acaricides, nematicides, fungicides, growth-regulating
substances or herbicides. The insecticides include, for example,
phosphates, carbamates, carboxylates, chlorinated hydrocarbons,
phenylureas and substances produced by microorganisms.
[0421] Examples of particularly advantageous mixture components are
the following compounds:
[0422] Fungicides:
[0423] 2-aminobutane; 2-anilino-4-methyl-6-cyclopropyl-pyrimidine;
2',6'-dibromo-2-methyl-4'-trifluoromethoxy4'-trifluoro-methyl-1,3-thiazol-
e-5-carboxanilide;
2,6-dichloro-N-(4-trifluoromethylbenzyl)-benzamide;
(E)-2-methoxyimino-N-methyl-2-(2-phenoxyphenyl)-acetamide;
8-hydroxyquinoline sulphate; methyl
(E)-2-{2-[6-(2-cyanophenoxy)-pyrimidi-
n-4-yloxy]-phenyl}-3-methoxyacrylate; methyl
(E)-methox-imino-[alpha-(o-to- lyloxy)-o-tolyl]-acetate;
2-phenylphenol (OPP), aldimorph, ampropylfos, anilazine,
azaconazole,
[0424] benalaxyl, benodanil, benomyl, binapacryl, biphenyl,
bitertanol, blasticidin-S, bromuconazole, bupirimate,
buthiobate,
[0425] calcium polysulphide, captafol, captan, carbendazim,
carboxin, quinomethionate, chloroneb, chloropicrin, chlorothalonil,
chlozolinate, cufraneb, cymoxanil, cyproconazole, cyprofuram,
[0426] dichlorophen, diclobutrazol, diclofluanid, diclomezin,
dicloran, diethofencarb, difenoconazole, dimethirimol,
dimethomorph, diniconazole, dinocap, diphenylamine, dipyrithion,
ditalimfos, dithianon, dodine, drazoxolon,
[0427] edifenphos, epoxyconazole, ethirimol, etridiazole,
[0428] fenarimol, fenbuconazole, fenfuram, fenitropan, fenpiclonil,
fenpropidin, fenpropimorph, fentin acetate, fentin hydroxide,
ferbam, ferimzone, fluazinam, fludioxonil, fluoromide,
fluquinconazole, flusilazole, flusulphamide, flutolanil,
flutriafol, folpet, fosetyl-aluminium, fthalide, fuberidazole,
furalaxyl, furmecyclox, guazatine,
[0429] hexachlorobenzene, hexaconazole, hymexazol,
[0430] imazalil, imibenconazole, iminoctadine, iprobenfos (IBP),
iprodione, isoprothiolane, kasugamycin, copper preparations such
as: copper hydroxide, copper naphthenate, copper oxychloride,
copper sulphate, copper oxide, oxine-copper and Bordeaux
mixture,
[0431] mancopper, mancozeb, maneb, mepanipyrim, mepronil,
metalaxyl, metconazole, methasulphocarb, methfuroxam, metiram,
metsulphovax, myclobutanil,
[0432] nickel dimethyldithiocarbamate, nitrothal-isopropyl,
nuarimol,
[0433] ofurace, oxadixyl, oxamocarb, oxycarboxin,
[0434] pefurazoate, penconazole, pencycuron, phosdiphen, phthalide,
pimaricin, piperalin, polycarbamate, polyoxin, probenazole,
prochloraz, procymidone, propamocarb, propiconazole, propineb,
pyrazophos, pyrifenox, pyrimethanil, pyroquilon,
[0435] quintozene (PCNB),
[0436] sulphur and sulphur preparations,
[0437] tebucanozole, tecloftalam, tecnazene, tetraconazole,
thiabendazole, thicyofen, thiophanate-methyl, thiram,
tolclophos-methyl, tolylfluanid, triadimefon, triadimenol,
triazoxide, trichlamide, tricyclazole, tridemorph, triflumizole,
triforine, triticonazole,
[0438] validamycin A, vinclozolin,
[0439] zineb, ziram.
[0440] Bactericides:
[0441] bronopol, dichlorophen, nitrapyrin, nickel
dimethyldithiocarbamate, kasugamycin, octhilinone, furancarboxylic
acid, oxytetracyclin, probenazole, streptomycin, tecloftalam,
copper sulphate and other copper preparations.
[0442] Insecticides/Acaricides/Nematicides:
[0443] abamectin, AC 303 630, acephate, acrinathrin, alanycarb,
aldicarb, alphamethrin, amitraz, avennectin, AZ 60541,
azadirachtin, azinphos A, azinphos M, azocyclotin,
[0444] Bacillus thuringiensis, bendiocarb, benfuracarb, bensultap,
beta-cyluthrin, bifenthrin, BPMC, brofenprox, bromophos A,
bufencarb, buprofezin, butocarboxin, butylpyridaben,
[0445] cadusafos, carbaryl, carbofuran, carbophenothion,
carbosulphane, cartap, CGA 157 419, CGA 184699, chloethocarb,
chlorethoxyfos, chlorfenvinphos, chlorfluazuron, chlormephos,
chlorpyrifos, chlorpyrifos M, cis-resmethrin, clocythrin,
clofentezine, cyanophos, cycloprothrin, cyfluthrin, cyhalothrin,
cyhexatin, cypermethrin, cyromazine,
[0446] deltamethrin, demeton-M, demeton-S, demeton-S-methyl,
diafenthiuron, diazinon, dichlofenthion, dichlorvos, dicliphos,
dicrotophos, diethion, diflubenzuron, dimethoate, dimethylvinphos,
dioxathion, disulphoton,
[0447] edifenphos, emarnectin, esfenvalerate, ethiofencarb, ethion,
ethofenprox, ethoprophos, etrimphos,
[0448] fenarniphos, fenazaquin, fenbutatin oxide, fenitrothion,
fenobucarb, fenothiocarb, fenoxycarb, fenpropathrin, fenpyrad,
fenpyroximate, fenthion, fenvalerate, fipronil, fluazinam,
flucycloxuron, flucythrinate, flufenoxuron, flufenprox,
fluvalinate, fonophos, formothion, fosthiazate, fubfenprox,
furathiocarb,
[0449] HCH, heptenophos, hexaflumuron, hexythiazox,
[0450] imidacloprid, iprobenfos, isazophos, isofenphos, isoprocarb,
isoxathion, ivemectin, lambda-cyhalothrin, lufenuron,
[0451] malathion, mecarbam, mevinphos, mesulphenphos, metaldehyde,
methacrifos, methamidophos, methidathion, methiocarb, methomyl,
metolcarb, milbemectin, monocrotophos, moxidectin,
[0452] naled, NC 184, NI 25, nitenpyram,
[0453] omethoate, oxamyl, oxydemethon M, oxydeprofos,
[0454] parathion A, parathion M, permethrin, phenthoate, phorate,
phosalone, phosmet, phosphamidon, phoxim, pirimicarb, pirimiphos M,
primiphos A, profenofos, promecarb, propaphos, propoxur,
prothiofos, prothoate, pymetrozin, pyrachlophos, pyradaphenthion,
pyresmethrin, pyrethrum, pyridaben, pyrimidifen, pyriproxifen,
[0455] quinalphos,
[0456] RH 5992,
[0457] salithion, sebufos, silafluofen, sulphotep, sulprofos,
[0458] tebufenozid, tebufenpyrad, tebupirimiphos, teflubenzuron,
tefluthrin, temephos, terbam, terbufos, tetrachlorvinphos,
thiafenox, thiodicarb, thiofanox, thiomethon, thionazin,
thuringiensin, tralomethrin, triarathen, triazophos, triazuron,
trichlorfon, triflumuron, trimethacarb,
[0459] vamidothion, XMC, xylylcarb, YI 5301/5302, zetamethrin.
[0460] Herbicides:
[0461] 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, pretilachlor 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 methabenz-thiazuron;
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; sulphonylureas such
as, for example, amidosulphuron, bensulphuron-methyl,
chlorimuron-ethyl, chlorsulphuron, cinosulphuron,
metsulphuron-methyl, nicosulphuron, primisulphuron,
pyrazosulphuron-ethyl, thifensulphuron-methyl, triasulphuron and
tribenuron-methyl; thiocarbamates such as, for example, butylate,
cycloate, di-allate, EPTC, esprocarb, molinate, prosulphocarb,
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.
[0462] The active compound according to the invention can
furthermore be present in its commercially available formulations
and in the use forms prepared from these formulations, as a mixture
with synergistic agents. Synergistic agents are compounds which
increase the action of the active compounds without it being
necessary for the synergistic agent added to be active itself.
[0463] The active compound content of the use forms prepared from
the commercially available formulations can vary within wide
limits. The active compound concentration of the use forms can be
from 0.0000001 to 95% by weight of active compound, preferably
between 0.0001 and 1% by weight.
[0464] The compounds are employed in a customary manner appropriate
for the use forms.
[0465] When used against hygiene pests and pests of stored
products, the active compound has excellent residual action on wood
and clay and also a good stability to alkali on limed
substrates.
[0466] The active compounds according to the invention are not only
active against plant, hygiene and stored-product pests, but also,
in the veterinary medicine sector, against animal parasites
(ectoparasites), such as ixodid ticks, argasid ticks, scab mites,
trombiculid mites, flies (stinging and sucking), parasitic fly
larvae, lice, hair lice, bird lice and fleas. These parasites
include:
[0467] From the order of the Anoplurida, for example, Haematopinus
spp., Linognathus spp., Pediculus spp., Phtirus spp., Solenopotes
spp.
[0468] From the order of the Mallophagida and the sub-orders
Amblycerina and Ischnocerina, for example, Trimenopon spp., Menopon
spp., Trinoton spp., Bovicola spp., Werneckiella spp., Lepikentron
spp., Damalina spp., Trichodectes spp., Felicola
[0469] From the order Diptera and the sub-orders Nematocerina and
Brachycerina, for example, Aedes spp., Anopheles spp., Culex spp.,
Simulium spp., Eusimulium spp., Phlebotomus spp., Lutzomyia spp.,
Culicoides spp., Chrysops spp., Hybomitra spp., Atylotus spp.,
Tabanus spp., Haematopota spp., Philipomyia spp., Braula spp.,
Musca spp., Hydrotaea spp., Stomoxys spp., Haematobia spp.,
Morellia spp., Fannia spp., Glossina spp., Calliphora spp., Lucilia
spp., Chrysomyia spp., Wohlfahrtia spp., Sarcophaga spp., Oestrus
spp., Hypoderma spp., Gasterophilus spp., Hippobosca spp.,
Lipoptena spp. and Melophagus spp.
[0470] From the order of the Siphonapterida, for example, Pulex
spp., Ctenocephalides spp., Xenopsylla spp. and Ceratophyllus
spp.
[0471] From the order of the Heteropterida, for example, Cimex
spp., Triatoma spp., Rhodnius spp. and Panstrongylus spp.
[0472] From the order of the Blattarida, for example, Blatta
orientalis, Periplaneta americana, Blattela germanica and Supella
spp.
[0473] From the sub-class of the Acaria (Acarida) and the orders of
the Meta- and Mesostigmata, for example Argas spp., Ornithodorus
spp., Otabius spp., Ixodes spp., Amblyomma spp., Boophilus spp.,
Dermacentor spp., Haemaphysalis spp., Hyalomma spp., Rhipicephalus
spp., Dermanyssus spp., Raillietia spp., Pneumonyssus spp.,
Sternostoma spp. and Varroa spp.
[0474] From the order of the Actinedida (Prostigmata) and Acaridida
(Astigmata), for example Acarapis spp., Cheyletiella spp.,
Ornithocheyletia spp., Myobia spp., Psorergates spp., Demodex spp.,
Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp.,
Caloglyphus spp., Hypodectes spp., Pterolichus spp., Psoroptes
spp., Chorioptes spp., Octodectes spp., Sarcoptes spp., Notoedres
spp., Knemidocoptes spp., Cytodites spp. and Laminosioptes spp.
[0475] The active compounds of the formula (I) according to the
invention are also suitable for controlling arthropods which attack
agricultural livestock, such as, for example, cattle, sheep, goats,
horses, pigs, donkeys, camels, buffalo, rabbits, chickens, turkeys,
ducks, geese, honey bees, other domestic animals, such as, for
example, dogs, cats, cage birds, aquarium fish, and so-called
experimental animals such as, for example, hamsters, guinea-pigs,
rats and mice. By controlling these arthropods, it is intended to
reduce mortality and decreased performance (in meat, milk, wool,
hides, eggs, honey and the like), so that more economical and
simpler animal keeping is made possible by using the active
compounds according to the invention.
[0476] In the veterinary sector, the active compounds according to
the invention are used in a known manner by enteral administration,
for example in the form of tablets, capsules, drinks, drenches,
granules, pastes, boluscs, the feed-through method, suppositories,
by parenteral administration, such as, for example, by means of
injections (intramuscular, subcutaneous, intravenous,
intraperitoneal and the like), implants, by nasal application, by
dermal administration, for example in the form of dipping or
bathing, spraying, pouring-on and spotting-on, washing, dusting,
and with the aid of shaped articles which comprise active compound,
such as collars, ear tags, tail marks, limb bands, halters, marking
devices and the like.
[0477] When administered to livestock, poultry, domestic animals
and the like, the active compounds of the formula (I) can be used
as formulations (for example powders, emulsions, flowables) which
comprise the active compounds in an amount of 1 to 80% by weight,
either directly or after dilution by a factor of 100 to 10,000, or
they may be used in the form of a chemical bath.
[0478] Furthermore, it has been found that the compounds of the
formula (I) according to the invention have a potent insecticidal
action against insects which destroy industrial materials.
[0479] The following insects may be mentioned by way of example and
as being preferred, but without any limitation:
[0480] Beetles, such as
[0481] Hylotrupes bajulus, Chlorophorus pilosis, Anobium punctatum,
Xestobium rufovillosum, Ptilinus pecticornis, Dendrobium pertinex,
Ernobius mollis, Priobium carpini, Lyctus brunneus, Lyctus
africanus, Lyctus planicollis, Lyctus linearis, Lyctus pubescens,
Trogoxylon aequale, Minthes rugicollis, Xyleborus spec.,
Tryptodendron spec., Apate monachus, Bostrychus capucins,
Heterobostrychus brunneus, Sinoxylon spec., Dinoderus minutus.
[0482] Dermapterans, such as
[0483] Sirex juvencus, Urocerus gigas, Urocerus gigas taignus,
Urocerus augur.
[0484] Termites, such as
[0485] Kalotermes flavicollis, Cryptotermes brevis, Heterotermes
indicola, Reticulitermes flavipes, Reticulitermes santonensis,
Reticulitermes lucifugus, Mastotermes darwiniensis, Zootermopsis
nevadensis, Coptotermes formosanus.
[0486] Bristletails, such as
[0487] Lepisma saccharina.
[0488] Industrial materials are to be understood as meaning, in the
present context, non-live materials such as, preferably, synthetic
materials, glues, sizes, paper and board, leather, wood and timber
products, and paint.
[0489] The materials to be very particularly preferably protected
against attack by insects are wood and timber products.
[0490] Wood and timber products which can be protected by the
composition according to the invention or mixtures comprising such
a composition are to be understood as meaning, for example:
construction timber, wooden beams, railway sleepers, bridge
components, jetties, wooden vehicles, boxes, pallets, containers,
telephone poles, wood lagging, windows and doors made of wood,
plywood, particle board, joiner's articles, or wood products which,
quite generally, are used in the construction of houses or in
joinery.
[0491] The active compounds can be used as such, in the form of
concentrates or generally customary formulations, such as powders,
granules, solutions, suspensions, emulsions or pastes.
[0492] The formulations mentioned can be prepared in a manner known
per se, for example by mixing the active compounds with at least
one solvent or diluent, emulsifier, dispersant and/or binder or
fixative, water repellent, if appropriate desiccants and UV
stabilizers and, if appropriate, colorants and pigments and other
processing auxiliaries.
[0493] The insecticidal compositions or concentrates used for the
protection of wood and wooden materials comprise the active
compound according to the invention at a concentration of 0.0001 to
95% by weight, in particular 0.001 to 60% by weight.
[0494] The amount of the compositions or concentrates employed
depends on the species and the occurrence of the insects and on the
medium. The optimum rate of application can be determined upon use
in each case by test series. However, in general, it suffices to
employ 0.0001 to 20% by weight, preferably 0.001 to 10% by weight,
of the active compound, based on the material to be protected.
[0495] The solvent and/or diluent used is an organochemical solvent
or solvent mixture and/or an oily or oil-type organochemical
solvent or solvent mixture of low volatility and/or a polar
organochemical solvent or solvent mixture and/or water and, if
appropriate, an emulsifier and/or wetting agent.
[0496] Organochemical solvents which are preferably employed are
oily or oil-type solvents having an evaporation number of above 35
and a flashpoint of above 30.degree. C., preferably above
45.degree. C. Substances which are used as such oily and oil-type
solvents which have low volatility and are insoluble in water are
suitable mineral oils or their aromatic fractions, or
mineral-oil-containing solvent mixtures, preferably white spirit,
petroleum and/or alkylbenzene.
[0497] Substances which are advantageously used are mineral oils
with a boiling range of 170 to 220.degree. C., white spirit with a
boiling range of 170 to 220.degree. C., spindle oil with a boiling
range of 250 to 350.degree. C., petroleum or aromatics of boiling
range 160 to 280.degree. C., essence of turpentine and the
like.
[0498] In a preferred embodiment, liquid aliphatic hydrocarbons
with a boiling range of 180 to 210.degree. C. or high-boiling
mixtures of aromatic and aliphatic hydrocarbons with a boiling
range of 180 to 220.degree. C. and/or spindle oil and/or
monochloronaphthalene, preferably .alpha.-monochloronaphthalene,
are used.
[0499] The organic oily or oil-type solvents of low volatility
having an evaporation number of above 35 and a flashpoint of above
30.degree. C., preferably above 45.degree. C., can be partially
replaced by organochemical solvents of high or medium volatility,
with the proviso that the solvent mixture also has an evaporation
number of above 35 and a flashpoint of above 30.degree. C.,
preferably above 45.degree. C., and that the insecticide/fungicide
mixture is soluble or emulsifiable in this solvent mixture.
[0500] In a preferred embodiment, part of the organochemical
solvent or solvent mixture is replaced by an aliphatic polar
organochemical solvent or solvent mixture. Substances which are
preferably used are aliphatic organochemical solvents having
hydroxyl and/or ester and/or ether groups, such as, for example,
glycol ether, esters and the like.
[0501] The organochemical binders used within the scope of the
present invention are the synthetic resins and/or binding drying
oils which are known per se and can be diluted with water and/or
are soluble or dispersible or emulsifiable in the organochemical
solvents employed, in particular binders composed of, or
comprising, an acrylate resin, a vinyl resin, for example polyvinyl
acetate, polyester resin, polycondensation or polyaddition resin,
polyurethane resin, alkyd resin or modified alkyd resin, phenol
resin, hydrocarbon resin, such as indene/coumarone resin, silicone
resin, drying vegetable and/or drying oils and/or physically drying
binders based on a natural and/or synthetic resin.
[0502] The synthetic resin used as the binder can be employed in
the form of an emulsion, dispersion or solution. Up to 10% by
weight of bitumen or bituminous substances can also be used as
binders. In addition, colorants, pigments, water repellents,
odour-masking substances and inhibitors or anticorrosives known per
se and the like can also be employed.
[0503] The composition or the concentrate preferably comprises, in
accordance with the invention, at least one alkyd resin or modified
alkyd resin and/or a drying vegetable oil as the organochemical
binder. Preferably used according to the invention are alkyd resins
with an oil content of over 45% by weight, preferably 50 to 68% by
weight.
[0504] All or some of the abovementioned binder can be replaced by
a fixative (mixture) or a plasticizer (mixture). These additives
are intended to prevent volatilization of the active compounds and
crystallization or precipitation. They preferably replace 0.01 to
30% of the binder (based on 100% of binder employed).
[0505] The plasticizers are from the chemical classes of the
phthalic esters, such as dibutyl phthalate, dioctyl phthalate or
benzylbutyl phthalate, the phosphoric esters, such as tributyl
phosphate, the adipic esters, such as di-(2-ethylhexyl) adipate,
the stearates, such as butyl stearate or amyl stearate, the
oleates, such as butyl oleate, the glycerol ethers or relatively
high-molecular-weight glycol ethers, glycerol esters and
p-toluene-sulphonic esters.
[0506] Fixatives are chemically based on polyvinyl alkyl ethers,
such as, for example, polyvinyl methyl ether, or ketones, such as
benzophenone or ethylene benzophenone.
[0507] Particularly suitable as a solvent or diluent is also water,
if appropriate as a mixture with one or more of the abovementioned
organochemical solvents or diluents, emulsifiers and
dispersants.
[0508] Particularly effective protection of wood is achieved by
large-scale industrial impregnation processes, for example vacuum,
double-vacuum or pressure processes.
[0509] If appropriate, the ready-to-use compositions can
additionally comprise other insecticides and, if appropriate,
additionally one or more fungicides.
[0510] Suitable additional components which may be admixed are,
preferably, the insecticides and fungicides mentioned in WO 94/29
268. The compounds mentioned in that document are expressly part of
the present application.
[0511] Very particularly preferred components which may be admixed
are insecticides, such as chlorpyriphos, phoxim, silafluofin,
alphamethrin, cyfluthrin, cypermethrin, deltamethrin, permethrin,
imidacloprid, NI-25, flufenoxuron, hexaflumuron and triflumuron,
and fungicides, such as epoxyconazole, hexaconazole, azaconazole,
propiconazole, tebuconazole, cyproconazole, metconazole, imazalil,
dichlorofluanide, tolylfluanide, 3-iodo-2-propinylbutyl carbamate,
N-octyl-isothiazolin-3-one and
4,5-dichloro-N-octylisothiazolin-3-one.
[0512] The preparation and the use of the active compounds
according to the invention can be seen from the examples below.
Examples
Example I-1-a-1
[0513] 63
[0514] At reflux temperature, 17.3 g of the compound of Example II
-1 in 160 ml of absolute toluene are added dropwise to 14.05 g
(0.125 mol) of potassium tert-butoxide in 54 ml of absolute
tetrahydrofuran (THF), and the mixture is stirred at this
temperature for another 1.5 hours. After cooling, 160 ml of water
are added, the phases are separated, the toluene phase is extracted
with 80 ml of water and the combined aqueous phases are acidified
with concentrated HCL at from 0 to 20.degree. C. The product is
filtered off with suction, washed, dried and then, for further
purification, stirred with methyl tert-butyl(MTB)ether/N-hexane,
filtered off with suction and dried. Yield: 12.1 g (77% of theory),
m.p.: 200.degree. C.
[0515] Similarly, and/or according to the general preparation
procedures, the following compounds of the formula (I-1-a) are
obtained:
4TABLE 4 (I-1-a) 64 Ex. No. V W X Y Z m.p. .degree. C. I-1-a-2 H
CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 219 I-1-a-3 H CH.sub.3 CH.sub.3
Br H >220 I-1-a-4 H H CH.sub.3 CH.sub.3 H 226 I-1-a-5 H H Cl Cl
H >220 I-1-a-6 H H CH.sub.3 CH.sub.3 CH.sub.3 130 I-1-a-7 H H
CH.sub.3 H CH.sub.3 187 I-1-a-8 H Br Cl CH.sub.3 H >220 I-1-a-9
H H CH.sub.3 Br CH.sub.3 >220 I-1-a-10 H Cl CH.sub.3 Cl H
>220 I-1-a-11 H H Br CH.sub.3 CH.sub.3 145 I-1-a-12 H CH.sub.3
CH.sub.3 H Br 194 I-1-a-13 H CH.sub.3 CH.sub.3 CH.sub.3 Br
Example (I-1-b-1)
[0516] 65
[0517] Under reflux, 2.88 g (0.010 mol) of the compound of Example
(I-1-a-1) and 2.1 ml (15 mmol) of triethylamine in 50 ml of
anhydrous ethyl acetate are admixed with 1.85 ml (0.15 mol) of
pivaloyl chloride in 5 ml of anhydrous ethyl acetate. The mixture
is stirred under reflux until the reaction has, according to
thin-layer-chromatographic analysis, ended. For work-up, the
reaction mixture is concentrated, taken up in methylene chloride,
washed twice with 50 ml of 0.5 N aqueous sodium hydroxide solution,
dried over magnesium sulphate and concentrated. The crude product
is recrystallized from MTB ether/N-hexane. Yield: 2.0 g (53% of
theory), m.p.: 193.degree. C.
[0518] Similarly, and/or according to the general preparation
procedures, the following compounds of the formula (I-b-1) are
obtained:
5TABLE 5 (I-1-b) 66 Ex. No. V W X Y Z R.sup.1 m.p. .degree. C.
I-1-b-2 H CH.sub.3 CH.sub.3 CH.sub.3 H i-C.sub.3H.sub.7 163 I-1-b-3
H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 i-C.sub.3H.sub.7 153 I-1-b-4
H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 2-thienyl >220 I-1-b-5 H
CH.sub.3 CH.sub.3 Br H i-C.sub.3H.sub.7 190 I-1-b-6 H CH.sub.3
CH.sub.3 Br H 2-thienyl >220 I-1-b-7 H CH.sub.3 CH.sub.3 Br H
4-Cl-phenyl 209 I-1-b-8 H CH.sub.3 H H CH.sub.3 i-C.sub.3H.sub.7
178 I-1-b-9 H CH.sub.3 H CH.sub.3 CH.sub.3 i-C.sub.3H.sub.7 173
I-1-b-10 H CH.sub.3 H CH.sub.3 CH.sub.3 s-C.sub.4H.sub.9 193
I-1-b-11 H CH.sub.3 H CH.sub.3 H i-C.sub.3H.sub.7 183 I-1-b-12 H Cl
H Cl H i-C.sub.3H.sub.7 108
Example (I-1-c-1)
[0519] 67
[0520] At 0-10.degree. C., 1.0 ml (0.010 mol) of ethyl
chloroforrnate in 5 ml of anhydrous methylene chloride are added
dropwise to 2.88 g (0.010 mol) of the compound of Example (I-1-a-1)
and 1.4 ml (0.010 mol) of triethylamine in 50 ml of anhydrous
CH.sub.2Cl.sub.2, and the mixture is stirred at room temperature
until the reaction has, according to thin-layer-chromatographic
analysis, ended. For work-up, the mixture is washed twice with 50
ml of 0.5 N aqueous sodium hydroxide solution, dried over magnesium
sulphate and concentrated. Yield: 2.8 g (77% of theory), m.p.:
157.degree. C.
[0521] Similarly, and/or according to the general preparation
procedures, the following compounds of the formula (I-1-c) are
obtained:
6TABLE 6 (I-1-c) 68 Ex. No. V W X Y Z L M R.sup.2 m.p. .degree. C.
I-1-c-2 H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 O O C.sub.2H.sub.5
163 I-1-c-3 H CH.sub.3 CH.sub.3 Br H O O C.sub.2H.sub.5 184 I-1-c-4
H H Cl Cl H O O C.sub.2H.sub.5 131
Example II-1
[0522] 69
[0523] At 30-40.degree. C., 29.1 g (0.1016 mol) of the compound of
Example (XXV-1) in 310 ml of anhydrous methylene chloride are
carefully added dropwise to 51.3 g (0.513 mol) of conc. sulphuric
acid, and the mixture is stirred at this temperature for 2 hours.
69 ml of absolute methanol are then added dropwise in such a way
that an internal temperature of approximately 40.degree. C.
results, and stirring is continued at from 40 to 70.degree. C. for
another 6 hours.
[0524] For work-up, the mixture is poured onto 0.51 kg of ice,
extracted with methylene chloride, washed with aqueous sodium
bicarbonate solution, dried and concentrated. The residue is
recrystallized from methyl tert-butyl ether/N hexane. Yield: 17.3 g
(53% of theory): m.p.: 168.degree. C.
[0525] Similarly to Example (II-1) and according to the general
preparation procedures, the following compounds of the formula (II)
are prepared.
7TABLE 7 (II) 70 Ex. No. V W X Y Z R.sup.8 m.p. .degree. C. II-2 H
CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 78 II-3 H CH.sub.3
CH.sub.3 Br H CH.sub.3 110 II-4 H H CH.sub.3 CH.sub.3 H CH.sub.3 68
II-5 H H Cl Cl H CH.sub.3 103 II-6 H H CH.sub.3 CH.sub.3 CH.sub.3
CH.sub.3 92 II-7 H Br Cl CH.sub.3 H CH.sub.3 114 II-8 H Cl CH.sub.3
Cl H CH.sub.3 204 II-9 H H CH.sub.3 H CH.sub.3 CH.sub.3 74 II-10 H
H CH.sub.3 H H CH.sub.3 85 II-11 H H Br CH.sub.3 CH.sub.3 CH.sub.3
81 II-12 H H CH.sub.3 Br CH.sub.3 CH.sub.3 110 II-13 H CH.sub.3
CH.sub.3 H Br CH.sub.3 134 II-14 H H Cl --O--CF.sub.2--O-- CH.sub.3
121 II-15 H CH.sub.3 CH.sub.3 CH.sub.3 Br CH.sub.3 97
Example XXV-1
[0526] 71
[0527] At 0-10.degree. C., 25 g of mesityleneacetyl chloride in 30
ml of absolute THF are added dropwise to 15.8 g of
3-aminotetrahydropyran-3-car- bonitrile (according to Example XXIV)
and 17.6 ml of triethylamine in 250 ml of absolute THF, and the
mixture is stirred until the reaction has ended. The mixture is
stirred into a mixture of 500 ml of ice-water and 200 ml of 1 N
HCl. The product is filtered off with suction and the residue is
taken up in methylene chloride, dried and concentrated. Yield: 29.1
g (81% of theory), m.p. 153.degree. C.
[0528] Similarly to Example (XXV-1), and/or according to the
general preparation procedures, the following compounds of the
formula (XXV) are prepared:
8TABLE 8 (XXV) 72 Ex. No. V W X Y Z m.p. .degree. C. XXV-2 H
CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 182 XXV-3 H CH.sub.3 CH.sub.3
Br H 187 XXV-4 H H CH.sub.3 CH.sub.3 H 137 XXV-5 H H Cl Cl H 162
XXV-6 H H CH.sub.3 CH.sub.3 CH.sub.3 159 XXV-7 H Br Cl CH.sub.3 H
158 XXV-8 H Cl CH.sub.3 Cl H 141 XXV-9 H H CH.sub.3 H CH.sub.3 148
XXV-10 H H CH.sub.3 H H 149 XXV-11 H CH.sub.3 CH.sub.3 H Br 176
XXV-12 H H Br CH.sub.3 CH.sub.3 135 XXV-13 H H CH.sub.3 Br CH.sub.3
166 XXV-14 H H Cl --O--CF.sub.2--O-- 115 XXV-15 H CH.sub.3 CH.sub.3
CH.sub.3 Br 212
Example I-2-a-1
[0529] 73
[0530] At 10.degree. C., 18.1 g (0.057 mol) of the compound of
Example III-1 in 30 ml of dry dimethylformamide (DMF) are slowly
added dropwise to 9.58 g (0.085 mol) of potassium tert-butoxide in
10 ml of dry DMF, and the mixture is stirred at room temperature
overnight. The DMF is distilled off and the residue is taken up in
1 l of water and slowly acidified using concentrated HCl. The
product is filtered off with suction, washed with water and dried
under reduced pressure at 50.degree. C. m.p. 261.degree. C.
[0531] Similarly to Example (1-2-a-1) and according to the general
procedures, the following compounds of the formula (I-2-a) are
obtained:
9 (I-2-a) 74 Ex. No. V W X Y Z m.p. .degree. C. I-2-a-2 H CH.sub.3
CH.sub.3 Cl H 266-269 I-2-a-3 H H CH.sub.3 CH.sub.3 CH.sub.3
213-214 I-2-a-4 H CH.sub.3 Br CH.sub.3 H 245 I-2-a-5 H CH.sub.3
CH.sub.3 Br H 270 I-2-a-6 H CH.sub.3 Cl CH.sub.3 H 248-250 I-2-a-7
H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 218
Example I-2-b-1
[0532] 75
[0533] 1.45 g (0.012 mol) of pivaolyl chloride are added dropwise
to 2.88 g (0.01 mol) of the compound of Example I-2-a-1 and 1.2 g
(0.012 mol) of triethylamine in 30 ml of anhydrous methylene
chloride, and the mixture is stirred until the reaction has ended.
This is followed by customary work-up. Yield: 3.47 g, m.p.:
108.degree. C.
[0534] Similarly to Example (I-2-b-1) and according to the general
procedures, the following compounds of the forrnula (I-2-b) are
obtained:
10 (I-2-b) 76 Ex. No. V W X Y Z R.sup.1 m.p. .degree. C. I-2-b-2 H
H CH.sub.3 CH.sub.3 CH.sub.3 i-C.sub.3H.sub.7 106-107 I-2-b-3 H
CH.sub.3 CH.sub.3 CH.sub.3 H i-C.sub.3H.sub.7 115 I-2-b-4 H
CH.sub.3 CH.sub.3 Cl H i-C.sub.3H.sub.7 109-110 I-2-b-5 H CH.sub.3
Br CH.sub.3 H i-C.sub.3H.sub.7 94 I-2-b-6 H CH.sub.3 CH.sub.3 Br H
i-C.sub.3H.sub.7 118 I-2-b-7 H CH.sub.3 Cl CH.sub.3 H
i-C.sub.3H.sub.7 96-98 I-2-b-8 H CH.sub.3 CH.sub.3 CH.sub.3
CH.sub.3 i-C.sub.3H.sub.7 115
Example I-2-c-1
[0535] 77
[0536] 1.64 g (0.012 mol) of isobutyl chlorofornate are added
dropwise to 2.88 g (0.01 mol) of the compound of Example I-2-a-1
and 1.2 g (0.012 mol) of triethylamine in 30 ml of anhydrous
methylene chloride, and the mixture is stirred until the reaction
has ended. This is followed by customary work-up. Yield: 3.8 g,
m.p.: 107.degree. C.
[0537] Similarly to Example (I-2-c-1) and according to the general
preparation procedures, the following compounds of the formula
(I-2-c) are obtained:
11 (I-2-c) 78 Ex. No. V W X Y Z M R.sup.2 m.p. .degree. C. I-2-c-2
H H CH.sub.3 CH.sub.3 CH.sub.3 O i-C.sub.4H.sub.9 102-103 I-2-c-3 H
CH.sub.3 CH.sub.3 CH.sub.3 H S i-C.sub.3H.sub.7 105-106 I-2-c-4 H
CH.sub.3 CH.sub.3 Cl H O i-C.sub.4H.sub.9 143 1-2-c-5 H CH.sub.3 Br
CH.sub.3 H O i-C.sub.4H.sub.9 89 I-2-c-6 H CH.sub.3 CH.sub.3 Br H O
i-C.sub.4H.sub.9 138 I-2-c-7 H CH.sub.3 Cl CH.sub.3 H O
i-C.sub.4H.sub.9 90-92 I-2-c-8 H CH.sub.3 CH.sub.3 CH.sub.3
CH.sub.3 O i-C.sub.4H.sub.9 95
Example I-2-a-2
[0538] Similarly to Example I-2-a-1, but starting with the compound
of Example (III-2), the compound 79
[0539] is obtained. m.p. 266-269.degree. C.
Example III-1
[0540] 80
[0541] 10 g (0.057 mol) of the compound of Example (XXVI) and 11.3
g of 2,4,6-trimethyl-phenyl-acetyl chloride are heated at
140.degree. C. for 6 hours and subsequently degassed.
[0542] Yield 18.1 g of an oil, mass spectrum (MS) (m/e): 334
(M.sup.+, 36%), 160 (38%), 133 (100%).
[0543] Similarly to Example (III-1), and/or according to the
general preparation procedures, the following compounds of the
formula (III) are obtained:
12 81 Ex. No. V W X Y Z m.p. .degree. C. III-2 H CH.sub.3 CH.sub.3
Cl H oil III-3 H H CH.sub.3 CH.sub.3 CH.sub.3 oil III-4 H CH.sub.3
Br CH.sub.3 H oil III-5 H CH.sub.3 CH.sub.3 Br H oil III-6 H
CH.sub.3 Cl CH.sub.3 H oil III-7 H CH.sub.3 CH.sub.3 CH.sub.3
CH.sub.3 oil
Example XXIV
[0544] 82
[0545] At room temperature, 116.8 g (1.17 mol) of
3-oxa-cyclohexa-1-one (see Bull. Soc. Chim. Fr. (1970), (10),
3521-3) are added dropwise to a mixture of 222.4 g (3.27 mol) of
25% strength ammonia solution, 75 g (1.4 mol) of ammonium chloride,
68.7 g (1.4 mol) of sodium cyanide and 210 ml of water, and the
mixture is stirred at 45.degree. C. overnight. Extraction with
methylene chloride gives 95.2 g (64% of theory) of the compound
depicted above which was used without any further purification for
preparing the compounds of the formula XXV.
Example XXVI
[0546] 83
[0547] At from 0 to -20.degree. C., the mixture of 89.3 g (0.7 mol)
of the compound of Example (XXVIa) in 420 ml of ethanol is
saturated with HCl. The mixture is stirred at 0.degree. C. for
another hour and then allowed to warm to room temperature over a
period of about 3 hours.
[0548] Excess HCl is removed under reduced pressure and the mixture
is then concentrated. The residue is admixed with 400 ml of cold
water and stirred for 1 hour. This mixture is extracted twice with
methylene chloride, and the extract is dried and concentrated.
[0549] Yield 90 g, bp.sub.0.06 66.degree. C.
Example XXVIa
[0550] 84
[0551] At room temperature, 24.3 g (0.9 mol) of hydrocyanic acid
are added dropwise to 85.0 g (0.85 mol) of 3-oxa-cyclohexa-1-one
(Bull. Soc. Chim. Fr. (1970) (10), 3521-3) and 0.72 ml of
triethylamine, and the mixture is stirred at room temperature for
another 1.5 hours. The mixture is stabilized with 0.12 ml of
o-phosphoric acid and degassed under water pump vacuum.
[0552] Yield: 102 g (94% of theory)
Use Examples
Example A
[0553] Myzus-Test
[0554] Solvent: 7 parts by weight of dimethylformamide
[0555] Emulsifier: 1 part by weight of alkylaryl polyglycol
ether
[0556] To produce a suitable preparation of active compound, 1 part
by weight of active compound is mixed with the stated amount of
solvent and the stated amount of emulsifier, and the concentrate is
diluted with water to the desired concentration.
[0557] Cabbage leaves (Brassica oleracea) which are heavily
infested by peach aphids (Myzus persicae) are treated by being
dipped into the preparation of active compound of the desired
concentration.
[0558] After the desired period of time, the kill in % is
determined. 100% means that all aphids have been killed; 0% means
that none of the aphids have been killed.
[0559] In this test, for example the compounds of Preparation
Examples (I-1-a-2), (I-1-a-3), (I-1-b-2) and (I-1-c-1) effected at
an exemplary concentration of active compound of 0.1%, a kill of
100% after 6 days.
Example B
[0560] Nephotettix-Test
[0561] Solvent: 20 parts by weight of dimethylformamide
[0562] Emulsifier: 1 part by weight of alkylaryl polyglycol
ether
[0563] To produce a suitable preparation of active compound, 1 part
by weight of active compound is mixed with the stated amount of
solvent and the stated amount of emulsifier, and the concentrate is
diluted with water to the desired concentration.
[0564] Rice seedlings (Oryzae sativa) are treated by being dipped
into the preparation of active compound of the desired
concentration and are populated with the green rice leaf hoppers
(Nephotettix cincticeps) while the seedlings are still moist.
[0565] After the desired period of time, the kill in % is
determined. 100% means that all leaf hoppers have been killed; 0%
means that none of the leaf hoppers have been killed.
[0566] In this test, for example the compounds of Preparation
Examples (I-1-a-1), (I-1-a-2), (I-1-a-3), (I-1-b-1), (I-1-b-2),
(I-1-b-3), (I-1-b-4), (I-1-b-5) and (I-1-c-3) effected, at an
exemplary concentration of active compound of 0.1%, a kill of 100%
after 6 days.
[0567] Example C
[0568] Phaedon larvae test
[0569] Solvent: 7 parts by weight of dimethylformamide
[0570] Emulsifier: 1 part by weight of alkylaryl polyglycol
ether
[0571] To produce a suitable preparation of active compound, 1 part
by weight of active compound is mixed with the stated amount of
solvent and the stated amount of emulsifier, and the concentrate is
diluted with water to the desired concentration.
[0572] Cabbage leaves (Brassica oleracea) are treated by being
dipped into the preparation of active compound of the desired
concentration and are populated with larvae of the mustard beetle
(Phaedon cochleariae) while the leaves are still moist.
[0573] After the desired period of time, the kill in % is
determined. 100% means that all beetle larvae have been killed; 0%
means that none of the beetle larvae have been killed.
[0574] In this test, for example the compounds of Preparation
Examples (I-1-a-1), (I-1-a-2), (I-1-a-3), (I-1-b-1), (I-1-b-2),
(I-1-b-3), (I-1-b-4), (I-1-b-5) and (I-1-c-1) effected, at an
exemplary concentration of active compound of 0.1%, a kill of 100%
after 7 days.
Example D
[0575] Spodoptera frugiperda test
[0576] Solvent: 7 parts by weight of dimethylformamide
[0577] Emulsifier: 1 part by weight of alkylaryl polyglycol
ether
[0578] To produce a suitable preparation of active compound, 1 part
by weight of active compound is mixed with the stated amount of
solvent and the stated amount of emulsifier, and the concentrate is
diluted with water to the desired concentration.
[0579] Cabbage leaves (Brassica oleracea) are treated by being
dipped into the preparation of active compound of the desired
concentration and are populated with caterpillars of the owlet moth
Spodoptera frugiperda) while the leaves are still moist.
[0580] After the desired period of time, the kill in % is
determined. 100% means that all caterpillars have been killed; 0%
means that none of the caterpillars have been killed.
[0581] In this test, for example the compounds of Preparation
Examples (I-1-b-4) and (I-1-c-1) effected, at an exemplary
concentration of active compound of 0.1%, a kill of 100% after 7
days.
Example E
[0582] Tetranychus test (OP-resistent/dip treatment)
[0583] Solvent: 3 parts by weight of dimethylformamide
[0584] Emulsifier: 1 part by weight of alkylaryl polyglycol
ether
[0585] To produce a suitable preparation of active compound, 1 part
by weight of active compound is mixed with the stated amount of
solvent and the stated amount of emulsifier, and the concentrate is
diluted with water to the desired concentration.
[0586] Bean plants (Phaseolus vulgaris) which are heavily infested
by all stages of the greenhouse red spider mite Tetranychus urticae
are dipped into a preparation of active compound of the desired
concentration.
[0587] After the desired period of time, the kill in % is
determined. 100% means that all spider mites have been killed; 0%
means that none of the spider mites have been killed.
[0588] In this test, for example the compounds of Preparation
Examples (I-1-a-1), (I-1-b-1), (I-1-b-2) und (I-1-c-1) effected, at
an exemplary concentration of active compound of 0.1%, a kill of
100% after 13 days.
* * * * *