U.S. patent application number 10/404723 was filed with the patent office on 2003-12-11 for novel substituted phenylketoenols.
Invention is credited to Andersch, Wolfram, Erdelen, Christoph, Fischer, Reiner, Hagemann, Hermann, Schneider, Udo, Wachendorff-Neumann, Ulrike.
Application Number | 20030228984 10/404723 |
Document ID | / |
Family ID | 7848233 |
Filed Date | 2003-12-11 |
United States Patent
Application |
20030228984 |
Kind Code |
A1 |
Hagemann, Hermann ; et
al. |
December 11, 2003 |
Novel substituted phenylketoenols
Abstract
The invention relates to novel phenyl-substituted cyclic
ketoenols of the formula (I) 1 in which A, B, G, X, Y, Z and W 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) ; Erdelen, Christoph; (Leichlingen, DE) ;
Wachendorff-Neumann, Ulrike; (Neuwied, DE) ;
Schneider, Udo; (Leverkusen, DE) ; Andersch,
Wolfram; (Bergisch-Gladbach, DE) |
Correspondence
Address: |
BAYER CROPSCIENCE LP
100 BAYER ROAD
PITTSBURGH
PA
15205
US
|
Family ID: |
7848233 |
Appl. No.: |
10/404723 |
Filed: |
April 1, 2003 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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10404723 |
Apr 1, 2003 |
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09530883 |
May 8, 2000 |
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09530883 |
May 8, 2000 |
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PCT/EP98/06866 |
Oct 29, 1998 |
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Current U.S.
Class: |
504/284 ;
514/409; 548/409; 549/419 |
Current CPC
Class: |
C07C 57/58 20130101;
C07D 491/10 20130101; C07D 309/14 20130101; C07C 69/63 20130101;
A01N 47/06 20130101; A01N 43/90 20130101 |
Class at
Publication: |
504/284 ;
514/409; 548/409; 549/419 |
International
Class: |
A01N 043/36; A01N
043/38; C07D 209/96; C07D 491/12; C07D 37/22 |
Foreign Application Data
Date |
Code |
Application Number |
Nov 11, 1997 |
DE |
197 49 720.9 |
Claims
1. Compounds of the formula (I) 72in which W represents hydrogen,
cyano, nitro, halogen, alkyl, alkenyl, alkinyl, alkoxy,
halogenoalkyl, halogenoalkoxy or represents phenyl, phenoxy,
phenylthio, phenylalkoxy or phenylalkylthio, each of which is
optionally substituted, X represents halogen, alkyl, alkenyl,
alkinyl, alkoxy, alkenyloxy, halogenoalkyl, halogenoalkoxy,
halogenoalkenyloxy, cyano, nitro or represents phenyl, phenoxy,
phenylthio, phenylalkyloxy or phenylalkylthio, each of which is
optionally substituted, Y represents hydrogen, halogen, alkyl,
alkoxy, halogenoalkyl, halogenoalkoxy, cyano or nitro, Z represents
hydrogen, halogen, alkyl, alkoxy, halogenoalkyl, halogenoalkoxy,
hydroxyl, cyano, nitro or represents phenoxy, phenylthio, 5- or
6-membered hetaryloxy, 5- or 6-membered hetarylthio, phenylalkyloxy
or phenylalkylthio, each of which is optionally substituted, A
represents alkyl or optionally substituted phenyl, B represents
hydrogen or alkyl, G represents hydrogen (a) or one of the radicals
73in which E represents a metal ion equivalent or an ammonium ion,
L represents oxygen or sulphur, M represents oxygen or sulphur,
R.sup.1 represents alkyl, alkenyl, alkoxyalkyl, alkylthioalkyl or
polyalkoxyalkyl, each of which is optionally substituted by halogen
or cyano, or represents cycloalkyl or heterocyclyl, each of which
is optionally substituted by halogen, alkyl or alkoxy, or
represents phenyl, phenylalkyl, hetaryl, phenoxyalkyl or
hetaryloxyalkyl, each of which is optionally substituted, R.sup.2
represents alkyl, alkenyl, alkoxyalkyl or polyalkoxyalkyl, each of
which is optionally substituted by halogen or cyano, or represents
cycloalkyl, phenyl or benzyl, each of which is optionally
substituted, R.sup.3, R.sup.4 and R.sup.5 independently of one
another each represent alkyl, alkoxy, alkylamino, dialkylamino,
alkylthio, alkenylthio or cycloalkylthio, each of which is
optionally substituted by halogen, or represent phenyl, benzyl,
phenoxy or phenylthio, each of which is optionally substituted,
R.sup.6 and R.sup.7 independently of one another each represent
hydrogen, represent alkyl, cycloalkyl, alkenyl, alkoxy,
alkoxyalkyl, each of which is optionally substituted by halogen or
cyano, represent phenyl or benzyl, each of which is optionally
substituted, or together with the linking N atom form a cycle which
optionally contains oxygen or sulphur and which is optionally
substituted.
2. Compounds; of the formula (I) according to claim 1, in which 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 or
C.sub.1-C.sub.4-halogenoalkoxy, 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.3-C.sub.6-alkenylo- xy, C.sub.1-C.sub.4-halogenoalkyl,
C.sub.1-C.sub.4-halogenoalkoxy, C.sub.2-C.sub.6-halogenoalkenyloxy,
cyano, nitro or represents phenyl, phenoxy, phenylthio,
phenyl-C.sub.1-C.sub.4-alkoxy or phenyl-C.sub.1-C.sub.4-alkylthio,
each of which is optionally substituted by 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, Y 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, 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 phenoxy, phenylthio,
thiazolyloxy, pyridinyloxy, pyrimidyloxy, pyrazolyloxy,
phenyl-C.sub.1-C.sub.4-alkyloxy or
phenyl-C.sub.1-C.sub.4-alkylthio, each of which is optionally
substituted by 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-halogenalkoxy, nitro or cyano, A represents
C.sub.1-C.sub.6-alkyl or represents phenyl which is optionally
substituted by halogen, C.sub.1-C.sub.4-alkyl,
C.sub.1-C.sub.4-alkoxy, nitro or cyano, B represents hydrogen or
C.sub.1-C.sub.6-alkyl. G represents hydrogen (a) or represents one
of the radicals 74in 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 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, each of which is
optionally substituted by halogen or cyano, or represents
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 and which is optionally substituted by halogen,
C.sub.1-C.sub.6-alkyl or C.sub.1-C.sub.6-alkoxy, represents phenyl
which is optionally substituted by 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,
represents phenyl-C.sub.1-C.sub.6-alkyl which is optionally
substituted by 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, represents 5- or 6-membered hetaryl
having one or two hetero atoms selected from the group consisting
of oxygen, sulphur and nitrogen which is optionally substituted by
halogen or C.sub.1-C.sub.6-alkyl, represents
phenoxy-C.sub.1-C.sub.6-alkyl which is optionally substituted by
halogen or C.sub.1-C.sub.6-alkyl or represents 5- or 6-membered
hetaryloxy-C.sub.1-C.sub.6-alkyl having one or two hetero atoms
selected from the group consisting of oxygen, sulphur and nitrogen
which is optionally substituted by halogen, amino or
C.sub.1-C.sub.6-alkyl. R.sup.2 represents 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, each of which
is optionally substituted by halogen or cyano, represents
C.sub.3-C.sub.8-cycloalkyl which is optionally substituted by
halogen, C.sub.1-C.sub.6-alkyl or C.sub.1-C.sub.6-alkoxy or
represents phenyl or benzyl, each of which is optionally
substituted by 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, R.sup.3 represents
C.sub.1-C.sub.8-alkyl which is optionally substituted by halogen or
represents phenyl or benzyl, each of which is optionally
substituted by 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, R.sup.4 and R.sup.5
independently of one another represent 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, each of which is optionally
substituted by halogen, or represents phenyl, phenoxy or
phenylthio, each of which is optionally substituted by 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, R.sup.6 and R.sup.7 independently of
one another represent hydrogen, represent 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,
C.sub.1-C.sub.8-alkoxy-C.sub.2-C.sub.8-alkyl, each of which is
optionally substituted by halogen or cyano or represents phenyl or
benzyl, each of which is optionally substituted by halogen,
C.sub.1-C.sub.8-alkyl, C.sub.1-C.sub.8-halogenoalkyl or
C.sub.1-C.sub.8-alkoxy, or together represent a
C.sub.3-C.sub.6-alkylene radical in which optionally one methylene
group is replaced by oxygen or sulphur and which is optionally
substituted by C.sub.1-C.sub.6-alkyl. Compounds of the formula (I)
according to claim 1, in which 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-halogenoal- kyl or
C.sub.1-C.sub.2-halogenoalkoxy, X represents fluorine, chlorine,
bromine, C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-alkoxy,
C.sub.3-C.sub.4-alkenyloxy, C.sub.1-C.sub.2-halogenoalkyl,
C.sub.1-C.sub.2-halogenoalkoxy, C.sub.2-C.sub.4-halogenoalkenyloxy,
cyano, nitro or represents phenyl or benzyloxy, each of which is
optionally substituted by 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,
nitro or cyano, 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-halogenoalkyl, 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 phenoxy or benzyloxy, each of
which is optionally substituted by 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, A represents C.sub.1-C.sub.4-alkyl or represents
phenyl, B represents hydrogen, methyl or ethyl, G represents
hydrogen (a) or represents one of the radicals 75in 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 C.sub.1-C.sub.61-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, each of which is
optionally substituted by fluorine, chlorine, or represents
C.sub.3-C.sub.7-cycloalkyl in which optionally one or two not
directly adjacent methylene groups are replaced by oxygen and/or
sulphur and which is optionally substituted by fluorine, chlorine,
C.sub.1-C.sub.5-alkyl or C.sub.1-C.sub.5-alkoxy, represents phenyl,
which is optionally substituted by 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-halogenoal- kyl, C.sub.1-C.sub.3-halogenoalkoxy,
C.sub.1-C.sub.4-alkylthio or C.sub.1-C.sub.4-alkylsulphonyl,
represents phenyl-C.sub.1-C.sub.4-alkyl which is optionally
substituted by fluorine, chlorine, bromine, C.sub.1-C.sub.4-alkyl,
C.sub.1-C.sub.4-alkoxy, C.sub.1-C.sub.3-halogenoal- kyl or
C.sub.1-C.sub.3-halogenoalkoxy, represents pyrazolyl, thiazolyl,
pyridyl, pyrimidyl, furanyl or thienyl, each of which is optionally
substituted by fluorine, chlorine, bromine or
C.sub.1-C.sub.4-alkyl, represents phenoxy-C.sub.1-C.sub.5-alkyl
which is optionally substituted by fluorine, chlorine, bromine or
C.sub.1-C.sub.4-alkyl or represents
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, each of which is optionally
substituted by fluorine, chlorine, bromine, amino or
C.sub.1-C.sub.4-alkyl, R.sup.2 represents 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, each of which is
optionally substituted by fluorine or chlorine, represents
C.sub.3-C.sub.7-cycloalkyl which is optionally substituted by
fluorine, chlorine, C.sub.1-C.sub.4-alkyl or C.sub.1-C.sub.4-alkoxy
or represents phenyl or benzyl, each of which is optionally
substituted by 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,
R.sup.3 represents C.sub.1-C.sub.6-alkyl which is optionally
substituted by fluorine or chlorine or represents phenyl or benzyl,
each of which is optionally substituted by 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, R.sup.4 and R.sup.5 independently of one another
represent 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, each of
which is optionally substituted by fluorine or chlorine, or
represent phenyl, phenoxy or phenylthio, each of which is
optionally substituted by 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. R.sup.6 and
R.sup.7 independently of one another particularly preferably
represent hydrogen, represent 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, each of which is
optionally substituted by fluorine or chlorine, or represent phenyl
or benzyl, each of which is optionally substituted by 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, or together
represent a C.sub.3-C.sub.6-alkylene radical in which optionally
one methylene group is replaced by oxygen or sulphur and which is
optionally substituted by C.sub.1-C.sub.4-alkyl.
4. Compounds/of the formula (I) according to claim 1, in which W
represents hydrogen, nitro, cyano, fluorine, chlorine, bromine,
methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, methoxy,
ethoxy, n-propoxy, isopropoxy, trifluoromethyl, difluoromethoxy or
trifluoromethoxy, X represents fluorine, chlorine, bromine, methyl,
ethyl, n-propyl, isopropyl, n-butyl, isobutyl, methoxy, ethoxy,
n-propoxy, isopropoxy, trifluoromethyl, trifluoromethoxy,
difluoromethoxy, cyano or nitro, Y represents hydrogen, fluorine,
chlorine, bromine, methyl, ethyl, n-propyl, isopropyl, n-butyl,
isobutyl, tert-butyl, methoxy, ethoxy, n-propoxy, isopropoxy,
trifluoromethyl, trifluoromethoxy, difluoromethoxy, cyano or nitro,
Z represents hydrogen, fluorine, chlorine, bromine, methyl, ethyl,
n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, methoxy,
ethoxy, n-propoxy, isopropoxy, trifluoromethyl, trifluoromethoxy,
difluoro-methoxy, cyano or nitro, A represents methyl or ethyl, B
represents hydrogen or methyl, G represents hydrogen (a) or
represents one of the radicals 76in 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
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, each of which is
optionally substituted by fluorine or chlorine, or represents
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 and which is optionally substituted by fluorine, chlorine,
methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, tert-butyl,
methoxy, ethoxy, n-propoxy or isopropoxy, represents phenyl which
is optionally substituted by fluorine, chlorine, bromine, cyano,
nitro, methyl, ethyl, n-propyl, i-propyl, methoxy, ethoxy,
trifluoromethyl, trifluoromethoxy, methylthio, ethylthio,
methylsulphonyl or ethylsulphonyl, represents benzyl which is
optionally substituted by fluorine, chlorine, bromine, methyl,
ethyl, n-propyl, i-propyl, methoxy, ethoxy, trifluoromethyl or
trifluoromethoxy, represents furanyl, thienyl or pyridyl, each of
which is optionally substituted by fluorine, chlorine, bromine,
methyl or ethyl, represents phenoxy-C.sub.1-C.sub.4-alkyl which is
optionally substituted by fluorine, chlorine, methyl or ethyl or
represents pyridyloxy-C.sub.1-C.su- b.4-alkyl,
pyrimidyloxy-C.sub.1-C.sub.4-alkyl or thiazolyloxy-C.sub.1-C.su-
b.4-alkyl, each of which is optionally substituted by fluorine,
chlorine, amino, methyl or ethyl, R.sup.2 represents
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, each of which is
optionally substituted by fluorine or chlorine, represents
C.sub.3-C.sub.6-cycloalkyl which is optionally substituted by
fluorine, chlorine, methyl, ethyl, n-propyl, isopropyl or methoxy,
or represents phenyl or benzyl, each of which is optionally
substituted by fluorine, chlorine, cyano, nitro, methyl, ethyl,
n-propyl, i-propyl, methoxy, ethoxy, trifluoromethyl or
trifluoromethoxy, R.sup.3 represents methyl, ethyl, n-propyl,
isopropyl, n-butyl, tert-butyl, each of which is optionally
substituted by fluorine or chlorine, or represents phenyl or
benzyl, each of which is optionally substituted by fluorine,
chlorine, bromine, methyl, ethyl, isopropyl, tert-butyl, methoxy,
ethoxy, isopropoxy, trifluoromethyl, trifluoromethoxy, cyano or
nitro, R.sup.4 and R.sup.5 independently of one another represent
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, each of which is optionally substituted
by fluorine or chlorine, or represent phenyl, phenoxy or
phenylthio, each of which is optionally substituted by fluorine,
chlorine, bromine, nitro, cyano, methyl, methoxy, trifluoromethyl
or trifluoromethoxy and R.sup.6 and R.sup.7 independently of one
another represent hydrogen, represent 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,
C.sub.1-C.sub.4-alkoxy-C.sub.2-C.sub.4-alkyl, each of which is
optionally substituted by fluorine or chlorine, or represent phenyl
or benzyl, each of which is optionally substituted by fluorine,
chlorine, bromine, methyl, methoxy or trifluoromethyl, or together
represent a C.sub.5-C.sub.6-alkylene radical in which optionally
one methylene group is replaced by oxygen or sulphur and which is
optionally substituted by methyl or ethyl.
5. Process, for preparing compounds of the formula (I) according to
claim 1, characterized in that (A) compounds of the formula (I-a)
77in which A, B, W, X, Y and Z are each as defined in claim 1, are
obtained when compounds of the formula (II) 78in which A, B, W, X,
Y and z are each as defined in claim 1 and R.sup.8 represents
alkyl, are intramolecularly condensed in the presence of a diluent
and in the presence of a base and, if appropriate subsequently
(B.alpha.) reacted with acyl halides of the formula (III) 79in
which R.sup.1 is as defined in claim 1 and Hal represents halogen
or .beta.) reacted with carboxylic anhydrides of the formula (IV)
R.sup.1--CO--O--CO--R.sup.1 (IV) 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 (C) reacted with
chloroformic esters or chloroformic thioesters of the formula (V)
R.sup.2-M-CO--Cl (V) in which R.sup.2 and M 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 (D) reacted with
chloromonothioformic esters or chlorodithioformic esters of the
formula (VI) 80in which M and R.sup.2 are each 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 sulphonyl chlorides
of the formula (VII) R.sup.3--SO.sub.2--Cl (VII) 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
(F) reacted with phosphorus compounds of the formula (VIII) 81in
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
f if appropriate in the presence of an acid binder; or (G) reacted
with metal compounds or amines of the formulae (IX) or (X)
Me(OR.sup.9).sub.t (IX) 82in which Me represents a mono- or
divalent metal, t represents the number 1 or 2 and R.sup.9,
R.sup.10, R.sup.11 independently of one another each represent
hydrogen or alkyl, if appropriate in the presence of a diluent; or
(H.alpha.) reacted with isocyanates or isothiocyanates of the
formula (XI) R.sup.6--N.dbd.C=L (XI) 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 B)
reacted with carbamoyl chlorides or thiocarbamoyl chlorides of the
formula (XII) 83in 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) 84in which A, B, W, X, Y and Z are
each as defined in claim 1 and R.sup.8 represents alkyl.
7. Compounds of the formula (XIII) 85in which A and B are each as
defined above and R.sup.8 represents alkyl.
8. Compounds of the formula (XV) 86in which A, B, W, X, Y and Z are
each as defined in claim 1.
9. Compounds of the formula (XVI) 87in which A and B are each as
defined in claim 1.
10. Compounds of the formula (XXII) 88in which A and B are each as
defined in claim 1.
11. Compounds of the formula (XXIII) 89in which A, B, X, Y, Z and W
are each as defined in claim 1.
12. Compounds of the formula (XVII) 90in which X.sup.1 represents
fluorine, chlorine or bromine (in particular chlorine or bromine),
Y.sup.1 represents ethyl and W.sup.1 represents hydrogen, fluorine
chlorine or bromine (in particular hydrogen, chlorine or
bromine).
13. Compounds of the formula (XVIII) 91in which X.sup.1, Y.sup.1
and W.sup.1 are each as defined in claim 9 and R.sup.8 represents
alkyl (in particular C.sub.1-C.sub.6-alkyl, specifically methyl or
ethyl).
14. Pesticides or herbicides, characterized in that they contain a
compound of the formula (I) according to claim 1. The use of
compounds of the formula (I) according to claim 1 for controlling
pests and weeds.
16. 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.
17. 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 in-secticides, 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, DE-196
49 665, WO 94/01 997, WO 95/01 358, WO 95/20 572, EP-A-668 267, WO
95/26 954, WO 96/25395, WO 96/35 664, WO 97/01 535 and WO 97/02
243) and their use as pesticides and, of some of them, as
herbicides, are known.
[0004] However, the herbicidal, acaricidal and insecticidal
activity and/or spectrum of activity and/or plant safety of these
compounds, in particular with respect to crop plants, is not always
satisfactory.
[0005] This invention, accordingly, provides novel compounds of the
formula (I) 2
[0006] in which
[0007] W represents hydrogen, cyano, nitro, halogen, alkyl,
alkenyl, alkinyl, alkoxy, halogenoalkyl, halogenoalkoxy or
represents phenyl, phenoxy, phenylthio, phenylalkoxy or
phenylalkylthio, each of which is optionally substituted,
[0008] X represents halogen, alkyl, alkenyl, alkinyl, alkoxy,
alkenyloxy, halogenoalkyl, halogenoalkoxy, halogenoalkenyloxy,
cyano, nitro or represents phenyl, phenoxy, phenylthio,
phenylalkyloxy or phenylalkylthio, each of which is optionally
substituted,
[0009] Y represents hydrogen, halogen, alkyl, alkoxy,
halogenoalkyl, halogenoalkoxy, cyano or nitro,
[0010] Z represents hydrogen, halogen, alkyl, alkoxy,
halogenoalkyl, halogenoalkoxy, hydroxyl, cyano, nitro or represents
phenoxy, phenylthio, S-- or 6-membered hetaryloxy, 5- or 6-membered
hetarylthio, phenylalkyloxy or phenylalkylthio, each of which is
optionally substituted,
[0011] A represents alkyl or optionally substituted phenyl,
[0012] B represents hydrogen or alkyl,
[0013] G represents hydrogen (a) or one of the radicals 3
[0014] in which
[0015] E represents a metal ion equivalent or an ammonium ion,
[0016] L represents oxygen or sulphur,
[0017] M represents oxygen or sulphur,
[0018] R.sup.1 represents alkyl, alkenyl, alkoxyalkyl,
alkylthioalkyl or polyalkoxyalkyl, each of which is optionally
substituted by halogen or cyano, or represents cycloalkyl or
heterocyclyl, each of which is optionally substituted by halogen,
alkyl or alkoxy, or represents phenyl, phenylalkyl, hetaryl,
phenoxyalkyl or hetaryloxyalkyl, each of which is optionally
substituted,
[0019] R.sup.2 represents alkyl, alkenyl, alkoxyalkyl or
polyalkoxyalkyl, each of which is optionally substituted by halogen
or cyano, or represents cycloalkyl, phenyl or benzyl, each of which
is optionally substituted,
[0020] R.sup.3, R.sup.4 and R.sup.5 independently of one another
each represent alkyl, alkoxy, alkylamino, dialkylamino, alkylthio,
alkenylthio or cycloalkylthio, each of which is optionally
substituted by halogen, or represent phenyl, benzyl, phenoxy or
phenylthio, each of which is optionally substituted,
[0021] R.sup.6 and R.sup.7 independently of one another each
represent hydrogen, represent alkyl, cycloalkyl, alkenyl, alkoxy,
alkoxyalkyl, each of which is optionally substituted by halogen or
cyano, represent phenyl or benzyl, each of which is optionally
substituted, or together with the linking N atom form a cycle which
optionally contains oxygen or sulphur and which is optionally
substituted.
[0022] 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 both pure
compounds and, if appropriate, mixtures having different
proportions of isomeric compounds are intended.
[0023] Including the various meanings (a), (b), (c), (d), (e), (f)
and (g) of the group G, the following principal structures (I-a) to
(I-g) result: 45
[0024] in which
[0025] A, B, E, L, M, 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.
[0026] Furthermore, it has been found that the novel compounds of
the formula (I) are obtained by one of the processes described
below:
[0027] (A) compounds of the formula (I-a) 6
[0028] in which
[0029] A, B, W, X, Y and Z are each as defined above,
[0030] are obtained when
[0031] compounds of the formula (II) 7
[0032] in which
[0033] A, B, W, X, Y and Z are each as defined above, and
[0034] R.sup.8 represents alkyl (preferably
C.sub.1-C.sub.6-alkyl),
[0035] are intramolecularly condensed in the presence of a diluent
and in the presence of a base.
[0036] Furthermore, it has been found
[0037] (B) that the compounds of the formula (I-b) shown above in
which R.sup.1, A, B, W, X, Y and Z are each as defined above are
obtained when compounds of the formula (I-a) shown above in which
A, B, W, X, Y and Z are each as defined above,
[0038] .alpha.) are reacted with acyl halides of the formula (III)
8
[0039] in which
[0040] R.sup.1 is as defined above and
[0041] Hal represents halogen (in particular chlorine or bromine)
or
[0042] .beta.) are reacted with carboxylic anhydrides of the
formula (IV)
R.sup.1--CO--O--CO--R.sup.1 (IV)
[0043] in which
[0044] R.sup.1 is as defined above,
[0045] if appropriate in the presence of a diluent and if
appropriate in the presence of an acid binder;
[0046] (C) that the compounds of the formula (I-c) shown above in
which R.sup.2, A, B, W, M, X, Y and Z are each as defined above and
L represents oxygen are obtained when compounds of the formula
(I-a) shown above in which A, B, W, X, Y and Z are each as defined
above,
[0047] are reacted with chloroformic esters or chloroformic
thioesters of the formula (V)
R.sup.2-M-CO--Cl (V)
[0048] in which
[0049] R.sup.2 and M are each as defined above,
[0050] if appropriate in the presence of a diluent and if
appropriate in the presence of an acid binder;
[0051] (D) that compounds of the formula (I-c) shown above in which
R.sup.2, A, B, W, M, X, Y and Z are each as defined above and L
represents sulphur are obtained when compounds of the formula (I-a)
shown above in which A, B, W, X, Y and Z are each as defined
above,
[0052] are reacted with chloromonothioformic esters or
chlorodithioformic esters of the formula (VI) 9
[0053] in which
[0054] M and R.sup.2 are each as defined above,
[0055] if appropriate in the presence of a diluent and if
appropriate in the presence of an acid binder;
[0056] (E) that compounds of the formula (I-d) shown above in which
R.sup.3, A, B, W, X, Y and Z are each as defined above are obtained
when compounds of the formula (I-a) shown above in which A, B, W,
X, Y and Z are each as defined above,
[0057] are reacted with sulphonyl chlorides of the formula
(VII)
R.sup.3--SO.sub.2--Cl (VII)
[0058] in which
[0059] R.sup.3 is as defined above,
[0060] if appropriate in the presence of a diluent and if
appropriate in the presence of an acid binder,
[0061] (F) that compounds of the formula (I-e) shown above in which
L, R.sup.4, R.sup.5, A, B, W, X, Y and Z are each as defined above
are obtained when compounds of the formula (I-a) shown above in
which A, B, W, X, Y and Z are each as defined above,
[0062] are reacted with phosphorus compounds of the formula (VIII)
10
[0063] in which
[0064] L, R.sup.4 and R.sup.5 are each as defined above and
[0065] Hal represents halogen (in particular chlorine or
bromine)i
[0066] if appropriate in the presence of a diluent and if
appropriate in the presence of an acid binder;
[0067] (G) that compounds of the formula (I-f) shown above in which
E, A, B, W, X, Y and Z are each as defined above are obtained when
compounds of the formula (I-a) in which A, B, W, X, Y and Z are
each as defined above,
[0068] are reacted with metal compounds or amines of the formulae
(IX) or (X)
Me(OR.sup.9).sub.t (IX)
[0069] 11
[0070] in which
[0071] Me represents a mono- or divalent metal (preferably an
alkali metal or alkaline earth metal such as lithium, sodium,
potassium, magnesium or calcium),
[0072] t represents the number 1 or 2 and
[0073] R.sup.9, R.sup.10, R.sup.11 independently of one another
each represent hydrogen or alkyl (preferably
C.sub.1-C.sub.8-alkyl),
[0074] if appropriate in the presence of a diluent;
[0075] (H) that compounds of the formula (I-g) shown above in which
L, R.sup.6, R.sup.7, A, B, W, X, Y and Z are each as defined above
are obtained when compounds of the formula (I-a) shown above in
which A, B, W, X, Y and Z are each as defined above,
[0076] .alpha.) are reacted with isocyanates or isothiocyanates of
the formula (XI)
R.sup.6--N.dbd.C=L (XI)
[0077] in which
[0078] R.sup.6 and L are each as defined above,
[0079] if appropriate in the presence of a diluent and if
appropriate in the presence of a catalyst, or
[0080] .beta.) are reacted with carbamoyl chlorides or
thiocarbamoyl chlorides of the formula (XII) 12
[0081] in which
[0082] L, R.sup.6 and R.sup.7 are each as defined above,
[0083] if appropriate in the presence of a diluent and if
appropriate in the presence of an acid binder.
[0084] Furthermore, it has been found that the novel compounds of
the formula (I) have very good activity as pesticides, preferably
as insecticides and as acaricides, and as herbicides, and that they
are additionally frequently very well tolerated by plants, in
particular by crop plants.
[0085] 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 formula mentioned hereinabove
and hereinbelow are illustrated below:
[0086] 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 or
C.sub.1-C.sub.4-halo-genoalkoxy.
[0087] 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.3-C.sub.6-alkenyloxy,
C.sub.1-C.sub.4-halogenoalkyl, C.sub.1-C.sub.4-halogenoalkoxy,
C.sub.2-C.sub.6-halogenoalkenyloxy, cyano, nitro or represents
phenyl, phenoxy, phenylthio, phenyl-C.sub.1-C.sub.4-alkoxy or
phenyl-C.sub.1-C.sub.4-alkylthio, each of which is optionally
substituted by 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.
[0088] 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.
[0089] 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,
hydroxyl, cyano, nitro or represents phenoxy, phenylthio,
thiazolyloxy, pyridinyloxy, pyrimidyloxy, pyrazolyloxy,
phenyl-C.sub.1-C.sub.4-alkyloxy or phenyl-C.sub.1-C.sub.4-a-
lkylthio, each of which is optionally substituted by halogen,
C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-alkoxy,
C.sub.1-C.sub.4-halogenoal- kyl, C.sub.1-C.sub.4-halogenalkoxy,
nitro or cyano.
[0090] A preferably represents C.sub.1-C.sub.6-alkyl or represents
phenyl which is optionally substituted by halogen,
C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-alkoxy, nitro or cyano.
[0091] B preferably represents hydrogen or
C.sub.1-C.sub.6-alkyl.
[0092] G preferably represents hydrogen (a) or represents one of
the radicals 13
[0093] in which
[0094] E represents a metal ion equivalent or an ammonium ion,
[0095] L represents oxygen or sulphur and
[0096] M represents oxygen or sulphur.
[0097] R.sup.1 preferably represents C.sub.1-C.sub.20-alkyl,
C.sub.2-C.sub.20-alkenyl, C.sub.1-CS-alkoxy-C.sub.1-C.sub.8-alkyl,
C.sub.1-CS-alkylthio-C.sub.1-C.sub.8-alkyl or
poly-C.sub.1-CS-alkoxy-C.su- b.1-C.sub.8-alkyl, each of which is
optionally substituted by halogen or cyano, or represents
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 and which is optionally substituted by halogen,
C.sub.1-C.sub.6-alkyl or C.sub.1-C.sub.6-alkoxy,
[0098] represents phenyl which is optionally substituted by
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,
[0099] represents phenyl-C.sub.1-C.sub.6-alkyl which is optionally
substituted by 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,
[0100] represents 5- or 6-membered hetaryl having one or two hetero
atoms selected from the group consisting of oxygen, sulphur and
nitrogen (for example pyrazolyl, thiazolyl, pyridyl, pyrimidyl,
furanyl or thienyl) which is optionally substituted by halogen or
C.sub.1-C.sub.6-alkyl,
[0101] represents phenoxy-C.sub.1-C.sub.6-alkyl which is optionally
substituted by halogen or C.sub.1-C.sub.6-alkyl or represents 5- or
6-membered hetaryloxy-C.sub.1-C.sub.6-alkyl having one or two
hetero atoms selected from the group consisting of oxygen, sulphur
and nitrogen (for example pyridyloxy-C.sub.1-C.sub.6-alkyl,
pyrimidyloxy-C.sub.1-C.sub- .6-alkyl or
thiazolyloxy-C.sub.1-C.sub.6-alkyl) which is optionally substituted
by halogen, amino or C.sub.1-C.sub.6-alkyl.
[0102] R.sup.2 preferably represents 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, each of which is
optionally substituted by halogen or cyano, represents
C.sub.3-C.sub.8-cycloalkyl which is optionally substituted by
halogen, C.sub.1-C.sub.6-alkyl or C.sub.1-C.sub.6-alkoxy or
[0103] represents phenyl or benzyl, each of which is optionally
substituted by 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.
[0104] R.sup.3 preferably represents C.sub.1-C.sub.8-alkyl which is
optionally substituted by halogen or represents phenyl or benzyl,
each of which is optionally substituted by 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.
[0105] R.sup.4 and R.sup.5 independently of one another each
preferably represent 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, each of
which is optionally substituted by halogen, or represents phenyl,
phenoxy or phenylthio, each of which is optionally substituted by
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.
[0106] R.sup.6 and R.sup.7 independently of one another each
preferably represent hydrogen, represent 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,
C.sub.1-C.sub.8-alkoxy-C.sub.2-C.sub.8-alkyl, each of which is
optionally substituted by halogen or cyano or represents phenyl or
benzyl, each of which is optionally substituted by halogen,
C.sub.1-C.sub.8-alkyl, C.sub.1-C.sub.8-halogenoalkyl or
C.sub.1-C.sub.8-alkoxy, or together represent a
C.sub.3-C.sub.6-alkylene radical in which optionally one methylene
group is replaced by oxygen or sulphur and which is optionally
substituted by C.sub.1-C.sub.6-alkyl.
[0107] 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 or
C.sub.1-C.sub.2-halogenoalkoxy.
[0108] X particularly preferably represents fluorine, chlorine,
bromine, C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-alkoxy,
C.sub.3-C.sub.4-alkenyloxy- , C.sub.1-C.sub.2-halogenoalkyl,
C.sub.1-C.sub.2-halogenoalkoxy, C.sub.2-C.sub.4-halogenoalkenyloxy,
cyano, nitro or represents phenyl or benzyloxy, each of which is
optionally substituted by 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.
[0109] 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.
[0110] 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 represents phenoxy or benzyloxy, each of
which is optionally substituted by 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,
nitro or cyano.
[0111] A particularly preferably represents C.sub.1-C.sub.4-alkyl
or represents phenyl.
[0112] B particularly preferably represents hydrogen, methyl or
ethyl.
[0113] G particularly preferably represents hydrogen (a) or
represents one of the radicals 14
[0114] (in particular represents one of the radicals (a), (b) or
(c)), in which
[0115] E represents a metal ion equivalent or an ammonium ion,
[0116] L represents oxygen or sulphur and
[0117] M represents oxygen or sulphur.
[0118] R.sup.1 particularly preferably represents
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, each of which is
optionally substituted by fluorine, chlorine, or represents
C.sub.3-C.sub.7-cycloalkyl in which optionally one or two not
directly adjacent methylene groups are replaced by oxygen and/or
sulphur and which is optionally substituted by fluorine, chlorine,
C.sub.1-C.sub.5-alkyl or C.sub.1-C.sub.5-alkoxy,
[0119] represents phenyl, which is optionally substituted by
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,
[0120] represents phenyl-C.sub.1-C.sub.4-alkyl which is optionally
substituted by 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,
[0121] represents pyrazolyl, thiazolyl, pyridyl, pyrimidyl, furanyl
or thienyl, each of which is optionally substituted by fluorine,
chlorine, bromine or C.sub.1-C.sub.4-alkyl,
[0122] represents phenoxy-C.sub.1-C.sub.5-alkyl which is optionally
substituted by fluorine, chlorine, bromine or C.sub.1-C.sub.4-alkyl
or
[0123] represents 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, each of which is optionally
substituted by fluorine, chlorine, bromine, amino or
C.sub.1-C.sub.4-alkyl.
[0124] R.sup.2 particularly preferably represents
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, each of which is
optionally substituted by fluorine or chlorine,
[0125] represents C.sub.3-C.sub.7-cycloalkyl which is optionally
substituted by fluorine, chlorine, C.sub.1-C.sub.4-alkyl or
C.sub.1-C.sub.4-alkoxy or
[0126] represents phenyl or benzyl, each of which is optionally
substituted by 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-halogenoal- kyl or
C.sub.1-C.sub.3-halogenoalkoxy.
[0127] R.sup.3 particularly preferably represents
C.sub.1-C.sub.6-alkyl which is optionally substituted by fluorine
or chlorine or represents phenyl or benzyl, each of which is
optionally substituted by 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.
[0128] R.sup.4 and R.sup.5 independently of one another
particularly preferably represent 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, each of which is optionally
substituted by fluorine or chlorine, or represent phenyl, phenoxy
or pheinylthio, each of which is optionally substituted by
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.
[0129] R.sup.6 and R.sup.7 independently of one another
particularly preferably represent hydrogen, represent
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, each of which is
optionally substituted by fluorine or chlorine, or represent phenyl
or benzyl, each of which is optionally substituted by 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, or together
represent a C.sub.3-C.sub.6-alkylene radical in which optionally
one methylene group is replaced by oxygen or sulphur and which is
optionally substituted by C.sub.1-C.sub.4-alkyl.
[0130] In the radical definitions referred to as being
(particularly) preferred, halogen in combination with other
radicals (for example in halogenoalkyl, halogenoalkoxy or
halogenoalkenyloxy) in particular represents fluorine, chlorine and
bromine, specifically fluorine and chlorine.
[0131] W very particularly preferably represents hydrogen, nitro,
cyano, fluorine, chlorine, bromine, methyl, ethyl, n-propyl,
isopropyl, n-butyl, isobutyl, methoxy, ethoxy, n-propoxy,
isopropoxy, trifluoromethyl, difluoromethoxy or
trifluoromethoxy.
[0132] X very particularly preferably represents fluorine,
chlorine, bromine, methyl, ethyl, n-propyl, isopropyl, n-butyl,
isobutyl, methoxy, ethoxy, n-propoxy, isopropoxy, trifluoromethyl,
trifluoromethoxy, difluoromethoxy, cyano or nitro.
[0133] Y very particularly preferably represents hydrogen,
fluorine, chlorine, bromine, methyl, ethyl, n-propyl, isopropyl,
n-butyl, isobutyl, tert-butyl, methoxy, ethoxy, n-propoxy,
isopropoxy, trifluoromethyl, trifluoromethoxy, difluoromethoxy,
cyano or nitro.
[0134] Z very particularly preferably represents hydrogen,
fluorine, chlorine, bromine, methyl, ethyl, n-propyl, isopropyl,
n-butyl, isobutyl, tert-butyl, methoxy, ethoxy, n-propoxy,
isopropoxy, trifluoromethyl, trifluoromethoxy, difluoromethoxy,
cyano or nitro.
[0135] A very particularly preferably represents methyl or
ethyl.
[0136] B very particularly preferably represents hydrogen or
methyl.
[0137] G very particularly preferably represents hydrogen (a) or
represents one of the radicals 15
[0138] (in particular represents one of the radicals (a), (b) or
(c)),
[0139] in which
[0140] E represents a metal ion equivalent or an ammonium ion,
[0141] L represents oxygen or sulphur and
[0142] M represents oxygen or sulphur.
[0143] R.sub.1 very particularly preferably represents
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, each of which is
optionally substituted by fluorine or chlorine, or represents
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 and which is optionally substituted by fluorine, chlorine,
methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, tert-butyl,
methoxy, ethoxy, n-propoxy or isopropoxy,
[0144] represents phenyl which is optionally substituted by
fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n-propyl,
i-propyl, methoxy, ethoxy, trifluoromethyl, trifluoromethoxy,
methylthio, ethylthio, methylsulphonyl or ethylsulphonyl,
represents benzyl which is optionally substituted by fluorine,
chlorine, bromine, methyl, ethyl, n-propyl, i-propyl, methoxy,
ethoxy, trifluoromethyl or trifluoromethoxy,
[0145] represents furanyl, thienyl or pyridyl, each of which is
optionally substituted by fluorine, chlorine, bromine, methyl or
ethyl,
[0146] represents phenoxy-C.sub.1-C.sub.4-alkyl which is optionally
substituted by fluorine, chlorine, methyl or ethyl or
[0147] represents 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, each of which is optionally
substituted by fluorine, chlorine, amino, methyl or ethyl.
[0148] R.sup.2 very particularly preferably represents
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- , each of which
is optionally substituted by fluorine or chlorine,
[0149] represents C.sub.3-C.sub.6-cycloalkyl which is optionally
substituted by fluorine, chlorine, methyl, ethyl, n-propyl,
isopropyl or methoxy,
[0150] or represents phenyl or benzyl, each of which is optionally
substituted by fluorine, chlorine, cyano, nitro, methyl, ethyl,
n-propyl, i-propyl, methoxy, ethoxy, trifluoromethyl or
trifluoromethoxy.
[0151] R.sup.3 very particularly preferably represents methyl,
ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, each of which is
optionally substituted by fluorine or chlorine, or represents
phenyl or benzyl, each of which is optionally substituted by
fluorine, chlorine, bromine, methyl, ethyl, isopropyl, tert-butyl,
methoxy, ethoxy, isopropoxy, trifluoromethyl, trifluoromethoxy,
cyano or nitro.
[0152] R.sup.4 and R.sup.5 independently of one another each very
particularly preferably represent 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, each
of which is optionally substituted by fluorine or chlorine, or
represent phenyl, phenoxy or phenylthio, each of which is
optionally substituted by fluorine, chlorine, bromine, nitro,
cyano, methyl, methoxy, trifluoromethyl or trifluoromethoxy.
[0153] R.sup.6 and R.sup.7 independently of one another each very
particularly preferably represent hydrogen, represent
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,
C.sub.1-C.sub.4-alkoxy-C- .sub.2-C.sub.4-alkyl, each of which is
optionally substituted by fluorine or chlorine, or represent phenyl
or benzyl, each of which is optionally substituted by fluorine,
chlorine, bromine, methyl, methoxy or trifluoromethyl, or together
represent a C.sub.5-C.sub.6-alkylene radical in which optionally
one methylene group is replaced by oxygen or sulphur and which is
optionally substituted by methyl or ethyl.
[0154] Especially preferred are compounds of the formula (I), in
which A represents CH.sub.3 and B represents hydrogen, in
particular in combination with the very particularly preferred
radicals mentioned for G.
[0155] 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.
[0156] 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).
[0157] 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.
[0158] 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.
[0159] Saturated or unsaturated hydrocarbon radicals such as alkyl
or alkenyl may be, also in connection with hetero atoms such as,
for example, in alkoxy, in each case straight-chain or branched as
far as this is possible.
[0160] Optionally substituted radicals may be mono- or
polysubstituted, it being possible for the substituents in the case
of polysubstitutions to be identical or different.
[0161] In addition to the compounds mentioned in the Preparation
Examples, the following compounds of the formula (I-a) may be
mentioned specifically:
1TABLE 1 (I-a) 16 A = CH.sub.3; B = H X W Y Z Br H Cl H Cl H Br H
Cl H Cl H Cl H F H F H Cl H Cl H OCH.sub.3 H Cl H CH.sub.3 H
OCH.sub.3 H Cl H OCH.sub.3 H OCH.sub.3 H CH.sub.3 H Cl H CH.sub.3 H
F H CH.sub.3 H OCH.sub.3 H CH.sub.3 H t-C.sub.4H.sub.9 H CH.sub.3 H
CH.sub.3 H Cl Cl H H Cl F H H Cl OCH.sub.3 H H Cl CH.sub.3 H H Cl
OC.sub.2H.sub.5 H H OCH.sub.3 OCH.sub.3 H H CH.sub.3 CH.sub.3 H H
Br CH.sub.3 Br H Cl Cl CH.sub.3 H CH.sub.3 Br CH.sub.3 H CH.sub.3
Cl CH.sub.3 H CH.sub.3 OCHF.sub.2 CH.sub.3 H CH.sub.3
OCH.sub.2CF.sub.3 CH.sub.3 H CH.sub.3 OC.sub.2H.sub.5 CH.sub.3 H
CH.sub.3 OCH.sub.3 CH.sub.3 H CH.sub.3 CH.sub.3 CH.sub.3 H Br Br
CH.sub.3 H Cl Cl CH.sub.3 H C.sub.2H.sub.5 C.sub.2H.sub.5 Br H
CH.sub.3 CH.sub.3 Br H CH.sub.3 CH.sub.3 OCH.sub.3 H Br Cl CH.sub.3
H Br CH.sub.3 Cl H Cl CH.sub.3 Br H C.sub.2H.sub.5 Br CH.sub.3 H
CH.sub.3 O--C.sub.3H.sub.7 CH.sub.3 H CH.sub.3 CH.sub.3 Cl H Cl H
Cl Cl CH.sub.3 H CH.sub.3 CH.sub.3 CH.sub.3 H Cl CH.sub.3 Br H Cl
CH.sub.3 Br H CH.sub.3 CH.sub.3 Cl H Br CH.sub.3 Cl H Cl CH.sub.3
CH.sub.3 H Br CH.sub.3 Cl H Cl F Cl H CH.sub.3 Cl CH.sub.3 H H H Cl
H H H Br H H H CF.sub.3 H H H OCH.sub.3 H H H 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 H
CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 F CH.sub.3 CH.sub.3 CH.sub.3 Cl
CH.sub.3 CH.sub.3 CH.sub.3 Br CH.sub.3 CH.sub.3 H Cl CH.sub.3
CH.sub.3 H Br Cl Cl H Br
[0162] Using according to process (A)
N-[(4-chloro-2,6-dimethyl)-phenylace-
tyl]-4-amino-4-carboxyethyl-2-methyl-tetrahydropyran as starting
material, the course of the process according to the invention can
be represented by the following equation: 17
[0163] Using according to process (Bo)
3-[(2-chloro-4-methyl)-phenyl]-5,5--
[(2-ethyl)-ethyleneoxyethyl]-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:
18
[0164] Using according to process (B) (variant .beta.)
3-[(2,4-dichloro)-phenyl]-5,5-[(2-methyl)-ethyleneoxyethyl]-pyrrolidine-2-
,4-dione and acetic anhydride as starting materials, the course of
the process according to the invention can be represented by the
following equation: 19
[0165] Using according to process (C)
8-[(2,4-dichloro)-phenyl]-5,5-[(2-me-
thyl)-ethyleneoxyethyl]-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: 20
[0166] Using according to process (D)
3-[(2,6-dibromo-4-methyl)-phenyl]-5,-
5-[(2-ethyl)-ethyleneoxyethyl]-pyrrolidine-2,4-dione and methyl
chloromonothioformate as starting materials, the course of the
reaction can be represented as follows: 21
[0167] Using according to process (E)
2-[(2,4,6-trimethyl)-phenyl]5,5-[(2m- ethyl)
ethyleneoxyethyl]-pyrrolidine-2,4-dione and methanesulphonyl
chloride as starting materials, the course of the reaction can be
represented by the following equation: 22
[0168] Using according to process (F)
2-[(4-bromo-2-chloro-6-methyl)-pheny-
l]5-4-hydroxy-5,5-[(2-methyl)-ethyleneoxyethyl]-pyrrolidine-2,4dione
and (2,2,2-trifluoroethyl) methanethio-phosphonyl chloride as
starting materials, the course of the reaction can be represented
by the following equation: 23
[0169] Using according to process (G)
3-[(2,4-dichloro)-6-methylphenyl]-5,-
5-[(2-ethyl)-ethyleneoxyethyl]-pyrrolidine-2,4-dione and NaOH as
components, the course of the process according to the invention
can be represented by the following equation: 24
[0170] Using according to process (H) (variant ax)
3-[(2-chloro-4-bromo-5--
methyl)-phenyl]-4-hydroxy-5,5-[(2-methyl)-ethyleneoxyethyl]-pyrrolidine-2,-
4-dione and ethyl isocyanate as starting materials, the course of
the reaction can be represented by the following equation: 25
[0171] Using according to process (H) (variant 1)
3-[(2-chloro-4,6-dimethy-
l)-phenyl]-5,5-[(2-methyl)-ethyleneoxyethyl]-pyrrolidine-2,4-dione
and dimethylcarbamidoyl chloride as starting materials, the course
of the reaction can be represented by the following equation:
26
[0172] The compounds of the formula (II) required as starting
materials in the process (A) according to the invention 27
[0173] in which
[0174] A, B, W, X, Y, Z and R.sup.8 are each as defined above, are
novel.
[0175] The acylamino acid esters of the formula (II) are obtained,
for example, when amino acid derivatives of the formula (XIII)
28
[0176] in which
[0177] A, B and R.sup.8 are each as defined above,
[0178] are acylated with substituted phenylacetyl halides of the
formula (XIV) 29
[0179] in which
[0180] W, X, Y and Z are each as defined above and
[0181] Hal represents chlorine or bromine,
[0182] (Chem. Reviews 52, 237-416 (1953); Bhattacharya, Indian J.
Chem. 6, 341-5, 1968) or when acylamino acids of the formula (XV)
30
[0183] in which
[0184] A, B, W, X, Y and Z are each as defined above,
[0185] are esterified (Chem. Ind. (London) 1568 (1968)).
[0186] The compounds of the formula (XV) 31
[0187] in which
[0188] A, B, W, X, Y and Z are each as defined above, are
novel.
[0189] The compounds of the formula (XV) are obtained, for example,
when 4-amino-tetrahydropyran-4-carboxylic acids of the formula
(XVI) 32
[0190] in which
[0191] A and B are each as defined above
[0192] are acylated according to Schotten-Baumann (Organikum, VEB
Deutscher Verlag der Wissenschaften, Berlin 1977, P. 505) with
substituted phenylacetyl halides of the formula (XIV) 33
[0193] in which
[0194] W, X, Y and Z are each as defined above and
[0195] Hal represents chlorine or bromine.
[0196] Some of the compounds of the formula (XIV) are novel and can
be prepared by known processes (cf., for example, DE-196 49
665).
[0197] The compounds of the formula (XIV) are obtained, for
example, by reacting substituted phenylacetic acids of the formula
(XVII) 34
[0198] in which
[0199] W, X, Y and Z are each as defined above
[0200] 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.
[0201] Some of the compounds of the formula (XVII) 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, DE-196 49 665).
[0202] The compounds of the formula (XVII) are obtained, for
example, by hydrolysing substituted phenylacetic esters of the
formula (XVIII) 35
[0203] in which
[0204] W, X, Y, Z and R.sup.8 are each as defined above
[0205] 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.
[0206] Some of the compounds of the formula (XVIII) are novel, they
can be prepared by processes known in principle.
[0207] The compounds of the formula (XVIII) are obtained, for
example, by reacting substituted 1,1,1-trichloro-2-phenylethanes of
the formula (XIX) 36
[0208] in which
[0209] W, X, Y and Z are each as defined above
[0210] 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).
[0211] Some of the compounds of the formula (XIX) are novel, they
can be prepared by processes known in principle.
[0212] The compounds of the formula (XIX) are obtained, for
example, when anilines of the formula (XX) 37
[0213] in which
[0214] W, X, Y and Z are each as defined above are reacted in the
presence of alkyl nitrite of the formula (XXI)
R.sup.13--ONO (XXI)
[0215] in which
[0216] R.sup.13 represents alkyl, preferably
C.sub.1-C.sub.6-alkyl,
[0217] 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 of from 0.degree. C. to 60.degree. C., with
vinylidene chloride (CH.sub.2.dbd.CCl.sub.2).
[0218] Some of the compounds of the formula (XX) are known. They
can be prepared by processes known from the literature, for example
by reduction of the corresponding nitro compounds or halogenation
of the anilines or acetanilides and subsequent re-cleavage.
[0219] The compounds of the formula (XXI) are known compounds of
organic chemistry. Copper(II) chloride and vinylidene chloride have
been known for a long time and are commercially available.
[0220] The substituted cyclic aminocarboxylic acids of the formula
(XVI) are generally obtainable by the Bucherer-Bergs synthesis or
by the Strecker synthesis and are in each case obtained in these
syntheses in different isomer forms. Thus, under the conditions of
the Bucherer-Bergs synthesis, the isomers (for simplicity called
.beta. below), in which the radicals R and the carboxyl group are
equatorial are predominantly obtained, while under the conditions
of the Strecker synthesis the isomers (for simplicity called a
below) in which the amino group and the radicals R are equatorial
are predominantly obtained. 38
[0221] The compounds of the formula (XIII) and (XVI) 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)).
[0222] Furthermore, the starting materials of the formula (II)
39
[0223] in which
[0224] A, B, W, X, Y, Z and R.sup.8 are each as defined above, used
in the above process (A) can be prepared when aminonitriles of the
formula (XXII) 40
[0225] in which
[0226] A and B are each as defined above, are reacted with
substituted phenylacetyl halides of the formula (XIV) 41
[0227] in which
[0228] W, X, Y, Z and Hal are each as defined above
[0229] to give compounds of the formula (XXIII) 42
[0230] in which
[0231] A, B, W, X, Y and Z are each as defined above
[0232] and these are subsequently subjected to acid
alcoholysis.
[0233] The compounds of the formula (XXIII) are also novel. The
compounds of the formula (XXII) are also novel.
[0234] The acyl halides of the formula (III), carboxylic anhydrides
of the formula (IV), chloroformic esters or chloroformic thioesters
of the formula (V), chloromonothioformic esters or
chlorodithioformic esters of the formula (VI), sulphonyl chlorides
of the formula (VII), phosphorus compounds of the formula (VIII)
and metal hydroxides, metal alkoxides or amines of the formula (IX)
and (X) and isocyanates of the formula (XI) and carbamoyl chlorides
of the formula (XII) furthermore required as starting materials for
carrying out the processes (B), (C), (D), (E), (F), (G) and (H)
according to the invention are generally known compounds of organic
or inorganic chemistry.
[0235] The compounds of the formulae (XIV), (XVII), (XVIII), (XIX)
and (XX) are furthermore known from the patent applications cited
at the outset and/or can be prepared by the methods given therein
(cf. also DE-196 49 665 and the Applicant's German Patent
Application having file reference 19613171.5 dated 02.04.1996,
which has not yet been laid open).
[0236] The process (A) is characterized in that compounds of the
formula (II), in which A, B, 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.
[0237] 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, isopropanol,
butanol, isobutanol and tert-butanol.
[0238] 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
(=methyltrialkyl(C.sub.8-C.sub.10)ammonium chloride) or TDA 1
(=tris-(methoxyetlhoxyethlyl)-amine). It is also possible to use
alkali metals such as sodium or potassium.
[0239] 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.
[0240] 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.
[0241] The process (A) according to the invention is generally
carried out under atmospheric pressure.
[0242] 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 (up to 3
mol).
[0243] The process (B.sub..alpha.) is characterized in that
compounds of the formula (I-a) are reacted with carbonyl halides of
the formula (III), if appropriate in the presence of a diluent and
if appropriate in the presence of an acid binder.
[0244] Suitable diluents for use in the process (B.sub..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 tetralin, furthermore
halogenated hydrocarbons, such as methylene chloride, chloroform,
carbon tetrachloride, chlorobenzene and o-dichlorobenzene,
furthermore ketones, such as acetone and methyl isopropyl ketone,
additionally ethers, such as diethyl ether, tetrahydrofuran and
dioxane, furthermore, 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.
[0245] Suitable acid binders for the reaction according to the
process (Boa) 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 alkali metal
hydroxides such as sodium hydroxide and potassium hydroxide.
[0246] The reaction temperature of the process (B.sub..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.
[0247] When carrying out the process (B.sub..alpha.) according to
the invention, the starting materials of the formula (I-a) and the
carbonyl halide of the formula (III) are generally each employed in
approximately equivalent amounts. However, it is also possible to
employ a relatively large excess (up to 5 mol) of the carbonyl
halide. Work-up is carried out by customary methods.
[0248] The process (B.beta.) is characterized in that compounds of
the formula (I-a) are reacted with carboxylic anydrides of the
formula (IV), if appropriate in the presence of a diluent and if
appropriate in the presence of an acid binder.
[0249] Suitable diluents for use in the process (B.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.
[0250] The acid binders which are added in the process (B.beta.),
if appropriate, are preferably those acid binders which are also
preferred when acyl halides are used.
[0251] The reaction temperature in the process (B.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.
[0252] When carrying out the process (B.beta.) according to the
invention, the starting materials of the formula (I-a) and the
carboxylic anhydride of the formula (IV) are generally each
employed in approximately equivalent amounts. However, it is also
possible to employ a relatively large excess (up to 5 mol) of the
carboxylic anhydride. Work-up is carried out by customary
methods.
[0253] 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.
[0254] The process (C) is characterized in that compounds of the
formula (I-a) are reacted with chloroformic esters or chloroformic
thiol esters of the formula (V), if appropriate in the presence of
a diluent and if appropriate in the presence of an acid binder.
[0255] Acid binders which are suitable for the process (C)
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.
[0256] Suitable diluents for use in the process (C) according to
the invention are all solvents which are inert towards the
chloroformic esters or chloroformic thiol 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, furthermore ketones, such as acetone and
methyl isopropyl ketone, moreover ethers, such as diethyl ether,
tetrahydrofuran and dioxane, furthermore carboxylic esters, such as
ethyl acetate, additionally nitrites such as acetonitrile and also
strongly polar solvents, such as dimethylformamide, dimethyl
sulphoxide and sulpholane.
[0257] 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 temperature is
between -20.degree. C. and +100.degree. C., preferably between
0.degree. C. and 50.degree. C.
[0258] The process (C) according to the invention is generally
carried out under atmospheric pressure.
[0259] When carrying out the process (C) according to the
invention, the starting materials of the formula (I-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.
[0260] The process (D) according to the invention is characterized
in that compounds of the formula (I-a) are reacted with compounds
of the formula (VI) in the presence of a diluent and, if
appropriate, in the presence of an acid binder.
[0261] In the preparation process (D), approximately 1 mol of
chloromonothioformic ester or chlorodithioformic ester of the
formula (VI) per mole of starting material of the formula (I-a) is
reacted at 0 to 120.degree. C., preferably at 20 to 60.degree.
C.
[0262] Diluents which may be added, if appropriate, are all inert
polar organic solvents, such as ethers, amides, sulphones,
sulphoxides, and also halogenoalkanes.
[0263] Preference is given to using dimethyl sulphoxide,
tetrahydrofuran, dimethylformamide, ethyl acetate or methylene
chloride.
[0264] If, in a preferred embodiment, the enolate salt of the
compounds of the formula (I-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.
[0265] Suitable bases for use in the process (D) 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).
[0266] 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.
[0267] The process (E) according to the invention is characterized
in that compounds of the formula (I-a) are in each case reacted
with sulphonyl chlorides of the formula (VII), if appropriate in
the presence of a diluent and if appropriate in the presence of an
acid binder.
[0268] In the preparation process (E), approximately 1 mol of
sulphonyl chloride of the formula (IX) per mole of starting
material of the formula (I-a) is reacted at -20 to 150.degree. C.,
preferably at 0 to 70.degree. C.
[0269] The process (E) is preferably carried out in the presence of
a diluent.
[0270] 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.
[0271] Preference is given to using dimethyl sulphoxide,
tetrahydrofuran, dimethylformamide, ethyl acetate, methylene
chloride.
[0272] If, in a preferred embodiment, the enolate salt of the
compounds of the formula (I-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.
[0273] If acid binders are used, then customary inorganic or
organic bases are suitable, examples being sodium hydroxide, sodium
carbonate, potassium carbonate, pyridine and triethylamine.
[0274] 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.
[0275] The process (F) according to the invention is characterized
in that compounds of the formula (I-a) are in each case reacted
with phosphorus compounds of the formula (VIII), if appropriate in
the presence of a diluent and if appropriate in the presence of an
acid binder.
[0276] In the preparation process (F), 1 to 2, preferably 1 to 1.3,
mol of the phosphorus compound of the formula (VIII) are reacted
per mole of the compounds of the formula (I-a) at temperatures
between -40.degree. C. and 150.degree. C., preferably between -10
and 110.degree. C., in order to obtain compounds of the formula
(I-e).
[0277] The process (F) is preferably carried out in the presence of
a diluent.
[0278] Suitable diluents are all inert, polar organic solvents such
as ethers, carboxylic esters, halogenated hydrocarbons, ketones,
amides, nitrites, sulphones, sulphoxides, etc.
[0279] Preference is given to using acetonitrile, dimethyl
sulphoxide, tetrahydrofuran, dimethylformamide, methylene
chloride.
[0280] 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.
[0281] 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 "incipient distillation", i.e. removal of the volatile
components under reduced pressure.
[0282] The process (G) is characterized in that compounds of the
formula (I-a) are in each case reacted with metal hydroxides or
metal alkoxides of the formula (IX) or amines of the formula (X),
if appropriate in the presence of a diluent.
[0283] Diluents which are preferred for use in the process (G)
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 (G) 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.
[0284] The process (H) according to the invention is characterized
in that compounds of the formula (I-a) are in each case reacted
with (H.alpha.) compounds of the formula (XI), if appropriate in
the presence of a diluent and if appropriate in the presence of a
catalyst, or (H.beta.) with compounds of the formula (XII), if
appropriate in the presence of a diluent and if appropriate in the
presence of an acid binder.
[0285] In the preparation process (H.alpha.), approximately 1 mol
of isocyanate of the formula (XI) is reacted per mole of starting
material of the formula (I-a) at 0 to 100.degree. C., preferably at
20 to 50.degree. C.
[0286] The process (H.alpha.) is preferably carried out in the
presence of a diluent.
[0287] Suitable diluents are all inert organic solvents, such as
aromatic hydrocarbons, halogenated hydrocarbons, ethers, amides,
nitrites, sulphones or sulphoxides.
[0288] 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.
[0289] The process is preferably carried out under atmospheric
pressure.
[0290] In the preparation process (H.beta.), approximately 1 mol of
carbamoyl chloride of the formula (XIII) is reacted per mole of
starting material of the formula (I-a) at 0 to 150.degree. C.,
preferably at 20 to 70.degree. C.
[0291] Diluents which may be added, if appropriate, are all inert
polar organic solvents such as ethers, carboxylic esters, nitriles,
ketones, amides, suiplhones sulphoxides or halogenated
hydrocarbons.
[0292] Preference is given to using dimethyl sulphoxide,
tetrahydrofuran, dimethylformamide or methylene chloride.
[0293] If, in a preferred embodiment, the enolate salt of the
compounds of the formula (I-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.
[0294] If acid binders are employed, then customary inorganic or
organic bases are suitable, examples including sodium hydroxide,
sodium carbonate, potassium carbonate, triethylamine or
pyridine.
[0295] 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.
[0296] The active compounds are suitable for controlling animal
pests, preferably arthropods and nematodes, in particular insects
and arachnids, which are encountered in agriculture, in forests, 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:
[0297] From the order of the Isopoda, for example, Oniscus asellus,
Armadillidium vulgare and Porcelijo scaber.
[0298] From the order of the Diplopoda, for example, Blaniulus
guttulatus.
[0299] From the order of the Chilopoda, for example, Geophilus
carpophagus and Scutigera spec.
[0300] From the order of the Symphyla, for example, Scutigerella
innaculata.
[0301] From the order of the Thysanura, for example, Lepisma
saccharina.
[0302] From the order of the Collembola, for example, Onychiurus
arnatus.
[0303] From the order of the Orthoptera, for example, Blatta
orientalis, Periplaneta americana, Leucophaea maderae, Blattella
germanica, Acheta domesticus, Gryllotalpa spp., Locusta migratoria
migratorioides, Melanoplus differentialis and Schistocerca
gregaria.
[0304] From the order of the Dermaptera, for example, Forficula
auricularia.
[0305] From the order of the Isoptera, for example, Reticulitermes
spp.
[0306] From the order of the Anoplura, for example, Phylloxera
vastatrix, Pemphigus spp., Pediculus humanus corporis, Haematopinus
spp. and Linognathus spp.
[0307] From the order of the Mallophaga, for example, Trichodectes
spp. and Damalinea spp.
[0308] From the order of the Thysanoptera, for example,
Frankliniella occidentalis, Hereinothrips femoralis, Thrips palmi,
and Thrips tabaci.
[0309] From the order of the Heteroptera, for example, Eurygaster
spp., Dysdercus intermedius, Piesma quadrata, Cimex lectularius,
Rhodnius prolixus and Triatoma spp.
[0310] From the order of the Homoptera, for example, Aleurodes
brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis
gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Aphis fabae,
Doralis pomi, Eriosoma lanigerum, Hyalopterus arundinis,
Macrosiphum avenae, Myzus spp., Phorodon humuli, Rhopalosiphum
padi, Empoasca spp., Euscelis bilobatus, Nephotettix cincticeps,
Lecanium comi, Saissetia oleac, Laodelphax striatellus, Nilaparvata
lugens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp.
and Psylla spp.
[0311] From the order of the Lepidoptera, for example, Pectinophora
gossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletis
blancardella, Hyponomeuta padella, Plutella maculipennis,
Malacosoma neustria, Euproctis chrysorrhoea, Lymantria spp.
Bucculatrix thurberiella, Phyllocnistis citrella, Agrotis spp.,
Euxoa 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,
Hofinannophila pseudospretella, Cacoecia podana, Capua reticulana,
Choristoneura fumiferana, Clysia ambiguella, Homona magnanima and
Tortrix viridana.
[0312] 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 varivestis, Atomaria spp.,
Oryzaephilus surinamensis, Anthonomus spp., Sitophilus spp.,
Otiorrhynchus sulcatus, 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.
[0313] From the order of the Hymenoptera, for example, Diprion
spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis and Vespa
spp.
[0314] 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., Hypodenna spp., Tabanus spp.,
Tannia spp., Bibio hortulanus, Oscinella frit, Phorbia spp.,
Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae and Tipula
paludosa.
[0315] From the order of the Siphonaptera, for example, Xenopsylla
cheopis and Ceratophyllus spp.
[0316] From the order of the Arachnida, for example, Scorpio maurus
and Latrodectus mactans.
[0317] 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.
[0318] The active compounds according to the invention have high
insecticidal and acaricidal activity after foliar and soil
application.
[0319] They can be employed particularly successfully against
insects which are harmful to plants, such as, for example, against
the larvae of the mustard beetle (Phaedon cochleariae), against the
larvae of the rice green leafhopper (Nephotettix cincticeps) and
against the larvae of the green peach aphid (Myzus persicae).
[0320] The active compounds according to the invention can
furthermore be used as defoliants, desiccants, haulm killers and,
especially, as weed-killers. By weeds, in the broadest sense, there
are to be understood all plants which grow in locations where they
are undesired. Whether the substances according to the invention
act as total or selective herbicides depends essentially on the
amount used.
[0321] The dosages of the active compounds according to the
invention necessary for controlling weeds are between 0.001 and 10
kg/ha, preferably between 0.005 and 5 kg/ha.
[0322] The active compounds according to the invention can be used,
for example, in connection with the following plants:
[0323] 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, Lindemia, Lamium, Veronica, Abutilon,
Emex, Datura, Viola, Galeopsis, Papaver, Centaurea, Trifolium,
Ranunculus and Taraxacum.
[0324] Dicotyledonous crops of the genera: Gossypium, Glycine,
Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia,
Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, Cucumis and
Cucurbita.
[0325] 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.
[0326] Monocotyledonous crops of the genera: Oryza, Zea, Triticum,
Hordeum, Avena, Secale, Sorghum, Panicum, Saccharum, Ananas,
Asparagus and Allium.
[0327] 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.
[0328] The compounds are suitable, depending on the concentration,
for the total controlling of weeds, for example on industrial
terrain and rail tracks, and on paths and squares with or without
tree plantings. Equally, the compounds can be employed for
controlling weeds in perennial cultures, for example
afforestations, decorative tree plantings, orchards, vineyards,
citrus groves, nut orchards, banana plantations, coffee
plantations, tea plantations, rubber plantations, oil palm
plantations, cocoa plantations, soft fruit plantings and hop
fields, on ornamental and sports lawns and meadow areas and for the
selective controlling of weeds in annual cultures.
[0329] The active compounds according to the invention are
particularly suitable for selectively controlling monocotyledonous
weeds in dicotyledonous crops by the pre- and post-emergence
method. For example, they can be employed very successfully for
controlling harmful grasses in cotton or sugar beet.
[0330] The active compounds can be converted into the customary
formulations, such as solutions, emulsions, wettable powders,
suspensions, powders, dusting agents, pastes, soluble powders,
granules, suspension-emulsion concentrates, natural and synthetic
materials impregnated with active compound, and very fine capsules
in polymeric substances.
[0331] These formulations are produced in a known manner, for
example by mixing the active compounds with extenders, that is
liquid solvents and/or solid carriers, optionally with the use of
surface-active agents, that is emulsifying agents and/or dispersing
agents and/or foam-forming agents.
[0332] If the extender used is water, it is also possible to
employ, for example, organic solvents as auxiliary solvents.
Suitable liquid solvents are essentially: aromatics, such as
xylene, toluene or alkylnaphthalenes, chlorinated aromatics and
chlorinated aliphatic hydrocarbons, such as chlorobenzenes,
chloroethylenes or methylene chloride, aliphatic hydrocarbons, such
as cyclohexane or paraffins, for example petroleum fractions,
mineral and vegetable oils, alcohols, such as butanol or glycol as
well as their ethers and esters, ketones, such as acetone, methyl
ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly
polar solvents, such as dimethylformamide and dimethyl sulphoxide,
and also water.
[0333] As solid carriers there are suitable:
[0334] for example, ammonium salts and ground natural minerals,
such as kaolins, clays, talc, chalk, quartz, attapulgite,
montmorillonite or diatomaceous earth, and ground synthetic
minerals, such as highly disperse silica, alumina and silicates; as
solid carriers for granules there are suitable: for example,
crushed and fractionated natural rocks such as calcite, marble,
pumice, sepiolite and dolomite, and also synthetic granules of
inorganic and organic meals, and granules of organic material such
as sawdust, coconut shells, maize cobs and tobacco stalks; as
emulsifying and/or foam-forming agents there are suitable: for
example, non-ionic and anionic emulsifiers, such as polyoxyethylene
fatty acid esters, polyoxyethylene fatty alcohol ethers, for
example alkylaryl polyglycol ethers, alkyl sulphonates, alkyl
sulphates, aryl sulphonates and also protein hydrolysates; as
dispersing agents there are suitable: for example, lignin-sulphite
waste liquors and methylcellulose.
[0335] Tackifiers such as carboxymethylcellulose and natural and
synthetic polymers in the form of powders, granules or latexes,
such as gum arabic, polyvinyl alcohol and polyvinyl acetate, and
also natural phospholipids, such as cephalins and lecithins, and
synthetic phospholipids, can be used in the formulations. Other
possible additives are mineral and vegetable oils.
[0336] 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.
[0337] The formulations in general contain between 0.1 and 95% by
weight of active compound, preferably between 0.5 and 90%, and
additionally preferably extenders and/or surfactants.
[0338] 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, baits, sterilizing agents,
acaricides, nematicides, fungicides, growth-regulating substances
or herbicides. The insecticides include, for example, phosphoric
acid esters, carbamates, carboxylic acid esters, chlorinated
hydrocarbons, phenylureas, substances produced by microorganisms,
and the like.
[0339] Particularly favourable mixing partners are, for example,
the following:
[0340] Fungicides:
[0341] 2-aminobutane; 2-anilino-4-methyl-6-cyclopropyl-pyrimidine;
2',6'-dibromo-2-methyl-4'-trifluoromethoxy-4'-trifluoro-methyl-1,3-thiazo-
le-5-carboxanilide;
2,6-dichloro-N-(4-trifluoromethylbenzyl)-benzamide;
(E)-2-methoxyimino-N-methyl-2-(2-phenoxy-phenyl)-acetamide;
8-hydroxyquinoline sulphate; methyl
(E)-2-{2-[6-(2-cyanophenoxy)-pyrimidi-
n-4-yloxy]-phenyl}-3-methoxyacrylate; methyl
(E)-methoximino[alpha-(o-toly- loxy)-o-tolyl]acetate;
2-phenylphenol (OPP), aldimorph, ampropylfos, anilazine,
azaconazole,
[0342] benalaxyl, benodanil, benomyl, binapacryl, biphenyl,
bitertanol, blasticidin-S, bromuconazole, bupirimate,
buthiobate,
[0343] calcium polysulphide, captafol, captan, carbendazim,
carboxin, quinomethionate, chloroneb, chloropicrin, chlorothalonil,
chlozolinate, cufraneb, cymoxanil, cyproconazole, cyprofuram,
[0344] dichlorophen, diclobutrazol, diclofluanid, diclomezin,
dicloran, diethofencarb, difenoconazole, dimethirimol,
dimethomorph, diniconazole, dinocap, diphenylamine, dipyrithion,
ditalimfos, dithianon, dodine, drazoxolon,
[0345] edifenphos, epoxyconazole, ethirimol, etridiazole,
[0346] fenarimol, fenbuconazole, fenfuram, fenitropan, fenpiclonil,
fenpropidin, fenpropimorph, fentin acetate, fentin hydroxide,
ferbam, ferimzone, fluazinam, fludioxonil, fluoromide,
fluquinconazole, flusilazole, flusulfamide, flutolanil, flutriafol,
folpet, fosetyl-aluminium, fthalide, fuberidazole, furalaxyl,
funnecyclox, guazatine,
[0347] hexachlorobenzene, hexaconazole, hymexazol,
[0348] 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,
mancopper, mancozeb, maneb, mepanipyrim, mepronil, metalaxyl,
metconazole, methasulfocarb, methfuroxam, metiram, metsulfovax,
myclobutanil, nickel dimethyldithiocarbamate, nitrothal-isopropyl,
nuarimol,
[0349] ofurace, oxadixyl, oxamocarb, oxycarboxin,
[0350] pefurazoate, penconazole, pencycuron, phosdiphen, phthalide,
pimaricin, piperalin, polycarbamate, polyoxin, probenazole,
prochloraz, procymidone, propamocarb, propiconazole, propineb,
pyrazophos, pyrifenox, pyrimethanil, pyroquilon, quintozene
(PCNB),
[0351] sulphur and sulphur preparations,
[0352] tebuconazole, tecloftalam, tecnazene, tetraconazole,
thiabendazole, thicyofen, thiophanate-methyl, thiram,
tolclophos-methyl, tolylfluanid, triadimefon, triadimenol,
triazoxide, trichlamide, tricyclazole, tridemorph, triflumizole,
triforine, triticonazole, validamycin A, vinclozolin,
[0353] zineb, ziram
[0354] Bactericides:
[0355] bronopol, dichlorophen, nitrapyrin, nickel
dimethyldithiocarbamate, kasugamycin, octhilinon, furancarboxylic
acid, oxytetracyclin, probenazol, streptomycin, tecloftalam, copper
sulphate and other copper preparations.
[0356] Insecticides/Acaricides/Nematicides:
[0357] abamectin, AC 303 630, acephate, acrinathrin, alanycarb,
aldicarb, alphamethrin, amitraz, avermectin, AZ 60541,
azadirachtin, azinphos A, azinphos M, azocyclotin, Bacillus
thuringiensis, bendiocarb, benfuracarb, bensultap, beta-cyfluthrin,
bifenthrin, BPMC, brofenprox, bromophos A, bufencarb, buprofezin,
butocarboxin, butylpyridaben,
[0358] cadusafos, carbaryl, carbofuran, carbophenothion,
carbosulfan, cartap, CGA 157 419, CGA 184 699, chloethocarb,
chlorethoxyfos, chlorfenvinphos, chlorfluazuron, chlormuephos,
chlorpyrifos, chlorpyrifos M, cis-resmethrin, clocythrin,
clofentezine, cyanophos, cycloprothrin, cyfluthrin, cyhalothrin,
cyhexatin, cypermnethrin, cyromazine,
[0359] deltamethrin, demeton-M, demeton-S, demeton-S-methyl,
diafenthiuron, diazinon, dichlofenthion, dichlorvos, dicliphos,
dicrotophos, diethion, diflubenzuron, dimethoate, dimethylvinphos,
dioxathion, disulfoton,
[0360] edifenphos, emamectin, esfenvalerate, ethiofencarb, ethion,
ethofenprox, ethoprophos, etrimphos,
[0361] fenamiplos, fenazaquin, fenbutatin oxide, fenitrothion,
fenobucarb, fenothiocarb, fenoxycarb, fenpropathrin, fenpyrad,
fenpyroximate, fenthion, fenvalerate, fipronil, fluazinam,
flucycloxuron, flucythrinate, flufenoxuron, flufenprox,
fluvalinate, fonophos, formothion, fosthiazate, fubfenprox,
furathiocarb, HCH, heptenophos, hexaflumuron, hexythiazox,
[0362] imidacloprid, iprobenfos, isazophos, isofenphos, isoprocarb,
isoxathion, ivermectin, lambda-cyhalothrin, lufenuron,
[0363] malathion, mecarbam, mevinphos, mesulfenphos, metaldehyde,
methacrifos, methamidophos, methidathion, methiocarb, methomyl,
metolcarb, milbemectin, monocrotophos, moxidectin,
[0364] naled, NC 184, NI 25, nitenpyram,
[0365] omethoate, oxamyl, oxydemethon M, oxydeprofos,
[0366] parathion A, parathion M, permethrin, phenthoate, phorate,
phosalone, phosmet, phosphamidon, phoxim, pirimicarb, pirimiphos M,
primiphos A, profenofos, promecarb, propaphos, propoxur,
prothiofos, prothoate, pymetrozin, pyrachlophos, pyridaphenthion,
pyresmethrin, pyrethrum, pyridaben, pyrimidifen, pyriproxifen,
quinalphos,
[0367] RH 5992,
[0368] salithion, sebufos, silafluofen, sulfotep, sulprofos,
[0369] tebufenozid, tebufenpyrad, tebupirimiphos, teflubenzuron,
tefluthrin, temephos, terbam, terbufos, tetrachlorvinphos,
thiafenox, thiodicarb, thiofanox, thiomethon, thionazin,
thuringiensin, tralomethrin, triarathen, triazophos, triazuron,
trichlorfon, triflumuron, trimethacarb,
[0370] vamidothion, XMC, xylylcarb, YI 5301/5302, zetamethrin.
[0371] Herbicides:
[0372] 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 acid 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, phennedipham 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
methabenzthiazuron; hydroxylamines, such as, for example,
alloxydim, clethodim, cycloxydim, sethoxydim and tralkoxydim;
imidazolinones, such as, for example, imazethapyr, imazamethabenz,
imazapyr and imazaquin; nitriles, such as, for example, bromoxynil,
dichlobenil and ioxynil; oxyacetamides, such as, for example,
mefenacet; sulfonylureas, such as, for example, amidosulfuron,
bensulfuron-methyl, chlorimuronethyl, chlorsulfuron, cinosulfuron,
metsulfuron-methyl, nicosulfuron, primisulfuron,
pyrazosulfuron-ethyl, thifensulfliron-methyl, triasulfuron and
tribenuron-methyl; thio-carbamates, such as, for example, butylate,
cycloate, di-allate, EPTC, esprocarb, molinate, prosulfocarb,
thiobencarb and tri-allate; triazines, such as, for example,
atrazine, cyanazine, simazine, simetryn, terbutryn 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.
[0373] 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 synergists. Synergists are compounds which increase
the action of the active compounds without it being necessary for
the synergist added to be active itself.
[0374] 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.
[0375] The compounds are used in a customary manner appropriate for
the use forms.
[0376] When used against hygiene pests and pests of stored
products, the active compound has outstanding residual action on
wood and clay and a stability to alkali on limed substrates.
[0377] The active compounds according to the invention have an
action not only against plant and hygiene pests and pests of stored
products, but also in the veterinary medicine sector against animal
parasites (ectoparasites), such as hard ticks, soft ticks, mange
mites, harvest mites, flies (biting and licking), parasitic fly
larvae, lice, hair lice, bird lice and fleas. These parasites
include: From the order of the Anoplurida, for example,
Haematopinus spp., Linognathus spp., Pediculus spp., Phtirus spp.
and Solenopotes spp.
[0378] From the order of the Mallophagida and the suborders
Amblycerina and Ischnocerina, for example, Trimenopon spp., Menopon
spp., Trinoton spp., Bovicola spp., Wemeckiella spp., Lepikentron
spp., Damalina spp., Trichodectes spp., Felicola spp.
[0379] From the order of the Diptera and the suborders 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.
[0380] From the order of the Siphonapterida, for example, Pulex
spp., Ctenocephalides spp., Xenopsylla spp. and Ceratophyllus
spp.
[0381] From the order of the Heteropterida, for example, Cimex
spp., Triatoma spp., Rhodnius spp. and Panstrongylus spp.
[0382] From the order of the Blattarida, for example, Blatta
orientalis, Periplaneta americana, Blattela germarnica and Supella
spp.
[0383] From the sub-class of the Acaria (Acarida) and the orders of
the Meta- and Mesostigmata, for example, Argas spp., Omithodorus
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.
[0384] 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., Otodectes spp., Sarcoptes spp., Notoedres
spp., Knemidocoptes spp., Cytodites spp. and Laminosioptes spp.
[0385] The active compounds of the formula (I) according to the
invention are also suitable for controlling arthropods which infest
agricultural productive livestock such as, for example, cattle,
sheep, goats, horses, pigs, donkeys, camels, buffalo, rabbits,
chickens, turkeys, ducks, geese and bees, other pets, such as, for
example, dogs, cats, cage birds and aquarium fish, and also
so-called test animals, such as, for example, hamsters, guinea
pigs, rats and mice. By controlling these arthropods, mortality and
reductions in productivity (for meat, milk, wool, hides, eggs,
honey, etc.) should be diminished, so that more economic and
simpler animal husbandry is possible by use of the active compounds
according to the invention.
[0386] The active compounds according to the invention are used in
the veterinary sector in a known manner by enteral administration
in the form of, for example, tablets, capsules, potions, drenches,
granules, pastes, boli, the feed-through process and suppositories,
by parenteral administration, such as, for example, by injections
(intramuscular, subcutaneous, intravenous, intraperitoneal, etc.),
implants, by nasal administration, by dermal use in the form, for
example, of dipping or bathing, spraying, pouring on and spotting
on, washing and powdering, and also with the aid of moulded
articles containing the active compound, such as collars, ear
marks, tail marks, limb bands, halters, marking devices, etc.
[0387] When used for livestock, poultry, pets 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, directly or
after 100 to 10,000-fold dilution, or they can be used as a
chemical bath.
[0388] It has furthermore been found that the compounds of the
formula (I) according to the invention display a high insecticidal
action against insects which destroy industrial materials.
[0389] The following insects may be mentioned as examples and
preferred--but without being limiting:
[0390] Beetles, such as
[0391] 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. and Dinoderus
minutus.
[0392] Hymenopterons, such as
[0393] Sirex juvencus, Urocerus gigas, Urocerus gigas taignus and
Urocerus augur.
[0394] Termites, such as
[0395] Kalotermes flavicollis, Cryptotermes brevis, Heterotermes
indicola, Reticulitermes flavipes, Reticulitermes santonensis,
Reticulitermes lucifugus, Mastotermes darwiniensis, Zootermopsis
nevadensis and Coptotermes formosanus.
[0396] Bristletails, such as
[0397] Lepisma saccharina.
[0398] Industrial materials in the present connection are to be
understood as meaning non-living materials, such as, preferably,
plastics, adhesives, sizes, papers and cards, leather, wood and
processed wood products, and lacquers and paints.
[0399] Materials to be protected from insect damage which are quite
particularly preferred are wood and processed wood products.
[0400] Wood and processed wood products which can be protected by
the agents according to the invention or mixtures comprising these
are to be understood as meaning, for example: building timber,
wooden beams, railway sleepers, bridge components, boat gangplanks,
wooden vehicles, crates, pallets, containers, telegraph poles, wood
lagging, wooden windows and doors, plywood, chipboards, joinery or
wood products used quite generally in house construction or
building joinery.
[0401] The active compounds can be used as such or in the form of
concentrates or generally customary formulations, such as powders,
granules, solutions, suspensions, emulsions or pastes.
[0402] 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, dispersing agent and/or binder
or fixing agent, water repellant, optionally siccatives and UV
stabilizers, and if appropriate dyestuffs and pigments, and also
other processing auxiliaries.
[0403] The insecticidal compositions or concentrates used for
preservation of wood and derived timber products comprise the
active compound according to the invention in a concentration of
0.0001 to 95% by weight, in particular 0.001 to 60% by weight.
[0404] The amount of composition or concentrate employed depends on
the nature and the occurrence of the insects and on the medium. The
optimum amount employed for the use can in each case be determined
by a series of tests. In general, however, it is sufficient 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 preserved.
[0405] The solvent and/or diluent used is an organochemical solvent
or solvent mixture and/or an oily or oil-like 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.
[0406] The organochemical solvents employed are preferably oily or
oil-like solvents having an evaporation number above 35 and a flash
point above 30.degree. C., preferably above 45.degree. C.
Corresponding mineral oils or aromatic fractions thereof or solvent
mixtures containing mineral oil, preferably white spirit, petroleum
and/or alkylbenzene, are used as such water-insoluble, oily and
oil-like solvents of low volatility.
[0407] Mineral oils having a boiling range from 170 to 220.degree.
C., white spirit having a boiling range from 170 to 220.degree. C.,
spindle oil having a boiling range from 250 to 350.degree. C.,
petroleum or aromatics having a boiling range from 160 to
280.degree. C., terpentine oil and the like are advantageously
employed.
[0408] In a preferred embodiment, liquid aliphatic hydrocarbons
having a boiling range from 180 to 210.degree. C. or high-boiling
mixtures of aromatic and aliphatic hydrocarbons having a boiling
range from 180 to 220.degree. C. and/or spindle oil and/or
monochloronaphthalene, preferably monochloronaphthalene, are
employed.
[0409] The organic oily or oil-like solvents of low volatility
having an evaporation number above 35 and a flash point above
30.degree. C., preferably above 45.degree. C., can be replaced in
part by organochemical solvents of high or medium volatility,
provided that the solvent mixture likewise has an evaporation
number above 35 and a flash point above 30.degree. C., preferably
above 45.degree. C., and that the insecticide/fungicide mixture is
soluble or can be emulsified in this solvent mixture.
[0410] According to a preferred embodiment, some of the
organochemical solvent or solvent mixture is replaced by an
aliphatic polar organochemical solvent or solvent mixture.
Aliphatic organochemical solvents containing hydroxyl and/or ester
and/or ether groups, such as, for example, glycol ethers, esters or
the like, are preferably used.
[0411] Organochemical binders which are used within the context of
the present invention are the synthetic resins and/or binding
drying oils which are water-dilutable and/or soluble or dispersible
or emulsifiable in the organochemical solvents employed and are
known per se, in particular binders consisting 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, phenolic
resin, hydrocarbon resin, such as indene-coumarone resin or
silicone resin, drying plant and/or drying oils and/or binders
which dry by physical means and are based on a naturally occurring
and/or synthetic resin.
[0412] The synthetic resin used as the binder can be employed in
the form of an emulsion, dispersion or solution. Bitumen or
bituminous substances can also be used as binders in an amount of
up to 10% by weight. In addition, dyestuffs, pigments,
water-repellant agents, odour correctants and inhibitors or
corrosion prevention agents and the like which are known per se can
be employed.
[0413] Preferably, according to the invention, the composition or
concentrate comprises at least one alkyd resin or modified alkyd
resin and/or one drying plant oil as an organochemical binder.
Alkyd resins having an oil content of more than 45% by weight,
preferably 50 to 68% by weight, are preferably used according to
the invention.
[0414] All or some of the binder mentioned can be replaced by a
fixing agent (mixture) or a plasticizer (mixture). These additives
are intended to prevent evaporation of the active compounds and
crystallization or precipitation They preferably replace 0.01 to
30% of the binder (based on 100% of the binder employed).
[0415] The plasticizers originate from the chemical classes of
phthalic acid esters, such as dibutyl, dioctyl or benzyl butyl
phthalate, phosphoric acid esters, such as tributyl phosphate,
adipic acid esters, such as di-(2-ethylhexyl) adipate, stearates,
such as butyl stearate or amyl stearate, oleates, such as butyl
oleate, glycerol ethers or higher molecular weight glycol ethers,
glycerol esters and p-toluenesulphonic acid esters.
[0416] Fixing agents are based chemically on polyvinyl alkyl
ethers, such as, for example, polyvinyl methyl ether, or ketones,
such as benzophenone or ethylenebenzophenone.
[0417] Water in particular is also a possible solvent or diluent,
if appropriate mixed with one or more of the abovementioned
organochemical solvents or diluents, emulsifiers and dispersing
agents.
[0418] Particularly effective wood preservation is achieved by
impregnation processes on a large industrial scale, for example
vacuum, double vacuum or pressure processes.
[0419] If appropriate, the ready-to-use compositions can also
comprise other insecticides, and if appropriate also one or more
fungicides.
[0420] Possible additional admixing partners are, preferably, the
insecticides and fungicides mentioned in WO 94/29 268. The
compounds mentioned in this document are an express constituent of
the present application.
[0421] Especially preferred admixing partners can be 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, dichlorfluanid,
tolylfluanid, 3-iodo-2-propinyl butylcarbamate,
N-octyl-isothiazolin-3-one and
4,5-dichloro-N-octylisothiazolin-3-one.
[0422] The preparation and the use of the active compounds
according to the invention can be seen from the following
examples.
EXAMPLE (I-a-1)
[0423] 43
[0424] At reflux temperature, 24.8 g of the compound of Example
(II-2) in 150 ml of anhydrous toluene are added dropwise to 18.4 g
(0.16 mol) of potassium tert-butoxide in 63 ml of anhydrous
tetrahydrofuran (THF), and the mixture is stirred at reflux for
another 1.5 hours. 240 ml of water are then added, the phases are
separated and the toluene phase is extracted with water. The
combined aqueous phases are washed with toluene and, at 10 to
20.degree. C., acidified with approximately 26 ml of conc.
hydrochloric acid. The precipitated solid is filtered off with
suction, washed and dried. For purification, the product is stirred
in a mixture of methyl tert-butyl ether (MTB ether) and
n-hexane.
[0425] Yield 15.6 g (69% of theory), m.p.: >220.degree. C.
[0426] Similar to this method, and/or according to the general
preparation procedures, the following compounds of the formula
(I-a) are obtained:
2TABLE 2 (I-a) 44 Ex. m.p. No. W X Y Z A B .degree. C. isomer I-a-2
CH.sub.3 CH.sub.3 CH.sub.3 H CH.sub.3 H 195 .alpha. I-a-3 H
CH.sub.3 CH.sub.3 H CH.sub.3 H 164 .alpha. I-a-4 H CH.sub.3
CH.sub.3 H CH.sub.3 H 196 .beta. I-a-5 C.sub.2H.sub.5
C.sub.2H.sub.5 CN H CH.sub.3 H 242 .beta. I-a-6 H Cl Cl H CH.sub.3
H >220 .beta. I-a-7 H Cl CH.sub.3 H CH.sub.3 H 194 .beta. I-a-8
Cl CH.sub.3 Cl H CH.sub.3 H >220 B I-a-9 Cl Cl CH.sub.3 H
CH.sub.3 H 211 .beta. I-a-10 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3
CH.sub.3 H >220 .beta. I-a-11 H CH.sub.3 Cl H CH.sub.3 H >220
.beta. I-a-12 CH.sub.3 CH.sub.3 CN H CH.sub.3 H >220 .beta.
I-a-13 CH.sub.3 CH.sub.3 H Cl CH.sub.3 H 210 .beta. I-a-14 H
CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H >220 .beta. I-a-15 H Cl Br
H CH.sub.3 H >220 .beta. I-a-16 CH.sub.3 CH.sub.3 Cl H CH.sub.3
H 211 .beta. I-a-17 CH.sub.3 CN CH.sub.3 H CH.sub.3 H >220
.beta. I-a-18 CH.sub.3 CH.sub.3 Br H CH.sub.3 H >220 .beta.
I-a-19 Br CH.sub.3 Cl H CH.sub.3 H 210 .beta. I-a-20 H CH.sub.3 H
CH.sub.3 CH.sub.3 H >220 .beta. I-a-21 Br Br C.sub.2H.sub.5 H
CH.sub.3 H >220 .beta. I-a-22 H Cl C.sub.2H.sub.5 H CH.sub.3 H
>220 .beta. I-a-23 CH.sub.3 CH.sub.3 CH.sub.3 H CH.sub.3
CH.sub.3 >220 .alpha. I-a-24 H CH.sub.3 CH.sub.3 H CH.sub.3
CH.sub.3 >220 .alpha. I-a-25 H Cl Cl CH.sub.3 CH.sub.3 H >240
.beta. I-a-26 H Cl CH.sub.3 Cl CH.sub.3 H >236 .beta. I-a-27 H
CH.sub.3 Cl CH.sub.3 CH.sub.3 H >227 .beta. I-a-28 H Br CH.sub.3
Br CH.sub.3 H >240 .beta. I-a-29 H CH.sub.3 Cl Cl CH.sub.3 H 206
.beta. I-a-30 Br Br i-C.sub.3H.sub.7 H CH.sub.3 H 233 .beta. I-a-31
Cl Cl Cl H CH.sub.3 H >234 .beta.
EXAMPLE (I-b-1)
[0427] 45
[0428] 2.52 mol (18 mmol) of triethylamine are added to 3.62 g of
the compound of Example (I-a-1) in 70 ml of anhydrous methylene
chloride. At 0 to 10.degree. C., 1.9 ml (18 mmol) of isobutyryl
chloride in 5 ml of anhydrous methylene chloride are added to this
mixture, and stirring is continued at room temperature until the
reaction has ended. The mixture is then washed twice with 50 ml of
0.5 N NaOH each time, dried and concentrated. The residue is
recrystallized from MTB ether/n-hexane.
[0429] Yield 1.6 g (35% of theory), m.p.: 209.degree. C.
[0430] Similar to this method, and/or according to the general
preparation procedures, the following compounds of the formula
(I-b) are obtained:
3TABLE 3 (I-b) 46 Ex. m.p. No. W X Y Z A B R.sup.1 .degree. C.
isomer I-b-2 CH.sub.3 CH.sub.3 CH.sub.3 H CH.sub.3 H CH.sub.3 176
.alpha. I-b-3 CH.sub.3 CH.sub.3 CH.sub.3 H CH.sub.3 H
i-C.sub.3H.sub.7 187 .alpha. I-b-4 H CH.sub.3 CH.sub.3 H CH.sub.3 H
i-C.sub.3H.sub.7 .alpha..sup.1) I-b-5 CH.sub.3 CH.sub.3 CH.sub.3 H
CH.sub.3 H CH.sub.3 187 .beta. I-b-6 H CH.sub.3 CH.sub.3 H CH.sub.3
H CH.sub.3 181 .beta. I-b-7 H CH.sub.3 CH.sub.3 H CH.sub.3 H
i-C.sub.3H.sub.7 211 .beta. I-b-8 H Cl CH.sub.3 H CH.sub.3 H
i-C.sub.3H.sub.7 155 .beta. I-b-9 Cl Cl CH.sub.3 H CH.sub.3 H
i-C.sub.3H.sub.7 178 .beta. I-b-10 CH.sub.3 Cl Cl H CH.sub.3 H
i-C.sub.3H.sub.7 204 .beta. I-b-11 CH.sub.3 CH.sub.3 CH.sub.3
CH.sub.3 CH.sub.3 H i-C.sub.3H.sub.7 >220 .beta. I-b-12 CH.sub.3
CH.sub.3 CN H CH.sub.3 H i-C.sub.3H.sub.7 214 .beta. I-b-13
CH.sub.3 C.sub.3 CN H CH.sub.3 H t-C.sub.4H.sub.9--CH.sub.2 >220
.beta. I-b-14 H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H
i-C.sub.3H.sub.7 210 .beta. I-b-15 H Cl Br H CH.sub.3 H
i-C.sub.3H.sub.7 170 .beta. I-b-16 H Cl Br H CH.sub.3 H
t-C.sub.4H.sub.9--CH.sub.2 194 .beta. I-b-17 H CH.sub.3 Cl H
CH.sub.3 H i-C.sub.3H.sub.7 178 .beta. I-b-18 CH.sub.3 CN CH.sub.3
H CH.sub.3 H i-C.sub.3H.sub.7 214 .beta. I-b-19 CH.sub.3 CN
CH.sub.3 H CH.sub.3 H t-C.sub.4H.sub.9--CH.sub.2 >220 .beta.
I-b-20 CH.sub.3 CH.sub.3 Br H CH.sub.3 H i-C.sub.3H.sub.7 >220
.beta. I-b-21 CH.sub.3 CH.sub.3 Br H CH.sub.3 H
t-C.sub.4H.sub.9--CH.sub.- 2 >220 .beta. I-b-22 H Cl
C.sub.2H.sub.5 H CH.sub.3 H i-C.sub.3H.sub.7 179 .beta. I-b-23 H Cl
C.sub.2H.sub.5 H CH.sub.3 H 47 152 .beta. I-b-24 H CH.sub.3
CH.sub.3 CH.sub.3 CH.sub.3 H 48 170 .beta. I-b-25 CH.sub.3 CH.sub.3
Cl H CH.sub.3 H i-C.sub.3H.sub.7 160 .beta. I-b-26 CH.sub.3
CH.sub.3 Cl H CH.sub.3 H s-C.sub.4H.sub.9 200 .beta. I-b-27 H
CH.sub.3 H CH.sub.3 CH.sub.3 H i-C.sub.3H.sub.7 193 .beta. I-b-28
CH.sub.3 CH.sub.3 CH.sub.3 H CH.sub.3 CH.sub.3 i-C.sub.3H.sub.7 191
.alpha. I-b-29 H Cl CH.sub.3 Cl CH.sub.3 H i-CH.sub.7 231 .beta.
I-b-30 H CH.sub.3 Cl CH.sub.3 CH.sub.3 H i-C.sub.3H.sub.7 210
.beta. I-b-31 H Br CH.sub.3 Br CH.sub.3 H i-C.sub.3H.sub.7 214-216
.beta. I-b-32 H Cl Cl CH.sub.3 CH.sub.3 H i-C.sub.3H.sub.7 202-205
.beta. I-b-33 Br Br C.sub.2H.sub.5 H CH.sub.3 H i-C.sub.3H.sub.7
217 .beta. I-b-34 CH.sub.3 CH.sub.3 Cl H CH.sub.3 H
(CH.sub.3).sub.2C.dbd.CH >248 .beta. I-b-35 Cl Cl Cl H CH.sub.3
H i-C.sub.3H.sub.7 207 .beta. I-b-36 Br Br i-C.sub.3H.sub.7 H
CH.sub.3 H i-C.sub.3H.sub.7 213 .beta. .sup.1)1H-NMR(200MHz,
CDCl.sub.3):.delta.=1.0-1.05(4s, 6H, CH(CH.sub.3).sub.2), 2.25,
2.28(25, 6H, ArCH.sub.3).
EXAMPLE (I-c-1)
[0431] 49
[0432] At 0 to 10.degree. C., 1.2 ml (12 mmol) of ethyl
chloroformate in 5 ml of anhydrous methylene chloride are added
dropwise to 3.62 g of the compound of Example (I-a-1) and 1.7 ml
(12 mmol) of triethylamine in 70 ml of anhydrous methylene
chloride, and the mixture is stirred at room temperature until the
reaction has ended. The mixture is then washed two times with 50 ml
of 0.5 N NaOH each time, dried and concentrated and the residue is
recrystallized from MTB ether/n-hexane.
[0433] Yield 2.70 g (60% of theory), m.p.: 217.degree. C.
[0434] Similar to this method, and/or according to the general
preparation procedures, the following compounds of the formula
(I-c) are obtained:
4TABLE 4 (I-c) 50 Ex. No. W X Y Z A B M R.sup.2 m.p. .degree. C.
isomer I-c-2 CH.sub.3 CH.sub.3 CH.sub.3 H CH.sub.3 H O
C.sub.2H.sub.5 201 .alpha. I-c-3 H CH.sub.3 CH.sub.3 H CH.sub.3 H O
C.sub.2H.sub.5 122 .alpha. I-c-4 H CH.sub.3 CH.sub.3 H CH.sub.3 H O
C.sub.2H.sub.5 197 .beta. I-c-5 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3
CH.sub.3 H O C.sub.2H.sub.5 211 .beta. I-c-6 CH.sub.3 CH.sub.3 CN H
CH.sub.3 H O C.sub.2H.sub.5 229 .beta. I-c-7 H CH.sub.3 CH.sub.3
CH.sub.3 CH.sub.3 H O C.sub.2H.sub.5 171 .beta. I-c-8 H Cl Br H
CH.sub.3 H O C.sub.2H.sub.5 201 .beta. I-c-9 H CH.sub.3 Cl H
CH.sub.3 H O C.sub.2H.sub.5 198 .beta. I-c-10 CH.sub.3 CN CH.sub.3
H CH.sub.3 H O C.sub.2H.sub.5 197 .beta. I-c-11 CH.sub.3 CH.sub.3
Br H CH.sub.3 H O C.sub.2H.sub.5 >220 .beta. I-c-12 H Cl Cl H
CH.sub.3 H O C.sub.2H.sub.5 171 .beta. I-c-13 H Cl C.sub.2H.sub.5 H
CH.sub.3 H O C.sub.2H.sub.5 196 .beta. I-c-14 CH.sub.3 CH.sub.3 Cl
H CH.sub.3 H O C.sub.2H.sub.5 205 .beta. I-c-15 H CH.sub.3 H
CH.sub.3 CH.sub.3 H O C.sub.2H.sub.5 185 .beta. I-c-16 CH.sub.3
CH.sub.3 CH.sub.3 H CH.sub.3 CH.sub.3 O C.sub.2H.sub.5 218 .alpha.
I-c-17 H Cl CH.sub.3 Cl CH.sub.3 H O C.sub.2H.sub.5 222 .beta.
I-c-18 H CH.sub.3 Cl CH.sub.3 CH.sub.3 H O C.sub.2H.sub.5 206
.beta. I-c-19 H Br CH.sub.3 CH.sub.3 CH.sub.3 H O C.sub.2H.sub.5
159-160 .beta. I-c-20 Br C.sub.2H.sub.5 Br H CH.sub.3 H O
C.sub.2H.sub.5 .beta.
EXAMPLE (II-1)
[0435] 51
[0436] At 30 to 40.degree. C., 27.8 g of the compound of Example
(XXIII-1) in 180 ml of methylene chloride are added dropwise to
45.4 g of concentrated sulphuric acid, and the mixture is stirred
for another 2 hours at 30 to 40.degree. C. 64 ml of anhydrous
methanol are then added dropwise, and the mixture is stirred for
another 6 hours at 40 to 70.degree. C. The mixture is then poured
onto 0.46 kg of ice and extracted with methylene chloride, and the
organic phase is washed with aqueous NaHCO.sub.3 solution, dried
and concentrated. The residue is recrystallized from MTB
ether/n-hexane.
[0437] Yield 19.80 g (64% of theory), m.p.: 101.degree. C.
EXAMPLE (II-2)
[0438] 52
[0439] At 0 to 10.degree. C., 19.6 g of mesityleneacetyl chloride
in 20 ml of anhydrous THF are added dropwise to 20.98 g of the
compound of Example (XIII-1) and 30.8 ml (0.22 mol) of
triethylamine in 200 ml of anhydrous THF, and the mixture is
stirred at room temperature until the reaction has ended. The
mixture is filtered off with suction, the filter cake is rinsed and
the filtrate is concentrated. The residue is taken up in methylene
chloride, washed with 200 ml 1 N HCl, dried and concentrated.
Silica gel column chromatography using cyclohexane/ethyl acetate
2/1 gives 24.0 g (72% of theory). .sup.1H NMR (200 MHz,
CDCl.sub.3): .delta.=1.12 (d, 3H, CH--CH.sub.3), 3.51 (.alpha.),
3.6 (.beta.) (2s, 2H, CH.sub.2, CONH, .beta./.alpha. approximately
3:1), 3.71, 3.75 (.alpha./.beta.) (2s, 3H, CO.sub.2CH.sub.3,
(.beta./.alpha. 3:1), 6.90 (.alpha.), 6.92 (.beta.) (2s, 2H,
ArH).
[0440] Similar to this method, and/or according to the general
preparation procedures, the following compounds of the formula (II)
are obtained:
5TABLE 5 (II) 53 Ex. m.p. iso- No. W X Y Z A B R.sup.8 .degree. C.
mer II-3 H CH.sub.3 CH.sub.3 H CH.sub.3 H CH.sub.3 71 .alpha. II-4
H CH.sub.3 CH.sub.3 H CH.sub.3 H CH.sub.3 .beta..sup.1) II-5
CH.sub.3 CH.sub.3 CH.sub.3 H CH.sub.3 CH.sub.3 CH.sub.3 106 .alpha.
II-6 H CH.sub.3 CH.sub.3 H CH.sub.3 CH.sub.3 CH.sub.3 96 .alpha.
II-7 C.sub.2H.sub.5 C.sub.2H.sub.5 CN H CH.sub.3 H CH.sub.3
.beta..sup.2) II-8 H Cl Cl H CH.sub.3 H CH.sub.3 .beta..sup.3) II-9
H Cl CH.sub.3 H CH.sub.3 H CH.sub.3 .beta..sup.4) II-10 CH.sub.3 Cl
Cl H CH.sub.3 H CH.sub.3 125- .beta. 127 II-11 Cl Cl CH.sub.3 H
CH.sub.3 H CH.sub.3 171 .beta. II-12 H Cl C.sub.2H.sub.5 H CH.sub.3
H CH.sub.3 .beta..sup.5) II-13 CH.sub.3 CH.sub.3 CN H CH.sub.3 H
CH.sub.3 111 .beta. II-14 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3
CH.sub.3 H CH.sub.3 150 .beta. II-15 H CH.sub.3 CH.sub.3 CH.sub.3
CH.sub.3 H CH.sub.3 122 .beta. II-16 CH.sub.3 CH.sub.3 H Cl
CH.sub.3 H CH.sub.3 159 .beta. II-17 H CH.sub.3 Cl H CH.sub.3 H
CH.sub.3 160 .beta. II-18 H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H
CH.sub.3 141 .beta. II-19 H Cl Br H CH.sub.3 H CH.sub.3 134 .beta.
II-20 CH.sub.3 Cl Br H CH.sub.3 H CH.sub.3 164 .beta. II-21
CH.sub.3 CH.sub.3 Cl H CH.sub.3 H CH.sub.3 118 .beta. II-22
CH.sub.3 CN CH.sub.3 H CH.sub.3 H CH.sub.3 135 .beta. II-23
CH.sub.3 CH.sub.3 Br H CH.sub.3 H CH.sub.3 156 .beta. II-24
CH.sub.3 Br Cl H CH.sub.3 H CH.sub.3 150 .beta. II-25 H CH.sub.3 H
CH.sub.3 CH.sub.3 H CH.sub.3 117 .beta. II-26 Br Br C.sub.2H.sub.5
H CH.sub.3 H CH.sub.3 141 .beta. II-27 Cl Cl Cl H CH.sub.3 H
CH.sub.3 156 .beta. II-28 Br Br i-C.sub.3H.sub.7 H CH.sub.3 H
CH.sub.3 126 .beta. II-29 H Cl Cl CH.sub.3 CH.sub.3 H CH.sub.3 150-
.beta. 152 II-30 H Cl CH.sub.3 Cl CH.sub.3 H CH.sub.3 118- .beta.
120 II-31 H CH.sub.3 Cl CH.sub.3 CH.sub.3 H CH.sub.3 144- .beta.
146 II-32 H Br CH.sub.3 Br CH.sub.3 H CH.sub.3 138- .beta. 140
II-33 H CH.sub.3 Cl Cl CH.sub.3 H CH.sub.3 146 .beta. .sup.1)1H
NMR(200MHz, CDCl.sub.3):1.12(d, 3H, CHCH.sub.3), 2.24(.alpha.),
2.28(.beta.), (2s, 3H, Ar-2-CH.sub.3), 2.37(s, 3H, Ar-4-CH.sub.3),
3.49(.alpha.), 3.55(.beta.), (2s, 2H, CH.sub.2-CONH), 3.62(.beta.),
3.65(.alpha.), (2s, 3H, CO.sub.2CH.sub.3,
.alpha./.beta.approximately 1:3) .sup.2)1H MNR(400MHz,
CDCl.sub.3):.delta.=1.13(.alpha.), 1.14(.beta.), (2d, 3H,
CHCH.sub.3); .alpha./.beta.approximately 1:3), 1.36(t, 6H,
(CH.sub.2CH.sub.3).sub.2), 2.70(q, 4H, (CH.sub.2--CH.sub.3).sub.2),
7.40(.alpha.), 7.42(.beta.), (2s, 2H, Ar--H,
.alpha./.beta.approximately 1:3 .sup.3)1H NMR(400MHz,
CDCl.sub.3):.delta.=1.15, 1.16 (2d, 3H, CHCH.sub.3), 3.67-3.71(3s,
5H, CH.sub.2CONH, CO.sub.2CH.sub.3), 7.21-7.32(m, 2H, ArH),
7.4-7.45(m, 1H, ArH) .sup.4)1H NMR(400MHz,
CDCl.sub.3):.delta.=1.14(d, 3H, CHCH.sub.3), 2.34(s, 3H,
ArCH.sub.3), 7.03-7.09(., 1H, Ar--H), 7.17-7.27(m, 2H, Ar--H).
.sup.5)1H NMR(400MHz, CDCl.sub.3):.delta.=1.14(2d, 3H, CHCH.sub.3),
1.23(t, 3H, CH.sub.2CH.sub.3), 2.53(q, 2H, CH.sub.2CH.sub.3),
7.08-7.12(m, 1H, ArH), 7.25-7.29(m, 2H, Ar--H).
EXAMPLE (XIII-1)
[0441] 54
[0442] At 0 to 5.degree. C., 73.2 ml (0.87 mol) of thionyl chloride
are added dropwise to 92.3 g of the compound of Example (XVI-1) in
870 ml of anhydrous methanol, and the mixture is stirred at
approximately 0.degree. C. for 30 minutes and then at approximately
40.degree. C. overnight. The mixture is filtered, the filtrate is
concentrated and the residue is stirred with a little MTB ether,
the mixture is filtered off with suction and the filter cake is
rinsed and dried.
[0443] Yield 87.0 g (86% of theory), m.p.: >220.degree. C.
EXAMPLE (XVI-1)
[0444] 55
[0445] 122.8 g of the compound of the example below and 130 g of
NaOH in 2.5 l of water are heated in an autoclave at 195.degree. C.
for 2 hours, the pressure increasing to approximately 20 bar. The
mixture is then concentrated to approximately 1/3 of its volume,
concentrated HCl is added at 0 to 10.degree. C. until the pH is 5
to 6, the mixture is concentrated, the residue is boiled with
methanol, the mixture is filtered off with suction and the filtrate
is concentrated.
[0446] Yield 92.3 g (86% of theory), m.p.: >220.degree. C.
EXAMPLE: COMPOUND OF THE FORMULA
[0447] 56
[0448] In an autoclave, a mixture comprising 76 g of
3-methyl-tetrahydropyran-4-one, 71.9 g (1.468 mol) of sodium
cyanide, 96 g (1 mol) of ammonium carbonate, 1.32 l of concentrated
ammonia solution and 1.32 l of ethanol is stirred at 120.degree. C.
for 3 hours, the internal pressure increasing to approximately 60
bar (prior to heating, 2/3 of the desired reaction pressure is
applied). The mixture is concentrated, dried with toluene, boiled
with methanol and filtered off with suction. The mother liquor is
concentrated to 400 ml, and further solid components are
precipitated by addition of MTB ether and are filtered off with
suction. The mother liquor is concentrated. The combined residues
are boiled in ethanol, the mixture is filtered off with suction (A)
and the filtrate is concentrated (B). (A) and (B) are combined.
[0449] Yield 126.0 g (100% of theory).
EXAMPLE (XXIII-1)
[0450] 57
[0451] At 0 to 10.degree. C., 21.6 g of mesitylene acetyl chloride
in 20 ml of anhydrous THF are added dropwise to 15.6 g of the
compound of Example (XXII-1) and 15.4 ml of tri-ethylamine in 220
ml of anhydrous THF, and the mixture is stirred at room temperature
until the reaction has ended. The mixture is stirred into 0.6 l of
ice-water and 0.2 l of 1 N HCl and filtered off with suction, and
the residue is taken up in methylene chloride. The solution is
dried and concentrated and the residue is recrystallized from MTB
ether/n-hexane.
[0452] Yield 27.8 g (84% of theory), m.p.: 121.degree. C.
[0453] Similar to this method, and/or according to the general
preparation procedures, the following compounds of the formula
(XXIII) are obtained:
6TABLE 6 (XXIII) 58 Ex. No. W X Y Z A B m.p. .degree. C. XXIII-2 H
CH.sub.3 CH.sub.3 H CH.sub.3 H 112 XXIII-3 CH.sub.3 CH.sub.3
CH.sub.3 H CH.sub.3 CH.sub.3 127 XXIII-4 H CH.sub.3 CH.sub.3 H
CH.sub.3 CH.sub.3 118
EXAMPLE (XIV-1)
[0454] 59
[0455] At 70.degree. C., 99.3 g of 2-chloro-4-ethylphenylacetic
acid and 109 ml (1.5 mol) of thionyl chloride are stirred until the
evolution of gas has ended. Excess thionyl chloride is removed at
50.degree. C. under reduced pressure. The residue is distilled.
[0456] Yield 99.10 g (91% of theory), b.p. 121.degree. C./0-35
mbar.
EXAMPLE (XVII-1)
[0457] 60
[0458] 102.5 g (16.9% strength, 0.05 mol) of the compound of
Example (XVIII-1), 14.1 g of KOH, 17.8 ml of water and 35.5 ml of
methanol are heated together under reflux for 5 hours. The mixture
is then concentrated and the residue is taken up in water. The
solution is washed with ethyl acetate and the aqueous phase is
acidified using conc. HCl (pH 1). The precipitate is filtered off
with suction and dried.
[0459] Yield 14.4 g (80.6% of theory), m.p.: 140-142.degree. C.
[0460] Similar to this method, and/or according to the general
preparation procedures, the following compounds of the formula
(XVII) are obtained:
7TABLE 7 (XVII) 61 Ex. No. W X Y Z m.p. .degree. C. XVII-2 Br Cl
C.sub.2H.sub.5 H 147 XVII-3 Cl Cl C.sub.2H.sub.5 H 146 XVII-4 H Cl
C.sub.2H.sub.5 H 89-91 XVII-5 H Br C.sub.2H.sub.5 H 109 XVII-6 Br
Br i-C.sub.3H.sub.7 H 154-155 XVII-7 H CH.sub.3 Cl Cl 103
EXAMPLE (XVIII-1)
[0461] 62
[0462] With cooling, 9.1 ml of 30% strength sodium methoxide are
added dropwise to 5 g (94.4% strength, 0.0119 mol) of the compound
of Example (XIX-1) in 5 ml of methanol, and the mixture is stirred
under reflux for 5 hours. After cooling, 0.01 ml of concentrated
sulphuric acid are added dropwise, and the mixture is stirred under
reflux for 1 hour. The mixture is then concentrated and the residue
is taken up in water. The solution is extracted with methylene
chloride, dried and concentrated.
[0463] Yield 1.80 g (43% of theory), oil.
[0464] Similar to this method, and/or according to the general
preparation procedures, the following compounds of the formula
(XVIII) are obtained:
8TABLE 8 (XVIII) 63 Ex. No. W X Y Z R.sup.8 b.p. .degree. C. (mbar)
XVIII-2 Br Cl C.sub.2H.sub.5 H CH.sub.3 105 0.06 XVIII-3 Cl Cl
C.sub.2H.sub.5 H CH.sub.3 92-94 0.05 XVIII-4 H Cl C.sub.2H.sub.5 H
CH.sub.3 82 0.03 XVIII-5 H Br C.sub.2H.sub.5 H CH.sub.3 135 0.15
XVIII-6 Br Br i-C.sub.3H.sub.7 H CH.sub.3 oil* XVIII-7 H CH.sub.3
Cl Cl CH.sub.3 oil* *After chromatographic purification, these
compounds were directly reacted to give the corresponding acids of
the formulae (XVII-6) and (XVII-7).
EXAMPLE (XIX-1)
[0465] 64
[0466] 1400 ml (17.4 mol) of 1,1-dichloroethane and then 320 g
(1.147 mol) of the compound of Example (XX-1) in 342 ml of
anhydrous acetonitrile are added dropwise to 208 ml (1.746 mol) of
butyl nitrite in 684 ml of anhydrous acetonitrile. The mixture is
stirred at room temperature overnight and then poured into 4.6 l of
20% strength HCl. The mixture is extracted with MTB ether and the
organic phase is washed with 2 l of water, dried and
concentrated.
[0467] Yield 434 g. The crude product reacted further without any
further purification.
[0468] Similar to this method, and/or according to the general
preparation procedures, the following compounds of the formula
(XIX) are obtained:
9TABLE 9 (XIX) 65 Ex. No. W X Y Z XIX-2 Br Cl C.sub.2H.sub.5 H oil*
XIX-3 Cl CI C.sub.2H.sub.5 H oil* XIX-4 H Cl C.sub.2H.sub.5 H oil*
XIX-5 H Br C.sub.2H.sub.5 H GC/MS: 314, 316, 318 12%, 14%, 12% 199
(100%) 197 (98%) XIX-6 Br Br i-C.sub.3H.sub.7 H oil* XIX-7 H
CH.sub.3 Cl Cl oil* *The crude mixtures were directly employed for
the alcoholysis for preparing the compounds of the formula
(XVIII).
EXAMPLE (XX-1)
[0469] 66
[0470] At 10-30.degree. C., 397 g (2.48 mol) of bromine in 744 ml
of glacial acetic acid are added dropwise to 150 g (1.24 mol) of
4-ethylaniline in 1990 ml of glacial acetic acid, and the mixture
is stirred at 30.degree. C. for another 3 hours. The mixture is
then diluted with water and made alkaline using 25% strength
ammonia solution. The precipitate is filtered off with suction,
taken up in methylene chloride, dried and concentrated.
[0471] Yield 320.0 g (93% of theory), m.p.: 74.degree. C.
EXAMPLE (XX-2)
[0472] Using the method of Example (XX-1) the compound of the
formula 67
[0473] is obtained
[0474] M.p.: 48.degree. C.
EXAMPLE (XXII-1)
[0475] 68
[0476] At room temperature, 30.5 g (0.27 mol) of
2-methyl-tetrahydropyran-- 4-one (preparation see further below)
are added dropwise to a mixture comprising 50.9 g (0.75 mol) of 25%
strength ammonia solution, 17.2 g (0.32 mol) of ammonium chloride
and 15.7 g (0.32 mol) of sodium cyanide in 48 ml of water and the
mixture is stirred at 45.degree. C. overnight. Customary work-up
gives 29.1 g (77% of theory) of the end product as an oil.
EXAMPLE (XXII-2)
[0477] 69
[0478] This compound is obtained in a similar manner as a brown
oil.
EXAMPLE: COMPOUND OF THE FORMULA
[0479] 70
[0480] At X (2-methyl-tetrahydropyran-4-one) At a temperature of
approximately 100.degree. C., 364.37 g of the compound of the
formula ClCH.sub.2CH.sub.2COCH.sub.2CHClCH.sub.3 (preparation see
the next example) are added dropwise over a period of approximately
75 minutes to 552.72 g (3.54 mol) of
NaH.sub.2PO.sub.4.times.2H.sub.2O and 179.7 g (1.55 mol) of 85%
strength o-phosphoric acid in 5500 ml of water, and the mixture is
stirred at 100.degree. C. for a further 8 hours.
[0481] The mixture is cooled to approximately 0.degree. C. and 10
molar NaOH is added dropwise until a pH of 5 to 6 is reached. 1500
ml of methylene chloride are added and the re-suiting salt is
filtered off with suction and the aqueous phase is extracted
3.times.with 1000 ml of methylene chloride each time. The organic
phase is dried, concentrated and distilled.
[0482] Yield: 119.6 g (55% of theory), b.p.: 62.degree. C./15
mbar.
EXAMPLE: COMPOUND OF THE FORMULA
ClCH.sub.2CH.sub.2COCH.sub.2CHClCH.sub.3
[0483] 71
[0484] At room temperature, 507.88 g of 3-chloropropionyl chloride
are added dropwise over a period of 15 minutes to 758.08 g (5.6
mol) of AlCl.sub.3 in 560 ml of methylene chloride, and 189 g (4.5
mol) of propylene are introduced into this mixture at approximately
28 to 30.degree. C. over a period of approximately 3 hours.
[0485] The reaction mixture is decanted off from excess AlCl.sub.3
and, at 0 to 10.degree. C, slowly added dropwise to a mixture of
508 ml of methylene chloride and 2032 ml of 1N HCl.
[0486] The organic phase is separated off, washed 3 times with 500
ml of water each time, dried and concentrated.
[0487] Yield: 470 g (70% of theory).
USE EXAMPLES
Example A
[0488] Myzus Test
10 Solvent: 7 parts by weight of dimethylformamide Emulsifier: 1
part by weight of alkylaryl polyglycol ether
[0489] 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.
[0490] 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.
[0491] 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.
[0492] In this test, at an exemplary active compound concentration
of 0.1%, for example the compounds of Examples I-a-9, I-a-10,
I-a-12, I-a-14, I-a-15, I-a-16, I-c-8, I-b-17, I-a-18, I-a-19,
I-a-20, I-a-21, I-c-11 and I-c-12 effected a kill of in each case
100% after 6 days.
Example B
[0493] Nephotettix Test
11 Solvent: 20 parts by weight of dimethylformamide Emulsifier: 1
part by weight of alkylaryl polyglycol ether
[0494] 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.
[0495] Rice seedlings (Oryzae sativa) are treated by being dipped
into the preparation of active compound of the desired
concentration and are populated with green rice leaf hoppers
(Nephotettix cincticeps) while the seedlings are still moist.
[0496] After the desired period of time, the kill in % is
determined. 100% means that all leaf hoppers have been killed; 0.1%
means that none of the leaf hoppers have been killed.
[0497] In this test, at an exemplary active compound concentration
of 0.1%, for example the compounds of Examples 1-b-2, I-b-4, I-c-3,
I-b-5, I-b-1, I-c-1, I-b-6, I-b-7, I-c-4, I-a-7, I-b-8, I-b-1,
I-c-5, I-c-7, I-b-17, I-c-11, I-a-22, I-b-22, I-b-23 and I-b-24
effected in each case a kill of 100% after 6 days.
Example C
[0498] Phaedon larvae Test
12 Solvent: 7 parts by weight of dimethylformamide Emulsifier: 1
part by weight of alkylaryl polyglycol ether
[0499] 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.
[0500] 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.
[0501] 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.
[0502] In this test, at an exemplary active compound concentration
of 0.1%, for example the compounds of Examples I-b-8, I-b-22,
I-b-23, I-c-13, I-b-4, I-c-3, I-a-7 and I-a-8 effected a kill of in
each case 100% after 7 days.
Example D
[0503] Spodoptera frugiperda Test
13 Solvent: 7 parts by weight of dimethylformamide Emulsifier: 1
part by weight of alkylaryl polyglycol ether
[0504] 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.
[0505] 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.
[0506] 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.
[0507] In this test, at an exemplary active compound concentration
of 0.1%, for example the compounds of Examples I-c-3, I-a-14,
I-c-15, I-a-20, I-c-13 and I-b-24 effected a kill of in each case
100% after 7 days.
Example E
[0508] Tetranychus Test (OP-Resistant/Dip Treatment)
14 Solvent: 3 parts by weight of dimethylformamide Emulsifier: 1
part by weight of alkylaryl polyglycol ether
[0509] 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.
[0510] 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.
[0511] 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.
[0512] In this test, at an exemplary active compound concentration
of 0.1%, for example the compounds of Examples I-b-2, I-b-3, I-b-4,
I-c-3, I-a-4, I-c-1, I-b-7, I-c-4, I-a-7, I-a-9 and I-b-8 had an
effect of in each case 100% after 14 days, and the compounds of
Examples I-b-15, I-b-16, I-b-17, I-b-22 and I-c-13 had this effect
at an exemplary active compound concentration of 0.02%.
Example F
[0513] Critical Concentration Test/Root-Systemic Action
15 Test insect: Aphis fabae Solvent: 4 parts by weight of acetone
Emulsifier: 1 part by weight of alkylaryl polyglycol ether
[0514] 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.
[0515] The preparation of active compound is intimately mixed with
soil. The concentration of the active compound in the preparation
is of practically no importance here, only the amount by weight of
active compound per unit volume of soil, which is given in ppm
(=mg/l), being decisive. The treated soil is transferred into pots
and these are planted with pregerminated broad beans. The active
compound can in this way be taken up from the soil by the roots of
the plants and be transported into the leaves.
[0516] To demonstrate the root-systemic effect, the leaves are
populated with the above-mentioned test animals after 7 days. After
a further 6 days, evaluation is carried out by counting or
estimating the dead animals. The root-systemic action of the active
compound is deduced from the mortality figures. It is 100% if all
the test animals have been killed and 0% if just as many test
insects are still alive as in the case of the untreated
control.
[0517] In this test, at an exemplary active compound concentration
of 20 ppm, for example the compounds of Examples I-a-1, I-b-4,
I-a-4, I-b-5, I-a-16, I-b-1, I-b-3, I-c-1, I-c-2, I-b-17, I-b-10,
I-a-16 and I-b-25 had an effect of in each case 100%.
Example G
[0518] Critical Concentration Test/Root-Systemic Action
16 Test insect: Myzus persicae Solvent: 4 parts by weight of
acetone Emulsifier: 1 part by weight of alkylaryl polyglycol
ether
[0519] 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.
[0520] The preparation of active compound is intimately mixed with
soil. The concentration of the active compound in the preparation
is of practically no importance here, only the amount by weight of
active compound per unit volume of soil, which is given in ppm
(=mg/l), being decisive. The treated soil is transferred into pots
and these are planted with peppers at the cotyledon stage. The
active compound can in this way be taken up from the soil by the
roots of the plants and be transported into the leaves.
[0521] To demonstrate the root-systemic effect, the leaves are
populated with the abovementioned test animals after 7 days. After
a further 6 days, evaluation is carried out by counting or
estimating the dead animals. The root-systemic action of the active
compound is deduced from the mortality figures. It is 100% if all
the test animals have been killed and 0% if just as many test
insects are still alive as in the case of the untreated
control.
[0522] In this test, at an exemplary active compound concentration
of 20 ppm, for example the compounds of Examples I-b-10, I-a-16 and
I-b-25 had an effect of in each case 100%.
* * * * *