U.S. patent application number 09/194994 was filed with the patent office on 2001-07-12 for 3-thiocarbamoylpyrazole derivatives as pesticides.
Invention is credited to ALIG, BERND, ANDERSCH, WOLFRAM, BERTSCH, ACHIM, BIELEFELDT, DIETMAR, ERDELEN, CHRISTOPH, LUI, NORBERT, MARHOLD, ALBRECHT, MENCKE, NORBERT, TURBERG, ANDREAS.
Application Number | 20010007876 09/194994 |
Document ID | / |
Family ID | 7813561 |
Filed Date | 2001-07-12 |
United States Patent
Application |
20010007876 |
Kind Code |
A1 |
ALIG, BERND ; et
al. |
July 12, 2001 |
3-THIOCARBAMOYLPYRAZOLE DERIVATIVES AS PESTICIDES
Abstract
The invention relates to new 3-thiocarbamoylpyrazole derivatives
of the formula (I) 1 in which Ar represents in each case optionally
substituted phenyl or pyridyl, R.sup.1 represents H.sub.2N--CS--
and R.sup.2 and R.sup.3 are as defined in the description, to a
plurality of processes for their preparation and to their use as
pesticides.
Inventors: |
ALIG, BERND; (LEVERKUSEN,
DE) ; BERTSCH, ACHIM; (LEVERKUSEN, DE) ;
BIELEFELDT, DIETMAR; (LEVERKUSEN, DE) ; LUI,
NORBERT; (LEVERKUSEN, DE) ; MARHOLD, ALBRECHT;
(LEVERKUSEN, DE) ; ERDELEN, CHRISTOPH;
(LEVERKUSEN, DE) ; ANDERSCH, WOLFRAM; (LEVERKUSEN,
DE) ; TURBERG, ANDREAS; (LEVERKUSEN, DE) ;
MENCKE, NORBERT; (LEVERKUSEN, DE) |
Correspondence
Address: |
PATENT DEPARTMENT
BAYER CORPORATION
100 BAYER ROAD
PITTSBURGH
PA
152059741
|
Family ID: |
7813561 |
Appl. No.: |
09/194994 |
Filed: |
May 6, 1999 |
PCT Filed: |
November 21, 1997 |
PCT NO: |
PCT/EP97/06503 |
Current U.S.
Class: |
514/404 ;
514/406; 514/407; 548/364.1; 548/367.4; 548/371.7 |
Current CPC
Class: |
C07D 231/38 20130101;
C07D 231/44 20130101; C07D 403/04 20130101; C07D 231/18
20130101 |
Class at
Publication: |
514/404 ;
548/364.1; 548/367.4; 548/371.7; 514/407; 514/406 |
International
Class: |
A01N 043/56; C07D
231/44; C07D 43/04 |
Foreign Application Data
Date |
Code |
Application Number |
Dec 4, 1996 |
DE |
19650197.0 |
Claims
1. Compounds of the general formula (I) 37in which R.sub.1
represents H.sub.2N--CS--, R.sup.2 represents halogenoalkyl,
halogenoalkenyl or halogenoalkinyl, R.sup.3 represents hydrogen,
amino or one of the following groups: 38where R.sup.4 represents
alkyl, halogenoalkyl, alkoxyalkyl or in each case optionally
substituted phenyl or pyridyl, R.sup.5 represents hydrogen or
alkyl, R.sup.6 represents hydrogen, alkyl or in each case
optionally substituted phenyl or pyridyl and R.sup.7 represents
alkyl, alkenyl, alkinyl, formyl, alkylcarbonyl,
halogenoalkylcarbonyl or alkoxycarbonyl; Ar represents in each case
optionally substituted phenyl or pyridyl and n represents a number
0, 1 or 2:
2. Process for the preparation of compounds of the formula (I)
according to claim 1, characterized in that a) 3-cyanopyrazole
derivatives of the formula (II) 39in which Ar, R.sup.2, R.sup.3 and
n are as defined in claim 1 are reacted with hydrogen sulphide, if
appropriate in the presence of a reaction auxiliary and if
appropriate in the presence of a diluent; or b)
3-thiocarbamoylpyrazole derivatives of the formula (III) 40in which
Ar is as defined above and R.sup.3-1 represents one of the
following groups: 41where R.sup.4, R.sup.5, R.sup.6 and R.sup.7 are
as defined above are reacted with sulphenyl halides of the formula
(IV) Hal-S-R.sup.2 (IV) in which R.sup.2 is as defined above and
Hal represents halogen, if appropriate in the presence of a diluent
and if appropriate in the presence of a reaction auxiliary; or c)
the 2-thiocarbamoylpyrazole derivatives of the formula (Ia) 42in
which Ar, R.sup.2 and R.sup.3 are as defined above and which can be
obtained by process (a) or (b) are oxidized with oxidants, if
appropriate in the presence of a diluent and if appropriate in the
presence of a catalyst.
3. Compounds of the formula (III) 43in which Ar is as defined above
and R.sup.3-1 represents one of the following groups: 44where
R.sup.4, R.sup.5, R.sup.6 and R.sup.7 are as defined in claim
1.
4. Compounds of the formula (VII) 45in which Ar is as defined
above.
5. Pesticides, characterized in that they comprise at least one
compound of the formula (I) according to claim 1.
6. Use of compounds of the formula (I) according to claim 1 for
controlling pests.
7. Method of controlling pests, characterized in that compounds of
the formula (I) according to claim 1 are allowed to act on pests
and/or their environment.
8. Process for the preparation of pesticides, characterized in that
compounds of the formula (I) according to claim 1 are mixed with
extenders and/or surfactants.
9. Use of compounds of the formula (I) according to claim 1 for the
preparation of pesticides.
Description
[0001] The invention relates to new 3-thiocarbamoylpyrazole
derivatives, to a plurality of processes for their preparation, and
to their use as pesticides.
[0002] It has already been disclosed that certain substituted
1-arylpyrazoles such as, for example,
5-amino-1-[2,6-dichloro-4-(trifluor- omethyl)phenyl]-3-cyano-4-[
(trifluoro-methyl)-sulphinyl]-1H-pyrazole, exhibit a good activity
against pests (cf. for example EP-A 295 117 and EP-A 352 944).
[0003] Also described are a large number of substituted
1-arylpyrazoles which can be employed for controlling pests (cf.,
for example, EP-A 201 852, EP-A 418 016 or EP-A 0 659 745).
[0004] However, the level of action or duration of action of the
prior-art compounds is not entirely satisfactory in all fields of
application, in particular in the case of specific insects or when
low concentrations are applied.
[0005] There have now been found new 3-thiocarbamoylpyrazole
derivatives of the general formula (I) 2
[0006] in which
[0007] R.sub.1 represents H.sub.2N--CS--,
[0008] R.sup.2 represents halogenoalkyl, halogenoalkenyl or
halogenoalkinyl,
[0009] R.sup.3 represents hydrogen, amino or one of the following
groups: 3
[0010] where
[0011] R.sup.4 represents alkyl, halogenoalkyl, alkoxyalkyl or in
each case optionally substituted phenyl or pyridyl,
[0012] R.sup.5 represents hydrogen or alkyl,
[0013] R.sup.6 represents hydrogen, alkyl or in each case
optionally substituted phenyl or pyridyl and
[0014] R.sup.7 represents alkyl, alkenyl, alkinyl, formyl,
alkylcarbonyl, halogenoalkylcarbonyl or alkoxycarbonyl;
[0015] Ar represents in each case optionally substituted phenyl or
pyridyl and
[0016] n represents a number 0, 1 or 2.
[0017] It has furthermore been found that the new
3-thiocarbarnoylpyrazole derivatives of the formula (I) are
obtained when
[0018] a) 3-cyanopyrazole derivatives of the formula (II) 4
[0019] in which
[0020] Ar, R.sup.2, R.sup.3 and n are as defined above
[0021] are reacted with hydrogen sulphide, if appropriate in the
presence of a reaction auxiliary and if appropriate in the presence
of a diluent;
[0022] or
[0023] b) 3-thiocarbarnoylpyrazole derivatives of the formula (III)
5
[0024] in which
[0025] Ar is as defined above and
[0026] R.sup.3-1 represents one of the following groups: 6
[0027] where
[0028] R.sup.4, R.sup.5, R.sup.6 and R.sup.7 are as defined
above
[0029] are reacted with sulphenyl halides of the formula (IV)
Hal--S--R.sup.2 (IV
[0030] in which
[0031] R.sup.2 is as defined above and
[0032] Hal represents halogen, in particular chlorine or
bromine,
[0033] if appropriate in the presence of a diluent and if
appropriate in the presence of a reaction auxiliary;
[0034] or
[0035] c) the 2-thiocarbamoylpyrazole derivatives of the formula
(Ia) 7
[0036] in which
[0037] Ar, R.sup.2 and R.sup.3 are as defined above and which can
be obtained by process (a)
[0038] or (b)
[0039] are oxidized with oxidants, if appropriate in the presence
of a diluent and if appropriate in the presence of a catalyst.
[0040] Finally, it has been found that the new
3-thiocarbamoylpyrazole derivatives of the formula (I) have highly
pronounced biological properties and are suitable, above all, for
controlling animal pests, in particular insects, arachnids and
nematodes which occur in agriculture, in forests, in the protection
of stored products and materials and in the hygiene sector.
[0041] Formula (I) provides a general definition of the compounds
according to the invention.
[0042] Preferred substituents or ranges of the radicals given in
the formulae hereinabove and hereinbelow are illustrated in the
following text.
[0043] R.sub.1 represents H.sub.2N--CS--.
[0044] R.sup.2 preferably represents
(C.sub.1-C.sub.6)-halogenoalkyl having 1 to 12 halogen atoms;
(C.sub.2-C.sub.6)-halogenoalkenyl having 1 to 8 halogen atoms or
(C.sub.2-C.sub.6)-halogenoalkinyl having 1 to 6 halogen atoms.
[0045] R.sup.3 preferably represents hydrogen, amino or one of the
following groups: 8
[0046] where
[0047] R.sup.4 represents (C.sub.1-C.sub.6)-alkyl,
(C.sub.1-C.sub.6)-halog- enoalkyl having 1 to 3 halogen atoms,
(C.sub.1-C.sub.6)-alkoxy-(C.sub.1-C.- sub.6)-alkyl, or represents
phenyl or pyridyl, each of which is optionally monosubstituted to
trisubstituted by identical or different substituents from the
series consisting of cyano, nitro, halogen, C.sub.1-C.sub.6-alkyl,
C.sub.1-C.sub.6-alkoxy, C.sub.1-C.sub.6-alkylthio,
C.sub.1-C.sub.4-halogenoalkyl, C.sub.1-C.sub.4-halogenoalkoxy or
C.sub.1-C.sub.4-halogenoalkylthio having in each case 1 to 5
halogen atoms,
[0048] R.sup.5 represents hydrogen or (C.sub.1-C.sub.6)-alkyl,
[0049] R.sup.6 represents hydrogen, (C.sub.1-C.sub.6)-alkyl, phenyl
which is optionally monosubstituted to trisubstituted by identical
or different substituents from the series consisting of cyano,
nitro, halogen, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-alkoxy,
C.sub.1-C.sub.6-alkylthio, C.sub.1-C.sub.4-halogenoalkyl,
C.sub.1-C.sub.4-halogenoalkoxy or C.sub.1-C.sub.4-halogenoalkylthio
having in each case 1 to 5 halogen atoms or hydroxyl, or represents
pyridyl which is substituted by cyano, nitro, halogen,
C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-alkoxy,
C.sub.1-C.sub.6-alkylthio, C.sub.1-C.sub.4-halogenoalkyl,
C.sub.1-C.sub.4-halogenoalkoxy or C.sub.1-C.sub.4-halogenoalkylthio
having in each case 1 to 5 halogen atoms, and
[0050] R.sup.7 represents (C.sub.1-C.sub.6)-alkyl,
(C.sub.2-C.sub.6)-alken- yl, (C.sub.2-C.sub.6)-alkinyl, formyl,
(C.sub.1-C.sub.6)-alkylcarbonyl,
(C.sub.1-C.sub.6)-halogenoalkylcarbonyl having 1 to 6 halogen atoms
or (C.sub.1-C.sub.6)-alkoxycarbonyl.
[0051] Ar preferably represents phenyl or pyridyl, each of which is
optionally monosubstituted to trisubstituted by identical or
different substituents from the series consisting of
halogeno(C.sub.1-C.sub.6)alkyl- ,
halogeno(C.sub.1-C.sub.6)alkylthio,
halogeno(C.sub.1-C.sub.6)alkoxy, (C.sub.1-C.sub.6)alkoxy, methoxy,
hydrazino, (C.sub.1-C.sub.6)-dialkylhyd- razino, amino,
(C.sub.1-C.sub.6)alkylamino, di(C.sub.1-C.sub.6)alkylamino,
(C.sub.1-C.sub.6)alkylimino, cyano, (C.sub.1-C.sub.6)alkylthio or
the group 9
[0052] in which
[0053] R.sup.8 and R.sup.9 are identical or different and represent
hydrogen or (C.sub.1-C.sub.6)-alkyl
[0054] n preferably represents a number 0, 1 or 2.
[0055] R.sub.1 represents H.sub.2N--CS--.
[0056] R.sup.2 particularly preferably represents
(C.sub.1-C.sub.4)-haloge- noalkyl having 1 or 9 identical or
different halogen atoms from the series consisting of fluorine,
chlorine and bromine, (C.sub.2-C.sub.4)-halogenoa- lkenyl having 1
to 5 identical or different halogen atoms from the series
consisting of fluorine, chlorine or bromine or
(C.sub.2-C.sub.4)-halogeno- alkinyl having 1 to 5 identical or
different halogen atoms from the series consisting of fluorine,
chlorine and bromine.
[0057] R.sup.3 especially preferably represents hydrogen, amino or
one of the following groups: 10
[0058] where
[0059] R.sup.4 represents (C.sub.1-C.sub.4)-alkyl,
(C.sub.1-C.sub.4)-halog- enoalkyl having 1-3 halogen atoms,
(C.sub.1-C.sub.4)-alkoxy-(C.sub.1-C.sub- .2)-alkyl, or phenyl which
is optionally monosubstituted to trisubstituted by identical or
different substituents from the series consisting of hydroxyl,
cyano, nitro, halogen, C.sub.1-C.sub.4-alkyl,
C.sub.1-C.sub.4-alkoxy, C.sub.1-C.sub.2-halogenoalkyl,
C.sub.1-C.sub.2-halogenoalkoxy or C.sub.1-C.sub.2-halogenoalkylthio
having in each case 1 to 3 halogen atoms,
[0060] R.sup.5 represents hydrogen or (C.sub.1-C.sub.4)-alkyl,
[0061] R.sup.6 represents hydrogen, (C.sub.1-C.sub.4)-alkyl or, or
phenyl which is optionally monosubstituted or disubstituted by
identical or different substitutents from the series consisting of
hydroxyl, cyano, nitro, halogen, C.sub.1-C.sub.4-alkyl,
C.sub.1-C.sub.4-alkoxy, C.sub.1-C.sub.2-halogenoalkyl,
C.sub.1-C.sub.2-halogenoalkoxy or C.sub.1-C.sub.2-halogenoalkylthio
having in each case 1 to 3 halogen atoms, in particular
4-hydroxy-3-methoxy-phenyl, and
[0062] R.sup.7 represents (C.sub.1-C.sub.4)-alkyl,
(C.sub.2-C.sub.4)-alken- yl, (C.sub.2-C.sub.4)-alkinyl, formyl,
(C.sub.1-C.sub.4)-alkylcarbonyl,
(C.sub.1-C.sub.4)-halogenoalkylcarbonyl having 1 to 5 identical or
different halogen atoms from the series consisting of fluorine,
chlorine or bromine or (C.sub.1-C.sub.4)-alkoxycarbonyl.
[0063] Ar especially preferably represents phenyl or pyridyl, each
of which is optionally monosubstituted to trisubstituted by
identical or different substituents from the series consisting of
fluorine, chlorine, trifluoromethyl, trifluoromethylthio,
trifluoromethoxy, methoxy, hydrazino, dimethylhydrazino, amino,
methylamino, dimethylamnino, iminomethyl, cyano, methylthio or the
group 11
[0064] where
[0065] R.sup.8 and R.sup.9 are identical or different and represent
hydrogen or (C.sub.1-C.sub.4)-alkyl.
[0066] n especially preferably represents a number 0, 1 or 2.
[0067] R.sup.1 represents H.sub.2N--CS--.
[0068] R.sup.2 most preferably represents one of the radicals:
[0069] --CF.sub.3, --CHF.sub.2
[0070] --CF.sub.2--CH.sub.3, --CF.sub.3--CHF.sub.2,
--CF.sub.2--CHFCl,
[0071] --CH.sub.2--CF.sub.3, --CH.sub.2--CF.sub.2Cl,
[0072] --CH.sub.2--CF.sub.2--CHF.sub.2,
[0073] --CF.sub.2--CFCl--CF.sub.3,
[0074] --C(Cl)(CF.sub.3)--CF.sub.2Cl,
--C(Cl)(CF.sub.3)--CHCl--CF.sub.3,
[0075] --C(CF.sub.3).dbd.CCl.sub.2
[0076] R.sup.3 most preferably represents hydrogen, amino or one of
the groups:
[0077] --NH--CO--CH.sub.3, --NH--CO--C.sub.2H.sub.5,
--N.dbd.CH--NH.sub.2, --N.dbd.C(CH.sub.3)--NH.sub.2,
[0078] --N.dbd.CH--N(CH.sub.3).sub.2,
--N.dbd.C(CH.sub.3)--N(CH.sub.3).sub- .2, 12
[0079] --NHC.sub.2H.sub.5 or --NH--CH.sub.2--CH.dbd.CH.sub.2.
[0080] Ar most preferably represents
[0081] (1) phenyl which is disubstituted or trisubstituted by
identical or different substituents, where fluorine or chlorine
occupies the 2-position, trifluoromethyl the 4-position and
fluorine, chlorine, cyano, methoxy, methylthio, trifluoromethyl,
trifluoromethoxy, trifluoromethylthio or hydrazino the 6-position;
or
[0082] (2) a 2-pyridyl radical which is substituted in the
4-position by trifluoromethyl and in the 6-position by fluorine or
chlorine.
[0083] n most preferably represents one of the integers 0, 1 or
2.
[0084] The definitions of radicals or explanations given above or
in preferred ranges apply to the end products and analogously to
the starting materials and intermediates. These definitions of
radicals may be combined with each other as desired, that is to say
combinations between the individual preferred ranges, are also
possible.
[0085] Preferred according to the invention are those compounds of
the formula (I) in which there exists a combination of the meanings
which have been mentioned above as being preferred (preferable
meanings).
[0086] Especially preferred according to the invention are those
compounds of the formula (I) in which there exists a combination of
the meanings mentioned above as especially preferred.
[0087] Most preferred according to the invention are those
compounds of the formula (I) in which there exists a combination of
the meanings mentioned above as most preferred.
[0088] In the definitions of radicals given hereinabove and
hereinbelow, hydrocarbon radicals such as alkyl or alkenyl--also in
compounds containing heteroatoms such as alkoxy or alylthio--are in
each case straight-chain or branched, as far as this is
possible.
[0089] Preferred compounds are those of the formula (1A) 13
[0090] in which
[0091] Ar, R.sup.2 and n are as defined above.
[0092] Examples of the new 3-thiocarbamoylpyrazole derivatives are
given in Tables 1 to 60:
Table 1
[0093] 14
[0094] Compounds of Table 1 correspond to the general formula
(IB)
[0095] in which 15
[0096] R.sup.3=NH.sub.2
[0097] n=the number 0
[0098] R.sup.2=as listed below:
[0099] R.sup.2
[0100] --CF.sub.3
[0101] --CF.sub.2--CH.sub.3
[0102] --CF.sub.3--CHF.sub.2
[0103] --CF.sub.2--CHFCl
[0104] --CH.sub.2--CF.sub.3
[0105] --CH.sub.2--CF.sub.2Cl
[0106] --CH.sub.2--CF.sub.2--CHF.sub.2
[0107] --CF.sub.2--CFCl--CF.sub.3,
[0108] --C(Cl)(CF.sub.3)--CF.sub.2Cl
[0109] --C(Cl)(CF.sub.3)--CHCl--CF.sub.3
[0110] --C(CF.sub.3).dbd.CCl.sub.2
Table 2
[0111] Table 2 contains compounds of the general formula (IB)
[0112] in which 16
[0113] R.sup.2, R.sup.3 and n=as listed in Table 1.
Table 3
[0114] Table 3 contains compounds of the general formula (IB),
[0115] in which 17
[0116] R.sup.2, R.sup.3 and n=as listed in Table 1.
Table 4
[0117] Table 4 contains compounds of the general formula (IB),
[0118] in which 18
[0119] R.sup.2, R.sup.3 and n=as listed in Table 1.
Tables 5 to 8
[0120] Tables 5 to 8 contain compounds of the general formula
(IB),
[0121] in which
[0122] R.sup.3.dbd.H
[0123] Ar, R.sup.2 and n=as listed in Tables 1 to 4.
Tables 9 to 12
[0124] Tables 9 to 12 contain compounds of the general formula
(IB),
[0125] in which 19
[0126] Ar, R.sup.2 and n=as listed in Tables 1 to 4.
Tables 13 to 16
[0127] Tables 13 to 16 contain compounds of the general formula
(IB),
[0128] in which 20
[0129] Ar, R.sup.2 and n=as listed in Tables 1 to 4.
Tables 17 to 20
[0130] Tables 17 to 20 contain compounds of the general formula
(IB),
[0131] in which 21
[0132] Ar, R.sup.2 and n=as listed in Tables 1 to 4.
Tables 21 to 40
[0133] Tables 21 to 40 contain compounds of the general formula
(IB),
[0134] in which
[0135] n=the number 1
[0136] Ar, R.sup.2 and R.sup.3=as listed in Tables 1 to 20.
Tables 41 to 60
[0137] Tables 41 to 60 contain compounds of the general formula
(IB),
[0138] in which
[0139] n=the number 2
[0140] Ar, R.sup.2 and R.sup.3=as listed in Tables 1 to 20.
[0141] If, for example, 5-amino-3-cyano4-( 1,1-difluoroethylthio)-1
-(2,6-dichloro-4-tri-fluoromethylphenyl)pyrazole and hydrogen
sulphide are used as starting materials, the course of the reaction
of process (a) according to the invention can be represented by the
following equation: 22
[0142] If, for example,
1-(2,6-dichloro-4-trifluoromethylphenyl)-3-thiocar-
bamoyl-5-(pyrrol-1-yl)pyrazole and 1,1-difluoroethylsulphenyl
chloride are used as starting materials, the course of the reaction
of process (b) according to the invention can be represented by the
following equation: 23
[0143] If, for example,
5-(pyrrol-1-yl)-3-thiocarbamoyl-4-(1,1-difluoroeth-
ylthio)-1-(2,6-di-chloro-4-trifluoromethylphenyl)pyrazole and
hydrogen sulphide are used as starting materials, the course of the
reaction of process (c) can be represented by the following
equation: 24
[0144] The 3-cyanopyrazole derivatives of the formula (II), which
are to be used as starting materials for carrying out process (a)
according to the invention, have been disclosed (cf., for example,
EP-A 0 295 117 and EP-A 0 659 745) and/or can be prepared
analogously to known processes.
[0145] The 3-thiocarbamoylpyrazole derivatives of the formula
(III), which are to be used as starting materials for carrying out
process (b) according to the invention, are new and also an object
of the invention.
[0146] The compounds of the formula (III) can be obtained by
reacting 2-cyanopyrazoles of the formula (V) 25
[0147] in which
[0148] Ar and R.sup.3-1 are as defined above
[0149] with hydrogen sulphide in accordance with process (a)
according to the invention, if appropriate in the presence of a
reaction auxiliary and if appropriate in the presence of a
diluent.
[0150] The 3-cyanopyrazoles of the formula (V) are known and/or can
be obtained in a known manner, for example by derivatizing the
corresponding 5-amino-3-cyanopyrazoles of the formula (VI) 26
[0151] in which
[0152] Ar is as defined above
[0153] on the amino group in the customary manner (cf., for
example, EP-A 0 659 745).
[0154] Alternatively, the compounds of the formula (III) can be
obtained by derivatizing 5-amino-3-thiocarbamoylpyrazoles of the
formula (VII) 27
[0155] in which
[0156] Ar is as defined above
[0157] on the amino group in the customary manner (cf., for
example, EP-A 0 659 745).
[0158] The 5-amino-3-thiocarbamoylpyrazoles of the formula (VII)
are new and also an object of the invention.
[0159] They are obtained by reacting 5-amino-3-cyanopyrazoles of
the formula (VI) with hydrogen sulphide in accordance with process
(a) according to the invention, if appropriate in the presence of a
diluent (cf. also the preparation examples).
[0160] The sulphenyl halides of the formula (IV), which are also to
be used as starting materials in process (b) according to the
invention, are generally known compounds of organic chemistry.
[0161] The 3-thiocarbamoylpyrazole derivatives of the formula (Ia)
which are to be used as starting materials for process (c)
according to the invention are compounds according to the
invention.
[0162] Process (a) according to the invention is preferably carried
out using a diluent. Suitable diluents are virtually all inert
organic solvents. These include, preferably, aliphatic and
aromatic, optionally halogenated hydrocarbons such as pentane,
hexane, heptane, cyclohexane, petroleum ether, benzine, ligroin,
benzene, toluene, xylene, methylene chloride, ethylene chloride,
chloroform, carbon tetrachloride, chlorobenzene and
o-dichlorobenzene, ethers such as diethyl ether and dibutyl ether,
glycol dimethyl ether and diglycol dimethyl ether, tetrahydrofuran
and dioxane, ketones such as acetone, methyl ethyl ketone, methyl
isopropyl ketone or methyl isobutyl ketone, esters such as methyl
acetate or ethyl acetate, nitriles such as, for example,
acetonitrile or propionitrile, amides such as, for example,
dimethylformamide, dimethylacetamide and N-methylpyrrolidone, and
also dimethyl sulphoxide, tetramethylene sulphone or
hexamethylenephosphoric triamide.
[0163] Reaction auxiliaries which may be used in process (a) are
all bases which can conventionally be used for reactions of this
type. The following are preferably suitable: basic nitrogen
compounds such as trimethylamine, triethylamine, tripropylamine,
tributylamine, diisobutylamine, dicyclohexylamine,
ethyldiisopropylamine, ethyldicyclohexylamine,
N,N-dimethylbenzylamine, N,N-dimethylaniline, pyridine, 2-methyl-,
3-methyl-, 4-methyl-, 2,4-dimethyl-, 2,6-dimethyl-, 2-ethyl-,
4-ethyl- and 5-ethyl-2-methylpyridine, 1,5-diazabicyclo[4,3,0]--
non-5-ene (DBN), 1,8-diazabicyclo[5,4,0]undec-7-ene (DBU) or
1,4-diazabicyclo-[2,2,2]octane (DABCO). It is also possible to use
an excess of reaction auxiliary as the diluent.
[0164] When carrying out process (a) according to the invention,
the reaction temperatures can be varied within a substantial range.
In general, the process is carried out at temperatures between
0.degree. C. and 100.degree. C., preferably at temperatures between
10.degree. C. and 80.degree. C.
[0165] Process (a) according to the invention is generally carried
out under atmospheric pressure. However, it is also possible to
carry out the process under elevated or reduced pressure.
[0166] To carry out process (a) according to the invention, an
excess of hydrogen sulphide is usually employed. In general, the
reactions are carried out in a suitable diluent in the presence of
a basic nitrogen compound. Work-up is carried out by customary
methods (cf. the preparation examples).
[0167] Suitable diluents for carrying out process (b) according to
the invention are inert organic solvents. These include, in
particular, aliphatic, alicyclic or aromatic, optionally
halogenated hydrocarbons such as, for example, benzine, benzene,
toluene, xylene, chlorobenzene, petroleum ether, hexane,
cyclohexane, dichloromethane, chloroform, carbon tetrachloride;
ethers such as diethyl ether, dioxane, tetrahydrofuran or ethylene
glycol dimethyl ether or ethylene glycol diethyl ether, ketones
such as acetone or butanone, nitriles such as acetonitrile or
propionitrile; amides such as dimethylformamide, dimethylacetamide,
N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoric
triamide, esters such as ethyl acetate, sulphoxides such as
dimethyl sulphoxide, or acids such as, for example, acetic
acid.
[0168] If appropriate, process (b) according to the invention can
be carried out in the presence of a reaction auxiliary. Suitable
reaction auxiliaries are all customary inorganic or organic bases.
These include, for example, alkali metal hydroxides such as sodium
hydroxide or potassium hydroxide, alkali metal carbonates or
hydrogen carbonates such as sodium carbonate, potassium carbonate
or sodium hydrogen carbonate, and tertiary amines such as
triethylamine, N,N-dimethylaniline, pyridine,
N,N-dimethylaminopyridine, diazabicyclooctane (DABCO),
diazabicyclononene (DBN) or diazabicycloundecene (DBU).
[0169] When carrying out process (b) according to the invention,
the reaction temperatures may be varied within a wide range. In
general, the process is carried out at temperatures between
-20.degree. C. and +120.degree. C., preferably at temperatures
between 0.degree. C. and +50.degree. C.
[0170] To carry out process (b) according to the invention, 1.0 to
2.5 mol, preferably 1.0 to 1.5 mol, of sulphenyl halide of the
formula (IV) and, if appropriate, 1.0 to 2.5 mol, preferably 1.0 to
1.5 mol, of reaction auxiliary are generally employed per mol of
1-arylpyrazole which is substituted in the 4-position, of the
formula (III). The reaction is carried out and the reaction
products are worked up and isolated by generally customary
processes.
[0171] Suitable oxidants for carrying out process (c) according to
the invention are all conventional oxidants which can be used for
sulphur oxidation. Especially suitable are hydrogen peroxide,
organic peracids such as, for example, peracetic acid,
m-chloroperbenzoic acid, p-nitroperbenzoic acid or atmospheric
oxygen.
[0172] Diluents which are suitable for carrying out process (c)
according to the invention are, again, inert organic solvents. The
following are preferably used: hydrocarbons such as benzine,
benzene, toluene, hexane or petroleum ether; chlorinated
hydrocarbons such as dichloromethane, 1,2-dichloroethane,
chloroform, carbon tetrachloride or chlorobenzene; ethers such as
diethyl ether, dioxane or tetrahydrofuran; carboxylic acids such as
acetic acid or propionic acid, or dipolar aprotic solvents such as
acetonitrile, acetone, ethyl acetate or dimethylformamide.
[0173] If appropriate, process (c) according to the invention can
be carried out in the presence of an acid binder. Suitable acid
binders are all organic and inorganic acid binders which can
normally be used. The following are preferably used: alkaline earth
metal hydroxides, alkaline earth metal acetates, alkaline earth
metal carbonates, alkali metal hydroxides, alkali metal acetates or
alkali metal carbonates, such as, for example, calcium hydroxcide,
sodium hydroxide, sodium acetate or sodium carbonate.
[0174] If appropriate, process (c) according to the invention can
be carried out in the presence of a suitable catalyst. Suitable
catalysts are all those which can normally be used for such sulphur
oxidations. Examples which may be mentioned are ammonium molybdate
and sodium tungstate.
[0175] When carrying out process (c) according to the invention,
the reaction temperatures can be varied within a substantial range.
In general, the process is carried out at temperatures between
-20.degree. C. and +70.degree. C., preferably at temperatures
between 0.degree. C. and +50.degree. C.
[0176] To carry out process (c) according to the invention, 0.8 to
1.2 mols, preferably equimolar amounts, of oxidant are generally
employed per mol of compound of the formula (la) if oxidation of
the sulphur is to be interrupted at the sulphoxide level. For
oxidization to the sulphone, 1.8 to 3.0 mols, preferably twice the
molar amounts, of oxidant are generally employed per mol of
compound of the formula (Ia). The reaction is carried out and the
end products are worked up and isolated by customary processes.
[0177] The active compounds are well tolerated by plants, show
advantageous toxicity to warm-blooded species and are thus suitable
for controlling animal pests, in particular insects, arachnids and
nematodes, which occur in agriculture, in forests, in the
protection of stored products and of materials, and in the hygiene
sector. They can preferably be used as crop protection agents. They
are active against normally sensitive and resistant species and
against all or individual development stages. The abovementioned
pests include:
[0178] From the order of the Isopoda, for example, Oniscus asellus,
Armadillidium vulgare and Porcellio scaber.
[0179] From the order of the Diplopoda, for example, Blaniulus
guttulatus.
[0180] From the order of the Chilopoda, for example, Geophilus
carpophagus and Scutigera spec.
[0181] From the order of the Symphyla, for example, Scutigerella
immaculata.
[0182] From the order of the Thysanura, for example, Lepisma
saccharina.
[0183] From the order of the Collembola, for example, Onychiurus
armatus.
[0184] 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.
[0185] From the order of the Dermaptera, for example, Forficula
auricularia.
[0186] From the order of the Isoptera, for example, Reticulitermes
spp.
[0187] From the order of the Anoplura, for example, Pediculus
humanus corporis, Haematopinus spp. and Linognathus spp.
[0188] From the order of the Mallophaga, for example, Trichodectes
spp. and Damalinea spp.
[0189] From the order of the Thysanoptera, for example,
Hercinothrips femoralis and Thrips tabaci.
[0190] From the order of the Heteroptera, for example, Eurygaster
spp., Dysdercus intermedius, Piesma quadrata, Cimex lectularius,
Rhodnius prolixus and Triatoma spp.
[0191] From the order of the Homoptera, for example, Aleurodes
brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis
gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Aphis fabae,
Aphis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Phylloxera
vastatrix, Pemphigus spp., Macrosiphum avenae, Myzus spp., Phorodon
humuli, Rhopalosiphum padi, Empoasca spp., Euscelis bilobatus,
Nephotettix cincticeps, Lecanium comi, Saissetia oleae, Laodelphax
striatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotus
hederae, Pseudococcus spp. and Psylla spp.
[0192] 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, Spodoptera
litura, Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella,
Pieris spp., Chilo spp., Pyrausta nubilalis, Ephestia kuehniella,
Galleria mellonella, Tineola bisselliella, Tinea pellionella,
Hofmannophila pseudospretella, Cacoecia podana, Capua reticulana,
Choristoneura fumiferana, Clysia ambiguella, Homona magnanima and
Tortrix viridana.
[0193] From the order of the Coleoptera, for example, Anobium
punctatum, Rhizopertha dominica, Bruchidius 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., Conoderus spp., Melolontha
melolontha, Amphimallon solstitialis and Costelytra zealandica.
[0194] From the order of the Hymenoptera, for example, Diprion
spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis and Vespa
spp.
[0195] 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., Stomoxys
spp., Oestrus spp., Hypoderma spp., Tabanus spp., Tannia spp.,
Bibio hortulanus, Oscinella frit, Phorbia spp., Pegomyia hyoscyami,
Ceratitis capitata, Dacus oleae and Tipula paludosa.
[0196] From the order of the Siphonaptera, for example, Xenopsylla
cheopis and Ceratophyllus spp.
[0197] From the order of the Arachnida, for example, Scorpio maurus
and Latrodectus mactans.
[0198] 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.
[0199] The plant-parasitic nematodes include, for example,
Pratylenchus spp., Radopholus similis, Ditylenchus dipsaci,
Tylenchulus semipenetrans, Heterodera spp., Globodera spp.,
Meloidogyne spp., Aphelenchoides spp., Longidorus spp., Xiphinema
spp. and Trichodorus spp.
[0200] The compounds of the formula (I) according to the invention
are distinguished, in particular, by a potent insecticidal activity
combined, in some cases, with root-systemic properties.
[0201] They can be employed particularly successfully for
controlling plant-damaging insects such as, for example, against
the mustard beetle larvae (Phaedon cochlaeriae), the caterpillars
of the diamond-back moth (Plutella maculipennis), the green rice
leafhopper (Nephotettix cinctriceps), the caterpillars of the fall
armyworm (Spodoptera frugiperda), the peach aphids (Mycus persicae)
or the larvae of the banded cucumber beetle (Diabrotica
bateata).
[0202] The active compounds can be converted into the customary
formulations such as solutions, emulsions, wettable powders,
suspensions, powders, dusts, pastes, soluble powders, granules,
suspoemulsion concentrates, natural and synthetic products
impregnated with active compound, and microencapsulations in
polymeric substances.
[0203] These formulations are prepared in the known manner, for
example by mixing the active compounds with extenders, that is to
say liquid solvents and/or solid carriers, if appropriate using
surfactants, that is to say emulsifiers and/or dispersants and/or
foam formers.
[0204] If water is used as extender, it is also possible, for
example, to use 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 mineral oil fractions, mineral and vegetable
oils, alcohols such as butanol or glycol and their ethers and
esters, ketones such as acetone, methyl ethyl ketone, methyl
isobutyl ketone or cyclohexanone, strongly polar solvents such as
dimethylformamide and dimethyl sulphoxide, and water.
[0205] Suitable solid carriers are:
[0206] for example ammonium salts and ground natural minerals such
as kaolins, clays, talc, chalk, quartz, attapulgite,
montmorillonite or diatomaceous earth, and ground synthetic
minerals such as highly disperse silica, alumina and silicates;
suitable solid carriers for granules are: for example crushed and
fractionated natural rocks such as calcite, marble, pumice,
sepiolite, dolomite, and synthetic granules of inorganic or organic
meals and granules of organic material such as sawdust, coconut
shells, maize cobs and tobacco stalks; suitable emulsifiers and/or
foam formers are: for example non-ionic and anionic emulsifiers
such as polyoxyethylene fatty acid esters, polyoxyethylene fatty
alcohol ethers, for example alkylaryl polyglycol ethers,
alkylsulphonates, alkyl sulphates, arylsulphonates and protein
hydrolysates; suitable dispersants are: for example lignin-sulphite
waste liquors and methylcellulose.
[0207] Adhesives such as carboxymethylcellulose, natural and
synthetic polymers in the form of powders, granules or lattices
such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and
natural phospholipids such as cephalins and lecithins and synthetic
phospholipids may be used in the formulations. Other additives may
be mineral and vegetable oils.
[0208] Colorants such as inorganic pigments, for example iron
oxide, titanium oxide, Prussian Blue, and organic dyestuffs such as
alizarin, azo and metal phthalocyanin dyes and micronutrients such
as salts of iron, manganese, boron, copper, cobalt, molybdenum and
zinc may be used.
[0209] In general, the formulations comprise between 0.1 and 95% by
weight of active compound, preferably between 0.5 and 90%.
[0210] In its commercially available formulations and in the use
forms prepared with these formulations, the active compound
according to the invention may be present in a mixture with other
active compounds such as insecticides, attractants, sterilants,
bactericides, acaridices, nematicides, fungicides, growth
regulators or herbicides. The insecticides include, for example,
phosphoric esters, carbamates, carboxylic esters, chlorinated
hydrocarbons, phenylureas, substances produced by microorganisms,
and the like.
[0211] Examples of particularly advantageous components in mixtures
are the following:
[0212] Fungicides:
[0213] 2-aminobutane; 2-anilino-4-methyl-6-cyclopropyl-pyrimidine;
2',6'
-dibromo-2-methyl-4'-trifluoromethoxy-4'-trifluoro-methyl-1,3-thizole-5-c-
arboxanilide; 2,6-di-chloroN-(4-trifluoromethylbenzyl)-benzamide;
(E)-2-methoxyimino-N-methyl-2-(2-phenoxyphenyl)-acetamide;
8-hydroxyquinoline sulphale; methyl
(E)-2-{2-[6-(2-cyanophenoxy)-pyrimidi- n-4-yloxy]-phenyl}
-3-methoxyacrylate; methyl (E)-methoximino[alpha-(o-tol-
yloxy)-o-tolyl]acetate; 2-phenylphenol (OPP), aldimorph,
ampropylfos, anilazine, azaconazole,
[0214] benalaxyl, benodanil, benomyl, binapacryl, biphenyl,
bitertanol, blasticidin-S, bromuconazole, bupirimate,
buthiobate,
[0215] calcium polysulphide, captafol, captan, carbendazim,
carboxin, quinomethionate, chloroneb, chloropicrin, chlorothalonil,
chlozolinate, cufraneb, cymoxanil, cyproconazole, cyprofuram,
dichlorophen, diclobutrazol, diclofluanid, diclomezin, dicloran,
diethofencarb, difenoconazole, dimethirimol, dimethomorph,
diniconazole, dinocap, diphenylamine, dipyrithion, ditalimfos,
dithianon, dodine, drazoxolon,
[0216] edifenphos, epoxyconazole, ethirimol, etridiazole,
[0217] 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,
furmecyclox,
[0218] guazatine,
[0219] hexachlorobenzene, hexaconazole, hymexazol,
[0220] 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,
[0221] mancopper, mancozeb, maneb, mepanipyrim, mepronil,
metalaxyl, metconazole, methasulfocarb, methfuroxam, metiram,
metsulfovax, myclobutanil,
[0222] nickel dimethyldithiocarbamate, nitrothal-isopropyl,
nuarimol,
[0223] ofurace, oxadixyl, oxamocarb, oxycarboxin,
[0224] pefurazoate, penconazole, pencycuron, phosdiphen, phthalide,
pimaricin, piperalin, polycarbamates, polyoxin, probenazole,
prochloraz, procymidone, propamocarb, propiconazole, propineb,
pyrazophos, pyrifenox, pyrimethanil, pyroquilon, quintozene
(PCNB),
[0225] sulphur and sulphur preparations,
[0226] tebuconazole, tecloftalam, tecnazene, tetraconazole,
thiabendazole, thicyofen, thiophanate-methyl, thiram,
tolclophos-methyl, tolylfluanid, triadimefon, triadimenol,
triazoxide, trichlamide, tricyclazole, tridemorph, triflumizole,
triforine, triticonazole,
[0227] validamycin A, vinclozolin,
[0228] zineb, ziram
[0229] Bactericides:
[0230] bronopol, dichlorophen, nitrapyrin, nickel
dimethyldithiocarbamate, kasugamycin, octhilinone, furancarboxylic
acid, oxytetracyclin, probenazole, streptomycin, tecloftalam,
copper sulphate and other copper preparations
[0231] Insecticides/Acaricides/Nematicides:
[0232] abamectin, AC 303 630, acephate, acrinathrin, alanycarb,
aldicarb, alphamethrin, amitraz, avermectin, AZ 60541,
azadirachtin, azinphos A, azinphos M, azocyclotin,
[0233] Bacillus thuringiensis, bendiocarb, benfuracarb, bensultap,
beta-cyfluthrin, bifenthrin, BPMC, brofenprox, bromophos A,
bufencarb, buprofezin, butocarboxin, butylpyridaben,
[0234] cadusafos, carbaryl, carbofuran, carbophenothion,
carbosulfan, cartap, CGA 157 419, CGA 184699, chloethocarb,
chlorethoxyfos, chlorfenvinphos, chlorfluazuron, chlormephos,
chlorpyrifos, chlorpyrifos M, cis-resmethrin, clocythrin,
clofentezine, cyanophos, cycloprothrin, cyfluthrin, cyhalothrin,
cyhexatin, cypermethrin, cyromazine,
[0235] deltamethrin, demeton-M, demeton-S, demeton-S-methyl,
diafenthiuron, diazinon, dichlofenthion, dichlorvos, dicliphos,
dicrotophos, diethion, diflubenzuron, dimethoate, dimethylvinphos,
dioxathion, disulfoton,
[0236] edifenphos, emamectin, esfenvalerate, ethiofencarb, ethion,
ethofenprox, ethoprophos, etrimphos,
[0237] fenamiphos, fenazaquin, fenbutatin oxide, fenitrothion,
fenobucarb, fenothiocarb, fenoxycarb, fenpropathrin, fenpyrad,
fenpyroximate, fenthion, fenvalerate, fipronil, fluazinam,
flucycloxuron, flucythrinate, flufenoxuron, flufenprox,
fluvalinate, fonophos, formothion, fosthiazate, fubfenprox,
furathiocarb,
[0238] HCH, heptenophos, hexaflumuron, hexythiazox,
[0239] imidacloprid, iprobenfos, isazophos, isofenphos, isoprocarb,
isoxathion, ivermectin, lambda-cyhalothrin, lufenuron,
[0240] malathion, mecarbam, mervinphos, mesulfenphos, metaldehyde,
methacrifos, methamidophos, methidathion, methiocarb, methomyl,
metolcarb, milbemectin, monocrotophos, moxidectin,
[0241] naled, NC 184, NI 25, nitenpyram,
[0242] omethoate, oxamyl, oxydemethon M, oxydeprofos,
[0243] parathion A, parathion M, permethrin, phenthoate, phorate,
phosalone, phosmet, phosphamidon, phoxim, pirimicarb, pirimiphos M,
pirimiphos A, profenofos, promecarb, propaphos, propoxur,
prothiofos, prothoate, pymetrozin, pyrachlophos, pyradaphenthion,
pyresmethrin, pyrethrum, pyridaben, pyrimidifen, pyriproxifen,
quinalphos,
[0244] salithion, sebufos, silafluofen, sulfotep, sulprofos,
[0245] tebufenozide, tebufenpyrad, tebupirimphos, teflubenzuron,
tefluthrin, temephos, terbam, terbufos, tetrachlorvinphos,
thiafenox, thiodicarb, thiofanox, thiomethon, thionazin,
thuringiensin, tralomethrin, triarathen, triazophos, triazuron,
trichlorfon, triflumuron, trimethacarb,
[0246] vamidothion, XMC, xylylcarb, YI 5301/5302, zetamethrin.
[0247] A mixture with other known active compounds, such as
herbicides, or with fertilizers and growth regulators is also
possible.
[0248] Furthermore, the active compounds according to the invention
in their commercially available formulations and in the use forms
prepared with these formulations, may be present in a mixture with
synergists. Synergists are compounds by which the activity of the
active compounds is increased without it being necessary for the
synergist added to be active itself.
[0249] The active compound content of the use forms prepared with
the commercially available formulations can vary within wide
limits. The active compound concentration of the use forms may
range from 0.0000001 to 95% by weight of active compound,
preferably between 0.0001 and 1 % by weight.
[0250] They are applied in a customary manner adapted to suit the
use forms.
[0251] When used against hygiene and stored-product pests, the
active compound is distinguished by an outstanding residual action
on wood and clay and by good stability to alkali on limed
substrates.
[0252] The active compounds according to the invention are not only
active against plant, hygiene and stored-product pests, but, in the
veterinary medicine sector, also against animal parasites
(ectoparasites) such as hard ticks, soft ticks, mange mites,
chiggers, flies (stinging and licking), parasitic fly larvae, lice,
hair lice, bird lice and fleas. These parasites include:
[0253] From the order of the Anoplurida, for example, Haematopinus
spp., Linognathus spp., Pediculus spp., Phtirus spp., Solenopotes
spp.
[0254] From the order of the Mallophagida and the suborders
Amblycerina and Ischnocerina, for example, Trimenopon spp., Menopon
spp., Trinoton spp., Bovicola spp., Werneckiella spp., Lepikentron
spp., Damalina spp., Trichodectes spp., Felicola spp.
[0255] From the order 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., Melophagus spp.
[0256] From the order of the Siphonapterida, for example, Pulex
spp., Ctenocephalides spp., Xenopsylla spp., Ceratophyllus spp.
[0257] From the order of the Heteropterida, for example, Cimex
spp., Triatoma spp., Rhodnius spp., Panstrongylus spp.
[0258] From the order of the Blattarida, for example, Blatta
orientalis, Periplaneta americana, Blattela germanica, Supella
spp.
[0259] From the subclass of the Acaria (Acarida) and the orders of
the Meta- and Mesostigmata, for example, Argas spp., Omithodorus
spp., Otobius spp., Ixodes spp., Amblyomma spp., Boophilus spp.,
Dermacentor spp., Haemophysalis spp., Hyalomma spp., Rhipicephalus
spp., Dermanyssus spp., Raillietia spp., Pneumonyssus spp.,
Stemostoma spp., Varroa spp.
[0260] 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., Laminosioptes spp.
[0261] For example, they show a good activity against flies (Musca
domestica), a development-inhibitory action against fly larvae of
Lucilla cuprina and a good activity against cockroaches
(Periplaneta americana) and against ticks (Boophilus microplus),
also as oviposition inhibitors.
[0262] The active compounds of the formula (I) according to the
invention are also suitable for controlling arthropods which attack
agricultural livestock such as, for example, cattle, sheep, goats,
horses, pigs, donkeys, camels, buffaloes, rabbits, chickens,
turkeys, ducks, geese, honey bees and other domestic animals such
as, for example, dogs, cats, cage birds, aquarium fish and
so-called animals for experimentation such as, for example,
hamsters, guinea pigs, rats and mice. Controlling these arthropods
is intended to reduce deaths and reduced performance (in meat,
milk, wool, hides, eggs, honey and the like), so that use of the
active compounds according to the invention allows more economical
and simpler animal keeping.
[0263] In the veterinary sector, the active compounds according to
the invention are applied in the known manner by enteral
administration in the form of, for example, tablets, capsules,
drinks, drenches, granules, pastes, boluses, the feed-through
method, suppositories, by parenteral administration, such as, for
example, by means of injection (intramuscular, subcutaneous,
intravenous, intraperitoneal and the like), implants, by nasal
administration, by dermal administration in the form of, for
example, dipping or bathing, spraying, pouring-on and spotting-on,
washing, dusting, and with the aid of shaped articles containing
active compound, such as collars, ear tags, tail tags, limb bands,
halters, marking devices and the like.
[0264] When used for livestock, poultry, domestic animals and the
like, the active compounds of the formula (I) can be applied as
formulations (for example powders, emulsions, flowables) which
contain the active compounds in an amount of 1 to 80% by weight,
either directly or after 100- to 10,000-fold dilution, or as a
chemical dip.
[0265] Moreover, it has been found that the compounds of the
formula (I) according to the invention have a potent insecticidal
action against insects which destroy industrial materials.
[0266] The following insects may be mentioned by way of example and
as being preferred, but without limitation:
[0267] Beetles such as
[0268] Hylotrupes bajulus, Chlorophorus pilosis, Anobium punctatum,
Xestobium rufovillosum, Ptilinus pecticomis, Dendrobium pertinex,
Ernobius mollis, Priobium carpini, Lyctus brunneus, Lyctus
africanus, Lyctus planicollis, Lyctus linearis, Lyctus pubescens,
Trogoxylon aequale, Minthes rugicollis; Xyleborus spec.
Tryptodendron spec. Apate monachus, Bostrychus capucins,
Heterobostrychus brunneus, Sinoxylon spec. Dinoderus minutus
[0269] Dermapterans such as
[0270] Sirex juvencus, Urocerus gigas, Urocerus gigas taignus,
Urocerus augur
[0271] Termites such as
[0272] Kalotermes flavicollis, Cryptotermes brevis, Heterotermes
indicola, Reticulitermes flavipes, Reticulitermes santonensis,
Reticulitermes lucifugus, Mastotermes darwiniensis, Zootermopsis
nevadensis, Coptotermes formosanus.
[0273] Bristletails such as Lepisma saccarina.
[0274] Technical materials are to be understood as meaning, in the
present context, non-live materials such as, preferably, polymers,
adhesives, sizes, paper and board, leather, wood and timber
products and paints.
[0275] Most preferably, the material to be protected from attack
from insects is wood and timber products.
[0276] Wood and timber products which can be protected by the agent
according to the invention or by mixtures comprising this agent are
to be understood as meaning, for example: construction timber,
wooden beams, railway sleepers, bridge components, jetties, wooden
vehicles, boxes, pallets, containers, telephone poles, wooden
claddings, windows and doors made from wood, or plywood, chipboard,
joiners' work or timber materials which, quite generally, are used
in domestic construction or in joinery.
[0277] The active compounds can be used as such, in the form of
concentrates or generally customary formulations such as powders,
granules, solutions, suspensions, emulsions or pastes.
[0278] The formulations mentioned can be prepared in a manner known
per se, for example by mixing the active compounds with at least
one solvent or diluent, emulsifier, dispersant and/or binder or
fixative, water repellant, if appropriate desiccants and UV
stabilizers and, if appropriate, dyes and pigments and other
processing auxiliaries.
[0279] The insecticides or concentrates employed for the protection
of wood and timber products contain 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.
[0280] The amount of agents or concentrates employed depends on the
species and the abundance of the insects and on the medium. The
optimal rate can be determined by test series for each application.
In general, however, it will suffice to employ 0.0001 to 20% by
weight, preferably 0.001 to 10% by weight, of the active compound,
based on the material to be protected.
[0281] The solvent and/or diluent used is an organochemical solvent
or solvent mixture and/or an oily or oil-type organochemical
solvent of low volatility or solvent mixture and a polar
organochemical solvent or solvent mixture and/or water and, if
appropriate, an emulsifier and/or wetter.
[0282] Organochemical solvents which are preferably employed are
oily or oil-type solvents with an evaporation number of above 35
and a flash point of above 30.degree. C., preferably above
45.degree. C. Such water-insoluble oily and oil-type solvents of
low volatility which are used are suitable mineral oils or their
aromatic fractions or mineral-oil-containing solvent mixtures,
preferably white spirit, petroleum and/or alkylbenzene.
[0283] Mineral oils which are preferably used are those with a
boiling range of 170 to 220.degree. C., white spirit with a boiling
range of 170 to 220.degree. C., spindle oil with a boiling range of
250 to 350.degree. C., petroleum and aromatics with a boiling range
of 160 to 280.degree. C., oil of turpentine and the like.
[0284] In a preferred embodiment, liquid aliphatic hydrocarbons
with a boiling range of 180 to 210.degree. C. or high-boiling
mixtures of aromatic and aliphatic hydrocarbons with a boiling
range of 180 to 220.degree. C. and/or spindle oil and/or
monochloronaphthalene are used, preferably
.alpha.-monochloronaphthalene.
[0285] The organic oily or oil-type solvents of low volatility and
with an evaporation number of above 35 and a flash point of above
30.degree. C., preferably above 45.degree. C., can be replaced in
part by organochemical solvents of high or medium volatility, with
the proviso that the solvent mixture also has an evaporation number
of above 35 and a flash point above 30.degree. C., preferably above
45.degree. C., and that the insecticide/fungicide mixture is
soluble or emulsifiable in this solvent mixture.
[0286] In a preferred embodiment, some of the organochemical
solvent or solvent mixture is also replaced an aliphatic polar
organochemical solvent or solvent mixture. Aliphatic organochemical
solvents which contain hydroxyl and/or ester and/or ether groups
are preferably used, such as, for example, glycol ethers, esters or
the like.
[0287] Organochemical binders used for the purposes of the present
invention are the binding drying oils and/or synthetic resins which
are known per se and which can be diluted in water and/or dissolved
or dispersed or emulsified in the organochemical solvents employed,
in particular binders composed of, or comprising, an acrylate
resin, a vinyl resin, for example polyvinyl acetate, polyester
resin, polycondensation or polyaddition resin, polyurethane resin,
alkyd resin or modified alkyd resin, phenol resin, hydrocarbon
resin such as indene/coumarone resin, silicone resin, drying
vegetable and/or drying oils and/or physically drying binders based
on a natural and/or synthetic resin.
[0288] The synthetic resin used as binder can be employed in the
form of an emulsion, dispersion or solution. Bitumen or bituminous
substances may also be used as binders, in amounts of up to 10% by
weight. In addition, colorants, pigments, water repellants,
flavour-masking agents and inhibitors or anticorrosive agents and
the like, all of which are known per se, can additionally be
employed.
[0289] The composition or the concentrate preferably comprises, in
accordance with the invention, at least one alkyd resin or modified
alkyd resin and/or a drying vegetable oil as organochemical binder.
Substances which are preferably used in accordance with the
invention are alkyd resins with an oil content of over 45% by
weight, preferably 50 to 68% by weight.
[0290] The abovementioned binder can be replaced fully or in parts
by a fixative (mixture) or a plasticizer (mixture). These additives
are intended to prevent volatilization of the active compounds, and
also crystallization or precipitation. They preferably replace 0.01
to 30% of the binder (based on 100% of the binder employed).
[0291] The plasticizers are from the chemical classes of the
phthalic esters, such as dibutyl phthalate, dioctyl phthalate or
benzyl butyl phthalate, phosphoric esters such as tributyl
phosphate, adipic 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 esters.
[0292] Fixatives are based chemically on polyvinyl alkyl ethers
such as, for example, polyvinyl methyl ether or ketones such as
benzophenone and ethylenebenzophenone.
[0293] Another solvent or diluent is, in particular, water, if
appropriate in a mixture with one or more of the abovementioned
organochemical solvents or diluents, emulsifiers and
dispersants.
[0294] Particularly effective protection of wood is achieved by
industrial-scale impregnating processes, for example vacuum,
double-vacuum or pressure processes.
[0295] If appropriate, the ready-to-use products may comprise
further insecticides and, if appropriate, also one or more
fungicides.
[0296] Additional components are preferably the insecticides and
fungicides mentioned in WO 94/29 268. The compounds mentioned in
this document are expressly part of the present invention.
[0297] Most preferred components which may be mentioned are
insecticides such as chlorpyriphos, phoxim, silafluofin,
alphamethrin, cyfluthrin, cypenmethrin, delta-methrin, 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-octylisothiazolin-3-one and
4,5-dichloro-N-octylisothiazolin-3-one.
[0298] Preparation and use of the active compounds according to the
invention can be seen from the examples which follow.
PREPARATION EXAMPLES
Example 1
[0299] 28
[0300] 11 g (0.024 mol) of
5-amino-3-cyano-4-(1,1-difluoroethylsulphonyl)--
1-(2,6-dichloro-4-trifluoromethylphenyl)-pyrazole are dissolved in
80 ml of pyridine and 10 ml of trimethylamine. Then, hydrogen
sulphide is passed in at room temperature for about 3 hours. The
reaction solution is subsequently treated with water and extracted
repeatedly with dichloromethane. After drying over magnesium
sulphate, the mixture is concentrated by distilling off the solvent
in vacuo, and the oily residue is stirred with diethyl ether and
filtered off with suction.
[0301] This gives 8 g (68% of theory) of
5-amino-4-(1,1-difluoroethylsulph-
onyl)-1-(2,6-di-chloro-4-trifluoromethylphenyl)-3-thiocarbamoylpyrazole
of melting point 228-29.degree. C.
[0302] The compounds of the formula (I) shown in Table A below are
obtained analogously Example 1 or in accordance with the general
preparation instructions:
1TABLE A (I) 29 Ex. m.p No. --S(O).sub.n--R.sup.2 R.sup.3 Ar
(.degree. C.) 2 --S--CF.sub.2CH.sub.3 NH.sub.2 30 101 3
--S--CH.sub.2CF.sub.2CF.sub.3 NH.sub.2 31 196 4 --SO--CF.sub.3
NH.sub.2 32 203 5 --SO--CF.sub.2CH.sub.3 NH.sub.2 33 200
Preparation of the New Starting Materials of the Formula (VII)
Example (VII-1)
[0303] 34
[0304] 3.8 (0.012 mol) of
5-amino-3-cyano-1-(2,6-dichloro-4-trifluoromethy- lphenyl)-pyrazole
are dissolved in 50 ml of pyridine and 5 ml of triethylamine. Then,
hydrogen sulphide is passed in for approx. 2 hours at room
temperature, and stirring is subsequently continued for a further
10 minutes at 50.degree. C. The reaction solution is concentrated
in vacuo, and the residue which remains is treated with water and
dichloromethane. The mixture is extracted repeatedly with
dichloromethane and the combined dichloromethane phases are dried
over magnesium sulphate and concentrated in vacuo.
[0305] This gives 3.4 g (81% of theory) of
5-amino-1-(2,6-dichloro-4-trifl-
uoro-methylphenyl)-3-thiocarbamoylpyrazole.
[0306] .sup.1H-NMR (in DMSO with TMS as the internal standard;
.delta. in ppm):
[0307] 9.49 (1H); 9.08 (1H); 8.21 (2H); 5.96 (1H); 5.69 (2H).
Preparation of the New Starting Materials of the Formula (III)
Example (III-1)
[0308] 35
[0309] Starting from
3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-5-(p-
yrrol-1-yl)-pyrazole, Example (III-1) is obtained analogously to
Example (VII-1).
[0310] .sup.1H-NMR (in DMSO with TMS as the internal standard;
.delta. in ppm):
[0311] 9.95 (1H); 9.58 (1H); 8.30 (2H); 7.19 (1H); 6.20 (2H); 6.13
(2H).
Use Examples
[0312] In the use examples which follow, compounds given below are
used as comparison substances: 36
[0313] (All compounds disclosed in EP-A 0 659 745)
Example A
[0314] Phaedon larvae test
[0315] Solvent: 7 parts by weight of dimethylformamide
[0316] Emulsifier: 1 part by weight of alkylaryl polyglycol
ether
[0317] To prepare 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.
[0318] Cabbage leaves (Brassica oleracea) are treated by being
dipped into the preparation of active compound of the desired
concentration and are populated with mustard beetle larvae (Phaedon
cochleariae) while the leaves are still moist.
[0319] After the desired time, the destruction rate is determined
in %. 100% means that all the beetle larvae have been destroyed; 0%
means that none of the beetle larvae have been destroyed.
[0320] In this test, an exemplary active compound concentration of
0.00001% of, for example, the compounds of Preparation Examples 1
and 2 caused a destruction rate of 100% after in each case 3 days,
while the destruction rate caused by the known compound (A) was
only 25%.
Example B
[0321] Plutella test
[0322] Solvent: 7 parts by weight of dimethylformamide
[0323] Emulsifier: 1 part by weight ofalkylaryl polyglycol
ether
[0324] To prepare 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.
[0325] 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
diamond-back moth (Plutella xylostella) while the leaves are still
moist.
[0326] After the desired time, the destruction rate is determined
in %. 100% means that all the caterpillars have been destroyed; 0%
means that none of the caterpillars have been destroyed.
[0327] In this test, an exemplary active compound concentration of
0.0001% of, for example, the compound of Preparation Example 1
caused a destruction rate of 75% and of the compound of Preparation
Example 2 a destruction rate of 100%, after in each case 3 days,
while the known compound (A) showed a destruction rate of only
15%.
Example C
[0328] Spodoptera frugiperda test
[0329] Solvent: 7 parts by weight of dimethylformamide
[0330] Emulsifier: 1 part by weight ofalkylaryl polyglycol
ether
[0331] To prepare 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.
[0332] 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 fall
armyworm (Spodoptera frugiperda) while the leaves are still
moist.
[0333] After the desired time, the destruction rate is determined
in %. 100% means that all the caterpillars have been destroyed; 0%
means that none of the caterpillars have been destroyed.
[0334] In this test, an exemplary active compound concentration of
0.01% of, for example, the compounds of Preparation Examples 1, 2
and 4 caused a destruction rate of 100% after in each case 7 days,
while the known compounds (B) and (C) showed a destruction rate of
only 10% and no destruction, respectively.
Example D
[0335] Nephotettix-Test
[0336] Solvent: 20 parts by weight of dimethylformamide
[0337] Emulsifier: 1 part by weight ofalkylaryl polyglycol
ether
[0338] To prepare 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.
[0339] Rice seedlings (Oryza sativa) are treated by being dipped
into the preparation of active compound of the desired
concentration and are populated with green rice leafhoppers
(Nephotettix cincticeps) while the seedlings are still moist.
[0340] After the desired time, the destruction rate is determined
in %. 100% means that all the leafhoppers have been destroyed; 0%
means that none of the leafhoppers have been destroyed.
[0341] In this test, an exemplary active compound concentration of
0.1% of, for example, the compounds of Preparation Examples 2 and 4
caused a destruction rate of 100% and of the compound of
Preparation Example 5 a destruction rate of 80% after in each case
6 days, while the known compounds (A) and (D) showed a destruction
rate of only 10% and no destruction, respectively.
Example E
[0342] Myzus-Test
[0343] Solvent: 7 parts by weight of dimethylformamide
[0344] Emulsifier: 1 part by weight ofalkylaryl polyglycol
ether
[0345] To prepare 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.
[0346] Cabbage leaves (Brassica oleracea) which are severely
infested with the peach aphid (Myzus persicae) are treated by being
dipped into the active compound preparation of the desired
concentration.
[0347] After the desired time, the destruction rate is determined
in %. 100% means that all the aphids have been destroyed; 0% means
that none of the aphids have been destroyed.
[0348] In this test, for example the compounds of the following
preparation examples caused the following destruction rates at an
exemplary active compound concentration of 0.1%:
[0349] 1=80%; 2=98% and 4=100%; in each case after 6 days, while
the known compound (C) showed an activity of only 50% and the known
compound (B) none.
Example F
[0350] Limit concentration test/soil-dwelling insects
[0351] Test insect: Diabrotica balteata larvae in the soil
[0352] Solvent: 4 parts by weight of acetone
[0353] Emulsifier: 1 part by weight of alkylaryl polyglycol
ether
[0354] To prepare a suitable preparation of active compound, 1 part
by weight of active compound is mixed with the stated amount of
solvent, the stated amount of emulsifier is added, and the
concentrate is diluted with water to the desired concentration. The
concentration of the active compound in the preparation is of
virtually no importance, only the amount by weight of active
compound per unit volume soil, which is given in ppm (mg/l), being
decisive. The soil is filled into 0.5 l pots and the pots are left
to stand at 20.degree. C.
[0355] Immediately after setting up the test, 5 pregerminated maize
kernels are placed into each pot. After 1 day, the test insects are
placed into the treated soil. After a further 7 days, the efficacy
of the active compound is determined in % by counting the dead and
live test insects. The efficacy is 100% when all test insects have
been destroyed and 0% when just as many test insects are still
alive as in the untreated control.
[0356] In this test, for example the compounds of Preparation
Examples 2, 4 and 5 caused a destruction rate of 100% at an
exemplary active compound concentration of 0.002%.
Example G
[0357] Limit concentration test/root-systemic action
[0358] Test insect: Phaedon cochleariae larvae
[0359] Solvent: 4 parts by weight of acetone
[0360] Emulsifier: 1 part by weight of alkylaryl polyglycol
ether
[0361] To prepare a suitable preparation of active compound, 1 part
by weight of active compound is mixed with the stated amount of
solvent, the stated amount of emulsifier is added, and the
concentrate is diluted with water to the desired concentration.
[0362] The active compound preparation is mixed intimately with
soil. The concentration of the active compound in the preparation
is of virtually no importance, only the amount by weight of active
compound per unit volume soil, which is given in ppm (=mg/l), being
decisive. The treated soil is filled into pots and the pots are
planted with cabbage (Brassica oleracea). In this manner, the
active compound can be taken up from the soil by the roots of the
plants and transported into the leaves.
[0363] To demonstrate the root-systemic effect, the leaves are
populated with the abovementioned test animals after 7 days. After
a further 2 days, the test is evaluated by counting or estimating
the dead animals. The root-systemic effect of the active compound
is deduced from the destruction figures. It is 100% when all the
test animals have been destroyed and 0% when just as many test
insects are still alive as in the untreated control.
[0364] In this test, for example the compounds of Preparation
Examples 1, 4 and 5 caused a destruction rate of 100% at an
exemplary active compound concentration of 0.002%.
Example H
[0365] Fly test (Musca domestica)
[0366] Test animals:
[0367] Adult Musca domestica, strain Reichswald
[0368] (OP, SP, carbamate-resistant)
[0369] Solvent:
[0370] 35 parts by weight of ethylene glycol monomethyl ether
[0371] 35 parts by weight of nonylphenyl polyglycol ether
[0372] To produce a suitable formulation, three parts by weight of
active compound are mixed with seven parts of the abovementioned
solvent/emulsifier mixture and the resulting emulsion concentrate
is diluted with water to the concentration desired in each
case.
[0373] 2 ml of this active compound preparation are pipetted onto
filter paper dishes (.phi.9.5 cm) which are located in Petri dishes
of a suitable size. After the filter discs have been dried, 25 test
animals are introduced into the Petri dish and covered.
[0374] The efficacy of the active compound preparation is
determined after 1, 3, 5 and 24 hours. 100% means that all of the
flies have been destroyed; 0% means that none of the flies have
been destroyed.
[0375] In this test, for example, the compounds of Preparation
Examples 1, 2, 4 and 5 showed an activity of 100% at an exemplary
active compound concentration of 100 ppm.
Example I
[0376] Fly larvae test/development-inhibitory action
[0377] Test animals:
[0378] All instars of Lucilia cuprina (OP-resistant)
[0379] [pupae and adults (no contact with the active compound)]
[0380] Solvent:
[0381] 35 parts by weight of ethylene glycol monomethyl ether
[0382] 35 parts by weight of nonylphenyl polyglycol ether
[0383] To produce a suitable formulation, three parts by weight of
active compound are mixed with seven parts of the abovementioned
solvent/emulsifier mixture and the resulting emulsion concentrate
is diluted with water to the concentration desired in each
case.
[0384] For each concentration, 30-50 larvae are transferred onto
horse meat (1 cm.sup.3) located in glass tubes, and 500 .mu.l of
the dilution to be tested are pipetted onto the horse meat. The
glass tubes are placed into plastic beakers whose bottoms are
covered with sea sand and kept in a controlled-environment cabinet
(26.degree. C..+-.1.5.degree. C., rel. humidity 70%.+-. 10 %). The
action is checked after 24 hours and after 48 hours (larvicidal
action). After the larvae have left the glass tubes (approx. 72
hours), the latter are removed, and the beakers are covered with
perforated plastic lids. After 11/2times the development time
(hatching of control flies), the hatched flies and the
pupae/puparia are counted.
[0385] The criterion for the effect is death in the case of the
treated larvae after 48 hours (larvicidal effect), or the
inhibition of the hatching of adults from the pupae, or the
inhibition of pupation. The criterion for the in-vitro action of a
substance is the inhibition of flea development, or a developmental
standstill prior to the adult stage. 100% larvicidal action means
that all larvae have died after 48 hours. 100%
development-inhibitory action means that no adult flies have
hatched.
[0386] In this test, for example the compounds according to
Preparation Examples 1, 2, 4 and 5 showed an activity of 100% at an
exemplary active compound concentration of 100 ppm.
Example J
[0387] Test with resistant Boophilus microplus/SP-resistant
Parkhurst strain
[0388] Test animals:
[0389] Female adults which have sucked themselves full
[0390] Solvent:
[0391] 35 parts by weight of ethylene glycol monomethyl ether
[0392] 35 parts by weight of nonylphenyl polyglycol ether
[0393] To produce a suitable formulation, three parts by weight of
active compound are mixed with seven parts of the abovementioned
solvent/emulsifier mixture and the resulting emulsion concentrate
is diluted with water to the concentration desired in each case. 10
resistant Boophilus microplus adults are immersed for 1 minute in
the active compound preparation to be tested. After they have been
transferred into plastic beakers and kept in a
controlled-environment cabinet, the degree of destruction is
determined.
[0394] 100% means that all the ticks have been destroyed; 0% means
that none of the ticks have been destroyed.
[0395] In this test, for example the compounds of Preparation
Examples 2, 4 and 5 showed an activity of 100% at an exemplary
active compound concentration of 100 ppm.
Example K
[0396] Test with resistant Boophilus microplus/SP-resistant
Parkhurst strain
[0397] Test animals:
[0398] Female adults which have sucked themselves full
[0399] Solvent:
[0400] Dimethylsulphoxide
[0401] 20 mg of the active compound are dissolved in 1 ml of
dimethyl sulphoxide, and lesser concentrations are prepared by
dilution with the same solvent.
[0402] The test is carried out in 5 replications. 1 .mu.l of the
solutions is injected into the abdomen and the animals are
transferred into dishes and kept in a controlled-environment
cabinet. The activity is determined via the inhibition of
oviposition. 100% means that none of the ticks has laid eggs.
[0403] In this test, the compounds of Preparation Examples 1, 3, 4
and 5 showed an activity of 100% at an exemplary active compound
concentration of 20 .mu.g/animal.
Example L
[0404] Cockroach test
[0405] Test animals Periplaneta americana
[0406] Solvent:
[0407] 35 parts by weight of ethylene glycol monomethyl ether
[0408] 35 parts by weight of nonylphenyl polyglycol ether
[0409] To produce a suitable formulation, three parts by weight of
active compound are mixed with seven parts of the abovementioned
solvent/emulsifier mixture and the resulting emulsion concentrate
is diluted with water to the concentration desired in each
case.
[0410] 2 ml of this active compound preparation are pipetted onto
filter paper discs (.phi.9.5 cm) located in Petri dishes of a
suitable size. After the filtered discs have dried, 5 test animals
Periplaneta americana are transferred and covered.
[0411] After 3 days, the activity of the active compound
preparation is determined. 100% means that all the cockroaches have
been destroyed; 0% means that none of the cockroaches have been
destroyed.
[0412] In this test, for example the compounds of Preparation
Examples 1 and 2 showed an activity of 100% at an exemplary active
compound concentration of 100 ppm.
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