U.S. patent application number 09/782629 was filed with the patent office on 2001-11-08 for pesticidal compositions.
Invention is credited to Hall, Roger Graham, Karrer, Friedrich.
Application Number | 20010039247 09/782629 |
Document ID | / |
Family ID | 25685105 |
Filed Date | 2001-11-08 |
United States Patent
Application |
20010039247 |
Kind Code |
A1 |
Karrer, Friedrich ; et
al. |
November 8, 2001 |
Pesticidal compositions
Abstract
A composition, which comprises at least one compound of the
formula 1 in which A.sub.1, A.sub.2, R.sub.1 and R.sub.2 are as
defined in claim 1, or, if appropriate, an E/Z isomer, an E/Z
isomer mixture and/or a tautomer thereof in each case in free form
or in aqrochemically utilizable salt form, as active ingredient and
at least one auxiliary, can used for pest control.
Inventors: |
Karrer, Friedrich;
(Zofingen, CH) ; Hall, Roger Graham; (Pfeffingen,
CH) |
Correspondence
Address: |
SYNGENTA CROP PROTECTION , INC.
PATENT AND TRADEMARK DEPARTMENT
410 SWING ROAD
GREENSBORO
NC
27409
US
|
Family ID: |
25685105 |
Appl. No.: |
09/782629 |
Filed: |
February 13, 2001 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
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09782629 |
Feb 13, 2001 |
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09230311 |
Jan 21, 1999 |
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Current U.S.
Class: |
504/326 ;
504/193 |
Current CPC
Class: |
A01N 37/42 20130101;
A01N 47/38 20130101; A01N 47/34 20130101; C07C 281/14 20130101;
A01N 35/10 20130101; C07C 311/05 20130101; A01N 37/52 20130101;
C07C 327/44 20130101; C07D 295/215 20130101; A01N 37/28 20130101;
A01N 37/48 20130101; A01N 47/12 20130101; A01N 47/40 20130101; C07C
251/86 20130101; A01N 37/50 20130101; C07C 257/02 20130101; C07C
271/20 20130101; C07C 255/66 20130101; C07C 323/48 20130101; A01N
37/34 20130101; A01N 47/24 20130101 |
Class at
Publication: |
504/326 ;
504/193 |
International
Class: |
A01N 055/08 |
Foreign Application Data
Date |
Code |
Application Number |
Jul 24, 1996 |
CH |
1853/96 |
Mar 13, 1997 |
CH |
607/97 |
Claims
What is claimed is:
1. A pesticidal composition, which comprises at least one compound
of the formula 30in which A.sub.1 and A.sub.2 are independent of
one another and are in each case a mono- or bioyolic aryl or
hetaryl radical, each hetaryl radical independently of the other
having 1 up to and including 4 hetero atoms selected from the group
consisting of N, O and S; A.sub.1 is substituted with a substituent
(R.sub.3a).sub.n1 and A.sub.2 with a substituent (R.sub.3b).sub.n2;
R.sub.1 is --CN, halo-C.sub.1-C.sub.6alkyl or
--C(.dbd.S)--N(R.sub.5).sub.2 (in which the two R.sub.5 are
independent of one another); R.sub.2 is hydrogen, --OH,
C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.6alkoxy,
C.sub.3-C.sub.6cycloalkyl, C.sub.3-C.sub.6alkenyl,
C.sub.3-C.sub.6alkynyl, halo-C.sub.1-C.sub.6alkyl- ,
halo-C.sub.3-C.sub.6alkenyl, halo-C.sub.3-C.sub.6alkynyl, benzyl or
benzoyl, in which the benzyl or benzoyl radical is unsubstituted or
mono- to trisubstituted in the aromatic ring by substituents which
are independent of one another and selected from the group
consisting of halogen, --CN, NO.sub.2, C.sub.1-C.sub.6alkyl,
C.sub.1-C.sub.6alkoxy, halo-C.sub.1-C.sub.6alkyl and
halo-C.sub.1-C.sub.6alkoxy;
C.sub.1-C.sub.6alkoxy-C.sub.1-C.sub.6alkyl,
cyano-C.sub.1-C.sub.6alkyl, --C(.dbd.X)--R.sub.7,
--OC(.dbd.O)--R.sub.7, --C(.dbd.O)--C(.dbd.O)--R.su- b.7,
--S(.dbd.O).sub.pN(R.sub.6).sub.2 (in which the two R.sub.6 are
independent of one another); cyano,
--C.sub.1-C.sub.6alkyl-N(R.sub.10)--C- (.dbd.O)--R.sub.8,
--C.sub.1-C.sub.6alkyl-S--C(.dbd.S)--R.sub.8,
--C.sub.1-C.sub.6alkyl-S(.dbd.O).sub.p--R.sub.9,
--S(.dbd.O).sub.p--R.sub- .9, or
--CH.sub.2--N(R.sub.10)--SO.sub.2--R.sub.9; R.sub.3a and R.sub.3b
are independently of each other halogen, C.sub.1-C.sub.6alkyl,
C.sub.2-C.sub.4alkenyl, C.sub.2-C.sub.4alkynyl,
halo-C.sub.1-C.sub.6alkyl- , halo-C.sub.2-C.sub.4alkenyl,
halo-C.sub.2-C.sub.4alkynyl, C.sub.1-C.sub.6alkoxy,
halo-C.sub.1-C.sub.6alkoxy, C.sub.2-C.sub.6alkenyloxy,
C.sub.2-C.sub.6alkynyloxy, halo-C.sub.2-C.sub.6alkenyloxy,
halo-C.sub.2-C.sub.6alkynyloxy, --OH, --SFs, --CHO,
--C(.dbd.O)--C.sub.1-C.sub.6alkyl, --C(.dbd.O)-halo-C.sub.1-
-C.sub.6alkyl, --C(.dbd.O).dbd.OC.sub.1-C.sub.6alkyl,
--C(.dbd.O)--O-halo-C.sub.1-C.sub.6alkyl,
--O--C(.dbd.O)N(R.sub.6).sub.2 (in which the two R.sub.6 are
independent of one another), --CN, --NO.sub.2,
--S(.dbd.O).sub.2N(R.sub.6).sub.2 (in which the two R.sub.6 are
independent of one another),
--S(.dbd.O).sub.p--C.sub.1-C.sub.6alkyl,
--S(.dbd.O).sub.p-halo-C.sub.1-C.sub.6alkyl,
--O--S(.dbd.O).sub.p--C.sub.- 1-C.sub.6alkyl,
--O--S(.dbd.O).sub.p-halo-C.sub.1-C.sub.6alkyl, phenyl, benzyl,
phenoxy or benzyloxy, each of the phenyl, benzyl, phenoxy or
benzyloxy radicals being unsubstituted or mono- to pentasubstituted
in the aromatic ring by substituents which are independent of one
another and selected from the group consisting of halogen, cyano,
NO.sub.2, C.sub.1-C.sub.6alkyl, halo-C.sub.1-C.sub.6alkyl,
C.sub.1-C.sub.6alkoxy and halo-C.sub.1-C.sub.6alkoxy; n.sub.1 and
n.sub.2 are 0 or, depending on the substitution options on the ring
systems A.sub.1 and A.sub.2 in question, independently of each
other 1, 2, 3, 4 or 5; X is O or S; p is 0, 1 or 2; R.sub.5
radicals independently of one another are H or
C.sub.1-C.sub.8alkyl; R.sub.6 radicals independently of one another
are H, C.sub.1-C.sub.8alkyl, C.sub.3-C.sub.6cycloalkyl, phenyl or
benzyl, the phenyl or benzyl group in the aromatic ring being
unsubstituted or mono- to trisubstituted by substituents which are
independent of one another and selected from the group consisting
of halogen, --CN, NO.sub.2, C.sub.1-C.sub.6alkyl,
C.sub.1-C.sub.4alkoxy, halo-C.sub.1-C.sub.6alkyl and
halo-C.sub.1-C.sub.6alkoxy; or two alkyl radicals R.sub.6 together
with the nitrogen atom to which they are bonded form a five- to
seven-membered ring in which a CH.sub.2 group may be replaced by a
hetero atom selected from the group consisting of O and S, or by
NH, and where the five- to seven-membered ring is unsubstituted or
mono- or di-substituted by C.sub.1-C.sub.4alkyl; R.sub.7 is H,
C.sub.1-C.sub.8alkyl, C.sub.2-C.sub.8alkenyl,
halo-C.sub.1-C.sub.8alkyl, halo-C.sub.2-C.sub.8alkenyl,
C.sub.1-C.sub.8alkoxy, halo-C.sub.1-C.sub.8alkoxy,
C.sub.3-C.sub.6cycloalkyl, phenyl, benzyl, phenoxy, benzyloxy or
--N(R.sub.6).sub.2 (in which the two R.sub.6 are independent of one
another); R.sub.8 is C.sub.1-C.sub.8alkyl, C.sub.1-C.sub.8alkoxy,
halo-C.sub.1-C.sub.8alkyl, halo-C.sub.1-C.sub.8alk- oxy,
C.sub.1-C.sub.8alkylthio, phenyl, benzyl or --N(R.sub.6).sub.2 (in
which the two R.sub.6 are independent of one another); R.sup.9 is
C.sub.1-C.sub.6alkyl, halo-C.sub.1-C.sub.4alkyl or aryl which is
unsubstituted or mono- to trisubstituted by substituents which are
independent of one another and selected from the group consisting
of C.sub.1-C.sub.6alkyl, C.sub.2-C.sub.4alkenyl,
C.sub.2-C.sub.4alkynyl, C.sub.1-C.sub.4alkoxy, halogen, cyano,
halo-C.sub.1-C.sub.4alkyl, halo-C.sub.2-C.sub.4alkenyl,
halo-C.sub.2-C.sub.4alkynyl, halo-C.sub.1-C.sub.4alkoxy and nitro;
and R.sub.10 is H, C.sub.1-C.sub.6alkyl, C.sub.3-C.sub.6cycloalkyl,
phenyl or benzyl, the phenyl and benzyl radicals being
unsubstituted or mono- to trisubstituted in the aromatic ring by
substituents which are independent of one another and selected from
the group consisting of C.sub.1-C.sub.4alkyl,
C.sub.1-C.sub.4alkoxy, halogen, cyano, halo-C.sub.1-C.sub.4alkyl,
halo-C.sub.1-C.sub.4alkoxy and nitro; or, if appropriate, an E/Z
isomer, an E/Z isomer mixture and/or a tautomer thereof, in each
case in free form or in agrochemically utilizable salt form, with
the exception of 1-phenyl-hydrazono-2-nitriloethylbenzene, as
active ingredient and at least one auxiliary.
2. A composition according to claim 1, which comprises a compound
of the formula (I), in free form.
3. A composition according to claim 1, which comprises a compound
of the formula (I), in which A.sub.1 and A.sub.2 independently of
one another are a substituent selected from the group consisting of
31R.sub.3 is halogen, --CN, NO.sub.2, halo-C.sub.1-C.sub.2alkyl,
C.sub.1-C.sub.2alkoxy or halo-C.sub.1-C.sub.2alkoxy,
halo-C.sub.2-C.sub.5alkenoxy or halo-C.sub.2-C.sub.5alkynyloxy;
where, if m+n is greater than 1, the radicals R.sub.3 are
independent of one another; R.sub.4 is H, C.sub.1-C.sub.4alkyl,
phenyl or benzyl; n is, depending on the possibilities for
substitution on the ring system, 0 to 5, and the value of n.sub.1
in A.sub.1 is independent of the value of n.sub.2 in A.sub.2; m,
depending on the possibilities for substitution on the ring system,
is 0 to 4, and the values of m in A.sub.1 are independent of the
values of m in A.sub.2; the total m+n in each radical A.sub.1 and
A.sub.2 is 0 to 5.
4. A composition according to claim 1, which comprises a compound
of the formula (I), in which A.sub.1 and A.sub.2 are phenyl.
5. A composition according to claim 1, which comprises a compound
of the formula (I), in which R, is --CN or
halo-C.sub.1-C.sub.2alkyl.
6. A composition according to claim 1, which comprises a compound
of the formula (1), in which R.sub.2 is hydrogen.
7. A composition according to claim 1, which comprises a compound
of the formula (1), in which R.sub.2 is --OH, C.sub.1-C.sub.6alkyl,
C.sub.1-C.sub.6alkoxy, C.sub.3-C.sub.6cycloalkyl,
C.sub.3-C.sub.6alkenyl, C.sub.3-C.sub.6alkynyl,
halo-C.sub.3-C.sub.6alkenyl, benzyl or benzoyl, the benzyl or
benzoyl radical being unsubstituted or mono- to trisubstituted in
the aromatic ring by substituents which are independent of one
another and selected from the group consisting of halogen, --CN,
NO.sub.2, C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.6alkoxy,
halo-C.sub.1-C.sub.6alkyl and halo-C.sub.1-C.sub.6alkoxy;
C.sub.1-C.sub.6alkoxy-C.sub.1-C.sub.6alkyl,
cyano-C.sub.1-C.sub.6alkyl, --C(.dbd.X)-R.sub.7,
--OC(.dbd.O)--R.sub.7, --C(.dbd.O)--C(.dbd.O)--R.sub- .7,
--S(.dbd.O).sub.pN(R.sub.6).sub.2 (in which the two R.sub.6 are
independent of one another); cyano,
--CH.sub.2--N(R.sub.5)--C(.dbd.O)--R.- sub.8,
--CH.sub.2--S--C(.dbd.S)--R.sub.8,
--C.sub.1-C.sub.4alkyl-S(.dbd.O)- .sub.p--R.sub.9,
--S(.dbd.O).sub.p--R.sub.9, or --CH.sub.2--N(R.sub.10)--S-
O.sub.2--R.sub.9.
8. A composition according to claim 1, which comprises a compound
of the formula (I), in which A.sub.1 is a pyridyl radical.
9. A composition according to claim 1, which comprises a compound
of the formula (I), inl which (R.sub.3a).sub.n1 is Cl, Cl.sub.2,
Cl.sub.3, --(CF.sub.3).sub.2, Cl.sub.3, --(CF.sub.3).sub.2,
NO.sub.2, --CN, Cl.sub.2--NO.sub.2, --OCF.sub.3, --CF.sub.3,
Cl--CF.sub.3, Cl.sub.2--CF.sub.3, Cl.sub.2--OCF.sub.3,
--Cl.sub.2--F, Cl.sub.2--Br, Cl--CF.sub.3--F,
Cl.sub.2--Br--CH.sub.3, --(CH.sub.3).sub.2--Br, Cl.sub.3--CF.sub.3,
Cl.sub.2--F--CF.sub.3, F.sub.2--C F.sub.3--Cl, Cl.sub.2--CN,
Cl.sub.2--CF.sub.3, Cl.sub.2--SCF.sub.3, Cl.sub.2--OCF.sub.3,
Cl.sub.2--O.sub.2CF.sub.3, Cl.sub.2--SO.sub.2CH.sub.- 3,
Cl.sub.2--OCF.sub.2Br, Cl.sub.2--OCF.sub.2H,
Cl.sub.2--C.sub.2F.sub.5, (NO.sub.2).sub.2--CF.sub.3,
(NO.sub.2).sub.2--Cl, Cl.sub.2--SO.sub.2CH.su- b.3 or
Cl.sub.2--OSO.sub.2CF.sub.3.
10. A composition according to claim 1, which comprises a compound
of the formula (I), in which (R.sub.3b).sub.n2 is --CN, Cl,
Cl.sub.2, F, F.sub.2, Br, --NO.sub.2, --(NO.sub.2).sub.2,
--NO.sub.2--CF.sub.3, CF.sub.3, --(CF.sub.3).sub.2, --CN--CF.sub.3,
Cl--CF.sub.3, F--CN, --Cl--CN, --OCF.sub.3, --Cl--NO.sub.2,
--CH.sub.3--NO.sub.2, --OCH.sub.3--NO.sub.2, --C.sub.6H.sub.5,
--C.sub.6H.sub.4--F, --C.sub.6H.sub.4--Cl,
--C.sub.6H.sub.4--CF.sub.3, --C.sub.6H.sub.4--CF.su- b.3,
--C.sub.6H.sub.4--NO.sub.2, --C.sub.6H.sub.3--(CF.sub.3).sub.2,
--C.sub.6H.sub.3--Cl.sub.2, --C.sub.6H.sub.3--(Cl--F), --F--CN,
F--NO.sub.2, --CHO or --C(.dbd.O)CF.sub.3.
11. A composition according to claim 1, which comprises a compound
of the formula (I), in which n.sub.1 is 1, 2, 3 or 4.
12. A composition according to claim 1, which comprises a compound
of the formula (I), in which n.sub.2 is 1 or 2.
13. A composition according to claim 1, which comprises a compound
of the formula (I), in which n.sub.1 is 2, 3 or 4 and n.sub.2 is 1
or 2.
14. A composition according to claim 1, which comprises a compound
of the formula (I), in which R.sub.7 is H, C.sub.1-C.sub.6alkyl,
C.sub.3-C.sub.6alkenyl, halo-C.sub.1-C.sub.6alkyl,
halo-C.sub.3-C.sub.6alkenyl, C.sub.1-C.sub.6alkoxy,
halo-C.sub.1-C.sub.6alkoxy, C.sub.3-C.sub.6cycloalkyl, phenyl,
benzyl, phenoxy, benzyloxy or --N(R.sub.6).sub.2 (in which the two
R.sub.6 are independent of one another).
15. A compound of the formula 32in which A.sub.1, A.sub.2, R.sub.1,
R.sub.2 and the substituents R.sub.3a and R.sub.3b of A.sub.1 and
A.sub.2 have the meanings given in claim 1 for formula (i); and
n.sub.1 and n.sub.2 are, depending on the substitution options on
the ring systems A.sub.1 and A.sub.2 in question, independently of
each other, 1, 2, 3, 4 or 5; or, if appropriate, an E/Z isomer, an
E/Z isomer mixture and/or a tautomer thereof, in each case in free
form or in salt form; with the proviso, that (P1) at least one of
the substituents R.sub.3a and R.sub.3b is
halogen-C.sub.1-C.sub.6-alkyl, halogen-C.sub.2-C.sub.4-alkenyl,
halogen-C.sub.2-C.sub.4-alkinyl, halogen-C.sub.1-C.sub.6-alkoxy,
C.sub.2-C.sub.6-alkenyloxy, C.sub.2-C.sub.6-alkynyloxy,
halogen-C.sub.2-C.sub.6-alkenyloxy,
halogen-C.sub.2-C.sub.6-alkynyloxy, --SF.sub.5, --CHO,
--C(.dbd.O)-halogen-C.sub.1-C.sub.6-alkyl,
--C(.dbd.O)--O-halogen-C.sub.1-C.sub.6-alkyl,
--O--C(.dbd.O)N(R.sub.6).su- b.2 (in which the two R.sub.6 are
independent of one another); --CN,
--S(.dbd.O).sub.2n(R.sub.6).sub.2 (in which the two R.sub.6 are
independent of one another);
--S(.dbd.O).sub.p--C.sub.1-C.sub.6-alkyl,
--S(.dbd.O).sub.p-halogen-C.sub.1-C.sub.6-alkyl,
--O--S(.dbd.O).sub.p-C.s- ub.1-C.sub.6-alkyl,
--O--S(--O).sub.p-halogen-C.sub.1-C.sub.6-Alkyl, phenyl, benzyl,
phenoxy or benzyloxy, each of the phenyl, benzyl, phenoxy or
benzyloxy radicals being unsubstituted or mono- to pentasubstituted
in the aromatic ring by substituents which are independent of one
another and selected from the group consisting of halogen, cyano,
NO.sub.2, C.sub.1-C.sub.6alkyl, halo-C.sub.1-C6alkyl,
C.sub.1-C.sub.6alkoxy and halo-C.sub.1-C.sub.6alkoxy; when n.sub.1
is 1 or 2; n.sub.2 is 1; and R.sub.1 is CN or
halogen-C.sub.1-C.sub.6-alkyl, and R.sub.2 is hydrogen; and with
the further proviso, that (P2) R.sub.3a is not 2--OH, when A.sub.2
is 4-nitrophenyl; R.sub.1 is CN; and R.sub.2 is hydrogen; and with
the further proviso, that (P3) A.sub.1 is not 4-chlorophenyl,
4-bromophenyl or 4-iodophenyl, when A.sub.2 is 2,4-dinitrophenyl;
R.sub.1 is CN; and R.sub.2 is hydrogen; and with the further
proviso, that (P4) A.sub.1 is not phenyl, when A.sub.2 is
tetrazolyl; R.sub.3a is 4-methyl, 4-methoxy, 4-Cl or 4-Br; R.sub.3b
is monobromo-n-hexyl or monobromo-n-octyl; n.sub.1 is 1; R.sub.1 is
CN; and R.sub.2 is hydrogen; and with the further proviso, that
(P5) A.sub.1 is not phenyl , when A.sub.2 is imidazolyl; at least
one R.sub.3b is CN; R.sub.1 is CN; and R.sub.2 is hydrogen; and
with the further proviso, that (P6) A.sub.1 is not 3-nitrophenyl,
when A.sub.2 is a hetaryl radical; R.sub.1 is --C(.dbd.S)NH.sub.2
and R.sub.2 is hydrogen; and with the further proviso, that (P7)
A.sub.1 is not 4-nitrophenyl or 3,4-dinitrophenyl; and with the
further proviso, that (P8) R.sub.3a is not 2-nitro, when A.sub.1 is
phenyl and n, is 1, 2 or 3.
16. A process for the preparation of a compound of the formula (la)
or, if appropriate, an E/Z isomer, an E/Z isomer mixture and/or a
tautomer thereof, in each case in free form or in salt form, which
comprises a) to prepare a compound of the formula (Ia) in which the
radicals R.sub.1, A.sub.1 and A.sub.2 have the same meanings as
mentioned above and R.sub.2 is hydrogen, and in which the same
provisos (P1) to (P8) as mentioned above hold true, aa) diazotizing
a compound of the formula A.sub.1--NH.sub.2 (III), in which A.sub.1
has the meanings mentioned above under formula (Ia), and ab)
reacting the diazonium salt with a compound of the formula 33in
which R.sub.1 and A.sub.2 have the meanings mentioned above under
formula (Ia) and W is hydrogen or a detachable group; or, b) to
prepare a compound of the formula 34in which A.sub.1, A.sub.2 and
R.sub.2 have the meanings given above for compounds of the formula
(Ia), and in which the same provisos (P1) to (P8) as mentioned
above hold true reacting a compound of the formula 35in which
A.sub.1, A.sub.2 and R.sub.2 have the meanings given above for the
compounds of the formula (Ia) and Hal is a halogen atom, with a
metal cyanide, preferably an alkali metal cyanide; or, c) to
prepare a compound of the formula (Ia) in which R.sub.2 is other
than H, reacting a compound of the formula (Ia) in which R.sub.2 is
hydrogen with a compound of the formula R.sub.2--Q (V), in which
R.sub.2 has the meanings given above under formula (Ia) and Q is a
leaving group; or, d) to prepare a compound of the formula (Ia) in
which R.sub.1 is halo-C.sub.1-C.sub.4alkyl or
--C(.dbd.S)--N(R.sub.5).sub.2, reacting a compound of the formula
36in which R.sub.1a is halo-C.sub.1-C.sub.4alkyl or a group
--C(.dbd.S)--N(R.sub.5).sub.2 and A.sub.2 has the meanings defined
for the compounds of the formula (Ia) with a compound of the
formula 37in which A.sub.1 and R.sub.2 have the meanings given
above for the compounds of the formula (Ia), and in each case, if
so desired, converting a compound of the formula (Ia) which can be
obtained in accordance with the process or by any other means, or
an E/Z isomer or tautomer thereof, in each case in free form or in
salt form, into a different compound of the formula (Ia) or into an
E/Z isomer or tautomer thereof, in each case in free form or in
salt form, resolving an E/Z isomer mixture which can be obtained in
accordance with the process and isolating the desired isomer and/or
converting a free compound of the formula (Ia) which can be
obtained in accordance with the process or by any other means, or
an E/Z isomer or tautomer thereof, into a salt or converting a salt
of a compound of the formula (I) which can be obtained in
accordance with the process or by any other means, or an E/Z isomer
or tautomer thereof, into the free compound of the formula (Ia) or
an E/Z isomer or tautomer thereof or into another salt.
17. A method of controlling pests, which comprises applying a
composition as described in claim 1 to the pests or to their
environment.
18. A method according to claim 17 for the protection of plant
propagation material, which comprises treating the propagation
material or the site where the propagation material is planted.
19. Plant propagation material which has been treated in accordance
with the method described in claim 18.
20. A process for the preparation of a composition as described in
claim 1, which comprises intimately mixing and/or grinding the
active ingredient with the auxiliary (auxiliaries).
21. The use of a compound of the formula (I) as described in claim
1, or, if appropriate, an E/Z isomer, an E/Z isomer mixture and/or
a tautomer thereof, in free form or in agrochemically utilizable
salt form, for the preparation of a composition as described in
claim 1.
22. The use of a composition as described in claim 1 for
controlling pests.
Description
[0001] The invention relates to a pesticidal composition which
comprises at least one compound of the formula 2
[0002] in which
[0003] A.sub.1 and A.sub.2 are independent of one another and are
in each case a mono- or bicyclic aryl or hetaryl radical, each
hetaryl radical independently of the other having 1 up to and
including 4 hetero atoms selected from the group consisting of N, O
and S;
[0004] A.sub.1 is substituted with a substituent (R.sub.3a).sub.n,
and A.sub.2 with a substituent (R.sub.3b).sub.n2;
[0005] R.sub.1 is --CN, halo-C.sub.1-C.sub.6alkyl or
--C(.dbd.S)--N(R.sub.5).sub.2 (in which the two R.sub.5 are
independent of one another);
[0006] R.sub.2 is hydrogen, --OH, C.sub.1-C.sub.6alkyl,
C.sub.1-C.sub.6alkoxy, C.sub.3-C.sub.6cycloalkyl,
C.sub.3-C.sub.6alkenyl, C.sub.3-C.sub.6alkynyl,
halo-C.sub.1-C.sub.6alkyl, halo-C.sub.3-C.sub.6alkenyl,
halo-C.sub.3-C.sub.6alkynyl, benzyl or benzoyl, in which the benzyl
or benzoyl radical is unsubstituted or mono- to trisubstituted in
the aromatic ring by substituents which are independent of one
another and selected from the group consisting of halogen, --CN,
NO.sub.2, C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.6alkoxy,
halo-C.sub.1-C.sub.6alkyl and halo-C.sub.1-C.sub.6alkoxy;
C.sub.1-C.sub.6alkoxy-C.sub.1-C.sub.6alkyl,
cyano-C.sub.1-C.sub.6alkyl, --C(.dbd.X)--R.sub.7,
--OC(.dbd.O)--R.sub.7, --C(.dbd.O)--C(.dbd.O)--R.su- b.7,
--S(.dbd.O).sub.pN(R.sub.6).sub.2 (in which the two R.sub.6 are
independent of one another); cyano,
--C.sub.1-C.sub.6alkyl-N(R.sub.10)--C- (.dbd.O)--R.sub.8,
--C.sub.1-C.sub.6alkyl-S--C(.dbd.S)--R.sub.8,
--C.sub.1-C.sub.6alkyl-S(.dbd.O).sub.p--R.sub.9,
--S(.dbd.O).sub.p--R.sub- .9, or
--CH.sub.2--N(R.sub.10)--SO.sub.2--R.sub.9;
[0007] R.sub.3a and R.sub.3b are independently of each other
halogen, C.sub.1-C.sub.6alkyl, C.sub.2-C.sub.4alkenyl,
C.sub.2-C.sub.4alkynyl, halo-C.sub.1-C.sub.6alkyl,
halo-C.sub.2-C.sub.4alkenyl, halo-C.sub.2-C.sub.4alkynyl,
C.sub.1-C.sub.6alkoxy, halo-C.sub.1-C.sub.6alkoxy,
C.sub.2-C.sub.6alkenyloxy, C.sub.2-C.sub.6alkynyloxy,
halo-C.sub.2-C.sub.6alkenyloxy, halo-C.sub.2-C.sub.6alkynyloxy,
--OH, --SF.sub.5, --CHO, --C(.dbd.O)--C.sub.1-C.sub.6alky),
--C(.dbd.O)-halo-C.sub.1-C.sub.6alkyl,
--C(.dbd.O)--OC.sub.1-C.sub.6alkyl,
--C(.dbd.O)--O-halo-C.sub.1-C.sub.6al- kyl,
--O--C(.dbd.O).sub.2N(R.sub.6).sub.2 (in which the two R.sub.6 are
independent of one another), --CN, --NO.sub.2,
--S(.dbd.O).sub.2N(R.sub.6- ).sub.2 (in which the two R.sub.6 are
independent of one another),
--S(.dbd.O).sub.p--C.sub.1-C.sub.6alkyl,
--S(.dbd.O).sub.p-halo-C.sub.1-C- .sub.6alkyl,
--O--S(.dbd.O).sub.p--C.sub.1-C.sub.6alkyl,
--O--S(.dbd.O).sub.p-halo-C.sub.1-C.sub.6alkyl, phenyl, benzyl,
phenoxy or benzyloxy, each of the phenyl, benzyl, phenoxy or
benzyloxy radicals being unsubstituted or mono- to
penta-substituted in the aromatic ring by substituents which are
independent of one another and selected from the group consisting
of halogen, cyano, NO.sub.2, C.sub.1-C.sub.6alkyl,
halo-C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.6alkoxy and
halo-C.sub.1-C.sub.6alkoxy;
[0008] n.sub.1 and n.sub.2 are 0 or, depending on the substitution
options on the ring systems A.sub.1 and A.sub.2 in question,
independently of each other 1, 2, 3, 4 or 5;
[0009] X is O or S;
[0010] p is 0, 1 or 2;
[0011] R.sub.5 radicals independently of one another are H or
C.sub.1-C.sub.8alkyl;
[0012] R.sub.6 radicals independently of one another are H,
C.sub.1-C.sub.8alkyl, C.sub.3-C.sub.6cycloalkyl, phenyl or benzyl,
the phenyl or benzyl group in the aromatic ring being unsubstituted
or mono- to trisubstituted by substituents which are independent of
one another and selected from the group consisting of halogen,
--CN, NO.sub.2, C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.4alkoxy,
halo-C.sub.1-C.sub.6alkyl and halo-C.sub.1-C.sub.6alkoxy; or two
alkyl radicals R.sub.6 together with the nitrogen atom to which
they are bonded form a five- to seven-membered ring in which a
CH.sub.2 group may be replaced by a hetero atom selected from the
group consisting of O and S, or by NH, and where the five- to
seven-membered ring is unsubstituted or mono- or di-substituted by
C.sub.1-C.sub.4alkyl;
[0013] R.sub.7 is H, C.sub.1-C.sub.8alkyl, C.sub.2-C.sub.8alkenyl,
halo-C.sub.1-C.sub.8alkyl, halo-C.sub.2-C.sub.8alkenyl,
C.sub.1-C.sub.8alkoxy, halo-C.sub.1-C.sub.8alkoxy,
C.sub.3-C.sub.6cycloalkyl, phenyl, benzyl, phenoxy, benzyloxy or
--N(R.sub.6).sub.2 (in which the two R.sub.6 are independent of one
another);
[0014] R.sub.8 is C.sub.1-C.sub.8alkyl, C.sub.1-C.sub.8alkoxy,
halo-C.sub.1-C.sub.8alkyl, halo-C.sub.1-C.sub.8alkoxy,
C.sub.1-C.sub.8alkylthio, phenyl, benzyl or --N(R.sub.6).sub.2 (in
which the two R.sub.6 are independent of one another);
[0015] R.sub.9 is C.sub.1-C.sub.6alkyl, halo-C.sub.1-C.sub.4alkyl
or aryl which is unsubstituted or mono- to trisubstituted by
substituents which are independent of one another and selected from
the group consisting of C.sub.1-C.sub.6alkyl,
C.sub.2-C.sub.4alkenyl, C.sub.2-C.sub.4alkynyl,
C.sub.1-C.sub.4alkoxy, halogen, cyano, halo-C.sub.1-C.sub.4alkyl,
halo-C.sub.2-C.sub.4alkenyl, halo-C.sub.2-C.sub.4alkynyl,
halo-C.sub.1-C.sub.4alkoxy and nitro; and
[0016] R.sub.10 is H, C.sub.1-C.sub.6alkyl,
C.sub.3-C.sub.6cycloalkyl, phenyl or benzyl, the phenyl and benzyl
radicals being unsubstituted or mono- to trisubstituted in the
aromatic ring by substituents which are independent of one another
and selected from the group consisting of C.sub.1-C.sub.4alkyl,
C.sub.1-C.sub.4alkoxy, halogen, cyano, halo-C.sub.1-C.sub.4alkyl,
halo-C.sub.1-C.sub.4alkoxy and nitro;
[0017] or, where appropriate, an E/Z isomer, EIZ isomer mixture
and/or a tautomer thereof, in each case in free form or in
agrochemically utilizable salt form, with the exception of
1-phenyl-hydrazono-2-nitriloe- thylbenzene, as active ingredient
and at least one auxiliary;
[0018] to compounds of the formula (Ia) defined below, E/Z isomers
and/or tautomers thereof, in each case in free form or in salt
form; to a process for the preparation and to the use of these
compounds, E/Z isomers and tautomers; to a process for the
preparation and to the use of these compositions; to intermediates,
in free form or in salt form, for the preparation of these
compounds, if appropriate to tautomers, in free form or in salt
form, of these intermediates; and to a process for the preparation
and to the use of these intermediates and tautomers thereof.
[0019] Certain phenylhydrazone derivatives are proposed in the
literature as active ingredients in pesticides. However, the
biological properties of these known compounds are not entirely
satisfactory in the field of pest control, which is why there is a
demand for providing further compounds which have pesticidal
properties, in particular for controlling insects and
representatives of the order Acarina, this object being achieved
according to the invention by providing the present pesticides
containing compounds of the formula (I).
[0020] Some compounds of the formula (I) contain asymmetric carbon
atoms, which is why optically active forms of the compounds can
occur. Owing to the presence of the C.dbd.N double bond, E- and
Z-isomeric forms of the compounds may occur. Moreover, atropisomers
of the compounds may occur. The formula (I) is intended to embrace
all these isomeric forms which are possible and mixtures of these,
for example racemates or E/Z isomer mixtures.
[0021] Unless otherwise defined, the general terms used hereinabove
and hereinbelow have the meanings given in the following text.
[0022] Unless otherwise defined, carbon-containing groups and
compounds contain in each case 1 up to and including 8, preferably
1 up to and including 6, in particular 1 up to and including 4,
especially 1 or 2, carbon atoms.
[0023] Alkyl--as a group per se and as structural element of other
groups and compounds, such as of haloalkyl, alkoxy or
alkylthio--is, in each case with due consideration of the number of
carbon atoms present in the relevant group or compound in every
single case, either straight-chain, i.e. methyl, ethyl, propyl,
butyl, pentyl or hexyl, or branched, e.g. isopropyl, isobutyl,
sec-butyl, tert-butyl, isopentyl, neopentyl or isohexyl.
[0024] Alkenyl--as a group per se and as structural element of
other groups and compounds, such as of alkenoxy, haloalkenyl or
haloalkenoxy--is, in each case with due consideration of the number
of carbon atoms present in the relevant group or compound in every
single case, either straight-chain, e.g. vinyl, 1-methylvinyl,
allyl, 1-butenyl or 2-hexenyl, or branched, e.g. isopropenyl.
[0025] Alkynyl--as a group per se and as structural element of
other groups and compounds, such as haloalkynyl--is, in each case
with due consideration of the number of carbon atoms present in the
relevant group or compound in every single case, either
straight-chain, e.g. propargyl, 2-butynyl or 5-hexynyl, or
branched, e.g. 2-ethynylpropyl or 2-propargylisopropyl.
[0026] C.sub.3-C.sub.6-cycloalkyl is cyclopropyl, cyclobutyl,
cyclopentyl or cyclohexyl.
[0027] Aryl is especially phenyl or naphthyl, in particular
phenyl.
[0028] Monocyclic hetaryl has 1 up to and including 4 ring hetero
atoms and is, for example, furyl, thienyl, pyridyl, imidazolyl,
thiazolyl, oxazolyl, pyrimidyl, oxadiazolyl, thiadiazolyi,
triazolyl or tetrazolyl.
[0029] Bicyclic hetaryl is to be understood as meaning a radical
which contains 1 up to and including 4 hetero atoms either in only
one ring--for example in quinolinyl, quinoxalinyl, indolinyl,
benzothiophenyl or benzofuranyl--or in both rings--for example in
pteridinyl or purinyl, the hetero atoms being independent of one
another.
[0030] Halogen--as a group per se and as structural element of
other groups and compounds, such as haloalkyl, haloalkenyl,
haloalkynyl and haloalkoxy--is fluorine, chlorine, bromine or
iodine, in particular fluorine, chlorine or bromine, especially
fluorine or chlorine, very particularly chlorine.
[0031] Halogen-substituted carbon-containing groups and compounds,
such as haloalkyl, haloalkenyl or haloalkynyl, can be partially
halogenated or perhalogenated, it being possible for the halogen
substituents to be identical or different in the case of
polyhalogenation. Examples of haloalkyl--as a group per se and as a
structural element of other groups and compounds, such as
haloalkenyl--are methyl which is mono- to trisubstituted by
fluorine, chlorine and/or bromine, such as CHF.sub.2 or CF.sub.3;
ethyl which is mono- to pentasubstituted by fluorine, chlorine
and/or bromine, such as CH.sub.2CF.sub.3, CF.sub.2CF.sub.3,
CF.sub.2CCl.sub.3, CF.sub.2CHCl.sub.2, CF.sub.2CHF.sub.2,
CF.sub.2CFCl.sub.2, CF.sub.2CHBr.sub.2, CF.sub.2CHClF,
CF.sub.2CHBrF or CClFCHClF; propyl or isopropyl, each of which is
mono- to heptasubstituted by fluorine, chlorine and/or bromine,
such as CH.sub.2CHBrCH.sub.2Br, CF.sub.2CHFCF.sub.3,
CH.sub.2CF.sub.2CF.sub.3 or CH(CF.sub.3).sub.2; and butyl or an
isomer thereof which is mono- to nonasubstituted by fluorine,
chlorine and/or bromine, such as CF(CF.sub.3)CHFCF.sub.3 or
CH.sub.2(CF.sub.2).sub.2CF.sub.3. Haloalkenyl is, for example,
CH.sub.2CH.dbd.CHCl, CH.sub.2CH.dbd.CCl.sub.2,
CH.sub.2CF.dbd.CF.sub.2 or CH.sub.2CH.dbd.CHCH.sub.2Br. Haloalkynyl
is, for example, CH.sub.2C.ident.CF, CH.sub.2C.ident.CCH.sub.2Cl or
CF.sub.2GF.sub.2C.ident.CCH.sub.2F.
[0032] Those skilled in the art will be familiar with the fact that
some compounds of the formula (I) can exist as tautomers,
particularly when R.sub.2 is H. The compounds of the formula (I)
are therefore also to be understood as meaning, hereinabove and
hereinbelow, the relevant tautomers, even when the latter are not
mentioned specifically in each individual case.
[0033] Compounds of the formula (I) which have at least one basic
centre can form, for example, acid addition salts. These acid
addition salts are formed for example with strong inorganic acids,
such as mineral acids, e.g. perchloric acid, sulfuric acid, nitric
acid, nitrose acid, a phosphorus acid or a hydrohalic acid, with
strong organic carboxylic acids, such as
C.sub.1-C.sub.4alkanecarboxylic acids which are unsubstituted or
substituted, for example by halogen, e.g. acetic acid, such as
saturated or unsaturated dicarboxylic acids, e.g. oxalic, malonic,
succinic, maleic, fumaric or phthalic acid, such as
hydroxycarboxylic acids, e.g. ascorbic, lactic, malic, tartaric or
citric acid, or such as benzoic acid, or with organic sulfonic
acids, such as C.sub.1-C.sub.4alkanoic or arylsulfonic acids which
are unsubstituted or substituted, for example by halogen, e.g.
methane- or p-toluenesulfonic acid. Furthermore, compounds of the
formula (I) which have at least one acidic group can form salts
with bases. Suitable salts with bases are, for example, metal
salts, such as alkali metal or alkaline earth metal salts, e.g.
sodium, potassium or magnesium salts, or salts with ammonia or an
organic amine, such as morpholine, piperidine, pyrrolidine, a
mono-, di- or tri-lower-alkylamine, e.g. ethyl-, diethyl-,
triethyl- or dimethylpropylamine, or with a mono-, di- or
trihydroxy-lower-alkylamine, e.g. mono-, di- or triethanolamine. If
appropriate, corresponding internal salts may furthermore be
formed. Because of the close relation between the compounds of the
formula (I) in free form and in the form of their salts, the free
compounds of the formula (I) or salts thereof are to be understood
as meaning, hereinabove and hereinbelow, in the spirit and for the
purposes of the present invention, the corresponding salts or the
free compounds of the formula (I), if so appropriate. The same
applies to tautomers of compounds of the formula (I) and the salts
of these tautomers. In general, the free form is preferred in each
case.
[0034] Preferred within the scope of the invention are the
following embodiments where--if necessary--(R.sub.3).sub.n in
A.sub.1 is designated (R.sub.3a).sub.n1 and (R.sub.3).sub.n in
A.sub.2 is designated (R.sub.3b).sub.n2, and where the proviso,
that 1-phenylhydrazono-2-nitril- oethylbenzene is excluded form the
scope in each case applies:
[0035] (1) a pesticidal composition comprising at least one
compound of the formula (1) in which A.sub.1 and A.sub.2
independently of one another are a substituent selected from the
group consisting of 3
[0036] especially phenyl, naphthyl, pyridyl or thiadiazolyl; very
especially phenyl or pyridyl; in particular phenyl;
[0037] R.sub.3 is halogen, --CN, NO.sub.2,
halo-C.sub.1-C.sub.2alkyl, C.sub.1-C.sub.2alkoxy or
halo-C.sub.1-C.sub.2alkoxy, halo-C.sub.2-C.sub.5alkenoxy or
halo-C.sub.2-C.sub.5alkynyloxy; especially chlorine, --CN, CF.sub.3
or OCF.sub.3; where, if m+n is greater than 1, the radicals R.sub.3
are independent of one another;
[0038] R.sub.4 is H, C.sub.1-C.sub.4alkyl, phenyl or benzyl;
especially H and methyl;
[0039] n is, depending on the possibilities for substitution on the
ring system, 0 to 5, especially 1 to 4, more specifically 1 to 3,
and the value of n.sub.1 in A1 is independent of the value of
n.sub.2 in A.sub.2;
[0040] m, depending on the possibilities for substitution on the
ring system, is 0 to 4, and the values of m in A.sub.1 are
independent of the values of m in A.sub.2;
[0041] the total m+n in each radical A.sub.1 and A.sub.2 is 0 to 5;
especially 1, 2,3 or 4; more specifically 1 to 3,
[0042] (2) a pesticidal composition comprising at least one
compound of the formula (I) in which A.sub.1 and A.sub.2 are
phenyl;
[0043] (3) a pesticidal composition comprising at least one
compound of the formula (I) in which R.sub.1 is --CN or
halo-C.sub.1-C.sub.2alkyl; especially --CN or trifluoromethyl, more
especially --CN;
[0044] (4) a pesticidal composition comprising at least one
compound of the formula (I) in which R.sub.2 is hydrogen,
C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4alkoxy-C.sub.1-C.sub.4alkyl,
--C(.dbd.O)--C.sub.1-C.sub.4a- lkyl,
--C(.dbd.O)-halo-C.sub.3-C.sub.6alkenyl ,
--C(.dbd.O)--C.sub.3-C.sub- .6cycloalkyl ,
--C(.dbd.O)--O--C.sub.1-C.sub.2alkyl,
--C(.dbd.O)--C(.dbd.O)--O--C.sub.1-C.sub.2alkyl,
--C(.dbd.O)--C(.dbd.O)--- N(R.sub.6).sub.2, cyano, benzoyl or
benzyl, the benzoyl or benzyl radical being unsubstituted or mono-
to trisubstituted in the aromatic ring by a substituent which is
independent at each occurence and selected from the group
consisting of halogen, --CN, --NO.sub.2, trifluoromethoxy and
trifluoromethyl; or --C(.dbd.O)--N(R.sub.6).sub.2; and
[0045] the two radicals R.sub.6 independently of one another are H,
C.sub.1-C.sub.4alkyl, C.sub.3-C.sub.6cycloalkyl, phenyl or benzyl,
the phenyl or benzyl group being unsubstituted or mono- or
disubstituted in the aromatic ring by substituents which are
independent of one another and selected from the group consisting
of halogen, --CN, C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4alkoxy,
halo-C.sub.1-C.sub.2alkyl and halo-C.sub.1-C.sub.2alkoxy; or two
alkyl radicals R.sub.6 together with the nitrogen atom to which
they are bonded form a five- or six-membered ring in which a
CH.sub.2 group may be replaced by an O atom or by NH and in which
the five- or six-membered ring is unsubstituted or mono- or
disubstituted by methyl; especially in which R.sub.2 is hydrogen,
C.sub.1-C.sub.3alkyl, C.sub.1-C.sub.2alkoxy-C.sub.1-C.sub.2alky- l,
--C(.dbd.O)--C.sub.1-C.sub.2alkyl,
--C(.dbd.O)-fluoro-C.sub.4-C.sub.6al- kenyl,
--C(.dbd.O)-cyclopropyl, --C(.dbd.O)--O--C.sub.1-C.sub.2alkyl,
--C(.dbd.O)--C(.dbd.O)--O--C.sub.1-C.sub.2alkyl,
--C(.dbd.O)--C(.dbd.O)--- N(R.sub.6).sub.2, cyano, benzyl or
o-nitrobenzyl; --C(.dbd.O)--N(R.sub.6).- sub.2; or
--C(.dbd.O)--C.sub.6H.sub.5 in which the phenyl ring is
unsubstituted or mono- to trisubstituted by a substituent selected
from the group consisting of halogen, NO.sub.2, trifluoromethoxy
and trifluoromethyl; and the two radicals R.sub.6 independently of
one another are H, C.sub.1-C.sub.4alkyl, cyclopropyl, phenyl or
benzyl, the phenyl or benzyl group being unsubstituted or mono- or
disubstituted in the aromatic ring by substituents which are
independent of one another and selected from the group consisting
of chlorine, --CN and OCF.sub.3; or two alkyl radicals R.sub.6
together with the nitrogen atom to which they are bonded form a
six-membered ring in which a CH.sub.2 group may be replaced by an O
atom or by NCH.sub.3;
[0046] (5) a pesticidal composition comprising at least one
compound of the formula (I) in which A.sub.1 is a pyridyl
radical;
[0047] (6) a pesticidal composition comprising at least one
compound of the formula (I) in which (R.sub.3a).sub.n1 is Cl,
Cl.sub.2, Cl.sub.3, --(CF.sub.3).sub.2, Cl--CF.sub.3, NO.sub.2,
--CN, Cl.sub.2--NO.sub.2, --OCF.sub.3, --CF.sub.3, Cl--CF.sub.3,
Cl.sub.2--CF.sub.3, Cl.sub.2--OCF.sub.3, --Cl.sub.2--F,
Cl.sub.2--Br, Cl--CF.sub.3--F, Cl--Br--CH.sub.3,
--(CH.sub.3).sub.2--Br, Cl.sub.3--CF.sub.3, Cl.sub.2--F--CF.sub.3,
F.sub.2--CF.sub.3--Cl, Cl.sub.2--CN, Cl.sub.2--CF.sub.3,
Cl.sub.2--SCF.sub.3, Cl.sub.2--OCF.sub.3,
Cl.sub.2--O.sub.2CF.sub.3, Cl.sub.2--SO.sub.2CH.sub.3,
Cl.sub.2--OCF.sub.2Br, Cl.sub.2--OCF.sub.2H,
Cl.sub.2--C.sub.2F.sub.5, (NO.sub.2).sub.2--CF.sub.3,
(NO.sub.2).sub.2--Cl, Cl.sub.2--SO.sub.2CH.su- b.3or
Cl.sub.2--OSO2CF.sub.3; especially
[0048] 2-Cl, 2,3-Cl.sub.2, 2,4-Cl.sub.2, 2,6-Cl.sub.2,
2,4,6-Cl.sub.3, 3,5-(CF.sub.3).sub.2, 2-Cl-4-CF.sub.3, 2-NO.sub.2,
2-CN, 3-CN, 4-CN, 2,6-Cl.sub.2-4-NO.sub.2, 4-OCF.sub.3, 4-CF.sub.3,
3-CF.sub.3, 2-Cl-4-NO.sub.2, 2,6-Cl.sub.2-4-CF.sub.3,
2,6-Cl.sub.2-4-OCF.sub.3, 2,6-Cl.sub.2-4-F, 2,6-Cl.sub.2-4-Br,
2-Cl-4-CF.sub.3-6-F, 2-Cl-4-Br-6-CH.sub.3,
2,6-(CH.sub.3).sub.2-4-Br, 2,3,6-Cl.sub.3-4-CF.sub.- 3,
2,6-Cl.sub.2-3-F-4-CF.sub.3, 2,3-F.sub.2-4-CF.sub.3-6-Cl,
2,6-Cl.sub.2-4-CN, 2,4-Cl.sub.2-6-CF.sub.3,
2,6-Cl.sub.2-4-SCF.sub.3, 2,6-Cl.sub.2-4-SOCF.sub.3,
2,6-Cl.sub.2-4-SO.sub.2CF.sub.3, 2,6-Cl.sub.2-4-SO.sub.2CH.sub.3,
2,6-Cl.sub.2-4-OCF.sub.2Br, 2,6-Cl.sub.2-4-OCF.sub.2H,
2,6-Cl.sub.2-4-C.sub.2F.sub.5, 2,6-(NO.sub.2).sub.2-4-CF.sub.3,
2,6-(NO.sub.2).sub.2-4-Cl, 2,6-Cl.sub.2-4-OSO.sub.2CH.sub.3, or
2,6-Cl.sub.2-4-OSO2CF.sub.3; very especially
[0049] 2,3-Cl.sub.2, 2,4-Cl.sub.2, 2,6-Cl.sub.2, 2,4,6-Cl.sub.3,
3,5-(CF.sub.3).sub.2, 2-Cl-4-CF.sub.3, 2-CN, 3-CN, 4-CN,
2,6-Cl.sub.2-4-NO.sub.2, 4-OCF.sub.3, 4-CF.sub.3, 3-CF.sub.3,
2-Cl-4-NO.sub.2, 2,6-Cl.sub.2-4-CF.sub.3, 2,6-Cl.sub.2-4-OCF.sub.3,
2,6-Cl.sub.2-4-F, 2,6-Cl.sub.2-4-Br, 2-Cl-4-CF.sub.3-6-F,
2-Cl-4-Br-6-CH.sub.3, 2,6-(CH.sub.3).sub.2-4-Br,
2,3,6-Cl.sub.3-4-CF.sub.- 3, 2,6-Cl.sub.2-3-F-4-CF.sub.3,
2,3-F.sub.2-4-CF.sub.3-6-Cl, 2,6-Cl.sub.2-4-CN,
2,4-Cl.sub.2-6-CF.sub.3, 2,6-Cl.sub.2-4-SCF.sub.3,
2,6-Cl.sub.2-4-SOCF.sub.3, 2,6-Cl.sub.2-4-C.sub.2F.sub.5,
2,6-(NO.sub.2).sub.2-4-CF.sub.3, 2,6-(NO.sub.2).sub.2-4-Cl,
2,6-Cl.sub.2-4-OSO.sub.2CH.sub.3, or
2,6-Cl.sub.2-4-OSO2CF.sub.3;
[0050] (7) a pesticidal composition comprising at least one
compound of the formula (I) in which (R.sub.3b).sub.n2 is --CN, Cl,
Cl.sub.2, F, F.sub.2, Br, --NO.sub.2, --(NO.sub.2).sub.2,
--NO.sub.2--CF.sub.3, CF.sub.3, --(CF.sub.3).sub.2, --CN--CF.sub.3,
Cl--CF.sub.3, F--CN, --Cl--CN, --OCF.sub.3, --Cl--NO.sub.2,
--CH.sub.3--NO.sub.2, --OCH.sub.3--NO.sub.2, --C.sub.6H.sub.5,
--C.sub.6H.sub.4--F, --C.sub.6H.sub.4-Cl,
--C.sub.6H.sub.4--CF.sub.3, --C.sub.6H.sub.4--CF.sub- .3,
--C.sub.6H.sub.4--NO.sub.2, --C.sub.6H.sub.3--(CF.sub.3).sub.2,
--C.sub.6H.sub.3--Cl.sub.2, --C.sub.6H.sub.3--(Cl--F), --F--CN,
F--NO.sub.2, --CHO or --C(.dbd.O)CF.sub.3; especially
[0051] 4-CN, 3-CN, 4-Cl, 3,4-Cl.sub.2, 2,3-Cl.sub.2, 3,5-Cl.sub.2,
2,5-Cl.sub.2, 3,5-F.sub.2, 2,6-F.sub.2, 4-Br, 2-F, 4-NO.sub.2,
2-NO.sub.2-4-CF.sub.3, 3-CF.sub.3, 4-CF.sub.3,
3,5-(CF.sub.3).sub.2, 2-CN-4-CF.sub.3, 2-Cl-4-CF.sub.3, 2-F-4-CN,
3-Cl-4-CN, 4-OCF.sub.3, 3-OCF.sub.3, 4-Cl-3-NO.sub.2,
2-Cl-4-NO.sub.2, 3-CH.sub.3-4-NO.sub.2, 3-OCH.sub.3-4-NO.sub.2,
4-C.sub.6H.sub.5, 4-C.sub.6H.sub.4-4-F, 4-C.sub.6H.sub.4-4-Cl,
4-C.sub.6H.sub.4-4-CF.sub.3, 4-C.sub.6H.sub.4-3-CF.sub.3,
4-C.sub.6H.sub.4-3-NO.sub.2, 4-C.sub.6H.sub.3-(3,5-CF.sub.3).sub.2,
4-C.sub.6H.sub.3-2,4-Cl.sub.2, 4-C.sub.6H.sub.3-3,4-Cl.sub.2,
4-C.sub.6H.sub.3-3,5-Cl.sub.2, 4-C.sub.6H.sub.3-(3-Cl-4-F),
2-F-4-NO.sub.2, 4-CHO or 4-C(.dbd.O)CF.sub.3; very especially
[0052] 4-NO.sub.2, 4-CN, 3-CN, 4-Cl, 3,4-Cl.sub.2, 2,3-Cl.sub.2,
3,5-Cl.sub.2, 2,5-Cl.sub.2, 3,5-F.sub.2, 2,6-F.sub.2, 2-F,
2-NO.sub.2-4-CF.sub.3, 3-CF.sub.3, 4-CF.sub.3,
3,5-(CF.sub.3).sub.2, 2-CN-4-CF.sub.3, 2-Cl-4-CF.sub.3, 2-F-4-CN,
3-Cl-4-CN, 4-OCF.sub.3, 3-OCF.sub.3, 4-Cl-3-NO.sub.2,
2-Cl-4-NO.sub.2, 3-CH.sub.3-4-NO.sub.2, 3-OCH.sub.3-4-NO.sub.2,
4-C.sub.6H.sub.5, 2-F-4-NO.sub.2, 4-CHO or 4-C(.dbd.O)CF.sub.3;
[0053] (8) a pesticidal composition comprising at least one
compound of the formula (1) in which (R.sub.3a).sub.n1 is 2-Cl,
2,3-Cl.sub.2, 2,4-Cl.sub.2, 2,6-Cl.sub.2, 2,4,6-Cl.sub.3,
3,5-(CF.sub.3).sub.2, 2-Cl-4-CF.sub.3, 4-NO.sub.2, 2-NO.sub.2,
2-CN, 3-CN, 4-CN, 2,6-Cl.sub.2-4-NO.sub.2, 4-OCF.sub.3, 4-CF.sub.3,
3-CF.sub.3, 2-Cl-4-NO.sub.2, 2,6-Cl.sub.2-4-CF.sub.3,
2,6-Cl.sub.2-4-OCF.sub.3, 2,6-Cl.sub.2-4-F, 2,6-Cl.sub.2-4-Br,
2-Cl-4-CF.sub.3-6-F, 2-Cl-4-Br-6-CH.sub.3,
2,6-(CH.sub.3).sub.2-4-Br, 2,3,6-Cl.sub.3-4-CF.sub.- 3,
2,6-Cl.sub.2-3-F-4-CF.sub.3, 2,3-F.sub.2-4-CF.sub.3-6-Cl,
2,6-Cl.sub.2-4-CN, 2,4-Cl.sub.2-6-CF.sub.3,
2,6-Cl.sub.2-4-SCF.sub.3, 2,6-Cl.sub.2-4-SOCF.sub.3,
2,6-Cl.sub.2-4-SO.sub.2CF.sub.3, 2,6-Cl.sub.2-4-SO.sub.2CH.sub.3,
2,6-Cl.sub.2-4-OCF.sub.2Br, 2,6-Cl.sub.2-4-OCF.sub.2H,
2,6-Cl.sub.2-4-C.sub.2F.sub.5, 2,6-(NO.sub.2).sub.2-4-CF.sub.3,
2,6-(NO.sub.2).sub.2-4-Cl, 2,6-Cl.sub.2-4-OSO.sub.2CH.sub.3, or
2,6-Cl.sub.2-4-OSO2CF.sub.3; and
[0054] (R.sub.3b).sub.n2 is 4-CN, 3-CN, 4-Cl, 3,4-Cl.sub.2,
2,3-Cl.sub.2, 3,5-Cl.sub.2, 2,5-Cl.sub.2, 3,5-F.sub.2, 2,6-F.sub.2,
4-Br, 2-F, 4-NO.sub.2, 2-NO.sub.2, 2,4-(NO.sub.2).sub.2,
2-NO.sub.2-4-CF.sub.3, 3-CF.sub.3, 4-CF.sub.3,
3,5-(CF.sub.3).sub.2, 2-CN-4-CF.sub.3, 2-Cl-4-CF.sub.3, 2-F-4-CN,
3-Cl-4-CN, 4-OCF.sub.3, 3-OCF.sub.3, 4-Cl-3-NO.sub.2,
2-Cl-4-NO.sub.2, 3-CH.sub.3-4-NO.sub.2, 3-OCH.sub.3-4-NO.sub.2,
4-C.sub.6H.sub.5, 4-C.sub.6H.sub.4-4-F, 4-C.sub.6H.sub.4-4-Cl,
4-C.sub.6H.sub.4-4-CF.sub.3, 4-C.sub.6H.sub.4-3-CF.sub.3,
4-C.sub.6H.sub.4-3-NO.sub.2, 4-C.sub.6H.sub.3-(3,5-CF.sub.3).sub.2,
4-C.sub.6H.sub.3-2,4-Cl.sub.2, 4-C.sub.6H.sub.3-3,4-Cl.sub.2,
4-C.sub.6H.sub.3-3,5-Cl.sub.2, 4-C.sub.6H.sub.3-(3-Cl-4-F),
2-F-4-NO.sub.2, 4-CHO or 4--C(.dbd.O)CF.sub.3; very especially
[0055] (R.sub.3a).sub.n1 is 2,3-Cl.sub.2, 2,4-Cl.sub.2,
2,6-Cl.sub.2, 2,4,6-Cl.sub.3, 3,5-(CF.sub.3).sub.2,
2-Cl-4-CF.sub.3, 2-CN, 3-CN, 4-CN, 2,6-Cl.sub.2-4-NO.sub.2,
4-OCF.sub.3, 4-CF.sub.3, 3-CF.sub.3, 2-Cl-4-NO.sub.2,
2,6-Cl.sub.2-4-CF.sub.3, 2,6-Cl.sub.2-4-OCF.sub.3,
2,6-CO.sub.2-4-F, 2,6-Cl.sub.2-4-Br, 2-Cl-4-CF.sub.3-6-F,
2-Cl-4-Br-6-CH.sub.3, 2,6-(CH.sub.3).sub.2-4-Br,
2,3,6-Cl.sub.3-4-CF.sub.- 3, 2,6-Cl.sub.2-3-F-4-CF.sub.3,
2,3-F.sub.2-4-CF.sub.3-6-Cl, 2,6-Cl.sub.2-4-CN,
2,4-Cl.sub.2-6-CF.sub.3, 2,6-Cl.sub.2-4-SCF.sub.3,
2,6-Cl.sub.2-4-SOCF.sub.3, 2,6-Cl.sub.2-4-C.sub.2F.sub.5,
2,6-(NO.sub.2).sub.2-4-CF.sub.3, 2,6-(NO.sub.2).sub.2-4-Cl,
2,6-Cl.sub.2-4-OSO.sub.2CH.sub.3, or 2,6-Cl.sub.2-4-OSO2CF.sub.3;
and
[0056] (R.sub.3b).sub.n2 is 4-CN, 3-CN, 4-Cl, 3,4-Cl.sub.2,
2,3-Cl.sub.2, 3,5-Cl.sub.2, 2,5-Cl.sub.2, 3,5-F.sub.2, 2,6-F.sub.2,
2-F, 4-NO.sub.2, 2-NO.sub.2-4-CF.sub.3, 3-CF.sub.3, 4-CF.sub.3,
3,5-(CF.sub.3).sub.2, 2-CN-4-CF.sub.3, 2-Cl-4-CF.sub.3, 2-F-4-CN,
3-Cl-4-CN, 4-OCF.sub.3, 3-OCF.sub.3, 4-Cl-3-NO.sub.2,
2-Cl-4-NO.sub.2, 3-CH.sub.3-4-NO.sub.2, 3-OCH.sub.3-4-NO.sub.2,
4-C.sub.6H.sub.5, 2-F-4-NO.sub.2, 4-CHO or 4-C(.dbd.O)CF.sub.3;
[0057] (9) a pesticidal composition comprising at least one
compound of the formula (I) in which R.sub.2 is hydrogen;
[0058] (10) a pesticidal composition comprising at least one
compound of the formula (I) in which R.sub.2 is --OH,
C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.6alkoxy,
C.sub.3-C.sub.6cycloalkyl, C.sub.3-C.sub.6alkenyl,
C.sub.3-C.sub.6alkynyl, halo-C.sub.3-C.sub.6alkenyl, benzyl or
benzoyl, the benzyl or benzoyl radical being unsubstituted or mono-
to trisubstituted in the aromatic ring by substituents which are
independent of one another and selected from the group consisting
of halogen, --CN, NO.sub.2, C.sub.1-C.sub.6alkyl,
C.sub.1-C.sub.6alkoxy, halo-C.sub.1-C.sub.6alkyl and
halo-C.sub.1-C.sub.6alkoxy;
C.sub.1-C.sub.6alkoxy-C.sub.1-C.sub.6alkyl,
cyano-C.sub.1-C.sub.6alkyl, --C(.dbd.X)--R.sub.7,
--OC(.dbd.O)--R.sub.7, --C(.dbd.O)--C(.dbd.O)--R.su- b.7,
--S(.dbd.O).sub.pN(R.sub.6).sub.2 (in which the two R.sub.6 are
independent of one another); cyano,
--CH.sub.2--N(R.sub.5)--C(.dbd.O)--R.- sub.8,
--CH.sub.2--S--C(.dbd.S)--R.sub.8,
--C.sub.1-C.sub.4alkyl-S(.dbd.O)- .sub.p--R.sub.9,
--S(.dbd.O).sub.p--R.sub.9, or --CH.sub.2-N(R.sub.10)--SO-
.sub.2--R.sub.9;
[0059] especially --CH.sub.3, --C.sub.2H.sub.5, n--C.sub.3H.sub.7,
i--C.sub.3H.sub.7, --CH.sub.2OC.sub.2H.sub.5, --CH.sub.2OCH.sub.3,
--CH.sub.2-S--CH.sub.3, --CN, --COCH.sub.3,
--CH.sub.2--CH.dbd.CH.sub.2, --CH.sub.2--CH.dbd.CCl.sub.2,
--CH.sub.2C.ident.CH, --CH.sub.2C.sub.6H.sub.5,
--CH.sub.2C.sub.6H.sub.4-2-NO.sub.2, 4
[0060] --CH.sub.2CN, --COC.sub.2H.sub.5, --CO-cyclo-C.sub.3H.sub.5,
--CO(CH.sub.2).sub.3CH.dbd.CF.sub.2, --CO.sub.2CH.sub.3,
--CO.sub.2C.sub.2H.sub.5,
--CO.sub.2C.sub.2H.sub.2CH(CH.sub.3).sub.2,
--CO.sub.2C.sub.8H.sub.17,
--CO.sub.2C.sub.2H.sub.2CH(CH.sub.3).sub.2,
--CO.sub.2C.sub.6H.sub.5, --CO.sub.2CH.sub.2C.sub.6H.sub.5,
--CO.sub.2CH.sub.2CH.sub.2Cl,
--CH.sub.2N(CH.sub.3)CO.sub.2C.sub.2H.sub.5- ,
--CH.sub.2N-CO.sub.2C.sub.6H.sub.5,
--CH.sub.2N(CH.sub.3)CO.sub.2CH.sub.- 3, --COCO.sub.2CH.sub.3,
--COCO.sub.2C.sub.2H.sub.5, --COCONHC.sub.2H.sub.5, --CONHCH.sub.3,
--CONHC.sub.2H.sub.5, --CONHC.sub.6H.sub.4-4-OCF.sub.3,
--COC.sub.6H.sub.4-4-Cl, --CH.sub.2N(CH.sub.3)SO.sub.2CH.sub.3,
--CH.sub.2N(CH.sub.3)SO.sub.2C.sub- .2H.sub.5,
--CH.sub.2N(CH.sub.3)SO.sub.2C.sub.6H.sub.5 or --CH.sub.2Cl;
[0061] (11) a pesticidal composition comprising at least one
compound of the formula (I) in which n.sub.1 is 1, 2, 3 or 4,
preferably 2 or 3;
[0062] (12) a pesticidal composition comprising at least one
compound of the formula (I) in which n.sub.2 is 1 or 2, preferably
1;
[0063] (13) a pesticidal composition comprising at least one
compound of the formula (I) in which n.sub.1 is 2, 3 or 4 and
n.sub.2 is 1 or 2;
[0064] (14) a pesticidal composition comprising at least one
compound of the formula (I) in which R.sub.7 is H,
C.sub.1-C.sub.6alkyl, C.sub.3-C.sub.6alkenyl,
halo-C.sub.1-C.sub.6alkyl, halo-C.sub.3-C.sub.6alkenyl,
C.sub.1-C.sub.6alkoxy, halo-C.sub.1-C.sub.6alkoxy,
C.sub.3-C.sub.6cycloalkyl, phenyl, benzyl, phenoxy, benzyloxy or
--N(R.sub.6).sub.2 (in which the two R.sub.6 are independent of one
another).
[0065] Especially preferred within the scope of the invention are
pesticides comprising at least one of the compounds of the formula
(I) listed in Tables 3 to 29 and, where appropriate, the E/Z
isomers and E/Z isomer mixtures thereof.
[0066] The invention furthermore relates to the compounds of the
formula 5
[0067] in which
[0068] A.sub.1, A.sub.2, R.sub.1, R.sub.2 and the substituents
R.sub.3a and R.sub.3b of A.sub.1 and A.sub.2 have the meanings
given hereinbefore for formula (I); and
[0069] n.sub.1 and n.sub.2 are, depending on the substitution
options on the ring systems A.sub.1 and A.sub.2 in question,
independently of each other, 1, 2, 3, 4 or 5; or, if appropriate,
the E/Z isomers, E/Z isomer mixtures and/or tautomers thereof, in
each case in free form or in salt form; with the proviso, that
[0070] (P1) at least one of the substituents R.sub.3a and R.sub.3b
is halogen-C.sub.1-C.sub.6-alkyl, halogen-C.sub.2-C.sub.4-alkenyl,
halogen-C.sub.2-C.sub.4-alkinyl, halogen-C.sub.1-C.sub.6-alkoxy,
C.sub.2-C.sub.6-alkenyloxy, C.sub.2-C.sub.6-alkynyloxy,
halogen-C.sub.2-C.sub.6-alkenyloxy,
halogen-C.sub.2-C.sub.6-alkynyloxy, --SF.sub.5, --CHO,
--C(.dbd.O)-halogen-C.sub.1-C.sub.6-alkyl,
--C(.dbd.O)--O-halogen-C.sub.1-C.sub.6-alkyl,
--O--C(.dbd.O)N(R.sub.6).su- b.2 (in which the two R.sub.6 are
independent of one another); --CN,
--S(.dbd.O).sub.2n(R.sub.6).sub.2 (in which the two R.sub.6 are
independent of one another);
--S(.dbd.O).sub.p--C.sub.1-C.sub.6-alkyl,
--S(.dbd.O).sub.p-halogen-C.sub.1-C.sub.6-alkyl,
--O--S(.dbd.O).sub.p--C.- sub.1-C.sub.6-alkyl,
--O--S(.dbd.O).sub.p-halogen-C.sub.1-C.sub.6-Alkyl, phenyl, benzyl,
phenoxy or benzyloxy, each of the phenyl, benzyl, phenoxy or
benzyloxy radicals being unsubstituted or mono- to pentasubstituted
in the aromatic ring by substituents which are independent of one
another and selected from the group consisting of halogen, cyano,
NO.sub.2, C.sub.1-C.sub.6alkyl, halo-C.sub.1-C.sub.6alkyl,
C.sub.1-C.sub.6alkoxy and halo-C.sub.1-C.sub.6alkoxy; when
[0071] n.sub.1 is 1 or 2; n.sub.2 is 1; and R.sub.1 is CN or
halogen-C.sub.1-C.sub.6-alkyl, and R.sub.2 is hydrogen;
[0072] and with the further proviso, that
[0073] (P2) R.sub.3a is not 2-OH, when A.sub.2 is 4-nitrophenyl;
R.sub.1 is CN; and R.sub.2 is hydrogen;
[0074] and with the further proviso, that
[0075] (P3) A.sub.1 is not 4-chlorophenyl, 4-bromophenyl or
4-iodophenyl, when
[0076] A.sub.2 is 2,4-dinitrophenyl; R.sub.1 is CN; and R.sub.2 is
hydrogen;
[0077] and with the further proviso, that
[0078] (P4) A.sub.1 is not phenyl, when A.sub.2 is tetrazolyl;
[0079] R.sub.3a is 4-methyl, 4-methoxy, 4-Cl or 4-Br;
[0080] R.sub.3b is monobromo-n-hexyl or monobromo-n-octyl;
[0081] n.sub.1 is 1; R.sub.1 is CN; and R.sub.2 is hydrogen;
[0082] and with the further proviso, that
[0083] (P5) A.sub.1 is not phenyl , when
[0084] A.sub.2 is imidazolyl; at least one R.sub.3b is CN;
[0085] R.sub.1 is CN; and R.sub.2 is hydrogen;
[0086] and with the further proviso, that
[0087] (P6) A.sub.1 is not 3-nitrophenyl, when A.sub.2 is a hetayl
radical;
[0088] R.sub.1 is --C(.dbd.S)NH.sub.2 and R.sub.2 is hydrogen;
[0089] and with the further proviso, that
[0090] (P7) A.sub.1 is not 4-nitrophenyl or 3,4-dinitrophenyl;
[0091] and with the further proviso, that
[0092] (P8) R.sub.3a is not 2-nitro, when A.sub.1 is phenyl and n,
is 1, 2 or 3.
[0093] As far as the compounds of the formula (Ia) are concerned,
the groups (1) to (14), which are mentioned hereinbefore as
defining preferred groups of compounds of the formula (I) used as
active ingredients in the compositions according to the invention,
define also preferred groups of compounds of the formula (Ia),
where, however, the provisos (P1) to (P8) mentioned hereinbefore
have to be taken into consideration appropriately in each case. The
invention furthermore relates to a process for the preparation of
the compounds of the formula (Ia) or, if appropriate, the E/Z
isomers, E/Z isomer mixtures and/or tautomers thereof, in each case
in free form or in salt form, which comprises,
[0094] a) to prepare a compound of the formula (la) in which the
radicals R.sub.1, A.sub.1 and A.sub.2 have the same meanings as
mentioned above and R.sub.2 is hydrogen, and in which the same
provisos (P1) to (P8) as mentioned above hold true,
[0095] aa) diazotizing a compound of the formula
A.sub.1--NH.sub.2 (III),
[0096] in which A.sub.1 has the meanings mentioned above under
formula (Ia), and
[0097] ab) reacting the diazonium salt with a compound of the
formula 6
[0098] in which R.sub.1 and A.sub.2 have the meanings mentioned
above under formula (Ia) and W is hydrogen or a detachable group;
or,
[0099] b) to prepare a compound of the formula 7
[0100] in which A.sub.1, A.sub.2 and R.sub.2 have the meanings
given above for compounds of the formula (Ia), and in which the
same provisos (P1) to (P8) as mentioned above hold true reacting a
compound of the formula 8
[0101] in which A.sub.1, A.sub.2 and R.sub.2 have the meanings
given above for the compounds of the formula (Ia) and Hal is a
halogen atom, preferably chlorine or bromine, especially chlorine,
with a metal cyanide, preferably an alkali metal cyanide,
especially sodium cyanide; or,
[0102] c) to prepare a compound of the formula (Ia) in which
R.sub.2 is other than H, reacting a compound of the formula (Ia) in
which R.sub.2 is hydrogen with a compound of the formula 9
[0103] in which R.sub.2 has the meanings given above under formula
(Ia) and Q is a leaving group, preferably chlorine, bromine or
iodine, especially iodine, preferably in the presence of a base;
or,
[0104] d) to prepare a compound of the formula (Ia) in which
R.sub.1 is halo-C.sub.1-C.sub.4alkyl or
--C(.dbd.S)--N(R.sub.5).sub.2, reacting a compound of the formula
10
[0105] in which R.sub.1a is halo-C.sub.1-C.sub.4alkyl or a group
--C(.dbd.S)--N(R.sub.5).sub.2 and A.sub.2 has the meanings defined
for the compounds of the formula (Ia)
[0106] with a compound of the formula 11
[0107] in which A.sub.1 and R.sub.2 have the meanings given above
for the compounds of the formula (Ia), and in each case, if so
desired, converting a compound of the formula (Ia) which can be
obtained in accordance with the process or by any other means, or
an E/Z isomer or tautomer thereof, in each case in free form or in
salt form, into a different compound of the formula (Ia) or into an
EIZ isomer or tautomer thereof, in each case in free form or in
salt form, resolving an E/Z isomer mixture which can be obtained in
accordance with the process and isolating the desired isomer and/or
converting a free compound of the formula (Ia) which can be
obtained in accordance with the process or by any other means, or
an E/Z isomer or tautomer thereof, into a salt or converting a salt
of a compound of the formula (I) which can be obtained in
accordance with the process or by any other means, or an E/Z isomer
or tautomer thereof, into the free compound of the formula (Ia) or
an E/Z isomer or tautomer thereof or into another salt.
[0108] The invention furthermore relates to a process for the
preparation of a compound of the formula (II), in which A.sub.1,
A.sub.2 and R.sub.2 have the meanings given above for the compounds
of the formula (Ia) and Hal is a halogen atom, and, if appropriate,
the E/Z isomers and tautomers thereof, in each case in free form or
in salt form, which comprises
[0109] e) reacting a compound of the formula 12
[0110] in which the radicals A.sub.11, A.sub.22 and R.sub.2 have
the same meaning as indicated above for A.sub.1 and A.sub.2 under
formula (Ia), with a halogenating agent, or
[0111] f) reacting a compound of the formula 13
[0112] in which R.sub.2 and the two radicals A.sub.111 and
A.sub.222 have the same meaning as given for A.sub.1 and A.sub.2
above under formula (Ia), with N-bromosuccinimide or
N-chlorosuccinimide in the presence of a thioether; and in each
case, if so desired, converting a compound of the formula (II)
which can be obtained in accordance with the process or by any
other means, or an E/Z isomer or tautomer thereof, in each case in
free form or in salt form, into a different compound of the formula
(II) or into an E/Z isomer or tautomer thereof, in each case in
free form or in salt form, resolving an E/Z isomer mixture which
can be obtained in accordance with the process and isolating the
desired isomer and/or converting a free compound of the formula
(II) which can be obtained in accordance with the process or by any
other means, or an E/Z isomer or tautomer thereof, into a salt or
converting a salt of a compound of the formula (II) which can be
obtained in accordance with the process or by any other means, or
an E/Z isomer or tautomer thereof, into the free compound of the
formula (II) or an E/Z isomer or tautomer thereof or into another
salt.
[0113] The reactions described hereinabove and hereinbelow are
carried out in a manner known per se, for example in the absence
or, normally, in the presence of a suitable solvent or diluent or a
mixture of these, the process being carried out, as required, with
cooling, at room temperature or with heating, for example in a
temperature range of from approximately 0.degree. C. to the boiling
point of the reaction medium, preferably from approximately
20.degree. C. to approximately +120.degree. C., in particular
60.degree. C. to 80.degree. C., and, if required, in a sealed
vessel, under pressure, in an inert gas atmosphere and/or under
anhydrous conditions. Especially advantageous reaction conditions
can be seen from the examples.
[0114] Variant a):
[0115] aa) Diazotation is effected under the conditions known to
those skilled in the art, that is to say in the presence of strong
inorganic acids, such as mineral acids, e.g. perchloric acid,
sulfuric acid, nitric acid, nitrous acid, phosphoric acid or a
hydrohalic acid, normally in the presence of water, but also in
pure sulfuric acid.
[0116] Depending on the basicity of the aromatic amine, the
reaction is carried out in a temperature range of approximately
-10.degree. C. to approximately +20.degree. C., or else, if
required, at higher temperatures, for example at 60.degree. C. to
80.degree. C.
[0117] The reaction is preferably carried out under atmospheric
pressure.
[0118] The reaction can be carried out without a protective gas
atmosphere; however, it is preferably carried out under a
protective gas atmosphere, e.g. nitrogen or argon, in particular
nitrogen.
[0119] The reaction time is preferably approximately 1 to
approximately 2 hours.
[0120] The product is normally not isolated, but processed
immediately in the next reaction step.
[0121] Especially preferred conditions for the reaction are
described in Example H6/a.
[0122] ab) The reaction is normally carried out in the presence of
water and, preferably, in the presence of an organic carboxylic
acid, e.g. formic acid, chloroacetic acid, trifluoroacetic acid,
cyanoacetic acid, oxalic acid, malonic acid, succinic acid, maleic
acid, fumaric acid or phthalic acid; it is especially preferred to
add acetic acid.
[0123] A detachable group W is to be understood as meaning an
electron-attracting group which is easily detachable under the
reaction conditions which prevail. Particularly suitable for this
purpose is a group --C(.dbd.O)R or --OC(.dbd.O)R in which R is H,
C.sub.1-C.sub.4alkyl, halo-C.sub.1-C.sub.4alkyl,
C.sub.1-C.sub.4alkoxy, halo-C.sub.1-C.sub.4alkoxy; --CN, or organic
sulfonates, such as C.sub.1-C.sub.4alkane- or arylsulfonates which
are unsubstituted or substituted, for example by halogen, e.g.
methane-, trifluoromethane- or p-toluenesulfonate.
[0124] The reaction is advantageously carried out in a temperature
range from approximately -10.degree. C. to approximately
+30.degree. C., preferably from approximately 0.degree. C. to
approximately +25.degree. C.
[0125] The reaction is preferably carried out under atmospheric
pressure.
[0126] The reaction can be carried out without a protective gas
atmosphere; however, it is preferably carried out under a
protective gas atmosphere, e.g. nitrogen or argon, in particular
nitrogen.
[0127] The reaction time is not critical; a reaction time of
approximately 0.5 to approximately 8 hours, in particular from
approximately 2 to approximately 4 hours, is preferred.
[0128] The product is isolated by customary methods, e.g. by
filtration, crystallization, distillation or chromatography, or any
suitable combination of these processes.
[0129] Especially preferred conditions for the reaction are
described in Example H6/b.
[0130] Variant b):
[0131] Suitable for the reaction are transition metal cyanides,
such as CuCN or Ni(CN).sub.2, and also alkaline earth metal and
alkali metal cyanides; especially KCN and NaCN.
[0132] The reactants can be reacted with each other as such, i.e.
without addition of a solvent or diluent, e.g. in the melt. In most
cases, however, the addition of an inert solvent or diluent or a
mixture of these is advantageous. Examples of such solvents or
diluents which may be mentioned are: aromatic, aliphatic and
alicyclic hydrocarbons and halohydrocarbons such as benzene,
toluene, xylene, mesitylene, tetralin, chlorobenzene,
dichlorobenzene, bromobenzene, petroleum ether, hexane,
cyclohexane, dichloromethane, trichloromethane, tetrachloromethane,
dichloroethane, trichloroethane or tetrachloroethene; esters such
as ethyl acetate; ethers such as diethyl ether, dipropyl ether,
diisopropyl ether, dibutyl ether, tert-butyl methyl ether, ethylene
glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene
glycol dimethyl ether, dimethoxydiethyl ether, tetrahydrofuran or
dioxane; ketones such as acetone, methyl ethyl ketone or methyl
isobutyl ketone; alcohols such as methanol, ethanol, propanol,
isopropanol, butanol, ethylene glycol or glycerol; amides such as
N,N-di-methylformamide, N,N-diethylformamide,
N,N-dimethylacetamide, N-methylpyrrolidone or hexamethylphosphoric
triamide; nitriles, such as acetonitrile or propionitrile; and
sulfoxides such as dimethyl sulfoxide; or water. Preferred are
alcohols and water, or alcohol/water mixtures.
[0133] The reaction is advantageously carried out in a temperature
range from approximately 0.degree. C. to approximately 80.degree.
C., preferably from approximately 20.degree. C. to approximately
30.degree. C., in many cases in the range between room temperature
and the reflux temperature of the reaction mixture.
[0134] The reaction is preferably carried out under atmospheric
pressure.
[0135] The reaction can be carried out without a protective gas
atmosphere; however, it is preferably carried out under a
protective gas atmosphere, e.g. nitrogen or argon, in particular
nitrogen.
[0136] The reaction time is not critical; a reaction time of
approximately 0.1 to approximately 24 hours, in particular from
approximately 3 to approximately 5 hours, is preferred.
[0137] The product is isolated by customary methods, e.g. by
filtration, crystallization, distillation or chromatography, or any
suitable combination of these processes.
[0138] In a preferred embodiment of variant b), a compound of the
formula (II) is reacted with sodium cyanide in an ethanol/water
mixture at room temperature. Especially preferred conditions for
the reaction are described in Example H5.
[0139] Variant c):
[0140] Examples of suitable leaving groups Q in the compounds of
the formula (V) are hydroxyl, C.sub.1-C.sub.8alkoxy,
halo-C.sub.1-C.sub.8alko- xy, C.sub.1-C.sub.8alkanoyloxy, mercapto,
Cl-Caalkylthio, halo-C.sub.1-C.sub.8alkylthio,
C.sub.1-C.sub.8alkanesulfonyloxy,
halo-C.sub.1-C.sub.8alkanesulfonyloxy, benzenesulfonyloxy,
toluenesulfonyloxy and halogen, preferably toluenesulfonyloxy,
trifluoromethanesulfonyloxy or halogen, in particular halogen,
especially chlorine, bromine or iodine, especially iodine. Examples
of suitable bases for facilitating the reaction are the hydroxides,
hydrides, amides, alkoxides, acetates, carbonates, dialkylamides or
alkylsilylamides of alkali metals or alkaline earth metals, or
alkylamines, alkylenediamines, free or N-alkylated, saturated or
unsaturated cycloalkylamines, basic heterocycles, ammonium
hydroxides and carbocyclic amines. Examples which may be mentioned
are sodium hydroxide, sodium hydride, sodium amide, sodium
methoxide, sodium acetate, sodium carbonate, potassium
tert-butoxide, potassium hydroxide, potassium carbonate, potassium
hydride, lithium diisopropylamide, potassium
bis(trimethylsilyl)amide, calcium hydride, triethylamine,
diisopropylethylamine, triethylenediamine, cyclohexylamine,
N-cyclohexyl-N,N-dimethylamine, N,N-diethylaniline, pyridine,
4-(N,N-dimethylamino)pyridine, quinuclidine, N-methylmorpholine,
benzyltrimethylammonium hydroxide, and
1,5-diazabicyclo[5.4.0]undec-5-ene (DBU). Alkali metal carbonates,
alkaline earth metal carbonates, alkylamines, alkali metal
alkoxides and alkaline earth metal alkoxides are preferred.
[0141] The reactants can be reacted with each other as such, i.e.
without addition of a solvent or diluent, e.g. in the melt. In most
cases, however, it is advantageous to add an inert solvent or
diluent or mixture of these. Examples of such solvents or diluents
which may be mentioned are: aromatic, aliphatic and alicyclic
hydrocarbons such as benzene, toluene, xylene, mesitylene,
tetralin, chlorobenzene, dichlorobenzene, bromobenzene, petroleum
ether, hexane, cyclohexane; ethers such as diethyl ether, dipropyl
ether, diisopropyl ether, dibutyl ether, tert-butyl methyl ether,
ethylene glycol monomethyl ether. ethylene glycol monoethyl ether,
ethylene glycol dimethyl ether, dimethoxydiethyl ether,
tetrahydrofuran or dioxane; esters such as ethyl acetate and methyl
acetate; and sulfoxides such as dimethyl sulfoxide. Preferred are
ethers, for example tert-butyl methyl ether, tetrahydrofuran or
dioxane, and esters, for example ethyl acetate.
[0142] The reaction is advantageously carried out in a temperature
range from approximately 0.degree. C. to approximately +120.degree.
C., preferably from approximately 0.degree. C. to approximately
+80.degree. C.
[0143] The reaction is preferably carried out under atmospheric
pressure.
[0144] The reaction time is not critical; a reaction time of from
approximately 0.1 to approximately 24 hours, in particular of from
approximately 0.5 to approximately 2 hours, is preferred.
[0145] The product is isolated by customary methods, e.g. by
filtration, crystallization, distillation or chromatography, or any
suitable combination of these processes. Especially preferred
conditions for the reaction are described in Examples H7 and
H8.
[0146] Variant d):
[0147] The reaction is preferably carried out in the presence of an
acidic catalyst, for example in the presence of a carboxylic acid
such as formic acid, acetic acid, malonic acid or oxalic acid, or
else of a sulfonic acid such as C.sub.1-C.sub.4alkane- or
arylsulfonic acid which is unsubstituted or substituted, for
example by halogen, e.g. methane-, trifluoromethane- or
p-toluenesulfonic acid.
[0148] The reactants can be reacted with each other as such, i.e.
without addition of a solvent or diluent, for example in the melt.
In most cases, however, it is advantageous to add an inert solvent
or diluent or a mixture of these. Particularly suitable are
solvents which are suitable for the azeotropic removal of water.
Examples of such solvents or diluents which may be mentioned are:
aromatic, aliphatic and alicyclic hydrocarbons and halohydrocarbons
such as benzene, toluene, xylene, mesitylene, tetralin,
chlorobenzene, dichlorobenzene, bromobenzene, petroleum ether,
hexane, cyclohexane, dichloromethane, trichloromethane,
tetrachloromethane, dichloroethane, trichloroethene or
tetrachloroethene; esters such as ethyl acetate; ethers such as
dipropyl ether, diisopropyl ether, dibutyl ether, tert-butyl methyl
ether, dimethoxydiethyl ether; ketones such as methyl isobutyl
ketone; alcohols such as ethanol, propanol, isopropanol, butanol,
ethylene glycol or glycerol.
[0149] The reaction is advantageously carried out in a temperature
range from approximately 60.degree. C. to approximately 180.degree.
C., preferably from approximately 80.degree. C. approximately
130.degree. C., in many cases at the reflux temperature of the
reaction mixture.
[0150] The reaction is preferably carried out under atmospheric
pressure.
[0151] The reaction can be carried out without a protective gas
atmosphere; however, it is preferably carried out under a
protective gas atmosphere, e.g. nitrogen or argon, in particular
nitrogen.
[0152] The preferred reaction time is approximately 6 to
approximately 72 hours, in particular from approximately 12 to
approximately 48 hours.
[0153] The product is isolated by customary methods, e.g. by
filtration, crystallization, distillation or chromatography, or any
suitable combination of these processes.
[0154] In a preferred embodiment of variant d), the reaction is
carried out at 80.degree. C. to 140.degree. C. in an alcohol or an
aromatic hydrocarbon in the presence of a C.sub.1-C.sub.4carboxylic
acid.
[0155] Especially preferred conditions for the reaction are
described in Example H10.
[0156] Variant e):
[0157] Preferred halogenating agents are Cl.sub.2, Br.sub.2, SOCl2,
SO.sub.2Cl.sub.2, POCl.sub.3, PCl.sub.3, PCl.sub.5 and
COCL.sub.2.
[0158] The reactants can be reacted with each other as such, i.e.
without addition of a solvent or diluent, for example in the melt.
In most cases, however, it is advantageous to add an inert solvent
or diluent or a mixture of these. Examples of such solvents or
diluents which may be mentioned are: aromatic, aliphatic and
alicyclic hydrocarbons and halohydrocarbons such as benzene,
toluene, xylene, mesitylene, tetralin, chlorobenzene,
dichlorobenzene, bromobenzene, petroleum ether, hexane,
cyclohexane, dichloromethane, trichloromethane, tetrachloromethane,
dichloroethane, trichloroethene or tetrachloroethene; esters such
as ethyl acetate; ethers such as diethyl ether, dipropyl ether,
diisopropyl ether, dibutyl ether, tertbutyl methyl ether, ethylene
glycol dimethyl ether, dimethoxydiethyl ether, tetrahydrofuran or
dioxane; ketones such as acetone, methyl ethyl ketone or methyl
isobutyl ketone; amides such as N,N-dimethylformamide,
N,N-diethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone or
hexamethylphosphoric triamide; and nitrites such as acetonitrile or
propionitrile.
[0159] The reaction is advantageously carried out in a temperature
range from approximately 0.degree. C. to approximately 180.degree.
C., preferably from approximately 50.degree. C. to approximately
100.degree. C., in many cases in the range between room temperature
and the reflux temperature of the reaction mixture.
[0160] The reaction is preferably carried out under atmospheric
pressure.
[0161] The reaction can be carried out without a protective gas
atmosphere; however, it is preferably carried out under a
protective gas atmosphere, e.g. nitrogen or argon, in particular
nitrogen.
[0162] The reaction time is not critical; preferred is a reaction
time of from approximately 0.1 to approximately 24 hours, in
particular from approximately 3 to approximately 6 hours.
[0163] The product is isolated by customary methods, e.g. by
filtration, crystallization, distillation or chromatography, or any
suitable combination of these processes.
[0164] Especially preferred conditions for the reaction are
described in Example H3.
[0165] Variant f):
[0166] The reactants can be reacted with each other as such, i.e.
without addition of a solvent or diluent, for example in the melt.
In most cases, however, it is advantageous to add an inert solvent
or diluent or a mixture of these. Examples of such solvents or
diluents which may be mentioned are: aromatic, aliphatic and
alicyclic hydrocarbons and halohydrocarbons such as benzene,
toluene, xylene, mesitylene, tetralin, chlorobenzene,
dichlorobenzene, bromobenzene, petroleum ether, hexane,
cyclohexane, dichloromethane, trichloromethane, tetrachloromethane,
dichloroethane, trichloroethene or tetrachloroethene; ethers such
as diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether,
tert-butyl methyl ether, ethylene glycol dimethyl ether,
dimethoxydiethyl ether, tetrahydrofuran or dioxane; and nitrites
such as acetonitrile or propionitrile.
[0167] Thioethers which are preferably added are dialkyl
thioethers, especially diethyl sulfide or dimethyl sulfide,
preferably dimethyl sulfide.
[0168] The reaction is advantageously carried out in a temperature
range of from approximately 0.degree. C. to approximately
-100.degree. C., especially at -50 to -80.degree. C., preferably at
approximately -60.degree. C.
[0169] The reaction is preferably carried out under atmospheric
pressure.
[0170] The reaction can be carried out without a protective gas
atmosphere; however, it is preferably carried out under a
protective gas atmosphere, e.g. nitrogen or argon, in particular
nitrogen.
[0171] The reaction time is not critical; preferred is a reaction
time of from approximately 0.1 to approximately 24 hours, in
particular from approximately 3 to approximately 6 hours.
[0172] The product is isolated by customary methods, e.g. by
filtration, crystallization, distillation or chromatography, or any
suitable combination of these processes.
[0173] The compounds of the formulae (I), (II) and (VIII) can be in
the form of one of the isomers which are possible or as a mixture
of these, for example depending on the number, absolute and
relative configuration of the asymmetric carbon atoms, as pure
isomers such as antipodes and/or diastereomers, or as isomer
mixtures, such as enantiomer mixtures, for example racemates,
diastereomer mixtures or racemate mixtures; the invention relates
to the pure isomers and also to all isomer mixtures which are
possible and is to be understood hereinabove and hereinbelow in
each case in this sense even when stereochemical details are not
mentioned specifically in each case.
[0174] Diastereomer mixtures and racemate mixtures of compounds of
the formulae (I), (II) and (VIII) which can be obtained in
accordance with the process--depending on the choice of starting
materials and procedures--or by other means can be resolved into
the pure diastereomers or racemates in the known manner on the
basis of the physico-chemical differences of the components, for
example by fractional crystallization, distillation and/or
chromatography.
[0175] Enantiomer mixtures which can be obtained accordingly, such
as racemates, can be separated into the optical antipodes by
customary methods, for example by recrystallization from an
optically active solvent, by chromatography on chiral adsorbents,
for example high-performance liquid chromatography (HPLC) on
acetylcellulose, with the aid of suitable microorganisms, by
cleavage with specific immobilized enzymes, via the formation of
inclusion compounds, for example using chiral crown ethers, where
only one enantiomer is complexed.
[0176] In addition to separating appropriate isomer mixtures, pure
diastereomers or enantiomers can also be obtained in accordance
with the invention by generally known methods of diastereoselective
or enantioselective synthesis, for example by carrying out the
process according to the invention with starting materials of a
suitable stereochemistry.
[0177] It is advantageous to isolate, or synthesize, in each case
the biologically more effective isomer, for example enantiomer, or
isomer mixture, for example enantiomer mixture, if the individual
components have different biological activity.
[0178] The compounds of the formulae (I), (II) and (VIII) can also
be obtained in the form of their hydrates and/or include other
solvents, for example, if desired, those which have been used for
crystallizing compounds in solid form.
[0179] The invention relates to all those embodiments of the
process which start from a compound which can be obtained as
starting material or intermediate at any level of the process and
where all or some of the missing steps are carried out or where a
starting material is used in the form of a derivative or salt
and/or the racemates or antipodes thereof or, in particular, such a
starting material is formed under the reaction conditions.
[0180] Starting materials and intermediates which are preferably
used in the process of the present invention are those which lead
to the compounds of the formula (I) which have been described at
the outset as being particularly valuable.
[0181] In particular, the invention relates to the preparation
processes described in Examples H5, H6, H7, H8 and H10.
[0182] The invention also relates to starting materials and
intermediates used for the preparation of the compounds of the
formula (I), in particular to those compounds of the formulae (II)
and (VIII), which are novel, and to their use and processes for
their preparation. The compounds of the formulae II and VIII, in
particular, can be prepared analogously to Examples Hi and H3,
respectively.
[0183] Those compounds of the formulae (III) to (VII) and (IX)
which are not already known can be prepared by processes known per
se.
[0184] The invention furthermore relates to a method of controlling
pests using a compound of the formula (I), in which A.sub.1,
A.sub.2, R.sub.1 and R.sub.2 are as indicated above for formula
(I), with the exception of
1-phenylhydrazono-2-nitriloethylbenzene.
[0185] The compounds of the formula (I) according to the invention
are preventively and/or curatively valuable active ingredients in
the field of pest control, even at low rates of concentration,
which have a very favourable biocide spectrum and are well
tolerated by warm-blooded species, fish and plants. The term pests
first of all includes in the frame of the present invention
insects, representatives of the order Acarina, microorganisms, and
representatives of the classes Nematoda and Trematoda; especially
insects, representatives of the order Acarina and phvtopathogenic
fungi, more particularly insects and representatives of the order
Acarina. The active ingredients according to the invention are
effective against all or individual developmental stages of
normally sensitive, but also resistant, animal pests such as
insects and representatives of the order Acarina. The insecticidal,
ovicidal and/or acaricidal activity of the active ingredients
according to the invention can manifest itself directly, i.e. in
mortality of the pests, which takes place immediately or only after
some time has elapsed, for example during ecdysis, or of their
eggs, or indirectly, for example in a reduced oviposition rate
and/or hatching rate, the good activity corresponding to a
mortality rate (mortality) of at least 50 to 60%.
[0186] Examples of the abovementioned animal pests are:
[0187] from the order Lepidoptera, for example,
[0188] Acleris spp., Adoxophyes spp., Aegeria spp., Agrotis spp.,
Alabama argillaceae, Amylois spp., Anticarsia gemmatalis, Archips
spp., Argyrotaenia spp., Autographa spp., Busseola fusca, Cadra
cautella, Carposina nipponensis, Chilo spp., Choristoneura spp.,
Clysia ambiguella, Cnaphalocrocis spp., Cnephasia spp., Cochylis
spp., Coleophora spp., Crocidolomia binotalis, Cryptophlebia
leucotreta, Cydia spp., Diatraea spp., Diparopsis castanea, Earias
spp., Ephestia spp., Eucosma spp., Eupoecilia ambiguella, Euproctis
spp., Euxoa spp., Grapholita spp., Hedya nubiferana, Heliothis
spp., Hellula undalis, Hyphantria cunea, Keiferia lycopersicella,
Leucoptera scitelia, Lithocollethis spp., Lobesia botrana,
Lymantria spp., Lyonetia spp., Malacosoma spp., Mamestra brassicae,
Manduca sexta, Operophtera spp., Ostrinia nubilalis, Pammene spp.,
Pandemis spp., Panolis flammea, Pectinophora gossypiella,
Phthorimaea operculella, Pieris rapae, Pieris spp., Plutella
xylostella, Prays spp., Scirpophaga spp., Sesamia spp.,
Sparganothis spp., Spodoptera spp., Synanthedon spp., Thaumetopoea
spp., Tortrix spp., Trichoplusia ni and Yponomeuta spp.;
[0189] from the order Coleoptera, for example,
[0190] Agriotes spp., Anthonomus spp., Atomaria linearis,
Chaetocnema tibialis, Cosmopolites spp., Curculio spp., Dermestes
spp., Diabrotica spp., Epilachna spp., Eremnus spp., Leptinotarsa
decemlineata, Lissorhoptrus spp., Melolontha spp., Orycaephilus
spp., Otiorhynchus spp., Phlyctinus spp., Popillia spp., Psylliodes
spp., Rhizopertha spp., Scarabeidae, Sitophilus spp., Sitotroga
spp., Tenebrio spp., Tribolium spp. and Trogoderma spp.;
[0191] from the order Orthoptera, for example,
[0192] Blafta spp., Blattella spp., Gryllotalpa spp., Leucophaea
maderae, Locusta spp., Periplaneta spp. and Schistocerca spp.;
[0193] from the order Isoptera, for example, Reticulitermes
spp.:
[0194] from the order Psocoptera, for example, Liposcelis spp.;
[0195] from the order Anoplura, for example, Haematopinus spp.,
Linognathus spp., Pediculus spp., Pemphigus spp. and Phylloxera
spp.;
[0196] from the order Mallophaga, for example, Damalinea spp. and
Trichodectes spp.; from the order Thysanoptera, for example,
Frankliniella spp., Hercinothrips spp., Taeniothrips spp., Thrips
palmi, Thrips tabaci and Scirtothrips aurantii;
[0197] from the order Heteroptera, for example, Cimex spp.,
Distantiella theobroma, Dysdercus spp., Euchistus spp. Eurygaster
spp. Leptocorisa spp., Nezara spp., Piesma spp., Rhodnius spp.,
Sahlbergella singularis, Scotinophara spp. and Triatoma spp.;
[0198] from the order Homoptera, for example, Aleurothrixus
floccosus, Aleyrodes brassicae, Aonidiella spp., Aphididae, Aphis
spp., Aspidiotus spp., Bemisia tabaci, Ceroplaster spp.,
Chrysomphalus aonidium, Chrysomphalus dictyospermi, Coccus
hesperidum, Empoasca spp., Eriosoma larigerum, Erythroneura spp.,
Gascardia spp., Laodelphax spp., Lecanium corni, Lepidosaphes spp.,
Macrosiphus spp., Myzus spp., Nephotettix spp., Nilaparvata spp.,
Paratoria spp., Pemphigus spp., Planococcus spp., Pseudaulacaspis
spp., Pseudococcus spp., Psylla spp., Pulvinaria aethiopica,
Quadraspidiotus spp., Rhopalosiphum spp., Saissetia spp.,
Scaphoideus spp., Schizaphis spp., Sitobion spp., Trialeurodes
vaporariorum, Trioza erytreae and Unaspis citri;
[0199] from the order Hymenoptera, for example, Acromyrmex, Atta
spp., Cephus spp., Diprion spp., Diprionidae, Gilpinia polytoma,
Hoplocampa spp., Lasius spp., Monomorium pharaonis, Neodiprion
spp., Solenopsis spp. and Vespa spp.;
[0200] from the order Diptera, for example, Aedes spp., Antherigona
soccata, Bibio hortulanus, Calliphora erythrocephala, Ceratitis
spp., Chrysomyia spp., Culex spp., Cuterebra spp., Dacus spp.,
Drosophila melanogaster, Fannia spp., Gastrophilus spp., Glossina
spp., Hypoderma spp., Hyppobosca spp., Liriomyza spp., Lucilia
spp., Melanagromyza spp., Musca spp., Oestrus spp., Orseolia spp.,
Oscinella frit, Pegomyia hyoscyami, Phorbia spp., Rhagoletis
pomonella, Sciara spp., Stomoxys spp., Tabanus spp., Tannia spp.
and Tipula spp.;
[0201] from the order Siphonaptera, for example, Ctenocephalides
felis, Ctenocephalides canis, Ceratophyllus spp. and Xenopsylla
cheopis;
[0202] from the order Thysanura, for example, Lepisma saccharina
and from the order Acarina, for example, Acarus siro, Aceria
sheldoni, Aculus schlechtendali, Amblyomma spp., Argas spp.,
Boophilus spp., Brevipalpus spp., Bryobia praetiosa, Calipitrimerus
spp., Chorioptes spp., Dermanyssus gailinae, Eotetranychus carpini,
Eriophyes spp., Hyalomma spp., Ixodes spp., Olygonychus pratensis,
Ornithodoros spp., Panonychus spp., Phyllocoptruta oleivora,
Polyphagotarsonemus latus, Psoroptes spp., Rhipicephalus spp.,
Rhizoglyphus spp., Sarcoptes spp., Tarsonemus spp. and Tetranychus
spp.
[0203] From the class Trematoda especially representatives of the
family Fasciolidae, especially Fasciola hepatica;
[0204] and from of the class Nematoda for example the families
Filariidae and Setariidae, especially the genera Haemonchus,
Trichostrongylus, Ostertagia, Nematodirus, Cooperia, Ascaris,
Bunostomum, Oesophagostomum, Chabertia, Trichuris, especially
Trichuris vulpis, Strongylus, Trichonema, Dictyocaulus, Capillaria,
Strongyloides, Heterakis, Toxocara, especially Toxocara canis,
Ascaridia, Oxyuris, Ancylostoma, especially Ancylostoma caninum,
Uncinaria, Toxascaris and Parascaris; Dirofilaria, especially
Dirofilaria immitis (heart worm).
[0205] The activity of the compositions comprising the compounds of
the formula (I) and of the compounds of the formula (Ia) can be
substantially broadened and adapted to prevailing circumstances by
the addition of other insecticides and/or acaricides. Examples of
suitable additional active ingredients include representatives of
the following classes of compounds: Thioureas, benzoylureas,
carbamoyloximes, halogated carboxylic acid derivatives,
organophosphates, organochloro derivatives, nitroenamines,
nitroguanidines, cyanoguanidines, carbamates, thiocarbamates,
carbodiimides, formamidines, benzilic acid derivatives, dioxolanes,
thiadiazinderivatives, unsymmetrical triazines, symmetrical
triazines, pyridazinones, pyrroles, phenoxyphenylethers, sulfonic
acid amides, bacillus thuringiensis-preparations, milbemycines,
avermectines und pyrethroids.
[0206] The active ingredients according to the invention can be
used for controlling, i.e. containing or destroying, pests of the
abovementioned type in particular on plants, mainly on crops of
useful plants and ornamentals in agriculture, in horticulture and
in silviculture, or on parts of such plants, such as fruits,
flowers, foliage, stalks, tubers or roots, and in some cases even
parts of plants which are formed at a later point in time are
afforded protection against these pests.
[0207] Target crops which are suitable are, in particular, cereals,
such as wheat, barley, rye, oats, rice, maize or sorghum; beet,
such as sugar or fodder beet; fruit, e.g. pomaceous fruit, stone
fruit and soft fruit, such as apples, pears, plums, peaches,
almonds, cherries or berries, for example strawberries, raspberries
or blackberries; leguminous plants, such as beans, lentils, peas or
soya; oil crops, such as oilseed rape, mustard, poppies, olives,
sunflowers, coconut, castor, cocoa or groundnuts; cucurbits, such
as pumpkins, cucumbers or melons; fibre plants, such as cotton,
flax, hemp or jute; citrus fruit, such as oranges, lemons,
grapefruits or tangerines; vegetables, such as spinach, lettuce,
asparagus, cabbages, carrots, onions, tomatoes, potatoes or bell
peppers; the laurel family, such as avocado, Cinnamonium or
camphor; and also tobacco, nuts, coffee, egg plants, sugar cane,
tea, pepper, grapevines, hops, the plantain family, latex plants
and ornamentals.
[0208] The active ingredients according to the invention are
especially suitable for controlling insects and representatives of
the order Acarina, in particular feeding insects which damage
plants, such as Anthonomus grandis, Diabrotica balteata, Heliothis
virescens larvae, Plutelia xylostella and Spodoptera littoralis
larvae, and spider mites such as Tetranychus spp. in cotton, fruit,
maize, soya, oilseed rape and vegetable crops.
[0209] Other fields of application of the active ingredients
according to the invention are the protection of stored roducts and
stores and of material, and, in the hygiene sector, in particular
the protection of domestic animals or productive livestock against
pests of the abovementioned type.
[0210] The invention therefore especially relates to a pesticidal
composition which comprises a compound of the formula (I), with the
exception of 1-phenylhydrazono-2-nitriloethylbenzene, in the form
of emulsifiable concentrates, suspension concentrates, directly
sprayable or dilutable solutions, spreadable pastes, dilute
emulsions, wettable powders, soluble powders, dispersible powders,
wettable powders, dusts, granules or encapsulations in polymeric
substances, all of which comprise--at least--one of the active
ingredients according to the invention and which are to be selected
to suit the intended aims and prevailing circumstances.
[0211] In these compositions,the active ingredient is employed
together with--at least--one of the auxiliaries conventionally used
in the art of formulation, such as extenders, e.g. solvents or
solid carriers, or such as surface-active compounds
(surfactants).
[0212] Examples of suitable solvents are: non-hydrogenated or
partially hydrogenated aromatic hydrocarbons, preferably the
fractions C.sub.8 to C.sub.12 of alkylbenzenes, such as xylene
mixtures, alkylated naphthalenes or tetrahydronaphthalene,
aliphatic or cycloaliphatic hydrocarbons such as paraffins or
cyclohexane, alcohols such as ethanol, propanol or butanol, glycols
and their ethers and esters such as propylene glycol, dipropylene
glycol ether, ethylene glycol, ethylene glycol monomethyl ether or
ethylene glycol monoethyl ether, ketones such as cyclohexanone,
isophorone or diacetone alcohol, strongly polar solvents such as
N-methyl-pyrrolid-2-one, dimethyl sulfoxide or
N,N-dimethylformamide, water, free or epoxidized rapeseed, castor,
coconut or soya oil, and silicone oils.
[0213] Solid carriers which are used for example for dusts and
dispersible powders are, as a rule, ground natural minerals, such
as calcite, talc, kaolin, montmorillonite or attapulgite. To
improve the physical properties, it is also possible to add
highly-disperse silicas or highly-disperse absorptive polymers.
Suitable particulate adsorptive carriers for granules are porous
types, such as pumice, brick grit, sepiolite or bentonite, and
suitable non-sorptive carrier materials are calcite or sand.
Moreover, a large number of granulated materials of inorganic or
organic nature can be used, in particular dolomite or comminuted
plant residues.
[0214] Suitable surface-active compounds are, depending on the
nature of the active ingredient to be formulated, non-ionic,
cationic and/or anionic surfactants or surfactant mixtures which
have good emulsifying, dispersing and wetting properties. The
surfactants listed below are only to be considered as examples;
many more surfactants conventionally used in the art of formulation
and suitable in accordance with the invention are described in the
relevant literature.
[0215] Suitable non-ionic surfactants are primarily polyglycol
ether derivatives of aliphatic or cyclo-aliphatic alcohols, of
saturated or unsaturated fatty acids and alkylphenols which can
contain 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the
(aliphatic) hydrocarbon radical and 6 to 18 carbon atoms in the
alkyl radical of the alkylphenols. Also suitable are water- soluble
polyethylene oxide adducts with polypropylene glycol,
ethylenediaminopolypropylene glycol and alkylpolypropylene glycol
having 1 to 10 carbons in the alkyl chain and 20 to 250 ethylene
glycol ether and 10 to 100 propylene glycol ether groups. The
abovementioned compounds normally contain 1 to 5 ethylene glycol
units per propylene glycol unit. Examples which may be mentioned
are nonylphenylpolyethoxyethanols, castor oil polyglycol ethers,
polypropylene/polyethylene oxide adducts,
tributylphenoxypolyethoxyethano- l, polyethylene glycol and
octylphenoxypolyethoxyethanol. Also suitable are fatty acid esters
of polyoxyethylene sorbitan, such as polyoxyethylene sorbitan
trioleate.
[0216] The cationic surfactants are mainly quaternary ammonium
salts which have, as substituents, at least one alkyl radical of 8
to 22 carbon atoms and, as further substituents, lower alkyl,
benzyl or lower hydroxyalkyl radicals which may be halogenated. The
salts are preferably in the form of halides, methylsulfates or
ethylsulfates. Examples are stearyltrimethylammonium chloride and
benzyldi(2-chloroethyl)ethylammoniu- m bromide.
[0217] Suitable anionic surfactants can be both water-soluble soaps
and water-soluble synthetic surface-active compounds. Soaps which
are suitable are the alkali metal salts, alkaline earth metal salts
and unsubstituted or substituted ammonium salts of higher fatty
acids (C.sub.10-C.sub.22), such as the sodium or potassium salts of
oleic or stearic acid, or of natural fatty acid mixtures which can
be obtained, for example, from coconut or tall oil; mention must
also be made of the fatty acid methyltaurinates. However, synthetic
surfactants, in particular fatty sulfonates, fatty sulfates,
sulfonated benzimidazole derivatives or alkylarylsulfonates, are
used more frequently. As a rule, the fatty sulfonates and fatty
sulfates exist as alkali metal salts, alkaline earth metal salts or
unsubstituted or substituted ammonium salts and generally have an
alkyl radical of 8 to 22 C atoms, alkyl also including the alkyl
moiety of acyl radicals; examples which may be mentioned are the
sodium or calcium salt of lignosulfonic acid, of the
dodecylsulfuric ester or of a fatty alcohol sulfate mixture
prepared with natural fatty acids. This group also includes the
salts of the sulfuric esters and sulfonic acids of fatty
alcohol/ethylene oxide adducts. The sulfonated benzimidazole
derivatives preferably contain 2 sulfo groups and one fatty acid
radical having approximately 8 to 22 C atoms. Examples of
alkylarylsulfonates are the sodium, calcium or triethanolammonium
salts of dodecylbenzenesulfonic acid, of dibutylnaphthalenesulfonic
acid or of a naphthalenesulfonic acid/formaldehyde condensate. Also
suitable are corresponding phosphates, such as salts of the
phosphoric ester of a p-nonylphenol (4-14)ethylene oxide adduct, or
phospholipids.
[0218] As a rule, the compositions comprise 0.0000001 to 99.99%,
especially 0.1 to 99%, in particular 0.1 to 95%, of active
ingredient and 0.01 to 99.9999999%, especially 1 to 99.9%, in
particular 5 to 99.9%, of--at least--one solid or liquid auxiliary,
it being possible, as a rule, for the surfactants to amount to 0 to
25%, in particular 0.1 to 20%, of the composition (% is in each
case percent by weight). While concentrated compositions are more
preferred as commercially available goods, the end user uses, as a
rule, dilute compositions, which have a considerably lower
concentration of active ingredient. Preferred compositions are
composed in particular as follows (%=percent by weight):
1 Emulsifiable concentrates: active ingredient: 1 to 90%,
preferably 5 to 20% surfactant: 1 to 30%, preferably 10 to 20%
solvent: 5 to 98%, preferably 70 to 85% Dusts: active ingredient:
0.1 to 10%, preferably 0.1 to 1% solid carrier: 99.9 to 90%,
preferably 99.9 to 99% Suspension concentrates: active ingredient:
5 to 75%, preferably 10 to 50% water: 94 to 24%, preferably 88 to
30% surfactant: 1 to 40%, preferably 2 to 30% Wettable powder:
active ingredient: 0.5 to 90%, preferably 1 to 80% surfactant: 0.5
to 20%, preferably 1 to 15% solid carrier: 5 bis 99%, vorzugsweise
15 bis 98% Granules: active ingredient: 0.5 to 30%, preferably 3 to
15% solid carrier: 99.5 to 70%, preferably 97 to 85%
[0219] The activity of the compositions according to the invention
can be widened considerably, and adapted to prevailing
circumstances, by adding other insecticidally, acaricidally and/or
fungicidally active ingredients. Examples of suitable additives of
active ingredients are representatives of the following classes of
active ingredients: organophosphorus compounds, nitrophenols and
derivatives, formamidines, ureas, carbamates, pyrethroids,
chlorinated hydrocarbons and Bacillus thuringiensis peparations.
The compositions according to the invention may also comprise other
solid or liquid auxiliaries such as stabilizers, for example
epoxidized or unepoxidized vegetable oils (e.g. epoxidized coconut
oil, rapeseed oil or soya oil), antifoams, e.g. silicone oil,
preservatives, viscosity regulators, binders and/or tackifiers, and
also fertilizers or other active ingredients for achieving specific
effects, for example bactericides, nematicides, molluscicides or
selective herbicides.
[0220] The compositions according to the invention are prepared in
a known manner, in the absence of auxiliaries for example by
grinding and/or screening a solid active ingredient, or active
ingredient mixture, for example to obtain a specific particle size,
and in the presence of at least one auxiliary for example by
intimately mixing and/or grinding the active ingredient, or active
ingredient mixture, with the auxiliary (or auxiliaries). These
processes for the preparation of the compositions according to the
invention and the use of the compounds of the formula (I) for the
preparation of these compositions are also subjects of the
invention.
[0221] The methods of application for the compositions, i.e. the
methods of controlling pests of the abovementioned type, such as
spraying, atomizing, dusting, brushing on, seed-dressing,
scattering or pouring, which are to be selected to suit the
intended aims and the prevailing circumstances, and the use of the
compositions for controlling pests of the abovementioned type are
also subjects of the invention. Typical use concentrations are
between 0.1 and 1000 ppm, preferably between 0.1 and 500 ppm, of
active ingredient. The rates of application per hectare are
generally 1 to 2000 g of active ingredient per hectare, in
particular 10 to 1000 g/ha, preferably 20 to 600 g/ha.
[0222] A preferred method of application in the field of crop
protection is application to the foliage of the plant (foliar
application), it being possible to adjust frequency and rate of
application to the degree or risk of infestation with the pest in
question. Alternatively, the active ingredient can reach the plants
via the root system (systemic action), by drenching the locus of
the plants with a liquid composition or by incorporating the active
ingredient in solid form into the locus of the plants, for example
in the soil, for example in the form of granules (soil
application). In the case of paddy rice crops, such granules can be
metered into the flooded paddy field.
[0223] The compositions according to the invention are also
suitable for the protection of plant propagation material, e.g.
seed such as fruits, tubers or kernels, or nursery plants, against
fungal infection and animal pests. The propagation material can be
dressed with the composition before planting, for example seed can
be dressed before sowing. It is also possible to apply the active
ingredients according to the invention to seed kernels (coating),
either by soaking the kernels in a liquid composition or by coating
them with a solid composition. Alternatively, the composition can
be applied to the site of application when the propagation material
is planted, for example into the seed furrow during sowing. These
treatment methods for plant propagation material and the plant
propagation material treated accordingly are further subjects of
the invention.
[0224] The examples which follow are intended to illustrate the
invention. They do not limit the invention. Temperatures are given
in degrees Celsius.
PREPARATION EXAMPLES
Example H1
[0225]
N'-(2,6-dichloro-4-trifluoromethylphenyl)-4-cyanobenzohydrazide
14
[0226] A solution of 14.2 g of 4-cyanobenzoyl chloride in 100 ml of
methylene chloride is added dropwise with stirring at from 10 to
15.degree. in the course of approximately 30 minutes to 20 g of
2,6-dichloro-4-trifluoromethylphenylhydrazine in 250 ml of
dichloromethane, and the mixture is stirred for a further 16 hours.
36 ml of aqueous sodium hydroxide solution (10%) is then run in
with vigorous stirring. 100 ml of methylene chloride are added, the
organic phase is washed three times using in each case 100 ml of
water and dried over sodium sulfate, and the solvent is removed on
a rotary evaporator. After the residue has been recrystallized from
toluene, the title product of melting point 185-186.degree. is
obtained (compound no. 1.6).
Example H2
[0227] The other compounds listed in Table 1 can also be prepared
analogously to the procedure described in Example H1.
2TABLE 1 15 No. (R.sub.3a).sub.n1 (R.sub.3b).sub.n2 R.sub.2 Melting
point (.degree. C.) 1.1 2-Cl, 4-CF.sub.3 4-Cl H 167-170 1.2 2-Cl,
4-CF.sub.3 4-NO.sub.2 H 208-209 1.3 2-Cl, 4-CF.sub.3 2-Cl H 170-171
1.4 2,6-Cl.sub.2, 4-CF.sub.3 4-CF.sub.3 H 192-193 1.5 2,4-Cl.sub.2
4-CF.sub.3 H 189-190 1.6 2,6-Cl.sub.2, 4-CF.sub.3 4-CN H 185-186
1.7 4-CF.sub.3 4-CN H 201-203 1.8 4-CF.sub.3 4-CF.sub.3 H 202-203
1.9 2,6-Cl.sub.2, 4-CF.sub.3 3-CN H 188-189 1.10 2,6-Cl.sub.2,
4-CF.sub.3 3-CF.sub.3 H 137-138 1.11 3,5-CF.sub.3 4-CN H 214-215
1.12 2-Cl, 4-CF.sub.3 4-CN H 215-216 1.13 2,6-Cl.sub.2, 4-CF.sub.3
4-NO.sub.2 H 192-193 1.14 2,4,6-Cl.sub.3 4-CN H 189-190 1.15
2,6-Cl.sub.2-4-CF.sub.3 2-Cl-4-NO.sub.2 H 205-206 1.16
2,6-Cl.sub.2-4-CF.sub.3 2,4-(NO.sub.2).sub.2 H 218-219 1.17
2,6-Cl.sub.2-4-CF.sub.3 3-OCH.sub.3-4-NO.sub.2 H 194-195 1.18
2,6-Cl.sub.2-4-CF.sub.3 3-CH.sub.3-4-NO.sub.2 H 192-193 1.19
2,4,6-Cl.sub.3 4-NO.sub.2 H 201-202 1.20 2,6-Cl.sub.2-4-NO.sub.2
4-NO.sub.2 H 242-243 1.21 2,6-Cl.sub.2-4-NO.sub.2 4-CN H 217-218
1.22 2,6-(CH.sub.3).sub.2-4-Br 4-CN H 181-182 1.23
2-Cl-4-Br-6-CH.sub.3 4-CN H 185-186 1.24 2-Cl-4-Br-6-CH.sub.3
4-NO.sub.2 H 200-201 1.25 2,6-(CH.sub.3).sub.2-4-Br 4-NO.sub.2 H
206-207 1.26 2,4,6-Cl.sub.3 3-NO.sub.2-4-Cl H 201-202 1.27
2,4,6-Cl.sub.3 4-CHO H 175-176 1.28 2,6-Cl.sub.2-4-CF.sub.3 4-Br H
207-208 1.29 2,4-Cl.sub.2-6-CF.sub.3 4-NO.sub.2 H 184-185 1.30
2,6-Cl.sub.2-3-F-4-CF.sub.3 4-NO.sub.2 H 208-209 1.31
2,6-Cl.sub.2-4-CF.sub.3 4-COCF.sub.3 H 182-183 1.32
2,6-Cl.sub.2-4-CF.sub.3 4-CO.sub.2CH.sub.3 H 213-214 1.33
2-Cl-4-CF.sub.3-6-F 4-NO.sub.2 H 168-170 1.34
2,3,6-Cl.sub.3-4-CF.sub.3 4-NO.sub.2 H 210-212
Example H3
[0228]
4-{1-[(2,6-dichloro-4-trifluoromethylphenyl)hydrazono]-chloromethyl-
}benzonitrile 16
[0229] 12.6 g of thionyl chloride are added dropwise with stirring
to a solution of 26.6 g of
N'-(2,6-dichloro-4-trifluoromethyl)phenyl-4-cyanobe- nzohydrazide
in 250 ml of toluene at room temperature. The mixture is then
heated to 900 and stirred for 5 hours. The mixture is evaporated to
dryness on a rotary evaporator and the residue is crystallized from
hexaneltoluene 1:1. This gives the title compound of melting point
168-1690 (compound no. 2.5).
Example H4
[0230] The other compounds listed in Table 2 can also be prepared
analogously to the procedure described in Example H3.
3TABLE 2 17 No. (R.sub.3a).sub.n1 (R.sub.3b).sub.n2 R.sub.2 Melting
point (.degree. C.) 2.1 2-Cl, 4-CF.sub.3 4-Cl H 116-117 2.2 2-Cl,
4-CF.sub.3 4-NO.sub.2 H 181-183 2.3 2,6-Cl.sub.2, 4-CF.sub.3
4-CF.sub.3 H 136-137 2.4 2,4-Cl.sub.2 4-CF.sub.3 H 127-128 2.5
2,6-Cl.sub.2, 4-CF.sub.3 4-CN H 168-169 2.6 4-CF.sub.3 4-CN H
174-176 2.7 4-CF.sub.3 4-CF.sub.3 H 127-128 2.8 2,6-Cl.sub.2,
4-CF.sub.3 3-CN H 157-158 2.9 2,6-Cl.sub.2, 4-CF.sub.3 3-CF.sub.3 H
97-98 2.10 3,5-(CF.sub.3).sub.2 4-CN H 234-236 2.11 2-Cl,
4-CF.sub.3 4-CN H 170-171 2.12 2,6-Cl.sub.2, 4-CF.sub.3 4-NO.sub.2
H 119-120 2.13 2,4,6-Cl.sub.3 4-ON H 184-185 2.14 2,6-Cl.sub.2,
4-CF.sub.3 4-Cl H 170-171 2.15 2,6-Cl.sub.2, 4-CF.sub.3 3-CH.sub.3,
4-NO.sub.2 H 154-155 2.16 2,6-Cl.sub.2, 4-CF.sub.3 3-OCH.sub.3,
4-NO.sub.2 H 169-170 2.17 2,4,6-Cl.sub.3 4-NO.sub.2 H 162-163 2.18
2,6-Cl.sub.2, 4-NO.sub.2 4-CN H 233-234 2.19 2,6-(CH.sub.3).sub.2,
4-Br 4-CN H 144-146 2.20 2,6-(CH.sub.3).sub.2, 4-Br 4-NO.sub.2 H
143-144 2.21 2-Cl-4-Br-6-CH.sub.3 4-CN H 172-173 2.22
2-Cl-4-Br-6-CH.sub.3 4-NO.sub.2 H 156-157 2.23 2,4,6-Cl.sub.3
3-NO.sub.2,4-Cl H 182-183 2.24 2,6-Cl.sub.2, 4-NO.sub.2 4-NO.sub.2
H 199-200 2.25 2,4,6-Cl.sub.3 4-CHO H 135-137 2.26 2,6-Cl.sub.2,
4-CF.sub.3 4-Br H 124-125 2.27 2,4-Cl.sub.2, 6-CF.sub.3 4-NO.sub.2
H 128-129 2.28 2,6-Cl.sub.2-3-F-4-CF.sub.3 4-NO.sub.2 H 143-144
2.29 2,6-Cl.sub.2, 4-CF.sub.3 4-C(O)CF.sub.3 H 107-108 2.30
2-Cl-4-CF.sub.3-6-F 4-NO.sub.2 H 135-137 2.31
2,3,6-Cl.sub.3-4-CF.sub.3 4-NO.sub.2 H 121-123
Example H5
[0231]
4-{1-[(2,6-dichloro-4-trifluoromethylphenyl)hydrazono]-2-nitriloeth-
yl}benzonitrile 18
[0232] 55 g of solid
4-{1-[(2,6-dichloro-4-trifluoromethylphenyl)hydrazono-
gchloromethyl}benzonitrile are added in portions in the course of
approximately one hour to 11.4 g of sodium cyanide in 270 ml of
water and 400 ml of ethanol. After the mixture has been stirred for
three hours at room temperature, 200 ml of ethanol and 135 ml of
water are added and the mixture is stirred for a further 5 hours.
100 ml of water are added slowly, the precipitate is filtered off
and washed with water, and the filter residue is dried in vacuo at
400. This gives the title compound of melting point 186-1870
(compound no. 3.4).
Example H6
[0233]
4-{1-[(2,6-dichloro-4-trifluoromethylphenyl)hydrazono]-2-nitriloeth-
yl}chlorobenzene 19
[0234] a) 1.5 g of sodium nitrite are added at room temperture to a
mixture of 14 ml of concentrated sulfuric acid and 14 ml of acetic
acid. The mixture is heated to 800 and stirred until all solids
have dissolved, and the solution is cooled to room temperature. To
this mixture there are added 4.6 g of
2,6-dichloro-4-trifluoromethylaniline, dissolved in 14 ml of
concentrated sulfuric acid, and the mixture is stirred for one hour
at room temperature and then for one hour at 50.degree..
[0235] b) The solution prepared in accordance with a) is added with
stirring at room temperature to 3.85 g of
3-oxo-2-(4-chlorophenyl)butyron- itrile in 28 ml of acetic acid and
40 ml of water, and the mixture is stirred for a further three
hours. The mixture is poured into 300 ml of ice-water and extracted
three times using in each case 100 ml of ethyl acetate. The
combined organic phases are washed with water, dried over sodium
sulfate and evaporated to dryness in vacuo. The residue is
crystallized from toluene/hexane 1:1. This gives the title compound
of melting point 164-1650 (compound no. 3.16).
Example H7
[0236]
4-{1-[(2,6-dichloro-4-trifluoromethylphenyl)methylhydrazono]-2-nitr-
iloethyl}-benzonitrile 20
[0237] To 0.96 g of
4-{1-[(2,6-dichloro-4-trifluoromethylphenyl)hydrazono]-
-2-nitriloethyl}benzonitrile in 30 ml of ethyl methyl ketone there
are added 0.7 g of finely pulverized potassium carbonate and 1.4 g
of methyl iodide. The mixture is heated to 80.degree. and stirred
for three hours. The reaction mixture is filtered, the filtrate is
concentrated in vacuo, and the residue is dissolved in ethyl
acetate. The ethyl acetate phase is washed with water and NaCl
solution, dried over sodium sulfate and evaporated to dryness in
vacuo. After the residue has been washed with hexane, the title
product of melting point 92-930 is obtained (compound no.
3.29).
Example H8
[0238] methyl
{N'-[1-(4-cyanophenyl)-2-nitriloethylidene]-N-(2,6-dichloro--
4-trifluoromethylphenyl)hydrazino]oxoacetate 21
[0239] 0.73 g of potassium tert-butoxide is added to 1.9 g of
4-{1-[(2,6-dichloro-4-trifluoromethylphenyl)hydrazono]nitrilomethyl}benzo-
nitrile in 40 ml of anhydrous tetrahydrofuran. A solution of 0.8 g
of methyl chlorooxalate in 5 ml of tetrahydrofuran is added
dropwise at 100 and the mixture stirred for 2 hours. The reaction
mixture is evaporated to dryness, the residue is taken up in ethyl
acetate, and the organic phase is washed with water and dried over
sodium sulfate. The solvent is evaporated and the residue is
chromatographed on silica gel using n-hexane/diethyl ethos (3:1) as
the eluent. This gives the title product of melting point 194-1950
(compound no. 3.36).
Example H9
[0240] The other compounds listed in Tables 3 and 4 can also be
prepared analogously to the procedure described for Examples H5 to
H8.
4TABLE 3 22 No. (R.sub.3a).sub.n1 R.sub.3b).sub.n2 R.sub.2 Melting
point (.degree. C.) 3.1 2-Cl, 4-CF.sub.3 4-Cl H 161-162 3.2 2-Cl,
4-CF.sub.3 4-NO.sub.2 H 204-205 3.3 2,6-Cl.sub.2, 4-CF.sub.3
4-CF.sub.3 H 133-136 3.4 2,6-Cl.sub.2, 4-CF.sub.3 4-CN H 186-187
3.5 2,4-Cl.sub.2 4-CF.sub.3 H 160-161 3.6 2,6-Cl.sub.2, 4-CF.sub.3
3-CN H 180-181 3.7 2,6-Cl.sub.2, 4-CF.sub.3 3-CF.sub.3 H 119-121
3.8 3,5-(CF.sub.3).sub.2 2-F H 198-199 3.9 3,5-(CF.sub.3).sub.2
4-CN H 272 (decomp.) 3.10 2-NO.sub.2 4-NO.sub.2 H 211-213 3.11 4-CN
4-Cl H 240-242 3.12 2-CN 4-Cl H 168-170 3.13 3-CN 4-Cl H 189-191
3.14 4-O--CF.sub.3 4-Cl H 162-163 3.15 4-CF.sub.3 4-Cl H 193-194
3.16 2,6-Cl.sub.2, 4-CF.sub.3 4-Cl H 164-165 3.17 2,6-Cl.sub.2,
4-CF.sub.3 4-O--CF.sub.3 H 133-134 3.18 2,6-Cl.sub.2, 4-CF.sub.3
3,5-(CF.sub.3).sub.2 H 121-122 3.19 2-Cl, 4-CF.sub.3 4-O--CF.sub.3
H 104-106 3.20 2-Cl, 4-CF.sub.3 3,5-(CF.sub.3).sub.2 H 129-131 3.21
2,6-Cl.sub.2,4-CF.sub.3 3,5-F.sub.2 H 148-150 3.22 2-Cl, 4-CF.sub.3
3,5-F.sub.2 H 158-159 3.23 2-Cl, 4-CF.sub.3 3-CF.sub.3 H 110-112
3.24 4-CF.sub.3 4-CF.sub.3 H 185-186 3.25 2-Cl, 4-CF.sub.3 4-CN H
189-190 3.26 2,6-Cl.sub.2, 4-CF.sub.3 3,4-Cl.sub.2 H 163-164 3.27
2,6-Cl.sub.2, 4-CF.sub.3 3,4-Cl.sub.2 --CH.sub.3 3.28 2,6-Cl.sub.2,
4-CF.sub.3 3,4-Cl.sub.2 --COCOOC.sub.2H.sub.5 3.29 2,6-Cl.sub.2,
4-CF.sub.3 4-CN --CH.sub.3 92-93 3.30 2,6-Cl.sub.2, 4-CF.sub.3 4-CN
--CH.sub.2OC.sub.2H.sub.5 Resin 3.31 2,6-Cl.sub.2, 4-CF.sub.3 4-CN
--CH.sub.2C.sub.6H.sub.5 Resin 3.32 2,6-Cl.sub.2, 4-CF.sub.3 4-CN
--COCH.sub.3 191-192 3.33 2,6-Cl.sub.2, 4-CF.sub.3 4-CN
--CH.sub.2C.sub.6H.sub.4-2-NO.sub.2 109-111 3.34 2,6-Cl.sub.2,
4-CF.sub.3 4-CN --COOC.sub.2H.sub.5 141-142 3.35 2,6-Cl.sub.2,
4-CF.sub.3 4-CN CN 117-118 3.36 2,6-Cl.sub.2, 4-CF.sub.3 4-CN
--COCOOCH.sub.3 194-195 3.37 2-Cl, 4-CF.sub.3 4-CN
--CH.sub.2OC.sub.2H.sub.5 Resin 3.38 2-Cl, 4-CF.sub.3 4-CN
--CH.sub.2C.sub.6H.sub.5 Resin 3.39 2-Cl, 4-CF.sub.3 4-CN
--CH.sub.2C.sub.6H.sub.4-2-NO.sub.2 81-83 3.40 2-Cl, 4-CF.sub.3
4-CN CH.sub.3 153-154 3.41 2-Cl, 4-CF.sub.3 4-CN --COCH.sub.3
124-125 3.42 2-Cl, 4-CF.sub.3 4-CN 23 "Foam" 3.43 2,4,6-Cl.sub.3
4-CN H 170-171 3.44 2,6-Cl.sub.2, 4-CF.sub.3 2,6-F.sub.2 H 108-109
3.45 2,6-Cl.sub.2, 4-CF.sub.3 4-CN --CONHC.sub.2H.sub.5 211-212
3.46 2,6-Cl.sub.2, 4-CF.sub.3 4-CN --CONHC.sub.6H.sub.4-4-OCF.sub.3
217-218 3.47 2,6-Cl.sub.2, 4-CF.sub.3 4-CN 24 Resin 3.48
2,6-Cl.sub.2, 4-CF.sub.3 4-CN --CO-cyclo-C.sub.3H.sub.5 192-193
3.49 2,6-Cl.sub.2, 4-CF.sub.3 4-CN --COC.sub.6H.sub.4-4-Cl 168-170
3.50 2,6-Cl.sub.2, 4-CF.sub.3 4-NO.sub.2 H 162-163 3.51
2,6-Cl.sub.2, 4-CF.sub.3 4-CN --C.sub.2H.sub.5 Resin 3.52
2,6-Cl.sub.2, 4-CF.sub.3 4-CN n-C.sub.3H.sub.7 95-96 3.53
2,6-Cl.sub.2, 4-CF.sub.3 4-CN i-C.sub.3H.sub.7 3.54 2,6-Cl.sub.2,
4-CF.sub.3 4-CN --CO(CH.sub.2).sub.3CH.dbd.CF.sub.2 120-121 3.55
2,6-Cl.sub.2, 4-CF.sub.3 3,5-Cl.sub.2 H 3.56 2,6-Cl.sub.2,
4-CF.sub.3 3,5-Cl.sub.2 --CH.sub.3 3.57 2,6-Cl.sub.2, 4-CF.sub.3
3,5-Cl.sub.2 --COOC.sub.2H.sub.5 3.58 2,6-Cl.sub.2, 4-CF.sub.3
2,3-Cl.sub.2 H 3.59 2,6-Cl.sub.2, 4-CF.sub.3 2,3-Cl.sub.2
--CH.sub.3 3.60 2,6-Cl.sub.2, 4-CF.sub.3 2,3-Cl.sub.2
--CH.sub.2OC.sub.2H.sub.5 3.61 2,6-Cl.sub.2, 4-CF.sub.3
2,5-Cl.sub.2 H 3.62 2,6-Cl.sub.2, 4-CF.sub.3 2,5-Cl.sub.2
--CH.sub.3 3.63 2,6-Cl.sub.2, 4-CF.sub.3 2,5-Cl.sub.2
--C.sub.2H.sub.5 3.64 2-Cl, 4-CF.sub.3 3,4-Cl.sub.2 H 3.65 2-Cl,
4-CF.sub.3 3,5-Cl.sub.2 H 3.66 2-Cl, 4-CF.sub.3 3,5-Cl.sub.2
--CH.sub.3 3.67 3-CF.sub.3 4-CN H 3.68 3-CF.sub.3 4-CN --CH.sub.3
3.69 2-Cl 4-CN H 3.70 2,3-Cl.sub.2 4-CN H 3.71 2,3-Cl.sub.2 4-CN
--CH.sub.3 3.72 2,4-Cl.sub.2 4-CN H 3.73 2,4-Cl.sub.2 4-CN
--CH.sub.3 3.74 2,4-Cl.sub.2 4-CN --COOCH.sub.3 3.75 2,6-Cl.sub.2,
4-CF.sub.3 4-CN 25 amorphous 3.76 2,6-Cl.sub.2, 4-CF.sub.3 4-CN
--CH.sub.2CN 201-202 3.77 2,6-Cl.sub.2, 4-CF.sub.3 4-NO.sub.2
--CH.sub.3 135-137 3.78 2,6-Cl.sub.2, 4-CF.sub.3 4-CN --CH.sub.2CCH
116-117 3.79 2,6-Cl.sub.2, 4-CF.sub.3 4-CN
--CH.sub.2N(CH.sub.3)CO.sub.2CH.s- ub.3 96-98 3.80 2,6-Cl.sub.2,
4-CF.sub.3 4-CN --CH.sub.2N(CH.sub.3)CO.sub.2C.sub.2H.sub.5 78-80
3.81 2,6-Cl.sub.2, 4-CF.sub.3 2-CN, 4-CF.sub.3 H 124-125 3.82
2,6-Cl.sub.2, 4-CF.sub.3 2-F, 4-CN H 192-193 3.83 2,6-Cl.sub.2,
4-CF.sub.3 3-Cl, 4-CN H 179-180 3.84 2,6-Cl.sub.2, 4-CF.sub.3 4-CN
--CO.sub.2CH.sub.3 122-123 3.85 2,6-Cl.sub.2, 4-CF.sub.3 4-CN
--CO.sub.2CH.sub.2CH.sub.2Cl 125-126 3.86 2,6-Cl.sub.2, 4-CF.sub.3
4-CN --CO.sub.2C.sub.6H.sub.5 105-107 3.87 2,6-Cl.sub.2, 4-CF.sub.3
4-CN --CO.sub.2CH.sub.2C.sub.6H.sub.5 158-159 3.88 2,6-Cl.sub.2,
4-CF.sub.3 4-CN --CO.sub.2CH.sub.2CH(CH.sub.3).sub.2 157-158 3.89
2,6-Cl.sub.2, 4-CF.sub.3 4-CN --CO.sub.2C.sub.8H.sub.- 17 61-62
3.90 2,6-Cl.sub.2, 4-CF.sub.3 4-NO.sub.2 --CO.sub.2C.sub.2H.sub.5
133-134 3.91 2,6-Cl.sub.2, 4-CF.sub.3 4-NO.sub.2
--CH.sub.2CO.sub.2H.sub.5 73-74 3.92 2,6-Cl.sub.2, 4-CF.sub.3
4-NO.sub.2 --C.sub.2H.sub.5 96-97 3.93 2,6-Cl.sub.2, 4-CF.sub.3
3-OCH.sub.3, 4-NO.sub.2 H 146-147 3.94 2,6-Cl.sub.2, 4-CF.sub.3
3-CH.sub.3, 4-NO.sub.2 H 172-173 3.95 2,6-Cl.sub.2, 4-CF.sub.3
2-Cl, 4-NO.sub.2 H 164-165 3.96 2,4,6-Cl.sub.3 4-NO.sub.2 H 180-181
3.97 2,6-Cl.sub.2, 4-CF.sub.3 4-NO.sub.2
--CH.sub.2N(CH.sub.3)CO.sub.2C.sub.2H.sub.5 100-101 3.98
2,6-Cl.sub.2, 4-CF.sub.3 4-NO.sub.2 --COCH.sub.3 175-176 3.99
2,6-Cl.sub.2, 4-CF.sub.3 4-NO.sub.2 --CH.sub.2CCH 165-166 3.100
2.6-Cl.sub.2, 4-CF.sub.3 4-NO.sub.2
--CH.sub.2C.sub.6H.sub.4-4-NO.sub.2 133-135 3.101 2,6-Cl.sub.2,
4-CF.sub.3 4-CN --COCONHC.sub.2H.sub.5 155-157 3.102 2,6-Cl.sub.2,
4-CF.sub.3 2-NO.sub.2, 4-CF.sub.3 H 116-117 3.103 2,6-Cl.sub.2,
4-CF.sub.3 2,4-(NO.sub.2).sub.2 H 143-145 3.104 2,6-Cl.sub.2,
4-CF.sub.3 2-NO.sub.2 H 134-135 3.105 2,6-Cl.sub.2, 4-NO.sub.2
2-NO.sub.2, 4-CF.sub.3 H 100-102 3.106 2,6-Cl.sub.2, 4-NO.sub.2
4-NO.sub.2 H 195-196 3.107 2,6-Cl.sub.2, 4-NO.sub.2 4-CN H 226-227
3.108 2-Cl, 4-Br, 6-CH.sub.3 4-NO.sub.2 H 185-186 3.109 2-Cl, 4-Br,
6-CH.sub.3 4-CN H 181-182 3.110 2,6-(CH.sub.3).sub.2, 4-Br 4-CN H
194-195 3.111 2,6-(CH.sub.3).sub.2, 4-Br 4-NO.sub.2 H 197-198 3.112
2,4,6-Cl.sub.3 4-NO.sub.2
--CH.sub.2N(CH.sub.3)CO.sub.2C.sub.2H.sub.5 110-112 3.113
2,4,6-Cl.sub.3 4-NO.sub.2 --CH.sub.2OC.sub.2H.sub.5 139-141 3.114
2,4,6-Cl.sub.3 4-NO.sub.2 --CO.sub.2C.sub.2H.sub.5 108-110 3.115
2,4,6-Cl.sub.3 4-NO.sub.2 --C.sub.2H.sub.5 94-96 3.116
2,6-Cl.sub.2, 4-CF.sub.3 2-Cl, 4-NO.sub.2 --CH.sub.2OC.sub.2H.sub.5
78-79 3.117 2,6-Cl.sub.2, 4-CF.sub.3 2-Cl, 4-NO.sub.2
--CO.sub.2C.sub.2H.sub.5 114-115 3.118 2,6-Cl.sub.2, 4-CF.sub.3
2-Cl, 4-NO.sub.2 --CH.sub.3 144-145 3.119 2,4,6-Cl.sub.3 4-Cl,
3-NO.sub.2 H 168-169 3.120 2-Cl, 4-Br, 6-CH.sub.3 4-CN CH.sub.3
140-142 3.121 2-Cl, 4-Br, 6-CH.sub.3 4-CN C.sub.2H.sub.5 94-95
3.122 2-Cl, 4-Br, 6-CH.sub.3 4-CN CH.sub.2OC.sub.2H.sub.5 89-90
3.123 2-Cl, 4-Br, 6-CH.sub.3 4-NO.sub.2 CH.sub.2OC.sub.2H.sub.5
103-104 3.124 2-Cl, 4-Br, 6-CH.sub.3 4-NO.sub.2 CH.sub.3 163-164
3.125 2-Cl, 4-Br, 6-CH.sub.3 4-NO.sub.2 C.sub.2H.sub.5 133-135
3.126 2,6-(CH.sub.3).sub.2, 4-Br 4-NO.sub.2 CH.sub.2CO.sub.2H.sub.5
116-118 3.127 2,6-(CH.sub.3).sub.2, 4-Br 4-CN
CH.sub.2CO.sub.2H.sub.5 82-83 3.128 2,6-(CH.sub.3).sub.2, 4-Br
4-NO.sub.2 CH.sub.3 182-183 3.129 2,6-(CH.sub.3).sub.2, 4-Br
4-NO.sub.2 C.sub.2H.sub.5 160-161 3.130 2,6-(CH.sub.3).sub.2, 4-Br
4-CN CH.sub.3 145-146 3.131 2,6-(CH.sub.3).sub.2, 4-Br 4-CN
C.sub.2H.sub.5 105-106 3.132 2,6-Cl.sub.2, 4-CF.sub.3 4-CN
CH.sub.2N(CH.sub.3)SO.sub.2CH.sub.3 143-145 3.133 2,6-Cl.sub.2,
4-CF.sub.3 4-NO.sub.2 CH.sub.2N(CH.sub.3)SO.su- b.2CH.sub.3 156-158
3.134 2,6-Cl.sub.2, 4-CF.sub.3 4-NO.sub.2 CH.sub.2OCH.sub.3 109-110
3.135 2,6-Cl.sub.2, 4-CF.sub.3 4-CN
CH.sub.2N(CH.sub.3)SO.sub.2C.sub.2H.sub.5 140-142 3.136
2,6-Cl.sub.2, 4-CF.sub.3 4-NO.sub.2
CH.sub.2N(CH.sub.3)SO.sub.2C.sub.2H.s- ub.5 128-130 3.137
2,4,6-Cl.sub.3 4-CHO H 152-154 3.138 2,6-Cl.sub.2, 4-CF.sub.3 4-CN
CH.sub.2N(CH.sub.3)SO.sub.2C.sub.6H.sub.5 178-180 3.139
2,6-Cl.sub.2, 4-CF.sub.3 4-NO.sub.2
CH.sub.2N(CH.sub.3)SO.sub.2C.sub.6H.sub.5 122-123 3.140
2,6-Cl.sub.2, 4-CF.sub.3 4-Br H 179-180 3.141 2,6-Cl.sub.2,
4-CF.sub.3 4-NO.sub.2 COCO.sub.2C.sub.2H.sub.5 145-146 3.142
2,6-Cl.sub.2, 4-CF.sub.3 4-NO.sub.2 COCONHC.sub.2H.sub.5 145-147
3.143 2,6-Cl.sub.2, 4-CF.sub.3 4-NO.sub.2 n-C.sub.3H.sub.7 103-104
3.144 2,6-Cl.sub.2, 4-CF.sub.3 4-NO.sub.2 COC.sub.2H.sub.5 153-154
3.145 2,6-Cl.sub.2, 4-CF.sub.3 4-NO.sub.2 CO.sub.2CH.sub.3 129-130
3.146 2,6-Cl.sub.2, 4-CF.sub.3 4-NO.sub.2
CO.sub.2--CH.sub.2CH.sub.2--Cl 130-131 3.147 2,6-Cl.sub.2,
4-CF.sub.3 4-COCF.sub.3 H 111-112 3.148 2,6-Cl.sub.2, 4-CF.sub.3
4-Br CH.sub.2CO.sub.2H.sub.5 78-79 3.149 2,6-Cl.sub.2, 4-CF.sub.3
4-C.sub.6H.sub.4-4-CF.sub.3 CH.sub.2CO.sub.2H.sub.5 107-108 3.150
2,4,6-Cl.sub.3 4-Cl, 3-NO.sub.2 CH.sub.3 3.151 2,4,6-Cl.sub.3 4-Cl,
3-NO.sub.2 C.sub.2H.sub.5 3.152 2,4,6-Cl.sub.3 4-Cl, 3-NO.sub.2
CH.sub.2OC.sub.2H.sub.5 3.153 2,4,6-Cl.sub.3 4-Cl, 3-NO.sub.2
CO.sub.2C.sub.2H.sub.5 3.154 2,6-Cl.sub.2, 4-CF.sub.3 4-Cl,
3-NO.sub.2 H 3.155 2,6-Cl.sub.2, 4-CF.sub.3 4-Cl, 3-NO.sub.2
CH.sub.3 3.156 2,6-Cl.sub.2, 4-CF.sub.3 4-Cl, 3-NO.sub.2
C.sub.2H.sub.5 3.157 2,6-Cl.sub.2, 4-CF.sub.3 4-Cl, 3-NO.sub.2
CH.sub.2OC.sub.2H.sub.5 3.158 2,6-Cl.sub.2, 4-CF.sub.3 4-Cl,
3-NO.sub.2 CO.sub.2C.sub.2H.sub.5 3.159 2,6-Cl.sub.2, 4-CF.sub.3
4-NO.sub.2 i-C.sub.3H.sub.7 124-126 3.160 2,6-Cl.sub.2, 4-CF.sub.3
4-NO.sub.2 --CH.sub.2SCH.sub.3 112-113 3.161 2,6-Cl.sub.2,
4-CF.sub.3 4-NO.sub.2 --CN 111-112 3.162 2,6-Cl.sub.2, 4-CF.sub.3
4-NO.sub.2 --CH.sub.2CH.dbd.CH.sub.2 60-61 3.163 2,6-Cl.sub.2,
4-CF.sub.3 4-NO.sub.2 --CH.sub.2CN 187-188 3.164 2,4-Cl.sub.2,
6-CF.sub.3 4-NO.sub.2 H 135-136 3.165 2,4-Cl.sub.2, 6-CF.sub.3
4-NO.sub.2 --CH.sub.2CO.sub.2H.sub.5 111-113 3.166 2,6-Cl.sub.2,
4-CF.sub.3 4-NO.sub.2 --C(O)(CH.sub.2).sub.3CH.dbd.CF.sub.2 124-125
3.167 2,6-Cl.sub.2, 3-F, 4-CF.sub.3 4-NO.sub.2 H 155-156 3.168
2,6-Cl.sub.2, 4-CF.sub.3 4-NO.sub.2 --CH.sub.2CH.dbd.CCl.sub.2
111-113 3.169 2,6-Cl.sub.2, 4-CF.sub.3 4-NO.sub.2
--C(O)-c-C.sub.3H.sub.5 199-200 3.170 2,6-Cl.sub.2, 3-F, 4-CF.sub.3
4-NO.sub.2 --CH.sub.2CO.sub.2H.sub.5 89-90 3.171 2,6-Cl.sub.2, 3-F,
4-CF.sub.3 4-NO.sub.2 --CO.sub.2C.sub.2H.sub.5 126-127 3.172
2,6-Cl.sub.2, 3-F, 4-CF.sub.3 4-NO.sub.2 --CH.sub.3 164-165 3.173
2,6-Cl.sub.2, 3-F, 4-CF.sub.3 4-NO.sub.2 --C.sub.2H.sub.5 109-111
3.174 2,6-Cl.sub.2, 4-CF.sub.3 4-C.sub.6H.sub.4-(4-CF.sub.3)
--CH.sub.2CO.sub.2H.sub.5 107-108 3.175 2,6-Cl.sub.2, 4-CF.sub.3
4-NO.sub.2 --CH.sub.2SC.sub.6H.sub.5 132-134 3.176 2,6-Cl.sub.2,
4-CF.sub.3 4-C.sub.6H.sub.4-(4-Cl) --CH.sub.2OC.sub.2H.sub.5 93-95
3.177 2-Cl, 4-CF.sub.3, 6-F 4-NO.sub.2 H 169-170 3.178 2-Cl,
4-CF.sub.3, 6-F 4-NO.sub.2 --CH.sub.3 74-76 3.179
2-Cl-4-CF.sub.3-6-F 4-NO.sub.2 --C.sub.2H.sub.5 111-112 3.180 2-Cl,
4-CF.sub.3, 6-F 4-NO.sub.2 --CH.sub.2OC.sub.2H.sub.5 Oil 3.181
2-Cl, 4-CF.sub.3, 6-F 4-NO.sub.2 --CO.sub.2C.sub.2H.sub.5 106-108
3.182 2,6-Cl.sub.2, 4-CF.sub.3
4-C.sub.6H.sub.3-(3,5-(CF.sub.3).sub.- 2) --CH.sub.2OC.sub.2H.sub.5
80-81 3.183 2,6-Cl.sub.2, 4-CF.sub.3 4-C.sub.6H.sub.4-(4-F)
--CH.sub.2OC.sub.2H.sub.5 81-82 3.184 2,6-Cl.sub.2, 4-CF.sub.3
4-C.sub.6H.sub.3-(2,4-Cl.sub.2) --CH.sub.2OC.sub.2H.sub.5 55-57
3.185 2,6-Cl.sub.2, 4-CF.sub.3 4-C.sub.6H.sub.3-(3,5-Cl.sub.2)
--CH.sub.2OC.sub.2H.sub.5 91-93 3.186 2,6-Cl.sub.2, 4-CF.sub.3
4-C.sub.6H.sub.4-(3-CF.sub.3) --CH.sub.2OC.sub.2H.sub.5 58-60 3.187
2,6-Cl.sub.2, 4-CF.sub.3 4-C.sub.6H.sub.3-(3-Cl-4-F)
--CH.sub.2OC.sub.2H.sub.5 78-79 3.188 2,6-Cl.sub.2, 4-CF.sub.3
4-C.sub.6H.sub.4-(3-NO.sub.2) --CH.sub.2OC.sub.2H.sub.5 104-105
3.189 2,3,6-Cl.sub.3, 4-CF.sub.3 4-NO.sub.2 H 143-145 3.190
2,3,6-Cl.sub.3, 4-CF.sub.3 4-NO.sub.2 --CH.sub.3 185-187 3.191
2,3,6-Cl.sub.3, 4-CF.sub.3 4-NO.sub.2 --C.sub.2H.sub.5 104-105
3.192 2,3,6-Cl.sub.3, 4-CF.sub.3 4-NO.sub.2
--CH.sub.2OC.sub.2H.sub.5 88-90 3.193 2,3,6-Cl.sub.3, 4-CF.sub.3
4-NO.sub.2 --CO.sub.2C.sub.2H.sub.5 152-153
[0241]
5TABLE 4 26 No. A.sub.1 (R.sub.3b).sub.n2 R.sub.2 Melting point
(.degree. C.) 4.1 2-pyridyl 4-Cl H 4.2 3-pyridyl 4-Cl H 4.3
4-pyridyl 4-Cl H 4.4 2-pyridyl 4-CN H 4.5 3-pyridyl 4-CN H 4.6
3-pyridyl 4-CN --CH.sub.3 4.7 3-pyridyl 4-CN --COOC.sub.2H.sub.5
4.8 3-pyridyl 4-CN --COOCH.sub.3 4.9 3-pyridyl 4-CN
--CH.sub.2OC.sub.2H.sub.5 4.10 4-pyridyl 4-CN H 4.11 2-pyridyl
4-CF.sub.3 H 4.12 3-pyridyl 4-CF.sub.3 H 4.13 4-pyridyl 4-CF.sub.3
H 4.14 2-pyridyl 4-CF.sub.3 --COOCH.sub.3 4.15 3-pyridyl 4-CF.sub.3
--COOCH.sub.3 4.16 4-pyridyl 4-CF.sub.3 --COOCH.sub.3 4.17
2-pyridyl 4-CF.sub.3 --CH.sub.3 4.18 3-pyridyl 4-CF.sub.3
--CH.sub.3 4.19 4-pyridyl 2-Cl, 4-CF.sub.3 --CH.sub.3 4.20
2-pyridyl 2-Cl, 4-CF.sub.3 --COOCH.sub.3 4.21 3-pyridyl 2-Cl,
4-CF.sub.3 --COOCH.sub.3 4.22 4-pyridyl 2-Cl, 4-CF.sub.3
--COOCH.sub.3 4.23 2-pyridyl 2-Cl, 4-CF.sub.3 --CH.sub.3 4.24
3-pyridyl 2-Cl, 4-CF.sub.3 --CH.sub.3 4.25 4-pyridyl 2-Cl,
4-CF.sub.3 --CH.sub.3 4.26 2-naphthyl 4-Cl H 4.27 3-naphthyl 4-Cl H
4.28 2-naphthyl 4-CN H 4.29 3-naphthyl 4-CN H 4.30 2-naphthyl
4-CF.sub.3 H 4.31 3-naphthyl 4-CF.sub.3 H 4.32 2-naphthyl
4-CF.sub.3 --COOCH.sub.3 4.33 3-naphthyl 4-CF.sub.3 --COOCH.sub.3
4.34 2-naphthyl 2-Cl, 4-CF.sub.3 --CH.sub.3 4.35 3-naphthyl 2-Cl,
4-CF.sub.3 --CH.sub.3
Example H10
[0242]
4-{1-[(2-chloro-4-trifluoromethylphenyl)hydrazono]-2,2,2-trifluoroe-
thyl}chlorobenzene 27
[0243] 3.15 g of 2-chloro-4-trifluoromethylphenylhydrazine, 3.75 g
of 2',2',2'-trifluoro-4-chloroacetophenone, 60 ml of anhydrous
ethanol and 0.2 ml of glacial acetic acid are heated for two days
in a water separator. The mixture is poured into 300 ml of
ice-water and extracted three times using in each case 100 ml of
ethyl acetate. The combined organic phases are washed with water,
dried over sodium sulfate and evaporated to dryness in vacuo. The
residue is crystallized from toluene/hexane 1:1. This gives the
liquid title compound; n.sub.D.sup.20: 1.5390 (compound no.
5.2).
Example H11
[0244] The other compounds listed in Table 5 can also be prepared
analogously to the procedure described in Example H10.
6TABLE 5 28 No. (R.sub.3a).sub.n1 (R.sub.3b).sub.n2 R.sub.1 R.sub.2
Physical data 5.1 2-Cl, 4-CF.sub.3 H CF.sub.3 H n.sub.D.sup.20:
1.5308 5.2 2-Cl, 4-CF.sub.3 4-Cl CF.sub.3 H n.sub.D.sup.20: 1.5390
5.3 2,6-Cl.sub.2, 4-CF.sub.3 4-Cl CF.sub.3 H m.p. 66.5-67.5.degree.
C. 5.4 2,6-Cl.sub.2 4-Cl CF.sub.3 H 5.5 2,6-Cl.sub.2, 4-CF.sub.3
4-CN CF.sub.3 H 5.6 2,6-Cl.sub.2, 4-CF.sub.3 4-Cl CF.sub.3 CH.sub.3
5.7 2-Cl, 4-CF.sub.3 4-Cl CF.sub.3 CH.sub.3 5.8 2,6-Cl.sub.2,
4-CF.sub.3 4-Cl CF.sub.3 COOCH.sub.3 5.9 2,6-Cl.sub.2, 4-CF.sub.3
CN --C(.dbd.S)NH.sub.2 H 5.10 2,6-Cl.sub.2, 4-CF.sub.3 CN
--C(.dbd.S)NH.sub.2 CH.sub.3 5.11 2,6-Cl.sub.2, 4-CF.sub.3
4-NO.sub.2 --C(.dbd.S)NH.sub.2 H 5.12 2,6-Cl.sub.2, 4-CF.sub.3
4-NO.sub.2 --C(.dbd.S)NH.sub.2 --CH.sub.3 5.13 2,6-Cl.sub.2,
4-CF.sub.3 4-NO.sub.2 --C(.dbd.S)NH.sub.2 --CH.sub.2OC.sub.2H.sub.5
m.p. 129-132.degree. C. 5.14 2,6-Cl.sub.2, 4-CF.sub.3 4-NO.sub.2
--C(.dbd.S)NH.sub.2 --CO.sub.2C.sub.2H.sub.5 5.15 2,6-Cl.sub.2,
4-CF.sub.3 4-NO.sub.2 --C(.dbd.S)NH.sub.2
--CH.sub.2N(CH.sub.3)CO.sub.2C.- sub.2H.sub.5 5.16 2,6-Cl.sub.2,
4-CF.sub.3 4-CN --C(.dbd.S)NH.sub.2 --CH.sub.2OC.sub.2H.sub.5 5.17
2,6-Cl.sub.2, 4-CF.sub.3 4-CN --C(.dbd.S)NH.sub.2
--CO.sub.2C.sub.2H.sub.5 5.18 2,6-Cl.sub.2, 4-CF.sub.3 4-CN
--C(.dbd.S)NH.sub.2 --CH.sub.2N(CH.sub.3)CO.sub.2C.sub.2H- .sub.5
5.19 2,4,6-Cl.sub.3 4-NO.sub.2 --C(.dbd.S)NH.sub.2 H 5.20
2,4,6-Cl.sub.3 4-NO.sub.2 --C(.dbd.S)NH.sub.2 --CH.sub.3 5.21
2,4,6-Cl.sub.3 4-NO.sub.2 --C(.dbd.S)NH.sub.2
--CH.sub.2OC.sub.2H.sub.5 5.22 2,4,6-Cl.sub.3 4-NO.sub.2
--C(.dbd.S)NH.sub.2 --CO.sub.2C.sub.2H.sub.5 5.23 2,4,6-Cl.sub.3
4-NO.sub.2 --C(.dbd.S)NH.sub.2
--CH.sub.2N(CH.sub.3)CO.sub.2C.sub.2H.sub.5 5.24 2,4,6-Cl.sub.3
4-CN --C(.dbd.S)NH.sub.2 --CH.sub.2OC.sub.2H.sub.5 5.25
2,4,6-Cl.sub.3 4-CN --C(.dbd.S)NH.sub.2 --CO.sub.2C.sub.2H.sub.5
5.26 2,4,6-Cl.sub.3 4-CN --C(.dbd.S)NH.sub.2
--CH.sub.2N(CH.sub.3)CO.sub.2C.sub.2H.sub.5 5.27 2,6-Cl.sub.2,
4-CF.sub.3 4-NO.sub.2 --CF.sub.3 H 5.28 2,6-Cl.sub.2, 4-CF.sub.3
4-NO.sub.2 --CF.sub.3 --CH.sub.3 5.29 2,6-Cl.sub.2, 4-CF.sub.3
4-NO.sub.2 --CF.sub.3 --CH.sub.2OC.sub.2H.sub.5 5.30 2,6-Cl.sub.2,
4-CF.sub.3 4-NO.sub.2 --CF.sub.3 --CO.sub.2C.sub.2H.sub.5 5.31
2,6-Cl.sub.2, 4-CF.sub.3 4-NO.sub.2 --CF.sub.3
--CH.sub.2N(CH.sub.3)CO.su- b.2C.sub.2H.sub.5 5.32 2,6-Cl.sub.2,
4-CF.sub.3 --CN --CF.sub.3 --CH.sub.3 5.33 2,6-Cl.sub.2, 4-CF.sub.3
--CN --CF.sub.3 --CH.sub.2OC.sub.2H.sub.5 5.34 2,6-Cl.sub.2,
4-CF.sub.3 --CN --CF.sub.3 --CO.sub.2C.sub.2H.sub.5 5.35
2,6-Cl.sub.2, 4-CF.sub.3 --CN --CF.sub.3
--CH.sub.2N(CH.sub.3)CO.sub.2C.sub.2H.sub.5
Example H12
[0245] The compounds listed in Tables 6 to 29 can also be prepared
analogously to the procedure described in Examples H5 to H11.
7 TABLE A No. R.sub.2 (R.sub.3b).sub.n2 A.1) H 4-CN A.2) H
4-NO.sub.2 A.3) H 4-CF.sub.3 A.4) H 2-Cl, 4-NO.sub.2 A.5) H
3-CH.sub.3, 4-NO.sub.2 A.6) H 4-C.sub.6H.sub.5 A.7) H
4-C.sub.6H.sub.4-4-Cl A.8) H 4-C.sub.6H.sub.3-2, 4-Cl.sub.2 A.9) H
4-C.sub.6H.sub.4-4-CF.sub.3 A.10) H 4-C.sub.6H.sub.4-3-CF.sub.3
A.11) H 4-C.sub.6H.sub.3-3, 4-Cl.sub.2 A.12) H 2-F-4-CN A.13) H
2-F, 4-NO.sub.2 A.14) H 4-COCF.sub.3 A.15) H 4-CHO A.16) H 4-Cl,
3-NO.sub.2 A.17) --CH.sub.3 4-CN A.18) --CH.sub.3 4-NO.sub.2 A.19)
--CH.sub.3 4-CF.sub.3 A.20) --CH.sub.3 2-Cl, 4-NO.sub.2 A.21)
--CH.sub.3 3-CH.sub.3, 4-NO.sub.2 A.22) --CH.sub.3 4-C.sub.6H.sub.5
A.23) --CH.sub.3 4-C.sub.6H.sub.4, 4-Cl A.24) --CH.sub.3
4-C.sub.6H.sub.3-2, 4-Cl.sub.2 A.25) --CH.sub.3
4-C.sub.6H.sub.4-4-CF.sub.3 A.26) --CH.sub.3
4-C.sub.6H.sub.4-3-CF.sub.3 A.27) --CH.sub.3 4-C.sub.6H.sub.3-3,
4-Cl.sub.2 A.28) --CH.sub.3 2-F, 4-CN A.29) --CH.sub.3 2-F,
4-NO.sub.2 A.30) --CH.sub.3 4-COCF.sub.3 A.31) --CH.sub.3 4-CHO
A.32) --CH.sub.3 4-Cl, 3-NO.sub.2 A.33) --C.sub.2H.sub.5 4-CN A.34)
--C.sub.2H.sub.5 4-NO.sub.2 A.35) --C.sub.2H.sub.5 4-CF.sub.3 A.36)
--C.sub.2H.sub.5 2-Cl, 4-NO.sub.2 A.37) --C.sub.2H.sub.5
3-CH.sub.3, 4-NO.sub.2 A.38) --C.sub.2H.sub.5 4-C.sub.6H.sub.5
A.39) --C.sub.2H.sub.5 4-C.sub.6H.sub.4-4-Cl A.40) --C.sub.2H.sub.5
4-C.sub.6H.sub.3-2, 4-Cl.sub.2 A.41) --C.sub.2H.sub.5
4-C.sub.6H.sub.4-4-CF.sub.3 A.42) --C.sub.2H.sub.5
4-C.sub.6H.sub.4-3-CF.sub.3 A.43) --C.sub.2H.sub.5
4-C.sub.6H.sub.3-3, 4-Cl.sub.2 A.44) --C.sub.2H.sub.5 2-F, 4-CN
A.45) --C.sub.2H.sub.5 2-F, 4-NO.sub.2 A.46) --C.sub.2H.sub.5
4-COCF.sub.3 A.47) --C.sub.2H.sub.5 4-CHO A.48) --C.sub.2H.sub.5
4-Cl, 3-NO.sub.2 A.49) --CH.sub.2OC.sub.2H.sub.5 4-CN A.50)
--CH.sub.2OC.sub.2H.sub.5 4-NO.sub.2 A.51)
--CH.sub.2OC.sub.2H.sub.5 4-CF.sub.3 A.52)
--CH.sub.2OC.sub.2H.sub.5 2-Cl, 4-NO.sub.2 A.53)
--CH.sub.2OC.sub.2H.sub.5 3-CH.sub.3, 4-NO.sub.2 A.54)
--CH.sub.2OC.sub.2H.sub.5 4-C.sub.6H.sub.5 A.55)
--CH.sub.2OC.sub.2H.sub.5 4-C.sub.6H.sub.4-4-Cl A.56)
--CH.sub.2OC.sub.2H.sub.5 4-C.sub.6H.sub.3-2, 4-Cl.sub.2 A.57)
--CH.sub.2OC.sub.2H.sub.5 4-C.sub.6H.sub.4-4-CF.sub.3 A.58)
--CH.sub.2OC.sub.2H.sub.5 4-C.sub.6H.sub.4-3-CF.sub.3 A.59)
--CH.sub.2OC.sub.2H.sub.5 4-C.sub.6H.sub.3-3, 4-Cl.sub.2 A.60)
--CH.sub.2OC.sub.2H.sub.5 2-F, 4-CN A.61) --CH.sub.2OC.sub.2H.sub-
.5 2-F, 4-NO.sub.2 A.62) --CH.sub.2OC.sub.2H.sub.5 4-COCF.sub.3
A.63) --CH.sub.2OC.sub.2H.sub.5 4-CHO A.64)
--CH.sub.2OC.sub.2H.sub.5 4-Cl, 3-NO.sub.2 A.65)
--CH.sub.2OCH.sub.3 4-CN A.66) --CH.sub.2OCH.sub.3 4-NO.sub.2 A.67)
--CH.sub.2OCH.sub.3 4-CF.sub.3 A.68) --CH.sub.2OCH.sub.3 2-Cl,
4-NO.sub.2 A.69) --CH.sub.2OCH.sub.3 3-CH.sub.3, 4-NO.sub.2 A.70)
--CH.sub.2OCH.sub.3 4-C.sub.6H.sub.5 A.71) --CH.sub.2OCH.sub.3
4-C.sub.6H.sub.4-4-Cl A.72) --CH.sub.2OCH.sub.3 4-C.sub.6H.sub.3-2,
4-Cl.sub.2 A.73) --CH.sub.2OCH.sub.3 4-C.sub.6H.sub.4-4-CF.sub.3
A.74) --CH.sub.2OCH.sub.3 4-C.sub.6H.sub.4-3-CF.sub.3 A.75)
--CH.sub.2OCH.sub.3 4-C.sub.6H.sub.3-3, 4-Cl.sub.2 A.76)
--CH.sub.2OCH.sub.3 2-F, 4-CN A.77) --CH.sub.2OCH.sub.3 2-F,
4-NO.sub.2 A.78) --CH.sub.2OCH.sub.3 4-COCF.sub.3 A.79)
--CH.sub.2OCH.sub.3 4-CHO A.80) --CH.sub.2OCH.sub.3 4-Cl,
3-NO.sub.2 A.81) --CN 4-CN A.82) --CN 4-NO.sub.2 A.83) --CN
4-CF.sub.3 A.84) --CN 2-Cl, 4-NO.sub.2 A.85) --CN 3-CH.sub.3,
4-NO.sub.2 A.86) --CN 4-C.sub.6H.sub.5 A.87) --CN
4-C.sub.6H.sub.4-4-Cl A.88) --CN 4-C.sub.6H.sub.3-2, 4-Cl.sub.2
A.89) --CN 4-C.sub.6H.sub.4-4-CF.sub.3 A.90) --CN
4-C.sub.6H.sub.4-3-CF.sub.3 A.91) --CN 4-C.sub.6H.sub.3-3,
4-Cl.sub.2 A.92) --CN 2-F, 4-CN A.93) --CN 2-F, 4-NO.sub.2 A.94)
--CN 4-COCF.sub.3 A.95) --CN 4-CHO A.96) --CN 4-Cl, 3-NO.sub.2
A.97) --COCH.sub.3 4-CN A.98) --COCH.sub.3 4-NO.sub.2 A.99)
--COCH.sub.3 4-CF.sub.3 A.100) --COCH.sub.3 2-Cl, 4-NO.sub.2 A.101)
--COCH.sub.3 3-CH.sub.3, 4-NO.sub.2 A.102) --COCH.sub.3
4-C.sub.6H.sub.5 A.103) --COCH.sub.3 4-C.sub.6H.sub.4-4-Cl A.104)
--COCH.sub.3 4-C.sub.6H.sub.3-2, 4-Cl.sub.2 A.105) --COCH.sub.3
4-C.sub.6H.sub.4-4-CF.sub.3 A.106) --COCH.sub.3
4-C.sub.6H.sub.4-3-CF.sub.3 A.107) --COCH.sub.3 4-C.sub.6H.sub.3-3,
4-Cl.sub.2 A.108) --COCH.sub.3 2-F, 4-CN A.109) --COCH.sub.3 2-F,
4-NO.sub.2 A.110) --COCH.sub.3 4-COCF.sub.3 A.111) --COCH.sub.3
4-CHO A.112) --COCH.sub.3 4-Cl, 3-NO.sub.2 A.113)
--CH.sub.2--CH.dbd.CH.sub.2 4-CN A.114) --CH.sub.2--CH.dbd.CH.sub.2
4-NO.sub.2 A.115) --CH.sub.2--CH.dbd.CH.sub.2 4-CF.sub.3 A.116)
--CH.sub.2--CH.dbd.CH.sub.2 2-Cl, 4-NO.sub.2 A.117)
--CH.sub.2--CH.dbd.CH.sub.2 3-CH.sub.3, 4-NO.sub.2 A.118)
--CH.sub.2--CH.dbd.CH.sub.2 4-C.sub.6H.sub.5 A.119)
--CH.sub.2--CH.dbd.CH.sub.2 4-C.sub.6H.sub.4-4-Cl A.120)
--CH.sub.2--CH.dbd.CH.sub.2 4-C.sub.6H.sub.3-2, 4-Cl.sub.2 A.121)
--CH.sub.2--CH.dbd.CH.sub.2 4-C.sub.6H.sub.4-4-CF.sub.3 A.122)
--CH.sub.2--CH.dbd.CH.sub.2 4-C.sub.6H.sub.4-3-CF.sub.3 A.123)
--CH.sub.2--CH.dbd.CH.sub.2 4-C.sub.6H.sub.3-3, 4-Cl.sub.2 A.124)
--CH.sub.2--CH.dbd.CH.sub.2 2-F, 4-CN A.125)
--CH.sub.2--CH.dbd.CH.sub.2 2-F, 4-NO.sub.2 A.126)
--CH.sub.2--CH.dbd.CH.sub.2 4-COCF.sub.3 A.127)
--CH.sub.2--CH.dbd.CH.sub.2 4-CHO A.128) --CH.sub.2--CH.dbd.CH.su-
b.2 4-Cl, 3-NO.sub.2 A.129) --CH.sub.2C.ident.CH 4-CN A.130)
--CH.sub.2C.ident.CH 4-NO.sub.2 A.131) --CH.sub.2C.ident.CH
4-CF.sub.3 A.132) --CH.sub.2C.ident.CH 2-Cl, 4-NO.sub.2 A.133)
--CH.sub.2C.ident.CH 3-CH.sub.3, 4-NO.sub.2 A.134)
--CH.sub.2C.ident.CH 4-C.sub.6H.sub.5 A.135) --CH.sub.2C.ident.CH
4-C.sub.6H.sub.4-4-Cl A.136) --CH.sub.2C.ident.CH
4-C.sub.6H.sub.3-2, 4-Cl.sub.2 A.137) --CH.sub.2C.ident.CH
4-C.sub.6H.sub.4-4-CF.sub.3 A.138) --CH.sub.2C.ident.CH
4-C.sub.6H.sub.4-3-CF.sub.3 A.139) --CH.sub.2C.ident.CH
4-C.sub.6H.sub.3-3, 4-Cl.sub.2 A.140) --CH.sub.2C.ident.CH 2-F,
4-CN A.141) --CH.sub.2C.ident.CH 2-F, 4-NO.sub.2 A.142)
--CH.sub.2C.ident.CH 4-COCF.sub.3 A.143) --CH.sub.2C.ident.CH 4-CHO
A.144) --CH.sub.2C.ident.CH 4-Cl, 3-NO.sub.2 A.145)
--CO.sub.2CH.sub.3 4-CN A.146) --CO.sub.2CH.sub.3 4-NO.sub.2 A.147)
--CO.sub.2CH.sub.3 4-CF.sub.3 A.148) --CO.sub.2CH.sub.3 2-Cl,
4-NO.sub.2 A.149) --CO.sub.2CH.sub.3 3-CH.sub.3, 4-NO.sub.2 A.150)
--CO.sub.2CH.sub.3 4-C.sub.6H.sub.5 A.151) --CO.sub.2CH.sub.3
4-C.sub.6H.sub.4-4-Cl A.152) --CO.sub.2CH.sub.3 4-C.sub.6H.sub.3-2,
4-Cl.sub.2 A.153) --CO.sub.2CH.sub.3 4-C.sub.6H.sub.4-4-CF.sub.3
A.154) --CO.sub.2CH.sub.3 4-C.sub.6H.sub.4-3-CF.sub.3 A.155)
--CO.sub.2CH.sub.3 4-C.sub.6H.sub.3-3, 4-Cl.sub.2 A.156)
--CO.sub.2CH.sub.3 2-F, 4-CN A.157) --CO.sub.2CH.sub.3 2-F,
4-NO.sub.2 A.158) --CO.sub.2CH.sub.3 4-COCF.sub.3 A.159)
--CO.sub.2CH.sub.3 4-CHO A.160) --CO.sub.2CH.sub.3 4-Cl, 3-NO.sub.2
A.161) --CO.sub.2C.sub.2H.sub.5 4-CN A.162)
--CO.sub.2C.sub.2H.sub.5 4-NO.sub.2 A.163) --CO.sub.2C.sub.2H.sub.5
4-CF.sub.3 A.164) --CO.sub.2C.sub.2H.sub.5 2-Cl, 4-NO.sub.2 A.165)
--CO.sub.2C.sub.2H.sub.5 3-CH.sub.3, 4-NO.sub.2 A.166)
--CO.sub.2C.sub.2H.sub.5 4-C.sub.6H.sub.5 A.167)
--CO.sub.2C.sub.2H.sub.5 4-C.sub.6H.sub.4-4-Cl A.168)
--CO.sub.2C.sub.2H.sub.5 4-C.sub.6H.sub.3-2, 4-Cl.sub.2 A.169)
--CO.sub.2C.sub.2H.sub.5 4-C.sub.6H.sub.4-4-CF.sub.3 A.170)
--CO.sub.2C.sub.2H.sub.5 4-C.sub.6H.sub.4-3-CF.sub.3 A.171)
--CO.sub.2C.sub.2H.sub.5 4-C.sub.6H.sub.3-3, 4-Cl.sub.2 A.172)
--CO.sub.2C.sub.2H.sub.5 2-F, 4-CN A.173) --CO.sub.2C.sub.2H.sub.-
5 2-F, 4-NO.sub.2 A.174) --CO.sub.2C.sub.2H.sub.5 4-COCF.sub.3
A.175) --CO.sub.2C.sub.2H.sub.5 4-CHO A.176)
--CO.sub.2C.sub.2H.sub.5 4-Cl, 3-NO.sub.2 A.177)
--CH.sub.2N(CH.sub.3)CO.sub.2C.sub.2H.sub.5 4-CN A.178)
--CH.sub.2N(CH.sub.3)CO.sub.2C.sub.2H.sub.5 4-NO.sub.2 A.179)
--CH.sub.2N(CH.sub.3)CO.sub.2C.sub.2H.sub.5 4-CF.sub.3 A.180)
--CH.sub.2N(CH.sub.3)CO.sub.2C.sub.2H.sub.5 2-Cl, 4-NO.sub.2 A.181)
--CH.sub.2N(CH.sub.3)CO.sub.2C.sub.2H.sub.5 3-CH.sub.3, 4-NO.sub.2
A.182) --CH.sub.2N(CH.sub.3)CO.sub.2C.sub.2H.sub.5 4-C.sub.6H.sub.5
A.183) --CH.sub.2N(CH.sub.3)CO.sub.2C.sub.2H.sub- .5
4-C.sub.6H.sub.4-4-Cl A.184) --CH.sub.2N(CH.sub.3)CO.sub.2C.sub-
.2H.sub.5 4-C.sub.6H.sub.3-2, 4-Cl.sub.2 A.185)
--CH.sub.2N(CH.sub.3)CO.sub.2C.sub.2H.sub.5
4-C.sub.6H.sub.4-4-CF.sub.3 A.186)
--CH.sub.2N(CH.sub.3)CO.sub.2C.sub.2H.sub.5
4-C.sub.6H.sub.4-3-CF.sub.3 A.187) --CH.sub.2N(CH.sub.3)CO.sub.2C-
.sub.2H.sub.5 4-C.sub.6H.sub.3-3, 4-Cl.sub.2 A.188)
--CH.sub.2N(CH.sub.3)CO.sub.2C.sub.2H.sub.5 2-F, 4-CN A.189)
--CH.sub.2N(CH.sub.3)CO.sub.2C.sub.2H.sub.5 2-F, 4-NO.sub.2 A.190)
--CH.sub.2N(CH.sub.3)CO.sub.2C.sub.2H.sub.5 4-COCF.sub.3 A.191)
--CH.sub.2N(CH.sub.3)CO.sub.2C.sub.2H.sub.5 4-CHO A.192)
--CH.sub.2N(CH.sub.3)CO.sub.2C.sub.2H.sub.5 4-Cl, 3-NO.sub.2 A.193)
--CH.sub.2N(CH.sub.3)CO.sub.2CH.sub.3 4-CN A.194)
--CH.sub.2N(CH.sub.3)CO.sub.2CH.sub.3 4-NO.sub.2 A.195)
--CH.sub.2N(CH.sub.3)CO.sub.2CH.sub.3 4-CF.sub.3 A.196)
--CH.sub.2N(CH.sub.3)CO.sub.2CH.sub.3 2-Cl, 4-NO.sub.2 A.197)
--CH.sub.2N(CH.sub.3)CO.sub.2CH.sub.3 3-CH.sub.3, 4-NO.sub.2 A.198)
--CH.sub.2N(CH.sub.3)CO.sub.2CH.sub.3 4-C.sub.6H.sub.5 A.199)
--CH.sub.2N(CH.sub.3)CO.sub.2CH.sub.3 4-C.sub.6H.sub.4-4-Cl A.200)
--CH.sub.2N(CH.sub.3)CO.sub.2CH.sub.3 4-C.sub.6H.sub.3-2,
4-Cl.sub.2 A.201) --CH.sub.2N(CH.sub.3)CO.sub.2CH.sub.3
4-C.sub.6H.sub.4-4-CF.sub.3 A.202) --CH.sub.2N(CH.sub.3)CO.sub.2C-
H.sub.3 4-C.sub.6H.sub.4-3-CF.sub.3 A.203) --CH.sub.2N(CH.sub.3)CO-
.sub.2CH.sub.3 4-C.sub.6H.sub.3-3, 4-Cl.sub.2 A.204)
--CH.sub.2N(CH.sub.3)CO.sub.2CH.sub.3 2-F, 4-CN A.205)
--CH.sub.2N(CH.sub.3)CO.sub.2CH.sub.3 2-F, 4-NO.sub.2 A.206)
--CH.sub.2N(CH.sub.3)CO.sub.2CH.sub.3 4-COCF.sub.3 A.207)
--CH.sub.2N(CH.sub.3)CO.sub.2CH.sub.3 4-CHO A.208)
--CH.sub.2N(CH.sub.3)CO.sub.2CH.sub.3 4-Cl, 3-NO.sub.2 A.209)
--COCO.sub.2C.sub.2H.sub.5 4-CN A.210) --COCO.sub.2C.sub.2H.sub.5
4-NO.sub.2 A.211) --COCO.sub.2C.sub.2H.sub.5 4-CF.sub.3 A.212)
--COCO.sub.2C.sub.2H.sub.5 2-Cl, 4-NO.sub.2 A.213)
--COCO.sub.2C.sub.2H.sub.5 3-CH.sub.3, 4-NO.sub.2 A.214)
--COCO.sub.2C.sub.2H.sub.5 4-C.sub.6H.sub.5 A.215)
--COCO.sub.2C.sub.2H.sub.5 4-C.sub.6H.sub.4-4-Cl A.216)
--COCO.sub.2C.sub.2H.sub.5 4-C.sub.6H.sub.3-2, 4-Cl.sub.2 A.217)
--COCO.sub.2C.sub.2H.sub.5 4-C.sub.6H.sub.4-4-CF.sub.3 A.218)
--COCO.sub.2C.sub.2H.sub.5 4-C.sub.6H.sub.4-3-CF.sub.3 A.219)
--COCO.sub.2C.sub.2H.sub.5 4-C.sub.6H.sub.3-3, 4-Cl.sub.2 A.220)
--COCO.sub.2C.sub.2H.sub.5 2-F, 4-CN A.221)
--COCO.sub.2C.sub.2H.sub.5 2-F, 4-NO.sub.2 A.222)
--COCO.sub.2C.sub.2H.sub.5 4-COCF.sub.3 A.223)
--COCO.sub.2C.sub.2H.sub.5 4-CHO A.224) --COCO.sub.2C.sub.2H.sub.-
5 4-Cl, 3-NO.sub.2 A.225) --COCONHC.sub.2H.sub.5 4-CN A.226)
--COCONHC.sub.2H.sub.5 4-NO.sub.2 A.227) --COCONHC.sub.2H.sub.5
4-CF.sub.3 A.228) --COCONHC.sub.2H.sub.5 2-Cl, 4-NO.sub.2 A.229)
--COCONHC.sub.2H.sub.5 3-CH.sub.3, 4-NO.sub.2 A.230)
--COCONHC.sub.2H.sub.5 4-C.sub.6H.sub.5 A.231)
--COCONHC.sub.2H.sub.5 4-C.sub.6H.sub.4-4-Cl A.232)
--COCONHC.sub.2H.sub.5 4-C.sub.6H.sub.3-2, 4-Cl.sub.2 A.233)
--COCONHC.sub.2H.sub.5 4-C.sub.6H.sub.4-4-CF.sub.3 A.234)
--COCONHC.sub.2H.sub.5 4-C.sub.6H.sub.4-3-CF.sub.3 A.235)
--COCONHC.sub.2H.sub.5 4-C.sub.6H.sub.3-3, 4-Cl.sub.2 A.236)
--COCONHC.sub.2H.sub.5 2-F, 4-CN A.237) --COCONHC.sub.2H.sub.5 2-F,
4-NO.sub.2 A.238) --COCONHC.sub.2H.sub.5 4-COCF.sub.3 A.239)
--COCONHC.sub.2H.sub.5 4-CHO A.240) --COCONHC.sub.2H.sub.5 4-Cl,
3-NO.sub.2 A.241) --CH.sub.2N(CH.sub.3)SO.sub.2CH.sub.3 4-CN A.242)
--CH.sub.2N(CH.sub.3)SO.sub.2CH.sub.3 4-NO.sub.2 A.243)
--CH.sub.2N(CH.sub.3)SO.sub.2CH.sub.3 4-CF.sub.3 A.244)
--CH.sub.2N(CH.sub.3)SO.sub.2CH.sub.3 2-Cl, 4-NO.sub.2 A.245)
--CH.sub.2N(CH.sub.3)SO.sub.2CH.sub.3 3-CH.sub.3, 4-NO.sub.2 A.246)
--CH.sub.2N(CH.sub.3)SO.sub.2CH.sub.3 4-C.sub.6H.sub.5 A.247)
--CH.sub.2N(CH.sub.3)SO.sub.2CH.sub.3 4-C.sub.6H.sub.4-4-Cl A.248)
--CH.sub.2N(CH.sub.3)SO.sub.2CH.sub.3 4-C.sub.6H.sub.3-2,
4-Cl.sub.2 A.249) --CH.sub.2N(CH.sub.3)SO.sub.2CH.sub.3
4-C.sub.6H.sub.4-4-CF.sub.3 A.250) --CH.sub.2N(CH.sub.3)SO.sub.2C-
H.sub.3 4-C.sub.6H.sub.4-3-CF.sub.3 A.251) --CH.sub.2N(CH.sub.3)SO-
.sub.2CH.sub.3 4-C.sub.6H.sub.3-3, 4-Cl.sub.2 A.252)
--CH.sub.2N(CH.sub.3)SO.sub.2CH.sub.3 2-F, 4-CN A.253)
--CH.sub.2N(CH.sub.3)SO.sub.2CH.sub.3 2-F, 4-NO.sub.2 A.254)
--CH.sub.2N(CH.sub.3)SO.sub.2CH.sub.3 4-COCF.sub.3 A.255)
--CH.sub.2N(CH.sub.3)SO.sub.2CH.sub.3 4-CHO A.256)
--CH.sub.2N(CH.sub.3)SO.sub.2CH.sub.3 4-Cl, 3-NO.sub.2 A.257)
--CH.sub.2Cl 4-CN A.258) --CH.sub.2Cl 4-NO.sub.2 A.259)
--CH.sub.2Cl 4-CF.sub.3 A.260) --CH.sub.2Cl 2-Cl, 4-NO.sub.2 A.261)
--CH.sub.2Cl 3-CH.sub.3, 4-NO.sub.2 A.262) --CH.sub.2Cl
4-C.sub.6H.sub.5 A.263) --CH.sub.2Cl 4-C.sub.6H.sub.4-4-Cl A.264)
--CH.sub.2Cl 4-C.sub.6H.sub.3-2, 4-Cl.sub.2 A.265) --CH.sub.2Cl
4-C.sub.6H.sub.4-4-CF.sub.3 A.266) --CH.sub.2Cl
4-C.sub.6H.sub.4-3-CF.sub.3 A.267) --CH.sub.2Cl 4-C.sub.6H.sub.3-3,
4-Cl.sub.2 A.268) --CH.sub.2Cl 2-F, 4-CN A.269) --CH.sub.2Cl 2-F,
4-NO.sub.2 A.270) --CH.sub.2Cl 4-COCF.sub.3 A.271) --CH.sub.2Cl
4-CHO A.272) --CH.sub.2Cl 4-Cl, 3-NO.sub.2
[0246] Table 6
[0247] Compounds of the general formula 29
[0248] in which (R.sub.3a).sub.n1 is 2,6-Cl.sub.2-4-CF.sub.3 and
R.sub.2 and (R.sub.3b).sub.n2 correspond to one line of Table
A.
[0249] Table 7
[0250] Compounds of the general formula (Ic), in which
(R.sub.3a).sub.n1 is 2,4,6-Cl.sub.3 and R.sub.2 and
(R.sub.3b).sub.n2 correspond to one line of Table A.
Table 8
[0251] Compounds of the general formula (Ic), in which
(R.sub.3a).sub.n1 is 2-Cl-4-CF.sub.3 and R.sub.2 and
(R.sub.3b).sub.n correspond to one line of Table A.
[0252] Table 9
[0253] Compounds of the general formula (Ic), in which
(R.sub.3a).sub.n1 is 2,6-Cl.sub.2-4-NO.sub.2 and R.sub.2 and
(R.sub.3b).sub.n2 correspond to one line of Table A.
[0254] Table 10
[0255] Compounds of the general formula (Ic), in which
(R.sub.3a).sub.n1 is 2,6-Cl.sub.2-4-OCF.sub.3 and R.sub.2 and
(R.sub.3b).sub.n2 correspond to one line of Table A.
[0256] Table 11
[0257] Compounds of the general formula (Ic), in which
(R.sub.3a).sub.n1 is 2,6-Cl.sub.2-4-F and R.sub.2 and
(R.sub.3b).sub.n2 correspond to one line of Table A.
[0258] Table 12
[0259] Compounds of the general formula (Ic), in which
(R.sub.3a).sub.n1 is 2,6-Cl.sub.2-4-Br and R.sub.2 and
(R.sub.3b).sub.n2 correspond to one line of Table A.
[0260] Table 13
[0261] Compounds of the general formula (Ic), in which
(R.sub.3a).sub.n1 is 2-Cl-4-CF.sub.3-6-F and R.sub.2 and
(R.sub.3b).sub.n2 correspond to one line of Table A.
[0262] Table 14
[0263] Compounds of the general formula (Ic), in which
(R.sub.3a).sub.n1 is 2,3,6-Cl.sub.3-4-CF.sub.3 and R.sub.2 and
(R.sub.3b).sub.n1 correspond to one line of Table A.
[0264] Table 15
[0265] Compounds of the general formula (Ic), in which
(R.sub.3a).sub.n1 is 2,6-Cl.sub.2-3-F-4-CF.sub.3 and R.sub.2 and
(R.sub.3b).sub.n2 correspond to one line of Table A.
[0266] Table 16
[0267] Compounds of the general formula (Ic), in which
(R.sub.3a).sub.n1 is 2,3-F.sub.2-4-CF.sub.3-6-Cl and R.sub.2 and
(R.sub.3b).sub.n2 correspond to one line of Table A.
[0268] Table 17
[0269] Compounds of the general formula (Ic), in which
(R.sub.3a).sub.n1 is 2,6-Cl.sub.2-4-CN and R.sub.2and
(R.sub.3b).sub.n2 correspond to one line of Table A.
[0270] Table 18
[0271] Compounds of the general formula (Ic), in which
(R.sub.3a).sub.n1 is 2,4-Cl.sub.2-6-CF.sub.3 and R.sub.2 and
(R.sub.3b).sub.n2 correspond to one line of Table A.
[0272] Table 19
[0273] Compounds of the general formula (Ic), in which
(R.sub.3a).sub.n1 is 2,6-Cl.sub.2-4-SCF.sub.3 and R.sub.2 and
(R.sub.3b).sub.n2 correspond to one line of Table A.
[0274] Table 20
[0275] Compounds of the general formula (Ic), in which
(R.sub.3a).sub.n1 is 2,6-Cl.sub.2-4-SOCF.sub.3 and R.sub.2 and
(R.sub.3b).sub.n2 correspond to one line of Table A.
[0276] Table 21
[0277] Compounds of the general formula (Ic), in which
(R.sub.3a).sub.n1 is 2,6-Cl.sub.2-4-SO.sub.2CF.sub.3 and R.sub.2
and (R.sub.3b).sub.n2 correspond to one line of Table A.
[0278] Table 22
[0279] Compounds of the general formula (Ic), in which
(R.sub.3a).sub.n1 is 2,6-Cl.sub.2-4-SO.sub.2CH.sub.3 and R.sub.2
and (R.sub.3b).sub.n2 correspond to one line of Table A.
[0280] Table 23
[0281] Compounds of the general formula (Ic), in which
(R.sub.3a).sub.n1 is 2,6-Cl.sub.2-4-OCF.sub.2Br and R.sub.2 and
(R.sub.3b).sub.n2 correspond to one line of Table A.
[0282] Table 24
[0283] Compounds of the general formula (Ic), in which
(R.sub.3a).sub.n1 is 2,6-Cl.sub.2-4-OCF.sub.2H and R.sub.2 and
(R.sub.3b).sub.n2 correspond to one line of Table A.
[0284] Table 25
[0285] Compounds of the general formula (Ic), in which
(R.sub.3a).sub.n1 is 2,6-Cl.sub.2-4-C.sub.2F.sub.5 and R.sub.2 and
(R.sub.3b).sub.n2 correspond to one line of Table A.
[0286] Table 26
[0287] Compounds of the general formula (Ic), in which
(R.sub.3a).sub.n1 is 2,6-(NO.sub.2).sub.2-4-CF.sub.3 and R.sub.2
and (R.sub.3b).sub.n2 correspond to one line of Table A.
[0288] Table 27
[0289] Compounds of the general formula (Ic), in which
(R.sub.3a).sub.n1 is 2,6-(NO.sub.2).sub.2-4-Cl and R.sub.2 and
(R.sub.3b).sub.n2 correspond to one line of Table A.
[0290] Table 28
[0291] Compounds of the general formula (Ic), in which
(R.sub.3a).sub.n1 is 2,6-Cl.sub.2-4-OSO.sub.2CH.sub.3 and R.sub.2
and (R.sub.3b).sub.n2 correspond to one line of Table A.
[0292] Table 29
[0293] Compounds of the general formula (Ic), in which
(R.sub.3a).sub.n1 is 2,6-Cl.sub.2-4-OSO.sub.2CF.sub.3 and R.sub.2
and (R.sub.3b).sub.n2 correspond to one line of Table A.
Formulation Examples
[0294] (%=percent by weight)
8 Example F1: Emulsion concentrates a) b) c) Active ingredient 25%
40% 50% Calcium dodecylbenzenesulfonate 5% 8% 6% Castor oil
polyethylene glycol 5% -- -- ether (36 mol of EO) Tributylphenol
polyethylene -- 12% glycol ether (30 mol of EO) Cyclohexanone --
15% 20% Xylene mixture 65% 25% 20% EO is the degree of ethoxylation
of the alcoholic group in question.
[0295] Mixing finely ground active ingredient and additives gives
an emulsion concentrate which gives emulsions of any desired
concentration by dilution with water.
9 Example F2: Solutions a) b) c) d) Active ingredient 80% 10% 5%
95% Ethylene glycol monomethyl ether 20% -- -- -- Polyethylene
glycol -- 70% -- -- (molecular weight 400) N-Methylpyrrolid-2-one
-- 20% -- -- Epoxidized coconut oil -- -- 1% 5% Petroleum ether --
-- 94% -- (boiling range: 160-190)
[0296] Mixing finely ground active ingredient and additives gives a
solution which is suitable for use in the form of microdrops.
10 Example F3: Granules a) b) c) d) Active ingredient 5% 10% 8% 21%
Kaolin 94% -- 79% 54% Highly disperse silica 1% -- 13% 7%
Attapulgite -- 90% -- 18%
[0297] The active ingredient is dissolved in dichloromethane, the
solution is sprayed onto the carrier mixture, and the solvent is
evaporated in vacuo.
11 Example F4: Dusts a) b) Active ingredient 2% 5% Highly disperse
silica 1% 5% Talc 97% -- Kaolin -- 90%
[0298] Ready-to-use dusts are obtained by mixing active ingredient
and carriers.
12 Example F5: Wettable powders a) b) c) Active ingredient 25% 50%
75% Sodium lignosulfonate 5% 5% -- Sodium lauryl sulfate 3% -- 5%
Sodium diisobutylnaphthalenesul- fonate -- 6% 10% Octylphenol
polyethylene glycol ether -- 2% -- (7-8 mol of EO) Highly disperse
silica 5% 10% 10% Kaolin 62% 27% --
[0299] Active ingredient and additives are mixed and the mixture is
ground in a suitable mill. This gives wettable powders which can be
diluted with water to give suspensions of any desired
concentration.
13 Example F6: Emulsion concentrate Active ingredient 10%
Octylphenol polyethylene glycol ether (4-5 mol of EO) 3% Calcium
dodecylbenzenesulfonate 3% Castor oil polyethylene glycol ether (36
mol of EO) 4% Cyclohexanone 30% Xylene mixture 50%
[0300] An emulsion concentrate, which gives emulsions of any
desired concentration by dilution with water, is obtained by mixing
finely ground active ingredient and additives.
14 Example F7: Dusts a) b) Active ingredient 5% 8% Talc 95% --
Kaolin -- 92%
[0301] Ready-to-use dusts are obtained by mixing active ingredient
and carrier and grinding the mixture in a suitable mill.
15 Example F8: Extruder granules Active ingredient 10% Sodium
lignosulfonate 2% Carboxymethylcellulose 1% Kaolin 87%
[0302] Active ingredient and additives are mixed, the mixture is
ground, the powder is moistened with water, extruded and
granulated, and the granules are dried in a stream of air.
16 Example F9: Coated granules Active ingredient 3% Polyethylene
glycol (MW 200) 3% Kaolin 94%
[0303] Dust-free coated granules are obtained by uniformly applying
the finely ground active ingredient, in a mixer, to the kaolin
which has been moistened with polyethylene glycol.
17 Example F10: Suspension concentrate Active ingredient 40%
Ethylene glycol 10% Nonylphenol polyethylene glycol ether (15 mol
of EO) 6% Sodium lignosulfonate 10% Carboxymethylcellulose 1%
Aqueous formaldehyde solution (37%) 0.2% Aqueous silicone oil
emulsion (75%) 0.8% Water 32%
[0304] A suspension concentrate, which gives suspensions of any
desired concentration by dilution with water, is obtained by mixing
finely ground active ingredient and additives.
Biological Examples
Example B1
[0305] Ovicidal Action on Heliothis virescens
[0306] Heliothis virescens eggs which have been deposited on filter
paper are briefly immersed into an acetonic/aqueous test solution
comprising 400 ppm of the active ingredient to be tested. After the
test solution has dried on, the eggs are incubated in Petri dishes.
After 6 days, the percentage hatching rate of the eggs is evaluated
in comparison with untreated control batches (% reduction in
hatching).
[0307] In this test, compounds of Tables 3 to 29 are very
effective. Compounds nos. 3.2 to 3.4, 3.18, 3.20, 3.26, 3.43, 3.48,
3.50, 3.54, 3.77 to 3.85, 3.90 to 3.98 and 3.101 to 3.103, in
particular, exhibit an activity of over 80%.
Example B2
[0308] Action Against Spodoptera littoralis Caterpillars
[0309] Young soya plants are sprayed with an aqueous emulsion spray
mixture which comprises 400 ppm of the active ingredient. After the
spray coating has dried on, the soya plants are populated with 10
third instar caterpillars of Spodoptera littoralis and introduced
into a plastic container. Three days later, the test is evaluated.
The percentage reduction in population, or the percentage reduction
in feeding damage (% activity), is determined by comparing the
number of dead caterpillars and the feeding damage on the treated
plants with those on the untreated plants.
[0310] In this test, compounds of Tables 3 to 29 are very
effective. Compounds nos. 3.2 to 3.4, 3.10,3.18,
3.20,3.21,3.31,3.31, 3.34 to 3.37,3.41,3.43,3.48 to 3.52,3.54,3.77
to 3.98 and 3.101 to 3.103, in particular, exhibit an activity of
over 80%.
Example B3
[0311] Activity Against Diabrotica balteata Larvae
[0312] Maize seedlings are sprayed with an aqueous emulsion spray
mixture which comprises 400 ppm of the active ingredient. After the
spray coating has dried on, the maize seedlings are populated with
10 second instar larvae of Diabrotica balteata and introduced into
a plastic container. 6 days later, the test is evaluated. The
percentage reduction in population (% activity) is determined by
comparing the number of dead larvae on the treated plants with
those on the untreated plants.
[0313] In this test, compounds of Tables 3 to 29 are very
effective. Compounds nos. 3.2 to 3.4, 3.7, 3.8, 3.10, 3.20, 3.21,
3.29 to 3.32, 3.34 to 3.37, 3.41, 3.43, 3.48, 3.49, 3.50 to 3.52,
3.77 to 3.80, 3.82 to 3.87, 3.90 to 3.98 and 3.100 to 3.103, in
particular, exhibit an activity of over 80%.
Example B4
[0314] Activity Against Plutella xylostella Caterpillars
[0315] Young cabbage plants are sprayed with an aqueous emulsion
spray mixture which comprises 400 ppm of the active ingredient.
After the spray coating has dried on, the cabbage plants are
populated with 10 third instar caterpillars of Plutella xylostella
and introduced into a plastic container. 3 days later, the test is
evaluated. The percentage reduction in population, or the
percentage reduction in feeding damage (% activity), is determined
by comparing the number of dead caterpillars and the feeding damage
on the treated plants with those on the untreated plants.
[0316] In this test, compounds of Tables 3 to 29 are very
effective. Compounds nos. 3.2 to 3.4, 3.7, 3.18,3.20, 3.21, 3.26,
3.29 to 3.32, 3.34 to 3.37, 3.41, 3.43, 3.48, 3.49, 3.50 to 3.52,
3.54, 3.77 to 3.98, 3.101 and 3.103, in particular, exhibit an
activity of over 80%.
Example B5
[0317] Activity Against Tetranychus urticae
[0318] Young bean plants are populated with a mixed population of
Tetranychus urticae and, 1 day later, sprayed with an aqueous
emulsion spray mixture which comprises 400 ppm of the active
ingredient. The plants are subsequently incubated for 6 days at
25.degree. C. and then evaluated. The percentage reduction in
population (% activity) is determined by comparing the number of
dead eggs, larvae and adults on the treated plants with those on
the untreated plants.
[0319] In this test, compounds of Tables 3 to 29 are very
effective. Compounds nos. 3.3, 3.17, 3.18, 3.20, 3.21, 3.29, 3.30,
3.34 to 3.37, 3.41, 3.48 to 3.52, 3.77, 3.78, 3.80, 3.82 to 3.92,
3.94, 3.95, 3.97, 3.98 and 3.101 to 3.103, in particular, exhibit
an activity of over 80%.
Example B6
[0320] Activity Against Heliothis virescens Caterpillars
[0321] Young soya plants are sprayed with an aqueous emulsion spray
mixture which comprises 400 ppm of the active ingredient. After the
spray coating has dried on, the soya plants are populated with 10
first instar caterpillars of Heliothis virescens and introduced
into a plastic container. 6 days later, the test is evaluated. The
percentage reduction in population, or the percentage reduction in
feeding damage (% activity), is determined by comparing the number
of dead caterpillars and the feeding damage on the treated plants
with those on the untreated plants.
[0322] In this test, compounds of Tables 3 to 29 are very
effective. Compounds nos. 3.2 to 3.4, 3.18, 3.20, 3.21, 3.29, 3.30,
3.32, 3.34, 3.35, 3.36, 3.41, 3.48 to 3.51, 3.54, 3.77 to 3.80,
3.82 to 3.85, 3.90 to 3.92, 3.94 to 3.98 and 3.101 to 3.103, in
particular, exhibit an activity of over 80%.
Example B7
[0323] Activity Against Panonychus ulmi (OP- and
Carb.-resistant)
[0324] Apple seedlings are populated with adult females of
Panonychus ulmi. After 7 days, the infected plants are sprayed to
drip point with an aqueous emulsion spray mixture comprising 400
ppm of the compound to be tested and grown in a greenhouse. After
14 days, the test is evaluated. The percentage reduction in
population (% activity) is determined by comparing the number of
dead spider mites on the treated plants with those on the untreated
plants.
[0325] In this test, compounds of Tables 3 to 29 are very
effective. Compounds nos. 3.34, 3.77, 3.78, 3.80 and 3.90 to 3.92,
in particular, exhibit an activity of over 80%.
Example B8
[0326] Activity Against Aphis craccivora
[0327] Pea seedlings are infected with Aphis craccivora and
subsequently sprayed with a spray mixture which comprises 400 ppm
of the active ingredient and incubated at 20.degree. C. 3 and 6
days later, respectively, the test is evaluated. The percentage
reduction in population (% activity) is determined by comparing the
number of dead aphids on the treated plants with those on the
untreated plants.
[0328] In this test, compounds of Tables 3 to 29 are very
effective. Compounds nos. 3.41, 3.77, 3.90, 3.92, 3.95, 3.97, 3.98
and 3.106, in particular, exhibit an activity of over 80%.
Example B9
[0329] Activity Against Myzus persicae
[0330] Pea seedlings are infected with Myzus persicae and
subsequently sprayed with a spray mixture which comprises 400 ppm
of the active ingredient and incubated at 20.degree. C. 3 and 6
days later, respectively, the test is evaluated. The percentage
reduction in population (% activity) is determined by comparing the
number of dead aphids on the treated plants with those on the
untreated plants.
[0331] In this test, compounds of Tables 3 to 29 are very
effective. Compounds nos. 3.77, 3.90, 3.92, 3.97 and 3.98, in
particular, exhibit an activity of over 80%.
Example B10
[0332] Activity Against Nilaparvata lugens
[0333] Rice plants are treated with an aqueous emulsion spray
mixture which comprises 400 ppm of the active ingredient. After the
spray coating has dried on, the rice plants are populated with 2nd
and 3rd instar larvae of Nilaparvata lugens. 21 days later, the
test is evaluated. The percentage reduction in population (%
activity) is determined by comparing the number of surviving leaf
hoppers on the treated plants with those on the untreated
plants.
[0334] In this test, compounds of Tables 3 to 29 are very
effective. Compounds nos. 3.18, 3.20, 3.30, 3.51, 3.77, 3.80, 3.92
and 3.98, in particular, exhibit an activity of over 80%.
Example B11
[0335] Activity Against Frankliniella occidentalis
[0336] Bell pepper plants in the greenhouse which are populated
with a natural mixed population of larvae, nymphs and adults of
Frankliniella occidentalis are sprayed three times to drip point at
10-day intervals with a spray mixture which comprises 10 g/hl of
the compound of the formula 1. Immeditely prior to the second and
one day after the third treatment, the nymphs on the treated plants
and on untreated control plants are counted,and the reduction in
the number of nymphs is determined.
[0337] In this test, compounds of Tables 3 to 29 are very
effective. Compounds nos. 3.2, 3.18, 3.20, 3.48, 3.77, 3.79, 3.80,
3.84, 3.89, 3.90 and 3.91, in particular, exhibit an activity of
over 80%.
* * * * *