Intermediates to pesticidal 1-arylpyrazoles

Details Intermediates to pesticidal 1-arylpyrazoles Intermediates to pesticidal 1-arylpyrazoles

2000-02-07

2001-01-30

Ramsuer, Robert W. (Department: 1626)

Organic compounds -- part of the class 532-570 series

Organic compounds

Heterocyclic carbon compounds containing a hetero ring...

C546S276100

Reexamination Certificate

active

06180798

ABSTRACT:

The present invention relates to novel arylpyrazoles, compositions containing them, processes for their preparation, and their uses as insecticides and nematicides.
This invention relates to 1-arylpyrazole derivatives, to compositions containing them and to the use of said compounds and compositions against arthropods, particularly insects and nematodes.
U.S. Pat. No. 5,232,940 describes N-phenylpyrazoles with, among others, 5-cycloalkylcarbonyl and 5-alkoxycarbonyl substituents.
DE 3509567 and EP 382034 describe 3-nitro-1-phenylpyrazoles as herbicides and insecticides.
DE 2701091 describes fungicidal pyrazoles with amides at positions 4 or 5.
EP 202169 describes 1-(4-alkoxy)phenyl pyrazoles as herbicides.
EP 398499 describes cyano-phenylpyrazoles as insecticides.
None of the foregoing publications describes or suggests that compounds of formula (1) possess or would be expected to possess activity against arthropods, especially insects or nematodes.
This invention provides novel arylpyrazoles of the formula (1):
wherein:
R
1
is selected from cyano, halogen, formyl, C(O)R
2
, H, and R
2
;
R
2
is selected from C
1
-C
4
alkyl; C
1
-C
4
haloalkyl, and cycloalkyl optionally substituted with one or more halogens;
R
3
is selected from halogen, C
1
-C
4
alkyl, C
1
-C
4
haloalkyl, nitro, CONR
4
R
5,
COOR
4
, and —S(O)
n
R
6;
R
4
and R are independently selected from H, C
1
-C
5
alkyl, and C
1
-C
5
haloalkyl;
R
6
is selected from C
1
-C
4
alkyl, C
1
-C
4
haloalkyl, and cycloalkyl optionally substituted with one or more halogens;
R
7
is selected from C(O)R
8
, C
1
-C
6
&agr;-hydroxyalkyl, C
1
-C
6
&agr;-hydroxyhaloalkyl, C(OR
9
)=CHR
10
, CHR
11
R
12
, —CR
13
=ND and
R
8
is selected from H, C
1
-C
5
alkyl, and C
1
-C
5
haloalkyl;
R
9
is selected from C(O)R
18
, CHO, —S(O)
2
R
18
, —S(O)
2
aryl, C
3
-C
18
trialkylsilyl, C
8
-C
18
dialkylarylsilyl, C
13
-C
20
diarylalkylsilyl and C
18
-C
24
triarylsilyl;
R
10
is selected from H, C
1
-C
4
alkyl, and C
1
-C
4
haloalkyl;
R
11
and R
12
are independently selected from C
1
-C
4
alkoxy, C
1
-C
4
haloalkoxy, C
1
-C
4
alkylthio, C
1
-C
4
haloalkylthio, NR
8
R
10
, C
3
-C
8
trialkylsilyl and cyano;
R
13
is selected from H, C
1
-C
5
alkyl, and C
1
-C
5
haloalkyl;
R
14
is selected from H, halogen, C
1
-C
4
alkyl, C
1
-C
4
haloalkyl, C
1
-C
4
alkoxy, C
1
-C
4
haloalkoxy, C
1
-C
4
alkylthio, C
1
-C
4
haloalkylthio, cyano and nitro;
R
15
and R
17
are independently selected from H and halogen;
R
16
is selected from halogen, C
1
-C
4
alkyl, C
1
-C
4
haloalkyl, C
1
-C
4
alkoxy, C
1
-C
4
haloalkoxy, cyano, nitro, C(O)R
18
, and —S(O)
q
R
19
;
R
18
is selected from C
1
-C
3
alkyl and C
1
-C
3
haloalkyl;
R
19
is selected from C
1
-C
3
alkyl and C
1
-C
3
haloalkyl;
X is selected from a nitrogen atom or C-R
20
;
R
20
is selected from H, halogen, cyano, nitro, C
1
-C
4
alkyl, C
1
-C
4
haloalkyl, C
1
-C
4
alkoxy, and C
1
-C
4
haloalkoxy;
A and E are independently selected from NR
21
, O and S;
R
21
is selected from H, C
1
-C
4
alkyl and C
1
-C
4
haloalkyl;
D is selected from OR
22
and NR
23
R
24
;
R
22
, R
23
and R
24
are independently selected from H, C
1
-C
4
alkyl, and Cl-C4 haloalkyl;
Z is (CH
2
m
;
m is 2, 3 or 4;
n is 0, 1 or 2;
q is 0, 1 or 2;
and pesticidally acceptable salts thereof;
provided that:
R
11
and R
12
are always the same except when R
12
is cyano; and
R
4
is not H when R
3
is COOR
4
.
By the term “pesticidally acceptable salts” is meant salts the anions of which are known and accepted in the art for the formation of pesticidally acceptable salts. Preferably such salts are water soluble. Suitable acid addition salts, formed by compounds of formula (I) containing an amine group, include salts with inorganic acids, for example hydrochlorides, phosphates, sulfates, nitrates; and salts with organic acids, for example acetates.
In this specification, “halogen” means the atoms fluorine, chlorine, bromine and iodine. Alkyl groups and moieties may be either linear or branched chain. “Cycloalkyl” means a cycloalkyl group having from three to seven carbon atoms in the ring, each of which optionally bears one or more C
1
-C
4
alkyl. “Aryl” means phenyl optionally substituted by one or more of the members of the group consisting of C
1
-C
4
alkyl and halogen which may be the same or different. It will be understood that in certain cases, compounds of formula (I) can be present in the form of optical and/or stereoisomers. All such forms are embraced by the invention.
Compounds of formula (1) above in which R
7
is formyl generally possess a lower level of activity as insecticides but are useful as intermediates in the preparation of more highly active species.
It will be understood that the provisos appearing in the above description are present for reasons of biological efficacy and synthetic accessibility.
A feature of the invention are those compounds having one or more of the following features:
R
1
is cyano;
R
3
is —S(O)
n
R
6
;
R
7
is selected from the group C(O)R
8
, C
1
-C
6
&agr;-hydroxyalkyl, C
1
-C
6
&agr;-hydroxyhaloalkyl, C(OR
9
)=CHR
10
, CHR
11
R
12
, and —CR
13
=ND;
R
14
is halogen;
R
15
and R
17
are H;
R
16
is C
1
-C
4
haloalkyl; and
X is C—R
20
.
Preferred compounds of formula (I) above are compounds wherein:
R
1
is selected from cyano, halogen, C(O)R
2
, H, and R
2
;
R
3
is —S(O)
n
R
6
;
R
7
is selected from C(O)R
8
, —CR
13
=ND, and —CHR
11
R
12
;
R
14
is halogen;
R
15
and R
17
are H; and
R
16
is C
1
-C
4
haloalkyl.
A further preferred class of compounds of formula (1) are those wherein:
R
1
is cyano;
R
3
is —S(O)
n
R
6
;
R
6
is C
1
-C
2
haloalkyl, preferably CF
3
;
R
7
is selected from C(O)R
8
, —CHR
11
R
12
and —CR
13
=ND;
R
11
is C
1
-C
4
alkoxy;
R
12
is selected from C
1
-C
4
alkoxy and cyano;
R
14
is halogen;
R
15
and R
17
are H;
R
16
is C
1
-C
2
haloalkyl, especially CF
3
.
The numbers 1-21 are assigned to these compounds for reference and identification. Hereinafter compounds of formula (I) include the following:
1. 5-Acetyl-3-cyano-1-(2,6-dichloro4-trifluoromethylphenyl)-4 trifluoromethylsulfonylpyrazole, m.p. about 161° C.;
2. 3-Cyano-1-(2,6-dichloro4-trifluoromethylphenyl)-5-formyl-4-trifluoromethylthiopyrazole, m.p. about 90° C.;
3. 5-{(N-amino)iminomethylidenyl}-3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-4-trifluoromethylthiopyrazole, m.p. about 130° C.;
4. 3-Cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-5-dimethoxymethyl-4-trifluoromethylthiopyrazole, m.p. about 93° C.;
5. 3-Cyano-1-(2,6dichloro-4-trifluoromethylphenyl)-5-{(N-methoxy)iminomethylidenyl}-4-trifluoromethylthiopyrazole, m.p. about 87° C.;
6. 3-Cyano-5-{(1-cyano-1-methoxy)methyl}-1-(2,6-dichloro-4-trifluoromethylphenyl)4-trifluoromethylthiopyrazole, an oil;
7. 3-Cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-5-(hydroxy)methyl-4-trifluoromethylthiopyrazole, m.p. about 118° C.;
8. 3-Cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-5-(1-hydroxy)ethyl-4-trifluoromethylthiopyrazole, m.p. about 123° C.;
9. 5-Acetyl-3-cyano-1-(2,6-dichloro4-trifluoromethylphenyl)4-trifluoromethylthiopyrazole, m.p. about 128° C.;
10. 5-Acetyl-3-cyano-1-(2,6-dichloro-trifluoromethylphenyl)-4-trifluoromethylsulfonylpyrazole, m.p. 156° C.;
11. 3-Cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-5-(N,N-dimethylaminominomethylidenyl)-4-trifluoromethylthiopyrazole, m.p. about 126 ° C.;
12. 3-Cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-5-(hydroxy)methyl , trifluoromethylsulfonylpyrazole, m.p. about 153° C;
13. 3-Cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-5-dimethoxymethyl-4-trifluoromethylsulfonylpyrazole, m.p. about 116° C.;
14. 3-Cyano-5-{(1-cyano-1-methoxy)methyl}-1-(2,6-dichloro4- trifluoromethylphenyl)-4-trifluoromethylsulfonylpyrazole, m.p. about 167° C.;
15. 3-Cyano-1-(2,6-dichloro-4trifluoromethylphenyl)-5-dimethoxymethyl-4-trifluoromethylsulfonylpyrazole, m.p. 137° C.;
16. 3-Cyano-5-{(1-cyano-1-methoxy)methyl}-1-(2,6-dichloro-4-trifluoromethylphenyl)4-trifluoromethylsulfonylp

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