INSECTICIDAL BIPHENYLTHIOHYDRAZIDES

INSECTICIDES A BASE DE BIPHENYLTHIOHYDRAZIDES

English Abstract

The present invention provides N-biphenylthiohydrazone derivatives of formula
(I) and compositions and methods for the use thereof in the control of insect
and acarid pests and for the protection of crops therefrom.

French Abstract

La présente invention concerne des dérivés N-biphénylthiohydrazone représentés par la formule (I). L'invention concerne également des compositions et les procédés d'emploi correspondant, d'une part contre les insectes et acariens nuisibles, et d'autre part pour protéger les récoltes contre ces nuisibles.

Claims

-37-

WHAT IS CLAIMED IS:

1. A compound of formula I

Image

wherein
R is hydrogen,
C1-C10alkyl optionally substituted with one or more
halogen,
C3-C6cycloalkyl,
C1-C4alkoxy,
C1-C4haloalkoxy,
(C1-C4-alkyl)SO x,
(C1-C4haloalkyl)SO y,
phenyl optionally substituted with one to
three halogen,
C1-C4alkyl,
C1-C4haloalkyl,
C1-C4alkoxy,
C1-C4haloalkoxy,
(C1-C4alkyl)SO x,
(C1-C4haloalkyl)SO y,
NO2 or CN groups, or
phenoxy optionally substituted with one to
three halogen,




-38-

C1-C4alkyl,
C1-C4haloalkyl,
C1-C4alkoxy,
C1-C4haloalkoxy,
(C1-C4alkyl)SO x,
(C1-C4haloalkyl)SO y,
NO2 or CN groups;
C3-C12cycloalkyl optionally substituted with one or
more halogens,
C1-C6alkyl,
C1-C4haloalkyl,
C1-C4alkoxy,
C1-C4haloalkoxy,
(C1-C4alkyl)SO x,
(C1-C4haloalkyl)SO x,
phenyl optionally substituted with
one to three halogen,
C1-C4alkyl
C1-C4haloalkyl,
C1-C4alkoxy,
C1-C4haloalkoxy,
NO2 or CN groups, or
phenoxy optionally substituted with one to
three halogen,
C1-C4alkyl,
C1-C4haloalkyl,
C1-C4alkoxy,
C1-C4haloalkoxy,
NO2 or CN groups; or
phenyl optionally substituted with one or more
halogen,
C1-C4alkyl,
C1-C4haloalkyl,




-39-

C1-C4alkoxy,
C1-C4haloalkoxy,
NO2 or CN groups;
with the proviso that when R is phenyl, then m must be 1
or 2;
R1 is R12;
C1-C10alkyl optionally substituted with one or more
halogen,
hydroxy,
phenyl optionally substituted with one or more
halogen,
C1-C4alkyl,
C1-C4haloalkyl,
C1-C4alkoxy,
C1-C4haloalkoxy,
NO2 or CN groups,
C1-C4alkoxy,
C1-C4haloalkoxy,
(C1-C4alkyl)SO x,
CONR8R9,
CO2R10,
R11,
R12.
C3-C6cycloalkyl optionally substituted with one
to three halogen,
C1-C4alkyl,
C1-C4 haloalkyl,
C1-C4alkoxy,
C1-C4haloalkoxy,
NO2 or CN groups,
phenyl optionally substituted with one or more
halogen,
C1-C4alkyl,




-40-

C1-C4haloalkyl,
C1-C4alkoxy,
C1-C4haloalkoxy,
NO2 or CN groups, or
pyridyl optionally substituted with one or more
halogen,
C1-C4alkyl,
C1-C4haloalkyl,
C1-C4alkoxy,
C1-C4haloalkoxy,
NO2 or CN groups;
C2-C10alkenyl optionally substituted with one or
more halogen,
hydroxy,
C1-C4alkoxy,
(C1-C4alkyl)SO x,
CONR8R9,
CO2R10,
R11,
R12,
C3-C6cycloalkyl optionally substituted with one
to three halogen,
C1-C4alkyl,
C1-C4halo-alkyl,
C1-C4alkoxy,
C1-C4haloalkoxy,
NO2 or CN groups,
phenyl optionally substituted with one or more
halogen,
C1-C4alkyl,
C1-C4haloalkyl,
C1-C4alkoxy,
C1-C4haloalkoxy,




-41-

NO2 or CN groups, or
pyridyl optionally substituted with one or more
halogen,
C1-C4alkyl,
C1-C4haloalkyl,
C1-C4alkoxy,
C1-C4haloalkoxy,
NO2 or CN groups;
C2-C10alkynyl optionally substituted with one or
more halogen,
hydroxy,
C1-C4alkoxy,
(C1-C4alkyl)SO x,
CONR8R9,
CO2R10,
R11,
R12,
C3-C6cycloalkyl optionally substituted with one
to three halogen,
C1-C4alkyl,
C1-C4halo-alkyl,
C1-C4alkoxy,
C1-C4haloalkoxy,
NO2 or CN groups,
phenyl optionally substituted with one or more
halogen,
C1-C4alkyl,
C1-C4haloalkyl,
C1-C4alkoxy,
C1-C4haloalkoxy,
NO2 or CN groups, or
pyridyl optionally substituted with one or more
halogen,




-42-

C1-C4alkyl,
C1-C4haloalkyl,
C1-C4alkoxy,
C1-C4haloalkoxy,
NO2 or CN groups; or
C3-C12cycloalkyl optionally substituted with one or
more halogen,
hydroxy,
C1-C4alkoxy,
(C1-C4alkyl)SO x,
CONR8R9,
CO2R10,
R11,
R12,
C3-C6cycloalkyl optionally substituted with one
to three halogen,
C1-C4alkyl,
C1-C4halo-alkyl,
C1-C4alkoxy,
C1-C4haloalkoxy,
NO2 or CN groups,
phenyl optionally substituted with one or more
halogen,
C1-C4alkyl,
C1-C4haloalkyl,
C1-C4alkoxy,
C1-C4haloalkoxy,
NO2 or CN groups, or
pyridyl optionally substituted with one or more
halogen,
C1-C4alkyl,
C1-C4haloalkyl,
C1-C4alkoxy,




-43-

C1-C4haloalkoxy,
NO2 or CN groups;
phenyl optionally substituted with one or more
halogen,
C1-C4alkyl,
C1-C4haloalkyl,
C1-C4alkoxy,
C1-C4haloalkoxy,
NO2 or CN groups, or
pyridyl optionally substituted with one or more
halogen,
C1-C4alkyl,
C1-C4haloalkyl,
C1-C4alkoxy,
C1-C4haloalkoxy,
NO2 or CN groups;
R2 is hydrogen or C1-C4alkyl;
R3, R4, R5, R6,and R7 are each independently hydrogen,
halogen, CN, NO2, C1-C6alkyl, C1-
C6haloalkyl, C1-C6alkoxy, C1-C6haloalkoxy,
or phenyl optionally substituted with one
to three halogen, C1-C4alkyl, C1-
C4haloalkyl, C1-C4alkoxy, C1-C4haloalkoxy,
(C1-C4alkyl)SO x, (C1-C4haloalkyl)SO y, NO2
or CN groups,
with the proviso that at least one of R3, R4, R5, R6 or
R7 must be phenyl optionally substituted with
one to three halogen, C1-C4alkyl, C1-
C4haloalkyl, C1-C4alkoxy, C1-C4haloalkoxy, (C1-
C4alkyl)SO x, (C1-C4haloalkyl)SO x, NO2 or CN
groups;
x and y are each independently 0, 1 or 2;
m is an integer of 0, 1 or 2;




-44-

R8, R9 and R10 are each independently hydrogen or C1-
C4alkyl;
R11 is NR13 R14,

Image

R12 is Image

R13, R14, and R15 are each independently hydrogen or C1-
C4alkyl;
R16 is hydrogen, halogen or C1-C4 alkyl;
X is O, S or NR15;
r is an integer of 0 or 1;
p and q are each independently an integer of 0, 1, 2, or
3 with the proviso that only one of p, q, or r can
be 0 and with the further proviso that the sum of p
+ q + r must be 4, 5 or 6; and
x is an integer of 0, 1 or 2; or
the acid addition salts thereof.

2. The compound according to Claim 1 wherein
R3 and R7 are each independently H or C1-C6alkoxy; and R4
and R6 are each independently H or phenyl optionally
substituted with one or more halogen, C1-C4haloalkoxy, or
C1-C4haloalkyl groups.





-45-

3. The compound according to Claim 2 wherein R
is C1-C6alkyl or C3-C6cycloalkyl optionally substituted
with one to three halogens.

4. The compound according to Claim 2, S-methyl-
2,2-dimethylthiopropionate, 2-(4-methoxy-3-biphenylyl)-
hydrazone; the S-oxide thereof; the S,S-dioxide thereof;
or the acid addition salt thereof.

5. A method for the control of insect or
acarid pests which comprises contacting said pests, their
food supply, habitat or breeding grounds with a
pesticidally effective amount of a compound of formula I

Image

wherein R is hydrogen,
C1-C10alkyl optionally substituted with one or more
halogen,
C3-C6cycloalkyl,
C1-C4alkoxy,
C1-C4haloalkoxy,
(C1-C4-alkyl)SO x,
(C1-C4haloalkyl)SO y,
phenyl optionally substituted with one to
three halogen,
C1-C4alkyl,
C1-C4haloalkyl,




-46-

C1-C4alkoxy,
C1-C4haloalkoxy,
(C1-C4alkyl)SO x,
(C1-C4haloalkyl)SO y,
NO2 or CN groups, or
phenoxy optionally substituted with one to
three halogen,
C1-C4alkyl,
C1-C4haloalkyl,
C1-C4alkoxy,
C1-C4haloalkoxy,
(C1-C4alkyl)SO x,
(C1-C4haloalkyl)SO y,
NO2 or CN groups;
C3-C12cycloalkyl optionally substituted with one or
more halogens,
C1-C6alkyl,
C1-C4haloalkyl,
C1-C4alkoxy,
C1-C4haloalkoxy,
(C1-C4alkyl)SO x,
(C1-C4haloalkyl)SO x,
phenyl optionally substituted with
one to three halogen,
C1-C4alkyl
C1-C4haloalkyl,
C1-C4alkoxy,
C1-C4haloalkoxy,
NO2 or CN groups, or
phenoxy optionally substituted with one to
three halogen,
C1-C4alkyl,
C1-C4haloalkyl,


-47-


C1-C4alkoxy,
C1-C4haloalkoxy,
NO2 or CN groups; or
phenyl optionally substituted with one or more
halogen,
C1-C4alkyl,
C1-C4haloalkyl,
C1-C4alkoxy,
C1-C4haloalkoxy,
NO2 or CN groups;
with the proviso that when R is phenyl, then m must be 1
or 2;
R1 is R12;
C1-C10alkyl optionally substituted with one or more
halogen,
hydroxy,
phenyl optionally substituted with one or more
halogen,
C1-C4alkyl,
C1-C4haloalkyl,
C1-C4alkoxy,
C1-C4haloalkoxy,
NO2 or CN groups,
C1-C4alkoxy,
C1-C4haloalkoxy,
(C1-C4alkyl)SO x,
CONR8R9,
CO2R10,
R11,
R12,
C3-C6cycloalkyl optionally substituted with one
to three halogen,
C1-C4alkyl,


-48-


C1-C4 haloalkyl,
C1-C4alkoxy,
C1-C4haloalkoxy,
NO2 or CN groups,
phenyl optionally substituted with one or more
halogen,
C1-C4alkyl,
C1-C4haloalkyl,
C1-C4alkoxy,
C1-C4haloalkoxy,
NO2 or CN groups, or
pyridyl optionally substituted with one or more
halogen,
C1-C4alkyl,
C1-C4haloalkyl,
C1-C4alkoxy,
C1-C4haloalkoxy,
NO2 or CN groups;
C2-C10alkenyl optionally substituted with one or
more halogen,
hydroxy,
C1-C4alkoxy,
(C1-C4alkyl)SO x,
CONR8R9,
CO2R10,
R11,
R12,
C3-C6cycloalkyl optionally substituted with one
to three halogen,
C1-C4alkyl,
C1-C4halo-alkyl,
C1-C4alkoxy,
C1-C4haloalkoxy,


-49-


NO2 or CN groups,
phenyl optionally substituted with one or more
halogen,
C1-C4alkyl,
C1-C4haloalkyl,
C1-C4alkoxy,
C1-C4haloalkoxy,
NO2 or CN groups, or
pyridyl optionally substituted with one or more
halogen,
C1-C4alkyl,
C1-C4haloalkyl,
C1-C4alkoxy,
C1-C4haloalkoxy,
NO2 or CN groups;
C2-C10alkynyl optionally substituted with one or
more halogen,
hydroxy,
C1-C4alkoxy,
(C1-C4alkyl)SO x,
CONR8R9,
CO2R10,
R11,
R12,
C3-C6cycloalkyl optionally substituted with one
to three halogen,
C1-C4alkyl,
C1-C4halo-alkyl,
C1-C4alkoxy,
C1-C4haloalkoxy,
NO2 or CN groups,
phenyl optionally substituted with one or more
halogen,


-50-


C1-C4alkyl,
C1-C4haloalkyl,
C1-C4alkoxy,
C1-C4haloalkoxy,
NO2 or CN groups, or
pyridyl optionally substituted with one or more
halogen,
C1-C4alkyl,
C1-C4haloalkyl,
C1-C4alkoxy,
C1-C4haloalkoxy,
NO2 or CN groups; or
C3-C12cycloalkyl optionally substituted with one or
more halogen,
hydroxy,
C1-C4alkoxy,
(C1-C4alkyl)SO x,
CONR8R9,
CO2R10,
R11,
R12,
C3-C6cycloalkyl optionally substituted with one
to three halogen,
C1-C4alkyl,
C1-C4halo-alkyl,
C1-C4alkoxy,
C1-C4haloalkoxy,
NO2 or CN groups,
phenyl optionally substituted with one or more
halogen,
C1-C4alkyl,
C1-C4haloalkyl,
C1-C4alkoxy,


-51-


C1-C4haloalkoxy,
NO2 or CN groups, or
pyridyl optionally substituted with one or more
halogen,
C1-C4alkyl,
C1-C4haloalkyl,
C1-C4alkoxy,
C1-C4haloalkoxy,
NO2 or CN groups;
phenyl optionally substituted with one or more
halogen,
C1-C4alkyl,
C1-C4haloalkyl,
C1-C4alkoxy,
C1-C4haloalkoxy,
NO2 or CN groups, or
pyridyl optionally substituted with one or more
halogen,
C1-C4alkyl,
C1-C4haloalkyl,
C1-C4alkoxy,
C1-C4haloalkoxy,
NO2 or CN groups;
R2 is hydrogen or C1-C4alkyl;
R3, R4, R5, R6,and R7 are each independently hydrogen,
halogen, CN, NO2, C1-C6alkyl, C1-
C6haloalkyl, C1-C6alkoxy, C1-C6haloalkoxy,
or phenyl optionally substituted with one
to three halogen, C1-C4alkyl, C1-
C4haloalkyl, C1-C4alkoxy, C1-C4haloalkoxy,
(C1-C4alkyl)SO x, (C1-C4haloalkyl)SO y, NO2
or CN groups,


-52-


with the proviso that at least one of R3, R4, R5, R6 or
R7 must be phenyl optionally substituted with
one to three halogen, C1-C4alkyl, C1-
C4haloalkyl, C1-C4alkoxy, C1-C4haloalkoxy, (C1-
C4alkyl)SO x, (C1-C4haloalkyl)SO x, NO2 or CN
groups;
6. The method according to Claim 5 wherein
said pests are acarid pests.
7. The method according to Claim 5 having a
formula I compound wherein R3 and R7 are each
independently H or C1-C6alkoxy; and R4 and R6 are each
independently H or phenyl optionally substituted with one
or more halogen, C1-C4haloalkoxy, or C1-C4haloalkyl
groups.
8. The method according to Claim 7 having a
formula I compound wherein R is C1-C6alkyl or C3-
C6cycloalkyl optionally substituted with one to three
halogens.
9. The method according to Claim 7 having the
formula I compound, S-methyl-2,2-dimethylthiopropionate,
2-(4-methoxy-3-biphenylyl)-hydrazone; the S-oxide
thereof; the S,S-dioxide thereof and the acid addition
salt thereof.
10. A method for the protection of growing or
harvested plants from attack or infestation by insect or
acarid pests which comprises applying to the foliage of
the plants, or to the soil or water in which they are


-53-


growing, a pesticidally effective amount of a compound of
formula I
Image
wherein
R is hydrogen,
C1-C10alkyl optionally substituted with one or more
halogen,
C3-C6cycloalkyl,
C1-C4alkoxy,
C1-C4haloalkoxy,
(C1-C4-alkyl)SO x,
(C1-C4haloalkyl)SO y,
phenyl optionally substituted with one to
three halogen,
C1-C4alkyl,
C1-C4haloalkyl,
C1-C4alkoxy,
C1-C4haloalkoxy,
(C1-C4alkyl)SO x,
(C1-C4haloalkyl)SO y,
NO2 or CN groups, or
phenoxy optionally substituted with one to
three halogen,
C1-C4alkyl,
C1-C4haloalkyl,
C1-C4alkoxy,




-54-

C1-C4haloalkoxy,
(C1-C4alkyl)SO x,
(C1-C4haloalkyl)SO y,
NO2 or CN groups;
C3-C12cycloalkyl optionally substituted with one or
more halogens,
C1-C6alkyl,
C1-C4haloalkyl,
C1-C4alkoxy,
C1-C4haloalkoxy,
(C1-C4alkyl)SO x,
(C1-C4haloalkyl)SO x,
phenyl optionally substituted with
one to three halogen,
C1-C4alkyl
C1-C4haloalkyl,
C1-C4alkoxy,
C1-C4haloalkoxy,
NO2 or CN groups, or
phenoxy optionally substituted with one to
three halogen,
C1-C4alkyl,
C1-C4haloalkyl,
C1-C4alkoxy,
C1-C4haloalkoxy,
NO2 or CN groups; or
phenyl optionally substituted with one or more
halogen,
C1-C4alkyl,
C1-C4haloalkyl,
C1-C4alkoxy,
C1-C4haloalkoxy,
NO2 or CN groups;




-55-

with the proviso that when R is phenyl, then m must be 1
or 2;
R1 i s R12;
C1-C10alkyl optionally substituted with one or more
halogen,
hydroxy,
phenyl optionally substituted with one or more
halogen,
C1-C4alkyl,
C1-C4haloalkyl,
C1-C4alkoxy,
C1-C4haloalkoxy,
NO2 or CN groups,
C1-C4alkoxy,
C1-C4haloalkoxy,
(C1-C4alkyl)SO x,
CONR8R9,
CO2R10,
R11,
R12,
C3-C6cycloalkyl optionally substituted with one
to three halogen,
C1-C4alkyl,
C1-C4 haloalkyl,
C1-C4alkoxy,
C1-C4haloalkoxy,
NO2 or CN groups,
phenyl optionally substituted with one or more
halogen,
C1-C4alkyl,
C1-C4haloalkyl,
C1-C4alkoxy,
C1-C4haloalkoxy,





-56-

NO2 or CN groups, or
pyridyl optionally substituted with one or more
halogen,
C1-C4alkyl,
C1-C4haloalkyl,
C1-C4alkoxy,
C1-C4haloalkoxy,
NO2 or CN groups;
C2-C10alkenyl optionally substituted with one or
more halogen,
hydroxy,
C1-C4alkoxy,
(C1-C4alkyl)SO x,
CONR8R9,
CO2R10,
R11
R12
C3-C6cycloalkyl optionally substituted with one
to three halogen,
C1-C4alkyl,
C1-C4halo-alkyl,
C1-C4alkoxy,
C1-C4haloalkoxy,
NO2 or CN groups,
phenyl optionally substituted with one or more
halogen,
C1-C4alkyl,
C1-C4haloalkyl,
C1-C4alkoxy,
C1-C4haloalkoxy,
NO2 or CN groups, or
pyridyl optionally substituted with one or more
halogen,




-57-

C1-C4alkyl,
C1-C4haloalkyl,
C1-C4alkoxy,
C1-C4haloalkoxy,
NO2 or CN groups;
C2-C10alkynyl optionally substituted with one or
more halogen,
hydroxy,
C1-C4alkoxy,
(C1-C4alkyl)SO x,
CONR8R9,
CO2R10,
R11,
R12,
C3-C6cycloalkyl optionally substituted with one
to three halogen,
C1-C4alkyl,
C1-C4halo-alkyl,
C1-C4alkoxy,
C1-C4haloalkoxy,
NO2 or CN groups,
phenyl optionally substituted with one or more
halogen,
C1-C4alkyl,
C1-C4haloalkyl,
C1-C4alkoxy,
C1-C4haloalkoxy,
NO2 or CN groups, or
pyridyl optionally substituted with one or more
halogen,
C1-C4alkyl,
C1-C4haloalkyl,
C1-C4alkoxy,





-58-

C1-C4haloalkoxy,
NO2 or CN groups; or
C3-C12cycloalkyl optionally substituted with one or
more halogen,
hydroxy,
C1-C4alkoxy,
(C1-C4alkyl)SO x,
CONR8R9,
CO2R10,
R11,
R12,
C3-C6cycloalkyl optionally substituted with one
to three halogen,
C1-C4alkyl,
C1-C4halo-alkyl,
C1-C4alkoxy,
C1-C4haloalkoxy,
NO2 or CN groups,
phenyl optionally substituted with one or more
halogen,
C1-C4alkyl,
C1-C4haloalkyl,
C1-C4alkoxy,
C1-C4haloalkoxy,
NO2 or CN groups, or
pyridyl optionally substituted with one or more
halogen,
C1-C4alkyl,
C1-C4haloalkyl,
C1-C4alkoxy,
C1-C4haloalkoxy,
NO2 or CN groups;




-59-

phenyl optionally substituted with one or more
halogen,
C1-C4alkyl,
C1-C4haloalkyl,
C1-C4alkoxy,
C1-C4haloalkoxy,
NO2 or CN groups, or
pyridyl optionally substituted with one or more
halogen,
C1-C4alkyl,
C1-C4haloalkyl,
C1-C4alkoxy,
C1-C4haloalkoxy,
NO2 or CN groups;
R2 is hydrogen or C1-C4alkyl;
R3, R4, R5, R6,and R7 are each independently hydrogen,
halogen, CN, NO2, C1-C6alkyl, C1-
C6haloalkyl, C1-C6alkoxy, C1-C6haloalkoxy,
or phenyl optionally substituted with one
to three halogen, C1-C4alkyl, C1-
C4haloalkyl, C1-C4alkoxy, C1-C4haloalkoxy,
(C1-C4alkyl)SO x, (C1-C4haloalkyl)SO y, NO2
or CN groups,
with the proviso that at least one of R3, R4, R5, R6 or
R7 must be phenyl optionally substituted with
one to three halogen, C1-C4alkyl, C1-
C4haloalkyl, C1-C4alkoxy, C1-C4haloalkoxy, (C1-
C4alkyl)SO x, (C1-C4haloalkyl)SO x, NO2 or CN
groups;

11. The method according to claim 10 wherein
said pests are acarid pests.



-60-

12. The method according to Claim 10 wherein
the compound of formula I is applied in a concentration
of about 10 ppm to 10,000 ppm.

13. The method according to Claim 10 wherein
the compound of formula I is applied in a concentration
in about 100 ppm to 5,000 ppm.

14. A composition for controlling insect or
acarid pests which comprises an agriculturally acceptable
carrier and a pesticidally effective amount of a compound
of formula I

Image

wherein
R is hydrogen,
C1-C10alkyl optionally substituted with one or more
halogen,
C3-C6cycloalkyl,
C1-C4alkoxy,
C1-C4haloalkoxy,
(C1-C4-alkyl)SO x,
(C1-C4haloalkyl)SO y,
phenyl optionally substituted with one to
three halogen,
C1-C4alkyl,


-61-

C1-C4haloalkyl,
C1-C4alkoxy,
C1-C4haloalkoxy,
(C1-C4alkyl)SO x,
(C1-C4haloalkyl)SO y,
NO2 or CN groups, or
phenoxy optionally substituted with one to
three halogen,
C1-C4alkyl,
C1-C4haloalkyl,
C1-C4alkoxy,
C1-C4haloalkoxy,
(C1-C4alkyl)SO x,
(C1-C4haloalkyl)SO y,
NO2 or CN groups;
C3-C12cycloalkyl optionally substituted with one or
more halogens,
C1-C6alkyl,
C1-C4haloalkyl,
C1-C4alkoxy,
C1-C4haloalkoxy,
(C1-C4alkyl)SO x,
(C1-C4haloalkyl)SO x,
phenyl optionally substituted with
one to three halogen,
C1-C4alkyl
C1-C4haloalkyl,
C1-C4alkoxy,
C1-C4haloalkoxy,
NO2 or CN groups, or
phenoxy optionally substituted with one to
three halogen,
C1-C4alkyl,


-62-

C1-C4haloalkyl,
C1-C4alkoxy,
C1-C4haloalkoxy,
NO2 or CN groups; or
phenyl optionally substituted with one or more
halogen,
C1-C4alkyl,
C1-C4haloalkyl,
C1-C4alkoxy,
C1-C4haloalkoxy,
NO2 or CN groups;
with the proviso that when R is phenyl, then m must be 1
or 2;
R1 is R12 ;
C1-C10alkyl optionally substituted with one or more
halogen,
hydroxy,
phenyl optionally substituted with one or more
halogen,
C1-C4alkyl,
C1-C4haloalkyl,
C1-C4alkoxy,
C1-C4haloalkoxy,
NO2 or CN groups,
C1-C4alkoxy,
C1-C4haloalkoxy,
(C1-C4alkyl)SO x,
CONR8R9,
CO2R10,
R11,
R12,
C3-C6cycloalkyl optionally substituted with one
to three halogen,


-63-

C1-C4alkyl,
C1-C4 haloalkyl,
C1-C4alkoxy,
C1-C4haloalkoxy,
NO2 or CN groups,
phenyl optionally substituted with one or more
halogen,
C1-C4alkyl,
C1-C4haloalkyl,
C1-C4alkoxy,
C1-C4haloalkoxy,
NO2 or CN groups, or
pyridyl optionally substituted with one or more
halogen,
C1-C4alkyl,
C1-C4haloalkyl,
C1-C4alkoxy,
C1-C4haloalkoxy,
NO2 or CN groups;
C2-C10alkenyl optionally substituted with one or
more halogen,
hydroxy,
C1-C4alkoxy,
(C1-C4alkyl)SO x,
CONR8R9,
CO2R10,
R11,
R12,
C3-C6cycloalkyl optionally substituted with one
to three halogen,
C1-C4alkyl,
C1-C4halo-alkyl,
C1-C4alkoxy,


-64-

C1-C4haloalkoxy,
NO2 or CN groups,
phenyl optionally substituted with one or more
halogen,
C1-C4alkyl,
C1-C4haloalkyl,
C1-C4alkoxy,
C1-C4haloalkoxy,
NO2 or CN groups, or
pyridyl optionally substituted with one or more
halogen,
C1-C4alkyl,
C1-C4haloalkyl,
C1-C4alkoxy,
C1-C4haloalkoxy,
NO2 or CN groups;
C2-C10alkynyl optionally substituted with one or
more halogen,
hydroxy,
C1-C4alkoxy,
(C1-C4alkyl)SO x,
CONR8R9,
CO2R10,
R11,
R12,
C3-C6cycloalkyl optionally substituted with one
to three halogen,
C1-C4alkyl,
C1-C4halo-alkyl,
C1-C4alkoxy,
C1-C4haloalkoxy,
NO2 or CN groups,
phenyl optionally substituted with one or more


-65-

halogen,
C1-C4alkyl,
C1-C4haloalkyl,
C1-C4alkoxy,
C1-C4haloalkoxy,
NO2 or CN groups, or
pyridyl optionally substituted with one or more
halogen,
C1-C4alkyl,
C1-C4haloalkyl,
C1-C4alkoxy,
C1-C4haloalkoxy,
NO2 or CN groups; or
C3-C12cycloalkyl optionally substituted with one or
more halogen,
hydroxy,
C1-C4alkoxy,
(C1-C4alkyl)SO x,
CONR8R9,
CO2R10,
R11,
R12,
C3-C6cycloalkyl optionally substituted with one
to three halogen,
C1-C4alkyl,
C1-C4halo-alkyl,
C1-C4alkoxy,
C1-C4haloalkoxy,
NO2 or CN groups,
phenyl optionally substituted with one or more
halogen,
C1-C4alkyl,
C1-C4haloalkyl,


-66-

C1-C4alkoxy,
C1-C4haloalkoxy,
NO2 or CN groups, or
pyridyl optionally substituted with one or more
halogen,
C1-C4alkyl,
C1-C4haloalkyl,
C1-C4alkoxy,
C1-C4haloalkoxy,
NO2 or CN groups;
phenyl optionally substituted with one or more
halogen,
C1-C4alkyl,
C1-C4haloalkyl,
C1-C4alkoxy,
C1-C4haloalkoxy,
NO2 or CN groups, or
pyridyl optionally substituted with one or more
halogen,
C1-C4alkyl,
C1-C4haloalkyl,
C1-C4alkoxy,
C1-C4haloalkoxy,
NO2 or CN groups;
R2 is hydrogen or C1-C4alkyl;
R3, R4, R5, R6,and R7 are each independently hydrogen,
halogen, CN, NO2, C1-C6alkyl, C1-
C6haloalkyl, C1-C6alkoxy, C1-C6haloalkoxy,
or phenyl optionally substituted with one
to three halogen, C1-C4alkyl, C1-
C4haloalkyl, C1-C4alkoxy, C1-C4haloalkoxy,
(C1-C4alkyl)SO x, (C1-C4haloalkyl)SO y, NO2
or CN groups,


-67-

with the proviso that at least one of R3, R4, R5, R6 or
R7 must be phenyl optionally substituted with
one to three halogen, C1-C4alkyl, C1-
C4haloalkyl, C1-C4alkoxy, C1-C4haloalkoxy, (C1-
C4alkyl)SO x, (C1-C4haloalkyl)SO x, NO2 or CN
groups;

15. The composition according to Claim 14 wherein
R3 and R7 are each independently H or C1-C6alkoxy; and R4
and R6 are each independently H or phenyl optionally
substituted with one or more halogen, C1-C4haloalkoxy, or
C1-C4haloalkyl groups.

16. The composition according to Claim 14 wherein R
is C1-C6alkyl or C3-C6cycloalkyl optionally substituted
with one to three halogens.

17. The composition according to Claim 15 wherein
the compound of formula I is 5-methyl-2,2-
dimethylthiopro-pinnate(4-methoxy-3-biphenylyl)hydrazone;
the S-oxide thereof; the S,S-dioxide thereof; or the acid
addition salt thereof.

18. A process for the preparation of a compound of
formula I

Image

wherein


-68-

R is hydrogen,
C1-C10alkyl optionally substituted with one or more
halogen,
C3-C6cycloalkyl,
C1-C4alkoxy,
C1-C4haloalkoxy,
(C1-C4-alkyl)SO x,
(C1-C4haloalkyl)SO y,
phenyl optionally substituted with one to
three halogen,
C1-C4alkyl,
C1-C4haloalkyl,
C1-C4alkoxy,
C1-C4haloalkoxy,
(C1-C4alkyl)SO x,
(C1-C4haloalkyl)SO y,
NO2 or CN groups, or
phenoxy optionally substituted with one to
three halogen,
C1-C4alkyl,
C1-C4haloalkyl,
C2-C4alkoxy,
C1-C4haloalkoxy,
(C1-C4alkyl)SO x,
(C1-C4haloalkyl)SO y,
NO2 or CN groups;
C3-C12cycloalkyl optionally substituted with one or
more halogens,
C1-C6alkyl,
C1-C4haloalkyl,
C1-C4alkoxy,
C1-C4haloalkoxy,
(C1-C4alkyl)SO x,


-69-

(C1-C4haloalkyl)SO x,
phenyl optionally substituted with
one to three halogen,
C1-C4alkyl
C1-C4haloalkyl,
C1-C4alkoxy,
C1-C4haloalkoxy,
NO2 or CN groups, or
phenoxy optionally substituted with one to
three halogen,
C1-C4alkyl,
C1-C4haloalkyl,
C1-C4alkoxy,
C1-C4haloalkoxy,
NO2 or CN groups; or
phenyl optionally substituted with one or more
halogen,
C1-C4alkyl,
C1-C4haloalkyl,
C1-C4alkoxy,
C1-C4haloalkoxy,
NO2 or CN groups;
with the proviso that when R is phenyl, then m must be 1
or 2;
R1 is R12;
C2-C10alkyl optionally substituted with one or more
halogen,
hydroxy,
phenyl optionally substituted with one or more
halogen,
C1-C4alkyl,
C1-C4haloalkyl,
C1-C4alkoxy,


-70-

C1-C4haloalkoxy,
NO2 or CN groups,
C1-C4alkoxy,
C1-C4haloalkoxy,
(C1-C4alkyl)SO x,
CONR8R9,
CO2R10,
R11,
R12,
C3-C6cycloalkyl optionally substituted with one
to three halogen,
C1-C4alkyl,
C1-C4 haloalkyl,
C1-C4alkoxy,
C1-C4haloalkoxy,
NO2 or CN groups,
phenyl optionally substituted with one or more
halogen,
C1-C4alkyl,
C1-C4haloalkyl,
C1-C4alkoxy,
C1-C4haloalkoxy,
NO2 or CN groups, or
pyridyl optionally substituted with one or more
halogen,
C1-C4alkyl,
C1-C4haloalkyl,
C1-C4alkoxy,
C1-C4haloalkoxy,
NO2 or CN groups;
C2-C10alkenyl optionally substituted with one or
more halogen,
hydroxy,


-71-

C1-C4alkoxy,
(C1-C4alkyl)SO x,
CONR8R9,
CO2R10,
R11,
R12,
C3-C6cycloalkyl optionally substituted with one
to three halogen,
C1-C4alkyl,
C1-C4halo-alkyl,
C1-C4alkoxy,
C1-C4haloalkoxy,
NO2 or CN groups,
phenyl optionally substituted with one or more
halogen,
C1-C4alkyl,
C1-C4haloalkyl,
C1-C4alkoxy,
C1-C4haloalkoxy,
NO2 or CN groups, or
pyridyl optionally substituted with one or more
halogen,
C1-C4alkyl,
C1-C4haloalkyl,
C1-C4alkoxy,
C1-C4haloalkoxy,
NO2 or CN groups;
C2-C10alkynyl optionally substituted with one or
more halogen,
hydroxy,
C1-C4alkoxy,
(C1-C4alkyl)SO x,
CONR8R9,


-72-

CO2R10,
R11,
R12,
C3-C6cycloalkyl optionally substituted with one
to three halogen,
C1-C4alkyl,
C1-C4halo-alkyl,
C1-C4alkoxy,
C1-C4haloalkoxy,
NO2 or CN groups,
phenyl optionally substituted with one or more
halogen,
C1-C4alkyl,
C1-C4haloalkyl,
C1-C4alkoxy,
C1-C4haloalkoxy,
NO2 or CN groups, or
pyridyl optionally substituted with one or more
halogen,
C1-C4alkyl,
C1-C4haloalkyl,
C1-C4alkoxy,
C1-C4haloalkoxy,
NO2 or CN groups; or
C3-C12cycloalkyl optionally substituted with one or
more halogen,
hydroxy,
C1-C4alkoxy,
(C1-C4alkyl)SO x,
CONR8R9,
CO2R10,
R11,
R12,




-73-

C3-C6cycloalkyl optionally substituted with one
to three halogen,
C1-C4alkyl,
Cl-C4halo-alkyl,
C1-C4alkoxy,
C1-C4haloalkoxy,
N02 or CN groups,
phenyl optionally substituted with one or more
halogen,
C1-C4alkyl,
C1-C4haloalkyl,
C1-C4alkoxy,
Cl-C4haloalkoxy,
N02 or CN groups, or
pyridyl optionally substituted with one or more
halogen,
Cl-C4alkyl,
Cl-C4haloalkyl,
C1-C4alkoxy,
C1-C4haloalkoxy,
NO2 or CN groups;
phenyl optionally substituted with one or more
halogen,
C1-C4alkyl,
Cl-C4haloalkyl,
C1-C4alkoxy,
Cl-C4haloalkoxy,
N02 or CN groups, or
pyridyl optionally substituted with one or more
halogen,
C1-C4alkyl,
C1-C4haloalkyl,
C1-C4alkoxy,




-74-

C1-C4haloalkoxy,
N02 or CN groups;
R2 is hydrogen or C1-C4alkyl;
R3, R4, R5, R6,and R7 are each independently hydrogen,
halogen, CN, N02, C1-C6alkyl, C1-
C6haloalkyl, C1-C6alkoxy, C1-C6haloalkoxy,
or phenyl optionally substituted with one
to three halogen, C1-C4alkyl, C1-
C4haloalkyl, C1-C4alkoxy, C1-C4haloalkoxy,
(C1-C4alkyl)SOx, (C1-C4haloalkyl)SOy, N02
or CN groups,
with the proviso that at least one of R3, R4, R5, R6 or
R7 must be phenyl optionally substituted with
one to three halogen, C1-C4alkyl, C1-
C4haloalkyl, C1-C4alkoxy, C1-C4haloalkoxy, (C1-
C4alkyl)SOx, (C1-C4haloalkyl)SOx, N02 or CN
groups;
x and y are each independently 0, 1 or 2;
m is an integer of 0 , 1 or 2 ;
R8,R9 and R10 are each independently hydrogen or C1-
C4alkyl;
R11 is NR13 R14'
Image
R12 is




-75-

R13, R14, and R15 and are each independently hydrogen or
C1-C4alkyl;
R16 is hydrogen, halogen or C1-C4 alkyl;
X is O, S or NR15;
r is an integer of 0 or 1;
p and q are each independently an integer of 0, 1, 2, or
3 with the proviso that only one of p, q, or r can
be 0 and with the further proviso that the sum of p
+ q + r must be 4, 5 or 6; and
x is an integer of 0, 1 or 2;
which process comprises reacting a compound of formula II
Image
wherein Xl is halogen and R, R2 , R3 , R4 , R5 , R6 ; and R7 are
as hereinbefore defined, with at least one molar
equivalent of a mercaptan of formula III
HS-R1
(III)
wherein R1 is as hereinbefore defined,
in the presence of a base, optionally in the presence of a
solvent, to form the compound of formula I wherein m is 0,
optionally reacting the compound of formula I wherein m is 0
with one or more molar equivalents of an oxidizing reagent
to form a compound of formula I wherein m is 1 or 2.

Description

CA 02450118 2003-12-05
WO 02/098841 PCT/USO1/18237
-1-
INSECTICIDAL BIPHENYLTHIOHYDRAZIDES
BACKGROUND OF THE INVENTION
Significant global economic losses in major
agronomic crop production are caused by the damage and
infestation'of insect and acarid pests. Crop reduction
due to said pests, for example, in cotton and peanuts,
can range as high as 39o and 78%, respectively. Pest
infestation can result in lower yields, lower crop
quality, reduced consumption, increased perishability,
increased risk of disease, higher processing cost, higher
transportation cost and increased market prices.
Therefore, new and effective insect and acarid control
agents and crop protection methods are a continuing
global need.
It is thus an object of this invention to provide N-
biphenylthiohydrazone derivatives which are effective
agents for the control of pestiferous insects and
especially, acarina.
It is another object of this invention to provide a
method for the protection of growing and harvested crops
from the harmful and deleterious effects caused by
insects and especially, acarid pests.
It is a further object of this invention to provide
insecticidal and acaricidal compositions for use in the
methods of the invention.
SUMMARY OF THE INVENTION
The present invention provides novel N
biphenylhydrazone compounds of formula I


CA 02450118 2003-12-05
WO 02/098841 PCT/USO1/18237
-2-
R
(O)mRi
R
R' Ra
(I)
wherein
R is hydrogen,
C1-ClOalkyl optionally substituted with one or more
halogen,
C3-C6cycloalkyl,
C1-C4alkoxy,
C1-C4haloalkoxy,
(C1-Cg-alkyl)SOx,
(C1-Cghaloalkyl)SOy,
phenyl optionally substituted with one.to
three halogen,
C1-C4alkyl,
C1-C4haloalkyl,
C1-C4alkoxy,
C1-C4haloalkoxy,
(C1-C4alkyl)SOx,
(C1-C4haloalkyl)SOy,
N02 or CN groups, or
phenoxy optionally substituted with one to
three halogen,
C1-C4alkyl,
C1-C4haloalkyl,
C1-C4alkoxy,
C1-Cghaloalkoxy,
(C1-C4alkyl)SOx,


CA 02450118 2003-12-05
WO 02/098841 PCT/USO1/18237
-3-
(C1-C4haloalkyl)SOy,
N02 or CN groups;
C3-Cl2cycloalkyl optionally substituted with one or
more halogens,
C1-C6alkyl,
C1-C4haloalkyl,
C1-C4alkoxy,
C1-Cghaloalkoxy,
(C1-C4alkyl)SOx,
(C1-C4haloalkyl)SOx,
phenyl optionally substituted with
one to three halogen,
C1-C4alkyl
C1-C4haloalkyl,
C1-C4alkoxy,
C1-C4haloalkoxy,
N02 or CN groups, or
phenoxy optionally substituted with one to
three halogen,
C1-C4alkyl,
C1-C4haloalkyl,
C1-C4alkoxy,
C1-C4haloalkoxy,
N02 or CN groups; or
phenyl optionally substituted with one or more
halogen,
C1-C4alkyl,
C1-C4haloalkyl,
C1-C4alkoxy,
C1-C4haloalkoxy,
N02 or CN groups;
with the proviso that when R is phenyl, then m must be 1
or 2;


CA 02450118 2003-12-05
WO 02/098841 PCT/USO1/18237
-4-
R1 is Rlz.
C1-ClOalkyl optionally substituted with one or more
halogen,
hydroxy,
phenyl optionally substituted with one or more
halogen,
C1-C4alkyl,
C1-C4haloalkyl,
C1-C4alkoxy,
C1-C4haloalkoxy,
N02 or CN groups,
C1-C~alkoxy,
C1-C4haloalkoxy,
(C1-C4alkyl)SOx,
CONRgR9,
C02R10,
R.11,
R12
C3-C6Cycloalkyl optionally substituted with
one to three halogen,
C1-C4alkyl,
C1_C4 haloalkyl,
C1-C4alkoxy,
C1-C4haloalkoxy,
N02 or CN groups,
phenyl optionally substituted. with one or more
halogen,
C1-Cgalkyl,
C1-C4haloalkyl,
C1-C4alkoxy,
C1-Cghaloalkoxy,
N02 or CN groups, or


CA 02450118 2003-12-05
WO 02/098841 PCT/USO1/18237
-5-
pyridyl optionally substituted with one or
more halogen,
C1-C4alkyl,
C1-C4haloalkyl,
C1-C4alkoxy,
C1-C4haloalkoxy,
N02 or CN groups;
C2-ClOalkenyl optionally substituted with one or
more halogen,
hydroxy,
C1-C4alkoxy,
C1-C4alkyl)SOx,
CONRgR9,
C02R10,
R11
R12
C3-C6cycloalkyl optionally substituted with
one to three halogen,
C1-Cgalkyl,
C1-C4halo-alkyl,
C1-C~alkoxy,
C1-C4haloalkoxy,
N02 or CN groups,
phenyl optionally substituted with one or more
halogen,
C1-C4alkyl,
C1-C4haloalkyl,
C1-C4alkoxy,
C1-C4haloalkoxy,
N02 or CN groups, or
pyridyl optionally substituted with one or
more halogen,
C1-C4alkyl,


CA 02450118 2003-12-05
WO 02/098841 PCT/USO1/18237
-6-
C1-C4haloalkyl,


C1-C4alkoxy,


C1-C4haloalkoxy,


N02 or CN groups;


C2-ClOalkynyl optionally substituted with one or


more halogen,


hydroxy,


C1-C4alkoxy,


(C1-C4alkyl)SOx,


CONRgR9,


C02R10,


R11


R12


C3-C6Cycloalkyl optionally substituted with


one to three halogen,


C1-C4alkyl,


C1-C4halo-alkyl,


C1-C4alkoxy,


C1-C4haloalkoxy,


N02 or CN groups,


phenyl optionally substituted with one or more


halogen,


C1-C4alkyl,


C1-C4haloalkyl,


C1-C4alkoxy,


C1-C4haloalkoxy,


N02 or CN groups, or


pyridyl optionally substituted with one or


more halogen,


C1-C4alkyl,


C1-C4haloalkyl,


C1-C4alkoxy,


C1-Cghaloalkoxy,




CA 02450118 2003-12-05
WO 02/098841 PCT/USO1/18237
N02 or CN groups; or


C3-Cl2Cycloalkyl optionally substituted with one or


more halogen,


hydroxy,


C1-C4alkoxy,


(C1-C4alkyl)SOx,


CONRgRg,


C02R10,


R11


R12.


C3-C6Cycloalkyl optionally substituted with


one to three halogen,


C1-C4alkyl,


C1-C,~halo-alkyl,


C1-C4alkoxy,


C1-C~haloalkoxy,


NO2 or CN groups,


phenyl optionally substituted with one or more


halogen,


C1-C4alkyl,


C1-C4haloalkyl,


C1-C,~alkoxy,


C1-C4haloalkoxy,


N02 or CN groups, or


pyridyl optionally substituted with one or


more halogen,


C1-C4alkyl,


C1-C4haloalkyl,


C1-C4alkoxy,


C1-C4haloalkoxy,


N02 or CN groups;


phenyl optionally substituted with one or more


halogen,




CA 02450118 2003-12-05
WO 02/098841 PCT/USO1/18237
_g_
C1-C4alkyl,
C1-C4haloalkyl,
C1-C4alkoxy,
C1-C4haloalkoxy,
N02 or CN groups, or
pyridyl optionally substituted with one or more
halogen,
C1-C4alkyl,
C1-C4haloalkyl,
ZO C1-C4alkoxy,
C1-C4haloalkoxy,
N02 or CN groups;
R2 is hydrogen or C1-C4alkyl;
R3, R4, R5, R6,and R~ are each independently hydrogen,
halogen, CN, N02, C1-C6alkyl, C1-
C6haloalkyl, C1-C6alkoxy, C1-C6haloalkoxy,
or phenyl optionally substituted with one
to three halogen, C1-C4alkyl, C1-
C4haloalkyl, C1-C4alkoxy, C1-C4haloalkoxy,
(C1-C4alkyl)SOx, (C1-C4haloalkyl)SOy, N02
or CN groups,
with the proviso that at least one of R3, R4, R5, R6 or
R~ must be phenyl optionally substituted with
one to three halogen, C1-C4alkyl, C1-
C4haloalkyl, C1-C4alkoxy, C1-C4haloalkoxy, (C1-
C4alkyl)SOX, (C1-C4haloalkyl)SOx, N02 or CN
groups;
x and y are each independently 0, 1 or 2;
m is an integer of 0, 1 or 2;
Rg, Rg and R10 are each independently hydrogen or C1-
C4alkyl;
R11 is NR13 R14'


CA 02450118 2003-12-05
WO 02/098841 PCT/USO1/18237
_g_
/(CH2)p \ ~(CH2)p
\Xr or CH/ \X
\ r
N ' t CH ) ~ ~ CH
2 q ~ 2 ) ~!
~~~Ris ~~~Ris
or ;
N p
R12 is I
Ris
R13, R14, and R15 are each independently hydrogen or C1-
C4alkyl;
X is O, S or NR15%
R16 is hydrogen, halogen or C1-C4 alkyl;
r is an integer of 0 or 1;
p and q are each independently an integer of 0, 1, 2, or
3 with the proviso that only one of p, q, or r can
be 0 and with the further proviso that the sum of p
+ q + r must be 4, 5 or 6; and
x is an integer of 0, 1 or 2; or
the acid addition salts thereof.
Also provided are methods and compositions for the
control of insect and acarid pests and for the protection
of growing and harvested crops from attack and
infestation thereby.
DETAILED DESCRIPTION OF THE INVENTION
A wide variety of insects and acarina cause great
economic loss by damaging or destroying agricultural
crops and horticultural and pharmaceutical plants; by
aiding in the spread and development of bacteria, fungi
and viruses that produce diseases of plants; and by
destroying or lowering the value of stored foods, other


CA 02450118 2003-12-05
WO 02/098841 PCT/USO1/18237
-10-
products and possessions. Insect and acarid attack and
infestation cause some of the farmers' greatest problems
the world over. The need for alternative and effective
insect and acarid control is a global concern.
It has now been found that the N-biphenylthio-
hydrazone compounds of formula I are highly effective
agents for the control of a wide variety of insect and,
particularly, acarid pests. As such, these compounds can
be used to advantage to combat mites of the species
Tetranychus uriticae (Koch). Moreover, compounds of the
present invention have been found to exhibit good
activity against mite species which have developed
resistance to existing commercial acaricides.
Advantageously, compounds of formula I not only
possess acaricidal activity but also exhibit useful
activity against insect pests including Spodoptera
eridania, southern army worms; Diabrotica virgifera,
western corn rootworms; Heliothis virescens, tobacco
budworms; Aphis fabae, bean aphids, and Aphis gossypii,
cotton aphids.
Preferred compounds of the invention are those
compounds of formula I wherein R4 and R6 are each
independently H or phenyl optionally substituted with one
or more halogen, C1-C4haloalkoxy, or C1-C4haloalkyl groups .
More preferred compounds of the invention are those
formula I compounds wherein R is C1-C6alkyl or C3-
C6cycloalkyl optionally substituted with one to three
halogens; R3 and R~ are each independently H or C1-
C6alkoxy; and R4 and R6 are each. independently H or
phenyl optionally substituted with one or more halogen,
C1-C4haloalkoxy or CI-C4haloalkyl groups .
The term " halogen" as used herein denotes chlorine,
fluorine, bromine or iodine. The term " haloalkyl" notes


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-11-
an alkyl group, CnH2n+1, which contains from one halogen
atom to 2n+1 halogen atoms. Similarly, the term
" haloalkoxy" denotes a OCnH2n+1 group which contains
from one to 2n+1 halogen atoms. The halogen atoms may be
the same or different.
The term " acid addition salts" denotes those salts
formed by acids commonly known in the art such as
hydrogen chloride, hydrogen bromide, hydrogen bisulfate,
hemi-hydrogen sulfate and the like.
In the above definition of formula I, when n is 0,
then Y is hydrogen.
Those compounds of formula I wherein m is an integer
of 1 or 2 may be prepared by the oxidation of the
appropriate precursor using standard oxidizing reagents
such as m-chloroperbenzoic acid (mcpba), hydrogen
peroxide and acetic acid, KMnO~, and the like in
accordance with standard known reaction conditions, for
instance, those described in U.S. 5,556,885. Typically
this reaction is conducted at room temperature for
periods of 1-4 days in a suitable solvent such as
methylene chloride. This reaction is shown below flow
diagram I.


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-12-
Flow Diagram I
R4 R3
S-R1
R5 ~ ~ N-N
R
Rz
R6 R
2 eq - mcpba (Ia) 1 eq - mcpba
R~ ~ R, O
Ri S-R
1
R~ O R -N
R
H'~ Rz R R7 R
I z
These compounds of formula I wherein m is 0 may
be prepared by reacting the appropriate hydrazinoyl
halide of formula II wherein X1 is halogen with a
suitable mercaptan of formula III wherein R1 is as
hereinbefore defined in the presence of a base as shown
below in flow diagram II.
Flow Diagram II
R4 R3 R4 R3
Xi SRi
R N-N~ + HSR1 base RS ~ ~ N-N
i R ~ I R
Rz R Rz
Rs R s R~
(II) 7 (III) (Ia)
Alternatively, the appropriate N-biphenylthio
hydra2ide of formula IV may be reacted with the


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-13-
appropriate alkyl halide in the presence of a suitable
base to give the desired N-biphenylthiohydrazone
compounds of formula Ia. The base utilized can be either
organic or inorganic, and typically is sodium or
potassium carbonate. Suitable solvents include those
such as acetone, and typically the reaction is conducted
at reflux temperature thereof for periods of about ~ to 4
hours. This reaction is illustrated below in flow
diagram III.
Flow Diaaram III
R
R,
base
+ R1 X.1
R R
R
R7 RZ
Rz
(IV) (Ia)
Compounds of formula IV may be readily prepared by
the reaction of the corresponding biphenyl hydrazide of
formula V with Lawesson's Reagent. Typically, this
reaction is conducted in a suitable solvent, such as
toluene or benzene, at temperatures ranging from about
50°C to about 80° for a period of about % to 4 hours.
The reaction scheme is shown in flow diagram IV.


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Flow Diagram TV
R4 R3 O R4 R3 S
Lawesson's
R ~ ~ N-N R R ~ ~ N-N R
H reagent 5 I H
Rz
Rz
Rs R~ Rs R~
(V) (IV)
Compounds of formula II may be prepared by reacting
triphenylphosphine and carbon tetrachloride with. the
corresponding biphenyl hydrazide of formula V.
Alternatively, the formula II compound may be prepared by
heating the appropriate formula V biphenyl hydrazide with
phosphorus pentachloride, and treating the reaction
mixture sequentially with carbon tetrachloride and
phenol. These reactions are illustrated below in flow
diagram V.


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-15-
Flow Diagram V
R4 R3 O
R ~ ~ N-N~R
s
Ra
R' 6 R
(V)
P(Ph)3, 1 ) PC15
CCI4 2) CCI4, phenol
r
R R
4 3
Cl
Rs ~ ~ N-N
R R
R 2
s R
(II)
Further, formula II compounds may be prepared using
conventional literature methods such as those described
by Tanaka Kiyoshi, Maeno Seiji, and Mitsuhashi Keiryo in
the Journal of HeterocyCliC Chemistry,22 (1985), pp. 565-
568.
Similarly, compounds of formula V may be readily
prepared by conventional methods such as those described
in WO 93/10083.
Growing or harvested crops may be protected from
attack or infestation by insect or, particularly, acarid
pests by applying to the foliage of the crops, or to the
soil or water in which they are growing, a pesticidally
effective amount of N-biphenylthiohydrazone derivative of
formula I.


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In actual agronomic practice, generally about 10 ppm
to 10,000 ppm, and preferably about 100 to 5,000 ppm, of
the formula I compound is dispersed in a liquid carrier.
When applied to the plants or the soil or water in which
they are growing, these amounts are effective to protect
the plants from insect and acarina attack and
infestation. Applications, such as spray applications,
of compositions of the invention are generally effective
at rates which provide about 0.125 kg/ha to about 250
kg/ha, preferably about 10 kg/ha to 100 kg/ha of active
ingredient. The rate of application may be dependent
upon the prevailing environmental circumstances such as
population density, degree of infestation, stage of plant
growth, soil conditions, weather conditions and the like.
Advantageously, the formula I compounds may be used
in conjunction with, or in. combination with, other
biological and chemical control agents including
insecticides, nematicides, acaricides, molluscicides, and
fungicides. Insecticides may include nuclear
polyhedrosis viruses, pyrroles, arylpyrroles,
halobenzoylureas, pyrethroids, carbamates, phosphates,
and similar conventional insect agents.
Typical formulations suitable for the formula I N-
biphenylthiohydrazone derivatives are sprays, granular
compositions, flowable compositions, wettable powders,
dusts, microemulsions, emulsifiable concentrates or any
conventional agricultural composition. All compositions
which lend themselves to soil, water and foliage
application and provide effective plant protection are
suitable. Compositions of the invention include the I N-
biphenylthiohydrazone derivative of formula I admixed
with an agriculturally acceptable solid or liquid
carrier.


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Where compositions of the invention are to be
employed in combination treatments with other biological
or chemical agents, the composition may be applied as an
admixture of the components or may be applied
sequentially to the target pest and/or crop. While not
required, the combination composition comprising a
formula I compound and a co-pesticide may also comprise
other components, for example, fertilizers, inert
formulation aides such as surfactants, emulsifiers,
defoamers, dyes, extenders and the like.
In order to aid in the understanding of the
invention, specific examples thereof are set forth below.
The invention described and claimed herein is not to be
limited in scope by these merely illustrative examples.
Indeed, various modifications of the invention in
addition to those exemplified and described herein will
become apparent to those skilled in the art from the
following examples and the foregoing description. Such
modifications are also intended to~fall within the scope
of the appended claims.
The terms 1H, 13C, 19g NMR designate proton, carbon
and fluorine nuclear magnetic resonance spectroscopy,
respectively. IR designates infrared spectroscopy.


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EXAMPLE Z
Preparation of ( 4 -methoxy~- 3 -bipheny15r1 ) hydraz ine
hydrochloride
NaNO~
OCH3 ~ ~ ~ ~ ~ OCH3
SnCl2
NH3
NHNHz ~ HC 1
A suspension of 5-phenyl-o-anisidine (10 g, 50.0
mmol)in water and hydrochloric acid (concentrated, 180
ml) is cooled to 0° C, treated dropwise with a 0° C
solution of sodium nitrite (3.45 g, 50.0 mmol) in water,
stirred. for one hour, treated with a -20° C solution of
tin chloride (45.2 g,238 mmol) in concentrated
hydrochloric acid (80 ml), stirred for one hour at 0° C
and filtered. The filter cake is mixed with hot water
and filtered. The filtrate is cooled and filtered to
obtain the title product, as beige crystals, in 64.3%
yield, mp 184-186° C.
EXAMPLE 2
Preparation of 2,2-dimethy~lpropionate, 2-(4-methoxy-3-
biphenwlyl)hydrazide
pCH Et3N ~ ~ ~ ~ OCH
3 ~ ~ 3
~Cl O
NHNH2 ~ HC 1 NHNH
A suspension of (4-methoxy-3-biphenylyl)hydrazine,
hydrochloride(25.07 g, 100 mmol) in methylene chloride is


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-19-
treated with triethylamine (21.25 g, 210 mmol). A
solution of trimethylacetyl chloride (12.06 g,100 mmol)
in methylene chloride is added dropwise to the reaction
mixture and stirred for four hours at room temperature.
After pouring the reaction mixture into water, the
mixture is extracted with ethyl acetate, and the extract
washed with 15% hydrochloric acid, water, and a saturated
aqueous solution of sodium chloride, dried over sodium
sulfate and filtered. The filtrate is concentrated in
vacuo and the resultant pink residue recrystallized from
hexane to afford the title product, as a white solid
(21.7 g), in 75.5% yield, mp 153-156° C. Identity is
confirmed by 1HNMR, 13CNMR, and IR.
EXAMPLE 3
Preparation of 1-chloro-2,2-dimethylpropionaldehtrde, 2-
(4-methoxy-3-biQhenylyl)hydrazone
OCH p(ph)3 ~ ~ ~ ~ OCH
CC14 ~ 3
O Cl
NHNH --~~ NHN
. A solution of 2,2-dimethylpropionate, 2-(4-methoxy-
3-biphenylyl)hydrazide(5.97 g, 20 mmol) and
triphenylphosphine (15.7 g,60 mmol) in acetonitrile is
treated with carbon tetrachloride (10.15 g, 66 mmol),
stirred for one hour and concentrated in vacuo to afford
an orange residue. The residue is dissolved in ether,
cooled to -32° C and filtered. The filtrate is
concentrated in vacuo to afford the title product, as a


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-20-
white solid (3.53 g), in 55.7% yield. Identity is
confirmed by 1HNMR and 13CNMR.
EXAMPLE 4
Preparation of 1-chloro-2,2-dimethylpropionaldehyde, 2-
(4-methox~r-3-biphenylwl)hydrazone
PC15/CC14
OCH3 phenol ~ ~ ~ ~ OCH3 Cl
O
N-N-
NH-NH \~ H
A suspension of 2,2-dimethylpropionate, 2-(4-
methoxy-3-biphenylyl)hydrazide (7.46 g,25 mmol) and
phosphorus pentaChloride (5.47 g,26 mmol) in carbon
tetrachloride is refluxed for 15 minutes. The reaction
mixture is cooled to 0° C, treated with phenol (7.9 g,84
mmol), warmed to room temperature and concentrated in
vacuo give a brown oil. The oil is reCrystallized from
hexane to afford the title product, as a beige solid
(4.66 g), in 58.9% yield. Identity is confirmed by 1HNMR,
13CNMR, and IR.
EXAMPLE 5
Preparation of S-methyl 2,2-dimethvlthiopropionate, (4-
methoxy-3-biphenylyl)hSrdrazone
OCH NaSMe ~ ~ ~ ~ OCH
3 3
S'CH3
Cl NHN
NH 'N
A solution of sodium thiomethoxide (1.12 g,16
mmol)in methylene chloride (150 ml) is treated with 1-


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-21-
chloro-2,2-dimethylpropionaldehyde, 2-(4-methoxy-3-
biphenylyl)hydrazone (4.6 g, 14.5 mmol)and stirred for
several hours at room temperature. The reaction mixture
is poured into water extracted with methylene chloride.
The extract is washed with dilute aqueous sodium
hydroxide solution, water, and aqueous saturated sodium
chloride, then dried over magnesium sulfate and filtered.
After concentration of the filtrate in vacuo, the
resultant yellow residue is dissolved in hexane and
filtered. The filtrate is concentrated in vacuo to
afford the title product; as a yellow oil (3.7 g), in
77.70 yield. Identity is confirmed by 1HNMR, 13CNMR, and
IR.
EXAMPLE 6
Preparation of 2,2-dimethylthiopropionate, 2-(5-fluoro-4-
methoxy-3-biphenylyl)hydrazide
F F
Lawesson's
OCH3 reagent CCHa
C ~ S
NHNH ~ NHNH
Lawesson's reagent (4.14 8,103 mmol) is added to a
solution of 2,2-dimethylthiopropionate, 2-(5-fluoro-4-
methoxy-3-biphenylyl)hydrazide (6.33 g,20 mmol) in
toluene and the reaction mixture heated to 80 °C. After
approximately three hours at 80° C, the reaction mixture
is cooled to room temperature and filtered. The filtrate
is concentrated in vacuo to give an oily residue which
was purified by silica gel flash chromatography. The
title product is obtained, as a white solid (4.1 g)in
61.70 yield, mp 96-97° C. Identity is confirmed by 1HNMR,
13CNMR, and IR.


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PAGE INTENTIONALLY LEFT BLANK


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EXAMPLE 7
Preparation of S-methyl 2,2-dimethylthiopropionate, 2-
(5-fluoro-4-methoxy-3-biphenylyl)hydrazone
F F
pCH3 K CO ~ ~ ~ ~ pCH3
g z s ~ S-CH3
NHN
NHNH
Methyl iodide (0.78 g, 5.5 mmol) is added slowly to
a suspension of 2,2-dimethylthiopropionate-,2-(5-fluoro-
4-methoxy-3-biphenylyl) hydra~ide(1.6 g, 5 mmol) and
potassium carbonate (0.76 g, 5.5 mmol) in acetone at
reflux. After three hours, the reaction mixture is
cooled, poured into water, and extracted with ethyl
acetate. The extract is washed with water and saturated
aqueous sodium chloride solution, dried over sodium
sulfate and filtered. The filtrate is concentrated in
vacuo to afford the title product as a yellow oil,(1.7
g)in 98.3% yield. Identity is confirmed by 1HNMR, 13CNMR,
and IR. .
EXAMPLES 8-14
Preparation of the N-Biphenylthiohydrazone Compounds
Using essentially the same procedures described in
Examples 1-7, and substituting the appropriate reagents,
the compounds specified in the following Table I are
prepared. The compounds obtained are oils, except where
indicated, and their identity is confirmed by 1HNMR,
13CNMR, IR, mass spectral and elemental analyses.


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WO 02/098841 PCT/USO1/18237
-24-
N N ~0


r-Ir~ r1 l0 Lf7111r)


U -,-1i 1 1 -~I


O O O ~ ~ ~ O



M M ~0


01 L~ 00


N o~ L~ M M iS1 L~01 d1


.~
v



M ~ U M M M M M


M M M M M M
' U U U


Q ~ M ~ U
''


x


U U U U U U U


U~ P-~'



M M M ~ M
U U


H i ~ U U U ~j U



z- x


r



H
x



x x x x


~ U


U



!~


x


U M


x x x x x I ~


M


w


U



x x u,~ x o x



x x x x x x x


x


x x x x x x x


x


~ ~


w o, ~ ~ ~ , ~
-1 -1


Z




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EXAMPLE 15
Preparation of S-methyl 2,2-dimethylthiopropionate, 2-__
(4-methoxy-3-biphenylyl)hydrazone, S,S-dioxide
OCH3 mcpba ~ ~ ~ ~ pCH3
CH3
S CH3 ~NH-N
NHN
A solution of S-methyl 2,2-dimethylthiopropionate,
(4-methoxy-3-biphenylyl)hydrazone(1.2 g,3.9 mmol) in
methylene chloride is treated dropwise with m-chloroper-
benzoic acid (1.3 g, 8.1 mmol) and stirred for 3 days at
room temperature. The reaction mixture is then poured
into water extracted with methylene chloride and the
extract washed with an aqueous solution of potassium
carbonate (10%), water, a saturated aqueous solution of
sodium chloride, and then dried over magnesium sulfate
and filtered. The filtrate is concentrated in vacuo to
afford an oil which is purified via flash chromatography
on silica gel. The title product is obtained, as a white
solid (0.5 g) in 35.5% yield, mp 134-136° C. Identity is
confirmed by 1HNMR, 13CNMR, IR and C, H, and N elemental
analyses.


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Examples 16-22
Preparation of N-Biphenylthiohydrazone, S,S-dioxide
Compounds
Using essentially the same procedure described in
Example 15, and substituting the appropriate reagents,
the following compounds specified in Table II are
prepared. The compounds obtained are oils, except where
indicated, and their identity is confirmed by 1HNMR,
13CNMR, IR, mass spectral and elemental analyses.


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-27-
d~,~co 0
O '~


N N di


~ r-Ic-Ic-I~
r1


~


p ~ N 01Lf1Lfl
~


' ~ N r1d~ ~
~'' Lfl


r1r1~-I~
r1


N M C~ O L~ di
N oho M
O CO f''1 l4 ~ L~ Lf7
n7 M lfl M r1
M M M M M M


U U _


M x x x x x


U U U U U


U .,


U U U U U U U



O-cn-O


'~


,~ x x x x x x x


U U U U L~ U U


H


H


N


r1 ~ x
r


~ ~ ~ ~
a


d U x
c x


U


U U M ~


w



x x x ~ x w x



U



x x x x ~ x x



U


x


U


x x x x x


U


U



x x x x ; x x


x


l0 L~ CO 01O c-IN


-~ r1 r1N N N


W




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EXAMPLE 23
Preparation of S-methyl 2,2-dimethylthioprot~ionate, 2-
[4'-(trifluoromethyl)-2-biphenylyllhydrazone, S-oxide
F3C ~ ~ ~ ~ mcpba ' F3C ~ ~ ~ ~ O
~,~ SCH3 ~~i SCH3
N~~ N
A solution of S-methyl 2,2-dimethylthiopropionate
2- [4' (trifluoromethyl) -2-biphenylyl] hydrazone (1 .2 g, 3 . 9
mmol) in methylene chloride is treated with 3-
chloroperbenzoic acid (1.3 g, 8.1 mole) and stirred
overnight at room temperature. After adding methylene
chloride, the reaction mixture is then washed with
potassium carbonate (10%), water, and a saturated aqueous
solution of sodium chloride. After drying over magnesium
sulfate and filtering, the filtrate is concentrated in
vacuo to afford an oil which is purified via silica gel
flash chromatography. The title product is obtained, as
an orange solid (0.09 g), in 15% yield, mp 139-140° C.
Identity is confirmed by 1HNMR, 13CNMR, IR and C, H, and N
elemental analyses.
EXAMPLE 24
Insecticidal Evaluation of N-Biphenylthiohydrazone, S-
methyl esters, and S-oxide, and S,S-dioxide Compounds
In these evaluations, test solutions are prepared by
dissolving the test compound in a 35% acetone in water
mixture to give a concentration of 10,000 ppm (4,000 ppm
for cotton aphids). Subsequent dilutions are made with
water as needed.


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Sp~ra eridania, 3rd instar larvae, southern arxnyworm
SAW
A Sieva limabean leaf expanded to 7-8 cm in
length is dipped in the test solution with agitation for
3 seconds and allowed to dry in a hood. The leaf is then
placed in a 100 x 10 mm petri dish containing a damp
filter paper on the bottom and ten 3rd instar
caterpillars. At 5 days, observations are made of
mortality, reduced feeding, or any interference with
normal molting.
Diabrotic viraifera ver~ifera Leconte, 3rd instar western
corn rootworm (TnTCR)
One cc of fine talc is placed in a 30 ml wide-
mouth screw-top glass jar. One mL of the appropriate
acetone test solution is pipetted onto the talc so as to
provide 1.25 mg of active ingredient per jar. The jars
are set under a gentle air flow until the acetone is
evaporated. The dried talc is loosened, 1 cc of millet
seed is added to serve as food for the insects and 25 ml
of moist soil is added to each jar. The jar is capped
and the contents thoroughly mixed on a Vortex Mixer.
Following this, ten 3rd instar root-worms are added to
each jar and the jars are loosely capped to allow air
exchange for the larvae. The treatments are held for 5
days when mortality counts are made. Missing larvae are
presumed dead, since they decompose rapidly and can not
be found. The concentrations used in this test
correspond approximately to 50 kg/ha.


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Heliothis virenscens, 3rd instar tobacco budworm (TBW~
Cotton cotyledons are dipped in the test
solution and allowed to dry in. a hood. When dry, each is
cut into quarters and ten sections are placed indi-
vidually in 30 mL plastic medicine cups containing a 5 to
7 mm long piece of damp dental wick. One 3rd instar
caterpillar is added to each cup and a cardboard lid
placed on the cup. Treatments are maintained for 3 days
before mortality counts and estimates of reduction in
feeding damage are made.
Tetransrchus urticae(OP-resistant strain), 2-spotted
spider mite (TSM)
Sieva limabean plants with primary leaves
expanded to 7-8 cm are selected and cut back to one plant
per pot. A small piece is cut back to one plant per pot.
A small piece is cut from an infested leaf taken from the
main colony and placed on each leaf of the test plants.
This is done about 2 hours before treatment to allow the
mites to move over to the test plant to lay eggs. The
size of the cut, infested leaf is varied to obtain about
100 mites per leaf. At the time of test treatment, the
piece of leaf used to transfer the mites is removed and
discarded. The newly mite-infested plants are dipped in
the test solution for 3 seconds with agitiation and set
in the hood to dry. After 2 days, one leaf is removed
and mortality counts are made. After 5 days, another
leaf is removed and observations are made of mortality of
the eggs and/or newly emerged nymphs.
Aphis fabae mixed instar, bean aphid (BA)
Pots containing single nasturtium plants
(Tropaeolum sp.) about 5 cm tall are infested with about


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100-200 aphids one day before the test. Each pot is
sprayed with the test formulation for 2 revolutions of a
4 rpm turntable in a hood, using a #154 DeVilbiss
atomizer. The spray tip is held about 15 cm from the
plant and the spray directed so as to give complete
coverage of the plants and the aphids. The sprayed pots
are set on their sides on white enamel trays and held for
2 days, following which mortality estimates are made.
Aphis qossynii (cotton aphid)
A heavily infested leaf is placed on top of a
cotton plant which had been grown to the cotyledon stage.
The aphids are allowed to transfer from the leaf section
to the host plant overnight. The resultant infested
leaves of the intact plant are dipped into the test
solution and then allowed to dry. Aphid mortality counts
are made after the test plants have been maintained under
GRO-LUXE lights (24 hour photoperiod) at 27-28° C for 5
days. Phytotoxicity to the cotton plant is also recorded
at this time.
The tests are rated according to the scale shown
below and the data obtained are shown in Table III. When
more than one test is conducted, the results are
averaged.
RATING SCALE
Rate % Mortality Rate % Mortality
0 no effect 5 56-65
1 10-25 6 66-75
2 26-35 7 76-85
3 36-45 8 86-99
4 46-55 9 100


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not tested
Table III
Insecticidal Evaluation Of N-Biphenylthiohydrazone, S-
oxide, and S-dioxide Compounds
S,



Mortality



SAW WCR TSM TBW BA CA


Compound 300 (50 (300/50 (300 (10 (100


( Ex . No ppm) perm) ppm) 7~pm) Ppm) ppm)
. )


5 0 0 9/9 0 0 0


7 0 9 9/9 0 0 8


8 7 9 9/8 0 7 8


9 - 0 9/8 0 0 5


9 0 0/0 - 0 0


11 0 9 8/- 4 7 8


12 2 0 9/0 0 0 8


13 7 0 9/- - - -


14 0 0 0/0 - - -


0 0 9/9 2 0 7


16 0 0 9/- 0 0 0


17 0 0 8/8 0 8 8


18 6 0 9/- 0 0 7


19 0 0 9/9 2 0 7


0 0 0/0 - - 0


23 2 0 0/0 - - 0




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EXAMPLE 25
Cotton Aphid (Aphis gossypii)
A heavily infested leaf is placed on top of a cotton
plant which had been grown to the cotyledon stage. The
aphids are allowed to transfer from the leaf section to
the host plant overnight. The resultant infested leaves
of the intact plant are dipped into the test solution and
then allowed to dry. Aphid mortality counts are made
after the test plants have been maintained under GRO-LUX
lights (24 hour photoperiod) at 27-28°C for 5 days.
Phytotoxicity to the cotton plant is also recorded at
this time,
Two-spotted Spider Mite (Tetranychus urticae - OP-
resistant strain)
Sieva limabean plants with primary leaves expanded to 7-8
cm are selected and out back to one plant per pot. A
small piece is cut from an infested leaf taken from the
main colony and placed on each leaf of the test plants.
This is done about 2 hours before treatment to allow the
mites to move over to the test plant to lay eggs. The
size of the cut, infested leaf is varied to obtain about
100 mites per Leaf. At the time of test treatment, the
piece of leaf used to transfer the mites is removed and
discarded. The newly mite-infested plants are dipped in
the test solution for 3 seconds with agitation and set in
the hood to dry. After 2 days, one leaf is removed and
mortality counts are made. After 5 days, another leaf is


CA 02450118 2003-12-05
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-34-
removed and observations are made of mortality of the
eggs and/or newly emerged nymphs.
Compounds are rated according to the following scale:
Rate % Mortalitv~


0 No effect


1 10-25


2 26-35


3 36-45


4 46-55


5 56-65


6 66-75


7 86-99


8 100




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Test Compounds
Br H SCH3
CH
NON 3 Compound A Art
\ H3C CH3
H SCH3 Compound B Invention
N\ / CH3
N
H3C CH3
H SCH3
CH
Br / ~ NON 3 Compound C Art
\ H3C CH3
H SCH3
\ / NON CH3 Compound D Invention
HsC CHs


CA 02450118 2003-12-05
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-36-
Table A
Comparative Insecticidal Evaluation of Test Compounds
Dose
Compound (ppm) CA TSM
A
300 0 0
[ART ]
300 9 8
B
100 8 8
[ INVENTI ON]
4 3
C
300 0 0
[ART ]
300 8 9
D
100 8 8
[ INVENTION]
10 - 3

Representative Drawing