Note: Descriptions are shown in the official language in which they were submitted.
CA 02296121 2000-O1-28
- 1 -
PYRAZOLE COMPOUNDS, AND THEIR PRODUCTION AND USE
This application has been divided out of Canadian
Patent Application Serial No. 2,005,786 filed December 18,
1989.
The present invention relates to pyrazole compounds,
their production and use.
Organophosphorus insecticides, organochlorinated
insecticides, carbamate insecticides, etc. have made a great
contribution to the prevention and extermination of pests.
Some of these insecticides, however, are highly toxic.
Further, their residual effect causes sometimes unfavorable
abnormality in the ecosystem of living things. Furthermore,
resistance to those insecticides has been noticed in house
flies, planthoppers, leafhoppers, rice borers, etc.
As a pesticide having a juvenile hormone-like
activity, there is known "methoprene" (U. S. patent
3,904,662). Further, Canadian patent 1,231,945 and EP-A1-
0287959 disclose certain compounds having a juvenile
hormone-like activity. However, the pesticidal acvitity of
those compounds is not always satisfactory.
As a result of extensive study, it has now
been found that some pyrazole compounds exert a noticeable
juvenile hormone-like activity and produce a remarkable
pesticidal effect against pests belonging to Diptera,
Hemiptera, Coleoptera, Lepidoptera, Orthoptera, Blattaria,
Thysanoptera, Siphonaptera, Isoptera, etc. in agricultural
fields, forest lands, granaries, stored products, sanitary
facilities, etc. at low concentrations. This invention is
based on the above finding.
The pyrazole compounds of the invention are
CA 02296121 2000-O1-28
- 2 -
represented by the formula:
N
R1-A-CH .--~-CH -~-N ' C 4 )
~2 ~3 ~ R m (I)
R R
wherein R1 is a C1-CB alkyl group, a CZ-C8 alkenyl group or a
C3-CB alkynyl group, these groups being unsubstituted or
substituted with halogen, hydroxy and/or C1-C6 alkoxy; R2and R'
are the same or different and each represent a hydrogen atom,
a halogen atom or a C1-C3alkyl group, R4is a hydrogen atom, a
halogen atom, a C1-C4 alkyl group or a halo (C1-C4) alkyl group; A
is either one of the formulae:
-X-CH2- ~ H-CH2-CH= ~ - or -X-CHz- ~ H-CHZ-CHz-CH-
Rs R~ Re R9
wherein R6, R', R8 and R9 are the same or different and each
represent a hydrogen atom, a halogen atom or a Cl-C3 alkyl
group; X is an oxygen atom, a sulfur atom, a methylene group,
a carbonyl group, a sulfoxide group, a sulfonyl group or a
single bond; p is an integer of 0 to 2; and m is an integer of
1 to 3.
The pyrazole compound (I) can be produced, for instance,
by reacting a compound of the formula:
R1-A-CH --~- Cfi -~-~-B
R2 R3
CA 02296121 2000-O1-28
- 3 -
wherein R1, Rz, R', A and p are each as defined above and B is
a halogen atom, a mesyloxy group or a tosyloxy group with a
compound of the formula:
H~ (R4) (III)
m
wherein R°and m are each as defined above in the presence of
an acid-eliminating agent.
The above reaction may be carried out in the presence or
absence of an inert solvent, of which preferred examples are
dimethylformamide, dimethylsulfoxide, tetrahydrofuran,
toluene, dimethoxyethane, dimethylacetamide, etc. As the
acid-eliminating agent, there may be employed an alkali metal,
an alkali metal hydride, an alkali metal amide, an alkali
metal hydroxide, an alkali metal carbonate, an organic base
(e.g. 4-dimethylaminopyridine), etc. For acceleration of the
reaction, a phase transfer catalyst, e.g.
benzyltriethylammonium chloride, tetra-n-butylammonium bromide
or tris(3,6-dioxaheptyl)amine may be present in the reaction.
In this instance, water can be used as the reaction medium.
The reaction is normally achieved at a temperature of
about -30°C to 200°C, preferably of about 0°C to
110°C, for a
period of about 0.5 to 30 hours. The molar ratio of the
compounds (II) and (III) is usually about 1 . 0.1 - 10
moles, preferably about 1 . 0.8 - 1.2 moles.
CA 02296121 2000-O1-28
- 4 -
Upon completion of the reaction, the reaction mixture is
subjected to ordinary post treatment, for example, extraction
with an organic solvent and concentration. When desired,
purification by chromatography, distillation, re-
crystallization or the like may be carried out.
The pyrazole compounds (I) of the invention include
optical isomers and geometrical isomers with respect to R2, R3,
R6, R', Re and/or R9 _ All of these isomers are included within
the scope of the invention.
Representative examples of the pyrazole compounds (I)
obtainable by the above procedure and as prepared in the
parent application are shown in Table 1.
CA 02296121 2000-O1-28
u1
x
' N
rx x x x x U x
1
M
I 1 1 I
x ~'~1 N ( 1 N N N
U -rx x N N x x x
U U U U U U
N 1 I N N N
H U Od U U-U U-W U U U
I 1 I 1 1 1 1
I
I
I t I 1 I
d' N N N N N
Ix 1 x x x x x
N U U U U U
x I 1 I I I
U O O O O O
O / i / ~ i
Z
O O O O O
I 1 I I 1
x
U- rx
x N
U - P4
I 1
.-i r.~ 1 N
1 N
rl x N
N rx U x
I i / U / 1
x x ~ I ~ I IN ~ I U
L~ U - U w 1
I U U
1 IIt
x ~-1 x
U U U
CA 02296121 2000-O1-28
M
w x
x x U x U x x x x
b -- 1 I
>~
.,.,
>~
0
U
1
N
U
1 I 1 I
x M I N N N N
U-x N x x x x
x U U U U
t' x IN IN IN IN (N IN IN
x N x N x x x x x x x
U-P4 U-U U U U U U U U
I I I 1 I 1 1 1 I
t
I I
x
U
II
x
a
1
1 1 N I ( ( 1
N N x N 1 t''~ N N N
x x U x x x x x x
U U I M U V-U U U U
I 1 w x I 1 1 I 1
O O U-U O O O O O
1
i i N i i ~ i i
w [ w I x w I w t w I w I ' I
U
O O v O O O O O
1 1 I I I 1 1 1
i
N
x
I ~ I x x'~' ~ I ~ I ~ [ ~ I ~ I
U- U
I
r~
x
U
CA 02296121 2000-O1-28
N
N r1
x x x a v v v
Tj'-' I 1 I
v ~ ~ ~ i
a
a
~i
s~
0
U
1 I I I I
x M N 1 ( ~"1 N N N N
v-x x N x x x x x x
U U U-U U U U U
N I c''7 N N N N N
x N x x x x x x x x
U- P4 U U-U U V U U U
1 1 1 1 I 1 1 1
1
n
I
1 I 1 1 I 1
1 ~ N N N N N N
U-U U U U U U U
I I I I I I 1
O O O O O O O
/ I i I / I / i
\ \ \ \ \ I ~ I \
O O O O O O O
1 1 t 1 I I 1
\ ~ \ \ ~ \
CA 02296121 2000-O1-28
~r
x x x x x x
b
v
.r.,
0
U
I 1 1
x M (N N N N
v-x x x x x
U U U U
1 1 1 1 1
N N N N N
x N x x x x x
V -c~ U U U U U
I 1 1 I 1 1
I
I
I I 1 I t
N N ('J N N
x x x x x
U U U U U
I 1 1 1 I
O O rl O rl O r-1 O
U U U
O O O O O
1 I 1 I I
\ \ I
i ~ \
w x w
CA 02296121 2000-O1-28
x x x x x
b
>~
.,.,
a
0
U
I 1 I t
U n: x x x N x
U U U ' U
N N N N N
U-~: U U U U U
I 1 1 I I I
I
a~
I
1 I 1 1 1
N N N N CJ
x x x x x
U U U U U
I 1 I 1 1
O O O O O
U
/ ~ / ~ / ~ /
\ \ \ \
O O O O O
1 I 1 1 1
G4 G4
/ ~ / ~ / ~ /
\ \
W O
W W W W x
CA 02296121 2000-O1-28
x x x x x x
ro
v
s~
.,
a
0
U
I I 1 1 1
U ~ U U U U U
1 I I i I
N N N N N
x N x x x x x
U- G~ U U U U U
1 I I 1 I i
I
0
I
I 1 I 1 1
N N N N N
x x x x x
U U U U U
1 1 1 1 1
O O O O O
1
O O O O O
I 1 1 1 I
~ I \ I
\ z ~ U
U U N x M U
z z o x U
CA 02296121 2000-O1-28
x x w x x x
b
a~
a
a
.r.,
s~
0
U
I 1
x ch N N
U-oc x x
U U
1 I 1 1 1
N N N N N
x N x x x x x
U-tx U U U U U
1 i t I 1 1
I
r
t I 1 I I
N N N N N
x x x x x
U U U U U
1 I 1 I 1
O O O O O
O O O O O
t 1 I I 1
'-r / 1 W
~ i / i
W W ~., G4 W
CA 02296121 2000-O1-28
x x x x x
b x
a~
.'.,
0
U
1 I I I 1
N N N N N
V -x x x x x x
U U V U V
N N N N N
x N x x x x x
U- P4 V U U U U
1 I 1 1 I 1
I
N
r-1
I
I 1 I I
N N N N N
x x x x x
U U U V U
1 I i 1 t
O O O O O
i ~ / ( i ~ / ( i
\ \ \ \ \
O O O O O
1 1 1 I I
/
\ ~ U c~
ri r-~ r-i M x
fsa U U U W U
CA 02296121 2000-O1-28
x x x x x x
b x
a
s~
.r.,
>~
0
U
1 1 1 1 1 I
x ~T1 N N N N N N
U ~ U U U U U U
1 I 1 I 1 I
N N N N N N
U P4 U U U U U U
1 I I 1 I I I I
M
r-~
1
1 1 I 1 1 1
N N N N N N
U U U U U U
O O O O O O
i ~ i ~ i ~ i
\ w \ ~ \
O O O O O O
i
\I
x o
i
U x O
x O ~' ~ ~ ~ ~ ~ ~ ' I
x II U v1
N U N III ri
w M x U x
a x U x U
CA 02296121 2000-O1-28
d. I x x x x x
b ~
a~
s~
.r.,
s~
0
U
1 I I I
U G4 x x x x
U U U U 1
1 I I 1
N N N N N
U Lt; U U U U U
I 1 1 1 I 1
1
~i
1
I I
N N I 1 1
x x N N N
v U x x x
1 I U U U
O O ~ O O
\ \
O O O O O
1 1 1 1 1
n
Q; ~ x
~r1 ~''~ I
V \
U ~ Gv Gv f=., fsr
CA 02296121 2000-O1-28
E
x x x x x. x
~sx
a~
s~
0
U
1 1 1
x ~ 1 N N N
U- x N x x x
x U U U
U 1 1 1 I 1
I ~''1 N N N N N
x N x x x x x x x
U- P: U - U U U U U U
I 1 1 I I I I
I
1
I
N
I 1 x I
I c~ N V N
N I r, x x I x
x x x U U o U
U U- U 1 1 1
I 1 O O ~ O
O O
~ I ~ ~ i ~
\ \ \ \ N \
x
O O ~ U =O U O
1 1 1 1 1 1
\ I
c>r \ I \ ( \ ~ \
W W W " Csa
CA 02296121 2000-O1-28
x x x x x x
b x
v
>~
0
U
1 1 1 1
x n'1 N N N N
u -x x x x x
U U U U
1 1 I I 1 1
N N N N N N
x N x x x x x x
U -fx U U U U U U
1 1 I I 1 1 I 1
1
1
N
1 s 1 I 1 x
N N N N N V
x x x x x I
U U U U U O
1 1 I I I
O O O O O /
\
\ ~ \ \ \ N
x
O O O O O U
1 1 1 1 1 1
1
\ 1 / ( \ ~ \
Q \ N tf1
x o ~n x ~n 1 x
U N N U N x N
N w w x x u-a
G~ U U U U t
cn x x II U ~n
x N N N ul x
v w w x a N
U U U x U
CA 02296121 2000-O1-28
x x x x
~ x
v
a
.,.,
0
U
I 1 1
x M N N N
U-x x x x
U U U
I 1 1 1
N N N N
x N x x x x
U-cx U U U U
r
I
1
N
x I I I
U N N N
I x x x
O U U U
1 I I
O O '-I O .-i
U U
N
x
U o 0 0
I 1 I 1
I
N 1
tt1 x N
I x a x
x N 1 ~ U
U-U x x x I x
I~ U- U O-U-U
x x
U U U
CA 02296121 2000-O1-28
x x x x
b x
v --
a
.,.,
0
U
1 I 1 1
V fx x x x x
U U U U
1 1 1 1
N N N N
x N x x x ~ x
U - P4 U U U U
I 1 1 1 I
I
I
1
N
I 1 I x
N N N U
U U U O
1 I i
O O O
w
i I ~ I i I w
N
-1 x
O U ~1=O O=~=O U
1 I 1 1
I
w ( w
w w
CA 02296121 2000-O1-28
x x x x x
b x
s~
.,.,
0
U
1 I I I 1
x M N N N N N
v- x x x x x x
U U U U U
1 I I 1 1
N N N N N
x N x x x x x
U-fx U U U U U
1 1 1 I 1 1
I
1
I I
M M
1 1
N N N N
U U xN U U
N N U 1 M 1 M
V U ~1 U-U U U
N
x x
U U
O O O
1
N
x 1
M U M N
x I x x
U-U- V ~ U
O U-U-V
x O
fsa G4 fl., U x
CA 02296121 2000-O1-28
x x x x x x
b x
a~
0
.,.,
s~
0
U
1 1 I I I I
x M N N N N N N
U -x x x x x x x
V U V U U U
N N N N N N
x N x x x x x x
U -G~U U U U U U
1 I 1 1 1 I 1
I
0
N
1
I
c~
N
x I I
V N N
x x
1 M U U
V-V Iw u'~ O O
1 1 ~.. ~.
N _~O x x / /
N N U U
U V p O O O
1 1 1 1 1 1
1 1 1
N N N I
r~ ~I c~1 ~I ~1 ch U c~1
P4 U-U U-U / i U-U V-U-U
1 1 ( ~ I 1
''' '~' w ~ x x
U U w w U U
CA 02296121 2000-O1-28
x x x x x x
rox
a~
a
.r.,
>~
0
U
1 1 I 1 1 1
x c~1 N rJ N N N N
v-x x x x x x x
U U U U U U
I 1 I 1 1 I
x N x x x x x x
U-fx U U U U U U
1 I 1 1 1 I t
I
N
1
1 1 I 1
N N N N
1 x 1 x x x
N U N U U V
U O U O O O
I I
O i O i / ~ /
O ~ O O O
1 1 1 I
1
N
1 1
N N N 1
1 x x 1 x N
N U U N a x
x I ~n I r, x -- V
r, v M x x x x v M 1 M I
x I x v U U- U 1 x x x x
-
fx U- U- U 1 I U- U U- U U
~ ~
M x x N ~., N
x N N x x x
U U U U U U
CA 02296121 2000-O1-28
a x x x x x
bx
v--
s~
0
U
1 I 1 1 1
x M N N N N N
U-x x x x x x
U U U U U
N N N N N
x N x x x x x
U- oG U U U U U
I 1 I 1 I 1
I
N
N
I
1 1 1 t11 1
N N N 1 x N
x x x x N x
U U U U-V U
1 I 1 I I
O O O O O
~ ~ ~ I
\ \ \
U U
O O O O ~ O
1 1 1 1 x 1 x
I
1 N
N
1 N
1 N ~ x
N x U
x U w --
U M -- M x I r,
I ~ x 1 x U x x
C4 U-U U- U- U v , V-U
1 I I
II I
~
x ~: x x
U U U U
CA 02296121 2000-O1-28
x
_ N
x x x x x a
a
s:
0
U
v?
I I I 1
x ~,., N N 1 I N N
N N x x
U U U U U U
N N I I N N
U ~ U U U- U U - U U
I I I i Gv I I
I
I
M
N
I
I 1 I 1 1
N N N N N
V ~N U U U U
O U O O O O
;x,, I
O ~ ' ~ I , '
/I
O O O O O
1 1
N N
x --
U N
r x
O U
I M '.'
,..., x x I
PG / U - U ~ / N i
IM
x
U U
CA 02296121 2000-O1-28
c~ M
x x U x U x x
rb(~ 1 I
n, r,
s~
s~
0
U
I I f I
U G4 x 1 N x ~C x
N CI x N N (N IN N
U-PG U U-U U U ' U U U
1 I I I I 1 1 I I
N
I i
x
U
11
x
U
1
1 1 1 N ( 1
N N N x N 1 M N
U U U ~I M U V-U U
I I I x x I 1 I
O O O U-U O O O
I
N ~ ~
1 ~ ~ / ~ ~~ ( 1
w w x ~ w w
a
0 0 0 -r o 0 0
I i I 1 I 1 I
i
f
I
N - Cl1
1 x N
N U x
x 1 M v
IY V i i V -U / / V
III I I ~''~ ( ~ IIN
V \ \ U ' \ U
CA 02296121 2000-O1-28
x x x x x x x
b x
o _..
>~
.r.,
0
U
1 I I I 1 I 1
x M N N N N N N N
U ~ U U U U U U
U 1 1 I 1 1 1
1
N N N N N N N
U U
U PG U U U U U
I I s I t I t I 1
N
1
x
I 1 1 I 1 t U
N N N N N N II
x x x x x x x
V U U U U U U
I 1 I I I I I
O O O O O O
N
'~ ~ I ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ U
I
O O O O O O O
I 1 I I t I I
i
I i i
t I
I V
i
I \ N U O ~ I ~ tnv
x x x o N x
rl U U ~-~ U U .-I x ii. U rl
fx U U-U x V-U U-U U-U i
r1 N U N III N
x x ~ x x x
U U U U U U
CA 02296121 2000-O1-28
x x x x x x
b x
a~
a
0
U
~?
1 1 1 I I 1
x M N N N N N N
U U U U
U I 1 1 U I
1 1
N N N N N N
x N x x x x x x
U - U U U U V U
I t G: I 1 I I 1 I
~o
N
1
M
1 x i
U-U U-frr I 1 1
II ti N N N
x x x x x
U U U U U
I I 1 I I I
w r~ c~~ O ~ O ~ O
V U
U _U _U I / I /
I 1 1
c~ O O O O O
1 I 1 I i I
W /
w / / i i
I I
w ~ ~ ~ ~ U .-~ ,-I
w W v U
CA 02296121 2000-O1-28
- 27 -
Practical and presently preferred embodiments for
preparation of the pyrazole compounds (I) including compounds
of the parent application are illustratively shown in the
following examples.
Example 1
To a mixture of anhydrous N,N-dimethylformamide (5
ml) and sodium hydride (60 % oil suspension; 39 mg),
pyrazole (66 mg) was added, and the resultant mixture was
stirred for 30 minutes. A solution of 3-(4-phenoxyphenoxy)-
propyl bromide (300 mg) in anhydrous N,N-dimethylformamide
(5 ml) was dropwise added thereto, followed by stirring at
room temperature for 5 hours. The reaction mixture was
diluted with ethyl acetate (50 ml), washed with a saturated
aqueous ammonium chloride solution twice , dried over
anhydrous magnesium sulfate and concentrated under reduced
pressure. The oily substance thus obtained was subjected to
column chromatography to give 246 mg of 1-[3-(4-phenoxy-
phenoxy)propyl]pyrazole as a colorless oil. np3.5 1,5777.
Example 2
To a mixture of anhydrous dimethylsulfoxide (5 ml)
and sodium hydride (60 % oil suspension'; 62 mg), pyrazole
(106 mg) was added, and the resultant mixture was stirred
for 30 minutes. A solution of 3-[4-(3-tolyloxy)phenoxy]-
propyl bromide (500 mg) in anhydrous dimethylsulfoxide (5
ml) was dropwise added thereto, followed by stirring at room
temperature for 3 hours. The reaction mixture was treated
in the same manner as in Example 1 to give 347 mg of 1-~3-
[4-(3-tolyloxy)phenoxy)propyl~ pyrazole as a colorless oil.
nD3.7 1.5738.
CA 02296121 2000-O1-28
- 28 -
In the same manner as above, there were prepared the
pyrazole compounds (I) including compounds of the parent
application, of which typical examples are shown in Table 2.
CA 02296121 2000-O1-28
t~ U
o r1 O1
n n
w m n
a~
~
ro r, u, .-,
a
Uro
w n
tn
N
~
Q N (.~ N (~ N A
W U f~ E~ >~ R
d: x x x x
x
IN
x
x M U
U - 1 I I
04
N N N
U U U
x N 1 1 1 I
U- ~, N N N N
I x x x x
U U U U
I 1 I I
I
o~
N
I f
N N N 1 N
U U U U-U
O O O O
/ i / i
\ I ~ I \ ~ \ I
0 0 0 0
x
U- PG
N U x x ~ ~ I ~
\ w w
'Q I
ro
E~ cx
~d
1
.-i N ~
O O O
U L~ ~
CA 02296121 2000-O1-28
m ~I u~ w n o0
p1 O O 01 N C ~D
00 I~ ~D 00 t0 I~
u1 u1 u1 u1 u'1 W 1 u1
"J
(d ~' r-1 e-1 r--1 e--1 r~ '-1 ri
U c0
-rl tt1 M tf1 u1 M M N
~
y .("',V' d' d' M sr U1 d'
O N (~ N (~ N O N O N (~ N (.a N
Ca
~ W U >~ s~ s~ ~ ~ ~ t~
1~
+~
N
O
U M M M
U
U U U
x x I I I -- x
Q', M ~ ~ I
x
M
U ~n; I I I 1 1
U U U U U U U
x -
x U I I I I 1 1
~~
U-Cr' IM N N N N N N
I x x x x x x x x
U-U U U U U U U
I I I t t 1 I
I
0
M
I
I I 1 1 ! 1 1
N N N N N N N
x x x x x x x
U U U U U U U
1 I i I 1 1 I
O O O O O O O
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CA 02296121 2000-O1-28
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CA 02296121 2000-O1-28
- 43 -
On the application of the pyrazole compound (I) as
a pesticide, it may be used as such or in an appropriate
preparation form, e.g, an oil spray, an emulsifiable
concentrate, a wettable powder, granules, a dust, an
aerosol, a fogging agent, a toxic bait, etc. In those
preparations, the pyrazole compound (I) is usually contained
in about 0.1 to about 99.9 $ by weight, preferably in about
2 to about 80 $ by weight.
Such preparations can be formulated in per se
conventional manners by mixing at least one of the pyrazole
compounds (I) with an appropriate solid, liquid or gaseous
carriers) or diluent(s) or a bait. An appropriate
adjuvant(s), e.g. a surfactant, an adherent, a dispersant or a
stabilizer may also be mixed therein to improve the
dispersibility and other properties of-the preparation.
Examples of the solid carriers or diluents are
fine powders or granules of clays (e. g. kaolin clay,
diatomaceous earth, synthetic hydrated silica, bentonite,
fubasami clay, terra alba), tales, ceramics, other inorganic
minerals (e. g. sericite, quartz, sulfur, active carbon,
calcium carbonate, hydrated silica), chemical fertilizers
(e. g. ammonium sulfate, ammonium phosphate, ammonium
nitrate, urea, ammonium chloride), etc. Examples of the
liquid carriers or diluents are water, alcohols (e. g.
methanol, ethanol), ketones (e. g. acetone, methylethyl-
ketone), aromatic hydrocarbons (e. g. benzene, toluene,
xylene, ethylbenzene, methylnaphthalene), aliphatic hydro-
carbons (e. g. Hexane, cyclohexane, kerosene, light oil),
CA 02296121 2000-O1-28
- 44 -
esters (e. g. ethyl acetate, butyl acetate), nitriles (e. g.
acetonitrile, isobutyronitrile), ethers (e. g. diisopropyl
ether, dioxane), acid amides (e. g. N,N-dimethylformamide,
N,N-dimethylacetamide), halogenated hydrocarbons (e. g.
dichloromethane, trichloroethane, carbon tetrachloride),
dimethylsulfoxide, botanical oils (e. g. soybean oil,
cotton-seed oil), etc. Examples of the gaseous carriers or
diluents are Freon gas, butane gas, LPG (liquefied petroleum
gas), dimethyl ether, carbon dioxide, etc.
The surfactants suitable for emulsification, dis-
persion or spreading may be any of the ionic and nonionic
types. Their examples include alkylsulfates, alkylaryl-
sulfonates, dialkylsulfosuccinates, polyoxyethylenealkyl-
arylphosphates, condensates of naphthalenesulfonic acid and
formalin, polyoxyethylene alkyl ethers, polyoxyethylene
polyoxypropylene block copolymers, sorbitan fatty acid
esters, polyoxyethylene sorbitan fatty acid esters, etc.
Examples of the adherents or dispersants may include casein,
gelatin, polyvalent alcohols (e.g. starch powder, gum
arabic, cellulose derivatives, alginic acid), lignin
derivatives, bentonite, saccharides, synthetic water-soluble
high molecular compounds (e. g. polyvinyl alcohol, polyvinyl-
pyrrolidone, polyacrylic acid), etc. As the stabilizers,
there may be used alkyl phosphates (e. g. PAP (isopropyl acid
phosphate), BHT (2,6-di-tert-butyl-4-methyl-phenol), BHA
(a mixture of 2-tert-butyl-4-methoxyphenol and 3-tert-butyl-
4-methoxyphenol), botanical oils, mineral oils, surfactaryts,
aliphatic acids or esters, etc.
CA 02296121 2000-O1-28
- 45 -
The base for toxic baits may comprise food (e. g.
grain powders, essential oils, sugar, crystalline cellu-
lose), an antioxidant (e. g. dibutylhydroxytoluene, butyl-
hydroxyanisole, nordihydroguaiaretic acid), a preservative
(e.g. dehydroacetic acid), a mis-feed inhibitor (e.g. red
pepper powders), a flavoring agent (e. g. cheese flavor,
onion flavor), etc.
The composition thus formulated may be applied as
such or in a form diluted with water. In addition; said
composition may contain other insecticides, nematocides,
acaricides, fungicides, herbicides, plant growth regulators,
synergistic agents, fertilizers, soil improvers, etc.
Particularly when employed in conjunction with conventional
insecticides, a broad spectrum of activity or a more
immediate effect on very heterogeneous populations is
provided. Examples of the insecticides include organic
phosphorus compounds (e.g. fenitrothion (O,O-dimethyl-O-
(3-methyl-4-nitrophenyl)phosphorothioate), malathion (S-
[1,2-bis(ethoxycarbonyl)ethyl] O,O-dimethylphosphorothio-
ate), dimethoate (O,O-dimethyl-S-(N-methylcarbamoylmethyl)-
phosphorodithioate), salithion (2-methoxy-4H-1,3,2-benzo-
dioxaphosphorin-2-sulfide), diazinon (O,O-diethyl-O-(2-
isopropyl-6-methyl-4-pyrimidinyl)phosphorothioate), trichlorfon
(2,2,2-trichloro-1-hydroxyethyl-0,0-dimethylphosphonate),
dichlorvos (O-(2,2-dichlorovinyl)-O,O-dimethylphosphate),
etc.), carbamate compounds (e. g. MPMC (3,4-dimethylphenyl
N-methylcarbamate), MTMC (m-tolyl N-methylcarbamate), BPMC
(2-sec-butylphenyl N-methylcarbamate), carbaryl (1-naphthyl
CA 02296121 2000-O1-28
- 46 -
N-methylcarbamate), etc.) and pyrethroid compounds (e. g.
permethrin (3-phenoxybenzyl-d,.~-cis,trans-3-(2,2-dichloro-
vinyl)-2,2-dimethylcyclopropanecarboxylate), fenvalerate
(a-cyano-m-phenoxybenzyl a-isopropyl-p-chlorophenylacetate),
etc . ) .
The composition may be applied to pests using a
conventional method, of which typical examples include
spreading, fuming, soil treatment, incorporation into food
for domestic animals or poultry, etc. It is further
noticeable that addition of the composition to sericiculture
food may lead to an increase of cocoons in number or
thickening the cocoon layer.
The dosage of the pyrazole compound (I) as the
active ingredient in an agricultural pesticidal composition
is generally from about 5 to about 500 grams per 10 ares.
When the composition is applied as an emulsifiable concen-
trate or a wettable powder, the concentration of the active
ingredient is normally from about 1 to about 500 ppm. In the
case of such formulations granules, fine granules and
dusts, the composition may be applied as such without
diluti..on with water. As a sanitary pesticidal composition,
the composition in the form of an emulsifiable concentrate,
an emulsifiable concentrate or a wettable powder may be
diluted with water in a concentration of the active in-
gredient being generally from about 1 to about 500 ppm and
applied. ~In the case of a formulation such as an oil spray,
an aerosol, a fumigant, a bait or the like, it may be
applied as such.
CA 02296121 2000-O1-28
- 47 -
Said amounts and concentrations are not definite and
may vary depending on the type of preparation, application
season, locus to be applied, mode of application, species of
pests, degree of damage, etc.
Some practical embodiments of the composition
according to the invention are illustratively shown in the
following Formulation Examples wherein % and parts) are by
weight and the compound numbers correspond to those in Table
2.
Formulation Example 1
One of Compounds Nos. 1 to 75 (20 parts), an
emulsifier (a mixture of polyoxyethylene styrylphenyl ether,
polymer of polyoxyethylene styrylphenyl ether and alkylaryl-
sulfonate) (20 parts) and xylene (60 parts) were well mixed to
make a 20% emulsifiable concentrate.
Formulation.Example 2
One of Compound Nos. 1 to 75 (20 parts), an
emulsifier (sodium laurylsulfate) (5 parts) and diatomaceous
earth (#300 mesh; 75 parts) were well mixed in a pulverizes to
make a 20% wettable powder.
Formulation Example 3
One of Compound Nos. 1 and 2 (3 parts), acetone (20
parts) and talc (#300 mesh: 97 parts) were well mixed in a
pulverizes, followed by removal of acetone by evaporation to
make a 3% dust.
Formulation Example 4
One of Compound Nos. 1 to 75 (5 parts), a dispersing
agent (calcium ligninsulfonate) (2 parts) and clay (93 parts)
CA 02296121 2000-O1-28
- 48 -
were well mixed, followed by addition of a small amount of
water. The resultant mixture was kneaded and granulated with
the aid of a granulator and dried to make 5-°s granules.
Formulation Example 5
Compound No. 1 (2 parts), a dispersing agent
(calcium ligninsulfonate) (2 parts) and clay (96 parts) were
well mixed, followed by addition of a small amount of water.
The resultant mixture was kneaded and granulated with the aid
of a fine granulator and dried to make 2% fine granules.
Formulation Exa~~le 6
Compound No. 1 (0.2 part), xylene (2 parts),
dimethylformamide (2 parts) and lamp oil (95.8 parts) were
well mixed to make an oil spray.
Formulation Example 7
Compound No. 1 (0.05 part), tetramethrin (N-
(3,4,5,6-tetrahydrophthalimido)methylchrysanthemate) (0.2
part), resmethrin (5-benzyl-3-furylmethyl (~)-cis,trans-
chysanthemate) (0.05 part), xylene (7 parts) and deodorized
lamp oil (42.7 parts) were well mixed and charged into an
aerosol container. Upon attachment of a valve portion, a
pressurizing agent (LPG) (50 parts) was charged through the
valve to make an aerosol.
Formulation Example 8
Compound No. 1 (1 part) and sesame oil (3 parts) are
mixed, and butyl hydroxyanisole (0.03 part), dehydroacetic
acid (0.1 part), black sugar (10 parts), crystalline cellulose
(30 parts) and potato starch (55.87 parts) were
CA 02296121 2000-O1-28
- 49 -
added thereto. The resultant mixture was uniformly mixed and
pressurized with a load of 15 kg/cm2 to make a toxic bait in
tablet form, each tablet having a weight of approx. 4 g and a
diameter of 30 mm.
The following Test~Examples present some typical
test data indicating the excellent pesticidal activity of
the pyrazole compounds (I). The compounds used for
comparison are shown in Table 3 below:
Table 3
Ca~ound
No. Structure Remarks
(A) CH3 CH3 CH3 Known as
~i "methoprene"
p~ ~ ( ( ;
3 U. S . patent
C (CH2 ) 3C~3CH2CH~C~ICOOCH (CH3) 2
3,904,662
(g) ~ Canadian
I
/ \ ~ patent
~ (CH2)3
iV
- 1, 231, 945;
a ~--~
Co~ound No
.
118
(C) ~' ~-287959;
/ \ / \ C~ound No .
N I4-1
~3
Test Example 1
An emulsifiable concentrate prepared according to
Formulation Example 1 was diluted with water to make a 400
fold dilution. The dilution (0.7 ml) was added to 100 ml of
distilled water. Last instar larvae of common mosquito
(Culex pipiens pallens) were released therein and reared for
7 days until their emergence. The rate of emergence was
observed with two replications. The results are shown in
Table 4.
CA 02296121 2000-O1-28
- 50 -
Table 4
Test compound Concentration Rate of emergence
I No. I (PPm) l
1 3.5 ~ 0
2 3.5 , 0
3 3.5 3 0
4 3.5 ~ 0
5 3.5 ~ 0
6 3.5 0
7 3.5 0
8 ! 3.5 ~ 0
9 3.5 0
10 3.5 0
11 3.5 0
12 3.5 0
13 3.5 0
14 3.5 0
15 3.5 0
16 3.5 0
17 3.5 0
18 3.5 0
19 3.5 0
20 3.5 0
21 3.5 0
22 3.5 0
23 3.5 0
24 3.5 0
25 3.5 0
26 3.5 0
27 3.5 0
28 3.5 0
29 3.5 0
30 3.5 0
31 3.5 0
32 3.5 0
33 3.5 0
34 3.5 0
35 3.5 0
36 3.5 0
37 3.5 0
38 3.5 0
39 3.5 0
40 3.5 0
41 3.5 0
42 3.5 0
43 3.5 0
44 3.5 0
45 3.5 0
46 3.5 , 0
47 3.5 0
48 3.5 0
CA 02296121 2000-O1-28
- 51 -
(Continued)
Test com ound Concentration Rate of emer once
p g
No. ' (ppm) ($)
49 3.5 ~ 0
50 3.5 0
51 3.5 0
52 3.5 0
53 3.5 0
54 3.5 0
55 3.5 0
56 3.5 0
57 3.5 0
58 3.5 0
59 3.5 0
60 3.5 0
61 3.5 0
62 3.5 0
63 3.5 0
64 3.5 0
65 3.5 0
66 3.5 0
67 3.5 0
68 3.5 0
69 3.5 0
70 3.5 0
7I 3.5 0
72 3.5 0
73 3.5 0
74 3.5 0
75 3.5 0
(A) 3.5 0
Untreated ~ - 90
Test Example 2
Powdered animal feed (2 g) was. thoroughly mixed
with bran (14 g). An emulsifiable concentrate prepared
according to Formulation Example 1 was diluted with water to
a sgec~:fi~ed concentration, and the dilution was added to the
above mixture. The resultant mixture was stirred well to
make an artificial culture. Thirty housefly larvae
(Musca domestica) were reared therein until their pupation.
CA 02296121 2000-O1-28
_ _ 52 _
The obtained pupae were placed into a plastic cup, and the
rate of emergence was determined. According to the follow-
ing equation, the emergence inhibition (%) was calculated:
Emergence Rate of emergence in treated plot
inhibition - (I ' Rate of emergence in untreated plot ) X i00
($)
The results are shown in Table 5.
Table 5
Test compound No. Emergence inhibition
($)
3 ppm I ppm
1 100 100
2 100 88
14 91 58
75 100 88
(A) 60 I3
(H) 40 0
(C) 5 0
