U.S. patent application number 11/931820 was filed with the patent office on 2008-05-29 for synergistic insecticidal compositions.
Invention is credited to Raymond Frank Borysewicz, Hassan Oloumi-Sadeghi, Paul E. Rensner, Kurt Allen Schwinghammer, Michael Frank TREACY.
Application Number | 20080125421 11/931820 |
Document ID | / |
Family ID | 26822413 |
Filed Date | 2008-05-29 |
United States Patent
Application |
20080125421 |
Kind Code |
A1 |
TREACY; Michael Frank ; et
al. |
May 29, 2008 |
SYNERGISTIC INSECTICIDAL COMPOSITIONS
Abstract
The present invention provides a synergistic insecticidal
composition comprising as essential active ingredients a neuronal
sodium channel antagonist in combination with one or more compounds
selected from the group consisting of pyrethroids, pyrethroid-type
compounds, recombinant nucleopolyhedroviruses capable of expressing
an insect toxin, organophosphates, carbamates, formamidines,
macrocyclic lactones, amidinohydrazones, GABA antagonists and
acetylcholine receptor ligands. Also provided are methods for
synergistic insect control and crop protection.
Inventors: |
TREACY; Michael Frank;
(Newton, PA) ; Borysewicz; Raymond Frank;
(Hamilton Square, NJ) ; Schwinghammer; Kurt Allen;
(Yardley, PA) ; Rensner; Paul E.; (Yardley,
PA) ; Oloumi-Sadeghi; Hassan; (Yardley, PA) |
Correspondence
Address: |
NOVAK DRUCE DELUCA + QUIGG LLP
1300 EYE STREET NW, SUITE 1000 WEST TOWER
WASHINGTON
DC
20005
US
|
Family ID: |
26822413 |
Appl. No.: |
11/931820 |
Filed: |
October 31, 2007 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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10145784 |
May 16, 2002 |
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11931820 |
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09521987 |
Mar 9, 2000 |
6479543 |
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10145784 |
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60124306 |
Mar 12, 1999 |
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60158201 |
Oct 7, 1999 |
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Current U.S.
Class: |
514/229.2 ;
514/403; 514/590 |
Current CPC
Class: |
A01N 37/50 20130101;
A01N 37/50 20130101; A01N 37/50 20130101; A01N 47/34 20130101; A01N
47/38 20130101; A01N 47/34 20130101; Y02A 50/356 20180101; A01N
47/34 20130101; A01N 43/56 20130101; A01N 47/34 20130101; A01N
47/38 20130101; A01N 43/56 20130101; A01N 43/56 20130101; A01N
47/38 20130101; A01N 37/52 20130101; A01N 47/24 20130101; A01N
2300/00 20130101; A01N 37/52 20130101; A01N 47/40 20130101; A01N
43/22 20130101; A01N 47/02 20130101; A01N 47/24 20130101; A01N
43/22 20130101; A01N 47/02 20130101; A01N 43/54 20130101; A01N
47/40 20130101; A01N 37/52 20130101; A01N 37/52 20130101; A01N
43/54 20130101; A01N 43/56 20130101; A01N 47/40 20130101; A01N
47/24 20130101; A01N 43/54 20130101; A01N 2300/00 20130101; A01N
47/40 20130101; A01N 63/00 20130101; A01N 2300/00 20130101; A01N
63/00 20130101; A01N 2300/00 20130101; A01N 47/24 20130101; A01N
47/24 20130101; A01N 53/00 20130101; A01N 47/40 20130101; A01N
43/56 20130101; A01N 53/00 20130101; A01N 43/22 20130101; A01N
47/40 20130101; A01N 53/00 20130101; A01N 43/22 20130101; A01N
63/00 20130101; A01N 47/24 20130101; A01N 47/40 20130101; A01N
63/00 20130101; A01N 43/22 20130101; A01N 37/52 20130101; A01N
47/02 20130101; A01N 53/00 20130101; A01N 43/22 20130101; A01N
47/02 20130101; A01N 47/02 20130101; A01N 63/00 20130101; A01N
47/02 20130101; A01N 53/00 20130101; A01N 63/00 20130101; A01N
37/52 20130101; A01N 43/22 20130101; A01N 47/24 20130101; A01N
63/00 20130101; A01N 53/00 20130101; A01N 37/52 20130101; A01N
43/56 20130101; A01N 47/02 20130101; A01N 53/00 20130101; A01N
47/38 20130101; A01N 47/34 20130101 |
Class at
Publication: |
514/229.2 ;
514/403; 514/590 |
International
Class: |
A01N 43/88 20060101
A01N043/88; A01N 43/56 20060101 A01N043/56; A01P 17/00 20060101
A01P017/00; A01N 47/34 20060101 A01N047/34 |
Claims
1.-33. (canceled)
34. A synergistic insecticidal composition comprising a
synergistically effective amount of a neuronal sodium channel
antagonist in combination with one or more acetylcholine receptor
ligand compounds, wherein the neuronal sodium channel antagonist is
a compound of formula (V) ##STR00006## wherein W is O or S; Y'' is
H; halogen; CN; SCN; C.sub.1-C.sub.6alkyl optionally substituted
with one or more halogen, NO.sub.2, CN, C.sub.1-C.sub.4alkoxy,
C.sub.1-C.sub.4alkylthio, phenyl, halophenyl,
C.sub.1-C.sub.4alkylsulfonyl, C.sub.1-C.sub.4haloalkylsulfonyl, or
C.sub.1-C.sub.4alkoxycarbonyl groups; C.sub.2-C.sub.4alkenyl;
C.sub.2-C.sub.4haloalkenyl; C.sub.2-C.sub.4alkynyl;
C.sub.2-C.sub.4haloalkynyl; C.sub.3-C.sub.6cycloalkyl;
C.sub.3-C.sub.6halocycloalkyl; phenyl optionally substituted with
one or more halogen, CN, NO.sub.2, C.sub.1-C.sub.4alkyl,
C.sub.1-C.sub.4haloalkyl, C.sub.1-C.sub.4alkoxy,
C.sub.1-C.sub.4haloalkoxy, C.sub.1-C.sub.4alkylthio,
C.sub.1-C.sub.4alkylsulfonyl or C.sub.1-C.sub.4haloalkylsulfonyl
groups; C.sub.1-C.sub.4alkylcarbonyl;
C.sub.1-C.sub.4haloalkylcarbonyl; or NR.sub.28R.sub.29; m is an
integer of 1, 2, 3, 4 or 5; G' is phenyl optionally substituted
with one or more groups which may be the same or different selected
from Y''; a 5-membered heteroaromatic ring containing one or two
heteroatoms selected from 0 or 1 oxygen, 0 or 1 sulfur and 0, 1 or
2 nitrogen atoms said 5-membered heteroaromatic ring being attached
via carbon and being optionally substituted with one or more groups
which may be the same or different selected from Y''; or a
6-membered heteroaromatic ring containing one or two heteroatoms
selected from 0 or 1 oxygen, 0 or 1 sulfur and 0, 1 or 2 nitrogen
atoms said 6-membered heteroaromatic ring being attached via carbon
and being optionally substituted with one or more groups which may
be the same or different selected from Y''; Q' is H;
C.sub.1-C.sub.6alkyl optionally substituted with one or more
halogen, CN, C.sub.1-C.sub.3alkoxy, C.sub.1-C.sub.6alkoxycarbonyl,
or phenyl optionally substituted with one or more halogen, CN,
NO.sub.2, C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4haloalkyl,
C.sub.1-C.sub.4alkylsulfonyl or C.sub.1-C.sub.4alkylsulfinyl
groups; C.sub.2-C.sub.6alkenyl; C.sub.2-C.sub.6alkynyl; or phenyl
optionally substituted with one to three groups, which may be the
same or different, selected from Y''; R.sub.26, R.sub.27, R.sub.28
and R.sub.29 are each independently H or C.sub.1-C.sub.4alkyl; and
the dotted line configuration CN represents a double bond or a
single bond; or a stereoisomer thereof.
35. The composition according to claim 34 wherein the dotted line
configuration CN represents a double bond.
36. The composition according to claim 35 wherein W is O.
37. The composition according to claim 36 wherein the one or more
acetylcholine receptor ligand compounds are selected from the group
consisting of imidacloprid, acetamiprid, nitenpyram and
thiamethoxam.
38. The composition according to claim 34 wherein the one or more
acetylcholine receptor ligand compounds are selected from the group
consisting of imidacloprid, acetamiprid, nitenpyram and
thiamethoxam.
39. A method for synergistic insect control which comprises
contacting said insects with a synergistically effective amount of
a neuronal sodium channel antagonist in combination with one or
more insecticidally active acetylcholine receptor ligand compounds,
wherein the neuronal sodium channel antagonist is a compound of
formula (V) ##STR00007## wherein W is O or S; Y'' is H; halogen;
CN; SCN; C.sub.1-C.sub.6alkyl optionally substituted with one or
more halogen, NO.sub.2, CN, C.sub.1-C.sub.4alkoxy,
C.sub.1-C.sub.4alkylthio, phenyl, halophenyl,
C.sub.1-C.sub.4alkylsulfonyl, C.sub.1-C.sub.4haloalkylsulfonyl, or
C.sub.1-C.sub.4alkoxycarbonyl groups; C.sub.2-C.sub.4alkenyl;
C.sub.2-C.sub.4haloalkenyl; C.sub.2-C.sub.4alkynyl;
C.sub.2-C.sub.4haloalkynyl; C.sub.3-C.sub.6cycloalkyl;
C.sub.3-C.sub.6halocycloalkyl; phenyl optionally substituted with
one or more halogen, CN, NO.sub.2, C.sub.1-C.sub.4alkyl,
C.sub.1-C.sub.4haloalkyl, C.sub.1-C.sub.4alkoxy,
C.sub.1-C.sub.4haloalkoxy, C.sub.1-C.sub.4alkylthio,
C.sub.1-C.sub.4alkylsulfonyl or C.sub.1-C.sub.4haloalkylsulfonyl
groups; C.sub.1-C.sub.4alkylcarbonyl;
C.sub.1-C.sub.4haloalkylcarbonyl; or NR.sub.28R.sub.29; m is an
integer of 1, 2, 3, 4 or 5; G' is phenyl optionally substituted
with one or more groups which may be the same or different selected
from Y''; a 5-membered heteroaromatic ring containing one or two
heteroatoms selected from 0 or 1 oxygen, 0 or 1 sulfur and 0, 1 or
2 nitrogen atoms said 5-membered heteroaromatic ring being attached
via carbon and being optionally substituted with one or more groups
which may be the same or different selected from Y''; or a
6-membered heteroaromatic ring containing one or two heteroatoms
selected from 0 or 1 oxygen, 0 or 1 sulfur and 0, 1 or 2 nitrogen
atoms said 6-membered heteroaromatic ring being attached via carbon
and being optionally substituted with one or more groups which may
be the same or different selected from Y''; Q' is H;
C.sub.1-C.sub.6alkyl optionally substituted with one or more
halogen, CN, C.sub.1-C.sub.3alkoxy, C.sub.1-C.sub.6alkoxycarbonyl,
or phenyl optionally substituted with one or more halogen, CN,
NO.sub.2, C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4haloalkyl,
C.sub.1-C.sub.4alkylsulfonyl or C.sub.1-C.sub.4alkylsulfinyl
groups; C.sub.2-C.sub.6alkenyl; C.sub.2-C.sub.6alkynyl; or phenyl
optionally substituted with one to three groups, which may be the
same or different, selected from Y''; R.sub.26, R.sub.27, R.sub.28
and R.sub.29 are each independently H or C.sub.1-C.sub.4alkyl; and
the dotted line configuration CN represents a double bond or a
single bond; or a stereoisomer thereof.
40. The method according to claim 39, wherein the dotted line
configuration CN represents a double bond.
41. The method according to claim 40, wherein W is O.
42. The method according to claim 41, wherein the one or more
acetylcholine receptor ligand compounds are selected from the group
consisting of imidacloprid, acetamiprid, nitenpyram and
thiamethoxam.
43. The method according to claim 39, wherein the one or more
acetylcholine receptor ligand compounds are selected from the group
consisting of imidacloprid, acetamiprid, nitenpyram and
thiamethoxam.
44. The method according to claim 39, wherein the insect is
selected from the group consisting of Blattaria, Isoptera, Diptera,
and Hymenoptera.
45. The method according to claim 44, wherein the insects are
lepidoptera or coleoptera.
46. A method for protecting a plant from infestation and attack by
insects which comprises applying to the foliage or stem of said
plant a synergistically effective amount of a composition according
to claim 34.
47. The composition according to claim 46, wherein the dotted line
configuration CN represents a double bond.
48. The composition according to claim 47, wherein W is O.
49. The method according to claim 48, wherein the one or more
acetylcholine receptor ligand compounds are selected from the group
consisting of imidacloprid, acetamiprid, nitenpyram and
thiamethoxam.
50. The method according to claim 46, wherein the one or more
acetylcholine receptor ligand compounds are selected from the group
consisting of imidacloprid, acetamiprid, nitenpyram and
thiamethoxam.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This is a Divisional of application Ser. No. 10/145,784,
filed on May 16, 2002, (pending), the entire disclosure of which is
herewith incorporated by reference, which is a divisional
application of application Ser. No. 09/521,987, filed on Mar. 9,
2000 (now U.S. Pat. No. 6,479,543), the entire disclosure of which
is herewith incorporated by reference, which claims the benefit of
provisional application Ser. No. 60/124,306 (filed Mar. 12, 1999)
and Ser. No. 60/158,201 (filed on Oct. 7, 1999), both abandoned,
the entire disclosures of which are herewith incorporated by
reference.
BACKGROUND OF THE INVENTION
[0002] Insecticidal agents and compositions have been developed to
control insect pests such as agrohorticultural pests, hygienic
pests, or wood-eating pests and in practice have been used as a
single or a mixed agent. However, economically efficient and
ecologically safe insect control compositions are still being
sought. Insecticidal compositions which allow for reduced effective
dosage rates, increased environmental safety and lower incidence of
insect resistance are highly desirable. Although the rotational
application of insect control agents having different modes of
action may be adopted for good pest management practice, this
approach does not necessarily give satisfactory insect control.
Further, even though combinations of insect control agents have
been studied, a high synergistic action has not always been found.
Obtaining an insecticidal composition which demonstrates no
cross-resistance to existing insecticidal agents, no toxicity
problems and little negative impact on the environment is extremely
difficult.
[0003] Therefore, it is an object of this invention to provide a
synergistic insecticidal composition which demonstrates a high
controlling effect with concomittant reduced crop production cost
and reduced environmental load.
[0004] It is another object of this invention to provide methods
for synergistic insect control and enhanced crop protection.
SUMMARY OF THE INVENTION
[0005] The present invention provides a synergistic insecticidal
composition comprising as essential active ingredients a
synergistically effective amount of a neuronal sodium channel
antagonist in combination with one or more compounds selected from
the group consisting of pyrethroids, pyrethroid-type compounds,
recombinant nucleopolyhedroviruses capable of expressing an insect
toxin, organophosphates, carbamates, formamidines, macrocyclic
lactones, amidinohydrazones, GABA (gamma-aminobutyric acid)
antagonists, and acetylcholine receptor ligands.
[0006] The present invention also provides a method for synergistic
insect control which comprises contacting said insect with a
synergistically effective amount of a neuronal sodium channel
antagonist in combination with one or more compounds selected from
the group consisting of pyrethroids, pyrethroid-type compounds,
recombinant nucleopolyhedroviruses capable of expressing an insect
toxin, organophosphates, carbamates, formamidines, macrocyclic
lactones, amidinohydrazones, GABA antagonists and acetylcholine
receptor ligands.
[0007] The present invention further provides a method for the
enhanced protection of plants from infestation and attack by
insects.
DETAILED DESCRIPTION OF THE INVENTION
Definitions
[0008] "Acetylcholine receptor ligand compound" as used in this
application means a compound which is capable of binding to the
acetylcholine receptor site.
[0009] "Group A" as used in this application means insecticidal
[0010] 1) pyrethroid compounds; [0011] 2) pyrethroid-type
compounds; [0012] 3) recombinant nucleopolyhedroviruses capable of
expressing an insect toxin; [0013] 4) organophosphate compounds;
[0014] 5) carbamate compounds; [0015] 6) formamidine compounds;
[0016] 7) macrocyclic lactone compounds; [0017] 8) amidinohydrazone
compounds; [0018] 9) GABA antagonist compounds; and [0019] 10)
acetylcholine receptor ligand compounds.
[0020] "Haloalkyl" as used in this application means an alkyl group
C.sub.xH.sub.2x+1 having 1 to 2x+1 halogen atoms which may be the
same or different, Similarly, the terms "haloalkenyl",
"haloalkynyl", "haloalkoxy", "halophenyl" and the like mean mono-
to perhalogen substitution wherein the halogens may be the same or
different.
[0021] "Halogen" as used in this application means Cl, Br, I or
F.
[0022] "Neuronal sodium channel antagonist" as used in this
application means a compound which is capable of preventing the
ability of a neuron cell to transfer sodium ions across the cell
membrane.
[0023] "Pyrethroid-type compounds" as used in this application
means those compounds characterized by a non-ester linked
aryl-phenoxybenzyl moiety.
[0024] "Synergism" as used in this application means a cooperative
action encountered in a combination of two or more biologically
active components in which the combined activity of the two or more
components exceeds the sum of the activity of each component
alone.
[0025] Surprisingly, it has now been found that a composition which
comprises a combination of a neuronal sodium channel antagonist and
a second insecticidal ingredient provides superior insect control
at lower levels of the combined active agents than may be achieved
when the neuronal sodium channel antagonist or the second
insecticidal ingredient is applied alone.
[0026] As previously stated, the term neuronal sodium channel
antagonist designates a compound which is capable of preventing the
ability of a neuron cell to transfer sodium ions across the cell
membrane. A neuron cell thus affected is unable to fire, resulting
in paralysis, and ultimately mortality, in the target host.
Descriptions of neuronal sodium channel antagonists and their mode
of action may be found in Pesticide Biochemistry and Physiology,
60: 177-185 or Archives of Insect Biochemistry and Physiology, 37:
91-103.
[0027] Neuronal sodium channel antagonists include compounds such
as those described in U.S. Pat. No. 5,543,573; U.S. Pat. No.
5,708,170; U.S. Pat. No. 5,324,837 and U.S. Pat. No. 5,462,938,
(the description of which are hereby incorporated by reference)
among other publications. Exemplary of the neuronal sodium channel
antagonist compounds useful in the composition of this invention
are those compounds having the structural formula
##STR00001##
wherein [0028] A is CR.sub.4R.sub.5 or NR.sub.6; [0029] W is O or
S; [0030] X, Y, Z, X', Y' and Z' are each independently H; halogen;
OH; CN; NO.sub.2; C.sub.1-C.sub.6alkyl optionally substituted with
one or more halogen, C.sub.1-C.sub.3alkoxy,
C.sub.1-C.sub.3haloalkoxy, C.sub.3-C.sub.6cycloalkyl,
C.sub.2-C.sub.6alkenyloxy or sulfonyloxy groups; [0031]
C.sub.1-C.sub.6alkoxy optionally substituted with one or more
halogen, C.sub.1-C.sub.3alkoxy or C.sub.3-C.sub.6cycloalkyl groups;
[0032] C.sub.1-C.sub.6alkoxycarbonyl,
C.sub.3-C.sub.6cycloalkylcarbonyloxy, phenyl optionally substituted
with one or more halogen, C.sub.1-C.sub.4alkyl, or
C.sub.1-C.sub.4alkoxy groups; [0033] aminocarbonyloxy optionally
substituted with one or more C.sub.1-C.sub.3alkyl groups; [0034]
C.sub.1-C.sub.6alkoxycarbonyloxy; C.sub.1-C.sub.6alkylsulfonyloxy;
C.sub.2-C.sub.6alkenyl; or NR.sub.12R.sub.13; [0035] m, p and q are
each independently an integer of 1, 2, 3, 4, or 5; [0036] n is an
integer of 0, 1 or 2; [0037] r is an integer of 1 or 2; [0038] t is
an integer of 1, 2, 3 or 4; [0039] R, R.sub.1, R.sub.2, R.sub.3,
R.sub.4 and R.sub.5 are each independently H or
C.sub.1-C.sub.4alkyl; [0040] R.sub.6 is H, C.sub.1-C.sub.6alkyl,
C.sub.1-C.sub.6haloalkyl, C.sub.1-C.sub.6alkoxyalkyl,
C.sub.1-C.sub.6alkoxy, C.sub.1-C.sub.6haloalkoxy,
C.sub.2-C.sub.6alkenyl, C.sub.2-C.sub.6alkynyl,
C.sub.1-C.sub.6alkylcarbonyl, C.sub.1-C.sub.6alkoxycarbonyl,
C.sub.1-C.sub.6alkylthio, or C.sub.1-C.sub.6haloalkylthio; [0041]
R.sub.7 and R.sub.8 are each independently H; halogen; [0042]
C.sub.1-C.sub.6alkyl; C.sub.1-C.sub.6alkylcarbonyloxy; or phenyl
optionally substituted with one or more halogen, CN, NO.sub.2,
C.sub.1-C.sub.6alkyl, C.sub.2-C.sub.6haloalkyl,
C.sub.1-C.sub.6alkoxy or C.sub.1-C.sub.6haloalkoxy groups; [0043]
R.sub.9 and R.sub.10 are each independently H, or
C.sub.1-C.sub.4alkyl; [0044] R.sub.11 is H, C.sub.1-C.sub.6alkyl,
C.sub.1-C.sub.6haloalkyl, C.sub.1-C.sub.4alkylcarbonyl,
C.sub.1-C.sub.6alkoxycarbonyl, or
C.sub.1-C.sub.6haloalkoxycarbonyl; [0045] R.sub.12 and R.sub.13 are
each independently H or C.sub.1-C.sub.6alkyl; [0046] G is H;
C.sub.1-C.sub.6alkyl optionally substituted with one or more
halogen, C.sub.1-C.sub.4alkoxy, C.sub.1-C.sub.6haloalkoxy, CN,
NO.sub.2S(O).sub.uR.sub.14, COR.sub.15, CO.sub.2R.sub.16, phenyl or
C.sub.3-C.sub.6cycloalkyl groups; [0047] C.sub.1-C.sub.6alkoxy;
C.sub.1-C.sub.6haloalkoxy; CN; NO.sub.2; S(O).sub.uR.sub.17;
COR.sub.18; CO.sub.2R.sub.19; phenyl optionally substituted with
one or more halogen, CN, C.sub.1-C.sub.3haloalkyl, or
C.sub.1-C.sub.3haloalkoxy groups; [0048] C.sub.3-C.sub.6cycloalkyl;
or phenylthio; [0049] Q is phenyl optionally substituted with one
or more halogen, CN, SCN, NO.sub.2, S(O).sub.uR.sub.20,
C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4haloalkyl,
C.sub.1-C.sub.4alkoxyalkyl, C.sub.1-C.sub.6alkoxy,
C.sub.1-C.sub.6haloalkoxy, or NR.sub.21R.sub.22 groups; [0050] u is
an integer of 0, 1 or 2; [0051] R.sub.14, R.sub.15, R.sub.16,
R.sub.18, R.sub.19, R.sub.21 and R.sub.22 are each independently H
or C.sub.1-C.sub.6alkyl; [0052] R.sub.17 and R.sub.20 are each
independently C.sub.1-C.sub.6alkyl or C.sub.1-C.sub.6haloalkyl;
[0053] R.sub.33 is CO.sub.2R.sub.34; [0054] R.sub.34 is H,
C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.6haloalkyl, phenyl or
halophenyl; and the dotted line configuration [0055] CN represents
a double bond or a single bond (i.e. C--N or C.dbd.N); or a
stereoisomer thereof.
[0056] Preferred neuronal sodium channel antagonists suitable for
use in the composition of the invention are those compounds of
formula I, II or III wherein the dotted line configuration CN
represents a double bond.
[0057] More preferred neuronal sodium channel antagonists suitable
for use in the inventive composition are those compounds of formula
I or formula III wherein the dotted line configuration represents a
double bond.
[0058] Particularly preferred neuronal sodium channel antagonists
useful in the composition of the invention are those compounds of
formula I or formula III wherein W is O; X is trifluoromethoxy and
is in the 4-position; Y is trifluoromethyl and is in the
3-position; Z is CN and is in the 4-position; A is CH.sub.2; n is
0; m, p and q are each 1; R and R.sub.1 are each H; Z, is C.sub.l;
R.sub.33 and G are each CO.sub.2CH.sub.3; Q is
p-(trifluoromethoxy)phenyl; and the dotted line configuration CN
represents a double bond; or a stereoisomer thereof.
[0059] Further neuronal sodium channel antagonist compounds include
those described in U.S. Pat. No. 5,116,850 and U.S. Pat. No.
5,304,573, (the description of which are hereby incorporated by
reference) among other publications. Exemplary of further neuronal
sodium channel antagonist compounds suitable for use in the
composition of the invention are those compounds having structural
formula
##STR00002##
wherein [0060] W is O or S; [0061] X'' and Y'' are each
independently H; halogen; CN; SCN; C.sub.1-C.sub.6alkyl optionally
substituted with one or more halogen, NO.sub.2, CN,
C.sub.1-C.sub.4alkoxy, C.sub.1-C.sub.4alkylthio, phenyl,
halophenyl, C.sub.1-C.sub.4alkylsulfonyl,
C.sub.1-C.sub.4haloalkylsulfonyl, or C.sub.1-C.sub.4alkoxycarbonyl
groups; [0062] C.sub.2-C.sub.4alkenyl; C.sub.2-C.sub.4haloalkenyl;
C.sub.2-C.sub.4alkynyl; C.sub.2-C.sub.4haloalkynyl;
C.sub.3-C.sub.6cycloalkyl; C.sub.3-C.sub.6halocycloalkyl; phenyl
optionally substituted with one or more halogen, CN, NO.sub.2,
C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4haloalkyl,
C.sub.1-C.sub.4alkoxy, C.sub.1-C.sub.4haloalkoxy,
C.sub.1-C.sub.4alkylthio, C.sub.1-C.sub.4alkylsulfonyl or
C.sub.1-C.sub.4haloalkylsulfonyl groups; [0063]
C.sub.1-C.sub.4alkylcarbonyl; C.sub.1-C.sub.4haloalkylcarbonyl; or
NR.sub.28R.sub.29; [0064] m is an integer of 1, 2, 3, 4 or 5;
[0065] G' is phenyl optionally substituted with one or more groups
which may be the same or different selected from X''; [0066] a
5-membered heteroaromatic ring containing one or two heteroatoms
selected from 0 or 1 oxygen, 0 or 1 sulfur and 0, 1 or 2 nitrogen
atoms said 5-membered heteroaromatic ring being attached via carbon
and being optionally substituted with one or more groups which may
be the same or different selected from X''; or [0067] a 6-membered
heteroaromatic ring containing one or two heteroatoms selected from
0 or 1 oxygen, 0 or 1 sulfur and 0, 1 or 2 nitrogen atoms said
6-membered heteroaromatic ring being attached via carbon and being
optionally substituted with one or more groups which may be the
same or different selected from X''; [0068] Q' is H;
C.sub.1-C.sub.6alkyl optionally substituted with one or more
halogen, CN, C.sub.1-C.sub.3alkoxy, C.sub.1-C.sub.6alkoxycarbonyl,
or phenyl optionally substituted with one or more halogen, CN,
NO.sub.2, C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4haloalkyl,
C.sub.1-C.sub.4alkylsulfonyl or C.sub.1-C.sub.4alkylsulfinyl
groups; [0069] C.sub.2-C.sub.6alkenyl; C.sub.2-C.sub.6alkynyl; or
phenyl optionally substituted with one to three groups, which may
be the same or different, selected from X''; [0070] R.sub.23,
R.sub.24, R.sub.25, R.sub.26, R.sub.27, R.sub.28 and R.sub.29 are
each independently H or C.sub.1-C.sub.4alkyl; and the dotted line
configuration CN represents a double bond or a single bond (i.e.
C--N or C.dbd.N); or a stereoisomer thereof.
[0071] Further preferred neuronal sodium channel antagonist
compounds of the invention are those compounds of formula IV or V
wherein the dotted line configuration CN represents a double
bond.
[0072] Other preferred neuronal sodium channel antagonist compounds
suitable for use in the composition of the invention are those
compounds of formula IV or V wherein W is 0; X'' and Y'' are each
independently H or C.sub.1-C.sub.6haloalkyl; m is 1; R.sub.23,
R.sub.24, R.sub.25, R.sub.26 and R.sub.27 are each H; G is phenyl
optionally substituted with one or more halogen atoms; Q' is
halophenyl or C.sub.1-C.sub.4alkyl optionally substituted with one
phenyl or halophenyl group; and the dotted line configuration CN
represents a double bond; or a stereoisomer thereof.
[0073] The second active ingredient of the insecticidal composition
of the invention includes one or more compounds selected from Group
A:
[0074] 1) pyrethroid compounds which are known to be insecticidally
active such as cypermethrin, cyhalothrin, cyfluthrin, permethrin or
the like;
[0075] 2) pyrethroid-type compounds which are known to be
insecticidally active such as ethofenprox, silafluofen, or the
like;
[0076] 3) recombinant nucleopolyhedroviruses capable of expressing
an insect toxin, preferably an insect neurotoxin such as
Androctonus australis insect toxin (AaIT), for example
HzNPV-AaIT;
[0077] 4) organophosphate compounds which are known to be
insecticidally active such as profenofos, acephate, sulprofos,
malathion, diazinon, methyl parathion, terbufos, or the like;
[0078] 5) carbamate compounds which are known to be insecticidally
active such as methomyl, thiodicarb, fenothiocarb, or the like;
[0079] 6) formamidine compounds which are known to be
insecticidally active such as amitraz, chlordimeform,
chlorfenamidine, or the like;
[0080] 7) macrocyclic lactone compounds which are known to be
insecticidally active such as spinosad, avermectin, emamectin,
milbemectin, nemadectin, moxidectin or the like;
[0081] 8) amidinohydrazone compounds which are known to be
insecticidally active such as hydramethylnon;
[0082] 9) GABA antagonist compounds which are known to be
insecticidally effective such as fipronil, endosulfan, or the
like;
[0083] 10) acetylcholine receptor ligand compounds which are known
to be insecticidally effective such as imidacloprid, acetamiprid,
nitenpyram, thiamethoxam, or the like.
[0084] Descriptions of the above-listed commercially available
compounds may be found in The Pesticide Manual, 11th Edition,
British Crop Protection Council (1997) among other publications.
Descriptions of recombinant nucleopolyhedroviruses capable of
expressing an insect toxin include Treacy et al, Proceedings
Beltwide Cotton Conference (1999), pp 1076-1083.
[0085] Preferred compositions of the invention are those
compositions having a neuronal sodium channel antagonist compound
of formula I or formula III in combination with one or more
compounds selected from Group A.
[0086] More preferred compositions of the invention are those
compositions having a formula I or formula III compound wherein W
is O; X is trifluoromethoxy and is in the 4-position; Y is
trifluoromethyl and is in the 3-position; Z is CN and is in the
4-position; A is CH.sub.3; n is 0; m, p and q are each
independently 1; R and R.sub.1 are each independently H; Z' is Cl;
R.sub.33 and G are each independently CO.sub.2CH.sub.3; Q is
p-(trifluoromethoxy)phenyl; and the dotted line configuration CN
represents a double bond in combination with one or more compounds
selected from Group A.
[0087] Each of the compounds of formula I, II, III, IV and V embody
assymetric centers which may be represented in the stereoisomeric
R-form or S-form. The present invention also includes the R-form,
the S-form or mixtures comprising the R-form and the S-form in an
arbitrary ratio. For compounds of formula III, the S-form is
preferred.
[0088] Advantageously, the neuronal sodium-channel antagonist
compound of formula I, II, III, IV or V or a mixture thereof may be
formulated with a second insecticidally effective ingredient and
optionally other customary formulation adjuvants. Said formulation
may be dispersed in a solid or liquid diluent for application to
the insect, its food supply, breeding ground or habitat as a dilute
spray or as a solid dust or dust concentrate.
[0089] The active ingredients of the inventive composition may also
be formulated separately as a wettable powder, emulsifiable
concentrate, aqueous or liquid flowable, suspension concentrate or
any one of the conventional formulations used for insect control
agents and tank-mixed in the field with water or other inexpensive
liquid for application as a liquid spray mixture. The separately
formulated compositions may also be applied sequentially.
[0090] Advantageously, the composition of the invention may be
formulated as a bait composition comprising a synergistically
effective amount of a combination of a neuronal sodium channel
antagonist plus one or more compounds selected from Group A and a
solid or liquid edible nutritive substance. A preferred bait
composition may contain by weight about 0.01% to 20% active
ingredients, preferably a neuronal sodium channel antagonist in
combination with hydramethylnon.
[0091] In actual practice, the composition of the invention may be
applied to the plant foliage or plant stem or to the insect habitat
or to the locus of a hygienic pest as a dilute spray prepared from
any of the above-said formulations. The ratio of the essential
active ingredients of the composition of the invention is about 1
weight part of a neuronal sodium channel antagonist to about
0.01-100 weight parts of one or more compounds selected from Group
A.
[0092] The compositions of the invention are superior insecticidal
compositions and are especially useful for the control of
agrohorticultural pests, hygienic pests or wood-eating pests. Said
compositions are highly effective for the protection of growing and
harvested plants including: leguminous crops such as soybeans, snap
beans, peas, wax beans and the like as well as cotton, forage
crops, cole crops, leafy vegetables, tobacco, hops, tomatoes,
potatoes, flowering ornamentals such as chrysanthemums, vine crops
such as grapes, squash, pumpkin or melon and fruit trees such as
cherry, peach, apple or citrus, from the ravages of insects.
[0093] The synergistic insecticidal composition of the invention is
found to be highly active against a wide variety of lepidopteran
and coleopteran insects such as Helicoverpa zea (cotton bollworm),
Heliothis virescens (tobacco budworm), Leptinotarsa decemlineata
(Colorado potato beetle), Diabrotica spp. (corn rootworm) and the
like.
[0094] Beneficially, the composition of the invention may be useful
for the prevention and control of hygienic or public health pests
such as: Diptera, e.g. houseflies, mosquitoes, or the like;
Hymenoptera, e.g. ants, parasitic wasps, wasps or the like;
Blattaria, e.g. cockroaches; or the like.
[0095] Further, the compositions of the invention may be
particularly useful for the prevention and control of wood-eating
insects such as termites (Isoptera), carpenter ants (Hymenoptera),
wood-destroying beetles (Coleoptera) or the like.
[0096] These and other advantages of the invention may become more
apparent from the examples set forth herein below. These examples
are provided merely as illustrations of the invention and are not
intended to be construed as a limitation thereof.
EXAMPLE 1
Evaluation of the Synerqistic Insecticidal Effect of a Combination
of a Neuronal Sodium Channel Antagonist Plus a Second
Insecticide
[0097] In this evaluation, Heliothis zea (cotton bollworm),
Heliothis virescens (tobacco budworm) and pyrethroid-resistant
Heliothis virescens larvae used are obtained from laboratory
colonies. Pyrethroid-resistant H. virescens are derived from the
PEG-strain [Campannola & Plapp, Proceedings of Beltwide Cotton
Conference (1988)].
[0098] Cotton leaves are immersed in 1:1 v/v, acetone/water
solutions of test compound, or solutions of a combination of test
compounds for a period of about 3 seconds. Following immersion,
leaves are allowed to air-dry for 2-3 hours. Plastic bioassay trays
containing multiple open-faced wells (4.0.times.4.0.times.2.5 cm)
are used as the test arenas. Cut portions of a treated leaf, a
moistened cotton dental wick and a single third-instar larva are
placed into each well, covered with an adhesive vented clear
plastic sheet and held under constant fluorescent light at about
27.degree. C. for a predetermined period of time. Larval
mortality/morbidity is evaluated at 5 days after treatment. All
treatments are replicated 4-5 fold in a randomized complete block
design with 16-32 larvae per treatment. Using conventional
log-probit analysis, the LC.sub.50 of each treatment is
determined.
[0099] Using the above protocol, a neuronal sodium channel
antagonist (Compound A) may be evaluated alone at dose rates of 0.1
ppm, 1.0 ppm and 10.0 ppm and in combination with 1.0 ppm of a
second insecticidal compound. Treatments which may be used are
shown in Table I.
TABLE-US-00001 TABLE I Second Dose Compound A1 Active Rate Dose
Rate Compound (ppm) (ppm) (ppm) (ppm) (ppm) cypermethrin 0 0 0.1
1.0 10.0 1.0 0 0.1 1.0 10.0 amitraz 0 0 0.1 1.0 10.0 1.0 0 0.1 1.0
10.0 fipronil 0 0 0.1 1.0 10.0 1.0 0 0.1 1.0 10.0 acetamiprid 0 0
0.1 1.0 10.0 1.0 0 0.1 1.0 10.0 spinsad 0 0 0.1 1.0 10.0 1.0 0 0.1
1.0 10.0 thiodicarb 0 0 0.1 1.0 10.0 1.0 0 0.1 1.0 10.0 1Compound A
= formula Ia neuronal sodium channel antagonist ##STR00003##
EXAMPLE 2
Evaluation of the Synersistic Insecticidal Effect of a Combination
of a Neuronal Sodium Channel Antagonist Plus an
Amidinohydrazone
[0100] In this evaluation, adult male German cockroaches (Blattella
germanica) are used. For each test, a 4.0 g portion of ground
Purina Dog Chow (Hi-Pro Glo.RTM.) is treated with an acetone
solution of test compound alone or in combination with a second
test compound. After treatment, the acetone is evaporated and the
treated dog chow is placed in a 3/4 oz plastic cup which is placed
in a harborage made of folded sheets of blotter paper placed in a
plastic box (16'' L.times.11'' W.times.6'' H). The plastic box
(test arena) is also fitted with a 1 oz narrow mouth bottle with 2
dental wicks inserted at the mouth. A control box is prepared in
the same manner using ground dog chow which has been treated with
reagent grade acetone. Each treatment is replicated three times.
Into each test arena are placed 20 healthy adult male cockroaches
which have been reared in an insectary. The test arenas are then
stored at 76.degree. F. and mortality is determined daily by visual
examination. The data obtained are shown in Table 11.
TABLE-US-00002 TABLE II Test % Mortality Com- % Active Days After
Treatment pound Ingredient 3 4 5 6 7 8 A.sup.1 0.05 0 0 0 0 0 0 A
0.10 1.7 11.7 11.7 11.7 18.3 18.3 A 0.50 5.0 5.0 5.0 5.0 5.0 5.0
B.sup.2 1.00 0 5.0 28.3 71.7 90.0 93.3 A + B 0.05 + 1.0 0 20.0 41.7
81.7 95.0 98.3 A + B 0.10 + 1.0 0 21.7 51.7 88.3 95.0 95.0 A + B
0.50 + 1.0 16.7 58.3 80.0 95.0 98.3 100.0 Control 0 0 1.7 3.3 3.3
3.3 5.0 .sup.1Compound A = formula Ia neuronal sodium channel
antagonist .sup.2Compound B = hydramethylnon ##STR00004##
[0101] As can be seen from the data shown in Table II, combinations
of a neuronal sodium channel antagonist plus an amidinohydrazone
insecticide demonstrate synergistic insect control.
EXAMPLE 3
Evaluation of the Synergistic Insecticidal Effect of a Combination
of a Neuronal Sodium Channel Antagonist Plus a Recombinant
Nucleopolyhedrovirus Capable of Expressing an Insect Toxin
[0102] In this evaluation, Helicoverpa zea (cotton bollworm) larvae
are obtained from a laboratory colony. Test compounds are dissolved
in 1:1 v/v acetone/water. Plastic bioassay trays (C-D
International, Pitman, N.J.) are used as test arenas. Each tray
contains 32 open-faced wells, 4.0.times.4.0.times.2.5 cm. A portion
(5 ml) of a wheat germ-soybean flour-based artificial diet
(Southland Products, Lake Village, Ark.) is poured into each well.
After the diet hardened, 0.4 ml of test solution is pipetted onto
the diet surface in each well. Test solutions are evenly spread
over surfaces of diet by picking up the tray and gently tilting it
from side to side. Trays are then held in a vented area for about 2
h, until water is no longer pooled on diet surfaces. A single
4-day-old H. zea larva is then placed on the surface of diet in
each well. After larval infestation, each well is covered with an
adhesive, vented, clear plastic sheet.
[0103] All test arenas are held under constant fluorescent light
and a temperature of about 27.degree. C. for duration of the assay.
Larval mortality is determined at 2, 3, 4 and 7 days after
treatment. A larva was considered to be dead if it exhibited little
to no movement, even after being shaken in the diet tray. A total
of 32 insects were tested for each treatment. The data obtained are
shown in Table III.
TABLE-US-00003 TABLE III Test Conc. of % Mortality Com- Active Days
After Treatment pound Ingredient 2 3 4 7 A.sup.1 0.1 ppm 43.8 46.9
53.1 53.1 B.sup.2 1000 OB.sup.3/ml 3.1 34.4 50.5 62.5 B 500 OB/ml
0.0 9.4 18.8 40.6 B 100 OB/ml 3.1 3.1 3.1 15.6 A + B 0.1 + 1000
87.5 90.6 93.8 96.9 A + B 0.1 + 500 75.0 78.1 84.4 87.5 A + B 0.1 +
100 62.5 75.0 75.0 78.1 Control 0 3.1 3.1 3.1 3.1 .sup.1Compound A
= formula Ia neuronal sodium channel antagonist .sup.2Compound B =
HzNPV-AaIT, Helicoverpa zea Nucleopolyhedrovirus which expresses
Androctonus australis insect toxin .sup.3OB = viral occlusion
bodies ##STR00005##
[0104] As can be seen from the data shown in Table III,
combinations of a neuronal sodium channel antagonist plus a
recombinant nucleopolyhedrovirus which is capable of expressing an
insect toxin demonstrate synergistic insect control.
* * * * *