U.S. patent application number 11/261595 was filed with the patent office on 2006-06-01 for synergistic and residual pesticidal compositions containing plant essential oils with enzyme inhibitors.
This patent application is currently assigned to EcoSmart Technologies, Inc.. Invention is credited to Steven M. Bessette.
Application Number | 20060115507 11/261595 |
Document ID | / |
Family ID | 23333169 |
Filed Date | 2006-06-01 |
United States Patent
Application |
20060115507 |
Kind Code |
A1 |
Bessette; Steven M. |
June 1, 2006 |
Synergistic and residual pesticidal compositions containing plant
essential oils with enzyme inhibitors
Abstract
Synergistic and residual pesticidal compositions containing
synergistic and residual mixtures of plant essential oils in
admixture with enzyme inhibitors, with or without other compounds
not previously used as active ingredients in pesticidal
formulations. In addition, the present invention is directed to a
method for controlling pests by applying a pesticidally-effective
amount of the above synergistic and residual pesticidal
compositions to a locus where pest control is desired.
Inventors: |
Bessette; Steven M.;
(Brentwood, TN) |
Correspondence
Address: |
NIXON & VANDERHYE, PC
901 NORTH GLEBE ROAD, 11TH FLOOR
ARLINGTON
VA
22203
US
|
Assignee: |
EcoSmart Technologies, Inc.
Franklin
TN
|
Family ID: |
23333169 |
Appl. No.: |
11/261595 |
Filed: |
October 31, 2005 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
09340391 |
Jun 28, 1999 |
6986898 |
|
|
11261595 |
Oct 31, 2005 |
|
|
|
Current U.S.
Class: |
424/406 ;
424/745 |
Current CPC
Class: |
A01N 31/04 20130101;
A01N 31/04 20130101; A01N 31/16 20130101; A01N 37/32 20130101; A01N
31/04 20130101; A01N 31/08 20130101; A01N 31/16 20130101; A01N
31/04 20130101; A01N 37/08 20130101; A01N 65/12 20130101; A01N
31/08 20130101; A01N 31/16 20130101; A01N 31/08 20130101; A01N
65/00 20130101; A01N 37/12 20130101; A01N 31/16 20130101; A01N
43/16 20130101; A01N 65/12 20130101; A01N 65/12 20130101; A01N
65/00 20130101; A01N 37/12 20130101; A01N 65/00 20130101; A01N
2300/00 20130101; A01N 35/02 20130101; A01N 37/08 20130101; A01N
43/30 20130101; A01N 37/32 20130101; A01N 37/32 20130101; A01N
43/30 20130101 |
Class at
Publication: |
424/406 ;
424/745 |
International
Class: |
A01N 25/32 20060101
A01N025/32; A01N 65/00 20060101 A01N065/00 |
Claims
1.-17. (canceled)
18. A pesticidal composition comprising: an inert carrier and a
pesticidally-effective active ingredient, wherein the active
ingredient consists of piperonyl butoxide and at least one plant
essential oil compound selected from the group consisting of thyme
oil and thymol, with the proviso that no other pesticidally active
ingredient is present.
19. The pesticidal composition of claim 18, wherein the plant
essential oil compound is thyme oil.
20. The pesticidal composition of claim 18 wherein the plant
essential oil compound is thymol.
21. The pesticidal composition of claim 18, wherein the piperonyl
butoxide and plant essential oil compound are present in a ratio of
about 1:2 parts by weight.
22. A method for killing or controlling a pest, comprising:
applying a pesticidally effective amount of the composition of
claim 18 to a locus where killing or control of pests is
desired.
23. The method of claim 22, wherein the pest is a cockroach.
Description
CROSS-REFERENCES TO RELATED APPLICATIONS
[0001] This application is a divisional of U.S. application Ser.
No.09/340,391, filed Jun. 28, 1999, the entire disclosure of which
is incorporated herein by reference.
FIELD OF THE INVENTION
[0002] The present invention relates, in general, to synergistic
and residual pesticidal compositions containing plant essential
oils and/or derivatives thereof with enzyme inhibitors. In one
aspect, the present invention relates to synergistic pesticidal
compositions containing one or more plant essential oils and/or
derivatives thereof in admixture with enzyme inhibitors. In another
aspect, the present invention relates to residual pesticidal
compositions containing one or more plant essential oils and/or
derivatives thereof in admixture with enzyme inhibitors. In still
another aspect, the present invention relates to synergistic and
residual pesticidal compositions containing one or more plant
essential oils and/or derivatives thereof in admixture with enzyme
inhibitors and other synergists. In a further aspect, the present
invention relates to a method for controlling pests by the
application of pesticidally effective amounts of the synergistic
and residual pesticidal compositions to a locus where pest control
is desired.
BACKGROUND OF THE INVENTION
[0003] Pests (invertebrates, insects, arachnids, larvae thereof,
etc.) are annoying to humans for a myriad of reasons. They have
annually cost humans billions of dollars in crop losses and in the
expense of keeping them under control. For example, the losses
caused by pests in agricultural environments include decreased crop
yield, reduced crop quality, and increased harvesting costs.
[0004] Over the years, synthetic chemical pesticides have provided
an effective means of pest control. For example, one approach
teaches the use of complex, organic insecticides, such as disclosed
in U.S. Pat. Nos. 4,376,784 and 4,308,279. Other approaches employ
absorbent organic polymers for widespread dehydration of the
insects. See, U.S. Pat. Nos. 4,985,251; 4,983,390; 4,818,534; and
4,983,389. Use of inorganic salts as components of pesticides has
also been tried, as disclosed in U.S. Pat. Nos. 2,423,284 and
4,948,013, European Patent Application No. 462 347, Chemical
Abstracts 1 19(5):43357q (1993) and Farm Chemicals Handbook, page
c102 (1987).
[0005] However, it has become increasingly apparent that the
widespread use of synthetic chemical pesticides has caused
detrimental environmental effects that are harmful to humans and
other animals. For instance, the public has become concerned about
the amount of residual chemicals that persist in food, ground water
and the environment, and that are toxic, carcinogenic or otherwise
incompatible to humans, domestic animals and/or fish. Moreover,
some target pests have even shown an ability to develop immunity to
many commonly used synthetic chemical pesticides. In recent times,
regulatory guidelines have encouraged a search for potentially less
dangerous pesticidal compositions via stringent restrictions on the
use of certain synthetic pesticides. As a result, elimination of
effective pesticides from the market has limited economical and
effective options for controlling pests. As an alternative,
botanical pesticides are of great interest because they are natural
pesticides, i.e., toxicants derived from plants that are safe to
humans and the environment. Historically, botanical pesticides,
such as tobacco, pyrethrum, derris, hellebore, quassia, camphor and
turpentine, have long been used. Of the botanical pesticides,
pyrethrum (also known as pyrethrum, Caucasian pyrethrum, dalmatic
pyrethrum, pesticide chrysanthemum, natural pyrethrum and
pyrethrin) has found widespread use.
[0006] Pyrethrum, which is extracted from the flowers of a
chrysanthemum grown in Kenya and Ecuador, acts on insects with
phenomenal speed causing immediate paralysis, while at the same
time exhibits negligible toxic effects on humans and warm-blooded
animals. Use of pyrethrum for industrial or agricultural
applications, however, is disadvantageous in that they require
frequent treatments because they become volatile when in contact
with water and readily decompose when exposed to direct sunlight
light. Pyrethrums are also neurotoxic to cold-blooded animals, such
as fishes, snakes, etc. Moreover, the supply of pyrethrums is
limited and substantial processing is required to bring the natural
product to market, and large-scale production of pyrethrum is very
expensive and unless pyrethrum is formulated with a synergist, most
initially paralyzed insects recover to once again become pests.
[0007] Synergists are compounds that, although typically possessing
no direct toxic effect at the dosage employed, are able to
substantially enhance the observed toxicity of a pesticide with
which they are combined. Synergists are found in most all
household, livestock and pet aerosols to enhance the action of the
fast knockdown pesticides, e.g., pyrethrum, allethrin, and
resmethrin, against flying insects. Synergists are required in
pesticidal formulations containing pyrethrum, for example, because
target insects produce an enzyme (cytochrome P-450) that attacks
pyrethrum and breaks it down, thereby making it effective in
knocking an insect down, but ineffective for killing in many cases.
As such, these synergists act by inhibiting P-450 dependent
polysubstrate monooxygenases enzymes (PSMOs) produced by
microsomes, which are subcellular units found in the liver of
mammals and in some insect tissues that degrade pyrethrum and other
pesticidal compounds, such as pyrethrum, allethrin, resmethrin, and
the like. These synergists inhibit P-450 enzymes and other like
compounds that are part of the gene battery that comprise Phase I
and Phase II drug metabolizing enzymes.
[0008] Because pyrethrum is limited in availability and is very
expensive, the industry has turned to synthetic pyrethroids, which
are very photostable in sunlight and are generally effective
against most agricultural insect pests. Pyrethroids are not as safe
as pyrethrums, however, and disadvantageously persist in the
environment for longer periods. Further, many insects
disadvantageously develop resistance to pyrethroids.
[0009] Many natural products used as insecticides, including plant
essential oils, do not provide adequate control of pests in that
they either act very slowly or are not very stable and break down
quickly, thereby failing to provide quick knockdown of insects or
toxic residual properties. Even products such as pyrethrum,
although highly toxic to pests on contact when used properly in
pesticidal formulations, are not effective pesticides for many
applications because they lack residual properties, thereby
increasing the frequency and cost of pesticide applications, as
well as increased risk and exposure to the environment.
[0010] Accordingly, there is a great need for novel synergistic and
residual pesticidal compositions containing no level or
substantially lower levels of pyrethrum, chlorinated hydrocarbons,
organo phosphates, carbamates and the like. In addition, there is a
need for methods for using same that address the problems described
above, i.e., are safe to humans and the environment and relatively
inexpensive to use in obtaining acceptable levels of insect or pest
control.
SUMMARY OF THE INVENTION
[0011] A primary object of the present invention is to provide
novel pesticidal compositions that contain mixtures of one or more
plant essential oils and/or derivatives thereof, natural or
synthetic, with so-called Phase I and Phase II drug metabolizing
enzyme inhibitors.
[0012] Another object of the invention is to provide pesticidal
compositions containing synergistic mixtures or blends of plant
essential oils and/or derivatives thereof, natural or synthetic,
and other synergists with Phase I and Phase II drug metabolizing
enzyme inhibitors.
[0013] A further object of the present invention is to provide
novel, residual pesticidal compositions that contain admixtures of
certain compounds, natural or synthetic, with one or more plant
essential oils and/or derivatives thereof, natural or synthetic,
that act to residualize the toxic effects of pesticidal
compositions containing the plant essential oils.
[0014] It is also an object of the present invention to provide a
pesticidal composition and method for mechanically, physiologically
and/or neurally controlling pests, e.g., invertebrates, insects,
arachnids, larvae thereof, etc.
[0015] It is a further object to provide a safe, non-toxic
pesticidal composition and method that will not harm the
environment.
[0016] It is still another object to provide a pesticidal
composition and method that has a pleasant scent or is unscented,
and that can be applied without burdensome safety precautions.
[0017] It is still another object to provide a pesticidal
composition and method as described above which can be
inexpensively produced or employed.
[0018] It is yet another object of the invention to provide a
pesticidal composition and method to which pests cannot build
immunity and/or resistance.
[0019] The above and other objects are accomplished by the present
invention which is directed to synergistic and residual pesticidal
compositions comprising plant essential oils and/or derivatives
thereof, natural or synthetic, in admixture with Phase I and Phase
II drug metabolizing enzyme inhibitors, or synergistic and residual
pesticidal compositions comprising plant essential oils and Phase I
and Phase II drug metabolizing enzyme inhibitors in admixture with
other synergists. In addition, the present invention is directed to
a method for controlling pests by applying a pesticidally-effective
amount of the above synergistic and residual pesticidal
compositions to a locus where pest control is desired.
[0020] Additional objects and attendant advantages of the present
invention will be set forth, in part, in the description that
follows, or may be learned from practicing or using the present
invention. The objects and advantages may be realized and attained
by means of the instrumentalities and combinations particularly
recited in the appended claims. It is to be understood that the
foregoing general description and the following detailed
description are exemplary and explanatory only and are not to be
viewed as being restrictive of the invention, as claimed.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
[0021] All patents, patent applications and literatures cited in
this description are incorporated herein by reference in their
entirety. In the case of inconsistencies, the present disclosure,
including definitions, will prevail.
[0022] In one embodiment, the present invention provides a
synergistic and residual pesticidal composition comprising, in
admixture with a suitable carrier and optionally with a suitable
surface active agent, comprising one or more plant essential oil
compounds and derivatives thereof, natural or synthetic, including
racemic mixtures, enantiomers, diastereomers, hydrates, salts,
solvates and metabolites, etc. in admixture with an enzyme
inhibitor, such as, for example, piperonyl butoxide (PBO),
N-(2-ethylhexyl)-bicyclo-(2,2,1)hept-5-ene 2,2-dicarboximide (MGK
264), and sesamex. In a preferred embodiment, the enzyme inhibitor
is a P-450 enzyme inhibitor.
[0023] Each plant essential oil or derivative thereof, comprises a
monocyclic, carbocyclic ring structure having six-members and
substituted by at least one oxygenated or hydroxyl functional
moiety. Examples of plant essential oils encompassed within the
present invention, include, but are not limited to, members
selected from the group consisting of aldehyde C16 (pure),
.alpha.-terpineol, amyl cinnamic aldehyde, amyl salicylate, anisic
aldehyde, benzyl alcohol, benzyl acetate, cinnamaldehyde, cinnamic
alcohol, carvacrol, carveol, citral, citronellal, citronellol,
p-cymene, diethyl phthalate, dimethyl salicylate, dipropylene
glycol, eucalyptol (cineole), eugenol, iso-eugenol, galaxolide,
geraniol, guaiacol, ionone, menthol, methyl anthranilate, methyl
ionone, methyl salicylate, .alpha.-phellandrene, pennyroyal oil,
perillaldehyde, 1- or 2-phenyl ethyl alcohol, 1 - or 2-phenyl ethyl
propionate, piperonal, piperonyl acetate, piperonyl alcohol,
D-pulegone, terpinen-4-ol, terpinyl acetate, 4-tert butylcyclohexyl
acetate, thyme oil, thymol, metabolites of trans-anethole,
vanillin, ethyl vanillin, and the like. As these plant essential
oil compounds are known and used for other uses, they may be
prepared by a skilled artisan by employing known methods.
[0024] For example, in a preferred embodiment, the present
invention is directed to a synergistic pesticidal composition for
controlling household pests comprising benzyl alcohol and piperonyl
butoxide. Data below shows that this embodiment is highly
effective, i.e., exhibited increased toxicity, against American
cockroaches and carpenter ants compared to either the individual
plant essential oil or piperonyl butoxide used alone.
[0025] In another embodiment, the present invention encompasses
synergistic and residual pesticidal compositions comprising at
least one of the above plant essential oil compounds with piperonyl
butoxide, and a member selected from the group consisting of
pyrethrolone, allethrolone, chrysanthemic acid, chrysanthemyl
alcohol, chrysanthemate ester, cis-jasmone, tetrahydrofurfuryl
alcohol (THFA), Lavendustin A
(N-(2',5'-Dihydroxybenzyl)-N-(2''-hydroxybenzyl)-3-aminosalicylic
Acid (CAS No.: 125697-92-9)), and PD 98059,
(2'-amino-3'-methoxyflavone), in admixture with a suitable carrier
and optionally a suitable surface active agent.
[0026] It will be appreciated by the skilled artisan that the
synergistic and residual pesticidal compositions of the present
invention unexpectedly exhibit excellent pesticidal activities
using one or more plant essential oils, in lieu of pyrethrum, in
admixture with Phase I and Phase II drug metabolizing enzyme
inhibitors such as piperonyl butoxide, MGK 264 and/or sesamex.
Further, it will be appreciated by the skilled artisan that the
synergistic and residual pesticidal compositions of the present
invention unexpectedly exhibit pesticidal activity for extended
periods of time, (i.e. using natural compounds as residual
insecticides that in and of themselves provide little, if any,
residual pesticidal properties). Without wishing to be bound by the
following theories, it is believed that plant essential oils
antagonize a pest's nerve receptors or may act as Phase I and/or
Phase II drug metabolizing enzyme inhibitors themselves.
Alternatively, plant essential oils may act via an alternative mode
of action. Further, another possibility is that Phase I and/or
Phase II drug metabolizing enzyme inhibitors synergize the plant
essential oils, and may act to reduce the volatility of the natural
compounds. The Phase I and/or Phase II drug metabolizing enzyme
inhibitors may also increase energy levels within the insect's
metabolism, thereby synergizing the antagonistic action of
so-called octopamine affectors. In any event, the net effect of the
increased toxicity and synergized action of the inventive
synergistic composition disclosed herein is heretofore unknown and
unexpected.
[0027] Use of synergistic and residual pesticidal compositions of
the present invention generally results in 100% mortality on
contact, and provides residual toxic properties for at least two
weeks. As such, they are advantageously employed as pesticidal
agents in uses such as, without limitation, agriculture, organic
farming, households, professional pest control, pet bedding,
foliage application, underwater or submerged application, solid
treatment, soil incorporation application, seedling box treatment,
stalk injection and planting treatment, ornamentals, termites,
mosquitoes, fire ants, head lice, dust mites, etc.
[0028] With respect to plants, the synergistic and residual
pesticidal compositions resist weathering which includes wash-off
caused by rain, decomposition by ultra-violet light, oxidation, or
hydrolysis in the presence of moisture or, at least such
decomposition, oxidation and hydrolysis as would materially
decrease the desirable pesticidal characteristic of the synergistic
and residual compositions or impart undesirable characteristics to
the synergistic and residual compositions. The synergistic and
residual compositions are so chemically inert that they are
compatible with substantially any other constituents of the spray
schedule, and they may be used in the soil, upon the seeds, or the
roots of plants without injuring either the seeds or roots of
plants. They may also be used in combination with other
pesticidally active compounds.
[0029] The term "carrier" as used herein means an inert or fluid
material, which may be inorganic or organic and of synthetic or
natural origin, with which the active compound is mixed or
formulated to facilitate its application to the plant, seed, soil
or other object to be treated, or its storage, transport and/or
handling. In general, any of the materials customarily employed in
formulating pesticides, herbicides, or fungicides, are suitable.
The inventive synergistic and residual pesticidal compositions of
the present invention may be employed alone or in the form of
mixtures with such solid and/or liquid dispersible carrier vehicles
and/or other known compatible active agents, especially plant
protection agents, such as other pesticides, or acaricides,
nematicides, fungicides, bactericides, rodenticides, herbicides,
fertilizers, growth-regulating agents, etc., if desired, or in the
form of particular dosage preparations for specific application
made therefrom, such as solutions, emulsions, suspensions, powders,
pastes, and granules which are thus ready for use. The synergistic
and residual pesticidal compositions of the present invention can
be formulated or mixed with, if desired, conventional inert (i.e.
plant compatible or herbicidally inert) pesticide diluents or
extenders of the type usable in conventional pesticide formulations
or compositions, e.g. conventional pesticide dispersible carrier
vehicles such as gases, solutions, emulsions, suspensions,
emulsifiable concentrates, spray powders,.pastes, soluble powders,
dusting agents, granules, foams, pastes, tablets, aerosols, natural
and synthetic materials impregnated with active compounds,
microcapsules, coating compositions for use on seeds, and
formulations used with burning equipment, such as fumigating
cartridges, fumigating cans and fumigating coils, as well as ULV
cold mist and warm mist formulations, etc.
[0030] Formulations containing the synergistic and residual
compositions of the present invention may be prepared in any known
manner, for instance by extending the synergistic and residual
compositions with conventional pesticide dispersible liquid diluent
carriers and/or dispersible solid carriers optionally with the use
of carrier vehicle assistants, e.g. conventional pesticide
surface-active agents, including emulsifying agents and/or
dispersing agents, whereby, for example, in the case where water is
used as diluent, organic solvents may be added as auxiliary
solvents. Suitable liquid diluents or carriers include water,
petroleum distillates, or other liquid carriers with or without
surface active agents. The choice of dispersing and emulsifying
agents and the amount employed is dictated by the nature of the
composition and the ability of the agent to facilitate the
dispersion of the synergistic and residual compositions of the
present invention. Generally, it is desirable to use as little of
the agent as is possible, consistent with the desired dispersion of
the synergistic and residual compositions of the present invention
in the spray so that rain does not re-emulsify the synergistic and
residual compositions of the present invention after it is applied
to the plant and wash it off the plant. Non-ionic, anionic,
amphoteric, or cationic dispersing and emulsifying agents may be
employed, for example, the condensation products of alkylene oxides
with phenol and organic acids, alkyl aryl sulfonates, complex ether
alcohols, quaternary ammonium compounds, and the like.
[0031] Liquid concentrates may be prepared by dissolving a
composition of the present invention with a non-phytotoxic solvent
and dispersing the synergistic and residual compositions of the
present inventions in water with the acid of suitable surface
active emulsifying and dispersing agents. Examples of conventional
carrier vehicles for this purpose include, but are not limited to,
aerosol propellants which are gaseous at normal temperatures and
pressures, such as Freon; inert dispersible liquid diluent
carriers, including inert organic solvents, such as aromatic
hydrocarbons (e.g. benzene, toluene, xylene, alkyl naphthalenes,
etc.), halogenated especially chlorinated, aromatic hydrocarbons
(e.g. chloro-benzenes, etc.), cycloalkanes, (e.g. cyclohexane,
etc.). paraffins (e.g. petroleum or mineral oil fractions),
chlorinated aliphatic hydrocarbons (e.g. methylene chloride,
chloroethylenes, etc.), alcohols (e.g. methanol, ethanol, propanol,
butanol, glycol, etc.) as well as ethers and esters thereof (e.g.
glycol monomethyl ether, etc.), amines (e.g. ethanolamine, etc.),
amides (e.g. dimethyl formamide etc.) sulfoxides (e.g. dimethyl
sulfoxide, etc.), acetonitrile, ketones (e.g. acetone, methyl ethyl
ketone, methyl isobutyl ketone, cyclohexanone, etc.), and/or water;
as well as inert dispersible finely divided solid carriers such as
ground natural minerals (e.g. kaolins, clays, vermiculite, alumina,
silica, chalk, i.e. calcium carbonate, talc, attapulgite,
montmorillonite, kieselguhr, etc.) and ground synthetic minerals
(e.g. highly dispersed silicic acid, silicates, e.g. alkali
silicates, etc.).
[0032] Surface-active agents, i.e., conventional carrier vehicle
assistants, that may be employed with the present invention
include, without limitation, emulsifying agents, such as non-ionic
and/or anionic emulsifying agents (e.g. polyethylene oxide esters
of fatty acids, polyethylene oxide ethers of fatty alcohols, alkyl
sulfates, alkyl sulfonates, aryl sulfonates, albumin hydrolyzates,
etc. and especially alkyl arylpolyglycol ethers, magnesium
stearate, sodium oleate, etc.); and/or dispersing agents such as
lignin, sulfite waste liquors, methyl cellulose, etc.
[0033] In the preparation of wettable powders, dust or granulated
formulations, the active ingredient is dispersed in and on an
appropriately divided carrier. In the formulation of the wettable
powders the aforementioned dispersing agents as well as
lignosulfonates can be included. Dusts are admixtures of the
compositions with finely divided solids such as talc, attapulgite
clay, kieselguhr, pyrophyllite, chalk, diatomaceous earth,
vermiculite, calcium phosphates, calcium and magnesium carbonates,
sulfur, flours, and other organic and inorganic solids which acts
carriers for the pesticide. These finely divided solids preferably
have an average particle size of less than about 50 microns. A
typical dust formulation useful for controlling insects contains 1
part of synergistic and residual composition and 99 parts of
diatomaceous earth or vermiculite. Granules may comprise porous or
nonporous particles. The granule particles are relatively large, a
diameter of about 400-2500 microns typically. The particles are
either impregnated or coated with the inventive pesticidal
compositions from solution. Granules generally contain 0.05-15%,
preferably 0.5-5%, active ingredient as the pesticidally-effective
amount. Thus, the contemplated are formulations with solid carriers
or diluents such as bentonite, fullers earth, ground natural
minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite,
montmorillonite or diatomaceous earth, vermiculite, and ground
synthetic minerals, such as highly-dispersed silicic acid, alumina
and silicates, crushed and fractionated natural rocks such as
calcite, marble, pumice, sepiolite and dolomite, as well as
synthetic granules of inorganic and organic meals, and granules of
organic materials such as sawdust, coconut shells, corn cobs and
tobacco stalks. Adhesives, such as carboxymethyl cellulose, natural
and synthetic polymers, (such as gum arabic, polyvinyl alcohol and
polyvinyl acetate), and the like, may also be used in the
formulations in the form of powders, granules or emulsifiable
concentrations.
[0034] If desired, colorants such as inorganic pigments, for
example, iron oxide, titanium oxide and Prussian Blue, and organic
dyestuffs, such as alizarin dyestuffs, azo dyestuffs or metal
phthalocyanine dyestuffs, and trace elements, such as salts of
iron, manganese, boron, copper, cobalt, molybdenum and zinc may be
used.
[0035] If desired, volatile organic compounds suitable as the
fragrance ingredient for use in formulations for household or pet
applications, include, but are not limited to, amyl salicylate,
citronellol, citronelloxyacetaldehyde, cyclamen aldehyde,
citronellyl isobutyrate, coumarin, cyclohexyl acetate, cyclohexyl
butyrate, diethyl malonate, ethyl 2-acetyl-5-ketohexanoate,
isobornyl acetate, linalool, phenethyl alcohol, undecanol,
alpha-hexylcinnamaldehyde, 2-methylhexanol, hexalon,
phenylacetaldehyde, cis-3-hexen-1-ol, cyclamal, veronol, eugenol,
Lyral, Galaxolide, Citralva, musk ambrette, terpinyl acetate,
geraniol, alpha-damascone, alpha-methylionone, and the like.
Illustrative of volatile essential oils are oil of Bergamot, cedar
leaf, cedar wood, geranium, lavender, white cedar, sandalwood oil,
rose extract, violet extract, galbanum oil, and the like. Synthetic
types of organic fragrances are described in publications such as
U.S. Pat. Nos. 4,314,915; 4,411,829; and 4,434,306.
[0036] In commercial or agricultural applications, the present
invention encompasses carrier composition mixtures in which the
synergistic and residual compositions are present in an amount
substantially between about 0.01-95% by weight, and preferably
0.5-90% by weight, of the mixture, whereas carrier composition
mixtures suitable for direct application or field application
generally contemplate those in which the active compound is present
in an amount substantially between about 0.0001-10%, preferably
0.01-1%, by weight of the mixture. Thus, the present invention
contemplates over-all formulations that comprise mixtures of a
conventional dispersible carrier vehicle such as (1) a dispersible
inert finely divided carrier solid, and/or (2) a dispersible
carrier liquid such as an inert organic solvent and/or water,
preferably including a surface-active effective amount of a carrier
vehicle assistant, e.g. a surface-active agent, such as an
emulsifying agent and/or a dispersing agent, and an amount of the
active compound which is effective for the purpose in question and
which is generally between about 0.0001-95%, and preferably
0.01-95%, by weight of the mixture.
[0037] The synergistic and residual compositions can also be used
in accordance with so-called ultra-low-volume process, i.e. by
applying such compounds or by applying a liquid composition
containing the same, via very effective atomizing equipment, in
finely divided form, e.g. average particle diameter of from 50-100
microns, or even less, i.e. mist form, for example by airplane crop
spraying techniques. Only up to at most about a few liters/hectare
are needed. In this process it is possible to use highly
concentrated liquid compositions with said liquid carrier vehicles
containing from about 20 to 95% by weight of the synergistic and
residual compositions or even the 100% active substances alone,
e.g. about 20-100% by weight of the synergistic and residual
compositions. The mixture of active materials may be applied,
without limitation, in sufficient amounts so as to provide about
0.2 to 2 and preferably about 0.5 to 1.5 pounds of active materials
per acre. Moreover, the required amount of the synergistic and
residual composition contemplated herein may be applied per acre
treated in from 1 to 200 gallons or more of liquid carrier and/or
diluent or in from about 5 to 500 pounds of inert solid carrier
and/or diluent. The concentration in the liquid concentrate will
usually vary from about 10 to 95 percent by weight and in the solid
formulations from about 0.5 to 90 percent by weight. Satisfactory
sprays, dusts, or granules for general use contain from about 1/4
to 15 pounds of active synergistic and residual compositions per
acre.
[0038] Furthermore, the present invention encompasses methods for
killing, combating or controlling pests, which comprises applying
to at least one of correspondingly (a) such pests and (b) the
corresponding habitat thereof, i.e. the locus to be protected, e.g.
to a growing crop, to an area where a crop is to be grown or to a
domestic animal, a correspondingly combative, a pesticidally
effective amount, or toxic amount of the particular synergistic and
residual compositions of the invention alone or together with a
carrier as noted above. The instant formulations or compositions
may be applied in any suitable usual manner, for instance by
spraying, atomizing, vaporizing, scattering, dusting, watering,
squirting, sprinkling, pouring, fumigating, and the like. The
method for controlling insects comprises applying the inventive
composition, ordinarily in a formulation of one of the
aforementioned types, to a locus or area to be protected from the
insects, such as the foliage and/or the fruit of plants. The
compound, of course, is applied in an amount sufficient to effect
the desired action. This dosage is dependent upon many factors,
including the targeted pest, the carrier employed, the method and
conditions of the application, whether the formulation is present
at the locus in the form of an aerosol, or as a film, or as
discrete particles, the thickness of film or size of particles, and
the like. Proper consideration and resolution of these factors to
provide the necessary dosage of the active compound at the locus to
be protected are within the skill of those versed in the art. In
general, however, the effective dosage of the compound of this
invention at the locus to be protected-i.e., the dosage with which
the pest comes in contact-is of the order of 0.001 to 5.0% based on
the total weight of the formulation, though under some
circumstances the effective concentration will be as little as
0.0001% or as much as 20%, on the same basis.
[0039] The synergistic and residual pesticidal compositions and
methods of the present invention are effective against a wide
variety of pests and it will be understood that the pests
exemplified and evaluated in the working Examples herein is
representative of such a wider variety. For instance, the present
invention can be used to control pests that attack plants or
warm-blooded animals, stored products and fabrics. Representative
crop plants that can be so treated include, without limitation, are
cotton, corn, deciduous and citrus fruits, tomatoes, maize,
ornamental plants potatoes, rice, soybean, sugar beets, tobacco,
wheat, etc. Representative animals that can be protected or treated
by the present invention include, without limitation, man, horses,
dogs, cats, cattle, sheep, goats, hogs, etc. Representative stored
products that can be protected from pest attack by the present
invention include, without limitation, grains, flour and flour
products, tobacco and tobacco products, processed foods, cereals
and the like. Representative fabrics that can be protected from
pest attack by the invention are wool, cotton, silk, linen and the
like.
[0040] The composition and method of the present invention will be
further illustrated in the following, non-limiting Examples. The
Examples are illustrative of various embodiments only and do not
limit the claimed invention regarding the materials, conditions,
weight ratios, process parameters and the like recited herein.
EXAMPLE 1
Synergistic and Residual Effects of Plant Essential Oils and
Piperonyl Butoxide on the American Cockroach
[0041] Plant essential oils, alone and in combination with
piperonyl butoxide (PBO), were evaluated for synergistic and
residual toxicity against American cockroaches. Glass jars were
treated with different concentrations of the materials diluted in
acetone solvent. The treated jars were left uncovered for
approximately one hour so that the acetone would evaporate, and
then the insects were introduced into the jars at different
intervals after jar treatment. Insect mortality was observed after
24 hour exposure to the treated jars. Five cockroaches were used
for each cross-walk treatment. Two replicates/treatment. This
experiment was repeated 3 times. TABLE-US-00001 Test % Mortality
(days after treatment) No. Chemical* 1 hr 7 14 21 28 35 45 50 1
Control (100) 0 0 0 0 0 0 0 0 2 PBO (100) 80 50 30 0 0 0 0 0 3 PBO
(100) + 100 100 100 100 20 0 0 0 BA (100) + C-ester (25) 4 PBO
(100) + 100 100 90 80 70 0 0 0 C-ester (25) 5 PBO (100) + 100 70 50
0 0 0 0 0 BA (100) 6 PBO (100) + 100 100 100 100 70 0 0 0 BA (50) 7
PBO (100) + 100 70 70 90 100 50 40 0 C-acid (25) 8 PBO (100) + 100
80 70 80 100 50 40 40 C-alcohol (25) 9 PBO (30) + 100 60 60 70 80
80 80 0 thymol (30) 10 PBO (100) + 100 100 100 0 0 0 0 0 eugenol
(500) *Measured in mg/jar of test substance BA = Benzyl Alcohol
C-Ester = Chrysanthemate ester C-Acid = Chrysanthemic acid
C-Alcohol = Chrysanthemyl alcohol
[0042] These examples show the synergistic properties of plant
essential oils combined with enzyme inhibitors such as PBO, along
with other synergists not expected to act as enzyme inhibitors. The
data clearly shows synergistic action, as well as strong residual
toxicity for almost two months with certain mixtures. The data also
demonstrates that the ratio of the items in the mixture is an
important factor in the resulting synergy and residual toxicity.
For example, a 1:1 mixture of PBO to benzyl alcohol did not produce
synergistic properties whereas a 2:1 mixture of the same compounds
respectively gave synergistic action and provided four weeks
residual toxicity. In contrast, PBO and thymol at 1:1 ratio
produced synergistic properties and provided residual toxicity for
more than a month. These data are unanticipated and demonstrate the
synergistic action among these compounds.
EXAMPLE 2
Synergistic Action of Piperonyl Butoxide on Plant Essential Oils
with Other Synergists Against the American Cockroach
[0043] Plant essential oils, in combination with piperonyl butoxide
(PBO) and/or other synergists, were evaluated for synergistic and
residual toxicity against American cockroaches. Glass jars were
treated with different concentrations of the materials diluted in
acetone solvent. The treated jars were left uncovered for
approximately one hour so that the acetone would evaporate, and
then the insects were introduced into the jars at different
intervals after jar treatment. Insect mortality was observed after
24 hour exposure to the treated jars. Five cockroaches were used
for each cross-walk treatment. Two replicates/treatment. This
experiment was repeated 3 times. TABLE-US-00002 % Mortality (days
after treatment) No. Test Chemical* 1 hr 7 14 21 28 11 Control
(100) 0 0 0 0 0 12 BA (50) + PBO (100) + 100 100 100 80 60 C-acid
(25) 13 BA (25) + PBO (100) + 100 100 100 100 100 C-acid (25) 14 BA
(50) + PBO (100) + 100 100 100 0 0 C-alcohol (25) 15 BA (25) + PBO
(100) + 100 100 100 50 0 C-alcohol (25) 16 BA (50) + C-ester 100
100 100 60 60 (25) + PBO (100) 17 BA (25) + C-ester 100 100 100 60
40 (25) + PBO (100) 18 BA (25) + PBO (100) + 100 100 100 100 60
C-acid (12.5) + C-alcohol (12.5) 19 Eugenol (50) + PBO (100) 100
100 100 100 60 20 Eugenol (50) + PBO 100 100 100 100 100 (100) + FK
(0.1) *Measured in mg/jar of test substance BA = Benzyl Alcohol
C-Ester = Chrysanthemate ester C-Acid = Chrysanthemic acid
C-Alcohol = Chrysanthemyl alcohol FK = Forskolin
[0044] These data clearly show the synergized action of the
mixtures, even at very low dosage rates and exposure levels. The
test chemicals by themselves are not totally effective on contact
at these levels and they certainly do not provide the unexpected
residual toxicity without the enzyme inhibitors and synergists.
Again, ratios are important in creating synergistic blends of these
compounds. In Example 2, PBO:eugenol at 1:5 did not produce
residual toxicity beyond 14 days, whereas PBO:eugenol at 2:1
provided residual toxicity for one month. Also, the addition of
other synergists to the mixture, even at very low levels, appears
to enhance the knockdown and residual toxicity of the mixtures. The
resulting synergistic action from these low levels of synergists is
clearly unexpected, especially since these synergists are not toxic
to insects when used alone.
[0045] As can be seen from the above discussion, the synergistic
and residual combinations of active compounds according to the
present invention are markedly superior to plant essential oils and
known pesticidal agents/active compounds conventionally used for
pest control in the household and agricultural crops. The
pesticidal effectiveness of the particular new synergistic and
residual combinations of active compounds of the present invention
is substantially (and surprisingly) higher than the sum of the
separate effects of the individual active compounds.
[0046] Although illustrative embodiments of the invention have been
described in detail, it is to be understood that the present
invention is not limited to those precise embodiments, and that
various changes and modifications can be effected therein by one
skilled in the art without departing from the scope and spirit of
the invention as defined by the appended claims.
* * * * *