Note: Descriptions are shown in the official language in which they were submitted.
2~
This invention is concerned with improvements in
or relating to pesticidal compositions.
Many pesticides in use are based on synthetic
organic chemicals. Although these substances are
frequently of relatively simple structure and can often
be produced from comparatively inexpensive precursors
they do suffer from various disadvantages. This is
particularly so with organochlorine insecticides which,
although having great value as insecticides, are now
increasingly finding disfavour because they are not
sufficiently biodegradable. Non-organochlorine insecticides
e.g. organophosphates, although not suffering from these
disadvantages, but various insect species often develop
resistance to them a~d their use becomes limited. Again
lS various synthetic insecticides possess levels of mammalian
toxicity and/or phytotoxicity in excess of that which would
ordinarily be desired. There is thus a need for new pesticides
which are either free from these disadvantages or possess
them to a more restricted degree. In particular, there is a
need for new pesticides which are in whole or in part of
natural origin.
Insecticides which have found wide acceptance include
those based on natural and synthetic pyrethroids. Natural
pyrethroids are referred to herein as "pyrethrum".
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Hitherto pyrethrum has been employed substantially
exclusively in formulations e~pecially adapted to household
use in the control of flyin~ insects e.g. flies a~d
mosquitoes These have generally been hydrocarbon oil
dispersions, such as moderately to highly refined kerosene
oil formulations.
Pyrethrum is an insecticide of the knock-down type.
Employed alone~ therefore, it functions to effect paralysis
upon contact. When used in very high concentration, it
can effect 90 per cent or better knock-down, measured in
a Peat Grady chamber, within a few minutes. Thus, its
immediate effectiveness is excellent. However, its power
to maintain knock-down control, i.e. bring about paralysis
and death of the insects to be controlled for a long
period of time, is not impressive.
Extensive research work has been carried out by
various workers to enhance the effectiveness of pyrethrum
so as to render it more widely usable. Thus synergistic
action has been found to result by using pyrethrum in
admixture with various substances, more particularly on
an extensive commercial scale with the synthetic substance
piperonyl butoxide.
It has previously been reported by Matsubara and
Tanimura in Bochu ~ 31(4) 162-7 (1966) that the
synergistic activities of piperine, chavicine and oleoresin,
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all constituents of pepper, on the effectiveness of
pyrethrum and allethrin (a synthetic pyrethroid) were
lower than those of piperonyl butoxide against female
adult houseflies However, in our hands the results
obtained with these pepper constituents have been
uncertain, although it was evident that some constituent
of pepper was contributing a measure of insecticidal
activity. Chavicine and plperine, to the extent that
they contribute such activity, exist in variable
concentrations in pepper extracts. Oleoresin, on the
other hand, is not a satisfactory material to use~in
insecticidal preparations because it causes blockage of
spray orifices as well as providing an unsatisfactory
level of insecticidal activity.
Extensive research has also been carried out on
synthetic pyrethroids e.g. allethrin, bioresmethrin and
phenothrin. These substances possess many of the advantages
of pyrethrum, e.g. biodegradability, but also possess other
advantages including, as appropriate,enhanced knock-down and kill
We have now found that the insecticidal activity of
natural and synthetic pyrethroids can be improved in
a synergistic manner if they are used in conjunction wit~ .
oil of pepper. This finding can be used to produce 7
pesticidal compositions havinga high degree of insecticidal
activity.
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Unlike constituents of pepper referred to in the
prior art, oil of pepper, when used in conjunction with
a natural or synthetic pyrethroid, provides significant
levels of insecticidal activity, and does not suffer from the -
major disadvantages of other pepper constituents. Althoughit is normally obtained and used as a multi-constituent
oil this can be readily manufactured by steam distillation
of pepper extracts to a substantially uniform specificationa ;
According to one aspect of the present invention
there is provided a pesticidal composition comprising a
natural or synthetic pyrethroid in admixture with oil of
pepper, these two constituents being used in such relative
proportions as to provide a synergistic effect.
The oil of pepper is conveniently manufactured from
15 pepper-derived oleoresin, a product prepared by extracting -
pepper with alcohol followed by removal of solvent at
reduced pressure. Oleoresin is a by-product of the spice
producing industry and its industrial utilisation is a
matter of some importance. By submitting the oleoresin
20 to a process of steam distillation or its equivalent the -
desired oil of pepper can be obtained. Steam distillation
is a relatively simple îndustrial process and can be used
to produce the desired oil of pepper adjacent to the
production site for the oleoresin. The oil of pepper
may alternatively be obtained by steam distillation of
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of crushed peppercornsO The oil can be separated into
various distinct fractions, and it is found that the first
fraction, i.e. the lowest boiling fraction, in particular
is the most insecticidally active. In practice, however,
it is generally convenient to use the whole oil unless
one is aiming at particularly high levels of insecticidal
efficiency in which event one would use the first fraction
or a mixture of the first and second fractions
It will be appreciated that oil of pepper contains
various constituents. A combination of two or more of
these probably contribute to the insecticidal activity of
the composition accD~ding to the invention.
The geographical source of the pepper used does
not appear to be importantO The amount of oil of pepper
present in the pepper as well as the characteristics of
the oil (e.g. its specific gravity and refractive index)
may vary from source to source and may also be dependant
on the age and physical condition of the peppercorns used.
Pepper is extensively cultivated in the Indian sub-
continent as well as throughout Couth East Asia and in parts
of Africa. Although one is concerned with a single species
Piper ni~rum there exist various sub-species which
contribute to variation of quantity and quality of oilO
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These variations are not believed to be significant for
the purpose of the invention.
Pyrethrum may be used as a commercial alcoholic
COTICentrate. Concentrates of this nature frequently
5 contain about 50% by weight of pyrethrin solids.
The term "synthetic pyrethroid" is used herein to
denote insecticidally active synthetic pyrethroid
compounds. Synthetic pyrethroids which may be used in -
the compositions according to the invention include bio-
allethrin, bioresmethrin, d-phenothrin and ~etrame~hrin
The amount of pyrethrum solids used may vary from
5 to 50% by weight of the oil of pepper. It will be
generally convenient to use from 20 to 45% by weight of
pyrethrum solids calculated on the weight of oil of
pepper.
When using synthetic pyrethroids the amount used
will vary according to the particular synthetic pyrethroid
used but will generally vary from 50 to 950~ by weight
of the oil of pepper.
A further ingredient which is advantageously present
in the composition is oil of eucalyptus.
As is known, oil of eucalyptus is obtained from
various species of Eucalyptus in the Southern and Northern
Hemispheres and the resulting oils do not possess a
uniform analysis. It isbelieved however~ that the
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properties of the composition according to the invention
are not dependant on a particular source of oil of
eucalyptus and one may use oil derived from Eucalyptus
globulus or Eucalyptus dives. It is, however, preferred
to employ oil obtained from the Australian species commonly
known as Blue Mallee, i.e. Eucalyptus polybractea, partly
owing to the efficacy of this oil and partly owing to the
relative ease with which Blue Mallee may be cultivated.
Such oil is rich in cineole (1,8-epoxy-p-menthane). In
general it is preferred to employ an oil of eucalyptus
containing at least 50% by weight of cineole.
The amount of eucalyptus oil used may vary
between wide limits e.g. 2 to 30 times the weight of oil
of pepper. Generally it will be convenient to use the oil of
eucalyptus in an amount of 4 to 20 times the weight of
oil of pepper.
There also are some indications that the insecticidal
activity of the composition according to the invention is
enhanced by the addition of geraniol (trans-3, 7-dime~hyl-
2,6-octadien-1-ol). This may be used in an amount of up
to 5 times the weight of oil of pepper e.g. 2 to 4 times.
The invention also includes within i-ts scope the various
novel synergistic compositions herein described for use
with natural and synthetic pyrethroids.
The conjoint use of sesame oil is also advantages
in preventing degradation of the pyrethrum and in improving
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insecticidal efficacy. This may be used in an amount
of l to 5 times by weight of the oil of pepper.
Further advantageous results may be obtained by
adding to the composition of the invention the bitter
substance known as quassia. The latter may be used as
Jamaica quassia or Surinam quassia. The quassia may be
used in an amount of 5 to 100% advantageously 10 to 50%
by weight of the oil of pepper The quassia is
conveniently used as an alcoholic extract.
Further substances which may be used include other
essential oils (and their components) eOg. oil of ;
citronella, oil of coriander, oil of cajeput, oil of
lemon and oil of thyme. Such substances may provide the
composition with a pleasing odour and/or improve its
pesticidal activity. Such substances may be used in
amounts of up to 5 times the weight of the oil of pepper.
Other substances which may be used include polyhydric ~ -
alcohols e.g. propylene glycol and triethylene glycol.
To facilitate the application of the compositions
according to the invention these may contain a di(lower
alkyl) sulphoxide, e.g. dimethyl sulphoxide, advantageously
in an amount of 50 to 150% by weight of the oil of pepper.
The sulphoxide appears to enhance the interfacial contact
of the pest and the pesticide and/or also to facilitate
the manufacture of homogeneous solutions of the active
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substances
The composition according to the invention may be
used in association with a solid or liquid diluent
adapted to facilitate the application of the pesticide
to the locus of application Where the locus of application
involves plant life then the carrier should be substantially
non-phytotoxic. The compositions according to the
invention have generally low phytotoxicity.
The compositions according to the invention may
contain conventional adjuvants e g. wetting agents,
emulsifying agents, pyrotechnic agents, opacifiers etc.
Conveniently they are formulated for spray application,
e g. as aerosols, but they may be applied in any convenient
manner.
The composition may be emulsified in an aqueous phase
with the aid of an emulsifying, wetting or dispersing agent,
e.g. diethanolamine lauryl sulphate, and preferably of a
biodegradable nature.
The composition may be prepared as a concentrate
e.g. in an aliphatic alcohol e.g. ethyl alcohol or
isopropyl alcohol and/or in an aliphatic hydrocarbon
for dilution to the required amount
When the composition of the invention is used as in
an aerosol formllation, the propellant advantageously
comprises a minor amount of a gas which is not in the
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liquid state, but which may be in solution, in the
aerosol container, e~g. nitrous oxide, together with a
major amount of conventional fluorocarbon propellant e.g.
11 and/12.
The invention includes within its scope a method of
controlling pests which comprises applying to a locus,
containing pests or which is susceptible to attack by
pests, an effective amount of a composition according to
the invention
The compositions according to the invention may be
used, inter alia, in the control of house fly (Musca
dome ) of various strains, sheep blow fly larvae
(Lucilla cuprina), cockroach (Blatella germanica),
:
= Colorado beetle larvae (Leptinot rsa decemlineata), rattle
tick larvae (Boophilus microphus), yellow fever mosquito
larvae (A s aegypti) and other mosquitoes (Culex fat gans)
and clothes moth larvae (Tineola pittoralis), including
str~ins re~istant to conventional pesticides.
~ . .
2 100 g. of refined oleoresin, an alcoholic extract
prepared from black pepper by Techno Chemical Industries
Ltd of Calicut, India was subjected to steam distillation
and the distillate (water plus oil) collected in 100 ml
portions. The oil was subsequently separated from the
aqueous distillate and weighed. In this way five fractions
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of oil were obtained.
Fraction Wt(g) Yield(%)
1 12.00 11.4
2 2.46 2.3
3 1.37 1.3
4 0.92 0.9
0.70 9.7
Total yield of oil 17.45 g (16.6% by weight of
oleoresin); refractive index at 200 1.4786; specific
gravity 2550 0.8603, 240 0.8580. -
Gas-liquid chromatography of the oil indicates that
the constituents fall into two main groups, the first with
relatively short retention times (about 1 minute) including
or equivalent to Fraction 1. Fraction 2 shows the first
appearance of ~laterial wlth retention time of 4.5 minutes.
Fraction 3 shows diminished peaks for low boiling material - :
but considerable enhancement of 4.5 minute peaks. Fractions
4 and 5 show only 4.5 minute retention material and no
lower retention material. It is not only remarkable that
such a clear cut degree of separation of constituents of the
::.
oil into groups is achieved by steam distillation but also :
that although all fractions are insecticidally active ~ .
Fractions 1 and 2, especially Fraction 1, were the most
active.
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For better understanding of the invention, the
following examples of various compositions according to
the invention are given. In the examples parts and
percentages are by weight unless otherwise stated.
In the examples, "oil of pepper" is a mixture of
Fractions 1-5 referred to above; "Pyrethrum"is natural
pyrethrin solids used as a 50% concentration in ethyl
alcohol (45% w/v~; "sesame oil" is commercial grade sesame
oil saturated with ozone, using ultraviolet irradiation;
quassia extract is a 9.8% solution in ethyl alcohol (45% w/v)
obtained by extraction of quassia chips. Eucalyptus polybractea
is the oil of eucalyptus obtained from that plant. "Propellant 11"
and " Propellant 12" are respectively Freon ll~and Freon 12.
All other ingredients are commercial grades.
Example 1
A. A pesticidal composition was made by admixing the
following ingredients:-
Oil of pepper 1.0 partPyrethrum 0.4 part
Ethyl alcohol (95%v/v~to 50 parts
B. This composition (A) was then packaged into aerosol
containers on the following basis:-
Composition (A) 50 partsPropellant ** 50 parts
** A mixture of equal parts of Propellant 11 and
Propellant 12.
Two comparison compositions A' and A" were made
up as follows:
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Oil of pepper 1.0 part
Ethyl alcohol (95% v/v) to 50 parts
Composition A'' i
Pyrethrum 0.4 part
Ethyl alcohol (95% v/v) to 50 parts
Compositions A' and A" were packaged into aerosol
containers in like manner to A. All three compositions
were tested for insecticidal activity in a Peat Grady
chamber against Kingsford (Australia) houseflies (Musca
domest ca). The stated weight of aerosol composition was . .
sprayed into the chamber containing about lOO of the flies
of the stated age and the percentage knock down estimated
n each case in two trials. The results were as follows: -~
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Comp. A A A' A' A " A "
Temp C 25 26 24 22 24 24
Age 5 6 4 4 5 5 ::
W t sp rayed 0 760.750,83 0.75 0.85 0,76 - ~ :
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Tlme(m) IC/OKD ¦ /~D ! C/OI~D ¦ V/~ D ¦ /~D ~/OKD : ;
2 16 13 7 8 4 7 .~: ~
4 32 ~ 21 13 16 15 17 ~ ~:
6 50 51 13 22 25 29
8 60 67 31 40 33 3~
~7 75 42 42 41 47
2 75 L _ 5l 59 47 54
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These results demonstrate that composition A was
acting in a synergistic fashion.
Example 2
This example shows the use of multi-component
composition.
A. A Composition was made up by admixing the following
ingredients:-
Oil of pepper 0,; part
Pyrethrum 0.04part
Geraniol 1.0 part
Eucalyptus polybractea 2.0 parts
Quassia extract 0.5 part
Dimethylsulphoxide 0.5 part
Triethylene glycol 0.5 part
Sesame oil 1.6 parts
Ethyl alcohol (45% v/v) to 78 parts
B. Composition A was then packaged into aerosol containers
on the following basis:
Composition A 78 partsPropellant 12 20 parts
Nitrous oxide 2 parts
- The resultant aerosol containers were then used in
a series of tests in a temperature controlled Peat Grady
test chamber using Klngsford flies as in Example 1.
Excellent knock down and kill results were obtained with a
medium-high level of aerosol spray.
The composition was also found to have a significant
level of fungicidal activity against various saprophytic
fungi such as Asper~illus niger.
Example 3
This example illustrates variations on the
formulation of Example 2.
A. Various compositions were made up by admixing the
following ingredients:-
Oil of pepper 0.05 to 0,1 part
Pyrethrum 0.04 part
Geraniol 1.0 part ::
Eucalyptus polybractea 2.0 parts :
Quassia extract 0. 5 part
Dimethylsulphoxide 0. 5 part
Triethylene glycol 0. 5 part :
Sesame oil 1.6 part
Ethyl alcohol (95%v/v) to 50 parts
B. The compositions of A were then packaged intoaerosol containers on the following basis:-
Composition A 50 partsPropellant 12 40 parts
Nitrous oxide 10 parts
and the products were tested in a Peat Grady chamber
as before with excellent results on knock down and kill. ~:
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Exa~ple 4 ~
A. A pesticidal composition was made by admixing the :
following ingredients:-
Oil of pepper 0.02 part
Phenothrin 0.09 part :
Bioresmethrin 0.09 part
Dimethylsulphoxide 0.25 part
Triethylene glycol 0. 25 part
Ethyl alcohol (95% v/v) to 50 parts
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B. Composition A was then packaged into aeroso,lcontainers on the following basis:-
Composition A 50 partsPropellant 12 40 parts
Nitrous oxide 10 parts
The resultant containers were then tested against
Kingsford flies as in Example 1~ Excellent knock dow~ -
and kill results were obtained.
Example 5
A. A pesticidal composition was made by admixing the
following ingredients:-
Oil of pepper 0.02 part
Phenothrin 0.09 part
Bioresmethrin 0.09 part
Eucalyptus polybractea 1.0 part
Geraniol 0.25 part
Ethyl alcohol (95% v/v) to 50 parts
Compositlon A uas then packaged into aerosol
containers on the same basis as in Example 4 for
testing against Kingsford flies, excellent knock down and
kill were also obtained.
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A. A pesticidal composition was made by admixing thefollowing ingredients:~
Oil of pepper 0.086 part ~-
Phenothrin 0.192 part
Eucalyptus polybractea 0.090 part
Ethyl alcohol (95% v/v) to 50 parts
Composition A was then packaged into aerosol containers
on the same basis as in Example 4 for testing against
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Kingsford flies3excellent knock down and kill were also
obtained.
Example 7
A. A pesticidal composition was made by admixing the ;
following ingredients:-
Oil of pepper 0.170 part
Phenothrin 0.097 part
Bioresmethrin 0.099 part .
Ethyl alcohol (95% v/v) to 50 parts
Composition A was then packaged into aerosol
containers on the same basis as in Example 4 for testing
against Kingsford flies,excellent knock down and kill were . ~
also obtained. ~: -
Example 8 .
A. A pesticidal comp~sition was made by admixing the
following ingredients:-
Oil of pepper 0.02 part:
Phenothrin 0.09 part
B~oresmethrin . . 0.09 part .~::
Eucalyptus polybractea 0.45 part
Geraniol 0.25 part ~
Triethylene glycol 0.25 part : . -
Dimethyl sulphoxide 0.25 part ~ :
Ethyl alcohol (95% v/v) to 50 parts .:
Composition A was then packaged into aerosol ;
containers on the same basis as in Example 4 for testing .
against Kingsford flies,excellent knock down and kill
were also obtained.
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