CA1092020A

CA1092020A - Pesticidal compositions

Info

Publication number: CA1092020A
Application number: CA282,045A
Authority: CA
Inventors: Louis Melnicake
Original assignee: INCHCAPE CHEMCO Ltd
Current assignee: INCHCAPE CHEMCO Ltd
Priority date: 1976-07-06
Filing date: 1977-07-05
Publication date: 1980-12-23
Also published as: DE2730340A1; PT66764A; FR2357177A1; AU2674177A; NO772391L; FR2357177B1; DD133389A1; PT66764B; BE856487A; DK300877A; ATA478577A; NZ184567A; LU77690A1; AT356460B; IE45739B1; IT1105103B; IE45739L; ZA774036B; GB1574609A; GR63751B

Abstract

ABSTRACT OF THE DISCLOSURE

A pesticidal composition comprising a natural or synthetic pyrethroid in combination with a synergistic amount of oil of pepper. The oil of pepper is conveniently obtained by steam distillation of crushed peppercorns or pepper-derived oleoresin. The composition may also contain oil of eucalyp-tus and/or geraniol and is preferably formulated with an aerosol propellant.

Description

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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 , ~C1921~æ~

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 ~ ~9 ~

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 _ g _ .

' , ~ ~ ~ 2 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 - 10 ~
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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.
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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 ~ Z~

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 - 14 - ~

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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 ..

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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Claims

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. A pesticidal composition comprising (a) a natural or synthetic pyrethroid in combination with a synergistic amount of (b) oil of pepper.

2. A composition as claimed in Claim 1 wherein the oil of pepper is unfractionated.

3. A composition as claimed in Claim 1 wherein the oil of pepper is essentially the first fraction only or a mixture of the first and second fractions of a fractionated oil of pepper.

4. A composition as claimed in Claim 1 wherein the pyrethroid is pyrethrum in an amount of 5 to 50%
by weight of solids calculated on the weight of oil of pepper.

5. A composition as claimed in Claim 4 wherein the pyrethrum is present in an amount of 20 to 45% by weight of solids calculated on the oil of pepper.

6. A composition as claimed in Claim 1, 2 or 3 wherein at least one synthetic pyrethroid is present in an amount of 50 to 950% by weight of the oil of pepper.

7. A composition as claimed in Claim 1 also con-taining oil of eucalyptus.

8. A composition as claimed in Claim 7 wherein said oil of eucalyptus is obtained from Eucalyptus polybractea.

9. A composition as claimed in Claim 7 wherein the oil of eucalyptus is present in an amount of 2 to 30 times the weight of oil of pepper.

10. A composition as claimed in Claim 9 wherein the oil of eucalyptus is present in an amount of 4 to 20 times the weight of oil of pepper.

11. A composition as claimed in Claim 1 also containing geraniol.

12. A composition as claimed in Claim 11 wherein the geraniol is present in an amount of 2 to 4 times the weight of oil of pepper.

13. A composition as claimed in Claim 1 in association with an aerosol propellant.

14. A pesticidal composition as claimed in Claim 1 comprising (a) a natural or synthetic pyrethroid in combination with a synergistic amount of (b) oil of pepper and (c) oil of eucalyptus.

15. A pesticidal composition as claimed in Claim 1 comprising (a) a natural or synthetic pyrethroid in combination with a synergistic amount of (b) oil of pepper, (c) oil of eucalyptus and (d) geraniol.

16. 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 pesticidal composition comprising (a) a natural or synthetic pyrethroid in combination with a synergistic amount of (b) oil of pepper.