Note: Descriptions are shown in the official language in which they were submitted.
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This invention is concerlled Witll insecticides and enhancing
their insecticldal effect using partial replacement compounds whlch are
more environmentally acceptable.
One of the main means of controlling lnsect infestation has
been through the use of chemical insecticides. ~t the present time there
are 15,000 registered pecticides within North America of which about
6,000 are sold in Canada. The pesticides generally fall into five major
categories viz: chlorinated hydrocarbons e.g. DDT, lindane, metho~ychlor,
etc.; organophosphates e.g. malathion, dibrom, dia~inon [trademarkl,
phosphamedon9 etc.; carbamate compounds e.g. baygon [trademark], sevin
[trademark], ~ectran ~trademark], etc.; inorganic compounds e.g. arsenic,
sulphur, borax, etc.; and botanical compounds e.g. pyrethrum, strychnine,
nicotine, etc. The chemical insecticides have been frequently used
against major forest pests, e.g. DDT against spruce budworm, and have in
many cases, been quite successful.
The chemical insecticides, with the exception of the botanical
ones, have several disadvantages. Most of them are highly toxic to Eish,
wildlife, and humans and must be used with caution. They are usually not
natural biological constituents and tend to persist for long lengths of
time after their initial application. This i8 best exèmplified by the
chlorinated hydrocarbons which because o~ their persistence have passed
througll the animal food chain and caused egg shell thinning and egg
breakage in many species of blrds.
BesLdes their initial toxic effect, these compounds can have
sub-acute effects on non-target fauna and flora thereby causing biochemi-
cal, behavioural and physiological changes as well as reproductive fail-
ure. Most of the chemical insecticides are ~uite expensive and with the
current petroleum shortage, difficult to obtain. The breakdown products
and secondary metabolites of most petrochemical pesticldes and their
impact on humans and other living organisms are poorly understood.
Recent research has shown that the unsaturated C18 fatty acids
or their salts (C18:X) are highly toxic to soft bodied insects including
aphids, mealybugs, whitefly, pear psylla, rose slugs, etc. (G. Puritch,
1978 Symposium on the Pharmacological ~ffects of LipLds AOCS monograph
No. 5, 105-112). During investigations, it was further discovered that
.~
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combination of the unsaturated 1~ carbon fatty acids and/or salts with
either organochlorines or organophosphates or carbamate insecticides gave
an unexpectedly high degree of ~nsecticidal activity when topically
appliedO Thls unique finding has permitted a reduction of the petrochem
ical pesticide required for suitable pest control and has provided an
increase in the spectrum of insect pests controlled. For example, we
found the C18:X acids, especially oleic and linoleic and their salts in
solution in concentrations from 0~25 to 5~0% in combination with the
or~anochlorines, especially methoxychlor in A conceDtration range of 50
ppm to 50,000 ppm or in combination with organophosphates, especially
diazinon in a concentration range of 50 ppm to 50,000 ppm, effective for
the control of insect pests.
Summary of the In~ention
The invention thus provides a mixture having enhanced insecti-
cidal activity comprlsing:
(a) an insecticide active against defoliating insects selected from
organochlorlne compounds, organic esters of phosphoric or thiophosphoric
acids and carbamates, and mixtures thereof, and
tb) an unsaturated fatty acid having 18 carbon atoms or its salt; the
fatty acid compound being at least about 50% by weight of (a) + (b~.
The invelltion includes a method of protecting susceptible
plants agains~ both sucking lnsects and defoliating insects comprisLng
providing concurrently on the plant surEaces or directly on the insects,
both (a) an insecticide active against defoliating insects selected from
organochlorine compounds, organic eseers of phosphoric or thiophosphoric
acids and carbamates, and mixtures thereof, and (b) an unsaturated fatty
acid having 18 carbon atoms or its salt; the fatty acid compound being at
least about 50% by wt. of (a) + (~). Preferably (a) and (b) are applied
together as a mixture.
The fatty acid (b) is selected from oleic acid, linoleic acid,
their soaps ~salts) and mixtures thereof. Linolenic acid or ricinoleic
acid may be present~ The cation forming the salt o~ soap with the fatty
acid usually is selected from sodium, potassium or ammonium. Other
cations that may be utllized include ~inc, copper and mono-, di- or tri-
ethanolamines.
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In the mixture, or in use, the proportions of ln6ecticide (a)
to fatty acid (b) may range from about 1:200 to about 1:1 by wt., prefer-
ably about 1:20 to about 1:2.
The mixture may be used in the form of a solution in any suit-
able solvent. In one preferred embodiment an aqueous solution i8 used inwhich the concentration of insecticide (a) ranges from about 0~005 to
about 5% by wt., and the concentration of fatty acid or its salt (b)
ranges from about 0.25 to about 5% by wt. P~eferably the soap of the
fatty acid is used in aqueous solution.
In another preferred aspec~, we formulate the concentrated
soaps with alcohols consisting of methanol, ethanol or lsopropanol at
various concentrations up to 35%. Preferably, we also use xylene in the
methoxychlor combination (xylene can reach up to 25% concentration).
Other suitable organic solvents such as kerosene~ hexane or acetone could
also be used in the formulation. In the acid form the fatty acids are
substantially water insoluble and along with ~08~ of ~he petrochemical
pesticides in the mixture, elther have to be solubllized ln organic
solvents or as emulsiflable concentrates.
We have used varlous anionic/nonionic blends of emulsifiers
such as Witco Chem. Canada Ltd. Sponto~ 300T and 500T partlcularly for
our methoxychlor-soap mixtures. Other types of emulsifiers; anionlc,
cationic and nonionic could all be used in the various mixtures. Concen-
tration~ would vary up to 10~ by weight.
Other solvents, detergents, wetting agents, carriers, ad~u-
vants, etc., may be used as known in the art.
Suitable organochlorine insecticides include methoxychlor[1~ trichloro-2,2-bistp-methoxyphenyl)ethane], lindane, benzene hexa-
chloride, endosulfan, fenitrothion, and pentachlorophenol.
Suitable insecticidal esters of phosphoric and thiophosphoric
acids include dia~inon ~ [phosphorothioic acid 0~0-diethyl-0-(2-isopro-
pyl-6-methyl-4-pyrimidinyl)ester], malathion [S-(1,2-dicarbethoxyethyl)-
O,O-dimethyldithiophosph~te], phosphamedon, meta-systox ~ trlchlorofon~
Abate ~ , dichlorovos and Dur~ban ~, also dimethoate.
Suitable carbamate insecticides include Sevln ~ [1-naphthyl-N-
methycarbamate], Zectran ~ , Baygon ~ and Matacil ~ O
The following examples are illustrative.Example 1 Test of unsaturated C18 salts (soaps) in combinatlon with
methoxychlor for wintermoth (Operophtera brumata) control.
Host plant: Apples, cv. Spartan
Sample Unlt and Procedure: Wintermoth larvae (4th or 5th lnstar) were
separated from their foliage and separated into groups of 25. ~Iree
groups were selected at random and assigned to the following 22
treatments:
(a) H20 (1) 0.005 MeO + 1~0 KO
10 (b) 0.001% MeO (methoxychlor) (m) 0.01 MeO + 1.0 KO
(c) 0.005 MeO (n) 0.05 MeO + 1.0 KO
(d) 0.01 MeO (o) 0.1 MeO + 1.0 KO
~e) 0.05 MeO (p) 0.01 MeO ~ 0.25 KO
(f) 0.10 MeO (q~ 0.01 MeO ~ 0O5 KO
15 (g) 0.5% KO (C18:X salts) (r) 0.01 MeO + 2.0 KO
(h) 1.0% KO (s) 0.01 MeO ~ 5.0 K0
(i) 2.0 KO (t) lZ Coco soap
(~) 5.0 KO (u) 2% Coco soap
(k~ 0.001 MeO ~ 1.0 KO (v~ 1% Coco soap ~ 0.05 MeO
These solutions were made up fresh be~ore use. The unsaturated fatty
acld salts were made by neutralizing oleic and l~noleic (77.0%:7.0%) with
potassium hydroxide (KO). The methoxyc~lor (MeO) was a standard retall
grade. Larvae were sprayed to wetting with a hand pump sprayer, blotted
dry and returned to fresh apple leaves. Mortality was assessed by count-
ing living and dead larvae 24 hours after treatment~ "Coco soap" is thepotassium soap of coconut oil fatty acids.
Results are given in Table 1.
Table 1
Percent Mortality
Solution % H20 0.25K0 005KO1.0KO2.0KO5,0K0 1%Coco 2%Coco
H20 0 ' 24.0 18.7 81.390.093.0 97.3
0.001 MeO 8.0 88.0
0.005 MeO 1.3 96.0
0.01 MeO 1.3 47.7 91.0 98.694.3100.0
0.05 ~feO 8.7 100.0 100.0
0.10 MeO 60.0 93.0
.
1/ Average of 3 replicates, each replicate had 25 larvae
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l'he synergistic interactlon of the methoxychlor with ~he unsaturated Cl8
salts is clearly evident. A combination of 1.0% KO with about 0.01% MeO
would provide a suitable degree of wintermoth control.
Example 2 Test of unsaturated C18 fatty acid salts (soaps) in
S combination with methoxychlor for control of wintermoth
(Operophtera brumata).
. .
Materials and Methods:
Larvae were obtained from a Gary oak and separated into groups
of 25. The insects were sprayed to wetting with the solutions using a
common hand-pump sprayer. Three groups of 25 were used for each treat-
ment concentration. After spraylng, the insects were put on fresh foli-
age in a plastic container and msintained for 24 hours before assessment.
Treatments conslsted of the following:
(a) O.Ol~ MeO (methoxychlor) (i) 0.13% MeO + 1% KO
(b) 0.03% MeO (~) 0.19% MeO + 1% KO
(c) 0.06% MeO (k) l.O% KO
(d) 0.13 MeO (1) H20 (control)
(e) 0.19 MeO (m) untreated control
(f) 0.01% MeO ~ l% KO (Clg:X salts)
2n (g) 0.03% MeO + 1% KO
(h) 0.06% MeO + 1% KO
The fatty acid treatment consisted of potassium oleate plus potassium
linoleate (77:7%)~
Results:
Results of this experltnent are shown in Table 2. The methoxy-
chlor (MeO)-soap combination gave higher mortallty than either the MeO or
soap alone, thus they acted synergistically. Increasing the MeO concen-
tration for .01% to 0.19% had virtually no effect on mortsllty. Even
when combined with soap, increasing the MeO concentration did not
increase mortality.
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Table 2
Effect of methoxychlor and soap on
mortality of wintermoth larvae
% Mortality
Solution % Rep 1 Rep 2 Rep 3 Aver
0.01 MeO 20* 44 35 32.9
0.03 MeO 46 56 52 51.3
0.06 MeO 44 56 52 50.6
0.13 MeO 50 52 44 48.6
0.19 MeO ~2 56 48 65.3
0.01 MeO ~ 1% KO 92 92 88 90.7
0.03 MeO + 1% KO 92 73 69 88.3
0.06 MeO ~ 1% KO 77 88 80 81.7
0.13 MeO + 1% KO 84 96 96 92.0
0.19 MeO + 1% KO 92.3 84 96 90.7
1% KO 48 48 68 54.7
Control (treated) 0 4 4 2.7
Control (untreated) O 4 4 2.7
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* each repllcation contained 25 larvae
Exflmple 3 Test of unsaturated Clg salts (soaps) in combination with
methoxychlor for control of gypsy moth (Lymantrla dispar L.)
Host plant: Oak
Materials and Methods:
A solution of 18 carbon atom, unsaturated fatty acid salts
oleate and linoleate (C18:1 ~ C18:2; 77%:7%) was made up fresh. ~irst
or second instar larvae of gypsy moth were selected and separated in~o
groups of 25, three groups were randomly selected and assigned to the
following treatments:
(a) 1% Clg:l + Clg:2 (77%:7%) salts (KO)
(b) 2~ KO
(c) 1% KO + 0.17 MeO
(d) 2% KO + 0.1% MeO
(e) Control~
Larvae were sprayed to wetting with a hand sprayer, placed on oak leaves
and mortality assessed after 24 hours.
Results are shown in Table 3.
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Table 3
% Mortality
Solution Ist Instar 2nd Instar
1% KO 52 0 5i.3
2% KO 48.7
1% KO + 0.1% MeO 100.0 86.6
2% KO ~ 0.1% MeO
Control 0~0 0.0
These results show that a comblnation of methoxychlor plus the
unsaturated C18 fatty acids gives a high degree of mortality to gypsy
moth larvae. Although methoxychlor alone was not incl~lded in this test,
results Erom tests by other groups have shown that it is relatively
ineffective against gypsy moth larvae.
E~ample 4 Test of unsaturated C18 salts (soaps) in combination with
methoxychlor for elm leaf beetle control
Test: cond~lcted by Dr. T.R. Renault, Canadian Forest~y Service, Maritime
Forest Research Center, P.O. Box 4000, Fredericton, New Brunswick,
E3B 5P7
Materi~ls and ~lethods:
~ duLt elm leaf beetles were collected and placed in three plas~
tlc transparent cages (30 x 30 x 46 cm) with nylon mesh tops. Beetles
were topically tre~ted and then returned to hardwood folLage in the cages.
Solutiolls were made up before use and consisted of (a) 3~0~ potassium
oleate ~ potassium linoleate; 77%:7% (KO)~ or KO + 0.01% methoxychlor (KO
MeO). ~fortality was assessed after 24 hours.
Results are given in Table 4. Table 4 shows the effect of KO and
KO + MeO combination on elm leaf beetle mortality.
Table 4
. _ . ... ~
Treanlent
Cage #1 Cage #2 (Mean) Control
Spray Regime % % % % % ~O % %
living dead living dead living dead living dead
_ . .... _ __ ~
3.Q%KO 62(34) 38(21) 60(27) 40(18) 61(61) 39(39) 96(22) 4(1)
1.0%KO+0.01% MeO 15(3) 85(71) 17(4) 83(19 ¦16(7) 84(36) 98(62) 2(1)
3.0~KO+0.01% MeO 10(3) 90(28) 8(2) 92(24) 9(5) 91(52) 100(63) 0(0)
~ . . _ .................... . . __
Note: Bracketed figures accompanying percentages represent actual
number of larvae.
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It is apparent from these results that both the soap/methoxy-
chlor ~ixture and soap alone produced significant kill when compared to
the small degree of mortality in the control (1ess than 3%). It also
shows that a combination of KO soap + methoxychlor is more effective than
soap alone. Although metho~ychlor alone was not tr-led, label recommenda-
tions indicate that 6.0% active ingredient is needed for acceptable con-
trol. ~lis is substantially greater than the 0.01% methoxychlor used in
the combination with the C1g unsaturated salts.
The eEfect of treatment on beetle mortality over ti~e is~ shown
in Table 5. For thls test, beetles in cage 1 were treated w1th water,
those in cage 2 w,ith 3.0% KO and those in Cage 3 with 3.0% KO + O.OlX MeO.
It is evident that tllere was little increase in mortality after the first
four hours after treatmellt.
Table S
. __
.~ ~ . ...
H20 treated 3.0% RO 3.0% KO + O.OlX MeO
CaRe ~1 Cage #2 Cage #3
. ~ _ (111 beeties = (116 beetles)
Mortallty: Cumulative Total
_____ ____
No. (%) No (%) No (%)
_ .. __ ... _.
4 hrs. after treatment l (0.8) 44 (39) 96 (83)
8 hrs. after treatment 2 (1.7) 46 ~41) 105 (91)
16 hrs. after treatment 2 (1.7) 48 (43) 113 (97)
24 hrs. after treatment 2 (1.7) 51 (46) 113 (97)
48 hrs. after treatment 3 (2.5) ~4 (67) _ (97)
Example 5 Test of unsaturated C18 fatty acid salts (soaps) in
combination with dlazlnon ~ for control of earwigs (Forficula
auricularia).
Materials and ~1ethods:
Adult F. auricularia were collected from the field and separated
into groups of 25. Three replicates of each group were assigned to the
following treatments:
(a) water
(~) 0.8% C18:1 + C18:2 (77:7%) salts (KO)
(c) 0.01 ~iazinon ~ (D2)
(d) 0.8% KO ~ 0.01% D2
Insects were treated topically to wetting with a hand pump
æprayer and returned to rearing containers. Mortality was assessed after
24 hours at room temperature.
Results are given ln Table 6.
Ta
% Mortality
Rep 1Rep 2 Rep 3 _ Rep 4 Rep 5_ AverO
Control 0* 0 0
0.8% K0 20 40 20 40 0 24
0.01X D2 20 8 12 16 8 12.8
0.8% K0 ~ 0.1% D2 100 92 100 100 100 98.4
* % mortality out of 25 insects
These results clearly show the synergism between the fatty acid
salts and diazinon ~
Exa~ple 6 Test of unsaturated C18 salts (soaps) in combination with
Malathion, Diazlnon ~ and Sevin ~ for control of cabbage aphid
Brevicoryne brassicae (L.)
.
Material and Methods:
Cabbage aphids, Brevicoryne brassicae (L.), were collected off
of field cabbage and were used as the target insect. Five hundred ml of
each treatment solution was made up fresh prior to use. Unsaturated fatty
acid salts were made by neutralizing oleic and 1inolPic (77.0%:7~0% KO)
with potassium hydroxide and a tall oil with its oleic and linoleic fatty
acids (59.2%:40.8%~ F4) also converted to their potassium salts. These
were formulated as a 50% liquid concentrate containing less than 0.03%
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excess alkali from which the appropriate dilu~Lons were made. The
malathion, Diazinon ~ and Sevin ~ were standard retail grade and used at
the concentrations recommen~d by the label~ Ftve replicates each con-
taining 20 aphids were randomly assigned to the following treatments.
5 (a) 1% KO (g) 1% K0 ~ 1% Diazinon
(b) 1% F4 (h) 1% KO + 0~31% Sevin
(c) 1% malathion (i) l~ F4 + 1% malathion
(d) 1% Diazlnon ~ (~) 1% F4 ~ 1% Dlazinon
(e) 0.31% Sevirl ~ (k) 1% F4 ~ 0.31% Sevin
lO (f) 1% KO + 1% malathion (l) H20 Control
Aphids were sprayed to wetting (3 ~L/replicate) on a glass plate, uslng a
hand pump sprayer, allowed to soak one minute in the solution, before
being transferred to petri plates (10 cm) lined with 9 cm Whatman filter
paper #1. Mortality was assessed by counting living and dead aphids 24
hours after treatment.
Results are gLven ln Tflble 7.
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The interaction of the malathion, Diazinon ~ and Sevin ~ with
the unsaturated C18 salts i8 again clearly evldent~ The combinations in
all cases showed enhanced activity greater than the individual formula-
tions.
Table 7
. . , _
Aphid Mortality (5 r~plicates eucll co~l~ainirlg % MorL.
20 aph;ds~
~ . . _____._
Replicates ( ) = Moribund
TREATMF.NTS 1 2 3 4 5 ._ ~
~120 ' O O ~ O O ()
1% K0 16 12 17 16 198()
1% F4 15 15 16 15 1273
1% Malathion 16 15(5) 19 1517 82
1% Uiazinon(~) 14(5) 15(5) 17(3) 13(7) 16(4) 75
0.31% Sevin~ 13 14 19 1720 83
1% K0 + 1%
Mul.aLI)ion 20 20 20 2020 100
1% K0 -~ 1%
Diaz;no~ 20 20 19 20 2099
1% K0 -~ 0.31%
S~vi~i~` 20 20 20 20 20100
IX F4 -t 1% 20 20 20 20 2U100
Mula~l~i on
l% F4 + 1%~,
Diazillo ~ 18(2) 19(1) 20 19(r) 17(3) 93
1% F4 -t Q.31~
S~vi~l~ 20 20 20 2() 20100
