Note: Descriptions are shown in the official language in which they were submitted.
WO 90/14006 PCI/GB90/OOX18
204~932
PESTICIDAL COMPOSITIONS
The present invention relates to novel compositions, their
preparation, formulations containing them and to their use for the
control of insect pests.
Insecticides have been increasingly used in agriculture over the past
thirty years to control insect pests, thereby increasing the yield per
acre that land under cultivation can provide. However, with
increasing use of a particular insecticide, the insect population
modifies its susceptibility to the insecticide and resistance to that
insecticide may occur. Thus, by 1980, resistance to the
organochlorine and organophosphorous insecticides was common and, by
1988, resistance to the pyrethroids in certain insect species was
becoming widespread. Thus, for example, pyrethroid resistance in
heliothis species in Australia, Thailand, Turkey and the Americas is
becoming a major problem in the cotton growing industry in these
countries.
There are a number of ways of countering increasing resistance of
insect species to insecticides. Qne way is to develop new series of
insecticides which have a different mode of action to existing
insecticides and are not cross-resistant with these. However, this is
time-consuming and expensive and there is no guarantee of success. A
further possibility is to increase the activity of existing series of
insecticides so that resistant insects become susceptible to the
insecticides. This can be done by developing more active analogues of
existing insecticides or by increasing the activity of existing
insecticides by combining them with a substance which increases their
activity (a "potentiator") or formulating them in a manner which
enables them to overcome or by-pass the insects' resistance mechanism.
Piperonyl butoxide is a potentiator that has been commonly used to
potentiate the activity of the pyrethrins and the pyrethroids against
susceptible and resistant insect species Piperonyl butoxide
W O 90/14006 PCT/GB90/00818
- 2
9 ~'~
(5-[2-(2-butoxyethoxy)ethoxymethyl]-6-propyl-1,3-benxodioxole) acts by
inhibiting enzymes, mixed function oxidases, which are present in
susceptible and more so in pyrethrin/pyrethroid and some carbamate
resistant insects and degrades these insecticides.
_-Propyl-gallate is an antioxidant that is commonly used in the food
industry as a preservative. It has also been used in insecticide
formulations, for example, Hungarian Patent Application No 34100
discloses insecticidal compositions containing inter alia permethrin,
piperonyl butoxide and an antioxidant such as _-propyl gallate We
have discovered that BHT and BHA can potentiate tne activity of
insecticides, such as the pyrethrins, the pyrethroids and the
organophosphorus series of insecticides, against susceptible and
resistant insect species including Musca domestica and heliothis s~p.
In addition, we have found that the potentiating effect of piperonyl
butoxide appears to be adversely effected by light, i.e. piperonyl
butoxide is photosensitive; the addition of gallic acid esters to
piperonyl butoxide protects piperonyl butoxide against light induced
degradation.
Accordingly, in a first aspect, the present invention provides a
composition which comprises piperonyl butoxide a gallic acid ester in
a ratio of 3:1 to 1:10 by weight. Suitable gallic acid esters include
alkyl esters, most suitably those formed from straight chain alkyl
esters where the alkyl substituent contains up to 12 carbon atoms, in
particular propyl, octyl and dodecyl gallate esters. Preferably the
gallic acid ester is _-propyl gallate.
In a further aspect, the present invention provides an insecticidal
composition which comprises an insecticide, piperonyl butoxide and
n-propyl gallate, wherein piperonyl butoxide and _-propyl gallate are
in a ratio of 3:1 to 1:10 by weight, suitably in a ratio of 2.5:1 to
1:7 and are preferably in a ratio of 2:1 to 1:5 by weight Suitable
insecticides include o.ganophosphorous, pyrethroid, pyrethrin and
lipid amide pesticides.
WO 90/14006 PCI`/GB90/00818
3 ..
20~932
Suitable organophosphorous insecticides include:-
0,0-diethyl-0-(3-chloro-4-methyl-7-coumarinyl)phosphorothioate
(coumaphos);
0,0-diethyl-0-(2,5-dichloro-4-bromophenyl) phosphorothiate (bromophos-
ethyl~;
0,0-diethyl-0-(2-isopropyl-6-methyl-pyrimidin-4-yl)phosphorothioate
(diazinon);
2,3-p-dioxanedithiol S,S-bis, 0,0-diethyl phosphorodithioate (diox-
athion);
0,0-diethyl-0-(3,5,6-erichloro-2-pyridyl)phosphorothioate
(chlorpyrifos);
0,0,0',0'-tetraethyl, S,S'-methylenediphosphorodithioate (ethion);
3-(Dimethoxyphosphinyloxy)-N-dimethyl-cis-crotonamide (dicrotophos);
S-(1,2-dicarbethoxy ethyl)-0,0-dimethylphosphorodithioate (malathion);
cis-l-methyl-2-(1-phenylethoxycarbonyl)vinylphosphate (crotoxyphos); .
0-ethyl-0-(quinol-8-yl)phenylphosphorothioate (oxinothiophos);
(S-(5,7-dichlorobenzoxazol-2-yl-methyl)-0,0-diethyl phosphorodithio-
ate) (benoxanphos);
S-[(4-chlorophenyl)-thio]-methyl)-0,0-diethyl phosphorodithioate
(carbo phenothion);
S-11,3-dihydro-1,3-dioxo-2H-isoindol-2-yl)-methyl)-0,0-dimethyl
phosphorodithioate (phosmet);
2-Chloro-1-(2,4-dichlorophenyl)vinyldiethylphosphate (chlorofenvin-
phos);
0,0-diethyl ~-cyanobenzylideneamino-oxyphosphonothioate (phoxim);
0,0-dimethyl cis-1-methyl-2-methylcarbamoylvinyl-phosphate (monocroto-
phos);
(E)-0-2-isopropoxycarbonyl-1-methylvinyl 0-methyl ethylphosphoramid-
othioate (propetampho);
0-2-diethylamino-6-methylpyrimidin-4-yl 0,0-dimethyl phosphorothioate
(pirimiphos methyl);
0-2-diechylamino-6-methylpyrimidin-4-yl 0,0-diethyl phosphorothioate
(pirimiphos ethyl)
0-4-dimethylsulphamoylphenyl-0,0-dimethylphosphorothioate (famphur).
W O 90/14006 PCT/GB90100818
2 0 ~ ~ 9'~ 2 - 4
Suitable pyrethroid insecticides il1clude those of the formula (I)
X ~)
~CI10 C-R
~}~ (I~
X~
where R is CH=OiJ
~ ,"~1
CN3 ~H~l
N--( --(NlJ)n~ Rl
(CH;~11C
or
and n is 0 or l,
- Rl is halo, CF3 or CHF20, R2 is hydrogen or halo, and Z and zl are
each independently selected from halo, CF3 and methyl, X is halo, and
X is H, CN or C~CH
:,
W O 90/14006 PCT/GB90/00818
2 0 ~
C2H50 ~ 0~)
_~} C _ CH~OCH2
CH3 ~
Preferred pyrethroids for inclusion within the present in~ention
include:-
3-phenoxybenzyl-(lRS)-cis,trans-3-(2,2-dichlorovinyl-2,2-dimethyl-
cyclopropan~-l-carboxylate (permethrin),
(RS)-~-cyano-3-phenoxybenzyl-(lRS)-cis,trans-3-(2,2-dichlorovinyl)-
2,2-dimethylcyclopropane-l-carboxylate (cypermethrin) and its indivi-
dual isomers such as the (lRS) cis isomer (alphamethrin)
(S)-~-cyano-3-phenoxybenzyl-(IR)-cis-3-(2,2-dibromovinyl)-2,2-dimethyl
cyclopropane- l-carboxylate (deltamethrin)
(RS)-~-cyano-3-phenoxybenzyl-(Z)-(IRS)-cis-3-(2-chloro-3,3,3-trifluoro
propenyl)-2,2-dimethylcyclopropanecarboxylate (cyhalothrin) and a
mixture of its (S)(Z)-(IR)-cis and (R)(Z)-(IS)-cis-isomers.
(RS)-~-cyano-3-phenoxybenzyl (RS)-2-(4-chlorophenyl)-3-methylbutyrate
(fenvalerate) and the single (S), (S) isomer (esfenvalerate)
(RS)-~-cyano-3-phenoxybenzyl (S)-2-(4-difluoromethoxyphenyl)-3-methyl
butyrate (flucythinate)
(RS)-~-cyano-3-phenoxybenzyl N(2-chloro-~ -trifluoro-p-tolyl)-D-
valinate (fluvalinate)
(RS~-~-cyano-4-fluoro-3-phenoxybenzyl(IRS)-cis-trans-3-(2,2-dichloro-
vinyl) -2,2-dimethylcyclopropanecarboxy late (cyfluthrin)
WO 90/l4006 PC~/G~90/00818
- 6 -
~,~ 4~9 ~ ~
(RS`)-c~-cyano-4-fluoro-3-phenoxybenzyl(IRS)-cis-trans-3-(2-chloro-2(4-
.hlorophenyl)vinyl)-2,2-dimethylcyclopropanecarboxylate (flumethrin)
2-methylbiphenyl-3-ylmethyl(Z)-(IRS,3RS)-3-(2-chloro-3,3,3-trifluoro-
prop-l- -enyl)2,2-dimethyl cyclopropoane carboxylate (Bifenthrin).
Suitable lipid amide pesticides include those described in European
Patent Application nos. 111 105, 164 187, 194 764, 209 289, 225 011,
251 472, 269 457 and 317 188.
The precise amount of insecticide to be applied will depend on the
inherent activity of the insecticide against the insect species to be
controlled, the method of application and the nature of the
formulation to be applied and whether or not piperonyl butoxide is
included in the formulation but in general the following quantities
will be applied.
Pyrethroids between 5 and 150 g/hectare
(i.e. 0.0125 and 0.4 lbs/acre)
Natural pyrethrin between 2 and 12 ozs/acre
Organophophorous insecticides between 50 and lOO g/hectare (0.125
and 2.5 lbs/acre)
Lipid amides between 5 and 150 g/hectare (0.0125 and 0.4
llbs/acre).
Piperonyl butoxide between lOO and 1200 g/hectare (0.25 and 3.0
lbs/acre).
_-Propyl gallate between 33 and 6000 g/hectare (0.08 - 15
lbs/acre).
The formulation for agrochemical use which comprises _-propyl gallate
and piperonyl butoxide and/or one or more insecticides from the
organophosphorous, pyrethroid, pyrethrin or lipid amide classes of
insecticides may contain a suitable carrier. The carrier may be
liquid, solid or gaseous or comprise a mixture of such substances, and
the composition of the present invention may be present in a
W O 90/14006 PCT/GB9~/OOX18
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20~6932
concentration of from 0.025 to 99~ w/v depending upon whether the
formulation requires further dilution.
Dusts, powders and granules and other solid formulations comprise the
compositions of the present invention in intimate admixture with a
powdered solid inert carrier for example suitable clays, kaolin,
bentonite, attapulgite, absorbent carbon black, talc, mica, chalk,
gypsum, tricalcium phosphate, powdered cork, magnesium siliate,
vegetable carriers, starch and diatomaceous earths. Such solid
formulations are generally prepared by impregnating the solid diluents
with solutions of the combinations of the present invention in
volatile solvents, evaporating the solvents and, if desired grinding
the products so as to obtain powders and, if desired, granulating,
compacting or encapsulating the products.
Sprays of the compositions of the present invention may comprise a
solution in an organic solvent (e.g. those listed below) or an
emulsion in water (dip wash or spray wash) prepared in the field from
an emulsifiable concentrate (otherwise known as a water miscible oil)
which may also be used for dipping purposes. The concentrate
preferably comprises a mixture of the active ingredients, with or
without an organic solvent and one or more emulsifiers. Solvents may
be present within wide limits but preferably in an amount of from 0 to
90% w/v of the composition and may be selected from kerosene, ketones,
alcohols, xylene, aromatic naphtha, and other solvents known in the
formulating art. The concentration of emulsifiers may be varied
within wide limits but is preferably in the range of 5 to 25% w/v and
the emulsifiers are conveniently non-ionic surface active agents
including polyoxyalkylene esters of alkyl phenols and polyoxyethylene
derivatives of hexitol anhydrides and anionic surface active agents
including Na lauryl sulphate, fatty alcohol ether sulphates, Na and Ca
salts of alkyl aryl sulphonates and alkyl sulphosuccinates, soaps,
leuthrins, hydrolysed glues, etc. Cationic emulsifiers include
benzalkonium chloride and quaternary ammonium ethosulphates.
W O 90/14006 2 ~ ~ ~ '3 ~ ~ - 8 - PCT/GB90/00818 ~
Amphoteric emulsifiers include carboxymethylated oleic imidazoline and
alkyl dimethyl betain.
Wettable powders comprise an inert solid carrier(s), one or more
surface active agents, and optionally stabilisers and/or
anti-oxidants.
Emulsifiable concentrates comprise emulsifying agents, and often an
organic solvent, such as kerosene, ketones, alcohols, xylenes,
aromatic naphtha, and other solvents known in the art.
Wettable powders and emulsifiable concentrates will normally contain
from 5 to 95~ by weight of the active ingredient, and are diluted, for
example with water, before use.
Aqueous suspensions of a compound of Formula (I) may comprise a
suspension in water together with suspending, stabilising or other
agents. The suspensions or solution may be applied p~ se or in a
diluted form in known fashion.
Aerosol sprays may be prepared as a simple solution or suspension of
the active ingredient in the aerosol propellant and co-solvent such es
halogenated alkanes and the solvents referred to above, respectively.
Pour-on formulations may be made as a solution or suspension of a
combination of the present invention in a liquid medium.
Suitably-moulded, shaped plastics articles impregnated with a
combination of the present invention including impregnated collars,
tags, bands, sheets and strips are also useful formulations. Suitably
the plastics material is a polyvinyl chloride (PVC).
The composition of the present invention may be used to control insect
and acarine pests.
Thus the present invention provides .a method for the control of
arthropods and which comprises adminis,ering to the arthropod or to
W O 90/14006 PC~/GB90/OOX~8
2046932
, , .
its environment an ar~hropodically effective amount of an insectlcidal
composition of the present invention. The present invention also
provides a method for the control and/or eradication of arthropod
infestations of animals and/or of plants, (including trees), and/or
stored products which comprises administering to the animal or locus
an effective amount of an insecticidal composition of the present
invention. The present invention further provides for the
insecticidal compositions of the present invention for use in human
and veterinary medicine, in public health control and in agriculture
for the control of arthropod and/or helminth pests.
The insecticidal compositions of the present invention are of
particular value in the protection of field, forage, plantation,
glasshouse, orchard and vineyard crops, of ornamentals and of
plantation and forest trees, for example, cereals (such as maize,
wheat, rice, sorghum), cotton, tobacco, vegetables and salads (such as
beans, cole crops, curcurbits, lettuce, onions, tomatoes and peppers),
field crops (such as potaeo, sugar beet, ground nuts, soyabean, oil
seed rape), sugar cane, grassland and forage (such as maize, sorghum,
lucerne), plantations (such as of tea, coffee, cocoa, banana, oil
palm, coconut, rubber, spices), orchards and groves (such as of stone
and pip fruit, citrus, kiwifruit, avocado, mango, olives and walnuts),
vineyards, ornamental plants, flowers and shrubs under glass and in
gardens and parks, forest trees (both deciduous and evergreen) in
forests, plantations and nurseries.
They are also valuable in the protection of timber (standing, felled,
converted, stored or structural) from attack by sawflies (e.g.
~rocerus) or beetles (e.g. scolytids, platypodids, lyctids,
bostrychids, cerambycids, anobiids).
They have applications in the protection of stored products such as
grains, fruits, nuts, spices and tobacco, whether whole, milled or
compounded into products. from moth, beetle and mite attack. Also
protected are stored animal products such as skins, hair, wool and
W O 90/14006 PCT/GB90/00818
- 10 -
2~9~
feathers in natural or converted fortD (e.g. as carpets or textiles)
from moth and beetle attack; also stored meat and fish from beetle,
mite and fly attac~.
The insecticidal compositions of the present invention are thus useful
in the control of arthropods e.g. insects and acarines in any
environment where these constitute pests, e.g. in agriculture, in
animal husbandry, in public health control and in domestic situations.
Insect pests include members of the orders Coleoptera (e.g. Anobium,
Ceutorhvnchus, Rhvnchoohorus, CosmoDolites, Lissorhoptrus, Meligethes,
Hvpothenemus, Hvlesinus, Acalvmma~ Lema, Psvlliodes, Leptinotarsa,
Gonocephalum, Agriotes, Dermole~ida, Heteronvchus, Phaedon, Tribolium,
Sitophilus, Diabrotica, Anthonomus or Anthrenus spp.), Lepidoptera
(e.g. Ephestia, Mamestra, Earias, Pectinoohora, Ostrinia,
Trichoplusia, Pieris, Laphvgma, Agrotis, Amathes, Wiseana, Trvporysa,
Diatraea, Soorganothis, Cvdia, Archips, Plutella, Chilo, Heliothis,
Spodootera cr Tineola spp.), Diptera (e.g. Musca, Aedes, Anopheles,
Culex, Glossina, Simulium, Stomoxvs, Haematobia, Tabanus, Hvdrotaea,
Lucilia, Chrvsomia, Callitroga, Dermatobia, Gasterophilus, Hvooderma,
; vlemvia, Atherigona, Chlorops, Phytomvza, Ceratitis, Liriomyza and
MeloDhagus spp.), Phthiraptera (Malophaga e.g. Damalina spp. and
Anoplura e.g. Linognathus and Haematooinus spp.), Hemiptera (e g.
Aphis, Bemisia, Phorodon, Aeneolamia, Empoasca, Parkinsiella, Pvrilla,
Aonidiella, Coccus, Pseudococus, Helopeltis, Lvgus, Dysdercus,
Oxycarenus, Nezara, Aleurodes, Triatoma, Psvlla, Mvsus, Megoura,
Phvlloxera, Adelves, Niloparvata, Neohrotetix or Cimex spp.),
Orthoptera (e.g. Locusta, Grvllus, Schistocerca or Acheta spp.),
Dictyoptera (e.g. Blattella, Peri,olaneta or Blatta spp.), Hymenoptera
(e.g. Athalia, Cephus, Atta, Solenopsis or Monomorium spp.), Isoptera
(e.g. Odontotermes and Reticulitermes spp.), Siphonaptera (e.g.
Ctence~halides or Pulex spp . ), Thysanura (e.g. Lepisma spp.),
Dermaptera (e.g. Forficula spp.), Pscoptera (e.g. Peripsocus spp.) and
Thysanoptera (e.g. Thrips tabaci),.
- ,. .. .
W 0 90/l4006 ~ P ~ /GB90~nOX18
20~6~32
Acarine pests include ticks, e.g. members of the genera BooDhllus,
Ornithodorus, RhiDicephalus, Amblyomma, Hyalomma, Ixodes,
Haemaphysalis, Dermacentor and Anocentor, and mites and manges such as
Acarus, Tetranvchus, PsoroDtes, Notoednes, Sarcoptes, Psorergates,
_orio~tes, Eutrombicula, Demodex, Panonvchus, Bryobia, Eriophyes,
Blaniulus, Polypha~otarsonemus, Scutigerella, and Oniscus spp.
The following Examples are provided by way of illustration of the
present invention and should not be construed as constituting a
limitation thereof in any way,
Example 1
General Purpose compositions for insecticidal formulations
~ w/w
Piperonyl butoxide 68.3 60.7 . .,
n-propyl gallate 22.730.3
Emulsifiers9.0 9.0
ratio piperonyl butoxide: 3:1 2:1
n-propyl gallate
Exam~le 2
General Purpose compositions for insecticidal formulations
% w/w
Piperonyl butoxide 56.25 50 10
_-propyl gallate 18.75 25 50
Emul~ifiers 9 9 g
Solvesso-200 8 8 15.5
propan-2-ol 8 8
l-methyl-2-pyrrolidone - - 15.5
ratio piperonyl butoxide: 3:1 2:1 1:5
n-propyl gallate
W O 90/14006 - 12 - PCT/GB90tO081X
Example 3
General PurPose com~osition for insecticidal formulations
9~ w/w
Piperonyl butoxide 56.25 50.0 12.5
_-propyl gallate18.75 25.0 62.5
propan-2-ol 6.5 6.5 6.5
Solvesso-2006.5 6.5 6.5
Emulsifiers 12.0 12.0 12.0
ratio piperonyl butoxide: 3:1 2:1 1:5
n-propyl gallate
Example 4
Half life data showin~ increased stabilitv of com~ositions
The half life of compositions were measured using standard methods.
The compositions were applied as a thin film onto glass plates at a
rate of 50mg piperonyl butoxide per m2 and maintained under lighting
conditions equivalent to tropical sunlight.
CompositionRatio of piperonvl T 1/2
butoxide n-propyl (Half life in
~allate minutes~
Piperonyl butoxide alone - 30
Piperonyl butoxide and 9:1 70
_-propyl gallate3:1 117
2:1 173
1:5 260
,
; ' .
. ~. ;.-- . .: :-,
-: :
W O 90J14006 - 13 - PCT/GB90/00818
2~ 32
E~ample 5
Field Trial Data
Heliothis on cotton
Cotton plants were sprayed according to the three treatments below.
Insects (Heliothis armigra) were caged onto the foliage at intervals
up to 6 days after spraying and the ~ control results were as
follows:
Trial l
Treatment~ Control of H.armigra
: Days after spraying
0.25 2 days 5 days
l) Alphacypermethrin 43 33 30
(40g/ha)
2) Alphacypermethrin 93 83 37
(40g/ha~
+ technical piperonyl butoxide
(200g/ha)
3) Alphacypermethrin
+ propyl gallate stabilised
piperonyl butoxide * lO0 lO0 50
(200g/ha)
* ratio propyl gallate:
piperonyl butoxide l:2
W O 90/14006 PCr/C,B90~00818
~U4~
Trial 2
1) Alphacypermethrin 80 26.6 20 13.3 6.6
(40g/ha)
2) Alphacypermethrin 100 60 40 26.6 3.0
( 40g/lla )
+ piperonyl butoxide
stabilised with BHT
(200g/ha)
3) Alphacypermethrin 100 66.6 46.6 30 6.6
( 40g/ha )
+ piperonyl butoxide
stabilised with
propyl gallate
(200g/ha)
Colorado Beetle on Potatoes
Potato plants were treated as indicated and the number of insects
present per five plants recorded at intervals as follows:
No. of insects/5 plants
Treatment lb acti~e Date: 29 Jun 5th Jul 10th Jul Season
ingredient/ Average
acre
Untreated - 44.5 157.8 133.0 111.8
Permethrin 0.006 26.5 98.3 124.0 82.9
( PRM)
..
.: ' " ~ '
:
W O 90/l4006 P(~r/CB90/OOXl8
- 15 - 2~9~2
PP~ + 0.006 + 0.25 17.3 60.5 68.8 48.9
piperonyl
butoxide (PB)
PRM + PB 0.006 + 0.25 15.3 36.8 64.5 38.9
( propyl
gallate
stabilised)
PRM 0.012 33.8 87.0 104.8 75.9
PRM + PB 0.006 + 0.50 14.8 38.3 33.8 29.0
PRM + PB + 0.006 + 0.50 10.5 24.5 26.5 20.5
propyl
gallate
