AU614410B2 - Pesticidal compositions containing BHT or BHA potentiators - Google Patents

Description

.4 /i p 614410 COMMONWEALTH OF AUSTRALIA PATENTS ACT 1 52 Form COMPLETE SPECIFICATION FOR OFFICE USE Short Title: Int. Cl: o 0 0 0 o 0 0 0 01 0 O 00 09 0 00 0 0 4 0 0 0 0 10 O 00 0 00 0 10 Application Number: Lodged; Complete Specification-Lodged: Accepted: Lapsed: Published: Priority: Related Art: 0 00 0 00** TO BE COMPLETED BY APPLICANT o oo 0 O 0 0 Name of Applicant: Address of Applicant: Actual Inventor: Address for Service: FAIRFIELD AMERICAN CORPORATION 809 Ha-rison Street, French Town, New Jersey 08825, United States of America Donald R. MACIVER GRIFFITH HACK CO.

71 YORK STREET SYDNEY NSW 2000

AUSTRALIA

Complete Specification for the inv'ti~on entitled: "Pesticidal compositions containing BHT or BHA potentiators".

The following statement is a full description of this invention, including the best method of performing it known to me/us:-

II

::3 COMMONWEALTH OF AUSTRALIA S009466 14/OS/89 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 modities its susceptibility tohe prinsecticide and resistance to that insecticide may occur. Thus, by S1980, resistance to the organochlorine and organophosphorous insecticides Sin heliothis species in Australia, Thailand, Turkey and the Americas is There are a number of ways of countering increasing resistance of insect that land under cultivation can provide. However, with increasing use of a 0 particular insecticide, the insect population modifies its susceptibility 0 o0 o Swhich have a different mode and resistance to thatexisting insecticide may ccur. Thus, by o 0o 0o00 cross-resistant with these. However, this is time-consuming and expensive a 0 ain heliothis speciesno guarantee of success. A further possibility is the Americas is 0 0 0 o 0 becoming a major problem in the cotton growing industry in these countries.

Sthe activityre a number of ways of series countering insecticides so that resistance of insect Sspecie susceptible to the to insecticides. One ay is to develop new series of insecticides which have analogu different mode of action to existing insecticides or by increasing the 0 0 o 00 cross-resistant with these. However, this is time-consuming and expensive o 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 ooo more active analogues of existing insecticides or by increasing the activity of existing insecticides by combining them with a substance which o00000 0ooo 0increases 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 pyrethins and the pyrethroids against susceptible and resistant insect species. Piperonyl butoxide (5-[2-(2-butoxyethoxy)ethoxymethyl]-6-propyl-l,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.

Butylated hydroxytoluene and butylated hydroxyanisole are antioxidants that are commonly used in the food industry as preservatives. AMD/JJ/7th July, 1989.

I A PW0020 They have also been used as stabilisers in insecticide formulations. We have now discovered that BHT and BHA can potentiate the activity of insecticides, such as the pyrethins, the pyrethroids and the organophosphorous series of insecticides, against susceptible and resistant insect species including Musca domestica and heliothis pp. 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; 000:0 the addition of BHT or BHA to piperonyl butoxide protects piperonyl 000 butoxide against light induced degradation.

0000 0 *0 0000 0 0 0 Accordingly, in a first aspect, the present invention provides an 0 organophosphorous, pyrethroid and/or pyrethrin insecticide in combination 01 0 0 with BHT or BRA in a -:atio of 1:5 to 1:100.

0 0 Suitable organophosphorous insecticides include:- 00 O,O-diethyl-O-( 3 -chloro-4-methyl-7-coumarinyl)phosphorothioate (couinaphos); 00 0 0,0-diethyl-0- 5-dichloro-4-bromophenyl) phosphorothiate (bromophosethyl); 0 00 0, O-diethyl 2 -isopropyl- 6 -me thyl -pyrimidin 4 -yl) phosphorothioate a 00 (diazinon); 2,3-p-dioxanedithiol S S-bis, 0,0-diethyl phosphorodithioate (dioxathion); 0000, O-diethyl-O-( 3 ,5, 6 -trichloro-2-pyridyl)phosphorothioate (chiorpyrifos); 0000 0 -tetraethyl, S,S' -methylenediphosphorodithioate (ethion); 0:000' 3- (Dimethoxyphosphinyloxy) -N-dimiethyl-cis-crotonamide (dicrotophos); (1,2-dicarbethoxy ethyl) -O,0-dimethylphosphorodithioate (malathion); cis-l-methyl-2- (l-phenylethoxycarbonyl)vinylphosphate (crotoxyphos); 0-ethyl-0- (quinol-8-yl)phenylphosphorothioate (oxinothiophos); (5,7-dichlorobenzoxazol-2-yl-methyl) -0,0-diethyl phosphorodithioate) (benoxanphos); S(4-chlorophenyl)-thio] -methyl) -0,0-diethyl phosphorodithioate (carbo phenothion); S-tl, 3 -dihydro-1, 3 -dioxo-2H.-isoindol-2-yl-methyl)Oo-dimethyl phosphorodithioate (phosmet); 2-Chloro-l- 4 -dichlorophenyl)vinyldiethylphosphate (chlorfenvinphos) 0, 0-diethyl aecyanobenzylideneamino-oxyphosphonothioate (phoxim) 0, 0-dimethyl cis-l-rethyl-2-methylcarbamoylvinyl-phosphato (monocrotophos) AMD/JJ/7th July, 1989.

0000 0000 o00 0000 cc00 0 0 0000 00 00 0 G0 00 *0 0 0 0 0 00 00 00 0 0 0 0 00 00 a 0 00 00a 0 0000 00000 0 0 PWO020 isopropoxycarbonyl- 1-methylvinyl 0-methyl ethylphosphoramidothioate (propetampho) 0- 2-diethylamino -6 -me thylpyrimidin-4-yl 0 ,0-dimethyl phosphorothioate (pirimiphos methyl) 0 -2 -die thylamino-6 -methylpyrimidin-4-yl 0 ,O-diethyl phosphorothioate (pirimiphos ethyl) 0 -4 -dime thyl sulphamoylphenyl 0 -dime thylphophoro thioate (famphur) Suitable pyrethroid insecticide include those of the formula (I) X 0 /CHO C-R 0 where R is

CH=CH

z CH 3 CH 3 H C (NH)n

I-,

3

HC

and n is 0 or I1 AMD/JJ/7th July, 1989 PWO020 1 21 R is halo, CF 3or CHF 20, R is hydrogen or halo, and Z and Z are each independently selected from halo, CF and methyl, X is halo, and X is H, 3 CN or C CH Cl 00 C 2 H 5 0 0 (0 o N 00000 o 0 0000 orCH 3 0010 00. CH0 CH OCH 2 0. 0 00 0Q 00 00 0 0 000,, 00" 00 0 Preferred pyrethroids for inclusion within the present invention include:- 0 00 00, 0 0 00 0 0 3 -phenoxybenzyl- (1RS) -cis,trans (2,2-dichlorovinyl- 2,2 -dimethyl 0 0 cyc lop rop ane -1-carboxylate (permethrin), (RS) -a-cyano-3 -phenoxybenzyl- (lRS) -ci,trans (2,2-dichlorovinyl) -2,2- 0000 dime thylcyc lopropane carb oxylate (cypermethrin) and its individual 0000 isomers sucb as the (lRS) ci isomer (alphamethrin) (S)-a-cyano-3- 0:0:phenoxybenzyl- (IR) -cis 3-(2,2-dibromovinyl) -2,2-dimethyl cyclopropane- 1-carboxylate (deltamethrin) (RS) -a-cyano-3 -phenoxybenzyl- (IRS) -cis (2-chloro-3, ,3 3-trif luoro propenyl) 2, 2 -dime thyl cyclopropane carboxylate (cyhalothrin) and a mixture of its (Z-(IR)-cji. and (R)(Z)-(IS)/-cis-isomers.

(RS) -a-cyano-3-phenoxybenzyl (RS) (4-chlorophenyl) -3-methylbutyrate (fenvalerate) and the single isomer (esfenvalerate) (RS) -a cyano- 3 -phenoxyb enzyl -2 -di fluo rome thoxyphenyl) -3 methylbutyrate (flucythrinate) (RS)-a-cyano-3-phenoxybenzyl N(2-chloro-a,ca,-trifluoro-p-tolyl)-Dvalimate (fluvalimate) (RS) -a-cyano-4- fluoro- 3-phenoxybenzyl (lRS)-is-trans 3-(2,2 dichlorovinyl) 2, 2 -dime thylcyclopropanecarboxy late (cyfluthrin) AMD/JJ/7th July, 1989.

PW0020 y (RS)-a-cyano-4-fluoro-3-phenoxybenzyl(IRS)-cis-trans-3-(2-chloro-2-(4chlorophenyl)vinyl)-2,2-dimethylcyclopropanecarboxylate (flumethrin) 2-methylbiphenyl-3-ylmethyl(Z)-(IRS,3RS)-3-(2-chloro-3,3,3-trifluoroprop-l- -enyl)2,2-dimethyl cyclopropane carboxylate (Bifenthrin) In a second aspect, the present invention provides an organophosphorous, pyrethroid and/or pyrethrin insecticide in combination with BHT or BHA and piperonyl butoxide in a ratio of 1:0.5:5 to 1:20:200, suitably 1:5:10 to o 1:10:200.

0. 0. The precise amount of insecticide to be applied will depend on the inherent 0 0 activity of the insecticide against the insect species to be controlled, the method of application and the nature of the formulation to be applied 00 09 and whether or not piperonyl bitoxide is included in the formulation but in general the following quantities will be applied.

o-Ce Pyrethroids between 5 and 150 g/hectare o 0 0 0. o 0.0125 and 0.4 Ibs/acre) 0 00 00oo°0 Natural pyrethrin between 2 and 12 ozs/acre 0 o0 Organophophorous insecticides between 50 and 1000 g/hectare (0.125 and o 0o 2.5 Ibs/acre) Piperonyl butoxide between 100 and 1200 g/hectare (0.25 and 000o lbs/acre) o000 BHT or BHA between 10 and 120 (0.02 and 0.3 lbs/acre) 0100000 0 O In a third aspect, the present invention provides BHT or BHA in combination with piperonyl butoxide in a ratio of 1:1 to 1:200. Suitably the ratio is between 1:2 and 1:20 and preferably about 1:10.

In a further aspect the present invention provides a formulation for agrochemical use which comprises BHT or BHA and piperonyl butoxide and/or one or more insecticides from the organophosphorous, pyrethroid or pyrethrin classes of insecticides and a suitable carrier. The carrier may be liquid, solid or gaseous or comprise a mixture of such substances, and the combination of the present invention may be present in a concentration of from 0.025 to 99% w/v depending upon whether the formulation requires further dilution.

AMD/JJ/7th July, 1989.

S* PW0020 Dusts, powders and granules and other solid formulations comprise the combinations of the present invention in intimate admixture with a powdered solid inert carrier for example suitable clays, kaolin, bentonite, attapulgite, adsorbant 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 'ii. desired grinding the products so as to obtain powders and, if desired, granulating, compacting or encapsulating the products.

oeU 0 0 0 Sprays of the combinations of the present invention may comprise a solution 0 oo o in an organic solvent those listed below) or an emulsion in water 0O 0 0(, oo (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 S 0 0 more emulsifiers. Solvents may be present within wide limits but Spreferably 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 emulifiers are conveniently non-ionic surface 00 active agents including polyoxyalkylene esters of alkyl phenols and polyoxyethylene derivatives of hexitol anyhydrides 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.

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 optionallly stabilisers and/'r anti-oxidants.

AMD/JJ/7th July, 1989.

S-4 PW0020 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 to 95% by weight of the active ingredient, and are diluted, for example with water, before use.

00000 o oo 0000 Aqueous suspensions of a compound of Formula may comprise a suspension ao o 0o o in water together with suspending, stabilizing or other agents. The 0000 o o suspensions or solutions may be applied per se or in a diluted form in o00 known fashion.

0 0 0 0 Aerosol sprays may be prepared as a simple solution or suspension of the active ingredient in the aeiosol propellant and co-solvent such as halogenated alkanes and the solvents referred to above, respectively.

00ooo Pour-on formulations may be made as a solution or suspension of a 00 combination of the present invention in a liquid medium. Suitably-moulded, shaped plastics articles impregnated with a combination of the present o invention including impregnated collars, tags, bands, sheets and strips are also useful formulations. Suitably the plastics material is a polyvinyl chloride (PVC).

0ooo 0 0000 0 The combinations of the present invention may be used to control insect and 000000 0° acarine pests.

Thus the present invention provides a method for the control of arthropods and which comprises administering to the arthropod or to its environment an arthropodically effective amount of a combination 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 a combination of the present invention. The present invention further provides for the combinations of the present invention for uso in human and veterinary medicine, in public health control and in agriculture for the control of I arthropod and/or helminth pests.

AMD/JJ/7th July, 1989.

i 't\ PW0020 The combinations 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 potato, sugar beet, ground nuts, soyabean, oil seed rape), sugar cane, grassland and forage (such as onaa maize, sorghum, lucerne), plantations (such as of tea, coffee, cocoa, 0 0 banana, oil palm, coconut, rubber, spices), orchards and groves (such as of 0 0 a stone and pip fruit, citrus, kiwifruit, avocado, mango, olives and 0 0 Co 0 a walnuts), vineyards, ornamental plants, flowers and shrubs under glass and o "o in gardens and parks, forest trees (both deciduous and evergreen) in .on 0 OB 0 forests, plantations and nurseries.

S 0 0 0 O They are also valuable in the protection of timber (standing, felled, converted, stored or structural) from attack by sawflies Urocerus) or o beetles scolytids, platypodids, lyctids, bostrychids, cerambycids, S anobiids).

oO o o0 They have applications in the protection of stored products such as grains, 0 00 fruits, nuts, spices and tobacco, whether whole, milled or compounded into products, from moth, beetle and mite attack. Also protected are stored oao animal products such as skins, hair, wool and feathers in natural or o0 converted form as carpets or textiles) from moth and beetle attack; 00..o 0 0 also stored meat and fish from beetle, mite and fly attack.

BHT and BHA have been found to potentiate the activity of pyrethroids against Misca domestica and Plutella xvlostella of org.nophophorous insecticides against Musca dohiestica and Tetranychus urticae and of pyrethrins against Musca domestica.

The combination 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.

AMD/JJ/7th July, 1989.

PWO020 Insect pests include members of the orders Coleoptera g.

Anobium, Ceutorhynchus ,Rhynchophorus. Cosmopolites, Lissorhoptrus, Meligethes, Hypothenemus, H-ylesinus, Acalymma, Lema, Psylliodes, Leptinotarsa, Gonocephalui, Agriotes, Derinolepida, Heteronychus, Phaedon, Tribolium, Sitophilus, Diabrotica, Anthonom-us or Anthrenus spp.), Lepidoptera Ephestia, lMamestra, Earias, Pectinophora, Ostrinia, Trichoplusia. Pieris, Laphygma. Agrotis, Amathes, Wiseana, Try-porysa, Diatraea, Sporganothis, Gydia, Archips, Plutella, Chilo, Heliothis, S0 od.optera or Tineola spp.), Diptera Musca, Aedes, Anopheles, Culex, Glossina. Slinuiu, Stomoxvs, Haematobia, Tabanus, HyIdrotaea, Lucilia, a,,Chrysomia, Callitroga, Dermatobia, Casterophilus, Hypoderma, Hylemnyia, Atherigona, Chiorops.. Phytomyza, Ceratitis, Liriomyza and Melophagus spp.), Phthiraptera (IMalophaga e.g. Damalina spp. and Ano-Plura e.g.

00 0 o 0 Linognathus and Haematopinus spp.), Hemiptera Aphis, Bemisia,Phorodon, Aeneolamia, Empoasca, Parkirisiella, Pyrilla, Aonidiella, Coccus, Pseudococus. Helopeltis, Lygus, Dysdercus, Oxycarenus, Nezara, Aleurodes, Triatoma, Psylla, Mysus, Megoura, Phylloxera, Adelyes, Niloparvata, Nephrotetix or Cimex spp.), Orthoptera Locusta, Gryllus, Schistocerca or Achetja spp.), Dictyoptera Blattella, Periplaneta or Blatta spp.), Hymenoptera Athalia, Ce-Phus, Atta, 004 Solenopsis or iMonomorium spp.), Isoptera Odontotermes and Reticulitermes spp.), Siphonaptera Ctenocephalides or Pulex spp.), Thysanura Lepisma spp.), Dermaptera Forficula spp.), Pscoptera Peripsocus spp. and Thysanoptera Thrips tabaci), Acarine pests include ticks, e.g. members of the genera Boophilus ,Ornithodorus, Rhipicephalus, Amblyomma, Hyalomma, Ixodes, Haemaphysalis, Dermacentor and Anocentor, and mites and manges such as Acarus, Tetranychus, Psoroptes, Notoednes, Sarcoptes, Psorergates, Chorioptes, Eutrombicula, Demodex, Panonychus, Bryobia, Eriophyes, a Blaniulus, Polyphagotarsonemus, Scutigerella, and Oniscus spp.

AMD/JJ/7th July, 1989.

Is~ PW0020 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 TEST METHOD o o 0 o Four day old Musca domestica L.adults (strain:F58WT2) were anesthetized o, o with CO 2 and treatments were applied to their dorsal thorax in one 1 of 09" 0 2 oo acetone. Treatments included pyrethrins alone and in combination with BHT S at 1:1, 5:1, and 10:1 ratios (BHT:pyrethrins). Each treatment was applied 00 00 o 0 at six concentrations to three replicates of 20 flies flies/concentration) and flies were maintained on a 10% sugar solution in 16 oz. plastic containers. Mortality (dead and moribund flies) was recorded at 48 hours post-treatment and data were subjected to probit 0o 0 0 0 o analysis by the SAS procedure. Synergism was considered significant when o 0, the 95% fiducial limits for the BHT treatments did not overlap the limits for pyrethrins alone.

0 06 TEST RESULTS 0 0 a 4 0 000 Toxicity data for house flies treated with pyrethrins plus BHT. LD valves were determined as g pyrethrins/fly.

Fiducial Fiducial Limits SR90* LD90 Limits Pyrethrins 0.69 0.63-0.76 1.48 1.26-1.87 1:1 BHT :Pyrethrins 0.69 0.64-0.73 1.00 1.21 1.09-1.39 1.22 5:1 BHT :Pyrethrins 0.57** 0.52-0.61 1.21** 1.06** 0.95-1.25 1.40** IC:l BHT :Pyrethrins 0.51** 0.37-0.58 1.35** 0.79 0.67-1.31 1.87 r AMD/JJ/7th July, 1989.

-11- PWO020 *SR=Synergist Ratio LD for Pyrethrins Alone LD xfor Pyrethrins +BH-T **These treatments were significantly (P=0.05) different than pyrethrins alone.

0 0 00'00 o9 0 0009 a 0 0 09 0 0 *00 o) 0 0 0 0 0000 0 0 0 0 0 0 00 0 0 0 0 0 o o 0 0 a0 0 00 0600 *0000 0 000000 Example 2 General Purpose Formulation for adding to insecticide formulation Piperonyl Butoxide (technical) Butylated Hydroxytoluene (BHT) Emulsifiers 81.9% 9 .1% 100,0% Example 3 Emulsifiable Conctenblate Piperonyl Butoxide (technical) Ethylan KEO Xylene Butylated Hydroxyanisole 50.0 20.0 25.0 100.00 AMD/JJ/7th July, 1989.

PWO020 Examle 4 Wettable Powder 0 0 0o 0 00 0 09 0 a 0 Piperonyl Butoxide (technical) Attapulgite Sodium isopropylbenzene suiphonate Sodium salt of condensed naphthalene sulphonic acid Butylated hydroxytoluene 25.0 66.0 100.00 000.

0, 0 0 00 a 0 00 0 0 0 0 00 0 00 0 00 0001) 0 0 o 0 Example Dust Pyrethrins Piperonyl Butoxide (technical) Butylated Hydroxyanisole Talc 0.1 97.9 100.00 AMD/JJ/7th July, 1989.

-13- PW0020 Exampole 6 Bait Pyrethrins Piperonyl Butoxide Icing Sugar 89.6 Butylated Hydroxytoluene 9, 100.00 Example 7 Aerosol Pyreth rins Piperonyl Butoxide (technical) Butylated Hydroxyanisole 1 1-Trichioroethane Odoui ass Kerosene Arcton 11/12. 50:50 mix 0.50 4 .00 0.40 5.00 10.10 80.00 100.00 AMD/JJ/7th July, 1989.

PWO020 Example 8 Sp~rayz 0 0 0 9 0 0 0 04 014 0 0 0~ 00 0~ 00 0 0 0 O 0 0 0 0 0 0 00 a0 00 00 0 0aa0 Piperonyl Butoxide (technical) Pyrethrins Butylated Hydroxyanisole Xylene Odourless Kerosene 5.00 5.00 89.00 100.00 Example 9 Potentiated Spray Pyrethrins Piperonyl Butoxide Butylated Hydroxyanisole Xylene Odourless Kerosene 1.00 10.00 1.00 5.00 83.00 100.00 AMD/JJ/7th July, 1989.