AU706835B2 - An arthropod control composition for plant protection - Google Patents

Description

AN ARTHROPOD CONTROL COMPOSITION FOR PLANT PROTECTION Field of the Invention The present invention relates to arthropod control compositions for plant protection. More specifically said invention relates to non-toxic arthropod control composition suitable for application to foliage for plant protection comprising a Behaviour-Interfering Compound, vegetable oil and optionally surface active compounds and diluents.

Background of the Invention Biocompatible Insect Control-agents (herein called "BICs") i.e. pest control agents which pose little hazard to humans and to the environment have been known for many years and their number is steadily growing. BICs can act as insect behavioral modifiers (such as feeding and oviposition detergents, repellents, etc.), hyperactivity inducers, knock down agents, physical barriers or physical poisons [J.J.

Kabara (1987), Fatty Acids and Esters as Antimicrobial/insecticidal Agents. In G.

Fuller and D. Nees Ecology and Metabolism of Plant Lipids. Washington: ACS, pp. 220-238].

BICs are related to many chemical classes such as certain carboxylic acids, alcohols, esters, ethers, amides, terpenoids, limonoids, sulfides and heterocyclic °o compounds Carlson (1978) Repellents. In: Kirk. Othmer Encyclo.

7 D o 2 1 o *o* *o o o oo Chem. Technol. pp. 786-805].

Increasingly, BIC are used as alternatives for neurotoxic insecticides mainly for human protection with (DE 3,211,632) and without (Carlson 1978) oils but also for veterinary purposes and to control food and store insects (IL Patent No. 53570).

Many BIC possess properties which are highly desirable also for plant protection, mainly on account of their rapid and safe action. However, most BIC cannot be applied to to foliage due to their phytotoxic nature (Kabara 1987). One solution to this problem is to formulate BIC in a way which decreases their phytotoxicity and at the same time preserves or promotes their activity against the target pest.

The term agricultural oils Helser and F.W. Plapp \S (1986) Combinations of Oils and Similar Compounds with Insecticides: Effect on Toxicity and Leaf Residues. South.

Entomol.: 75-81] is used rather loosely to describe different mixtures of lipophilic chemicals [such as mineral oils, vegetable (corp) oils (hereinafter called and 2 silicones], which differ enormously in their on-leaf behavior Veierov, M.J. Berlinger and A. Fenigstein (1988), The Residual Behavior of Fenpropathrin and Chlorpyrifos Applied as Aqueous Emulsions and Oil Solution to Greenhouse Tomato Leaves. Med. Fac. Landbouww, Gent 53:1535-1541]. Vegetable oils (VO) have been used for many years directly for control o* o 27/04 '99 17:53 27/4 '9 1:53 ''61 3 9882 9854 CARTER SMITH B PATENT OFFICE I 0/0 R003/007 of weeds, fungi and insects, and as solvents and additives in conventional pesticide formulations. Vegetable oils are fatty oils, i.e. triesters of glycerol with fatty acids that are liquid at ambient temperature.

Oils of various types were found to increase penetration of pesticides into leaf interiors (Veicrov 1988). This in part explained the enhancement phytotoxicity of herbicides when applied to foliage together with oils.

The ability of vegetable oils to enhance intrinsic phytotoxicity of agrochemicals is well documented (Arnold 1989; Kirkwood, R.C. 1993; Lundegardh 1991). The use of vegetable oils can greatly enhance the activity of foliage applied herbicide (Kirkwood 1993). Formulation with vegetable oils can enhance absorption adpyYotoxicity ofherbicides (Kirkwood 199). hus vegetable oils have been used on an increasingly large scale (as additives to herbicides) during rccent years. The most common are oils from soybeans and rape 0 0*(Lundegardh 1991). Oils from cotton and sunflowers can also be used (Lundegardli 15 1991). However, vegetable oils have not been suggested for use in reducing the phytotoxicity of agrochemicals.

Bref Description of the Inventionl The present invention provides in one form a method for controlling arthiropods on foliar plants by applying an effective amount of a non-toxic arthiropod composition including: S(a) at least one -non-toxic Behaviour-Interfering Compound selected from

C

10

-C

22 alcohols, lauryl alcohol, cetyl alcohol, oleyl alcohol, myristyl alcohol, stearyl alcohol, 2-ethyl-i ,3-hex-anediol, 2-butyl-2-ethyl- 1,3 -propanediol;

C

1 0

-C

2 2 carbonyl compounds, methyl-nonyl ketone, butopyronoxyl (indalone), citronellal, citral;

CID-C

22 carboxylic acids, myristic acid, stearic acid; terpenoids, camphor, camphene, terpinen-4-ol, isoborneol, borneol, isobornyl acetate, bomnyl acetate, phytol, .f-farnesene, farnesol, geramiol, terpineol, pcymeme, ocimene, lirnonene, thymnol, pinene; polybasic carboxylic acids, oxalic acid, fuxuaric acid, succinic acid, malic acid, fiimaric acid, malic acid, oleic acid; DVGJ:J17121CL P PH 1999 27/04 '99 TUIE 16:48 [TX/RX NO 7436] Z~003 27i0 '99 17:4 ~6 3 882 854CARTER SMITH B PATENT OFFICE 000o4/007 27/04 '99 17:54 V61 3 9882 9854 0e S. *5 0*s*

OSSS

9 *9 5 0 See S 59

S~*

substituted mono and polybasic carboxylic acids, adipic acid, sebacic acid, latic acid, tartaric acid, citric acid, aconitic acid, acidoleic acid, sorbic acid; N-butylacetanillide, N,N-diethyl-3-methylbenzrnide (DEET, NNdeithyl-m-toluamide), benzyl benzoate, 2-hydroxethyl n-octyl sulfide (MGK-874); butoxypoly(propylene glycol); esters of carboxylic acids, dimethyl phithalate, diethyl phthalate, dibutyl phthalate, dibutyl succinate, dibutyl sebacate, dibutyl adipate, myri state esters, methyl myristate.

at least one vegetable oil present at a level of at least 50% w/w of the 10 Behaviour-Interfering Compound;, optionally surface active compounds; and optionally diluents.

An arthropod control composition will be considered non-toxic when it comprises natural and/or synthetic components which are non-hazardous to vertebrates, are 15 safe to humans and are permitted to be used in food, cosmetics, clothing, hygienics, or in other products that may become in direct contact with humans or food- The Behaviour-Interfering Compound is an agent having properties DVO;JT'D#241 19-CL 27 April I W9 4a 5**0 5 0 05 55*5

OS

5* 5 5* 5S 27/04 '99 TUE 16:48 [TX/RX NO 7436] 9~004 relying on either, behaviour controlling (modifying) properties or physical disruption of host acceptance by an insect target, but is non-hazardous to arthropods and is safe to humans. Accordingly, Behaviour Interfering Compounds exclude conventional insecticides.

Vegetable oils are known for their ability to enhance intrinsic phytotoxicity of foliar applied agrochemicals. Therefore, the use of vegetable oils with Behaviour- Interfering Compound for reducing the phytotoxicity of the Behaviour-Interfering Compound is unexpected. Furthermore, the compositions of the present invention not only perform effectively with or without minimal phytotoxicity symptoms, but also surprisingly show synergism.

Detailed description of the Invention The present invention relates to a non-toxic arthropod control composition suitable for application to foliage for plant protection comprising: at least one non-toxic Behaviour-Interfering Compound; at least one vegetable oil in an amount effective to reduce the go phytotoxicity of the Behaviour-Interfering Compound; oooo surface active compounds emulsifiers); and diluents (such as water or an appropriate organic solvents).

According to the present invention the Behaviour-Interfering Compounds phytotoxicity is masked and their efficacy is increased by formulating them with vegetable oils in the absence or presence of additional adjuvants.

Vegetable oils mask the Behaviour-Interfering Compounds phytotoxicity by reducing the contact between the Behaviour-Interfering Compound residue and leaf- 25 surface, or by retarding the Behaviour-Interfering Compound foliar penetration. The efficacy of the Behaviour-Interfering Compound is promoted due to the action of the 0. oil component as synergistic and/or a complementary control measure. The oil component acts also as an extender.

Formulation of the Behaviour-Interfering Compound with a vegetable oil resulted in a very fast and persistent action, which is a prerequisite to control of some of the most serious types of agricultural pests.

DVG:JMD'#24119CLM 22 February 1999 Quick action is required to prevent the setting of migration stages of the target pest, and to deter egg deposition and/or virus transmission.

S.

OSS

S. S S

S.

SS *5 0 0 *0S S 5 S S

S*

0* S 50 0 5 00 S. 0* 00 55 0 0 5 S 55 DVG:JMD:#24119 CLM 2 erayI~ 22 Febmary 1999 5A Persistent action guarantee prolonged protection both by repelling migrating stages and by killing the less mobile ones (such as certain types of larvae).

In summary, the Behaviour-Interfering Compound functions are: a) To provide fast activity as behaviour modifiers, knock-down agents and/or physical barriers. b) To extend the effective duration of the oil residue.

Vegetable oil function: a) To reduce phytotoxicity. b) To synergise, or to provide complementary control activity. c) To extend Behaviour-Interfering Compound effective duration.

The Behaviour-Interfering Compound is any known conventional compound that can interrupt or alter the normal behavioral sequences of the target. The Behaviour-Interfering Compound can be any repellent or deterrent agent, hyperactivity inducer or irritant, narcotic, knock-down agent, physical barrier agent or physical poison. Examples are general purpose arthropod repellent, C 1 0

-C

22 alcohols, Clo-C22 carbonyl compounds, Clo-C 22 carboxylic acids and terpenoids, polybasic carboxylic acids, substituted mono and polybasic carboxylic acids and esters of the mentioned carboxylic acids. More specifically the Behaviour- Interfering Compound is selected from methyl-nonyl ketone, N-butyl acetanilide, N,N-diethyl-3-methylbenzmide (DEET), dibutyl phthalate, dimethyl phthalate, dibutyl succinate, dibutyl adipate, butopyronoxyl (Indalone), butoxypoly (propylene glycol), benzyl benzoate, 2-ethyl-l-,3-hexanedroil, 2-butyl-2-ethyl-1,3propanediol, 2-hydroxyethyl n-octyl sulfide, citronella, camphor, camphene, terpinen-4-ol, linalool, isoborneol, borneol, isobornyl acetate, bornyl acetate, phytol, B-farnesene, lauryl alcohol, cetyl alcohol, oleyl alcohol, myristic acid, stearic acid, famesol, geranoil, citral, terpineol, beta-farnesene, p-cymene, ocimene, limonene, thymol, pinene, myristyl alcohol, stearyl alcohol, oxalic acid, fumaric acid, succinic acid, adipic acid, sebacic acid, malic acid, fumaric acid, maleic acid, tartaric acid, citric acid, aconitic acid, aconitic acid, lactic acid, oleic acid, sorbic acid, myristate .esters and diethyl phthalate.

*o *o BMH:SM:#24119.DIV -6- 17 December 1996 The vegetable oil can be selected from cottonseed oil, soybean oil, rapeseed oil, castor oil, sunflower oil, groundnut oil, palm oil, safflower oil, coconut oil, sesame oil, corn oil, linseed oil, tung oil and palm kernel oil.

The composition according to the present invention can be used against many types of arthropods e.g. sucking arthropods. Said composition can be applied against whiteflies (Aleurodidea) and aphids (Aphidoidiea) and soft bodied organisms such as mites, hoppers, mealy bugs and thrips.

The present invention relates also to a method for protection of plants against arthropod comprising application or spraying of the arthropod control composition defined above to foliage.

The invention will be clarified and exemplified by means of the following examples. Said examples are in no way intended to limit the scope of the invention.

Formulation Examples Example 1.

a) Emulsifiable concentrate (without co-solvent) 6-24 parts of active ingredient 88-70 parts of vegetable oil 6 parts of surfactant (high hlb surfactant such as Tween 80 Tween b) Emulsifiable concentrate (including co-solvent) -1 BMH:SM:#24119.DIV 7 17 December 1996 D m 1 *oo* *o BM :M*41.I 7 *7Dcebr1 parts of active ingredient 41 parts of vegetable oil 41 parts of aromatic co-solvent (such as xylene) 3 parts of surfactant (preferably high hlb surfactant such as Tween 80 or Tween c) Emulsifiable concentrate (including co-solvent) parts of active ingredient 16 parts of vegetable oil 78 parts of polar co-solvent (such as ethanol) 1 parts of surfactant (preferably high hlb surfactant such as Tween 80 or Tween By dilution of such a concentrate with water it is possible to prepare emulsions of the desired concentration which are especially suitable for leaf application.

d) Oil solution (for Ultra Low Volume spray) 1-3 parts of active ingredient 7-9 parts of vegetable oil 0-1 parts of surfactant (preferably high hlb surfactant such as Tween 80 or Tween 20 Biological Examples: PHYTOTOXICITY

TESTS

Example 2.

Greenhouse test: The phytotoxicity of Behaviour-Interfering Compound vegetable oil emulsions (examples la-d) was compared to that of emulsions of the separated S. components and to untreated controls. The emulsions were sprayed onto potted 25 seedlings of cotton (Acala BMH:SM:#24119.DIV 8 17 Decmber 1996 SJ-2) and tomato (Marmande) at the 4 leaf stage, and to pepper (Wyndal) and cucumber (Beit Alfa) at the 2 leaf stage. Sprays beyond runoff were made with hand-held sprayer at 4-6 psi. Discrete drops sprays (Ultra Low Volume, ULV) were applied with a commercial aerodynamic atomizer (Atomist, Root-Lowell Crop., To ensure LV-spray uniformity the potted plants were placed individually on a rotating table in front of the sprayer. The treated plants were held under greenhouse at average minimum and maximum temperatures were 15 and 22 0

C,

respectively. Leaf damages were determined twice, 7 and 14 days post treatments.

Individual leaves were visually assessed by averaging give samples, each consist of ten potted plants. A rating of 0, 1, 2, 3, 4 indicated 1-10%, 11-25%, 26- >50% average leaf damage respectively.

For all test plant species, treatments with Behaviour-Interfering Compound vegetable oil formulations resulted in significantly lower level of foliar damage than treatment with Behaviour-Interfering Compound alone:

S

S S S.

S.

S

S SS

S

Injury Indices on the Indicated Test Plants Chemical' Oil Cotton Tomato Paper Cucumber Comments 2 Esters BP 4 4 4 BP 4 4 4

ULV

BP Cottonseed oil 0 0 0 BP Cottonseed oil 0 0 0

ULV

BP Rapeseed oil 0 0 0 BP Castor oil 0 0 0 BP Soybean oil 0 0 1 BMH:SM:#24119.DIV -9- 17 Dccember 1996 Injury Indices on the Indicated Test Plants Cheical 1Oil Cotton Tomato Paper Cucumber _Ccsments 2

BNBN

S-BNBN

BNBN

BNBN

BNBN

BNBN

~oBNBN

MAC

MAC

SMAC

MAC

MAC

SAC

SAC

Cottonseed oil Cottonseed oil Rapeseed oil Castor oil Soybean oil Cotosed)i Cottonseed oil Cottonseed oil Cottonseed oil Cottonseed oil Rapeseed oil Soben) i Cottonseed oil Rape-seed oil Soybean oil Cotosed)i Cottonseed oil

ULV

ULV

Carboxylic acids O 2 2 O 0 0 O 0 0 O 0 0 O 1 0 O 0 0 Ethanol Xylene Xylene Xylene CAl CAl CAl CAl Fatty alcohols O 1 2 O 0 0 0 0 0 O 0 0 a a a.

a. a a. a *a*aa.

2SLAJ.

LAl LA1 LAl

TER

TER.

TER.

MIX.

MIX.

mix.

Terpenoids 4 4 O 2 O 1 Ethanol 5\ Miscellaneous Dept(- 9 Deet Castor oil MGK-874 MSK-874 Castor oil Injury Indices on the Indicated Test Plants 1 7 Chemical Oil Cotton Tomato Paper Cucumber Ccments 2 Oils Untreated 0 0 0 0 Cottonseed oil 0 0 0 0 Rapeseed oil 0 0 0 0 Soybean oil 0 0 0 0 Castor oil 0 0 0

S

\o 1 BNBN Benzyl benzoate, BP dibutyl phthalate, CAl cetyl alcohol, Deet N,N-diethyl-m-toluamide, LA1 lauryl alcohol, M3K-874 2-hydroxy-n-octyl sulfide, MAc myristic Acid, SAc Stearic acid, TER.MIX terpenoid mixture consists of Phytol Linalool Geraniol Carvone BIC concen. l 1% wt/wt, formulated with no co-solvent, if not specified otherwise.

2 Ethanol contains 3% ethanol, LV low volume spray, Xylene contains 3% xylene.

Example 3.

Field test: Commercial cotton (H-23) was sown in regular row width (96.5cm) during mid April 1991 in Kibbutz Ein-Hahoresh, Israel. Drip irrigation (385m 3 water per 1000m 2 and other standard agronomic practices were employed including insecticides sprays against moths and aphids (combination of Thionex 350g/1000m 3 Supracide 2 50g/1000m 3 on 21th June 1991 and Monocron 200g/1000m 3 on 6th September 1991). The plots were sprayed twice by BIC+VO emulsions (on 8th and 14th August 1991) at 70 liter/1000m 3 rate using portable mist blower.

Prior to the commercial harvest (6th October 1991), 11 bolls were sampled from the inner rows of each replicate and weighed and ginned. Lint quality was assessed by standard tests in the laboratories of the Cotton Production and Marketing Board Ltd., Herzellia, Israel. Foliar injuries s assessed visually as described in Example 2.

No phytotoxic symptoms or significant changes in agronomic traits were found on plots treated with BIC+VO formulations compared to the control plots; plots treated with BIC alone suffered heavy foliar damage.

tL Boll -emi 1 2 Injury Size Lint Sugars Cmical Oil Index Homogeneity Control 0 7.8 40.3 0.032 85.0 Cottonseed oil 0 7.0 39.8 0.026 86.2 BP 4 BP Cottonseed oil 0 7.0 39.9 0.024 86.2 CAl Cottonseed oil 0 7.5 40.0 0.036 85.9 LA1 Cottonseed oil 0 7.7 40.7 0.027 85.0 Control 0 Zo Soybean oil 0 BP 4 S BP Soybean oil 0 CA1 Soybean oil 0 SLA1 Soybean oil 0 S 1 1% wt/wt aqueous emulsion of BP dibutyl phthalate, CA1 cetyl alcohol, LAI lauryl alcohol.

2 Oil concentration 3%.

*12 Biological Examples: BIOACTIVITY TESTS: Example 4.

Tobacco Whitefly adults response to various Behaviour-Interfering Compounds: Tobacco Whitefly, (TWF, Bemisia tabaci) was reared on cotton seedlings in green house. Female whiteflies were caught with aspirator equipped with contraption, and transfer to clip-on leaf cage (transparent cylinder, base diameter 2cm, height 7cm).

The leaf cages, each containing twenty females, were attached to lower side of leaves of pre-treated cotton seedlings. The cotton seedlings had been sprayed to runoff with Behaviour-Interfering Compound and Behaviour-Interfering Compound vegetable oil and held under controlled conditions for various aging intervals.

TWF settling and mortality were recorded after exposures of 1.5, 5 and 24hr.

Mortality results were corrected according to Abbott's formula Abbott, J.

Econ. Entomol. 18:265-267 (1925)]; settling deterrence was expressed as Settling Ratio where T C are the percentage of adults settled on treatment and control respectively after t hours of exposure). All experiments replicated 9-12 times.

A strong settling deterrence followed by death of TWF-adults were observed for the various Behaviour-Interfering Compound types. The activity of all combinations were stronger than those of each component separately (in several

S.

cases activity of Behaviour-Interfering Compound alone could not be measured due to severe leaf injuries).

*0 *6 00 179 Settling Ratio Mortality After the 2 After the Plant C2danicald IRPiaetz E epdieat Injurg wt/wt) 4 hr. 24 hrs. 4 hrs. 24 hrs. Index 0O CO Oil alone 18

BP

l0 BP CO

BNBN

BNBN CC

BS

1 BS CO Arcmatic esters 0 0 0 99 100 0 61 MAc MAc 00 MAc+CA1 00 CAl CAl CO OA 00 Aliphatic esters 123 100 o 7 Carboxylic acids 31 83 0 12 1 2 Fatty alcohols 76 98 12 29 2 Terpenoids 15 17 125 100 58 42 9 20 Miscellaneous 83 97 6 31

S

TER. MIX.

TER. MIX. 00 Camphene Camphene GD Camphor 00

ETH

ETH CC) 26 6 0 0 76 31 0 48 24- Aqueous emulsions of BNBN benzyl benzoate, BP dibutyl phthalate, BS dibutyl sebacate, CA) cetyl alcohol, 00 cottonseed oil, ETH 2-Ethyl-l, 3-hexanediol, LA1 lauryl alcohol, MAc myristic Acid, MAc+CA of each), OA) Oleyl alcohol, TER. MIX. terpenoid mixture consists of Phytol Linalool Geraniol Carvone 00 corcen. 3% and BIC concen. 1% wt/wt, formulated with no co-solvent, if not specified otherwise.

2 Three days post spray to cotton seedlings.

3 A rating of 0, 1, 2, 3, 4 indicated 1-10%, 11-25%, 26-50%, an average leaf damage.

Example 4: CONTINUED.

(Responses of Tobacco Whitefly adults to various BIC) SETTLING RATIO MORTALITY PLANT

AFTER

2

AFTER

2

INJURY

INDEX

3

CHEMICALS

1 wt/wt) 4h 24h 4h 24h Carboxylic acids CIA 100 93 0.5 2.8% 0 CIA CO 1.6 2.6 6.0 94 0 MALE CO 34.8 8.3 34.4 86.5 0 MALI CO 0 0.3 27 98.5 0 SUCC CO 34.8 8.6 7.8 62.3 0 1 CIA citric acid, MALE Maleic acid, MALI malic acid, SUCC succinic acid CO cottonseed oil, CO concen 3% and BIC concen 1% wt/wt, formulated with 15 no cosolvent, if not specified otherwise.

2 Three days post spray to cotton seedlings.

3 A rating of 0, 1, 2, 3, 4 indicated 1-10%, 10-25%, 25-50%, >50% an average leaf damage.

Example 4a The synergistic effects of Behaviour-Interfering Compound and vegetable oil composition The compositions of Behaviour-Interfering Compound and vegetable oil produce produce synergistic effects [calculated after Limple in Richer DL (1987). Pest. Sci.

19:309-3151]. The following table is based on Example 4 above and includes all Behaviour-Interfering Compounds whose damage to the plants was sufficiently slow to permit assessment of their intrinsic action or the target-insect.

BMH:SM:#24119.DIV 15 17 Dcember 1996 COMPOSITION SETTLING RATIOMOTLY after after 4 nr 24 hr 24 ir BS+ Co Expected Observed synergism synergism MAc 1-CC Expected Otserved CAI CO Camph. *CO Expected Observed Expected Observed Expected Observed Expected Observed 6.2 a synergism 15 12 synergism 25 58 synergism 16 6 synergism 20 1.8 synergism 51 12 synergism 60 29 synergism 62 42 synergism 60 31 synergism 65 2.6 synergism synergism 39 56 synergism 37 synergism 63 31 synergism 33 48 synergism 39 94 synergism

ETH+CO,

CIA+CO

-1 5A Example TWF adults response to dibutyl phthalate in combination with various vegetable oils performed as described in example 3.

The four vegetable oil dibutyl phthalate combinations showed a very strong and persistent deterrence followed by death of TWF adults: uays Posto1 Spray 2 Settling Ratio Oil alone Oil BP Is- 7 17 Oil type Cottonseed Soybean Rapeseed Castor Cottonseed Soybean Rapeseed Castor Cottonseed Soybean Rapeseed Castor Mortality Oil alone Oil BP 1.1 2.0 2.3 5.9 85 90 0.0 5.5 84 90 5.3 9.1 0.0 0.0 0.0 0.0 7.3 12.3 0.0 0.0 7.0 12.0 0.0 0.0 69 91 72 91 15 6.8 83 72 0.9 0.0 54 44 99 100 100 100 69 100 99 37 56 98 Aqueous emulsions of 3% oil and of 3% oil 1% dibutyl phthalate.

SR where T C are the percentage of adults settled on treatment and control respectively.

Example 6.

Responses of development stages of TWF to various Behaviour-Interfering Compounds: Cotton seedlings sprayed with Behaviour-Interfering Compound combinations and with cottonseed oil and were held indoors A week postspray, leaf cages, each containing twenty females, were attached to lower leaf side for 24 hours. The number of eggs laid was counted under binocular microscope and compared with the control. The nymphs developing from the eggs, until the pupal state, were counted 15-17 days after oviposition.

Seven-days old residues of CA1+CO were active against developmental stages, whereas BP+CO residue was still active primarily against developmental stages, whereas BP+CO residue was still active primarily against adults.

Mortality No. Eggs Relative Relative Relative of Adults per No. Eggs No. Pupae No. Pupa Chemicals' Female per Female per Female Per Eggs Control 0 5.6 100 100 100 CO 15 4.2 75 39 52 BP CO 91 0 0 0 0 CA1 CO 15 2.5 45 7 16 LA1 CO 4 4.7 75 15 a a *e..a 1 Aqueous emulsions of CO cottonseed oil, BP dibutyl phthalate, CA1 cetyl alcohol, LA1 lauryl alcohol, Concentrations wt/wt) were CO BIC when not specified otherwise.

Example 6: CONTINUED.

(Responses of developments stages of TWF to various Behaviour-Interfering Compounds) BMH:SM:#24119.DIV 17- 17 Dccmbr 1996

L

17 December 1996

CHEMICALS

1 MORTALITY NO. RELATIVE RELATIVE RELATIVE OF ADULTS EGGS NO. EGGS NO. PUPAE NO. PUPA PER PER PER PER EGGS FEMALE FEMALE FEMALE (Con=100%) (Con=100%) (Con=100%) 0 4.7 100 100 100 Non-treated CO 15 3.5 75 39 100 CIA 0 6.3 114 116 103 CIA CO 90 0.2 4.5 3.3 MALE CO 87 0.1 3.0 0.6 SUCC CO 62 0.2 6.0 6.0 100 MMYR 0 5.7 122 89 73 MMYR CO 2 3.7 79 31 39 1 Aqueous emulsions of CO cottonseed oil, CIA Citric acid, MALE Maleic acid, SUCC succinic acid, MMYR methyl myristate Concentrations wt/wt) were CO=3%, BIC when not specified otherwise.

Responses of development stages or TWF to direct spray of various Behaviour- Interfering Compounds S. S S

S

Cotton seedlings infected with a developmental stages of TWF were sprayed to runoff, after counting the eggs or the larvae presented. The plants were held under controlled conditions and the fraction of an immature stage developed into adults were measured and compared to that of the untreated control. The spray toxicity of Behaviour-Interfering Compound vegetable oil against various developmental 20 stages of TWF is demonstrated in the following example.

Survival of whitefly after direct spray of the indicated immature stage Chemicals' Egg L1 L2 L3 L4(P) CO 87 3.60 1.90 4.65 9.09 LAL +CO 49 0.00 0.28 0.00 0.74 CAL +CO 59 1.33 9.30 12.90 66.7 SAL +CO 93 0.74 0.27 0.22 13.0 OAL +CO 56 0.00 1.15 0.24 0.18 BMH:SM:#24119.DIV 18- 17 December 1996 1. Aqueous emulsions of: CO cottonseed oil, LAL lauryl alcohol, CAL cetyl alcohol, SAL stearyl alcohol, OAL Oleyl alcohol. Concentrations (%wt/wt) were CO BIC when not specified otherwise 2. LI 1st instar nymph, L2= 2nd instar nymph, L3 3rd instar nymph, L4 4th instar nymph (pupa) 3. Survival [fraction of a treated immature stage developed into adults] [fraction of an untreated immature stage developed into adults] Example 7.

Test of Dibutyl phthalate VO combination as protectant against nonpersistent virus transmitted by Aphids (Myzus persicae): Healthy cucumber seedlings (Beit Alfa) which served as a test plants were sprayed to runoff with Behaviour-Interfering Compound vegetable oil combinations and allowed to dry.

1%-Virol spray was used as standard treatment. The control leaves were sprayed with surfactant solution. Aphid adults apterae (Myzus persicae), starved for 2 hours, were allowed 3 minutes access to untreated infected cucumber which served as a source for the non-persistent Zucchini Yellow Mosaic Virus (ZYMV). The aphids were subsequently confined for 24 hours on test plants by placing a tube around each test plant, and the survivors were killed. The test seedlings were allowed to grow until no more plants developed symptoms.

Behaviour-Interfering Compound vegetable oil combination prevented completely the plant disease transmission, whereas VO emulsions and the standard mineral oil (Virol) sprays were less effective.

25 Relative Transmission Transmission (control 100%) Oil type Oil Alone Oil BP Oil Alone Oil BP Cottonseed 24 0.0 40 0.0 Soybean 33 0.0 55 0.0 Virol 36 60 Control 60 100 1 1% mineral oil applied as an aqueous emulsion (a standard treatment).

BMH:SM:#24119.DIV 19- 17 December 1996 Example 8.

Control of TWF under field conditions: commercial cotton (H-23) was sown in regular row width (96.5 cm) during mid April 1991 in Kibbutz Ein-Hahoresh, Israel. Drip irrigation (385m 3 water per 1000m 2 and other standard agronomic practices except sprays against Bemisia tabaci were employed.

Experimental plots were arranged in a randomized complete-block design with four replications per treatment. Each plot consisted of four rows X 12m long with untreated plots separating replicates. The plots were sprayed twice by Behaviour-Interfering Compound vegetable oil emulsions (on 8th and 14th August 1991) at 70 liter/100 3 rate using portable mist blower. Leaves samples consisted of 10 leaves per replicate were collected the fifth node from the top of the main stem, twice a week started on 14th August 1991. Number of all living larvae and pupae (neonate excluded) on each sampled leaf was determined by the aid of magnifying glass The ability of the three types of Behaviour-Interfering Compound vegetable oil combinations to control field population of TWF is demonstrated in Fig. 1.

It will be understood, unless the context requires otherwise, that the term "comprises" or its grammatical variants as used herein is equivalent to the term "includes" and is not to be taken as excluding the presence of other elements or features.

ee e e *oe BMH:SM:#24119.DIV 20 17 December 1996 27/04 '99 17:54 'e61 3 9882 9854 CARTER SMITH B -4 PATENT OFFICE Z005/007 THE CLAIMS DEFINING THE INVENTION ARE AS FOLLOWS: IL A method for controlling arthropods on foliar plants by applying an~ effective amount of a non-toxic arthropod composition including: at least one non-toxic Behaviour-Interfering Compound selected from

C

10 -C22 alcohols, lauryl alcohol, cetyl alcohol, oleyl alcohol, rnyristyl alcohol, stearyl alcohol, 2-ethyl-i ,3-hex-anediol, 2-butyl-2-ethyl- 1,3 -propanediol;

C

10

-C

22 carbonyl compounds, methyl-nonyl ketone, butopyronoxyl (indalone), citronellal, citral;

C

10 -C2 2 carboxylic acids, myristic acid, stearic acid; terpenoids, camphor, camphene, terpinen-4-ol, isoborneol, borneol, isobornyl **acetate, bornyl acetate, phytol, 13-famnesene, farnesol, geraniol, terpineol, pcymneme, ocimene, limonecne, thyrnol, pinene; C **polybasic carboxylic acids, oxalic acid, fumaric acid, succinic acid, 15 malic acid, fumnaric acid, rnalic acid, oleic acid; substituted mono and polybasic carboxylic acids, adipic acid, sebacic acid, latic acid, tartaric acid, citric acid, aconitic acid, acidoleic acid, sorbic acid; N-butylacetanillidc, N,N-diethyl-3 -methylbenzmide (DEET, N,Ndeithyl-m-toluatnide), benzyl benzoate, 2-hydroxethyl n-octyl sulfide (MGK-874); butoxypoly(propylene glycol); see* esters of carboxylic acids, dimethyl phithalate, diethyl phithalate, dibutyl. phthalate, dibutyl succinate, dibutyl sebacate, dibutyl adipate, myri state esters, methyl myristate.

at least one vegetable oil present at a level of at least 50% w/w of the 2S Behaviour-Interfering Compound; optionally surface active compounds; and optionally diluents.

2, A method according to claim 1 wherein the Behaviour-Interfering Compound is a repellent or deterrent agent, hyperactivity i-nducer or irritant, narcotic, knock-down agent, physical barrier agent or physical poison- DV~:JN4:;'24l]9-CL 27 Apil 199 -21- 27/04 '99 TUE 16:48 [TX/RX NO 7436] Z005

Claims (3)

1. 3. A method according to any one of claims 1 or 2 wherein the Behaviour- Interfering Compound is selected from C 10 -C 2 2 alcohols, CI 0 -C 2 7 carbonyl compounds, C 10 -C2 carboxylic acids and terpenoids, polybasic carboxylic acids, substituted mono and polybasic carboxylic acids anid esters of the mentioned carboxylic acids.
2. 4. A method according to any one of claims It to 3 wherein the Behaviour- Interfering Compound is selected from methybrionyl ketone, N-butyl acetanilide, NN-diethyl-3-methylbenzmide (DEIET), dibutyl plithalate, dirnethyl phithalate, dibutyl succinate, dibutyl adipate, butopyronoxyl (Indalone), butoxypoly(propylene glycol), benzy), benzoate, 2-ethyl-i ,3-hexanediol, 2-butyl-2-ethyl- I, 3-propanediol, 2- hydroxyethyl n-octyl sulfide, citronella, camphor, camphene, terpinen-4-ol, 06 0isobomneol, bomneol, isobornyl acetate, bomyl acetate, phytol, J3-farnesene, lauryl 0, 15 alcohol, cetyl alcohol, oleyl alcohol, rnyrisitic acid, stearic acid, farnesol, acidoleic, dibutyl sebcate, methyl myristate, geraniol, citral, terpineol, beta-farnesene, p- cymnene, ocimene, limonene, thymol, piene, myristyl alcohol, steary] alcohol, oxalic acid, fumaric acid, succinic acid, adipic acid, sebacic acid, malic acid, fiurnaric acid, maleic acid, tartaric acid, citric acid, aconitic acid, aconitic acid, lactic acid,. oleic acid, sorbic acid, myristate esters and diethyl phthalate. A method according to any one of claims I to 4 wherein the vegetable oil is
3. 9. selected from cottonseed oil, soybean oil, rapeseed oil, castor oil, sunflower oil, -4 groundnut oil, palm oil, safflower oil, coconut oil, sesame oil, corn oil, linseed oil, tang oil and palm kernel oil. 6. A method according to any one of claims 1 to 5 wherein the diluent is water or an appropriate organic solvent. 7. A method according to any one of claims 1 to 6 wherein said arthropods are sucking arthropods. '~JM:024 WCL27 April 1999 -22- 27/04 '99 TUE 16:48 [TX/RX NO 7436] lQ006 27/4 '9 1:55~613 982 854CARTER SMITH PATENT OFFICE tI007/007 27/04 '99 17:55 '061 3 9882 9854 a *8 0#* 00 0 S. *0 eve. C *400 60 a a C. 9 0C*e en *0 0* be 8. A method according to any one of claims 1 to 7 wherein said arthropods are whiteflies (A ~i)and aphids hg&) and soft-bodied organisms. 9. A method according to claim 8 wherein said soft-bodied organisms aWe mites, S hoppers, mealy bugs, or thrips- A method according to any one of claims I to 9 wherein the composition is applied to foliage, 10 11. A method for protecting plants substantially as hereinbefore described with reference to any one or more of the non-comparative examples and/or drawings. DATED: 27 Apr-il 1999 15 CARTER SMITH BEADLE Patent Attorneys for the Applicant: THE STATE OF ISRAEL AS REP~RESENTED BY THE MINISTRY OF AGRICULTURE AND THlE AGRICULTURAL RESEARCH ORGANISATION I. .5 S.. a C C PVC;:,NM.fi241J9-CL 27Apl 1999 23 27/04 '99 TUE 16:48 [TX/RX NO 7436] 00jO7 ABSTRACT The invention relates to arthropod control composition for plant protection and to methods of application of such compositions to plants. The invention particularly relates to compositions comprising; behavior interfering compounds such as feeding and oviposition detergents and repellents, hyperactivity inducers, knock down agents, physical barriers or physical poisons, or antimicrobial/insecticidal agents, (ii) agricultural oils and/or surface active compounds, and (iii) diluents. o oo*ooo