AU2020201911A1 - Pesticidal Mixtures - Google Patents

Abstract

The invention provides a pesticidal mixture which includes two active ingredients chosen from buprofezin, pyriproxyfen and spirotetramat. The pesticidal mixture is useful to control any of the following pests in the indicated crops: 5 - California red scale (Aonidiella aurantii) in a crop being citrus, including cv Eureka; - Grapevine scale (Parthenolecanium persicae) in a crop being grape, including cv Cabernet Sauvignon; - Tomato-potato psyllid (Bactericera cockerelli) in a crop being tomato, including cv Roma; 10 - Citrus whitefly (Orchamoplatus citri) in a crop being citrus, including cv Eureka; and - Silverleaf whitefly (Bemisia tabaci) in a crop chosen citrus, including lemon cv Eureka, or cotton, including cv 71RRF and US-7067. 27

Description

Pesticidal Mixtures

Technical Field

The invention relates to novel pesticidal mixtures containing two of buprofezin, pyriproxyfen

and spirotetramat. The novel mixtures of the invention are surprisingly efficacious and, in most cases, exhibit synergy.

Background Art

Buprofezin, pyriproxyfen and spirotetramat are pesticides used primarily as foliar

applications to control of a range of insect pests in agricultural, horticultural and ornamental crops/plants. Buprofezin and pyriproxyfen are broadly classified as insect growth regulators

(IGRs), however their modes of action are completely different at the biochemical level and

they are in separate groupings for insecticide resistance management. Spirotetramat is a cyclic ketoenole with a mode of action that interferes with lipid biosynthesis, leading to

death of immature stages of the target insect a few days after application.

Buprofezin (IUPAC name (2Z)-3-isopropyl-2-[(2-methyl-2-propanyl)imino]-5-phenyl-1,3,5

thiadiazinan-4-one) inhibits chitin biosynthesis and subsequent cuticle deposition, as well as effecting hormone levels in nymphs associated with moulting and prostaglandin synthesis.

Insect pests controlled by buprofezin mainly include Homoptera (such as aphids, cicadas, leafhoppers and scale insects), with some Coleoptera (beetles) and Acarina (mites and ticks)

species also susceptible. The effects of buprofezin include inhibiting moulting of nymphs and

larvae, suppression of oviposition in adults and treated insects laying sterile eggs.

Pyriproxyfen (IUPAC names 4-phenoxypheny (R/S)-2-(2-pyridyloxy)propyl ether or 2-[1-4

phenoxyphenoxy)propan-2-yloxy]pyridine) is an insect juvenile hormone analogue that inhibits insect development, suppressing embryogenesis, metamorphosis and reproduction.

Target insect species include whiteflies, thrips, scale and public health pests i.e. fly, beetles, midges, mosquitoes.

Spirotetramat (IUPAC name cis-4-(ethoxycarbonyloxy)-8-methoxy-3-(2,5-xylyl)-1 azaspiro[4.5]dec-3-en-2-one) is a spirocyclic tetramic acid derivative that inhibits lipid biosynthesis in a wide range of sucking pests and some lepidopterous pests. Its mode of action is particularly effective against juvenile stages of sucking pests as well as reducing the fecundity and fertility of the female adult. Spirotetramat is ambimobile and moves upwards and downwards through the plant in the vascular tissue. Due to its mode of action, the speed of activity of spirotetramat is slower than some alternative products, such as the neonicotinoids.

It has been known to use buprofezin, pyriproxyfen and spirotetramat in rotation with each

other in certain crops, for suppression or control of pests like scale and whitefly. Additionally, each of these three active ingredients has a good profile on beneficial insects

and is generally less disruptive where integrated pest management (IPM) based programs

are used.

It has now been found that, surprisingly, two of buprofezin, pyriproxyfen and spirotetramat

may form synergistic mixtures that are particularly effective on one or more pest species. By applying them in a mixture, better control, protection of the crop or plant and greater

efficacy/productivity/quality can be achieved. By combining these IPM compatible insecticides into two-way mixtures, synergistic target pest activity can be achieved without

significantly impacting beneficial insects.

It was unexpected that synergistic mixtures would be formed by these active ingredients:

their modes of action do not suggest that combining them would be synergistic. In the case

of buprofezin and pyriproxyfen, both are IGRs; their effects can take longer to become apparent in the field and are not always as effective on target pest species, compared with

active ingredients having other modes of action.

Summary of the Invention

Accordingly, the present invention provides a mixture of at least two insecticides selected from the group consisting of spirotetramat, pyriproxyfen and buprofezin.

In one form, the present invention provides a composition comprising (i) at least two insecticides selected from the group consisting of Spirotetramat, Pyriproxyfen and

buprofezin and (ii) an agriculturally acceptable carrier

In one form, the present invention provides a synergistic mixture of at least two insecticides

selected from the group consisting of spirotetramat, pyriproxyfen and buprofezin.

In one form, the present invention provides a synergistic composition comprising (i) at least

two insecticides selected from the group consisting of spirotetramat, pyriproxyfen and buprofezin and (ii) an agriculturally acceptable carrier.

It is particularly preferred that the invention provides a pesticidal mixture which includes an effective quantity of two active ingredients chosen from buprofezin, pyriproxyfen and

spirotetramat, for control of pests, including but not limited to the following pests, in a crop including but not limited to the following crops:

- California red scale (Aonidiella aurantii) in a crop being citrus, including cv Eureka;

- Grapevine scale (Parthenolecanium persicae) in a crop being grape, including cv Cabernet Sauvignon;

- Tomato-potato psyllid (Bactericera cockerelli) in a crop being tomato, including cv Roma;

- Citrus whitefly (Orchamoplatus citri) in a crop being citrus, including cv Eureka; and

- Silverleaf whitefly (Bemisia tabaci) in a crop being citrus, including lemon cv Eureka, or cotton, including cv 71RRF and US-7067.

The invention also provides a method of controlling one or more of pests, including but not limited to the pests listed above in a crop, including but not limited to one of the crops listed

above, the method including the step of applying to the crop the pesticidal mixture according

to the invention.

In a further aspect, the invention provides use of at least two of buprofezin, pyriproxyfen and

spirotetramat in the manufacture of a pesticidal mixture for controlling one or more pests, including but not limited to the pests listed above, in a crop, including but not limited to one

of the crops listed above, the crop being infested by one or more of the pests.

The pesticidal mixtures of the invention are preferably a mixture of:

(a) Pyriproxyfen and buprofezin; or

(b) Buprofezin and spirotetramat; or

(c) Pyriproxyfen and spirotetramat.

In some embodiments, the pesticidal mixture comprises buprofezin and pyriproxyfen.

In some embodiments, the pesticidal mixture comprising buprofezin and pyriproxyfen is for

controlling a pest selected from nymphs, California red scale (Aonidiellaaurantii), Grapevine scale (Parthenolecanium persicae), Tomato-potato psyllid (Bactericera cockerelli), Citrus

whitefly (Orchamoplatus citri) and Silverleaf whitefly (Bemisia tabaci).

In some embodiments, the pesticidal mixture comprising buprofezin and pyriproxyfen is for

controlling a pest in a crop selected from citrus, including cv Eureka, grape, including cv

Cabernet Sauvignon; tomato, including cv Roma and cotton, including cv 71RRF.

In some embodiments, the pesticidal mixture comprising buprofezin and pyriproxyfen is for

controlling nymphs, California red scale (Aonidiella aurantii) in a crop being citrus, including cv Eureka; Grapevine scale (Parthenolecanium persicae) in a crop being grape, including cv

Cabernet Sauvignon; Tomato-potato psyllid (Bactericera cockerelli) in a crop being tomato, including cv Roma;- Citrus whitefly (Orchamoplatus citri) in a crop being citrus, including cv

Eureka; or Silverleaf whitefly (Bemisiatabaci) in a crop being citrus, including lemon cv Eureka, or cotton, including cv 71RRF'.

In some embodiments, the pesticidal mixture comprises spirotetramat and buprofezin.

In some embodiments, the pesticidal mixture comprising spirotetramat and buprofezin is for controlling a pest selected from nymphs, California red scale (Aonidiella aurantii) and

Silverleaf whitefly (Bemisia tabaci).

In some embodiments, the pesticidal mixture comprising spirotetramat and buprofezin is for

controlling pest in a crop selected from citrus, including cv Eureka and cotton, including cv 71RRF.

In some embodiments, the pesticidal mixture comprising spirotetramat and buprofezin is for

controlling nymphs, California red scale (Aonidiella aurantii) in a crop being citrus, including cv Eureka or Silverleaf whitefly (Bemisia tabaci) in a crop being citrus, including lemon cv

Eureka, or cotton, including cv 71RRF.

In some embodiments, the pesticidal mixture comprises spirotetramat and pyriproxyfen.

In some embodiments, the pesticidal mixture comprising spirotetramat and pyriproxyfen is for controlling a pest selected from nymphs, California red scale (Aonidiellaaurantii) and

Silverleaf whitefly (Bemisia tabaci).

In some embodiments, the pesticidal mixture comprising spirotetramat and pyriproxyfen is

for controlling pest in a crop selected from citrus, including cv Eureka and cotton, including cv

71RRF.and US-7067.

In some embodiments, the pesticidal mixture comprising spirotetramat and pyriproxyfen is

for controlling nymphs, California red scale (Aonidiella aurantii) in a crop being citrus, including cv Eureka or Silverleaf whitefly (Bemisia tabaci) in a crop being citrus, including

lemon cv Eureka, or cotton, including cv 71RRF and US-7067.

The active ingredients are provided in a proportion sufficient to provide a synergistic or

efficacious effect. A synergistic effect exists wherever the action of a mixture of active ingredients is greater than the sum of the action of the ingredients alone. Thus, a

synergistically effective mixture or proportion as discussed herein is a mixture or proportion

that exhibits greater pesticidal activity than the sum of the pesticidal activities of the individual components.

In the context of the present subject matter, the term 'synergy' is as defined by Colby S R in an article 'Calculation of the synergistic and antagonistic responses of herbicidal

combinations' published in the journal Weeds 1967, 15, p 20-22, incorporated herein in its entirety.

Foliar applications of mixtures of buprofezin + pyriproxyfen, buprofezin + spirotetramat and pyriproxyfen + spirotetramat have been found to be synergistic on one or more pest species.

Field testing of each of these mixtures demonstrate that they provide greater control than equivalent rates of solo applications of buprofezin, pyriproxyfen or spirotetramat. Using the

Colby formula, the results consistently demonstrated that these mixtures are synergistic, with Colby values between 1.02 and 5.34.

The ratio of active ingredients in the mixtures of the invention may be any effective ratio. Some ratio examples are given in the tables below, but these are not to be regarded as

limiting.

In some embodiments, the weight ratio between the two insecticides in the mixture is from

10:1 to 1:10. In some embodiments, the weight ratio between the two insecticides in the mixture is from 5:1 to 1:5. In some embodiments, the weight ratio between the two

insecticides in the mixture is from 4:1 to 1:4. In some embodiments, the weight ratio

between the two insecticides in the mixture is from 2:1to 1:2.

In some embodiments, the weight ratio between the spirotetramat to buprofezin in the

mixture is from 10:1 to 1:10. In some embodiments, the weight ratio between spirotetramat to buprofezin in the mixture is from 5:1 to 1:5. In some embodiments, the weight ratio

between the spirotetramat to buprofezin in the mixture is from 4:1 to 1:4. In some embodiments, the weight ratio between the spirotetramat to buprofezin in the mixture is

from 2:1 to 1:2.

In some embodiments, the weight ratio between the pyriproxyfen + spirotetramat in the

mixture is from 10:1 to 1:10. In some embodiments, the weight ratio between the

pyriproxyfen + spirotetramat in the mixture is from 5:1 to 1:5. In some embodiments, the weight ratio between the pyriproxyfen + spirotetramat in the mixture is from 4:1 to 1:4. In

some embodiments, the weight ratio between the pyriproxyfen + spirotetramat in the mixture is from 2:1to 1:2.

In some embodiments, the weight ratio between the buprofezin + pyriproxyfen in the mixture is from 10:1 to 1:10. In some embodiments, the weight ratio between the buprofezin

+ pyriproxyfen in the mixture is from 5:1 to 1:5. In some embodiments, the weight ratio between the buprofezin + pyriproxyfen in the mixture is from 4:1 to 1:4. In some embodiments, the weight ratio between the buprofezin + pyriproxyfen in the mixture is from

2:1 to 1:2.

Preferred ratios are:

pyriproxyfen to buprofezin: a range of about 1:2 to about 1:18, especially 1:2.64, 1:5.28, 1:8.8 or 1:17.6;

pyriproxyfen to spirotetramat: a range about 1:0.9 to about 1:2.4., especially 1:0.96, 1:1.44, 1:2.1 or 1:2.4;

buprofezin to spirotetramat: a range about 1:0.10 to 1:0.55, especially 1:0.10, 1:0.18, 1:0.21, 1:0.27, 1:0.36, 1:0.42, 1:0.43, 1:0.45 or 1:0.54.

Preferred rates for application of pyriproxyfen to a crop are 5 g ai/100 L or 25 to 50 g ai/ha.

Preferred rates for application of buprofezin is applied to a crop are 13.2 to 26.4 g ai/100 L or 220 to 440 g ai/ha.

Preferred rates for application of spirotetramat to a crop are 4.8 to 7.2 g ai/100 L; or 48 to 105 g ai/ha.

The formulation types for each of buprofezin, pyriproxyfen and spirotetramat for the mixtures of the invention may be any convenient or appropriate formulation type, such as DC

(dispersible concentrate), WG (water-dispersible granules), WP (wettable powder), EC (emulsifiable concentrate), EW (emulsion), SE (aqueous suspo-emulsion), SC (aqueous

suspension concentrate), CS (aqueous capsule suspension), OW (emulsion, oil in water) and

ZC (mixed formulation of CS and SC). Preferred are EC, SC, SE, EW, OW, WG or WP (in water soluble packaging). The formulation types are preferably mixed into a tank mix.

The mixtures may be mixed with any suitable adjuvants, as will be apparent to the person skilled in the art.

The active ingredients in the mixture of the invention may be applied simultaneously or contemporaneously.

As used herein, the term "simultaneous" when used in connection with application of agrochemicals means that the agrochemicals are applied in an admixture, for example, a tank mix. For simultaneous application, the combination may be the admixture or separate containers each containing an agrochemical that are combined prior to application.

As used herein, the term "contemporaneous" when used in connection with application of agrochemicals means that an individual agrochemical is applied separately from another

agrochemical or premixture at the same time or at times sufficiently close together that an activity that is additive or more than additive or synergistic relative to the activity of either

agrochemical alone at the same dose is achieved.

As used herein, the term "mixture" refers to, but is not limited to, a combination in any

physical form, e.g., blend, solution, suspension, dispersion, emulsion, alloy, or the like.

As used herein, the term "tank mix" means one or more of the components of the combination, mixture or composition of the present invention are added are mixed in a spray

tank at the time of spray application or prior to spray application.

As used herein, the term "agriculturally acceptable carrier" means carriers which are known

and accepted in the art for the formation of compositions for agricultural or horticultural use.

In order that the invention in its various aspects may be more readily understood and put

into practice, one or more non-limiting preferred embodiments thereof will now be described.

Detailed Description of Preferred Embodiments

In the examples below, unless otherwise stated, the following materials were used:

Product Active Ingredient Conc (g ai/L) Adjuvant

Lascar 100 EC pyriproxyfen 100

Admiral 100 pyriproxyfen 100

Applaud 440 SC buprofezin 440

Applaud 25% SC buprofezin 250

Mortar 440 SC buprofezin 440

Product Active Ingredient Conc (g ai/L) Adjuvant

Movento 240 SC spirotetramat 240 Hasten 704 EC @ 50 mL/100 L Movento 150 OD spirotetramat 150

Lascar is available from Adama Australia Pty Ltd, Suite 1, Level 4, Building B, 207 Pacific

Highway, St Leonards NSW 2065, Australia.

Admiral can be obtained from Sumitomo Chemical Australia Pty Limited, 501 Victoria

Avenue, Chatswood NSW 2067, Australia.

Applaud 440 SC is available from DowAgroScience Australia Limited, at 67 Albert Avenue, Chatswood NSW 2067, Australia.

Applaud 25% SC is available from Rallis India Limited, 3301, GIDC, Ankeshwar (Gujarat), India.

Mortar is available from Lonza NZ Limited, Hudson Road, New Plymouth, New Zealand.

Movento240 SC is available from Bayer Crop Science Pty Limited, Level 1, 8 Redfern Road, Hawthorn East, Victoria 3123, Australia.

Movento 150 OD can be obtained from Bayer Crop Science, Bayer House, Central Avenue, Hiranandani Estate, Thane (West) 400607, Maharashra, India.

Hasten (an adjuvant containing ethyl and methyl esters of fatty acids) is obtainable from

Victorian Chemical Company (Vicchem), 83 Maffra Street, Coolaroo, Victoria 3048, Australia.

Example 1

In this example, buprofezin, pyriproxyfen and spirotetramat were applied to lemon crops (cv. Eureka), as single active ingredients and in the tank mixes shown in Tables 1 and 2 below, to

assess efficacy and synergy for control of Aonidiella auranti (California red scale - CRS).

The control percentages were compared, both as to severity of fruit infestation (Table 1) and

incidence of fruit infestation (Table 2). In Tables 1 and 2, buprofezin, pyriproxyfen and spirotetramat are abbreviated in the mixtures to B, P and S respectively.

The adjuvant, Hasten, was included at 50 mL per 100 L together with Spirotetramat, whether

alone or in a mixture with pyriproxyfen or buprofezin.

The active ingredient, alone or in a mixture as set out in the Tables, was applied by spraying,

with the first spray applied during early spring, when scale crawlers became active. The active ingredient was applied as a dilute spray to the point of runoff.

A second spray was applied 22 days after the first.

The severity of fruit infestation and the incidence of fruit infestation were observed at the 22

day stage, just prior to the second spray ('22 DAB' in the Tables below) and at 45 days after the first spray ('45 DAB' in the Tables below).

Table 1: Severity of CRS infestation on fruit

% Control % Control Colby ratio o/e observed expected Application Active Ingredient 22 45 22 45 22 45 rate (ai) DAB DAB DAB DAB DAB DAB (g ai/100 )

Pyriproxyfen (P) 5 78.33 54.55 - - -

Buprofezin (B) 13.2 41.67 18.18 - - -

Buprofezin (B) 26.4 61.67 60.61 - - -

Spirotetramat (S) 4.8 83.33 100.00 - - -

Spirotetramat (S) 7.2 91.67 90.91 - - -

P+B 5+13.2 61.67 90.91 87.36 62.81 0.71 1.45

P+B 5+26.4 83.33 100.00 91.69 82.09 0.91 1.22

P+S 5+4.8 100.00 93.94 96.39 100.00 1.04 0.94

P+S 5+7.2 95.00 100.00 98.19 95.87 0.97 1.04

B+S 13.2+4.8 61.67 100.00 91.69 95.87 0.67 1.04

B+S 13.2+7.2 88.33 100.00 96.39 100.00 0.92 1.00

B+S 26.4+4.8 91.67 100.00 100.00 97.25 0.92 1.03

B+S 26.4+7.2 78.33 100.00 98.92 100.00 0.79 1.00

Table 2: Incidence of CRS infestation on fruit

%Control % Control Colby ratio o/e observed expected

Application Active Ingredient 22 45 22 45 22 45 rate (ai) DAB DAB DAB DAB DAB DAB (g ai/100 L) Pyriproxyfen (P) 5 64.31 24.95 - - -

Buprofezin (B) 13.2 28.51 -12.57 - - -

Buprofezin (B) 26.4 35.69 49.91 - - -

Spirotetramat (S) 4.8 64.31 100.00 - - -

Spirotetramat (S) 7.2 78.56 75.05 - - -

P+B 5+13.2 42.87 75.05 74.48 15.52 0.58 4.84

P+B 5+26.4 64.31 100.00 77.05 62.41 0.83 1.60

P+S 5+4.8 100.00 87.43 87.26 100.00 1.15 0.87

P+S 5+7.2 85.74 100.00 92.35 81.27 0.93 1.23

B+S 5+4.8 42.87 100.00 79.61 81.27 0.54 1.23

B+S 5+7.2 71.38 75.05 87.26 100.00 0.82 0.75

B+S 13.2+4.8 78.56 87.43 100.00 90.57 0.79 0.97

B+S 13.2+7.2 57.13 87.43 94.91 100.00 0.60 0.87

The results established that:

- mixtures of pyriproxyfen and buprofezin were synergistic in controlling severity and

incidence of California red scale in lemon Eureka variety at a ratio of 1: 2.64 and also at a ratio of 1: 5.28; - mixtures of pyriproxyfen and spirotetramat were synergistic in controlling severity

and incidence of California red scale in lemon Eureka variety at a ratio of 1: 0.96 and

also at a ratio of 1: 1.44;

- mixtures of buprofezin and spirotetramat were synergistic in controlling severity of

California red scale in lemon Eureka variety at a ratio of 1: 0.9, with effective results at ratios of 1: 1.44, 1: 0.545, and 1: 0.36 during the times in the trial.

Example 2

In this example, buprofezin (as Applaud 440 SC, having a concentration of 440 g/L) and pyriproxyfen (as Admiral 100 OW, having a concentration of 100 g/L) were applied to

grapevines (cv: Cabernet Sauvignon) to treat grapevine scale (Parthenolecanium persicae). Buprofezin and pyriproxyfen were applied alone and also together as a tank mix. All

treatments were compared with untreated control vines.

The grapevines chosen for the trial had been infested with grapevine scale the previous season and dormant scale was observed on shoots in spring. Seven days prior to application

of the active ingredients, shoots were inspected for scale: there were crawlers present at a low level on more than one third of shoots.

Two applications of active ingredient were made, at an interval of 31 days when berries were 6-7 mm. The active ingredient was applied as a dilute spray to the point of runoff. The

average water application volume was 837 L/ha.

At 28 days after the first application of active ingredient (28 DAA1), leaves were assessed for

grapevine scale crawlers. Further assessments were made at 55 days after the second

application (55 DAA2) and again at 89 days after the second application (89 DAA2). The results are shown in Tables 3, 4 and 5.

The percentage of shoots with scale and the scales per shoot were also assessed at 55 DAA2 and at 89 DAA2. The results are in Tables 6 and 7.

In Tables 3 to 7, buprofezin and pyriproxyfen are abbreviated in the mixtures to B and P respectively.

Table 3: Grapevine scale in Cabernet Sauvignon Variety 28 DAA1 %Control % Control Colbyratiooe observed expected Active Appln % % Crawler rate Leaves Crawlers Leaves Leaves Crawlers Ingredient g ai/100 with perleaf with super with perleaf (ai) L crawlers crawlers leaf crawlers Pyriproxyfen 5 23.33 37.14 - - -

Buprofezin 13.2 46.67 71.43 - - -

P+B 5+13.2 63.33 86.67 59.11 82.04 1.07 1.06

Table 4: Grapevine scale in Cabernet Sauvignon Variety 55 DAA2 %Control % Control Colby.ratiooe observed expected Active Appln % %

% rate shoots Scales/ shoots Scales/ shoots Scales/ Ingredient g ai/100 with shoot with shoot with shoot (ai) L scale scale scale Pyriproxyfen 5 7.69 20.87 - - -

Buprofezin 13.2 35.90 71.36 - - -

P+B 5+13.2 48.72 79.13 40.83 77.34 1.19 1.02

Table 5: Grapevine scale in Cabernet Sauvignon Variety 89 DAA2 % Control % Control 1Colbyratioo/e observed expected obrto/ Active Appln rate Ingredient gai/100 % shoots with scale (ai) Pyriproxyfen 5 20.00

Buprofezin 13.2 32.50 -

P+B 5+13.2 47.50 46.00 1.03

The results established that a mixture of pyriproxyfen and buprofezin was synergistic in

controlling grapevine scale in Cabernet Sauvignon grapevines at a ratio of 1: 2.64.

Example 3

In this example, buprofezin (as Applaud 440 SC, having a concentration of 440 g/L) and

pyriproxyfen (as Admiral 100 OW, having a concentration of 100 g/L) were applied to a lemon crop (cv. Eureka), as single active ingredients and in the tank mixes shown in Table 6

below, to assess efficacy and synergy for control of Aonidiella auranti (California red scale) in lemons. All treatments were compared with untreated control vines.

Two applications of active ingredient were made, the first during early spring when scale

crawlers become active and the second at a 21 day interval. The active ingredient was applied as a dilute spray to the point of runoff. An assessment of pest density on fruit, leaves

and stems was made 45 days after the first application (45 DAAB).

Table 6: Red scale in Citrus 45 DAA2 %Control % Control Colbyratioo/e observed expected Active Appln Ingredient rate -g Incidence Severity Incidence Severity Incidence Severity (ai) ai/100 L

Pyriproxyfen 5 13.30 54.55 - - -

Buprofezin 13.2 -6.70 18.18 - - -

Buprofezin 26.4 26.60 60.61 - - -

P+B 5+13.2 40.00 90.91 7.49 62.81 5.34 1.45

P+B 5+26.4 53.30 100.00 36.36 82.09 1.47 1.22

The results established that mixtures of pyriproxyfen and buprofezin were synergistic in controlling red scale in citrus at a ratio of 1: 2.64 and also at a ratio of 1: 5.28. The ratio of

1:2.64 was particularly effective in relation to controlling incidence.

Example 4

In this example, buprofezin (as Mortar SC, having a concentration of 500 g/L) and pyriproxyfen (as Lascar EC, having a concentration of 100 g/L) were applied to tomatoes (cv.

Roma), as single active ingredients and in the tank mixes shown in Table 7 below, to assess efficacy and synergy for control of tomato potato psyllid (Bactericera cockerelli).

All treatments were compared with untreated control plants.

Four applications of active ingredient were made at 7-11 day intervals. Pyriproxyfen was

applied at 500 mL/ha. Pyriproxyfen was tank mixed with buprofezin at 307 mL/ha. All treatments had non-ionic surfactant CONTACT XCEL (trademark) added at 40 mL/100 L.

Applications were made in 600 L/ha of water.

Psyllid (TPP) nymphs were counted on 10 leaves per plot on four occasions during the trial period. At harvest, tomatoes were sorted and assessed based on colour and yield and overall

crop heath was evaluated. Crop health and harvest parameters were not affected by any of the treatments.

In Table 7, buprofezin and pyriproxyfen are abbreviated in the mixtures to B and P respectively. 6 DAA3 means '6 days after the third application'. 7 DAA4 means '7 days after

the fourth application'.

Table 7: TPP infestation in Roma Tomatoes % Control % Control Colbyratioo/e observed expected Incidence Incidence Incidence Active Application TPP/Leaf small TPP/Leaf small TPP/Leaf small Ingredient rate (g 6 DAA3 nymphs 6DAA3 nymphs 6 DAA3 nymphs (ai) ai/ha) 7DAA4 7DAA4 7DAA4 Pyriproxyfen 50 72 52.5 - - -

Buprofezin 132 15 32.5 - - -

P+B 50+132 89 70 76.3 67.5 1.16 1.03

The results establish that a mixture of pyriproxyfen and buprofezin was synergistic in controlling TPP in tomatoes at a ratio of 1: 2.64.

Examples 5 and 6 Example 5: Table 8 below provides a further example of a different aspect of the invention:

synergy in a mixture of pyriproxyfen and buprofezin in treating citrus whitefly (Orchamoplatus citri) including nymphs, in citrus.

Example 6: Tables 9 to 11 show synergy in mixtures of pyriproxyfen and buprofezin, and of

buprofezin and spirotetramat, in treating silverleaf whitefly (Bemisia tabaci) in cotton. The mixtures were synergistic in control of nymphs and pupae.

Example 5: Table 8: Density of Citrus Whitefly on Old Citrus Leaves 12 DAA1

% Control observed % Control expected Colby ratio o/e

ai Appin rate (g ai/100L) Adults Eggs Nymphs Adults Eggs Nymphs Adults Eggs Nymphs

Pyriproxyfen 5 22.0 87.0 34.0 - - - - - Buprofezin 13.2 38.0 72.0 75.5 - - - - - P+B 5+13.2 62.7 97.0 100.0 51.6 96.4 83.8 1.21 1.01 1.19

Example 6: Table 9: Silverleaf whitefly (Bemisia tabaci) in Cotton (cv 71RRF) Bemisia tabacinymphs per leaf

ai Appnrate % Control observed % Control expected Colby ratio o/e 3 7 11 19 23 3 7 11 19 23 3 7 11 19 23 DAA DAA DAA DAA DAA DAA DAA DAA DAA DAA DAA DAA DAA DAA DAA Buprofezin 220 60.0 55.6 77.8 87.0 61.5 - - - - - Buprofezin 440 55.6 83.3 71.1 65.2 38.5 - - - - -- Spirotetramat 48 93.3 44.4 100.0 78.3 76.9 - - - - - Spirotetramat 96 37.8 83.3 100.0 65.2 61.5 - - - - Pyriproxyfen 25 71.1 72.2 93.3 87.0 100.0 - - - - - Pyriproxyfen 50 48.9 83.3 93.3 65.2 23.1 - - - - -- S+B 48+220 66.7 44.4 82.2 87.0 76.9 97.3 75.3 100.0 97.2 91.1 0.68 0.59 0.82 0.89 0.84 S+B 96+220 88.9 100.0 100.0 78.3 100.0 75.1 92.6 100.0 95.5 85.2 1.18 1.08 1.00 0.82 1.17 S+B 48+440 60.0 55.6 77.8 87.0 100.0 97.0 90.7 100.0 92.4 85.8 0.62 0.61 0.78 0.94 1.17 S+B 96+440 66.7 83.3 71.1 100.0 100.0 72.3 97.2 100.0 87.9 76.3 0.92 0.86 0.71 1.14 1.31 P+B 25+440 60.0 27.8 77.8 100.0 61.5 87.2 95.4 98.1 95.5 100.0 0.69 0.29 0.79 1.05 0.62 P+B 50+440 88.9 44.4 66.7 34.8 76.9 77.3 97.2 98.1 87.9 52.7 1.15 0.46 0.68 0.40 1.46

Example 6: Table 10: Silverleaf whitefly (Bemisia tabaci) in Cotton

Bemisia tabaci nymphs and pupae per leaf

. Application % Control observed % Control expected Colbyratioo/e ai rate (g ai/ha) 7 13 21 30 7 13 21 30 7 13 21 30 DAA DAA DAA DAA DAA DAA DAA DAA DAA DAA DAA DAA

Buprofezin 220 32.9 73.3 79.1 17.2 - - - - - - -

Buprofezin 440 53.7 77.6 85.3 68.2 - - - - - - -

Spirotetramat 48 45.8 62.7 75.0 54.5 - - - - - - -

Spirotetramat 96 -7.7 58.8 88.0 59.1 - - - - - - -

Pyriproxyfen 25 36.6 57.3 -64.7 13.6 - - - - - - -

Pyriproxyfen 50 25.6 52.7 57.4 30.9 - - - - - - -

S+B 48+220 47.6 61.1 77.8 90.9 63.7 90.0 94.8 62.4 0.75 0.68 0.82 1.46

S+B 96+220 46.3 81.7 76.2 40.9 27.7 89.0 97.5 66.1 1.67 0.92 0.78 0.62

S+B 48+440 43.9 73.3 82.4 77.3 74.9 91.6 96.3 85.5 0.59 0.80 0.85 0.90

S+B 96+440 62.2 77.9 80.9 59.1 50.1 90.8 98.2 87.0 1.24 0.86 0.82 0.68

P+B 25+440 54.6 77.9 92.6 77.0 70.6 90.4 75.8 72.5 0.77 0.86 1.22 1.06

P+B 50+440 46.3 71.0 92.6 81.8 65.5 89.4 93.7 78.0 0.71 0.79 0.99 1.05

Example 6: Table 11: Silverleaf whitefly (Bemisia tabaci) in Cotton

Bemisia tabaci nymphs per leaf

Application AplictionColby Al% Control ratio o/e Al rate observed % Control expected 7 13 21 27 7DAA 13 21 27 7 13 21 27 DAA DAA DAA DAA DAA DAA DAA DAA DAA DAA DAA Buprofezin 220 54.5 63.0 46.2 64.1 - - - - - - - Buprofezin 440 -15.4 54.5 81.0 34.6 - - - - - - - Spirotetramat 48 48.1 55.9 -19.0 33.7 - - - - - - -

Spirotetramat 96 -90.6 103.3 -3.5 55.5

Pyriproxyfen 25 -13.3 60.7 5.8 76.8 - - - - - - -

Pyriproxyfen 50 41.4 73.0 74.5 63.8 - - - - - - -

S+B 48+220 -18.6 69.2 56.0 88.4 76.4 83.7 35.9 76.2 -0.24 0.83 1.56 1.16

S+B 96+220 -47.2 39.8 20.4 70.5 13.2 24.8 44.3 84.1 -3.57 1.60 0.46 0.84

S+B 48+440 49.2 -18.0 83.4 87.2 40.1 79.9 77.4 56.7 1.23 -0.23 1.08 1.54

S+B 96+440 66.9 13.7 43.6 72.8 -120.0 7.5 80.4 70.9 -0.56 1.83 0.54 1.03

P+B 25+440 11.0 59.2 85.7 64.2 -30.8 82.1 82.1 84.9 -0.36 0.72 1.04 0.76

P+B 50+440 37.5 65.7 46.8 49.9 32.3 87.7 95.2 76.3 1.16 0.75 0.49 0.65

Example 7

In this example, spirotetramat and pyriproxyfen were applied to a cotton crop (cv US 7067) as single active ingredients and in the tank mixes shown in Table 12.

Table 12: Treatment Details

Dose Productrate Active Ingredient/s (g ai/ha) (g or ml/ha)

Spirotetramat 150 OD 105 700

Pyriproxyfen 100 EC 50 500

Spirotetramat + Pyriproxyfen 105+50 700+500

At trial initiation, the crop age was 96 days after sowing (DAS).

Five plants in each plot were tagged for observation. A pre-count of whitefly nymphs

was taken separately on two leaves from the bottom and three leaves from the middle

of each tagged plant, and then at 1, 3, 5, 7 and 10 days after application (DAA).

A total of 25 leaves were counted per plot and per replication in each treatment.

The results are set out in Tables 13 and 14.

Table 13: Efficacy on Silverleaf Whitefly Nymphs in Cotton (Nymph Density per Plant)

Treatments Dose Product rate Pre- 1 3 5 7 (g ai/ha) (g or ml/ha) Count DAA DAA DAA DAA

Untreated NA NA 27.1 27.5 35.9 48.9 47.5 Control

Spirotetramat 105 700 21.1 21.1 19.2 11.1 6.93 150 OD

Pyriproxyfen 50 500 19.1 21.8 21.1 17.0 14.1 100 EC

Spirotetramat 105+ 19.3 18.7 15.8 1.33 0.80 + Pyriproxyfen 50

Table 14: % Reduction in Silverleaf Whitefly Nymphs over Control Dose Product rate 1 DAA 3 DAA 5 DAA 7 DAA Treatments (g a./ha) (g or ml/ha) (Colby* in (Colby* al/ha) bold in bold) Spirotetramat 105 700 23 47 77 85 150 OD Pyriproxyfen 50 500 21 41 65 70 100 EC

Spirotetramat 105+ 32 56 97 98 + Pyriproxyfen 50 700+500 (1.0549) (1.026)

* Colby ratio is calculated using formula:

E = X + Y - XY/100

Colby ratio = Observed %reduction/E

where

E = expected % reduction;

X = spirotetramat % reduction,

Y = pyriproxyfen % reduction.

It will be observed that the mixture of pyriproxyfen and spirotetramat exhibits synergy in control of nymphs of Silverleaf whitefly (Bemisia tabaci), with the mixture in the

ratio of 1: 2.1 exhibiting synergy at 5 and 7 days after application.

The foregoing embodiments are intended to be illustrative of the invention, without

limiting the scope thereof. The invention is capable of being practised with various modifications and additions as will readily occur to those skilled in the art.

Accordingly, it is to be understood that the scope of the invention is not to be limited

to the exact construction and operation described and illustrated.

The term "comprise" and variants of that term such as "comprises" or "comprising"

are used herein to denote the inclusion of a stated integer or integers but not to exclude any other integer or any other integers, unless in the context or usage an exclusive interpretation of the term is required.

Reference to prior art disclosures in this specification is not an admission that the

disclosures constitute common general knowledge in Australia or elsewhere.

Claims (27)

Claims

1. A pesticidal mixture which includes an effective quantity of two active ingredients chosen from buprofezin, pyriproxyfen and spirotetramat.

2. A pesticidal mixture according to claim 1, wherein the weight ratio between the two active ingredients is from 10:1 to 1:10.

3. The pesticidal mixture of claim 1 or 2, for controlling a pest, wherein the pest is selected from nymphs, California red scale (Aonidiellaaurantii), Grapevine scale (Parthenolecanium persicae), Tomato-potato psyllid (Bactericera cockerelli), Citrus whitefly (Orchamoplatus citri) and Silverleaf whitefly (Bemisia tabaci).

4. The pesticidal mixture of claim 1 or 2, for controlling a pest in a crop, wherein the crop is selected from citrus, including cv Eureka, grape, including cv Cabernet Sauvignon, tomato, including cv Roma and cotton, including cv 71RRF and US-7067.

5. The pesticidal mixture of claim 1 or 2, wherein the two active ingredients comprise buprofezin and pyriproxyfen, for controlling a pest selected from nymphs, California red scale (Aonidiella aurantii), Grapevine scale (Parthenolecanium persicae), Tomato potato psyllid (Bactericera cockerelli), Citrus whitefly (Orchamoplatus citri) and Silverleaf whitefly (Bemisia tabaci).

6. The pesticidal mixture of claim 5, for controlling the pest in a crop selected from citrus, including cv Eureka, grape, including cv Cabernet Sauvignon; tomato, including cv Roma and cotton, including cv 71RRF.

7. The pesticidal mixture of claim 1 or 2, wherein the two active ingredients comprise spirotetramat and buprofezin, for controlling a pest selected from California red scale (Aonidiella aurantii) and Silverleaf whitefly (Bemisia tabaci).

8. The pesticidal mixture of claim 7, for controlling the pest in a crop selected from citrus, including cv Eureka and cotton, including cv 71RRF.

9. The pesticidal mixture of claim 1 or 2, wherein the two active ingredients comprise

spirotetramat and pyriproxyfen, for controlling a pest selected from nymphs, California red scale (Aonidiella aurantii) and Silverleaf whitefly (Bemisia tabaci).

10. The pesticidal mixture of claim 9, for controlling the pest in a crop selected from

citrus, including cv Eureka and cotton, including cv 71RRF and US-7067.

11. The pesticidal mixture of any one of claims 1 to 10, which has a synergistic effect.

12. A pesticidal mixture which includes an effective quantity of two active ingredients chosen from buprofezin, pyriproxyfen and spirotetramat, for control of any of the

following pests:

- California red scale (Aonidiella aurantii) in a crop being citrus, including cv Eureka;

- Grapevine scale (Parthenolecanium persicae) in a crop being grape, including cv Cabernet Sauvignon;

- Tomato-potato psyllid (Bactericera cockerelli) in a crop being tomato, including cv

Roma;

- Citrus whitefly (Orchamoplatus citri), including nymphs, in a crop being citrus, including cv Eureka; and

- Silverleaf whitefly (Bemisia tabaci), includinh nymphs, in a crop chosen from citrus,

including lemon cv Eureka, or cotton, including cv 71RRF and US-7067.

13. The pesticidal mixture of claim 12, wherein the active ingredients are pyriproxyfen

and buprofezin.

14. The pesticidal mixture of claim 13, wherein the quantity of pyriproxyfen to

buprofezin is in the range about 1:2 to about 1:18.

15. The pesticidal mixture of claim 14, wherein the ratio of pyriproxyfen to buprofezin is chosen from: 1:2.64, 1:5.28, 1:8.8 and 1:17.6.

16. The pesticidal mixture of claim 12, wherein the active ingredients are pyriproxyfen and spirotetramat, the pests are, separately, nymphs, California red scale

(Aonidiella aurantii) and Silverleaf whitefly (Bemisiatabaci) and the crop is chosen

from:

- citrus, including lemon cv Eureka; and

- cotton, including cv US-7067.

17. The pesticidal mixture of claim 16, wherein the ratio of pyriproxyfen to spirotetramat is in the range about 1:0.9 to about 1:2.4.

18. The pesticidal mixture of claim 17, wherein the ratio of pyriproxyfen to spirotetramat is chosen from: 1:0.96, 1:1.44, 1:2.1and 1:2.4.

19. The pesticidal mixture of claim 12, wherein the active ingredients are buprofezin and spirotetramat, the pests are, separately, nymphs, California red scale

(Aonidiella aurantii) and Silverleaf whitefly (Bemisiatabaci) and the crop is chosen from:

- citrus, including lemon cv Eureka; and

- cotton, including cv 71RRF and US-7067.

20. The pesticidal mixture of claim 19, wherein the ratio of buprofezin to spirotetramat

is in the range about 1:0.10 to 1:0.55.

21. The pesticidal mixture of claim 20, wherein the ratio of buprofezin to spirotetramat

is chosen from: 1:0.10, 1:0.18, 1:0.21; 1:0.27; 1:0.36; 1:0.42, 1:0.43, 1:0.45 and 1:0.54.

22. The pesticidal mixture of any one of claims 12 to 21, wherein pyriproxyfen is applied to the crop at a rate of 5 g ai/100 L or 25 to 50 g ai/ha.

23. The pesticidal mixture of any one of claims 12 to 21, wherein buprofezin is applied

to the crop at a rate of 13.2 to 26.4 g ai/100L or 220 to 440 g ai/ha.

24. The pesticidal mixture of any one of claims 12 to 21, wherein spirotetramat is

applied to the crop at a rate of 4.8 to 7.2 g ai/100 L or 48 to 105 g ai/ha.

25. The pesticidal mixture of any one of claims 1 to 24, which includes an agriculturally

acceptable carrier.

26. A method of controlling one or more of the pests listed in claim 12 in one of the

crops listed in claim 12, the method including the step of applying to the crop the

pesticidal mixture according to any one of claims 1 to 25.

27. Use of any one of the pesticidal mixtures in any one of claims 1 to 25 in the

manufacture of a pesticidal mixture for controlling one or more of the pests listed in claim 12 in one of the crops listed in claim 12, the crop being infested by one or more

of the pests.