DESC:FIELD OF THE INVENTION

The present invention relates to a synergistic formulation comprising Pyriproxyfen as a free base or its agrochemically acceptable salts as a free base or its agrochemically acceptable salts and Diafenthiuron as a free base or its agrochemically acceptable salts in the form of suspo-emulsion (SE). The invention also relates to the process for the preparation of the said formulation.

BACKGROUND OF THE INVENTION

Insecticide or pesticides are used widely and very frequently in commercial agriculture and have enabled an enormous increase in crop yields and product quality which ultimately increased the ease to farmers in term of economic advantage as well as ease of farming activities.

Pyriproxyfen, is chemically known as 4-phenoxyphenyl (RS)-2-(2-pyridyloxy)propyl ether 2-[1-(4-phenoxyphenoxy)propan-2-yloxy]pyridine and having chemical structure as below;

Pyriproxyfen is a pyridine-based pesticide which is found to be effective against a variety of arthropoda. Pyriproxyfen is a solid (melting range 48-50ºC) of low volatility and only slightly soluble in water. It has no discernible acidic or basic characteristics and is stable to hydrolysis at pH 4-9 at 25°C, but is prone to slow photolysis.

It was introduced to the US in 1996, to protect cotton crops against whitefly. It has also been found useful for protecting other crops. It is also used as prevention for fleas on household pets. Pyriproxyfen is a juvenile hormone analog, preventing larvae from developing into adulthood and thus rendering them unable to reproduce.

In USA, Pyriproxyfen is often marketed under the trade name Nylar. In Europe Pyriproxyfen is known under the brand names Cyclio (Virbac).

Diafenthiuron, is chemically known as 1-tert-butyl-3-(2,6-di-isopropyl-4-phenoxyphenyl)thiourea or N-[2,6-bis(1-methylethyl)-4-phenoxyphenyl]-N'-(1,1-dimethylethyl)thiourea and having chemical structure as below;

Diafenthiuron acts after conversion by either light, or in vivo, to the corresponding carbodiimide, which is an inhibitor of mitochondrial respiration. Mode of action as insecticide and acaricide which kills larvae, nymphs and adults is by contact and/or stomach action; also shows some ovicidal action. It is commonly used as insecticide and acaricide effective against phytophagous mites (tetranychidae, tarsonemidae), aleyrodidae, aphididae and jassidae on cotton, various field and fruit crops, ornamentals and vegetables. Diafenthiuron also controls some leaf-feeding pests in cole crops (Plutellaxylostella), soya beans (Anticarsiagemmatalis) and cotton (Alabama argillacea). Diafenthiuron is marketed under the brand name of Pegasus and polo.

Certain mixtures of active compounds are proposed for pest control in the earlier literature. U.S. Patent No.4,104,376 discloses a synergistic formulation for insect control comprised of a combination of phosphorodithioate and formamidine at a ratio of 1 to 0.1 - 1.0, preferably 1 to about 0.2 - 0.5.

U. S. Patent No.4,613,617 discloses synergistic compositions for insect control comprising dione esters and other insecticides, such as pyrethroids, carba- mates and organophosphates.

U.S. Patent No.4,767,773 discloses synergistic compositions for insect control comprising benzoyl ureas and pyrethroids, carbamates, and organophosphates.

U.S. Patent No.5,187,184 discloses that synergistic compositions for insect control comprising adding arylnitropyrrole or arylpyrrole- carbonitrile to a compositions of arylpyrazolecarboximide pro- vides superior pest control at lower levels of the combined active ingredients than may be achieved with the arylnitropyrrole or arylpyrrolecarbonitrile or arylpyrazolecarboximide applied alone at equal or higher levels than the total amount of active agent used in the combination treatment.

U.S. Patent No.5,491,168 discloses synergistic compositions for insect control comprising propargite (tert. butyl phenoxycyclohexylpropynyl sulfite) and a pyrethroid. Finally, JP Kokai (A) H8-198719 published August 6, 1996 discloses agricultural and horticultural fungicides comprised of a synergistic combination of a substance which inhibits the complex I enzyme reaction of the mitochondria electron transfer system (e.g., Pyridaben) and a substance which inhibits the complex III enzyme reaction of the mitochondria electron transfer system (e. g., kresoxim-methyl). (Entire content of all these prior arts are expressly incorporated hereinto by reference).

753/MUM/2012 relates to a composition comprising an effective amount of lambda Cyhalothrin in the range of 0.5% to 12%; an effective amount of Diafenthiuron in the range of 15% to 70% wherein the ratio of Lambda Cyhalothr into Diafenthiuron is in the range of 1:4 to 1:35; and at least one agrochemical excipient.

However, the biological properties of these mixtures of known compounds are not completely satisfactory in the field of pest control.

In general use, the pesticide actives are used in the form of a dilute aqueous composition because it can attain a good interaction with the target organism, such as plants, fungi and insects. However, most active pesticide compounds that are used as pesticides are only sparingly or even insoluble in water. The low solubility of such compounds present the challenges and difficulties to formulator in formulating pesticide compounds in stable formulations that can be easily stored for a long time and which still have a high stability and effective activity until end use. This problem especially occurs and may get worsen if more than one active compoundis present in the composition.

For the reasons mentioned above there is a need to provide further formulation of combination of two actives having synergistic pest control properties. This object is achieved according to the invention by providing the present formulation.

SUMMARY OF THE INVENTION

The present invention relates to a synergistic combination suspo-emulsion formulation comprising A) Pyriproxyfen as a free base or its agrochemically acceptable salts b) Diafenthiuron as a free base or its agrochemically acceptable salts c) Dispersant d) Anti-freezing agent e) Anti-foaming agent f) Suspending agent g) Antimicrobial agent h) Thickener and i) Buffering agent.

Yet another aspect of the present invention is a suspo-emulsion formulation comprising a) 1 to 15% Pyriproxyfen as a free base or its agrochemically acceptable salts b) 25 to 55% Diafenthiuron as a free base or its agrochemically acceptable salts c) 15 to 25% Dispersant d) 2 to 6% Anti-freezing agent e) 0.05 to 0.25% Anti-foaming agent f) 1 to 3% Suspending agent g) Anti-microbial agent h) 0.05 to 0.25% Thickener and i) Buffering agent.

Yet one more aspect of the present invention is a suspo-emulsion formulation comprising a) 5 to 10% Pyriproxyfen as a free base or its agrochemically acceptable salts b) 45 to 55% Diafenthiuron as a free base or its agrochemically acceptable salts c) 15 to 25% Dispersant d) 2 to 6% Anti-freezing agent e) 0.05 to 0.25% Anti-foaming agent f) 1 to 3% Suspending agent g) Anti-microbial agent h) 0.05 to 0.25% Thickener and i) Buffering agent.

One more aspect of the present invention is a suspo-emulsion formulation comprising a) 5 to 10% Pyriproxyfen as a free base or its agrochemically acceptable salts b) 45 to 55% Diafenthiuron as a free base or its agrochemically acceptable salts c) 15 to 25% ethoxylates of Octyl Phenol & Poly Aryl Phenol d) 2 to 6% polyethylene glycols e) 0.05 to 0.25% silicone emulsion f) 1 to 3% Magnesium Aluminium Silicate g) anti-microbial agent h) 0.05 to 0.25% xanthan gum and i) buffering agent.

Yet another aspect of the present invention is a suspo-emulsion formulation comprising a) 1 to 15% Pyriproxyfen as a free base or its agrochemically acceptable salts b) 25 to 55% Diafenthiuron c) 15 to 25% Dispersant d) 2 to 6% Anti-freezing agent e) 0.05 to 0.25% Anti-foaming agent f) 1 to 3% Suspending agent g) Anti-microbial agent h) 0.05 to 0.25% Thickener and i) Buffering agent wherein the ratio of Pyriproxyfen as a free base or its agrochemically acceptable salts to Diafenthiuron as a free base or its agrochemically acceptable salts is from 29:1 to 1:29.

The present invention also related to process for preparing the supso-emulsion formulation comprising Pyriproxyfen as a free base or its agrochemically acceptable salts and Diafenthiuron as a free base or its agrochemically acceptable salts along with other inactive excipients.

Yet one more aspect of the present invention is to provide a suspo-emulsion formulation, comprising a) Pyriproxyfen as a free base or its agrochemically acceptable salts b) Diafenthiuron as a free base or its agrochemically acceptable salts in the ratio of 29:1 to 1:29 which provides treatment against sucking pests Aphids, Jassids, whitefly, Thrips and phytophagous mites (Tetranychidae, Tarsonemidae, Aleyrodidae, Aphididae) and Jassidae on cotton, leaf-feeding pests in cole crops (Plutellaxylostella), soya beans (Anticarsiagemmatalis) and cotton (Alabama argillacea) and Leaf miner, Liriomyza trifolii infesting Tomato crop.

DETAILED DESCRIPTION OF THE INVENTION

The term "synergistic", as used herein, refers the combined action of two or more active agents blended together and administered conjointly that is greater than the sum of their individual effects.

A suspo-emulsion (SE) formulation is essentially a mixture of a suspension concentrate with an oil-in-water emulsion.

The insecticidal formulations of this invention will necessarily include an effective amount of Pyriproxyfen as a free base or its agrochemically acceptable salts that is disclosed in U.S. Patent No. 4,751,225 (the entire content of which is expressly incorporated hereinto by reference).Pyriproxyfen as a free base or its agrochemically acceptable salts is present in the range of 1 to 15%, preferably in the range of 5 to 10% in the formulation.

The agrochemically acceptable salts of the Pyriproxyfen are, for example, acid addition salts of inorganic and organic acids, in particular of hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, perchloric acid, phosphoric acid, formic acid, acetic acid, trifluoroacetic acid, oxalic acid, malonic acid, toluenesulfonic acid or benzoic acid.

The insecticidal formulations of this invention will necessarily include an effective amount of Diafenthiuron as a free base or its agrochemically acceptable salts that is disclosed in U.S. Patent No. 4, 939,257 (the entire content of which is expressly incorporated hereinto by reference).Diafenthiuron as a free base or its agrochemically acceptable salts is present in the range of 25 to 55%, preferably in the range of 45 to 55 % of the formulation.

The agrochemically acceptable salts of the Diafenthiuron are, for example, acid addition salts of inorganic and organic acids, in particular of hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, perchloric acid, phosphoric acid, formic acid, acetic acid, trifluoroacetic acid, oxalic acid, malonic acid, toluenesulfonic acid or benzoic acid.

Further as per the present invention the ratio of Pyriproxyfen as a free base or its agrochemically acceptable salts to Diafenthiuron as a free base or its agrochemically acceptable salts is in the range from 29:1 to 1:29.

The formulations are preferably applied to controls –sucking pests, mites and white fly (bemisiatabaci family Aleyrodidae). Due to totally different mode of actions of both molecules- once based on thiourea which is acting through degradation of Diafenthiuron as a free base or its agrochemically acceptable salts by light into carbodiimide that disrupts oxidative phosporylation by inhibition of mitochondrial ATP synthase, an enzyme with essential role in cellular bioenergetics. Pyriproxyfen as a free base or its agrochemically acceptable salts is a new pyridine –based insect growth regulator that mimics the action of juvenile hormone.

In case of Diafenthiuron biochemistry it is converted by light, or in vivo, to the corresponding carbodiimide, which is an inhibitor of mitochondrial respirationwhereas in case of Pyriproxyfen, it acts as an insect growth regulator. In white flies, the mode of action of Pyriproxyfen is by accumulating in developing larvae where it apparently acts like juvenile hormone to maintain genes that direct production of larval cuticle. The presence of Pyriproxyfen during metamorphosis prevents whitefly from successfully completing either the larval-pupal or pupal-adult moult causing the flea to transform into a larval-pupal or a pupal-adult intermediate that can neither function nor reproduce.

Mode of action of insecticide and acaricide which kills larvae, nymphs and adults by contact and/or stomach action also shows some ovicidal action.

The said formulation is effective against sucking pests Aphids, Jassids, whitefly, Thrips and phytophagous mites (Tetranychidae, Tarsonemidae, Aleyrodidae, Aphididae) and Jassidae on cotton, various field and fruit crops, ornamentals and vegetables. The said formulation also controls some leaf-feeding pests in cole crops (Plutellaxylostella), soya beans (Anticarsiagemmatalis) and cotton (Alabama argillacea). The said formulation is also found to be active against Leaf miner, Liriomyza trifolii infesting Tomato crop.

The formulationofthe present invention is safe on adults of all beneficial groups (Anthocoridae, Coccinellidae, Miridae) and on adults and immature stages of predatory mites (Amblyseiusandersoni, Typhlodromuspyri), spiders (Erigonidae, Lycosidae), and Chrysopacarnea. Non-selective to immature stages of Heteroptera (Anthocoridae, Miridae).Compatible with the biological control of Aleyrodidae and mites in glasshouses.

The formulation of the present invention can be applied by spraying. For end use the formulation is to be diluted 1 litre in 500 litre of water for one hectare.

The formulation of this invention may also be applied in conjunction with other inactive excipients commonly employed in the art. Examples of such ingredients include dispersing agents,anti-freezing agent, anti-foaming agents, suspending agents, anti-microbial agents, thickeners, solvent and buffering agents and combinations thereof and other such adjuvants well known in the art.

Additional applications of these amounts may be required over the course of the growing season, depending on the presence of insect pests.

A suspo-emulsion formulation is essentially a mixture of a suspension concentrate with an oil-in-water emulsion. They are designed to allow the widest possible combination of active ingredients in a single formulation, particularly where one active ingredient is a solid like Diafenthiuron as a free base or its agrochemically acceptable salts and other active ingredient is liquid like Pyriproxyfen as a free base or its agrochemically acceptable salts. A three-way mixed formulation is possible if one of the active ingredients is soluble in water. Suspo-emulsion formulation consists of three phases.
• Insoluble solid phase as dispersed particles
• Insoluble liquid phase as oil droplets
• Water as bulk phase

However, it is not usually possible to make a suspo-emulsion by simply mixing a suspension concentrate (SC) formulation with an oil-in-water (EW) formulation because the correct balance of dispersing and emulsifying agents may not be achieved. This may lead to preferential adsorption on one surface or the other, resulting in heteroflocculation problems. To determine the optimum type and concentration of dispersing and emulsifying agents prepare a stable suspo-emulsion formulation is very difficult.

The general process for preparing SE formulations is outlined below.
1. Preparing a concentrated suspension of the solid active ingredient using a bead milling process with particle size < 10 microns.
2. Preparing an o/w emulsion by a high shear mixing process droplet size of 2-5 microns
3. Mixing together the suspension and emulsion with low shear mixing
4. Adding thickening agent and other additives as necessary

An alternative procedure may sometimes be used in order to obtain a higher concentration of active ingredients in the formulation, as shown below:
1. Preparing concentrated suspension as above
2. Emulsifying liquid active ingredient into suspension using high shear mixer
3. Adding thickening agents and other additives.

There are many advantages of suspo-emulsion formulation as outlined below;
• Multiple solid and liquid active ingredients in a single formulation
• Water based – no organic solvent VOC’s in external bulk phase
• Ready mixed formulation
• Have high flash point and water-miscible
• Have high compatibility with high density polyethylene (HDPE) containers
• Are easy to handle, measure, dust free and non-flammable
• Easy to pour and measure
• Possible reduction in skin and eye toxicity
• Avoids tank mix compatibility problems
• May be reduced cost due to low or no solvent usage

Advantage of suspo-emulsion in comparison of wettable powder (WP) and emulsifiable concentrate (EC) formulation is outline below;
• The particle size (less than 1 micron) of Suspo – emulsion formulation is smaller than particle size (30 – 50 micron) of WP formulation.
• SE formulation is eco – friendly formulation as it is water based whereas WP formulation is dusty.
• SE formulation has contains no organic solvent whereas EC formulation has contains organic solvent.
• As non –ionic surfactants are used in SE formulation, so it gives better bio - efficacy than EC & WP formulation.

Dispersing agent as used herein can be selected from the group comprising of ethoxylates of Octyl Phenol & Poly Aryl Phenol, sodium naphthalene formaldehyde condensate and ethoxylated polyoxypropylene or mixtures thereof. Dispersant can be used in the range of 15 to 25 % of the formulation. Preferred one is ethoxylates of Octyl Phenol & Poly Aryl Phenol.

Anti-freezing agent as used herein can be selected from the group comprising of polyethylene glycols, methoxypolyethylene glycols, polypropylene glycols, polybutylene glycols, glycerin and ethylene glycol or mixtures thereof.Anti-freezing agent can be used in the range of 2 to 6% of the formulation. Preferred one is polyethylene glycol.

Anti-foaming agent as used herein is used for reducing or preventing the formation of foam within the mixture and can be selected from the group comprising of silicone emulsion, perfluoroalkylphosphonic acids, perfluoroalkylphosphinic acids and perfluoroaliphatic polymeric esters or mixtures thereof. The anti-foaming agent may also facilitate movement of entrapped air out of the mixture. The antifoaming agent may enable the wetting agent and the dispersant, when included, to function properly within the mixture, and may facilitate spraying of the insecticide while reducing the chances of the sprayer becoming clogged with foam or entrained air. Anti-foaming agent can be used in the range of 0.05 to 0.25% of the formulation. Preferred one is silicone emulsion.

Suspending agent as used herein can be selected from the group comprising of Magnesium Aluminium Silicate, fumed silica and magnesium montmorillonite or mixtures thereof. Suspending agent can be used in the range to 1 to 3% of the formulation. Preferred one is Magnesium Aluminium Silicate.

Anti-microbial agent as used herein can be selected from the group comprisingof2-bromo-2-nitropropane-1,3-diol, 1,2-benzisothiazolin-3-one, 2-methyl-4-isothiazolin-3-one and 5-chloro-2-methyl-4-isothiazolin-3-one.

Thickener as used herein can be selected from the group comprising of xanthan gum, carboxymethylcellulose, hydroxyethylcellulose, dextrine, gum arabicandpolyvinyl alcohol or mixtures thereof. A thickener are generally used as an additive in the formulation which may increase viscosity, change consistency, stabilize and/or facilitate suspending of the active particles within the liquid mixture. The thickener may also enable the liquid mixture to be applied to areas of a surface and may form a wet, gel-like deposit prior to drying. This may enable the active particles to stick to the insect by way of the thickening agent while the applied mixture is wet. Thickener can be used in the range of 0.05 to 0.25% of the formulation. Preferred one is xanthan gum.

Solvent as used herein is selected from either aqueous or non-aqueous. Preferable solvent is demineralizedwater (DM water).

Buffering agent as used herein is selected from group consisting of Potassium Dihydrogen Phosphate & Sodium Hydroxide or mixtures thereof.

The present invention will now be explained in detail by reference to the following formulation examples and a test example, which should not be construed as limiting the scope of the present invention.

EXAMPLES
Examples 1 (SE formulation)
Formulation (1000 Kg lot)
Step No. 1 (OIL PHASE)
Ingredients Kg
Octyl phenol ethoxylates 100.00
Pyriproxyfen 54.00
Ethoxylates of Poly Aryl Phenol 51.00
Propylene Glycol 25.00
Octyl phenol ethoxylates and Pyriproxyfen as a free base or its agrochemically acceptable salts are mixed thoroughly with a high speed homogenizer. Ethoxylates of Poly Aryl Phenol and propylene glycol are added sequentially and material homogenized for about 2 hours with 1500 RPM at room temperature.
Step No.2 (AQUEOUS PHASE)
Ingredients Kg
Diafenthiuron 262.50
Acrylic polymer of Amine Salt 5.00
Magnesium Aluminium Silicate 5.00
Silica 5.00
Silicon Antifoam Emulsion 1.00
DM water Q.s
In a separate vessel, Acrylic polymer of Amine Salt, Magnesium Aluminium Silicate, Silica and Silicon Antifoam Emulsion are added sequentially then finally Diafenthiuron as a free base or its agrochemically acceptable salts is added slowly and material stirred for about 2 hours with 2000RPM.
Step No.3
The homogenize material from Step 1 (OIL PHASE) is transferred to the material prepared in Step 2 (AQUEOUS PHASE) and further homogenized with a high speed homogenizer with 2000RPM for about 2 hours.
Step No.4
After homogenization the material from Step 3 is passed through horizontal bead mill for around 6 cycles and the milled material is collected in the vessel.
Step 5: Preparation of Gum Solution (2%)
Ingredients Kg
DM Water Q.s
Pot. Dihydrogen phosphate 1.5
Sod. Hydroxide 0.25
Benzisothiazoline 2.25
Rhodopol 23W 1.00
Take the ingredients in a mixer and homogenize thoroughly in 2 KL vessel with maintaining the temperature around 50 degrees.

Step No.6
To the milled material of Step 4 Gum solution prepared in step 5 is added slowly and material homogenized with high speed homogenizer with 2000RPM for around 2 hours.

Example 2 (SE formulation)
S. No. Ingredients Quantity Gms
1 Pyriproxyfen 1.05 5.25 10.50 15.75 21.00 26.25 30.45
2 Diafenthiuron 30.21 26.00 20.80 15.60 10.40 5.20 1.04
3 Alkyl phenol ethoxylates 10 10.00 10.00 10.00 10.00 10.00 10.00
4 Tristyrylphenolethoxylate 2.15 2.15 2.15 2.15 2.15 2.15 2.15
5 Ethoxylatedtristyrylphenol
sulfate, ammonium salt 1.15 1.15 1.15 1.15 1.15 1.15 1.15
6 Ethoxylatedtristyrylphenol 1.8 1.80 1.80 1.80 1.80 1.80 1.80
7 Silicon dioxide 1 1.00 1.00 1.00 1.00 1.00 1.00
8 Triethanolaminepolyacrylate 0.5 0.50 0.50 0.50 0.50 0.50 0.50
9 Monoethylene glycol 2.7 2.70 2.70 2.70 2.70 2.70 2.70
10 DM Water 48.43 48.44 48.39 48.34 48.29 48.24 48.20
11 Polysaccharide 0.8 0.80 0.80 0.80 0.80 0.80 0.80
12 Silicon based antofoam 0.01 0.01 0.01 0.01 0.01 0.01 0.01
13 1,2-Benzisothiazolin-3-one 0.2 0.20 0.20 0.20 0.20 0.20 0.20
Total 100 100 100 100 100 100 100

Procedure:This is carried out according to Example 1.

Example 3 (WG formulation)
S. No. Ingredients Quantity Gms
1 Pyriproxyfen 1.05 21.00 5.25 51.45
2 Diafenthiuron 51.04 31.20 26.00 1.04
3 Sodium alkylnaphthalenesulfonate, formaldehyde condensate 5 5.00 5.00 5.00
4 Styrine acrylic polymer 2 2.00 2.00 2.00
5 Sodium salt of sulphated product 3 3.00 5.00 3.00
6 Sodium alkyl napthalenesulphonate 3 3.00 4.75 3.00
7 Silicon dioxide 15 15.00 18.00 14.60
8 Kaolin 12 11.89 18.00 12.00
9 Silicon based antifoam 1 1.00 1.00 1.00
10 Diatomaceous earth 6.91 6.91 15.00 6.91
Total 100 100 100 100

Procedure:

Part -A
Measured quantity of Diafenthiuron as a free base or its agrochemically acceptable salts and Pyriproxyfen as a free base or its agrochemically acceptable salts were added into the blender. With continued stirring, charged quantity of other raw materials were added in blender. After completion of raw material stirring was stopped within 30 min. The pre-blended material was micronized for at least 6 hrs. After completion of grinding through air classifier mill, post blinding was performed for about 1 to 2 hrs.

Part-B
Powder obtained from step 1) was wetted by addition of DM water to prepare paste.

Part-C
Extrusion granulation was performed from the paste of step B by pressing it through an extrusion screen to give elongated wet granules which are then dried. The granules formed are usually about 2-10 mm in length and the diameter depends on the screen size.

Example 4 (EC formulation)
S. No. Ingredients Quantity Gms
1 Pyriproxyfen 4.21 4.20 4.20
2 Diafenthiuron 8.33 12.48 16.64
3 Blend of calcium salt of alkylbenzene and sulfonic acid polyethanoxy ether of benzyl phenol/ fatty alcohol 13.15 13.15 13.15
4 Normal butylated alcohol 6 6.00 6.00
5 Aromatic hydrocarbon solvent 56 51.86 47.70
6 Cyclohexanone 12.31 12.31 12.31
Total 100 100 100

Procedure:
•Pyriproxyfen as a free base or its agrochemically acceptable salts and Diafenthiuron as a free base or its agrochemically acceptable salts were added in to vessel followed by emulsifier and stabilizer.
• Stirring of above mixture was performed.
•Inter circulation started for getting transparency of material through sparkler filter.

The finely ground active Suspo emulsion formulation of Diafenthiuron as a free base or its agrochemically acceptable salts and Pyriproxyfen as a free base or its agrochemically acceptable salts are prepared as per above examples with the additives. This gives a Suspo emulsion formulation of Diafenthiuron as a free base or its agrochemically acceptable salts and Pyriproxyfen as a free base or its agrochemically acceptable salts.

Cotton is an important fiber crop of global significance cultivated in more than seventy countries. It is an important raw material for the Indian textile industry and plays a key role in the national economy in terms of both employment generation and foreign exchange. Main losses in cotton production are due to its susceptibility to about 162 species of insect pests and a number of diseases (Manjunath, T. M. (2004) Bt cotton in India: Thetechnology wins as the controversy wanes. http:// www.Monsanto.co.uk/news/ukshowlib.html?wid=8478.). Among insects, cotton bollworms are the most serious pests of cotton in India causing annual losses to the tune of Rs.1200 crores. After introduction of Bollgard technology (Bt) in 2002, the productivity of cotton is increased, losses due to insect pests are decreased and the insecticide use is also reduced. However, these changes have allowed other pests to survive and emerge as economic pests. Among the important key pests of cotton the sucking pests viz., leafhopper, Amrascabiguttulabiguttula (Ishida), aphid, Aphis gossypii (Glover), whitefly Bemisiatabaci (Gennadius) and thrips, Thripstabaci (Linnman) cause severe damage and serious threat to the crop at early stage of the crop growth and can also affect the crop stand and yield of cotton. Heavy infestation at times reduces the crop yield to the extent of 21.2 per cent (Patil (1998) Developing IPM schedule. Proc. Seminar on IPM.Specialissue.ICPA.Mumbai.pp. 101-110.Dhawan, A. K. and Sidhu, A. S. (1986) Assessment oflosses due to attack of cotton jassid on hirsutumcotton.Indian J. Plant Prot., 14: 45-50). Some sucking pests are cosmopolitan, polyphagus, widely distributed in tropical, subtropical and temperate regions and are also vectors for a number of viral diseases in large number of plants (Serdar et al., 1999 Selection of chestnut (Castanea sativa Mill.) in Sinop vicinity. ActaHortic 494: 327-332). Therefore chemical control is necessary to keep the population of sucking pests below ETL. In the present study some new insecticides have been used to test their efficacy against the sucking pests.

Whitefly Bemisiatabaci (Gennadius) is the most serious sucking pests of cotton in India almost all the cotton growing area. It also acts as a carrier of virus which causes CLCV (Cotton Leaf Curl Virus) in Northern part of India. Both the Nymphs and adults of whitefly cause severe damage to the crop by sucking cell sap and inhibiting plant growth which results in to direct yield. Therefore it is important to manage these pests from beginning. There are many insecticides which are used for control of whitefly as a solo, as a tank mixes and premix also.

Biological examples

A synergistic effect is always present when the action of the combination of the active ingredient in novel formulation of Suspo emulsion formulation of Diafenthiuron as a free base or its agrochemically acceptable salts and Pyriproxyfen as a free base or its agrochemically acceptable salts exceeds the total of the action of the active ingredients applied individually.

For example, the expected pesticidal action for a given novel formulation of Suspo emulsions formulation of Diafenthiuron as a free base or its agrochemically acceptable salts and Pyriproxyfen as a free base or its agrochemically acceptable salts. If the actually observed action exceeds the expected value, synergism is present.

Example 5
Activity / Efficacy on cotton, effective control of whitefly

In order to provide effective control of whitefly and longer duration of cotton, various formulations of Diafenthiuron as a free base or its agrochemically acceptable salts and Pyriproxyfen as a free base or its agrochemically acceptable salts were prepared and tested. The test of bio efficacy was performed and the results are listed in below Table.

Table: 1
No. Treatment Compositions Active Ingredients (grams per hectare) Formulation per hectare Average Number of Whitefly per Leaf
Bemisiatabaci Nymphs
0
DAT 3
DAT 10
DAT 15
DAT 20
DAT
1 Diafenthiuron 29% + Pyriproxyfen 1% SE * 290+10 1000 ml 3.18 6.26 16.67 22.73 38.34
2 Diafenthiuron 25% + Pyriproxyfen 5% SE 250+50 1000 ml 4.26 1.87 3.84 5.38 6.92
3 Diafenthiuron20% + Pyriproxyfen 10% SE 200+100 1000 ml 2.94 2.23 4.18 5.27 6.28
4 Diafenthiuron 15% + Pyriproxyfen 15% SE 150+150 1000 ml 3.27 2.60 6.82 8.87 10.26
5 Diafenthiuron 10% + Pyriproxyfen 20% SE 100+200 1000 ml 4.23 3.27 8.26 10.92 16.23
6 Diafenthiuron 5% + Pyriproxyfen 25% SE 50+250 1000 ml 2.84 2.93 11.23 13.82 21.83
7 Diafenthiuron 1% + Pyriproxyfen 29% SE 10+290 1000 ml 3.26 4.28 19.39 28.77 38.72
8 Diafenthiuron 8% + Pyriproxyfen 4% EC ** 80+40 1000 ml 3.82 6.27 23.58 39.62 45.83
9 Diafenthiuron 12% + Pyriproxyfen 4% EC 180+60 1500 ml 4.12 5.32 16.27 27.24 36.17
10 Diafenthiuron 16% + Pyriproxyfen 4% EC 240+60 1500 ml 3.79 3.28 6.92 19.92 30.27
15 Diafenthiuron 49% + Pyriproxyfen 1% WDG *** 245+5 500 g 3.62 4.28 29.38 36.28 46.44
16 Diafenthiuron 30% + Pyriproxyfen 20% WDG 150+100 500 g 4.26 2.67 12.54 18.35 22.16
17 Diafenthiuron 25% + Pyriproxyfen 5% WDG 125+25 500 g 4.40 2.64 10.83 11.39 14.28
18 Diafenthiuron 1% + Pyriproxyfen 49% WDG 2.5+122.5 500 g 3.28 5.82 25.73 42.84 45.26
19 Diafenthiuron 50% WP + Pyriproxyfen 10% EC (Tank mix) 150+50 300g + 500ml 4.26 2.83 8.23 10.93 15.77
20 Diafenthiuron 50% WP + Pyriproxyfen 10% EC (Tank mix) 312.5+100 600g + 1000ml 3.82 5.12 10.92 13.73 15.28
21 Diafenthiuron 50% WP 312.5 600g 4.26 4.26 9.33 11.83 20.22
22 Pyriproxyfen 10% EC 100 1000ml 4.63 2.83 10.73 12.81 21.17
23 Untreated Control (No Insecticide) 0 0 3.86 14.25 30.72 41.83 61.37
DAT- Days After Treatment, * SE- Suspo-Emulsion, ** EC -Emulsifiable Concentration
*** WDG -Wettable Powder, # SC -Suspension Concentrate, ## SP -Soluble Powder

Table:2
No. Treatment Compositions Active Ingredients (grams per hectare) Formulation per hectare Average Number of Whitefly per Leaf
Bemisiatabaci Adults
0 DAT 3 DAT 10 DAT 15 DAT 20 DAT
1 Diafenthiuron29% + Pyriproxyfen 1% SE * 290+10 1000 ml 4.67 1.07 10.13 13.87 16.60
2 Diafenthiuron 25% + Pyriproxyfen 5% SE 250+50 1000 ml 3.23 0.07 0.53 0.80 1.07
3 Diafenthiuron 20% + Pyriproxyfen 10% SE 200+100 1000 ml 4.16 0.13 0.67 0.93 1.27
4 Diafenthiuron 15% + Pyriproxyfen 15% SE 150+150 1000 ml 3.57 1.13 2.60 3.90 7.67
5 Diafenthiuron 10% + Pyriproxyfen20% SE 100+200 1000 ml 3.87 1.40 3.47 4.60 9.80
6 Diafenthiuron 5% + Pyriproxyfen 25% SE 50+250 1000 ml 4.28 2.00 8.80 9.87 14.53
7 Diafenthiuron 1% + Pyriproxyfen 29% SE 10+290 1000 ml 3.17 2.22 11.64 22.81 27.31
8 Diafenthiuron 8% + Pyriproxyfen 4% EC ** 80+40 1000 ml 4.83 2.27 18.83 29.84 38.92
9 Diafenthiuron 12% + Pyriproxyfen 4% EC 180+60 1500 ml 3.57 1.63 13.60 22.20 32.60
10 Diafenthiuron 16% + Pyriproxyfen 4% EC 240+60 1500 ml 3.30 1.13 10.80 18.87 23.93
15 Diafenthiuron49% + Pyriproxyfen 1% WDG *** 245+5 500 g 4.53 1.23 15.73 24.84 31.28
16 Diafenthiuron 30% + Pyriproxyfen20% WDG 150+100 500 g 4.83 1.27 9.13 12.87 14.60
17 Diafenthiuron 25% + Pyriproxyfen 5% WDG 125+25 500 g 3.00 0.93 2.12 3.42 6.93
18 Diafenthiuron 1% + Pyriproxyfen 49% WDG 2.5+122.5 500 g 3.94 1.97 14.63 19.64 30.27
19 Diafenthiuron 50% WP + Pyriproxyfen 10% EC (Tank mix) 150+50 300g + 500ml 3.27 1.60 5.47 6.33 8.33
20 Diafenthiuron 50% WP + Pyriproxyfen 10% EC (Tank mix) 312.5+100 600g + 1000ml 4.23 0.60 2.83 4.23 8.40
21 Diafenthiuron 50% WP 312.5 600g 4.52 1.00 6.93 8.20 11.20
22 Pyriproxyfen 10% EC 100 1000ml 3.94 1.93 7.27 8.33 12.13
23 Untreated Control (No Insecticide) 0 0 3.97 8.23 26.30 33.60 44.72
DAT- Days After Treatment, * SE- Suspo-Emulsion, ** EC -Emulsifiable Concentration
*** WDG -Wettable Powder, # SC -Suspension Concentrate, ## SP -Soluble Powder

Conclusion: Among the various formulations of premix of Diafenthiuron and Pyriproxyfen tested against cotton whitefly, Suspo Emulsion (SE) formulation of Diafenthiuron+ Pyriproxyfen(205+50, 200+100, 150+150 and 100+200 g.a.i. per ha.) found most effective against whitefly adults as well as nymphs. They also provide longer residual control of both whitefly adults and nymphs. It is also highly effective and provides longer duration of Whitefly nymphs on cotton crop.
Other premix formulations of Diafenthiuron as a free base or its agrochemically acceptable salts and Pyriproxyfen as a free base or its agrochemically acceptable salts, like Emulsifiable Concentrate (EC), Water Dispersible Granules (WDG) are also effective against Whitefly Adults and Nymphs but does not provides longer residual control as compared to Suspo emulsion formulation when compared to rate per hectare used.
Suspo emulsion formulation of premix of Diafenthiuron as a free base or its agrochemically acceptable salts and Pyriproxyfen as a free base or its agrochemically acceptable salts was found to be more efficacious as compared to their individual component like Diafenthiuron50% WP (solo) and Pyriproxyfen10% EC (solo).
Suspo emulsion formulation of premix of Diafenthiuron as a free base or its agrochemically acceptable salts and Pyriproxyfen as a free base or its agrochemically acceptable salts provides higher efficacy and longer duration of control when compared to the on farm tank mixing of individually commercially available formulation of Diafenthiuron50% WP and Pyriproxyfen10% EC.
Example 6
Activity / Efficacy on Tomato Leaf miner, Liriomyza trifolii
Experiment on Leaf miner, Liriomyza trifolii infesting Tomato crop conducted with various formulations and different use rate of Diafenthiuron as a free base or its agrochemically acceptable salts and Pyriproxyfen as a free base or its agrochemically acceptable salts. The test of bio efficacy is performed and the results are listed in below Table.
Table 3:
Sr. No. Treatment Compositions Active Ingredients (grams per hectare) Formulation per Hectare % Leaf Infection by Liriomyza trifolii
0 DAT 5 DAT 10 DAT 15 DAT
1 Diafenthiuron 29% + Pyriproxyfen 1% SE * 290+10 1000 ml 1.16 2.63 3.17 4.26
2 Diafenthiuron 25% + Pyriproxyfen 5% SE 250+50 1000 ml 1.06 1.12 0.97 1.06
3 Diafenthiuron 20% + Pyriproxyfen 10% SE 200+100 1000 ml 1.25 1.09 1.12 1.22
4 Diafenthiuron 15% + Pyriproxyfen 15% SE 150+150 1000 ml 1.18 1.16 1.20 1.30
5 Diafenthiuron 10% + Pyriproxyfen 20% SE 100+200 1000 ml 1.52 1.18 1.25 1.36
6 Diafenthiuron 5% + Pyriproxyfen 25% SE 50+250 1000 ml 0.96 2.85 4.83 7.16
7 Diafenthiuron 1% + Pyriproxyfen 29% SE 10+290 1000 ml 1.08 3.16 5.28 8.10
8 Diafenthiuron 8% + Pyriproxyfen 4% EC ** 80+40 1000 ml 1.26 4.12 6.28 8.36
9 Diafenthiuron 12% + Pyriproxyfen 4% EC 180+60 1500 ml 1.30 1.42 1.68 1.83
10 Diafenthiuron 16% + Pyriproxyfen 4% EC 240+60 1500 ml 1.20 1.20 1.30 1.42
15 Diafenthiuron 49% + Pyriproxyfen 1% WDG *** 245+5 500 g 0.90 2.81 4.40 7.28
16 Diafenthiuron 30% + Pyriproxyfen 20% WDG 150+100 500 g 1.12 2.12 3.68 4.28
17 Diafenthiuron 25% + Pyriproxyfen 5% WDG 125+25 500 g 1.26 3.15 5.82 7.88
18 Diafenthiuron 1% + Pyriproxyfen 49% WDG 5+245 500 g 1.18 4.28 6.25 8.16
19 Diafenthiuron 50% WP + Pyriproxyfen 10% EC (Tank mix) 150+50 300g + 500ml 1.08 2.93 5.72 7.10
20 Diafenthiuron 50% WP + Pyriproxyfen 10% EC (Tank mix) 300+100 600g + 1000ml 1.30 2.10 4.16 6.82
21 Diafenthiuron 50% WP 300 600g 1.21 4.52 7.26 8.84
22 Pyriproxyfen 10% EC 100 1000ml 1.12 4.84 7.68 9.10
23 Untreated Control (No Insecticide) 0 0 1.10 3.16 8.62 15.26
DAT- Days After Treatment, * SE- Suspo-Emulsion,
** EC -Emulsifiable Concentration *** WDG -Wettable Powder,

The results shows excellent efficacy of Suspo emulsion formulation of Diafenthiuron as a free base or its agrochemically acceptable salts and Pyriproxyfen as a free base or its agrochemically acceptable salts on tomato leaf miner as compared to their individual components and on site tank mixers, thereby showing synergistic effect.
Example 7
Stability of Example 1
Stability study of formulation as prepared in Example 1 was performed at 54 °C for 70 days and evaluated at regular interval for below mentioned parameters. Results are mentioned in below table.
Table 4:
Results
Parameter Initial 14 days 42 days 56 days 70 days Remarks
Active (%)
P:5.24%
D:25.21% P:5.16%
D:25.30% P:5.12%
D:25.24% P:5.10%
D:25.21% P:5.10%
D:25.22% Pass

Suspensibility
P:98.17%
D:97.26% P:95.60%
D:95.08% P:95.05%
D:93.01% P:95.06%
D:93.02% P:95.06%
D:93.02% Pass
Viscosity @ 20 RPM 363 CPS 350 CPS 345 CPS 340 CPS 340 CPS Pass
pH (1% Aqsoln) 6.89 6.8 6.78 6.75 6.75 Pass
Persistent foam
(5 ml Max after 1 minute) By Cipac 1.5 ml 1.5 ml 1.5 ml 2 ml 2 ml Pass
Spontaneity P:98.25%
D:97.78% P:98.20%
D:97.75% P:97.80%
D:97.20% P:97.83%
D:97.18% P:97.83%
D:97.19% Pass
Pourability
1% max by Cipac 0.64% 0.64% 0.65% 0.65% 0.65% Pass
P: Pyriproxyfen D: Diafenthiuron
The above results show that suspo-emulsion formulation of Pyriproxyfen and Diafenthiuron is stable.

,CLAIMS:CLAIMS:
1. A Synergistic Suspo emulsion formulation comprising of a) Pyriproxyfen as its free base or its agrochemically acceptable salts and b) Diafenthiuron as its free base or its agrochemically acceptable salts along with inactive excipients wherein, the ratio of Pyriproxyfen to Diafenthiuron is in the ratio from 29:1 to 1:29.
2. The Synergistic suspo emusion formulation according to claim 1 wherein, Pyriproxyfen is present in the range of 1 to 15% and Diafenthiuron is present in the range of 25 to 55 %.
3. The Synergistic suspo emulsion formulation according to claim 1 wherein, inactive excipients comprises of dispersant, anti-freezing agent, anti-foaming agent, suspending agent, antimicrobial agent, thickener and buffering agent.
4. The Synergistic suspo emulsion formulation according to claim 3 wherein dispersant is selected from the group comprising of ethoxylates of Octyl Phenol & Poly Aryl Phenol, sodium naphthalene formaldehyde condensate and ethoxylated polyoxypropylene and the like or mixtures thereof and the said dispersant is present in the range of 15 to 25 %.
5. The Synergistic suspo emulsion formulation according to claim 3 wherein anti-freezing agent is selected from the group comprising of polyethylene glycols, methoxypolyethylene glycols, polypropylene glycols, polybutylene glycols, glycerin, ethylene glycoland the like or mixtures thereof and the said anti-freezing agent is present in the range from 2 to 6 %.
6. The Synergistic suspo emulsion formulation according to claim 3 wherein anti-foaming agent is selected from the group comprising of silicone emulsion, perfluoroalkylphosphonic acids, perfluoroalkylphosphinic acids and perfluoroaliphatic polymeric esters and the like or mixtures thereof and the said anti-foaming agent is present in the range of 0.05 to 0.25 %.
7. The Synergistic suspo emulsion formulation according to claim 3 wherein suspending agent is selected from the group comprising of Magnesium Aluminium Silicate, fumed silica, magnesium montmorillonite and the like or mixtures thereof and the said suspending agent is in the range of 1 to 3 %.
8. The Synergistic suspo emulsion formulation according to claim 3 wherein anti-microbial agent is selected from the group comprising of 2-bromo-2-nitropropane-1,3-diol, 1,2-benzisothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one and the like.
9. The Synergistic suspo emulsion formulation according to claim 3 wherein thickner is selected from the group comprising of xanthan gum, carboxymethyl cellulose, hydroxyethyl cellulose, dextrine, gum Arabic, polyvinyl alcohol and the like or mixtures thereof and the said thickener is in the range of 0.025 to 0.5 %.
10. The Synergistic suspo emulsion formulation according to claim 3 wherein buffering agent is selected from the group comprising of Pottasium Dihydrogen Phosphate, Sodium Hydroxide and the like or mixtures thereof.
11. The Synergistic suspo emulsion formulation as claimed in any of the preceding claims wherein the said formulation is stable.
12. The Synergistic suspo emulsion formulation as claimed in any of the preceding claims wherein the said formulation comprising of Pyriproxyfen and Diafenthiuron is effective against sucking pests Aphids, Jassids, whitefly, Thrips and phytophagous mites (Tetranychidae, Tarsonemidae, Aleyrodidae, Aphididae) and Jassidae on cotton, leaf-feeding pests in cole crops (Plutellaxylostella), soya beans (Anticarsiagemmatalis) and cotton (Alabama argillacea) and Leaf miner, Liriomyza trifolii infesting Tomato crop.
13. The Synergistic suspo emulsion formulation of Pyriproxyfen as a free base or its agrochemically acceptable salts and Diafenthiuron as a free base or its agrochemically acceptable salts as claimed in any of the preceding claims and exemplified with working examples disclosed herein.