DESC:Synergistic Insecticidal Combination of Diafenthiuron and Fipronil
FIELD OF THE INVENTION
The present invention relates to a synergistic insecticidal composition comprising the combination of thiourea insecticide and pyrazole insecticide in EC / WDG / SC / SL / OD / OS / Solid Granules and other formulations in different percentages. More precisely, the subject of the present invention is a synergistic insecticidal composition based on a combination of diafenthiuron and fipronil with at least one agrochemical acceptable excipient(s) which will facilitate in the preparation of desired formulations. The present invention also relates to the process for the preparation of synergistic and broad-spectrum insecticidal composition thereof and use of this combination for combating insecticides in and on the seeds and plants at different growth stages for crop protection and provides good yields which is environment friendly to control insect-pests and mites in one shot application.
BACKGROUND OF THE INVENTION
Crop protection is the practice of protecting the crop yields from pests, weeds, plant diseases, and other organisms that damage agricultural crops, which is critical from initial stages of crop development. Preventing pests and diseases in the entire crop cycle, i.e., from root development to maturing crop, leads to increased crop quality and yield. The control of insects is extremely important in achieving high crop efficiency. Generally, insects are very destructive to crop plants and can significantly reduce crop yields and quality. Insecticides help to minimize this damage by controlling insect pests. For this purpose, in the field of agrochemical industry, numerous formulations are available for delivering active ingredients or combinations, but there is still a continues need to develop new insecticidal combinations which are more effective, less costly, less toxic, environmentally safer and have different sites of action. The use of two or more appropriate active ingredient combinations in specific dose ratios leads to synergism in crop protection.
Therefore, it is indeed necessary to use the insecticidal combinations in lower doses, fast acting with the different mode of action in a suitable formulation that can provide long lasting control against broad spectrum insects. The composition should have high synergistic action, no cross resistance to existing insecticides, avoid excess loading residue of the toxicant to the environment and negligible impact to environmental safety. A need also exists for synergistic insecticidal compositions which could be physico-compatible formulations in the form of storage stable, safely packed, ready to use formulation.
To reduce the risk of the selection strains, mixtures of different active compounds are employed for controlling insect-pests. It is possible to ensure successful control over a relatively long period of time by combining active compounds having different mechanisms of action.
Thus, the present inventors have intensively studied to solve these problems, identified a need for a granular formulation and advantages of ease of use, safety, and environmental compatibility.
OBJECTS OF THE INVENTION
The principal object of the present invention is to provide an insecticidal mixture or combination which solves at least one of the major problems discussed above like reducing the dosage rate, broadening the spectrum of activity, or combining activity with prolonged pest control and resistance management with improved environmental safety by reducing toxicity and residue deposit in soil and in crops.
The details of one or more embodiments of this disclosure are set forth in the accompanying description below and other features, objects, and advantages will be apparent from the description and the claims.

SUMMARY OF THE INVENTION
In an embodiment of the present invention provides a synergistic insecticidal composition comprising thiourea insecticide and pyrazole insecticide with at least one or more agrochemical acceptable excipients.
In an aspect of the present invention provides an insecticidal comprising thiourea insecticide and pyrazole insecticide with one or more suitable agrochemical auxiliaries, wherein the suitable agrochemical excipients are selected from the group comprising of a carrier, surfactant, stabilizer, anti-freezing agent, antifoaming agent, anticaking agent, dispersing agent, and adjuvant(s).
Accordingly, in a further aspect of present invention the present insecticidal composition can be applied as a foliar spray, soil drenching, seed dressing, application to the targeted crops, plants and trees.
In an embodiment of the present invention the formulation excipients or inactive excipients are used in present suspension concentrate formulation are selected from carrier, wetting agent, dispersing agent, anti-freezing agent, anti-bacterial agent, antifoaming agent, and adjuvant(s).
DETAILED DESCRIPTION OF THE INVENTION
The present disclosure / specification refers to a synergistic insecticidal composition and the process for the preparation for crop protection.
The term “combination” can be replaced with the words “mixture” or “composition” or “formulation” defined or refers to as combining two or more active ingredients formulated in desired formulations.
The term “agrochemical auxiliaries” can be replaced with the words “formulation excipients” or “inactive excipients” or “agriculturally acceptable excipients” or “agrochemical excipients” or “agrochemical acceptable excipients”.
The term “pesticide” as used in this specification refers to a substance or mixture of substances intended for preventing, destroying, repelling, or mitigating any pest or weeds which causes damage to the crop. Herbicides, insecticides, and fungicides are mainly used as pesticides which control weeds and insect pests and disease-causing pathogens respectively that eventually leads to high yield of crops.
The term “insecticide” as used in this specification refers to a type of chemical compound or substance or substance mixtures, specifically designed to protect crops by inhibition, control or reduce the damage of crops from insects and kill insects in various agricultural, residential, and public health settings. Integrated pest management practices are encouraged, combining multiple strategies, including cultural, biological, and chemical methods, to reduce reliance on insecticides solely and promote pest control. Insecticides may be a chemical substance, a biological agent such as virus or bacteria, an antimicrobial agent, a disinfectant or any other agent. Many insecticides are harmful for the human by causing disease and threat, so the formulation / combination of insecticides manufacturers always searches the ways for developing the mixture of insecticides in a way that is safer for the environment, humans and other non-targeted organisms to provides more effective and economical use against the targeted insects.
The term “synergism” as used in this specification refers to the interaction between two or more active compounds or other factors to produce a combined effect greater than the sum of their individual effects. The present invention involves the mixture of two active ingredients which has increased efficacy when compared to individual use and admixture of those components.
Conventional insecticides have poor activity, limited to certain insects, and are not satisfactorily maintained for prolonged periods. Even though some insecticides may bear satisfactory insecticidal effects, but they require improvements in respect of environment and health safety and are also required to achieve a high insecticidal effect at a smaller dosage and lack resistance management.
We found that this objective in part or can be achieved by the combination of active compounds defined at the outset. The present inventors have intensively studied to solve these problems. We have found that by combining insecticide composition having thiourea insecticide and pyrazole insecticide optionally with at least one agrochemical acceptable excipient(s) in different formulation and percentages have astonishing effects of controlling insects and by reducing amount of dosage than in a case of using an active compound alone and admixture of those compounds.
Therefore, the present invention provides a novel synergistic insecticidal composition having thiourea insecticide and pyrazole insecticide and purpose thereof. The synergy of insecticide composition has the main effective components of diafenthiuron and fipronil acts by inhibiting oxidative phosphorylation and mitochondrial adenosine triphosphatase (ATPase) and also disrupts the insect central nervous system by blocking the ligand-gated ion channel of the GABA (?-aminobutyric acid) receptor and glutamate-gated chloride (GluCl) channels, respectively and can generate efficient synergism by means of contact, stomach and ovicidal action and can enable broad spectrum satisfactory insect control and protect the several crop from sucking, chewing, caterpillars, borer pests and soil insects and check the resistance development in insects in several crops for prolonged period at lower dose with no phytotoxic effect. This combination is also helpful in controlling insect vectors which transmit viral diseases in plants, and it can also be used in public health and household purposes for pest control
According to current practice, formulations of diafenthiuron and fipronil can be developed in the form of Emulsifiable Concentrates (EC), Dispersible Concentrates (DC), Oil Dispersions (OD), Suspension Concentrates (SC), Soluble Liquids (SL), Suspoemulsion (SE), Emulsion Concentrates (EW), Microemulsions, Wettable Powders (WP), Water-Dispersible Granules (WG), Soluble Powders (SP), Granules (G), Oil Solutions (OS), Aqueous Suspensions (AS), Aqueous Solutions (AS), Microencapsulated Suspensions (ME), and Microencapsulated Emulsions (MEC), mixed formulation of Suspension Concentrate and Capsule Suspension (ZC) and other conventional formulation and with different percentages and can be used as curative, and preventive combination for foliar applications or soil applications.
Furthermore, the formulation comprising diafenthiuron and fipronil that are used together in suspension concentrates (SC) formulation according to the present invention have been observed to provide great efficacy at low dose, exhibit insecticidal and acaricidal action against the insects damaging the agricultural crops and achieve the successful results, which were not possible to obtain previously with any insecticide combination.
The present invention involves the mixture of two active ingredients which are classified under thiourea insecticide and pyrazole insecticide are described herein thereof.
Thioureas are a relatively new class of insecticides and acaricides and have a novel mode of action by inhibition of mitochondrial respiration by its carbodiimide product. Thiourea is a sulfhydryl compound, found effective in mitigating drought stress in crops which imparts plant tolerance to dehydration stress. Thiourea has been widely used for enhancing plant growth, stress tolerance and crop yield.
Diafenthiuron is a thiourea insecticide/acaricide (having IUPAC name: 1-tert-butyl-3-[4-phenoxy-2,6-di(propan-2-yl) phenyl] thiourea; Molecular formula: C23H32N2OS) broad spectrum, contact and stomach action with some ovicidal activity by inhibiting oxidative phosphorylation and acts in insects as a mitochondrial adenosine triphosphatase (ATPase) inhibitor following metabolic activation to the corresponding carbodiimide.
Pyrazole insecticides acts mainly through the inhibition of the mitochondrial electron transport system, whereas neonicotinoids target insects' nervous systems via nicotinic acetylcholine receptors (nAChRs), exhibiting high selective toxicity.
Fipronil mainly belongs to phenyl pyrazole insecticides is a systemic, selective insecticide having IUPAC name: 5-amino-1-[2,6-dichloro-4-(trifluoromethyl) phenyl]-4-(trifluoromethylsulfinyl) pyrazole-3-carbonitrile; Molecular formula: C12H4Cl2F6N4OS. Fipronil disrupts the insect central nervous system by blocking the ligand-gated ion channel of the GABA (?-aminobutyric acid) receptor and glutamate-gated chloride (GluCl) channels. Disruption of the GABA receptors by fipronil prevents the uptake of chloride ions resulting in excess neuronal stimulation and death of the target insects. This photoproduct exerts high neurotoxicity by blocking the ?-aminobutyric acid (GABA)-regulated chloride channels. Fortunately, this metabolite is not formed in mammals.
The first embodiment of the present invention provides a synergistic insecticidal composition comprising:
at least one thiourea insecticide; and
at least one pyrazole insecticide.
The first aspect of the first embodiment, the thiourea insecticide is selected from diafenthiuron.
The second aspect of the first embodiment, the pyrazole insecticides, is selected from the group comprising but not limited to acetoprole, dimpropyridaz, ethiprole, fipronil, flufiprole, pyrafluprole, pyriprole, tolfenpyrad, and vaniliprole.
The third aspect of the first embodiment, synergistic insecticidal composition comprising a combination of thiourea insecticide and pyrazole insecticide; wherein thiourea insecticide and pyrazole insecticide are present in the weight ratio of (1-80):(1-80).
The second embodiment of the present invention provides a synergistic insecticidal composition comprising:
diafenthiuron;
at least one pyrazole insecticide; and
at least one agrochemical acceptable excipient.
First aspect of the second embodiment, the pyrazole insecticides is selected from the group comprising but not limited to acetoprole, dimpropyridaz, ethiprole, fipronil, flufiprole, pyrafluprole, pyriprole, tolfenpyrad, and vaniliprole; preferably fipronil.
The second aspect of the second embodiment, synergistic insecticidal composition comprising a combination of diafenthiuron insecticide and pyrazole insecticide; wherein diafenthiuron insecticide and pyrazole insecticide are present in the weight ratio of (1-80):(1-80); preferably in the weight ratio of (1-40):(1-40)
The third aspect of the second embodiment, agrochemical acceptable excipient selected from but not limited to the group comprising carrier, surfactant, stabilizer, anti-freezing agent, antifoaming agent, anticaking agent, dispersing agent, and adjuvant(s). These are selected according to the respective types of formulation requirements, and which will facilitate in the preparation different formulations.
Further aspect of the second embodiment, carrier can be selected from liquid medium or solid medium which will provides a stable environment to the formulation. Wherein liquid medium selected from but not limited to water and organic solvents incudes hydrocarbon solvents and cycloalkanes, ether solvents, ester solvents, ketones solvents, alcohols solvents and polar-aprotic solvents.
Further aspect of the second embodiment, surfactant includes wetting agent and emulsifier.
Further aspect of the present invention, emulsifier includes anionic emulsifiers, cationic emulsifiers, non-ionic emulsifiers, amphoteric emulsifiers, phospholipids, glyceryl esters and other commercially available emulsifiers.
Further aspect of the present invention, anionic emulsifiers selected from but not limited to sodium lauryl sulfate (SLS), sodium dodecyl benzenesulfonate (SDBS), alkyl sulfates, alkyl ethoxylate sulfates and calcium alkyl benzene sulfonate.
Further aspect of the present invention, cationic emulsifiers selected from but not limited to cetyl trimethyl ammonium bromide (CTAB) and stearalkonium chloride.
Further aspect of the present invention nonionic emulsifiers selected from but not limited to polysorbate 80, polysorbate 20, sorbitan monolaurate, alkyl ethoxylates, sorbitan monooleate and polyaryl sulfate esters.
Further aspect of the present invention, amphoteric emulsifiers selected from but not limited to cocamidopropyl betaine, lauramidopropyl betaine; ethoxylated emulsifiers: ethoxylated nonylphenol (nonylphenol ethoxylate), ethoxylated sorbitan esters, and ethoxylated fatty alcohols.
Further aspect of the second embodiment, wetting agent is selected from but not limited to alkyl aryl sulfonates, alkyl phenol ethoxylates/ propoxylates, alkoxylates, ethoxylated alkoxylates, alkyl aryl poly alkoxy ether, alkyl polyglucosides, polysorbates, polyethylene glycol esters, polysorbate, polyethylene oxide (PEO), ethoxylated or propoxylated fatty alcohols and/or acids and/or amines, ethoxylated or propoxylated synthetic alcohols, alkyl aryl sulphates, ethoxylated alkyl aryl sulphates, ethoxylated vegetable oils, ethoxylated sorbitan esters, phosphated esters, propylene glycol esters, sodium lauryl sulfate, cocoamidopropyl betaine and block copolymers selected from the but not limited to styrene-butadiene block copolymer (SBS), butyl based block copolymer, poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (PEO-PPO-PEO), polystyrene-poly(ethylene oxide) (PS-PEO), poly(butadiene)-poly(styrene) (PB-PS), poly(methyl methacrylate)-poly(butadiene)-poly(methyl methacrylate) (PMMA-PB-PMMA), poly(capro lactone)-poly(ethylene glycol) (PCL-PEG), poly(ethylene glycol)-poly(propylene glycol)-poly(ethylene glycol) (PEG-PPG-PEG), and other commercially available wetting agents.
Further aspect of the second embodiment, stabilizer includes antioxidant, chelating agent, pH adjusters, UV absorber, stabilizing polymers, and inert material.
Further aspect of the second embodiment, stabilizers selected from group vegetable and seed oils selected from but not limited to soybean oil, sunflower seed oil, coconut oil, peanut oil, corn oil, castor oil, palm oil, rapeseed oil, safflower oil, olive oil, corn oil, cottonseed oil, linseed oil, tung oil and sesame oil and oxidized forms of the above oils.
Further aspect of the second embodiment, inert material selected from but not limited to quartz, kaolin clay, attapulgite clay, acidic clay, attapulgite, zeolite, bentonite, montmorillonite, acid white clay, pyrophyllite, talc, diatomaceous earth and calcite, china clay, corn rachis powder, walnut husk powder, urea, calcium carbonate, ammonium sulfate, silicon oxides (precipitated silica) and other commercially available inert materials.
Further aspect of the second embodiment, anti-freezing agent selected from but not limited to ethylene glycol, propylene glycol, glycerol, calcium chloride, sodium acetate, potassium acetate, urea, and other commercially available anti-freezing agents.
Further aspect of the second embodiment, antifoaming agents selected from but not limited to silicone-based antifoams, polyethylene glycol-based antifoams, mineral oil-based antifoams, ethylene glycol-based antifoams, polysorbate-based antifoams, dimethicone-based antifoams, polypropylene glycol-based antifoams, vegetable oil-based antifoams, alkyl siloxane-based antifoams, fatty acid-based antifoams, and other commercially available antifoaming agents.
Further aspect of the second embodiment, anticaking agent selected from silica-based compounds includes silicon dioxide (silica), precipitated silica (amorphous form of silicon dioxide), calcium silicate, magnesium stearate, sodium aluminosilicate, potassium aluminium silicate, tricalcium phosphate, sodium ferrocyanide, calcium carbonate, diatomaceous earth, sodium bicarbonate, and other commercially available anticaking agents.
Further aspect of the second embodiment, dispersing agents selected from but not limited to polyethylene glycol, polysorbate, poly acrylate, poly(methyl methacrylate), polyvinyl alcohol, poly ethoxylated alcohol, poly ethoxylated fatty acids, polyacrylic acid, polyvinylpyrrolidone, alkyl sulfonates, aryl sulfonates, sodium tripolyphosphate, sodium dodecyl sulfate, sodium lignosulfonate, sodium carboxymethyl cellulose, hydroxypropyl methylcellulose, sorbitan esters (e.g., sorbitan monolaurate, sorbitan monooleate), gum arabic and carbomer and/or their comb polymers; preferably poly(methyl methacrylate), polyethylene glycol comb polymer, and other commercially available dispersing agents.
Further aspect of the second embodiment, adjuvant includes but not limited to colorant, spreader, modifier, sticker, penetrant, drift control agent, buffering agent, thickener, compatibility agent, binders and safener.
A further aspect of the second embodiment, colorant is color dye selected from natural, synthetic and commercially available dyes.
Further aspect of the second embodiment, binder / sticking agent selected from but not limited to methyl cellulose, ethyl cellulose, hydroxy propyl methyl cellulose, hydroxy propyl cellulose, gum, sodium carboxy methyl cellulose, polyvinyl pyrrolidone, polyethylene glycol, polyvinyl alcohol, polymethacrylates and other commercially available binders.
Further aspect of second embodiment, thickener selected from but not limited to polysaccharides / carboxymethyl cellulose / bentonite clay, hydroxy propyl cellulose montmorillonite, bentonite, magnesium aluminium silicate, attapulgite and other commercially available thickeners.
Further aspect of the second embodiment, modifier includes drift control modifiers, rain fastness modifiers, anti-foaming modifiers, UV stabilizers, pH modifiers, compatibility modifiers and rheology modifier.
Further aspect of the second embodiment, rheology modifier is bentonite and pH modifiers is triethanolamine and phosphoric acid.
Further aspect of the second embodiment, preservatives is antibacterial agent selected from but not limited to triclosan, triclocarban, clotrimazole, miconazole, copper-based compounds, chlorothalonil, benzisothiazolin-3-one (BIT), 5-chloro-2-methyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one (MIT), octylisothiazolinone (OIT), dodecylbenzenesulfonic acid, sodium salt (DBSA) and and other commercially available preservatives.
The third embodiment of the present invention provides a synergistic insecticidal composition comprising:
diafenthiuron;
fipronil;
carrier;
wetting agent;
stabilizer;
anti-freezing agent;
antifoaming agent;
dispersing agent; and
adjuvant(s).
The first aspect of the third embodiment, synergistic insecticidal composition comprising a combination of diafenthiuron and fipronil; wherein diafenthiuron and fipronil are present in the weight ratio of (1-80):(1-80); preferably weight ratio of (1-40):(1-40); more preferably in the weight ratio of (1-40):(1-10).
The second aspect of the third embodiment, agriculturally acceptable excipient selected from but not limited to carrier, wetting agent, stabilizer, anti-freezing agent, antifoaming agent, dispersing agent, and adjuvant(s). These are selected according to the respective types of formulation requirements, and which will facilitate in the preparation different formulations.
Further aspect of third embodiment, carrier can be selected from liquid medium or solid medium which will provides a stable environment to the formulation. Wherein liquid medium selected from but not limited to water and organic solvents incudes hydrocarbon solvents and cycloalkanes, ether solvents, ester solvents, ketones solvents, alcohols solvents and polar-aprotic solvents, preferably water.
Further aspect of the third embodiment, wetting agent is selected from but not limited to alkyl aryl sulfonates, alkyl phenol ethoxylates / propoxylates, alkoxylates, ethoxylated alkoxylates, alkyl aryl poly alkoxy ether, alkyl polyglucosides, polysorbates, polyethylene glycol esters, polysorbate, polyethylene oxide (PEO), ethoxylated or propoxylated fatty alcohols and/or acids and/or amines, ethoxylated or propoxylated synthetic alcohols, alkyl aryl sulphates, ethoxylated alkyl aryl sulphates, ethoxylated vegetable oils, ethoxylated sorbitan esters, phosphated esters, propylene glycol esters, sodium lauryl sulfate, cocoamidopropyl betaine and block copolymers selected from the but not limited to styrene-butadiene block copolymer (SBS), butyl based block copolymer, poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (PEO-PPO-PEO), polystyrene-poly(ethylene oxide) (PS-PEO), poly(butadiene)-poly(styrene) (PB-PS), poly(methyl methacrylate)-poly(butadiene)-poly(methyl methacrylate) (PMMA-PB-PMMA), poly(capro lactone)-poly(ethylene glycol) (PCL-PEG), poly(ethylene glycol)-poly(propylene glycol)-poly(ethylene glycol) (PEG-PPG-PEG), and other commercially available wetting agents.
Further aspect of the third embodiment, stabilizer selected from group vegetable and seed oils selected from but not limited to soybean oil, sunflower seed oil, coconut oil, peanut oil, corn oil, castor oil, palm oil, rapeseed oil, safflower oil, olive oil, cottonseed oil, linseed oil, tung oil and sesame oil and their oxidized forms.
Further aspect of the third embodiment, anti-freezing agent selected from but not limited to ethylene glycol, propylene glycol, glycerol, calcium chloride, sodium acetate, potassium acetate and urea; preferably propylene glycol.
Further aspect of the third embodiment, antifoaming agent selected from but not limited to silicone-based antifoams, polyethylene glycol-based antifoams, mineral oil-based antifoams, ethylene glycol-based antifoams, polysorbate-based antifoams, dimethicone-based antifoams, polypropylene glycol-based antifoams, vegetable oil-based antifoams, alkyl siloxane-based antifoams and fatty acid-based antifoams; preferably alkyl siloxane-based antifoams; more preferably siloxane polyalkyleneoxide.
Further aspect of the third embodiment, dispersing agent selected from but not limited to polyethylene glycol, polysorbate, poly acrylate, poly(methyl methacrylate), polyvinyl alcohol, poly ethoxylated alcohol, poly ethoxylated fatty acids, polyacrylic acid, polyvinylpyrrolidone, alkyl sulfonates, aryl sulfonates, sodium tripolyphosphate, sodium dodecyl sulfate, sodium lignosulfonate, sodium carboxymethyl cellulose, hydroxypropyl methylcellulose, sorbitan esters (e.g., sorbitan monolaurate, sorbitan monooleate), gum arabic and carbomer and/or their comb polymers; preferably poly(methyl methacrylate) and polyethylene glycol comb polymer.
Further aspect of the third embodiment, adjuvant includes but not limited to colorant, spreader, modifier, sticker, penetrant, drift control agent, buffering agent, thickener, compatibility agent, binders, and safener.
Further aspect of the third embodiment, thickener selected from but not limited to polysaccharides / carboxymethyl cellulose / bentonite clay, hydroxy propyl cellulose montmorillonite, bentonite, magnesium aluminium silicate and attapulgite; preferably water-soluble polysaccharides.
Further aspect of the third embodiment, rheology modifier is bentonite and pH modifiers is triethanolamine and/or phosphoric acid.
Further aspect of the third embodiment, preservatives is antibacterial agent selected from but not limited to triclosan, triclocarban, clotrimazole, miconazole, copper-based compounds, chlorothalonil, benzisothiazolin-3-one (BIT), 5-chloro-2-methyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one (MIT), octylisothiazolinone (OIT), dodecylbenzenesulfonic acid, sodium salt (DBSA), and other commercially available preservatives; preferably benzisothiazolin-3-one (BIT).
The fourth embodiment of the present invention provides a synergistic insecticidal composition comprising:
diafenthiuron;
fipronil;
water;
butyl based block copolymer;
propylene glycol;
siloxane polyalkyleneoxide;
comb polymer;
polysaccharides; and
benzisothiazolin-3-one.
First aspect of the fourth embodiment, synergistic insecticidal composition comprising a combination of diafenthiuron and fipronil; wherein diafenthiuron and fipronil are present in the weight ratio of (1-80):(1-80); preferably weight ratio of (1-40):(1-40); more preferably in the weight ratio of (1-40):(1-10).
Further aspect of the fourth embodiment, the composition of fourth embodiment is formulated as suspension concentrates (SC).
Another embodiment of the present invention provides a process for the preparation of suspension concentrates (SC) formulation comprising:
add water into premix vessel,
add wetting agent, anti-freezing, dispersing agent, anti-bacterial agent, and antifoaming agent to the above vessel under continuous stirring;
add diafenthiuron and fipronil to the above slurry and stirred for 30-60 minutes to get homogenous mixture;
after mixing the above material, optionally mill or grind to get the desired particle size of minimum 99% by passing through 500 bss by wet sieving method and remove any oversized particles or agglomerate.
the obtained wet milled slurry particles with size d50 <5-micron material, then transfer into the blender and add thickener 2% gum solution to get desired viscosity; and
mix well until a homogenous mixture is obtained, pack the formulation and seal it.
Another embodiment of the present invention, the other alternative formulations other than described herein can be prepared using conventional processes and different methods known in the art by selecting appropriate agrochemical acceptable excipient(s) to get the suitable desired formulation of present invention combination.
Another embodiment of the present invention, the insecticidal composition obtained from the present used to control and destroys insect pests such as but not limited to aphids, whiteflies, trims, leafhoppers, leaf miners, sawflies, mole cricket, white grubs, jassids, thrips, lace bugs, billbugs, beetles, mealybugs, sawfly larvae, fleas, cockroaches, ticks, ants, carpet beetles, and mosquitoes on several crops. It controls the insects of numerous crops such as but not limited to paddy, cereals, fruits, vegetables, flowers and ornamental plants, trees, and others. Fruit crops such as apples, citrus fruits, grapes, and berries. Vegetable crops include tomatoes, peppers, cucumbers, and leafy greens. Field crops like corn, soybeans, cotton, and wheat.
Another embodiment of the present invention, the insecticidal composition further comprises at least another agrochemical selected from a fungicide, insecticide, herbicide, biocide, nutrient, plant growth regulator, plant activator, fertilizers and likewise.
Another embodiment of the present invention, the insecticidal composition obtained from the present inventions shows synergistic effects of better pest control with minimum resistance and resurgence and improved crop yield and quality.
Another embodiment of the present invention, the synergistic insecticidal composition can be used for prophylactic application and control the pests by applying effective amount of insecticidal composition over the target areas by conventional spraying methods, such as foliar application soil drenching etc., and avoiding excessive drift or runoff of the composition, securing thorough coverage.
Another embodiment of the present invention, synergistic insecticidal combination decreases natural hazardous effect of single active ingredient and minimizes the residue deposition in environment.
Another embodiment of the present invention, a method of controlling pests and insects comprising synergistic insecticidal composition applying to crop in effective amount by conventional methods.
The best mode of carrying present invention is described in the below given examples. These examples are merely for illustrative purposes only, not to determine the scope of the invention and in no way limit the scope or spirit of the present invention.
EXAMPLES:
EXAMPLE 1: DIFFERENT FORMULATIONS OF SYNERGISTIC INSECTICIDAL COMPOSITION OF THE PRESENT INVENTION:
TABLE 1: SUSPENSION CONCENTRATES (SC)
S. No Ingredient Weight/ Weight %
1 Diafenthiuron 32.5
2 Fipronil 7.5
3 Butyl based block copolymer 2.5
4 Propylene Glycol 5
5 Siloxane polyalkyleneoxide 0.5
6 Comb polymer 2.5
7 Polysaccharides 0.3
8 Benzisothiazolin-3-one 0.1
9 Water QS
Total 100
EXAMPLE 2: PROCESS FOR PREPARATION OF SUSPENSION CONCENTRATES (SC) FORMULATION OF SYNERGISTIC INSECTICIDAL COMPOSITION OF THE PRESENT INVENTION
The present invention of the suspension concentrate (SC) formulation process involves dispersing fine solid particles of the diafenthiuron and fipronil in a liquid phase typically by using water, to create a stable suspension. This procedure mainly starts with milling the diafenthiuron and fipronil to achieve the desired particle size, followed by mixing it with dispersing agents, stabilizers, and other additives like anti-freezing, anti-foaming, and anti-bacterial agents while prevent settling and agglomeration. The mixture is then now homogenized to ensure uniform particle distribution and subjected to quality control tests for its stability, viscosity, and particle size distribution. It is then packaged in air-tight, moisture-proof containers to maintain stability and effectiveness during storage and handling, ensures a high-quality, user-friendly pesticidal formulation that adheres to regulatory standards, and maintaining efficacy over its shelf life.
EXAMPLE 3: BIO EFFICACY AND PHYTOTOXICITY TESTS OF THE PRESENT INVENTION
Methodology:
Presently to evaluate the efficacy of novel combination against different pests on different crops. The insecticidal combinations i.e. Diafenthiuron 32.5% + Fipronil 7.5% SC formulations was evaluated against different pests on different crops and to test their phytotoxicity on the crop after two sprayings have been conducted. For evaluation of Diafenthiuron 32.5% + Fipronil 7.5% SC EC, the efficacy was tested on sucking pests like Thrips and mites in chilli crop and against Whitefly in cotton crop were tested. The combination tested at three dose levels viz., low, medium, and high along with the sole molecule as individual treatments and their efficiency comparison is done with the current competitive market standards. The test combination are tested at three different formulation strengths i.e., Diafenthiuron 32.5% + Fipronil 7.5% SC (600ml/ha 750ml/ha and 900ml/ha), the market standards used for chilli mites i.e., Fenpyroximate 2.50% EC @ 600ml/ha and Propargite 42% + Hexythiazox 2% EC @ 1250ml/ha, chilli thrips i.e., Emamectin Benzoate 1.5% + Fipronil 3.5% SC @ 750ml/ha and for whitefly in Pyriproxyfen 5% + Diafenthiuron 25% SE @ 1250ml/ha and Fipronil 15% + Flonicamid 15% WDG @ 400 g/ha. To justify the results the overall effect and other parameters are calculated over untreated check and to see their effect on crop, its yield is recorded. The crops are first divided into plots for each treatment and replicated three times following Randomized Block Design. The spraying method followed was foliar application with the help of a knapsack sprayer and two sprays are done when the pests reach their ETL. The interval between two sprays is 15 Days.

Method of Observations:
a. Thrips / Mites / Whiteflies - No. of adults or nymphs /plant: select 5 random plants in the plot.
The observations were taken at 1 day before spraying and at 1 day, 4 days, 7 Days, and 10 Days after spraying. The average number of insects were also calculated at the end of each spray (two sprays).
Take the observation on the crop safety of the insecticide i.e., Phytotoxicity / softener observation of insecticide after application at 5 and 10 Days after application.
Parameters of Observations:
The insect pests controlled in each treatment are counted as the number of pest per plant and then calculated as percent reduction in population over untreated or controlled plot. The percentage reduction is calculated by the following formula:
% reduction = (No.of pest in control plot-No.of pest in treated plot )/(No.of pest in control plot)× 100
The effect of these insecticides in combination and alone when applied on crops is assessed based on the yield (quintal per hectare).
Results:
The insecticide combination i.e., Diafenthiuron 32.5% + Fipronil 7.5% SC formulation is effective against wide range of insect pests, so the different insect pests controlled in different crops in the field experiments were enlisted below:
Chilli – Thrips (Scirtothrips dorsalis)
Chilli – Mites (Polyphagotrsonemus latus)
Cotton – Whitefly (Bemesia tabaci)
Example – 3.1: Chilli - Thrips
Table 1. Efficacy of first spray application of Diafenthiuron 32.5% + Fipronil 7.5% SC formulation against Thrips in Chilli:
Treatments Dose
(g or ml / ha) No. of Nymphs or Adults Per Plant
(Days After Spraying) % Reduction in Pest Population
Pre 1 4 7 10 AVG
Diafenthiuron 32.5% + Fipronil 7.5% SC 600 16 6 4 3 6 7.00 83.72
Diafenthiuron 32.5% + Fipronil 7.5% SC 750 15.5 7 3 4 5 6.90 83.95
Diafenthiuron 32.5% + Fipronil 7.5% SC 900 15 5 1 0 0 4.20 90.23
Diafenthiuron 50% WP 600 15.6 12 14 16.34 20.12 15.61 63.69
Fipronil 5% SC 1000 18 13.23 15 17.87 22 17.22 59.95
Emamectin benzoate 1.5% + Fipronil 3.5% SC 750 15.7 10 8 11 13 11.54 73.16
UNTREATED 30 35 42 51 57 43.00 0.00
The thrips population before initiating the spraying was recorded in between 15-18 thrips per plant in chilli. After the first application of different insecticide treatments, the insecticide combination treatments Diafenthiuron 32.5% + Fipronil 7.5% SC when applied at 750 ml/ha and 900 ml/ha showed maximum reduction. The treatment Diafenthiuron 32.5% + Fipronil 7.5% SC when applied @ 900ml/ha thrips population of 5 thrips/plant at 1 days after spraying and 1, 0, 0 thrips/plant at 4, 7, 10 das. When applied at 750 ml/ha recorded 7 thrips/plant at 1 das, and 3, 4, 5 thrips/plant at 4, 7 and 10 das. The average thrips population after the entire spraying was recorded to be lowest in Diafenthiuron 32.5% + Fipronil 7.5% SC @ 900 ml/ha with 4.20 thrips/plant followed by Diafenthiuron 32.5% + Fipronil 7.5% SC @ 750 ml/ha with 6.90 thrips/plant which were performing superior to market standards by the end of first spray. The percent reduction in thrips population recorded in all the treatments proved that Diafenthiuron 32.5% + Fipronil 7.5% SC when applied at 900ml/ha was showing maximum reduction in thrips population as 90.23% and at 750ml/ha recorded 83.95% there by proving that these molecules when applied in combination at the doses of 900, 750 ml/ha showed synergistic activity and thrips population control was superior to market standard. Even the treatment Diafenthiuron 32.5% + Fipronil 7.5% SC when applied at 600 ml/ha (lowest dose of the insecticide combination) also showed a percentage reduction of 83.72% which was also superior to the market standard. Though the first spray application of combination insecticides showed significant reduction in thrips population in chilli.
Table 2. Efficacy of second spray application of Diafenthiuron 32.5% + Fipronil 7.5% SC formulation against Thrips in Chilli.
Treatments Dose
(g or ml / ha) No. of Thrips Per Plant
(Days After Spraying) % Reduction in Pest Population Colby’s Ratio
Pre 1 4 7 10 AVG
Diafenthiuron 32.5% + Fipronil 7.5% SC 600 6 1.80 0.00 0.58 2 1.10 98.59 1.22
Diafenthiuron 32.5% + Fipronil 7.5% SC 750 5 0.00 0.00 0 1 0.25 99.68 1.23
Diafenthiuron 32.5% + Fipronil 7.5% SC 900 0 0.00 0.00 0 0 0.00 100.00 1.24
Diafenthiuron 50% WP 600 20.12 22.44 28.00 36 45 32.86 57.60 0.71
Fipronil 5% SC 1000 22 23.77 29.00 38.55 48 34.83 55.06 0.68
Emamectin benzoate 1.5% + Fipronil 3.5% SC 750 13 11.00 9.00 15 17 13.00 83.23 1.03
UNTREATED 57 64.00 75 83 88 77.50 0.00 0.00
The thrips population before initiating the second spray was recorded in between 0-20.12 thrips per plant in chilli. This pre-treatment population the thrips population recorded at the end of the first spraying. After the second application of different insecticide treatments, the insecticide combination treatments Diafenthiuron 32.5% + Fipronil 7.5% SC when applied at 900ml/ha showed maximum reduction in thrips population by recording 0 thrips/plant at 1, 4, 7, 10 Days after spraying and when applied at 750ml/ha recorded 0 thrips/plant at 1, 4, 7 days after spraying and 1 thrips/plant at 10 days after spraying. The average thrips population after the entire spraying was recorded to be lowest in Diafenthiuron 32.5% + Fipronil 7.5% SC @ 900 ml/ha with 0 thrips/plant followed by Diafenthiuron 32.5% + Fipronil 7.5% SC @ 750 ml/ha with 0.25 thrips/plant which were performing superior to market standards. The percent reduction in thrips population recorded in all the treatments proved that Diafenthiuron 32.5% + Fipronil 7.5% SC when applied at 900 ml/ha was showing maximum reduction in thrips population as 100% followed by Diafenthiuron 32.5% + Fipronil 7.5% SC @ 750 ml/ha with 99.68% reduction and Diafenthiuron 32.5% + Fipronil 7.5% SC @ 600 ml/ha recorded 98.59% there by proving that these molecules when applied in combination at the doses of 900, 750 and 600 ml/ha showed synergistic activity and thrips population control was superior to market standard. Though they are significantly controlling the thrips population the same molecules when applied in combination with lesser strength recorded higher control, to check synergy colby’s ratio was calculated and it recorded >1 in case of the combination Diafenthiuron 32.5% + Fipronil 7.5% SC at all the doses i.e., 1.22, 1.23, 1.24 thereby proving combination insecticide is more reliable.
Table 3. Effect of Diafenthiuron 32.5% + Fipronil 7.5% SC EC formulation on yield in Chilli.
Treatments Dose (g or ml / ha) Yield (q/ha)
Diafenthiuron 32.5% + Fipronil 7.5% SC 600 33
Diafenthiuron 32.5% + Fipronil 7.5% SC 750 34.21
Diafenthiuron 32.5% + Fipronil 7.5% SC 900 36.77
Diafenthiuron 50% WP 600 25
Fipronil 5% SC 1000 23
Emamectin benzoate 1.5% + Fipronil 3.5% SC 750 29.76
UNTREATED 20
The yield of chilli recorded in different treatments as shown in the table above (Table 3.) implies that the combination molecule at the three doses positively affected the yield of the crop. The highest yield was recorded in Diafenthiuron 32.5% + Fipronil 7.5% SC EC @ 900 ml/ha with 36.77 q/ha, followed by Diafenthiuron 32.5% + Fipronil 7.5% SC @ 750 ml/ha with 34.21 q/ha and Diafenthiuron 32.5% + Fipronil 7.5% SC @ 600 ml/ha with 33 q/ha. While the individual molecules and market standards recorded yields ranging between 23-29.76 q/ha which were inferior to the yield recorded in the combination molecule treatments.
Table 4. Phytotoxicity of Diafenthiuron 32.5% + Fipronil 7.5% SC EC formulation on Chilli:
The phytotoxicity effect of the insecticide combination i.e., Diafenthiuron 32.5% + Fipronil 7.5% SC on chilli crop was tested after 5 and 10 Days after spraying. The crop was checked for symptoms like yellowing, necrosis, wilting, vein clearing, leaf tip or leaf margin dying and stunting or dwarfing of plants. After thorough observations, it could be concluded that the crop did not show any symptoms of phytotoxicity. Therefore, the present insecticide combination can be considered a safe molecule.
Treatments Days Visual Rating Scale
Yellowing Necrosis Wilting Vein
Clearing Leaf tip / Margin Dying Stunting / Dwarfing
Diafenthiuron 32.5% + Fipronil 7.5% SC @ 600ml/ha 5 0 0 0 0 0 0
10 0 0 0 0 0 0
Diafenthiuron 32.5% + Fipronil 7.5% SC @ 750ml/ha 5 0 0 0 0 0 0
10 0 0 0 0 0 0
Diafenthiuron 32.5% + Fipronil 7.5% SC @ 900ml/ha 5 0 0 0 0 0 0
10 0 0 0 0 0 0
Diafenthiuron 50% WP @ 600g/ha 5 0 0 0 0 0 0
10 0 0 0 0 0 0
Fipronil 5% SC @ 1000ml/ha 5 0 0 0 0 0 0
10 0 0 0 0 0 0
Emamectin Benzoate 1.5% + Fipronil 3.5% SC @ 750ml/ha
5 0 0 0 0 0 0
10 0 0 0 0 0 0
Untreated
5 0 0 0 0 0 0
10 0 0 0 0 0 0

Example – 3.2: Chilli - Mites
Table 5. Efficacy of first spray application of Diafenthiuron 32.5% + Fipronil 7.5% SC formulation against Mites in Chilli.
Treatments Dose
(g or ml / ha) No. of Nymphs or Adults Per Plant
(Days After Spraying) % Reduction in Pest Population
Pre 1 4 7 10 AVG
Diafenthiuron 32.5% + Fipronil 7.5% SC 600 18.13 8.06 1.89 3.25 4.8 7.23 74.56
Diafenthiuron 32.5% + Fipronil 7.5% SC 750 13.83 5.26 0 0 3 4.42 84.44
Diafenthiuron 32.5% + Fipronil 7.5% SC 900 16.33 4.26 0 0 0 4.12 85.50
Diafenthiuron 50% WP 600 16.25 14.02 15.41 20.79 22.34 17.76 37.46
Fipronil 5% SC 1000 18.73 16.26 14.09 18.23 20.67 17.60 38.04
Fenpyroximate 5% EC 600 16.43 13.6 10.79 9.95 12.2 12.59 55.65
Propargite 42% + Hexythiazox 2% EC 1250 20.66 7.69 4.00 9.00 12.00 10.67 62.43
Untreated check 18 23 29 33 39 28.40 0.00
The mites population before initiating the spraying was recorded in between 13.83-20.66 mites per plant in chilli. After the first application of different insecticide treatments, the insecticide combination treatments Diafenthiuron 32.5% + Fipronil 7.5% SC when applied at 900 ml/ha and 750 ml/ha showed maximum reduction in mites population of 4.26 and 5.26 mites/plant at 1 days after spraying and 0 mites/plant at 4, 7 das and 3 mites/plant at 10 das when applied at 750ml/ha and 0 mites/plant at 4, 7 and 10 das when applied at 900ml/ha. The average mites population after the entire spraying was recorded to be lowest in Diafenthiuron 32.5% + Fipronil 7.5% SC @ 900 ml/ha with 4.12 mites/plant followed by Diafenthiuron 32.5% + Fipronil 7.5% SC @ 750 ml/ha with 4.42 mites/plant which were performing superior to market standards by the end of first spray. The percent reduction in mites’ population recorded in all the treatments proved that Diafenthiuron 32.5% + Fipronil 7.5% SC when applied at 900ml/ha was showing maximum reduction in mites’ population as 85.50% and at 750ml/ha recorded 84.44% there by proving that these molecules when applied in combination at the doses of 900, 750 ml/ha showed synergistic activity and mites population control was superior to market standard. Even the treatment Diafenthiuron 32.5% + Fipronil 7.5% SC when applied at 600 ml/ha (lowest dose of the insecticide combination) also showed a percent reduction of 74.56% which was also superior to the market standard. Though the first spray application of combination insecticides showed significant reduction in mites’ population in chilli. While the market standards Fenpyroximate 5% EC @ 600ml/ha with 55.65% reduction and Propargite 42% + Hexythiazox 2% EC @ 1250ml/ha recorded 62.43% reduction.
Table 6. Efficacy of second spray application of Diafenthiuron 32.5% + Fipronil 7.5% SC formulation against Mites in Chilli:
Treatments Dose
(g or ml / ha) No. of Thrips Per Plant
(Days After Spraying) % Reduction in Pest Population Colby’s Ratio
Pre 1 4 7 10 AVG
Diafenthiuron 32.5% + Fipronil 7.5% SC 600 4.8 3.06 0.00 0 3.26 2.22 95.08 1.25
Diafenthiuron 32.5% + Fipronil 7.5% SC 750 3 0.00 0.00 0 2.26 1.05 97.67 1.29
Diafenthiuron 32.5% + Fipronil 7.5% SC 900 0 0.00 0.00 0 1.26 0.25 99.44 1.31
Diafenthiuron 50% WP 600 22.34 21.26 15.26 22.26 30.26 22.28 50.73 0.67
Fipronil 5% SC 1000 20.67 18.26 12.26 26.26 33.26 22.14 51.02 0.67
Fenpyroximate 5% EC 600 12.2 14.26 15.26 18.26 25.26 17.05 62.29 0.82
Propargite 42% + Hexythiazox 2% EC 1250 12 15.26 19.26 22.26 25.26 18.81 58.40 0.77
Untreated check 39 42.26 45.26 48.26 51.26 45.21 0.00 0.00
The mites population before initiating the second spray was recorded in between 0-22.34 thrips per plant in chilli. This pre-treatment population the mites population recorded at the end of the first spraying. After the second application of different insecticide treatments, the insecticide combination treatments Diafenthiuron 32.5% + Fipronil 7.5% SC when applied at 900ml/ha showed maximum reduction in mites population by recording 0, 0, 0, 1.26 thrips/plant at 1, 4, 7, 10 Days after spraying and when applied at 750ml/ha recorded 0, 0, 0 mites/plant at 1, 4, 7 days after spraying and 2.26 mites/plant at 10 days after spraying. The average mites population after the entire spraying was recorded to be lowest in Diafenthiuron 32.5% + Fipronil 7.5% SC @ 900 ml/ha with 0.25 mites/plant followed by Diafenthiuron 32.5% + Fipronil 7.5% SC @ 750 ml/ha with 1.05 mites/plant which were performing superior to market standards. The percentage reduction in mites population recorded in all the treatments proved that Diafenthiuron 32.5% + Fipronil 7.5% SC when applied at 900 ml/ha was showing maximum reduction in mites population as 99.44% followed by Diafenthiuron 32.5% + Fipronil 7.5% SC @ 750 ml/ha with 97.67% reduction and Diafenthiuron 32.5% + Fipronil 7.5% SC @ 600 ml/ha recorded 95.08% there by proving that these molecules when applied in combination at the doses of 900, 750 and 600 ml/ha showed synergistic activity and mites population control was superior to market standard. While the market standards Fenpyroximate 5% EC @ 600ml/ha with 62.29% reduction and Propargite 42% + Hexythiazox 2% EC @ 1250ml/ha recorded 58.40% reduction. Though they are significantly controlling the mites population the same molecules when applied in combination with lesser strength recorded higher control, to check synergy colby’s ratio was calculated and it recorded >1 i.e., 1.25-1.31 in case of the combination Diafenthiuron 32.5% + Fipronil 7.5% SC at all the doses thereby proving combination insecticide is more reliable.

Table 7. Effect of Diafenthiuron 32.5% + Fipronil 7.5% SC EC formulation on yield in Chilli.
Treatments Dose (g or ml / ha) Yield (q/ha)
Diafenthiuron 32.5% + Fipronil 7.5% SC 600 33.75
Diafenthiuron 32.5% + Fipronil 7.5% SC 750 35.58
Diafenthiuron 32.5% + Fipronil 7.5% SC 900 38.58
Diafenthiuron 50% WP 600 29.84
Fipronil 5% SC 1000 25.51
Fenpyroximate 5% EC 600 23.63
Propargite 42% + Hexythiazox 2% EC 1250 20.2
Untreated check 17.08
The yield of chilli recorded in different treatments as shown in the table above (Table 7.) implies that the combination molecule at the three doses positively affected the yield of the crop. The highest yield was recorded in Diafenthiuron 32.5% + Fipronil 7.5% SC @ 900 ml/ha with 38.58 q/ha, followed by Diafenthiuron 32.5% + Fipronil 7.5% SC @ 750 ml/ha with 35.58 q/ha and Diafenthiuron 32.5% + Fipronil 7.5% SC @ 600 ml/ha with 33.75 q/ha. While the individual molecules and market standards recorded yields ranging between 23.63-29.84 q/ha which were inferior to the yield recorded in the combination molecule treatments.
Table 8. Phytotoxicity of Diafenthiuron 32.5% + Fipronil 7.5% SC EC formulation on Chilli
The phytotoxicity effect of the insecticide combination i.e., Diafenthiuron 32.5% + Fipronil 7.5% SC on chilli crop was tested after 5 and 10 Days after spraying. The crop was checked for symptoms like yellowing, necrosis, wilting, vein clearing, leaf tip or leaf margin dying and stunting or dwarfing of plants. After thorough observations, it could be concluded that the crop did not show any symptoms of phytotoxicity. Therefore, the present insecticide combination can be considered a safe molecule (Table 8).

Treatments Days Visual Rating Scale
Yellowing Necrosis Wilting Vein
Clearing Leaf tip / Margin Dying Stunting / Dwarfing
Diafenthiuron 32.5% + Fipronil 7.5% SC @ 600ml/ha 5 0 0 0 0 0 0
10 0 0 0 0 0 0
Diafenthiuron 32.5% + Fipronil 7.5% SC @ 750ml/ha 5 0 0 0 0 0 0
10 0 0 0 0 0 0
Diafenthiuron 32.5% + Fipronil 7.5% SC @ 900ml/ha 5 0 0 0 0 0 0
10 0 0 0 0 0 0
Diafenthiuron 50% WP @ 600g/ha 5 0 0 0 0 0 0
10 0 0 0 0 0 0
Fipronil 5% SC @ 1000ml/ha 5 0 0 0 0 0 0
10 0 0 0 0 0 0
Fenpyroximate 5% EC @ 600ml/ha 5 0 0 0 0 0 0
10 0 0 0 0 0 0
Propargite 42% + Hexythiazox 2% EC @ 1250ml/ha 5 0 0 0 0 0 0
10 0 0 0 0 0 0
Untreated check 5 0 0 0 0 0 0
10 0 0 0 0 0 0

Example – 3.3: Cotton Whitefly:
Table 9. Efficacy of first spray application of Diafenthiuron 32.5% + Fipronil 7.5% SC formulation against Whitefly in Cotton.
Treatments Dose
(g or ml / ha) No. of Larva Per Plant
(Days After Spraying) % Reduction in Population
Pre 1 4 7 10 AVG
Diafenthiuron 32.5% + Fipronil 7.5% SC 600 22 10 3 6 7 9.60 76.70
Diafenthiuron 32.5% + Fipronil 7.5% SC 750 18 8 3 5 6 8.00 80.58
Diafenthiuron 32.5% + Fipronil 7.5% SC 900 21 5 0 3 5 6.80 83.50
Diafenthiuron 50% WP 600 20 8 13 16 21 15.60 62.14
Fipronil 5% SC 1000 23 13 10 14 18 15.60 62.14
Pyriproxyfen 5% + Diafenthiuron 25% SE 1250 21 8 11 14 19 14.60 64.56
Fipronil 15% + Flonicamid 15% WDG 400 21 9 12 15 18 15.00 63.59
UNTREATED 34 35 40 45 52 41.20 0.00
The Whitefly population before initiating the spraying was recorded in between 18-23 whiteflies per plant in Cotton. After the first application of different insecticide treatments, the insecticide combination treatments Diafenthiuron 32.5% + Fipronil 7.5% SC when applied at 900 ml/ha showed maximum reduction in Whitefly population of 5, 0, 3, 5 whiteflies/plant at 1, 4, 7 and 10 Days after spraying and Diafenthiuron 32.5% + Fipronil 7.5% SC @ 750ml/ha recorded 8, 3, 5 whiteflies/plant at 1,4,7 das and 6 whiteflies/plant at 10 das. The average Whitefly population after the entire spraying was recorded to be lowest in Diafenthiuron 32.5% + Fipronil 7.5% SC @ 900 ml/ha with 6.80 whiteflies/plant followed by Diafenthiuron 32.5% + Fipronil 7.5% SC @ 750 ml/ha with 8.0 whiteflies/plant which were performing superior to market standards. The percentage reduction in whitefly population recorded in all the treatments proved that Diafenthiuron 32.5% + Fipronil 7.5% SC when applied at 900 ml/ha was showing maximum reduction in whitefly population as 83.50% and at 750 ml/ha recorded 80.58% there by proving that these molecules when applied in combination at the doses of 900, 750 ml/ha showed synergistic activity and Whitefly population control was superior to market standard. Even the treatment Diafenthiuron 32.5% + Fipronil 7.5% SC when applied at 600 ml/ha (lowest dose of the insecticide combination) also showed a percent reduction of 76.70% which was also superior to the market standard. The market standards recorded 64.56% reduction in Pyriproxyfen 5% + Diafenthiuron 25% SE @ 1250ml/ha and 63.59% reduction in Fipronil 15% + Flonicamid 15% WDG @ 400g/ha.
Table 10. Efficacy of second spray application of Diafenthiuron 32.5% + Fipronil 7.5% SC formulation against Whitefly in Cotton.
Treatments Dose
(g or ml / ha) No. of Larva Per Plant
(Days After Spraying) % Reduction
in Whitefly Population Colby’s Ratio
Pre 1 4 7 10 AVG
Diafenthiuron 32.5% + Fipronil 7.5% SC 600 7 6.00 0.00 3 5 3.50 94.04 1.01
Diafenthiuron 32.5% + Fipronil 7.5% SC 750 6 3.00 0.00 2 4 2.25 96.17 1.04
Diafenthiuron 32.5% + Fipronil 7.5% SC 900 5 0.00 0.00 1 3 1.00 98.30 1.06
Diafenthiuron 50% WP 600 21 18.00 15.00 17.56 21 17.89 69.55 0.75
Fipronil 5% SC 1000 18 12.00 10.00 14 19 13.75 76.60 0.82
Pyriproxyfen 5% + Diafenthiuron 25% SE 1250 19 10.00 12.00 17 20 14.75 74.89 0.81
Fipronil 15% + Flonicamid 15% WDG 400 18 10.00 11.00 16.7 21 14.68 75.02 0.81
UNTREATED 52 53.00 55 61 66 58.75 0.00 0.00
The Whitefly population before initiating the second spray was recorded in between 5-21 whiteflies per plant in Cotton. This is the whitefly population recorded at the end of the first spraying. After the second application of different insecticide treatments, the insecticide combination treatments Diafenthiuron 32.5% + Fipronil 7.5% SC when applied at 900 ml/ha and 750ml/ha showed maximum reduction in Whitefly population. The treatment Diafenthiuron 32.5% + Fipronil 7.5% SC @ 900ml/ha recorded 0 whiteflies/plant at 1, 4, das and 1, 3 whiteflies/plant at 7, 10 Days after spraying, followed by Diafenthiuron 32.5% + Fipronil 7.5% SC @ 750ml/ha recorded 3, 0, 2, 4 whiteflies / plant at 1, 4, 7, and 10 das and Diafenthiuron 32.5% + Fipronil 7.5% SC @ 600ml/ha recorded 6, 0 whiteflies/plant at 1, 4 das and 3 at 7 das and 5 at 10 das in the three combination treatments. The average Whitefly population after the entire spraying was recorded to be lowest in Diafenthiuron 32.5% + Fipronil 7.5% SC @ 900 ml/ha with 1 whiteflies/plant followed by Diafenthiuron 32.5% + Fipronil 7.5% SC @ 750 ml/ha with 2.25 whiteflies / plant which were performing superior to market standards. The percent reduction in whitefly population recorded in all the treatments proved that Diafenthiuron 32.5% + Fipronil 7.5% SC when applied at 900 ml/ha was showing maximum reduction in whitefly population as 98.30% followed by Diafenthiuron 32.5% + Fipronil 7.5% SC @ 750 ml/ha with 96.17% reduction and Diafenthiuron 32.5% + Fipronil 7.5% SC @ 600 ml/ha recorded 94.04% there by proving that these molecules when applied in combination at the doses of 900, 750 and 600 ml/ha showed synergistic activity and Whitefly population control was superior to market standard. The market standards recorded 74.89% reduction in Pyriproxyfen 5% + Diafenthiuron 25% SE @ 1250ml/ha and 75.02% reduction in Fipronil 15% + Flonicamid 15% WDG @ 400g/ha. Though they are significantly controlling the whitefly population the same molecules when applied in combination with lesser strength recorded higher control in whitefly population and the colby’s ratio recorded in the three doses of Diafenthiuron 32.5% + Fipronil 7.5% SC was also >1 i.e., 1.01-1.06 proving the synergistic interaction in the combination insecticide.

Table 11. Effect of Diafenthiuron 32.5% + Fipronil 7.5% SC formulation on yield in Cotton.
Treatments Dose (g or ml / ha) Yield (q/ha)
Diafenthiuron 32.5% + Fipronil 7.5% SC 600 252
Diafenthiuron 32.5% + Fipronil 7.5% SC 750 265
Diafenthiuron 32.5% + Fipronil 7.5% SC 900 281
Diafenthiuron 50% WP 600 223
Fipronil 5% SC 1000 230
Pyriproxyfen 5% + Diafenthiuron 25% SE 1250 244
Fipronil 15% + Flonicamid 15% WDG 400 248
UNTREATED 200
The yield of Cotton recorded in different treatments as shown in the table above (Table 11.) implies that the combination molecule at the three doses positively affected the yield of the crop. The highest yield was recorded in Diafenthiuron 32.5% + Fipronil 7.5% SC @ 900 ml/ha with 281q/ha, followed by Diafenthiuron 32.5% + Fipronil 7.5% SC @ 750 ml/ha with 265 q/ha and Diafenthiuron 32.5% + Fipronil 7.5% SC @ 600 ml/ha with 252 q/ha. While the individual molecules and market standards recorded yields ranging between 223-248 q/ha which were inferior to the yield recorded in the combination molecule treatments
Table 12. Phytotoxicity of Diafenthiuron 32.5% + Fipronil 7.5% SC on Cotton
Treatments Days Visual Rating Scale
Yellowing Necrosis Wilting Vein
Clearing Leaf Tip / Margin Dying Stunting / Dwarfing
Diafenthiuron 32.5% + Fipronil 7.5% SC @ 600ml/ha 5 0 0 0 0 0 0
10 0 0 0 0 0 0
Diafenthiuron 32.5% + Fipronil 7.5% SC @ 750ml/ha 5 0 0 0 0 0 0
10 0 0 0 0 0 0
Diafenthiuron 32.5% + Fipronil 7.5% SC @ 900ml/ha 5 0 0 0 0 0 0
10 0 0 0 0 0 0
Diafenthiuron 50% WP @ 600g/ha 5 0 0 0 0 0 0
10 0 0 0 0 0 0
Fipronil 5% SC @ 1000ml/ha 5 0 0 0 0 0 0
10 0 0 0 0 0 0
Pyriproxyfen 5% + Diafenthiuron 25% SE @ 1250ml/ha 5 0 0 0 0 0 0
10 0 0 0 0 0 0
Fipronil 15% + Flonicamid 15% WDG @ 400g/ha 5 0 0 0 0 0 0
10 0 0 0 0 0 0
Untreated 5 0 0 0 0 0 0
10 0 0 0 0 0 0
The phytotoxicity effect of the insecticide combination i.e., Diafenthiuron 32.5% + Fipronil 7.5% SC on Cotton crop was tested after 5 and 10 Days after spraying. The crop was checked for symptoms like yellowing, necrosis, wilting, vein clearing, leaf tip or leaf margin dying and stunting or dwarfing of plants. After thorough observations, it could be concluded that the crop did not show any symptoms of phytotoxicity. Therefore, the present insecticide combination can be considered a safe molecule.
It is to be understood that this disclosure is not limited to a particular compositions or specific constituents, which can, of course, vary and that the terminology used herein is for the purpose of describing embodiments only and is not intended to be limiting the scope of the invention. As used in this specification and the appended claims, the singular forms "a," "an," and "the" include plural referents unless the content clearly dictates otherwise, and equivalents thereof known to those skilled in the art and so forth.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art to which this disclosure pertains. Although any methods and materials similar or equivalent to those described herein can be used in the practice for testing of the disclosure(s), specific examples of appropriate materials and methods are described herein.
The examples set forth above are provided to give those of ordinarily skilled in the art a complete description of how to make and use the embodiments of the particular compositions or specific constituents, methods of practice, and are not intended to limit the scope of what the inventors regard as their invention. Modifications of the above-described modes for carrying out the invention that is obvious to persons skilled in the art are intended to be within the scope of the following claims. All patents and publications mentioned in the specification are indicative of the levels of skill of those skilled in the art to which the disclosure pertains.
While specific embodiments of the present invention are explicitly disclosed herein, the above specification and examples herein are illustrative and not restrictive. It will be understood that various modifications may be made without departing from the spirit and scope of the invention. Many variations of the disclosure will become apparent to those skilled in the art upon review of this specification and the embodiments below. The full scope of the invention should be determined by reference to the embodiments, along with their full scope of equivalents and the specification, along with such variations. Accordingly, other embodiments are within the scope of the following claims. ,CLAIMS:CLAIMS:
We Claim:
1. A synergistic insecticidal composition comprising:
(a) at least one thiourea insecticide;
(b) at least one pyrazole insecticide; and
(c) at least one agrochemical acceptable excipient.
2. The composition as claimed in claim 1, wherein the thiourea insecticide is selected from diafenthiuron.
3. The composition as claimed in claim 1, wherein the pyrazole insecticides is selected from the group comprising but not limited to acetoprole, dimpropyridaz, ethiprole, fipronil, flufiprole, pyrafluprole, pyriprole, tolfenpyrad, and vaniliprole.
4. The composition as claimed in preceding claims, wherein diafenthiuron and fipronil are formulated in suspension concentrates (SC) and present in the weight ratio of (1-40): (1-10).
5. The composition as claimed in preceding claims, wherein the insecticidal composition is used for prophylactic application, destroy and/or control the pests applying effective amount of insecticidal composition over the target areas by conventional methods by for preventive and curative action.
6. The composition as claimed in preceding claims, wherein the insecticidal composition is used for destroying and/or control the pests in rice, wheat, fruits, roots, tubers, vegetables, maize, grains, sugarcane, cereals, field crops and various other crops for general pest control.