FIELD OF THE INVENTION
The present invention relates to synergistic insecticidal composition. More particularly, the present invention relates to a synergistic insecticidal composition comprising nitenpyram, pymetrozine and any one of buprofezin or dinotefuran.
BACKGROUND OF THE INVENTION
Insecticide compositions that can be applied at as low a dose as possible and be effective in controlling pest species of insects while causing as little harm as possible to beneficial insects and minimal disturbance in the environment are in demand by the farming community. Insects are very destructive to crops and can result in significant loss of crop yield and quality, which results in economic loss to the grower and increased costs to the consumer.
Combinations of insecticides are typically used to broaden the spectrum of insect control, to minimize the doses of chemicals use, to retard resistance development and to reduce the cost of treatment through additive effect. Although, many combinations of insecticidal agents have been studied, a synergistic effect is rarely attained.
Therefore, there is still a need for novel insecticidal compositions that exhibit synergistically enhanced action, a broader scope of activity and reduced cost of treatment.
SUMMARY OF THE INVENTION
The inventors of the present invention have surprisingly found that a combination of nitenpyram, pymetrozine and any one of buprofezin or dinotefuran provides enhanced synergistic insecticidal activity.
Accordingly, the present invention provides a synergistic insecticidal composition comprising a) nitenpyram; b) pymetrozine; and any one of c) buprofezin or dinotefuran.

In an embodiment the composition of the present invention, comprises nitenpyram in an amount in the range from about 0.1 to 4% w/w, pymetrozine in an amount in the range from about 5 to 20% w/w and buprofezin in an amount in the range from about 10 to 30% w/w.
In another embodiment the composition of the present invention, comprises nitenpyram in an amount in the range from about 0.1 to 4% w/w, pymetrozine is present in an amount in the range from about 5 to 20% w/w and dinotefuran in an amount in the range from about 2 to 8% w/w.
In yet another embodiment the composition of the present invention further comprises an excipient. The excipient is selected from the group comprising dispersing agent, wetting agent, anti-freezing agent, defoamer, stabilizer, biocide, disintegration agent, thickener and filler.
In another embodiment, the composition is formulated as Capsule suspension (CS), Dispersible concentrate (DC), Dustable powder (DP), Powder for dry seed treatment (DS), Emulsifiable concentrate (EC), Emulsifiable granule (EG), Emulsion water-in-oil (EO), Emulsifiable powder (EP), Emulsion for seed treatment (ES), Emulsion oil-in-water (EW), Flowable concentrate for seed treatment (FS), Granules (GR), Micro-emulsion (ME), Oil-dispersion (OD), Oil miscible flowable concentrate (OF), Oil miscible liquid (OL), Oil dispersible powder (OP), Suspension concentrate (SC), Suspension concentrate for direct application (SD), Suspo-emulsion (SE), Water soluble granule (SG), Soluble concentrate (SL), Spreading oil (SO), Water soluble powder (SP), Water soluble tablet (ST), Ultra-low volume (ULV) suspension, Tablet (TB), Ultra-low volume (ULV) liquid, Water dispersible granules (WG), Wettable powder (WP), Water dispersible powder for slurry seed treatment (WS), Water dispersible tablet (WT), a mixed formulation of CS and SC (ZC) or A mixed formulation of CS and SE (ZE), a mixed formulation of CS and EW (ZW), preferably as suspension concentrate or water dispersible granules.

In one another embodiment, the excipient is selected from the group comprising dispersing agent, wetting agent, anti-freezing agent, defoamer, biocide and thickener, and wherein the composition is formulated as suspension concentrate.
In another embodiment, the excipient is selected from the group comprising dispersing agent, wetting agent, disintegration agent, defoamer and filler, and wherein the composition is formulated as water dispersible granule.
In yet another embodiment, the dispersing agent is selected from the group comprising amine salt of phosphate tristyryl phenol ethoxylated, acrylic copolymer, graft copolymer, naphthalene sulphonate of formaldehyde condensate, acrylic copolymer, lignin based sulphonate and combinations thereof, and present in an amount in the range from 1 to 10% w/w.
In one another embodiment, the wetting agent is selected from the group comprising ethoxylated polyarylphenol phosphate ester, dioctyl sulphosuccinate, non-ionic ethoxylate, naphthalene alkyl aryl sulphonate, dioctyl sulfosuccinate, sodium lauryl sulfate and combinations thereof, and present in an amount in the range from 1 to 5% w/w.
In an embodiment, the anti-freezing agent is selected from the group consisting of propylene glycol, diethylene glycol, monoethylene glycol and combinations thereof, and present in an amount in the range from 2 to 10% w/w.
In another embodiment, the defoamer is dimethyl polysiloxane emulsion and present in an amount in the range from 0.01 to 1% w/w.
In one another embodiment, the biocide is selected from the group consisting of 20% aqueous dipropylene glycol solution of l,2-benzisothiazolin-3-one, formaldehyde and combinations thereof and present in an amount in the range from 0.01 to 0.50% w/w.
In an embodiment, the disintegration agent is selected from citric acid and sodium bicarbonate and present in an amount in the range from 1 to 5% w/w.
In another embodiment, the thickener is xanthan gum and is present in an amount in the range from 0.01 to 0.50% w/w.

In yet another embodiment, the filler is selected from bentonite clay, china clay, silica, kaolin and diatomaceous earth.
BRIEF DESCRIPTION OF DRAWINGS
Figure 1. is a flowchart for preparing synergistic insecticidal composition comprising nitenpyram, pymetrozine and buprofezin in the form of suspension concentrate.
Figure 2. is a flowchart for preparing synergistic insecticidal composition comprising nitenpyram, pymetrozine and buprofezin in the form of water-dispersible granule.
Figure 3. is a flowchart for preparing synergistic insecticidal composition comprising nitenpyram, pymetrozine and dinotefuran in the form of suspension concentrate.
Figure 4. is a flowchart for preparing synergistic insecticidal composition comprising nitenpyram, pymetrozine and dinotefuran in the form of water-dispersible granule.
DETAILED DESCRIPTION OF THE INVENTION
Discussed below are some representative embodiments of the present invention. The invention in its broader aspects is not limited to the specific details and representative methods. The illustrative examples are described in this section in connection with the embodiments and methods provided. The invention according to its various aspects is particularly pointed out and distinctly claimed in the appended claims read in view of this specification and appropriate equivalents.
It is to be noted that, as used in the specification and the appended claims, the singular forms "a", "an" and "the" include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to a composition containing "a compound" includes a mixture of two or more compounds. It should also be noted that the term "or" is generally employed in its sense including "and/or" unless the content clearly dictates otherwise.

The expression of various quantities in terms of "% w/w" or "%" means the percentage by weight, relative to the weight of the total solution or composition unless otherwise specified.
The term "active ingredient" (A.I.) or "active agent" used herein refers to that component of the composition responsible for control of insect-pests.
As used herein, the expressions "SL formulation", "SC formulation" "WDG or WG formulation" "GR formulation", "DF formulation", "CG formulation", "EC formulation", "EW formulation", "ME formulation", "WP formulation" are the international denominations adopted by the FAO (Food and Agricultural Organization of the United Nations) to designate "soluble liquid", "aqueous suspension concentrate", "water dispersible granules", "granular", "dry flowable", "capsulated granules", "emulsion concentrate", "emulsion", "micro-emulsion" and "wettable powder" respectively.
In accordance with an embodiment of the invention, there is provided a synergistic insecticidal composition comprising a) nitenpyram; b) pymetrozine; and any one of c) buprofezin or dinotefuran.
Nitenpyram is an insecticide used to control various insect pests. It belongs to the class of neonicotinoid insecticides.
Nitenpyram is represented by following structural formula-
"V


cr CH2

Ctta

IUPAC: (E)-N-(6-chloro-3-pyridylmethyl)-N-ethyl-N'-methyl-2-
nitrovinylidenediamine
Nitenpyram acts as an agonist of the nicotinic acetylcholine receptor, affecting cholinergic transmissions in the insect central nervous system. It is a systemic insecticide with translaminar activity and with contact and stomach action. It

provides control of aphids, thrips, leafhoppers, whitefly and other sucking insects in rice and other crops.
Pymetrozine is a pyridine azomethine insecticide and is represented by the following structural formula-
6
IUPAC: (E)-4,5-dihydro-6-methyl-4-(3-pyridylmethyleneamino)-l,2,4-triazin-3(2H)-one
Pymetrozine is selective against Homoptera, causing them to stop feeding. It provides control of juvenile and adult stages of aphids and whiteflies in vegetables, potatoes, ornamental, cotton, deciduous fruit, citrus, tobacco and hops and planthoppers in rice.
Buprofezin belongs to the class of chitin synthesis inhibitor- type 1. Buprofezin is represented by following structural formula-

HjC

;>i.
,CH3

IUPAC: (Z)-2-tert-butylimino-3-isopropyl-5-phenyl-l,3,5-thiadiazinan-4-one
Buprofezin acts as a persistent insecticide and acaricide with contact and stomach action and is not translocated in the plant. It inhibits moulting of nymphs and larvae, leading to death. It also suppresses oviposition by adults and treated insects lay sterile eggs. It controls Cicadellidae, Deltocephalinae and Delphacidae in rice, Coccinellidae in potatoes; Aleyrodidae in citrus, cotton and vegetables;

Coccidae, Diaspididae and Pseudococcidae in citrus and top fruit; Tarsonemidae in vegetables.
Dinotefuran belongs to the class of neonicotinoid insecticides. Dinotefuran is represented by following structural formula-
O
A
IUPAC: (EZ)-(RS)-l-methyl-2-nitro-3-(tetrahydro-3-furylmethyl)guanidine
Dinotefuran is an agonist of the nicotinic acetylcholine receptor, affecting the synapses in the insect central nervous system. It is a systemic insecticide with translaminar activity and with contact and stomach action. It is readily taken up by the plant and further distributed acropetally. It controls sucking insects, such as whiteflies, plant bugs, leafhoppers and mealybugs; Coleoptera such as Colorado beetles and flea beetles; Diptera, such as leaf miner flies; and certain Lepidoptera, such as fruit moths, in vegetables, fruit, paddy rice and turf.
The present invention relates to a synergistic insecticidal composition comprising
a) nitenpyram;
b) pymetrozine; and any one of c) buprofezin or dinotefuran.
In an aspect of the invention, nitenpyram is present in an amount in the range from about 0.1 to 4% w/w, pymetrozine is present in an amount in the range from about 5 to 20% w/w and buprofezin is present in an amount in the range from about 10 to 30% w/w. Preferably, nitenpyram is present in an amount in the range from about 1 to 3% w/w, pymetrozine is present in an amount in the range from about 10 to 20% w/w and buprofezin is present in an amount in the range from about 15 to 25% w/w. More preferably, nitenpyram is present in an amount of 2% w/w, pymetrozine is present in an amount of 15% w/w and buprofezin is present in an amount of 20% w/w.

In another aspect of the invention, nitenpyram is present in an amount in the range from about 0.1 to 4% w/w, pymetrozine is present in an amount in the range from about 5 to 20% w/w and dinotefuran is present in an amount in the range from about 2 to 8% w/w. Preferably, nitenpyram is present in an amount in the range from about 1 to 3% w/w, pymetrozine is present in an amount in the range from about 10 to 20% w/w and dinotefuran is present in an amount in the range from about 3 to 8% w/w. More preferably, nitenpyram is present in an amount of 2% w/w, pymetrozine is present in an amount of 15% w/w and dinotefuran is present in an amount of 4% w/w.
The ratio of the nitenpyram, pymetrozine and buprofezin in the composition of the present invention is in the range of 1 to 40: 1.25 to 200: 2.5 to 250. In a preferred aspect of the invention, when the ratio of nitenpyram to pymetrozine is about 1:7.5; the ratio of pymetrozine to buprofezin is about 3:4.
The ratio of the nitenpyram, pymetrozine and dinotefuran in the composition of the present invention is in the range of 1 to 40: 1.25 to 200: 0.5 to 80. In a preferred aspect of the invention, when the ratio of nitenpyram to pymetrozine is about 1:7.5; the ratio of pymetrozine to dinotefuran is about 7.5:2.
The synergistic insecticidal composition of the present invention further comprises an excipient. The excipient is selected from the group comprising dispersing agent, wetting agent, anti-freezing agent, defoamer, biocide, disintegrating agent, thickener and filler.
The synergistic composition of the present invention may be formulated as Capsule suspension (CS), Dispersible concentrate (DC), Dustable powder (DP), Powder for dry seed treatment (DS), Emulsifiable concentrate (EC), Emulsifiable granule (EG), Emulsion water-in-oil (EO), Emulsifiable powder (EP), Emulsion for seed treatment (ES), Emulsion oil-in-water (EW), Flowable concentrate for seed treatment (FS), Granules (GR), Micro-emulsion (ME), Oil-dispersion (OD), Oil miscible flowable concentrate (OF), Oil miscible liquid (OL), Oil dispersible powder (OP), Suspension concentrate (SC), Suspension concentrate for direct application (SD), Suspo-emulsion (SE), Water soluble granule (SG), Soluble

concentrate (SL), Spreading oil (SO), Water soluble powder (SP), Water soluble tablet (ST), Ultra-low volume (ULV) suspension, Tablet (TB), Ultra-low volume (ULV) liquid, Water dispersible granules (WG), Wettable powder (WP), Water dispersible powder for slurry seed treatment (WS), Water dispersible tablet (WT), a mixed formulation of CS and SC (ZC), a mixed formulation of CS and SE (ZE), a mixed formulation of CS and EW (ZW). The abbreviations provided for various formulations are the international denominations adopted by the FAO (Food and Agricultural Organization of the United Nations).
Preferably, the composition of the present invention is formulated as suspension concentrate or water dispersible granules.
In an embodiment, the excipient is selected from the group comprising dispersing agent, wetting agent, anti-freezing agent, defoamer, biocide, thickener, and the composition is in the form of a suspension concentrate (SC). The term "suspension concentrate" used herein refers to a suspension of the active insecticide and excipients in a small quantity of liquid, usually water.
In another embodiment, the excipient is selected from the group comprising dispersing agent, wetting agent, disintegration agent, defoamer, filler, and wherein the formulation is water dispersible granule. The term "water dispersible granules" used herein refers to granules that are obtained by blending and agglomerating a ground solid active ingredient together with excipients.
It is generally observed that solid particles in a liquid undergo spontaneous aggregation to form lumps. Hence it is recommended to add a dispersing agent which prevents agglomeration of solid particles and keep them suspended in fluid. Accordingly, the composition of the present invention contains dispersing agents such as amine salt of phosphate tristyryl phenol ethoxylated, acrylic copolymer, graft copolymer, naphthalene sulphonate of formaldehyde condensate, acrylic copolymer, lignin based sulphonate. One or more dispersing agents may be used in the synergistic composition of the present invention. The dispersing agent is present in an amount in the range from 1 to 10% w/w.

Wetting is the first stage of dispersion, in which air surrounding the granular composition is substituted with water. Wetting of the composition with water cannot occur if the surface tension of the liquid is very high. Hence, it is recommended to add a wetting agent to the composition to facilitate the process of dispersion of the granules in the liquid. Non-limiting examples of wetting agents that can be used in the present invention include ethoxylated polyarylphenol phosphate ester, dioctyl sulphosuccinate, non-ionic ethoxylate, dioctyl sulfosuccinate, sodium lauryl sulfate, naphthalene alkyl aryl sulphonate. The alkyl aryl sulphonates in which the alkyl group contains approximately 1 to 5 carbon atoms and in which the aryl nucleus is selected from the group consisting of benzene and naphthalene. One or more wetting agents may be used in the synergistic composition of the present invention. The wetting agent is present in an amount in the range from 1 to 5% w/w.
An anti-freezing agent is generally added to the composition, to prevent the aqueous compositions from freezing. Suitable anti-freezing agents useful herein, but not limited to, include propylene glycol, diethylene glycol, monoethylene glycol and combinations thereof. Preferably, the anti-freezing agent is present in an amount in the range from 2 to 10% w/w.
A defoamer, also called as anti-foaming agent, is generally added to the composition as foam formation prevents the efficient filling of a container. Preferably, the defoamer is polydimethyl siloxane emulsion. In the insecticidal composition of the present invention the defoamer is present in an amount in the range from 0.01 to 1% w/w.
The synergistic insecticidal composition comprises a biocide selected from the group consisting of 20% aqueous dipropylene glycol solution of 1,2-benzisothiazolin-3-one, formaldehyde and combinations thereof, and present in an amount in the range from 0.01 to 0.50% w/w. The biocide is added to the composition of the present invention for its preservation against spoilage from bacteria, yeasts and fungi.

The disintegration agent is selected from citric acid and sodium bicarbonate and present in an amount in the range from 1 to 5% w/w.
It is necessary to add a thickener to the composition to reduce the tendency of the composition to disperse when sprayed, and decrease the likelihood of it being rinsed off from the crops. Preferably, the synergistic insecticidal composition comprises xanthan gum as thickener in an amount in the range from 0.01 to 0.50%
w/w.
A filler is added to the composition to improve the handling and storage characteristics of the composition. Fillers also add mass and/or volume to the active ingredient in order to facilitate precise measurement of the doses. Suitable fillers that may be used in the composition of the present invention include, but not limited to, bentonite clay, china clay, silica, kaolin and diatomaceous earth.
The compositions of the present invention also provide control of insects belongs
to the order Hemiptera and Thysanoptera. The present invention provides
effective control of a broad spectrum of insect pests of ornamental, vegetable,
field, cereal, greenhouse, fruit, vine crops and cotton. These insects
include Brevicoryne brassicae, Hydaphis pseudobrassicae, Acyrthosiphon
pisum, Aphis craccivora, Aphis fabae, Macrosiphum rosae, Macrosiphum
euphorbiae, Hyalopterus amygdali, Brachycaudus persicaecola, Aphis
pomi, Sappaphis piricola, Aphis citricola, Nasonovia ribisnigri, Eriosoma
lanigerum, Megoura viciae, Pemphigus spp., Toxoptera spp, Phorodon
humuli, Diuraphis noxia, Lipaphis erysimi, Metopolophium
dirhodium, Therioaphis spp., Schizaphis graminum, Sitobion
avenae,Rhopalosiphum spp., Aphis gossypii,Myzus nicotianae and
particularly Myzus persicae. The insects also include Bemisia tabaci, Trialeurodes
vaporariorum, Nilaparvatalugens, Nephotettix spp., Philaenusspumarius, Empoas ca spp., Spissistilusfestinus, Laodelphaxstriatellus, Erythroneura sp., Typhlocyba pomaria, Adelges abietis, Icerya purchasi, Aonidiella aurantii, Quadraspidiotus perniciosus, Gossyparia

spuria,Planococcuscitri, Phenacoccus spp., Pseudococcus spp., Centrococcus spp ., Eriococcusazaleae,Oebaluspugnax, Nezaraviridula, Lygus spp., Euschistusspp., Chlorochroa spp., Pachypsylla celtidismama, Paratriozacockerelli,
Cacopsyllapyricola, Pseudatomoscelis seriatus, Thrips spp., Frankliniella
occidentalis, Pineus strobi and other genera and species closely related to these insects.
The present invention also relates to a process of preparation of synergistic insecticidal composition comprising nitenpyram, pymetrozine, and any one of buprofezin or dinotefuran.
The composition of the present invention is relatively safer to human beings, animals and abiotic factors. The present invention provides an improved stable and ready to use insecticidal composition comprising nitenpyram, pymetrozine, and any one of buprofezin or dinotefuran which overcomes the problems faced by the farmers in the field of physically mixing the individual, commercially available formulations at the desired field.
The synergism manifested by the composition of the present invention comprising nitenpyram, pymetrozine, and any one of buprofezin or dinotefuran allow a substantial reduction in the application rates of each of these active ingredients, while maintaining good insecticidal efficacy. Decreasing application rates reduces treatment cost to the farmer and also eases the burden on the environment both from manufacturing waste and crop protection chemical residues.
It has been surprisingly found that the synergistic insecticidal composition of the present invention provides a wide spectrum control of insects, high efficacy against wide range of insects, delaying the appearance of the resistant strains.
In another aspect the present invention provides a method for controlling insects, comprising contacting crops or their environment with an effective amount of the composition of the present invention.
The embodiments of the present invention are more particularly described in the following examples that are intended as illustrations only, since numerous

modifications and variations within the scope of the present invention will be apparent to those of skill in the art. Unless otherwise noted, all parts, percentages and ratios reported in the following examples are on a weight basis and all reagents used in the examples were obtained or are available from the chemical suppliers.
EXAMPLES
The synergistic insecticidal composition of the present invention comprising nitenpyram, pymetrozine and buprofezin in the form of suspension concentrate is provided in Table 1. The unit of each component of the composition are expressed in "% w/w" i.e. the percentage by weight, relative to the weight of the total solution or composition.
Table 1: Synergistic insecticidal composition comprising nitenpyram, pymetrozine and buprofezin in suspension concentrate (SC) form

QS: quantity sufficient required to make 100% w/w formulation
Table 2 provides quantities of active ingredients and raw material charged to prepare the synergistic composition of the present invention in SC form. The active ingredients such as nitenpyram, pymetrozine and buprofezin are in technical grade. The entries for active ingredients, nitenpyram, pymetrozine and buprofezin in table 2 varies from that of table 1, as the entries in table 1 are for 100% pure compounds whereas the entries in Table 2 are for technical ones with certain percentage of impurities. Hence, nitenpyram 2% w/w, pymetrozine 15% w/w and buprofezin 20% w/w of 100% purity of Table 1 corresponds to nitenpyram 2.11 kg, pymetrozine 15.80 kg and buprofezin 21.10 kg of 95% purity each of Table 2.
Table 2: Quantities of active ingredients and raw material charged

Example 1: Process of preparing synergistic insecticidal composition comprising nitenpyram, pymetrozine and buprofezin in suspension concentrate (SC) form
All the components were weighed as per table 2. The graft copolymer (5 kg) and non-ionic ethoxylate (3 kg) were diluted in deminerahsed water (47.69 kg) and solubilized by high shear mixing. Then propylene glycol (5 kg), nitenpyram (2.11 kg), pymetrozine (15.80 kg), buprofezin (21.10 kg), dimethyl polysiloxane emulsion (0.10 kg), 20% aqueous dipropylene glycol solution of 1,2-benzisothiazolin-3-one (0.10 kg) were added and mixed to obtain a homogeneous mass. The homogeneous mass was grinded in bead mill. The grinding was carried out until a mean particle size of 3-5(D-90) microns was obtained. After grinding, 2% water solution of xanthan gum was added under low stirring to obtain the title insecticidal composition.
Table 3 provides synergistic insecticidal composition comprising nitenpyram, pymetrozine and buprofezin in the form of water dispersible granules. The unit of each component of the composition are expressed in "% w/w" i.e. the percentage by weight, relative to the weight of the total solution or composition.

Table 3: Synergistic insecticidal composition comprising nitenpyram, pymetrozine and buprofezin in water dispersible granules (WG) form
QS: quantity sufficient required to make 100% w/w formulation
Table 4 provides quantities of active ingredients and raw material charged to prepare the synergistic composition of the present invention in WG form. The entries for active ingredients, table 4 varies from that of table 3, as the entries in table 3 are for 100% pure compounds whereas the entries for active ingredients in Table 4 are for technical ones with certain percentage of impurities.
Table 4: Quantities of active ingredients and raw material charged

Example 2: Process of preparing synergistic insecticidal composition comprising nitenpyram, pymetrozine and buprofezin in water dispersible granules (WG) form
All the components were weighed as per table 4 and mixed well using proper ribbon blender type mixer to obtain a mixture. The mixture was milled with suitable jet mill. The mixture was milled to achieve a particle size below 10 microns and then mixed properly in a post blender. A dough was prepared using the milled mixture and 10% to 20% water in suitable dough-mixer. The dough was then extruded using proper extruder having suitable screen while maintaining the temperature of the screen below 50°C to obtain extruded granules. The extruded granules were dried using a fluid bed dryer. The air flow was kept at 75% and the temperature of the air was maintained at 50°C. The granules were dried until free flowing granules were obtained.
Table 5 provides synergistic insecticidal composition of the present invention comprising nitenpyram, pymetrozine and dinoterfuran in the form of suspension concentrate. The unit of each component of the composition are expressed in "% w/w" i.e. the percentage by weight, relative to the weight of the total solution or composition.

Table 5: Synergistic insecticidal composition comprising nitenpyram, pymetrozine and dinotefuran in suspension concentrate (SC) form
QS: quantity sufficient required to make 100% w/w formulation
Table 6 provides quantities of active ingredients and raw material charged to prepare the synergistic composition of the present invention in SC form. The entries for active ingredients, nitenpyram, pymetrozine and dinotefuran in table 6 varies from that of table 5, as the entries in table 5 are for 100% pure compounds whereas the entries in Table 6 are for technical ones with certain percentage of impurities. Hence, nitenpyram 2% w/w, pymetrozine 15% w/w and dinotefuran 4% w/w of 100% purity of Table 5 corresponds to nitenpyram 2.11 kg,

pymetrozine 15.80 kg and dinotefuran 4.08 kg of 95%, 95% and 98% purity respectively, of Table 6.
Table 6: Quantities of active ingredients and raw material charged
Example 3: Process of preparing synergistic insecticidal composition comprising nitenpyram, pymetrozine and dinotefuran in suspension concentrate (SC) form
All the components were weighed as per Table 6. The graft copolymer (5 kg) and non-ionic ethoxylate (3 kg) were diluted in de-mineralised water (64.69 kg) and solubilized by high shear mixing. Then propylene glycol (5 kg), nitenpyram (2.11 kg), pymetrozine (15.80 kg), dinotefuran (4.08 kg), dimethyl polysiloxane emulsion (0.10 kg), 20% aqueous dipropylene glycol solution of 1,2-

benzisothiazolin-3-one (0.10 kg) were added and mixed to obtain a homogeneous mass. The homogeneous mass was grinded in bead mill. The grinding was carried out until a mean particle size of 3-5(D-90) microns was obtained. After grinding, 2% water solution of xanthan gum was added under low stirring to obtain the title insecticidal composition.
Table 7 provides synergistic insecticidal composition comprising nitenpyram, pymetrozine and dinotefuran in the form of water dispersible granules. The unit of each component of the composition are expressed in "% w/w" i.e. the percentage by weight, relative to the weight of the total solution or composition.
Table 7: Synergistic insecticidal composition comprising nitenpyram, pymetrozine and dinotefuran in water dispersible granules (WG) form
QS: quantity sufficient required to make 100% w/w formulation
Table 8 provides quantities of active ingredients and raw material charged to prepare the synergistic composition of the present invention in WG form. The entries for active ingredients, mesotrione, atrazine and 2,4-D acid in table 8 varies

from that of table 7, as the entries in table 7 are for 100% pure compounds whereas the entries for active ingredients in Table 8 are for technical ones with certain percentage of impurities. Hence, nitenpyram 2% w/w, pymetrozine 15% w/w and dinotefuran 4% w/w of 100% purity of Table 7 corresponds to nitenpyram 2.11 kg, pymetrozine 15.80 kg and dinotefuran 4.08 kg of 95%, 95% and 98% purity respectively, of Table 8.
Table 8: Quantities of active ingredients and raw material charged
Example 4: Process of preparing synergistic insecticidal composition comprising nitenpyram, pymetrozine and dinotefuran in water dispersible granules (WG) form
All the components were weighed as per table 8 and mixed well using proper ribbon blender type mixer to obtain a mixture. The mixture was milled with suitable jet mill. The mixture was milled to achieve a particle size below 10 microns and then mixed properly in a post blender. A dough was prepared using the milled mixture and 10% to 20% water in suitable dough-mixer. The dough was then extruded using proper extruder having suitable screen while maintaining the temperature of the screen below 50°C to obtain extruded granules. The extruded granules were dried using a fluid bed dryer. The air flow was kept at

75% and the temperature of the air was maintained at 50°C. The granules were dried until free flowing granules were obtained.
Evaluation of bio-efficacy of the synergistic insecticidal composition comprising nitenpyram, pymetrozine and any one of buprofezin or dinotefuran against brown plant hopper in paddy crop
Trials were performed at three different agro climatic zones of the country to evaluate the biological efficacy of the synergistic insecticidal composition of present invention (Tl to T4) and reference products (T5 - T13) against brown plant hopper in paddy crop. Table 9 provides treatment details of insecticidal compositions for evaluation of bio-efficacy against brown plant hopper in paddy crop. The evaluation was performed by comparing the synergistic insecticidal composition of the present invention (nitenpyram, pymetrozine and buprofezin in SC and WG forms and nitenpyram, pymetorzine and dinotefuran in SC and WG forms) against the reference products, such as nitenpyam and pymetrozine; nitenpyram and buprofezin; pymetrozine and buprofezin; nitenpyram and dinotefuran; pymetrozine and dinotefuran; solo formulations of nitenpyram, pymetrozine, buprofezin and dinotefuran.
Table 9: Treatment details for evaluation of bio-efficacy of synergistic insecticidal composition

The experiment was laid out in Randomized Block Design (RBD) with three replications. The plot size was 50 sq. mts. All the recommended agronomic practices were followed throughout the cropping period. The various insecticidal compositions as per Table 9 were sprayed on paddy crop to evaluate the control of brown plant hopper. Hollow cone nozzle was used for spraying. The spray volume used was 500 litres per hectare.
To assess the effect of synergistic insecticidal composition field trials were conducted in three different agro-climatic location with plot size of 50 sq. meter per treatment replicated thrice. Observation for brown plant hopper (BPH) count were made in randomly tagged 20 hills per plot and total number of brown plant hopper (BPH) were recorded before spraying and at 5 days and 10 days after spraying (DAS) and expressed as BPH per hill.
The bio-efficacy effect of different treatment against BPH on paddy crop and treatment wise yield data of paddy is summarized in Table 10.

Table 10:

BS - Before spraying; DAS - Days after spraying;
Figures in parentheses are square root transformed values
A synergistic effect exists whenever the action of an active ingredient combination is greater than the sum of the actions of the individual components. Synergism was calculated by using Colby's method, Weeds, vol 15 No. l(Jan
1967), pp 20-2.
The synergistic action expected for a given combination of three active components can be calculated as follows:
E = X+Y+Z - XY+YZ+XZ + XYZ
100 10000

in which E represents the expected percentage of insecticidal control for the combination of the three insecticides at defined doses (for example equal to x, y and z respectively), X is the percentage of insecticidal control observed by the compound (I) at a defined dose (equal to x), Y is the percentage of insecticidal control observed by the compound (II) at a defined dose (equal to y) , Z is the percentage of insecticidal control observed by the compound (III) at a defined dose (equal to z) . When the percentage of insecticidal control observed for the combination is greater than the expected percentage, there is a synergistic effect.
Table 11 summarizes the synergistic impact of the composition of the present invention.
Table 11

Phytotoxicity Observations
For phytotoxicity evaluation on paddy, following observations were made by observing temporary or long lasting damage to the leaves if any viz., leaf injury on tips and leaf surface, wilting, vein clearing, necrosis, epinasty and hyponasty at 5 and 10 days after spray of the synergistic insecticidal composition of the present invention (Tl- T4). Crop injury was observed on visual rating from 1-10 scale as given in table 11.
Table 11:

Table 12. Phytotoxic effect of synergistic composition of the present invention on paddy crop
The synergistic insecticidal composition of the present invention gave good control of insects along with increase in yield and better economics to farmers as compared to the reference products. Further, the use of the synergistic insecticidal composition resulted in better crop condition, i.e. fresh green leaves and did not produce any phytotoxic symptoms on the plants.
From the foregoing it will be observed that numerous modifications and variations can be effectuated without departing from the true spirit and scope of the novel concepts of the present invention. It is to be understood that no limitations with respect to the specific embodiments illustrated is intended or should be inferred. It should be understood that all such modifications and improvements have been deleted herein for the sake of conciseness and readability but are properly within the scope of the following claims.

We Claim:
1. A synergistic insecticidal composition comprising:
a) nitenpyram;
b) pymetrozine; and any one of
c) buprofezin or dinotefuran.

2. The synergistic insecticidal composition as claimed in claim 1, wherein nitenpyram is present in an amount in the range from about 0.1 to 4% w/w, pymetrozine is present in an amount in the range from about 5 to 20% w/w and buprofezin is present in an amount in the range from about 10 to 30% w/w.
3. The synergistic insecticidal composition as claimed in claim 1, wherein nitenpyram is present in an amount in the range from about 0.1 to 4% w/w, pymetrozine is present in an amount in the range from about 5 to 20% w/w and dinotefuran is present in an amount in the range from about 2 to 8% w/w.
4. The synergistic insecticidal composition as claimed in claim 1, further comprises an excipient.
5. The synergistic insecticidal composition, as claimed in claim 4, wherein the excipient is selected from the group comprising dispersing agent, wetting agent, anti-freezing agent, defoamer, biocide, disintegration agent, thickener and filler.
6. The synergistic insecticidal composition as claimed in claim 4, wherein the composition is formulated as Capsule suspension (CS), Dispersible concentrate (DC), Dustable powder (DP), Powder for dry seed treatment (DS), Emulsifiable concentrate (EC), Emulsifiable granule (EG), Emulsion water-in-oil (EO), Emulsifiable powder (EP), Emulsion for seed treatment (ES), Emulsion oil-in-water (EW), Flowable concentrate for seed treatment (FS), Granules (GR), Micro-emulsion (ME), Oil-dispersion (OD), Oil miscible flowable concentrate (OF), Oil miscible liquid (OL), Oil dispersible powder (OP), Suspension concentrate (SC), Suspension concentrate for direct

application (SD), Suspo-emulsion (SE), Water soluble granule (SG), Soluble concentrate (SL), Spreading oil (SO), Water soluble powder (SP), Water soluble tablet (ST), Ultra-low volume (ULV) suspension, Tablet (TB), Ultra-low volume (ULV) liquid, Water dispersible granules (WG), Wettable powder (WP), Water dispersible powder for slurry seed treatment (WS), Water dispersible tablet (WT), a mixed formulation of CS and SC (ZC) or A mixed formulation of CS and SE (ZE), a mixed formulation of CS and EW (ZW).
7. The synergistic insecticidal composition as claimed in claim 6, wherein the composition is formulated as suspension concentrate or water dispersible granules.
8. The synergistic insecticidal composition, as claimed in claim 5 and 7, wherein the excipient is selected from the group comprising dispersing agent, wetting agent, anti-freezing agent, defoamer, biocide and thickener, and wherein the composition is formulated as suspension concentrate.
9. The synergistic insecticidal composition, as claimed in claim 5 and 7, wherein the excipient is selected from the group comprising dispersing agent, wetting agent, disintegration agent, defoamer and filler, and wherein the composition is formulated as water dispersible granule.
10. The synergistic insecticidal composition as claimed in claim 5, wherein the dispersing agent is selected from the group comprising amine salt of phosphate tristyryl phenol ethoxylated, acrylic copolymer, graft copolymer, naphthalene sulphonate of formaldehyde condensate, acrylic copolymer, lignin based sulphonate and combinations thereof, and present in an amount in the range from 1 to 10% w/w.
11. The synergistic insecticidal composition as claimed in claim 5, wherein the wetting agent is selected from the group comprising ethoxylated polyarylphenol phosphate ester, dioctyl sulphosuccinate, non-ionic ethoxylate, naphthalene alkyl aryl sulphonate, dioctyl sulfosuccinate, sodium lauryl sulfate and combinations thereof, and present in an amount in the range from 1 to 5% w/w.

12. The synergistic insecticidal composition as claimed in claim 5, wherein the anti-freezing agent is selected from the group comprising propylene glycol, diethylene glycol, monoethylene glycol and combinations thereof, and present in an amount in the range from 2 to 10% w/w.
13. The synergistic insecticidal composition as claimed in claim 5, wherein the defoamer is dimethyl polysiloxane emulsion and present in an amount in the range from 0.01 to 1% w/w.
14. The synergistic insecticidal composition as claimed in claim 5, wherein the biocide is selected from the group consisting of 20% aqueous dipropylene glycol solution of l,2-benzisothiazolin-3-one, formaldehyde and combinations thereof and present in an amount in the range from 0.01 to 0.50% w/w.
15. The synergistic insecticidal composition as claimed in claim 5, wherein the disintegration agent is selected from citric acid and sodium bicarbonate and present in an amount in the range from 1 to 5% w/w.
16. The synergistic insecticidal composition as claimed in claim 5, wherein the thickener is xanthan gum and present in an amount in the range from 0.01 to 0.50% w/w.
17. The synergistic insecticidal composition as claimed in claim 5, wherein the filler is selected from the group comprising bentonite clay, china clay, silica, kaolin, diatomaceous earth and combination thereof.