Title of Invention

A SYNERGISTIC INSECTICIDAL COMPOSITION CONTAINING CHLORONICOTYNYLE AND ORGANOPHOSPHORUS COMPOUNDS

Abstract A synergistic insecticidal composition comprising one or more Chloronicotynyle compound, in an amount ranging from 0.1 to 5 % by weight of the composition , one or more compounds falling within the group of Organophosphorus compounds in an amount ranging from 30 to 75% by weight of the composition and 20 to 69.9 % by weight of agriculturally acceptable carrier(s) and excepient(s).
Full Text FORM-2
THE PATENTS ACT, 1970
(39 of 1970)
COMPLETE SPECIFICATION
(See Section 10)
A SYNERGISTIC INSECTICIDAL COMPOSITION
CONTAINING CHLORONICOTYNYLE AND
ORGANOPHOSPHORUS COMPOUNDS.
We , UNITED PHOSPHORUS LIMITED, a company incorporated under the Companies Act, 1956 and having its
registered office at 3-11, GIDC, Vapi - 396 195, State of
Gujarat, India and having its office at Uniphos House, 11 th
Road. C.D.Marg, Khar (West), Mumbai - 400 052, State of
Maharashtra, India, INDIAN.
The following specification particularly describes the nature of this invention and the manner in which it is to be performed:

The present invention relates to a synergistic insecticidal composition containing Chloronicotynyle and Organophosphorus compounds. The composition of the present invention is especially useful for the control of agricultural pests, hygienic pests. The composition is highly effective for the protection of growing plants including: cotton, paddy, rice forage crops, sugarcane, cole crops, leafy vegetables, tobacco, tomatoes, potatoes, flowering ornamentals, vine crops and fruit trees from the ravages of insects. The insecticidal composition is found to be highly active against a wide variety of chewing, boring and sucking insects, e.g. Aphids, thrips, lepidopterous larvae, sawflies, leafminers, leafhoppers, cutworms, whiteflies, soil insects, termites and some species of bitting insects, such as rice water weevil on Colarado beetle etc.
Enhancement of the agricultural produce requires the protection of the crops and its produce from pest damage. Various chemicals and their formulations have been developed and are in use currently for the effective management of the insects pests. Due to non-judicious use of the hitherto known pesticides, the pests gain resistance and becomes hard to get them killed . Physically compatible pesticide mixtures exhibits a better pest management. These mixture shows multifaceted advantages than when applied individually, showing the synergistic effect.
The need for more food has to be met through higher yields per unit of the land, water, energy and time. Excessive use of mineral fertilizers and chemical pesticides have caused soil degradation, ground water pollution and the spread of the pests resistant to pesticides in several areas. Hence their judicious use includes avoiding prophylactic sprays, adopting strip treatment, spot application to only those areas with heavy incidence of pests, applying to the soil to avoid direct contact with the natural enemies and using selective or non-persistent pesticides. The systemic pesticides are sprayed at a concentration of 0.02 to 0.05 percent a.i., the contact pesticides are sprayed at 0.05 to 0.07 or even 0.1 percent a.i.. the soil application of the granular systemic insecticides varies from 1 to 2 kg a.i./ha, the fungicides are applied up to 2 g/1 depending upon the chemical used, pest species and season of the application.
Process for insecticidal agents and compositions have been developed to control insect pests and in practice have been used as a single or a mixed agent. However, process for the economically efficient and ecologically safe insect control compositions are still being sought. Process for the preparation of insecticidal compositions which allow for reduced effective dosage rates,

increased environmental safety and lower incidence of insect resistance are highly desirable. Although the rotational application of insect control agents having different modes of action may be adopted for good pest management practice, this approach does not necessarily give satisfactory insect control. Further, even though combinations of insect control agents have been studied, a high synergistic action has not always been found. Obtaining an insecticidal composition which demonstrates no cross-resistance to existing insecticidal agents, no toxicity problems and little negative impact on the environment is extremely difficult.
PRIOR ART
US patent application number 20010025050 dated September 27,2001 and other application number 20020193352 dated December 19, 2002 describe the insecticidal mixtures of Chloronicotynyle compounds with one or more synergistic compound (s) selected from certain specific insecticide compounds. Amongst these synergistic compounds only three compounds belonging to the oragnophosphorus compounds , namely 0,0-dimethyl S-(4-oxo-1,2,3-benzotriazine-3-methyl) dithiophosphate (of trade name M-Gusathion, common name Azinphos-methyl); O-ethyl 0-(4-bromo-2-chloropheriyl)-s-N-propyl thiophosphate (of trade name Curacron, common name Profenofos); 0,S-dimethyl phosphoamidothioate (of trade name Tamaron, common name Methamidophos) have been specified to impart synergism . No other compounds falling under this group have been stated . This means that the other compounds falling within the group of Organophosphorus compounds do not effect any synergism when combined with Chloronicotynyle compounds according the invention disclosed in the said US patent applications .
The compounds other than Organophosphorus compounds which can be combined with Chloronicotynyle compounds consist of 3,5-dimethyl-4-methylthiophenyl N-methyl carbamatefMesurol]; 4-bromo-2-(4-chlorophenyl)-2-(emoxymemyl)-5-(trifluoromethyl)-lH-pyixol-e-3-carbonitrile [AC 303, 630]; N-[2,6-bis(-l-memylemyl)-4-phenoxyphenyl)-N'-(l,l-dimethylethy- l)-thiourea [CGA 106 630; Polo]; abamectin; ethyl 3-t-butyl-l-dimethylcar-bamoyl-lH-l,2,4-triazol-5-ylthio)-acetate [Triazuronj; 6,7,8,9,10,10 - hexa chloro-l,5,5A,6,9,9A-hexahydro-6,9-methane - 2,4,3 - benzodioxa thiepine 3-oxide [Endosulfan; Thiodan]; trans-5-(4-chlorophenyl)-N-cyclohexyl-4-methyl-2-oxo-3-thiazolidine - carboxamide [Cesar; Hexythiazox]; 3,6-bis-(2-chlorophenyl)-1,2,4,5-tetrazine [Clofentezin; Apollo]; ethyl [2-(4-phenoxyphenoxy)-ethyl]carbamate [Fenoxycarb; Insegar]; 2-[l-methyl-2-(4-phenoxyphenoxy) ethoxy]pyridine [Pyriproxyfen; Tiger]; N - cyclopropyl -1,3,5 - triazine -2,4,6-

triamine [Cyromazine]; benzoic acid [-2-benzoyl-l-(l,l-dimethyl)]hydrazide [RH 5849]; 5-amino-3-cyano - 1 - ( 2, 6- dichloro-4-trifiuoromethylphenyl)-4-trifluoro methyl thiono pyrazole [Fipronil]; cis-(2,3,5,6-tetrafluoro-4-methylphenyl)methyl - 3 - (2-cWoro-3,-3,3-trifluoro-l-propenyl)-2,2-dimethyl-cyclo propane-carboxylate [Tefluthrin; Force]; l,5-bis-(2,4-dimethylphenyl) -3-methyl-l,3,5-triazape- nta-l,4-dione [Amitraz]; 3,5-dimethylbenzoic acid 1-(1,1-dimethyle%l)-2-(4-ethylbenzoyl)hydrazide [RH 5992]; N-[[2,5-dichloro-4-(1,1,2,3,3,3-hexafluoropropoxy) phenyl]-aniinocarbonyl]-2,6-difluorobenzamide [Match];(4-ethoxyphenyl)-[3-(4-fluoro-3-phenoxyphenyl) propyl] dimethylsilane [HOE 498]; and (E)-4,5-dmydro-6-memyl-4-[(3-pyridinylmethylene)amino]-1,2,4- triazin-3-(2H)-one [Chess].
Most of the above mentioned compounds employed in the composition specified in the above mentioned US patent applications resulting in synergism are all earlier generation insecticides having high toxicity . These compounds are currently restricted and / or banned for use in certain countries due to the toxicity
Therefore, though the compositions disclosed in the above said US applications have synergistic activity, their practical application for use however is either limited or banned
The invention disclosed in the said US applications does not disclose the use of any other advance and safer organophosphorus insecticide such as Acephate, Phosphamidon, Chlorpyrifos Azamethiphos, Azinphos-ethyl, Cadusafos, Chlorethoxyfos, Chlorfenvinphos, Chlormephqs, Chlorpyrifos, Chlorpyrifos-methyl, Cumaphos, Cyanophos, Demeton-S-methyl, Diazinon, Dichlorvos, Dicrotophos, Dimethoate, Dimethylvinphos, Dioxabenzofos, Disulfoton, Ethion, Ethoprophos, Famphur, Fenitrothion, Fenthion, Fonofos, Formothion Heptenophos, Isazofos, Isofenphos, Isoxathion, Malathion, Mecarbam, Mephosfolan, Methidathion, Mevinphos, Monocrotophos, Naled, Omethoate, Oxydemeton-methyl, Parathion, Parathion-methyl, Phenthoate, Phorate, Phosalone, Phosmet, Phosphamidon, Phoxim, Prirniphos-ethyl, Primiphos-methyl, Propaphos, Propetamphos, Prothiofos, Pyraclofos, Quinalphos, Sulfotep, Sulrpofos, Temephos, Terbufos, Tetrachlorvinphos, Thiometon, Triazophos, Vamidothion. This mean that these advanced and safer organophosphorus compounds have no synergistic effect when combined with Chloronicotynyle compounds
In addition the invention disclosed in the said US applications describes only the effect of using two insecticidal compounds as admixture in a tank-mix form

at the time of the application on crops. In other words the ingredients have to be mixed as and when required at the place of application. In short the inventions disclosed in these patent applications do not result in a compatible and storage stable formulation product, prepared in the manufacturing plant and made available to use in a packed container, on shelf. It also does not disclose the specific concentrations or concentration range of the compound that exhibits synergistic effect.
This means that if the ingredients are mixed in advance and kept, their activity may be either be reduced or totally lost. Thus the composition cannot be used as ready to use one
Thus there is need to develop and improve insecticidal composition to increase agricultural yield , the composition having high synergistic action, having no cross resistance to existing insecticidal agents, avoid excess loading of the toxicant to environment and neglligible impact to environmental safety. It also necessitates the need for synergistic insecticidal composition which could be physico-compatible formulations in the form of storage stable, safely packed, ready to use formulation. The invention achieves the above objective by providing a synergistic composition with many advantages
Therefore, it is an object of this invention to provide a synergistic insecticidal composition containing Chloronicotynyle and Organophosphorus compounds which demonstrates a high controlling effect with reduced crop protection cost, increased crop yield and reduced environmental load.
Another objective of the present invention is to provide a synergistic insecticidal composition containing Chloronicotynyle and Organophosphorus compounds useful for the synergistic insect control and enhanced crop protection.
Yet another objective of the present invention is to provide a synergistic insecticidal composition containing Chloronicotynyle and Organophosphorus compounds which delays the dominance of the resistant strains of pests.
Still another objective of the present invention is to provide a synergistic insecticidal composition containing Chloronicotynyle and Organophosphorus
compounds which has a broader spectrum of activity and reduces risk of developing resistance.

Another objective of the present invention is to provide a synergistic insecticidal composition containing Chloronicotynyle and Organophosphorus compound (s) which can achieve effective and economic control of undesirable species.
Yet another objective of the present invention is to provide a synergistic insecticidal composition containing Chloronicotynyle and Organophosphorus compounds which can improve biological performance in single application and minimise occupational exposure and hazards.
Still another objective of the present invention is to provide a synergistic insecticidal composition containing Chloronicotynyle and Organophosphorus compounds which decreases the cost of application, save fuel cost, labour cost and save applicator's precious time and therefore very economical
Another objective of the present invention is to provide a synergistic insecticidal composition containing Chloronicotynyle and Organophosphorus compounds which reduces the wear of equipment and losses caused by mechanical damage to crops and soil.
Accordingly the present invention provides a synergistic insecticidal composition containing Chloronicotynyle and Organophosphorus (OP) compounds for insect control comprising one or more compounds falling within the group of Chloronicotynyle in an amount ranging from 0.1 to5 % by weight of the composition , one or more compounds selected from the group of Organophosphorus (OP) compounds except Azinphos-methyl, Profenofos and Methamidophos, in an amount ranging from 30 to 75% by weight of the composition and 69.9 to 20 % by weight of conventional agriculturally acceptable carrier(s) and or excipients.
The compound(s) falling under the group of Chloronicotynyle may be selected
from Inndacloprid^^^AjEetamiprid, preferably Imidacloprid which may be
T^cJWc^jrnid^ The compound(s) falling under
the group of Organophosphorus compounds may be selected from Acephate. Phosphamidon preferably, Acephate (purity 97% minimum) and Phosphamidor (purity 92% rmnimum).
The amounts of the compounds falling within the groups of Chloronicotynyle like Imidacloprid, may preferably ranges from 0.1 to 5.0% by weight and Organophosphorus like Acephate, Phosphamidon, preferably may be in the range of 30 to 75 % by weight of the composition, more preferably in the range of 0.5 to 3.0 % of Chloronicotynyle compounds and 35 to 60 % of Organophsophorus compounds by weight of the composition.


The amounts of the Chloronicotynyle and Organophosphorus (OP) groups of compounds used in the process may be selected from Acephate, Phosphanridon, Chlorpyrifos, Dichloryous, Monocrotophos, Profenophos, Quinalphos and others and may vary accordingly to prevailing
compound present, insect pest attack strength, type of pests, application timing, weather conditions, soil conditions, mode of application, topographical character, target crop and the like.
The compound(s) falling under the group of Chloronicotynyle may be selected
from imidacloprid , Acetamiprid, preferably hnidacloprid which may be
Technical grade and purity of 95% rninimum. The compound(s) falling under
the group of Organophosphorus compounds may be selected from Acephate,
Phosphamidon preferably, Acephate (purity 97% minimum) and Phos£hamidcm
(purity 92% minimum).
The Organophosphorus (OP) group of compounds which can be used in the
process of me present invention may be selected from Acephate, Azamethiphos,
Azinphos-ethyl, Cadusafos, Chlorethoxyfos, Chlorfenvinphos, Chlormephos,
Chlorpyrifos, Chlorpyrifos-memyl, Cumaphos, Cyanophos, Demeton-S-methyl,
Diazinon, Dichlorvos, DicTotophos, Dimethoate, Dimethylvinphos,
Dioxabenzofos, Disulfoton, Emion, Ethoprophos, Famphur, Fenitrothion,
Fenmion, Fonofos, Formomion, Heptenophos, Isazofos, Isofenphos, Isoxathion,
Malathion, Mecarbam, Mephosfolan, Methidaraion, Mevinphos,
Monocrotophos, Naled, Omethoate, Oxydemeton-methyl, Paramion,
Parathion-methyl, Phenmoate, Phorate, Phosalone, Phosmet, Phosphamidon, Phoxim, Primiphos-ethyl, Primiphos-methyl, Propaphos, Propetamphos, Promiofos, Pyraclofos, Quinalphos, Sulfotep, Sulrpofos, Temephos, Terbufos, Tetrachlorvinphos, Thiometon, Triazophos, Vamidothion. The more preferred insecticidal compound selected are Acephate and Phsophsmidon and their mixtures.
The first active ingredient of the insecticidal composition of the invention includes one or more compounds selected from Chloronicotynyle group. The preferred insecticidal compounds for use in the process of the invention are Acetamiprid and imidacloprid . The more preferred insectieidal eompound for use in the process of the invention is Imidacloprid.
An agriculturally acceptable carriers) may he solid, liquid or both. Solid carries are essentially: mineral earth such as silicas, silica gels, silicates, talc, kaolin, montmorillonite, attapulgite, pumice, sepiolite, bentonite, limestone, lime,

chalk, bole, loes, clay, dolomite, diatomaceous earth, calcite, calcium sulfate, magnesium sulfate, magnesium sulfate, magnesium oxide, sand, ground plastics, ferilizers such as ammonium sulfate, ammonium phosphat, ammonium nitrate, ureas, and crushed products of vegetable origin such as cereal meal, tree bark meal, wood meal and nutshell meal, cellulose powders, or other solid carriers.
The surfactant(s) which are non-ionic, cationic and/or anionic in nature and surfactant mixtures which have good emulsifying, dispersing and wetting properties, depending on the nature of the active ingredient to be formulated. Suitable anionic surfactants can be both so-called water-soluble soaps and water-soluble synthetic surface-active compounds. Soaps which may be mentioned are the alkali metal, alkaline earth metal or substituted or unsubstituted ammonium salts of higher fatty acids (C10 - C22 ), for example the sodium or potassium salt of oleic or stearic acid, or of natural fatty acid mixtures.
According to another feature of the present invention there is provided a process for preparing synergistic insecticidal composition which comprises mixing thoroughly, one or more compounds falling within the group of Chloronicotynyle in an amount ranging from 0.1 to 5 % by weight of the composition , one or more compounds falling within the group of Organophosphorus compounds except Azinphos-methyl, Profenofos and Methamidophos, in an amount ranging from 30 to 75% by weight of the composition and 69.9 to 20 % by weight of the composition conventional agriculturally acceptable excipient(s) and or carrier(s).
The process of this invention include intensive mixing and/or milling of the active ingredients with other substances, such as stabilizer, emetic agent, disintegrating agent, antifoaming agent, wetting agent, dispersing agent, binding agent, dye(s), fillers, carriers, surface active compounds (surfactants), and optionally solid and/or liquid auxiliaries and/or adjuvants such as wetters, adhesives, dispersants or emulsifiers.
Such a process has been made the subject matter of our co pending application no 55?> MUM 02 from which this application has been divided out under Section 16 of the Patents Act, 1970.
The compound(s) falling under the group of Chloronicotynyle may be selected from Imidacloprid , Acetamiprid, preferably Imidacloprid which may be Technical grade and purity of 95% minimum. The compound(s) falling under the group of Organophosphorus compounds may be selected from Acephate, Phosphamidon preferably , Acephate (purity 97% minimum) and Phosphamidon (purity 92% minimum).

The amounts of the compounds falling within the groups of Chloronicotynyle like Imidacloprid, may preferably ranges from 0.1 to 5.0% by weight and Organophosphorus compounds, except Azinphos-methyl, Profenofos and Methamidophos, like Acephate, Phosphamidon, preferably may be in the range of 30 to 75 % by weight of the composition, more preferably in the range of 0.5 to 3.0 % of Chloronicotynyle compounds and 35 to 60 % of Organophsophorus compounds by weight of the composition.
The amounts of the Chloronicotynyle and Organophosphorus (OP) groups of compounds used in the process may be selected from Acephate, Phosphamidon, Chlorpyrifos, Dichlorvous, Monocrotophos, Quinalphos and others and may vary accordingly to prevailing conditions such as the particular OP compound present, insect pest attack strength, type of pests, application timing, weather conditions, soil conditions, mode of application, topographical character, target crop and the like.
The Organophosphorus (OP) group of compounds which can be used in the
process of the present invention may be selected from Acephate, Azamethiphos,
Azinphos-ethyl, Cadusafos, Chlorethoxyfos, Chlorfenvinphos, Chlormephos,
Chlorpyrifos, Chlorpyrifos-methyl, Cumaphos, Cyanophos, Demeton-S-methyl,
Diazinon, Dichlorvos, Dicrotophos, Dimethoate, Dimethylvinphos,
Dioxabenzofos, Disulfoton, Ethion, Ethoprophos, Famphur, Fenitrothion,
Fenthion, Fonofos, Formothion, Heptenophos, Isazofos, Isofenphos, Isoxathion,
Malathion, Mecarbam, Mephosfolan, Methidathion, Mevinphos,
Monocrotophos, Naled, Omethoate, Oxydemeton-methyl, Parathion,
Parathion-methyl, Phenthoate, Phorate, Phosalone, Phosmet, Phosphamidon, Phoxim, Primiphos-ethyl, Primiphos-merhyl, Propaphos, Propetamphos, Prothiofos, Pyraclofos, Quinalphos, Sulfotep, Sulrpofos, Temephos, Terbufos, Tetrachlorvinphos, Thiometon, Triazophos, Vamidothion. The more preferred insecticidal compound selected are Acephate and Phsophsmidon and their mixtures.
The preferred compounds selected from the Chloronicotynyle group in the process of preparing the insecticidal composition of the present invention includes Acetamiprid and Imidacloprid . The more preferred compound for use in the process of the invention is Imidacloprid .
The name "Acetamiprid " describes a chemical substance having a molecular weight 222.7; is in the form of colourless crystals, m.pt. 98.9 ° C; solubility in water at 25 ° C , 4200 mg/1. Soluble in acetone, methanol, ethanol, dichloromethane, chloroform, acetonitrile and tetrahydrofuron. Stable in buffered solutions at pH 4,5,7. Degraded slowly at pH 9 and 45° C. Stable under

sunlight. The molecule have following formula :

(E)- N'-[(6-chloro-3-pyridyl)methyl]-N- cyano-N - methylacetamidine. It is a systemic insecticide for soil and foliar application. Controls Hemiptera, especially aphids, Thysanoptera and Lepidoptera on wide range of crops, especially vegetables, fruits and tea.
Its acute oral LDso for male rats 217, female rats 146, male mice 198, female mice 184 mg/Kg . Acute percutaneous LDso for male and female rats > 2000 mg/Kg . Non irritating to skin and eyes ( rabbits) During inhalation LCso (4 h) for male and female rats is about > 0.29 mg/1.
The name "Imidacloprid " describes a chemical substance having a molecular weight 255.7; is in the form of colourless crystals with a week characteristic odour, m.pt. 144 ° C; solubility in water at 20° C , 0.61 g/1. In dichloromethane 55, isopropanol 1.2, toluene 0.68, n.hexane
l-(6-chloro-3-pyridylmethyl)-N-nitroinddazolidin-2-yldeneamine. It acts on the central nervous system, causing blockage of postsynaptic nicotinergic acetylcholine receptors. It is a systemic insecticide with contact and stomach action. Readily taken up by the plant and further distributed acropetally, with good root-systemic action. It controls the sucking insects, including rice-hoppers, aphids, thrips and whiteflies. Also effective against soil insects, termites and some species of biting insects, such as rice water weevil and Colorado beetle. It has no effect on nematodes and spider mites. Used as seed dressing, as soil treatment and as foliar treatment in different crops,e.g. rice, cotton, cereals maize sugar beet, potatoes, vegetables citrus fruit, pome fruit and stone fruit.

Its acute oral LDso for male and female rats 450, mice 150 mg/Kg. Acute percutaneous LDso (24h) for rats > 5000 mg/Kg . Non irritating to skin and eyes ( rabbits). Not a skin sensitiser. During inhalation LCso (4 h) for female rats is > 5323 mg/m 3 air (aerosol). Not mutagenic or teratogenic .
Descriptions of the above-listed commercially available compounds may be found in "The Pesticide Manual" 11th Edition, British Crop Protection Council (1997) among other publications.
The organophosphorus compounds have high insecticidal and acaricidal activity; have wide spectrum of the action on plant pests; low persistence and breakdown to form products nontoxic to human and animals; systemic action of a number of the compounds; low dosage of the compound per unit area treated; relatively rapid metabolism in vertebrate organism and absence of accumulation in then-bodies, and also comparatively low chronic toxicity; rapidity of action on plant pests.
The preferred compounds for use as Organophosphorus compounds are Acephate and Phosphamidon.
"Acephate" (0,S-dimethylacetylphosphoramidothioate) belongs to
organophosphorus group and has the structural formula as follows:

(OfS-dimethylacetylphosphoramidothioate)
It is a cholinesterase inhibitor . It is a systemic insecticide with contact and stomach action and is of moderate persistence with residual activity lasting about 10-21 days. It controls a wide range of chewing and sucking insects , e.g. aphids, thrips, lepidopterous larvae, sawflies, leaf miners, leafhoppers, cutworms, etc. in fruits (including citrus), vines, hops, olives, cotton soyabean, peanuts, macadamia nuts, beet, brassicas, celery, beans, potatoes, rice, tobacco , ornamentals, forestry, and other crops. It is non-phytotoxic to most crop plants but marginal leaf burn may occur on Red Delicious apples.

Technical grade Acephate is > 97 % pure. It has a molecular weight of 183.2 is a colourless solid; melting point 88 -90°C; solubility at room temperature : about 790 g/1 water ( 20 Q C) ; 151 acetone, > 100 ethanol; 35 ethyl acetate, 16 benzene, 0.1 hexane (all in g/1, 20 ° C ). Relatively stable to hydrolysis ; DTso 40°C60h(pH9),710h(pH3).
The "Phosphamidon" as a commercial compound contains 70 % m/m (Z) -isomer (P -isomer) (which has the greater insecticidal activity) and 30 % m/m (E)-isomer (a- isomer). Phosphamidon is a systemic insecticide and acaricide with stomach and slight contact action. It is a pale yellow liquid with the molecular structure as follows:

2-chloro-2-diethylcarbamoyl-l-methylvinyldimethylphosphate
It is absorbed by the leaves and roots. It is cholinesterase inhibitor. It is used in control of sucking, chewing and boring insects, and spider mites on a very wide range of crops. Specifically used in control of leaf beetles and stem borers in rice; stem borers in sugarcane; colarado beetles in potatoes; thrips in cotton; etc. It is also used to control aphids, sawflies, suckers, fruit flies, leaf miners, moth and beetle larvae, and many other insects in fruits, vines, olives, vegetables, ornamentals, cereals, beet, maize, alfalfa, many other crops and in forestry. It is non-phytotoxie, except some varieties of cherry, plum, peach and sorghum. It is compatible with many other pesticides, but incompatible with alkaline materials
It has a boiling point 162 ° C (at 1.5 mm Hg); Solubility- miscible with water, acetone, dichloromethane, toluene and other common organic solvents, with the exception of aliphatic hydrocarbons e.g. solubility in hexane 32 g/1 (25 °C). It gets rapidly hydrolysed in alkali: DT so ( calculated) (20 °C) 60 d ( pH 5); 54 d (pH 7); 12 d (pH 9).

Its acute oral LD 50 for rats 17.9-30 mg/Kg. Acute percutaneous LD 50 for rats 374-530, rabbits 267 mg/Kg. Slight skin irritation, moderate eye irritation in rabbits observed. During inhalation LC 50 (4 h) for rats is about 0.18, mice 0.033 mg/lair.
In mammals, following oral administration, 85- 90 % of the dose is excreted within 24 hours, almost entirely in the urine. Complete metabolism occurs during the passage, by oxidative dealkylation of the amide group and hydrolysis of the phosphorus ester bond.
In plants, an ethyl group is split off from the amide group and simultaneously or subsequently the ester bond between the side chain and phosphorus atom is hydrolyticaUy cleaved. De-chlorination also occurs, as does further degradation to small fragments.
Pesticidal compositions are often formulated and transported in a concentrated form which is subsequently diluted by the user before application. The presence of small amounts of a surfactant facilitate this process of dilution. Thus, preferably a composition according to the invention comprises if desires at least one surfactant. For example, the composition may contain one or more carriers and at least one surfactant.
A carrier in a composition according to the invention is any material with which the active ingredient is formulated to facilitate application to the locus to be treated, which may for example be a plant, seed or soil, or to facilitate storage, transport or handling. A carrier may be a solid or a liquid, including material which is normally a gas but which has been compressed to form a liquid or a combination thereof. The combination composition of the invention may also contain other additive such as surfactants, emulsifiers, defoamers, buffers, thickeners, dyes, extenders, emetic agent(s) and the like.
Surprisingly, it has been found that the composition prepared by the process of the present invention has superior insect control at lower level of the combined concentrations of the active agents employed than that may be achieved when the active ingredients are applied alone. In other words , the process of preparing the composition of the present invention and the composition resulting there from , is not a mere admixture of the active ingredients resulting in the aggregation of the properties of the active ingredients employed in the composition. The process involves judicial selection of the appropriate amounts of the active ingredients which combination only imparts synergism to the resulting composition imparting to it the unexpected and unique properties

Advantageously, known adjuvants which are known to enhance the activity, may also be incorporated in the process of preparing the composition.. The composition resuting from the process may be dispersed in a solid or liquid diluent for application to the insect, its food supply, breeding ground or habitat as a dilute spray or as a solid dust or dust concentrate.
As a commodity the composition is generally is in a ready to use form which may be diluted at the place of application for suitable concentarion of the active ingredients.
In general, the synergistic effect may be achieved at application rates of the active ingredient of about 20 to 25 g/ha of Imidacloprid in combinaiton with 250 to 750 g/ha of Acephate; preferably in about 1 to 1500 g/ha. In general, the synergistic effect may be achieved at application rates of the active ingredient of about 20 to 25 g/ha of Imidacloprid in combinaiton with 0.03 to 600 g/ha of Phosphamidon; preferably in about 0. 5 to 750 g/ha.
Preferred combination of the composition prepared by the process of the present invention are those combination wherein the active ingredient ratio (weight/weight) of Chloronicotynyle : Organophosphorus compound is about 1 : 1 to 1 : 1000. More preferred combination of the invention are combination of Chloronicotynyle (Imidacloprid) and Organophosphorus (Acephate) wherein the active ingredient ratio (weight/weight) of Imidacloprid : Acephate is about 1 : 2 to 1 : 800, most preferred is about 1 : 5 to 1 : 800. More preferred combination of the invention are combination of Chloronicotynyle (Imidacloprid) and Organophosphorus (Phosphamidon) wherein the active ingredient ratio (weight/weight) of Imidacloprid : Phosphamidon is about 1 : 2 to 1 : 800, most preferred is about 1 : 5 to 1 : 800.
Advantageously, the Chloronicotynyle compound or a mixture thereof may be formulated with a second insecticidally effective ingredient alone or a mixture thereof and optionally other agriculturally acceptable carrier and formulation adjuvants. Said formulation may be dispersed in a solid or liquid diluent for application to the insect, its food supply, breeding ground or habitat as a dilute spray or as a solid dust or dust concentrate.
As a commodity the compositions may preferably be in a concentrated form (i.e. 30.1 to 80 %) whereas the end user generally employs diluted compostions. The compositions may be diluted to a concentration down to 0.001% of active ingredient. Preferably, the formulation comprise approximately from 30.1 to 80

% by weight, of active ingredients. The doses usually are in the range from 0.01 to 10 kg a.i./ha. The ratio of the essential active ingredients of the composition of the invention is about 0.1- 5.0 weight part of Imidacloprid to about 30 -75 weight parts of one or more compounds selected from Organophosphorus group .
Advantageously, the composition of the invention may be formulated in powder, solid or liquid form . A preferred powder form comprises of a synergistically effective amount of a combination of Chloronicotynyle plus one or more compounds selected from Organophosphorus group and solid or liquid inert substance(s). A preferred soluble powder composition may contain by weight about 30.1 % to 80 % active ingredients preferably Imidacloprid in combination with Acephate and or Phosphamidon .
The forms of application of the compositions according to this invention depend on the intended purposes; in any case, they guarantee uniform a distribution of the active ingredients. They can be applied, for example, in the form of directly sprayable aqueous solutions, powders, suspensions, also highly-concentrated aqueous suspensions or dispersions, dusts, materials for spreading or granules, by spraying, atomizing, dusting or pouring. Aqueous use forms can be prepared from soluble powders (SP) by adding water.
Alternatively, concentrates which consist of insecticidally active ingredients, wetter, adhesive, dispersant or surfactants and, if appropriate solvent or oil may be prepared, and such concentrates are suitable for dilution with water.
Aqueous dispersions and suspensions, for example compositions obtained by diluting the formulated product according to the invention with water, also lie within the scope of the invention.
The biological activity of the active ingredient can also be increased by including an adjuvant in the spray dilution. An adjuvant is defined here as a substance which can increase the biological activity of an active ingredient but is not itself significantly biologically active. The adjuvant can either be included in the formulation as a co-formulant or carrier, or can be added to the spray tank together with the formulation containing the active ingredient.
In actual practice, the composition of the invention may be applied to the plant foliage or plant stem or to the insect habitat or to the locus of a hygienic pest as a dilute spray prepared from any of the above-said formulations.

The synergistic effective amount of the combination of hnidacloprid and Organophosphorus (OP) compound selected from Acephate, Phosphamidon, Chlorpyrifos, Dichlorvous, Monocrotophos, Quinalphos and others may vary accordingly to prevailing conditions such as the particular OP compound present, insect pest attack strength, type of pests, application timing, weather conditions, soil conditions, mode of application, topographical character, target crop and the like.
The composition of the present invention is superior insecticidal compositions and are especially useful for the control of agricultural pests, hygienic pests. Said compositions are highly effective for the protection of growing plants including: cotton, paddy, rice forage crops, sugarcane, cole crops, leafy vegetables, tobacco, tomatoes, potatoes, flowering ornamentals, vine crops and fruit trees from the ravages of insects.
The synergistic insecticidal composition prepared by the process of the invention is found to be highly active against a wide variety of chewing, boring and sucking insects, e.g. Aphids, thrips, lepidopterous larvae, sawfkes, leafminers, leafhoppers, cutworms, whiteflies, soil insects, termites and some species of bitting insects, such as rice water weevil on Colarado beetle etc.
The present invention highlights the synergistic effect of the combination of the the compounds falling under Chloronicotynyle and Organophosphorus insecticide groups. Following the right use of the invented technology and the composition of the invention with a formulations having a multi-pesticide components i.e. pesticide mixture, formulation prepared with an extra care of physical compatibility by purposefully specially selected solvents, carriers and the surfactants, thickeners, stabilisers etc. exhibits better pest management.
These and other advantages of the invention may become more apparent from the examples set forth herein below. These examples are provided merely as illustrations of the invention and are not intended to be construed as a limitation thereof.
Example-1
A composition containing hnidacloprid 1.8% + Acephate 50 % [ 51.8 % SP] :

Composition
Ingredient Quantity (% w/w)
Imidacloprid Techical (purity 95%) 1.8948
Acephate Technical (purity 97%) 51.5465
Stabilizer (Sodium alginate) 3.0000
Emetic agent (Bitrex) 0.0002
Disintegrating agent (Zeolite) 5.0000
Antifoaming agent (Antimousse 426 -R) 0.1000
Wetting cum dispersing agent (Lisapol BN - 200) 1.5000
Anticaking agent (anhydrous Magnesium sulphate) 0.0100
Dye(s) 0.0010
Fillers (s) (Insilco and Kaolex) 36.9475
Total 100.00 % (w/w)
The above said synergistic insecticidal composition can be prepared by mixing thoroughly, for 1/2 an hour, Imidacloprid, antimousse 426 -R, Lisapol BN -200,anhydrous Magnesium sulphate, and insilco , Kaolex Acephate, sodium alginate ,Bitrex, Zeolite), and Ocean blue in a pre-blender equipped with agitator to get a homogenous mixture of all the ingredients. Thereafter the homogenous mixture obtained is micronised to get particle size of 2 - 10 microns which is post-blended to yield the synergistic above mentioned insecticidal composition
Example-2
A composition containing Imidacloprid 2.0 % + Acephate 45.0 % [47%SP] :

Composition Ingredient Ouantitv (% w/w)
Imidacloprid Techical (purity 95%) 2.1053
Acephate Technical (purity 97%) 46.3918
Stabilizer (Sodium alginate) 2.7500
Emetic agent (Bitrex) 0.0002
Disintegrating agent (Zeolite) 5.3000
Antifoaming agent (Antimousse 426- R) 0.1000
Wetting cum dispersing agent (Lisapol BN -200) 1.5000
Anticaking agent (anhydrous Magnesium sulphate) 0.0100
Dye(s) (Malachite green) 0.0010
Fillers (s) (Insilco and Kaolex) 41.8417
Total 100.00% (w/w)

The above said synergistic insecticidal composition can be prepared by mixing thoroughly, for 1/2 an hour, Imidacloprid, antimousse 426 -R, Lisapol BN -200,anhydrous Magnesium sulphate, and insilco , Kaolex Acephate, sodium alginate ,Bitrex , Zeolite and malachite green in the above menhtioned proportions in a pre-blender equipped with agitator to get a homogenous mixture of all the ingredients. Thereafter the homogenous mixture obtained is micronised to get particle size of 2 - 10 microns which is post-blended to yield the synergistic above mentioned insecticidal composition
Example-3
A composition containing Imidacloprid 3.0 % + Acephate 40.0 % [ 43 % SP] :
Composition
Ingredient Quantity (% w/w)
Imidacloprid Techical (purity 95%) 3.1579
Acephate Technical (purity 97%) 41.2372
Stabilizer (Magnesium stearate) 3.5000
Emetic agent (Bitrex) 0.0003
Disintegrating agent (Zeolite) 6.0000
Antifoaming agent (Antimousse 426 -R) 0.0500
Wetting cum dispersing agent (Lisapol - D) 2.0000
Anticaking agent (anhydrous Magnesium sulphate) 0.0200
Dye(s) (Methyl Violet) 0.0015
Fillers (s) (Insilco and Kaolex ) 44.0331
Total 100.00 % (w/w)
The above said synergistic insecticidal composition can be prepared by mixing thoroughly, for 1/2 an hour, Imidacloprid, antimousse 426 -R, Lisapol D,anhydrous Magnesium stearate insilco , Kaolex Acephate, magnesium stearate ,Bitrex , Zeolite, and methyl violet in a pre-blender equipped with agitator to get a homogenous mixture of all the ingredients. Thereafter te homogenous mixture obtained is micronised to get particle size of 2 - 10 microns which is post-blended to yield the synergistic above mentioned insecticidal composition
Example-4
A composition containing Imidacloprid 2.5 % + Acephate 55 % +[57.5 % SP] :

Composition
Ingredient Quantity (% w/w)
Imidacloprid Techical (purity 95%) 2.6316
Acephate Technical (purity 97%) 56.7011
Stabilizer (Potassium alginate) 4.0000
Bmetic agent (Amrex) 0.0003
pisintegrating agent (Zeolite) 6.0000
Antifoaming agent (Antimousse 426-R) 0.1000
Wetting cum dispersing agent (Lisapol - D) 1.2500
Anticaking agent (anhydrous Magnesium sulphate) 0.0200
Pye(s) (Ocean Blue) 0.0020
Fillers (s) (Insilco and kaolex) 29.2950
Total 100.00 % (w/w)
The above said synergistic insecticidal composition can be prepared by mixing thoroughly, for 1/2 an hour, Imidacloprid, #ntimousse 426 -R, Lisapol D,anhydrous Magnesium sulphate, and insilco, Kaolex, Acephate, Potassium alginate Amrex, Zeolite, end Ocean blue in the above said proportions in a pre-blender equipped with agitator to get a homogenous mixture of all the ingredients. Thereafter te homogenous mixture obtained is micronised to get particle size of 2 - 10 microns which is post-blended to yield the synergistic above mentioned insecticidal composition
Example -5 A composition containing Imidacloprid 1.8 % + Acephate 50.0 % [51.8 % SP]

Composition
Component Content (%w/w)
Acephate active ingredient 50.00
Imidacloprid active ingredient 1.80
Surfactant -[Alkyl Naphthalene Sulfonate] 3.00
Inert carrier [Precipitated Silical 45.20
Total WO.W%wlw
The above said synergistic insecticidal composition can be prepared by mixing thoroughly, for 1/2 an hour, Acephate , Imidacloprid Alkyl Naphthalene Sulfonate Precipitated Silica in the above mentioned proportions in a pre-blender equipped with agitator to get a homogenous mixture of all the ingredients

Thereafter Ije homogenous mixture obtained is micronised to get particle size of 2-10 microns which is post-blended to yield the synergistic above mentioned insecticidal composition
Example-6
A composition containing Imidacloprid 1.8 % + Acephate 50% [51.8 % Dry Flowable]:
Composition
Ingredient Quantity (% w/w)
Acephate Technical (purity 97%) 51.5465
Imidacloprid Techical (purity 95%) 1.8948
Stabilizer (Ammonium sulphate) 3.0000
Emetic agent (Bitrex) 0.0002
Disintegrating agent (Attapulgite) 5.0000
Antifoaming agent (Antimousse 426 -R) 0.1000
Wetting cum dispersing agent (Lisapol - D) 1.5000
Anticaking agent (anhydrous Magnesium sulphate) 0.0100
Dye(s)(Oceanblue) 0.0010
Fillers (s) (Insilco and Kaolex) 36.9475
Total 100.00 % (w/w)
The above said synergistic insecticidal composition can be prepared by mixing Acephate Imidacloprid Techical (purity 95%), Ammonium sulphate, Bitrex, Attapulgite, Antimousse 426 -R, Lisapol - D, anhydrous Magnesium sulphate, ocean blue , Insilco and Kaolex in the above said proportions in a pre-blender equipped with agitator to get a homogenous mixture of all the ingredients. Thereafter the homogenous mixture obtained is micronised to get particle size of 2 - 10 microns which is post-blended to yield the synergistic above mentioned insecticidal composition
The resulting homogenous mixture is thereafter granulated through granulator maintaining the inlet temperature in the range of 30 - 35 ° C and the outlet temperature of in the range of 40 - 45 ° C and the rate and quantity of material fed to the granulator to minimize clumping together of the granulated product.; The resulting product is conditioned, dried, sieved, sized and post-blended to yield the synergistic insecticidal composition of the invention in dry flowable form.

Example -7 A composition containing Imidacloprid 2.0 % + Phosphamidon 40% [42 % SP] :
Composition
Ingredient Quantity (% w/w)
Imidacloprid Technical (purity 95%) 2.1053
Phosphamidon Technical (purity 92%) 43.4783
Stabilizer (Priochem PN) 2.0000
Emetic agent (Bitrex) 0.0030
Disintegrating agent (Zeolite) 5.0000
Antifoaming agent (Antimousse 426 -R) 1.0000
Wetting agent (Supragil MNS -90) 3.0000
Dispersing agent (Supragil WP) 7.0000
Binding agent (PVP K-30) 0.5000
Dye(s) (Methyl violet) 0.5000
Filler(s) (Insilco and Kaolex) 35.4134
total 100.00 % (w/w)
The above said synergistic insecticidal composition can be prepared by mixing Imidacloprid Technical (purity 95%), Phosphamidon Technical (purity 92%) Priochem PN, Bitrex, Zeolite, Antimousse 426 -R, Supragil MNS -90, Supragil WP, PVP K-30, Methyl violet, Insilco and Kaolex in the above said proportions in a pre-blender equipped with agitator to get a homogenous mixture of all the ingredients. Thereafter the homogenous mixture obtained is micronised to get particle size of 2 - 10 microns which is post-blended to yield the synergistic above mentioned insecticidal composition
Example -8
A composition containing Imidacloprid 3.0 % + Phosphamidon 45% [48 % SP]:
Composition
Ingredient Quantity (% w/w)
Imidacloprid Technical (purity 95%) 3.1579
Phosphamidon Technical (purity 92%) 48.9131
Stabilizer (Priochem BL) 2.5000
Emetic agent (Amerex) 0.0040
Disintegrating agent (Zeolite) 6.0000
Antifoaming agent (Antimousse 426 - R) 0.7500
Wetting agent (Supragil MNS-90) 2.0000
Dispersing agent (Supragil WP) 7.0000
Binding agent (Agrimer) 0.2000
Dye(s) (Ocean blue) 0.6000
Filler(s) (Insilco and kaolex) 28.8750
total 100.00 % (w/w)

The above said synergistic insecticidal composition can be prepared by mixing Imidacloprid Technical (purity 95%) Phosphamidon Technical (purity 92%), priochem BL ,Amerex„ Zeolite,, Antimousse 426 - R, Supragil MNS-90, Supragil WP, Agrimer, Ocean blue, Insilco and kaolex in the above said proportions in a pre-blender equipped with agitator to get a homogenous mixture of all the ingredients. Thereafter the homogenous mixture obtained is micronised to get particle size of 2 - 10 microns which is post-blended to yield the synergistic above mentioned insecticidal composition
Example -9
A composition containing Imidacloprid 1.0 % + Phosphamidon 40.0% [41 %
SP] :
Composition
Ingredient Quantity (% w/w)

Imidacloprid Technical (purity 95%) 1.0527
Phosphamidon Technical (purity 92%) 43.4783
Stabilizer (Priochem PN) 3.0000
Emetic agent (Bitrex) 0.0030
Disintegrating agent (Zeolite) 7.0000
Antifoaming agent (Antimousse 426 -R) 1.0000
Wetting agent (Supragil WP) 4.0000
Dispersing agent (Supragil MNS-90) 7.5000
Binding agent (VA-6) 0.4000
Dye(s)(Methyl violet) 0.4000
Filler(s) (Insilco and Kaolex) 32.1660
total 100.00 % (w/w)
The above said synergistic insecticidal composition can be prepared by thoroughly mixing Imidacloprid Technical (purity 95%) Phosphamidon Technical (purity 92%) ,Priochem PN, Bitrex, , Zeolite, Antimousse 426 -R,Supragil WP,Supragil MNS-90,VA -6, Methyl violet, Insilco and Kaolex in the above said proportions in a pre-blender equipped with agitator to get a homogenous mixture of all the ingredients. Thereafter the homogenous mixture obtained is micronised to get particle size of 2 - 10 microns which is post-blended to yield the synergistic above mentioned insecticidal composition
Example -10
A composition containing Imidacloprid 2.0 % + Phosphamidon 40% [42 % SP] :

Composition
Ingredient Ouantitv (% w/w)
Phosphamidon active ingredient 40.0000
Imidacloprid active ingredient 2.0000
Surfactant - (Alkyl Naphthalene Sulfonate) 7^0000
Dye(s)- (Methyl violet) 0.0500
Fillers -Inert (Precipitated Silica) 50.9500.
total 100.00 % (w/w)
The above said synergistic insecticidal composition can be prepared by mixing Phosphamidon active ingredient, Imidacloprid active ingredient ,Alkyl Naphthalene Sulfonate, Methyl violet and Precipitated Silica in the above said proportions in a pre-blender equipped with agitator to get a homogenous mixture of all the ingredients. Thereafter the homogenous mixture obtained is micronised to get particle size of 2 - 10 microns which is post-blended to yield the synergistic above mentioned insecticidal composition
Example-11
Evaluation of the synergistic insecticidal effect of the Chloronicotynyle (Imidacloprid plus a second insecticide Organophosphorus group ( Acephate, Phosphamidon) can be establishedby using any composition prepared by the process described in the above examples.
hi this evaluation, Brown plant hopper, Green plant hoppers used are obtained from laboratory colonies. Paddy leaves are immersed in 1:1 v/v, acetone/water solutions of the test compound, or solution of a combination of the test compounds for a period of about 4 seconds. Following immersion, leaves are allowed to air-dry for 2-3 hours. Plastic bioassay trays containing multiple open-faced wells (4.0 times.4.0.times.2.5 cm) are used. Cut portions of a treated leaf, a moistened cotton dental wick and a single third-instar larva are placed into each well . These wells are covered with an adhesive vented clear plastic sheet which is held under constant fluorescent light at about 30 ° C for a predetermined period of time. Larval mortality/morbidity is evaluated at 5 days after treatment. All treatments are replicated 3-4 fold in a randomized complete block design with 15-30 larvae per treatment. Using conventional log-probit analysis, the LC50 of each treatment is determined.
Using the above process, a Chloronicotynyle compound may be evaluated alone and in combination with second insecticidal compound, Imidacloprid at dose rates of 0, 15, 18, 21, 24, 27 and 30 ppm and in combination with Acephate 0, 400, 500, 600, 700, 800 ppm in various combination of these strengths.

For other insecticidal compound, Phosphamidon, by using the above process, may be evaluated alone and in combination with second insecticidal compound, Imidacloprid at dose rates of 0, 11, 14, 17, 20, 27 and 30 ppm and in combination with Phosphamidon 0, 160, 200, 240, 280, 320, 370, 400 ppm in various combination of these strengths.
Treatments which are used are shown in following Table 1.

J

I

The results of the above experiment shows that out of a large number of the above all combinations tried, some of them shows the synergistic insecticidal control. These combinations are shown in the bold values in the above table.
The following example confirm the synergistic effect of the strength selected from the example -11.
Example -12
Synergism can be calculated by using the Colby's method i.e. the expected (or predicted) response of the combination is calculated by taking the product of the observed response for each individual component of the combinaiton when applied alone divided by 100 and subtracting this value from the sum of observed response for each component when applied alone. Synergism of the combination is then determined by comparing the observed response of the

combination to the expected (or predicted) response as calculated from the observed response of each individual component alone. If the observed response of the combination is greater than the expected (or predicted) response then the combination is said to be synergistic and falls within the definition of synergistic effect. (Colby,S. R., Weeds, 1967(15), p. 20-22)

As can be seen from the data shown in Table 2, combinations of Imidacloprid plus a organophosphoms compound (Acephate) demonstrate synergistic insect control.


As can be seen from the data shown in Table 3, combinations of Imidacloprid plus a organophosphorus compound (Phosphamidon) demonstrate synergistic insect control.
Example 13
Evaluation of the Synergistic Insecticidal Effect Of a Combination of Chloronicotynyle (Imidacloprid) plus Organophosphorus (Acephate) against pests of Paddy.
In this example most of the composition prepared by the process described in this invention is used to evaluate their activities.
In this evaluation, per cent mortality of hoppers is worked out based on the number of hoppers counted before and after sprays and based on dead heart counts before and after sprays. The data is averaged and analyzed for the test of significance.

Details of the experiment:
a. Design
b. Replication
c. Product
d. Treatment
Table-4

: Randomised block design
: Three
: Imidacloprid + Acephate (1.8 + 50) %
: Seven ( as shown in details in the table -4)




S.No.
Active Ingredient (g a.i./ha) dose
1 Imidacloprid + Acephate 311
2 Imidacloprid + Acephate 388.8
3 Imidacloprid + Acephate 518
4 Imidacloprid + Acephate 647.5
5 Imidacloprid 17.8% SL 20
585
6 Acephate 75 %SP
7|Water spray only

Formulation quantity (g/ha)
600
750
1000
1250
112
780

e. Plot size
f. Variety
g. Spacing
h. Fertilizer
i. Sprayer used j. Spray volume
Imidacloprid + Acephate (1.8 + 50) % at 2000 and 4000 g/ha laid out separately by the side of bio-efficacy trial plot to avoid drift of chemical.
5x4 m = 20 sq. m.
Jyothi
20 x 10 cm
100:50:50 NPK Kg/ha
Knapsack sprayer
1.5 litre per 20 sq. m. plot

k. Time of application 1. Method
m. Observations recorded
: When the hoppers and dead heart symptoms are noticed.
: Required quantity of spray fluid is prepared before spray application and for phytotoxicity studies concentration of Imidacloprid + Acephate (1.8 + 50) % at 2000 and 4000 g/ha is laid out separately by the side of the bio¬efficacy trial plot to avoid drift of the chemical.
: i. Pre and post treatment data of green leaf hopper in three leaves from the base, middle and top position of the plants, brown plant hoppers on the stem portions, ii. Phytotoxicity of higher concentrations, iii. Grain yield.
n. Method of Observation: Phytotoxicity in terms of yellowing or blightening of
leaves is recorded in the higher concentrations of 2000 and 4000g/ha. When the crop - attained maturity the ear heads are harvested, dried, threshed and grain yield per 20 sq. m. plot is recorded and it is then computed to quintals per hectare. The data is analyzed staistically to discriminate the treatment superiority for control leaf eating pests and variation in the yield.
o. Results : The results of the field trial carried out to evaluate
the bioefficacy of and standardisation of doses of Imidacloprid + Acephate (1.8 + 50) % at doses 600, 750, 1000,1250 g/ha as compared Imidacloprid 17.8% SL 20g/ha, Acephate 75%SP 780 g/ha and untreated check are presented in the following tables.


Conclusion: From table-5 and 6 , Imidacloprid + Acephate (1.8 + 50) % at concentrations oflOOO and 1250 g/ha are effective and superior at first and second sprays respectively which are superior and or on par with standard checks tested against green leaf hoppers Imidacloprid + Acephate (1.8 + 50) % at 1250 is highly effective while @ 1000 g is as effective as standard checks after the first spray. After second spray at 1000 and 1250 g are on par with standard checks.

Table - 7 Reduction (%) of dead hearts due to stem borer after pesticide application



Conclusion : From table -7 against stem borers Imidacloprid + Acephate (1.8 + 50) % at 1250 is on par with Imidacloprid and at 1000 is on par with Acephate and differed from other treatments. Imidacloprid + Acephate (1.8 + 50) % at 1250 g/ha proved superioe followed by 1000 g/ha which is on par with Imidacloprid. Imidacloprid + Acephate (1.8 + 50) % at 750 g/ha is on par with Acephate at 780 g/ha after second spray.
Table -8 Grain yield after spray application


S.
No.
Treatment in g a.i./ha
1 Emidacloprid + Acephate (1.8 + 50)% 311
2 Imidacloprid + Acephate (1.8 + 50)% 388.5
3 Imidacloprid + Acephate (1.8 + 50) % 518
4 Imidacloprid + Acephate (1.8 + 50) % 647.5
5 Imidacloprid 17.8 SL @ 20 gal/ha
6 Acephate75%SP @ 585 g a.i./ha
7|Water spray

Dose g/ha
600
750
1000
1250
112
780

Grian yield (Quintal/ha)
134.65
138.5
138.6
138.8
136.5
92
77.5

Conclusion : Grain yield levels, as shown in table-8, are maximum in Imidacloprid + Acephate (1.8 + 50) % at all cencentrations which is on par with Imidacloprid @ 112 ml/ha and differed significantly from Acephate @ 780 g/ha. Phytoxocity levels at 2000 and 4000 g/ha varied from 2-3% leaf injury.



NP = No phytoxocity
*= Observation for phytoxicity was taken for 14 days after sprayon necrosis, hyponasty, leaf tip injury, leaf surface injury, wilting, vein clearing etc.
Conclusion : Imidacloprid + Acephate (1.8 + 50) % at 1000 and 1250 g/ha are effective against BPH, GLH and stem borers. Irrespective of concentrations grain yields are superios over standard checks . Phytotoxicity is negligible (2 and 3%) at the highest concentrations of 2000 and 4000 g/ha.
Example -14
Evaluation of the Synergistic Insecticidal Effect of a combination of Chloronicotynyle (Imidacloprid) plus Organophosphorus (Phosphamidon )
against pests of Paddy.
In this example most of the composition prepared by the process described in this invention is used to evaluate their activities.
In this evaluation, per cent mortality of hoppers is worked out based on the number of hoppers counted before and after sprays and based on dead heart counts before and after sprays. The data is averaged and analyzed for the test of significance.

Details of the experiment:
a. Design
b. Replication
c. Product
d. Treatment

Randomised block design
Three
Imidacloprid + Phosphamidon (2 + 40) %
Eight (The table -10 describes the eight

treatments, in details, studied during this example).
Table -10 Details of the eight treatments


S.No.
Active Ingredient (g a.i./ha) dose
1 Imidacloprid + Phosphamidon 126

Formulation quantity (g/ha)
300



2 Imidacloprid + Phosphamidon 168
3 Imidacloprid + Phosphamidon 210
4 Imidacloprid + Phosphamidon 252

400
500
600



5 Imidacloprid + Phosphamidon 294
6Imidacloprid 17.8 % SL 20
7Phosphamidon 40 %SL 300

700
112
750

8[Water spray only
Imidacloprid + Phosphamidon (2+ 40) % at 1200 and 2400 g/ha laid out separately by the side of bio-efficacy trial plot to avoid drift of chemical.

e. Plot size
f. Variety
g. Spacing
h. Fertilizer
i. Sprayer used j. Spray volume k. Time of application
1. Method
m. Observations recorded
n. Method of Observation

5x4 m = 20 sq. m.
Jyothi
20 x 10 cm
100:50:50 NPK Kg/ha
Knapsack sprayer
1.5 litre per 20 sq. m. plot
When the hoppers and dead heart symptome are noticed.
: Required quantity of spray fluid is prepared before spray application and for phytotoxicity studies concentration of Imidacloprid + Phosphamidon (2 +40) % at 1200 and 2400 g/ha is laid out separately by the side of the bio-efficacy trial plot to avoid drift of the chemical.
: i. Pre and post treatment data of green leaf hopper in three leaves from the base, middle and top position of the plants, brown plant hoppers on the stem portions, ii. Phytotoxicity of higher concentrations, iii. Grain yield.
: Phytotoxicity in terms of yellowing or blightening of leaves is recorded in the higher concentrations of 1200 and 2400 g/ha.

o. Results

When the crop-attained maturity the ear heads are harvested, dried, threshed and grain yield per 20 sq. m.plot is recorded and it is then computed to quintals per hectare. The data is analyzed staistically to discriminate the treatment superiority for control leaf eating pests and variation in the yield.
: The results of the field trial carried out to evaluate the bioefficacy of and standardisation of doses of Imidacloprid + Phosphamidon (2 + 40) % at doses 300, 400, 500, 600and 700 g/ha as compared Imidacloprid 17.8% SL 20g/ha, Phosphamidon 40 %SL 300 g/ha and untreated check are presented in the following tables.





Conclusion : From 11 and 12, toxicity of Imidacloprid + Phosphamidon (2 + 40) % increased with increase in the concentrations. Against brown plant hoppers Imidacloprid + Phosphamidon (700 g) is superior followed by its doses at 500 and 600 gm which differed significantly over other insecticides tested. Trend is similar after second spray . Maximum mortality of green leaf hoppers is at 700 g/ha and the toxicity differed significantly over other toxicants . Similar trend remained even after second spray.

Conclusion : From table 13, against stem borers maximum reduction of ded hearts is noticed in the Imidacloprid + Phosphamidon (2 + 40) % at 600 and 700 g/ha which differed from other toxicants. But it is inferior to imidacloprid however after second spray Imidacloprid + Phosphamidon (2+ 40) at 500 to 700 g are superior over other pesticides tested.


Conclusion; From table 14, the grain yield levels are maximum in Imidacloprid + Phosphamidon (2 + 40) % upto 700 g/ha which is on par with 600 g/ha and it differed significantly over 500,400 and 300 g/ha and others chemicals tested.
Table-15 Phytotoxicity due to application of pesticides


S. No.
Treatment in g a.i./ha
1 Imidacloprid + Phosphamidon 126
2 Imidacloprid + Phosphamidon 168
3 Imidacloprid + Phosphamidon 210
4 Imidacloprid + Phosphamidon 252
5 Imidacloprid + Phosphamidon 294
6 Imidacloprid + Phosphamidon 504
7 Imidacloprid + Phosphamidonl008
8 Imidacloprid 17.8 %SL 20
9 Phosphamidon 40 %SL 300
10|Water spray only

Dose g/ha
300
400
500
600
700
1200
2400
112
750

* Cumulative
Phytotoxicity (%)
on 14 th day
NP
NP
NP
NP
NP
1.00%
2.00%
NP
NP
NP

NP = No phytoxocity
*= Observation for phytoxicity was taken for 14 days after sprayon necrosis, hyponasty, leaf tip injury, leaf surface injury, wilting, vein clearing etc.
Conclusion: From table 15, the phytoxocity is negligible in Imidacloprid + Phosphamidon (2 + 40) % at 300 to 700 g/ha and are at 1-2 % in highest concentrations of 1200 and 2400 g/ha.
Result : Imidacloprid + Phosphamidon (2 + 40) % at 300 and 700 g/ha reduced hoppers and stem borers effectively. However, doses at 700 g is most effective followed by 400 and 500g and on par with standard check chemicals even at 300 g/ha. The yields increased with the concentrations of Imidacloprid + Phosphamidon (2+40)% upto 700 g/ha. Phytotoxicity is negligible at all concentrations of Imidacloprid + Phosphamidon (2+40)% and even at 1200 to 2400 g/ha which recorded 1-2% leaf blightening.
The synergistic insecticidal composition prepared by the process of this invention can be applied as per prescribed recommendation on the label by mixing the pesticide and water at right dosage and spray. It can be sprayed by using high volume sprayer viz. Knapsack sprayer, using 500 - 1000 litres of water per hactare.

Advantages of the invention
The composition of the present invention helps to :
- delay the dominance of the resistant strains of pests;
- have a broader spectrum of activity and reduces risk of developing resistance;.
- achieve effective and economic control of undesirable species;
- improve biological performance in single application;
- minimise occupational exposure and hazards;
- decrease the cost of application;
- save fuel cost, labour cost;
- save applicator's precious time;
- reduce wear of equipment and losses caused by mechanical damage to crops and soil.

We claim :
1 A synergistic insecticidal composition comprising one or more Chloronicotynyle compound, in an amount ranging from 0.1 to 5 % by weight of the composition , one or more compounds falling within the group of Organophosphorus compounds in an amount ranging from 30 to 75% by weight of the composition and 20 to 69.9 % by weight of agriculturally acceptable carrier(s) and excepient(s).
2. A composition as claimed in claim 1 wherein Imidacloprid is used in the range of 0.1 to 5.0 % by weight of the composition and one or more compounds selected from Organophosphorus group are in the range of 30 to 75 % by weight of the composition.
3. A composition as claimed in claim 1 and claim 2 wherein the soluble powder composition contains 0.1 to 5.0% of Imidacloprid by weight of the composition and 30 to 75 % Acephate or Phosphamidon by weight of the composition.
4. A composition as claimed in claims 1 to claim 3 wherein the agriculturally acceptable carrier(s) and /or excepient(s) is (are) selected from solid, liquid carrier (s) and /or excepient(s) or both selected from mineral earth like silicas, silica gels, silicates, talc, kaolin, montmorillonite, attapulgite, pumice, sepiolite, bentonite, limestone, lime, chalk, clay, dolomite, diatomaceous earth, calcite, calcium sulfate, magnesium sulfate, magnesium sulfate, magnesium oxide, sand, ground plastics, fertilizers like ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas, and crushed products of vegetable origin such as cereal meal, tree bark meal, wood meal, nutshell meal and cellulose powders.
5. A composition as claimed in claims 1 to 4 wherein the excipient(s) such as surfactant(s) is (are) non-ionic, cationic and /or anionic in nature is (are) used which have good emulsifying, dispersing and wetting properties.
6. A composition as claimed in claim 5 wherein excipient(s) such as anionic surfactants used is both water-soluble soaps and water-soluble synthetic surface-active compounds such as soaps like the alkali metal, alkaline earth metal or substituted or unsubstituted ammonium salts of higher fatty acids (C10 - C22 ), for example the sodium or potassium salt of oleic or stearic acid, or of natural fatty

7. A composition as claimed in claims 1 to 6 wherein excipient(s) such as stabilizer used is selected from ethoxylate of vegetable oil, salts of higher fatty acids, the preferred stabilizer being a blend of the derivatives of epoxylated vegetable oil, Ethoxylated polyoxyethylene amine and pyroolidine and/or lactone or a mixture thereof.
8. A composition as claimed in claims 1 to 7 wherein excipient(s) such as wetting cum dispersing agent used is selected from alkyl phenol ethoxylate, salts of alkyl naphthyl sulphonate, salts of alkyl aryl sulphonate, derivative of sulfonated fatty alcohol.
9. A composition as claimed in claims 1 to 8 wherein the excipient(s) such as wetting agent selected form calcium /sodium salt(s) of alkyl aryl sulphonate.
10 A composition as claimed in claims 1 to 9 wherein excipient(s) such as emetic agent selected from lignocaine derivative and /or a formulation of lignocaine derivative.
11. A composition as claimed in claims 1 to 10 wherein the excipient(s) such as antifoaming agent used is silicone oil derivative.
12. A composition as claimed in claims 1 to 11 wherein excipient(s) such as disintegrating agent used is selected from absorbing type clays like bentonite, zeolite, attapulgite and inorganic salts like sodium and aluminium sulphate.
13. A composition as claimed in claim 13-wherein excipient(s) such as filler used is precipitated Silica and diatomaceous earth kaolin/clay.
14. A composition as claimed in claims 1 to 13 wherein the mixture of active ingredients to carriers (excipients) are used in the ratio 1 : 1 to 1 : 10000.
15. A composition as claimed in claims 1 to 14- wherein excipient(s) such as anticaking agent used is selected from Fumed silica, anhydrous Magnesium sulphate, a blend of sucrose and starch derivatives.
16. A composition as claimed in claims 1 to ljf wherein the excipient(s) such as dye(s) used selected is water soluble, water insoluble or a combination thereof.
17. A composition as claimed in claims 1 to IS wherein the Acephate used is of Technical grade of purity 97% minimum.

18. A composition as claimed in claims 1 to 18 wherein the Imidacloprid used is of technical grade of purity 95% minimum.
19. A composition as claimed in claims 1 to 18 wherein the Phosphamidon used is of technical grade of purity 92% minimum.
20 A composition as claimed in claims 1 to 19 wherein the excipient(s) such as dispersing agent used is formaldehyde condensate of alkyl phenols.
21. A composition as claimed in claims 1 to 20wherein the excipient(s) such as binding agent used is pyrralidone derivative.
22. A composition as claimed in claims 1 to 21. wherein the powder form has an average particle size of 2-1500 microns.
23. A composition for the preparation of a synergistic insecticidal composition substantially as herein described with reference to the Examples 1 to 10.




Documents:

991-mum-2001-form 5(22-09-2003).pdf

991-mum-2001-petition under rule 137-(12-03-2004).pdf

991-mum-2003-abstract(granted)-(23-10-2007).pdf

991-MUM-2003-ANNEXURE TO FORM 3(4-8-2010).pdf

991-mum-2003-cancelled pages(28-09-2007).pdf

991-mum-2003-claims(complete)-(22-9-2003).pdf

991-mum-2003-claims(granted)-(23-10-2007).pdf

991-mum-2003-correspondence(1-7-2011).pdf

991-MUM-2003-CORRESPONDENCE(4-8-2010).pdf

991-mum-2003-correspondence(ipo)-(24-10-2007).pdf

991-mum-2003-correspondence-(28-09-2007).pdf

991-mum-2003-correspondence-(ipo)-(17-10-2007).pdf

991-mum-2003-description(complete)-(22-9-2003).pdf

991-mum-2003-description(granted)-(23-10-2007).pdf

991-mum-2003-form 1(22-09-2003).pdf

991-mum-2003-form 19(22-09-2003).pdf

991-mum-2003-form 2(complete)-(22-9-2003).pdf

991-mum-2003-form 2(granted)-(23-10-2007).pdf

991-mum-2003-form 2(title page)-(complete)-(22-9-2003).pdf

991-mum-2003-form 2(title page)-(granted)-(23-10-2007).pdf

991-MUM-2003-FORM 3(1-7-2011).pdf

991-mum-2003-form 3(22-09-2003).pdf

991-mum-2003-form 3(22-9-2003).pdf

991-mum-2003-form 3(28-09-2007).pdf

991-mum-2003-form 3(28-9-2007).pdf

991-mum-2003-pct isa 210(22-09-2003).pdf

991-MUM-2003-PETITION UNDER RULE 137(1-7-2011).pdf

991-mum-2003-petition under rule 137(27-10-2004).pdf

991-mum-2003-specification(amended)-(28-9-2007).pdf

991-mum-2003-wo international publication report (28-9-2007).pdf


Patent Number 211250
Indian Patent Application Number 991/MUM/2003
PG Journal Number 45/2007
Publication Date 09-Nov-2007
Grant Date 23-Oct-2007
Date of Filing 22-Sep-2003
Name of Patentee UNITED PHOSPHORUS LIMITED
Applicant Address 3-11, GIDC, VAPI-396 195 GUJARAT, INDIA
Inventors:
# Inventor's Name Inventor's Address
1 PRAKASH MAHADEV JADHAV 12 HASYAVADAN SOCIETY, TEJPAL SCHEME NO.4, VILE PARLE (EAST) MUMBAI 400 057.
2 JAIDEV RAJANIKANT SHROFF 4-B, SUMMER PALACE, NARGIS DUTT ROAD, PALIHILL, BANDRA (WEST), MUMBAI 400 050.
PCT International Classification Number A01N55/00
PCT International Application Number N/A
PCT International Filing date
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 NA