Title of Invention	A SYNERGISTIC HERBICIDAL COMPOSITION
Abstract	A synergistic herbicidal composition which mixing thorughly Pyrazosulfuron ethyl, in an amount rqnging from 0.01 to 5% by weight of composition, one of the othher herbicide preterabty out of Butachlor, Pretilachlor, and in an amount ranging from 1 to 50% by preferably out of Butacholr, Pretiachlor, and 2,4-D, in an amount ranging from 1 to 50% by weight of composition and 45 to 98.99% by weight of conventional agriculturally accepted carrier (s), adjuvant (s) for preparing synergistic herbicidal compositions as per the following process: 1) the first part, comprising of Pyrazosulfuron ethyl and an agriculturally accepetable coarrier (s), surfactants (s); and premixing these ingredient (s) and or adjuvants throughly for atleast 1/2 hour in a per-blender/mixer to have a homogeous mixture of all the ingredient (s) of the part as described; 2) the second part, comprising of stabilizers, solublizers, adjuvants and second herbicide preferably one or from, Butachlor, Pretilachlor or 2,4-D mixing these (stabilizers, solubizers, adjuvants and herbicide) in a mixer equipped with mixing arrangements to have homogeneous mixture of all ingredients (s) of the second part; 3) adding gradually the first part of the combination, as a whole or a part therof, to the first part; at a rate of addition of 0.1 to 100kg/hour 4) thereafter the whole material of the step (3) is mixid throughly for atleast 1 hour to have a nomogenous mixture;

Title of Invention

A SYNERGISTIC HERBICIDAL COMPOSITION

Abstract

A synergistic herbicidal composition which mixing thorughly Pyrazosulfuron ethyl, in an amount rqnging from 0.01 to 5% by weight of composition, one of the othher herbicide preterabty out of Butachlor, Pretilachlor, and in an amount ranging from 1 to 50% by preferably out of Butacholr, Pretiachlor, and 2,4-D, in an amount ranging from 1 to 50% by weight of composition and 45 to 98.99% by weight of conventional agriculturally accepted carrier (s), adjuvant (s) for preparing synergistic herbicidal compositions as per the following process: 1) the first part, comprising of Pyrazosulfuron ethyl and an agriculturally accepetable coarrier (s), surfactants (s); and premixing these ingredient (s) and or adjuvants throughly for atleast 1/2 hour in a per-blender/mixer to have a homogeous mixture of all the ingredient (s) of the part as described; 2) the second part, comprising of stabilizers, solublizers, adjuvants and second herbicide preferably one or from, Butachlor, Pretilachlor or 2,4-D mixing these (stabilizers, solubizers, adjuvants and herbicide) in a mixer equipped with mixing arrangements to have homogeneous mixture of all ingredients (s) of the second part; 3) adding gradually the first part of the combination, as a whole or a part therof, to the first part; at a rate of addition of 0.1 to 100kg/hour 4) thereafter the whole material of the step (3) is mixid throughly for atleast 1 hour to have a nomogenous mixture;

Full Text	FORM 2 THE PATENTS ACT, 1970 (39 of 1970) COMPLETE SPECIFICATION (See Section 10) "A SYNERGISTIC HERBICIDAL COMPOSITION " 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 , 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 herbicidal composition containing selective herbicides and improvements in the use of selective herbicides like Pyrazosulfuron ethyl and other herbicide(s) preferably one or more from Butachlor, Pretilachlor and 2,4-D (2,4-dichloro phenoxy acetic acid). This application is divided out of our application no 553/MUM/2002 In modernized agriculture today, considerable attention is being given to all aspects of crop production, especially to those which concern defence of crops against weeds, diseases and pests. In last few years a spurt in agricultural production is due to the green revolution, increased fertilizer use, crop production, improved irrigation and mfrastructural facilities. The important challenges confronted in the fanning today in the production practices is weed management. This invention is based on the strengths and weaknesses of ones approach in weed control and what better strategies can be adopted to contain their menacing impact on farming. Weed control using chemicals is much older . From 1940 onwards chemicals became the principal tools of weed control in the most developed nations and have been expanding slowly to developing nations , Weeds are the plants, which grows where they are not wanted. They grow in the fields where they compete with the crops for water, soil nutrients, light and space and thus reduce crop yields. They also harbour insects, pests and micro-organism. Certain weeds release into the soil the inhibitors or poisonous substances which are harmful to the plants, human beings and live stocks. They increase the expenditure on labour and equipment, render harvesting difficult, and reduces the quality and marketability of the agricultural produce. They block the drainage and impede the flow of the water in canals and water -transport channels and their growth in the rivers renders navigation very difficult. The dense growth of the weeds in water pollutes the water because they deoxygenate the water and kill the fish. Weeds seeds germinate earlier, their seedlings grow faster, they flower earlier, and form seeds in profusion, and mature ahead of the crop they infest. Weeds have a remarkable capacity to germinate under varied conditions but very characteristically they are season bound and the peak period of the germination always takes place in certain season in the regular succession year after year. Weeds belongs to the class Angiospermae (flowering plants) which have two subclass : Monocotyledoneae ( monocots) and Dicotyledoneae ( dicots). On the basis of the habitat, they are divided into terrestrial and aquatic categories, and on the basis of the duration of life they are divided into annuals, biennials and perennials. Annuals live and produce their seeds in a single growing season . Biennials need two growing season ; in one season they pass through their vegetative or rosette stage, followed by the reproductive stage in the next season. The multiplication of both the annuals and biennials is through seed. Perennials live indefinitely and are propagated not only through seeds but often vegetatively through underground structures such as rhizomes, stolons, bulbs and tubers. Perennials are of two types the simple and the creeping. The former multiply through seeds. They have no normal means of spreading vegetatively. However, if they are injured or cut, the severed portions produce new plants. Creeping perennials are spread by creeping roots, creeping above ground stems( stolons) and creeping underground stems ( rhizomes). In non-irrigated areas, the competition between weeds and crops is largely for water. A saving of 750 to 1250 tonnes of water per hectare of soil, forming a one meter deep column, is possible by keeping the soil free from weeds. In irrigated tracts, the competition is severe for nutrients . The unchecked growth of weeds, in a wheat field measuring one hectare, removes about 20 Kg of Nitrogen , reducing the grain yield by about 12 Quintals. The minerals requirements of weeds are high. Weeds in a fallow land deplete the soil of both moisture and nutrients. Weeds generate a formidable competition with crop plants for light. One of the secrets behind the high-yield potential of the dwarf varieties of crop plants is that they can capture solar energy more efficiently. Unchecked weed growth in the fields cropped with dwarf variety will intercept solar radiation to detriment of the crop plants. Likewise, the competition that weeds offer to the valuable crop plants may assume, at times , so alarming proportions as to smother the latter. Both the nature of the weed and the crop which they infest, influence the action of weedicides. Measures against weeds comprise mechanical (cultivation and mowing), cultural or cropping, biological and chemical means. Each of these methods has certain merits and a prudent farmer can make use of one means or a combination of them to control weeds efficiently and economically. The controlling of weeds in the growing crops with weedicide increases their yields and ensure the efficient use of irrigation , fertilizer and plant protection measures.such as the spraying of insecticides and fungicides. The removing of weeds from the growing crop facilitates easy harvesting and gives a high-quality produce without admixture with the weed seeds. Chemical weed control can be adapted in time and in situations and under conditions which make manual, or mechanical weeding difficult. A great advantage of this method lies in killing weeds in the crop row or in the immediate vicinity of the crop plant. The chemical method is easier, less time consuming and less costly than weeding by hired labourers. Chemicals as herbicides began to be produced in 1950 through industrial research. As a consequence, world agriculture has been the recipient of a continuously expanding range of herbicides. A "herbicide" as a compound modifies or controls plant growth. The quantity of a compound which is capable of producing such an effect is termed as "herbicidally effective amount". Modifying or controlling modes includes all deviations from natural development, e.g. Killing, defoliation, retardation, dessication, regulation, stunting, leaf burn, tillering, dwarfing and the like. The germinating seeds, emerging seedlings and established vegetation, including roots and above-ground portions are termed as "Plants". In modern agriculture, chemical weed control through herbicides is the most popular method. Herbicides usage in a polyculture system prevailing in India is, however, not as simple as in monoculture due to differential selectivity and development of resistance in plant species as also due to herbicide persistence. Most of the presently available herbicides provide only a narrow-spectrum of weed control. These herbicides control either grasses or broad leaf weeds but not both. Many of them have activity only on annual species while a few are only effective against perennials. For example in broad leaf crops particularly in oilseeds and pulses, herbicides are available to control grassy weeds. It is difficult to control the broad leaf weeds like Lathyrus spp. in chickpea, vicia spp. in lentil and Asphodel"s tenuifolius in mustard and chickpea. Thus there is a danger of species replacement and hitherto less dominant weed becoming prominent and devastating. Selectively, therefore is also an important consideration in intercropping systems, which limits choice of herbicides. With the continuous use of herbicides in monoculture systems, herbicide resistance development is becoming problematic. Herbicide resistance is the inherited ability not to be controlled by herbicide. The indiscriminate use of agricultural chemicals led to two different problems due to persistence. One being harmful/inhibitive effect on sensitive crop growth in succession in a cropping system and thus reducing choice of crops. The second being the toxic chemical residues left undegraded, which may result in potential ecological hazard and pollution In addition there are problems of secondary pests and resurgence of weeds. As a result, change in weed communities are observed. In many cases, active herbicides in-combination have shown multi-facet advantage than when applied individually. Since the combination demonstrates a potency or/and activity level, exceeding that which might be expected from a mere addition of the individual potencies of the components are there by called as ""synergism". The present invention highlights the synergistic effect of a combination of two known active herbicides. Both the individual herbicides forming this combination, which is subject to this invention, are known to be potent herbicides , for their activity independent of each other. In the WO patent no WO/03/024224 a herbicidal composition has been disclosed in which in addition to customary inert formulation adjuvants conatins as active ingredient a mixture of at least two compounds selected from the group oxadiargyl , oxadiazon, fentrazamide, ethoxy sulfur on , quinchlorac, pyrazolate , amicarbazone, bromobutide, cafe ntrazone(-ethyl) pyrazolate , pyraflufen(-ethyl), sulfentarzone , tepraloxydim, clodinafop- propargyl, pretilachlor, butachlor, oxaziclomefone,fentrazamide benzobicyclon, molinate , quinchlorac, bentazone ,Pyrazolynate ,pentoxazone ,metamifop, cinosufuran, imazo sulfur an, pyrazosulfuroan(ethyl),Azimsulfuran, benzsulfuran-methyl) triasulfuran, prosulfuran, halo sulfur an(-methyl) sulfometuron(-methyl), sulfo sulfur an, chlorimuron,( -ethyl) cyclosulfamuron , trisulfuran and idosulfuran . The above patent states that any mixing ratio can be used but usually has an excess of one component over the other . The preferred ratio being 10: 1 to 1:10 preferably 5:1 to 1:5 especially 1:1 Though the composition disclosed includes amongst others a combination pretilachor , pyrazo sulfur an (ethyl) and butachlor, it is pertinent to note that none of the examples stipulates use of particular active ingredient mentioned . There is no example or description about the synergistic combination of pretilachor , pyrazosulfuran(ethyl) and butachlor. Further the composition, the patent says , may be in form of emulsifying concentrates, directly sprayable or dilutable solutions , wettable powders granules or micrpores . In the CN patent no 1286910 ,a compoition has been disclosed wherein the composition contains 10 to 50 % by weight of pretilachlor , 0.2.to 10 % by weight of Pyrazo zulfuron , PVC 1.0 to 2,0% by weight, sulfate 0.5 to 1% by weight, sodium lignosulphate 5 to 15 % by weight and carrier being the rest. 4 The composition is in the form of granules or wettable powders only. The present invention provides a improved synergistic herbicidal composition containing Pyrazosulfuron ethyl and another one or more herbicide, selected from Butachlor, Pretilachlor or 2,4-D along with agriculturally acceptable carrier (s ) , adjuvants and other excipients. The composition in the present invention is preferably in the form liquid or Emulsifying concentrate. Therefore , it is an object of the present invention to provide a composition of a herbicidal combination containing Pyrazo sulfur on ethyl and another herbicide (s), preferably from Butachlor,Pretilachlor,2,4-D, which demonstrates a high controlling effect with reduced environmental load and reduced crop production as well as reduced crop protection cost. Another object of the present invention is to provide a herbicidal composition containing a synergistically effective amount of a combination of Pyrazosulfuron ethyl plus other herbicide (s), preferably from Butachlor,Pretilachlor,2,4-D, useful for the synergistic herbicidal control and enhanced crop protection. Another object of the present invention is to provide a herbicidal composition, containing a synergistically effective amount of a combination of Pyrazosulfuron ethyl plus other herbicide (s), preferably, from Butachlor,Pretilachlor,2;4-D , in concentrated liquid, powder, granular form. These herbicidal composition is used in undiluted/ diluted form in fields. Yet another object of the present invention is to provide a herbicidal composition, containing a synergistically effective amount of a combination of Pyrazosulfuron ethyl plus other herbicide (s), preferably from Butachlor,Pretilachlor,2,4-D , which delays the dominance of the resistant strains of pests. Still another object of the present invention is to provide a herbicidal composition, containing a synergistically effective amount of a combination of Pyrazosulfuron ethyl plus other herbicide (s), preferably form Butachlor,Pretilachlor,2,4-D , which can achieve effective and economic control of undesirable weeds. Yet another object of the present invention is to provide a herbicidal composition, containing a synergistically effective amount of a combination of Pyrazosulfuron ethyl plus other herbicide (s), preferably from Butachlor,Pretilachlor,2,4-D,which can improve biololgical performance in single application and minimize occupational exposure and hazards Still another object of the present invention is to provide a herbicidal composition, containing a synergistically effective amount of a combination of Pyrazosulfuron ethyl plus other herbicide (s), preferably from Butachlor,Pretilachlor,2,4-D , which can decrease the cost of application, save fuel cost, labour cost and save applicator"s precious time and therefore very economical. Another object of the present invention is to provide a herbicidal composition, containing a synergistically effective amount of a combination of Pyrazosulfuron ethyl plus other herbicide (s), preferably from Butachlor,Pretilachlor,2,4-D , which reduces the wear of equipment and losses caused by mechanical damage to the soil. The process of this invention include intensive mixing and/ or milling of the active ingredients with other substances, such as stabilizers, emetic agents, rain-fasteners, solubilizers, adjuvants, antifoaming agent, wetting agent, dispersing agent, dye (s), fillers, carriers, surface active compounds (surfactants and / or emulsifiers ) and optionally solid and/ or liquid auxiliaries, as per the following process: Thus the WO patent does not discuss the synergestic composition of the present invention. The synergistic herbicidal compositions containing Pyrazosulfuron ethyl and another one or more herbicide, preferably from Butachlor, Pretilachlor or 2, 4-D, can be prepared per the following process: i) the first part, comprising of Pyrazosulfuron ethyl and an agriculturally accepetable carrier (s), surfactants (s); and premixing these ingredient (s) thoroughly for at least half an hour in a pre -blender/mixer to have a homogeneous mixture of all the ingredient(s) of the first part as described earlier; ii) the second part, comprising of stabilizers ,solublizers, adjuvants and second herbicide preferably one or more from Butachlor,Pretilachlor or 2,4-D and mixing these (stabilizers, solublizers,adjuvants and second herbicide ) in a mixer equipped with mixing arrangements to have a homogeneous mixture of all ingredients(s) of the second part; iii) adding gradually the first part of the combination ,as a whole or a part thereof, to the first part, at a rate of addition of 0.1 to 100 kg/hour; iv) thereafter the whole material of the step (3) is mixed thoroughly for at least one hour to have a homogeneous mixture. The synergistic herbicidal combinations contain herbicidally effective amount of Pyrazosulfuron ethyl and another one or more herbicide, preferably from Butachlor, Pretilachlor or 2,4-D, in about 0.01 : 105 to 1 : 800 and agriculturally acceptable carrier (s), adjuvant(s), surfactant (s). Agriculturally acceptable carrier (s), adjuvant (s), excepient (s) is / are selected from solid carrier(s) 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 phosphat, ammonium nitrate, ureas, and crushed products of vegetable origin such as cereal meal, tree bark meal, wood meal and nutshell meal, cellulose powders and the like . Suitable liquid carriers are essentially ; Aromatic hydro carbons,preferably the fractions containing 8 to 12 carbon atoms, such as xylene mixtures or mineral oil fractions of medium to high boiling point such as kerosine and diesel oil, furthermore coal tar oils and oils of vegetable or animal origin; aliphatic, cyclic and aromatic 6 hydrocarbons, for example cyclohexane,paraffins,tetrahydronaphthalene, alkylated naphthalenes and their derivates,alkylated benzenes and their derivatives; phthalic acid esters, such as dibutyl or dioctyl phthalate,alcohols and glycols and as well as their ethers and esters e.g. Methanol,propanol,butanol,cyclohexanol , ethylene glycol mono- and dimethyl ether; ketones such cyclohexanone; strongly polar solvents.for example amines such as N-methyl pyrrolidone, N- octylpyrrolidone and N-cyclohexylpyrrolidone or lactones such as butyrolactone;epoxidized plant oil esters such as methylatied coconut soyabean oil ester,and water mixtures of different liquid carriers are often suitable. The surfactant(s) such as non-ionic, cationic and /or anionic in nature is / are used 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 acids (CIO—C22), for example the sodium or potassium salt of oleic or stearic acid or of natural fatty acid mixtures. Pyrazosulfuron ethyl and other herbicide preferably Butachlor, Pretilachlor and 2, 4-D, is a ready mix synergistic action product which qualifies all the requirements of a good herbicides mixture. In this invention all the components are compatible. Along with this, the proportion of the active components is precisely chosen to gain best biological results. Being a ready mix, it makes much easier and less troublesome to prepare a proper and effective liquid spray than the preparation of tank mixtures. The composition of the present invention gives a quick and effective control of the weeds in crop fields to control weeds like Echinochloa crusgalli, Digitaria senguinalis, Setria app., Commelina benghalensis, Fimbristylis miliacoa, Cyperus iria, Eleusine indica, Panicum spp, Cyperus difformis, Cyperus rotunds, Alternanthera sessile, Caesulia axillaris, Cynotis cucullata, Ludwigia parviflora, Marsilae quadrifoliata, Monochoria vginalis, Echinochloa colonum, Eclipta alba, Sphenoclea zeylamica etc. The name "Pyrazosulfuron ethyl" belongs to sulfonyl urea group herbicide describes a chemical substance having a molecular weight 414.4, is in the form of colourless crystals, m.p. 181 -182 ° C ; solubility in water of 0.0145 g/1 ( 20 °C) ; in methanol 0.7, hexane 0.2, benzene 15.6, chloroform 234.4, acetone 31.7 ( all in g/1 20 ° C) . Stable at 50 ° C for 6 months. Relatively stable at pH 7 . Unstable in acidic or alkaline media. The molecule is having a structural formula : Ethyl 5-(4,6-dimethoxypyrimidin-2yl-carbaravIsulfamoyl)-l-methylpyrazole-4-carboxylate (IUPAC). It inhibits the branched chain amino-acid synthesis ( acetolactate synthase or ALS). Acts by inhibiting biosynthesis of the essential amino acids valine and isoleucine, hence stopping cell division and plant growth. Selectivity derives from rapid metabolism ( demethylation of 7 methoxy group) in the crop. It acts as systemic herbicide, absorbed by roots and /or leaves and translocated to the meristem. It controls the annual and perennial broad-leaved weeds, and sedges, pre-or post-emergence in wet- sown and transplanted rice crops, at 15-30 g/ha. Acute oral LD 50 for rats and mice >5000 mg/Kg. Acute percutaneousLD 50 for rats > 2000 mg/Kg. In rats after 48 hours, 80 % of applied pyrazosulfuron- ethyl is excreted in urine and faeces. The major metabolic reaction is demethylaton of methoxy group. The name "Butachlor" belongs to chloroacetanilide group herbicide describes a chemical substance having a molecular weight 311.9, is in the form of light yellow to purple liquid with a faint, sweet odour; m.p. -2.8 ° C to 1.7 ° C; b.point 156 ° C / 0.5 mm Hg; solubility in water of 20 mg/1 ( 20 °C) ; soluble in most organic solvents, including diethyl ether, acetone, benzene, ethanol, ethyl acetateand hexane. Decomposes at a temperature above 164 ° C, stable to UV light stable indefinetely below 45 ° C. The molecule is having a structural formula : ,\-butoxymethyl-2-chloro-2",6"-diethylacetani!ide ( IUPAC ) It acts as a protein synthesis inhibitor. It is selective systemic herbicide, absorbed primarily by the germinating shoots and secondarily by the roots, with translocation throughout the plant; giving higher concentration in vegetative parts then in reproductive parts. Used as pre-emergence for the control of annual grasses and certain broad-leaved weeds in rice, both seeded and transplanted. It shows selectivity in barley, cotton, peanuts, sugarbeets, wheat and several brassica crops. Activity is dependent on water availability such as rainfall following treatment, overhead irrigation of application to standing water as in rice culture. Non-phytotoxic to rice, cotton, barley, wheat, peanuts, sugarbeet and some brassicas. Acute oral LD50 for rats 2000, mice 4747, rabbits > 5010 mg/Kg. Acute percutaneous LD50 for rabbits > 13000 mg/Kg. In animals, it gets metabolized to water soluble metabolites and excreted. In plants it rapidly metabolized to water soluble metabolites, leading, eventually to mineralization. The name "Pretilachlor"1 belongs to chloroacetanilide group herbicide describes a chemical substance having a molecular weight 311.9, is in the form of colourless liquid ; b.point 135 ° C / 0.001 mm Hg; solubility in water of 50 mg/1 ( 20 °C) ; very soluble in benzene, hexane, methanol and dichloromethane . Relatively stable to hydrolysis ; DT50 (clc.) (20°C) > 200 days ( pH 1 - pH 9), 14 days ( pH 13) . Flash point 129 ° C. The molecule is having a structural formula : 2-chloro-2",6"-diethyl-N-(2-propoxyethyl) acetanilide (IUPAC) It inhibits the cell division. It is selective herbicide. It is taken up readily by the hypocotyl, mesocotyls and coleoptiles, and to a lesser extent by the roots of the germinating weeds. It is effective against main annual grasses, broad-leavec weeds and sedges in transplanted and seeded rice. Applied alone, pretilachlor will cause injury to direct seeded rice. Acute oral LD50 for rats 6099 mg/Kg. Acute percutaneous LD50 for rats > 3100 mg/Kg. Moderate irritation to skin; non-irritatant to eyes (rabbits). Non-toxic to birds. In animals, substitution of the chlorine atom for glutathione to form a conjugate. Cleavage of the ether bond to yield an ethyl alcohol derivative. Both metabolites axe susceptible to further degradation . In plants, the substitutionof the chlorine atom to form a conjugate occurs. Cleavage of the ether bond to an ethyl alcohol derivative occurs. Hydrolytic and reductive removal of the chlorine atom occurs. In soil/ environment when applied to paddy water, pretilachlor disappeared from water by adsorption to the soil, wrhere it is rapidly degraded under practical condition, median DT50 (lab.) 30 days. Due to strong soil adsorption, unlikely to leach. The name " 2,4-D" (2,4-dichlorophenoxy)acetic acid belongs to aryloxyalkanoic acid group herbicide describes a chemical substance having a molecular weight 221.0, is in the form of colourless powder; m.point. 140.5 ° C; solubility in water of 311 mg/1 ( pH 1,25° C); 0.6 g/1 ( 20 °C) ; in ethanol 1250, diethyl ether 243, heptane 1.1; toluene 6.7, xylene 5.8(all in g/Kg, 20 ° C). Insoluble in petroleum oils. Mono-n-butylamine salt; in water at 30 ° C, 18 g/kl . 2,4-D is atrong acid, and form water-soluble salt with alkali metals and amines Hard water leads to precipitation of the calcium and magnesium salts, but a sequestring agent is included in the formulations to prevent this. The molecule is having a structural formula : CI OH (2,4-dichloro phenoxy) acetic acid. (IUPAC) It is selective systemic herbicide. Salts are readily absorbed by the roots, whilst esters are readily absorbed by the foliage. Translocation occurs, with accumulation principally at meristematic regions of shoots and roots. Acts as a growth inhibitor. Use post-emergence control of annual and perennial broad-leaved weeds in cereals, maize, sorghum, grassland, established turf, grass seed crops, orchards,cranberries, asparagus, sugarcane, rice, forestry and on non-crop land ( including the areas adjacent to water) at 0.28-2.3 Kg/ha. Control of broad leaved aquatic weeds weeds. The isopropyl ester can be also be used as a plant growth regulator to prevent premature fruit fall in citrus fruits. Phytotoxic to most broad leaved crops, especialliy cotton, vines,tomatoes, ornamentals, fruit trees, oilseed rape and beet. Acute oral LDso for wild ducks > 1000, Japanese quail 668, pigeon 668, pheasants 472 mg/Kg. 9 LC50 (96h) for mallard ducks > 5620 mg/1 . Some formulations are toxic to fish, whilst others are not. Not toxic to bees . It does not appear to produce direct toxic effects on any animal species. In rats, following oral administration, elimination is rapid, and mainly as the unchanged substance. Following single doses of upto 10 mg/Kg, excretion is almost complete after 24 hours, although, with higher doses, complete elimination takes longer. The maximum concentration in organs is reached after 12 hours. In plants, metabolism involves hydroxylation, decarboxylation, cleavage of the acid side-chain, and ringopening. In soil, microbial degradation involves hydro xylation, decarboxylation, cleavage of the acid side-chain, and ring opening. Rapid degradation in the soil prevents significant downeward movement under normal conditions.Process for selectively combating weeds in the culturing of paddy (rice), which comprises the Pyrazo sulfur on ethyl and others, sufficient to selectively hinder the growth of weeds during the culturing of paddy, applied as a selective pre and early post emergence herbicide. Application rates depend upon the weeds to be controlled and the degree of control desired. The product provided by this invention is relatively more advantageous and exhibit very desirable characteristic noted herein after. The herbicidal composition can be applied to weed surfaces after dilution with water in recommended dilution rates. 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 pest 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 resulting 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 concentration of the active ingredients. In general, the synergistic effect may be achieved at application rates of the active ingredient of about 10 to 20 g/ha of Pyrazosulfuron ethyl in combinaiton with 700 to 1500 g/ha of Butachlor; preferably in about 14 g/ha. Pyrazosulfuron ethyl to 1000 g/ha g/ha of Butachlor. In general, the synergistic effect may be achieved at application rates of the active ingredient of about 10 to 20 g/ha of Pyrazosulfuron ethyl combinaiton with 280 to 575 g/ha of Pretilachlor, preferably in about 14 g/ha of Pyrazosulfuron ethyl to 400 g/ha of Pretilachlor. In general, the synergistic effect may be achieved at application rates of the active ingredient of about 10 to 20 g/ha of Pyrazosulfuron ethyl combinaiton with 350 to 715 g/ha of 2, 4-D, preferably in about 14 g/ha of Pyrazosulfuron ethyl to 500 g/ha g/ha of 2, 4-D. Preferred combination of the composition prepared by the process of the present invention are those combination wherein the active ingredient ratio (weight/weight) of Pyrazosulfuron ethyl and others preferably Butachlor, Pretilachlor or 2,4-D , is about 0.01 : 5 to 1 : 50 More preferred combination of the invention are combination of Pyrazosulfuron ethyl -and Butachlor wherein the active ingredient ratio (weight/weight) of Pyrazosulfuron ethyl : Butachlor is about 0.01 : 5 to 2 : 50. More preferred combination of the invention are combination of Pyrazosulfuron ethyl and Pretilachlor wherein the active ingredient ratio (weight/weight) of Pyrazosulfuron ethyl: Pretilachlor is about 0.01 : 5 to 5 : 50. More preferred combination of the invention are combination of Pyrazosulfuron ethyl and 2,4-D wherein the active ingredient ratio (weight/weight) of Pyrazosulfuron ethyl : 2,4-D is about 0.01 : 5 to 1 : 50 . The ratios of active ingredients in this invention are found tobe different than the ratios of that are disclosed in WO patent. The composition of this invention is preferably in the liquid form. It can also be in emulsifyable concentrate. Advantageously, the composition of the invention may be formulated in powder, solid or liquid form. A preferred liquid form comprises of a synergistically effective amount of a combination of Pyrazosulfuron ethyl plus other herbicide (s), preferably from Butachlor, Pretilachlor, 2, 4-D and / or solid or liquid inert substance(s). A preferred solid composition may be in a form of a homogeneous powder containing a synergistically effective amount of a combination of Pyrazosulfuron ethyl plus other herbicide (s), preferably from Butachlor,Pretilachlor,2,4-D and/ or in granular form of size ranging from 50 to 2000 micron containing a synergistically effective amount of a combination of Pyrazosulfuron ethyl plus other herbicide (s), preferably from Butachlor.Pretilachlor, 2,4-D. The forms of application of the compositions according to this invention depend on the intended purposes; in any case, they guarantee uniform 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. Alternatively, concentrates which consist of herbicidally 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 as a dilute spray prepared from any of the above-said formulations. The synergistic effective amount of the combination of Pyrazo sulfur on ethyl may vary accordingly to prevailing conditions such as the particular second herbicide present, , type of weeds, application timing, weather conditions, soil conditions, mode of application, topographical character, target crop and the like. The composition prepared by the process of the present invention is superior herbicidal compositions and are especially useful for the control of weeds. 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 herbicidal composition prepared by the process of the invention are found to be highly active against a wide variety of weeds like Echinochloa crusgalli, Digitaria senguinalis, Setria app., Commelina benghalensis, Fimbristylis miliacoa, Cyperus iria, Eleusine indica, Panicum spp, Cyperus difformis, Cyperus rotunds, Alternanthera sessile, Caesulia axillaris, Cynotis cucullata, Ludwigia parviflora, Marsilae quadrifoliata, Monochoria vginalis, Echinochloa colonum, Eclipta alba, Sphenoclea zeylamica etc. The present invention highlights the synergistic effect of the combination of Pyrazo sulfuron ethyl and containing a synergistically effective amount of a combination of Pyrazo sulfuron ethyl plus another herbicide(s), preferably from Butachlor,Pretilachlor,2,4-D . Following the right use of the invented technology and the composition of the invention with a formulation 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 and helps to ; - delay the dominance of the resistance strains of weeds - have a broader spectrum of activity and reduces risk of developing resistance - achieve effective and economic control of undesiretl weeds - improve biological performance in single applications - minimise occupational exposure and hazards -decrease the cost of appliation - save fruel cost, labour cost - save applicator"s precious time - reduce wear of equipment and losses caused by mechanical damage to crops. 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. The general composiiton of Pyrazosulfuron ethyl and Butachlor is as follows : Composition Ingredient Quantity (% w/wl Pyrazosulfuron ethyl Techical (purity 95%) Min. 0.01 to 5.00 Max. Butachlor Technical (purity 85%) Min. 2.00 to 50.00 Max. Stabilizer (Sodium alginate) Min. 0.01 to 10.00 Max Emetic agent (Bitrex ) Min. 0.00 to 0.005 Max Disintegrating agent (Zeolite) Min. 0.00 tolO.OO Max Antifoaming agent (Antimousse 426 -R) Min. 0.00 to 1.00 Max Wetting cum dispersing agent (Lisapol BN - 200) Min. 0.01 to 10.00 Max Anticaking agent (anhydrous Magnesium sulphate) Min. 0.01 to 5.00 Max Dye(s) Min. 0.05 to 1.00 Max Adjuvant (s) Min. 0.05 to 10.00 Max Emulsifier (s) Min. 0.1 to 10.00 Max Solvent(s) _ Q.S. Total 100.00 %(w/w) Above mentioned synergistic herbicidal composition"s preparation comprises mixing thoroughly, for half an hour, Pyrazosulfuron ethyl, with one or more another herbicide preferably from Butachlor,Pretilachlor or 2,4-D, adjuvant (s), solid and/ or liquid carriers, surfactant (s),with/ without dye in a mixer equipped with agitator to get a homogenous mixture of all the ingredients of above mentioned herbicidal composition. The final product can be in the form of wettable powders, granules.liquid and or any other suitable form in the given compositions. Pyrazosulfuron ethyl and Butachlor, in liquid form in following given combinations: Table-1 Shows synergistic herbicidal composition of Pyrazosulfuron Component PSE PSE +Butachlor PSE + Butachlor +Butachlor (1+45) %w/w (0.7+50) %w/w (3+35) %w/w ethyl (PSE) + Butachlor PSE PSE +Butachlor +Butachlor (1+50) (5+50) %w/w %w/w Pyrazosulfuron ethyl Tech@95 3.16 1.05 0.74 1.05 5.26 Butachlor_Tech @85 41.18 52.94 58.82 58.82 52.82 Stabilizer 1.00 1.00 1.00 1.00 1.00 Surfactant (s) 2.00 3.00 3.00 3.00 5.00 Disintegrating agent 2.00 2.50 2.50 2.50 3.00 Adjuvants 3.00 3.00 3.00 4.00 4.00 Emulsifiers 10.00 10.00 10.00 10.00 12.00 Dye 0.10 0.10 0.10 0.10 0.10 Liquid carrier(s) 37.56 26.41 20.84 19.53 16.82 Total (% ) 100.00 100.00 100.00 100.00 100.00 The general composiiton of Pyrazosulfuron ethyl and Pretilachlor is as follows : Ingredient Quantity (% w/w) Pyrazosulfuron ethyl Techical (purity 95%) Min. 0.01 to 5.00 Max. Pretilachlor Technical (purity 94%) Min. 5.00 to 50.00 Max. Stabilizer (Sodium alginate) Min. 0.01 to 10.00 Max Emetic agent (Bitrex ) Min. 0.00 to 0.005 Max Disintegrating agent (Zeolite) Min. 0.00 tolO.OO Max Antifoaming agent (Antimousse 426 -R) Min. 0.00 to 1.00 Max Wetting cum dispersing agent (Lisapol BN - 200) Min. 0.01 to 10.00 Max Anticaking agent (anhydrous Magnesium sulphate) Min. 0.01 to 5.00 Max Dye(s) Min. 0.05 to 1.00 Max Adjuvant (s) Min. 0.05 to 10.00 Max Emulsifier (s) Min. 0.1 to 10.00 Max Solvent(s) Q.S. Total 100.00 %(w/w) 15 Pyrazosulfuron ethyl and Pretilachlor, in liquid form in following given combinations: Table-2 Shows the synergistic herbicidal composition of Pyrazosulfuron ethyl (PSE) + Pretilachlor Component PSE + PSE + PSE ■ PSE + PSE Pretilachlor Pretilachlor Pretilachlor Pretilachlor Pretilachlor (3+35) %w/w (1+40) %w/w (1.4+40) %w/w (2+40) %w/w (5+50) %w/w Pyrazosulfuron ethyl Tech@95 3.16 1.05 1.47 2.11 5.26 Pretilachlor Tech @ 94 37.23 42.55 42.55 42.55 53.19 Stabilizer 1.00 1.00 1.00 1.00 1.00 Surfactant(s) 2.00 2.00 2.50 3.00 4.00 Disintegrating agent 3.00 3.00 3.00 3.00 3.00 Adjuvants 3.00 3.00 3.00 4.00 4.00 Emulsifiers 8.00 10.00 10.00 10.00 12.00 Dye 0.10 0.10 0.10 0.10 0.10 Liquid carrier(s) 42.51 37.30 36.38 34.24 17.45 Total (%) 100.00 100.00 100.00 100.00 100.00 The general composition of Pyrazosulfuron ethyl and 2,4-D is as follows : Ingredient Quantity (% w/w) Pyrazosulfuron ethyl Techical (purity 95%) Min. 0.01 to 5.00 Max. 2, 4-D Technical (purity 80%) Min. 1.00 to 50.00 Max. Stabilizer (Sodium alginate) Min. 0.01 to 10.00 Max Emetic agent (Bitrex ) Min. 0.00 to 0.005 Max Disintegrating agent (Zeolite) Min. 0.00 tolO.OO Max Antifoaming agent (Antimousse 426 -R) Min. 0.00 to 1.00 Max Wetting cum dispersing agent (Lisapol BN-200) Min. 0.01 to 10.00 Max Anticaking agent (anhydrous Magnesium sulphate) Min. 0.01 to 5.00 Max Dye(s) Min. 0.05 to 1.00 Max Adjuvant (s) Min. 0.05 to 10.00 Max Emulsifier (s) Min. 0.1 to 10.00 Max Fillers (s) (Insilco and Kaolex ) / solvent(s) Q.S. Total 100.00 %(w/w) 17 Pyrazosulfuron ethyl and 2,4-D. in powder form in following given combinations: Table-3 Shows the synergistic herbicidal composition of Pyrazosulfuron ethyl ( PSE ) + 2,4-D Component PSE + 2,4-D PSE + 2,4-D PSE + 2,4-D PSE + 2,4-D PSE -2,4-D (0.1+20) (1+25) %w/w (1+35) %w/w (2.5+40) (5+50) %w/w %w/w %w/w Pyrazosulfuron ethyl Tech@95 0.11 1.05 1.05 2.63 5.26 2,4-DTech @ 80 25.00 31.25 Stabilizer 1.00 1.00 Surfactant(s) 5.00 5.00 Disintegrating agent 5.00 4.00 Adjuvants 2.00 3.00 Antifoaming agent 1.00 1.00 Dye 0.10 0.10 Solid carrier(s) 60.79 53.60 Total (%) 100.00 100.00 43.75 50.00 62.50 1.00 2.00 2.50 6.00 7.00 10.00 5.00 5.00 5.00 3.00 2.00 2.00 1.00 1.00 1.00 0.10 0.20 0.30 39.10 30.17 11.44 100.00 100.00 100.00 18 Pyrazosulfuron ethyl and 2,4-D, in granular form in following given combinatios: Table-4 Shows the synergistic herbicidal composition of Pyrazosulfuron ethyl+2,4-D Component PSE + 2,4-D PSE + 2,4-D PSE + 2,4-D PSE + 2,4-D PSE+2,4-D (0.07+2.5) % (1+2.5) % w/w (0.01+5) % w/w (l+5)%w/w (2+10) w/w % w/w Pyrazosulfuron ethyl Tech@95 0.07 0.11 0.01 1.05 2.11 2,4-DTech @ 85 3.13 3.12 1.00 6.25 0.50 6.25 1.00 12.50 Stabilizer 1.00 2.00 Surfactant(s) 2.00 2.00 3.00 3.00 5.00 Disintegrating agent 2.00 2.00 2.00 2.00 4.00 Adjuvants 1.00 1.00 2.00 2.00 3.00 Binding agent (adjuvant) 2.00 2.00 2.00 3.00 4.00 Dye 0.10 0.10 0.10 0.10 0.10 Solid carrier(s) 88.70 88.67 84.14 81.60 67.29 Total (%) 100.00 100.00 100.00 100.00 100.00 Example Evaluation of the synergistic herbicidal effect of the Pyrazo sulfuron ethyl plus a second herbicide preferably from Butachlor,Pretilchlor and 2,4-D can be established by using any composition prepared by the process described in the above examples. For these evaluations one or more of the cornpositons prepared in the examples are used here. In this evaluation, one of the important weeds of Rice ( paddy ) corps , namely Echinochloa crusgalli is grown in standard greenhouse soil until its plants have reached the 6-leaf stage.Said plant are then sprayed with an aqueous solution of the test copound Pyrazosulfuron ethyl and a second herbicide preferably one of the following Butachlor,Pretilachlor or 2,4-D,using a spray nozzle opetating at 30 psi for a predetermined time so as to obtain a range of application rates of about 10 g/ha to 1500 g/h . Each treatment is replicated 3 times.Afier spraying, the plants are placed on greenhouse benches and are cared for in a manner commensurate with standard greenhouse practice. At 4 weeks after treatment, the plants are examined, and the % weed control as compared to the untreated check is recorded. Synergism can be calculated by using the Colby"s method i.e. the expected (or predicted) response ( E ) of the combination is calculated by taking the product of the observed response for each individual component X and Y, of the combination when applied alone divided by 100 and subtracting this value from the sum of observed response ( X + Y ) for each component when applied alone. E = (X + Y)-{ [X. Y]/100} where E - expected or predicted response X- observed response for "A" component Y- observed response for "B" component Synergism of the combination is then determined by comparing the observed response ( O ) of the combination to the expected (or predicted) response ( E )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) e.g. a. if E > O then result is antagonistic effect; b. if E = O then result is simply additional effect; c. if E The treatment comprises different doses of Pyrazo sulfuron ethyl with a second herbicide preferably Butachlor, Pretilachlor or 2,4-D at doses specified specificallly below within relative examples. Using the above process, Pyrazo sulfuron ethyl may be evaluated alone and in combination with second herbicidal compound. 20 For example, the synergistic effect may be achieved at application rates of the active ingredient of about 10 to 20 g/ha of Pyrazosulfuron ethyl in combinaiton with 700 to 1500 g/ha of Butachlor; preferably in about 14 g/ha of Pyrazosulfuron ethyl to 1000 g/ha. For example, the synergistic effect may be achieved at application rates of the active ingredient of about 10 to 20 g/ha of Pyrazosulfuron ethyl combinaiton with 280 to 575 g/ha of Pretilachlor, preferably in about 14 g/ha of Pyrazosulfuron ethyl to 400 g/ha of Pretilachlor. For example, the synergistic effect may be achieved at application rates of the active ingredient of about 10 to 20 g/ha of Pyrazosulfuron ethyl combinaiton with 350 to 715 g/ha of 2,4-D, preferably in about 14 g/ha of Pyrazosulfuron ethyl to 500 g/ha of 2,4-D. Treatments which are used are shown in following table 5 . As can be seen from the data shown in Table 5 below, application of a combination of Pyrazosulfuon ethyl and Butachlor gives significantly greater weed control [of Rice ( paddy ) crop weed Echinochloa crusgall ] than that which could be predicted from the weed control resulting from the application of either Pyrazosulfuron ethyl alone or Butachlor alone. Table -5 Shows the synergistic effect for Pyrazosulfuron and Butachlor 4iA" Butachlor (active "B" Pyra2osulruron ethyl Observed Mortality (%) Expected Mortality (%) =E Difference (%) D= O - E ingredient g/ha) (active ingredient g/ha) Y =0 0 0 0 0 10 Y-22.62 0 20 44.86 0 30 60.97 700 0 X= 16.75 1500 0 37.11 700 10 59.35 35.58 23.77 700 20 95.2 54.09 41.11 700 30 88.66 67.50 21 16 1500 10 68.84 51.33 1751 1500 20 95 65.32 29.68 1500 30 97 75.45 21.55 Colby"s formula worked out for expected mortality (E) for the row number 7 from above table as : E = (X + Y)-{[XxY]/100} where E - expected or predicted response X- observed response for "A" (700) component = 16.75 Y- observed response for "B" (10) component = 22.62 E for a combination (Butachlor 700 + Pyrazosulfuron ethyl 10)= ( X + Y) - { [ X x Y]/100} = (16.75 + 22.62) - {[16.75 x 22.62]/100} = (39.37) - { [378.885}/100} = (39.37)-{3.7885} =35.58115 =35.58 0-59.35 Here E As can be seen from the data shown in Table 6 below, application of a combination of Pyarzosulfuon ethyl and Pretilachlor gives significantly greater weed control [of Rice ( paddy ) crop weed Echinochloa crussall ] than that which could be predicted from the weed control resulting from the application of either Pyrazosulfuron ethyl alone or Pretilachlor alone. Table - 6 Shows the synergistic effect for Pyrazosulfuron ethyl and Pretilachlor Pretilachlor (active ingredienl g/ha) Pyrazosulfuron Observed : ethyl (active Mortality (%) -■ ingredient g/ha) Expected -O Mortality (%) =E Difference D=0-E 0 0 0 0 10 22.52 0 20 44.96 0 30 60.87 280 0 59.44 575 0 59.78 280 10 84 68.57 15.43 280 20 92 77.68 14,32 280 30 95.49 84.13 11.36 575 10 87.78 68.84 18.94 575 20 99.53 77.86 21.67 575 30 97.52 84.26 13.26 (%) As can be seen from the data shown in Table 7 below, application of a combination of Pyarzosulfuon ethyl and 2,4-D gives significantly greater weed control [of Rice ( paddy ) crop weed Echinochloa cruseall ] than that which could be predicted from the weed control resulting from the application of either Pyrazosulfuron ethyl alone or 2,4-D alone. Table - 7 Shows the synergistic effect for Pyrazosulfuron ethyl and 2,4-D 2,4-D (active Pyrazosulfuron Observed Expected Difference (%) ingredient g/ha) ethyl (active Mortality (%) =0 Mortality (%) = E " D= 0 - E 13.10 18.60 11.38 15.50 20.30 13.60 ingredient g/ha) 0 22.4 44.9 60.95 30 62.25 58.78 45.68 80.03 61.43 84.04 72.66 86.20 70.70 99.50 79.20 98.85 85.25 Conclusion: From above tables 5, 6, 7, it reflects that the Pyrazosulfuron ethyl shows a synergistic effect when applied with other herbicides like Buatchlor, Pretilachlor and 2, 4-D and vice-versa. Synergism was more when the combinations were in the range of ,as stated in examples earlier for Pyrazosulfuron ethyl plus Butachlor, Pyrazosulfuron ethyl plus Pretilachlor and Pyrazosulfuron ethyl plus 2,4-D,respectively. Result : Pyrazosulfuron ethyl with another one herbicide preferably from Butachlor, Pretilachlor or 2,4-D gives synergistic effects as shown in table 5, 6 and 7. This synergistic results were observed when above mentioned combinations of herbicides were tried out on one of the most important weed of Rice ( paddy ) crop, Echinochloa erusgalli. The above mentioned herbicidal synergistic compositions of this invention can be applied as per the prescribed recommendations on the label by mixing the herbicides and water at right dosages. Advantages of the invention The composition prepared by the process of the present invention helps to : delay the dominance of the resistant strains of weeds; have a broader spectrum of activity and reduces risk of developing resistance;, achieve effective and economic control of undesirable weed species; improve biological performance in single application; minimize occupational exposure and hazards; decrease the cost of application; save fuel cost, labor cost; save applicator"s precious time; reduce wear of equipment and losses caused by mechanical damage to crops and soil. 24 We claim: 1. An improved synergistic herbicidal composition which demonstrates a high controlling effect with reduced environmental load and increased crop production as well as reduced crop protection cost preferably in the form of liquid or emulsifiable concentrate which comprises Pyrazosulfuron ethyl, in an amount ranging from 0.01 to 5 % by weight of composition, another herbicide selected from Butachlor, Pretilachlor and 2,4-D, in an amount ranging from 1 to 50 % by weight of composition and 45 to 98.9 % by weight of conventional agriculturally acceptable carrier(s) and excepient(s). 2. A synergistic herbicidal composition as claimed in claim 1 wherein the total active ingredient content is 1.00 to 60 % by weight of the composition , preferably 1.01 to 55 % by weight of the composition. 3. A synergistic herbicidal composition as claimed in claim 2 wherein the amount of Pyrazosulfuron ethyl active ingredient is from 0.01 to 5.0% by weight of composition, and one or more selected from Butachlor, Pretilachlor or 2,4-D from 1 to 50 % by weight of the composition. 4. A composition as claimed in claim 1 wherein the composition contains 0.01 to 5 % of Pyrazosulfuron ethyl and 2 to 50 % by weight of Butachlor. 5. A composition as claimed in claims 1 wherein the composition contains 0.01 to 5 % of Pyrazosulfuron ethyl and 5 to 50 % by weight of Pretilachlor, 6. A composition as claimed in claims 1 wherein the composition contains 0.01 to 5 % of Pyrazosulfuron ethyl and 1 to 50 % by weight of 2,4-D. 7. A composition as claimed in claims 1 to 6 wherein the composition contains agriculturally acceptable carrier/ (s), excepient(s), is / are selected from solid, liquid carrier/ (s), 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, ferilizers like 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. 8. A composition as claimed in claims 1 and claim 7 wherein excipient such as the surfactant(s) is non-ionic, cationic and /or anionic in nature is / are used which have good emulsifying, dispersing and properties. 9. A composition as claimed in claim 8 wherein the anionic surfactants used is both so-called 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 acid mixtures. 10. A composition as claimed in claims 1 to claim 9 wherein the excipient 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 pyrolidine and/or lactone or a mixture of thereof. 11. A composition as claimed in claims 1 to claim 10 wherein the excipient 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. 12. A composition as claimed in claims 1 to claim 11 wherein excipient such as wetting agent used is calcium /sodium sait(s) of alkyl aryl sulphonate. 13. A composition as claimed in claims 1 to claim 12 wherein excipient such as emetic agent used is selected lignocaine derivative and /or a formulation of lignocaine derivative. 14. A composition as claimed in claims 1 to claim 13 wherein excipient such as the antifoaming agent used is silicone oil derivative. 15. A composition as claimed in claims 1 to claim 14 wherein excipient such as the disintegrating agent used is selected from absorbing type clays like bentonite, Zeolite, Attapulgite and inorganic salts like sodium and Aluminium sulphate. 16. A composition as claimed in claims 1 to claim 15 wherein the filler(s) used is / are selected from silica, kaoline, clay and /or a mixture thereof. 17. A composition as claimed in claims 1 to claim 16 wherein the ratio of active to carrier is in the range of 1 : 1 to 1 : 10000. 18. A composition as claimed in claims 1 to claim 17 wherein the anticaking agent used is selected from Fumed silica, anhydrous Magnesium sulphate, a blend of sucrose and starch derivatives. 19. A composition as claimed in claims 1 to claim 18 wherein the dye(s) used selected is water soluble, water insoluble or a combination thereof. 20. A composition as claimed in claims 1 to claim 19 wherein the Pyrazo sulfur on ethyl used is of Technical grade of purity 95 % minimum. 21. A composition as claimed in claims 1 to claim 20 wherein the Butachlor used is of technical grade of purity 85 % minimum. 22. A composition as claimed in claims 1 to claim 21 wherein the Pretilachlor used is of technical grade of purity 94 % minimum. 23. A composition as claimed in claims 1 to 22 wherein the 2, 4-D used is of technical grade of purity 80 % minimum. 26 24. A composition as claimed in claims 1 to 23 wherein the dispersing agent used is formaldehyde condensate of alkyl phenols. 25. A composition as claimed in claims 1 to 24 wherein the solvent (s ) used are essentially: Aromatic hydrocarbons, preferably the fractions containing 8 to 12 carbon atoms, such as xylene mixtures or mineral oil fractions of medium to high boiling point such as kerosene and diesel oil, furthermore coal tar oils and oils of vegetable or animal origin; aliphatic, cyclic and aromatic hydrocarbons, for example cyclohexane, parafms, tetrahydronaphthalene, alkylated naphthalenes and their derivates,alkylated benzenes and their derivates, phthalic acid esters,such as dibutyl or dioctyl phthalate,alcohols and glycols and as well as their ethers and esters e.g. Methanol,propanol,butanol,cyclohexanol , ethylene glycol mono- and dimethyl ether; ketones such cyclohexanone; strongly polar solvents,for example amines such as N- methyl pyrrolidone, N- octylpyrrolidone and N-cyclohexylpyrrolidone or lactones such as butyrolactone;epoxidized plant oil esters such as methylated coconut soyabean oil ester and water mixtures of different liquid carriers are often suitable. 26. An improved herbicidal composition substantially as herein described with reference to the Examples 1 to 10.

Full Text

FORM 2
THE PATENTS ACT, 1970
(39 of 1970)
COMPLETE SPECIFICATION
(See Section 10)
"A SYNERGISTIC HERBICIDAL COMPOSITION "
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 ,
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 herbicidal composition containing selective herbicides and improvements in the use of selective herbicides like Pyrazosulfuron ethyl and other herbicide(s) preferably one or more from Butachlor, Pretilachlor and 2,4-D (2,4-dichloro phenoxy acetic acid).
This application is divided out of our application no 553/MUM/2002
In modernized agriculture today, considerable attention is being given to all aspects of crop production, especially to those which concern defence of crops against weeds, diseases and pests. In last few years a spurt in agricultural production is due to the green revolution, increased fertilizer use, crop production, improved irrigation and mfrastructural facilities. The important challenges confronted in the fanning today in the production practices is weed management. This invention is based on the strengths and weaknesses of ones approach in weed control and what better strategies can be adopted to contain their menacing impact on farming. Weed control using chemicals is much older . From 1940 onwards chemicals became the principal tools of weed control in the most developed nations and have been expanding slowly to developing nations ,
Weeds are the plants, which grows where they are not wanted. They grow in the fields where they compete with the crops for water, soil nutrients, light and space and thus reduce crop yields. They also harbour insects, pests and micro-organism. Certain weeds release into the soil the inhibitors or poisonous substances which are harmful to the plants, human beings and live stocks. They increase the expenditure on labour and equipment, render harvesting difficult, and reduces the quality and marketability of the agricultural produce. They block the drainage and impede the flow of the water in canals and water -transport channels and their growth in the rivers renders navigation very difficult. The dense growth of the weeds in water pollutes the water because they deoxygenate the water and kill the fish.
Weeds seeds germinate earlier, their seedlings grow faster, they flower earlier, and form seeds in profusion, and mature ahead of the crop they infest. Weeds have a remarkable capacity to germinate under varied conditions but very characteristically they are season bound and the peak period of the germination always takes place in certain season in the regular succession year after year.
Weeds belongs to the class Angiospermae (flowering plants) which have two subclass : Monocotyledoneae ( monocots) and Dicotyledoneae ( dicots). On the basis of the habitat, they are divided into terrestrial and aquatic categories, and on the basis of the duration of life they are divided into annuals, biennials and perennials. Annuals live and produce their seeds in a single growing season . Biennials need two growing season ; in one season they pass through their vegetative or rosette stage, followed by the reproductive stage in the next season. The multiplication of both the annuals and biennials is through seed. Perennials live indefinitely and are propagated not only through seeds but often vegetatively through underground structures such as rhizomes, stolons, bulbs and tubers. Perennials are of two types the simple and the creeping. The former multiply through seeds. They have no normal means of spreading vegetatively. However, if they are injured or cut, the severed portions produce new plants. Creeping perennials are spread by creeping roots, creeping above ground stems( stolons) and creeping underground stems ( rhizomes).

In non-irrigated areas, the competition between weeds and crops is largely for water. A saving of 750 to 1250 tonnes of water per hectare of soil, forming a one meter deep column, is possible by keeping the soil free from weeds. In irrigated tracts, the competition is severe for nutrients . The unchecked growth of weeds, in a wheat field measuring one hectare, removes about 20 Kg of Nitrogen , reducing the grain yield by about 12 Quintals. The minerals requirements of weeds are high. Weeds in a fallow land deplete the soil of both moisture and nutrients.
Weeds generate a formidable competition with crop plants for light. One of the secrets behind the high-yield potential of the dwarf varieties of crop plants is that they can capture solar energy more efficiently. Unchecked weed growth in the fields cropped with dwarf variety will intercept solar radiation to detriment of the crop plants. Likewise, the competition that weeds offer to the valuable crop plants may assume, at times , so alarming proportions as to smother the latter. Both the nature of the weed and the crop which they infest, influence the action of weedicides.
Measures against weeds comprise mechanical (cultivation and mowing), cultural or cropping, biological and chemical means. Each of these methods has certain merits and a prudent farmer can make use of one means or a combination of them to control weeds efficiently and economically. The controlling of weeds in the growing crops with weedicide increases their yields and ensure the efficient use of irrigation , fertilizer and plant protection measures.such as the spraying of insecticides and fungicides. The removing of weeds from the growing crop facilitates easy harvesting and gives a high-quality produce without admixture with the weed seeds. Chemical weed control can be adapted in time and in situations and under conditions which make manual, or mechanical weeding difficult. A great advantage of this method lies in killing weeds in the crop row or in the immediate vicinity of the crop plant. The chemical method is easier, less time consuming and less costly than weeding by hired labourers.
Chemicals as herbicides began to be produced in 1950 through industrial research. As a consequence, world agriculture has been the recipient of a continuously expanding range of herbicides. A "herbicide" as a compound modifies or controls plant growth. The quantity of a compound which is capable of producing such an effect is termed as "herbicidally effective amount". Modifying or controlling modes includes all deviations from natural development, e.g. Killing, defoliation, retardation, dessication, regulation, stunting, leaf burn, tillering, dwarfing and the like. The germinating seeds, emerging seedlings and established vegetation, including roots and above-ground portions are termed as "Plants".
In modern agriculture, chemical weed control through herbicides is the most popular method. Herbicides usage in a polyculture system prevailing in India is, however, not as simple as in monoculture due to differential selectivity and development of resistance in plant species as also due to herbicide persistence.
Most of the presently available herbicides provide only a narrow-spectrum of weed control. These herbicides control either grasses or broad leaf weeds but not both. Many of them have activity only on annual species while a few are only effective against perennials. For example in broad leaf crops particularly in oilseeds and pulses, herbicides are available to control grassy weeds. It is difficult to control the broad leaf weeds like Lathyrus spp. in chickpea, vicia spp. in lentil and Asphodel"s tenuifolius in mustard and chickpea. Thus there is a danger of species

replacement and hitherto less dominant weed becoming prominent and devastating. Selectively, therefore is also an important consideration in intercropping systems, which limits choice of herbicides.
With the continuous use of herbicides in monoculture systems, herbicide resistance development is becoming problematic. Herbicide resistance is the inherited ability not to be controlled by herbicide. The indiscriminate use of agricultural chemicals led to two different problems due to persistence. One being harmful/inhibitive effect on sensitive crop growth in succession in a cropping system and thus reducing choice of crops. The second being the toxic chemical residues left undegraded, which may result in potential ecological hazard and pollution In addition there are problems of secondary pests and resurgence of weeds. As a result, change in weed communities are observed.
In many cases, active herbicides in-combination have shown multi-facet advantage than when applied individually. Since the combination demonstrates a potency or/and activity level, exceeding that which might be expected from a mere addition of the individual potencies of the components are there by called as ""synergism". The present invention highlights the synergistic effect of a combination of two known active herbicides. Both the individual herbicides forming this combination, which is subject to this invention, are known to be potent herbicides , for their activity independent of each other.
In the WO patent no WO/03/024224 a herbicidal composition has been disclosed in which in
addition to customary inert formulation adjuvants conatins as active ingredient a mixture of at
least two compounds selected from the group oxadiargyl , oxadiazon, fentrazamide,
ethoxy sulfur on , quinchlorac, pyrazolate , amicarbazone, bromobutide, cafe ntrazone(-ethyl)
pyrazolate , pyraflufen(-ethyl), sulfentarzone , tepraloxydim, clodinafop- propargyl, pretilachlor,
butachlor, oxaziclomefone,fentrazamide benzobicyclon, molinate , quinchlorac, bentazone
,Pyrazolynate ,pentoxazone ,metamifop, cinosufuran, imazo sulfur an,
pyrazosulfuroan(ethyl),Azimsulfuran, benzsulfuran-methyl) triasulfuran, prosulfuran,
halo sulfur an(-methyl) sulfometuron(-methyl), sulfo sulfur an, chlorimuron,( -ethyl)
cyclosulfamuron , trisulfuran and idosulfuran .
The above patent states that any mixing ratio can be used but usually has an excess of one component over the other . The preferred ratio being 10: 1 to 1:10 preferably 5:1 to 1:5
especially 1:1
Though the composition disclosed includes amongst others a combination pretilachor , pyrazo sulfur an (ethyl) and butachlor, it is pertinent to note that none of the examples stipulates use of particular active ingredient mentioned . There is no example or description about the synergistic combination of pretilachor , pyrazosulfuran(ethyl) and butachlor.
Further the composition, the patent says , may be in form of emulsifying concentrates, directly sprayable or dilutable solutions , wettable powders granules or micrpores .
In the CN patent no 1286910 ,a compoition has been disclosed wherein the composition contains 10 to 50 % by weight of pretilachlor , 0.2.to 10 % by weight of Pyrazo zulfuron , PVC 1.0 to 2,0% by weight, sulfate 0.5 to 1% by weight, sodium lignosulphate 5 to 15 % by weight and carrier being the rest.
4

The composition is in the form of granules or wettable powders only.
The present invention provides a improved synergistic herbicidal composition containing Pyrazosulfuron ethyl and another one or more herbicide, selected from Butachlor, Pretilachlor or 2,4-D along with agriculturally acceptable carrier (s ) , adjuvants and other excipients. The composition in the present invention is preferably in the form liquid or Emulsifying concentrate.
Therefore , it is an object of the present invention to provide a composition of a herbicidal combination containing Pyrazo sulfur on ethyl and another herbicide (s), preferably from Butachlor,Pretilachlor,2,4-D, which demonstrates a high controlling effect with reduced environmental load and reduced crop production as well as reduced crop protection cost.
Another object of the present invention is to provide a herbicidal composition containing a synergistically effective amount of a combination of Pyrazosulfuron ethyl plus other herbicide (s), preferably from Butachlor,Pretilachlor,2,4-D, useful for the synergistic herbicidal control and enhanced crop protection.
Another object of the present invention is to provide a herbicidal composition, containing a synergistically effective amount of a combination of Pyrazosulfuron ethyl plus other herbicide (s), preferably, from Butachlor,Pretilachlor,2;4-D , in concentrated liquid, powder, granular form. These herbicidal composition is used in undiluted/ diluted form in fields.
Yet another object of the present invention is to provide a herbicidal composition, containing a synergistically effective amount of a combination of Pyrazosulfuron ethyl plus other herbicide (s), preferably from Butachlor,Pretilachlor,2,4-D , which delays the dominance of the resistant strains of pests.
Still another object of the present invention is to provide a herbicidal composition, containing a synergistically effective amount of a combination of Pyrazosulfuron ethyl plus other herbicide (s), preferably form Butachlor,Pretilachlor,2,4-D , which can achieve effective and economic control of undesirable weeds.
Yet another object of the present invention is to provide a herbicidal composition, containing a synergistically effective amount of a combination of Pyrazosulfuron ethyl plus other herbicide (s), preferably from Butachlor,Pretilachlor,2,4-D,which can improve biololgical performance in single application and minimize occupational exposure and hazards
Still another object of the present invention is to provide a herbicidal composition, containing a synergistically effective amount of a combination of Pyrazosulfuron ethyl plus other herbicide (s), preferably from Butachlor,Pretilachlor,2,4-D , which can decrease the cost of application, save fuel cost, labour cost and save applicator"s precious time and therefore very economical.
Another object of the present invention is to provide a herbicidal composition, containing a synergistically effective amount of a combination of Pyrazosulfuron ethyl plus other herbicide (s), preferably from Butachlor,Pretilachlor,2,4-D , which reduces the wear of equipment and losses caused by mechanical damage to the soil.

The process of this invention include intensive mixing and/ or milling of the active ingredients with other substances, such as stabilizers, emetic agents, rain-fasteners, solubilizers, adjuvants, antifoaming agent, wetting agent, dispersing agent, dye (s), fillers, carriers, surface active compounds (surfactants and / or emulsifiers ) and optionally solid and/ or liquid auxiliaries, as per the following process:
Thus the WO patent does not discuss the synergestic composition of the present invention.
The synergistic herbicidal compositions containing Pyrazosulfuron ethyl and
another one or more herbicide, preferably from Butachlor, Pretilachlor or 2, 4-D, can be prepared
per the following process:
i) the first part, comprising of Pyrazosulfuron ethyl and an agriculturally accepetable carrier (s), surfactants (s); and premixing these ingredient (s) thoroughly for at least half an hour in a pre -blender/mixer to have a homogeneous mixture of all the ingredient(s) of the first part as described earlier;
ii) the second part, comprising of stabilizers ,solublizers, adjuvants and second herbicide preferably one or more from Butachlor,Pretilachlor or 2,4-D and mixing these (stabilizers, solublizers,adjuvants and second herbicide ) in a mixer equipped with mixing arrangements to have a homogeneous mixture of all ingredients(s) of the second part;
iii) adding gradually the first part of the combination ,as a whole or a part thereof, to the first part, at a rate of addition of 0.1 to 100 kg/hour;
iv) thereafter the whole material of the step (3) is mixed thoroughly for at least one hour to have a homogeneous mixture.
The synergistic herbicidal combinations contain herbicidally effective amount of Pyrazosulfuron ethyl and another one or more herbicide, preferably from Butachlor, Pretilachlor or 2,4-D, in about 0.01 : 105 to 1 : 800 and agriculturally acceptable carrier (s), adjuvant(s), surfactant (s).
Agriculturally acceptable carrier (s), adjuvant (s), excepient (s) is / are selected from solid carrier(s) 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 phosphat, ammonium nitrate, ureas, and crushed products of vegetable origin such as cereal meal, tree bark meal, wood meal and nutshell meal, cellulose powders and the like . Suitable liquid carriers are essentially ; Aromatic hydro carbons,preferably the fractions containing 8 to 12 carbon atoms, such as xylene mixtures or mineral oil fractions of medium to high boiling point such as kerosine and diesel oil, furthermore coal tar oils and oils of vegetable or animal origin; aliphatic, cyclic and aromatic
6

hydrocarbons, for example cyclohexane,paraffins,tetrahydronaphthalene, alkylated
naphthalenes and their derivates,alkylated benzenes and their derivatives; phthalic acid esters, such as dibutyl or dioctyl phthalate,alcohols and glycols and as well as their ethers and esters e.g. Methanol,propanol,butanol,cyclohexanol , ethylene glycol mono- and dimethyl ether; ketones such cyclohexanone; strongly polar solvents.for example amines such as N-methyl pyrrolidone, N- octylpyrrolidone and N-cyclohexylpyrrolidone or lactones such as butyrolactone;epoxidized plant oil esters such as methylatied coconut soyabean oil ester,and water mixtures of different liquid carriers are often suitable.
The surfactant(s) such as non-ionic, cationic and /or anionic in nature is / are used 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 acids (CIO—C22), for example the sodium or potassium salt of oleic or stearic acid or of natural fatty acid mixtures.
Pyrazosulfuron ethyl and other herbicide preferably Butachlor, Pretilachlor and 2, 4-D, is a ready mix synergistic action product which qualifies all the requirements of a good herbicides mixture. In this invention all the components are compatible. Along with this, the proportion of the active components is precisely chosen to gain best biological results. Being a ready mix, it makes much easier and less troublesome to prepare a proper and effective liquid spray than the preparation of tank mixtures.
The composition of the present invention gives a quick and effective control of the weeds in crop fields to control weeds like Echinochloa crusgalli, Digitaria senguinalis, Setria app., Commelina benghalensis, Fimbristylis miliacoa, Cyperus iria, Eleusine indica, Panicum spp, Cyperus difformis, Cyperus rotunds, Alternanthera sessile, Caesulia axillaris, Cynotis cucullata, Ludwigia parviflora, Marsilae quadrifoliata, Monochoria vginalis, Echinochloa colonum, Eclipta alba, Sphenoclea zeylamica etc.
The name "Pyrazosulfuron ethyl" belongs to sulfonyl urea group herbicide describes a chemical substance having a molecular weight 414.4, is in the form of colourless crystals, m.p. 181 -182 ° C ; solubility in water of 0.0145 g/1 ( 20 °C) ; in methanol 0.7, hexane 0.2, benzene 15.6, chloroform 234.4, acetone 31.7 ( all in g/1 20 ° C) . Stable at 50 ° C for 6 months. Relatively stable at pH 7 . Unstable in acidic or alkaline media. The molecule is having a structural formula :

Ethyl 5-(4,6-dimethoxypyrimidin-2yl-carbaravIsulfamoyl)-l-methylpyrazole-4-carboxylate (IUPAC).
It inhibits the branched chain amino-acid synthesis ( acetolactate synthase or ALS). Acts by inhibiting biosynthesis of the essential amino acids valine and isoleucine, hence stopping cell division and plant growth. Selectivity derives from rapid metabolism ( demethylation of
7

methoxy group) in the crop. It acts as systemic herbicide, absorbed by roots and /or leaves and translocated to the meristem. It controls the annual and perennial broad-leaved weeds, and sedges, pre-or post-emergence in wet- sown and transplanted rice crops, at 15-30 g/ha.
Acute oral LD 50 for rats and mice >5000 mg/Kg. Acute percutaneousLD 50 for rats > 2000 mg/Kg. In rats after 48 hours, 80 % of applied pyrazosulfuron- ethyl is excreted in urine and faeces. The major metabolic reaction is demethylaton of methoxy group.
The name "Butachlor" belongs to chloroacetanilide group herbicide describes a chemical substance having a molecular weight 311.9, is in the form of light yellow to purple liquid with a faint, sweet odour; m.p. -2.8 ° C to 1.7 ° C; b.point 156 ° C / 0.5 mm Hg; solubility in water of 20 mg/1 ( 20 °C) ; soluble in most organic solvents, including diethyl ether, acetone, benzene, ethanol, ethyl acetateand hexane. Decomposes at a temperature above 164 ° C, stable to UV light stable indefinetely below 45 ° C.
The molecule is having a structural formula :

,\-butoxymethyl-2-chloro-2",6"-diethylacetani!ide ( IUPAC )
It acts as a protein synthesis inhibitor. It is selective systemic herbicide, absorbed primarily by the germinating shoots and secondarily by the roots, with translocation throughout the plant; giving higher concentration in vegetative parts then in reproductive parts. Used as pre-emergence for the control of annual grasses and certain broad-leaved weeds in rice, both seeded and transplanted. It shows selectivity in barley, cotton, peanuts, sugarbeets, wheat and several brassica crops. Activity is dependent on water availability such as rainfall following treatment, overhead irrigation of application to standing water as in rice culture.
Non-phytotoxic to rice, cotton, barley, wheat, peanuts, sugarbeet and some brassicas. Acute oral LD50 for rats 2000, mice 4747, rabbits > 5010 mg/Kg. Acute percutaneous LD50 for rabbits > 13000 mg/Kg. In animals, it gets metabolized to water soluble metabolites and excreted. In plants it rapidly metabolized to water soluble metabolites, leading, eventually to mineralization.
The name "Pretilachlor"1 belongs to chloroacetanilide group herbicide describes a chemical substance having a molecular weight 311.9, is in the form of colourless liquid ; b.point 135 ° C / 0.001 mm Hg; solubility in water of 50 mg/1 ( 20 °C) ; very soluble in benzene, hexane, methanol and dichloromethane . Relatively stable to hydrolysis ; DT50 (clc.) (20°C) > 200 days ( pH 1 - pH 9), 14 days ( pH 13) . Flash point 129 ° C. The molecule is having a structural formula :

2-chloro-2",6"-diethyl-N-(2-propoxyethyl) acetanilide (IUPAC) It inhibits the cell division. It is selective herbicide. It is taken up readily by the hypocotyl, mesocotyls and coleoptiles, and to a lesser extent by the roots of the germinating weeds. It is effective against main annual grasses, broad-leavec weeds and sedges in transplanted and seeded rice. Applied alone, pretilachlor will cause injury to direct seeded rice.
Acute oral LD50 for rats 6099 mg/Kg. Acute percutaneous LD50 for rats > 3100 mg/Kg. Moderate irritation to skin; non-irritatant to eyes (rabbits). Non-toxic to birds. In animals, substitution of the chlorine atom for glutathione to form a conjugate. Cleavage of the ether bond to yield an ethyl alcohol derivative.
Both metabolites axe susceptible to further degradation . In plants, the substitutionof the chlorine atom to form a conjugate occurs. Cleavage of the ether bond to an ethyl alcohol derivative occurs. Hydrolytic and reductive removal of the chlorine atom occurs. In soil/ environment when applied to paddy water, pretilachlor disappeared from water by adsorption to the soil, wrhere it is rapidly degraded under practical condition, median DT50 (lab.) 30 days. Due to strong soil adsorption, unlikely to leach.
The name " 2,4-D" (2,4-dichlorophenoxy)acetic acid belongs to aryloxyalkanoic acid group herbicide describes a chemical substance having a molecular weight 221.0, is in the form of colourless powder; m.point. 140.5 ° C; solubility in water of 311 mg/1 ( pH 1,25° C); 0.6 g/1 ( 20 °C) ; in ethanol 1250, diethyl ether 243, heptane 1.1; toluene 6.7, xylene 5.8(all in g/Kg, 20 ° C). Insoluble in petroleum oils. Mono-n-butylamine salt; in water at 30 ° C, 18 g/kl . 2,4-D is atrong acid, and form water-soluble salt with alkali metals and amines Hard water leads to precipitation of the calcium and magnesium salts, but a sequestring agent is included in the formulations to prevent this. The molecule is having a structural formula :
CI OH
(2,4-dichloro phenoxy) acetic acid. (IUPAC) It is selective systemic herbicide. Salts are readily absorbed by the roots, whilst esters are readily absorbed by the foliage. Translocation occurs, with accumulation principally at meristematic regions of shoots and roots. Acts as a growth inhibitor. Use post-emergence control of annual and perennial broad-leaved weeds in cereals, maize, sorghum, grassland,
established turf, grass seed crops, orchards,cranberries, asparagus, sugarcane, rice, forestry and on non-crop land ( including the areas adjacent to water) at 0.28-2.3 Kg/ha. Control of broad leaved aquatic weeds weeds. The isopropyl ester can be also be used as a plant growth regulator to prevent premature fruit fall in citrus fruits. Phytotoxic to most broad leaved crops, especialliy cotton, vines,tomatoes, ornamentals, fruit trees, oilseed rape and beet.
Acute oral LDso for wild ducks > 1000, Japanese quail 668, pigeon 668, pheasants 472 mg/Kg.
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LC50 (96h) for mallard ducks > 5620 mg/1 . Some formulations are toxic to fish, whilst others are not. Not toxic to bees .
It does not appear to produce direct toxic effects on any animal species. In rats, following oral administration, elimination is rapid, and mainly as the unchanged substance. Following single doses of upto 10 mg/Kg, excretion is almost complete after 24 hours, although, with higher doses, complete elimination takes longer. The maximum concentration in organs is reached after 12 hours. In plants, metabolism involves hydroxylation, decarboxylation, cleavage of the acid side-chain, and ringopening. In soil, microbial degradation involves hydro xylation, decarboxylation, cleavage of the acid side-chain, and ring opening. Rapid degradation in the soil prevents significant downeward movement under normal conditions.Process for selectively combating weeds in the culturing of paddy (rice), which comprises the Pyrazo sulfur on ethyl and others, sufficient to selectively hinder the growth of weeds during the culturing of paddy, applied as a selective pre and early post emergence herbicide.
Application rates depend upon the weeds to be controlled and the degree of control desired. The product provided by this invention is relatively more advantageous and exhibit very desirable characteristic noted herein after. The herbicidal composition can be applied to weed surfaces after dilution with water in recommended dilution rates.
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 pest 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 resulting 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 concentration of the active ingredients.
In general, the synergistic effect may be achieved at application rates of the active ingredient of about 10 to 20 g/ha of Pyrazosulfuron ethyl in combinaiton with 700 to 1500 g/ha of Butachlor; preferably in about 14 g/ha. Pyrazosulfuron ethyl to 1000 g/ha g/ha of Butachlor.
In general, the synergistic effect may be achieved at application rates of the active ingredient of about 10 to 20 g/ha of Pyrazosulfuron ethyl combinaiton with 280 to 575 g/ha of Pretilachlor, preferably in about 14 g/ha of Pyrazosulfuron ethyl to 400 g/ha of Pretilachlor.
In general, the synergistic effect may be achieved at application rates of the active ingredient of about 10 to 20 g/ha of Pyrazosulfuron ethyl combinaiton with 350 to 715 g/ha of 2, 4-D, preferably in about 14 g/ha of Pyrazosulfuron ethyl to 500 g/ha g/ha of 2, 4-D.
Preferred combination of the composition prepared by the process of the present invention are those combination wherein the active ingredient ratio (weight/weight) of Pyrazosulfuron ethyl and others preferably Butachlor, Pretilachlor or 2,4-D , is about 0.01 : 5 to 1 : 50
More preferred combination of the invention are combination of Pyrazosulfuron ethyl -and Butachlor wherein the active ingredient ratio (weight/weight) of Pyrazosulfuron ethyl : Butachlor is about 0.01 : 5 to 2 : 50.
More preferred combination of the invention are combination of Pyrazosulfuron ethyl and Pretilachlor wherein the active ingredient ratio (weight/weight) of Pyrazosulfuron ethyl: Pretilachlor is about 0.01 : 5 to 5 : 50.
More preferred combination of the invention are combination of Pyrazosulfuron ethyl and 2,4-D wherein the active ingredient ratio (weight/weight) of Pyrazosulfuron ethyl : 2,4-D is about 0.01 : 5 to 1 : 50 .
The ratios of active ingredients in this invention are found tobe different than the ratios of that are disclosed in WO patent. The composition of this invention is preferably in the liquid form. It can also be in emulsifyable concentrate.
Advantageously, the composition of the invention may be formulated in powder, solid or liquid form. A preferred liquid form comprises of a synergistically effective amount of a combination of Pyrazosulfuron ethyl plus other herbicide (s), preferably from Butachlor, Pretilachlor, 2, 4-D and / or solid or liquid inert substance(s). A preferred solid composition may be in a form of a homogeneous powder containing a synergistically effective amount of a combination of Pyrazosulfuron ethyl plus other herbicide (s), preferably from Butachlor,Pretilachlor,2,4-D and/ or in granular form of size ranging from 50 to 2000 micron containing a synergistically effective amount of a combination of Pyrazosulfuron ethyl plus other herbicide (s), preferably from Butachlor.Pretilachlor, 2,4-D.

The forms of application of the compositions according to this invention depend on the intended purposes; in any case, they guarantee uniform 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.
Alternatively, concentrates which consist of herbicidally 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 as a dilute spray prepared from any of the above-said formulations.
The synergistic effective amount of the combination of Pyrazo sulfur on ethyl may vary accordingly to prevailing conditions such as the particular second herbicide present, , type of weeds, application timing, weather conditions, soil conditions, mode of application, topographical character, target crop and the like.
The composition prepared by the process of the present invention is superior herbicidal compositions and are especially useful for the control of weeds. 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 herbicidal composition prepared by the process of the invention are found to be highly active against a wide variety of weeds like Echinochloa crusgalli, Digitaria senguinalis, Setria app., Commelina benghalensis, Fimbristylis miliacoa, Cyperus iria, Eleusine indica, Panicum spp, Cyperus difformis, Cyperus rotunds, Alternanthera sessile, Caesulia axillaris, Cynotis cucullata, Ludwigia parviflora, Marsilae quadrifoliata, Monochoria vginalis, Echinochloa colonum, Eclipta alba, Sphenoclea zeylamica etc.
The present invention highlights the synergistic effect of the combination of Pyrazo sulfuron ethyl and containing a synergistically effective amount of a combination of Pyrazo sulfuron ethyl plus another herbicide(s), preferably from Butachlor,Pretilachlor,2,4-D . Following the right use of the invented technology and the composition of the invention with a formulation 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 and helps to ;

- delay the dominance of the resistance strains of weeds
- have a broader spectrum of activity and reduces risk of developing resistance
- achieve effective and economic control of undesiretl weeds
- improve biological performance in single applications
- minimise occupational exposure and hazards -decrease the cost of appliation
- save fruel cost, labour cost
- save applicator"s precious time
- reduce wear of equipment and losses caused by mechanical damage to crops.
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.
The general composiiton of Pyrazosulfuron ethyl and Butachlor is as follows : Composition
Ingredient Quantity (% w/wl
Pyrazosulfuron ethyl Techical (purity 95%) Min. 0.01 to 5.00 Max.
Butachlor Technical (purity 85%) Min. 2.00 to 50.00 Max.
Stabilizer (Sodium alginate) Min. 0.01 to 10.00 Max
Emetic agent (Bitrex ) Min. 0.00 to 0.005 Max
Disintegrating agent (Zeolite) Min. 0.00 tolO.OO Max
Antifoaming agent (Antimousse 426 -R) Min. 0.00 to 1.00 Max
Wetting cum dispersing agent (Lisapol BN - 200) Min. 0.01 to 10.00 Max
Anticaking agent (anhydrous Magnesium sulphate) Min. 0.01 to 5.00 Max
Dye(s) Min. 0.05 to 1.00 Max
Adjuvant (s) Min. 0.05 to 10.00 Max
Emulsifier (s) Min. 0.1 to 10.00 Max
Solvent(s) _ Q.S.
Total 100.00 %(w/w)
Above mentioned synergistic herbicidal composition"s preparation comprises mixing thoroughly, for half an hour, Pyrazosulfuron ethyl, with one or more another herbicide preferably from Butachlor,Pretilachlor or 2,4-D, adjuvant (s), solid and/ or liquid carriers, surfactant (s),with/ without dye in a mixer equipped with agitator to get a homogenous mixture of all the ingredients of above mentioned herbicidal composition. The final product can be in the form of wettable powders, granules.liquid and or any other suitable form in the given compositions.

Pyrazosulfuron ethyl and Butachlor, in liquid form in following given combinations:

Table-1 Shows synergistic herbicidal composition of Pyrazosulfuron
Component PSE PSE +Butachlor PSE + Butachlor
+Butachlor (1+45) %w/w (0.7+50) %w/w (3+35) %w/w

ethyl (PSE) + Butachlor
PSE PSE
+Butachlor +Butachlor
(1+50) (5+50)
%w/w %w/w

Pyrazosulfuron
ethyl Tech@95 3.16 1.05 0.74 1.05 5.26
Butachlor_Tech
@85 41.18 52.94 58.82 58.82 52.82
Stabilizer 1.00 1.00 1.00 1.00 1.00
Surfactant (s) 2.00 3.00 3.00 3.00 5.00
Disintegrating
agent 2.00 2.50 2.50 2.50 3.00
Adjuvants 3.00 3.00 3.00 4.00 4.00
Emulsifiers 10.00 10.00 10.00 10.00 12.00
Dye 0.10 0.10 0.10 0.10 0.10
Liquid
carrier(s) 37.56 26.41 20.84 19.53 16.82
Total (% ) 100.00 100.00 100.00 100.00 100.00

The general composiiton of Pyrazosulfuron ethyl and Pretilachlor is as follows :
Ingredient Quantity (% w/w)
Pyrazosulfuron ethyl Techical (purity 95%) Min. 0.01 to 5.00 Max.
Pretilachlor Technical (purity 94%) Min. 5.00 to 50.00 Max.
Stabilizer (Sodium alginate) Min. 0.01 to 10.00 Max
Emetic agent (Bitrex ) Min. 0.00 to 0.005 Max
Disintegrating agent (Zeolite) Min. 0.00 tolO.OO Max
Antifoaming agent (Antimousse 426 -R) Min. 0.00 to 1.00 Max
Wetting cum dispersing agent (Lisapol BN - 200) Min. 0.01 to 10.00 Max
Anticaking agent (anhydrous Magnesium sulphate) Min. 0.01 to 5.00 Max
Dye(s) Min. 0.05 to 1.00 Max
Adjuvant (s) Min. 0.05 to 10.00 Max
Emulsifier (s) Min. 0.1 to 10.00 Max
Solvent(s) Q.S.
Total 100.00 %(w/w)
15

Pyrazosulfuron ethyl and Pretilachlor, in liquid form in following given combinations:
Table-2 Shows the synergistic herbicidal composition of Pyrazosulfuron ethyl (PSE) + Pretilachlor

Component PSE + PSE + PSE ■ PSE + PSE
Pretilachlor Pretilachlor Pretilachlor Pretilachlor Pretilachlor
(3+35) %w/w (1+40) %w/w (1.4+40) %w/w (2+40) %w/w (5+50)
%w/w
Pyrazosulfuron
ethyl
Tech@95 3.16 1.05 1.47 2.11 5.26
Pretilachlor
Tech @ 94 37.23 42.55 42.55 42.55 53.19
Stabilizer 1.00 1.00 1.00 1.00 1.00
Surfactant(s) 2.00 2.00 2.50 3.00 4.00
Disintegrating
agent 3.00 3.00 3.00 3.00 3.00
Adjuvants 3.00 3.00 3.00 4.00 4.00
Emulsifiers 8.00 10.00 10.00 10.00 12.00
Dye 0.10 0.10 0.10 0.10 0.10
Liquid
carrier(s) 42.51 37.30 36.38 34.24 17.45
Total (%) 100.00 100.00 100.00 100.00 100.00

The general composition of Pyrazosulfuron ethyl and 2,4-D is as follows :
Ingredient Quantity (% w/w)
Pyrazosulfuron ethyl Techical (purity 95%) Min. 0.01 to 5.00 Max.
2, 4-D Technical (purity 80%) Min. 1.00 to 50.00 Max.
Stabilizer (Sodium alginate) Min. 0.01 to 10.00 Max
Emetic agent (Bitrex ) Min. 0.00 to 0.005 Max
Disintegrating agent (Zeolite) Min. 0.00 tolO.OO Max
Antifoaming agent (Antimousse 426 -R) Min. 0.00 to 1.00 Max
Wetting cum dispersing agent (Lisapol BN-200) Min. 0.01 to 10.00 Max
Anticaking agent (anhydrous Magnesium sulphate) Min. 0.01 to 5.00 Max
Dye(s) Min. 0.05 to 1.00 Max
Adjuvant (s) Min. 0.05 to 10.00 Max
Emulsifier (s) Min. 0.1 to 10.00 Max
Fillers (s) (Insilco and Kaolex ) / solvent(s) Q.S.
Total 100.00 %(w/w)
17

Pyrazosulfuron ethyl and 2,4-D. in powder form in following given combinations:

Table-3 Shows the synergistic herbicidal composition of Pyrazosulfuron ethyl ( PSE ) + 2,4-D
Component PSE + 2,4-D PSE + 2,4-D PSE + 2,4-D PSE + 2,4-D PSE -2,4-D
(0.1+20) (1+25) %w/w (1+35) %w/w (2.5+40) (5+50)
%w/w %w/w %w/w
Pyrazosulfuron
ethyl
Tech@95 0.11 1.05 1.05 2.63 5.26
2,4-DTech @
80 25.00 31.25
Stabilizer 1.00 1.00
Surfactant(s) 5.00 5.00
Disintegrating
agent 5.00 4.00
Adjuvants 2.00 3.00
Antifoaming
agent 1.00 1.00
Dye 0.10 0.10
Solid carrier(s) 60.79 53.60
Total (%) 100.00 100.00

43.75 50.00 62.50
1.00 2.00 2.50
6.00 7.00 10.00
5.00 5.00 5.00
3.00 2.00 2.00
1.00 1.00 1.00
0.10 0.20 0.30
39.10 30.17 11.44
100.00 100.00 100.00

18

Pyrazosulfuron ethyl and 2,4-D, in granular form in following given combinatios:
Table-4 Shows the synergistic herbicidal composition of Pyrazosulfuron ethyl+2,4-D
Component PSE + 2,4-D PSE + 2,4-D PSE + 2,4-D PSE + 2,4-D PSE+2,4-D
(0.07+2.5) % (1+2.5) % w/w (0.01+5) % w/w (l+5)%w/w (2+10)
w/w % w/w

Pyrazosulfuron ethyl Tech@95 0.07 0.11 0.01 1.05 2.11
2,4-DTech @ 85 3.13 3.12 1.00 6.25 0.50 6.25
1.00 12.50
Stabilizer 1.00

2.00
Surfactant(s) 2.00 2.00 3.00 3.00 5.00
Disintegrating agent 2.00 2.00 2.00 2.00 4.00
Adjuvants 1.00 1.00 2.00 2.00 3.00
Binding agent (adjuvant) 2.00 2.00 2.00 3.00 4.00
Dye 0.10 0.10 0.10 0.10 0.10
Solid carrier(s) 88.70 88.67 84.14 81.60 67.29
Total (%) 100.00 100.00 100.00 100.00 100.00

Example
Evaluation of the synergistic herbicidal effect of the Pyrazo sulfuron ethyl plus a second herbicide preferably from Butachlor,Pretilchlor and 2,4-D can be established by using any composition prepared by the process described in the above examples. For these evaluations one or more of the cornpositons prepared in the examples are used here.
In this evaluation, one of the important weeds of Rice ( paddy ) corps , namely Echinochloa crusgalli is grown in standard greenhouse soil until its plants have reached the 6-leaf stage.Said plant are then sprayed with an aqueous solution of the test copound Pyrazosulfuron ethyl and a second herbicide preferably one of the following Butachlor,Pretilachlor or 2,4-D,using a spray nozzle opetating at 30 psi for a predetermined time so as to obtain a range of application rates of about 10 g/ha to 1500 g/h . Each treatment is replicated 3 times.Afier spraying, the plants are placed on greenhouse benches and are cared for in a manner commensurate with standard greenhouse practice. At 4 weeks after treatment, the plants are examined, and the % weed control as compared to the untreated check is recorded.
Synergism can be calculated by using the Colby"s method i.e. the expected (or predicted) response ( E ) of the combination is calculated by taking the product of the observed response for each individual component X and Y, of the combination when applied alone divided by 100 and subtracting this value from the sum of observed response ( X + Y ) for each component when applied alone.
E = (X + Y)-{ [X. Y]/100} where E - expected or predicted response
X- observed response for "A" component Y- observed response for "B" component
Synergism of the combination is then determined by comparing the observed response ( O ) of
the combination to the expected (or predicted) response ( E )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)
e.g. a. if E > O then result is antagonistic effect;
b. if E = O then result is simply additional effect;
c. if E The treatment comprises different doses of Pyrazo sulfuron ethyl with a second herbicide preferably Butachlor, Pretilachlor or 2,4-D at doses specified specificallly below within relative examples.
Using the above process, Pyrazo sulfuron ethyl may be evaluated alone and in combination with second herbicidal compound.
20

For example, the synergistic effect may be achieved at application rates of the active ingredient of about 10 to 20 g/ha of Pyrazosulfuron ethyl in combinaiton with 700 to 1500 g/ha of Butachlor; preferably in about 14 g/ha of Pyrazosulfuron ethyl to 1000 g/ha.
For example, the synergistic effect may be achieved at application rates of the active ingredient of about 10 to 20 g/ha of Pyrazosulfuron ethyl combinaiton with 280 to 575 g/ha of Pretilachlor, preferably in about 14 g/ha of Pyrazosulfuron ethyl to 400 g/ha of Pretilachlor.
For example, the synergistic effect may be achieved at application rates of the active ingredient of about 10 to 20 g/ha of Pyrazosulfuron ethyl combinaiton with 350 to 715 g/ha of 2,4-D, preferably in about 14 g/ha of Pyrazosulfuron ethyl to 500 g/ha of 2,4-D.
Treatments which are used are shown in following table 5 .
As can be seen from the data shown in Table 5 below, application of a combination of Pyrazosulfuon ethyl and Butachlor gives significantly greater weed control [of Rice ( paddy ) crop weed Echinochloa crusgall ] than that which could be predicted from the weed control resulting from the application of either Pyrazosulfuron ethyl alone or Butachlor alone.
Table -5 Shows the synergistic effect for Pyrazosulfuron and Butachlor
4iA" Butachlor (active "B" Pyra2osulruron ethyl Observed Mortality (%) Expected Mortality (%) =E Difference (%) D= O - E
ingredient g/ha) (active ingredient g/ha) Y =0
0 0 0
0 10 Y-22.62
0 20 44.86
0 30 60.97
700 0 X= 16.75
1500 0 37.11
700 10 59.35 35.58 23.77
700 20 95.2 54.09 41.11
700 30 88.66 67.50 21 16
1500 10 68.84 51.33 1751
1500 20 95 65.32 29.68
1500 30 97 75.45 21.55
Colby"s formula worked out for expected mortality (E) for the row number 7 from above table as :
E = (X + Y)-{[XxY]/100} where E - expected or predicted response
X- observed response for "A" (700) component = 16.75 Y- observed response for "B" (10) component = 22.62
E for a combination (Butachlor 700 + Pyrazosulfuron ethyl 10)= ( X + Y) - { [ X x Y]/100}
= (16.75 + 22.62) - {[16.75 x 22.62]/100} = (39.37) - { [378.885}/100}
= (39.37)-{3.7885} =35.58115 =35.58 0-59.35 Here E

As can be seen from the data shown in Table 6 below, application of a combination of Pyarzosulfuon ethyl and Pretilachlor gives significantly greater weed control [of Rice ( paddy ) crop weed Echinochloa crussall ] than that which could be predicted from the weed control resulting from the application of either Pyrazosulfuron ethyl alone or Pretilachlor alone.
Table - 6 Shows the synergistic effect for Pyrazosulfuron ethyl and Pretilachlor

Pretilachlor (active ingredienl g/ha) Pyrazosulfuron Observed
: ethyl (active Mortality (%) -■ ingredient g/ha) Expected -O Mortality (%) =E Difference D=0-E
0 0 0
0 10 22.52
0 20 44.96
0 30 60.87
280 0 59.44
575 0 59.78
280 10 84 68.57 15.43
280 20 92 77.68 14,32
280 30 95.49 84.13 11.36
575 10 87.78 68.84 18.94
575 20 99.53 77.86 21.67
575 30 97.52 84.26 13.26

(%)

As can be seen from the data shown in Table 7 below, application of a combination of Pyarzosulfuon ethyl and 2,4-D gives significantly greater weed control [of Rice ( paddy ) crop weed Echinochloa cruseall ] than that which could be predicted from the weed control resulting from the application of either Pyrazosulfuron ethyl alone or 2,4-D alone.
Table - 7 Shows the synergistic effect for Pyrazosulfuron ethyl and 2,4-D

2,4-D (active Pyrazosulfuron Observed Expected Difference (%)
ingredient g/ha) ethyl (active Mortality (%) =0 Mortality (%) = E " D= 0 - E

13.10 18.60 11.38 15.50 20.30 13.60
ingredient g/ha)

0
22.4
44.9
60.95
30
62.25
58.78 45.68
80.03 61.43
84.04 72.66
86.20 70.70
99.50 79.20
98.85 85.25
Conclusion: From above tables 5, 6, 7, it reflects that the Pyrazosulfuron ethyl shows a synergistic effect when applied with other herbicides like Buatchlor, Pretilachlor and 2, 4-D and vice-versa. Synergism was more when the combinations were in the range of ,as stated in examples earlier for Pyrazosulfuron ethyl plus Butachlor, Pyrazosulfuron ethyl plus Pretilachlor and Pyrazosulfuron ethyl plus 2,4-D,respectively.

Result : Pyrazosulfuron ethyl with another one herbicide preferably from Butachlor,
Pretilachlor or 2,4-D gives synergistic effects as shown in table 5, 6 and 7.
This synergistic results were observed when above mentioned combinations of herbicides were tried out on one of the most important weed of Rice ( paddy ) crop, Echinochloa erusgalli.
The above mentioned herbicidal synergistic compositions of this invention can be applied as per the prescribed recommendations on the label by mixing the herbicides and water at right dosages.
Advantages of the invention
The composition prepared by the process of the present invention helps to : delay the dominance of the resistant strains of weeds;
have a broader spectrum of activity and reduces risk of developing resistance;, achieve effective and economic control of undesirable weed species;
improve biological performance in single application;
minimize occupational exposure and hazards;
decrease the cost of application;
save fuel cost, labor cost;
save applicator"s precious time;
reduce wear of equipment and losses caused by mechanical damage to crops
and soil.
24

We claim:
1. An improved synergistic herbicidal composition which demonstrates a high controlling effect with reduced environmental load and increased crop production as well as reduced crop protection cost preferably in the form of liquid or emulsifiable concentrate which comprises Pyrazosulfuron ethyl, in an amount ranging from 0.01 to 5 % by weight of composition, another herbicide selected from Butachlor, Pretilachlor and 2,4-D, in an amount ranging from 1 to 50 % by weight of composition and 45 to 98.9 % by weight of conventional agriculturally acceptable carrier(s) and excepient(s).
2. A synergistic herbicidal composition as claimed in claim 1 wherein the total active ingredient content is 1.00 to 60 % by weight of the composition , preferably 1.01 to 55 %
by weight of the composition.
3. A synergistic herbicidal composition as claimed in claim 2 wherein the amount of Pyrazosulfuron ethyl active ingredient is from 0.01 to 5.0% by weight of composition, and one or more selected from Butachlor, Pretilachlor or 2,4-D from 1 to 50 % by weight of the composition.
4. A composition as claimed in claim 1 wherein the composition contains 0.01 to 5 % of Pyrazosulfuron ethyl and 2 to 50 % by weight of Butachlor.
5. A composition as claimed in claims 1 wherein the composition contains 0.01 to 5 % of Pyrazosulfuron ethyl and 5 to 50 % by weight of Pretilachlor,

6. A composition as claimed in claims 1 wherein the composition contains 0.01 to 5 % of Pyrazosulfuron ethyl and 1 to 50 % by weight of 2,4-D.
7. A composition as claimed in claims 1 to 6 wherein the composition contains agriculturally acceptable carrier/ (s), excepient(s), is / are selected from solid, liquid carrier/ (s), 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, ferilizers like 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.
8. A composition as claimed in claims 1 and claim 7 wherein excipient such as the surfactant(s) is non-ionic, cationic and /or anionic in nature is / are used which have good emulsifying, dispersing and properties.
9. A composition as claimed in claim 8 wherein the anionic surfactants used is both so-called 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 acid mixtures.

10. A composition as claimed in claims 1 to claim 9 wherein the excipient 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 pyrolidine and/or lactone or a mixture of thereof.
11. A composition as claimed in claims 1 to claim 10 wherein the excipient 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.
12. A composition as claimed in claims 1 to claim 11 wherein excipient such as wetting agent used is calcium /sodium sait(s) of alkyl aryl sulphonate.
13. A composition as claimed in claims 1 to claim 12 wherein excipient such as emetic agent used is selected lignocaine derivative and /or a formulation of lignocaine derivative.
14. A composition as claimed in claims 1 to claim 13 wherein excipient such as the antifoaming agent used is silicone oil derivative.
15. A composition as claimed in claims 1 to claim 14 wherein excipient such as the disintegrating agent used is selected from absorbing type clays like bentonite, Zeolite,
Attapulgite and inorganic salts like sodium and Aluminium sulphate.
16. A composition as claimed in claims 1 to claim 15 wherein the filler(s) used is / are selected from silica, kaoline, clay and /or a mixture thereof.
17. A composition as claimed in claims 1 to claim 16 wherein the ratio of active to carrier is in the range of 1 : 1 to 1 : 10000.
18. A composition as claimed in claims 1 to claim 17 wherein the anticaking agent used is selected from Fumed silica, anhydrous Magnesium sulphate, a blend of sucrose and starch derivatives.
19. A composition as claimed in claims 1 to claim 18 wherein the dye(s) used selected is water soluble, water insoluble or a combination thereof.
20. A composition as claimed in claims 1 to claim 19 wherein the Pyrazo sulfur on ethyl used is of Technical grade of purity 95 % minimum.
21. A composition as claimed in claims 1 to claim 20 wherein the Butachlor used is of technical grade of purity 85 % minimum.
22. A composition as claimed in claims 1 to claim 21 wherein the Pretilachlor used is of technical grade of purity 94 % minimum.
23. A composition as claimed in claims 1 to 22 wherein the 2, 4-D used is of technical grade of purity 80 % minimum.
26

24. A composition as claimed in claims 1 to 23 wherein the dispersing agent used is formaldehyde condensate of alkyl phenols.
25. A composition as claimed in claims 1 to 24 wherein the solvent (s ) used are
essentially: Aromatic hydrocarbons, preferably the fractions containing 8 to 12 carbon
atoms, such as xylene mixtures or mineral oil fractions of medium to high boiling point
such as kerosene and diesel oil, furthermore coal tar oils and oils of vegetable or animal
origin; aliphatic, cyclic and aromatic hydrocarbons, for example cyclohexane, parafms,
tetrahydronaphthalene, alkylated naphthalenes and their derivates,alkylated benzenes and
their derivates, phthalic acid esters,such as dibutyl or dioctyl phthalate,alcohols and
glycols and as well as their ethers and esters e.g.
Methanol,propanol,butanol,cyclohexanol , ethylene glycol mono- and dimethyl ether;
ketones such cyclohexanone; strongly polar solvents,for example amines such as N-
methyl pyrrolidone, N- octylpyrrolidone and N-cyclohexylpyrrolidone or lactones such as
butyrolactone;epoxidized plant oil esters such as methylated coconut soyabean oil ester
and water mixtures of different liquid carriers are often suitable.

26. An improved herbicidal composition substantially as herein described with reference to
the Examples 1 to 10.

Documents:

1010-mum-2003-abstract(30-08-2007).doc

1010-mum-2003-abstract(30-08-2007).pdf

1010-mum-2003-abstract.doc

1010-mum-2003-abstract.pdf

1010-mum-2003-cancelled pages(25-09-2003).pdf

1010-mum-2003-claims(granted)-(30-08-2007).doc

1010-mum-2003-claims(granted)-(30-08-2007).pdf

1010-mum-2003-claims.doc

1010-mum-2003-claims.pdf

1010-mum-2003-correspondence(14-09-2007).pdf

1010-mum-2003-correspondence(ipo)-(28-11-2007).pdf

1010-mum-2003-correspondence(ipo).pdf

1010-mum-2003-correspondence.pdf

1010-mum-2003-description(granted).doc

1010-mum-2003-description(granted).pdf

1010-mum-2003-form 1(30-08-2007).pdf

1010-mum-2003-form 1-25-09-2003.pdf

1010-mum-2003-form 1-30-08-2007.pdf

1010-mum-2003-form 13(14-09-2007).pdf

1010-mum-2003-form 13(30-08-2007).pdf

1010-mum-2003-form 13.pdf

1010-mum-2003-form 19(25-09-2003).pdf

1010-mum-2003-form 19.pdf

1010-mum-2003-form 2(granted)-(30-08-2007).doc

1010-mum-2003-form 2(granted)-(30-08-2007).pdf

1010-mum-2003-form 2(granted).doc

1010-mum-2003-form 2(granted).pdf

1010-mum-2003-form 2(provisional specification).pdf

1010-mum-2003-form 2(title page).pdf

1010-mum-2003-form 3(20-12-2006).pdf

1010-mum-2003-form 3(25-09-2003).pdf

1010-mum-2003-form 3.pdf

1010-mum-2003-form 5(14-09-2007).pdf

1010-mum-2003-form 5(25-09-2003).pdf

1010-mum-2003-form 5-14-09-2007.pdf

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Patent Number

210952

Indian Patent Application Number

1010/MUM/2003

PG Journal Number

47/2007

Publication Date

23-Nov-2007

Grant Date

16-Oct-2007

Date of Filing

25-Sep-2003

Name of Patentee

UNITED PHOSPHORUS LIMITED

Applicant Address

3-11 GIDC, Vapi-396 195, GUJARAT

Inventors:

#	Inventor's Name	Inventor's Address
1	JAIDEV RAJANIKANT SHROFF	4-B Summer Palace, Nargis Dutt Road, Palihill, Bandra (W), Mumbai-400 057
2	SHROFF JAIDEV RAJNIKANT	4-B, SUMMER PALACE, NARGIS DUTT ROAD, PALI HILL, BANDRA(WEST), MUMBAI 400 050

PCT International Classification Number

A61 45/00

PCT International Application Number

N/A

PCT International Filing date

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1			NA