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Title:
A PESTICIDAL EMULSIFIABLE CONCENTRATE FORMULATION
Document Type and Number:
WIPO Patent Application WO/2019/186575
Kind Code:
A1
Abstract:
A pesticidal emulsifiable concentrate with widened spectrum of action on a plurality of pest insects and a plurality of fungal diseases includes a synergistically effective amount of an insecticide; a synergistically effective amount of a fungicide; and, an aprotic solvent as a co-solvent. In use, the insecticide is present in an amount ranging from about 1 % to about 6% weight percent ratio with respect to the concentrate and in further use, the fungicide is present in an amount ranging from about 10% to about 30% weight percent ratio with respect to the concentrate. Also, the insecticide is Fipronil, and, the fungicide is Isoprothiolane.

Inventors:
KUMARI NIDHI (IN)
DHIMAN SARVIND (IN)
JOSHI MONA (IN)
DATTA SANDEEP (IN)
ANAND KESHAV (IN)
Application Number:
PCT/IN2018/050703
Publication Date:
October 03, 2019
Filing Date:
October 31, 2018
Export Citation:
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Assignee:
PARIJAT INDUSTRIES INDIA PRIVATE LTD (IN)
International Classes:
A01N25/02; C07D231/12; C05G3/60
Foreign References:
EP2819513B12017-08-02
Other References:
SARKAR P K ET AL.: "Field efficacy of premix formulation fipronil 5% + isoprothiolane 28% EC against yellow stem borer, brown planthopper and blast disease of rice", INDIAN JOURNAL OF PLANT PROTECTION, vol. 45, no. 1, 2017, pages 57 - 63, XP055640070
PRASANNA KUMAR, M.K. ET AL.: "Compatibility and efficacy of insecticides and fungicide mixtures against major pests and diseases in rice", PESTOLOGY, vol. XXXV, no. 5, May 2011 (2011-05-01), pages 17 - 21
Attorney, Agent or Firm:
DEV, Rahul (IN)
Download PDF:
Claims:
Claims

1. A pesticidal emulsifiable concentrate with widened spectrum of action on a plurality of pest insects and a plurality of fungal diseases, said

5 pesticidal emulsifiable concentrate comprising:

a synergistically effective amount of an insecticide;

a synergistically effective amount of a fungicide; and,

an aprotic solvent as a co-solvent;

wherein said insecticide is present in an amount ranging from about 10 1 % to about 6% weight percent ratio with respect to said concentrate and wherein said fungicide is present in an amount ranging from about 10% to about 30% weight percent ratio with respect to said concentrate.

2. The pesticidal emulsifiable concentrate as claimed in claim 1 ,

15 wherein said insecticide is Fipronil.

3. The pesticidal emulsifiable concentrate as claimed in claim 1 , wherein said fungicide is Isoprothiolane. 0 4. The pesticidal emulsifiable concentrate as claimed in claim 1 , wherein Fipronil and Isoprothiolane are present in a ratio between 1 :20 and 20:1 .

5. The pesticidal emulsifiable concentrate as claimed in claim 4, 5 wherein Fipronil and Isoprothiolane are present in a ratio between 10:1 and

1 :10.

6. The pesticidal emulsifiable concentrate as claimed in claim 4, wherein Fipronil and Isoprothiolane are present in a ratio between 1 :6 to 6:1. 0

7. The pesticidal emulsifiable concentrate as claimed in claim 1 , wherein said co-solvent is present in an amount ranging from about 1 % to about 10% weight percent ratio with respect to said concentrate. 8. The pesticidal emulsifiable concentrate as claimed in claim 1 , wherein said co-solvent is selected from a group comprising of Dimethylformamide, N-Methyl-2-pyrrolidone, 2-Ethylhexyl Acetate, 2-

5 Ethylhexyl Acrylate or a mixture thereof.

9. The pesticidal emulsifiable concentrate as claimed in claim 1 , wherein said co-solvent is Dimethylformamide.

10 10. The pesticidal emulsifiable concentrate as claimed in claim 1 , wherein said pesticidal emulsifiable concentrate is effective against at least one pest insect of said plurality of pest insects found in Paddy, Onion, Okra, Garlic, leeks, Chilies, Capsicum, Celery, Peas, Melon, Choy sum, Bitter melon, Chinese Broccoli, Long Melon, Snake Bean and Pod vegetables.

15

11. The pesticidal emulsifiable concentrate as claimed in claim 1 , wherein said plurality of fungal diseases comprises at least one disease found in Paddy, Onion, Garlic, leeks, Chilies, Capsicum, Celery, Peas, Melon, Choy sum, Bitter melon, Chinese Broccoli, Long Melon, Snake Bean 0 and Pod vegetables.

12. The pesticidal emulsifiable concentrate as claimed in claim 1 , wherein said pesticidal emulsifiable concentrate is effective against Yellow stem borer, Whorl maggot, Brown planthopper, Green leafhopper, Thrips, 5 Magnaporthe oryzae, Podosphaera xanthii, Alternaria porri and Alternaria alternata.

13. The pesticidal emulsifiable concentrate as claimed in claim 1 , wherein said pesticidal emulsifiable concentrate further comprises a 0 plurality of adjuvants. 14. The pesticidal emulsifiable concentrate as claimed in claim 13, wherein said plurality of adjuvants include an emulsifier, an organic solvent and said co-solvent in combinations thereof.

5 15. The pesticidal emulsifiable concentrate as claimed in claim 14, wherein said emulsifier is selected from a group comprising linear dodecylbenzene sulphonate, calcium salt in 2-ethylexanol solution, benzenesulphonic acid 4-C 10-14 derivatives calcium salt, sodium dioctyl sulfosuccinate, ethoxylated fatty glyceride ethopropoxylated polyarylphenol, 10 thiophosphoro succinate salt, taurine derivatives (in particular alkyl taurate), polyoxyethylene alcohol or phenol phosphoric acid ester, fatty acid esters of polyols, ethoxylated fatty glyceride, and the like.

16. The pesticidal emulsifiable concentrate as claimed in claim 14, 15 wherein said organic solvent comprises at least one substantially water- immiscible solvent selected from a group comprising aromatic hydrocarbons, aliphatic hydrocarbons, alkylesters and alkenyl esters.

17. The pesticidal emulsifiable concentrate as claimed in claim 14, 0 wherein said organic solvent is dimethylformamide used in combination with a light aromatic solvent naphtha (petroleum).

18. The pesticidal emulsifiable concentrate as claimed in claim 1 , wherein said pesticidal emulsifiable concentrate further comprises a 5 plurality of auxiliary agents for formulating a stable composition .

19. A method for applying a pesticidal emulsifiable concentrate for action against a plurality of pest insects and/or a plurality of fungal diseases, said method comprises applying said pesticidal emulsifiable concentrate during 0 30 to 65 days after transplant.

20. A method for applying a pesticidal emulsifiable concentrate for action against a plurality of pest insects and/or a plurality of fungal diseases, said method comprises applying said pesticidal emulsifiable concentrate in a dosage range of about 800 ml/hectare to about 1500 ml/hectare.

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Description:
A PESTICIDAL EMULSIFIABLE CONCENTRATE FORMULATION FIELD OF THE INVENTION

Embodiments of the present invention generally relate to the field of pesticidal formulation, and, more particularly, to pesticidal emulsifiable 5 concentrate formulations comprising an effective amount of insecticide and fungicide, along with corresponding methods of uses and applications thereof.

BACKGROUND OF THE INVENTION

Pesticides are substances that are meant to control pests (Insects, 10 Diseases or Weeds). The Food and Agriculture Organization (FAO) has defined pesticide as: any substance or mixture of substances intended for preventing, curating, controlling or destroying any pest, including vectors of human or animal disease, unwanted species of plants or animals, causing harm during or otherwise interfering with the production, processing, 15 storage, transport, or marketing of food, agricultural commodities, wood and wood products or animal feedstuffs, or substances that may be administered to animals for the control of insects, arachnids, or other pests in or on their bodies. The term includes substances intended for use as a plant growth regulator, defoliant, desiccant, or agent for thinning fruit or 0 preventing the premature fall of fruit. Also used as substances applied to crops either before or after harvest to protect the commodity from deterioration during storage and transport.

Insecticides are agents of chemical or biological origin that control insects. Control may result from killing the insect or otherwise preventing it from 5 engaging in behaviors deemed destructive. Insecticides may be natural or manmade and are applied to target pests in a myriad of formulations and delivery systems. The science of biotechnology has, in recent years, even incorporated bacterial genes coding for insecticidal proteins into various crop plants that deal death to unsuspecting pests that feed on them.

0 The primary benefits are the consequences of the pesticides' effects - the direct gains expected from their use and it must be safe to the soil and has very little negative impact on natural beneficial predators, parasites and pollinator such as coccinellids, spiders, egg parasitoids and mirid bugs. Fauna of natural enemies in different Rice ecosystems are known to occur in families Carabidae, Coccinellidae, Cicindelidae, Staphylinidae, 5 Geocoridae, Miridae, Libellulidae, Coenagrionidae, Empusidae, Mantodae, Sciomyzidae, Syrphidae, Platystomatidae, Ephydridae, Ascalaphidae, Dermistidae, lchneumonidae, Braconidae, Mutillidae, Lycosidae, Oxyopidae and Tetragnathidae (Parasappa H. H et al. ,“Rice insect pests and their natural enemies complex in different Rice ecosystem of Cauvery 10 command areas of Karnataka’’ Journal of Entomology and Zoology Studies 2017; 5(5): 335-338).

Pests such as Yellow stem borer, Whorl maggot, Brown planthopper, Green leafhopper, Thrips, Magnaporthe oryzae, Alternaria porri, Alternaria alternate and Podosphaera xanthii causes serious damages to plants, such 15 as Paddy, Onion, Garlic, leeks, Chilies, Capsicum, Celery, Peas, Melon, Choy sum, Bitter melon, Chinese Broccoli, Long Melon, Snake Bean and Pod vegetables.

Paddy becomes Rice after the removal of husk by threshing. Therefore, Rice is a part of paddy, hence paddy is the Rice grain with husk. The term 0 paddy was derived from Malay word with the meaning of“Rice in the straw or husk”. Generally, Rice plant also is called paddy. This is a crop which belongs to the family Graminae. Botanical name of the paddy is Oryza sativa. It is a traditional wetland crop but in recent times upland /dryland crop is in practice, which extensively grows all over the worlds.

5 Rice is a major food crop for the people of the world in general and Asians in particular; nearly 90% of the world's Rice is produced and consumed in this region. The other major producers of Rice are South and Central America and Africa. In South and Central America, Rice production is scattered throughout the region.

0 India is one of the world's largest producers of Rice and brown Rice, accounting for 20% of all world Rice production. Rice is India's pre-eminent crop, and is the staple food of the people of the eastern and southern parts of the country. Rice is one of the chief grains of India. Moreover, this country has the largest area under Rice cultivation, as it is one of the principal food crops. It is in fact the dominant crop of the country. India is one of the leading producers of this crop. Rice is the basic food crop and being a tropical plant, it 5 flourishes comfortably in hot and humid climate. Rice is mainly grown in rain fed areas that receive heavy annual rainfall.

It demands temperature of around 25 degree Celsius and above and rainfall of more than 100 cm. Rice is also grown through irrigation in those areas that receives comparatively less rainfall. Rice is the staple food of eastern 10 and southern parts of India.

The regions cultivating this crop in India is distinguished as the western coastal strip, the eastern coastal strip, covering all the primary deltas, Assam plains and surrounding low hills, foothills and Terai region- along the Himalayas and states like West Bengal, Bihar, eastern Uttar 15 Pradesh, eastern Madhya Pradesh, northern Andhra Pradesh and Odisha.

India, being a land of eternal growing season, and the deltas of Kaveri River, Krishna River, Godavari River, Indravati River and Mahanadi River with a thick set-up of canal irrigation like Hirakud Dam and Indravati Dam, permits farmers to raise two, and in some pockets, even three crops 0 a year. Irrigation has made even three crops a year possible. Irrigation has made it feasible even for Punjab and Haryana, known for their baked climate, to grow Rice. They even export their excess to other states. Punjab and Haryana grow prized Rice for export purposes. Kaveri delta region of Thanjavur is historically known as the Rice bowl of Tamil Nadu 5 and Kuttanadu is called the Rice bowl of Kerala.

The agricultural GDP rises after the Kharif harvest, but declines in the next nine months. After the harvest of Rabi crops, the value of agricultural output declines by almost one-fifth, despite a good Kharif.

Rice has maintained a positive growth in yield, while it is negative for wheat. 0 So, if the agricultural GDP has to grow, it would seem that Rice output needs to grow even faster than it is at present. Rice, it does seem, is more important for India’s GDP. Similarly, onion crop is also affected by insects and diseases which result in the less production of onion. Biggest producers of onion are China, India and the USA. These countries produce around half of the world’s dry onions. Other countries, with annual production above 1 million tonnes, are Brazil, 5 Iran, Japan, Pakistan, Turkey and Russia. India is the second largest onion growing country in the world. Indian onions are famous for their pungency and are available round the year. Indian onions has two crop cycles, first harvesting starts in November to January and the second harvesting from January to May.

10 There is a lot of demand of Indian Onion in the world, the country has exported 24, 15,757.11 MT of fresh onion to the world for the worth of Rs. 3,106.50 crores/ 464.02 USD Millions during the year 2016-17.

Modern pack houses for sorting, grading and packing of the quality onions are available at production zones. Guidelines has been framed to determine 15 the compliance with maximum residue levels (MRLs) for the identified pesticides and Grade designation and quality development parameters has been set up. The major varieties found in India are Agrifound Dark Red, Agrifound Light Red, NHRDF Red, Agrifound White, Agrifound Rose and Agrifound Red, Pusa Ratnar, Pusa Red, Pusa White Round. There are 0 certain varieties in yellow onion which are suitable for export in European countries Tana F 1 , Arad-H, Suprex, Granex 55, HA 60 and Granex 429. The Major Onion producing states in India are Maharashtra, Karnataka, Madhya Pradesh, Gujarat, Bihar, Andhra Pradesh, Rajasthan, Haryana and Telangana. Maharashtra ranks first in Onion production with a share of 5 28.32%.

Pod vegetables are a type of fruit vegetables where pods are eaten, much of the time as they are still green. There are different categories of pod vegetable such as Bean, Black turtle bean, Edamame, Flat bean, Green bean, Okra, Raphanus caudatus, Snap pea, Snow pea and Winged bean. 0 These vegetables provides adequate amounts of essential nutrients like vitamins, minerals and dietary fiber. Some of these vegetables such as pea pods, okra are dense with these nutrients, as well as being low-calorie, low- fat and cholesterol-free which give human diet a boost of nutrition. Pests such as Yellow stem borer, Whorl maggot, Brown planthopper, Green leafhopper, Thrips, Magnaporthe oryzae, Alternaria porri, Alternaria alternate and Podosphaera xanthii causes serious damages to plants. If thrips population is high the leaves of plant may be distorted. Leaves are 5 covered in coarse stippling and may appear silvery and speckled with black feces. This insect is small (1.5 mm) and slender and best viewed using a hand lens. Adult thrips are pale yellow to light brown and the nymphs are smaller and lighter in color. Mostly powdery mildew is the major cause of low yield and loss for Pod vegetables.

10 Therefore, there is a need to protect Paddy, Onion, Garlic, leeks, Chilies, Capsicum, Celery, Peas, Melon, Choy sum, Bitter melon, Chinese Broccoli, Long Melon, Snake Bean and Pod vegetables from effects of insects and disease.

Major insects and diseases

15 The Rice when affected by insects like whorl maggot, yellow stem borer, brown plant hopper, green leaf hopper, and also diseases viz, Leaf blast disease, panicle blast and Neck blast disease, reduces the crop yield and thus country's Rice production get declined.

Standing water in Paddy during the vegetative stage, presence of host 0 plants year-round, and transplanting of young seedlings favor the development of Rice whorl maggot.

The Rice whorl maggot is semi-aquatic. It is common in irrigated fields and feeds on the central whorl leaf of the vegetative stage of the Rice plant. It does not occur in upland Rice. It also prefers ponds, streams and lakes or 5 places with abundant calm water and lush vegetation.

The insect does not prefer direct-seeded fields and seedbeds. The adult is active during the day and rests on Rice leaves near the water. It floats on the water or perches on floating vegetation. At midday, it is sedentary or it clings on upright vegetation. It prefers thick vegetation and is attracted to 0 open standing water around seedbeds. Neonate maggots feed on the unopened central leaves where larval development is completed in 10-12 days. The full-grown maggots pupate outside the feeding stalk. The feeding damage of whorl maggots causes yellow spots, white or transparent patches, and pinholes.

The larva uses its hardened mouth hooks to rasp the tissues of unopened leaves or the growing points of the developing leaves. The damage 5 becomes visible when the leaves grow old. Mature larva prefers to feed on the developing leaves of the new developing tillers at the base of the Rice plant.

The stem borer larvae bore at the base of the plants during the vegetative stage. On older plants, they bore through the upper nodes and feed toward 10 the base.

The yellow stem borer is an insect of deepwater Rice. It is found in aquatic environments where there is continuous flooding. Second instar larvae enclose themselves in body leaf wrappings to make tubes and detach themselves from the leaf and falls onto the water surface. They attach 15 themselves to the tiller and bore into the stem.

Stem borers can destroy Rice at any stage of the plant from seedling to maturity.

They feed upon tillers and causes deadhearts or drying of the central tiller, during vegetative stage; and causes whiteheads at reproductive stage. 0 Two species of planthopper infest Rice. These are the brown planthopper (BPH), Nilaparvata lugens (Stal); and the whitebacked planthopper (WBPH), Sogatella furcifera (Horvath).

Planthoppers can be a problem in rainfed and in irrigated wetland environments. It also occurs in areas with continuous submerged conditions 5 in the field, high shade, and humidity.

Closed canopy of the Rice plants, densely seeded crops, excessive use of nitrogen, and early season insecticide spraying also favors insect development.

High population of planthoppers cause leaves to initially turn orange-yellow 0 before becoming brown and dry and this is a condition called hopperburn that kills the plant.

BPH can also transmit Rice Ragged Stunt and Rice Grassy Stunt diseases. Neither disease can be cured. Two species of green leafhoppers (GLH) can spread tungro: Nephotettix malayanus and Nephotettix virescens.

Green leafhoppers are common in rainfed and irrigated wetland environments. They are not prevalent in upland Rice. Both the nymphs and 5 adults feed on the dorsal surface of the leaf blades rather than the ventral surface. They prefer to feed on the lateral leaves rather than the leaf sheaths and the middle leaves. They also prefer Rice plants that have been fertilized with large amount of nitrogen.

Blast can occur wherever blast spores are present. It occurs in areas with 10 low soil moisture, frequent and prolonged periods of rain shower, and cool temperature in the daytime. In upland Rice, large day-night temperature differences that cause dew formation on leaves and overall cooler temperatures favor the development of the disease.

Rice can have blast in all growth stages. However, leaf blast incidence tends 15 to lessen as plants mature and develop adult plant resistance to the disease.

Node and neck blast commonly occur together and have similar symptoms and when a node or neck blast infection is present, it can cause plants to develop few or no grains at all.

0 Blast is caused by the fungus Pyricularia oryzae (sexual morph Magnaporthe oryzae). It can affect all above ground parts of a Rice plant: leaf, collar, node, neck, parts of panicle, and sometimes leaf sheath.

Major insect problem of onion is Thrips which sucks the succulent leaves reducing to dry and chaffy. The significant disease problem is Purple blotch 5 caused by Alternaria porri, the initial symptoms of purple blotch are small, water-soaked lesions with white centers that appear usually on older leaves. As the disease progresses, the lesions enlarge (individual lesions can be as long as 1-2 inches) and become purplish with light yellow concentric rings on the margins. As severity increases, leaves turn yellow brown, lose 0 erectness, and wilt. Windborne conidia from previous crop debris initiate infection, which is favored by high temperatures and humid conditions. Prolonged leaf wetness increases the probability of further infection. Further, Chilli is one of the spices used to enhance the flavour and taste of cooked food. Insects like thrips and fungal diseases are the main biological constraints in chilli production, and Alternaria leaf spot disease, one of the most devastating diseases of chilli caused by the species of Alternaria 5 (Alternaria alternate).

In pod vegetables the major problem is from insect like Thrips and disease caused from species of phylum Ascomycota, especially Magnaporthe oryzae, Alternaria porri and Alternaria alternate and Podosphaera xanthii. Here phylum is a level of classification or taxonomic rank below Kingdom 10 and above Class having a group of organisms with a certain degree of morphological or developmental similarity.

Powdery mildew is a fungal disease that affects a wide range of plants. Infected plants display white powdery spots on the leaves and stems. The lower leaves are the most affected, but the mildew can appear on any 15 above-ground part of the plant. As the disease progresses, the spots get larger and denser as large numbers of asexual spores are formed, and the mildew may spread up and down the length of the plant. This fungal disease is caused by Podosphaera xanthii.

Thrips cause direct damage by using their piercing and sucking mouthparts 0 to pierce plant cells and suck the cell contents, which results in the deformation of flowers, leaves, stems, shoots, and fruits. Damage appears as silvering and flecking on the leaves of seedlings. Severe infestations can result in bronzing, yellowing and stunting of leaves. Thrips can also damage buds and flowers through laying eggs, causing deformed fruit to develop. 5 The fungal disease caused by Alternaria result in the serious damages to plant leaves and fruits which reduce the final yield from field.

Previously people have tried many alternatives and option to overcome the problem of insects and disease. For managing the disease effectively in Onion, people are doing crop rotation of 2-3 years with non-related crops. 0 Further, formulations like Mancozeb @ 0.25% or Chlorothalonil @ 0.2% or Rovral @ 0.25% are sprayed at fortnightly interval commencing from one month after transplanting. For managing the disease effectively in Rice (Paddy), farmer are using Fipronil Granule Chloropyriphos, Carbofuran, Cartap hydrochloride (GR), Lamda cyhalothrin and Fipronil SC formulation in order to control Stem borer and leaf folder. This will be followed by the application of 5 Isoprothiolane for the control of Blast and Buprofenzin for controlling BPH.

With regards to management of Alternaria diseases of chili, lowest per cent disease index was observed in combination spray of Propiconazole (Tilt 25% EC) @ 0.05% + Eucalyptus spp. @ 10% + Pseudomonas fluorescens @ 5g/ liter which was followed by spray with Propiconazole (Tilt 25% EC) 10 @ 0.05% + P. fluorescens@ 5g/ liter.

For vegetables to control thrips and disease caused by Alternaria species people does application of neem cake (once immediately after germination and again at flowering) in soil followed by NSPE @ 4% and neem soap 1 % alternately at 10-15 days interval. They spray any systemic insecticides like 15 Acephate 75 SP @ lg/1 or Dimethoate 30 EC @ 2ml/l or one foliar spray of Chlorothalonil @ 0.2% alternated by thiophenate-methyl@ 0.1 % after 8-10 day.

So, there was the need of formulation having the widened spectrum of action on the insect and disease in tandem. The present invention of a 0 pesticidal emulsifiable concentrate formulation provides the best control against pest and disease like Yellow stem borer, Whorl maggot, Brown planthopper, Green leafhopper, Thrips, Magnaporthe oryzae, Podosphaera xanthii, Alternaria species like Alternaria porri and Alternaria alternata. Fipronil is a broad-spectrum insecticide that belongs to the phenylpyrazole 5 chemical family. Fipronil disrupts the insect central nervous system by blocking GABA-gated chloride channels and glutamate-gated chloride (GluCI) channels. This causes hyperexcitation of contaminated insects' nerves and muscles. Fipronil's specificity towards insects is believed to be due to its greater affinity to the GABA receptor in insects relative to 0 mammals and its effect on GluCI channels, which do not exist in mammals.

It is chemically known as (RS)-5-Amino-1-[2, 6-dichloro-4-(trifluoromethyl) phenyl]-4-(trifluoromethylsulfinyl) pyrazole-3-carbonitrile and having chemical structure formula represented as below,

Fipronil

Because of its effectiveness on a wide range of insects, Fipronil is used as

5 the active ingredient in flea control products for pets and home roach traps as well as field pest control for corn, golf courses, and commercial turf. Its widespread use makes its specific effects the subject of considerable attention. This includes ongoing observations on possible off-target harm to humans or ecosystems as well as the monitoring of resistance

10 development. Fipronil was discovered and developed by Rhone- Poulenc between 1985 and 1987, and placed on the market in 1993 under the US Patent 5232940A.

Isoprothiolane is a systemic fungicide with curative and protective effects. Isoprothiolane is a chemical compound from the group of Dithiolanes and

15 introduced in 1974 by Nihon Noyaku as fungicide. Isoprothiolane has a conspicuous ketene- di thioacetal structure. It is chemically known as Diisopropyl 2- (1 , 3-dithiolane-2-ylidene) malonate and having chemical structure formula represented as below,

0 Isoprothiolane

The main concern of this invention is the development of effective pesticidal emulsifiable concentrate formulation, which is on one hand is effective in wider range to control insects like Thrips, Aphids, Jassids, whorl maggot, Yellow stem borer, Brown plant hopper, Green leaf hopper and diseases like leaf blast neck blast and purple blotch on one hand with ensuring environmental safety and intrinsic property of stability on another hand.

5 The prior arts are replete with various references which disclose various methods, combinations or formulations of Fipronil and Isoprothiolane to overcome the problem of insects and disease.

Chinese Patent Application No. 101194606 A, discloses an agricultural chemical miscible oil preparation with biological diesel oil dissolvent, the 10 ingredient comprises agricultural chemical original raw pesticide, dissolvent, and emulsifying agent, wherein the dissolvent is biological diesel oil or is mixed dissolvent which is mixed by biological diesel oil and conventional agricultural chemical in any proportion. This document discloses Abamectin and Fipronil combination. This document does not disclose a pesticidal 15 emulsifiable concentrate composition comprising an effective amount of Fipronil and Isoprothiolane in combination

Chinese Patent No. 102258022 B is relates to a bactericidal and insecticidal composition of Isoprothiolane to Flubendiamide in weight ratio of 50:1 to 1 :50, which provides a synergism effect, used for controlling paddy diseases 0 and pests. This document does not disclose a pesticidal emulsifiable concentrate comprising an effective amount of insecticide and fungicide in combination. Also, Fipronil‘s specificity towards insects is believed to be due to its greater affinity to the GABA receptor in insects relative to mammals and its effect on GluCI channels, which do not exist in mammals 5 so pesticidal emulsifiable concentrate comprising Fipronil and Isoprothiolane is more safe.

Indian Patent Application No. 255/MUM/2015, discloses a novel composition comprising of Pymetrozine and Thifluzamide in synergistic bioactive amounts and one or more inactive excipients. This composition is 0 any of the form selected from group comprising Suspension Concentrate (SC), Oil Dispersion (OD) and Water dispersible granules. Thus, this document does not discloses a pesticidal emulsifiable concentrate comprising an effective amount of insecticide and fungicide effective for curing disease in onion.

Chinese Patent Application No. 105766908 A, discloses an emulsifiable concentrate with sec-butyl acetate as a solvent. This document discloses 5 formulation of one insecticide, thus this document does not disclose a pesticidal emulsifiable concentrate composition comprising an effective amount of Fipronil and Isoprothiolane.

Chinese Patent Application No. 106035349 A, discloses a composition for preventing and removing the harmful organisms includes a combination of 10 one or more than two compounds of an effective component A and an effective component B. The effective component A includes compounds such as Isoprothiolane, Buprofezin, Flutotanil, Fenpyroximate, Pyraflufen- ethyl, Tiadinil, basic Chrome sulphate, and Fluoromide. The effective component B includes compounds such as Acetamiprid, Isoprocarb, and 15 Ethofenprox, thus this document does not disclose a pesticidal emulsifiable concentrate composition comprising an effective amount of Fipronil and Isoprothiolane.

WO 2013/083372A1 , discloses an emulsifiable concentrate comprising a water-insoluble pesticide, benzyl alcohol, alkyl lactate and not more than 0 40% by weight of dimethyl sulfoxide., thus this document does not disclose a pesticidal emulsifiable concentrate composition comprising an effective amount of Fipronil and Isoprothiolane and wherein the said formulation comprises aprotic solvent as co-solvent.

WO 2015/200428A1 , discloses an emulsifiable foaming concentrate. This 5 document discloses formulation of one insecticide, thus this document does not disclose a pesticidal emulsifiable concentrate composition comprising an effective amount of Fipronil and Isoprothiolane.

However, for crops protection against effect of Yellow stem borer, Whorl maggot, Brown planthopper, Green leafhopper, Thrips, Magnaporthe 0 oryzae, Alternaria porri, Alternaria alternate and Podosphaera xanthii still there was the need of improvement to make a formulation having enhanced stability, significant advantages in packaging, ease of handling and safety and can be prepared easily without much complex manufacturing process. This leads the inventor to prepare a pesticidal emulsifiable concentrate comprising in effective amount of Fipronil and Isoprothiolane widening the spectrum of action on the insects and disease which can be controlled. Surprisingly, it has now been found that a pesticidal emulsifiable 5 concentrate formulation of present invention comprising an effective amount of Fipronil and Isoprothiolane have enhanced efficacy and have widespread scope in end use. Thus, the present invention has widen the spectrum of action on the pests and disease with high efficiency on one hand and safety, environmental protection, and low toxicity on another hand.

10 Accordingly, there remains a need in the art for effective pesticidal emulsifiable concentrate with widened spectrum of action on various pest insects and various fungal diseases, which overcome the shortcomings of the prior art.

15 SUMMARY OF THE INVENTION

It is an object of the present invention to develop an effective pesticidal emulsifiable concentrate formulation, which is effective to overcome the existing problems in wider range in pesticidal effect to control multiple pests, such as, for example, but not limited to, Whorl maggot, Yellow Stem borer, 0 Brown plant hopper, Green leaf hopper, blast diseases like Leaf blast, Node blast, Neck blast in Rice (Paddy) caused by Magnaporthe oryzae, and the like.

It is yet another object of the present invention to provide an effective control of Thrips, fungal disease like Purple blotch, Alternaria leaf spot caused by 5 Alternaria species like Alternaria porri, Alternaria alternata and powdery mildew by Podosphaera xanthii in Rice (Paddy), Onion, Garlic, Leeks, Chilies, Capsicum, Celery, Peas, Melon, Choy sum, Bitter melon, Chinese Broccoli, Long Melon, Snake Bean and Pod vegetables while ensuring environmental safety due to low toxicity and intrinsic property of stability. 0 The present invention relates to a pesticidal emulsifiable concentrate formulation comprising an effective amount of Fipronil and Isoprothiolane, which widen the spectrum of action on the pest insects and fungal disease. The pesticidal emulsifiable concentrate of present invention is effective against Yellow stem borer, Whorl maggot, Brown planthopper, Green leafhopper and Blast disease in Paddy and effect of Thrips and fungal disease in Rice (Paddy), Onion, Garlic, leeks, Chilies, Capsicum, Celery, Peas, Melon, Choy sum, Bitter melon, Chinese Broccoli, Long Melon, Snake 5 Bean and Pod vegetables. Thus, this pesticidal emulsifiable concentrate comprising in effective amount of Fipronil and Isoprothiolane has high efficiency, safety, environmental protection, and low toxicity.

A pesticidal emulsifiable concentrate formulation according to the present invention used for controlling pests or diseases comprising wherein, Fipronil 10 and Isoprothiolane are in the ratio between 1 :6 to 6:1. A pesticidal emulsifiable concentrate according to the present invention comprises Fipronil and Isoprothiolane with other auxiliary agents is a stable formulation.

Embodiments of the present invention disclose a pesticidal emulsifiable 15 concentrate with widened spectrum of action on a plurality of pest insects and a plurality of fungal diseases, including, a synergistically effective amount of an insecticide; a synergistically effective amount of a fungicide; and, an aprotic solvent as a co-solvent. In use, the insecticide is present in an amount ranging from about 1 % to about 6% weight percent ratio with 0 respect to the concentrate and in further use, the fungicide is present in an amount ranging from about 10% to about 30% weight percent ratio with respect to the concentrate. Also, the insecticide is Fipronil, and, the fungicide is Isoprothiolane.

Other aspects of the invention will be set forth in the description which 5 follows, and in part will be apparent from the description, or may be learnt by the practice of the invention.

DETAILED DESCRIPTION OF THE INVENTION

Various embodiments of the present invention are aimed at providing 0 pesticidal emulsifiable concentrate formulations comprising an effective amount of insecticide and fungicide, along with corresponding methods of uses and applications thereof. In use, a pesticidal emulsifiable concentrate according to the present invention comprises of Fipronil which is an insecticide and Isoprothiolane which is a fungicide. Generally, the pesticidal emulsifiable concentrates as disclosed herein include an effective amount of Fipronil and Isoprothiolane, which has significant broad spectrum efficacy, safety, environmental protection, and low toxicity.

5 In accordance with an embodiment of the present invention, a pesticidal emulsifiable concentrate with widened spectrum of action on a plurality of pest insects and a plurality of fungal diseases includes, a synergistically effective amount of an insecticide; a synergistically effective amount of a fungicide; and, an aprotic solvent as a co-solvent. In use, the insecticide is 10 present in an amount ranging from about 1 % to about 6% weight percent ratio with respect to the concentrate and in further use, the fungicide is present in an amount ranging from about 10% to about 30% weight percent ratio with respect to the concentrate. Also, the insecticide is Fipronil, and, the fungicide is Isoprothiolane.

15 In accordance with an embodiment of the present invention, Fipronil and Isoprothiolane are present in a ratio between 1 :20 and 20:1. In one embodiment, Fipronil and Isoprothiolane are present in a ratio between 10:1 and 1 :10. In another embodiment, Fipronil and Isoprothiolane are present in a ratio between 1 :6 to 6:1. Those of ordinary skills in the art will appreciate 0 that a ratio of Fipronil and Isoprothiolane may be changed to suit the exact need for embodying the present invention.

In accordance with an embodiment of the present invention, the co-solvent is present in an amount ranging from about 1 % to about 10% weight percent ratio with respect to the concentrate. In use, the co-solvent is selected from 5 a group including of dimethylformamide, N-Methyl-2-pyrrolidone, 2- Ethylhexyl Acetate, 2-Ethylhexyl Acrylate or a mixture thereof. In one embodiment, the co-solvent is dimethylformamide.

In accordance with an embodiment of the present invention, the pesticidal emulsifiable concentrate is effective against at least one pest insect of the 0 plurality of pest insects found in Paddy, Onion, Okra, Garlic, leeks, Chilies, Capsicum, Celery, Peas, Melon, Choy sum, Bitter melon, Chinese Broccoli, Long Melon, Snake Bean and Pod vegetables. In accordance with an embodiment of the present invention, the plurality of fungal diseases includes at least one disease found in Paddy, Onion, Garlic, leeks, Chilies, Capsicum, Celery, Peas, Melon, Choy sum, Bitter melon, Chinese Broccoli, Long Melon, Snake Bean and Pod vegetables.

5 In accordance with an embodiment of the present invention, the pesticidal emulsifiable concentrate is effective against Yellow stem borer, Whorl maggot, Brown planthopper, Green leafhopper, Thrips, Magnaporthe oryzae, Podosphaera xanthii, Alternaria porri and Alternaria alternata.

In accordance with an embodiment of the present invention, the pesticidal 10 emulsifiable concentrate further includes a plurality of adjuvants. In use, the plurality of adjuvants include an emulsifier, an organic solvent and the co- solvent in combinations thereof. In further use, the emulsifier is selected from a group including linear dodecylbenzene sulphonate, calcium salt in 2- ethylexanol solution, benzenesulphonic acid 4-C 10-14 derivatives calcium 15 salt, sodium dioctyl sulfosuccinate, ethoxylated fatty glyceride ethopropoxylated polyarylphenol, thiophosphoro succinate salt, taurine derivatives (in particular alkyl taurate), polyoxyethylene alcohol or phenol phosphoric acid ester, fatty acid esters of polyols, ethoxylated fatty glyceride, and the like.

0 Additionally, as per one embodiment of the present invention, the organic solvent includes at least one substantially water-immiscible solvent selected from a group including aromatic hydrocarbons, aliphatic hydrocarbons, alkylesters and alkenyl esters. In one embodiment, the organic solvent is dimethylformamide used in combination with a light aromatic solvent 5 naphtha (petroleum).

In accordance with an embodiment of the present invention, the pesticidal emulsifiable concentrate further includes multiple auxiliary agents for formulating a stable composition. In use, such auxiliary agents may be optionally added to the pesticidal emulsifiable concentrate of present 0 invention. Here, auxiliary agents may include one or more of, anti-freezing agent, anti-foaming agent, and anti-microbial agent. Optionally, anti- freezing agent as used in the present invention is selected from the group comprising propylene glycols, polypropylene glycols, polyethylene glycols, ethylene glycols and glycerin, most preferably in the range of 0.25% to 10% by weight of the formulation. Optionally, anti-foaming agent is used to prevent formation of foam which are present in the present invention is selected from the group comprising silicones, polydimethylsiloxane, 5 polymethylhydrosiloxane, cyclomethicones and salts of fatty acids, most preferably in the range of 0.25% to 10% by weight of the formulation. Optionally, anti-microbial agent as used in the present invention is selected from the group comprising isothiazolinone derivatives such as methylisothiazolinone, chloroisothiazolinones and benzisothiazolinones, 10 most preferably in the range of 0.05% to 0.5% by weight of the formulation.

In accordance with an embodiment of the present invention, a method for applying a pesticidal emulsifiable concentrate for action against a plurality of pest insects and/or a plurality of fungal diseases includes applying the pesticidal emulsifiable concentrate during 30 to 65 days after transplant.

15 In accordance with an embodiment of the present invention, a method for applying a pesticidal emulsifiable concentrate for action against a plurality of pest insects and/or a plurality of fungal diseases includes applying the pesticidal emulsifiable concentrate in a dosage range of about 800 ml/hectare to about 1500 ml/hectare.

0 The present invention discloses a pesticidal emulsifiable concentrate formulation comprising an effective amount of insecticide and fungicide, as explained hereinbelow. A pesticidal emulsifiable concentrate according to the present invention comprises Fipronil which is an insecticide and Isoprothiolane which is a fungicide. A pesticidal emulsifiable concentrate 5 formulation according to the present invention used for controlling pests or diseases in Rice (Paddy), Onion, Garlic, leeks, Chilies, Capsicum, Celery, Peas, Melon, Choy sum, Bitter melon, Chinese Broccoli, Long Melon, Snake Bean and Pod vegetables, wherein, Fipronil and Isoprothiolane are in the ratio between 1 :6 to 6:1. A pesticidal emulsifiable concentrate according to 0 the present invention comprises Fipronil and Isoprothiolane with other auxiliary agents is a stable formulation.

The term“pesticide” or“pesticidal” is similar to“insecticide” or“insecticidal” and is used interchangeably in this whole specification. The term “fungicide or fungicides” used in this specification is biocidal chemical compounds or biological organisms used to kill parasitic fungi or their spores which causes fungal disease.

"Effective amount or effective amounts” as mentioned herein means that 5 amount which, when applied treatment of crops, is sufficient to effect such treatment.

The term composition and formulation described herein, are synonyms and can be used interchangeably and convey the same meaning.

A pesticidal emulsifiable concentrate according to the present invention 10 comprises an effective amount of insecticide and fungicide. A pesticidal emulsifiable concentrate according to the present invention comprises Fipronil which is an insecticide and Isoprothiolane which is a fungicide. According to the present invention, Fipronil and Isoprothiolane are present in the ratio between 1 :20 and 20:1 , especially between 10:1 and 1 :10, more 15 preferably between 1 :6 to 6:1. These ratios are to be understood as meaning, on the one hand, weight ratios, and on the other hand molar ratios. In accordance with a preferred embodiment of the present invention, (a) Fipronil is present in an amount ranging from 1 % to 6% w/w and (b) Isoprothiolane is present in an amount ranging from 10% to 30% w/w. The 0 w/w in the present invention is the weight percent ratio of Fipronil and Isoprothiolane with respect to the formulation.

In accordance with a preferred embodiment of the present invention, Fipronil and Isoprothiolane act synergistically when applied to the crops. Aprotic solvent in this invention is a co-solvent which is added to a pesticidal 5 emulsifiable concentrate according to the present invention, when the solubility of actives in aromatic solvents is not sufficient to obtain a suitable active content in the formulation.

Preferably, a pesticidal emulsifiable concentrate of the present invention comprises aprotic solvent as co-solvent which is selected from the group 0 comprising dimethylformamide, N-Methyl-2-pyrrolidone, 2-Ethylhexyl Acetate, 2-Ethylhexyl Acrylate or a mixture thereof, preferably between the ranges of 1 % to 10% by total weight of the formulation. Preferred one is dimethylformamide. An adjuvant is any material that is added to an agrochemical solution to enhance or modify the performance of the formulation or composition. Preferably, an adjuvant comprises emulsifier, anti-freezing agent, dispersing agent, antifoaming agent, suspending agent and thickener. The 5 formulation of this present invention comprises emulsifier, organic solvent and co-solvent in combinations thereof.

Emulsifier used in the present invention is selected from the group comprising linear dodecylbenzene sulphonate, calcium salt in 2-ethylexanol solution, benzenesulphonic acid 4-C 10-14 derivatives calcium salt, sodium 10 dioctyl sulfosuccinate, ethoxylated fatty glyceride ethopropoxylated polyarylphenol, thiophosphoro succinate salt, taurine derivatives (in particular alkyl taurate), polyoxyethylene alcohol or phenol phosphoric acid ester, fatty acid esters of polyols. Preferred one is ethoxylated fatty glyceride.

15 At least one substantially water-immiscible solvent is preferably selected from the group of aromatic hydrocarbons, aliphatic hydrocarbons, alkylesters and alkenyl esters. It has been found that, when dimethylformamide is used in combination with light aromatic solvent naphtha (petroleum), such a solvent system is able to afford 0 formulations of a higher than normally used concentration, which are both stable in concentrate form and stable to crystallization upon dilution in water. In accordance with the present invention, an effective amount of Fipronil and Isoprothiolane, is used for insect and disease in Paddy, Onion, Garlic, Leeks, Chilies, Capsicum, Celery, Peas, Melon, Choy sum, Bitter melon, 5 Chinese Broccoli, Long Melon, Snake Bean and Pod vegetables (such as Bean, Black turtle bean, Edamame, Flat bean, Green bean, Okra,

Raphanus caudatus, Snap pea, Snow pea and Winged bean).

In accordance with a preferred embodiment of the present invention, (a) Fipronil and (b) Isoprothiolane are used in an amount sufficient to induce a 0 synergistic pesticidal effect while still showing excellent crop compatibility (i.e., their use in crops does not result in any damage to crops when compared to the individual application of the pesticide compounds (a) or (b)). As described in the Herbicide Handbook of the Weed Science Society of America, Ninth Edition, 2007, p. 429,“synergism” [is] an interaction of two or more factors such that the effect when combined is greater than the predicted effect based on the response to each factor applied separately. Colby's formula is applied to determine synergistic effect, as provided in 5 WEEDS 1967, 15, 22

E = (X + Y) - ((X x Y)/100)

For Synergy, O/E > 1

wherein;

X=effect in percent (%) using (a) Fipronil

10 Y=effect in percent (%) using (b) Isoprothiolane

E=expected effect (in %) of (a) + (b) at application rates a and b.

0=Observed effect (in %) of (a) + (b)

The following examples are intended to illustrate, but in no way limit the scope of, the present invention.

15 EXAMPLES

Example 1 : Preparation of Fipronil and Isoprothiolane Emulsifiable concentrate (EC) formulation

In an appropriately sized beaker, aromatic solvent was charged. After it charge required quantity of Fipronil & Isoprothiolane under stirring, followed 0 by the addition of co solvent, stir the whole mass till the active ingredients are fully dissolved. After dissolution of active ingredients emulsifier was added. Continue stirring for another 30 min. Filter the mass through sparkler filter to obtain a pesticidal emulsifiable concentrate comprising Fipronil and Isoprothiolane. An exemplary composition obtained from the above process 5 is tabulated below:

Table: 1 : Chemical Composition Examples 2: Stability Study

Storage stability study data of In-house developed Fipronil 5.0 % + Isoprothiolane 28 % Emulsifiable concentrate (EC) formulation is tabulated 5 in Table 2.

Table 2: Storage stability study data

EXAMPLE 3: FIELD EFFICACY TRIALS

The objective of the field trial experiments was:

1 ) To find out pesticidal effect of emulsifiable concentrate of present

5 invention comprising Fipronil and Isoprothiolane on control of pests like stem borer, BPH, Thrips, & diseases predominated by Ascomycota . Blast disease caused by Magnaporthe oryzae, Purple blotch disease caused by Alternaria porri, Powdery mildew disease caused by Podosphaera xanthii. In the case of Blast and Purple

10 blotch, the effect exhibited by the combination is both prophylactic as well as curative.

2) To study the effect of application window of spray of present invention pesticidal emulsifiable concentrate formulation when applied during 30 to 65 days after transplant, which provides one

15 solution against problem of pest and disease like Yellow stem borer,

Whorl maggot, Brown planthopper, Green leafhopper, Thrips, Magnaporthe oryzae, Podosphaera xanthii, Alternaria species like Alternaria porri and Alternaria alternata.

3) To study the effect of formulation of present invention in significant 0 yield and plant growth after crop treatment.

4) To study the effect of formulation of present invention on natural enemies

Example 3.1 : Experiment against Stem borer. Blast disease and Brown 5 Plant Hopper (BPH) in Rice (Paddy)

Rice is regarded as one of the most important staple crop of our nation. India Ranks Second after China in Rice production. The crop is affected by various diseases and insects that cause a considerable loss in food grain production and is one of the main challenges that needs to be addressed to, in order to attain food security for the nation. The current pesticide usage in Rice is that of multiple spraying as per the pest prevalence. In this context 5 pesticidal emulsifiable concentrate comprising Fipronil and Isoprothiolane was tested for different windows of application and was found to give excellent control over stem borer, leaf folder, Blast and also showed prophylactic effect on BPH following its two applications. A pesticidal emulsifiable concentrate comprising Fipronil and Isoprothiolane was 10 developed at in-house R&D laboratory.

The general population dynamics of the pests

Stem borer infestation started from mid-July (30-35 DAT= Days After Treatment). Initially the infestation was very minor (around 2%). This population started building up and reached its peak (60-65 % infestation) at 15 around 45 DAT. It then took a declining trend and kept on falling towards the maturity of the crop. Leaf folder infestation up to 2%, beginning from 35- 40 days after transplanting was observed. Leaf folder showed up after Stem borer, but with a higher intensity. The population reached a peak, with 70- 75% infestation, at 50-55 DAT, it remained constant for a while and then 0 followed a declining trend. Brown plant hopper was sighted beginning from 65 days after transplanting with an infestation of 50%. The population reached its peak (80 -90% infestation) in 75 to 80 DAT. Hopper burn was also observed due to severe pest density. The population then followed a declining trend similar to the other pests. Very few plants (1 or 2/metre 2 ) 5 showed the symptoms of blast initially but latter the disease did not spread further due to non-conducive environment and good plant vigor. It was recorded that in the hierarchy of appearance, Stem borer was first followed by leaf folder and Brown Plant Hopper respectively, however the pest with the maximum intensity was BPH, followed by Leaf folder and Stem borer 0 respectively. Considering the standard package of practices, normally a farmer will go for Fipronil SC, Fipronil Granule, Chlopropyrifos, Cartap hydrochloride (GR), Lamda cyhalothrin and Fipronil SC formulation in order to control Stem borer and leaf folder. Subsequently, Isoprothiolane and Buprofezin are used to control Blast and BPH respectively.

In light of the above stated facts a trial was conducted at Research Farm Ambala in the state of Haryana, to assess the bio efficacy of pesticidal 5 emulsifiable concentrate comprising Fipronil and Isoprothiolane was done against the major insect of Rice with special reference to Stem borer, Leaf folder, Brown plant hopper and disease like Rice blast. Filed trials were laid out in a randomized block design with nine treatments, replicated thRice. Rice variety PUSA BASMATI 1121 (135 days duration) susceptible to 10 different insect pest and disease was planted at a spacing of 15 c 15 cm.

The sprays were carried out as per the treatments, using a battery operated knapsack sprayer (15 lit capacity). 200 lit water per Acre was used for conducting the spray. The observations were taken 3, 5, 7 and 15 days after the spray.

15

Observation Methodology for Stem borer

Percent Control for stem Borer (Observed Value) = ((No. of Dead hearts before spray - No. of Dead hearts after spray)/No. of Dead hearts before spray) *100) 0 The result of study are recorded in Table 3.

Table 3: Efficacy study for Stem borer (Sciropophaga Incertulas)

* a. /. /ha. = Active Ingredient per Hectare

Observation Methodology for Blast

Percent Control for Blast (Observed value) = Percent disease incidence before spray - Percent disease incidence after spray

5 The result of study are recorded in Table 4.

Table 4: Efficacy study for Blast Pyricularia Oryzae (sexual morph

Magnaporthe oryzae) * a. /. /ha. = Active Ingredient per Hectare

Observation Methodology for Brown Plant Hopper

5 Percent control for BPH = ((No. of Nymph/Adult before spray - No. of Nymph/Adult after spray)/No. of Nymphs/Adult before spray) *100)

The result of study are recorded in Table 5.

Table 5: Efficacy study for Brown Plant Hopper ( Nilaparvata lugens) * a. /. /ha. = Active Ingredient per Hectare

Phytotoxicity

As per the standard testing, no phytotoxicity was observed with Fipronil 5% + Isoprothiolane 28% EC either at dose 1000 ml / ha (X) and double dose 5 2000 ml / ha (2X), the observations are recorded in Table 6.

Table 6: Observations on phytotoxicity of Fipronil 5%+ Isoprothiolane 28% EC at different concentrations * X = 1000 ml/ ha and 2X = 2000 ml /ha and a. i. /ha. = Active Ingredient per Hectare

Grain Yield

Significantly highest grain yield (kg/hectare) was registered after Fipronil 5 5%+ Isoprothiolane 28% EC @ 1000 ml/ha treatment, which was closely followed by Fipronil 5% SC alone @ 1000 and Isoprothiolane 40% EC @ 750 ml/ha treatments.

Table 7: Grain yield data (kg ha -1 )

* a. i. /ha. = Active Ingredient per Hectare and kg ha 1 = Kilogram per Hectare

Effects of EC formulation of present invention on natural enemies are 5 studied. Spider and Myrid bug are considered as one of the important bio- agents / predators in Rice crop eco-system, the result of application of EC formulation of present invention is found good for the beneficial insects.

Table 8: Result of impact of EC formulation of present invention on Spider population and Mirid bug in Rice crop eco-system in 1 meter 2 area of 10 sampling * a. /. /ha. = Active Ingredient per Hectare

Example 3.2: Experiment against Thrips and Purple blotch disease in Onion

5

Purple Blotch is caused by the fungus Alternaria porri. It is an important disease in warm, humid onion-growing regions around the world. Garlic and leeks also get affected by purple blotch. And on another hand Thrips, order Thysanoptera, are tiny, slender insects with fringed wings. They feed by 10 puncturing the epidermal (outer) layer of host tissue and sucking out the cell contents, which results in stippling, discolored flecking, or silvering of the leaf surface. Thrips feeding is usually accompanied by black varnish like flecks of frass (excrement). Specie Onion thrips (Thrips tabaci) cause damage to Onion, Garlic, leeks, Chilies, Capsicum, Celery, Peas, Melon, Choy sum, Bitter gourd , Chinese Broccoli, Long Melon and Snake Bean. in the same manner.

The efficacy of pesticidal emulsifiable concentrate formulation of present 5 invention comprising an effective amount of Fipronil and Isoprothiolane was evaluated against Thrips and Purple blotch disease in Onion in two ways viz. by one and two consecutive applications.

Experiment-1 : Two consecutive applications of pesticidal emulsifiable concentrate comprising Fipronil and Isoprothiolane.

10 Field experiment was carried out at Taluka Niphad of Nashik district in the state of Maharashtra. The crop was raised with standard agronomic practices.

Design: Random Block Design (RBD)

Plot size: 4m c 5m

15 Spacing: 8 inches c 8 inches

Variety: Gabran

Two consecutive applications were made at 15 days interval by Knapsack sprayer at vegetative, bulb formation and bulb fill stage and then the pest and disease assessment were done at 5 days after second application. The 0 summary of trail is provided in the following Table No. 9.

Table No.9: Summary of trial against Thrips and Purple blotch in Onion

Observation Observations taken after 5 days of application of 50 DAT at advance vegetative to reproductive i.e. bulb formation stage is provided in the Table 10.

Methodology applied for taking observations

5

Observation Methodology for Thrips

Reduction of population (% Thrips Control) = ((No. of thrips in control - No. of thrips after spray)/No. of thrips before spray) *100)

Observation Methodology for Alternaria porri (Pathogen of Purple blotch)

100 leaflets from the entire plot were randomly assessed and rated visually by rating scale and Percent Disease Index was calculated.

Percent disease Index (PDI) was calculated by using following formula

PDI = _ Sum of all disease

Ratings x 100 Total no of leaves/bunches assessed x Maximum Disease grade Table No.10: Observation of trial against Thrips and Purple blotch in Onion

Results

5 Results obtained after treatment of Fipronil 5% + Isoprothiolane 28% EC formulation of present invention, which was conducted at advance vegetative to reproductive stages i.e. bulb formation stage is recorded in the Table 11.

Table No.11 : Results of trial against Thrips and Purple blotch in Onion

The result shows that treatment T3 by spray of Fipronil 5% + Isoprothiolane 28% EC formulation with application of 3ml/1 liter of water provide better result as compared to T2 and T1 treatment.

5

Experiment-2: One application of pesticidal emulsifiable concentrate comprising Fipronil and Isoprothiolane.

The trial was conducted at Research Farm Ambala in the state of Haryana. The experiment was laid out in randomized complete block design and 10 replicated thRice with a single plot area of 33.3 m 2 . The test sample as per the treatment schedule was applied at pest appearance by using 500 liters of water/ hectare using a knapsack sprayer.

Pre-count for Thrips and Purple blotch was taken prior to the application of formulation. After application the observation had taken for Thrips at 3, 5 15 and 7 DAS (Days after Spray) and for Purple blotch observation was recorded at 10 and 15 DAS (Days after spray) of formulation of present invention.

Methodology applied for taking observations

0

Observation Methodology for Thrips

The population of Thrips was counted on randomly tagged plants. Further the reduction in population was worked out by the formula as follows and recorded in Table 12: 5 Reduction of population (% Thrips Control) = ((No. of thrips in control - No. of thrips after spray)/No. of thrips before spray) *100)

Table No.12: Results of trial against Thrips in Onion Observation Methodology for Purple blotch

Prior to spray, around 60-65% incidence of the disease was recorded in Onion.

5 Findings after the spray revealed that the disease spread stopped after application and thus the severity did not increase and the Phytotonic effect enhanced the greenness and chlorophyll content. The results were recorded in Table 13:

Table No.13: Results of Percent Plant greenness after trial against Purple 10 blotch in Onion

Example 3.3: Experiment against Podosphaera xanthii causing Powdery mildew in Okra (Pod vegetable)

5 Field experiment was carried out at Taluka Niphad of Nashik district in the state of Maharashtra. The crop was raised with standard agronomic practices.

Design: Random Block Design (RBD)

Plot size: 4m c 5m

10 Spacing: 8 inches c 8 inches

Variety: JK 713

Two consecutive applications were made at 15 days interval by Knapsack sprayer at vegetative, bulb formation and bulb fill stage and then the pest and disease assessment were done at 5 days after second application. The 15 summary of trail is provided in the following Table No. 14

Table No. 14: Summary of trial against Podosphaera xanthii in Okra (Pod vegetable)

Observation

0 Observations taken after 16 days of application of 50 DAT in Okra (Pod vegetable)

is provided in the Table 15.

Methodology applied for taking observations 100 leaflets from the entire plot were randomly assessed and rated visually by rating scale and Percent Disease Index was calculated.

Percent disease Index (PDI) was calculated by using following

5 formula.

PDI = _ Sum of all disease

Ratings _ x 100

Total no. of leaves/bunches assessed x Maximum Disease

10 grade

Table No.15: Observation of trial against Podosphaera xanthii in Okra

Results

Results taken are of height, leaf index and chlorophyll content in Okra plant obtained after treatment of Fipronil 5% + Isoprothiolane 28% EC 5 formulation, are provided in the Table 16.

Table No.16: Results of trial against Podosphaera xanthii in Okra (Pod vegetable)

10

The results of experimental data of the present invention reveals the followings:

1 ) The EC formulation of present invention shows synergistic effect on control of pests like stem borer, BPH, Blast in Rice (Paddy); Thrips

15 and Purple blotch in Onion; Powdery mildew caused by Podosphaera xanthii in okra (Pod vegetable). In the case of Blast and BPH, the effect exhibited by the formulation is both prophylactic as well as curative.

2) Two sprays of the EC formulation of present invention alone serves

5 good control over the intended pests in Paddy, Onion and Okra (Pod vegetable).

3) EC formulation of present invention alone (2 Sprays) gives effective control over pest when applied during 30 to 65 days after transplant.

4) The use of EC formulation of present invention as one shot solution

10 for the major damage cause by insect and disease in wide range of crops against pest and disease like Yellow stem borer, Whorl maggot, Brown planthopper, Green leafhopper, Thrips, Magnaporthe oryzae, Podosphaera xanthii, Alternaria species like Alternaria porri and Alternaria alternata. The reduced number of sprays also mean

15 less buildup of residues in the plant. Also it benefits the farmer as his cost of crop protection will come down significantly which will sequentially increase his profit margin by reducing of multiple types of sprayings.

5) Lesser number sprays also means superior efficacy of applied 0 invented product which make the product more eco-friendly and good for the beneficial insects.

6) Apart from pest management the EC formulation of present invention also shows significant Phytotonic effect.

7) The EC formulation of present invention can be used in the main crop 5 as well in the nursery also.

8) This formulation of present invention will lead to better crop yield and significant harvests without any chemical residue.

Those of ordinary skills in the art will appreciate that various embodiments of the present invention as disclosed hereinabove provide significant 0 advantages over prior art, such as, for example, but not limited to, (a) requirement of only two sprays of the emulsifiable concentrate formulation of insecticide and fungicide for delivering highly cost effective treatment; (b) providing better control over the intended insects and disease in Rice, Onion, Garlic, leeks, Chilies, Capsicum, Celery, Peas, Melon, Choy sum, Bitter melon, Chinese Broccoli, Long Melon, Snake Bean and Pod vegetables; (c) providing a better application window of spray of the 5 pesticidal emulsifiable concentrate during 30 to 65 days after transplant; (d) providing a single solution against problem of pest and disease like Yellow stem borer, Whorl maggot, Brown planthopper, Green leafhopper, Thrips, Magnaporthe oryzae, Podosphaera xanthii, Alternaria species like Alternaria porri and Alternaria alternate; (e) illustrating a conspicuous 10 Phytotonic effect; (f) providing significant grain yield after crop treatment; (g) no harmful effects on natural enemies, and the like.

While this invention has been described in detail with reference to certain preferred embodiments, it should be appreciated that the present invention is not limited to those precise embodiments rather, in view of the present 15 disclosure, which describes the current best mode for practicing the invention, many modifications and variations, would present themselves to those skilled in the art without departing from the scope and spirit of this invention. This invention is susceptible to considerable variation in its practice within the spirit and scope of the appended claims. 0

5

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