The present invention is related to a pesticidal emulsifiable concentrate formulation comprising 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. This pesticidal emulsifiable concentrate comprising an effective amount of Fipronil and Isoprothiolane has significant broad spectrum efficacy, safety, environmental protection, and low toxicity.
BACKGROUND OF THE INVENTION
Pesticides are substances that are meant to control pests (Insects, 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, 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 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 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.

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, Geocoridae, Miridae, Libellulidae, Coenagrionidae, Empusidae, Mantodae, Sciomyzidae, Syrphidae, Platystomatidae, Ephydridae, Ascalaphidae, Dermistidae, Ichneumonidae, 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 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 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 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.
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. 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 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 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 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 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 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. 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, 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.
There is a lot of demand of Indian Onion in the world, the country has exported 24, 15,757.11MT 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 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 certain varieties in yellow onion which are suitable for export in European countries Tana Fl, 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 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. 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 covered in coarse stippling and may
5 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.
Therefore, there is a need to protect Paddy, Onion, Garlic, leeks, Chilies, Capsicum,
10 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
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
15 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 plants year-round, and transplanting of young seedlings favor the development of Rice whorl maggot.
20 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 places with abundant calm water and lush vegetation. The insect does not prefer direct-seeded fields and seedbeds. The adult is active
25 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 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
30 the feeding stalk.
Page 6 of 36

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 becomes visible when the
5 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 the base.
The yellow stem borer is an insect of deepwater Rice. It is found in aquatic
10 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 themselves to the tiller and bore
into the stem.
Stem borers can destroy Rice at any stage of the plant from seedling to maturity.
15 They feed upon tillers and causes deadhearts or drying of the central tiller, during
vegetative stage; and causes whiteheads at reproductive stage.
Two species of planthopper infest Rice. These are the brown planthopper
(BPH), Nilaparvata lugens (Stal); and the whitebacked planthopper
(WBPH), Sogatella furcifera (Horvath).
20 Planthoppers can be a problem in rainfed and in irrigated wetland environments. It
also occurs in areas with continuous submerged conditions 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.
25 High population of planthoppers cause leaves to initially turn orange-yellow 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.
30 Two species of green leafhoppers (GLH) can spread tungro: Nephotettix
malayanus and Nephotettix virescens.
Page 7 of 36

Green leafhoppers are common in rainfed and irrigated wetland environments. They
are not prevalent in upland Rice. Both the nymphs and 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
5 Rice plants that have been fertilized with large amount of nitrogen.
Blast can occur wherever blast spores are present. It occurs in areas with 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
10 disease.
Rice can have blast in all growth stages. However, leaf blast incidence tends 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
15 no grains at all.
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
20 to dry and chaffy. The significant disease problem is Purple blotch 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
25 increases, leaves turn yellow brown, lose 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
30 food. Insects like thrips and fungal diseases are the main biological constraints in
Page 8 of 36

chilli production, and Alternaria leaf spot disease, one of the most devastating
diseases of chilli caused by the species of Alternaria (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
5 porri and Alternaria alternate and Podosphaera xanthii. Here phylum is a level of
classification or taxonomic rank below Kingdom 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
10 the most affected, but the mildew can appear on any 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 to pierce
15 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.
20 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. Further, formulations like
25 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
30 folder. This will be followed by the application of Isoprothiolane for the control of
Blast and Buprofenzin for controlling BPH.
Page 9 of 36

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) @ 0.05% + P. fluorescens@
5 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 Acephate 75 SP @ lg/l or
10 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 pesticidal emulsifiable
concentrate formulation provides the best control against pest and disease like
15 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
chemical family. Fipronil disrupts the insect central nervous system by blocking
20 GABA-gated chloride channels and glutamate-gated chloride (GluCl) 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 mammals and its effect on GluCl channels, which do
not exist in mammals. It is chemically known as (RS)-5-Amino-1-[2, 6-dichloro-4-
25 (trifluoromethyl) phenyl]-4-(trifluoromethylsulfinyl) pyrazole-3-carbonitrile and
having chemical structure formula represented as below,
Page 10 of 36

F
F
5
10
15

F
Cl H2N
O 1 I J
F. S
V \=N Cl
//
N
Fipronil
Because of its effectiveness on a wide range of insects, Fipronil is used as 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 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 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,

CH3
20

O
O

H3C
O H3C—( O CH3
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

Page 11 of 36

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 is 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 ingredient
10 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 discloses a pesticidal emulsifiable concentrate composition
15 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 and pests. This document does not discloses a pesticidal emulsifiable concentrate comprising
20 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 GluCl channels, which do not exist in mammals so pesticidal emulsifiable concentrate comprising Fipronil and Isoprothiolane is more safe.
25 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 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
30 emulsifiable concentrate comprising an effective amount of insecticide and
fungicide effective for curing disease in onion.
Page 12 of 36

Chinese Patent Application No. 105766908 A, discloses an emulsifiable
concentrate with sec-butyl acetate as a solvent. This document discloses
formulation of one insecticide, thus this document does not discloses a pesticidal
emulsifiable concentrate composition comprising an effective amount of Fipronil
5 and Isoprothiolane.
Chinese Patent Application No. 106035349 A, discloses a composition for preventing and removing the harmful organisms includes a combination of 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,
10 Buprofezin, Flutotanil, Fenpyroximate, Pyraflufen-ethyl, Tiadinil, basic Chrome
sulphate, and Fluoromide. The effective component B includes compounds such as Acetamiprid, Isoprocarb, and Ethofenprox, thus this document does not discloses a pesticidal emulsifiable concentrate composition comprising an effective amount of Fipronil and Isoprothiolane.
15 WO 2013/083372A1, discloses an emulsifiable concentrate comprising a water-
insoluble pesticide, benzyl alcohol, alkyl lactate and not more than 40% by weight of dimethyl sulfoxide., thus this document does not discloses a pesticidal emulsifiable concentrate composition comprising an effective amount of Fipronil and Isoprothiolane and wherein the said formulation comprises aprotic solvent as
20 co-solvent.
WO 2015/200428A1, discloses an emulsifiable foaming concentrate. This document discloses formulation of one insecticide, thus this document does not discloses a pesticidal emulsifiable concentrate composition comprising an effective amount of Fipronil and Isoprothiolane.
25 However, for crops protection against effect of Yellow stem borer, Whorl maggot,
Brown planthopper, Green leafhopper, Thrips, Magnaporthe 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
30 without much complex manufacturing process.
Page 13 of 36

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 concentrate formulation of present invention
5 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 OBJECTIVE AND ADVANTAGES OF THE INVENTION
It is a principal object of the present invention to develop an effective pesticidal
emulsifiable concentrate formulation, which is on one hand is effective to
overcomes the existing problems in wider range in pesticidal effect to control pest
like Whorl maggot, Yellow Stem borer, Brown plant hopper, Green leaf hopper,
15 blast diseases like Leaf blast, Node blast, Neck blast in Rice (Paddy) caused by
Magnaporthe oryzae. Effective control of Thrips, fungal disease like Purple blotch,
Alternaria leaf spot caused by 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,
20 Chinese Broccoli, Long Melon, Snake Bean and Pod vegetables with ensuring
environmental safety due to low toxicity and intrinsic property of stability on another hand. The present invention also has the following other advantages:
1) Only two sprays of the emulsifiable concentrate formulation of insecticide
25 and fungicide delivers highly cost effective treatment. This combination
chemistry alone serves good 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. The application window of spray of present invention pesticidal
30 emulsifiable concentrate when applied during 30 to 65 days after transplant.
Page 14 of 36

2) The emulsifiable concentrate formulation of present invention provides one
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
5 Alternaria alternata. Apart from pest management the emulsifiable
concentrate formulation of insecticide and fungicide of present invention also shows conspicuous Phytotonic effect.
3) The formulation of present invention results in significant grain yield after
crop treatment
10 4) The formulation of present invention is not having harmful effects on
natural enemies
SUMMARY OF THE INVENTION
The present invention is related to a pesticidal emulsifiable concentrate formulation
15 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,
20 Chilies, Capsicum, Celery, Peas, Melon, Choy sum, Bitter melon, Chinese
Broccoli, Long Melon, Snake 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.
25 A pesticidal emulsifiable concentrate formulation according to the present
invention used for controlling pests or diseases comprising wherein, Fipronil and Isoprothiolane are in the ratio between 1:6 to 6:1. A pesticidal emulsifiable concentrate according to the present invention comprising Fipronil and Isoprothiolane with other auxiliary agents is a stable formulation.
Page 15 of 36

Other aspects of the invention will be set forth in the description which follows, and in part will be apparent from the description, or may be learnt by the practice of the invention.
5 DETAILED DESCRIPTION OF THE INVENTION
The present invention is related to a pesticidal emulsifiable concentrate formulation comprising 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. A pesticidal
10 emulsifiable concentrate 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
15 the present invention comprising Fipronil and Isoprothiolane with other auxiliary
agents is a stable formulation.
The term “pesticide” or “pesticidal” is similar to “insecticide” or “insecticidal” is used interchangeably in this whole specification. The term “fungicide or fungicides” used in this specification is a biocidal chemical
20 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 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
25 used inter changeably and convey the same meaning.
A pesticidal emulsifiable concentrate according to the present invention 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.
30 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 preferably
Page 16 of 36

between1:6 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
5 in an amount ranging from 10% to 30% w/w. The 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 acts synergistically when applied to the crops.
10 Aprotic solvent in this invention is a co-solvent which is added to a pesticidal
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
15 aprotic solvent as co-solvent which is selected from the group 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
20 modify the performance of the formulation or composition. Preferably, an adjuvants
comprises emulsifier, anti-freezing agent, dispersing agent, antifoaming agent, suspending agent and thickener. The 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
25 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, thiophosphoro succinate salt, taurine derivatives (in particular alkyl taurate), polyoxyethylene alcohol or phenol phosphoric acid ester, fatty acid esters of
30 polyols. Preferred one is ethoxylated fatty glyceride.
Page 17 of 36

The 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
5 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, Chinese Broccoli, Long
10 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 synergistic
15 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
20 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 WEEDS 1967, 15, 22 E = (X + Y) – ((X × Y)/100) For Synergy, O/E > 1
25 wherein;
X=effect in percent (%) using (a) Fipronil
Y=effect in percent (%) using (b) Isoprothiolane
E=expected effect (in %) of (a) + (b) at application rates a and b.
O=Observed effect (in %) of (a) + (b)
30 A pesticidal emulsifiable concentrate according to the present invention comprising
Fipronil and Isoprothiolane with other auxiliary agents is a stable composition.
Page 18 of 36

The following examples are intended to illustrate, but in no way limit the scope of, the present invention.
EXAMPLES
Example 1: Preparation of Fipronil and Isoprothiolane Emulsifiable
5 concentrate (EC) formulation
In an appropriately sized beaker, aromatic solvent was charged. After it charge
required quantity of Fipronil & Isoprothiolane under stirring, followed 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
10 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 is tabulated below:
Table: 1: Chemical Composition

Chemical Composition Content (% w/w)
Isoprothiolane a.i 28.00
Fipronil a.i 05.00
Dimethylformamide 05.00
Calcium alkyl aryl sulfonate & phenol ethylene oxide condensate blend (non-ionic) 08.00
Light aromatic solvent naphtha (petroleum) QS to make 100 %
Total 100.00
15 Examples 2: Stability Study
Storage stability study data of In-house developed Fipronil 5.0 % + Isoprothiolane 28 % Emulsifiable concentrate (EC) formulation is tabulated in Table 2. Table 2: Storage stability study data

Parameters Specification Initial Heat stability at 54±2 °C for 14 days

Batch No. 1 Batch No. 2
Page 19 of 36

Physical Description Yellow to light brown color, clear transparent liquid Yellow
colored,
clear
transparent
liquid Yellow colored, clear transparent liquid Yellow colored, clear transparent liquid
a.i % w/w Fipronil Content 5.24 % 5.19% 5.10%

Isoprothiolane Content 28.31 % 28.16% 28.13%
Acidity 0.50 % max. 0.0 18% 0.0 15 % 0.0 17 %
Density at 20 °C (g/ml) 0.95-1.05 0.99 0.99 0.99
Emulsion Stability Any
separation of cream or sediments shall not exceed more than 2.0 ML NIL NIL NIL
Similarly, modifications and variations in process without departing from the
scope and spirit of this invention would results in Emulsifiable concentrate (EC) formulation as per the scope and spirit of present invention.
EXAMPLE 3: FIELD EFFICACY TRIALS
5 The objective of the field trial experiments was:
1) To find out pesticidal effect of emulsifiable concentrate of present 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
10 porri, Powdery mildew disease caused by Podosphaera xanthii. In the case
of Blast and Purple 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
Page 20 of 36

65 days after transplant, which provides one 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.
5 3) To study the effect of formulation of present invention in significant 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 Plant
10 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
15 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 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
20 prophylactic effect on BPH following its two applications. A pesticidal emulsifiable
concentrate comprising Fipronil and Isoprothiolane was 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).
25 Initially the infestation was very minor (around 2%). This population started
building up and reached its peak (60-65 % infestation) at 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
30 population reached a peak, with 70-75% infestation, at 50-55 DAT, it remained
Page 21 of 36

constant for a while and then 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
5 declining trend similar to the other pests. Very few plants (1 or 2/metre2) 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,
10 followed by Leaf folder and Stem borer 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 Isoprothiolan is used to control of Blast and BPH e and Buprofenzin are used
15 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 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
20 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 different insect pest and disease was planted at a spacing of 15 × 15 cm. The sprays were carried out as per the treatments, using a battery operated knapsack
25 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.
Observation Methodology for Stem borer
Percent Control for stem Borer (Observed Value) = ((No. of Dead hearts before
30 spray – No. of Dead hearts after spray)/No. of Dead hearts before spray) ×100)
The result of study are recorded in Table 3.
Page 22 of 36

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

Treatments gm a. i./ha Observed Value Expected
Value
(Colby
Value ) Ratio (Observed
over Expected) Synergy
Fipronil + Isoprothiolane (EC) 50 + 280 89 77.97 1.14 Yes
Fipronil + Isoprothiolane (EC) 40 + 220 87 77.97 1.12 Yes
Fipronil + Isoprothiolane (EC) 30 + 160 55 77.97 0.71 No
Fipronil + Isoprothiolane (EC) 20 + 100 49 77.97 0.63 No
Fipronil +
Isoprothiolane
(Tank mix) 50 + 300 73 77.97 0.94 No
Fipronil +
Isoprothiolane
(Tank mix) 25 + 150 32 77.97 0.41 No
Isoprothiolane 40% EC @ 750 300 10
Fipronil 5% SC @ 1000 50 75
Untreated Control - 0
*a. i. /ha. = Active Ingredient per Hectare
Observation Methodology for Blast
5
Percent Control for Blast (Observed value) = Percent disease incidence before spray – Percent disease incidence after spray The result of study are recorded in Table 4.
10
Page 23 of 36

Table 4: Efficacy study for Blast Pyricularia Oryzae (sexual morph Magnaporthe oryzae)
Treatments gm a. i./ha Observed Value Expected
Value
(Colby
Value ) Ratio (Observed
over Expected) Synergy
Fipronil + Isoprothiolane (EC) 50 + 280 82 76.25 1.08 Yes
Fipronil + Isoprothiolane (EC) 40 + 220 80 76.25 1.05 Yes
Fipronil + Isoprothiolane (EC) 30 + 160 58 76.25 0.76 No
Fipronil + Isoprothiolane (EC) 20 + 100 45 76.25 0.59 No
Fipronil +
Isoprothiolane
(Tank mix) 50 + 300 72 76.25 0.94 No
Fipronil +
Isoprothiolane
(Tank mix) 25 + 150 25 76.25 0.33 No
Isoprothiolane 40% EC @ 750 300 75
Fipronil 5% SC @ 1000 50 5
Untreated Control - 0
*a. i. /ha. = Active Ingredient per Hectare
5
Observation Methodology for Brown Plant Hopper
Percent control for BPH = ((No. of Nymph/Adult before spray – NO. of Nymph/Adult after spray)/No. of Nymphs/Adult before spray) ×100)
10 The result of study are recorded in Table 5.
Page 24 of 36

Table 5: Efficacy study for Brown Plant Hopper (Nilaparvata lugens)

Treatments gm a. i./ha Observed Percent control Expected Control (Colby Value) Ratio Synergy
Fipronil + Isoprothiolane (EC) 50 + 280 85 82.72 1.03 Yes
Fipronil + Isoprothiolane (EC) 40 + 220 82.34 82.72 1.00 Yes
Fipronil + Isoprothiolane (EC) 30 + 160 60.32 82.72 0.73 No
Fipronil + Isoprothiolane (EC) 20 + 100 58.54 82.72 0.71 No
Fipronil +
Isoprothiolane
(Tank mix) 50 + 300 70.20 82.72 0.85 No
Fipronil +
Isoprothiolane
(Tank mix) 25 + 150 38.34 82.72 0.46 No
Isoprothiolane 40% EC @ 750 300 36.00
Fipronil 5% SC @ 1000 50 73.00
Untreated Control - 0.00
*a. i. /ha. = Active Ingredient per Hectare
Phytotoxicity
As per the standard testing no phytotoxicity was observed with Fipronil 5% +
5 Isoprothiolane 28% EC either at dose 1000 ml / ha (X) and double dose 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

Treatments Epinasty Hyponasty Necrosis Vein clearing Wilting

X 2X X 2X X 2X X 2X X 2X
Fipronil +
Isoprothiolane
EC (50gm
a. i./ha + 280gm
a. i./ha) 0 0 0 0 0 0 0 0 0 0
Page 25 of 36

Fipronil + 0 0 0 0 0 0 0 0 0 0
Isoprothiolane
EC (100gm
a. i./ha + 560gm
a. i./ha)
Untreated 0 0 0 0 0 0 0 0 0 0
Control
* 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)

Treatments Gm a. i./ha Grain
yield
(kg ha-1)
Fipronil + Isoprothiolane (EC) 50 + 280 6188 .2
Fipronil + Isoprothiolane (EC) 40 + 220 5673.9
Fipronil + Isoprothiolane (EC) 30 + 160 5397.2
Fipronil + Isoprothiolane (EC) 20 + 100 4095.3
Fipronil +
Isoprothiolane
(Tank mix) 50 + 300 5067.8
Fipronil +
Isoprothiolane
(Tank mix) 25 + 150 4196.4
Isoprothiolane 40% EC @ 750 300 4447.4
Fipronil 5% SC @ 1000 50 5161.1
Untreated Control - 4148.9
*a. i. /ha. = Active Ingredient per Hectare and kg ha-1= Kilogram per Hectare
Page 26 of 36

Effect of EC formulation of present invention on natural enemies are studied. Spider and Myrid bug are considered as one of the important bio-agent / predator in Rice crop eco-system, the result of application of EC formulation of present invention is found good for the beneficial insects.
5 Table 8: Result of impact of EC formulation of present invention on Spider
population and Mirid bug in Rice crop eco-system in 1 meter2 area of sampling

Treatments gm a.i./ha No. of Spider No. of Mirid bug

Pre-count 5 Days 10 Days 15 Days Pre-count 5 Days 10 Days 15 Days
Fipronil +
Isoprothiolane
(EC) 50 + 280 3 2 2 3 5 6 7 5
Fipronil +
Isoprothiolane
(EC) 40 + 220 2 2 2 2 5 5 5 5
Fipronil +
Isoprothiolane
(EC) 30 + 160 1 0 1 2 1 3 5 3
Fipronil +
Isoprothiolane
(EC) 20 + 100 3 2 2 3 5 7 7 5
Untreated Control - 1 0 1 2 1 3 5 3
*a. i. /ha. = Active Ingredient per Hectare
Example 3.2: Experiment against Thrips and Purple blotch disease in Onion
10
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
Page 27 of 36

tiny, slender insects with fringed wings. They feed by 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
5 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 invention
comprising an effective amount of Fipronil and Isoprothiolane was evaluated
10 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.
Field experiment was carried out at Taluka Niphad of Nashik district in the state of
15 Maharashtra. The crop was raised with standard agronomic practices.
Design: Random Block Design (RBD)
Plot size: 4m × 5m
Spacing: 8 inches × 8 inches
Variety: Gabran
20 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 summary of trail is
provided in the following Table No. 9
Table No.9: Summary of trial against Thrips and Purple blotch in Onion

Considering that Standard water used 200 liters per acre
Treatments Spray
[Fipronil 5% + Isoprothiolane 28% EC
(ml)/ liter of water] Replication
T3 3ml/1 liter ×3 times
Page 28 of 36

T2 2.5ml/1 liter ×3 times
T1 2ml/1 liter ×3 times
T4 (Control) No spray ×3 times
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. 5
Methodology applied for taking observations
Observation Methodology for Thrips
Reduction of population (% Thrips Control) = ((No. of thrips in control – No. of
10 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.

Score Symptoms
0 No symptom on the leaf
1 Small irregular brown spots covering 1% or less of the leaf area
3 Small, irregular, brown spots with concentric rings covering 1 – 10% of the leaf area
5 Lesions enlarging, irregular, brown with concentric rings, cover 11 – 25% of leaf area
7 Lesions coalesce to form irregular, dark brown patches with concentric rings covering 26 – 50% of leaf area. Lesions on stems and petioles
9 Lesions coalesce to form irregular, dark brown patches with concentric rings covering more than 51% of leaf area. Lesions on stems and petioles
15
Page 29 of 36

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

Considering that Standard water used 200 liters per acre
Treatments Spray
[Fipronil 5% +
Isoprothiolane 28% EC
(ml)/ liter of water] Control on
Thrips attack
(%) Purple blotch (% PDI)
T3 3ml/1 liter 98 98
T2 2.5ml/1 liter 85 85
T1 2ml/1 liter 70 70
T4 (Control) No spray 5 5
5
Results
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.
10 Table No.11: Results of trial against Thrips and Purple blotch in Onion

Considering that Standard water used 200 liters per acre
Treatments Spray [Fipronil 5% + Isoprothiolane 28% EC (ml)/ liter of water] Height (Inch) Weight (Gm) Leaf Index (Inch) Chlorophyll
Content
(%) Collar/ Sheath
Grith/ Sheath
Braid/
Circumference
(Inch)
T3 3ml/1 liter 17 210 1 98 1.6
T2 2.5ml/1 liter 15 120 0.7 95 1.3
T1 2ml/1 liter 14 80 0.5 90 1.2
T4(Control) No spray 13 65 0.5 75 1
Page 30 of 36

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 replicated
thRice with a single plot area of 33.3 m2. The test sample as per the treatment
10 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 and 7 DAS (Days after Spray) and for Purple blotch observation was recorded at 10 and
15 15 DAS (Days after spray) of formulation of present invention.
Methodology applied for taking observations
Observation Methodology for Thrips
20 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:
Reduction of population (% Thrips Control) = ((No. of thrips in control – No. of thrips after spray)/No. of thrips before spray) ×100)
25 Table No.12: Results of trial against Thrips in Onion

Treatment Dose (ml/Acre) % Control 3 DAS % Control 5 DAS % Control 7 DAS
Fipronil 5% + Isoprothiolane 28% EC 400 20 25 60
Fipronil 5% + Isoprothiolane 28% EC 500 30 55 75
Page 31 of 36

Fipronil 5% + Isoprothiolane 28% EC 600 35 60 75
Control No spray 0 0 0
Observation Methodology for Purple blotch
Prior to spray around 60-65% incidence of the disease was recorded in Onion.
Findings after the spray revealed that the disease spread stopped after application
5 and thus the severity did not increase and the Phytotonic effect enhanced the
greenness and chlorophyll content. The results was recorded in Table 13:
Table No.13: Results of Percent Plant greenness after trial against Purple blotch in Onion

Treatment Dose (ml/Acre) Prior to spray Chlorophyll
Content (%) 5 days after
spray Chlorophyll
Content (%) 7 days after
spray Chlorophyll
Content (%)
Fipronil 5% + Isoprothiolane 28% EC 400 20 50 88
Fipronil 5% + Isoprothiolane 28% EC 500 25 53 90
Fipronil 5% + Isoprothiolane 28% EC 600 22 52 90
Control No spray 22 30 30
10 Example 3.3: Experiment against Podosphaera xanthii causing Powdery
mildew in Okra (Pod vegetable)
Field experiment was carried out at Taluka Niphad of Nashik district in the state of
Maharashtra. The crop was raised with standard agronomic practices.
15 Design: Random Block Design (RBD)
Plot size: 4m × 5m Spacing: 8 inches × 8 inches
Page 32 of 36

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 summary of trail is
5 provided in the following Table No. 14
Table No. 14: Summary of trial against Podosphaera xanthii in Okra (Pod vegetable)

Considering that Standard water used 200 liters per acre
Treatments Spray
[Fipronil 5% + Isoprothiolane 28% EC
(ml)/ liter of water] Replication
T3 3ml/1 liter ×3 times
T2 2.5ml/1 liter ×3 times
T1 2ml/1 liter ×3 times
T4 (Control) No spray ×3 times
Observation
10 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
15 scale and Percent Disease Index was calculated.

Score Symptoms
0 No symptom on the leaf
1 Small irregular brown spots covering 1% or less of the leaf area
3 Small, irregular, brown spots with concentric rings covering 1 – 10% of the leaf area
Page 33 of 36

5 Lesions enlarging, irregular, brown with concentric rings, cover 11 – 25% of leaf area
7 Lesions coalesce to form irregular, dark brown patches with concentric rings covering 26 – 50% of leaf area. Lesions on stems and petioles
9 Lesions coalesce to form irregular, dark brown patches with concentric rings covering more than 51% of leaf area. Lesions on stems and petioles
Percent disease Index (PDI) was calculated by using following formula
PDI = Sum of all disease Ratings x 100
5 Total no of leaves/bunches assessed x Maximum Disease grade
Table No.15: Observation of trial against Podosphaera xanthii in Okra

Considering that Standard water used 200 liters per acre
Treatments Spray
[Fipronil 5% +
Isoprothiolane 28% EC
(ml)/ liter of water] Powdery mildew (% PDI)
T3 3ml/1 liter 97
T2 2.5ml/1 liter 80
T1 2ml/1 liter 72
T4 (Control) No spray 4
Results
10 Results taken are of height, leaf index and chlorophyll content in Okra plant
obtained after treatment of Fipronil 5% + Isoprothiolane 28% EC formulation, are provided in the Table 16
Page 34 of 36

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

Considering that Standard water used 200 liters per acre
Treatments Spray [Fipronil 5% + Isoprothiolane 28% EC (ml)/ liter of water] Height (Inch) Leaf Index (Inch) Chlorophyll
Content
(%)
T3 3ml/1 liter 22 15 98
T2 2.5ml/1 liter 19.0 11 92
T1 2ml/1 liter 11.5 9 87
T4(Control) No spray 9 9 85
The results of experimental data of the present invention reveals the followings:
1) The EC formulation of present invention shows synergistic effect on control
5 of pests like stem borer, BPH, Blast in Rice (Paddy); Thrips 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 good
10 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 for the major damage cause by insect and disease in wide range of crops against
15 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 less buildup of residues in the plant. Also it benefits the farmer as his cost of crop protection will come down
Page 35 of 36

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 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 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.
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 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.

We Claim:

A pesticidal emulsifiable concentrate comprising Fipronil and Isoprothiolane.
A pesticidal emulsifiable concentrate as claimed in claim 1, wherein Fipronil and
Isoprothiolane is present in the ratio ranging from 1:6 to 6:1
A pesticidal emulsifiable concentrate as claimed in claim 1, wherein Fipronil is
present in an amount ranging from 1% to 6% w/w.
A pesticidal emulsifiable concentrate as claimed in claim 1, wherein Isoprothiolane
is present in an amount ranging from 10% to 30% w/w.
A pesticidal emulsifiable concentrate as claimed in claim 1, comprising synergistic
effective amount of Fipronil and Isoprothiolane.
A pesticidal emulsifiable concentrate as claimed in claim 1, wherein the said
formulation comprises aprotic solvent as co-solvent.
A pesticidal emulsifiable concentrate as claimed in claim 6, wherein the amount of
co-solvent is present in an amount ranging from 1% to 10% w/w.
A pesticidal emulsifiable concentrate as claimed in claim 6, wherein the co-solvent
is selected from the group comprising dimethylformamide, N-Methyl-2-
pyrrolidone, 2-Ethylhexyl Acetate, 2-Ethylhexyl Acrylate or a mixture thereof.
A pesticidal emulsifiable concentrate as claimed in claim 6, wherein the said
formulation comprises aprotic solvent as co-solvent is dimethylformamide. ). A pesticidal emulsifiable concentrate as claimed in any of the preceding claims,
wherein the said formulation comprising Fipronil and Isoprothiolane is effective
against insects in Paddy, Onion, Garlic, leeks, Chilies, Capsicum, Celery, Peas,
Melon, Choy sum, Bitter melon, Chinese Broccoli, Long Melon, Snake Bean and
Pod vegetables. . A pesticidal emulsifiable concentrate as claimed in any of the preceding claims,
wherein the said formulation comprising Fipronil and Isoprothiolane is effective
against fungal disease in Paddy, Onion, Garlic, leeks, Chilies, Capsicum, Celery,

Peas, Melon, Choy sum, Bitter melon, Chinese Broccoli, Long Melon, Snake Bean
and Pod vegetables. . A pesticidal emulsifiable concentrate as claimed in any of the preceding claims,
wherein the said formulation comprising Fipronil and Isoprothiolane is effective
against Yellow stem borer, Whorl maggot, Brown planthopper, Green leafhopper ,
Thrips, Magnaporthe oryzae, Podosphaera xanthii, Alternaria porri and Alternaria
alternata. . A pesticidal emulsifiable concentrate as claimed in any of the preceding claims,
wherein the said formulation comprising Fipronil and Isoprothiolane is effective
against Yellow stem borer, Whorl maggot, Brown planthopper, Green leafhopper ,
Thrips, Magnaporthe oryzae, Podosphaera xanthii, Alternaria porri and Alternaria
alternata in Paddy, Onion and Okra . The use of a pesticidal emulsifiable concentrate comprising Fipronil and
Isoprothiolane as claimed in any of the preceding claims, in Paddy, Onion, Garlic,
leeks, Chilies, Capsicum, Celery, Peas, Melon, Choy sum, Bitter melon, Chinese
Broccoli, Long Melon, Snake Bean and Pod vegetables. . The use of a pesticidal emulsifiable concentrate comprising Fipronil and
Isoprothiolane as claimed in any of the preceding claims, against Yellow stem
borer, Whorl maggot, Brown planthopper, Green leafhopper, Thrips, Magnaporthe
oryzae, Podosphaera xanthii, Alternaria porri and Alternaria alternate. . A pesticidal emulsifiable concentrate as claimed in any of the preceding claims,
wherein the said formulation comprising Fipronil and Isoprothiolane is effective
when applied during 30 to 65 days after transplant. . The method of application of a pesticidal emulsifiable concentrate as claimed in
any of the preceding claims, wherein the said formulation comprising Fipronil and
Isoprothiolane applied during 30 to 65 days after transplant. . A pesticidal emulsifiable concentrate as claimed in any of the preceding claims,
wherein the said formulation comprising Fipronil and Isoprothiolane is effective
when applied in the dosage range of 800-1500 ml/hectare.

The method of application of a pesticidal emulsifiable concentrate as claimed in any of the preceding claims, wherein the said formulation comprising Fipronil and Isoprothiolane applied in the dosage range of 800-1500 ml/hectare. A pesticidal emulsifiable concentrate comprising Fipronil and Isoprothiolane in synergistic effective amounts as claimed in any of the preceding claims and exemplified with working example as disclosed.