Claims:CLAIMS:
We claim;
1. A synergistic non aqueous agrochemical composition comprising:
a) Tert-butyl4-[[(E)-(1,3-dimethyl-5-phenoxypyrazol-4-yl)methylidene amino] oxymethyl ]benzoate, a compound of formula I present in an amount of 1% - 20% w/w;

b) an active ingredient is selected from class of an insecticide or a fungicide or a plant health additive or combination thereof present in an amount of 0.1% - 50% w/w;
c) Polyalkyleneoxide modified Heptamethyl trisiloxane (modified trisiloxane), a super wetting-spreading-penetrating agent is present in an amount of 1% to 10% w/w.
d) carrier is selected from pongamia oil or palm oil or jojoba oil or combination thereof or blend with vegetable oil present in an amount of 10% to 80% w/w;
and one or more formulation excipients.

2. The synergistic non aqueous agrochemical composition as claimed in claim 1, wherein combination of active ingredient is selected from compound of Formula I +Insecticide; or Compound of Formula I + InsecticideA + InsecticideB; or Compound of Formula I + Fungicide; or Compound of Formula I + FungicideA + FungicideB; or Compound of Formula I + Plant Health Additive; or Compound of Formula I + Insecticide+Plant Health Additive; or Compound of Formula I + Fungicide+Plant Health Additive; or Compound of Formula I + Insecticide+ Fungicide.

3. The synergistic non aqueous agrochemical composition as claimed in claim 1 or 2, wherein an insecticide is selected from class of Carbamates; Organophosphates; Phenylpyrazole; Pyrethroids; Nicotinic insecticides; Spinosyns; Mectins; Juvenile hormone mimics; Chordotonal organs modulators; Mite growth inhibitors; Microbial disruptors of insect midgut membrane; Inhibitors of mitochondrial ATP synthase; Uncouplers of oxidative phosphorylation; Nereis toxin; Chitin biosynthesis inhibitors; Inhibitors of the chitin biosynthesis type 1; Moulting disruptors; Ecdyson receptor agonists; Octopamin receptor agonists; METI (mitochondrial electron transport inhibitors; Voltage-dependent sodium channel blockers; Inhibitors of the lipid synthesis, inhibitors of acetyl CoA carboxylase; Diamides; Metadiamides; Isoxazolines; Baculoviruses; compounds of unknown or uncertain mode of action.

4. The synergistic non aqueous agrochemical composition as claimed in claim 1 or 2, wherein a fungicide compound is selected from Nucleic acid synthesis inhibitors; Cytoskeleton and motor proteins/cell division Inhibitors; Respiration inhibitors; Amino acids and protein synthesis inhibitors; Signal transduction inhibitors; Lipid or transport and membrane synthesis inhibitors; Sterol biosynthesis Inhibitors; Cell wall biosynthesis Inhibitors; Melanin synthesis in cell wall Inhibitors; Plant defence inducers; Unknow mode of action; Not classified (N); Chemicals with multisite activities (M)-multisite contact activities; Biologicals with multiple modes of action (BM).

5. The synergistic non aqueous agrochemical composition as claimed in claim 1 or 2, wherein plant health additives are selected from bio-stimulants, plant growth regulators, microbial agents and micronutrients or mixture thereof.

6. The synergistic non aqueous agrochemical composition as claimed in claim 1-claim 5, wherein combinations of active ingredients in the agrochemical composition comprises:
i. compound of Formula I 6% + Etoxazole 10% ;
ii. compound of Formula I 4% + Hexythiazox 4%;
iii. compound of Formula I 3% + Abamectin 2%;
iv. compound of Formula I 3% + Cyenopyrafen 10%;
v. compound of Formula I 4% + Spiromesifen 15%;
vi. compound of Formula I 4% + Spirodiclofen 15%;
vii. compound of Formula I 4% + Spirotetramat 15%;
viii. compound of Formula I 4% + Spiropidion 12%;
ix. compound of Formula I 4% + Spidoxamat 12%;
x. compound of Formula I 2.4% + Diafenthiuron 25%;
xi. compound of Formula I 2.4% + Bifenazate 16%;
xii. compound of Formula I 2.4% + Bifenthrin 8%;
xiii. compound of Formula I 6% + Lambda cyhalothrin 8%;
xiv. compound of Formula I 3% + Chlorantraniliprole 4%;
xv. compound of Formula I 3% + Cyantraniliprole 8%;
xvi. compound of Formula I 3% + Tetraniliprole 8%;
xvii. compound of Formula I 3% + Cyclaniliprole 8%;
xviii. compound of Formula I 6% + Broflanilide 3%;
xix. compound of Formula I 6% + Fluxametamide 3%;
xx. compound of Formula I 6% + Clothianidin 8%;
xxi. compound of Formula I 6% + Thiamethoxam 8%;
xxii. compound of Formula I 6% + Dinotefuran 8%;
xxiii. compound of Formula I 3% + Flonicamid 8%;
xxiv. compound of Formula I 3% + Chlorfenpyr 10%;
xxv. compound of Formula I 1.5% + Cyflumetofen 10%;
xxvi. compound of Formula I 1.5% + Dicofol 20%;
xxvii. compound of Formula I 1.5% + Fenazaquin 7.5%;
xxviii. compound of Formula I 1.5% + Flufenzine 7.5%;
xxix. compound of Formula I 3% + Flufenoxuron 7.5%;
xxx. compound of Formula I 3% + Milbemectin 0.6%;
xxxi. compound of Formula I 1.5% + Propargite 30%;
xxxii. compound of Formula I 1.5% + Pyridaben 7.5%;
xxxiii. compound of Formula I 6% + Etoxazole 10% + Gibberellic acid 1%;
xxxiv. compound of Formula I 6% + Hexythiazox 5% + Gibberellic acid 1%;
xxxv. compound of Formula I 3% + Cyenopyrafen 10% + Gibberellic acid 0.5%;
xxxvi. compound of Formula I 3% + Spiromesifen 15% + Gibberellic acid 0.5%;
xxxvii. compound of Formula I 3% + Spirodiclofen 15% + Gibberellic acid 0.5%;
xxxviii. compound of Formula I 3% + Spirotetramat 15% + Gibberellic acid 0.5%;
xxxix. compound of Formula I 3% + Spiropidion 12% + Gibberellic acid 0.5%;
xl. compound of Formula I 3% + Spidoxamat 12% + Gibberellic acid 0.5%;
xli. compound of Formula I 2.4% + Diafenthiuron 25% + Gibberellic acid 0.4%;
xlii. compound of Formula I 2.4% +Bifenazate 16% + Gibberellic acid 0.4%;
xliii. compound of Formula I 2.4% + Bifenthrin 8% + Gibberellic acid 0.4%;
xliv. compound of Formula I 6% + Lambda cyhalothrin 8% + Gibberellic acid 1%;
xlv. compound of Formula I 3% + Chlorantraniliprole 4% + Gibberellic acid 0.4%;
xlvi. compound of Formula I 3% + Cyantraniliprole 10% + Gibberellic acid 0.4%;
xlvii. compound of Formula I 3% + Tetraniliprole 8% + Gibberellic acid 0.4%;
xlviii. compound of Formula I 3% + Cyclaniliprole 8% + Gibberellic acid 0.4%;
xlix. compound of Formula I 6% + Broflanilide 3% + Gibberellic acid 0.8%;
l. compound of Formula I 6% + Fluxametamide 3% + Gibberellic acid 0.8%;
li. compound of Formula I 6% + Clothianidin8% + Gibberellic acid 0.8%;
lii. compound of Formula I 6 % + Thiamethoxam 8 % + Gibberellic acid 0.8 %;
liii. compound of Formula I 6% + Dinotefuran 8% + Gibberellic acid 0.8%;
liv. compound of Formula I 3% + Flonicamid 8% + Gibberellic acid 0.4%;
lv. compound of Formula I 2.4% + Etoxazole 4% + Paclobutrazol 8%;
lvi. compound of Formula I 2.4% + Hexythiazox 2% + Paclobutrazol 8%;
lvii. compound of Formula I 2.4% + Cyenopyrafen 8% + Paclobutrazol 8%;
lviii. compound of Formula I 2.4% + Spiromesifen 12% + Paclobutrazol 8%;
lix. compound of Formula I 2.4% + Spirodiclofen 12% + Paclobutrazol 8%;
lx. compound of Formula I 2.4% + Spirotetramat 12% + Paclobutrazol 8%;
lxi. compound of Formula I 2.4% + Spiropidion 9.6% + Paclobutrazol 8%;
lxii. compound of Formula I 2.4% + Spidoxamat 9.6% +Paclobutrazol 8%;
lxiii. compound of Formula I 1.2% + Diafenthiuron 12.5% + Paclobutrazol 4%;
lxiv. compound of Formula I 2.4% + Bifenazate 16% + Paclobutrazol 8%;
lxv. compound of Formula I 2.4% + Bifenthrin 8% + Paclobutrazol 8%;
lxvi. compound of Formula I 2.4% + Lambda cyhalothrin 3.2% + Paclobutrazol 8%;
lxvii. compound of Formula I 2.4% + Chlorantraniliprole 4% + Paclobutrazol 8%;
lxviii. compound of Formula I 2.4% + Cyantraniliprole 10% + Paclobutrazol 8%;
lxix. compound of Formula I 2.4% + Tetraniliprole 8% + Paclobutrazol 8%;
lxx. compound of Formula I 2.4% + Cyclaniliprole 8% + Paclobutrazol 8%;
lxxi. compound of Formula I 4.8% + Broflanilide 3%+ Paclobutrazol 16%;
lxxii. compound of Formula I 4.8% + Fluxametamide 3% + Paclobutrazol 16%;
lxxiii. compound of Formula I 2.4% + Clothianidin 4% + Paclobutrazol 8%;
lxxiv. compound of Formula I 2.4% + Thiamethoxam 4% + Paclobutrazol 8%;
lxxv. compound of Formula I 2.4% + Dinotefuran 4% + Paclobutrazol 8%;
lxxvi. compound of Formula I 2.4% + Flonicamid 8% + Paclobutrazol 8%;
lxxvii. compound of Formula I 2.4% + Etoxazole 4% + Fulvic acid 4%;
lxxviii. compound of Formula I 2.4% + Hexythiazox 2% + Fulvic acid 4%;
lxxix. compound of Formula I 2.4% + Cyenopyrafen 8% + Fulvic acid 4%;
lxxx. compound of Formula I 2.4% + Spiromesifen 12% + Fulvic acid 4%;
lxxxi. compound of Formula I 2.4% + Spirodiclofen 12% + Fulvic acid 4%;
lxxxii. compound of Formula I 2.4% + Spirotetramat 12% + Fulvic acid 4%;
lxxxiii. compound of Formula I 2.4% + Spiropidion 9.6% + Fulvic acid 4%;
lxxxiv. compound of Formula I 2.4% + Spidoxamat 9.6% + Fulvic acid 4%;
lxxxv. compound of Formula I 1.2% + Diafenthiuron 12.5% + Fulvic acid 2%;
lxxxvi. compound of Formula I 2.4% + Bifenazate 16% + Fulvic acid 4%;
lxxxvii. compound of Formula I 2.4% + Bifenthrin 8% + Fulvic acid 4%;
lxxxviii. compound of Formula I 2.4% + Lambda cyhalothrin 3.2% + Fulvic acid 4%;
lxxxix. compound of Formula I 2.4% + Chlorantraniliprole 4% + Fulvic acid 4%;
xc. compound of Formula I 2.4% + Cyantraniliprole 10% + Fulvic acid 4%;
xci. compound of Formula I 2.4% + Tetraniliprole 8% + Fulvic acid 4%;
xcii. compound of Formula I 2.4% + Cyclaniliprole 8% + Fulvic acid 4%;
xciii. compound of Formula I 4.8% + Broflanilide 3% + Fulvic acid 8%;
xciv. compound of Formula I 4.8% + Fluxametamide 3% + Fulvic acid 8%;
xcv. compound of Formula I 2.4% + Clothianidin 4% + Fulvic acid 4%;
xcvi. compound of Formula I 2.4% + Thiamethoxam 4% + Fulvic acid4%;
xcvii. compound of Formula I 2.4% + Dinotefuran 4% + Fulvic acid 4%;
xcviii. compound of Formula I 2% + Abamectin 1.2% + Cyantraniliprole 8%;
xcix. compound of Formula I 2% + Abamectin 1.2% + Broflanilide 1.2%;
c. compound of Formula I 2% + Abamectin 1.2% + Fluxametamide 1.2%;
ci. compound of Formula I 2% + Hexythiazox 3% + Cyantraniliprole 8%;
cii. compound of Formula I 2% + Hexythiazox 3% + Broflanilide 1.2%;
ciii. compound of Formula I 2% + Hexythiazox 3% + Fluxametamide 1.2%;
civ. compound of Formula I 2% + Etoxazole 4% + Cyantraniliprole 8%;
cv. compound of Formula I 2% + Etoxazole 4% + Broflanilide 1.2%;
cvi. compound of Formula I 2% + Etoxazole 4% + Fluxametamide 1.2%;
cvii. compound of Formula I 2% + Hexythiazox 4% + Abamectin 1.2%;
cviii. compound of Formula I 2% + Hexythiazox 4% + Abamectin 1.2%;
cix. compound of Formula I 2% +Hexythiazox 4% + Abamectin 1.2%.
cx. compound of Formula I 1.2% +Tolfenpyrad 7.5% + Cyantraniliprole 4%.

7. The synergistic non aqueous agrochemical composition as claimed in claim 1-claim 5, wherein preferred combinations of active ingredients in the agrochemical composition comprises:
i. compound of Formula I 6% + Etoxazole 10%;
ii. compound of Formula I 3% + Cyantraniliprole 8%;
iii. compound of Formula I 4% + Hexythiazox 4%.
iv. compound of Formula I 1.2% +Tolfenpyrad 7.5% + Cyantraniliprole 4%.

8. The synergistic non aqueous agrochemical composition as claimed in claim 1, wherein oil phase as a carrier/solvent is selected from pongamia oil; or palm oil; or pongamia oil and palm oil; or pongamia oil and jojoba oil; or palm oil and jojoba oil; or pongamia oil and vegetable oil; or paml oil and vegetable oil; or pongamia oil and palm oil and vegetable oil; and it may be alkylated or ethoxylated or epoxylated or esterified.

9. The synergistic non aqueous agrochemical composition as claimed in claim 1, wherein vegetable oil may be selected from one or mixture of two or more selected from soybean soybean (Glycine max) oil, groundnut (Arachis hypogaea) oil, rapeseed (Brassica napus subspecies) oil, mustard (Brassica juncea) oil, sesame (Sesamum indicum) oil, Corn (Zea mays) oil, rice (Oryza sativa) bran oil, castor (Ricinum communis) seed oil, cotton (Gossypium hirsutum) seed oil, linseed (Linum usitatissimum), coconut (Cocos nucifera) oil, Kapok (Ceiba pentandra) oil, Papaya (Carica papaya) seed oil, Tea seed (Camellia oleifera) oil, sunflower (Helianthus annuus) oil, safflower (Carthamus tinctorius) seed oil, Eucalyptus (Eucalyptus globulus) oil, Olive (Olea europaea) oil, Jatropha (Jatropha curcas) oil, Garlic acid (Allium sativum), Ginger oil (Zingiber officinale), D-limonene, Citronella oil or Ceylon ironwood (Mesua ferrea) oil, Mahua (Madhuca longifolia) oil.

10. The synergistic non aqueous agrochemical composition as claimed in claim 1, wherein formulation excipients are selected from category of emulsifying agent is present in amount of 5% - 10% w/w; dispersing agent is present in amount of 1 % - 10% w/w; stabilizer is present in amount of 1% - 5 % w/w; antifoaming agent is present in amount of 0.1% - 2 % w/w; preservative is present in amount of 0.1% - 1 % w/w; anti-freezing agent is present in amount of 1% - 10 % w/w and optionally a co-solvent.

11. The synergistic non aqueous agrochemical composition as claimed in claim 10, wherein an emulsifying agent is selected from castor oil ethoxylates, alcohol ethoxylates, fatty acid ethoxylates, sorbitan ester ethoxylates, sulphosuccinate, calcium salts of dodecylbenzene sulphonate, alkylammonium salts of alkylbenzene sulphonate, alkylsulphosuccinate salts, ethylene oxide-propylene oxide block copolymers, ethoxylated alkylamines, ethoxylated alkyl phenols, polyoxyethylene sorbitan monolaurate.

12. The synergistic non aqueous agrochemical composition as claimed in claim 10, wherein dispersing agent is selected from condensed naphthalene sulfonate, Propoxylated Ethoxylated copolymer monoalkylether (ethylhexanol), alkyl sulfonates, alkyl benzene sulfonates, alkyl aryl sulfonates, alkylphenolalkoxylates, tristyrylphenol ethoxylates, natural or synthetic fatty ethoxylate alcohols, natural or synthetic fatty acid alkoxylates, natural or synthetic fatty alcohols alkoxylates, alkoxylated alcohols (such as n-butyl alcohol poly glycol ether), block copolymers (such as ethylene oxide-propylene oxide block copolymers and ethylene oxide-butylene oxide block copolymers), fatty acid-polyalkylene glycol condensates, polyamine-fatty acid condensates, polyester condensates, salts of polyolefin condensates, sodium ligno sulfonate, sodium ploycarboxylate, EO/PO based copolymer, phenol sulfonate, sodium methyl oleoyl taurate, acrylic copolymer blend, styrene acrylic acid copolymer, propyleneoxide-ethyleneoxide-copolymer, polyethylene glycol 2,4,6-tristyrylphenyl ether, tristyrylphenol-polyglycolether-phosphate, tristyrylphenole with 16 moles EO, tristyrylphenol-polyglycolether-phosphate, oleyl-polyglycolether with ethylene oxide, tallow fattyamine polyethylene oxide, nonylphenol polyglycolether with 9-10 moles ethylene oxide.

13. The synergistic non aqueous agrochemical composition as claimed in claim 10, wherein stabilizer is selected from bentonite clay, aluminium magnesium silicate, bentonite clay, silica, silicon dioxide, attapulgite clay.

14. The synergistic non aqueous agrochemical composition as claimed in claim 10, wherein antifoaming agent is selected from silicone oil, silicone compound, C10~C20 saturated fat acid compounds or C8~C10 aliphatic alcohols compound, silicone antifoam emulsion, dimethyl siloxane, poly dimethyl siloxane.

15. The synergistic non aqueous agrochemical composition as claimed in claim 10, wherein anti-freezing agent is selected from ethylene glycol, propane diols, glycerine or the urea, glycol (Monoethylene glycol, Diethylene glycol, Propylene glycol, Polypropylene glycol, Polyethylene glycol), glycerine, urea, magnesium sulfate heptahydrate, sodium chloride.

16. The synergistic non aqueous agrochemical composition as claimed in claim 10, wherein Preservative is selected from 1,2-benzisothiazolin-3(2H)-one, sodium salt, sodium benzoate, 2-bromo-2-nitropropane-1,3-diol, formaldehyde, sodium o phenylphenate, 5-chloro-2-methyl-4-isothiazolin-3-one & 2-methyl-4 isothiazolin-3-one, Butyl hydroxyl toluene.

17. The synergistic non aqueous agrochemical composition as claimed in claim 10, wherein buffering agent is selected Citric acid, sodium carbonate, sodium bicarbonate, sulphuric acid, hydrochloric acid, sodium hydroxide, potassium hydroxide, acetic acid, sorbic acid.

18. The synergistic non aqueous agrochemical composition as claimed in claim 10, wherein polar co-solvent present optionally is selected from Cyclohexanone, Acetophenone, NMP (N-methyl pyrrolidinone), Dimethyl sulfoxide, Benzyl alcohol, Butanol, N-octanol, N-Propanol, 2-ethyl hexanol, Tetrahydro furfuryl alcohol, Isophorone, Fatty acid dimethyl amide, 2- hexylethyl lactate, Propylene carbonate present in an amount of 2%-15% w/w.

Dated this 23rd day of December 2021
, Description:FIELD OF INVENTION:
The present invention relates to a synergistic agrochemical composition. More particularly the present invention relates to a synergistic non aqueous agrochemical composition comprising bioactive amount of component (A) an acaricide insecticide compound tert-butyl 4-[[(E)-(1,3-dimethyl-5-phenoxypyrazol-4-yl)methylideneamino] oxymethyl]benzoate of Formula I; and component (B) atleast one more of active ingredients selected from class of an insecticide; or a fungicides; or a plant health additive; or combination thereof. The present invention further relates to selection of suitable formulation excipients, process of preparation of the said non aqueous formulation and its application in the field of agriculture.

BACKGROUND OF THE INVENTION:
These days cultivation of crops and agriculture in general is cost intensive. Receiving a high yield from the cultivated crops is a key. Hence, to achieve higher yield, protecting crops from pests and diseases is vital. Hence, the most effective way to control crop pests and diseases is the application of pesticides in accordance with the appropriate management practices with proper formulation thereof.
Treating plants with such a pesticides and plant health additives or combination thereof in appropriate formulation helps to reduce the crops/plants damage. Another advantage of treating the plants with the said combination is the improvement in plant growth overall plant health and increase in the crop yield.
Various kinds of agrochemical formulations are developed based upon active ingredients and scope of application thereof. Pesticides for agriculture purpose are available both in the pure form and as well as incorporated into agrochemical formulations, which typically comprise one or more active ingredients (AIs) and additional excipients substances that enhance the effects and facilitate the application thereof, such as carriers, adjuvants or additives. These formulations can be directly applied onto the crops or, more commonly, are applied after being diluted and the spray mixture formed. The formulation type to be used is primarily defined on the basis of physicochemical characteristics of the AI(s) and can be: soluble concentrate (SL), emulsifiable concentrate (EC), emulsion in water (EW), suspension concentrate (SC), suspo-emulsion (SE), micro-emulsion (ME), oil dispersion (OD) or suspension concentrate (SC), dispersible concentrate (DC), capsule suspension (CS), dispersible granules (WG), wettable powder (WP) and others.
The various types of agrochemical formulations are the result of the existence of a large variety of AIs of different chemical natures. For example, a water soluble AI can be easily included into a water based SL while a high melting, water insoluble AI is commonly found in the form of a EC (Emulsifiable concentrate). For this reason, agrochemical formulations are distinct and can contain different inert components.
In recent years, non aqueous [OD (Oil Dispersion)] formulations have been the subject of studies by companies and formulators because of their advantages with respect to the agronomic performance in the field as compared with conventional formulations. Active ingredients (AIs) formulated in different types of formulations usually exhibit different physicochemical characteristics based on type of formulation they are incorporated in. The different performance between them is due to the fact that ODs already contain in their composition oil, such as a mineral or vegetable oil, and emulsifiers, which can act as penetration adjuvants when applied in the field. Penetration adjuvants aid in the absorption of AIs by the plant and, in the case of some conventional formulations, they are used in association with the formulation in the spray mixture, ensuring agronomical effectiveness of the AI. Thus, OD formulations can be deemed “adjuvanted” formulations and do not require additional associated adjuvants to be applied in the field.
Though OD formulation is called as adjuvated formulation it still requires various adjuvants along with formulation excipients. OD formulation presents several challenges in the process of manufacturing and developing stable and effective formulation with choice of proper formulation excipient or adjuvants. To obtain a good and stable formulation over time, optimal formulation additives are required in addition to optimum processes. There were several development and research done in the filed field of formulation development of Oil Dispersion (OD) formulation. Dispersion and activation of active ingredients is the key to the stability of the formulation over time. Solvents or carrier used as a petroleum based or the aromatic solvent we replaced by the solvents in the form of vegetable oils. Vegetable oils application as a formulation excipients in OD formulation further have their own challenges for stable formulation due to stability issue associated with vegetable oil used and corresponding active ingredient. Although various research has been done in formulation development it has got many draw backs as having high dose of active ingredients and thereby maximizing the pesticidal load into the environment. Many OD formulations has less thermal and chemical stability over a broad range of conditions; increases the toxicity hazards to the applicators and thereby decreasing the safety of applicators at the time of handling and spraying the pesticides. Further some OD formulation with less suitable formulation excipients may lead to have less leaf penetration of spray droplets, and increases evaporation loss and minimize the absorption of active ingredients.
Therefore there is further need and scope in the formulation development of the OD formulation comprising one or more active ingredients with better stability profile and increases the synergistic effect of the active ingredients, reduces the toxicity with less introduction of toxic material in environment, which may reduce the dose of the pesticides and eventually produce less chemicals in environment, with better safety profile for contact pesticides.
CN106982852A relates to a pesticide composition of fenpyroximate and lufenuron, said composition is made up of active ingredient fenpyroximate and lufenuron, and its active ingredient mass percent is 5~80%;The weight ratio of fenpyroximate and lufenuron is 40:1 to 1:10;The composition pesticide is used to prevent and treat On aphid in fruit and vegetables and the downy mildew in the application and vegetables of rice hoppers, gray mold, anthracnose and fruit tree The disease such as shot hole, anthracnose, scab application.
CN109744244A relates to a miticide composition of a kind of fluazinam and fenpyroximate, effective component is fluazinam and fenpyroximate, and the weight ratio of effective component fluazinam and fenpyroximate is 80:1 ~ 1:80, and both fluazinam and fenpyroximate mass percentage are 1% ~ 90%. Miticide composition of the invention can be used for preventing and treating harmful mite class such as fruit tree, vegetables, the Tetranychus urticae on field crop, yellow tea mite, Tetranychus cinnabarinus, it is used in combination by the two, not only there is good preventive effect to multiple resistance acarid.
CN105309441B relates to a pesticides composition containing nitrile pyrrole mite ester and its purposes in prevention and treatment harmful mite, effective component to be made of the first active constituent nitrile pyrrole mite ester, the second active constituent fenpyroximate; Wherein, it is calculated according to weight ratio, the ratio of the first active constituent and the second active constituent is 40:1 to 1:40, and the sum of content is the 2% to 40% of the composition total weight.This composition can be configured to the aqueous emulsion agriculturally allowed, suspending agent, water dispersible granules, microcapsule suspending agent.Instant component is reasonable, it is good to panonychus ulmi, tetranychus vinenensis zacher, Tetranychus urticae, Tetranychus cinnabarinus, yellow tea mite effect.
There is however a need for improvement of these combinations. Single active combination used over a long period of time has resulted in resistance. With the onset of resistance to certain pests, there is a need in the art for a combination of actives that decrease the chances of resistance and improves the spectrum of insect-pests and diseases control.
In general use, the pesticide actives are used in the form of a dilute aqueous composition because it can attain a good interaction with the target organism, such as plants, insect-pests and diseases. However, most active pesticide compounds that are used as pesticides are only sparingly or insoluble in water. The low solubility of such compounds present the challenges and difficulties to formulator in formulating pesticide compounds in stable formulations that can be easily stored for a long time and which can still have a high stability and effective activity until end use. This problem especially occurs and may get worsen if more than one active compound is present in the mixture.
Therefore there is further need to formulate the novel non aqueous (OD) formulation which increases the synergistic activities between active ingredients by using the appropriate formulation excipients; enhance the duration of control of insect-pests, fungal and bacterial diseases; reduce the doses of active ingredients and thereby minimizing the pesticidal load into the environment; has thermal and chemical stability over a broad range of weather conditions; reduces the toxicity hazards to the applicators, i.e. improves the safety of applicators at the time of handling and spraying the pesticides; and improves leaf penetration of spray droplets, retard evaporation loss and enhance the absorption of active ingredients.
There is however a need for improvement of non aqueous formulations. Many a times it has been found that single or combination of active ingredients requires a high loading dose for the better results. Further this will create a higher loading of the pesticides in the environment. Further many of the non aqueous formulation recipe is prone to lose stability when exposed to the higher temperature. In addition there are higher chances of formulation applied gets evaporated resulting in the loss of the active ingredients before penetration.
Therefore, one object of the present invention is to provide improved combinations of (A) an acaricide insecticide compound tert-butyl 4-[[(E)-(1,3-dimethyl-5-phenoxypyrazol-4-yl)methylideneamino] oxymethyl]benzoate of Formula I; and (B) atleast one more of active ingredients selected from class of insecticides or fungicides or plant health additive or combination thereof for the control of insect-pest. Another object of the present invention is to provide a method and a composition for controlling insect pests and diseases (fungal diseases and bacterial diseases) on a full grown plant.
Yet another object of the present invention is to provide improved combinations of (A) an acaricide insecticide compound tert-butyl 4-[[(E)-(1,3-dimethyl-5-phenoxypyrazol-4-yl)methylideneamino] oxymethyl]benzoate of Formula I; and (B) atleast one more of active ingredients selected from class of insecticides; or fungicides; or plant health additive; or combination thereof that promote plant health and increase plant yield in the field.
Further object of the present invention is to provide suitable formulation excipients for the present non aqueous (Oil Dispersion) formulation in order to produce stable and synergistic formulation.
Another object of the present invention is to provide a method and a composition for the non aqueous formulation.
Embodiment of the present invention can ameliorate one or more of the above mentioned problems.
Inventors of the present invention have surprisingly found that the novel synergistic mixture of non aqueous formulation for plant treatment comprising of (A) an acaricide insecticide compound tert-butyl 4-[[(E)-(1,3-dimethyl-5-phenoxypyrazol-4-yl)methylideneamino] oxymethyl]benzoate of Formula I; and (B) any one of active ingredients selected from class of insecticides or fungicides or plant health additive or combination thereof can provide solution to the above mentioned problems.

SUMMARY OF INVENTION
Therefore an aspect of the present invention provides a synergistic agrochemical non aqueous composition comprising bioactive amount of (A) an acaricide insecticide compound tert-butyl 4-[[(E)-(1,3-dimethyl-5-phenoxypyrazol-4-yl)methylideneamino] oxymethyl]benzoate of Formula I (hereafter compound of Formula I); and (B) atleast one more of active ingredients selected from class of insecticides or fungicides or plant health additive or combination thereof; along with formulation excipients.
More particularly the aspect of the present invention is to provide the a synergistic agrochemical non aqueous composition comprising possible combinations of Compound of Formula I +Insecticide; or Compound of Formula I + InsecticideA + InsecticideB; or Compound of Formula I + Fungicide; or Compound of Formula I + FungicideA + FungicideB; or Compound of Formula I + Plant Health Additive; or Compound of Formula I + Insecticide+Plant Health Additive; or Compound of Formula I + Fungicide+Plant Health Additive; or Compound of Formula I + Insecticide+ Fungicide.
Further aspect of the present invention is to provide novel agrochemical non aqueous formulation comprising at least one active ingredient suspended in oil phase shows synergistic activity and stability over wide range of the conditions.
Further aspect of the present synergistic non aqueous composition is to provide selection of suitable formulation excipients selected from category of super wetting-spreading-penetrating agent, carrier or solvent, emulsifying agent, dispersing agent, stabilizers, antifoaming agent, preservative, anti-freezing agent and buffering agents.
Another aspect of the present invention is to provide synergistic agrochemical non aqueous formulation comprising Super Wetting-spreading-penetrating agent- Polyalkyleneoxide modified Heptamethyl trisiloxane (Modified trisiloxane).
Further aspect of the present invention is to provide synergistic agrochemical non aqueous formulation comprising carrier or solvent selected from Pongamia/karanja/karanj oil; or palm oil; or pongamia oil and palm oil; or pongamia oil and jojoba oil; or palm oil and jojoba oil; or pongamia oil and vegetable oil; or palm oil and vegetable oil; or pongamia oil and palm oil and vegetable oil; or solvent; or both.
In a further embodiment of the present invention, an insecticide may be selected from Carbamates; Organophosphates; Phenylpyrazole; Pyrethroids; Nicotinic insecticides; Spinosyns; Mectins; Juvenile hormone mimics; Chordotonal organs modulators; Mite growth inhibitors; Microbial disruptors of insect midgut membrane; Inhibitors of mitochondrial ATP synthase; Uncouplers of oxidative phosphorylation; Nereis toxin; Chitin biosynthesis inhibitors; Inhibitors of the chitin biosynthesis type 1; Moulting disruptors; Ecdyson receptor agonists; Octopamin receptor agonists; METI (mitochondrial electron transport inhibitors; Voltage-dependent sodium channel blockers; Inhibitors of the lipid synthesis, inhibitors of acetyl CoA carboxylase; Diamides; Metadiamides; Isoxazolines; Baculoviruses; compounds of unknown or uncertain mode of action.
In a further embodiment of the present invention, a fungicide may be selected from Nucleic acid synthesis inhibitors; Cytoskeleton and motor proteins/cell division Inhibitors; Respiration inhibitors; Amino acids and protein synthesis inhibitors; Signal transduction inhibitors; Lipid or transport and membrane synthesis inhibitors; Sterol biosynthesis Inhibitors; Cell wall biosynthesis Inhibitors; Melanin synthesis in cell wall Inhibitors; Plant defence inducers; Unknow mode of action; Not classified (N); Chemicals with multisite activities (M)-multisite contact activities; Biologicals with multiple modes of action (BM); others.
In a further embodiment of the present invention, plant health additives are selected from bio-stimulants, plant growth regulators, microbial agents and micronutrients or mixture thereof.
The present synergistic agrochemical non aqueous [Oil Dispersion (OD)] composition comprising bioactive amount of (A) an insecticide compound of Formula I; and (B) atleast one more of active ingredients selected from class of insecticides or fungicides or plant health additive or combination thereof described herein is obtained by a process comprising a step of preparing the liquid premix by charging the oil or solvent or both followed by adding super wetting-spreading-penetrating agent. The further step is adding the active ingredients and homogenize thoroughly into the premixed through milling for the proper size distribution. Further adding the thickening agent followed by stirring the slurry get prepared by milling process to prepare the final formulation. These agrochemical non aqueous formulations can be used in spray mixtures in agriculture.

BRIEF DESCRIPTION OF THE DRAWINGS:
The objects, features and advantages of the invention will best be understood from the following description of various embodiments thereof, selected for purposes of illustration, and shown in the accompanying figures.
Figure 1. Discloses field performance of different recipes of treatment (T1 to T4) of novel non aqueous (OD) formulation on chilly crops over conventional recipes as descrived in details in Experiment 2 of field bioefficacy study.

DETAIL DESCRIPTION OF THE INVENTION:
Formulation technology in the field of an agriculture is now seen as an “enabling technology” which can provide safe and effective products which are convenient to use. It can also modify the toxicity of active ingredients and improve their ability to target a specific pest. At a time when the discovery of new agrochemical compounds is more difficult and certainly a high risk and expensive operation, formulation technology can extent the useful patent life of an active ingredient. It can also provide a competitive edge by improving product quality of existing formulations, or by introducing a new formulation of an active ingredient.
OD formulations are non-aqueous dispersion intended for dilution into water before use, and represent the most complex of the non-aqueous suspension formulations. Oil dispersion (OD) formulations consist of a suspension of a solid technical in oil. The oil also serve as a carrier or solvent for additives. The oil dispersion is usually dispersed in water prior to spraying.
An Oil Dispersion is a non-aqueous suspension concentrate. It combines a very good biological efficacy with an environmental friendly formulation. The active ingredient is dispersed in oils or methylated crop oils.
Oil Dispersion formulation comprises with some features as it comprises no aromatic solvent or reduced amount of aromatic solvent; is non-aqueous formulation; non-flammable and low volatility; higher efficiency.
Oil Dispersion (OD) have several advantages over standard formulations. Emulsifiable Concentrate (ECs) formulations are under a strong regulatory pressure to replace toxic and flammable solvents with a less toxic and non-flammable solutions. The novel ODs meets these needs: the oil content gives a favourable eco-toxicological profile guarantying a very high biological efficacy. Further the novel OD formulations are non-toxic and non-flammable formulations. Over the EC formulation the novel OD formulation is having very high biological efficacy.
Suspension concentrate (SC) formulations are very safe formulations but the aqueous media is normally not ideal to boost the pesticide’s biological efficacy. As an agriculture growers standard practice, tank mix adjuvants are added to guarantee a higher performance. The novel OD, with its oil content, guarantees the best biological results. For water sensitive active ingredients, the novel OD represents the sole technical solution to liquid formulation. The novel OD formulation over SC formulation is very safe formulation along with high biological performance. Further the novel OD formulation is ideal for all the active ingredients not stable in water.
Water dispersible granules (WDG) formulations are very safe but quite expensive. Optimal biological efficacy requires adjuvants. The novel OD, with its oil content and better particle size distribution, combines high efficacy with better cost. The novel OD formulation over WDG has economic significance as having better efficacy at a lower cost.
OD formulation presents several challenges in preparation and manufacturing phase. To obtain a good and stable formulation over time, optimal formulation additives are required in addition to optimum processes. Particular attention must be given to choice of all the formulation excipients. Its dispersion and activation are key to the stability of the formulation over time.
Some important requirement of the formulation excipients are perfectly dispersible in oil, no phase separation, easy milling, with no agglomeration, excellent oil emulsification, stable dilution, good coverage and penetration, even distribution through the whole formulation, provide the right yield value of active ingredients.
Therefore an aspect of the present invention provides a synergistic agrochemical non aqueous [Oil Dispersion (OD)] composition comprising bioactive amount of (A) an acaricide insecticide compound tert-butyl 4-[[(E)-(1,3-dimethyl-5-phenoxypyrazol-4-yl)methylideneamino] oxymethyl]benzoate of Formula I (Fenpyroximate); and (B) atleast one more of active ingredients selected from class of insecticides or fungicides or plant health additive or combination thereof.
Further aspect of the present invention is to provide novel agrochemical non aqueous formulation comprising at least one active ingredient suspended in oil phase shows synergistic activity and stability over wide range of the conditions.
In an especially preferred embodiment of the invention, the yield of the treated plant is increased.
In another preferred embodiment of the invention, the yield of the plants treated according to the method of the invention, is increased synergistically.
The term "synergistic", as used herein, refers the combined action of two or more active
agents blended together and administered conjointly that is greater than the sum of their individual effects.
Another aspect of the present invention is to provide the a synergistic agrochemical non aqueous composition comprising possible combinations of compound of Formula I +Insecticide; or Compound of Formula I + InsecticideA + InsecticideB; or Compound of Formula I + Fungicide; or Compound of Formula I + FungicideA + FungicideB; or Compound of Formula I + Plant Health Additive; or Compound of Formula I + Insecticide+Plant Health Additive; or Compound of Formula I + Fungicide+Plant Health Additive; or Compound of Formula I + Insecticide+ Fungicide.
Further aspect of the present invention is to provide synergistic agrochemical non aqueous formulation comprising formulation excipients from the category of Super Wetting-spreading-penetrating agent, Solvent, emulsifying agent, dispersing agent, stabilizers, antifoaming agent, preservative, anti-freezing agent and buffering agents.
In an embodiment of the present synergistic agrochemical non aqueous formulation, atleast one more of active ingredient component (B) is selected from compound from group of insecticide, or fungicide, or plant health additives or combination thereof.
In an embodiment of the present invention, an insecticide may be selected from Carbamates; Organophosphates; Phenylpyrazole; Pyrethroids; Nicotinic insecticides; Spinosyns; Mectins; Juvenile hormone mimics; Chordotonal organs modulators; Mite growth inhibitors; Microbial disruptors of insect midgut membrane; Inhibitors of mitochondrial ATP synthase; Uncouplers of oxidative phosphorylation; Nereis toxin; Chitin biosynthesis inhibitors; Inhibitors of the chitin biosynthesis type 1; Moulting disruptors; Ecdyson receptor agonists; Octopamin receptor agonists; METI (mitochondrial electron transport inhibitors; Voltage-dependent sodium channel blockers; Inhibitors of the lipid synthesis, inhibitors of acetyl CoA carboxylase; Diamides; Metadiamides; Isoxazolines; Baculoviruses; compounds of unknown or uncertain mode of action.
In a further embodiment of the present invention, an insecticide may be selected from: Carbamates:-carbaryl, carbofuran, carbosulfan, methomyl, oxamyl, pirimicarb, thiodicarb; Organophosphates:-acephate, cadusafos, chlorpyrifos, chlorpyrifos-methyl, demeton-S-methyl, dimethoate, ethion, fenamiphos, fenitrothion, fenthion, fosthiazate, methamidophos, monocrotophos, oxydemeton-methyl, parathion, parathion-methyl, phenthoate, phorate, phosalone, phosphamidon, profenofos, quinalphos, triazophos; Phenylpyrazole:-ethiprole, fipronil, flufiprole, nicofluprole, pyrafluprole, or pyriprole; Pyrethroids:-bifenthrin, cyfluthrin, beta-cyfluthrin, cyhalothrin, lambda-cyhalothrin, gamma-cyhalothrin, cypermethrin, alpha-cypermethrin, beta-cypermethrin, theta-cypermethrin, zeta-cypermethrin, cyphenothrin, deltamethrin, fenpropathrin, fenvalerate, tau-fluvalinate, permethrin, phenothrin, prallethrin, profluthrin, pyrethrin (py rethrum);
Nicotinic insecticides:- neonicotinoids: acetamiprid, clothianidin, dinotefuran, imidacloprid, nitenpyram, thiacloprid, thiamethoxam, flupyrimin, cycloxaprid, paichongding, guadipyr, cycloxylidin; sulfoximines-sulfoxaflor; butenolides- flupyradifurone; mesoionics- triflumezopyrim, dichloromezotiaz, fenmezoditiaz; spinosyns:- spinosad, spinetoram;
Mectins:-abamectin, emamectin benzoate, ivermectin, lepimectin, milbemectin; Juvenile hormone mimics:- hydroprene, kinoprene, methoprene, fenoxycarb, pyriproxyfen; Chordotonal organs modulators-pymetrozine, pyrifluquinazon, afidopyropen, flonicamid; Mite growth inhibitors:- clofentezine, hexythiazox, diflovidazin or etoxazole; Microbial disruptors of insect midgut membrane:-Bacillus thuringiensis and insecticidal proteins; Inhibitors of mitochondrial ATP synthase:- diafenthiuron, azocyclotin, cyhexatin, fenbutatin oxide, propargite, or tetradifon;
Uncouplers of oxidative phosphorylation:- chlorfenapyr, DNOC, or sulfluramid; Nereis toxin:-bensultap, monosultap, cartap hydrochloride, thiocyclam, thiocyclam hydrogen oxalate, thiocyclam hydrochloride, thiosultap sodium; Chitin biosynthesis inhibitors: - benzoylureas-bistrifluron, chlorfluazuron, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, noviflumuron, teflubenzuron, triflumuron; Inhibitors of the chitin biosynthesis type 1:- buprofezin; Moulting disruptors:- cyromazine; Ecdyson receptor agonists:- diacylhydrazines- methoxyfenozide, tebufenozide, halofenozide, fufenozide or chromafenozide; Octopamin receptor agonists:- amitraz; METI (mitochondrial electron transport inhibitors: - fenazaquin, pyrimidifen, pyridaben, tebufenpyrad, tolfenpyrad, flufenerim, rotenone, cyenopyrafen, cyflumetofen, pyflubumidemm, hydramethylnon, acequinocyl, flometoquin, fluacrypyrim, pyriminostrobin or bifenazate; Voltage-dependent sodium channel blockers: - oxadiazines-indoxacarb, semicarbazones-metaflumizone; Inhibitors of the lipid synthesis, inhibitors of acetyl CoA carboxylase:- Tetronic and tetramic acid derivatives-spirodiclofen, spiromesifen, spirotetramat, spidoxamat or spiropidion; Diamides:-chlorantraniliprole, cyantraniliprole, cyclaniliprole, cyhalodiamide, cyproflanilide, flubendiamide, tetraniliprole, tetrachlorantraniliprole, tyclopyrazoflor; Metadiamides- broflanilide; Isoxazolines- fluxametamide, isocycloseram; Baculoviruses:- granuloviruses and nucleopolyhedrosis viruses; Compounds of unknown or uncertain mode of action: - azadirechtin, benzpyrimoxan, pyridalyl, oxazosulfyl, dimpropyridaz, flometoquin, fluhexafon, cyetpyrafen, flupentiofenox, acyonapyr, cyclobutrifluram, fluazaindolizine, tioxazafen.

In a further embodiment of the present invention, a fungicide may be selected from Nucleic acid synthesis inhibitors; Cytoskeleton and motor proteins/cell division Inhibitors; Respiration inhibitors; Amino acids and protein synthesis inhibitors; Signal transduction inhibitors; Lipid or transport and membrane synthesis inhibitors; Sterol biosynthesis Inhibitors; Cell wall biosynthesis Inhibitors; Melanin synthesis in cell wall Inhibitors; Plant defence inducers; Unknow mode of action; Not classified (N); Chemicals with multisite activities (M)-multisite contact activities; Biologicals with multiple modes of action (BM); others.

In a further embodiment of the present invention, a fungicide may be selected from:
a) Nucleic acid synthesis inhibitors:-
benalaxyl, benalaxyl-M (=kiralaxyl), furalaxyl, metalasxyl, metalaxyl-M (=mefenoxam)), butyrolactones(ofurace), bupirimate, dimethirimol, ethirimol, octhilinone, hymexazole, oxolinic acid; fluorocytosine, 5- fluoro-2-(p-tolylmethoxy)pyrimidin-4-amine, 5-fluoro-2-(4-fluorophenylmethoxy)pyrimidin-4-amine;
b) Cytoskeleton and motor proteins/cell division Inhibitors:-
benomyl, carbendazim, fuberidazole, thiabendazole, thiophanate, thiophanate-methyl, diethofencarb; zoxamide, ethaboxam, pencycuron, fluopicolide, flufenoxadiazam, fluopimomide, phenamacril, metrafenone, pyriofenone;
c) Respiration inhibitors:-
benodanil, flutolanil, mepronil, isofetamid, fluopyram, fenfuram, carboxin, oxycarboxin, thifluzamide, benzovindiflupyr, bixafen, fluindapyr, fluxapyroxad, furametpyr, isopyrazam, penflufen, penthiopyrad, sedaxane, flubeneteram, pyrapropoyne, inpyrfluxam, isoflucypram, pydiflumetofen, boscalid, pyraziflumid;
pyribencarb, fluoxastrobin, fenamidone, mandestrobin, azoxystrobin, coumoxystrobin, enoxastrobin, flufenoxystrobin, picoxystrobin, pyraoxystrobin; methoxy carbamates-pyraclostrobin, pyrametostrobin, triclopyricarb; oxazolidine diones-famoxadone; oximino acetamides-dimoxystrobin, fenamistrobin, metominostrobin, orysastrobin, kresoxim methyl, Trifloxystrobin, cyazofamid, amisulbrom, fenpicoxamid, florylpicoxamid, metarylpicoxamid, metyltetraprole, binapacryl, meptyldinocap, dinocap, 2,6-dinitro anilines (C5)-fluazinam, fentin acetate, fentin chloride, fentin hydroxide, silthiofam, ametoctradin;
d) Amino acids and protein synthesis inhibitors- cyprodinil, mepanipyrim, pyrimethanil, blasticidin-S, kasugamycin, streptomycin, oxytetracycline;
e) Signal transduction inhibitors:- aryloxyquinoline (E1)- quinoxyfen, proquinazid, fenpiclonil, fludioxonil, chlozolinate, dimethachlone, iprodione, procymidone, vinclozolin;
f) Lipid or transport and membrane synthesis inhibitors:- isoprothiolane, edifenphos, iprobenfos (IBP), pyrazophos, biphenyl, chloroneb, dicloran, quintozene, tecnazene, tolcofos methyl, etridiazole, iodocarb, propamocarb, prothiocarb, extract from Melaleuca arternifolia (tea tree), plant oils (mixtures); eugenol, geraniol, thymol, natamycin (pimaricin), oxathiapipronil, fluoxapipronil, fluoxapiprolin-s;
g) Sterol biosynthesis Inhibitors:- imazalil, oxpoconazole, pefurazoate, procloraz, triflumizole, triforine, pyrifenox, pyrisoxazole, fenarimo, naurimol, azaconazole, bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole, epoxiconazole, etaconazole, fenbuconazole, fluquinconazole, flusilazole, frutriafol, hexaconazole, imibenconazole, ipconazole, mefentrifluconazole, metconazole, myclobutanil, penconazole, propiconazole, prothioconazole, simconazole, tebuconazole, tetraconazole, tiradimefon, tiradimenol, triticonazole, fluoxytioconazole, aldimoprh, dedomorph, tridemorph, fenpropimorph, fenpropidin, piperalin, spiroxamine, fenpyrazamine, fenhexamid, naftifine, terbinafine, pyributicarb;
h) Cell wall biosynthesis Inhibitors:- polyoxin, dimethomorph, flumorph, pyrimorph, mandipropamid, benthiavalicard, iprovalicarb, valifenalate;
i) Melanin synthesis in cell wall Inhibitors:- fthalide, pyroquilon, tricyclazole, diclycymet, carpropamid, fenoxanil, tolprocarb;
j) Plant defence inducers:- acibenzolar-S-methyl, probenazole, tiadinil, isotianil, laminarin, extract from Reynoutria sachalinensis (giant knowweed), bacterial Bacillus (P6)-Bacillus mycoides isolate J, cell awall of Saccharomyces erevisiae strain LAS117, phosphonates(P7)-fosetyl-AL, phosphoric acid and salts;
k) Unknow mode of action:- cymoxanil, teclofthalam, triazoxide, fluslfamide, diclomezine, cyflufenamid, dodine, flutianil, ferimzone, flumetylsulforim, tebufloquin, picarbutrazox, validamycin;
l) Not classified (N)- mineral oils, inorganic oils, organic oils, potassium bicarbonates, materials of biological origin;
m) Chemicals with multisite activities (M)-multisite contact activities- copper (copper hydroxide, copper oxychloride, copper (II) sulphate, bordeaux mixture, copper salicylate, cuprous oxide, sulphur, ferbam, mancozeb, maneb, metiram, propineb, thiram, zinc thiazole, zineb, ziram, captan, captafol, folpet, chlorothalonil, dichlofluanid, tolylfluanid, guazatine, iminoctadine, anilazine, dithianon, chinomethionat / quinomethionate, fluoroimide, methasulfocarb;

n) Biologicals with multiple modes of action (BM)- polypeptide (lectin)-extract from the cotyledons of lupine plantlets (“BLAD”), Plant extract-Phenols, Sesquiterpenes, Triterpenoids, Coumarins, microbial (living microbes or extract metabilites-Trichoderma atroviride strain SC1, Trichoderma atroviride strain I-1237, Trichoderma atroviride strain LU132, Trichoderma asperellum strain T34, Gliocladium catenulatum strain J1446 , Clonostachys rosea strain CR-7 , Bacillus amyloliquefaciens strain QST713, strain FZB24, strain MBI600, strain D747, strain F727, Bacillus subtilis strain AFS032321, Pseudomonas chlororaphis strain AFS009, Streptomyces griseovirides strain K61, Streptomyces lydicus strain WYEC108, polyoxin D zinc salt;
o) Others: - Ipflufenoquin, pyridachlometyl, quinofumelin, dichlobentiazox, aminopyrifen, dipymetitrone, seboctylamine, chloroinconazide;

Plant health additives:
Plant health additives are products that reduce the need for fertilizers and increase plant growth, resistance to water and abiotic stresses. In small concentrations, these substances are efficient, favouring the good performance of the plant’s vital processes, and allowing high yields and good quality products. In addition, plant health additives applied to plants enhance nutrition efficiency, abiotic stress tolerance and/or plant quality traits, regardless of its nutrient contents. Several researches have been developed in order to evaluate the plant health additives in improving plant development subjected to stresses, saline environment, and development of seedlings, among others. Furthermore, various raw materials have been used in plant health additives compositions, such as humic acids, hormones, algae extracts, and plant growth-promoting bacteria. In this sense, this chapter aims to approach the use of plant health additives in plant growth according to the raw material used in their compositions as well as their effects on plants subjected to abiotic stresses.
In a further embodiment of the present invention, plant health additives are selected from bio-stimulants, plant growth regulators, microbial agents and micronutrients or mixture thereof.
In further embodiment of the present invention, plant health additives from the class of Bio stimulants are humic acid (salts), fulvic acid (salts), amino acids (alanine, arginine, aspartic acid, cysteine, glutamic acid, glycine, histidine, isoleucine, leucine, lysine, methionine, phenylalanine, proline, serine, threonine, tryptophan, tyrosine, valine or mixture thereof), protein hydrolysates, peptides, organic acid, acetyl thioproline, thiazolidine carboxylic acid, jasmonic acid, methyl jasmonate, chitosan, chitin, Probenazole, acibenzolar-s-methyl, seaweed extract (Ascophyllum nodosum), polyamines, silicic acid (salts)-orthosilicic acid (H4Si04), salicylic acid, lactic acid, phenyl lactic acid, fumaric acid, acibenzolar-s-methyl, nitrobenzene, (Homo)brassinolide, forchlorfenuron, triacontanol, nitrophenolate (sodium para-nitrophenolate, ortho-nitrophenolate, sodium-5-nitroguaiacolate or mixture thereof;

Plant growth regulators are Auxins: Indole acetic acid, Indole butyric acid, alpha-naphthyl acetic acid; Cytokinins: kinetin, zeatin, 6-benzylaminopurine, 6-benzyladenine, dipheylurea, thidiazuron, anisiflupurin; Ethylene modulators: aviglycine, prohexadione, prohexadione calcium, trinexapac, trinexapac-ethyl, aminoethoxyvinylglycine (AVG); Gibberellins: gibberelline, gibberellic acid, GA3; Growth inhibitors: abscisic acid, chlorpropham, flumetralin, maleic hydrazide, mepiquat, mepiquat chloride, mepiquat pentaborate; Growth retardants: chlormequat, chlormequat chloride, paclobutrazol, uniconazole-P; or mixture thereof;
Microbial agents are Rhizobium spp., Azotobacter spp., Azospirillum spp., Acetobacter spp., Bacillus megaterium var. phosphaticum, Bacillus polymyxa, Bacillus licheniformis, Frateuria aurantia, Thiobacillus thiooxidans, VAM (Vesicular Arbuscular Mycorrhiza) (Acaulospora spp., Gigaspora spp., Sclerocystis spp., Scutellospora spp., Glomus spp. Etc.), Acinetobacter calcoaceticus, Bacillus subtilis, Bacillus thuringiensis var. kurstaki, Pseudomonas fluorescens, Beauveria bassina, Metarrhizium anisopliae, Varticillium lecanii, Trichoderma viride, Trichoderma harzianum, Paecilomyces lilacinus, Trichoderma spp. etc. or mixture thereof;
Micronutrients are zinc (zinc sulphate heptahydrate, zinc sulphate mono hydrate, Zn-EDTA, zinc oxide, zinc lactate gluconate, zinc polyflavonoid), ferrous sulphate, copper sulphate, Manganese sulphate, boron (borax-sodium tetraborate, boric acid (H3BO3), di-sodium octa borate tetra hydrate (Na2B8O13.4H2O), di-sodium tetra borate penta hydrate, anhydrous borax, ) and sulphur (elemental sulphur, bentonite sulphur, boronated sulphur or a sulphate and thiosulphate salt) or mixture thereof.

The present inventors believe that the combination of the present invention synergistic agrochemical non aqueous composition comprising bioactive amount of (A) compound of Formula I; and (B) atleast one more of active ingredients selected from class of insecticides or fungicides or plant health additive or combination thereof surprisingly results in a synergistic action. The combination of the present invention allows for a broad spectrum of insect-pest and diseases control and has surprisingly improved plant vigour and yield. The broad spectrum of the present combination also provides a solution for preventing the development of resistance.
The synergistic agrochemical mixture has very advantageous curative, preventive and systemic pesticidal properties for protecting cultivated plants. As has been mentioned, said active ingredient composition can be used to inhibit or destroy the insect-pests and fungal and bacterial diseases that occur on plants or parts of plants of useful crops. The synergistic agrochemical composition of specific active ingredient has the special advantage of being highly active against insect pests and fungal and bacterial diseases that mostly occur on plant parts.
The synergistic agrochemical composition of the present invention is used to protect the crops and plants from insect pest and fungal and bacterial diseases. Examples of the crops on which the present compositions may be used include but are not limited to GMO (Genetically Modified Organism) and Non GMO varieties of Cotton (Gossypium spp.), Paddy (Oryza sativa), Wheat (Triticum aestavum), Barley (Hordeum vulgare), Maize (Zea mays), Sorghum (Sorghum bicolor), Oat (Avena sativa), Pearl millet (Pennisetum glaucum), Sugarcane (Saccharum officinarum) , Sugarbeet (Beta vulgaris), Soybean (Glycin max), Peanut (Arachis hypogaea), Sunflower (Helianthus annuus) , Mustard (Brassica juncea), Rape seed (Brassica napus), Linseed (Linum usitatissimum), Sesame (Sesamum indicum), Green gram (Vigna radiata), Black gram (Vigna mungo), Chickpea (Cicer aritinum), Cowpea (Vigna unguiculata), Redgram (Cajanus cajan), Frenchbean (Phaseolus vulgaris), Indian bean (Lablab purpureus), Horse gram (Macrotyloma uniflorum), Field pea (Pisum sativum), Cluster bean (Cyamopsis tetragonoloba), Lentils (Lens culinaris), Brinjal (Solanum melongena), Cabbage (Brassica oleracea var. capitata), Cauliflower (Brassica oleracea var. botrytis), Okra (Abelmoschus esculentus) , Onion (Allium cepa L.), Tomato (Solanum lycopersicun) , Potato (Solanum tuberosum) , Sweet potato (Ipomoea batatas), Chilly (Capsicum annum), Garlic (Allium sativum), Cucumber (Cucumis sativus), Muskmelons (Cucumis melo), Watermelon (Citrullus lanatus), Bottle gourd (Lagenaria siceraria), Bitter gourd (Momordica charantia), Radish (Raphanus sativus), Carrot (Dacus carota subsp. sativus), Turnip (Brassica rapa subsp rapa), Apple (Melus domestica), Banana (Musa spp.), Citrus groups (Citrus spp.), Grape (Vitis vinifera), Guava (Psidium guajava), Litchi (Litchi chinensis), Mango (Mangifera indica), Papaya (Carica papaya), Pineapple (Ananas comosus), Pomegranate (Punica granatum) , Sapota (Manilkara zapota), Tea (Camellia sinensis), Coffea (Coffea Arabica), Turmeric (Curcuma longa), Ginger (Zingiber officinale), Cumin (Cuminum cyminum), Fenugreek (Trigonella foenum-graecum), Fennel (Foeniculum vulgare), Coriander (Coriandrum sativum), Ajwain (Trachyspermum ammi), Psyllium (Plantago ovate), Black Pepper (Piper nigrum), Stevia (Stevia rebaudiana), Safed musli (Chlorophytum tuberosum), Drum stick (Moringa oleifera), Coconut (Coco nucifera), Mentha ( Mentha spp.), Rose (Rosa spp.), Jasmine (Jasminum spp.), Marigold ( Tagetes spp.), Common daisy (Bellis perennis), Dahlia (Dahlia hortnesis), Gerbera ( Gerbera jamesonii), Carnation (Dianthus caryophyllus), vegetables: solanaceous vegetables such as eggplant, tomato, pimento, pepper, potato, etc., cucurbit vegetables such as cucumber, pumpkin, zucchini, water melon, melon, squash, etc., cruciferous vegetables such as radish, white turnip, horseradish, kohlrabi, Chinese cabbage, cabbage, leaf mustard, broccoli, cauliflower, etc., asteraceous vegetables such as burdock, crown daisy, artichoke, lettuce, etc, liliaceous vegetables such as green onion, onion, garlic, and asparagus, ammiaceous vegetables such as carrot, parsley, celery, parsnip, etc., chenopodiaceous vegetables such as spinach, Swiss chard, etc., lamiaceous vegetables such as Perilla frutescens, mint, basil, etc, strawberry, sweet potato, Dioscorea japonica, colocasia, etc., flowers, foliage plants, turf grasses, fruits: pome fruits such apple, pear, quince, etc, stone fleshy fruits such as peach, plum, nectarine, Prunus mume, cherry fruit, apricot, prune, etc., citrus fruits such as orange, lemon, rime, grapefruit, etc., nuts such as chestnuts, walnuts, hazelnuts, almond, pistachio, cashew nuts, macadamia nuts, etc. berries such as blueberry, cranberry, blackberry, raspberry, etc., grape, kaki fruit, olive, plum, banana, coffee, date palm, coconuts, etc. , trees other than fruit trees; tea, mulberry, flowering plant, trees such as ash, birch, dogwood, Eucalyptus, Ginkgo biloba, lilac, maple, Quercus, poplar, Judas tree, Liquidambar formosana, plane tree, zelkova, Japanese arborvitae, fir wood, hemlock, juniper, Pinus, Picea, and Taxus cuspidate, etc.

The synergistic agrochemical non aqueous composition comprising bioactive amount of (A) compound of Formula I; and (B) atleast one more of active ingredients selected from class of insecticides or fungicides or plant health additive or combination is most suitable against wide range of insect-pests. The major insects pests controlled with Novel non aqueous formulations are belongs to the order Hemiptera, for example, rice leafhopper/green leaf hopper (GLH) Nephotettix nigropictus, rice brown plant hopper (BPH) Nilaparvata lugen, rice backed plant hopper (WBPH) Sogatella furcifera, Apple Mealy bug Phenococcus aceris, bean aphid Aphis fabae, black citrus aphid Toxoptera aurantii, citrus black scale Saissetia oleae, cabbage aphid Brevicoryne brassicae, Lipaphis erysimi, citrus red scale Aonidiella aurantii, yellow scale Aonidiella citrine, citrus mealybug Planococcus citri, corn leaf aphid Rhopalosiphum maidis, aphid Aphis gossypii, jassid Amrasca biguttula biguttla, mealy bug Planococcus spp. And Pseudococcus spp., cotton stainer Dysdercus suturellus, whitefly Bemisia tabaci, cowpea aphid Aphis crassivora, grain aphid Sitobion avenae, golden glow aphid Uroleucon spp., grape mealybug Pseudococcus maritimus, green peach aphid Myzus persicae, greenhouse whitefly Trialeurodes vaporariorum, papaya mealy bug Pracoccus marginatus, pea aphid Acyrthosiphon pisum, sugarcane mealybug Saccharicoccus sacchari, potato aphid Myzus persicae, potato leaf hopper Empoasca fabae, cotton whitefly Bemisia tabaci, tarnished plant bug Lygus lineolaris, wooly apple aphid Eriosoma lanigerum, mango hopper Amritodus atkinsoni, Idioscopus spp. ; order Lepidoptera, army worm Mythimna unipuncta, asiatic rice borer Chilo suppressalis, bean pod borer Maruca vitrata, beet armyworm Spodoptera exigua, black cutworm Agrotis ipsilon, bollworm Helicoverpa armigera , cabbage looper Trichoplusia ni, codling moth Cydia pomonella, croton caterpillar Achea janata, diamond backmoth Plutella xylostella, cabbage worm Pieris rapae, pink bollworm Pectinophora gossypiella, sugarcane borer Diatraea saccharalis, sugarcane early shoot borer Chilo infuscatellus tobacco budworm Heliothis virescens, tomato fruitworm Helicoverpa zea, velvet bean caterpillar Anticarsia gemmatalis, yellow stem borer Scirpophaga incertulas, spotted bollworm Earias vittella, rice leaffolder Cnaphalocrocis medinalis, pink stem borer Sesamia spp., tobacco leafeating caterpillar Spodoptera litura; brinjal fruit and shoot borer Leucinodes orbonalis, bean pod borer Maruca vitrata, Maruca testulalis, armyworm Mythimna separata, cotton pinkbollworm Pectinophora gossypiella, citrus leafminer Phyllocnistis citrella, cabbage butterfly Pieris bras-sicae, diamond backmoth Plutella xylostella, paddy stem borer Scirpophaga excerptallis, Scirpophaga incertulas, Scirpophaga innotata, wheat stem borer Sesamia inferens, Sitotroga cerealella, Spilosoma obliqua, fall armyworm Spodoptera frugiperda, Spodoptera littoralis, Spodoptera litura, Trichoplusia ni, Tryporyza nivella, Tryporyza incertulas, Tuta absoluta.
from the order Coleoptera, for example, apple twig borer Amphicerus spp., corn root worm Diabrotica virgifera, cucumber beetle diabrotica balteata, boll weevil Anthonomus grandis, grape flea beetle Altica chalybea, grape root worm Fidia viticola, grape trunk borer Clytoleptus albofasciatus, radish flea beetle Phyllotreta armoraciae, maize weevil Sitophilus zeamais, northern corn rootworm Diabrotica barberi, rice water weevil Lissorhoptrus oryzophilus, Anthonomus grandis, Bruchus lentis, Diabrotica semipunctata, Diabrotica virgifera, Dicladispa armigera, Epila-chna varivestis, various species of white grubs are Holotrichia bicolor, Holotrichia consanguinea, Holotrichia serrata, Leptinotarsa decemlineata, Phyllotreta chrysocephala, Popillia japonica etc; from the order Orthoptera, for example, Gryllotalpa spp., Locusta spp., and Schistocerca is spp.; from the order Thysanoptera, for example, Thrips- Frankliniella spp., Thrips palmi, Thrips tabaci and Scirtothrips dorsalis, Thrips parvispinus; termites (Isoptera), e.g. Calotermes flavicollis, Coptotermes formosanus, Heterotermes aureus, Leucotermes flavipes, Microtermes obesi, Odontotermes obesus, Reticulitermes flavipes, Termes natalensis; from the order Heteroptera, for example, Dysdercus spp., Leptocorisa spp., from the order Hymenoptera, for example, Solenopsis spp. ; from the order Diptera, for example, Antherigona soccata, Dacus spp., Liriomyza spp., Melanagromyza spp., from the order Acarina, for example, Aceria mangiferae, Brevipalpus spp., Eriophyes spp., Oligonychus mangiferus, Oligonychus punicae, Panonychus citri, Panonychus ulmi, Polyphagotarsonemus latus, Tarsonemus spp., Tetranychus urticae, Tetranychus cinnabarinus.

The novel OD formulations have very good fungicidal bactericidal properties and can be employed for controlling phytopathogenic fungi such as Ascomycetes, Basidiomycetes, Chytridiomycetes, Deuteromycetes, Oomycetes, Plasmodiophoromycetes, Zygomycetes, and the like.
Examples which may be mentioned, but not by limitation, are some pathogens of fungal diseases which come under the above generic terms:
Diseases caused by pathogens causing powdery mildew such as, for example, Blumeria species such as, for example, Blumeria graminis; Podosphaera species such as, for example, Podosphaera leucotricha; Oidium species such as, for example Oidium mangiferae, Sphaerotheca species such as, for example, Sphaerotheca fuliginea; Uncinula species such as, for example, Uncinula necator; Leveillula species such as, for example Leveillula taurica, Erysiphe species such as for example Erysiphe polygoni, diseases caused by pathogens of rust diseases such as, for example, Gymnosporangium species such as, for example, Gymnosporangium sabinae, Hemileia species such as, for example, Hemileia vastatrix; Phakopsora species such as, for example, Phakopsora pachyrhizi and Phakopsora meibomiae; Puccinia species such as, for example, Puccinia graminis, Puccinia recondita or Puccinia triticina, Puccinia striiformis; Uromyces species such as, for example, Uromyces phaseoli; diseases caused by pathogens of smut diseases such as, for example, Sporisorium species such as , for example, Sporisorium scitamineum; Ustilago species such as, for example Ustilago maydis, Tilletia species such as for example Tilletia tritici, Ustilaginoidea species such as , for example Ustilaginoidea virens, diseases caused by pathogens of ergot diseases such as, for example Claviceps species, Claviceps purpurea; diseases caused by pathogens from the group of the Oomycetes such as, for example, Bremia species such as, for example, Bremia lactucae; Peronospora species such as, for example, Peronospora pisi or P. brassicae; Phytophthora species such as, for example, Phytophthora infestans; Plasmopara species such as, for example, Plasmopara viticola; Pseudoperonospora species such as, for example, Pseudoperonospora humuli or Pseudoperonospora cubensis; Pythium species such as, for example, Pythium ultimum; leaf spot diseases and leaf wilt caused by, for example, Alternaria species such as, for example, Alternaria solani; Cercospora species such as, for example, Cercospora arachidicola; Cladiosporum species such as, for example, Cladiosporium cucumerinum; Cochliobolus species such as, for example, Cochliobolus sativus (conidial form: Drechslera, syn: Helminthosporium);
Colletotrichum species such as, for example, Colletotrichum lindemuthanium; Cycloconium species such as, for example, Cycloconium oleaginum; Diaporthe species such as, for example, Diaporthe citri;
Elsinoe species such as, for example, Elsinoe fawcettii; Gloeosporium species such as, for example, Gloeosporium laeticolor; Glomerella species such as, for example, Glomerella cingulata; Guignardia species such as, for example, Guignardia bidwelli; Leptosphaeria species such as, for example, Leptosphaeria maculans; Magnaporthe species such as, for example, Magnaporthe grisea;
Mycosphaerella species such as, for example, Mycosphaerella graminicola; Phaeosphaeria species such as, for example, Phaeosphaeria nodorum; Pyrenophora species such as, for example, Pyrenophora teres;
Ramularia species such as, for example, Ramularia collo-cygni; Rhynchosporium species such as, for example, Rhynchosporium secalis; Septoria species such as, for example, Septoria apii;
Typhula species such as, for example, Typhula incarnata; Venturia species such as, for example, Venturia inaequalis; root and stalk diseases, caused by, for example, Corticium species such as, for example, Corticium graminearum; Fusarium species such as, for example, Fusarium oxysporum;
Gaeumannomyces species such as, for example, Gaeumannomyces graminis; Rhizoctonia species such as, for example, Rhizoctonia solani; Tapesia species such as, for example, Tapesia acuformis;
Thielaviopsis species such as, for example, Thielaviopsis basicola; ear and panicle diseases (including maize cobs), caused by, for example, Alternaria species such as, for example, Alternaria spp.;
Aspergillus species such as, for example, Aspergillus flavus; Cladosporium species such as, for example, Cladosporium spp.; Claviceps species such as, for example, Claviceps purpurea;
Fusarium species such as, for example, Fusarium culmorum; Gibberella species such as, for example, Gibberella zeae; Monographella species such as, for example, Monographella nivalis;
diseases caused by smuts such as, for example, Sphacelotheca species such as, for example, Sphacelotheca reiliana; Tilletia species such as, for example, Tilletia caries; Urocystis species such as, for example, Urocystis occulta; Ustilago species such as, for example, Ustilago nuda;
fruit rot caused by, for example, Aspergillus species such as, for example, Aspergillus flavus;
Botrytis species such as, for example, Botrytis cinerea; Penicillium species such as, for example, Penicillium expansum; Sclerotinia species such as, for example, Sclerotinia sclerotiorum;
Verticilium species such as, for example, Verticilium alboatrum; seed- and soil-borne rots and wilts, and seedling diseases, caused by, for example, Fusarium species such as, for example, Fusarium culmorum; Phytophthora species such as, for example, Phytophthora cactorum; Pythium species such as, for example, Pythium ultimum; Rhizoctonia species such as, for example, Rhizoctonia solani;
Sclerotium species such as, for example, Sclerotium rolfsii; cankers, galls and witches' broom diseases, caused by, for example, Nectria species such as, for example, Nectria galligena; wilts caused by, for example, Monilinia species such as, for example, Monilinia laxa; deformations of leaves, flowers and fruits, caused by, for example, Taphrina species such as, for example, Taphrina deformans; degenerative diseases of woody species, caused by, for example, Esca species such as, for example, Phaemoniella clamydospora; flower and seed diseases, caused by, for example, Botrytis species such as, for example, Botrytis cinerea; diseases of plant tubers caused by, for example, Rhizoctonia species such as, for example, Rhizoctonia solani; diseases caused by bacterial pathogens such as, for example, Xanthomonas species such as, for example, Xanthomonas campestris pv. oryzae; Pseudomonas species such as, for example, Pseudomonas syringae pv. lachrymans; Erwinia species such as, for example, Erwinia amylovora.
The present non aqueous formulation comprising bioactive amount of (A) compound of Formula I; and (B) atleast one more of active ingredients selected from class of an insecticides; or a fungicides; or a plant health additive; or combination thereof provides:
• Improved leaf penetration of spray droplets, retards evaporation loss and enhances the absorption of active ingredients;
• Increase spreading properties on leaf surfaces, better wetting of waxy leaf surfaces;
• Increase penetration of active ingredients into the insect cuticles and insects with waxy cuticles like mealybug and scale insects;
• Improve rain fast properties.
Further present invention further provides increases in the synergistic activities between active ingredients.
The present novel synergistic OD formulation improves the residual control i.e. enhance the duration of control of insect-pests, mites and fungal and bacterial diseases.
The inventor has found that with the novel recipe of OD formulation, we can reduce the doses of active ingredients and thereby minimizing the pesticidal load into the environment.
The present novel OD formulations composition is without or reduced amount of aromatic solvent, so it’s safe to the applicator and reducing the loading of aromatic solvent into the environment.
Non aqueous formulation of the present invention comprises carrier or solvent as Pongamia, Palm or jojoba oil. Due to High flash point (smoke points) of Pongamia (>220 Celcius), Palm oil (>240 C), Jojoba oil (>290 C), the novel recipe of OD formulations are more stable and safer for storage at elevated temperature. Therefore the present novel recipe of OD formulations has thermal and chemical stability over a broad range of conditions.
The novel recipe of OD formulations has better pourability, so it will minimize the wastage. The novel recipe of OD formulations are stable with wider pH range.
In the composition of the present OD formulation, we can reduce the toxicity hazards to the applicators, i.e. improves the safety of applicators at the time of handling and spraying the pesticides.
The process for preparing the present synergistic non aqueous formulation can be modified accordingly by any person skilled in the art based on the knowledge of manufacturing the formulation. However, all such variations and modifications are covered by the scope of the present invention.
The composition of the present invention in addition to bioactive amounts of active ingredients further comprises inactive excipients including but not limited to Super Wetting-spreading-penetrating agent, carrier or solvent, dispersant or dispersing agent, emulsifying agent, anti-freezing agent, anti-foam agent, preservatives and buffering agent.
Examples of super wetting-spreading-penetrating agent used herein for present non aqueous formulation include but not limited to Polyalkyleneoxide modified Heptamethyl trisiloxane (Modified trisiloxane).

Polyalkyleneoxide modified heptamethyltrisiloxane:
Polyalkyleneoxide modified heptamethyltrisiloxane can improve the penetration effect of pesticides and reduce the spray volume. It is used in the fields of pesticides, herbicides, insecticides, acaricides, fungicides, plant growth regulating agents, and other aspects. (Polyalkyleneoxide modified heptamethyltrisiloxane, a registered product of GE Silicones)

Molecular formula: (C2H4O)n•C11H30O3Si3
Examples of Carrier or solvents used herein for present non aqueous formulation include but not limited to Pongamia/karanja/karanj (Millettia pinnata/Pongamia pinnata/Pongamia glabra) oil alone; or Palm (Elaeis spp.) oil (Palm oil and palm kernel oil) alone; or Blend of Pongamia oil and palm oil; or Blend of Pongamia oil and Jojoba (Simmondsia chinensis); or Blend of Palm oil and Jojoba oil; or Blend of Pongamia oil and vegetable oil; or Blend of Palm oil and vegetable oil; or Blend of Pongamia oil, Palm oil and vegetable oil; the vegetable oil may be any one or mixture of two or more selected from soybean (Glycine max) oil, groundnut (Arachis hypogaea) oil, rapeseed (Brassica napus subspecies) oil, mustard (Brassica juncea) oil, sesame (Sesamum indicum) oil, Corn (Zea mays) oil, rice (Oryza sativa) bran oil, castor (Ricinum communis) seed oil, cotton (Gossypium hirsutum) seed oil, linseed (Linum usitatissimum), coconut (Cocos nucifera) oil, Kapok (Ceiba pentandra) oil, Papaya (Carica papaya) seed oil, Tea seed (Camellia oleifera) oil, sunflower (Helianthus annuus) oil, safflower (Carthamus tinctorius) seed oil, Eucalyptus (Eucalyptus globulus) oil, Olive (Olea europaea) oil, Jatropha (Jatropha curcas) oil, Garlic acid (Allium sativum), Ginger oil (Zingiber officinale), D-limonene, Citronella oil or Ceylon ironwood (Mesua ferrea) oil, Mahua (Madhuca longifolia) oil.
All the solvents or combination or blend thereof, used hereby for the present OD formulation may be present in their alkylated or ethoxylated or epoxylated or esterified form. Examples include methyl ester of karanj oil, methyl ester of palm oil, methyl ester of karanj oil and soybean oil, methyl ester of palm oil and corn oil, methyl ester of palm oil and rapeseed oil etc.
All the said oils used as a carrier or diluent are procured from the vendor based in Gujarat State.
Pongamia oil/ karanja oil:
Pongamia oil is derived from the seeds of the Millettia pinnata tree, which is native to tropical and temperate Asia. Millettia pinnata, also known as Pongamia pinnata or Pongamia glabra, is common throughout Asia and thus has many different names in different languages, many of which have come to be used in English to describe the seed oil derived from M. pinnata; Pongamia is often used as the generic name for the tree and is derived from the genus the tree was originally placed in. Other names for this oil include honge oil, kanuga oil, karanja oil, and pungai oil.
Pongamia oil is extracted from the seeds by expeller pressing, cold pressing, or solvent extraction. The oil is yellowish-orange to brown in colour. It has a high content of triglycerides, and its disagreeable taste and odour are due to bitter flavonoid constituents including karanjin, pongamol, tannin and karanjachromene. The physical properties of crude pongamia oil are as flash point of the pongamia oil is 225°C.
Its fruits are used in abdominal remedies. Its seeds are used in tumor treatment. Oil is used for curing rheumatism. Leaves are used against Micrococcus. Their leaves juices are used for the treatment of diarrhea cold and cough. It has curative effect for leucoderma and itches. Its oil is used as a lubricant, water paint binder. Utilization of Seed Cake as a Manure for having the proper N, P & K content and ratio. As a material for biogas (Methane) production. As a Material for Producing Proteins for Food, Pharmaceutical and Industrial Applications by Chemical and Biochemical Technologies. Production of Soluble Fibers for Food Uses.
It is medium sized tree and is found throughout India. The tree is drought resistant. Major producing countries are East Indies, Philippines, and India. The oil content varies from 27- 39%.Its cake is used as pesticide and fertilizer. The deoiled cake when applied to soil, has pesticidal value, especially against nematodes and also helps in improving soil fertility. Karanja is often planted in home steads as a shade or ornamental tree and in avenue planting along roadside and canals. It is preferred species help in controlling soil erosion and binding sand dunes due to its dense network of lateral roots.
The persistence of karanj is greater than other tested botanical insecticides. The dosages at 1 and 2% of karanj oil give better control of insect pests compared with lower concentrations. Karanj oil and karanjin shows greater biological activity than other karanj extracts. The karanj oil shows good synergistic effect with a number of chemical insecticides. Therefore, karanj has great potential to be used as biopesticide because of its antifeedant; oviposition deterrent, ovicidal, roachicidal, juvenile hormone activity and insecticidal properties against a wide range of insect pests [Mukesh Kumar a & Ram Singh, Department of Entomology, Potential of Pongamia glabra Vent as an Insecticide of Plant Origin, CCS Haryana, Agricultural University, Hisar, 125 004, India, Published online: 24 Apr 2012].
Botanical pesticides are also very potent insecticides and, due to their composition, they can help to fight the global problem of insects developing resistance to insecticides. Insecticides based on karanja oil shows efficiency against L. decemlineata larvae at different concentrations [ Katerina Kovarikova and Roman Pavela; United Forces of Botanical Oils: Efficacy of Neem and Karanja Oil against Colorado Potato Beetle under Laboratory Conditions; Plants 2019, 8, 608; doi:10.3390/plants8120608].
Palm oil
Palm oil is an edible vegetable oil derived from the mesocarp (reddish pulp) of the fruit of the oil palms, primarily the African oil palm Elaeis guineensis, and to a lesser extent from the American oil palm Elaeis oleifera and the maripa palm Attalea maripa.
The use of palm oil in food and beauty products has attracted the concern of environmental groups; the high oil yield of the trees has encouraged wider cultivation, leading to the clearing of forests in parts of Indonesia and Malaysia to make space for oil-palm monoculture. This has resulted in significant acreage losses of the natural habitat of the three surviving species of orangutan. One species in particular, the Sumatran orangutan, has been listed as critically endangered.
PME (Palm-based Methyl Esters) as carrier solvents appear to enhance pesticide efficacy, which may allow for a reduction in dosage or frequency of application, help to control adverse effects and reduce the cost spent on pesticides. Therefore, PME as a carrier solvent in pesticide formulations is a promising prospect for the agrochemical industry [ Sumaiyah Megat Nabil Mohsin; Ismail Ab Raman; Zafarizal Aldrin Azizul Hasan and Zainab Idris; Palm-based Methyl Esters as Carrier Solvents in Pesticide Formulations, Technical Report, January 2018, Page no. 32-38].
Jojoba Oil:
Jojoba oil is the liquid produced in the seed of the Simmondsia chinensis (jojoba) plant, a shrub, which is native to southern Arizona, southern California, and northwestern Mexico. The oil makes up approximately 50% of the jojoba seed by weight. The terms "jojoba oil" and "jojoba wax" are often used interchangeably because the wax visually appears to be a mobile oil, but as a wax it is composed almost entirely (~97%) of mono-esters of long-chain fatty acids and alcohols (wax ester), accompanied by only a tiny fraction of triglyceride esters. This composition accounts for its extreme shelf-life stability and extraordinary resistance to high temperatures, compared with true vegetable oils.
Jojoba oil shows an insecticidal activity. At lower as well has higher concentration jojoba oil has insecticidal properties and can be use plant protection management [Tahany, R. Abd El-Zaher; Biological Activity of Four Plant Oils in the Form of Nano Products on the Larvae of Cotton leaf worm; Middle East Journal of Applied Sciences; Volume : 07, Issue :02, April-June 2017, Pages: 239-249].
Vegetable Oil:
The term "vegetable oil" can be narrowly defined as referring only to substances that are liquid at room temperature, or broadly defined without regard to a substance's state (liquid or solid) at a given temperature. While a large majority of the entries in this list fit the narrower of these definitions, some do not qualify as vegetable oils according to all understandings of the term.
Vegetable oils are triglycerides extracted from plants. Some of these oils have been part of human culture for millennia. Edible vegetable oils are used in food, both in cooking and as supplements. Many oils, edible and otherwise, are burned as fuel, such as in oil lamps and as a substitute for petroleum-based fuels. Some of the many other uses include wood finishing, oil painting, and skin care.
Vegetable oils, or vegetable fats, are oils extracted from seeds or from other parts of fruits. Like animal fats, vegetable fats are mixtures of triglycerides. Soybean oil, grape seed oil, and cocoa butter are examples of fats from seeds. Olive oil, palm oil, and rice bran oil are examples of fats from other parts of fruits. In common usage, vegetable oil may refer exclusively to vegetable fats which are liquid at room temperature. Vegetable oils are usually edible; non-edible oils derived mainly from petroleum are termed mineral oils.
Most, but not all vegetable oils are extracted from the fruits or seeds of plants. For instance, palm oil is extracted from palm fruits, while soybean oil is extracted from soybean seeds. Vegetable oils may also be classified by grouping oils extracted from similar plants, such as "nut oils". Although most plants contain some oil, only the oil from certain major oil crops complemented by a few dozen minor oil crops is widely used and traded.
Oils from plants are used for several different purposes. Edible vegetable oils may be used for cooking, or as food additives. Many vegetable oils, edible and otherwise, are burned as fuel, for instance as a substitute for petroleum-based fuels. Some may be also used for cosmetics, medical purposes, wood finishing, oil painting, formulation ingredient in many pharmaceutical or agricultural formulations and other industrial purposes.
The vegetable Oil for preparing blend with karanj oil or palm oil or jojoba oil used herein as solvent or carrier for present non aqueous formulation include but not limited to any one or mixture of two or more selected from soybean (Glycine max) oil, groundnut (Arachis hypogaea) oil, rapeseed (Brassica napus subspecies) oil, mustard (Brassica juncea) oil, sesame (Sesamum indicum) oil, Corn (Zea mays) oil, rice (Oryza sativa) bran oil, castor (Ricinum communis) seed oil, cotton (Gossypium hirsutum) seed oil, linseed (Linum usitatissimum), coconut (Cocos nucifera) oil, Kapok (Ceiba pentandra) oil, Papaya (Carica papaya) seed oil, Tea seed (Camellia oleifera) oil, sunflower (Helianthus annuus) oil, safflower (Carthamus tinctorius) seed oil, Eucalyptus (Eucalyptus globulus) oil, Olive (Olea europaea) oil, Jatropha (Jatropha curcas) oil, Garlic acid (Allium sativum), Ginger oil (Zingiber officinale), D-limonene, Citronella oil or Ceylon ironwood (Mesua ferrea) oil, Mahua (Madhuca longifolia) oil.
Examples of polar cosolvents used herein optionally for present non aqueous formulation include but not limited to cyclohexanone, acetophenone, NMP (N-methyl pyrrolidinone), dimethyl sulfoxide, benzyl alcohol, butanol, n-octanol, n-propanol, 2-ethyl hexanol, tetrahydro furfuryl alcohol, isophorone, fatty acid dimethyl amide, 2-hexylethyl lactate and propylene carbonate.
A dispersant or a dispersing agent is a substance which adsorbs onto the surface of particles and helps to preserve the state of dispersion of the particles and prevents them from re-aggregating. Examples of dispersing agent used herein for used herein for present non aqueous formulation include but not limited to condensed naphthalene sulfonate, propoxylated Ethoxylated copolymer monoalkylether (ethylhexanol), alkyl sulfonates, alkyl benzene sulfonates, alkyl aryl sulfonates, alkylphenolalkoxylates, tristyrylphenol ethoxylates, natural or synthetic fatty ethoxylate alcohols, natural or synthetic fatty acid alkoxylates, natural or synthetic fatty alcohols alkoxylates, alkoxylated alcohols (such as n-butyl alcohol poly glycol ether), block copolymers (such as ethylene oxide-propylene oxide block copolymers and ethylene oxide-butylene oxide block copolymers), fatty acid-polyalkylene glycol condensates, polyamine-fatty acid condensates, polyester condensates, salts of polyolefin condensates, sodium ligno sulfonate, sodium ploycarboxylate, EO/PO based copolymer, phenol sulfonate, sodium methyl oleoyl taurate, styrene acrylic acid copolymer, propyleneoxide-ethyleneoxide-copolymer, polyethylene glycol 2,4,6-tristyrylphenyl ether, tristyrylphenol-polyglycolether-phosphate, tristyrylphenole with 16 moles EO, tristyrylphenol-polyglycolether-phosphate, oleyl-polyglycolether with ethylene oxide, tallow fattyamine polyethylene oxide, nonylphenol polyglycolether with 9-10 moles ethylene oxide.
Antifoaming agent for the present formulation is selected from various compounds and selectively used according to the formulation. Generally, there are two types of antifoam agents, namely silicones and non-silicones. Silicones are usually aqueous emulsions of dimethyl poly siloxane while the non-silicone anti-foam agents are water- insoluble oils, such as octanol and nonanol, or silica. In both cases, the function of the anti-foam agent is to displace the surfactant from the air-water interface.
Examples of Antifoaming agent used herein for present non aqueous formulation include but not limited to silicone oil, silicone compound, C10~C20 saturated fat acid compounds or C8~C10 aliphatic alcohols compound, silicone antifoam emulsion, dimethyl siloxane, poly dimethyl siloxane.
Examples of Anti-freezing agent used herein for present non aqueous formulation include but not limited ethylene glycol, propane diols, glycerine or the urea, glycol (Monoethylene glycol, Diethylene glycol, Polypropylene glycol, Polyethylene glycol), glycerine, urea, magnesium sulfate heptahydrate, sodium chloride.
Preservative used herein for the present non aqueous formulation include but not limited to 1,2-benzisothiazolin-3(2H)-one, sodium salt, sodium benzoate, 2-bromo-2-nitropropane-1,3-diol, formaldehyde, sodium o-phenylphenate, 5-chloro-2-methyl-4-isothiazolin-3-one & 2-methyl-4-isothiazolin-3-one, Butyl hydroxyl toluene.
Emulsifying agent used herein for the present non aqueous formulation includes but not limited to castor oil ethoxylates, alcohol ethoxylates, fatty acid ethoxylates, sorbitan ester ethoxylates, ethoxylated sorbitol oleates, sulphosuccinate, calcium salts of dodecylbenzene sulphonate, alkylammonium salts of alkylbenzene sulphonate, alkylsulphosuccinate salts, ethylene oxide-propylene oxide block copolymers, ethoxylated alkylamines, ethoxylated alkyl phenols, polyoxyethylene sorbitan monolaurate.
Examples of buffering agent used herein for present non aqueous formulation is selected Citric acid, sodium carbonate, sodium bicarbonate, sulphuric acid, hydrochloric acid, sodium hydroxide, potassium hydroxide, acetic acid, sorbic acid.
Stabilizers or stabilizing agent used herein for the present non aqueous formulation includes but not limited to hectorite clay, aluminum magnesium silicate, bentonite clay, silica, attapulgite clay.
While the foregoing written description of the invention enables one of ordinary skill to make and use what is considered presently to be the best mode thereof, those of ordinary skill will understand and appreciate the existence of variations, combinations, and equivalents of the specific embodiment, method, and examples herein. The invention should therefore not be limited by the above described embodiment, method, and examples, but by all embodiments and methods within the scope and spirit of the invention. The invention shall now be described with reference to the following specific examples. It should be noted that the example(s) appended below illustrate rather than limit the invention, and that those skilled in the art will be able to design many alternative embodiments without departing from the scope of the present invention.
These and other aspects of the invention may become more apparent from the examples set forth herein below. These examples are provided merely as illustrations of the invention and are not intended to be construed as a limitation thereof.
EXAMPLE 1:
Procedure: Manufacturing process for Non-aqueous [Oil dispersion (OD)] formulation

Part A- Preparation of the liquid premix
Step 1 Charge the oil (pongamia oil or palm oil or pongamia oil+palm oil or pongamia oil+jojoba oil or palm oil+jojoba oil or pongamia oil+vegetable oil or paml oil+vegetable oil or pongamia oil+palm oil+vegetable oil) or solvent or both into a vessel with anchor stirrer.
Step 2 Under stirring, add the emulsifier/super wetting-spreading-penetrating agent (Polyalkyleneoxide modified Heptamethyl trisiloxane) and dispersing agent and stir until all ingredients are dissolved completely.
Part B- Preparation of the slurry
Step 1 Now, charge the liquid premix into a second vessel, equipped with a cooling and heating device and a high shear stirrer.
Step 2 Add the active ingredient(s) and homogenize thoroughly. Pre-mill this mixture and finally mill it using a bead mill/sand mill/attritor to achieve a particle size distribution as required by the specification.
Part C- Preparation of the Thickener gel
Step 1 Charge the remaining oil or solvent to the vessel, equipped with a high shear stirrer.
Step 2 Add gradually the thickening agent, maintaining high-shear mixing throughout. Stirring is continued until thoroughly mixed.
Step 3 Under stirring, the thickener is added. Allow the gel to swell whilst maintaining mixing.
Part C- Preparation of the final formulation
Step 1 Now add the thickener gel solution into milled slurry and disperse the mixture by using a high shear stirrer.
Step 2 Check the finished formulation to specification.
Step 3 After approval, material is packed in required pack sizes.

EXPERIMENT 1:
EXAMPLE 2:
Tert-butyl4-[[(E)-(1,3-dimethyl-5-phenoxypyrazol-4-yl)methylideneamino]oxymethyl ]benzoate [compound of Formula I] 6%+Etoxazole 10% OD (Recipe-1-Novel OD)

Ingredients Percent (w/w)
compound of Formula I a.i. 6.00
Etoxazole a.i. 10.00
Dispersing agent-Tristyrylphenol-polyglycolether-phosphate 4.50
Emulsifier-Octylphenol ethoxylate 8.00
Stabilizer-Bentonite clay 3.00
Antifoam-Polydimethyl siloxane 0.30
Preservative-1,2-benzisothiazolin-3(2H)-one 0.20
Antifreezing agent-Polypropylene glycol 5.00
Buffering agent-citric acid 0.15
Wetting agent-Polyalkyleneoxide modified Heptamethyltrisiloxane 5.00
Solvent-Methyl ester of Karanj oil 57.85
Total 100.00

Storage Stability Study:
Compound of Formula I 6%+Etoxazole 10% OD (Recipe-1-Novel OD)
Storage stability- compound of Formula I 6%+Etoxazole 10% OD (Recipe-1-Novel OD)
Laboratory storage for 14 days
Parameters Specification (in house) Initial At 54±2 0C At 0±2 0C
compound of Formula I content percent by mass 5.70 to 6.60 6.50 6.10 6.45
Etoxazole content percent by mass 9.50 to 10.50 10.40 10.16 10.36
compound of Formula I suspensibility percent min. 80 98.00 97.00 97.00
Etoxazole suspensibility percent min. 80 98.00 97.00 97.50
pH range (1% aq. Suspension) 5.0 to 7.5 6.20 6.00 6.10
Pourability 95% min. 99.00 98.40 99.70
Specific gravity 1.00-1.05 1.01 1.01 1.01
Viscosity at spindle no. 62, 20 rpm 350-800 cps 660 700 670
Particle size (micron) D50<3, D90<10 2.2,8.5 2.5,8.7 2.4,8.8
Persistent foam ml (after 1 minute) max. 60 nil 3 nil
Room temperature storage
Parameters Specification (in house) 1 month 6 months 12 months
compound of Formula I content percent by mass 5.70 to 6.60 6.50 6.40 6.30
Etoxazole content percent by mass 9.50 to 10.50 10.40 10.30 10.25
compound of Formula I suspensibility percent min. 80 98.00 98.00 97.50
Etoxazole suspensibility percent min. 80 98.00 98.00 97.20
pH range (1% aq. Suspension) 5.0 to 7.5 6.20 6.10 6.00
Pourability 95% min. 99.00 98.90 98.50
Specific gravity 1.00-1.05 1.01 1.01 1.01
Viscosity at spindle no. 62, 20 rpm 350-800 cps 660 670 680
Particle size (micron) D50<3, D90<10 2.2,8.5 2.4,8.7 2.6,8.8
Persistent foam ml (after 1 minute) max. 60 nil 2 2

The novel OD formulation of compound of Formula I 6%+Etoxazole 10% meets the all inhouse specifications for storage stability studies in laboratory (at 54±2 C & At 0±2 C for 14 days) and room temperature (for 12 months).
EXAMPLE 3:
Tert-butyl4-[[(E)-(1,3-dimethyl-5-phenoxypyrazol-4-yl)methylideneamino]oxymethyl ]benzoate [compound of Formula I] 6%+Etoxazole 10% OD (Recipe-2-Novel OD)
Ingredients Percent (w/w)
compound of Formula I a.i. 6.00
Etoxazole a.i. 10.00
Dispersing agent-Tristyrylphenol-polyglycolether-phosphate 4.50
Emulsifier-Octylphenol ethoxylate 8.00
Stabilizer-Bentonite clay 3.00
Antifoam-Polydimethyl siloxane 0.30
Preservative-1,2-benzisothiazolin-3(2H)-one 0.20
Antifreezing agent-Polypropylene glycol 5.00
Buffering agent-citric acid 0.15
Wetting agent-Polyalkyleneoxide modified Heptamethyltrisiloxane 5.00
Solvent-Methyl ester of Palm oil 57.85
Total 100.00

EXAMPLE 4:
Tert-butyl4-[[(E)-(1,3-dimethyl-5-phenoxypyrazol-4-yl)methylideneamino]oxymethyl ]benzoate [compound of Formula I] 6%+Etoxazole 10% OD (Recipe-3-Novel OD)
Ingredients Percent (w/w)
compound of Formula I a.i. 6.00
Etoxazole a.i. 10.00
Dispersing agent-Tristyrylphenol-polyglycolether-phosphate 4.50
Emulsifier-Octylphenol ethoxylate 8.00
Stabilizer-Bentonite clay 3.00
Antifoam-Polydimethyl siloxane 0.30
Preservative-1,2-benzisothiazolin-3(2H)-one 0.20
Antifreezing agent-Polypropylene glycol 5.00
Buffering agent-citric acid 0.15
Wetting agent-Polyalkyleneoxide modified Heptamethyltrisiloxane 5.00
Solvent-Methyl ester of Palm oil and Mahuva oil 57.85
Total 100.00

Tert-butyl4-[[(E)-(1,3-dimethyl-5-phenoxypyrazol-4-yl)methylideneamino]oxymethyl ]benzoate [compound of Formula I] 2.4%+Etoxazole 10% SC (conventional formulation)
Ingredients Percent (w/w)
Fenpyroximate a.i. 2.40
Etoxazole a.i. 10.00
Naphthalenesulfonic acid-formaldehyde condensate 4.00
Alkylphenol polyoxyethylene 2.50
Fatty alcohol 1.00
Propane diols 5.00
Organic silicone oil 0.50
Xanthane gum 0.20
Butylated hydroxyl anisole 0.10
Water qs
Total 100

Tert-butyl4-[[(E)-(1,3-dimethyl-5-phenoxypyrazol-4-yl)methylideneamino]oxymethyl ]benzoate [compound of Formula I] 4.8%+Etoxazole 20% WG (conventional formulation)
Ingredients Percent (w/w)
Fenpyroximate a.i. 4.80
Etoxazole a.i. 20.00
Sodium alkyl benzene sulfonate 10.00
Naphthalenesulfonic acid-formaldehyde condensate 10.00
Starch 2.00
Ammonium sulfate 15.00
Organic silicone oil 0.50
Precipitated calcium carbonate 20.00
Adularescent kaolin qs
Total 100.00

EXPERIMENT 2:
EXAMPLE 5:
Tert-butyl4-[[(E)-(1,3-dimethyl-5-phenoxypyrazol-4-yl)methylideneamino]oxymethyl ]benzoate [compound of Formula I] 3%+Cyantraniliprole 8% OD (Recipe A-Novel OD)
Ingredients Percent (w/w)
compound of Formula I a.i. 3.00
Cyantraniliprole a.i. 8.00
Dispersing agent-Tristyrylphenol-polyglycolether-phosphate 4.50
Emulsifier-Octylphenol ethoxylate 8.00
Stabilizer-Bentonite clay 2.00
Antifoam-Polydimethyl siloxane 0.30
Preservative-1,2-benzisothiazolin-3(2H)-one 0.20
Antifreezing agent-Polypropylene glycol 5.00
Buffering agent-citric acid 0.15
Wetting agent-Polyalkyleneoxide modified Heptamethyltrisiloxane 6.00
Solvent-Methyl ester of Palm oil 62.85
Total 100.00

Storage stability study: compound of Formula I 3%+Cyantraniliprole 8% OD (Recipe A-Novel OD)
Storage stability- compound of Formula I 3%+Cyantraniliprole 8% OD (Recipe A-Novel OD)
Laboratory storage for 14 days
Parameters Specification (in house) Initial At 54±2 0C At 0±2 0C
compound of Formula I content percent by mass 2.85 to 3.30 3.25 3.10 3.15
Cyantraniliprole content percent by mass 7.60 to 8.80 8.60 8.30 8.50
compound of Formula I suspensibility percent min. 80 98.80 98.20 98.60
Cyantraniliprole suspensibility percent min. 80 98.80 97.60 97.80
pH range (1% aq. Suspension) 5.0 to 7.5 6.20 6.15 6.15
Pourability 95% min. 98.80 97.60 98.50
Specific gravity 1.00-1.05 1.01 1.01 1.01
Viscosity at spindle no. 62, 20 rpm 350-800 cps 640 670 660
Particle size (micron) D50<3, D90<10 2.1,8.3 2.5,8.7 2.4,8.6
Persistent foam ml (after 1 minute) max. 60 nil 1 nil
Room temperature storage
Parameters Specification (in house) 1 month 6 months 12 months
compound of Formula I content percent by mass 2.85 to 3.30 3.25 3.20 3.18
Cyantraniliprole content percent by mass 7.60 to 8.80 8.60 8.45 8.30
compound of Formula I suspensibility percent min. 80 98.80 98.40 98.00
Cyantraniliprole suspensibility percent min. 80 98.80 98.20 97.80
pH range (1% aq. Suspension) 5.0 to 7.5 6.20 6.20 6.10
Pourability 95% min. 98.80 98.20 97.50
Specific gravity 1.00-1.05 1.01 1.01 1.01
Viscosity at spindle no. 62, 20 rpm 350-800 cps 640 670 690
Particle size (micron) D50<3, D90<10 2.1,8.3 2.2,8.4 2.3,8.7
Persistent foam ml (after 1 minute) max. 60 nil 1 1

The novel OD formulation compound of Formula I 3%+Cyantraniliprole 8% OD (Recipe A-Novel OD) meets the all inhouse specifications for storage stability studies in laboratory (at 54±2 C & At 0±2 C for 14 days) and room temperature (for 12 months).

EXAMPLE 6:
Tert-butyl4-[[(E)-(1,3-dimethyl-5-phenoxypyrazol-4-yl)methylideneamino]oxymethyl ]benzoate [compound of Formula I] 3%+Cyantraniliprole 8% OD (Recipe B-Novel OD)
Ingredients Percent (w/w)
compound of Formula I a.i. 3.00
Cyantraniliprole a.i. 8.00
Dispersing agent-Tristyrylphenol-polyglycolether-phosphate 4.50
Emulsifier-Octylphenol ethoxylate 8.00
Stabilizer-Bentonite clay 2.00
Antifoam-Polydimethyl siloxane 0.30
Preservative-1,2-benzisothiazolin-3(2H)-one 0.20
Antifreezing agent-Polypropylene glycol 5.00
Buffering agent-citric acid 0.15
Wetting agent-Polyalkyleneoxide modified Heptamethyltrisiloxane 4.00
Solvent-Methyl ester of Mahuva oil and soybean oil 64.85
Total 100.00

Storage stability study: compound of Formula I 3%+Cyantraniliprole 8% OD (Recipe B-Novel OD)
Storage stability- compound of Formula I 3%+Cyantraniliprole 8% OD (Recipe B-Novel OD)
Laboratory storage for 14 days
Parameters Specification (in house) Initial At 54±2 0C At 0±2 0C
compound of Formula I content percent by mass 2.85 to 3.30 3.25 3.15 3.23
Cyantraniliprole content percent by mass 7.60 to 8.80 8.60 8.25 8.50
compound of Formula I suspensibility percent min. 80 98.80 98.00 98.40
Cyantraniliprole suspensibility percent min. 80 98.80 97.80 98.00
pH range (1% aq. Suspension) 5.0 to 7.5 6.20 6.10 6.15
Pourability 95% min. 98.80 97.50 98.50
Specific gravity 1.00-1.05 1.01 1.01 1.01
Viscosity at spindle no. 62, 20 rpm 350-800 cps 640 680 660
Particle size (micron) D50<3, D90<10 2.1,8.3 2.3,8.5 2.4,8.7
Persistent foam ml (after 1 minute) max. 60 nil 1 1
Room temperature storage
Parameters Specification (in house) 1 month 6 months 12 months
compound of Formula I content percent by mass 2.85 to 3.30 3.25 3.22 3.19
Cyantraniliprole content percent by mass 7.60 to 8.80 8.45 8.35 8.30
compound of Formula I suspensibility percent min. 80 98.80 98.40 98.00
Cyantraniliprole suspensibility percent min. 80 98.80 98.40 98.00
pH range (1% aq. Suspension) 5.0 to 7.5 6.20 6.10 6.00
Pourability 95% min. 98.80 98.40 97.60
Specific gravity 1.00-1.05 1.01 1.01 1.01
Viscosity at spindle no. 62, 20 rpm 350-800 cps 640 660 680
Particle size (micron) D50<3, D90<10 2.1,8.3 2.2, 8.4 2.3, 8.5
Persistent foam ml (after 1 minute) max. 60 nil 1 nil

The novel OD formulation recipe of compound of Formula I 3%+Cyantraniliprole 8% OD (Recipe B-Novel OD) meets the all inhouse specifications for storage stability studies in laboratory (at 54±2 C & At 0±2 C for 14 days) and room temperature (for 12 months).
EXAMPLE 7:
Tert-butyl4-[[(E)-(1,3-dimethyl-5-phenoxypyrazol-4-yl)methylideneamino]oxymethyl ]benzoate [compound of Formula I] 3%+Cyantraniliprole 8% OD (Recipe C-Novel OD)
Ingredients Percent (w/w)
compound of Formula I a.i. 3.00
Cyantraniliprole a.i. 8.00
Dispersing agent-Tristyrylphenol-polyglycolether-phosphate 4.50
Emulsifier-Octylphenol ethoxylate 8.00
Stabilizer-Bentonite clay 2.00
Antifoam-Polydimethyl siloxane 0.30
Preservative-1,2-benzisothiazolin-3(2H)-one 0.20
Antifreezing agent-Polypropylene glycol 5.00
Buffering agent-citric acid 0.15
Wetting agent-Polyalkyleneoxide modified Heptamethyltrisiloxane 5.00
Solvent-Methyl ester of Karanj oil and rape seed oil 63.85
Total 100.00

Storage stability study: compound of Formula I 3%+Cyantraniliprole 8% OD (Recipe C-Novel OD)
Storage stability- compound of Formula I 3%+Cyantraniliprole 8% OD (Recipe C-Novel OD)
Laboratory storage for 14 days
Parameters Specification (in house) Initial At 54±2 0C At 0±2 0C
compound of Formula I content percent by mass 2.85 to 3.30 3.25 3.12 3.22
Cyantraniliprole content percent by mass 7.60 to 8.80 8.60 8.40 8.20
compound of Formula I suspensibility percent min. 80 98.80 97.50 98.20
Cyantraniliprole suspensibility percent min. 80 98.60 97.20 98.00
pH range (1% aq. Suspension) 5.0 to 7.5 6.20 6.00 6.10
Pourability 95% min. 99.00 97.50 98.20
Specific gravity 1.00-1.05 1.01 1.01 1.01
Viscosity at spindle no. 62, 20 rpm 350-800 cps 650 720 680
Particle size (micron) D50<3, D90<10 2.2,8.5 2.6,8.8 2.4,8.6
Persistent foam ml (after 1 minute) max. 60 nil 2 nil
Room temperature storage
Parameters Specification (in house) 1 month 6 months 12 months
compound of Formula I content percent by mass 2.85 to 3.30 3.25 3.23 3.20
Cyantraniliprole content percent by mass 7.60 to 8.80 8.60 8.55 8.50
compound of Formula I suspensibility percent min. 80 98.60 98.00 97.50
Cyantraniliprole suspensibility percent min. 80 98.40 97.80 97.20
pH range (1% aq. Suspension) 5.0 to 7.5 6.20 6.10 6.00
Pourability 95% min. 98.80 98.00 97.40
Specific gravity 1.00-1.05 1.01 1.01 1.01
Viscosity at spindle no. 62, 20 rpm 350-800 cps 650 680 720
Particle size (micron) D50<3, D90<10 2.3,8.5 2.5,8.6 2.6,8.8
Persistent foam ml (after 1 minute) max. 60 nil 2 2

The novel OD formulation recipe of compound of Formula I 3%+Cyantraniliprole 8% OD (Recipe C-Novel OD) meets the all inhouse specifications for storage stability studies in laboratory (at 54±2 C & At 0±2 C for 14 days) and room temperature (for 12 months).
Conventional OD Recipe:
Fenpyroximate 3%+Cyantraniliprole 8% OD (Conventional OD Recipe)
Ingredients Percent (w/w)
Fenpyroximate a.i. 3.00
Cyantraniliprole a.i. 8.00
Dodecyl benzene sulphonate in methylated and ethoxylated seed oil 25.00
Polyoxyethylene sorbitol fatty acid 5.00
Tristyrylphenol-polyglycolether-phosphate 5.00
Fumed silica 1.31
Citric acid 0.02
Propylene glycol 5.00
1,2-benzisothiazolin-3(2H)-one 0.20
Methylated seed oil 47.47
Total 100.00

Storage stability- Fenpyroximate 3%+Cyantraniliprole 8% OD (Conventional OD Recipe)
Storage stability-Fenpyroximate 3%+Cyantraniliprole 8% OD (Conventional OD Recipe)
Laboratory storage for 14 days
Parameters Specification (in house) Initial At 54±2 0C At 0±2 0C
Fenpyroximate content percent by mass 2.85 to 3.30 3.25 3.05 3.12
Cyantraniliprole content percent by mass 7.60 to 8.80 8.60 8.10 8.40
Fenpyroximate suspensibility percent min. 80 98.80 97.60 98.20
Cyantraniliprole suspensibility percent min. 80 98.80 97.40 98.00
pH range (1% aq. Suspension) 5.0 to 7.5 6.10 6.00 5.90
Pourability 95% min. 98.50 93.50 95.10
Specific gravity 1.00-1.05 1.01 1.01 1.01
Viscosity at spindle no. 62, 20 rpm 350-800 cps 660 810 690
Particle size (micron) D50<3, D90<10 2.2,8.6 4.9,12.7 2.8, 8.8
Persistent foam ml (after 1 minute) max. 60 nil 3 nil
Room temperature storage
Parameters Specification (in house) 1 month 6 months 12 months
Fenpyroximate content percent by mass 2.85 to 3.30 3.25 3.12 3.05
Cyantraniliprole content percent by mass 7.60 to 8.80 8.60 8.40 8.10
Fenpyroximate suspensibility percent min. 80 98.80 97.40 96.00
Cyantraniliprole suspensibility percent min. 80 98.80 97.20 95.40
pH range (1% aq. Suspension) 5.0 to 7.5 6.10 6.00 5.90
Pourability 95% min. 98.50 95.50 94.20
Specific gravity 1.00-1.05 1.01 1.01 1.02
Viscosity at spindle no. 62, 20 rpm 350-800 cps 670 750 790
Particle size (micron) D50<3, D90<10 2.2,8.6 2.8, 10.2 3.9, 13.4
Persistent foam ml (after 1 minute) max. 60 nil 4 5

Storage stability of Fenpyroximate 3%+Cyantraniliprole 8% OD (Conventional OD recipe) does not meet the pourability and particle size criteria during 14 days Laboratory storage and 12 months room storage. This will results in wastage of material while handling the product and uneven distribution of active ingredients while spraying in the field.

EXPERIMENT 3:
EXAMPLE 8:
Tert-butyl4-[[(E)-(1,3-dimethyl-5-phenoxypyrazol-4-yl)methylideneamino]oxymethyl ]benzoate [compound of Formula I] 4%+Hexythiazox 4% OD (Recipe-1-Novel OD)
Ingredients Percent (w/w)
compound of Formula I a.i. 4.00
Hexythiazox a.i. 4.00
Dispersing agent-Tristyrylphenol-polyglycolether-phosphate 4.50
Emulsifier-Octylphenol ethoxylate 8.00
Stabilizer-Bentonite clay 3.00
Antifoam-Polydimethyl siloxane 0.30
Preservative-1,2-benzisothiazolin-3(2H)-one 0.20
Antifreezing agent-Polypropylene glycol 5.00
Buffering agent-citric acid 0.15
Wetting agent-Polyalkyleneoxide modified Heptamethyltrisiloxane 5.00
Solvent-Methyl ester of Karanj oil 65.85
Total 100.00

Storage stability- compound of Formula I 4%+Hexythiazox 4% OD (Recipe-1-Novel OD)
Storage stability- compound of Formula I 4%+Hexythiazox 4% OD (Recipe-1-Novel OD)
Laboratory storage for 14 days
Parameters Specification (in house) Initial At 54±2 0C At 0±2 0C
compound of Formula I content percent by mass 3.80 to 4.40 4.25 4.10 4.23
Hexythiazox content percent by mass 3.80 to 4.40 4.24 4.11 4.23
compound of Formula I suspensibility percent min. 80 98.80 98.20 98.60
Hexythiazox suspensibility percent min. 80 98.80 97.60 97.80
pH range (1% aq. Suspension) 5.0 to 7.5 6.20 6.15 6.15
Pourability 95% min. 98.80 97.60 98.50
Specific gravity 1.00-1.05 1.01 1.01 1.01
Viscosity at spindle no. 62, 20 rpm 350-800 cps 640 670 660
Particle size (micron) D50<3, D90<10 2.1,8.3 2.5,8.7 2.4,8.6
Persistent foam ml (after 1 minute) max. 60 nil 1 nil
Room temperature storage
Parameters Specification (in house) 1 month 6 months 12 months
compound of Formula I content percent by mass 3.80 to 4.40 4.25 4.22 4.20
Hexythiazox content percent by mass 3.80 to 4.40 4.24 4.21 4.19
compound of Formula I suspensibility percent min. 80 98.80 98.40 98.00
Hexythiazox suspensibility percent min. 80 98.80 98.20 97.80
pH range (1% aq. Suspension) 5.0 to 7.5 6.20 6.20 6.15
Pourability 95% min. 98.80 98.20 97.50
Specific gravity 1.00-1.05 1.01 1.01 1.01
Viscosity at spindle no. 62, 20 rpm 350-800 cps 640 670 690
Particle size (micron) D50<3, D90<10 2.1,8.3 2.2,8.4 2.3,8.7
Persistent foam ml (after 1 minute) max. 60 nil 1 1

The novel OD formulation compound of Formula I 4 %+Hexythiazox 4% OD (Recipe A-Novel OD) meets the all inhouse specifications for storage stability studies in laboratory (at 54±2 C & At 0±2 C for 14 days) and room temperature (for 12 months).
EXAMPLE 9:
Lists of preferred combinations of Novel non aqueous formulation:
Compound A Compound B Active ingredients (%) Formulation Strength (%)
Compound A Compound B
compound Formula I Etoxazole 6 10 16.00
compound Formula I Hexythiazox 4 4 8.00
compound Formula I Abamectin 3 2 5.00
compound Formula I Cyenopyrafen 3 10 13.00
compound Formula I Spiromesifen 4 15 19.00
compound Formula I Spirodiclofen 4 15 19.00
compound Formula I Spirotetramat 4 15 19.00
compound Formula I Spiropidion 4 12 16.00
compound Formula I Spidoxamat 4 12 16.00
compound Formula I Diafenthiuron 2.4 25 27.40
compound Formula I Bifenazate 2.4 16 18.40
compound Formula I Bifenthrin 2.4 8 10.40
compound Formula I Lambda cyhalothrin 6 8 14.00
compound Formula I Chlorantraniliprole 3 4 7.00
compound Formula I Cyantraniliprole 3 8 11.00
compound Formula I Tetraniliprole 3 8 11.00
compound Formula I Cyclaniliprole 3 8 11.00
compound Formula I Broflanilide 6 3 9.00
compound Formula I Fluxametamide 6 3 9.00
compound Formula I Clothianidin 6 8 14.00
compound Formula I Thiamethoxam 6 8 14.00
compound Formula I Dinotefuran 6 8 14.00
compound Formula I Flonicamid 3 8 11.00
compound Formula I Chlorfenpyr 3 10 13.00
compound Formula I Cyflumetofen 1.5 10 11.50
compound Formula I Dicofol 1.5 20 21.50
compound Formula I Fenazaquin 1.5 7.5 9.00
compound Formula I Flufenzine 1.5 7.5 9.00
compound Formula I Flufenoxuron 3 7.5 10.50
compound Formula I Milbemectin 3 0.6 3.60
compound Formula I Propargite 1.5 30 31.50
compound Formula I Pyridaben 1.5 7.5 9.00

Compound A Compound B Compound C Active ingredients (%) Formulation Strength (%)
Compound A Compound B Compound C
compound Formula I Etoxazole Gibberellic acid 6 10 1 17.00
compound Formula I Hexythiazox Gibberellic acid 6 5 1 12.00
compound Formula I Cyenopyrafen Gibberellic acid 3 10 0.5 13.50
compound Formula I Spiromesifen Gibberellic acid 3 15 0.5 18.50
compound Formula I Spirodiclofen Gibberellic acid 3 15 0.5 18.50
compound Formula I Spirotetramat Gibberellic acid 3 15 0.5 18.50
compound Formula I Spiropidion Gibberellic acid 3 12 0.5 15.50
compound Formula I Spidoxamat Gibberellic acid 3 12 0.5 15.50
compound Formula I Diafenthiuron Gibberellic acid 2.4 25 0.4 27.80
compound Formula I Bifenazate Gibberellic acid 2.4 16 0.4 18.80
compound Formula I Bifenthrin Gibberellic acid 2.4 8 0.4 10.80
compound Formula I Lambda cyhalothrin Gibberellic acid 6 8 1 15.00
compound Formula I Chlorantraniliprole Gibberellic acid 3 4 0.4 7.40
compound Formula I Cyantraniliprole Gibberellic acid 3 10 0.4 13.40
compound Formula I Tetraniliprole Gibberellic acid 3 8 0.4 11.40
compound Formula I Cyclaniliprole Gibberellic acid 3 8 0.4 11.40
compound Formula I Broflanilide Gibberellic acid 6 3 0.8 9.80
compound Formula I Fluxametamide Gibberellic acid 6 3 0.8 9.80
compound Formula I Clothianidin Gibberellic acid 6 8 0.8 14.80
compound Formula I Thiamethoxam Gibberellic acid 6 8 0.8 14.80
compound Formula I Dinotefuran Gibberellic acid 6 8 0.8 14.80
compound Formula I Flonicamid Gibberellic acid 3 8 0.4 11.40
compound Formula I Etoxazole Paclobutrazol 2.4 4 8 14.40
compound Formula I Hexythiazox Paclobutrazol 2.4 2 8 12.40
compound Formula I Cyenopyrafen Paclobutrazol 2.4 8 8 18.40
compound Formula I Spiromesifen Paclobutrazol 2.4 12 8 22.40
compound Formula I Spirodiclofen Paclobutrazol 2.4 12 8 22.40
compound Formula I Spirotetramat Paclobutrazol 2.4 12 8 22.40
compound Formula I Spiropidion Paclobutrazol 2.4 9.6 8 20.00
compound Formula I Spidoxamat Paclobutrazol 2.4 9.6 8 20.00
compound Formula I Diafenthiuron Paclobutrazol 1.2 12.5 4 17.70
compound Formula I Bifenazate Paclobutrazol 2.4 16 8 26.40
compound Formula I Bifenthrin Paclobutrazol 2.4 8 8 18.40
compound Formula I Lambda cyhalothrin Paclobutrazol 2.4 3.2 8 13.60
compound Formula I Chlorantraniliprole Paclobutrazol 2.4 4 8 14.40
compound Formula I Cyantraniliprole Paclobutrazol 2.4 10 8 20.40
compound Formula I Tetraniliprole Paclobutrazol 2.4 8 8 18.40
compound Formula I Cyclaniliprole Paclobutrazol 2.4 8 8 18.40
compound Formula I Broflanilide Paclobutrazol 4.8 3 16 23.80
compound Formula I Fluxametamide Paclobutrazol 4.8 3 16 23.80
compound Formula I Clothianidin Paclobutrazol 2.4 4 8 14.40
compound Formula I Thiamethoxam Paclobutrazol 2.4 4 8 14.40
compound Formula I Dinotefuran Paclobutrazol 2.4 4 8 14.40
compound Formula I Flonicamid Paclobutrazol 2.4 8 8 18.40
compound Formula I Etoxazole Fulvic acid 2.4 4 4 10.40
compound Formula I Hexythiazox Fulvic acid 2.4 2 4 8.40
compound Formula I Cyenopyrafen Fulvic acid 2.4 8 4 14.40
compound Formula I Spiromesifen Fulvic acid 2.4 12 4 18.40
compound Formula I Spirodiclofen Fulvic acid 2.4 12 4 18.40
compound Formula I Spirotetramat Fulvic acid 2.4 12 4 18.40
compound Formula I Spiropidion Fulvic acid 2.4 9.6 4 16.00
compound Formula I Spidoxamat Fulvic acid 2.4 9.6 4 16.00
compound Formula I Diafenthiuron Fulvic acid 1.2 12.5 2 15.70
compound Formula I Bifenazate Fulvic acid 2.4 16 4 22.40
compound Formula I Bifenthrin Fulvic acid 2.4 8 4 14.40
compound Formula I Lambda cyhalothrin Fulvic acid 2.4 3.2 4 9.60
compound Formula I Chlorantraniliprole Fulvic acid 2.4 4 4 10.40
compound Formula I Cyantraniliprole Fulvic acid 2.4 10 4 16.40
compound Formula I Tetraniliprole Fulvic acid 2.4 8 4 14.40
compound Formula I Cyclaniliprole Fulvic acid 2.4 8 4 14.40
compound Formula I Broflanilide Fulvic acid 4.8 3 8 15.80
compound Formula I Fluxametamide Fulvic acid 4.8 3 8 15.80
compound Formula I Clothianidin Fulvic acid 2.4 4 4 10.40
compound Formula I Thiamethoxam Fulvic acid 2.4 4 4 10.40
compound Formula I Dinotefuran Fulvic acid 2.4 4 4 10.40
compound Formula I Abamectin Cyantraniliprole 2 1.2 8 11.20
compound Formula I Abamectin Broflanilide 2 1.2 1.2 4.40
compound Formula I Abamectin Fluxametamide 2 1.2 1.2 4.40
compound Formula I Hexythiazox Cyantraniliprole 2 3 8 13.00
compound Formula I Hexythiazox Broflanilide 2 3 1.2 6.20
compound Formula I Hexythiazox Fluxametamide 2 3 1.2 6.20
compound Formula I Etoxazole Cyantraniliprole 2 4 8 14.00
compound Formula I Etoxazole Broflanilide 2 4 1.2 7.20
compound Formula I Etoxazole Fluxametamide 2 4 1.2 7.20
compound Formula I Hexythiazox Abamectin 2 4 1.2 7.20
compound Formula I Hexythiazox Abamectin 2 4 1.2 7.20
compound Formula I Hexythiazox Abamectin 2 4 1.2 7.20
compound Formula I Tolfenpyrad Cyantraniliprole 1.2 7.5 4 12.70

Biological Examples:
A synergistic effect exists wherever the action of a combination of active ingredient is greater than the sum of the action of each of the components alone. Therefore, a synergistically effective amount or an effective amount of a synergistic composition or combination is an amount that exhibits greater pesticidal activity than the sum of the pesticidal activities of the individual components.
In the field of agriculture, it is often understood that the term “synergy” is as defined by Colby S.R. in an article entitled “ Calculation of the synergistic and antagonistic responses of herbicide combinations” published in the journal Weeds, 1967, 15, p.20-22, incorporated herein by reference in its entirety. The action expected for a given combination of two or three active components can be calculated as follows:

Colby’s formula to check the synergism between three active ingredients.

FIELD BIO-EFFICACY STUDIES:
The novel non aqueous (OD) formulation of compound of Formula I with different insecticide, fungicides and plant health additives has been developed in the laboratory and evaluated for its efficacy, residual control and rain-fast action in comparison with prior art formulations and tank mixes.

Experiment 1: Efficacy and residual control of Red spider mite (Tetranychus urticae) by Novel non aqueous (OD) formulation
Crop : Brinjal
Target insect : Red spider mite
Location : Umreth, Dist. Anand, Gujarat
Treatments : 7
Plot size : 40 sq.m.
Crop age : 75 days after transplanting.
Spray water volume : 450 liter per hectare
Method of Application: Foliar spray with battery operated knapsack sprayer fitted with hollow cone nozzle.
Agronomic Practices : All agronomic practices followed as per the crop requirement.
Observation Methods:
Red spider mite (%):
Count the number of live/motile stages of red spider mite per spot. Record the observations from 10 spots per plant and 5 plants per plot. Record the observations at 3, 7, 10 and 14 days after spraying.

% Red spider mite control data (as observed value) were used to check the synergism by applying Colby’s formula given above.
Table 1: Treatment details
Treatment Number Treatment details Use rate (gai/h)
T1 compound Formula I 6%+Etoxazole 10% OD (Recipe-1-Novel OD), 12+20 gai/h
T2 Fenpyroximate 6%+Etoxazole 10% SC (conventional formulation), 12+20 gai/h
T3 Fenpyroximate 6%+Etoxazole 10% WG (conventional formulation), 12+20 gai/h
T4 Fenpyroximate 5% EC+Etoxazole 10% SC (tank mix), 12 gai/h+20 gai/h
T5 Fenpyroximate 5% EC, 12 gai/h
T6 Etoxazole 10% SC, 20 gai/h
T7 UTC (Untreated Check)
*Novel OD formulation recipes.

Table 2: Bio efficacy and residual control of Red spider mite by Novel non aqueous (OD) formulation
Treatment Number % Red spider mite
3 DAA 7 DAA 10 DAA 14 DAA
OV CV Colby's ratio Synergism (Y/N) OV CV Colby's ratio Synergism (Y/N) OV CV Colby's ratio Synergism (Y/N) OV CV Colby's ratio Synergism (Y/N)
T1 97.4 88.74 1.10 Y 97.0 86.97 1.12 Y 93.6 80.73 1.16 Y 90.2 72.99 1.24 Y
T2 93.2 88.74 1.05 Y 90.6 86.97 1.04 Y 80.2 80.73 0.99 Y 68.4 72.99 0.94 N
T3 91.2 88.74 1.03 Y 88.4 86.97 1.02 Y 77.6 80.73 0.96 N 63.6 72.99 0.87 N
T4 90.2 88.74 1.02 Y 85.2 86.97 0.98 Y 75.2 80.73 0.93 N 58.8 72.99 0.81 N
T5 68.2 64.6 55.8 46.4
T6 64.6 63.2 56.4 49.6
T7 0.0 0.0 0.0 0.0

The treatment number T1 to T4 shows synergism in terms of red spider mite control at 3 DAA (Days after application). The only novel OD formulation (T1) provides synergistic larval control (>90%) up to 14 DAA. The conventional treatments does not show synergism on 14 DAA. The novel OD formulations (T1) provides higher control as compared to all conventional treatment (T2, T3, T4) on 14 DAA.

Experiment 2: Field performance of different recipes of novel non aqueous (OD) formulation
Crop : Chilly
Target insects : Thrips (Scirtothrips dorsalis)
Location : Bochasan, Dist. Anand, Gujarat
Treatments : 7
Plot size : 30 sq.m.
Crop age : 82 days after transplanting.
Spray water : 440 liter per hectare
Method of Application: Foliar spray with battery operated knapsack sprayer fitted with hollow cone nozzle.
Agronomic Practices : Except insecticidal applications, all agronomic practices followed as per the crop requirement.
Observation Methods: same as given in Experiment 1.
Table 3: Treatment details for field performance of novel non aqueous (OD) formulation recipes.
Treatment Number Treatment details with Use Rate (gai/h)
T1 compound Formula I 3%+Cyantraniliprole 8% OD (Recipe A-Novel OD), 15+40 gai/h
T2 compound Formula I 3%+Cyantraniliprole 8% OD (Recipe B-Novel OD), 15+40 gai/h
T3 compound Formula I 3%+Cyantraniliprole 8% OD (Recipe C-Novel OD), 15+40 gai/h
T4 Fenpyroximate 3%+Cyantraniliprole 8% OD (Conventional OD Recipe), 15+40 gai/h
T5 Fenpyroximate 5% EC, 15 gai/h
T6 Cyantraniliprole 10.26% (10% w/v) OD, 40 gai/h
T7 UTC (Untreated Check)

Table 4: Field performance of novel non aqueous (OD) formulation recipes.
Treatment Number % Thrips control Increase in thrips control over T4 at 14 DAA
3 DAA 7 DAA 14 DAA
Obs. Value Cal. Value Colby's ratio Synergism (Y/N)
T1 94.6 86.77 1.09 Y 90.8 84.6 11.0 (T1-T4)
T2 95.2 86.77 1.10 Y 91.4 85.8 12.2 (T2-T4)
T3 93.8 86.77 1.08 Y 90.2 83.8 10.2 (T3-T4)
T4 90.2 86.77 1.04 Y 85.4 73.6
T5 60.4 55.2 46.2
T6 66.6 61.8 54.4
T7 0.00 0.00 0.00

Figure I of the present invention illustrates the filed study of the present experiment and results obtained therefrom in table 4 depicts that all the treatment (T1 to T4) shows synergism in terms of larval control at 3 DAA (Days after application). The observations on residual control shows that all the novel OD recipes (T1, T2 and T3) provides higher thrips control as compared to conventional OD recipe (T4) on 14 DAA.

Experiment 3: Dose response with novel non aqueous (OD) formulation
Crop : Okra
Target pests : Red spider mite
Location : Umreth, Dist. Anand, Gujarat
Treatments : 4
Plot size : 50 sq.m.
Crop age : 66 days after transplanting.
Spray water : 460 liter per hectare
Method of Application: Foliar spray with battery operated knapsack sprayer fitted with hollow cone nozzle.
Agronomic Practices : Except insecticidal applications, all agronomic practices followed as per the crop requirement.
Observation Methods: same as given in Experiment 1.
Table 5: Dose response of novel non aqueous (OD) formulation
Treatment Number Treatment details with application Rate (ml/h)
T1 compound Formula I 4%+Hexythiazox 4% OD (Recipe-1-Novel OD), 300 ml
T2 compound Formula I 4%+Hexythiazox 4% OD (Recipe-1-Novel OD), 250 ml
T3 Fenpyroximate 4%+Hexythiazox 5.45% EC (Conventional), 300 ml
T4 Fenpyroximate 4%+Hexythiazox 5.45% EC (Conventional), 250 ml

Table 6: Dose response of novel non aqueous (OD) formulation
Treatment Number Reduction in % larval control due to dose reduction
3 DAA 7 DAA 10 DAA 14 DAA 20 DAA
T1-T2 2.4 4.0 4.4 10.0 13.8
T3-T4 6.0 6.2 8.4 15.2 20.8

The bio-efficacy of novel non aqueous (OD) recipe of compound Formula I 4%+Hexythiazox 4% does not drop drastically when dose reduced from 300 ml/h to 250 ml/h (~16.67% dose reduction), where as the % mite control drop drastically (6%, 6.2%, 8.4%, 15.2% and 20.8% at 3,7, 10, 14 and 20 DAA respectively) in the conventional OD formulation. With novel OD formulation, we reduce the field use rate to achieve the desirable larval control.

Experiment 4: Synergistic control of thrips and mite in chilly crop
Crop : Chilly
Target insects : Thrips (Scirtothrips dorsalis), Yellow mite (Polyphagotarsonemus latus)
Location : Borsad, Dist. Anand, Gujarat
Treatments : 14
Plot size : 24 sq.m.
Crop age : 72 days after transplanting.
Spray water volume : 400 liter per hectare
Method of Application: Foliar spray with battery operated knapsack sprayer fitted with hollow cone nozzle.
Agronomic Practices : Except insecticidal applications, all agronomic practices followed as per the crop requirement.
Observation Methods:
Yellow mite (%): as given Experiment 1.
Thrips (%): Count the number of live thrips per twig by shaking the twigs on black color piece of paper on 5th day after application (DAA). Record the count from 3 twigs per plant and 5 plants per plot.
Fruit count: count the number of healthy marketable fruits per plant. Record the
Observations from 5 plants per plot on 14th day after application.
Leaf curling rating: Observe 10 plants per plot. Rate the individual plant by following
rating.
Scale on 14th DAA.
Rating Score Description for rating (Leaf curling symptoms due to Thrips and mite damage)
0 No leaf curling
1 1 to 10% leaves were curled.
2 11 to 20% leaves were curled.
3 21 to 40% leaves were curled. Little dropping of flowers and flower buds.
4 41 to 60% leaves were curled. Moderate dropping of flowers, flowers bud and young fruits. Fruits become twisted and abnormal shape. Little stunting of plant.
5 61 to 100% leaves were curled. Heavy dropping of flowers, flowers bud and young fruits. Fruits become twisted and abnormal shape. Plants become stunted.
Table 7: Treatment details
Treatment number Treatment details with application Rate (ml or g per Hectare)

T1 compound Formula I 3%+Abamectin 2% OD, 12+8 gai/h
T2 compound Formula I 3%+Cyenopyrafen 10% OD, 12+40 gai/h
T3 compound Formula I 2.4%+Diafenthiuron 25% OD, 12+125 gai/h
T4 compound Formula I 2.4%+Bifenazate 16% OD, 12+80 gai/h
T5 compound Formula I 2.4%+Bifenthrin 8% OD, 12+40 gai/h
T6 compound Formula I 6%+Lambda cyhalothrin 8% OD, 12+16 gai/h
T7 Fenpyroximate 5% EC, 12 gai/h
T8 Abamectin 1.9% EC, 8 gai/h
T9 Cyenopyrafen 30% SC, 40 gai/h
T10 Diafenthiuron 47.8% SC, 125 gai/h
T11 Bifenazate 22.6% SC, 80 gai/h
T12 Bifenthrin 10% EC, 40 gai/h
T13 Lambda cyhalothrin 4.9% CS, 16 gai/h
T14 UTC (Untreated Check)
*T1 to T6 were novel OD formulation.
Table 8: Synergistic control of thrips and mites in chilly.
Treatment number % Mite control at 5 DAA % Thrips control at 5 DAA Leaf curling Rating at 14 DAA Number of fruits/plant at 14 DAA
Obs. Value Cal. Value Colby's ratio Synergism (Y/N) Obs. Value Cal. Value Colby's ratio Synergism (Y/N)
T1 96.4 90.11 1.07 Y 94.6 85.94 1.10 Y 0.6 44.8
T2 94.8 89.69 1.06 Y 88.2 82.53 1.07 Y 1.2 40.4
T3 93.6 87.65 1.07 Y 91.2 86.55 1.05 Y 0.8 41.2
T4 92.4 88.65 1.04 Y 87.8 85.74 1.02 Y 1.4 39.8
T5 93.6 86.12 1.09 Y 88.8 84.93 1.05 Y 0.8 38.4
T6 92.2 85.19 1.08 Y 89.2 86.34 1.03 Y 1.2 39.2
T7 70.2 58.4 2.4 31.6
T8 66.8 66.2 2.2 34.8
T9 65.4 58.0 3.2 28.6
T10 62.8 60.2 3.0 28.4
T11 65.8 57.8 3.2 27.5
T12 58.2 55.4 2.6 26.9
T13 55.4 59.6 2.8 27.3
T14 0.00 0.00 4.0 17.8

The novel non aqueous (OD) formulations of Fenpyroximate with different insecticides (T1 to T6) provides synergistic control of thrips and yellow mite in chilly crop. Also produces higher number of green marketable fruits.

Experiment 5: Synergistic control of mite in marigold (flower crop)
Crop : Marigold
Target insects : Red spider mite
Location : Ode, Gujarat
Treatments : 14
Plot size : 20 sq.m.
Crop age : 80 days after transplanting.
Spray water volume : 500 liter per hectare
Method of Application: Foliar spray with battery operated knapsack sprayer fitted with hollow cone nozzle.
Agronomic Practices : Except insecticidal applications, all agronomic practices followed as per the crop requirement.
Observation Methods:
Red spider mite (%): as given Experiment 1.
Table 9: Treatment details
Treatment number Treatment details with application Rate (ml or g per Hectare)

T1 compound Formula I 4%+Spiromesifen 15% OD, 16+60 gai/h
T2 compound Formula I 4%+Spirodiclofen 15% OD, 16+60 gai/h
T3 compound Formula I 4%+Spirotetramat 15% OD, 16+60 gai/h
T4 compound Formula I 4%+Spiropidion 12% OD, 16+48 gai/h
T5 compound Formula I 3.2%+Chlorfenpyr 10% OD, 16+50 gai/h
T6 compound Formula I 1.6%+Fenazaquin 7.5% OD, 16+75 gai/h
T7 Fenpyroximate 5% EC, 16 gai/h
T8 Spiromesifen 22.9% SC, 60 gai/h
T9 Spirodiclofen 24% SC, 60 gai/h
T10 Spirotetramat 15.31% OD, 60 gai/h
T11 Spiropidion 20% SC, 48 gai/h
T12 Chlorfenpyr 10% SC, 50 gai/h
T13 Fenazaquin 10% EC, 75 gai/h
T14 UTC (Untreated Check)
T1 to T6 were Novel non aqueous (OD) formulation
Table 10: Control of red spider mite in marigold
Treatment number % Mite control at 5 DAA
Obs. Value Cal. Value Colby's ratio Synergism (Y/N)
T1 92.6 80.95 1.14 Y
T2 95.4 82.44 1.16 Y
T3 86.0 77.28 1.11 Y
T4 90.6 79.66 1.14 Y
T5 93.8 81.77 1.15 Y
T6 97.4 82.96 1.17 Y
T7 58.4
T8 54.2
T9 57.8
T10 50.4
T11 55.6
T12 60.2
T13 62.8
T14 0.00

All the novel OD formulations of Fenpyroximate+Insecticides provides synergistic control of red spider mite in marigold crop.

Experiment 6: Synergistic control of thrips and mite in chilly crop
Crop : Chilly
Target insects : Thrips (Scirtothrips dorsalis), Yellow mite (Polyphagotarsonemus latus)
Location : Borsad, Dist. Anand, Gujarat
Treatments : 16
Plot size : 20 sq.m.
Crop age : 75 days after transplanting.
Spray water volume : 420 liter per hectare
Method of Application: Foliar spray with battery operated knapsack sprayer fitted with hollow cone nozzle.
Agronomic Practices : Except insecticidal applications, all agronomic practices followed as per the crop requirement.
Observation Methods:
Yellow mite (%) at 7 DAA: as given in Experiment 4.
Thrips (%) at 7 DAA: as given in Experiment 4.
Table 11: Treatment details
Treatment Number Treatment details Rate (gai/h)
T1 compound Formula I 2%+Abamectin 1.2%+Cyantraniliprole 8% OD 10+6+40
T2 compound Formula I 2%+Abamectin 1.2%+Broflanilide 1.2% OD 10+6+6
T3 compound Formula I 2%+Hexythiazox 3%+Cyantraniliprole 8% OD 10+15+40
T4 compound Formula I 2%+Hexythiazox 3%+Broflanilide 1.2% OD 10+15+6
T5 Fenpyroximate 5% EC+Abamectin 1.9% EC 10+6
T6 Fenpyroximate 5% EC+Hexythiazox 5% SC 10+15
T7 Abamectin 1.9% EC+Cyantraniliprole 10.26% OD 6+40
T8 Abamectin 1.9% EC+Broflanilide 30% SC 6+6
T9 Hexythiazox 5.45% EC+Cyantraniliprole 10.26% OD 15+40
T10 Hexythiazox 5.45% EC +Broflanilide 30% SC 15+6
T11 Fenpyroximate 5% EC 10
T12 Abamectin 1.9% EC 6
T13 Hexythiazox 5.45% EC 15
T14 Cyantraniliprole 10.26% OD 40
T15 Broflanilide 30% SC 6
T16 UTC (Untreated Check) 0

Table 12: Control of yellow mite and thrips in chilly crop
Treatment Number Thrips control (%) at 7 DAA Yellow mite control (%) at 7 DAA
Obs. Value Exp. Value Ratio O/E Synergism (Y/N) Obs. Value Exp. Value Ratio O/E Synergism (Y/N)
T1 86.8 81.05 1.07 Y 96.2 91.85 1.05 Y
T2 85.4 81.47 1.05 Y 93.4 91.56 1.02 Y
T3 86.8 81.58 1.06 Y 91.2 86.73 1.05 Y
T4 87.4 81.99 1.07 Y 92.6 86.26 1.07 Y
T5 76.2 76.72 0.99 Y 77.8 79.52 0.98 Y
T6 75.8 77.37 0.98 N 65.4 66.65 0.98 N
T7 64.6 65.16 0.99 N 80.6 81.13 0.99 N
T8 65.6 66.14 0.99 N 68.2 69.27 0.98 N
T9 65.2 66.14 0.99 N 68.6 69.27 0.99 N
T10 64.8 66.89 0.97 N 67.4 68.19 0.99 N
T11 45.6 56.8
T12 57.2 52.6
T13 58.4 22.8
T14 18.6 60.2
T15 20.4 58.8
T16 0.0 0.0

All the Novel non aqueous (OD) formulation combinations of compound Formula I (T1 to T4) provides excellent synergistic control of chilly yellow mite and thrips even at 7 DAA (days after application).
Experiment 7: Synergistic control of thrips and mite in Capsicum chilly
Crop : Capsicum Chilly
Target insects : Thrips (Thrips parvispinus), Yellow mite (Polyphagotarsonemus latus)
Location : Umreth, Dist. Anand, Gujarat
Treatments : 7
Plot size : 40 sq.m.
Crop age : 50 days after transplanting.
Spray water volume : 400 liter per hectare
Method of Application: Foliar spray with battery operated knapsack sprayer fitted with hollow cone nozzle.
Observation Methods: Same as given in Experiment 4.
Table 13: Treatment details
Treatment Number Treatment details Rate (gai/h)
T1 compound Formula I 1.2%+Tolfenpyrad 7.5%+Cyantraniliprole 4% OD 12+75+40
T2 Fenpyroximate 5% EC+Tolfenpyrad 15% EC 12+75
T3 Tolfenpyrad 15% EC+Cyantraniliprole 10.26% OD 75+40
T4 Fenpyroximate 5% EC 12
T5 Tolfenpyrad 15% EC 75
T6 Cyantraniliprole 10.26% OD 40
T7 UTC (Untreated Check) 0

Table 14: Synergistic control of Thrips and mite in capsicum chilly.
Treatment Number Thrips control (%) at 7 DAA Yellow mite control (%) at 7 DAA
Obs. Value Exp. Value Ratio O/E Synergism (Y/N) Obs. Value Exp. Value Ratio O/E Synergism (Y/N)
T1 98.4 91.31 1.08 Y 97.2 89.01 1.09 Y
T2 74.6 79.88 0.93 Y 80.6 84.65 0.95 Y
T3 78.2 82.89 0.94 N 60.4 67.49 0.89 N
T4 49.2 66.2
T5 60.4 54.6
T6 56.8 28.4
T7 0.0 0.0

The novel non aqueous (OD) compound Formula I 1.2%+Tolfenpyrad 7.5%+Cyantraniliprole 4% OD provides synergistic residual control of Thirps and mites in Capsicum chilly.

Overall summery of field trials:
The field trials results shows many benefits/advantages of novel non aqueous (OD) formulations of compound of Formula I.
• Novel OD formulation shows synergism between compound Formula I and insecticide
• Novel OD formulation of compound Formula I with insecticide shows strong synergism in comparison to their conventional formulations.
• Novel OD formulation of compound Formula I with insecticide provides longer residual control in comparison to their conventional formulations. The longer residual control experienced due to improved spreading properties of spray solution over leaf surface, increase in penetration in to the leaf surface. Addition of Polyalkyleneoxide modified Heptamethyltrisiloxane as wetting agent and palm oil and karanj oil as carrier cum solvent improves the wetting, spreading and penetration properties of novel OD formulation of Emamectin benzoate with insecticide.
• Novel OD formulation of compound Formula I +insecticide, we can reduce the doses of active ingredients to get desirable insect control and thereby minimizing the pesticidal load into the environment.
• The improved rain fastness properties of novel OD formulation of compound of Formula I + insecticide experienced due to better retention of spray solution over the leaf surface.
• The novel OD formulations meets all the inhouse parameters of storage stability studies.
Spreading properties study:
Method: Spreading properties test conducted by preparing 1% solution (1 ml formulation in 100 ml water). Drop the solution on leaf surface and measure the spreading diameter (mm) after 30 seconds. Spreading diameter measured by graph paper.

Table 1: Spreading properties of Novel non aqueous (OD) formulation of compound Formula I 6%+Etoxazole 10%
Recipes Room temperature storage
1 month 6 months 12 months
(Spreading diameter in mm)
compound Formula I 6%+Etoxazole 10% OD (Recipe-1-Novel OD) 24 22 21
compound Formula I 6%+Etoxazole 10% OD (Recipe-2-Novel OD) 23 20 19
compound Formula I 6%+Etoxazole 10% OD (Recipe-3-Novel OD) 24 21 18
Fenpyroximate 2.4%+Etoxazole 10% SC (conventional formulation) 11 9 8
Fenpyroximate 4.8%+Etoxazole 20% WG (conventional formulation) 5 4 2

All the recipes of novel non aqueous (OD) formulations of compound Formula I 6%+Etoxazole 10% shows excellent spreading properties. This will improves the bio-efficacy under field condition, ensures quick control of target insect-pests and also improves the rain-fast properties during rainy days.

Table 2: Spreading properties of Novel non aqueous (OD) formulation of compound of Formula I 4%+Hexythiazox 4%
Formulations Room temperature storage
1 month 6 months 12 months
(Spreading diameter in mm)
compound Formula I 4%+Hexythiazox 4% OD 23 22 22
Fenpyroximate 4%+Hexythiazox 4% EC (conventional formulation) 13 12 9

The novel non aqueous (OD) formulation of compound Formula I 4%+Hexythiazox 4% OD shows excellent spreading properties as compared to their conventional formulations. This will improves the bio-efficacy under field condition, ensures quick control of target insect-pests and also improves the rainfast properties during rainy days.