Description:A FUNGICIDAL COMPOSITION
FIELD OF THE INVENTION:
The present invention relates to a stable, synergistic fungicidal composition comprising Mandipropamid, Dimethomorph and Soy protein, for control of fungal pests in various agricultural crops. The present invention further relates to a process for preparing the fungicidal composition.
BACKGROUND OF THE INVENTION:
Achieving production of high-quality, nutritional crops with efficient yield, amidst the rampant onslaught of pest infestation in crops, is a priority for farmers. Thus, providing optimal growth conditions for plants under existing field conditions and protecting them from damage by pests including weeds, insects and fungal pathogenic microorganisms is incumbent on farmers. Plant diseases result in an annual estimated loss of 10-15% of the world's major crops, with direct economic losses, 70-80% of plant diseases are caused by pathogenic fungi.
The main issue with using fungicides is the emergence of pest resistance to that specific fungicide, necessitating the use of a more concentrated fungicide formulations. A higher concentration of fungicide may be hazardous to human beings and have negative effects on the environment. In the past, people have explored a variety of alternatives and options to solve this issue, leading to the development of poly fungicide mixtures, the use of non-toxic chemicals, and the development of innovative formulations that deliver an effective amount of the fungicide just where it is needed. However, using a poly combination with a lot of fungicides can be problematic for certain people because it's like mixing up a bunch of fungicides with distinct chemical, behavioural, and physical characteristics. Additionally, it presents difficulties for the formulator in terms of the stability and compatibility of each fungicide as well as the excipients utilized in the formulation.
There is therefore a continuing need to a find new compounds and new compositions having superior biological properties for use in controlling or preventing infestation of plants by phytopathogenic fungi; for example, compounds possessing a greater biological activity, an advantageous spectrum of activity, an increased safety profile, improved physio-chemical properties, or compositions possessing a broad spectrum of activity, improved crop tolerance, synergistic interactions or potentiating properties, or compositions which display a more rapid onset of action or which have long lasting residual activity or which enable a reduction in the number of applications and/or a reduction in the application rate of the compounds and compositions required for effective control of a phytopathogen, thereby enabling beneficial resistance-management practices, reduced environmental impact and reduced operator exposure.
Patent no. CN101953356 relates to a dimethomorph-containing thermal smoke agent (hot fogging concentrate) for preventing and controlling downy mildew of vinyl house in cucumbers. The thermal smoke agent comprises the following active ingredients: dimethomorph and azoxystrobin, dimethomorph and chlorothalonil, dimethomorph and cymoxanil, dimethomorph and metalaxyl, or dimethomorph and hymexazol, and also comprises the following auxiliaries: an emulsifying agent, a dispersing agent, a solvent, a viscosity regulating agent, a defoaming agent and the like.
Patent no. CN101653128 relates to a bactericidal composition, the effective ingredients of which are zoxamide and dimethomorph, wherein the mass ratio of the zoxamide to the dimethomorph is 30:1-1:50 and other ingredients are acceptable and allowed auxiliary ingredients in pesticides.
The present invention does not fall within the scope of the mentioned closest state of the art as it relates to a unique trimix in the form of a ready to use composition of Mandipropamid, Dimethomorph and Soy protein. The references mentioned in the prior art do not disclose any three-way mixture nor the synergistic composition according to the present invention, nor the concentration ranges of the components in the mixture.
Surprisingly, the inventors of the present invention have found that the novel and synergistic composition of Mandipropamid, Dimethomorph and Soy protein, as described herein, provide a solution to the above-mentioned problems.
OBJECT(S) OF THE INVENTION:
It is an object of the present invention to provide a synergistic fungicidal combination for effectively controlling infestation by phytopathogenic fungi.
It is another object of the present invention to provide a fungicidal composition comprising said fungicidal combination for control of fungal pests in various agricultural crops.
It is yet another object of the present invention to provide a fungicidal composition for enhanced efficacy against fungal pests and enhanced crop yield without any phytotoxicity.
It is yet another object of the present invention to provide a process for preparing said fungicidal composition.
It is yet another object of the present invention to provide a method of combating fungus at a locus which comprises plants subject to or subjected to fungal attack.
SUMMARY OF THE INVENTION
The present invention discloses a novel, synergistic, fungicidal composition that comprises Mandipropamid, Dimethomorph and Soy protein along with at least one agriculturally acceptable excipient. The synergistic fungicidal composition of the present invention is especially effective against downy mildew disease, in various agricultural crops, particularly grapes.
In an aspect, the present invention discloses a synergistic fungicidal composition comprising:
a. Mandipropamid;
b. Dimethomorph;
c. Soy protein; and
d. at least one agriculturally acceptable excipient.
In another aspect, the present invention discloses a synergistic fungicidal composition comprising of:
a. mandipropamid in an amount in the range of 5-40% w/w;
b. dimethomorph in an amount in the range of 5-50% w/w;
c. soy protein in amount in the range of 0.08-2% w/w; and
d. at least one agriculturally acceptable excipient.
In yet another aspect, said agriculturally acceptable excipient is selected from the group consisting at least one anti-freeze agent, at least one dispersing agent, at least one wetting agent, at least one deformer, at least one anti-bacterial or biocide, at least one thickener, and a combination thereof.
In another aspect, the present invention discloses a synergistic fungicidal composition which is in the form selected from the group consisting of water-soluble concentrates (SL), emulsifiable concentrates (EC), emulsions (EW), micro-emulsions (ME), Suspension concentrates (SC), oil-based suspension concentrates (OD), flowable suspensions (FS), water-dispersible granules (WG), water-soluble granules (SG), wettable powders (WP), water soluble powders (SP), granules (GR), encapsulated granules (CG), fine granules (FG), macro granules (GG), dry flowable (DF), aqueous suspo-emulsions (SE), capsule suspensions (CS) and microgranules (MG).
In a preferred aspect of the present invention, the synergistic fungicidal composition is in a form of a suspension concentrates (SC).
In another aspect, the synergistic fungicidal composition of the present invention, the composition comprises of:
a. mandipropamid in an amount in the range of 8 to 20% w/w;
b. dimethomorph in an amount in the range of 15 to 30% w/w;
c. soy protein in an amount in the range of 0.08 to 1.2% w/w; and
d. at least one agriculturally acceptable excipient.
In another aspect, the synergistic fungicidal composition of the present invention, comprises of
a. mandipropamid in an amount of 7% w/w;
b. dimethomorph in an amount of 25% w/w;
c. soy protein in an amount of 0.1% w/w; and
d. at least one agriculturally acceptable excipient.
In yet another aspect, the present invention provides a process for preparing said synergistic fungicidal composition, comprising:
(i) solubilizing at least one wetting agent and anti-freezing agent in demineralized water through high speed, followed by defoamer to obtain a homogeneous mixture;
(ii) adding mandipropamid technical, and dimethomorph technical to the homogenous mixture of step (i);
(iii) grinding the mixture of step (ii) in sand mill until the mean particle size of less than 5 micron is achieved;
(iv) preparing 2% of gel by adding 10gm of D.M water 0.5 gm of formaldehyde solution, followed by 0.20 gm xanthan gum under slow stirring; and
(v) subjecting 2% of gel and soy protein to the mixture of step (iii) to obtain a homogeneous mixture in suspension concentrates formulation.
In another aspect of the present invention, the process of preparation comprises of mandipropamid in an amount in the range of 5 to 40% w/w; dimethomorph in an amount in the range of 5 to 50% w/w; and soy protein in an amount in the range of 0.08 to 2% w/w.
In another aspect the present invention provides a method of combating fungus at a locus which comprises treating the locus with a fungicidally effective amount of the composition. The locus comprises plants subject to or subjected to fungal attack.
TECHNICAL ADVANCEMENTS OF THE INVENTION
The synergistic fungicidal composition as disclosed in the present invention comprises Mandipropamid, Dimethomorph and Soy protein as described herein above and has several associated technical advantages including but not limited to:
? enhanced disease control;
? synergistic effects;
? plant health benefits; and
? reduced environmental impact.
DETAILED DESCRIPTION OF THE INVENTION
The present invention does not use any biological material originating in India. Soy Protein used in the present invention is not obtained from India and was procured from an imported source (Sales Office 1900 Crown Colony Drive, 3rd Floor, Quincy, Massachusetts, USA).
Abbreviations
D.M. Demineralised Water
RTU Ready to Use
SC Suspension Concentrate
QS Quantum satis
A.I/ a.i Active Ingredients
PDI Percent Disease Index
DAA Days After Application

Those skilled in the art will be aware that the invention described herein is subject to variations and modifications other than those specifically described herein. It is to be understood that the invention described herein includes all such variations and modifications. The invention also includes all such steps, features, compositions and compounds referred to or indicated in this specification, individually or collectively, and all combinations of any two or more of said steps or features.
Unless otherwise specified, all terms used in disclosing the invention, including technical and scientific terms, have the meaning as commonly understood by one of the ordinary skills in the art to which the invention belongs. For further guidance, term definitions may be included to better appreciate the teaching of the present invention.
As used herein, the term “plant” refers to any plant or part thereof including serial and subterranean parts of the plant. It is contemplated that the parts of the plant may be for example, flowers, fruits or vegetables, shoots, leaves, needles, stalks, stems, fruiting bodies, seeds also roots and that parts of the plants may or may not be attached to the remainder of the plant.
The term ‘disease control’ as used herein denotes control and prevention of a disease. Controlling effects include all deviation from natural development, for example: killing, retardation, decrease of the pests. The term ‘plants’ refers to all physical parts of a plant, including seeds, seedlings, saplings, roots, tubers, stems, stalks, foliage and fruits.
It is to be understood that the singular forms “a,” “an,” and “the” include plural referents unless the context clearly dictates otherwise.
Features that are described and/or illustrated with respect to one embodiment may be used in the same way or in a similar way in one or more other embodiments and/or in combination with or instead of the features of the other embodiments.
It should be emphasized that the term “comprises/comprising” when used in this specification is taken to specify the presence of stated features, steps or components but does not preclude the presence or addition of one or more other features, steps, components or groups thereof.
The term "fungicidal" also called antimycotic, any toxic substance used to kill or inhibit the growth of fungi.
The terms “weight percent”, “wt-%”, “percent by weight”, “% by weight” and variations thereof, as used herein, refer to the concentration of a substance as the weight of that substance divided by the total weight of the composition and multiplied by 100. It is understood that, as used here, “percent “, “%” and the like are intended to be synonymous with “weight percent”, “wt. %”, etc.
As used herein, the term “agriculturally acceptable excipient” refers to an ingredient, additive, component or supplement, liquid or solid, suitable for incorporation in agricultural compositions.
Mandipropamid is an amide bactericide. Mandipropamid is chemically known as 2-(4-chlorophenyl)-N-[2-(3-methoxy-4-prop-2-ynoxyphenyl)ethyl]-2-prop-2-ynoxyacetamide having chemical structure as below:

It inhibits the biosynthesis of phospholipid, and the compound has good control effect on most of leaf and fruit diseases caused by oomycetes. Has high activity on spore in germination stage and can inhibit hypha growth and sporulation. Can be rapidly absorbed by the leaf and stay in the surface wax layer of the leaf, thereby protecting the leaf.
Dimethomorph is a systemic fungicide belonging to the chemical class of cinnamic acid amides, used on vines, potatoes, and greenhouse crops. Dimethomorph is chemically known as (E)-3-(4-chlorophenyl)-3-(3,4-dimethoxyphenyl)-1-morpholin-4-ylprop-2-en-1-one having chemical structure as below:

It has a role as a xenobiotic, an environmental contaminant, and an antifungal agrochemical. The mode of action of Dimethomorph lies in disrupting fungal cell wall development, resulting in death of the fungal cells at all stages in development - germination, penetration, colonization, sporulation. Therefore, it has significant effect on and inside the leaf.
The details of biological material used in the present invention:
Soy protein basically serves as plant-derived bio-stimulant which is readily available in the markets. Traditionally, it is made from soybean meal that has been dehulled and defatted. Soy protein extract contains various amino acids – Aspartic, Threonine, Serine, Glutamic acid, Proline, Glycine, Valine, Cystine, Isoleucine, Methionine, Tyrosine, Phenylalanine, Lysine, Histidine, Arginine, and the percentage of each amino acid may vary in the mixture.
Increasing frequency of adverse environmental conditions for crop growth, have driven the development of biostimulants. These are substances whose function is to stimulate nutrient uptake, nutrient use efficiency, tolerance to abiotic stresses and crop quality. Soy protein has a bio stimulating effect on the health of the crops.
Soy protein function as micronutrients and act synergistically along with the fungicidal active ingredients in the composition in improving plant immune system. Soy protein improves the formulation, stability, and adhesion of the fungicide to plant surfaces and help the fungicide spread more effectively and adhere to the plant, which can enhance its overall effectiveness. Further, addition of soy protein enhances protein synthesis in the meristematic tissues. The enhanced protein synthesis increases photosynthetic pigments in plants and that in turn results in accelerated photosynthetic reaction. Hence, addition of soy protein to the active ingredients additionally restores plant health.
The best results are however obtained when soy protein is in the optimum range and such optimum range needs to be determined. Excess amount of soy protein in the biological system will affect plant cells leading to adverse effects on the plant physiology, finally leading to phytotoxicity. Hence, the optimum range of soy protein in the composition is very significant.
Source of Soy protein: Soy Protein was procured from Sales Office 1900 Crown Colony Drive, 3rd Floor, Quincy, Massachusetts, USA.
Many types of formulations for various compositions are known and commercially available. However, Suspension Concentrates (SC) have grown in popularity due to benefits such as the absence of dust, ease of use, and effectiveness when compared to other formulation types such as emulsifiable concentrate (EC) and wettable powder (WP). These formulations are water based, which provides good safety and user convenience. Additionally, these formulations are suitable for active ingredients with low water solubility and small particle sizes.
Accordingly, the present invention provides a synergistic fungicidal composition comprising of mandipropamid, dimethomorph, soy protein and at least one agriculturally acceptable excipient. Further, the present invention provides a method for preparation of the synergistic fungicidal composition.
The synergistic fungicidal composition of the present invention is a Ready to Use Formulation (RTU). The ready to use formulation has various advantages over the tank mix of the active ingredients. These advantages include very few or no inhalation hazards, easy handling, low chances of sedimentation, being environmentally safer, good efficacy without phytotoxicity, lower transportation costs, and scientific practice as the formulation is prepared after stability and compatibility studies.
In another embodiment of the present invention, the synergistic fungicidal composition comprises of:
a. mandipropamid in an amount in the range of 8 to 20% w/w;
b. dimethomorph in an amount in the range of 15 to 30% w/w;
c. soy protein in an amount in the range of 0.08 to 1.2% w/w; and
d. at least one agriculturally acceptable excipient.
In a preferred embodiment, Mandipropamid is present in an amount of 7% w/w, Dimethomorph is present in an amount of 25% w/w and Soy protein is present in an amount of 0.1% w/w of the fungicidal composition.
Surprisingly, inventors of the present invention have found that the presently claimed fungicidal composition when applied at significantly lesser dosages than their individual recommended dosages when applied separately, exhibit superior efficacy as measured in terms of percent control of target pest. In other words, it was surprising to find that these conventional fungicides when combined at desired weight percentages at reduced individual AI (Active Ingredient) dosages, the fungicidal effect of the composition is unexpectedly enhanced.
Further, it has been found that the active compound combination of the presently claimed composition exhibits a synergistic effect and not merely an additive effect. Thus, clearly, the customary dosages of the individual actives are substantially reduced, leading to lesser amount of soil residues and environmental pollution when the composition of the present invention is used.
In an embodiment, the fungicidal composition further comprises at least one agriculturally acceptable excipient.
In another embodiment, the agriculturally acceptable excipient is selected from the group consisting at least one anti-freeze agent, at least one dispersing agent, at least one wetting agent, at least one deformer, at least one anti-bacterial or biocide, at least one thickener, and a combination thereof.
In a preferred embodiment, the agriculturally acceptable excipient comprises a combination of at least an anti-freeze agent, wetting agent, deformer, anti-bacterial and thickener.
In an embodiment, the anti-freeze agent is selected from the group consisting of mono ethylene glycol, diethylene glycol, polypropylene glycol, ethylene alcohols, polyethylene glycols, glycerine, epichlorohydrin, urea, glycerol and sorbitol.
In a preferred embodiment, the anti-freeze agent is propylene glycol.
In an embodiment, the anti-freeze agent is present in an amount ranging from 1-15%w/w.
In a preferred embodiment, the anti-freeze agent is present in an amount of 7% w/w.
In an embodiment, the wetting agent is selected from the group consisting of blend of alkyl naphthalene sulfonate, sodium salt, amine salt of poly aryl phenyl ether phosphate, Sodium laurel sulphate, poly alkyl aryl ethylene oxide phosphate ester.
In a preferred embodiment, the wetting agent is poly alkyl aryl ethylene oxide phosphate ester.
In an embodiment, the wetting agent is present in an amount ranging from 0.5-10%w/w. In a preferred embodiment, the wetting agent is present in an amount of 3% w/w.
In an embodiment, the deformer is selected from the group consisting of silicone emulsions, long-chain alcohols, fatty acids, organic fluorine compounds.
In a preferred embodiment, the deformer is silicon based.
In an embodiment, the deformer is present in an amount ranging from 0.01-3%w/w. In a preferred embodiment, the deformer is present in an amount of 0.50% w/w.
In an embodiment, the anti-bacterial is selected from the group consisting of Clavulanic acid, Avibactam, stigmasterol and formaldehyde.
In a preferred embodiment, the anti-bacterial is formaldehyde.
In an embodiment, the anti-bacterial is present in an amount ranging from 0.01- 2%w/w.
In a preferred embodiment, the anti-bacterial is present in an amount of 0.20% w/w.
In an embodiment, the thickener is selected from the group consisting of polyacrylamide, polyethylene polymers, polysaccharides (long-chain sugars), or vegetable oils and xanthan gum.
In a preferred embodiment, the thickener is xanthan gum.
In an embodiment, the thickener is present in an amount ranging from 0.02-5%w/w.
In a preferred embodiment, the thickener is present in an amount of 0.25% w/w.
The present composition may work well as several formulations selected from the group comprising , water-soluble concentrates (SL), emulsifiable concentrates (EC), emulsions (EW), micro-emulsions (ME), Suspension concentrates (SC), oil-based suspension concentrates (OD), flowable suspensions (FS), water-dispersible granules (WG), water-soluble granules (SG), wettable powders (WP), water soluble powders (SP), granules (GR), encapsulated granules (CG), fine granules (FG), macro granules (GG), dry flowable (DF), aqueous Suspo-emulsions (SE), capsule suspensions (CS) and microgranules (MG), while the preferred formulation according to the present invention is a suspension concentrate (SC).
This formulation offers certain advantages, particularly the ones listed below:
1) It is safe and ecofriendly pesticide formulation,
2) It is easy to mix as it is water-based formulation.
3) Provides enhanced efficacy against target pest
4) Better adhesion and penetration on target.
5) Does not use organic solvents. Solvent may increase toxicity to operator/environment and degrades spray equipment parts, freezing may initiate crystal formation.
The present invention also provides a method for controlling pests in various agriculture crops, said method comprising applying an effective amount of the fungicidal composition to the area to be treated in a spraying mode, foliar application, foliar over top application or sprinkler application.
In a preferred embodiment, the method of treating downy mildew comprises applying an effective amount of the fungicidal composition to grape crop by spraying mode.
The synergistic fungicidal composition is effective against wide range of plant diseases, but not limited to rice sheath blight disease, rice flax spot, rice bakanae disease, rice seedling rot, corn northern leaf blight, corn downy mildew, corn curvularia leaf spot, soybean downy mildew, apple tree rot, apple rust, apple defoliation, apple anthracnose, grape white rot, grape black pox, grape downy mildew, grape anthracnose, grape cob brown rot, tomato leaf mold, tomato canker, tomato blight, tomato early blight, cucumber downy mildew, cruciferous soft rot, tomato leaf blight, crucifer downy mildew and the like.
In a preferred embodiment, the synergistic fungicidal composition is highly effective against grape downy mildew.
Further, the synergistic fungicidal composition of the present invention provides protection against diseases caused by species Bremia lactucae Peronospora effusa; P. destructor; P. manshurica urica; P. parasitica; P. parasitica; P. tabacina; P. trifoliorum; P. schactii; Phytophthora phaseoli; Plasmopara viticola; Pseudoperonospora cubensis; and Pseudoplasmopara humuli.
In another embodiment, the present invention further provides a process of preparing a fungicidal composition comprising a) Mandipropamid b) Dimethomorph and c) Soy protein, wherein Mandipropamid is present in an amount ranging from 5-40% w/w, Dimethomorph is present in an amount ranging from 5-50% w/w, and Soy protein is present in an amount ranging from 0.08-2% w/w of the fungicidal composition; as a suspension concentrates formulation, said process comprising the following steps:
Step a: The mixture of wetting agent and anti-freezing agent were first diluted in D.M water and solubilized in high-speed mixer. After this, defoamer was added and was mixed to obtain a homogeneous mixture;
Step b: Mandipropamid technical, and Dimethomorph technical were added to the homogeneous mixture of step 1;
Step c: The above-mentioned mixture was subjected to grinding in a sand mill. Grinding was carried out until a mean particle size of less than 5 micron was obtained;
Step d: Preparation of 2% gum solution: 10gm of DM water was taken and added to 0.5gm of formaldehyde solution, then 0.20gm xanthan gum (thickener) was added under slow stirring;
Step e: After grinding, 2% water solution of xanthan gum was added to the mixture obtained from step 4 under low stirring followed by addition of soy protein and was homogeneously mixed. Finally quality parameters (appearance, pourability, spontaneity, pH) were checked (as shown in table 2).
There was no effluent generation during the formulation of this product. All the process steps were carried out at a temperature range of 25-30 degree Celsius.
In another embodiment, the present invention further provides a method of combating fungus at a locus which comprises treating the locus with a fungicidally effective amount of the composition. The locus comprises plants subject to or subjected to fungal attack.

EXAMPLES
The examples below are given solely for the purpose of illustration and are not to be construed as limitations of the present invention, as many variations thereof are possible without departing from the spirit and scope of the invention.
Example 1: Preparation of fungicidal composition as Suspension concentrates (SC)
Table no. 1 below provides a fungicidal composition as described in the present invention, formulated as suspension concentrates (SC)
Table 1: Chemical Composition of CF- 7251 SC
Ingredients Tentative percentage w/w
Mandipropamid technical (Basis of 100.0%) 7.00% w/w
Dimethomorph technical (Basis of 100.0%) 25.00% w/w
Soy protein (Basis of 100%) 0.1% w/w
Anti-freezing agent (Propylene Glycol) 6% w/w
Wetting agent (alkyl aryl ethylene oxide phosphate ester) 3% w/w
Deformer (Silicon based) 0.5% w/w
Anti-bacterial (Formaldehyde) 0.2% w/w
Thickener (Xanthan gum) 0.25% w/w
D.M Water QS to 100%

Table 2: Quality parameters of SC formulation
S.No Parameter Desired Quality
1 Appearance Material shall be in the form of free-flowing suspension
2 A.I. Content Mandipropamid – 7% w/w (±5%)
Dimethomorph – 25% w/w (±5%)
Soy protein – 0.1% w/w (±5%)
3 Pourability Residue shall not be more than 5% w/w
4 Spontaneity of dispersion Shall not be less than 50% w/w
5 Wet sieve test 98% min (passes through 45 microns sieve)
6 Persistence of foam Not more than 60ml in 1 min
7 Suspensibility not less than 90% w/w
8 pH of 1% aq. Solution 5.0- 8.0
9 Heat stability test Take 100 ml sample & keep it in 54°C±2 for 14 days check for all parameters listed above thereafter
10 Cold stability test Take 100 ml sample & keep it in 5°C±2 for 7 days, check for all parameters listed above thereafter

Example 2: Field evaluation of the bio efficacy of the present fungicidal composition
The presently disclosed fungicidal trimix (coded as CF-7251 SC) was tested for its bio efficacy against downy mildew in grape crop in a local variety during Kharif season 2022 at Nashik, Maharashtra. The plants were aligned in the plot size of 10 vines per treatments. The trail was laid out in a random block design consisting of a total of 10 treatments in three replications. The trial was conducted at a temperature of 35oC under 70% relative humidity, no winds and under optimum soil moisture conditions.
Measured quantity of the chemical was added to required volume of water @ 375 lit. /ha for spraying. The spray tank was filled with ½ the quantity of clean required volume of water and then the measured chemical (according to the dose) was added followed by the rest half quantity of water. The solution was stirred well before application. Knapsack sprayer fitted with boom along with flood jet nozzle was used to apply the fungicidal composition.
Table 3 below provides the treatment details of the grape crop in the trial experiment conducted. For purpose of convenience, the present composition has been represented by the code “CF-7251 SC”.
Treatments Treatment Details Dose(gm)
(a.i/hectare) Dose (ml)/hectare
Control (T-1) Untreated Control - -
CF-4201 SC (T-2) Mandipropamid 4% + Dimethomorph 20% + Soy Protein 0.1 % SC 40 + 20 + 1 1000 ML
CF-0420 SC (T-3) Mandipropamid 4% + Dimethomorph 20% SC 40 + 20 1000 ML
CF-7251 SC (T-4) Mandipropamid 7% + Dimethomorph 25% + Soy Protein 0.1 % SC 70 + 250 + 1 1000 ML
CF-0725 SC (T-5) Mandipropamid 7% + Dimethomorph 25% SC 70 + 250 1000 ML
CF-1031 SC (T-6) Mandipropamid 10% + Dimethomorph 35% + Soy Protein 0.1 % SC 100 + 350 + 1 1000 ML
CF-1003 SC (T-7) Mandipropamid 10% + Dimethomorph 35% SC 100 + 350 1000 ML
MKTS-1 (T-8) Dimethomorph 50% WP MKTS-1 500 1000 GM
MKTS-2 (T-9) Mandipropamid 23.4% SC 93.6 400 ML

EVALUATION OF BIO-EFFICACY AGAINST DISEASE MANAGEMENT
Evaluation method for grape downy mildew disease
Observe randomly selected 75 leaves/replication and 3 replication/plot and rate visually each disease as per the ratings below. Calculate the per cent disease index (PDI) as per given formula

Grade Spots on Leaves
0 No visible symptoms
1 < 1% leaf area affected
3 1-10% leaf area affected
5 11-25% leaf area affected
7 26-50% leaf area affected
9 >50 leaf area affected

Sum of numerical rating
PDI = ---------------------------------------------------------------------------- x 100
Total no. of plants/Leaves observed X Maximum grade

Table 4: Effect of fungicide treatment on Grapes Downy mildew disease at 7 days after 1st, 2nd and 3rd application for CP-7251 SC comprising Mandipropamid 7% + Dimethomorph 25% + Soy protein 0.1%
Treatments gm a.i./Ha Dose/Ha 7 DA1A % Control 7 DA2A % Control 7 DA3A % Control
Untreated (T-1) - - 15 - 29 - 36.5 -
CF-4201 SC (T-2) 40 + 20 + 1 1000 ML 3.4 77.33 5.6 80.69 8.8 75.89
CF-0420 SC (T-3) 40 + 20 1000 ML 4.2 72.00 6 79.31 9.5 73.97
CF-7251 SC (T-4) 70 + 250 + 1 1000 ML 1.1 92.67 2.4 91.72 4.3 88.22
CF-0725 SC (T-5) 70 + 250 1000 ML 2 86.67 3.7 87.24 5.8 84.11
CF-1031 SC (T-6) 100 + 350 + 1 1000 ML 1.2 92.00 2.7 90.69 4.8 86.85
CF-1003 SC (T-7) 100 + 350 1000 ML 2 86.67 3.9 86.55 5.4 85.21
MKTS-1 (T-8) 500 1000 GM 4.9 67.33 6.9 76.21 9.7 73.42
MKTS-2 (T-9) 93.6 400 ML 2.9 80.67 3.8 86.90 8.9 75.62

As seen in Table 4, treatment with Mandipropamid alone at 93.6 g a.i/ha results in about 80% control of the disease after the first application. Dimethomorph alone at 500 g a.i/ha results in about 67% control of the disease after the first application. Treatment with the combination of Mandipropamid and Dimethomorph at the concentration of 40 g a.i/ha + 20 g a.i/ha respectively results in about 72% control of the disease after the first application. However, unexpectedly and surprisingly, advantageously, the combination of Mandipropamid + Dimethomorph + Soy protein at concentration of 70 g a.i/ha + 250 g a.i/ha + 1 g a.i/ha respectively results in about 93% control of the disease after first application. It can be observed that when soy protein is used with the combination of Mandipropamid and Dimethomorph, it synergistically enhances the overall activity of the fungicidal composition. The Results obtained were superior to other possible combinations.
Example 3: Evaluation of Phytotoxicity
Visual observations were recorded at 3, 7 and 10 days after application (DAA) of testing products. The parameters observed were leaf injury on tip/surface, necrosis, vein clearing, epinasty, hyponasty and wilting. The score scale (1-10) followed for leaf injury on tips/surface is given below in Table.
Table 5: Phytotoxicity symptoms scoring and rating for leaf injury on tip/surface
Leaf injury on tips/surface Rating
0-10% 1
11-20% 2
21-30% 3
31-40% 4
41-50% 5
51-60% 6
61-70% 7
71-80% 8
81-90% 9
91-100% 10

Table 6: Phytotoxic effect of various treatments on grape downy mildew diseased crop after 7 DAA
Treatments gm a.i/Ha Dose/Ha 3 DAA
Y N E H B SH
Untreated (T-1) - - 0 0 0 0 0 0
CF-4201 SC (T-2) 40 + 20 + 1 1000 ML 0 0 0 0 0 0
CF-0420 SC (T-3) 40 + 20 1000 ML 0 0 0 0 0 0
CF-7251 SC (T-4) 70 + 250 + 1 1000 ML 0 0 0 0 0 0
CF-0725 SC (T-5) 70 + 250 1000 ML 0 0 0 0 0 0
CF-1031 SC (T-6) 100 + 350 + 1 1000 ML 3 3 0 0 0 0
CF-1003 SC (T-7) 100 + 350 1000 ML 1 1 0 0 0 0
MKTS-1 (T-8) 500 1000 GM 0 0 0 0 0 0
MKTS-2 (T-9) 93.6 400 ML 0 0 0 0 0 0

Note:
DAA – Days after application,
Y: Yellowing, N: Necrosis, E: Epinasty, H: Hyponesty, B: Burning, SH: Shortening
As seen in Table 6, there is no phytotoxicity associated with treatment of any of the ingredients to the plants, suggesting that said composition is completely safe to use.
The present invention provides a novel and synergistic combination of Mandipropamid, Dimethomorph and Soy protein, which significantly enhances the economic value of crops. While the present specification illustrates various concentrations across which enhanced results are seen, in particular, the combination of Mandipropamid, Dimethomorph and Soy protein at concentration of 70 gm a.i/ha, 250 gm a.i/ha and 1 gm a.i/ha respectively shows the best results in controlling grapes downy mildew disease. There is a clear and significant enhancement which is not anticipated or expected.
From the foregoing it will be observed that numerous modifications and variations can be effectuated without departing from the true spirit and scope of the novel concepts of the present invention. It is to be understood that no limitations with respect to the specific embodiments illustrated is intended or should be inferred. It should be understood that all such modifications and improvements have been deleted herein for the sake of conciseness and readability but are properly within the scope of the following claims. , Claims:We Claim:
1. A synergistic fungicidal composition comprising:
a. mandipropamid;
b. dimethomorph;
c. soy protein; and
d. at least one agriculturally acceptable excipient.
2. The synergistic fungicidal composition as claimed in claim 1, wherein the composition comprises of:
a. mandipropamid in an amount in the range of 5-40% w/w;
b. dimethomorph in an amount in the range of 5-50% w/w;
c. soy protein in amount in the range of 0.08-2% w/w; and
d. at least one agriculturally acceptable excipient.
3. The synergistic fungicidal composition as claimed in claim 1 or 2, wherein the agriculturally acceptable excipient is selected from the group comprising of anti-freeze agent, dispersing agent, wetting agent, deformer, anti-bacterial or biocide, thickener, and a combination thereof.
4. The synergistic fungicidal composition as claimed in claim 1, wherein said fungicidal composition is formulated in a form selected from the group consisting water-soluble concentrates (SL), emulsifiable concentrates (EC), emulsions (EW), micro-emulsions (ME), Suspension concentrates (SC), oil-based suspension concentrates (OD), flowable suspensions (FS), water-dispersible granules (WG), water-soluble granules (SG), wettable powders (WP), water soluble powders (SP), granules (GR), encapsulated granules (CG), fine granules (FG), macro granules (GG), dry flowable (DF), aqueous Suspo-emulsions (SE), capsule suspensions (CS) and microgranules (MG).
5. The synergistic fungicidal composition as claimed in claim 4, wherein the composition is a suspension concentrates (SC) formulation.
6. The synergistic fungicidal composition as claimed in claim 1, wherein the composition comprises of:
a. mandipropamid in an amount in the range of 8 to 20% w/w;
b. dimethomorph in an amount in the range of 15 to 30% w/w;
c. soy protein in an amount in the range of 0.08 to 1.2% w/w; and
d. at least one agriculturally acceptable excipient.
7. The synergistic fungicidal composition as claimed in claim 1, wherein the composition comprises of:
a.mandipropamid in an amount of 7% w/w,
b. dimethomorph in an amount of 25% w/w;
c. soy protein in an amount of 0.1% w/w; and
d. at least one agriculturally acceptable excipient.
8. A process for preparation of a synergistic fungicidal composition, the process comprises of:
(i). solubilizing at least one wetting agent and anti-freezing agent in demineralized water through high speed, followed by defoamer to obtain a homogeneous mixture;
(ii). adding mandipropamid technical, and dimethomorph technical to the homogenous mixture of step (i);
(iii) grinding the mixture of step (ii) in sand mill until the mean particle size of less than 5 micron is achieved;
(iv). preparing 2% of gel by adding 10gm of D.M water 0.5 gm of formaldehyde solution, followed by 0.20 gm xanthan gum under slow stirring; and
(v). subjecting 2% of gel and soy protein to the mixture of step (iii) to obtain a homogeneous mixture in suspension concentrates formulation.
9. The process as claimed in claim 8, wherein the mandipropamid in an amount in the range of 5 to 40% w/w; dimethomorph in an amount in the range of 5 to 50% w/w; and soy protein in an amount in the range of 0.08 to 2% w/w.
10. A method of combating fungus at a locus which comprises treating the locus with a fungicidally effective amount of the composition according to claim 1.
11. The method as claimed in claim 10, wherein said locus comprises plants subject to or subjected to fungal attack.