A FUNGICIDAL FORMULATION AND A PROCESS FOR PREPARING THE SAME

FIELD

The present disclosure relates to a fungicidal formulation of dodine and a process for preparing the same.

DEFINITIONS

As used in the present disclosure, the following terms are generally intended to have the meaning as set forth below except to the extent that the context in which they are used indicate otherwise.

Median: Median value is defined as the value where half of the population resides above this point, and half resides below this point.

D50: The term D50 is defined as the median of the particle size distribution of the solid particles in a formulation. The D50 value is the diameter of the particle in microns that splits the distribution with 50% solid particles having diameter above the D50 value and 50% solid particles having diameter below the D50 value. Hereinafter, the median particle size will be referred to as D50.

Graft Comb Polymer: A graft comb polymer is a comb shaped polymer consisting of a main chain of one polymer that acts as a backbone and two or more linear side chains of same or different polymer.

Pourability: The term pourability of an aqueous formulation is defined as the amount of an aqueous formulation remaining in a test cylinder after pouring a standard amount of the aqueous formulation using a standardized pouring procedure. Before carrying out the standardized pouring procedure the sample of the aqueous formulation is allowed to stand for a defined standard time.

Rinse residue: The term rinse residue of an aqueous formulation is defined as the amount of residue remaining in the test cylinder after rinsing the test cylinder used for pourability measurements.

Pour residue: The term pour residue of an aqueous formulation is defined as the amount of the aqueous formulation remaining in a container after a standardized pouring procedure is carried. Before pouring, the formulation in the container is allowed to stand for a definite time.

BACKGROUND

The background information herein below relates to the present disclosure but is not necessarily prior art

Dodine is a local systemic foliar fungicide with protective and curative action. Dodine is used for control of scab on apples, pears, pecans, leaf spot disease, olives, blackcurrants, celery, and foliar disease of strawberries. Dodine is also used on other fruits, vegetables, nuts and ornamental crops and on shade trees.

Dodine has been attempted to be made in an aqueous formulation. The trials of aqueous fungicidal formulations comprising dodine have low storage stability particularly with respect to viscosity increase at low particle size. Further, the attempted aqueous fungicidal formulations comprising dodine are associated with issues such as low pourability and low efficacy.

Therefore, there is felt a need for developing a stable fungicidal formulation comprising dodine to mitigate the drawbacks mentioned herein above.

OBJECTS

Some of the objects of the present disclosure, which at least one embodiment herein satisfies, are as follows:

It is an object of the present disclosure to ameliorate one or more problems of the prior art or to at least provide a useful alternative.

An object of the present disclosure is to provide a stable fungicidal formulation of dodine.

Another object of the present disclosure is to provide a process for the preparation of a fungicidal formulation of dodine.

Other objects of the present invention will be more apparent to a person skilled in the art from the description provided hereinafter. SUMMARY

The present disclosure relates to a fungicidal formulation comprising dodecylguanidine or a carboxylic acid salt of dodecylguanidine and graft comb polymer.

The present disclosure further relates to a process for preparing a fungicidal formulation. The process comprises adding an anti-freeze agent, a graft comb polymer, a preservative, an anti foaming agent, an adjuvant, an anticaking agent and dodecylguanidine or a carboxylic acid salt of dodecylguanidine to water and mixing to obtain a homogenized mixture. The homogenized mixture is wet milled to obtain a milled slurry having particle size within a predetermined range. A thickening agent and balance quantity of water is added to the milled slurry to obtain the formulation of dodecylguanidine or a carboxylic acid salt of dodecylguanidine.

DETAILED DESCRIPTION

Embodiments, of the present disclosure, will now be described herein. Embodiments are provided so as to thoroughly and fully convey the scope of the present disclosure to the person skilled in the art. Numerous details are set forth, relating to specific components, and methods, to provide a complete understanding of embodiments of the present disclosure. It will be apparent to the person skilled in the art that the details provided in the embodiments should not be construed to limit the scope of the present disclosure. In some embodiments, well-known processes, well-known apparatus structures, and well-known techniques are not described in detail.

The terminology used, in the present disclosure, is only for the purpose of explaining a particular embodiment and such terminology shall not be considered to limit the scope of the present disclosure. As used in the present disclosure, the forms "a,” "an," and "the" may be intended to include the plural forms as well, unless the context clearly suggests otherwise. The terms "comprises," "comprising,"“including,” and“having,” are open ended transitional phrases and therefore specify the presence of stated features, integers, steps, operations, elements, modules, units and/or components, but do not forbid the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof. The particular order of steps disclosed in the method and process of the present disclosure is not to be construed as necessarily requiring their performance as described or illustrated. It is also to be understood that additional or alternative steps may be employed. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed elements.

The terms first, second, third, etc., should not be construed to limit the scope of the present disclosure as the aforementioned terms may be only used to distinguish one element, component, region, layer or section from another component, region, layer or section. Terms such as first, second, third etc., when used herein do not imply a specific sequence or order unless clearly suggested by the present disclosure.

The present disclosure relates to a fungicidal formulation and a process for preparing the same.

The conventional aqueous fungicidal formulations comprising dodine are associated with issues such as low storage stability and low pourability. It has also been observed that aqueous formulations of dodine, on storage, develop increased viscosity, thereby further hampering pourability and efficacy.

In accordance with an aspect of the present disclosure there is provided a fungicidal formulation comprising dodecylguanidine or a carboxylic acid salt of dodecylguanidine and graft comb polymer.

In an embodiment of the present disclosure, the fungicidal formulation comprises dodecylguanidine or a carboxylic acid salt of dodecylguanidine in an amount in the range of 1 % to 65 % by weight of the total mass of the formulation and graft comb polymer in an amount in the range of 0.1 % to 10 % by weight of the total mass of the formulation.

In an exemplary embodiment of the present disclosure, the carboxylic acid salt of dodecylguanidine is dodecylguanidine acetate.

/V-dodecylguanidine acetate (CAS No. 2439-10-3) is a commercial fungicide known by the common name Dodine, and represented by the following structure.

Dodine is a fungicide of the guanidine group of chemicals and is considered a general toxophore with several sites of action that may differ among members of the guanidine group. Primarily, dodine’ s mode of action is through disruptions of cell membranes. Dodine acts as a systemic fungicide and also provides protective and eradicative action. Graft comb polymers have a comb shaped structure and consist of a backbone and two or more branches which differ from the backbone. This comb shaped structure assists in efficiently stabilizing suspended particles, thereby improving stability of suspension concentrates. The graft comb polymer gives robust stabilization when used as primary dispersant or as a co-dispersant, gives strong adsorption at the solid/liquid interface, gives steric stabilization by high molecular weight hydrophilic chains and inhibits Ostwald ripening for water-soluble pesticides. Further, the graft comb polymer effectively reduces the viscosity of the suspension concentrate and therefore reduces the tendency of the suspended particles to form a sediment.

The graft comb polymer used in the present invention comprises a modified styrene/maleic anhydride co-polymer and a glycol ether.

The modified styrene/maleic anhydride co-polymer is a reaction product of a styrene/maleic anhydride resin and a polyether amine. This reaction product can also be referred to as amic acid.

The styrene maleic anhydride resin forms the backbone of the co-polymer whereas polyether amine forms the hydrophilic portion of the graft comb polymer. The polyether amine used makes the co-polymer water-soluble or water-dispersible.

In accordance with an exemplary embodiment of the present disclosure, the glycol ether can be dipropylene glycol monoethyl ether.

In accordance with an embodiment of the present disclosure, the graft comb polymer is 40 % to 50 % modified styrene/maleic anhydride co-polymer and 50 % to 60 % dipropylene glycol monoethyl ether.

In an embodiment of the present disclosure, the fungicidal formulation further comprises at least one agrochemically acceptable excipient.

In an embodiment of the present disclosure, the agrochemically acceptable excipient is present in an amount in the range of 1 % to 60 % by weight of the total mass of the formulation.

In an embodiment of the present disclosure, the agrochemically acceptable excipient is selected from the group consisting of anti-freeze agent, anti-foaming agent, thickening agent, adjuvant, anti-caking agent and preservative.

An anti-freeze agent lowers the freezing point of a water-based formulation. The anti-freeze agent is selected from the group consisting of propylene glycol, ethylene glycol, diethylene glycol, triethylene glycol, dipropylene, tripropyleneglycol and glycerol.

During the preparation of formulations, various foam-inducing materials can cause foaming in the formulation, which can lead to processing difficulties. Therefore, anti-foaming agent can be added to the formulations to reduce or control foaming. The anti-foaming agent is selected from the group consisting of silicon oil, acetylene-based deformers, perfluroalkyl phosphonic acid and polydimethyl siloxanes.

A thickening agent is a substance, which can increase the viscosity of the liquid phase without substantially changing its other properties. A thickening agent can be added to the fungicidal formulation in a predetermined quantity to achieve a formulation having a desired viscosity. The thickening agent is selected from the group consisting of hydroxy ethyl cellulose, gum powder and hydroxy propyl methyl cellulose.

The adjuvant is selected from the group consisting of alcohol ethoxylate, ethoxylated isodecyl alcohol and organo silicon surfactant.

Due to interaction at the interface of solid particles, the solid particles in the formulation may settle to the bottom of the container resulting in the formation of a cake of solid particles. An anti-caking agent may be added to the formulation to prevent the interaction at the interface of surfaces between the solid particles. The anti-caking agent is selected from the group consisting of silane, dichlorodimethyl reaction products with silica, PPT silica and fumed silica.

A preservative is added to a formulation to prevent degradation or undesirable chemical changes of the active ingredients. The preservative is 1, 2-benzisothizolin-3-one. The fungicidal formulation of dodine is characterized in that the median particle size (D50) of the formulation is in the range of 2 microns to 7 microns.

In an embodiment of the present disclosure, the fungicidal formulation comprises dodecylguanidine or a carboxylic acid salt of dodecylguanidine in an amount in the range of 1 % to 65 % by weight of the total mass of the formulation, graft comb polymer in an amount in the range of 0.1 % to 10 % by weight of the total mass of the composition and at least one agrochemically acceptable excipient in an amount in the range of 1 % to 60 % by weight of the total mass of the formulation, characterized in that the median particle size (D50) of the formulation is in the range of 2 microns to 7 microns.

In an embodiment of the present disclosure, the fungicidal formulation comprises dodecylguanidine or a carboxylic acid salt of dodecylguanidine in an amount in the range of 1 % to 65 % by weight of the total mass of the formulation, graft comb polymer in an amount in the range of 0.1 to 10% by weight of the total mass of the formulation and agrochemically acceptable excipient comprising anti-freeze agent in an amount in the range of 0.1 % to 10 % by weight of the total mass of the formulation, anti-foaming agent in an amount in the range of 0.1 % to 3% by weight of the total mass of the formulation, thickening agent in an amount in the range of 0.1 % to 1 % by weight of the total mass of the formulation, adjuvant in an amount in the range of 0.1 % to 10 % by weight of the total mass of the formulation, anti caking agent in an amount in the range of 0.1 % to 1 % by weight of the total mass of the formulation, preservative in an amount in the range of 0.1 % to 1 % by weight of the total mass of the formulation and water in an amount in the range of 15 % to 50 % by weight of the total mass of the formulation, characterized in that the median particle size (D50) of the formulation is in the range of 2 microns to 7 microns.

In another embodiment of the present disclosure the fungicidal formulation comprises dodecylguanidine acetate in an amount in the range of 1 % to 65% by weight of the total mass of the formulation, graft comb polymer in an amount in the range of 0.1 % to 10 % by weight of the total mass of the formulation and at least one agrochemically acceptable excipient in an amount in the range of 1 % to 60 % by weight of the total mass of the formulation, characterized in that the median particle size (D50) of the formulation is in the range of 2 microns to 7 microns.

It is observed that the formulation of the present disclosure is stable upon storage for 14 days or more at 54 °C. Under specific conditions, for example, according to the nature of the target phytopathogenic fungi, a lower dose of the fungicidal formulation may offer adequate protection, whereas, certain climatic conditions, resistance offered by the fungi or nature of the target phytopathogenic fungi may necessitate application of higher doses of the fungicidal formulation.

The optimum dose usually depends on several factors, for example on the type of phytopathogenic fungi to be treated, on the type or level of development of the infested plant, on the density of vegetation or alternatively on the method of application of the fungicidal formulation.

In accordance with the embodiment of the present disclosure, the fungicidal formulation can be in the form of a suspension concentrate containing solid particles having median particle size (D50) in the range of 2 microns to 7 microns.

Suspension concentrates in accordance with the present disclosure are usually produced so as to obtain a stable, non-sedimenting flowable product. The suspension concentrates in accordance with the present disclosure allow the inclusion of high loadings of one or more adjuvant in a one-pack formulation with a fungicide and, therefore, offer the advantage of an optimized and easy-to-use formulation of the crop protection active compound. The separate addition of an adjuvant by the end-user before application has therefore become unnecessary.

Low particle size of the solid particles effectively improves the penetration property of the fungicidal formulation, which correlates to improved efficacy of the formulation. It is observed that the fungicidal formulation of dodine has an enhanced fungicidal activity.

Surprisingly, it is observed that the fungicidal formulation of dodine has high pourability in spite of having solid particles with a particle size in the range of 2 to 7 microns.

It is observed that the present disclosure provides a highly concentrated formulation of dodine. Therefore, the dodine formulation of the present disclosure is convenient and economical for transportation and application.

The formulations can be of any type known in the art that is suitable for application onto all types of cultures or crops. These formulations, which can be prepared in any manner known by a person skilled in the art, also form part of the invention. In accordance with an embodiment of the present disclosure, the fungicidal formulation may be used for foliar application, ground application or application to plant propagation materials.

The present disclosure envisages a simple, efficient and economical process for preparing a fungicidal formulation of dodine.

In another aspect of the present disclosure there is provided a process for preparing a fungicidal formulation of dodine. The process comprises adding an anti-freeze agent, a graft comb polymer, a preservative, an anti-foaming agent, an adjuvant, an anticaking agent and dodecylguanidine or a carboxylic acid salt of dodecylguanidine to water and mixing to obtain a homogenized mixture. The homogenized mixture is wet milled to obtain a milled slurry having particle size within a predetermined range. A thickening agent and balance quantity of water is added to the milled slurry to obtain the formulation of dodecylguanidine or a carboxylic acid salt of dodecylguanidine.

In accordance with an embodiment of the present disclosure, the step of mixing can be carried out using a homogenizer known in the art.

In accordance with an embodiment of the present disclosure, the step of milling can be carried out by grinding. The fungicidal formulation of dodine can be prepared by wet grinding, i.e. milling of materials in the presence of water or other liquid. The milled slurry can be blended with additional formulation auxiliaries.

In accordance with an embodiment of the present disclosure, the mill can be selected from batch bead mills, continuous bead mills, and toothed colloid mills.

In accordance with an embodiment of the present disclosure, the fungicidal formulation of dodine can be prepared using a known method in the art.

The fungicidal formulation of the present disclosure can have a predetermined pourability. In one embodiment, the fungicidal formulation of the present disclosure can have a predetermined pour residue and a predetermined rinsed residue.

In accordance with another embodiment of the present disclosure, the fungicidal formulation can have a predetermined viscosity.

In accordance with still another aspect of the present disclosure, there is provided a method of controlling and eliminating fungal diseases from plants. The method comprises applying to the soil, a locus of infection, a plant and/or propagation material thereof susceptible to attack by fungi, an effective amount of the fungicidal formulation of the present disclosure.

The fungicidal formulation of the present disclosure can be applied either before or after the plants or propagation material thereof is infected by fungi. It may be applied to the soil before emergence of the plants, either pre -planting or post-planting or as a foliar spray at different stages of crop development, with one or more applications early or late post-emergence.

The fungicidal formulation of the present disclosure has enhanced fungicidal activity and combats resistance shown by the fungi. The fungicidal formulation may be used to control diseases in agricultural lands for cultivating plants without any phytotoxic effect on the plants.

The present disclosure provides a fungicidal formulation of dodine and a simple, efficient and economical process for preparing the same.

The present disclosure is further described in light of the following experiments which are set forth for illustration purpose only and not to be construed for limiting the scope of the disclosure. The following experiments can be scaled up to industrial/commercial scale and the results obtained can be extrapolated to industrial scale.

The foregoing description of the embodiments has been provided for purposes of illustration and not intended to limit the scope of the present disclosure. Individual components of a particular embodiment are generally not limited to that particular embodiment, but, are interchangeable. Such variations are not to be regarded as a departure from the present disclosure, and ah such modifications are considered to be within the scope of the present disclosure.

EXAMPLES

1. Formulations for Dodine 400g/l SC

Example 1: To 400gm of water, 50gm propylene glycol, 20gm graft comb polymer, 3gm of 1, 2-benisothizolin-3-one, 20gm silicon oil, 1 gm PPT silica and 423gm of Dodine Technical were added, mixed and wet milled to obtain a milled slurry having particle size in the range of 4 microns to 6 microns. 3gm gum powder and 80gm water were mixed into the milled slurry to obtain a suspension concentrate of Dodine 400g/l. Example 2: To 400gm of water, 80gm propylene glycol, 40gm graft comb polymer, 3gm of 1, 2-benisothizolin-3-one, 20gm silicon oil, lgm adjuvant, 1 gm PPT silica and 423gm of Dodine Technical were added, mixed and wet milled to obtain a milled slurry having particle size in the range of 4 microns to 6 microns. 4gm gum powder and 28gm water were mixed into the milled slurry to obtain a suspension concentrate of Dodine 400g/l.

Example 3: To 400gm of water, 80gm propylene glycol, 60gm graft comb polymer, 3gm of 1, 2-benisothizolin-3-one, 20gm silicon oil and 423gm of Dodine Technical were added, mixed and wet milled to obtain a milled slurry having particle size in the range of 4 microns to 6 microns. 4gm gum powder and lOgm water were mixed into the milled slurry to obtain a suspension concentrate of Dodine 400g/l.

Example 4: To 400gm of water, 50gm propylene glycol, 80gm graft comb polymer, 3gm of 1, 2-benisothizolin-3-one, 20gm silicon oil, 1 gm PPT silica and 423gm of Dodine Technical were added, mixed and wet milled to obtain a milled slurry having particle size in the range of 4 microns to 6 microns. 4gm gum powder and l9gm water were mixed into the milled slurry to obtain a suspension concentrate of Dodine 400g/l.

2. Formulations for Dodine 500g/l SC

Example 5: To 300gm of water, 80gm propylene glycol, 20gm graft comb polymer, 3gm of 1, 2-benisothizolin-3-one, 20gm silicon oil and 53lgm of Dodine Technical were added, mixed and wet milled to obtain a milled slurry having particle size in the range of 4 microns to 6 microns. 3gm gum powder and 43gm water were mixed into the milled slurry to obtain a suspension concentrate of Dodine 500g/l.

Example f >: To 300gm of water, 80gm propylene glycol, 40gm graft comb polymer, 3gm of 1, 2-benisothizolin-3-one, 20gm silicon oil, 1 gm PPT silica, lgm adjuvant and 53lgm of Dodine Technical were added, mixed and wet milled to obtain a milled slurry having particle size in the range of 4 microns to 6 microns. 3gm gum powder and 2lgm water were mixed into the milled slurry to obtain a suspension concentrate of Dodine 500g/l.

Example 7: To 300gm of water, 50gm propylene glycol, 60gm graft comb polymer, 3gm of 1, 2-benisothizolin-3-one, 20gm silicon oil, 1 gm adjuvant and 53 lgm of Dodine Technical were added, mixed and wet milled to obtain a milled slurry having particle size in the range of 4 microns to 6 microns. 3gm gum powder and 32gm water were mixed into the milled slurry to obtain a suspension concentrate of Dodine 500g/l. Example 8: To 300gm of water, 50gm propylene glycol, 80gm graft comb polymer, 3gm of 1, 2-benisothizolin-3-one, 20gm silicon oil, 1 gm PPT silica and 53 lgm of Dodine Technical were added, mixed and wet milled to obtain a milled slurry having particle size in the range of 4 microns to 6 microns. 3gm gum powder and l2gm water were mixed into the milled slurry to obtain a suspension concentrate of Dodine 500g/l.

3. Formulations for Dodine 600g/l SC

Example 9: To 300gm of water, lOgm propylene glycol, 20gm graft comb polymer, 3gm of 1, 2-benisothizolin-3-one, 20gm silicon oil and 620gm of Dodine Technical were added, mixed and wet milled to obtain a milled slurry having particle size in the range of 4 microns to 6 microns lgm gum powder and 26gm water were mixed into the milled slurry to obtain a suspension concentrate of Dodine 600g/l.

Example 10: To 300gm of water, lOgm propylene glycol, 40gm graft comb polymer, 3gm of 1, 2benisothizolin-3-one, 20gm silicon oil and 620gm of Dodine Technical were added, mixed and wet milled to obtain a milled slurry having particle size in the range of 4 microns to 6 microns lgm gum powder and 6gm water were mixed into the milled slurry to obtain a suspension concentrate of Dodine 600g/l.

Example 11: To 286gm of water, lOgm propylene glycol, 60gm graft comb polymer, 3gm of 1, 2benisothizolin-3-one, 20gm silicon oil and 620gm of Dodine Technical were added, mixed and wet milled to obtain a milled slurry having particle size in the range of 4 microns to 6 microns lgm gum powder was mixed into the milled slurry to obtain a suspension concentrate of Dodine 600g/l.

Example 12: To 264gm of water, lOgm propylene glycol, 80gm graft comb polymer, 3gm of 1, 2benisothizolin-3-one, 20gm silicon oil, 1 gm silica, lgm adjuvant and 620gm of Dodine Technical were added, mixed and wet milled to obtain a milled slurry having particle size in the range of 4 microns to 6 microns lgm gum powder was mixed into the milled slurry to obtain a suspension concentrate of Dodine 600g/l.

Surprisingly, for the suspension concentrates containing 600g/l Dodine, a stable formulation was obtained and an increase in viscosity during storage was prevented. This was due to the use of a specific grade of silica having the following properties:

EXPERIMENTS:

1. ACCELERATED STABILITY STUDY

The formulations of Examples 1 to 4 were subjected to accelerated storage stability for a 5 period of 14 days at 54°C.

Table 1: Accelerated Stability Study

As observed in Table 1, Example 2 shows no change in viscosity and particle size after the accelerated stability study whereas in Examples 1, 3 and 4 there is change in viscosity, particle size and separation is observed in the sample.

0 Similarly, the formulations of Examples 5 to 8 were subjected to accelerated stability study for a period of 14 days at 54 °C.

Table 2: Accelerated Stability Study

As observed in Table 2, Example 6 shows no change in viscosity and particle size after the accelerated stability study whereas in Examples 5, 7 and 8 there is change in viscosity, particle size and separation is observed in the sample.

Further, the formulations of Examples 9 to 12 were subjected to accelerated stability study for a period of 14 days at 54 °C.

Table 3: Accelerated Stability Study

As observed in Table 3, Example 12 shows no change in viscosity after accelerated stability study whereas in Examples 9, 10 and 11 there is change in viscosity and separation.

Use of a combination of anticaking agent, adjuvant and graft comb polymer at a specified ratio enables stabilization of the formulation in terms of viscosity and particle size parameter.

2. EVALUATION FOR BIO-EFFICACY AGAISNT SCAB ( Venturia inaequalis ) DISEASE

The formulations of Examples 2, 6 and 12 were tested against standard fungicides i.e., Dodine 65% WP, Dodine 40% SC and untreated control against scab of apple. The fungicides were applied as foliar spray with Knapsack Sprayer fitted with solid cone nozzle. Application was initiated as preventive in the field. The sprayings were done at 10 days interval. The appearance of the visible symptom of the diseases was recorded before I ^st spray and

subsequent observations were recorded after 10 days of each spray. The observations were assessed and graded on (0-5) disease scoring scale for apple scab.

Disease Ratings: Rating scale for apple scab (0-5 scale) and subsequently calculate the PDI:

5 * 0 (no disease)

• 1% (one to four small spots on about a quarter of the leaves),

• 5% (almost every leaf infected with scab areas covering approximately 25% of the

leaf surface on about one-quarter of the leaves),

• 10% (every leaf infected with scab areas covering approximately 25% of the leaf

10 surface on half the leaves)

• 25% (every leaf infected with scab areas covering 50% of the leaf surface on half the

leaves)

• 50% (all leaves infected, with scab areas covering 50% of the leaf surface on half the

leaves).

15 Percent Disease Index (PDI) was calculated using the following formula:

Sum of all Numerical Ratings

PDI x 100

Total Plants Observed x Maximum Rating Scale

The PDI values were transformed by angular transformation and analyzed statistically. The

20 Disease Control (DC %) was calculated by the following formula.

Disease % in Control - Disease % in Treatment

DC(%) x 100

Disease % in Control

TABLE 4: Bio-Efficacy of Dodine against Scab ( Venturia inaequalis )

PDC

20

DAA

3 ^rd

Figures in parenthesis are arcsine transformed values. PDI- Percent Disease Incidence; PDC-

Percent Disease Control; DAA- Days After Application; NS- Non significant

The results presented in Table 4 show that at the time of initiation of trial there was no Scab disease in any treatment which indicates the uniformity of trial plot across all the treatments. At 10 days after first application, the highest Scab was recorded in control T6 (1.40%). All the fungicide treatments significantly reduced the disease severity than untreated control, but the significant lowest Scab disease was observed in Tl to T3, which was at par with each other. These treatments (Tl to T3) are significantly superior over rest of all treatments. At 10 days after second application, the highest disease was recorded in control T6 (3.50%). The significant lowest Scab disease was observed in T1-T3 (0.10%) which was superior over treatments T4 (1.85%) and T5 (1.40%). These treatments (Tl to T3) are significantly superior over rest of all treatments. At 10 days after third application also similar trend observed as of after second application. Where, the significant lowest Scab disease was observed in Tl & T2 (0.20%) which was on par with T3 (0.40%). The highest disease was observed in untreated 5 control T6 (6.50%). These treatments (Tl to T3) were significantly superior over rest of all treatments. At 20 days after third application also similar trend observed as of after 10 days after third application. Where, the significant lowest Scab disease was observed in Tl (0.50), T2 (0.55%) which was on par with T3 (0.60%). The highest disease was observed in untreated control T6 (8.15%). These treatments (Tl to T3) were significantly superior over 10 rest of all treatments. The highest percent disease control (PDC) was recorded in treatment Tl (93.87%), followed by T2 (93.25%), T3 (92.64%), which were superior over T4 (65.64) and T5 (73.01%).

3. YIELD

15 Individual plot wise yield was recorded and calculated treatment wise yield and converted into yield per hectare (tonnes/ha) at harvest and statistically analyzed the data.

Table 5: Effect of Dodine on Yield

As observed in Table 5, All the treatments significantly increase the yield than Untreated Control T6 (3.88 t/ha). The highest yield was observed in treatment Tl (6.50 t/ha), which was on par with T2 (6.33 t/ha), T3 (6.30 t/ha) followed by T5 (5.33 t/ha) and T4 (4.98 t/ha). All test fungicide treatments (Tl to T3) were significantly superior over other treatments (T5 to T4).

4. PHYTOTOXICITY

Observations were taken on damage caused to plants, if any, by the application of different treatments taking into the account phytotoxic symptoms viz. leaf injury on tips and leaf surface, wilting, vein clearing, necrosis, epinasty and hyponasty on ten plants per plot. The observations were recorded before spray and 1, 3, 5, 7, 10 & l5 ^th day after applications. For Phytotoxicity study on leaf injury on tips and leaf surface the Scale (0-10) used is given below.

Phytotoxicity Rating Scale (PRS)

Crop response/ Crop injury Rating

(TOO 0

1-10% 1

11-20% 2

21-30% 3

31-40% 4

41-50% 5

51-60% 6

61-70% 7 71-80%

81-90% 9

91-100% 10

Table 6: Phyto-Toxicity Effect Of Dodine On Apple Crop

As observed in Table 6, The test fungicides were sprayed at doses X (0.05 g a.i. /I) and 2X 5 (0.10 g a.i./l) to check the phytotoxic effects like leaf injury on tips/surface, vein clearing, wilting, necrosis, hyponasty and epinasty on the Apple crop. The observations on these phytotoxicity parameters were observed on before spray and at 3, 5, 7, 10 and 15 days after application. But there was no any phytotoxicity observed on Apple crop after spraying in any treatment. Even there was no any adverse effect noticed on Apple crop in the field applied with fungicides combinations at highest dose of @ 0.10 g a.i./l.

Overall, the test fungicides showed effective in controlling the diseases. Also to prolong the effectiveness of fungicides liable to encounter resistance problems and to limit crop losses, the test fungicides can be used effectively and safely for the management of diseases than Dodine 65% WP (T4) and Dodine 400 g/l SC (T5).

5. POURABILITY OF SUSPENSION CONCENTRATE

The formulations of Examples 2, 6 and 12 were evaluated for pourability as per the CIPAC Method 148.

Table 7: Pourability

As observed in Table 7, the fungicidal formulations of Examples 2, 6 and 12 show enhanced pourability.

TECHNICAL ADVANCEMENT

The process of the present disclosure described herein above has several technical advantages including but not limited to the realization of a fungicidal formulation of /V-dodecylguanidine acetate having improved efficacy and which is stable upon prolonged storage.

The embodiments herein and the various features and advantageous details thereof are explained with reference to the non-limiting embodiments in the following description. Descriptions of well-known components and processing techniques are omitted so as to not unnecessarily obscure the embodiments herein. The examples used herein are intended merely to facilitate an understanding of ways in which the embodiments herein may be practiced and to further enable those of skill in the art to practice the embodiments herein. Accordingly, the examples should not be construed as limiting the scope of the embodiments herein.

The foregoing description of the specific embodiments so fully reveal the general nature of the embodiments herein that others can, by applying current knowledge, readily modify and/or adapt for various applications such specific embodiments without departing from the generic concept, and, therefore, such adaptations and modifications should and are intended to be comprehended within the meaning and range of equivalents of the disclosed embodiments. It is to be understood that the phraseology or terminology employed herein is for the purpose of description and not of limitation. Therefore, while the embodiments herein have been described in terms of preferred embodiments, those skilled in the art will recognize that the embodiments herein can be practiced with modification within the spirit and scope of the embodiments as described herein.

The use of the expression“at least” or“at least one” suggests the use of one or more elements or ingredients or quantities, as the use may be in the embodiment of the invention to achieve one or more of the desired objects or results. While certain embodiments of the inventions have been described, these embodiments have been presented by way of example only, and are not intended to limit the scope of the inventions. Variations or modifications to the formulation of this invention, within the scope of the invention, may occur to those skilled in the art upon reviewing the disclosure herein. Such variations or modifications are well within the spirit of this invention.

The terms first, second, third, etc., should not be construed to limit the scope of the present disclosure as the aforementioned terms may be only used to distinguish one element, component, region, layer or section from another component, region, layer or section. Terms such as first, second, third etc., when used herein do not imply a specific sequence or order unless clearly suggested by the present disclosure.

Any discussion of documents, acts, materials, devices, articles or the like that has been included in this specification is solely for the purpose of providing a context for the disclosure. It is not to be taken as an admission that any or all of these matters form a part of the prior art base or were common general knowledge in the field relevant to the disclosure as it existed anywhere before the priority date of this application.

The numerical values given for various physical parameters, dimensions, and quantities are only approximate values and it is envisaged that the values higher than the numerical value assigned to the physical parameters, dimensions and quantities fall within the scope of the invention unless there is a statement in the specification to the contrary.

While considerable emphasis has been placed herein on the specific features of the preferred embodiment, it will be appreciated that many additional features can be added and that many changes can be made in the preferred embodiment without departing from the principles of the disclosure. These and other changes in the preferred embodiment of the disclosure will be apparent to those skilled in the art from the disclosure herein, whereby it is to be distinctly understood that the foregoing descriptive matter is to be interpreted merely as illustrative of the disclosure and not as a limitation.