FIELD OF THE INVENTION
The present invention relates to stable synergistic fungicidal compositions comprising a
pyrazole-carboxamide derivative and a triazole derivative, methods of preparation and
methods of controlling a broad spectrum of plant diseases.
BACKGROUND OF THE INVENTION
The present invention relates to new drug combinations on the one hand and a stable
synergistic composition of fungicidal active ingredients on the other hand consisting of
pyrazole-carboxamide derivatives and triazole derivatives which are highly suitable for
protecting, controlling fungi such as phytopathogenic fungi.
It is already known that certain carboxamides have fungicidal properties. However, at
low application rates, the activity of these substances is unsatisfactory. Furthermore,
though it is already known that numerous triazole derivatives and dicarboximides and
other heterocycles are used in combating fungi, the effect of these substances at low
application rates is not always sufficient.
Penthiopyrad is a chemical compound belonging to the class of fungicidal compounds
known as pyrazole-carboxamide derivatives. Its chemical structure is as below:
(RS) -N- [2- (1,3-dimethylbutyl) -3-thienyl] -1-methyl-3- (trifluoromethyl) pyrazole-4-
carboxamide
3
Penthiopyrad produces its fungicidal effect by acting as a Succinate Dehydrogenase
Inhibitor. It inhibits the enzyme complex Succinate Dehydrogenase or Complex II, which
is a key enzyme in the mitochondrial respiratory chain. This results in the inhibition of
spore germination, germ tubes, and mycelial growth thereby disrupting the cellular
metabolism and ATP production. It has a residual, preventive and post infection action.
Furthermore, it has excellent efficacy against Scab, Powdery mildew, Botrytis,
Anthracnose, Alternaria diseases of fruits & vegetables and different diseases of
cereals.
Hexaconazole is a chemical compound belonging to a class of fungicidal compounds
known as triazole derivatives. Its chemical structure is as below:
2-(2, 4-Dichlorophenyl)-1-(1H-1, 2, 4-triazol-1-yl) hexan-2-ol
Hexaconazole produces its fungicidal effect by inhibiting the enzyme Demethylase in
sterol biosynthesis thereby disrupting membrane function. It is a highly effective
systemic fungicide with protective and curative action and is used to control both seedborne
and soil-borne diseases especially Ascomycetes and Basidiomycetes spp. In
particular, it effectively controls a wide range of diseases such as Erysiphales (Powdery
mildew) Ascomycetes (Scab) Basidiomycetes (Rust), Fungi imperfecti (Wilt), Apple
(Scab), Rice (sheath blight), Groundnut (Leaf spot), Mango, Grapes (Powdery mildew).
4
It has been found that when used in conjunction, a pyrazole-carboxamide derivative and
a triazole derivative produce an improved, synergistic effect against wide range of
fungal pathogens.
Fungi damage agricultural crops and cause diseases in plants. Several methods of
using fungicides to control fungal growth are known in the art.
Generally, farmers are using different combinations of fungicides to control the fungal
growth without knowing the mode of action and the fungal spectrum. At times, due to
inappropriate and/or under dosage of the product, there is fungicide resistance
development or poor control of the fungal growth. It is usually not possible to predict
synergistic activity for combinations of known fungicides, even if the compounds show a
close structural similarity to known synergistic combinations. The problem of fungal
growth is addressed more effectively when one uses pyrazole-carboxamide derivatives
such as Penthiopyrad and triazole derivatives such as Hexaconazole in Pre-mix
combination. The pre-mix combination of these two fungicides show good synergistic
effect in addressing the fungal growth which is not obtained through the combination
being made by the farmers or by already existing similar combinations.
The fungicides or combination of fungicides can be applied in different ways for
example sequential application, tank-mix application and pre-mix application. In
sequential application, farmers use different fungicides, wherein the fungicide selection
is not based on the technical knowhow and fungicides having the same mode of action
are being used, which leads to resistance development. In tank-mix application, farmers
use different combinations of fungicides, most of the times without having training to
properly mix products. Homemade tank mixes may therefore not be as stable as a premix.
The tank-mix usually results in non-judicious use of individual fungicides and end
up with poor fungal control. Moreover, the tank mixture is less convenient and
potentially hazardous to people who are not trained to properly mix products.
5
The pre-mix application is a combination of two or more fungicides as active ingredients
but the rates of application of the active ingredients are unchangeable, the component
rates and composition are optimized during development, hence no mixing or stability
issue exists. The pre-mix application also helps in reducing the development of
fungicidal resistance.
The sequential application and tank-mix application of fungicides, when employed to
address fungal growth, results in development of fungicide resistance. The pre-mix
application being convenient to use has not been applied so far for management of
fungal growth. It has been found that the combination of Penthiopyrad and
Hexaconazole provides synergies in controlling fungal growth and also contributes in
Fungicide Resistance Management (FRM) for sustainability of the life of this chemistry.
It is therefore desired that a stable synergistic agrochemical composition comprising a
pyrazole-carboxamide derivative and a triazole derivative be provided that exhibit a
synergistic activity, is easy to use, is less toxic, and possess increased efficiency
against wide variety of fungi and possesses a synergistic activity.
OBJECTS OF THE INVENTION
The primary object and advantage of the present invention is to provide a stable
agrochemical composition comprising a pyrazole-carboxamide derivative and a triazole
derivative as active ingredients which possesses synergistic activity.
A further object and advantage of the present invention is to provide a stable synergistic
agrochemical composition comprising a pyrazole-carboxamide derivative and a triazole
derivative with a preventive and post infection activity.
A further object and advantage of the present invention is to provide a stable synergistic
agrochemical composition comprising a pyrazole-carboxamide derivative and a triazole
derivative having translaminar and locally systemic movement within the plant.
6
A further object and advantage of the present invention is to provide a stable synergistic
agrochemical composition comprising a pyrazole-carboxamide derivative and a triazole
derivative which efficaciously contributes in Fungicide Resistance Management (FRM).
Another object and advantage of the invention is to provide a stable synergistic
agrochemical composition, which has broad fungicidal spectrum against wide variety of
fungal pathogens.
A further object and advantage of the invention is to provide a stable synergistic
agrochemical composition, which is low in toxicity on ecosystem besides showing
outstanding fungicidal activities.
Another object and advantage of the invention is to provide a stable synergistic
agrochemical composition, which is a pre-mix combination of a pyrazole-carboxamide
derivative and a triazole derivative which have different modes of action.
SUMMARY OF THE INVENTION
In one aspect of the present invention, there is provided a stable synergistic
agrochemical composition comprising a pyrazole-carboxamide derivative preferably
penthiopyrad and a triazole derivative preferably hexaconazole as active ingredients
having economic significance and being cost effective.
In yet another aspect of the present invention, there is provided a method for the
preparation of said stable synergistic agrochemical composition comprising a pyrazolecarboxamide
derivative preferably penthiopyrad and a triazole derivative preferably
hexaconazole.
In a further aspect of the present invention, there is provided a use of the stable
synergistic agrochemical composition comprising a pyrazole-carboxamide derivative
preferably penthiopyrad and a triazole derivative preferably hexaconazole as active
ingredients which results in broad fungicidal spectrum against wide range of fungal
7
pathogens, preventive and post infection activity, gives phytotonic effect to plant and
improves visible quantity and quality characteristics of plant produce.
In another aspect of the present invention, there is provided a method of use of the
stable synergistic agrochemical composition a pyrazole-carboxamide derivative
preferably penthiopyrad and a triazole derivative preferably hexaconazole as active
ingredients which results in broad fungicidal spectrum against wide range of fungal
pathogens, preventive and post infection activity.
In another aspect, there is provided a stable synergistic agrochemical composition,
which is a pre-mix combination.
In yet another aspect, there is provided a stable synergistic agrochemical composition,
which is a pre-mix combination of a pyrazole-carboxamide derivative preferably
penthiopyrad and a triazole derivative preferably hexaconazole as active ingredients
which have different modes of action.
DETAILED DESCRIPTION OF THE INVENTION
It is known that combined application of certain fungicides with specific and different
modes of action might result in an enhanced activity of a fungicide component in
comparison with a simple additive action. Such an enhanced activity is also termed a
synergism or synergistic activity. As a consequence, it is possible to reduce the
application rates of active compounds required for controlling the harmful fungi which
are responsible for a wide range of diseases.
Accordingly, the present invention relates to a stable synergistic agrochemical
composition comprising a pyrazole-carboxamide derivative (A), a triazole derivative
compound (B), and agriculturally acceptable formulation additives (C), wherein the
weight percentage of (A) is 7 to 37% , weight percentage of (B) is 3 to 13% and weight
percentage of (C) is 10 to 50%.
8
The compositions according to the present invention have better fungicidal activity
against harmful fungi than would have been expected by the fungicidal activity of the
individual compounds. In other words, the joint action of a pyrazole-carboxamide
derivative (fungicide A) and a triazole derivative (fungicide B) results in an enhanced
activity against harmful fungi in the sense of a synergy effect (synergism). For this
reason, the compositions can, based on the individual components, be used at lower
application rates to achieve a fungicidal effect comparable to the individual components.
Moreover, the compositions of the present invention provide good post-emergence
fungicidal activity, i.e. the compositions are particularly useful for combating/controlling
harmful fungi and the diseases caused by them after their emergence. Apart from that,
the compositions of the present invention show good crop compatibility, i.e. their use in
crops leads to a reduced damage of the crop plants and/or does not result in increased
damage of the crop plants.
Moreover, it has been found that the use of a pyrazole-carboxamide derivative
preferably penthiopyrad and a triazole derivative preferably hexaconazole, in
combination, extends the spectrum of fungicidal activity. Therefore the said
combinations represent an important technological advance. The term "combination" as
used in this specification refers to the "combination" of a pyrazole-carboxamide
derivative preferably Penthiopyrad and a triazole derivative preferably hexaconazole.
The compositions according to the present invention are suitable for preventing,
controlling and eradicating a wide range of harmful fungi and diseases caused by them.
The compositions of the present invention are in particular suitable for preventing,
controlling and eradicating a wide range of diseases such as Erysiphales (Powdery
mildew) Ascomycetes (Scab) Basidiomycetes (Rust), Fungi imperfecti (Wilt), Apple
(Scab), Rice (sheath blight), Groundnut (Leaf spot), Mango, Grapes (Powdery mildew),
Scab, Powdery mildew, Botrytis, Anthracnose, Alternaria diseases of fruits & vegetables
and different diseases of cereals.
9
The compositions of the present invention can be applied in conventional manner by
using techniques a skilled person is familiar with. Suitable techniques include spraying,
atomizing, dusting, spreading or watering. The type of application depends on the
intended purpose in a well-known manner; in any case, the techniques should ensure
the finest possible distribution of the active ingredients according to the invention.
The present invention also relates to compositions, besides the active ingredients,
having one or more kinds of agriculturally acceptable formulation additives (C) such as
surfactant, carrier, binder, disintegrant, pH adjuster, thickener, preservative, antifreezing
agent, defoamers and/or coloring agent customary for crop protection
compositions can be added.
The composition may be in the form of a single package composition for pre-mix
application containing both the fungicide A and the fungicide B together with
agriculturally acceptable formulation additives (C) customary for crop protection
compositions. The composition may be in the form of a two package composition,
wherein one package contains a composition fungicide A while the other package
contains a composition of the at least one fungicide B and wherein both compositions
contain agriculturally acceptable formulation additives (C) customary for crop protection
compositions. In the case of two package compositions the composition containing
fungicide A and the composition containing the fungicide B are mixed prior to
application. Preferably the mixing is performed as a tank mix, i.e. the compositions are
mixed immediately prior or upon dilution with water.
In the composition of the present invention the active ingredients, i.e. fungicide A,
fungicide B and optional further actives are formed to several types of formulations such
as not being limited to, suspension concentrate (SC), water dispersible granules (WG),
wettable powder (WP), emulsifiable concentrate (EC), etc.
10
Depending on the composition type, they comprise one or more kinds of agriculturally
acceptable formulation additives such as surfactant, carrier, binder, disintegrant, pH
adjuster, thickener, preservative, anti-freezing agent, defoamers and/or coloring agent
Suitable surfactants (a dispersant, a wetting agent, a spreader, an adjuvant for
penetration enhancement, rain fastness, soil leaching control etc.) are nonionic or
anionic or a combination of these surfactants. It is preferred to use more than two kinds
of surfactants which have different chemical structure. Suitable surfactants are, for
example, sugar esters (such as sorbitan monolaurate, polyoxyethylene sorbitan
monolaurrate), polyoxyethylene alkyl ethers (such as polyoxyethylene lauryl ether or
polyoxyethylene coconut fatty alcohol ether), polyoxyethylene aryl ethers (such as
polyoxyethylene nonylphenyl ether or polyoxyethylene trystyrylphenyl ether),
polyoxyethylene vegetable oil ethers (such as polyoxyethylene castor oil),
polyoxyethylene fatty acid esters (such as polyoxyethylene monolaurate),
polyoxyethylene polyoxypropylene block co-polymers, polyoxyethylene
polyoxypropylene alkyl ether (such as polyoxyethylene polyoxypropylene lauryl ether),
polyoxyethylene alkyl amines (such as polyoxyethylene stearyl fatty amine), alkyl
sulfates (such as sodium lauryl sulfate), polyoxyethylene alkyl ether sulfates (such as
sodium polyoxyethylene lauryl ether sulfate), polyoxyethylene aryl ether sulfates (such
as sodium polyoxyethylene nonylphenyl ether sulfate or ammonium polyoxyethylene
tristyrylphenyl ether sulfate), alkane sulfonates (such as sodium dodecyl sulfonate),
‘alpha’-olefin sulfonate, aryl sulfonates (such as sodium dodecylbenzene sulfonate,
sodium alkylnaphthalene sulfonate, sodium ‘beta’-naphthalene sulfonate formaldehyde
condensate or sodium alkyl diphenyl ether sulfonate), alkylsulfosuccinates (such as
sodium dioctylsulfosuccinate), lignosulfonates, polyoxyethylene alkyl ether phosphate,
polyoxyethylene aryl ether phosphates (such as polyoxyethylene phenyl ether
phosphate) and polyoxyethylene polyoxypropylene block co-polymer phosphate or a
combination thereof.
Suitable liquid carriers are, for example, water, alcohols (such as ethanol, propanol,
isopropanol ethylene glycol, diethylene glycol, propylene glycol, polyethylene glycol,
11
glycerin), polyol ether (such as ethylene glycol monopropyl ether, diethylene glycol
monomethyl ether), ketones (such as methyl isobutyl ketone, cyclohexanone), ethers
(such as dipropyl ether, dioxane, ethylene glycol monoethyl ether, tetrahydrofuran,
dipropylene glycol dimethyl ether), aliphatic hydrocarbons (such as normal paraffin,
naphthene, isoparaffin, kerosene, mineral oil), aromatic hydrocarbons (such as xylene,
solvent naphtha, alkyl naphthalene), esters (such as ethyl acetate, diisopropyl phthalate,
dimethyl adipate), lactones (such as gamma-butyrolactone), amides (such as
dimethylformamide, N-methylpyrrolidone, N,N-dimethyldecanamide), nitriles (such as
acetonitrile), sulfur compounds (such as dimethyl sulfoxide) and vegetable oils (such as
soybean oil, rapeseed oil, cotton seed oil). These liquid carriers may be used alone or in
a combination of two or more kinds.
Suitable solid carriers are, for example, natural minerals (such as talc, kaolinite,
pyrophyllite, montmorillonite, attapulgite, bentonite, calcite, diatomaceous earth),
synthetic minerals (such as precipitated silica, fumed silica and calcium carbonate),
inorganic salts (such as calcium carbonate, ammonium sulfate, sodium sulfate,
potassium chloride) and organic materials (such as urea, lactose, starch, cellulose,
plant powders). These solid carriers may be used alone or in a combination of two or
more kinds.
Suitable binders are, for example, polyvinyl alcohol, dextrin, denatured dextrin, soluble
starch, carboxymethyl cellulose and bentonite or a combination thereof.
Suitable disintegrants are, for example, sodium tripolyphosphate, sodium
hexametaphosphate, carboxymethyl cellulose, sodium polycarbonate and bentonite or a
combination thereof.
Suitable pH adjusters are, for example, sodium or potassium carbonate, sodium or
potassium hydrogen carbonate, sodium or potassium dihydrogenphosphate, disodium
or dipotassium hydrogenphosphate, citric acid, malic acid and triethanolamine or a
combination thereof.
12
Suitable thickeners are, for example, xanthan gum, welan gum, guar gum, polyvinyl
alcohol, carboxymethyl cellulose and its salt, silica and bentonite or a combination
thereof.
Suitable preservatives are, for example, 4-hydroxybenzoic acid esters, 2-methyl-4-
isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one and 1,2-benzisothiazolin-3-
one or a combination thereof.
Suitable anti-freezing agents are, for example, glycerin, ethylene glycol, propylene
glycol, diethylene glycol, dipropylene glycol and urea or a combination thereof.
Suitable defoamers are, for example, silicone compounds and organic fluorine
compounds or a combination thereof.
Suitable coloring agents are, for example, organic dyestuffs (such as azo dye,
phthalocyanine dye or alizarin dye) and inorganic pigments (such as iron oxide) or a
combination thereof.
In one embodiment of the present invention, the composition of the wettable powder
formulation is provided. The composition of wettable powder comprises a pyrazolecarboxamide
derivative and a triazole derivative as active ingredients, surfactant and
carrier. Other formulation additives such as pH adjuster and colorant may be
additionally used.
A method for preparing the wettable powder formulation of the present invention is also
provided. The wettable powder formulation can be prepared by mixing the active
ingredients, surfactant and carrier. Usually active ingredients, surfactant, carrier and
other formulation additives are mixed uniformly in a mixer and milled by a mill such as
an air jet mill to median diameter 5 to 50 micrometer.
13
In another embodiment of the present invention, the composition of the water
dispersible granule formulation is provided. The composition of water dispersible
granule comprises a pyrazole-carboxamide derivative and a triazole derivative as active
ingredients, surfactant, binder, disintegrant and carrier. Other formulation additives such
as pH adjuster and colorant may be additionally used.
A method for preparing the water dispersible granule formulation of the present
invention is also provided. The water dispersible granule formulation can be prepared
by mixing the active ingredients, surfactant, binder, disintegrant and carrier. Usually the
active ingredients, surfactant, binder, disintegrant, carrier and other formulation
additives are mixed uniformly in a mixer and milled by a mill such as an air jet mill to
median diameter 5 to 50 micrometer. The milled mixture is kneaded by adding 2 to
10 % of water, extruded and dried. Other granulation method such as spray dry may be
used. In this case, the milled mixture is well mixed with enough amount of water to get
slurry.
In yet another embodiment of the present invention, the composition of the suspension
concentrate formulation is provided. The composition of suspension concentrate
comprises a pyrazole-carboxamide derivative and a triazole derivative as active
ingredients, surfactant, thickener, preservative, anti-freezing agent and water. Other
formulation additives such as defoamer, pH adjuster and colorant may be additionally
used.
A method for preparing the suspension concentrate formulation of the present invention
is also provided. The suspension concentrate formulation can be prepared by wet
milling of the active ingredients mixed with surfactant, water and other formulation
additives. Usually the active ingredients, surfactant and anti-freezing agent are mixed by
dissolving or dispersing in water. The mixture is preliminary milled by a homogenizer
such as a colloid mill and then milled by a bead mill till median diameter reaches to 1 to
10 micrometer. Defoamer may be used during milling. After the milling, aqueous
solution of thickener containing preservative is added.
14
Example: Suspension concentrate (SC)
Composition of Penthiopyrad 20% Hexaconazole 7% SC
Penthiopyrad technical 20.0 w/v% (as a.i.)
Hexaconazole technical 7.0 (as a.i.)
Polyoxyethylene tristyrylphenyl ether 2.0
Sodium naphthalenesulfonate
formaldehyde condensate 4.0
Sodium dioctylsulfosuccinate 2.0
4-hydroxybenzoic acid esters 0.1
Xanthan gum 2% aqueous solution 1.9
Propylene glycol 5.0
Silicone defoamer 0.5
Water 57.5 (Balance)
Total 100.0 w/v%
The composition or composition according to the present invention has a reduced or
zero phytotoxicity with respect to important agricultural crops. This results in the present
invention being effective in the selective control of fungal growth.
At other occasions, the composition or composition of the present invention can also be
used for total elimination of fungal growth, in relation to the quantity of active principles
adopted.
For practical use in agriculture, the composition or composition of the present invention
can be applied in such quantities as to guarantee applicative dosages of the synergistic
combination.
The term “fungicide” is used herein to mean an active ingredient that kills, controls or
otherwise adversely modifies the growth of fungi. A fungicidally effective amount is an
15
amount of active ingredient which causes an adversely modifying effect and includes
deviations from natural development, killing, regulation, desiccation, retardation and the
like. The terms plants, fungal growth and vegetation include germinant seeds, emerging
seedlings, plants emerging from vegetative propagules and established vegetation.
Thus, from the foregoing description, it will be apparent to one of ordinary skill in the art
that many changes and modifications can be made thereto without departing from the
spirit or scope of the invention as set forth in the claims. Accordingly, it is not intended
that the scope of the foregoing description be limited to the description set forth above,
but rather that such description be construed as encompassing such features that
reside in the present invention, including all the features and embodiments that would
be treated as equivalents thereof by those skilled in the relevant art.
Following test results illustrate the present invention and not intended to limit the
present invention.
Effect of Penthiopyrad 20 % +Hexaconazole 7 % SC against the early blight of tomato.
Field Study:
Two field experiments were conducted in tomato at Karnal district in Haryana and at
Indore district in Madhya Pradesh during Kharif 2015, to evaluate the efficacy of
Penthiopyrad 20% SC + Hexaconazole 7% SC along with Penthiopyrad, Hexaconazole,
Propineb, Mancozeb and combination of Pyraclostrobin 5 % + Metiram 55 % WG. The
experiments were carried out with variety Himsona in plots having 5m x 4m size in
randomized block design with 7 treatments and replicated thrice. Two applications were
done at 15 days interval. Bio-efficacy in terms of percent disease index (PDI) was
calculated after each spray.
Validations for Inventions Concepts:
16
The above mentioned field studies were undertaken with the following objectives.
 To determine the effective dose of the combination fungicide against the early
blight of tomato.
 To establish the synergistic action in terms of increased efficacy and broad
spectrum control over the solo application of both fungicide.
 Compatibility of the formulations in terms of physical appearance of mixture
solution safety to crop plants, spray operator etc.
A. Effective Dose: -
Two trials were conducted to observe the efficacy of different fungicides against early
blight of tomato. Bio-efficacy, in terms of Percent Disease Index (PDI) is presented in
Table -1.1 and Table 2.1.It is revealed from tables that the ready mix combination of
Penthiopyrad 20 %+ Hexaconazole 7 % SC @ 135 g a.i/ha gave the least PDI of 3.27%
and 2.50 % at both locations respectively, followed by solo application of Penthiopyrad
20 % SC @ 100 g a.i/ha (4.40% and 5.40 %) and Pyraclostrobin 5 %+ Metiram 55 %
WG @ 900 g a.i./ha (5.13% and 5.13%) over control (21.47% and 19.13 %) at both
locations respectively.
B. Establishment of synergistic action:
Extensive literatures survey and more number of trials revealed that the fungicide of
different groups will have synergistic effect than additive or deleterious effect. Based on
the literature available, combinations of fungicides have been developed and globally
used on to combat on many fungus. Such combinations also provide enhanced
spectrum of activity and avoid resistance development for longer period.
Present study also provides evidence on the synergistic effect of combination of
Penthiopyrad 20% + Hexaconazole 7% SC @ 135 g a.i./ha showing effective control
against early blight of tomato with least PDI, as compared to solo application of both
molecules.
17
C. Compatibility of combination:-
Physical observation on the treated plants involving either solo products or the
combination does not affect the safety of the crop plants and provided the normal yield.
It has been observed that no detrimental effect on the skin and eyes irritation to the
spray operators either by combination or solo products (Table -1.3 & 2.3).
D. Yield:-
Yield data was also recorded and presented in Table-1.2 and Table-2.2. Highest
yield was recorded in the combination involving Penthiopyrad 20% + Hexaconazole 7%
SC @ 135 g a.i./ha (283.73 q/ha and 286.10 q/ha) as compared to control (251.33 q/ha
and 256.67 q/ha) at both the location respectively. It is evident from the table that the
combination developed for the control of early blight of tomato was very effective
against the disease and thereby increased the yield.
Location: - 1
Location Name : Karnal
Crop and Variety : Tomato, Himsona
Method of sowing : Transplanted
Date of Transplanting : 20/7/2015
Date of application : 10/09/2015 & 25/09/2015
Treatment detail: -
Sr. No. Treatment
Dose/ha Dilution
in
g a.i./ha Water/ha
Formulatio
n
(g or ml)
T1 Penthiopyrad 20 % SC 100 500 500 L
T2 Hexaconazole 5 % SC 35 700 500 L
18
T3 Penthiopyrad 20 % + Hexaconazole 7 %
SC 135 500 500 L
T4 Pyraclostrobin 5 % Metiram 55 % WG 900 1500 500 L
T5 Mancozeb 75 %WP 1500 2000 500 L
T6 Propineb 70 % WP 1050 1500 500 L
T7 Control - - -
19
Table-1.1: - Bio-efficacy of different treatments on the early blight of Tomato.
Sr.
no
.
Treatment
Dose/ha PDI after first spray PDI after second spray
g a.i./ha Formulatio
n g or ml BS 7 DAS 14 DAS BS 7 DAS 14 DAS
1 Penthiopyrad 20 % SC 100 500 1.38(1.19
) 2.47(1.59) 3.90 (1.99) 3.90 (1.99) 4.09 (2.04) 4.40 (2.11)
2 Hexaconazole 5 % SC 35 700 1.32
(1.17) 6.53 (2.57) 11.90 (3.46) 11.90
(3.46) 13.83 (3.73) 17.80
(4.22)
3 Penthiopyrad 20 % +
Hexaconazole 7 % SC 135 500 1.42
(1.21) 1.53 (1.26) 2.30 (1.53) 2.30 (1.53) 2.55 (1.61) 3.27 (1.82)
4 Pyraclostrobin 5 % Metiram
55 % WG 900 1500 1.42
(1.21) 3.37 1.85) 4.20 (2.06) 4.20 (2.06) 4.60 (2.16) 5.13 (2.28)
5 Mancozeb 75 %WP 1500 2000 1.50
(1.25) 5.43 (2.34) 7.60 (2.77) 7.60 (2.77) 8.80 (2.97) 10.77
(3.29)
6 Propineb 70 % WP 1050 1500 1.43
(1.21) 6.24 (2.51) 10.80 (3.29) 11.43
(3.39) 13.40 (3.67) 15.80
(3.98)
7 Control - - 1.43
(1.21) 8.73 (2.96) 15.57 (3.95) 15.57
(3.95) 17.90 (4.24) 21.47
(4.64)
CD (0.05%) NA 0.057 0.104 0.134 0.074 0.121
*BS – Before Spray; DAS – Days after spray Figures in parenthesis are square root value
20
Table -1.2: - Impact of different treatments on yield data
Sr.
no. Treatment
Dose/ha Yield data
g a.i./ha
Formulatio
n
g or ml
q/ha
1 Penthiopyrad 20 % SC 100 500 277.10 (16.66)
2 Hexaconazole 5 % SC 35 700 261.67 (16.50)
3 Penthiopyrad 20 % SC + Hexaconazole
7 % SC 135 500 283.73 (16.92)
4 Pyraclostrobin 5 % Metiram 55 % WG 900 1500 275.77 (16.66)
5 Mancozeb 75 %WP 1500 2000 271.77 (16.52)
6 Propineb 70 % WP 1050 1500 269.00 (16.43)
7 Control - - 251.33 (16.02)
CD (0.05 %) 0.068
Figures in parenthesis are square root value
21
Table – 1.3 Impact of different treatments on crop health.
DAS – Days
after spray
Sr.
No. Treatment
Dose/ha Phytotoxicity (0-10 scale) in terms of yellowing,
necrosis, wilting, epinasty, hyponasty etc.
g a.i./ha
Formulatio
n
g or ml
1
DAS
3
DAS
5
7DAS
7
DAS
10
DAS
1. Penthiopyrad 20 % SC 100 500 0 0 0 0 0
2. Hexaconazole 5 % SC 35 700 0 0 0 0 0
3. Penthiopyrad 20 % +
Hexaconazole 7 % SC 135 500 0 0 0 0 0
4. Pyraclostrobin 5 % Metiram 55 %
WG 900 1500 0 0 0 0 0
5. Mancozeb 75 %WP 1500 2000 0 0 0 0 0
6. Propineb 70 % WP 1050 1500 0 0 0 0 0
7. Control - - 0 0 0 0 0
22
Location: - 2
Location Name : Indore
Crop and Variety : Tomato, Himsona
Method of sowing : Transplanted
Date of Transplanting : 18/7/2015
Date of application : 08/09/2015 & 23/09/15
Treatment detail: -
Sr. No. Treatment
Dose/ha Dilution in
g Water/ha
a.i./ha
Formulation
(g or ml)
T1 Penthiopyrad 20 % SC 100 500 500 L
T2 Hexaconazole 5 % SC 35 700 500 L
T3 Penthiopyrad 20 % SC + Hexaconazole
7% SC 135 500 500 L
T4 Pyraclostrobin 5 % Metiram 55 % WG 900 1500 500 L
T5 Mancozeb 75 %WP 1500 2000 500 L
T6 Propineb 70 % WP 1050 1500 500 L
T7 Control -
23
Table-2.1: - Bio-efficacy of different treatments against early blight of tomato.
Sr.
no
.
Treatment
Dose/ha PDI after first spray PDI after second spray
g a.i./ha
Formulatio
n
g or ml
BS 7 DAS 14 DAS BS 7 DAS 14 DAS
1 Penthiopyrad 20 % SC 100 500 1.41
(1.21) 3.20 (1.79) 4.57 (2.14) 4.57 (2.14) 4.43 (1.84) 5.40 (2.31)
2 Hexaconazole 5 % SC 35 700 1.28
(1.15) 7.20 (2.69) 9.20 (3.04) 9.20 (3.04) 13.17 (3.63) 14.80
(3.85)
3 Penthiopyrad 20 % SC +
Hexaconazole 7 % SC 135 500 1.42
(1.21) 2.20 (1.47) 2.80 (1.68) 2.80 (1.68) 1.88 (1.32) 2.50 (1.60)
4 Pyraclostrobin 5 % Metiram
55 % WG 900 1500 1.42
(1.21) 4.03 (2.01) 4.70 (2.17) 4.70 (2.17) 3.93 (1.98) 5.13 (2.28)
5 Mancozeb 75 %WP 1500 2000 1.53
(1.26) 6.10 (2.47) 8.10 (2.85) 8.10 (2.85) 8.13 (2.86) 10.77
(3.29)
6 Propineb 70 % WP 1050 1500 1.43
(1.22) 6.91 (2.63) 11.30 (3.37) 11.30
(3.37) 12.73 (3.57) 15.80
(3.98)
7 Control - - 1.49
(1.24) 9.40 (3.07) 16.07 (4.01) 16.07
(4.01) 17.23 (4.15) 19.13
(4.38)
CD (0.05%) NA 0.101 0.093 0.093 0.180 0.341
Figure in parenthesis is square root transformation value
24
Table -2.2: - Impact of different treatments on yield data.
Sr.
no.
Treatment Dose/ha Yield data
g a.i./ha Formulation
g or ml
q/ha
1 Penthiopyrad 20 % SC 100 500 277.50 (16.66)
2 Hexaconazole 5 % SC 35 700 272.33 (16.50)
3 Penthiopyrad 20 % SC + Hexaconazole
7 % SC 135 500 286.10 (16.92)
4 Pyraclostrobin 5 % Metiram 55 % WG 25 62.5 277.50 (16.66)
5 Mancozeb 75 %WP 120 250 272.83 (16.52)
6 Propineb 70 % WP 187.5 750 270.00 (16.43)
7 Control - - 256.67 (16.02)
CD (0.05 %) 0.073
Figures in parenthesis are square root value
25
Table – 2.3 Evaluation of impact of different treatment on crop health.
*DAS – Days after spray
Sr.
No. Treatment
Dose/ha Phytotoxicity (0-10 scale) in terms of yellowing,
necrosis, wilting, epinasty, hyponasty etc.
g a.i./ha g or ml 1
DAS
3
DAS
5
7DAS
7
DAS
10
DAS
1. Penthiopyrad 20 % SC 100 500 0 0 0 0 0
2. Hexaconazole 5 % SC 35 700 0 0 0 0 0
3. Penthiopyrad 20 % SC +
Hexaconazole 7 % SC 135 500 0 0 0 0 0
4. Pyraclostrobin 5 % Metiram 55 % WG 25 62.5 0 0 0 0 0
5. Mancozeb 75 %WP 120 250 0 0 0 0 0
6. Propineb 70 % WP 187.5 750 0 0 0 0 0
7. Control - - 0 0 0 0 0

WE CLAIM:
1. A stable synergistic agrochemical composition 5 comprising a pyrazolecarboxamide
derivative (A), a triazole derivative compound (B), and agriculturally
acceptable formulation additives (C), wherein the weight percentage of (A) is 7 to 37% ,
weight percentage of (B) is 3 to 13% and weight percentage of (C) is 10 to 50%.
10 2. The composition as claimed in claim 1, wherein the preferred component (A) is
penthiopyrad.
3. The composition as claimed in claim 1 and 2, wherein the preferred component (B) is
hexaconazole.
15
4. The composition as claimed in claim 1, wherein (C) is selected from at least one
organic or inorganic carrier material including agriculturally acceptable formulation
additives such as surfactant, solid carrier, liquid carrier, binder, disintegrate, pH adjuster,
thickener, preservative, anti-freezing agent, defoamers and coloring agent, or a
20 combination thereof.
5. The composition as claimed in claim 4, wherein suitable surfactants include
sugar esters (such as sorbitan monolaurate, polyoxyethylene sorbitan monolaurrate),
polyoxyethylene alkyl ethers (such as polyoxyethylene lauryl ether or polyoxyethylene
25 coconut fatty alcohol ether), polyoxyethylene aryl ethers (such as polyoxyethylene
nonylphenyl ether or polyoxyethylene trystyrylphenyl ether), polyoxyethylene vegetable
oil ethers (such as polyoxyethylene castor oil), polyoxyethylene fatty acid esters (such
as polyoxyethylene monolaurate), polyoxyethylene polyoxypropylene block co-polymers,
polyoxyethylene polyoxypropylene alkyl ether (such as polyoxyethylene
30 polyoxypropylene lauryl ether), polyoxyethylene alkyl amines (such as polyoxyethylene
stearyl fatty amine), alkyl sulfates (such as sodium lauryl sulfate), polyoxyethylene alkyl
ether sulfates (such as sodium polyoxyethylene lauryl ether sulfate), polyoxyethylene
27
aryl ether sulfates (such as sodium polyoxyethylene nonylphenyl ether sulfate or
ammonium polyoxyethylene tristyrylphenyl ether sulfate), alkane sulfonates (such as
sodium dodecyl sulfonate), ‘alpha’-olefin sulfonate, aryl sulfonates (such as sodium
dodecylbenzene sulfonate, sodium alkylnaphthalene sulfonate, sodium ‘beta’-
naphthalene sulfonate formaldehyde condensate or sodium 5 alkyl diphenyl ether
sulfonate), alkylsulfosuccinates (such as sodium dioctylsulfosuccinate), lignosulfonates,
polyoxyethylene alkyl ether phosphate, polyoxyethylene aryl ether phosphates (such as
polyoxyethylene phenyl ether phosphate) and polyoxyethylene polyoxypropylene block
co-polymer phosphate or a combination thereof.
10
6. The composition as claimed in claim 4, wherein suitable liquid carriers include
water, alcohols (such as ethanol, propanol, isopropanol ethylene glycol, diethylene
glycol, propylene glycol, polyethylene glycol, glycerin), polyol ether (such as ethylene
glycol monopropyl ether, diethylene glycol monomethyl ether), ketones (such as methyl
15 isobutyl ketone, cyclohexanone), ethers (such as dipropyl ether, dioxane, ethylene
glycol monoethyl ether, tetrahydrofuran, dipropylene glycol dimethyl ether), aliphatic
hydrocarbons (such as normal paraffin, naphthene, isoparaffin, kerosene, mineral oil),
aromatic hydrocarbons (such as xylene, solvent naphtha, alkyl naphthalene), esters
(such as ethyl acetate, diisopropyl phthalate, dimethyl adipate), lactones (such as
20 gamma-butyrolactone), amides (such as dimethylformamide, N-methylpyrrolidone, N,Ndimethyldecanamide),
nitriles (such as acetonitrile), sulfur compounds (such as dimethyl
sulfoxide) and vegetable oils (such as soybean oil, rapeseed oil, cotton seed oil) or a
combination thereof.
25 7. The composition as claimed in claim 4, wherein suitable solid carriers include
natural minerals (such as talc, kaolinite, pyrophyllite, montmorillonite, attapulgite,
bentonite, calcite, diatomaceous earth), synthetic minerals (such as precipitated silica,
fumed silica and calcium carbonate), inorganic salts (such as calcium carbonate,
ammonium sulfate, sodium sulfate, potassium chloride) and organic materials (such as
30 urea, lactose, starch, cellulose, plant powders) or a combination thereof.
28
8. The composition as claimed in claim 4, wherein suitable binders include polyvinyl
alcohol, dextrin, denatured dextrin, soluble starch, carboxymethyl cellulose and
bentonite or a combination thereof.
9. The composition as claimed in claim 4, wherein suitable 5 disintegrants include
sodium tripolyphosphate, sodium hexametaphosphate, carboxymethyl cellulose, sodium
polycarbonate and bentonite or a combination thereof.
10. The composition as claimed in claim 4, wherein suitable pH adjusters include
10 sodium or potassium carbonate, sodium or potassium hydrogen carbonate, sodium or
potassium dihydrogenphosphate, disodium or dipotassium hydrogenphosphate, citric
acid, malic acid and triethanolamine or a combination thereof.
11. The composition as claimed in claim 4, wherein suitable thickeners include
15 xanthan gum, welan gum, guar gum, polyvinyl alcohol, carboxymethyl cellulose and its
salt, silica and bentonite or a combination thereof.
12. The composition as claimed in claim 4, wherein suitable preservatives include 4-
hydroxybenzoic acid esters, 2-methyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-
20 isothiazolin-3-one and 1,2-benzisothiazolin-3-one or a combination thereof.
13. The composition as claimed in claim 4, wherein suitable anti-freezing agents
include glycerin, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol
and urea or a combination thereof.
25
14. The composition as claimed in claim 4, wherein suitable defoamers include for
example, silicone compounds and organic fluorine compounds or a combination thereof.
15. The composition as claimed in claim 4, wherein suitable coloring agents include
30 organic dyestuffs (such as azo dye, phthalocyanine dye or alizarin dye) and inorganic
pigments (such as iron oxide) or a combination thereof.
29
16. A method for the preparation of a stable synergistic agrochemical composition as
claimed in claim 1 comprising a pyrazole-carboxamide derivative (A), a triazole
derivative compound (B), and agriculturally acceptable formulation additives (C).