Note: Descriptions are shown in the official language in which they were submitted.
107'~5g9
The present invention relates to a method of treating fungal
infections in cultivated plants, particularly cereals, and to fungicidal
formulations useful in said method.
According to a first aspect of the present invention there is
provided a fungicidal formulation which comprises as active ingredients
l-[~-(allyloxy)-2,4-dichlorophenethyl~imidazole, or a non-phytotoxic salt
thereof, and a pyrimidine methanol of fonmula (I):
X
[~3
N 0 } ~ (I)
15 ~ ~ Cl
where X is halogen; associated with a non-phytotoxic carrier therefor.
l-[~-(Allyloxy)-2,4-dichlorophenethyl]imida~ole, hereinafter
abbreviated to "the imidazole", is a compound known to possess antifungal
properties - see U.S. Patent Specification No. 3,658,813. The pyrimidine
methanols of formula (I) are also known to possess antifungal properties -
see U.K. Patent Specification No. 1,218,632.
It has now surprisingly been discovered that combined treatment
with the two active ingredients is particularly effective in controlling
mildew, helminthosporium, eyespot, bunt, smut and other fungal infections
of cereal crops such as barley, especially winter barley, oats and wheat.
For instance, in accordance with the well-known "Colby-equation", see
Weeds, 15 20-~2 (1967), a synergistic effect has been demonstrated in the
treatment of wheat rust. However, the combination of the invention is
possibly of greatest value when used as a seed treatment, especially in
connection with winter barley. In this connection it has been found
that the level of protection obtained by the seed treatment of the invention
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compares favourably with that hitherto only derivable by treatment with
organomercury compounds. However, the active ingredients of the
invention are far less toxic than such organomercury compounds and thus
the formulations and methods of the invention provide a useful addition
S to the range of antifungal treatments available.
~ccording to a second aspect of the present invention there is
provided a method of treating or preventing fungal infections of plants which
comprises applying to the leaves or seeds of the plant a pyrimidine methanol
of formula (I) and l-[~-(allyloxy)-2,4-dichlorophenethyl]imidazole, or a
non-phytotoxic salt thereof.
Preferred pyrimidine methanols of formula (I) are those in which
X is fluorine or chlorine, viz. ~-(2-chlorophenyl)-a-(4-chlorophenyl~-5-
pyrimidinemethanol (also known by the generic name "fenarimol") and
a-(2-chlorophenyl)-~-(4-fluorophenyl)-5-pyrimidinemethanol (also known by
the generic name "nuarimol"). The imidazole is preferably used in the
form of its free base, although non-phytotoxic salts such as the acetate,
hydrochloride,nitrate or sulphate may be utilised.
The pyrimidine methanols of use in the present invention are
preferably applied to cereal seeds at a rate of from 0.05 to 1.0 g/Kg,
preferably 0.1 to 0.3 g/Kg. The imidazole is preferably used in the
cereal seed treatment aspect of the invention in amoun~ts of from O.Ol to 0.5
g/Kg of seed, preferably 0.02 to 0.1 g/Kg of seed. In the treatment of
cereal plants, the pyrimidine methanol is usually applied as a spray in
amountst~of from 10 to 200 g/hectare, whilst the imidazole may be used in
amounts of from 50 to 1,000 g/hectare.
In the combined treatment of seeds according to the present
invention, it is preferred that the ratio of pyrimidine methanol to imidazole
is 20:1 to 1:5, most advantageously 15:1 to 5:1 by weight. In the case of
a foliar spray, a preferred ratio of pyrimidine methanol to imidazole is from
1:20 to 1:1 by weight.
The pyrimidine methanol and the imidazole may be applied separately
or together to the cereal plants or seeds and the treatments of the former
will usually be repeated at intervals up to harvest time, the actual
frequency and duration of treatment being detennined by the severity
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of the actual or expected disease. Particularly where there has been
severe infe~tion conditions, it may also be desirable in accordance with the
method of the present invention to treat both the cereal seeds and plants.
When, as mentioned above~ the pyrimidine methanol and the imidazole are
applied together, this combined treatment may be accomplished by mixing
the two active ingredients just prior to use or more preferably the two
actiVe ingredients are formulated together in the desired proportions and
this formulation is merely diluted prior to use. In either case, the
diluted formulation containing both active ingredients in the amounts and
ratios described above as being usable in the method of the present invention
is novel and forms a part of this invention. AS well as the active
ingredients~ such formulations contain traces of any surfactants, inert
carriers and the like~ Which were present in the concentrate compositions
used to prepare the diluted formulation, and water to make 100%. When
the plants or seeds are treated sequentially with the pyrimidine methanol
and the imidazole it is important that the active ingredients are applied
within 24 hours of each other.
AS stated above, the diluted formu~ tions of the present invention
may be produced by mixing the active ingredients just prior to use or by
diluting a ready-prepared co-formulation of the two active ingredients.
In either c8se, the active ingredients will usually be in the form of
concentrate compositions so formulated as to be capable of ready dispersion
or dilution in water. Alternatively, the concentrate compositions may
be applied direct to the seeds.
In the case where the active ingredients are separately formulated~
the imidazole component may be pUt up in the form of a wettable powder for
example one containing 20% by weight Of the active ingredient. Similarly
the pyrimidine methanol component may be formulated for example as a 4% or
10% wettable powder or as a 5% emulsifiable concentrate. Generally
however~ any appropriate concentrate compositions may be used and may contain
from about to 90~/. by weight of th ~ndividual active ~ngreùient.
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In this cAse where the active ingredients are formulated together
in concentrate compositions, the latter are novel and form a part of this
invention. Such concentrates may contain from 5 to 90% total weight of the
active ingredients, the latter preferably being present in the ratio of
pyrimidine methanol to the imidazole of from 10:1 to 1:5. In the
concentrates the pyrimidine methanol is most advantageously present in the
amount of 1 to 15% by weight.
The concentrate compositions of the present invention normally
comprise the active ingredients in the above stated amounts, one or more
inert carriers and optionally one or more surfactants~ thickening agents~
antifreezing agents and preservatives, and in the case of formulations
destined for use in seed dressing, insecticides and bird repelleints.
The concentrates may be solids usualty known as wettable powders, dusts or
liquids which may be aqueous suspensions, solutions or emulsifiable
concentrates.
Wettable powders or dusts comprise an intimate mixture of the activ
ingredients, one or more inert carriers and appropriate surfactants. The
inert carrier may be chosen from the attapulgite clays, the montmorillonite
clays~ the diatomaceous earths~ kaolins, micas, talcs and purified silicates.
Effective surfactants may be found among the sulfonated lignins, the
naphthalene sulfonates and condensed naphthalene sulfonates, the alkyl
succinates, the alkylbenzene sulfonates, the alkyl sulfates and nonionic
surfactants such as ethylene oxide adducts of phenol. Wettable powder
formulations falling within the scope of the invention will normally comprise
the following ingredients:
(a) For seed dressing use % by weight
Pyrimidine methanol 2 to-15
Imidazole 0.5 to 10
Surfactant(s) 2 to 10
Insecticide 0 to 30
Bird-repellent 0 to 30
Inert carrier(s) to 100
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(b) For foliar spray use % by weight
Pyrimidine methanol 1 to 10
Imidazole 5 to 50
Surfactants(s) 1 to 10
Inert carrier(s) to 100
Dusts falling within the scope of the invention will normally
comprise the following ingredients:
(c) For seed dressing use % by weight
Pyrimidine methanol 2 to 15
Imidazole 0.5 to 10
Insecticide 0 to 30
Bird-repellent 0 to 30
Surfactant(s) 0 to 5
Dust-binding oil 0 to 5
Inert carrier(s) to 100.
Aqueous suspensions, solutions and emulsifiable concentrates
comprise the active ingredients suspended or dissolved in water or suitable
solvents respectively together with any desired surfactants, thickening
agents, antifreezing agents or preservatives. Suitable surfactants may
be chosen from those mentioned above in connection with wettable powders.
Thickening agents, if used, are normally chosen from appropriate cellulose
materials and natural gums whilst glycols will generally be used when an
antifreezing agent is required. Preservatives may be chosen from a
wide range of materials such as the various paraben antibacterials, phenol,
o-chlorocresol, phenyl mercuric nitrate and formaldehyde. Suitable
solvents include alkyl substituted benzenes, o-chlorotoluene, heavy aromatic
naphthalenes, glycol ethers and cyclic ketones. Typical examples of aqueous
suspensions, falling within the ~cope of the invention are; -
(d) For seed dressin~_use % weighttvolume
Pyrimidine methanol 2 to 15
Imidazole 0.5 to 10
Surfactant(s) 1 to 15
Thickening agent 0 to 3
Antifreezing agent 0 to 20
j Preservative 0 to 1
I Water ~o 100.
(e) ~OR ~OL~AR SPRAY USE % weighttvolume
_
Pyrimidine methanol l to 10
Imidazole 5 to 50
Surfactants (s) l to 15
Thickening agent O to 3
Antifreezing agent O to 20
Preservative O to 1
Water to 100.
Typical examples of solutions and emulsifiable concentrates are:
(f) For seed dressing use % weight/volulne j
Pyrimidine methanol 2 to 15
Imidazole 0.5 to 10
Surfactant~s) O to 15
Organic solvent(s) to 100.
(g) For foliar spray use % weight/volume
Pyrimidine methanol 1 to 10
Imidazole 5 to 50
Surfactant(s) 1 to 15
Organic solvent(s) to 100.
Whilst the foregoing general examples will adequately demon~strate
to those skilled in the art the types of concentrate compositions of use
in the present invention, the following specific examples are given to further
illustrate the invelltion but are not to be construed as limiting the
invention in any way. In these examples, fenarimol is the compound
~-(2-chlorophenyl)-~-(4-chlorophenyl)-5-pyrimidine methanol and nuarimol
is the compound ~-(2-chlorophenyl)--(4-fluoropheny~-5-pyrimidine methanol.
Examples 1 to 8 illustrate the preparation of wettable powders.
EXAMPLE 1
% by weight
Nu3rimol 10
Imidazole nitrate 2.5
Ethoxylated nonylphenol 4 1
Sodium lignin sulfonate 3
Silica 8
Clay 10
The active ingredients, Nuarimol and the imidazole nitratejwere
milled and then blended with the other ingredients in conventional mixing
equipment. The blend was then milled in a fluid energy mill to a size
range of from 1 to 10 microns and finally the mixt;ure- was reblended and
deaerated prior to being packaged.
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Similarly,the following other wettable powders were prepared:
EXAMPLE 2.
% by weight
Fenarimol 8
Imidazole sulphate 1.25
Sodium lauryl sulfate 4
Sodium lignin sulfonate 2
Kaolin to lO0.
EXAMPLE 3.
/~ by weight
Nuarimol 4
: Imidazole nitrate 40
Sodium succinate 8
Mica 5
Clay to 100.
EXAMPLE 4.
% by weight
: 15 Fenarimol 3
: Imidazole nitrate 50
Sodium lignin sulfonate 4
Sodium succinate 2
Clay to lO0.
.,
EX~MPLE 5.
. 20 % by weight
Fenarimol 5
Imidazole nitrate 20
Sodium lauryl sulfate 7
. Silica 8
Clay to 100.
EXAMPLE 6.
: __
% by weight
. Nuarimol 10
Imidazole sulphate 5
Sodium alkyl succinate 3
. Sodium lignin sulfonate 2
. Clay to 100.
EXAMPLE 7.
: 30 % by weight
Nuarimol lO
Imidazole base 2
Polyvinylpyrrolidone 1.5
. Sodium alkyl aryl sulphonate 2.
Sodium silico aluminate 7.5
. Clay to 100.
'., j _ ~ _
I ~
. - .
.
¦' In this example, the imidazole base was impregnated onto sodium silico
¦l aluminate as a 25% concentrate before use.
~I EXAMPLE 8.
li % by weight.
¦! Nuarimol 10.0
Imidazole nitrate 2.0
Polyvinylpyrrolidone 1.5
! "Bio Terge AS-9~F"* 1.0
I Silica 1.5
I Permanent Red R 5.0
I Clay to 100.
*Tr~d~ marh for a blend of sodium C14 olefin and sodium C16d - a
olefin sulphonates.
Examples 9 to 12 illustrate the preparation of aqueous suspensions
of the inventic.n.
EXAMPLE 9.
% weight/volume
Nuarimol 10
Imidazole nitrate 50
Sodium naphthalene sulfonate 8
Sodium lauryl sulfate 4
Gum arabic 1
o-chlorocresol 0.5
Water to 100.
Both active ingredients, size reduced by conventional means, if
~20 l necessary, were dispersed in water containing the surfactant system,
¦ preservative and part of the thickening agent. The particle size of both
¦ toxicants was further reduced by liquid milling, the balance of the
thickening agent added, the mixture allowed to hydrate and the product
I diluted to volume with water.
l Similarly, the following other aqueous suspensions were prepared:
EXAMPLE 10.
% weight/volume
I Fenarimol lO
: ! Imidazole sulphate 5
Calcium dodecylbenzene sulfonate 1
Ethoxylated nonylphenol blend 8
-30 ~ Xanthan gum 0.2
; ' Water to 100.
",.', .`
' , _ g _
~ .
~/ . ,
. '.
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EXAMPLE 11.
/~ weight/volume
Nuarimol 10.0
Imidazole base 2.5
Sodium silico aluminate 7.5
Polyoxyethylene-polyoxypropylene
glycol block copolymer 2.0
Xanthan gum 0.3
Acrylic polymer 2.0
Permanent Red R 5.0
Water to 100.
EXAMPLE 12.
% weight/volume
Nuarimol 10.0
Imidazole sulphate 2.5
Fatty alcohol polyglycol ether 2.0
Xanthan gum 0.3
Polyvinyl pyrrolidone2.0
i Water to 100.
Examples 13 and 14 illustrate the preparation of dusts according
to the invention.
EXAMPLE 13.
I lO weight
Nuarimol 10.0
Imidazole base 2.5
i Iron oxide (red) 5.0
Sodium silico aluminate7.5
1 20 Clay (75% <2~) 10.0
Mineral oil 1.5
Slate powder (50% ~10~to 100.
EXAMPLE 14.
% by weight
Fenarimol 10
Imidazole base 2.5
Permanent Red R 5,0
Sodium silico aluminate 7.5
Mineral oil 2.0
I Talc (50% <20~) to 100.
,
~i The imidazole base was absorbed onto sodium silico aluminate and
the combined material, together with pyrimidine methanol was milled to a
; particle size in the range of from 1 to 10 microns in a fluid energy mill,
The milled material was then blended with the other dry ingredients and the
oil sprayed onto the blend.
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Examples 15 and 16 illustrate the preparation of solutions of
the invention.
EXAMPLE 15
% weight/volume
Fenarimol 10
Imidazole base 2
Dimethylformamide 8
Xylene to 100
EXAMPLE 16
% weight/volume
Nuarimol 8
Imidazole base 2.5
Dimethylformamide 10
Xylene to 100
The active ingredients were dissolved with stirring in the dimethylformamide
in the presence of half the aromatic solvent. After dissolutlon of the
active ingredients the remainder of the aromatic solvent was added and
the solution thus formed filtered and packaged.
Examples 17 and 18 illustrate the preparation of emulsifiable
concentrates of the invention.
.
EXAMPLE 17
% weight/volume
Fenarimol 5
Imidazole base 10
Ethoxylated nonyl phenol 3
Calcium dodecylbenzene sulphonate 2
~` 2-Ethoxyethanol 20
Xylene to 100
EXAM~LE 18
,.`
% weight/volume
' ~5 Nuarimol 10
: Imidazole base 10
. Polyoxyethylene glyceride ester 2.5
~ Calcium dodesylbenzene sulphonate 2.5
: 2-Methoxyethanol 25
Heavy aromatic naphtha to 100
,
¦ The active ingredients and surfactants were dissolved in the aliphatic
solvents and the aromatic solvents were then added to the solution thus
fo med, Af ~r filtrati~n the emulsifi:ble concentrate was p~ck~ged.
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