FONGICIDES

FUNGICIDAL COMBINATIONS

Abrégé anglais

ABSTRACT
A fungicidal formulation comprising as one fungicidally active
ingredient a triazole or pyrimidine compound of the formula :-
<IMG> or
<IMG>
I(a) I(b)
where X is chlorine or fluorine, and as a second fungicidally active
ingredient a benzimidazole or aluminium salt of the formula :-
<IMG> or <IMG>
II(a) II(b)
and methods of treating fungal infections of grapes or cereals therewith.

Revendications

The embodiments of the invention m which an exclusive
property or privilege is claimed are defined as follows:
1. A fungicidal formulation comprising as one fungicidally active
ingredient a triazole or pyrimidine compound of the formula :-
<IMG> or
<IMG>
I(a) I(b)
where X is chlorine or fluorine, and as a second fungicidally
active ingredient a benzimidazole or aluminium salt of the
formula :-
<IMG> or <IMG>
II(a) II(b)
associated with one or more inert, non-phytotoxic carrier(s) therefor,
said compounds of formula I and formula II being present in said fungicidal
formulation in a ratio of the formula I compound to the formula II compound
which ranges from 5:1 to 1:300 by weight.
2. A fungicidal formulation as claimed in claim 1, which comprises
from 0.5 to 90% by weight of active ingredients, the remainder consisting of
one or more inert, non-phytotoxio carrier(s) therefor.
11

3. A fungicidal formulation as claimed in claim 2, which comprises
a compound of formula I(b) in which X is chlorine.
4. A fungicidal formulation as claimed in Claim 1
which comprises a compound of formula II(b) and additionally
2-[(trichloromethyl)-thio]-lH-isoindole-1,3(2H)-dione in a ratio
by weight of from 3:1 to 1:1 of said compound of formula II(b) to said dione.
5. A method of preparing a fungicidal formulation as claimed in
claim 1 or claim 2 which comprises admixing a Formula I compound and a
Formula II compound, in a ratio of said formula I compound to said formula
II compound which ranges from 5:1 to 1:300, with one or more inert, non
phlytotoxic carriers) therefor.
6. A method of treating or preventing fungal infections in plants which
comprises treating said plants with a formulation as claimed in
claim 1 or claim 3 or with a formulation as claimed in claim 4 diluted
with water.
7. A method for treating or preventing downy mildew
in grapes which comprises spraying said grapes with an aqueous dispersion of
a formulation as claimed in claim 1 or 2 which comprises a pyrimidine
of formula I(b) in which X is chlorine and the aluminium salt of formula
II(b).
8. A method for treating or preventing fungal
infections in cereals which comprises spraying said cereals with an aqueous
dispersion of a formulation according to claim 1 which comprises a
pyrimidine of formula I(b) in which X is fluorine and the benzimidazole of
formula II(a).
12

Description

q~ ~
1 The present invention relates to a method of treating funga~ lnfections
of cultivated plants with novel combinations of chemicals and also provides
fungicidal formulations containing said novel combinationsO
According to one aspect of the present inventlon therefore, there is
provided a fungicidal formulation comprlsing as o~e fungicidally active
ingredient a triazole or pyrimidine compound of the formula :-
~ ~ ~ N ~ ~ Cl
~ 3--o l co C(CH3~3 ~N ~
~ I(b)
where X is chlorine or fluorine9 and as a second fungicidally active
ingredient a benzimidazole or aluminium salt of the formula :-
~ C - NH-C-OCH3 ~ [C2H50-¦-O( ~ AL
~ H
i II(a~ II(b)
I - 2 ~
.~, . .

1 associated with one or more inert~ non-phytotoxic carriers therefor.
All of the aorementioned compounds are known compounds and may be
prepared by methods well-defined in the literature. The combinations of
active ingredients defined in the above formulation are novel and have been
found to be surprisingly effective in controlling or combatting fungal
infections of cultivated plants, the combination of a compound of
formula I(a) or I(b) and II(b) being particularly useful in controlling
mildew infections of grapes whilst the combination of a formula I(a)
or I(b) and for~ula II(a) compound has been found to be especially valuable
in the treatment of cereal diseases such as powdery mlldew9 foot rot,
and other foliar or ear diseases affecting cereals at the ripening 3tage.
According to a second aspect of the invention thereforeg there is
provided a method of treating fungal infections of plants especially
cereals and grapes which comprises applying to said plants a fungicidally
effective amount of a fungicidal formulation as defined above~ In the
aforesaid method, the formulatlon is preferably applied by foliar application
at any time after crop emergence until harvesting takes place, the amount
and frequency of application being de~ermined by the severity or expected
severity of the fungal disease. However it is a feature of the invention
and a particular advantage obtained from the use of the above-defined
combinations that a reduced frequency of treatment7 for example only once
every 2 to 3 weeks to control grape mildew infectionsg may be effectively
employed thus achieving a valuable reduction in labour co~ts.
The preferred pyrimidine for use in grape treatment is that in which
I ~ is chlorine whereas the formula I(b) compound in which X is fluorlne is
preferred for use in connection with fungal infections of cereals~
I
I
- 3 -
Il ~
, . `~ ' -~ ~';,

ll~ I' t'
~ `4~ ~
The components of the formulations of this invention may be applied
sequentially or simultaneously to the plant being treated, the latter being
preferred in accordance with the invention. The compound of formula I(a)
is preferably applied in an amount of from 10 to 500g. per hectare and the
compo~lnds of formula I(b) are preferably applied in sn amount of from 10 to
lOOg~ ost preferably 1to 30g per hectare in the treatment of grapes~
whereas the compounds of formula II(a) or II(b) are preferably
applied in amounts of from 100 to 3000g. per hectare. Thùs the ratio of
compounds of formula I to compounds of fo~mula II in the combinations of the
invention may range from 5:1 to 1:300 by weight~ Preferably the ratio of
formula I(a) to formula II(a~ compound lies between 2:1 and 1:~5 with from
20 to 200g. per hectare of formula I(a) compound being applied, and the ratio ;
of formula I(b) to formula II(a) compound lies between 1:1 and 1-25 with from
20 to lOOg. per hectare of formula I(b) compound being applied, whilst from
100 to SOOg. per hectare of formula LI(a) compound may be used. Preferably
the ratio of formula I(a) to formula II(b) compound ls in the range of
1:5 to 1:100 with again 20 to 200g. per hectare of the formula I(a) compound
being used, and the ratio of formula I(b) to Eormula II(b) compound is in
the range of 1:10 to 1:100 with 20 to lOOg. per hectare of formula I(b)
compound being used~ with from 1000 to 2000g. per hectare of the compound
of formula II(b) being employed. ~
The formula II(b) compound,aluminium sslt of ethylphosphite (AEP)~ is
! preferably used in comblnation with a further fungicide for example
1 ~ancozeb or- possibly folpet, 2-[(trichloromethyl)-thio~-lH-isolndole-1,3~2H)-
i dio~e (see Phvtiarie Phytoe~armacie 1 (1977)). When used in con~unction with
I` the further fungicide the ratio of AEP to said fun~icide will lie in the
li range 3:1 to 1:2 by weight.
- 4
,.,
~ . .

~ 6
l In order to simplify manufacture~ storage and transport~ the
combinations of the formulae I and II compounds will be normally produced
in concentrate form intended for dilution in wa~er to the degree necessary
to enable the abovementioned application rates to be easily achieved. Such
concentrated formulations may contain from 0.5 to 90%, preferably 5 to 90%,
by weight of active ingredients associated with one or more inert non
ph~totoxic ca~rier(s) therefor. Such formulations will usually be in the
form o a wettable powder or dust~ or aqueous suspension, although it should
be noted that aqueous suspensions of AEP tend to be unstable because of
the relatively short half-life (approximately 100 da~s) of AEP in aqueous
media. The concentrate formulations are intended for appropriate dilution
with water prior to use. This formation of an aqueous dispersion can be
carried out in conventional spray tanks suitable for the purpose.
Wettable powders or dusts comprlse an intimate mixture of ~he active
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, kaolins7 micas7 talcs and purified silicates.
Effective surfactants may be found among the sulfonated lignins,
the naphthslene sulfonates and condensed naphthalene sulfonates, the alkyl
succinates, the alkylbenzene sulfonates, the alkyl sulfates and nonionic
surfactants such as ethylene oxide adducts of phenolO Illustrative of
wettable powders falling within the scope of the in~ention are those having
the following composition :
Wettable Pouders
~!~
Formula I compound0.25 to 10
Formula II compound 10 to 80
¦ Surfactant~s) 0 to 10
¦ Dispersing Agent 0 to 10
Anticaking agent 0 to 10
I~ert carrier~s) to 100

1 Aqueous suspensions and solutions comprise the active lngredients
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 Thickenin~
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 chlorocresol9
phenyl mercuric nitrate and formaldehyde. Typical examplas of aqueous
suspensions 9 falling within the scope of the inventions are :
~)
Formula I compound 0.1 to 8
Formula II(a) compound 20 to 52
Surfactant(s~ 0 to 15
Thickening agent 0 to 3
Antifreezing agent 0 to 20
Preservative 0 to
Antifoaming agent 0 to 0.5
Water to 100
¦ Whilst the foregoing general examples will adequately demonstrate to
those skilled in the art the types of concentrate compositions of use
in the present invention, the following non-limitative Examples will serve
to ~urther illustrate the formulation aspects of the present invention.
- 6 -

1 In these Examples~ the term "CCPM" represents the ormula I(b) compound
in which X is chlorine whilst the re ated compound in which X is fluorine
is representea by the latters "CFPM". Similarly~ the formula I(a) compound
is denoted by the symboL "CTDB", the formula II(a) compound "MBC" and the
fonmula II(b) compound "AF,P",
EXAMPLES 1 to 8
The following wettable powders were prepared ~-
(1) ~ ~ weight
. CCPM 0-5
A~P 50,0
Sodium dioctylsulphosuccinate2.0
Ethox~lated nonylphenol 2.0
Sodium lignin sulphonate 3,0
Silica 6.0
Kaolin clay to 100.0
(2)
CFPM loO
AEP 50.0
Sodium lauryl sulphate 3.0
Sulphonated lignin 2.0
Diatomaceous earth to 100.0
(3)
CTDB 0.5
AEP 37 5
¦ Sodium alkyl ether sulphate5.0
Sulphite lye powder 3.0
Silica 4~0
Talc to 100.0

1 t4) ZL~
CCPM 500
MBC 50.0
Sodium dioctyl sulphosuccinate 4.0
Sodium lignin sulphonate 1.5
Precîpitated silica 2.5
Attapulgi~e to 100.0
~5) % b~ weight
CFPM 3.0
MBC 45 0
Sodium allcylnaphthalene sulphonate 8.0
Diatomaceous earth 6.0
Montmorillonite to 100.0
(6)
CTDB 12.0
MBC 6010
Sodium salt o condensed napthalene
sulphonic acids 5.0
Sodium tridecyl sulphate 2.0
~0 Silica 5.0
Kaolin to 100.0
~7) ~L~~L
CCPM L~0
~ .~EP 30OO
Folpet 15.0
j Sodium lauryl sulphate 2,5
¦ Sodium lignin sulphonate 4~0
Precipitated silica 8.0
l Kaolin to 100.0
- B -

1 ~8) % bv wei~
CTDs 2.0
AEP 40~0
Mancozeb 20.0
S Ethoxylated nonyl phenol 2~0
Sodium dioctyl sulphosuccinate 2.0
Sodlum.lignin sulphonate 300
Hydrated sodium silicoaluminate 7.5
Talc to 100.0
In each Example, the active ingredients were carefully blended
~ith the specified exclpients in con~entional mixi~g equipment. The
blend was then further milled in a fluid enargy mill to a size range of
from 1 to 10 microns and finally the mixture was reblended and deaerated
prior to being packaged.
EX MPLES 9 to.ll
The following aqueous suspensions were prepared :-
(9) ~L~2
CFPM 40~
MBC 40 0
Polyoxyethylene polyoxypropylene
block copolymer 2,0
Xanthan gum 004
Silicone antifoam 0.1
Water to 100.0
~0 _ 9 _

( 10) ~
CTDB 2.5
MBC 50.0
Sodium lauryl sulphate 3.0
Bentonite 3.0
Ethylene glycol 5.0
Formaldehyde 0.2
Water to 100~0
(11) ~
CCPM 5~0
~sC 40.0
Ethoxylated nonyl phenol 4~0
Hydroxymethyl cellulose 2.0
Silicone antifoam 0.15
Propylene glycol 6 0
Water to ~~
Both active ingredients, size rèduced by conventional means~ where
appropriate, were dispersed in water containing the surfactant system,
preservative and part of the thickening agent. The particle si~e of
both actives was further reduced by liquid millingl the balance of the
thickeni~g agent added, allowed to hydrate and the product diluted to
Yolume with water.
~ 10