Fungicidal composition comprising a 2-imidazolin-5-one

A fungicidal composition comprising a compound A having the formula: ##STR1## wherein M is an oxygen or sulphur atom, n is 0 or 1, and Y is a fluorine or chlorine atom or a methyl radical; and at least one fungicidal compound B. A method for preventing or controlling phytopathogenic fungi on crops by applying an effective and non-plant-poisonous amount of said compound on the exposed parts of the plants is also disclosed.

The subject of the present invention is a fungicidal composition comprising 
a 2-imidazolin-5-one type compound and a process using the said 
composition and intended for protecting, curatively or preventively, crops 
against fungal attacks. 
Racemic compounds derived from 2-imidazolin-5-ones with fungicidal action, 
which make it possible to prevent the growth and development of 
phytopathogenic fungi capable of attacking crops, are known especially 
through European Patent Application EP 551048. 
It is however always desirable to enhance the activity spectrum and the 
efficacy of such compounds with fungicidal action. 
It is also desirable to have available fungicidal products having a 
curative activity since in this case it is possible to decrease the number 
of systematic preventive treatments while ensuring good control of 
parasites. 
It is also highly desirable to have available fungicidal products with 
lasting enhanced action such that the number of plant-protection 
treatments necessary for good control of parasites can be spaced out over 
time. 
It is in all cases particularly advantageous to be able to decrease the 
quantity of chemical products spread in the environment while ensuring 
effective protection of crops against fungal attacks. 
It has now been found that one (or several) of the preceding objectives 
could be achieved by means of the fungicidal composition according to the 
present invention. 
The subject of the present invention is therefore, firstly, a fungicidal 
composition comprising a compound A of formula (I): 
##STR2## 
in which: M represents an oxygen or sulphur atom; 
n is an integer equal to 0 or 1; 
Y is a fluorine or chlorine atom, or a methyl radical; 
and at least one fungicidal compound B chosen from the group comprising: 
the derivatives of dithiocarbamic acid and its salts such as maneb, 
mancozeb, zineb, metiram-zinc, 
the derivatives of phosphorous acid such as metallic phosphites such as 
fosetyl-Al, phosphorous acid itself and its alkali metal or alkaline-earth 
metal salts, 
the chlorinated derivatives of benzene, such as chlorothalonil, 
the derivatives comprising a heterocycle containing from 1 to 2 nitrogen 
atoms such as fluazinam, fludioxonil, prochloraz, 
the derivatives of triazoles such as bromuconazole, cyproconazole, 
difenoconazole, diniconazole, epoxyconazole, fenbuconazole, flusilazole, 
flutriafol, hexaconazole, metconazole, tebuconazole, tetraconazole, 
triticonazole, 
the dicarboximide derivatives such as captan, folpel, captafol, iprodione, 
procymidone, vinchlozolin, 
copper or the organic or inorganic derivatives of copper, such as copper 
oxychloride or copper hydroxide, 
amides such as cymoxanil, metalaxyl, benalaxyl and oxadixyl, 
the derivatives of morpholine such as dimethomorph, dodemorph, tridemorph, 
fenpropimorph, fenpropidin, triadimenol, 
the derivatives of the methoxyacrylate type such as 
methyl-(E)-2-{2-6-(2-cyanophenoxy)pyrimidin-4-yloxy!phenyl}-3-methoxyacry 
late, methyl-(E)-methoxyimino.alpha.-(o-tolyloxy)-o-tolyl!acetate, or 
alternatively N-methyl-(E)-methoxyimino2-(2,5-dimethyl 
phenoxymethyl)phenyl!acetamide, 
the derivatives of guanidine such as dodine, 
a derivative of the phenylbenzamide type of formula (II): 
##STR3## 
in which: R.sup.1 and R.sup.2.sub.1 which are identical or different, are 
a hydrogen or halogen atom, or an optionally halogenated alkyl radical, 
and 
R.sup.3 and R.sup.4, which are identical or different, are an alkyl radical 
of 1 to 4 carbon atoms.

The fungicidal composition according to the invention advantageously 
comprises the components A and B in a weight ratio A/B of between 0.0005 
and 50, preferably of between 0.001 and 10. 
It is clearly understood that the said fungicidal composition may contain a 
single compound B or more than one such compound, for example 1, 2 or 3 B 
compounds depending on the use for which it is intended. 
The fungicidal composition according to the invention for which compound A 
is the compound of formula (I) in which M is a sulphur atom and n is equal 
to 0, also called 
(4S)-4-methyl-2-methylthio-4-phenyl-1-phenylamino-2-imidazolin-5-one is 
preferred. 
One of the following derivatives is preferred for the meaning of compound 
B: 
a derivative of dithiocarbamic acid and its salts chosen from maneb, 
mancozeb, metiram-zinc, 
a derivative of phosphorous acid chosen from fosetyl-Al, and phosphorous 
acid itself and its calcium or potassium salts, 
chlorothalonil, 
a derivative comprising a heterocycle containing from 1 to 2 nitrogen atoms 
chosen from fluazinam, fludioxonil, prochloraz, 
a triazole derivative chosen from bromuconazole, difenoconazole, 
epoxyconazole, tebuconazole, triticonazole, 
a dicarboximide derivative chosen from folpel or iprodione, 
a copper derivative chosen from copper oxychloride or copper hydroxide, 
an amide chosen from cymoxanil, metalaxyl or oxadixyl, 
dimethomorph, 
the derivative of the phenylbenzamide type which corresponds to the formula 
(I) in which R.sup.1 represents a hydrogen atom, R.sup.2 represents a 
trifluoromethyl radical, R.sup.3 represents a methyl radical and R.sup.4 
represents an ethyl radical; in other words the derivative of the 
phenylbenzamide type called 
N-methyl-N-ethyl-2-(3,4-dimethoxyphenyl)-4-trifluoromethylbenzamide. 
Among the meanings more especially preferred for compound B which are 
defined above, fosetyl-Al, mancozeb, cymoxanil, dimethomorph, oxadixyl or 
N-methyl-N-ethyl-2-(3,4-dimethoxyphenyl)-4-trifluoromethylbenzamide is 
again preferred. Quite unexpectedly, the composition according to the 
invention thus considerably enhances the action of the active substances 
taken separately for a number of fungi which are particularly harmful for 
crops, such as in particular vine or solanaceous crops. This enhancement 
results especially in a decrease in the doses of each of the constituents, 
which is particularly advantageous for the user and the environment. The 
fungicidal product thus has synergistic properties confirmed by applying 
the Tammes method, "Isoboles, a graphic representation of synergism in 
pesticides" Netherlands Journal of Plant Pathology, 70 (1964), p. 73-80 or 
as defined by Limpel, L. E., P. H. Schuldt and D. Lammont, 1962, Proc. 
NEWCC 16: 48-53, using the following formula, also called Colby formula: 
EQU E=X+Y-X.Y/100 
in which: 
E is the expected percentage inhibition of the growth of the fungus by a 
mixture of two fungicides A and B at defined doses, equal to a and b 
respectively; 
X is the observed percentage inhibition by fungicide A at dose a, 
Y is the observed percentage inhibition by fungicide B at dose b. 
When the observed percentage inhibition of the mixture is greater than E, 
there is synergy. 
Preferably, when component B is a phosphorous acid derivative, and is 
especially fosetyl-Al, the A/B ratio is between 0.001 and 2, preferably 
between 0.002 and 1. 
Preferably, when component B is a derivative of formula (II), and is 
especially 
N-methyl-N-ethyl-2-(3,4-dimethoxyphenyl)-4-trifluoromethylbenzamide, the 
A/B ratio is between 0.1 and 10, preferably between 0.2 and 10, and still 
more preferably between 0.25 and 4. 
Preferably, when component B is cymoxanil, the A/B ratio is between 0.05 
and 4, preferably between 0.2 and 4, and still more preferably between 
0.25 and 4. 
Preferably, when component B is oxadixyl, the A/B ratio is between 0.5 and 
30, preferably between 0.5 and 10. 
Preferably, when component B is a dithiocarbamic acid derivative such as 
mancozeb, the A/B ratio is between 0.02 and 2, preferably between 0.1 and 
1. 
Preferably, when component B is a morpholine derivative and especially 
dimethomorph, the A/B ratio is between 0.1 and 2, preferably between 0.2 
and 1. 
Compound A is described in European Patent Application No. 94420167.2 which 
was unpublished on the filing date of the present patent application. 
The compound A of formula (I) in which M is a sulphur atom and n is equal 
to 0, in other words 
(4S)-4-methyl-2-methylthio-4-phenyl-1-phenylamino-2-imidazolin-5-one, can 
be prepared in the following manner. 
Preparation of 
(4S)-4-methyl-2-methylthio-4-phenyl-1-phenylamino-2-imidazolin-5-one 
This preparation is carried out in two stages. 
First stage 
In a first stage, methyl (2S)-2-isothiocyanato-2-phenylpropionate is first 
prepared according to one of the procedures mentioned in Sulfur Reports 
Volume 8 (5) pages 327-375 (1989), from the corresponding amino ester 
which is itself easily obtained from the .alpha.-amino acid. 
Thus, 780 g (3.61 moles) of (+)-methyl (2S)-2-amino-2-phenylpropionate 
hydrochloride! are introduced into a 20-1 reactor, followed by 3.4 l of 
water. The temperature is adjusted to 20.degree. C. 3.4 l of toluene are 
added and then 911 g (10.8 moles) of sodium hydrogen carbonate are added 
in fractions over 1 hour. The temperature decreases to 8-9.degree. C. 276 
ml (3.61 moles) of thiophosgene are poured in over 2 hours. The reaction 
is accompanied by a gaseous emission and a rise in temperature which 
reaches 24.degree. C. at the end of the pouring in. The medium is again 
maintained stirring for 2 hours. After decantation, the aqueous phase is 
extracted with 2 l of toluene. The combined toluene phases are washed with 
4 l of water and then dried over magnesium sulphate. The solution is 
concentrated under reduced pressure. 
682 g of (+)-methyl (2S)-2-isothiocyanato-2-phenylpropionate! are thus 
obtained in the form of a slightly coloured oil (yield=85%). 
A specific rotation, equal to +16.degree. (+ or -6.4%), is measured 
according to the usual method and for a solution of 0.78 g of product in 
100 ml of chloroform, at a temperature of 29.degree. C. 
Second stage 
In a second stage, 682 g (3.08 moles) of methyl 
(2S)-2-phenyl-2-isothiocyanatopropionate, prepared in the manner which has 
just been described, are dissolved in 4 l of anhydrous tetrahydrofuran and 
then introduced into a 20-1 reactor through which runs an argon stream. 
The whole is cooled to 15.degree. C. 343 g (3.08 moles) of 
phenylhydrazine, dissolved in 2 l of tetrahydrofuran, are poured in over 
30 min while the temperature is maintained between 15.degree. C. and 
18.degree. C. The medium is maintained stirring for 40 min and then cooled 
to 0.degree.. A solution of 346 g (3.08 moles) of potassium tert-butoxide 
is poured into 4 l of tetrahydrofuran over 1 hour while the temperature is 
maintained at 0.degree. C. The stirring of the medium is continued for 2 
hours at 0.degree. C. and the formation of a light pink precipitate is 
observed. 218 ml (3.39 moles) of methyl iodide are poured in over 15 min 
while the temperature is maintained between 0.degree. C. and 3.degree. C. 
then the temperature is allowed to rise to room temperature while the 
stirring is maintained for 2 hours. The reaction mixture is poured over 5 
l of water. After decantation, the aqueous phase is extracted with three 
times 3 l of is ethyl acetate. The combined organic phases are washed with 
5 l of water, dried over magnesium sulphate then concentrated under 
reduced pressure. 1,099 g of a brown solid are obtained. The latter is 
recrystallized from 2 l of toluene. 
After drying, 555 g of 
(+)-(4S)-4-methyl-2-methylthio-4-phenyl-1-phenylamino-2-imidazolin-5-one 
are obtained in the form of an off-white solid melting at 138.degree. C. 
(yield=58%). 
A specific rotation equal to +61.1.degree. (+ or -2.9.degree.) is measured 
according to the usual method and for a solution of 0.86 g of product in 
100 ml of ethanol, at 27.degree. C. 
An enantiomeric excess (e.e) greater than 98% is measured by 
high-performance liquid chromatography on a chiral phase. 
The compound A of formula (I) in which M is an oxygen atom and n is equal 
to 0 is obtained by reacting 
(4S)-4-methyl-2-methylthio-4-phenyl-1-phenylamino-2-imidazolin-5-one with 
methanol and in the presence of sodium, according to a procedure described 
in Patent Application EP 599749. 
The compound A of formula (I) in which n is equal to 1 is obtained from the 
embodiments indicated above with modifications of the starting reagents 
which are easily within the means of persons skilled in the art. 
The structures corresponding to the common names of the fungicidal active 
substances appearing in the definition of B are indicated in at least one 
of the following two books: 
"The pesticide manual" edited by Charles R. Worthing and Raymond J. Hance 
and published by the British Crop Protection Council, 9th Edition; 
Index phytosanitaire 1994, published by the Association de Coordination 
Technique Agricole, 30th Edition. 
As regards the methoxyacrylate type derivatives, 
methyl-(E)-2-{2-6-(2-cyano-phenoxy)-pyrimidin-4-yloxy!phenyl}-3-methoxyac 
rylate is described in International Application WO 9,208,703; 
methyl-(E)-methoxyamino.alpha.-(o-tolyloxy)-o-tolyl!acetate is described 
in European Patent Application EP 253213; 
N-methyl-(E)-methoxyimino2-(2,5-dimethylphenoxy-methyl)phenyl!acetamide 
is described in European Patent Application EP 398692. 
The phenylbenzamide type derivative is described in European Patent 
Application EP 0,578,586 published on Jan. 12, 1994. 
The fungicidal composition according to the invention comprises, as active 
substance, compound A and at least one compound B in the form of a mixture 
with solid or liquid carriers which are agriculturally acceptable, and 
surface-active agents which are also agriculturally acceptable. In 
particular, inert and customary carriers and customary surface-active 
agents can be used. These compositions include not only compositions ready 
to be applied to the crop to be treated by means of an appropriate device, 
such as a spraying device, but also, commercially available concentrated 
compositions which must be diluted before application to the crop. Active 
substance designates the combination of compound A with at least one 
compound B. 
These compositions may also contain all sorts of other ingredients such as, 
for example, protective colloids, adhesives, thickeners, thixotropic 
agents, penetrating agents, stabilizers, sequestrants and the like. More 
generally, compounds A and B may be combined with all solid or liquid 
additives corresponding to the usual formulation techniques. 
Generally, the compositions according to the invention usually contain from 
0.05 to 95% (by weight) of active substance, one or more solid or liquid 
carriers and, optionally, one or more surface-active agents. 
The term "carrier", in the present text, designates a natural or synthetic 
organic or inorganic substance with which the active substance is combined 
to facilitate its application to the aerial parts of the plant. This 
carrier is therefore generally inert and must be agriculturally 
acceptable, especially on the treated plant. The carrier may be solid 
(clays, natural or synthetic silicates, silica, resins, waxes, solid 
fertilizers and the like) or liquid (water, alcohols, especially butanol 
and the like). 
The surface-active agent may be an emulsifier, dispersing or wetting agent 
of the ionic or nonionic type or a mixture of such surface-active agents. 
There may be mentioned for example polyacrylic acid salts, lignosulphonic 
acid salts, phenolsulphonic or naphthalenesulphonic acid salts, 
polycondensates of ethylene oxide with fatty alcohols or fatty acids or 
fatty amines, substituted phenols (alkylphenols or arylphenols in 
particular), ester salts of sulpho-succinic acids, taurine derivatives 
(alkyltaurates in particular), phosphoric esters of alcohols or of 
polyoxyethylated phenols, esters of fatty acids and of polyols, 
derivatives containing sulphate, sulphonate and phosphate functional 
groups of the preceding compounds. The presence of at least one 
surface-active agent is generally essential when the active substance 
and/or inert carrier are insoluble in water and when the vector agent for 
the application is water. 
Consequently, the compositions for agricultural use according to the 
invention may contain the active substance within very wide limits, 
ranging from 0.05% to 95% (by weight). Their content of surface-active 
agent is advantageously between 5% and 40% by weight. 
These compositions according to the invention are themselves in fairly 
diverse, solid or liquid, forms. 
As solid composition forms, there may be mentioned powders for dusting 
(with an active substance content which may be as high as 100%) and 
granules, especially those obtained by extrusion, by compacting, by 
impregnation of a granulated carrier or by granulation from a powder (the 
active substance content in these granules being between 0.5 and 80% for 
these latter cases), effervescent tablets or lozenges. 
The fungicidal composition according to the invention may furthermore be 
used in the form of powders for dusting; a composition comprising 50 g of 
active substance and 950 g of talc may also be used; a composition 
comprising 20 g of active substance, 10 g of finely divided silica and 970 
g of talc may also be used; these constituents are mixed and ground and 
the mixture is applied by dusting. 
As liquid composition forms or forms intended to constitute liquid 
compositions during application, there may be mentioned solutions, in 
particular water-soluble concentrates, emulsifiable concentrates, 
emulsions, concentrated suspensions, aerosols, wettable powders (or powder 
for spraying), pastes and gels. 
The emulsifiable or soluble concentrates most often comprise 10 to 80% of 
active substance, the emulsions or solutions ready for application 
containing, for their part, 0.001 to 20% of active substance. 
In addition to the solvent, the emulsifiable concentrates may contain, when 
necessary, 2 to 20% of appropriate additives such as the stabilizers, 
surface-active agents, penetrating agents, corrosion inhibitors, 
colourings or adhesives previously mentioned. 
From these concentrates, emulsions of any desired concentration, which are 
particularly suitable for application to the crops, may be obtained by 
dilution with water. 
By way of example, here is the composition of some emulsifiable 
concentrates: 
EXAMPLE EC 1 
______________________________________ 
active substance 400 g/l 
alkali metal 
dodecylbenzenesulphonate 
24 g/l 
oxyethylated nonylphenol 
containing 10 molecules of 
ethylene oxide 16 g/l 
cyclohexanone 200 g/l 
aromatic solvent qs 1 liter 
______________________________________ 
According to another emulsifiable concentrate formula, the following is 
used: 
EXAMPLE EC 2 
______________________________________ 
active substance 250 g 
epoxydized vegetable oil 25 g 
mixture of alkylarylsulphonate 
100 g 
and polyglycol ether and fatty 
alcohols 
dimethylformamide 50 g 
xylene 575 g 
______________________________________ 
The concentrated suspensions, which can also be applied by spraying, are 
prepared so as to obtain a stable free-flowing product which does not 
settle and they usually contain from 10 to 75% of active substance, from 
0.5 to 15% of surface-active agents, from 0.1 to 10% of thixotropic 
agents, from 0 to 10% of appropriate additives such as antifoams, 
corrosion inhibitors, stabilizers, penetrating agents and adhesives and, 
as carrier, water or an organic liquid in which the active substance is 
poorly soluble or insoluble: some organic solid substances or inorganic 
salts may be dissolved in the carrier to help prevent sedimentation or as 
antifreeze for the water. 
By way of example, there is a composition of a concentrated suspension: 
EXAMPLE CS 1 
______________________________________ 
active substance 500 g 
polyethoxylated 50 g 
tristyrylphenol phosphate 
polyethoxylated alkylphenol 
50 g 
sodium polycarboxylate 20 g 
ethylene glycol 50 g 
organopolysiloxane oil 
(antifoam) 1 g 
polysaccharide 1.5 g 
water 316.5 g 
______________________________________ 
The wettable powders (or powder for spraying) are usually prepared so that 
they contain 20 to 95% of active substance, and they usually contain, in 
addition to the solid carrier, from 0 to 30% of a wetting agent, from 3 to 
20% of a dispersing agent, and, when necessary, from 0.1 to 10% of one or 
more stabilizers and/or other additives, such as penetrating agents, 
adhesives, or anticaking agents, colourings and the like. 
In order to obtain the powders for spraying or wettable powders, the active 
substances are intimately mixed in the appropriate mixers with the 
additional substances and ground using mills or other appropriate 
grinders. Powders for spraying are thereby obtained whose wettability and 
capacity to form suspensions are advantageous; they can be suspended with 
water at any desired concentration and these suspensions can be used very 
advantageously in particular for application to plant leaves. 
In place of wettable powders, pastes can be made. The conditions and 
methods of preparing and using these pastes are similar to those of 
wettable powders or powders for spraying. 
By way of example, here are various compositions of wettable powders (or 
powders for spraying): 
EXAMPLE WP 1 
______________________________________ 
active substance 50% 
ethoxylated fatty alcohol 
2.5% 
(wetting agent) 
ethoxylated phenylethylphenol 
5% 
(dispersing agent 
chalk (inert carrier) 42.5% 
______________________________________ 
EXAMPLE WP 2 
______________________________________ 
active substance 10% 
C.sub.13 branched-type oxo 
0.75% 
synthetic alcohol ethoxylated 
by 8 to 10 ethylene oxides 
(wetting agent) 
neutral calcium 12% 
lignosulphonate (dispersing 
agent) 
calcium carbonate (inert 
qs 100% 
filler) 
______________________________________ 
EXAMPLE WP 3 
This wettable powder contains the same ingredients as in the preceding 
example, in the proportions below: 
______________________________________ 
active substance 75% 
wetting agent 1.50% 
dispersing agent 8% 
calcium carbonate (inert 
qs 100% 
filler) 
______________________________________ 
EXAMPLE WP 4 
______________________________________ 
active substance 90% 
ethoxylated fatty alcohol 
4% 
(wetting agent) 
ethoxylated phenylethylphenol 
6% 
(dispersing agent) 
______________________________________ 
EXAMPLE WP 5 
______________________________________ 
active substance 50% 
mixture of anionic and nonionic 
2.5% 
surfactants (wetting agent) 
sodium lignosulphonate 5% 
(dispersing agent) 
kaolinic clay (inert carrier) 
42.5% 
______________________________________ 
The aqueous dispersions and emulsions, for example the compositions 
obtained by diluting a wettable powder or an emulsifiable concentrate 
according to the invention with water, are included within the general 
scope of the present invention. The emulsions may be of the water-in-oil 
or oil-in-water type and they may have a thick consistency like that of a 
"mayonnaise". 
The fungicidal compositions according to the invention may be formulated in 
the form of water-dispersible granules which are also included within the 
scope of the invention. 
These dispersible granules, with an apparent density generally of between 
about 0.3 and 0.6 have a particle size generally of between about 150 and 
2,000 and preferably between 300 and 1,500 microns. 
The active substance content of these granules is generally between about 
1% and 90%, and preferably between 25% and 90%. 
The rest of the granule is essentially composed of a solid filler and 
optionally of surface-active adjuvants which confer water-dispersibility 
properties on the granule. These granules may be essentially of two 
distinct types depending on whether the chosen filler is soluble in water 
or otherwise. When the filler is water-soluble, it may be an inorganic or 
preferably an results filler. Excellent results are obtained with urea. In 
the case of an insoluble filler, the latter is preferably an inorganic 
filler such as for example kaolin or bentonite. It is, in this case, 
advantageously accompanied by surface-active agents (in an amount of 2 to 
20% by weight of the granule) of which more than half for example consists 
of at least one, essentially anionic, dispersing agent such as an alkali 
metal or alkaline-earth metal polynaphthalenesulphonate or an alkali metal 
or alkaline-earth metal lignosulphonate, the rest consisting of nonionic 
or anionic wetting agents such as an alkali metal or alkaline-earth metal 
alkylnaphthalenesulphonate. 
Moreover, although this is not essential, other adjuvants such as 
antifoaming agents may be added. 
The granule according to the invention may be prepared by mixing the 
necessary ingredients followed by granulation by means of several 
techniques which are known per se (coating device, fluidized bed, 
atomizer, extrusion, and the like). The procedure generally ends with 
crushing followed by sieving to the chosen particle size within the limits 
mentioned above. It is also possible to use granules obtained as above and 
then impregnated with a composition containing the active substance. 
Preferably, it is obtained by extrusion, the procedure being carried out as 
indicated in the examples below. 
EXAMPLE DG1 
dispersible granules 
90% by weight of active substance and 10% of pearl urea are mixed in a 
mixer. The mixture is then ground in a toothed roll crusher. A powder is 
obtained which is moistened with about 8% by weight of water. The wet 
powder is extruded in a perforated roll extruder. A granule is obtained 
which is dried, then crushed and sieved, so that only granules with a size 
of between 150 and 2,000 microns are kept respectively. 
EXAMPLE DG2 
dispersible granules 
The following constituents are mixed in a mixer: 
______________________________________ 
active substance 75% 
wetting agent (sodium 2% 
alkylnaphthalenesulphonate) 
dispersing agent (sodium 8% 
polynaphthalenesulphonate) 
water-insoluble inert filler (kaolin) 
15% 
______________________________________ 
This mixture is granulated in a fluidized bed, in the presence of water, 
and then dried, crushed and sieved so as to obtain granules with a size of 
between 0.15 and 0.80 mm. 
These granules may be used alone, dissolved or dispersed in water so as to 
obtain the desired dose. They may also be used to prepare combinations 
with other active substances, especially fungicides, the latter being in 
the form of wettable powders, or granules or aqueous suspensions. 
As regards the compositions suitable for storage and for transport, they 
contain more advantageously from 0.5 to 95% (by weight) of active 
substance. 
The subject of the invention is finally a process for controlling, 
curatively or preventively, phytopathogenic crop fungi, characterized in 
that an effective and nonphytotoxic quantity of a fungicidal composition 
according to the invention is applied to the aerial parts of the plants. 
The phytopathogenic crop fungi which can be controlled by this process are 
especially those: 
of the Oomycetes group: 
of the genus Phytophthora such as Phytophthora infestans (blight of 
solanaceous crops, especially potato or tomato blight), Phytophthora 
citrophthora, Phytophthora capsici, Phytophthora cactorum, Phytophthora 
palmivora, Phytophthora cinnamoni, Phytophthora megasperma, Phytophthora 
parasitica, 
of the Peronosporaceae family, especially Plasmopara viticola (vine downy 
mildew), Plasmopara halstedei (sunflower downy mildew), Pseudoperonospora 
sp (especially cucurbit and hop downy mildew), Bremia lactucae (lettuce 
downy mildew), Peronospora tabacinae (tobacco downy mildew), 
of the Adelomycetes group: 
of the genus Alternaria, for example Alternaria solani (solanaceous crop, 
especially tomato and potato diseases caused by Alternaria), 
of the genus Guignardia, especially Guignardia bidwelli (black rot of the 
vine), 
of the genus Oidium, for example vine powdery mildew (Uncinula necator); 
powdery mildew of leguminous crops, for example Erysiphe polygoni 
(crucifer powdery mildew); Leveillula taurica, Erysiphe cichoracearum, 
Sphaerotheca fuligena; (powdery mildew of Cucurbitaceae, of compositae, of 
tomato); Erysiphe communis (beet and cabbage powdery mildew); Erysiphe 
pisi (pea and lucerne powdery mildew); Erysiphe polyphaga (bean and 
cucumber powdery mildew); Erysiphe umbelliferarum (powdery mildew of 
umbellifers, especially of carrot); Sphaerotheca humuli (hop powdery 
mildew); Erysiphe graminis (cereal powdery mildew); 
of the genus Septoria, for example Septoria nodorum or Septoria tritici 
(septoria spot of cereals); 
of the Basidiomycetes group: 
of the genus Puccinia, for example Puccinia recondita or striiformis (wheat 
rust). 
The fungicidal composition which is the subject of the invention is applied 
by means of various methods of treatment such as: 
spraying a liquid comprising the said composition onto the aerial parts of 
the crops to be treated, 
dusting, incorporation of granules or powders into soil, sprinkling, 
injection into trees or daubing. 
The spraying of a liquid onto the aerial parts of the crops to be treated 
is the preferred method of treatment. 
"Effective or nonphytotoxic quantity" is understood to mean a quantity of 
composition according to the invention which is sufficient to allow the 
control and the destruction of the fungi present or which may appear on 
the crops, and not causing any symptoms of phytotoxicity for the said 
crops. Such a quantity may vary within wide limits depending on the fungus 
to be controlled, the type of crop, the climatic conditions and the nature 
of the compound B included in the fungicidal composition according to the 
invention. This quantity may be determined by systematic field trials 
within the capability of persons skilled in the art. 
Under the usual conditions of agricultural practice, the doses of 
fungicidal composition according to the invention per volume of liquid for 
spraying ranging from 1 g/hl to 500 g/hl, corresponding essentially to 
doses per hectare of between 10 g/ha and 5,000 g/ha generally give good 
results. 
The following examples are given purely to illustrate the invention which 
they do not limit in any manner. 
In these examples, the compound A used is 
(4S)-4-methyl-2-methylthio-4-phenyl-1-phenylamino-2-imidazolin-5-one. 
In the figures accompanying the present text, the dose of each active 
substance taken separately, required for the control of phytopathogenic 
fungus at the indicated level, is compared with that of the 2 active 
substances taken in the form of a mixture. The effective dose of each 
active substance taken separately is indicated on the x-axis and on the 
y-axis and a straight line is drawn which cuts across these 2 axes and 
links these 2 doses. While an active substance taken separately is not 
effective (for example fosetyl-Al in FIG. 1) the straight line is parallel 
to the coordinate axis which indicates the doses of this active substance. 
As regards the 2 active substances taken in the form of a mixture, the 
dose of the mixture in a given ratio is indicated by a dot. A straight 
line is drawn between this dot and the origin of the system of axes, such 
that the ratio of active substances may be conveniently indicated for each 
ratio tested. 
EXAMPLE 1 
In vivo trial of the combination of A with fosetyl-Al on Phytophthora 
infestans (tomato blight) by preventive treatment at 48 hours 
A 60 mg suspension is prepared comprising compounds A and B in a liquid 
mixture consisting of 0.3 ml of a surface-active agent (oleate of a 
polyoxyethylenated derivative of sorbitan) diluted 10% in water and of 60 
ml of water. 
Component B is fosetyl-Al; the A/B ratio is 0.05-0.1-1. 
Tomato plants (Marmande variety) are cultivated in pots. When these plants 
are one month old (5 to 6-leaf stage, height 12 to 15 cm), they are 
treated by spraying the above suspension. 
At the end of 48 hours, each plant is contaminated by spraying using an 
aqueous suspension of Phytophthora infestans spores (30,000 sp/cm.sup.3). 
After this contamination, the tomato plants are incubated for 7 days at 
about 20.degree. C. in an atmosphere saturated with moisture. 
The reading is made 7 days after the contamination, in comparison with the 
control plants. 
The results obtained are presented in the form of points, corresponding to 
90% destruction of the pest and are placed in a Tammes diagram which 
comprises, on the x-axis, the doses of A expressed in mg/l and on the 
y-axis the doses of B also in mg/l. 
The diagram of FIG. 1 is obtained in which it appears that fosetyl-Al, when 
it is applied alone, is not effective under the trial conditions. It 
appears, nevertheless, that the addition of fosetyl-Al makes it possible, 
quite unexpectedly, to decrease the dose of A necessary for the 
destruction of 90% of the pest below 309 mg/l which corresponds to the 
dose of A alone which it is necessary to apply in order to obtain the same 
percentage destruction. 
The arrangement of the points which is obtained therefore indicates an 
effect termed, according to the Tammes method mentioned above, "one-sided 
effect". This arrangement corresponds to a type II isobole according to 
the said method (page 74 of the corresponding bibliographic reference 
already mentioned) and is characteristic of a synergy. 
EXAMPLE 2 
In vivo trials of the combination of A with fosetyl-Al on Plasmopara 
viticola (vine downy mildew) by preventive treatment at 72 hours 
A 60 mg suspension is prepared comprising compounds A and B in a liquid 
mixture consisting of 0.3 ml of a surface-active agent (oleate of a 
polyoxyethylenated derivative of sorbitan) diluted 10% in water and of 60 
ml of water. 
Component B is fosetyl-Al; the A/B ratio is 0.002-0.004-0.02. 
Vine cuttings (Vitis vinifera) Chardonnay variety, are cultivated in pots. 
When these plants are 2 months old (8 to 10-leaf stage, height 10 to 15 
cm), they are treated by spraying using the above suspension. 
Plants used as controls are treated with a similar suspension but not 
containing any active substance (formulation blank). 
After drying for 72 hours, each plant is contaminated by spraying an 
aqueous Plasmopara viticola spore suspension obtained from sporulated 
leaves contaminated 7 days earlier. These spores are suspended in an 
amount of 100,000 units per cm.sup.3. 
The contaminated plants are then incubated for two days at about 18.degree. 
C., in an atmosphere saturated with moisture, and then for 5 days at 
20-22.degree. C. under a relative humidity of 90-100%. 
The reading is made 7 days after the contamination, in comparison with the 
control plants. 
The results obtained are presented in the form of points, corresponding to 
90% destruction of the pest and are placed in a Tammes isobole diagram 
which has, on the x-axis, the doses of A expressed in mg/l and on the 
y-axis the doses of B also in mg/l. 
The diagram of FIG. 2 is obtained in which it appears that fosetyl-Al, when 
it is applied alone, is not effective under the trial conditions. It 
appears, nevertheless, that the addition of fosetyl-Al makes it possible, 
quite unexpectedly, to decrease the dose of A necessary for the 
destruction of 90% of the pest below 20 mg/l, which corresponds to the 
dose of A alone which it is necessary to apply in order to obtain the same 
percentage destruction. 
The arrangement of the points which is obtained therefore indicates an 
effect termed according to the Tammes method mentioned above "one-sided 
effect". This arrangement corresponds to a type II isobole according to 
the said method (page 74 of the corresponding bibliographic reference 
already mentioned) and is characteristic of a synergy. 
EXAMPLE 3 
In vivo trial of the combination of A with mancozeb on Plasmopara viticola 
(vine downy mildew) by preventive treatment at 24 hours 
Example 2 is repeated using as component B mancozeb, using A and B 
concentrations in the suspension for treating the plants equal to 3.2 and 
12.5 mg/l respectively, and finally carrying out the contamination 24 
hours after the treatment. 
The efficacy measured, as well as the efficacy of products A and B alone 
measured under the same conditions, is indicated in the table below. 
______________________________________ 
Dose (in mg/l) 
Efficacy (in %) 
______________________________________ 
Compound A 3.2 80.8 
Mancozeb 12.5 0 
Compound A + 3.2 + 12.5 90.4 
mancozeb 
______________________________________ 
EXAMPLE 4 
In vivo trial of the combination of A with cymoxanil on Phytophthora 
infestans (tomato blight) by preventive treatment at 48 hours 
Example 1 is repeated using as component B cymoxanil, using A/B ratios in 
the suspension for treating plants equal to 0.25-0.5-2-4. 
The diagram of FIG. 3 is obtained which shows an arrangement of the points 
similar to Example 1, which is characteristic of a synergy. 
EXAMPLE 5 
In vivo trial of the combination of A with 
N-methyl-N-ethyl-2-(3,4-dimethoxyphenyl)-4-trifluoromethylbenzamide on 
Phytophthora infestans (tomato blight) by preventive treatment at 48 hours 
Example 1 is repeated using as component B 
N-methyl-N-ethyl-2-(3,4-dimethoxyphenyl)-4-trifluoromethylbenzamide, and 
using A/B ratios in the suspension for treating plants equal to 
0.25-0.5-1-2-4. 
The results obtained are presented in the form of points, corresponding to 
90% destruction of the pest and are placed in a Tammes diagram which 
comprises, on the x-axis, the doses of A expressed in mg/l and on the 
y-axis the doses of B also in mg/l. 
The diagram of FIG. 4 is obtained in which it appears that the addition of 
a dose of A of less than 163 mg/l (which corresponds to the dose of A 
alone which it is necessary to apply in order to obtain the destruction of 
90% of the pest) makes it possible, quite unexpectedly, to decrease the 
dose of B necessary for the destruction of 90% of the pest below 166 mg/l 
(this value corresponding to the dose of B alone which it is necessary to 
apply in order to obtain the same percentage of destruction). 
The arrangement of the points which is obtained therefore indicates an 
effect termed according to the Tammes method mentioned above "two-sided 
effect". This arrangement corresponds to a type III isobole according to 
the said method (page 75 of the corresponding bibliographic reference 
already mentioned) and is characteristic of a synergy. 
EXAMPLE 6 
In vivo trial of the combination of A with dimethomorph on Phytophthora 
infestans (tomato blight) by preventive treatment at 48 hours 
Example 1 is repeated using as component B dimethomorph, and using A/B 
ratios in the suspension for treating plants equal to 0.25-0.5-1. 
The diagram of FIG. 5 is obtained in which the arrangement of the points is 
similar to that obtained for Example 5 and is characteristic of a synergy. 
EXAMPLE 7 
In vivo trial of the combination of A with oxadixyl on Plasmopara viticola 
(vine downy mildew, strain sensitive to phenylamides) by curative 
treatment at 48 hours 
A 60 mg suspension is prepared comprising compounds A and B in a liquid 
mixture consisting of 0.3 ml of a surface-active agent (oleate of a 
polyoxyethylenated derivative of sorbitan) diluted 10% in water and of 60 
ml of water. 
Component B is oxadixyl; the A/B ratio is 0.5-1-2-4. 
Vine cuttings (Vitis vinifera), Chardonnay variety, are cultivated in pots. 
When these plants are 2 months old (8 to 10-leaf stage, height 10 to 15 
cm), they are contaminated by spraying an aqueous Plasmopara viticola 
spore suspension obtained from sporulated leaves contaminated 7 days 
earlier. These spores are suspended in an amount of 100,000 units per 
cm.sup.3. 
The contaminated plants are then treated 48 hours after contamination by 
spraying using the suspension of fungicidal product prepared above. 
Plants used as controls are treated with a similar suspension but not 
containing any active substance (formulation blank). 
The plants contaminated, then treated are then incubated for two days at 
about 18.degree. C. in an atmosphere saturated with moisture and then for 
5 days at 20-22.degree. C. under a relative humidity of 90-100%. 
The reading is made 7 days after the contamination, in comparison with the 
control plants. 
The results obtained are presented in the form of points, corresponding to 
70% destruction of the pest and are placed in a Tammes isobole diagram 
which comprises, on the x-axis, the doses of A expressed in mg/l and on 
the y-axis the doses of B also in mg/l. 
The diagram of FIG. 6 is obtained in which the arrangement of the points is 
similar to that obtained for Example 5 and is characteristic of a synergy. 
EXAMPLE 8 
In vivo trial of the combination of A with chlorothalonil on Phytophthora 
infestans (tomato blight) by preventive treatment at 48 hours 
Example 1 is repeated using as compound B chlorothalonil; the A/B ratio is 
0.125-0.25-0.5-1-2. The results corresponding to 70% destruction of the 
pest are presented. 
The diagram of FIG. 7 is obtained which shows an arrangement of points 
similar to Example 5, characteristic of a synergy. 
EXAMPLE 9 
In vivo trial of the combination of A with dimethomorph on Plasmopara 
viticola (vine downy mildew) by curative treatment at 48 hours 
Example 7 is repeated using as compound B dimethomorph; the A/B ratio is 
0.25-0.5-1-2-4. The results corresponding to 90% destruction of the pest 
are presented. 
The diagram of FIG. 8 is obtained which shows an arrangement of points 
similar to Example 1, characteristic of a synergy. 
EXAMPLE 10 
In vivo trial of the combination of A with metalaxyl on Phytophthora 
infestans (tomato blight, strain sensitive to phenylamides) by preventive 
treatment at 48 hours 
Example 1 is repeated using as compound B metalaxyl; the A/B ratio is 
0.25-0.5-1-2. A strain sensitive to phenylamides is used. 
The diagram of FIG. 9 is obtained which shows an arrangement of the points 
similar to Example 1, and which is characteristic of a synergy. 
EXAMPLE 11 
In vivo trial of the combination of A with metalaxyl on Plasmopara viticola 
(vine downy mildew) by preventive treatment at 24 hours 
Example 2 is repeated using as compound B metalaxyl; the A/B ratio is 
2-4-8. The vine plants are contaminated 24 hours after having treated them 
with the suspension comprising the mixture of A and B. 
The diagram of FIG. 10 is obtained which shows an arrangement of the points 
similar to Example 5, and which is characteristic of a synergy. 
EXAMPLE 12 
In vivo trial of the combination of A with phosphorous acid on Phytophthora 
infestans (tomato blight) by preventive treatment at 48 hours 
Example 1 is repeated using as compound B phosphorous acid; the A/B ratio 
is 0.025-0.05-0.1-0.2-1. The results corresponding to 70% destruction of 
the pest are presented. 
The diagram of FIG. 11 is obtained which shows an arrangement of the points 
which is also similar to Example 1, and which is characteristic of a 
synergy. 
EXAMPLE 13 
In vivo trial of the combination of A with the sodium salt of phosphorous 
acid on Plasmopara viticola (vine downy mildew) by preventive treatment at 
24 hours 
Example 2 is repeated using as compound B the sodium salt of phosphorous 
acid; the A/B ratio is: 0.025-0.05-0.1. The vine plants are contaminated 
24 hours after having treated them with the suspension comprising the 
mixture of A and B. 
The diagram of FIG. 12 is obtained which shows an arrangement of the points 
which is also similar to Example 2, and which is characteristic of a 
synergy. 
EXAMPLE 14 
In vivo trial of the combination of A with cymoxanil on Phytophthora 
infestans (tomato blight) by preventive treatment at 48 hours 
Example 1 is repeated using as compound B cymoxanil; the A/B ratio is 
0.25-0.5-1-2. The results corresponding to 70% destruction of the pest are 
presented. 
The diagram of FIG. 13 is obtained which shows an arrangement of the points 
similar to Example 5, and which is characteristic of a synergy. 
EXAMPLE 15 
In vivo trial of the combination of A with cymoxanil on Phytophthora 
infestrans (tomato blight) by curative treatment at 24 hours 
A 60 mg suspension is prepared comprising compounds A and B in a liquid 
mixture consisting of 0.3 ml of a surface-active agent (oleate of a 
polyoxyethylenated derivative of sorbitan) diluted 10% in water and of 60 
ml of water. 
Component B is cymoxanil; the A/B ratio is 0.25-0.5-1-2. 
Tomato plants (Marmande variety) are cultivated in pots. When these plants 
are one month old (5 to 6-leaf stage, height 12 to 15 cm), they are 
contaminated by spraying using an aqueous Phytophthora infestans spore 
suspension (30,000 sp/cm.sup.3). 
At the end of 24 hours, these plants are contaminated by spraying the above 
suspension. 
Next, the tomato plants are incubated for 7 days at about 20.degree. C. in 
an atmosphere saturated with moisture. 
The reading is made 7 days after the contamination, in comparison with the 
control plants. 
The results obtained are presented in the form of points, corresponding to 
90% destruction of the pest and are placed in a Tammes diagram which 
comprises, on the x-axis, the doses of cymoxanil expressed in mg/l and on 
the y-axis the doses of A also in mg/l. 
The diagram of FIG. 14 is obtained in which the arrangement of the points 
indicates a one-sided effect characteristic of a synergy. 
EXAMPLE 16 
In vivo trial of the combination of A with 
N-methyl-N-ethyl-2-(3,4-dimethoxyphenyl)-4-trifluoromethylbenzamide on 
Plasmopara viticola (vine downy mildew) by curative treatment at 48 hours 
Example 7 is repeated using as component B 
N-methyl-N-ethyl-2-(3,4-dimethoxyphenyl)-4-trifluoromethylbenzamide, using 
A/B ratios in the suspension for treating plants equal to 0.25-0.5-1-4. 
The diagram of FIG. 15 is obtained which shows an arrangement of the points 
similar to Example 5, and which is characteristic of a synergy. 
EXAMPLE 17 
In vivo trial of the combination of A with 
methyl-(E)-methoxyimino.alpha.-(o-tolyloxy)-o-tolyl!acetate on Plasmopara 
viticola (vine downy mildew) by preventive treatment at 24 hours 
Example 2 is repeated using as component B 
methyl-(E)-methoxyimino.alpha.-(o-tolyloxy)-o-tolyl!acetate, using A/B 
ratios in the suspension for treating plants equal to 0.25-0.5-1. The vine 
plants are contaminated 24 hours after they have been treated with the 
suspension comprising the mixture of A and B. 
The diagram of FIG. 16 is obtained which shows an arrangement of the points 
similar to Example 5, and which is characteristic of a synergy. 
EXAMPLE 18 
In vivo trial of the combination of A with 
methyl-(E)-methoxyimino.alpha.-(o-tolyloxy)-o-tolyl!acetate on Plasmopara 
viticola (vine downy mildew) by curative treatment at 48 hours 
Example 7 is repeated using as compound B methyl-(E)-methoxyimino 
.alpha.-(o-tolyloxy)-o-tolyl!acetate; the A/B ratio is 0.25-0.5-1. The 
results corresponding to 90% destruction of the pest are presented. 
The diagram of FIG. 17 is obtained which shows an arrangement of the points 
similar to Example 5, and which is characteristic of a synergy. 
EXAMPLE 19 
In vivo trial of the combination of A with 
methyl-(E)-2-{2-6-(2-cyanophenoxy)pyrimidin-4-yloxy!phenyl}-3-methoxyacry 
late on Phytophthora infestans (tomato blight) by preventive treatment at 
48 hours 
Example 1 is repeated using as compound B 
methyl-(E)-2-{2-6-(2-cyanophenoxy)pyrimidin-4-yloxy!phenyl}-3-methoxyacry 
late; the A/B ratio is 0.25-0.5-1. The results corresponding to 90% 
destruction of the pest are presented. 
The diagram of FIG. 18 is obtained which shows an arrangement of the points 
similar to Example 5, and which is characteristic of a synergy. 
EXAMPLE 20 
In vivo trial of the combination of A with fluazinam on Phytophthora 
infestans (potato blight, strain which is sensitive to phenylamides) by 
curative treatment at 24 hours 
Example 15 is repeated using potato plants (Bintje variety) and taking as 
compound B fluazinam; the A/B ratio is 0.11-0.33-1. 
The diagram of FIG. 19 is obtained. 
EXAMPLE 21 
In vivo trial of the combination of A with epoxyconazole on Septoria 
nodorum (wheat septoria spot) by preventive treatment at 24 hours 
An aqueous concentrated suspension of A at 500 g/l is prepared. 
Component B is epoxyconazole of which an aqueous concentrated suspension at 
125 g/l is used. 
Suspensions are then prepared comprising A and/or B diluted in water, so as 
to give the following values to the A/B ratio: 0.25-0.5. In all cases, a 
homogenous dilute suspension is obtained. 
Wheat seeds of the Talent variety are cultivated in pots placed in a 
climatic cell in which the temperature is about 10.degree. C. and the 
relative humidity about 70%. When these plants are 15 days old (size 8 to 
10 cm), they are treated by applying a dilute suspension, as prepared 
above. 
This application is made by means of a nozzle system which sprays the 
liquid by forming a cone whose angle at the vertex is between 70 and 
110.degree. C. Such a system is termed beam jet nozzle. This nozzle system 
is attached to a trolley which makes a translational movement relative to 
the pots placed on a fixed plate. 
Such a system makes it possible to express the applied dose of A and/or B 
in g per hectare. 
The experimental conditions are such that the volume of dilute aqueous 
suspension applied to the pots is 250 l/ha. 
At the end of 24 hours, each plant is contaminated by spraying with an 
aqueous suspension of Septoria nodorum spores (500,000 sp/cm.sup.3). 
After this contamination, the wheat plants are incubated for 7 days at 
about 20.degree. C. 
The reading is made 7 days after the contamination, in comparison with the 
control plants contaminated with the pest, but which are not treated. 
The results obtained are presented in the form of points corresponding to 
90% destruction of the pest and which are placed in a Tammes diagram which 
comprises, on the x-axis, the dose of epoxyconazole expressed in g/ha and 
on the y-axis the dose of A also in g/ha. 
The diagram of FIG. 20 is obtained which shows an arrangement of points 
similar to Example 1 and which is characteristic of a synergy. 
EXAMPLE 22 
In vivo trial of the combination of A with epoxyconazole on Puccinia 
recondita (wheat brown rust) by preventive treatment at 24 hours 
Example 21 is repeated by giving the following values to the A/B ratio: 
0.1-0.2-1-2, and by carrying out the contamination with an aqueous 
suspension of Puccinia recondita spores (100,000 sp/cm.sup.3). 
The reading is made 10 days after the contamination, in comparison with the 
control plants contaminated with the pest, but not treated. 
The diagram of FIG. 21 is obtained. 
EXAMPLE 23 
In vivo trial of the combination of A with epoxyconazole on Septoria 
tritici (wheat septoria spot) by preventive treatment at 24 hours 
Example 21 is repeated by giving the following values to the A/B ratio: 
0.25-0.5-1 and by using wheat seeds of the Darius variety. 
The contamination is carried out with an aqueous suspension of Septoria 
tritici spores (500,000 sp/cm.sup.3) and the incubation is carried out at 
a temperature of 18.degree. C. and of 15.degree. C. at night for a period 
of 21 days. 
The reading is made 21 days after the contamination, in comparison with the 
control plants contaminated with the pest, but not treated. 
The diagram of FIG. 22 is obtained which shows an arrangement of the points 
similar to Example 21, and which is characteristic of a synergy. 
EXAMPLE 24 
In vivo trial of the combination of A with propiconazole on Puccinia 
recondita (wheat brown rust) by preventive treatment at 24 hours 
Example 22 is repeated by taking as compound B propiconazole of which a 
soluble concentrate at 125 g/l is used, and by giving the following values 
to the A/B ratio: 0.5-1-2. 
The results corresponding to 70% destruction of the pest are presented. 
The diagram of FIG. 23 is obtained which shows an arrangement of the points 
similar to Example 5, and which is characteristic of a synergy. 
EXAMPLE 25 
In vivo trial of the combination of A with propiconazole on Septoria 
nodorum (wheat septoria spot) by preventive treatment at 24 hours 
Example 21 is repeated by taking as compound B propiconazole of which a 
soluble concentrate at 125 g/l is used, and by giving the following values 
to the A/B ratio: 0.5-1-2. 
The diagram of FIG. 24 is obtained which shows an arrangement of the points 
characteristic of a synergy. 
This example is also repeated by giving the following values to the A/B 
ratio: 0.1-0.2-1. 
The diagram of FIG. 25 is obtained which shows an arrangement of the points 
characteristic of a synergy. 
EXAMPLE 26 
In vivo trial of the combination of A with propiconazole on Septoria 
tritici (wheat septoria spot) by preventive treatment at 24 hours 
Example 23 is repeated by taking as compound B propiconazole of which a 
soluble concentrate at 125 g/l is used, and by giving the following values 
to the A/B ratio: 0.1-0.2-1. 
The results corresponding to 90% destruction of the pest are presented. 
The diagram of FIG. 26 is obtained which shows an arrangement of the points 
similar to Example 1, and which is characteristic of a synergy. 
EXAMPLE 27 
In vivo trial of the combination of A with prochloraz on Septoria nodorum 
(wheat septoria spot) by preventive treatment at 24 hours 
Example 21 is repeated by taking as compound B prochloraz, and by preparing 
emulsifiable concentrates of A and B at 150 and 320 g/l, respectively, in 
a mixture of benzyl alcohol and an aromatic type solvent into which a 
surfactant pair consisting of castor oil ethoxylated with 33 moles of 
ethylene oxide and of calcium alkylarylsulphonate has been introduced. 
The emulsions comprising A and/or B diluted in water are prepared so as to 
give the following values to the A/B ratio: 0.25-1-2. In all cases, a 
homogeneous dilute emulsion is also obtained. 
The diagram of FIG. 27 is obtained which shows an arrangement of the points 
characteristic of a synergy. 
EXAMPLE 28 
In vivo trial of the combination of A with tebuconazole on Septoria nodorum 
(wheat septoria spot) by preventive treatment at 24 hours 
Example 21 is repeated by taking as compound B tebuconazole of which a 
concentrated suspension at 25 g/l is used, and by giving the following 
values to the A/B ratio: 0.1-1-2. The dilute suspensions comprising A 
and/or B are homogeneous. 
The diagram of FIG. 28 is obtained which shows an arrangement of the points 
characteristic of a synergy. 
EXAMPLE 29 
In vivo trial of the combination of A with tebuconazole on Puccinia 
recondite (wheat brown rust) by preventive treatment at 24 hours 
Example 22 is repeated by taking as compound B tebuconazole of which a 
concentrated suspension at 25 g/l is used, and by giving the following 
values to the A/B ratio: 0.1-0.2-1-2. The dilute suspensions comprising A 
and/or B are homogeneous. 
The diagram of FIG. 29 is obtained which shows an arrangement of the points 
characteristic of a synergy.