Fungicides comprising iprodione and a triazole

(1) Fungicidal combinations and compositions, comprising a compound A of the formula: ##STR1## wherein the symbol ##STR2## represents ##STR3## and a compound B chosen from bromuconazole, tebuconazole, epoxiconazole, cyproconazole, flusilazole, metconazole, hexaconazole and difenoconazole. (2) Process for treating crops using these combinations/compositions.

The subject of the present invention is a fungicidal combination or 
composition which is useful for treating fungal attacks on crops and which 
is based on a compound whose formula comprises a triazole group. It also 
relates to a process for treating crops having the same aim. 
Compounds whose formula comprises a triazole group are well-known to 
farmers, especially for their effectiveness against the group of diseases 
which affect or are capable of affecting barley, such as powdery mildew, 
rust, rhynchosporium disease and helminthosporium disease. 
However, the effectiveness of these compounds against helminthosporium 
disease is often considered to be insufficient. 
As a matter of fact, this last-mentioned disease has become much more 
prevalent in recent years due to changes in cultivation methods, such as 
intensification of cultivation, with the increase in the input of 
nitrogenous fertilizers, and due to the adoption, by an increasing number 
of farmers, of the cultivation of winter barley. 
It is, moreover, always desirable to reduce the doses of chemicals 
distributed in the environment for treating fungal diseases of crops, 
especially by reducing the application doses of the chemicals, and to 
widen the possibilities of choice offered to the farmer, in order for the 
latter to find the solution which is best suited to his particular 
problem. 
An aim of the invention is thus to provide a new fungicidal combination or 
composition which is useful for the problem described above. 
Another aim of the invention is to propose a new fungicidal combination or 
composition which is useful in the preventive or curative treatment of 
powdery mildew, rust or rhynchosporium disease. 
Another aim of the invention is to propose a fungicidal combination or 
composition which has improved effectiveness, preventively or curatively, 
against helminthosporium disease of barley. 
It has now been found that these aims could be achieved in all or in part 
by virtue of the fungicidal combination or composition according to the 
present invention, which makes it possible to observe noteworthy 
synergistic effects. 
The fungicidal combination and the fungicidal composition according to the 
invention comprise a fungicidally effective amount of a compound A, 
corresponding to the formula (I): 
##STR4## 
wherein the symbol 
##STR5## 
represents 
##STR6## 
and a compound B chosen from bromuconazole, tebuconazole, epoxiconazole, 
cyproconazole, flusilazole, metconazole, hexaconazole and difenoconazole. 
The fungicidal composition of the invention further comprises an 
agriculturally acceptable vehicle and/or an agriculturally acceptable 
surface-active agent. 
The compound A, as defined above, corresponds to one of the following 
active materials: iprodione, vinclozolin or procymidone. 
Bromuconazole is 
1-[4-bromo-2-(2,4-dichlorophenyl)tetrahydro-2-furylmethyl]-1H-1,2,4-triazo 
le, which is described in European Patent Publication No. 0246982. 
Epoxiconazole is 
(2RS,3SR)-1-[3-(2-chlorophenyl)-2-(4-fluorophenyl)oxiran-2-ylmethyl]-1H-1, 
2,4-triazole, which is described in at least one of the two European Patent 
Publication Nos. 0094564 and 0196038. Metconazole is 
(1RS,5RS)-5-(4-chlorobenzyl)-2,2-dimethyl-1-(1H-1,2,4-triazol-1-ylmethyl)c 
yclopentanol, which is described in European Patent Publication No. 
0267778. The other active materials mentioned above are described in the 
work: "The Pesticide Manual", 9th Edition, by Charles R. Worthing and 
Raymond J. Hance, published by the British Crop Protection Council. 
Tebuconazole is 
(RS)-1-(4-chlorophenyl)-4,4-dimethyl-3-(1H-1,2,4-triazol-1-ylmethyl)pentan 
-3-ol. Cyproconazole is 
(2RS,3RS;2RS,3SR)-2-(4-chlorophenyl)-3-cyclopropyl-1-(1H-1,2,4-triazol-1-y 
l)butan-2-ol. Flusilazole is 
1-[[bis(4-fluorophenyl)(methyl)silyl]methyl]-1H-1,2,4-triazole. 
Hexaconazole is 
(RS)-2-(2,4-dichlorophenyl)-1-(1H-1,2,4-triazol-1-yl)hexan-2-ol. 
Difenoconazole is cis, 
trans-3-chloro-4-[4-methyl-2-(1H-1,2,4-triazol-1-ylmethyl)-1,3-dioxolan-2- 
yl phenyl 4-chlorophenyl ether. 
The combination of the invention and the composition of the invention 
comprising this combination are useful for treating fungal diseases of 
various crops. They are thus effective in treating powdery mildew, rust, 
rhynchosporium disease or helminthosporium disease of barley or in 
treating powdery mildew, rusts, septoria diseases and fusarium diseases of 
wheat. They are also effective in controlling grey mould, alternaria 
disease, sclerotinia disease, cercospora disease, helminthosporium disease 
and fusarium disease of proteinaceous and oleaginous plants (especially 
pea, oilseed rape and maize), as well as for treating diseases of the lawn 
such as rust, fusarium disease, sclerotinia disease and rhizoctonia 
disease. Moreover, they are effective in controlling alternaria disease, 
powdery mildew and monilia disease of fruit trees and for controlling 
alternaria disease of vegetable crops comprising, especially, potato, 
tomato, radish and carrot. 
The compound B/compound A ratio by weight in the combination or composition 
according to the invention is generally between about 0.05 and about 10, 
preferably between about 0.08 and about 3, and more preferentially still 
between about 0.1 and about 1. 
According to an advantageous variant of the invention, the compound B 
included in the combination or composition according to the invention is 
chosen from bromuconazole, tebuconazole, epoxiconazole and flusilazole. 
According to another advantageous variant of the invention, the compound A 
included in the combination or composition according to the invention is 
3-(3,5-dichlorophenyl)-N-isopropyl-2,4-dioxoimidazolidine-1-carboxamide, 
also known as iprodione. 
According to yet another advantageous variant of the invention, the 
compound B included in the combination or composition according to the 
invention is bromuconazole. 
The combination or composition resulting from these last two variants taken 
simultaneously is particularly advantageous due to its outstanding 
activity with respect to phytopathogenic fungi, especially for diseases of 
barley, and due to its selectivity with respect to crops. 
The combinations and compositions according to the invention are again 
advantageous due to the spectrum of activity and the low doses which can 
be used for the active materials, this last quality being particularly 
important for easily understandable ecological reasons. 
The fungicidal composition according to the invention generally contains 
from about 0.5 to about 95% of a mixture of the compound A and the 
compound B. 
It can be the concentrated composition, that is to say the commercial 
product combining the two active materials. It can also be the dilute 
composition ready to be sprayed on the crop to be treated. In this latter 
case, dilution with water can be carried out either from a commercial 
concentrated composition containing the two active materials (this mixture 
being known as "ready mix") or by means of the mixture prepared at the 
time of use (known as "tank mix") of two commercial concentrated 
compositions each containing one active material. 
The composition according to the invention can additionally comprise all 
the usual additives or adjuvants of plant-protection compositions, 
especially vehicles, surface-active agents, adhesion agents and 
flow-improving agents. 
In the present account, the term "vehicle" denotes a natural or synthetic, 
organic or inorganic material with which the active materials are combined 
to facilitate their application on the plant. This vehicle is thus 
generally inert and it must be acceptable in agriculture, especially on 
the treated plant. The vehicle can be solid (clays, natural or synthetic 
silicates, silica, resins, waxes, solid fertilizers and the like) or 
liquid (water, alcohols, ketones, petroleum fractions, aromatic or 
paraffinic hydrocarbons, chlorinated hydrocarbons, liquefied gases, and 
the like). 
The surface-active agent can be an emulsifying, dispersing or wetting agent 
of ionic or nonionic type. There may be mentioned, for example, salts of 
polyacrylic acids, salts of lignosulfonic acids, salts of phenolsulfonic 
or naphthalenesulfonic acids, polycondensates of ethylene oxide with fatty 
alcohols or with fatty acids or with fatty amines, substituted phenols 
(especially alkylphenols or arylphenols), salts of esters of sulfosuccinic 
acids, taurine derivatives (especially alkyltaurates) or phosphoric esters 
of polyoxyethylenated phenols or alcohols. The presence of at least one 
surface-active agent is desirable to promote dispersion of the active 
materials in water and their ready application on the plants. 
The composition of the invention can also contain any kind of other 
ingredients such as, for example, protective colloids, adhesives, 
thickening agents, thixotropic agents, penetrating agents, stabilizing 
agents, sequestering agents, pigments, dyes or polymers. 
More generally, the composition according to the invention can include all 
the solid or liquid additives corresponding to the usual techniques for 
the formulation of plant-protection products. 
The composition according to the invention can be in the solid, gel or 
liquid form and, in the latter case, in the form of solutions or 
suspensions or emulsions or emulsifiable concentrates. Liquid compositions 
are preferred, due both to their convenience of use and to their 
simplicity of manufacture. 
There may be mentioned, as forms of solid compositions, powders for dusting 
or dispersion (with an active compounds content which can range up to 
100%), wettable powders and granules for dry spreading, as well as 
dispersible or soluble granules. 
Wettable powders (or powders to be sprayed), as well as dispersible 
granules, generally contain 20 to 95% of active materials and, in addition 
to the solid vehicle, from 0 to 5% of a wetting agent, from 3 to 10% of a 
dispersing agent and, when necessary, from 0 to 10% of one or more 
stabilizing agents and/or other additives, such as pigments, dyes, 
penetrating agents, adhesives, or antidumping agents, dyes, and the like. 
It is well understood that some of these compositions, such as wettable 
powders or dispersible granules, are intended to constitute liquid 
compositions at the time of application. 
There may be mentioned, as forms of liquid compositions, solutions, in 
particular water-soluble concentrates, emulsifiable concentrates, 
emulsions, suspension concentrates, aerosols or pastes. 
The emulsifiable or soluble concentrates most often comprise 10 to 80% of 
active materials, the emulsions or solutions ready for application 
containing, for their part, 0.01 to 20% of active materials. In addition 
to the solvent, the emulsifiable concentrates can contain, when necessary, 
2 to 20% of suitable additives such as the stabilizing agents, 
surface-active agents, penetrating agents, corrosion inhibitors, dyes or 
adhesives mentioned above. From these concentrates, it is possible to 
obtain, by dilution with water, emulsions of any desired concentration, 
which are particularly suitable for application on the aerial parts of the 
plant to be treated. As has already been said, aqueous dispersions and 
emulsions, for example the compositions obtained by diluting a wettable 
powder or an emulsifiable concentrate according to the invention with 
water, come within the general scope of the present invention. The 
emulsions can be of the water-in-oil or oil-in-water type and they can 
have a thick consistency, like that of a "mayonnaise". 
The suspension concentrates, also applicable by spraying, are a stable 
fluid product, which does not thicken or form a sediment after storage, 
and they generally contain from 10 to 75% of active materials, from 0.5 to 
15% of surface-active agents, from 0.1 to 10% of thixotropic agents and 
from 0 to 10% of suitable additives, such as pigments, dyes, antifoaming 
agents, corrosion inhibitors, stabilizing agents, penetrating agents and 
adhesives and, as vehicle, water or an organic liquid in which the active 
materials are insoluble or nearly insoluble: certain organic solid 
materials or inorganic salts can be dissolved in the vehicle to aid in 
preventing sedimentation or as antigels for water. 
The composition according to the invention is prepared according to 
processes known per se. 
Thus, to obtain powders to be sprayed or wettable powders, the active 
materials are intimately mixed, in suitable mixers, with the additional 
substances and the mixture is milled with mills or other grinders. Powders 
to be sprayed are thereby obtained with advantageous wettability and 
suspensibility; they can be suspended in water at any desired 
concentration and these suspensions can be used very advantageously, in 
particular for application on the aerial parts of the plants. 
Pastes or suspension concentrates can be produced in place of wettable 
powders. The conditions and modes of production and use of these pastes 
are similar to those of wettable powders or powders to be sprayed, part of 
the milling operation necessary simply being carried out in a liquid 
medium. 
The dispersible granules are generally prepared by agglomeration or 
extrusion or compacting, in suitable granulation systems, of compositions 
of wettable powder type. The granules for dry spreading are generally 
obtained by impregnating a granulated vehicle with a solution or an 
emulsion of the active materials. 
The invention finally relates to a treatment process intended to control or 
prevent fungal attacks on crops, characterized in that an effective and 
non-phytotoxic dose of a combination or composition according to the 
invention is applied on the aerial parts of the plants. 
These combinations and compositions are advantageously used so that the 
dose applied of the mixture of the compounds A and B is between about 5 
and about 5000 g/ha and preferably between about 150 and about 3000 g/ha. 
This dose is a function of the plant treated, the degree of infestation 
and the weather conditions. 
Mention may be made among the crops which are suitable for the treatment 
process according to the invention, of cereals, especially barley and 
wheat; proteinaceous and oleaginous plants, such as peas, oilseed rape, 
sunflower and maize; the lawn; fruit trees and vegetable crops comprising 
especially potato, tomato, radish and carrot. Barley is a preferred crop 
for the treatment process according to the invention.

The following examples are given as nonlimiting examples of the 
advantageous properties of the combinations and compositions according to 
the invention. 
In these examples, the compound A is iprodione and the compound B is 
1-[4-bromo-2-(2,4-dichlorophenyl)tetrahydro-2-furylmethyl]-1H-1,2,4-triazo 
le, also known as bromuconazole. 
EXAMPLE 1 
In Vitro Test of a Composition Comprising a Mixture of Bromuconazole and 
Iprodione on Dreschlera teres Responsible for Helminthosporium Disease of 
Barley 
A nutrient medium consisting of maize flour and gelose is introduced in the 
supercooled state into a series of petri dishes (20 ml per dish). 
During the filling of the dishes, injection is carried out of 200 .mu.l of 
a solution of the active materials to be tested (alone or as a mixture) in 
acetone, so as to obtain the desired final concentration. 
Petri dishes analogous to the above, into which similar amounts of a 
nutrient medium not containing active material are poured, are used as 
control. 
After 24 hours, a pellet with a diameter of 5 mm, comprising a fragment of 
mycelium, withdrawn from a Dreschlera teres stock culture, is deposited at 
the center of each dish. The petri dishes are stored at 20.degree. C. for 
1 week. 
The growth of the fungus (measured by the diameter of the mycelial growth) 
in the dishes containing the active material or the mixture of active 
materials to be tested is then compared with that of this same fungus in 
the dish used as control. 
The degree of inhibition of the fungus, expressed as a percentage, is thus 
determined for each active material or mixture of active materials, at the 
dose shown. 
The degree of inhibition results collated in the table below correspond to 
the mean of three repetitions. 
______________________________________ 
DEGREE OF INHIBITION AS % 
BROMUCONAZ IPRODIONE (mg/l) 
OLE (mg/l) 0 0.06 0.125 
0.25 0.5 1 2 
______________________________________ 
0 0 8.2 3.2 21.7 39.2 49.2 49.2 
0.03 15.7 
0.06 14.2 16.7 
0.125 17.5 26.8 30 42.5 
0.25 40 49.3 56.7 68.2 
0.5 56.7 81.3 75.7 89 
1 68.2 75.8 90.7 100 
______________________________________ 
EXAMPLE 2 
In Vivo Test of a Composition Comprising a Mixture of Bromuconazole and 
Iprodione on Alternaria brassicae, Responsible for Alternaria Disease of 
Radish 
A suspension is prepared comprising bromuconazole and/or iprodione in a 
liquid mixture consisting of 0.3 ml of a surface-active agent (oleate of 
polyoxyethylenated derivative of sorbitan) diluted to 10% in water and of 
40 ml of water. The dose(s) of the active material(s) is/are shown in the 
table below. 
Radish seedlings are grown in pots filled with peat/pozzolana. When these 
seedlings have reached the stage of development of the first visible leaf, 
they are treated by spraying with the above suspension. 
After 24 hours, each seedling is infected by spraying by means of an 
aqueous suspension of Alternaria brassicae spores (400,000 sp/cm.sup.3). 
After this infection, the radish seedlings are incubated for 9 days at 
approximately 20.degree. C. in an atmosphere saturated with moisture. 
The results are then read, by comparison with radish seedlings infected 
without having received fungicidal treatment, known as control seedlings. 
The fungicidal efficiency, expressed as a percentage, which is shown in the 
table below, is thus determined for each active material or mixture of 
active materials, at the dose shown. 
______________________________________ 
FUNGICIDAL EFFICIENCY AS % 
BROMUCONAZOLE IPRODIONE (mg/l) 
(mg/l) 0 6 12 25 50 100 
______________________________________ 
0 0 5 15 92.5 98.2 99.5 
25 2.5 30 77.5 95 99 99.5 
50 7.5 90 92.5 97.5 100 
100 27.5 97.5 100 100 
200 86.2 97 
______________________________________ 
EXAMPLE 3 
In Vitro Test of a Composition Comprising a Mixture of Bromuconazole and 
Iprodione on Sclerotinia homeocarpa, Responsible for Sclerotinia Disease, 
or Dollar Spot, of the Lawn 
A nutrient medium consisting of a mixture of agar, dextrose and starch is 
introduced in the supercooled state into a series of petri dishes (20 ml 
per dish). 
During the filling of the dishes, the injection is carried out of 200 .mu.l 
of a solution of the active materials to be tested (alone or as a mixture) 
in acetone, so as to obtain the desired final concentration (shown in the 
table below). 
Petri dishes analogous to the above, into which similar amounts of a 
nutrient medium not containing active material are poured, are used as 
control. 
After 24 hours, a pellet with a diameter of 5 mm, comprising a fragment of 
mycelium, withdrawn from a Sclerotinia homeocarpa stock culture, is 
deposited at the center of each dish. The petri dishes are stored at 
20.degree. C. for 4 days. 
The growth of the fungus (measured by the diameter of the mycelial growth) 
in the dishes containing the active material or the mixture of active 
materials to be tested is then compared with that of this same fungus in 
the dish used as control. 
The degree of inhibition of the fungus, expressed as a percentage, which is 
shown in the following table, is thus determined for each active material 
or mixture of active materials, at the dose shown: 
______________________________________ 
DEGREE OF INHIBITION AS % 
IPRODIONE (mg/l) 
BROMUCONAZOLE (mg/l) 
0 0.25 0.5 1 
______________________________________ 
0 0 0 0 89.3 
0.06 26.2 60.5 
0.125 26.2 66.3 83.6 
0.25 32.8 72 74.1 99.4 
0.5 82.7 98 85.6 88.5 
1 98 99.4 99.4 100 
______________________________________ 
While the invention has been described in terms of various preferred 
embodiments, the skilled artisan will appreciate that various 
modifications, substitutions, omissions, and changes may be made without 
departing from the spirit thereof. Accordingly, it is intended that the 
scope of the present invention be limited solely by the scope of the 
following claims, including equivalents thereof.