FR2745466A1 - Use of 1-phenyl pyrazole compounds - Google Patents

Abstract

Protection of crops, especially rice crops, against fungal and bacterial attack by application of an effective quantity of a 1-phenyl pyrazole (I) is new. (I) is preferably 1-(2,6-dichloro-4-trifluoromethyl phenyl)-3-cyano-4-(sulphinyl-trifluoromethyl)-5-amino-pyrazole.

Description

Pyrazoles fungicides
The present invention relates to a method of treating plants against fungal or bacterial attack.

 A first object of the invention is to fight against fungal or bacterial diseases in a curative or preventive manner.

 Another object of the present invention is to protect plants against attacks or fungal or bacterial diseases.

 Another object of the present invention is to protect rice cultures against fungal or bacterial attacks or diseases.

 Another object of the present invention is to protect the plants against fungi or fungi attacks, these attacks being optionally combined with attacks by insects.

 Another object of the present invention is to protect plants, by treatment with a single product, both against attacks by fungi or fungi and attacks by insects or arthropods.

 In other words, another object of the present invention is to protect the plants, by a single treatment, using a single product that is effective against both fungal or fungi attacks and insect attacks. or arthropods.

Another object of the invention is to protect plants against attacks or fungal or bacterial diseases selected from the group consisting of those listed in the following table:

<tb> N "<SEP> Term <SEP> English <SEP> Term <SEP> Latin <SEP> Term <SEP> French
<tb> i <SEP> Sheath <SEP> blight <SEP> Rhizoctonia <SEP> solani <SEP> = <SEP> Pellicularia <SEP> Rhizoctonia <SEP> = <SEP> pelliculariose
<tb><SEP> sasakii <SEP>
<tb> 2 <SEP> Brown <SEP> spot <SEP> Helminthosporium <SEP> oryzae <SEP> = <SEP> Helminthosporiosis <SEP> =
<tb><SEP> Cochliobolus <SEP> miyabeanus <SEP> burn <SEP> of <SEP> nz <SEP>
<tb> 3 <SEP> Leafblast <SEP> Pyricularia <SEP> oryzae <SEP> = <SEP> Magnaporthe <SEP> Pyriculariasis <SEP> = <SEP> speckle
<tb><SEP> sae <SEP>
<tb> 4 <SEP> Neck <SEP> blast <SEP> Pyricularia <SEP> oryzae <SEP> culariasis <SEP>
<Tb>

<tb> 5 <SEP> Leaf <SEP> scald <SEP> = <SEP> leaf <SEP> Rhynchosporium <SEP> oryzae <SEP> = <SEP> Necrosis <SEP> on <SEP> leaf <SEP> and <SEP > stalk <SEP> of <SEP> rice
<tb><SEP> tip <SEP> blight <SEP> Monographelia <SEP> albescens <SEP> = <SEP> rhyncosporosis <SEP> of <SEP> rice
<tb><SEP> Gerlachia <SEP> orvzae <SEP>
<tb><SEP> 6 <SEP> Sheath <SEP> rot <SEP> Acrocylindrium <SEP> oryzae <SEP> = <SEP> Decay <SEP> of <SEP> Sheaths <SEP> Foliar
<tb><SEP> Sarocladium <SEP> oryzae <SEP> +
<tb><SEP> Gacumannomyces <SEP> graminis <SEP> =
<tb><SEP> Ophiobolus <SEP> oryznus <SEP> + <SEP>
<tb><SEP> Helminthosporum <SEP> oryzae <SEP>
<tb><SEP> 7 <SEP> Grain <SEP> j <SEP> Bacteria <SEP>: <SEP> Pseudomonas <SEP> avenae <SEP> + <SEP> Decolorization <SEP> of <SEP> grains <SEP> (the
<tb><SEP> discoloration <SEP> \ Pseudomonas <SEP> syringae <SEP> + <SEP> gains <SEP> are <SEP> normally <SEP> yellow
<tb><SEP> Pseudomonas <SEP> glumae <SEP> + <SEP> and <SEP> it <SEP> appears <SEP> of <SEP> stains <SEP> bnmes)
<tb><SEP> Pseudomonas <SEP> fuscovaginae <SEP> + <SEP>
<tb><SEP> Erwinia <SEP> herbicola <SEP> + <SEP>
<tb><SEP> pine nuts <SEP> Fungi <SEP> = <SEP> mushrooms:
<tb><SEP> Helminthosporium <SEP> oryzae <SEP> + <SEP>
<tb><SEP> tAltemariaspp <SEP>
<Tb>
The discoloration of the grains corresponds to the result of the destructive action of a complex set of fungi or fungi, and of pathogenic bacteria, the detrimental result being due to one or more of the various fungi or bacteria mentioned. in the table above.

 It has now been found that these goals can be achieved by the method according to the invention.

This relates to a method for protecting crops, and more particularly rice crops, against fungal or bacterial attacks characterized in that
an effective amount of 1-phenyl pyrazole is applied.

More precisely, the invention also relates to a method for protecting
rice cultures against fungal or bacterial attack and attacks by
arthropods or insects, both types of attacks being simultaneous or
be simultaneous or expected to occur in a single
period of time.

The invention further relates to a method of protecting rice crops
against fungal or bacterial attacks such as rhizoctonia,
pelluciaria, helminthosporiosis, rice blight, blastosis,
speckling, rhynchosporiosis of rice.

 On a practical level. the protection of i-phenyl pyrazole cultures is generally better for insects or arthropods. With regard to fungal or bacterial attacks, the protection conferred by the products according to the invention may not be perfect, but it is in general sufficient, and in any case it constitutes a very valuable complement of the insecticidal or arthropodicidal activity for to protect the crops as much as possible against the most diverse external attacks.

dans laquelle:
R1 est CN ou méthyle;
R2 est S(O)nR3;
R3 est alkyl ou haloalkyl;
R4 représente un atome d'hydrogène ou d'halogène; ou un radical NRsR6,
S(O)mR7, C(O)R7, alkyl, haloalkyl ou OR8 ou un radical -N=C(R9)(RIO);
R5 et R6 représentent indépendamment l'atome hydrogène ou un radical alkyl, haloalkyl, C(O)alkyl, S(O)rCF3; ou R5 et R6 peuvent former ensemble un radical alkylene divalent qui peut être interrompu par un ou deux hétéroatomes divalents, tels que l'oxygène ou le soufre;
R7 représente un radical alkyl ou haloalkyl;
R8 représente un radical alkyl, haloalkyl ou un atome d'hydrogène;
Rg représente un radical alkyl ou un atome d'hydrogène;
R10 représente un groupe phenyl ou heteroaryl éventuellement substitué par un ou plusieurs atomes d'halogène ou groupes tels que OH. -O-alkyl. -S-alkyl. The 1-phenyl pyrazoles which may be used in the invention are advantageously products of formula (I):

in which:
R1 is CN or methyl;
R2 is S (O) nR3;
R3 is alkyl or haloalkyl;
R4 represents a hydrogen or halogen atom; or an NRsR6 radical,
S (O) mR7, C (O) R7, alkyl, haloalkyl or OR8 or a radical -N = C (R9) (R10);
R5 and R6 independently represent the hydrogen atom or an alkyl, haloalkyl, C (O) alkyl, S (O) rCF3 radical; or R5 and R6 may together form a divalent alkylene radical which may be interrupted by one or two divalent heteroatoms, such as oxygen or sulfur;
R7 represents an alkyl or haloalkyl radical;
R8 represents an alkyl radical, haloalkyl radical or a hydrogen atom;
Rg represents an alkyl radical or a hydrogen atom;
R10 represents a phenyl or heteroaryl group optionally substituted with one or more halogen atoms or groups such as OH. -O-alkyl. -S-alkyl.

cyano. or alkyl;
R1 and R12 are independently of one another. a hydrogen or halogen atom;
R13 represents a halogen atom or a haloalkyl, haloalkoxy group,
S (O) qCF3 or SF5;
m, n, q, r represent, independently of one another, an integer of 0.1 or 2;
X represents a trivalent nitrogen atom or a C-R12 radical, the other three valencies of the carbon atom being part of the aromatic ring;
with the proviso that when R1 is methyl, then R3 is haloalkyl, R4 is NH2,
R11 is Cl, R13 is CF3, and X is N.

 A preferred class of compounds of formula (I) are compounds such that R 1 is CN, R 3 is haloalkyl, R 4 is NH 2, R 11 and R 12 are independently of each other a halogen atom, and R13 is haloalkyl.

A compound of formula (I) which is very particularly preferred in the invention is
1- [2,6-C12 4-CF 3 phenyl] 3-CN 4- [SO-CF 3] 5 -NH 2 pyrazole,
hereinafter referred to as compound A.

 The preparation of compounds of formula (I) can be made according to one or the other of the methods described in patent applications WO 87/3781, 93/6089, 94/21606 or European patent 295117, or any other method relating to the skill of those skilled in the art of chemical synthesis.

 Formulations that can be used in the invention are described in particular in the patent applications WO 87/3781, 93/6089, 94/21606 and in European application 295117. The formulations described in the prior art can be adapted to make them even more suitable. more adapted to their particular use according to the local conditions, in particular by additions of appropriate adjuvants.

 Advantageously, the 1-arylpyrazoles used in the invention can be formulated as fluid or liquid compositions, wettable powders, microemulsions. Such formulations generally include one or more inert carriers or diluents. solid or liquid. and agronomically acceptable in the case of application to crop areas.

 Formulations suitable for carrying out the process according to the invention contain from 0.0001 to 95% by weight of active material of formula (I). As regards concentrated formulations for commercial use (for storage, sale or transport), they advantageously contain from 0.1 to 15% by weight of active material. The compositions as used by the applicator are generally much more dilute compositions. Apart from this active ingredient, the compositions according to the invention contain various solid or liquid carriers, surfactants and other adjuvants of various kinds, but agronomically acceptable.

 Formulations of wettable powders or concentrated granules can be prepared by grinding an 1-arylpyrazole of formula (I) with about 1% to 20% by weight of anionic solid surfactant. A suitable anionic surfactant is the dioctyl ester of the sodium salt of sulfosuccinic acid. About 85% to 95%, by weight, of inert diluent such as montmorillonite, attapulgite, lime, talc, kaolin, diatomaceous earth, pumice, silicates or other similar products may be included in such formulations, as well as the other adjuvants previously indicated.

 In addition to the granules and wettable powders described above, it is possible to use fluid formulations, and in particular formulations that are easily dispersible in water, to facilitate dispersion at the application site, especially in agriculture.

 The pyrazoles used in the present invention have low solubility but can be used at low doses. They can therefore be used in solutions or emulsions or, preferably, in the form of aqueous or non-aqueous suspensions, comprising the appropriate adjuvants and / or co-solvents. Acetone and methyl ethyl ketone can be used as co-solvents. Any liquid medium may be used provided it is not toxic to plants or the environment.

When the active ingredient is poorly soluble, co-solvents and / or wetting or dispersing agents may be used. Other additives may also be used, such as talc. The active ingredients of formula (I) can be absorbed on supports. for example vermiculite, clay. talcum kaolin or others. especially for making granules.

 The 1-aryl-triazoles of the invention can be used as a foliar treatment, or in soil treatment or, preferably, in seed treatment. The precise amount of phenyl pyrazole employed can be determined by a small number of experiments. The quantity must not be phytotoxic.

 In practical terms, the doses applied either directly by the foliage or by the soil, or by means of the treated seeds, are generally between 5 and 500 g / ha, preferably between 10 and 200 g / ha, and even more preferably between 20 and 80 g / ha. The dose applied to the seed depends on the quantity of seed sown, and it is admitted that at the first sowing as well as during the second sowing, the sown seed quantities are of the same order of magnitude. Once the seed sown, the dose brought to the ground by means of the treated grains corresponds to what has just been indicated. In the case of rice, the quantities of seeds sown are of the order of 0.5 to 3 quintals per hectare.

 The seeds can be treated by coating, coating, impregnating or soaking in liquid or pasty formulations. Such formulations are known per se. The drying is generally carried out subsequently. Treated seeds most often comprising about 2 to 200 g per quintal of seeds, preferably 5 to 80 g / q.

 The following examples, given as non-limiting, illustrate the invention and show how it can be implemented.

Example 1
40 g of rice seed were treated. active ingredient per hectare.

The seeds were sown at a rate of 150 kg / ha on dry land, and the seeds were covered with a thin layer of soil.

 These seeds were germinated. After a few weeks when the temperature was between 25 ° C and 35 ° C, the soil was covered with water by the rains and the results were observed after 2 months. The trials were repeated on 20 plots of 10 m2 each (harvest after about 105 days).

 The results reported in Table 1 (generally expressed as a percentage) were obtained (unless otherwise indicated by visual assessment) compared to the control consisting of similar cultivated plots of land treated with standard insecticides (in practice). carbofuran or pyrethroids) at normally active doses.

Example 2
Example I is repeated but sowing the seeds at a rate of 200 kg / ha.

 The results shown in Table 1 were obtained.

Example 3
Example 1 is repeated but pre-germinating the rice seed.

 The results shown in Table 1 were obtained.

Example 4
Example 2 is repeated but pre-germinating the rice seed.

 The results shown in Table 1 were obtained.

Table 1:

<tb> Attack <SEP> of <SEP> type <SEP> NO <SEP> Property <SEP> observed <SEP> for <SEP> determine <SEP> expressed <SEP> Result <SEP> observed <SEP>
<tb><SEP> result <SEP> in <SEP> percentage <SEP>
<tb><SEP> Ex.1 <SEP> Ex.2 <SEP> Ex.3 <SEP> Ex.4
<tb> I <SEP> number <SEP> of <SEP> attacked <SEP><SEP> 55 <SEP> 60 <SEP> 55 <SEP> 60
<tb> 2 <SEP> surface <SEP> of <SEP><SEP> sheets attacked <SEP> 79 <SEP> 87 <SEP> 79 <SEP> 87
<tb> 3 <SEP> number <SEP> of <SEP> times <SEP> attacked <SEP> 82 <SEP> 90 <SEP> 82 <SEP> 90
<tb> 4 <SEP> number <SEP> of <SEP> plants <SEP> attacked <SEP> just <SEP> in <SEP> 35 <SEP> 39 <SEP> 35 <SEP> 39
<tb><SEP> below <SEP> of <SEP> the kepi <SEP>
<tb> 5 <SEP> 0 <SEP> number <SEP> of <SEP> leaves <SEP> having <SEP> one <SEP> part <SEP> 57 <SEP> 63 <SEP> 57 <SEP> 63
<tb><SEP> desiccated
<tb> 6 <SEP> number <SEP> of <SEP> times <SEP> attacked <SEP> 80 <SEP> 88 <SEP> 80 <SEP> 88
<tb> 7 <SEP> number <SEP> of <SEP> grains <SEP> losing <SEP><SEP> color <SEP> 63 <SEP> 70 <SEP> 63 <SEP> 70
<tb><SEP> normal <SEP> yellow <SEP> at <SEP><SEP> profit from <SEP><SEP> brown spots
<Tb>

Claims (14)

claims  A method for protecting cultures against fungal or bacterial attack characterized in that an effective amount of 1-phenyl pyrazole is applied.  2. Method according to claim 1 used for the protection of rice crops.  3. Method according to one of the preceding claims characterized in that it is implemented for protection against both fungal or bacterial attack and against attacks by arthropods or insects.  4. Method according to one of the preceding claims characterized in that it is implemented against fungal attacks such as rhizoctonia, pelliculariose, helminthosporiosis, rice blight, blast, blotch, rhinchosporiosis.  5. Method according to one of the preceding claims characterized in that it is implemented against bacterial attacks such as those from the Pseudomonas or Erwinia.  6. Process according to claim 1, characterized in that the 1-phenyl pyrazole has the formula (I)

 in which:  R1 is CN or methyl;  R2 is S (O) nR3;  R3 is alkyl or haloalkyl;  R4 represents a hydrogen or halogen atom; or an NRsR6 radical, S (O) mR7, C (O) R7, alkyl, haloalkyl or OR8 or a radical -N = C (R9) (R10);  R5 and R6 are independently hydrogen, alkyl, haloalkyl, C (O) alkyl, S (O) rCF3; or R5 and R6 may together form a divalent alkylene radical which may be interrupted by one or two divalent heteroatoms, such as oxygen or sulfur;  R7 represents an alkyl or haloalkyl radical;  R8 represents an alkyl radical, haloalkyl radical or a hydrogen atom;  Rg represents an alkyl radical or a hydrogen atom;  R10 represents a phenyl or heteroaryl group optionally substituted with one or more halogen atoms or groups such as OH, -O-alkyl, -S-alkyl, cyano, or alkyl;  R1 and R12 represent, independently of one another, a hydrogen or halogen atom;  R13 represents a halogen atom or a haloalkyl, haloalkoxy group, S (O) qCF3 or SFg;  m, n, q, r represent, independently of one another, an integer of 0.1 or 2;  X represents a trivalent nitrogen atom or a radical> C-R 1 2;  with the proviso that when R1 is methyl, then R3 is haloalkyl, R4 is NH2, R1 is Cl, R13 is CF3, and X is N.  7. Method according to one of the preceding claims characterized in that the 1-phenyl pyrazole has the formula (I) wherein R1 is CN, R3 is haloalkyl, R4 is NH 2, R 1 1 and R 12 are independently of one another a halogen atom, and R 13 is haloalkyl.  8. Method according to one of the preceding claims characterized in that the 1-phenyl pyrazole is the  1- [2,6-Cl 2 4-CF 3 phenyl] 3-CN 4- [SO-CF 3] 5-NH 2 pyrazole.  9. Method according to one of the preceding claims characterized in that the treatment is performed on the foliage or on the ground or on the seeds.  10. The method of claim 1 characterized in that the treatment is carried out at a rate of compound of formula (I) between 5 and 500 g / ha, preferably between 10 and 200 g / ha.  11. Method according to one of the preceding claims characterized in that 1-phenyl pyrazole is applied at doses of between 20 and 80 g / ha.  12. Method according to one of the preceding claims characterized in that the 1-phenyl pyrazole is applied seed treatment at a rate of 2 to 200 g. per quintal of seeds, preferably from 5 to 80 g / q.  13. Method according to one of the preceding claims characterized in that the 1-phenyl pyrazole is applied seed treatment at a rate of 5 to 60 g. per hundredweight of seed  14. Compositions for the implementation of a method according to one of the preceding claims characterized in that they contain from 0.0001 to 95 by weight of active ingredient of formula (I).