FR2694161A1 - Fungicidal compositions comprising a 1-hydroxyethyl azole derivative and an alkoxylate of an aliphatic alcohol. - Google Patents

Abstract

A fungicidal composition is provided which comprises a compound of the general formula: (CF DRAWING IN BOPI) in which: R preferably represents a t-butyl radical; X preferably represents a nitrogen atom; Y preferably represents a -CH2 -CH2 - group; and Zm is preferably a 4-halogen substituent; and an aliphatic alcohol alkoxylate, for example an ethoxylate, with an average of 5 - 9 ethylene oxide units per molecule, of a C9 - 15 aliphatic alcohol, as an adjuvant. It has been found that the presence of the alkoxylate significantly increases the fungicidal efficacy of a compound of general formula I, particularly in leaf applications against fungi pathogenic to cereals.

Description

The present invention relates to novel fungicidal compositions, their

  The present invention relates in particular to novel fungicidal compositions which incorporate 1-hydroxyethyl compounds.

  azoles as disclosed in U.S. Patent No. 4723984.

  It has now been discovered that the fungicidal activity of the abovementioned compounds is surprisingly and significantly increased when an adjuvant selected from a particular class, namely the fungicides, is added to a plant to be treated at the same time. Aliphatic alcohol alkoxylates Such alkoxylates are substantially non-phytotoxic

  they are very suitable for the development of practical formulations.

  In accordance with a first aspect of the present invention, there is provided a fungicidal composition comprising a compound having the general formula o H

Y-C R

CH 2

  Wherein: R represents an alkyl radical, an optionally substituted cycloalkyl radical or an optionally substituted phenyl radical; X represents a nitrogen atom or a CH group; Y is -OCH 2, -CH 2 CH 2 or -CH = CH-; Z represents a halogen atom, an alkyl, cycloalkyl, alkoxy, alkylthio, haloalkyl, haloalkoxy or haloalkylthio radical, an optionally substituted phenyl radical, an optionally substituted phenoxy radical, an optionally substituted phenylalkyl radical or an optiomally substituted phenylalkoxy radical; and m is 0, 1, 2 or 3; or an acidic additive salt, or a metal salt complex thereof;

  and an alkoxylate of an aliphatic alcohol.

  In accordance with a second aspect of the present invention, there is provided a method for controlling a fungus at a locus, comprising treating said locus with a composition of the first aspect. The locus may be a locus.

agricultural or horticultural.

  The locus can be plants prone to fungal attack, seeds of such plants, or the medium in which the plants grow or must be grown. The method may include fighting fungi that are already present on the locus and / or or a prophylactic fungicidal treatment on a locus The composition can be used to control a large number of plant fungal diseases, for example Erysiphe, Puccinia, Rincosporium, Pyrenophora and Septoria In particular, the plants can suitably be cereals, in particular wheat or barley plants, because of the control which can be obtained by the process according to the invention against fungal invasions

  Erysiphe graminis (oidium) and Leptosphaeria nodorum (septoria).

  The process according to the present invention preferably involves

  the treatment of the leaves of the plants with the composition.

  The method according to the present invention preferably comprises treating the locus with an aqueous composition which comprises a

  the general formula I and an alkoxylate of an aliphatic alcohol.

  An alkoxylate of a preferred aliphatic alcohol is based on alkoxy units having 2 carbon atoms, thus being an ethoxylate, and 2 and 3 carbon atoms, thus being a mixed ethoxylate / propoxylate. An ethoxylate of such alcohol ethoxylates is preferred. are available from various sources and can be prepared by alkoxylating an appropriate aliphatic alcohol under conditions

known.

  In the aliphatic alcohol alkoxylates preferred for use in the context of the present invention, the alkoxylate chain may have at least 5 parts of alkoxy molecule, suitably 5 to 25 parts of alkoxy molecules,

  preferably from 5 to 15, and most preferably from 5 to 9.

  In the alcohol alkoxylates preferred for use in the context of the present invention, the alcohol molecule portion is derived from a C 9-18 aliphatic alcohol, preferably a C 8-15 aliphatic alcohol. As is well known, such alcohols are normally available in the form of mixtures. However, it can be established that, in the context of the present invention, the preferred alcohols are primary, or predominantly primary, straight chain alcohols. or predominantly straight chain, and hydroxy, or predominantly hydroxy. They may be saturated or unsaturated but are preferably saturated alcohol alkoxylates, or alcohol alkoxylates in which saturated alcohol molecules predominate The words "predominant" and "predominantly" mean "more than 50% by weight" and preferably "not less than 80% by weight"

% by mass ".

  Alcohol alkoxylates in which the alcohol is derived can be used

  vegetable, animal or mineral oil.

  In the process according to the present invention, the presence of an alkoxylate of an aliphatic alcohol can substantially reduce the amount of a compound of the general formula I to be applied to a locus in order to obtain a level of In practice, a compound of the general formula I may suitably be applied at a locus in an amount in the range of 10 to 600 g / ha, preferably 50 to 300 g / ha. Suitably, the adjuvant can be applied at a locus in an amount ranging from 60 to 2000 g / ha, preferably from 300 to 200 g / ha.

1500 g / ha.

  Although a composition comprising an aliphatic alcohol alkoxylate and a compound of the general formula I may have other fungicidal applications, it is likely that its primary utility lies in therapeutic applications on the leaves. Activity can be increased or increased. expanded when applying at the same time another fungicidal compound, of which suitable examples are dithianone, chlorothalonil and fenpropimorph Preliminary tests have shown that the effect of increasing the alkoxylate adjuvant on a compound of the general formula Where such a compound is also applied, such a compound, when applied at the same time, may suitably be applied at the same time in an amount in the range of 20 to 20%.

  1200 g / ha, preferably from 100 to 800 g / ha.

  It may be desirable to apply other compounds at the same time to the locus, for example an insecticide, an acaricide, a herbicide, a nematocide

or a fertilizer.

  In accordance with another aspect of the present invention, there is provided an aqueous composition for use in the process according to the present invention, and to be applied to said locus. Such a composition may be prepared by mixing an aliphatic alcohol ethoxylate and a composition containing a compound of the general formula I from different sources in water contained in a tank; or preferably, by adding to water contained in a tank, a "single" premixed formulation containing both an aliphatic alcohol alkoxylate and a compound of the general formula I Such a premixed formulation may, conveniently, be a liquid or a powder that can be wet, products that can both be

manufactured in a standard way.

  If desired, an anti-foaming agent may be used in accordance with current practice. An anti-foaming agent may be a constituent of a "single" formulation When the aqueous composition is to be prepared by mixing an alcohol ethoxylate aliphatic and a composition containing a compound of the general formula I, the anti-foaming agent can practically

  be formulated with the ethoxylate component.

  In the traditional way, anti-foaming agents are chosen according to their compatibility with the formulation to be prepared; For example, the solubility of the antifoaming agent in the composition should be controlled. Selection according to such criteria is merely a formality in the formulation technology. In accordance with the present invention, and particularly for "single" formulations, traditional compatible anti-foaming agents, including silicone products, would be suitable. However, it has been discovered that conventional agents such as silicone are in fact not suitable for use with compositions in accordance with

the present invention.

  Surprisingly, it has now been discovered that certain paraffinic oils, which are not traditional anti-foaming agents, are not only compatible with the compositions of the present invention, but also provide useful antifoam properties when necessary. It is therefore preferred that the composition according to the present invention is used in conjunction with a paraffinic oil as an anti-foaming agent, for example as an ingredient of the composition or as an additive to the formulation ingredients. in an aqueous mixture contained in

a tank.

  In general, paraffinic oils are derived from petroleum and are composed of paraffinic and aromatic hydrocarbons, generally naphthenic hydrocarbons. Paraffinic oils suitable for use as anti-foaming agent in compositions according to the present invention. have a molecular weight in the range of from 180 to 180 and contain a quantity of hydrocarbons included in the range

  ranging from 45 to 100%, preferably from 50 to 100%.

  The concentration of the components in the aqueous composition can be calculated from the amount of a compound of the general formula I and the alkoxylate to be supplied, and depending on the degree of application of the composition. that is, the volume applied). Characteristically, the degree of application of the composition may be from 100 to 1000 l / ha. Thus, when the degree of application of the composition should be 1000 l / ha, and that of a compound of the general formula I and the alkoxylate of 100 g / ha and 400 g / ha respectively, the aqueous composition will contain 0.1 g / l of a compound of the general formula I and 0.4 g In general, the aqueous composition may contain

  0.02 to 6.0 g / l of a compound of the general formula I and from 0.08 to 20 g / l of alkoxylate.

  In accordance with another aspect of the present invention, there is provided a concentrated formulation containing an alkoxylate of an aliphatic alcohol and a

  compound of the general formula I, to be dispersed or dissolved in water.

  Such a concentrated formulation may conveniently contain 200 g / kg, preferably 120 g / kg of a compound of the general formula I, and 100 1000 g / kg, preferably 400 700 g / kg of an adjuvant, the rest of the formulation

  concentrated being made of other usual materials.

  With reference to the compounds of the general formula I, it will be appreciated that they will have optical isomers due to the presence of an optical center. The process according to the present invention may use a compound of the general formula I under the form of a single optical isomer, or in the form of a racemic mixture, or in the form of any other mixture of optical isomers Similarly, if Y represents the group -CH = CH-, the compounds of the general formula I may additionally exist in two geometric isomeric forms, and the method according to the present invention may also be applicable to an individual geometric isomer, or to any

  mixture of geometric isomers.

  The preferred 1-hydroxyethyl azole derivatives used in the composition and process according to the present invention are those wherein R represents a straight or branched chain alkyl radical with 1 to 4 carbon atoms, a cycloalkyl radical having 3 to 7 carbon atoms and which is optionally substituted with alkyl having 1 or 2 carbon atoms, or a phenyl radical which is optionally monosubstituted or polysubstituted with the same or different substituents, the preferred substituents being: halogen, alkyl with 1 to 4 carbon atoms, and haloalkyl with 1 or 2 carbon atoms and 1 to 5 identical or different halogen atoms (such as, in particular, fluorine and chlorine atoms) ; Z represents a halogen atom, a straight or branched chain alkyl radical with 1 to 4 carbon atoms, a cycloalkyl radical with 5 to 7 carbon atoms, an alkoxy or alkylthio radical with, in each case, 1 to 4 atoms carbon, a haloalkyl, haloalkoxy, or haloalkylthio radical with, in each case, 1 or 2 carbon atoms and 1 to 5 identical or different halogen atoms (such as, in particular fluorine and chlorine atoms), or a phenyl, phenoxy, phenylalkyl or phenylalkoxy radical, in each case optionally substituted, the phenylalkyl radical and the phenylalkoxy radical having 1 or 2 carbon atoms in the alkyl part or in the alkoxy part, and preferred substituents which may be mentioned being halogen and alkyl having 1 to 4 carbon atoms; and X, Y and m have the

meanings indicated above.

  Particularly preferred compounds of formula I are those in which R represents a tert-butyl, isopropyl or methyl radical, or a cyclopropyl, cyclopenthyl or cyclohexyl radical, in each case optionally substituted by methyl or phenyl which is optionally monosubstituted or distributed by identical or different substituents selected from fluorine, chlorine, methyl and trifluoromethyl; Z represents a fluorine, chlorine or bromine atom, a methyl, tert-butyl, cyclohexyl, methoxy, methylthio, trifluoromethyl, trifluoromethoxy or trifluoromethylthio radical, or a phenyl, phenoxy, benzyl or benzyloxy radical, in each case optionally monosubstituted or distributed by identical or different substituents selected from fluorine, chlorine and methyl; and X, Y and m have

  the meanings given above.

  Preferably, m represents 1 Preferably Zm represents a single substituent located in the 4 position. Most preferably, Zm

  represents a 4-chloro substituent.

  Specific compounds of the general formula I which may be used in the composition and process according to the present invention are

  given in U.S. 4723984, which is incorporated herein by reference.

  In a particularly preferred compound of formula I for use in the compositions and method according to the present invention, Zm

  represents a part of 4-chloro molecule, Y represents a group -CH 2 CH 2

  X represents a nitrogen atom and R represents a tert-butyl group This compound

  is known as the common chemical name of tebuconazole.

  The preparation of the compounds of the general formula I is described in

U Patent 4723984.

  The present invention also relates to a preparation process

  of a composition as described above.

  The present invention will now be described further by making

  reference to Accompanying Examples.

Examples 1

  a) Materials The commercially available emulsifiable concentrate (EC) formulation of a compound of the general formula I, which is sold under the brand name HORIZON, which contains the active ingredient tebuconazole ( CASE

  RN 1 107534-96-3 1) at a concentration of 250 g / I.

  The materials used were the EC HORIZON formulation, an aliphatic alcohol alkoxylate and tap water. The particular alcohol ethoxylate chosen was DOBANOL 91-6 (Registered Trade Mark) available from SHELL. an aliphatic alcohol ethoxylate derived from mineral oil, predominantly having portions of Cg-11 primary alcohol molecules, and a

  average of 6 ethoxy units per molecule.

  h) Us seedlings Winter wheat, Homet cv, was sown in 7 cm square pots We obtained 20 to 25 plants per pot After a period of 12 days in

  normal greenhouse conditions (initially, watering from above, then

  automatic irrigation; temperature of 20 250 C; photoperiod of 16 hours of daylight, supplemented by mercury vapor lamps and / or sodium lamps if necessary), after which the seedlings were in the 1-2 leaf stage, the plants were inoculated with Erisphe graminis fsp tritici, from culture broth The treatment was applied on day 13, usually about 28 hours after inoculation. The plants were left in a controlled environment compartment of a greenhouse using a spray design.

  double random rows to reduce variations due to placement.

  The watering was carried out by means of an automatic system of under-irrigation

by matting.

  c) Preparation and application of the spray solutions.

  All test solutions were sprayed at four strengths, the difference between assays being a multiplication factor of 2, the application rates being 25, 50, 100 and 200 g / ha of the active ingredient (IA Tebuconazole The mass of a single amount of the product was determined for all the assays of the product. When the adjuvant was added as a single ratio IA: adjuvant, the whole batch was prepared for concentration. the highest, then the appropriate aliquots were diluted with tap water to obtain the appropriate concentrations for the lowest dosages When the adjuvant was added as a single dose per hectare for all treatments, the base formulation was set at twice the required concentration, then each dose was diluted to the correct concentration with adjuvant culture broth All applications were performed using a mobile vaporizer mount rail mounted and equipped with a single flattened spraying tip, calibrated

  to spray 400 1 / ha 4 pots (replicates) were sprayed for each treatment.

  In this Example 1, the alcohol ethoxylate adjuvant was added to give a single dose per hectare, 1 kg / ha, for all treatments. d) Evaluation The assessment of the infection was done first after one week, then after two weeks In general, the first assessment was made against a scale of results from 0 to 9, in which O means: not of infection, and 9 means very strong infection Subsequent assessments were usually expressed as percentage of leaf area

infected with powdery mildew.

ç) Results

  The results are given below in the form of a graph.

  The results after one week were analyzed in a standard way, using a sample analysis to determine the ED 9c number, ie the degree of application of the active ingredient needed to provide a control to 90% of the fungus, and the 95% limit mark These figures are given in Table 1 below.

4

  o 3 Q M In it 7 days after treatment DOBANOL at 1000 giha Without DOBANOL

g / ha of i a.

% infected go 6 - 2 O C -

50 L 00

Table 1

g / ha of Ti a.

  Product / mixture ED 9 o (g) Brand Limit 95% HORIZON only 80 64 102

HORIZON / Dobanol

at kg / ha 32 22-44 a- 2) 5

Example 2

  Further series of tests were performed in accordance with those described in Example 1, also using HORIZON as commercially available, but using I A dosage levels of 6.25, 12. However, in these tests, DOBANOL was used both at a rate of 1 kg / ha as above, and in a proportion of 10 parts by weight for 1 part of 1%. active ingredient The ED 9 o results calculated from the results are

  given in Table 2 below.

Table 2

  It should be noted that the alcohol ethoxylate has been added to a commercial sample formulated with the active ingredient In this context, the high level of increase in activity of a pre-formulated source of tebuconazole which is

  has managed using an alcohol ethoxylate is surprising.

  It should be noted that the use of capital letters in this text to write words for materials indicates that these words are

  trademarks, or that we think they are.

  It should be noted that the information that has been provided regarding the chemical constitution of the various materials designated by Trademarks, has been from what is commonly known and from the information provided

  by the manufacturer or distributor where available.

  Product / mixture ED 9 o (g) Brand Limit 95% HORIZON only 88 69 117

HORIZON / Dobanol

at 1 kglha 15 12 20

HORIZON / Dobanol

at 1:10 32 25 41

Claims (10)

  A fungicidal composition comprising a compound having the general formula O OH I Y-C -R   Wherein R represents an alkyl radical, an optionally substituted cycloalkyl radical or an optionally substituted phenyl radical; X represents a nitrogen atom or a CH group; Y is -OCH 2, -CH 2 CH 2 or -CH = CH-; Z represents a halogen atom, an alkyl, cycloalkyl, alkoxy, alkylthio, haloalkyl, haloalkoxy or haloalkylthio radical, an optionally substituted phenyl radical, an optionally substituted phenoxy radical, an optionally substituted phenylalkyl radical or an optionally substituted phenylalkoxy radical; and m is 0, 1, 2 or 3; or an acidic additive salt, or a metal salt complex thereof;   and an alkoxylate of an aliphatic alcohol.   A composition according to claim 1 wherein the alkoxylate comprises   from 5 to 25 parts of alkoxy molecule.   3 A composition according to one of the preceding claims, wherein   the alkoxylate is an ethoxylate or a mixed ethoxylate / propoxylate.   4 A composition according to one of the preceding claims, wherein   the aliphatic alcohol is a C 9-18 aliphatic alcohol.   A composition according to one of the preceding claims, wherein the   part of the alcohol molecule is a part of the primary alcohol molecule, or, when there is a mixture of parts of alcohol molecules, they are, so predominant, primary.   A composition according to one of the preceding claims, wherein the   part of the alcohol molecule is straight chain, or when there is a mixture of   parts of alcohol molecules, they are predominantly straight-chain.   A composition according to one of the preceding claims, wherein the   part of the alcohol molecule has only one hydroxy group or, when there is a mixture of parts of alcohol molecules, the parts of alcohol molecules with a   only hydroxy group are predominant.   8 A composition according to one of the preceding claims, wherein the   part of the alcohol molecule is saturated or, when there is a mixture of parts of   alcohol molecules, the parts of saturated alcohol molecules are predominant.   9 A composition according to one of the preceding claims, wherein Zm   represents a part of 4-chloro molecule, Y represents the group -CH 2CH 2,   X represents a nitrogen atom and R represents a t-butyl group.   A composition according to one of the preceding claims, which is a   concentrated formulation to be added to water and containing from 5 to 200 g / kg of a compound of the general formula I, and from 100 to 1000 g / kg of an alkoxylate of a aliphatic alcohol.   A method of controlling a fungus at a locus, said method comprising treating the locus with a composition according to one of Claims 1 to 9.   Use of a fungicide of a composition according to one of claims 1 to 9.