IL74170A

2-phenyl 2((azol-1-yl)methyl)tetrahydrofuran-5-ol derivatives,their preparation and fungicidal compositions containing them

Abstract

This record has no abstract on file.

IL74170A, drawing sheet 1 — Sheet 1 of 21

Term

No projected expiry on record.

15 claims: 3 independent, 12 dependent

1
CLAIMS:I. A compound of the formula: in which:. X is a halogen atom or a cyano or nitro group or a C x -C 13 alkyl or alkoxy group, optionally halogenated, n is 0, 1, 2 or 3 W denotes a trivalent group consisting of either a =CHgroup or a nitrogen atom =Nr x denotes a hydrogen atom or a C x -C 4 alkyl radical, R 2 denotes a hydrogen atom or an alkyl, cycloalkyl, phenyl or naphthyl radicals, optionally substituted by halogen atoms, preferably chlorine and fluorine, and alkoxy, phenoxy or naphthyloxy radicals.
3
A compound according to one of claims 1 or 2, in which n equals 2.
4
A compuond according to one of claims 1 to 3, in which X is fluorine, bromine or chlorine or an alkyl or alkoxy radical having from 1 to 4 carbon atoms, or CF^.
8
A process for preparing compounds according to one I of claims 1 to 7, wherein a compound of formula in which Z is a chlorine or bromine atom and X, n, 2 and R have one of the significances given in one of claims 1 to 7, is reacted with an alkali metal derivative of an imidazole or triazole.
10
A fungicidal composition which contains, as active substance, a product according to claims 1 to 7, this active substance being mixed with at least one inert support which is acceptable in agriculture.
13
A process for controlling fungal diseases of crops, wherein there is applied an effective dose of an active substance according to one of claims 1 to 7.
15
A process according to one of claims 13 and 14, wherein the crop treated isacereal and/or the crop is attacked, or capable of being attacked, by eyespot.

Independent claims7

593 paragraphs in 7 sections, as filed

The present invention relates to new products for use ' in plant protection containing triazole or imidazole groups and oliogoether groups. The invention also relates to processes for preparing the said products as well as their : application for. the protection of plants, especially in the ! field of controlling parasitic fungi,: but also in the regulation of plant growth.

Many products containing a triazole group, especially fungicides, are already known. British Patent No, 2,115,400 ׳' discloses triazole derivatives having fungicidal activity also comprising a substituted tetrahydrofuran ring, however, it does not disclose the -OR2 substituents on the tetrahydrofuran ring: as in the compounds of the present invention.

An object of the invention is to provide new products ־ which make possible new ways of treating plants. Another object of the invention is to provide products which are highly active especially, against rust and mildew, and more particularly against cereal mildew. Another object of the invention is to provide products which have polyvalent activity covering, in particular, grey mould (Botrytis), leaf spot, eyespot and diseases of seeds. Further objects and advantages of the invention will become clear during the description which follows.

It has now been found that these objects could be attained by means of the products of the invention. These products are of the

in which

X is a halogen atom preferably fluorine, bromine or chlorine, or a cyano or nitro group or a Cx-Ci3 alkyl or alkoxy group, optionally halogenated n 0, 1, 2 or 3.

W denotes a trivalent group consisting of either a =CHgroup or a nitrogen atom =NRx denotes a hydrogen atom or a C!-C4 alkyl radical,

R2 denotes a hydrogen atom or an alkyl, cycloalkyl, phenyl or naphthyl radicals, optionally substituted by halogen atoms, preferably chlorine and fluorine, and alkoxy, phenoxy or naphthyloxy radicals.

Among the compound of formula (I), the compounds in which W denoted a nitrogen atom are preferred for fungicidal applications.

For the purpose of use against eyespot, the compounds in

number of asymmetric centres in the molecule. The inven־ 10 tion hence . re lates both to these optical isomers and to their racemic mixtures and the corresponding diastereo־ isomers. Separation of the diastereoisomers and/or optical isomers can be accomplished according to methods known per s e .

,15 The invention also relates to the salt forms of the compounds according to the invention, and more especially the hydrochlorides, sulphates, oxalates and nitrates.

The present invention also relates to processes for preparing the compounds according to the invention.

According to a first process, a compound of the formu I a

CH2Z (II) in which 2 is a chlorine or bromine

1־ atom and X. n, R and r2 have the same significance as in formula (I), is reacted with an alkali metal derivative (for example a sodium or potassium salt) of an imidazole or triazole.

The reaction is usually performed in an aprotic polar solvent medium and can also be catalysed, for example by adding an alkali metal iodide; the temperature is gener10 ally between 50 and 250°C, preferably between 70 and 230°C. for economic reasons, overall reagent concentrations of between 1 and 50X are most frequently used.

The compounds of formula (II) can be prepared by re reacting an alcohol R OH with a compound of the formula

OR3 (III) in the presence of an acidic catalyst, R1, R^, χζ χ anc| n having the same significance as above, and being an organic radical, preferably a lower alkyl (0-,.4) radical, and two radicals R^ can together form a divalent organic radical, preferably a lower alkylene radical.

The catalytic acid used in this reaction can be either a protic or an aprotic acid. As protic acids, there may be mentioned hydrochloric, sulphuric, trif luoroacetic, perchloric, benzenesuLphonic, tolulenesulphonic and methane sulphonic acids. As aprotic acids, there may be mentioned Lewis acids such as BF3, AICI3 and SnCl4. When hydrochloric aCid is used as catalyst, it may be generated in situ, for example by means of an acyl chloride, especially acetyl chloride,, which reacts with the alcohol present tb give rise to HCl.

The reaction, is normally performed by simply heating the reagents mentioned. The temperature is generally within the temperature range from 50°C to the boiling point of the reaction medium. The alcohol R^OH usually performs the role of solvent in the reaction medium. An inert cosolvent can also be added, in particular an aliphatic, alicyclic or aromatic hydrocarbon which may be halogenated or unhaLogenated, or, an ether.

The compounds of formula (III) are usually prepared by reacting a carbonyl compound of formula (X)n

CO - ch2z (Illa) with the organomagnesium derivative prepared from a compound of formula

R1 OR5־

I I

Z' - CH- - CH - CH - OR5־ 2 (Illb) in which formulae Z' is a halogen atom, preferably bromine, and X, Z, R*', and n have the signif icance given above. The 0rganomagnesium derivative can be prepared, in a manner known per se, by the action of a -haLoaLdehyde acetal on magnesium in a solvent medium. This -haloalde15 hyde acetal can itself be prepared according to known methods, for example according to G. Buchi and H. Wuest,

J. Org. Chem. 34 1122 (1969) and H. Meerwein, Houben-Weyl, Methoden der Org. Chem. vol. VI/3 page 204, 4th edition (1965),.

־ 7 ־

The reaction of the compound of formula (Illa) with the organomagnesiurn derivative of the compound of formula (Illb) is most frequently performed at a temperature between -70°C and +100°C, preferably between -50°C and +50°C. As solvent, there may be mentioned ethers, es- pecially diethyl ether and tetrahydrofuran, or aliphatic, alicyclic or aromatic hydrocarbons, or mixtures thereof.

The examples which follow, which are given without implied Limitation, illustrate the invention and show how it can be used.

Examples 1 to 3 and Table (I) illustrate particular methods of preparing compounds according to the invention, as well as these compounds themselves. Among the physical propertiesgiven for these compounds, the values of the NMR shifts (delta) of the proton in the -0-CH-0- (acetal) group have been given. These shifts are ׳measured in ppm and they are read with respect to a reference product, tetramethyIsi lane. The NMR is performed at 100 MHz in deuterated chloroform.

Examples 4 to 7 illustrate the fungicidal properties of the compounds according to the invention, as well as their applications.

In these examples, the spraying of solutions or suspensions of active substance is performed under conditions such that the spraying of. a solution or suspension of concentration equal to 1 g / L corresponds on av.erage to the application of approximately 2 microgrammes of active substance per cm^ of plant leaf.

Under the conditions of Examples 4 to 7, the com-, pounds illustrated did not show phytotoxicity.

In these examples, a product is regarded as providing complete protection against a fungal disease when the protection is at least 95%; the protection is regarded as good when it is at Least 80% (but less than 95%), as fairly good when it is at least 70% (but less than 80%) and as average when it is at least 50% (but less than 70%).

In the present account, the percentages are, except where otherwise stated and except in regard t-0 yields, percentages by weight. In the case of percentages expressed relative to the stoichiometry, these are mole percentages. As regards concentrations, some of these are expressed in ppm (parts per million) which corresponds to mg/l. Example 1:

An organomagnesiurn derivative is prepared by activation of magnesium (9.7 g; 0.4 mole) with di bromoethane (0.5 ml) in anhydrous tetrahydrofuran (10 ml) (abbreviated THF). While the temperature is maintained below 15°C, a solution of 2-( -bromoethy I)-1,3-dioxo lane (47 ml; 0.4 mole) in THF (200 ml) is added dropwise. A quarter of an hour after, the addition is completed, the mixture is cooled to - 45°C and a solution of chloromethyl para-ch loropheny I ketone (56.7 g; 0.3 mole) in THF (150 ml) is added, the temperature being maintained at -45°c. After half an hour, the mixture is neutralised by means of pure acetic acid (120 ml), and then poured into water (one litre). Extraction is performed using ethyl acetate. The solution in ethyl acetate is dried and the solvent evaporated. A chlorohydrin (100 g) is obtained, m.p. 99°C (after recrystallisation in cyclohexane), of formula

OH p - Cl 6H4 - c - CH2 - ch2 . ch - i

Ch2c1

- Ch2 (VI)

A mixture of acetylchloride (0.1 ml) and a solution of the product of formula (VI) (6 g; 0.02 mole) in methanol (30 ml) is heated to boil under reflux for 2 hours.

The reaction mixture is then poured into an aqueous solution containing 5% by weight of sodium carbonate in water. The mixture is extracted with ethyl ether, the ethereal solution dried and the ether evaporated. An oil is obtained which is distilled at 140°C under an absolute pressure of 0.04 mmHg, and an oily product (4.7 g) is obtained of formula:

(VII)

CH2C1

A mixture obtained by adding the product of formula (VII) (4.2 g; 0.016 mole) to dimethyl sulphoxide (40 ml) 15 containing triazole sodium salt, prepared from triazole (1.6 g; 0.024 mole) and sodium hydride (0.7 g; 0.024 mole) in 80% strength oily suspension, is heated for 3 hours at 1700¢ under an inert atmosphere.

The solution is poured into water (200 ml). The mixture is extracted with ethyl ether, the ethereal solution dried and the ether evaporated. The residue is purified by chromatography on a silica column. An oil (3.1 g) is thereby obtained which consists of a mixture in sub- stantially equal proportions of two diastereoisomers of structural formula:

/ן^י

Example 2:

The product of formula:

is prepared by a process similar to that for preparing the product of formula (VI) in Example 1, but using chloromethyl ortho, para-dichlorophenyl ketone as reagent in place of chloromethyl parach 10rophenyL ketone.

A mixture of the product of formula (IX) (0.3 mole) with aqueous sodium hydroxide solution at 15X concentration by weight (400 ml) is stirred for 12 h at room temperature. The organic phase is diluted with ethyl ether, separated by decantation, washed, with water, dried and evaporated.

On distillation, a colourless viscous oil (64 g) is obtained of b.p. 147 to 150°C under an absolute pressure reduced to 0.02 mm Hg, which has the formula

A mixture of the following is heated for 6 hours at

110°C:

- a solution of the product of formula (X) (5.8 g; 0.02 mole) in n-butanol, (20 ml),

- triazole (1.4 g; 0.02 mole),

- triazole sodium salt (0.09 g; 0.01 mole).

The mixture is cooled to room temperature, diluted with water and extracted with ether, and the ethereal solu tion is then concentrated. The residue is purified by chromatography on a silica column, using as eluent a meth15 anol/ethyl acetate/hexane mixture containing the respective proportions 5:47.5:47.5 by volume.

A product (5.1 g) is obtained of m.p. 131°C, which has the formula:

(XI)

A mixture of acetyl chloride (0.10 ml) with a solution of the product of formula (XI) (3.1 g) in absolute ethanol (30 ml) is heated to boil under reflux for 4 h. The mixture is allowed to cool. The crystals formed are filtered off and washed with cold ethanol. White crystals (1.2 g) are thereby obtained, m.p. 162°C, which correspond to the more polar diastereoisomer (observed in thin layer chromatography) of the product of structural formula

The mother liquors from this filtration are concentrated, the residue is diluted with ethanol (1 ml) and then isopropyl ether (2 ml), and the crystals formed are separated. A further 0.2 g of the same diastereoisomer is obtai ned, m.p. 164°c .

By chromatography on silica of the residual oil from the crystallisation, a second diastereoisomer, the less polar, is obtained, m.p. 61°C. Examp Ie 3:

Using processes similar both to that of Example 1 and those of Examples 2 and 9, various other compounds were prepared which had the formula:

(XIII) of the substituents in this formula (XIII) characteristics of the compounds 1 to 50

OR2 c:

The nature and some physical are shown in Table (I), which also includes the products 5 prepared (Nos. 1, 10, 11 and 29) in Examples 1, 2 and 9.

However, as regards the compounds Nos. 49 and 50, instead of containing a para-ch lorophenyl group substituted with X1 in the ortho position, they contain a para-fiuorophenyl group substituted with in the ortho position.

Furthermore, compound No. 50 has an imidazole group instead of a triazole group, the preparation process remaining the same but the reactants been chosen appropriately.

In the case where is a hydrogen atom, the compounds contain 2 asymmetric carbon atoms, and the two di15 astereoisomers can be distinguished by thin layer chromatography on silica, using as eluent a methanol/ethyl acetate hexane mixture containing the respective proportions 5:20: 75 by volume. The less polar diastereoisomer migrates faster in chromatography and is referred to as A. The 20 more polar migrates more slowly in chromatography and is referred to as B.

In the case where r1 is other than a hydrogen atom, the compounds contain 3 asymmetric carbon atoms and there are 4 dו astereoisomers. These diastereoisomers are arbitrarily called A, B, C and D. They are sometimes difficult to separate by chromatography, but when this is possible, A is the. least polar, D the most polar, and B and C have intermediate polarities.

Example 4:

Test in vivo on Erysiphe graminis on barley (barley mildew)

By fine grinding, there is prepared an aqueous emulsion of the active substance to be tested, having the following composition:

- active substance to be tested 40 mg

- Tween 80 (surfactant consisting of an oleate of a polycondensate of ethyleneoxide with a sorbitan derivative) diluted to 1 OX in water 0.4 ml

-water 40ml.

This aqueous emulsion is then diluted with water to obtain the desired concentration.

Barley, sown in pots in loam, is treated at the stage where it is 10 cm in height by spraying it with an aqueous emulsion (referred to as spray mixture) at the concentration stated below. The trial is repeated twice. After 48 hours, the barley plants are dusted with Erysiphe graminis spores, the dusting being accomplished with the aid of diseased plants.

Readings are taken 8 to 12 days after contamination. Under these conditions, the following results are observed:

At a dose of 1 g/L, good or complete protection with the compounds

I, 2, 4, 5, 6, 7, 8, 17, 18, 19, 20.

At a dose of 0.33 g/l, complete protection with the compounds 8, 14, 16, 27.

At a dose of 0.11 g/l, complete protection with the compounds

II, 12, 13, 15, 28.

At a dose of 0.033 g/L, complete protection with the compounds 9 and 10.

Example

Test in vivo on Puccinia recondita responsible for wheat rust Wheat, sown in pots in Loam, is treated at the stage where it is 10 cm in height by spraying it with aqueous emulsions (referred to as spray mixtures) of the same composition as that described in Example 4, and at various concentrations of the compound to be tested. The trial is. repeated twice with each concentration.

After 48 hours, an aqueous suspension of spores (50,000 sp/cc) is sprayed onto the wheat; this suspension has been obtained from contaminated plants. The wheat is then placed for 48 hours in an incubation cell at approximately 18°c and 100X relative humidity.

After these 2 days, the relative humidity is Lowered to 60%. The condition of the plants is .verified between the 11th and 15th day after contamination by comparison with the untreated control.

Under these conditions, the following results are observed:

At a dose of 1 g/l, good protection with the compounds 4, 5, 6, 7, 9, 13, 14, 15, 16, 17, 18 and 21.

At a dose of 0.33 g/l complete protection with the compounds 5 10 and 11.

Example

Test on Botrytis cinerea on tomato:

Greenhouse-cultivated tomatoes (Marmande variety) from 30 to 40 days old are treated by spraying with aqueous 10 emulsions (referred to as spray mixtures) of the same composition as that described in Example 4 and at various concentrations of the compound to be tested. The trial is repeated twice with each concentration.

After 24 or 48 hours, the leaves are cut and placed 15 into 2 Petri dishes (diameter 11 cm) the base of which has been previously provided with a disc of damp filter paper (5 leaflets per dish).

The innoculum is then applied with the aid of a syringe by depositing drops (3 drops per Leaflet) of a 20 spore suspension. This suspension of spores of Bot ryt i s cinerea has been obtained from a 15-day culture which has been suspended in a nutrient solution (80,000 units/cc).

Verification is carried out 3 days after contamination by comparison with an untreated control.

Under these conditions, good or complete protection is observed at a dose of 1 g/l with compounds No. 8, 10 and

16.

Example 7:

Test in vitro on seed fungi and soil fungi

The action of the compounds according to the invention is studied on the following fungi responsible for

<td> 5</td><td> secondary diseases of cereals:</td><td></td>

<td></td><td> Cercospore I La herpotrichoides</td><td> (CERC)</td>

<td></td><td> He I mint hosporiurn gramineum</td><td> (HELM G)</td>

<td></td><td> Pyrenophorae avenae</td><td> (PYRE)</td>

<td></td><td> Septoria nodorum</td><td> (SEPT N)</td>

<td> 10</td><td> HeLminthosporiurn teres</td><td> (HELM T)</td>

<td></td><td> Fusarium roseum</td><td> (FUS ROS)</td>

<td></td><td> Fusarium nivale</td><td> (FUS NIV)</td>

<td></td><td> Fusarium culmorum</td><td> (FUS CULM)</td>

<td></td><td> Rhizoctonia cerealis</td><td> (RHIZ C)</td>

<td> 15</td><td> The designations given</td><td> in parenthesis will be used</td>

to denote these fungi in Table (II).

For each trial, the procedure is as follows: a nutrient medium consisting of potato, glucose and agar (PDA medium) is introduced supercooled into a series of

Petri dishes (20 ml per dish) after sterilisation in the autoclave at 120°c .

As the dishes are being filled, an acetone solution of the active substance is injected into the supercooled medium to obtain the desired final concentration.

As a control, Petri dishes similar to the above are taken in which there are poured similar amounts of a nutrient medium not containing active substance.

After 24 or 48 h, each dish is seeded by depositing a fragment of mycelium originating from a previous culture of the same fungus.

The dishes are kept for 2 to 10 days (according to the fungus tested) at 22°C, and the growth of the fungus in the dishes containing the active substance to be tested is compared with that of the same fungus in the dish used as cont rol.

For each compound tested, the weakest dose is thus 10 determined which enables development of the fungus in question to be 80 - 100% inhibited. This dose is referred to as the '1minimal inhibitory dose.

These minimal inhibitory doses, expressed in ppm, are recorded in Table (II), in which the abbreviations

1.5 have the significance given above.

The compounds according to the invention can thus be used for both preventive and curative control of fungi, especially of the type basidomycetes, ascomycetes, adelomycetes or fungi imperfect!, in particular rusts, mildews, 20 eyespot, fusarisoses, heLminthosporioses, septorioses and rhizoctones of vegetables and plants in general and, in particular, of cereals such as wheat, barley, rye, oats and their hybrids, and. also rice and maize.

The products of the invention are particularly 25 valuable by virtue of, their broad spectrum in regard to diseases of cerea I s (mi Idew, rust, eyespot, helminthosporioses, septorioses and especially the fusarioses which are difficult to control). They are. also very valuable by reason of their activity towards grey mould (Botrytis) and the cercosporioses and, for this reason, they can be applied to crops as varied as vine, market-gardening crops and arboriculture.

Finally, they show excellent selectivity towards crops.

They are advantageously applied at doses from 0.02 to 5 kg/ha, preferably from O.O5 and more specifically 0.1 t 0 2 kg /h a.

To use them in practice, the compounds according to the invention are rarely used alone. They most frequently form part of compositions. These compositions, which can be used for the protection of plants against fungal diseases, or in compositions for regulating plant growth, contain as an active substance a compound according.to the invention, as described above, in combination with solid or liquid supports which are' acceptable in agricul- . ture, and surfactants which are also acceptable in agriculture. The usual inert supports and usual surfactants can, in particular, be used.

These compositions can also contain any other type of ingredient, e.g. protective colloids, adhesives, thickeners, thixotropic agents, penetrants, stabilisers, sequestering agents and the like, as well as other known active substances having pesticidal properties (especially insecticidal or fungicidal properties), or properties which encourage plant growth (especially fertilisers) or pro22 perties of regulating plant growth. More generally, the compounds according to the invention can be combined with all the solid or liquid additives which correspond to the customary techniques of formulation.

These doses for use, in the case of using the com- pounds according to the invention as fungicides, can vary within broad limits, especially according to the virulence of the fungi and the climatic conditions.

Compositions containing 0.5 to 5,000 ppm of active 10 substance are generally very suitable; these values apply to the compositions ready for application. Ppm means parts per million. The range from 0.5 to 5,000 ppm is equivalent to a range from 5 x 10’^ to 0.5% (percentages by weight) .

5ן As regards compositions intended for storage and transportation, these more advantageously contain from 0.5 to 95% (by weight) of active substance.

Thus, the compositions for agricultural use according to the invention can hence contain the active sub20 stances according to the invention within very broad limits ranging from 5 x 10”^% to 95% (by weight).

According to what has already been stated, the compounds according to the invention are generally mixed with supports and optionally with surfac25 tants.

In the present account, the term support denotes an organic or inorganic, natural or synthetic material which is in combination with the active substance to facilitate the application of the latter to the plant, the seeds or the soil. This support is hence generally inert, and it must be acceptable in agriculture, especially 5 on the plant treated. The support can be solid (clays, natural or synthetic silicates, silica, resins, waxes, solid fertilisers, and the like) or liquid (water, alcohols, ketones, petroleum fractions, aromatic or paraffinic hydrocarbons, chlorinated hydrocarbons, liquefied gases, and 1 0 the I i ke) .

The surfactant can be an emulsifier, dispersant or wetting agent of ionic or nonionic type. There may be mentioned, e.g., salts of polyacrylic acids, salts of lignosulphonic acids, salts of pheno I su Iphonic or naphthalene15׳ sulphonic acids, polycondensates of ethylene oxide with fatty alcohols or fatty acids or fatty amines, substituted phenols (especially alkylphenols or arylphenols), salts of sulphosuccinic acid esters, taurine derivatives (especially alkyltaurates), and phosphoric acid esters of polyconden20 sates of ethylene oxide with alcohols or phenols. The presence of at Least one surfactant is generally essential when the active substance and/or the inert support are not water-soluble and the vector agent for the application is water.

For their application, the compounds of formula (I) are generally in the form of compositions; these compositions according to the invention are themselves in fairly diverse solid or liquid forms.

As solid forms of compositions, there may be mentioned powders for dusting or scattering (with a content of the compound of formula (I) ranging up to 100%) and 5 pellets, especially.those obtained by extrusion, by compacting, by impregnation of a granulated support, or by granulation starting from a powder (the content of the compound of formula (I) in these pellets being between 1 and 80% in the latter cases).

As Liquid forms of compositions, or forms designed to constitute liquid compositions when applied, there may be mentioned solutions, especially the water-soluble concentrates, emulsifiable concentrates, emulsions, flowables, aerosols, wettable powders (or powder for spraying) and pastes.

The emulsifiable or soluble concentrates most frequently contain 10 to 80% of active substance, whereas the emulsions or solutions ready for application contain 0.01 to 20% of active substance. In addition to the solvent, 20 the emulsifiable concentrates can contain, when necessary, to 20% of suitable additives such as stabilisers, surfactants, penetrants, corrosion inhibitors, colourings and adhesives. By way of example, the composition of a few concentrates is as follows:

Example F (formulation) 1::

- active substance 400 g/l

- alkali metal dodecyLbenzenesulphonate 24 g/L

:1 ethylene oxide/nonyLphenoI condensate 16 g/l

- cyclohexanone 200 g/l

- aromatic solvent q.s. 1 Litre.

According to another formula for an emulsifiable concentrate, there are used: Example F2 : ־active substance250 ׳g

- epoxide־trested vegetable oil25 g

- mixture of alkylaryl sulphonate, polyglycol ether and fatty alcohols 100g

- dimethyIformamide 50g

- xylene 575g

From these concentrates, by dilution with water, it is possible to obtain emulsions of any desired concentration, which are especially suitable for application to leaves.

FLowables, which can also be applied by spraying, are prepared so as to obtain a stable fluid product which does not settle, and they usually contain from 10 to 75% of active substance, from 0.5 to 15% of surfactants, from 0.1 to 10% of thixotropic agents, from 0 to 10% of suitable additives such as antifoams, corrosion inhibitors, stabilisers, penetrants and adhesives and, as a support, water or an organic liquid in which the active substance is of low solubility or insoluble: some solid organic substances or inorganic salts can be dissolved in the support to assist in preventing sedimentation, or as antifreeze for the water.

The wettable powders (or powder for spraying) are usually prepared so as to contain 20 to 95% of active substance, and they usually contain, in addition to the solid support, from 0 to 5% of a wetting agent, from 3 to 10% of a 5 dispersant and, when necessary, from 0 to 10% of one or more stabilisers and/or other additives such as penetrants, adhesives, or anti-caking agents, colourings, and the like. ' By way of example, various compositions of wettable powders are as follows:

Example F3 :

- active substance 50%

- calcium Lignosulphonate (deflocculant) 5%

- isopropyl naphthalenesulphonate (anionic wetting agent)

- anti-caking silica 5%

- kaolin (filler) 39%

Another composition of powder for spraying, at 70%. strength, uses the following constituents: Example F4:

- active substance700 g

- sodium dibutyInaphthaLenesuLphonate50g

- condensation product of naphthalenesulphonic acid, phenoLsulphonic acid and formaldehyde in proportions 3:2:130 g ־ kaolin100g

- whitening120 g

Another composition of powder for spraying, at 40% strength, uses the following constituents:

Example F5:

- active substance 400g

- sodium lignosulphonate 50g

- sodium dibutylnaphthalene sulphonate 10g

-silica540g

Another composition of powder for spraying, at 25% strength, uses the following constituents: Example F6:

- active substance 250g

- calcium Lignosulphonate 45g

- mixture of whitening and hydroxyethyl cellulose in equal parts by weight 19g

- sodium dibutylnaphthalenesulphonate 15g

- si Li ca 195g

-whitening 195g

-kaolin 281g

Another composition of powder for spraying, at25% strength, uses the foLLowing constituents:'

Example F7:

- active substance 250g

I - isooctylphenoxy-polyoxyethylene-ethanol 25g i - mixture of whitening and hydroxyethyl cellulose in equal parts by weight17 g .- sodium aluminosilicate543 g

- ki eseIguh r165 g

Another composition of powder for spraying, at 10% strength, uses the following constituents: Example F8:

- active material100 g

- mixture of sodium salts of sulphates of saturated fatty acids30 g

- condensation product of naphtha lenesulphonic acid and formaldehyde50 g

- kaolin820 g

To obtain these powders for spraying or wettable powders, the active substances are intimately mixed in suitable mixers with the additional substances, and the mixtures are ground in suitable mills or other grinders. Powders for spraying are thereby obtained, the wettability and suspendabiLity of which are advantageous; they can be suspended in water at any desired concentration and these suspensions can be very advantageously used, especially for application to plant leaves.

Instead of wettable powders, pastes can be produced. The conditions and methods of production and use of these pastes are similar to those for wettable powders or powders for spraying.

As already stated, the .dispersions and aqueous emulsions, e.g. the compositions obtained by diluting with water a wettable powder or an emulsifiable concentrate according to the . i nvent i on, are included withi-n the general scope of the present invention. The emulsions can be of the water-in-oiI or oi l-in-water type, and they can have

־ a thick consistency like that of mayonnaise.

Pellets intended for placing on the soil are usually prepared so as to be between 0.1 and 2 mm in size, and they can be manufactured by agglomeration or impregnation. In general, the pellets contain 0.5 to 25X of active substance and 0 to 10X of additives such as stabilisers, slow release modification agents, binders and solvents.

According to an example of a pellet composition, the following constituents are used:

Example F9;

- active substance50 g

- epichlorohydrin '2.5 g

- cetyl polyglycol ether2.5 g

- po lyethy lene g lyco I35 g

- kaolin (particle size: 0.3 to 0.8 mm) 910 g.

In this particular case, the active substance is mixed with the epichlorohydrin and dissolved in 60 g of acetone; the polyethylene glycol and cetyl polyglycol ether are then added. The kaolin is wetted with the solution obtained and the acetone is then evaporated under vacuum. Such a micropellet is advantageously used to control soil fungi.

The compounds of formula (I) can further be used in the form of powders for dusting; a composition comprising 50 g of active substance and 950 g of talc can also be used; a composition comprising 20 g of active substance, 10 g of finely divided silica and 970 g of talc can also be used; these constituents are mixed and ground, and the mixture is applied by dusting.

Further examples were also made. In these examples.

<td></td><td> the following abbreviations have</td><td> been used:</td>

<td></td><td> Botrytis cinerea</td><td> BOT</td>

<td></td><td> Erysiphe graminis .</td><td> ERYG</td>

<td> 5</td><td> Puccini a recondita</td><td> PUCR</td>

<td></td><td> Plasmopara viticola</td><td> PLA</td>

<td></td><td> Piricularia oryzae</td><td> PIR</td>

<td></td><td> Cercospora beticola</td><td> CBET</td>

<td></td><td> Peronospora tabacina</td><td> PERO</td>

<td> 10</td><td> Puccini a stri i formis</td><td> ‘ PUCS</td>

<td></td><td> Erysiphe cichoracearum</td><td> ERYC</td>

<td></td><td> Fusarium oxysporum (meloni)</td><td> FUS OX</td>

<td></td><td> Pytnium spp</td><td> PYT</td>

<td></td><td> Pyrenopnora avenae</td><td> PYR</td>

<td> 15</td><td> Septoria tritici</td><td> SEPT T</td>

<td></td><td> Venturia inequaLis</td><td> VENT</td>

<td></td><td> Whetzelinia scierotiorum</td><td> WHE</td>

<td></td><td> Mycosphaerella fijiensis</td><td> MSPH</td>

<td> 20.</td><td> Marssonina panattdniana</td><td> MARS</td>

<td></td><td> Alternari a solani</td><td> ALT</td>

<td></td><td> Aspergillus niger</td><td> ASP</td>

<td></td><td> Cercospora arachidicola</td><td> CARA</td>

<td></td><td> Cladospori 11m herbarum</td><td> CLAD׳.,</td>

<td> 25</td><td> HeLminthosporium oryzae .</td><td> HELM OR</td>

<td></td><td> Penici Ilium expans urn</td><td> PEN</td>

<td></td><td> Pestalozzia sp</td><td> PES</td>

<td> Phialophora cinerescens</td><td> PHI</td>

<td> Phoma betae</td><td> PHB</td>

<td> Phoma foveata</td><td> PHF</td>

<td> Phoma lingam</td><td> PHL</td>

<td> Listi Iago maycis</td><td> US I</td>

<td> Ascochyta pisi</td><td> ASCO</td>

<td> Guignardia bidwellii</td><td> GUIG</td>

<td> Cortici um rolfsi i</td><td> CRO</td>

<td> Phomopsis viticola</td><td> PHV</td>

<td> Sclerotinia sclerotiorum</td><td> SCL S</td>

<td> Sc Lerotinia minor</td><td> SCL M</td>

<td> Phytophthora cinnamomi</td><td> PHY CI</td>

<td> Phytophthora cactorum</td><td> PHY CC</td>

<td> Phytophthora capsici</td><td> PHY CP</td>

<td> Phytophthora infestans</td><td> PHY IN</td>

<td> Phytophthora parasitica</td><td> PHY PA</td>

<td> Phytophthora megasperma</td><td> PHY ME</td>

<td> Phytophthora syringae</td><td> PHY SY</td>

<td> Coryneum cardinale</td><td> CORY</td>

<td> Rhi zoctoni a solani</td><td> RHIZ S</td>

The symbol > signifies greater than

The symbol £ signifies Less .than or equal to

Eyespot is designated CercosporeL la herpotrichoides, above, but it is normally called PseudocercosporeLla herpotrichoides .

Tables (III), (IV) and (VI) show the minimal inhibitory dose in vitro of various compounds in respect of various fungii according to the method of application used in the example.

Table (V) shows the minimal inhibitory dose under glass (in vivo) of various compounds in respect of various fungii according to the methods of application used in Examples 4 to 6.

Table (VII) shows the efficacy of the products in the open field as regards various compounds.

The nature of the test used under glass'(in vivo) as regards Cercospora beticola (Example 8) and the conditions of the open field tests (Example 8a) are given below.

Example 8:

Sugar-beet plantlets 7 to 10 cm tall are treated preventively with the spray mixture to be tested, this spray mixture being similar to that described in Example 4. The trial is repeated twice at each concentration.

hours after treatment, the beet plantlets are contaminated by spraying them with an aqueous suspension of 0.2 g/ml of mycelium of Cercospora beticola.

Incubation is allowed to continue for 72 h at 25°c and 100% relative humidity, and after 3 days the plantlets are then placed in the light (10,000 lux; 14 hours per day). Verification of the condition of the plants is carried out 14 days after contamination, and is expressed as a percentage relative to an untreated control. An identical effect in the control is noted as OX. Complete protection of the plant is noted as 100X.

Example 8a:

The particular conditions of the various tests are given in the Table (VII). The general conditions are as follows: the tests were repeated 4 times each, on plots of land from 3 to 5 m2 in area. Contamination is natural for mildew (ERYG), and artificial for eyespot (CERC) and yellow rust (PUCR). The plants were treated with a spray mixture, spread in the proportion of 500 to 1,000 l/ha under a pressure of 3 kg/cm2.

The treatment was preventive for mildew and yellow rust (treatment repeated every 15 days), and curative for eyespot. The results were observed on a sample of 25 leaves for mildew and yellow rust (determination of the percentage of leaf surface attacked by the disease), or on a sample of 25 stems for eyespot (determination of the percentage of stems attacked).

Example 9:

A solution of methacrolein (296 g; 4.23 moles) in dichloromethane (1 I) is cooled to 0°C. Gaseous HBr (343 g) is bubbled in while the temperature is maintained. After 1/4 hour, methanol (0.9 L) is added at 0°C, at which temperature the mixture is maintained for 3 h. Water (2 I) containing concentrated (aqueous) ammonia solution (100 ml) is added. The mixture is decanted, the organic phase separated and the aqueous phase extracted with dichloromethane (200 ml). The organic phases are combined and washed with aqueous sodium bisulphite solution; the mixture is concentrated and then distilled in the presence 5 of diethyIani I ine. The bromoacetal (452 g) of formula

Θr-CHj'CH(CH3)-CH(OCH3)2 is obtained. Yield: 54%; b.p. 44 to 50°C under reduced pressure of 4 mm Hg. A magnesium derivative is then prepared by adding a solution of bromoacetal (19.7 g) in tetrahydrofuran (40 ml) 10 dropwise to magnesium at between 15 and 22°c and in the presence of 1,2-dibromoethane (a few drops).

Tetrahydrofuran (40 ml) is then added, the mixture is cooled to -20°C and a solution of tri chloroacetophenone (20.1 g) in THF (50 ml) is then added dropwise. The tern15 perature is still maintained at -20°C. Acetic acid (6 ml) is added and the mixture is poured into water (500 ml) at room temperature. The mixture is extracted with ether; the organic solution is dried and concentrated so as to obtain a yellow oil (30 g) consisting chiefly of the chloro20 hydrin of formula

Cl OH

Cl C - CH2 - CH(CH3) - CH(0CHj)2

CH2C1 (This procedure for preparing a non-cyclic acetal is that which can give rise to compounds of Example 3 in which It* is other than a hydrogen atom).

Into a solution of chlorohydrin (442 g) in ethanol (1.5 1), there is poured a solution of KOH (1 mole) in methanol (200 ml) until the medium becomes basic. The mixture is concentrated under vacuum, diluted with ether, washed with water, dried over sodium sulphate, evaporated and distilled under reduced pressure (121 to 140°c under 0.01 mm Hg). There is obtained a mixture (138 g) of two diastereoisomers of general formula

ch2 ch(ch3) - ch(0ch3)2

To a solution of this epoxide (126.5 g) in dimethyl formamide (500 ml) there is added triazole (57.2 g) and then K2C03 (172 g). The mixture is heated to 120°C for 4 hours, filtered, washed with dimethyl formamide and evaporated. The residue is poured into water (2 1), extracted with CHClj, washed with water, dried over Na2S04 and evaporated under vacuum. A pale brown oil (148.2 g) is obtained which is triturated in heptane (100 ml). The mixture is filtered and a beige powder (117.5 g), m.p. 117°C, is obtained (yield: 78X) which consists of a mixture of the two diastereoisomers of formula

Cl OH

Cl _// \\_ c - CH2 - CH(CH3) - CH(0CH3)2

The NMR shifts (delta) at 1QO megahertz in deuter ated chloroform are read for the protons of the methoxy group. Shifts at 3.23 and 3.19 ppm are observed for one 5 diastereoisomer, and at 3.38 and 3.20 ppm for the other di astereoi somer.

To a solution of this hydroxytriazole (75 g) in ethanol (700 ml) there is added gaseous HCl (7.3 g), and the mixture is then heated to boil under reflux for 15 hours.

The ethanol is evaporated under vacuum; the residue is taken up in ethyl acetate, washed with aqueous sodium bicarbonate solution, washed with water and dried over

The solvent is evaporated. A pale brown oil (68.6 g) is obtained. Yield: 96% of product of formula

Among the products of formulae (I) and (la) according to the invention, the compounds are preferred in which is the radical being an alkyl radical.

These compounds form a class which has especially advantageous properties, and are a special subject of the present invention. Corresponding to these compounds, the intermediate products of formulae (II), (Ila), (III), (Illb), (IIIc), (IV) and (V) in which R1 is R10 also form a class of compounds which are a subject of the present invention. Likewise, the processes by which these various compounds can be prepared, according to the routes described above but choosing in place of R1, are also . a special subject, of the invention.

Still more preferably, in these various compounds and processes, R^P denotes a lower alkyl (C1 to C4) radical, and, still more specifically, a methyl radical.

The various processes described above are applied to the various compounds of formulae (I) to (V) both when

R^ is a hydrogen atom and when R״! is R^O. However, the preparation of the compound of formula (III) from reagents of formulae (Illa) and (Illb) differs according to whether R1 is H or R1 is R1^: when R1 is a hydrogen atom, the reagent of formula (Illb) is a reagent of formula

Z' - CH2 - CH2 - CH(0R3)2 (IIIb1) in which Z' has the significance already mentioned and the two radicals R3 can either be distinct (identical or different) or alternatively (and this is preferred) they can constitute, a single divalent radical; when is r10, the reagent of formula (Illb) has the formula

Z1 - CH2 - CH - CH - OR30 (IIIb2)

I I R10 OR30 in which Z* and have the signficance already mentioned and the two radicals have the same significance as that given for R^ except that the two radicals R must be distinct (and not constitute a single divalent radical). The reference H. Wuest, J. Org. Chem. 34 1122 (1969) relates to products of formula (Illb) in which the two radicals R^ constitute a single divalent radical. The reference Houben-Weyl vol. VI/3 p. 204, 4th ed., 1965 is concerned with products of formula (IIIb2) in which the two radicals Ρ^θ are distinct.

The products of formulae (I) and (la) in which is a halogenated alkyl radical, especially a chlorinated or fluorinated radical, also.form a subject of the invention.

The application of the various compounds of formulae (I) and (la), in which and R^ and the other substituents have the various significances mentioned above, in controlling fungal attack of cereals forms yet another subject of the invention.

In addition to the applications already described above, the products according to the invention also have excellent biocidal activity in respect of many other varieties of microorganisms, among which there may be mentioned, without implied limitation, fungii such as those ofthegenera:

- Pullularia, e.g. the species P. pullulans,

- Chaetomium, e.g. the species C. globosum,

- Aspergillus, e.g. the species Aspergillus niger.

- Coniophora, e.g. the species C. p.uteana, As a result of their biocidal activity, the products of the invention permit effective control of the micro־ organisms the proliferation of which creates many problems in the agricultural and industrial fields. For this purpose, they are most ׳ especia I ly suitable for the protection of plants or industrial products such as wood, leather, paints, paper, rope, plastics and industrial water systems. They are most especially well suited to the protection of lignocellulose products and especially timber, whether furnishing timber, structural timber or timber exposed to the elements such as fencing timber, vine stakes and railway sleepers.

In the compositions of the invention, the products according to the invention used in the treatment of timber can optionally be mixed with one or more known biocidal products such as pentachlorophenol, metal salts, especially those of copper, manganese, cobalt, chromium and zinc derived from inorganic or carboxylic acids (heptanoic, octanoic and naphthenic acids), organic complexes of tin, and mercaptobenzothiazole.

Example No. 10 which follows illustrates the biocidal activity of compounds according to the invention. Examp le 10:

A microsuspension of the product is prepared for determination of its fungistatic threshold. This microsuspension is prepared in the following manner:

In a bead milling apparatus, each tube is charged with

- an aqueous solution (6 ml) containing two wetting agents (4% polyglycol 400 and 0.4% Tween 80)

- glass beads 3 mm in diameter (5 g)

- glass beads 5 mm in diameter (3 g).

This charge is subjected to agitation until a homo־ geneous microsuspension is obtained.

Specified quantities of microsuspension thus ob־ tained are introduced into an agar-containing culture medium present in haemolysis tubes. Each medium is then seeded with a specified strain of fungus. For each culture, the amount of biocidal product is varied. The fungistatic threshold is expressed as the amount of biocidal product per 100 ml of culture medium at which an influence of the product on the development of the strain begins to be observed.

The mixtures were classified in five categories of increasing fungistatic efficacy: Class

<td> 0</td><td> completely ineffective at</td><td> 1 x</td><td> 10'2</td>

<td> 0+</td><td> efficacy in the region of</td><td> 1 x</td><td>2־10</td>

<td> 1</td><td>e 2 efficacy between 1 x 10</td><td> and</td><td> 1 x 103 *־</td>

<td> 1 +</td><td> efficacy in the region of</td><td> 1 x</td><td>3־10</td>

efficacy between 1 x 10“3 and 1 x 10^

2+ efficacy in the region of 1 x 10“^ efficacy between 1 x 10^ and 1 x 10^

3+ efficacy in the region of 1 x 105

efficacy between 1 x 1Q and 1x10^

4+ efficacy in the region of 1 x 10 efficacy between 1 x 10 and 1 x 10“7

The fungistatic thresholds of the mixtures are deter mined for the following strains:

- Coriolus versicolor,

- Coniophora puteana,

- Pullularia pullulans,

- Chaetomium globosum,

- Sterrigmatocystis nigra (Aspergillus niger).

The results obtained are recorded in the table which follows and are given by comparison with those obtained under the same experimental conditions with pentachlorophenol.

<td rowspan="2"> Fungicidal activity on</td><td colspan="2"> Threshold of efficacy (Class)</td>

<td> Compound No. 28</td><td> PENTACHLOROPHENOL</td>

<td> Coriolus versicolor</td><td> 4</td><td> 3</td>

<td> Coniophora puteana</td><td> 4 +</td><td> 3</td>

<td> Pullularia pullulans</td><td> 4</td><td> 3</td>

<td> Chaetomium globosum</td><td> '. 3</td><td> 3</td>

<td> AspergiI Lus niger</td><td> 2 +</td><td> 3</td>

The products according to the invention are hence especially advantageous for treating timber.

<td> TABLE</td><td colspan="3"> JI)</td>

<td> 1 5 1______________________</td><td> 1 1 1 H 1</td><td> Η 1</td><td> n-CjjHy-</td><td> 1 1 B</td><td> 1 oil 1 1 1</td><td> 5,12</td>

4׳4

TABLE (I) (continued)

<td colspan="2"> 1 1 1 I Compound | I n°- | χΐ | I I I</td><td> R1</td><td> Γ 1 I r2</td><td colspan="2"> iDiastereo- |Meltlng! I isomers I *point! 1 1</td><td> /1 delta 1 :(NMF?)</td>

<td> 1 1 17</td><td> 1 Cl 1 1 1</td><td> H</td><td> Γ־...... 1 n-CziHy- 1</td><td> A (85 %) 1 1</td><td> oil</td><td> 1 1 5,30 1</td>

<td> 1 23 1</td><td> I ci 1</td><td> H</td><td> 1 ' 1 cyclohexyl</td><td> A+B ׳|</td><td> ;oil</td><td> 1 5,47 | 1 5,31 I</td>

<td> 1 1 24</td><td> 1 1 1 C1I 1 1</td><td> H</td><td> 1 cyclohexyl</td><td> B |</td><td> 118</td><td> 1 1 1 5,31 |</td>

TABLE (I)' (continued)

<td colspan="2"> 1 I T !Compel׳. | jound nT χΐ I 1 1 1</td><td> r!</td><td> 1 1 r2 1 1 ________________________________________________________</td><td> 1 1 iDiastereo- belting 1 isomers 1 point !present I in °C 1 1</td><td> 1 1 1 delta 1 1 (NMR) 1 1 1 1 1</td>

<td> 1 1 31</td><td> 1 1 1 Cl I 1 1'</td><td> nrCjH7-</td><td> 1 1 CH3- 1</td><td> 1 A+B+C+D 1 oil</td><td> 1 1 1 1</td>

TABLE I (continued)

<td> 1 I'Ccm!pound 1 n°</td><td> 1 1 lx1 1 1 1</td><td> , ' 1 R1 1 1 1</td><td> 1 r2 1 1</td><td colspan="2"> lOiastereo-Melting lisomeis׳: !point !present 1 in °C 1 1</td><td> 1 1 delta 1 (.NNR.)</td>

| 50 I F | Η I C2H5- I A+B I oil | 5,24 !ABLE (II)

Minimal inhibitory doses .in ppm

<td> pound l־n°</td><td> 1 CERC 1 1 ' 1</td><td> 1 HELM G 1</td><td> I pyre:</td><td colspan="6"> 1 b£LM T !SEPT NlFUS ROSlFUS NIV |FUS CULM| 1 1 1 1 1 1</td><td> RHIZ ci</td>

I 25 I I 100 | 100 I 100 I

TABLE (III)

<td rowspan="2"> 1 Fungus</td><td colspan="2"> Minimal inhibitory doses in nnm . .</td>

<td> ן compound n° ן</td><td> Minimal inhibitory dose</td>

<td> 1 BUT resistant</td><td> 1 29 I</td><td> 10</td>

<td> I to iprodione</td><td> 1 1</td><td></td>

<td> 1 1</td><td> TABLE</td><td> (111) (continued)</td>

<td colspan="2"> TABLE</td><td> (III) (continued)</td>

TABLE . (IV )

Minimal inhibitory dose in ,npip

<td colspan="2"> | Compound n°</td><td> 128 I 29 I</td><td> 30 1</td><td> 31 1</td><td> 32 1</td><td> 33 I</td><td> 34 1</td><td> 35 |</td><td> 36 |</td><td> 37 |</td>

1> 1001 1 1001>100i !>1001 i I Γϊϋόι ז I sept

TABLE (continued)

Minimal inhibitory dose in oom,

<td> compound n° Fiinaus</td><td> 1 38 •1</td><td> 39 1 1</td><td> 40 1</td><td> 41 1</td><td> 42 1 1</td><td> 43 1</td><td> 44 I 1</td><td colspan="2"> 49 [ 50 F ...Γ----1</td>

sept ז I 1001 I I I l> 1001>1001׳

TABLE

Minimal inhibitory dose in ppm

<td> ן ccntpound n°</td><td> 1 28 I</td><td> 29 I</td><td> 30 I 31 1</td><td> 32 1</td><td> 33 1 34 |</td><td> 35 1 36 1 37 |</td>

<td> | Fungus</td><td> T ־ ' 1</td><td> 1</td><td> | ן</td><td> |</td><td> | ן</td><td> 1 1 1</td>

<td></td><td> TABLE___(y! Minimal inhibitory</td><td> (continued) dose . in ppm</td><td></td>

<td> !Compound n° I Funqds</td><td> I 38 I 39 I 40 I 41 1 1 1</td><td> 44 1 43 1 42 I Γ ־־־־ 1 1</td><td> 1 49 I 50 1</td>

<td> I PLA 1</td><td> I 1)1000 bl 0001</td><td> yioooi 1</td><td> 1 1)10001</td>

TABLE . (VI)

Minimal inhibitory dose : in ppm

The figures in brackets show the degree of inhibition as a percentage at the stated dose

<td> !Compound n°</td><td> 1 45</td><td> 1 29 1</td><td> 1 12 I</td><td> 35 I</td><td> 9 1</td><td> 28</td><td> 1 47 |</td><td> 48 |</td>

<td colspan="9"> | Fungus | 1 1 1 1 1 1 1 1</td>

<td> I FUS CULM 1</td><td> I 100 1</td><td> 1 30 1 1 Ί</td><td> 1 1001 1 1</td><td> 30 1 1</td><td> 11 I 1</td><td> 30</td><td colspan="2"> 1 ΙΟΟΙΜΟΟΙ 1 1(80)1</td>

־ 55 ־

TABLE (VI [)

<td> 1 i Fungus</td><td> 1 i i Compound 11 1 No. I</td><td> Dose in g/Ha</td><td> י percentage 1 of spikes I diseased</td><td> of leaf 1 surface !diseased</td><td> 1 Procedure for observing 1 the results I 1 ________________________________l</td>

<td> i PUC5</td><td> 1 (control) 1</td><td> 0</td><td> |</td><td> 1 4Q</td><td> __1 23 days after treatment;</td>

<td> i</td><td> 1 1</td><td> 250</td><td> 1</td><td> 1 17-5</td><td> 1 observation on the 1</td>

<td> 1</td><td> 1 45 1</td><td> 500</td><td> 1</td><td> 1 16-3</td><td> 1 whole diseased plant 1</td>

<td> . 1</td><td> | ן</td><td> 250</td><td> 1</td><td> 1 7-9</td><td> 1 at the 4 leaf stage i</td>

<td> 1 PUC5 i</td><td> [ (control) | 1 a-j I</td><td> 0 123</td><td> 1</td><td> 82-3 1 . r4 ׳ ר</td><td> 1 14 days after treatment; ί observation on the I</td>

<td> 1 PUCS 1</td><td> i (control) 1 i 45 |</td><td> 0 125</td><td> 1</td><td> “Γ 253 i 6-7</td><td> __J5 days after 1st treatment; | observation on the .ן</td>

<td> 1 ERYG</td><td> i (control) 1 1 45 1</td><td> 0 250</td><td> 1 .......־ר</td><td> 9־25 .' 1 T 43</td><td> __I 14 days after treatment!; I observation on the i</td>

<td> i PUCS I</td><td> I (control) | 1 12 1</td><td> 0 125</td><td> i 100 I 88</td><td> 1 47-7 1 5-8</td><td> i 22 days after second ί ! treatment for the I</td>

<td> 1 1</td><td> 1 28 1 1 i</td><td> ...125</td><td> 1 64 1 1 1</td><td> 1 0-8 1 1</td><td> I spikes; 7 days after I I 2nd treatment for veri־l i fication on the 2nd I I leaf i</td>

<td> 1 £RYG 1</td><td> I (control) | 1 12 1 1 ...25 1</td><td> 0 125 ...125</td><td> 1 . 1 '11 ׳1׳</td><td> 1 10? 3 1 0-9 T 04</td><td> I 20 days after second I I treatment, verificatiorl I on the 1st leaf I</td>

<td> i PUCS 1 1</td><td> 1 (control) 1 1 45 I 1____________L</td><td> 0 ־־lE~ 25U</td><td> 1 96 1 74 1 74</td><td> 1 T 1</td><td> _l 24 days after, the I _ I treatment I _l I</td>

<td colspan="6"> 1 III percentage II Ί 1 1 1 1 of stems 1 1 1 1 I | !diseased | | ן</td>

<td> 1 CERC</td><td> I (control) I</td><td> 0</td><td> 1 93</td><td> 1</td><td> | ן</td>

<td> i</td><td> 1 29 1 i_________________l_ 1 12 1 1 1</td><td> 500 1000 500 1000</td><td> 1 82 1 72 1 95 1 85</td><td> 1 1</td><td> __l 56 days after treatmentl; _|verification on the I |main stem |</td>

Contents7

151 members in 43 offices

This recordMember, by publication datePriority claim33 more offices are in the list below

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Priority claims
Document	Office	Kind	Date
8401424	France	A	1984-01-26
8401424	France	A	1984-01-26
8401424	–	–	–
FR19840001424	–	–	–

Members151

Family members, oldest first
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FI850285A0	Finland	A0	1985-01-22
DK33885D0	Denmark	D0	1985-01-25
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IL74170A0	Israel	A0	1985-04-30
IL74170D0	Israel	D0	1985-04-30
GR850183B	Greece	B	1985-05-13
IE850157L	Ireland	L	1985-07-26
DK33885A	Denmark	A	1985-07-27
FI850285L	Finland	L	1985-07-27
AU3805185A	Australia	A	1985-08-01
FR2558834A1	France	A1	1985-08-02
EP0151084A2	European Patent Office (EPO)	A2	1985-08-07
KR850005440A	Republic of Korea	A	1985-08-26
BR8500306A	Brazil	A	1985-09-03
JPS60174779A	Japan	A	1985-09-09
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ES8605942A1	Spain	A1	1986-04-01
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PL255849A1	Poland	A1	1986-11-04
CS247095B2	Czechoslovakia (until 1993)	B2	1986-11-13
EP0151084A3	European Patent Office (EPO)	A3	1986-11-20
OA07939A	African Intellectual Property Organization (OAPI)	A	1987-01-31
PT79888B	Portugal	B	1987-02-03
RO91074A	Romania	A	1987-02-27
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ES550937A0	Spain	A0	1987-08-01
ES8707526A1	Spain	A1	1987-08-01
PH21220A	Philippines	A	1987-08-21
PL141880B1	Poland	B1	1987-09-30
PL141908B1	Poland	B1	1987-09-30
IE871033L	Ireland	L	1987-10-23
DK203987A	Denmark	A	1987-10-24
FI871752A	Finland	A	1987-10-24
FI871752L	Finland	L	1987-10-24
NO871634L	Norway	L	1987-10-26
NO905452L	Norway	L	1987-10-26
AU7181787A	Australia	A	1987-10-29
FR2597868A1	France	A1	1987-10-30
IL82271A0	Israel	A0	1987-10-30
IL82271D0	Israel	D0	1987-10-30
JPS62270578A	Japan	A	1987-11-24
EP0246982A2	European Patent Office (EPO)	A2	1987-11-25
ZA872803B	South Africa	B	1987-11-25
KR870010046A	Republic of Korea	A	1987-11-30
MA20949A1	Morocco	A1	1987-12-31
YU11285A	Yugoslavia, later Serbia and Montenegro (until 2006)	A	1987-12-31
FR2558834B1	France	B1	1988-01-08
BR8701922A	Brazil	A	1988-02-02
EP0246982A3	European Patent Office (EPO)	A3	1988-02-24
HUT44124A	Hungary	A	1988-02-29
BG43181A3	Bulgaria	A3	1988-04-15
TR22730A	Türkiye	A	1988-05-24
YU73487A	Yugoslavia, later Serbia and Montenegro (until 2006)	A	1988-06-30
PL265327A1	Poland	A1	1988-07-21
FR2597868B1	France	B1	1988-09-02
FR2611714A2	France	A2	1988-09-09
NZ210932A	New Zealand	A	1988-09-29
DK600788D0	Denmark	D0	1988-10-28
HU196107B	Hungary	B	1988-10-28
OA08586A	African Intellectual Property Organization (OAPI)	A	1988-11-30
DK600788A	Denmark	A	1989-05-01
AU2448488A	Australia	A	1989-05-04
FR2622582A1	France	A1	1989-05-05
CN1032789A	China	A	1989-05-10
EP0318400A1	European Patent Office (EPO)	A1	1989-05-31
TR23170A	Türkiye	A	1989-06-02
JPH01151560A	Japan	A	1989-06-14
KR890006600A	Republic of Korea	A	1989-06-14
IL88136A0	Israel	A0	1989-06-30
IL88136D0	Israel	D0	1989-06-30
MA21418A1	Morocco	A1	1989-07-01
EP0323443A2	European Patent Office (EPO)	A2	1989-07-05
CA1257278A	Canada	A	1989-07-11
BR8805766A	Brazil	A	1989-07-25
DD270231A5	German Democratic Republic (until 1990)	A5	1989-07-26
AU586812B2	Australia	B2	1989-07-27
US4863943A	United States of America	A	1989-09-05
CS287587A2	Czechoslovakia (until 1993)	A2	1989-10-13
PL275558A1	Poland	A1	1989-10-30
AU3923389A	Australia	A	1989-11-16
EP0323443A3	European Patent Office (EPO)	A3	1989-12-06
HUT50140A	Hungary	A	1989-12-28
PT84746B	Portugal	B	1989-12-29
TNSN87057A1	Tunisia	A1	1990-01-01
FR2622582B1	France	B1	1990-01-19
TR23491A	Türkiye	A	1990-02-01
CS270224B2	Czechoslovakia (until 1993)	B2	1990-06-13
ZA888121B	South Africa	B	1990-06-27
RO99432B1	Romania	B1	1990-08-30
IL74170AThis record	Israel	A	1990-09-17
NZ220050A	New Zealand	A	1990-09-26
AU601973B2	Australia	B2	1990-09-27
YU44624B	Yugoslavia, later Serbia and Montenegro (until 2006)	B	1990-10-31

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