AP221A

AP221A - Fungicidal compositions for seed dressing.

Info

Publication number: AP221A
Application number: APAP/P/1991/000277A
Authority: AP
Inventors: Alfred Greiner; Jean Hutt; Jacques Mugnier; Regis Pepin
Original assignee: Rhone Poulenc Agrochimie
Priority date: 1990-06-13
Filing date: 1991-06-12
Publication date: 1992-10-21
Also published as: US5290791A; IL98400A0; AP9100277A0; DE69109560T2; CN1063396A; HUT58465A; EP0467792A1; PT97934A; CS178491A3; AU656320B2; KR920000230A; IE67894B1; ZA914529B; DE69109560D1; ATE122205T1; MA22180A1; PT97934B; FI97195B; EG19259A; TR25435A

Abstract

The present invention relates to the protection from fungal disease

Description

Fungicidal composition for seed dressing The present invention relates to a method for the protection against fungal diseases of plant propagation products and plants obtained from them, to the treated products and plants, and to compositions useful in the method.

The invention provides a method for protecting plant propagation products and the plants obtained from them which comprises applying to the propagation product (a) 2-(4-chlorobenzylidene)-5,5-dimethyl-l-(1H-1,2,4triazol-l-ylmethyl)-1-cyclopentanol and (b) one or more fungicides suitable for the protection of the propagation products. The invention also relates to the treated, eg coated, propagation products.

The invention also provides a fungicidal composition intended, in particular, for the protection of the propagation products of plants against fungal diseases, comprising (a) 2-(4-chlorobenzylidene,' -5,5-dimethyl-l-(lh’1,2,4-triazol-l-ylmethyl)-1-cyclcpentanoi. (b) one or more fungicides suitable for the protection of the propagation products, an agriculturally acceptable inert carrier and/or an agriculturally acceptable surfactant.

2- (4-Chlorobenzylidene) -5,5-dimethyl-l- (ΙΙί-l, 2,4triazol-l-ylmethyl)-1-cyclopentanol is described _n

European Patent Publication No. 0373953 published or 25th July 1990.

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By the term propagation product is meant all the generative parts of the plant which can be used for its propagation. These include, e.g., the seeds, roots, fruits, tubers, bulbs, rhizomes, and plant sections.

Germinated plants and young plants which are to be transplanted after germination or after emergence from the soil, may also be mentioned. These young plants may be protected, for example, before transplantation by a total or partial treatment by immersion. It is to be understood that the plant propagation products, for example seeds, can be treated in situ in the soil.

To choose the fungicides (b) suitable for the protection of the propagation products, those skilled in the art may usefully refer to the information given in reference works and which mention the absence of phytotoxicity of the said products.

Among these works, the plant-protection index, 1990 edition, ACTA 75595 PARIS CEDEX 12., may be mentioned.

The compositions according to the invention usually 20 contain between 0.5 and 95 % of active material. In this specification unless otherwise specified all percentages are by weight.

The term carrier in the present description denotes a natural or synthetic, organic or inorganic .5 material with which the active substance is combined in order to facilitate its application to the plant, to the

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AP000221

- 3 plant propagation product, eg the seeds, or to the soil. This carrier is hence generally inert, and it must be agriculturally acceptable, in particular to the plant being treated. The carrier may be solid (eg clays, natural or synthetic silicates, silica, resins, waxes and solid fertilisers) or liquid (eg water, alcohols, ketones, petroleum fractions, aromatic or paraffinic hydrocarbons, chlorinated hydrocarbons and liquefied gases).

The surfactant can be an emulsifying, dispersant or 10 wetting agent of the ionic or nonionic type. There may be mentioned, e.g., polyacrylic acid salts, lignosulphonic acid salts, phenolsulphonic or naphthalenesulphonic acid salts, polycondensates of ethylene oxide with fatty alcohols or with fatty acids or with fatty amines, substituted phenols (in particular alkylphenols or arylphenols), salts of sulphosuccinic acid esters, taurine derivatives (in particular alkyltaurides) and polycondensates of ethylene oxide with phosphoric esters of alcohols or phenols. The presence of at least one surfactant is often required when the active substance and/or the inert carrier are not soluble in water and the carrier agent for the application is water.

These compositions can also contain other ingredients, such as, e.g., protective colloids, adhesives, thickeners, thixotropic agents, penetrating agents, stabilisers, sequestering agents, pigments, colourants and

BAD ORIGINAL polymers.

More generally, the compositions according to the invention may be combined with solid or liquid additives corresponding to the usual techniques of formulation for application to seed dressing, in particular.

It will be noted, in this connection, that, in the jargon of those skilled in the art, the term seed dressing refers, in fact, to treatment of the fertilised and ripened ovule.

The techniques of application are well known to those skilled in the art, and may be used within the scope of the present invention.

There may be mentioned, e.g., film-coating or encapsulation.

Among compositions, solid or liquid compositions may be mentioned.

As solid forms of compositions, there may be mentioned powders for dusting or dispersion (having a content of active material which can range up to 100 %) and granules, in particular those obtained by extrusion, by compaction, by impregnation of a granular carrier or by granulation from a powder (the content of active material in these granules being between 1 and 80 % for these latter cases).

The composition may also be used in the form of a dusting powder; a composition comprising active substance

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- 5 (50 g), finely divided silica (10 g) , organic pigment (10 g) and talc (970 g) may thus be used; these constituents are mixed and ground and the mixture is applied by dusting.

As liquid forms of compositions, or forms intended for making liquid compositions when they are applied, there may be mentioned solutions, especially water-soluble concentrates, emulsifiable concentrates, emulsions, flowables, aerosols, wettable powders (or powder for spraying), pastes and dispersible granules.

The emulsifiable or soluble concentrates generally comprise 10 to 80 % of active substance, the emulsions or solutions ready for application containing for their part 0.01 to 20 % of active substance.

For example, in addition to the solvent, the emulsifiable concentrates can contain, when necessary, 2 to 20 % of suitable additives such as the stabilisers, surfactants, penetrating agents, corrosion inhibitors, colourants or adhesives mentioned above.

From these concentrates, emulsions of any desired concentration, which are especially suitable for application to seeds, may be obtained by dilution with water.

The flowables, also applicable by spraying, are prepared so as to obtain a stable fluid product which does not settle out, and they usually contain from 10 to 75 % of active substance, from 0.5 to 15 % of surfactants, from C.i

BAD ORIGINAL to 10 % of thixotropic agents, from 0 to 10 % of suitable additives such as pigments, colourings, antifoams, corrosion inhibitors, stabilisers, penetrating agents and adhesives, and, as a carrier, water or an organic liquid in which the active substance is soluble to only a slight extent if at all: some solid organic substances or inorganic salts may be dissolved in the carrier to assist in preventing sedimentation or as antifreezes for the water.

The wettable powders (or powder for spraying) are usually prepared so that they contain 20 to 95 % of active substance, and they usually contain, in addition to the solid carrier, from 0 to 5 % of a wetting agent, from 3 to 10 % of a dispersant agent and, when necessary, from 0 to

10 % of one or more stabilisers and/or other additives such as pigments, colourings, penetrating agents, adhesives or anti-caking agents.

To obtain these powders for spraying or wettable powders, the active substances are mixed intimately in suitable blenders with the additional substances and the mixture is ground using mills or other suitable grinders. Powders for spraying are thereby obtained, the wettability and suspendibility of which are advantageous; they may be suspended in water at any desired concentration, and these

-5 suspensions are very advantageously usable, especially for application to seeds.

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- 7 In place of wettable powders, pastes may be made. The conditions and procedures for making and using these pastes are similar to those for the wettable powders or powders for spraying.

The dispersible granules are usually prepared by agglomeration, in suitable granulation systems, of compositions of the wettable powder type.

As already stated, the aqueous dispersions and emulsions, e.g. the compositions obtained by diluting a wettable powder or an emulsifiable concentrate according to the invention with water, are included in the general scope of the present invention. The emulsions can be of the water-in-oil or oil-in-water type, and they can have a thick consistency such as that of a '•mayonnaise''.

Among these compositions, those skilled in the art will advantageously choose that or those which are suitable according to the chosen combinations.

Preferably the weight ratio of the fungicide a) 2(4-chlorobenzylidene)-5,5-dimethy1-1-(1H-1,2,4-triazol-lylmethyl) -1-cyclopentanol to the fungicide(s) b) is between 1/400 and 400.

The propagation product is preferably a seed of a cereal, maize, rape, sunflower, soybean, alfalfa and rice. For potatoes, it is advantageously a tuber.

Compositions can be binary, ternary or quaternary according to the use for which they are intended.

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According to a preferred first feature of the invention, the fungicide b) is a broad-spectrum fungicide chosen from dithiocarbamic acid derivatives, of which the following (according to the common name agreed by the British Standard Institution or BSI or the IUPAC name) may be mentioned:

- ferbam, ie iron tris(dimethyldithiocarbamate),

- ziram, ie zinc bis(dimethyldithiocarbamate) ,

- nabam, ie disodium ethylenebis(dithiocarbamate),

- zineb, ie zinc ethylenebis(dithiocarbamate) (polymer),

- maneb, ie manganese ethylenebis(dithiocarbamate) (polymer),

- mancopper,

- mancozeb, ie the complex of manganese ethylenebis(dithiocarbamate) (polymer) with a zinc salt,

- propineb, ie polymeric zinc propylenebis(dithiocarbamate) ,

- metam-sodium,

- cuprobam,

- thiram, ie tetramethylthiuram disulphide or TMTD,

- carbatene or metiram, or from dicarboximide derivatives, of which the following may be mentioned:

- captan, ie N-(trichloromethylthio)cyclohex-4-ene-l,2dicarboximide,

- folpel, ie N-(trichloromethylthio)phthalimide,

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- 9 - captafol, ie N-(l,1,2,2-tetrachloroethylthio)cyclohex-4ene-1,2-dicarboximide,

- ditalimfos,

- iprodione, ie 3-(3,5-dichlorophenyl)-N-isopropyl-2,45 dioxoimidazolidine-l-carboxamide,

- procymidone, ie N-(3,5-dichlorophenyl)-1,2dimethylcyclopropane-1,2-dicarboximide,

- vinclozolin, ie (RS)-3-(3,5-dichlorophenyl)-5-methyl-5vinyl-1,3-oxazolidine-2,4-dione.

Among these derivatives, the following broadspectrum fungicides are especially preferred: captan, thiram, maneb.

According to a second feature of the invention, optionally taken in combination with the first feature when the fungicide b) is a mixture, the fungicide b) is a fungicide having anti-Fusarium activity, preferably an imidazole, of which the following may be mentioned:

- prochloraz, ie N-propyl-N- [2-(2,4,6-tnchlorophenoxy)ethyl]imidazole-l-carboxamide, ^nr) - iraazalil, ie allyl 1-(2,4-dichlorophenyl)-2-iraidazol-lylethyl ether, or from carbamates, of which the following may be mentioned:

- benomyl, ie methyl 1-(butylcarbamoyl)benzimiaazol-2> ylcarbamate,

- thiabendazole, ie 2—(thiazol-4-yl)benzimidazole,

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- carbendazim, ie methyl benzimidazol-2-ylcarbamate, or from pyrroles, of which the following may be mentioned:

- fenpiclonil, ie 4-(2,3-dichlorophenyl)pyrrole-3carbonitrile or alternatively oxine-copper.

According to a third feature of the invention, optionally taken in combination with one or both of the first and second features when b) is a mixture, the fungicide b) is a fungicide having anti-Rhizoctonia activity, preferably chosen from dicarboximides, of which the following may be mentioned:

- iprodione, or phenylureas, of which the following may be mentioned:

- pencycuron, ie 1-(4-chlorobenzyl)-l-cyclopentyl-3phenylurea, or anilides, of which the following may be mentioned:

- mepronil,

- flutolanil, ie a,a,a-trifluoro-3’-isopropoxy-otoluanilide, or phosphorus derivatives such as tolclofos-methyl, ie 02,6-dichloro-p-tolyl 0,0-dimethyl phosphorothioate.

According to a fourth feature of the invention, taken independently or otherwise in combination with one or two of the first three, or all three, the fungicide b) is a fungicide having anti-Oomycetes activity, preferably chosen from acylalanines:

- benalaxyl, ie methyl N-phenylacetyl-N-(2,6-xyly1)-DLBAD ORIGINAL $

AP 0 0 0 2 2 1

- 11 alaninate,

-furalaxyl, ie methyl N-(2-furoyl)-N-(2,6-xylyl)-DLalaninate,

- metalaxyl, ie methyl N-(2-methoxyacetyl)-N-(2,6-xylyl) DL-alaninate,

- oxadixyl, ie 2-methoxy-N-(2-oxo-l,3-oxazolidin-3-yl)acet2’ , 6’-xylidide, thiadiazoles, of which the following may be mentioned: -etridiazole, ie ethyl 3-trichloromethyl-l,2,4-thiadiazol5-yl ether, isoxazoles, of which the following may be mentioned:

- hymexazol, ie 5-methylisoxazol-3-ol, metal monoethyl phosphites, of which the following may be mentioned:

- fosetyl-Al, ie aluminium ethyl hydrogen phosphonate,

- phosphorous acid or its alkali metal (for example sodium or potassium) or alkaline earth metal (for example calcium) salts.

According to a fifth feature of the invention, taken independently or otherwise in combination with one, two or three of the first four, or all four, the fungicide b) is a fungicide having anti-Oidium activity, preferably chosen from:

morpholines at a non-phytotoxic dose:

- fenpropidin, ie (RS)-l-[3-(4-tert-butylphenyl)-2methylpropy1]p iperidine,

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- fenpropimorph, ie (±)-cis-4-[3-(4-tert-butylphenyl)-2methylpropyl]-2,6-dimethylmorpholine,

- tridemorph, ie 2,6-dimetyl-4-tridecylmorpholine,

- 4-[3-(4-chlorophenoxyphenyl)-2-methylpropyl]-2,6dimethylmorpholine described in EP-A-262,870 of 24th September 1987;

pyrimidines such as:

- ethirimol, ie 5-butyl-2-ethylamino-6-methylpyrimidin-4ol.

According to a sixth feature of the invention, taken independently or otherwise in combination with one or more of the first five, the fungicide b) is a fungicide having anti-Helminthosporium or anti-caries, anti-smut or anti-septorioses activity, preferably chosen from:

- triazoxide,

- fenfuram, ie 2-methyl-3-furanilide,

- carboxin, ie 5,6-dihydro-2-methyl-l,4-oxathiine-3carboxanilide,

- guazatine,

- iminoctadine dodecylbenzenesulphonate,

- ampropylfos, ie 1-aminopropylphosphonic acid.

According to a further feature of the invention the fungicidal composition as described above, may in addition, comprise one or more insecticides c) which are -uitable for the protection of the propagation products.

Among the insecticides, the following may be

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- 13 mentioned :

tefluthrin, cypermethrin, thiodicarb, lindane, furathiocarb, acephate, butocarboxim, carbofuran, NTN, endosulfan, diethion, aldoxycarb, methiocarb, oftanol (isofenphos), chlorpyrifos, bendiocarb, benfuracarb, oxamyl, parathion, capfos, dimethoate, fonofos, chlorfenvinphos, cartap, fenthion, fenitrothion, HCH, deltamethrin, malathion, diazinon and disulfoton.

The compositions according to the invention may be used for both the prophylactic and the curative protection of the propagation products of plants against fungi, in particular of the basidiomycete, ascomycete, adelomycete or Fungi imperfecti type, especially rusts, smuts, oidia, eyespot, fusarioses, Fusarium roseum. Fusarium nivale. helminthosporioses, rhynchosporioses, septorioses and rhizoctonia disease of vegetable organisms and plants in general, and especially of cereals such as wheat, barley, rye, oats and hybrids thereof, and also rice and maize.

The compositions according to the invention are especially active against fungi, in particular of the basidiomycete, ascomycete, adelomycete or Fungi Imperfect! type, sucii as Botrvtis cinerea. Ervsiphe graminis. Puccinia graminis. Puccinia reccndita. Piricularia orvzae,

Cercospora beticola, Puccinia striiformis. Erysiphe cichoracearum, Rhlnchosporium secalis. Fusarium solani, Fuoarium oxysporum (e.g. meIonis), Pyrenophora avenae,

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Septoria tritici. Septoria avenae. Whetzelinia scl erot jorum. Mvcosphaerella f ii iensis. Alternaria solani.,

Aspergillus njger. Cercospora arachidicola. Cladosporium herbarum. Tilletia caries. Tilletia contreversa. Fusarium culmorum. Fusarium roseum. Fusarium nivale.

Helminthosporium orvzae. Helminthosporium teres.

Helminthosporium gramineum. Helminthosporium sativum. Penicillium expansum. Pestalozzia sp, Phoma betae. Phoma foveata. Phoma 1ingam. Ustilago mavdis. Ustilago nuda.

Ustilago hordei. Ustilago avenae. Verticillium dahliae,

Ascochvta pisi. Guignardia bidwellii. Corticium rolfsii.

Phomopsis viticola. Sclerotinia sclerotiorum. Sclerotinia minor. Corvneum cardinale. Rhizoctonia solani.

Acrostalagmus koningi. Alternaria. Colletotrichum.

Corticium rolfsii, Diplodia natalensis. Gaeumannomyces graminis. Gibberella fuiikuroi. Hormodendron cladosporioides. Mvrothecium verrucaria. Paecylomyces varioti. Pellicularia sasakii. Phellinus megaloporus.

Sclerotium rolfsii. Stachybotris atra. Trichoderma pseudokoningi. Trichothecium roseum and Pythium arrhenomanes.

The compositions of the invention are especially advantageous on account of their broad spectrum in respect of diseases of cereals (oidia, rust, eyespot, rhynchosporioses, helminthosporioses, septorioses and fusarioses). They are also of great interest on account of

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AP 000 22 1

- 15 their activity against grey mould (Botrytis) and cercosporioses, and as a result they may be applied to propagation products of crops as varied as vine, marketgarden crops and arboriculture, and tropical crops such as groundnut, banana tree, coffee bush, pecan nut and others.

These compositions are also useful in the disinfection of cereal seeds against Ustilago nuda.

Septoria nodorum. Tilletia caries and Tilletia controversa. Helminthosporium gramineum and many species of the Fusarium sp.

According to a further feature of the invention the mixtures of the fungicide a) and one or more fungicides b) may optionally comprise one or more insecticides c) with their preferred variants as described above.

These mixtures are useful in the fungicidal compositions according to the invention.

Preferably the compositions of the invention comprise a marker, preferably visible, eg a pigment or colorant, by which treated plant propagation products, eg seeds, can be distinguished.

The present invention also provides a method for the protection against fungal diseases of plant propagation products and the plants obtained from them which comprises applying to the propagation product, eg by coating, (a) 225 (4-chlorcbenzy1idene)-5,5-dimethvl-l-(1H-1,2,4-triazol-lv^!methyl)-1-cyclopentanol, (b) one or mere fungicides

BAD ORIGINAL suitable for the protection of the propagation product.

The compositions of the invention may be used. It will be understood that a fungicidal and non-phytotoxic dose will be used.

Coating processes are well known in the art, and employ, for seeds, the techniques of film-coating or encapsulation, or for the other propagation products, the techniques of immersion.

The invention has proved especially advantageous 10 for protecting seeds. Among these seeds, cereal (eg barley, wheat, rye, oat and triticale), maize and rice seeds may be mentioned.

Preferably, the said seed is coated with 1 to 400 g of fungicide a) and 1 to 400 g of fungicide b) per quintal of seeds.

Within these ranges, those skilled in the art will choose, on the basis of their general knowledge and, where appropriate, routine experiments, doses which are nonphytotoxic but fungicidally effective.

When one or more insecticides are employed, they should be applied at non-phytotoxic doses which are well known to those skilled in the art.

The present invention also provides plant propagation products which comprise, eg as coating (for example of a composition according to the invention) or as absorbate, 2-(4-chlorobenzylidene)-5,5-dimethyl-l-(1HBAD ORIGINAL ft

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-171,2,4-triazol-l-ylmethyl)-1-cyclopentanol and one or more fungicides suitable for the protection of the propagation product.

The invention is illustrated by the Examples given below.

EXAMPLES

In vivo trial bv seed dressing application:

Application slurry:

An aqueous dispersion of the active substance 10 mixture to be tested, having the following composition, is prepared by fine grinding:

- active substance or active substance mixture (a and/or b) , : 60 mg,

- Tween 80 (surfactant) consisting of an oleate of a 15 polycondensate of ethylene oxide with a sorbitan derivative, diluted to 10 % in water, : 0.3 mg,

- the mixture is made up to 60 ml with water.

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

Example 1

On Pvthium arrhenomanes:

Barley seeds, variety Robbin, inoculated artifically with Pvthium arrhenomanes. are treated with the slurry defined above at the doses shown in the table below.

·> 20 seeds are placed in pots 10 cm x 10 cm

BAD ORIGINAL containing a peat/pozzolana (1:1) mixture.

The plantlets grow and, 15 days after sowing, the spate of the latter is observed in comparison with the control, on which colonies of Pvthium arrhenomanes have grown.

The results below are given for an average of 40 plants (2 pots).

Note: in the subsequent tables, the fungicide a) is designated by the letter a.

	dose g/quintal	% efficacy
maneb	250	38
captan	160	97
thiram	160	100
a + thiram	100 + 150	100 I
a + captan	100 + 100	i 90 ^!
a + maneb	100 + 250	i ⁷⁷
a	100	⁰ 1

No phytotoxic effect is observed.

Example 2

On Fusarium culmorum:

Barley seeds, variety Robbin, naturally contaminated with Fusarium culmorum are treated with a slurry defined above at the doses shown in the table below, and planted as described in the above trial.

days after sowing, the state of the plantlets is

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AP000221

- 19 verified in comparison with the untreated control, on which colonies of Fusarium culmorum have grown.

The results below are given for an average of forty plants (2 pots).

	dose g/quintal	i 1 % efficacy
thiabendazole	50	100
imazalil	5	100
benomyl	100	100
prochloraz	50	100
a +
thiabendazole	i 25+50 I I	100
a + imazalil	25 + 5 i I	100
a + prochloraz	25 + 50 ! i	100
a	25 1	ICO

No phytotoxicity is observed.

Example 3

On Rhizoctonia solani:

The trials are performed in the same manner as above, and lead to the results shown in the table below.

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		dose g/quintal	% efficacy
	flutolanil	200	70
5	mepronil	500	55
	iprod Lone	400	71
	pencycuron	400	55
	a + flutolanil	100 + 200	82
	a + mepronil	100 + 500	73
10	a + iprodione	100 + 400	70
	a + pencycuron	100 + 400	72
	a	100	70

No phytotoxicity is observed.

Example 4

On Pythium arrhenomanes:

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	dose g/quintal	% efficacy
benalaxyl	150	93
furalaxyl	15Θ	99
etridiazole	150	98
fosetyl-Al	300	90
metalaxyl	120	90 1
hymexazol	300	³⁷
a + benalaxyl	100 + 150	95 '
a + furalaxyl	100 + 150	⁹⁷ !
a + etridiazole	100 + 150	93 i
a + fosetyl-Al	100 + 300	80
a + metalaxyl	100 + 120	93
a + hymexazol	100 + 300	32 S
a	100	⁰ ; 1---- - --. -

No phytotoxicity is observed.

Example 5

Combination of phosphite (KgHFO₄) and fungicide a:

Earley seeds coated with the slurry define·: above are sown in fields on the basis of 120 kg of seeds per hectare.

Reading is. performed relative to ar. uncreated control at the time of germination, to which the figure -. 100 is assigned.

A

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The biological effect is observed by counting the plants which have emerged, and is expressed in the table below:

Treatment g/q	% of plants emerged relative to the control
control	100
fungicide a 25 + phosphite	126
200
fungicide a 25 + phosphite	142
40

At 79 days, the plants are uprooted and the number of roots per plant is counted on an average of 20 plants.

Treatment g/q	Number of roots per plant
control	0.8
fungicide a 25 + phosphite	5.8
200
fungicide a 25 + phosphite	5.5
40

On day 156, the plants are uprooted and the roots are weighed.

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Treatment g/q	Weight of the roots
average of 20 plants	per plant in mg
control	74.7
fungicide a 25 + phosphite	105.5
200
fungicide a 25 + phosphite	106
40

* Average of 20 plants

Thus, it is observed that combination promotes rooting, prevents damping-off disease and promotes cereal growth.

2-(4-Chlorobenzylidene)-5,5-dimethyl-l-(1H-1,2,4triazol-l-ylmethyl)-1-cyclopentanol may be obtained in the following manner:

% aqueous sodium hydroxide solution (133 ml) is added to a mixture of 2,2-dimethylcyclopentanone (10 >;) and 4-chlorobenzaldehyde (13.8 g) in etnanol (100 τ1« at 0'C. f\fter 30 minutes, a thick slurry is filtered end the solid is washed and then dried. 2,2-Dimethyl-5-(4chlcrobenzylidene)-1-cyclopentanone (12.5 g) , m.p. ’20'C, is obtained. This compound, dissolved in THF (50 mlt, is added to a solution formed in the following manner: soaium hydride (80 i dispersion in mineral oil) (1.9 g, in

BAD ORIGINAL anhydrous DMSO (50 ml) is heated to 80*c until the solid has dissolved completely. The solution is then diluted with THF (100 ml) and then cooled to -10’C. A solution of trimethylsulphonium iodide (11.5 g) in dimethyl sulphoxide (80 ml) is added to the mixture in the course of 10 minutes and the mixture is stirred for 15 minutes at -10*C. A solution of 2,2-dimethyl-4-chloro-5-(4-chlorobenzylidene)1-cyclopentanone (11.8 g) in THF (100 ml) is then added.

The mixture thereby produced is left at room 10 temperature, then poured into water and extracted with ether, and the organic phase is washed with water, dried and distilled. 7-(4-Chlorobenzylidene)-4,4-dimethyl-loxaspiro[2.4]heptane is obtained, which product is used directly for the next step.

A mixture of the product (5 g) with 1,2,4triazole (2.8 g) and potassium carbonate (11 g) is heated in Ν,Ν-dimethylformamide (40 ml) for 4 hours. The mixture is poured into water and extracted with ethyl acetate. The organic phase is washed and dried and the product is recrystallised to obtain the stated compound, m.p. 143 °C.

The structure of the compound is generally obtained (>95 %) with the para-chlorophenyl group in the E position relative to the carbon bearing the hydroxyl group.

2,2-Dimethylcyclopentanone may be obtained in a manner known from the literature, or is available on the market (see Fine Chemical Directory).

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- 25 The chemical structure of the fungicide a, ie 2(4-chlorobenzylidene)-5,5-dimethyl-l-(lH-l,2,4-triazol-iylmethyl)-1-cyclopentanol is given below.

Claims

1. A method for the protection against fungal diseases of plant propagation products and the plants obtained from them which comprises applying to the

5 propagation product (a) 2-(4-chlorobenzylidene)-5,5dimethyl-1-(1H-1,2,4-triazol-l-ylmethyl)-1-cyclopentanol, and (b) one or more fungicides suitable for the protection of the propagation product.

2. A method according to claim 1 wherein the 10 propagation product is a seed.

3. A method according to claim 1 cr 2 wherein the seed is a seed of a cereal, maize, rape, sunflower, soybean, alfalfa or rice.

4. A method according to claim 1, 2 cr 3 in 15 which the weight ratio of the fungicide a) 2-(4chlorobenzylidene)-5,5-dimethyl-l-(1H-1,2,4-triazol-lylmethyl) -1-cyclopentanol to the fungicide(s) b) is between 1/400 and 400.

5. A method according to any one of the ^?0 preceding claims in which the fungicide b) is a broadspectrum fungicide chosen from dithiocarbamic acid or dicarboximide derivatives.

δ. A method according to claim 5, in which the fungicide is captan, thiram or maneb.

5 7. A method according to any one of claims 1 to 4, in which the fungicide b) is an anti-Fusarivm

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- 27 fungicide.

8. A method according to claim 7, in which the fungicide (b) is thiabendazole, imidazole, benomyl, prochloraz, carbendazim, fenpiclonil or imazalil.

5

9. A method according to any one of claims l to 4, in which the fungicide b) is an anti-Rhizoctonia fungicide.

10. A method according to claim 9, in which the fungicide b) is flutolanil, mepronil, iprodione,

10 pencycuron or tolclofos-methyl.

11. A method according to any one of claims I to 4, in which the fungicide b) is an anti-Oomvcetes fungicide.

12. A method according to claim 11, in which 15 the fungicide is benalaxyl, furalaxyl, oxadixyl, etridiazole, fosetyl-Al, metalaxyl, hymexazol or phosphorous acid or one of its sodium, potassium or calcium salts.

13. A method according to any one of claims 1 20 to 4, in which the fungicide b) is an antiHelminthosporium, anti-caries, anti-smut or antiseptorioses fungicide.

14. A method according to claim 13, in which the fungicide b) is triazoxide, fenfuram, carboxin, °5 guazatine, iminoctadine dodecylbenzenesulphonate or ampropyIfos.

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15. A method according to any one of claims 1 to 4, in which the fungicide b) is an anti-Oidium fungicide.

16. A method according to claim 15, in which 5 the fungicide b) is ethirimol, fenpropidin, fenpropimorph, tridemorph or 4-[3-(4-chlorophenoxyphenyl)-2-methylpropyl] 2,6-dimethylmorpholine.

iT-' A method according to any one of the preceding claims in which a seed is coated with 1 to 400 g of fungicide a) and 1 to 400 g of fungicide b) per

15 quintal of seeds.

ις*. A plant propagation product comprising 2(4-chlorobenzylidene)-5,5-dimethyl-l-(1H-1,2, 4-triazol-l20 ylmethyl)-1-cyclopentanol and (b) one or more fungicides suitable for the protection of the propagation product.

H· A plant propagation product according to claim 20 which is a seed.

2d' A plant propagation product according to

25 claim 21 in which the seed is a seed cf a cereal, maize, rape, sunflower, soybean, alfalfa or rice.

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- 29 \, A plant propagation product according to claim 20, 21 or 22 which comprises 1 to 400 g of fungicide

a) and 1 to 400 g of fungicide b) per quintal of seeds.

2 2.. ^A plant propagation product treated by a

5 method according to any one of claims l to 19.

A fungicidal composition for the protection of plant propagation products against fungal

10 disease which comprises a) 2-(4-chlorobenzylidene)-5,5dimethyl-1-(1H-1,2,4-triazol-l-ylmethyl)-l-cyclopentanol and b) one or more fungicides suitable for the protection of plant propagation products, in association with an agriculturally acceptable diluent or carrier and/or surface

15 active agent.

· A composition according to claim 25 in which the weight ratio of a) to t) is 1/400 to 400.

A composition according to claim 26 in which the fungicide b) is as defined in any one of claims

20 5 to 16.

76- A composition according to claim 26, 2? or

28 which comprises 0.5 to 95% by weight of active material.

y A composition according to any cne of claims 26 to 29 which comprises a marker.