IE922013A1 - Alkoxyamino ketals, their preparation and intermediate¹products therefor, and their use as fungicides - Google Patents

Abstract

Alkoxyamino ketals of formula (I), wherein A represents a single or a double bond, R<1> is C1-C10alkyl, unsubstituted or alkylsubstituted cycloalkyl having up to 6 ring carbon atoms or cycloalkylalkyl having up to 10 carbon atoms in all, R<2> and R<3> each independently represents hydrogen, C1-C10alkyl, unsubstituted, alkylsubstituted, alkoxysubstituted or alkoxyalkylsubstituted cycloalkyl, alkenyl having up to 10 carbon atoms, alkynyl, alkoxyalkyl, dialkoxyalkyl, dioxolanylalkyl, oxolanyl, oxolanylalkyl, dioxanylalkyl, furanyl, furanylalkyl or unsubstituted or alkylsubstituted cycloalkylalkyl, at least one of the substituents R<2> and R<3> being an oxygen-containing alkyl or cycloalkyl group, or R<2> and R<3> when taken together with the nitrogen atom to which they are attached form a saturated or unsaturated heterocyclic ring which is furthermore substituted once, twice or three times by alkoxy or alkoxyalkyl groups, and the preparation of these compounds and intermediate products therefor are described. The compounds (I) have fungicidal, particularly plant-fungicidal activity.

Description

The present invention relates to novel alkoxyamino ketals, a process for their preparation and novel intermediate products therefor. Moreover, the invention relates to the use of the novel alkoxyamino ketals as fungicides, particularly plant-fungicides.

It is already known that certain alkoxyaminomethyl-dioxolanes , e.g., ,O.

No. 74 have fungicidal properties, confer Danish patent ap30 plication No. 1201/ΘΘ corresponding to EP 0 281 842 Al .

However, the fungicidal activity of said knowr: compounds, especially at low amounts of application and low concentrations, is not quite satisfactory on all fields of application. Λ rIE 922013 huKOXYAMINO KETALS, THEIR PREPARATION THW’™15 ---AND INTERMEDIATE PRODUCTS THEREFOR, AND THEIR USE AS FUNGICIDES '» * λ|Τ ' _ j βο, * /5^1 ?O-EM TO PL’T-UC ^oPECTiONl i , I SECT'Gi J AAD RULE 33 i j.lHL I APPLICATION No.. 92201.3^., SPECIFICATION ph Fn .......

CHEMINOVA AGRO A/S, a of P.O. Box 9, DK-7620 company organized under the Lemvig, Denmark laws °f Denmark, -1IE 922013 Alkoxyamino ketals, their preparation and intermediate products therefor, and their use as fungicides.

The present invention relates to novel alkoxyamino ketals, a process for their preparation and novel intermediate products therefor. Moreover, the invention relates to the use of the novel alkoxyamino ketals as fungicides, particularly plant-fungicides.

It is already known that certain alkoxyaminomethyl-dioxolanes, e.g., have fungicidal properties, confer Danish patent ap30 plication No. 1201/88 corresponding to EP 0 281 842 Al.

However, the fungicidal activity of said known compounds, especially at low amounts of application and low concentrations, is not quite satisfactory on all fields of application.

According to this invention there are now provided amino ketals having a generally superior fungicidal activity, viz. novel alkoxyamino ketals of the general formula I wherein A represents a single or a double bond, R1 represents a substituent selected from straight or branched chain alkyl having up to 10 carbon atoms, unsubstituted or alkylsubstituted cycloalkyl having up to 6 ring carbon atoms and cycloalkylalkyl having up to 10 carbon atoms in all, R2 and R3 each independently represents hydrogen, straight or branched chain alkyl having up to 10 carbon atoms, unsubstituted, alkylsubstituted, alkoxysubstituted or alkoxyalkylsubstituted cycloalkyl, alkenyl having up to 10 carbon atoms, alkynyl, alkoxyalkyl, dialkoxyalkyl, dioxolanylalkyl, oxolanyl, oxolanylalkyl, dioxanylalkyl, furanyl, furanylalkyl or unsubstituted or alkylsubstituted cycloalkylalkyl, at least one of the substituents R2 and R3 being an 2.5 oxygen-containing alkyl or cycloalkyl group, or R2 and R3 when taken together with the nitrogen atom to which they are attached form a saturated or unsaturated heterocyclic ring which is furthermore substituted once, twice or three times by alkoxy or alkoxyalkyl groups.

The symbols R^-R3 in the above formula I have preferably, or by way of example, the following meanings : R1: alkyl is preferably alkyl having 4-10 carbon atoms, more preferably branched chain alkyl having 4-8 carbon atoms, substituted cycloalkyl is preferably 1-methylcyclohexyl, cycloalkylalkyl is preferably 1-methyll-cyclohexylethyl, R2 and R3: straight and branched chain alkyl is preferably alkyl having up to 6 carbon atoms and more preferably up to 4 carbon atoms , cycloalkyl is preferably cyclopropyl or cyclopentyl, cycloalkylalkyl is preferably cyclopropylmethyl, alkenyl is preferably allyl, methallyl or 3-butenyl, alkynyl is preferably propargyl, alkoxyalkyl is preferably methoxyethyl, ethoxyethyl, methoxypropyl or ethoxypropyl, dialkoxyalkyl is preferably 2,2-dimeth20 oxyethyl or 2,2-diethoxyethyl, dioxolanylalkyl is prefebrably 2-dioxolanylmethyl, oxolanylalkyl methyl, is preferably 2-oxolanyl- 25 dioxanylalkyl 2-ylmethyl, is preferably 1,3-dioxan- furanylalkyl is preferably 2-furanyl- methyl, the alkoxysubstituted heterocyclic ring 30 is preferably 2-, 3- or 4-methoxypiperidino or 2- or 3-methoxypyrrolidino, and the alkoxyalkylsubstituted heterocyclic ring is preferably 2-, 3- or 4-methoxymethylpiperidino or 2- or 3-methoxy35 methylpyrrolidino.

The compounds of formula I can exist as geometrical and/or optical isomers or isomer mixtures of varying composition. The present invention relates to both the pure isomers and isomer mixtures.

Furthermore, it has been found that the novel alkoxyamino ketals of the general formula I, wherein A, 5 R1, R2 and R3 have the above defined meanings, are obtainable by reacting a ketal of the general formula II II wherein A and R1 have the above defined meanings, and wherein Z represents an exchangeable electron-attracting group as, e.g., a halogen atom or an alkanesulphonyloxy group or an arylsulphonyloxy group, with an alkoxy amine of the general formula III wherein R2 and R3 have the above defined meanings, 25 optionally in the presence of a solvent and optionally in the presence of a catalyst, and optionally in the presence of an acid-binding agent in addition to a possible excess of the amine III. Optionally, the reaction between the ketals II and the amines III under the above-mentioned conditions can furthermore take place in an autoclave at a pressure above atmospheric pressure.

Suitable solvents are, e.g., methyl-t-butyl ether, tetrahydrofuran, dimethylformamide, acetoni35 trile, toluene, xylene, 1,2-dichloroethane or dimethylsulphoxide. Suitable acid-binding agents are, e.g.. sodium carbonate, potassium carbonate, triethylamine, pyridine or diazabicyclooctane (DABCO).

The reaction temperature at the reaction between the ketals II and the amines III can vary within a wide range. Usually, there is operated in a temperature 0 0 range of between 20 C and 200 C, preferably between 100°C and 180°C .

For the preparation of alkoxyamino ketals of the general formula I wherein A represents a double bond, 10 use can be made of a ketal of the general formula II wherein A represents a double bond, and Z represents a methanesulphonyloxy group or a chlorine or bromine atom, i.e. a ketal of the general formula IV wherein R1 has the above defined meaning, and Z' represents a methanesulphonyloxy group or a chlorine or bromine atom.

The ketals of formula IV, e.g. when it is a 25 question of methanesulphonates (Z = OSO2CH3), are obtainable by reacting a ketal alcohol of formula V wherein R1 has the above defined meaning, with methane35 sulphonyl chloride of formula VI CH3SO2C1 VI in a manner known per se in the presence of a solvent as for example methyl-t-butyl ether, toluene, methyl5 ene chloride or acetonitrile, and in the presence of an acid-binding agent as for example potassium carbonate, triethylamine or pyridine, at temperatures of between 0 C and 100 C.

Corresponding ketals of formula II, wherein A represents a single bond, can be prepared in a similar way to that described in Danish patent application No. 516/91 (Patent Application No. 920753).

The ketal alcohols of formula V can be prepared in a generally known manner by reacting an enolether which is known from J. Org. Chem. 35 , 715 (1970) and has the formula VII wherein R1 has the above defined meaning, with 1,2,4- butanetriol of formula VIII VIII 25 OH OH HO' 30 in the presence of an aprotic toluene or 1,2-dichloroethane, organic and in solvent such as the presence of an acidic catalyst such as p-toluenesulphonic acid at the boiling point of the solvent concerned while simultaneously azeotropically distilling off the methanol formed during the ketalization reaction.

Furthermore, the ketals of formula V, when it is a question of chloroketals (Z = Cl) are obtainable by reacting a ketone which is known from J. Org. Chem. 35, 715 (1970) and has the formula IX wherein R1 has the above defined meaning, with 1,2epoxy-4-chlorobutane which is known from Liebigs Ann.

Chem. 596, 141-2 (1955) and has the formula X in a manner known per se in the presence of a solvent and in the presence of a catalyst (confer what is stated in React. Kinet. Catal. Lett. 1981, 17(3-4), 281-6) .

Suitable solvents are, e.g., aliphatic or aro20 matic hydrocarbons such as hexane, cyclohexane or toluene, chlorinated hydrocarbons such as methylene chloride, 1,2-dichloroethane or chlorobenzene, esters such as ethyl acetate, nitriles such as acetonitrile, or compounds containing the atomic grouping SO2 such as sulphur dioxide itself, dimetyl sulfone or sulfolane.

Suitable catalysts can be metal halides such as FeCl3, TiCl4, A1C13, ZnCl2, NiBr2, PdBr2, AlF3, SbF3, Cul and the like, or halides of boron and silicon such as BF3, BBr3 and SiCl4, or an acidic silicate-catalyst such as bentonite, montmorillonite and the like, which can optionally be activated by treatment with acid and/ or ion exchange and/or drying. Two examples of the catalysts used are BF3 added in the form of its complex with diethyl ether and aluminium-activated bentonite.

The catalyst can be used in an amount of from 0.1 to 50% by weight, preferably from 1 to 10% by weight.

During the reaction the temperature of the 0 reaction mixture is kept between about -30 C and about 0 0 + 200 C, preferably between about +20 C and about +100°C.

The reactants can be present in the solvent in a concentration of between 10 and 100% by weight, based on the solvent.

The ketals of formula IV wherein Z = OSO2CH3, the ketals of formula IV wherein Z = Cl or Br, and the ketal alcohols of formula V are novel compounds and are also the object of the invention in the form of an intermediate product and a starting material as stated in claims 4 and 5, respectively.

It has been found that the novel alkoxyamino ketals of formula I have fungicidal activity. Surprisingly, the alkoxyamino ketals of the general formula I according to the invention exhibit a fungicidal activity superior to that of the alkoxyaminomethyl dioxolanes known from the state of the art, for example 2-(N-ethyl-N-2-methoxyethylaminomethyl)-8-(1,1-dimethylethyl)-1,4-dioxaspiro[4.5]decane, 2-(N-propyl-N-(2-oxolanylmethyl)-aminomethyl )-8-(1,1dimethylethyl)-1,4-dioxaspiro[4.5 Jdecane and 2-(N-2-methoxyethylaminomethyl)-8-(1,1-dimethylethyl) 1,4-dioxasplro[4.5]decane, which chemically and in respect of activity are closely related compounds.

The active substances of the invention can be used in practice for combating phytopathogenic fungi as for example Plasmodiophoromycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and Deuteromycetes.

The active substances of the invention can be used, e.g., for combating the plant diseases Puccinla recondlta, Puccinla striiformls and other rust diseases on wheat, Puccinia hordei, Puccinia striiformis and other rust diseases on barley and rust on other host plants as for example coffee, apples, vegetables and ornamental plants.

Eryslphe graminls (mildew) on barley and wheat and 5 other true mildew species on various host plants such as Sphaerotheca fuliglnea on cucumber, Podosphaera leucotrlcha on apples and Unclnula necator on vines. Helminthosporium spp., e.g. Pyrenophora teres (net blotch) on barley.

Rhynchosporlum spp. and Pseudocercosporella herpotrichoides on cereals .

Cercospora arachidicola on peanuts and other Cercospora species on for example sugar beet, banana and soya bean.

Botrytis cinerea (grey mold) on tomato, strawberry, vine and other host plants.

Venturia Inaequalis (scab) on apples.

Pyricularia oryzae on rice.

The active substances are active in vitro against a broad spectrum of fungi.

The active substances are active as seed dressing agents against Fusarlum spp., Septorla spp. , Tilletla spp., Ustilago spp., Helminthosporium spp. and Pseudocercosporella herpotrlcholdes on cereals, Rhizoctonia solani on cotton and Cortlcium sasakii on rice .

Besides an excellent curative activity the active substances of the invention also show extremely good protective properties as well as systemic activi30 ty.

In addition to this some of the compounds are sufficiently volatile to be active in the gaseous phase against fungi on plants.

The compounds may also be useful as industrial 35 (as opposed to agricultural) fungicides, e.g. in the prevention of fungal attack on wood, hides, leather and especially paint films.

The compounds are also useful for the treatment of human fungal infections as for example candidiasis and dermatophyte infections.

In accordance with the above the invention also 5 relates to a fungicidal composition, particularly a plant-fungicidal composition, and more particularly a cereal-fungicidal composition for combating mildew, rust and other significant foliage diseases, which composition is characterized by containing as an active component at least one compound selected from the alkoxyamino ketals of the above formula I.

Moreover, the invention relates to the use of an alkoxyamino ketal of the above formula I for combating fungi, particularly phytopathogenic fungi, and more particularly mildew, rust and other significant foliage diseases on cereals.

Furthermore, the invention relates to a method of combating fungi, particularly phytopathogenic fungi, and more particularly mildew, rust and other signifi20 cant foliage diaseses on cereals, which method is characterized by allowing an alkoxyamino ketal of the above formula I to affect the fungi concerned and/or their biotope.

The compounds can be applied in a number of 25 ways. For example they can be applied, formulated or unformulated, directly to the foliage of a plant, or they can be applied to bushes and trees, to seeds or to other media in which plants, bushes or trees are growing or are to be planted, or they can be sprayed 3 0 on, dusted on or applied as a cream or paste formulation, or they can be applied as a vapour, or as slow release granules. Application can be to any part of the plant, bush or tree, for example to the foliage, stems, branches or roots, or to soil surrounding the roots, 35 or to the seed before it is planted, or to soil generally, to paddy water or to hydroponic culture systems. The compounds of the invention may also be injected into plants or trees and they may also be sprayed onto vegetation using electrodynamic spraying techniques .

Furthermore, the invention relates to a process of preparing a fungicidal composition, particularly a plant-fungicidal composition, and more particularly a cereal-fungicidal composition for combating mildew, rust and other significant foliage diseases, which process is characterized by mixing an alkoxyamino ketal of the above formula I with one or more agents selected from extending agents, surface active agents and other conventional auxiliary agents.

The compositions may be in the form of dusting powders or granules comprising the active ingredient and a solid diluent or carrier, for example fillers such as kaolin, bentonite, kieselguhr, dolomite, calcium carbonate, talc, powdered magnesia, Fuller's earth, gypsum, Hewitt's earth, diatomaceous earth and China clay. Such granules can be preformed granules suitable for application to the soil without further treatment. These granules can be made either by impregnating pellets of filler with the active ingredient or by pelleting a mixture of the active ingredient and powdered filler. Compositions for dressing seed, for example, may comprise an agent (for example a mineral oil) for assisting the adhesion of the composition to the seed. Alternatively, the active ingredient can be formulated for seed dressing purposes using an organic solvent (for example N-methylpyrrolidone or dimethylformamide ) .

The compositions may also be in the form of dispersible powders or granules comprising a wetting agent to facilitate the dispersion in liquids of the 35 powder or granules which may contain also fillers and suspending agents.

The aqueous dispersions or emulsions may be prepared by dissolving the active ingredient(s) in an organic solvent optionally containing wetting, dispersing or emulsifying agents and then adding the mixture to water which may also contain wetting, dispersing or emulsifying agents. Suitable organic solvents are ethylene dichloride, isopropyl alcohol, propylene glycol, diacetone alcohol, toluene, kerosene, methylnaphthalene, the xylenes, trichloroethylene, furfuryl alcohol, tetrahydrofurfuryl alcohol, and glycol ethers (e.g. 2-ethoxyethanol and 2-butoxyethanol).

The compositions to be used as sprays may also be in the form of aerosols wherein the formulation is held in a container under pressure in the presence of a propellant, e.g. fluorotrichloromethane or dichlorodifluoromethane.

The compounds can be mixed in the dry state with a pyrotechnic mixture to form a composition 20 suitable for generating in enclosed spaces a smoke containing the compounds.

Alternatively, the compounds may be used in a micro-encapsulated form. They may also be formulated in biodegradable polymeric formulations to obtain a slow, controlled release of the active substance.

By including suitable additives, for example additives for improving the distribution, adhesive power and resistance to rain on treated surfaces, the different compositions can be better adapted for various utilities.

The compounds can be used as mixtures with fertilisers (e.g. nitrogen-, potassium- or phosphorus-containing fertilisers). Compositions comprising only granules of fertiliser incorporating (for example 35 coated with) the compound are preferred. Such granules suitably contain up to 25% by weight of the compound.

The invention therefore also provides a fertiliser composition comprising the compound of general formula I.

The compositions may also be in the form of 5 liquid preparations for use as dips or sprays which are generally aqueous dispersions or emulsions containing the active ingredient in the presence of one or more surfactants, e.g. wetting agents, dispersing agents, emulsifying agents or suspending agents, or which are spray formulations of the kind suitable for use in electrodynamic spraying techniques. The foregoing agents can be cationic, anionic or non-ionic agents. Suitable cationic agents are quaternary ammonium compounds, for example cetyltrimethylammonium bromide.

Suitable anionic agents are soaps, salts of aliphatic monoesters of sulphuric acid (for example sodium lauryl sulphate), and salts of sulphonated aromatic compounds (for example sodium dodecylbenzenesulphonate, sodium, calcium or ammonium lignosul20 phonate, butylnaphthalene sulphonate, and a mixture of sodium diisopropyl- and triisopropyl-naphthalene sulphonates ) .

Suitable non-ionic agents are the condensation products of ethylene oxide with fatty alcohols such as 25 oleyl or cetyl alcohol, or with alkyl phenols such as octyl- or nonyl-phenol and octylcresol. Other non-ionic agents are the partial esters derived from long chain fatty acids and hexitol anhydrides, the condensation products of the said partial esters with ethylene 30 oxide, and the lecithins. Suitable suspending agents are hydrophilic colloids (for example polyvinylpyrrolidone and sodium carboxymethylcellulose), and the vegetable gums (for example gum acacia and gum tragacanth).

The compositions for use as aqueous dispersions or emulsions are generally supplied in the form of a concentrate containing a high proportion of the active ingredient (s), and the concentrate is to be diluted with water before use. These concentrates often should be able to withstand storage for prolonged periods and after such storage be capable of dilution with water in order to form aqueous preparations which remain homogeneous for a sufficient time to enable them to be applied by conventional and electrodynamic spray equipment. The concentrates may conveniently contain up to 95%, suitably 10-85%, for example 25-60%, by weight of the active ingredient(s). These concentrates suitably contain organic acids (e.g. alkyl or aryl sulphonic acids such as xylenesulphonic acid or dodecyl benzenesulphonic acid) since the presence of such acids can increase the solubility of the active ingredients in the polar solvents often used in the concentrates. The concentrates suitably contain also a high proportion of surfactants so that sufficiently stable emulsions in water can be obtained. After dilution to form aqueos preparations, such preparations may contain varying amounts of the active ingredients depending upon the intended purpose, but an aqueous preparation containing 0.0005% or 0.01% to 10% by weight of active ingredient may be used.

The compositions of this invention can comprise also other compounds having biological activity, e.g. compounds having similar or complementary fungicidal activity or compounds having plant growth regulating, herbicidal or insecticidal activity.

The other fungicidal compound can be, for example, one which is capable of combating ear diseases of cereals (e.g. wheat) such as Septoria, Gibberella and Helminthosporium spp., seed and soil borne diseases and downy and powdery mildews on vines and powdery mildew and scab on apples etc. These mixtures of fungicides can have a broader spectrum of activity than the compound of general formula I alone. Furthermore, the other fungicide can have a synergistic effect on the fungicidal activity of the compound of general formula I.

Examples of the other fungicidal compound are carbendazim, benomyl, thiophanate-methyl, thiabendazole, fuberidazol, etridazol, dichlofluanid, cymoxanil, oxadixyl, ofurace, metalaxyl, furalaxyl, benalaxyl, fosetyl-aluminium, fenarimol, iprodion, procymi10 dion, vinclozolin, penconazol, myclobutanil, R0151297, S33O8, pyrazophos, ethirimol, ditalimfos, tridemorph, triforin, nuarimol, triazbutyl, guazatin, triacetate salt of 1,l'-iminodi(octamethylene)-diguanidine, propiconazol, prochloraz, flutriafol, hexaconazol, i.e. the compound 1-(l,2,4-triazol-l-yl)-2-(2,4-dichlorophenyl)hexan-2-ol, DPX H6573 (1-((bis-4-fluorophenyl) methyl-silyl)methyl-1H-1,2,4-triazol, triadimefon, triadimenol, diclobutrazol, fenpropimorph, pyrifenox, (2RS,3RS)-2-(4-chlorophenyl) - 3-cyclopropyl-1-(1H-1,2,420 triazol-l-yl)butan-2-ol, (RS)-1-(4-chlorophenyl-4,4-dimethyl-3-(1H-1,2,4-triazol-1-yImethyl)-pentan-3-ol, 4chloro-N-(cyano(ethoxy)methyl) benzamide, fenpropidin, chlorozolinate, diniconazol, imizalil, fenfuram, carboxin, oxycarboxin, methfuroxam, dodemorph, BAS 454, blasticidin S, kasugamycin, edifenphos, kitazin P, cycloheximide, phthalide, probenazol, isoprothiolan, tricyclazol, pyroquilon, chlorbenzthiazon, neoasozin, polyoxin D, validamycin A, mepronil, flutolanil, pencycuron, diclomezin, phenazineoxide, nickel dimethyldi30 thiocarbamate, techlofthalam, bitertanol, bupirimat, etaconazol, streptomycin, cypofuram, biloxazol, quinomethionate, dimethirimol, 1-(2-cyano-2-methoxyiminoacetyl) -3-ethyl urea, fenapanil, tolclofosmethyl, pyroxyfur, polyram, maneb, mancozeb, captafol, chloro35 thalonil, anilazin, thiram, captan, folpet, zineb, propineb, sulphur, dinocap, binapacryl, nitrothalisoIE 922013 propyl, dodine, dithianon, fentin hydroxide, fentin acetate, tecnazene, quintozen, dichloran, copper-containing compounds such as copper oxychloride, copper sulphate and Bordeaux mixture as well as organic mercury compounds.

The compounds of general formula I can be mixed with soil, peat or other rooting media for the protection of the plants against seed-borne, soil-borne or foliar fungal diseases.

Suitable insecticides that can be incorporated in the composition of the invention include pirimicarb, dimethoate, demeton-s-methyl, formothion, carbaryl, isoprocarb, XMC, BPMC, carbofuran, carbosulfan, diazinon, fenthion, fenitrothion, phenthoate, chlor15 pyrifos, isoxathion, propaphos, monocrotophos, buprofezin, ethoproxyfen and cycloprothrin.

Plant growth regulating compounds for use in compositions of the invention are compounds which control weeds or seedhead formation or selectively 20 control the growth of less desirable plants (e.g. grasses).

Examples of suitable plant growth regulating compounds for use with the compositions of the invention are the gibberellins (e.g. GA3, GA4 or GA7), the 25 auxins (e.g. indoleacetic acid, indolebutyric acid, naphthoxyacetic acid or naphthylacetic acid), the cytokinins (e.g. kinetin, diphenylurea, benzimidazole, benzyladenine or benzylaminopurine), phenoxyacetic acids (e.g. 2,4-D or MCPA), substituted benzoic acids (e.g. triiodobenzoic acid), morphactins (e.g. chlorfluorecol), maleic hydrazide, glyphosate, glyphosine, long chain fatty alcohols and acids, dikegulac, paclobutrazol, fluorprimidol, fluoridamid, mefluidide, substituted quaternary ammonium and phosphonium com35 pounds (e.g. chlormequat, chlorphonium or mepiquatchloride), ethephon, carbetamide, methyl-3,6-dichloroIE 922013 anisate, daminozide, asulam, abscisic acid, isopyrimol, 1-(4-chlorophenyl)-4,6-dimethyl-2-oxo-l,2-dihydropyridine-3-carboxylic acid, hydroxybenzonitriles (e.g. bromoxynil), difenzoquat, benzoylprop-ethyl 3,6-di5 chloropicolinic acid, fenpentezol, inabenfid, triapenthenol, and tecnazene.

The invention is further illustrated by means of the following Preparations, Preparation Examples and Application Examples.

Preparation 1 Preparation of the intermediate product 2-(2-methanesulphonyloxyethyl)-8-(1,1-dimethylethyl)-1,4-dioxa15 spiro[4.5]decene-7_ A solution of 2-(2-hydroxyethyl)-8-(1,1-dimethylethyl ) -1 , 4-dioxaspiro[ 4 . 5 ]decene-7 (12.7 g, 0.053 mol) and triethylamine (7.5 g, 0.074 mol) in methylene 20 chloride (60 ml) is cooled in an ice bath, while a solution of methanesulphonyl chloride (7.5 g, 0.066 mol) in methylene chloride (15 ml) is added dropwise at 0 such a rate that the temperature does not exceed 15 C. After completion of the dropwise addition the reaction mixture is stirred at room temperature for an hour and then the solvent is evaporated in vacuo. The residue from evaporation is redissolved in methyl-t-butyl ether (150 ml) and extracted with water (2 x 100 ml). The organic phase is separated, dried over sodium sulphate and evaporated in vacuo to obtain a viscous oil of n^p 1.4848. The product thus obtained is used without further purification for further reaction.

Preparation 2 Preparation of the starting material 2-(2-hydroxyethyl)-8-(1,1-dimethylethyl)-1,4-dioxaspiro[4.5]de5 cene-7 A mixture of 4-(1,1-dimethylethyl)-1-methoxycyclohexa-1,4-diene (16.6 g, 0.1 mol), 1,2,4-butanetriol (10.6 g, 0.1 mol) and p-toluenesulphonic acid (100 mg), dissolved in toluene (120 ml), is heated 15 under reflux and simultaneous removal of the methanol formed by means of a water-separator. After 2 hours a gas chromatografic analysis shows that the reaction is complete. The reaction mixture is cooled to room temperature and triethylamine (1 ml) is added to neu20 tralize the acidic catalyst. Extraction with water (100 ml) is performed and the organic phase is separated, dried over sodium sulphate and evaporated in vacuo. The resulting oil is purified by distillation. Yield 12.7 g (53%) of a colourless Hg; n^6: 1.4812.

In a similar manner the are prepared oil of b.p. 170 C/10 mm following ketal alcohols Refractive Index (26C) 1.4866 Preparation of the starting material 2-(2-chloroethyl) 15 8-(1,1-dimethylethyl)-1,4-dioxaspiro[4.5]decene-7 A mixture of 4-(1,1-dimethylethyl)-3-cyclohexene-l-one (10.4 g, 0.068 mol) and 3 g of aluminiumactivated montmorillonite K 10 in toluene (30 ml) is 0 heated while vigorously stirring to 60 C. To this a so25 lution of 1,2-epoxy-4-chlorobutane (8.75 g, 0.082 mol) in toluene (15 ml) is added dropwise during 30 minutes.

The reaction mixture is kept at 60 C for one hour and then heated under reflux for another hour, whereafter the catalyst is filtered off on a paper filter and the filtrate evaporated in vacuo. The resulting oil is purified by distillation. Yield 6.1 g (37%) of an oil of b.p. 150-156°C/10 mm Hg; 1.4847.

Preparation Example 1 Preparation of 2-(2-(N-ethyl-N-(2-oxolanylmethyl)) aminoethyl )-8-(1,1,2-trimethylpropyl)-1,4-dioxaspiro[4.5]5 decane, compound No. 4 8_ A mixture of 2-(2-chloroethyl)-8-(1,1,2-trimethylpropyl ) -1 , 4-dioxaspiro[ 4 . 5 ]decane (1.73 g, 0.006 mol), N-ethyl-N-(2-oxolanylmethyl)amine (1.29 g, 0.010 mol), sodium iodide (0.2 g) and potassium carbonate (2.0 g) in dimethylformamide (10 ml) is heated under reflux for 2 hours. The reaction mixture is cooled and diluted with water (200 ml) and then extracted with methyl-t-butyl ether (100 ml). The organic phase is separated dried over sodium sulphate and evaporated in vacuo. The resulting oil is purified by kugelrohr distillation. Yield 1.83 g (80%) of a viscous oil of o 26 b.p. 230 C/0.01 mm Hg; nD : 1.4838.

Preparation Example 2 Preparation of 2-(2-(N-(2-methoxyethyl)-N-propyl) aminoethyl )-8-(1,1-dimethylethyl )-1,4-dioxaspiro[4.5] — decane, compound No. 3 In an autoclave with glass liner a mixture of 2-(2-methanesulphonyloxyethyl)-8-(1,1-dimethylethyl) 1,4-dioxaspiro[4.5]decane (3.20 g, 0.01 mol) and N-(2-methoxyethyl)-N-propylamine (3.51 g, 0.03 mol) is 0 placed. The autoclave is heated to 150 C and kept at said temperature for one hour. After cooling to room temperature the reaction mixture is poured into a 5% aquous sodium carbonate solution (50 ml) and extracted with methyl-t-butyl ether (100 ml). The organic phase is separated, dried over sodium sulphate and evaporated in vacuo. The residual oil is purified by kugelrohr distillation. Yield 2.39 g (70%) of a viscous oil of b.p. 170 C/0.08 mm Hg; n^: 1.4653.

Preparation Example 3 Preparation of 2-(2-(N-allyl-N-(3-methoxypropyl))aminoethyl-8-(1,1-dimethylethyl)-1,4-dioxaspiro[4.5]decene-7, compound No. 47 A mixture of 2-(2-methanesulphonyloxyethyl)-81,1-dimethylethyl)-1,4-dioxaspiro[4.5]decene-7 (1.91 g, 0.006 mol), N-allyl-N-(3-methoxypropyl) amine 1.29 g, 0.010 mol), sodium iodide (0.2 g) and potassium carbonate (2.0 g) in dimethylformamide (10 ml) is heated under reflux for two hours. Workup of the reaction mixture is carried out as stated in Preparation Example 1. Yield 1.30 g (62%) of a viscous oil 0 26 of b.p. 175 C/0.01 mm Hg; nD: 1.4802.

Preparation Example 4 Preparation of 2-(2-(N-(2-methoxyethyl)-N-propyl)aminoethy1)-8-(1,1-dimethylethyl)-1,4-dioxaspiro[4.5 Jdecene7, compound No. 41 A mixture of 2-(2-chloroethyl)-8-(1,1-dimethylethyl ) -1 , 4-dioxaspiro[ 4 . 5 ]decene-7 (1.55 g, 0.006 mol), N-(2-methoxyethyl)-N-propylamine (1.17 g, 0.010 mol) sodium iodide (0.2 g) and potassium carbonate (2.5 g) in diethyleneglycoldimethylether (diglyme, 15 ml) is heated under reflux for three hours. Workup of the reaction mixture is carried out as stated in Preparation Example 1. Yield 1.12 g (55%) of a viscous oil of o Ofi b.p. 190 C/0.01 mm Hg; nD: 1.4746.

The alkoxyamino ketals of formula I according to the invention are exemplified by specific examples of compounds as stated in the following Table 1 wherein 0 the term Refractive Index (26 C) is identical to Re5 tractive Index ηθ.

Table 1 No.

No.

No.

No.

No.

No.

No.

No.

No. .0 Q-> νθχ'^Ν’^οοΗ., och3 NH.

NH och3 och3 .OC2H5 Refractive Index (26 ’C) 1.4681 Refractive Index (26 ‘C) 1.4729 Refractive Index (26 *C) 1.4653 Refractive Index (26 ’C) 1.4715 Refractive Index (26 ’C) 1.4708 Refractive Index (26 ’C) 1.4723 Refractive Index (26 ’C) 1.4731 Refractive Index (26 ’C) 1.4711 Refractive Index (26 ’C) 1.4786 Refractive Index (26 ‘C) 1.4779 Refractive Index (26 ’C) 1.4890 Refractive Index (26 °C) 1.4813 Refractive Index (26 ’C) 1.4800 Refractive Index (26 *C) 1.4910 Refractive Index (26 °C) 1.4658 Refractive Index (26 *C) 1.4690 Refractive Index (26 °C) 1.4673 Refractive Index (26 °C) 1.4670 Refractive Index (26 *C) 1.4727 Refractive Index (26 ’C) 1.4782 Refractive Index (26 ’C) 1.4656 Refractive Index (26 ’C) 1.4650 Refractive Index (26 ’C) 1.4708 Refractive Index (26 ’C) 1.4726 Refractive Index (26 *C) 1.4732 Refractive Index (26 ’C) 1.4705 Refractive Index (26 ’C) 1.4700 ΙΕ 922013 No.

Refractive Index (26 ’C) l.4707 Refractive Index (26 *C) 1.4761 Refractive Index (26 ’C) 1.4758 Refractive Index (26 *C) 1.4810 Refractive Index (26 *C) 1.4690 Refractive Index (26 ’C) 1.4682 Refractive Index (26 *C) 1.4738 Refractive Index (26 ’C) 1.4756 Refractive Index (26 ’C) 1.4761 No.

No.

No.

No.

N^o N^o Λ N^o Refractive Index (26 ’C) 1.4704 Refractive Index (26 °C) 1.4698 Refractive Index (26 °C) 1.4758 Refractive Index (26 °C) 1.4752 Refractive Index (26 °C) 1.4746 Refractive Index (26 °C) 1.4737 Refractive Index (26 °C) 1.4731 Refractive Index (26 *C) 1.4784 Refractive Index (26 °C) 1.4791 No.

No.

No.

No.

No.

No.

No.

No.

No.

Refractive Index (26 *C) 1.4814 Refractive Index (26 ‘C) 1.4802 Refractive Index (26 *C) 1.4838 Refractive Index (26 ’C) 1.4695 Refractive Index (26 ’C) 1.4759 Refractive Index (26 ’C) 1.4766 Refractive Index (26 *C) 1.4839 Refractive Index (26 ’C) 1.4768 Refractive Index (26 *C) 1.4744 Refractive Index (26 *C) 1.4740 Refractive Index (26 °C) 1.4732 Refractive Index (26 °C) 1.4788 Refractive Index (26 °C) 1.4706 Refractive Index (26 °C) 1.4701 Refractive Index (26 °C) 1.4759 Refractive Index (26 °C) 1.4804 Refractive Index (26 °C) 1.4690 Refractive Index (26 °C) 1.4684 Refractive Index (26 ’C) 1.4737 Refractive Index (26 *C) 1.4753 Refractive Index (26 ’C) 1.4712 Refractive Index (26 *C) 1.4711 Refractive Index (26 *C) 1.4680 Refractive Index (26 *C) 1.4739 Refractive Index (26 ’C) 1.4737 Refractive Index (26 ’C) 1.4705 Refractive Index (26 *C) 1.4702 Refractive Index (26 *C) 1.4671 Refractive Index (26 ’C) 1.4703 Refractive Index (26 *C) 1.4701 Refractive Index (26 ‘C) 1.4684 Refractive Index (26 ’C) 1.4733 Refractive Index (26 ’C) 1.4750 Refractive Index (26 *C) 1.4734 Refractive Index (26 ’C) 1.4722 Refractive Index (26 ’C) 1.4716 Έ922013 Refractive Index (26 ’C) 1.4784 Refractive Index (26 *C) 1.4736 Refractive Index (26 °C) 1.4720 Refractive Index (26 °C) 1.4780 Refractive Index (26 °C) 1.4768 Refractive Index (26 °C) 1.4825 Refractive Index (26 °C) 1.4844 Refractive Index (26 °C) 1.4711 Refractive Index (26 °C) 1.4798 No.

No.

No.

No.

No.

No.

No. r°' FY'' OJ Refractive Index (26 °C) 1.4709 Refractive Index (26 ‘C) 1.4710 Refractive Index (26 *C) 1.4830 Refractive Index (26 °C) 1.4743 Refractive Index (26 °C) 1.4745 Refractive Index (26 ’C) 1.4750 Refractive Index (26 °C) 1.4806 Refractive Index (26 °C) 1.4803 Refractive Index (26 °C) 1.4794 No.

No. 107 ΝΗ^.Ο^ Refractive Index (26 ’C) 1.4724 Refractive Index (26 *C) 1.4870 Refractive Index (26 *C) 1.4939 Refractive Index (26 *C) 1.4745 Refractive Index (26 ‘C) 1.4708 Refractive Index (26 ’C) 1.4677 Refractive Index (26 ’C) 1.4702 Refractive Index (26 ‘C) 1.4682 Refractive Index (26 °C) No. 108 1.4732 Refractive Index (26 ’C) 1.4724 Refractive Index (26 ’C) 1.4655 Refractive Index (26 ’C) 1.4686 Refractive Index (26 ’C) 1.4688 Refractive Index (26 *C) 1.4689 Refractive Index (26 ’C) 1.4719 Refractive Index (26 *C) 1.4721 Refractive Index (26 *C) 1.4649 Refractive Index (26 ’C) 1.4681 Refractive Index (26 *C) 1.4711 Refractive Index (26 ’C) 1.4680 Refractive Index (26 ‘C) 1.4834 Refractive Index (26 ’C) 1.4861 Refractive Index (26 ’C) 1.4858 Refractive Index (26 'C) 1.4888 Refractive Index (26 *C) 1.4713 Refractive Index (26 C) 1.4736 Refractive Index (26 ’C) 1.4734 No. 127 No. 128 No. 129 No. 130 No. 131 No. 132 No. 133 No. 134 No. 135 A N. Λ- Λ· Ο Λλ Ο. ~ ο Λ.

Refractive Index (26 *C) 1.4733 Refractive Index (26 °C) 1.4768 Refractive Index (26 ’C) 1.4725 Refractive Index (26 *C) 1.4751 Refractive Index (26 *C) 1.4758 Refractive Index (26 ’C) 1.4781 Refractive Index (26 *C) 1.4778 Refractive Index (26 ’C) 1.4777 Refractive Index (26 ’C) 1.4811 37a No. 136 Refractive Index (26 ’C) 1.4750 No. 137 Refractive Index (26 *C) 1.4781 No. 138 Refractive Index (26 *C) 1.4796 No. 139 Refractive Index (26 *C) 0 —' 1.4821 No. 140 Refractive Index (26 ’C) 0—' 1.4815 No. 141 0-f Refractive Index (26 *C) 1.4814 No. 142 Refractive Index (26 ’C) 1.4850 No. 143 Refractive Index (26 *C) 0 1.4843 No. 144 Refractive Index (26 *C) 1.4641 37b No. 145 Refractive Index (26 ’C) 1.4672 No. 146 Refractive Index (26 *C) 1.4673 No. 147 O-f Refractive Index (26 ’C) 1.4708 No. 148 Refractive Index (26 *C) 1.4833 No. 149 Refractive Index (26 ’C) 1.4857 No. 150 Refractive Index (26 ’C) 1.4846 No. 151 Refractive Index (26 *C) 1.4880 No. 152 Refractive Index (26 *C) 1.4666 No. 153 Refractive Index (26 ’C) 1.4696 37c No. 154 Refractive Index (26 ’C) 1.4698 No. 155 Refractive Index (26 *C) 1.4728 No. 156 Refractive Index (26 *C) 1.4776 No. 157 Refractive Index (26 ’C) 1.4800 No. 158 Refractive Index (26 *C) 1.4834 No. 159 Refractive Index (26 *C) 1.4789 No. 160 Refractive Index (26 ’C) 1.4821 No. 161 0-7 Refractive Index (26 *C) 1.4799 No. 162 Refractive Index (26 *C) 1.4833 37d No. 163 Refractive Index (26 *C) 1.4828 ,E 922013 37e No. 172 Refractive Index (26 ’C) 1.4765 No. 173 Refractive Index (26 *C) 1.4870 No. 174 O-f Refractive Index (26 ’C) 1.4936 No. 175 y^N ' Refractive Index (26 *C) 1.4789 No. 176 Refractive Index (26 ’C) 1.4871 No. 177N χ^ο' Refractive Index (26 *C) 1.4857 No.N '-XSO'Z 178 Refractive Index (26 ’C) 1.4839 No. 179 Refractive Index (26 'C) 1.4919 No. 180 Refractive Index (26 ’C) 1.4868 37f No. 187 Refractive Index (26 *C) 1.4808 No. 188 Refractive Index (26 *C) 1.4710 No. 189 Refractive Index (26 ’C) 1.4802 37g Refractive Index (26 ’C) 1.4752 No. 190 No. 191 Refractive Index (26 *C) 1.4710 No. 192 QJ Refractive Index (26 *C) 1.4799 No. 193 Refractive Index (26 ‘C) 1.4851 No. 194 ^y-Cs? OJ Refractive Index (26 *C) 1.4840 No. 195 Refractive Index (26 *C) 1.4710 No. 196 Refractive Index (26 *C) 1.4837 No. 197 Refractive Index (26 *C) 1.4768 No. 198><Q°y^ -s ° CH3O^OCH3 Refractive Index (26 *C) 1.4767 Έ922013 37h No. 199 y^N, Refractive Index (26 ’C) 1.4721 No. 200 Refractive Index (26 *C) 1.4898 No. 201 \ OCH3 Refractive Index (26 *C) 1.4779 No. 202 Refractive Index (26 ’C) 1.4781 37i No. 211 Refractive Index (26 *C) 1.4810 No. 212 Refractive Index (26 ’C) 1.4742 37j 37k No. 232 Refractive Index (26 *C) 1.4702 1.4790 1 APPLICATION EXAMPLES In the following Application Examples the compounds mentioned below and known from Danish patent 5 application No. 1201/88 (EP 0 281 842 Al) are used as compounds of comparison. 2-(N-ethyl-N-2-methoxyethyl) aminomethyl )-8-(1,1-dimethylethyl)-1,4-dioxaspiro[4.5 Jdecane No. 7 4 2-(N- ethyl-N-(2-oxolanylmethyl)-aminomethyl)-8-(l,1dimethylethyl)-1,4-dioxaspiro[4.5 Jdecane 2-(N-2-methoxyethylaminomethyl)-8-(1,1-dimethylethyl) 1,4-dioxaspiro[4.5 Jdecane Application Example l Erysiphe graminis hordei (Mildew on barley).

Curative spraying of young barley plants.

Solvent : 10% acetone in water.

Emulsifier: Triton X-155, 100 ppm.

To prepare an appropriate composition of active 10 substance the active substance is dissolved in the specified solvent with emulsifier to the concentration desired. Further dilution is carried out by a solution containing 10% acetone in water and 100 ppm Triton X-155.

To test for curative activity young barley plants are sprayed to leaf wetness with the composition of active substance 2 days after the plants have been inoculated with mildew conidia by the brush method. After inoculation and until spraying the plants are left at 18°C and 100% RH, and after spraying they are left in a growth chamber at 18 C and 70-80% RH.

Days after inoculation the activity of the substance is evaluated. A clear superiority in activity in relation to the state of the art is shown by the compounds according to the Examples Nos. 2, 3, 13, 23, 24, 28, 29, 30, 31, 35, 37, 39, 40, 41, 42, 43, 44, 45, 47, 48, 51, 58, 60, 64, 66.

Application Example 2 Puccinia recondita test (wheat, protective spray).

Solvent : 10% acetone in water.

Emulsifier: Triton X-155, 100 ppm.

To prepare an appropriate composition of active substance the active substance is dissolved in the specified solvent with emulsifier to the concentration desired. Further dilution is carried out by a solution containing 10% acetone in water and 100 ppm Triton X-155.

To test for protective activity young wheat plants are sprayed to leaf wetness with the composition of active substance. After drying the plants are inoculated with brown rust spores in an aqueous slurry which is sprayed on. The plants are left for 48 hours at 18 C and 100% RH, whereafter they are transferred to a growth chamber at the same temperature and 70-80 RH.

Days after inoculation the activity of the substances is evaluated. A clear superiority in activity in relation to the state of the art is shown by the compounds according to the Examples Nos. 2, 3, 4, , 6, 10, 11, 14, 16, 17, 18, 19, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 33, 34, 35, 37, 38, 39, 40, 42, 43, 46, 53, 54, 55, 56, 57, 58, 59, 60.

Application Example 3 Erysiphe graminis trltlcl (Mildew on wheat).

Curative spraying of young wheat plants.

Solvent : 10% acetone in water.

Emulsifier: Triton X-155, 100 ppm.

To prepare an appropriate composition of active substance the active substance is dissolved in the specified solvent with emulsifier to the concentration desired. Further dilution is carried out by a solution containing 10% acetone in water and 100 ppm Triton X-155.

To test for curative activity young wheat plants are sprayed to leaf wetness with the composition of active substance 24 hours after the plants have been inoculated with mildew conidia by the brush method.

After inoculation and until spraying the plants are 0 left at 18 C and 100% RH, and after spraying they are left in a growth chamber at 18°C and 70-80% RH.

Days after inoculation the activity of the substance is evaluated. A clear superiority in activity in relation to the state of the art is shown by the compounds according to the Examples Nos. 2, 3, 4, 5, 6, 7, 8 , 13 , 23 , 24 , 30, 31, 32, 36, 38, 39, 44 , 53, 57 , 58, 65, 66, 72. 41a Test results (EDgq) obtained according to Application Examples 2 and 3 are summarized in the following Table 2.

Table 2t BIOLOGICAL TESTS Comp. Puccinia Erysiphe Comp. Puccinia Erysiphe No. recondite graminis No. recondita graminis (wheat) tritici (wheat) tritici (wheat) (wheat) EDgo (ppm) BD90 (ppm) EDgo (ppm) B°9Q (PPm) A* 512 32 53 32 2 B* 128 16 54 64 4 C* >512 64 55 64 4 2 64 1 56 32 4 3 64 2 57 32 2 4 32 2 58 32 2 5 64 2 59 32 4 6 64 2 60 32 4 7 - 4 61 32 4 8 - 4 62 32 4 10 32 2 63 32 4 11 64 - 64 16 4 13 - 4 65 32 2 14 64 2 66 16 2 16 64 4 67 16 4 17 32 2 70 32 4 18 64 2 71 32 4 19 32 2 72 32 2 21 32 8 73 32 4 22 32 2 74 16 4 23 32 2 75 16 - 24 64 4 76 16 - 25 64 4 77 32 - 26 32 2 78 32 - 27 32 4 79 16 4 28 16 4 80 16 - 29 32 4 81 16 - 30 16 <2 82 16 - 31 - 2 87 16 - 33 64 <2 88 32 4 34 32 4 89 32 4 35 64 4 90 32 2 36 64 2 91 32 4 37 32 <2 94 16 4 38 32 2 95 64 8 39 32 2 97 32 - 40 32 4 98 32 4 42 32 4 99 64 - 43 32 4 100 16 8 44 64 2 101 64 2 45 16 4 110 64 4 46 32 4 111 64 4 41b Table 2: BIOLOGICAL TESTS CONT.

Comp. No. Puccinia recondite (wheat) E°9o (PP««) Erysiphe graminis tritici (wheat) EDgo (ppm) Comp. Puccinia Erysiphe graminis tritici (wheat) EDgo (PPm) No. recondite (wheat) EDg0 (ppm) 112 32 2 178 16 113 32 2 179 16 - 114 64 2 180 32 4 115 - 8 182 16 - 116 - <2 183 16 - 117 64 2 185 16 2 118 16 2 188 16 2 119 32 4 189 64 2 120 32 4 190 64 2 121 32 2 193 32 2 122 32 4 195 - 2 123 64 4 196 32 4 124 32 4 197 64 2 125 16 4 201 32 - 126 16 4 202 64 127 - 2 207 32 - 128 - 2 208 32 - 129 - 4 211 32 - 130 - 2 214 16 4 131 32 4 215 32 - 132 64 <2 216 32 - 133 16 4 217 16 - 134 - 4 218 - 2 135 16 4 219 32 2 136 - 2 220 32 4 139 64 4 221 32 4 140 32 4 224 16 4 144 32 4 225 16 4 145 32 4 226 8 - 146 32 4 228 16 2 147 64 4 229 16 4 160 32 4 230 32 - 165 64 - 231 16 4 166 64 - 232 16 - 167 64 - 233 16 4 170 64 - 234 32 - 172 32 8 237 32 - 175 32 - 238 16 4 176 32 4 240 32 — * Compounds A, B and C are compoun ds of comparison and are identical to compounds Nos. 74, 143 and 42, respectively, as known from EP 0 281 842 A1, see page 38 of the present specification.

•E 922013

Claims (19)

1. Alkoxyamino ketals, characterized by having the general formula I wherein A represents a single or a double bond, R 1 represents a substituent selected from straight or branched chain alkyl having up to 10 carbon atoms,

2. A process for the preparation of alkoxyainino ketals of the general formula I wherein A, R 1 , R 2 and R 3 have the meanings defined in claim 1, characterized by reacting a ketal of the general formula II II wherein A and R 1 have the above defined meanings, and wherein Z represents an exchangeable electron-attracting group, with an amine of the general formula III ,R' HN III wherein R 2 and R 3 have the above defined meanings, 30 optionally in the presence of a solvent and optionally in the presence of a catalyst, and optionally in the presence of an acid-binding agent in addition to a possible excess of the amine III. 35

3. A process according to claim 2 for the preparation of compounds of the general formula I, wherein A represents a double bond, characterized by using a ketal of the general formula II, wherein A represents a double bond, and Z represents a methanesulphonyloxy group or a chlorine or bromine

4. An intermediate product for use in the process according to claim 3, characterized by having the general formula IV V IV wherein R 1 has the above defined meaning, and Z' represents a methanesulphonyloxy group or a chlorine or 20 bromine atom.

5. A starting material for the preparation of an intermediate product according to claim 4 of formula IV wherein Z' represents a methanesulphonyloxy group, 25 by reaction with methanesulphonyloxy chloride, characterized by having the formula V 35 wherein R 1 has the above defined meaning. 5 atom.

6. A fungicidal composition, particularly a plant-fungicidal composition, and more particularly a cereal-fungicidal composition for combating mildew, rust and other significant foliage diseases, charac5 terized by containing as an active component at least one compound selected from the alkoxyamino ketals of formula I as defined in claim 1.

7. Use of an alkoxyamino ketal of formula I as

8. A method of combating fungi, particularly

9. A process of preparing a fungicidal composition, particularly a plant-fungicidal composition, and more particularly a cereal-fungicidal composition for combating mildew, rust and other significant foliage 25 diseases, characterized by mixing an alkoxyamino ketal of formula I as defined in claim 1 with one or more agents selected from extending agents, surface active agents and other conventional auxiliary agents. -4610. An alkoxyamino ketal of the general formula I given and defined in claim 1, substantially as hereinbefore described and exemplified.

10. Defined in claim 1 for combating fungi, particularly phytopathogenic fungi, and more particularly mildew, rust and other significant foliage diseases on cereals.

11. A process for the preparation of an alkoxyamino ketal of the general formula I given and defined in claim 1, substantially as hereinbefore described and exemplified.

12. An alkoxyamino ketal of the general formula I given and defined in claim 1, whenever prepared by a process claimed in any one of claims 2, 3 or 11 .

13. An intermediate product of the general formula IV given and defined in claim 4, substantially as hereinbefore described and exemplified.

14. A starting material of the formula V given in claim 5, substantially as hereinbefore described and exemplified.

15. A fungicidal composition according to claim 6, substantially as hereinbefore described and exemplified. 15 phytopathogenic fungi, and more particularly mildew, rust and other significant foliage diseases on cereals, characterized by allowing an alkoxyamino ketal of formula I as defined in claim 1 to affect the fungi concerned and/or their biotope. 15 unsubstituted or alkylsubstituted cycloalkyl having up to 6 ring carbon atoms and cycloalkylalkyl having up to 10 carbon atoms in all, R and R J each independently represents hydrogen, straight or branched chain alkyl having up to 10 carbon 20 atoms, unsubstituted, alkylsubstituted, alkoxysubstituted or alkoxyalkylsubstituted cycloalkyl, alkenyl having up to 10 carbon atoms, alkynyl, alkoxyalkyl, dialkoxyalkyl, dioxolanylalkyl, oxolanyl, oxolanylalkyl, dioxanylalkyl, furanyl, furanylalkyl or 25 unsubstituted or alkylsubstituted cycloalkylalkyl, at least one of the substituents R 2 and R 3 being an oxygen-containing alkyl or cycloalkyl group, or R 2 and R 3 when taken together with the nitrogen atom to which they are attached form a saturated or un30 saturated heterocyclic ring which is furthermore substituted once, twice or three times by alkoxy or alkoxyalkyl groups.

16. A process of preparing a fungicidal composition according to claim 6, substantially as hereinbefore described and exemplified.

17. A fungicidal composition according to claim 6, whenever prepared by a process claimed in claim 9 or 16.

18. Use according to claim 7, substantially as hereinbefore described and exemplified.

19. A method according to claim 8 of combating fungi, substantially as hereinbefore described and exemplified.