WO1993002074A1

WO1993002074A1 - Alkoxyamino ketals, their preparation and intermediate products therefor, and their use as fungicides

Info

Publication number: WO1993002074A1
Application number: PCT/DK1992/000199
Authority: WO
Inventors: Axel Svendsen; Anita Wengel; Niels Jacobsen; Hans Kolind-Andersen
Original assignee: Cheminova Agro A/S
Priority date: 1991-07-15
Filing date: 1992-06-25
Publication date: 1993-02-04
Also published as: ZA924723B; PT100654A; DK135091D0; AU2348892A; IE922013A1

Abstract

Alkoxyamino ketals of formula (I), wherein A represents a single or a double bond, R1 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 R3¿ each independently represents hydrogen, C¿1?-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 R3¿ being an oxygen-containing alkyl or cycloalkyl group, or R?2 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, and the preparation of these compounds and intermediate products therefor are described. The compounds (I) have fungicidal, particularly plant-fungicidal activity.

Description

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 application 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 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 R¹-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-methyl- 1-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-dimethoxyethyl or 2,2-diethoxyethyl,

dioxolanylalkyl is prefebrably 2-dioxolanylmethyl,

oxolanylalkyl is preferably 2-oxolanylmethyl,

dioxanylalkyl is preferably 1,3-dioxan¬

2-ylmethyl,

furanylalkyl is preferably 2-furanylmethyl,

the alkoxysubstituted heterocyclic ring 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-methoxymethylpyrrolidino.

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, R¹, R² and R³ have the above defined meanings, are obtainable by reacting a ketal of the general formula 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, 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, acetonitrile, 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 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, 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 question of methanesulphonates (Z = OSO₂CH₃), are obtainable by reacting a ketal alcohol of formula v

wherein R¹ has the above defined meaning, with methane- sulphonyl chloride of formula VI CH₃SO₂Cl VI in a manner known per se in the presence of a solvent as for example methyl-t-butyl ether, toluene, methyl- 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 (International Application No. PCT/DK92/00066).

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

in the presence of an aprotic organic solvent such as toluene or 1,2-dichloroethane, and in 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 1,2- epoxy-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 aromatic 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, AlCl₃, ZnCl₂, NiBr₂, PdBr₂, AIF₃, 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 reaction mixture is kept between about -30°C and about +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 alkoxy- aminomethyl dioxolanes known from the state of the art, for example

2- (N-ethyl-N-2-methoxyethylaminomethyl)-8-(1,1-dime- thylethyl)-1,4-dioxaspiro[4.5]decane,

2-(N-ethyl-N-(2-σxolanylmethyl)-aminomethyl)-8-(1,1- dimethylethyl)-1,4-dioxaspiro[4.5]decane and

2-(N-2-methoxyethylaminomethyl)-8-(1,1-dimethylethyl)- 1,4-dioxaspiro[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 Puccinia recondita, Puccinia striiformis 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.

Erysiphe graminis (mildew) on barley and wheat and other true mildew species on various host plants such as Sphaerotheca fuliginea on cucumber, Podosphaera leucotricha on apples and Uncinula necator on vines. Helminthosporium spp., e.g. Pyrenophora teres (net blotch) on barley.

Rhynchosporium 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 Fusarium spp., Septoria spp., Tilletia spp., Ustilago spp., Helminthosporium spp. and Pseudocercosporella herpotrichoides on cereals,

Rhizoctonia solani on cotton and Corticium sasakii on rice.

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

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 (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 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 significant 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 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 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, 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 dimethyl- formamide).

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 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 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 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 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 dodecylbenzene- sulphonate, sodium, calcium or ammonium lignosul- 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 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 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, procymidion, vinclozolin, penconazol, myclobutanil, R0151297, S3308, pyrazophos, ethirimol, ditalimfos, tridemorph, triforin, nuarimol, triazbutyl, guazatin, triacetate salt of 1,1'-iminodi(octamethylene)-diguanidine, propiconazol, prochloraz, flutriafol, hexaconazol, i.e. the compound 1-(1,2,4-triazol-1-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-1,2,4- triazol-1-yl)butan-2-ol, (RS)-1-(4-chlorophenyl-4,4-di- methyl-3-(1H-1,2,4-triazol-1-ylmethyl)-pentan-3-ol, 4-chloro-N-(cyano(ethoxy)methyl) benzamide, fenpropidin, chlorozolinate, diniconazol, imizalil, fenfuram, carb- oxin, 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 dimethyldithiocarbamate, techlofthalam, bitertanol, bupirimat, etaconazol, streptomycin, cypofuram, biloxazol, quinomethionate, dimethirimol, 1-(2-cyano-2-methoxyiminoacetyl)-3-ethyl urea, fenapanil, tolclofosmethyl, pyroxyfur, polyram, maneb, mancozeb, captafol, chlorothalonil, anilazin, thiram, captan, folpet, zineb, propineb, sulphur, dinocap, binapacryl, nitrothaliso 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, chlorpyrifos, 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 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 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 compounds (e.g. chlormequat, chlorphonium or mepiquatchloride), ethephon, carbetamide, methyl-3, 6-dichloro anisate, daminozide, asulam, abscisic acid, isopyrimol, 1-(4-chlorophenyl)-4,6-dimethyl-2-oxo-1,2-dihydropyridine-3-carboxylic acid, hydroxybenzonitriles (e.g. bromoxynil), difenzoquat, benzoylprop-ethyl 3,6-di- chloropicolinic acid, fenpentezol, inabenfid, tria- penthenol, 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-methane- sulphonyloxyethyl)-8-(1,1-dimethylethyl)-1,4-dioxa- 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 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 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 124848. The product thus obtained is used

without further purification for further reaction. Preparation 2

Preparation of the starting material 2-(2-hydroxy- ethyl)-8-(1,1-dimethylethyl)-1,4-dioxaspiro[4.5]decene-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 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 neu- 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 oil of b.p. 170°C/10 mm Hg; 1.4812.

In a similar manner the following ketal alcohols are prepared

Refractive Index (26C) 1.4866

Refractive Index (26C)

1.4952

__________________________________________________________________________

Refractive Index (26C)

1.4911

Preparation 3

Preparation of the starting material 2-(2-chloroethyl) 8-(1,1-dimethylethyl)-1,4-dioxaspiro[4.5]decene-7

A mixture of 4-(1,1-dimethylethyl)-3-cyclohexene-1-one (10.4 g, 0.068 mol) and 3 g of aluminium- activated montmorillonite K 10 in toluene (30 ml) is heated while vigorously stirring to 60ºC. To this a solution 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]- decane, compound No. 48

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 b.p. 230º C/0.01 mm Hg; 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 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; 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)-8- 1,1-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 of b.p. 175ºC/0.01 mm Hg;

1.4802. Preparation Example 4

Preparation of 2-(2-(N-(2-methoxyethyl)-N-propyl) amino- ethyl)-8-(1,1-dimethylethyl)-1,4-dioxaspiro[4.5]decene- 7, 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 b.p. 190°C/0.01 mm Hg; 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 the term Refractive Index (26°C) is identical to Refractive Index

APPLICATION EXAMPLES

In the following Application Examples the compounds mentioned below and known from Danish patent application No. 1201/88 (EP 0 281 842 A1) are used as compounds of comparison.

2-(N-ethyl-N-2-methoxyethylaminomethyl)-8-(1,1-dimethylethyl)-1,4-dioxaspiro[4.5]decane

No. 74

2-(N-ethyl-N-(2-oxolanylmethyl)-aminomethyl)-8-(1,1- dimethylethyl)-1,4-dioxaspiro[4.5]decane

No. 143

2-(N-2-methoxyethylaminomethyl)-8-(1,1-dimethylethyl) 1,4-dioxaspiro[4.5]decane

No. 42

Application Example 1

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 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.

7 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.

10 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, 5, 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 tritici (Mildew on wheat).

Curative spraying of young wheat plants.

Solvent : 10% acetone in water.

Emulsifier: Triton X-155, 100 ppm.

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 left at 18°C and 100% RH, and after spraying they are left in a growth chamber at 18°C and 70-80% RH.

8 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.

Test results (ED₉₀) obtained according to Application Examples 2 and 3 are summarized in the following Table 2.

* Compounds A, B and C are compounds of comparison and are identical to compounds Nos. 74, 143 and 42, respectively, as known from EP 0 281 842 A1 , see page 50 of the present specification.

Claims

P A T E N T C L A I M S

1 . Alkoxyamino ketals , characterized by having the general formula I

wherein A represents a single or a double bond,

2. A process for the preparation of alkoxyamino ketals of the general formula I

wherein A, R¹, R² and R³ have the meanings defined in claim 1, characterized by reacting a ketal of the general formula II

wherein A and R¹ have the above defined meanings, and wherein Z represents an exchangeable electron-attracting group, with an amine of the general formula III

wherein R² and R³ have the above defined meanings, 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.

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 atom.

4. An intermediate product for use in the process according to claim 3 , characterized by having the general formula IV

5. A starting material for the preparation of an intermediate product according to claim 4 of formula IV wherein Z' represents a methanesulphonyloxy group, by reaction with methanesulphonyloxy chloride, characterized by having the formula V

wherein R¹ has the above defined meaning,

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

8. A method of combating fungi, particularly 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.

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 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.