PT100654A - ALCOXYAMINOCETHES, ITS PREPARATION, ITS INTERMEDIATE PRODUCTS AND ITS USE AS FUNGICIDES - Google Patents

Description

74 076 Nor / JF / 20753

-2-

The present invention relates to novel alkoxyaminocetides, a process for their preparation and novel intermediates therefor. The invention further relates to the use of novel alkoxyaminocetides as fungicides, particularly plant fungicides. It is known that certain alkoxyaminomethyldioxolanes, e.g.

have fungicidal properties, see Danish Patent Application No. 1201/88 which corresponds to EP 0 281 842 A1.

However, and especially at low application rates and low concentrations, the fungicidal activity of said compounds is not satisfactory in all fields of application.

According to this invention aminoacetals having generally higher fungicidal activity are provided, in particular novel alkoxyaminoalkyls of the general formula I-3-C 'JS. 74 076

Nor / JF / 20753

in which A represents a single or double bond, R 1 represents a substituent selected from straight or branched chain alkyl groups containing up to 10 carbon atoms, unsubstituted or alkyl substituted cycloalkyl containing up to 6 ring carbon atoms and cycloalkylalkyl , containing up to 10 carbon atoms in the total, R 2 and R 3 independently of one another represent hydrogen, straight or branched chain alkyl groups of up to 10 carbon atoms, unsubstituted, substituted or unsubstituted alkoxy substituted or unsubstituted cycloalkyl alkenyl, alkoxyalkyl, dialkoxyalkyl, dioxolanylalkyl, oxynyl, oxolanylalkyl, dioxanylalkyl, furanyl, furanylalkyl or cycloalkylalkyl, wherein at least one of the substituents R 2 and R 3 is cycloalkyl or oxygen-containing alkyl, or R2 and R3 when taken together with the nitrogen atom to which they are attached form a heterocyclic, saturated or unsaturated ring which is further substituted once, twice or three times with alkoxy or alkoxyalkyl groups.

R1 -R3 in the above formula I preferably have, or as an example, the following meanings: R1: the alkyl group is preferably an alkyl group having 4-10 carbon atoms, more preferably a branched chain alkyl group having 4 -8-carbon atoms, the substituted cycloalkyl group is, preferably,

The cycloalkylalkyl group is preferably 1-methyl-1-cyclohexylethyl, and R 1 is the straight or branched chain alkyl group, is preferably 1-methylcyclohexyl, , an alkyl group having up to 6 carbon atoms and more, preferably up to 4 carbon atoms, the cycloalkyl group is preferably cyclopropyl or cyclopentyl, the cycloalkylalkyl group is preferably cyclopropylmethyl, the alkenyl group is preferably , allyl, methallyl or 3-butenyl group, the alkynyl group is preferably propargyl, the alkoxyalkyl group is preferably methoxyethyl, ethoxyethyl, methoxypropyl or ethoxypropyl, the dialkoxyalkyl group is preferably 2,2-dimethoxyethyl or 2,2-diethoxyethyl, the dioxolanylalkyl group is preferably 2-dioxolanylmethyl, the oxolanylalkyl group is preferably 2-oxolanylmethyl, the dioxanylalkyl group is preferably 1,3-dioxan-2-ylmethyl, the furanylalkyl group is preferably alkenyl substituted heterocyclic ring is preferably 2-, 3- or 4-methoxypiperidino or 2- or 3-methoxypyrrolidino, and the alkoxyalkyl-substituted heterocyclic ring is preferably 2-, 3- or 4-methoxymethylpiperidino or 2- or 3-methoxymethylpyrrolidino.

The compounds of formula I may exist as geometric and / or optical isomers or as mixtures of isomers of variable composition. The present invention relates to both pure isomers and mixtures of isomers.

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Nor / JF / 20753

It has further been found that the novel alkoxyaminoalkyls of the general formula I, wherein A, R 1, R 2 and R 3 are as defined above, are obtained by reacting a ketal of formula II

in which A and R 1 are as defined above, and in Z represents an exchangeable electron withdrawing group such as, for example, a halogen atom or an alkanesulfonyloxy group or an arylsulfonyloxy group, with an alkoxyamine of the general formula III

in which R2 and R3 are as defined above, 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 amine III. Optionally, the reaction between the ketals II and the amines III under the above-mentioned conditions may further occur 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 dimethylsulfoxide. Suitable acid binding agents are, e.g., sodium carbonate, potassium carbonate, triethylamine, pyridine or diazabicyclooctane (DABCO). The reaction temperature of the reaction between the ketals II and the amines III may vary within a wide range. is usually operated in a temperature range between 20 ° C and 200 ° C, preferably between 100 ° C and 180 ° C. / · 74 076 Nor / JF / 20753

(3-methoxyphenyl) -1-

For the preparation of alkoxyamino ceftals of general formula I wherein A represents a double bond, a ketal of formula II wherein A is double bond and Z represents a methanesulfonyloxy group or a chlorine or bromine atom, ie ketal of formula IV

in which R1 has the meaning defined above, and Z7 represents a methanesulfonyloxy group or a chlorine or bromine atom.

Ketals of formula IV, e.g., when used in the presence of methanesulfonates (Z = OCH2 CH3), may be obtained by reaction of a ketal alcohol of formula V

in which R 1 is as defined above, with methanesulfonyl chloride of formula VI

in a manner known per se. in the presence of a solvent such as methyl t-butyl ether, toluene, methylene chloride or acetonitrile, and in the presence of an acid binding agent such as, for example, potassium carbonate, triethylamine or pyridine, at temperatures between 0 ° C and 100 ° C.

The corresponding ketals of formula II, wherein A represents a single bond, may be prepared from a compound of formula (I).

-7-

similar to that described in Danish Patent Application No. 516/91 (International Application No. PCT / DK92 / 00066, Portuguese Patent Application No. 100 273).

Ketal alcohols of formula V may be prepared in a generally known manner by reaction of an enol ether which is known from J. Org. Chem. 35, 715 (1970) and has the formula VII R1

VII

in which R 1 is as defined above, with 1,2,4-butanetriol of formula VIII

HO

OH

VIII in the presence of an aprotic organic solvent such as toluene or 1,2-dichloroethane and in the presence of an acid catalyst such as p-toluenesulfonic acid at the boiling point of the solvent in question, while simultaneously withdrawing by means of azeotropic distillation the methanol formed during the ketalization reaction.

In addition, the ketals of formula V when chloroalkanes (Z = cl) are obtained by reacting a ketone which is known from J. Org. Chem. 35, 715 (1970) and has the formula IX R1

in which R 1 is as defined above with 1,2-epoxy-4-chlorobutane which is known from Liebigs Ann. Chem. 596, 141-2 (1955) and has the formula X-8- > / -8- > / -

Nor / JF / 20753

in a manner known per se. in the presence of a solvent and in the presence of a catalyst (as described in React Kinet, Catt., 1981, 17 (3-4), 281-6.

Suitable solvents are, eg, 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 a > 2 atomic group such as sulfur dioxide, dimethyl sulphone or sulfolane itself.

Suitable catalysts may be metal halides such as FeCl 3, TiCl 4, AlCl 3, ZnCl 2, NiBr 2, PdBr 2, AIF 3, SbF 3, Cul and the like, or boron and silicon halides such as BF 3, BBr 3 and S 1 Cl 4 or a acid silicate, such as bentonite, montmorillonite and the like, which may optionally be activated by acid treatment and / or ion exchange and / or drying. Two examples of catalysts used are BF3 added in complex form with ethyl ether and aluminum activated bentonite. The catalyst may be used in an amount of 0.1 to 50% by weight, preferably 1 to 10% by weight.

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

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

The ketals of formula IV in which Z = OCH2 CH3, the ketals of formula IV in which Z = Cl or Br, and the ketal alcohols of formula V are novel compounds and are also the object of the present invention under N 74 / / 20753 -9-

the form of an intermediate product and a starting material as set forth in claims 4 and 5, respectively.

The novel alkoxyaminocetials of formula I have been found to have fungicidal properties. Surprisingly, the alkoxyaminoalkyls of the general formula I according to the invention exhibit higher fungicidal activity than the known alkoxyaminomethioxolanes of the prior art, for example 2- (N-ethyl-N-2-methoxyethylaminoethyl) -8- (1,1- 1-dimethylethyl) -1,4-dioxaspiro [4.5] decane, 2- (N-propyl-N- (2-oxolanylmethyl) -aminomethyl) -8- (1,1-dimethylethyl) -1,4- dioxaspiro [4,5] decane and 2- (N-2-methoxyethylaminoethyl) -8- (1,1-dimethylethyl) -1,4-dioxaespiro [4,5] decane, which are, from the chemical and activity, closely linked compounds.

The active substances of the present invention may be used in practice in the control of phytopathogenic fungi, for example Plasmodiophomycetes, Citrityomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and Deuteromycetes.

The active substances of the present invention may be used, e.g., in the control of diseases of plants Puccinia recondita, Puccinia striiformis and other diseases of wheat rust, Puccinia hordei. Puccinia striiformis and other diseases of rust on barley and rust on other host plants such as coffee, apple, vegetables and ornamental plants. Ervsiohe qraminis (mildew) in barley and wheat and other species of true downy mildew in various host plants, such as Sphaerotheca fuliainea in cucumber, Podosphaera leucotricha in apples and Uncinula necator in vines. Species Helminthospo-rium, e.g., Pyrenophora teres (bark rash) on barley. Species Rhvnchosporium and Pseudocercosporella herpotrichoides Λ '/ 74 076 Nor / JF / 20753 -10- / -γ >'

Ϊ0 in cereals. Cercospora arachidicola in peanuts and other Cercospora species in, for example, sugar beet, banana and soya bean. Botrytis cinerea (gray mold) on tomatoes, strawberries, vines and other host plants; venturia inaeaualis (crust) on apples. Pyricularia orvzae in rice.

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

The active substances are active as seed coating agents against Fusarium species. Septoria. Til-letia. Ustilago, Helminthosporium and Pseudocercosporella herpotri-choides on Rhizoctonia solani cereals on cotton and Corticium sa-sakii on rice.

In addition to excellent curative activity, the active substances of the present invention also show extremely good protective properties as well as systemic activity.

In addition, some of the compounds are sufficiently volatile to be active in the gas phase against fungi in plants.

The compounds may also be useful as industrial (other than agricultural) fungicides, e.g., in the prevention of fungal attacks on wood, hides, skins and especially paint films.

The compounds are also useful in the treatment of fungal infections in humans, for example, candidiasis and dermatophyte infections.

In accordance with the foregoing, the present invention also describes a fungicidal composition, particularly a fungicidal composition for plants, and, more particularly, a fungicidal composition for cereals, for combating mildew, rust and other significant diseases of foliage, which composition is characterized in that it contains, as the active component,

Nor / JF / 20753 11-

.

less a compound selected from the aminoethylcellals of formula I above.

In addition, the present invention relates to the use of an aminoethylketal of formula I above to combat fungi, particularly phytopathogenic fungi, and more particularly, mildew, rust, and other significant diseases of cereal foliage.

In addition, the present invention relates to a process for combating fungi, particularly phytopathogenic fungi, and more particularly, mildew, rust, and other significant diseases of cereal foliage, which process is characterized in that a aminoethylketal of formula 1 will affect the fungi in question and / or their biotope.

The compounds may be applied in various ways. For example, they can be applied, formulated or unformulated, directly onto the foliage of a plant, or can be applied to shrubs and trees, seeds or other means where plants, shrubs or trees are growing or will be planted , or they may be vaporized, sprayed or applied in the form of a cream or paste formulation, or they may be applied in the form of steam, or in the form of slow release granules. The application can be made anywhere on the plant, shrub or tree, for example in the foliage, stems, branches or roots, or in the soil in the vicinity of the roots, or in the seed before being planted or in the soil in general, in the water or in hydroponic farming systems. The compounds of the present invention may also be injected into plants or trees and may also be sprayed into the vegetation using electrodynamic spray techniques. The present invention further relates to a process for the preparation of a fungicidal composition, particularly a fungicidal composition for plants and more particularly a fungicidal composition for cereals, for combating mildew, rust and other significant diseases of the foliage, process 74 076

Which is characterized in that an aminoethylketal of formula I is mixed with one or more agents selected from extenders, surfactants and other conventional auxiliaries. The compositions may be in the form of 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, plaster, Hewitt earth, diatomaceous earth and China clay. These granules may be preformed granules suitable for application to the soil without any further treatment. These granules can be prepared either by impregnating filler pellets with the active ingredient, or by preparing the pellets from a mixture of active ingredient and powder filler. Seed coating compositions, for example, may comprise an agent (for example a mineral oil) to aid adhesion of the composition to the seed. Alternatively the active ingredient may be formulated for seed coating 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 dispersion in liquids of the powder or granules which may also contain fillers and suspending agents.

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 agents or emulsifiers. Suitable organic solvents include ethylene dichloride, isopropyl alcohol, propylene glycol, diacetone alcohol, toluene, kerosene, methylnaphthalene, xylenes, trichlorethylene, furfuryl alcohol, tetrahydrofurfuryl alcohol and glycol ethers (eg, 2-ethoxyethanol and 076

Nor / JF / 20753 2-butoxyethanol).

The vaporization compositions may also be in the form of aerosols in which the formulation is maintained in a vessel under pressure in the presence of a propellant, e.g. fluorotrichloromethane or dichlorodifluoromethane.

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

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

Including suitable additives, for example additives for improving the distribution, adhesive power and rain resistance on the treated surfaces, the different compositions may be better adapted for the various uses.

The compounds may be used in mixtures with fertilizers (e.g., fertilizers containing nitrogen, potassium, or phosphorus). Preferred are compositions comprising only fertilizer granules incorporating the compound (for example, coated therewith). These granules suitably contain up to 25% by weight of the compound. Accordingly, the present invention also provides a fertilizer composition comprising the compound of formula I.

The compositions may also be in the form of liquid preparations for use in baths or sprays which are generally aqueous dispersions or emulsions containing the active ingredient in the presence of one or more surfactants, eg, wetting agents, dispersing agents, emulsifiers or suspending agents, or which are vaporization formulations of the type suitable for use in electrodynamic vaporization techniques. Previous agents

Mp 74 076

Nor can be cationic, anionic or non-ionic. Suitable cationic agents include the quaternary ammonium compounds, for example, cetyltrimethylammonium bromide.

Suitable anionic agents include soaps, sulfuric acid aliphatic monoesters salts (for example sodium lauryl sulfate) and salts of sulfonated aromatic compounds (e.g., sodium dodecylbenzenesulfonate, sodium lignosulfonate, calcium or ammonium, butylnaphthalenesulfonate and a mixture of di -isopropyl- and sodium triisopropylnaphthalenesulfonates).

Suitable nonionic agents include 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 nonionic agents are the partial esters derived from long chain fatty acids and hexitol anhydrides, the condensation products of said partial esters with ethylene oxide and lecithins. Suitable suspending agents include hydrophilic colloids (for example, polyvinylpyrrolidone and sodium carboxymethylcellulose), and vegetable gums (for example acacia gum and tragacanth gum).

Compositions for use in the form of aqueous dispersions or emulsions are generally provided in the form of a concentrate containing a high proportion of the active ingredient (s) and the concentrate is diluted with water prior to use. These concentrates are sometimes able to remain in storage for prolonged periods and after such storage can be diluted with water to form aqueous preparations which remain homogeneous long enough to be able 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 arylsulfonic acids such as xylenesulfonic acid or N, N,

dodecylbenzenesulfonic acid) since the presence of these acids may increase the solubility of the active ingredients in the polar solvents often used in the concentrates. The concentrates also suitably contain a high proportion of surfactants so that sufficiently stable emulsions in water can be obtained. After dilution to form the aqueous preparations, these preparations may contain various amounts of active ingredients depending on the intended purpose, but an aqueous preparation containing 0.0005% or 0.01% to 10% by weight active ingredient may be used.

The compositions of the present invention may also comprise other compounds having biological activity, e.g., compounds having similar or complementary fungicidal activity, or compounds having activity in plant growth regulation, herbicidal activity or insecticide. The other fungicidal compound may be, for example, one that is able to combat diseases in the ear of cereals (e.g. wheat) such as those of Septoria species. Gibberella and Helminthosnorium. seed and soil diseases, mild and powdery mildews in vines and powdery mildew and crust on apples, etc. These fungicidal mixtures may have a broader spectrum of activity than the compound of formula I alone. In addition, the other fungicides may have a synergistic effect on the fungicidal activity of the compound of formula I.

Examples of other fungicides include carbendazim, benomyl, thiobendazole, fuberidazole, etridazole, diclofluanid, cymoxanyl, oxadixyl, ofurazo, metalaxyl, furalaxyl, benalaxyl, alumino-foseyl, fenarimol, iprodione, procymidione, vinclozoline, penconazole, myclobutanyl, R0151297, S3308, pyrazophos, ethyrimol, ditalimphos, tridemorph, triforine, nuarimol, triazbutyl, guazatine, 1,1'-imidodi- (octamethylene) -diguanidine triacetate salt, propiconazole, prochloraz, flutriafol, hexaconazole, ie 1- ( 1,2,4-triazol-1-yl) -2- (2,4-dichlorophenyl) hexan-2-ol, 747-675 DPX H6573 (1- (2RS, 3RS) -2- (4-chlorophenyl) -3-methyl-1H-1,2,4-triazole, triadimenol, diclobutrazol, fenpropimorph, cyclopropyl-1- (1H-1,2,4-triazol-1-yl) butan-2-ol, (RS) -1- (4-chlorophenyl) -4,4-dimethyl-3- 1H-1,2,4-triazol-1-ylmethyl) -pentan-3-ol, 4-chloro-N- (cyano (ethoxy) methyl) benzamide, fenpropidine, chloro-linate # dini conazol, imizalyl, fenfuram, carboxy, oxycarboxine, metfuroxamo, dodemorfo, BAS 454, blasticidin S, kasugamycin, edifenfos, chitazin P, cycloheximide, phthalide, probenazole, isoprothiolane, tricyclazole, pyroquilone, chlorbenzothiazone, neoasozine, polyoxine D, validamycin A , mepronyl, flutolanil, pencycurone, diclomezine, fenazineoxide, nickel dimethyldithiocarbamate, teclophthalam, bitertolol, bupi-rimate, etaconazole, streptomycin, cypfuram, biloxazole, quinthionate, dimethyrimol, 1- (2-cyano-2-methoxyiminoacetyl) -3 -ethyl urea, phenapanyl, tolclofosmethyl, piroxifur, poliramo, manebo, mancozebo, captafol, chlorothalonil, anilazine, tiramo, captan, folpet, zinebo, propinebo, sulfur, dinocapo, binapacryl, nitrotalisopropyl, dodine, dithianone, fentin hydroxide, fenton acetate, tecnazene, quintozene, dichloran, copper containing compounds such as copper oxychloride, copper sulfate and Bordeaux mixture as well as organic mercury compounds.

The compounds of formula I may be mixed with the soil, with peat or other planting media to protect against diseases caused by fungi, seeds, soils or foliage.

Suitable insecticides which may be incorporated into the composition of the present invention include pyrimicarb, dimethoate, demeton-methyl, formothion, carbaryl, isoprocarb, XMC, BPMC, carbofuran, carbosulfan, diazinone, fention, fenitrothione, phentoate, chlorpyrifos, isoxationa, propafos, monocrotophos, buprofezine, etoproxyfen and cycloprotrin.

Plant growth regulating compounds for use in the compositions of the invention are compounds which control the herbs 74 076 Nor / JF / 20753 ϊΗ

/ '·' And / is' " and &

Or selectively control the growth of less desirable plants (e.g., herbs).

Examples of plant growth regulating compounds, suitable for use in the compositions of the invention, are gibberellins (eg GA3, GA4 or GA7), auxins (eg indole acetic acid, indole butyric acid, naphthoxyacetic acid or naphthylacetic acid), cytokinins (eg, quinetine, diphenylurea, benzimidazole, benzyladenine or benzylaminopurine), phenoxyacetic acids (eg 2,4-D or NCPA), substituted benzoic acids (eg triiodobenzoic acid), morphantins (eg chlorfluorecol), maleic hydrazide, glyphosate, glyphosine , alcohols and long chain fatty acids, dikegulate, paclobutrazol, fluoropentol fluoridamide, mefluide, substituted ammonium and phosphonium quaternary compounds (eg chlormequat, chlorphonium or mepiquat chloride), ethephon, carbetamide, methyl 3,6-dichloroanisate, daminozide, asulam, absisic acid, isopyrimol, 1- (4-chlorophenyl) -4,6-dimethyl-2-oxo-1,2-dihydropyridine-3-carboxylic acid, and hydroxybenzonitriles (eg, moxinyl), difenzoquate, benzoylprop-ethyl, 3,6-dichloropicolinic acid, fenpentezol, inabenfide, triapentenol and tecnazene. The invention is best illustrated by the following Preparations, Preparation Examples and Application Examples

Preparation 1

Preparation of intermediate 2- (2-methanesulfonyloxyethyl) -8- (1,1-dimethylethyl) -1,4-dioxaspiro [4.51] deeno-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) in an ice bath, while dropwise addition of a solution of methanesulfonyl chloride (7.5 g, 0.066 mol) in methylene chloride (15 ml) at a rate such that the temperature does not exceed 15 ° C. After the dropwise addition was complete,

The residue resulting from the evaporation is redissolved in methyl t-butyl ether (150 ml) and extracted with water (2 x 100 ml), dried over anhydrous sodium sulfate ) The organic phase is separated, dried over sodium sulfate and evaporated in vacuo to give a viscous oil of 1.4848 g.

D obtained is used without further purification for other reactions.

Preparation 2

Preparation of the starting material 2- (2-hydroxyethyl) -8- (1,1-dimethylethyl) -1,4-dioxaspiro [4,5] decan-

A mixture of 4- (1,1-dimethylethyl) -1-methoxy-cyclohexa-1,4-diene (16.6 g, 0.1 mol), 1,2,3,4- 4-butanetriol (10.6 g, 0.1 mol) and p-toluenesulfonic acid (100 mg), dissolved in toluene (120 ml), and simultaneously removing the formed methanol through a water separator . Two hours after gas chromatographic analysis the reaction is complete. The reaction mixture is cooled to room temperature and triethylamine (1 ml) is added, in order to neutralize the acid catalyst. The extraction is carried out with water (100 ml) and the organic phase is separated, dried over sodium sulfate and evaporated in vacuo. The resulting oil is purified by distillation. Yield: 12.7 g (53%) of a colorless oil of boiling point 170øC / 10 mm Hg; n26: 1.4812.

D

The ketal-alcohols below are prepared in a similar manner

Refractive index (26C) 1.4866 -19-74 076 Nor / JF / 20753

Refractive index (26C) 1.4952 Refractive index (26C) 1.4911

Preparation 3

Preparation of the starting material 2- (2-chloro-ethyl) -8- (1,1-dimethylethyl) -1,4-dioxaespiro [4.5] decan-

Cl

A mixture of 4- (1,1-dimethylethyl) -3-cyclohexen-1-one (10.4 g, 0.068 mol) is heated with 3 g of aluminum-activated montmorillonite K 10 in toluene (30 ml). ml) under vigorous stirring to 60 ° C. To this mixture is added dropwise a solution of 1,2-epoxy-4-chlorobutane (8.75 g, 0.082 mol) in toluene (15 ml) over 30 minutes. The reaction mixture is then held at 60 ° C for 1 hour and then heated at reflux for an additional 1 hour, then the catalyst is withdrawn by filtration on a filter paper and the filtrate is evaporated in vacuo. The resulting oil is purified by distillation. Yield 6.1 g (37%) of an oil of boiling point 150-156 ° C / 10 mm Hg: n26: 1.4847.

D

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Preparation Example 1

Preparation of 2- (2- (N-ethyl-N- (2-oxolanylmethyl) aminoethyl) -8- (1,1,2-trimethylpropyl) -1,4-dioxaespiro [4,5] decane, compound 48_

A mixture of 2- (2-chloroethyl) -8- (1,1,2-trimethylpropyl) -1,4-dioxaspiro [4.5] decane (1.73 g, 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) ). 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 and dried over sodium sulfate and evaporated in vacuo. The resulting oil is purified by Kugelrohr distillation. Yield 1.83 g (80%) of a viscous oil of boiling point 230 ° C / 0.01 mm Hg; n26: 1.4838.

D

Example 2 Preparation 2

Preparation of 2- (2- (N- (2-methoxyethyl) -N-propyl) -aminoethyl) -8- (1,1-dimethylethyl) -1,4-dioxaspiro4.51-decane, compound 3

A mixture of 2- (2-methanesulfonyloxyethyl) -8- (1,1-dimethylethyl) -1,4-dioxaspiro [4.5] decane (3.20 g, 0.01 mol) mol) and N- (2-methoxyethyl) -N-propylamine (3.51 g, 0.03 mol). The autoclave is heated to 150Â ° C and held at said temperature for one hour. After cooling to room temperature the reaction mixture is poured into 5% aqueous sodium carbonate solution (50 ml) and extracted with methyl t-butyl ether (100 ml). The organic phase is separated, dried over sodium sulfate and evaporated in vacuo. The residual oil is purified by Kugelrohr distillation. Yield: 2.39 g (70%) of a viscous oil of boiling point 170øC / 0.08 mm Hg; n26: 1.4653.

D 74 076 Nor / JF / 20753

Exemplary of Preparation 3

Preparation of 2- (2- (N-allyl-N- (3-methoxypropyl)) aminoethyl-8- (1,1-dimethylethyl) -1,4-dioxaspiro [4,5] decene-7, compound na 47

A mixture of 2- (2-methanesulfonyloxyethyl) -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 ). Processing of the reaction mixture is performed as set forth in Preparation Example 1. Yield 1.30 g (62%) of a viscous oil of boiling point 175øC / 0.01 mm Hg; n26: 1.4802.

D

Preparation Example 4

Preparation of 2- (2- (N- (2-methoxyethyl) -N-propyl) aminoethyl) -8- (1,1-dimethylethyl) -1,4-dioxaspiro [4.5] decene-7, compound ns 41_

The mixture of 2- (chloroethyl) -8- (1,1-dimethyl-ethyl) -1,4-dioxaspiro [4,5] decene-7 (1.55 g, , Sodium iodide (0.2 g) and potassium carbonate (2.5 g) in diethyleneglycol dimethyl ether (diglyme, methanol, 15 ml). Processing of the reaction mixture is performed as set forth in Preparation Example 1. Yield: 1.12 g (55%) of a viscous oil of boiling point 190øC / 0.01 mm Hg; n26: 1.4746.

D

According to the present invention, the alkoxyaminocethers of formula I are exemplified by the specific examples of compounds as shown in the following Table 1, in which the term Refractive index (26 ° C) is identical to the index of

Refraction n26.

D

74/06 / JF / 20753 -22-TABLE I C / F).

No. 1No.2No.3No.4No.5No. 6No.7No. 8No.

Refractive index (26 ° C) 1.4681 Refractive index (26 ° C) 1.4729

Refractive Index (2 ° C) 1.4653 9

Refractive index (26 ° C) 1.4715 Refraction index (26 ° C) 1.4708 Refraction index (26 ° C) 1.4723 Refraction index (26 ° C) 1.4731 Refraction index (26 ° C) C) 1.4711 Refractive index (26 <1. C) 1.4786

74 076

(26 ° C) 1.4779 No. / 11 0J Refractive Index (26 ° C) 1.4890 No. 12 Refractive Index (%) 26 ° C) 1.4813 No. I 13 Index of Refraction (26 ° C) 0- * 1.4800 No. 14 ^ 0 ij} 0J Refractive Index (26 ° C) 1.4910 No. 15 Refractive Index (26 ° C) 1.4658 No. 16 / Ό- * Refractive index (26 ° C) 1.4690 No. 17 Q-! Refractive index (26 ° C) 1.4673 No. 18 CM Index of Refraction (26 ° C) 1.4670 74 076

Nor / JF / 20753

Refractive Index (26 ° C) 1) 4727 Refractive Index (26 ° C) 1.4782 Refractive Index (26 ° C) 1.4656 Refraction Index (26 ° C) 1.4650 Refraction Index (26 ° C) C) 1.4708 Refraction index (26 ° C) 1.4726 25 No.26 No.27

Refractive index (26 ° C) 1.4732 Refraction index (26 ° C) 1.4705

index of Refraction at 26 ° C) 1.4700 74 076 Nor / JF / 20753 / l

-25-

Refractive Index (26 ° C) 1.4707 Refraction Index (26 ° C) 1.4761 Refraction Index (26 ° C) 1.4758 Refraction Index (26 ° C) 1.4810 Refraction Index (26 ° C) 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 74 076 Nor / JF / 20753 -26-

.. and \

No.37No.38No.39No.40No.41

Refractive index (26 ° C) 1.4704 Refraction index (26 ° C) 1.4698 Refraction index (26 ° C) 1.4758 Refraction index <26 ° C) 1.4752 Refraction index ° C) 1.4746

Refractive index (26 ° C) 1.4737 Refractive index (26 ° C) 1.4731 Refractive index (26 ° C) 1.4784 Refraction index (2 ° C) 1.4791 74 076 Nor / JF / 20753 Γ / fí /: Ojsaae · · &amp; -27-

No. 46 No. 47 No. 48 No. 49 No. 50 No. 51 No. 52 No. 53 No. 54

Refractive Index (26 ° C) 1.4759 Refraction Index (26 ° C) 1.4766 Refraction Index (26 ° C) ) 1.4839 Refractive Index (26 ° C) 1.4768 Refractive Index (26 ° C) 1.4744 -28- Nor / JF / 20753

(26 ° C) 1.4740 Refraction Index (26 ° C) 1.4732 Refraction Index (26 ° C) 1.4788 Refraction Index (26 ° C) 1.4706 Refraction Index (26 ° C) C) 1.4701 Refractive index (26 ° C) 1.4759 Refractive index (26 ° C &lt; 1.4804 Refractive index (26 ° C) 1.4690 Refraction index (26 ° C) 1.4684 - 29-74 076

Nor / JF / 20753

No. 64 oJ Refractive Index (26 ° C) 1.4737 No. 65 QJ Refractive Index (26 ° C) 1.4753 No. 66 oJ Refractive Index (260C) 1.4712 No./v / 67 of Refractive index (26 ° C) 1.4711 No. s / 68 0- &gt; Refractive Index (26 ° C) 1.4680 No. 69 Refractive Index (26 ° C) 1.4739 No. JL, 70 Refractive Index (26 ° C) 1.4737 No. 71 Refractive Index (26 ° C) C) 1.4705 No. 72 Refractive index (26 ° C) 1.4702 74.076 Nor / JF / 20753 -30-

Ct-

Refractive Index (26 ° C) 1.4671 Refraction Index (26 ° C) 1.4703 Refraction Index (26 ° C) 1.4701 Refraction Index (26 ° C) 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 74 076 Nor / JF / 20753 &quot; /:

No. 82 No. 83 No. 83 No. 85 No. No. 86 No. No. No. No. No. No. No. No. No. No. No. No. No. (26 ° C) 1.4784 Refractive Index (26 ° C) 1.4736 Refractive Index (26 ° C) 1.4720 Refractive Index (26 ° C) ° C) 1.4780 Refractive Index (26 ° C) 1.4768 Refractive Index (26 ° C) 1.4825 Refractive Index (2 ° C) 1.4844 Refractive Index (26 ° C) 1.4711 Refractive index (26 ° C) 1.4798 74 076 Nor / JF / 20753 -32-

P

No.91 No.92 No.93 No.94 No.95No.96No.97 No.98No.99

The N &quot; Refraction index (26 ° C) 1.4709

No. &quot; Refractive index (26 ° C) 1.4710

Refractive Index (26 ° C) 1.4830 Refractive Index (26 ° C) 1.4743 Refractive Index (26 ° C) 1.4745 ° C Refractive Index (2 ° C) 1.4750

(26 ° C) 1.4803 Refractive Index (26 ° C) 1.4794 AÀ 74626 Nor / JF / 20753

..A * / A '

(1)

No.100 No. 101 No.102 No. 103 No. 104 No. 105

Refractive Index (26 ° C) 1.4724 Refractive Index (26 ° C) 1.4870 Refractive Index (26 ° C) 1.4939

oCHO, Refractive Index (26 ° C), 1.4745

No. 106 No. 107 No. 108

(26 ° C) 1.4708 Refraction Index (26 ° C) 1.4677 Refraction Index (26 ° C) 1.4702 Refraction Index (26 ° C) 1.4682 Refraction Index (26 ° C) C) 1.4732 -34- Nor / JF / 20753

Refractive Index (26 ° C) 1.4724 Refraction Index (26 ° C) 1.4655 Refraction Index (26 ° C) 1.4686 Refraction Index (26 ° C) C) 1.4689 Refraction Index (26 ° C) 1.4719 Refraction Index (26 ° C) 1.4721 Refraction Index (26 ° C) 1.4649 Refraction Index (26 ° C) 1.4681 / V-35-% 74 076 Nor / JF / 20753

Refractive Index (26 ° C) 1.4711 Refractive Index (26 ° C) 1.4780 Refractive Index (26 ° C) 1.4780 Refractive Index (26 ° C) , 4858 Refractive Index (26 ° C) 1.4888 Refractive Index (26 ° C) 1.4713 Refractive Index (26 ° C) 1.4736 Refractive Index C26 ° C) 1.4734 4 -36% 74 076

Nor / JF / 20753

Refractive index (26 ° C) 1.4733 Refraction index (26 ° C) 1.4768 Refraction index (26 ° C) 1.4725 Refraction index (26 ° C) 1.4751 Refraction index ° 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 -37- 74 076 //

Nor / JF / 20753

No. 136 CM Refractive Index (26 ° C) 1.4750 No. 137 Λν -, Refractive Index (26 ° C) 1.4781 No. 138 0 - * Refractive Index (26 ° C) 1.4796 No. 139 0J Refractive Index (26 ° C) 1.4821 No. 140 o Refractive Index (26 ° C) 1.4815 No. 141 o Refractive Index (26 ° C) 1.4814 No. 142 o Index of Refraction (26 ° C) 1.4850 No. 143 (° C) Refractive Index (26 ° C) 1.4843 No. 144% ° C) 1.4641 -38- 74 076

Nor / JF / 20753

No.145

Refractive index (26 ° C) 1.4672

No.148

No. 149 Refractive Index (26Â ° C) Refractive Index (26Â ° C) 0.J_1.4857

No. 150 j / W Refractive index &lt; 26 ° C) _1.4846_

No. Refractive Index (26 ° C) 151 1.4880 No. 152 0 -i Refractive Index (26 ° C) 1.4666 Refractive Index No. (26 ° C) 153 1.4696 74 076 Nor / JF / 20753 /

Yes

No. 158

Refractive index (26 ° C) 1.4834

No. 159 o Refractive Index (26 ° C) 1.4789 No. 160 Refractive Index (26 ° C) 1.4821 No. 161 o Refractive Index (26 ° C) 1.4799 No. 162 o - / refractive index (26 ° C) 1.4833 74 076 Nor / JF / 20753 -40-

.i: 4 '

No. 163 CM Refractive Index (26 ° C) 1.4828 No. 164 ° C Refractive Index (26 ° C) 1.4767 No. 165 CM Refractive Index (26 ° C) 1.4796 No. 166 No. of Refraction Index (26Â ° C) 1.4819 No. 167 No. of Refraction Index (26Â ° C) 1.4773 No. 168 CM index of Refraction (26Â ° C) 1.4873 No. 169/460 Refractive Index (26Â ° C) 1.4811 No. 170 / 1.4795 No. 171 CM Index of Refraction (26 ° C) 1.4813 -41-4: Ϋ :: rL'.® 25 74 076

Nor / JF / 20753

No. Refractive Index (26 ° C) 172 CM 1.4765 No. 173 CM Refractive Index (26 ° C) 1.4870 No. 174 // Q <y-Cc> O-1 Refractive Index (26 ° C) 1.4936 No. 175 CM Refractive Index (26 ° C) 1.4789 No. I. 176 ° C Refractive index (26 ° C) 1.4871 No. Ref. No. (26 ° C) 1.4857 No. μ3 ° -τ-ν '0- 178 Refractive Index (26 ° C) 1.4839 No. 179 Refractive Index (26 ° C) 1.4919 No. 1 180 Refractive Index (26 ° C) 1.4868 74 076

Nor / JF / 20753 -42-

'' ~ τ ~ T &quot; eur-lex.europa.eu eur-lex.europa.eu

No. 181 o Refractive index (26 ° C) 1.4858 No. 182 Refractive index (26 ° C) 1.4867 No. oj 183 Refractive index (26 ° C) 1.4826 No. ^ Qo ^ Cq 0J 184 Refraction index ( 26 ° C) 1.4938 No. 185 ° C Refractive index (26 ° C) 1,5001 No. 186 ° C. (26 ° C) 1.4871 No. 187 o Refractive Index (26 ° C) 1.4808 No. 188 O-Refractive Index <26 ° C) 1.4710 No. 189 o &quot; index of refraction (26 ° C) 1.4802 74 076 Nor / JF / 20753 0 / .. -43-: Ί _

No. 190

index of Refraction (26'C) 1.4752

No. 191

Refractive index (26 ° C) 1.4710

No. 192

# Refractive index (26 ° C) 1.4799

No. 193

No. 194

Refractive index (26 ° C) 1.4851 Refractive index (26 ° C) 1.4840

No. 195

Refractive index (26 ° C) 1.4710

No. 196

Refractive index (26 ° C) 1.4837_

No. 197

At the.

Refractive index (26 ° C) 1.4768 Refraction index (26 ° C) 1.4767 -r --- 198

^ ΜίΜβΚί® *. ' a. 74 076

Nor / JF / 20753 -44-

No. Refraction Index (26 ° C) 1.4721 No. 200 Refraction Index (26 ° C) 1.4898 No. 201 Refraction Index (26 ° C) 1.4779 No. 202 Hi Refraction Index 26 ° C) 1.4781 No. 203 Refractive index (26 ° C) 1.4791 No. 203 CH3 OCHO, refractive index (26 ° C) 1.4817 No. 205 (26 ° C) 1.4789 No. 206, Refractive Index (26 ° C), 1.4716, No. 207, and COCH3 OCH3. refractive index (26 ° C) 1.4746 74 076 Nor / JF / 20753 -45-

Sj

No. 208 0 CH, (OCH, Refractive Index (26 ° C) 1.4778 No. 209) Refractive index (26 ° C) 1.4785 No. 210 Y Ç> CH / Refractive Index (26 ° C) 1.4810 No. 212 CH Refractive Index (26 ° C) 1.4659 No. 211 Refractive index (26 ° C) 1.4690 No. 214 CM Refractive index (26 ° C) 1.4742 No. 213 / ) 1.4838 No. 215 AG., Y OCH, l ^ r0Y''V ~ 'NY'OCH, CM Refractive index (26 ° C) 1,4722 No. 216 ^^ Qo-Χς) Refraction index ( 26 ° C) 1.4808. 74 076

Nor / JF / 20753 -46- d1

No.217

OCH, Refractive index (26 ° C)

No. 218 Refractive Index (26 ° C) 1.4656 No. 219 0J Refractive Index (26 ° C) 1.4676 No. 220 Refractive Index (26 ° C) 1.4655 No. 221 ol Refractive Index (26 ° C) 1.4690 No. 222 ° C Refractive Index (26 ° C) 1.4704 No. 223 / 4688 No. 224 Refractive Index (2 ° C) 1.4688 No. 225 Refractive Index (26 ° C) 1.4703 74 076 Nor / JF / 20753 -47-

0

No. 229

No. 230

Refractive index (26 ° C) 1.4720

No. 231

index of Refraction (26 ° C) 1.4687_

No. 232 Refractive Index (26 ° C) 1.4702 No. 233 Refractive Index (26 ° C) 1.4794

Refractive index (26 ° C) 1.4790_ -48- 74 076

Nor / JF / 20753

No. 235 Refractive Index (26 ° C) 1.4804 No. 237 0J Refractive Index (26 ° C) 1.4759 No. (26 ° C) 1.4787 No. 239 Refractive Index (26 ° C) 1.4786 No. 240 O Refractive Index (26 ° C) 1.4787 ν 74 076 - Θ -.7.

Nor / JF / 20753

APPLICATION EXAMPLES

In the following Examples of Application the compounds mentioned below and known from Danish Patent Application No. 1201/88 (EP-A-281,842) are used as comparison compounds. 2- (N-ethyl-N-2-methoxyethyl) aminomethyl) -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

2- (γ-2-methoxyethylaminomethyl) -8- (1,1-dimethylethyl) -1,4-dioxaspiro [4,5] decane

74 076 Nor / JF / 20753

-6-

Application Example 1

Erysiphe qraminis hordei (Barley Mildew)

Curative spraying of new barley plants

Solvent: 10% acetone in water.

Emulsifier: Triton X-155, 100 ppm

In order to prepare a suitable active substance composition, the active substance is dissolved in said solvent with the emulsifier to the desired concentration. Further dilution is performed through a solution containing 10% acetone in water and 100 ppm Triton X-155.

To test the curative activity, fresh barley plants are sprayed until the leaves are wetted with the active ingredient composition two days after the plants have been inoculated with mildew conidia by the brushing method. After inoculation and until spraying the plants are left at 18 ° C and 100% RH and then sprayed are left in a growth chamber at a temperature of 18 ° C and 70-80% RH.

The activity of the substance is evaluated seven days after inoculation. A clear superiority of activity relative to the state of the art is shown by the compounds according to Examples 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.

Nor / JF / 20753

Application Example 2

Test: Puccinia recôndita (wheat, protective spray)

Solvent: 10% acetone in water. Emulsifier: Triton X-155, 100 ppm

In order to prepare a suitable active substance composition, the active substance is dissolved in said solvent with the emulsifier to the desired concentration. Further dilution is carried out through a solution containing 10% acetone in water and 100 ppm Triton X-155 .

To test the protective activity, fresh wheat plants are sprayed until the leaves are wetted with the active substance composition. After drying the plants are inoculated with brown rust spores in an aqueous suspension which is sprayed on top. The plants are left for 48 hours at 18 ° C and 100% RH, and are then transferred to a growth chamber at the same temperature and 70-80 HR.

The activity of the substances is evaluated ten days after inoculation. An obvious superiority of activity relative to the state of the art is shown by the compounds according to the present invention.

Examples 2, 3, 4, 5, 6, HO 11, 14, 16, 17, co H 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.

Nor / JF / 20753

Application Example 3

Ervsiohe araminis tritici (Wheat millet)

Curative spraying of new wheat plants

Solvent: 10% acetone in water.

Emulsifier: Triton X-155, 100 ppm

In order to prepare a suitable active substance composition, the active substance is dissolved in said solvent with the emulsifier to the desired concentration. Further dilution is performed through a solution containing 10% acetone in water and 100 ppm Triton X-155.

To test the curative activity, fresh wheat plants are sprayed until the leaves are wetted with the active substance composition 24 hours after the plants have been inoculated with mildew conidia by the brushing method. After inoculation and until spraying the plants are left at 18 ° C and 100% RH, and after spraying are left in a growth chamber at a temperature of 18 ° C and 70-80% RH.

The activity of the substance is evaluated eight days after inoculation. A clear superiority of activity relative to the state of the art is shown by the compounds according to Examples 2, 3, 4, 5, 6, 7, 8, 13, 23, 24, 30, 31, 32, 36, 38, 39, 44, 53, 57, 58, 65, 66, 72. 74 076

Nor / JF / 20753 The test results (EDgo) obtained according to Application Examples 2 and 3 are synthesized in Table 2 below

Table 2: BIOLOGICAL TESTS

Comp. Puccinia NE recondite (wheat)

Comp. Puccinia N2 recondite (wheat)

Erysiphe graminis tritici (wheat) Erysiphe graminis tritici (wheat) ED90 (PPm) ED90 (PPm) ED50 (PPm) ED50 (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 S - 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 &lt; 2 88 32 4 34 32 4 89 32 4 35 64 4 90 32 2 36 64 2 91 32 4 37 32 &lt; 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 74 076 Nor / JF / 20753 -54

Table 2: BIOLOGICAL TESTS (cont.)

Comp. N2 Puccinia recôndita (wheat) EDgo (ppm) Erysiphe graminis tritici (wheat) EDg0 (PPm) Comp. N2 Puccinia recondite (wheat) ED90 <PPm) Erysiphe graminis tritici (wheat) EDg 0 (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 - Compounds A, B and C are comparison compounds and are, respectively, compounds identical to those in Nos. 74, 143 and 42, according to EP 0 281 842 AI (see 49 of the present disclosure)

Claims (8)

74 076 Nor / JF / 20753 Alkoxyamino-cetainers, characterized in that they have the general formula I wherein A represents a single bond or a double bond, R1 represents a substituent selected from straight or branched chain alkyl having up to 10 carbon atoms, unsubstituted or alkyl substituted cycloalkyl having up to 6 ring carbon atoms and cycloalkylalkyl having up to 10 carbon atoms in the total, R 1 and R 3 are each independently hydrogen, straight or branched chain alkyl having up to 10 carbon atoms, unsubstituted, substituted alkyl, alkoxyalkyl or alkoxyalkyl substituted cycloalkyl, alkenyl having up to 10 carbon atoms, alkynyl, alkoxyalkyl, dialkoxyalkyl, dioxolanylalkyl, oxolanyl, oxolanylalkyl, dioxanylalkyl, furanyl, furanylalkyl or cycloalkylalkyl, wherein at least one of R1 and R3 is an oxygen-containing alkyl or cycloalkyl group , or R1 and R3 when taken together with the nitrogen atom to which they are attached form a saturated or unsaturated heterocyclic ring which is further substituted one, two or three times with alkoxy or alkoxyalkyl groups. General I A process for the preparation of alkoxyaminocetials of formula 74 076 Nor / JF / 20753 in which A, R 1, R 2 and R 3 are as defined in claim 1, characterized in that a ketal of the general formula II R II wherein A and R1 are as defined above and wherein Z represents an electron withdrawing group, exchangeable, with an amine of formula III III wherein R 2 and R 3 are as defined above, 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. A process according to claim 2 for the preparation of compounds of general formula I in which A represents a double bond, characterized in that a ketal of formula II is used wherein A represents a double bond and Z represents a methanesulfonyloxy or a chlorine or bromine atom. Intermediate product for use in the process according to claim 3, characterized in that it has the general formula IV IV wherein R 1 is as defined above and Z '-57- 74 076 Nor / JF / 20753 represents a methanesulfonyloxy group or a chlorine or bromine atom. A starting material for the preparation of an intermediate product according to claim 4 of formula IV in which Z 'represents a methanesulfonyloxy group by reaction with methanesulfonyloxy chloride, characterized in that it has the formula V v wherein R 1 is as defined above. A fungicidal composition, particularly a fungicidal composition for plants, and more particularly a fungicidal composition for cereals for combating mildew, rust and other significant diseases of the foliage, characterized in that it contains as an active component at least one compound selected from the alkoxyaminocetides of formula I as defined in claim 1. Use of an alkoxyaminocetal of formula I as defined in claim 1 for combating fungi, particularly phytopathogenic fungi and more particularly to mildew, rust and other significant diseases of cereal foliage. Process for controlling fungi, particularly phytopathogenic fungi and more particularly to mildew, rust and other diseases of cereal foliage, characterized in that an alkoxyiminocetal of formula I as defined in claim 1 is allowed to affect the fungi concerned and / or your biotope. A process for the preparation of a fungicidal composition, particularly a fungicidal composition for plants and more particularly a fungicidal composition for cereals, for combating mildew, rust and other significant diseases of the foliage, characterized by mixing an alkoxyaminocetal of formula I as defined in claim 1 with one or more agents selected from diluents, surfactants and other conventional auxiliaries. Lisbon, &quot; 2. JUL 1992 By CHEMINOVA AGRO A / S = 0 0FICIAL AGENT =