Alpha-sulfin-and alpha-sulfonamino acid amides

Abstract

The invention relates to α-sulfin- and α-sulfonamino acid amides of the general formula I 1

Description

[0001] The present invention relates to novel α-sulfin- and α-sulfonamino acid amides of formula I below. It relates to the preparation of those substances and to agrochemical compositions comprising at least one of those compounds as active ingredient. The invention relates also to the preparation of the said compositions and to the use of the compounds or of the compositions in controlling or preventing the infestation of plants by phytopathogenic microorganisms, especially fungi.

[0002] The invention relates to α-sulfin- and α-sulfonamino acid amides of the general formula I 2

[0003] including the optical isomers thereof and mixtures of such isomers,

[0004] wherein

[0005] n is a number zero or one;

[0006] R1 is C1-C12alkyl, C1-C12alkyl substituted with C1-C4alkoxy, C1-C4alkylthio, C1-C4alkylsulfonyl, C3-C8cycloalkyl, cyano, C1-C6alkoxycarbonyl, C3-C6alkenyloxycarbonyl or C3-C6alkynyloxycarbonyl; C3-C8cycloalkyl; C2-C12alkenyl; C2-C12alkynyl; C1-C12haloalkyl; or a group NR12R13 wherein R12 and R13 are each independently of the other hydrogen or C1-C6-alkyl, or together are tetra- or penta-methylene;

[0007] R2 and R3 are each independently hydrogen; C1-C8alkyl; C1-C8alkyl substituted with hydroxy, mercapto, C1-C4alkoxy or C1-C4alkylthio; C3-C8alkenyl; C3-C8alkynyl; C3-C8cycloalkyl;

[0008] C3-C8cycloalkyl-C1-C4alkyl; or the two groups R2 and R3 together with the carbon atom to which they are bonded form a three- to eight-membered hydrocarbon ring;

[0009] R4, R5, R6 and R7 are each independently hydrogen or C1-C4alkyl;

[0010] R8 is C1-C6alkyl, C3-C6alkenyl or C3-C6alkynyl;

[0011] R9, R10, R14, R15, R16 and R17 are each independently hydrogen or C1-C4alkyl;

[0012] A is optionally substituted phenyl.

[0013] The above definition the phenyl group of radical A may carry one or more identical or different substituents. Normally not more than three substituents are present at the same time. Examples of the phenyl group are: alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkyl-alkyl, phenyl and phenyl-alkyl, it being possible in turn for all of the preceding groups to carry one or more identical or different halogen atoms; alkoxy; alkenyloxy; alkynyloxy; alkoxyalkyl; haloalkoxy, alkylthio; haloalkylthio; alkylsulfonyl; formyl; alkanoyl; hydroxy; halogen; cyano; nitro; amino; alkylamino; dialkylamino; carboxy; alkoxycarbonyl; alkenyloxycarbonyl; alkynyloxycarbonyl.

[0014] In the above definitions “halogen” includes fluorine, chlorine, bromine and iodine.

[0015] The alkyl, alkenyl and alkynyl radicals may be straight-chain or branched. This applies also to the alkyl, alkenyl or alkynyl parts of other alkyl-, alkenyl- or alkynyl-containing groups.

[0016] Depending upon the number of carbon atoms mentioned, alkyl on its own or as part of another substituent is to be understood as being, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and the isomers thereof, for example isopropyl, isobutyl, tert-butyl or sec-butyl, isopentyl or tert-pentyl.

[0017] Cycloalkyl is, depending upon the number of carbon atoms mentioned, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl.

[0018] Depending upon the number of carbon atoms mentioned, alkenyl as a group or as a structural element of other groups is to be understood as being, for example, vinyl, allyl, 1-propenyl, buten-2-yl, buten-3-yl, penten-1-yl, penten-3-yl, hexen-1-yl, 4-methyl-3-pentenyl or 4-methyl-3-hexenyl.

[0019] Alkynyl as a group or as a structural element of other groups is, for example, ethynyl, propyn-1-yl, propyn-2-yl, butyn-1-yl, butyn-2-yl, 1-methyl-2-butynyl, hexyn-1-yl, 1-ethyl-2-butynyl or octyn-1-yl.

[0020] A haloalkyl group may contain one or more (identical or different) halogen atoms, and for example stands for CHCl2, CH2F, CCl3, CH2Cl, CHF2, CF3, CH2CH2Br, C2Cl5, CH2Br, CHClBr, CF3CH2, etc.

[0021] Where R2 and R3 together with the carbon atom to which they are attached form a hydrocarbon ring the ring corresponds to cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane or cyclooctane

[0022] The presence of at least one asymmetric carbon atom and/or at least one asymmetric oxidized sulfur atom in the compounds of formula I means that the compounds may occur in optically isomeric forms. As a result of the presence of a possible aliphatic C═C double bond, geometric isomerism may also occur. Formula I is intended to include all those possible isomeric forms and mixtures thereof.

[0023] Preferred subgroups of compounds of formula I are those wherein

[0024] n is one; or

[0025] R1 is C1-C12alkyl, C1-C12alkyl substituted with C1-C4alkoxy, C1-C4alkylthio, or C1-C4alkylsulfonyl; C2-C12alkenyl; C2-C12alkynyl; C1-C12haloalkyl; or a group NR12R13 wherein R12 and R13 are each independently of the other hydrogen or C1-C6-alkyl, or together are tetra- or penta-methylene; or

[0026] R1 is C1-C12alkyl, C2-C12alkenyl; C1-C12haloalkyl; or a group NR12R13 wherein R12 and R13 are each independently of the other hydrogen or C1-C6-alkyl; or

[0027] R1 is C1-C4alkyl, C2-C4alkenyl; C1-C4haloalkyl; or C1-C2-dialkylamino; or

[0028] R1 is C1-C4alkyl, vinyl; C1-C4haloalkyl; or dimethylamino; or

[0029] R2 is hydrogen and R3 is C1-C8alkyl; C1-C8alkyl substituted with hydroxy, mercapto, C1-C4alkoxy or C1-C4alkylthio; C3-C8alkenyl; C3-C8alkynyl; C3-C8cycloalkyl; C3-C8cycloalkyl-C1-C4alkyl; or

[0030] R2 is hydrogen and R3 is C1-C4alkyl; C3-C4alkenyl or cyclopropyl; or

[0031] R2 is hydrogen and R3 is C3-C4alkyl; allyl or cyclopropyl; or

[0032] R2 is hydrogen and R3 is isopropyl; or

[0033] R4 is hydrogen or C1-C4alkyl and R5, R6 and R7 are each hydrogen; or

[0034] R4 is hydrogen, methyl or ethyl and R5, R6 and R7 are each hydrogen; or

[0035] R4 is hydrogen or methyl and R5, R6 and R7 are each hydrogen; or

[0036] R4, R5, R6 and R7 are each hydrogen; or

[0037] R8 is C1-C6alkyl; or

[0038] R8 is methyl or ethyl; or

[0039] R8 is methyl; or

[0040] R9, R10, R14, R15, R16, R17 are each independently hydrogen or methyl; or

[0041] R9, R10, R14, R15, R16, R17 are each hydrogen; or

[0042] A is phenyl, optionally substituted by 1 to 3 substituents selected from C1-C8-alkyl, C2-C8-alkenyl, C2-C8-alkynyl, C3-C8-cycloalkyl, C3-C8-cycloalkyl-C1-C4-alkyl, phenyl, phenyl-C1-C4-alkyl wherein the hydrogens of all the preceding substituents may be in turn optionally substituted by one or several same or different halogens; C1-C8-alkoxy; C3-C8-alkenyloxy; C3-C8-alkynyloxy; C1-C8-alkoxy-C1-C4-alkyl; C1-C8halogenalkoxy; C1-C8-alkylthio; C1-C8-halogenalkylthio; C1-C8-alkylsulfonyl; formyl; C2-C8-alkanoyl; hydroxy; halogen; cyano; nitro; amino; C1-C8-alkylamino; C1-C8-dialkylamino; carboxy; C1-C8-alkoxycarbonyl; C1-C8-alkenyloxycarbonyl or C1-C8-alkynyloxycarbonyl; or

[0043] A is phenyl, optionally substituted by 1 to 3 substituents selected from C1-C8-alkyl, C2-C8-alkenyl wherein the hydrogens of all the preceding substituents may be in turn optionally substituted by one or several same or different halogens; C1-C8-alkoxy; C1-C8halogenalkoxy; C1-C8-alkylthio; C1-C8-halogenalkylthio; halogen; cyano; nitro or C1-C8-alkoxycarbonyl; or

[0044] A is phenyl, optionally substituted by 1 to 3 substituents selected from C1-C8-alkyl; C1-C8-haloalkyl; C1-C8-alkoxy; C1-C8halogenalkoxy; C1-C8-alkylthio; C1-C8-halogenalkylthio; halogen; cyano; nitro or C1-C8-alkoxycarbonyl.

[0045] Further preferred subgroups of the compounds of formula I are those wherein

[0046] R1 is C1-C12alkyl, C1-C12alkyl substituted with C1-C4alkoxy, C1-C4alkylthio, or C1-C4alkylsulfonyl; C2-C12alkenyl; C2-C12alkynyl; C1-C12haloalkyl; or a group NR12R13 wherein R12 and R13 are each independently of the other hydrogen or C1-C6-alkyl, or together are tetra- or penta-methylene; and

[0047] R2 is hydrogen and R3 is C1-C8alkyl; C1-C8alkyl substituted with hydroxy, mercapto, C1-C4alkoxy or C1-C4alkylthio; C3-C8alkenyl; C3-C8alkynyl; C3-C8cycloalkyl; C3-C8cycloalkyl-C1-C4alkyl; and

[0048] R4 is hydrogen or C1-C4alkyl and R5, R6 and R7 are each hydrogen; or those wherein

[0049] n is one; and

[0050] R1 is C1-C12alkyl, C2-C12alkenyl; C1-C12haloalkyl; or a group NR12R13 wherein R12 and R13 are each independently of the other hydrogen or C1-C6-alkyl; and

[0051] R2 is hydrogen and R3 is C1-C4alkyl; C3-C4alkenyl or cyclopropyl; and

[0052] R4 is hydrogen, methyl or ethyl and R5, R6 and R7 are each hydrogen; and

[0053] R8 is C1-C6alkyl; or those wherein

[0054] n is one; and

[0055] R1 is C1-C4alkyl, C2-C4alkenyl; C1-C4haloalkyl; or C1-C2-dialkylamino; and

[0056] R2 is hydrogen and R3 is C3-C4alkyl; allyl or cyclopropyl; and

[0057] R4 is hydrogen or methyl and R5, R6 and R7 are each hydrogen; and

[0058] R8 is methyl or ethyl; or those wherein

[0059] n is one; and

[0060] R1 is C1-C4alkyl, vinyl; C1-C4haloalkyl; or dimethylamino; and

[0061] R2 is hydrogen and R3 is isopropyl; and

[0062] R4, R5, R6 and R7 are each hydrogen; and

[0063] R8 is methyl.

[0064] Amongst the above preferred subgroups of compounds of formula I in turn those are preferred wherein

[0065] R9, R10, R14, R15, R16, R17 are each independently hydrogen or methyl; and

[0066] A is phenyl optionally substituted by 1 to 3 substituents selected from C1-C8-alkyl, C2-C8-alkenyl, C2-C8-alkynyl, C3-C8-cycloalkyl, C3-C8-cycloalkyl-C1-C4-alkyl, phenyl, phenyl-C1-C4-alkyl wherein the hydrogens of all the preceding substituents may be in turn optionally substituted by one or several same or different halogens; C1-C8-alkoxy; C3-C8-alkenyl; C3-C8-alkynyl; C1-C8-alkoxy-C1-C4-alkyl; C1-C8halogenalkoxy; C1-C8-alkylthio; C1-C8-halogenalkylthio; C1-C8-alkylsulfonyl; formyl; C2-C8-alkanoyl; hydroxy; halogen; cyano; nitro; amino; C1-C8-alkylamino; C1-C8-dialkylamino; carboxy; C1-C8-alkoxycarbonyl; C1-C8-alkenyloxycarbonyl or C1-C8-alkynyloxycarbonyl; or those wherein

[0067] R9, R10, R14, R15, R16, R17 are each hydrogen; and

[0068] A is phenyl optionally substituted by 1 to 3 substituents selected from C1-C8-alkyl, C2-C8-alkenyl wherein the hydrogens of all the preceding substituents may be in turn optionally substituted by one or several same or different halogens; C1-C8-alkoxy; C1-C8halogenalkoxy; C1-C8-alkylthio; C1-C8-halogenalkylthio; halogen; cyano; nitro or C1-C8-alkoxycarbonyl; or those wherein

[0069] R9, R10, R14, R15, R16, R17 are each hydrogen; and

[0070] A is phenyl optionally substituted by 1 to 3 substituents selected from C1-C8-alkyl; C1-C8-haloalkyl; C1-C8-alkoxy; C1-C8halogenalkoxy; C1-C8-alkylthio; C1-C8-halogenalkylthio; halogen; cyano; nitro or C1-C8-alkoxycarbonyl.

[0071] Preferred individual compounds are:

[0072] (S)-2-ethanesulfonylamino-N-(2-{4-[2-(4-chloro-phenyl)-propoxy]-3-methoxy-phenyl}-ethyl)-4-pentanoylamide,

[0073] (R,S)-2-ethanesulfonylamino-N-(2-{4-[2-(4-chloro-phenyl)-propoxy]-3-methoxy-phenyl}-ethyl)-3-methyl-butyramide,

[0074] (S)-2-ethanesulfonylamino-N-(2-{4-[2-(4-chloro-phenyl)-propoxy]-3-methoxy-phenyl}-ethyl)-3-methyl-butyramide,

[0075] (S)-2-ethanesulfonylamino-N-(2-{4-[2-(4-fluoro-phenyl)-propoxy]-3-methoxy-phenyl}-ethyl)-3-methyl-butyramide,

[0076] (S)-2-ethanesulfonylamino-N-(2-{4-[2-(4-chloro-phenyl)-propoxy]-3-methoxy-phenyl}-ethyl)-2-cyclopropyl-acetamide,

[0077] (S)-2-ethanesulfonylamino-N-(2-{4-[2-(2-fluoro-phenyl)-propoxy]-3-methoxy-phenyl}-ethyl)-3-methyl-butyramide,

[0078] (S)-2-methanesulfonylamino-N-(2-{4-[2-(2-fluoro-phenyl)-propoxy]-3-methoxy-phenyl}-ethyl)-3-methyl-butyramide,

[0079] (S)-2-ethanesulfonylamino-N-(2-{4-[2-(4-chloro-phenyl)-propoxy]-3-methoxy-phenyl}-ethyl)-butyramide, and

[0080] (S)-2-ethanesulfonylamino-N-(2-{4-[2-(4-fluoro-phenyl)-propoxy]-3-methoxy-phenyl}-ethyl)-butyramide,

[0081] Certain α-sulfin- and α-sulfonamino acid derivatives having a different kind of structure have already been proposed for controlling plant-destructive fungi (for example in WO 95/030651, WO 98/38160 and WO 98/38161). The action of those preparations is not, however, satisfactory in all aspects of agricultural needs. Surprisingly, with the compound structure of formula I, a new group of microbicides having a high level of activity have been found.

[0082] The α-sulfin- and α-sulfonamino acid amides of formula I may be obtained according to one of the following processes: 3

[0083] An amino acid of formula II or a carboxy-activated derivative of an amino acid of formula II wherein R1, n, R2 and R3 are as defined for formula I is reacted with an amine of formula III wherein R4, R5, R6, R7, R8, R9, R10, R14, R15, R16, R17 and A are as defined above optionally in the presence of a base and optionally in the presence of a diluting agent (step B). Carboxy-activated derivatives of the amino acid of formula II encompasses all compounds having an activated carboxyl group like an acid halide, such as an acid chloride, like symmetrical or mixed anhydrides, such as mixed anhydrides with O-alkylcarbonates, like activated esters, such as p-nitrophenylesters or N-hydroxysucinimidesters, as well as in situ produced activated forms of the amino acid of formula II by condensating agents, such as dicyclohexylcarbodiimid, carbonyldiimidazol, benzotriazol-1-yloxy-tris(dimethylamino)-phosphonium hexafluorophosphate, O-benzotriazol-1-yl N,N,N′,N′-bis(pentamethylene)-uronium hexafluorophosphate, O-benzotriazol-1-yl N,N,N′,N′-bis(tetramethylene)uronium hexafluorophosphate, O-benzotriazol-1-yl N,N,N′,N′-tetramethyluronium hexafluorophosphate or benzotriazol-1-yloxy-tripyrrolidinophosphonium hexafluorophosphate. The mixed anhydrides of the amino acids of the formula II may be prepared by reaction of an amino acid of formula II with chloroformic acid esters like chloroformic acid alkylesters, such as ethyl chloroformate or isobutyl chloroformate, optionally in the presence of an organic or inorganic base like a tertiary amine, such as triethylamine, N,N-diisopropyl-ethylamine, pyridine, n-methyl-piperidine or N-methyl-morpholin.

[0084] The present reaction is preferably performed in an inert solvent like aromatic, non-aromatic or halogenated hydrocarbons, such as chlorohydrocarbons e.g. dichloromethane or toluene; ketones, e.g. acetone; esters, e.g. ethyl acetate; amides, e.g. N,N-dimethylformamide; nitrites e.g. acetonitrile; or ethers e.g. diethylether, tert-butyl-methylether, dioxane or tetrahydrofurane or water. It is also possible to use mixtures of these solvents. The reaction is preformed optionally in the presence of an organic or inorganic base like a tertiary amine, e.g. triethylamine, N,N-diisopropyl-ethylamine, pyridine, n-methyl-piperidine or N-methyl-morpholine, like a metal hydroxide or a metal carbonate, preferentially an alkali hydroxide or an alkali carbonate, such as lithium hydroxide, sodium hydroxide or potassium hydroxide at temperatures ranging from −80° C. to +150° C., preferentially at temperatures ranging from −40° C. to +40° C.

[0085] The compounds of formula II may be prepared by reaction of an amino acid of formula IV where R2 and R3 are as defined for formula I with a sulfonyl halide or a sulfinyl halide of formula V where R1 and n have the same meanings as defined above and where X is halide, preferentially chlorine or bromine (step A).

[0086] The reaction may be performed in an inert solvent like aromatic, non-aromatic or halogenated hydrocarbons, such as chlorohydrocarbons, e.g. dichloromethane or toluene; ketones, e.g. acetone; esters, e.g. ethyl acetate; ethers, e.g. diethylether, tert-butyl-methylether, dioxane or tetrahydrofurane or water. It is also possible to use mixtures of these solvents. The reaction is performed optionally in the presence of an organic or inorganic base like a tertiary amine, such as triethylamine, N,N-diisopropyl-ethylamine, pyridine, n-methyl-piperidine or N-methyl-morpholine, like a metal hydroxide or a metal carbonate, preferentially an alkali hydroxide or an alkali carbonate, such as lithium hydroxide, sodium hydroxide or potassium hydroxide at temperatures ranging from −80° C. to +150° C., preferentially at temperatures ranging from −40° C. to +40° C. 4

[0087] The compounds of formula I may also be prepared by reaction of an amino acid derivative of formula VI wherein R4, R5, R6, R7, R8, R9, R10, R14, R15, R16, R17 and A are as defined for formula I with a sulfonyl halide or a sulfinyl halide of formula V wherein R1 and n are as defined for formula I and X is halide, preferentially chlorine or bromine (step C). The reaction is performed in the same manner as described for step A. 5

[0088] The compounds of formula I may also be prepared by reaction of a phenol of formula VII wherein R1, n, R2, R3, R4, R5, R6, R7 and R8 are as defined for formula I with a compound of formula VIII wherein R9, R10, R14, R15, R16, R17 and A are as defined for formula I and Y is a leaving group like a halide such as a chloride or bromide or a sulfonic ester such as a tosylate, mesylate or triflate (step D).

[0089] The reaction may be performed in an inert solvent like aromatic, non-aromatic or halogenated hydrocarbons, such as chlorohydrocarbons e.g. dichloromethane or toluene; ketones e.g. acetone or 2-butanone; esters, e.g. ethyl acetate; ethers, e.g. diethylether, tert-butyl-methylether, dioxane or tetrahydrofurane, amides, e.g. dimethylformamide, nitriles, e.g. acetonitrile, alcohols, e.g. methanol, ethanol, isopropanol, n-butanol or tert-butanol, sulfoxides e.g. dimethylsulfoxide or water. It is also possible to use mixtures of these solvents. The reaction is performed optionally in the presence of an organic or inorganic base like a tertiary amine, such as triethylamine, N,N-diisopropyl-ethylamine, pyridine, N-methyl-piperidine or N-methyl-morpholine, like a metal hydroxide, a metal carbonate or a metal alkoxide, preferentially an alkali hydroxide, an alkali carbonate or an alkali alkoxide, such as lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide, sodium tert-butoxide or potassium tert-butoxide at temperatures ranging from −80° C. to +200° C., preferentially at temperatures ranging from 0° C. to +120° C. 6

[0090] The compounds of formula Ia may also be prepared via formula IX wherein R1, n, R2, R3, R4, R5, R6, R7, R8 and A are as defined for formula I by reacting of a phenol of formula VII wherein R1, n, R2, R3, R4, R5, R6, R7 and R8 are as defined for formula I with a compound of formula VIIIa wherein R9, R10 and A are as defined for formula I and Y is a leaving group like a halide such as a chloride or bromide or a sulfonic ester such as a tosylate, mesylate or triflate (step E).

[0091] The reaction is performed in the same manner as described for step D.

[0092] The compounds of formula Ia where R14, R15, R16 and R17 are hydrogen and A is as defined for formula I may be prepared by reaction of compounds of formula IX with hydrogen. The reaction is performed in a solvent like ethers, e.g. diethylether, dioxane or tetrahydrofuran, or like alcohols, e.g. methanol or ethanol, or water in the presence of transition metals or transition metal salts, e.g. nickel, cobalt, palladium, platinum or rhodium, optionally in the presence of bases, e.g. ammonia, or in the presence of salts, e.g. barium sulfate, at temperatures ranging from −20° C. to +160° C. and at pressures ranging from 1 to 200 bar. 7

[0093] The compounds of formula Ib, where R1, n, R2, R3, R4, R5, R6, R7, R8, R9, R10, R14 and R16 are as defined for formula I, may be prepared by reaction of compounds of formula X with hydrogen. The reaction is performed in a solvent like ethers, e.g. diethylether, dioxane or tetrahydrofuran, or like alcohols, e.g. methanol or ethanol, or water in the presence of transition metals or transition metal salts, e.g. nickel, cobalt, palladium, platinum or rhodium, optionally in the presence of bases, e.g. ammonia, or in the presence of salts, e.g. barium sulfate, at temperatures ranging from −20 to +160° C. and at pressures ranging from 1 to 200 bar (step H).

[0094] The compounds of formula X, where R1, n, R2, R3, R4, R5, R6, R7, R8, R9, R10, R14 and R16 are the same as defined for formula I, may also be prepared by reacting a phenol of formula VII wherein R1, n, R2, R3, R4, R5, R6, R7 and R8 are as defined for formula I with a compound of formula VIIIb wherein R9, R10, R14, R16 and A are defined for formula I and Y is a leaving group like halide such as chloride or bromide or a sulfonic ester such as tosylate, mesylate or triflate (step G). The reaction is performed in the same manner as described for step D.

[0095] aa) The Intermediate Amines of Formula III May be Obtained by One of the Following Processes: 8

[0096] Step 1 is the alkylation of a phenol with a compound of formula VIII. The reaction is performed in the same manner as described for procedure c).

[0097] Step 2 is the reaction of an aromatic aldehyde with nitromethane. This reaction is performed in a solvent like an organic carboxylic acids, e.g. acetic acid optionally in the presence of the ammonium salt of this carboxylic acid, e.g. ammonium acetate at temperatures ranging from 0° C. to +200° C.

[0098] Step 3 is the reduction of an unsaturated nitrogen-compound. This reaction is performed in a solvent like an ether, e.g. diethylether, dioxane or tetrahydrofuran, or an alcohol, e.g. methanol, ethanol or isopropanol, with borohydride, with a boron-complex, e.g. the complex of borohydride with tetrahyrofuran, with an alkaliborohydride, with an alkalialuminiumhydride, e.g. lithiumaluminiumhydride, with aluminiumhydride, with an aluminiumalkoxyhydride or with hydrogen optionally in the presence of a transition metal, a transition metal salt or a transition metal complex, e.g. nickel, cobalt, palladium, platinum or rhodium at temperatures ranging from −50° C. to +200° C.

[0099] Step 4 is the reaction of an aldehyde or a ketone of formula with hydroxylamine or with a salt of hydroxylamine. This reaction is performed in a solvent like an alcohol, e.g. methanol, ethanol or isopropanol, like an ether, e.g. diethylether, dioxane or tetrahydrofuran, like an amide, e.g. dimethylformamide, or in water or in a mixture of these solvents optionally in the presence of an organic or inorganic base like a tertiary amine, e.g. triethylamine, like a heterocyclic compound containing nitrogen, e.g. pyridine, or like an alkalicarbonate, e.g. sodium carbonate or potassium carbonate, at temperatures ranging from −20° C. to +150° C.

[0100] Step 5 is the exchange of hydroxy by cyanide. This reaction is performed in an organic solvent like an amide, e.g. dimethylformamide using a metal cyanide like an alkali cyanide, e.g. sodium cyanide or potassium cyanide, at temperatures ranging from 0° C. to +200° C.

[0101] Step 6 is the hydrolysis of an alkyl ester. This reaction is performed in a solvent like an alcohol, e.g. methanol, ethanol or isopropanol, like an ether, e.g. diethylether, dioxane or tetrahydrofuran, like a halogenated hydrocarbon, e.g. dichloromethane, or water or in a mixture of these solvents optionally in the presence of an alkali hydroxide, e.g. lithium hydroxide, sodium hydroxide or potassium hydroxide, or optionally in the presence of an acid, e.g. hydrogen chloride, sulfuric acid or trifluoroacetic acid at temperatures ranging from −20° C. to +160° C.

[0102] Step 7 is the reaction of a carboxylic acid or the activated form of this carboxylic acid with hydrogen azide or an azide-salt. An activated form of a carboxylic acid can be the acid halogenide, e.g. acid chloride, a symmetric or a mixed anhydride. Azide-salts can be alkali azides, e.g. sodium azide. The reaction is performed in a solvent like a hydrocarbon, e.g. toluene or xylene, like a halogenated hydrocarbon, e.g. chloroform, like an ether, e.g. dioxane, like a ketone, e.g. acetone or 2-butanone, like an alcohol, e.g. methanol, ethanol or tert-butanol, or water or in a mixture of these solvents optionally in the presence of an acid like an inorganic acid, e.g. sulfuric acid or hydrogen chloride at temperatures ranging from −40° C. to +200° C.

[0103] In a preferred form the compounds of formula XXVI are prepared starting from compounds of the formula XXV by applying step 5 and step 1 in the same pot.

[0104] bb) Amines of Formula VI can be Obtained by the Following Process: 9

[0105] Step 8 is the amidation of an BOC protected amino acid of formula XXI with an amine of formula XXII. The reaction is performed in the same manner as described for step A.

[0106] Step 9 is the alkylation of a phenol of formula XXIII with an compound of formula VIII. The reaction is performed in the same manner as described for step D.

[0107] Step 10 is the hydrolysis of a carbamate of formula XIX. The reaction is performed in a solvent like hydrocarbons, e.g. toluene, like halogenated hydrocarbons, e.g. dichloromethane, like ketones, e.g. acetone, like esters, e.g. ethyl acetate, like ethers, e.g. dioxane or tetrahydrofuran, or like water or in mixtures of these solvents optionally in the presence of an organic acid like carboxylic acid, e.g. trifluoroacetic acid, or like a sulfonic acid, e.g. methanesulfonic acid or toluenesulfonic acid, or in the presence of an inorganic acid, e.g. hydrogen chloride or sulfuric acid, at temperatures ranging from −40° C. to +160° C.

[0108] The compounds of formula I are oils or solids at room temperature and are distinguished by valuable microbicidal properties. They can be used in the agricultural sector or related fields preventively and curatively in the control of plant-destructive microorganisms. The compounds of formula I according to the invention are distinguished at low rates of concentration not only by outstanding microbicidal, especially fungicidal, activity but also by being especially well tolerated by plants.

[0109] Surprisingly, it has now been found that the compounds of formula I have for practical purposes a very advantageous biocidal spectrum in the control of phytopathogenic microorganisms, especially fungi. They possess very advantageous curative and preventive properties and are used in the protection of numerous crop plants. With the compounds of formula I it is possible to inhibit or destroy phytopathogenic microorganisms that occur on various crops of useful plants or on parts of such plants (fruit, blossom, leaves, stems, tubers, roots), while parts of the plants which grow later also remain protected, for example, against phytopathogenic fungi.

[0110] The novel compounds of formula I prove to be effective against specific genera of the fungus class Fungi imperfecti (e.g. Cercospora), Basidiomycetes (e.g. Puccinia) and Ascomycetes (e.g. Erysiphe and Venturia) and especially against Oomycetes (e.g. Plasmopara, Peronospora, Pythium and Phytophthora). They therefore represent in plant protection a valuable addition to the compositions for controlling phytopathogenic fungi. The compounds of formula I can also be used as dressings for protecting seed (fruit, tubers, grains) and plant cuttings from fungal infections and against phytopathogenic fungi that occur in the soil.

[0111] The invention relates also to compositions comprising compounds of formula I as active ingredient, especially plant-protecting compositions, and to the use thereof in the agricultural sector or related fields.

[0112] In addition, the present invention includes the preparation of those compositions, wherein the active ingredient is homogeneously mixed with one or more of the substances or groups of substances described herein. Also included is a method of treating plants which is distinguished by the application of the novel compounds of formula I or of the novel compositions.

[0113] Target crops to be protected within the scope of this invention comprise, for example, the following species of plants: cereals (wheat, barley, rye, oats, rice, maize, sorghum and related species); beet (sugar beet and fodder beet); pomes, stone fruit and soft fruit (apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries and blackberries); leguminous plants (beans, lentils, peas, soybeans); oil plants (rape, mustard, poppy, olives, sunflowers, coconut, castor oil plants, cocoa beans, groundnuts); cucurbitaceae (marrows, cucumbers, melons); fibre plants (cotton, flax, hemp, jute); citrus fruit (oranges, lemons, grapefruit, mandarins); vegetables (spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, paprika); lauraceae (avocado, cinnamon, camphor) and plants such as tobacco, nuts, coffee, sugar cane, tea, pepper, vines, hops, bananas and natural rubber plants, and also ornamentals.

[0114] The compounds of formula I are normally used in the form of compositions and can be applied to the area or plant to be treated simultaneously or in succession with other active ingredients. Those other active ingredients may be fertilisers, micronutrient donors or other preparations that influence plant growth. It is also possible to use selective herbicides or insecticides, fungicides, bactericides, nematicides, molluscicides or mixtures of several of those preparations, if desired together with further carriers, surfactants or other application-promoting adjuvants customarily employed in formulation technology.

[0115] The compounds of formula I can be mixed with other fungicides, resulting in some cases in unexpected synergistic activities.

[0116] Mixing components which are particularly preferred are azoles such as azaconazole, bitertanol, propiconazole, difenoconazole, diniconazole, cyproconazole, epoxiconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imazalil, imibenconazole, ipconazole, tebuconazole, tetraconazole, fenbuconazole, metconazole, myclobutanil, perfurazoate, penconazole, bromuconazole, pyrifenox, prochloraz, triadimefon, triadimenol, triflumizole or triticonazole; pyrimidinyl carbinoles such as ancymidol, fenarimol or nuarimol; 2-amino-pyrimidine such as bupirimate, dimethirimol or ethirimol; morpholines such as dodemorph, fenpropidin, fenpropimorph, spiroxamin or tridemorph; anilinopyrimidines such as cyprodinil, pyrimethanil or mepanipyrim; pyrroles such as fenpiclonil or fludioxonil; phenylamides such as benalaxyl, furalaxyl, metalaxyl, R-metalaxyl, ofurace or oxadixyl; benzimidazoles such as benomyl, carbendazim, debacarb, fuberidazole or thiabendazole; dicarboximides such as chlozolinate, dichlozoline, iprodine, myclozoline, procymidone or vinclozolin; carboxamides such as carboxin, fenfuram, flutolanil, mepronil, oxycarboxin or thifluzamide; guanidines such as guazatine, dodine or iminoctadine; strobilurines such as azoxystrobin, kresoxim-methyl, metominostrobin, SSF-129, methyl 2-[(2-trifluoromethyl)-pyrid-6-yloxymethyl]-3-methoxyacrylate or 2-[α{[(α-methyl-3-trifluoromethyl-benzyl)imino]-oxy}-o-tolyl]-glyoxylic acid-methylester-O-methyloxime; dithiocarbamates such as ferbam, mancozeb, maneb, metiram, propineb, thiram, zineb or ziram; N-halomethylthio-dicarboximides such as captafol, captan, dichlofluanid, fluoromide, folpet or tolyfluanid; copper compounds such as Bordeaux mixture, copper hydroxide, copper oxychloride, copper sulfate, cuprous oxide, mancopper or oxine-copper; nitrophenol derivatives such as dinocap or nitrothal-isopropyl; organo phosphorous derivatives such as edifenphos, iprobenphos, isoprothiolane, phosdiphen, pyrazophos or toclofos-methyl; and other compounds of diverse structures such as acibenzolar-S-methyl, anilazine, blasticidin-S, chinomethionat, chloroneb, chlorothalonil, cymoxanil, dichlone, diclomezine, dicloran, diethofencarb, dimethomorph, dithianon, etridiazole, famoxadone, fenamidone, fentin, ferimzone, fluazinam, flusulfamide, fenhexamid, fosetyl-aluminium, hymexazol, kasugamycin, methasulfocarb, pencycuron, phthalide, polyoxins, probenazole, propamocarb, pyroquilon, quinoxyfen, quintozene, sulfur, triazoxide, tricyclazole, triforine or validamycin.

[0117] Suitable carriers and surfactants may be solid or liquid and correspond to the substances ordinarily employed in formulation technology, such as e.g. natural or regenerated mineral substances, solvents, dispersants, wetting agents, tackifiers, thickeners, binders or fertilisers. Such carriers and additives are described, for example, in WO 95/30651.

[0118] A preferred method of applying a compound of formula I, or an agrochemical composition comprising at least one of those compounds, is application to the foliage (foliar application), the frequency and the rate of application depending upon the risk of infestation by the pathogen in question. The compounds of formula I may also be applied to seed grains (coating) either by impregnating the grains with a liquid formulation of the active ingredient or by coating them with a solid formulation.

[0119] The compounds of formula I are used in unmodified form or, preferably, together with the adjuvants conventionally employed in formulation technology, and are for that purpose advantageously formulated in known manner e.g. into emulsifiable concentrates, coatable pastes, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granules, and by encapsulation in e.g. polymer substances. As with the nature of the compositions, the methods of application, such as spraying, atomising, dusting, scattering, coating or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances.

[0120] Advantageous rates of application are normally from 1 g to 2 kg of active ingredient (a.i.) per hectare (ha), preferably from 10 g to 1 kg a.i./ha, especially from 25 g to 750 g a.i./ha. When used as seed dressings, rates of from 0.001 g to 1.0 g of active ingredient per kg of seed are advantageously used.

[0121] The formulations, i.e. the compositions, preparations or mixtures comprising the compound(s) (active ingredient(s)) of formula I and, where appropriate, a solid or liquid adjuvant, are prepared in known manner, e.g. by homogeneously mixing and/or grinding the active ingredient with extenders, e.g. solvents, solid carriers and, where appropriate, surface-active compounds (surfactants).

[0122] Further surfactants customarily used in formulation technology will be known to the person skilled in the art or can be found in the relevant technical literature.

[0123] The agrochemical compositions usually comprise 0.01 to 99% by weight, preferably 0.1 to 95% by weight, of a compound of formula 1, 99.99 to 1% by weight, preferably 99.9 to 5% by weight, of a solid or liquid adjuvant, and 0 to 25% by weight, preferably 0.1 to 25% by weight, of a surfactant.

[0124] Whereas commercial products will preferably be formulated as concentrates, the end user will normally employ dilute formulations.

[0125] The compositions may also comprise further ingredients, such as stabilisers, antifoams, viscosity regulators, binders and tackifiers, as well as fertilisers or other active ingredients for obtaining special effects.

[0126] The Examples which follow illustrate the invention described above, without limiting the scope thereof in any way. Temperatures are given in degrees Celsius.

PREPARATION EXAMPLES FOR COMPOUNDS OF FORMULA I

Example A1.1

(S)-2-Ethanesulfonylamino-N-(2-{4-[2-(4-fluoro-phenyl)-propoxy]-3-methoxy-phenyl}-ethyl)-3-methyl-butyramide

[0127] 10

[0128] To a mixture of (S)-2-ethanesulfonylamino-3-methyl-butyric acid (0.7 g), 2-{4-[3-(4-fluoro-phenyl)-propoxy]-3-methoxy-phenyl}-ethylamine (1.0 g) and diethyl-isopropylamine (1.2 ml) in dimethylformamide (30 ml) is added benzotriazol-1-yloxy-tris(dimethylamino)phosphonium hexafluorophosphate (1.5 g) in one portion. The reaction mixture is stirred for 2 hours at room temperature. Water (200 ml) is then added. It is extracted with ethyl acetate (2×200 ml). The organic layers are washed with brine (2×200 ml), dried (MgSO4) and evaporated. The residue is purified by flash column chromatography on silica gel (ethyl acetate/hexane 2:1) and recrystallisation (ethyl acetate/hexane). Pure (S)-2-ethanesulfonyl-amino-N-(2-{4-[3-(4-fluoro-phenyl)-propoxy]-3-methoxy-phenyl}-ethyl)-3-methyl-butyramide is obtained, m.p. 107-111° C.

[0129] According to example A1.1 the compounds listed in Table 1 are obtained.

TABLE A1:
11
No	R1	R3	*)	CR9R10—CR14R15—CR16R17—A	m.p. (° C.)
A1.01	C2H5	C3H7-i	(S)	—(CH2)3-(4-F—Ph)	107-111
A1.02	C2H5	—CH2—CH≡CH2	(R, S)	—(CH2)3-(4-Cl—Ph)	98-99
A1.03	C2H5	C3H7-i	(S)	—(CH2)3—Ph	102-103
A1.04	C2H5	—CH2—C≡CH	(R, S)	—(CH2)3-(4-Cl—Ph)	123-125
A1.05	C2H5	C3H7-i	(R, S)	—(CH2)3-(4-Cl—Ph)	109-110
A1.06	C2H5	C3H7-i	(S)	—(CH2)3-(4-Cl—Ph)	134-136
A1.07	CH3	C3H7-i	(S)	—(CH2)3—Ph	Oil
A1.08	CH3	C3H7-i	(S)	—(CH2)3-(4-F—Ph)	125-127
A1.09	C2H5	C3H7-n	(S)	—(CH2)3-(4-F—Ph)	124-126
A1.10	C2H5	C2H5	(S)	—(CH2)3-(4-F—Ph)	114-116
A1.11	C2H5	C3H5-cycl	(S)	—(CH2)3-(4-Cl—Ph)	119-120
A1.12	C2H5	C4H9-s	(S)	—(CH2)3-(4-Cl—Ph)	120-122

[0130] *) Configuration on the α-C-atom in the amino acid moiety

Example A2.0

(S)-2-Ethanesulfonylamino-N-(2-{3-methoxy-4-[3-(3-trifluoromethyl-phenyl)-propoxy]-phenyl}-ethyl)-3-methyl-butyramide

[0131] 12

[0132] A mixture of (S)-2-ethanesulfonylamino-N-[2-(4-hydroxy-3-methoxy-phenyl)-ethyl]-3-methyl-butyramide (2.1 g), 1-(3-chloro-propenyl)-3-trifluoromethyl-benzene (2.0 g) and sodium methoxide (12 ml 1M solution in methanol) in methanol (50 ml) is heated to reflux for 4 hours. Upon cooling water (500 ml) is added. It is extracted with ethyl acetate (2×400 ml). The organic layers are washed with brine (150 ml), dried (MgSO4) and evaporated. The residue is dissolved in tetrahydrofuran (40 ml) and hydrogenated over palladium (5% on charcoal, 0.14 g) at room temperature and normal pressure. The reaction mixture is filtered. The filtrate is evaporated. (S)-2-Ethanesulfonylamino-N-(2-{3-methoxy-4-[3-(3-trifluoro-methyl-phenyl)-propoxy]-phenyl}-ethyl)-3-methyl-butyramide is obtained, m.p. 119-120° C.

[0133] According to example A2.01 the compounds listed in Table A2 are obtained.

TABLE A2
13
No	R1	R2	R3	*)	CR9R10R11	m.p. (° C.)
A2.01	C2H5	H	C3H7-i	(S)	—(CH2)3-(3-CF3—Ph)	119-120
A2.02	CH3	H	C3H7-i	(S)	—(CH2)3-(3-CF3—Ph)	94-95
A2.03	(CH3)2N	H	C3H7-i	(S)	—(CH2)3-(3-CF3—Ph)	89-91
A2.04	C2H5	H	C3H7-i	(S)	—(CH2)3-(2-F—Ph)	97-99
A2.05	CH3	H	C3H7-i	(S)	—(CH2)3-(2-F—Ph)	101-102
A2.06	C2H5	H	C2H5	(S)	—(CH2)3-(4-Cl—Ph)	118-120
A2.07	C2H5	H	C3H7-n	(S)	—(CH2)3-(4-Cl—Ph)	112-115
A2.08	C2H5	—(CH2)4—	—	—(CH2)3—Ph	117-118
A2.09	(CH3)2N	H	C3H7-i	(S)	—(CH2)3-(2-F—Ph)	92-95
A2.10	C2H5	H	C3H7-i	(S)	—(CH2)3-(4-Br—Ph)	129-131
A2.11	C2H5	H	CH(OH)—CH3	(S)	—(CH2)3-(4-Cl—Ph)	112-115
A2.12	CH3	H	C3H7-i	(S)	—(CH2)3-(3,4-di-Cl—Ph)	126-128
A2.13	C2H5	H	C3H7-i	(S)	—(CH2)3-(3,4-di-Cl—Ph)	115-117
A2.14	(CH3)2N	H	C3H7-i	(S)	—(CH2)3-(3,4-di-Cl—Ph)	117-119
A2.15	(CH3)2N	H	C3H7-i	(S)	—(CH2)3-(4-Br—Ph)	128-130
A2.16	CH3	H	C3H7-i	(S)	—(CH2)3-(1-Naphthyl)	resin
A2.17	C2H5	H	C3H7-i	(S)	—(CH2)3-(1-Naphthyl)	resin
*) Configuration on the α-C-atom in the amino acid moiety

Example A3.01

(S)-2-Methanesulfonylamino-N-(2-{3-methoxy-4-[3-(4-chloro-phenyl)-propoxy]-phenyl}-ethyl)-3-methyl-butyramide

[0134] 14

[0135] A mixture of 4-hydroxy-3-methoxybenzyl alcohol (76.1 g) and sodium cyanide (19.9 g) in dimethylformamide (250 ml) is stirred under an atmosphere of nitrogen for 3 hours at +120° C. The reaction mixture is cooled to +90° C. and 1-chloro-4-(3-chloro-propenyl)-benzene is added. The mixture is stirred at said temperature for 2 hours. After cooling it is poured into water (1000 ml) and extracted with ethyl acetate (2×500 ml). The organic layers are washed with brine (2×500 ml), dried (MgSO4) and evaporated. The residue is purified by flash column chromatography using silica gel and ethyl acetate/hexane (1:3). The product obtained is dissolved in methanol (400 ml) and hydrogenated over Raney-cobalt at +40° C. and 100 bar. Water (300 ml) and ethyl acetate (200 ml) are added. After filtration the reaction mixture is extracted with ethyl acetate (2×500 ml). The organic layers are washed with brine (2×200 ml), dried (K2CO3) and evaporated. 2-{4-[3-(4-Chloro-phenyl)-allyloxy]-3-methoxy-phenyl}-ethylamine is obtained.

[0136] BOC-L-Valine (31.4 g) and N-methylmorpholine (15.9 ml) are dissolved in tetrahydrofuran (250 ml) and cooled to −20° C. Isobutyl chloroformate (18.9 ml) is added dropwise during 20 minutes. The resulting mixture is stirred for 15 min and allowed to warm to −7° C. It is then cooled again to −20° C. and a solution of 2-{4-[3-(4-chloro-phenyl)-allyloxy]-3-methoxy-phenyl}-ethylamine (41.7 g) in tetrahydrofuran (150 ml) is added dropwise during 40 min. The reaction mixture is stirred at room temperature during 4 hours. 1M Hydrochloric acid (500 ml) is added carefully. It is extracted with ethyl acetate (2×500 ml). The organic layers are washed with 1M hydrochloric acid (500 ml) and brine (500 ml), dried (MgSO4) and evaporated. The residue is dissolved in tetrahydrofuran (500 ml) and hydrogenated over palladium (5% on charcoal, 0.14g) at room temperature and normal pressure. The reaction mixture is filtered and evaporated. The residue is dissolved in dioxane (130 ml) and added dropwise to 4M sulfuric acid (650 ml). The resulting mixture is stirred for 8 hours at +50° C. After cooling it is extracted with diethyl ether (2×1000 ml). The aqueous phase is saturated with potassium carbonate and then extracted with diethyl ether (2×1500 ml). The organic layers are dried (K2CO3) and evaporated. (S)-2-Amino-N-(2-{4-[3-(4-chloro-phenyl)-propoxy]-3-methoxy-phenyl}-ethyl)-3-methyl-butyramide is obtained. To (S)-2-amino-N-(2-{4-[3-(4-chloro-phenyl)-propoxy]-3-methoxy-phenyl}-ethyl)-3-methyl-butyramide (2 g) and triethylamine (0.9 ml) in dioxane (30 ml) is added methanesulfonyl chloride (0.4 ml). The reaction mixture is stirred overnight at room temperature. Water (200 ml) is then added. It is extracted with ethyl acetate (2×200 ml). The organic layers are washed with brine (2×200 ml), dried (MgSO4) and evaporated. (S)-2-Methanesulfonyl-aminoN-(2-{3-methoxy-4-[3-(4-chloro-phenyl)-propoxy]-phenyl}-ethyl)-3-methyl-butyramide is obtained.

[0137] According to example A3.01 the compounds listed in table A2 are obtained.

TABLE A3
15
No	R1	R2	R3	*)	CR9R10R11	m.p. (° C.)
A3.01	CH3	H	C3H7-i	(S)	—(CH2)3-(4-Cl—Ph)	128-130
A3.02	CH2═C(CH3)—CH2	H	C3H7-i	(S)	—(CH2)3-(4-Cl—Ph)	120-123
A3.03	(CH3)2N	H	C3H7-i	(S)	—(CH2)3-(4-Cl—Ph)	117-119
*) Configuration on the α-C-atom in the amino acid moiety

Example B1.1

[3-Methoxy-4-(3-phenyl-prop-2-ynyloxy)-phenyl]-acetonitrile

[0138] 16

[0139] A mixture of 4-hydroxy-3-methoxy-benzyl alcohol (17.4 g) and sodium cyanide (6.6 g) in dimethylformamide (250 ml) is stirred under an atmosphere of nitrogen for 3 hours at +1 20° C. The mixture is then cooled to +60° C. and toluene-4-sulfonic acid 3-phenyl-prop-2-ynyl ester (39 g) in dimethylformamid (50 ml) is added during 5 minutes. It is stirred at +65° C. for another 4 hours. Upon cooling water (800 ml) is added. The mixture is extracted with ethyl acetate (2×500 ml). The organic phases are washed with brine (2×500 ml), dried (MgSO4) and evaporated. The residue is purified by flash column chromatography on silica gel (ethyl acetate/hexane 1:3) and recrystallised from ethyl acetate/hexane. [3-Methoxy-4-(3-phenyl-prop-2-ynyloxy)-phenyl]-acetonitrile is obtained, m.p. 74-75° C.

[0140] Analogously to example B1.1 the compounds listed in table B1 are obtained.

[0141] Ph means phenyl

TABLE B1
17
No	A	m.p. (° C.)
B1.01	Ph	74-75
B1.02	4-Cl—Ph	108-109
B1.03	4-F—Ph	oil

Example B2.1

2-[3-Methoxy-4-(3-phenyl-propoxy)-phenyl]-ethylamine

[0142] 18

[0143] A mixture of [3-methoxy-4-(3-phenyl-prop-2-ynyloxy)-phenyl]-acetonitrile (2.0 g), liquid ammonia (5 g) and Raney-nickel (1 g) in methanol (100 ml) is shaken in an autoclave under hydrogen (100 bar) at +70° C. for 2 hours. The reaction mixture is filtered and evaporated. 2-[3-Methoxy-4-(3-phenyl-propoxy)-phenyl]-ethylamine is obtained as an oil.

[0144] Analogously to example B2.1 the compounds listed in table B2 are obtained.

[0145] Ph means phenyl

TABLE 2
19
No	CR9R10CR14R15CR16R17—A	m.p. (° C.)
B2.01	—(CH2)3—Ph	oil
B2.02	—(CH2)3(4-Cl—Ph)	oil
B2.03	—(CH2)3—(4-F—Ph)	oil

[0146] Analogously to the above Examples the following compounds of Tables 1 to 37 may be prepared.

TABLE 1
Compounds represented by the Formula I.1 wherein the combination of the
groups R1, R3, R9, R10, R14, R15, R18,
R17 and A corresponds to each row in table A.
20 I.1

[0147]

TABLE 2
Compounds represented by the Formula I.2 wherein the combination of the
groups R1, R3, R9, R10, R14, R15,
R16, R17 and A corresponds to each row in table A.
21 I.2

[0148]

TABLE 3
Compounds represented by the Formula I.3 wherein the combination of
the groups R1, R3, R9, R10, R14, R15, R16,
R17 and A corresponds to each row in table A.
22 I.3

[0149]

TABLE 4
Compounds represented by the Formula I.4 wherein the combination of the
groups R1, R3, R9, R10, R14, R15,
R16, R17 and A corresponds to each row in table A.
23 I.4

[0150]

TABLE 5
Compounds represented by the Formula I.5 wherein the combination
of the groups R1, R3, R9, R10, R14,
R15, R16, R17, and A corresponds to each row in table A.
24 I.5

[0151]

TABLE 6
Compounds represented by the Formula I.6 wherein the combination
of the groups R1, R3, R9, R10, R14, R15,
R16, R17 and A corresponds to each row in table A.
25

[0152]

TABLE 7
Compounds represented by the Formula I.7 wherein the combination
of the groups R1, R3, R9, R10, R14, R15,
R16, R17 and A corresponds to each row in table A.
26

[0153]

TABLE 8
Compounds represented by the Formula I.8 wherein the combination
of the groups R1, R3, R9, R10, R14, R15,
R16, R17 and A corresponds to each row in table A.
27

[0154]

TABLE 9
Compounds represented by the Formula I.9 wherein the combination
of the groups R1, R3, R9, R10, R14, R15,
R16, R17 and A corresponds to each row in table A.
28

[0155]

TABLE 10
Compounds represented by the Formula I.10 wherein the combination
of the groups R1, R3, R9, R10, R14, R15,
R16, R17 and A corresponds to each row in table A.
29

[0156]

TABLE 11
Compounds represented by the Formula I.11 wherein the combination
of the groups R1, R3, R9, R10, R14, R15,
R16, R17 and A corresponds to each row in table A.
30

[0157]

TABLE 12
Compounds represented by the Formula I.12 wherein the combination
of the groups R1, R3, R9, R10, R14, R15,
R16, R17 and A corresponds to each row in table A.
31

[0158]

TABLE 13
Compounds represented by the Formula I.13 wherein the combination
of the groups R1, R3, R9, R10, R14, R15,
R16, R17 and A corresponds to each row in table A.
32

[0159]

TABLE 14
Compounds represented by the Formula I.14 wherein the combination
of the groups R9, R10, R14, R15, R16, R17
and A corresponds to each row in table B.
33

[0160]

TABLE 15
Compounds represented by the Formula I.15 wherein the combination
of the groups R9, R10, R14, R15, R16, R17
and A corresponds to each row in table B.
34

[0161]

TABLE 16
Compounds represented by the Formula I.16 where the combination of the
groups R9, R10, R14, R15, R16, R17 and
A corresponds to each row in table B.
35 I.16

[0162]

TABLE 16
Compounds represented by the Formula I.17 where the combination of the
groups R9, R10, R14, R15, R16,
R17 and A corresponds to each row in table B.
36 I.17

[0163]

TABLE 18
Compounds represented by the Formula I.18 where the combination of the
groups R9, R10, R14, R15, R16, R17
and A corresponds to each row in table B.
37 I.18

[0164]

TABLE 19
Compounds represented by the Formula I.19 where the combination of the
groups R9, R10, R14, R15, R16, R17
and A corresponds to each row in table B.
38 I.19

[0165]

TABLE 20
Compounds represented by the Formula I.20 where the combination of the
groups R9, R10, R14, R15, R16, R17
and A corresponds to each row in table B.
39 I.20

[0166]

TABLE 21
Compounds represented by the Formula I.21 where the combination of the
groups R9, R10, R14, R15, R16, R17
and A corresponds to each row in table B.
40 I.21

[0167]

TABLE 22
Compounds represented by the Formula I.22 where the combination of the
groups R9, R10, R14, R15, R18, R17
and A corresponds to each row in table B.
41 I.22

[0168]

TABLE 23
Compounds represented by the Formula I.23 where the combination of the
groups R9, R10, R14, R15, R16, R17
and A corresponds to each row in table B.
42 I.23

[0169]

TABLE 24
Compounds represented by the Formula I.24 where the combination of the
groups R9, R10, R14, R15, R16, R17
and A corresponds to each row in table B.
43 I.24

[0170]

TABLE 25
Compounds represented by the Formula I.25 where the combination of the
groups R9, R10, R14, R15, R16, R17
and A corresponds to each row in table B.
44 I.25

[0171]

TABLE 26
Compounds represented by the Formula I.26 where the combination of the
groups R9, R10, R14, R15, R16, R17 and A corresponds to each row in table B.
45 I.26

[0172]

TABLE 27
Compounds represented by the Formula I.27 where the combination of the
groups R9, R10, R14, R15, R16, R17 and A corresponds to each row in table B.
46 I.27

[0173]

TABLE 28
Compounds represented by the Formula I.28 where the combination of the
groups R9, R10, R14, R15, R16, R17 and A corresponds to each row in table B.
47 I.28

[0174]

TABLE 29
Compounds represented by the Formula I.29 where the combination of the
groups R9, R10, R14, R15, R16, R17 and A corresponds to each row in table B.
48 I.29

[0175]

TABLE 30
Compounds represented by the Formula I.30 where the combination of the
groups R9, R10, R14, R15, R16, R17 and A corresponds to each row in table B.
49 I.30

[0176]

TABLE 31
Compounds represented by the Formula I.31 where the combination of the
groups R9, R10, R14, R15, R16, R17 and A corresponds to each row in table B.
50 I.31

[0177]

TABLE 32
Compounds represented by the Formula I.32 where the combination of the
groups R9, R10, R14, R15, R16, R17 and A corresponds to each row in table B.
51 I.32

[0178]

TABLE 33
Compounds represented by the Formula I.33 where the combination of the
groups R9, R10, R14, R15, R16, R17 and A corresponds to each row in table B.
52 I.33

[0179]

TABLE 34
Compounds represented by the Formula I.34 where the combination of the
groups R9, R10, R14, R15, R16, R17 and A corresponds to each row in table B.
53 I.34

[0180]

TABLE 35
Compounds represented by the Formula I.35 where the combination of the
groups R9, R10, R14, R15, R18, R17 and A corresponds to each row in table B.
54 I.35

[0181]

TABLE 36
Compounds represented by the Formula I.36 where the
combination of the groups R9, R10, R14,
R15, R16, R17 and A corresponds to
each row in table B.
I.36
55

[0182]

TABLE 37
Compounds represented by the Formula I.37 where the combination of the
groups R9, R10, R14, R15, R16, R17 and A corresponds to each row
in table B.
	I.37
56
No.	R1	R3	CR9R10CR14R15CR16R17-A
Table A:
001	CH3	C3H7-i	CH2—CH2—CH2—(4-Cl—Ph)
002	C2H5	C3H7-i	CH2—CH2—CH2—(4-Cl—Ph)
003	(CH3)2N—	C3H7-i	CH2—CH2—CH2—(4-Cl—Ph)
004	C3H7-i	C3H7-i	CH2—CH2—CH2—(4-Cl—Ph)
005	C3H7-n	C3H7-i	CH2—CH2—CH2—(4-Cl—Ph)
006	ClH2C—CH2—CH2—	C3H7-i	CH2—CH2—CH2—(4-Cl—Ph)
007	H2C═CH—	C3H7-i	CH2—CH2—CH2—(4-Cl—Ph)
008	CH3—SO2—CH2—	C3H7-i	CH2—CH2—CH2—(4-Cl—Ph)
009	CF3	C3H7-i	CH2—CH2—CH2—(4-Cl—Ph)
010	57	C3H7-i	CH2—CH2—CH2—(4-Cl—Ph)
011	CH3	C2H5	CH2—CH2—CH2—(4-Cl—Ph)
012	C2H5	C2H5	CH2—CH2—CH2—(4-Cl—Ph)
013	(CH3)2N—	C2H5	CH2—CH2—CH2—(4-Cl—Ph)
014	C3H7-i	C2H5	CH2—CH2—CH2—(4-Cl—Ph)
015	C3H7-n	C2H5	CH2—CH2—CH2—(4-Cl—Ph)
016	ClH2C—CH2—CH2—	C2H5	CH2—CH2—CH2—(4-Cl—Ph)
017	H2C═CH—	C2H5	CH2—CH2—CH2—(4-Cl—Ph)
018	CH3—SO2—CH2—	C2H5	CH2—CH2—CH2—(4-Cl—Ph)
019	CF3	C2H5	CH2—CH2—CH2—(4-Cl—Ph)
020	58	C2H5	CH2—CH2—CH2—(4-Cl—Ph)
021	CH3	C3H7-n	CH2—CH2—CH2—(4-Cl—Ph)
022	C2H5	C3H7-n	CH2—CH2—CH2—(4-Cl—Ph)
023	(CH3)2N—	C3H7-n	CH2—CH2—CH2—(4-Cl—Ph)
024	C3H7-i	C3H7-n	CH2—CH2—CH2—(4-Cl—Ph)
025	C3H7-n	C3H7-n	CH2—CH2—CH2—(4-Cl—Ph)
026	ClH2C—CH2—CH2—	C3H7-n	CH2—CH2—CH2—(4-Cl—Ph)
027	H2C═CH—	C3H7-n	CH2—CH2—CH2—(4-Cl—Ph)
028	CH3—SO2—CH2—	C3H7-n	CH2—CH2—CH2—(4-Cl—Ph)
029	CF3	C3H7-n	CH2—CH2—CH2—(4-Cl—Ph)
030	59	C3H7-n	CH2—CH2—CH2—(4-Cl—Ph)
031	CH3	C4H9-s	CH2—CH2—CH2—(4-Cl—Ph)
032	C2H5	C4H9-s	CH2—CH2—CH2—(4-Cl—Ph)
033	(CH3)2N—	C4H9-s	CH2—CH2—CH2—(4-Cl—Ph)
034	C3H7-i	C4H9-s	CH2—CH2—CH2—(4-Cl—Ph)
035	C3H7-n	C4H9-s	CH2—CH2—CH2—(4-Cl—Ph)
036	ClH2C—CH2—CH2—	C4H9-s	CH2—CH2—CH2—(4-Cl—Ph)
037	H2C═CH—	C4H9-s	CH2—CH2—CH2—(4-Cl—Ph)
038	CH3—SO2—CH2—	C4H9-s	CH2—CH2—CH2—(4-Cl—Ph)
039	CF3	C4H9-s	CH2—CH2—CH2—(4-Cl—Ph)
040	60	C4H9-s	CH2—CH2—CH2—(4-Cl—Ph)
041	CH3	C3H5-cycl	CH2—CH2—CH2—(4-Cl—Ph)
042	C2H5	C3H5-cycl	CH2—CH2—CH2—(4-Cl—Ph)
043	(CH3)2N—	C3H5-cycl	CH2—CH2—CH2—(4-Cl—Ph)
044	C3H7-i	C3H5-cycl	CH2—CH2—CH2—(4-Cl—Ph)
045	C3H7-n	C3H5-cycl	CH2—CH2—CH2—(4-Cl—Ph)
046	ClH2C—CH2—CH2—	C3H5-cycl	CH2—CH2—CH2—(4-Cl—Ph)
047	H2C═CH—	C3H5-cycl	CH2—CH2—CH2—(4-Cl—Ph)
048	CH3—SO2—CH2—	C3H5-cycl	CH2—CH2—CH2—(4-Cl—Ph)
049	CF3	C3H5-cycl	CH2—CH2—CH2—(4-Cl—Ph)
050	61	C3H5-cycl	CH2—CH2—CH2—(4-Cl—Ph)
051	CH3	CH2—CH═CH2	CH2—CH2—CH2—(4-Cl—Ph)
052	C2H5	CH2—CH═CH2	CH2—CH2—CH2—(4-Cl—Ph)
053	(CH3)2N—	CH2—CH═CH2	CH2—CH2—CH2—(4-Cl—Ph)
054	C3H7-i	CH2—CH═CH2	CH2—CH2—CH2—(4-Cl—Ph)
055	C3H7-n	CH2—CH═CH2	CH2—CH2—CH2—(4-Cl—Ph)
056	ClH2C—CH2—CH2—	CH2—CH═CH2	CH2—CH2—CH2—(4-Cl—Ph)
057	H2C═CH—	CH2—CH═CH2	CH2—CH2—CH2—(4-Cl—Ph)
058	CH3—SO2—CH2—	CH2—CH═CH2	CH2—CH2—CH2—(4-Cl—Ph)
059	CF3	CH2—CH═CH2	CH2—CH2—CH2—(4-Cl—Ph)
060	62	CH2—CH═CH2	CH2—CH2—CH2—(4-Cl—Ph)
061	CH3	CH2—C≡CH	CH2—CH2—CH2—(4-Cl—Ph)
062	C2H5	CH2—C≡CH	CH2—CH2—CH2—(4-Cl—Ph)
063	(CH3)2N—	CH2—C≡CH	CH2—CH2—CH2—(4-Cl—Ph)
064	C3H7-i	CH2—C≡CH	CH2—CH2—CH2—(4-Cl—Ph)
065	C3H7-n	CH2—C≡CH	CH2—CH2—CH2—(4-Cl—Ph)
066	ClH2C—CH2—CH2—	CH2—CH≡CH	CH2—CH2—CH2—(4-Cl—Ph)
067	H2C═CH—	CH2—C≡CH	CH2—CH2—CH2—(4-Cl—Ph)
068	CH3—SO2—CH2—	CH2—C≡CH	CH2—CH2—CH2—(4-Cl—Ph)
069	CF3	CH2—C≡CH	CH2—CH2—CH2—(4-Cl—Ph)
070	63	CH2—C≡CH	CH2—CH2—CH2—(4-Cl—Ph)
071	CH3	C3H5-cycl-CH2—	CH2—CH2—CH2—(4-Cl—Ph)
072	C2H5	C3H5-cycl-CH2—	CH2—CH2—CH2—(4-Cl—Ph)
073	(CH3)2N—	C3H5-cycl-CH2—	CH2—CH2—CH2—(4-Cl—Ph)
074	C3H7-i	C3H5-cycl-CH2—	CH2—CH2—CH2—(4-Cl—Ph)
075	C3H7-n	C3H5-cycl-CH2—	CH2—CH2—CH2—(4-Cl—Ph)
076	ClH2C—CH2—CH2—	C3H5-cycl-CH2—	CH2—CH2—CH2—(4-Cl—Ph)
077	H2C═CH—	C3H5-cycl-CH2—	CH2—CH2—CH2—(4-Cl—Ph)
078	CH3—SO2—CH2—	C3H5-cycl-CH2—	CH2—CH2—CH2—(4-Cl—Ph)
079	CF3	C3H5-cycl-CH2—	CH2—CH2—CH2—(4-Cl—Ph)
080	64	C3H5-cycl-CH2—	CH2—CH2—CH2—(4-Cl—Ph)
081	CH3	H3C—CH2(OH)—	CH2—CH2—CH2—(4-Cl—Ph)
082	C2H5	H3C—CH2(OH)—	CH2—CH2—CH2—(4-Cl—Ph)
083	(CH3)2N—	H3C—CH2(OH)—	CH2—CH2—CH2—(4-Cl—Ph)
084	C3H7-i	H3C—CH2(OH)—	CH2—CH2—CH2—(4-Cl—Ph)
085	C3H7-n	H3C—CH2(OH)—	CH2—CH2—CH2—(4-Cl—Ph)
086	ClH2C—CH2—CH2—	H3C—CH2(OH)—	CH2—CH2—CH2—(4-Cl—Ph)
087	H2C═CH—	H3C—CH2(OH)—	CH2—CH2—CH2—(4-Cl—Ph)
088	CH3—SO2—CH—	H3C—CH2(OH)—	CH2—CH2—CH2—(4-Cl—Ph)
089	CF3	H3C—CH2(OH)—	CH2—CH2—CH2—(4-Cl—Ph)
090	65	H3C—CH2(OH)—	CH2—CH2—CH2—(4-Cl—Ph)
091	CH3	H3C—S—CH2—CH2—	CH2—CH2—CH2—(4-Cl—Ph)
092	C2H5	H3C—S—CH2—CH2—	CH2—CH2—CH2—(4-Cl—Ph)
093	(CH3)2N—	H3C—S—CH2—CH2—	CH2—CH2—CH2—(4-Cl—Ph)
094	C3H7-i	H3C—S—CH2—CH2—	CH2—CH2—CH2—(4-Cl—Ph)
095	C3H7-n	H3C—S—CH2—CH2—	CH2—CH2—CH2—(4-Cl—Ph)
096	ClH2C—CH2—CH2—	H3C—S—CH2—CH2—	CH2—CH2—CH2—(4-Cl—Ph)
097	H2C═CH—	H3C—S—CH2—CH2—	CH2—CH2—CH2—(4-Cl—Ph)
098	CH3—SO2—CH2—	H3C—S—CH2—CH2—	CH2—CH2—CH2—(4-Cl—Ph)
099	CF3	H3C—S—CH2—CH2—	CH2—CH2—CH2—(4-Cl—Ph)
100	66	H3C—S—CH2—CH2—	CH2—CH2—CH2—(4-Cl—Ph)
101	CH3	HS—CH2	CH2—CH2—CH2—(4-Cl—Ph)
102	C2H5	HS—CH2	CH2—CH2—CH2—(4-Cl—Ph)
103	(CH3)2N—	HS—CH2	CH2—CH2—CH2—(4-Cl—Ph)
104	C3H7-i	HS—CH2	CH2—CH2—CH2—(4-Cl—Ph)
105	C3H7-n	HS—CH2	CH2—CH2—CH2—(4-Cl—Ph)
106	ClH2C—CH2—CH2—	HS—CH2	CH2—CH2—CH2—(4-Cl—Ph)
107	H2C═CH—	HS—CH2	CH2—CH2—CH2—(4-Cl—Ph)
108	CH3—SO2—CH2—	HS—CH2	CH2—CH2—CH2—(4-Cl—Ph)
109	CF3	HS—CH2	CH2—CH2—CH2—(4-Cl—Ph)
110	67	HS—CH2	CH2—CH2—CH2—(4-Cl—Ph)
111	CH3	C3H7-i	CH2—CH2—CH2—(4-F—Ph)
112	C2H5	C3H7-i	CH2—CH2—CH2—(4-F—Ph)
113	(CH3)2N—	C3H7-i	CH2—CH2—CH2—(4-F—Ph)
114	C3H7-i	C3H7-i	CH2—CH2—CH2—(4-F—Ph)
115	C3H7-n	C3H7-i	CH2—CH2—CH2—(4-F—Ph)
116	ClH2C—CH2—CH2—	C3H7-i	CH2—CH2—CH2—(4-F—Ph)
117	H2C═CH—	C3H7-i	CH2—CH2—CH2—(4-F—Ph)
118	CH3—SO2—CH2—	C3H7-i	CH2—CH2—CH2—(4-F—Ph)
119	CF3	C3H7-i	CH2—CH2—CH2—(4-F—Ph)
120	68	C3H7-i	CH2—CH2—CH2—(4-F—Ph)
121	CH3	C2H5	CH2—CH2—CH2—(4-F—Ph)
122	C2H5	C2H5	CH2—CH2—CH2—(4-F—Ph)
123	(CH3)2N—	C2H5	CH2—CH2—CH2—(4-F—Ph)
124	C3H7-i	C2H5	CH2—CH2—CH2—(4-F—Ph)
125	C3H7-n	C2H5	CH2—CH2—CH2—(4-F—Ph)
126	ClH2C—CH2—CH2—	C2H5	CH2—CH2—CH2—(4-F—Ph)
127	H2C═CH—	C2H5	CH2—CH2—CH2—(4-F—Ph)
128	CH3—SO2—CH2—	C2H5	CH2—CH2—CH2—(4-F—Ph)
129	CF3	C2H5	CH2—CH2—CH2—(4-F—Ph)
130	69	C2H5	CH2—CH2—CH2—(4-F—Ph)
131	CH3	C3H7-n	CH2—CH2—CH2—(4-F—Ph)
132	C2H5	C3H7-n	CH2—CH2—CH2—(4-F—Ph)
133	(CH3)2N—	C3H7-n	CH2—CH2—CH2—(4-F—Ph)
134	C3H7-i	C3H7-n	CH2—CH2—CH2—(4-F—Ph)
135	C3H7-n	C3H7-n	CH2—CH2—CH2—(4-F—Ph)
136	ClH2C—CH2—CH2—	C3H7-n	CH2—CH2—CH2—(4-F—Ph)
137	H2C═CH—	C3H7-n	CH2—CH2—CH2—(4-F—Ph)
138	CH3—SO2—CH2—	C3H7-n	CH2—CH2—CH2—(4-F—Ph)
139	CF3	C3H7-n	CH2—CH2—CH2—(4-F—Ph)
140	70	C3H7-n	CH2—CH2—CH2—(4-F—Ph)
141	CH3	C4H9-s	CH2—CH2—CH2—(4-F—Ph)
142	C2H5	C4H9-s	CH2—CH2—CH2—(4-F—Ph)
143	(CH3)2N—	C4H9-s	CH2—CH2—CH2—(4-F—Ph)
144	C3H7-i	C4H9-s	CH2—CH2—CH2—(4-F—Ph)
145	C3H7-n	C4H9-s	CH2—CH2—CH2—(4-F—Ph)
146	ClH2C—CH2—CH2—	C4H9-s	CH2—CH2—CH2—(4-F—Ph)
147	H2C═CH—	C4H9-s	CH2—CH2—CH2—(4-F—Ph)
148	CH3—SO2—CH2—	C4H9-s	CH2—CH2—CH2—(4-F—Ph)
149	CF3	C4H9-s	CH2—CH2—CH2—(4-F—Ph)
150	71	C4H9-s	CH2—CH2—CH2—(4-F—Ph)
151	CH3	C3H5-cycl	CH2—CH2—CH2—(4-F—Ph)
152	C2H5	C3H5-cycl	CH2—CH2—CH2—(4-F—Ph)
153	(CH3)2N—	C3H5-cycl	CH2—CH2—CH2—(4-F—Ph)
154	C3H7-i	C3H5-cycl	CH2—CH2—CH2—(4-F—Ph)
155	C3H7-n	C3H5-cycl	CH2—CH2—CH2—(4-F—Ph)
156	ClH2C—CH2—CH2—	C3H5-cycl	CH2—CH2—CH2—(4-F—Ph)
157	H2C═CH—	C3H5-cycl	CH2—CH2—CH2—(4-F—Ph)
158	CH3—SO2—CH2—	C3H5-cycl	CH2—CH2—CH2—(4-F—Ph)
159	CF3	C3H5-cycl	CH2—CH2—CH2—(4-F—Ph)
160	72	C3H5-cycl	CH2—CH2—CH2—(4-F—Ph)
161	CH3	CH2—CH═CH2	CH2—CH2—CH2—(4-F—Ph)
162	C2H5	CH2—CH═CH2	CH2—CH2—CH2—(4-F—Ph)
163	(CH3)2N—	CH2—CH═CH2	CH2—CH2—CH2—(4-F—Ph)
164	C3H7-i	CH2—CH═CH2	CH2—CH2—CH2—(4-F—Ph)
165	C3H7-n	CH2—CH═CH2	CH2—CH2—CH2—(4-F—Ph)
166	ClH2C—CH2—CH2—	CH2—CH═CH2	CH2—CH2—CH2—(4-F—Ph)
167	H2C═CH—	CH2—CH═CH2	CH2—CH2—CH2—(4-F—Ph)
168	CH3—SO2—CH2—	CH2—CH═CH2	CH2—CH2—CH2—(4-F—Ph)
169	CF3	CH2—CH═CH2	CH2—CH2—CH2—(4-F—Ph)
170	73	CH2—CH═CH2	CH2—CH2—CH2—(4-F—Ph)
171	CH3	CH2—C≡CH	CH2—CH2—CH2—(4-F—Ph)
172	C2H5	CH2—C≡CH	CH2—CH2—CH2—(4-F—Ph)
173	(CH3)2N—	CH2—C≡CH	CH2—CH2—CH2—(4-F—Ph)
174	C3H7-i	CH2—C≡CH	CH2—CH2—CH2—(4-F—Ph)
175	C3H7-n	CH2—C≡CH	CH2—CH2—CH2—(4-F—Ph)
176	ClH2C—CH2—CH2—	CH2—C≡CH	CH2—CH2—CH2—(4-F—Ph)
177	H2C═CH—	CH2—C≡CH	CH2—CH2—CH2—(4-F—Ph)
178	CH3—SO2—CH2—	CH2—C≡CH	CH2—CH2—CH2—(4-F—Ph)
179	CF3	CH2—C≡CH	CH2—CH2—CH2—(4-F—Ph)
180	74	CH2—C≡CH	CH2—CH2—CH2—(4-F—Ph)
181	CH3	C3H5-cycl-CH2—	CH2—CH2—CH2—(4-F—Ph)
182	C2H5	C3H5-cycl-CH2—	CH2—CH2—CH2—(4-F—Ph)
183	(CH3)2N—	C3H5-cycl-CH2—	CH2—CH2—CH2—(4-F—Ph)
184	C3H7-i	C3H5-cycl-CH2—	CH2—CH2—CH2—(4-F—Ph)
185	C3H7-n	C3H5-cycl-CH2—	CH2—CH2—CH2—(4-F—Ph)
186	ClH2C—CH2—CH2—	C3H5-cycl-CH2—	CH2—CH2—CH2—(4-F—Ph)
187	H2C═CH—	C3H5-cycl-CH2—	CH2—CH2—CH2—(4-F—Ph)
188	CH3—SO2—CH2—	C3H5-cycl-CH2—	CH2—CH2—CH2—(4-F—Ph)
189	CF3	C3H5-cycl-CH2—	CH2—CH2—CH2—(4-F—Ph)
190	75	C3H5-cycl-CH2—	CH2—CH2—CH2—(4-F—Ph)
191	CH3	H3C—CH2(OH)—	CH2—CH2—CH2—(4-F—Ph)
192	C2H5	H3C—CH2(OH)—	CH2—CH2—CH2—(4-F—Ph)
193	(CH3)2N—	H3C—CH2(OH)—	CH2—CH2—CH2—(4-F—Ph)
194	C3H7-i	H3C—CH2(OH)—	CH2—CH2—CH2—(4-F—Ph)
195	C3H7-n	H3C—CH2(OH)—	CH2—CH2—CH2—(4-F—Ph)
196	ClH2C—CH2—CH2—	H3C—CH2(OH)—	CH2—CH2—CH2—(4-F—Ph)
197	H2C═CH—	H3C—CH2(OH)—	CH2—CH2—CH2—(4-F—Ph)
198	CH3—SO2—CH2—	H3C—CH2(OH)—	CH2—CH2—CH2—(4-F—Ph)
199	CF3	H3C—CH2(OH)—	CH2—CH2—CH2—(4-F—Ph)
200	76	H3C—CH2(OH)—	CH2—CH2—CH2—(4-F—Ph)
201	CH3	H3C—S—CH2—CH2—	CH2—CH2—CH2—(4-F—Ph)
202	C2H5	H3C—S—CH2—CH2—	CH2—CH2—CH2—(4-F—Ph)
203	(CH3)2N—	H3C—S—CH2—CH2—	CH2—CH2—CH2—(4-F—Ph)
204	C3H7-i	H3C—S—CH2—CH2—	CH2—CH2—CH2—(4-F—Ph)
205	C3H7-n	H3C—S—CH2—CH2—	CH2—CH2—CH2—(4-F—Ph)
206	ClH2C—CH2—CH2—	H3C—S—CH2—CH2—	CH2—CH2—CH2—(4-F—Ph)
207	H2C═CH—	H3C—S—CH2—CH2—	CH2—CH2—CH2—(4-F—Ph)
208	CH3—SO2—CH2—	H3C—S—CH2—CH2—	CH2—CH2—CH2—(4-F—Ph)
209	CF3	H3C—S—CH2—CH2—	CH2—CH2—CH2—(4-F—Ph)
210	77	H3C—S—CH2—CH2—	CH2—CH2—CH2—(4-F—Ph)
211	CH3	HS—CH2	CH2—CH2—CH2—(4-F—Ph)
212	C2H5	HS—CH2	CH2—CH2—CH2—(4-F—Ph)
213	(CH3)2N—	HS—CH2	CH2—CH2—CH2—(4-F—Ph)
214	C3H7-i	HS—CH2	CH2—CH2—CH2—(4-F—Ph)
215	C3H7-n	HS—CH2	CH2—CH2—CH2—(4-F—Ph)
216	ClH2C—CH2—CH2—	HS—CH2	CH2—CH2—CH2—(4-F—Ph)
217	H2C═CH—	HS—CH2	CH2—CH2—CH2—(4-F—Ph)
218	CH3—SO2—CH2—	HS—CH2	CH2—CH2—CH2—(4-F—Ph)
219	CF3	HS—CH2	CH2—CH2—CH2—(4-F—Ph)
220	78	HS—CH2	CH2—CH2—CH2—(4-F—Ph)
Table B:
No.	CR9R10CR14R15CR16R17-A
001	CH2—CH2—CH2—Ph
002	CH2—CH2—CH2—(4-Br—Ph)
003	CH2—CH2—CH2—(4-CH3—Ph)
004	CH2—CH2—CH2—(4-Ph—Ph)
005	CH2—CH2—CH2—(4-CN—Ph)
006	CH2—CH2—CH2—(4-Et—Ph)
007	CH2—CH2—CH2—(4-NO2—Ph)
008	CH2—CH2—CH2—[4-(CH2═CH)—Ph]
009	CH2—CH2—CH2—(4-H5C2—Ph)
010	CH2—CH2—CH2—(4-CH3O—Ph)
011	CH2—CH2—CH2—[4-(O—CH2—CH═CH2)—Ph]
012	CH2—CH2—CH2—(4-OCF3—Ph)
013	CH2—CH2—CH2—(4-CH3S—Ph)
014	CH2—CH2—CH2—(4-CF3S—Ph)
015	CH2—CH2—CH2—[4-(CH3—SO2)—Ph]
016	CH2—CH2—CH2[4-(CH3—CO)—Ph]
017	CH2—CH2—CH2—[4-(CH3)2N—Ph]
018	CH2—CH2—CH2—[4-(CH3OOC)—Ph]
019	CH2—CH2—CH2—(3-Cl—Ph)
020	CH2—CH2—CH2—(3-F—Ph)
021	CH2—CH2—CH2—(3-Br—Ph)
022	CH2—CH2—CH2—(3-CH3—Ph)
023	CH2—CH2—CH2—(3,4-di-F—Ph)
024	CH2—CH2—CH2—(3,4-di-Cl—Ph)
025	CH2—CH2—CH2—(3,4-di-CH3—Ph)
026	CH2—CH2—CH2—(3-Cl-4-F—Ph)
027	CH2—CH2—CH2—(4-Cl-3-F—Ph)
028	CH2—CH2—CH2—(2,4-di-Cl—Ph)
029	CH2—CH2—CH2—(2,5-di-Cl—Ph)
030	CH2—CH2—CH2—(2-Cl—Ph)
031	CH2—CH2—CH2—(4-Cl-2-F—Ph)
032	CH2—CH2—CH2—(2,4,5-tri-Cl—Ph)
033	CH(CH3)—CH2—CH2—(4-F—Ph)
034	CH(CH3)—CH2—CH2—(4-Cl—Ph)
035	CH(C2H5)—CH2—CH2—(4-F—Ph)
036	CH(C2H5)—CH2—CH2—(4-Cl—Ph)
037	CH2—CH(CH3)—CH2—(4-F—Ph)
038	CH2—CH(CH3)—CH2—(4-Cl—Ph)
039	CH2—CH2—CH(CH3)—(4-F—Ph)
040	CH2—CH2—CH(CH3)—(4-Cl—Ph)
041	C(CH3)2—CH2—CH2—(4-F—Ph)
042	C(CH3)2—CH2—CH2—(4-Cl—Ph)
043	CH2—C(CH3)2—CH2—(4-F—Ph)
044	CH2—C(CH3)2—CH2—(4-Cl—Ph)

[0183] Formulations may be prepared analogously to those described in, for example, WO 95/30651.

Biological Examples

[0184] D-1: Action Against Plasmopara viticola on Vines

[0185] a) Residual-Protective Action

[0186] Vine seedlings are sprayed at the 4- to 5-leaf stage with a spray mixture (0.02% active ingredient) prepared from a wettable powder formulation of the test compound. After 24 hours, the treated plants are infected with a sporangia suspension of the fungus. Fungus infestation is evaluated after incubation for 6 days at 95-100% relative humidity and 20° C.

[0187] b) Residual-Curative Action

[0188] Vine seedlings are infected at the 4- to 5-leaf stage with a sporangia suspension of the fungus. After incubation for 24 hours in a humidity chamber at 95-100% relative humidity and 20° C., the infected plants are dried and sprayed with a spray mixture (0.02% active ingredient) prepared from a wettable powder formulation of the test compound. After the spray coating has dried, the treated plants are placed in the humidity chamber again. Fungus infestation is evaluated 6 days after infection.

[0189] Compounds of Tables 1 to 37 exhibit a good fungicidal action against Plasmopara viticola on vines. Compounds A1.01, A1.03, A1.04, A1.05, A1.06, A1.07, A1.08, A1.09, A1.10, A1.11, A1.12. A2.04, A2.05 and A2.06 completely inhibit fungal infestation in this test.

[0190] D-2: Action Against Phytophthora on Tomato Plants

[0191] a) Residual-Protective Action

[0192] After a cultivation period of 3 weeks, tomato plants are sprayed with a spray mixture (0.02% active ingredient) prepared from a wettable powder formulation of the test compound. After 48 hours, the treated plants are infected with a sporangia suspension of the fungus. Fungus infestation is evaluated after incubation of the infected plants for 5 days at 90-100% relative humidity and 20° C.

[0193] b) Systemic Action

[0194] After a cultivation period of 3 weeks, tomato plants are watered with a spray mixture (0.02% active ingredient based on the volume of the soil) prepared from a wettable powder formulation of the test compound. Care is taken that the spray mixture does not come into contact with the parts of the plants that are above the ground. After 96 hours, the treated plants are infected with a sporangia suspension of the fungus. Fungus infestation is evaluated after incubation of the infected plants for 4 days at 90-100% relative humidity and 20° C.

[0195] Compounds of Tables 1 to 37 exhibit a long-lasting effect against fungus infestation. Compounds A1.01, A.1.03, A.1.04, A.1.05, A.1.06, A.1.07, A.1.08, A.1.09, A1.10, A1.11, A1.12. A2.04, A2.05 and A2.06 completely inhibit fungal infestation in this test.

[0196] D-3: Action Against Phytophthora on Potato Plants

[0197] a) Residual-Protective Action

[0198] 2-3 week old potato plants (Bintje variety) are sprayed with a spray mixture (0.02% active ingredient) prepared from a wettable powder formulation of the test compound. After 48 hours, the treated plants are infected with a sporangia suspension of the fungus. Fungus infestation is evaluated after incubation of the infected plants for 4 days at 90-100% relative humidity and 20° C.

[0199] b) Systemic Action

[0200] 2-3 week old potato plants (Bintje variety) are watered with a spray mixture (0.02% active ingredient based on the volume of the soil) prepared from a wettable powder formulation of the test compound. Care is taken that the spray mixture does not come into contact with the parts of the plants that are above the ground. After 48 hours, the treated plants are infected with a sporangia suspension of the fungus. Fungus infestation is evaluated after incubation of the infected plants for 4 days at 90-100% relative humidity and 20° C. Fungal infestation is effectively controlled with compounds of Tables 1 to 37. Compounds A1.01 and A1.06 completely inhibit fungal infestation in this test.

Claims

1. α-Sulfin- and α-sulfonamino acid amides of formula I

2. A compound according to claim 1 wherein R1 is C1-C12alkyl, C1-C12alkyl substituted with C1-C4alkoxy, C1-C4alkylthio, or C1-C4alkylsulfonyl; C2-C12alkenyl; C2-C12alkynyl; C1-C12haloalkyl; or a group NR12R13 wherein R12 and R13 are each independently of the other hydrogen or C1-C6-alkyl, or together are tetra- or penta-methylene; and R2 is hydrogen and R3 is C1-C8alkyl; C1-C8alkyl substituted with hydroxy, mercapto, C1-C4alkoxy or C1-C4alkylthio; C3-C8alkenyl; C3-C8alkynyl; C3-C8cycloalkyl; C3-C8cycloalkyl-C1-C4alkyl; and R4 is hydrogen or C1-C4alkyl and R5, R6 and R7 are each hydrogen.

3. A compound of formula I according to claim 1 wherein n is one; and R1 is C1-C12alkyl, C2-C12alkenyl; C1-C12haloalkyl; or a group NR12R13 wherein R12 and R13 are each independently of the other hydrogen or C1-C6-alkyl; and R2 is hydrogen and R3 is C1-C4alkyl; C3-C4alkenyl or cyclopropyl; and R4 is hydrogen, methyl or ethyl and R5, R6 and R7 are each hydrogen; and R8 is C1-C6alkyl.

4. A compound of formula I according to claim 1 wherein n is one; and R1 is C1-C4alkyl, C2-C4alkenyl; C1-C4haloalkyl; or C1-C2-dialkylamino; and R2 is hydrogen and R3 is C3-C4alkyl; allyl or cyclopropyl; and R4 is hydrogen or methyl and R5, R6 and R7 are each hydrogen; and R8 is methyl or ethyl.

5. A compound of formula I according to claim 1 wherein n is one; and R1 is C1-C4alkyl, vinyl; C1-C4haloalkyl; or dimethylamino; and R2 is hydrogen and R3 is isopropyl; and R4, R5, R6 and R7 are each hydrogen; and R8 is methyl.

6. A compound of formula I according to any one of claims 1 to 5 wherein R9, R10, R14, R15, R16, R17 are each independently hydrogen or methyl; and A is phenyl optionally substituted by 1 to 3 substituents selected from C1-C8-alkyl, C2-C8-alkenyl, C2-C8-alkynyl, C3-C8-cycloalkyl, C3-C8-cycloalkyl-C1-C4-alkyl, phenyl, phenyl-C1-C4-alkyl wherein the hydrogens of all the preceding substituents may be in turn optionally substituted by one or several same or different halogens; C1-C8-alkoxy; C3-C8-alkenyloxy; C3-C8-alkynyloxy; C1-C8-alkoxy-C1-C4-alkyl; C1-C8halogenalkoxy; C1-C8-alkylthio; C1-C8-halogenalkylthio; C1-C8-alkylsulfonyl; formyl; C2-C8-alkanoyl; hydroxy; halogen; cyano; nitro; amino; C1-C8-alkylamino; C1-C8-dialkylamino; carboxy; C1-C8-alkoxycarbonyl; C1-C8-alkenyloxycarbonyl or C1-C8-alkynyloxycarbonyl.

7. A compound of formula I according to any one of claims 1 to 5, wherein R9, R10, R14, R15, R16, R17 are each hydrogen; and A is phenyl optionally substituted by 1 to 3 substituents selected from C1-C8-alkyl, C2-C8-alkenyl wherein the hydrogens of all the preceding substituents may be in turn optionally substituted by one or several same or different halogens; C1-C8-alkoxy; C1-C8halogenalkoxy; C1-C8-alkylthio; C1-C8-halogenalkylthio; halogen; cyano; nitro or C1-C8-alkoxycarbonyl.

8. A compound of formula I according to any one of claims 1 to 5, wherein R9, R10, R14, R15, R16, R17 are each hydrogen; and A is phenyl optionally substituted by 1 to 3 substituents selected from C1-C8-alkyl; C1-C8-haloalkyl; C1-C8-alkoxy; C1-C8halogenalkoxy; C1-C8-alkylthio; C1-C8-halogenalkylthio; halogen; cyano; nitro or C1-C8-alkoxycarbonyl.

9. A process for the preparation of a compound of formula I according to claim 1, which comprises reacting a) an amino acid of formula II or a carboxy-activated derivative thereof 80wherein R1, n, R2 and R3 are as defined for formula I is reacted with an amine of formula III 81wherein R4, R5, R6, R7, R8, R9, R10, R14, R15, R16, R17 and A are as defined for formula I optionally in the presence of a base and optionally in the presence of a diluting agent, or b) an amino acid derivative of formula VI 82wherein R4, R5, R6, R7, R8, R9, R10, R14, R15, R16, R17 and A are as defined for formula I with a sulfonyl halide or a sulfinyl halide of formula V 83wherein R1 and n are as defined for formula I and X is halide, preferentially chlorine or bromine, or c) a phenol of formula VII 84wherein R1, n, R2, R3, R4, R5, R6, R7 and R8 are as defined for formula I with a compound of formula VIII 85wherein R9, R10, R14, R15, R16, R17 and A are as defined for formula I and Y is a leaving group like a halide such as a chloride or bromide or a sulfonic ester such as a tosylate, mesylate or triflate.

10. A process for the preparation of a compound of formula Ia

11. A composition for controlling and protecting against phytopathogenic microorganisms, comprising a compound of formula I according to claim 1 as active ingredient together with a suitable carrier.

12. The use of a compound of formula I according to claim 1 in protecting plants against infestation by phytopathogenic microorganisms.

13. A method of controlling and preventing an infestation of crop plants by phytopathogenic microorganisms, which comprises the application of a compound of formula I according to claim 1 as active ingredient to the plant, to parts of plants or to the locus thereof.

14. A method according to claim 13, wherein the phytopathogenic microorganisms are fungal organisms.