DE3923202A1 - New 1-azolyl-3-phenyl-alkanol derivs. - Google Patents

Abstract

Azole derivs. of formula (I), their stereosomers and their salts and metal complexes are new: R1 = alkyl (when R5 is not H0, 2-R7-ethynylor C(R8)-CR9R10; R7-R10=H, halo, alkyl, alkenyl or alkynyl; R2 0 H, alkyl, alkenyl or alkynyl provided that there is no unsatdn. on the C adjacent the O, R3-R6 = H, alkyl, alkenyl or alkynyl; X,Y and Z = H, halo, alkyl (opt. substd. by halo or cycloalkyl, cycloalkyl, alkenyl, alkynyl, opt. substd. aryl, opt. substd. aralkyl, alkoxy, cryloxy, haloalkoxy or aralkoxy; Az = imidazol-1-yl or 1,2,4-triazol-1-yl; provided that when (1) R3=R4=Me, R5=R6-H and Az-1,2,4-triazol-1-yl; then R1 is not 2-alkyl-ethynyl; and (2) R3=R4=alkyl, R5=H and R6 = alkyl, alkenyl or alkynylthen R8-R10 are not all H,

Description

The invention relates to heterocyclic compounds, which are useful as fungicides, to methods of preparation the compound containing fungicides Compositions and methods using the same for controlling fungi, in particular fungal infestation in plants.

The invention relates to compounds of the general Formula (I)

and stereoisomers thereof, wherein R¹ is alkyl (when R⁵ something other than hydrogen) or for a group of general formula (II)

-C≡C-R⁷ (II)

or a group of the general formula (III)

wherein R⁷, R⁸, R⁹ and R¹⁰ are independently hydrogen, Halogen, alkyl, alkenyl or alkynyl; R² for Is hydrogen, alkyl, alkenyl or alkynyl (provided that the carbon atom is in the vicinity of the oxygen not involved in unsaturation); R³, R⁴, R⁵ and R⁶ are independently hydrogen, alkyl, alkenyl or  Alkynyl; X, Y and Z are independently selected Hydrogen, halogen, alkyl, haloalkyl, cycloalkyl, Cycloalkylalkyl, alkenyl, alkynyl, optionally substituted Aryl, optionally substituted aralkyl, Alkoxy, optionally substituted aryloxy, haloalkoxy or optionally substituted aralkoxy; and Az for Imidazol-1-yl or 1,2,4-triazol-1-yl; with the proviso that when R³ and R⁴ are both methyl, R⁵ and R⁶ are both are hydrogen and Az is 1,2,4-triazol-1-yl, R¹ is not -C≡C-alkyl, and with the further proviso, that when R³ and R⁴ are both alkyl, R⁵ is Is hydrogen and R⁶ is alkyl, alkenyl or alkynyl R,, R⁹ and R¹⁰ are not all hydrogen; and Salts and metal complexes thereof.

The compounds of the invention are in general obtained in the form of mixtures of geometric isomers, such as B. of diastereoisomers and isomers with E and Z double bonds, including cis and trans double bonds. These and other mixtures of optical isomers can into individual isomers by methods known in the art be separated. Such isomers form part of the present invention Invention.

Alkyl groups having 1 to 4 carbon atoms, which by R³ to R¹⁰ are either straight-chain or branched-chain Groups, such as Methyl, ethyl, n-propyl, Isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl. Alkyl groups of 1 to 6 carbon atoms represented by R¹ or R² are either straight-chain or Branched-chain groups, such. Methyl, ethyl, n-propyl, Isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl (straight or branched) or hexyl (straight or branched). Alkyl groups and the alkyl portions of alkoxy, haloalkyl, Haloalkoxy, aralkyl and aralkoxy represented by X, Y and Z are either straight-chain or Branched-chain groups of 1 to 6 carbon atoms, such as z. Methyl, ethyl, propyl, butyl, pentyl or hexyl, inclusive  the above-mentioned specific isomers.

Alkenyl groups of 2 to 4 carbon atoms represented by R³ to R¹⁰ are shown and the same or different can be, for. Alk-1-enyl, alk-2-enyl or alk-3-enyl, such as Vinyl, 2-prop-1-enyl, 1-prop-1-enyl, allyl, 2-but-2-enyl, 1- (2-methylprop-1-enyl), 1-but-1-enyl, 2-but-2-enyl, 1- (1-methylprop-2-enyl), 1- (2-methylprop-2-enyl). 1-but-2-enyl, or 1-but-3-enyl. Alkenyl groups with 3 to 6 carbon atoms represented by R² and either E or Z geometry (including cis and trans), z. Alk-2-enyl, alk-3-enyl, Alk-4-enyl or alk-5-enyl, such as. Allyl, 1- (1-methylprop-2-enyl), 1- (2-methylprop-2-enyl), 1-but-2-enyl, 1-but-3-enyl, Pent-2-enyl, pent-3-enyl, pent-4-enyl, hex-2-enyl, hex-3-enyl, Hex-4-enyl or hex-5-enyl. Alkenyl groups by X, Y and Z are shown, the same or different can be and the E or Z geometry (including cis and trans) are either straight chain or branched-chain groups having 2 to 6 carbon atoms, such as Vinyl or allyl, or any of the above Examples.

Alkynyl groups of 2 to 4 carbon atoms represented by R³ to R¹⁰ are shown and the same or different can be, for. Ethynyl, prop-1-ynyl, propargyl, 2-but-3-ynyl, but-1-ynyl, but-2-ynyl or but-3-ynyl. Alkynyl groups of 3 to 6 carbon atoms represented by R² are shown, for. Alk-2-ynyl, alk-3-ynyl, alk-4-ynyl or alk-5-ynyl, such as. As propargyl or but-2-inyl. Alkynyl groups represented by X, Y and Z, can be either straight or branched groups of 2 to 6 Be carbon atoms, such as. Ethinyl or propargyl, or any of the examples above.

Cycloalkyl groups represented by X, Y and Z, may be C₃-C₇-cycloalkyl, such as. Cyclopropyl,  Cyclobutyl, cyclopentyl, cyclohexyl or cycloheptyl.

Cycloalkylalkyl groups represented by X, Y and Z. are, z. B. C₃-C₇-cycloalkyl (C₁-C₆) alkyl groups, such as z. Cyclopropylmethyl, cyclohexylmethyl or 1-cyclopropylethyl.

Examples of X, Y and Z when these aryl, aralkyl, aryloxy or aralkoxy groups are phenyl, benzyl, phenoxy and benzyloxy. These rings can be substituted by Halogen (fluorine, chlorine or bromine), C₁-C₆-alkyl (eg. Ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl), C₁-C₆ alkoxy (e.g., methoxy, ethoxy, propoxy or butoxy), halo-C₁-C₆-alkyl (eg trifluoromethyl), Halo-C₁-C₆alkoxy (eg trifluoromethoxy), nitro, phenyl or phenoxy.

Halogen atoms are fluorine, chlorine, bromine or iodine atoms.

The invention further relates to compounds of the general Formula (I)

and stereoisomers thereof, wherein R¹ is an alkyl group with 1 to 6 carbon atoms (for cases where R⁵ is something other than hydrogen) or a group of the general ones Formula (II)

-C≡C-R⁷ (II)

or a group of the general formula (III)

wherein R⁷ to R¹⁰, which are the same or different can, a hydrogen atom, an alkyl group with 1 to 4 carbon atoms or an alkenyl or alkynyl group with 2 to 4 carbon atoms or a halogen atom (fluorine, Chlorine, bromine or iodine); R² represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a Alkenyl or alkynyl group having 3 to 4 carbon atoms (assuming that the carbon atom is adjacent to the oxygen atom not involved in unsaturation is); R³ to R⁶, which may be the same or different can each represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an alkenyl or alkynyl group with 2 to 4 carbon atoms; X, Y and Z, which may be the same or different, each for one Hydrogen atom, a halogen atom (fluorine, chlorine or bromine), an alkyl, cycloalkyl, cycloalkylalkyl, alkenyl, alkynyl, Aryl, aralkyl, alkoxy, aryloxy or aralkoxy group; and Az is 1-imidazole or 1,2,4-triazole; with the proviso when R³ and R⁴ are both methyl, R⁵ and R⁶ both are hydrogen and Az is 1,2,4-triazol-1-yl R¹ is not -C≡C-alkyl, and with the other when R³ and R⁴ are both alkyl, R⁵ is hydrogen and R⁶ is alkyl, alkenyl or alkynyl R,, R⁹ and R¹⁰ are not all hydrogen; and Salts and metal complexes thereof.

The invention further relates to compounds of the general Formula (I)  

and stereoisomers thereof, wherein R¹ is C₁-C₆ alkyl (when R⁵ is something other than hydrogen) or a group of general formula (II)

-C≡C-R⁷ (II)

or a group of the general formula (III)

wherein R⁷, R⁸, R⁹ and R¹⁰ are independently hydrogen, Halogen, C₁-C₄-alkyl, C₂-C₄-alkenyl or C₂-C₄-alkynyl; R² is hydrogen, C₁-C₆-alkyl, C₃-C₆-alkenyl or C₃-C₆ alkynyl (provided that the carbon atom in the vicinity of the oxygen not in an unsaturation is included); R³ to R⁶ independently represent hydrogen, C₁-C₄ alkyl, C₂-C₄ alkenyl or C₂-C₄ alkynyl; X, Y and Z are independently selected from hydrogen, halogen, C₁-C₆alkyl, halo (C₁-C₆) alkyl, C₃-C₇cycloalkyl, C₃-C₇cycloalkyl (C₁-C₆) alkyl, C₂-C₆ alkenyl, C₂-C₆ alkynyl, phenyl, Phenyl (C₁-C₆) alkyl, C₁-C₆-alkoxy, halo (C₁-C₆) alkoxy, Phenoxy or phenyl (C₁-C₆) alkoxy; and Az for imidazol-1-yl or 1,2,4-triazol-1-yl; wherein the above phenyl radicals optionally substituted by halogen, C₁-C₆-alkyl, C₁-C₆ alkoxy, halo (C₁-C₆) alkyl, halo (C₁-C₆) alkoxy, Nitro, phenyl or phenoxy; with the proviso that when R³ and R⁴ are both methyl, R⁵ and R⁶ are both Are hydrogen and Az is 1,2,4-triazol-1-yl, R¹ is not -C≡C-alkyl, and with the further proviso, that when R³ and R⁴ are both alkyl, R⁵ is hydrogen  R und is alkyl, alkenyl or alkynyl, R⁸, R⁹ and R¹⁰ are not all hydrogen; and salts and metal complexes thereof.

The invention further relates to compounds of the general Formula (I)

and stereoisomers thereof, wherein R¹ is C₃-C₄ alkyl; R, R³ and R⁶ are independently hydrogen or C₁-C₄ alkyl; R⁴ is hydrogen; R⁵ is C₁-C₄ alkyl; X, Y and Z is independently hydrogen, halogen, C₁-C₄-alkyl, C₁-C₄-alkoxy, Phenoxy or phenyl; and Az for imidazol-1-yl or 1,2,4-triazol-1-yl; and salts and metal complexes from that.

The invention further relates to compounds of the formula (I) wherein R¹ is C₃-C₄-alkyl; wherein R² is hydrogen or Methyl is; R³, R⁴ and R⁶ are all hydrogen; R⁵ is C₁-C₂-alkyl; Az is 1,2,4-triazol-1-yl; and X, Y and Z are independently hydrogen, chlorine or fluorine atoms stand; and salts and metal complexes thereof.

The invention further relates to compounds of the general Formula (I)

and stereoisomers thereof, wherein R¹ is a group of the general Formula (II)

-C≡C-R⁷ (II)

or a group of the general formula (III)

wherein R⁷, R⁸, R⁹ and R¹⁰ are independently hydrogen, Halogen, C₁-C₄-alkyl, C₂-C₄-alkenyl or C₂-C₄-alkynyl; R² is hydrogen, C₁-C₄-alkyl, C₃-C₆-alkenyl or C₃-C₆-alkynyl (provided that the carbon atom in Neighborhood to oxygen is not in an unsaturation is included); R³, R⁴, R⁵ and R⁶ are independently hydrogen, C₁-C₆ alkyl, C₂-C₄ alkenyl or C₂-C₄ alkynyl; X, Y and Z are independently hydrogen, chlorine or fluorine stand; and Az represents imidazol-1-yl or 1,2,4-triazol-1-yl stands; with the proviso that when R³ and R⁴ are both for Methyl, R⁵ and R⁶ both represent hydrogen and Az is 1,2,4-triazol-1-yl, R 1 is not -C≡C-alkyl, and with the further proviso that when R³ and R⁴ both are alkyl, R⁵ is hydrogen and R⁶ is alkyl, alkenyl or alkynyl, R⁸, R⁹ and R¹⁰ not all mean hydrogen; and salts and metal complexes thereof.

The invention further relates to compounds of the general Formula (XXXIV)

and stereoisomers thereof, wherein R¹ is a group of the general Formula (II)

-C≡C-R⁷ (II)

or a group of the formula (III)

wherein R⁷, R⁸, R⁹ and R¹⁰ are independently hydrogen or C₁-C₄alkyl; R² is hydrogen, C₁-C₄-alkyl, Allyl or propargyl; X, Y and Z are independently hydrogen, Chlorine or fluorine; and salts and metal complexes from that.

The invention further relates to compounds of the general Formula (XXXV)

and stereoisomers thereof, wherein R¹ is a group of the general Formula (II)

-C≡C-R⁷ (II)

or a group of the general formula (III)

wherein R⁷ is C₁-C₄-alkyl, R⁸ is hydrogen and one of the symbols R⁹ and R¹⁰ is hydrogen and the other is C₁-C₄alkyl; R² for hydrogen or Methyl is; and X and Y are hydrogen, chlorine or fluorine stand; and salts and metal complexes thereof.

The invention further relates to the compound

(Compound 233 in Table I) and their stereoisomers; and Salts and metal complexes thereof.

In the following Table I are the meanings of the abbreviations as follows:

Me is methyl
Et is ethyl
n _Pr is normal propyl
i _Pr is isopropyl
n _Bu is normal butyl
i _Bu is isobutyl
s _Bu is secondary butyl
t _Bu is tertiary butyl
Tr is 1,2,4-triazol-1-yl

All melting points in Table I are expressed in ° C.

Although the azole (Az) in column 11 of Table I is labeled with Tr (ie, 1,2,4-triazol-1-yl), it should be understood that it is just as likely to be Im (ie, imidazol-1-yl). can exist. This description should be read to include in all cases the 1-imidazol-1-yl which corresponds to the specified 1,2,4-triazol-1-yl.

Table II shows proton NMR data for certain compounds those described in Table I and characterized therein as oils are. The chemical shifts are in ppm Downfield measured from tetramethylsilane. deuterochloroform was used throughout as a solvent. The following Abbreviations are used:

br = wide
s = singlet
d = doublet
dd = doublet of doublets
Hz = Hertz
t = triplet
q = Quartet
m = multiplet
J = coupling constant

connection 8th 8.20 (1H, s), 7.92 (1H, s), 7.41 (2H, m), 7.20 (1H, m), 4.38 (1H, d, J 12Hz), 4.29 (1H, d, J 12Hz), 3.39 ( 3H, s), 3.11 (2H, s), 1.80 (3H, s). 14 8.14 (1H, s), 7.85 (1H, s), 7.38 (1H, m), 7.34 (1H, m), 7.13 (1H, m), 4.32 (1H, d, J 12Hz), 4.24 (1H, d , J 12Hz), 3.32 (3H, s), 3.04 (2H, s), 2.09 (2H, q, J 7Hz), 0.99 (3H, t, J 7Hz) 25 8.08 (1H, s), 7.93 (1H, s), 7.36 (2H, m), 7.21 (1H, m), 5.46 (2H, m), 4.28 (1H, d, J 13Hz), 4.18 (1H, d , J 13Hz), 3.45 (1H, s), 3.00 (2H, m), 1.56 (3H, d, J 7Hz) 43 8.05 (1H, br s), 7.81 (1H, br s), 7.30 (2H, m), 7.10 (1H, m), 5.43 (1H, dd, J 15 and 7Hz), 5.33 (1H, d, J 15Hz ), 2.96 (1H, d, J 12Hz), 2.89 (1H, d, J 12Hz), 2.88 (1H, s), 1.83 (2H, Quintet, J 7Hz), 0.75 (3H, t, J 7Hz). 68 8.21 (1H, s), 7.91 (1H, s), 7.48 (1H, m), 7.38 (1H, m), 7.22 (2H, m), 4.39 (1H, d, J 13Hz), 4.29 (1H, d , J 13Hz), 3.40 (3H, s), 3.19 (2H, m), 1.79 (3H, s). 74 8.21 (1H, s), 7.90 (1H, s), 7.49 (1H, m), 7.37 (1H, m), 7.21 (2H, m), 4.39 (1H, d, J 13Hz), 4.30 (1H, d , J 13Hz), 3.41 (3H, s), 3.18 (2H, s), 2.14 (2H, q, J 7Hz), 1.05 (3H, t, J 7Hz). 85 8.12 (1H, br s), 7.92 (1H, br s), 7.38 (2H, m), 7.20 (2H, m), 5.50 (2H, m), 4.31 (1H, d, J 13Hz), 4.19 (1H , d, J 13Hz), 3.32 (1H, br s), 3.05 (2H, m), 1.56 (3H, d, J 7Hz). 87 8.18 (1H, br s), 7.91 (1H, br s), 7.30 (2H, m), 7.22 (2H, m), 5.55 (1H, m), 5.19 (1H, d, J 16Hz), 4.34 (1H , d, J 13Hz), 4.21 (1H, d, J 13Hz), 3.32 (3H, s), 3.15 (1H, d, J 13Hz), 3.06 (1H, d, J 13Hz), 1.67 (3H, d, J 7Hz). 103 8.11 (1H, br s), 7.91 (1H, br s), 7.38 (2H, m), 7.20 (2H, m), 5.57 (2H, m), 4.31 (1H, d, J 13Hz), 4.20 (1H , d, J 13Hz), 3.39 (1H, br s), 3.10 (1H, d, J 12Hz), 3.02 (1H, d, J 12Hz), 1.89 (2H, m), 0.83 (3H, t, J 7Hz ). 105 8.17 (1H, br s), 7.89 (1H, br s), 7.30 (2H, m), 7.21 (2H, m), 5.52 (1H, m), 5.16 (1H, d, J 16Hz), 4.34 (1H , d, J 13Hz), 4.24 (1H, d, J 13Hz), 3.32 (3H, s), 3.10 (2H, m), 2.01 (2H, Quintet, J 7Hz), 0.91 (3H, t, J 7Hz) , 128 8.20 (1H, s), 7.94 (1H, s), 7.28 (4H, m), 4.30 (1H, d, J 12Hz), 4.20 (1H, d, J 12Hz), 3.39 (3H, s), 2.87 ( 2H, s), 1.82 (3H, s). 133 8.18 (1H, s), 7.94 (1H, s), 7.28 (4H, m), 4.30 (2H, m), 3.69 (1H, br s), 2.94 (2H, m), 2.09 (2H, q, J 7Hz), 1.03 (3H, t, J 7Hz). 134 8.19 (1H, s), 7.93 (1H, s), 7.29 (4H, m), 4.33 (1H, d, J 13Hz), 4.21 (1H, d, J 13Hz), 3.39 (3H, s), 2.21 ( 2H, q, J 7Hz), 1.09 (3H, t, J 7Hz). 147 8.13 (1H, s), 7.92 (1H, s), 7.27 (4H, m), 5.54 (1H, m), 5.17 (1H, d, J 16Hz), 4.20 (1H, d, J 13Hz), 4.10 ( 1H, d, J 13Hz), 3.31 (3H, s), 2.95 (1H, d, J 13Hz), 2.76 (1H, d, J 13Hz), 1.70 (3H, d, J 7Hz). 153 8.16 (1H, s), 7.93 (1H, s), 7.25 (4H, m), 5.88 (1H, m), 5.56 (1H, m), 5.21 (3H, m), 4.23 (2H, m), 4.01 (2H, m), 2.95 (1H, d, J 12Hz), 2.80 (1H, d, J 12Hz), 1.70 (3H, d, J 7Hz). 163 8:09 (1H, s), 7.92 (1H, s), 7.27 (2H, m), 7.14 (2H, m), 5.50 (1H, m), 5:34 (3H, m, J 16Hz), 4.19 (2H, m ), 3.15 (1H, s), 2.86 (1H, d, J 12Hz), 2.73 (1H, d, J 12Hz), 1.92 (2H, Quintet, J 7Hz), 0.84 (3H, t, J 7Hz). 165 8.13 (1H, s), 7.91 (1H, s), 7.28 (2H, m), 7.20 (2H, m), 5.56 (1H, m), 5.17 (1H, d, J 16Hz), 4.22 (1H, d , J 12Hz), 4.15 (1H, d, J 12Hz), 3.31 (3H, s), 2.96 (1H, d, J 12Hz), 2.79 (1H, d, J 12Hz), 2.04 (2H, m), 0.93 (3H, t, J 7Hz). 193 8.21 (1H, s), 7.99 (1H, s), 7.54 (1H, m), 7.14 (1H, m), 6.98 (1H, m), 4.33 (2H, m), 3.28 (1H, d, J 12Hz ), 3.14 (1H, d, J 12Hz), 2.08 (2H, q, J 7Hz), 1.00 (3H, t, J 7Hz). 223 8.24 and 8.22 (1H, 2xs), 7.99 and 7.96 (1H, 2xs), 7.45 (2H, m), 7.14 (1H, m), 6.99 (1H, m), 5.49 (2H R¹ is CH = CHCH₂CH₃, m) , (is 2H, R CH = CHCH₂CH₃, quintet, J 7 Hz) 4:40 to 4:00 (2H, m), 3:00 (2H, m), 1.92, 1:45 to 1:25 (6H, compound R¹ is ⁿ Bu, m), 0.91 and 0.85 (3H, 2xt, J 7 Hz). 421 8.15 (1H, s), 7.91 (1H, s), 7.81 (1H, m), 7.36 (1H, m), 7.19 (1H, m), 4.48 (1H, q, J 7 Hz), 4.29 (1H, s), 3.43 (1H, d, J 13 Hz), 3.17 (1H, d, J 13 Hz), 1.71 (1H, d, J 7Hz), 1.91 (9H, s). 424 Major diastereoisomer 8.15 (1H, s), 7.88 (1H, s), 7.80 (1H, m), 7.34 (1H, m), 7.18 (2H, m), 4.54 (1H, q, J 7Hz), 4.16 (1H , s), 3.45 (1H, d, J 13 Hz), 3.23 (1H, d, J 13 Hz), 1.72 (3H, d, J 7Hz), 1.92 (9H, s). Sub diastereoisomer 7.96 (1H, s), 7.80 (1H, m), 7.63 (1H, s), 7.40-7.00 (3H, m), 4.79 (1H, s), 4.66 (1H, q, J 7 Hz), 3.35 (1H, d, J 13 Hz), 3.05 (1H, d, J 13 Hz), 1.81 (3H, d, J 7Hz), 1.11 (9H, s). 426 Major diastereoisomer 17.08 (1H, s), 7.90 (1H, s), 7:57 (1H, m), 7.25-6.80 (3H, m), and 4.50 (1H, q, J 7 Hz), 3.86 (1H, s), 3:34 (1H, d, J 12 Hz), 3.09 (1H, d, J 12 Hz), 1.68 (3H, d, J 7Hz) and 0.89 (9H, s). 426 Sub diastereoisomer 7.95 (1H, s), 7.62 (1H, s), 7.57 (1H, m), 7.25-6.80 (3H, m), 4.65 (1H, q, J 7 Hz), 4.23 (1H, s), 3.05 (1H, d, J 12 Hz), 2.91 (1H, d, J 12Hz), 1.79 (3H, d, J 7Hz), 1.10 (9H, s). 430 8.15 (1H, s), 7.89 (1H, s), 7.82 (1H, m), 7.09 (1H, m), 6.94 (1H, m), 4.48 (1H, q, J 7 Hz), 4.24 (1H, s), 3.41 (1H, d, J 13 Hz), 3.15 (1H, d, J 13 Hz), 1.70 (1H, d, J 7Hz), 0.91 (9H, s). 432 8.09 (1H, s), 7.81 (1H, s), 7.62 (1H, m), 6.82 (1H, m), 6.70 (1H, m), 4.44 (1H, q, J 7Hz), 3.98 (1H, s), 3.69 (3H, s), 3.30 (1H, d, J 13Hz), 3.07 (1H, d, J 13Hz), 1.64 (3H, d, J 7Hz), 0.81 (9H, s).

Compounds of the general formula (I)

wherein Az, R¹ to R⁶, X, Y and Z are as defined above unless R² is not hydrogen, can be prepared from compounds of the general Formula (IV) (Compounds of formula (I) wherein R² is hydrogen)

wherein Az, R¹, R³ to R⁶, X, Y and Z are as defined above own, by treatment with a base, such as z. Sodium hydride, and an alkyl halide, an alkenyl halide or an alkynyl halide, R 2 Hal, where Hal is chlorine, Bromine or iodine, in a suitable solvent, such as B. tetrahydrofuran.

Compounds of general formula (IV) wherein R¹ is a Group of the general formula (III), wherein R⁸ and R⁹ or R⁸ and R¹⁰ are hydrogen  by reduction of compounds of general formula (V) (Compounds of general formula (IV) wherein R¹ is for a group of the general formula (II) stands)

wherein Az, R³ to R⁷, X, Y and Z are as defined above have. In cases where both R⁸ and R⁹ may represent hydrogen (a trans double bond) be achieved by an aluminum hydride reducing agent, such as As sodium bis (2-methoxyethoxy) aluminum hydride or Lithium aluminum hydride in a corresponding solvent, such as B. tetrahydrofuran. In cases where both R⁸ and R¹⁰ are hydrogen (a cis double bond) this can be achieved by catalytic hydrogenation over a suitable catalyst, such as. B. palladium on barium sulfate.

Compounds of the general formula (V) can be prepared are treated by treating compounds of the general Formula (VI)

wherein Az, R³ to R⁶, X, Y and Z are as defined above possess, with a metal acetylide of the general Formula (VII)

M-C≡C-R⁷ (VII)

wherein R⁷ has the meaning given above and M for a Metal, such as. As lithium, magnesium or titanium, stands M can also be silicon, in the presence of a suitable Fluoride catalyst.

As an alternative, compounds of the general formula (IV) wherein R¹ is a group of the general formula (III) is prepared by treatment of compounds of general formula (VI) with compounds of general Formula (VIII)

wherein R⁸ to R¹⁰ have the meanings given above and M for magnesium (a Grignard reagent) or lithium is, in a suitable solvent, such. B. tetrahydrofuran.

Compounds of general formula (IV) wherein R¹ is a Alkyl group is (and R⁵ is not hydrogen) be prepared by treatment of compounds of general formula (VI) with compounds of general Formula R¹M wherein R¹ has the meaning given above  and M is a metal, such as. As lithium or Magnesium.

Compounds of general formula (VI) can be prepared are treated by treating compounds of the general Formula (IX)

wherein Hal, R³ to R⁶, X, Y and Z are as defined above possess, with an azole (imidazole or 1,2,4-triazole) in the presence of a suitable base, such as. For example, potassium carbonate, in a suitable solvent, such as. B. dimethylformamide.

As an alternative, compounds of the general formula (V) can be prepared by treating compounds of general formula (IX) with compounds of general Formula (VII) wherein M is lithium, magnesium or titanium and then by treatment with an azole (Imidazole or 1,2,4-triazole).

As a further alternative, compounds of the formula (IV) wherein R¹ is a group of the general formula (III), be prepared by treatment of compounds of general formula (IX) with a compound of general Formula (VIII) wherein M is lithium or magnesium, and subsequent treatment with an azole (imidazole or 1,2,4-triazole).

Compounds of the general formula (IX) can be prepared are obtained by oxidation of compounds of the general  formula

wherein Hal, R³ to R⁶, X, Y and Z are as defined above possess, with a suitable oxidizing agent, such as B. Jones reagent.

Compounds of the general formula (X) in which R⁵ and R⁶ are hydrogen can be prepared by treatment of compounds of general formula (XI)

wherein R³, R⁴, X, Y and Z are as defined above possess, with a solution of the appropriate halogen, such as z. As bromine, in water.

Compounds of general formula (XI) wherein R³ and R⁴ are hydrogen, can be prepared by Treatment of Grignard reagents of the general formula (XII)  

in which Hal, X, Y and Z have the meanings given above, with allyl bromide, optionally in the presence of a Copper (I) catalyst, in a suitable solvent, such as B. diethyl ether.

Compounds of the general formula (XII) can be prepared are determined by methods described in the literature.

As an alternative, compounds of the general formula (IX) can be prepared by treating Grignard reagents the general formula (XIII)

wherein Hal, R³, R⁴, X, Y and Z are as defined above possess, with an acid chloride of the general formula (XIV)

in which Hal, R⁵ and R⁶ have the meanings given above, in a suitable solvent, such as. B. diethyl ether or tetrahydrofuran, at low temperature.

Compounds of the general formula (XIII) and (XIV) can be are prepared by methods derived from the literature are known.

As a further alternative, compounds of the general Formula (VI) can be prepared by oxidation of compounds of general formula (XV)

wherein Az, R³ to R⁶, X, Y and Z are as defined above have. A convenient oxidation method is the Swern modification of the Moffat oxidation (dimethyl sulfoxide, Oxalyl chloride and triethylamine in dichloromethane) or the Moffat oxidation (dimethyl sulfoxide, acetic anhydride and triethylamine in dichloromethane) or use from Jones reagents.

Compounds of the general formula (XV) in which R⁵ and R⁶ are hydrogen can be prepared by treatment an epoxide of general formula (XVI)  

wherein R³, R⁴, X, Y and Z are as defined above possess, with an azole (imidazole or 1,2,4-triazole) in a suitable solvent, such as. For example, ethanol.

Compounds of general formula (XVI) can be prepared be by epoxidation of compounds of the general Formula (XI) with a suitable peracid such. B. peracetic acid or m-chloroperbenzoic acid.

As an alternative, compounds of the general formula (XVI) can be prepared by treating a compound of general formula (X) (wherein R⁵ and R⁶ are hydrogen stand) with a suitable base, such. For example, sodium hydroxide, in a suitable solvent, such as. For example, methanol or Ethanol.

As an alternative, compounds of the general formula (IV) wherein R⁶ is hydrogen by treatment of compounds of the general formula (XVII)

wherein R¹, R³ to R⁵, X, Y and Z are as defined above possess, with an azole (imidazole or 1,2,4-triazole) in a suitable solvent, such as. B. ethanol

Compounds of general formula (XVII) can be prepared are treated by treating compounds of the general Formula (XVII)

wherein R¹, R³, R⁴, X, Y and Z are as defined above possess, with a sulfur ylide of the general formula (XIX)

wherein R⁵ has the meaning given above and R is for Methyl is, if R⁵ is hydrogen, or R is phenyl if R⁵ is not hydrogen, in a suitable Solvents, such as. For example, dimethyl sulfoxide. Sulfur ylides of the general formula (XIX) can be prepared by Methods known from the literature.

Compounds of the general formula (XVIII) in which R¹ represents a group of the general formula (II) can be prepared are known by methods known from the literature  are, such. B. by treatment of compounds the general formula (XX)

wherein R³, R⁴, X, Y and Z are as defined above possess, with a compound of general formula (VII), wherein R² has the meaning given above and M is for Copper (I) or M is trialkyltin or hydrogen in the presence of a palladium catalyst.

As an alternative, compounds of the general formula (XVIII) wherein R¹ is a group of the general formula (II) is prepared by treatment of compounds the general formula (XXI)

wherein R³, R⁴, X, Y and Z are as defined above possess, with a compound of general formula (VII), wherein M is lithium or magnesium, and subsequent Oxidation with a suitable oxidizing agent, such as. B. Chromium trioxide.

As a further alternative, compounds of the general  Formula (XVIII) wherein R¹ is a group of the general Formula (II) can be prepared by treating a Compound of the general formula (XXII)

wherein R³, R⁴, X, Y and Z are as defined above and NR₂ is a suitable amide group, such as z. B. NMeOMe, with a compound of the general formula (VII) wherein M is lithium or magnesium in one suitable solvents, such as. B. tetrahydrofuran.

Compounds of the general formula (XVIII) in which R¹ represents a group of general formula (III) can be prepared be by methods which from the literature are known, for example by treatment of compounds of general formula (XX) with compounds of general Formula (VII) wherein M is copper (I) or manganese (I) or tributyltin or magnesium, in the presence of a Palladium catalyst in a suitable solvent, such as B. tetrahydrofuran.

As an alternative, compounds of the general formula (XVIII) wherein R¹ is a group of the general formula (III) can be prepared by treating compounds the general formula (XXII) or the general Formula (XXIII)  

wherein R³, R⁴, X, Y and Z are as defined above have, with a compound of general formula (VIII), wherein M is lithium, in a suitable solvent, such as For example, ethers.

As a further alternative, compounds of the general Formula (XVIII) wherein R¹ is a group of the general Formula (III) can be prepared by treatment of Compounds of general formula (XXI) with compounds of general formula (VIII) wherein R is lithium or Magnesium stands, and subsequent oxidation with a suitable Oxidizing agents, such as. As chromium trioxide or manganese dioxide.

As a further alternative, compounds of the general Formula (XVIII) wherein R¹ is a group of the general Formula (III) and R¹⁰ is not hydrogen, prepared are treated by treating a compound of the general Formula (XXI) with compounds of the general formula (XXIV)

in which Hal, R⁸ and R⁹ have the meanings given above, and the formula R¹¹CH₂ = R¹⁰, and subsequent oxidation with a suitable oxidizing agent, such as. B. Chromium trioxide, and subsequent acid catalyzed rearrangement.

As a further alternative, compounds of the general Formula (XVIII) wherein R¹ is a group of the general Formula (III) is prepared by treatment a compound of general formula (XX) with a compound of the general formula (VIII) wherein M is trialkylsilyl (eg, trimethylsilyl) in the presence of a suitable Lewis acid, such as. B. aluminum trichloride.

As a further alternative, compounds of the general Formula (XVIII) wherein R¹ is a group of the general Formula (III) wherein R⁸ and R⁹ or R⁸ and R¹⁰ is hydrogen are prepared by hydrogenation of compounds of general formula (XVIII) wherein R¹ is a Group of the general formula (II) stands. In cases, in where R⁸ and R⁹ are hydrogen (a trans double bond), is a suitable reducing agent lithium or sodium in liquid ammonia. In cases where R⁸ and R¹⁰ are hydrogen stand (a cis double bond) is a suitable one Reducing agent hydrogen over a suitable catalyst, such as B. palladium on barium sulfate. As alternative may be compounds wherein R⁸ and R⁹ are hydrogen (a trans double bond) are prepared by isomerization of compounds wherein R⁸ and R¹⁰ are hydrogen are (a cis double bond) with a suitable catalyst, such as Iodine.

Compounds of the general formula (XVIII) in which R¹ represents is an alkyl group can be prepared by methods, which are known from the literature, for example by treatment of compounds of general formula (XX) with compounds of the general formula R¹M, wherein R¹ is the has the meaning given above and M is copper (I)  or M is magnesium (at low temperature), in a suitable solvent, such as. B. tetrahydrofuran.

As an alternative, compounds of the general formula (XVIII) wherein R¹ is an alkyl group are treated by treating compounds of the general Formula (XXI) with compounds of the general formula R¹M, wherein R¹ has the meaning given above and M is for Lithium or magnesium, and subsequent oxidation with a suitable oxidizing agent, such as. Chromium trioxide.

As a further alternative, compounds of the general Formula (XVIII) wherein R¹ is an alkyl group are treated by treating compounds of the general Formula (XXII) or the general formula (XXIII) with compounds of the general formula R¹M, wherein R¹ is the has the meaning given above and M is lithium, with a suitable solvent, such as. For example, ethers.

As a further alternative, compounds of the general Formula (XVII) wherein R¹ is an appropriate alkyl group can be prepared by hydrogenation of compounds of the general formula (XVIII) wherein R¹ is a group of general formula (II) or a group of general Formula (III) stands.

As an alternative, compounds of the general formula (VIII) wherein R¹ is an alkyl group are treated by treating a compound of the general Formula (XXV)

wherein R¹ has the meaning given above, with compounds of general formula (XIII), optionally in  Presence of a copper (I) catalyst, in a suitable Solvents, such as. For example, ethers.

As a further alternative, compounds of the general Formula (XVIII) wherein R¹ is an alkyl group are treated by treating compounds of the general Formula (XXVI)

wherein R¹ has the meaning given above, with compounds the general formula (XIII) or compounds of general formula (XXVII)

wherein R³, R⁴, X, Y and Z are as defined above have, in a suitable solvent, such. B. diethyl ether, and subsequent oxidation with a suitable oxidizing agent, such as Chromium trioxide.

As a further alternative, compounds of the general Formula (XVIII) wherein R¹ is an alkyl group are treated by treating compounds of the general Formula (XXVIII)

wherein R¹ has the meaning given above, or compounds the general formula (XXIX)  

wherein R¹ and NR₂ have the meaning given above (eg NR₂ is NMeOMe), with compounds of the general Formula (XXVII) in a suitable solvent, such. B. Diethyl ether.

Compounds of the general formula (XX), (XXI), (XXII), (XXIII), (XXIV), (XXV), (XXVI), (XXVII), (XXVIII) and (XXIX) can be prepared by methods known from the literature become.

As a further alternative, compounds of the general Formula (IV) can be prepared by treatment of compounds the general formula (XXX)

wherein Az, R¹, R⁵ and R⁶ are as defined above, with a Grignard reagent of the general formula (XIII) in a suitable solvent, such as. B. diethyl ether.

Compounds of the general formula (XXX) can be prepared are treated by treating compounds of the general Formula (XXXI)

wherein Hal, R¹, R⁵ and R⁶ are as defined above possess, with an azole (imidazole or 1,2,4-triazole) in Presence of a suitable base, such as. As potassium hydride, in a suitable solvent, such as. B. dimethylformamide.

Compounds of general formula (XXXI) wherein R¹ is for is an alkyl group can be prepared by Treatment of compounds of general formula (XIV) with compounds of the general formula R¹M, wherein R¹ is the has the meaning given above (an alkyl group) and M is copper (I) or M is magnesium (lower Temperature), in a suitable solvent, such as. B. Tetrahydrofuran.

Alternatively, when R¹ is a tertiary alkyl group (e.g. tert-butyl), compounds of the general formula (XXXI) can be prepared by treating compounds the general formula (XXXII)

wherein R¹, R⁵ and R⁶ have the meanings given above, with a suitable halogen (eg, chlorine or bromine), as is described in the literature.

Compounds of the general formula (XXXII) can be prepared are by methods which are known from the literature.

As a further alternative, compounds of the general Formula (IV), wherein R³ and R⁴ are hydrogen, prepared are treated by treating compounds of the general Formula (XXXIII)  

wherein Az, R¹, R⁵ and R⁶ are as defined above possess, with a Grignard reagent of the general formula (XII) in the presence of a copper (I) catalyst.

The compounds of general formula (XXXIII) can be prepared are treated by treating compounds of the general Formula (XXX) with the sulfur ylide of the formula Me₂S⁺CH₂⁻.

The compounds, their salts and metal complexes are active Fungicides, especially against the diseases Puccinia recondita, Puccinia striiformis and other rust diseases on wheat, Puccinia hordei, Puccinia striiformis and others Rust diseases on barley and rust on other host plants, such as As coffee, apples, vegetables and ornamental plants.

Furthermore, they are active fungicides against Erysiphe graminis (Powdery mildew) on barley and wheat and other powdery mildew diseases on various host plants, such. B. Sphaerotheca fuliginea on pumpkin (eg cucumbers), Podosphaera leucotricha on apples and uncinula necator on the vine, Helminthosporium spp., z. B. Pyrenophora teres, Pseudocercospurella herpotrichiodes, Rhynchosporium spp., Septoria spp. and Rhizoctonia spp., E.g. B. cerealis, Cercospora arachidicola on peanuts and other Cercospora species and for example Sugar beets, bananas and soybeans, Venturia inaequalis (Scab) on apples.

Some of the links also show a wide range of activities against fungi in vitro. You own one Activity against various occurring after harvest  Diseases of fruits (eg Penicillium diagatum and italicum of oranges, Gloeosporium musarum of bananas and Botrytis cinerea on grape fruits). There are still some the compounds active as a seed dressing against Fusarium spp., Septoria spp., Tilletia spp. (ie wheat brandy, one seed-borne wheat disease), Ustilago spp. and Helminthosporium spp. on cereals.

The compounds can migrate acropetally into plant tissue. In addition, the compounds can be so volatile, so that they are active in the gas phase against fungi on plants.

They can also be used as industrial fungicides (as opposed to agricultural fungicides), for example in preventing a fungal attack on wood, Hides, leather and in particular paint films.

The compounds of the invention have a useful one pharmaceutical activity as aromatase inhibitors. Aromatase is an enzyme that aromatizes on the Ring A in the metabolic formation of various Causes steroid hormones. Certain tumors are regarding dependent on their maintenance and growth circulating steroids containing an aromatic ring A contain. A chemical agent that aromatizes of ring A in the heats of such steroids inhibits, probably causes the inhibition of growth of such hormone-dependent tumors.

The compounds as such can be fungicidal for many Purposes are used, but they will be useful for one such application formulated in compositions. The invention therefore also relates to fungicidal compositions which a compound of general formula (I) according to the above Definition, a salt or a complex thereof and optionally contain a carrier or diluent.  

The invention also relates to a method for controlling of mushrooms, which is carried out by being on a plant, on the seeds of a plant or on the Location of plant or semen a connection, a Salt or a complex thereof as defined above.

The compounds and their complexes and salts can be added different ways are applied. For example, you can put them in formulated or unformulated form directly onto the Foliage of a plant can be applied. But you can also on bushes and trees, on seeds and other media, in which plants, shrubs or trees grow or in which they are to be planted. You can finally also sprayed or dusted or as Cream or paste formulation can be applied. Also can they as vapor or as granules with slow release of active ingredient be applied. The application can be up any part of the plant, the bush or the tree carried out, for example, on the foliage, the Stems, the branches or the roots. It is also an application on the ground surrounding the roots or on the ground Seeds possible before sowing. In general is also one Apply to the ground, an introduction into the irrigation water or in a hydroponic culture system possible. The invention Compounds can also be found in plants or trees be injected. Finally, they can also be put on vegetation Use of electrodynamic spraying techniques applied become.

The term "plant" as used herein includes Seedlings, bushes and trees. Furthermore, the fungicidal method includes invention a preventive, protective, prophylactic or eradicating treatment.

The compounds are used for agricultural and horticultural Purposes preferably in the form of a composition  used. The type of used in a particular case Composition depends on the intended purpose.

The compositions may be in the form of dusting powders or Granules containing the active ingredient and a solid diluent or carrier material, such as. B. Fillers, for example kaolin, bentonite, kieselguhr, Dolomite, calcium carbonate, talc, powdered magnesia, Fuller's earth, gypsum, Hewitt's earth, diatomaceous earth and China clay. Such granules may be previously prepared Granules that are suitable for application to the ground without further treatment are suitable. These granules can be made are either by impregnating pellets the filler with the active ingredient or by pelleting a mixture of the active ingredient and the powdered filler. Compositions for seed dressing For example, an agent (such as a mineral oil) may be used. contain the liability of the composition increased on the seed. Alternatively, the active ingredient for Seed dressing using an organic solvent be formulated (such as N-methyl-pyrrolidone or dimethylformamide).

The composition may also be in the form of dispersible Powders, granules or grains are present, the Wetting agents contain the distribution of the powder or the grains containing fillers or suspending agents can lighten in liquids.

The aqueous dispersions or emulsions can thereby be prepared such that one or more active ingredient (s) dissolved in an organic solvent, which optionally containing wetting, dispersing or emulsifying agents, then add the mixture in water, which also wetting, dispersing or emulsifying may contain. Suitable organic solvents are Ethylene dichloride, isopropyl alcohol, propylene glycol, diacetone alcohol,  Toluene, kerosene, methylnaphthalene, the xylenes, Trichlorethylene, furfuryl alcohol, tetrahydrofurfuryl alcohol and glycol ethers (e.g., 2-ethoxyethanol and 2-butoxyethanol).

The compositions to be used as sprays may also be in the form of aerosols, the formulation in a container in the presence of a propellant, such as B. fluorotrichloromethane or dichlorodifluoromethane, kept under pressure.

The compounds can be in the dry state with a pyrotechnic Mixture be mixed to a composition produce, which is used to produce one of the compounds containing smoke in closed spaces.

Alternatively, the compound can be used in microcapsule form become. They can also be biodegradable Polymeric formulations are incorporated to a slow and to achieve controlled release of the active ingredient.

By incorporating suitable additives, such. B. additives to improve distribution, adhesion and resistance against rain on the treated surfaces, can the different composition better adapted for different applications.

The compounds can be used as mixtures with fertilizers (such as nitrogen, potassium or phosphorus Fertilizer). Compositions made only from fertilizer granules exist that contain the connection and coated therewith, for example, are preferred. Such granules suitably contain up to 25% by weight. from the connection. The invention therefore relates also a fertilizer composition which is a compound of the general formula (I), a salt or a metal complex of which contains.  

The compositions may also be in the form of liquid Preparations for use as a dipping or spraying agent are present, which are generally aqueous dispersions and emulsions that are the active ingredient in the presence of one or more surfactants Contain means such. B. wetting agents, dispersants, Emulsifier or suspending agent. It may too to act spray formulations of this kind, which are for the Use in electrodynamic spraying techniques suitable are. The above-mentioned agents may be cationic, anionic or non-ionic nature. Suitable cationic Agents are quaternary ammonium compounds, such as. B. cetyltrimethylammonium bromide. Suitable anionic agents are Soaps, salts of aliphatic monoesters of sulfuric acid (such as sodium lauryl sulfate) and salts of aromatic Sulfonate compounds (such as sodium dodecyl benzene sulfonate, Sodium, calcium or ammonium lignosulfonate, Butylnaphthalenesulfonate and a mixture of sodium diisopropyl and triisopropylnaphthalenesulfonates).

Suitable nonionic agents are the condensation products of ethylene oxide with fatty alcohols, such as. B. oleyl or Cetyl alcohol, or with alkylphenols, such as. B. octyl or Nonylphenol and octylcresol. Other nonionic agents are the partial esters that are different from long-chain fatty acids and Hexitanhydriden derive the condensation products of this Partial ester with ethylene oxide and the lecithins. suitable Suspending agents are hydrophilic colloids (such as polyvinylpyrrolidone and sodium carboxymethylcellulose) and the vegetable gums (such as acacia gum and tragacanth gum).

The compositions for use as aqueous dispersions or emulsions are generally in the form of a Concentrate supplied, which has a high proportion of active Ingredient or contains the active ingredients, wherein The concentrate should be diluted with water before use.  

These concentrates often have to endure longer storage times and after such storage still with water can be diluted to produce aqueous preparations, which remain stable for a sufficient time that they pass through a conventional or electrodynamic spray device can be applied. The concentrates may be appropriate up to 95% by weight, suitably 10 to 85% by weight, such as From 25 to 60% by weight of the active ingredient (s) contain. These concentrates contain in suitable Organic acids (such as alkaryl or arylsulfonic acids, z. Xylenesulfonic acid or dodecylbenzenesulfonic acid), because the presence of such acids the Solubility of the active ingredient or ingredients increased in the polar solvents, often be used in such concentrates. The concentrates also contain a high proportion of surfactants, so that sufficiently stable emulsions can be obtained in water. After dilution for the preparation of aqueous preparations, such Preparing different amounts of the active ingredient or the active ingredients, what is intended Application depends, but an aqueous preparation, 0.0005 or 0.01 to 10% by weight of the active ingredient or containing the active ingredients may be used become.

The composition of the invention may also include or several other compounds with biological activity included, such as B. compounds with a similar or complementary fungicidal activity or compounds with a growth regulating activity or with a herbicidal or insecticidal activity.

The further fungicidal compound, for example, a those that are capable of ear diseases Combat cereals (such as wheat, for example Septoria, Gibberella and Helminthosporium spp.), From seed  and ground borne diseases and fluffy and Powdery mildew diseases on grape fruits and powdery mildew and scabs of apples, etc. These mixtures of Fungicides has a broader spectrum of activity than the compound of general formula (I) alone. also The other fungicides can have a synergistic effect on the fungicidal activity of the compound of the general Exercise formula (I). Examples of other fungicidal compounds are carbendazim, benomyl, thiophanate methyl, Thiabendazole, Fuberidazole, Etridazole, Dichlorofluanid, Cymoxanil, Oxadixyl, Ofurace, Metlaxyl, Furalaxyl, Benalaxyl, fosetyl-aluminum, fenarimol, iprodione, Procymidion, Vincloroline, Penconazole, Myclobutanil, RO 151 297, pyrazophos, ethirimol, ditalimofos, tridemorph, Triforin, nuarimol, triazobutyl, guazatine, propiconazole, Prochloraz, flutriafol, hexaconazole, d. H. 1- (1,2,4-triazol-1-yl) .2. (2,4-dichlorophenyl) hexan-2-ol, Flusilazole, d. H. DPX H6573 (1 - ((bis-4-fluorophenyl) methylsilyl) methyl) -1H-1,2,4-triazole, Triadimefon, Triadimenol, Dichlobutrazole, Terbucconazole, furconazole, cis-furconazole, cyproconazole, Fenpropimorph, fenpropidin, chlorozolinate, diniconazole, Imazilil, fenfuran, carboxin, oxycarboxin, dithianon, Methfuroxan, dodemorph, BAS 454, blasticidin S, kasugamycin, Edifenphos, kitazine P, cycloheximide, phthalide, probenazole, Isoprothiolane, tricyclazole, pyroquillan, chlorobenzthiazone, Neoasocin, Polyoxin D, Validamycin A, Repronil, Fluotolanil, Pencycuron, diclomezine, phenazine oxide, nickel dimethyldithiocarbamate, Techlorthalem, Bitertanol, Bupirate, Etaconazole, streptomycin, cypofuran, biloxazole, quinomethionate, Dimethyrimole, 1- (2-cyano-2-methoxyimino-acetyl) -3-ethyl-urea, Fenapanil, tolclofosmethyl, pyroxyfur, Polyram, Maneb, Mancozeb, Captafol, Chlorothalonil, Anilazine, Thiram, Captan, Polpet, Zineb, Propineb, Sulfur, Dinocap, binapactryl, nitrothalisopropyl, dodin, dithianon, Fentin hydroxide, Fentin acetate, Tecnazene, Chintoren, Dichloran, copper-containing compounds such. B. copper oxychloride, Copper sulfate and Bordeaux mixture as well Organomercury compounds.  

The compounds of the general formula (I) can be mixed be around with soil, peat and other rotting media Plants against seed-living or soil-dwelling fungi Protect diseases or foliar fungus diseases.

Suitable insecticides present in the compositions according to the invention can be incorporated, are pirimicarb, Dimethoate, demeton-s-methyl, formothion, carbaryl, isoprocarb, XMC, BPMC, carbofuran, carbosulfan, diazinon, fenthion, Fenitrothion, phenothoate, chlorpyrifos, isoxathione, Propaphos, Monocrotophos, Buprofezin, Ethroproxyfen and Cycloprothrin.

Plant growth regulating compounds for use in the compositions according to the invention are compounds, which influence the grass formation or seed formation or selectively the growth of less desirable plants control (eg of grasses).

Examples of suitable compounds that promote plant growth regulate and in the inventive Compositions can be used are the Gibberellins (eg GA₃, GA₄ or GA₇), the auxins (eg. Indole acetic acid, indolebutyric acid, naphthoxyacetic acid or naphthylacetic acid), the cytokinins (eg kinetin, Diphenylurea, benzimidazole, benzyladenine or benzylaminopurine), Phenoxyacetic acids (eg 2,4-D or MCPA), substituted benzoic acids (eg, trÿodobenzoic acid), Morphactins (eg chlorofluoroecole), maleic hydrazide, Glyphosate, glyphosine, long-chain fatty alcohols and acids, Dikegulac, paclobutrazole, fluoropurimidine, fluoride amide, Mefluidide, substituted quaternary ammonium and phosphonium compounds (eg, chloromequat, chlorophonium or Mepiquat chloride), ethephon, carbetamide, methyl 3,6-dichloroanisate, Daminozide, asulam, abscizic acid, isopyrimil, 1- (4-chlorophenyl) -4,6-dimethyl-2-oxo-1,2-dihydropyridine-3-carboxylic-acid, Hydroxybenzonitriles (eg bromoxynil), Difenzoquat, benzoylpropethyl-3,6-dichloropicolinic acid,  Fenpentazole, Inhabenfid, Triapenthenol and Tecnazen.

The following examples illustrate the invention. temperatures are given in ° C. Reactions in which water-sensitive Intermediates occurred under one dry nitrogen atmosphere carried out.

Example 1

This example illustrates the preparation of 1- (2,4-dichlorophenyl) -2- (1,2,4-triazolyl) methylpent-3-yn-2-ol (Compound No. 7 of Table I).

2,4-dichlorobenzyl chloride (20 g, 102 mmol) in dry Diethyl ether (20 ml) was added dropwise to a stirred Mixture of magnesium turnings (2.5 g, 102 mmol) in dry Diethyl ether (20 ml) added at such a rate, that a steady reflux was maintained. Dry tetrahydrofuran (40 ml) was then added while diethyl ether removed by distillation has been. The mixture was then cooled to room temperature and then dropwise over a period of 30 minutes to a stirred one Solution of chloroacetyl chloride (23 g, 204 mmol) in dry Tetrahydrofuran (100 ml) was added at -78 ° C. The mixture was allowed to warm to room temperature during 1 h, to which was added water. The mixture was washed with diethyl ether extracted, and the combined extracts were with 2M aqueous sodium hydroxide solution and brine washed, dried (MgSO₄) and evaporated in vacuo. Chromatography (SiO 2, ethyl acetate-hexane (5:95) to (10:90)) gave 1-chloro-3- (2,4-dichlorophenyl) acetone (3.5 g, 14%), Mp 62 ° C.

1-chloro-3- (2,4-dichlorophenyl) acetone (6.0 g, 25 mmol) in Acetonitrile (10 ml) was added dropwise to a stirred Mixture of 1,2,4-triazole (3.5 g, 50 mmol) and potassium carbonate (7.0 g, 50 mmol) in dry acetonitrile (40 mL) at 50 ° C added. After 4 hours, the mixture was added to water.  

The mixture was extracted with ethyl acetate and the combined Extracts were taken with saline until neutral washed, dried (MgSO₄) and evaporated in vacuo, Trituration (isopropyl alcohol and hexane) 1- (1,2,4-triazolyl) -3- (2,4-dichlorophenyl) acetone (3.5 g, 52%), mp 110 ° C.

n-Butyllithium (3 ml of a 1.55 M solution in hexane, 4.6 mmol) was slowly added to a stirred solution of propyne (0.18 g, 4.6 mmol) in dry tetrahydrofuran (9 ml) at -78 ° C added. After 30 minutes, chlorotitanium triisopropoxide became (5.1 ml of a 1.0 M solution in hexane, 5.1 mmol) dropwise added. After 20 minutes, 1- (1,2,4-triazolyl) -3- (2,4-dichlorophenyl) acetone was obtained (1.0 g, 4.0 mmol) in dry tetrahydrofuran (20 ml) was added dropwise and the mixture was allowed to warm to room temperature and into saturated poured aqueous ammonium chloride solution. The obtained Mixture was filtered and the precipitate was washed with water and ethyl acetate. The filtrate was washed with water and brine, dried (MgSO₄) and im Vacuum evaporated. Chromatography (SiO₂, ethyl acetate) gave 1- (2,4-dichlorophenyl) -2- (1,2,4-triazolyl) methylpent-3-yn-2-ol (Compound No. 7 of Table 1) (0.21 g, 17%), Mp 110-113 ° C.

example 2

This example illustrates the preparation of 1- (4-chlorophenyl-2- (1,2,4-triazolyl) methylpent-3-yn-2-ol (Compound No. 127 of Table I).

4-Chlorobenzyl chloride (32.8 g, 204 mmol) in dry Diethyl ether (30 ml) was added dropwise to a stirred Mixture of magnesium turnings (5.0 g, 204 mmol) in dry Diethyl ether (50 ml) added at such a rate, that a steady reflux was maintained. Dry tetrahydrofuran (80 ml) was then added while Diethyl ether was removed by distillation. The  The mixture was cooled to room temperature and dropwise for 1 h to a stirred solution of chloroacetyl chloride (46 g, 408 mmol) in dry tetrahydrofuran (200 mL) at -78 ° C was added. The mixture was left on for 1 h Let warm to room temperature and then poured into water. The mixture was extracted with diethyl ether and the combined extracts were washed with 2 M aqueous sodium hydroxide solution and brine, dried (MgSO₄) and evaporated in vacuo. Chromatography (SiO₂, Hexane-ethyl acetate (95: 5)) gave 1-chloro-3- (4-chlorophenyl) -acetone (16.8 g, 40%) mp 47-49 ° C.

1-Chloro-3- (4-chlorophenyl) acetone (6.0 g, 30 mmol) in acetonitrile (5 ml) was added dropwise to a stirred mixture from 1,2,4-triazole (4.2 g, 60 mmol) and potassium carbonate (8.8 g, 60 mmol) in dry acetonitrile (50 mL) at 50 ° C added. After 3½ h, the mixture was cooled and filtered. The filtrate was poured into water and the Mixture was extracted with ethyl acetate. The United Extracts were taken with saline (to neutrality) washed, dried (MgSO₄) and evaporated in vacuo. Chromatography (SiO₂, ethyl acetate-hexane (50:50) to 100: 0)) gave 1- (1,2,4-triazolyl) -3- (4-chlorophenyl) -acetone (3.23g, 46%).

n-Butyllithium (24 ml of a 2.4 M solution in hexane, 60 mmol) was added dropwise to propyne (2.4 g, 60 mmol) in dry Tetrahydrofuran (100 ml) was added at -78 ° C under nitrogen. After 30 minutes, chlorotitanium triisopropoxide became (67 mL of a 1.0 M solution in hexane, 67 mmol) dropwise added. After 20 minutes, 1- (1,2,4-triazolyl) -3- (4-chlorophenyl) acetone (10.75 g, 50 mmol) in dry tetrahydrofuran (200 ml) was added dropwise. The mixture was Let warm to room temperature and then into saturated poured aqueous ammonium chloride solution. The mixture was filtered and the precipitate was washed with water and ethyl acetate washed. The filtrate was separated, and the organic fraction was washed with brine,  dried (MgSO₄) and evaporated in vacuo. chromatography (SiO₂, ethyl acetate-hexane (50:50) gave 1- (4-chlorophenyl) -2- (1,2,4-triazolyl) methylpent-3-yn-2-ol (Connection No. 127 of Table I) 5.25 g, 41%), m.p. 99.5-101.5 ° C.

example 3

This example illustrates the preparation of 1- (4-chlorophenyl-2-methoxy-2- (1,2,4-triazolyl) methylpent-3-yne (Compound No. 128 of Table I).

1- (4-chlorophenyl) -2- (1,2,4-triazolyl) methylpent-3-yn-2-ol (1.0 g, 3.63 mmol) in dry tetrahydrofuran (12 ml) was added dropwise to a stirred suspension of Hexane washed sodium hydride (0.17 g of a 55% Dispersion in oil, 3.9 mmol) in dry tetrahydrofuran (12 ml) was added. After 20 minutes, iodomethane (1.1 g, 7.75 mmol) was added. added dropwise. After 2½ h, the mixture became poured into water, and the resulting mixture was washed with Extracted ethyl acetate. The combined extracts were with Brine, washed (MgSO₄) and in vacuo evaporated. Chromatography (SiO 2, ethyl acetate) 1- (4-chlorophenyl) -2-methoxy-2- (1,2,4-triazolyl) methyl-pent-3-yne (Compound No. 128 of Table I) (0.79 g, 75%).

example 4

This example illustrates the preparation of E-1- (4-chlorophenyl) -2- (1,2,4-triazolyl) methylpent-3-en-2-ol (Compound No. 145 of Table I).

1- (4-chlorophenyl) -2- (1,2,4-triazolyl) methylpent-3-yn-2-ol (2.0 g, 7.26 mmol) in dry tetrahydrofuran (15 mL) was added dropwise to a stirred solution of sodium bis (2-methoxyethoxy) aluminum hydride (8.5 ml of a 3.4 M Solution in toluene, 29 mmol) in dry tetrahydrofuran (24 ml) at 0 ° C under nitrogen. The mixture was warmed to room temperature and after 4½ h at 0 ° C cooled, then carefully added with water.  

The mixture was extracted with ethyl acetate, and the combined Extracts were washed with brine, dried (MgSO₄) and evaporated in vacuo. chromatography (SiO 2, ethyl acetate) gave E-1- (4-chlorophenyl-2- (1,2,4-triazolyl) methylpent-3-en-2-ol (Compound No. 145 from Table I) 1.50 g, 74%), mp 116.5-117.5 ° C.

example 5

This example illustrates the preparation of E-1- (4-chlorophenyl) -2-allyloxy-2- (1,2,4-triazolyl) methylpent-3-ene (Compound No. 153 of Table I).

1- (4-chlorophenyl) -2- (1,2,4-triazolyl) methyl-pent-3-en-2-ol (0.56 g, 2.02 mmol) in dry tetrahydrofuran (6 mL) was added dropwise to a stirred suspension of Hexane washed sodium hydride (0.1 g of a 55% Dispersion in oil, 2.3 mmol) in dry tetrahydrofuran (6 ml) under nitrogen. After 20 min, allyl bromide became (0.49 g, 4.0 mmol) and the mixture became heated to reflux. After 2 h, the mixture was cooled and poured into water. The resulting mixture was washed with Extracted ethyl acetate, and the combined extracts were washed with brine, dried (MgSO₄) and im Vacuum evaporated. Chromatography (SiO₂, ethyl acetate) gave E-1- (4-chlorophenyl) -2-allyloxy-2- (1,2,4-triazolyl) -methylpent-3-ene (Compound No. 153 of Table I) (0.41 g, 64%).

example 6

This example illustrates the preparation of 1- (2-chloro-4-fluorophenyl) -2- (1,2,4-triazolyl) methylhex-3-yn-2-ol (Compound No. 193 of Table I).

2-Chloro-4-fluoroiodobenzene (50 g, 200 mmol) in dry Diethyl ether (100 ml) became a stirred mixture Magnesium turnings (4.9 g, 200 mmol) in dry diethyl ether (30 ml) was added at such a rate that  a steady reflux was maintained. After that The resulting mixture was heated at reflux for a further 45 min allyl bromide (27.2 mL, 200 mmol) was added dropwise Added to such a speed that a steady Reflux was maintained. After another 30 minutes at Reflux, the mixture was poured on ice, whereupon 2 M Hydrochloric acid was added to dissolve the precipitate. The mixture was extracted with ether and the combined Extracts were dried (MgSO₄) and evaporated in vacuo. Chromatography (SiO₂, hexane) gave 3- (2-chloro-4-fluorophenyl) prop-1-ene (25g, 74%).

m-chloroperoxybenzoic acid (13.3 g, 85%, 89 mmol) became a stirred solution of 3- (2-chloro-4-fluorophenyl) -prop-1-ene (13.3 g, 78 mmol) in dry dichloromethane (150 mL) at 0 ° C. After 6 h, the mixture was washed with aqueous sodium sulfite solution and then with 2M aqueous sodium hydroxide solution washed. The mixture was then dried (MgSO₄) and evaporated in vacuo to give 1,2-epoxy-3- (2-chloro-4-fluorophenyl) propane (12.5 g, 86%) was obtained that was used without further purification.

A stirred mixture of 1,2-epoxy-3- (2-chloro-4-fluorophenyl) propane (1 g, 6 mmol), potassium carbonate (0.8 g, 6 mmol) and 1,2,4-triazole (0.5 g, 8 mmol) in industrial methyl alcohol (10 ml) was heated to reflux. After 3 h was the mixture is poured into water, and the resulting mixture was extracted with ethyl acetate. The combined extracts were washed (water), dried (MgSO₄) and in vacuo evaporated. Chromatography (SiO₂, isopropyl alcohol-dichloromethane (20:80)) gave 1- (1,2,4-triazolyl) -3- (2-chloro-4-fluorophenyl) propan-2-ol (0.8g, 52%).

Jones reagent (9.6 ml) (J. Chem. Soc., 1946, 39) dropwise over 45 minutes to a stirred solution 1- (1,2,4-triazolyl) -3- (2-chloro-4-fluorophenyl) propan-2-ol (1.1g, 4.3mmol) in 8N sulfuric acid (22ml) at 15 ° C.  After 30 minutes, the mixture was cooled to 10 ° C, and isopropanol (6 ml) was added. 2N sodium hydroxide solution was added to make the reaction alkaline to make, which then extracted with ethyl acetate (3 times) has been. The combined extracts were dried (MgSO₄) and evaporated in vacuo. There was thus obtained 1- (1,2,4-triazolyl) -3- (2-chloro-4-fluorophenyl) acetone (0.76 g, 70%), mp 60 ° C.

n-Butyllithium (1.4 ml of a 2.5 M solution in hexane, 3.5 mmol) was added slowly to a stirred solution of but-1-yne (0.2 g, 3.5 mmol) in dry tetrahydrofuran (7 ml) at -78 ° C added. After 30 minutes, chlorotitanium triisopropoxide became (3.8 ml of a 1.0 M solution in hexane, 3.8 mmol) dropwise added. After 20 minutes, 1- (1,2,4-triazolyl) -3- (2-chloro-4-fluorophenylacetone (0.76 g, 3 mmol) in dry Tetrahydrofuran (7 ml) was added dropwise, whereupon the Allow mixture to warm to room temperature and place in saturated was poured in aqueous ammonium chloride solution. The mixture was filtered and the precipitate was washed with Washed water and ethyl acetate. The filtrate was separated, and the organic fractions were washed with water and brine, dried (MgSO₄) and im Vacuum evaporated. Chromatography (SiO₂, ethyl acetate) gave 1- (2-chloro-4-fluorophenyl) -2- (1,2,4-triazolyl) -methylhex-3-yn-2-ol (Compound No. 193 of Table I) (0.088 g, 10%).

example 7

This example illustrates an alternative preparation of 1- (2-chloro-4-fluorophenyl) -2- (1,2,4-triazolyl) methylhex-3-yn-2-ol (Compound No. 193 of Table I).

Ethylmagnesium bromide (3.0 ml of a 3 M solution in diethyl ether (9.0 mmol) was added dropwise to a solution of but-1-yne (0.61 g, 11 mmol) in dry tetrahydrofuran (14 mL) 0 ° C was added. After further but-1-in through the mixture 1-Chloro-3- (2-chloro-4-fluorophenylacetone  (1.0 g, 4.5 mmol) in dry tetrahydrofuran (6 ml) was added dropwise and the mixture became stirred at room temperature for 2 h. Water (approximately 50 ml) was then added and the resulting mixture was washed with Extracted ethyl acetate. The combined extracts were with Brine, washed (MgSO₄) and in vacuo evaporated. Chromatography (SiO₂, ethyl acetate-hexane (50:50)) gave 1- (2-chloro-4-fluorophenyl) -3-chloromethylhex-3-yn-2-ol (1.18 g, 99%).

1,2,4-triazole (0.93 g, 14 mmol), 1- (2-chloro-4-fluorophenyl) -2-chloromethylhex-3-yn-2-ol (1.18 g, 4.5 mmol) and potassium carbonate (1.25 mg, 9 mmol) were added to dimethylformamide (25 mL) added and the mixture was refluxed. After 3 h, the mixture was cooled and added to water. The resulting mixture was extracted with ethyl acetate and The combined extracts were washed with water and brine washed, dried (MgSO₄) and evaporated in vacuo. Chromatography (SiO 2, ethyl acetate) gave 1- (2-chloro-4-fluorophenyl) -2- (1,2,4-triazolyl) methylhex-3-yn-2-ol (Compound No. 193 of Table I) (0.60 g, 43%).

example 8

This example illustrates the preparation of Z-1- (2-chloro-4-fluorophenyl) -2- (1,2,4-triazole) methylhex-3-en-2-ol (Compound No. 224 of Table I).

1- (2-chloro-4-fluorophenyl) -2- (1,2,4-triazolyl) methylhex3-in-2-ol (0.20 g, 4.65 mmol) and palladium on charcoal (100 mg) in ethanol (2 ml) were hydrogenated at room temperature. After 18 ml of hydrogen had been taken up the reaction mixture is filtered (Celite) and evaporated in vacuo, an approximate 80:20 mixture of Z-1- (2-chloro-4-fluorophenyl) -2- (1,2,4-triazolyl) methylhex-3-en-2-ol and 1- (2-chloro-4-fluorophenyl) -2- (1,2,4-triazolyl) methylhexan-2-ol (Compound No. 224 of Table I) (0.061 g, 30%), mp 83 ° C was obtained.  

example 9

This example illustrates the preparation of 1- (2-chloro-4-fluorophenyl) -2-t-butyl-3- (1,2,4-triazolyl) butan-2-ol (Compound No. 430 of Table I).

2-Chloro-4-fluorobenzyl chloride (4.0 g, 22 mmol) in dry Diethyl ether (10 ml) was added dropwise to a stirred Mixture of magnesium turnings (0.54 g, 22 mmol) and iodine (approximately 1 mg) in dry diethyl ether (10 ml) Added to such a speed that a steady Reflux was maintained. The mixture then became dropwise to a stirred mixture of 2,2-dimethyl-4- (1,2,4-triazolyl) pentan-3-one (2.5 g, 13.8 mmol) in dry Diethyl ether (20 ml) was added at approximately 10 ° C. The Mixture was then heated at reflux for 2 hours. After cooling At room temperature, the mixture of any unreacted Magnesium decanted and saturated Washed aqueous ammonium chloride solution. The aqueous layer was separated and extracted into ether. The United organic extracts were washed with brine, dried (MgSO₄) and evaporated in vacuo. chromatography (SiO₂, ethyl acetate-hexane (50:50) gave 1- (2-chloro-4-fluorophenyl) -2-t-butyl-3- (1,2,4-triazolyl) butan-2-ol (Compound No. 430 of Table I) (1.2 g, 27%).

example 10

This example illustrates the preparation of 1- (2-chlorophenyl) -2- (1,2,4-traizolyl) methyl-3-methylpent-3-en-2-ol (Compound No. 452 of Table I).

2,4-dichlorobenzyl chloride (20.0 g, 102 mmol) in dry Diethyl ether (20 ml) was added dropwise to a stirred Suspension of magnesium turnings in dry diethyl ether (20 ml) was added at such a rate that a steady reflux was maintained. dry Tetrahydrofuran (40 ml) was then added at such a rate  added that maintain a constant volume was while solvent by distillation was removed. The mixture became chloroacetyl chloride (23 g, 204 mmol) in dry tetrahydrofuran (100 ml) -78 ° C for approximately 30 minutes. The mixture was heated to room temperature for about 1 h, whereupon Water (200 ml) was added. The resulting mixture was extracted with ether (3 x 50 ml) and the combined Extracts were mixed with 2 M sodium hydroxide and saline washed, dried (MgSO₄) and evaporated in vacuo. Chromatography (SiO₂, hexane-ethyl acetate (95: 5) to (90:10)) gave 1-chloro-3- (2-chlorophenyl) acetone (3.5 g, 14%), Mp 62 ° C.

2-Bromobut-2-ene (1.35 g, 10 mmol) in dry tetrahydrofuran (20 ml) was added to a stirred suspension of Magnesium turnings (0.25 g, 10 mmol) in dry tetrahydrofuran (20 ml) added at such a rate, that a steady reflux was maintained. After a Reflux time of 1½ h, the mixture was cooled to 0 ° C, and 1-chloro-3- (2-chlorophenyl) acetone (1.0 g, 5 mmol) in dry tetrahydrofuran (10 ml) was added dropwise added. The mixture was warmed to room temperature and poured into saturated aqueous ammonium chloride solution. The resulting mixture was extracted with diethyl ether, and the combined extracts were washed with brine, dried (MgSO₄) and evaporated in vacuo, wherein 1- (2-chlorophenyl) -2-chloromethyl-3-methylpent-3-en-2-ol (1.3 g), which without further purification was used. 1- (2-Chlorophenyl) -2-chloromethyl-3-methylpent-3-en-2-ol (1.3 g from the previous reaction), 1,2,4-triazole (1.04 g, 15 mmol) and potassium carbonate (1.38 g, 10 mmol) were refluxed in dimethylformamide (25 ml). stirred for 3 h. The mixture was then cooled, in Poured water and extracted with ethyl acetate. The United Extracts were washed with water and brine, dried (MgSO₄) and evaporated in vacuo. Chromatography (SiO 2, ethyl acetate) gave 1- (2-chlorophenyl) -2- (1,2,4-triazolyl) methyl-3-methylpent-3-en-2-ol  (Compound No. 452 of Table I) (0.012 g, 1% on 1-chloro-3- (2-chlorophenyl) acetone, mp 88 ° C.

example 11

An emulsifiable concentrate was prepared by the following ingredients were mixed and the mixture while stirring until all ingredients were dissolved.

Compound No. 223 of Table I | 10% ethylene dichloride 40% calcium dodecylbenzenesulfonate 5% "Lubrol" L 10% "Aromasol" H 35%

example 12

A composition in the form of powders that are easily absorbed in a liquid, such as. As water, could be dispersed, was made by first adding up the first three ingredients were ground in the presence of added water and then the sodium acetate was mixed. The obtained Mixture was dried and passed through a British standard sieve, Size 44-100, passed to the desired To achieve grain size.

Compound No. 223 of Table I | 50% "Disperol" T 25% "Lubrol" APN5 1.5% sodium 23.5%

example 13

The ingredients were all ground together to one Make powder preparation that easily dispersed in liquid could be.

Compound No. 223 of Table I | 45% "Disperol" T 5% "Lisapol" NX 0.5% "Cellofas" B600 2% sodium 47.5%

example 14

The active ingredient was dissolved in a solvent and the resulting liquid was on china clay granules injected. The solvent was then evaporated off to obtain a granular composition has been.

Compound No. 223 of Table I | 5% China clay granules 95%

example 15

A composition for use as a seed dressing was prepared by mixing the following three ingredients:

Compound No. 223 of Table I | 50% mineral oil 2% kaolin 48%

example 16

A dusting powder was prepared by adding the active ingredient mixed with talc.

Compound No. 223 of Table I | 5% talc 95%

example 17

A colloidal formulation was prepared by milling the ingredients listed below in a ball mill and subsequent preparation of an aqueous suspension from the ground mixture with water.

Compound No. 223 of Table I | 40% "Disperol" T 10% "Lubrol" APN5 1% water 1%

example 18

A dispersible powder formulation was prepared by mixing together the ingredients given below and then the mixture was ground until everything was carefully mixed.

Compound No. 223 of Table I | 25% "Aerosol" OT / B 2% "Disperol" AC 5% kaolin 28% silica 40%

example 19

This example illustrates the preparation of a dispersible Powder formulation. The ingredients were mixed, and the mixture was ground in a mill.

Compound No. 223 of Table I | 25% "Perminal" BX 1% "Disperol" T 5% polyvinylpyrrolidone 10% silica 25% kaolin 34%

example 20

The ingredients given below were in a dispersible powder formulated by mixing and then ground.

Compound No. 223 of Table I | 25% "Aerosol" OT / B 2% "Disperol" AC 5% kaolin 68%

In Examples 11 to 20, the ingredients are by weight specified.

The remaining compounds of Table I were in similar Formulated as described specifically in Examples 11 to 20 is described.

An explanation of the compositions or substances follows, which were named above based on trademarks.

LUBROL L:
a condensate of nonylphenol (1 mole) with ethylene oxide (13 moles)

AROMASOL H:
a solvent mixture of alkylbenzenes

DISPERSOL T & AC:
a mixture of sodium sulfate and a condensate of formaldehyde with sodium naphthalenesulfonate

LUBROL APN5:
a condensate of nonylphenol (1 mole) with naphthalene oxide (5.5 moles)

CELLOFAS B600:
a sodium carboxymethylcellulose thickener

LISSAPOL NX:
a condensate of nonylphenol (1 mole) with ethylene oxide (8 moles)

AEROSOL OT / B:
Dioctyl sodium sulfosuccinate

PERMINAL BX:
a sodium alkylnaphthalenesulfonate.

Example 03721 00070 552 001000280000000200012000285910361000040 0002003923202 00004 03602l 21

The compounds were against a number of fungal diseases studied on the foliage of plants. The technique used  was as follows:

The plants were grown in John Innes potting compost (# 1 or no. 2) in mini pots of 4 cm diameter. The Test compounds were formulated either in a ball mill with aqueous Dispersol T or as a solution in acetone or acetone / ethanol, which immediately before use was diluted to the desired concentration. For the Foliage diseases were the formulations (100 ppm active ingredients) sprayed on the foliage and then applied to the roots of the plants in the soil. The Sprays were up to a maximum retention applied and the soil drinks were up to a final concentration corresponding to approximately 40 ppm of active ingredient (dry soil) applied. Tween 20 was added up to a final concentration of 0.05% if the sprays were applied to cereals.

For most tests, the compounds were on the ground (Roots) and applied to the foliage (by spraying), one or two days before the plant starts having the disease was inoculated. One exception was the test Erysiphe graminis, taking the plants 24 h before treatment were inoculated. Leaf pathogens were by spraying as spore suspension on the leaves of the test Plants applied. After inoculation the plants became placed in a suitable environment to prevent the infection could develop. Then the plants were incubated, until the disease was ripe for the determination. The Time between inoculation and destination varied from 4 to 14 days, depending on the disease and the environment.  

The disease control was classified as follows:

4 = no illness
3 = trace to 5% disease, relative to untreated plants
2 = 6 to 25% disease, based on untreated plants
1 = 26 to 59% disease, based on untreated plants
0 = 60 to 100% disease, relative to untreated plants.

The results are given in Table III.  

Table III

Claims (13)

1. Compounds of the general formula (I) and stereoisomers thereof, wherein R¹ is alkyl (when R⁵ is other than hydrogen) or is a group of general formula (II) -C≡C-R⁷ (II) or is a group of general formula (III) wherein R⁷, R⁸, R⁹ and R¹⁰ are independently hydrogen, halogen, alkyl, alkenyl or alkynyl; R² is hydrogen, alkyl, alkenyl or alkynyl (provided that the carbon atom adjacent to the oxygen is not involved in unsaturation); R³, R⁴, R⁵ and R⁶ are independently hydrogen, alkyl, alkenyl or alkynyl; X, Y and Z are independently selected from hydrogen, halogen, alkyl, haloalkyl, cycloalkyl, cycloalkylalkyl, alkenyl, alkynyl, optionally substituted aryl, optionally substituted aralkyl, alkoxy, aryloxy, haloalkoxy or aralkoxy; and Az is imidazol-1-yl or 1,2,4-triazol-1-yl; with the proviso that when R³ and R⁴ are both methyl, R⁵ and R⁶ are both hydrogen and Az is 1,2,4-triazol-1-yl, R¹ is not -C≡C-alkyl, and with with the further proviso that when R³ and R⁴ are both alkyl, R⁵ is hydrogen and R⁶ is alkyl, alkenyl or alkynyl, R⁸, R⁹ and R¹⁰ are not all hydrogen; and salts and metal complexes thereof. 2. Compounds according to claim 1 of the general formula (I) and stereoisomers thereof, wherein R¹ is an alkyl group having 1 to 6 carbon atoms (for cases where R⁵ is other than hydrogen) or a group of the general formula (II) -C≡C-R⁷ (II) or a group of general formula (III) wherein R⁷ to R¹⁰, which may be the same or different, represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkenyl or alkynyl group having 2 to 4 carbon atoms or a halogen atom (fluorine, chlorine, bromine or iodine); R² represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an alkenyl or alkynyl group having 2 to 4 carbon atoms (provided that the carbon atom adjacent to the oxygen atom is not included in unsaturation); R³ to R⁶, which may be the same or different, each represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkenyl or alkynyl group having 2 to 4 carbon atoms; X, Y and Z, which may be the same or different, each represents a hydrogen atom, a halogen atom (fluorine, chlorine or bromine), an alkyl, cycloalkyl, cycloalkylalkyl, alkenyl, alkynyl, aryl, aralkyl, Alkoxy, aryloxy, aralkoxy group; and Az is 1-imidazole or 1,2,4-triazole; with the proviso that when R³ and R⁴ are both methyl, R⁵ and R⁶ are both hydrogen and Az is 1,2,4-triazol-1-yl, R¹ is not -C≡C-alkyl, and with with the further proviso that when R³ and R⁴ are both alkyl, R⁵ is hydrogen and R⁶ is alkyl, alkenyl or alkynyl, R⁸, R⁹ and R¹⁰ are not all hydrogen; and salts and metal complexes thereof. 3. Compounds according to claim 1 of the general formula (I) and stereoisomers thereof, wherein R¹ is C _1-6 alkyl (when R⁵ is other than hydrogen) or is a group of the general formula (II) -C≡C-R⁷ (II) or a group of the general formula ( III) wherein R⁷, R⁸, R⁹ and R¹⁰ are independently hydrogen, halogen, C _1-4 alkyl, C _2-4 alkenyl or C _2-4 alkynyl; R 2 is hydrogen, C _1-6 alkyl, C _3-6 alkenyl or C _3-6 alkynyl (provided that the carbon atom adjacent to the oxygen is not involved in unsaturation); R³ to R⁶ are independently hydrogen, C _1-4 alkyl, C _2-4 alkenyl or C _2-4 alkynyl; X, Y and Z are independently selected from hydrogen, halogen, C _1-6 alkyl, halo (C _1-6 ) alkyl, C _3-7 cycloalkyl, C _3-7 cycloalkyl (C _1-6 ) alkyl, C _2-6 alkenyl, C _2-6 alkynyl, phenyl, phenyl (C _1-6 ) alkyl, C _1-6 alkoxy, halo (C _1-6 ) alkoxy, phenoxy or phenyl (C _1-6 ) alkoxy; and Az is imidazol-1-yl or 1,2,4-triazol-1-yl; wherein the above phenyl radicals are optionally substituted by halogen, C _1-6 alkyl, C _1-6 alkoxy, halo (C _1-6 ) alkyl, halo (C _1-6 ) alkoxy, nitro, phenyl or phenoxy; with the proviso that when R³ and R⁴ are both methyl, R⁵ and R⁶ are both hydrogen and Az is 1,2,4-triazol-1-yl, R¹ is not -C≡C-alkyl, and with with the further proviso that when R³ and R⁴ are both alkyl, R⁵ is hydrogen and R⁶ is alkyl, alkenyl or alkynyl, R⁸, R⁹ and R¹⁰ are not all hydrogen; and salts and metal complexes thereof. 4. Compounds according to any one of claims 1, 2 or 3 of the general formula (I) and stereoisomers thereof, wherein R¹ is C _3-4 alkyl; R², R³ and R⁶ are independently hydrogen or C _1-4 alkyl; R⁴ is hydrogen; R⁵ is C _1-4 alkyl; X, Y and Z are independently hydrogen, halo, C _1-4 alkyl, C _1-4 alkoxy, phenoxy or phenyl; and Az is imidazol-1-yl or 1,2,4-triazol-1-yl; and salts and metal complexes thereof. 5. Compounds according to claim 4, wherein R¹ is C _3-4 alkyl; R² is hydrogen or methyl; R³, R⁴ and R⁶ are all hydrogen; R⁵ is C _1-2 alkyl; Az is 1,2,4-triazol-1-yl; and X, Y and Z are independently hydrogen, chlorine or fluorine atoms; and salts and metal complexes thereof. 6. Compounds according to one of claims 1, 2 or 3 of the general formula (I) and stereoisomers thereof, wherein R¹ is a group of the general formula (II) -C≡C-R⁷ (II) or a group of the general formula (III) wherein R⁷, R⁸, R⁹ and R¹⁰ are independently hydrogen, halogen, C _1-4 alkyl, C _2-4 alkenyl or C _2-4 alkynyl; R² is hydrogen, C _1-4 alkyl, C _3-6 alkenyl or C _3-6 alkynyl (provided that the carbon atom adjacent to the oxygen atom is not involved in unsaturation); R³, R⁴, R⁵ and R⁶ are independently hydrogen, C _1-6 alkyl, C _2-4 alkenyl or C _2-4 alkynyl; X, Y and Z are independently hydrogen, chlorine or fluorine; and Az is imidazol-1-yl or 1,2,4-triazol-1-yl; with the proviso that when R³ and R⁴ are both methyl, R⁵ and R⁶ are both hydrogen and Az is 1,2,4-triazol-1-yl, R¹ is not -C≡C-alkyl, and with with the further proviso that when R³ and R⁴ are both alkyl, R⁵ is hydrogen and R⁶ is alkyl, alkenyl or alkynyl, R⁸, R⁹ and R¹⁰ are not all hydrogen; and salts and metal complexes thereof. 7. Compounds according to any one of claims 1, 2, 3 or 6 of the general formula (XXXIV) and stereoisomers thereof, wherein R¹ is a group of the general formula (II) -C≡C-R⁷ (II) or a group of the formula (III) wherein R⁷, R⁸, R⁹ and R¹⁰ are independently hydrogen or C _1-4 alkyl; R² is hydrogen, C _1-4 alkyl, allyl or propargyl; X, Y and Z are independently hydrogen, chlorine or fluorine; and salts and metal complexes thereof. 8. Compounds according to one of claims 1, 2, 3, 6 or 7 of the general formula (XXXV) and stereoisomers thereof, wherein R¹ is a group of the general formula (II) -C≡C-R⁷ (II) or a group of the general formula (III) wherein R⁷ is C _1-4 -alkyl, R⁸ is hydrogen and one of the symbols R⁹ and R¹⁰ is hydrogen and the other is C _1-4 -alkyl; R² is hydrogen or methyl; and X and Y are hydrogen, chlorine or fluorine; and salts and metal complexes thereof. 9. The connection (Compound 223 in Table I) and their stereoisomers; and salts and metal complexes thereof. 10. Process for the preparation of compounds of general formula (I) in which an alcohol of the general formula (IV) wherein Az, R¹, R³ to R⁶, X, Y and Z have the meanings given in claim 1, by treatment with a base such. As sodium hydride, and an alkyl halide, R² Hal, wherein Hal is chlorine, bromine or iodine and R² has the meaning given in claim 1, is etherified in a suitable solvent, wherein the compounds of general formula (IV) are prepared by treatment of compounds of general formula (VI) wherein Az, R³ to R⁶, X, Y and Z have the meanings given in claim 1, with a metal acetylide of the general formula (VII) MC≡C-R⁷ (VII) wherein R⁷ has the meaning given in claim 1 and M is a Metal, such as. As lithium, magnesium or titanium, or M may also be silicon, in the presence of a suitable fluoride catalyst (for cases where R¹ is a group of general formula (II)), or with a compound of general formula (VIII ) wherein R⁸ to R¹⁰ have the meanings given in claim 1 and M is magnesium (a Grignard reagent) or lithium, in a suitable solvent, such as. For example, tetrahydrofuran (for cases where R¹ is a group of the general formula (III)) or with a compound of the general formula R¹M wherein R¹ is an alkyl group as defined in claim 1 and M is a metal such. Lithium or magnesium (for cases where R¹ is an alkyl group and R⁵ is not hydrogen). 11. Fungicide composition, which is an ingredient A compound according to claim 1 or a stereoisomer Salt or a metal complex thereof and optionally contains a carrier or diluent. 12. A method for controlling fungi, in which on a plant or on the seeds connect to Claim 1 or a stereoisomer, a salt or a metal complex thereof or a composition according to claim 11 is applied. 13. Novel intermediates of the formulas (IV), (V) and (XVI), in which R¹, R², R³, R⁴, R⁵, R⁶, X, Y, Z and Az are as defined in claim 1 have given meanings.