FI64360C - SOM FUNGICIDER ANVAENDBARA ALKYL- OCH ARYLSUBSTITUERADE ALFA-AZOLYLMETYLSULFIDER - Google Patents

Description

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National Board of Patents and Registration Niht »yiksip.non j. Date of publication - 2Q 07 83

Patent- och registerstyrelaen Ansöksn utl »gd och uti.ikrtfwn pubtic * r» d ~ '(32) (33) (31) Privilege requested — Begird prlorltet O ^ -Oo. 77

Federal Republic of Germany Förbundsrepubliken Tyskland (DE) P 273531 * 4.6 (71) BASF Aktiengesellschaft, Ludwigshafen, Federal Republic of Germany Förbunds-republiken Tyskland (DE) (72) Hubert Sauter., Ludwigshafen, Ernst-Heinrich Pommer, Lim

Bernd Zeeh, Ludwigshafen, Costin Rentzea, Heidelberg, Federal Republic of Germany Förbundsrepubliken Tyskland (DE) (7 * +) Oy Kolster Ab (5 * 4) Alkyl and aryl substituted as fungicides. o <-Azolylmethylsulfides - Som fungieider användbara alkyl- och arylsubstitu-Erade (X-azolylmethylsulfider

The invention relates to novel alkyl- and aryl-substituted «X-azolylmethylsulfides and their derivatives, (X-azolylsulfoxides and <X-azolylsulfones and their salts and metal complexes) for use as fungicides.

It is known that imidazole derivatives, e.g. 1- [2,4-dichlorophenyl-allylethyl ether] -imidazole (DE application 20 63 857) have a good fungicidal effect. The effect is not always satisfactory in terms of low operating costs and low operating concentrations. In addition, fungal toxicity is often linked to the high toxicity of the substance to plants, so that the concentrations required to control rust fungi also damage crops. On this basis, they are not always and not suitable for plant protection products for fungicides for all plant species.

The invention relates to c * -azolylmethyl sulphides of the formula 64360 s2 (O) i n \ 1 3

R - C - S - R

Az wherein R 1 is hydrogen, C 1 -C 4 alkyl, (C 1 -C 4 alkoxycarbonyl. Or optionally substituted aryl, R is hydrogen or C 1-4 alkyl, R is C 1 -C 4 alkyl). -alkyl, C 1 -C 4 -alkenyl, C 1 -C 4 -alkynyl, optionally substituted phenyl or optionally substituted aryl (C 1 -C 4 -alkyl), Az is imidazol-1-yl, pyrazol-1-yl , 1,2,4-triazol-1-yl, 1,2,4-triazol-4-yl, tetrazol-1-yl or tetrazol-2-yl, and n is 0, 1 or 2, and their salts and metal complexes with copper, zinc, manganese, iron, cobalt and nickel.

The compounds of the formula I act against fungi, in particular those belonging to the class Ascomycetes and Basidiomycetes.

R is, for example, hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, methoxycarbonyl, phenyl, 4-nitrophenyl, 4-bromophenyl, 4-cyanophenyl , 2-methylphenyl, 4-t-butylphenyl, 3-trifluoromethylphenyl, 4-trifluoromethylphenyl, 4-fluorophenyl, 2-chlorophenyl, 4-chlorophenyl, 2,4-dichlorophenyl, 2,6-dichlorophenyl, 3,4 -dichlorophenyl, -naphthyl.

2 R denotes, for example, hydrogen, methyl, n-propyl.

3 R denotes, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, n-pentyl, n-hexyl, allyl, propargyl, phenyl, 4-methoxyphenyl, 4-tolyl, 4-chlorophenyl, 3, 4-dichlorophenyl, 2,4-dichlorophenyl, 2,3,6-trichlorophenyl, benzyl, 3-trifluoromethylbenzyl, 4-chlorobenzyl, 4-bromobenzyl, 3,4-dichlorobenzyl, 2,4-dichlorobenzyl, 2, 3,6-trichlorobenzyl, 2-phenylethyl.

Salts are, for example, hydrochlorides, bromides, sulphates, nitrates, phosphates, oxalates or dedecylbenzene sulphonates. The effect of the salts is due to the cation, so the choice of anion is arbitrary.

The metal complexes are compounds of the following formula: 3 64360 r2 1 '(0) n 7 / Me (RX - C - S -R) m7 Xk (II)

Az wherein 12 3 R, R: 11a, R: 11a, Az and n have the meanings given above and

We denote a metal, e.g. copper, zinc, tin, manganese, iron, cobalt or nickel, X denotes an anion of an inorganic acid, e.g. hydrochloric acid, sulfuric acid, phosphoric acid, hydrobromic acid, m and k are numbers 1-4.

Azolyl sulfides of formula I (where n = 0) are prepared by reacting a c <-chlorosulfide of formula III R2 1 '3 R - C - S - R (III)

Cl wherein R 3, R and R are as defined above, to react with the azole H-Az, optionally in the presence of a base and optionally a diluent, wherein Az has the meaning given above. Oxidation of the α-azolyl sulfide of formula I (n = 0) thus obtained gives the α-azolyl sulfoxide of formula I (n = 0) and the α-azolyl sulfone of formula I (n = 2).

In the preparation of azolyl sulphides of the formula I (n = 0), it is expedient to react the X-chlorosulphide of the formula III at about 0-200 ° C, preferably 20-160 ° C, in a homogeneous or inhomogeneous phase, without diluent or diluent. in the presence of about 0.5-2 equivalents of the alkali salt of a suitable azole, optionally with the addition of 0.5-4 equivalents of base.

As the diluent, for example, methanol, ethanol, isopropanol, n-butanol, diethyl ether, tetrahydrofuran, dioxane, acetone, acetonitrile, dimethylformamide, dimethyl sulfoxide, chloroform, methylene chloride or toluene can be used.

As bases, for example, organic amines such as triethyl

4 6 A 3 6 O

amine, pyridine or inorganic compounds e.g. potassium carbonate or sodium hydroxide.

The cX-chlorosulphides III used as starting materials are partly known from the literature and can be prepared according to methods known in the literature, e.g.

a) by chlorinating sulphides with N-chlorosuccinimide (see e.g. BL Tuleen and TB Stephens, J. Org. Chem. 34, 31 (1969)) according to the following reaction scheme: 0 r2 1 '3 (1- \ R - CH - S - R + I N-Cl ->

V

oof Jt R1 - C - S - R3 ♦ 1 / ™ (III) 0 or b) in the reaction between aldehydes and thiols in the presence of hydrogen chloride (see e.g. H. Fischer and K. Frank, Liebigs Ann. Chem. 563, 54 (1949)) ) according to the following reaction scheme R1-CO + HSR3 + HCl - ^

B

R1-C ~ SR3 + H90

Cl (III)

To prepare azolyl sulfoxides of formula I (n = 1), cis-azolyl sulfide is reacted, optionally in the presence of a diluent, with about one equivalent of a suitable oxidant at a temperature of about -30 to + 100 ° C. The c <-azolyl sulfones (formula I, n = 2) are obtained in a similar manner by oxidizing the c <-azolyl sulphides (I, n = 0) with at least two equivalents of a suitable oxidant or by oxidizing the 0 <-azolyl sulphoxides (I, n = 1)

II

5,64360 with at least one equivalent of oxidant.

As the oxidant, for example, potassium permanganate, hydrogen peroxide or percarboxylic acids such as peracetic acid, perbenzoic acid or 3-chlorobenzoic acid can be used. As the diluent, for example, water, acetic acid, methanol, acetone, chloroform or methylene chloride can be used. Sulfoxides (I, n = 1) are preferably prepared by reacting sulfide (I, n = 0) with one equivalent of 3-chloroperbenzoic acid in methylene chloride at 0-25 ° C. The sulfones are preferably prepared by reacting the sulfide (I, n = 0) with two equivalents of 3-chloroperbenzoic acid in methylene chloride at a temperature of 15-41 ° C.

The compounds of formula I (n = 0, 1, 2) are readily soluble in various organic solvents, e.g. ethyl acetate, acetone, ethanol, methylene chloride, chloroform, dimethyl sulfoxide, dimethylformamide and N-methylpyrrolidone. c * s -azolyl sulfides (I = 0) are also highly soluble in toluene.

They can be converted into their salts by means of acids, for example into hydrochlorides, sulphates, nitrates, oxalates, formates, acetates or dodecylbenzyl sulphonates.

Metal complexes of formula II are prepared by reacting o <-azolyl sulfide or a derivative thereof of formula I with a metal salt of formula IV in the presence of a solvent.

MeXk. a H 2 O (IV) in which formula

Me, X and k have the same meaning as above and a is 0-4.

Here, We denote primarily metals belonging to side groups I, II and (IV to VIII) of the Periodic Table of the Elements and metals belonging to the main groups of Ilre and IV, especially copper, zinc, tin, manganese, iron, cobalt and nickel.

The metal salts of formula IV are well known, readily available compounds.

In the preparation of metal complexes of the formula II, all water-miscible solvents are suitable, e.g.

64360 methanol, ethanol, isopropanol, acetone, tetrahydrofuran and dioxane. In this case, work is generally carried out at temperatures between 0 and 100 ° C, mainly at 10-35 ° C.

Sulfides (I, n = 0) and sulfones (I, n = 2) sometimes contain an asymmetric carbon atom and accordingly form mixtures of enantiomers which can be separated into optically active compounds. In the case of sulphoxides I (n = 1), due to the asymmetric sulfur atom adjacent to the asymmetric carbon atom, mixtures of diastereomers exist which can be separated into the individual components in the usual manner, e.g. by crystallization or chromatography.

However, the separation of enantiomers or diastereomers is not normally necessary if the compounds are used as fungicides or plant growth regulators.

The novel oC-azolyl sulfides, o <5-azolyl sulfoxides and? -Azolyl sulfones and their salts have a much broader fungicidal effect than the known 1- [2,4-dichlorophenyl-N-allylethyl ether] imidazole and are more suitable for plants than said compound. The new active substances can also be used in their salt form, e.g. as the hydrochloride, oxalate or nitrate.

The fungicidal compositions according to the invention are of great interest in the case of various fungal diseases of crops, for example:

Ustilago scitaminea (sugar cane rust)

Hemileia vastatrix (coffee rust)

Uromyces fabae or appendiculatus

Puccinia Arten (grain rust)

Erysiphe graminis (cereal fungus)

Botrytis cinerea on a vine, strawberries,

Uncinula necator,

Sphaerotheca fuliginea,

Erysiphe cichoracearum,

Podosphaera leucotricha.

Crops in this context refer in particular to wheat, rye, barley, oats, rice, maize, apple trees, cucumbers, beans, coffee, sugar cane, vines, strawberries and ornamental plants for the garden.

7 64360

The active substances according to the invention are systemically active. The systemic effect of these substances is particularly useful in the control of internal plant diseases, e.g. cereal rust, cereal fungus.

The substances according to the invention can control two or more of said fungi simultaneously, and these substances are well tolerated by plants. The amounts required for the control of phytopathogenic fungi are 0.05-2 kg of active substance / ha of cultivated area.

The active compounds according to the invention can be prepared in the form of conventional preparations, such as solutions, emulsions, suspensions, powders, pastes and granulated products. These are prepared in a known manner, e.g. by mixing the active ingredient with a solvent and / or a carrier, optionally using an emulsifier and a dispersant, in which case, in the case of water as diluent, other organic solvents can also be used as co-solvent. Suitable excipients are: solvents such as aromatics (eg xylene, benzene), chlorinated aromatics (eg chlorobenzene), paraffins (eg petroleum granules), alcohols (eg methanol, butanol), amines (eg ethanolamine, dimethylformamide) , and water, carriers such as natural stone powders (e.g. kaolin, alumina, talc, chalk) and synthetic rock powders (e.g. fine silica, silicates): emulsifiers such as non-ionic or anionic emulsifiers (e.g. polyoxyethyl -lene fatty alcohol ethers, alkyl sulfonates and aryl sulfonates) and dispersants such as lignin, sulfite waste liquor and methylcellulose.

The preparations generally contain from 0.1 to 95% by weight of active ingredient, in particular from 0.5 to 90%. The preparations or ready-to-use products obtained therefrom, such as solutions, emulsions, suspensions, powders, pastes or granules, are used in the usual manner, e.g. by spraying, spraying, delivering, sprinkling, pickling or wetting.

In these applications, the substances according to the invention can be combined with other active substances, e.g. herbicides, insecticides, growth rate regulators and fungicides, or they can also be mixed with fertilizers. Fungicides with which the compounds of the invention can be combined include, for example, dithiocarbamates and derivatives thereof, such as ferridimethyldithiocarbamate, zinc dimethyldithiocarbamate, manganese ethylene bisdithiocarbamate, manganese zinc ethylenediamine, bis-dithiocarbate, ethylene bis-dithiocarbamate) and N-N'-polyethylene bis- (thiocarbamoyl) disulfide ammonia complex, zinc (N, N'-propylene bis-dithiocarbamate), tin (N, N'-propylene ammonia complex of bis-dithiocarbamate and N, N'-polypropylene-bis- (thiocarbamoyl) -disulfide.

A nitrophenol derivative such as dinitro- (1-methylheptyl) phenyl crotonate, 2-sec-butyl-4,6-dinitrophenyl-3,3-dimethylacrylate, 2-sec-butyl-4,6-dinitrophenyl isopropyl carbonate;

Heterocyclic compounds such as N-trichloromethylthio-tetrahydrofralimide, N-trichloromethylthio-phthalimide, 2-heptadecyl-2-imidazoline acetate, 2,4-dichloro-6- (O-chloroanilino) -s-triazine, O, O-Diethyl phthalimidophosphonothioate, 5-amino-1- (bis- (dimethylamino) phosphinyl) -3-phenyl-1,2,4-triazole, 5-ethoxy-3-trichloromethyl-1,2,4- thiadiazole, 2,3-dicyano-1,4-dithianitraquinone, 2-thio-1,3-dithio- (4,5-b) -quinoxaline, 1- (butylcarbamoyl) -2-benzimidazolecarbamic acid methyl ester, 2-methoxycarbamoylamino-benzimidazole, 2-Rhodanemethylthio-benzithiazole, 4- (2-chlorophenylhydrazono) -3-methyl-5-isoxazolone, pyridine-2-thiol-1-oxide, 8-hydroxyquinoline or its copper salt, 2,3-dihydro-5-carboxanilido-6-methyl -1,4-oxatin-4,4-dioxide, 2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxatin, 2- (furyl- (2)) -benzimidazole, piperazine-1,4-diyl -bis-1- (2,2,2-trichloroethyl) -formamide, 9,64360 2- (thiazolyl- (4)) -benzimidazole, 2-butyl-2-dimethyl ylamino-4-hydroxy-6-methyl-pyridine, bis- (p-chlorophenyl) -3-pyridinemethanol, thioureido) benzene, 1,2-bis- (3-methoxycarbonyl-2-thioureido) benzene, and various fungicides such as dodecylguanidine acetate, 3- (2- (3,5-dimethyl-2-oxycyclohexyl) -2-hydroxyethyl) glutarimide, hexachlorobenzene, N-dichlorofluoromethylthio-N'N'-dimethyl-N-phenyl-sulfuric acid diamide, 2,5-Dimethyl-furan-3-carboxylic acid anilide, 2,5-Dimethyl-furan-3-carboxylic acid-cyclohexylamide, 2-methyl-benzoic acid anilide, 2-iodo-benzoic acid anilide, 1- (3,4-dichloroanilino) -1-formylamino- 2,2,2-trichloroethane, 2,6-dimethyl-N-tripecyl-morpholine or its salts, 2,6-dimethyl-N-cyclododecyl-morpholine or its salts, 2,3-dichloro-1,4-naphthoquinone, 1,4-dichloro-2, 5-dimethoxybenzene, p-dimethylaminobenzene diazodium sulfonate, 1-chloro-2-nitrolpropane, polychloronitrobenzene such as pentachloronitrobenzene, methyl isocyanate, fungicide antibiotics such as griseofulvin or seasonal gamycin, tetrafluorodichloroacetone, 1-phenylthiosemicarbazide, "Bordeaux" alloy, nickel-containing compounds and sulfur.

In the following experiments demonstrating the fungicidal activity of the compounds of the invention, the following known biologically active substance (A) was used as a reference.

Cl / = ^ T \ Cl N N-CH, ~ CH -v / - V 2 I w (A) O-CH2 ~ CH = CH2 Compound known from DE-A-2 063 857 ίο 64 3 60

In Experiment 1, compounds known from FI patent application 752 614 ^ H2 H2 .HCl were also used for comparison.

OF

0 (B) C1 ^ 1!

L .1 H CH

^ I H7 cn2 h2 h2 1. HC1

OF

^ // (C)

\___OF

Test 1

Barley mildew

The leaves of potted barley (Firlbecks Union) seedlings are sprayed with a water emulsion containing 80% (w / w) of active substance and 20% emulsifier and, after drying, the pollen is dusted with the spores of barley powdery mildew (Erysiphe graminis var. Hordei). The test plants are then grown in a greenhouse at a temperature of 20-22 ° C and a relative humidity of 75-80%. After 10 days, the rate of development of downy mildew is determined. Rating scale: 0-5, where 0 = no infection 5 = infection complete N1 11 11 64 360

Degree of leaf adhesion after spraying with 0.05 and 0.025% active substance

Active substance_0.05_0.025 4 2 6 0 3 9 0 3 10 0 4 12 0 2 14 0 2 15 0 3 18 0 3 21 0 2-3 25 0 2 26 0 3 27 0 3 30 0 0 31 0 3 40 2 - 41 0 2 48 0 2 N.

\ 50 0 3 54 0 2-3

OF

\ 59 0 2 ^ 64 0 2 65 0 3 7 0 0 80 0 0 85 0 0 90 0 0 92 0 0 94 - 0 0 104 0 0 113 0 0 114 0 0 115 0 0 116 0 0 i2 64360

Degree of leaf adhesion after spraying with 0.05 and 0.025% active substance

Active substance_ Q, 05_0,025 125 0 0 126 0 0 127 0 0 128 0 0 B 3 4 C 3 4

Check 5

It can be stated that the potency of the reference compounds B and C is clearly inferior to that of the compounds according to the invention.

Test 2

Wheat powdery mildew

As described in Experiment 1, the leaves of potted wheat seedlings (variety "Jubilar") are infected with spores of wheat powdery mildew (Erysiphe graminis var. Tritici) and otherwise treated as in Experiment 1.

Degree of leaf adhesion after spraying with 0.05 and 0.025% active substance

Active substance_0.05_0.025 4 0 2 30 0 0 40 0 2 80 0 0 85 0 0 90 0 0 92 0 0 94 0 0 104 0 0 113 0 0 114 0 0 115 0 0 116 0 0 125 0 0 126 0 0 127 0 1 128 0 2 A 1 3

Control (untreated) 5

II

64360

Test 3

Wheat brown rust

The leaves of potted wheat seedlings (variety "Jubilar") are artificially infected with spores of wheat brown rust (Puccinia recondita) 24 hours before spraying and the seedlings are taken to a room saturated with water vapor, 20-25 ° C. The plants are then sprayed with an aqueous emulsion containing 80% (w / w) of active substance and 20% of emulsifier. After the spray preparation has dried, the test plants are placed in a greenhouse with a temperature of 20-22 ° C and a relative humidity of 75-80%. After 10 days, the rate of rust development is checked.

Leaf adhesion rate 0.05% Active substance after spraying with active substance_ 4 2 12 0 27 0 30 0 7 0 80 0 85 0 90 0 92 0 104 0 113 0 116 0 125 0 126 0 127 0 A 3

Control (untreated) 5 14 64360

Example 1

Tert-butyl- (2,4-dichlorophenyl) -1,2,4-triazol-1-ylmethyl-7-sulfide (Compound No. 65)

To a solution of 22.1 g of 1,2,4-triazole in 500 ml of anhydrous acetone is added 60.5 g of tert. -butyl - [(2,4-dichlorophenyl) -chloromethyl] sulfide. 44.2 g of finely ground potassium carbonate are then added and the mixture is heated with stirring and reflux for 7 hours. The insoluble constituents are then filtered off, the filtrate is concentrated to dryness in vacuo and the residue is diluted with 300 ml of water. Extract the aqueous phase 3 times with 200 ml of methylene chloride, wash the combined extracts with 200 ml of water, dry and concentrate in vacuo. 100 ml of diisopropyl ether are added to give 35.6 g (53%) of colorless crystals, m.p. 9 5-9 7 ° C.

1 H-NMR (10 MHz, CDCl 3 / 1.3 / s (9H), 6.9 δ (s, 1H), 7.0-7.4 (m, 3H, ABX), 8.0 (s, 1H), 8.8 ppm (s, 1H).

Example 2

Bis <tert. -butyl-./ (2,4-dichlorophenyl) -1,2,4-triazol-1-ylmethyl-7-sulfide-copper- (II) chloride to a solution of 9.5 g of tert. -butyl [N- (2,4-dichlorophenyl) -1,2,4-triazol-1-ylmethyl] sulfide in 100 ml of ethanol, 15 ml of a 1 molar solution of copper II chloride dihydrate in ethanol are added dropwise. After standing for two days at 0 [deg.] C., 9.8 g of blue crystals are isolated from this deep blue solution, which is washed with ethanol and ether, m.p. 130 ° C.

Example 3 1 Pentyl-N- (1,2,4-triazol-1-yl) -pentyl- (10-sulfide (Compound No. 75)) 15 64360

A solution of 43.5 g of triazole in 200 ml of dimethylformamide is added dropwise with stirring to a suspension of 13.0 g of sodium hydride in 100 ml of dimethylformamide. After completion of the hydrogen addition, 97.0 g of 1-pentyl / 1-chloropentyl- (1) -7-sulfide are added dropwise to the mixture cooled to room temperature, whereupon the mixture is heated. It is then stirred for a further 8 hours at 80 ° C. The reaction mixture is then concentrated in vacuo, diluted with 500 ml of water and extracted 5 times with methylene chloride. The combined and concentrated extracts are chromatographed on silica gel (5 x 70 cm) first using methylene chloride as solvent. After the first brownish fraction, increasing amounts of acetone (up to 10% acetone) are added to the methylene chloride. As a second fraction, 15.0 g of product are then isolated as a pale yellow oil. IR (film): 2955, 2925, 2860, 1496, 1460, 1271, 1190, 1133, 1008, 677 cm -1.

1 H-NMR (270 MHz, CDCl 3): δ 9 ("tr", 6H), 1.3 (m, 8H), 1.5 (m, 2H), 2.1 (m, 2H), 2.4 ( m, 2H), 5.4 (tr. 1H), 8.0 (s, 1H), 8.4 ppm (s, 1H).

Example 4 1-Pentyl-N- (1,2,4-triazol-1-yl) -pentyl- (1) -N-sulfone (Compound No. 71)

To a solution of 10.0 g of 85% 3-chloroperbenzoic acid in 140 ml of methylene chloride is added dropwise, with stirring, a solution of 6.0 g of 1-pentyl-7T- (1,2,4-triazol-1-yl) -pentyl- (1) -7-sulfide. After completion of the initial warming, stir for a further 2 days at 25 ° C. The mixture is then washed with sodium carbonate solution, sodium sulfite solution and water and the organic phase is dried. After concentration, a bright yellow oil remains, which is triturated with diisopropyl ether to give colorless crystals, m.p. 69-71 ° C.

NMR (CDCl 3, 100 MHz): of0.9 (m, 6H), 1.4 (m, 8H), 1.8 (m, 2H), δ 64360 2.5 (m, 2H), 2.8 ( "dd", 2H), 5.4 (dd, 1H), 8.1 (s, 1H), 8.5 ppm (s, 1H).

Example 5

Tert-butyl - [(2-methyltenyl) -imidazol-1-yl] -methyl] sulfide (Compound No. 89)

A solution of 43.6 g of imidazole in 300 ml of acetone is added dropwise with stirring to 82 g of tert-butyl / (2-methylphenyl) chloromethylsulfide. After the addition of 88 g of finely ground potassium carbonate, the mixture is heated under reflux for 5 hours. The insoluble components are then filtered off and the filtrate is concentrated.

The residue diluted with 300 ml of water is extracted with 3 x 200 ml of methylene chloride. After washing, drying and concentration, 69 g of a brownish oil are obtained from the combined organic phases, which are dissolved in 1 l of diisopropyl ether. Addition of 90 ml of a 2.85 molar hydrogen chloride solution in diisopropyl ether with stirring and dropwise addition gives pale yellow crystals of the hydrochloride from this solution, which are recrystallized from acetone. 51 g of colorless tert-butyl [(2-methylphenyl) imidazol-1-ylmethyl] sulphide hydrochloride are obtained, m.p. 168-170 ° C (comp. No. 110).

After pouring the hydrochloride into an aqueous solution containing 25 g of sodium bicarbonate, the free base is extracted with 3 x 200 ml of ether. After drying and concentration, a pale yellow oil (27 g) is obtained which gradually crystallizes (m.p. 93-95 ° C).

1 H-NMR (60 MHz, CDCl 3): 1.3 (s, 9H), 2.4 (s, 3H), 6.25 (s, 1H), 6.7-7.1 (m, 6H), 7.65 ppm (dd, 1 H).

Example 6 4-Chlorophenyl - ((4'-chlorophenyl) imidazolylmethyl] sulfide (Compound No. 7)

A mixture of 60.7 g of 4-chlorophenyl- (chloromethyl- (4'-chlorophenyl)) sulphide, 27.2 g of imidazole and 55.4 g of potassium carbonate in 400 ml of acetone is refluxed with stirring for 5 hours. Filter, then concentrate the filtrate to dryness and dilute with 500 ml of water. This mixture is extracted 3 times with 200 ml of methylene chloride. The combined extracts are dried over sodium sulfate. After trituration with diisopropyl ether, 26 g (38%) of colorless crystals, m.p. At 88 ° C.

1 H-NMR (60MHz, CDCl 3): δ 6.3 (s, 1H, 6.9-7.4 (m, 10H), 7.5 (algae, s, 1H).

Example 7

Tert-butyl / (2,6-dichlorophenyl) -pyrazolylmethyl] sulfide (Compound No. 53)

To a solution of 193 g of tert-butyl (chloromethyl- (2,6-dichlorophenyl)) sulfide and 44 g of pyrazole in 1 l of toluene is added dropwise 66 g of triethylamine and the mixture is refluxed for a further hour after completion of the slight exotherm. The insolubles are filtered off, the filtrate is concentrated and the residue is diluted with 500 ml of water. After extraction 3 times with 200 ml of methylene chloride, concentration of the combined extracts gives a solid residue which, after washing with diisopropyl ether, gives 117 g (57%) of colorless crystals, m.p. 97-98 ° C.

1 H-NMR (60 MHz), CDCl 3): </ 1.4 ppm (s, 9H), 6.2 ("tr.", 1H, 7.0-7.3 (m, 3H), 7.4 ("d", 1H), 8.2 ("d", 2H).

Example 8 2,4-Dichlorobenzyl- (1,2,4-triazolylmethyl) sulfide (Compound No. 78)

A mixture of 60.4 g of chloromethyl- (2,4-dichlorobenzyl) sulphide, 35 g of 1,2,4-triazole and 69 g of crushed potassium carbonate in 300 ml of anhydrous acetone is refluxed for 10 hours. The insoluble constituents are then filtered off, the filtrate is concentrated to dryness in vacuo and the residue is diluted with 300 ml of water. It is then extracted three times with 200 ml of methylene chloride, the combined extracts are dried and concentrated in vacuo. From the residual brown oil, 39.8 g (58%) of colorless crystals are obtained by crystallization from diisopropyl ether / methanol at -60 [deg.] C., m.p. 68-70 ° C.

1 H-NMR (60 MHz, CDCl 3: 3.8 (s, 2H), 5.0 (s, 2H), 7.0-7.5 (m, 3H), 7.9 (s, 1H), δ , 2 (s, 1 H).

18 64360

Example 9 2,4-Dichlorobenzyl- (2 ', 4'-dichlorophenyl-1,2,4-triazol-1-ylmethyl) sulfide (Compound No. 61) and 2,4-Dichlorobenzyl / (2', 4'-Dichlorophenyl- (1,2,4-triazol-4-yl) methyl] sulfide (Compound No. 64).

A mixture of 200 g of 2,4-dichlorobenzyl-N- (2 ', 4'-dichlorophenyl) -chloromethyl / sulphide, 145 g of 1,2,4-triazole and 138 g of crushed potassium carbonate in 2 l of anhydrous acetone is refluxed with vigorous stirring for 9 hours. The solids are then filtered off, the filtrate is concentrated to dryness in vacuo and the oily residue is extracted 5 times with 2-0 ml of methylene chloride after addition of 500 ml of water. The combined organic phases are dried over sodium sulfate and concentrated to dryness in vacuo. Trituration of the residue in diisopropyl ether gives 157 g of colorless crystals containing 8: 2 isomers of triazolyl compounds.

This mixture is extracted several times with hot hexane. 122 g (65%) of 2,4-dichlorobenzyl - (2 ', 4'-dichlorophenyl) -1,2,4-triazol-1-ylmethyl / sulfide are obtained in the form of colorless crystals by distilling off the solvent in vacuo from the combined hexane solutions, mp. 120-125 ° C.

1 H-NMR (220 MHz), λ max (λ max): δ 3.9 ppm (broad s, 2H), 6.65 (s, 1H), 7.0-7.5 (m, 6H), 8.0 (s. 1H), 8.6 (s. 1H).

The colorless, insoluble residue of the hexane fraction consists of 27 g of (12%) 2,4-dichlorobenzyl - ['(2', 4'-dichlorophenyl) - (1,2,4-triazol-4-yl) methyl] -sulfidia, m.p. 132-133 ° C.

1 H-NMR (220 MHz, CDCl 3): δ = 3.9 ppm (s, 2H), 6.5 (s, 1H), 7.0-7.5 (m, 6H), δ 45 (p. 2H).

Example 10

Tert-butyl N- (4-chlorophenyl) -1,2,4-triazol-1-ylmethyl-7-sulfide (Compound No. 30)

To a solution of 78 g of tert-butyl-((4-chlorophenyl) -chloromethyl] sulfide in 175 ml of dry dimethylformamide (DMF) is added dropwise with stirring 350 ml of one molar 1,2,4-triazolyl sodium in DMF (prepared from 0 , 35 moles of sodium hydride and 0.35 moles of 1,2,4-triazole in 350 ml of DMF After completion of the slight exotherm, the mixture is stirred for a further 4 hours at 80 [deg.] C. The mixture is poured into 1 [deg.] C. water and extracted 3 times with 200 ml of methylene chloride The combined organic phases are washed with water, dried over sodium sulphate and evaporated in vacuo to give a residue in 150 ml of diisopropyl ether by trituration with 40.0 g (46%) of colorless crystals, m.p. 95 ° C.

1 H-NMR (60 MHz, CDCl 3): cf = 1.3 ppm (s, 9H), 6.6 (s, 1H) 7.2 (AA1BB ', 4H), 8.0 (s, 1H) , 8.7 (s. 1H).

Example 11

Tert-butyl - ((4-chlorophenyl) -1,2,4-triazolylmethyl) sulfoxide (Compound No. 31).

To a solution of 9.7 g of tert-butyl / (4-chlorophenyl) -1,2,4-triazolylmethyl-7-sulfide in 20 ml of methylene chloride is added dropwise in a ice bath a solution of 7.1 g of 85% 3-chloro perbenzoic acid in 70 ml of methylene chloride. Stir for a further two hours at 0 ° C until sulphide (R and 0.20). The solution is washed until the evolution of Cl2 has ceased with aqueous sodium hydrogen carbonate solution. After washing the organic phase with water, this is dried, concentrated and the solid residue is washed with a small amount of ether. 7.0 g (67%) of colorless crystals are obtained, m.p. 125-128 ° C.

1 H-NMR (220 MHz, CDCl 3): 1.10 and 1.15 (two s, additional 9H), 6.18 and 6.24 (two s, additional 1H), 7.3-7.7 ( m, 4K), 8.01 and 8.07 (two s, plus 1H), 8.41 and 8.51 (two s, plus 1H).

Example 12

Tert. -butyl - [(4-chlorophenyl) -1,2,4-triazolylmethyl] -N-sulfone (Compound No. 32).

To a solution of 10.7 g of tert-butyl (N-chlorophenyl) -1,2,4-triazolylmethyl / sulfoxide in 50 ml of methylene chloride at 20 ° C is added dropwise a solution of 7.3 g. 85% 3-chloroperbenzoic acid in 100 ml of methylene chloride. According to the result of thin layer chromatography (DC), the less polar sulfoxide oxidizes more rapidly, only after a longer stirring at room temperature does the more polar sulfoxide oxidize more strongly. After 18 hours, according to DC (SiO 2, methylene chloride / acetone 7: 3), the exchange reaction is complete. The sulfone (Rf = 0.46) is isolated by washing the solution with sodium bicarbonate solution and water, drying and concentrating the organic phase.

Washing of the residue with diisopropyl ether gives 8.7 g (77%) of colorless crystals, m.p. 150 ° C.

1 H-NMR (220 MHz, XDCl 3): δ 1.3 ppm (s, 9H), 6.75 (s, 1H), 7.5 (AA'BB1, 4H), 8.03 (s, 1H ), 8.84 (s, 1 H).

Example 13 4-Chloro-phenyl - ['(4 + -chloro-phenyl) -tetrazol-1-yl) -methyl] -sulfide and 4-chloro-phenyl - ((4'-chloro-phenyl) - (tetrazol-2-yl) -methyl / sulfide (Compound No. 15).

To a mixture of 26.1 g of tetrazole and 102 g of 4-chlorophenyl- [(4'-chlorophenyl) -chloromethyl] sulfide in 3.5 l of toluene is added dropwise at room temperature 37.4 g of triethylamine with stirring. The mixture is then heated to reflux for 4 hours. The insoluble constituents are filtered off, the filtrate is washed with water and the organic phase is dried over sodium sulfate. Distillation of the solvent in vacuo left a solid residue which crystallized after the addition of 50 ml of diisopropyl ether to give 74.7 g (67%) of yellowish crystals, m.p. 104-106 ° C.

1 H-NMR (60 MHz, CDCl 3): δ 6.7-7.6 ppm (m, 9H), 8.4 and 8.9 (two s, additional 2H).

Examples of other compounds of formula I are given in Table no. 1.

Table 1 21 64360

Compound R1 Hg At ^ amla "a3 SP. (° C

1 <ÖV HN ^ S> 0 ~ @) 132-13 «\ J_N V- / .—« IR (Films): 2 H, C- KN /) 0 - <OVcl 1 * 495, 1 * 470, -5 'iN v = - / 1270, 1192, 1131, 1088, 1007, 8} 7, 666 en -1.

fr \ Ji / - \ IR (Filr.j), 3 HM O -CH, - (O) 3060, 3C20, 21142, 1'* 50, "1271, 1190, 1131, 1008, 695, 677, ^ / —V 658 cm 1 ** Cl · © - H ^ 0 “\ θ) 98 5 cl- © - H> Q 1 - © 131-139 °» 6 Cl - (^ y H 2 ^ o) 215 7 Cl · © - H 0 - ^ 5 ^ -Cl 88 8 Cl-®-H. (C00H) 2 0 85-87 9 Cl- ^ 5 ^ - H 0 ~ (0) ~ Cl 62 "61) 1 ° driving) - H 1 -? the structure of all prepared compounds is confirmed by 1 H-NMR spectrum.

Table 1 (continued) 22 64360

Compound R1 R2_Azide salt n _ ^ _ Sp. (° c) 13 Ci ^ g) - a '0 1 Cl 1,7,1 11 C1 ^ 5> H 0 2 - <§> -0! 20.

t M) 15 Cl- ©> - h 0. Q4 o - <@ K1 10.-106 16 Cl ^ ÖV h Λ. 0 1 110-1124 °

N — y ^ N— 'N-N

17 01- / 5V H Λ. 0 ’2 - @ K1 123-125

N-7 N “N

I _ 18 Cl "(C ^" H ^ 0 "^ XCH3 150 t 19 Cl- ^ o) - H 1; ^ 5 ^ 'CH3 l! * 7" lt, 9 ++) f 20 cl "<§) “H 1 * {0) * 0Η3 15l '" 155 ++ *) »21 ci ^ oy h 2 ko ^ h3 24.5 H _yC1 22 Cl • <Ö> -" <J 0 - <2λ ° ι 107 i Cl 23 ci · ®- H 0 - @ ci 135-137

Cl · IRiFilniJ: 2 * »C1“ (0> - HCJ 0 tert.-fautyy-? Slo * 1362 ',' - '' —N li 1212, 1152, 1096, ioen, 10 * »3, 81» «, 787, 657cm "1 +) mixture of tetrazole isomers ++) mixture of diastereesters of sulphoxides +++) more strongly polar sulphoxide, crystallized purified from dlastereaneerlsedks no. 19 li

Table 1 (continued) 23 64 360

Compound R1__AtsfrMsimla n _ ^ _ SP · (C) t 25 Cl - @ - H 0 ^ Ö ^ OCK, ”6 26 Cl-®- H £ 2> 98 27 Cl -®- HQ 0 - ™ 2 <Ö) 6> 57 -58, -. N IR (Circuit); 28 Cl / o H N 7) 0 ethyl 2965, 2925,

Nirl / l * »90, 1271, 1131, 1088 *.

, 1010,675cm J

/ - \, / Ns Λ IR (Movies); 29 ci- <0> - H ny 0 n-butyl 29 ^ 5, 2920 * - «i486, 1268, 1127, 108HA1 1007,671cm '/ - v ^ nn„ tert.- _e 30 Cl · © * ho 95 f , -V -N tert.- 31 1 butyl 125-128 t 32 c 1 H 2 H 2 N 2 O 7. 150 \ NJ Ni_N butyl • IR (Film): / —v 305¾. 10'3 °, 33 cl \ oy H \ (! 0 aiiyyii 1003, 1270, * -N 1130, 1087, 1007,.

• -t-ö-v-t- 672 cm -1 tGJTt 1 “3 * i Br- ^ y- H N ^ jj) 0 77-78 N tert.-

35 h 0 102-10U

f 36 »o @ - H Λ o 73-75 .—. tert.- 37 02N- (O) -H 0 butyl 76-78

Diastereaner mixture 24 64360

Table I (continued)

The compound R1_R ^ _Azide (salt) n_R3_Sp. (° c) CH, _ 38 V | ° tert-butyl 94 39 H H ύ ° Cl 47- ^ 9 ΊΟ (θ) ~ H N * "/) 0 ~ (0) 91

VI-N

s' Ci j! | / -V

* »1 <2 / H 1 \ Q / 70-88 °" 2 <Q> ^ H νΛ 2 1 «5 ^ C1 li * 3 (oy HM '> 0 tert.- 8¾ N butyl ^ * Ό *' 5 «-.57 '> pre ij ^ 5 \ Q / ~ -h / ^ 2 tert.- 126 Ί- N-butyl / - \ M ^ _> CF, IR (Filnd):

'6 p- »Q« - ™ 2 ^> U & iSS

1115, 1070 3 790, 625,

660 cm A

ci £ cl \ ¢ 7 01 \ ^ 7 H · (cooh) 2 0 -CH2- ^ C ^ C1 ^ 3-135 * 8 Cl ^ Ö> - H νΛ> O -CK2 ^ C1 101

CI's. E1 Cl2 -CH2h (Q) u: 1 195-197 * 'Diastereomeric mixture

Table X (continued) 25 64360

Compound R1__Azide (salt) n _ ^ _ ^ P · ^ c ^ 50 01¾). H> »'j> 0 -Cl!, - <§) ci 82-8» 51 01¾). «(]} '* Ö' '^ λΙ ^ 1 ^ -110 ° 52 01 ^) - H * t (% 2 -CH2 ^ gKl 100-105

r-SCl N

53 (OJ H n '> o tert-butyl 97-9? ^ Ci' - '«54 Λ- <α1 h /% o tert.-butyl 110-112 (pr' - ^ ci 55 \ Ql / H ΐΛ) 0 tert-butyl 112-115 (O / * <ö> Ji o 56? oV ~ H 1 tert-butyl 122-127 '(¾ 57 <0> - H / **> 2 tert-butyl 180-183

i-n

58 Cl <öf H Ö 0 ~ ^ cl 128 59 01 ^ H Φ 0 - <2 ^ C1 ,, 8-15 °

Ci A

60 Cl- ^ H Mj 0 -CH2- (O) ci 105 +) Diastereomeric mixture

Table I (continued) 26 64360

Compound R1__Azide (salt) n_r3_Sp. (° c) 61 Cl- ^ 5 ^ - H 0 (CH2 '^)' C1 120-125 62 Cl k A 1 -CH2i ^> Cl 125-131 ° 63 C1- <Q> - H 2 -CH ^ Cl I63-I65 WC1 N-C1v 64 C1- \ 0 / H f ^ 0 "CH2 '<(Ö} -C1 132-133 65 ci- (o) -H o tert-butyl 95-97 .d Λ 66 Cl / oV- HN ^ '% 0 -CH, 66-88 \ _y \ L_N 3 _ci;} 67 C1- (Q> - H / j? 0 95-97 «χΝ. / - \ IR (Film) cm- 188 CH.-OC- .HN y 0 ~ \ 0) 2950, 1748, ^ i— N '1433, 1260, 1196, 1128, 994, 746, 689, 672 t 69 n-hexyl H Λ o - <Ö > -C1 2850, 1490, 1471, 1270, 1132, 1089, .1008, 818,, 674 cm-70 n-butyl H n '> O "(oVcl IR (Film):' i-K 2950, 2920, 1496-, 1472, 1270, 1132, 1089, 1008, 8l8,672cm_1 +) Diastereaner mixture

Table I (continued) 27 6 4 3 6 0

Compound R1 R2 Azide (salt) n R "5 Sp, t 71 n-butyl H n '% 2 n-pentyl 69_71

t_N

72 H3C- H3C- (O 0 - ^) - C1 v M _ IR (Filni): "} - H Ό ° - @ ^ ci» n: ^ 1130, 1050, 1007, 815, 673 cm-1 ethyl H n '> 0 n-propyl f? | §' ^ 70, 'N 1192! 1133, 1CO 3, §17, 675 cm -1, IR (Film): N. 295 ^ 2 ° 25 75 n-butyl h n '' ^ O n-pentyl ^ αβό ', 1 ^ 96' Ι-n 1460, 1271, 1190, 1133, 1008, -1677 cm -1, IR (Film):. Ί. A UIT 2955> 2925> 7 6 n-pentyl h N> 0 n-hexyl 2860, 1497, vt-N 1460, 1272, 1192, 1135, 1012,, 678 cm 77 h- k ö 0 - «“ s · ^ ) * ·· ^ -45 • Ä C1> _ 78 H- H 0 -CH2 - <^^ C1 68-70 i CV- <C1 79 H- H 0 -CH2 ~ (oV 60-63 N ciN ^

Table I (continued)

Compound r1 r2 Azide (vein R3 ςη (° c) _La) _? P * 8 ° H ° 10C "103 31“ ö 1 Ά _ / C1 ^ tert 82 \ y) ~ H ιζ ** Ίΐ 2 butyl 164 -165 'ci' 83 n-butyl H 0 ίϊ ^ ϊ * · Η iH (Filni): ^ 'LH butyl 2953, 1459, 13-: 4, 1272, 1190, 1153, 1134, _t 1010, 677 en 84 i -butyl H Λ o IR (Fnn i): N-butyl 2962, 2662, 1494, 1457, 1364, 1270, 1189, 1157, 1132, 1007, 675 cm-85 i-butyl h ΐζ1 ^ 0 - ^ Q ^ -Cl 45-46 86 i-butyl H 1 ~ (Ö) -C1 110-112 87 i-butyl H nQ 2 i4o-i4i 64360 29

Table I (continued)

Compound r1 r2 Acid (salt) n__Sp. (° o) .CH, j — K 3 Λ tert.- 88 {äy H '\ jH 0 fcutyyii 98-ioi 89 <ö £ 3 - 0 ° Sii 93 · 55 90 3-heptyl H τζ ^ 7) 0 / o \ ci iR (Milk): LN Nf 295a, 2 ° 22.

1 72, 1269, 1131, 1088, 1008, 819,, 673 cm -1 * OJ H MfN 3 O 3 -methyl-IR (Film): * -butyl 2962, 1 899, yy 1271, 1130, 1088, 1012, _1 p 676 cm 92 <Ö) - H 0 <ö> Cl 105-107, -, λ tert.- 93 (O) -H ^ 0 butyl 106 “103

FjC f tert.- 94 / qV h Ö 0 ^ 1 ^ 11 «H Ö 0 ra 85'97

., CN

96 <5) - H Ö 1'0'112 97 <? ^ - H> Q 0 9 * -? 5 / -ccl 98 (öy H o ethyl 59-61 99 <^ ^ ^ - H 2 ethyl 103-10 *

Table I (continued) 30 6 4 3 6 0

Compound R1 R2 Azide (salt) n R3 'Sp. / Oc, 100 (o). H Λ o n_butyl IM Filmy.

L.- 2958, 2928, 1440, 1274, 1132, 1008,.

Cl 748, 678 cm 101 / nV H o n -hexyl iR (Film):

XlJ 2955, 2923, 1491, 1271, 1129, 1007, <, C1 (744, 675 er 102 <ö> HQ 0 _ch2 ^ p) 96-93 103 (Q) ~ H n (j! 2 _CH2 ^ \ 5 / / Cl 104 (p) ~ H 0 -CH 2 -CH 2 ^ 2 ^ 58-61 / Cl 105 (py H 2 -CH 2 -CH 2 - <g> 129-130, C1 106 ci- ^ Cy- H 0 ^ p) ~ zl 108-110 CV \ 107 HH t (* jj o - \ Oy-Cl 84-37

Cl 108 h H 1 KOVci 152-155 'L.N' —f

Cl 109 H H 2 - ^ 0 ^> - Cl / ^ 3 110 (ny H. HCl 0 tert.- 163-170 tert-butyl m »Ö · HCl 0 n-butyl 136-139 * 31

Table I (continued) 64 360

Compound H1 R2 Azide (salt) n R3 Sp. (° c) yCl 112 (oy H iQ. HCl O -CH2-CH2- / o ^) 1 ^ 5-155 113 P "(? ^ · H 0" “(o)" 01 90-92 Π »F © K, Q 0 © Cl 119-120, Cl 115 (2 / h δ 0 69-71 s Cl 116 (2 / H 10 Q 0 ^ (2) ^ 01 i3i · * 136, C1 117 ^ OV H Λ 0 tert. - iR (? iiai): n-butyl 3098, 2950, 1 ^ 63, 1211, 1153, 1002, 1040, 739, _ «.Cl ^ 657 and 118 Cl. ©. H» {j »2 940 .Ci / - \ h tert.- 119 C1H \ 2 / H ö 2 i 53-156 120 <Ö> ”0 W'U5 / CH,> 2 '<ö>« Ö 2 SSil 160-162 32 64360

Table I (continued)

Compound R1 r2 Acid (salt) n R3 Sp '° c) vcl 122 <0> H ζΚ 2 tert · "113-U6> -' bu style zcl 123 H fÖ 2 ^ Ö) -C1 155-158 C / - \ 1H (Film): h 0 - <0> C1 2956, 2922, ({N- / 1 972, 1968, 1168, 1090, 1009, 817, rv »61) 7 cm *

.3 / K

125 CH3-C-CH2- H // 0 - / O Vei 33-86 CHj U_N '-' CH3> 1 126 CH ^ C-CHg H 0 4? - 51 CH »

OF

127 (O) -H 2 O - <Oy-c: 89-90

Cl / - <r ~ \ 1H (Fllmi): 128 Cl- (O) - H \\ // O -CHp- (0) -Cl 3103, 1586, '—f' “N d \ —f 1953, 1373 , 1217, 1090, 1067, 1048, 1012, 825, 659 cm 1 '

Claims (2)

64360 Alkyl and aryl-substituted oC-azolylmethyl sulfides for use as fungicides, characterized in that they have the formula r2 (O) n R1 - C - S - R3 (I) t Az wherein R1 is hydrogen, C1-C4-alkyl, (C 1 -C 4 alkoxy) carbonyl or optionally substituted aryl, R 2 is hydrogen or C 1 -C 4 alkyl, 3 R is C 1 -C 4 alkyl, C 2 -C 6 alkenyl, C 1 -C 4 alkyl alkynyl, optionally substituted phenyl or optionally substituted aryl- (C 1 -C 4 alkyl), Az is imidazol-1-yl, pyrazol-1-yl, 1,2,4-triazol-1-yl, 1,2,4- triazol-4-yl, tetrazol-1-yl or tetrazol-2-yl and n is 0, 1 or 2, and their salts and metal complexes with copper, zinc, manganese, iron, cobalt and nickel. Compounds of formula I according to claim 1, characterized in that R 1 is phenyl, halophenyl, trifluoro-2-methylphenyl, R is hydrogen and R is halophenyl or tert-butyl, and their salts and metal complexes.