CA1112647A - .alpha.-AZOLYL SULFIDES AND THEIR DERIVATIVES - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE :
The present invention is concerned with .alpha.-azolyl sulfides, and their derivatives consisting of .alpha.-azolyl sulfoxides and .alpha.-azolyl sulfones of the formula

Description

~h~6~
The present invention relates to new and valuahle ~ -azolyl sulfides and -their derivatives, ~-azolyl sulfoxides and ~-azolyl sul~ones, and their salts and metal complexes,processes for their production and their use as fungicides~

It has been disclosed that imidazole deriv-atives, e.g. l-L2/4-dichlorophenyl-~ -allylethyl ether]-imidazole (German Laid-Open application DOS 2,063,857) have a fungicidal action. At low application rates and concentrations, this action is not always satisfactory. Furthermore, the fungitoxic action is often accompanied by a high phytotoxicity; conse~
quently, at the concentration necessary for combatting rusts the crop plants are also damaged. For these reasons, they are not always suitable, and not in every plant species, for use as crop protection agents for combatting fungi.

We have now found that the new ~ -azolyl sulfides, and their derivatives consisting of ~-azolyl sulfoxides and ~-azolyl sulfones, o~ the formula R2 (O) Rl _ C - ~ - R3 (I), where R denotes hydrogen, alkyl, alkoxycarbonyl, or unsub-stituted aryl or aryl substituted by halogen, NO2, alkyl or haloalkyl; R denotes hydrogen or alkyl, R3 denotes alkyl, alkenyl, alkynyl, unsubstituted phenyl or phenyl substituted by alkoxy, alkyl or halogen, or unsubstituted aralkyl or aralkyl substituted by halogen, Az denotes imidazol-l-yl, pyrazol-l-yl, 1,2,4-triazol-1-yl, 1,2,4-triazol-4-yl, tetrazol-l-yl or tetrazol-2-yl, and n denotes one of the integers 0,1 and 2, and their salts and metal complexes of copper, tin, zinc,manga-nese, iron, cobalt and nickel.

~h~ L7 O.Z0 32,728 Examples o~ meanings ~or R are hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, n-pentyl, n-hexyl, n-heptyl-(3), methoxycarbonyl, phenyl, 4-nitrophenyl, 4 bromophenyl, 4-cyano-phenyl, 2-methylphenyl, 4-tert-butylphenyl, 3-trifluoromethyl-phenyl, 4-trifluoromethylphenyl, 4-fluorophenyl, 2-chlorophenyl, 4-chlorophenyl, 2g4-dichlorophenyl, 2,6-dichlorophenyl, 3,4-dl-chlorophenyl, and ~ -naphthyl~ -Examples of meanings for R2 are hydrogen, methyl and n-propyl.
Examples of meanings for R3 are methyl, ethyl, n-propyl, isopropyl, n butyl, tert-butyl, n-pentyl, n~hexyl, ally~ propargyl, phenyl, 4-methoxyphenyl, 4-tolyl,4-chlorophenyl, 3,4-dichloro-phenyl, 2,4-dichlorophenyl, 2,3,6-trichlorophenyl, benzyl, 3-trifluoromethylbenzyl, 4-chlorobenzyl, 4-bromobenzyl, 3,4~di-chlorobenzyl, 2,4-dichlorobenzyl, 2,3,6-trichlorobenzyl and

2~phenylethyl.
Examples o~ salts are hydrochlorides, bromides, sulfates, nitrates, phosphates, oxalates and dodecylbenzenesulfonates. As the action of the salts is attributable to the cationl any anion may be selected.
The metal complexes are compounds of the formula rMe(R1 - C - S n_ R3) ~ Xk (II), Az where Rl, R2, R3, Az and n have the above meanings and Me denotes a metal, e.g. 3 copper, zinc, tin, manganese, iron, cobalt or nickel, X denotes the anion o~ an inorganic acid, e.g., hydrochloric acid, sul~uric acid, phosphoric acid or hydrobromic acid, m denotes one o~ the integers 1, 2, 3 and 4, and k denotes one of the integers 1, 2, 3 and 4.

% ~ ~ 7 O.Z. 32,728 We have ~urther found that ~-azolyl sulfides of the formula I (n - O) are obtained by reacting ~ -chlorosulfides o~
the ~ormula R1 _ C - S - R3 (III), Cl where R1, R2 and R3 have the above meanings~ with azoles H-Az, where Az has the above meanings, in the presence or absence of a basa and of a diluent. Oxidation of the ~-aæolyl sulfides of the formula I (n - O) formed gives ~ ~azolyl sulfoxides of the formula I
(n - 1) and ~-azolyl sulfones o~ the formula I (n - 2).
For the production of the ~ -azolyl sulfides of the formula I
(n = O) it is advantageous to react the ~-chlorosulfides of the ~ormula III, with or without a diluent, with about 0.5 to 2 equi-valents of an alkali metal salt of the azole in question, or with about 0.5 to 4 equivalents o~ the azole in question, if desired with the addition of from 0 5 to 4 e~uivalents of a base, at tem peratures o~ ~rom about 0 to 200C, preferably from 20 to 160C, ~; and in homogeneous or inhomogeneous phase.
Examples of diluents are methanol, ethanol, isopropanol, n~butanol, diethyl ether, tetrahydrofuran, dioxane, acetone, acetonitrile, dimethylformamide, dimethyl sulfoxideg chloroform~
methylene chloride and toluene. Examples of bases are organic amines such as triethylamine and pyridine, or inorganic compounds, e.g., potassium carbonate or sodium hydroxide.
Some of the ~-chlorosuI~ides III used as starting materials are known Yrom the literature or may be produced by processes known from the literature 5 e.g~
a) chlorination o~ sulfides with N-chlorosuccinimide (see, for example, B.L. Tuleen and T.B. Stephens, J. Org. Chem., 34, 31, lg69), as follows:

6~7 o. z. 32l 728 o ., R1 _ CH - S ~ R3 ~ ~ N~Cl --O
~2 0 R1 _ C - S R3 ~ ~ NH
Cl (III) ~

or b) reaction of aldehydes with thiols in the presence of hydrogen chloride (see, for example, H. Bohme. H~ Fischer and R. Frank, Liebigs Ann. Chem. 563, 54, 1~49) as follows:

R -C0 + HSR + HCl - ~ -H
R l- C-SR3 H 20 Cl (III) ~ o produce the ~ -azolyl sulfo~ides of the formula I (n - 1), the ~-azolyl sulfides are reacted, in the presence or absence of .
a diluent, with about 1 equivalent of a suitable oxidant at from about -30 to +100 5. The ~-azolyl sulfones (I, n - 2) are obtained ;~
in similar ~anner by oxidizing the ~-azolyl sulfides (I, n - 0) with at least 2 equivalents of a suitable oxidant or by oxidizing 10 the d-azolyl sulfoxides (I, n = 1) with at least 1 equi~alent Or an oxidant.
Examples of suitable oxidants are potassium permanganate, hydrogen peroxide and percarboxylic acids such as peracetic acid, perbenzoic acid and 3-chloroperbenzoic acid. Examples of diluents are water, acetic acid, methanol, acetone, chloroform, and methylene chloride. A preferred process for producing the sulfoxides (I~
n = 1) is the reaction of the sulfides (I, n = 0) wlth 1 equivalent of 3-chloroperbenzoic acid in methylene chloride at from 0 to 25C.
A preferred process for producing the sulfones is the reaction of the sulfides (I, n = 0) with 2 equivalents of 3-chloroperbenzoic acid in methylene chloride at from 15 to 41C.

O.Z. 32,728 The compounds of the formula I (n = 03 1 or 2) are readily soluble substances in numerous organic solvents, e.g.~ ethyl acetate, acetone, ethanol~ methylene chloride, chloroform, dimethyl sul~oxide, dimethylformamide and N-methylpyrrolidone.
The ~ ~azolyl sul~ides (I, n = 0) also dissolve well in toluene.
They may be converted into their salts~ e.g., hydrochlorides, sulfates, nitrates, oxalates 3 formates, acetates and dodecyl~
benzenesulfonates, with acids.
We have also found that the metal complexes of the ~ormula II
are obtained by reacting the ~ -azolyl sulfides or their derivatives of the formula I with metal salts of the formula MeXk . a H20 (IV), where Me, X and k have the above meanings and a denotes one of the integers 0, 1, 2, 3 and 4g in the presence of a solvent. Here, Me preferably stands for metals of subgroups I, II and IV to VIII, and of main groups II and IV, of the Period~c Table, especially copper, zinc, tin, manganese, iron, cobalt and nickel.
The metal salts of the formula IV are generally known and readily accessible compounds.
For the production of the metal complexes of the ~ormula II, 2~ all water-miscible solvents are suitable, preferably methanol, ethanol, isopropanol, acetone, tetrahydrofuran and dioxaneO The temperatures employed ~re generally from 0 to 100~, preferably ~rom 10 to 35C.
The sulfides (I, n = 0) and sulfones (I, n = 2) contain an asymmetric carbon akom and are therefore obtained as enantiomorphous mixtures which may be separated into the optically active compoundsf In the case of the sulfoxides (I, n = 1)~ diastereoisomeric mix-tures occur as a result of the asymmetric sulfur atom adjacent to the asy~netric carbon atom; these mixtures may be separated into their individual cornponents in con~entional manner, e.g., O.Z. 32,728 crystallization or chromatography Howe~er, for use as fungicides or agents for regulating plant growth it is normally not neces-sary to separate the enantiomorphs and diastereoisomers.

tert-butyl- ~2,4-dichlorophenyl)-1,2,4-triazol-1-yl-methyl~ osul fide (compound no. 65) 60.5 g of tert-butyl-[(2,4~dichlorophenyl~-chloromethyl3 -sul-fide is added to a solution o~ 22.1 g of 1,2g4-triazole in 500 ml of anhydrous acetone. After the addition of 44.2 g of finely powderedpotassium carbonate the mixture is refluxed for 7 hours while stirring. The insoluble components are then filtered off, the filtrate is concentrated to dryness in vacuo, and 300 ml of water is added to the residue, The aqueous phase is extracted three times with methylene chloride (200 ml each time) and the combined extracts are washed with 200 ml of water, dried and ~
concentrated in vacuo. After the addition of 100 ml o~ diiso- ~-propyl ekher~ there is obtained ~rom the residue 3~.6 g (53%)of colorless crystals; m.p.: 95-97C.
H-nmr (100 MHz, CDCl~ = 1.3 (s~ 9H)~ 6.95 (s~ lH), 7.0-7.4 (m. 3H, ABX), 8.0 (s, lH), 8.8 ppm (s, lH).

bis-<tert-butyl-[(2,4-dichlorophenyl)-1,2,4-triazol-1-yl-methyl]-sul-fide~-copper(II) chloride 15 ml of a molar ethano]ic solution of copper(II) chloride dihydrate is dripped into a solution o~ 9.5 g of tert-butyl-[(2,4-dichlorophenyl)-1,2,4~triazol~1-yl-methyl]-sulfide in 100 ml of ethanol. After this deep blue solution has stood for 2 days at 0C, there is isolated from it 9.8 g of blue crystals, which are washed with ethanol and ether; m.p.: 130C.

~$~69~7 O.Z. 32,72 l-pentyl Ll-(1,2,4~triazol-1-yl)-pentyl-tlj~-sulfide (compound no. 75) While stirring, a solution of 43.5 g of triazole in 200 ml o~ dimethylformamide is dripped into a suspension of 13.0 g of sodium hydride in 100 ml of dimethylformamide. Upon completion of the hydrogen evolution, the mixture is cooled to room tem-perature and 97~0 g of l-pentyl-[l-chloropentyl-(l)]-sulfide is added, whereupon the mixture heats up again. It is subsequently stirred for a further 8 hours at 80 C. It is then concentrated in vacuo, 500 ml of water is added, and the mixture is extracted 5 times with methylene chloride. The combined and concentrated extracts are chromatographed on silica gel (5 x 70 cm), initially using methylene chloride as developer. After the first, brownish, zone has passed through, increasin~ amounts (up to 10%) of acetone are added. In this manner, 15.0 g of the desired product is isolated as the second zone as a pale yellow oil. IR (film): 2955, 2925, 2860, 1496~ 1460, 1271, 1190, 11~3, 1008, 677 cm 1~
H-nmr (270 MHz, CDCl3): ~ = 0.9 ("tr", 6H), 1.3 (m, 8H)g 1.5 (m, 2H), 2.1 (m, 2H), 2.4 (m, 2H), 5.4 (tr, lH), 8.0 (s, lH), 8,4 ppm (s, lH)o l~pentyl~ (1,2,4-triazol-1 yl)-pentyl-(l)]-sulfone (compound no. 71) While stirring and cooling with ice, a solution of 6.0 g o~
l-pentyl- [1-(1,2~4-triazol-1-yl)-pentyl-(1 ~sulfide is dripped into a solution of 10.0 g of 85% strength 3-chloroperbenzoic acid in 140 ml of methyl chloride. When the heat evolution - which takes place initially - ceases, the mixture is then stirred for 2 days at 25C. It is then washed with sodium carbonate solution, sodium ~ 7 --~gL%~
O.Z, 32,728 sulfite solution and water~ and the organic phase is dried. After concentration, a pale yellow oil remains from which, upon trituration with diisopropyl etherg there is obtained 3. 5 g of colorless crystals;
m.p.0 69-71C.
nmr (CDCl3, 100 r~z): ~- 0.9 (m, 6H), 1.4 (m~ 8H), 1.8 (m, 2H), 2.5 (m, 2H), 2.8 (l'dd"~ 2H), 5.4 (dd~ lH)~ 8.1 ~s, lH), 8.5 ppm (s, lH).

tert-butyl-~(2-methylphenyl)-imidazol-l yl-methyl~-sulfide (compound no. 89) While stirring9 82 g of tert~butyl-[(2-methylphenyl)-chloro-methyl -sulfide is dripped into a solution of 43.6 g of imidazole in 300 ml of acetone. Arter the addition of 88 g of finely powdered potassium carbonate, the mixture is refluxed for 5 hours. The un-dissolved constituents are filtered off and the filtrate is con-centrated. 300 ml of water is added to the residue, and extraction carried out ~ith 3 x 200 ml of methylene chloride. The organic phases are combined, washed with water~ dried and concentrated.
There is obtained 69 g of a brownish oil which i~ dissolved in 1 liter of diisopropyl ether. Dropwise addition of 90 ml o~ a 2.85 molar solution of hydrogen chloride in diisopropyl ether, while stirring~ gives pale yellow crystals of the hydrochloride. After recrystallization ~rom acetone, there is obtained 51 g of colorless tert butyl- E2-methylphenyl) imidazol-1-yl-methyl~-sulfide hydro-chloride; m.p.: 16B-170C (compound no. 110).
After an aqueous solution of 25 g of sodium bicarbonate has been poured onto the hydrochloride, the free base is extracted with 3 x 200 ml of ether. After drying and concentration, it is obtained as a pale yellow oil (27 g), which gradually crystallizes m p 93-95C~
H-nmr (ÇO MHz, CDCl3)~ 3 (s, 9H), 2.4 (s, 3H), 6.25 (s~ ~H), 6.7-7.1 (m, 6H), 7.65 ppom (dd, lH).

'7 O.Z. 32,728 4-chlorophenyl-[4'-chlorophenyl)-imidazolyl-methyl]-sul~ide (compound no. 7) A mixture of 60.7 g of 4-chlorophenyl-(chloromethyl~4'-chloro-phenyO -sulfide, 27.2 g of imidazole and 55.4 g of potassium carbonate in 400 ml of acetone is refluxed for 5 hours while stirring. The mixture is then filteredg the ~iltrate is evaporated to dryness and 500 ml of water is added. This mixture is extracted 3 times with methylene chloride (200 ml each time). The combined extracts are dried over sodium sul~ate, The solution is concentrated to dryness in vacuo, and 26 g (38%)of colorless crystals (m.p.: 88C) are isolated, after trituration with diisopropyl ether.
lH-nmr (60 MHzs CDCl3): ~= 6.3 (s, lH), 6.9-7.4 (m, lOH), 7.5 (broad s, lH).

tert butyl-[(2,6-dichlorophenyl)-pyrazolylmethy~ -sulfide (compound no. 53) 66 g o~ triethylamine is dripped into a solution o~ 193 g of tert-butyl-(chloromethyl-(2,6-dichlorophenyl-sulfide and 44 g o~
pyrazole in 1 liter of toluene; upon completion of the slightly exothermic reaction, the mixture is refluxed for 1 hour. The undissolved constituents are filtered o~f, the filtrate is con-centrated, and 500 ml of water is added to the residue. After extraction 3 times with methylene chloride (200 ml each time), a solid residue is obtained upon concentration of the combined extracts which gives, after washing with diisopropyl ether, 117 g (57%) of colorless crystals; m.p.: g7-98c.
H-nmr (60 MHz, CDCl3): d - 1.4 ppm (s, 9H), 6.2 ("tr", lH), 7~0-7.3 (m, 3H), 7.4 ("d", lH), 8.2 ("d", 2H).

2,4-dichlorobenzyl-(1,2,4-triazolylmethyl)-sulfide (compound no~ 78)

3 A mixture of 60.4 g of chloromethyl-(2,4-dichlorobenzyl)-sulfide, Æ Of 1,2,ll-triazole and ~ ~ o~ po~/~ered potassiu~ carbonate ln ~ 9 _ '7 0.Z. 32,728 300 ml of anhydrous acetone is refluxed a' the boil for 10 hours.
The insoluble constituents are then filtered off, the filtrate is concentrated to dryness in vacuo, and 300 ml of water is added to the residue. The mixture is then extracted 3 times with methylene chloride (200 ml each time), and the combined extracts are dried and concentrated in vacuo. 39.8 g (58%) of colorless crys~als (m.p.: 68-70C) are obtained from the brown oil which remains, by crystallization from diisopropyl ethertmethanol at -60C.
lH-nmr (60 MHz, CDC13: ~'= 308 (S9 2H), 5.0 (s~ 2H), 7.0-7.5 10 (m, 3H), 7.9 (s, lH), 8.2 (s, lH).

2,4-dichlorobenæyl-(2',4' dichlorophenyl-1,2,4-triazol-1-yl-methyl)-sulfide (compound no. 61) and 2,4-dichlorobenzyl- [(2',4'-dichloro-phenyl-(1,2,4-triazol-4-yl)-methyl]-sulfide (compound no. 64) A mixture of 200 g of 2,4-dichlorobenzyl- L(2'34'-dichloro-phenyl)-chloromethyl~-sulfide3 145 g o~ 1,2,4-triazole and 138 g of powdered potassium carbonate in 2 liters of anhydrous acetone is refluxed, while stirring vigorously, for 9 hours. The solid con-stituents are then removed by filtration, the filtrate is then con-centrated to dryness in vacuo, and 500 ml of water is added to the 20 oily residue which is then extracted 5 times with methylene chloride (200 ml each time). The combined organic phases are dried over sodium sulfate and concentrated to dryness in vacuo. Upon trituration of the residue with diisopropyl ether there is obtained 157 ~ o~ color-less crystals containing the isomeric triazolyl compounds in a ratio of 8:2.
This mixture is extracted several times with hot hexane. The hexane solutions are combined and, after removal of the solvent in vacuo, there is obtained 122 g (65%) of 2,4-dichlorobenzyl- [(2'94'-di-chlorophenyl)-1,2,4-triazol-1 yl methyl~-sulfide in the form of 3~ colorless crystals; m.pO: 120-125C.

H-nmr (220 MHz, CDC13): ~ - 3.9 ppm (broad s, 2H), 6.65 (8, lH), 7.0-7.~ (m, ~H), ~.0 (s, 1H), R.~ (s~ lH).

O.Z. 323728 The colorless insoluble residue from the hexane extractions is 27 g (12%) of 2~4-dichlorobenzyl-C(2',4'-dichlorophenyl)~1~2,4-triazol 4-yl)-methyl~-sulfide; m.p.: 132-133C.
lH-nmr (220 MHz) CDCl3): ~- 3~9 ppm (s, 2H), 6.5 (s, lH), 7.0-7.5 (m, 6H), 8.45 (s, 2H).

tert-butyl-[(4-chlorophenyl)-1~2,4-triazol~1-yl-meth~Jl~ -sulfide (compound no. 30) While stirring, 350 ml of a molar solution of lg2,4-triazolyl sodium in dimethylformamide (DMF) (prepared from 0.35 mole of sodium hydride and 0.35 mole o~ 1,2,4-triazole in 350 ml of DMF) is dripped into a solu~ion of 78 g of tert-butyl-[(4~chlorophenyl)-chloro-methy~ -sulfide in 175 ml of dry DMF. Upon completion of the slightly exothermic reaction, the mixture is stirred for 4 hours at 80C. The batch is then poured into 1 liter of water and extracted 3 times with 200 ml of methylene chloride. The combined organic phases are washed with water, dried over sodium sulfate and concentrated in vacuo. When the residue is triturated with 150 ml of diisopropy~
ether~ there is obtained 40.0 g (46%) of colorless crystals;
m.p.: 95C.
H-nmr (60 MHzg CDCl3): ~= 1.3 ppm (s, 9H), 6.6 (s, lH), 7.2 (AA'BB', 4H)~ 8.o (S5 lH), 8.7 (S3 lH).

tert-butyl-((4-chlorophenyl)-1,2,l1-kriazolylmethyl)-sulfoxide (compound no. 31) While cooling with ice, a solutlon of 7.1 g of 85% strength 3-chloroperbenzoic acid in 70 ml of methylene chloride is dripped into a solution of 9.7 g of tert-butyl- ~(4-chlorophenyl)-1,2,4-tri-azolylmethyl~-sulfide in 20 ml of methylene chloride. The mixture is stirred for 2 hours at 0 C until there is no more sulfide (RF = 757) present according to the thin-layer chromatogram ;~ 30 (5io2, 7:3 mixture of methylene chloride and acetone), and only the 2 diastereoisomeric sulfoxides are distinguisha~le (RF - 0.38 7 o.z. 32,728 and 0.20). The solution is then washed with aqueous sodium bi-carbonate solution until no more C02 evolves. The organic phase is washed with water, dried and concentrated, and the solid residue is washed with a srnall amount of ether. There is obtained 7.0 g (67~) of colorless crystals, m.p.: 125-128C.
H-nmr (220 MHz, CDCl3): - 1.10 and 1.15 (two s, tog. 9H), 6.18 und 624 (two s~ tog. lH), 703-707) (m,4H), 8.01 and 8.07 (two s, tog.lH), 8.41 and 8051 (two s, tog.lH).

tert-butyl [(4-chlorophenyl)-1,2,4-triazolylmethyl]-sulfone (compound no. 32) At 20C, a solution of 7.~ g of 85% strength 3-chloroperbenzoic acid in 100 ml of methylene chloride is dripped into a solution of 10.7 g of tert-butyl-L(4-chlorophenyl)-1,2,4-triazolylmethyl~-sulfoxide in 50 ml of methylene chloride. According to thin-layer chromatography, the less polar sulfoxide oxidizes more quickly;
only after stirring for a fairly long time at room temperature does the more strongly polar sulfoxide oxidize. According to thin-layer chromatography (SiO2, 7:3 mixture of methylene chloride and acetone), the reaction is over after 18 hours. The sulfone (RF = o.46) is isolated by wash mg the solution with sodiurn bicarbonate solution and water, and drying and concentrating the organic phase. After the residue has been washed with diisopropyl etherg there is o~tained 8.7 g (77%) of colorless crystals; m.p.: 150C, lH-~nr ~220 MHz, CDCl3): ~- 1.3 ppm (s~ 9Hj, 6.75 (s, lH), 7.5 (AA'BB', 4H), 8.03 (s, lH), 8.84 (s~ lH).

4-chlorophenyl- ~4'-chlorophenyl)tetrazol 1-yl)-methyl~-sulfide and 4 chlorophenyl-[(4~--chlorophenyl)-(tetrazol-2-yl)-methyl~-sulfide (compound no. 15) ; At room temperature and while stirring~ }7.4 g of triethylarnine is dripped into a mixture of 26.1 g of tetrazole and 102 g of 4~chloro-~phenyl- L~ 4~-chlorophenyl)-chloromethyl~-sulfide in 3 5 liters of '7 O.Z. 32,728 toluene. The mixture is then refluxed for 4 hours. The insoluble material is filtered o~f, the filtrate is washed with water, and the organic phase is dried over sodium sulfate. After removal of the solvent in vacuo, a solid residue remains, from which, after the addition of 50 ml of diisopropyl ether, 74.7 g (67%) of yellowish crystals are isolated; m.p.: 104-106C.
H-nmr (60 ~z, CDCl3): ~- 6.7-7.6 ppm (m, 9H), 8.4 and 8.9 ~two s~ tog. 2H).
Examples of compounds Or formula I according to the invention are given in the following Table 1.

O. Z. 32,728 Table 1 Compound ) R1 R2 Az (salt j n R3 m p (C) N~ 0 ~ 13 2-13 4 ~N IR~ilm): .
2 H3C- H h~ 0 ~Cl 14,5 1ll920, ~131, 108a, 6667c~--~7 ' 3 ~ H ~ 0 -CH2~ ~OoO, ~020, 127 1, 1 190, 1131, 100~, -4 Cl~. H N ~ 0 ~ 98 Cl~ E~ N~N~ 1 ~ 151-139 ) 6 Cl~ H ~ ~ 2 ~ ~15 7 Cl~ H ~? 0 ~Cl 88 .:. 8 Cl~)~ > ,~COOE132 0 ~Cl 85-~7 9 Cl~ ~ ~ 0. ~Cl 62-6~1 10 Cl~ \~ 1 ~Cl il6-ll~) 11 Cl~- H N~ 2 ~Cl 147-150 12 Cl~ }} `I 4~'Cl 136-138 )Diastereoisomeric mixture of sulfoxides +~)The s'cructures of all the compounds l1sted have been confirmed by lH nlnr spectra~

~''; .

7 o.z. ~2,728 Compound Rl R2 Az (salt ) n R3 m.p . (C) 1~Cl~ ;`' 3J~ i ~Cl 147~) 14Cl~ }~ N~? 2 ~Cl 204 . . .

~5Cl~ H ~h N ~ ~ > Q ~Cl 104-106 . 16Cl~ ~ N ~ + N~ ~ 1 ~Cl 110-112+ 1 ) 17Cl~ N N~_~N ~ 2 --~--t:l 123-125 18Cl~ ~ ~_N ~CEI3 1JO

19Cl~ H QN 1 .~CH3 147-149~ ~) ,., 20Cl~ }~ N ~ 1 ~CH3 154-15 21C1~ ~ ~ ~l 2 ~C~3 245 22Cl~ ~ N ~ 0 ~Cl 102 :~ CI
23Cl~ X ~f~N~ 0 ~Cl 13~ 7 Cl ~ IRS~ilm):
24Cl~ ~ 0 te~ ~t.",l 2960, 1581, : 1096, 10~ 4, 7a73'6574~
; :
) mixture of tetrazole isomers ) diastereolsomeric mixture of sulfoxides ;~ +f ) more strongly polar sulfoxide, separated from the ;~ diastereoisomeric mixture no~ 19 by crystallization . - 15 -7 o.z. 32,728 Compound Rl R2 Az ( salt ) nR3 m.p . ( C ) Cl~ ~ N~ o ~OC~3 116 26. Cl ~ H ~ ~ 2 ~ OCH3 198 27 Cl ~ ~ - N -CH2 ~ Cl 57-58 N IR(~ilm):
28 Cl ~ ~ N ~ O e~hy~~ 2965, ?227~, , 1010,675cm ' 29 Cl ~ H N ~ 0 294485, 22508 1127, 1084~, 1~07,67Lcm ' Cl ~ ~ N~_~ O tert,-butyl 95 31 Cl ~ .. ~ N 1 tert.-~utyl 125-128l) 32 Cl ~ ~I~N~ 2 tert~- ~tyl 150 I~( film): ::
33 Cl ~ X ~ N~ O allyl 3054~ 11480, 1007, -1 672 C~
34 Br ~ H N~_? O tert. ~ butyl 77 ~78 F ~ H N ~ o tsrt.-~utyl 102-104 36 NC ~ ~ ~N~ O terk.-~utyl 73-75 37 2~ ~ H U~ O tert.- ~tyl 76-78 .
) diastereoisomeric mixture .,~
, . . .

- 16 - ~
. .

,i 7 O.Z. 32,728 Compound R1 R2 Az (salt ) n R3 m.p, ( C) 38 3 _~_ H N~NN~ tert .wb~tyl 94 39 H H , N~-> 0 ~Cl 47-49 <~ N N~ 0 ~ 9 ~
<~Cl N 1 ~) 70-88 4 2 (~ H U )~ 2 ~ 14 3 Cl N 0 tert.-~utg l 84 ~N 1 tert.-~utyl 154-157 ) . ~ 45 ~ H N ~ 2 tert.-butyl 126 ,CF3 IR t ~il~ ):
46 ~ ~? -CH24~ 127 11 ,. C~ 790, o2~.
3 660 c~n .

~ ~ . (COO~d)2 0 -Ca2~Cl ~33-135 48 Cl~ ~ N~ ;~ O -CH24~Cl 101 Cl~_ H ~3 2 -CH2~;1 1.95-19 î

) diastereoisomeric mixture ~ 17 -~7 o.z. 32~728 Compound R1 R2 Az (salt) n R3 m.p. (C) Cl~ H ~ N -C~2~Cl g2-~4 C~ 1 -CH2~C1 104 110 ) 52 Cl~ ~ 2 -CH2~1 100-105 ~ Cl ~. tert.-~utyl 97-98 ~, 54 ~ H N~ 0 tert.-butyl 110-112 Cl s 8- H ~ 0 tPrt.-buoy1 112-115 ; 56 ~ ~ N ~ 1 tert.-butyl 122-127 ) 57 ~ ~ ~ 2 t2rt.-~utyl 1~0-la3 .. 58 Cl ~ H N > 0 ~ Cl 128 59 Cl ~ H ~N N7 ~ Cl 148-150 . ~:

Cl ~ ~-N -CH2 ~ Cl 105 :~ ) diastereoisomeric mixture '. ' O.Z. 32,728 6~L'7 Compound Rl R2 Az (~alt) n R3 m.p. (C) 61 ~ ~N~ o -C~2~-C1 120 125 62 ~l- .N\~ CH2~C1 125-131+) 63 Cl~ E~ N~ 2 -CH2~C1 163-165 64 Cl~ H ~ 0 -CH2~Cl 132-133 Cl~ H N~;,~ 0 tert.-butyl 95-97 ` 67 C1~ X N~ 0 ~ - g5-97 ~ IR ~nlm) cm~1 :~ 6~ c~3 N ~ O ~> 1433~ 1250, 1~96, 1128, 994, 746, , . 689, 672 69 n hexyl H Nl~_ 0 ~ 29845, 2C20, 1471, 127G, ;' 1132, 1o~9, ~ - 67l~8cm8~8 n-butyl ~N~ ~ 2950, 2020, ~496, 1~72, - 1270, ~132, :~; ' 81889872s ~ ) diastereoisomeric mixture : -- 19 -O.Z. 32,728 '7 Compound R1 R2 Az (salt ) nR3 m.p. ( C) 71 n-butyl ~ N ~ 2n-Pe~tyl 69-71 . ~ N o~ Cl 76~79 72 H3C- H3C- N~
ilm):
\ ~N~ ~\ 2955, 1494, 73 ~-- . H N~ 1/ 0 ~ /-Cl 1471, 1279, ~ 1130, 1050, - . 1007, 8~5, 67} cm : Ih~film):
74 ethyl H N~ ~ O n-propyI 1495, 1270, 1192, 11~3, ~^ o753cmQ17' IR~ilm):
2955, 2925, ~:
n-butyl ~ N~_ ~ O n-~enty.l 1460, 1271, ~ ~ 1190, ~133, "~ , , 670708C~
, IR(fil~):
~: 76 n-Pen~yl H ~N~ 0 n- ~xyl 2860, 1~97, ~- 1012, 6?8 cm~
77 H ~N~ 0 -CH2 ~ r 46-49 78 H~ ~N~ o -CH2 ~ Cl 68-70 79 H- H. ~ ~ -OH2 ~ 60-63 ..

':

O . Z . 32 1 72 8 7 :~

2 ~ O
Compound R R Az n R m~ p . ( C ) ( salt ) ~ ~3 H .`f~ 0 ~C} 100-10 Cl 81 ~1 \~N 1 ter~.~butyl 1~5-116+) . C1 82 ~ H .`1~ ~ 2 tert.-b~tyl 154-165 :~ 8~ n-b~tyl ~ ~N~ 0 tert.~butyl IR(fil~)~
58, 1495, 145~, 13c4, 1272, 1190, 1158, 1134, 1010, 677 4 l-but~ O t~rt.-butyl I~
952, 28c2, .~ . 1494, 1457, : 1~6", 1270, ~: ~ 1189, 1157, . . 1132~ 6757 i-butyl ~ o ~Cl 45-4 6 i-hlt~l X .~ ~ 1 ~3Cl 110-1~2 87 i-butyl H ~ 2 ~C1 140-14 '' . :
:~

Com" Rl R2 A~ n R3 m.p. (C) pound ( salt ) 3 ' O tert.-but~l 98-101 ~ ~3 ' 0 tert~-but71 93-95 go3-heptyl H ~/> 0 ~ Cl (film) 1472, 126S, 1131, 1088, I008, 6873'C~-1 ; 91Cl ~ N~ 2 o 3-lnethyl- 2962, 148 , F 108S, 6 ." 92 ~ 0 ~ Cl 105-107 93~ - H ~N~ o tert,-~ut~l 106-108 94 ~ H ~ ~ 0 tert.~ yl 4C-43 ~"~ 95 ~ ~ 0 tert.-butyl 8S-87 96 ~ X N ~ ~ 0 tert~-bu~yl 1~0-112 -~

97~ - H ~ 0 tert.-~utyl ~-S5 Cl 98~ _ ~ o ethyl S9 Cl 9~~ ~ Q N 2 ethyl 102,-10 0, ~

~ L26~ -Z. 32,728 Com- Rl F~2 Az n R3 m,p. (C) : .
pound ( salt ) 100 ~ H ~ 0 n~ Ut'~ L~):
~_N 2958~ 2928, 14~4, ~274, : 1132~ 1008 . ~ ` C1 748~ 678 Cm ` 101 <~ H N~ 0 n-heXJ1 IRt~i1m):
. ~N 2955~ 2923, ~r `: 1491, 1271, C1 ~ ~ 744~ 675 C~
102 ~ H N~N~ ~C~2~ > 96-98 :~ C1 103 ~ L_~ 2~ 13O-133 ~:

104 <~ H N~?~ -CX~-CX2~ 58-6 105 ~ 2 -C~2-C~2~ 129-L3CI

, ~, 106 C l ~ ~ ,~ ,~-C 1 10 8- 110 . : 107 n X ~ o ~cl 84-87 ~: : Cl 108 H ~ 3C1152-155 Cl 109 H 'd \~N 2 ~C1 110 ~ ~ HCl 0 tert.-bu~l;yl 163-170 x ,~a dCl 0 n-.~u,,yl , 135-139 O.Z. 32,728 Com- R1 R2 Az n R3 m . p O ( C ) pound ( salt ) ., _. . ... . . ~ . .
Cl 112 ~ H ~,1t . HCl 0 -C~2-C.'12~ 145-155 113 F~ H 6N~ ~Cl 90-92 114 F~3 H N~N~ 0 ~Cl 119-120 Cl 115 ~_ X 6~? 0 ~Cl cg 71 Cl 115 ~ H 1~ ijr O ~Cl 134~ 130 ~Cl -:: 117 ~ H ~ 0 tert.-?3utyl I~(1il;~):
3098, Zg50, :
~463, 1211, . 115a, 1002, . Cl 104~, 739~ -1 118Cl~ ~ N'N~ 2 tert.-butyl 940 119Cl~ H 6~q 1~' 2 tert.-butyl 153-156.
;: F
' >
- ~ 120(~ :~N 2 tert.-but~l 143-145 : ~ Cf~ -121~,~~ H N~ 2 t~rt.-butyl 160-162 ~:

122(~ H ~N~ 2 t2r~.-3ltv~ ll;-llo Cl 123 ~ H N~ 2 ~Cl l-r5-1~8 1243^heptyl H ~ 0 ~ 1472, 1 468, 1160, ~090, 1009, 817, C%3 ~ 647 Cl;t ~
125C~3-C-C'd2- H N~? ~Cl 83 86 126CX3-C-C~2 ~ 3-C1 47- 51 127~~ ~N~ 0 _~ Cl 89 - 90 ~1 t 128Cl-(~ TN~ -C~2-<~-C1 3103 15a6, 1217, 1090, 1067, 1048, ~~ 24 -- ~59 a;r~

O~Z. 32,728 The new ~-azolyl sulfides 3 ~-azolyl sulfoxides and ~-azolyl sulfones and their salts have a much "ider spectrum o~
fungicidal action and are better tolerated by crop plants than the prior art compound 1-[2,4-dichlorophenyl-~-allylethyl ether]-imidazole. The new active ingredients may also be uEed in the i~ form of their salts, e.gO hydrochlorides~ oxalaltes and nitrates.
The fungicidal agents according to the invention are of considerable interest for combatting fungus diseases in various - crop plants, e.g., Ustilago scitaminea, Hemileia vastatrix, 10 Uromyces fabae or appendiculatus, Puccinia species, Erysiphe graminis, Botrytis cinerea in grapes and strawberries, Uncinula necator, Sphaerotheca fuliginea, Erysiphe cichoracearum and Podosphaera leucotricha.
; By "crop plants" we mean in this connection especially wheat, rye, barley, oats, rice, Indian corn~ apples, cucumbers, beans, coffee, sugarcane, grapes, strawberries and ornamentals in horti-culture.
The active ingredients have a systemic action, which is of particular interest in connection with the control of internal 20 plant diseases, e.g~, rust and mildew in cereals~
The agents according to the invention may suppress the growth of two or more of the abovementioned ~ungi at the same time, and are well tolerated by crop plants. The application rates necessary ~or combatting phytopathogenic fungi are from 0.05 to 2 kg of active ingredient per hectare.
The compounds of the invention can be converted into the con-ventional formulations, e~g. solutions, emulsions, suspensions, powders, pastes and granules. The formulations are prepared in the conventional manner, for example by diluting the active ingredient 30 with solvents and/or carriers, with or without the addition of emulsifiers and dispersants and, where water is used as the diluent, with or without an organic auxiliary solvent. Suitable O.Z. 32,728auxiliaries are, essentially, solvents, ~or example aromatics, e.g. xylene and benzene, chloroaromatics, e.g. chlorobenzene, paraffins~ e.g. petroleum fractions, alcohols, e.g. methanol and butanol, amines, e.g. ethanolamine and dimethylformamide, and water; carrlers, for example natural rock powders, e.g. kaolin, alumina, talc and chalk, and synthetic rock powders, e.g. highly disperse silica and silicates; emulsifiers, for example non-ionic -' and anionic emulsifiers, e.g. polyoxyethylene fatty alcohol ethers, alkylsul~onates and arylsulfonates, and dispersants, for example li~nin, sul~ite waste liquors and methylcellulose.
The formulations in general contain from 0.1 to 95 per cent .
by weight of active ingredient, preferably form 0.5 to 90 per cent. -~
The formulations, and the ready-to use prepara~ions obtained therefromg e.g. solutions, emulsions, suspensionsg powders, dusts, pastes or granules, are applied in the conventional manner, e.g by spraying, atomizing, dustinga cattering or watering.
The above-ready-to-use preparations may contain other active ingredients toge~her with those according to the invention, e.~.
herbicides, insecticides, growth regulators and other fungicides or may be mixed with ~ertilizers and applied together with these.
Examples of fungicides which can be combined with the compounds of the invention are: dithiocarbamates and their derivatives, e.g.
iron(III~ dimethyldithiocarbamate, zinc dimethyldithiocarbamate3 manganese N,N-ethylene-bis-dithiocarbamate, manganese zinc N,N-ethylenediamine-bis-dithiocarbamate, zinc N,N-ethylene-bis~di-thiocarhamate, tetramethylthiuram disulfide, the ammonia complex o~ zinc N,N-ethylene-bis-dithiocarbamate and N,Nl-polyethylene- bis (thiocarbamoyl)-disulfide, zinc N,N'-propylene-bis-dithiocarbamate, and the ammonia complex of zinc N,N'-propylene-bis dithiocarbamate and N-N'-polypropylenè-bis-(thiocarbamoyl)-disulfide; nitro deriv-atives, e.g. dinitro-(1 methylheptyl)-phenyl crotonate, 2-sec~--butyl~
4,6-dinitrophenyl 3,3-dimethylacrylate and 2-sec.~butyl-4,6-di-nitrophenyl isopropyl carbonate; heterocyclic compounds, e.g.

~126~7 0,Z. 32,728 N-trichloromethylthiotetrahydrophthalimide, N-trichloromethyl-thio-phthalimide, 2-heptadecyl-2-imidazoline acetate, 2,4-di-chloro-6-(o-chloroanilino)-s-triazine, 0,0-diethyl phthalimido-phosphonothioate, 5-amino-1-(bis-(dimethylamino)-phosphinyl)-3-phenyl-1,2,4-triazole, 5-ethoxy-3-trichloromethyl-1,2,4-thia-diazole, 2,3-dicyano-1,4-dithiaanthraquinone, 2-thio-1,3-dithio-~4,5-b)-quinoxaline, methyl 1-(butylcarbamOyl)-2-benzimidazole-carbamate, 2-methoxycarbonylamino-benzimidazole, 2-thiocyanato-. methylthio-benzthiazole, 4-(2-chlorophenylhydrazono)-3-methyl-S-isoxazolone, pyridine-2-thio-1-oxide, 8-hydroxyquinoline and its copper salts, 2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiine-4,4-dioxide, 293-dihydro-5-carboxanilido-6-methyl-1,4-oxathiine, 2-fur-2-yl-benzimidazole, piperazine-1,4-diyl-bis-(1-~2,2,2-tri-chloroethyl)-formamide), 2-thiazol-4-yl-benzimidazole, 5-butyl-2-dimethylamino-4-hydroxy-6-methyl-pyrimidine, bis-(p-chlorophenyl)-3-pyridinemethanol, 1,2-bis-(3-ethoxycarbonyl-2-thioureido)-benze~ne, 1,2-bis-(~-methoxycarbonyl-2-thioureido)-benzene and various fungicides, e.g. dodecylguanidine acetate, 3-(2-(3,5-dimethyl-2-hydroxycyclohexyl)-2-hydroxyethyl)-glutarimide 9 hexachlorobenzene, N-dichlorofluoromethylthio-N',N1-dimethyl-N-phenyl-sulfuric acid diamide, 2,5~methyl-furan 3-carboxylic acid anilide, 2,5-di-methylfuran-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-tridecyl-morpholine and its salts, 2,6-dimethyl-N-cyclododecyl-morpholine and its salts, 2~3-dichloro-l~4-n~hthoquinone~ 1,4-dichloro-2,5-di methoxybenzene, p-dimethylaminobenzene diazosodium sulfonate, 1-chloro-2-nitropropane, polychloronitrobenzenes such as penta-chloronitrobenzene, methyl isocyanate, fungicidal antibiotics such 3 as griseofulvin or kasugamycin, tetrafluorodichloroacetone, 1-phenyl-~thiosemicarbazide, Bordeaux mixture, nickel~containing compounds and sul~ur.

~ OOZ. 32,728 In the following experiments demonstrating the fungicidal action of the compounds according to the invention, the following prior art active ingredient was used for comparison purposes ,;
Cl ~ N~V,N-CH2'fH ~ Cl (A) ;` O-CH2-CH-CH2 (disclosed in German Laid~Open Application DOS 2,063,857) Action on barley mildew Leaves of pot-grown barley seedlings of the "Firlbecks Union"
. , `~' variety are sprayed with aqueous emulsi'ons'consisting of 80% (by ~ weight) of active ingredient and 20% of emulsifier, and dusted, after ;-- the sprayed~on layer has dried3 with spores of barley mildew (Rrysiphe graminis var. hordei). The plants are then placed in a greenhouse at 20 to 22 ~ and 75 to 80% relative humidity. The extent of mildew spread is determined after 10 days.
O - no attack~ graduated down to 5 = total attack Compound Leaf attack after spraying with liquor containing compound in amounts of 0.05% 0.025%

~2 0 2 ' ~ 25 0 2 -- 2~ -~' ;

O~Zr 32~728 Compound Leaf attack after spraying with liquor containing compound in amounts o~
0~05% 0~025%

~1 0 2 ` 50 0 3 0 3 ~`

; 125 126 ~ 0 Control (untréated) 5 - 29 o ~: ' , ' ' ' '.' :. ..

~ ,7 O.Z. 32,728 Action on wheat mildew In the same manner as in Example 14, lea~es of pot-grown wheat seedlings of the "Jubilar" variety are treated and infected with spores of wheat mildew (Erysiphe graminis var. tritici). The procedure is otherwise the same as in Example 14.

Compound Lea~ attack after spraying wi~h liquor containing compounds in amounts of 0.05% 0.02~%
:

: 85 0 0 92 - 0 . 0 ; 94 0 0 126 o 0 Control (untreated) 5 , ; . ~ 30 ~' ~ O.Z. 32,728 Action on leaf rust of wheat Leaves of pot~grown seedlings of the "Jubilar" variety are ; artiflcially infected~ 24 hours before being sprayed, with spores of leaf rust (Puccinia recondita). The pots are then placed in a high humidity chamber at from 20 to 22C. The plants are then sprayed with aqueous emulsionsS the solids comprising 80% of active ingredient and 20% of emulsifier. After the spray coating has dried~ the test plants are set up in a greenhouse at from 20 to 22C and from 75 to 80% relative humidity. After 10 days, the degree of development of the rust fungi on the leaves is determined.

10 Active ingredient Infection of the leaves after spraying with a ingredient liquor containing 0.05% of active ingredient 12 `

9~

11~ o Conkrol (untreated) 5 , .

/

O.Z. 32,728 90 parts by weight of compound 1 is mixed with 10 parts by weight of N-methyl-~-pyrrolidone. A mixture is obtained which is ~; suitable ~or application in the form of very fine drops.

20 parts by weight of compound 2 is dissolved in a mixture consisting of 80 parts by weight o~ xylene, 10 parts by weight of the adduct of 8 to 10 moles of ethylene oxide to 1 mole of oleic acid-N-monoethanolamide, 5 parts by weight of the calcium salt of dodecylbenzenesulfonic acid, and 5 parts by weight of the adduct of 40 moles of ethylene oxide to 1 mole of castor oil. By pouring the solution into 1003000 parts by weight of water and uni~ormly distributing i~ therein, an aqueous dispersion is obtained con-taining 0.02% by weight of the actlve ingredient.
EXAMPLE lg 20 parts by weight o~ compound 3 is dissolved in a mixture consisting o~ 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the adduct o~ 7 moles of ethylene oxide to 1 mole of isooctylphenol, and 10 parts by weight o~ the adduct o~ 40 moles o~ ethylene oxide to 1 mole of castor oil. By pouring the solution into 100~000 parts by weight of water and finely distributing it therein, an aqueous dispersion is obtai~ed containing 0.02% by weight o~ the active ingredient.

20 parts by weight of compound 1 is dissolved in a mixture consisting of 25 parts by weight of cyclohexanol~ 65 parts by weight of a mineral oil fraction having a boiling point between 210 and 280C, and 10 parts by weight of the adduct of 40 moles of ethylene oxide to 1 mole of castor oil. By pouring the solution int`o 100,000 parts by weight o~ water and uni~ormly distributing it therein, an aqueous dispersion is obtained containing 0.02% by weight of the active ingredient.

"

/

~ '7 O.Z. 32,728 20 parts by weight of compound 2 is well mixed with 3 parts by weight of the sodium salt of diisobutylnaphthalene-~-sulfonic ; acid, 17 parts by weight Or the sodium salt of a lignin-sulfonic acid obtained from a sulfite waste liquor, and 60 parts by weight of powdered silica gel, and trituraked in a hammer mill. By uni-~ormly distributing the mixture in 20,000 parts by weight of water~
a spray liquid is obtained containing 0.~% by weight of the active ingredient~

3 parts by weight of compound 3 is intimately mixed with 97 parts by weight of particulake kaolin. A dust is obtained con- '~
taining 3% by weight of the active ingredient.

30 parts by weighk of compound 4 is intimately mixed with a mixture consisting of 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil whlch has been sprayed onto the surface o~ this silica gel. A formulation of the active ingre-; dient is obtained having good adherence.

40 parts by weight of compound 1 is intimately mixed with 10 parts of the sodium salt of a phenolsul~onic acid-urea form-aldehyde condensate, 2 parts of silica gel and 48 parts of water.
A stable aqueous dispersîon is obtained. Dilution in 100,000 parts by weight of water gives an aqueous dispersion containing o.o4wt%
of active ingredient.

20 parts of compound 2 is intimately mixed with 2 parts of ,., the calcium salt o~ dodecylbenzenesulfonic acid, 8 parts of a fatty alcohol polyglycol ether, 2 parts of the sodium salt of a phenol-sulfonic acid-urea-formaldehyde condensate and 68 parts of a paraf-finic mineral oil. A stable oily dispersion is obtained.

,~;

Claims (4)

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. .alpha.-azolyl sulfides, and their derivatives consisting of .alpha.-azolyl sulfoxides and .alpha.-azolyl sulfones, of the formula ( I ), where R1 denotes hydrogen, alkyl, alkoxycarbonyl, or unsub-stituted aryl or aryl substituted by halogen, NO2, alkyl or haloalkyl; R2 denotes hydrogen or alkyl, R3 denotes alkyl, alkenyl, alkynyl, unsubstituted phenyl or phenyl substituted by alkoxy, alkyl or halogen, or unsubstituted aralkyl or aralkyl substituted by halogen, Az denotes imidazol-1-y1, pyrazol-1-yl, 1,2,4-triazol-1-y1, 1,2,4-triazol-4-y1, tetrazol-1-y1 or tetrazol-2-y1, and n denotes one of the integers 0,1 and 2, and their salts and metal complexes of copper, tin, zinc, manganese, iron, cobalt and nickel.

2. A process for combatting fungi, comprising treating the plants with an .alpha.-azolyl sulfide, or a derivative thereof consisting of .alpha.-azolyl sulfoxides and .alpha.-azolyl sulfones, of the formula (I), where R1 denotes hydrogen, alkyl, alkoxycarbonyl, or unsub-stituted aryl or aryl substituted by halogen, NO2, alkyl or haloalkyl; R2 denotes hydrogen or alkyl, R3 denotes alkyl, alkenyl, alkynyl, unsubstituted phenyl or phenyl substituted by alkoxy, alkyl or halogen, or unsubstituted aralkyl or aralkyl substituted by halogen, Az denotes 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 denotes one of the integers 0,1 and 2, and a salt thereof or a metal complex of copper, tin, zinc, manganese, iron, cobalt and nickel.

3. A process for producing an .alpha.-azolyl sulfide, or a derivative thereof, consisting of .alpha.-azolyl sul-foxides and .alpha.-azolyl sulfones, of the formula (I), where R1 denotes hydrogen, alkyl, alkoxycarbonyl, or unsub-stituted aryl or aryl substituted by halogen, NO2, alkyl or haloalkyl; R2 denotes hydrogen or alkyl, R3 denotes alkyl, alkenyl, alkynyl, unsubstituted phenyl or phenyl substituted by alkoxy, alkyl or halogen, or unsubstituted aralkyl or aralkyl substituted by halogen, Az denotes imidazol-1-yl, pyrazol-1-yl, 1,2,4-triazol-1-yl, 1,2,4-triazol-4-yl, tetra-zol-1-yl or tetrazol-2-yl, and n denotes one of the integers 0,1 and 2, and a salt thereof or a metal complex of copper, tin, zinc, manganese, iron, cobalt and nickel, wherein an .alpha.-chlorosulfide of the formula where R1, R2 and R3 have the above meanings, is reacted with an azole H-Az, where Az has the above meanings, in the presence or absence of a base and of a diluent, and the .alpha.-azolyl sul-fide thus obtained is if desired converted with an acid into a salt, with a metal salt into a metal complex, or with a suitable oxidant into an .alpha.-azolyl sulfoxide or .alpha.-azolyl sulfone.

4. An .alpha.-azolyl sulfide selected from the group consisting of tert-butyl-[(4-chlorophenyl)-1,2,4-triazol-l-methyl]-sulfide, 4-chlorophenyl- [(2-chlorophenyl)-1,2,4-triazol-1-y1-methyl]-sulfide, 4-chlorophenyl-[(2-chlorophenyl)-imidazol-1-y1-methyl]-sulfide, 4-chlorophenyl-[(4-fluorophenyl)-1,2,4-triazol-1-y1-methyl]-sulfide, 4-chlorophenyl-[(4-fluorophenyl)-imidazol-1-y1-methyl]-sulfide, 4-chlorophenyl-[(phenyl)-1,2,4-triazol-1-y1-methyl]-sulfide, 4-chlorophenyl-[(phenyl)-imidazol-1-y1-methyl]-sulfide 2-phenylethyl- [(2-chlorophenyl)-1,2,4-triazol-1-y1-methyl]-sulfide, tert-butyl-[3-trifluoromethylphenyl)-1,2,4-triazol-1-y1-methyl]-sulfide, 4-chlorophenyl-[2-fluorophenyl)1,2,4-triazol-1-y1-methyl]-sulfide, 4-chlorophenyl-[1-(1,2,4-triazol-1-y1)-2-ethylhexyl]-sulfide, 4-chlorophenyl-[1-(1,2,4-triazol-1-y1)-3-methylbutyl]-sulfide, 4-chlorophenyl-[1-(1,2,4-triazol-1-y1)-2-methylpropyl]-sulfide, 4-chlorophenyl-[(4-chlorophenyl)-imidazol-1-y1-methyl]-sulfide, tert-butyl-[(2,4-dichlorophenyl)3-1,2,4-triazol--1-yl-me-thyl]-sulfide, 4-chlorophenyl-[1-(1,2,4-triazol-1-yl)-3,3-dimethylbutyl]-sulfide, 4-chlorophenyl-[1-(imidazol-l-yl)-3,3-dimethylbutyl]-sulfide, tert-butyl-[(2-cyanophenyl)-1,2,4-triazol-1-yl-methyl]-sulfidc, tert-butyl-[(2-me-thylphenyl)-1,2,4-triazol-1-yl-methyl]-sulfide, tert-butyl- [l-(1,2,4-triazol-1-yl)-butyl]-sulfide, and tert-butyl- [1-(1,2,4-triazol-1-yl)-3-methylbutyl]-sulfide.