CS200238B2 - Fungicide - Google Patents

Abstract

Neue wertvolle α-Azolylsutfide und deren Salze und Metallkomplexe, die eine gute fungizide Wirkung haben sowie Mittel zur Bekämpfung von Pilzen, die diese Verbindungen enthal

Description

The present invention relates to a fungicidal composition comprising as active ingredient at least one of the novel alpha-azolyl sulfides and derivatives thereof, alpha-azolyl sulfoxides and alpha-azolyl sulfones, as well as their salts and metal complexes. The invention further relates to a process for the preparation of these novel compounds as well as to their use as fungicides.

It is already known that imidazole derivatives, for example 1- (2,4-dichlorophenyl-beta-allylethyl ether) imidazole (cf. DOS 2,063,857), exhibit good fungicidal activity. However, this effect is not always sufficient at low rates of application and concentrations.

In addition, the fungitoxic effect is often associated with phytotoxicity, so that damage to crop plants also occurs at the concentrations required to combat rust-like fungi. For these reasons, these substances are not always suitable for use as plant protection agents for combating fungi in all plant species.

It has now been found that the novel alpha-azolyl sulfides and their derivatives of formula (I)

And in which

R ¹ represents hydrogen, a straight or branched alkyl group having 1 to 7 carbon atoms, an alkylene group having 2 to 7 carbon atoms, an alkynyl group having 3 to 7 carbon atoms or an alkoxycarbonyl group having 2 to 7 carbon atoms or optionally 1 to 3 identical; different substituents from the group consisting of fluorine, chlorine, bromine, cyano, nitro, trifluoromethyl or C 1 -C 4 alkyl, substituted phenyl or naphthyl,

R is hydrogen or (C1-C4) -alkyl,

Rb is not directly ^b o branched alkyl slcu ^pi nu в ^1-6 and ^t om ^y u ^ magnesium, ^alk enyl group with 2-6 carbon atoms or alkynyl group having 3-6 carbon atoms or optionally one to three substituents selected a group consisting of fluorine, chlorine, bromine, trifluoromethyl, C 1 -C 4 alkyl or C 1 -C 4 alkoxy, substituted phenyl or benzyl;

Az means imidazol-1-yl, pyrazol-1-yl, 1,2,4-triazol-1-yl-, 1,2,4-triazol-4-yl-, tetrazol-1-yl or tetrazol-2- and a, n is 0, 1 or 2, and their salts and complex compounds with metals are well effective against harmful fungi, in particular from the class of Ascomycetes and Basidiomycetes.

^R1 is at ^{the example,} waters, ^and the methyl ^{ethyl, n-p} ro ^p y ^l ₁ isopropyl, ^n-butyl-l, n-pentyl, n-hexyl, 3-n-heptyl, methoxycarbonyl ', phenyl, 4-nitrofeinr ^1- (4-bromophenyl), 4-cyanophenyl, 2-methylphenyl, 4-tert-butylphenyl, 3-trifluoromethylphenyl, 4-trifluoromethylphenyl, 4-fluorophenyl, 2-chlorophenyl, 4-chlorophenyl, 2,4-dichlorophenyl, 2, 6-dichlorophenyl, 3,4-dichlorophenyl, naphthyl.

R is, for example, hydrogen, methyl and n-propyl.

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

Salts are, for example, hydrochlorides, bromides, sulfates, nitrates, phosphates, oxalates or dodecylbenzenesulfonates. Salt activity refers to a cation, so the choice of anion is free.

The metal complexes are compounds of formula II

X _k (II) wherein

R, R, R, Az. and n are as defined above and

Me means metal, for example, copper, zinc, tin, manganese, iron, cobalt or nickel,

X is an anion of an inorganic acid such as hydrochloric acid, sulfuric acid, phosphoric acid, hydrobromic acid, and mec is 1, 2, 3 or 4.

Particularly preferred are fungicidal compositions according to the invention which contain as the active ingredient alpha-azolyl sulfide selected from the group consisting of:.

tert-butyl - [(4-chlorophenyl) -1,2,4-triazol-1-ylmethyl] sulfidein,

4-chlorophenyl - [(2-chlorophenyl) -1,4,4-triazol-1-ylmethyl] sulfide,

4-chlorophenyl - [(2-chlorophenyl) imidazol-1-ylmethyl] sulfide,

4-chlorophenyl - [(4-fluorophenyl)] - 1,2,4-triazol-1-ylmethyl / sulfide,

3. 200238

4-chlorophenyl - [(4-fluorophenyl) imidazol-1-ylmethyl] sulfide, 4-chlorophenyl - [(phenyl) -1,2,4-triazole-methyl] sulfide, 4-chlorophenyl - [(phenylimidazole)] -1-ylmethyl / 8-sulfide,

2-Phenylethyl - [(2-chlorophenyl) -1,2,4-triazol-1-ylmethyl] sulfide, tert. butyl - / (3-trifluorrnetlhyLfeiny ^L) -1,2,4-triazol-l-ylmethyl / sulfide, 2-phenylethyl - / (2-cťLorfeiqrl) - '1 _t 2,4-triazol-1-ylmethyl / 8ulfidem, target. butyl - ((3-trifluoromethylphenyl) -1,2,4-triazol-1-ylmethyl) 8-sulfide, 4-chlorophenyl - [(2-fluorophenyl) -1,2,4-triazol-1-ylmethyl] 8-sulfide, 4-chlorophenyl- [1- (1,2,4-triazol-1-yl) -2-ethylhexyl] sulfide, 4-chlorophenyl- [1- (1,2,4-triazol-1-yl) -3- methylbutyl (8-sulfide), 4-chlorophenyl- [1- (1,2,4-triazol-1-yl) -2-methylpropyl] 8-fluoride, 4-chlorophenyl - [(4-chlorophenyl) imidazol-1-ylmethyl] 8i; 11-tert-butyl- [(2,4-dichlorophenyl) -1,2,4-trlazol-1-ylmethyl] 8-sulfide,

4-chlorophenyl- [1- (1,2,4-triazol-1-yl) -3,3-dimethylbutyl] 8-sulfide, 4-chlorophenyl- [1- (imidazol-1-yl) -3,3-dimethylbutyl] 8-sulfide, tert-butyl - [(2-cyanophenyl) -1,2,4-triazol-1-ylmethyl] sulfide, tert-butyl - [(2-methylphenyl) -1,2,4-triazol-1-ylmethyl] / 8ilLfidem.

It has further been found that the alpha-azolylaulfides of formula I (n = 0) 8e are obtained when the alpha-chloro-sulfides of formula III. '

I Cl in which

3

R ^1, R a · R have the above 8hora ', are reacted azoles of formula 8

H - Az in which

A is as defined above, optionally in the presence of a base and optionally in the presence of a diluent.

Oxidation of the thus obtained alpha-azolyl sulfides of formula I (n = 0) 8e 'yields the alpha-azolyl8 sulfoxides of formula I (h = 1) and alpha-azolyleulfones of formula I (n = 2).

In the preparation of the alpha-azolyleulfides of formula 1. (n = 0), it is useful to react the alpha-chlorosulfides of formula III without diluent or in the presence of a diluent of 8 and 8 with 0.5 to 2 equivalents of. 4 equivalents pří8lušného azole ^{p p} lean and ^DE for přídavku'0,5 to 4 eJkvLvalentů ^bá from ^{when t th} e ^p lo c ^h from the A8 ^{and 0-200} ° ^. The advantage <IN ^{of + 20 °, and + 160} ° ^C in a homogeneous or heterogeneous fázJL ^s.

As diluents 8e, for example, methanol, ethanol, isopropanol, n-butanol, diethyl ether, tetrahydrofuran, dioxane, acetone, acetonitrile, dimethylformamide, dimethyl sulfoxide, chloroform, methylene chloride or toluene may be used.

As the base 8e, for example, organic amines, such as triethylamine, pyridine or inorganic compounds, for example potassium carbonate or sodium hydroxide, can be used.

The alpha-chlorosulfides of formula III which are used as starting materials are partially known in the literature or can be prepared by methods known in the literature, for example: a) chlorination of sulfides with N-chlorosuccinimide (see for example BL Tuleen and TB Stephens, J. Org. Chem. 34, 31 (1969)) according to the scheme;

Cl

NH (III) or

b) reaction of the aldehydes with thiols in the presence of hydrogen chloride (see, for example, H. BOhme, H. Fischer and R. Frank, Liebigs Ann. Chem. £ 54, 1949 (1949) according to the scheme:

H

R ¹ - CO + HSR ³ + HCl - ►R ¹ - C - SR ³ + HgO.

Cl (III)

For the preparation of the alpha-azolyl sulfoxides of formula I (n-1), the alpha-azolyl sulfides are reacted, optionally in the presence of a diluent and about one equivalent of a suitable oxidizing agent, at temperatures between about -30 and + 100 ° C. Alpha-azolylsulfones. (formulas I, n 2) are obtained in a similar manner when oxidizing alpha-azolyl sulfides (I, n 0) with at least two equivalents of a suitable oxidizing agent or oxidizing alpha-azolyl sulfoxides (I, η = 1) with at least one equivalent of an oxidizing agent.

As oxidizing agents, for example, potassium permanganate, hydrogen peroxide or percarboxylic acids such as peracetic acid, perbenzoic acid or 3-chloroperbenzoic acid can be used.

Water, acetic acid, methanol, acetone, chloroform or methylene chloride can be used as diluents. A preferred method of preparing sulfoxides (I, n = 1) is by reacting sulfides (I, to 0) with one equivalent of 3-chloroperbenzoic acid in methylene chloride at a temperature of 0 to 25 ° C. The preferred method for producing the sulfone by reacting the sulfide (I, X = O) with two equivalents ⁱ va ^l ents ^{3-chloro p} erbenzoov KYSE ^é ^ ny in mettylencfcioridu ^{EXAMPLE l} ep ^t rev ^{of 15th} to ⁴¹ ° C.

Compounds of formula I (n = 0, 1, 2) are readily soluble in a number of organic solvents, for example, ethyl acetate, acetone, ethanol, methylene chloride, chloroform, dimethylsulfoxide, dimethylformamide and N-methylpyrrolidone, alpha-azolylsulfides (1 = 0). moreover, it is also soluble in toluene.

By treatment with acids, these compounds can be converted into their salts, for example, hydrochlorides, sulphates, nitrates, shlelates, formates, acetates or dodecylbenzene salts.

Furthermore, it has been found that the complexes and metals of formula II are obtained. if the alpha-azolyl sulfides or their derivatives of the formula I are reacted with the metal salts of the formula IV

Mef. and HgO (IV) wherein

Me, X and k are as defined above and a is 0, 1, 2, 3 and 4, in the presence of a solvent.

^In the present case, Me means metals I, II, and IV. to VIII. minor groups of the Periodic System of Elements, as well as metals of II. and IV ,. the main groups, but in particular have zinc, tin, manganese, iron, cobalt or nickel.

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

All solvents which are miscible and water are suitable for the production of metal complexes of the formula II. These include, preferably, methanol, ethanol, isopropanol, acetone, tetrabutylammonium ^dro furan or ^{dioxan. gloom} OM generally RAC ^{p p} e ^{p t} ru ^Lot ch between ⁰ and 1 ⁰ ° C, preferably between '10 and 35 ° C.

Sulfides (I, n = O) and sulfonyl (I, n = 2), each containing an asymmetric carbon atom, are thus formed as mixtures of enantiomers that can be separated into optically active compounds. In the case of the sulfoxides of the formula I (η = 1), due to the presence of an asymmetric sulfur atom adjacent to the asymmetric carbon, mixtures of diastereomers occur which can be separated in the usual manner, for example by crystallization or by chromatography into individual components. However, separation of enantiomers or diastereomers is not usually required for use as fungicides or as plant growth control agents.

Example 1

Terc.Butyi - / (2,4- ^d ichiorfenyl) -1,2,4-triazol-1-ylmethyl / sulfide "(compound no. 65)

To a solution of 22.1 g of 1,2,4-triazole in 500 ml of anhydrous acetone was added 60.5 g terc.butyi - / (2,4-dichlorophenyl) Chloromethyl / u sulphonic ^d. After adding 44.2 g of finely powdered of potassium carbonate, the mixture was heated to reflux with stirring for 7 hours. The mixture is then filtered to remove insolubles, the filtrate is concentrated to dryness in vacuo and 300 ml of water are added to the residue. The aqueous phase is extracted three times with 200 ml each. The combined extracts were washed with 200 ml of water, dried and concentrated in vacuo. After addition of 100 ml of diisopropyl ether, 35.6 g (53%) of colorless crystals of melting point 95 DEG-97 DEG C. are obtained from the residue.

^H-NMR sp ^e ktrum (100 1Uta, CDCl₃)

1.3 (s, 9H), 6.95 (s, 1H), 7.0-7.4 (m, 3H, ABX), 8.0 (s, 1H), 8.8 ppm (s, 1H ). Example. 2

Bis- / tert. ^butyl-l - ^{/ (2,} 4-dichlorophenyl ^e phenyl) ^{-1, 2,4-triazol-1-yl} ^ dZ etbyVsul ^ Cu ^ -cMorid

To a solution of 9.5 g t-butyl - / (2,4-dichlorophenyl) -1,2,4-triazol-1-yIaethyl / sulfo ^d u in

100 ml of ethanol was added dropwise 15 ml of 1 molar ethanolic sodium chloride dihydrate ^EI m nat ^é it. From this ^Y T ^E mofrtoo extended ^ ^k u ⁱ from ^l ^ U is two nnha at ^{ck at} '0 ° C, ^{9.8 g} of blue ^to RYSTA ^{and U,} which promývaj ^{te th} em yes ^l and ether pulse of ^{L t} and counting ^{to 130.} ° C.

Example 3

1-Pentyl- [1- (1,2,4-triazol-1-yl) pent-1-yl] sulfide (Compound No. 75)

A solution of 43.5 g of triazole in 200 ml of dimethylformamide was added dropwise with stirring to a suspension of 13.0 g of sodium hydride in 100 ml of dimethylformamide. When the evolution - hydrogen was added dropwise to the mixture cooled to room temperature, 97.0 g of 1-pentyl / chiorpent 1-1-yl / the sulfide while a mixture ^of a heated. Otom ^P is CH ^and m ^s is the ^ETE hofón ^{8 at 80} ° C.

The reaction mixture is then concentrated in vacuo, water (500 ml) is added and the reaction is carried out. with 5x methylene chloride extraction. The combined and concentrated extracts are chromatographed on silica gel (5 x 70 cm) first using methylene chloride as the solvent system. After the first brownish zone, acetone (up to 1% acetone) is slowly increasing. ^J as the second zone is recovered and 15.0 grams of product as a light yellow oil.

IR (Film): 2955, ⁹² 5 ^'86 ° ² 1 ⁹ 4 6 1 46 °, 1 271, 1 1 ^ ^1133, 1008, 677 aa' ^1. ''H-NMR spektruia (270 MHz, CDCl ^{j) 0} 0 ^(tr, 6H), 1.3 (nu 8H), ^1, 5 U, 2H), 2.1 (s, 2H);

2.4 (m, 2H), 5.4 (tr, 1H), 8.0 (s, 1H), 8.4 ppm (s, 1H).

Example 4

1-Pentyl- [1- (1,2,4-triatol-1-yl) piperidin-1-yl] sulfone (compound δ. 71)

To a solution of 10.0 g of 85% 3-chloroperbenzoic acid in 140 ml of methyl chloride, while stirring and under ice-cooling, a solution of 6.0 g of 1-pentyl- [1- (1,2,4-triazol-1-yl) pent] was added dropwise. -1-yl / sulfide. After unwinding the initial heat discoloration, the reaction mixture was stirred for 2 days at ² 5 ° ^{C. MES} is then promývéi solution at ^hličit ane solution of ^{the extensible} em sodntoo Na sulfite and water phases aOrganická · dried. After concentration left a pale yellow oil from which at roztíráš s diieo ^p ro ^py ^ repent ether of 3.5 ^g without arvých ^{b k} r ^y hundred ^profiles for heartbeat! ^I Subtraction of ^{69 s} and ^{from 71} ° ^C.

Nuclear Magnetic Resonance Spectrum (CDCl3, 100 MHz) δ = 0.9 (m, 6H), 1.4 (m, 8H), 1.8 (m, 2H), 2.5 (m, 2H), 2.8 (dd, 2H), 5.4 (dd, lift β &gt; 1 (s, 1H), 8.5 ppm (s, 1H).

Example 5

Tert -Butyl- (2-methylphenyl) imidazol-1-ylmethyl) sulfide (Compound No. 89)

To a solution of 43.6 g of imidazole in 300 ml of acetone was added dropwise with stirring 82 g of tert-butyl - ((2-methylphenylchloromethyl) methyl). After the addition of 88 g of finely divided carbonate The insoluble material is filtered off and the filtrate is concentrated, 300 ml of water are added to the residue, and extraction is carried out 3 times with 200 ml of methylene chloride each time, and the combined organic phases are washed with water, dried and dried. concentrating 69 g of a brownish oil which was dissolved in 1 liter of diisopropyl ether. By dropping 90 ml of a 2.85 molar solution of hydrogen chloride in diisopropyl ether with stirring, pale yellow hydrochloride crystals precipitated from this solution which were recrystallized from acetone. g of colorless tert-butyl - [(2-methylfelnyl) imidazol-1-ylmethyl] sulfide hydrochloride, m.p. 168-170 [deg.] C. (compound 8. 110).

After the hydrochloride is poured into an aqueous solution of 25 g of sodium hydrogen carbonate, the free base is extracted 3 times with ether. After drying and concentration, the precipitated pale yellow oil (27 g) which slowly Cr ^y hundred ^l U is (te ^pl OTA t ^ck 93 and ⁹⁵ ° ^C).

@ 1 H-NMR (60 MHz, CDCl3): .delta. = 1.3 (a, 9Hb 2.4 (a, 3H), 6.25 (s, 1H), 6.7-7.1 ( ia, 6H), 7.65 ppm (dd, 1H).

Example 6

4-chlorophenyl- / t 4 * -chlαrfonyl) lmtdezolylmethyl / eulfI ^d (compound no. 7)

Mixture 60.7 3; Chlorophenyl / chloromethyl-N, N-chlorophenyl / sulfide, 27.2 g of imidazole and 55.4 g of potassium carbonate in 400 ml of acetone are heated under reflux for 5 hours. After the mixture was filtered, the filtrate was concentrated to dryness and water (500 ml) was added. This mixture was extracted three times with 200 l of methylene chloride each time. Combined extract? dried over sodium sulfate. From flowable foolhardy in vacuo after trituration with dV »^ .eopropyl3.U RelA isolated 26 g ⁽³⁸ £) Cr ^{y b} ezbarvých St.AM ^profiles of ^the temperature ^{t of} th ^e 88 ° ^C.

'H-NMR spektrurn (6 ⁰ MHz CIX31 ^j) <6.3 · (s, IH), 6.9 to 7.4 (m, 1 ⁰ H), 7.5 (broad s, 1H ).

Example 7

Tert -Butyl - (2,6-dichlorophenyl) pyrazolylimethyl / sulfide (Compound No. 53)

To a solution of 193 g of tert-butyl / chloromethyl- _(2> 6-dicfcú.offeiyrl) / 8ulfidu and 44 g of pyrazole ... in 1 liter of toluene is added dropwise 66 g of triethylamine and the mixture was heated subsided slightly exothermic reaction for 1 hour to reflux. The insolubles were filtered off, the filtrate was concentrated and the residue was concentrated. add 500 ml of water. Extraction three times with 200 ml of methylene chloride gave a solid residue upon concentration of the combined extracts. After washing with diisopropyl ether, 117 (57%) of colorless crystals were obtained, mp 97-98 ° C.

^@ 1 H-NMR spectrum (60 MHz, CDCl3): .delta.4.1.4 ppm (a, 9H), 6.2 (tr, 1H), 7.0-7.3 (m, 3H), 7, Δ (d, 1H), 8.2 (d, 2H).

Příklaae

2,4-Dichlorobenzyl- (1,2,4-triazolyl-eth-1) sulfide (compound S. 78)

A mixture of 60.4 g of chloromethyl- (2,4-dichlorobenzyl) sulfide, 35 g of 1,2,4-triazole and 69 g of sprayed potassium carbonate was heated to reflux in 300 l of anhydrous acetone for 10 hours. The insolubles were then filtered off, the filtrate was concentrated to dryness in vacuo and 300 ml of water were added to the residue. It is extracted three times with 200 ml of methylene chloride each time, the combined extracts are dried and concentrated in vacuo. Of the remaining brown oil was crystallized from a mixture of methanol and diiaopropylatharu at -60 ° C gave 39.8 g (58%) of colorless crystals ^of te ^pl ol mp 68-7 ° C.

K-NME spectrum (60 MHz, CDCl3):? 3.8 (s, 2H) 5.0 (s, 2H), 7.0-75 (m, 3H), 7.9 (s, 1H) ,

8.2 (s, 1 H).

Example 9

(4-Dichlorobenzyl-C2 *, 4 * 10 &lt; 10 &gt;, 8 ' (1,1,2,4-triazol-1-ylmethyl) sulfide). (Compound no. 61) and 2,4-dichlorbanzyl- / 2 *, 4 * -dichlorfany ^ - _(1.2> 4-triazol-4-yl) me.Uh ^ '/ ^u and lfid (compound no. 64 '

A mixture of 200 g of 2,4-dichlorobenzyl- [(2 ', 4'-dichlorophenyl) chloromethyl] sulfide. 145 g of 1,2,4-triazole and 138 g of sputtered potassium carbonate in 2 liters of anhydrous acetone are heated under reflux for 9 hours with vigorous stirring. The solids are then removed by filtration, the filtrate is concentrated to dryness in vacuo and the oily residue is extracted 5 times with 200 ml of methylene chloride each time after addition of 500 ml of water. The combined organic phases are dried over sodium sulphate and then concentrated to dryness in vacuo. On trituration of the residue with diamethyletheram, 157 g of colorless crystals are obtained which contain isomeric triazolyl derivatives in a ratio of 8: 2.

This mixture was extracted several times with hot hexane. From the combined hexane solutions, 122 g of (65 2,4-dichlorobenzyl-X2 ', 4 ° -dichlorophenyl; -1,2,4-trinzol-1-ylmethyl) sulfide were obtained as colorless crystals by distilling off the solvent in vacuo. mp 120-125 ° C.

XřMR-.íioíiktrum (220 MHz, "CDCl J <- ^3, 9 PP® (Wide 4 .65 1HL 6 _R ^7, C-7.5

8.0 (s, 1H), 8.6 (s, 1H). '.

Colorless insoluble residue after extraction with hexane consists of 27 g (12 D'Rhlo 2,4-benz-l- ^{y / (2 *,} 4 * ~ · dich orffcвн ^l <V ^ - ⁽² 2 ⁴ 1 -t i ^{r d} «oll4 ^{- lL} Jactz y ^l l / 8 ^{fif. i} .t ⁱ of point ^{3 32 133} ° C.

8 200 238 H-NMH-spektruB (220 MHS, CDCl₃) ^/ «3.9 ^ppm (в, ^2H), 6. 5 (s, 1H). 7.0-7.5 (a, 6H); 8.45 (a, 2H). ·

Example 10

Tert -Butyl- (4-chlorophenyl) -1,4,4-triazol-1-yl-ethyl sulfide (Compound No. 30)

To a solution of 78 g of tert-butyl - (4-chlorophenyl) n-methylmethylsulfide in 175 ml of absolute dimethylformamide (DMF) is added dropwise, with stirring, 350 µl of a 1 molar solution of 1,2,4-triazolylnatrium in dimethylformamide (prepared from 0). , 35 mol of sodium hydride and 0.35 mol of 1,2,4-triazole in 350 ml of dimethylformamide). After a slightly exothermic reaction subsided, the mixture was stirred at 80 ° C for 4 hours. The mixture was then poured into 1 L of water and extracted with 3 x 200 mL of methylene chloride. The combined organic phases are washed with water, dried over sodium sulphate and evaporated in vacuo. The residue, when triturated with 150 ml of diisopropyl ether, forms 40.0 g (46%) of colorless crystals, m.p. 95 ° C.

¹ H-NMR ^spe kt ^ ^m (MH ^ 60 ^ h CDCl 1.3 ^pp m (s, 9H ^ 6.6 ^(s, 1H), 7.2 (Αα'ββ '4HH 8.0 (s 1 H, 8.7 (s, 1 H).

They did

Tert-Bityl - / (4-chlorophenyl) -1,2 _> 4-triazolyll-ethyl / βilfoxide (Compound No. 31)

To a solution of 9.7 g of tert-butyl [(4-chloro-phenyl) -1,2,4-triazolylmethyl] sulfide in 20 ml of methylene chloride was added dropwise a 7.1 solution under ice-cooling. g 85% 3-chloroperbenzoic acid in 70 m^l methylene chloride.^WITHThe mixture is stirred for a while^E 2^hO^diny^{at 0} °^C up to^dle chromato There is no sulphide present (Rf = 0.57) and only both diastereomeric sulphoxides (Rf = 0.38 and 0.20) are detectable. This solution is then washed until the evolution of CO 2 with an aqueous solution of sodium bicarbonate is complete. After washing the organic phase with water, the organic phase is dried, concentrated and the solid residue is washed with a small amount of ether. 7.0 g (67%) of colorless crystals of melting point 125 DEG-128 DEG C. are obtained.

^ ¹ HN S ^p e ^kt rum ⁽²²⁰ MHz, СГИЗИ ^) ^'1.10 and ^{1 1} 5 (two s, p e ^C No ^{PL H} 9 b ^{6, 18} and ^{6.24 (d} VA. together 1H) 7.3-7.7 (m, 4H), 8.01 and 8.07 (two s, together 1H), 8.41 and 8.51 (two s, together 1H).

Example 12

Tert-Bityl - / (4-chlorophenyl) -1,2,4-triazolylmethyl) 8ilfone (Compound No. 32)

To a solution of 10.7 g of tert-bityl - [(4-chlorophenyl) -1,2 ^{* *} , 4-triazolylmethyl] silfoxide in 50 ml of methylene chloride was added dropwise a solution of 7.3 g of 85% 3-chloroperbenzic acid in 20 ml.

100 ml methylene chloride. According to the result of thin layer chromatography, the less polar sulfoxide is oxidized more rapidly; only a longer stirring at room temperature oxidises the strongly polar sulfoxide. After 18 hours, the reaction was complete according to thin layer chromatography (SiO 2, methylene chloride / acetone 7: 3). The sulfone (Rf = 0.46) is isolated by washing the solution with sodium bicarbonate solution and water, drying and concentrating the organic phase. After washing the residue with diisopropyl ether, 8.7 g (77%) of colorless crystals of melting point 150 DEG C. are obtained.

'HN ^ ^- e ^ ^{u pe} KTR (220 MHA CDCl₃) ^/ = 1.3 ^ppm (s, 9H), 6.75 U, 1H), 7.5 (AA * BB', 44 ^

8.03 (s, 1 H), 8.84 (s, 1 H).

Example 13

4-Chlorophenyl - [(4'-chlorophenyl) - (tetrazol-1-yl) ethyl] sulfide and 4-chlorophenyl - [(4'-chlorophenyl) 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 was added dropwise at room temperature 37.4 g of triethylamine with stirring. The mixture was then heated at reflux for 4 hours. The insolubles were filtered off, the filtrate was washed with water and the organic phase was dried over sodium sulfate. After evaporation of the solvent in vacuo left a solid residue which, after addition of 50 ml of diisopropyl ether recovered 74.7 ^{g (6} 7 $ 9 ^ylw utavýc ^hk r ^y hundred ^profiles of ^t ep ^l ot point ^{of 10 4-106} ° C.

'н-NMR (60 MH ^z, CDCl ^) = 6.7-7.6 ppm (пц W, ^8, 4 and 8.9 ^{(two and s,} together 2H).

Examples of compounds of the invention of formula I 'are given in Table 1 below:

Compound ’ r ' R2 Az ⁽ salt) 1 1 H ° \  Ό O HjC- H 1 AND 2 w

r3

T. t.

(° C)

- @ - ^a

132 to 134

IR spectrum (film); 1

470,

495, 1. 270, 1 192, 131, 1 - 007, ⁶⁶⁶ cm-1

088, .817,

O- © -

^c, X0 &gt;.

c <O> -

^-Ch 2 ^- ^ O ⁾

IR spectrum (film)

3,060, 3 020 1 492 1 450 1 271, 1 190 1 131, 1 008: 695, 677 ' 658 cm ' -1

_- <2> 98

^And 131 M ^{+ L39)}

- (o) 215

- / Q ^ CI 88

- @> c.

to 87

to 64

Compound * · * ⁰ R ¹ R ² Az (salt) 1 n R ³ Mp (° C) 10 H O 1 4 ° λ ' 116 to 18 ⁺⁾ 11 H O 2 42> ^c ' 147 to 150 12 H AND in) 0 - <č> ^cl 136 to 138

The diastereomeric mixture of sulfoxides the structure of all the compounds was confirmed by 1 H-NMR-spectra

Merge- R ¹ R ² Az (salt) n R ³ T. t. (° C) nina 13 H ά 1 147 ⁺⁾ 14 0./5)- H O 2 4D- ^c ' 204 15 Dec H 0 * O 0 104 to 106 16 H 1 1 +) / ^N \ / ^N \ O ⁺ n> NN 1 - <2> ^CI 110 up to 112 ⁺⁺⁾ 17 H А A ”  in) 2 Χθ> <= ' 123 to 125 mixture tetrazole isomers ⁺⁺ ) diastereomeric mixture and sulfoxides Compound R ¹ ' R ² Az (salt) n R ³ T. t . (° C) 1Θ H | й 0 h (o> ch ₃ 130 19 Dec ^c, <°> H O 1 Ηθ / εΗ ₃ 147 up to 149 ⁺⁺⁾ 20 May Cl Yo) - H 1 ~ ^ O ^ ~ ch ₃ 154 up to 155 ⁺⁺⁺⁾

Compound R ^{1 r2} Az ⁽ 8Ů1 ⁾ n _R 3 Mp (° C) 21 ^C 'X °> - 1 / ^N \ ^H 2 - <o) -ch ₃ 245

⁺⁺⁾ diastereomeric mixture of sulfoxides +++) stronger · polar sulfoxide, separated by crystallization from mixture of diastereomers C. 19

COMPOUND ¹ nina

Cl - (&

R ² Az (salt)

R ³ T. m.p. (° C)

Cl

Cl

102 °

135-137 t-butyl IR (film):

2 950. 1 581 1 460, · 1 362, 1 211 », · 1 152, 1 096, 1 064, 1 043, 844, 787, 675 cm

25 ^or X °> H From ^N \ N from> in / 26 H O 27 Mar: ^cl <2> H ά 28 H O 29 ^and X 0> H 1 / N \ V_ií

116

198 to 58

0 ethyl IR (film) 2 · 965, 2 925, 1 490, 1 271, 1 131, 1 088, ¹ 010, 675 ^{cm -1} 0 n-butyl IR spectrum (film) 2,945, 2,920, 1,486, 1,268, 1,127, 1,084, ^{1,671 cm_1} 0 tert-butyl 95

200238 Compound R ¹ R ² Az (salt) 1 31 e, ^ O> - H O 32 e, £ 4> - H ό 33 H ά 34 H ά

12 η 1 R ³ tert -butyl Mp (° C) 125 to 128 * ^} 2 tert.butyl 150 0 allyl IR (film) 3054, 1489, 1 403, 1270, 1130, 1080, 1,007, 672 cm &^lt; -1 & gt ^; 0 tert.butyl 77 to 78

a mixture of diastereomers

Compound R ¹ R ² Az (salt) AND η R ³ Mp (° C) 35 H From ^N \ v> 0 tert-butyl 102 to 104 36 ^NCH © ^_ H 1 C) 0 tert.butyl 73 to 75 37 ° ₂ n / 5 / - H O 0 tert-butyl 76 to 78 38 <f ^H 3 - / ^{CH 3} tA H 1 From ^N \ Ό 0 tert.butyl 94 39 H Cl H ж O 0 / θ / с. 47 to 49 40 AND H AND 0 XD 91 41 Cl <θ5 H ά 1 70 to 88 ⁺⁾ 42 H ά 2 143 43 AND H ά 0 tert.butyl 84

mix of diastereomers ´ З 200238

Merge- R ¹ R ² Az (salt) nina Cl | 44 H ^{/ N} \ V-ií Cl 1 45 H Q 46 ^CF 3 H O

n R ³ Mp (° C) 1 tert-butyl 154 to 157 * ⁾ 2 tert-butyl 126 CF / ³ 0 -CH ₂ - IR spectrum (film) 1,445, 1,323, 1,270, 1,160, 1,115, 1,070, 790, 695, 660 cm @ -1

+) mixture of diaatereomers

Combination R ¹ nina

Cl

Cl

mixture of diastereomers

R ³ T. m.p. (° G)

133 to 135

101

195 to 197 to 84

104-110

100 to 105 tert-butyl tert-butyl to 98

110 to 112

tert-butyl diastereomers

AND

OF*\

V> o

R ¹ R ² Az (salt) η я ³ τ "AND H O N ~ N 0 - <2> - " Cl ^, 4o H AND 0 "AND H AND w 0 CI- _{2 2} - ^ О О -р1 Cl ^Cl H AND V> 1 Cl ₂ --CH 2 --O 4 -ci Cl ci- ^ Q ^ - AND Q 2 Cl- ^{CH2- (} O) -Cl

. t (° C)

112 to 115

122-127 ⁺⁾

180 to 183

128 t (° C)

148 to 150

105

120 to 125

125 to 131 ⁺⁾

163-165 ⁺ ) a mixture of diastereomers

MergeR ²

Az (salt)

R ¹

Cl

n-hexyl n-butyl H

T n

R ³

t (° C)

I / N \ whose in N — N O —Ch ₂ ? O? 132 to 133 | 0 1 0 tert-butyl 95 to 97 From ^N \ Q 0 -CH ^ 66 to 88 1 Z ^N \ ^ -N 0 95 to 97 O O ΐδ-spectrum (film): 2,950, 1,748, 1,494. 1,433, 1,260, 1,196: 1,138, 994, 746 ' 698,672

^{/ N} \ n-butyl H

H-C- H ₃ c- of ^N \ o ά_. _ν 1 > - H G AT

ethyl

ΐδ-spectrum (film):

2 945, 2 920 2 850, 1 496 1 471, 1 270 1 132, 1 089. 1 008, 1 818. 674 cm “

ΐδ-spectrum (film)

950, 2,920,

496, 1,472,

270, 1 132,

089 i 008

818, 672 cm ^-1 n-pentyl to 71

up to 79 ΐδ spectrum (film):

955, 1 · 494

471, 1 279, · 130, 1 050,

007, 815

673 cm ¹

/ ⁿ \ N 0

n-propyl δ-spectrum (film):

2 960, 2 925, 1 495, 1 270, 1 192, 1 133, 1 003, 817, 675 cm ’ -1

n-pentyl n-butyl

R ² Az (remaining) n

n-pentyl

Mp (° C)

IR spectrum (film):

955, 2 925,

860, 1,496,

460, 1,271,

1. 190, 1 133 »

008,

677 cm ^-1 n-hexyl IR (film):

2 955, 2 925 2 860, 1 497 1 460, 1 272 1 192, 1 135 1 012 • 1 678 cm '

HHH-

Cl

Cl Cl

n-butyl

H

H H H

H

H

H

O 0 1 / ^N \ o I 0 1 o I - 0 1 / ^N \ I O ^{/ N} \ Ό I 1 / ^N \ 2 ό O

tert-butyl tert-butyl to 49 to 70 to 63

100 to 103

115 ^and 116 ⁺ f>

164-165 i-butyl i-butyl

^{/ N} \ O 0 1 / ^N \ 0 O

tert-butyl I

1! -Spectrum (film):

958, 1 495, 459, 1 364, 272, 1 190, 158, 1 134, _ 010, 677 cm

tert-butyl

ič-spectrum (film):

952,

494,

364,

189,

132,

862, 457, 270, 157

007, 675

to 46

Compound R ¹ R ² As (salt) 1 86 ' i-butyl H Ό 87 i-butyl H | C ^H 3 88 (o / ^X \ ^H o ^ -N 1 СИ ₃ 89 H <> AND 90 3-heptyl H ^{/ N} \

17 200238 Mp (° C) n r3 1 110 to 112 2 - (δ} - α 140 to 141 0 tert.butyl 98 to 101 0 tert-butyl 93 to 95 0 - <O> -Cl IR spectrum (film): 4 2,924, 2,922, 1,472, 1,269, 1,131, 1,088, 1,008, 819,. 673 cm ¹

3-methylbutyl

H O v_ _N 0 41Χ ^α H 1 / ^N \ u 0 tert-butyl H O 0 tert-butyl H 1 of ^N \ o | 0 tert-butyl  G 1 0 tert-butyl H ^{/ N} \ I 0 tert-butyl H 1 / ^N \ O 0 ethyl H 1 / ^N \ o X- N 2 ethyl

IR spectrum (film):

962 1489

271 1130

088, 1 012.

105 to 107

106 to 108 to 43 to 87

110 to 112 to 95 to 61

103 to 104

Mp (° C)

IR-spectrum (film):

δ-spectrum (film): 2,956, 2,926, 1,494, 1,274,

132, 1008, 746, 678 cm @ 3 n-hexyl

-сн ₂ —сн ₂ - —CH-CH3—

CH2 — CH2— (δ)

955, 2 923, 491, 1 271, 129, 1 007, 744, 675 < 96 to 96 130 to 133 56 to 61

cm ^-1

Compound

113

114

115

116

117

118

119

120

121

122

123

124

125

/ ^N \ ^ -N 2 O 2 O 2 1 Z ^N \ 2 N) AND 0 2 1 / ^N \ 2 W 1 0 С У N-N

R ³ T. m.p. (° C)

to 92

119 to 120 to 71

134 to 136 tert-butyl tert-butyl tert-butyl tert-butyl tert-butyl tert-butyl δ-spectrum (film):

940 γ ^η 3 СН.-С-СНл, ³ OH ₃ ²

153 to 156

143 to 145

160 to 162

113 to 116

155 to 158 ΐδ spectrum (film)

956, 2 922,

472, 1 468,

168, 1,090,

009, 817.4

674 cm ^-1 to 86

200238 Compound R ¹ R ² Az (salt) 126 CHj CH2-C-CH3 CHj H ά 127 (O)- H ά 128 Cl H ά

η R ³ Mp (° C) 0 ^d - ^г · ' 47 to 51 0 89 to 90 0 -CH ₂ - © —C. IR (film) 3,103, 1,586, 1,468, 1,378, 1,217, 1,090, 1,067, 1,048, 1,012, 825,. ⁶ 59'cm ¹

The novel alpha-azolyleulficides, alpha-atolylaulfoxides and alpha-azolylsulfones and their salts show a considerable broad fungicidal effect and are better tolerated by plants than the known 1- (2,4-dichlorophenyl-beta-allylethyl ether) imidazole. The novel active compounds can also be used in the form of their salts, for example hydro-chlorides, slavelanes or nitrates.

Of great importance are fungicidal compositions according to the invention in fungal diseases on various crop plants, for example:

Ustilago scitaminea,

Hemileia vastetrix, Uromyces fabae or appendiculatus, Puccinia species, powdery mildew (Erysiphe graminis), mold (Botrytis cinerea) on vines, strawberry plants,

Uncinula necator,

Sphaerotheca fuliginea,.

Erysiphe cichoracearum, Podospehaera leucotricha. *

In this context, crop plants include, in particular, wheat, rye, barley, oats, rice, maize, apple, cucumber, beans, coffee, sugarcane, grapevine, strawberry plants and ornamental horticultural plants.

The active compounds according to the invention are active systemically. The systemic effectiveness of these compositions is of particular importance in the context of combating internal plant diseases, for example, rust on cereals and powdery mildew on cereals.

The compositions of the invention can simultaneously suppress the growth of two or more of said fungi and have high plant compatibility. The application rates required for combating phytopathogenic fungi are between 0.05 and 2 kg of active ingredient per 1 ha of culture area.

The active compounds according to the invention can be applied to the customary formulations such as solutions, emulsions, suspensions, powders, pastes and granules. These compositions are prepared in a manner known per se, for example by mixing the active ingredient with solvents and / or carriers, optionally with emulsifiers and dispersants, where further organic solvents, such as co-solvents, can also be used when the water is used as a diluent. As excipients. - 200238, in particular: solvents such as aromatics (e.g. xylene, benzene), chlorinated aromatics (e.g. chlorobenzenes), paraffinic hydrocarbons (e.g. petroleum fractions), alcohols (e.g. methanol, butanol), amines (e.g. ethanolamine, dimethylformamide) and water; carriers such as natural stone meal (for example kaolins, clays, talc, chalk) and synthetic stone meal (for example highly disperse silicic acid, silicates); emulsifiers such as non-ionic and anionic emulsifiers (for example polyoxyethylene fatty alcohol ethers, alkylsulfonates and arylsulfonates) and dispersants such as lignin, sulfite waste liquors and methylcellulose.

The compositions generally contain between 0.1 and 95% by weight of active ingredient, preferably between 0.5 and 90% by weight of active ingredient. These compositions or ready-to-use dosage forms made therefrom, such as solutions, emulsions, suspensions, powders, pastes or granules, are used in a known manner, for example by spraying, fogging, dusting, scattering or potting.

The compositions according to the invention may also be present in these dosage forms together with other active ingredients, such as herbicides, insecticides, growth regulators and fungicicycles, or they may be mixed together with the fertilizer.

Fungicides which may be combined with the compounds of the invention are, for example: dithiocarbamates and derivatives thereof, such as ferric dimethyldithiocarbamate; zinc dimethyldithiocarbamate, manganese zinc ethylene-bis-dithiocarbamate, manganese zinc ethylenediamine-bis-dithiocarbamate, zinc ethylene-bis-dithiocarbamate, tetramethylthiuram disulfides, N, N-ethylenebiamethylbenzenesulfonate, Zinc i, Ν'-propylene-bis-dithiocarbamate, stannous i, Ν-propylene-bis-dithiocarbamate, ammoniacal complex

N, N * -polypropylene-bis- (thiocarbanoyl) disulfide.

Nitrophenol derivatives, such as dinitro- (1-methylheptyl) phenyl crotonate, 2-sec-butyl; 4,6-dinitrophenyl-3,3-dimethylmethylene; acetate, 2-6-6, 171-4, 6-dinitrophenylisopropyl carbonate;

heterocyclic compounds such as

N-trichloromethylthiotetrahydrophthaliride, N-trichlorinethylthiophthaline, 2-heptadecyl-2-imidazoline acetate, 2,4-dichloro-6- (o-chloroanilino) -s-triazine,

O, O-diethylphthalimidophoafonothioate,

5-amino-1- (bis- (dimethylamino) phosphoryl) -3-phenyl-1,2,4-triazole, 5-ethoxy-3-trichloromethyl-1,2,4-triazole,

2,3-4-cyano-1,4-dithiaanthraquinone, 2-thio-1 H -dithCo [1,5-b] amino] -cyclohexyl, 1-butylcarbamoyl-2-benzimidazoCalbamic acid methyl ester, 2-methoxycarbonylaminobenzinidazole, 2-1H-thanomethylthihenzobenzyl

4- (2-Chlorophenylidyl) -3-methyl-5-Cxxazolone, pyridine-4-thiol-1-oxide, 8-iydroxyciinoline _and optionally a copper salt thereof;

2,3-diyl-5-calboxanec1-4-6-methyl-1,4-hexathiine-4,4-4-dioxide,

2,3-4-methyl-4-methyl-1-oxanilido-6-methyl-1'-oxanthin,

2- (fur-2-yl) benzimidazole, piperazine-1,4-diyl-18-1- (2,2,2-trichloroethyl) -formamide,

2-thiazol-4-ylbenzimidazole,

5-1и1у1-2 ^ Гте1Су1ап1Гпо-4-Суй1тоху “6-те1Су1ру1гЬпГД1п, b8- (p-chlorophenyl) -3-pyridiioBethiHuOL,

1,2-br8- (3-ethoxycarbonyl-2-thioureido) benzene ₉

1,2-bie- (3-methoxycarbonyl-2-thioureido) benzene, and various fungicides such as dodecylguanidine acetate,

3- / 2- _(3> 5-dimethy1-2-oxychk1oCeχh1) -2-CydroxyetCy1 / glutarrπid, hexachlorobenzene

N-thiophenoxythiomethylsulfonyl-N, N-hexylamine,

2. S-dimethylfuran-4-caroboxanilide, cyclohexane-2, S-dimethylfuran-4-carboxylic acid, 2-methylbenzoic anilide, 2-iodobenzoic anilide,

1- (3,4-Dichlooanilino) -1-phenylamino-2,2,2-trichloroethane,

2,6-drmetCy1-N-tridecylmorpholine or its salts,

2,6-Dimethyl-N-chlorododecylmorpholine or its salts,

2,3-Dichloro-1,4-naphthoquinone

1,4-dicC1OO-2,5-dimithoxyoxybenzene, p-dimethylaminobenzene-diazine-nitrosulfurol,

1-chloro-2-nitoopoopane, polychloonitoobenzene, such as pentachloronitrobenzene, ωγ-γ-β-β, an antifungal, antibiotics such as goiseofulvin or causgamycin, tetrafluordichloroacetone,

1-Phenylthiosemicobazide, Boodeaux south, nickel and sulfur containing compounds.

For the following experiments demonstrating the fungiidal activity of the compounds according to the invention, the following known active substances

O - CH ₂ -CH = CH 2 (cf. DOS 2 063 · 857).

Example 14

Test for barley powdery mildew

The leaves of barley plants grown in Fiolbecks Union pots are sprayed with an aqueous emulsion consisting of 80% by weight of the active ingredient and 20% by weight of the emulsion and, after the spraying layer has dried, the plants are dusted with powdery mildew is of the name (Erysiphe goaminis var. hordei). The test plants are then placed in a greenhouse at temperatures between 20 and 22 ° C and at 75 to 80% relative humidity. After 10 days, the level of powdery mildew is found.

2Q023Q

The results are shown in the following table, with 0 ³ no attack, graded to 5, which means complete attack.

Table

Active Substance Attacking the leaves after spraying

...% suspensions effective 0.05 substances 0,025 4 2 - 6 0 3 9 0 3 10 0 4 12 0 2 14 0 2 15 Dec 0 3 16 0 3 21 0 2 to 3 25 0 2 26 0 3 27 Mar: 0 3 30 0 0 31 0 3 40 2 - 41 0 2 46 0 2 50 0 3 54 0 2 to 3 59 0 2 64 0 2 65 0 3 7 0 0 60 0 0 65 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 O 0

Active Substance Attacking the leaves after spraying

...% Biiapension of the active substance

0.05 0,025 128 0 0 control (untreated) 5

Example 15

Wheat powdery mildew test

Correspondingly, as described in Example 9, the leaves of Jubilar wheat plants growing in pots are treated and then infested with oid powdery mildew (Erysiphe graminis var. Tritici) and the rest proceeding as in Example 9.

Active substance Leaves attack after spraying 4 0 2 30 0 0 40 0 2. 80 0 0 85 o o 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 i 128 0 2 AND 13

inspection (untreated)

Example 16

Wheat rust test

Leaves of Jubilar wheat seedlings grown in pots are artificially infected with spores of Puccinia econdita 24 hours before spraying and then placed in a chamber where the atmosphere is saturated with water vapor at 20-25 ° C. The plants are then sprayed with aqueous emulsions consisting of 80% by weight of active ingredient and 20% by weight of emulsifiers. After the spray layer has dried, the test plants are placed in a greenhouse at a temperature between 20 and 22 ° C and a relative air humidity of 75 to 80%. After 10 days, the degree of rust development is determined.

The results of this test are shown in the following table:

Active substance Attacking leaves after spraying with 0.05% active substance suspensions 4 2 12 0 27 Mar: 0 30 0 7 0 80 0 85 0 90 0 92 0 104 0 113 0 114 0 116 0 125 0 126 0 Ϊ27 0 AND 3 inspection (untreated) 5

Example 17

90 parts by weight of compound 1 are mixed with 10 parts by weight of N-methyl-alpha-pyrrolidone to give a solution which is suitable for application as minimal drops.

Example 18 parts by weight of compound 2 are dissolved in a mixture consisting of 80 parts by weight of xylene, 10 parts by weight of the editorial product 8 to 10 moles of ethyl oxide with 1 mol.

Oleic acid N-monoethanolamide, 5 parts by weight of dodecylbenzene sulfo200238 new acid calcium salt, and 5 parts by weight of the 40 mol ethylene oxide-1 mol castor oil edition product. Pouring this solution into 100,000 parts by weight of water and finely distributing it yields a water dispersion containing 0.02% by weight of the active ingredient. substances.

Example 19 parts by weight. compound 3 is dissolved in a mixture consisting of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of an adduct of 7 moles of ethylene oxide with 1 mole of isooctylphenol and 10 parts by weight of an adduct of 40 moles of ethylene oxide with 1 mole of castor oil. Pouring this solution into 100,000 parts by weight of water and finely distributing it gives an aqueous dispersion containing 0.02% by weight of the active ingredient.

Example 20 parts by weight of compound 1 are dissolved in a mixture consisting of 25 parts by weight of cyclohexanol, 65 parts by weight of a mineral oil fraction, boiling point 210 DEG-280 DEG C. and 10 parts by weight of an adduct of 40 moles of ethylene oxide. 1 mol of castor oil. Pouring this solution into 100,000 parts by weight of water and finely distributing it gives an aqueous dispersion containing 0.02% by weight of the active ingredient.

Example 21 parts by weight of active ingredient 2 are well mixed with 3 parts by weight of diisobutylnaphthalene-alpha-sulfonic acid sodium salt, 17 parts by weight of ligninsulfonic acid sodium salt from sulphite waste liquors and 60 parts by weight of powdered silica gel and this mixture is ground in a hammer mill. A fine dispersion of this mixture in 20,000 parts by weight of water is obtained by spraying a suspension containing 0.1% by weight of the active ingredient.

Example 22 parts by weight of compound 3 are intimately mixed with 97 parts by weight of finely dispersed kaolin. In this way, a dust containing 3% by weight of the active ingredient is obtained.

Example 23 parts by weight of compound 4 is intimately mixed with a mixture consisting of 92 parts by weight of silica gel and 8 parts by weight of paraffin oil which has been sprayed onto the surface of this silica gel. In this way, the active substance form with good adhesion is obtained. .

Example 24 parts by weight of active ingredient 1 are intimately mixed with 10 parts by weight of the sodium salt of the condensation product of phenolsulfonic acid, urea and formaldehyde, 2 parts of silica gel and 48 parts of water. A stable aqueous dispersion is obtained. Dilution with 100,000 parts by weight of water gives an aqueous dispersion containing 0.04% by weight of active ingredient.

EXAMPLE 25 parts of active ingredient 2 are intimately mixed with 2 parts of calcium dodecylbenzenesulfonic acid, 8 parts of polyglycol ether of fatty alcohol, 2 parts of sodium salt of phenolsulfonic acid, urea and formaldehyde condensation product and 68 parts of perefin mineral oil. A stable oil dispersion is obtained.

SUBJECT OF THE INVENTION

Claims (1)

SUBJECT OF THE INVENTION A fungicidal composition comprising a solid or liquid carrier and, as an active ingredient, at least one alpha-azolyl sulfide or a derivative thereof having the general formula: R2 (O) ⁿ . II “ ₃ R ¹ - C - S - R ^J AND In which _R @ 1 represents hydrogen, a straight or branched alkyl group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, an alkynyl group having 3 to 7 carbon atoms or an alkoxycarbonyl group having 2 to 7 carbon atoms or optionally 1 to 3 identical or different substituents from the group consisting of fluorine, chlorine, bromine, cyano, nitro, trifluoromethyl or C 1 -C 4 alkyl, substituted phenyl or naphthyl, R is hydrogen or (C1-C4) -alkyl, R ³ represents ^{PR and} direct no ^b of branched ^{ive out of five} Venom ^l k ^yl cord for ^the u ^pi nu s ^{is from 1} to 6 atoms in ^{H if u} · alkenytovou group having 2-6 carbon atoms or alkynyl of 3 to ' 6 carbon atoms or optionally 1 to 3 substituents selected from the group consisting of fluoro, chloro, bromo, trifluoromethyl, (C 1 -C 4) alkyl or (C 1 -C 4) alkoxy, substituted phenyl or benzyl; Az is imidazol-1-yl, pyrazol-1-yl, 1,2,4-triazol-1-yl, 1,2,4,4-trazol-4-yl, tetrazol-1-yl, or tetrazol-2- yl and _л n represent the number 0, 1 or 2, or a salt or complex thereof with a metal » Sevorography. n. p., plant 7, Most