DK145597B - ALFA-AZOLYL SULFIDES AND DERIVATIVES THEREOF USED AS FUNGICIDES FOR PLANT PROTECTION - Google Patents

Description

(19) DENMARK

® (12) PUBLICATION ON 145597 B

DIRECTORATE OF THE PATENT AND TRADEMARKET SYSTEM

(21) Application No. 3456/78 (51) IntCI * C 07 D 247/00 (22) Filing Day 4. Slug. 1978 C 07 D 249/08 (24) Race day 4 Aug. 1978 C 07 D 257/04 (41) Aim. available Feb 6 1979 A 01 N 43/48 (44) Submitted 20 Dec. 1982 A 01 N 43/64 (86) International application no. - (86) International filing day (85) Transfer day - (62) Common application no. -

(30) Priority Aug. 5 1977, 2735314, DE

(71) Applicant BASF AKTIENGESELLSCHAFT, 6700 Ludwigshafen, DE.

(72) Inventor Hubert Sauter, DE: Ernst-Heinrich Pommer, DE: Bernd

Zeeh, DE: Costin Rentzea, DE.

(74) Associate Engineer Hofman-Bang & Boutard.

(54) Alpha-azolyl sulfides and derivatives thereof for use as fungicides for plant protection.

The invention relates to new, valuable <3-azolylsulfides and their derivatives, α-azolylsulfoxides and alpha-azolylsulfones, and their salts for use as plant protection fungicides.

It is known that imidazole derivatives, e.g. 1- [2- (2,4-Dichloro-phenyl) -2-allyloxy-ethyl] -imidazole (DE of fentilization, see Specification 20 63 857) exhibits good fungicidal activity. The effect of low QQ levels and application concentrations is not always satisfactory. In addition, the fungitoxic effect is often associated with a high phytotoxicity, so that the culture plants are also damaged Ώ at the concentrations necessary for rust fungi. Of these

J

i— causes are not always suitable for all plant species.

*

Q

145597 2

It is an object of the invention to provide α-azolyl sulfides and derivatives thereof which exhibit good fungicidal activity while not damaging cultured plants at such concentrations in which they exhibit good fungicidal activity.

The novel α-azolyl sulfides of the invention and their derivatives are characterized by the features of the claim.

It has been found that these novel α-azolyl sulfides and their derivatives have good activity against harmful fungi, especially from the class comprising ascomycetes and basidiomycetes, in combination with good plant-plant compatibility.

It is known from German publication no.

2,541,833 are chemically related to the α-azolyl sulfides and their derivatives according to the invention, but these known compounds exhibit a far poorer fungicidal activity than the α-azolyl sulfides and their derivatives according to the invention.

R1 means e.g. methyl, ethyl, n-propyl, isopropyl, n-butyl, n-pentyl, n-hexyl, phenyl, 4-nitrophenyl, 4-bromophenyl, 4-cyano-phenyl, 2-methylphenyl, 4-t-butylphenyl, 3- trifluoromethylphenyl, 4-trifluoromethylphenyl, 4-fluorophenyl, 2-chlorophenyl, 4-chlorophenyl, 2,4-dichlorophenyl, 2, β-dichlorophenyl, 3s4-dichlorophenyl, a-naphthyl.

2 R means e.g. hydrogen, methyl, n-propyl.

R means e.g. methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, allyl, phenyl, 4-methoxy-phenyl, 4-totyl, 4-chlorophenyl, 3,4-dichlorophenyl, 2,4-dichlorophenyl, 2, 3,6-trichloro-phenyl, benzyl, 4-chlorobenzyl, 4-bromobenzyl, 3} 4-dichlorobenzyl, 2,4-dichlorobenzyl, 2,3,6-trichlorobenzyl and 2-phenylethyl.

Salts are e.g. the hydrochlorides, bromides, sulfates, nitrates, phosphates, oxalates or dodecylbenzenesulfonates. The activity of the salts originates from the cation, so that the choice of the anion is arbitrary.

3 145597

The subject <= t-azolyl sulfides of formula I (with n = 0) can be prepared by reacting ot * chlorosulfides of formula R2 R1 - C - S - R3 (III) t

Cl wherein 12 3 R, R and R have the meanings specified in the claim, with the azoles H-Az, wherein Az has the meaning given in the claim, optionally in the presence of a base and optionally in the presence of a diluent. Oxidation of the thus-obtained β-azolyl sulfides of formula I (n = 0) gives the Λ-azolyl sulfoxides of formula I (n = 1) and the "c-azolyl sulfones of formula I (n = 2).

For the preparation of the "C-azolyl sulfides of formula I (n = O), it is convenient to react" the C-chlorosulfides of formula III without diluent or in the presence of a diluent of about 10%. 0.5 to 2 equivalents of an alkali salt of the azole in question or by approx. 0.5 to 4 equivalents of the azole concerned, optionally with the addition of 0.5 to 4 equivalents of a base at temperatures of approx. 0 to 200 ° C, preferably + 20 ° C to + 160 ° C, in homogeneous or inhomogeneous phase.

As a diluent, for example, methanol, ethanol, isopropanol, n-butanol, diethyl ether, tetrahydrofuran, dioxane, acetone, acetonitrile, dimethylformamide, dimethylsulfoxide, chloroform, methylene chloride or toluene may be used. As bases, for example, organic amines such as triethylamine, pyridine or inorganic compounds, e.g. potassium carbonate or sodium hydroxide.

The α-chlorosulfides III used as starting materials are known from the literature or can be prepared according to methods known from the literature, e.g.

4 145597 (a) by chlorinating sulfides with N-chlorosuccinimide (see e.g.

B. L. Tuleen and T.B. Stephen, J. Org. Chem., 3H, 31 (1969)) according to the reaction scheme: R2 0 R1 - CH - S - R3 + cf N-Cl -} n 0 rj2 0 R tt

R1 - c - s - H · 5 + f ^ NH

Cl (IXI) W

0 or (b) by reacting aldehydes with thiols in the presence of hydrogen chloride (see, e.g., H. Bohme, H. Fischer, and R. Frank,

Liebigs Ann. Chem. 563 * 5 ^ (19 ^ 9) according to the reaction scheme: R1-CHO + HSR3 + HCl ->

H

R-C-SR3 + HpO Cl (III)

To prepare the <RTI ID = 0.0> azolylsulfoxides of formula I (n = 1), </RTI> the dC-azolylsulfides, optionally in the presence of a diluent, are reacted with approximately an equivalent of a suitable oxidizing agent at temperatures between ca. -30 and + 100 ° C.

The Λ-azolylsulfones (formula I, n = 2) are similarly obtained by oxidation of the «C-azolylsulfides (I, n = 0) with at least two equivalents of a suitable oxidizing agent or by oxidation of the oC-azolylsulfoxides (I, n = 1) with at least one equivalent of an oxidizing agent.

5 U5597

For example, as the oxidizing agent, potassium permanganate, hydrogen peroxide or percarboxylic acids such as peracetic acid, perbenzoic acid or 3-chloroperbenzoic acid may be used. As diluent, for example, water, acetic acid, methanol, acetone, chloroform or methylene chloride may be used. A preferred method of preparing the sulfoxides (I, n = 1) is reacting the sulfides (I, n = 0) with an equivalent of 3-chloroperbenzoic acid in methylene chloride at 0 to 25 ° C. A preferred process for preparing the sulfones is the reaction of the sulfides (I, n = 0) with two equivalents of 3-chloroperbenzoic acid in methylene chloride at 15 to 41 ° C.

The compounds of formula I (n = 0, 1, 2) are readily soluble in many organic solvents, e.g. in vinegar ester, acetone, ethanol, methylene chloride, chloroform, dimethyl sulfoxide, dimethylformamide and N-methylpyrrolidone. In addition, the <4-azolyl sulphides (1 = 0) are also easily soluble in toluene.

They are allowed to transfer to their salts with acids, e.g. hydrochlorides, sulfates, nitrates, oxalates, formates, acetates or dodecylbenzylsulfonates.

The sulfides (I, n = 0) and the sulfones (I, n = 2) in each case contain an asymmetric carbon atom and therefore appear as an enantiomer mixture which can be separated into the optically active compounds.

* 1 'In the case of the sulfoxides (n = 1), due to the asymmetric sulfur atom adjacent to the asymmetric carbon, diastereomeric mixtures which occur in the usual manner, e.g. by crystallization or chromatography, can be separated into individual components. For use as fungicides or as a means of regulating plant growth, separation of the enantiomers or diastereomers is usually not necessary.

6 145597

In order to investigate the fungicidal activity of the compounds described in German Patent Specification No. 2,541,833, the experiments set forth below were carried out. The compounds listed in the following Example 10 were used as well as the compounds A and B listed below, which correspond to the prior art German publication specification No. 2 541 833.

0¾ ¾ · HC1 ύ <λ>

Cl CHg H2 Hg · HCl (B)

In the experiment, the effect on barley mildew was assessed. Leaves of seedlings propelled in herbal pots of the "Firlbecks Union" variety were sprayed with aqueous emulsions consisting of 80% by weight of active ingredient and 20% of emulsifier; after the sprayed layer had dried, the leaves were powdered with spores of barley mildew (Erysiphe graminis var. hordei). The plants were then introduced into a greenhouse at 20 to 22 ° C and 75 to 80% relative humidity. The extent of mildew spread was determined after 10 days.

145597 7 O = no attack, graduated down to 5 = total attack

Leaf attack after spraying with liquid Compound containing the compound in amounts of _0.0¾¾_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 O 3 27 0 3 30 0 0 31 0 3 40 2 41 0 2 48 0 2 50 0 3 54 0 2-3 59 0 2 64 0 2 65 0 3 70 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 0 125 0 0

126 0 O.

127 0 0 128 0 0 A3 4 B 3 4

Control (Untreated) EXAMPLE 1 8 £ i§_if2 £ 2is ^ §i22_22i_§5)

To dissolve 22.1 g of 1,2,4-triazole in 500 ml of anhydrous acetone, 60.5 g of tert-butyl-Zr (2,4-dichlorophenyl) chloromethyl7 sulfide are added. After the addition of 44.2 g of finely powdered potassium carbonate, the mixture is heated under stirring for 7 hours under reflux. The insoluble components are then filtered off, the filtrate is evaporated in vacuo to dryness and the residue is mixed with 300 ml of water. The aqueous phase is extracted 3 times, each time with 200 ml of methylene chloride, the combined extracts are washed with 200 ml of water, dried and evaporated in vacuo. After the addition of 100 ml of diisopropyl ether, 35.6 g (.53%) of colorless crystals were obtained from the residue, mp 95-97 ° C.

1 H NMR (100 MHz, CDCl 3): δ = 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 Μηάβΐ3β_ηηΛ_892

To dissolve 43.6 g of imidazole in 300 ml of acetone, 82 g of tert-butyl-f (2-methylphenyl) -chloromethyl-7-sulfide is added dropwise with stirring. After adding 88 g of finely powdered potassium carbonate, it is heated for 5 hours under reflux. Then, the undissolved constituents are filtered and the filtrate is concentrated.

The residue mixed with 300 ml of water is extracted with 3 x 200 ml of methylene chloride. From the combined organic phases, after washing with water, drying and concentrating, 69 g of a brownish oil is left, which is dissolved in 1 liter of diisopropyl ether.

By dropwise addition of 90 ml of a 2.85 molar solution of hydrogen chloride in diisopropyl ether with stirring, this solution precipitates pale yellow crystals of the hydrochloride which is recrystallized from acetone. There is obtained 51 g of colorless tert-butyl-Zr (2-methylphenyl) -imidazol-1-yl-methyl7-sulfide hydrochloride, mp 168 to 170 ° C (Compound No. 110).

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

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

EXAMPLE 3

The mixture of 60.7 g of 4-chlorophenyl (chloromethyl- (4'-chlorophenyl)) sulfide, 27.2 g of imidazole and 55.4 g of potassium carbonate in 400 ml of acetone is heated under stirring for 5 hours under reflux. The filtrate is then filtered, the filtrate is concentrated to dryness and mixed with 500 ml of water. This mixture is extracted three times with 200 ml of methylene chloride each time. The combined extracts are dried over sodium sulfate. From the solution concentrated in vacuo to dryness, after rubbing with diisopropyl ether, 26 g (38¾) of colorless crystals having a melting point of 88 ° C were isolated.

1 H-NMR (60 MHz, CDCl 3): i = 6.3 (s, 1H) 6.9 - 7.4 (m, 10H) 7.5 (br, s, 1H) Example 4 ] 2B5Zil 2 (16dichloro) hen2l) EY £ azol2lmeth2l7; Sulfide_ (Compound No. 53)

To dissolve 193 g of tert.-butyl- (chloromethyl- (2,6-dichlorophenyl)) -sulfide and 44 g of pyrazole in toluene, 66 g of triethylamine are added dropwise and heated, after the slight exothermic reaction is quenched, Reflux · Filter the undissolved material, concentrate the filtrate and mix the residue with 500 ml of water. After extraction with three times 200 ml of methylene chloride is obtained by. concentration of the combined extracts a solid residue which, after washing with diisopropyl ether, produces 117 g (57 $) colorless crystals, mp 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 5 22iii ^ _i £ 2E2i2§2M2i2S_2rj._§i) _2S_2i4-dichloro-benzyl; £ t 2 ^ a4_ | _; πγλ_64)

A mixture of 200 g of 2,4-dichlorobenzyl- (f (2 ', 4'-dichlorophenyl) chloromethyl17 sulfide, 145 g of 1,2,4-triazole and 138 g of powdered potassium carbonate in 2 liters of anhydrous acetone is heated with vigorous stirring). for 9 hours with stirring. The solids are then removed by filtration, the filtrate is concentrated in vacuo to dryness and the oily residue is extracted by the addition of 500 ml of water and five times with 200 ml of methylene chloride each time. The combined organic phases are dried over sodium sulfate and then concentrated in vacuo to dryness. By rubbing the residue with di-isopropyl ether 157 g of colorless crystals containing the 8: 2 isomeric triazolyl compounds are obtained.

This mixture is extracted several times with hot hexane. On the basis of the combined hexane solutions, by extracting the solvent in vacuo, 122 g (65z) of 2,4-dichlorobenzyl-Z "(2,4,4-dichlorophenyl) -1,2,4-triazol-1-yl-methyl7 is obtained. -sulfide in the form of colorless crystals, m.p. 120 - 125 ° C.

1 H NMR (220 MHz, CDCl 3): i = 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 from the hexane extractions consists of 27 g (12¾) of 2,4-dichlorobenzyl- [2,4,4-dichlorophenyl) - (1,2,4-triazol-4-yl) methyl7-sulfide with mp 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) 8.45 (s, 2H).

EXAMPLE 6 SESil ^ HSiiljrLiilShlorghenyl) -1 ^ 2 ^ 4-triazol-1-ylmethyl ^ sulfide

To a solution of 78 g of tert.-butyl-OT (4-chlorophenyl) -chloromethyl7-sulfide in 175 ml of dry dimethylformamide (DMF), 350 ml of a molar solution of 1,2,4-triazolyl sodium in DMP (prepared of 0.35 mol of sodium hydride and 0.35 mol of 1,2,4-triazole in 350 ml of DMF). After the weak exotherrae reaction is quenched, stir for another 4 hours at 80 ° C. The portion is poured into 1 liter of water and extracted three times with 200 ml of methylene chloride each time. The combined organic phases are washed with water, dried over sodium sulfate and concentrated in vacuo. Upon trituration with 150 ml of diisopropyl ether, the residue forms 40.0 g (46 $) colorless crystals, mp 95 ° C.

2 H NMR (60 MHz, CDCl 3): S = 1.3 ppm (s, 9H) 6.6 (s, 1H) 7.2 (AA'BB *, 4H) 8.0 (s, 1H) 8.7 (s, 1H).

EXAMPLE 7 (S) Eilililililic acid (2ilic acid 2,4-triazolylmethyl) sulfoxide (Compound No. 31)

To the solution of 9.7 g of tert.-butyl - [(4-chlorophenyl) -1,2,4-triazolylmethyl7-sulfide in 20 ml of methylene chloride, a solution of 7.1 g of 85 per cent of 3-chloroperbenzoic acid is added dropwise. in 70 ml of methylene chloride. Stir for another 2 hours at 0 ° C until, after thin layer chromatogram (SiO₂g methylene chloride / acetone 7: 3), there is no longer any sulfide (R₂, = 0.57) and only the two diastereomeric sulfoxides can be detected (R₂, = 0 , 38 and '0.20). The solution is then washed with aqueous sodium hydrogen carbonate solution to complete the CO 2 evolution. After washing the organic phase with water, the one which is concentrated is dried and the solid residue is washed with a little ether. 7.0 g (67¾) of colorless crystals were obtained, mp 125 - 128 ° C.

1 H NMR (220 MHz, CDCl 3): δ = 1.10 and 1.15 (two s, together, 9H) 6.18 and 6.24 (two s, together, 1H) 7.3 - 7.7 (m , 4H) 8.01 and 8.07 (two s, together, 1H) 8.4l and 8.51 (two s, together, 1H).

EXAMPLE 8 TSE ^ I ^ ySYil ^ I ^ lShlorghenYll-l ^^ - triazolylmethYllJ-sulfone ί £ 2ϊΕΐ] ϊ§ £ ΐ§ £ _2ϊ! 0.1 to 222

To a solution of 10.7 g of tert-butyl-β (4-chlorophenyl) -1,2,4-triazolylmethyl7-sulfoxide in 50 ml of methylene chloride, a solution of 7.3 g of 85 per cent is dropped at 20 ° C. 3-chloroperbenzoic acid in 100 ml of methylene chloride. Following the result similar to thin-layer chromatography (DC), the less polar sulfoxide is more rapidly oxidized; only after longer stirring at room temperature, the stronger polar sulfoxide is also oxidized. After 18 hours, the reaction is completed according to DC (SiC> 2, methylene chloride / ace tone). The sulfone (R „= 0.46) is isolated by washing the solution Γ with sodium bicarbonate solution and water, drying and concentrating the organic phase. After washing the residue, the organic phase is isolated. After washing the residue with diisopropyl ether, 8.7 g (77%) of colorless crystals were obtained, mp 150 ° C.

1 H NMR (220, MHz, CDCl 3): i = 1.3 ppm (s, 9H) 6.75 (s, 1H) 7.5 (AA'BB *, 4H) 8.03 (s, 1H) 8.84 (s, 1H).

EXAMPLE 9.

(phenyl, 2-yl) -methyl7 = sulfide in £ 2 £ £ iS £ 2i§EJ2 £: _ i22

To a mixture of 26.1 g of tetrazole and 102 g of 4-chlorophenyl- (4'-chlorophenyl) -chloromethyl7-sulfide in 3.5 liters of toluene, 37.4 g of triethylamine are added dropwise with stirring. The mixture is then heated for 4 hours under reflux. The insoluble material is filtered off, the filtrate is washed with water and the organic phase is dried over sodium sulfate. After extracting the solvent in vacuo, a solid residue remains, on the basis of which 74.7 g (67%) of yellow crystals of melting point 104-106 ° C are isolated after the addition of 50 ml of diisopropyl ether.

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

Examples of the compounds of the invention of formula I are set forth in the following Table 1: TABLE 1

Example ++ R 2 R 2 Az (salt) n R 2 Mp. (° C) 1 H O - (Q) 132-13¾

Jl / - \ IR (filff-): 2 H, C- Η N /) O - (O / * 01 iif95, 1470, 3 Ί-η 1270, 1192, 1131, 1038, 1007, 8J7, 666 ca ' ±.

3 {5V H O -CK2- / o) 3060 ^ 3020, d 1492, 1450, lN 1271, 1190, 1131, 1008, 695, 677, • 658 cm Α 4 Οΐφ. HO "(O) 98 .5 d - @ - H /% .1 131-139 +) 6 Cl- ^ V Η 2" (O) 215 '7 Cl-®- · HO - @ K1 38 8 CLOV H. (CCOH) and O ~ (O) -Cl 85-27

V.N

9 Cl - ^ - Η ^ O. - @ - Cl 62-64 10 Cl- ©. Η · - .Λ,! - <§> - Cl 11β-1ΐ8 +) 11 Cl - @ - H · 2 - ^ 5) · Cl 147-150 12 Cl- <g> - H / j) O - <§> - Cl 136-138, + ^ Diastereomeric mixture of the sulfur oxides ++ The structures of all listed compounds were confirmed by spectra.

ΐδ 145597

Fort). R1 R2 Az (salt) n Srap. (° C) l 13 ci <o) - a Λ t - (o) -ci H7 *> “01 · @ - Η Ό * Cl 20¾ t 15 Οΐφ- ff ΐζ \ * Λ +) 0 '- ^ Cl 104 -106 I 1 16 H + 'ζ ^ 1 ÆVci 110-112 ++) 17 C1 ^ 0> Η Λ. ('f. 2' - © -Cl 123-125 Η- 'ΪΓΝ

18 C1- ^ Q> - H ^ 0 ^ 5} -CH3 HO

19 Cl · ®- Η 1 lJf7 “l! F3 ++) I ^ - ίί 20 Cl - @ - H 1 - ^ CH3 15 * -155 +++) t 21 01 · ^ - HN ^ S 2 ^) - CH3 2¾ 5 22 01- ^ H 0 Cl 102 • Cl 23 Ol · ®- H - Q 0 - ^ 5 ^ -Cl 135-137 's-ζ1' A IRCfiln): 2¾ Η O 0 tert * -butyl 1? SS; ? 362! 1212, 1152, 1096, 106¾, 10 * 13, 844 ,.

787, 657ca-- "^ Mixture of tetrazolisomeric Dias tomer mixture of sulfoxides +++)

Stronger polar sulfoxide, separated by crystallization from diastereomer mixture # 19.

17 145597

Fort). R1 R2 Az (salt) n R3 Slip. (° C)! 25 ci · ®- Η ° - <O> 0ra3 116 t 26. ci®- a 2 -®-0CH3 158 27 01- (py a Λ 0 -ca2 ^ 0) ci 57-52 NN IR (iila): 28 <a®- a> Q 0 ethyl 2965, 2925, 1131, 1088 ,, ..

f 1010,675cra '29 Cl- / oV- H ί'ί ° n-butyl 2 ^ 5 ^ 2920 V- / 1-N I486, 1263, 1127, 108Ha, 1007,671c = i * 30 Cl ~ <g) - H '0 pie. -butyl 95 31 ci - @ - H -. . 1 tert.-butyl 125-128 +) »32 H Κ-ί 2 tert ,, 'b''utyi 150» IR (film): / - \ / Ns ft Ollvl 3054> lIl89> .33 Cl- (oV H n "0" allyl 1 ^ 03, 1270, N 1130, 1087, 1007 ,.

672 cm cm¾ (3¾ Br- ^ 5) H N₂O> tert.-butyl 77-78

N

35 p- ^ j) - H / J} 0 tert.-butyl 102-10¾ t 36 NO- 5) - H /% 'tert.-butyl 73-75 # 37 ° 2Ν · ^ 5} "H ° tert * -tutyl 76-78 + K ~

Diastereorrhea mixture.

Conn. H 1 R 2 Az (salt) n R 2 Mp. (° C) 145597 18 38 ch3 * ύ 0 tert, "Duty'1 '? 2 <1) 0 ({£ - Η Λ o" © 91

.- 'i-JJ

D1 (^ -C1 H KJ] 1 70-38 +), 2 η Λ 2 · ® 143

.Cl N

ijj H ^ 7 O tert-butyl 8D

. ^ Cl.

I'D (Or H 1 tert.-butyl 154-157 * '' - 'm_n / -C01 D5 \ Q / ~ g n' /) 2 tert.-butyl 126 '

- tt-H

__> / CF, 1H (filr.): 46 H lQ 0 -CK2 - @> ϊαίο / N 1115, 1070 cp3. 790, 6tf, 660 era * »Cl D7 ci- ^ C ^ - · H /%. CCOOK) 20 0 -CH 2 Cl 133-135 48 Cl ^ - H 0 -Ch'2 - ^^ - Cl 101 GX N r-fC1 49 Cl - @ - H iQ 2 -CH2 - ^) Ci 195-197 " ^ Diastereomeric Blend 19 145597

Conn. R1 R2 Az (salt) n R3 Snp. (° C) 50 01 ^ - H fy O 82-8 * 51 o% ^ B fy * fy 1 io * -no *> CL · _ Λ v, _ £ 1 52 «φ- H lQ <* Q 8 - CH2- @ K: 1 100-105 53 EV Η /> 0 tert.-butyl 57-58 ^ Cl 'y -Cl XNV I- 54 r ~ \ H il> O tert.-butyl 110-112 (oV ύ- Μ 55> 0 / - H 'N ^^ /) 0. tert.-butyl 112-115 «-» · ___ ©' A 0 56 / ^ Λ_ Η 1 tert.-butyl 122-127; © 57 ®- Η Ό 2 tert.-butyl 180-183 58 βφ Η Λ O - © - «128 59 oi · ^ -1 · r ό °. 1, s'150 60 Cl H O -CE2 ^ C1 105 +).

Diastereomeric mixture

Conn. R1 R2 A2 (salt) n_R3 Snp. (° C) U5597 20 61 Cl · ^. H · / j> O -CH ^ -Cl 120-125 62 Cl ^ c £ Η Nj) 1 -CH2 ^). C1 125-131 +) · _JC1 j'j Cl_ 63 Cl ^ gy- H nj> 2 · . -CK ^ Cl 163-165 fil C1> - \ 64 tt- © - H (f_> 'O -CH2- <g ^ l 132-133 65 cl * ^ C>) - H 0 tert.-butyl 95-S7 cx * 66 Cl & »Q 0 -CH3 -66-88

«7 Cl · ^ H £ '° 95'5T

69 'n-hsxyl Η' Λ ° »5ff? 920, J 2850, 1ts6, 1471, 1270, 1132, 1089, .1008, 818,, 67¾ cm 1 70 n-butyl H / * /? 0 - (oVcl 'IRC'fila)! · Tt_N '-Z' 2950, 2920, 1496 ·, 1472, 1270, 1132, 1089, 1008, 8l8,672cin ** l "Diastereomeric mixture

Porb. R1 R2 Az (salt) n R3 Snp. (° C) U5597 21 72 H ^ C- H3C- 0 “\ 0)“ cl 76-79 \ A r-Λ IRC; file): 73} - · a \ i 0 - € >> - «= ¾¾ 1130 , 1050, 1007, 815, 673 6a 1 £ IRtfila): 7 * ethyl H lQ o nF - epsa? F «; Jig.

"1192, 1133, 1003, 817, 675 cm" 1 80 <H> ° H (o) -ci 100-103 * _scl 81 \ 2 / "H ^. 1 ter "*> 115 115S +) '01 / C1 j 82 \ 2 /" H 2 tert: · -butyl 164-155 NC1

if'K

83 n-butyl H, N-tert.-Cutyl IRClf) 2953, 1495, 1459, 1364, 1272, liso, 1153, 1134; 1010, 677 ca ~ 84 i-butyl H tert.-fcutyi IR (filo).

2952, 2862, 1494, .1457 1364, 1270, * II89, 1157,, H32, 1007,, / TK i-v 6? 5 ca - 85 i-butyl H 0 - \ 0 \ ci butyl H 'Q 1 * 0 0 01 UO-112 87 i-butyl H' {\? 2 -®-Cl 140-141 No. R1 R2 Az (salt) n R3 Mp. (° C)

Compound - xylene xCH 3 88 µl / · E 0 tert.-butyl 98-101 'H 0 tert.-butyl 93-95 92 0 <Q> C1 105-107' 93 (S) - H 0 tert.-butyl 105-108 94: 0 0 tert.-butyl 40-lf3 '95 H3fe-Η Λ 0 tert.-butyl 85-37

^ CN

96 H 0. tert.-butyl 110-112 97 h Q 0 tert.-butyl 9 ^ -95 / - <C1 98 Y ^) ethyl o ethyl 59-81. -10 It U5597 23

Relations

døXsG

No. R1 R2 Az (salt) n R3 Mp. (° C) / - <C1 100 <0> - H0 n-butyl IR (fUa): \ -f t_N 2958, 2928, 149 ^, 1274, 1132, 1008, - XI. (f 748, 678 cs * 102 EV HQ 0 - ° Η2 · {θ) 96-93 103 {Oy H 2 ^ z (Qj 130-133 / Cl i ° 4 (q \. H iQ 0 -CH2-CH2 ^ 0 ^ 58-61 / Cl 105 EV H Λ 2 -cvch2- <o) 129-130, C1 10 $ »· © - H 0 {o) -1 108-110 110 EV H o tert.-liutyl 163- 170

_XI

111 Æ / · H * EC1 0 »'I« * 1 135-139 24 14559?

Compound R1 R2 Az (salt) n R3 Sop. (° C), 01 112 (g \ H ·. HCl 0 -CH 2 -CH 2 - / o ^> 145-155 p- (o) - H 0 SO 0 92 114- 'H 01 Π5 <0> HQ 0 · © *! 69-7-.

/ Cl 116 / qV HQ 0 ^ o) "" 13Ί-136 WC1 117 / oV H 0 t is t.-butyl IH (filn): \ / · Ϊ_Ν 3098, 2950, 1463, 1211, 1153, ICO2, 1040, 739, <^ 01 t 657 cm 118 ci H H tert.-b-utyl 940/01 119 Cl- ^ Oy * H 2 tert.-butyl 153-156 120 / new H 2 tert.-butyl 143-145

XZJ

_ / CH3 121 \ 0 / H 2 160-162

V ^

\ 145597 25

Compound No. # R1 R2 Az (salt) n R · ^ Snp. (° C) vcl 122 (O} - K 2 tert.-butyl 113-116. Cl 123 φ H 2 <Ο> 0! 155-158 CH, HN ^ // o - {Oj-Cl 33. -86 • ch3 n CH, y 126 CH ^ -C-CHg- H yjj. 0 - (Oj-Cl 47 - 51 • 'ch3 f

N

127 <0> H (_) 0 - <0) -c- 89 - 90

Cl ·.

_ / N _ IH (fllm): 188 01- <S> - H Q ° - = - V <0) - “310J, 1586, 1217, 1090, 1067, 1048, 1012, 825, 659 at ir

The new J 1 -azolyl sulfides, «C-azolyX sulfoxides and C-azolyl sulfones and their salts exhibit a significantly wider fungicidal effect and superior plant compatibility with the known 1- [2- (2,4-dichlorophenyl) -2-allyloxy ethyl] imidazole. The new active substances can also be used in the form of their salts, e.g. hydrochlorides, oxalates or nitrates.

Of great interest are the fungicidal agents of the invention in fungal diseases in various culture plants, e.g. by

Ustilago seitaminea (sugar cane)

Hemileia vastatrix

Uromyces fabae or appendiculatud (bean rust)

Puccinia species (grain rest)

Erysiphe graminis (cereal mildew)

Botrytis cinera for wine, strawberries,

Uncinula necator,

Sphaerotheca fuliginea,

Erysiphe cichoracearum,

Podosphaera leucotricha.

Cultural plants in this context mean in particular wheat, rye, barley, oats, rice, corn, apple trees, cucumbers, beans, coffee, sugar cane, grapes, strawberries and ornamental plants in gardens.

The active substances according to the invention are systemically active. The systemic activity of these agents is of particular interest in the context of the control of internal plant diseases, e.g. grain rust, grain mildew.

The agents of the invention may simultaneously suppress the growth of two or more of the indicated fungi and exhibit high plant compatibility. The amounts needed to control the phytopathogenic fungi are between 0.05 and 2 kg of active substance / ha of culture area.

The active substances of the invention can be transferred to the usual formulations such as solutions, emulsions, suspensions, powders, pastes and granules. These are prepared in known manner, e.g. by mixing the active substance with solvents and / or carriers, optionally using emulsifiers and dispersants, whereby in the case of using water as a diluent, other organic solvents can also be used as auxiliary solvents. As auxiliaries for this purpose, the following are mainly considered: solvents such as aromatics (eg xylene, benzene), chlorinated aromatics (eg chlorobenzene), paraffins (eg petroleum fractions), alcohols (e.g. methanol, butanol), amines (e.g., ethanolamine, dimethylformamide) and water; carriers such as natural stone flour (e.g. kaolin, clay, talc, chalk) and synthetic stone flour (e.g. high-dispersion silicic acid, silicates); emulsifiers such as nonionic and anionic emulsifiers (e.g. polyoxyethylene fatty alcohol ethers, alkylsulfonates and arylsulfonates) and dispersants such as lignin, sulfite waste liquors and methylcellulose.

The formulations generally contain between 0.1 and 95% by weight of active ingredient, preferably between 0.5 and 90%. The formulations or the ready-to-use preparations based on them, such as solutions, emulsions, suspensions, powders, pastes or granules, are used in known manner, e.g. by spraying, misting, spraying, spraying, pickling or pouring.

In these applications, the compounds of the invention may also be present with other active substances, e.g. herbicides, insecticides, growth regulators and fungicides, or mixed with fertilizers.

For the following experiments, which illustrate the fungicidal activity of the compounds of the invention, the following known active substance was used for comparison purposes: c '' 0-CH2-CH = CH2 known from DE Publication No. 20 63 857 28 145597 EXAMPLE 10

barley mildew

Leaves of barley-propelled barley seedlings of the species "Firl-becks Union" are sprayed with aqueous emulsions of 80% (wt.%) Of active substance and 20¾ emulsifier and powdered after the initial drying of the spray coating with oidia (spores) of barley mildew (Erysiphe graminis var. ). The test plants are then set up in greenhouses at temperatures between 20 and 22 ° C and 75 to 80 ° C relative humidity. After 10 days, the extent of fungal development of mildew is assessed.

145597 29 O = no attack, escalated to 5 = total attack.

Active substance Attack of the leaves after spraying with active substance spray liquid 0.05 0.025 4 2 6 0 3 7 0 0 9 0 3 10 o 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 50 0 3 54 0 2-3 59 0 2 64 o 2 65 o 3 80 0 0 85 0 0 90 oo 92 oo 94 oo 104 0 o 113 oo 114 oo 115 oo 116 oo 125 oo 30 145597

Active substance Attack of leaves after spraying with spray with active substance .0.05 0.025 126 0 0 127 0 0

Control (untreated) EXAMPLE 11

Wheat

Corresponding to the example described in Example 10, leaves of wheat-seed-propagated wheat seedlings of the species' 'Jubilar1' are treated, and they are infected with oidia (spores) of wheat mildew (Erysiphe graminis var. Tritici) and otherwise treated as described in Example 10-

Active substance Attack of leaves after spraying with spray with 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 oo 114 oo 115 oo 116 oo 125 0 o 126 0 o 127 0 1 128 0 2

Al 3 31 145597

Active substance Attack of the leaves after spraying with active substance spray 0,05 0,025

Control (untreated) EXAMPLE 12

Wheat Leaf Rust

Leaves of wheat-germ-driven seedlings of the species "Jubilar" are artificially infected for 24 hours prior to spraying with wheat brown spores (Puccinia recondita) and set at 20 to 25 ° C in a steam-saturated chamber. Then the plants are sprayed with aqueous emulsions of 80¾ (wt.%) Of active substance and 20¾ emulsifier. After the initial drying of the spray coating, the experimental plants are set up in greenhouses at temperatures between 20 and 22 ° C and 75 to 80 ° C relative humidity. After 10 days, the extent of the development of rust fungus is assessed.

Active substance Attack of the leaves after spraying with active substance spray liquid 4 2 7 0 12 0 27 0 30 0 80 0 85 0 90 0 92 0 104 0 113 0 114 0 116 0 125 0 12 6 0 127 0 A 3. 32 145597

Active substance Attack of leaves after spraying with active substance spray liquid

Control (untreated) EXAMPLE 13

90 parts by weight of Compound 1 are mixed with 10 parts by weight of N-methyl-i-pyrrolidone to give a solution suitable for use in the form of very small droplets.

EXAMPLE 14 20 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 preparation product of 8 to 10 moles of ethylene oxide to 1 mole of oleic acid N-monoethanolamide, 5 parts by weight of calcium salt of dodecylbenzenesulfonic acid and 5 parts by weight of the preparation of 4 mole of ethylene oxide to 1 mole of castor oil. By pouring and finely distributing the solution in 100,000 parts by weight of water, an aqueous dispersion containing 0.02% by weight of the active substance is obtained.

EXAMPLE 15 20 parts by weight of compound 3 are dissolved in a mixture consisting of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the product of 7 moles of ethylene oxide and 1 mole of isooctyl-phenol and 10 parts by weight of the product of 40 moles of ethylene oxide. castor oil. By pouring and finely distributing the solution in 100,000 parts by weight of water, an aqueous dispersion containing 0.02% by weight of the active substance is obtained.

EXAMPLE 16 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 of boiling point 210 to 280 ° C, and 10 parts by weight of the preparation product 33 moles of ethylene oxide to 1 mole of castor oil. By pouring and finely distributing the solution in 100,000 parts by weight of water, an aqueous dispersion containing 0.02% by weight of the active substance is obtained.

EXAMPLE 17 20 parts by weight of the active substance 2 are well mixed with 3 parts by weight of the sodium salt of diisobutylnaphthalene <c -sulfonic acid, 17 parts by weight of the sodium salt of a lignin sulfonic acid from a sulfite waste liquor and 60 parts by weight of powdered silica gel and ground in a hammer mill, of the mixture in 20,000 parts by weight of water, a spray liquid containing 0.1% by weight of the active substance is obtained.

EXAMPLE 18 3 parts by weight of compound 3 are thoroughly mixed with 97 parts by weight of finely divided kaolin. In this way, a powder containing 3% by weight of the active substance is obtained.

EXAMPLE 19 30 parts by weight of compound 4 are thoroughly mixed with a mixture of 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil sprayed onto the surface of this silica gel.

In this way, a preparation of the active substance with good adhesiveness is obtained.

EXAMPLE 20 40 parts by weight of the active substance 1 are thoroughly mixed with 10 parts of sodium salt of a phenolic sulfonic acid urea-formaldehyde condensate, 2 parts of silica gel and H8 parts of water. Stable dispersion is obtained.

By dilution with 100,000 parts by weight of water, an aqueous dispersion containing 0.04% by weight of active substance is thus obtained.

EXAMPLE 21 20 parts of the active substance 2 are thoroughly mixed with 2 parts of calcium salt of dodecylbenzenesulfonic acid, 8 parts of fatty alcohol polyglycol ether, 2 parts of sodium salt of a phenolic sulfonic acid urea-form aldehyde condensate and 68 parts of a paraffinic mineral oil. A stable, oily dispersion is obtained.