DD202977A5 - BIOCIDE MEDIUM - Google Patents

Abstract

The invention relates to biocidal agents for use in agriculture, in material and storage protection and in the hygiene sector. The aim of the invention is the provision of new agents with a strong fungicidal action and a broad spectrum of activity. According to the invention, imidazolyl-propionitriles of general formula I are used as active ingredient in the new compositions, in which R is optionally mono- or polysubstituted, identically or differently, by halogen, (C 1 -C 4 -alkyl), (C 1 -C 4) -Alkoxy, (& ind1! -C & ind4!) - alkylthio, trifluoromethyl or the nitro group-substituted aromatic hydrocarbon radical and R & ind1! (C & ind1! -C & ind10!) - alkyl, (C & ind3! -C & ind8!) - alkenyl, (& ind3! -C & ind8!) - alkynyl or an optionally mono- or polysubstituted by identical or different halogen, (C & ind1! -C & ind4!) Alkyl, (C & ind1! -C & ind4) - alkoxy, (C & ind1! -C & ind4!) -Alkylthio, trifluoromethyl or the nitro group substituted phenylalkyl radical.

Description

The invention relates to novel imidazolylpropionitriles containing biocidal agents, in particular having a fungicidal action *

Characteristic of the known technical solutions

Imidazolyl-propionitrile derivatives with fungicidal action are already known (DE-OS 2,604,47). However, these have a relatively narrow spectrum of action, which is unsatisfactory.

Object of the invention

The aim of the invention is the provision of new imidazolylpropionitriles, which open up a wide range of possible applications, in particular in the field of crop protection, and have a broad spectrum of fungicidal activity.

Explanation of the essence of the invention

The invention has for its object to develop new Imidazolylpropionitrile with the desired properties.

According to the invention are in the new biocidal agents as active ingredient imidazolyl-propionitrile of the general!

0 - R.

^η CT

/ 1 ? RQ? - ^ - ^Ä - 61 087 18

*. ^ I L · UOL · 23.3.83

applied in the

H an optionally mono- or polysubstituted by identical or different substituents from shark gen, (C ₁ -C) - alkyl, (O ₁ -C ^) - alkoxy, (O ₁ -C ₂ J _-) -Alky ITMO, trifluoromethyl or the nitro group substituted aromatic hydrocarbon radical and

("'E ₁ (O ₁ -C ₁₀ ) alkyl, (Cn-Cg) alkenyl, (Co-O ₈ ) alkynyl or an optionally mono- or polysubstituted by identical or different halogen, (C ₁ -C ₂ ,) - alkyl, (C ₁ -C ₂ J _- ) - alkoxy, (C ₁ -C ₂ J _- ) -AlkyltMo, irifluoromethyl or the nitro group substituted phenylalkyl radical and their acid addition salts with inorganic and organic acids «

The erfindungsgeniäßen compounds are biocidal in the broadest sense, but are characterized in particular by a fungicidal action, in which they surprisingly exceed known active ingredients analogous constitution and direction of action *

The fungicidal action surprisingly extends to fungi of various systematic position. In the treatment of aboveground plant parts they protect against wind-borne pathogens "Against seed-borne pathogens can be used the compounds for seed treatment. In addition, these act systemically, d, tu, they are from the roots of the plants z. B. added after introduction to the seed, are transported to the aerial parts of the plants and protect them against pathogens.

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Other effects include growth-regulating and bactericidal effects.

Because of the wide spectrum of activity recognized, the compounds are not only suitable for the protection of crop plants, but also for the protection of materials and for the control of human pathogenic and animal pathogenic microbes, before there are a wide range of possible applications.

Depending on the particular importance of the substituents, this results in typical applications in which the compounds exhibit outstanding effects. So they can be used as fungicides, plant growth regulators or bactericides »

In the compounds represented by the general formula I, for. B. mean:

H 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenol, 2-bromophenyl, 3-bromophenyl, 4-bromophenyl, 2-iodophenyl, 3-iodophenyl, 4- Iodophenyl, 2,3-dichlorophenyl, 2,4-dichlorophenyl, 3,4-dichlorophenyl, 2,6-dichlorophenyl, 2-methylphenyl, 3-ethylhexylphenyl, 4-methylphenyl, 2-thylphenyl, 3 Ethyl phenyl, 4-phenylethyl, 2-propylphenyl, 3-phenylphenyl, 4-propylphenyl, 2-isopropylphenyl, 3-isopropylphenyl, 4-isopropylphenyl, 2-butylphenyl, 3-butylphenyl , 4-butylphenyl, 2-sec, -butylphenyl, 3-sec, -butylphenyl, 4-sec, -butylphenyl, 2-tert-butylphenyl, 3-tert-butylphenyl, 4-tert-butyne phenyl, 2-methoxyphenyl, 3-ethoxy-2-phenyl, 4-methoxy

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phenyl, 2-ethoxyphenyl, 3-ethyl: xyphenyl, 4-ethoxyphenyl, 2-methylthiophenyl, 3-methylthiophenyl, 4-methylthiophenyl, 2-ethylthiophenyl, 3-ethylthiophenyl, 4-ethylthiophenyl, 2-irifluo: methylphenyl, 3-T3 ? ifluormethylphenyl, 4-Tsifluormethy! phenyl, 2-nitrophenyl, 3-mtrophenyl, U- nitrophenyl, 3-5 ¹ lu-or-4-methosyphenyl, 2-chloro-5-

^v - nitrophenyl, 4-chloro-2-fluorophenyl, 2,4,5-trimethoylphenyl

nyl or 5-chloro-2-nitrophenyl and

H ₁ (G ₁ -C ₁₀ ) -alkyl, eg, methyl, ethyl, propyl, butyl, pentyl, hesyl, heptyl, octyl, etonyl, decyl, isopropyl, 2,2-dimethylpropyl-1,3,3- Dimethyl '-butyl-2, (C ₃ -C ₈ ) -alkenyl, e.g. 2-buten-1-yl, 3-methyl-2-buten-1-yl, hexenyl, heptenyl, octenyl, (Co-Cg) -a-13sinyl, 3-propargyl, butynyl, pentynyl, hexynyl, heptynyl, octynyl, phenylalkyl, e.g., benzyl, 2-fluorobenzyl, 3-i ¹ luo2? benzyl, 4-fluorobenzyl, 2-chlorobenzyl, 3- ^ hlorbenzyl, 4 ~ chlorobenzyl, 2-bromobenzyl, 3-bromobenzyl, 4-bromobenzyl , 2,4-dichloro

{* - benzyl, 2,6-dichlorobenzyl, 3 _f 4-dichlorobenzyl, 2-methyl-

benzyl, 3-methylbenzyl, 4-methylbenzyl, 2-ethyltirobenzyl, 3-methylbenzyl, 4-nitrobenzyl, 2-trifluoromethylbenzyl ,. 3-tri-methylbenzyl, 4-trifluoroethylbenzyl, 2-methoxybenzyl, 3-methoxybenzyl, 4-4-ethylcyclobenzyl, 2-ethylbenzyl, 3-ethylbenzyl, 4-ethylbenzyl, 2-propylbenzyl, 3-propylbenzyl, 4-propylbenzyl, 2-butoxybenzyl, 3 Butoxybenzyl, 4-butenylbenzyl, 2-methylthiobenzyl, 3-methylthiobenzyl, 4-methylthiobenzyl, 2-ethylthiobenzyl, 3-ethylthiobenzyl, 4-ethylthiobenzyl, 2-butylthiobenzyl, 3-butylthiobenzyl, 4-butylthiobenzyl are for example

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Examples of inorganic and organic acids which may be used to form the acid addition salts include the hydrohalic acid, such as, for example, hydrochloric acid and hydrobromic acid, phosphoric acid, sulfuric acid, especially nitric acid, mono- and bifunctional carboxylic acids and hydroxycarboxylic acids, such as e.g. B, acetic acid, maleic acid, succinic acid, fumaric acid, tartaric acid, citric acid, salicylic acid, sorbic acid, lactic acid, and sulfonic acids, such as B. p-toluenesulfonic acid and 1,5-Naphthalindisulf onsäure.

These acid addition salts can be obtained by the usual salt formation processes, for example by dissolving a compound of formula I in a suitable solvent and adding the acid.

Of the compounds of the invention are characterized by a fungicidal action, in particular those in which in the general formula I, the radical

E is an optionally mono- or polysubstituted by identical or different halogen, (C, .- _C4) -alkyl, (C ^ -C ^ ₂₎ - alkoxy, CC.-C ₂ J _-) alkylthio, trifluoromethyl or Hitro group substituted phenyl radical and

E ₁ (C ₁ -C ₄ ) -alkyl, allyl, propargyl or an optionally mono- or polysubstituted by identical or different halogen, (C ₁ -C ₄ ) -alkyl, (C ₁ -C ₄ ) -alkoxy, (C C ₁ -C ₄ ) -alkylthio, trifluoromethyl or the methyl group substituted benzyl radical.

24 125 9 2 - ^ - ⁶ - ll ° ^a? _s : ^a

Preferably, such compounds are to be mentioned, in which

R is phenyl, 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, 2,4-dichlorophenyl, 2,6-dichlorophenyl, 3,4-dichlorophenyl, 2-fluorophenyl, 4-pluorophenyl, 4-bromophenyl, 2-methylphenyl , 4-methylphenyl, 4-methoxyphenyl, 4-mthenyl and

R 1 represents methyl, ethyl, propyl, isopropyl, pentyl, hesyl, allyl, propargyl, benzyl, 2-chlorobenzyl, 4-chlorobenzyl, 2,4-dichlorobenzyl, 3,4-dichlorobenzyl »

Clay outstanding effect are the following compounds of the invention:

2-n-butoxy-2- (2-chlorophenyl) -3- (imidazol-1-yl) -propionitrile, hydronitrate

2-n-Butoxy-2- (2-chlorophenyl) -3- (imidazol-1-yl) -propioni-

2-n-Butoxy- (4-chlorophenyl) -3- (imidazol-1-yl) -propionitrile, hydronitrate

2- (4-chlorophenyl) -3- (imidazol-1-yl) -2-n-propoxypropionitril,

Hydronitrate.

2- (2-Chlorophenyl) -3- (imidazol-1-yl) -2-n'-proposypropionitril ♦

The compounds according to the invention exhibit in particular fungicidal effects, but at the same time are distinguished by growth-regulatory effects in a number of crop plants.

As already mentioned, the compounds according to the invention are systemically transported in the plant.

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Accordingly, they develop their growth-regulatory effect both in applications via the soil and in a spray treatment,

Particularly noticeable are growth-inhibiting effects of cress and organic wool,

In addition to the aforementioned effects, the compounds of the invention also develop a bactericidal action, which allows further applications.

The compounds of the invention may be used either alone, in admixture with each other or with other active ingredients. If necessary, other crop protection or pest control agents may be added according to the desired purpose.

The marked active substances or mixtures thereof are expediently used in the form of preparations, such as powders, scattering agents, granules, solutions, emulsions or suspensions, with the addition of liquid and / or solid carriers or diluents and optionally wetting, tackifying, emulsifying and / or or dispersing agents applied. Suitable liquid carriers are z, B, water, aliphatic and aromatic hydrocarbons, such as benzene, toluene, xylene, cyclohexanone, isophorone, dimethyl sulfoxide, dimethylformamide, furthermore mineral oil fractions and vegetable oils,

Suitable solid carriers are mineral earths, z, 3, tonsil, silica gel, talc, kaolin, attapulgite, limestone,

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Silica and vegetable products, e.g. B. Flours »

Surfactants include: B. Calciumligninsulfonat, Polyo ^ Äthäthylenalkylphnenyl ether, naphthalenesulfonic acids and their salts, phenolsulfonic acids and '• their salts, formaldehyde condensates, Fettalkoholsulf ate and substituted benzenesulfonic acids and their salts.

If the active ingredients are to be used for seed dressing, it is also possible to admix dyes to give the seed which has been stained a clearly visible coloration *

The proportion of the active substance (s) in the various preparations can vary within wide limits. For example, the agents contain about 10 to 90% by weight of active ingredients, about 90 to 10% by weight of liquid or solid carriers and optionally up to 20% by weight of surface-active substances. The application of funds can be done in the usual way / ~ \, z. B. using water as a carrier in spray amounts of about 100 to 1000 liters / ha · An application of the funds in the so-called "low-volume" or "ultra-low-volume Yerfahren" is just as possible as their application in the form of so-called microgranules *

For the preparation of the preparations z. For example, the following ingredients are used:

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A, spray powder

a) 40% by weight of active compound 25% by weight of clay minerals 20 % by weight of silica 10% by weight of Zellpech

5% by weight of surfactants based on a mixture of the calcium salt of lignin sulfonic acid with alkylphenol polyglycol ethers

I)) 25% by weight of active compound 60% by weight of kaolin 10% by weight of silica

5% by weight of surfactants based on the i-sodium salt of N-methyl-N-oleyl-tauirine and the calcium salt of lignosulfonic acid.

c) 10% by weight of active ingredient 60% by weight of clay minerals 15% by weight of silica 10% by weight of cell pitch

5 Ge ® .-% surface-active substances based on the sodium salt of N-methyl-JT-oleyl-taurine and the galcium salt of lignosulfonic acid.

Paste

% By weight of active compound% by weight of sodium aluminum silicate, wt. 55 cetyl polyglycol ether with 8 moles of ethylene oxide wt.% Spindle oil

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10% w / w polyethylene glycol 23 parts water

G. Emulsion concentrate

25% by weight of active compound 15% by weight of cyclohexanone 55% by weight of xylene

5 wt .-% mixture of Fonylphenylpolyosyäthylen or Oalciumdodecylbenzolsulfonat.

The new compounds of the invention can be z. B. produce by Propionitrile the general formula

0-R ₁

EC-CH ₂ -Y II

CF

with imidazole of the formula HC - BH

HC CH

in the presence of a solvent and optionally in the presence of a base, wherein S and S ^. have the abovementioned meaning and Y is halogen or the optionally halogenated in the side chain AlkylsuIfo nylozy- or arylsulfonylosy radical.

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As the halogen, there may be mentioned, for example, chlorine, bromine or iodine, and as the alkylsulfonylosyl residue, methyl, ethyl, propyl and the trifluoromethylsulfonylosy group are suitable, and as the arylsulfonyloxy group, there are exemplified the benzylsulfonyloxy and p-toluenesulfonylosyl groups.

The Eeaktion can both with an excess of imidazole, optionally in the presence of a solvent, as well as with the addition of a strong base, for. B, sodium or potassium hydroxide. In addition, one can also use imidazole alkali metal instead of imidazole.

Solvents which are inert towards the reactants are preferably polar, aprotic, such as N, H-dimethylformamide, Ν, υ-dimethylacetanide, F-methylpyrrolidone, tetramethylurea, hexamethylphosphoric triamide and benzonitrile, but also higher-boiling aromatic and aliphatic ones Hydrocarbons such as toluene, chlorobenzene or xylene.

The Eeaktionstemperatur can be varied within wide limits "a temperature between 100 ⁰ C and 200 ⁰ C. Preferably, the reactions take place under normal or overpressure *

The imidazolyl-propionitriles according to the invention are in general. common almost colorless and odorless oils. The derived acid addition salts are colorless and odorless, crystalline compounds. "The oils dissolve poorly in water

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and more or less well in organic solvents like ζ. As alcohols, ethers or chlorinated hydrocarbons. The acid addition salts dissolve partly in water and well in polar organic solvents such as acetonitrile, HjN-dimethylformamide, lower alcohols, chloroform and methylene chloride.

Exemplary embodiment

The invention is explained in more detail below with reference to some examples. The following examples illustrate the preparation of the compounds of the invention.

example 1

3- (imidazol-1-yl) -2-phenyl-2-propoxy-propionitrile,

Hydro nitrate

(Compound Fr. 1)

15 g (0.053 mol) of 3-Methylsulfonylo2y-2-phenyl-2-propo2ypropionitrile and 17.89 g (0.263 mol) of imidazole were kept under exclusion of moisture with the addition of 1 ml of dimethylformamide for 16 h at 140 ⁰ G.

Ss is poured onto ice water, extracted twice with 75 ml of methylene chloride, the methylene chloride phase · washed twice with water, dried with magnesium sulfate and concentrated by filtration after filtering off the drying agent in vacuo. The residual dark oil is dissolved in isopropanol and treated with slightly more than the theoretical amount of 100% nitric acid, to complete the precipitation

4 1259- 2

a little diethyl ether, »The precipitated product is filtered off with suction and dried. Yield: 12 g = 71 % of theory 168 to 171 ⁰ C (decomposition)

Example 2

3- (imidagol-1-yl) -2-phenyl-2-propyl-7-propionitrile (compound no. 2)

6.2 g (0.0195 mole) of the hydraulic nitrate is dissolved in methanol and basified with dilute with ice bath cooling gestellt- A m m oniaklösung, After dilution with water is extracted with Bssigsäureäthylester, the organic phase washed with water and then dried with magnesium sulfate. Each filtration is concentrated in vacuo. It leaves an oil, which is dried in vacuo

Yield: 4.85 g = 97% of theory n _r 31 = 1.5260

In an analogous manner, the following compounds according to the invention can be prepared ·

Name of the connection Physical constant

3. 2-Butoxy-3- (imidazol-1-yl) -2-phenyl- Pp .: 155 to -propionitrile, hydronitrate 157 ⁰ C (Z)

4. 2-Butoxy-3- (imidazol-1-yl) -2-phenyl-n _D 39 = 1.5208 propionitrile

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Harne of the compound Physical

constant

5. 2-Allylosy-3- (imidazol-1-yl) -2-phenyl- Mp .: 162 "to propionitrile, hydronitrate 164 ⁰ C (Z)

6. 2-Allylosy-3- (imidazol-1-yl) -2-phenyl-n _D 33 = 1.5402 propionitrile

7. 2-Ethoxy-3- (iiaidazol-1-yl) -2-phenyl-5p ,: 182 "to propionitrile, hydronitrate 186 ⁰ C (Z)

8. 2-Ethoxy-3- (imidazol-1-yl) -2-phenyl-n _D 44 = 1.5247 propionitrile

9 »3- (imidazol-1-yl) -2-methoxy-2-phenyl-ip. 189 bis

propionitrile, hydronitrate 191 ⁰ C (Z)

10. 3- (imidazol-1-yl) -2-methosy-2-phenyl-propionitrile m.p .: 57 to 60 ⁰ C.

11. 2- (2-chlorophenyl) -3- (imidazol-1-yl) -2-prop _e mp: 162 to oxypropionitril, hydronitrate 165 ⁰ C (Z)

12. 2-Butoxy-2- (4-chlorophenyl) -3- (iaiidasol-1-yl) - m.p .: 178 to propionitrile, hydronitrate 181 ⁰ C (Z)

13. 2-Butosy-2- (2-Ghlorphenyl) -3- (imidazol mp .: 177 to 1 yl) -propionitrile, hydronitrate 178 ⁰ C (Z)

14. 2-Allylo3y-2- (2-chlorophenyl) -3- (imidazol mp .: 153 to 1 yl) -propionitrile, hydronitrate 155 ⁰ C (Z)

15. 2- (4-chlorophenyl) -3- (iaidazol-1-yl) -2- m.p .: 174 to propoxy-propionitrile hydronitrate 177 ⁰ C (Z)

16. 2-Allylosy-2- (4-chlorophenyl) -3- (imidazole-mp: 152 to 1-yl) -propionitrile, hydronitrate 155 ⁰ G (Z)

17. 2- (2-chlorophenyl) -3- (imidazol-1-yl) -2- n _D 41 = 1.5343 propoxy-propionitrile

18. 2-Butoxy-2- (4-chlorophenyl) -3- (imidazole-1-n_j41 = 1.5288 yl) -propionitrile

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Name of the connection Physical constant

19. 2-Buto2y-2- (2-chlorophenyl) -3- (imidazol n _D 41 = 1.5329 1-yl) - propionitrile

20. 2-Allylo2y-2- (2-chlorophenyl) -ii! Iida2ol-1- n _D 41 = 1.5490 yl) -propionitrile

21. 2- (4-Chlorophenyl) -3- (imidazol-1-yl) -2-> 1 → 41 = 1.5337 propan-propionitrile

22. 2-Allylo2 ^ -2- (4-chlorophenyl) -3-imidazole-2 ^ 41 = 1,5476 1-yl) -propionitrile

23. 2-Benzyloxy-3- (iniidazol-1-yl) -2- phenylpropionitrile, hyduonitrate

24 .. 2-Benzylosy-3- (imidazol-1-yl) -2-phenylpropionitrile

25. 3- (1-Bis-L-lol-1-yl) -2-isopropyloxy-2-phenylpropionitrile, hydronitrate

26. 3- (imidazol-1-yl) -2-isopropyl-2-phenylpropionitrile

27. 2- (4-chlorophenyl) -2-he2ylosy-3- (imidazol-1-yl) -propionitrile, hydronitrate

28. 2- (4-chlorophenyl) -2-hexyloxy-3- (iinidazol-1-yl) -propionitrile

29. 2-Allylosy-3- (imidazol-1-yl) -2- (2-ethylphenyl) -propionitrile, hydronitrate

30. 2- (3,4-dichlorophenyl) -3- (iinidazol-1-yl) -2-propylpropionitrile, hydronitrate

31. 2-Butoxy-2- (2,4-dichlorophenyl) -3- (imidazol-1-yl) -propionitrile, hydronitrate

32. 2-Allylosy-2- (2,4-dichlorophenyl) -3- (imidazol-1-yl) -propionitrile, hydronitrate

Mp. • • 0 0 0 0 0 0 0 • • O • * O 166 to , 5638 , 5254 , 5197 168 * • • «« σ (ζ) to to ⁰ G = 1 σ (ζ) σ (ζ) Mp. * • 165 ₌ 1 = 1 to 168 152 160 Z) n _D 4 to φ. 169 Z) 154 σ ( to 148 z). Mp. σ ( (Z) 158 Mp. G ( 170 Mp. 150 Mp. 160

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TTame of the "Connection Physical

constant

33. 2-Äthozy-2 -. (3, ⁱ ^ -dichlo2Γphenyl) -3- (imida- mp.: 105 bis-zol-1-yl) -propionitr_l, hydronitrate 106 ⁰ C (Z)

34. 2-Allyloxy-3- (imidazol-1-yl) -2- (2-methyl-- n _D 40 = 1.5383 phenyl) -piopionitril

35. 2- (3, ^z i-Dichlorophenyl) -3- (iiaidazol-1-yl) -2-n _D 40 = 1.5360 propyl propionitrile

36. 2-Allyloxy-2- (3,4-dichlorophenyl) -3- (iniidan _D 40 = 1.5500 zol-1-yl) -propionitrile

37. 2-But027-2- (2,4-dichlorophenyl) -3- (imidazol n _D 4-0 = 1.5381 1-yl) -p £ opion_tril

38. 2-Allylozy-2- (2,4-dioxorophenyl) -3- (iniidan _D 40 = 1,5531-zol-1-yl) -pxopionitrile

39. 2-ethoxy-2- (3,4-dichlorophenyl) -2- (imidazol n _D 40 = 1.5372 1-yl) -propionitrile

40. 3- (imidazol-1-yl) -2-phenyl-2- (1,2,2-tuimethyl-FP .: 168-propyl) -propionitrile, hydronitrate 173 ⁰ C (Z)

41. 3- (Iaidazol-1-yl) -2- (2-methoxy-ethyl) -2- m.p .: 158 to phenyl-propionitrile, bydronitrate

42. 2- (2,2-Dimethyl-propyl) -3- (imidazol-1-yl) -2-phenylpropionitrile, hydronitrate

43. 2- (2,2-Dimethyl-propoxy) -3- (iinidazol-1-yl) -2-phenylpropionitrile

44. 2- (2-fluorophenyl) -3- (imidazol-1-yl) -2-propoxy-propionitrile, hydroxonitrate

45. 2-Butoxy-2- (2-fluorophenyl) -3- (imidazol-1-yD-propionitrile, bydronitrate

46. 2- (4-Fluoro-2-phenyl) -3- (izaidazol-1-yl) -2-propoxy-puopionitrile, hydronitrate

160 G ⁰ (Z) σ 170 to mp .: 168 to ⁰ C (Z) 171 ⁰ C (Z) 173 to mp .: 89 to. ⁰ C (Z) 91 ° 150 to Fp " ⁰ C (Z) 172 mp .: 176 mp .: 152

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Harne of the compound Physical

constant

47. 2-Butoxy-2- (4-fluorophenyl) -3- (imidazole EP: 162 to 1-yl) propionitrile, hydronitrate 165C

48. 2-Allyloxy-2- (2-fltiorophenyl) -3- (imidazole. Pp .: 169 to 1-yl) -propionitrile, hydronitrate 171 ⁰ C (Z)

49. 2-Ethoxy-2- (2-fluorophenyl) -3- (inimidazole-1-PP: 172 to yl) -propionitrile, hydronitrate 175 ⁰ C (Z)

50. 2- (2-fluorophenyl) -3- (iiaidazol-1-yl) -2- m.p .: 177 to methoxy-propionitrile, Hydronitiat 179 ° C (Z)

51. 3- (Iiaidazol-1-yl) -2-phenyl-2- (i, 2,2-tri- Pp .: 113 to methyl-proposyO-propionitxil 116 ⁰ C.

52. 3- (imidazol-1-yl) -2- (2-niethosyl-ethhoxy) -2-n _D 40: 1.5212 phenylpropionitrile ν

53. 2- (2-Plomo2-phenyl) -3- (imidazol-1-yl) -2- ^ 40: 1.514-3 propoxy-propionitrile

54. 2-Butoxy-2- (2-fluoro-phenyl) -3- (imidazol-1-yl) - ^ 40: 1.5108. propionitrile.

55. 2- (4-Pluphenyl) -3- (imidazol-1-yl) -2-n _D 40: 1,5115 propoxy-propionitrile

56. 2-Butoxy-2- (4-fluorophenyl) -3- (imidazol-1-n _D 40: 1.5085 yl) -p 2 -opinitrile

57. 2- (2-Pluorophenyl> 3-CLmidazol-1-yl) -2-n _D 40: 1,5280 methoxy-propionitol

58 x 2-ethyl-2- (2-fluorophenyl) -3- (imidazole-1-n _D 40: 1,5187 y1) -propionitrile

59. 2-Allylosy-2- (2-fluorophenyl) -3- (iiaidazole- ^ 40: 1,5258 1-yl) -propionitrile

60. 2-Allyloxy-2- (4-fluorophenyl) -3- (imidazole-PP: 159-1-yl) -propionitrile, hydronitrate 161 ⁰ G (Z)

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ifame of the connection Physical

constant

61. 2-Äthozy-2- (4-fluorophenyl) -3- (imidazole-Fp .: 182 to 1-yl) -propionitrile, hydronitrate 184 ⁰ C (Z)

62. 2- (4-fluorophenyl) -3- (imidazol-1-yl) -2- mp ..: 194 to methoxy-propionitrile hydronitrate 196 ⁰ C (Z)

63. 2-lthoxy-2- (4-fluorophenyl) -3- (imidazole-1-Fp: 54 to yl) -propionitrile 57 ⁰ C

64. 2- (4-fluorophenyl) -3- (imidazol-1-yl) -2- m.p .: 88 ⁰ G methoxy-propionitrile

65 ^ 2-Allyloxy-2- (4-fluorophenyl) -3- (imidazole- ^ O: 1,5219 1-yl) -propionitrile

66. 2-Decyloxy-3- (imidazol-1-yl) -2-phenylpropionitrile, hydronitrate

67. 2- (3,3-Dimethylbutoxy) -3- (imidazol-1-yl) -2-phenyl-propibonitrile, hydronitrate

68. 3- (Iioiclazol-1-yl) -2-octyloxy-2-phenylpropionitrile

69. 2- (3,3-dimethoxybutoxy) -3-ojimidazol-1-yl) -2-phenyl-propionitrile

70. 2- (4-Bromophenyl) -2-butoxy-3- (imidazol-1-yl) -propionitrile, hydronitrate

71. 2- (4-Bromophenyl) -3- (imidazol-1-yl) -2-propoxy-propionitrile, hydronitrate

72. 2- (4-Bromophenyl) -2-hezyloxy-3- (imidazol-1-yl) -propionitrile, hydronitrate

73. 3- (imidazol-1-yl) -2- (2-methylphenyl) -2-propyl-propionitrile, hydronitrate

74. 2-Hesyloxy-3- (imidazol-1-yl) -2- (2-methylphenyl) -propionitrile, hydronitrate

Fd .: 126 to 128 ° G (Z) mp .: 195 to 198 ° G (Z) n _D 40: 1.5055 n _D 40: 1.5093 Mp: 171 to 174 ° G (Z) mp .: 162 to 165. ° G (Z) mp .: 135 to 138 ° G (Z) mp .: 180 to 183 ° G (Z) Fo. : 170 to 173 ° G (Z)

241259 2 -

61 087 18 23.3.83

Name of the connection Physical constant

47. 2-Butox7-2- (4-fluorophenol) -3- (imidazole ZP: 162 to 1-7 l) -propionitrile, H7dronitrate 165 ⁰ G

48. 2-All-7-oxy-2-C2-fluoro-phenyl) -3- (imida-2-ol-mp: 169 to 1-7 l) -propionitrile, bydronitrate 171 ⁰ C (Z)

49. 2-lthoxy-2- (2-fluorophenol) -3- (imidazole-1-Fp ,:172 to yl) -propionitrile, H7dr0m.trat 175 ⁰ G (Z)

50. 2- (2-fluorophenol) -3- (imidazole-1-7l) -2-Fp ,: 177-methoxy-propionitrile, hydronitrate 179 G (Z)

51. 3- (imidazole-1-7l) -2-phen7l-2- (1,2,2-tri-Fp, 113 to meth.7l-propos7) -propionitrile 116 ⁰ G

52. 3- (imidazole-1-7l) -2- (2-methos7-ethhos7) -2-n-p.40: 1-5212 phenolpropionitrile

53. 2- (2-Fluo-biphenyl) -3- (imidazole-1 -7I) -2- ^ 40 :. 1.5143 propox7-propionitrile

54. 2-Butos-7-2- (2-fluoropienl) -3- (imidazol-1 -7l) - ^ 40: 1.5108 propionitrile

55. 2-C4-Fluo2-phenyl) -3- (imidazol-1-yl) -2-n _D 40: 1,5115-propano-propionitrile

56. 2-Butos-2- (4-fluorophenol) -3- (imidazole-1-40: 1,5085 7l) -propionitrile

57. 2- (2-fluorophenyl) -3- (imidazole-1-7l) -2- ⁿ D ^40: 1 → 5280 methoxy-7-propyl trimethane

58. 2-etho27-2- (2-fluorophenol) -3- (imidazole-1-n _D 40: 1.5187 7I) -propionitrile

59. 2-All7lox7-2- (2-fluorphen7l) -3- _(imidazol-p n 40: 1.5258 1-7I) propionitrile

60. 2-All7lo27-2- (4-fluorophyllene-7l) -3- (imidazole-mp: 159 to 1-7 l) -propionitrile, H7dronitrate 161 ⁰ G (Z)

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$ iame the connection

61. 2-ethoxy-2- (4-fluorophenyl) -3- (iiiiidazole)

1-yl) -propionitzil, hydronitrate

62. 2- (4-Fluorophenyl) -3- (imidazol-1-yl) -2-methoxy-propionitrile, hydronitrate

63. 2-lthosyl-2- (4-fluorophenyl) -3- (iinidazol-1-yl) -propionitrile

64. 2- (4-Plnorphenyl) -3- (imidazol-1-yl) -2-methoxy-propionitrile

65 * 2-allylosy-2- (4-fluorophenyl) -3- (imidazol-1-yl) -piopronitrile

66. 2-Decylocy-3- (imidazol-1-yl) -2-phenylpropionitrile, hydronitrate

67. 2- (3,3-Diynethylbutoxy) -3- (iaiidazol-1-yl) -2-phenyl-propionitrile, hydronitrate

68. 3- (imidazol-1-yl) -2-octyl-2-phenylpropionitrile

69. 2- (3,3-Dimetho-27-butoxy) -3-midazol-1-yl) -2-phenyl-propionitrile

70. 2- (4-Bromophenyl) -2-butoxy-3- (imidazol-1-yl) -propionitrile, hydronitrate

71. 2- (4-Bromophenyl) -3- (imidazol-1-yl) -2-propyl-propionitrile, hydronitrate

72. 2- (4-Bromophenyl) -2-hexyloxy-3- (2-iidazol-1-yl) -propionitrile, hydroxonitrate

73. 3- (imidazol-1-yl) -2- (2-methylphenyl) -2-propyl-propionitrile, eydronitrate

74. 2-Hesylosy-3- (imidazol-1-yl) -2- (2-methylphenyl) -propionitrile, hydronitrate

physical : 182 to : 126 to : 171 to constant ⁰ C (Z) ⁰ C (Z) G ⁰ (Z) Mp. : 194 to : 195 bis : 162 to 184 ⁰ C (Z) ⁰ C (Z) ⁰ C (Z) Mp. : 54 to O: 1.5055 : 135 to 196 ⁰ C n _D 40: 1,5093 ⁰ C (Z) Mp. : 00 0 Mp. : 180 to 57 γθ: 1.5219 174 ⁰ C (Z) Mp. Mp. Mp. : 170 bis 128 165, ⁰ C (Z) Mp. Mp. 198 138 Mp. 183 Mp. 173

241259 2

61 087 18 23.3.83

Name of the connection Physical

, Otherwise ante

75. 2- (4-B-Comphenyl) -2-butoxy-3- (imidazole-1-n _D 40: 1.5405 yl) -piopionitrile

76. 2- (4-Broiirphenyl) -3- (imidazol-1-yl) -2-n _D 40: 1.5 * 18 propoxy-propionitrile

77. 2- (4-Bromophenyl) -2-hesylosy-3- (imidazole-1: 4-0: 1,5274 1-yl) -propionitrile

78. 2-Butoxy-3- (imidazol-1-yl) -2- (2-methyl-N, O: 1.5248phenyl) -propionitrile

79. 2-Butoxy-3- (imidazol-1-yl) -2- (2-methyl-Fp .: 184-phenyl) -propionitrile, hydronitrate 186 ⁰ G

80. 2-He2yloxy-3- (imidazol-1-yl) -2- (2-niethynyl- _D 40: 1,5163phenyl) -propionitrile

81. 2-Decylosy-3 - (imidazole-1- ^ 1) -2-phenyl- ^ 40: 1,5020 propionitrile

82. 3- (imidazol-1-yl) -2- (2-methylphenyl) -2-n _D 40: 1,5276 propylpropionitrile

83. 2-Butoxy-2- (3-chloro-2-phenyl) -3- (imidazol-1-n _D 40: 1,5282 yl) -propionit

84 »2- (3-Gnlorophenyl) -2-hexylosy-3- (imidazole-mp: 162 to 1-yl) -piopionitiil, hydronitrate 165 ⁰ C (Z)

85 "2-Decylosy-3- (imidazol-1-yl) -2- (2-methyl-Fp: 151-phenyl) -propionitiil, hydronitrate 155 ⁰ C (Z)

86. 3- (1-Diimidazol-1-yl) -2- (2-methylphenyl) -2- 1 → 40: 1.5173 octyloxy-propionitrile

87. 2-Deoxylosy-3- (imidazol-1-yl) -2- (2-methyl-40: 1,5139phenyl) -propionitrile

88. 2-Butoxy-3- (imidazol-1-yl) -2- (4-methoxy-Fp: 163-phenyl) -propionitiil, hydronitrate 167 ⁰ G (Z)

LH S L O Ό L -? & - Ζ ° - 61 087 18

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Name of the compound Physical « Eonstante

89. 2-Butoxy-3- (imidasol-1-yl) -2- (4-methoxy- _D, O: 1.5228phenyl) -propionitrile

90. 2- (4-Chlorophenyl) -2-hesylosy-3- (imidazole, mp: 195 bis, "1-yl) -propionitrile, hydrogen zalate 197 ⁰ C (Z)

91. 2- (4-chloro-2-phenyl) -2-he2yloxy-3- (imidazole-5p .: 158-1-yl) -p 2 -opinitrile, hydrogen sulfate 163 ⁰ C (Z)

(Z) = decomposition

The starting materials to be used as 3-aryl- or 3-alkyl-sulfonylo2y-propionitriles of general formula II with Y in the meaning aryl or Alkylsulfonylosy are not yet described in the literature. These aryl- or alkylsulfonyloxy compounds of the general formula II are obtained by reacting the methods which are known in some cases or are known per se (cf., for example, Hubin et al., JACS 67, 192 f C- (194-5)} Hess et al., Ber et al., Ges. 50, 394 (1917)) accessible phenylacetonitrile of the general formula III

0 - E I

Z-CH III

CN

wherein Z and H have the meaning given for formula I, hydroxymethylated according to methods known per se and the thus obtained 3-hydroxypyrionitriles of the general formula

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23/3/53

O - E I

ZC-CH ₂ -OH IY

err

wherein Z and R have the meaning given for formula I, with suitable sulfonic acid derivatives, isie z, B. SuIfonsäurechloride, optionally with the addition of an acid binder, reacted »The hydrosymethyl compounds of general formula IT are not yet known from the literature.

The literature known 3-halo-propionitriles of the general formula H with T in the meaning of halogen is obtained by reacting the above-mentioned phenylacetonitrile of general formula III with dihalomethanes by methods known per se.

The following describes the preparation of a starting product.

3 ^ 1ethylsulfonyl-2-phenyl-2-propoxy-propionitrile

27 g (0.154 mol) of 2-phenyl-2-propo: xy-acetonitrile are dissolved in 120 ml of pyridine and mixed with 18.5 g (0.614 mol) of paraformaldehyde. Tetrabutylammonium hydrosulfide (TBAOH) is added to this suspension under ice-cooling, 7.7 ml, and stirred vigorously for 17 h. The reaction mixture is poured onto sis-water and extracted twice with ether. Then you wash

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the ether phase twice with aqueous sodium chloride solution and dried with magnesium sulfate, after filtering off the drying agent and rotary evaporation in vacuo remains a colorless oil, which turns out to be uniform thin-layer chromatography and can be further processed without further purification

 ('Yield: 28.4 g = 90% of theory

, 3-hydroxy-2-phenyl-2-propoxy-propionitrile

28 g (0.136 mol) of 3-hydroxy-2-phenyl-2-propoxy-propionitrile are dissolved in 200 ml of toluene and treated with 19.5 g (0.171 mol) of methanesulfonyl chloride. At 10 ⁰ C, 18.6 g (0.184 mol) of triethylamine are added dropwise. The mixture is stirred for 30 minutes at room temperature, filtered from the precipitated triethylamine hydrochloride and concentrated. The residue is taken up in Ither, washed with dilute HCl solution, water and sodium bicarbonate solution and twice more with water. It is dried with magnesium sulfate, the drying agent is filtered off and concentrated. The oily residue is in Va - ^(_,: uum dried He proves purely as thin layer chromatography..

Yield: 32.27 g = 86% of theory n _D = 1.5000 3-methylsulfonyl-2-phenyl-2-propoxy-propionitrile

The following exemplary embodiments serve to explain the possible uses of the compounds according to the invention, which took place in the form of the above-mentioned preparations.

2A1 ? 5 9 2

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Example 3

Effect of seed treatment against Eelminthosporium spec., On barley.

Barley seed with natural infestation by Helminthosporium gramineum was treated with urine or as described in the table (treated in plant pots with soil and left to germinate at temperatures below +16 ⁰ C. After emergence, the seedlings were illuminated daily for 12 hours with artificial light Eirssa 5 weeks, all accumulated plants, as well as the plants attacked by fungi, were counted per test subject

 The fungicidal effect is obtained as follows:

100 - 100 · infestation _{= 3 %} infestation in untreated

The compounds were present as 20% wettable powder.

Inventive g Active substance % action

Verbinduno; Hr «100 kg of seed

1 50 95.6

2 50 100

3 50 100

4 50 100

5 50 100

6 50 100

7 50 100

8 50 100

9 50 100 10 50 100

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Active ingredient % Effect Compound No. 100 kg Seed

100 100 100 100 100 100 100 100 100 100 100

11 50 12 50 13 50 14 50 15 50 16 50 17 50 18 50 19 50 20 50 21 50 Comparative, dt el Me thoxyethyl-Hg- 2 ' silicate Example 4 O

Effect of prophylactic foliar treatment against Erysiphe cichoracearuin on greenhouses in the greenhouse "Dripped with the indicated concentrations of active ingredient sprayed Kirbisjungpflanzen were after drying the spray coating by dusting dry powdery mildew spores of Erysiphe cichoracearuin and incubated together with inoculated untreated control plants in a greenhouse at 24 ⁰ C. After one week, the affected powdery mildew area was estimated in% of the total leaf area. The fungicidal activity was calculated as follows:

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_100-100 infestation treated _{=% active #} infestation in untreated

The substances were formulated as 20% wettable powders,

Wirkstoffkon- invention% operative connection ITr. concentration %

0,025 100 0.005 100 0.001 100 0,025 100 0.005 100 0.001 100 0,025 100 0.005 100 0.001 100 0,025 100 ' 0.005 100 0.001 100 0,025 100 0.005 100 0.001 100 0,025 100 0.005 100 0.001 100 0,025 100 0.005 100 0.001 100 0,025 100 0.005 100 0.001 100

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Inventive compound no.

10 11 12 13 14

15 16 17 18

Wirkstoffkon % Effect concentration% 0,025 100 0.005 100 0.001 100 0,025 100 0.005 100 0.001 100 0,025 100 0.005 100 0.001 100 0,025 100 0.005 100 0.001 100 0,025 100 0.005 100 0.001 100 0,025 100 0.005 100 0.001 -87 0,025 100 0.005 100 0.001 100 0,025 100 0.005 100th 0.001 100 0,025 100 0.005 100 0.001 100 0,025 100 0.005 100 0.001 100

23/3/83

According to the Invention Active Ingredient Effect Hr. cent rati ο_n_%

0.025 '100

0.005 100

0.001 100

0.025 100

0.005 100

0.001 100

0.025 100

0.005 100 0.001 x 100

0.001 100

0,0002 100

'0.001 100

0,0002 100

0.001 100

0,0002 100

0.001 100

0,0002 100

, 0.001 100

0,0002 100

0.001 100

0,0002 100

0.001 100

0,0002 100

0.0Oi 100

0,0002 100

0.001 100

0,0002 100

0.001 1QO

0,0002 100

1259 2 - * - * <- 61 Οδ? 18 23.3.83

Binding Compound No. 32 33

35 36 37 38 39 40 41 42 43 44 45 46

Wirkstoffkon % Effect concentration% 0,0Oi 100 0.0002 100 0.001 100 0.0002 100 0.001 100 0.0002 100 0.001 100 0.0002 100 0.001 100 0.0002 98 0.001 100 0.0002 100 0.001 100 0.0002 100 0.001 100 0.0002 100 0.001 100 0.0002 100 0.001 100 0.0002 100 0.001 100 0.0002 100 0.001 100 0.0002 100 0.001 100 0.0002 100 0.001 100 0.0002 100 0.001 100 0.0002 100

24 125 9 61 087 18 23.3.83

Inventive compound no.

Wirkstoffkon % Effect concentration % 0.001 100 0.0002 100 0.001 100 0.0002 100 0.001 100 0.0002 100 0.001 100 0.0002 100 0.001 100 0.0002 100 0.001 100 0.0002 100 0.001 100 0.0002 100 0.001 100 0.0002 100 0.001 100 0.0002 100 0.001 100 0.0002 100 0.001 100 0.0002 100 0.001 100 0.0002 100 0.001 100 0.0002 100 0.001 100 0.0002 100 0.001 100 0.0002 100

47 48 49 50 51 52 53 54 55 56 57 58 59 60 61

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_{61 087 18}

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Invention compound ΪΓΐ.

62 63 64 65 66 67 68 69 70 71 72 73 7475

Wirkstoffkon % Ecom concentration % 0.001 ' 100 0.0002 100 0.001 100 0.0002 100 0.001 100 0.0002 100 0.001 100 0.0002 100 0.0025 100 0.00025 100 0.0025 100 0.00025 100 0.0025 100 0.00025 100 0.0025 100 0.00025 100 0.0025 100 0.00025 100 0.0025 100 0.00025 100 0.0025 100 0.00025 100 0.0025 100 0.00025 100 0.0025 100 0.00025 100 0.0025 100 0.00025 100

4 1259 2

61 087 18 23.3.83

! rfindungsgemäße Wirkstoffkon % Effect Connection no. concentration% 76 0.0025 100 0.00025 100 77 0.0005 99 0.00005 100 78 0.0005 100 0.00005 100

Example 5

Effect of foliar treatment against Piricularia oryzae on hot seedlings in the greenhouse.

Young corn plants were sprayed to drip point with the substance concentration indicated in the table. After drying the spray coating, the treated plants and untreated control plants were inoculated by spraying a suspension of spores (about 200,000 per ml) of the leaf spot pathogen Piricularia oryzae and incubated moist at +25 to +27 ⁰ G in a greenhouse.

After 5 days, the percentage of leaf area was determined. From these infestations, the fungicidal action was calculated as follows:

100 -

100 * Infestation Treated infestation in untreated

=% Effect

The substances were formulated as 20% wettable powders,

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Inventive

11 12 13 14 15

16 17 18 19 20 21

Wirkstoffkon % Effect concentration% 0.1 89 0,002 63 0.1 97.3 0,002 89 0.1 94.5 0.02 70 0.1 95 0.02 77.5 0.1 95 0.02 80 0.1 95 0.02 65 0.1 92.5 ' 0.02 70 0.1 95 0.02 80 0.1 98 0.02 65 0.1 95 0.02 55 0.1 97.5 0.02 90 0.1 95 0.02 80 0.1 92.5 0.02 65 0.1 95 0.02 85 0.1 95 0.02 80

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Example 6

Effect of prophylactic foliar treatment against Botrytis aea on tomato plants in the greenhouse.

Young tomato plants were sprayed to drip point with the active ingredient concentration indicated in the table. The treated plants were dried and sprayed inoculated by spraying a suspension of spores (about 1 million ml of fruit juice solution) of the gray rot pathogen Botrytis cinerea and moist at about 20 G im Greenhouse incubated. After the collapse of the untreated plants (= 100% infestation), the degree of infestation of the treated was determined. The fungicidal activity was calculated as follows:

100 - 100 * Infestation Treated _{= % ¥ i: Ektmg} Infestation in Untreated

The compounds of the invention were present as 20% formulations.

Inventive Wirkstoffkon-% effect

Connections No. Center%

3 12 13 14 15

0,025 95 0,025 80 0,025 90 0,025 95 0,025 60 0,025 85

1259 2 -x- ^JY -61087

23/3/83

concentration% 70 0,025 90 0,025 90 0,025 95 0,025 90 0,025 80 0,025

Inventive Wirkstoffkon-% effect

Connections Hr.

Comparative Experiment 1- (4-chlorophenoxy) -3,3-dimethyl-1- (i, 2,4-triazol-1-yl) -2-butanone 0.025

Example 7

Effect of prophylactic foliar treatment against Plasmopara viticola on grapevine plants in the greenhouse. Young grapevine plants with about 5 to 8 leaves were sprayed dripping wet with the specified concentration, sprayed after drying of the spray coating with an aqueous slurry of sporangia of the fungus (about 20 000 per ml) leaf underside and immediately in a greenhouse at 22 to 24 ⁰ C and possibly water vapor saturated Atmosphere incubated.

From the second day the humidity was reduced to normal for 3 to 4 days (30 to 70 % saturation)

4 12 5 9 2 '#? - ^3f - . 61 087 18

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and then kept at water vapor saturation for one day. Subsequently, the percentage of mushroom-affected area of each leaf was noted, and the average of each treatment was calculated to determine the IT fungicide effect, as follows:

100-100 ·· infection in _{treated% = Wi: rkmi} g infestation in ünbehandelt

The substances were formulated as a 20% spray powder «

Inventive Wirkstoffkon-% action Terbindungen no. Concentration%

11 0,025 89 12 0,025 93.3 13 0,025 92.5 14 0,025 73 15 0,025 95.4 16 0,025 82 17 0,025 92.7 18 , 0,025 94.6 19 0,025 95.5 20 0,025 65 21 0,025 81 Example 8

In the laboratory, plant seeds were treated with an aqueous emulsion of the compositions according to the invention.

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Concentration of the active ingredients in the emulsion was 100 ppm, and a slide was placed in a 200 ml glass vial with 10 ml of active ingredient emulsion and filter paper was mounted on the slide, so that the filter paper was soaked with the solution Cress seeds were evenly distributed, then the lid of a Petri dish was placed on the neck and two glass vials were prepared for each substance.

For evaluation, the sprouts and roots were measured after 7 days from germinated seeds.

In the table, the values are set in relation to the control and expressed in percentages.

It can be seen that the compounds according to the invention exert a strong influence on cress and shoot growth in cress. This becomes clear in the promotion (> 100%) or inhibition (<100 %) of the individual parts.

invention wax turn in% Connections Fr. Soros root 1 71 57 2 36 71 3 67 100 4 · 67 57 5 67 43 6 67 71 7 83 86 8th 67 71

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Erfindtingsgemäße Growth in% root Yelbindungen Hi. shoot 71 9 67 71 10 83 67 11 100 22 12 50 22 13 50 78 14 100 44 15 67 44 16 50 56 17 83 67 18 67 56 19 100 78 20 83 44 21 50 57 22 50 Example 9

Cotton soil under greenhouse conditions "dressed up to cotyledon stadium"

The compounds according to the invention were sprayed onto the plants in quantities of 1 and 2 kg of active ingredient / ha. 3 weeks after the application, the total length of the plants and the length of the first internode were measured. In the table, the results are given in the form of percentages as a comparison to the control. A reduction of the growth, which in Hegel is stronger than that of the Comparative is.

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-3e -

61 087 18 23.3.83

Kg of active substance according to the invention substance / ha overall length Length of 1, Ye rb indungen Fr. 1 of plants% Internodes% 11 2 75 32 1 46 9 12 2 83 60 1 59 19 13 2 69 , 34 1 37 4 14 2 82 57 1 65 42 15 2 83 66 1 60 42 16 2 87 66 1 69 42 17 2 60 32 1 41 9 18 2 69 15 1 52 13 19 2 48 15 1 45 9 20 2 75 43 1 52 9 21 2 95 72 1 71 34 22 2 100 70 55 62 comparison means 2-Ghloräthylentri- methyiammonium- 1 chloride 2 52 23 44 23

4Γ259 2 - j ^ - 2 * - 61 087

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Example 10

Effect of seed treatment against cereal powdery mildew Erysiphe graminis on barley "Seed of spring barley was untreated or pickled with 100 g of active ingredient / 100 kg sown in plant pots with soil and left at temperatures around 20 ⁰ C in the greenhouse germination, After the formation of the first leaf leaves were the plants by inoculating with mildew-fallen plants. A week later, it was noted what percentage of the leaf area was covered by mildew. A fungicidal action was calculated as follows:

100 -. 100 _{infested infested = % wia3nmg} infestation in untreated

Any incompatibility of the treatment was assessed after emergence of the plants. The evaluation was done according to the scheme

0 = total annihilation

1 = 90% destruction

2 = 80% annihilation

3 = 70% annihilation

4 = 60% annihilation

5 = 50% annihilation

6 = 40% destruction

7 = 30 annihilation

8 = 20% destruction

9 = 10% destruction = undamaged.

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The compounds according to the invention were in the form of wettable powders with 20% Wixkstoffgehalt.

In contrast to the comparison means, the invention showed! proper compounds against Srysiphe graminis not only fully effective, but also completely compatible with barley »

According to the invention% action Compatibility Compounds Mr.

10 10 10 10 10 10 10 10 10 10 10 10 10 10

1- (4-Chlorpheno2y) -3,3-dimethyl-1- (1,2,4-triazol-1-yl) -2-butanone

1 100 2 100 5 100 6 100 7 100 8th 100 9 99.5 10 100 11 93 15 100 16 99 17 95 21 100 22 100 Comparative agent -

4

12 59 2 - # -

Example 11

Effect of prophylactic foliar treatment against leaf spot disease (Cercospora beticola) on sugar beets (Beta vulgaris).

Sugar beet plants with 4 well-developed leaves were sprayed dripping wet with the indicated concentrations. After the spray coating had dried, the treated plants and untreated control plants were sprayed uniformly with a suspension of 15,000 Cercospora spores per milliliter. At 26 ⁰ C and steam-saturated air, the plants were incubated for four days in the greenhouse and then kept at about 22 ⁰ C for a further 10 days in the greenhouse. Then the proportion of affected leaf area was noted. "The effect of the insecticides was calculated as follows:

100 - ¹⁰ ° 'infestation treated _{= % w ± D3cang} infestation in untreated

Inventive Wirkstoffkon- effect%

Yerbindungeη Fr, centering %

2 '4

5 11

0.05 100 0.01 100 0.05 100 0.01 100 0.05 100 0.01 99 0.05 100 0.01 96 0.05 100 0.01 100

241259 2

invention Wirkstoffkon Effect% Connections Ni ?. concentration% • 12 0.05 100 0.01 99.6 13 0.05 100 0.01 93 14 0.05 100 0.01 99.6 15 0.05 100 0.01 98 17 0.05 100 0.01 99 18 0.05 100 0.01 99.6 19 0.05 100 0.01 99.3 20 0.05 100 0.01 98 21 0.05 100 0.01 99.6 Vergieichsmittel Manganäthylen bis di t hi ο c arb am at 0.05 100 0.01 79 ' Example 12

61 087 18 23.3.83

Henrnrang of mushroom growth on nutrient solution.

20 ml of a nutritive solution of grape juice and water (1: 1)

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were placed in 100 ml glass vials and mixed with the 'powdered Wirkstoffabubereitungen. Then with conidia (spores) of Penicillium digitatum was inoculated "laughing, an incubation period of 5 days at 22 to 24 ⁰ O ^? Urde the fungal development on the surface of the nutrient solution assessed

 Rating: 0 = no fungal growth

1 = single fungal colonies on the surface

2 = surface 5 to 10 % covered by mushroom grass

3 = surface 10 to 30 % covered by mushroom grass

4 = surface 30 to 60% covered by mushroom grass

5 = surface 60 to 100% covered by mushroom grass

Active ingredients, active substance concentrations in the nutrient solution and results are listed in the table below.

Concentration of active compound according to the invention Mushroom irrigation "Compounds No. in the nutrient solution;%

5 0.0005 4

0.001 0

6 0.0005 4

0.001 1

17 0,0005 0

0.001 0

20 0.0005 0

0.001 0

21 0,0005 2

0.001 0

23 0,0005 0

0.001 0

24 1259 2

A. · * 9 &, ^ ^ ^. _ Zi ^ r _ Ai-t / - 61 087

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Inventive drug concentration fungal development

Compounds No. in the nutrient solution %

24 0.0005 1

0.001 0

27 0,0005 0

0.001 0

28 0,0005 0

0.001 0

29 0,0005 0

0.001 0

31 0,0005 0

0.001 0

32 0,0005 0

, 0.001 0

34 0,0005 0

0.001 0

37 0,0005 0

0.001 0

38 0,0005 0

0.001 0

Comparative agent (according to DS-OS 2 604 047) 3- (imidazol-1-yl) -2-phenyl-2-butyl-propionitrile

Hydronitrate 0.0005 5

0.001 4 ünbehandelte

Nutrient solution - 5

control

12 5 9 2 ^'5 ^' ^ ^'61 ° ⁸⁷¹⁸

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Example 13

Effect of prophylactic foliar treatment against the powdery mildew of vine Uncinula nacator.

Young grape varieties of the variety Silvaner with about 8 to 10 leaves were sprayed dripping wet with the concentrations given in the table. After the spray coatings had dried on, the plants were dusted dry with conidiospores of the fungus Uncinula necator and incubated at about 22 ^° C. for 12 days in the greenhouse. Then the proportion of mildew-infested leaf area was estimated in percent and the fungicidal effect calculated as follows,

100 - infestation in treatment - 100 _{= % WilknBge} infestation in untreated

The infestation reached 88.3% in untreated. The funds were in the form of 20% wettable powder. The effects are to be taken from the table «

According to the invention% effect against Uncinula necator with compounds Nr, 0.025 active ingredient 0.005 % active ingredient

2 93 85

3 100 100

4 100 100

5 100 100

6 100 99

7 100 89

8th . - 100 95

9 87 63

241259 2

- Η-θ - 61 08? 18

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According to the invention % action against Uncinula necator with compounds no. 0,025 active ingredient 0.005 % active ingredient

49 100 63 95 43 100

89 100 80 89 8 $ 100 92

10 100 11 100 12 100 13 100 14 66 15 100 16 99 17 100 18 86 19 100 20 93 21 100 22 100 Example 14

Effect of prophylactic foliar treatment against apple scab Venturia inaequalis in Preiland *

Growing shoots of apple variety Mi! 106 were drenched wet with 0.1% drug concentration. After the spray coatings had dried on, a suspension of conidiospores (330,000 per milliliter) was sprayed onto the leaves, and then the shoots were left to infect by the fungus for 3 days under light shade of polyethylene bute for half a second. After that, the bags were removed. After a total of 2 The proportion of scab-affected area in

l>

61 087 18 23.3.83

Percent estimated. The untreated control shows 99% infestation. The success of the treatments ^ ^- Urde it follows "calculated:

100. - infestation in treated »100 _{= % Wll] cnilg} infestation in untreated

The compounds were present as 20% wettable powder.

Brfindungsg em % Effect Connections ITr, 18 100 19 85 Example 15

Effect of curative foliar treatment against apple scab Yenturia inaequalis in the Ireiland «

In-growth shoots of apple plants of sow IM 106 were sprayed with a suspension of conidiospores (330,000 per milliliter) and kept moist immediately by slipping over polyethylene bags. "The plants were in partial shade. After 3 days, the bags were removed. Seven days after inoculation, the plants were treated with a 0.1 % concentration of active agent dripping wet. After a further 11/2 weeks, the proportion of apple scab infected leaf area was estimated in percent, it was untreated 99%. The bonds according to the invention were in the form of 20% wettable powders. The effect of the treatment was calculated as follows:

24 1259 .2 - * - ** -

100 - _infested infestation - 100 _{= % active} infestation in untreated

% Effect Compounds Fr.

2 93

18 100

19 100

Yergleichsmittel

2-butyl-3- (imidazol-1-yl) -2-phenylpropionitrile,

Hydronitrate 90

Example 16

Prophylactic foliar treatment against Erysiphe graminis on barley,

Barley plants at the stage of the first leaf were sprayed dropwise at the stated active compound concentration with addition of an alkaryl polyglycol ether as wetting agent (0.05%). Subject to the drying of the spray coating vrarden these plants and untreated control plants uniformly with mildew.-infected cereal plants coated and then incubated in the greenhouse at 20 to 22 ⁰ G for one week. Subsequently, the average powdery mildew per planter (18 to 20 plants) was noted. The Pungizidwirkung was calculated according to the formula

24125 9 2 - ^ r- V * - 61087 18

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100 - 100 _{infested infested = % of infested} infestation

The eufindungsgemäßen substances were present as 20% formulations.

would be suitable % Wi Yelbindungen Hr. 0.02 3 100 100 5 100 6 100 7 100 8th 100 9 100 10 92 11 100 12 100 13 100 14 100 15 100 16 100 17 100 18 100 19 100 20 100 21 100 22 100

0.023% active ingredient $ 0.00 % active compound

100 100 100 100 100 100 92 90 100 100 100 100 100 100 100 100 100 100 100 100

24 1259 2 __ "_".

23/3/83

Example 17

Effect of prophylactic foliar treatment against Uromyces .. appendiculatus (bean rust) in the greenhouse. Bush bean plants in the stage of the semi-developed primary leaves were sprayed to drip point with 100 ppm active ingredient concentration. After the spray coatings had dried on, the treated plants and untreated control plants were sprayed with a suspension of the urosces appendiculatus uredospore. For two days, the plants were then incubated in a humid chamber at 22 ⁰ C and then kept under Gewächshausb'edingungen at about 22 ⁰ C. 11 days after the spraying of the spores, the food pustules were counted (on average 253 d ^e leaf in the untreated control). The fungicidal effect was calculated as follows:

100 - P ^ wet in treated * 100 _{= %} g

Pustules in untreated

The substances according to the invention were present as 20% formulations and showed over 90 % activity.

In accordance with the invention % Effect Connection Ur. 1 91 2 96 3 95 94 12 100 15 99.5

2412 59 2

61,087 23.3.83

% Effect according to the invention

Connection no.   95 16 99 Λ 17 99.9 18 98 19 98.6 21 95 22 95 97 27 28 Example 18

Effect of prophylactic leaf treatment against Helminthosporium teres (= Pyrenophora teres), net blotch of the barley.

Young barley plants at the stage of the first leaf were sprayed with the specified concentrations of dribble. After drying the spray coatings, the treated plants and untreated control plants were sprayed with a suspension of the conidiospores of Helminthosporium teres and.Cultivated in a humid chamber for 2 days at 20 to 22 ⁰ C. One week after inoculation, the percentage of leaf area was noted. The fungicidal activity was calculated as follows:

100 - Infestation Treated * 100 _{= % We] £ Unge} Infestation in Untreated

The compounds were present as 20% formulations.

2Ä1259 2

- 63 - 61 .087 18 23.3.83

invention % Effect 90 Connection no. 500 ppm 100 ppm 90 35 90 90 36 95 90 37 95 95 38 95 100 39 95 98 40 100 100 4-1 100 100 42 100 100 43 100 100 44 100 100 46 100 89 47 100 100 48 100 96 49 100 100 50 100 89 51 100 100 52 98 96 53 100 100 54 96 100 55 100 96 57 100 89 58 100 59 100 Example 19

Effect of prophylactic leaf treatment against dwarf rust Puccinia hordei on barley in conditioned plant growth chamber.

12 5 9 2 - ^ - ^όδ " 61.08? 18

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Young barley plants at the stage of the first leaf were sprayed dripping wet at the indicated concentration. After the spray coatings had dried on, the treated plants and untreated control plants were inoculated by brushing over with frost-frozen plants and placed in a plant growth chamber. At 15 ⁰ C and den.beiden first days, under almost moist saturated air, the plants were cultivated 10 days. Thereafter, the percentage of rust-infected leaf area was noted. The ITungizidwirkung was calculated as follows:

100 - infestation treated. 100 _{= % Bef serious} infestation in untreated

The compounds were present as 20 / sige formulations. The table shows good to very good effects on numerous compounds according to the invention.

Effect of the invention%

Compounds No. 500 ppm 32 100

42 100

43 100 4-5 100

46 100

47 100

48 100

49 100

54 100

55 100 58 100

241259 2

61-087 18 23.3.83

Effect of the Invention% Compounds Hr. 300 ppm

61 100 64 100 65 100 66 100 67. 100 69 100 71 100 72 100 74 100 75 100 76 100 77 100 78 100 79 100 80 100 Example 20

Effect of prophylactic leaf treatment against yellow rust Puccinis striiformis on barley in conditioned plant growth chamber.

Young barley plants were sprayed dripping wet at the stage of the first leaf with the indicated concentrations. After drying the spray coatings were the treated plants. and untreated control plants with a suspension of the uterine pores of Puccinia striiformis in 1,1,2-trifluoro-1,2,2-trichloroethane sprayed and in a Pflanzerrarachskammer

2 4 12 5 9 2 ~ ^ ~ ^εε ~ ^6108718

23/3/83

incubated at 150 ^° C. In the first two days, almost humid air was taken care of. After 15 days, the percentage of roach-infected leaf area was noted. The fungicidal activity was calculated as follows:

100 - infestation treated. 100 _{= % Effect #} Infestation in discomfort

% Effect according to the invention with compounds ITr. 100 33 11 ppm

5 100 ο- - 12 100 Ι 00 100 14 100 - - 15 100 100 100 16 100 - - 17 100 100 100 18 100 100 93rd 28 100 98 78 Example 21

Effect of seed treatment against Helminthosporium sativum on barley in climatic plant growth chamber. Barley seed with artificial infestation by Helminthosporium sativum was powdered with 50 g.Wirstoff inventive agent per 100 kg. For each test element, 2 g of treated or untreated seed were sown in plastic pots of 6.5 s: 6.5 cm. The substrate was sand. For each Yersuchsglied 2 repetitions were created. The pots were in

125

61,087 23.3.83

plant growth chamber "at 15 ^° C. Each 4 weeks, the crops were examined for percent infestation of the stem base and from the average of the repetitions, the fungicidal effect was calculated as follows:

100 - infestation treated. 100 _{=% effect #} infestation in untreated

Die.erfindungsgemäßen funds were present as 20% formulations.

% Action according to the invention against compounds No. Helminthosporium sativum

7 99 98.5 2-butyl-3- (imidazol- 98 17 99 1-yl) -2-phenyl- 21 99.5 propionitrile, 25 100 Hydro nitrate 26 100 29 100 32 100 38 100 comparison means 2-butyl-3- (iinidazole) 1-yl) -2-phenyl- propionitrile

125 9 2 - ^ - $ "7- 61,087 18

23/3/83

Example 22

Action against Pseudomonas phaseolicola, causative agent of the Ifett blotch disease of the colonies, in vitro.

Diomalzagar was after. Heat sterilization cooled to about 4-5 ⁰ G and then mixed with the test substances in aqueous preparation mixed in Kunststoffpetrischalen poured. After solidification of the culture medium, the dishes of treated agars and dishes with untreated agar as a control were inoculated with a suspension of the fatty spot exciter Pseudomonas phaseolicola in the center by means of a loop. Then the dishes were incubated at 22 ⁰ C. After 2 1/2 weeks, the radial extent of the grown colonies of the bacteria was measured. * From the average of two replicates per each test subject, the bacteriostatic effect was calculated as follows:

100 - Hadial Growth Treated ♦ 100 _{=% Home} Impact Radial Growth Untreated

The compounds were present as 20% formulations. % Inhibitory effect of 250 ppm active ingredient in agar against Pseudomonas phaseolicola.

% Inhibitory Effect According to the Invention Compounds No.

3 71

4 71

11 67

12 86

61,087 18 23.3.83

invention % Inhibitory effect 2-butyl-3- (imidazol- 42 Connections no. 1-yl) -2-phenyl- 13 78 propionitrile, 15 75 Hydro nitrate 17th 67 Example 23 18 75 19 71 21 71 comparison means

Effect of prophylactic foliar treatment against powdery mildew Erysiphe graminis on barley in the greenhouse. Young barley plants in the stage of the first leaf were sprayed dripping wet with the specified concentrations. After the spray coatings had dried on, the treated plants and untreated Kievert plants were inoculated with powdery mildew spores by covering the Yersuch plantlets with infested plants. Thereafter, the test plants were cultivated in the greenhouse at about 20 to 22 ⁰ C and. after one week, scored for percent blade area infection. The fungicidal effect was calculated as follows:

100 - infestation in treated * _{=% Wirkunge} infestation in ünbehandelt 100

125 9 2 - * - ⁵⁹ ~ «

23/3/83

The compounds were present as 20% formulations.

Inventive % Action Compounds Hr. 100 ppm 20 ppm

50 *

100 100 100 100 100 99 100 100 - 100 100 100 100 100 100 100 100 100 100 100 100 100 98 90 100 91 100 100 100 100 96 91 100 100 100 96 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100

24 12 5 9 2 - ^ 2-- ^ - 61.087 18

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Brfindungsgemäße % Effect 20 ppm links 100 ppm 100 54 100 100 55 100 100 56 100 100 57 .100 87 58 100 100 59 100 98 60 100 100 61 100 100 62 100 100 63 100 95 64 99 100 65 100

Claims (4)

Ή
- NI, R is an optionally mono- or polysubstituted by identical or different halogen, (G.-G ₂ ^) - alkyl, (G ₁ -G ^) - alkoxy, (G ₁ -G ^) - alkylthio, trifluoromethyl or the nitro group aromatic hydrocarbon radical and E ₁ (G ₁ -G ₁₀ ) -alkyl, (G ₃ -G ₈ ) -alkenyl, (G ₃ -G ₈ ) -alkynyl or an optionally mono- or polysubstituted by identical or different halogen, (G ₁ -C ^) - AIlSyI, (G ₁ -C ^) - Alkosy, (G ₁ -G ^) - alkylthio, trifluoromethyl or the FITRO group substituted phenylalkyl radical and their acid addition salts with inorganic and organic acids, in admixture with carriers and / or excipients « Biocidal agent according to item 1, characterized in that E is an optionally mono- or polysubstituted by identical or different halogen, (G ₁ -G ^) - alkyl, (C ₁ -G ^) - alkoxy, (C ₁ -C _Z) _) - alkylthio, trifluoromethyl or the Nitro group substituted phenyl radical and 12 5 9 2 - ^ - ei 087 23/3/83 R ₁ (G ^ -CG) alkyl, allyl, propargyl or a given substituted one or more times by identical or different halogen, (O ^ -C) - alkyl, (Cj-C ^ _-) -alkoxy ,, (C ₁ -C ₄ ) alkylthio, trifluoromethyl or the nitro group substituted benzyl radical. 3. Biocidal agent ganäß points 1 and 2, characterized in that they have fungicidal activity. 4. Biocidal agent according to items 1 and 2, characterized in that they have growth-regulatory activity. 5. Biocidal compositions according to items 1 and 2, characterized in that they have bactericidal activity *