LU84246A1 - IMIDAZOLYL PROPIONITRILE METHOD FOR THE PRODUCTION OF THESE COMPOUNDS AND THE BIOCIDES CONTAINING THEM - Google Patents

Description

SCHERINGAG

Intellectual Property

The invention relates to new iraidazolyl-propionitriles, processes for the preparation of these compounds and biocidal compositions containing them, in particular with a fungicidal action.

Imidazolyl-propionitrile derivatives with fungicidal activity are known; already known (DE-OS 26 Ok 0 ^ 7) · However, these have a relatively narrow spectrum of activity, which is unsatisfactory.

The object of the present invention is to develop new imidazolyl-propio-nitriles which open up a wide range of applications, in particular in the field of crop protection, and which have a broad fungicidal spectrum of action.

This object is achieved according to the invention by imid & zolyl! -Propio-nitriles of the general formula I ~ Rl

R - C - CH - NZ

I 2 X!

CN A

in which R is substituted one or more times, identically or differently, by halogen, (C1 ~ C ^) - alkyl, (C ^ -C ^) - alkoxy, (C ^ -C ^) - alkylthio, trifluoromethyl or the nitro group aromatic hydrocarbon radical and R1 (CrC10) -alkyl, (C ^ -Cg) -alkenyl -, (C ^ Cg) -alkynyl or one optionally one or more, the same or different! f \ -1 · -

Board: Dr. Herbert Asmis Dr. Christian BruhnHans-Jürgen Hamann Postal address: SCHERING AG - D-1000 Berlin 65Postbox 65031t Z Πγ Hain? Hannaa * Karl Otto Mltte («ten« rhAÎH. Dr. Horst Witvel ___, »» ____i_i

_10_ SCHERINGAG

Commercial legal protection through halogen, (C ^ -C ^) - alkyl, (C ^ -C ^) - alkoxy, (C ^^ - C ^) - alkylthio,

Trifluoromethyl or the nitro group substituted phenylalkyl radical and their acid addition salts with inorganic and organic acids.

The compounds according to the invention are biocidally active in the broadest sense, but are particularly notable for a fungicidal action, in which they surprisingly outperform known active compounds of analogous constitution and direction of action.

The fungicidal action surprisingly extends against fungi of various systematic positions. When treating above-ground parts of plants, they protect against wind-borne pathogens. The compounds can be used for seed treatment against pathogens that can be transmitted by eaves. In addition, these act systemically, that is, they are absorbed by the roots of the plants, for example after being introduced into the seeds, are transported to the aerial parts of the plants and protect them against pathogens.

%

Further effects include a growth regulatory and a bactericidal effect.

Because of the wide spectrum of Wirklings recognized, the connections are not only suitable for the protection of crops but also for fl - "11_ c Board: Dr. Herbert Asmls · Dr. Christian Bruhn - Hans-Jürgen Hamann Postal address: SCHERING AG · D-1000 Berlin 65 · PO Box KC311 7 rtr U.; «·. Uann.A _ V..I rtM. Sltli.l.» η. I f iék.J.1

_u_ SCHERINGAG

-- " Intellectual Property

Material protection and to combat human pathogenic and animal pathogenic microbes, which results in a wide range of possible applications.

Depending on the special meaning of the substituents, there are focal areas of application in which the compounds have outstanding effects. So they can be used as fungicides, plant growth regulators or bactericides.

In the compounds represented by the general formula I can mean, for example: R 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, 2-bromophenyl, 3 ”bromophenyl, 4-bromophenyl , 2-iodophenyl, 3-joclphenyl, 4-iodophenyl, 2,3-dichlorophenyl, 2,4-dichlorophenyl, 3i ^ “dichlorophenyl, 2,6-dichlorophenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2-ethylphenyl, 3-ethylphenyl, 4-ethylphenyl, 2-propylphenyl, 3-propylphenyl, 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-butylphenyl, 2-methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl, 2-ethoxyphenyl, 3 “ethoxyphenyl, 4-ethoxyphenyl, 2-methylthiophenyl, 3“ methylthiophenyl, 4-methylthiophenyl, 2-ethylthiophenyl, 3-ethylthiophenyl, 4-ethylthio-m ΰ phenyl, 2-trifluoromethylphenyl, 3 ~ trifluoromethylphenyl, 4-tri- I and \ -12- £ Board: Dr. Herbert AsmisDr. Christian BruhnHans-Jürgen Hamann Postal address: SCHERING AG D-100Q Berlin 65 - P.O.Box 65 0311? Dr. Heinz Hannse - Karl Otto MittelstenscheidDr. Horst Witzei r »ν '« »·« «. B.ritn.ura. » nant-ia; wt> hi in rnn-tn

SCHERING AG

_12- Commercial law * protect fluoromethylphenyl, 2-nitrophenyl, 3-nitrophenyl, 4-nitrophenyl, 3-fluoro-4-methoxyphenyl, 2-chloro-5-uitrophenyl, 4-chloro-2-fluorophenyl, 3,4,5- Trimethoxyphenyl, or 5-chloro-2-nitrophenyl and (C ^ -C ^ q) alkyl, for example methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, xsopropyl, 2 , 2-dimethyl-propyl-1, 3,3-dimethyl-butyl-2, (C ^ -Cg) alkenyl, for example 2-buten-1-yl, 3-methyl-2-buten-l-yl , Hexenyl, heptenyl, octenyl, (CyCg) alkynyl, for example propargyl, butynyl, pentynyl, hexynyl, heptynyl, octynyl,

Phenylalkyl, for example benzyl, 2-fluorobenzyl, 3_fluorobenzyl, 4-fluorobenzyl, 2-chlorobenzyl, 3 “chlorobenzyl, 4-chlorobenzyl, 2-bromobenzyl, 3-bromobenzyl, 4-bromobenzyl, 2,4-dichlorobenzyl, 2,6- Dichlorobenzyl, 3,4-dichlorobenzyl, 2-methylbenzyl, 3-methylbenzyl, 4-methylbenzyl, 2-nitrobenzyl, 3-nitrobenzyl, 4-nitrobenzyl, 2-trifluoromethylbenzyl, 3-trif * luormethylbenzyl, 4-tri- fluoromethylbenzyl, 2-methoxybenzyl, 3-methoxybenzyl, 4-methoxybenzyl, 2-ethoxybenzyl, 3-ethoxybenzyl, 4-ethoxybenzyl, 2-propoxy «benzyl, 3-propoxybenzyl, 4-propoxybenzyl, 2-butoxybenzyl, 3-butoxybenzyl 4-butoxybenzyl, 2-methylthiobenzyl, 3-methylthio-benzyl, 4-methylthiobenzyl, 2-ethylthiobenzyl, 3-ethylthiobenzyl, 4-ethylthiobenzyl, 2-butylthiobenzyl, 3-butylthiobenzyl, 4-butylthiobenzyl are for example benzene.

Examples of inorganic and organic acids for the formation of the acid addition salts are the hydrogen halide *? o «/ _.

ΊΆ -3-3- jï! Board: Dr. Herbert Asmis Dr. Christian Bruhn - Hans-Jürgen Hamann Postal address: SCHERING AGD-1000 Berlin 65Postbox 65 0311 / Z I Dr. Heinz HannseKarl Otto MittelstenscheidDr. Horst Witzei postal check account: Berlin-West 1175-101. Bankleltzah! 10010010

SCHERING AG

Commercial legal protection • ff acid, such as hydrochloric acid and hydrobromic acid, also phosphoric acid, sulfuric acid, especially nitric acid, mono- and bifunctional carboxylic acids and hydroxycarboxylic acids, such as acetic acid, maleic acid, succinic acid, fumaric acid, tartaric acid, citric acid, salicylic acid,%

Sorbic acid, lactic acid, and sulfonic acids, such as * p-toluenesulfonic acid and 1,5-naphthalenedisulfonic acid ·,

These acid addition salts can be obtained by the usual salt formation methods, for example by dissolving a compound of formula 1 in a suitable solvent and adding the acid.

f

Of the compounds according to the invention are notable for a fungicidal action, in particular those in which, in the general formula I, the radical R is one or more, optionally the same or different, halogen, (C 1 -C 4) -alkyl, (C 1 -C 4) -C ^) - alkoxy, (C ^ -C ^) - alkylthio, trifluoromethyl or the nitro group substituted phenyl radical and R ^ (C ^ -Cg) alkyl, allyl, propargyl or one, if appropriate one or more times, the same or different mean by halogen, (C ^ -Cj ^) - alkyl, (C ^ -Cj ^) - alkoxy, (C ^ -C ^,) - alkyl thio, trifluoromethyl or the nitro group substituted benzyl group.

, k a cn

T

VnretflπΗ · Πγ Parharf Aemie. rir Chrieflan Rruhn. Munc-tnrnen Hamann Drtefanerhrlff · Ci ^ WPDIWrt ΑΛ. Berlin ttR. Drteffwrh # Ä ftt

SCHERING AG

H-4- Intellectual Property Law

Of these, preference should be given to those compounds in which R is phenyl, 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, 2,4-dichlorophenyl, 2,6-dichlorophenyl, 3,4-dichlorophenyl, 2-fluorophenyl, 4 -Fluorophenyl, 4-bromophenyl, 2-methylphenyl, 4-methylphenyl, 4-methoxyphenyl, 4-nitrophenyl and * t methyl, ethyl «Freyyl, leeyreyyl« Peatyl, Inqrlt hllyl «

Propargyl, benzyl, 2-chlorobenzyl, 4-chlorobenzyl, 2,4-dichlorobenzyl, 3,4-dichlorobenzyl.

The following compounds according to the invention are of outstanding activity; 2-n-butoxy-2- (l-chleryheayl) -3- (laida-1-1-yl) -yreflealtril,

Hydronitrate 2-n-butoxy-2- (2-chlorophenyl) -3- (imidazol-l-yl) propionitrile 2-n-butoxy- (4-chlorophenyl) -3- (imidazol-1-yl) propionitrile, Hydronitrate 2- (4-chlorophenyl) -3 “(imidazol-1-yl) -2-n-propoxypropionitrile, hydronitrate 2- (2-chlorophenyl) -3- (imidazol-l-yl) -2-n-propoxypropionitrile

The compounds according to the invention show fungicidal effects in particular, but are also notable for growth-regulating effects in a number of crop plants.

\ & \ ll5-

û Board: Dr. Herbert AamisDr. Christlsn BruhnHana-JOrgen Hamann Postal address: SCHERING AG. D-1000 Berlin «5 · Poetfach HH TI

_15_ SCHERING AG

Intellectual Property Law «s

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

Accordingly, they develop their growth-regulating properties both in applications over the floor and in spray treatment

S

Effect.

The growth-inhibiting effects of cress and tree roll are particularly noticeable.

In addition to the above-mentioned effects, the compounds according to the invention also have a bactericidal action which permits further possible uses.

The compounds according to the invention can be used either alone, in a mixture with one another or with other active compounds. If necessary, other pesticides or pesticides can be added depending on the desired purpose.

The labeled active ingredients or their

Mixtures 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, if appropriate, Wets-r, adhesives, emulsifiers and /

L

w N - 8 -16- W - · - W * * ^ I / Arefanri · Or. Hsrhort Aemfe. ΓΊγ rhrietlan roe. Uane ^ tilroan Mamnnn Dnatanerfirlft · Af'MßBlkJrt Aft. Π-1Π (ΥΙ Rarlfn AS. Drtatfar + i

SCHERING AG

—16- Protection of industrial property rights or dispersion aids applied.

Suitable liquid carriers are, for example, water, aliphatic and aromatic hydrocarbons, such as benzene, toluene,

Xylene, cyclohexanone, isophorone, dimethyl sulfoxide, dimethylformamide, mineral oil fractions and vegetable oils.

* r

Mineral soils are suitable as solid carriers, for example i *

Tonsil, silica gel, talc, kaolin, atbapulgite, limestone, silica and vegetable products, for example flours

Examples of surface-active substances include: calcium lignin sulfonate, polyoxyethylene alkylphenyl ether, naphthalene sulfonic acids and their salts, phenol sulfonic acids and their salts, formal dehyde condensates, fatty alcohol sulfates and substituted benzenesulfonic acids and their salts.

If the active ingredients are to be used for seed dressing, dyes can also be added in order to give the seed dressing a clearly visible color.

The proportion of the active ingredient (s) in the various preparations can vary within wide limits. For example, the agents contain about 10 to 90 percent by weight of active ingredients, about 90 to 10 percent by weight of liquid or solid carriers and optionally up to 20 percent by weight of surface-active agents.

l / r'v -17- r- Z- L: Board of Directors: Dr. Herbert AsmisDr. Christian BruhnHans-Jürgen Hamann Postal address: SCHERING AGD-1000 Berlin 65 - P.O.Box 65 0311 Z Dr. Heinz Hannse * Karl Otto MiitelstensRhelri. no Mnrxt Wit7 «1 ______ L __. .

SCHERINGAG

Commercial law I utz

The agents can be applied in a customary manner, for example using water as a carrier in spray liquor amounts of about 100 to 1000 liters / ha. The application of the agents in the so-called "low-volume" or ultra-low-volume process is just as possible as their application in the form of so-called microgranules.

*. For the preparation of the preparations, for example, the following ingredients are used: A. wettable powder a) kO weight percent active ingredient 25 weight percent clay minerals 20 weight percent silica 10 weight percent cell pitch 5 weight percent surfactants based on a

Mixture of the calcium salt of lignin sulfonic acid with alkylphenol polyglycol ethers b) 25 percent by weight of active ingredient 60 percent by weight of kaolin 10 percent by weight of silica 5 percent by weight of surfactants based on

Sodium salt of N-methyl-N-oleyl-taurine. and the calcium salt of lignin sulfonic acid.

«- -18- 0

A

T- c board: Dr. Herbert Astnis - Dr. Christian BruhnHans-Jürgen Hamann Postal address: SCHERING AGD-1000 Berlin 65 - PO Box 650311

_18_ SCHERINGAG

- Commercial legal protection 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% by weight of surface-active substances based on

Sodium salt of N-methyl-N-oleyl-taurine and the calcium salt of lignin sulfonic acid.

B. Fast 45 percent by weight of active ingredient 5 percent by weight of sodium aluminum silicate 15 percent by weight of cetyl polyglycol ether with 8 moles of ethylene oxide 2 percent by weight of spindle oil 10 percent by weight of polyethylene glycol t 23 parts of water C. Emulsion concentrate 25 percent by weight of active ingredient 15 percent by weight of cyclohexanone 55 percent by weight of xylene 5 percent by weight of mixture of nonylphenylpolyoxyethylene 1 or C aiebenum sulf onate.

The new compounds of the invention can be prepared, for example, by propionitriles of the general formula / - "· £. Board of Directors: Dr.Herbert AsmisDr. Christian BruhnHans-Jürgen Hamann Postal address: SCHERING AGD-1000 Berlin 65Postbox 650311 Z Dr. Heinz HannseKarl Otto Mittelstenscheid - Dr. Horst WitzeiFu> riin-We * t n7S-ini Hankleitzahl 10010010

SCHERINGAG

Intellectual Property Rights 0 - R *

R - C - CHn- Y II

iN 2 with imidazole of the formula

HC - NH

1 l

, HC CH

in the presence of a solvent and, if appropriate, in the presence of a base, in which R and R ^^ have the meaning given above and Y is halogen, or the alkylsuifoayloxy or arylsuifoayloxy radical which may be halogenated in the side chain.

Halogen is, for example, chlorine, bromine or iodine; Suitable alkylsulfonyloxy radicals are methyl, ethyl, propyl and the tr if lu r me t hy 1 suif ony 1 oxy groups, and arylsulfonyloxy radicals which may be mentioned are, for example, the benzylsulfonyloxy and p-toluenes "lfoayltzy-finipp" i.

The reaction can be carried out either with an excess of imidazole, optionally in the presence of a solvent, or with the addition of a strong base, for example sodium or potassium hydroxide. In addition, imidazole alkali metal can also be used instead of imidazole.

Suitable solvents are inert, preferably polar, aprotic substances, such as N, N-dimethyl-2 / -20-3. Herbert AsmisDr. Christian BruhnHans-Jürgen Hamann Postal address: SCHERING AGD-1000 Berlin 85 - P.O.Box 85 0311

Z Ptr UoinT Uennia Har! ΠΗη UitfeletenerbôIH. Πι * garbage Wit70i n i> i. i / i. . no: _ ur._s 4flAim <A

SCHERING AG

Commercial legal protection formamide, Ν, Ν-dimethylacetamide, N-methylpyrrolidone, tetramethyl urea, hexaraethylphosphoric acid triamide and benzonitrile, but also high-boiling aromatic and aliphatic hydrocarbons such as toluene, chlorobenzene or xylene.

H

The reaction temperature can hardly be varied widely. A temperature between 100 ° C. and 20.0 ° C. is preferred.

The implementations take place under normal or overpressure.

The xmidazolyl-propionitriles according to the invention are generally almost colorless and odorless oils. The acid addition salts derived from them are colorless and odorless, crystalline compounds.

The oils dissolve poorly in water and more or less well in organic solvents such as alcohols, ether or chlorinated hydrocarbons. The acid addition salts partly dissolve in water and well in polar organic solvents such as acetonitrile, Ν, Ν-dimethylformamide, lower alcohols, chloroform and methylene chloride.

The following examples illustrate the preparation of the compounds of the invention.

EXAMPLE 1 3- (Imidazol-1-yl) -2-phenyl-2-propoxypropionitrile, hydronitrate - (Compound No. 1)! k

IV

SCHERING AG

- r 21- Commercial legal protection 15 S (0.053 mol) of 3-methylsulfonyloxy-2-phenyl-2-propoxypropionitrile and 17.89 g (0.263 mol) of imidazole were kept under exclusion of moisture for 16 hours at 14 ° C. with the addition of 1 ml of dimethylformamide.

It is poured onto ice water, extracted twice with 75 »1 methylene chloride, the methylene chloride phase is washed twice with Vasser, dried with magnesium sulfate and, after filtering off the drying agent, concentrated in vacuo. The remaining, dark oil is dissolved in isopropanol and a little more than the theoretical amount of 100? 6 nitric acid is added. A little diethyl ether is added to complete the precipitation. The precipitated product is filtered off and dried.

Yield: 12 g = 71 S of theory. Mp .: 16-171 ° C (decomposition) EXAMPLE 2 3- (Imidazol-1-yl) -2-phenyl-2-propoxy-grogionitrile (Compound No. 2) 6.2 g (0.0195 mol) of the hydronitrate are dissolved in methanol and made basic with dilute ammonia solution while cooling in an ice bath. After dilution with Vasser, the mixture is extracted with ethyl acetate, the organic phase is washed with water and then dried with magnesium sulfate. After filtration, the mixture is concentrated in vacuo. An 01 remains, which is dried in vacuo. fj yield: 4.85 g = 97% of theory 1 Kv1 = i’526 ° -22- •; . "~ .Z.Z. ', Lï. - _ ·· - £ '1 -1 J ~ - ^ c • y-y * r \ -er *. * w

_22. SCHERING AG

Intellectual Property

The following compounds according to the invention can be prepared analogously *

Name of the compound Physical constant 3 · 2-butoxy-3-ii®i <iazol-l-yl) -2-phenyl-propioiiitrile, mp: 155-157 C (Z)

Hydronitrate 4. 2-Butoxy-3- (imidazol-l-yl) -2-phenyl-propionitrile 1 ^ 39 »1.5208 5 * 2-allyloxy-3- (imidazol-l-yl) -2-phenyl-propionitrile , Mp: l62-l64 ° C (Z) hydronitrate 6. 2-allyloxy-3- (imidazol-l-yl) -2-phenyl-propionitrile njj33 = 1.5402 7 · 2-ethoxy-3- (imidazole- l-yl) -2-phenyl-propionitrile, mp: l82-l86°C(Z)

Hydronitrate 8. 2-ethoxy-3- (imidazol-l-yl) -2-phenyl-propionitrile '1 ^ 44 = 1.5247 9.3- (imidazol-l-yl) -2-methoxy-2-phenyl-propionitrile, mp .: l89-191 ° C (Z)

Hydronitrate

10. 3- (Imidazol-l-yl) -2-methoxy-2-phenyl-propionitrile mp: 57-60 ° C

11. 2- (2-chlorophenyl) -3 "(imidaz ° ll-yl)" 2-propoxy- mp: l62-l65°C(Z) propionitrile, hydronitrate 12. 2-butoxy-2- (4-chlorophenyl ) -3- (imidazol-l-yl) - mp: 178-l8l°C(Z) propionitrile, hydronitrate 13 · 2-butoxy-2- (2-chlorophenyl) -3- (imidazol-l-yl) - Mp: 177-178 ° C (Z) propionitrile, hydronitrate l4. 2-allyloxy-2- (2-chlorophenyl) -3- (imidazol-l-yl) - mp: 155-155 ° C (Z) propionitrile, hydronitrate 15.2- (4-chlorophenyl) -3- (imidazole -l-yl) -2-propoxy- mp .: 174-177 ° C (Z] propionitrile, hydronitrate 16. 2-allyloxy-2- (4-chlorophenyl) -3- (imidazol-l-yl) - mp. : 152-155 ° C (Z) propionitrile, hydronitrate

Lx. -23- m ά m w t-

SCHERING AG

2-3- Intellectual Property Law

Name of the compounds Pbyeifcaliecbe constant 17.2- (2-chlorophenyl) -3- (imidazol-l-yl) -2-propoxy-np4l = 1 »53 ^ 3 propionitrile 18. 2-butoxy-2- (4- chlorphenyl) - 3- (imidazol-l-yl) - η ^ 4ΐ ~ 1.5288 propionitrile 19 · 2-butoxy-2- (2-chlorophenyl) -3 ”(imidazol-l-yl) - * ij) 4l * li5329 propionitrile 20. 2-allyloxy-2- (2-chlorophenyl) imidazole-l-yl) - * ijj4l = 1 »5 ^ 90 j propionitrile 21 .. 2- (4-chlorophenyl) -3- (imidazole-l -yl) -2-propoxy- ^ 41 = * '' 5337 propionitrile 22. 2-allyloxy-2- (4-chlorophenyl) -3-iniidazol-l-yl) - 1 = * »5476 propionitrile 23 * 2-benzyloxy -3- (imidazol-l-yl) -2-phenyl-propionitrile, m.p.ïl66-l68 ° C (Z) hydronitrate 24 * - 2-benzyloxy-3- (imidazol-l-yl) -2-phenyl-propionitrile Λρ4θ * 1.5638 25. 3- (Imidazol-1-yl) -2-i «opropyloxy-2-p ^^ ï-pro | ^ MÎtïtriI" Wjfl'i

Hydronitrate (%) 26. 3- (imidazol-l-yl) -2-i »opropyloxy-2-phenyl-propionitrii n ^ O. ^ 5254 27.2- (4-Chlorophenyl) -2-hexyloxy- 3- (imidazol-l-yl) -propiö- Fig. : 152-154 ° C nitrile, hydronitrate - (Z) 28. 2- (4-chlorophenyl) -2-hexyloxy-3- (imidazol-1-yl) -propio- il.40: 1 5197 nitrile "29" 2 -Allyloxy-3- (imidazol-l-yl) -2- (2-methylphenyl) propio-pp.; 16 ° C (Z) nitrile, hydronitrate

30th 2- (3 * 4-dichlorophenyl) -3- (imidazol-l-yl) -2-propoxy- mp.; I69-170 ° C

propionitrile, hydronitrate (Z)

31.2-Butoxy-2- (2,4-dichlorophenyl) -3- (imidazol-l-yl) propio mp; l48-50 ° C

nitrile, hydronitrate (Z)

32 · 2-allyloxy-2- (2,4-dichlorophenyl) -3- (imidazol-1-yl) - mp ::158-60 ° C

propionitrile, hydronitrate (Z)

33 · 2-ethoxy-2- (3 »4-dichlorophenyl) -3- (imidazol-l-yl) - Ppi: 105-06 ° C

propionitrile, hydronitrate - (¾) I /). * / VftmfanH · Dr. Hprhurf. ttr chrSetian finihn. HamtJuroen Η> πβηπ postal address! SCHËRINû AG * D * 1Û0Û Berlin 65 * Poetic 656311

· SCHERING AG

“24- Intellectual Property Law

Nsm of the connections Pbymikaliechei leastM- __t ·

34. 2-Allyloxy-3- (imidazol-l-yl) -2- (2-mathylphanyl) prepio- n ^ kOi 1.53W

nitrile.

35. 2- (3,4-dichlorophenyl) -3- (imidazol-l-yl) -2-propoxy-pro- Hp40: 1.53 ^ ° pionitrile 36. 2-allyloxy-2- (3 »4-dichlorophenyl ) -3- (imidazol-l-yl) - ^ 40.1 ^ 5500 "propionitrile 37.2-butoxy-2- (2,4-dichlorophenyl) -3- (imidazol-l-yl) -propio- • nitrile" d i1.5381 38. 2-allyloxy-2- (2,4-dichlorophenyl) -3- (imidazol-l-yl) -pro ^ - ’ss; pionitrile n ^ 40ï1 * 5531 39l. 2-ethoxy-2- (3,4-dichlorophenyl) -3- (imidazol-l-yl) propioniirii - V0! 1.5Î7Ï 4o .3- (imidazol-l-yl) -2-phenyl-2- (1,212-trimethyl-propoxy) propionitrile, hydronitrate mp: 168-173 ° <, x, (Z '4l.3- ( Imidazol-l-yl) -2- (2-methoxy-ethoxy) -2-phenyl-propionitrile, hydronitrate m.p .: 158-ΐ6θ ° ((Z] 42.2- (212-dimethylpropoxy) -3- (imidazole-l- yl) -2-phenyl-

propionitrile, hydronitrate mp: 16-171 ° C

(z: .- 43 · 2 “(212-dimethyl-propoxy) -3- (imidazol-l-yl) -2-phenyl-propionitrile mp: 89-91 ° <" 44.2- (2-fluorophenyl) -3 - (imidazol-l-yl) -2-propoxy-propionitrile, hydronitrate mp: 170-172 ° <(z: 45.2-butoxy-2- (2-fluorophenyl) -3- (imidazol-l-yl) propionitrile ,

Hydronitrate mp: 173-176 ° <(z: 46.2- (4-fluorophenyl) -3- (imidazol-l-yl) -2-propoxypropionitrile,

Hydronitrate Mp .: I5O-I52 ° ((z;! * 4? .2-Butoxy-2- (4-fluorophenyl) -3- (imidazole-1-ÿl) -propionitrile,

Hydronitrate mp: l62-l6 ^ (- ^ 8.2-allyloxy-2- (2-fluorophenyl) -3- (imidazol-l-yl) propionitrile,

Hydronitrate Mp .: l69-171 ° <--- ------— - - / -7 '

- · 49, 2-ethoxy-2- (2-fluorophenyl) -3- (imidazol-l-yl) propionitrile, V

Hydronitrate Mp .: 172-175 ° <1 / .......: (z: ../ ... - _i * _ »ir. I_i cr'UCQiKi / Î iß. 0-1000 Berlin 65 65 0311 _ 1

SCHERINGAG

Industrial property protection 50 .. 2- (2-fluorophenyl) -3- (imidazol-l-yl) -2-methoxy-propionitrile,

Hydronitrate mp: 177-179 ° C

(Z) 51 * 3- (imidazol-l-yl) -2-phenyl-2- (1,2,2-trimethyl-propoxy) -

propionitrile m.p .: 113 -116 ° C

52 ^ 3- (Imidazol-1-yl) -2- (2-methoxy-ethoxy) -2-phenylpropionitrile nD * · 1.5212 53? „2- (2-fluorophenyl) -3- (imidazol-l-yl ) -2-propoxy-propioniteil np: 1.51 ^ 3 54 * 2-butoxy-2- (2-fluorophenyl) -3- (imidazol-l-yl) propionitrile

Sp: 1.5108 55. 2- (4-fluorophenyl) -3- (imidazol-l-yl) -2-propoxypropionitrile. : 1.5115 56. 2-butoxy-2- (4-fluorophenyl) -3- (imidazol-l-yl) propionitrile, x Λ np ° * 1.5085 57 .. 2- (2-fluorophenyl) -3 -imidazol-l-yl) -2-methoxy-propionitrile ',. . nP T 1.5280 58. ’2-Ethoxy-2- (2-fluorophenyl) -3- (imidazol-l-yl) propionitrile

PP : 1.5187 592-allyloxy-2- (2-fluorophenyl) -3- (imidazol-l-yl) propionitrile n £: 1.5258 60. 2-allyloxy-2- (4-fluorophenyl) -3- ( imidazol-l-yl) propionitrile,

Hydronitrate Mp .: 159 -166 ° C

(Z) 61 '2-ethoxy-2- (4-fluorophenyl) -3- (imidazol-l-yl) propionitrile,

Hydronitrate mp: l82 -84 ° C

(Z) Ê2. * 2- (4-fluorophenyl) -3- (imidazol-1-yl) -2-methoxypropionitrile,

Hydronitrate mp: 194-196 ° C

(Z) g 3 2-ethoxy-2- (4-fluorophenyl) -3- (imidazol-l-yl) propionitrile

Mp: 54-57 ° C

64. ' 2- (4-fluorophenyl) -3- (imidazol-l-yl) -2-methoxypropionitrile

Mp: 88 ° C

g9 2-allyloxy-2- (4-fluorophenyl) -3- (imidazol-l-yl) propionitrile np * 1.5219 g-g 2-decyloxy-3- (imidazol-l-yl) -2-phenyl-propionitrile,

Hydronitrate mp: 126-128 ° C

(Z) 67 .. 2- (3,3-dimethylbutoxy) -3- (imidazol-l-yl) -2-phenyl-

propionitrile, hydronitrate mp: 195-198 ° C

s (Z) 68. 3- (imidazol-l-yl) -2-octyloxy-2-phenyl-propionitrile nD: 1.5055 69 ^. 2- (3,3-Dimethoxybutoxy) -3-imidazol-l-yl) -2-phenyl-propionitrile n4o. li5093 -26- «O»

CO

w »I * Board: Dr. Herbert AsmisDr. Christian BruhnHans-Jürgen Hamann Postal address: SCHERING AGD-1000 Berlin 65Postbox 65 0311

_26_ SCHERINGAG

Intellectual Property 702- (4-bromophenyl) -2 ~ bntoxy-3- (imidazol-l-yl) propionitrile,

Hydronitrate mp: 171-174 ° C (Z) 71. 2- (4-bromophenyl) -3 ~ (iraidazol-l-yl) -2-propoxy-propionitrile, hydronitrate mp: l62-l65 ° C (Z) 722- (4-bromophenyl) -2-hexyloxy-3-iraidazol-l-yl) propionitrile,

Hydronitrate mp: 135-138 ° C (z) 3- (imidazol-l-yl) -2- (2-methylphenyl) -2-propoxypropionitrile, * hydronitrate mp: l8 © -l83 ° C (Z) 2-hexyloxy-3- (imidazol-l-yl) -2- (2-methylphenyl) propionitrile, hydronitrate mp: 170-173 ° C (Z) • 75 2- (4-bromophenyl) -2-butoxy- 3 “(iraidazol-l-yl) propionitrile ngO: 1.5405 76 2- (4-bromophenyl) -3- (imidazol-l-yl) -2-propoxy-propionitrile ngO: 1.5418 77i 2- (4 -Bromphenyl) -2-hexyloxy-3- (imidazol-l-yl) propionitrile ngO: 1.5274 7Q 2-Butoxy-3- (imidazol-l-yl) -2- (2-methylphenyl) propionitrile ngO: 1.5248 79e 2-butoxy-3- (imidazol-1-yl) -2- (2-methylphenyl) propionitrile,

"Hydronitrate mp. · 184-86 ° C

80 2-hexyloxy-3- (imidazol-l-yl) -2- (2-methylphenyl) propionitrile ngO: 1.5163 8l; 2-decyloxy-3- (imidazol-l-yl) -2-phenyl-propionitrile ngO: 1.5020 * 3- (imidazol-1-yl) -2- (2-methylphenyl) -2-propoxypropionitrile ngO: 1.5276 83 2-butoxy-2- (3-chlorophenyl) -3- (imidazol-l-yl) propionitrile nGO: 1.5282 §4 2- (3-chlorophenyl) -2-hexyloxy-3- (imidazole -l-yl) -propionitrile, hydronitrate mp: l62-l65 ° C (Z) 85.2-decyloxy-3- (imidazol-l-yl) -2- (2-methylphenyl) -propionitrile,

Hydronitrate Mp. 151_155 ° c (z) B6. 3- (imidazol-l-yl) -2- (2-methylphenyl) -2-octyloxypropionitrile ngO: 1.5173 87. 2-decyloxy-3- (imidazol-l-yl) -2- (2-methylphenyl ) -propionitrile 40 n0: 1.5139 r \ i -27- «0 3« r “2 Board of Directors: Dr. Herbert AsmisDr. Christian BruhnHans-Jürgen Hamann Postal address: SCHERING AG D-1000 Berlin 65 - P.O.Box 65 0311

'' SCHERINGAG

Intellectual Property & 8. 2-butoxy-3- (imidazol-l-yl) -2- (4-methoxyphenyl) propionitrile,

Hydronitrate mp: l63-l67 ° C (Z) 89. . 2-butoxy-3- (imidazol-l-yl) -2 - (^ - methoxyphenyl) propionitrile 90. 2- (4-chlorophenyl) -2-hexyloxy-3- (imidazol-l-yl) propionitrile,

Hydrogen oxalate m.p .; 195-197 ° C (Z) 91> ‘2- (4-chlorophenyl) -2-hexyloxy-3- (imidazol-l-yl) propionitrile,

Hydrogen sulfate Mp .: 158 -63 ° C (Z) »(Z = decomposition)

The 3-aryl- or 3-alkyl-sulfonyloxy-propionitriles of the general formula II with Y in the meaning aryl- or alkylsulfonyloxy to be used as starting materials have not hitherto been described in the literature. These aryl or alkylsulfonyloxy compounds of the general formula II are obtained by using the methods which are known or known per se (cf. for example Rubin et al., JACS 67, 192 f (19 ^ 5) »Hess et al ., Ber. German.

Ges; 50, 39¾ (1917)) accessible phenylacetonitriles of the general formula III,

0 - R

Z - CH XII

L ______ -28- u cn cn m w T “2 Board: Dr. Herbert AsmisDr. Christian BruhnHans-Jürgen Hamann Postal address: SCHERING AGD-1000 Berlin 65Postbox 65 0311

-28- SCHERINGAG

’! - Commercial * »1 legal protection where Z and R * have the meaning given for formula I, hydroxymethylated by methods known per se and the 3-hydroxypropionitriles of the general formula IV thus obtained,

* the 0 - R

Z - C - CH - OH IV

. CN

where Z and R have the meaning given for formula I, with suitable sulfonic acid derivatives, such as, for example, sulfonic acid chlorides, if appropriate with the addition of an acid binder. The hydroxymethyl compounds of the general formula IV are hitherto not known from the literature.

The 3 “halogen-propionitriles of the general formula II with Y meaning halogen, which are known from the literature, are obtained by reacting the above-mentioned phenylacetonitriles of the general formula III with dihalomethanes by methods known per se.

The production of a starting product is described below.

3iMethylsulfonyl-2; -j) henyi-2-pro £ oxy- £ ropionitrll 27 g (0.154 mol) 2-phenyl-2-propoxy-acetonitrile are dissolved in 120 ml pyridine and 18.5 g (0.6l4 mol) Paraformaldehyde added. 7i7 ml of tetrabutyl- \ L · c board is added to this suspension while cooling with biscuits. Herbert Aamis * Dr. Christian BruhnHans-Jürgen Hamann Postal Address: SCHERING AGD-1000 Bariin 65Pox 650311 2I Dr. Heinz HannseKarl Otto Mittelstenarheid. Dr. Horst Witzei n *> l. m * ____- λλ *****

SCHERING AG

^ 9 “Intellectual Property Protection” «ammonium hydroxide (TBAOH) and stirs vigorously for 17 hours. The reaction mixture is poured onto ice water and extracted twice with ether. Then the ether phase is washed twice with aqueous sodium chloride solution and dried with magnesium sulfate. After filtering off the desiccant and spinning in a vacuum, 9 remains a colorless oil, which turns out to be chromatographic as a thin layer and can be 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 19.5 S (0.171 mol) of methanesulfonic acid chloride were added. 18.6 g (0.184 mol) of triethylamine are added dropwise at 10 ° C. The mixture is stirred at room temperature for 30 minutes, filtered from the precipitated triethylarain hydrochloride and concentrated. The residue is taken up in ether, washed with dilute HCl solution, water and sodium bicarbonate solution and again twice with water. It is dried with magnesium sulfate, the drying agent is suctioned off and concentrated. The oily residue is dried in vacuo. It turns out to be pure by thin layer chromatography. Yield: 32.27 S - 86% of theory ηρ = 1.5000 3-methylsulfonyl-2-phenyl-2-propoxypropionitrile j u · L · '. . . _....... ... . . . .. .. .. _. .. __________ .. .. ___

SCHERING AG

" Intellectual Property

The following exemplary embodiments serve to explain the possible uses of the compounds according to the invention, which were carried out in the form of the preparations listed above. EXAMPLE 3

Effect of seed treatment against Helminthosporium spec. on barley.

Barley seed naturally attacked by Helminthosporium gra-mineum was sown untreated or treated as indicated in the table in plant pots with soil and left to germinate at temperatures below + 16 ° C. After emergence, the seedlings were illuminated with artificial light for 12 hours a day.

After about 5 weeks, all of the plants that had emerged and those infected with fungi were counted for each test element.

The fungicidal activity was calculated as follows: 100 - 10 · ° ·. ? —Befa11 ..in treatment _% efficacy ΐυυ infestation in untreated * wxrKung

The compounds were in the form of 20% wettable powder.

L

-¾ <7 a w V “2 Board: Dr. Herbert AsmisDr. Christian Bruhn - Hans-Jürgen Hamann Postal address: SCHERING AGD-1000 Berlin 65Postbox K 0311 Z Dr. Heinz Hannse - Karl Otto MittelstenscheidDr. Horst Witzei postal check account: Berlin-West 1175-KH. Bank code 10010010 5 Chairman of the Supervisory Board: Dr. Edward v. Schwartzkoppen Berliner Commerzbank AG, Berlin, account no. 100 7006 00, bank code 100 400 00 1 ..... D .. ·; ... ß B »tin 441 / C / VM Rnntlaifrshl 1ίϊΊ 7fifl nn

SCHERING AG

31 “Intellectual Property Law» ·

G Active substance according to the invention

Compound No. 100 kg of seed S Effect 1 50 95.6 2 50 100 3 50 100 h 50 100 ’5 50 100 6 50 100 7 50 100 8 50 100 9 50 100 10 50 100 11 50 100 12 50. 100 13 50 100 lk 50 100 15 50 100 16 50 100 17 50 100 18 50 100 19 50 100 20 50 100 21 50 100

Comparative agent methoxyethyl Hg silicate 2.63 87 EXAMPLE k

Effect of prophylactic leaf treatment against Erysiphe cichora-cearum on pumpkin plants in the greenhouse.

, / d Board: Dr. Herbert AsmisDr. Christian BruhnHans-Jürgen Hamann Postal address: SCHERING AGD-1000 Berlin 65Postbox 650311 i. Heinz HannseKarl Otto Mitteistenscheid - Dr. Horst Witzei postal check account: Berlin-West 1175-101. Bank code 100 10010

Jf Chairman of the Board of Supervisors * · Dr PHtiarrl v firhwarf7l6nnruin fUrMner r.nmfnnr7hBnIr ß Rertln i ^ nnfruMr RanVUlhthl ΙΟΓϋΜΜ —— * ms * · _ni__ '· 7 · - -i J * L..Î ._A »-y * · Τ * »'ι» ν · »—ΜΓ» - ^

SCHERING AG

^ 32- Intellectual Property Law

Pumpkin seedlings sprayed to runoff with the specified active compound concentrations were inoculated after the spray coating had dried on by dusting Erysiphe cichoraceanun flour powder and incubated together with inoculated, untreated control plants in a greenhouse at 2 ° C. After a week, the infected flour surface in S was estimated from the entire leaf area. The fungicidal activity was calculated as follows: 100. Infection in Treated «,

100 - Infection in PnbehMd.lt- ’* Wirku“ S

The substances were formulated as 20 sig spray powder. Active ingredient con

Compound no. Concentration%% effect 1 0.025 100 0.005 100 0.001 100 2 0.025 100 0.005 100

0.001 100

3 0.025 100 0.005 100 0.001 100 4 0.025 100 0.005 100 0.001 100 5 0.025 100 0.005 100 0.001 100 6 0.025 100 0.005 100 0.001 100 1 i {/ ~ \ -i33- * -; Board: Dr. Herbert AsmisDr. Christian Bruhn * Hans-Jürgen Hamann Postal address: SCHERING AG - D-1000 Berlin 65 * Postfach 65 0311 2 Dr. Heinz HannseKarl Otto MittelstenscheidDr. Horst Witzei Postschedc account: Berlin-West 1175-101. Bankfeitzah! 10010010

SCHERINGAG

-33-, Commercial legal protection% «

Krfindvtnf »{·« & · Virkatoffkon-

Bond Mr. »eatration%% effect 7 0.025 100 0.005 100 0.001 100, 8 0.025 100 0.005 100 0.001 100 9 0.025 100 0.005 100 0.001 100 10 0.025 100 0.005 100 0.001 100 11 0.025 100 0.005 100 0.001 100 12 0.025 100 0.005 100 0.001 100 13 0.025 100 0.005 100 0.001 100 14 0.025 100 0.005 100 0.001 -87 15 0.025 100 0.005 100 0.001 100 16 0.025 100 0.005 100 0.001 100 17 0.025 100 0.005 100 0.001 100 18 0.025 100 0.005 100 / ° »001 100 -3k- : Board of Directors: Dr. Herbert Asmls Christian Bruhn - Hans-Jürgen Hamann Postal address: SCHERING AG · D-100Q Berlin 65 · Postfach 650311 i "Dr. Heinz Hannse · Karl Otto Mittelstensdieid · Dr. Horst Witzei Postal check account: Berlin-West 1175-101, Bankleltzah! 10010010

, 34. SCHERINGAG

Commercial legal slot «* ftrf ±» d «agag ** M & · Virkatoffkoa-

Varbiadung Kr, _ »aatration% _% Effect 19 0.025 100 0.005 100 0.001 100 20 0.025 100 0.005 100 0.001 100 s 21 0.025 100 0.005 100 0.001 100 4 22 0.001 100 0.0002 100 23 0.001 100 0.0002 100 2k 0.001 100 0.0002 100 25 0.001 100 0.0002 100 26 0.001 100 0.0002 100 27 0.001 100 0.0002 100 28 0.001 100 0.0002 100 29 0.001 100 0.0002 100 30 0.001 100 0.0002 100 31 0.001 100 0 , 0002 100 4 32 0.001 100 0.0002 100 33 0.001 100 0.0002 100

3k 0.001 100

0.0002 100

/ U

CO

Ol ta -a- V "·: Board of Directors: Dr. Herbert AsmisDr. Christian BruhnHans-Jürgen Hamann Postal address: SCHERING AG D-1000 Berlin 65Postbox 65 031t z Dr. Heinz HannseKarl Otto Mittelstenscheid - Dr. Horst Witzei postal check account: Berlin-West 1175-101. Bank code 10010010 S Chairman of the Supervisory Board: Dr. Edward v. Schwartzkoooen Berliner Commerzbank AG. Berlin. Account number. 108 7006 00. Bank code 100 4001

.35- SCHERINGAG

Intellectual Property • "

He inventions active ingredient% effect

Compound no. Concentration% 35 0.001 100 0.0002 100 36 0.001 100 0.0002 98 37 0.001 100 0.0002 100 38 0.001 100 0.0002 100 39 0.001 100 5 0.0002 100 4o 0.001 100 0.0002 100 hl 0.001 100 0.0002 100 42 0.001 100 0.0002 100 43 0.001 100 0.0002 100 44 0.001 100 0.0002 100 45 0.001 100 0.0002 100 46 0.001 100 0.0002 100 47 0.001 100 0.0002 100 48 0.001 100 0.0002 100 49 0.001 100 0.0002 100 50 0.001 100 0.0002 100 51 0.001 100 0.0002 100 52 0.001 100 0.0002 100 53 0.001 100 0.0002 100 (f \ -36- * s «·· '

CD

CT

w £ Board: Dr. Herbert Asmis Dr. Christian BruhnHans-Jürgen Hamann Postal address: SCHERING AG - D-1000 Berlin 65Postfach 65 0311 i DrHeinz HannseKarl Otto Mittelstenscheid Horst Wltzel postal check account: Berlin-West 1175-101. Bank code 100 10010 S Chairman of the Supervisory Board: Dr. Edward v. SchwartzkODDen Berlin Commerzbank AG. Berlin. Account number. 108 7006 00. Bank code 100 400 00

-36- SCHERINGAG

Commercial legal protection ♦ *

% Active ingredient according to the invention

Compound no. Concentration% 5k 0.001 100 0.0002 100 55 0.001 100 0.0002 100 56 0.001 100 0.0002 100 57 0.001 100 0.0002 100 58 0.001 100 0.0002 100 * 59 0.001 100 0.0002 100 60 0.001 100 0.0002 100 61 0.001 100 0.0002 100 62 0.001 100 0.0002 100 63 0.001 100 0.0002 100 6k 0.001 100 0.0002 100 65 0.001 100 0.0002 100 66 0.0025 100 0.00025 100 167 0.0025 100 0.00025 100 68 0.0025 100 0.00025 100 69 0.0025 100 0.00025 100 70 0.0025 100 0.00025 100 71 0.0025 100 0.00025 100 72 0.0025 100 0 , 00025 100 «n ·· '

CD

03 he T * c board: Dr. Herbert AsmisDr. Christian Bruhn - Hans-Jürgen Hamann Postal address: SCHERING AGD-1000 Berlin £ 5Postbox 65 0311 7 DrHeinz Hannse - Karl Otto Mittelstenscheid - Dr. Horst Witzei postal check account: Berlin-West 1175-101. Bank code 100 10010 »«

.37- SCHERING AG

Intellectual Property

% Active ingredient according to the invention

Compound no. Concentration% 73 0.0025 1 °° 0.00025 100 7¾ 0.0025 100 0.00025 10 ° 75 0.0025 10 ° 0.00025 10 ° 76 0.0025 100 0.00025 100 77 0.0005 99 0.00005 100 7 & 0.0005 100, 0.00005 100 EXAMPLE 5

Effect of leaf treatment against Piricularia oryzae on rice seedlings in the greenhouse.

Young rice plants were sprayed to runoff point with the active ingredient concentration given in the table. After the spray coating had dried on, the treated plants and untreated control plants were inoculated by spraying on a suspension of spores (approximately 200,000 ml of leaf spot pathogen Piricularia oryzae) and incubated moist in the greenhouse at +25 to + 27 ° C.

After 5 days it was determined what percentage of the leaf area was affected. From these infestation numbers, the fungicide effect was calculated as follows: "" "100. Infection in treated «,, 100 - infestation in untreated '“ * Effective

The substances were formulated as 20 pounds wettable powder.

S / -38- ml * rl L’V ——- Board: Dr. Herbert AsmisDr. Christian BruhnHans-Jürgen Hamann Postal address: SCHERING AGD-1000 Berlin 65 - Postfach 650311 t Dr. Heinz HannseKarl Otto MittelstenscheidDr. Horst Witzei postal check account: Berlin-West 1175-101. Number of bank seats 100 10010 • Chairman of the Supervisory Board: Dr. Edward v. Schwartzkoppen Berliner Commerzßank AG. Berlin. Account number. 1087 006 00. Bank code 100 400 00

.38- SCHERING AG

Commercial legal push; •%

Active ingredient con

Prevention No. concentration%% effect 1 0.1 89 0.02 63 2 0.1 97.3 0.02 89 * 4 0.1 9 ^. 5 0.02 70 5 0.1 95 0.02 77, 5 11 0.1 95 0.02 80 12 0.1 95 0.02 65 13 0.1 92.5 0.02 70 14 0.1 95 0.02 80 15 0.1 98 0.02 65 16 0 , 1 95 0.02 55 17 0.1 97.5 0.02 90 18 0.1 95 0.02 80? A.

·: / Board: Dr. Herbert AsmisDr. Christian BruhnHans-Jürgen Hamann Postal address: SCHERING AGD-10CÛ Berlin 65Postbox 65 6311 Z Dr. Heinz HannseKarl Otto Mittelstenscheid - Dr. Horst Witzei postal check account: Berlin-West 1175-101. Bank code 100 10010 J! Chairman of the supervisory board: Dr. Edward v. Schwartzkoppen Berliner Commerzbank AG, Berlin, account no. 108 7006 00, bank code 100 400 00

3 * ·>; .__ t__λ ___ ii_ l.u. ____> η ___ 1_____ Rerliner nisrnntrvRanV ΑΩ Rerlin KonfruWr 9l1ffinnA Ranlrt «if7» hl 1M 7D0QQ

• »

SCHERINGAG

~ Commercial legal protection

Compound no. Concentration% S effect 19 0.1 92.5 0.02 65 20 0.1 95 0.02 85 a 21 0.1 95, 0.02 80 EXAMPLE 6

Effect of prophylactic leaf treatment against Botrytis cinerea on tomato plants in the greenhouse.

Young tornate plants were sprayed to runoff point with the active compound concentration given in the table. After the spray coating had dried on, the treated plants and untreated plants were inoculated by spraying on a suspension of spores (about 1 million per ml of fruit juice solution) of the gray mold pathogen Botrytis cinerea and incubated moist at about 20 ° C. in the greenhouse. After the untreated plants collapsed (= 100% infection), the degree of infection of the treated ones was determined. The fungicidal activity was calculated as follows: 100. Infection in treated ",

100 - Infestation in Pnverarbeitung.lt = * WirtamS

The compounds according to the invention were present in 20 formulations. -kO-

Board: Dr. Herbert Asmis * Dr. Christian BruhnHans-Jürgen Hamann Postal address: SCHERING AG - D-1000 Berlin 65Postbox 65 0311! Ψ Dr. Heinz Hannst * Karl Otto Mittelstenscheid * Dr. Horst Witzel Postschedc account: Berlin-West 1175-101. Bank code 100 10010 <1 yes Chairman of the Supervisory Board: Dr. Edward v. Schwartzkoppen Berliner Commerzbank AG, Berlin, account no. 1087 006 00, bank code 100 400 00 a r p. . ..Φ n i. <n i! _ Lr_ Αλλα ΗΛΛ 7ΙΙΛ Art

.40. SCHERING AG

Commercial law * slot

Invention active ingredient con

Compounds No.centration # # Effect 2 0.025 95 3 0.025 80 12 0.025 90 13 0.025 95 14 0.025 6o 15 0.025 85 * 16 0.025 '70 17 0.025 90 18 0.025 90 19 0.025 95 20 0.025 90 21 0.025 8ο

Comparative experiment 1- (4-chlorophenoxy) -3.3 “din» ethyl-1- (1,2,4-tria- * ol-l-yl) -2-butanone 0.025 6θ B1ISPI1L 7 .......

Effect of prophylactic leaf treatment against Plasmopara viticola on vine plants in the greenhouse.

Young grapevine plants with about 5 to 8 leaves were sprayed to runoff point with the stated concentration, after the spray coating had dried on, sprayed with an aqueous suspension of sporangia of the fungus (about 20,000 per ml) underneath the leaf and immediately in the greenhouse at 22 to 24 ° C. and saturated with water vapor if possible Atmosphere incubated

From the second day onwards, the humidity was reduced to normal level for 3 Li 4 days (30 to 70 # saturation) and then kept at Vaaserdaapf saturation for one day. Then iJU -ii- J / \ Board of Directors: Dr. Herbert Asmia «Dr. Christian Bruhn · Hans-Jürgen Hamann Postal address: SCHERING AG · 0-1000 Berlin 65 * Postfach 60311 2 fir Hninr Hanna «. Karl ÛÜA UittelctentrhjiM. fV Harif Witznl n __.__> ___ w__. «% __ ur__. yaj m _____ * .m .m. «*»

t SCHERING AG

- ii- “Commercial law protects each leaf of the percentage of fungus-infested area, and the average per treatment was calculated as follows to determine the fungicidal effect: 100. Infested in Treated.

100 - Infestation "" in 'Untreated - * Effect i • The substances were formulated as 20 spray powder.

Active ingredient con

Connections no. Concentration% # effect 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

Cress seeds were treated in the laboratory with an aqueous emulsion of the agents according to the invention.

1 / y / Board: Dr. Herbert AsmisDr. Christian BruhnHans-Jürgen Hamann Postal address: SCHERING AGD-1000 Berlin 65Postbox 65 0311? ---- U3r. Heinz HannseKarl Otto Mittelstenscheid - Dr. Horst Witzei postal check account: Berlin-West 1175-101. Bank code 10010010 Ü Chairman of the Supervisory Board: Dr. Edward v. Schwartzkoppen Berliner Commerzbank AG, Berlin, account no. 108 7006 00, bank code 100 400 00 I ««

SCHERING AG

Intellectual Property

The concentration of the active ingredients in the emulsion was 100 ppm.

For this purpose, a slide was placed in a 200 ml glass nozzle with 10 ml active ingredient emulsion. Filter paper was drawn on the slide. When the filter paper was saturated with the solution, 10 cress seeds were evenly distributed on it.

i

Then the lid of a petri dish was placed on the neck.

Two glass nozzles were used for each substance.

For evaluation, the lengths of the shoots and roots were measured from the germinated seeds after 7 days.

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

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

α οι w V “c Board: Dr. Herbert AsmisDr. Christian ßruhn - Hans-Jürgen Hamann Postal address: SCHERING AGD-1000 Berlin 65- PO Box 050311 2 Dr. Heinz HannseKarl Otto Mittelstenscheid - Dr. Horst Witzei postal check account: Berlin-West 1175-101. Bank code 10010010

SCHERING AG

-4 3 “Intellectual Property Protection” «

Growth according to the invention in%

Compounds No. Sproß_root 1 71 57 2 86 71 3 67 100 4 67 57 5 67 43 6 67 71 7 83 86 8 67 71 9 67 71 10 83 71 11 100 67 12 50 22 13 50 22 14 100 78 15 67 44 16 50 44 17 83 56 18 67 67 19 100 56 20 83 78 21 50 44 22 50 57 EXAMPLE 9

Cotton was grown to the cotyledon stage under greenhouse conditions.

The compounds according to the invention were sprayed onto the plants at a rate of 1 and 2 kg of active ingredient / ha. 3 weeks after 2 of the application, the total length of the plants and the length I - -44- π% i ,, _ Board: Dr. Herbert Asmis * Dr. Christian Bruhn * Hans-Jörgen Hamann Postal address: SCHERING AGD-1000 Berlin 65 * Postfach 650311 \ Dr. Heinz Hannse «Karl Otto Mittetstenscheid« Dr. Horst Witzei postal check account: Berlin-West 1175-101, Bankfeltzah! 10010010 * h

-44- SCHERING AG

Commercial legal protection of the first internode measured. The results are given in the table in the form of percentages as a comparison with the control.

There is a reduction in growth, which is usually stronger than that of the comparator.

* * Kg effective length according to the invention Length of the 1st

Compounds No. substance / ha of plants K Intemodiums% 11 '1 75 32 2 46 9 12 1 83 60 2 59 19 13 1 69 34 2 37 4 14 1 82 57 2 65 42 15 1 83 66 2 60 42 16 1 87 66 2 69 42 17 i 60 32 2 4l 9 18 1 69 15 2 52 13 19 1 48 15 2 45 9 20 1 75 43 2 52 9 21 1 95 72 2 71 34 22 1 100 70 2 55 62

Comparative agent 2-chloroethyltrimethyl-1 52 23 ammonium chloride 2 44 23 l / _4 ^ 'g' Board: Dr. Herbert AsmisDr. Christian Bruhn - Hans-Jürgen Hamann Postal address: SCHERING AGD-1000 Berlin 65 - P.O.Box 650311 Dr. Heinz HannseKarl Otto MittelstenscheidDr. Horst Witzel postal check account: Berlin-West 1175-101, bank code 10010010

VnreitTanrfor <4ae litfoirhferat ·· f * lr Prlnar / 4 u ftrhwnrhircnrMtn Rflrlin «r AfSrnmarrhank Aß Rerlin linntr \ .Nr 1Π87ΤΪ ¥ ΐ1ΥΙ Rahlrlulbflhi IflOiflOfll * 1

SCHERING AG

Intellectual Property Law EXAMPLE 10

Effect of seed treatment against powdery mildew Erÿsiphe gra-minis on barley.

Seeds of spring barley were sown untreated or dressed with 100 g active ingredient / 100 kg in planters with soil and left to germinate in the greenhouse at temperatures around 20 ° C. After the first leaves had grown or fertilized, the plants were inoculated by coating them with mildew-infested plants. A week later it was noted what percentage of the leaf area was covered by mildew.

A fungicidal effect was calculated as follows: 100 - 10 ° · Treated = χ effective

Infestation xn Untreated e

Any intolerance to the treatment was assessed after the plants emerged. The evaluation was carried out according to the scheme 0 = total destruction 1 = 90% destruction 2 = 80% destruction 3 = 70 5% destruction 4 = 60% destruction 5 = 50 56% destruction 6 = 40% destruction 7 = 30 5% Annihilation 8 = 20? 4 annihilation 9 = 10 5 ^ annihilation 10 = undamaged

gL

1 board: Dr. Herbert Asmis Dr. Christian BruhnHans-Jürgen Hamann Postal address: SCHERING AGD-1000 Berlin 65- PO Box 650311 \ Dr. Heina Hannse Karl Otto Mittelstenscheid - Dr. Horst Witzei postal check account: Berlin-West 1175-101. Bank code 10010010 • Chairman of the Supervisory Board: Dr. Edward v. Schwartzkoppen Berliner Commerzbank AG, Berlin. Account number. 100 7006 00, bank number 100 400 00 9 ___ ^ ....... __ Dnrlinar niernnfrv.Cenl · 'Aß Rarlin knnfnAlr 9Ü / IVY1A Ranlrleibahl 1ΙΥΙ700 / ΙΠ

SCHERING AG

Intellectual Property " ".

The compounds according to the invention were in the form of wettable powders with an active substance content of 20%.

In contrast to the comparative agent, the compounds according to the invention were not only fully active against Erysiphe graminis but also completely compatible with the barley.

s

% Effectiveness tolerance according to the invention

Connections No. _ _ 1 100 10 2 100 10 5 100 10 6 100 10 7 100 10 8 100 10 9 99.5 10 10 100 10 11 93 10 15 100 10 16 99 io 17 95 10 21 100 10 22 100 10

Comparative 1- (4-chlorophenoxy) - 3,3-dimethyl-1- (1,2,4-triazol-l-yl) -2-butanone 100 4 EXAMPLE 11

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

y / -47-

Board: Dr. Herbert AsmisDr. Christian BruhnHans-Jürgen Hamann Postal address: SCHERING ASD-1000 Berlin 65 - P.O.Box 0311 Z Dr. Heinz HannseKarl Otto Mittelstenscheid - Dr. Horst Witzei postal check account: Berlin-West 1175-101, bank number 10010010 "5 Chairman of the supervisory board: Dr. Eduard v. Schwartzkoppen Berliner Commerzbank AG, Berlin, account no. 108700600, bank sorting number 10040000 # 4

SCHERING AG

-47- Commercial legal protection

Sugar beet plants with 4 well-developed leaves were sprayed to runoff point at the specified concentrations. After the spray coating had dried on, the treated plants and untreated control plants were uniformly sprayed with a suspension of 15,000 Cer-cospora spores per milliliter. The plants were incubated in the greenhouse at 26 ° C and water vapor-saturated air for four days and then kept at around 22 ° C for a further 10 days in the greenhouse. Then the proportion of leaf area affected was noted. The effects of the fungicides were calculated as follows: 100. Infestation in Treated, 100 - -—-— - =% effect

Infection in untreated

Active ingredient according to the invention

Compounds No. concentration # Effect S

1 0.05 100 0.01 100 2 0.05 100 0.01 100 4 0.05 100 0.01 99 5 0.05 100 0.01 96 11 0.05 100 0.01 100 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 t, ”S: S - #> - iti! Board of Directors: Dr.Herbert Asmis - Dr.Christian BruhnHans-Jürgen Hamann Postal address: SCHERING AGD-1000 Berlin 65 P.O.Box 650311 z Dr. Heinz HannseKarl Otto MittelstenscheidDr. Horst Witzei postal check account: Berlin-West 1175-101. Bank code 10010010 * Chairman of the Supervisory Board: Dr. Eduard V. Schwartzkoppen Berliner Commerzbank AG, Berlin, account no. 108 7006 00. Bank code 100 400 00

, R SCHERING AG

Commercial Legal Protection TF »

Active ingredient con

Compounds No concentration% Effect% 18 0.05 100 0.01 99.6 19 0.05 100 0.01 99.3 20 0.05 100 ο, οι 98 21 0.05 100 0.01 99.6

Means of comparison

Manganese ethylene bis-0.05 100 dithiocarbamate 0.01 79 EXAMPLE 12

Inhibition of fungal growth on nutrient solution.

20 ml of a nutrient solution consisting of grape juice and water (l: l) were placed in 100 ml glass flasks and the powdered active substance preparations were added. Subsequently, conidia (spores) of Pénicillium digitatum were inoculated. After an incubation period of 5 days at 22-24 ° C, the fungal development on the surface of the nutrient solution was assessed.

Rating: 0 = no fungal growth 1 = individual fungal colonies on the surface 2 = surface 5-10% covered by the fungal lawn 3 = surface 10-30% covered by the fungal lawn h = surface 30-60 # covered by the fungal lawn 5 = surface 60-100% covered with mushroom lawn

Active substances, active substance concentrations in the nutrient solution and results are listed in the table below. ^ ij J [/ \ Board: Dr. Herbert Asmls Christian BruhnHans-Jürgen Hamann Postal address: SCHERING AGD-1000 Berlin 65Postbox 650311 z Dr. Heinz HannseKarl Otto MittelstenscheidDr. Horst Witzei postal check account: Berlin-West 1175-101, bank code 10010010

“Chairman of the Supervisory Board: Dr. Edward v. Schwartzkoppen Berliner Commerzbank AG, Berlin, account no. 106 7006 00, bank code 100100 OC

c Site of the company: Berlin ..nd Rerakamen Berliner Disconto-Bank AG. Berlin, account no. 241/5008. Bank code 10070000

_k SCHERING AG

_ Commercial Redits Schütz «*

Active ingredient concentration according to the invention

Links. No. in the nutrient solution S 'winding 5 0.0005% k

0.001% O

6 0.0005 56 k, 0.001 56 1 17 0.0005 56 0 0.001 56 0 20 0.0005 56 0 0.001 56 0 21 0.0005 56 2 0.001 56 0 23 0.0005 S 0 0.001 56 0 2k 0.0005 56 1 0.001 56 0

27 0.0005% O

0.001 56 0 28 0.0005% 0 0.001 56 o 29 0.0005% 0 0.001 56 0 31 0.0005% 0 0.001% 0 32 0.0005 56 0 0.001% 0 • »4 0.0005 56 0 0.001% o -50- / u

CO

8 'c Board: Dr. Herbert Asmis - Dr, Christian BruhnHans-Jürgen Hamann Postal address: SCHERING AG - D-1000 Berlin 65 - P.O.Box 65 0311 Z Dr. Heinz HannseKarl Otto Mittelstenscheid Dr. Horst Witzei postal check account: Berlin-West 1175-101. Bank code 10010010

Chairman of the supervisory board: Dr. Edward v. SchwartzkODDen Berlin Commerzbank AG. Berlin. Account number. 108 7006 00, bank code 100 400 00

SCHERING AG

Intellectual Property " "

Active ingredient concentration according to the invention

Compounds No. in nutrient solution% winding 37 0.0005% 0 0.001% 0

38 0.0005% O

0.001% 0 *

Comparative agent (according to DE-OS 26 Ok 0k7) 3- (imidazol-1-yl) -2-phenyl-2-butyl-propionitrile - hydronitrate 0.0005 # 5 0.001% *

Untreated nutrient solution

Control “· * Αλ i * -51- m

CQ

Ç 4 Board: Dr. Herbert AsmisDr. Christian Bruhn Hans-Jürgen Hamann Postal address: SCHERING AG · D-1000 Berlin 65 · Postfach 65 0311 1 5r ‘,! ΠΖ, Τβ; ? rl 01.0 With, elstenschei £! Dr. Horst Witzei postal check account: Berlin-West 1175-101. Bank code 10010010 · = Chairman of the Supervisory Board: Dr. Edward v. Scfiwartzkoppen Berliner Commerzbank AG. Berlin. Account number. 108 7006 00, bank code 100 400 00

_51_ SCHERINGAG

Intellectual Property Law EXAMPLE 13 * *

Effect of prophylactic leaf treatment against the real one. Vine powdery mildew Uncinula nacator.

Young vines of the Silvaner variety with about 8 to 10 leaves were sprayed to runoff point 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. in a greenhouse for 12 days. The percentage of leaf area affected by mildew was then estimated in percent and the fungicidal activity was calculated as follows: 100 - Infested in Treated. 100 =% effect

Infection in untreated

The infection reached 88.3% in untreated. The agents were in the form of 20% wettable powder. The effects are shown in the table.

% Activity against Uncinula necator according to the invention

Compounds No. 0.025 0.005% w active ingredient 2 93 85 3 100 100 4 100 100 5 100 100 6 100 99 7 100 89 8 100 95 9 87 63 10 100 49 11 100 100 12 100 63 13 100 95 14 66 43 15 100 100 é \ -52- md »m« ci Board: Dr. Herbert AsmisDr. Christian BruhnHans-Jürgen Hamann Postal address: SCHERING AG D-1000 Berlin 65Postbox 650311 ç Pr ’Η1ηζ HannseKarl Otto Mittelstenscheid Horst Witzei postal check account: Berlin-West 1175-101, bank code 10010010 * *

_52_ SCHERING AG

Intellectual Property

% Activity against Uncinula necator according to the invention

Compounds No. 0.025 0.005% active ingredient 16 99 89 17 100 100 18 86 80 19 100 89 20 93 86. 21 100 100 22 100 92 EXAMPLE 1¾

Effect of prophylactic leaf treatment against apple scab Venturia inaequalis in the field.

Shoots of apple plants of the cultivar MM 106 which were in growth were treated to runoff with 0.1% active ingredient. Concentration

A suspension of conidiospores (330,000 per milliliter) was sprayed onto the leaves, and then the shoots were put on for 3 days after being put on polyethylene bags

Partial shade left to the infection by the fungus.

The bags were then removed. After a total of 2 1/2 weeks of testing, the percentage of the area affected by scab was estimated in percent. The untreated

Control showed 99% infestation. The success of the treatments was calculated as follows:

Infested in Treated. 100 o / ....

100_ _ =% effect

Infection in untreated

The compounds were in the form of 20% wettable powder.

k -53- <n a 60 «w T- c Board: Dr. Herbert AsmisDr. Christian BruhnHans-Jürgen Hamann Postal address: SCHERING AGD-1000 Berlin 65Postbox 65 0311 z Dr. Heinz HannseKarl Otto MittelstenscheidDr. Horst Witzei postal check account: Berlin-West 1175-101, bank code 100 £ 10010 Chairman of the Supervisory Board: Dr. Edward v. Schwartzkoppen Berlin Commerzbank AG. Berlin, account no. 108 7006 00, bank code 100 4001

-53- SCHERINGAG

Commercial legal protection • 4

% Effect according to the invention

Connections No.

18 100 19 85 EXAMPLE 15

Effect of curative leaf treatment blessing apple scab Venturia inaequalis in the field.

Sprouts of apple plants of the ί MM 106 variety that were growing were sprayed with a suspension of conidiospores (330,000 per milliliter) and immediately kept moist by putting polyethylene bags on them. The plants were in partial shade. The bags were removed after 3 days. Seven days after the inoculation, the plants were treated with 0.1% active substance concentration. After a further 1 1/2 weeks, the percentage of leaf area affected by apple scab was estimated in percent, it was 99% in the untreated state. The compounds according to the invention were in the form of 20 ml of wettable powder. The effect of the treatment was calculated as follows: 100. Infection in treated. 100 =% effect

Infection in untreated

% Effect V erb according to the invention in fertilizing no.

2 93 18 100 19 100 Véjfrglelchsmittel 2-butyl-3- (imidazol-l-yl) -2-phenyl- 90 propionitrile, hydronitrate L ^ \ -54-

CO

CB

CO

·: Board of Directors: Dr.Herbert Asmis · Dr. Christian Bruhn - Hans-Jürgen Hamann Postal address: SCHERING AGD-1000Berlin 65 - P.O.Box 650311 z Dr. Heinz Hannse - Karl Otto MittelstenscheidDr. Horst Witzei postal check account: Berlin-West 1175-101. Bank code 10010010

_54. SCHERING AG

Intellectual Property Law "" EXAMPLE 16

Prophylactic foliar treatment against Erysiphe graminis on barley.

|

Barley plants in the stage of the first leaf were sprayed to runoff point with the specified active ingredient concentration with the addition of an alkaryl polyglycol ether as wetting agent (0.05 9 »). After the spray coating had dried on, these plants and untreated control plants were uniformly coated with mildew-infested cereal plants and then incubated in a greenhouse at 20 to 22 ° C. for one week.

'Then the average mildew infestation was ever

Planter (18 to 20 plants) noted. The fungicidal activity was calculated using the formula 100-100 »attack in treated =% effect infection in untreated

The substances according to the invention were present as 20% formulations.

% Effect according to the invention

Compounds No. 0.025% 0.005%

Active ingredient Active ingredient 3 100 100 4 100 100 5 100 100 6 100 100 7 100 100 8 100 100 9 100 92 10 92 90 11 100 100 / -55- t \

CO

Ô £ 2 board: Dr. Herbert AsmisDr. Christian BruhnHans-Jürgen Hamann Postal address: SCHERING AGD-1000 Berlin 65Postbox 65 0311 i. Dr-Heinz Hann3eKarl otto Mittelstenscheid. Dr. Horst Witzei Postschedc account: Berlin-West 1175-101. Bank code 10010010 • Ï Chairman of the Supervisory Board: Dr. Edward v. Schwartzkoppen Berlin Commerzbank AG. Berlin, account no. 108 7006 00. Bank code 100400 00 2 Cif »rla ·· ßBealle« J.a (». ... J B ... L____ Rprliner nier rt ntfwRanif Aß Berlin 911 / 4VM Ranlrtttitrahl infl7flrtflü

., 5. SCHERINGAG

Intellectual Property Law t

Effect according to the invention with 0.005%

Compounds No. 0 »025 active ingredient

Active ingredient 12 100 100 13 100 100 2¾ 100 100 15 100 100 16 100 100 4 17 100 100 28 100 100 29 100 100 20 100 100 21 100 100 22 100 100 Λ -56- «o s ί Board: Dr. Herbert Asmis - Dr. Christian BruhnHans-Jürgen Hamann Postal address: SCHERING AGD-1000 Berlin 65 P.O.Box 65 0311 9 «

.56- SCHERING AG

Intellectual Property Law EXAMPLE 17

Effect of prophylactic leaf treatment against Uromyces appendiculatus (bean rust) in the greenhouse.

Bush bean plants at the stage of calf-developed primary leaves were sprayed to runoff point with 100 ppm active ingredient concentration. After the spray coating had dried on, the treated plants and untreated control plants were sprayed with a suspension of the Uredospore of Uromyces * appendiculatus. The plants were then incubated in a wet room at 22 ° C for two days and then kept at about 22 ° C under greenhouse conditions.

The rust pustules were counted 11 days after the spores were sprayed on (an average of 253 per leaf in the untreated control). The fungicidal activity was calculated as follows:. Pustules in treated. 100 .T. «100 - ——-——-- = 70 effect

Untreated pustules

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

% Effect according to the invention

Connection no.

1 91 2 96 3 95 4 94 12 100 15 99.5 16 95 17 99.4 18 99.9 -57- co 0 03 <1 Board of Directors: Dr. Herbert AsmisDr. Christian BruhnHans-Jürgen Hamann Postal address: SCHERING AG D-1000 Berlin ESPox 65 0311 z Dr. Heinz Hannse - Karl Otto MittelstenscheidDr. Horst Witzei postal check account: Berlin-West 1175-101, bank code 100 10010 Λ Chairman of the Supervisory Board: Dr. Edward v. Schwartzkoppen Berliner Commerzbank AG, Berlin, account no. 108 7006 00, bank code 100 400 00 # «

SCHERING AG

”57 Intellectual Property Law

% Wirkling according to the invention

Connection no.

19 93 21 93.6 22 95 27 95 28 97 EXAMPLE 18

Effect of prophylactic leaf treatment against Helmin-thosporium teres (= Pyrenophora teres), barley mesh spot disease.

Young barley plants in the stage of the first leaf were sprayed to runoff point with the stated concentrations. After the spray coatings had dried on, the treated plants and untreated control plants were sprayed with a suspension of the conidiospores of Helminthosporium teres and cultured in a drying chamber at 20-22 ° C. for 2 days. One week after the inoculation, the percentage attack on the leaf areas was noted. The fungicidal activity was calculated as follows:, Infection in treated. 100 0 / TT. , 100 - ---% effect

Infection in untreated

The compounds were in the form of 20% formulations.

% Effect according to the invention

Compound No. 5 ° U PPra 100 ppm 35 90 90 36 95 90 37 95 90 38 95 90. 39 95 95 | / “58-J t — x Board of Directors: Dr. Herbert AsmisDr. Christian BruhnHans-Jürgen Hamann Postal address: SCHERING AG D-1000 Berlin 65Postbox 65 0311 3C N Hr_ Weiny Hanne # ». Karl nttn UittoletencrheM. no Wnr «t Wit-rei ___. _________ -

-58- SCHERING AG

Intellectual Property *

% Effect according to the invention

Compound No. 500 ppm 100 ppm 40 100 100 41 100 98 42 100 100 43 loo loo 44 loo loo • ^ 6 loo loo Ä 47 100 100 48 100 ß9 '100 100 50' 100 96 51 100 100 52 98 89 22 100 100 54 96 96 55 100 100 27 100 100 58 100 96 59 100 89 fU \ -59- es

Co en ▼ T ~ 4 Board of Directors: Dr. Herbert AsmisDr. Christian Bruhn Hans-Jürgen Hamann Postal address: SCHERING AGD-1000 Berlin 65Postbox 65 0311 i Dr. Heinz HannseKarl Otto MittelstenscheidDr. Horst Wittel postal check account: Berlin-West 1175-101, bank code 10010010

.5 ,. SCHERINGAG

Industrial property protection ψ «nrctßPlEL 19 y ^ jdcung prophylactic foliar treatment against dwarf rust put; pinia hordei on barley in an air-conditioned plant growth chamber.

Barley plants at the stage of the first leaf were sprayed to runoff point at the specified concentration. After the spray coverings had been applied, the treated plants and untreated control plants were inoculated by painting over plants suffering from dwarf rust and taken to a plant growth chamber. At 15 ° G and in the two Erjite days under almost moisture-saturated air, the # plants were cultivated for 10 days. The percentages of rust-infested leaf area were then noted. The fungicide swing was calculated as follows:

Infested in Treated. 100 100 ---—— =% effect

Infection in untreated

Div> compounds were present as 20% formulations.

The table shows good to very good activity for numerous compounds according to the invention.

5% 0 ppm 32 100 42 100 43 100 45 100 46 100 47 100 48 100 49 100 54 100 u

W

Oi tn T-1; Dr * Herbert AsmïsDr. Christian BruhnHans-Jürgen Hamann Postal address: SCHERING AG * D-1000 Berlin 65 * Postfach 650311 z Dr.Hr - rtannse * Karl 0tto MittelstenscheidDr.Horst Witzei Postal check account: Berlin-West 1175-101, bank number 10010010

* V

.60. SCHERING AG

Intellectual Property

Effect according to the invention%

Compounds No. 500 ppm 55 100 58 100 6l 100 64 100 65 100 66 100 67 100 69 100 71 100 72 100 7¾ 100 75 100 76 100 77 100 78 100 7 g 100 80 100

L

-61- «9

A

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c. Board: Dr. Herbert AsmisDr. Christian Bruhn - Hans-Jürgen Hamann Postal address: SCHERING AGD-1000 Berlin 65Postbox 65 0311 i DrHeinz Hannse 'Karl 0110 MittelstenscheidDr. Horst Witzei postal check account: Berlin-West 1175-101. Bank code 100 10010 -Ï Chairman of the Supervisory Board: Dr. Eduard V. Schwartzkoppen of Berlin Commerzbank AG. Berlin, account no. 108 7006 00, bank code 100 400 00

SCHERING AG

- ~ Commercial legal protection 0.

EXAMPLE 20

Effect of prophylactic leaf treatment against yellow rust Puccinis striiformis on barley in an air-conditioned plant fox chamber.

Young barley plants were sprayed to runoff point at the stage of the first leaf with the stated concentrations.

After the spray coating had dried on, the treated plants and untreated control plants were sprayed with a suspension of the Uredospores of Puccinia striiformis in 1,2,2-trifluoro-1,2,2-trichloroethane and incubated in a * plant growth chamber at 150 ° C. Almost moisture-saturated air was provided in the first two days. After 15 days, the percentage of leaf area affected by rust was noted.

The fungicidal activity was calculated as follows:

Infested in Treated. 100 100 - --—— =% effect

Infection in untreated

% Effect according to the invention

Compounds No. 100 33 11 ppm 5 100 12 100 100 100 14 100 15 100 100 100 16 100 17 100 100 100; * 18 100 100 93 28 100 98 78, -62- n 09

CO

w- 4 Board: Dr. Herbert AsmisDr. Christian BruhnHans-Jürgen Hamann Postal address: SCHERING AG - D-1000 Berlin 65Postbox 65 0311? Dr. Heinz HannseKarl Otto MittelstenscheidDr. Horst Witzei ... _ ιι., ·), ^ Μηη <ινι (η i .....,. J „, postal check account: Berlin-West 1175-101, bank sort code! 10010010 * Chairman of the Board of Directors: Dr. Eduard v. Schwertzlrnnnan ___ ι, .λ is .. u. Mo7nncnn nvtiiwm EXAMPLE 21

SCHERING AG

“” Intellectual Property Law t «.

Effect of seed treatment against Helminthosporium sativum on barley in climatic plant growth chamber. Barley seed with artificial attack by Helminthosporium sativum was powdered with 50 g of active ingredient according to the invention per 100 kg. 2 g of treated or untreated seed were sown in plastic pots of 6.5 x 6.5 cm for each test element.

* Sand was used as a substrate. Two were

Repetitions created. The pots were placed in a plant growth chamber at 15 ° C. After k weeks, the emerged plants were examined for percentage attack on the stem base. The fungicidal activity was calculated from the average of the repetitions as follows:

Infested in Treated. 100 100- --- =% effect

Infection in untreated

The agents according to the invention were in the form of 20% formulations.

% Action against

Compounds No. Helminthosporium sativum 7 99 17 99 21 99.5 25 100 26 100 29 100 32 10 ° 38 100

Comparative agent 2-butyl-3- (imidazol-l-yl) -2-phenyl-98.5 propionitrile 2-butyl-3- (imidazol-l-yl) -2-phenyl-98 propionitrile, hydronitrate

J

C3; 1

V-N

J Board: Dr. Herbert AsmisDr. Christian Bruhn Hans-Jürgen Hamann Postal address: SCHERING AGD-1000 Berlin 65Postbox 65 0311 i Dr. Heinz HannseKarl Otto MittelstenscheidDr. Horst Witzei postal check account: Berlin-West 1175-101, bank code 10010010 S Chairman of the supervisory board: Dr. Edward v. Schwartzkoppen Berlin Commerzbank AG. Berlin. Account number. 108 7006 00.Bankie number 100 400 (

.63. SCHERING AG

Intellectual Property Law f * EXAMPLE 22

Effect against Pseudomonas phaseolicola, causative agent of bean stain, in vitro.

Biomalt agar was cooled to about 45 ° C. after heat sterilization, and then mixed with the test substances in an aqueous preparation and poured into plastic petri dishes.

After the nutrient medium had solidified, the dishes of treated agars and dishes with untreated agar were inoculated as a control with a suspension of the fat stain pathogen Pseudomonas phaseolicola in the center by means of an inoculation loop. Then the dishes were incubated at 22 ° C.

After 2 1/2 weeks, the radial expansion of the grown colonies of the bacteria was measured. The bacteria-inhibiting effect was calculated as follows from the average of two repetitions per test element:

Radial growth in treated. 100 100- - ------------- =% inhibitory effect

Radial growth in untreated

The compounds were in the form of 20% formulations.

% Inhibitory effect of 250 ppm active ingredient in agar against Pseudomonas phaseolicola.

Inventional fa inhibitory effect

Connections No.

3 71 4 71 11 67 12 86 13 78 15 75 17 67 / U -64- / 1 / <? o co II board: Dr. Herbert Asmis - Dr. Christian BruhnHans-Jürgen Hamann Postal address: SCHERING AG - D-1C00 Berlin £ 5Postbox 65 0311 2 Dr. Heinz HannseKarl Otto Mittelstenscheid - Dr. Horst Witzei postal check account: Berlin-West 1175-101. Bank code 100 10010 «\ / ΛΓ« ΐ * τβηΗβΓ Häb AtifcirMerat «· Dr. PritiarH V. ftrfiwartyWnnnen Rerliner rnrnmerrhanl · in Reriin lfnntn.Klr 1 7lYtfi m RanWIoitTaM 1ΠΛ Affi ΛΛ <»

-64- SCHERING AG

Intellectual Property

% Inhibitory effect according to the invention

Connections No.

18 75 19 71 21 71

Comparative agent 2-butyl-3- (imidazol-l-yl) -2-phenyl-42 propionitrile, hydronitrate l · -65- co

CD

m * · ·: Board of Directors: Dr. Herbert AsmisDr. Christian BruhnHans-Jörgen Hamann Postal address: SCHERING AGD-1000 Berlin 65Postbox 65 0311 Z Dr. Heinz HannseKarl Otto Mittelstenscheid Dr. Horst Witzei postal check account: Berlin-West 1175-101. BanWeitzahl 100 10010 * Chairman of the Supervisory Board: Dr. Edward v. Schwartzkoppen Berlin Commerzbank AG. Berlin. Account number. 108 7006 00. Bank code 100 400

.6 ,. SCHERING AG

Intellectual Property Law 4 * EXAMPLE 23

Effect of prophylactic leaf treatment against powdery mildew Erysiphe graminis on barley in the greenhouse.

Young barley plants in the stage of the first leaf were sprayed to runoff point with the stated concentrations. After the spray coating had dried on, the treated plants and untreated control plants were inoculated with dry powdery pores by coating the test plants with infected plants. The test plants were then cultivated in a greenhouse at about 20 to 22 ° C. and, after a week, were rated for percent infestation of the leaf surface. The fungicidal activity was calculated as follows: traded in Befa11 in 100 = $ Wir] cu31g

Infection in untreated

The compounds were in the form of 20% formulations.

% Effect according to the invention

Compounds No. 100 ppm 20 ppm 28 100 100 29 10 ° 10 ° 30 100 99 31 100 100 32 - 100 33 100 100 3¾ 100 100 35 100 100 36 100 100 37 100 100 38 100 100 39 98 90 40 100 91 41 100 100 42 100 100 43 96 91 -66- T "1- · Board: Dr. Herbert Asmis Dr. Christian Bruhn · Hans-Jürgen Hamann Postal address: SCHERING AG - D-1000 Berlin 65 · Postfach 65 0311 A Dr · Heinz Hannse · Karl 0tto Mittelstenscheid - Dr. Horst Witzei postal check account: Berlin-West 1175-101. Bank code 100 10010 -S Chairman of the supervisory board: Dr. Eduard v. Schwartzkoppen Berliner Commerzbank AG. Berlin. Account number 106 7006 00. Bank code 100 400 00

_66. SCHERING AG

Commercial legal protection y *

% Effect according to the invention

Compounds No. 100 ppm 20 ppm 44 100 100 45 100 96 46 100 100 47 100 100 48 100 100 49 100 100 50 100 100 51 100 100 52 100 100 53 100 100 54 100 100 55 100 100 56 100 100 57 100 100 58 100 87 59 100 100 60 100 98 61 100 100 62 100 100 63 100 100 64 99 95 65 100 100 -67-

L

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«R» * · c Board: Dr. Herbert Asmis Dr. Christian Bruhn Hans-Jürgen Hamann Postal address: SCHERING AGD-1000 Berlin 65 - P.O.Box 65 0311 z Dr. Heinz HannseKarl Otto MittellenscheidDr. Horst Witzei postal check account: Berlin-West 1175-101. Bank code 100 10010

Claims (7)

1. Imidazolyl-propionitrile of the general formula 0.R. w R - Ç - CH - N (I 2 \ _ 1 CN - in which R is one or more, optionally, similar or different by halogen, alkyl, (C ^ -C ^ alkoxy, (C ^ C ^) - alkyl thio, trifluoromethyl or the nitro group-substituted aromatic hydrocarbon radical and 3 ^ (C ^ C ^ q) alkyl, (C ^ -Cg) alkenyl, (C ^ -Cg) alkynyl or an optionally - Phenylalkyl radical substituted by halogen, (C ^ -C ^ J ^ alkyl, (C1 ~ C ^> alkoxy, (C ^ C ^) - alkylthio, trifluoromethyl or the nitro group) and their acid addition salts with inorganic and organic acids. » 2. imidazolyl-propionitrile according to claim 1, wherein R is optionally one or more, identical or different by halogen, (C ^ -C ^ alkyl, (C ^ -C ^) - alkoxy, (C ^ -C ^) -Alkylthio, trifluoromethyl or the nitro group substituted phenyl radical and R ^ (C ^ -Cg) alkyl, allyl, propargyl or a given? · 1 / -2- I · / / \ Board: Dr. Herbert Asmis - Dr. Christian Bruhn * Hans-Jürgen Hamann postal address: SCHERING AG · D-1000 Berlin 65 * PO Box 65 0311 SCHERING AG _ 2_ industrial property protection <<if one or more, the same or different by halogen, XC ^ -C ^) - alkyl, (C -C4) alkoxy, (C ^ C ^) - alkylthio, trifluoromethyl or the nitro group substituted benzyl radical. 3- 3- (imidazol-1-yl) -2-phenyl-2-propoxypropionitrile, - hydronitrate 4. 3- (imidazol-1-yl) -2-phenyl-2-propoxypropionitrile * 5 · 2- Butoxy-3-4imidazol-1-yl) -2-phenyl-propionitrile, hydronitrate 6. 2-butoxy-3- (imidazol-1-yl) -2-phenyl-propionitrile 7 · 2-allyloxy-3- (imidazole- 1-yl) -2-phenyl-propionitrile, hydronitrate 8. 2-allyloxy-3- (imidazol-1-yl) -2-phenyl-propionitrile 9 · 2-ethoxy-3- (imidazol-l-yl) -2 -phenyl-propionitrile, hydronitrate 10. 2-ethoxy-3- (imidazol-l-yl) -2-phenyl-propionitrile 11. 3- (imidazol-l-yl) -2-methoxy-2-phenyl-propionitrile, hydronitrate 12. 3- (imidazol-1-yl) -2-methoxy-2-phenyl-propionitrile 13. 2- (2-chlorophenyl) -3- (imidazol-l-yl) -2-propoxy-propionitrile, hydronitrate '14 . 2-butoxy-2- (4-chlorophenyl) -3- (imidazol-l-yl) propionitrile, hydronitrate 15. 2-butoxy-2- (2-chlorophenyl) -3- (imidazol-l-yl) propionitrile , Hydronitrate 16. 2-allyloxy-2- (2-chlorophenyl) -3- (imidazol-l-yl) propionitrile, hydronitrate 17-2- (4-chlorophenyl) -3- (imidazol-l-yl) -2 -propoxy-propionitrile, hydronitrate 18. 2-allyloxy-2- (4-chlorophenyl) -3- (imidazol-l-yl) -propionitrile, hydronitrate? u • * Unrafanrlhr UarkArf A.mt. . your Ahfletlen bruhn. Uene Lurnen Msmann DftdflrivhHÎt ’N6 Aß. b-10Û0 ΒβΗΐπ β5PoStf & ch 65 H SCHERING AG Gmmfalichtr Rtchtsubub 19. 2- (2-chlorophenyl) -3- (imidazol-l-yl) -2-propoxypropionitrile 20. 2-butoxy-2- (4-chlorophenyl ) -3- (imidazo1-1-yl) propionitrile 21. 2-Butoxy-2- (2-chlorophenyl) -3- (imidazol-l-yl) propionitrile 22. 2-allyloxy-2- (2-chlorophenyl ) -imidazol-l-yl) -, propionitrile 23. 2- (4-chlorophenyl) -3- (imidazol-l-yl) -2-propoxy-propionitrile 24. 2-allyloxy-2- (4-chlorophenyl) - 3-imidazol-l-yl) -propionitrile 25.2-benzyloxy-3- (imidazol-l-yl) -2-phenyl-propionitrile, hydronitrate 26. 2-B »n * yloxy-3” (i * id * * ol-l-yl) · 2 · ρλ · ηγ1-ρΓ «ρ1θΒΐΐΓΐ1 27. 3- (imidazo1-1-yl) -2-ieopropyloxy-2-pkenyl-prepienitrile hydronitrate 28. 3- (imidazol-l-yl) -2-isopropyloxy-2-phenyl-propionitrile 29.2- (4-chlorophenyl) -2-hexyloxy-3- (imidazol-l-yl) propionitrile, hydronitrate 30. 2- (4-chlorophenyl) -2-hexyloxy -3- (imidazol-l-yl) propionitrile 31. 2-allyloxy-3- (imidazol-l-yl) -2- (2-methylphenyl) propionitrile, hydronitrate 32. 2- (3,4-dichlorophenyl) -3- (imidazol-l-yl) -2-propoxypropionitrile , Hydronitrate 33. 2-butoxy-2- (2,4-dichlorophenyl) -3- (imidazol-l-yl) propionitrile, hydronitrate 34. 2-allyloxy-2- (2,4-dichlorophenyl3-3- (imidazole -l-yl) -propionitrile, hydronitrate 35.2-ethoxy-2- (314-dichlorophenyl) -3- (imidazol-l-yl) -propionitrile, hydronitrate 36. 2-allyloxy-3- (imidasol-l-yl ) -2- (2-aathylpheayl) -prapio- ß nitrile -4- Ifc board: Dr. Herbart Asmts Dr. Christian Bruhn - Hans-JQrgen Hamann Poatanediritt: SCHERING AQ · D-10 »Berlin« 5 · Poetfach «8311 /1Dr.Heinz Hanns · * Kar! Otto Mitte IstanscfteidDr. Horst Witz ·! Hi. vui. · «** - ·« sw - «m BT.nan.-ii>« m «nma -4- SCHERING AG Intellectual Property 37. 2- (3,4-dichlorophenyl) -3- (imidazole-1 -yl) -2-propoxy-propionitrile 38.2-allyloxy-2- (3,4-dichlorophenyl) -3- (imidazol-l-yl) propionitrile 39.2-butoxy-2- (2,4 -dichlorophenyl) -3- (imidazol-l-yl) -propionitrile ß 40. - 2-allyloxy-2- (2,4-dichlorophenyl) -3- (imidazol-l-yl) -pro-. pionitrile 41.2-ethoxy-2- (3 * 4-dichlorophenyl) -3- (imidazol-1-yl) propionitrile __________________________________________ 42.3 "(imidazol-1-yl) -2-phenyl-2 - (1, 2,2-trimethyl-propoxy) -propionitrile, hydronitrate 43.3- (imidazol-1-yl) -2- (2-methoxy-ethoxy) -2-phenyl-propionitrile, hydronitrate 44. 2- (2.2- Dimethylpropoxy) -3- (imidazol-1-yl) -2-phenyl-propionitrile * hydronitrate 45.2- (2,2-Dimethyl-propoxy) -3- (imidazol-l-yl) -2-phenyl-propionitrile 46 2- (2-fluorophenyl) -3- (imidazol-l-yl) -2-propoxypropionitrile, hydronitrate 47.2-butoxy-2- (2-fluorophenyl) -3- (imidazol-l-yl) - propionitrile, hydronitrate 48. 2- (4-fluorophenyl) -3- (imidazol-l-yl) -2-propoxypropionitrile, hydronitrate 49.2-butoxy-2- (4-fluorophenyl) -3- (imidazole-1 -ÿl) -propionitrile, hydronitrate 50. 2-allyloxy-2- (2-fluorophenyl) -3- (imidazol-l-yl) -propionitrile, hydronitrate 51. 2-ethoxy-2- (2-fluorophenyl) -3 ~ (imidazol-l-yl) propionitrile, hydrinitrate L and GS SCHERINGAG ^ Intellectual Property 52. 2- (2-fluorophenyl) -3- (imidazol-l-yl) -2-me thoxypropionitrile, hydronitrate 53.3- (imidazol-l-yl) -2-phenyl-2- (1,2,2-trimethyl-propoxy) propionitrile 54.3- (imidazol-l-yl) -2- (2-methoxy-ethoxy) -2-phenylpropionitrile 55.2- (2-fluorophenyl) -3- (imidazol-l-yl) -2-propoxypropionitrile ^ 56. 2-butoxy-2- (2-fluorophenyl) -3- (imidazol-l-yl) propionitrile * 57. 2- (4-fluorophenyl) -3- (imidazol-l-yl) -2-propoxypropionitrile «58» 2-butoxy-2- (4-fluorophenyl) -3- (imidazol-l-yl) propionitrile 59 2- (2-fluorophenyl) -3-imidazol-l-yl) -2-methoxypropionitrile 60. 2-ethoxy-2- (2-fluorophenyl) -3- (imidazol-l-yl) propionitrile 61. 2-allyloxy-2- (2-fluorophenyl) -3- (imidazol-l-yl) propionitrile 62. 2-allyloxy-2- (4-fluorophenyl) -3- (imidazol-l-yl) propionitrile, hydronitrate 63. 2-ethoxy-2- (4-fluorophenyl) -3- (imidazol-l-yl) propionitrile, hydronitrate 64. 2- (4-fluorophenyl) -3- (imidazol-l-yl) -2-methoxy -propionitrile, hydronitrate 65.2-ethoxy-2- (4-fluorophenyl) -3- (imidazol-l-yl) -propionitrile 66. 2- (4-fluorophenyl) -3- (imidazol-l-yl) -2 -methoxy-propionitrile 67.2-allyloxy-2- (4-fluorophenyl) -3- (imidazol-l-yl) -propionitrile 68.2-decyloxy-3- (imidazol-l-yl) -2-phenyl-propionitrile ,. Hydronitrate 69.2- (3 »3-bimethylbutoxy) -3- (imidazol-l-yl) -2-phenylpropionitrile, hydronitrate 70.3" (imidazol-l-yl) -2-octyloxy ~ 2-phenyl-propionitrile 71 . 2- (3, 3-Dimethoxyhutoxy) -3-imidazol-l-yl) -2-phenyl-propionitrile -6- L mo> m T *. Herbert A «m? R. Dr Dhrîstîan firnhn. Hana-.lnrnen Hamann Pnefanaj-brlft · .QDWPOIWß Aß. D-1fVY1 Berlin 65 · Pöstfaeh 65 0311 '' SCHERINGAG "D“ Intellectual Property 72. 2- (4-Bromophenyl) -2-butoxy-3- (imidazol-l-yl) propionitrile, hydronitrate 73. 2- (4th -Bromphenyl) -3- (imidazol-l-yl) -2-propoxypropionitrile, hydronitrate 74.2- (4-bromophenyl) -2-hexyloxy-3-imidazol-l-yl) propionitrile, hydronitrate 75.3 - (Imidazol-l-yl) -2- (2-methylphenyl) -2-propoxy-propionitrile M hydronitrate 761 2-Hexyloxy-3- (imidazol-l-yl) -2- (2-methylphenyl) propionitrile, hydronitrate 77 · 2- (4-bromophenyl) -2-butoxy-3- (imidazol-l-yl) propionitrile 78. 2- (4-bromophenyl) -3- (imidazol-l-yl) -2-propoxypropionitrile 79 · 2- (4-bromophenyl) -2-hexyloxy-3- (imidazol-l-yl) propionitrile 80. 2-butoxy-3- (imidazol-l-yl) -2- (2-methylphenyl) propionitrile 81. 2-butoxy-3- (imidazol-l-yl) -2- (2-methylphenyl) propionitrile, hydronitrate 82. 2-hexyloxy-3- (imidazol-l-yl) -2- (2-methylphenyl) -propionitrile 83. 2-decyloxy-3- (imidazol-l-yl) -2-phenyl-propionitrile 84. 3- (imidazol-l-yl) -2- (2-methylphenyl) -2-propoxypropionitrile 85. 2-butoxy-2 - (3-Chlorophenyl) -3- (imidazol-l-yl) propionitrile 86. 2- (3-chlorophenyl) -2-hexyloxy-3- (imidazol-l-yl) propionitrile, hydronitrate §7. 2-decyloxy-3- (imidazol-l-yl) -2- (2-methylphenyl) propionitrile,? Hydronitrate 88.3- (imidazol-l-yl) -2- (2-methylphenyl) -2-octyloxypropionitrile 89.2-decyloxy-3- (imidazol-l-yl) -2- (2-methylphenyl) - propionitrile k CO ca Sr T “I: Board of Directors: Dr. Herbert AsmisDr. Christian Bruhn · Hans-Jürgen Hamann Postal address: SCHERING AG · D-1000 Berlin 65 · PO Box 650311 1-7- SCHERINGAG Intellectual Property Law • 9o. 2-butoxy-3- (imidazol-l-yl) -2- (4-methoxyphenyl) propionitrile, hydronitrate 91 2-butoxy-3- (imidazol-l-yl) -2 - (^ - methoxyphenyl) propionitrile 92. 2- (4-chlorophenyl) -2-hexyloxy-3- (imidazol-l-yl) propionitrile, hydrogen oxalate 93.2- (4-chlorophenyl) -2-hexyloxy-3- (imidazol-l-yl) -propionitrile, hydrogen sulfate M m 9 (T. Process for the preparation of imidasolyl-propionitrilane according to claims 1 to 93, characterized in that compounds of the general formula R - C - CH2 - Y with imidazole of the formula HC - NH HC ^ ßE in In the presence of a solvent and, if appropriate, in the presence of a base, in which R and R ^ have the abovementioned meaning and Y is halogen, or the alkylsulfonyloxy or arylsulfonyloxy radical which may be halogenated in the side chain. M cn cn w Board of Directors: Dr. Herbert Asmis · Dr. Christian Bruhn · Hans-Jürgen Hamann Postal address: SCHERING AG · D-1000 Berlin 65 · Postfach 65 0311 ί. 1! -8- SCHERING AG i Intellectual Property Law i t i 95 ·, biocidal agents, characterized by a content of at least one compound according to claims 1 to 93. 96. iBiocidal agents according to claim 95 with fungicidal activity, * * Λ 97 biocidal agents according to claim 95 98 · Biocidal agents according to claim 95 with bactericidal activity. 99 · Biocidal agents according to claim 95 in a mixture with carriers and / or auxiliaries. 'vA- —...... -9- m ~~ CB ---- m V— * - · Board: Dr. Herbert AsmisDr. Christian BruhnHans-Jürgen Hamann Postal address: SCHERING AG - D-1000 Berlin 65Postbox 65 0311