LU84771A1 - 1,2,4-TRIAZOL-1-YL-PROPIONITRILE, METHOD FOR PRODUCING THESE COMPOUNDS AND BIOCIDES CONTAINING THEM - Google Patents

Description

»R

I SCHERING AG

i -6- Commercial Reafrfsschut * 5 The invention relates to new 1,2,4-triazol-l-yl-propionitrile

Process for the preparation of these compounds and biocidal compositions containing them, in particular with a fungicidal action.

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

The object of the present invention is to propionitrile | To develop 15 derivatives which are widely used a! open up opportunities, particularly in the field of crop protection, and a broad spectrum of fungicidal activity $.

|| exhibit.

* {I This object is achieved according to the invention by imidazolyl- propionitriles of the general formula I 5 i 0 - R. ✓N— i ^: .i r - c - ch2 - n

ä 25 J: N

s in the JR one optionally one or more times, identically or differently, by halogen, (C ^ -C ^ alkyl, (C ^ -C ^) - alkoxy, (C ^ - 'C.) - Alkvlthio , Trifluoromethyl or the nitrogrunpe-substituted aromaxx hydrocarbon resx and 1 R ^ (C ^ -C ^ q) alkyl, (C ^ -Cg) alkenyl, (C ^ -Cg) alkynyl or one optionally one or more times, the same or different; by halogen, (C., - C, t) -A.lkyl, (C ^ -C ^ J-alkoxy, (C ^ -C ^) -

Alkylthio, trifluoromethyl or nitroerunoe substituted 35

Phenylalkyl radical; and their acid addition salts with inorganic and organic acids.

-7- 4 8 koj * -! , / r \ -C Vc-s; and: \ Dr_ He'öer Aöt! 1S. "=" "| Df. «E.nz fannse ·« ad Otto M:! JB.siër.S '=>., E D- ~ a ~ 3nr · »oraaswr.S · SCHES! N'6 AG - D--.CX Sa -un 55-. Postfa «·. SS £ 8.1 i £ rs: tte: eer 3e £ v & **** «,:« ι ««; § Jj-T: 'r.une% V: Z- ^ = τ ^ ·: ¾3 »* .Ba ^ .e.-aw-χ« ® *

SCHERING AG

7- Commercial Commercial Protection i j 5 The compounds according to the invention are biocidally active in the broadest sense, but are particularly notable for * fungicidal activity, in which they surprisingly outperform known active substances of analogous constitution and direction of action '4 years.

I '10 3 s The fungicidal activity surprisingly extends jsj 1 against fungi of various systematic positions.

'·! I! · When treating above-ground parts of plants I protect them against wind-borne pathogens. The compounds can be used for seed treatment against seed-borne pathogens. In addition, these have a systemic effect, that is, they are taken up by the roots of the plants j, for example after they have been introduced into the seed, are transported to the aerial parts of the plant - 20 ij and protect them against pathogens.

Further effects include a growth regulator-fj. see and a bactericidal effect.

·! 25th

Because of the recognized broad spectrum of activity, the compounds are not only suitable for protecting crops, i but also for protecting materials and combating human f | pathogenic and animal pathogenic microbes, which results in a wide range of possible applications.

= 1 3 °

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

'w; In the situation marked by the general formula 1! For example, gen can mean: \ l t £ Vofsfane: Cr. Herssrr As. "! '1 n ··' -» r ...-- a ..

1 s.a ser oess- sæn.jSs' .. · 1 Se - =. S-B- Α · 2. _______ * i

I SCHERING AG

! -8- GeiredsKcr.sr Rec-rfstdiuiz i! 5 R 2-FTuorphenyl, 3 “fluorophenyl, 4-fluorophenyl, 2-chlorophenyl, | 3-chlorophenyl, 4-chlorophenyl, 2-bromophenyl, 3 “bromophenyl, | 4-bromophenyl, 2-iodophenyl, 3-iodophenyl, 4-iodophenyl, 2,4-

Dichlorophenyl, 3> 4-dichlorophenyl, 2,6-dichlorophenyl, 2- 14 methylphenyl, 3-methylphenyl, 4-methylphenyl, 2-ethylphenyl, * 10 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.-butylph.en-J 15 yl, 2-methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl, 2-ethoxyphenyl, 3 ** ethoxyphenyl, 4 -Ethoxyphenyl, 2-methylthio-a phenyl, 3-methylthiophenyl, 4-methylthiophenyl, 2-ethylthiophenyl, 3-ethylthiophenyl, 4-ethylthiophenyl, 2-trifluoromethyl- \ phenyl, 3-trifluoromethylphenyl, 4-trifluoromethylphenyl, 20 Nitrophenyl, 3 "nitrophenyl, 4-nitrophenyl, 3-flu-or-4- j methoxyphenyl, 3-chloro-5-nitrophenyl, 4-chloro-2-fluorophenyl, i 3,4,5-trimethoxyphenyl, or 2-chlorine -2-nitrophenyl i and R (Ci ~ Cio) alkyl, for example methyl, ethyl, propyl, butyl, | Pentyl, Hexyl, Heptyl, Octyl, Nonyl, Decyl, Isopropyl, 2,2- | Dimethylpropyl-1, 3t3-biraethyl-butyl-2, (C ^ -Cg) alkenyl, for example 2-buten-1-yl, 3-methyl-2-buten-1-yl, hexenyl,

Heptenyl, octenyl, phenylalkyl, for example benzyl, 2-fluorobenzyl, 3-fluorobenzyl, 4-fluorobenzyl, 2-chlorobenzyl, 3-chlorobenzyl, 4-chlorobenzyl, 2-bromobenzyl, 3-bromobenzyl, 4-bromine -benzyl, 2,4-dichlorobenzyl, 2,6-dichlorobenzyl, 3i4-dichlorobenzyl, 2-methylbenzyl, 3 ~ methylbenzyl, 4-methylbenzyl, 2-nitrobenzyl, 3 “nitrobenzyl, 4-nitrobenzyl, 2-Tr ± fluoromethyl - |; benzyl, 3- "TriI'l '^ ormethylbenzyl, 4-trifluoromethylbenzyl, 2- I methoxybenzyl, 3-methoxybenzyl, 4-methoxybenzyl, 2-ethoxy-j. benzyl, 3-ethoxybenzyl, 4-ethoxvbenzyl, 2-propoxybenzyl,: 3-Propoxybenzyl, 4-Propoxybenzyl, 2-Butoxybenzyl, 3-Sutcxy-benzyl, 4-Butoxybenzyl, 2-Methylthiobenzyl, 3-Mezkylihio-: j 1 -9- j Varstand: Sr. «erae'S Asm · *. 3r. Ch -stiar B-un-

Cr. ne.-Ä nannse - Karl C «a Μ. ;; β · 8ΐ, -. Ββ1βιά £ Pesans =, f; ft; S = HE * «NG A3 - Β-ΠΧ B-r! F-« r ev eese-.ssna ·? .JSsrur.-Nc Sa ^ ar-a- 5:,: .-, :: ZZZ *** ™ = ··· »·. Kcnta no. «Oa ^ ^, ·.

SCHERING AG

-9 _ Gewerfeiicher R ^ rtisdmtz 5

* I

; 5 benzyl, ^ -methylthiobenzyl, 2-ethylthiobenzyl, 3 “ethylthio-benzvl, 4-ethylthiobenzyl, 2-butylthiobenzyl, 3-butylthio-i.i benzyl, ^ -butylthiobenzyl.

; Examples of inorganic and organic acids to form the acid addition salts are halogen, hydrochloric acid, such as hydrochloric acid and hydrobromic acid, 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 r.

. and 1,5-naphthalenedisulfonic acid · I «20

These acid addition salts can be prepared by the customary salt formation processes, for example by dissolving a compound; J of the formula I in a suitable solvent and adding

Igen of the acid can be obtained.

2p 'of the compounds according to the invention are notable for! f; I a fungicidal effect especially from those in which! in the general formula I, the radical ‘1 R phenyl, 2-chlorophenyl, 3 ″ chlorophenyl, 4-chlorophenyl,’ I 2,4-dich.lorphenvl, 3 j - “bichloronhenyl, k_bromnhenyl,; 30 i I * 2-fluorophenyl, ^ -fluorophenyl or 2-methylphenyl: I · | . and * 'is ethyl, allyl, propyl, isopropyl, butyl or hexyl f.

.1 35 »f ι? if \: .1 ...... k: k jt

SCHERING AG

Commercial legal protection i ii Ί j a 5 Preferably, such connections are to be mentioned,

S where R is phenyl, 4-chlorophenyl or 2-methylphenyl and IR ^ propyl, isopropyl or butyl.

* 10 The following compounds according to the invention are of outstanding activity: 2-isopropoxy-2-phenyl-3- (1,2,4-triazol-1-yl) propionitrile,

Hydronitrate 2-butoxy-2- (2-methylphenyl) -3- (1,2,4-triazol-1-yl) propion? itril, hydronitrate each 2-phenyl-2-propoxy-3- (1,2,4-triazol-1-yl) propionitrile, D hydronitrate 2-butoxy-2- (4-chlorophenyl) -3 “(1,2 , 4-triazol-1-yl) propionitrile, hydronitrate 2- (4-chlorophenyl) -2-propoxy-3- (1,2,4-triazol-1-yl) propionitrile, hydronitrate | 2-isopropoxy-2-phenyl-3- (1,2,4-triazol-1-yl) propionitrile f, 20 2-butoxy-2- (2-methylphenyl) -3- (1,2,4-triazole -1-yl) -propion- £ '"itril 2-kexyloxy-2-phenyl-3- (1,2,4-triazol-1-yl) -propionitrile,

SjHydronitrate 1¾ 2-butoxy-2- (4-chlorophenyl) -3- (1,2,4-triazol-1-yl) propionitrile I 2- (4-chlorophenyl) -2-propyloxy-3- (1st , 2,4-triazol-1-yl) -propion- j | itril 1 2 3 4 5 25 2-hexyloxy-2- (2-methylphenyl) -3- (1,2,4-triazol-1-yl) propionitrile, hydronitrate I 2-butoxy-2-phenyl-3 - (1,2,4-triazol-1-yl) propionitrile, | Hydronitrate | 2-butoxy-2- (2-chlorophenyl) -3- (1,2,4-triazol-1-yl) propionitrile | Hydronitrate 2-Athoxy-2-phenyl-3- (1,2,4-triazol-1-yl) propionitrile; 'i 30 "hydronitrate * 2-allyloxy-2-phenyl-3- (1,2,4 -triazol-1-yl) -propionitrile, ij: * "hydronitrate 2js * v 2- (2-chlorophenyl) -2-propoxy-3- (1,2,4-triazol-1-yl) -propion-itrile , Hydronitrate 1? 2- (4-chlorophenyl) -2-hexyloxy-3- (1,2,4-triazol-1-yl) propion itril, hydronitrate 2-hexyloxv-2- (2-methviohenyl) -3- (1, £ , 4-triazol-1-yl) -propχοήν ^ "'itril, 3 jr 2-butoxy-2-phenyl-3- (1,2,4-triazol-1-yl) -propionitrile 2- (2-chlorophenyl) -2-butoxy-3- (1,2,4-triazol-I-yl) propionitrile 2-ethoxy-2-phenyl-3- (1,2,4-triazol-1-yl) propionitrile 4 I 2 -Allyloxy-2-phenyl-3- (1,2,4-triazol-1-yl) propionitrile: § 'tO 2- (2-chloro) henyl) -2-propoxy-3- (1,2,4 -triazol-1-yl) -propioni tri, i P! -: "e" *.-srs · '' λ'-ΙΓ "£ ~ s" "'cstE-scrr.f:: S = rX =:' N 3 AG - D-vDCC SS. PosriaCv 65 0311 ^ ~ i = - = :. ä-fv.S.-4S-, Kt5.

5 AV.zjrs s *? '· .- * - ii, = .- i-% ZZ- 3 * «L · *. ** 1» -11-

SCHERINGAG

Gew & rsÎidier Eschtrsahuiz j 5 The compounds according to the invention in particular show fungicidal effects, but are at the same time distinguished in a number of crop plants by growth-regulatory effects.

’IO

Depending on the type of plant and the application rate, herbicidal effects also result.

Since the compounds according to the invention cause both qualitative and quantitative changes in plants and also changes in the metabolism of the plants, they are to be classified into the class of plant growth regulators, which are characterized by the following possible applications: i! ?! ί Inhibition of vegetative growth in woody and herbaceous 1 * 20 plants, for example on roadsides, track systems, etc., ’j lim to prevent abundant growth. Inhibition of growth in | * i grain to prevent storage or twisting, in | Cotton to increase yield.

I 25 Influencing the branching of vegetative and generative organs in ornamental or cultivated plants to increase the | Flower base or tobacco and tomato to inhibit side shoots.

30 Improve fruit quality, for example a sugar horny! "i | increase in the content of sugar cane, sugar beet or • fruit, and more uniform ripening of the crop, which leads to higher yields.

I increase resistance to climatic influences; I like cold and drought.

Influencing the lay flow in tussipi1ances.

. «.

I. -12- * I '^ c LärsisnätOr. Lord! Arnis Dr. Chnst.an S'unn Î-is'îS-.srçe ': re-v.a-.r, Bcsisr.ssr.riii'- Sd-'EPtiSS AS - S-’SCErlitt SS

? Dr. Heinz HannseKart Otto Mirte: s: ens: re> a - Dr. advised W as. Btr-ir-Wes: UTS-sw. Ssr.eieÆahi TMiOCIC

SCHERINGAG

1 ^ 0 Intellectual Property Rights - 1 ii- i 15 Formation of parthenocarpic fruits, pollen sterility and ύβ ε bad influence are also possible applications · 1 th 3] | Check the germination of seeds or the budding of buds.

Defoliation or influencing the crop in order to facilitate harvesting.

15! The compounds according to the invention are suitable, in particular j, for influencing the growth of beta beets, but also show desired growth-regulatory effects in cereals, soybeans and cotton.

Ί ij, 20 | Depending on the intended use, the application rates are generally from 0.05 to 5 kg of active ingredient / ha, if appropriate ii can also be used at higher application rates.

ij The application time depends on the application goal and ii 25 j: the climatic conditions.

Surprisingly, the compounds according to the invention ij are broader or more effective than products 20 of the same direction of action which are known in practice.

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

35 j1 The compounds according to the invention can be used either alone, in a mixture with one another or with other active ingredients. If necessary, other crop protection or pesticides can be added depending on the desired kq purpose.

1 '/ _ -13- ^ “Presidency: Dr. hertsr; - s—! £ - Dr. Chnszian Brunn-nans-JZ-gsr Hmtm 'psr ^ ns ^ r: ^: ZC-ZP.'. RSB AS - D-rSX Btfiir. & - rcstiz & i S3211 i Dr · r2irI *** »· ter One · Dr. - first. Pwtssnee-Kon :::. Se-ir-Vi-est **.? 5-ttK. SoiMeîSBft! -! ® naw

'' SCHERING AG

_ Gswerbfic & er Resvhfchuiz 5 'The labeled active ingredients or mixtures thereof are expedient 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, wetting agents -, Emulsifying and / or dispersing agents applied.

k 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.

Mineral soils are suitable as solid carriers, for example tonsil, silica gel, talc, kaolin, attapulgite, limestone, ΛΛ

Silicic acid and vegetable "products, for example flour.

Examples of surface-active substances include: calcium lignin sulfonate, polyoxyethylene alkylphenyl ether, naphthalene sulfonic acids and their salts, formaldehyde 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 mixed in to give the 30-seeded seed a clearly recognizable color.

The proportion of the active ingredient (s) in the various preparations can vary within wide limits. For example, the mixels contain about 10 to 90 weight percentages

Percent of active ingredients, about 90 to 10 percent by weight of liquid or solid carriers and optionally up to 20 percent by weight of surfactants.

40 1 L ^ · -xk- _ »Vorsia’xh Dr. He'bert AsmisDr. ChrtsSisn Bruhn · Hans-Dcfaer n.rräm »rrtsnicnri? :: SC-ESiNS A3 D -. DC: Berlin 65 · Po ** îf— £ 6« * »-, 1 0r · he" "r” annse · Gt4c MrXsissenscneic - Dr. -ors: Λ · = β Poitureac-ilsns: Ss-.T-rtast -.175 - f ,. EaiKlsiroa / ‘» V «rei? 7cr.Wer r-oe ti.rc rsie · Γ '« · TZ **? n WF * .. C: —r * · »» · / - »i- - ö-> - - p» _ - *. _ 1_ . -j. m '~. .

m V

SCnhfiiNG AG

- l4- GsrwsrbîHrer Rechisseiiutz |; 5 The funds may be spent in the usual way, for example with water as a carrier in spray liquor quantities of

About 100 to 1000 liters / ha. An application of funds in the so-! The so-called "low-volume" or "ultra-low-volume method" is just as possible as their application in the form of so-called micro-granules.

For the preparation of the preparations, for example, the following 1 ingredients are used: 5: i lj 15 A. wettable powder j a) kO weight percent active ingredient jj 25 weight percent. Clay minerals tj \ 20 weight percent silica i 10 weight percent cell pitch jj 20 5 weight percent surfactants based! j a mixture of the calcium salt of lig-; j'ninsulfonic acid with alkylphenol polyglycol

S

kolathern? i \?! 25 b) 25 percent by weight of active ingredient ij 60 percent by weight of kaolin 10 percent by weight of silica! J 5 percent by weight of surface-active substances based on the Sodium salt of N-methyl-N-oleyl- * 30 taurine and calcium salt of lignin sulfonic acid! c) 10 percent by weight of active ingredient 60 percent by weight of clay minerals 35 15 percent by weight of silica 10 percent by weight of cell pitch 5 percent by weight of surfactants based on

Sodium salt of N-methyl-N-oleyi-! taurine and the calcium salt of lig- IIQ / n ninsulfonic acid «7 \ {_. / ~ \ -15- j. Vo'stanö: Dr. he.'Mrt Asshs - Dr. ChrsEar. = rahr, Haw.B'Mn * sr * ns = r: tn: ED .-: ER! \ C- A-3 D-'KC Bartin ES · Ppsîîk * c £ 33 «-7 Dl. r.eir: hanrse - * .a ··. C “3 - __u -7 *. , _ _. ^! 5. . . _ ------ πτί- ’". ’2: tic

* X

_15_ SCHERiNG AG

7 G * w8îsîich * r_Rechtssehutr 5 B. Paste 45 percent by weight of active ingredient 5 percent by weight sodium aluminum silicate 15 percent by weight cetyl polyglycol ether with 8 moles of ethylene oxide ° 10 2 percent by weight spindle oil 10 percent by weight polyethylene glycol 23 parts of water C. Emulsion concentrate 15 25 percent by weight active ingredient 15 percent by weight cyclohexanone 55 percent by weight xylene 5 Weight percent mixture of nonylphenyl polyoxyethylene or calcium dodecylfenzene sulfonate.

* 20

The new compounds according to the invention can be prepared, for example, by propionitriles of the general formula o-Rl

25 R - C - CH. - Y II

! ^

CN

with 1,2, ^ - triazole of the formula

N - CH

-30 i! I.

; HC 5

V

H

or its alkali metal compounds in the presence of an external solvent, and optionally in the presence of a base, in which R and R., which have the abovementioned meaning and Y are halogen, or the alkylsulfonyl or arvisulfonyl radical, which may be halogenated in the side chain.

I ^ 0 '- / / T \ -l6- J ^ snr.se <a ~ 0:; s sf:; 5 “s'-s L c” “I:' = 's-a6n”? Estara. 3 ^ .. ^ ’V3r ... -T. *“. f fc * «« 3 «

,, SCHERINGAG

_lfc ~ Gevearâlieher legal protection / * j \ i

Sfj Î5 Examples of halogen are chlorine, bromine or

Iodine; Suitable alkylsulfonyloxy radicals are, for example, methyl, ethyl, propyl and the trifluoromethylsulfonyloxy group and “arylsulfonyloxy radicals include the IBenzylsulfonyloxy and p-toluenesulfonyloxy groups.

»10

The reaction can be carried out either with an excess of 1,2,4-triazole, optionally in the presence of a solvent, or with the addition of a strong base, for example sodium or potassium hydroxide. You can also.

* 5 Use 1,2,4-triazole alkali metal instead of 1,2,4-triazole.

| Compared with the reactants, inert substances are preferably polar, aprotic in character, such as | - Ν, Ν-dimethylformamide, N, N-dimethylacetamide, N-methylpyrroli- | don, tetramethyl-urea, hexamethylphosphoric triamide jl and benzonitrile, but also higher-boiling aromatic and 1 aliphatic hydrocarbons such as toluene, chlorobenzene or II I Xvlol.

25 | The reaction temperature can be varied within wide limits the. A temperature between 100 C and 200 C is preferred.

| The implementations take place under normal or overpressure.

30, .. · The 1,2, “- triazol-1-yl-propionitriles according to the invention are - p generally almost colorless and odorless solids. The da- | Derived from acid addition salts are also colorless and odorless, crystalline compounds. The free bases dissolve poorly in water and more or less well in organic solvents such as alcohols, xther or chlorinated hydrocarbons. Some of the acid addition salts are dissolved in water and well in polar organic solvents such as acetonitrile, X, X-D ± i5ethylformamide, lower alcohols, chloroform and methylene chloride.

'2 ’° / -17- i ^ Se £ = - £»: f * 3 ÄS - g., ;;. «. SS ~ 11 I _ ....

SCHERING AG

- 17 - Intellectual property law. ê: ί 5 The following examples explain the production of the

! J

I *! compounds according to the invention.

1 EXAMPLE 1 1 2-IsoproT3Qxy-2-phenyl-3 ~ (1,3,4-triazol-1-yl) propionitrile 1 -'10 hydronitrate 8 - * - - - | _ Connection No. 2

0.55 mol of I 15 1,2,4-triazole are added to sodium nitric anhydride (0.55 mol) suspended in 50 ml of dry DMF with stirring and cooling. Then 0.11 mol of 2-isopropoxy-3-methyl-I sulfonyloxy-2-phenyl-propionitrile in 50 ml of DMF are added! and the batch was held at a bath temperature of 150 ° C. for 1.5 hours.

After cooling, the mixture is extracted 3 times with 100 ml of ether, I the combined ether phases are washed 2 times with water and I '20 dried with MgSO 4. The ether is rotated in a vacuum, j y is added to the residue with 50 ml of isopropanol and dripped uni J; cooling 6.8 ml nitric acid conc. with stirring. To

The addition of 80 ml of ether is stirred for a further 1/4 hour and then; ! aspirated. It is recrystallized from isopropanol.

1] 25

Fn .: l85-l89 ° C (decomposition) ï *,

Yield: 15 g =% of theory

* K

3® DMF = dimethylformamide Λ - ίί - 35 / -iS- f JA_ - ÎC'i.Sri. _τ ".'Ser * Asr ~ .is _ ·. · C ^ rrsf.er S '^ nr ha" .s-jj.'qe "-a —anr = -..-.- ..

g “rB’ "’ -tr.r.se Kan Z - :: o M-r: s.s: ens =: s.e - 0 '. hors: vt.se ·' -f; ' SChsÄNS AG D-’COC Sanas 65 - Patifasn SS 3211

ΐ Vori.tte -. = e- CSÏ Aw: s: = n: sra: ç Gr. £ = _ae = ·, 5 = .- «a.-1z-C30 =" '£ sr: -. R- "cs:" Sanioe-csn * X 130 IC

? c Srîr r.p. ’/*.oî£:.î^-o·.· = ... r. ~ Z. · · -Lè-'n-â. '"· *' ·“ * Eç'LI. “V 'V» · «Tr P.Ä« »Ä -s *. ·

SCHERING AG

Commercial wicker protection; ! i 5 EXAMPLE 2 \\ 2-Isopropoxy-2-phenyl-3- (* ^ 2, 4-triazol-1-yl) -propionitrile jf Compound No. 3 ü || 10 g of 2-isopropoxy-2-phenyl-3 ~ (1,2,4-triazol-1-yIÖ-propion- |. 10 itrile, hydronitrate - are dissolved in methanol and with 8 ml

J

’Lj 32% ammonia water added. You give on water, ex-a! | tracts with ethyl acetate, dries over MgSO ^, 1 rotates the ethyl acetate in vacuo, adds a little 2 ethyl acetate and activated carbon, boils briefly, sucks off and I ^ rotates again. The solid produced in this way is pure for analysis.

! ä o

J.J. Mp .: 176-177 C

II Yield: 6.65 g = 83% of theory; . 20 Ί i '

The following connections according to the invention can be prepared in an analogous manner.

! ji i! 30: "1 Ί i: 35 11 i 40 /“ 15 “h? [R \ Ä 'Vc'srsnü: Dr. Herbert Asm- - Dr. Christian Brunn - Hans-jOrgeha.-r.tm>» KtanKr .rift: £ 0: -. == ^ A "·" -'KT Se-a> «· sw« «- sw- -7 Dr. Heins Kannse · Kan Öko M.re:3 tallerss skillei3 · ur. r.tts ·. * .ce. - .. —is «a .. - · ** ae. *, .. ------------ = In front of each other ces Aufsicmsras: Or. Eduard v Sa'we'tzKissan ^ '31 · xl * __________

SCHEKNG AG

-19 "Gt-arsrând * sf £ γ <ΑΑ '- *': ιπζ! ..

5 Kr. Name of the connection Physical constant

| 1. 2-Hexyloxy-2- (2-methylphenyl) -3- (1,2,4-triazole- m.p.:159-62^C

] l-yl) propionitrile, hydronitrate (Z)

14. 2-Butoxy-2- (2-methylphenyl) -3- (1,2,4-triazole- mp: 58-62 ° C

l-yl) propionitrile 10, v Λ

5. 2-Butoxy-2- (2-methylphenyl) -3- (1,2,4-triazole- mp.158-61 C)

l-yl) propionitrile, hydronitrate (Z )’s S. 2-Hexyloxy-2- (2-methylphenyl) -3- (1 »2,4-triazole- ηη4θ l-yl) propionitrile D: ^ 5121

7. 2-Butoxy-2-phenyl-3- (1,2,4-triazol-l-yl) - m.p.:159-6oC

propionitrile, hydronitrate (Z)

8. 2-Butoxy-2- (2-chlorophenyl) -3- (1i2,4-triazole- mp: 142.5-44 ° C

! l-yl) propionitrile, hydronitrate (Z)

| 9. 2-Ethoxy-2-phenyl-3- (1,2,4-triazol-l-yl) - mp: 16-70 ° C

a propionitrile, hydronitrate (Z)

j 10. 2-Phenyl-2-propoxy-3- (1,2,4-triazol-l-yl) - mp: 178-79 ° C

propionitrile, hvdronitrate (Z)

20 v / y 11. 2- (3-chlorophenyl) -2-hexyloxy-3- (1,2,4-triazole- mp: 173-75 ° C

; j l-yl) propionitrile, hydronitrate (2)

\ 12. 2-Butoxy-2-phenyl-3- (1,2,4-triazol-l-yl) - mp: 67-68 ° C

i propionitrile

; 13 ·· 2-phenyl-2-propoxy-3- (1,2,4-triazol-l-yl) - mp: 107-08 ° C

| propionitrile

14. 2-Xthoxy-2-phenyl-3- (1,2,4-triazol-l-yl) - mp: 7I4-75 ° C

propionitrile

15 x 2-Hexyloxy-2-phenyl-3- (1,2,4-triazol-l-yl) - mp.158-6oC

i propionitrile, hydronitrate (Z) c (

- 16. 2-Allyloxy-2-phenyl-3- (1,2,4-triazol-l-yl) - mp: 145-47 ° C

propionitrile, hydronitrate (Z)

17 * 2-Butoxy-2- (4-chlorophenyl) -3- (1,2,4-triazole- mp: 173 ~ 75 ° C

l-yl) propionitrile, hydronitrate (Z)

. 18. 2-Allyloxy-2-phenyl-3- (1,2,4-triazol-l-yl) - mp: 86-88 ° C

| propionitrile

19th c2-Methoxy-2-phenyl-3- (1,2,4-triazol-l-yl) - · &> -. 7 "7- ~ a ° C

propionitrile * '35

20. 2-Hexyloxy-2-phenyl-3- (1,2,4-triazol-l-yl) - mp. * 58-6c ° C

1 propionitrile

21. 2- (2-chlorophenyl) -2-hexyloxy-3- (1,2,4-triazole-; 157-5 ^ CC

i l-yl) -propionitrile, hydronitrate ^ 2} 4θ Z = decomposition _9q \ - Vtrsiand: Dr.l-ierberi Asmis - Dr. Christian BrynnHans-Jürgen Hemenn "cs; zns = nrif £: A3 - Γ- ·; 3 Ε- * πΐη * S. S ~. Xlt

[f Οι. Heinz HaanseKan Otto MifeisterscieiäDr. «First pessscftes · -1 '- ^^» sr ..— * ss? * »* 05IC

• · = Voreittenaer des AUs> cn: srsts: Or. Ecuard ». ScbwarSKOcpen Serüner Zsx:., .- * .. zsrr.A2 ser-ir .. Cons »..« ,. ·. 7335 OC & £ o.-s »ît3s.Y α« X 0 * ^ »

_20_ SCHERING AG

\ ».

f% 5 No. Name of the connection Physical constant

22. 2- (2-chlorophenyl) -2-propoxy-3- (1,2,4-triazole- mp: 138-39 ° C

1-yl) propionitrile, hydronitrate (Z)

; 23 »2- (4-Chlorophenyl) -2-propoxy-3- (1,2,4-triazole- mp.15:15-57 ° C

1-yl) propionitrile, hydronitrate (Z)

i; 1024. 2- (4-chlorophenyl) -2-hexyloxy-3- (1,2,4-triazole - mp: 155-59 ° C

1-yl) propionitrile, hydronitrate (Z)

25. 2- (4-chlorophenyl) -2-propyloxy-3- (1,2,4-triazole mp: 115-19 ° C

î 1-yl) propionitrile

26.''2-Butoxy-2- (4-chlorophenyl) -3- (1,2,4-triazole - mp: 54-6o ° C

1-yl) propionitrile

15 27. 2- (2-methylphenyl) -2-octyloxy-3- (1,2,4-triazole mp: 128-34 ° C

1-yl) propionitrile, hydronitrate (Z) 28. 2-decyloxy-2- (2-methylphenyl) -3- (1,2,4-triazole mp: Il6-20 ° C 1-yl) propionitrile, hydronitrate (Z) 29. 2- (2-methylphenyl ) -2-octyloxy-3- (l, 2,4-triazol-n-20. ^ 4930 1-yl) -propionitrile.1 j 20 30. 2- (2-chlorophenyl) -2-butoxy-3- ( 1,2,4-triazole-1 ^ 40: 1.5273 1-yl) propionitrile 31. 2- (2-chlorophenyl) -2-propoxy-3- (1,2,4-triazole-1.53 ° ^ Π - 1-yl) propionitrile

32. 2-Butoxy-2- (2,4-dichlorophenyl) -3- (1,2,4-triazole mp: 163-66 C)

1-yl) propionitrile, hydronitrate 2533. 2-butoxy-2- (2,4-dichlorophenyl) -3- (1,2,4-triazole mp: 53-55 ° C 1-yl) propionitrile

; 34. 2-Allyloxy-2- (2,4-dichlorophenyl) -3- (1,2,4- mp.104-07 ° C

I - triazol-1-yl) propionitrile

35. 2- (3,4-dichlorophenyl) -2-propoxy ~ 3- (1,2,4- m.p.:152-55 ° C

triazol-1-yl) -nronxonitrile, hydronitrate (Z) f * o

I ^^ 36. 2- (3,4-dichlorophenyl) -2-propoxy-3- (1,2,4- mp: 60-66 C)

I. triazol-1-yl) propionitrile

Syj ^ 2- (3,4-dichlorophenyl) -2-hexyloxy-3- (1,2,4- mp: 16-66 C)

triazol-1-vl) -nropionitrile, hydronitrate «t '^ 8. 2- (3,4-dichlorophenylî-2-hexyloxy-3- (1 «2,4- n ^ 40" Λ -240 - triazol-1-yl) propionitrile *

\ 35 2- (4-fluorophenyl) -2-propoxy-3- (1,2,4-triazole mp: 172-75 C)

! * 1-yl) propionitrile, hydronitrate (^

|. 2- (4-fluorophenyl) -2-propoxy-3- (1,2,4-triazole- mp: 96-100 ° C

1-yl) propionitrile

ΐχΛ ^ 2-Buxoxy-2-i4-fInorphenyl) -3- (1,2,4-triazoi- mp: 173-75 ~ C

1-yl) propionitrile, hydronitrar i 40 1 "? - 2 i - |; | Z = decomposition ».. * w - Board of Directors - Df. Herbert Asmt * · Dr. Chricüsn Erc.V; - 'rtne-JOrçen h &. * r «anft Postsnearw? * :: SCHESïHG AG - &> tC5 35 - each CSC *? t 2 V_ - Pr. He.nz Hanns © - Karl Ottc Mi« e.srensc: eiC · Dr. no'sî W'ref ^ er: ic: IVTi-iC ·, -

Chair * ces. Ajisiçrtsrê.; ·: Dr. ccuerä v. Srws.tzt :: c c-sn r ** r, .r. ** rtr,? · £ "riip, t 7D3v · β

- -. ^ _______— ____ ___ - ·> * ίο rA

Λ

SCHERNS AG

'ϊ: 5 yr <Name of the connection Physical constant

^ 2. 2-butoxy-2- (4-fluorophenyl) -3- (1,2,4-triazole) mp: ^ 6-p8 ° C

Il-yl) propionitrile hj. 2- (2-fluorophenyl) -2-propoxy-3 ~ (1,2,4-triazole- mp .: 150-53 ° C 1-yl) propionitrile, hydronitrate '(Z) 2- (2-fluorophenyl) -2-propoxy-3- (1i2,4-triazole m.p .; 66-6 $ ° C 1-yl) propionitrile o lk3. 2-butoxy-2- (2-flnorphenyl) -3- (l, 2,4-triazole- mp: 138-43 ° C 1-yl) propionitrile, hydronitrate (Z) 46. 2-butoxy-2- (2-riuorphenyl) -3- (1,2,4-triazole m.p .; 76-79 ° C 1-yl) propionitrile

15 m 2- (2-fluorophenyl) -2-hexyloxy-3- (1,2,4-triazole-FP *: 13 ^ -37 C

1-yl) propionitrile, hydronitrate (z '

2- (2-fluorophenyl) -2-hexyloxy-3- (1,2,4-triazole m.p .: 58-60 ° C

1-yl) propionitrile 2- (4-bromophenyl) -2-propoxy-3- (1,2,4-triazole) mp: 150-53 0 1-yl) propionitrile, hydronitrate (Z)

-20 j-q ^ 2- (4-bromophenyl) -2-propoxy-3- (1,2,4-triazole - mp: 118-21 C

1-yl) propionitrile

| 2- (4-bromophenyl) -2-hexyloxy-3- (1,2,4-triazole- mp: 16l-64 ° C

Ü * 1-yl) propionitrile, hydronitrate (Z)

; ^ 2 2- (4-bromophenyl) -2-hexyloxy-3- (1,2,4-triazole- mp: 60-62 ° C

| 1-yl) propionitrile

j 53. 2- (2,4-Bichlorophenyl) -2-propoxy-3- (1,2,4-tria-F-p.: 166-7Ο C

! -Ζ0Ι-1-yl) -propionitrile, hydronitrate ί 54.2- (2,4-dichlorophenyl) -2-propoxy-3- (l, 2,4-tria-m.p .: 61-63 c II zol) - propionitrile. ... _

I 55. 2- (2-methylphenyl) -2-pentyl-3- (1,2,4-triazole- mp.15:15-5½ C)

J l_yl) propionitrile, hydronitrate i 56. 2- (2-methylphenyl) -2-pentyl-3- (1,2,4-triazol-,, 1-yl) propionitrile I 57. 2- (4-methyl -phenyl) -2-propoxy-3- (1,2,4-tria- mp: 170-7 ^ 0 l - zol-1-vlJ-pronionitrile, hydronitrate I- __c! - ° r; 58.2- Hexyloxy-2- (4-methylphenyl; -3- (1,2,4-tria- mp .: f zol-1-vl) -nronionitrile, hydronitrate 'z "i! -Y - r; f O / * • 59.2- (4-Methylphenyl) -2-propoxy-3- (1,2,4-xria- mp .: 120 - ^ -: zol-1-yl) propionitrile f 60.2 -Hexyloxy-2- (4-methylphenyl) -3- (1,2,4-tria- n £ °: zol-1-yl) -propionitrile. ^ * - * 9 6l. 2-3ntoxy-2- (4-niethyl-pher.yl) -2- (1,2,4-tria- mp .: zol-1-vl) -nropionitrile ^, \ - £ l- 1 I · Ί / \ ”Vorsta-i: 3r.He-bs- · Ast. * · O-, Cvistiar Hr-n - rar.i - ;: "« · -. "2-a ^ r. = —R :::: SS-.E =! ! NS A3 Eê .- .. τ. 55 sesray ·; Z r * if. W '= * ·. ÔÎÎC. R - - Γ: * =: Λ 12 2 --------__ E - -f "· C .'-" "J-> · - ^ - λγ« iTC Î

SCHchiNG AG

~ --- Commercial legal protection 5 The 3-aryl or

3-alkylsulfonyloxy-propionitriles of the general formula II with Y meaning aryl- or alkylsulfonyloxy have not hitherto been described in the literature.

10 They are obtained by using the methods that are known or known per se (cf. for example Rubin et al., JACS 67, 192 f (19 ^ 5); Hess et al., Ber. Dt. Chem. Ges. 30% 394 (1917)) accessible phenylacetonitrile of the general 15 ^ _ I 20 25 i 30! ' f! 1 . fs! · '35 1 · il 4o I - 2 Ιιύ- c Vorsrans: Dr. Herten As.-r: sDr. DVie-.s.- Sri.hr. Hars-Jc-ser. hsr-anr. r’csTarccrrif:: 3C .-: E “: nS A3 5.-¾ .. ç“ .. r ”. _ β · "..

5 hM = Har * «·« Sr! Ctrc U. ^ - srer. «.« Dr. hcs VV à. : E9r. * - V.-es · '' £ Vars.trenier ces Ac: s.crssr2a: er. ssaarc v. Heavy — rcccer. oê.-i.> »he Darrnerrsarw. κ-s. oeri ». k .... ... - «î. > Y A '«" · "ν' 4

5 Formula III

_. SCHERING AG

-22 -;) j [J Gcvjerbüdiar Rschtrs: r: uti f j 1 * 0 - R.

i 1

R - CH III

CN

«10 where R 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

•. ? - Ri

15 R - C - CH0 - OH IV

I 2

CN

I with suitable sulfonic acid derivatives, such as I sulfonic acid chlorides, optionally with the addition of a! Acid binder, implemented. The Hvdroxvmethvlverbindungen of 20 "general formula IV are not yet known literature.

“Il ¥ f The production of a starting product 1 is described below.

1 25 | 3 ~ methylsulfonyl-2-t> henyl-2-propoxy-t> ro-dionitrile! 27 g (0.15¾ mol) of 2-phenyl-2-propoxy-acetonitrile are dissolved in J 120 ml of pyridine and mixed with 18.5 g (0.61¾ mol) of paraformal I dehyde. To this suspension, 7.7 ml of tetrabutylammonium hydroxide (als0Η) is added as a ^ / oige i solution under ice cooling and the mixture is stirred vigorously. After a few hours (DC-? ’. Control) is poured onto ice water and extracted with ether’ '. The ether phase is washed with dilute hydrochloric acid and then with sodium chloride solution and dried with magnesium sulfate. After filtering off the desiccant and rotating in a vacuum, a colorless 01 remains, which turns out to be uniform by thin layer chromatography and can be processed without further purification.

Yield: 28, ¾ g = 90% of theory 3- ^ ydroxy-2-phenyl-2-f 2Q propoxy-propionitrile | nd: ^ 5027 _23.

* (/ Vwaed: Dr. Keroeri Asmis - Dr C.-r; s: a *> Br.-t-.r '- = -s-.î-.ûr-er. -Ar-.εηρ SCV-ERING AG - D-'S0: âarlin SS - Pcstïear 53 2Ξ - *

| Dr. he: n: Her-.se Kart CScV.r.e-sîsnscr *, ^ Dr. «'S: V. ss fsr ^ .cr - ^ -.- r.rs. 5 = Π - = - ν.δκ v.rs - '. DC

5

SCHERING AG

Gewsîàüshs.- Rs-chisschirtz I 28 g (0.136 mol) 3-hydroxy-2-phenyl-2-propoxy-propionitrile • are dissolved in 200 ml toluene and 19.5 g (0.171 mol)

Methanesulfonic acid chloride added.

^ At 10 ° C, 8.6 g (0.184 moles) of triethylamine are added dropwise.

The mixture is stirred for 30 minutes at room temperature, filtered from! "precipitated triethylamine hydrochloride and concentrated.

The residue is taken up in ether, washed with water,! dried over magnesium sulfate and concentrated. The oily residue proves to be pure by thin layer chromatography.

I Yield: 32.27 g = 86% of theory 3 ~ methylsulfonyl-2-! phenyl-2-propoxy-I propionitrile [20 nd: 1.5000 20 I "25; 30 35 u -2h- \ ko <0 03

: CO

i Z Board of Directors; Dr. MertsT Asrr.s ·>. Christian Brunn · Hsrs-J & ser. na.-r.snn: S3- = F .. '\ 3 * 3> "JT. 5s-: ir. S · ros-Vrr SS"

S Dr. heins Hamse · Ks ·· Ott av: t * s: r = - .; 5r.eici 3'- Sers:? 5S! .jr.e »** ': n: c Ee · * .tw-ssr rtTï- 'r. Sa-we-sran: * 50 * X1C

! i rie. A. - 3r rnusrrt v SmuamKOCO · !, 5e '.. ner r.s-nr.eriss-.t A3. E «r nt-ts-v. tx & SAK.S = 2 * ·· * x «5 - 24-

SCHERING AG

“* Commercial Rs-cHsPcr.wiz 5 The following exemplary embodiments serve to explain the possible uses of the compounds according to the invention, which was carried out in the form of the preparations mentioned above.

.10 EXAMPLE 3

Effect of prophylactic leaf treatment against powdery mildew Krysiphe graminis on barley in the greenhouse 15

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 dried with 20

Inoculated flour spores by covering the test plants with infected plants. The test plants were then cultivated in the greenhouse at about 20 to 22 ° C.

and rated after one week on percent / leaf area.

The fungicidal activity was calculated as follows: 25

Infested in Treated. 100,

Infestation in Uno changed ù

The compounds were in the form of 20% formulations.

3 ° 35 col · '-25'! 'j. Mind: Zr. rerbert As; r: s · Dr. Christian Sruiir. · Hans-Jürcer = .rc-.cr “cs'Erscr.rrft: SCHERING AG - D-iCOG Berlin £ 5 * Pcs-cä £ 5 X ΐί" t -'r- r-. £ ~ nse · <£ r . C ”c - ~ r. -.CrEi tre Pcsr-crscx-K: Ser;: r - VYesr" 75-'X. Sanr-iSr-tranl l0C “CC: Li

_ £ Chairman ces Au ^ cr.tsrEts; Dr. Ecuard v. SchwartZKCOpen Ee '.r. = R Ci rr.merzzέ. << AG. rs-.in, K ^ ntD-Kr. “3c 73Cz CG. EahKre tzv.- “3? <X X

SCHERING AG

Commercial legal protection .1 J 5 Erysiphe graminis according to the invention

Compound No.% Effect j! _pOOppni_100 ppm; 1 100 95 2 100 59 10 3 loo loo Γ j k 100 100; 5 100 95:; 6 100 9¾ 7 100 100 15 8 100 100 j 9 100 100 I 10 100 100 I 11 100 9¾ i · 12 100 100 I 20 I 13 loo loo I ik 100 100 | '15 100 100 Ï; : I 16 100 100 * 17 100 100 I 25 1 18 100 100 6.

I 19 100 100 | 20 100 100! 21 100 95 22 100 100 30 23 100 100 \ 2k 100 I '25 100 26 100 35 • 40 / d -86.

• ‘I rt

Vors * snc: Dr. he'berî Aetîîg - Dr. Christian B'unr. - “acs-vü'C“ 'rjrznr “ostansanrirt; £ C “He: is“ 2 A3 Berlin 55 · Posb'ecr 5c ZZ 11

2 Dr. right: r.r h & nnse · Kar- Otto eisrer.scneic · Dv “C'3’: 2 £ Pps ’. ^ cr-eo 5er Bank'e'trah 1DC-“ XrC

® Vsrsli? <~ R> ri5r des Aijfsicr.tsfais: Dr. Bcjjare v. Scr.wartz. *: Ccner. Εεγ \ ιΓ: £ '7e "r'hi'rr & rr A3. Eer :: n. Sorto-Nr, 17 * 5 72½ OC ρξγλ e-tzan' OC * 0

_ "6_ SCHERINGAG

Commercial account: sschiiiz \ Ά \ Λ || 5 Erysiphe graminis || according to the invention Compound No.% Effect S ____500 ppm_100 ppm 28 100 95 30 100 100 10 31 100 100 33 100 100 3¾ 100 100 35 100 100 '36 100 100 15 38 100 100 kl 100 100 k2 100 100 kk 100 100 iS on ^ 8 100 95 "and"

|| k $ 100 100 $ 50 100 100; 51 100 100 I 52 100 100 I 25 53 100 100! 5k 100 100

II

i 55 100 100 '\ 57 100 100 I 58 100 100 I 30 59 100 100 t _' 60 100 100 I - 61 100 100 ¥ - 35 t "if; I -; kO! H h --3 5 each mind 2r. Hsrse-t Asmis - Zsr Brjnr. Hans-JZ'esr - = -51 :, P - =: = r £ G .-. :: 'r: 2Z-' ~ P '\ 3 -3 ~ - " ZZ: Es.-: r- ££ -cz'-icr 65 3Γ "fir no." 'Ms-ncc. ifsr ί ”" * »*« *! M t ·· »Mir: · 1Λ. · * —c. - -.. _ _ ^ - - - ______ I 5 EXAMPLE 4

SCHERiNG AG

- - 1 - Gev; srà! Ichsr Eechisscnuiz! Lj

S

; j Effect of prophylactic foliar treatment against Erysiphe ^

Icichoracearum on pumpkin plants in the greenhouse • 10 Pumpkin plants sprayed to runoff with the specified active ingredient concentrations were inoculated after drying the spray coating by dusting dry flour spores from Erysiphe J. cichoracearum and together with inoculated untreated control plants in the greenhouse incubated ·.

! 15 After a week, the infected flour surface was estimated in% of t i of the total leaf area. The fungicide effect was calculated as follows: ‘20 mo - 100 · infestation in treated _ W1_ku__

100 infestation in untreated ~ * effects

'3! (! The note "s" in the table below means that

Fungicidal activity could also be assessed from the growth of the plants (after the treatment) and was found to be positive. This means that the active ingredients were systemically transported into the growth and also had a one hundred percent effect on mildew.

* 30 jf The compounds according to the invention were present as 20% formulations.

f £ 55. 110 (Λ -28-! - Board: Dr. Heroert Asmis - Dr. Ct> r: s «ön Sn.hn · Kans-JC-e- -s-ans Psstar.s * r.?!: SCnE» ' », 3 A3 C-tSCS Berlin SS. Poaîîadt Sf 53«

t Dr 'He, M Hs "-nse Ot: o" H ** "™ *» * · Dr. n0'3: * .Ä Fsrsx. ^ cr.rs · £? e -..- * esr r. "*". San ". = M -xτχ'C

C * iir \ rr • »oni-af nse L · ·. ici »r red · Or Crfi: arW vr C ______ .- ^. · __. .... ... - _ _____ 4 ►

SCHERING AG

- 2o- Commercial legal protection j 5 Erysiphe cichoracearum fj compounds according to the invention No. 9¾ Effect 3 250 25 5 2.5 0.5 ppm I 1 100s 100s 100s !! 10 2 100s 100s 100s' | ’3 100s 100s 100s 11/4 100s 100s 100 I 5 100s 100s 100 * 6 100s 100s 100 15 7 100 100 100 8 100s 98 100 9 100s 100s 100s | 10 100s 100s 100 tj 11 100s 100s 100 I 20 12 100s 100s 100 | 13 100s I; _ 14 100s 100s 100 for 15 100s 100 100 | 16 100s 100 99.5 I 25 17 100s 100s 100s | 18 100s 100s 100 6, js 19 100s 100 97 Î20 100s 21 100s 100 90 30 22 100s 100 100 r: l p ’i 35 t; π i i i, 40 / J9- [i k. Stow - Dr. Herbert As; mis - Dr. Crrirt ar · BtuOn · = Hermann ^ ~ £ ’to £ crnit: £ 0ί ~ Ε ~ ι'Ν · 3 A3 - D-tCOC 3-ar.in 65 - -“ '- Ersttaer 65 03 1t

* * T: Dr. r-e.nz Haonse 3t: o M ^ te.-brer.scr.e-c - Dr. “2'2 -.- tze; = 5r: -. * Äs: r.Ee ^ k.s · 'XtXtC

b __- ». _ r-s _ r ~ c · r-_. - "i. * ri H: α <·. “P & l'W ΠΟ ^ i * c. ’*, Ol. Α.Ύ

-2? - SCHERING AG

Intellectual Property Law yy Erysiphe cichloracearum j;> Invention% Effect 5 Compounds No.

1 250 I.

! 27 100s! : io 29 1005! 32 100s i 37 100s jf = 39 100s; | 4θ 100s 15 43 100s \ l 45 ioos l 46 ioos! 47 100s · "56 100s I; i || 20

Ij 25 tf

II

l | ii 30 i. 'i: *; i t 35 -30- 40 j; Association: Dr. hùTteri Asm-s - Dr. “Caresser, - SC · 1- ^“ - ^ 3 A3 3 - "" 3Γ SerJr 55 *? C5 "Gcr. Er * TD? _ Hc, r, 7th Karr ΓΊrm» »'» »c.-c- sr.c-'rp ^ r ''. Hr ί-η * · «? · * r = r -._________ · _- -, - · _________ i" 5 EXAMPLE 5

SCHERiNG AG

- 30. Gswsràltrâer Redïts & drjtz

Effect {%) of prophylactic leaf treatment against Helminthosporium teres (= Pyrenophora teres), mesh spot disease of barley 10

Young barley plants at the first leaf stage were sprayed to runoff at the concentrations indicated. After the spray coating had dried on, the treated plants and untreated control plants were sprayed with a suspension of the 15 conidiospores of Helminthosporium teres and incubated in a moist chamber at 20 to 22 ° C. for 2 days. The plants were then cultivated in a greenhouse at 20 to 22 ° C. One week after the inoculation, the percentage attack on the leaf areas was noted. The fungicidal activity was calculated 20 as follows:. Infested in Treated. 100.

* 100 - -----—: ^; - =% effect

Infestation m treated Ο ζ

The compounds were present as 20% formulations.

u 30 35, _3l_ ko co 0

CO

d Vorsiane: Dr. Fsraert Astres - Dr. Chrisiiar Brsnr Hans-Jirje1 'Hamann Pcstar.acr.rift: SCF'E3! N3 AG · D -'- CC: Berlin £ 5 - Psst ^ aiii £ 5 C311 1 Dr · ίιβ'Μ Hannse · Kar: Otto M.nsistenssie -aDr. Hors: Wrîzei s-sstssnsÄ-Komc: Ser: .-- V.es: “Vr. 3ar.Kie: 2a! H IX1X10 mW «*. r «___ .. r * .__—. _. . ... r —___ * __ * r * «_« _. __.... r Λ r. «... L * ^ _« ... m .¾ ^ fVlC fy, S r. κ 4 Throws

SCHERING AG

- j y Commercial legal protection kt * I * »'’ 6, *' 1 Î5 Helminthosporium teres according to the invention

Compounds No.% Effect 500 ppm 100 ppm lOppm: j - I 1 100 100 10 2 100 100 100 3 100 100 90. 4 95 95 90 5 100 100; | j 6 99 j | 15 7 98 90 il 8 83 I 9 100 85 i | 10 95 95 i | 11 100 90 I 20 12 94 90 -j ’13 92 85 4, i4 89 80 .j; 15 94 90 I lé 94 80 I 25 17 89! 18 100 70 fl 19 94 I 20 70 i-! 23 85 30 24 95 90? ^ 25 95 95 I 1 26 80 27 90

"L

40 '^ r? ca Π5 «l · ^ j. Board: Dr. Herbert Asmls * Dr. Christian Bruhn - Hs-îs-Jô '^ en Hamann Pas ^ rrsarrift: SCHERING AG - D - ** 3CC Beriin SSPostfecn SÎ211

* r Dr. Heinz hsnnse - Kar, Otto Minetstsnscbeid - Dr. Herst W.tze: "csrzrnezx-Kcrnc: 5e -". ^ - VVesr 1175-: 0 :. Bankie.izahi 1001QG1C

c * 5 EXAMPLE 6

SCHERING AG

_32 _ Qewerblîsr.sr RecärtsKhuiz

Effect of prophylactic leaf treatment against dwarf rust, Puccinia hordei, on barley in an air-conditioned plant growth chamber; . 10 | ! Young barley plants in the stage of the first leaf were j - - | sprayed to runoff with the specified concentration. After arrival | The treated plants I and untreated control plants were dried by painting over the spray coatings! 15 [J dwarf plants infested with rust and put in a plant o | brought growth chamber. At 15 C and in the first two days! The plants were cultivated for 10 days under almost moisture-saturated air. The percentage of leaf area affected by rust was then noted. The fungicidal activity 20 was calculated as follows: Î! Infested in Treated. 100 ./ ....

! 100 - Infection in untreated- = * WlrfamS

! 25 i;

The compounds were in the form of 20% formulations.

:; ! Î. 30: I ^! I -: 35 i (i ii ii! Ko • en ί; ή i 05 3 Voreîand: Or. Herbert Asrnis - Dr. Chrrstiar Sruhn · Hs.ns - «; Crçen Ktmann Psstansatrift: SCHEHINS AG - Ö * 3K Berlin «- Poetiaej ββ11 i Z Dr. heira Hennse - Kai Otto M: K6: r.erweRe» a Dr. ncret W.228.Possæesfc-Kotwo: Berim-West riTS-ix.BanMeitzaM 13B19C10

: SCHERING AG

“33- Commercial legal protection h: r 5 Puccinia hordei according to the invention! Compounds No. o / 0 w ± r \ cang ’500 ppm 100 ppm 20ppm Γ 1 100 77 10 2 100 83 ;; '3. 4 100 100 89 5 100 100 9½ [6 100 9½ 15 7 100 98 89 I * 8 100 9¾ 9¾ 9 80 10 100 98 94 § 11 89 ijj 20 12 84 i 13 89 1 i4 95 80 I '15 95 I 16 78 .. ran I 25 17 100 100 100 l8 98 <: 19 95 I 20 85 21 100 70 30 22 100 100 j 23 79 I * 24 90 70 jft I 25 90 90 27 85 * 35 30 95 5 31 95? 7 f z "'

Ls * 40 - 34- <? ! "Board: Dr. Herbert Asm" · Dr. Christian Brunn KsnWSfoen Hexssr. Posai -. * = NrtS: SCH == "'iG AG C-'DGC s.riin« - I Dr · Heinz h8nnw Karl Ct: c Mfceisrensweid - Dr. Hors: W; ae. ^ «Sccea account: Bertm-ftest r.rs- ^. Sanfae ^ I'-w-x-e “- · Chairman of the Supervisory Board: Dr. Edward v. ScfiwartZKccser. ser:; "sr Ci.TiTt-csrt»: ag Kr.rt.-_ tœ = ««

SCHERING AG

“GeK £ -rhtid> er Rsdtisschutr ί Ä I 5 EXAMPLE 7

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

’10 Bioraalzagar was heated to about 45 ° C after heat sterilization

cooled and then - mixed with the test substances in aqueous preparation - 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:.

r; 1 100 - Ra ^ al ^ cfrs. * · £ Treated. 100% inhibitory effect 1 25 radial growth in untreated 7 s 4 ç! | The compounds were in the form of 20% formulations.

f1 · $ I Compound according to the invention% activity with 250 ppm _Nr_ active ingredient concentration 3 ° | 12 62 J - 15 73 * 21 64 24 66 35 3! ? · Z "t- m: * 1 ^ Board: D · -. Herbert Asmis * Dr. Christian Brunn - ris-rann? Or: 3ns = iinfî: SCHEINS AG - D-nOX Benin G5 - rcs-ecn 65 C211 \ Df -. '»To Hannse - Kan Otto Mittelstenseieid · Or. Hors:». £: ·:: Serim-Wee »11Ä-151. Ss« »l« eiS56fi. «MC 10

Λ __...... ^ Λ- C- .. Λλ —arM-.r «& A KDrl ·. IVnt. »_ Wr ΓΚ 7ΓΥΎ; ΠΓ) «Γ Î ft a T ί 1 ÛD 4GC

ψ «· jj 5 EXAMPLE 8

SCHERING AG

~ 33 ~ Commercial R & shisKhutz | Steam activity against Helminthosporiura teres on barley if in the greenhouse il I-10 To determine the steam activity, a pot with approx. 20 barley seedlings at the stage of the beginning of the second leaf was placed between two barley pots with a dried spray coating from a dripping wet treatment. The dripping wet treatment was carried out with an active ingredient concentration of 0.1%! 15. One was placed over all three pots per test element

Conidia suspension sprayed from the network stain Helminthosporium jl teres, which is prepared with an aqueous solution of 0.05% I sodium oleate and 0.02% gelatin and made up to 100 000 i | Had set spores per milliliter. After spraying i | In 20 of the spores, the three pots per test element were enclosed in polyethylene bags for three days and kept under greenhouse conditions of about 20 ° C. The bags were then opened by cutting off at the height of the leaf tip *: iî zen. After 8 days, the number of net spots per pot was counted 25. The fungicidal steam effect was calculated from this; as follows: $ _ net spots on exposed barley. 100 $ "" net spots on unexposed barley “ir 12212! . The substances according to the invention were present as 20% formulations. All exposures to steam were compatible with plants.

i

Invention

Compound No.__% Effect 2 100 35 3 100 4 99 10 100 13 85

Comparative agent m l- (4-chlorophenoxy) -3,3-dimethyl-l- 86 -36- | / (1,2,4-triazol-1-yi) -butanone L orstsnd: Dr. Herbert AsmisDr. Christian Sruhn Kans-Jü-oer. r-.err.anr. rcs’.sn53irift: SCHERiNG AG - D-’OX Benin 65 · postfä—. £ 5 6311 t Dr. Hemz HannesKarl Otto Minetsten & cneie Dr. Horst W-tzei Ps * ts = reoc-Kon »: Ss'lin-Weat« 7S-1K. Sanfcleli number * Λ

SCKERiNG AG

_3 & _ Commercial r.echis schüfet; j i 1 5 EXAMPLE 9 | Systemic effect of soil treatment before emergence *! against sugar beet powdery mildew Erysiphe polygoni in the greenhouse 1 ^ planting pots were sprayed with 0.3 active ingredient per hectare after sowing sugar beet and placed next to untreated pots in the greenhouse at about 20 ° C. After the beet plants had opened up (12 to 1¾ per pot), they were allowed to wait until the plants had developed the first two leaves 1 15; J and then inoculated by dusting the dry spores J of the beet powdery Erysiphe polygoni. Three weeks later (six weeks after the soil treatment) the infestation J of the leaves was rated. The fungicidal effect could only be achieved by absorbing the substances via the plant roots; i. $ 20 and was calculated as follows: '’100 -! E ^ a ^ in ^ e!? A” d ^ ti; -1 ° 0 · =% effect

Infestation xn Untreated e si -I The compounds were present as 20% formulations. All 25 S treatments proved to be contractual for the plants and led to a more vigorous, compact growth compared to the untreated control.

·! ^ According to the invention

Compound No._% Effect_ ll - 12 100 ^ 13 100 l4 100 35 40 -37- '? // s ~ \ k. Executive: Dr. HerOer? AsmisDr Christian Bruhfi - ri3r.E-J0r? Sr rigrnann Sw * "sk. NG AG - D-’OOC Befiin £ 5 * PO Box 5SC311

? Dr.fiem2 Hannse Kars Otto Mitteistersscaeio - Dr. Horst Witsei »cstsar.eoi-ncr.ts: BerrirvVvesi uTS-iCK, BanKisisans' XtX'C

^ ... - 7Ύ «r> r S r ··.« '.> · ..! dSf) 0 5 EXAMPLE 10

SCHERING AG

-37- Intellectual Property Law »Λ ί i.

Soy and wheat were sprayed with emulsions of the test substances in the pre-emergence. The amount applied was the equivalent of 2 kg of active ingredient / ha. Then the plants were cultivated in the greenhouse and measured after three weeks.

j - The table shows the registered percentage growth inhibitions.

! i 15 Growth inhibition according to the invention in%

Compounds No. Soybean Wheat • 2 39 28 3 22 28! 7 17 7 - 20 9 0 17 13 4 1½ 14 17 24 18 13 14 19 k 14 25 22 65 21! 23 30 17 1 25 35 24 26 35 24? 30 ’* comparison compound i2-chloroethyltrimethylammonium chloride 0 17

It can be seen that the compounds according to the invention are generally more active in 35% than the comparison compound.

i ät ϊ 4p _ 3a? ? / H «—-’- Mind: Or. Kerosrt Asrp.is · Or. Christian Brunn · Hsns-Jû? $ En rarann Posteriscnrifi: AG · D-10X Berlin SS * Pcsîi & cft SS 03 2 Dr. he.nz hsnnse »Kar« One M? t: eis: e ^ ss-.e! C · Dr. Horst jokes! ? ç £ îs2rec »Kon? c: 5er: in-Wett 1175-151, Ssntcfetefthi 1051X10 <1. . ... .... _ _ _ _ ___ _ _ ______ Bf * XI L. * rv- «·· *% * · tv. .

* H

SCHERÎNG AG

- GQvrtAlï & or legal protection! 38 s: i 5 EXAMPLE 11 I rice was treated with the compounds according to the invention in a pre-emergence application rate of 2 kg of active ingredient / ha.

I After three weeks of culture in the greenhouse, the percentage I-10 growth inhibition was determined.

This is shown in the table.

I Compounds j according to the invention No. _ Growth inhibition in% _ 4 j 22 11 i · 25 7 ï i 26 1¾ I 20:

Comparative compound 2-chloroethyltrimethyl-] ammonium chloride 0 25 f.

The growth inhibition of the compounds according to the invention does not give the comparison compound in the present application.

35 i! · Ι kd - 39- et »// I /« “___ ^%: Vorstana: Dr. Herbert Asmis * Dr. Christian öruhn * Ha ^ s-Jürcen Harr.ann rostansciinfi: SCHcR'NS AG - D-1K3C Benin 65 · PcrstfEZTi SS £ 311? Dr. neir «z Hannse · Karl Otto Miüe! ster.scre» d · Or. ricrst Wttrei Pc'tscr.eer-KDme '1175-1G1 1031X10 i ». _______- -. _. r, _________ ________ L · · - .w -r-y.- M SS w .. «ΛΛ ίΤΓ. fl J * I 5 EXAMPLE 12

SCKERiNG AG

-39 “Gewerfeüs & ar Rschisschutï ί!: 1 ii 1 - I sugar beets were sprayed in pre-emergence in an amount of '3 I 2 kg of active ingredient / ha. The percentage growth inhibition

The color of the plants was recorded after three weeks of greenhouse culture.

* ί The results are shown in the following table, j 115 Compound No._ growth inhibition according to the invention in% staining * _ 1 9 1! 3 34 1 I 7 3¾ 0 I 8 37 0; 'a 20! J' 9 25 1 j 10 37 0 f 12 22 0 13 4i 0 i | 1% 4l 0 1 25? 5 16 53 0 J 17 53 o I 18 22 1; Sj I 19 37 0 i 20 37 1.? 30 6 22 37 1! J 23 53 2 24 22 1 25 09 2 35 26 37 2

Comparative agent 2-chloroethyltrimethylammonium chloride 0 0 4o, I -40- ^ Board: Dr. Herbert Asmis Dr. Christian Brunn Hens-JDrgen Hamann Postal address: AG · D-1DX E-erün SS Fosifacr. SSC311 2 Dr. Heinz HannseKarl Otto MitteisienscneiQ - Dr. ttbrs ’A’; tZB> Pestssieac-Kontc: Bôfiln-tfeeî 1175 ^ 01. Bsnttieitrshf 1X1X10 40

SCHERING AG

- - Commercial legal protection t; j 5 * Coloring table: 0 = vie control jj | 1 = more intense green 1 2 = dark green i | The compounds according to the invention influence the growth of the beet, which is not achieved by the comparison compound in the present application.

| | 15. (S \! · S I · 20!;

M

H

fjj 5t y i »; j 25 ί · j j; 30 Î -

iS

Γ «*) 35 -kl - ko w Board: Dr. Herbert As ~ n: s * Dr. Christian 3 clock. · Hans-v: ûrgen HerrsaB SCHERÏNG AG D-19GC Benin 65 · Pcstfacü 6 £ 2311

ξ Dr. Heinz Hanr.se - Kari Gt’.c Mitteisienscneia · Dr. r.crs: W: ze. P; «ïa -. E: * - Kan: c: Be ^ m-Aes: Î175-1C ;. Bar.Kiettcti * lOC ^ XIO

«\ / NrC '% on / iar riM Hr Ρπμ-ρΗ cRe-iînflf Γ.Γ; ίτηρΓ -? Ηί A & rtflr'ir Kento-Mr. 1ß & TQTft Often? .Snrifei * 3AfV 1 tt * 400 «% | 5 EXAMPLE 13

SCHERING AG

_ ^ 1_ Hereditary legal protection i I Effect of prophylactic leaf treatment against the leaf stain pathogen Fusaritim culmorum on millet (Pennise-i tum glaucum) in the greenhouse.

. 10th

Young millet plants (approx. 30 per pot) at the stage of the beginning of the second leaf were sprayed to runoff with the specified concentra- tions. After the spray coatings had dried on, the treated and the untreated control plants were sprayed with a conidia suspension of Fusarium culmorum and placed in a moist greenhouse at about 22 ° C. After k days, the percentage of leaf area affected was estimated. The fungicidal activity was calculated as follows: 1: I 20! 100 - -? Efatf. i \ Be!; a? de— = «Effect! Infestation xn treated Î "The compounds according to the invention were in the form of 20% formulations.

1 25 I.

"% Activity according to the invention with ΐ compound No. 500 ppm 100 ppm I 2 100 100 * 3 91 30 9 80 I 12 90 I 13 100: 1½ 100 16 95 35 17 95 18 95 19 90 20 8ö 22 99 90! ^ 0 - k2r \ z “Board: Dr. herCsrt Armis - Dr. Christ! ar Eroim. Psns-J & fcer: Hair.anr Postanscnrif :: SCHE" 'N3 A3 · D-1033 Berlin 65 rdstfech 65 0311 = Dr. heinz hannse Kar CM Mitt.tster.stnaw · Cr. Ηβτκ Like * - Pastscnear-KontC: Berim-WestlUMM. BanldeiSsiS 10010010 Λ \ .T ^ rpit ^ »ûn rinr nac £ t ^ IF» _ pp «'·. ff. ... - - for I Lr. w rt <f uff C.AWi.r fe. f ^ flfl ΛίΙΙ

I _ 4β. SCHERING AG

I Gewersüshcr R &chisschuiz; ! 5% ¥ ir3mng rait j compound No._ 500 r> pm_100 ppm according to the invention! 23 100 99 | 24 100 97 | 25 100 98! io 26 98 93 | 27 90 I - 29 97 90 I 30 97 90 j 31 100 98 15! h \ j 20 y! 25 I; 30 35 i} ’j I - 43.

4o! *? ! i c Board: Dr. Herbert Asm. «· Dr. Christian Eruhn - Hans-Jürgen Hatr.ann “ostansshrift: SCHEFJWG AG - D - '. SX Eeriin 6 £ - FostfiJd’ 5: 3211

? Df. Heins hannseKar! Otto MitteistenseteidDr. hear joke «Fostsaea account: E9 -. n-v.est UTS-toi. EiarleiCtN VJB108IC

"Vrtres ^ enrii" r Πί "" ι Aiif. <Etrttt ": rstr" t * for Priuprrf v. Srf? W? Rt? Icnnr »en Γπγ, -, γ -« · '»o« ·, -r.e— £ Λ ’^ vür fc'r-.ni-wfcr Spnkîtf: SÄh! 1QD ^ 0C 00

SCKERiNG AG

- h 3- Intellectual Property Law - * f -1 5 EXAMPLE 1¾

Effect of prophylactic leaf treatment against the leaf stain pathogen Cercospora beticola on sugar beets in the greenhouse.

, 10 sugar beet plants with at least 2 well-developed leaves were sprayed to runoff point with the specified concentrations. After the spray coatings had dried on, the treated plants and untreated control plants were sprayed with a conidia suspension of Cercospora beticola be-1-5 and incubated in a greenhouse at 26 ° C. for 2 days in a moist state.

The plants were then cultivated under normal greenhouse conditions. The percentage of infestation was rated two weeks after the treatment.

. 20 Fungicidal activity was calculated as follows: 100. Infection in treated .....

100 - Infection in untreated- * * WlrtomS

The compounds were in the form of 20% formulations.

25th

% Effect according to the invention

Compound No. 500 ppm 100 ppm 3 100 100 11 93 30 12 93 13 100 i4 93 16 100 17 87 35 19 93 20 87 21 100 96 22 100 100 23 100 100 / - <ih- 1 ii Y— ^ Board of Directors: Cr. Herbe ^ t Acmis - Dr. Cïirst an Sruhn Ha ^ s-Jûrçen K & r.ann Fosanssnrift: SCHERING AG * D-10QG B ^ riin 63 Rostiadi

Or. * "* E * n ^ Hannse * Karl Oho - ur. Horst Witzei Poststr. &Si-Konic; Seriirs-Wes * 1173-1Öl. Sanfcieifeshî 1001031G

* Vftrftifyjancer des Ai: f & iffr> rsra? S! Dr Pecsrß v_ Scnwsrfriccrr.eri SArîifïor ilorrtiTierrfcanfc AG_ Seriin Kcnta-Nr. 1Π8 7Βί ¥> 0Π_ RanfcifefiT’sfti 1X 400 ûfi

hk SCHERiNG AG

~ ~ Gewesisiiehsr legal protection i 5 Invention% effect with j compounds No. 500 ppm 100 ppm 2 100 100 25 96 96 10 26 100 96 27 98 98 28 100 98 29 100 98 30 100 100 15 31 100 100

/ K

20 25 r f r! i; 30 i -.

! [: j 35

P

- ^ 5-hO

J. Board: Dr. Herbert Asmî *. Dr. Christian ârtthn · Kans-Jü'gen Hamenn Rostansonritt: SCHERiNG AG - D-1ÖCC Berlin 65 - Pcsi «sfi Eé 0311 Z Dr. Heinz Hannse - Kan Ctto Miüetste-ssr.eid Dr. Hc'st Wttfet Posts — a = <- Cor.! C: Een-n-Wes; 11 / 5-101. BanUettsahl 1X10010 S Chairman oes Supervision * «- no cw ,, = rrin P — warntccEsen Seritner ComtnerzEamc AG. Berlin. Account number. 105 7035-X. SanfcleitzahMXaoni * V · »-

SCHERING AG

- 45- Commercial Ee-cbiiscnutz j j 5 5 EXAMPLE 15 ij - J | Effect of seed treatment against seed-bearing Helminthosporium sativum (pathogen of foot disease) on barley.

i #i j i I 10 Barley seed contaminated with Helminthoporium sativum I was treated with 50 mg of active ingredient per 100 grams. Of each }

Treatment and untreated, 2 g of seed were sown in 2 repetitions in pots and incubated at 15 ° C in a climatic chamber. From the emergence of the plants, a 15-hour rhythm was artificially illuminated. After 4 weeks, the% rate of plants with foot disease was determined. All of the plants were diseased in Untreated.

| | i: I 120 compound according to the invention% action 2 100 3 99.5: | 4 loo j | 5 99.5 f 25

The compounds were in the form of 20% formulations.

Î *

: I

30 • r £ -} '- £ 35 _ 46.

4o m ot r? ~ Board: Df. Herbert Asmis · Dr. Christian Brufir * Hans-Jprcan Hamann Pcstanscnrift: SCHERING AG *! MOOß Benin ÊS. Fostfa: »S5Ö11 Z Pr, Heinz tfannseKari Otto Mittefstsr.scneid - 0-r- ~ 3rsi W-tze. Posiscr.esr account: Bs'f’r-V / sfSt saniete

1_ ____ fi I. r '-_______ <Λ W »_ n..-S- -Λν r. .. «-1 Λ nr> X

SCHbHlNG AG

”~ Ge ^ erEIiehsr -cf.uia: i '<!' L <ς EXAMPLE l6 4 ^ -; rj Î I Effect of seed treatment against seed-bearing Phoma I betae on sugar beet.

i fl 1. 10 Sugar beet seed contaminated with Phoma betae was treated with ß

Ij treated with 250 mg of active ingredient per 100 grams. Of repetitive I · deltera and untreated seeds, k repetitions I of 25 seeds each were sown in pots and placed in a climate chamber at 15 ° C. After the plants had emerged, lighting was carried out artificially in the! Jj 15 12-hour rhythm. Until the trial was completed after 7 weeks, the diseased plants were counted and removed weekly. Overall sick in the un-! treated control 76.1% of the emerged plants. The ; The protective effect of the treatment was calculated as follows: tj. 20, "F infestation in treated. 100 fl 100 -„ -r- r-3—7 ^ - =% effect 5 infestation in treated 0

The compounds according to the invention were in the form of formulations.

1 25 ri invention

Compound no. _% Effect 2 100! 3 97 30 * 97! ’5 100!: 6 83 12 92 13 99 35 14 96

Comparative agent beta- (1,1'-biphenyl-4-yloxy) -alpha- 51 (1,1-oleimethylethyl) -1H-1,2,4-triazol-1-ethanolamine 1- (4-chlorophenoxy) -3 » 3-dimethyl-1- (1,2, 4-57 triazol-1-yl) -2-butanone, 4o / -47- 3 // _ · £ Board: Dr. Hs-Oert AsmisDr. Christian BruhnHans-Jârçen Hamann Postar.scrtri “: SCK ==: nS AG - D-100C Seriin S5 · rustproof £ 5 03 Π ~ Dr. Heinz Hannse Kari Otto Mittetstenssteiü Dr. Horst Witze * Pottr -: “-» - Kcntc - Seriir-'A'est r! 75-10t. Sênicieitzafil IX10010

- M l / nreiiTan ^ nr rioc · iti <r. t “i. .. p -i. £. *. *. '<- **** - »« ·· -. -.ar · .s nr i. c teriir ΓΥ ~ · r = Pt «·. ' . * e I <ΗΠ ΑΠΟ C

Claims (6)

5 PATENT CLAIMS f 1. 1,2,4-triazol-1-yl-propionitrile of the general formula 1-10, 1 = 7 I R - Ç - ch2 - N | X I An il in the [j ’R one possibly one or more times, same or Fj k | ^ different from halogen, (C ^ -C ^) - alkyl, (C ^ -C ^) - ï alkoxy, (C ^ -C ^) - alkylthio, trifluoromethyl or the | Nitro group-substituted aromatic hydrocarbon residue and 1 'R1 ^ Ci "Ci ^ ^" alkyl1 (c ^ -Cg) alkenyl, (C ^ -Cg) alkynyl, or "^ one optionally one or more times, identically or differently by Halogen, (C ^ -C ^) - alkyl, (C ^ -C ^) - j, J. Alkoxy, (C ^ -C ^) alkyl thio, trifluoromethyl or the I nitro group substituted Fnenylalkylrest mean 1 and their Acid addition salts with inorganic and organic acids. 25:: 2. 1,2, ^ - Triazol-l-yl-propionitrile according to Claim 1, in which ** I5 R is optionally one or more, identical or i !; different from halogen, (C ^ -C ^) - alkyl, (C ^ -C ^) - alkoxy, ;; (Ci ~ C ^) - alkylthio, trifluoromethyl or the nitro group substituted phenyl group,. and h R ^ ( C1-C10) -alkyl, (C ^ -Cg) -alkenyl or, if necessary, one or more times, identically or differently by halogen, (C ^ C ^) -alkyl, (c 1 “cZl) -alkoxy, (C1 -C ^) - Alkylthio, trifluoromethyl or the nitro group substituted benzyl radical. / R 'U -2-, ή 4to £ X ° rf.îan0 * tPr 'Asrn: s - Dr. Chr.s:; to Bruhn - ^ ans-Jùrtis- '. .- 'amar.n Pcstcnszru: * 4 - SO ^ iN "ih. •" j.-'- rr r "r [.. - _____" Dr. Heinz hannss - Karl Gîte M:! Ïe.s: erscn &? C. Dr. rrorst jokes' - ^ "Z '^ Au X ter, îrî 5o · ^ ssracr 650311 - = Chairman ces Awfsicnt5.'2ts: Z: £ c-ard v S ~ α ^ γ-κ · -' · -.en s -r7â ^ *! MÎ!: öe: r'T ^ -st EsnKieitzah * "X10310 g Sit- dr G, * SehSr ~ p-„ * - v ^ v ^ fin rcr;, rer ser: · «. Konrc-fcf. 103 7005-X. Sar, *; *; = ** -OCUOOCX 2 bit *. u_r jeseliscr.a .. Benin and aeroKam »^ aer..ner Disccnto-eanK A £? R «= r; r» k'rr.fL.wr «-ντο _________,« SCHERING AG J _ 9 Gererblk & ar R & ctts schütz i Î 3. isopropoxy-2-phenyl-3- (1,2,4-triazol-l-yl) propionitrile, hydronitrate 4. 2-isopropoxy-2-phenyl-3- (1,2,4-triazol-1- yl) - propionitrile 5. 2-hexyloxy-2- (2-methylphenyl) -3- (1,2,4-triazol-l_yl) propionitrile, hydronitrate 10 6. 2-butoxy-2- (2-methylphenyl) - 3- (1,2,4-triazol-1-yl) propionitrile 7 · 2-butoxy-2- (2-methylphenyl) -3- (1,2,4-triazol-1-yl) propionitrile, hydronitrate ; 8. 2-Hexyloxy-2- (2-methylphenyl) -3- (1,2,4-triazol-: 1-yl) propionitrile 15 9 · 2-butoxy-2-phenyl-3- (1,2, 4-triazol-1-yl) propionitrile, hydronitrate 10. 2-Butoxy-2- (2-chlorophenyl) -3- (1,2,4-triazol-1-yl) propionitrile, hydronitrate 11. 2-ethoxy -2-phenyl ~ 3- (1,2,4-triazol-1-yl) - • propionitrile, hydronitrate I 20 12. 2-phenyl-2-propoxy-3- (1,2,4-triazol-1- yl) - propionitrile, hydronitrate 13.2- (3-chlorophenyl) -2-hexyloxy-3 ~ (1,2,4-triazol-1-yl) propionitrile, hydronitrate 14. 2-butoxy-2-phenyl-3 - (1,2,4-triazol-1-yl) -I propionitrile i 15 ·· 2-phenyl-2-propoxy-3- (1,2,4-triazol-1-yl) propionitrile; i 16 »2-Athoxy-2-phenyl-3- (1,2,4-triazol-1-yl) -1 propionitrile i 17.2-hexyloxy-2-phenyl-3- (1,2,4-triazole -1-yl) - propionitrile, hydronitrate! orv l8. 2-allyloxy-2-phenyl-3- (1,2,4-triazol-1-yl) propionitrile, hydronitrate I =. 19 · 2-butoxy-2- (4-chloropnenyl) -3- (112,4-triazol-1-yl) propionitrile, hydronitrate 20. 2-allyloxy-2-phenyl-3- (1,2,4- triazol-1-yl / -propionitrile; 21. 2-methoxy-2-phenyl-3- (1,2,4-triazol-1-yl) - i propionitrile 22. 2-hexyloxy-2-phenyl-3- ( 1,2,4-triazol-1-yl) -l propionitrile j23.2- (2-chlorophenyl) -2-hexyloxy-3 ~ (112.4-trxazole- |; «1-yl) -ropionitrile, hydronitrate M 7 '-3- 1. He'De-: Ae - s - Dr Ch'-stia' ·. = Γυ.-η _____; g ur.jteaiz hannse Kan C- «o Μ.« β-κβ. ·, ε = · .β <· it -ο.ΐv.r. ~ Z '"s'r'e" "Psstansenrift: SCHeHJNQ AQ - 5-iOOG S * <- Bn SS. PesSSds 650311; - = V3 '£.: Zeacer res At,' 3.3i? S.- £! E = -ua. „Ve <2 — .1, '==' «—.Er * .Account: BerSm-West nrS-ic: SarKieitza'- '' OG-IOC'D I Sia cer Gese.! * - a ': Ser.« · · - ^ San-rer Co-rmerrsani: AG. Benrn. Kome- * ·. 136 ^ 006 ab. Ba-nbeccK? X * OCOO i = ïâniüw: ·. «», Ic ____ Γ “ser .ner u-scomo-eanK AG. Fearun. Koato-Nr. 241 / soas Bannieirrafii-îoûrac3; SCHERiNG AG _ 3_ Intellectual Property Law «ii 15: Ί î; | 5 24. 2- (2-chlorophenyl) -2-propoxy-3- (1,2, -i-triazole- i | 1 -yl) -propionitrile, hydronitrate ij 25. 2- (4-chlorophenyl) -2-propoxy-3- (1,2,4-triazole-; i 1-yl) -propionitrile, hydronitrate h 26. 2- (4 -Chlorphenyl) -2-hexyloxy-3- (1,2,4-triazol-jj 1-yl) propionitrile, hydronitrate il 10 27. 2- (4-chlorophenyl) -2-propyloxy-3- (1,2 , 4-triazol-jî 1-yl) -propionitrile I 28. 2-butoxy-2- (4-chlorophenyl) -3- (1,2,4-triazol-îj 1-yl) -propionitrile I; 29. 2. - (2-methylphenyl) -2-octyloxy-3- ( 1,2,4-triazole; "1-yl) propionitrile, hydronitrate! 15 30. 2-decyloxy-2- (2-methylphenyl) -3- (l, 2,4-triazole- | j 1-yl) propionitrile, hydronitrate 31. 2- (2-methylphenyl) -2-octyloxy-3- (1,2,4-triazol-1-yl) propionitrile 32. 2- (2-chlorophenyl) -2-butoxy-3- (1,2,4- triazol-1-yl) propionitrile .20 33. 2- (2-chlorophenyl) -2-propoxy-3- (1,2,4-triazol-1-yl) propionitrile 34. 2-butoxy-2- ( 2,4-dichlorophenyl) -3- (1,2,4-triazol-1-yl) propionitrile, hydronitrate 35. 2-butoxy-2- (2,4-dichlorophenyl) -3- (1,2,4 -triazol- {1-vl) -propionitrile 'i * i * 25 36. 2-allyloxy-2- (2,4-dichlorophenyl) - 3 “(11 2,4-triazol-1-yl) -propionitrile 37 · 2- (3,4-dichlorophenyl) -2-propoxy-3- (1,2,4-triazol-1-yl) propionitrile, hydronitrate 38. 2- (3,4-dichlorophenyl) -2-propoxy-3 - (1,2,4-triazol-1-yl) propionitrile 30 29. 2- (3,4-dichlorophenyl) -2-hexyloxy-3- (1,2,4- 'triazol-1-yl) - propionitrile, hydronitrate 40. 2- (3,4-dichlorophenyl) -2-hexyloxy-3- (1,2,4- -i; 'triazol-1-yl) propionitrile 41. 2- (4-pluorphenyl) - 2-propoxy-3- (1,2,4-triazol-1-yl) propion itril, hydronitrate 35 42- 2- (4-Pluorphenyl) -2-propoxy-3- (1,2,4-triazol-1-yl) propionitrile 43. 2-Butoxy-2- (4-fluorophenyl) -3 - (1,2,4-iriazol-l_yl) propionitrile, hydronitrate 44. 2-butoxy-2- (4-fluorophenyl) -3- (1,2,4-triazol-1-yl) propionitrile § k0 h -4 - £ Æe “e'we, c '" â “5 ™ S0HE?! MS AS - D-1030 Serlin 65. Postfecn 650511 Vorsiir = r * 3er de £ ÂLiiSiCf.îSrgTî “·· £ = - * '= v. Eor ^^ eT ipc 10010 S Sics <SW S * »» saœ «· sfr'i" Μ Berg «* .- * - ser.mer —.C3 ri * A; - ιή" k Vt ". -I ™ - . ri. - - - * <SCHERING AG _ 4 _ Intellectual Property Law -I;;! 5 45. 2- (2-fluorophenyl) -2-propoxy-3- (1,2,4-triazole- j 1- yl) -propionitrile 46.2- (2-fluorophenyl) -2-propoxy-3- (1,2,4-triazol-! 1-yl) -propionitrile 47- 2-butoxy-2- (2-fluorophenyl) - 3- (1,2,4-triazol-1-yl) propionitrile, hydronitrate 10 48. 2-butoxy-2- (2-fluorophenyl) -3- (1,2,4-triazol-1-yl) - propionitrile 49. 2- (2-fluorophenyl) -2-hexyloxy-3- (1,2,4-triazol-1-yl) propionitrile, hydronitrate j 50. 2- (2-fluorophenyl) -2-hexyloxy-3 - (1,2,4-triazol-j - 1-yl) propionitrile 51, 2- (4-broraphenyl) -2-propoxy-3- (1,2,4-triazol-1-yl) propionitrile, Hydronitrate 52. 2- (4-bromophenyl) -2-propoxy-3- (1,2,4-triazol-1-yl) propionitrile I 53 «2- (4-bromophenyl) -2-hexyloxy-3- ( 1,2,4-triazol-I 1-yl) propionitrile, hydronitrate I "^ 54. 2- (4-bromophenyl) -2-hexyloxy-3- (1,2,4-triazol-1-yl) - propionitrile! 55 «2 - (2,4-dichlorophenyl) -2-propoxy-3- (1,2,4-triazol-l-yl) propionitrile, hydronitrate j 56. 2- (2,4-dichlorophenyl) -2- propoxy-3- (1,2,4-triazol-1-yl) -1 propionitrile ^. 57- 2- (2-methylphenyl) -2-pentyl-3- (1,2,4-rriazol-l-yl) - i propionitrile, hydronitrate '/ 58. 2- (2-methylphenyl) -2-pentyl- 3- (1,2,4-triazol-1-yl) propion-I 59.2- (4-Kethylphenyl) -2-propoxy-3- {1,2,4-triazol-1-yl) - I propionitrile, hydronitrate! t 60. 2-Hexyloxy-2- (4-methylphenyl) -3- (1,2,4-triazol-1-yl) - i) '4 30 propionitrile, hydronitrate j 61.2- (4-methyl- phenyl) -2-propoxy-3- (1,2,4-triazol-1-yl) - j! = propionitrile i 62. 2-Hexyloxy-2- (4-methylphenyl) -3- (1,2,4-triazol-1-yl) -; propionitrile 63. 2-butoxy-2- (4-methylphenyl) -3- (1,2,4-triazole-1-vl) -is; 35 propionitrile! fl SS \%; 1; '/ Λ tA 4o û - y - Vorstanc: Cr. Herbert A $ rr- $. Dr. Christian Brunn Hans-Jü-cer -ετ.εππ? Cs: =. R. £ Gr.r; * î: SG “B?:? Î2 * 3 Serra 65 ^ cst'acr S: CC *" 1 'τ Dr Heinz H2nnse - Karl Otto Mirtesstenscneiß ♦ Dr. Horsî VV> ize: -.xce · r * i · ·? Ηπ imin SCHERING AG 3. Commercial legal protection | 'I 5 64. Process for the preparation of 1,2,4-triazol-1-yl-propion-I itrilai according to Claims 1 to 63, characterized in that I that compounds of the general formula il 0 - R. ii 1 R - C - CH - Y 10 Ah i j with 1,2,4-triazole of the formula i N - CH I 1. 115 HCv ß * xn / H or its alkali compounds in the presence of a solvent and optionally in the presence of a base; {I 20 sets in which R and R have the meaning given above and 5. c * I Y halogen or the alkylsulfonyloxy or arylsulfonyloxy radical which is optionally halogenated in the side chain 'means. i I r - | 25 · Biocidal agents, characterized by a content of at least one compound according to claims 1 to 63 · e i I 66 .. Biocidal agents according to claim öS with fungicidal activity. j. Ä ΛΛ ΐ * 67. Biocidal agent according to claim% 5 with growth-regulating l | ·. , Effect. I "68 ^ Biocidal agents according to claim 65 with bactericidal activity.: N 35 69. Biocidal agents according to claim 65 in a mixture with carriers and / or auxiliaries. \ AAK i, S - 6 - ir T board: Dr. Herbert Asmis - Dr. Christian BrunnKans-JS-çen Hsrr.enn ^ cstarscrriî: SCn'EP.îNG AG - D-iGCC Benin £ 5Pcstracr. € 5 2311 i Dr. Hsiuz Hanr.se * Kar. Cftc M:; te : st £ it = raici - Dr.Hcrs? Wrîze1> - '<cr. * c Ee'. ^ - Aest 1175-13: EsnKfe.îza * .: lOGIOCIC Chairwoman * · css Supervisory Board xsrats: Dr. E0u2f0 v. Scnwenzr.ozosr Sür -n ~ r Czrr.r? ^ ErzssnK AG.Benin.Kor: o-No.106 TDK OC.Sani-neiîzan '-.X <00 OC