NZ200967A

NZ200967A - Imidazopropionitriles and biocidal compositions

Info

Publication number: NZ200967A
Application number: NZ200967A
Authority: NZ
Inventors: D Baumert; C Skotsch; H Krahmer; E Pierch
Original assignee: Schering Ag
Priority date: 1981-06-30
Filing date: 1982-06-15
Publication date: 1985-07-12
Also published as: GB2101995B; PT75147A; DK291582A; MA19512A1; NO822231L; FR2519635B1; AU8546482A; NL8202339A; ZA824688B; IT8221939A0; PT75147B; DD202977A5; KR840000506A; CH655311A5; BR8203803A; BG37373A3; PH19047A; FI822033L; CS236480B2; PL129716B1

Description

<div class="application article clearfix" id="description"> New Zealand Paient Spedficaiion for Paient Number £00967 70096 Priority Dat^aj; A Complete Specification Filed: Class: .... Publication Date: ... JkJ.2 AvT p-0. Jourr/il. No: «/?"?« NEW ZEALAND Patents Act 1953 COMPLETE SPECIFICATION "IMIDAZOLYLPROPIONITRILES, PROCESS FOR THE MANUFACTURE OF THESE COMPOUNDS AND THEIR USE AS BIOCIDAL AGENTS." We, SCHERING AKTIENGESELLSCHAFT, a body corporate organized according to the laws of Germany, of 170-178 Mullerstrasse, D-1000 Berlin 65, Germany and Waldstrasse 14, 4619 Bergkamen, Germany, do hereby declare the invention, for which we pray that a Patent may be granted to us, and the method by which it is to be performed to be particularly described in and by the follov.d nc- ,<r LtitomoivL _ 1 _ 200967 - 2 - The invention relates to imidazolylpropionitriles and biocidal agents containing them. Imidazolylpropionitrile derivatives having fungicidal action have already been disclosed. 5 These, however, have a relatively narrow spectrum of action, and this is unsatisfactory. This present invention provides imidazolylpropionitriles of the general formula 10 in which represents an aromatic hydrocarbon radical that is unsubstituted or substituted by one or more of the same or different substituents selected from halogen atoms, (C^-C^)-alkyl, (C^-C4)-alTcoxy and (C^-C^-alkylthio radicals, and trifluoromethyl and nitro groups, and represents a (C^-C^Q)-alkyl, (C^-CgJ-alkenyl, (C3-C3)-alkynyl or phenylalkyl radical each of which is unsubstituted or substituted by one or more of the same or different substituents selected from halogen atoms, (C^-C^)-alkyl, (C^-C^)-alkoxy and (C^-C^J-alkylthio radicals, and tri-fluoromethyl and nitro groups, and acid addition salts thereof with inorganic and 25 organic acids. 15 R< - 3 - (f^ ^ /? • . i /J ^ // It will be understood that compounds of the invention can exist in the form of isomers and the written nomenclature and structural formulae shown in the specification and claims should be taken to include the 5 individual isomers as well as mixtures thereof. The imidazolylpropionitriles according to the invention are biocidally active in the widest sense but are especially distinguished by a fungicidal action in which, surprisingly, they are superior to known active 10 substances of analogous constitution and mode of action. They have a broad spectrum of fungicidal action. Thus the imidazolylpropionitriles of the present invention open up a wide range of possible uses, especially in the field of plant protection. 15 Surprisingly, their fungicidal action extends to combating fungi of the most varied systematic position. In the treatment of parts of the plant above the soil, they provide protection against wind-borne causative organisms. The compounds can also be used for treating 20 seeds for protection against seed-transferable causative organisms. In addition, they have systemic action, that is, they are absorbed by the roots of the plants, for example, after being introduced during sowing, and are transported to the parts of the plant above the soil 25 and protect these against causative organisms. Further actions that may be mentioned are growth-regulating and bactericidal actions. ?00967 - 4 - Because of their recognised broad spectrum of action, the compounds are suitable not only for protecting crop plants but also for protecting material and for combating human-pathogenic and animal-pathogenic 5 microbes and they therefore have a wide range of possible uses. The fields of application in which the compounds exhibit outstanding effects depend on the particular meaning of the substituents. Thus, they can be used as 10 fungicides, plant growth regulators or bactericides, as the case may be. In the compounds "of the invention I, an alkyl, alkenyl or alkynyl radical or a phenylalkyl radical represented by is unsubstituted or substituted as 15 specified above. An alkyl, alkenyl or alkynyl radical may, for example, be substituted by one or more alkoxy radicals, although an alkenyl or alkynyl radical, especially, is preferably unsubstituted. Thus, R may represent, for example, 2-fluoropheny1, 3-fluoro-20 phenyl, 4-f luorophenyl, 2-chlorop'nenyl, 3-chlorophenyl, 4-chlorophenyl, 2-bromophenyl, 3-bromopheny1, 4-bromo-phenyl, 2-iodophenyl, 3-iodophenyl, 4-iodophenyl, 2,3-dichlorcphenyl, 2,4-dichlorophenyl, 3,4-dichlorophenyl, 2,6-dichlorophenyl, 2-methylphenv1, 3-methylphenyl, ^ 4-methylpheny1, 2-ethylphenyl, 3-ethylphenyl, 4-ethyl- phenyl, 2-prcpylphenyl, 3-propylphenyl, 4-propylphenyl, 2-isopropylpheny1, 3-isopropylphenyl, 4-isopropylphenyl, - 00967 - 5 - 2-butylpheny1, 3-butylpnenyl, 4-fcutylphenyl, 2-sec — butylphenyl, 3-sec—butylphenyl, 4-sec—butylphenyl, 2-tert-butylphenyl, 3-tert-butylphenyl, 4-tert-butylphenyl, 2-methoxypheny 1, 3-methoxypheny 1, 4-methoxypheny1, 2-ethoxypheny1, 3-ethoxypheny1, 4-ethoxypheny1, 2-methyl-thiophenyl, 3-methylthiophenyl, ^-methylthiophenyl, 2-ethylthiophenyl, 3-ethylthiophenyl, 4-ethylthiophenyl, 2-trifluoromethylphenyl, 3-trifluoromethylphenyl, 4-trifluoromethylphenyl, 2-nitrophenyl, 3-nitrophenyl, 4-nitrophenyl, 3-fluoro-4-methoxyphenyl, 2-chloro-5-nitrophenyl, 4-chloro-2-fluorophenyl, 3,4,5-trimethoxy-phenyl, or 5-chloro-2-nitrophenyl, may represent, for example, (C^-C^0)-alkyl, for example methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, isopropyl, 2,2-dimethylprop-l-yl , 3 , 3-dimethylbut-2-yl,(C -CQ)-alkenyl, for -5 o example 2-buten-l-yl, 3-methyl-2-buten-l-yl, hexenyl, heptenyl, octenyl, (C^-Cg^alkynyl, for example propargyl, butynyl, pentynyl, hexynyl, heptvnyl, octynyl, or phenylalkyl, for example benzyl, 2-fluorobenzyl, 3-fluorobenzyl, 4-fluorobenzyl, 2-chlorobenzyl, 3-chloro-benzyl, 4-chlorobenzyl, 2-bromobenzyl, 3-bromobenzyl, 4-bromobenzyl, 2,4-dichlorobenzvl, 2,6-dichlorobenzyl, 3,4-dichlorobenzyl, 2-methylbenzyl, 3-methylbenzyl, 4-methylbenzyl, 2-nitrobenzyl, 3-nitrobenzyl, 4-nitro-benzyl, 2-trifluoromethylbenzyl, 3-trifluoromethylbenzyl, 4-trifluoromethylbenzyl, 2-methoxybenzyl, 3-methoxy- "009 6 7 - 6 - benzyl, 4-methoxybenzyl, 2-ethcxybenzyl, 3-ethoxybenzyl, 4-ethoxybenzyl, 2-propoxybenzyl, 3-propoxybenzyl, 4-propoxybenzyl, 2-butoxybenzy1, 3-butoxybenzyl, 4-butoxybenzyl, 2-rriethyl thiobenzyl, 3-methylthiobenzvl, 4-methylthiobenzyl, 2-ethylthiobenzyl, 3-ethylthiobenzvl 4-ethylthiobenzyl, 2-butylthiobenzyl, 3-butylthiobenzyl and 4-butylthiobenzyl. may also represent, for example, an alkoxyalkyl or dialkoxyalkyl group, for example 2-methoxyethyl or 3,3-dimethoxybutyl. Suitable inorganic and organic acids for forming the acid addition salts are, for example, hydrohalic acids, such as, for example, hydrochloric acid and hyarobromic acid; phosphoric acid, sulphuric acid, and, especially, nitric acid; monofunctional and bifunc-tional carboxylic acids and hydroxycarboxylic acids, such as, for example, acetic acid, maleic acid, succinic acid, fumaric acid, tartaric acid, citric acid, salicylic acid, sorbic acid and lactic acid: and sulphonic acids, such as, for example, £-toluenesulphonic acid and 1,5-naphthalenedisulphonic acid. Compounds according to the invention having an especially good fungicidal action are those in which R represents a phenyl group unsubstituted or substituted by one or more of the same or different substituents selected from halogen atoms, (C^-C^)-alkyl, (C^-C^J-alkoxy and (C^-C^J-alkylthio - 7 - •'00967 radicals, and trifluoromethyl and nitro groups, and represents a (C^-C^J-alkyl radical, an allyl or propargyl group, or a benzyl group unsubstituted or substituted by one or more of the same or dif-5 ferent substituents selected from halogen atoms, (C1-C4)-alkyl, (C1-C4)-alkoxy and (C1-C^)-alkyl-thio radicals, trifluoromethyl and nitro groups, and their salts. Especially, there should be mentioned those in 10 which R represents a phenyl, 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, 2,4-dichlorophenyl, 2,6-dichloro-phenyl, 3,4-dichlorophenyl, 2-fluorophenyl, 4-fluorophenyl, 4-bromophenvl, 2-methylphenyl, 15 4-methylphenyl, 4-methoxyphenyl or 4-nitrophenyl group, and R.j represents a methyl, ethyl, propyl, isopropyl, pentyl, hexyl, allyl, propargyl, benzyl, 2-cnloro-20 benzyl, 4-chlorobenzyl, 2., 4-dic'hlorobenzyl or 3,4- dichlorobenzyl group, and their salts. The following compounds have outstanding action: 2-n-butoxv-2-(2-chlorophenyl)-3-(imi dazol-1-yl)-propio-25 nitrile, hydronitrate, 2-n-butoxy-2-(2-chlorophenyl)-3-(imidazol-1-yl)-propio-nitrile, 200967 - 8 - 2-n-butoxy-2-(4-chlorophenyl)-3-(imidazol-1-yl)-propio- nitrile, hydronitrate 2-(4-chlorophenyl)-3-(imidazol-1-yl)-2-n-propoxypropio-nitrile, hydronitrate 2-(2-chlorophenyl)-3-(imidazol-1-yl)-2-n-propoxypropio-nitrile. The present invention also provides a process for preparing a compound of the general formula I or a salt thereof, which comprises reacting a propionitrile of the general formula 0 - R, 1 ' R - C - CH_ - Y II I 2 CN in which R and R^ have the meanings given above and Y represents a halogen atom or an alkylsulphonyloxy or arylsulphonyloxy radical which is optionally halogenated in the side chain, with imidazole of the formula HC - NH II I HC CH \/ N or a salt thereof, in the presence of a solvent and optionally in the presence of a base. A halogen atom represented by Y is, for example, chlorine, bromine or iodine; an alkylsulphonyloxy 2 009 6 - 9 - radical is, for example, a methyl-, ethyl-, propyl- or trifluoromethyl-sulphonyloxy group, and an aryl-sulphonyloxy radical is, for example, a benzylsulphonyloxy or p-toluenesulphonyloxy group. 5 The reaction may be carried out both with an excess of imidazole, if desired in the presence of a solvent, or with the addition of a strong base, for example sodium or potassium hydroxide. Further, it is possible to use an alkali metal imidazole instead of imidazole. 10 Suitable solvents are substances that are inert towards the reactants, preferably substances of polar, aprotic cuaracter, such, for example, as N,N-dimethyl-formamide, N,N-dimethylacetamide, N-methylpyrrolidone, tetramethylurea, hexamethylphosphoric acid triamide and 15 benzonitrile, and also higher-boiling optionally substituted aromatic and aliphatic hydrocarbons, such, for example, as toluene, chlorobenzene or xylene. The reaction temperature may be varied within wide limits. A temperature of from 100°C to 200°C is 20 preferred. The reaction is generally carried out under normal or excess pressure. The acid addition salts can be obtained according to conventional salt-forming processes, for example by dissolving a compound of the formula I in a suitable 25 solvent and adding the acid. The imidazolylpropionitriles of the general formula I according to the invention are generally almost -10- colourless and odourless oils. The acid addition salts derived therefrom are generally colourless and odourless crystalline compounds. The oils dissolve sparingly in water and more or less readily in organic solvents, 5 such as, for example, alcohols, ethers or chlorinated hydrocarbons. The acid addition salts dissolve partially in water and readily in polar organic solvents, such, for example, as acetonitrile, N,N-dirnethylformamide, lower alcohols, chloroform and methylene chloride. 10 Compounds of the general formula I and their salts have, especially, fungicidal action but they are at the same time distinguished by growth-regulating effects on a number of crop plants. As already mentioned, the compounds are transported 15 svstemically in the plant. Accordingly, they exhibit their growth-regulating action both in the case of applications over the soil and also in the case of spray treatment. Growth-inhibiting effects on cress and cotton are 20 particularly pronounced. Apart from the actions specified above, compounds of the general formula I and their salts also exhibit a bactericidal action which permits further possible uses. 25 The active substances of the invention may be used alone, in admixture with one another or with other active substances. Other plant-protecting or pest- -11- combating agents may, if desired, be added, depending on the desired purpose. The active substances or mixtures mentioned above are advantageously used in the form of preparations, 5 such, for example, as powders, strewable agents, granulates, solutions, emulsions or suspensions, with the addition of liquid and/or solid carriers or diluents and, if desired, wetting, adhesion, emulsifying and/or dispersion auxiliaries. 10 Suitable liquid carriers are, for example, water, aliphatic and aromatic hydrocarbons, e.g. benzene, toluene and xylene, cyclohexanone, isophorone, dimethyl sulphoxide, dimethylformamide, and also mineral oil fractions and vegetable oils. 15. Suitable solid carriers are mineral earths, for example tonsil, silica gel, talcum, kaolin, attapulgite, limestone, silicic acid and vegetable products, for example meals. Surface-active substances that may be present in 20 the preparations are, for example, calcium ligninsul- phonate, polyoxyethylene alkylphenyl ethers, naphthalene-sulphonic acids and their salts, phenolsulphonic acids and their salts, formaldehyde condensates, fatty alcohol sulphates and substituted benzenesulphonic acids and 25 their salts. If the active substances are to be used for dressing seeds, colouring substances may also be admixed in 200967 - 1? - order to give the dressed seeds a clearly visible colour. The proportion of the active substance(s) in the various preparations may vary within wide limits. For example, preparations may contain from 10 to 90 % by 5 weight of active substances, from 90 to 10 % by weight of liquid or solid carriers and, if desired, up to 20 % by weight of surface-active substances. The agents may be applied in customary manner, for example with water as the carrier in quantities of 10 spray liquor of from 100 to 1000 litres/ha. The application of the agents by the so-called "low-volume process" or "ultra-low-volume process" is also possible, as is their application in the form of so-called microgranulates. 15 3-Arylsulphonyloxypropionitriles or 3-alkylsul- phonyloxypropionitriles of the general formula II used as starting materials for preparing compounds of the general formula I, in whiich Y represents an arylsulphonyloxy or alkylsulphonyloxy radical, have hitherto 20 not been described in the literature. Accordingly, the present invention provides a compound of the general formula II in which R and have the meanings given above and Y represents an unsubstituted or halogen-substituted arylsulphonyloxy radical 25 or alkylsulphonyloxy radical, and a process for its preparation. The alkylsulphonyloxy radical preferably has 1 to 4 carbon atoms. 2009 - 13 - Arylsulphonyloxy and alkylsulphonyloxy compounds of the general formula II may be obtained by methods known per se, for example by hydroxymethylating a phenylacetonitrile of the general formula 0 - R, 1 1 R - CH III I CN in which and R have the meanings given under formula I, and reacting the resulting 3-hydroxypropionitrile of the general formula 0 - R, 1 1 R - C - CH0 - OH IV l 2 CN 10 in which and R have the meanings given under formula I, with a suitable sulphonic acid derivative, such as, for example, a sulphonic acid chloride, optionally with the addition of an acid binder. Some of the phenylacetonitriles of the general 15 formula III are known; others may be obtained according to methods known per se (cf., for example, Rubin et a_l. , JACS 67, 192 f (1945); Hess. et , Ber. dt. chem. Ges. 50, 394 (1917)). The hydroxymethyl compounds of the general formula 20 IV have not been described hitherto in the literature. Accordingly, the present invention provides a - 14 - compound of the general formula IV given above and a process for its preparation by the method described above. The 3-halopropionitriles of the general formula II 5 in which Y represents a halogen atom are known in literature and may be obtained by reacting the above-mentioned phenylacetonitriles of the general formula III with dihalomethanes according to methods known per se. 10 The following Examples 1 to 91 illustrate the manufacture of imidazolylpropionitriles according to the invention. Example 92 illustrates the manufacture of an alkylsulphonyloxypropionitrile suitable as starting material. 15 Examples (i) to (iii) illustrate preparations con taining compounds of the invention and Examples A to U illustrate their use. - 15 - EXAMPLE 1 3 - (Irnidazol-l-yl )-2-phenyl-2-propoxypropionitrile# hydronitrate (Compound no. 1) 15 g (0.053 mol) of 3-methylsulphonyloxy-2-phenyl~2-propoxypropionitrile and 17.89 g (0.263 mol) of imidazole are maintained at 140°C for 16 h, during which period 1 ml of dimethylformamide is added and moisture is excluded. The mixture is poured into ice-water, extracted twice with 75 ml of methylene chloride each time, the methylene chloride phase is washed twice with water, dried with magnesium sulphate and concentrated in vacuo after filtering off the drying agent. The remaining dark oil is dissolved in isopropanol and a little more than the theoretical quantity of 100 % nitric acid is added. A little diethyl ether is added to complete the precipitation. The precipitated product is filtered off with suction and dried. Yield: 12 g = 71 % of the theoretical yield M.p.: 168-171°C (decomposition) EXAMPLE 2 3-(Imidazol-l-yl)-2-phenyl-2-propoxypropionitrile (Compound no. 2) 6.2 g (0.0195 mol) of the hydronitrate are dissolved in methanol and rendered basic with dilute ammonia solution 20096 - 1 6 - while cooling with an ice bath. After diluting with water the solution is extracted with ethyl acetate, the organic phase is washed with water and then dried with magnesium sulphate. After filtering, concentration is effected in vacuo. An oil remains which is dried iri vacuo. Yield: 4.85 g = 97 % of the theoretical yield n^1 = 1.5260 Examples 3-91 The following compounds according to the invention can be manufactured in an analogous manner. Name of the compound Physical constant 3C 2-Butcxy-3-(imidazol—1-yl)-2- m.p«:155-157°C(D) phenylpropionitrile, hydronitrate 4. 2-5utoxy-3-(imidazol—1-yl)-2- n^ = 1.5208 phenylpropionitrile 5. 2-Allvloxy-3-(imiaazol-l-yl )-2— m.p. : 162—164°C (D ) phenylpropionitrilet hydronitrate 6. 2-Allylcxy—3-(imidazol—1-yl)-2— nD^ = 1*5402 phenylpropionitrile 7. 2-Ethoxy—3-(imidazol—1—yl)-2- m.p.:182-186°C(D) phenylpropionitrilet hydronitrate 44 8. 2-Ethoxy-3-(imidazol—1-yl)-2- nQ = 1.5247 phenylpropionitrile 9„ 3—(Imidazol-l-yl )—2-mathoxy-2- m.'p. : 189—191°C (D) phenylpropionitrile, hydronitrate 10. 3—(Imidazol-l-yl)-2—methoxy-2- m.p.: 57— 60°C phenylpropionitrile 2 009 6 7 Name of the compound Physical constant 11. 2-(2-Chlorophenyl)-3-(imidazol-l-yl)- 2-propoxypropionitrile, hydronitrate m.p. :162-165°C(D) 12. 2-Butoxy-2-( 4-chlorophenyl)-3-( imidazol- l-yl )-propionitrile , hydronitrate m.p.: 178-181°C(D) 13. 2-Butoxy-2-(2-chlorophenyl)-3-{irnidazol- 1-yl)-propionitrile, hydronitrate m.p.:177-178°C(D) 14. 2-Allyloxy-2-(2-chlorophenyl)-3- (imidazol-l-yl)-propionitrile, hydronitrate m.p. :153-155°C(D) 15. 2-(4-Chlorophenyl)-3-(imidazol-l-yl)-2- propoxypropionitrile, hydronitrate m.p.:174-177°C(D) 16. 2-Allyloxy-2-(4-chlorophenyl)-3- (imidazol-l-yl)-propionitrile, hydronitrate m.p.:152-155°C(D) 17. 2-(2-Chlorophenyl)-3-(imidazol-l-yl)-2-propoxypropionitrile n^ = 1.5343 18. 2-Butoxy-2-(4-chlorophenyl) -3- 41 (imidazol-l-yl)-propionitrile nQ = 1.5288 19. 2-Butoxy-2-(2-chlorophenyl)-3- 4 1 (imidazol-l-yl)-propionitrile n^ = 1.5329 20. 2-Allyloxy-2-(2-chlorophenyl)-3- 4 1 (imidazol-l-yl)-propionitrile nQ = 1.5490 21. 2-(4-chlorophenyl)-3-(imidazol-l-yl)- 4 1 2-propoxypropionitrile - n^ = 1.5337 22. 2-Allyloxy-2-(4-chlorophenyl)-3- 4 1 (imidazol-l-yl)-propionitrile nD = 1.5476 23. 2-Benzyloxy-3-(imidazol-l-yl )-2-phenyl- propionitrile, hydronitrate m.p.:166-168°C(D) Name of the compound Physical constant 24- 2-Benzyloxy-3-(imidazol-l-yl)-2- phenylpropionitrile n^° = 1.5638 25. 3-(Imidazol-l-yl)-2 — isopropoxy-2- phenylpropionitrile, hydronitrate m.p.: 165-168°C(D) 26. 3-(Imidazol-l-yl)-2-isopropoxy-2-phenylpropionitrile n^° : 1.5254 27. 2-(4-Chlorophenyl)-2-hexyloxy-3- (imidazol-l-yl)-propionitrile, hydronitrate m.p.:152-154°C(D) 28. 2-(4-Chlorophenyl)-2-hexyloxy-3- (imidazol-l-yl)-prcpionitrile n^ : 1.5197 29. 2-Allyloxy-3-(imidazol-l-yl)-2-(2-methvlphenyl)-propionitrile, hydronitrate m.p.: 160°C (D) 30. 2-(3,4-Dichlorophenyl)-3-(imidazol-l-yl )-2-propoxypropionitrile, hydronitrate m.p.: 169-170°C (D) 31. 2-Butoxy-2-(2,4-dichlorophenyl)-3-(imidazol-l-yl)-propionitrile, hydronitrate m.p.: 148-50°C (D) 32. 2-Allyloxy-2-(2,4-dichlorophenyl)-3-(imidazol-1-yl)-propionitrile, hydronitrate m.p.: 158-60°C (D) 33. 2-Ethoxy-2-(3,4-dichlorophenyl)-3-(imidazol-l-yl)-propionitrile, hydronitrate m.p. : 105-06°C (D) Name of the Compound Physical constant 34. 2-Allyloxy-3-(imidazol-1-yl)-2- (2-methylphenyl)-propionitrile n^° : 1.5388 D 35. 2-(3,4-Dichlorophenyl)-3-(imidazol-1- .40 36. 2-Allyloxy-2-(3,4-dichlorophenvl)-3- yl)-2-propoxypropionitrile n^ : 1.5360 ,.40 37. 2-Butoxy-2-(2,4-dichlorophenyl)- 3- (imidazol-l-yl)-propionitrile nQ : 1.5500 (imidazol-l-yl)-propionitrile n^ : 1.5381 38. 2-Allyloxy-2-(2,4-dichlorophenyl)-3- (imidazol-l-yl)-propionitrile n^® : 1.5531 39. 2-Ethoxy-2-(3,4-dichlorophenyl)-3- (imidazol-l-yl)-propionitrile n^ : 1.5372 40. 3-(Imidazol-l-yl)-2-phenyl-2-(1,2,2-trimethylpropoxy)-propionitrile , hydronitrate m.p.: 168-173°C (D) 41. 3-(Imidazol-1-yl)-2-(2-methoxy-ethoxy)-2-phenylpropionitrile, hydronitrate m.p.: 158-160°C (D) 42. 2-(2,2-Dimethylpropoxy)-3- (imidazol-l-yl)-2-phenylpropionitrile, hydronitrate m.p.: 168-171°C (D) 4 3. 2-(2,2-Dimethylpropoxy)-3- (imidazol-l-yl)-2-phenylpropionitriie m.p.: 89- 91°C 44. 2-(2-Fluorophenyl)-3-(imidazol-l- yl )-2-prop"oxypropionitrile, hydronitrate m.p.: 170-172°C (D) 200967 Name of the compound Physical constant 45. 2-Butoxy-2-(2-fluorophenyl)-3-(imidazol-l-yl)-propionitrile, hydronitrate m.p.: 173-176°C (D) 4 6. 2-(4-Fluorophenyl)-3-(imidazol-l-yl) - 2-propoxypropionitrile, hydronitrate m.p.: 150-152°C (D) 47. 2-Butoxy-2-(4-fluorophenyl)-3-(imidazol-l-yl)-propionitrile, hydronitrate m.p.: 162-165°C (D) 48. 2-Allyloxy-2-(2-fluorophenyl)-3-(imidazol-l-yl)-propionitrile, hydronitrate m.p.: 169-171°C (D) 49. 2-Ethoxy-2-(2-fluorophenyl)-3-(imidazol-l-yl)-propionitrile, hydronitrate m.p.: 172-175°C (Z) 50. 2-(2-Fluoropheny1)-3-(imidazol-l-yl)- 2-methoxypropionitrile, hydronitrate m.p.: 177-179°C (D) 51. 3-(Imidazol-l-yl)-2-phenyl-2-(1,2,2- trimethylpropoxy)-propionitrile m.p.: 113-116°C 52. 3-(Imidazol-1-yl)-2-(2-methoxy- ethoxy)-2-phenylpropionitrile n^ : 1.5212 53. 2-(2-Fluorophenyl)-3-(imidazol-l-yl)- '•D 40 2-propoxypropionitrile > n : 1.5143 54. 2-Butoxy-2-(2-fluorophenyl)-3- ... 40 (imidazol-l-yl)-propionitrile nD : 1.5108 55. 2-(4-Fluorophenyl)-3-(imidazol-1- ... 40 yl)-2-propoxypropionitrile n^ : 1.5115 - 21 - 2 009 6 7 Name of the compound Physical constant 56. 2-Butoxy-2-(4-fluorophenyl)-3- (imidazol-l-yl)-propionitrile n^° : 1.5085 57. 2-(2-Fluorophenyl)-3-(imidazol-l- yl )-2-methoxypropionitrile n£° : 1.5280 58. 2-Ethoxy-2-(2-fluorophenyl)-3- (imidazol-l-yl)-propionitrile n40 : 1.5187 D 59. 2-Allyloxy-2-(2-fluorophenyl)-3- (imidazol-l-yl)-propionitrile n^° : 1.5258 60. 2-Allyloxy-2-(4-fluorophenyl)-3-(imidazol-l-yl)-propionitrile, hydronitrate m.p.: 159-161°C (D) 61. 2-Ethoxy-2-(4-fluorophenyl)-3-(imidazol-l-yl)-propionitrile, hydronitrate m.p.: 182-184°C (D) 62. 2-(4-Fluorophenyl)-3-(imidazol-l-yl )-2-methoxypropionitrile, hydronitrate m.p.: 194-196°C (D) 63. 2-Ethoxy-2-(4-fluorophenyl)-3- (imidazol-l-yl)-propionitrile m.p.: 54- 57°C 64. 2-(4-Fluorophenyl)-3-(imidazol-1- yl)-2-methoxypropionitrile m.p.: 88°C 65. 2-Allyloxy-2-(4-fluorophenyl)-3- (imidazol-l-yl)-propionitrile n^° : 1.5219 66. 2-Decyloxy-3-(imidazol-l-yl) - 2- phenylpropionitrile, hydronitrate m.p.: 126-128°C (D) - 2? - Name of the compound Physical constant 67. 2-(3,3-Dimethylbutoxy)-3- (imidazol-l-yl)-2-phenylpropio- nitrile, hydronitrate m.p.: 195-198°C (D) 68. 3-(Imidazol-l-yl)-2-octyloxy-2- phenylpropionitrile n^° : 1.5055 69. 2-(3,3-Dimethoxybutoxy)-3- (imidazol-l-yl)-2-phenylpropionitrile n^° : 1.5093 70. 2-(4-Bromophenyl)-2-butoxy-3- ( imidazol-l-yD-propionitrile, hydronitrate m.p.: 171-174°C (D) 71. 2-( 4-Bromophenyl)-3-(imidazol-l-yl)- 2-propoxypropionitrile, hydronitrate m.p.: 162-165°C (D) 72. 2-(4-Bromophenyl)-2-hexyloxy-3- (imidazol-l-yl)-propionitrile, hydronitrate m.p.: 135-138°C (D) 73. 3-(Imidazol-l-yl)-2-(2-methyl-phenyl)-2-propoxypropionitrile, hydronitrate m.p.: 180-183°C (D) 74. 2-Hexyloxy-3-(imidazol-l-yl)-2-(2-methylphenyl)-propionitrile, hydronitrate m.p.: 170-173°C (D) 7 5. 2-(4-Bromophenyl)-2-butoxy-3- 40 (imidazol-l-yl)-propionitrile nQ : 1.5405 76. 2-(4-Bromophenyl)-3-(imidazol-l-yl)- 40 2-propoxypropionitrile nQ : 1.5418 77. 2-(4-Bromophenyl)-2-hexyloxy-3- 40 (imidazol-l-yD-propionitrile n : 1.5274 - 23 - J O (H) Q) (£ Name of the compound Physical constant 78. 2-Butoxy-3-(imidazol-l-yl)-2- (2-methylphenyl)-propionitrile : 1.5248 79. 2-Butoxy-3-(imidazol-l-yl)-2-( 2-rnethylphenyl)-propionitrile, hydronitrate m.p.: 184-186°C 80. 2-Hexyloxy-3-(imidazol-l-yl)-2- ( 2-rnethylphenyl)-propionitrile n^ : 1.5163 81. 2-Decyloxy-3-(imidazol-l-yl)-2- £0 phenylpropionitrile nQ : 1.5020 82. 3-(Imidazol-l-yl')-2-( 2-methylphenyl)-2-propoxypropionitrile n^° : 1.5276 83. 2-Butoxy-2-(3-chlorophenyl)-3- (imidazol-l-yl)-propionitrile n^° : 1.5282 84. 2-(3-Chlorophenyl)-2-hexyloxy-3-(imidazol-l-yl)-propionitrile, hydronitrate m.p.: 162-165°C (D) 85. 2-Decyloxy-3-(imidazol-l-yl)-2-(2-methylphenyl)-propionitrile, hydronitrate m.p.: 151-155°C (D) 86. 3-(Imidazol-l-yl)-2-(2-methyl- 40 phenyl)-2-octyloxypropionitrile, n^ : 1.5173 87. 2-Decyloxy-3-(imidazol-l-yl)-2- (2-methylphenyl)-propionitrile n^° : 1.5139 88. 2-Butoxy-3-(imidazol-l-yl)-2-( 4-methoxyphenyl)-propionitrile, hydronitrate m.p.: 163-167°C (D) - 24 - 200967 Name of the compound Physical constant 89. 2-Butcxy-3-(imidazol-l-yl)-2-(4-methoxyphenyl)-propionitrile 90. 2-(4-Chlorophenyl)-2-hexyloxy-3-(imidazol-l-yl)-propionitrile, hydrogen oxalate 91. 2-(4-Chlorophenyl)-2-hexyloxy-3-(imidazol-l-yl)-propionitrile, bisulohate m.p. : 195-197°C (D) m.p.: 158-163°C (D) (D = decomposition) In the following, the manufacture of a starting material is described. Example 9 2 3-methyl sulphonyl-2-phenyl - 2-propox\fr)ropioni tr i le 27 g (0.154 mol) of 2-phenyl-2-propoxyacetcnitrile are dissolved in 120 ml of pyridine, and 18.5 g (0.614 mol) of paraformaldehyde are added. 7.7 ml of tetra-butylammonium hydroxide (TBA0H) are added to this suspension while cooling with ice and the mixture is stirred 200967 vigorously for 17 hours. The reaction mixture is poured into ice-water and extracted twice with ether. The ether phase is then washed twice with aqueous sodium chloride solution and dried with magnesium sulphate. After filtering off the drying agent and concentrating by rotation in vacuo, a colourless oil remains which proves to be uniform according to thin layer chromatography and can be further processed without further purification. Yield: 28.4 g = 90 % of the theoretical yield 3-hydroxy-2-phenyl-2-propoxypropionitrile 28 g (0.136 mol) of 3-hydroxy-2-phenyl-2-propoxypropionitrile are dissolved in 200 nil of toluene, and 19.5 g (0.171 mol) of methanesulphcnic acid chloride are added. 18.6 g (0.184 mol) of triethylamine are added dropwise at 10°C. The mixture is then stirred for 30 minutes at room temperature, the precipitated triethylamine hydrochloride is filtered off and the filtrate is concentrated. The residue is taken up in ether, washed with dilute HCl solution, water and sodium bicarbonate solution and twice more with water. The residue is dried with magnesium sulphate, the drying agent is filtered off with suction and concentration is carried out. The oily residue is dried _in vacuo. According to thin layer chromatography, it is pure. Yield: 32.27 g = 86 % of the theoretical yield nD = 1. 5000 3-methylsulphonyl-2-phenyl-2-propoxypropionitrile IJ Sv - _ 26 - ™ w O ^ 7 Examples of preparations Example (i) Wettable powder a) 40 % by weight active substance 5 25 % by weight clay minerals 20 % by weight silicic acid 10 % by weight cellulose pitch 5 % by weight surface-active substances based on a mixture of the calcium salt of 10 ligninsulphonic acid with alkylphenol polyglycol ethers b) 25 % by weight active substance 60 % by weight kaolin 10 % by weight silicic acid 15 5 % by weight surface-active substances based on the sodium salt of N-methyl-N-oleyl-taurine and the calcium salt of ligninsulphonic acid. c) 10 % by weight active substance 20 60 % by weight clay minerals 15 % by weight silicic acid 10 % by weight cellulose pitch -5 % by weight surface-active substances based on the sodium salt of N-methyl-N-oleyl-25 taurine and the calcium salt of ligninsulphonic acid. - 27 - % 009 67 Example (ii) Paste 45 % by weight active substance 5 % by weight sodium aluminium silicate 5 15 % by weight cetyl polyglycol ether with 8 moles of ethylene oxide 2 % by weight spindle oil 10 % by weight polyethylene glycol 23 parts water 10 Example (iii) Emulsion concentrate 25 % by weight active substance 15 0/ /o by weight cyclohexanone 55 % by weight xylene 15 5 e/ /o by weight mixture of nonylphenylpolyoxyethylene or calcium dodecylbenzenesulphonate. % 009 6 The following Examples illustrate possible uses of the compounds according to the invention which were used in the form of the above-mentioned preparations. EXAMPLE A Effect of seed treatment against Helminthosporium spec, in barley. Barley seeds infected naturally with Helminthosporium oramineum were sown either untreated or treated as indicated in the Table in soil-filled plant containers and left to germinate at temperatures below +16°C. After emergence, the seedlings were illuminated with artificial light for 12 hours daily. After approximately 5 weeks, all the plants that had emerged and the plants attacked by fungi were counted per test unit. The fungicidal action was calculated as follows: 100 x attack in treated group 100 - = % action attack in untreated group The compounds were in the form of 20 % wettable powders. - ?9 - Compound according to g active substance the invention no. loo kg seeds % action 1 50 95.6 2 50 100 3 50 100 4 50 100 5 50 loo 6 50 ioo 7 50 100 8 50 100 9 50 100 10 50 100 11 50 IOO 12 50 100 13 50 100 14 50 100 15 50 100 16 50 loo 17 50 100 18 50 loo 19 50 100 20 50 100 21 50 100 Comparison aaent methoxyethyl mercury silicate 2.63 87 200967 EXAMPLE B Effect of prophylactic leaf treatment against Erysiphe cichoracearum in pumpkin plants in a greenhouse. Young pumpkin plants sprayed until dripping wet with the indicated active substance concentrations were inoculated, after the spray coating had dried on, by dusting with dry mildew spores of Erysiphe cichoracearum and incubated in a greenhouse at 24°C together with inoculated untreated control plants. After one week, the surface area of the leaves attacked by mildew was estimated as a percentage of the total surface area of the leaf. The fungicidal action was calculated as follows: 100 x attack in treated plants 100 - = '% action attack in untreated plants The substances were in the form of 20 % wettable powders. Compound according to active substance the invention no. concentration as % action -5 ©/ a /o 1 0.025 100 0.005 100 0.001 100 2 0.025 100 0.005 100 0.OOl 100 3 0.025 100 0.005 100 O.OOl 100 200967 Compound according to active substance the invention no. concentration as a % % action 4 0. 025 100 0.005 loo O.OOl 100 5 0.025 100 0.005 lOO O.OOl 100 6 0.025 100 0. 005 100 O.OOl lOO 7 0.025 100 0.005 100 O.OOl 100 8 O. 025 100 0.005 100 O.OOl 100 9 O. 025 100 O. 005 100 O.OOl 100 10 0.025 100 0. 005 100 0. 001 100 11 0.025 100 O. 005 100 O.OOl 100 12 O. 025 loo 0.005 100 O.OOl loo 13 0.025 100 0.005 100 O.OOl loo 14 O. 025 loo O.005 - • 100 O.OOl -87 15 0.025 100 0.005 loo « O.OOl loo 16 0.025 loo 0.005 100 O.OOl 100 2 009 6/ Compound according to active substance the invention no. concentration as a % % action 17 0.025 lOO 0.005 lOO O.OOl 100 18 0.025 100 O. 005 100 0. OOl 100 19 0.025 100 0. 005 lOO 0. OOl loo 20 O. 025 100 0. 005 loo O. 001 100 21 0.025 100 O. 005 100 0. OOl • 100 22 O.OOl 100 0. 0002 100 23 0.001 100 0.0002 100 24 O.OOl 100 O.0002 100 25 0. 001 100 O. 0002 100 26 O. 001 100 O.0002 100 27 0. 001 100 0.0002 100 28 O. 001 100 O.0002 100 29 0.001 . 100 \ 0.0002 100 30 O. 001 100 0.0002 loo 31 O.OOl O.0002 100 100 Compound according to active substance the invention no. concentration as a % % action 32 O.OOl 100 0.0002 100 33 O.OOl 100 0.0002 100 34 O.OOl 100 O.0002 100 35 O.OOl 100 0.0002 lOO 36 O.OOl 100 O.0002 98 37 O.OOl 100 O.0002 lOO 38 O.OOl 100 O.0002 100 39 O. OOl 100 0.0002 100 4-0 O.OOl 100 O.0002 100 41 O.OOl 100 O.0002 100 42 0.001 100 0.0002 - lOO 43 0.001 100 0.0002 100 44 O.OOl 100 O.0002 100 45 0.001 100 O.0002 • 100 46 O.OOl 100 0.0002 100 47 O.OOl 100 0.0002 100 48 " O.OOl 100 O.0002 100 J00?67 Compound according to active substance the invention no. concentration as a % % action 49 O.OOl 100 0.0002 • 100 50 O.OOl 100 O.0002 100 51 0. OOl 100 0. 0002 100 52 O.OOl 100 0.0002 100 53 O. 001 100 0.0002 100 54 O. OOl 100 0.0002 100 55 0. 001 100 O.0002 100 56 O. 001 100 0.0002 100 57 O. 001 100 0.0002 100 58 O.OOl 100 O.0002 100 59 O.OOl 100 0.0002 100 60 O. OOl 100 0.0002 100 61 O.OOl 100 0.0002 100 62 0.001 100 0.0002 100 63 0. 001 loo O.0002 100 64 O.OOl 100 - O.0002 100 65 0.001 O.0002 100 100 - 35 - 2 009 67 Compound according to active substance the invention no. concentration as a % % action 66 0.0025 100 0.00025 lOO 67 0.0025 100 O.00025 100 68 0.0025 lOO O.00025 lOO 69 0.0025 lOO O.00025 100 70 0.0025 lOO 0.00025 lOO 71 O.0025 100 O.00025 100 72 0.0025 100 O.00025 100 73 0.0025 lOO 0.00025 100 74 0.0025 lOO O.00025 lOO 75 0.0025 100 0.00025 100 76 0.0025 100 0.00025 100 77 0.0005 99 0.00005 100 78 O.0005 100 O.00005 100 EXAMPLE C Effect of leaf treatment against Piricularia oryzae in rice seedlings in a greenhouse. Young rice plants were sprayed until dripping wet - 36 - ,-=Ss i i 10 with the active substance concentrations indicated in the Table. After the spray coating had dried on, the treated plants and the untreated control plants were inoculated by being sprayed with a suspension of spores (approximately 200,000 per ml) of the causative organism of leaf spot, Piricularia oryzae, and incubated in the moist state at from +25 to +27°C in a greenhouse. After 5 days, the percentage of the surface area of the leavesthat had been attacked was ascertained. From these attack figures, the fungicidal action was calculated as follows: 100 x attack in treated plants lOO - : = % action attack in untreated plants The substances were in the form of 20 % wettable powders. 15 Compound according to the invention no. active substance concentration as a % % action 20 25 1 2 4 5- 11 12 0.1 0.02 0. 1 0. 02 O. 1 0.02 0. 1 0. 02 0.1 0. 02 0.1 0.02 89 63 97.3 89 9A.5 70 95 77.5 95 80 95 65 200967 Compound according active substance to the invention no. concentration as a % % action 13 O. 1 92.5 0.02 70 14 O. 1 95 0.C2 80 15 O. 1 98 0.02 65 16 0.1 95 O. 02 55 17 0.1 97.5 O. 02 90 18 O. 1 95 O. 02 80 19 O.l 92.5 O. 02 65 20 O. 1 95 0.02 85 21 O. 1 95 0.02 80 EXAMPLE D Effect of prophylactic leaf treatment against Botrytis cinerea in tomato plants in a greenhouse. Young tomato plants were sprayed until dripping wet with the active substance concentrations indicated in the Table. After the spray coating had dried on, the treated plants and the untreated plants were inoculated by being sprayed with a suspension of spores (approximately 1 million per ml fruit juice solution) of the causative organism of grey mould, Botrvtis cinerea. and - 38 - *©0967 incubated in the moist state at approximately 20°C in a greenhouse. After the untreated plants had collapsed (= lOO % attack), the degree of attack in the treated plants was ascertained. The fungicidal action was calculated as follows: lOO x attack in treated plants 100 - = % action attack in untreated plants The compounds according to the invention were in the form of 20 % formulations. Compound according active substance to the invention no. concentration as a % % action 2 0.025 95 3 O. 025 80 12 0. 025 90 13 0.025 95 14 O. 025 60 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 80 Comparison test 1-(4-chlorophenoxy)-3,3-dimethyl-l-(1,2,4~tria— zol-l-yl)-butan-2-one 0.025 60 EXAMPLE'E Effect of prophylactic leaf treatment against Plasmooara viticola in vines in a greenhouse. Young vines having approximately 5 to 8 leaves were sprayed until dripping wet with the indicated concentration and, after the spray coating had dried on, the undersides of their leaves and of leaves of control plants were sprayed with an aqueous suspension of sporangia of the above fungus (approximately 20,000 per ml) and the plants were immediately incubated in a greenhouse at from 22 to 24°C in an ato'msphere that was as saturated as possible with steam. After the second day, the air humidity was reduced to the normal level for from 3 to L days (30 to 70 % saturation) and then maintained at steam saturation for one day. The percentage surface area attacked by the fungus was then noted for each leaf and the average per treatment was then calculated as follows to ascertain the fungicidal action: 100 x attack in treated plants lOO - = % action attack in untreated plants The substances were in the form of 20 % wettable powders. Compound according to the invention no. - 40 - 20096 active substance concentration as a % % action 10 11 O. 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 O. 025 95.5 20 0.025 65 21 0.025 81 EXAMPLE F In a laboratory, cress seeds were treated with an aqueous emulsion of the agents according to the invention. The concentration of the active substances in the emulsion was lOO ppm. For this purpose, a slide was placed in a 200 ml glass vessel containing 10 ml of 2o active substance emulsion. Filter paper was drawn onto the slide. When the filter paper was thoroughly soaked with the emulsion, 10 cress seeds were evenly distributed over it. The lid of a petri dish was then placed on the vessel. Two glass vessels were used for each substance 25 For the evaluation, the length of the shoots and roots of the germinated seeds was measured after -41 - 15 20 25 200961 7 days. In the Table, the values are given in relation to a control and expressed as percentages. It is apparent that the compcunds according to 5 the invention exert a strong influence on the growth of roots and shoots in cress. This is clearly shown by the results. Promotion would be indicated by a result of 100 % and inhibition by <C100 %. Compound according Growth as a % of normal growth lO to the invention no. shoot 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 42 - 2009B? Compound according Growth as a % of normal growth to the invention no. shoot root 17 83 56 18 67 67 19 100 56 20 83 78 21 50 44 22 50 57 EXAMPLE G 10 Cotton was grown under greenhouse conditions until the cotyledon stage was reached. The compounds according to the invention and a comparison agent were sprayed onto the plants in application quantities of 1 and 2 kg active substance/ha. 15 3 weeks after application, the total length of the plants and the length of the first internode were measured. In the Table, the results are given as percentages in comparison with a control. There is a reduction in growth which, in most I 20 cases, is greater than in the case of the comparison preparation. - A *J 009 67 Compound according to the invention no. kg active substance/ha :otal length :f the plants is a % of lormal length length of the 1st internode as a % of normal length 10 15 20 25 11 12 13 14 15 16 17 18 19 20 21 22 1 2 1 2 1 2 1 2 1 2 1 2 1 2 1 2 1 2 1 2 1 2 1 2 Comparison aoent 30 2-chloroethyltrimethyl- 1 ammonium chloride 2 75 46 83 59 69 37 82 65 83 60 87 69 60 41 69 52 48 45 75 52 95 71 100 55 52 44 32 9 60 19 34 4 57 42 66 42 66 42 32 9 15 13 15 9 43 9 72 34 70 62 23 23 - 44 - 200967 EXAMPLE H _ Effect of seed treatment against the cereal mildew Erysiphe oraminis in barley. Seeds of summer barley were sewn untreated or dressed with lOO g of active substance/100 kg in soil-filled plant containers and left to germinate at temperatures of approximately 20°C in a greenhouse- After the formation of the first foliage leaf, the plants were inoculated by brushing them with plants attacked by mildew. One week later, a note was made of the percentage of the surface area of the leaves covered in mildew. The fungicidal action was calculated as follows : lOO x attack in treated group lOO - —— — = % action attack in untreated group Any incompatibility of the treatment with the barley was assessed after the plants had emerged. The assessment was according to the scheme: 0 = total destruction 1 = 90 % destruction 2 = 80 % destruction 3 = 70 % destruction 4 = 60 % destruction 5 = 50 % destruction 6 = 40 % destruction 7 = 30 % destruction 8 = 20 % destruction - 45 - :• "\ f\ , v< y 9 = 10 % destruction 10 = undamaged. The compounds according to the invention were in the form of wettable powders with a 20 % active substance content. In contrast to the comparison agent used, the compound according to the invention proved to be not only completely effective against Erysiphe craminis but also completely compatible with the barley. 10 Compound according to the invention no. % action 1 100 2 lOO 5 lOO 15 6 100 7 100 8 100 9 99.5 10 lOO 20 11 93 15 100 16 99 17 95 21 100 25 22 100 Comparison agent 1-(4-chlorophenoxy)-3,3-dimethyl-l-(1,2,4-triazol-l-yl)-butan-2-one 100 compatibility lO lO 10 10 10 10 lO lo lo io lo lo lo io 46 - 7.00967 EXAMPLE I Effect of prophylactic leaf treatment against the leaf spot disease (Cercospora beticola) in sugarbeet (Beta vulgaris). 5 Sugarbeet plants having 4 well developed foliage leaves were sprayed until dripping wet with the indicated concentrations, After the spray coating had dried on, the treated plants and . untreated control plants were evenly sprayed with a suspension of 15,000 Cercospora 10 spores per millilitre. The plants were incubated for four days in a greenhouse at 26°C in steam-saturated air and then maintained at approxirr.ately 22°C for a further 10 days in the greenhouse. The proportion of the surface area of the leaves attacked was then noted. 15 From this, the action of the fungicides was calculated as follows: lOO x attack in treated plants 100 - = % action attack in untreated plants Compound according active substance 20 to the invention no. concentration as a % % action 1 0.05 100 0.01 100 2 0.05 100 0.01 100 25 4 0.05 100 0.01 99 5 0.05 100 0.01 96 - 47 - 7.0096 7 Compound according active substance to the invention no. concentration as a % % action 11 0.05 lOO O.Ol 100 5 12 0.05 lOO O.Ol 99.6 13 0.05 lOO O.Ol 93 14 0.05 lOO 10 O.Ol 99.6 15 0.05 100 0.01 98 17 0.05 100 0.01 99 15 18 O.05 100 O.Ol 99.6 19 O.05 100 0.01 99.3 20 0.05 100 20 O.Ol 98 21 0.05 100 0.01 99.6 Comparison agent manqanese ethylene bis- 0.05 100 25 J 0.01 79 dithiocarbamate EXAMPLE J' Inhibition of fungal growth on a nutrient solution. 20 ml of a nutrient solution consisting of grape juice and water (1:1) were poured into 100 ml glass 30 flasks the pulverulent active substance preparations were added. Inoculation of the treated nutrient solutions and of an untreated nutrient solution was then carried out with conidia (spores) of PeniciIlium cicitatum. After an - 48 - ? 7 «w"f/ ** 10 incubation period of 5 days at from 22 to 24°C, the development of the fungus on the surface of the nutrient solution was assessed. Evaluation: 0 = no fungal growth 1 = individual fungal colonies on the surface 2 = 5-10 % of the surface covered in fungus 3 = 10-30 % of the surface covered in fungus 4 = 30-60 % of the surface covered in fungus 5 = 60-100 % of the surface covered in fungus. Active substances, active substance concentrations in the nutrient solution, and results are given in the following Table. 15 Compound according to the invention no. active substance concentration in the nutrient solution as a % fungal development 5 0.0005 c/i 4 0.001 % 0 6 0.0005 % 4 O.OOl % 1 20 17 0.0005 % 0 O.OOl % 0 20 0.0005 % 0 0.001 % 0 21 0.0005 % 2 25 0.001 % 0 23 0.0005 % 0 O.OOl % 0 24 0.0005 % 1 • 0.001 % 0 30 27 0.0005 % 0 0.001 % 0 & . ^ »l * \ • \ . * \ 4 9 - \jj y) Compound according active substance concen- fungal to the invention no. tration in the nutrient cevelop- solution 'as a % reent 28 0.0005 % 0 5 0.001 % 0 29 0.0005 % 0 O.OOl % 0 31 0.0005 % 0 O.OOl % 0 10 32 0.0005 % 0 O.OOl % O 34 0.0005 % O O.OOl % O 37 0.0005 % O 15 O.OOl % 0 N 33 0.0005 % O O.OOl % O Comparison aoent (according to DE-CS 26 04 0^7) 3-(imidazol-l-yl)-2-phenyl-20 2-butvlpropionitrile hydronitrate ' 0.0005 % 5 0.001 % 4 untreated nutrient solution control - 5 25 EXAMPLE K Effect of prophylactic leaf treatros."z against: the true vine mildew Uncinula nacator. Young vines of the Silvaner type having approximately 8 to 10 leaves were sprayed until dripping wet 30 with the concentrations indicated in the Table. ■ After the spray coatings had dried on, the plants together with untreated control plants were ousted in the dry state with conidiospores of the fungus : 15 20 25 - 50 - 100967 Uncinula necator and incubated in a greenhouse for 12 days at approximately 22°C. The proportion of the surface area cfthe leaves attacked by mildew was then estimated as a percentage and the fungicidal action 5 was calculated as follows: attack in treated plants x lOO lOO - = % action attack in untreated plants The degree of attack in the untreated plants was 88.3 %. The agents were in the form of 20 % wettable powders. IO The action is shown in the Table. Compound according to % action against Uncinula necator with the invention no. 0.025 0.005 % active substance 2 93 85 3 lOO 100 4 lOO 100 5 100 100 6 lOO 99 7 100 89 8 lOO 95 9 87 63 10 100 49 11 lOO lOO 12 100 63 13 lOO 95 14 66 43 15 lOO 100 - 51 - ->00967 Compound according % action against Uncinula necator with to the invention no. 0.025 0.005 % active substance 16 99 89 17 lOO 100 18 86 80 19 100 89 20 93 86 21 100 100 22 100 92 10 EXAMPLE L Effect of prophylactic leaf treatment against apple scab, Venturia inaeaualis sin the open air. Growing shoots of apple plants of the MM 106 type were treated until dripping wet with O.l % active substance 15 concentration. After the spray coalings had dried on, a suspension of conidiospores (330,000 per millilitre) was sprayed onto the leaves and, after polythene bags, had been slipped over the shoots, the plants were left for three days in half-shadow to be infected by the fungus. 20 The bags were then removed. After the experiment had lasted 2h weeks, the proportion of the surface area attacked by scab was estimated as a percentage. An untreated control showed a 99 % attack. The success of the treatments was calculated as follows: 25 attack in treated plants x 100 lOO - ; = % action attack in untreated plants t - 52 - The compounds were in the form of 20 % wettable powders. Compound according % action to the invention no. 18 100 5 19 85 EXAMPLE M Effect of curative leaf treatment against apple scab, Venturia inaequalis, in the open air. Growing shoots of apple plants of the MM 106 type 10 were sprayed with a suspension of conidiospores (330,000 per millilitre) and immediately maintained in the moist state by slipping polythene bags over them. The plants stood in half-shadow. After 3 days, the bags were removed. Seven days after inoculation, seme plants were treated until 15 dripping wet with 0.1 % active substance concentration. After a further 1% weeks, the proportion of the surface area of the leaf attached by apple scab was estimated as a percentage; in the untreated plants it was 99 %. The compounds according to the invention were in the 20 form of 20 % wettable powders. The effect of the treatment was calculated as follows: attack in treated plants x 100 100 - = % action attack in untreated plants * • 10 • 15 - 53 7 Compound according to the invention no. % action 2 93 18 100 19 100 Comparison aaent 2-butyl-3-( irnidazol-l-yl)-2- 90 phenylpropionitrile, hydronitrate EXAMPLE N Prophylactic leaf treatment against Erysiphe craminis in barley. Barley plants at the stage of having their first leaf were sprayed until dripping wet with the indicated active substance concentration with the addition of an alkaryl polyglycol ether as wetting agent (0.05 %). After the spray coating had dried on, these plants and untreated control plants were evenly brushed with cereal plants attacked by mildew and then incubated in a greenhouse at from 20 to 22°C for a week. The average mildew attack per plant container (18 to 20 plants) was then noted. The fungicidal action was calculated according to the formula 100 x attack in treated plants 100 - = % action attack in untreated plants The substances according to the invention were in the form of 20 % formulations. - 54 - " 0 9 <g> J Compound according % action with % action with 0.025 % O.005 % to the invention no. active substance active substance 3 100 100 4 100 lOO 5 100 100 6 100 100 7 100 lOO 8 100 lOO 9 lOO 92 10 92 90 11 lOO lOO 12 100 lOO 13 100 100 14 lOO lOO 15 100 lOO '16 lOO lOO 17 100 100 18 100 lOO 19 100 100 20 100 100 21 100 100 22 100 100 EXAMPLE O Effect of prophylactic leaf treatment against Uromyce appendiculatus (bean rust) in a greenhouse French bean plants at the stage of having half- 2009 developed primary leaves were sprayed until dripping wet with lOO pprn active substance concentration. After the spray coatings had dried on, the treated plants and untreated control plants were sprayed with a suspension of the uredospores of Uromyces appendiculatus. The plants were then incubated for two days in a moist charrbe at 22°C and subsequently maintained at approximately 22°C under greenhouse conditions. 11 days after spraying the spores, the rust pustules were counted (an average of 253 per leaf in the untreated control plants). The fungicidal action was calculated as follows: pustules in treated plants x 100 lOO - = % act pustules in untreated plants The substances according to the invention were in the form of 20 % formulations and exhibited over 90 % acticn. Compound according to the invention no. % action 1 91 2 96 3 95 4 94 12 100 15 99.5 16 95 17 99.4 18 . 99.9 « - 56 - 20096 Compound according to the invention no. % action 19 98 21 98.6 5 22 95 27 95 28 97 EXAMPLE P Effect of prophylactic leaf treatment against Kelmintho-lO sporium teres (= Pyrenophora teres), net blotch, in barley. Young barley plants at the stage of having their first leaf were sprayed until dripping wet with the indicated concentrations. After the spray coatings had dried on, the treated plants and untreated control 15 plants were sprayed with a suspension of the conidiospores of Helminthosporium teres and cultivated in a moist chamber for 2 days at from 20 to 22°C. One week after inoculation, the percentage of the surface area of the leaves that had been attacked was noted. The fungicidal 20 action was calculated as follows: lOO _ attack in treated Dlanfcs x IOO = attack in untreated plants The compounds were in the form of 20 % formulations. Compound according to the invention no. % action 500 ppm 100 ppm 35 36 37 38 39 40 41 42 43 44 46 47 48 49 50 51 52 53 54 55 57 58 59 90 90 90 90 95 100 98 100 100 lOO 100 100 89 100 96 100 89 100 96 lOO 100 96 89 90 95 95 95 95 100 100 100 100 100 100 100 100 100 100 lOO 98 100 9c IOC 103 lOO 100 - 58 - 20096 EXAMPLE Q Effect of prophylactic leaf treatment against brown rust, Puccinia horde_i,in barley in a climatised plant-growing chamber. 5 Young barley plants at the stage of having their first leaf were sprayed until dripping wet with the indicated concentration. After the spray coatings had dried on, the treated plants and untreated control plants were inoculated by brushing them with plants attacked 10 by brown rust and then placed in a plant-growing chamber. The plants were cultivated for 10 days at 15°C, cultivation for the first two days being in air practically saturated with moisture. The percentage proportion of the surface area of the leaves attacked by rust was then noted. The 15 fungicidal action was calculated as follows: attack in treated plants x 100 100 - = % action attack in untreated plants The compounds were in the form of 20 % formulations. The Table indicates good to very good action for numerous 20 compounds according to the invention. Compound according to the invention no. % action 5oo ppm 32 100 42 100 25 43 100 45 lOO - 59 - ?H09 67 Compound according to the invention no. % action 46 100 47 100 48 lOO 49 lOO 54 lOO 55 lOO 58 lOO 61 lOO 64 lOO 65 100 66 lOO 67 lOO 69 100 71 lOO 7 2 lOO 74 100 75 lOO 76 lOO 7 7 lOO 78 100 79 100 80 1O0 EXAMPLE R Effect of prophylactic leaf treatment against yellow rust Puccinia striiformis in barley in a climatised plant- growing chamber. 5 Young barley plants at the stage of having their first leaf were sprayed until dripping wet with the indicated concentrations. After the spray coatings had dried on, the treated plants and untreated control plants were sprayed with a suspension of the uredospores of 10 Puccinia striiformis in 1,1,2-trifluoro-1,2,2-tricnloro- ethane and incubated at 150°C in a plant-growing chamber. For the first two days, it was ensured that the air was almost completely saturated with moisture. After 15 days, the percentage proportion of the surface area 15 of the leaves attacked by rust was noted. The fungicidal action was calculated as follows: attack in treated plants x 100 100 - = % action attack in untreated plants Compound according to % action with 20 the invention no. 100 33 11 ppm 5 100 — - 12 100 100 100 14 loo - - 15 loo 100 100 16 100 - - 17 100 100 100 18 100 100 93 28 100 98 78 - 61 - ©09 5,7 EXAMPLE S Effect of seed treatment against Helminthosporium sativum in barley in a climatised plant-grcwing chamber. Barley seeds infected artificially with Helminthospor ium sativum were dusted with 50 g of active substance according to the invention and of comparison agent per 100 kg. For each test unit, 2 g of treated seeds and 2 g of untreated seeds were sowti in plastics pots measuring 6.5 x 6.5 cm. Sand was used as the substrate. The experiment was repeated twice for each unit. The pots were placed in a plant-growing chamber at 15°C. After 4 weeks, the plants that had emerged were examined for percentage attack of the base of the stem. Tne fungicidal action was calculated as follows from the average of the repeated tests attack in treated group x lOO 100 - = % action attack in untreated group The agents according to the invention were in the form of 20 % formulations. Compound according to % action against the invention no. Helminthosporium sativum 7 99 17 99 21 99.5 25 lOO 26 lOO 29 lOO - 62 ~ **00967 Compound according to % action against the invention no. Helminthosporium sativum 3 2 lOO 38 100 Comparison agent 2-butyl-3-(imida2ol-l-yl)-2- phenylpropionitrile 98. 5 2-butyl-3-(imidazol-l-yl)-2-phenylpropionitrile, hydronitrate 98 EXAMPLE T Effect against Pseudomonas phaseolicola, causative organism of grease spot disease in beans, _in vitro. After heat sterilisation, biomalt agar was cooled to approximately 45°C and then, mixed with the test substances in aqueous preparation, poured into plastics petri dishes. After the nutrient substrate had solidified, the dishes of treated agar and dishes of untreated agar as the control were inoculated in the centre with a suspension of the causative organism of grease spot, Pseudomonas phaseolicola, by means of an inoculation loop. The dishes were then incubated at 22°C. After 2\ weeks, the radial spread of the bacteria colonies that had grown was measured. The bacteria-inhibiting action was calculated as follows from the average of two repeats per test unit: - 6? 2 00967 radial growth in treated agar x 100 lOO - — —— = % inhibiting radial growth in untreated agar action The compounds were in the form of 20 % formulations. % inhibiting action of 250 ppm active substance 5 in agar against Pseudomonas phaseolicola: Compound according to the invention no. % inhibiting action 3 71 4 71 IO 11 67 12 86 13 78 15 75 17 67 15 18 75 19 71 21 71 Comparison aoent 2-butyl-3-(imidazol-l-yl)-2- 20 phenylpropionitrile, hydronitrate 42 EXAMPLE U Effect of prophylactic leaf treatment against true mildew Erysiphe qraminis in barley in a greenhouse. Young barley plants at the stage of having their 25 first leaf were sprayed until dripping wet with the - 64 - ; v) >J indicated concentrations. After the spray coatings had dried on, the treated plants and untreated control plants were inoculated with dry mildew spores by brushing the small test plants with infected plants. The test plants were then cultivated in a greenhouse at approximately from 20 to 22°C and after a veek the percentage of the surface area of the leaves that had been attacked was assessed. The fungicidal action was calculated as follows: attack in treated plants x 100 lOO - = % action attack in untreated plants The compounds were in the form of 20. % formulations. Compound according to % action the invention no. lOO pprr. 20 ppm 28 lOO 100 29 100 100 30 lOO 99 31 lOO 100 32 - 100 33 100 100 34 100 100 35 lOO 100 36 lOO 100 37 100 100 38 lOO " 100 39 98 90 </div>

Claims

<div class="application article clearfix printTableText" id="claims"> - 65 ~ 2 009 67 Compound according to % action the invention no. 100 ppn 20 ppm 40 100 91 41 IOO 100 42 IOO 100 43 96 91 44 IOO 100 45 IOO 96 46 100 100 47 100 100 48 IOO 100 49 100 100 50 100 100 51 100 100 52 IOO 100 53 loo 100 54 loo 100 55 loo 100 56 loo 100 57 100 100 58 100 87 59 loo 100 60 100 98 61 loo 100 62 loo 100 63 loo loo 64 .99 95 65 100 100 V'.'HAT ■fc'VVr. CLAIM IS: - 66 - 1. 00967 1 . An irnidazolylpropionitrile of the general formula 0 " R1 . — -N R - C - CH2 - N CN in which 5 R represents an aromatic hydrocarbon radical that is unsubstituted or substituted by one or more of the same or different substituents selected from halogen atoms, (Ci"C^)-alkyl, (C,-CA)-alkoxy and (C ^-C^)-alkylthio radicals and trifluoromethyl and 10 nitro groups, and R.j represents a (C ^-C1 ^ )-alkyl, (C^-Cg)-alkenyl, (C^-Cg)-alkvnyl or phenylalkyl radical each of which is unsubstituted or substituted by one or more of the same or different 15 substituents selected from halogen atoms, (C^-C^)- alkyl, (C^-C^)-alkoxy and (C,-C^)-alkylthio radicals and trifluoromethyl and nitro groups, or an acid addition salt thereof with an inorganic or organic acid. 2. A compound as claimed in claim 1, wherein R. 1 represents a (C^-C^^)-alkyl radical unsubstituted or substituted by one or more of the sane or different (C.-C.)-alkoxy radicals: a (C_,-CQ )-alkenyl radical; a 14 Jo (C^-Cg)-alkynyl radical; or a phenylalkyl radical that - 67 - ? 009 t is unsubstituted or substituted by one or more of the same or different substituents selected from halogen atoms, (C1-C^ )-al"kyl , (C.j-C4)-alkoxy and (C^-C^)-alkylthio radicals and trifluoromethyl and nitro groups. 3. A compound as claimed in claim 2, v.-herein represents a (C.-C.n)-alkyl radical, a (C_-Ca)-alkenyl 1 1 u Jo radical or a (C^-Cg)-alkynyl radical or a phenylalkyl radical that is unsubstituted or substituted by one or more of the same or different substituents selected from halogen atoms, (C^-C^)-alkyl, (C^-C^)-alkoxy and (C^-C^)-alkylthio radicals and trifluoromethyl and nitro groups. 4. A compound as claimed in claim 1, in which R represents a phenyl group unsubstituted or substituted by one or more of the same or different substituents selected from halogen atoms, (C^-C^)-alkyl, (C^-C^)-alkoxy and (C)-alkylthio radicals and trifluoromethyl and nitro groups, and R.j represents a (C ^-C^ )-alkyl radical, an allyl or propargyl group, or a benzyl group that is unsubstituted or substituted by one or more of the same or different substituents selected from halogen atoms, (C.j-C4)-alkyl, (C.j-C^-alkoxy and (C^-C^)-alkylthio radicals and trifluoromethyl and nitro groups. 5. A compound as claimed in claim 1, in which R represents a phenyl, 2-chlorophenyl, 3-chlorophenyl, - 68 - 2CC967 4-chlorophenyl, 2,4-dichlorophenyl, 2,6-dichloro-phenyl, 3,4-dichlorophenyl, ?-fluorophenyl, 4-fluorophenyl, 4-bromophenyl, ?-methylphenyl, 4-methylphenyl, 4-methoxyphenyl or 4-nitrophenyl group, and R.j represents a methyl, ethyl, propyl, isopropyl, pentyl, hexyl, allyl, propargyl, benzyl, 2-chloro-benzyl, 4-chlorobenzyl, 2,4-dichlorobenzyl or 3,4-dichlorobenzyl group. 6. A compound as claimed in any one of claims 1 to 5, in which the acid addition salt is the ■nitrate. 7 . 3-(Imidazol-l-yl)-2-phenyl-2-propoxypropionitrile, nitrate. 8. 3-(Imidazol-l-yl)-2-phenyl-2-propoxypropionitrile. 9 . 2-Butoxy-3-(imidazol-l-yl)-2-phenylpropionitrile, nitrate. 10. 2-Butoxy-3-(imidazol-l-yl)-2-pnenylpropionitrile. 1 1 . 2-Allylcxy-3-(imidazol-l-yl)-2-phenylpropionitrile, nitrate. 1 2. 2-Allyloxy-3-(imidazol-l-yl)-2-phenylpropionitrile. 1 3. 2-Ethoxy-3-(imidazol-l-yl)-2-phenylpropionitrile, nitrate. 14^ 2-Ethoxy-3-( imidazol-l-yl)-2-ph"enylpropionitrile. 15. 3-(Imidazol-l-yl)-2-methoxy-2-phenylpropionitrile, . nitrate. 16. 3-(Imidazol-l-yl)-2-methoxy-2-phenylpropionitrile. - 69 - 200967 17. 2- (2-Chlorophenyl)-3-(imidazol-l-yl)-2-propoxypropionitrile , nitrate. 18. 2-Butoxy-2-(4-chlorophenyl)-3-(imidazol-1-yl)-propionitrile, nitrate. 19. 2-Butoxy-2-(2-chlorophenyl)-3-(imidazol-l-yD-propionitrile , nitrate. 20. 2-Allyloxy-2-( 2-chlorophenyl-)-3-( imidazol-l-yl)-propionitrile, nitrate. 21 . 2-(4-Chlorophenyl)-3-(imidazol-l-yl)-2-propoxy-propionitrile, nitrate. 22. 2-Allyloxy-2-( 4-chlorophenyl)-3-( imidazol-l-yD-propionitrile, nitrate. 23. 2-(2-Chlorophenyl)-3-(imidazcl-l-yl)-2-propoxy-propionitrile. 24. 2-Butoxy-2-(4-chlorophenyl)-2-(imidazol-l-yD-propionitrile. 25. 2-Butoxy-2-(2-chlorophenyl)-3-(imidazol-l-yl)-propionitrile. 26. 2-Allyloxy-2-(2-chlorophenyl)-3-(imidazol-l-yl) -propionitrile. 27. 2-(4-Chlorophenyl)-3-(imidazci-l-yl)-2-propoxy-propionitrile. 28. 2-Allyloxy-2-(4-chlorophenyl)-3-(imidazol-l-yl)-propionitrile. 29. 2-Benzyloxy-3-(imidazol-l-yl)-2-phenylpropionitrile, nitrate. 30. 2-Benzyloxy-3-(imidazol-l-yl)-2-phenylpropionitrile. - 70 - 200967 31. 3-(Imidazol-l-yl)-2-isopropoxy-2-phenylpropionitrile, nitrate. 32. 3-(Imidazol-l-yl)-2-isopropoxy-2-phenylpropionitrile. 33. 2-(4-Chlorophenyl)-2-hexyloxy-3-(imidazol-l-yl )-propionitrile, nitrate. 34. 2-( 4-Chlorophenyl)-2-hexyloxy-3-( imidazol-l-yD-propionitrile. 35. 2-Allyloxy-3-(imidazol-l-yl)-2-(2-methylphenyl)-propionitrile, nitrate. 36. 2—(3,4-Dichlorophenyl)-3-(imidazol-l-yl)-2-propoxy-propionitrile, . nitrate. 37. 2-Butoxy-2-(2,4-dichlorophenyi)-3-(imidazol-l-yD-propionitrile , • nitrate. 38. 2-Allyloxy-2-(2,4-dichlorophenyl)-3-(imidazol-l-yD-propionitrile, .• nitrate. 39. 2-Ethoxy-2-(3,4-dichlorophenvl)-3-(imidazol-l-yl)-propionitrile, nitrate. 40. 2-Allyloxy-3-(imidazol-l-yl)-2-(2-methylphenyl)-propionitrile. 41. 2-(3,4-Dichlorophenyl)-3-(imidazol-1-yl)-2-propoxy-propionitrile. 42. 2-Allyloxy-2-( 3, 4-dichlorophenyl)-3-( imidazol-l-yD-propionitrile. 43. 2-Butoxy-2-(2,4-dichlorophenyl)-3-(imidazol-l-yD-propionitrile. 44. 2-Allyloxy-2-( 2, 4-dichlorophenyl)-3-' * propionitrile. - 71 - 2G0967 45. 2-Ethoxy-2-(3,4-dichlorophenyl)-3-(imidazol-l-yD-propionitrile. 46. 3-(Imidazol-l-yl)-2-phenyl-2-(1,2,2-trimethylpropoxy ) propionitrile, - nitrate. 47. 3-(Imidazol-l-yl)-2-(2-methoxyethoxy)-2-phenyl-propionitrile, nitrate. 48. 2-(2,2-Dimethylpropoxy)-3-(imidazol-l-yl)-2-phenyl-propionitrile, nitrate. 49. 2-(2,2-Dimethylpropoxy)-3-(imidazol-l-yl)-2-phenyl-propionitrile. 50. 2-(2-Fluorophenyl)-3-(imidazol-l-yl)-2-propoxypropionitrile , nitrate. 51 . 2-Butoxy-2- ( 2-f luorophenyl)-3-( imidazol-l-yD-propionitrile, nitrate. 52. 2-(4-Fluorophenyl)-3-(imidazol-l-yl)-2-propoxypropionitrile , -nitrate. 53. 2-Butoxy-2-( 4-f luorophenyl)-3-( imidazol-l-yD-propionitrile, .. nitrate. 54. 2-Allyloxy-2-(2-fluorophenyl)-3-(imidazol-l-yl)-propionitrile, nitrate. 55. 2-Ethoxy-2-(2-fluorophenyl)-3-(imidazol-l-yl)-propionitrile, nitrate. 56. 2-(2-Fluorophenyl)-3-(imidazol-l-yl)-2-methoxy-propionitrile, nitrate. 57. 3-(lmidazol-l-yl)-2-phenyl-2-(l,2,2-trimethylpropoxy) -propionitr ile. 58. 3-(lmidazol-l-yl)-2-(2-methoxyethoxy)-2-phen#^ ; propionitrile. jrY \\ 2Smtf: -12 - 2C0967 59. 2-(2-Fluorophenyl)-3-(imidazol-l-yl)-2-propoxy-propionitrile. 60. 2-Butoxy-2-(2-fluorophenyl)-3-(imidazol-l-yl)-propionitrile. 61. 2-(4-Fluorophenyl)-3-(imidazol-l-yl)-2-propoxy-propionitrile. 62. 2-Butoxy-2-(4-fluorophenyl)-3-(imidazol-l-yD-propionitrile. 63. 2-(2-Fluorophenyl)-3-(imidazcl-l-yl)-2-methoxy-propionitrile. 64. 2-Ethoxy-2-(2-fluorophenyl)-3-(imidazol-l-yl)-propionitrile. 65. 2-Allyloxy-2-(2-fluorophenyl)-3-(imidazol-l-yl)-propionitrile. 66. 2-Allyloxy-2-( 4-f luorophenyl)-3-( imidazol-l-yD-propionitrile, _ " nitrate. 67. 2-Ethoxy-2-(4-fluorophenyl)-3-(imidazol-l-yl)-propionitrile, .nitrate. 68. 2-(4-Fluorophenyl)-3-(imidazol-l-yl)-2-methoxy-propionitrile, .. nitrate. 69. 2-Ethoxy-2-(4-fluorophenyl)-3-(imidazol-l-yD-propionitrile. 70. 2-(4-Fluorophenyl)-3-(imidazol-l-yl)-2-methoxy-propionitrile. 71. 2-Allyloxy-2-(4-fluorophenyl)-3-(imidazol-l-yl)-~-opionitrile. 2-Decyloxy-3-( imidazol-l-yl)-2-pheny lpropionj.tr ile o| - 73 - 200967 73. 2-(3,3-Dimethylbutoxy)-3-(imidazol-l-yl)-2-phenyl-propionitrile, . =nitrate. 74. 3-(Imidazol-l-yl)-2-octyloxy-2-phenylpropionitrile. 75. 2-(3,3-Dimethoxybutoxy)-3-(imidazol-l-yl)-2-phenyl-propionitrile. 76. 2-(4-Bromophenyl)-2-butoxy-3-(imidazol-l-yl)-propionitrile, . .nitrate. 77. 2-(4-Bromophenyl)-3-(imidazol-l-yl)-2-propoxypropionitrile, . nitrate. 78. 2-(4-Bromophenyl)-2-hexyloxy-3-( imidazol-l-yD-propionitrile, nitrate. 79. 3-(Imidazol-l-yl)-2-(2-methylphenyl)-2-propoxy-propionitrile, nitrate. 80. 2-Hexyloxy-3-(imidazol-l-yl)-2-(2-methylphenyl)-propionitrile, ■. _,r nitrate. 81 . 2-(4-Bromophenyl)-2-butoxy-3-(imidazol-l-yl)-propionitrile. 82. 2-(4-Bromophenyl)-3-(imidazol-l-yl)-2-propoxy-propionitrile. 83. 2-(4-Bromophenyl)-2-hexyloxy-3-(imidazol-l-yl)-propionitrile. 84. 2-Butoxy-3-(imidazol-l-yl)-2-(2-methylphenyl)-propionitrile. 85. 2-Butoxy-3-(imidazol-l-yl)-2-(2-methylphenyl)-propionitrile, * ^nitrate. 86. 2-Hexyloxy-3-(imidazol-l-yl)-2-(2-methylphenyl)-propionitrile. 74 200967 87. 2-Decyloxy-3-(imidazol-l-yl)-2-phenylpropionitrile. 88. 3-(Imidazol-l-yl)-2-(2-methylphenyl)-2-propoxypropionitrile. 89. 2-Butoxy-2-(3-chlorophenyl)-3-(imidazol-l-yD-propionitrile. 90. 2-(3-Chlorophenyl)-2-hexyloxy-3-(imidazol-l-yl)-propionitrile, nitrate. 91. 2-Decyloxy-3-(imidazol-l-yl)-2-(2-methylphenyl)-propionitrile, nitrate. 92. 3-(Imidazol-l-yl)-2-(2-methylphenyl)-2-octyloxy-propionitrile. 93. 2-Decyloxy-3-(imidazol-l-yl)-2-(2-methylphenyl)-propionitrile. 94. 2-Butoxy-3-(imidazol-1-yl)-2-(4-methoxyphenyl)-propionitrile, nitrate. 95. 2-Butoxy-3-(imidazol-l-yl)-2-(4-methoxyphenyl)-propionitrile. 96. 2-( 4-Chlorophenyl)-2-hexyloxy-3- (imidazol-l-yD-propionitrile, hydrogen oxalate. 97. 2-(4-Chlorophenyl)-2-hexyloxy-3-(imidazol-l-yl)-propionitrile, bisulphate. ■98. A process for the preparation of a compound as claimed in claim 1, which comprises reacting a compound of the general formula O - R 1 R - C - CH 2 Y CN 2 ;/ / 2 009 i 75 5 in which R and R^ have the meanings given in claim 1 and Y represents a halogen atom or an alkylsulphonyloxy radical which is unsubstituted or substituted by one or more of the same or different halogen atoms or an unsubstituted or substituted aryl- or aralkyl-sulpiionyloxy 10 radical, with imidazole of the formula or a salt thereof in the presence of a solvent and, if desired, in the presence of a base, and, if desired, converting a compound of the general 15 formula I into a salt thereof and/or a salt of a compound .of the general formula I into a compound of the general formula I. 99. A process as claimed in claim 98, wherein the arylsulphonyloxy or aralkylsulphonyloxy radical represented by Y is unsubstituted or substituted by one or more of the same or different substituents selected from halogen atoms and alkyl radicals. 100. A process as claimed in claim 98, carried out substantially as described in any one of the Examples 1 to 91 herein. 101. A compound as claimed in claim 1, whenever prepared by a process as claimed in any one of claims 98 to 100. 102. A biocidal preparation which comprises a compound HC - NH li I HC CH N I 'S* 11 fcyi a ■' i 2009b7 -leas claimed in any one of claims 1 to 97 and 101 , in admixture or conjunction with a suitable carrier. 103. A biocidal preparation as claimed in claim 102, which is in the form of a powder, strewable agent, granulate, solution, emulsion or suspension. 104. A biocidal preparation as claimed in claim 102 or claim 103, which contains from 10 to 90 % by weight of compound of the general formula I or salt thereof, from 90 to 10 % by weight of liquid or solid carrier and, if desired, up to 20 % by weight of a surface active substance. 105. A biocidal preparation as claimed in claim 102, having a composition substantially as described in any one of Examples (ia), (ib), (ic), (ii) and (iii) herein. 106. A process for combating microbes, which comprises applying to a microbial infestation or to an area, object or material infested with or liable to infestation by microbes a compound as claimed in any one of claims 1 to 97 and 101 or a biocidal preparation as claimed in any one of claims 102 to 105. 107. A process as claimed in claim 106, for combating bacteria. 108. A process as claimed in claim 106, for ; combating fungi, | 109. A process as claimed in any one of claims g MI / ^ ,1 M l 106 to 108, wherein the compound or preparation is - 77 - 2009 f? 7 applied to a plant, seed, plant area or soil. 110. A process for regulating the growth of plants, which comprises applying a compound as claimed in any one of claims 1 to 97 and 101 or a preparation as claimed in any one of claims 102 to 105 to a plant, seed, plant area or soil. 111. A process as claimed in claim 109 or claim 110, wherein a preparation containing a compound as claimed in claim 1 is applied in an amount of from 100 to 1000 litres/ha. 112. A process as claimed in claim 106 or claim 110, carried out substantially as described in any one of the Examples A to U herein. SCHERING AKTIENGESELLSCHAFT By Their Attorneys HENRY HUGHES LIMITED By: ;9S5 </div>