GB2101995A - Biocidal imidazolylpropionitrile derivatives - Google Patents

Abstract

Novel imidazolylpropionitriles of the general formula <IMAGE> in which R represents an aromatic hydrocarbon radical that is unsubstituted or substituted by one of more of the same or different substituents selected from halogen atoms, (C1-C4)- alkyl, (C1-C4)-alkoxy and (C1-C4)-alkylthio radicals and trifluoromethyl and nitro groups, and R1 represents a (C1-C10)-alkyl, (C3-C8)-alkenyl, (C3-C8)-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, (C1-C4)-alkyl, (C1-C4)-alkoxy and (C1-C4)-alkylthio radicals and trifluoromethyl and nitro groups, and their acid addition salts with inorganic and organic acids, possess a fungicidal, growth-regulating and bactericidal action.

Description

SPECIFICATION Imidazolylpropionitriles, process for the manufacture of these compounds and their use as biocidal agents The invention relates to imidazolylpropionitriles and biocidal agents containing them.

Imidazolylpropionitrile derivatives having fungicidal action have already been disclosed in DE-OS 26 04 047. These, however, have a relatively narrow spectrum of action, and this is unsatisfactory.

This present invention provides imidazolylpropionitrile of the general formula

in which 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, (C1-C4)-alkyl, (C,-C4)alkoxy and (C1-C4)-alkylthio radicals, and trifluoromethyl and nitro groups, and R1 represents a (C1-ClO)-alkyl, (C3-C8)-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, (C1-C4)-alkyl, (C,-C4)-alkoxy and (C,-C4)-alkylthio radicals, and trifluoromethyl and nitro groups, and acid addition salts thereof with inorganic and organic acids.

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 individual isomers as well as mixtures thereof.

The imidazolylpropionitrile 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 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.

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 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 and protect these against causative organisms.

Further actions that may be mentioned are growth-regulating and bactericidal actions.

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 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 fungicides, plant growth regulators or bactericides, as the case may be.

In the compounds of the invention 1, an alkyl, alkenyl or alkynyl radical or a phenylalkyl radical represented by R, is unsubstituted or substituted as 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-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, 2-bromophenyl, 3-bromophenyl, 4-bromophenyl, 2-iodophenyl, 3-iodophenyl, 4-iodophenyl, 2,3-dichlorophenyl, 2,4-dichlorophenyl, 3,4-dichlorophenyl, 2,6dichlorophenyl, 2-methylpheny, 3-methylphenyl, 4-methylphenyl, 2-ethylphenyl, 3-ethylphenyl, 4-ethylphenyl, 2-propylphenyl, 3-propylphenyl, 4-propylphenyl, 2-isopropylphenyl, 3-isopropylphenyl, 4-isopropylphenyl, 2-butylphenyl, 3-butylphenyl, 4-butylphenyl, 2-sec-butylphenyl, 3sec-butylphenyl, 4-sec-butylphenyl, 2-tert-butylphenyl, 3-tert-butylphenyl, 4-tert-butylphenyl, 2methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl, 2-ethoxyphenyl, 3-ethoxyphenyl, 4-ethoxyphenyl, 2-methylthiophenyl, 3-methylthiophenyl, 4-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-5nitrophenyl, 4-chloro-2-fluorophenyl, 3,4,5-trimethoxyphenyl, or 5-chloro-2-nitrophenyl.

R, may represent, for example, (C,-C,O)-alkyl, for example methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, isopropyl, 2,2-dimethylprop-l -yl, 3, 3-dimethylbut-2-yl, (C3-C8)-alkenyl, for example 2-buten-1-yl, 3-methyl-2-buten-1-yl, hexenyl, heptenyl, octenyl, (C3-C8)-alkynyl, for example propargyl, butynyl, pentynyl, hexynyl, heptynyl, octynyl, or phenylalkyl, for example benzyl, 2-fluorobenzyl, 3-fluorobenzyl, 4-fluorobenzyl, 2-chlorobenzyl, 3-chlorobenzyl, 4-chlorobenzyl, 2-bromobenzyl, 3-bromobenzyl, 4-bromobenzyl, 2,4-dichlorobenzyl, 2,6-dichlorobenzyl, 3,4-dichlorobenzyl, 2-methylbenzyl, 3-methylbenzyl, 4-methylbenzyl, 2-nitrobenzyl, 3-nitrobenzyl, 4-nitrobenzyl, 2-trifluoromethylbenzyl, 3-trifluoromethylbenzyi, 4 trifluoromethylbenzyl, 2-methoxybenzyl, 3-methoxybenzyl, 4-methoxybenzyl, 2-ethoxybenzyl, 3ethoxybenzyl, 4-ethoxybenzyl, 2-propoxybenzyl, 3-propoxybenzyl, 4-propoxybenzyl, 2-butoxybenzyl, 3-butoxybenzyl, 4-butoxybenzyl, 2-methylthiobenzyl, 3-methylthiobenzyl, 4-methylthiobenzyl, 2-ethylthiobenzyl. 3-ethylthiobenzyl, 4-ethylthiobenzyl, 2-butylthiobenzyi, 3-butythiobenzyl and 4-butylthiobenzyl.

R, may also represent, for example, an alkoxyalkyl or dialkoxyalkyl group, for example 2methoxyethyl 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 hydrobromic acid; phosphoric acid, sulphuric acid, and, especially, nitric acid; monofunctional and bifunctional 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, ptoluenesulphonic 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, (C1-C4)-alkyl, (C,-C4)-alkoxy and (C1-C4)alkylthio radicals, and trifluoromethyl and nitro groups, and R, represents a (C,-C6)-alkyl radical, an allyl or propargyl group, or a benzyl group unsubstituted or substituted by one or more of the same or different substituents selected from halogen atoms, (C,-C4)-alkyl, (Ci-Ca)-alkoxy and (C,-C4)-alkylthio radicals, trifluoromethyl and nitro groups, and their salts.

Especially, there should be mentioned those in which R represents a phenyl, 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, 2,4-dichlorophenyl, 2,6-dichlorophenyl, 3,4-dichlorophenyl, 2-fluorophenyl, 4-fluorophenyl, 4-bromophenyl, 2-methylphenyl, 4-methylphenyl, 4-methoxyphenyl or 4-nitrophenyl group, and R, represents a methyl, ethyl, propyl, isopropyl, pentyl, hexyl, allyl, propargyl, benzyl, 2chlorobenzyl, 4-chlorobenzyl, 2,4-dichlorobenzyl or 3,4-dichlorobenzyl group, and their salts.

The following compounds have outstanding action: 2-n-butoxy-2-(2-chlorophenyl)-3-(imidazol1-yl)-propionitrile, hydronitrate, 2-n-butoxy-2-(2-chlorophenyl)-3-(imidazol-1 -yl)-propionitrile, 2-n-butoxy-2-(4-chlorophenyl)-3-(imidazol- 1 yI)-propionitrile, hydronitrate 2-(4-chlorophenyl)-3-(imidazol-l -yl)-2-n-propoxypropionitrile, hydronitrate 2-(2-chlorophenyi)-3-(imidazol-1 -yl)-2-n-propoxypropionitrile.

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

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

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 radical is, for example, a methyl-, ethyl-, propyl- or trifluoromethyl-sulphonyloxy group, and an arylsulphonylozy radical is, for example, a benzylsulphonyloxy or ptoluenesulphonyloxy group.

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.

Suitable solvents are substances that are inert towards the reactants, preferably substances of polar, aprotic character, such, for example, as N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, tetramethylurea, hexamethylphosphoric acid triamide and 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 1 00'C to 200"C is 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 solvent and adding the acid.

The imidazolylpropionitriles of the general formula I according to the invention are generally almost 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, 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-dimethylformamide, lower alcohols, chloroform and methylene chloride.

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 systemically 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 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.

The active substance of the invention may be used alone, in accordance with one another or with other active substances. Other plant-protecting or pest-combating agents may, if desired, be added, depending on the desired purpose.

The active substance or mixtures mentioned above are advantageously used in the form of preparations, such, for example, as powders, strewable agents, granulates, solution, emulsions or suspensions, with the addition of liquid and/or solid carriers or diluents and, if desired, wetting, adhesion, emulsifying and/or dispersion auxiliaries.

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.

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 the preparations are, for example, calcium ligninsulphonate, polyoxyethylene alkylphenyl ethers, naphthalenesulphonic acids and their salts, phenolsulphonic acids and their salts, formaldehyde condensates, fatty alcohol sulphates and substituted benzenesulphonic acids and their salts.

If the active substances are to be used for dressing seeds, colouring substances may also be admixed in 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 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 spray liquor of from 100 to 1000 litres/ha. The applications 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.

3-Arylsulphonyloxypropionitriles or 3-alkylsulphonyloxypropionitriles of the general formula II used as starting materials for preparing compounds of the general formula I, in which Y represents an arylsulphonyloxy or alkylsulphonyloxy radical, have hitherto not been described in the literature.

Accordingly, the present invention provides a compound of the general formula II in which R and R, have the meanings given above and Y represents an unsubstituted or halogensubstituted arylsulphonyloxy radical or alkylsulphonyloxy radical, and a process for its preparation. The alkylsulphonyloxy radical preferably has 1 to 4 carbon atoms.

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

in which R, and R have the meanings given under formula I, and reacting the resulting 3hydroxypropionitrile of the general formula

in which R, 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 formula Ill are known; others may be obtained according to methods known per se (cf., for example, Rubin et al., JACS 67, 1 92 f (1945); Hess et al., Ber. dt. chem. Ges. 50, 394 (1917)).

The hydroxymethyl compounds of the general formula IV have not been described hitherto in the literature.

Accordingly, the present invention provides a 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 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.

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.

Examples (i) to (iii) illustrate preparations containing compounds of the invention and Examples A to U illustrate their use.

EXAMPLE 1 3-(lmidazol- 1 -yl)-2-phenyl-2-propoxypropion itrile, h ydronitrate (Compound no. 1) 1 5 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 isopropanole and a little more than the theoretical quantity of 100% nitric acid is added. A little diethyi 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-(lmidazol- I -yl)-2-ph en yl-2-p ropoxyp rop ion itrile (Compound no. 2) 6.2 g (0.0195 mol) of the hydronitrate are dissolved in methanol and rendered basic with dilute ammonia solution while cooloing 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 in vacuo.

Yield: 4.85 g = 97% of the theoretical yield n3d = 1.5260 Examples 3-9 The following compounds according to the invention can be manufactured in an analogous manner.

Name of the compound Physical constant 3. 2-Butoxy-3-(imidazol-1-yl)-2- m.p. : 155-157 C(D) phenylpropionitrile, hydronitrate 4. 2-Butoxy-3-(imidazol-1-yl)-2- n3D9= 1.5208 phenylpropionitrile 5. 2-Allyloxy-3-(imidazol-1-yl)-2- m.p. 162-164 C(D) phenylpropionitrile hydronitrate 6. 2-Allyloxy-3-(imidazol-1-yl)-2- n3D3= 1.5402 phenylpropionitrile 7. 2-Ethoxy-3-(imidazol-1-yl)-2 m.p. : 182-186 C(D) phenylpropionitrile, hydronitrate 8. 2-Ethoxy-3-(imidazol-1-yl)-2- n44D = 1.5247 phenylpropionitrile 9. 3-(lmidazol-1 -yl)-2-methoxy-2- m.p. 189-1 91 'C(D) phenylpropionitrile, hydronitrate 10. 3-(lmidazol-1 -yl)-2-methoxy-2- m.p.:57-60 C phenylpropionitrile 11. 2-(2-Chlorphenyl)-3-(imidazol-1-yl)2-propoxypropionitrilo, hydronitrate m.p. : 162-165 C(D) 12. 2Butoxy-2-(-4-chlorophenyl)-3-(imidazol 1 -yl)-propionitrile, hydronitrate m.p.: 178- 181 çC(D) 13. 2-Butoxy-2-(2-chlorophenyl)-3-(imidazol1-yl)-propionitrile, hydronitrate m.p. : 177-178 C(D) 14. 2-Allyloxy-2-(2-chlorophenyl)-3 (imidazol-1-yl)-propionitrile, hydronitrate m.p. : 153-155 C(D) 15. 2-(4-Chloropheneyl)-3-(imidazol-1-yl)-2propoxypropionitrile, hydronitrate m.p. : 174-177 C(D) 16. 2-Allyloxy-2-(4-chlorophenyl)-3 (imidazol-1-yl)-propionitirle, hydronitrate m.p. : 152-155 C(D) 17. 2-(2-Chlorophenyl)-3-(imidazol-1-yl)-2propoxypropionitrile n41D = 1.5343 18. 2-Butoxy-2-(4-chlorophenyl~3 (imidazol-1-yl)-propionitrile n41D = 1.5288 19. 2-Butoxy-2-(2-chlorophenyl)-3 (imidazol-1-yl)-propionitrile n41D = 1.5329 20. 2-Allyloxy-2-(2-chlorophenyl)-3 (imidazoi-l -yl)-propionitriie n4D1= 1.5490 21. 2-(4-chlorophenyl)-3-(imidazol-1-yl)2-propoxypropionitrile n41D=1.5337 22. 2-Allyloxy-2-(4-chlorophenyl)-3 (imidazol-1-yl)-propionitrile n41D=1.5476 23. 2-Benzyloxy-3-(imidazol-1-yl)-2-phenylpropionitrile, hydronitrate m.p. ; 166-168 C(D) 24. 2-Benzyloxy-3-(imidazol-1-yl)-2phenylpropionitrile n4D0= 1.5638 25. 3-(lmidazol-1-yl)-2-isopropoxy-2phenylpropionitrile, hydronitrate m.p. : 165-168 C(D) 26. 3-(Imidazol-1-yl)-2-isopropoxy-2phenylpropionitrile n40D : 1.5254 27. 2-(4-Chlorophenyl)-2-hexyloxy-3- (imidazol-1-yl)-propionitrile, hydronitrate m.p. : 152-154 C(D) 28. 2-(4-Chlorophenyl)-2-hexyloxy-3 (imidazol-1-yl)-propionitrile n40D : 1.5197 29. 2-Allyloxy-3-(imidazol-l -yl)-2- (2-methylphenyl)-propionitrile, hydronitrate m.p.: 160"C (D) Name of the compound Physical constant 30. 2-(3,4-Dichlorophenyl)-3-(imidazol1-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) 34. 2-Allyloxy-3-(imidazol-l -yl)-2- (2-methylphenyl)-propionitrile n4D0 1.5388 35. 2-(3,4-dichlorophenyl)-3-(imidazol-1yl)-2-propoxypropionitrile n4D0 1.5360 36. 2-Allyloxy-2-(3,4-dichlorophenyl)-3 (imidazol-1-yl)-propionitrile n40D : 1.5500 37. 2-Butoxy-2-(2,4-dichlorophenyl)-3 (imidazol-1-yl)-propionitrile n40D : 15381 38. 2-Allyloxy-2-(2,4-dichlorophenyl)-3 (imidazol-1-yl)~-propionitrile n40D : 1.5531 39. 2-Ethoxy-2-(3,4-dichlorophenyl)-3 (imidazol-l -yl)-propionitrile n4Da 1.5372 40. 3-(lmidazol-l -yl)-2-phenyl-2- (1,2,2-trimethylpropoxy)-propionitrile.

hydronitrate m.p. : 168-173 C(D) 41. 3-(lmidazol-1-yl)-2-(2-methoxy- ethoxy)-2-phenylpropionitrile, hydronitrate m.p.: 158-160 C (D) 42. 2-(2,2-Dimethylpropoxy)-3 (imidazol-1 -yl)-2-phenylpropionitrile, hydronitrate m.p. 168-171 C(D) 43. 2-(2,2-Dimethylpropoxy)-3- (imidazol-l -yl)-2-phenylpropionitrile m.p.: 89-91 C 44. 2-(2-Fluorophenyl)-3-(imidazol-1yl)-2-propoxypropionitrile, hydronitrate m.p.: 170-172 C (D) 45. 2-Butoxy-2-(2-fluorophenyl)-3 (imidazol-1 -yl)-propionitrile, hydronitrate m.p.: 173-176 C (D) 46. 2-(4-Fluorophenyl)-3-(imidazol-1-yl)2-propoxypropionitrile, hydronitrate m.p. : 15-152 C(D) 47. 2-Butoxy-2-(4-fluorophenyl)-3 (imidazol- 1 -yl)-propionitrile, hydronitrate m.p.: 162-165 C (D) 48. 2-Allyloxy-2-(2-fluorophenyl)-3 (imidazol-1 -yl)-propionitrile, hydronitrate m.p.: 169-171 C (D) 49. 2-Ethoxy-2-(2-fluorophenyl)-3 (imidazol-1 -yl)-propionitrile, hydronitrate m.p.: 172-175 C (D) 50. 2-(2-Fluorophenyl)-3-(imidazol-1-yl)2-methoxypropionitrile. hydronitrate m.p.: 177-179 C (D) 51. 3-(Imidazol-1-yl)-2-phenyl-2-(1,2,2trimethylpropoxy)-propionitrile m.p.: 113-116 C 52. 3-(lmidazol-l -yl)-2-(2-methoxy- ethoxy)-2-phenylpropionitrile n4D0 1.5212 53. 2-(2-Fluorophenyl)-3-(imidazol-l -yl)- 2-propoxypropionitrile n40D::1.5143 54. 2-Butoxy-2-(2-fluorophenyl)-3 (imidazol-1-yl)-propionitrile n40D:1.5108 Name of the compound Physical constant 55. 2-(4-Fluorophenyl)-3-(imidazol-1yl)-2-propoxypropionitrile n40D : 1.5115 56. 2-Butoxy-2-(4-fluorophenyl)-3- (imidazol-1-yl)-propionitrile n40D : 1.5085 57. 2-(2-Fluorophenyl)-3-(imidazol- 1 - yl)-2-methoxypropionitrile n40D : 1.5280 58. 2-Ethoxy-2-(2-fluorophenyl)-3 (imidazol-1 -yl)-propionitrile n4D0: 1.5187 59. 2-Allyloxy-2-(2-fluorophenyl)-3 (imidazol-1-yl)-propionitrile n40D : 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-iluorophenyl)-3- (imidazol-1 -yl)-propionitrile, hydronitrate m.p.: 182-184 C (D) 62. 2-(4-Fluorophenyl)-3-(imidazol-1yl)-2-methoxypropionitrile, hydronitrate m.p.: 194-196 C (D) 63. 2-Ethoxy-2-(4-fluorophenyl)-3 (imidazol-1-yl)-propionitrile m.p. : 54-57 C 64. 2-(4-Fluorophenyl)-3-(imidazol-l- yl)-2-methoxypropionitrile m.p. : 88 C 65. 2-Allyloxy-2-(4-fluorophenyl)-3 (imidazol-1-yl)-propionitrile n40D : 1.5219 66. 2-Decyloxy-3-(imidazol-1-yl)-2phenylpropionitrile, hydronitrate m.p.: 126-128 C (D) 67. 2-(3, 3-Dimethylbutoxy)-3 (imidazol-1 -yl)-2-phenylpropionitrile, hydronitrate m.p.: 195-198 C (D) 68. 3-(lmidazol-1 -yl)-2-octyloxy-2phenylpropionitrile n40D : 1.5055 69. 2-(3,3-Dimethoxybutoxy)-3 (imidazol-1-yl)-2-phenylpropionitrile n40D ; 1.5093 70. 2-(4-Bromophenyl)-2-butoxy-3 (imidazol-1-yl)-propionitrile, hydronitrate m.p.: 171-174 C (D) 71. 2-(4-Bromophenyl)-3-(i midazol- 1 -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-(lmidazol-1-yl)-2-(2-methylphenyl)-2-propoxypropionitrile, hydronitrate m.p.: 180-183'C(D) 74. 2-Hexyloxy-3-(imidazol-1-yl)-2 (2-methylphenyl)-propionitrile, hydronitrate m.p.: 170-173 C (D) 75. 2-(4-Bromophenyl)-2-butoxy-3 (imidazol-1-yl)-propionitrile n40D : 1.5405 76. 2-(4-Bromophenyl)-3-(imidazol-1-yl)- 2-propoxypropionitrile n40D : 1.5418 77. 2-(4-Bromophenyl)-2-hexyloxy-3 (imidazol-1-yl)-propionitrile n40D : 1.5274 78. 2-Butoxy-3-(imidazol-1 -yl)-2- (2-methylphenyl)-propionitrile n40D : 1.5248 79. 2-Butoxy-3-(imidazol-1-yl)-2- (2-methylphenyl)-propionitrile, hydronitrate m.p.: 184-186 C 80. 2-Hexyloxy-3-(imidazole-l -yi)-2- (2-methylphenyl)-propionitrile n40D : 1.5163 Name of the compound Physical constant 81. 2-Decyloxy-3-(imidazol-1-yl)-2- phenylpropionitrile n4Da 1.5020 82. 3-(lmidazol-l -yl)-2-(2-methylphenyl)- 2-propoxypropionitrile n%0: 1.5276 83. 2-Butoxy-2-(3-chlorophenyl)-3 (imidazol-1 yl)-propionitrile n45. 1.5282 84. 2-(3-Chlorophenyl)-2-hexyloxy-3 (imidazol-1 -yl)-propionitrile, hydronitrate m.p.:: 162-165'C(D) 85. 2-Decyloxy-3-(imidazol-1 -yl)-2- (2-methylphenyl)-propionitrile, hydronitrate m.p.: 151 -155 C (D) 86. 3-(lmidazol-l -yl)-2-(2-methyl- phenyl)-2-octyloxypropionitrile, n4C. 1.5173 87. 2-Decyloxy-3-(imidazol-l -yl)-2- (2-methylphenyl)-propionitrile n4,0: 1.5139 88. 2-Butoxy-3-(imidazol-1 -yl)-2-(4methoxyphenyl)-propionitrile, hydronitrate m.p.: 163-167'C (D) 89. 2-Butoxy-3-(imidazole-l -yl)-2- (4-methoxyphenyl)-propionitrile n4D. 1.5228 90. 2-(4-Chlorophenyl)-2-hexyloxy-3 (imidazol-1 -yl)-propionitrile, hydrogen oxalate m.p.:: 195-1 97'C (D) 91. 2-(4-Chlorophenyl)-2-hexyloxy-3 (imidazol-1 -yl)-propionitrile, bisulphate m.p.: 158-163 C (D) (D = decomposition) In the following, the manufacture of a starting material is described.

Example 92 3-methylsulphonyl-2-phenyl-2-propoxypropionitrile 27 9 (0. 1 54 mol) of 2-phenyl-2-propoxypropionitrile are dissolved in 120 ml of pyridine, and 18.5 9 (0.614 mol) of paraformaldehyde are added. 7.7 ml of tetra butylammonium hdroxide (TBAOH) are added to this suspension while cooling with ice and the mixture is stirred 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 9 = 90% of the theoretical yield 3-hydroxy-2-phenyl-2-propoxypropionitrile 28 9 (0.136 mol) of 3-hydroxy-2-phenyl-2-propoxypropionitrile are dissolved in 200 ml of toluene, and 19.59(0.171 mol) of methanesulphonic 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 HCI 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 9 = 86% of the theoretical yield nD= 1.5000 3-methylsulphonyl-2-phenyl-2-propoxypropionitrile Examples of preparations Example (i) Wettable powder a) 40% by weight active substance 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 ligninsulphonic acid with alkylphenol polyglycol ethers b) 25% by weight active substance 60% by weight kaolin 10% by weight silicic acid 5% by weight surface-active substances based on the sodium salt of N-methyl-N-oleyltaurine and the calcium salt of ligninsulphonic acid.

c) 10% by weight of active substance .60% by weight of 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-oleyltaurine and the calcium salt of ligninsulphonic acid.

Example (ii) Paste 45% by weight active substance 5% by weight sodium aluminium silicate 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 Example (iii) Emulsion concentrate 25% by weight active substance 15% by weight cyclohexanone 55% by weight xylene 5% by weight mixture of nonylphenylpolyoxyethylene or calcium dodecylbenzenesulphonate.

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 Helm in thosporium spec. in barley.

Barley seeds infected naturally with Helminthosporium gramineum 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 1 2 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.

Compound according to g active substance the invention no. 100 kg seeds % action 1 50 95.6 2 50 100 3 50 100 4 50 100 5 50 100 6 50 100 7 50 100 8 50 100 9 50 100 10 50 100 11 50 100 12 50 100 13 50 100 14 50 100 15 50 100 16 50 100 17 50 100 18 50 100 19 50 100 20 50 100 21 50 100 Comparison agent methoxyethyl mercury silicate 2.63 87 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 a% % action 1 0.025 100 0.005 100 0.001 100 2 0.025 100 0.005 100 0.001 100 3 0.025 100 0.005 100 0.001 100 4 0.025 100 0.005 100 0.001 100 5 0.025 100 0.005 100 0.001 100 6 0.025 100 0.005 100 0.001 100 7 0.025 100 0.005 100 0.001 100 8 0.025 100 0.005 100 0.001 100 9 0.025 100 0.005 100 0.001 100 10 0.025 100 0.005 100 0.001 100 11 0.025 100 0.005 100 0.001 100 12 0.025 100 0.005 100 0.001 100 13 0.025 100 0.005 100 0.001 100 14 0.025 100 0.005 100 0.001 100 15 0.025 100 0.005 100 0.001 100 Compound according to active substance the invention no. concentration as a% % action 16 0.025 100 0.005 100 0.0Q1 100 17 0.025 100 0.005 100 0.001 100 18 0.025 100 0.005 100 0.0Q1 100 19 0025 100 0.005 100 0.001 100 20 0.025 100 0.005 100 0.001 100 21 0.025 100 0.005 100 0.001 100 22 0.001 100 0.0002 100 23 0.001 100 0.0002 100 24 0.001 100 0.0002 100 25 0.001 100 00002 100 26 0.001 100 0.0002 100 27 0.001 100 0.0002 100 28 0.001 100 0.0002 100 29 0.001 100 0.0002 100 30 0.001 100 0.0002 100 31 0.0001 100 0.0002 100 32 0.001 100 0.0002 100 33 0.001 100 0.0002 100 Compound according to active substance the invention no. concentration as a% % action 34 0.001 100 0.0002 100 35 0.001 100 0.0002 100 36 0.001 100 0.0002 100 37 0.001 100 0.0002 100 38 0.001 100 0.0002 100 39 0.001 100 0.0002 100 40 0.001 100 0.0002 100 41 0.001 100 0.0002 100 42 0.001 100 0.0002 100 43 0.001 100 0.0002 100 44 0.001 100 0.0002 100 45 0.001 100 0.0002 100 46 0.001 100 0.0002 100 47 0.001 100 0.0002 100 48 0.001 100 0.0002 100 49 0.001 100 0.0002 100 50 0.001 100 0.0002 100 51 0.001 100 0.0002 100 52 0.001 100 0.0002 100 53 0.001 100 0.0002 100 Compound according to active substance the invention no. concentration as a% % action 54 0.001 100 0.0002 100 55 0.001 100 0.0002 100 56 0.001 100 0.0002 100 57 0.001 100 0.0002 100 58 0.001 100 0.0002 100 59 0.001 100 0.0002 100 60 0.001 100 0.0002 100 61 0.001 100 0.0002 100 62 0.001 100 0.0002 100 63 0.001 100 0.0002 100 64 0.001 100 0.0002 100 65 0.001 100 0.0002 100 66 0.0025 100 0.00025 100 67 0.0025 100 0.00025 100 68 0.0025 100 0.00025 00 69 0.0025 100 0.00025 100 70 0.0025 100 0.00025 100 71 0.0025 100 0.00025 100 72 0.0025 100 0.00025 100 73 0.0025 100 0.00025 100 Compound according to active substance the invention no. concentration as a% % action 74 0.0025 100 0.00025 100 75 0.0025 100 0.00025 100 76 0.0025 100 0.00025 100 77 0.0005 99 0.00005 100 78 0.0005 100 0.00005 100 EXAMPLE C Effect of leaf treatment against Piricularia oryzae in rice seedlings in a greenhouse.

Young rice plants were sprayed until dripping wet 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 leaves that had been attacked was ascertained. From these attack figures, the fungicidal action was calculated as follows: 100 X attack in treated plants 1 00 - ~~~~~~~~~~~~~~~~~~~~~~~~~ = % action attack in untreated plants The substances were in the form of 20% wettable powders.

Compound according active substance to the invention no. concentration as a % % action 1 0.1 89 0.02 63 2 0.1 97.3 0.02 89 4 0.1 94.5 0.02 70 5 0.1 95 0.02 77.5 11 0.1 95 0.02 80 12 0.1 95 0.02 65 13 0.1 92.5 0.02 70 14 0.1 95 0.02 80 15 0.1 98 0.02 65 16 0.1 95 0.02 55 17 0.1 97.5 0.02 90 18 0.1 95 0.02 80 19 0.1 92.5 0.02 65 20 0.1 95 0.02 85 21 0.1 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, Botrytis cinerea, and incubated in the moist state at approximately 20 C in a greenhouse. After the untreated plants had collapsed (= 100% attack), the degree of attack in the treated plants was ascertained.The fungicidal action was calculated as follows: 100 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 0.025 80 12 0.025 90 13 0.025 95 14 0.025 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-dimethy-1 -(1 ,2,4-tria- zol-1-yl)-butan-2-one 0.025 60 EXAMPLE E Effect of prophylactic leaf treatment against Plasmopara 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 atmosphere 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 4 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 100- = % action attack in untreated plants The substances were in the form of 20% wettable powders.

Compound according active substance to the invention no. concentration as a % % action 11 0.025 89 12 0.025 93.3 13 0.025 92.5 14 0.025 73 15 0.025 95.4 16 0.025 82 17 0.025 92.7 18 0.025 94.6 19 0.025 95.5 20 0.025 65 21 0.025 81 EXAMPLE 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 100 ppm. For this purpose, a slide was placed in a 200 ml glass vessel containing 10 ml of 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 glasses were used for each substance.

For the evaluation, the length of the shoots and roots of the germinated seeds was measured after 7 days.

In the Table, the values are given in relation to a control and expressed as percentages.

It is apparent that the compounds according to 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 < 100%.

Compound according Growth as a % of normal growth to the invenion 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 17 83 56 18 67 67 19 100 56 20 83 78 21 50 44 22 50 57 EXAMPLE G 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. 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 cases, is greater than in the case of the comparison preparation.

Compound kg active total length length of according to substance/ha of the plants the 1st the invention no. as a % of internode normal length as a % of normal length 11 1 75 32 2 46 9 12 1 83 60 2 59 19 13 1 69 34 2 37 4 14 1 82 57 2 65 42 15 1 83 66 2 60 42 16 1 87 66 2 69 42 17 1 60 32 2 41 9 18 1 69 15 2 52 13 19 1 48 15 2 45 9 20 1 75 43 2 52 9 21 1 95 72 2 71 34 22 1 100 70 2 55 62 Comparison agent 2-chloroethyltrimethyl- 1 52 23 ammonium chloride 2 44 23 EXAMPLE H Effect of seed treatment against the cereal mildew Erysiphe graminis in barley.

Seeds of summer barley were sown untreated or dressed with 100 g of active substance/ 1 00 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: 100 X attack in treated group 100 = % 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: O = 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 9 = 1 0% 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 compounds according to the invention proved to be not only completely effective against Erysipha graminis but also completely compatible with the barley.

Compound according to the invention no. % action compatibility 1 100 10 2 100 10 5 100 10 6 100 10 7 100 10 8 100 10 9 99.5 10 10 100 10 11 93 10 15 100 10 16- 99 10 17 95 10 21 100 10 22 100 10 Comparison agent 1 -(4-chlorophenoxy)3,3-dimethyl-1 -(1,2,4- triazol-1-yl)-butan-2-one 100 4 EXAMPLE I Effect of propylactic leaf treatment against the leaf spot disease (Cercospora beticola) in sugarbeet (Beta vulgaris).

Sugarbeet plants having 4 well developed foliage leaves were sprayed until dripping wet with the indicated concentration. After the spray coating had dried on, the treated plants and untreated control plants were evenly sprayed with a suspension of 15,000 Cercospora spores per millilitre. The plants were incubated for four days in a greenhouse at 26"C in steamsaturated air and then maintained at approximately 22"C for a further 10 days in the greenhouse. The proportion of the surface area of the leaves attacked was then noted.From this, the action of the fungicides was calculated as follows: 100 X attack in treated plants 100- = % action attack in untreated plants Compound according active substance to the invention no. concentration as a % % action 1 0.05 100 0.01 100 2 0.05 100 0.01 100 4 0.05 100 0.01 99 5 0.05 100 0.01 95 11 0.05 100 0.01 100 12 0.05 100 0.01 99.6 13 0.05 100 0.01 93 14 0.05 100 0.01 99.6 15 0.05 100 0.01 98 17 0.05 100 0.01 99 18 0.05 100 0.01 99.6 19 0.05 100 0.01 99.3 20 0.05 100 0.01 98 21 0.05 100 0.01 99.6 Comparison agent manganese ethylene bis- 0.05 100 dithiocarbamate 0.01 79 EXAMPLE 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 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 Penicillium digitatum. After an 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: O = 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.

Compound according active substance concento the invention no. tration in the nutrient fungal solution as a % development 5 0.005% 4 0.001% 0 6 0.0005% 4 0.001% 1 17 0.0005% 0 0.001% 0 20 0.0005% 0 0.001% 0 21 0.0005% 2 0.001% 0 23 0.0005% 0 0.001% 0 24 0.0005% 1 0.001% 0 27 0.0005% 0 0.001% 0 28 0.0005% 0 0.001% 0 29 0.005% 0 0.001% 0 31 0.005% 0 0.001% 0 32 0.0005% 0 0.001% 0 34 0.0005% 0 0.001% 0 37 0.0005% 0 0.001% 0 38 0.0005% 0 0.001% 0 Comparison agent (according to DE-OS 26 04 047) 3-(imidazol-1 -yl)-2-phenyl2-butylpropionitrile hydronitrate 0.0005% 5 0.001% 4 untreated nutrient solution control EXAMPLE K Effect of prophylactic leaf treatment against the true vine mildew Unicinula nacator.

Young vines of the Silvaner type having approximately 8 to 10 leaves were sprayed until dripping wet with the concentrations indicated in the Table. After the spray coatings had dried on, the plants together with untreated control plants were dusted in the dry state with conidiospores of the fungus Uncinula necator and incubated in a greenhouse for 1 2 days at approximately 22"C. The proportion of the surface area of the leaves attacked by mildew was then estimated as a percentage and the fungicidal action was calculated as follows: attack in treated plants X 100 100- = % 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. The action is shown in the Table.

Compound according to % action against Uncinula necatorwith the invention no. 0.025 0.005% active substance 2 93 85 3 100 100 4 100 100 5 100 100 6 100 99 7 100 89 8 100 95 9 87 63 10 100 49 11 100 100 12 100 63 13 100 95 14 66 43 15 100 100 16 99 89 17 100 100 18 86 80 19 100 89 20 93 86 21 100 100 22 100 92 EXAMPLE L Effect of prophylactic leaf treatment against apple scab, Venturia inaequalis, in the open air.

Growing shoots of apple plants of the MM 106 type were treated until dripping wet with 0.1 % active substance concentration. After the spray coatings 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. The bags were then removed. After the experiment had lasted 2 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: attack in treated plants x 100 100- = % action attack in untreated plants The compounds were in the form of 20% wettable powders.

Compound according % action to the invention no.

18 100 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 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, some plants were treated until dirpping wet with 0.1% active substance concentration. After a further 1 ' weeks, the proportion of the surface area of the leaf attacked by apple scab was estimated as a percentage; in the untreated plants it was 99%. The compounds according to the invention were in the 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 Compound according to the invention no. % action 2 93 18 100 19 100 Comparison agent 2-butyl-3-(imidazol-1 -yl)-2- 90 phenylpropionitrile, hydronitrate EXAMPLE N Prophylactic leaf treatment against Erysiphe graminis 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 (0.55%). 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 110 x > < attack in treated plants 100 - ~~~~~~~~~~~~~~~~~~~~~~~~~~ = % action attack in untreated plants The substances according to the invention were in the form of 20% formulations.

Compound according % action with % action with to the invention no. 0.025% 0.005% active substance active substance 3 100 100 4 100 100 5 100 100 6 100 100 7 100 100 8 100 100 9 100 92 10 92 90 11 100 100 12 100 100 13 100 100 14 100 100 15 100 100 16 100 100 17 100 100 18 100 100 19 100 100 20 100 100 21 100 100 22 100 100 EXAMPLE O Effect of prophylactic leaf treatment against Uromyces appendiculatus (bean rust) in a greenhouse French bean plants at the stage of having half-developed primary leaves were sprayed until dripping wet with 100 ppm 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 chamber 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 100 100 - ~~~~~~~~~~~~~~~~~~~~~~~~~~~~ = % action Pustules in untreated plants The substances according to the invention were in the form of 20% formulations and exhibited over 90% action.

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 19 98 21 98.6 22 95 27 95 28 97 EXAMPLE P Effect of prophylactic leaf treatment against Helm in thosporium 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 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 action was calculated as follows: attack in treated plants > c x 100 100 - ~~~~~~~~~~~~~~~~~~~~~~~~~~ = % action attack in untreated plants The compounds were in the form of 20% formulations.

Compound according % action to the invention no. 500 ppm 100 ppm 35 90 90 36 95 90 37 95 90 38 95 90 39 95 95 40 100 100 41 100 98 42 100 100 43 100 100 44 100 100 46 100 100 47 100 100 48 100 89 49 100 100 50 100 96 51 100 100 52 98 89 53 100 100 54 96 96 55 100 100 57 100 100 58 100 96 59 100 89 EXAMPLE Q Effect of prophylactic leaf treatment against brown rust, Puccinia hordei, in barley in a climatised plant-growing chamber.

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 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 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 compounds according to the invention.

Compound according % action to the invention no. 500 ppm 32 100 42 100 43 100 45 100 46 100 47 100 48 100 49 100 54 100 55 100 58 100 61 100 64 100 65 100 66 100 67 100 69 100 71 100 72 100 74 100 75 100 76 100 77 100 78 100 79 100 80 100 EXAMPLE R Effect of prophylactic leaf treatment against yellow rust Puccinia strii form is in barley in a climatised plant-growing chamber.

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 Puccinia striiformis in 1,1 ,2-trifluoro-1 ,2,2-trichloroethane 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 of the leaves attacked by rust was noted.The fungicidal action was calculated as follows: attack in treated plants X 100 1 00 - ~~~~~~~~~~~~~~~~~~~~~~~~~~ = % action attack in untreated plants Compound according to % action with the invention no. 100 33 11 ppm 5 100 - - 12 100 100 100 14 100 - - 15 100 100 100 16 100 - - 17 100 100 100 18 100 100 93 28 100 98 78 EXAMPLE S Effect of seed treatment against Helm in thosporium sativum in barley in a climatised plantgrowing chamber.

Barley seeds infected artificially with Helminthosporium 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 af untreated seeds were sown 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 1 5 C. After 4 weeks, the plants that had emerged were examined for percentage attack of the base of the stem. The fungicidal action was calculated as follows from the average of the repeated tests attack in treated group X 100 100- = % 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. Helm in thosporium sativum 7 99 17 99 21 99.5 25 100 26 100 29 100 32 100 38 100 Comparison agent 2-butyl-3-(imidazol- -yl)-2- phenylpropionitrile 98.5 2-butyl-3-(imidazole- 1 -yi)-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 22 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: radial growth in treated agar X 100 100 - ~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~ - % inhibiting action radial growth in untreated agar The compounds were in the form of 20% formulations.

% inhibiting action of 250 ppm active substance in agar against Pseudomonas phaseolicola: Compound according to the invention no. % inhibiting action 3 71 4 71 11 67 12 86 13 78 15 75 17 67 18 75 19 71 21 71 Comparison agent 2-butyl-3-(imidazol-1 -yl)-2phenylpropionitrile, hydronitrate 42 EXAMPLE U Effect of prophylactic leaf treatment against true mildew Erysiphe graminis in barley in a greenhouse.

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 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 week the percentages 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 100 100- = % action attack in untreated plants The compounds were in the form of 20% formulations.

Compound according to % action the invention no. 100 ppm 20 ppm 28 100 100 29 100 100 30 100 99 31 100 100 32 - 100 33 100 100 34 100 100 35 100 100 36 100 100 37 100 100 38 100 100 39 98 90 40 100 91 41 100 100 42 100 100 43 96 91 44 100 100 45 100 96 46 100 100 47 100 100 48 100 100 49 100 100 50 100 100 51 100 100 52 100 100 53 100 100 54 100 100 55 100 100 56 100 100 57 100 100 58 100 87 59 100 100 60 100 98 61 100 100 62 100 100 63 100 100 64 99 95 65 100 100

Claims (123)

1. An imidazolylpropionitrile of the general formula

in which 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, (C,-C4)-alkyl, (C,-C4)alkoxy and (C,-C4)-alkylthio radicals and trifluoromethyl and nitro groups, and R, represents a (C,-C,)-alkyl, (C3-C8)-alkenyl, (C3-C8)-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,-C4)-alkyl, (C,-C4)-alkoxy and (C-,-C4)-alkythio 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, represents a (C,-C10)-alkyl radical unsubstituted or substituted by one or more of the same or different (C,-C4)-alkoxy radicals; a (C3C8)-aikenyl radical; a (C3-C8)-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, (C1 -C4)-alkyl, (C1 -C4)-alkoxy and (Cr-C4)-alkylthio radicals and trifluoromethyl and nitro groups.

3. A compound as claimed in claim 2, wherein R, represents a (C,-C,0)-alkyl radical, a C3-C8)-alkenyl radical or a (C3-C8)-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,-C4)-alkyl, (C,-C4)-alkoxy and (C1 -C4)-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, (C1-C4)-alkyl, (C,-C4)-alkoxy and (C1-C4)alkylthio radicals and trifluoromethyl and nitro groups, and R1 represents a (C1-C4)-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, (C1-C4)-alkyl, (C1-C4)-alkoxy and (C,-C4)-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, 4-chlorophenyl, 2,4-dichlorophenyl, 2, 6-dichlorophenyl, 3,4-dichlorophenyl, 2-fluorophenyl, 4-fluorophenyl, 4-bromophenyl, 2-methylphenyl, 4-methylphenyl, 4-methoxyphenyl or 4-nitrophenyl group, and R, represents a methyl, ethyl, propyl, isopropyl, pentyl, hexyl, allyl, propargyl, benzyl, 2chlorobenzyl, 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 hydronitrate.

7. 3-(lmidazole-l -yl)-2-phenyl-2-propoxypropionitrile, hydronitrate.

8. 3-(lmidazol-l -yl)-2-phenyl-2-propoxypropionitrile.

9. 2-Butoxy-3-(imidazol-1 -yl)-2-phenylpropionitrile, hydronitrate.

1 0. 2-Butoxy-3-(imidazol-1 -yl)-2-phenylpropionitrile.

11. 2-Allyloxy-3-(imidazol-l -yl)-2-phenylpropionitrile, hydronitrate.

1 2. 2-Allyloxy-3-(imidazol-l -yl)-2-phenylpropionitrile.

13. 2-Ethoxy-3-(imidazol-1-yl)-2-phenylpropionitrile, hydronitrate.

1 4. 2-Ethoxy-3-(imidazol-1 -yl)-2-phenylpropionitrile.

1 5. 3-(l midazol- 1 -yl)-2-methoxy-2-phenylpropionitrile, hydronitrate.

1 6. 3-(lmidazol-l -yl)-2-methoxy-2-phenylpropionitrile.

1 7. 2-(2-Chlorophenyl)-3-imidazol- 1 -yl)-2-propoxypropionitrile, hydronitrate.

1 8. 2-Butoxy-2-(4-chlorophenyl)-3-(imidazol- -yl)-propionitrile, hydronitrate.

1 9. 2-Butoxy-2-(2-chlorophenyl)-3-(imidazol-1 -yl)-propionitrile, hydronitrate.

20. 2-Allyloxy-2-(2-chlorophenyl)-3-(imidazol-1-yl)-propionitrile, hydronitrate.

21. 2-(4-Chlorophenyl)-3-(imidazol- 1 -yl)-2-propoxypropionitrile, hydronitrate

22. 2-Allyloxy-2-(4-chlorophenyl)-3-(imidazol-1-yl)-propionitrile, hydronitrate.

23. 2-(2-Chlorophenyl)-3-(imidazol- 1 -yl)-2-propoxypropionitrile.

24. 2-Butoxy-2-(4-chlorophenyl)-3-(imidazol-1-yl)-propionitrile.

25. 2-Butoxy-2-(2-chlorophenyl)-3-(imidazol-1-yl)-propionitrile.

26. 2-Allyloxy-2-(2-chlorophenyl)-imidazol-l -yl)-propionitrile.

27. 2-(4-Chlorophenyl)-3-(imidazol-1-yl)-2-propoxypropionitrile.

28. 2-Allyloxy-2-(4-chlorophenyl)-3-imidazol-1-yl)-propionitrile.

29. 2-Benzyloxy-3-(imidazol-1-yl)-2-phenylpropionitrile. hydronitrate.

30. 2-Benzyloxy-3-(imidazol-1-yl)-2-phenylpropionitrile.

31. 3-(lmidazol-l -yl)-2-isopropoxy-2-phenylpropionitrile, hydronitrate.

32. 3-(lmidazol-1-yl)-2-isopropoxy-2-phenylpropionitrile.

33. 2-(4-Chlorophenyl)-2-hexyloxy-3-(imidazol-1-yl)-propionitrile, hydronitrate.

34. 2-(4-Chlorophenyl)-2-hexyloxy-3-(uimidazol-1-yl)-propionitrile.

35. 2-Allyloxy-3-(imidazol-1-yl)-2-(2-methylphenyl)-propionitrile, hydronitrate.

36. 2-(3,4-Dichlorophenyl)-3-(imidazol-1-yl~-2-propoxypsropionitrile, hydronitrate.

37. 2-Butoxy-2-(2,4-dichlorophenyl)-3-(imidazol-1-yl)-propionitrile, hydronitrate.

38. 2-Allyloxy-2-(2,4-dichlorophenyl)-3-(imidazol-1-yl)-propionitrile, hydronitrate.

39. 2-Ethoxy-2-(3,4-dichlorophenyl)-3-(imida -yl)-propionitrile, hydronitrate.

40. 2-Allyloxy-3-(imidazol-l -yl)-2-(2-methylphenyl)-propionitrile.

41. 2-(3,4-Dichlorophenyl)-3-(imidazol-1-yl)-2-propoxypropionitrile.

42. 2-Allyloxy-2-(3,4-dichlorophenyl)-3-(imidazol-1-yi)-propionitrile.

43. 2-Butoxy-2-(2,4-dichlorophenyl)-3-(imidazol-1-yl)-propionitrile.

44. 2-Allyloxy-2-(2,4-dichlorophenyl)-3-(imidazol-1-yl)-propionitrile.

45. 2-Ethoxy-2-(3,4-dichlorophenyl)-3-(imidazol-1-yl)-propionitrile.

46. 3-(Imidazol-1-yl)-2-phenyl-2-(1,2,2-trimothylpropoxy)-propionitrile, hydronitrate

47. 3-(Imidazol-1-yl)-2-(2-methoxyethoxy)-2-phenylpropionitrile. hydronitrate.

48. 2-(2.2-Dimethylpropoxy)-3-(imidazol-1-yl)-2-phenylpropionitrile, hydronitrate.

49. 2-(2,2-Dimethylpropoxy)-3-(imidazol-1-yl)-2-phenylpropionitrile.

50. 2-(2-Fluorophenyl)-3-(imidazol-1 -yl)-2-propoxypropionitrile, hydronitrate.

51. 2-Butoxy-2-(2-fluorophenyl)-3-(imidazol-1 -yI)-propionitrile, hydronitrate.

52. 2-(4-Fluorophenyl)-3-(imidazol-1 -yl)-2-propoxypropionitrile, hydronitrate.

53. 2-Butoxy-2-(4-fluorophenyl)-3-(imidazol-1-yl)-propionitrile, hydronitrate.

54. 2-AIIyIoxy-2-(2-fluorophenyl)-3-(imidazol-1 -yl)-propionitrile, hydronitrate.

55. 2-Ethoxy-2-(2-fluorophenyl)-3-(imidazol-1 -yI)-propionitrile, hydronitrate.

56. 2-(2-Fluorophenyl)-3-(imidazol-1 -yl)-2-methoxypropionitrile, hydronitrate.

57. 3-(lmidazol-1 -yI)-2-phenyl-2-( 1 2, 2-trimethylpropoxy)-propionitrile.

58. 3-(lmidazol-1-yl)-2-(2-methoxyethoxy)-2-phenylpropionitrile.

59. 2-(2-Fluorophenyl)-3-(imidazol-1 -yl)-2-propoxypropionitrile.

60. 2-Butoxy-2-(2-fluorophenyl)-3-(imidazol- 1 -yl)-propionitrile.

61. 2-(4-Fluorophenyl)-3-(imidazol-1 -yl)-2-propoxypropionitrile.

62. 2-Butoxy-2-(4-fluorophenyl)-3-(imidazol-1 -yl)-propionitrile.

63. 2-(2-Fluorophenyl)-3-(imidazol-l -yl)-2-methoxypropionitrile.

64. 2-Ethoxy-2-(2-fluorophenyl)-3-(imidazol-1 -yI)-propionitrile.

65. 2-AllyIoxy-2-(2-fluorophenyl)-3-(imidazol-1 -yl)-propionitrile.

66. 2-AIIyIoxy-2-(4-fluorophenyl)-3-(imidazol-1 -yl)-propionitrile, hydronitrate.

67. 2-Ethoxy-2-(4-fluorophenyl)-3-(imidazol-1 -yI)-propionitrile, hydronitrate.

68. 2-(4-Fluorophenyl)-3-(im idazol- 1 -yl)-2-methoxy propion itrile, hydronitrate.

69. 2-Ethoxy-2-(4-fluorophenyl)-3-(imidazol- 1 -yl)-propionitrile.

70. 2-(4-Fluorophenyl)-3-(imidazol-l -yl)-2-methoxypropionitrile.

71. 2-Allyloxy-2-(4-fluorophenyl)-3-(imidazol-1-yl)-propionitrile.

72. 2-Decyloxy-3-(imidazol-1 -yl)-2-phenylpropionitrile, hydronitrate.

73. 2-(3-Dimethylbutoxy)-3-(imidazol-1-yl)-2-phenylpropionitrile. hydronitrate.

74. 3-(lmidazol-l -yl)-2-octyloxy-2-phenylpropionitrile.

75. 2-(3,3-Dimethyoxybutoxy)-3-(imidazol-1 -yl)-2-phenylpropionitrile.

76. 2-(4-Bromophenyl)-2-butoxy-3-(imidazol-1-yl)-propionitrile, hydronitrate.

77. 2-(4-Bromophenyl)-3-(imidazol- 1 -yl)-2-propoxypropionitrile, hydronitrate.

78. 2-(4-Bromophenyl)-2-hexyloxy-3-(imidazol-1 -yl)-propionitrile, hydronitrate.

79. 3-(lmidazol-1 -yI)-2-(2-methylphenyl)-2-propoxypropionitrile, hydronitrate.

80. 2-Hexyloxy-3-(imidazol-1-yl)-2-(2-methylphenyl)-proipionitrile, hydronitrate.

81. 2-(4-Bromophenyl)-2-butoxy-3-(imidazol-l -yl)propionitrile.

82. 2-(4-Bromophenyl)-3-(imidazol-1-yl)-2-propoxypropionitrile.

83. 2-(4-Bromophenyl)-2-hexyloxy-3-(imidazol-1 -yl)-propionitrile.

84. 2-Butoxy-3-(imidazol-1 -yl)-2-(2-methylphenyl)-propionitrile.

85. 2-Butoxy-3-(imidazol-1 -yl)-2-(2-methylphenyl)-propionitrile, hydronitrate.

88. 2-Hexyloxy-3-(imidazol-1-yl)-2-(2-methylphenyl)-propionitrile.

87. 2-Decyloxy-3-(imidazol-1 -yl)-2-phenylpropionitrile.

88. 3-(lmidazoi-1-yl)-2-(2-methylphenyl)-2-propoxypropionitrile.

89. 2-Butoxy-2-(3-chlorophenyl)-3-(imidazol- 1 -yl)-propionitrile.

90. 2-(3-Chlorophenyl)-2-hexyloxy-3-(imidazol-I yI)-propionitrile, hydronitrate.

91. 2-Decyloxy-3-(imidazol-1-yl)-2-(2-methylphenyl)-propionitrile, hydronitrate.

92. 3-elmidazol-1-yl)-2-(2-methylphenyl)-2-octyloxypropionitrile.

93. 2-Decyloxy-3-(imidazol-1-yl)-2-(2-methylphenyl)-propionitrile.

94. 2-Butoxy-3-(imidazol-1 -yl)-2-(4-methoxyphenyl)-propionitrile, hydronitrate.

95. 2-Butoxy-3-(imidazol-1 -yl)-2-(4-methoxyphenyl)-propionitrile.

96. 2-(4-Chlorophenyl)-2-hexyloxy-3-(imidazol-1-yl)-propionitrile, hydrogen oxalate.

97. 2-(4-Chlorophenyl)-2-hexyloxy-3-(i midazol-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

in which R and R, have the meanings given in claim 1 and Y represents a halogen atom or analkylsulphonyloxy 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-sulphonyloxy 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 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.

1 02. A biocidal preparation which comprises a compound as 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.

1 04. 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 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 106 to 108, wherein the compound or preparation is applied to a plant, seed, plant area or soil.

11 0. 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 11 0, wherein a preparation containing a compound as claimed in claim 1 is applied in an amount of from 100 to 1000 litres/ha.

11 2. A process as claimed in claim 106 or claim 11 0, carried out substantially as described in any one of the Examples A to U herein.

11 3. An area, object or material which has been treated by a process as claimed in any one of claims 106 to 112.

11 4. A seed, plant, plant area or soil which has been treated by a process as claimed in any one of claims 109 to 112.

11 5. A crop or other plant grown from seed or in an area or soil which has been treated by a process as claimed in any one of claims 109 to 11 2.

11 6. A plant as claimed in claim 114 or claim 11 5 which is a crop plant.

11 7. A compound of the general formula

in which R and R, have the meanings given in any one of claims 1 to 5 and Z represents a hydroxy group 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 aralkylsulphonyloxy radical.

11 8. A compound as claimed in claim 11 7, wherein the arylsulphonyloxy or aralkylsulphonyloxy radical represented by Z is unsubstituted or substituted by one or more of the same or different substituents selected from halogen atoms and alkyl radicals.

11 9. A compound as claimed in claim 11 7, wherein Z represents a hydroxy group or a methyl-, ethyl-, propyl- or trifluoromethyl-sulphonyloxy group or a benzylsulphonyloxy or p toluenesulphonyloxy group.

1 20. 3-Methylsulphonyl-2-phenyl-2-propoxypropionitrile.

121. 3-Hydroxy-2-phenyl-2-propoxypropionitrile.

122. A process for the preparation of a compound claimed in claim 11 7, which comprises hydroxymethylating a compound of the general formula

in which R and R, have the meanings given in claim 11 7, to give a compound of the general formula V in which Z represents a hydroxy group, and, if desired, reacting the compound of the general formula V with an appropriate sulphonic acid derivative to give a compound of the general formula V in which Z represents an unsubstituted or halogen-substituted alkylsulphonyloxy radical or an unsubstituted or substituted aryl- or aralkyl-sulphonyloxy radical

1 23. A process as claimed in claim 1 22, carried out substantially as described in Example 92 herein.