GB2119374A

GB2119374A - 1,2,4 -Triazol-1-yl-propionitrile derivatives

Info

Publication number: GB2119374A
Application number: GB08311220A
Authority: GB
Inventors: Carlo Skotsch; Dietrich Baumert; Hansjorg Krahmer
Original assignee: Schering AG
Current assignee: Bayer Pharma AG
Priority date: 1982-04-26
Filing date: 1983-04-25
Publication date: 1983-11-16
Also published as: MA19779A1; KR840004413A; PH21063A; FR2525596B1; RO86358B1; GB2119374B; CA1195992A; SU1264830A3; FR2525596A1; NL8300748A; CS244127B2; DD212641A5; PT76582A; ES8401050A1; FI830994A0; BE896558A; GR78840B; DE3216301A1; FI830994L; ATA145783A

Abstract

1,2,4 -Triazol-1-yl- propionitriles of the general formula <IMAGE> in which R represents an aryl radical optionally substituted by one or more of the same or different substituents selected from halogen atoms and (C1-C4) - alkyl, (C1-C4)alkoxy, (C1-C4)alkylthio, trifluoromethyl and nitro groups and R1 represents a (C1-C10)alkyl, (C3-C8)alkenyl, or (C3-C8)alkynyl radical, or a phenylalkyl radical optionally substituted by one or more of the same of different substituents selected from halogen atoms and (C1-C4)alkyl, (C1-C4)alkoxy (C1-C4)alkylthio, trifluoromethyl and nitro groups, acid addition salts thereof with inorganic and organic acids, a process for the preparation of these compounds, and biocidal agents containing them are provided. The agents have a herbicidal, fungicidal, plant growth-regulatory action and also a bactericidal action.

Description

1 ,2,4-triazol-1 -yl-propionitrile derivatives, their pre paration and use The present invention is concerned with new 1,2,4 ,triazol-1 -yl-propionitrile derivatives, their preparation and use as biocidal agents, especially those having a fungicidal, herbicidal, bactericidal and growth regulating action.

Imidazolyl-propionitrile derivatives having a fungi cidal action are already known (see German Offenle gungsschrift No. 2604 047). These, however, have a relatively narrow range of action, which is unsatisfactory.

It is an aim of the present invention to provide new propionitrile derivatives that offer a wide variety of possible applications, especially in the field of plant protection, and have a broad fungicidal range of action.

The present invention provides a compound ofthe general formula

in which R represents an aryl radical which is unsubstituted or substituted by one or more of the same or different substituents selected from halogen atoms, (C1-C4) alkyl groups, (C1-C4) alkoxy groups, (C1-C4) alkylthio groups,trifluoromethyl groups and nitro groups, and R1 represents a (C1-C10) alkyl radical, a (C3-C8) alkenyl radical, a (C3-C8) alkyl radical ora phenylalkyl radical which is unsubstituted or substituted by one or more ofthe same or different substituents selected from halogen atoms, (C1-C4) alkyl groups, (C1-C4) alkoxy groups, (C1-C4) alkylthio groups, trifluoromethyl groups and nitro groups, or an acid addition saltthereofwith an inorganic or organic acid.

The compounds according to the present invention are, in the broadest sense, biocidally active, but are distinguished in particular by a fungicidal action in which they are surprisingly superior to known active substances of analogous constitution and mode of action.

Thefungicidal action surprisingly extends to action againstfu ngi which attack different systematic positions in plants. In the treatment of parts ofthe plant above soil level the compounds of the present invention can give protection against wind-borne pathogens. To control seed-transmitted pathogens, the compounds can also be usedfortreating seeds themselves. In addition, these compounds can act systemically, that is to say they can be taken up by the roots of the plant, for example after being applied to the seed, and be transported to the parts of the plant above soil level to protect those parts against pathogens.

Further actions exhibited by compounds ofthe present invention which may be mentioned are growth-regulatory action and bactericidai action.

Owing to the broad range of action which they have been found to possess, the compounds are suitable not onlyforthe protection of crop plants but also for the general protection of materials and for the control of, for example, microbes causing disease in humans and animals, and, as a result, their possible applications are very varied.

As may be appreciated, the fields of application in which the compounds exhibit outstanding actions can vary in accordance with the specific meaning of the substituents. Thus, they can be used as fungicides, plant growth regulators or bactericides.

An alkyl group present in a compound ofthe invention may be a straight-chain or branched-chain alkyl group. Similarly an alkenyl oralkynyl group present in a compound ofthe invention may be a straight-chain or branched-chain alkenyl or alkyl group.

In the compounds of the general formula I R may represent, for example, any of the following groups: phenyl, 2-fluorophenyl, 3-fluorophenyl, 4- fluorophenyl, 2-chlorophenyl, 3-chlorophenyl, 4chlorophenyl, 2-bromophenyl, 3-bromophenyl, 4bromophenyl, 2-iodophenyl, 3-iodophenyl, 4iodophenyl, 2,4-dichlorophenyl, 3,4-dichlorophenyl, 2,6-dichiorophenyl, 2-methyiphenyl, 3-methylphenyl, 4-methyiphenyl, 2-ethylphenyl, 3-ethylphenyl, 4-ethylphenyl, 2-propylphenyl, 3-propylphenyl, 4-propylphenyl, 2-isopropylphenyl, 3-isopropylphenyl, 4-isopropyiphenyl, 2-butylphenyl, 3butylphenyl, 4-butylphenyl, 2-sec.-butylphenyl, 3sec.-butylphenyl, 4-sec.-butylphenyl, 2-tert.-butylphenyl, 3-tert.-butylphenyl, 4-tert.-butylphenyl, 2methoxyphenyl, 3-methoxyphenyl, 4-methoxy phenyl, 2-ethoxyphenyl, 3-ethoxyphenyl, 4-ethoxy- phenyl, 2-methylthiophenyl, 3-methylthiophenyl, 4methylthiophenyl, 2-ethylthiophenyl, 3-ethylthiophenyl, 4-ethylth iophenyl, 2-trifluoromethyl- phenyl, 3-trifluoromethylphenyl, 4-trifluoromethylphenyl, 2-nitrophenyl, 3-nitrophenyl,4-nitrophenyl, 3-fluoro-4-methoxyphenyl, 3-chloro-5-nitrophenyl, 4 chloro-2-fluorophenyl,3,4,5-trimethoxyphenyl, and 2-chloro-2-nitrophenyl and R1 may represent, for example, any one of the following groups: (C1-C10) alkyl, for example methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, isopropyl, 2,2-dimethylprop-1 -yl, 3,3-dimethylbut-2-yl, (C3-C8) alkenyl, for example allyl, 2-buten-1- yl, 3-methyl-2-buten-1 -yl, hexenyl, heptenyl, octenyl, phenylalkyl, for example benzyl, 2-fluorobenzyl, 3- fluorobenzyl, 4-fluorobenzyl, 2-chlorobenzyl, 3-chlorobenzyl, 4-ch lorobenzyl, 2-bromobenzyl, 3-bromobenzyl, 4-bromobenzyl, 2,4-dichlorobenzyl, 2,6dich lorobenzyl, 3,4-dichlorobenzyl, 2-methylbenzyl, 3-methylbenzyl, 4-methylbenzyl, 2-nitrobenzyl, 3nitrobenzyl, 4-nitrobenzyl, 2-trifluoromethylbenzyl, 3-trifluoromethylbenzyl, 4-trifluoromethylbenzyl, 2methoxybenzyl, 3-methoxybenzyl, 4-methoxybenzyl, 2-ethoxybenzyl, 3-ethoxybenzyl, 4-ethoxybenzyl, 2propoxybenzyl, 3-propoxybenzyl, 4-propoxybenzyl, 2-butoxybenzyl, 3-butoxybenzyl, 4-butoxybenzyl, 2 methylthiobenzyl, 3-methylthiobenzyl, 4-methylthiobenzyl, 2-ethylthiobenzyl, 3-ethylthiobenzyl, 4ethylthiobenzyl, 2-butylthiobenzyl, 3-butylthiobenzyl, and 4-butylthiobenzyl.

An aryl radical represented by R is preferably a phenyl group, especially an alkyl, or haolgen-substituted phenyl group.

A radical represented by F1 is preferably a (C1-C10) alkyl group oran allyl group.

Inorganic and organic acids fortheformation of the acid addition salts of the present invention which may be mentioned byway of example are hydrohalic acids, such as, for example, hydrochloric acid and hydrobromic acid, phosphoric acid, sulphuric acid, nitric acid, especially conc. nitric acid, mono- or bi-functional carboxylic acids and hydroxycarboxylic acids, such as, for example, acetic acid, maleic acid, succinic acid, fumaric acid, tartaric acid, citric acid, salicyclic acid, sorbic acid, lactic acid, and also sulphonic acids, such as, for example, p-toluenesulphonic acid and 1,5-naphthalenedisulphonicacid.

The acid addition salts of the present invention may be obtained by the customary salt formation proces ses,for example by dissolving a compound ofthe general formula I in a suitable solvent and adding the desired acid.

Asan acid addition salt a compound ofthe present invention, a hydronitrate salt is preferred.

The compounds ofthe present invention that are distinguished by an outstanding fungicidal action are especiallythose compounds of the general formula I in which the radical R represents any one ofthefollowing groups: phenyl, 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, 2,4dichlorophenyl, 3,4-dichlorophenyl, 4-bromophenyl, 2-fluorophenyl, 4-fluorophenyl and 2-methylphenyl and the radical R1 represents any one ofthefollowing groups: ethyl, allyl, propyl, isopropyl, butyl and hexyl.

Preferably, of these compounds, there areto be mentioned those in which R represents a phenyl, 4-chlorophenyl or2-methylphenyl group and R1 represents a propyl, isopropyl or butyl group.

Thefollowing compoundsaccordingtotheinven- tion have been found to have an outstanding action: 2-isopropoxy-2-phenyl-3-(1 ,2,4-triazol-l-yl)-propionitrile hydronitrate, 2-butoxy-2-(2-methylphenyl)-3-(l ,2,4-triazol-l-yl)- propionitrile hydronitrate, 2-phenyl-2-pro poxy-3-( 1 ,2,4-triazo l-l-yl)- propionitrile hydronitrate, 2-butoxy-2-(4-chlorophenyl)-3-(1 ,2,4-triazol-l-yl)propionitrile hydronitrate, 2-(4-chlorophenyl)-2-propoxy-3-(1 ,2,4-triazol-l-yl)- propionitrile hydronitrate, 2-isopropoxy-2-phenyl-3-(1 ,2,4-triazol-l-yl)propionitrile, 2-butoxy-2-(2-methylphenyl)-3-(1 ,2,4-triazol-l-yl)- propionitrile, 2-hexyloxy-2-phenyl-3-(1 ,2,4triazol-l-yl)- propionitrile hydronitrate, 2-butoxy.2-(4-chlorophenyl)-3-(1 ,2,4-triazol-l-yl)propionitrile, 2-(4-chlorophenyl)-2-propoxy-3-(1 ,2,4-triazol-l-yl)propionitrile, 2-hexyloxy-2-(2-methylphenyl)-3-( 1 ,2,4-triazol-l-yl)propionitrile hydronitrate, 2-butoxy-2-phenyl-3-(1 ,2,4-triazol-l-yl)propionitrile hydronitrate, 2-butoxy-2-(2-chlorophenyl)-3-(1 ,2,4-triazol-l-yl)propionitrile hydronitrate, 2-ethoxy-2-phenyl-3-(1 ,2,4-triazol-l-yl)- propionitrile hydronitrate, 2-al Iyloxy-2-phenyl-3-( 1 ,2,4-triazol-l-yl )- propionitrile hydronitrate, 2-(2-chlorophenyl)-2-propoxy-3-(1 ,2,4-triazol-l-yl)propionitrile hydronitrate, 2-(4-chlorophenyl)-2-hexyloxy-3-(1 ,2,4-triazol-l-yl)propionitrile hydronitrate, 2-hexyloxy-2-(2-methylphenyl)-3-(1 ,2,4-triazol-l-yl)propionitrile, 2-butoxy-2-phenyl-3-(1 ,2,4-triazol-l-yI)-prnpionitrile, 2-(2-chlorophenyl)-2-butoxy-3-(1 ,2,4-triazol-l-yl)propionitrile, 2-ethoxy-2-phenyl-3-( 1 ,2,4-triazol-l-yl)propionitrile, 2-allyloxy-2-phenyl-3-(1 ,2,4-triazol-l-yl)propionitrile, 2-(2-chlorophenyl)-2-propoxy-3-(1 ,2,4-triazol-1 -yl)propionitrile.

The compounds according to the present invention exhibit, in particular,fungicidal actions but, atthe same time, are distinguished by a growth-regulatory action in a number of crop plants. Further, depending onthetype of plant and the application quantity, herbicidal effects also are produced and make possible weed control in such cases.

Sincethe compounds according to the invention can both bring about quantitative and qualitative changes in the plants and alterthe metabolism of plants,theyareto be classified as plant growth regulators, which are distinguished bythefollowing possible applications: inhibition ofthevegetative growth in woody and herbaceous plants,forexample on roadsides, railway tracks, etc., to prevent lush growth, growth inhibition in cerealsto prevent lodging or snapping offhand in cotton to increasetheyield, influencing of branching of vegetative and generative organs in ornamental and crop plants to increasethe amount of blossom or in tobacco and tomatoesto inhibittheformation of side shoots, improvementoffruitquality,forexamplean increase in the sugar content in sugar cane, in sugar beet or in fruit, and a more even maturation ofthe crop which results in higher yields, raising ofthe resistance to climatic effects such as cold and drought, influencing ofthe latex flow in rubber plants, Other possible applications are: development of pa rthenocarpicfruits, pollen sterility and sex determination, control ofthe germination of seeds orthe production of buds, defoliation or influencing of fruit drop to facilitate harvesting.

The compounds according to the invention are especially suitable for influencing the growth of Beta (beet) crops, but also have desirable growth-regula- tory effects in cereals, soya and cotton or also generally in plantation crops.

Itwill be appreciated that not every compound will havethesame herbicidal,fungicidalandlorregulat- ing actionswith everytype of plant, type of application, time of application or concentration applied.

Depending on the purpose of application, the application quantities are generally in the range of from 0.05 to 5 kg of active substance/hectare, but greater application quantities may be used if appropriate. When two or more compounds are used the range of from 0.05 to 5 kg per hectare refers, of course, to the total application quantities.

The time of application varies in accordance with the purpose of application and the climatic conditions.

The compounds ofthe present invention can be applied to seeds1 germinating seeds (before or after emergence), roots, stalks, leaves, blossom, produce or other parts of the plants as desired.

Surprisingly,theaction of the compounds according to the present invention is broader or stronger than that of known products having the same direction of action.

In addition to the actions described above, the compounds according to the present invention also havea bactericidalaction which allowsfurther possible applications. Treatment of animate, for example living plants, and inanimate substrates to protect against bacterial attack is thus possible.

The present invention accordingly also provides a biocidal preparation which comprises at least one compound selected from compounds ofthe general formula land salts thereof with inorganic and organic acids, in admixture or conjunction with a suitable carrier.

The present invention further provides a method of protecting a living plant againstweeds and/or phyto pathogenic fungi and/or of regulating its growth, wherein the living plant and/orthe area in the vicinity ofthe living plant is/are treated with a compound selected from compounds of the general formula I and salts thereof with inorganic and organic acids.

The present invention further provides a method of protecting a crop area against weeds and/or phyto pathogenic fungi and/or of regulating the growth of plants in the area, wherein the crop area is treated with a compound selected from compounds ofthe general formula land salts thereof with inorganic and organic acids.

The present invention further provides a method of dressing seeds, wherein the seeds a retreated with a compound selected from compounds of the general formula land salts thereof with inorganic and organic acids.

The present invention also provides a method of protecting a substrate against bacteria, wherein the substrate is treated with a compound selected from compounds of the general formula land salts thereof with inorganic and organic acids.

The present invention further provides a pack which comprises a compound selected from com pounds ofthe general formula land salts thereofwith inorganic and organic acids, togetherwith instructions for its use as a herbicide and/orfungicide and/or bactericide and/or for regulating the growth of a living plant.

The compounds according to the invention can be used on their own or in admixture with one another or with other active substances. Other plant-protective agents or pest-controlling agents or defoliants may optionally be added, depending on the desired application.

The active substances of the present invention or mixtures thereof are advantageoulsy applied in the form of biocidal preparations, for example powders, strewable agents, granules, solutions, emulsions or suspensions, with the addition of solid and/or liquid carriers, and diluents and, if desired, wetting agents, adhesive agents, emulsifiers and/or dispersing au xiliaries.

Suitable liquid carriers are, for example, water, aliphatic and aromatic hydrocarbons, for example benzene, toluene, xylene, cyclohexanone, isophor one, dimethyl sulphoxide, dimethylformamide, and also mineral oil fractions and vegetable oils.

As solid carriers there are suitable mineral earths, for example Tonsil (a trade mark), silica gel,talc, kaolin, attapulgite, limestone, silicic acid and veget able products, for example meals.

Surface-active substances which may be mentioned are, for example, calcium lignin sulphonate, polyoxyethylene-alkylphenyl ethers, naphthalene sulphonic acids and saltsthereof,formaldehyde condensates, fatty alcohol sulphates and also substituted benzenesulphonicacids andsaltsthereof.

Where the active substances are to be used for dressing seeds, they may also be admixed with colouring substances to give the dressed seed a clearly visible colour.

The total amount of the active substance or substances in the various preparations can vary within wide limits. For example, the agents may contain in the range of from approximately 10 to 90% by weight active substance(s), from approximately 90 to 10% byweight liquid orsolid carrier(s) and also, if desired, up to 20% by weight surface-active agent(s).

The agents may be applied in customary manner, for example with water as the carrier in spray liquor quantities of in the range of from approximately 100 to 1000 litres/hectare. It is equally possible to use the agents in a so-called "Low-Volume-Process" or "U ltra-Low-Volu me-Process" and to apply them in the form of so-called microgranules.

The following constituents, for example, may be usedforthe manufacture of a preparation ofthe invention: A. Sprayable powder a) 40% byweightactivesubstance 25% by weight clay minerals 20% by weight silicic acid 10% by weight cellulose pitch 5% by weight surface-active substance based on a mixture of the calcium salt of ligninsulphonic acid a nd a I and alkylphenolpolyglycol ethers b) 25% byweightactive substance 60% by weight kaolin 10% by weight silicic acid 5% byweight surface-active substances based on the sodium salt of N - methyl - N - oleyltaurine and the calcium salt of ligninsulphonic acid c) 10% byweightactivesubstance 60% by weight clay minerals 15% byweightsilicicacid 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 B. Paste 45% by weight active substance 5% by weight sodium aluminium silicate 15% by weight cetylpolyglycol ether with 83 moles of ethylene oxide 2% by weight spindle oil 10% byweight polyethyleneglycol 23 parts water C. Emulsion concentrate 25% by weight active substance 15% byweightcyclohexanone 55% byweightxylene 5% by weight mixture of nonylphenylpolyox- yethylene or calcium dodecylbenzene sulphonate.

The present invention further provides a process forthe preparation of a compound of the invention, or a saltthereof, which comprises reacting a compound ofthe general formula

in which R and R1 havethe meanings given above and Y represents a halogen atom of an alkylsulphonyloxy orarylsulphonyloxy radical which is optionally halogenated in the side chain with a compound ofthe formula

oran alkali metal derivative thereof ifdesired in the presence of a solvent and, optionally, in the presence of a base and, ifdesired, a compound ofthe general formula I is converted into an acid addition salt thereof with an inorganic or organic acid and /our acid addition salt is converted into a corresponding free compound ofthe general formula I.

As a halogen atom represented by Y, there may be mentioned,forexample,a chlorine, bromine and iddine atom; as an alkylsulphonyloxy radical repre sented by there are suitable, for example a methyl-, ethyl-, propyl- and trifluoromethylsulphonyloxy group, and as an arylsulphonyloxy radical repre sented byYthere maybe mentioned,forexample,a benzenesulphonyloxyand p-toluenesulphonyloxy group.

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

In addition, a 1, 2, 4-triazole-alkali metal derivative may be used instead of 1,2, 4-triazole.

Suitable solvents are those which are inerttowards the reactants, preferably those a polar, aprotic nature, such as N, N-dimethylformamide, N, N - dimethy låcetamide, N - methylpyrrolidone, tetramethylu rea, hexamethlyphosphoric acid triamide ancl benzonitrile, but higher boiling point aromatic and aliphatic hydrocarbons, such astoluene, chlorobenzene or xylene, may also be used.

The reaction temperature may be varied within wide limits. Atemperature in the range of from 100 C to 200 C is preferred. The reaction may be carried out under normal or excess pressure.

The 1,2, 4-triazol - I -yl - propionitriles according to the invention are, in general, almost colourless and odourless solid substances. The acid addition salts derived therefrom are also colourless and odourless, crystalline compounds. The free bases are sparingly soluble in water and more or less readily soluble in organic solvents, such as, for example, alcohols, ethers or chlorinated hydrocarbons. The acid addition salts are to some extent soluble in water and readily soluble in polar organicsolvents such as acetonitrile, N, N-dimethylformamide, lower alcohols, chloroform and methylene chloride.

The following Examples illustrate the invention.

Unless otherwise specified, percentages are given hereinafter on a weight basis.

Example 1 2-lsopropoxy-2-pheny1-3- (1,2,4-triazol-l- yl)- propionitrile hydronitrate (Compound no.2) 0.55 mol of 1,2, 4-triazole is added, while stirring and cooling, to sodium hydride (0.55 mol) suspended in 50 ml of dry dimethyl formamide (DMF). 0.11 mol of 2 - isopropoxy -3 - methylsulphonyloxy- 2 phenylpropionitrile in 50 ml of DMF is then added and the whole is maintained at a bath temperature of 1 500Cfor 1.5 hours. Aftercooling,the mixture is extracted three times with 100 ml of ether, the combined ether phases are washed twice with water and dried with magnesium sulphate, MgSO4.The ether is concentrated by rotary evaporation in vacuo, 50 ml of isopropanol are added to the residue and, while stirring and cooling, 6.8 ml of concentrated nitric acid are added dropwise. Afterthe addition of 80 ml of ether, the mixture is stirred for a further 1/4 hour and then suction-filtered. Fecrystallisation is effected from isopropanol.

m.p. 185-189"C (with decomposition) Yield: 15g = 43% ofthetheoreticalyield.

Example2 2-Isopropoxy-2 - phenyl - 3- (1, 2, 4 - triazol - 1- yl) - propion itrile (Compound no.3) 10g ofthe hydronitrate of 2 - isopropoxy- 2 - phenyl -3-(1,2,4-triazol-l-yl)-propionitrileobtainedin Example 1 are dissolved in methanol and 8 ml of 32% strength ammonia water are added. The mixture is poured into water, extracted with ethyl acetate, dried over magnesium sulphate, MgSO4, the ethyl acetate is concentrated by rotary evaporation in vacuo, a little ethyl acetate and active carbon are added, the mixture is boiled briefly, suction-filtered and again concentrated by rotary evaporation. The resulting solid is analytically pure.

m.p.176-177 C Yield: 6.65 g = 83% ofthetheoretical yield.

The following compounds according to the invention can be prepared in an analogous mannerto that described in Example 1 or Example 2. "D" under physical constant indicates "decomposition".

Compound no. Name of compound Physical constant 1. 2-Hexyloxy-2-(2 methylphenyi)-3 (1 ,2,4-triazol-l- yl)-propionitrile hydronitrate m.p. 159-162"C (D) 4. 2-Butoxy-2-(2 methylphenyl)-3 (1 ,2,4-triazol-l- yl)-propionitrile m.p. 58-62 C 5. 2-Butoxy-2-(2 methylphenyl)-3 (1,2,4-triazol-l- yl)-propionitrile hydronitrate m.p.158-161 C (D) 6. 2-Hexyloxy-2-(2 methylphenyl)-3 (1 ,2,4-triazol-l- yl)-propionitrile nD40: 1.5121 7. 2-Butoxy-2-phenyl 3-(1,2,4-triazol (-yl)-propionitrile hydronitrate m.p. 159-160"C (D) 8. 2-Butoxy-2-(2- chlorophenyl)-3 (1,2,4-triazol-l yl)-propionitrile hydronitrate m.p. 142.5-144 C (D) 9. 2-Ethoxy-2-phenyl 3-(1 ,2,4-triazol-l- yl)-propionitrile hydronitrate m.p. 169-170"C (D) 10. 2-Phenyl-2-propoxy 3-(1 ,2,4-triazol-l- yl)-propionitrile hydronitrate m.p. 178-179 C (D) 11. 2-(3-Chlorophenyl) 2-hexyloxy-3-(1,2,4 triazol-l-yl)-propio nitrile hyronitrate m.p. 173-175 C (D) 12. 2-Butoxy-2-phenyl- 3-(1,2,4-triazol I-yl)-propionitrile m.p. 67-68 C 13. 2-Phenyl-2-propoxy 3-(1,2,4-triazol I-yl)-propionitrile m.p. 107-108 C 14. 2-Ethoxy-2-phenyl 3-(1,2,4-triazol I-yl)-propionitrile m.p. 74-75 C 15. 2-Hexyloxy-2-phenyl 3-( 1 ,2,4-triazol- I-yl)-propionitrile hydronitrate m.p. 158-160 C (D) 16. 2-Allyloxy-2 phenyl-3-(1 ,2,4- triazol-l-yl) propionitrile hydronitrate m.p. 145-147 C (D) 17. 2-Butoxy-2(4 chlorophenyl)-3 (1,2,4-triazol I-yl)-propio nitrile hydro nitrate m.p. 173-175"C (D) 18. 2-Allyloxy-2-phenyl 3-(1,2,4-triazol I-yl)-propionitrile m.p. 86-88 C 19. 2-Methoxy-2-phenyl 3-(1,2,4-triazol I-yl)-propionitrile m.p. 77-79 C 20. 2-Hexyloxy-2-phenyi- 3-(1,2,4-triazol- I-yl)-propionitrile m.p. 58-60 C 21. 2-(2-Chlorophenyl) 2-hexyloxy-3-(1,2,4- triazol-l-yl) propionitrile hydro nitrate m.p. 157-159 C (D) 22. 2-(2-Chlorophenyl) 2-propoxy-3-(1,2,4 triazol-l-yl)-pro pionitrile hydro nitrate m.p. 138-139"C (D) 23. 2-(4-Chlorophenyl) 2-propoxy-3-(1,2,4 triazol-l-yl)-pro pionitrile hydro nitrate m.p. 155-157 C (D) 24. 2-(4-Chlorophenyl) 2-hexyloxy-3-(1,2,4- triazol-l-yl)-pro pionitrile hydro nitrate m.p. 155-159 C (D) 25. 2-(4-Chlorophenyl) 2-propoxy-3-(1,2,4 triazol-l-yl)-pro pionitrile m.p. 115-119 C 26. 2-Butoxy-2-(4 chlorophenyl)-3 (1,2,4-triazol-l- yl)-propionitrile m.p. 54-60 C 27. 2-(2-Methylphenyl) 2-octyloxy-3-(1,2,4- triazol-l-yl)-pro pionitrile hydro nitrate m.p. 128-134 C (D) 28. 2-Decyloxy-2 (2-methylphenyl) 3-(1,2,4-triazol- I-yl)-propionitrile hydronitrate m.p. 116-120 C (D) 29. 2-(2-Methylphenyl) 2-octyloxy-3-(1,2,4- triazol-l-yl)-pro pionitrile nD20: 1.4930 30. 2-(2-Chlorophenyl) 2-butoxy-3-( 1,2,4- triazol-l-yl)-pro pionitrile nD40: 1.5273 31. 2-(2-Chlorophenyl) 2-propoxy-3-(1,2,4 triazol-l-yl)-pro pionitrile nD40: 1.5308 32. 2-Butoxy-2-(2,4 dichlorophenyl) 3-(1,2,4-triazol I-yl)-propionitrile hydronitrate m.p. 163-166 C 33. 2-Butoxy-2-(2,4 dichlorophenyl) 3-(1,2,4-triazol I-yl)-propionitrile m.p. 53-55 C 34. 2-Allyloxy-2 (2,4-dichloro phenyl)-3-(1 ,2,4- triazol-l-yl)-pro pionitrile m.p. 104-107"C 35. 2-(3,4-Dichloro phenyl)-2-propoxy- 3-(1,2,4-triazol I-yl)-propionitrile hydronitrate m.p. 152-155"C (D) 36. 2-(3,4-Dichloro phenyl)-2-propoxy 3-(1,2,4-triazol I-yl)-propionitrile m.p. 60-66 C 37. 2-(3,4-Dichloro phenyl)-2-hexyloxy 3-(1,2,4-triazol I-yl)-propionitrile hydronitrate m.p. 166-168"C 38. 2-(3,4-Dichloro phenyl)-2-hexyloxy 3-(1,2,4-triazol l-yl)-propionitrile nD40:: 1.5240 39. 2-(4-Fluorophenyl) 2-propoxy-3-(1,2,4- triazol-l-yl )-pro pionitrile hydro nitrate m.p. 172-175 C (D) 40. 2-(4-Fluorophenyl) 2-propoxy-3-(1 2,4- triazol-l-yl )-pro pionitrile m.p. 98-100 C 41. 2-Butoxy-2-(4 fluorophenyl)-3 (1 ,2,4-triazol- l-yl)-propionitrile hydronitrate m.p. 173-175 C (D) 42. 2-Butoxy-2-(4 fluorophenyl) 3-(1,2,4-triazol I-yl)-propionitrile m.p. 56-58 C 43. 2-(2-Fluorophenyl) 2-propoxy-3-(1,2,4 triazol-l-yl)-pro pionitrile hydro nitrate m.p. 150-153 C (D) 44. 2-(2-Fluorophenyl) 2-propoxy-3-(1,2,4 triazol-l-yl)-pro pionitrile m.p. 66-69 C 45. 2-Butoxy-2-(2 fluorophenyl)-3 (1 ,2,4-triazol-l- yl)-propionitrile hydronitrate m.p. 138-143 C (D) 46. 2-Butoxy-2-(2 fluorophenyl)-3 (1,2,4-triazol- I-yl)-propionitrile m.p. 76-79"C 47. 2-(2-Fluorophenyl) 2-hexyioxy-3-(1,2,4 triazol-l-yl)-pro pionitrile hydro nitrate m.p. 134-137 C (D) 48. 2-(2-Fluorophenyl) 2-hexyloxy-3-(1 ,2,4- triazol-l-yl)-pro pionitrile m.p. 58-600C 49. 2-(4-Bromophenyl) 2-propoxy-3-(1,2,4- triazol-l-yl)-pro pionitrile hydro nitrate m.p. 150-153 C (D) 50. 2-(4-Bromophenyl) 2-propoxy-3-( 1,2,4- triazol-l-yl)-pro pionitrile m.p. 118-121 C 51. 2-(4-Bromophenyl) 2-hexyloxy-3-(1 ,2,4- triazol-l-yl)-pro pionitrile hydro nitrate m.p. 161-164"C (D) 52. 2-(4-Bromophenyl) 2-hexyloxy-3-(1 ,2,4- triazol-l-yl)-pro pionitrile m.p. 60-62 C 53. 2-(2,4-Dichloro phenyl)-2-propoxy 3-(1,2,4-triazol l-yl)-propionitrile hydronitrate m.p. 166-170 C (D) 54. 2-(2,4-Dichloro phenyl)-2-propoxy 3-(1,2,4-triazol I-yl)-propionitrile m.p. 61-63"C 55. 2-(2-Methylphenyl) 2-pentyl-3-(1,2,4 triazol-l-yl)-pro pionitrile hydro nitrate m.p. 151-154 C (D) 56. 2-(2-Methylphenyl) 2-pentyl-3-(1,2,4 triazol-l-yl)-pro pionitrile nD40: 1.5111 57. 2-(4-Methylphenyl) 2-propoxy-3-(1,2,4 triazol-l-yl)-pro pionitrile hydro nitrate m.p. 170-171 C (D) 58. 2-Hexyloxy-2-(4 methylphenyl)-3 (1 ,2,4-triazol-l- yl)-propionitrile hydronitrate m.p. 177-181 C (D) 59. 2-(4-Methylphenyl) 2-propoxy-3-(1,2,4 triazol-l-yl)-pro pionitrile m.p. 120-124 C 60. 2-Hexyloxy-2-(4 methylphenyl)-3 (1,2,4-triazol-l yl)-propionitrile nD40: 1.5065 61. 2-Butoxy-2-(4 methylphenyl)-3 (1 ,2,4-triazol-l- yl)-propionitrile m.p. 71-73"C The 3-aryl- and 3-al kyi-sulphonyloxypropionitriles ofthe general formula II in which Y represents respectively aryl- and alkyl-sulphonyloxy which are to be used as starting materials have not hitherto been described in the literature.

They may be obtained by hydroxymethylating, by methods known perse, phenylacetonitriles of the general formula

in which R and R1 have the meanings given above, some ofwhich are known or can be obtained by methods known perse (cf. for example Rubin etal., JACS 67, 192f (1945); Hess etal., Ber. dt. chem. Ges.

50,394(1971)) or by reacting the3-hydroxypropionitriles ofthe general formula

with a suitable sulphonic acid derivative, for exam ple, a sulphonic acid chloride, optionally with the addition ofan acid binder. The hydroxymethyl compounds ofthe general formula IV have not hitherto been known from the literature.

The manufacture of a starting material is described below.

3-Methylsulphonyl-2phenyl-2-propoxy-propionitrile 27 g (0.154 mol) of 2-phenyl-2-propoxy-aceto nitrile are dissolved in 120 ml of pyridine, and 18.5 g (0.614 mol) of paraformaldehyde are added. To this suspension, 7.7 ml oftetrabutylammonium hydroxide (TBAOH) are added as a 40% strength solution while cooling with ice and the whole is mixed throughly by vigorous stirring. After a few hours (TLC monitoring), the mixture is poured into ice-water and extracted with ether. The ether phase is washed with dilute hydrochloric acid and then with sodium chloride solution and dried over magnesium sulphate.After removing the drying agent by filtration and concentrating by rotary evaporation in vacuo, a colourless oil remains behind which is found to be homogeneous according tothin-layer chromatography and can.be further processed without further purification.

Yield: 28.49 = 90% ofthetheoretical yield of 3-hydroxy-2-phenyl-2-propoxy-propionitrile nD20:1.5027 28 g (0.136 mol) of 3-hydroxy-2-phenyl-2-propoxypropionitrile are dissolved in 200 ml oftoluene, and 19.5 Kg (0.171 mol) of methanesulphonyl chloride are added. At 1 00C, 18.6 g (0.184 mol) oftriethylamine are added dropwise. The mixture is stirred for 30 minutes at room temperature, filtered from the precipitated triethylamine hydrochloride and concentrated. The residue istaken up in ether, washed with water, dried over magnesium sulphate and concentrated. The oily residue isfoundto be pure according to thin-layer chromatography.

Yield: 32.27g = 86% of the theoretical yield of 3-methylsulphonyl-2-phenyl-2-propoxy-propionitrile nD20: 1.5000 The following exemplary embodiments illustrate the possible applications ofthe compounds accord ingtotheinvention,intheformofthepreparations mentioned above.

Example 3 Effect of prohylactic leaf treatment against true mildew Erysiphegraminis in barley in a greenhouse Young barley plants atthefirst leaf stage were sprayed until dripping wet with the stated concentrations. When the spray coatings had dried, the treated plants and also untreated control plants were inoculated with dry mildew spores by being stroked with infected plants.The test plants were then cultivated in a greenhouse at approximately 20 to 220C and, after one week, were assessed for the percentage attack of the leaf surface. The fungicidal effectwas calculated asfollows: 100- Attack in treated . 100 =%effect Attack in untreated The compounds were used as 20 /O strength formulations.

Compound according Erysiphe graminis to the invention No. % effect 500 ppm 100 ppm 1 ago 95 2 100 59 3 100 100 4 100 100 5 100 95 6 100 94 7 100 100 8 100 100 9 100 100 10 100 100 11 100 94 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 22 100 100 23 100 100 24 100 - 25 100 - 26 100 - 28 100 100 30 100 100 31 100 100 33 100 100 34 100 100 35 100 100 Compound according Erysiphe graminis to the invention No. % effect 500 ppm 100 ppm 36 100 100 38 100 95 41 100 42 100 100 44 100 100 48 100 100 49 100 100 50 100 100 51 100 100 52 100 100 53 100 100 54 100 100 55 100 57 58 59 60 61 Example4 Effect of prophylactic leaf treatment against Erysiphe cichoracearum in gourd plants in a greenhouse Gourd plants sprayed until dripping wet with the stated concentrations were inoculated, after the spray coating had dried, by being dusted with dry mildew spores of Erysiphe cichoracearum and incubated together with inoculated untreated control plants in a greenhouse at 24"C. After one week, the surface area affected by mildew as a percentage of the entire leaf surface area was estimated.The fungicidal effect was calculated asfollows: 100 - 100 'Attack in treated = % effect Attack in untreated The letter "s" in thefollowing table denotesthatthe fungicidal action could also be assessed in the growth ofthe plants (after treatment) and was found to be positive. That is to say, the active substances were transported systemicallyin the additional growth and showed one hundred per cent action against mildew in that growth also.

The compounds according to the invention were used as 20 % strength formulations.

Compound according Erysiphe cichoracearum to the invention No. % effect 250 25 5 2.5 0.5ppm 1 100s 100s 1 100s 2 100s 100s 100s 3 100s 100s 100s 4 100s 100s 100 5 100s 100s 100 6 100s 100s 100 7 100 100 100 8 100s 98 100 9 lOOs 100s 100s 10 100s 100s 100 11 100s 100s 100 12 100s 100s 100 13 100s 14 100s 100s 100 15 100s 100 100 16 100s 100 99.5 17 100s 100s 100s 18 100s 100s 100 19 100s 100 97 20 100s 21 100s 100 90 22 100s 100 100 27 100s 29 100s 32 100s 37 100s 39 100s 40 100s 43 100s 45 100s 46 100s 47 100s 56 100s Example 5 Effect(%) of prophylactic leaftreatmentagainst Helminthosporium teres (=Pyrenophora teres), net blotch disease, in barley Young barley plants atthefirstleafstage were sprayed until dripping wet with the stated concentrations. When the spray coatings had dried, the treated plants and untreated control plants were sprayed with a suspension ofthe conidiospores of Helminthosporium teresand incubated in a moist chamber for 2 days at from 20 to 22"C. The plants were then cultivated in a greenhouse at 20 to 22"C. One week after inoculation, the percentage attack ofthe leaf surfaces was noted. The fungicidal effect was calculated as follows: 100 - Attack in treated. 100 = % effect Attack in untreated The compounds were used as 20 % strength formulations.

Compound according Helminthosporium teres to the invention No. % effect 500 ppm 100 ppm 10 ppm 1 100 100 2 100 100 100 3 100 100 90 4 95 95 90 5 100 100 6 99 7 98 90 8 83 9 100 85 10 95 95 11 100 90 12 94 90 13 92 85 14 89 80 15 94 90 16 94 80 17 89 18 100 70 19 94 20 70 23 85 24 95 90 25 95 95 26 80 27 90 Example 6 Effect of prophylactic leaf treatment against dwarf rust Puccinia hordeiin barley in a controlled climate plant growth chamber Young barley plants at the first leaf stage were sprayed until dripping wet with the stated concentration. When the spray coatings haddried,thetreated plants and untreated control plants were inoculated by being stroked with plants affected by dwarf rust and placed in a plantgrowth chamber.At 150C, and in almost moisture-saturated air forth first two days, the plants were cultivated for 10 days. The percentage proportion of the leaf surface attacked by rust was then noted.Thefungicidal effect was calculated as follows: Attack in treated .100 100- = % effect Attack in untreated The compounds were used as 20% strength formulations.

Compound according Puccinia hordei to the invention No. % effect 500 ppm 100 ppm 20 ppm 1 100 77 2 100 83 3 4 100 100 89 5 100 100 94 6 100 94 7 100 98 89 8 100 94 94 9 80 10 100 98 94 11 89 12 84 13 89 14 95 80 15 95 16 78 17 100 100 100 18 98 19 95 20 85 21 100 70 22 100 100 23 79 24 90 70 25 90 90 27 85 30 95 31 95 Example 7 Action against Pseudomonas phaseolicola, the cause of halo blight in beans, in vitro Biomalt agarwas cooled, after heat sterilisation, to approximately45 C and was then poured,together with the test substances which had been mixed together in an aqueous preparation, into plastics petri dishes.When the nutrient medium had set, the dishes oftreated agarand also dishes containing untreated agar as a control were inoculated in the centre by means of an inoculating loop with a suspension of the halo blight pathogen Pseudomonas phaseolicola.

The dishes were then incubated at 220C. After 21/2 weeks, the radial spread of the colonies of bacteria which had grown were measured. From the average oftwo repititions per test sample, the bacteria inhibiting action was calculated as follows: Radial growth in treated . 100 100 - = % inhibiting Radial growth in untreated action The compounds were used as 20% strength formulations.

Compound according % action with 250 ppm to the invention No. active substance concentration 12 62 15 73 21 64 24 66 Example 8 Activity of substances in vapour form against Helminthosporium teresin barley in a greenhouse.

To determine the vapour activity, a pot containing approximately20 barley seedlings with the second leaf beginning to appear ways placed between two pots of barley on which a dry spray coating had dried after a dripping wettreatment. The dripping wet treatment was carried out at an active substance concentration of 0.1 %.Asuspension oftheconidia of the net biotch pathogen Helminthosporium teres, prepared with an aqueous solution of 0.05% sodium oleate and 0.02% gelatine and adjusted to 100,000 spores per millilitre, was sprayed over all three pots in each test sample.After spraying ofthe spores, the three pots in each test sample were enclosed in a polyethylene bag forthree days and kept under greenhouse conditions of approximately 20"C. The bagswerethen opened by cutting them at the level of the leaf tips. After 8 days, the number of net blotches per potwas counted. From this, the fungicidal vapour action was calculated as follows: 100 ~ net blotches on exposed barley. 100 - % action net blotches on unexposed barley The substances according to the invention were used as 20 % strength formulations. All vapour exposures could be tolerated by the plants.

Compound according % effect to the invention No.

2 100 3 100 4 99 10 100 13 85 Comparison agent 1-(4-Chlorophenoxy- 3,3-dimethyl-1 -(1,2,4- triazol-l-yl)-butanone 86 Example9 Systemic effect of soil treatment before emergence against sugar beet mildew Erysiphe polygoni in a greenhouse Plant pots sown with sugar beetwere sprayed with 0.3 kg of active substance per hectare and placed beside untreated pots in a greenhouse at approx imately 20"C. Afterthe beet plants had emerged (12 to 14 per pot), a waiting period was observed until the firsttwotrue leaves had developed and the plants were then inoculated by being dusted with the dry spores of true beet mildew Erysiphe polygoni. Three weeks later (six weeks after soil treatment) the attack ofthe leaves was assessed.Thefungicidal effect could have been achieved only as a result of the substances being absorbed via the plant roots and was calculated as follows: 100 - Attack in treated .100 = % effect Attack in untreated The compounds were used as 20 % strength formulations. All treatments were found to be toler able bythe plants and resulted in more vigorous and more compact growth in comparison with the untre ated control.

Compound according % effect to the invention No.

12 100 13 100 14 100 Example 10 Soya andwheat were sprayed in pre-emergence with emulsions of the test substances. The quantity applied was approximately 2 kg of active substance/ hectare. The plantswerethen cultivated in a greenhouse and measured after three weeks.

The recorded percentage growth inhibition is given intheTable.

Compound according Growth inhibition in % to the invention No. Soya Wheat 2 39 28 3 22 28 7 17 7 9 0 17 13 4 14 14 17 24 18 13 14 19 4 14 22 65 21 23 30 17 25 35 24 26 35 24 Comparison compound 2-Chloroethyltrimethylammonium chloride 0 17 Itwill be seen that, as a rule, the action ofthe compounds according to the invention is stronger than that ofthe comparison compound.

Example ii Rice was treated in pre-emerg ence with the com pounds according to the invention in application quantities of 2 kg of active substance/hectare. After three weeks' cultivation in a greenhouse, the percentage growth inhibition was determined.

This is shown in the Table.

Compound according Growth inhibition in % to the invention No.

22 11 25 7 26 14 Comparison compound 2-Chloroethyltrimethylammonium chloride 0 The growth inhibition by the compounds according to the invention was not achieved bythe comparison compound with the application used here.

Example 12 Sugar beet was sprayed in pre-emergence with an application quantity of 2 kg of active substance/ hectare. The percentage growth inhibition and the colour ofthe plants afterthree weeks' cultivation in a greenhouse were recorded.

The results are shown inthefollowingTable.

Compound according Growth inhibition in % Colour to the invention No.

1 9 1 3 34 1 7 34 0 8 37 0 9 25 1 10 37 0 12 22 0 13 41 0 14 41 0 16 53 0 17 53 0 18 22 1 19 37 -0 20 37 1 21 6 1 22 37 1 23 53 2 24 22 1 25 69 2 26 37 2 Comparison agent 2-Chloroethyltrimethylammonium chloride 0 0 * Keytocolour: 0 = as control 1 = intense green 2 = darkgreen The compounds according to the invention affect the growth of the beets whilstthe same is not achieved bythecomparison compound in the application used here.

Example 13 Effect of prophylactic leaf treatment against the leaf spot pathogen Fusarium culmorum in Italian millet (Pennisetum glaucum) in a greenhouse Young millet plants (approximately 30 per pot) with the second leaf beginning to appearwere sprayed until dripping wet with the stated concentrations.

When the spray coatings had dried, the treated plants and untreated control plants were sprayed with a suspension ofthe conidia of Fusarium culmorum and placed damp in a greenhouse at approximately 22"C.

After4days,the percentage proportion of the leaf surface attacked was estimated. The fungicidal effect was calculated as follows: 100 - 100 . Attack in treated = % effect Attack in untreated The compounds according to the invention were used as 20 % strength formulations.

Compound accprding % effect with to the invention No. 500 ppm 100 ppm 2 100 100 3 91 9 80 12 90 13 100 14 100 16 95 17 95 18 95 19 90 20 80 22 99 90 23 100 99 24 100 97 25 100 98 26 98 93 27 90 29 97 90 30 97 90 31 100 98 Example 14 Effect of prophylactic leaf treatment against the leaf spot pathogen Cercospora beticola in sugarbeetin a greenhouss Sugar beet plants having at least two well developed true leaves were sprayed until dripping wet with the stated concentrations. When the spray coatings had dried,thetreated plants and untreated control plants were sprayed with a suspension ofthe conidia of Cercospora beticola and incubated damp for 2 days in a greenhouse at 26 C.The plants were then cultivated undernormal greenhouseconditions.

Two weeks aftertreatment, the percentage attackwas assessed.

The fungicidal effectwascalculated asfollows: 100- 100 Attack in treated = % effect Attack in untreated Thecompoundswere usedas20 % strength formulations.

Compound according % effect with to the invention No. 500 ppm 100 ppn 3 100 100 11 93 12 93 13 100 14 93 16 100 17 87 19 93 20 87 21 100 96 22 100 100 23 100 100 24 100 100 25 96 96 26 100 96 27 98 98 28 100 98 29 100 98 30 100 100 31 100 100 Example 15 Effect of seed treatment against seed-borne Helmin thosporium sativum (cause offoot rot) in barley.

Barley seed infected with Helminthosporium sati vumwas treated with the activesubstance in an application quantity of 50 mg of active substance per 100 gram. 2 g of treated seed and 2 g of untreated seed were in each case sown in pots in two repetitions and incubated at 15 C in a climatic chamber. From thetimethatthe plants emerged, artificial lighting was given in a 12 hour cycle. After 4 weeks,the percentage of plants showing footrotwas determined. All the untreated plants were diseased.

Compound to the invention No. % effect 2 100 3 99.5 4 100 5 99.5 The compounds were used as 20 % strength formulations.

Example 16 Effect of seed treatment against seed-borne Phoma betaeinsugarbeet Sugar beet seed infected with Phoma betaewas treated with 250 mg of active substance per 700 gram.

25 grains of treated and of untreated seed were in each case sown in pots in four repetitions.When the plants had emerged, artificial lighting was given in a 12 hourcycle. Until the end of the test after 7 weeks, the diseased plants were counted weekly and removed. Atotal of 76.1% ofthe emerged plants in the untreated controlwerediseased.lle protective elfectofthetreatrnentwascalculated as follows: Attack in treated - 100 100 = % effect Attack in untreated The compounds according totheinventionwere used as 20% strength formulations.

Compound according to the invention No % effect 2 100 3 97 4 97 5 100 6 83 12 92 13 99 14 96 Comparison agents beta-(1,1'-Biphenyl-4-yloxy)- alpha-(1,1-dimethylethyl)- 1H-1,2,4-triazol- 1-ethanol 51 1-(4-Chlorophenoxy)- 3,3-dimethyl-1 -(1,2,4-triazol- lyl)-2-butanone 57

Claims

1. A 1,2,4-triazol-l-yl-propionitrile of the general formula

in which R represents an aryl radical which is unsubstituted or substituted by one or more of the same or different substituents selected from halogen atoms, (C1-C4) alkyl groups, (C1-C4) alkoxy groups, (C1-C4) alkylthio groups, trifluoromethyl groups and nitro groups, and R7 represents a (C1-C10) alkyl radical, (C3-C8) alkenyl radical, (C3-C8)alkynyl radical,ora phenylalkyl radical which is unsubstituted or substituted by one or more ofthe same or different substituents selected from halogen atoms, (C1-C4) allyl groups, (C1-C4) alkoxy groups, (C1 -C4) alkylthio groups, trifluoromethyl groups and nitro groups.

2. A compound as claimed in claim 1, n which R represents a phenyl radical which is unsubstituted or substituted by one or more ofthe same or different substituents selected from halogen atoms, (C1-C4) alkyl groups, (C1-C4) alkoxy groups, (C1-C4) alkylthio groups, trifluoromethyl groups and nitro groups, and R1 represents a (C1-C10) alkyl radical, (C3-C8) alkenyl radical, ora benzyl radical which is unsubstituted or substituted by one or more of the same or different substituents selected from halogen atoms, (C1-C4) alkyl groups, (C1-C4) alkoxy groups, (C1-C4) alkylthio groups,trifluoromethyl groups and nitro groups.

3. A compound as claimed in claim 2, wherein R represents a phenyl group which is unsubstituted or substituted by one or more alkyl groups and/or halogen atoms, and R1 represents a (C1-C10) alkyl group or an allyl group.

4. A compound as claimed in claim 3, wherein R represents a phenyl, 2 - chlorophenyl, 3 - chlor ophenyl, 4-chlorophenyl,2,4- dichlorophenyl, 3,4 - dichlorophenyl,4- bromophenyl, 2 -fluorophenyl,4- fluorophenyl or 2 - methylphenyl group and R1 represents an ethyl, allyl, propyl, isopropyl, butyl or hexyl group.

5. A compound as claimed in claim 4, wherein R represents a phenyl, 4 - chlorophenyl or 2 methylphenyl group and R1 represents a propyl, isopropyl or butyl group.

6. An acid addition salt of a compound as claimed in any one of claims 1 to 5 with an inorganic or organic acid.

7. An acid addition salt as claimed in claim 6, which is a hydronitrate salt.

8. 2- Isopropoxy- 2-phenyl -3- (1, 2,4-triazol - I yl) - propionitrile hydronitrate.

9. 2-Isopropoxy-2-phenyl-3-(1,2,4-triazol yl) - propionitrile.

10. 2-Hexyloxy-2-(2- methylphenyl) -3-(1,2,4- triazol - I - yl) - propionitrile hydronitrate.

11. 2-Butoxy-2-(2- methylphenyl)-3-(1,2,4- triazol-l-yl)- propionitrile.

12. 2-Butoxy-2-(2-methylphenyl)-3-(1,2,4- triazol - I -yl) - propionitrile hydronitrate.

13. 2-Hexyloxy-2-(2- methylphenyl)-3-(1,2,4- triazol - I -yl) - propionitrile.

14. 2-Butoxy-2-phenyl-3-(1,2,4-triazol-l-yl)- propionitrile hydronitrate.

15. 2-Butoxy-2-(2-chlorophenyl)-3-(1,2,4- triazol - I -yl)- propionitrile hydronitrate.

16. 2-Ethoxy-2-phenyl-3-(1,2,4-triazol-l-yl)- propionitrile hydronitrate.

17. 2-Phenyl-2-propoxy-3-(1,2,4-triazol-lyl)- propionitrile hydronitrate.

18. 2-(3-Chlorophenyl)-2-hexyloxy-3-(1,2,4- triazol-l-yl)- propionitrile hydronitrate.

19. 2-Butoxy-2-phenyl-3-(1,2,4-triazol-l-yl)- propionitrile.

20. 2-Phenyl-2-propoxy-3-(1,2,4-triazol - I yl) - propionitrile.

21. 2-Ethoxy-2-phenyl-3-(1,2,4-triazol-l-yl)- propionitrile.

22. 2-Hexyloxy-2-phenyl-3-(1,2,4-triazol-l- yl) - propionitrile hydronitrate.

23. 2-Allyoxy-2-phenyl-3-(1,2,4-triazol-l-yl) - propionitrile hydronitrate.

24. 2-Butoxy-2-(4-chlorophenyl)-3-(1,2,4- triazol - I -yl) - propionitrile hydronitrate.

25. 2 -Allyloxy-2- phenyl-3-(1,2, 4-triazol-l-yl) - propionitrile.

26. 2-Methoxy-2-phenyl- 3-(1,2,4-triazol-I- yl) - propionitrile,

27. 2- Hexyloxy- 2 - phenyl -3 - (1,2,4-triazol - I yl) - propionitrile.

28. 2-(2-Chlorophenyl)-2-hexyloxy-3-(1,2,4- triazol - I -yl)- propionitrile hydronitrate.

29. 2 - (2- Chlorophenyl) -2-propoxy-3- (1,2,4- triazol - I -yl)- propionitrile hydronitrate.

30. 2-(4-Chlorophenyl)-2-propoxy-3- (1,2,4triazol - I -yl) - propionitrile hydronitrate.

31. 2-(4-Chlorophenyl)-2-hexyloxy-3- (1,2,4triazol - I -yl)- propionitrile hydronitrate.

32. 2- 4-Chlorophenyl)-2-propoxy-3- (1,2,4- triazol - I -yl) - propionitrile.

33. 2- Butoxy-2- (4-chlorophenyl)-3-(1, 2,4 triazol - l -yl) propionitrile.

34. 2-(2-Methylphenyl)-2-octyloxy-3-(1,2,4triazol - I -yl) - propionitrile hydronitrate.

35. 2-DecyIoxy-2- (2- methylphenyl)-3-(1,2,4 triazol - l-yl)- propionitrile hydronitrate.

36. 2-(2-Methylphenyl-2-octyloxy-3- (1,2,4- triazol - I -yl) - propionitrile.

37. 2-Butoxy-2-(2- chlorophenyl)-3-(l, 2,4- triazol - I -yl) propionitrile.

38. 2-(2-Chlorophenyl)-2- propoxy-3-(1,2,4- triazol - I - yl) - propionitrile.

39. 2- Butoxy-2- (2,4-dichlorophenyl)-3-(1,2,4 - triazol - I - yl) - propionitrile hydronitrate.

40. 2- Butoxy-2- (2,4- dichlorophenyl) -3 - (1,2,4 -triazol - I -yl) - propionitrile.

41. 2-Allyoxy-2- (2,4 - dichlorophenyl) - 3 - (1,2, 4-triazol - I -yl) - propionitrile.

42. 2 - (3,4 - Dichlorophenyl)-2 - propoxy-3- (1,2, 4-triazol - I -yl) - propionitrile hydronitrate.

43. 2 - (3,4 - Dichlorophenyl) -2 - propoxy-3- (1,2, 4-triazol - I -yl) - propionitrile.

44. 2 - (3,4 - Dichlorophenyl)- 2- hexyloxy-3- (1, 2,4 -triazol - I -yl)- propionitrile hydronitrate.

45. 2- (3,4- Dichlorophenyl)- 2- hexyloxy-3- (1, 2,4-triazol-l-yl)-propionitrile.

46. 2-(4-Fluorophenyl)- 2-propoxy-3-(1,2, 4- triazol - I -yl)- propionitrile hydronitrate.

47. 2-(4-Fluorophenyl)-2-propoxy-3-(1,2,4- triazol - I -yl) - propionitrile.

48. 2-Butoxy-2- (4-fluorophenyl)-3- (1,2,4- triazol - I -yl) - propionitrile hydronitrate.

49. 2-Butoxy-2-(4-fl uorophenyl)-3-(1,2, 4- triazol - I -yl) - propionitrile.

50. 2 - (2 - Fluorophenyl)-2-propoxy-3-(1,2,4- triazol - I - yl) - propionitrile hydronitrate.

51. 2-(2-Fluorophenyl)-2-propoxy-3-(1,2,4 triazol - I - yl) - propionitrile.

52. 2-Butoxy-2- (2-fluorophenyl)-3-(1,2,4triazol - I - yl) - propionitrile hydronitrate.

53. 2-Butoxy-2-(2-fluorophenyl)-3-(1,2,4- triazol-l-yl)- propionitrile.

54. 2-(2-Fluorophenyl)-2-hexyloxy-3-(1,2,4- triazol - l-yl)- propionitrile hydronitrate.

55. 2- (2 - Fluorophenyl) -2-hexyloxy-3- (1,2,4- triazol -I-yI)-propionitrile.

56. 2- (4-Bromophenyl)- 2- propoxy-3 (1,2,4triazol - I-yl) - propionitrile hydronitrate.

57. 2-(4- Bromophenyl) -2- propoxy-3- (1,2,4 triazol-l-yl)- propionitrile.

58. 2-(4-Bromophenyl)-2- hexyloxy-3(1,2, 4triazol - I - yl) - propionitrile hydronitrate.

59. 2-(4-Bromophenyl) -2- hexyloxy-3-(1,2,4- triazol - I - yl) - propionitrile.

60. 2-(2,4-Dichlorophenyl) -2- propoxy-3- (1,2, 4-triazol - I -yl) - propionitrile hydronitrate.

61. 2 - (2,4 - Dichlorophenyl) -2 - propoxy-3-(1,2, 4-triazol -I -yl) - propionitrile.

62. 2- (2- Methylphenyl) -2- pentyl -3- (1,2,4- triazol - I - yl) - propionitrile hydronitrate.

63. 2-(2- Methylphenyl)2- pentyl -3- (1,2,4 triazol - I -yl) - propionitrile.

64. 2- (4- Methylphenyl)-2- propoxy - 3 (1,2,4- triazol - l-yl) - propionitrile hydronitrate.

65. 2-Hexyloxy-2- (4- -Hexyloxy-2-(4- methylphenyl) -3- (1,2,4triazol - I - yl) - propionitrile hydronitrate.

66. 2-(4- Methylphenyl) -2 - propoxy-3- (1,2,4- triazol - I - yl) - propionitrile.

67. 2 - Hexyloxy - 2 - (4 - methylphenyl) - 3- (1,2,4- triazol - I - yl) - propionitrile.

68. 2- Butoxy-2-(4-methylphenyl)-3-(l, 2,4- triazol - I - yl) - propionitrile.

69. A processforthe preparation of a compound ofthe general formula i as claimed in claim 1, or an acid addition salt thereof, which comprises reacting a compound of the general formula

in which R and R1 have the meanings given in claim 1 and Y represents a halogen atom or an alkylsul phonyloxy or aryl sulphonyloxy radical which is optionally halogenated in the side chain with 1,2,4 triazole ofthe formula

oran alkali metal derivative thereof if desired in the presence of a solvent and, optionally, in the presence of a base and, if desired, a compound ofthe general formula I is converted into an acid addition salt thereof with an inorganic or organic acid and/or an acid addition salt is converted into a corresponding free compound ofthe general formula I.

70. A process as claimed in claim 69, which is carried out at a temperature in the range of from 100 to 200*C.

71. A process as claimed in claim 69, which is carried out substantially as described herein.

72. A process as claimed in claim 69, which is carried out substantially as described in Example 1 or Example 2 herein.

73. A compound as claimed in claim 1, or an acid addition saltthereof, whenever prepared buy a pro cess as claimed in any one of claims 69 to 72.

74. A biocidal preparation which comprises at least one compound selected from compounds of the general formula I given in claim 1 and salts thereof with inorganic and organic acids, in admixture or conjunction with a suitable carrier.

75. A biocidal preparation which comprises a compound as claimed in any one of claims 2 to 5,7 to 68 and 73, in admixture or conjunction with a suitable carrier.

76. A preparation as claimed in claim 740rclaim 75, which is in theform of a powder, a strewable preparation, granules, a solution, an emulsion or a suspension.

77. A preparation as claimed in any one of claims 74to 76, which also contains one or more active substances selected from defoliants, plant-protecting agents and pesticides otherthan compounds ofthe general formula land salts thereof.

78. A preparation as claimed in any one of claims 74to 77, wherein the total amount present of active substance or substances is in the range offrom 10 to 90% by weight.

79. A preparation as claimed in any one of claims 74to 78, containing asurface-active agent in an amount of upto 20% by weight.

80. A preparation as claimed in any one of claims 74to 79, which also contains colouring matter.

81. A biocidal preparation as claimed in claim 76, which is substantially as described herein.

82. A biocidal preparation as claimed in claim 76, which is substantially as described in any one of Examples 3 to 16 herein.

83. A method of protecting a living plant against weeds and/orphytopathogenicfungi and/orofreg- ulating its growth, wherein the living plant and/or the area in the vicinity of the living plantis/aretreated with a compound selected from compounds of the general formula I given in claim 1 and saltthereof with inorganic or organic acid.

84. A method as claimed in claimed 83, wherein the treatment is carried out with a compound as claimed in any one of claims 2 to 5, 7to 68 and 73.

85. A method as claimed in claim 83, wherein the treatment is carried out with a preparation as claimed in any one of claims 74to 79,81 and 82.

86. A method as claimed in any one of claims 83 to 85,wherein a compound selected from compounds of the general formula land salts thereof is used for the treatment in an amount in the range of from 0.05 to 5 kg per hectare.

87. A method as claimed in claim 83, conducted substantially as described in any one of Examples 3 to 6and8to 14 herein.

88. A method of protecting a crop area against weedsand/orphytopathogenicfungi and/orof reg ulating the growth of plants in the area, wherein the crop area is treated with a compound selected from compounds ofthe general formula I given in claim 1 and saltsthereofwith inorganic and organic acids.

89. A method as claimed in claim 88, wherein the treatment is carried out with a compound as claimed in any one of claims 2 to 5,7 to 68 and 73.

90. A method as claimed in claim 88, wherein the treatment is carried out with a preparation as claimed in any one of claims 74to 79,81 and 82.

91. A method as claimed in anyone of claims 88 to 90, wherein a compound selected from compounds ofthe general formula I and salts thereof is used for the treatment in an amount in the range of from 0.05 to 5 kg per hectare.

92. A method as claimed in any one of claims 88 to 91, wherein the crop is a plantation crop.

93. A method as claimed in any one of claims 88 to 91, wherein the crop is a cereal, cotton, sugar, or soya bean crop.

94. A method of dressing seeds, wherein the seeds are treated with a compound selected from compounds of the general formula I given in claim 1 and salts thereof with inorganic and organic acids.

95. A method as claimed in claim 94, wherein the treatment is carried out with a compound as claimed inanyoneofclaims2to5,7to68and73.

96. A method as claimed in claim 94, wherein the treatment is carried out with a preparation as claimed in any one of claims 74 to 82.

97. A method as claimed in claim 92, conducted substantially as described in Example 15or 16 herein.

98. A method of protecting a substrate against bacteria, wherein the substrate is treated with a compound selected from compounds of the general formula I given in claim 1 and salts thereof with inorganic and organic acids.

99. A method as claimed in claim 98, wherein the treatment is carried outwith a compound as claimed in any one of claims2to 5,7to 68and73.

100. A method as claimed in claim 98, wherein the treatment is carried out with a preparation as claimed in any one of claims 74to 79, 81 and 82.

101. A method as claimed in anyone of claims 98 to 100, wherein the substrate is a living plant or an area in the vicinity ofthe living plant.

102. A method as claimed in any one of claims 98 to 100, wherein the substrate is an inanimate object.

103. A method as claimed in claim 98, conducted substantially as described in Example 7 herein.

104. A packwhich comprises a compound selected from compounds of the general formula I given in claim 1, and saltsthereofwith inorganic and organic acids, together with instructions for its use as a herbicide and/orfungicide and/or bactericide and/or for regulating the growth of a living plant.

105. A packwhich comprises a compound as claimed in any one of claims 2to 5,7to 68, and 73 togetherwith instructionsfor its use as a herbicide and/orfungicide and/or bactericide and/orfor reg ulating growth of a living plant.

106. Acompound of the general formula

in which R, R and Y have the meanings specified in claim 69.

107. A compound of the general formu la

in which R and R1 have the meanings specified in claim 1.