NL8300748A - 1,2,4-TRIAZOL-1-YL-PROPIONITRILLES, PROCESS FOR THE PREPARATION OF THESE COMPOUNDS, AND BIOCIDES CONTAINING THESE COMPOUNDS. - Google Patents

Description

• * ^ w '> VO 4592 Λ

Title 1, 1,2,4-Triazol-1-yl-propionitrile process for the preparation of these compounds, as well as biocides containing these compounds.

The invention relates to new 1,2,4-triazol-1-yl-pro-pionitriles, to a process for the preparation of these compounds, as well as to biocides containing these compounds, in particular those having a fungicidal activity .

Imidazolyl-propionitrile derivatives with a fungicidal activity are already known (DE-OS '2604047}. However, they show a relatively narrow spectrum of action, which is unsatisfactory.

The object of the present invention is to develop new propionitrile derivatives which open up wide-ranging applications, in particular in the field of plant protection, and which exhibit a wide spectrum of action as a fungicide.

This problem is solved according to the invention by immidazolyl-propionitriles of the general formula 1, in which R is an optionally single or multiple, mutually equal or different by halogen, (C 1 -C 2 -alkyl, (C 1 - C 1 -alkoxy, (C 1 -C 2) -alkylthio, trifluoromethyl or a nitro group substituted aromatic hydrocarbon radical and R 1 (C 1 -C 12 Ql-alkyl, (C 1 -C 8 alkenyl, (Cg-Cg) -) alkynyl or an optionally single or multiple, mutually identical or different by halogen, (C 1 -C 2) alkyl, (C 1 -C 1) alkoxy, (C 1 -C 1 J -alkylthio, trifluoromethyl or a nitro - 2Q represents a substituted phenylalkyl radical and its acid addition salts with inorganic and organic acids.

The compounds of the invention act in the broadest sense as biocides; they stand out. however, in particular due to their fungicidal action, in which they surprisingly surpass known active compounds having analogous constitution and direction of action.

The fungicidal activity is surprisingly directed against fungi in the most diverse systematic places. In the treatment of itself. Above ground plant parts provide protection against wind-borne pathogens. Against seed-transmitting pathogens, the compounds can be used for seed treatment. In addition, they work systemically, ie they are absorbed by the roots of the plants, for example, after they have been introduced during sowing, they are transported to the above-ground parts of the plants and protect them. these against pathogens.

As other actions can be mentioned: a growth regulating action and a bactericidal action.

Due to the observed broad spectrum of action, the compounds are suitable not only for the protection of cultivated plants, but also for the protection of material and for the control of human pathogenic and animal pathogenic micro-organisms, resulting in widely spread applications. .

Depending on the special significance of the substituents, areas of application with a center of gravity emerge here, whereby the compounds develop excellent properties. For example, they can always be used as fungicides, plant growth regulators or bactericides.

For the compounds represented by the general formula 1, 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, 3-2Q iodophenyl, 4-iodophenyl, 2,4-dichlorophenyl, 3,4-dichlorophenyl, 2,6-di-a · ... /, .. chlorphenyl, 2-meth.ylphenyl, 3 -methylphenyl, 4-methylphenyl, 2-ethylphenyl, 3-ethylphenyl, 4-ethylphenyl, 2-propylphenyl, 3-propylphenyl, 4-propylphenyl, 2-isopropylphenyl, 3-isopropylphenyl, 4-isopropylphenyl, 2-butylphenyl, 3- butylphenyl ,. 4-Butylphenyl, 2-sec-butylphenyl, 3-sec-butylphenyl, 4-sec-butylphenyl, 2-tert-butylphenyl, 3-tert-butylphenyl, 4-tert-butylphenyl, 2-methoxy-phenyl, 3-methoxyphenyl, 4-methoxyphenyl, 2-ethoxyphenyl, 3-ethoxyphenyl, 4-ethoxyphenyl, 2-methylthiophenyl, 3-methylthiophenyl, 4-methylthiophenyl, 2-ethylthiophenyl, 3-ethylthiophenyl, 4-ethylth ± ofenyl, 2 -trifluoromethylphenyl, 3-trifluoromethylphenyl, 4-trifluoromethylphenyl, 2-nitrophenyl, 3-nitro-3 phenyl, 4-nitrophenyl, 3-fluoro-4-methoxyphenyl, 3-chloro-5-nitrophenyl, 4- chloro-2-fluorophenyl, 3,4,5-trimethoxyphenyl or 2-chloro-2-nitrophenyl and may

For example, propose: (C 1 -C 3, JL-alkyl, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, isopropyl, 2,2-dimethylpropyl-1,3,3- dimethyl-hutyl-2., (Cg-Cg] -alkenyl, For example 2-Buten-1-yl, 3-methyl 1-2- 8300748 «4 - 3-buten-1-yl, hexenyl, heptenyl, octenyl phenylalkyl, for example benzyl, 2-fluorobenzyl, 3-fluorobenzyl, 4-fluorobenzyl, 2-chlorobenzyl, 3-chlorobenzyl, 4-chlorobenzyl, 2-bromobenzyl, 3-bromobenzyl, 4-bromobenzyl, 2,4-dichlorobenzyl, 2,6-dichlorobanzyl, 3,4-dichlorobenzyl, 2-methylbenzyl, 5-methylbenzyl, 4-methylbenzy1, 2-nitrobenzy1, 3-nitxobenzyl, 4-nitrobenzyl, 2-trifluoromethylbenzy 1,3, 3-trifluoromethylbenzy 1,4 -trifluoromethylbenzy 1,2-methoxybenzyl, 3-methoxybenzyl, 4-methoxybenzy1, 2-ethoxybenzyl, 3-ethoxybenzyl, 4-ethoxybenzyl, 2-propoxybenzyl, 3-propoxybenzyl, 4-propoxybenzyl, 1-butoxybenzyl, 3-butoxybenzyl , 4-butoxybenzyl, 2-methylthio-benzyl, 3-methylthiobenzyl, 4-methylthiobenzyl, 2-ethylthiobenzyl, 3-th thylthiobenzyl, 4-ethylthiobenzyl, 2-butylthiobenzyl, 3-butylthiobenzyl, 4-butylthiabenzyl.

As inorganic and organic acids for the formation of acid addition salts, mention may be made, for example, of hydrohalic acid, such as, for example, hydrochloric acid and hydrobromic acid, furthermore phosphosic acid, sulfuric acid, and in. in particular nitric acid, mono and bifunctional carboxylic acids and hydroxycarboxylic acids, such as, for example, acetic acid, maleic acid, tartaric acid, fumaric acid, tartaric acid, citric acid, salicylic acid, sorbic acid, lactic acid, as well as sulfonic acids, such as, for example, p-toluenesulfonic acid and 1, 5-naphthalene disulfonic acid.

These acid addition salts can be prepared in accordance with the usual salt form; Methods, for example by dissolving a compound of the formula I in a suitable solvent and adding the acid, are obtained.

The compounds according to the invention are distinguished by a fungicidal action, in particular those representatives, wherein in the general formula 1 the residue R is phenyl, 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, 2,4-dichlorophenyl, 3Q 3 4-dichlorophenyl, 4-bromophenyl, 2-fluorophenyl, 4-fluorophenyl or 2-methylphenyl and R 1 ethyl, allyl, propyl, isopropyl, butyl or hexyl.

Of these, preferred compounds are those compounds wherein 8300748 * * - 4 - R phenyl, 4-chlorophenyl and 2-methylphenyl and R 1 propyl, isopropyl or butyl.

The following compounds of the invention show excellent activity 2-isopropoxy-2-phenyl-3- (1,2 ', 4-triazol-1-yl) -propionitrile, hydronitrate, 2-butoxy-2- (2-methylphenyl 3-(1,2,4-triazol-1-yl) -propionitrile, hydronitrate, 2-phenyl-2-propoxy-3- (1,2,4-triazol-1-yl) -propionitrile, hydronitrate, 2-butoxy-2- (4-chlorophenyl) -3- (1,2,4-triazol-1-yl) -propionitrile, hydronitrate 10, 2- (4-chlorophenyl) -2-propoxy-3 - (1,2,4-triazol-1-yl) -propionitrile, hydronitrate, 2-isopropoxy-2-phenyl-3- (1,2,4-triazol-1-yl) -propionitrile, 2-butoxy-2 - (2-methylphenyl) -3- (1,2,4-triazol-1-yl) -propionitrile, 2-hexyloxy-2-phenyl-1-3- (1,2,4-triazol-1-yl) - propionitrile, hydronitrate, 2-butoxy-2- (4-chlorophenyl) -3- (1,2,4-triazol-1-yl) -propionitrile, 2- (4-chlorophenyl) -2-propyloxy-3- (1 2,4-triazol-1-yl) -propionitrile, 2-hexyloxy-2- (2-methylphenyl) -3- (1,2,4-triazol-1-yl) -propionitrile; .hydro-nitrate, 2-butoxy-2-phenyl-3- (1,2,4-triazol-1-yl 1-propionitrile, hydronitrate, 2-butoxy-2- (2-chlorophenyl-3- (1 2,4-triazol-1-yl) -propionitrile, hydronitrate, 2-ethoxy-2-phenyl-3- (1,2,4-triazol-1-yl) -propionitrile, hydronitrate, 2-allyloxy -2- phenyl-3- (1,2,4-triazol-1-yl-propionitrile, hydronitrate, 2- (2-chlorophenyl) -2-propoxy-3- (1,2,4-triazol-1-yl-propionitrile) , hydronitrate, 2- (4-chlorophenyl 1 -2-hexyloxy-3— (1,2,4-triazol-1-yl) -propionitrile, hydronitrate, 2-hexyloxy-2- (2-methylphenyl 1 -3- (1,2,4-triazol-1-yl) -propionitrile, 3Q 2-butoxy-2-phenyl-3- (1,2,4-triazol-1-yl-propionitrile, 2- (2- chlorophenyl) -2-butoxy-3- (1,2,4-triazol-1-yl) -propionitrile, 2-ethoxy-2-phenyl-3- (1,2,4-triazol-1-yl-propionitrile , 2-allyloxy -2-phenyl-3— (1,2,4-triazole-1-yl i-propionitrile, 2- (2-chlorophenyl-2-propoxy-3- (1,2,4-triazole) 1-yl) -propionitrile.

The compounds according to the invention show in particular a fungicidal action, but at the same time are distinguished in a series of cultivated plants by growth-regulating effects.

Depending on the type of plant and the amount used, herbicidal effects also occur.

Since the compounds of the invention cause both qualitative and quantitative changes in plants and changes in plant metabolism, they should be classified in the class of plant growth regulators, which are distinguished by the following uses: vegetative growth on woody and herbaceous plants, for example on the edges of streets, on rail yards and others, in order to prevent lush growth; growth inhibition in corn, prevention of lying down and bending, increase of yield in cotton; Influencing the branching of vegetative and generative organs in ornamental or cultivated plants to increase the number of leaf principles, or in tobacco, and tomatoes to slow down side shoots; improvement of the fruit quality, for example an increase in the sugar content of cane sugar, sugar beet or ooft, and a 2Q more uniform ripeness of the crop, which leads to higher yields; increasing resistance to climatic influences, such as cold and drought; influencing latex flow in rubber plants; Parthenocarpic fruit formation, pollen sterility and sex influences are also applications; control of seed germination or bud budding; defoliation or influencing the falling of fruit to facilitate the harvest.

The compounds of the invention are particularly suitable for influencing the growth of beet roots; however, they also show desirable growth-regulating effects in corn, soy and cotton.

The amounts to be applied are generally from 0.5 to 5 kg of active compound / ha, depending on the application purpose; possibly larger quantities can also be used.

The time of application depends on the application purpose and the 8300748 »i - 6 climatic conditions.

Surprisingly, the compounds of the invention are active in a broader range or to a greater extent than the products known in practice with the same direction of action.

v.

In addition to the aforementioned actions, the compounds according to the invention also have a bactericidal effect, which makes other applications possible.

The compounds of the invention can be used either alone or mixed together or mixed with other active compounds. If desired, other plant protection agents or pest control agents may be added according to the desired purpose.

It is recommended that the labeled active compounds or their mixtures be in the form of preparations, such as powders, litters, granules, solutions, emulsions or suspensions, with the addition of liquid and / or solid carriers or diluents and optionally wetting, adhesive - to use emulsifying and / or dispersing agents. -

Suitable liquid carriers are, for example, water, aliphatic and aromatic hydrocarbons, such as benzene, toluene, xylene, cyclo-2Q hexanone, isophorone, dimethyl sulfoxide, dimethyiformamide, further fractions of mineral oils, and vegetable oils.

Suitable solid carriers are mineral earths, for example tonsil, silica gel, talc, kaolin, attapulgite, limestone, silicic acid and vegetable products, for example flours.

25. As surface active compounds can be mentioned, for example, calcium lignin sulfonate, polyoxyethylene alkyl phenyl ethers, naphthalene sulfonic acids and their salts, formaldehyde condensation products, fatty alcohol sulfates, as well as substituted benzene sulfonic acids and salts thereof.

If the active compounds are to be used for pickling seeds 30, dyes can also be mixed to give the pickled seeds a clearly visible color.

The content of the active compound (and 1 in the various preparations may vary within wide limits. For example, the agents may comprise from about 10 to 30% by weight of active compounds, from about 90 to 35% by weight of liquid or solid carriers, as well as optionally highest 2Q wt% surfactants.

8300748! | Ti - 7 -

The application of the agents can take place in the usual manner, for example, with water as a carrier, in amounts to be sprayed of about 100 to 1000 liters / ha. The use of the agents in the so-called "Low-volume" or "Ultra-low-volume" process is just as possible as their use in the form of so-called micro-granulates.

For example, the following ingredients are used for the preparation of the preparations; A. Spray powder a) 40 wt.% Active compound ^ 25 wt.% Clay minerals 20 wt.% Silicic acid 10 wt.% Celpek 5 wt.% Surfactants based on a mixture of the calcium salt of lignin sulfonic acid with alkyl phenol polyglycol ethers b 25 wt% active compound 60 wt% kaolin 10 wt% silica 5 wt% surfactants based on the sodium salt of 20 N-methyl-N-oleyl-taurine and the calcium salt of lignin sulfonic acid c) 10 wt% active compound 6Q wt. % clay minerals 15 wt% silica 25 10 wt & cell pitch 5 wt% surfactants based on the sodium salt of N-methyl-N-oleyl-taurine and the calcium salt of lignin sulfonic acid.

B. Paste 30 45 wt.% Active compound 5 wt.% Sodium aluminum silicate 15 wt.% Cetylpolyglycol ether with 8 mol ethylene oxide 2 wt. % spindle oil 10 wt. % polyethylene glycol 35 23 parts water 8300748-8 ° C. Emulsion concentrate 25% by weight active compound 15% by weight cyclohexanone 55% by weight xylene 5% by weight mixture of nonylphenylpolyoxyethylene and calcium dodecylbenzenesulfonate.

The new compounds of the invention can be prepared.

. using a method known for analog connections.

The new compounds according to the invention can be prepared, for example, by propionitriles of the general formula 2 in opposition. in the presence of a solvent and optionally in the presence of a base to be reacted with 1,2,4-tazazole of the formula III or its alkali compounds, wherein in the formula II Ren have the above meaning and Y halogen or an optional halogenated alkyl-15 sulfonyloxy or an arylsulfonyloxy residue in the side chain.

For example, the following can be mentioned as halogen: chlorine, bromine or iodine? suitable alkylsulfonyloxy radicals are, for example, methyl, ethyl, propyl and the trifluoromethylsulfonyloxy group, while arylsulfonyloxy radicals may include, for example, the benzylsulfonyloxy group and the p-toluene-2Q sulfonyloxy group.

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

Suitable solvents are: relative to the reaction compo. inert substances, preferably with a polar, aprotic character, such as N, N-dimethylformamide, ΙΓ, Ν-dimethylacetamide, N-methylpyrrolidone, tetramethylurea, hexamethylphosphoric triamide and benzonitrile, but also high-boiling aromatic and aliphatic hydrocarbons, such as toluene, chlorine or xylene.

The reaction temperature can. are varied within wide limits.

Preference is given to a temperature between 100 ° C and 20 ° C. The conversions take place at normal or elevated pressure.

The 1,2,4-triazol-1-yl-propionitriles of the invention are generally substantially colorless and odorless solids. The acid addition salts derived therefrom are 8300748-9. also colorless and odorless, crystalline compounds. The free bases are only soluble in water and somewhat soluble in organic solvents, such as, for example, alcohols, ethers or chlorinated hydrocarbons. The acid addition salts 5 are partially soluble in water and readily soluble in polar organic solvents, such as acetonitrile, N, N-dimethylformamide, low alcohols, chloroform and methylene chloride.

The preparation of the compounds according to the invention is further illustrated by the following examples.

10 Example X

2-Isopropoxy-2-phenyl-3 ~ (1,2,4-triazol-1-yl) -propionitrile, hydronitrate compound number 2.

To sodium hydride (0.55 mol) suspended in 50 ml of dry DMF was added 0.55 mol of 1,2,4-triazole with stirring and cooling. Then 0.11 mol of 2-isopropoxy-3-methyl-sulfonyloxy-2-phenyl-propionitrile in 50 ml DMF was added and the mixture was kept at a bath temperature of 150 ° C for 1.5 hours ... After cooling, three times extracted with 100 ml ether, the combined ether phases were washed twice with water and dried with MgSO 4. The ether was concentrated by rotary evaporation under reduced pressure, after which 50 ml of isopropanol was added to the residue and 6.8 ml of concentrated nitric acid was added dropwise with cooling and stirring. After addition of 80 ml of ether, the mixture was stirred for another 1/4 hour and then filtered off. Recrystallized from isopropanol.

M.p .: 185-189 ° C (decompn.). Yield: 15 g * 43% of theory.

DMF * dimethylfonnami.de Example IX

2-Isopropoxy-2-phenyl-3- (1,2,4-triazol-1-yl) -propionitrile Compound number 3 3Q In methanol, 10 g of 2-isopropoxy-2-phenyl-3- (1,2,4 triazol-1-yl) propionitrile, hydronitrate dissolved, 8 ml of 32% ammonia water was added. It was then poured onto water, extracted with ethyl acetate, dried with MgSO4, the ethyl acetate was concentrated by rotary rotation under reduced pressure, a little ethyl acetate and activated carbon were added, boiled briefly, filtered off 8300748-10 and concentrated again by rotation. The thus solidified solid was analysis pure.

M.p .: 176-177 ° C

Yield: 6/65 g = 83% of theory. In an analogous manner, the following compounds according to the invention could be prepared.

No. and name of the compound Physical constant 1. 2-Hexyloxy-2- (2-methylphenyl) -3- (1,2,4-triar * Mp .: 159-62 ° C · 10 zol-1-yl } -propionitrile, hydronitrate (dec.)

4.2-Butoxy-2- (2-methylphenyl) -3- (1,2,4-triazole- Mp: 58-62 ° C

1-yl) -propionitrile

5.2-Butoxy-2- (2-methylphenyl) -3- (1,2,4-triazole- Mp: 158-61 ° C

1-yl) -propionitrile, hydronitrate (dec.) 15 6. 2-Hexyloxy-2- (2-methylphenyl) -3- (1,2,4-triria.n. 40: 1.5121 sole-1- yl) -propionitrile

7.2-Butoxy-2-phenyl-3- (1,2,4-triazol-1-yl) - Mp: 159-60 ° C

propionitrile, hydronitrate (dec.)

8.2-Butoxy-2- (2-chlorophenyl) -3- (1,2,4-tria- Mp: 142.5-44 ° C

20-sol-1-yl) -propionitrile, hydronitrate (dec.)

2-Ethaxy-2-pheny 1-3- (1,2,4-triazol-1-yl) - m.p .: 169-70 ° C

propionitrile, hydronitrate (dec.)

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

propionitrile, hydronitrate (dec.)

25 11. 2- (3-Chlorophenyl) -2-hexyloxy-3- (1,2,4-tria- Mp: 173-75 ° C

sole-l-yl) -propionitrile, hydronitrate (dec.)

2-Butoxy-2-pheny1-3- (1,2,4-triazol-1-yl) - Mp: 67-68 ° C

propionitrile

13. 2-Phenyl-2-propoxy-3- (1,2,4-triazol-1-yl) - Mp: 107-08 ° C

Propionitrile

14. 2-Ethoxy-2-pheny1-3- (1,2,4-triazol-1-yl) - Mp: 74-75 ° C

propionitrile

15. 2-Hexyloxy-2-pheny1-3- (1,2,4-triazol-1-yl) - Mp: 158-60 ° C

propionitrile, hydronitrate (dec.)

35 16. 2-Allyloxy-2-pheny 1-3- (1,2,4-triazol-1-yl) - m.p .: 145-47 ° C

propionitrile, hydronitrate (dec.) 8300748

No. and name of, the connection Physical constant - 11 -

17. 2-Butoxy-2- (4-chlorophenyl} -3- (1,2,4-tria- Mp: 173-75 ° C

sole-l-yl) -propionitrile, hydronitrate (dec.)

5 18. 2-Allyloxy-2-phenyl-3- (1,2,4-triazol-1-yl) - Mp: 86-88 ° C

propionitrile 19.2-Methoxy-2-phenyl-3- (1,2,4-triazol-1-yl) - m.p .: 77-79 ° C propionitrile

20. 2-Hexyloxy-2-phenyl-3- (1,2,4-triazol-1-yl) - Mp: 58-60 ° C

Propionitrile

21. 2- (2-Chlorophenyl-2-hexyloxy-3- (1,2,4-tria- m.p .: 157-59 ° C

sole-l-yl} -propionitrile, hydronitrate (dec.)

22. 2- (2-Chlorophenyl) -2-propoxy-3- (1,2,4-tria- Mp: 138-39 ° C

sole-l-yl) -propionitrile, hydronitrate (dec.)

15 23. 2- (4-Chlorophenyl) -2-propoxy-3- (1,2,4-tria- Mp: 155-57 ° C

sole-l-yl) -propionitrile, hydronitrate (dec.)

24. 2- (4-Chlorophenyl) -2-hexyloxy-3- (1,2,4-tria- Mp: 155-59 ° C

sole-l-yl) -propionitrile, hydronitrate (dec.)

25. 2- (4-Chlorophenyl) -2-propyloxy-3- (1,2,4-tria-m.p .: 115-19 ° C

20 sole-1-yl) -propionitrile

26. 2-Butoxy-2- (4-chlorophenyl) -3- (1,2,4-tria- Mp: 54-60 ° C

sole-1-yl) -propionitrile

27. 2- (2-Methylphenyl) -2-octyloxy-3- (1,2,4-tria- Mp: 128-34 ° C

sole-l-yl) -propionitrile, hydronitrate (dec.)

25 28. 2-Decyloxy-2- (2-methylphenyl) -3 '(1,2,4-tria-m.p .: 116-20 ° C

sole-1-yl) -propionitrile, hydronitrate (decomposition) 29. 2- (2-Methylphenyl) -2-octyloxy-3- (1,2,4-triannQ2Q: 1.4930.

sole-1-yl) -propionitrile 3Q. 2- (2-Chloro-phenyl) -2-Butoxy-3- (1,2,4-triphenol 40: 1,5273 sole-1-yl) -propionitrile 31. 2- (2-Chlorophenyl) -2 -propoxy-3- (1,2,4-tria-nQ40: 1,5308 sole-1-yl) -propionitrile

32. 2-Butoxy-2— (2,4-dichlorophenyl) -3- (1,2,4- m.p .: 163-66 ° C

triazol-1-yl) -propionitrile, hydronitrate

35 33. 2-Butoxy-2- (2,4-dichlorophenyl) -3- (1,2,4- Mp: 53-55 ° C

triazol-1-yl) -propionitrile 8300748

No. and name of the connection Physical constant - 12 -

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

triazol-1-yl) -propionitrile

5 35. 2- (3,4-Dichlorophenyl) -2-propoxy-3- (1,2,4- Mp: 152-55 ° C

triazol-1-yl) -propionitrile, hydronitrate (dec.) 36. 2- (3,4-Dichlorophenyl] -2-propoxy-3- (1,2,4- m.p .: 60-66 ° C triazole -1-yl) -propionitrile

37. 2- (3,4-Dichlorophenyl) -2-hexyloxy-3- (1,2,4- m.p .: 166-68 ° C

10 triazol-1-yl) -propionitrile, hydronitrate 38. 2- (3,4-Dichlorophenyl) -2-hexyloxy-3- (1,2,4-η ^ 40: 1,5240 triazol-1-yl) - propionitrile

39. 2- (4-Fluorophenyl) -2-propoxy-3- (1,2,4-tria- Mp: 172-75 ° C

sole-l-yl) -propionitrile, hydronitrate (dec.)

15 4Q. 2- (4-Fluorophenyl) -2-propoxy-3- (1,2,4-tria- m.p .: 98-100 ° C

sole-1-yl) -propionitrile

41. 2-Butoxy-2- (4-fluorophenyl) -3- (1,2,4-tria- Mp: 173-75 ° C

sole-l-yl) -propionitrile, hydronitrate (dec.)

42. 2-Butoxy-2- (4-fluorophenyl) -3- (1,2,4-tria- Mp: 56-58 ° C

2Q sole-1-yl) propionitrile

43. 2- (2-Fluorophenyl) -2-propoxy-3- (1,2,4-tria- Mp: 150-53 ° C

sole -l-yl) -propionitrile, hydronitrate (dec.)

'44. 2- (2-Fluorophenyl) -2-propoxy-3- (1,2,4-tria- Mp: 66-69 ° C

sole-1-yl) -propionitrile

25 45. 2-Butoxy — 2- (2-fluorophenyl) -3- (1,2,4-tria- Mp: 138-43 ° C

sole-l-yl) -propionitrile, hydronitrate (dec.)

46. 2-Butoxy-2- (2-fluorophenyl) —3- (1,2,4-tria- Mp: 76-79 ° C

sole-1-yl) -propionitrile

47. 2- (2-Fluorophenyl) -2-hexyloxy-3- (1,2,4-tria- Mp: 134-37 ° C

3Q sole-1-yl] -propionitrile, hydronitrate (dec.)

48. 2- (2-Fluorophenyl) -2-hexyloxy-3- (1,2,4-tria- Mp: 58-60 ° G

sole-1-yl) -propionitrile

49. 2— (4-Bromophenyl) -2-propoxy-3- (1,2,4-tria- m.p .: 150-53 ° C

sole-l-yl) -propionitrile, hydronitrate (dec.)

35 50. 2- (4-Bromophenyl) -2-propoxy-3- (1,2,4-tria- Mp: 118-21 ° C

sole-1-yl) -propionitrile 8300748

No. and name. of the compound Physical constant - 13 -

51. 2- (4-Bromophenyl) -2-hexyloxy-3- (1,2,4-triacryl-16L-64 ° C

sole-l-yl) -propionitrile, hydronitrate ,, \ ontiX /

5 52. 2— (4-Bromophenyl) -2-hexyloxy-3- (1,2,4-tria- Mp: 60-62 ° C

sole-1-yl) -propionitrile

53. 2- (2,4-Dichlorophenyl) -2-propoxy-3- (1,2,4-tria- Mp: 166-70 ° C

sole-l-yl) -propionitrile, hydronitrate (dec.)

54. 2- (2,4-Dichlorophenyl) -2-propoxy-3- (1,2,4- Mp: 61-63 ° C

Triazole) -propionitrile

55. 2— (2-Methylphenyl) -2-penty 1-3- (1,2,4-tria- Mp: 151-54 ° C

sole-1-yl) -propionitrile, hydronitrate (dec.) 56. 2- (2-Methylphenyl) -2-pentyl-3- (1,2,4-triand40: 1,5111 sole-1-yl) propionitrile

57. 2- (4-Methylphenyl) -2-propoxy-3- (1,2,4-tria- Mp: 170-71 ° C

sole-l-yl) -propionitrile, hydronitrate (dec.)

58. 2-Hexyloxy-2- (4-methylphenyl) -3- (1,2,4-tria- Mp: 177-81 ° C

sole-l-yl) -propionitrile, hydronitrate (dec.)

59. 2- (4-Methylphenyl) -2-propoxy-3- (1,2,4-tria-m.p .: 120-24 ° C

20-sol-1-yl) -propionitrile 60. 2-Hexyloxy-2- (4-methyl-phenyl-1-3- (1,2,4-triandD4Q: 1 ^ 5065) -sole-1-yl) -propionitrile

61. 2-Butoxy-2- (4-methylphenyl1-3- (1,2,4-tria- Mp: 71-73 ° C)

sole-1-yl) -propionitrile 25

The 3-aryl or 3-alkylsulfonyloxypropionitriles of the general formula II with Y as aryl or alkylsulfonyloxy to be used as starting material have not been described in the literature so far.

3Q. These can be obtained by the methods known in part or by methods known per se (compare, for example, Rubin et al., JACS67, 192 et seq. (1945); Hess et al., Ber. Dt. Chem. Ges. 50, 394 (1917)) phenylacetonitriles of the general formula 4, in which R and R 1 have the meaning stated for formula 1, by hydroxymethylation by methods known per se and the 3-hydroxypropionitriles of the general formula 5 thus obtained with suitable sulfonic acid derivatives, 8300748 - 14 - such as, for example, sulfonic acid chlorides / optionally with the addition of an acid binder, - The hydroxymethyl compounds of the general formula 4 are not known so far in the literature.

The preparation of a starting product is described below.

5 3-Methylsulfonyl-2-phenyl-2-propoxy-propionitrile

In. 120 ml of pyridine, 27 g (0.154 mol) of 2-phenyl-2-propoxy-acetonitrile were dissolved and 18.5 g (0.614 mol) of paraformadehyde were added. On. this suspension was added with ice cooling 7.7 ml of tetrabutyl ammonium hydroxide (TBAOH) as 40% solution, followed by vigorous stirring. After several hours (DC control was poured onto ice water and extracted with ether. The ether phase was washed with dilute hydrochloric acid and then with sodium chloride solution, then dried with magnesium sulfate. After the desiccant had been filtered off and concentrated by rotation under reduced pressure, a colorless oil remained, which was found to be homogeneous by thin layer chromatography and which could be further processed without further purification.

Yield! 28.4 g (® 90% of the theoretical 3-Hydroxy-2-phenyl-2-propoxy-propionitrile.

20 ηβ: υ; 1.5027.

28 g (0.136 mole of 3-hydroxy-2-phenyl-2-propoxy-propionitrile) were dissolved in 200 ml of toluene, after which 19.5 g (0.171 mole of methanesulfonic acid chloride was added.

18.6 g (0.184 mol of triethylamine) was added dropwise at 1 ° C. After stirring at ambient temperature for 30 minutes, the precipitated triethylamine hydrochloride was filtered off and the filtrate was concentrated. The residue was taken up in ether, washed with water and magnesium sulfate dried and concentrated The oily residue was found to be pure by thin layer chromatography.

Yield: 32.27 g (= 86% of the theoretical 3-methylsulfonyl-2-phenyl-2-pro-3Q poxypropionitrile.

20 nD * h: 1.5QQQ.

The following exemplary embodiments serve to illustrate the application possibilities of the compounds according to the invention, which were in the form of the above-mentioned preparations.

Example III

8300748 - 15 -

Prophylactic leaf treatment against powdery mildew /

Erysiphe graminis, bee barley in a greenhouse »

Young barley plants in the stage of the first leaf were sprayed with the indicated concentrations dripping wet. After the spray coat had dried, the treated plants, as well as untreated control plants, were inoculated with dry mildew spores by coating the test plates with infested plants. Then, the test plants were grown in a greenhouse at about 20-22 ° C and after one week the percentage of leaf surface attack was appreciated. The fungicidal activity was calculated as follows: attack on treatment. 100 100 - -............- '- - —------------------ -------—' »% effect damage without treatment

The compounds were used as 20% FS formulations.

15

Compound according to the Erysiphe graminis, invention No. % Operation 500 ppm 100 ppm 20 ‘l 10Q 95 2 100 59 3 100 100 4 100 100 5 '100 95 25 6 100 94 7 100 100 8 1QQ 100 9 100 100 IQ 1QQ 100 30 11 100 94

12 10Q 1QQ

13 1QQ 1Q0 14 100 1Q0

15 100 1QQ

35 16 100 10Q

8300748

Compound according to the Erysiphe graminis, invention No. % Operation 500 ppm 100 ppm - 16 - 17 100 100 5 18 100 100 19 100 100 20 100 100 21 100 95 22 100 100 10 23 100 100 24 100 25 100 - 26 100 28 100 95 15 30 100 100 31 100 100 33 100 100 34 100 100 35 100 100 20 36 100 100 38 100 100 41 100 100 42 100 100 44 100 100 25 48 100 95 49 100 100 50 100 1Q0 51 100 100 52 10Q 100 30 53 100 1Q0 54 100 100 55 100 1Q0

57 10Q 1QQ

58 100 100 35 59 100 100 6Q 100 '100 8300748

Compound according to the Erysiphe graminis, invention No. % Operation 500 ppm 100 ppm - 17 - 61, 100 100 5

Example IV

Effect of the prophylactic leaf treatment against Erysiphe cichoacearuni in pumpkin plants in a greenhouse.

IQ Pumpkin plants sprayed with dripping wet spray with the indicated concentrations of active compound were dried after drying the sprayed layer by dusting dry mildew spores of Erysiphe: Cichoracearum and incubated together with the inoculated untreated control plants at 24 ° C. After a week, the affected mildew area in% of the total leaf area was estimated. The fungicidal activity was calculated as follows: 10Q. damage during treatment - 10Q - —..... ...... »% effect ---- damage without treatment

2Q

The designation "s" in the table below means that the fungicidal activity could also be assessed by the growth of the plants (after treatment} 'and found positive. That is, the active compounds were systemic transported to fouling and also had a 10% mildew activity therein.

The compounds of the invention were used as 20% formulations.

Connections 3Q. according to the invention Erysiphe cichoracearum,

No% Operation 250 25 5 2.5 0.5 ppm 1 lOQs 100s 100s 2 lOQs 100s 100s 35 3 100s 100s 100s 4 lOQs lOOs 100 8300748

Compounds..according to the Erysiphe cichoracearum, invention No% Effect 250 25 5 2.5 0.5 ppm -18- 5 100s 100s 100 5 6 100s 100s 100 7 100 100 100 8 100s 98 100 9 100s 100s 100s -10 100s 100s 100 '10 - 11 100s 100s 100 12 100s lOQs 100 13 lOQs' 14 lOQs 100s 100 15 100s 100 1Q0 15 16 lOQs 100 99.5 17 1'OOs 100s lOQs 18 100s IQOs 100 19 lOQs 100' 97 20 100s 20 21 100s 100 90 22 100s 100 100 27 lOQs 29 LOOs 32 lOOs 25 37 lOOs 39 lOOs 40 lQOs 43 lOQs 45 lOOs 3Q 46 lOOs 47 lOOs 56 lOOs

Example V

35 Effect (%) in prophylactic leaf treatment against Helminth osporium 8300748 - 19 - teres (- Pyrenophora teres), net spot disease in barley.

Young barley plants in the stage of the first leaf were sprayed with the indicated concentrations dripping wet. After the spray coat had dried on, the treated plants and untreated control plants were sprayed with a suspension of the conidio spores of Helminthosporium teres and incubated in a damp room for 2 days at 20-22 ° C. The plants were then grown in a greenhouse at 20-22 ° C. One week after inoculation, the percentage of leaf surface attack was noted. The fungicidal activity was calculated as follows: attack on treatment. 100 100 - ...... ...........- - ---------- -% effect of attack without treatment

The compounds were used as 20 * s formulations.

15

Compounds according to the Helminthosporium teres invention No. fc operation 500 ppm 100 ppm 10 ppm 1 1QQ 100 '20 2' 100 100 100 3 100 100 90 4 95 95 90 5 100 100 6 99 25 7 98 90 8 83 9 1QQ 85 IQ. 95 95 11 100 90 3Q 12 94 90 13 92 85 14 89 80 15 94 90 IS 94 80 35 17 89 8300748

Compounds according to the Helminthosporium teres invention No. % Operation 500 ppm 100 ppm 10 ppm - 20 - 18 1Ό0 70 5 19 94 20 70 23 85 - 24 95. 90 25 95 95 10 26 80 27 90

Example VI

Action of the prophylactic leaf treatment against dwarf rust, Puccinia 15 hordei / bee barley in a plant culture room with climate control.

Young barley plants in the first leaf stage were treated with. sprayed the specified concentration dripping wet. After the spray coating had dried on, the treated plants, as well as untreated control plants, were inoculated by coating with dwarf corroded plants and placed in a plant culture chamber. The plants were grown at 15 ° C for 10 days and in substantially air-saturated air for the first two days. Thereafter, the percentage of leaf surface affected by rust was noted. The fungicidal activity was calculated as follows:

damage to treatment, 1QQ

1QQ - - =% effect attack without treatment. The compounds were used as 20% formulations.

Compounds according to Puccinia hordei, the invention No. % Operation .500 ppm .. 1QQ ppm 20 ppm.

35 1 100 77 2 100 83 .8300 74 8

Compounds according to Puccinia hordei, the invention No. % Operation 500 ppm 100 ppm 20 ppm - 21 - 3 5 4 100 100 89 5 100 100 94 6 100 94 7 100 98 89 8 100 94 94 10 9 80 10 100 98 94 11 89 12 84 13 89 15 14 95 80 15 95 16 78 17 100 100 100 18 98 20 19 95 20 85 21 100 70 22 100 100 23 79 25 24 r 90 70 25 90 90 27 85 3Q 95 31. 95 30

Example VII

Action against Pseudomonas phaseolicola, causative agent of the fat spot disease in beans, in vitro.

Biomout agar was cooled to about 45 ° C after heat sterilization and then poured into the Petri dishes made of plastic, mixed with the test compounds into an aqueous preparation. After solidification of the culture medium, the dishes with treated agar, as well as the dishes with untreated agar as control in the center, were inoculated by means of an oculation eye with a suspension of the fat stain agent Pseudomonas phaseolicola. The dishes were then incubated at 22 ° C. After 2.5 weeks, the radial expansion of the grown colonies of the bacteria was measured. From the average of 2 replicates per test unit, the bacterial inhibitory activity was calculated as radial growth upon treatment as follows. 100 100 - '..............' '................... —......% braking effect radial growth without treatment

The compounds were used as 20% formulations.

Compound of% Activity at Concentration of Invention, No. 250 ppm active compound 12. 62 15 73 21 '64 20 24 66

Example VIII

Effect of the vapor against Helminthosporlum teres in barley in a greenhouse.

To determine the action of the vapor, a pot containing about 2Q

barley seedlings at the stage of the incipient second leaf placed between two barley pots with dried, sprayed layer from a drip-wet treatment. The dripping treatment was performed with. a concentration of active compound of 0.1%. Per test unit, a conidial suspension of the net stain agent, Helminth osporium teres, which was prepared with an aqueous solution of Q, Q5% sodium molate and 0.02% gelatin and sprays per ml on all 30 pots was sprayed. was set. After spraying on the spores, the three pots per test unit were locked in polyethylene bags for 3 days and kept under greenhouse conditions of about 20 ° C. The bags were then opened by cutting them at the blade tips. After 8 days, the number of 8300748 - 23 - net spots per pot was counted. From this the vapor action as a fungicide was calculated as follows: net spots on exposed barley. 100 100 - -------------- 1 .....- —'1 - =% effect 5 net spots on barley not exposed

The compounds of the invention were used as 20% formulations. All vapors were tolerable for the plants.

10

Compound of the invention, No. % Operation 2 100 3 100 15 4 99 10 100 13 85

Comparative agent 2Q 1- (4-Chlorophenyl-3,3-dimethyl-1-86 (1,2,4-triazol-1-yl-butanone)

Example IX

Systemic action of the treatment of the soil, before hatching, against milkweed mildew, Eryslphe polygon !, in a greenhouse.

Plant pots were sprayed with Q, 3 kg of active compound per ha after sowing sugar beets, and placed next to untreated pots in a greenhouse at about 20 ° C. After the beet plants (12 - 14 per pot) emerged, they waited until the first two deciduous leaves had developed in the plants, after which inoculation was carried out by pollinating the dry spores of the true beet mildew, Erysiphe polygoni. Three weeks later (6 weeks after the soil treatment, the attack of the leaves was appreciated. The action as fungicide could only be effected by the incorporation of the compounds via the plant roots and was calculated as follows: 8300748 - 24 - treatment attack. 100 * 100 - ............... 1 --------------—............. =% effect ^ attack without treatment

The compounds were used as -20% formulations. All treatments were found to be tolerable for the plants and, compared to the untreated control, led to more vigorous, more compact growth.

Compound of the invention, No. % Operation 12 100 13 1Q0 14 100

Example X.

Soy and wheat were sprayed with emulsions of the test compounds before emergence. The amount used, converted, was 2 kg of active compound / ha. The plants were then grown in a greenhouse and measured after 3 weeks.

The registered percentage growth inhibitions are shown in the table.

*

Compounds, according to the Growth inhibition in% 25 invention, No, ...... Soy Wheat 2 39 28 3 22 28 7 17 .7 30 9 0 17 13 4 14 14 17 24 18 13 14 19 4 14 35 22 65 21 23 30 17 8 300 748

Compounds, According to the Growth Inhibition in% Invention, No. Soy Wheat - 25 - 25 35 24 26 35 24 5 Comparative compound 2 - <-> ear ethyl trimethyl ammonium chloride 0 17

It has been found that the compounds according to the invention are generally more effective than the compound used for comparison.

Example XI

Rice became. treated with the compounds according to the invention in amounts of 2 kg active compound / ha. The percentage growth inhibition was established after 3 weeks of cultivation in a greenhouse. This is listed in the following table.

15

Compounds of the invention, No. Growth inhibition in% 22 11 20 25 7 26 14

Comparison connection

2-Chloroethyl trimethyl ammonium chloride Q

The growth inhibition caused by the compounds of the invention did not occur in the present administration of the comparative compound.

Example XXX

Sugar beets were sprayed at a rate of 2 kg of active 3Q compound / ha before emergence. The percentage growth inhibition and the coloring of the plants was registered after 3 weeks Greenhouse culture. The results are shown in the following table.

35 8300748

Compound according to the invention, No Growth inhibition in% Staining ^ - 26 - 1 9 1 3. 34 1 5 7 34 0 8 37 0 9 25 1 '10 37 0 12 22' 0 10 13 41 0 14 41 0 • 16 53 0 17 53 0 18 22 1 15 19 37 0 20 37 1 21 6 1 22 37 1 23 53 2 20 24 22 1 25 69 2 26 37 2

Comparative agent 2-Chloroethyltimeth.yl-25 anmonium chloride% Staining table: 0 = as in control 1 = intensive green 2 = dark green 30 The compounds of the invention influence the growth of the beets, which is due to the comparative compound in the present administration was not reached.

Example XIII

Effect of the prophylactic treatment against the leaf spot softener, Fusarium culmorum, on millet cob (Pennisetum glaucum). in a greenhouse 8300748 - 27 -.

Young millet plants (about 30 per pot) in the early second leaf stage were sprayed with the indicated concentrations dripping wet. After the spray coating had dried on, the treated and untreated control plants were sprayed with a conidia suspension of Fusarium culmorum and placed moist in a greenhouse at about 22 ° C. After four days, the percentage of affected leaf area was estimated. The effect as a fungicide was calculated as follows: 10 1 (90. Attack With Treatment 1Q0 -, .... - - a% effect ---- - attack without Treatment

V

The compounds of the invention were used as 20% formulations.

15

Compound according to% Effect with the invention, No ..... 5Q0.dpm ....... 100, ppm 1 8300748 100 100 20 3 91 9 .80 12 90

13 1QQ

14 100 25 16 95 17 95 18 95 19 90 20 80 30 22 99 90 23 10Q 99 24 100 97 25 100 98 26 98 93

35 27 9Q

29. 97 90 /; - 28 -

Compound according to% Operation with the invention 500 ppm 100 ppm 30 97 90 31 100 98 5

Example XIV

Effect of the prophylactic leaf treatment against the leaf spot causative agent Cercospora beticola in sugar beets in a greenhouse.

Sugar beet plants with at least two well-developed deciduous leaves were sprayed with the indicated concentrations dripping wet. After the spray coating had dried on, the treated plants and the untreated control plants were sprayed with a conidium suspension of Cercospora beticola. and incubated moist in a greenhouse at 26 ° C for 2 days. The plants were then grown under normal greenhouse conditions. Percentage impairment was assessed two weeks after treatment.

The fungicidal activity was calculated as follows: 1QQ. impairment of treatment 1QQ - · ............ 1 =% effect of impairment without treatment 20

The compounds were used as 20% formulations.

Compound according to% Operation with the invention, No ...... SQQ.dpm. .. 100 ppm 25 -: -: - * --- 3 1QQ 100 11 93 12 93 '

13 1CLQ

3Q 14 93

16.1QG

17 87 19 93 20. 87 35 21 1QQ 96 22 1QQ 100 8300748

Compound according to% Operation with the invention, No. 500 ppm 100 ppm - 29 - 23 100 100 24 100 100 5 25 96 96 26 100 96 27 98 98 28 100 98 29 - 100 · 98 10 30 100 100 31 100 100

Example XV

Effect of the treatment of seeds against seed borne Helminthosporxum sativum (causative agent of foot disease) in barley. _____ ____

Helminthoporium sativum, contaminated barley seed was treated with an amount of 50 mg of active compound per 100 g. For each treatment, as well as no treatment, 2 g of seed was sown in pots with 2 repetitions and at 15 ° C in a room Incubated with climate control. From the emergence of the plants, met. a 12-hour rhythm artificially exposed. After 4 weeks, the percentage of plants with foot disease was determined. In the cases where no treatment took place, all plants were diseased.

25 'Connection according to the.

invention, No.% Operation

2 1QQ

3 99.5 30 4 100 5 99.5

The compounds were used as 2Q% formulations.

Example XVI

35 Effect of seed treatment against seed-carried Phoma betae 8300748 - 30 - for sugar beet »

Sugar beet seed contaminated with Phoma betae was treated with an amount of 250 mg of active compound per 100 g. Of the treated, as well as of. the untreated seeds were sown in a pot for 4 repetitions per 5 grains and placed in a room with air-conditioning at 15 ° C. After the plants hatched, artificial lighting was performed with a 12-hour rhythm. Until the end of the 7 week trial, the diseased plants were counted weekly and removed. In total, 76.1% of the emerging plants fell ill during the untreated control. The protective effect of the treatment was calculated as follows: attack on treatment. 100 100 - --------------. - ... ........ - - ss% effect attack without treatment The compounds according to the invention were used as 20% formulations.

Compound of the invention, Nr% Effect 20: 2 100 3 / .97 4 97 5 100 25 6 83 12 92 13 99 14 96 Comparative ^ 0- (1,11-Biphenyl-^-yloxy) -a- (1, 1-dimethylethyl) - 1H-1,2, U-triazole-1-ethanol 51 1 - (i + -Chloro-phenoxy) -3,3- <umethyl-1 - (1,2, h-triazol-1-yl -2-butanone 57 35 8300748

Claims (7)

64. Process for the preparation of 1,2,4-triazol-1-yl-propionitrile-10 len, characterized in that the compounds according to any one of claims 1-63 are prepared using a known for analogous compounds method. 65. A process for the preparation of 1,2,4-triazol-1-yl-propionitrile, characterized in that the compounds according to any one of claims 1 to 63 are prepared by compounds of the general formula 2 in presence of a solvent and. optionally in the presence of a base react with 1,2,4-triazole of the formula 3 or its alkali compounds, wherein in the formula R 2 have R 1 and the above meaning and Y halogen or an optionally halogenated alkyl - 20 represents sulfonyloxy residue or an arylsulfonyloxy residue. 66. A process for the preparation of biocides, characterized in that one or more compounds according to any one of claims 1-63 are introduced into a biocidal dosage form. 67. A method according to claim 66, characterized in that the compositions according to any one of claims 1-63 have a fungicidal action. 68. A method according to claim 66, characterized in that the compounds according to any one of claims 1-63 have a growth regulating effect. 62. A method according to claim 66. characterized in that the compounds according to any one of claims 1 to 63 have a bacterial effect. 70. Formed biocides obtained by using the method according to any one of claims 66-62. 35 8300748 J. κ 0. R, 1 1 R - C - CH_ - TST j i * 2 ^ —A 2 3 O - R. N - CH R C - CH - Y I ^ R | U 2 HC N C N XN / H '4 5 <? “R1? * R1 R - CH R - C - CH2 - OH CN CN 8 3 0 0 7 4 8 Schering Aktiengesellschaft