CS244127B2 - Fungicide,growth regulating and bactericidal agent - Google Patents

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

The present invention relates to a fungicidal, growth-regulating and bactericidal composition comprising 1,2,4-triezol-1-ylpropionitrile as active ingredient and to a process for the preparation of these active ingredients.

Inidazolylpropionitrile derivatives with fungicidal activity are already known, for example from German Patent Publication No. 26 04 047. However, these compounds show relatively narrow epectrons of activity, which is unsatisfactory.

SUMMARY OF THE INVENTION It is therefore an object of the present invention to provide novel propionitrile derivatives which open wide-ranging applications, particularly in the field of plant protection, and which exhibit a broad spectrum of fungicidal activity.

According to the invention, this object is solved by the discovery of a novel fungicidal, growth-regulating bactericidal composition which contains, as active ingredient, imidasols of propionitriles of the general formula X

(I) Who

R is phonyl optionally substituted once or twice with halogen or C1-C4alkyl, and

R 6 represents a C 1 -C 10 alkyl or allyl group, and / or a hydronitrate thereof.

In the broadest sense, the compounds according to the invention are fungicidally, growth-regulating and bactericidally active, but which are particularly fungicidal. Surprisingly, the novel compounds outperform the tolerant active ingredients of analgesic constitution and type of action.

Surprisingly, the fungicidal effect is recorded against fungi of various systetic classification. Plants are protected from wind-borne diseases when applied to the adhesive parts. Seeds can be treated with the indicated compounds against seed germs. In addition, the compounds according to the invention act systematically, that is, for example, from roots of roabs, after planting treatment, they reach the aerial parts of the plants and protect the aerial parts against disease.

Further effects of the composition according to the invention consist in growth-regulating and bactericidal action.

Due to their broad spectrum of activity, the compounds are suitable not only for the protection of crop plants, but also for the protection of material and for the control of pathogenic microorganisms in humans and animals, where they offer a wide range of applications.

. ^ hyl is>

Depending on the special meaning of the industry, the application in a particular field of

They can be used as fungicides, growth regulators or bytecericides.

Particular values of the substituents of the compounds of formula I include:

R 2 -fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 2-chlorophenyl, 3-chlorophenyl,

4-chlorophenyl, 2-bronzeines, 3-bromumphenes, 4-bromumphenyl-1,2-iodophenyl, 3-iodophenyl, 2,4-dichlorophenyl, 2,4-dichlorophenyl, 3,4-dichlorophenyl, 2,6-dichlorophenyl ,

2-methylphenyl-3-methylphenyl, 4-methylphenyl-2- (1-yl) -1,3-ethylphenyl, 4-ethylphenyl, 2-propylphenyl, 3-ylphenylphenyl, propylphenyl, 2,2-propylphenyl,

3-isoyroylpentyl-1,4-isoylopropyl-1,2-sec-butylphenyl, 1,2-sec-butylphenyl, 1,2-sec-butylphenol, 3-sec. 2-tert-butylphenyl, 2-tert-butylphenyl, 2-tert-butylphenyl, 2-tert-butylphenyl, 2-tert-butylphenyl, 4-chloro-2-fluorophenyl or 4-chloro-2-fluorophenyl; R, C1-C10alkyl such as methyl, ethyl, propyl, buuyl, pentyl, hexyl, heppyl, octpl, nonpl, decyl, isoproppl, 2,2-dimethyl-1-yooyl, 3,3-dimethyl -2-butyl or allyl.

The substrate of the compound of formula (I) may be obtained by conventional salt-forming procedures, for example by dissolving the compound of formula (I) in a suitable solvent and adding an acid to the solution.

Ze. The compounds according to the invention are characterized by fungicidal activity, in particular those compounds in which, in the general formula (I), the substituent R denotes phenyl, 2-chlorophenyl, 3-chlorophenyl, 4- (2,4-dihydrophenyl), 3,44 bromobutyl, 1,2-methyl, 1,4-pentyl or 2-methylphenyl; and R, ethyl, allyl, propyl, isopropyl, butyl or hexyl.

Preferred are compounds in which R is phenyl, 4-chlorophenyl or β-methylphenyl and R is phenyl, isuyruyl or butyl.

Significant effects are shown by the following compounds: 2-isopropoxy-2-: phenyl-3- (1,2,4-thiazol-1-yl) -thiol-3-one, hyddootraate, 2-№2-α2- (2-№4) .1) -3- (1,2,4-toiazul-1-1l) -youpotetril, hydrotrihydrate, 2-phenylethyl-1,2,3-triazol-1-yl 3-butyrotriole, 2-butoxy-4- (4-trifluoromethyl) -3- (1,2,4-triazole-1-iD-youpiiotetril), halo-rotate, 2- (4-cM) (1 ', 4', 1 ', 4', 3 ', 2', 4 ', 4', 8'(1'-2'-yl) -pyrrolidinotriol, 2-isoyropyloyl-2'-isopropyl-2- (1', 2,4 '). thiazol-1-yl) -pyrrolidin-3-one, 2-butO2 -12- (2-methyl-1-yl) -3- (1,2,4-triazol-1-yl)) -rooioitrile, 2-hydroxy-12-oxo-1-en (1) 2,4-thiazol-1-yl) -10-oxo-thioate, 2-butyloxy, 2-butyloxy-2- (4-chloro-phenyl) -3- (1,2,4-thiazol-1-yl-4-yroo-pioitrile), 2- (4-chloro-pyrrole) 2-pyrrolyl-3- (1,2,4-thiazol-1-yl-D-yroo-propyl) -2-hexyl-1,3-yl-2- (2-methylphenyl) -3- (1,2,4-toiazol-1-yl) - yrooioottril, hydronate, 2-Sulfoyl-2-yl-1- (1,2,4,4-triazol-1-yl) -yrroleOttt01, hyldootiret,

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) -2-hexyloxy-3- (1,2,4-triazol-1-yl) -propionitrile, hydronitrate,

2-hexyloxy-2- (2-methylphenyl) -3- (1,2,4-triazol-1-yl) propionitrile,

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-triazol-1-yl) -propionitrile,

2- (2-chlorophenyl) -2-propoxy-3- (1,2,4-triazol-1-yl) propionitrile

The compounds of the present invention exhibit particularly fungicidal effects, but at the same time, a number of crop plants exhibit a growth-regulating effect.

Depending on the type of plant and the amount applied, a herbicidal effect also occurs.

Since the compounds of the present invention cause both qualitative and quantitative changes in plants as well as changes in plant metabolism, they are classified in the plant growth regulators class, characterized by the following uses:

Suppression of vegetative growth of woody and herbaceous plants, for example at roadside, rail subsoil and the like, to prevent lush growth. Suppression of grain growth to prevent lodging or breaking, or cotton to increase yield.

Influencing the branching of vegetative and generative organs of ornamental or cultural plants to increase their deployment to the flower or, in the case of tobacco and tomatoes, suppression of side shoots;

Improving the quality of the products, such as increasing the sugar content of sugar cane, sugar beet or fruit and more uniform ripeness at harvest, which leads to increased yields.

Increasing plant resistance to climatic conditions such as cold and drought.

Influence of latex flowability in rubber trees.

Other uses include the creation of fetuses without fertilization, pollen sterility and affecting the genera.

Check seed germination or seed buds.

Distilling or influencing fruit falling to facilitate harvesting.

The compounds according to the invention are particularly suitable for influencing the growth of sugar beet, but they also show growth-regulating effects on cereals, salts and bsvloy.

Depending on the intended use, the application rate is generally 0.05 to 5 kg of active substance per hectare, or higher doses may be used.

Usage time depends on the purpose of use and climatic conditions ·

Surprisingly, the compounds of the present invention are broader or more potent than known products of the same type of action.

In addition to the above-mentioned effects, the active compounds according to the invention also exhibit bacterial effects which open up further possibilities for the use of the preparation.

The active compounds according to the invention can be applied alone, in admixture with one another or in admixture with other active substances. Depending on the intended use, other protective or pest control agents may optionally be added.

Suitably, they apply the active compounds according to the invention or mixtures thereof in the form of preparations such as powders, sprinkles, granules, solutions, emulsions or suspensions, with the addition of liquid and / or solid carriers or diluents and with the addition of binders, emulsifiers and / or dispersing aids.

Suitable carriers are, for example, water, aliphatic and aromatic hydrocarbons such as benzene, toluene, xylene, cyclohexanone, isophorone, dimethylsulfoxide, dimethylformemide, mineral oil fractions and vegetable oils.

Suitable solid carriers are minerals such as tonsil, silica gel, talc, kaolin, attapulgite, limestone, silicic acid, and also plant products such as flour.

Suitable surfactants include, for example, calcium ligninsulfonate, polyoxyethylene alkylphenyl ether, naphthalenesulfonic acids and their salts, formaldehyde condensates, fatty alcohol sulfates, and substituted benzenesulfonic acids and their salts.

Where the active substances in question are to be used for seed dressing, colorants may be added to them in order to give the pickled seed a distinct coloring.

The proportion of the active compounds according to the invention in the various preparations can vary within wide limits. For example, the composition contains 10 to 90% by weight of active ingredient, 90 to 10% by weight of liquid or solid carrier, and optionally up to 20% by weight of surfactant.

Application of the compositions can take place by conventional means, for example with water as the carrier in spray quantities of 100 to 1000 liters per hectare. The use of the so-called low-volume or ultra-low-volume means is also possible, as well as so-called microgranules.

For example, the following components may be used to manufacture the formulations:

A. Dust

(a) 40% by weight% by weight% by weight of the active substance mineral clay silicic acid pitch surfactants based on a mixture of lignin sulphonic acid calcium salt with alkylphenol polyglycoliters

(b) 25% by weight% by weight

(c) 10% w / w% by weight of the active substance kaolin silicic acid surfactant based on sodium salt of N-methyl-N-oleyl-teurine and calcium salt of lignin sulphonic acid:

Mineral clay active compounds Silicic acid pitch Surfactants based on the sodium salt of N-methyl-N-oleyl-taurine and calcium selinine sulphonic acid ·

B. Paste by weight% by weight% by weight 10% by weight 23% by weight of the active substance sodium aluminum silicate cetyl polyglycol * ter with 8 moles of spindle oil ethylene oxide polylylene glycol water.

C. Emulsion concentrate% by weight 15% by weight 55% by weight of the active substance cyclohexanone xylene nonylphenyl polyoxyethylene or calcium dodecylbenzenesulfonate

The present invention further provides a process for the manufacture of an active ingredient. The novel compounds are prepared according to the invention by reacting the propionitrile of the general formula II.

H-C-CH-Y (II)

AND

CN wherein R and R R are as defined above and

Y is methylsulfonyloxy, with 1,2,4-triazole of the formula

N — CH

II hc. _n , m

H

The reaction is conveniently carried out in the presence of a solvent and optionally in the presence of a base.

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

Suitable solvents are substances inert to the reactants, preferably of a polar aprotic nature, such as, for example, dim, Ν-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, tetramethylurea, phosphoric acid hexamethylamide and benzonitrile, but also higher boiling aromatic and aliphatic. hydrocarbons such as toluene, chlorobenzone or xylene

The reaction temperature can vary within a wide range. Temperatures of 100 to 200 ° C are preferred. The reaction can take place under normal pressure and under positive pressure.

The 1,2,4-triazol-1-ylpropionitriles which are the active compounds according to the invention are generally solids, practically colorless and odorless. The acid addition salts derived therefrom are also colorless and odorless, formed by crystalline substances. The free bases are poorly dissolved in water but more or less well in organic solvents such as alcohols, ethers or chlorinated hydrocarbons. some dissolve in water and well in polar organic solvents such as acetonitrile, Ν, Ν-dimethylformamide, lower alcohols, chloroform and methylene chloride. The following examples illustrate the preparation of the active compounds according to the invention.

Example 1

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

Compound # 2

0.55 mol of 1,2,4-triazole is added to 0.55 moles of sodium hydride suspended in 50 ml of dried dimethylformamide with stirring and cooling. Then 2-isopropoxy-3-methylsulfonyloxy-2 is added to the reaction mixture. of phenyl-propionitrile in 50 ml of dimethylformamide and the batch is left for 1.5 hours at a bath temperature of 150 ° C. After cooling, the mixture is extracted three times with 100 ml of ether, the combined ether phases are washed twice with water and dried over anhydrous magnesium sulphate. 6.8 ml of concentrated nitric acid. After addition of 80 ml of diethyl ether, the reaction mixture is stirred for a further 15 minutes and then filtered off with suction. The residue was recrystallized from isopropyl alcohol.

Melting point: 185-189 ° C (decomposition)

Yield: 15 g - 43% of theory

Example 2

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

Compound No. 3 g of 2-isopropoxy-2-phenyl-3- (1,2,4-triezol-1-yl) -propionitrile was dissolved in methanol and treated with 8 mL of 32% ammonia water. The reaction mixture is poured into ₍ water, extracted with ethyl acetate, dried and anhydrous magnesium sulphate and ethyl acetate are evaporated on a rotary evaporator in vacuo. The residue is mixed with a small amount of ethyl acetate and activated carbon, briefly charged with activated carbon The mixture is filtered and the solvent is again evaporated on a rotary evaporator under vacuum.

Melting point: 176-177 ° C

Yield: 6.65 g 83% of theory ·

The following compounds can be prepared in an analogous manner.

No. Compound name β physical constant

I. 2-nicox103x-2- (2-ethylphenyl) -3- (1,2,4-triezol-1-yl) -propiooitrile, hydro-hydrate m.p .: 159-162 ° C (decomposition)

4. Glycerin-4- (2-methylphenyl) -3-1,2,4-tert-16-zol-llyl (bis-capilnitiil) melting point: 58 to 62 ° C

5 · 2-butt "yi-2 (2--1 ₉ 2.4-t ^ id ^ asoi-i ^ (i ^ l (<^ i ^ i ^ pj ^ <^ 2ntt ^ i ^ l _l tydronltrát temperature m.p .: 158-161 ° C (decomposition)

6. 2-Hexyloxi-2- (2-methylphenyl) -3- (1,2,4-triezolyl) piropionitrile

Λ ⁴⁰ : 1.512 1

7 * 2-butoxi-2-phenil-3- (1,2,4-thiazol-1-yl) (piperidinolithi) hydronitoate melting point: 159-160 ° C (decomposition)

8. 2-b □ tory-2- (2-e] tLorriftl1-II _((2-f 44lriβazr1l y 1) - ^^ ^^ 01 1 hyddoontrát mp 142.5 DEG -144 DEG C. (decomposition)

9. 2-tert-2-yl-3- (1,2,4-thiazol-1-yl) -irpiotin-1-one, hydrate m.p .: 169-170 ° C (decomposition)

10. 2-Phenyl-2-linker-3- (1 _L 2,4-thienylphenyl) -piperidine, hytooonate melting point: 178-179 ° C (decomposition)

II. 2- (3-Chlorophenyl) 12H-hexylQr-3- (1,2 _{9 4-} thienyl) (»1L) -fluoride, hydrate m.p .: 173-175 ° C (decomposition)

12. 2lbцtrχ1-2-ftøг1-3- (1 _> 2 ₉ Ч-thii8zrlli-1l (· piώpio: itril melting point: 67 to 68 ° C)

13. 2-Phenyl-2-nitro-1,2,3-thiazol-1-yl-1-nitro-nitrile, m.p .: 107-108 ° C

14. 4-Ethoxy-2-phenyl-3- (1,2,4-triazol-11-yl), melting point: 74-75 ° C

15. 2 H-X 1 - (2 R) -3- (1,2,4-Thiophenyl-1 H) -imidazole, hydronitrate Melting point: 158-160 ° C (decomposition)

16. 2-Alyl-2-felyl-lz (1 _> 2.44 triaorotil) liirpionitrile, hydro-hydrate, m.p. 145-147 ° C. (decomposition)

17. 2-Butoxy-12- (44-chlorophilt-11) 11 - ((2,4,4-triazol-1-yl) -1-piperidinyl) thiosulfate, melting point: 173-175 ° C (decomposition)

18. 2-E1,11x1x1,21-naphthyl1,21 (1,2,4-thiiezryl-1l) -piperidine temperature, m.p. 86-88 ° C

19. 2-Et122-phenyl-3- (1,2,4-thienyl-11-piperidinyl) melting point: 77 to 79 ° C

No. Name of compound and physical constant

20. 2-Hexyloxy-2-phenyl-3- (1,2,4-triezol-1-yl) -propionitrile Melting point: 58-60 ° C

21. 2- (2-Chlorophenyl) -3-hexyloxy-3- (1,2,4-triazol-1-yl) -propionitrile, hydronitrate Melting point: 157-159 ° C (decomposition)

22. 2- (2-Chloro-phenyl) -2-propoxy-3- (1,2,4-triazol-1-yl) -propionitrile, hydronitrate Melting point: 138 to 139 ° C (decomposition)

23. 2- (4-Chloro-phenyl) -2-propoxy-3- (1,2,4-triazol-1-yl) -propionitrile, hydronitrate Melting point: 155 to 157 ° C (decomposition)

24. 2- (4-Chloro-phenyl) -2-hexyloxy-3- (1,2,4-triazol-1-yl) -proplonitrile, hydronitrate Melting point: 155-159 ° C (decomposition)

25. 2- (4-Chloro-phenyl) -2-propyloxy-3- (1,2,4-triazol-1-yl) -propionitrile, m.p .: 115-119 ° C

26. 2-butoxy-2- (4-chlorophenyl) -3- (1,2,4-triazol-1-yl) -propionitrile, m.p .: 54-60 ° C

27. 2- (2-Methylphenyl) -2-octyloxy-3- (1,2,4-triazol-1-yl) -propionitrile, hydronitrate Melting point: 128-134 ° C

28. 2-Decyloxy-2- (2-methylphenyl) -3- (1,2,4-triazol-1-yl) -propionitrile, hydronitrate Melting point: 116 to 120 ° C (decomposition)

29. 2- (2-Methylphenyl) -2-octyloxy-3- (1,2,4-triazol-1-yl) propionitrile L> ²⁰ : 1,493 0

30. 2- (2-chlorophenyl) -2-butoxy-3- (1,2,4-triazol-1-yl) propionitrile ⁴⁰ ; 1,527 3

31 2- (2-chlorophenyl) -2-propoxy-3- (1,2,4-triazol-1-yl) propionitrile ⁴⁰ ; 1,530 8

32. 2-butoxy-2- (2,4-dichlorophenyl) -3- (1,2,4-triazol-1-yl) -propionitrile, hydronitrate melting point: 163-166 ° C

33. 2-butoxy-2- (2,4-dichlorophenyl) -3- (1,2,4-triazol-1-yl) -propionitrile, melting point: 53 to 55 ° C

34. 2-allyloxy-2- (2,4-dichlorophenyl) -3- (1,2,4-triazol-1-yl) propionitrile melting point: 104 to 107 ° C

35. 2- (3,4-dichlorophenyl) -2-propoxy-3- (1,2,4-triazol-1-yl) -propionitrile, hydronitrate melting point: 152 to 155 ° C (decomposition)

36. 2- (3,4-dichlorophenyl) -2-propoxy-3- (1,2,4-triazol-1-yl) -propionitrile, m.p .: 60-66 ° C

37. 2- (3,4-Dichloro-phenyl) -2-hexyloxy-3- (1,2,4-triazol-1-yl) -propionitrile, hydronitrate Melting point: 166-168 ° C

δ. Name of compound e physical constant

38. 2- (3,4-Dichloro-phenyl) -2-healoxy-3- (1,2,4-triazol-1-yl) -mis tris ^M °: 1,524 0

39. 2- (4-Fluorophenyl) 22-roopoxy-3- (1,2,4-triisol-1-yl) -propioniirr, hydronitrate, melting point: 172-175 ° C (dec.

40. 2- (4-Fluorophenyl) -2-phogooo-3 - (), 1,44-trizol-1-yl-p-phoopioyl, melting point: 98 to 100 ° C

41. 2-buttoy-22 (44 _: fluorophenyl) -ZZ ((, 2,44-thiazol-) 1-yl) -propionyl, hydrate, melting point: 173 to 175 ° C (decomposition)

42. 2-Butyl-1- (4-fluorophenyl) -13- (1,2,4-triazol-1-yl) -propionitrile, melting point: -56 to 58 ° C

43. - 2- (2-fUuoffeiyrl) -2proopoxy-3- _(1> 2,4-triiZol-yl) · -propioriiгrl, hydrozntrát; mp: 150 153 ° C EŽ (rozkledL

44. 2- (2-Fluorophenyl-L-2-pentopoxy-3- (1,2,4-triezol-1-yl) -L-pentopionitrile, m.p .: 66-69 ° C

45. 2-butO2χy22) 2 fluoгfaiУ.) - 3- (1, _2> 4-triazol-l) yl) -propioliirrl, hydrznntrát mp: 138-143 ° C (rozkledL

46. 2-Butoxy-2- (2-fluorophenyl) -3- (1.2 _l 4-triazol-l-yl) -propionitrii taro temperature: 76-79 ° C

47. 2- (2-fluoro-phenyl) -2-methyl-3-yl-1H-nitro-1-yl-propyl, hydronate m.p. 134-137 ° C (dec.

48. 2- (2-Fluorophane) -2-ha: qroyoy-3- ((1,244-g and α / β) -propiointril melting point: 58 to 60 ° C

49. 2- (4-Bromo-phenyl) -2-propoyl-1,3 (1,2,41-trione-10-10) -propylizine, mp: 150-153 ° C (dec.

50. 2i (4 ^ - ^ b ^ r ^ M ^ <^ in ^ ll ^ ^<i2ipro ^ <^ 3y ^ il ^ - ^ (1,2,4-rriiOl1101l0) -prnpinnitri0 mp: 118-121 ° C

51. 2- (41? 0? 01? 1) 12-hhзaУ.loyyЗ- (1 (2,2,4-triazol-1-11) -prrionitrile, tyronitrate) melting point: 161 to 164 ° C (dec.

52. 2-44-Bronphenyl) -2-hayyloyyl-1,3 (1,2,4-trione-10-10) -piperidine: Melting point: 60-62 ° C

53. 2. (2,41-Trifluoro-L12-prooonyyl13) »2,4-triazol-1-yl-1-propyl-thiamine, melting point: 166-170 ° C

54. 21 (2,4-Dichloro-phenyl) -2-propenyl-13- (1,2,4-trione-10-10) -propionitrile, m.p .: 61-63 ° C

55. 2- (21-tert-butan-1-yl) -1-1-butyloxy-1 () (1,2-trioazl-1-yl) 1-prolineolin hydrate, m.p. 151-154 ° C (dec.

No. Name of compound and physical constant

56. 2- (2-Methylphenyl) -2-pentyloxy-3- (1,2,4-trisol-1-yl) -poopoonitrile

D ⁴⁰ : 1,511 1

57. 2- (4-metylfenylA2 poopoxy-3- (1, 2,4-L-triizol ylApropiooitril, hydrooitrát melting point: ¹⁷⁰ to ^I-71 DEG C. (detuning)

58. 2-Hexyyo-γ- (4-4-ethylethyl) γ3- (3 (2,2-4-isopropyl-γ-APP P P θ θ ir il il il il il il il il do) meldoontrate, m.p. 177-180 ° C

59. 24 (4-TetylphenylA-2-poopoyl-34 (1,2,4-triisol-1-yl) proplonilil) m.p .: 120-124 ° C;

60. 2-heyyloyy-2- (4-tethylphenyl) -3-11,2,4-triazol-1-yl-propionitrile D ⁴⁰ : 1,506 5

61. 2-Buttoyl-γ- (4-methylphenyl A3-d, 2,4-4-triol-1-yl) propionitrile, melting point: ^{7 to 73} ° C.

34-PhenylphosphorylpyrimoniumPonitriles and 3-alkylstlphonyloxyypiperidils of the general formula II, in which 'Y represents an arylstromo-pyrrolidine group and an alkylstromo-pyrrinoxy group. used as starting materials have not been described in the literature yet.

The compounds can be obtained by partial or known methods (see, for example, Rubin et al., JACS 67, 192f (1945); Hess et al., Ber. Dt. Chem. Ges. 50, 394 ( (1917i) accessible to formula III

0-R,

R-CH (III)

AND

CN in which R and R, as defined above, are in a known manner hydroxymethyl and the thus obtained 3-hydronylpooioniyls of the general formula IV

R-C-CN-OH 1 CN (IV), in which R and Rf are as hereinbefore defined, are reacted with suitable sulfonic acid derivatives, such as chlorosulfonates, optionally with the addition of an acid binding agent. Hydroxymethyl compounds of formula IV have not been described in the art.

The preparation of the starting product is described below.

AND

3-methylsulphoryl-2-phenyl-2-propoxy-propionitrile, g (0.154 mole) of S-phenyl-4-propoxyacetonitrile was dissolved in 120 ml of pyridine and this solution was mixed with 18.5 g (0.614 mole) of psraformsldehyde. 7.7 ml of tetrabutylmmmonium hydroxide in solution are added under ice-cooling and the mixture is stirred vigorously. After several hours, the reaction mixture was poured into ice water and extracted with a kettle. The diethyl ether phase is diluted with dilute hydrochloric acid and then with sodium chloride solution and finally dried over anhydrous magnesium sulfate. After filtering off the drying agent and evaporating the solvent on a rotary evaporator under vacuum, a colorless oily liquid is obtained which is shown to be a uniform substance on a thin layer as a uniform substance and can be further processed without further purification.

The yield of 3-pyrrolidin-3-ylpyrrolidone-propionyltril was 28.4 g, corresponding to 90% of theory.

D ^{20: 1,} 502, 7 g (0.136 mole) 3PH Droo ^{y y} felnrt ^tp-2-yl rrcpon tpronronitoilu rczpusSÍ with 200 ml of toluene and this solution was mixed with 19.5 g (0.171 Mooy) chloride mmtexrnulfonové. ^To this reaction mixture, ^p s at ¹⁰ ° ^C at ^{the p} and e ^{(18.6 g DEG, 18} 4 mobo triethylaluminium ^and em ^and IU. Reelcční mixture was stirred for 30 minutes at místnoost, odd-t- swarms precipitates ^f or ^e Eny ethyl am ^{i e} r ^HTD roehlor ^id and the zahuet.í. tytek ^{Z p} o zahušttoí in JME ^y ^ ^d the ethyl / ester and for the ^ with water, dried using: anhydrous !! The oily residue is identified as a chemically uniform substance by means of a thin film layer.

The yield ^of 3-t-merotsulfoτn 2 feiylp2prroroc; otprooionitrilu render 32.27 g, corresponding to 86%.

d ²⁰ : 1 ^, 500.

In the following, examples will serve to illustrate moCeioSí p ^ ^ they used ^the preparation ^{of p} ccording translated in ^y finding. ^J

Row d 3

Effect of rrcft1rktec ^on listůhc sheet processing against genuine. oidii Erysiphe gnmiints not Barley in the greenhouse.

The young leaflets of barley at the first leaf stage are treated with the active ingredient of said concentration to the droplet stage. After the sprayed composition has dried, the treated plants as well as the unprocessed control plants are sporulated by soaking the test plants with the infected plants. Thereafter, the test plants in ^the užtivžží Pleníku at te ^ OTE 'esi 20 and ²² DEG C., ^and about one-Nu ^{characterized} it stay overnight ^ ^d ^ ocento leaf surface free of damage. The furngoid effect is calculated according to the following formula:

Λ for processed .100% effect = 100 - --------------------------------------- damage unprocessed

The compounds are revoluted as 20% preparations.

500 ppm

100 ppm

Compound No.

Erysiphe greminis% effect

1 100 ALIGN! 95 2 100 ALIGN! 59 3 100 ALIGN! 100 ALIGN! 4 100 ALIGN! 100 ALIGN! 5 100 ALIGN! 95 6 ' 100 ALIGN! 94 7 100 ALIGN! 100 ALIGN! 8 100 ALIGN! 100 ALIGN! 9 100 ALIGN! 100 ALIGN! 10 100 ALIGN! 100 ALIGN! 11 100 ALIGN! 94 12 100 ALIGN! 100 ALIGN! 13 100 ALIGN! 100 ALIGN! 14 . 100 ALIGN! 100 ALIGN! 15 Dec 100 ALIGN! 100 ALIGN! 16 100 ALIGN! 100 ALIGN! 17 100 ALIGN! 100 ALIGN! 18 100 ALIGN! 100 ALIGN! 19 Dec 100 ALIGN! 100 ALIGN! 20 May 100 ALIGN! 100 ALIGN! 21 100 ALIGN! 95 22nd 100 ALIGN! 100 ALIGN! 23 - 100 ALIGN! 100 ALIGN! 24 100 ALIGN! 25 100 ALIGN! 26 100 ALIGN! . - 28 100 ALIGN! 95 30 100 ALIGN! 100 ALIGN! 31 100 ALIGN! 100 ALIGN! 33 100 ALIGN! 100 ALIGN! 34 100 ALIGN! 100 ALIGN! 35 100 ALIGN! 100 ALIGN! 36 100 ALIGN! 100 ALIGN! 38 100 ALIGN! 100 ALIGN! 41 100 ALIGN! 100 ALIGN! 42 100 ALIGN! 100 ALIGN! 44 100 ALIGN! 100 ALIGN! 48 100 ALIGN! 95 49 100 ALIGN! 100 ALIGN! 50 100 ALIGN! 100 ALIGN! 51 100 ALIGN! 100 ALIGN! 52 100 ALIGN! 100 ALIGN! 53 100 ALIGN! 100 ALIGN! 54 100 ALIGN! 100 ALIGN! 55 100 ALIGN! 100 ALIGN! 57 100 ALIGN! 100 ALIGN! 58 100 ‘ 100 ALIGN! 59 100 ALIGN! 100 ALIGN! 60 100 ALIGN! 100 ALIGN! 61 100 ALIGN! 100 ALIGN!

Example 4

Effect of prophylactic treatment of pumpkin plant leaves against Erysiphe cichoracearum in a greenhouse

The spray concentrations of the sprayed plant pumpkin are sprayed with dry spores of Erysiphe cichoracearum after spraying and incubated in a greenhouse at 24 DEG C. together with unprocessed inoculated plants. After one week of cultivation, the percentage of total leaf area was evaluated for areas infected with oidia. The fungicidal effect is calculated from the following equation:

100 · damage in processed% effect »100 damage in unprocessed

The designation s in the following table indicates that the fungicidal effect could also be assessed on plant increments (after processing) and found positive. This means that the active substances have been systematically transported into increments and also have a 100% anti-oid effect.

The active compounds were applied as 20% preparations.

Compound No. Erysiphe cichoracearum% effect

250 25 5 2.5 0.5 1 100s 1008 100s 2 1008 1 OOs 100s 3 100s 1008 1008 4 100a 1008 100 ALIGN! 5 100s 100s 100 ALIGN! 6 100s 100s 100 ALIGN! 7 100 ALIGN! 100 ALIGN! 100 ALIGN! 8 100s 98 100 ALIGN! 9 100s 100s 1008 10 100a 100a 100 ALIGN! 11 100s 100s 100 ALIGN! 12 100a 100s 100 ALIGN! 13 100s 14 100s 100s 100 ALIGN! 15 Dec 100s 100 ALIGN! 100 ALIGN! 16 100s 100 ALIGN! 99 ,! 17 100s 100s 100a 18 100a 100s 100 ALIGN! 19 Dec 100s 100 ALIGN! 97 20 May 1008 21 1008 100 ALIGN! 90 22nd 100a 100 ALIGN! 100 ALIGN! 27 Mar: 1008 29 100a 32 1008 37 ЮОз 39 1008 40 100s 43 1008 45 100a 45 100a

Compound No.

250

2.5

0.5 ppm 100s

100s lOOs

Example 5 of barley

Effect (%) prophylactic treatment of leaves against Helminothosporium teres (= Pyrenophora teres), causing the first leaf foliar spots are sprayed with the indicated concentration of processed rostlixa and untreated control

Young barley plants in the active substance stage. After the spray has dried, the plants are sprayed with a conidospore suspension of Helminthosporium teres and incubated in a humid chamber at a temperature between 20 and 22 ° C for 2 days. The rostlixes are then cultured in a greenhouse at a temperature in the range of 20 to 22 ° C. One week after inoculation, the percent leaf infestation is evaluated. The fuxngicidal effect is calculated from the following formula:

100 ALIGN! damaged in processed% effect = 100 damaged in unprocessed

The active compounds are used in the form of 20 preparations

Helminthosporium teres% effect

Compound No.

500 ppm 100 ppm 10 1 100 ALIGN! 100 ALIGN! 2 100 ALIGN! 100 ALIGN! 100 ALIGN! 3 100 ALIGN! 100 ALIGN! 90 4 95 95 90 5 100 ALIGN! 100 ALIGN! 6 99 7 98 90 8 83 9 100 ALIGN! 85 10 95 95 11 100 ALIGN! 90 12 94 90 13 92 85 14 89 80 15 Dec 94 90 16 94 80 17 89 18 100 ALIGN! 70 19 Dec 94 20 May 70 23 85 24 95 90 25 95 95 26 80 27 Mar: 90

ppm

Examples

Effect of prophylactic treatment of barley leaves against rust caused by Puccinia hordei in climatic growth chamber

The young leaflets of barley at the first leaf stage are sprayed with the indicated concentration of active ingredient. After the spray coating has dried the treated plants as well 'as the untreated control plants were inoculated overcoating prote ^ us infected rust then placed in a conditioned environment ^for the growth OMI ^s ^ e. Ros clay ^. ^ Is that when you r ^^ t ePlot-E ¹⁵ ° C for ^{10 d} Nu, the ^{price P h} rvníc two days, maintaining the air practically saturated vlhkoosí · Then vyhodnnoí poddl leaf area attacked by rust. Ршп1с ^ 1пС effect is calculated by following equation: *

100 · damaged in processed% effect - 100 - ---------------------------------- damaged in unprocessed

The active ingredients are used as 205% preparations.

Compound No. Puccinia hordei * effect 500 ppm 100 ppm 20 ppm 1 100 ALIGN! 77 2 100 ALIGN! 83 3 4 100 ALIGN! 100 ALIGN! 89 5 100 ALIGN! 100 ALIGN! 94 6 100 ALIGN! 94 7 100 ALIGN! 98 89 8 100 ALIGN! 94 94 9 80 10 100 ALIGN! 98 94 11 89 12 84 13 89 14 95 80 15 Dec 95 16 78 17 100 ALIGN! 100 ALIGN! 100 ALIGN! 18 98 19 Dec 95 20 May 85 21 100 ALIGN! 70 22nd 100 ALIGN! 100 ALIGN! 23 79 24 90 70 25 90 90 27 Mar: 85 30 95 31 95

Example 7

Protection against Pseudomonas phaseeSiisla in vitro, the agent of facial oily stains

Severography, n. P., MOST

Price 2,40 Kčs

After the heat sterilization, the sweetening egas is cooled to about 45 ° C and then mixed with the test substance in the form of an aqueous preparation. The treated soil is then poured into petri dishes with artificial hmooy. After the broth has solidified, ee plates are treated with an ager-treated agar as well as untreated egar as a control by inoculating them into the center of the plate with suspensions of the pathogenic agent Pseudomonas phaseelicola. Then the flasks were formed at 22 ° C. After 2 1/2 weeks, the radial enlargements of the growing cage are measured. From the average of two replicates of each experimental member, the backericidal effect is evident. as follows:

100 ALIGN! radial growth in processing soil% effect = 100 - ------------------------------------ radial growth in untreated The active substances were used in the form of 20% of the preparation.

Compound No.

15 21% effect with conc. active substance

250 ppm

Example 8

AAUvita vapor against Helminthosporium teres on barley in greenhouse

To determine the vapor activity, one cup with about 20 barley seedlings at the beginning of the second hooks stage was placed between two cups with barley, which was spray-treated with an active substance concentration of 0.1%, and then the spray-dried. A suspension of the helminthosporium teres pathogens prepared from an aqueous solution of 0,05% sodium oleate and 0,02% gelatin, containing 100 000 spores per milliliter, is cut over all three cups of each test member. After spraying the spores, the three cups of each test member were sealed for three days in polyethylene film and left under glasshouse conditions at about 20 ° C. The packages are then opened by cutting the foil at the height of the leaf tops. After eight days, the number of force spots in each cup is scaled. From the values obtained, calculate the fungicidal effect of the vapors as follows:

force spots on exp. barleyex. . 100% effect with 100 - ---------- —.......-.........

force spots on unexp. barley

The active compounds are used in the form of 20% of preparations. All exposures wash tulle for plants acceptable.

Compound No.

% effect

100 ALIGN!

100 ALIGN!

100 ALIGN!

Compound δ% of effect comparative

1- (4-Chloro-phenoxy) -3,3-dimethyl-1- (1,2,4-triazol-1-yl) -butanone 86

Example 1 and d 9

The systemic effect of soil tillage before the emergence of plants against oid sugar beet Erysiphe polygon! in the greenhouse

The pots, after sowing sugar beet after spraying 0.3 kg of active ingredient per hectare, were placed next to unprocessed pots in a greenhouse at a temperature of about 20 ° C. After emergence of beet plants (12-14 in a pot), the plants wait for the first two leaves to be inoculated by dusting with a dry spore! right beet oidia Erysiphe polygon !. Three weeks later (six weeks after tillage) leaf infestation was determined. Fungicidal action can only occur through the absorption of the active substance by the roots of plants and is calculated according to the following formula:

attack in processed. 100% effect »100 - - ------------------------------------- attack in unprocessed

The active substances are used in the form of 20% of preparations. All treatments appear acceptable to plants and lead to stronger and more compact growth compared to untreated control plants

Compound No. % effect 12 100 ALIGN! 13 100 ALIGN! 14 100 ALIGN!

Example 10

Soybean and diaper sprayed with an emulsion of wound substance before emergence · The amount used is 2 kg of active substance per hectare. Then they are cultivated in a greenhouse for three weeks.

The following table shows the percentage growth inhibition.

Compound No. Suppression of rose in% soya diapers 2 39 28 3 22nd 28 7 17 7 9 0 17 13 4 14 14 17 24 18 13 14 19 Dec 4 14 22nd 65 21 23 30 17

Suppression of growth in% soybean

35

35 compar.

2-chloroethyl ethyltriethylaluminum chloride 0

Compound No.

yženiee

It has been shown that the active compounds according to the invention are generally more effective than the comparative compound.

Example 11

The sown rice was treated with a quantity of 2 kg of active ingredient per hectare before emergence. After three weeks of growth in the greenhouse, the percentage of growth inhibition was determined and the results are shown in the table below.

Compound No.

Growth Suppression% Comparative Comb.

2-chlorophthyltriethylaminoethyl chloride

The inhibition of growth that occurs with the application of the active compounds according to the invention does not occur in the same application of the comparative compound.

Example 12

Seeded tulle beet before spraying was sprayed in moossi with 2 kg of active substance not one hectare. After three weeks of cultivation in the greenhouse, growth suppression and coloring of the plants were evaluated. The results are shown in the table below.

Compound No. Suppression of growth in% coloration 1 9 1 3 34 1 7 34 0 3 37 0 9 25 1 10 37 0 12 32 0 13 41 0 14 41 0 16 53 0 17 53 0 18 22nd 1 19 Dec 37 0 20 May 37 1 21 6 1 22nd 37 1 23 53 2 24 22nd 1 25 69 2

Compound No. Suppression of growth in% coloration 26 37 2 comparative ² -hhlnrttyrtrtmtУyltιoontιm- chloride 0 0

Coloring table:. 0 = as control.

= intensive green · dark green

The active compounds according to the invention inhibit the growth of sugar beet, which has not been achieved with the reference compound.

Example 13

Effect of leaf prophylactic treatment against Fusarium culmorum leaf spot agent in millet (glaucum) in a greenhouse.

The young millet plants (about 30 in each pot) at the second leaf stage are coated with the indicated concentration of active ingredients. After the spraying has been dried, the treated as well as the untreated control plants are suspended in Fusimum culmorum and pontchaai in a glass at a temperature of ²² ° C. ^p o ^th y ^of all days vyhodnnoí poodle percentage of infected leaf areas. The fungicidal effect is calculated according to the following equation:

100 ALIGN! attack in processed% effect »100 - -------------------- i --------------------- assault on unprocessed

The active ingredients were used in the form of 20% of the preparation. The results are shown in the table below.

Compound #% Effect% Effect

500 ppm 100 ppm

2 100 ALIGN! 100 ALIGN! 3 91 9 80 12 90 13 100 ALIGN! 14 100 ALIGN! 16 95 17 95 18 95 19 Dec 90 20 May 80 22nd 99 90 23 100 ALIGN! 99 24 100 ALIGN! 97 25 100 ALIGN! 98 26 98 93 27 Mar: 90 29 97 90 30 97 90 31 100 ALIGN! 98 ‘

Example 14

Effect of prophylactic processing of sugar beet leaves in a greenhouse against the leaf spot agent Cercospora beticola

Sugar beet roots with at least two developed leaves are sprayed with the indicated concentrations of active substances. After spray drying, the treated plants, as well as the untreated control plants, are sprayed with a koji suspension of Cercospora beticola and incubated for 2 days in a greenhouse at 26 ° C wet. The plants are then cultured from normal greenhouse conditions, and the percentage of plants affected is evaluated two weeks after treatment. The fungicidal effect is calculated from the following equation.

100 ALIGN! infestation for processed% effect = 100- ----------------------------- infestation for untreated

The active ingredients were used in the form of 20 preparations.

Compound No. «effect

500 ppm 100 ALIGN! 3 100 ALIGN! 100 ALIGN! 1 1 93 12 93 13 100 ALIGN! 14 . 93 16 100 ALIGN! 17 87 19 Dec 93 20 May 87 21 100 ALIGN! 96 22nd '100 100 ALIGN! 23 100 ALIGN! 100 ALIGN! 24 100 ALIGN! 100 ALIGN! 25 96 96 26 100 ALIGN! 96 27 Mar: 98 98 28 100 ALIGN! 98 29 100 ALIGN! 98 30 100 ALIGN! 100 ALIGN! 31 100 ALIGN! 100 ALIGN!

Example 15

Effect of seed treatment against the action of Helminthosporium sativum (causative agent of helminthosporiosis) on barley.

Unspoiled barley seed of Helminthosporium satvvum was treated with 50 mg of active ingredient not 100 g. For each treatment, 2 g of seed was sown in pots in duplicate and unprocessed seed was used as a control. The pots were incubated at 15 ° C in an air-conditioned chamber. After the plants have risen, the ummie is illuminated in a 12-hour rhythm. After four weeks, the percentage of plants affected by helminthosporiasis is examined. Unprocessed plants became ill all.

The active ingredients were used as 20% preparations. The results are shown in the table below.

244127 22nd Compound No. % effect 2 3 4 5 100 ALIGN! 99.5 100 ALIGN! 99.5

Example 16

Effect of seed treatment against Phoma betae in sugar beet.

Beet seed infected with Phoma betae is treated with 250 mg of active ingredient per 100 g of seed. ²⁵ seeds are sewn from the treated and unprocessed seeds in four replicates in four shots and placed at ^{15 [} deg.] C. in an oiled tamato. After the emergence of rosslin, these artificially become twelve-hour rhythm. Until the end of the experiment after seven weeks, the infected plants were traumatized weekly. In untreated control seed, these infected 76.1 * emerging plants were infected. The protective effect of the processing is calculated from the dividing equation.

100 ALIGN! infested in processed * effect »100 --- infested in unprocessed

^The active ^{ingredients p} ^ t ^ ^u ^ i ^ '^ i ^ ^y ZL as a 20% pHprav ^. Výsletoy Uve ^d enes are in the following table.

Compound No. * of effect

2100

397 .97

5100

683

1292

99 *

96 Comparative Beta- (1,1'-biphenyl-4-yloxy) -alpha- (1,1-dimethylphenyl) -1H-112,4-triazol-1-yl-11

1-U-chloro-enoxyl-4-dimethyl-1- (1,2,4-traazol-yl) -b-methyl-57

Claims (3)

SUBJECT OF THE INVENTION First with growth and tobacco ^ i ^^ ^ prostřtíek taujísi ^marks in said compound being 1,2,4-íritzsl L-ylcropiosttíil formula I R = C-CH CN where (I), K * 1 represents fetyl, which is optionally mono- or di-substituted by a halogen atom or a C 1 -C 4 alkyl group and denotes a C 1 -C 10 alkyl group or an allyl group and / or a hydrate thereof, 2 · Funticidini baktsrictdní and plant growth regulating composition according to claim 1, ye ²ⁿ nčudící as active ingredient a tslprolOXl-2yfefyl-У - (((214-tгitУoO-yl) -oiooiltyddClitrát. 3.: common A process for the preparation of an active ingredient according to claim 1, characterized in that the compound (i) of formula (II) STEED. AND RC-GH ₀ -Y r CN (II) where R a * Y It has the meaning given above and denotes methylsulphonylmethyl is reacted with 11414 titanium