CH633281A5 - Fungicidal compound - Google Patents

Description

The invention relates to a fungicidal compound comprising substituted 1,2,4-triazoles, their addition salts with acids and their complexing agents of the metal salt type, which can be used as so-called systemic or teletoxic fungicides (because they are capable of 'exert their effect on the plant far from their point of application) broad spectrum, as well as processes for their preparation. The compounds included in the scope of the invention are represented by the following general formula (I):

„1

50

I

Z "<CH2> m" Ç * (CH2) n "Q U2

(I)

in which:

Z is a C6 to C10 aryl radical which is optionally substituted;

R1 is a cyano radical;

R2 is: 1) hydrogen, 2) a Ct to C12,3 alkyl radical) a C3 to C8,4 cycloalkyl radical) a C2 to C8 alkenyl radical, 5) a C5 to C8 cycloalkenyl radical, 6) a C2 to 60 alkynyl radical C8,7) a C6 to C10 aryl radical which is optionally substituted, 8) a C7 to C14 aralkyl radical which is optionally substituted in the aryl portion, 9) a C alkoxy radical ! to C4.10) a C2-4 alkenoxy radical, 11) a C2-4 alkynoxy radical.12) a hydroxy radical, 13) a C6 to C10 aryloxy radical which is optionally substituted 65, or 14) a C7 aralkoyloxy radical C14 which is optionally substituted in the aryl portion;

Q is an optionally substituted l- (1,2,4-triazolyl) or 4- (1,2,4-triazolyl) radical;

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m is 0 or 1;

n is 1 or 2;

as well as addition salts, with an agronomically acceptable acid, and complexes of the agronomically acceptable metal salt type of such a compound.

When Z or R2 is an optionally substituted aryl radical, such a radical is of the phenyl or naphthyl type which is optionally substituted with up to three substituents chosen from the group consisting of halo, nitro, trihalomethyl, cyano, C7 to C14 aralkyl, Ct to C4 alkyl, C to C4 alkoxy, C to C4 alkylthio, C to C4 alkylsulfinyl, C to C4 alkylsulfonyl, and phenoxy, phenylthio, phenylsulfinyl, phenylsulfonyl, and phenoxy, phenylthio, phenylsulfonyl substituted with up to two substituents selected from the group consisting of halo, nitro, trifluoromethyl, cyano, methyl, methoxy, methylthio, methylsulfinyl and methylsulfonyl.

Typical substituted aryl radicals are 4-chlorophenyl, 2,4-dibromophenyl, 3,5-difluorophenyl, 2,4,6-trichlorophenyl, 2,3,5-tribromophenyl, 3,4-dichlorophenyl, 2-chloro-4- iodophenyl, 3-chloro-4-nitrophenyl, 2,4-dinitrophenyl, 4-phenoxyphenyl, 2-phenylthiophenyl, 3-phenylsulfinylphenyl, 4-phenylsulfonyl-phenyl, 4-chlorophenoxyphenyl, 2,4-dibromophenoxyphenyl, 3,5-difluorophenyl 4-chloro-2-methylphenylsulfinylphenyl, 3,4-diiodophenylthiophenyl, 4-trifluoromethyl-2-chlorophenyl-sulfonylphenyl, 2-cyano-4-methoxyphenylsulfinylphenyl, 4-methylthiophenoxyphenyl-3-phenylphenyl-3-phenylphenyl 5,6-trimethylphenyl, 2-nitro-4-methoxyphenyl, 2-chloronaphthyl, 2-nitronaphthyl, 2,4-dimethoxyphenyl, 4-trifluoromethylphenyl, 2-nitro-4-trifluoro-methylphenyl, 3,5-dimethylthiophenyl, 2- cyano-5-methylphenyl, 2,4-dimethylsulfinylphenyl, 2,4-dimethylsulfonylphenyl, 2,4-di-iodonaphthyl, 2-iodo-4-benzylphenyl, e t 3,4,5-trimethylphenyl and 2-iodo-4-methylphenyl.

When R2 is a substituted aralkyl radical, such a radical can be, for example, a 2,4-dichlorobenzyl, 2,4-dibromobenzyl, 2,5-dinitrobenzyl, 2,4,6-trichlorobenzyl radical, 3,5 -dimethoxy-phenethyl, 2,5-dimethylthiophenylpropyl, 2,4-diiodophenyl-2-methylpropyl, 3,4-dimethylsulfinylbenzyl, 2,3-dimethylsulfonyl-phenylethyl, 2,4,5-trimethylphenylbutyl, 2,4-dicyanonaphtyl-methyl , 2-nitronaphthylpropyl, 2,4-dibromonaphthylbutyl, 1-nitro-naphthylethyl and 2-nitronaphthylethyl.

The term alkyl as used in the present description and in the claims should be understood as including within its scope the above-specified alkyl radicals, both in branched chain and in straight chain. Typical alkyl radicals included within the scope of this term for the purpose of defining the present invention are methyl, ethyl, n-propyl, isopropyl; n-butyl, secondary butyl, isobutyl, tertiary butyl, n-pentyl, neopentyl, isopentyl, n-hexyl, n-heptyl, isooctyl, n-nonyl, n-decyl, isodecyl, n-undecyl and n-dodecyl.

When Q is substituted by- (1,2,4-triazolyl) or 4- (1,2,4-triazolyl), these two radicals can have up to two substituents chosen from halo, C1-C4 alkyl, nitro and cyano.

Among the acids which can be used to prepare the addition salts with an acid according to the present invention, mention may in particular be made of hydrochloric, hydrobromic, nitric, sulfuric, phosphoric, hydroiodic, hydrofluoric, perchloric, p-toluenesulfonic, methanesulfonic acids , acetic, citric, tartaric, malic, maleic, oxalic, fumaric, and phthalic.

The complexes of the metal salt type according to the invention are, for example, those which are represented by the following formula (II):

R1 1 00

z- (° H2) a -? * (CH2) n- * "

R

in which Z, R1, R2, Q, m and n are as defined for formula (I) above, and M is a cation chosen from the metals of groups IIA, IB, IIB, VIB, VIIB and VIII of the periodic classification of the elements according to the American standardization (or groups 2a, lb, 2b, 6a, 7a and 8 according to the French standardization), and X is a counterion of the anion type chosen in such a way that the sum of the charges of valence of cation M and anion X is zero. Typical cations are the magnesium, manganese, copper, nickel, zinc, iron, cobalt, calcium, tin, cadmium, mercury, chromium, lead and barium cations. Typical anions are chloride, bromide, iodide, fluoride, sulfate, bisulfate, perchlorate, nitrate, nitrite, phosphate, carbonate, bicarbonate, acetate, citrate, oxalate, tartrate, malate, maleate, fumarate, p-toluenesulfonate, methane anions. sulfonate, dithiocarbamate of mono- or dialkyl in C! to C4 and C4-alkylene bis-dithiocarbamate.

Mention may in particular be made of the compounds, salts and complexes represented by formulas (I) and (II), in which Z is a phenyl or naphthyl radical, preferably a phenyl radical optionally substituted with up to three substituents, and preferably up to 'with two substituents chosen from the group consisting of halo, nitro, trihalomethyl, cyano, C1-C4 alkyl, C-alkoxy! to C4, C1 to C4 alkylthio, alkyl (C1 to C4) sulfinyl and alkyl (C1 to C4) sulfonyl; R2 is chosen from Ct to C12 alkyl (more particularly C to C alkyl), C5 to C7 cycloalkyl (for example cyclohexyl), C2 to C4 alkenyl (for example allyl), Cs to C6 cycloalkenyl (for example cyclohexenyl) , C2 to C4 alkynyl (for example propargyl), phenyl, benzyl or phenethyl unsubstituted, or else phenyl, benzyl or phenethyl the aromatic portion of which is substituted with up to two halogen atoms; Q is an unsubstituted 1- or 4- (1,2,4-triazole); m is 0; and n is the integer 1.

Mention may also be made of compounds, salts and complexes represented by formulas (I) and (II), in which Z is a phenyl radical optionally substituted with up to three substituents, preferably up to two substituents, chosen from the group consisting of chloro, bromo, methyl, methoxy, nitro and methylthio; R2 is C1-C2 alkyl, cyclohexenyl, propargyl, phenyl, benzyl or phenethyl, or phenyl, benzyl or monochloro-substituted phenethyl; Q is an unsubstituted 1- or 4- (1,2,4-triazole); m is equal to

0; and n is the integer 1.

As individual compounds, the following may be mentioned in particular:

1 - [p-cyano-P- (2,4-dibromophenyl) hexyl] 1,2,4-triazole 4- [p-cyano-p- (2,5-dinitrophenyl) octyl] 1,2,4-triazole l- [P-cyano-y- (3,5-ditrifiuoromethylphenyl) nonyl] 1,2,4-triazole 4- [P-cyano-S- (2,4,6-trichlorophenyl) dodecyl] 1,2,4 -triazole

1 - [P-cyano-P- (2,4,5-trimethylphenyl) tetradecyl] 1,2,4-triazole 4- [P-cyano-P- (2,4-dimethoxyphenyl) hexyl] 3-methyl-1 , 2,4-triazole 1 - [P-cyano-P- (2,4-dimethylthiophenyl) hexyl] 5-chloro-1,2,4-thiazole 4- [P-cyano-P- (3-iodophenyl) decyl ] 1,2,4-triazole l- [P-cyano-P- (2,6-dichlorophenyl) pentyl] 1,2,4-triazole 4- [P-cyano-P- (4-cyanophenyl) propyl] 1 , 2,4-triazole 4- [ß-cyano-ß- (2,4-difluorobenzyl) octyl] 1,2,4-triazole 4- [P-cyano-P- (4-iodophenyl) undecyl] 1,2 , 4-triazole 1- [ß-cyano-p- (4-tolyl) hexyl] 1,2,4-triazole 4- [ß-cyano-ß- (4-anisyl) hexyl] 1,2,4-triazole

4- [P-cyano-P- (2,4-dichlorophenyl) "P-cyclopropylethyl] 1,2,4-triazole 4- [P-cyano-P- (2,4-dichlorophenyl)" P-cyclopentylethyl] l , 2,4-triazole l- [ß-cyano-P- (2,4-dichloronaphthyl) hexyl] 1,2,4-triazole 4- [P-cyano-ß- (2-fluoronaphthyl) hexyl] 1,2 , 4-triazole 1 - [ß-cyano-ß- (2-nitronaphthyl) hexyl] 1,2,4-triazole 4- [P-cyano-P- (3,4-dichlorophenyl) octyl] 1,2,4 -triazole 1 - [P-cyano-P- (2,3-difiuorophenyl) propyl] 1,2,4-triazole 4- [P-cyano-P "(2,5-diethylphenyl) -tetradecyl] 1,2, 4-triazole 4- [P-cyano-P "(4-trichloromethylphenyl) pentyl] 1,2,4-triazole 1 - [P-cyano-p- (4-ethylsulfonylphenyl) hexyl] 5-cyano-1,2, 4-triazole 4- [P-cyano-P- (2-bromo-4-nitrophenyl) hexyl] 3-bromo-1,2,4-triazole l- [P-cyano-P- (3-methylsulfinylphenyl) butyl] 3-ethyl-1,2,4-triazole 1 - [P-cyano-P "(2,4-dichlorophenyl) -4-chlorophenethyl] 1,2,4-triazole

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633,281

4

4 - $ - cyano-P- (4-chlorophenal) -4-chlorophenethyl] 1,2,4-triazole and the derivatives with agronomically acceptable acids, as well as the complexes of the metal salt type of the above-mentioned compounds.

The substituted 1,2,4-triazoles included in the scope of the present invention can be prepared by implementing standard synthetic methods, more particularly by implementing those which are known per se for the preparation of analogous compounds. A preferred method for the preparation of compounds included in the scope of the present invention corresponds to the following scheme:

R1

Z- (CH,) „- Ç- (CH,)„ - Y + [Q] Formula (I)

R2

(III)

In this sequence of reactions, Z, R1, R2, Q, m and n are as defined for formula (I); Y can be halide, alkanesulfonate or arylsulfonate, and the metal of the metal salt is preferably sodium or potassium. The reaction can be carried out either in the absence of solvent, or in the presence of an appropriate solvent such as benzene, toluene, xylene, glyme, N, N-dimethylformamide or dimethylsulfoxide. Reaction temperatures can be between 0 and 150 ° C.

When the raw material represented by the formula (III) is allowed to react with the free base 1H-1,2,4-triazole in place of its metal salt (usually at temperatures between 50 and 180 ° C), we obtains a mixture of 1,2,4-triazoles substituted in position 1 and in position 4, and these triazoles are easily separable using conventional chemical separation techniques such as extraction, chromatography or crystallization.

Another preferred method for preparing the substituted triazoles in question is shown schematically as follows:

R1

I

Z- (CH2) m-Ç- (CH2) n-NH2 (IV)

R2

CH3 / CH3

+ J> T-CR3 = N-N = CR4-N -► Formula (1) (V)

ch3 xch3

In this succession of reactions, Z, R1, R2, m and n are as defined above for formula (I) and R3 and R4 are chosen from the group consisting of hydrogen, halogen, C alkyl! to C4, nitro or cyano. This reaction is usually carried out in an inert solvent such as benzene, toluene or xylene. The reaction is usually carried out at temperatures between 0 and 150 ° C in the presence or absence of a suitable catalyst such as p-toluenesulfonic acid, benzenefulfonic acid or methane-sulfonic acid. During this preparation, an excess of either reagent can be used, and the mode of addition is not critical.

The raw materials represented by formula (III) can be prepared by normal synthesis methods. Examples of such preparation methods are described in BE patent No. 838928 or its equivalent DT OLS P No. 2604047.

The raw materials represented by formula (IV) can be prepared by first preparing the corresponding raw materials represented by formula (III), in which Y is chlorine or bromine, then by reacting them with ammonia, either in the absence, or in the presence of a suitable solvent such as diethyl ether, tetrahydrofuran or methanol at temperatures usually between -40 and + 100 ° C.

The addition salts of substituted 1,2,4-triazoles included in the scope of the invention can be prepared by using normal and conventional techniques, well known to those skilled in the art. For example, a compound represented by formula (I) can be dissolved in a suitable solvent such as diethyl ether, tetrahydrofuran, ethanol or methanol, and treated with an equivalent amount or with an excess of a mineral or organic acid which can whether or not it is dissolved in an appropriate solvent. Then, the mixture is cooled or evaporated, thereby obtaining the salt which can either be used as it is or recrystallized from an appropriate solvent or from a combination of suitable solvents.

The metal salt complexes of the compounds represented by formula (I) can be prepared by adding dropwise, and while stirring, a stoichiometric amount of a metal salt (dissolved in a suitable solvent) to a solution of a compound represented by formula (I) dissolved in a suitable solvent. The reaction mixture can be briefly stirred, then the solvent is removed under reduced pressure, and the desired metal salt is thus obtained.

Metal salt complexes can also be prepared by mixing stoichiometric or excess amounts of the metal salt and a compound represented by formula (I) in the desired amount of solvent containing the appropriate adjuvants just before spraying fungicidal compositions on plants. The adjuvants which can be incorporated into these preparations prepared in situ can be detergents, emulsifiers, wetting agents, spreading agents, dispersing agents, thickeners, adhesives and other adjuvants conventionally used in view of agricultural applications.

Among the solvents which can be used for the in situ preparation of such compositions, mention may in particular be made of various polar solvents, for example water, methanol, ethanol, isopropanol or ethylene glycol and various dipolar aprotic solvents such as for example, that dimethylsulfoxide, acetonitrile, dimethylformamide, nitromethane or acetone.

The following examples 1 to 4 illustrate the preparation of compounds in which R1 is cyano. The compounds prepared by operating as described in Examples 1 to 4, as well as other similar compounds which have been prepared by following one of the procedures which are described therein, are listed in Table I, however, appropriate analytical data are presented in Table II.

Example 1:

4- [2-cyano-2- (2,4-dichlorophenyl) hexyl] -1,4,4-triazole (compound No. 1 of table I)

Heated to 185 ° C overnight a mixture of 12 g (0.036 mol) of 2-cyano-2- (2,4-dichlorophenyl) hexyl bromide and 10 g (0.145 mol) of lH-1,2,4 -triazole. The reaction mixture is then cooled and poured into water, then extracted with ether. When the combined ethereal extracts are washed with water, a white precipitate separates from the ethereal layer. This precipitate is collected by filtration and dried under vacuum, which gives 1 g of a white solid, mp 46-49 ° C. Analysis by chromatography and by nuclear magnetic resonance reveals that this substance is indeed 4- [2-cyano-2- (2,4-dichlorophenyl) hexyl] -1,2,4-triazole. NMR (CDC13): 80.7-3.2 (complex multiplets, 9H),

5.0 (q, 2H), 7.2-7.8 (m, 3H), 8.15 (s, 2H)

Example 2:

Preparation of 1-f2-cyano-2- (2,4-dichlorophenyl) hexyl] -1,2,4-triazolium nitrate (compound No. 3 of table I)

A. 2-Cyano-2- (2,4-dichlorophenyl) hexyl bromide: a solution containing 1.0 mol of n-butyl bromide and 1.0 mol of 2,4-dichlorophenyl cyanide in 250 ml of chloride methylene is added to a solution (500 ml) 25% aqueous sodium hydroxide with 5.0 g of tetraethylammonium bromide. The reaction mixture is stirred vigorously under reflux for 3 h, which gives, with a yield of 90%, the desired product whose chromatographic analysis reveals that it is at a degree of purity of 90%, this

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which is also confirmed by nuclear magnetic resonance spectroscopy. The cyanide is then mixed with 1.3 mol of methylene bromide and is added to a 50% aqueous solution of sodium hydroxide containing as catalyst either tetraethyl ammonium bromide or benzyltriethylammonium chloride. The reaction mixture is heated at reflux (90 ° C) for 3 h until 95% of the raw material has been consumed. There is always about 5% of α-n-butyl-2,4-dichlorobenzyl cyanide unreacted during this reaction.

B. 1- [2-cyano-2- (2,4-dichlorophenyl) benzyl] -1,4,4-triazole: to a solution, in 25 ml of dimethylsulfoxide (DMSO), of sodium-1,2,4 -triazole, produced from 3.2 g (0.046 mol) of 1H-1,2,4-triazole and 1.85 g (0.046 mol) of sodium hydroxide, added dropwise at 110 ° C , 2-cyano-2- (2,4-dichloro-phenyl) hexyl bromide. The whole is stirred at 110 ° C. for 1 hour. The reaction mixture is poured into 400 ml of water and extracted with ether. The ethereal extracts are combined, washed with water, then dried over MgSO4. The drying agent is separated by filtration and, to the filtrate, concentrated nitric acid is added dropwise until the formation of precipitate is stopped. 8.0 g of precipitate are collected by filtration, which is characterized as being the nitric acid salt (RH 45.136) of the desired product.

NMR (DMSO): 50.6-2.5 (complex multiplets, 9H), 5.2 (q, 2H), 7.5-7.9 (m, 3H), 8.3 (s, 1H), 8.7 (s, 1H), 14.7 (s, 1H)

Example 3:

Compound No. 4 of Table I is obtained in the form of the free base when the salt (nitrate) of Example 2 is neutralized in return with a 10% aqueous solution of ammonium hydroxide. NMR (CDC13): S0.7-2.8 (complex multiplets, 9H), 5.0 (q, 2H), 10 7.1-7.6 (m, 3H), 7.9 (s, 1H) , 8.0 (s, 1H)

Example 4:

Complex, with zinc chloride, of] - [2-cyano-2-phenylhexylJ-15 1,2,4-triazole (compound N "9, table I)

To 6.5 g (0.0256 mol) of l- [2-cyano-2-phenylhexyl] -1,2,4-triazole in 120 ml of methanol, 1.5 g (0.0111 mol) of zinc chloride and stirred for 15 min. The methanol is then removed by distillation, which gives 9.6 g of residue. This residue is taken up in moderately hot ethanol, and the solid product precipitates. This substance is separated by filtration, which gives 5.9 g (yield 59%) of the desired product, m.p. 175-177 ° C.

Table I CN

z-c-ch2-qy I

R2

Compound #

Z

R2

Q

y

1

2,4-Cl2 — C <jh3

n-C4H9

4- (1,2,4-triazolyl)

-

2

2,4-Cl2 — C6H3

n-C4H9

1 and 4- (1,2,4-triazolyl)

hno3

3

2,4-Cl2 — C6H3

n-C4H9

l- (1,2,4-triazolyl)

hno3

4

2,4-Cl2 — C6H3

n-C4H9

l- (1,2,4-triazolyl)

-

5

4-C1 — C6H4

ch3

l- (1,2,4-triazolyl)

-

6

4-C1 — C6H4

ch3

l- (1,2,4-triazolyl)

hno3

7

c6hs n-C4H9

l- (1,2,4-triazolyl)

HCl

8

c6h5

n-C4H9

l- (1,2,4-triazolyl)

-

9

c6hs n-C4H9

l- (1,2,4-triazolyl)

% ZnCl2

10

2,4-Cl2 - C6H3

n-C8H17

l- (1,2,4-triazolyl)

HCl

11

2,4-Cl2 - C6H3

n-C8H17

l- (1,2,4-triazolyl)

-

12

2,4-Cl2 - C6H3

CH2CH = CH2

l- (1,2,4-triazolyl)

-

(Table II at the top of the next page)

The substituted 1,2,4-triazoles, their addition salts with acids and their metal salt complexes, included within the scope of the present invention, are broad spectrum fungicides which have a high degree of activity at against phytopathogenic cryptogams which are sensitive to it. These compounds, salts and complexes are particularly effective at application rates of between approximately 50 and approximately 2000 ppm for controlling the network spot of barley (Helminthosporium teres) on barley plants, against gray mold ( Botrytis cinerea) on bean plants, against powdery bean rust (Erysiphe polygoni) on bean plants, against fluffy grape rust (Plasmo-spora viticola) on young vine plants, against rice wilt ( Piricularia oryzae) on rice plants, against late tomato rust (Phytophthora infestons) on young tomato plants, and against wheat stem rust (Puccinia graminis, f. Sp. Tritici, race 15B-2 ) on wheat seedlings.

To assess the efficacy of the compounds in question, a preliminary evaluation of the fungicidal efficacy is carried out by using the compounds on a support or in a vehicle at a concentration of 300 ppm and by spraying the composition onto the plants up to with runoff at a rate of approximately 14001 of composition-50 per hectare.

The general procedure consists in taking potted plants which have reached a suitable growth state so that they are sensitive to the cryptogamic disease against which it is a question of evaluating the effectiveness, of submitting the plants to jar, moving on 55 a conveyor belt, spraying, and letting them dry. The plants are then inoculated with the appropriate fungal spores which are allowed to incubate until the disease develops. The percentage of destruction of phytopathogenic cryptogams is then evaluated.

60 Typical compounds, as well as their addition salts with acids and their metal salt complexes, included within the scope of the invention, have manifested (when evaluated using the procedure described above, and at a concentration of 300 ppm) a capacity for complete destruction or up to an efficiency rate of 70 to 90% of: 1) Helminthosporium teres on barley plants (var. Wong), 2) Botrytis cinerea on bean plants (var. Vicia faba), 3) Erysiphe polygoni on bean plants (var. Drawf Hort), 4) Plasmospora viticola on young vine plants

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Table II

Elementary analysis: Calculated value (value found)

Compound No.

M.p. (° C)

VS

H

Cl

NOT

Where

1

46-49

55.74

4.99

21.94

17.33

(55.40)

(5.12)

(21.82)

(17.18)

2

110-120

46.65

4.44

18.36

18.13

12.43

(46.41)

(4.30)

(18.55)

(18.36)

(12.77)

3

156-158

46.65

4.44

18.36

18.13

12.43

(46.30)

(4.61)

(18.50)

(18.27)

(12.54)

4

oil

55.74

4.99

21.94

17.33

(55.91)

(5.09)

(22.07)

(17.21)

5

114-116

58.43

4.49

14.37

22.71

(57.40)

(5.03)

(13.37)

(19.48)

6

163 (dec.)

46.54

3.90

11.45

22.61

15.50

(47.28)

(3.90)

(11.50)

(21.97)

(16.00)

7

162-165

61.95

6.59

12.19

19.27

(61.10)

(6.35)

(10.49)

(17.91)

8

oil

70.84 (71.36)

7.13 (7.19)

-

22.03 (20.82)

9

175-177

55.87

5.60

10.99

17.37

10.13

(56.10)

(5.70)

(12.05)

(17.01)

(9.04)

10

125-131

54.88

6.60

25.58

13.48

(54.80)

(5.95)

(24.77)

(13.76)

11

oil

60.16

6.37

18.70

14.77

(56.97)

(6.48)

(17.93)

(14.25)

12

88-90

54.74

3.94

23.08

18.24

(54.97)

(3.97)

(22.85)

(18.59)

(var. Siebel 1000), 5) Piricularia oryzae on rice plants (var. Nova 66), 6) Phytophthora infestons on tomato plants (var. Rutgers), and 7) Puccinia graminis (f. sp. tritici race 15B-2) on wheat plants.

The compounds represented by formula (I), as well as their addition salts with acids and their complexes of the metal salt type, lend themselves to a wide variety of applications as broad spectrum fungicides, for example for silage of cereal grains and as fungicides on lawns, fruit or vegetable orchards, golf courses.

When used as fungicides, the active ingredients included in the scope of the invention are usually applied to combat phytopathogenic cryptogams on growing plants, on seedlings of plants or on the habitat of these plants, for example on the ground, in a fungididally effective amount.

The substituted 1,2,4-triazoles, as well as their addition salts with acids and their complexes of the metal salt type, included in the scope of the present invention, during their application as agricultural fungicides, are applicable on various places such as seeds, soil or foliage, especially when it comes to processing a marketable agronomic crop. For these purposes, the compounds in question can be used in technical or pure form as they have been prepared, or in the form of solutions or other types of compositions. Said compounds are usually used in the form of mixtures with an agronomically acceptable diluent, vehicle or support making it possible to make them subsequently dispersible as fungicides. For example, these fungicidally active ingredients can be used to establish compositions with a vehicle, support or diluent, in the form of powders, 45 granules, aerosols, emulsifiable concentrates, wettable powders or concentrates in fluid emulsions, the compositions of the last three types containing usually a surfactant with a liquid or solid vehicle. Details of suitable methods for the preparation of compositions and other pesticides useful in conjunction with the fungicidally active compounds in question can be found in the description of West German patent OLS PN 2604047 and in the various corresponding patents registered in other countries.

R

Claims (9)

633281 2 1. Fungicide compound of the following formula (I): R1 I C - '2 Z m <CH2> n * agronomically acceptable carrier or vehicle for the active ingredient. 7. Process for the preparation of a compound of the following formula: (I) R I 1 in which: Z is a C6 to C10 aryl radical which is optionally substituted; R1 is a cyano radical; R2 is: 1) hydrogen, 2) a Q to C12 alkyl radical, 3) a C3 to C8 cycloalkyl radical, 4) a C2 to C8 alkenyl radical, 5) a C5 to C8 cycloalkenyl radical, 6) a C2 to C8 alkynyl radical 7,7) an optionally substituted C6 to C10 aryl radical, 8) an optionally substituted C 1 to C 14 aralkyl radical in the aryl portion, 9) a C1 to C4 alkoxy radical ) a C2 to C4,11 alkenoxy radical) a C2 to C4,12 alkynoxy radical) a hydroxy radical, 13) a C6 to C10 aryloxy radical which is optionally substituted, or 14) a C7 to C14 aralkoyloxy radical which is optionally substituted in the aryl portion; Q is an optionally substituted l- (1,2,4-triazolyl) or 4- (1,2,4-triazolyl) radical; m is 0 or 1, and n is 1 or 2; as well as addition salts with an agronomically acceptable acid, and complexes of the agronomically acceptable metal salt type of such a compound. 2. Compound according to claim 1, characterized in that: R1 is cyano; Z is phenyl or naphthyl, each optionally substituted with up to three substituents chosen from halo, nitro, trihalogenomethyl, cyano, C 1 alkyl! to C4, C1 to C4 alkoxy, alkyl (C1 to C4) thio, alkyl (C1 to C4) sulfinyl and alkyl (C1 to C4) -sulfonyl; R2, when it is optionally substituted aryl, is as defined for Z in the present claim, and, when it is optionally substituted aralkyl, is phenyl C1 to C4 or naphthyl C1 to C4, each optionally substituted aryl group in the same manner as defined for Z in the present claim, and Q is l- (1,2,4-triazolyl) or 4- (1,2,4-triazolyl), each optionally substituted with up to two substituents selected from halo, C 1-6 alkyl! to C4, nitro and cyano. 3. Compound according to claim 2, characterized in that: Z is phenyl optionally substituted with up to three halogen atoms; R2 is C1 to C8 alkyl or C2 to C8 alkenyl; Q is an unsubstituted l- (1,2,4-triazolyl) or 4- (1,2,4-triazolyl) radical; m is 0, and n is 1. 4. Compound according to claim 3, characterized in that Z is phenyl; R2 is n-C4H9, and Q is 1- (1,2,4-triazolyl) unsubstituted. 5. Use of the fungicidal compound according to one of claims 1 to 4 for combating phytopathogenic cryptogams on plants, characterized in that the compound, an addition salt with an acid, is applied in an effective fungicidal amount, or a metal salt type complex, growing plants, plant seeds or plant habitat. 6. Use according to claim 5, characterized in that the compound is in a composition in the form of: a) a powder or granules, or b) an emulsifiable concentrate, an emulsion concentrate fluid or wettable powder each containing a surfactant and containing a diluent or Z - (CHJ - C - (CHJ 2 m, 2 n 10 I - RZ characterized in that a compound of formula is reacted: , 1 Z - (CHJ - C - (CHJ - NH-Z m - 2 n 2 2 20 R with a compound of the following formula: CH- N - CR3 = N - N = CR ** - N " CH. CH. In which Z, m, R1, R2 and n are as defined in claim 1, while R3 and R4, which may be the same or different, represent hydrogen, or a halo, Ct to C4 alkyl radical , nitro or cyano. 35