CS221276B2 - Fungicide means - Google Patents

Abstract

1. Claims for the contracting states BE, CH, DE, FR, GB, IT, LU, NL, SE 1,2,4-Triazol-1-yl compounds of the general formula I see diagramm : EP0010298,P12,F3 where R**1 denotes phenyl substituted by clyclohexyl, phenyl, 1 to 3 halogen atoms or alkyl of 1 to 4 carbon atoms, and Y denotes OR**2 or see diagramm : EP0010298,P12,F4 where R**2 denotes alkynyl of 3 to 15 carbon atoms, R**3 denotes hydrogen, alkyl of 1 to 20 carbon atoms, alkenyl of 3 to 15 carbon atoms, phenyl or cyanoethyl, and R**4 denotes phenyl or benzyl optionally substituted by 1 or 2 halogen atoms, trifluoromethyl or alkyl of 1 to 4 carbon atoms, or alkenyl or alkynyl of 3 to 15 carbon atoms, phenylethyl, naphthyl or cyanoethyl, and their plant-compatible salts and metal complexes. 1. Claims for the contracting state AT A fungicide containing a 1,2,4-triazol-1-yl compound of the general formula I see diagramm : EP0010298,P13,F3 where R**1 denotes phenyl substituted by cyclohexyl, phenyl, 1 to 3 halogen atoms or alkyl of 1 to 4 carbon atoms, and Y denotes OR**2 or see diagramm : EP0010298,P13,F4 where, R**2 denotes alkynyl of 3 to 15 carbon atoms, R**3 denotes hydrogen, alkyl of 1 to 20 carbon atoms, alkenyl of 3 to 15 carbon atoms, phenyl or cyanoethyl, and R**4 denotes phenyl or benzyl optionally substituted by 1 or 2 halogen atoms, trifluoromethyl or alkyl of 1 to 4 carbon atoms, or alkenyl or alkynyl or 3 to 15 carbon atoms, phenylethyl, naphthyl or cyanoethyl, and its plant-compatible salts and metal complexes.

Description

SUMMARY OF THE INVENTION The present invention provides fungicidal compositions containing the active ingredient 1,2,4-triazol-1-yl derivative of the formula I

ye which

A represents a halogen atom, a phenyl group, an alkyl group having 1 to 6 carbon atoms, a cyclohexyl group, a benzyl group or a radical of formula

where

Hal represents a halogen atom,

V represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 4 carbon atoms,

C represents a hydrogen or halogen atom,

X is oxygen or sulfur; and

Y is C 3 -C 6 alkyloxy or the remainder of the formula

R ⁷ /

N \

R ⁸ where

R ⁷ is hydrogen, C 1 -C 4 alkoxy, C 1 -C 6 alkyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl, C 1 -C 4 cyanalkyl an alkyl moiety or a benzyl group; and

NH-CS-NH-CO-OCH 2

R ⁸ represents a hydrogen atom, a phenyl or benzyl radical which may be mono- or disubstituted by halogen, an alkyl group having 1 to 6 carbon atoms or a trifluoromethyl group, furthermore a cyclohexyl group, a naphthyl group, a cyanalkyl group having 1 to 4 carbon atoms C 3 -C 6 alkenyl, the residue

or • J •. (Or a plant-tolerable salt thereof and / or a metal complex.

Salts compatible with plants include, for example, hydrochlorides, hydrobromides, sulfates, nitrates, phosphates or dodecylbenzenesulfonates.

The metal complexes mentioned above are compounds of formula IX

in which

А, В, С, X and Y are as defined above and

Me is a metal cation such as copper, zinc, tin, manganese, iron, cobalt or nickel,

Z is an anion of an inorganic acid, for example hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid or hydrobromic acid, and where they have a value of 1,2,3 or 4.

The 1,2,4-triazolyl derivatives of the above general formula (I) may be prepared by the production of:

(a) compounds of the general formula

In X

in which

A, V, and C are as defined above, or salts thereof, and with trlazole of formula IV

(II) wherein X and Y are as defined above and

L ¹ and L ² represent the same or different nucleophilically cleavable groups, react with a compound of formula III or salts thereof, optionally in the presence of a solvent or diluent, and / or an inorganic or organic base at a temperature between 0 and 180 ° C, optionally with the addition of a reaction accelerator, or that

(b) a compound of formula (V)

(V) in which

A, В and C are as defined above and

M represents a hydrogen atom, a metal cation equivalent or an optionally substituted ammonium ion, reacted with a compound of formula VI

HY (VI) wherein

Y is as defined above, after addition or concomitant addition of reagents suitable for converting an acid to a derivative thereof, optionally in the presence of a solvent or diluent, and / or an inorganic or organic base at a temperature between -20 and +180 ° C, optionally in the presence of an accelerator. reaction, and optionally sulfur is then introduced into the compounds thus obtained, or is added

c) reacting a compound of the above formula V with a compound of the formula VII

L ³ Y (VII) wherein

Y is as defined above and

L ³ represents a nucleophilically cleavable group, optionally in the presence of a solvent or diluent, and / or an acid binding agent at a temperature between -20 and +180 ° C, optionally in the presence of a reaction accelerator, and optionally sulfur is introduced into the compounds thus obtained; se

d) compounds of formula VIII

in which

A, V, C, Y and L ² are as defined above, reacted with trlazole of the above formula IV, optionally in the presence of a solvent or diluent, and / or an inorganic or organic base at a temperature between -20 and +180 ° C optionally in the presence of a reaction accelerator, and optionally the sulfur is then introduced into the compounds thus obtained, whereupon the compounds obtained according to processes a) to d) are optionally converted into their plant-compatible salts or metal complexes.

The nucleophilically cleavable groups L ¹ and L ² mentioned in the reactions according to paragraphs

a) and d) are, for example, halogen atoms such as chlorine, bromine or iodine, a hydrogen sulphate residue, a sulphonate residue, or an optionally substituted alkylsulphonyloxy-, arylsulphonyloxy-, alkylsulphate, phenoxy, phenylthio, oxonium, sulphonium or ammonium radicals. Suitable inorganic bases which may also be used as; acid binding agents in the reaction of paragraph a) are, for example, alkali metal and alkaline earth metal hydroxides such as sodium hydroxide, potassium hydroxide or calcium hydroxide, alkali metal carbonates such as potassium carbonate or sodium carbonate, alkali metal hydrides such as sodium hydride, alkoxides alkali or alkaline earth metals such as sodium methoxide, magnesium ethoxide or sodium isopropoxide, or tertiary amines such as trimethylamine, triethylamine, N, N-dimethylamine, N, N-dimethylcyclohexylamine, N-methylpiperidine or pyridine, or further azoles such as- 1,2,4-triazole or imidazole. However, other conventional bases may also be used for this purpose.

Suitable salts of the compounds of formulas III and IV above are, for example, alkali metal, alkaline earth metal or optionally substituted ammonium salts of these compounds.

Preferred solvents or diluents include halogenated hydrocarbons such as methylene chloride, chloroform,

1,2-dichloroethane or chlorobenzene, aliphatic or aromatic hydrocarbons such as cyclohexane, petroleum ether, benzene, toluene or xylenes, alcohols such as methanol, ethanol, isopropanol or n-butanol, esters such as ethyl acetate, amides such as dimethylformamide, nitriles, such as acetonitrile, sulfoxides such as dimethyl sulfoxide, ketones such as acetone or methyl ethyl ketone, ethers such as diethyl ether, tetrahydrofuran or dioxane, or mixtures of these solvents. The solvent or diluent is suitably used in an amount of from 100 to 2000% by weight, preferably from 100 to 1000% by weight, based on the starting materials of the general formula used.

II and III respectively.

Suitable reaction accelerators are preferably metal halides, such as sodium bromide or potassium iodide, crown ethers, quaternary ammonium compounds, such as

221278 trabutylammonium iodide or acids, or a combination of these reaction accelerators.

The reaction according to the invention is generally carried out at a temperature between 40 and 150 ° C, under normal pressure or under positive pressure, continuously or discontinuously, the reaction time being from 1 to 60 hours.

In general, 0.5 to 2 moles of the starting materials of formulas III and IV, preferably 0.9 to 1.3 moles of the starting materials of formulas III and IV, and from 1 to 1 to 2 moles are used per mole of the compound of the formula II. 4 mol, preferably 1.8 to 2.3. mol of a base and optionally 0.01 to 0.1 mol of a reaction accelerator.

In accordance with a preferred embodiment of paragraph (a) above, the reaction is carried out by mixing the starting materials of formulas III and IV in any order with a base and a diluent, adding the starting material of formula II and optionally a reaction accelerator, and allowing 0.5 to 120 hours, preferably 1 to 60 hours, to react at a temperature which may be between 40 and 150 ° C.

The isolation of the compounds according to the invention is carried out, for example, by evaporating the diluent, removing the residue with a suitable solvent and washing the solution with water to remove excess base and unreacted starting materials of formulas III and IV. The products remaining after evaporation of the solvent generally do not need further purification, but if necessary they can be further purified by a known method such as recrystallization, extraction or chromatography.

Among the known reagents suitable for converting an acid to its derivative at work within the meaning of variant b), examples include, but are not limited to, proton or Lewis acids, inorganic or organic acid halides, such as thionyl chloride, phosphorus pentachloride, acetyl chloride or the like. a chlorocarbonic acid ester such as the corresponding ethyl, tert-butyl or benzyl ester, anhydrides such as ketene, diimides such as N, N'-dicyclohexylcarbodiimide or carbonyl or sulfonyldiazoles such as carbonyldiimidazole, carbonylditriazole, sulfonyldiimidazole or sulfonylditriazole.

Particularly suitable for use in variant c) are those compounds of formula VII wherein L ³ is a nucleophilically cleavable leaving group such as a halogen atom such as chlorine, bromine or iodine, an optionally substituted alkylsulfonyloxy or arylsulfonyloxy group such as mesyloxy, trifluoromethylsulfonyloxy, broro, or a tosyloxy group, an alkyl sulfate moiety such as a methyl sulfate moiety, or a diazo group.

Suitable solvents or diluents and acid binding agents, preferably used in the process according to variants b), c and d), are suitable substances mentioned above for the process according to variant a).

Generally described reactions in terms of variants

b), c) and d) as well as isolation of the compounds according to the invention are carried out by methods known per se [see Houben-Weyl, Vol. 8, p. 508 et seq. And p. 653 et seq., Stuttgart (1952); 15, Stuttgart (1974)).

All known methods of introducing sulfur, such as reaction with dimeric phosphorus pentasulfide (PIT1) or with dialkoxy-dithiophosphoric acids, can be used to prepare the corresponding thions of formula I in which X is sulfur [see Houben-Weyl, Vol. 8, p. 672, Stuttgart (1952) and Vol. 9, p. 745 et al., Stuttgart (1955); Bull. Soc. Chim. Belg. 86 (1977) 321].

The starting materials of the above-mentioned general formula (V) can be prepared by reacting a compound of the general formula (X)

(X) in which

L ¹ , L ² and M are as defined above, reacted with a hydroxy compound of formula III

in which

A, V and C are as defined above, or with salts thereof, and with the triazole of formula IV

(iv) or salts thereof, optionally in the presence of a diluent and / or an acid binding agent at a temperature between 0 and 180 ° C, optionally with the addition of a reaction accelerator.

The starting materials of formula (VIII) may be prepared by known methods, for example by halogenation of the corresponding aryl- or heteroaryloxyalkanoic acid derivatives (see DOS 18 08 034).

The compounds of formula I contain one or more chiral centers. Pure isomers can be obtained from mixtures of isomers resulting from the synthesis in a manner known per se.

Both pure isomers and mixtures thereof can be used in accordance with the invention.

22127S

Preparation of the compounds illustrated by the following Examples in which the VSA ^to the extent ^y n and ^l in cut way limited ^to day.

Preparation of starting materials and 81.5 parts of ^{2,4-dichlorophenyl} 34.5 ^d ua clay 1,2,4-triazole in 300 parts of ethanol are added 90 parts of commercial sodium methoxide solution (30 parts of sodium in 100 parts of ^the organic solution in the methanol), and after a short ^{straight p} romíchání is added to ¹⁰⁹ ibromoctové ^{d y y} Selin. After čtrn ctiho ^{s d s} m INOV reflux, the solvent was evaporated, the residue taken up in about 1000 ml of water, after cooling acidified with concentrated hydrochloric acid to pH 1, the precipitate is suctioned off and washed with isopropanol. After drying, 121 children ^{2 (2 ', 4'} tdichlorf ENOX ^yl) -2- (R + P riazoP •• l'- ^y I) ^'alkyl acetate petroleum jelly tajteí decomposition ^at 211-213 ° C.

b) To 1080 parts of a technical solution of sodium methoxide in methanol (30 parts of sodium methoxide in 100 parts of solution) were added 771 parts of 4-chlorophenol and 414 parts of 1,2,4-triazole. After stirring briefly, 774 parts of dichloroacetic acid are added to the mixture at about 60 ° C. From a mixture ^of methanol was then odctestitevává and simultaneously isopropanol added to it so as to re ^{ALI tup} was easily stirrable. Jekmile temperature of the mixture rose to 80 ° C, the mixture is stirred for 10 hours, then distilled rozpouštedto of ^d to ss ^ t ^k at the ^instance water was added to the 'ice and acidified with concentrated hydrochloric acid. The resulting precipitate which formed was ^F sucks a ^{d p} rom ^{y p} Iso ro anol ^p and ^y su ^Si. Yielding 676 parts ⁽⁵ 8%) of ^{2 (4'-chlorophenoxy)} - ² - (l ^{', 2',} 4'-triazole ^{t azetidinyl)} acetic acid ^{ee 's alkyl} Selin melting point ^- at 205-207 ° C.

c) To a solution of 23 parts of sodium in 600 parts of isopropanol was added 94 parts of phenol and 70 days 1,2,4-tílazoluj ^p and ^{k p} Rida 29 parts dicteoroctové ^alkyl selrn ^y and 1 part of sodium ^iodide, and the reaction was 5 hours ^refluxed ° p ^{d p} from Etna c ^hl and em ^nr. Thinner from ^p Ari ytek ^b of the extended ^P estuary in the water and acidified with dilute ^ga Nou ^alkyl Seun -chlorovodíkovou. The ^y lo ^on prize SR ^and the precipitate is sucked by ^{d p} rom ^y Iso ^p ropanotem and dried ^š Í. Yielding 142 parts ⁽⁶⁶ percent of theory) of 2-t-fAnoxx tr, 2 ', 4'ttríazollrt • l-yl) acetic acid to ^{y y} Selin M.P. s ^p 180-183 ° C.

When ^{p p} rava resulting genus ^KTU

Example 1

To 115 parts of imidazole in ^{1000 says} Lech tetrahydro ^y bottomed flask under chlazern at room teptote ^p s and ^p e ^{to 5} 0 ^parts thrnnytehloridu. After 1 hour MICL te ^p s ^p mfetBosti ture, then ^y in the precipitated precipitate ^Ž emna aspirated. The ^filters were also ^to e and ^{p for p} Enzi 110 sus child ² • (Г Х ^ + пзгоРГ-у) -2- (2 ^{', 4'} - ^d ic ^h lorfenot xy) acetic acid in 400 parts of ^{tetrahydrofuran,} the mixture 3 hoďlny MTE ^hook at room temperature and then to it were added portionwise 85 parts of N - ^ - ^ -N ^ aminophenyl methiox ^ arbonylthiomoěoviny and the resulting mixture 24 hours MIC ^hook te ^p s ^p mfetoostí ture. ^p o ^h at U ^S CLEANING reaction mixture was poured into water, the precipitate was filtered with suction and dried ^p o ^{s s} is triturated with cold ethyl acetate. ^Yielding 140 parts Nt) of 2- [2 '- ^(l', 2 ", 4" -triazolll "t ^s] jt t ^{2", 4} "tdichlorfenox ^yl) acet ^yl] aminophenyl ^yl} -N-methoxykarbonylthtomočoviny tajlrí with decomposition at 139-142 ° C.

EXAMPLE 2 parts of 2 - ^ (10 ^ ^^^) -2- (l ', ^2', 4'-triazolll'- ^yl) acetic acid ^alkyl selrn ^y is charged <fo WO parts of methylene chloride and added with 0.5 parts dimethylformamide and 15 parts of trimethylamine. To the mixture, cooled to -10 ° C under mtehání ^{EXAMPLES 15} and ^p e Clito thionytehtoridu. The reaction mixture was stirred at room temperature overnight. A solution of 12 parts of triethylamine and 12 parts of aniline in 20 parts of methylene chloride was added dropwise under cooling at + 10 ° C. The resulting mixture was heated at reflux for 1 hour, then cooled, the precipitate formed was filtered off with suction, washed with methylene chloride and the organic phase was evaporated. After filtration of the oily residue over silica gel using as metoytenchloridu ^- elučmho agents zi'ská 18 parts · Single -oleate which upon standing overnight - crystallized under ether.

With ^k and ^September 15 parts of aniline 2- ^{(4'-chlorophenoxy} -ch ^l) ^ - (+ Г ^^ НзяоРГ-у) -acetic acid te ^p ture mp 134-136 ° C.

Example 3

In ^{150 d h} iTec tetrahydro ^y sus bottomed flask with ^p en ^d u e ^j 23 ^parts of 2- ^{(4'-phen yl} lf ENOX ^yl) -2- (1'2 ^{'4'ttr and} azol1Γ ^1-yl) -acetic acid ^alkyl Selin if ^y sus Enzi ^p is the ^{p p} lstech parts ^{and 13} parts. N, N'-carbonyldiimidazole ^y carbon. After stirring at room temperature přikaje solution of 9 parts of ^ ftooranitínu ^{20 d} ílech tetrahydrofuran rea ^{CZK nus} smfe stirred for ¹² h, ^p, and the vyhje into ^{1,000 parts of} a ^{dy 1 edema, - characterized} in the precipitated precipitate was suction filtered and it is dried.

^Získá se²⁶ child^p-^fluoranilide²- (4‘-Fen.)^ylfenoxy) -² (F ^^ P + Riazohr-y^- ) acetic acid m.p. 92-96 ° C.

EXAMPLE 4 parts of 2- (4'-chlorophenoxy) -2- (P.JP + ^ -acetic acid methyl ester riazoolr-acid are suspended in 150 parts of tetrahydrofuran and the suspension was added portionwise 24 parts of carbonyldiimidazole. After stirring at room temperature ^to a mixture of ^BC, i ^ e and ^p mites ^{to 25.8} parts of o-meth - ^N-1 nu cyklohexylhydroxy1ami in 50 parts of tetrahydrofuran. Reakčrt mixture was stirred overnight, then added with stirring to 1000 parts of ice water and the precipitated oil is separated Filtration through silica gel yielded 10.5 parts of 2- (4'-chlorophenoxy) -2- (1 ', 2', 4'-triazole-1 'N-cyclohexyl-O-methylhydroxylamide)

m.p. 103-104 ° C).

For example, the following compounds can be prepared in an analogous manner:

Table

X Y

4-C1 — C6H4—

2.4- diCl — C6H3—

4-C1 — C6H4—

2.4- С1 — СбНз—

2.4- diCl - C6H5 -

4-C1 — C6H4—

2.4- diCl — C6H3—

2.4- diCH3 — C6H3—

2.4-diCl-C6H3-4-C1-C6H4-

2,4-diCl-C6H3-4-C1-C6H4- 2,4,5-triCl-C6H2-

2,4-diLC1-C6H3-4-C1-C6H4-

2.4-dlCl — CeH3—

2,4-diCl-C6H3-2, - (-) - - - - - - - - - - - -

2,4-diCl — C6H3-4-C1 — C6H4—

2,4-diCl-CeH5-4-C-C6H4-

2,4-diCl — C3H3-4-C — C6H4—

4-C — C6H4—

4-C1 — C6H4—

4-C1 — C6H4—

O O O O

OC (CH 3) C C = CH

OC (CH 3) 2 C 5 CH

_0-CH3

NHC (CH 3) 2 C = CH

NHC (CH 3) 2 C 5 CH

NHC6H5

NHC6H5

About NHC6H5

O NH-2-F — C6H4

O NH-3-F — C6H4

O NH-3-F — C6H4

O NH-4-F — C6H4

O NH-4-F — C6H4

O NH-4-F — C6H4

O NH-4-C 1 -C 6 H 4

NH-2,4-diF-CeH3

O NH-3,5-diCl-C6H3

O NH-2-itC 3 H 7 -C 6 H 4

O NHt3-1 ^ 6] ^ C (C1-4H9-C6H4

O NH-3-thi-C (C: 4H9-C6H4

O NH-3-CF 3 - C 6 H 4

O NH-3-CF 3 - C 6 H 4

O N (CH 3) -4-C 1 -C 6 H 4

O NH — CH2 — C6H5

O N (CH 3) CHCl 6 H 5

CH 2 CN melting point (° C) of ind6x refraction

91— 94

60—63

103—104

92— 94

112—115

74—82

92—95 114—116

92—98

99—101

102—105

80—84

138— 142

136—140

139— 142

146—149

122—124

170—173

90—94

153— 158

154— 155

121—124

115—122

125—127

72—75

1,5652

144—146

95—103

85—90

C

melting point (° C) refractive index

2,4-diCl - СбНз -

4-C1 — СбШ—

4-C1 — СбН4—

4-C1 — СбН44-F — СбН4—

106—108

152—156

1,526

1,530

102—110

2,4-diCl — СбНз — O

2.4-diCl — СбНз — O

3.5-diCH3 — СбНз — O ⁰

4-tert-C 4 H 9 -C 6 H 4 -O

2,4-diCl — СбНз — O

4-C1 — СбН4 — O <>2> 4-C1 — СбН4 — O

4-C1 — СбН4 — O

O-o <(6)

2,4,5-triCl — СбНз — O

4-F — СбН4 — O

Ы (СНз) СбН5 N-CHxCH = CH ₉ é 145—148 76—77 N (CH 3) C 6 H 5 101—103 NH-4F-CeH4 94—96 NH-4F — CeH4 N-2,4-diCl — СбНз 123—125 109—111 СНз N (CH 2 CH 2 CN) 2 1,529 NH — СбНб 120—123 N — СбНб 74-76 1 СНз — СеНб N (CH 3 -CH = CH 2) 2 1.5280 NH — СбН5 110—113 NHC (CH 3) 2 C = CH NH-4F-Si ₄ 176—185 127—135

melting point (° C) refractive index

2,4,5-triCl — СбН ₂ -

N (CH 3) C 6 H 5

105—111

168—172

158—163

4-C1 — СбН4—

69—74

1,532

2,4-diCl — СеНз—

2,4-diCl-C 6 H ₃ -

2,4-diCl — CeH3—

O

CH3

NH - CH 2 - 2 Cl - CeH 4

NHCeHs

NH4C1-CeH4

NHCH2C6H5

N (CH 2 —CH = CH ₂ ) 2

H NH - 3 CF 3 - C 6 H 4

90—92

112—114

102—103

102— 105

103— 106

120—125

71—76

49—54

120—125

The following example illustrates the preparation of metal complexes.

Example 66 parts of 2- (4'-phenylphenoxy) -2- (1 ', 2', 4'-triazol-1'-yl) acetic acid 4-fluoroanilide was dissolved in 200 parts of ethanol at 35 ° C and the resulting solution a solution of 14 parts of copper (I) chloride in 100 parts of ethanol is added. After stirring for 2 hours, the reaction mixture is cooled to 15 ° C and the precipitate formed is filtered off with suction.

13 parts of bis [2- (4'-phenylphenoxy-2- (1 ', 2'4'-triazol-1'-yl) acet-4-fluoroanilide] copper (I) chloride are obtained, m.p. 176-180. degrees Celsius.

In a similar manner, the other compounds of the invention can also be converted into metal complexes.

The compounds of the invention and their salts and metal complexes are distinguished by excellent activity against a wide variety of phytopathogenic fungi, in particular from the class of Ascomycetes and Basidiomycetes. The disclosed compounds are partially systemically active and can be used as foliar and soil fungicides.

Of particular interest is the usefulness of the fungicidally active compounds for controlling numerous fungi on various crop plants or their seeds.

In this context, crop plants include, in particular, wheat, rye, barley, oats, rice, maize, cotton, soy, coffee, sugarcane, fruit and ornamental plants in garden architecture, as well as vegetables such as cucumbers, beans, gods and cucurbits.

The novel compounds described are particularly suitable for combating the following plant diseases:

Erysiphe graminis (powdery mildew) on cereals

Erysiphe cichoracearum (Powdery mildew) on cucurbits

Podosphaera leucotricha (apple powdery mildew) on apple trees

Uncinula necator (powdery mildew) on grapevine

Erysiphe polygoni (powdery mildew) on beans and beans

Sphaerotheca pannosa (powdery mildew) on roses Puccinia species (rust) on cereals Rhizoctonia solani (cotton potato) on cotton Helminthosporium species (helminthosporosis) on cereals Ustilago species on cereals and sugar cane

Rhynchosporium secale (rhynchosporium spots) on cereals

Venturia inaequalis (apple scab).

The compounds of the invention are applied by spraying or dusting the plants with the active compounds or by treating the seeds of the plants with the active compounds. The application is carried out before infection of the plants or seeds by the fungus.

The active compounds according to the invention can be converted into the customary formulations, such as solutions, emulsions, suspensions, dusts, powders, pastes and granules. The dosage forms depend entirely on the intended use, but in any case are intended to ensure a fine and uniform distribution of the active ingredient. These compositions are prepared in a manner known per se, for example by mixing the active ingredient with solvents and / or carriers, optionally with an emulsifier and a dispersant.

Suitable carriers and auxiliaries are, in particular, solvents: aromatics (e.g. xylene or benzene), chlorinated aromatics (e.g. chlorobenzene), paraffins (e.g. petroleum fractions), alcohols (e.g. methanol or butanol), amines (e.g. ethanolamine) dimethylformamide and water; carriers such as natural stone meal (for example kaolins, alumina, talc or chalk) and synthetic stone meal (for example highly disperse silicic acid or silicates); emulsifiers such as non-ionic and anonic emulsifiers (e.g. polyoxyethylene fatty alcohol ethers, alkylsulfonates and arylsulfonates) and dispersants such as lignin, sulfite waste liquors and methylcellulose.

The concentrates generally contain between 0.1 and 95 wt. % of active ingredient, preferably 0.5 to 90 wt. % Of the active substance.

Depending on the type of effect desired, the active substance consumption is between 0.01 and 3, preferably between 0.01 and 1 kg of active substance per hectare.

The concentrates, or compositions which can be prepared therefrom, such as solutions, emulsions, suspensions, powders, dusts, pastes or granules, are applied in a known manner, for example by spraying, fogging, dusting, pickling or dressing.

The following preparations are exemplified by the above compositions:

I. 90 parts by weight of the compound of Example 6 are mixed with 10 parts by weight of N-methyl-.alpha.-pyrrolidone to give a solution which is suitable for application as small droplets.

II. 20 parts by weight of the compound of Example 1 are dissolved in a mixture consisting of 80 parts by weight of xylene, 10 parts by weight of an adduct of 8 to 10 moles of ethylene oxide per mole of N-monoethanolamide oleic acid, 5 parts by weight of calcium dodecylbenzenesulfonic acid and 5 parts by weight. of an addition product of 40 moles of ethylene oxide per mole of castor oil. By pouring and finely distributing the solution in 100,000 parts by weight of water, an aqueous dispersion is obtained which contains 0.02% by weight of active ingredient.

III. 20 parts by weight of the compound of Example 2 are dissolved in a mixture consisting of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of an adduct of 7 moles of ethylene oxide per mole of isooctylphenol and 10 parts by weight of an adduct of 40 moles of ethylene oxide per mole of castor. oils. By pouring and finely distributing the solution in 100,000 parts by weight of water, an aqueous dispersion is obtained which contains 0.02% by weight of the active ingredient.

IV. 20 parts by weight of the compound of Example 1 are dissolved in a mixture consisting of 25 parts by weight of cyclohexanol, 65 parts by weight of a mineral oil fraction

boiling point 210 DEG-280 DEG C. and 10 parts by weight of an adduct of 40 moles of ethylene oxide per mole of castor oil. By pouring and finely distributing the solution in 100,000 parts by weight of water, an aqueous dispersion is obtained which contains 0.02% by weight of the active ingredient.

V. 20 parts by weight of the active compound of Example 2 are mixed well with 3 parts by weight of diisobutylnaphthalene-α-sulfonic acid sodium salt, 17 parts by weight of ligninsulphonic acid sodium salt from waste sulphite lyes and 60 parts by weight of powdered silica gel and ground in a hammer. mill. By finely distributing the mixture in 20,000 parts by weight of water, a spray suspension is obtained which contains 0.1% by weight of active ingredient.

VI. 3 parts by weight of the compound of Example 23 are intimately mixed with 97 parts by weight of finely divided kaolin. In this way, a dust containing 3% by weight of the active ingredient is obtained.

VII. 30 parts by weight of the compound of Example 2 are intimately mixed with a mixture of 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil which has been sprayed onto the surface of the silica gel. In this way, an effective formulation with good adhesion is obtained.

VIII. 40 parts by weight of the active compound of Example 2 are intimately mixed with 10 parts of the sodium salt of the phenol sulfonic acid, urea and formaldehyde, 2 parts of silica gel and 48 parts of water to obtain a stable aqueous dispersion. By diluting this dispersion with 100,000 parts by weight of water, an aqueous dispersion containing 0.04% by weight of the active ingredient is prepared.

IX 20 parts of the active compound of Example 3 are mixed intimately with 2 parts of calcium dodecylbenzenesulfonic acid, 8 parts of polyglycol ether of fatty alcohol, 2 parts of sodium salt of phenolsulfonic acid, urea and formaldehyde condensation product and 68 parts of the paraffinic fraction of mineral oil. stable oil dispersion.

The active compounds according to the invention can be present in these compositions in combination with other active compounds, such as herbicides, insecticides, growth regulators and fungicides, or they can also be mixed with fertilizers and applied in this form. At. mixing with the fungicides takes place. in many cases, it will increase the spectrum of efficiency and synergism.

The following list of fungicides with which the compounds of the present invention may be combined illustrates these combination possibilities in more detail, but is by no means at all. does not limit.

Fungicides with which the compounds of the present invention may be combined are, for example, di-dicarbamates and derivatives thereof, such as ferric dimethyldithicarbamate, zinc dimethyldithiocarbamate, manganese ethylene-bis-dithiocarbamate, manganosin-zinc manganese zinc di-ethylenediamine-bis, amethylenodiocarbamate, tetramethylthiuramide sulfide, zinc ammoniacal complex of N, N'-ethylene-bis-dithiocarbamate and N, N'-polyethylene-bis- (thiocarbamoyl) disulfide,

Zinc N, N‘-propylene-bis-dithiocarbamate, ammoniacal complex of N, N‘-propylene-bis-dithocarbamate zinc and N, N‘-polypropylene-bis- (thmcarbamoyl) -disulfide;

nitro derivatives, such as dinitr o- (1-methylheptyl) phenyl cronate, 2-sec-butyl-4,6-dinitrophenyl-3,3-dimethyl acrylate,

2-secibutyl-1,4,6-dinitrophenylisopropyl carbonate;

heterocyclic compounds such as

N-trichloromethylthio-tetrahydrothiophthalimide, N-trichloromethylthiophthalimide, 2-heptadecyl-2-imidazoline acetate,

2,4-dichloro-6- (o-chloroanilino) -s-triazine,

5-Amino-1- [bis- (dimethylamino) phosphonyl] -3-phenyl-1,2,4-triazole, 5-ethoxy-3-trichloromethyl-1,2,4-thiadiazole ,

2,3-dicyano-1,4-dithiaanthraquinone, 2-thio-1,3-dithio [4,5-b] quinoxaline, 1-butylcarbamoyl-2-benzimidazole-carbamic acid methyl ester,

2-methoxycarbonyl-benzimidazole, 2-thiocyanatomethylthiobenzthiazole,

4- (2-chlorophenylhydrazino) -3-methyl-5-isoxazolone, pyridine-2-thicyl-1-oxide,

8-hydroxyquinoline or its copper (II) salt,

2,3- dihydro-l ^ _{-karboxanilido-methyl-1} 4-cχ.athiin-4,4-dioxide,

2.3-Oxidro-5-cetraoxanilido-6-methyl-1,4-oxathiin

2- (2-furyl) benzimidazole, piperazin-1,4-diylbiphenyl- [1- (2,2,2-trifluoromethyl) formamide],

2- (4-thiazolyl) benzimidazole,

5-butyl-2-dimethylamino-4-hydroxy-6-methylpyrimidine, bis- (p-chlorophenyl) pyridine-methanol, 1,2-bis- (3-ethoxycarbonyl-2-thioureid.c) benzene,

1,2-bis- (3-methoxycarbonyl-4'-benzoyl) benzene;

and various fungicides such as dodecylguanidine acetate,

3- [3- (3,5-dimethyl-2-hydroxy-oxy-cyclohexyl) -2-hydroxyethyl] -glutarimide, hexachlorobenzene, N-dichlorofluoromethylthio-N ‘, N‘-dimethyl-N-phenyldiamide sulfuric acid,

2,5-dimethylfuran-3-carboxanilide, cyclohexylamide 2,5-dimethylfuran-3-

-carboxylic acids, 2-methylbenzoic acid anilide, 2-iodobenzoic acid anilide,

1- (3,4-dichloroanilino) -1-formylamino-2,2,2-richethanol,

2,6-dimethyl-N-tridecylmorpholine and its salts,

2,6-dimethyl-N-cyclododecylmorpholine and its salts,

D, L-methyl-N- (2,6-dimethylphenyl) -N-2-fluoroaneate, D, LN- (2,6-dimethylphenyl) -N- (2'-methoxyacetyl) aniline methyl ester , 5-nitroisophthalic acid diisopropyl ester,

1- (1‘, 2‘, 4‘-triazol-1--yl) - [1- (4‘-chlorophenoxy)] -3,3-dimethylbutan-2-one,

1- (1‘, 2 2, 4‘-triazol-1--yl) - [1- (4‘-chlorophenoxy)] -3,3-dimethylbutan-2-ol,

N- (2,6-methylbutyl) -N-chloroacelyl-D, L-2-aminobutyrolactone,

N- (n-propyl) -N- (2,6-richlorophenoxyethyl) -N‘-imidazolylurea.

Biological effect of the novel compounds according to. The invention is illustrated by the following Example A. 2-Phenyl-2- (1 ', 2', 4'-triazol-1'-yl) -acetic acid tert-butyl ester (N), known from DOS No. 26 38 470 . '

Example A

The leaves of germinated wheat plants ('Caribo'), grown in a greenhouse, are sprayed with aqueous emulsions containing 80% by weight of the active ingredient and 20% emulsifier in the dry matter, and dusted with spores (oidiemi) of Erysiphe graminis var. . The test plants are then kept in a greenhouse at 18 to 24 degrees Celsius, and after 10 days, the extent of the infestation by the powdery mildew is evaluated.

The results are summarized in the following table, with values of 0 to 5, where 0 means no fungus occurrence and 5 represents complete fungal infestation of the leaves.

Table

active substance (example #) attacking the leaves after spraying with the active substance concentration agent. (%) 0.025 0.012 0.006 1 0 1 1 2 0 0 0 3 0 0 0 4 0 0 2 5 0 2 3 8 1 2 2 9 0 0 2 11 0 0 2 12 1 1 2 13 0 0 0 14 0 0 0 21 0 1 2 23 0 0 2 - 3 26 0 0 1 27 Mar: 0 2 2-3 28 0 0 2 29 0 0 0 31 0 0 2 32 0 0 0 34 0 1 2 35 0 0 0 36 0 0 3 37 0 0 0 38 0 0 0 40 0 0 0 45 1 1 1 46 0 0 0 47 0 0 0

......... 2,212 7 6

П 22

active substance (example no.) 0,025 infestation of the leaves after spraying with an agent concentration of 0.006 48 0 0 0 49 0 0 2 51 0 0 0 52 0 0 0 53 0 0 0 54 0 0 0 55 0 0 0 56 0 0 2 - 3 57 0 0 1 58 0 1 1 59 0 0 0 60 0 0 0 61 0 2 2 62 0 0 2 63 0 0 0 64 0 0 0 65 0 0 1 66 0 0 0 N 2 3 4 control 5 (untreated)

Example 1 a d B

Leaves of potted wheat plants are artificially infected with spores of Puccinia recondita (wheat rust) and kept in a water-saturated chamber at 20-25 ° C for 48 hours. The plants are then sprayed with an aqueous spray formulation prepared by dissolving a mixture containing 80% of the test drug and 20% sodium lignin sulphonate in water. The treated plants are then further preserved. in a greenhouse at a temperature between 20 and 22 ° C and a relative air humidity of 75 to 80 ° / o. After 10 days, the rust infestation of the plants was evaluated.

The results obtained are summarized in the following overview, expressed on a scale of 0 to 5, where 0 means no fungal growth and 5 represents complete leaf infestation.

Table

active substance (example no.) attacking the leaves after spraying with a concentration of effective. substances (%) 0,025 0.012 0.006 3 0 0 0 52 0 0 1 54 0 0 0 55 0 0 1 62 0 0 0 64 0 0 1 66 0 0 1 control 5 (untreated)

Claims (1)

A fungicidal composition comprising a solid or liquid carrier and, as the active ingredient, a 1,2,4, -triazolyl-yl derivative of the formula I R7 / N in which A represents a halogen atom, a phenyl group, an alkyl group having 1 to 6 carbon atoms, a cyclohexyl group, a benzyl group or a radical of formula wherein: Hal represents a halogen atom, B represents a hydrogen atom, a halogen atom or a (C1-C4) alkyl group, C represents a hydrogen or halogen atom, X is oxygen or sulfur; and Y is C 3 -C 6 alkyloxy or a radical of formula wherein R ⁷ is hydrogen, C 1 -C 4 alkoxy, C 1 -C 6 alkyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl, C 1 -C 4 cyanalkyl an alkyl moiety or benzyl group; and R 8 represents a hydrogen atom, a phenyl or a benzyl radical which are. optionally mono- or disubstituted with halogen, C 1 -C 6 alkyl or trifluoromethyl, furthermore cyclohexyl, naphthyl, C 1 -C 4 cyanalkyl. in the alkyl moiety, a C 3 -C 6 alkenyl group, a plant-tolerant residue or or a salt thereof and / or a metal complex.