CH629079A5 - Fungicide - Google Patents

Description

629 079

PATENT CLAIM Fungicide, containing a solid or liquid carrier and a ß-Azolkylketone of formula I.

R ^ CO-CH.-CH-R2

\ -J (i),

in which R1 is alkyl with up to 7 carbon atoms, cycloalkyl and optionally substituted aryl, R2 is furanyl, thiophenyl, naphthyl, biphenylyl or phenyl, where the phenyl radical can be substituted by halogen, alkyl, alkoxy, alkenyloxy, nitro, trifluoromethyl and R1 and R2 do not simultaneously mean phenyl, and their salts.

The present invention relates to a fungicide which contains new β-azolyl ketones and their salts.

It is known that 1,2,4-triazole derivatives, for example l- [l, 2,4-triazolyl- (l)] - 2- (4'-chlorophenoxy) -4,4-dimethylpentane 3-one show good fungicidal activity. The effect of these substances is unsatisfactory at low application rates and concentrations. In addition, their fungitoxic effect is associated with a high level of phytotoxicity, so that the crops are also damaged in the concentrations necessary for combating rust fungi. For these reasons, they are not always suitable for use as crop protection agents for combating fungi and not for all types and types of cereals.

It has been found that the new β-azolyl ketones of the formula I

R1-CO-CH "-CH-R2

2 I

\ -j (I),

in which R1 is alkyl with up to 7 carbon atoms, cycloalkyl, preferably with 3 to 8 carbon atoms, and optionally substituted aryl, R2 is furanyl, thiophenyl, naphthyl, biphenylyl or phenyl, the phenyl radical being halogen, preferably with 1 to 4 carbon atoms, alkoxy, preferably 1 to 3 carbon atoms, alkenyloxy, nitro, trifluoromethyl and R1 and R2 cannot simultaneously be phenyl and their salts are highly effective against harmful fungi, in particular from the class of the Ascomycetes and Basidiomycetes are.

R1 means, for example, methyl, isopropyl, tert-butyl, neopentyl, norbornyl, phenyl, p-chlorophenyl or 2,4-dichlorophenyl.

R2 means, for example, phenyl, tolyl, p-isopropylphenyl, naphthyl, thienyl, furyl, m- and p-chlorophenyl, p-bromophenyl, 2,4-dichlorophenyl, 3,4-dichlorophenyl, p-methoxy-phenyl, 3,5-dichloro-4-allyloxy-phenyl, o-allyloxy-phenyl, p-nitro-phenyl or p-trifluoromethyl-phenyl.

β-Azolyl ketones of the formula I or their salts can by reacting a, β-unsaturated ketones of the formula II

RI_CO-CH = CH-R2 (II),

in which R1 and R2 have the meaning given above, with 1,2,4-triazole optionally in the presence of a basic catalyst and optionally in the presence of a diluent. This manufacturing method is preferred. The compounds are also obtained if β-haloketones of the formula III

RI-CO-CH2-CH-R2 (III),

in which R1 and R2 have the meaning given above and X is halogen, with 1,2,4-triazole if appropriate in the presence of an acid binder and if appropriate in the presence of a diluent. Finally, the compounds are obtained if ketones of the formula R ^ CO-CHs (IV) and aldehydes of the formula OCH-R2 (V), in which R1 and R2 have the meaning given above, with 1,2,4-triazole, if appropriate in the presence of a basic catalyst and optionally in the presence of a diluent. The salts can be prepared from the compounds obtained by these processes using acids.

The reaction of a, β-unsaturated ketones with 1,2,4-triazole by the process described above is conveniently carried out without a diluent or in an indifferent diluent, e.g. Methanol, ethanol, iso-propanol, n-butanol, tetrahydrofuran, dioxane, toluene, xylene, dimethylformamide at temperatures of about 0 to 100 ° C. “preferably +20 to + 50 ° C.

It is expedient to add an alkaline compound, for example sodium hydroxide or potassium hydroxide or triethylamine or N, N-dimethylcyclohexylamine, in a catalytic amount.

The compounds II used as starting materials are known from the literature and can be prepared from ketones of the formula IV and aldehydes of the formula V by customary processes. If the necessary amount of triazole is added, the active compounds of the formula I are obtained directly in one step. These reactions are carried out, for example, in alcohols such as methanol or ethanol or isopropanol or in amides, e.g. Dimethylformamide, at temperatures from about 0 to 100 ° C, preferably +20 to + 50 ° C, and in the presence of a basic catalyst dissolved in water, e.g. Sodium hydroxide or potassium hydroxide.

The compounds of formula I are colorless crystalline products, readily soluble in ethyl acetate, acetone, ethanol, tetrahydrofuran, methylene chloride, chloroform, dimethyl sulfoxide, dimethylformamide and N-methylpyrrolidone.

The new ß-azolyl-ketones and their salts show a considerably broader fungicidal activity and superior plant tolerance than the known l- [l, 2,4-triazolyl- (l)] - 2- (4'-chlorophenoxy) - 4,4-dimethyl-pentan-3-one.

The new active ingredients can also be in the form of their salts, e.g. Hydrochloride, oxalate or nitrate can be used.

The fungicidal compositions according to the invention are of great interest in the case of fungal diseases on various crop plants, e.g. at

Ustilago scitaminae (sugar cane fire)

Hemileia Vastatrix (coffee rust)

Uromyces fabae or appendiculatus (bean rust) Puccinia species (grain rust)

Erysiphe graminis (powdery mildew)

2nd

5

10th

15

20th

25th

30th

35

40

45

50

55

60

65

3rd

629 079

Botrytis cinerea on vine, strawberries,

Uncinula necator,

Sphaerotheca fuliginea,

Erysiphe cichoracearum,

Podosphaera leucotricha.

In this context, we understand crops in particular wheat, rye, barley, oats,

Rice, corn, apple growing, cucumber, beans, coffee, sugar cane, grapevine, strawberries and ornamental plants in horticulture.

The active ingredients of the formula I are systemically active. The systemic effectiveness of these agents is of particular interest in connection with the control of internal plant diseases, for. B. grain rust, powdery mildew.

The agents according to the invention can simultaneously suppress the growth of two or more of the fungi mentioned and are highly tolerated by plants. The application rates required to combat the phythopathogenic fungi are between 0.05 and 2 kg of active ingredient / ha of cultivated area.

Examples of the active substances which can be used according to the invention are:

1 - [1,2,4-Triazolyl- (I)] - 1 -phenyl-4,4-dimethyI-pentan-3-one l- [l, 2,4-triazolyl- (l)] - l- (p-tolyl) -4,4-dimethylpentan-3-one l- [l, 2,5-triazolyl- (l)] - l- (4'-isopropylphenyl) -4,4-dimethyl- pentan-3-one

1 - [1,2,4-Triazolyl- (l)] - 1 - (1'-naphthyl) -4,4-dimethylpentan-3-one

1 - [1,2,4-Triazolyl- (1)] - 1 - (3'-thienyl) -4,4-dimethylpentan-3-one

1 - [1,2,4-TriazolyH 1)] - 1 - (2'-furyl) -4,4-dimethylpentan-3-one 1- [1,2,4-triazolyH 1)] - 1 - (4'-Chlorophenyl) butan-3-one 1 - [1,2,4-Triazolyl- (1)] - 1 - (4'-chlorophenyl) -4-methylpentan-3 -on

1 - [1,2,4-TriazolyH 1)] - 1 - (4'-chlorophenyl) -5,5-dimethyl-he-xan-3-one

1 - [1,2,4-Triazolyl- (l)] - 1 - (4'-chlorophenyl) -

4,4-dimethylpentan-3-one 1 - [1,2,4-TriazolyH 1)] - 1 - (4'-bromo-phenyl) -4,4-dimethyl-pen-tan-3-one

1 - [1,2,4-TriazolyH 1)] - 1 - (3'-chlorophenyl) -4,4-dimethyl-pen-tan-3-one

1 - [1,2,4-TriazolyH 1) H - (2 ', 4'-dichlorophenyl) -4,4-dimethylpentan-3-one

1 - [1,2,4-TriazolyH 1)] - 1 - (3 ', 4'-dichlorophenyl) -4,4-dimethyl-

1-1-

5

1-3-lo 3-3-3-

15

3-3-

3-

20th

3-

pentan-3-one

1,2,4-TriazolyH 1)] - 1 - (4'-trifluoromethyl-phenyl) -4,4-dimethylpentan-3-one [1,2,4-Triazolyl- (l)] - 1 - (4'-nitro-phenyl) -4,4-dimethyl-pen-tan-3-one

[1,2,4-TriazolyH 1)] - 1 - (4'-methoxyphenyl) -4,4-dimethyl-

pentan-3-one [1,2,4-TriazolyH 1)] - 3- (4'-methoxyphenyl) -

1 - (2-norbonyI) -propan-1 -one [1,2,4-triazolyl- (1)] - 3- (2'-allyloxyphenyl) -l - (4'-chlorophe-

nyl) propan-l-one [1,2,4-triazolyl- (1)] - 3- (2'-allyloxyphenyl) -1 - (2 ', 4'-dichloro-

phenyl) propan-1-one [1,2,4-triazolyl- (1)] -1-phenyl-3- (4'-chlorophenyl) propan-1-one

{1,2,4-T riazolyl- (1)] - 1,3-bis- (4'-chlorophenyl) propan-1 -one [1,2,4-T riazolyH 1)] - 1 - (4'-chlorophenyl) -3- (p-tolyl) propan-l-one

[1,2,4-Triazolyl- (l)] - 1 - (2 ', 4'-dichlorophenyl) -3-phenyl-pro-pan-l-one

[1,2,4-Triazolyl- (1)] - 1 - (4 / -chlorophenyl) -3- (2 ', 4'-dichlorophenyl) propan-1 -one

25th

30th

Example 1 -C0-CHo-CH-

C- I

Ù

-Cl

HCl

24.8 g (0.1 mol) l-phenyl-3- (4'-chlorophenyl) prop-2-en-1-one, 11 g 1,2,4-triazole (0.15 mol) and 0 , 3 g of potassium hydroxide are dissolved in 200 ml of dimethylformamide and stirred at 45 ° C for 10 hours. The solvent is then distilled off in vacuo, the residue is dissolved in 300 ml of ether and the organic solution is washed twice with 100 ml of water each time. The organic phase is then dried over sodium sulfate, filtered off and gassed with hydrogen chloride gas. The precipitate of 40 3- [l, 2,4-triazolyH 1)] -1 -phenyl-3- (4'-chlorophenyl) propan-1-one hydrochloride is suction filtered and dried.

Yield: 20 g of white crystals with a melting point of 156 to 158 ° C. (83%) in addition to 7.4 g of recovered 1-phenyl-3- (4'-chlorophenyl) prop-2-en-l-one. The compounds listed in Table 1 below are prepared analogously.

Table 1 F ^ -CO-CI - ^ - CH-R2

Connection R1 no.

R2

Melting point "C

Base hydrochloride

(ch3) 3c-

(ch3), c

141-143

153-155

No.

4th

5

6

7

8th

9

10th

11

12th

13

14

15

16

17th

18th

19th

Table 1 (continued)

R1

R2

Melting point "C

Base hydrochloride

(CH3) 3C-

(CH3) 3C- (CH3) 3C-

(ch3) 3c-

(CH3) 2CH-

(CH3) 3c-

(ch3) 3c-ch2-ch3-

(ch3) 3c-

(CH3) 3c- (CH3) 3c-

(Ch3) 3C-

(CH3) 3C- (CH3) 3C- (CH3) 3c-

he ch3

/

ch

3rd

oro "

// w

0

Cl

Cl

Cl

Cl

- © • - <o>

OÏ

Cl Br

Cl-

- <Ö>

CH3 ° - <5> -

F3C

0 ~ N

.CH, 0

69-71

155-157

162-164 118-120

156-160 118-120 139-141

110-111

69-72

146-147

142-145 154-156

158-160

166-168 164-167 158-161 78-82

5

Table 1 (continued)

629 079

Connection R1 no.

R2

Melting point ° C

Base hydrochloride

20th

21st

22

23

24th

25th

26

27th

28

30th

31

32

33

ci-®-

C «H« -

C1 Cl

- <§> -

° i ^ o>

(CH3) 3C-

Cl-

Cl

(CH3) 2CH-

(CH3) 3C-CH2-

c2n5, CH-z '

"CH-

O

0-CH2-CH = CH2

-CH2-CH = CH2

Cl Cl

- <2>

H, C

c6h5-

cl - <^ o) -

©

ch2 = ch-ch2-ox: i

CH2 = CH-CH2-0 Cl wCl &

CH2 = CH-CH2-0 '^ C1

ci- (0> -

81-82

49-50

156-158

94-95

156-158

115-117

136-139

135-138

151-153

105-107 145-148

162-165

143-145

164-169

126-128

34

ci- <Of

Cl

165-167

629 079

6

Table 1 (continued)

Connection no.

R1

R2

Base melting point

Hydrochloride

35

36

37

38

39

40

41

42

(CH3) 3C-

(CH3) 3C-

(CH3) 3c-

104-106

130-132

50-52

* <o> - <ö> -

(CH3) 2CH-CH2-

(CH3) 3c- (CH3) 3c-

(CH3) 3c-

No

111-113

113-115

70-72

104-106

163-166

The active compounds according to the invention can be converted into the customary formulations, such as solutions, emulsions, suspensions, powders, pastes and granules. These are manufactured in a known manner, e.g. B. by mixing the active ingredient with solvents and / or carriers, optionally using emulsifiers and dispersants, and in the case of using water as a diluent, other organic solvents can also be used as auxiliary solvents. The following are essentially suitable as auxiliaries: solvents, such as aromatics (e.g. xylene, benzene), chlorinated aromatics (e.g. chlorobenzenes), paraffins (e.g. petroleum fractions), alcohols (e.g. methanol, butanol), amines (e.g. Ethanolamine, dimethylformamide) and water; Carriers such as natural stone powder (e.g. kaolins, clays, talc, chalk) and synthetic stone powder (e.g. highly disperse silica, silicates); Emulsifiers such as non-ionic and anionic emulsifiers (e.g. polyoxyethylene fatty alcohol ether, alkyl sulfonates and aryl sulfonates) and dispersants such as lignin, sulfite liquor and methyl cellulose.

The formulations generally contain between 0.1 and 95 percent by weight of active compound, preferably between 0.5 and 90%. The formulations or the ready-to-use preparations produced therefrom, such as solutions, emulsions, suspensions, powders, pastes or granules, are used in a known manner, for example by spraying, atomizing, dusting, scattering, pickling or pouring.

In these application forms, the agents according to the invention can also be present together with other active ingredients, e.g. Herbicides, insecticides, growth regulators and fungicides, or can also be mixed with fertilizers. Fungicides which can be combined with the compounds according to the invention are, for example, disothiocarbamates and their derivatives, such as ferridimethyldithiocarbamate,

Zinc dimethyldithiocarbamate, manganese ethylene bisdithiocarbamate, manganese zinc ethylenediamine bisdithiocarbamate, 55 zinc ethylene bisdithiocarbamate,

Tetramethylthiuram disulfide,

Ammonia complex of zinc (N, N-ethylene-bis-dithiocarbamate) and N, N'-polyethylene-bis- (thiocarbamoyl) -disulfide

6o zinc (N, N'-propylene-bis-dithiocarbamate), ammonia complex of zinc (N, N'-propylene-bis-dithio-carbamate) and N, N'-polypropylene-bis- (thiocarbamoyl) - disulfide

65 nitrophenol derivatives, such as

Dinitro- (1-methylheptyl) phenylcrotonate,

2-sec-butyl-4,6-dinitrophenyl-3,3-dimethylacrylate,

2-sec-butyl-4,6-dinitrophenyl-isopropyl carbonate;

629 079

heterocyclic structures such as N-trichloromethylthio-tetrahydrophthalimide, N-trichloromethylthio-phthalimide, 2-heptadecyl-2-imidazoline acetate,

2,4-dichloro-6- (o-chloroanilino) -s-triazine, 0.0-diethyl-phthalimidophosphonothioate,

5-amino-1 - [bis- (dimethylamino) phosphinyl] -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-methoxycarbonylamino-benzimidazole, 2-rhodanmethylthio-benzothiazole,

4- (2-chlorophenylhydrazono) -3-methyl-5-isoxazolone, pyridine-2-thiol-1-oxide,

8-hydroxyquinoline or its copper salt, 2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiin-4,4-dioxide,

2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiin, 2- [furyl- (2)] benzimidazole,

Piperazin-1,4-diyl-bis-1 - (2,2,2-trichloroethyl) formamide,

2- [thiazolyl- (4)] benzimidazole,

5-butyl-2-dimethylamino-4-hydroxy-6-methyl-pyrimidine, bis- (p-chlorophenyl) -3-pyridinemethanol, 1,2-bis- (3-ethoxycarbonyl-2-thioureido) -benzene, l, 2-bis (3-methoxycarbonyl-2-thioureido) benzene,

and various fungicides such as dodecylguanidine acetate,

3- [2- (3,5-dimethyl-2-oxycyclohexyl) -2-hydroxyethyl] glutarimide,

Hexachlorobenzene,

N-dichlorofluoromethylthio-N ', N'-dimethyl-N-phenyl-sulfuric acid diamide,

2,5-dimethyl-furan-3-carboxylic acid anilide, 2,5-dimethyl-furan-3-carboxylic acid cyclohexylamide,

2-methylbenzoic acid anilide,

2-iodo-benzoic acid anilide,

1 - (3,4-dichloroanilino) -1-formylamino-2,2,2-trichloroethane, 2,6-dimethyl-N-tridecyl-morpholine or its salts, s 2,6-dimethyl-N-cyclodecyl-morpholine or its salts,

2,3-dichloro-1,4-naphthoquinone,

1,4-dichloro-2,5-dimethoxybenzene, p-dimethylaminobenzene diazo sodium sulfonate, 1-chloro-2-nitrole-propane,

k> Polychloronitrobenzenes, such as pentachloronitrobenzene, methyl isocyanate, fungicidal antibiotics, such as griseofulvin or kausgamycin, tetrafluorodichloroacetone, l-phenylthiosemicarbazide, Bordeaux mixture, nickel-containing compounds and sulfur.

When combating mildew and rust diseases on cereals, an effect-increasing effect (synergism) was found when using l- [l, 2,4-triazolyl- (l)] - l- (4'-chlorophenyl) -4.4 -dimethylpentan-3-one or l- [l, 2,4-triazolyl- (1)] - 1 - (2 ', 4'-dichlorophenyl) -4,4-dimethyl-pentan-3-one, ent -2o neither as bases nor in the form of their salts in a mixture with N-tridecyl-2,6-dimethylmorpholine and its salts. The increase in effectiveness can be observed particularly clearly with the mixing ratios 1: 2 to 1: 4 parts by weight.

25 The following examples explain the fungicidal activity of the new active ingredients.

Example 28 30 barley mildew

Leaves of barley seedlings grown in pots are sprayed with aqueous emulsions of 80% active ingredient and 20% emulsifier and, after the spray coating has dried on, are dusted with oidia (spores) of the barley powdery mildew 35 (Erysiphe graminis var. Hordei). The test plants are then placed in a greenhouse at temperatures between 20 and 22 ° C and 75 to 80% relative humidity. After 10 days, the extent of the development of mildew is determined.

0 no infection, graded to 5 total infection

Active ingredient

Infection of the leaves after spraying with ...% active ingredient broth

0.1

0.05

0.025

0.012

3rd

0

0

0

0

9

0

0

0

0

14

0

0

0

0

15

0

0

0

0

known (DE-OS 2 335 020) control (untreated)

Example 29 Powdery mildew of leaves from potted wheat seedlings of the "Jubilar" variety are sprayed with aqueous emulsions of 80% (weight percent) active ingredient and 20% emulsifier and, after the spray coating has dried on, with

Oidia (spores) of powdery mildew (Erysiphe graminis var. Tritici) pollinated. The test plants are then placed in a greenhouse at temperatures between 20 and 22 ° C and 75 to 80% relative humidity. After 10 days, the extent of the mildew development is determined.

629079

8th

0 no infection, graded to 5 total infection

Active ingredient

CH,

»J

ch, -c-co-0H

2 I

CH ..

N

-®c:

known (DE-OS 2 335 020)

Control (untreated)

Example 30 Cucumber Powdery Mildew

Leaves of cucumber seedlings grown in pots are sprayed with aqueous emulsions of 80% active ingredient and 20% emulsifier and after drying

Infection of the leaves after spraying with ...% active ingredient broth

0.05

0.025

0.012

9

0

0

0

10th

0

0

0

13

0

0

0

14

0

0

0

15

0

0

0

sprinkled with oidia (spores) of cucumber powdery mildew (Erysiphe cichoriacearum). The test plants 25 are then placed in the greenhouse at temperatures between 20 and 22 ° C and 75 to 80% relative humidity. After 10 days, the extent of the mildew development is determined.

0 no infection, graded to 5 total infection

Active ingredient

Infection of the leaves after spraying with ...% active ingredient broth 0.1

0

Control (untreated) * slight leaf damage

Example 31

90 parts by weight of compound 9 are mixed with 10 parts by weight of N-methyl-a-pyrrolidone, and a solution is obtained which is suitable for use in the form of tiny drops.

Example 32

20 parts by weight of compound 2 are dissolved in a mixture consisting of 80 parts by weight of xylene, 10 parts by weight of the adduct of 8 to 10 moles of ethylene oxide and 1 mole of oleic acid-N-monoethanolamide, 5 parts by weight of calcium salt of dodecylbenzenesulfonic acid and 5 parts by weight of the adduct of 40 moles of ethylene oxide of 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and finely distributing it therein, an aqueous dispersion is obtained which contains 0.02% by weight of the active ingredient.

Example 33

20 parts by weight of compound 3 are dissolved in a mixture consisting of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the adduct of 7 mol of ethylene oxide and 1 mol of isooctylphenol and 10 parts by weight of the adduct

45 of 40 moles of ethylene oxide to 1 mole of castor oil. Pouring the solution into 100,000 parts by weight of water and finely distributing it therein gives an aqueous dispersion which contains 0.02% by weight of the active ingredient.

Example 34

20 parts by weight of compound 4 are dissolved in a mixture consisting of 25 parts by weight of cyclohexanol, 65 parts by weight of a mineral oil fraction from the boiling point 210 55 to 280 ° C and 10 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil. Pouring the solution into 100,000 parts by weight of water and finely distributing it therein gives an aqueous dispersion which contains 0.02% by weight of the active ingredient.

Example 35

20 parts by weight of active ingredient 5 are mixed well with 3 parts by weight of the sodium salt of diisobutylnaphthalenesulfonic acid, 17 parts by weight of the sodium salt of lignosulphonic acid from a sulfite waste liquor and 60 parts by weight of pulverulent silica gel and ground in a hammer mill. By finely distributing the mixture

9

629 079

in 20,000 parts by weight of water, a spray liquor is obtained which contains 0.1 percent by weight of the active ingredient.

Example 36

3 parts by weight of compound 6 are intimately mixed with 97 parts by weight of finely divided kaolin. In this way a dust is obtained which contains 3 percent by weight of the active ingredient.

Example 37

30 parts by weight of compound 7 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 this silica gel. In this way, a preparation of the active ingredient with good adhesiveness is obtained.

Example 38

40 parts by weight of active ingredient 9 are intimately mixed with 10 parts of sodium salt of a phenolsulfonic acid-urea-form aldehyde condensate, 2 parts of silica gel and 48 parts of water. A stable aqueous dispersion is obtained. Dilution with 100,000 parts by weight of water gives an aqueous dispersion which contains 0.04% by weight of active ingredient.

Example 39

20 parts of active ingredient 8 are intimately mixed with 2 parts of calcium salt of the dodecylbenzenesulfonic acid-urea-formaldehyde condensate and 68 parts of sodium salt of a phenol-sulfonic acid-urea-formaldehyde condensate and 68 parts of a paraffinic mineral oil. A stable oily dispersion is obtained.

s