DK157812B - SUBSTITUTED AZOLYLGYCUL SULPHONATES, FUNGICID CONTAINING SUCH COMPOUNDS AND PROCEDURES TO COMBAT FUNGI USING THE COMPOUNDS - Google Patents

Abstract

1. Claims for the Contracting states : BE, CH, DE, FR, GB, IT, LI, LU, NL, SE An azolylglycol sulfonate of the general formula see diagramm : EP0056860,P10,F3 where R**1 is alkyl of 1 to 6 carbon atoms, which is unsubstituted or substituted by fluorine, chlorine, bromine or iodine, or is alkoxy of 1 to 4 carbon atoms, or is phenyl which is unsubstituted or substituted by fluorine, chlorine, bromine, iodine, cyano, alkyl of 1 to 6 carbon atoms, alkoxy of 1 to 4 carbon atoms, phenyl or phenoxy, R**2 has the same meanings as R**1 and R**1 and R**2 can be identical or different, R**3 is hydrogen, halogen, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, cyano, phenyl or phenoxy, the last two being unsubstituted or substituted by halogen or alkyl of 1 to 4 carbon atoms, n is an integer from 1 to 5, X is S or O and Y is N or CH. 1. Claims for the Contracting state : AT A fungicide containing an azolylglycol sulfonate of the general formula see diagramm : EP0056860,P11,F2 where R**1 is alkyl of 1 to 6 carbon atoms, which is unsubstituted or substituted by fluorine, chlorine, bromine or iodine, or is alkoxy of 1 to 4 carbon atoms, or is phenyl which is unsubstituted or substituted by fluorine, chlorine, bromine, iodine, cyano, alkyl of 1 to 6 carbon atoms, alkoxy of 1 to 4 carbon atoms, phenyl or phenoxy, R**2 has the same meanings as R**1 and R**2 can be identical or different, R**3 is hydrogen, halogen, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, cyano, phenyl or phenoxy, the last two being unsubstituted or substituted by halogen or alkyl of 1 to 4 carbon atoms, n is an integer from 1 to 5, X is S or O and Y is N or CH.

Description

DK 157812B

The invention relates to novel azolyl glycol sulfonates, a fungicide containing such compounds, and a method for controlling fungi using the compounds.

It is known that imidazoly lethers, e.g. 1- (2- (2,4-Dichlorophenyl) -2- (2-propenyloxy-ethyl) -1H-imidazole (GB-PS

1 318 590), has fungicidal activity. However, the effect of these substances is unsatisfactory. It is also known to use zinc-ethylene bisdithiocarbamate as a fungicide (Chemical Week, booklet of July 26, 1972, page 41). However, its effect is unsatisfactory.

It is thus the object of the invention to provide new compounds having better fungicidal activity than the above-mentioned fungicidally active compounds.

The triazolyl-glycolsulfonates of the invention are useful in the features of the characterizing part of claim 1. These compounds have been found to have a better fungicidal activity.

It is known from EP Publication Nos. 1414, 3049, 4303 and 21345 that compounds which are closely related to the compounds of the invention have a good fungicidal activity. However, it has been found that the compounds of the invention exhibit an even better fungicidal activity than these known fungicides and that, unlike the known fungicides, they also do not cause any leaf damage.

The compounds of the invention have two (possibly even more) centers of chirality. They arise from the synthesis in the form of diastereomer mixtures if the alcohols used as starting materials were also available in the form of diastereomer mixtures. By fractional crystallization, pure diastereomers which are also included in the invention can be prepared.

DK 157812 B

2

The compounds of the invention can be prepared on the basis of the alcohols of the formula, O-R / / CH-CH-H H = * R3 which can be prepared according to known methods and described in the literature and which can be is prepared by reaction with alkali hydrides or amides or with bases such as NaOH, KOH, in the presence of catalysts such as quaternary ammonium or phosphonium salts in aprotic solvents, e.g. THF (tetrahydrofuran), DMF (dimethylformamide), dioxane, to the corresponding alcohols of formula R -G-CH - ~ ----- where M is sodium or potassium and these are reacted with sulfonic acid halides of formula 0

II

Hal-S-R2,

TEN

wherein Hal represents a halogen atom, preferably with sulfonic acid chlorides, for the compounds of formula 1, in one of the solvents indicated.

DK 157812 B

EXAMPLE 1 1- (4-Chlorophenoxy) -3,3-dimethyl-2- (4-methylphenylsulfonyl) -1- (1,2,4-triazol-1-yl) -butane.

44.6 g (0.15 mol) of 1- (1,2,4-triazol-1-yl) -1- (4-chlorophenoxy) -3,3-dimethyl-butan-3-ol form of diastereomer mixture dissolved in 500 ml of absolute THE (tetrahydrofuran) and stirred at room temperature mixed with 4.5 g of sodium hydride (80 °) · Then stirred for 6 to 8 hours at 40 - 50 ° C and after cooling drop 28.5 .g (0.15 mol) of p -toluene sulfochloride, dissolved in an amount of THF as small as possible. The mixture is stirred for 5 to 6 hours at room temperature, then hydrolyzed with water, extracted several times with 500 ml of methylene chloride, dried over the organic phase over sodium sulfate and distilled off in solvent. The residual residue is crystallized fractionally by vinegar ester to give 23.5 g (35¾ of theory) of a diastereoisomer mixture, m.p. 156 - 157 ° C (Compound No. 1).

In accordance with Example 1, the following additional derivatives were prepared:

DK 157812B

4

Compound R1 R2 R3 η YX M.p. No. _______ 1 L - _ 2 (CH3) 3C-4-methyl-2,4,5-Cl 3 N 0 122-126 phenyl 3 (CH3) 3C- "4-Br 1 "168-170 4 (CH3) 3C-" 2-C1-1 "" 82-85 5 5 (CH3) 3C- "3,5-Cl2", r 210-212 6 (CH3) 3C- "4- C (CH3) 3 1 "" 113 7 (CH3) 3C- "3-CF3 1" "136-1378 (CH3) 3C-" 4-phenyl1 "" 155-156 9 (CiH3) 3C- "2, 4-Cl 2 11 "134-136 10 10 Phenyl" 4-Br 1 "" 86-89 11 Phenyl "2-C1 1 11" 126-129 12 Phenyl 11 4-pheny 1 1 11 11 84-87 13 (C 3) 3C- 4-Br 1 "S 139-141 + 14 (CH3) 3C- n 4-Br 1" S 127-129 + 15 + diastereoisomer pairs

The active substances are particularly suitable for the control of fungal diseases in various cultural plants, e.g. Erysiphe graminis in cereals, Uncinula necator in wine, Podosphaera leucotricha in apples, Erysiphe cichoracearum in pumpkin plants, Mycosphaerella musicola in bananas, Phytophthora infestans in tomatoes and potatoes, Plasmopaera viticola in wine, Pseudoperonosle hum.

Some of the active substances of the invention are systemically active in plants affected by a fungus; the amounts needed to control phytopathogenic fungi range from 0.025 to 2 kg of active substance / ha of culture surface; the other active ingredients of the invention are fungicidal but not systemic fungicidal.

The new active substances are also suitable for the protection of 30 trees against infestation caused by wood-eaten fungi, such as Coniophora puteana, Lenzites trabea, Trametes versi.

DK 157812B

5 color. Depending on the nature of the desired effect, the amounts used are 0.001 to 5% (wt%) calculated in relation to the weight of the material to be protected, but preferably between 0.01 and 3%.

5 The use as a fungicide takes place e.g. in the form of directly extrudable solutions, powders, suspensions or dispersions, emulsions, oil dispersions, pastes, powders, scrubbing agents, granules by spraying, coating, impregnating, misting, spraying, scrubbing or pouring. The forms of dispensing are entirely according to the application purpose and they must in each case ensure the finest possible distribution of the active substances.

For the preparation of directly sprayable solutions, emulsions, pastes and oil dispersions, medium to high boiling mineral oil fractions such as petroleum or diesel oil, in addition coal oil, etc., as well as oils of vegetable or mineral origin, aliphatic, cyclic and aromatic hydrocarbons, f. eg.

20 benzene, toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphtha lenders or their derivatives, e.g. methanol, ethanol, propanol, butanol, chloroform, tetrachloro carbon, eyelohexanol, eyelohexanone, chlorobenzene, isophorone, etc., highly polar solvents, e.g.

25 dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, water, etc. are considered.

Aqueous applications can be prepared from emulsion concentrates, pastes or wettable powders (spray powders), oil dispersions by the addition of water. For the preparation of emulsions, pastes or oil dispersions, the substances may be dissolved in an oil or solvent, homogenized in water by wetting, adhesion, dispersing or emulsifying agents. But

DK 157812 B

It is also possible to prepare concentrates consisting of active substance, wetting, adhesive, dispersing or emulsifying agent and optionally solvent or oil which are suitable for dilution with 5 water.

The fungicides contain e.g. 5 to 95¾ (weight-o) active substance, especially between 10 and 80¾ active substance.

As examples of surfactants may be mentioned: alkali metal, alkaline earth metal, ammonium salts of lignin sulfonic acid, napbthalene sulfonic acids, phenolic sulfonic acids, alkylarylsulfonates, alkyl sulfates, alkylsulfonates, alkali metal and alkaline earth sulfonates, and alkaline earth metal salts, salts of sulphated ihexadecanols, heptadecanols, oetadecanols, salts of sulphated fatty alcohol glycol ethers, condensation products of sulphonated, naphthalene and naphthalene phenylsulfonylsulphonic acid or naphthalene , ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenol polyglycol ether, tributylphenyl polyglycol ether, alkyl arylpolyetber alcohols, isotridecylalcohol, fatty alcohol ethylene oxide condensates, ethoxylated polyethylene condensates, ethoxylated polyethylene condensates ropylene, lauryl alcohol polyglycol ether acetal, sorbitester, lignin, sulfite waste liquor and methyl cellulose.

Powders, scatters and powders can be prepared by mixing or co-grinding the active substances with a solid carrier.

Granules, e.g. envelope, impregnation and homogeneous granules can be prepared by binding of the active

DK 157812 B

7 substances for solid carriers. Solid carriers are e.g. mineral soils such as silicas, silicates, talc, kaolin, lime, bolus, lass, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, milled molds, fertilizers, such as e.g. ammonium sulphate, ammonium phosphate, ammonium nitrate, urea and vegetable products such as cereal, wood bark, wood and nut shell flour, cellulose powder and other solid carriers.

PREPARATION a 10 90 parts by weight of Compound 1 are mixed with 10 parts by weight of N-methyl-1-pyrrolidone to obtain a solution suitable for use in very small droplets.

PREPARATION b 10 parts by weight of compound 2 are dissolved in a mixture consisting of 90 parts by weight xylene, 6 parts by weight of the preparation product of 8 to 10 moles of ethylene oxide to 1 mole of oleic acid N-mono-ethanolamide, 2 parts by weight of calcium salt of dodecyl benzene sulfate phonic acid and 2 parts by weight of the preparation product of 40 moles of ethylene oxide to 1 mole of castor oil.

20 PREPARATION c 20 parts by weight of compound 3 are dissolved in a mixture consisting of 60 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 5 parts by weight of the product of 7 moles of ethylene oxide to 1 mole of isooctylphenol and 5 parts by weight of the product of 4Ό moles of ethylene oxide. to 1 mole of castor oil.

PREPARATION 20 parts by weight of the compound 1 'are dissolved in a mixture consisting of 25 parts by weight of cyclohexanone, 65 parts by weight of a

DK 157812 B

8 mineral oil fraction with boiling point 210 to 280 ° C and 10 parts by weight of the preparation product of 40 moles of ethylene oxide to 1 mole of castor oil.

PREPARATION 5 80 parts by weight of the active substance 1 are well mixed with 3 parts by weight of the sodium salt of diisobutylnaphthalene-a-sulfonic acid, 10 parts by weight of the sodium salt of a lignin sulfonic acid from a sulfite waste liquor and 7 parts by weight of powdered silicic acid gel and ground in a hammer mill. .

10 PREPARATION For 5 parts by weight of Compound 1, mix thoroughly with 95 parts by weight of finely divided kaolin. In this way, a powder containing 5% by weight of the active substance is obtained.

PREPARATION 13 13 wt Si of compound 1 is thoroughly mixed with a mixture of 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil sprayed onto the surface of this silica gel. In this way, a preparation of the active substance with good adhesiveness is obtained.

PREPARATION h 40 parts by weight of the active substance 1 are thoroughly mixed with 10 parts of sodium salt of a phenolic sulfonic acid urea-forma 1-dehyde condensate, 2 parts of silica gel and 48 parts of water. A stable aqueous dispersion is obtained. Dilution with 25 100,000 parts by weight of water gives an aqueous dispersion containing 0.04% by weight of the active substance.

DK 157812 B

9 PREPARATION in 20 parts of the active substance 1 is thoroughly mixed with 12 parts of calcium salt of dodecylbenzenesulfonic acid, 8 parts of fatty alcohol polyglycol ether, 2 parts of sodium salt of a phenolic sulfonic acid-urea-formaldehyde condensate and 68 parts of a paraffinic mineral oil. A stable, oily dispersion is obtained.

The fungicides in these uses may also be present with other active substances such as e.g. herbicides, 10 insecticides, growth regulators and fungicides, or also mixed and applied together with fertilizers.

By mixing with fungicides, an increase in the fungicidal spectrum of action is thereby achieved in many cases.

Fungicides which may be combined with the compounds of the invention are, for example: dithiocarbamates and their derivatives such as ferridimethyldithiocarbamate, zinc dimethyl dithiocarbamate, manganese ethylene bisdithiocarbamate, manganese rzinc diamide diacetamide, zinc diamide , N-ethylene bis-dithiocarbamate) and 25 N, N'-polyethylene bis (thiocarbamoyl) disulfide, zinc (N, N'-propylene bis-dithiocarbamate), ammonia complex of zinc (lsl, N 1 -propylene bis-dithiocarbamate) and N, N'-polypropylene bis (thiocarbamoyl) disulfide; nitro derivatives such as dinitro (1-methylheptyl) phenylcrotonate, 2-sec-buty 1-4,6-dinitrophenyl-3,3-dimethyl acrylate, 2-sec-butyl-4,6-dinitrophenyl isopropyl carbonate;

DK 157812B

Heterocyclic structures such as N-trichloromethylthio-tetrahydrophthalimide, N-trichloromethylthiophthalimide, 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, dicyano-1,4-dithioanthraquinone, 2-thio-1,3-dithio- (4,5-b) -quinoxaline, 1- (butylcarbamoyl) -2-benzimidazole-carbamic acid methyl ester, 2-methoxycarbonylamino-benzimidazole, 2-rhodanemethylthio -benzthiazole, 4- (2-chlorophenylhydrazono) -3-methyl-5-isoxazolone, pyridine-2-thio-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, piperazine-1,4-diyl-bis - (1- (2,2,2-trichloro-ethyl) -formamide), 2- (thiazolyl- (4)) -benzimidazole, 5-butyl-2-dimethylamino-4-hydroxy-6-methyl-pyrimidine, bis (p-chlorophenyl) -3-pyridinmet hanol, 1,2-bis- (3-ethoxycarbonyl-2-thioureido) -benzene, 1,2-bis- (3-methoxycarbonyl-2-thioureido) -benzene, and various fungicides such as dodecylguanidine acetate, 3- (3- (3, 5-dimethyl-2-oxycyclohexyl) -2-hydroxyethyl) glutarimide, hexachlorobenzene,

DK 157812 B

11 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-methyl-benzoic 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, 2,6-dimethyl-N-cyclododecyl -morpholino or its salts, DL-methyl-N- (2,6-dimethyl-phenyl) -N-furoyl (2) -alaninate, DL-N- (2,6-dimethyl-phenyl) -N- (2 '-Methoxyoxyethyl) -alanine methyl ester, 5-nitro-isophthalic acid di-isopropyl ester, 1- (1 *, 2', 4'-triazolyl-1 ') - [1- (4'-chlorophenyl) )] - 3,3-dimethylbutan-2-one, 1- (1 ', 2', 4'-triazolyl-1 ') - [1- (4'-chlorophenoxy)] - 3,3-dime -thylbutan-2-ol, N- (2,6-dimethylphenyl) -N-chloroacetyl-D, L-2-aminobutyro-lactone, N- (n-propyl) -N- (2,4,6-trichlorophenoxyethyl) ) -N'-imidazolyl urea,

The following experiments explain the good fungicidal action of the active substances in comparison with known active substances.

The following known compounds were used as comparative agents: 1- (2 '- (2 ", 4" -dichlorophenyl) -2' - (2 "-propyleneoxy) -ethyl-1H-imidazole (compound A) zinc-ethylene-bis dithiocarbamate (compound B) EXPERIMENT 1

DK 157812 B

12

Wheat mildew activity

Leaves of wheat seed-driven "Jubilar" seedlings are sprayed with aqueous emulsions of 80% 5 (wt.%) Of active substance and 20% emulsifier (based on the dry matter), and after the initial drying of the spray coating, they are dusted with oidium (spores). ) of wheat mildew (Erysiphe graminis var. tritici). The test plants are then set up in greenhouses at temperatures between 20 and 22 ° C and at a relative humidity between 75 and 80%. After 10 days, the extent of mildew development is assessed.

During this experiment, the new compounds 1 and 6 showed a better fungicidal activity than the known active substance A.

EXPERIMENT 2

Activity against cucumber mildew

Leaves of cucumber-driven cucumber seedlings are sprayed with aqueous emulsions of 80% active substance and 20% emulsifier (based on dry matter), and they are polluted after the initial drying of the spray coating with oidia (spores) avaguer mildew (Erysiphe cicho raccoon). . The test plants are then set up in greenhouses at temperatures between 20 and 22 ° C and at a relative humidity between 75 and 80%. After 10 days 25 the extent of the development of mildew fungus is assessed.

In this experiment, active substances 1, 3 and 4 showed excellent fungicidal activity.

EXPERIMENT 3

DK 157812 B

13

Activity against Phytophthora infestans in tomatoes

Leaves of tomato plants of the "Professor Rudluff" variety are sprayed with aqueous suspensions containing 80¾5 (wt) of the active substance to be tested and 20¾ sodium lignin sulfonate, calculated in terms of dry weight.

0.025, 0.006 and 0.0015¾ spray liquid (calculated in relation to the dry matter) is used. After the initial drying of the spray coating, the leaves are infected with a zoo-10 spore slurry of the fungus Phytophthora infestans. The plants are then placed in a water vapor-saturated chamber at temperatures between 16 and 18 ° C. After 5 days, the disease has developed so strongly on the untreated but infected control plants that you can judge the 15 fungicidal activity of the substances:

During this experiment, the new active substance 6 showed a better fungicidal activity than the known active substance B.

TEST 4 (comparative trial)

Wheat Milk Activity 20 Leaves of wheat Jubilar-driven wheat seedlings are sprayed with an aqueous spray liquid containing 80¾ active substance and 20¾ emulsifier, and are sprayed 24 hours after the initial drying of the spray coating with oidium (spores) ) of wheat-25 mildew (Erysiphe graminis var. tritici). The test plants are then set up in greenhouses at temperatures between 20 and 22 ° C and 75 to 80 ° C relative humidity. After 12 days, the extent of mildew development is assessed.

DK 157812 B

14

Assessment: O = no fungal attack, escalated to 5 = total swan attack A = minor leaf damage 5 B = medium leaf damage

R

CH 2 O 2 C 1 \.

ch3 p ° - (O) —ci 0 EXPERIMENT 4

Attack on leaves after treatment Active substance with spray liquid with. ...? ό active substance R_0,025 0j0125 0.006_ 5Q2 ~ ^ 0 ^) ~ CH5 0 0 0 (according to invention # 9)

H 0A 0A 0A

(corresponding to EP-A-1414) 0 c- <g> 0ft 0Λ 2 (corresponding to EP-A-4303) 0 C-NH- @ 0A 0A 1 (corresponding to EP-A-3049)

Untreated 5

DK 157812 B

15

It can be seen from the comparison experiment that the new compounds have a better fungicidal effect than the known compounds or that, unlike the known compounds, they do not cause any leaf damage.

Claims (4)

1. Azolyl glycol sulfonate, characterized in that it has the general formula Λ3 Λ t / R-C-CH. SO where N 3 is 22 R a n wherein R 2 is (CH 2) 3 C or phenyl, 4 is methylphenyl, 5 is Cl, Br, (CH 1, 2 or 3, X is S or 0 and Y is N. Fungicide, characterized in that it contains an azolyl glycol sulfonate according to claim 1. A fungicide, characterized in that it contains a solid or liquid carrier and an azolyl glycol sulfonate according to claim 1. Method for controlling fungi, characterized in that the fungi or articles to be protected from fungal attack are treated with an azolyl glycol sulfonate according to claim 1.