IE51887B1

IE51887B1 - Substituted azolylglycol sulfonates,fungicides containing these compounds,and their preparation

Info

Publication number: IE51887B1
Application number: IE10/82A
Authority: IE
Original assignee: Basf Ag
Priority date: 1981-01-08
Filing date: 1982-01-05
Publication date: 1987-04-15
Also published as: EP0056860B1; DE3169210D1; EP0056860A1; DK2382A; ATE12039T1; DK157812C; DE3100260A1; DK157812B; IE820010L; GR75398B

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

The present invention relates to novel triazolylglycol sulfonates, a process for their preparation and their use as fungicides.

It is known that imidazolyl ethers, e.g. l-(2,4-di5 chloroplhenyl)-2-(prop-2-enyloxy)-ethyl)-lH-imidazole ' (British Patent 1,318,590), have a fungicidal activity. However, the action of these compounds is unsatisfactory. It is also known that zinc ethylene-bis-(dithiocarbamate) can be used as a fungicide (Chemical Week, 26th July 1972, page 41), but its action is unsatisfactory. Imidazolylether compounds with fungicidal activity are disclosed in European Published Patent Applications Nos. 1,414, 3,049 and 4,303.

We have found that triazolylglycol sulfonates of the formula I where K1 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 carbon atoms, alkoxy of 1 to 4 carbon atoms, phenyl or ο 1 phenoxy, R is selected from the same meanings as R , ip 3 R and R being identical or different, R is halogen, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 - 3 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 zero or an integer from 1 to 5, the Rs being identical or different when n is more than 1, X is S or 0 and Y is N or CH, exhibit a good fungicidal action.

The compounds of the formula 1 have two or more chiral centers. They are obtained as diastereomer mixtures if the alcohols used as synthesis starting materials are also diastereomer mixtures. The invention also comprises the pure diastereomers, which can be obtained by fractional crystallization.

The novel compounds can be obtained when an alcohol of the formula which can be prepared by a conventional process and is described in the literature, is reacted with an alkali metal hydride or an amide, or with a base, eg. NaOH or KOH, in the presence of a catalyst, such as a quaternary ammonium or phosphonium salt, in an aprotic solvent, eg. tetrahydro20 furan, dimethylformamide or dioxane, to give the corresponding alcoholate of the formula - 4 where M is sodium or potassium, and this product is reacted with a sulfohalide of the formula II o Hal-S-R II where Hal is halogen, preferably with a sulfochloride, in one of the solvents mentioned, to give the-compound of the formula 1.

EXAMPLE 1 1-(4-Chlorophenoxy)-3,3-dimethyl-2-(4-methylphenylsulfonyl) 1-(1,2,4-triazol-l-yl)-butane 44.6 g (0.15 mole) of l-(l,2,4-triazol-l-yl)-l-(4chlorophenoxy)-3,3-dimethyl-butan-3-ol, in the form of a distereomer mixture,were dissolved in 500 ml of absolute tetrahydrofuran and 4.5 g of about 80% strength sodium hydride were added to the solution while it was stirred at room temperature. The mixture was then stirred at 4050°C for 6-8 hours and was cooled, and 28.5 g (0.15 mole) of p-toluenesulfocnloride, dissolved in a very little tetrahydrofuran, wei-e added dropwise. The mixture was stirre'd for a further 5-6 hours at room temperature, then hydrolyzed with water and extracted several times with 500 ml of methylene chloride, the organic phase was dried over sodium sulfate, and the solvent was distilled off under reduced pressure. The residue was fractionally crystal25 lized from ethyl acetate. 23.5 g (35% of theory) of a diastereomer mixture of melting point 156-157°C were obtained (Compound No. 1). - 5 The further derivatives below were prepared by the method of Example 1.

Com- pound No. R1 R2 R3 n Y X Melting point in °C 2 (ch3)3c- 4-methyl- phenyl 2,4,5 Cl 3 N 0 122-126 3 (ch3)3c- II 4-Br 1 It II 168-170 4 (ch3)3c- If 2-C1 1 II II 82- 85 10 5 (ch3)3c- II 3,5-Cl 2 II II 210-212 6 (ch3)3c- II 4-C(CH3)3 1 II II 113 δ (ch3)3c- II 4-phenyl 1 II tl 155-156 9 (ch3)3c- II 2,4-Cl 2 ll II 134-136 10 phenyl II 4-Br 1 It It 86- 89 15 11 phenyl II 2-C1 1 II II 126-129 12 phenyl II 4-phenyl 1 II II 84- 87 13 (ch3)3c- ii 4-Br 1 II s 139-141+ 14 (ch3)3c- II 4-Br 1 II s 127-129+ diastereoisomer pair - δ The new active ingredients are particularly suitable for combating fungus diseases in various crop plants, e.g., Erysip'ne graminis in cereals, (Jncinula necator in grapes, Podosphaera leucotricha in apples, Erysiphe ciehoracearum in Cucurbitaceae, ?4ycosphaerella musicola in bananas, Phytophthora infestans in tomatoes and potatoes, Plasmopara viticola in grapes, and Pseudoperonospora humuli in hops.

Some of the active ingredients have a systemic action. The aoolication rates necessary for combating phytophatogenic fungi are generally from 0.025 to 2 kg of active ingredient per hectare.

The new active ingredients are also suitable for protecting wood against attack by wood-destroying fungi such as Coniophora puteana, Lenzites trabea, and Trametes versicolor. The application rates depend on the effect desired, and may vary from 0.001 to 5 wt, based on the weight of the material to be protected; she preferred range is, however, 0.01 to 5 wtS.

Application as fungicide may be effected for instance in the form of directly sprayable solutions, powders, suspensions, dispersions, emulsions, oil dispersions, pastes, dusts, broadcasting agents, or granules by spraying, atomising, dusting, broadcasting or watering. The forms of application depend entirely on the purpose for which the agents are being used; in any case they should ensure as fine a distribution of the active ingredient as possible. ?or the preparation of solutions, emulsions, pastes and oil dispersions to be sprayed direct, mineral oil fractions of medium co high boiling point, such as kerosene or diesel oil, - 7 further coal-tar oils, and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons such as benzene, toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes and their derivatives such as methanol, ethanol, propanol, butanol, chloroform, carbon tetrachloride, cyclohexanol, cyclohexanone, chlorobenzene, isophorone, etc., and strongly polar solvents such as dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone, water, etc. are suitable.

Aqueous formulations may be prepared from emulsion concentrates, pastes, oil dispersions or wettable powders by adding water. To prepare emulsions, pastes and oil dispersions the ingredients as such or dissolved in an oil or solvent may be homogenized in water by means of wetting or dispersing agents, adherents or emulsifiers. Concentrates which are suitable for dilution with water may be prepared from active ingredient, wetting agent, adherent, emulsifying or dispersing agent and possibly solvent or oil.

The fungicides contain, for example, from 5 to 95, and particularly from 10 to 80, wt? of active ingredient.

Examples of surfactants are: alkali metal, alkaline earth metal and ammonium salts of ligninsulfonic acid, naphthalenesulfonic acids, phenolsulfonic acids, alkylaryl sulfonates, alkyl sulfates, and alkyl sulfonates, alkali metal and alkaline earth metal salts of dibutylnaphthalenesulfonic acid, lauryl ether sulfate, fatty alcohol sulfates, alkali metal and alkaline earth metal salts of fatty acids, salts of sulfated hexadecanols, heptadecanoIs, and octadecanols, salts of sulfated fatty alco51887 - 8 nol glycol ethers, condensation products of sulfonated naphthalene and naphthalene derivatives with formaldehyde, condensation products of naphthalene or naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ethers, ethoxylated isooctylphenol, ethoxylated octylphenol and ethoxylated nonylphenol, alkylphenol polyglycol ethers, tributylphenyl polyglycol ethers, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol esters, lignin, sulfite waste liquors and methyl cellulose.

Powders, dusts and broadcasting agents may be prepared by mixing or grinding the active ingredients with a solid carrier.

Granules, e.g., coated, impregnated or homogeneous granules, may be prepared by bonding the active ingredients to solid carriers. Examples of solid carriers are mineral earths such as silicic acid, silica gels, silicates, talc, kaolin, Attaclay, limestone, lime, chalk, bole, loess, clay, dolomite^ diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground plastics, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, and ureas, and vegetable products such as grain flours, bark meal, wood meal, and nutshell meal, cellulosic powders, etc.

EXAMPLE a parts by weight of compound 1 was mixed with 10 parts by weight of N-methyl-j/rpyrrolidone. A mixture was obtained suitable for application in the form of very fine drops.

S1887 - 9 EXAMPLE b parts by weight of compound 2 was dissolved in a mixture consisting of 90 parts by weight of xylene, 6 parts by weight of the adduct of 8 to 10 moles of ethylene oxide with 1 mole of oleic acid-N-monoethanolamide, 2 parts by weight of the calcium salt of dodecylbenzenesulfonic acid, and 2 parts by weight of the adduct of 40 moles of ethylene oxide with 1 mole of castor oil.

EXAMPLE c parts by weight of compound 3 was dissolved in a mixture consisting of 60 parts by weight of cyclohexanone, parts by weight of isobutanol, 5 parts by weight of the adduct of 7 moles of ethylene oxide with 1 mole of isooctylphenol, and 5 parts by weight of the adduct of 40 moles of ethylene oxide with 1 mole of castor oil.

EXAMPLE d parts by weight of compound 1 was dissolved in a mixture consisting of 25 parts by weight of cyclohexanone, 65 parts by weight of a mineral oil fraction having a boiling point between 210° and 280°C, and 10 parts by weight of the adduct of 40 moles of ethylene oxide with 1 mole of castor oil.

EXAMPLE e parts by weight of compound 1 was well mixed with 3 parts by weight of the sodium salt of diisobutylnaphthalene25 -^-sulfonic acid, 10 parts by weight of the sodium salt of a lignin-sulfonic acid obtained from a sulfite waste liquor, and 7 parts by weight of powdered silica gel, and triturated in a hammer mill. - 10 EXAMPLE f parts by weight of compound 1 was intimately mixed with 95 parts by weight of particulate kaolin. A dust was obtained containing 5? by weight of the active ingredient.

EXAMPLE g parts by weight of compound 1 was intimately mixed with a mixture consisting of 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil which had been sprayed onto the surface of this silica gel. A formulation of the active ingredient was obtained having good adherence.

EXAMPLE h parts by weight of compound 1 was intimately mixed with 10 parts of the sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate, 2 parts of silica gel and 48 parts of water. Dilution in 100,000 parts by weight of water gave an aqueous dispersion containing 0.04 wt? of active ingredient. EXAMPLE i parts of compound 1 was intimately mixed with 12 parts of the calcium salt of dodecylbenzenesulfonic acid, 8 parts of a fatty alcohol polyglycol ether, 2 parts of the sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate and 63 parts of a paraffinic mineral oil. A stable oily dispersion was obtained.

The fungicides may, in these application forms, contain other active ingredients together witn those according to the invention, e.g. herbicides, insecticides, growth regulators and other fungicides or may be mixed with fertilizers and applied - 11 together with these. When the active ingredients are mixed with other fungicides, the fungicidal spectrum of action is in many cases broadened.

The list of fungicides given below, with which the compounds according to the invention can be combined, is intended to illustrate the possible combinations, but the invention is in no way limited to these.

Examples of fungicides which can be combined with the compounds of the invention are: dithiocarbamates and their derivatives, e.g. iron(III) dimethyldithioearbamate, zinc dimethyldithiocarbamate, manganese M,N-ethylene-bis-dithiocarbamate, manganese zinc Ν,Ν-ethylenediamine-bis-dithiocarbamate, zinc Ν,Ν-ethylene-bis-dithiocarbamate, tetramethylthiuram disulfide, the ammonia complex of zinc Ν,Ν-ethylene-bis-dithiocarbamate and zinc Μ,Ν'-propylene-bis-dithiocarbamate, and the ammonia complex of zinc Ν,Ν'-propylene-bis-dithiocarbamate and N,N'-polypropylene-bis-(thiocarbamoyl)-disulfide; nitro derivatives, e.g. dinitro-(1-methylheptyl)-phenyl crotonate, 2-sec.-butyl-4,6-dinitropheny1-3,3-dimethylacrylate and 2-sec.-butyl-4,6-dinitrophenyl isopropyl carbonate; heterocyclic compounds, e.g. N-trichloromethylthiotetrahydrophthalimide, N-trichloromethylthio-phthalimide, 2-heptadecyl-2-imidazoline acetate, 2,4-dichloro-b-(o-cnloroanilino)-s-triazine, 0,0-diethyl phthalimidophosphonothioate, 5-amino-l-(bis-(dimethylamino)-phosphinyl)-3-phenyl-l,2,4-triazole, 5-ethoxy-3-trichloromethy1-1,2,4-thiadiazole, 2,3-dicyano-l,4-dithiaanthraquinone, 2-thio-l,3-dithio-(4,5-b)-quinoxaline, methyl l-(butylcarbamoyl)-2-benzimidazole-carbamate, 2-methoxy51887 - 12 carbonylaraino-benzimidazole, 2-thiocyanatomethyltnio-benzthiazole, 4- (2-chlorophenylhydrazone)-3-methyl-5isoxazolone, pyridine-2-thio-1-oxide, 8-hydroxyquinoline and its copper salt, 2,3-dihydro-5-carboxanilido-6-methy1-1,4-oxathiin-4,4-dioxide, 2,3-dihydro-5-carboxanilido-6-methyl-l,4-oxathiin, 2-fur-2-yl-benzimidazole, piperazine-l,4-diyl-bis-(1-(2,2,2-trichloroethyl)-formamide), 2-thiazol-4-yl-benzimidazole, 5-butyl-2-dimethylamino-4-hydroxy-6-methyl-pyrimidine, bis-(D-chlorophenyl)-3-pyridinemethanol, l,2-bis-(3-ethoxycarbonyl-2-thioureido)10 -benzene, l,2-bis-(3-methoxycarbonyl-2-thioureido)-benzene and various fungicides, e.g. dodecylguanidine acetate, 3-(2-(3j5-dime thyl-2-hydroxy cy clohexy1)-2-hydroxyethyl)-glutarimide, hexachlorobenzene, N-dicnlorofluoromethylthio-N',N'-dimethyl-N-phenyl-sulfuric acid diamide, 2,5-dimethyl-furan-3-carboxylic acid anilide, 2,5"dimethylfuran-3~carboxylic acid cyclohexylamide, 2-methyl-benzoic acid anilide, 2-iodo-benzoic acid anilide, 1-(3,4-dichloroanilino)-l-formylamino-2,2,2-trichloroethane, 2,6-dimethy1-N-tridecyl-morpholine and its salts, 2,6-dimethyl-N-cyclodecyl-morpholine and its salts, DL-methyl-N20 -(2,6-dimethyl-phenyl)-N-fur-2-yl-alanate, methyl DL-N-(2,6-dimethy1-pheny1)-N-(2'-methoxyacetyl)-alanate, diisopropyl - nitroisophthalate, 1-(11,2',4'-triazol-l'-yl)-(4'-chloro— phenoxy)-3,3-dimethylbutan-2-one, 1-(1',2',4’-triazol-l'-yl)-(4 -ehlorophenoxy)-3,3-dimethylbutan-2-ol, N- (2,6-dimethylpheny1)25 -N-chloroacetyl-D,L-2-aminobutyrolactone and N-(n-propyl)-N-(2,4,6-trichlorophenoxyethyl)-N'-imidazolylurea.

The good fungicidal action of the new compounds is - 13 demonstrated in the examples below. The prior art compounds (1-(2(2,4-dichlorophenyl)-2'-(2-propenyloxy)-ethy1)-1H-imidazole) (A) and zinc Ν,Ν-ethylene-bis-dithiocarbamate (B) were used for comparison purposes.

EXAMPLE 1 Action on wheat mildew Leaves of pot-grown wheat seedlings of the Jubilar variety were sprayed with aqueous emulsions the solids of whicn consisted of 80% (by weight) of active ingredient and 20% of emulsifier, and dusted, after the sprayed-on layer had dried, with spores of wheat mildew (Erysiphe graminis var. tritici). The plants were then placed in a greenhouse at 20° to 22°C and 75 to 80% relative humidity. The extent of mildew spread was determined after 10 days.

In this experiment, compounds nos. 1 and 6 had a better fungicidal action than active ingredient A.

EXAMPLE 2 Action on cucumber mildew Leaves of pot-grown cucumber seedlings were sprayed with aqueous emulsions, the solids comprising 80% of active ingredient and 20% of emulsifier, and dusted, after the sprayed-on layer had dried, with spores of cucumber mildew (Erysiphe cichoracearum). The plants were then placed in a greenhouse at from 20° to 22°C and from 75 to 80% relative humidity. The extent of fungus development was determined after 10 days.

In this experiment, active ingredients nos. 1, 3 and 4 had a very good fungicidal action. - 14 EXAMPLE 3 Action on Phytophthora infestans in tomatoes Leaves of tomato plants of the Professor Rudloff variety were sprayed with aqueous suspensions containing (dry basis) 80S (wt?) of active ingredient and 20? of sodium lignin sulfonate 0.025, 0.006 and 0.0015? (dry basis) spray liquors were used. After the sprayed-on layer had dried, the leaves were infected with a zoospore suspension of Phytophthora infestans. The plants were then placed for 5 days in a steam-saturated (moist) chamber kept at 16° to l8°C. After this period, the disease had spread on the untreated infected control plants to such as extent that the fungicidal action of the compounds was able to be assessed.

In this experiment, active ingredient no. 6 had a better fungicidal action than prior art active ingredient B.

S1887

Claims

1. An azolylglycol sulfonate of the formula 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 0 4 carbon atoms, phenyl or phenoxy, R is selected from the same meanings as R 1 , R 1 and R 2 being identical or different, R 3 is 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 zero or an integer from 1 to 5, the R 3 s being identical or different when n is more than 1, X is S or 0 and Y is N or CH.

2. An azolylglycol sulfonate as claimed in claim 1, l 2 wherein R is alkyl of 1 to 4 carbon atoms or phenyl, R is optionally substituted phenyl, R is chlorine, bromine, alkyl of 1 to 4 carbon atoms or phenyl and n is 1, 2 or 3.

3. An azolylglycol sulfonate as claimed in claim 1 and hereinbefore identified as any of compounds 1 to 6 or 8 to 14.

4. A process for producing an azolylglycol sulfonate - 16 31887 as claimed in claim 1, wherein an alcoholate of the formula is reacted with a sulfohalide of the formula π 2 Hal-S-R It 12 3 5. Where R , R , R , X and Y have the meanings given in claim 1, Hal denotes a halogen atom, and M denotes an alkali metal, a quaternary ammonium or a phosphonium ion.

5. An azolylglycol sulfonate as claimed in claim 1 when produced by a process as claimed in claim 4. 10

6. The use of an azolylglycol sulfonate as claimed in any of claims 1 to 3 or 5 as a fungicide.

7. A fungicide comprising a solid or liquid carrier and an azolylglycol sulfonate as claimed in any of claims 1 to 3 or 5. 15

8. A process for combating fungi, wherein the fungi or objects to be protected against fungus attack are treated with an azolylglycol sulfonate as claimed in any of claims 1 to 3 or 5.

9. A process for combating fungal disease in crop 20 plants wherein an azolylglycol sulfonate as claimed in any of claims 1 to 3 or 5 is applied to the crop area.