CA1119605A - L,3-bis-(trihalomethylsulfenyl)-imidazoline-2,4- diones - Google Patents
L,3-bis-(trihalomethylsulfenyl)-imidazoline-2,4- dionesInfo
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Abstract
ABSTRACT OF THE DISCLOSURE
A 1,3-bis-(trihalomethylsulfenyl)-imidazoline-2,4-dione of the formula
A 1,3-bis-(trihalomethylsulfenyl)-imidazoline-2,4-dione of the formula
Description
O.Z~ 0050/032590 1,3-BIS-(TRIHALO~ETHYLSULFENYL)~IMIDAZOLINE-2,4~DIONES
The present invention relates to new and valuable 1,~-bis--(trihalomethylsulfenyl)~imidazoline-2,4-diones and their use as fungicides.
It is known (E.J. Lien and co-workers, Pestic. Biochem.
and Physiol.g 4~ 289, 1974) that bis S-CC13 derivatives o~
5,5-diphenyl- and 5-ethyl-5-phenylimidazoline-294-dione have fungicidal properties.
We have now found that new imidazoline-2,4-dione derivatives of the formula O R
r~
XCC12-S-N~,,N-S CC12Y
where X and Y are idential or different and each denotes chlorine or ~luorine, and R1 and R2 are identical or different and each denotes hydrogen or lower alkyl (C1-C4), or R1 and R2 are directly linked with each other, or together denote the radical -(CH2)n-, n denoting one o~ the integers 1, 2, 3, 4, 5 and 6, have a strong ~ungicidal action. I~e new co~pounds have a broad spectrum of act;on and may be used especially on Phycomycetes and Fungi imperfecti, but also on Ascomycetes and Basidiomycetes. The new compounds are for example particularly suitable for protecting plants against phytopathogenic fungi, e.g., Plasmopara viticola in grapes, Pseudoperonospora humuli in hops, Phytophthora in-festans in potatoes and tomatoes, Pythium ultimum in pea seedlingsS
Botrytis cinerea in grapes, strawberries~and pimientos, Septoria nodorum in cereals, and Venturia inaequalis (scab) in apple ~rees.
-- 1 -- .
.~ ~ .
os O.Z. 0050/032590 In the concentrations necessary ~or combating fungi, the com-pounds cause no damage to crop plants.
We have further found that compounds of the ~ormula I are obtained by reacting an imidazoline-2,4-dione of the formula O Rl \~ R2 ~N y NH II
- O
with a sulfenyl chloride of the formula XCC12-S-Gl (IIIa) or YCC12-S-Cl tIIIb), R1, R2, X and Y having the above meanings, if desired in the presence of an acid binder and if desired in the presence of a diluent.
The compounds of the formula I may also be obtained by reacting an imidazoline-2~4-dione of the ~ormula O Rl ~ R2 XCC 12-S~N~,NH IV, o R1, R2 and X having the above meanings, with a sulfenyl chloride of the formula IIIb, i~ desired in the presence of an acid binder and if desired in the presence of a diluent.
The compounds of the formula I according to the invention may further be obtained by reacting an N-cyclopropylimidazoline-
The present invention relates to new and valuable 1,~-bis--(trihalomethylsulfenyl)~imidazoline-2,4-diones and their use as fungicides.
It is known (E.J. Lien and co-workers, Pestic. Biochem.
and Physiol.g 4~ 289, 1974) that bis S-CC13 derivatives o~
5,5-diphenyl- and 5-ethyl-5-phenylimidazoline-294-dione have fungicidal properties.
We have now found that new imidazoline-2,4-dione derivatives of the formula O R
r~
XCC12-S-N~,,N-S CC12Y
where X and Y are idential or different and each denotes chlorine or ~luorine, and R1 and R2 are identical or different and each denotes hydrogen or lower alkyl (C1-C4), or R1 and R2 are directly linked with each other, or together denote the radical -(CH2)n-, n denoting one o~ the integers 1, 2, 3, 4, 5 and 6, have a strong ~ungicidal action. I~e new co~pounds have a broad spectrum of act;on and may be used especially on Phycomycetes and Fungi imperfecti, but also on Ascomycetes and Basidiomycetes. The new compounds are for example particularly suitable for protecting plants against phytopathogenic fungi, e.g., Plasmopara viticola in grapes, Pseudoperonospora humuli in hops, Phytophthora in-festans in potatoes and tomatoes, Pythium ultimum in pea seedlingsS
Botrytis cinerea in grapes, strawberries~and pimientos, Septoria nodorum in cereals, and Venturia inaequalis (scab) in apple ~rees.
-- 1 -- .
.~ ~ .
os O.Z. 0050/032590 In the concentrations necessary ~or combating fungi, the com-pounds cause no damage to crop plants.
We have further found that compounds of the ~ormula I are obtained by reacting an imidazoline-2,4-dione of the formula O Rl \~ R2 ~N y NH II
- O
with a sulfenyl chloride of the formula XCC12-S-Gl (IIIa) or YCC12-S-Cl tIIIb), R1, R2, X and Y having the above meanings, if desired in the presence of an acid binder and if desired in the presence of a diluent.
The compounds of the formula I may also be obtained by reacting an imidazoline-2~4-dione of the ~ormula O Rl ~ R2 XCC 12-S~N~,NH IV, o R1, R2 and X having the above meanings, with a sulfenyl chloride of the formula IIIb, i~ desired in the presence of an acid binder and if desired in the presence of a diluent.
The compounds of the formula I according to the invention may further be obtained by reacting an N-cyclopropylimidazoline-
-2~4-dione of the ~ormula O Rl ~ R2 D~Ny NH V, b with a sulfenyl chloride of the formula XCC12-S-Cl (IIIa) or YCC12-S-Cl (IIIb), R1, R2, X and Y having the above meanings, ~9~(~S
O.Z. 0050/032590 with elimination of the cyclopropyl group as allyl chloride and if desired in the presence of an acid binder and if desired in the pre~ence o~ a diluent.
Finally, the compounds of the formula I according to the inv~ntion in which X or X and Y denote fluorine m~y be obtained by reacting an imidazoline-2 4-dione of ~he formula O R
Cl C-S- ~ ;S-CCl VI, R1 and R2 having the above meanings, with anhydrous hydrofluoric acid, in order to exchange one or two ~luorine atoms in the tri chloromethylthio side chain ~or one or two chlorine atoms.
The first three of the abo~e reactions according to the in-vention of imidazoline-2,4-diones of the ~ormul~e II, IV and V
are advantageously carried out in solvents or diluents inert to the reactants~ e.g., toluene, xylen~, diethyl ether, tetrahydro-~uran, dioxane, dimethoxyethane, acet~ne, methyl ethyl ketone, ethyl acetate, methylene chloride, and chloro~orm.
The reaction with a compound o~ the formula VI can be carried out in an excess o~ hydrofluoric acid as diluent.
Examples o~ suitable acid binders are inorganic bases such as hydroxides or carbonates of alkali metals and alkaline earth metals (e.g., NaOH, Na2C03), and particularly tertiary amines, ~uch as triethylamine, dimethylaniline, and p~ridine.
me reactions are carried out at, for instance, from -30 to ~100 C, pre~erably from -10 to+25C~ and at atmospheric pre3~ure. The imidazoline-2,4-diones o~ the formulae II and IV
used as starting materials are known from the literature and may be prepared in accordance with Bucherer ~J. Prakt. Chem.
140, 303, 1934) or Cremlyn (J. Chem. Soc. 6240, 1964) _ 3 _ ~9~
O.Z. 0050/0325~0 The first reaction described above, employing a compound of the formula II, is preferred.
The compounds of the formula I according to the invention are colorless crystalline products readily soluble in ethyl - acetate, acetone, ethanol9 tetrahycLrofuran, methylene chloride, chloroform, dimethyl sulfoxide, dimethyl~ormamide, and N-methyl-pyrrolidone.
Individual examples of the new active ingredients are given below (the imidazoline-2,4-diones are designated "hydant;oins"
in the following):
1,3-bis-(trichloromethylthio)-hydantoin 1,3-bis-(dichlorofluoromethylthio)-hydantoin 1-trichloromethylthio-3-dichlorofluoromethylthiohydantoin 1-dichlorofluoromethylthio-3-trichloromethylthiohydantoin 1,3-bis-(trichloromethylthio)-~-methylhydantoin - 1,3-bis-(dichloro~luoromethylthio)-5-methylhydantoin 1~3-bis-(trichloromethylthio)-5,5-dimethylhydantoin 1,3-bis-(dichloro~luoromethylthio)-5,5 dimethylhydantoin 1~3-bis-(trichloromethylthio)-5-methyl-5-ethylhydantoin 1-dichlorofluoromethyl-3-trichloromethylthio-5-methyl-5-ethyl-hydantoin 1,3-bis-~trichloromethylthio)-trans-cyclohexanespiro-5-hydantoin 1,3-bis-~dichlorofluoromethylthio)-trans-cyclohexanespiro-5-hydantoin.
The manufacture o~ the active ingredients is illustrated by the following examples.
O~>~ ` , ClC13-S~ N~N-S-Cl~12F
At about 0 t;o ~5 C, 16.9 g (0~1 mole) of dichlorofluoro methylsulfenyl chloride and subsequently 10.1 g (0.1 mole)o~ tri-ethylamine are dripped, while stirring thoroughly, into a sus~
s O.Z. 0050/032590 pension of 24.9 g (0.1 mole) of 3-trichloromethylthiohydantoin in 200 ml of anhydrous ethyl acetate. After stirring for 2 hours at room temperature (20 C) the precipitated triethylamine hydro-chloride is filtered off and washed with 50 ml of ethyl acetate.
The filtrate is extracted by shaking with 250 ml of water, dried3 clarified with 1 g of animal charcoal, and concentrated. The residue crystallizes at 0C after the addition of 50 ml of n-pentane. There is obtained 31.3 g (82% of theory) of 1-dichloro-fluoromethylthio-3-trichloromethylthiohydantoin; m.p.: 114-116C.
The 3-trichloromethylthiohydantoin (m.p.o 184C) used as starting material was prepared in accordanGe with R.J.W. Cremlyn (J. Chem. Soc., 6240, 1964).
O q~
y O
a) At about 0C, 37.2 g (0.2 mole) of trichloromethylsulfenyl chloride and subsequently 20.2 g (0.2 mole) of triethylamine are dripped, while stirring thoroughly3 into a suspension of 10 g (0.1 mole) of hydantoin in 150 ml of anhydrous ethyl acetate.
After stirring for 90 minutes at room temperature, the precipitated triethylamine hydrochloride is filtered off and washed with 100 ml of ethyl acetate. The filtrate is concentrated and the residue is crystallized by trituration with n-pentane. There is obtained 36.1 g (~0.5% o~ theory) o~ 1,3-bis-(trichloromethyl-thio)-hydantoin, mOp.: 142C.
b) At about 25C, 37.2 g (0.2 mole) of trichloromethylsul-fenyl chloride and subsequently 20.2 g (0.2 mole) of triethylamine are dripped, while stirring thoroughly, into a suspension of 14.0 g (0.1 mole)of 3-cyclopropylhydantoin in 150 ml of anhydrous hydantoin. After stirring for 12 hours at room temperature, the ~.
os O.Z. 0050/032590 precipitated triethylamine hydrochloride is filtered off and the reaction mixture is worked up as in Example 1. There is obtained 23.5 g (59% of theory) of 1,3-bis-(trichloromethyl-thio)-hydantoin; m.p. 140 -142 C.
The 3-cyclopropylhydantoin (m.p.: 137-139C) used as starting material was prepared in accordance with A. Mouneyrat (Chem. Ber., 33, 2393, 1900) from cyclopropyl isocyanate and glycocoll.
The compounds in Table 1 below were prepared analogously:
0 Rl ~R2 XCC12-S-N~N-S-CC12Y
Example No. R1 R X Y m.p.C
O.Z. 0050/032590 with elimination of the cyclopropyl group as allyl chloride and if desired in the presence of an acid binder and if desired in the pre~ence o~ a diluent.
Finally, the compounds of the formula I according to the inv~ntion in which X or X and Y denote fluorine m~y be obtained by reacting an imidazoline-2 4-dione of ~he formula O R
Cl C-S- ~ ;S-CCl VI, R1 and R2 having the above meanings, with anhydrous hydrofluoric acid, in order to exchange one or two ~luorine atoms in the tri chloromethylthio side chain ~or one or two chlorine atoms.
The first three of the abo~e reactions according to the in-vention of imidazoline-2,4-diones of the ~ormul~e II, IV and V
are advantageously carried out in solvents or diluents inert to the reactants~ e.g., toluene, xylen~, diethyl ether, tetrahydro-~uran, dioxane, dimethoxyethane, acet~ne, methyl ethyl ketone, ethyl acetate, methylene chloride, and chloro~orm.
The reaction with a compound o~ the formula VI can be carried out in an excess o~ hydrofluoric acid as diluent.
Examples o~ suitable acid binders are inorganic bases such as hydroxides or carbonates of alkali metals and alkaline earth metals (e.g., NaOH, Na2C03), and particularly tertiary amines, ~uch as triethylamine, dimethylaniline, and p~ridine.
me reactions are carried out at, for instance, from -30 to ~100 C, pre~erably from -10 to+25C~ and at atmospheric pre3~ure. The imidazoline-2,4-diones o~ the formulae II and IV
used as starting materials are known from the literature and may be prepared in accordance with Bucherer ~J. Prakt. Chem.
140, 303, 1934) or Cremlyn (J. Chem. Soc. 6240, 1964) _ 3 _ ~9~
O.Z. 0050/0325~0 The first reaction described above, employing a compound of the formula II, is preferred.
The compounds of the formula I according to the invention are colorless crystalline products readily soluble in ethyl - acetate, acetone, ethanol9 tetrahycLrofuran, methylene chloride, chloroform, dimethyl sulfoxide, dimethyl~ormamide, and N-methyl-pyrrolidone.
Individual examples of the new active ingredients are given below (the imidazoline-2,4-diones are designated "hydant;oins"
in the following):
1,3-bis-(trichloromethylthio)-hydantoin 1,3-bis-(dichlorofluoromethylthio)-hydantoin 1-trichloromethylthio-3-dichlorofluoromethylthiohydantoin 1-dichlorofluoromethylthio-3-trichloromethylthiohydantoin 1,3-bis-(trichloromethylthio)-~-methylhydantoin - 1,3-bis-(dichloro~luoromethylthio)-5-methylhydantoin 1~3-bis-(trichloromethylthio)-5,5-dimethylhydantoin 1,3-bis-(dichloro~luoromethylthio)-5,5 dimethylhydantoin 1~3-bis-(trichloromethylthio)-5-methyl-5-ethylhydantoin 1-dichlorofluoromethyl-3-trichloromethylthio-5-methyl-5-ethyl-hydantoin 1,3-bis-~trichloromethylthio)-trans-cyclohexanespiro-5-hydantoin 1,3-bis-~dichlorofluoromethylthio)-trans-cyclohexanespiro-5-hydantoin.
The manufacture o~ the active ingredients is illustrated by the following examples.
O~>~ ` , ClC13-S~ N~N-S-Cl~12F
At about 0 t;o ~5 C, 16.9 g (0~1 mole) of dichlorofluoro methylsulfenyl chloride and subsequently 10.1 g (0.1 mole)o~ tri-ethylamine are dripped, while stirring thoroughly, into a sus~
s O.Z. 0050/032590 pension of 24.9 g (0.1 mole) of 3-trichloromethylthiohydantoin in 200 ml of anhydrous ethyl acetate. After stirring for 2 hours at room temperature (20 C) the precipitated triethylamine hydro-chloride is filtered off and washed with 50 ml of ethyl acetate.
The filtrate is extracted by shaking with 250 ml of water, dried3 clarified with 1 g of animal charcoal, and concentrated. The residue crystallizes at 0C after the addition of 50 ml of n-pentane. There is obtained 31.3 g (82% of theory) of 1-dichloro-fluoromethylthio-3-trichloromethylthiohydantoin; m.p.: 114-116C.
The 3-trichloromethylthiohydantoin (m.p.o 184C) used as starting material was prepared in accordanGe with R.J.W. Cremlyn (J. Chem. Soc., 6240, 1964).
O q~
y O
a) At about 0C, 37.2 g (0.2 mole) of trichloromethylsulfenyl chloride and subsequently 20.2 g (0.2 mole) of triethylamine are dripped, while stirring thoroughly3 into a suspension of 10 g (0.1 mole) of hydantoin in 150 ml of anhydrous ethyl acetate.
After stirring for 90 minutes at room temperature, the precipitated triethylamine hydrochloride is filtered off and washed with 100 ml of ethyl acetate. The filtrate is concentrated and the residue is crystallized by trituration with n-pentane. There is obtained 36.1 g (~0.5% o~ theory) o~ 1,3-bis-(trichloromethyl-thio)-hydantoin, mOp.: 142C.
b) At about 25C, 37.2 g (0.2 mole) of trichloromethylsul-fenyl chloride and subsequently 20.2 g (0.2 mole) of triethylamine are dripped, while stirring thoroughly, into a suspension of 14.0 g (0.1 mole)of 3-cyclopropylhydantoin in 150 ml of anhydrous hydantoin. After stirring for 12 hours at room temperature, the ~.
os O.Z. 0050/032590 precipitated triethylamine hydrochloride is filtered off and the reaction mixture is worked up as in Example 1. There is obtained 23.5 g (59% of theory) of 1,3-bis-(trichloromethyl-thio)-hydantoin; m.p. 140 -142 C.
The 3-cyclopropylhydantoin (m.p.: 137-139C) used as starting material was prepared in accordance with A. Mouneyrat (Chem. Ber., 33, 2393, 1900) from cyclopropyl isocyanate and glycocoll.
The compounds in Table 1 below were prepared analogously:
0 Rl ~R2 XCC12-S-N~N-S-CC12Y
Example No. R1 R X Y m.p.C
3 H H F F 92- 94
4 H H F Cl 132-133 H -CH3 C~ Cl 106-108 6 H -CH3 ~ F 87- 89 -CH3 -CH3 Cl Cl 114-116 9 -CH3 -C2H5 Cl Cl 110-112 -C~3 -C2H5 Cl F 97- 98 11 Cl Cl 14~ 9 12 -(CH2)5- F F 87- 88 The compounds according to the invention may be converted into the usual ~ormulations, e.g. solutions~ emulsions, suso penslons, dusts, powders, pastes and granules. The formulations are prepared in conventional manner, e.g., by extending the active ingredient with solvents and/or carriers 9 if desired using emulsifiers and dispersants. Where water is used as diluent, other organic solvents may also be employed as auxiliary sol-O.Z. 0050/032590 vents. Suitable compounds ror preparing such formulations are 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 rock flours (e.g., ~aolins, diatomaceous earth, talc, chalk) and synthetic rock flours (e.g.~ highly disperse silicic acid, silicate~); emulsifiers such as nonionic and anionic emulsi~ying agents (e.g. polyoxyethylene-~atty alcohol ether alkyl sulfonates and aryl su}fonates); and dispersants such a~
lignin, sulfite waste liquors and methyl cellulose.
Thè formulations generally contain from 0.1 to 95, and pre~erably ~rom 0.5 to 90, wtZ of active ingredient.
The formulation~ and the ready-to-use products made there from, e.g., solutions, emulsions, suspensions, powders, dusts, pastes or granules, are applied in known manner, for example by spraying, atomizing~ dusting, scattering, seed-disinfecting, pouring, painting or impregnating.
me application rates depend on the ef~ect desired, and range ~rom 0.01 to 3 kg of active ingredient per hectare, or mcre.
Some of the compounds also have a good bactericidal action on bacteria such as Staphylococcus aureus. When the active ingre-dients according to the invention are used to protect materials~
fungi such as Aspergillus-niger, Aspergillus flavus, A~pergillus versicolor, Penicillium funiculosum, Chaetomium globosum, Cladosporium herbarum, Pullularia pullulans, Humicola grisea, and Sclerophoma pityophila are combated. When the active ingre-dients are used to protect materials, e.g., as fungicides for sur~ace coatings and soft PVC (polyvinyl chloride) ,the application rates are fran 0.05 to 5~ (by weight) of active ingredient, based on the total weight of the paints to be preserved or the PVC to be micro-bicidally treated. The new active ingredients may also be used ~., ' ~ ' ~ .
, . . .
O.Z. 0050~032590 as fungicidally ef~ective components of preservatives ~or protecting wood against wood-discoloring fungi. Application is e~ected by tre~ting, e.g., impregnating or painting, the wood with these agents.
The agents according to the invention may also be mixed and applied with other acti~e ingrQdients, e.g., herbicides, insecticides, growth regulators, bactericides, fungicides and fertilizers. When mixed with other fungicides, the spectrum of fungicidal action is in many ca~es increased; with a number of these fungicidal compositionsy synergistic ef~ects also occur;
i.e., the fungicidal action of the combination product is greater than the effect of the individual components added together.
Examples of fungicides which may be combined with the com~
pounds according to the invention are: dithiocarbamates and their derivatives, e.g~ iron(III) dimethyldithiocarbamate, zinc dimethyldithiocarbamate9 manganese N,N-ethylene-bis-dithiocarb-amate, manganese zinc N,N-ethylenediamine-bis-dithiocarbamate, zinc N,N-ethylene-bis-dithiocarbamate, tetramethylthiuram di-sul~ide, the ammonia complex o~ zinc N,N-ethylene-bis-dithio-carbam~te and N,N'-polyethylene- bis (thiocarbamoyl)-disulfide, zinc N,N'-propylene-bis-dithiocarbamate, and the ammonia complex of zinc N,N'-propylene-bis-dithioc~rbamate and N-Nt-polypropylene--bis-(thiocarbamoyl)-disul~ide; nitro derivatives, e.g. dinitro--(1-methylheptyl)-phenyl crotonate, 2-sec.-butyl-4,6-dinitro-phenyl 3,3-dimethylacrylate and 2-sec.-butyl-4,6-dinitrophenyl isopropyl carbonate; heterocyclic compounds, e.g. N-trichloro-methylthiotetrahydrophthalimide, N-trichloromethylthio-pnthal-imide, 2-heptadecyl-2-imidazoline acetate, 294-dichloro-6-(o -chloroanilino~-s-triazine, 0,0-diethyl phthalimidophosphono-thioate, 5-amino-1-(bis-(dimethylamino)-phosphinyl)-3-phenyl--1,2~4-triazole, 5-ethoxy-3-trichloromethyl-1,2,4-thiadiazole, iO5 O.Z. 0050/032590 2,~-dicyano-1,4~dithiaanthraquinone, 2-thio-1,3-dithio(4,5-b)-quinoxaline, methyl 1-(butylcarbamoyl)-2-benzimidazole-carbamate, 2-methoxycarbonylamino-benzimidazol~, 2-thiocyanatomethylthio--benzthia~ole, 4-(2-chlorophenylhydrazono)-3-methyl-5-i~oxazolone, pyridine-2-thio-1-oxide, 8-hydroxyquinoline and its copper salts,, 2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiine-4,4--dioxide, 2,3-dihydro-5~carboxaniliclo-6-methyl-1,4-oxathiine, 2-fur-2-yl-benzimidazole, piperazine-1,4-diyl-bis-(1-(2,2,2-tri-chloroethyl)-formamide) 9 2-thiazol-4-yl-benzimidazole, 5 butyl--2-dimethylamino-4-hydroxy-6-methyl-pyrimidine, bis-(p-chloro-phenyl)-3-pyridinemethanol, 1,2-bis-(3-ethoxycarbonyl-2 thio-ureido)-benzene, 1,2-bis-(3-methoxycarbonyl-2-thioureido)-ben-zene and various fungicides~ e.g. dodecylguanidine acetate, 3-~2-(3,5-dimethyl-2-hydroxycyclohexyl)-2-hydroxyethy].)-glutar-imide, hexachlorobenzene, N-dichlorofluoromethylthio-N',N'-di-methyl-N-phenyl-sulfuric acid diamide, 2,5-dimethyl-furan-3--carboxylic acid anilide, 2~5-dimethylfuran-~-carboxylic acid cyclohexylamide, 2-methyl-benzoic acid anilide, 2-iodo-benzoic acid anilide, 1-(3,4-dichloroanilino)-1-formylamino-2,2,2-tri-chloroethane, 2,6-dimethyl-N-tridecyl-morpholine and its salts, and 2,6-dimethyl-N-cyclododecyl-morpholine and its salts.
In the following experiment~ demon~trating the fungicidal action of the compounds according to the invention, the following prior art active ingredients were used for comparison purposes.
1,3-bis-(trichloromethylthio)-5-ethyl-5-phenylhydantoin (comparative compound A) 1,3-bis-(trichloromethylthio)-5,5-diphenylhydantoin (comparative compound B).
~ 9 _ , . . . .
O.Z. 0050/032590 E.YAMPLE 13 Plasmopara viticola in grapes LeaYes of potted vines o~ the ~I~ller-Thurgau variety are sprayed with aqueous dispersions containing ~dry basis) 80~ (wt%) of the active ingredient and 20~ of sodium lignin sulfonate.
0.1, 0.05 and 0.025~ (dry basis) spray liquors are used. After the spra~ed-on liquor has dried, tXe leaves are infected with a zoospore suspension o~ Plasmopara viticola. The plants are ~irst placed for 16 hours in a steam-saturated (moist)chamber at 20C, and then in a greenhouse for 8 day~ at from 20 to 30C. To accelerate and intensify the sporangicphore discharge, the plants are then again placed in the moist chamber ~or 16 hours. The spore sites on the underside of the lea~es are then counted; 0 denotes no ~ungus attack, graduated down to 5, which denotes total attack (control).
Active Leaf attack after spraying with liquor con-ingredient taining active ingredients in amounts of 0.1% 0.05% 0.025g . . ~
g 0 2 2 Control tuntreated~ 5 .. ....
~ . ... _ ~9605 O.Z. 0050/032590 EXA~LE 14 Phytophthora infestans in tomatoes Leaves of tomatoes of the "GroRe Fleischtomate" variety are sprayed with aqueous dispersions containing (dry basis) 80% (wt%) of active ingredient and 20% of soditlm lignin sulfonate. 0.1%
(dry basis) spray liquors are used. After the sprayed-on layer has dried, the leaves are infected with a zoospore suspension of Phytophthora infestansO The plants are then placed for 5 days in a steam-saturated (moist) chamber kept at 16C. After this period, the disease has spread on the untreated control plants to such an extent that from 80 to 100~ of the leaf surface is covered.
Active Leaf attack after spraying with liquor con-in~redient taining 0.1% of active ingredient A (prior art) 2 B (prior art) 2 Control (untreated) 4 . .
O = no ~ungus atta~k, graduated down to 5 = total attack Botrytis cinerea in pimientos Pimiento seedl.ings of the "Neusiedler ldeal Elite" variety with 4 to 5 well developed leaves were sprayed to runaff with 0.1% (wt~) aqueous spray liquors containing (dry basis) 80% of active ingredient and 20% of sodium lignin sulfonate~ After the 60~
O.Z. 0050/032590 sprayed-on layer had dried, the plants were sprayed with a conidial suspension o~ the fungus Botrytis clnerea and placed, at 22 to 24C, in a high-humidity chamber to obtain optimum conditions for fungus growth. After 5 days, the disease had spread on the untreated plants to such an extent that the necroses covered most of the leaf surface.
Active ingredient Leaf necroses a~ter spraying with 0.1% l'iquor ~ _ .
7 o o A (prior art) 5 B (prior art) 5 Control (untreated) 5 . . _ 0 = no necroses, graduated down to 5 = 2/3 of lea~ ~urface covered with necroses EXAk~LE 16 Septoria nodorum in wheat Leaves of pot-grown wheat plants of the l'Jubilar" variety are sprayed to runoff with aqueous liquors containing 0.2 and 0.1% (wt%) of active ingredient in emulsi~ied ~orm. After the sprayed-on layer ha~ dried, the plants are sprayed with a spore suspension of the ~ungus Septoria nodorum and placed, at 16 to 18C, in a high-humidity chamber to obtain optimum conditions for fungus growth. After 14 days, the disease has spread on the untreated control plants to such an extent that the lea~ blotches cover m st o~ the lea~ surface.
3o - ~2 -~ s O.Z~ 0050/032590 Active ingredient Leaf attack a~ter spraying with liquor containing active ingredient in amounts of 0.2% 0.1%
2 3.5 3.5 ~ 2 2 8 _ 2.5 2 3.5 11 2.5 3.5 12 - 2.5 A (prior art) 5.5 5.5 B (prior art) 4~5 4 Control (untreated) 5.5 , 0 = no blotches, graduated down to 7 - more than 2/3 of leaf surface covered with blotches Pythium spec. in pea seedling~
Pea seeds of the "Senator'l variety are ehoroughly dusted with a disin~ectant formulation containing, in triturated ~orm, 40~ (wt%) of active ingredient and 60~ of talc, in amounts of O.3 g per 100 g of seed. The seeds treated in this manner are ~; -placed, in pots, in 30il heavily infected with Pythium. After 21 days, the dam2ge c~used by the disease is compared with that on the untreated control plan~s.
O~
O.Z. 0050/032590 Active ingredient Percentages of diseased pea plants (21 day~ after emergence) A (prior art) 85 B (prior art) 90 Control (untreated) 90 EX~MPLE 18 Aspergillus niger The active ingredients are added to a nutrient solution ideally 3uited for promoting the growth of the fungus Aspergillus niger, in amounts of 100, 50, 25 and 10 parts by weight per million parts of nutrient solution. 20 ml lots of the nutrient soluti~n treated in thi manner are placed in 100 ml glass fla~ks and in~
oculated with 0.3 mg of Aspergillus spores. The flasks are incubated at 36 C for 120 hour~ and the extent of fungus spread - pre-dominantly on the surface of the nutrient solutions - is then asse~sed.
C = no fungus growth, graduated down to ~:
lignin, sulfite waste liquors and methyl cellulose.
Thè formulations generally contain from 0.1 to 95, and pre~erably ~rom 0.5 to 90, wtZ of active ingredient.
The formulation~ and the ready-to-use products made there from, e.g., solutions, emulsions, suspensions, powders, dusts, pastes or granules, are applied in known manner, for example by spraying, atomizing~ dusting, scattering, seed-disinfecting, pouring, painting or impregnating.
me application rates depend on the ef~ect desired, and range ~rom 0.01 to 3 kg of active ingredient per hectare, or mcre.
Some of the compounds also have a good bactericidal action on bacteria such as Staphylococcus aureus. When the active ingre-dients according to the invention are used to protect materials~
fungi such as Aspergillus-niger, Aspergillus flavus, A~pergillus versicolor, Penicillium funiculosum, Chaetomium globosum, Cladosporium herbarum, Pullularia pullulans, Humicola grisea, and Sclerophoma pityophila are combated. When the active ingre-dients are used to protect materials, e.g., as fungicides for sur~ace coatings and soft PVC (polyvinyl chloride) ,the application rates are fran 0.05 to 5~ (by weight) of active ingredient, based on the total weight of the paints to be preserved or the PVC to be micro-bicidally treated. The new active ingredients may also be used ~., ' ~ ' ~ .
, . . .
O.Z. 0050~032590 as fungicidally ef~ective components of preservatives ~or protecting wood against wood-discoloring fungi. Application is e~ected by tre~ting, e.g., impregnating or painting, the wood with these agents.
The agents according to the invention may also be mixed and applied with other acti~e ingrQdients, e.g., herbicides, insecticides, growth regulators, bactericides, fungicides and fertilizers. When mixed with other fungicides, the spectrum of fungicidal action is in many ca~es increased; with a number of these fungicidal compositionsy synergistic ef~ects also occur;
i.e., the fungicidal action of the combination product is greater than the effect of the individual components added together.
Examples of fungicides which may be combined with the com~
pounds according to the invention are: dithiocarbamates and their derivatives, e.g~ iron(III) dimethyldithiocarbamate, zinc dimethyldithiocarbamate9 manganese N,N-ethylene-bis-dithiocarb-amate, manganese zinc N,N-ethylenediamine-bis-dithiocarbamate, zinc N,N-ethylene-bis-dithiocarbamate, tetramethylthiuram di-sul~ide, the ammonia complex o~ zinc N,N-ethylene-bis-dithio-carbam~te and N,N'-polyethylene- bis (thiocarbamoyl)-disulfide, zinc N,N'-propylene-bis-dithiocarbamate, and the ammonia complex of zinc N,N'-propylene-bis-dithioc~rbamate and N-Nt-polypropylene--bis-(thiocarbamoyl)-disul~ide; nitro derivatives, e.g. dinitro--(1-methylheptyl)-phenyl crotonate, 2-sec.-butyl-4,6-dinitro-phenyl 3,3-dimethylacrylate and 2-sec.-butyl-4,6-dinitrophenyl isopropyl carbonate; heterocyclic compounds, e.g. N-trichloro-methylthiotetrahydrophthalimide, N-trichloromethylthio-pnthal-imide, 2-heptadecyl-2-imidazoline acetate, 294-dichloro-6-(o -chloroanilino~-s-triazine, 0,0-diethyl phthalimidophosphono-thioate, 5-amino-1-(bis-(dimethylamino)-phosphinyl)-3-phenyl--1,2~4-triazole, 5-ethoxy-3-trichloromethyl-1,2,4-thiadiazole, iO5 O.Z. 0050/032590 2,~-dicyano-1,4~dithiaanthraquinone, 2-thio-1,3-dithio(4,5-b)-quinoxaline, methyl 1-(butylcarbamoyl)-2-benzimidazole-carbamate, 2-methoxycarbonylamino-benzimidazol~, 2-thiocyanatomethylthio--benzthia~ole, 4-(2-chlorophenylhydrazono)-3-methyl-5-i~oxazolone, pyridine-2-thio-1-oxide, 8-hydroxyquinoline and its copper salts,, 2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiine-4,4--dioxide, 2,3-dihydro-5~carboxaniliclo-6-methyl-1,4-oxathiine, 2-fur-2-yl-benzimidazole, piperazine-1,4-diyl-bis-(1-(2,2,2-tri-chloroethyl)-formamide) 9 2-thiazol-4-yl-benzimidazole, 5 butyl--2-dimethylamino-4-hydroxy-6-methyl-pyrimidine, bis-(p-chloro-phenyl)-3-pyridinemethanol, 1,2-bis-(3-ethoxycarbonyl-2 thio-ureido)-benzene, 1,2-bis-(3-methoxycarbonyl-2-thioureido)-ben-zene and various fungicides~ e.g. dodecylguanidine acetate, 3-~2-(3,5-dimethyl-2-hydroxycyclohexyl)-2-hydroxyethy].)-glutar-imide, hexachlorobenzene, N-dichlorofluoromethylthio-N',N'-di-methyl-N-phenyl-sulfuric acid diamide, 2,5-dimethyl-furan-3--carboxylic acid anilide, 2~5-dimethylfuran-~-carboxylic acid cyclohexylamide, 2-methyl-benzoic acid anilide, 2-iodo-benzoic acid anilide, 1-(3,4-dichloroanilino)-1-formylamino-2,2,2-tri-chloroethane, 2,6-dimethyl-N-tridecyl-morpholine and its salts, and 2,6-dimethyl-N-cyclododecyl-morpholine and its salts.
In the following experiment~ demon~trating the fungicidal action of the compounds according to the invention, the following prior art active ingredients were used for comparison purposes.
1,3-bis-(trichloromethylthio)-5-ethyl-5-phenylhydantoin (comparative compound A) 1,3-bis-(trichloromethylthio)-5,5-diphenylhydantoin (comparative compound B).
~ 9 _ , . . . .
O.Z. 0050/032590 E.YAMPLE 13 Plasmopara viticola in grapes LeaYes of potted vines o~ the ~I~ller-Thurgau variety are sprayed with aqueous dispersions containing ~dry basis) 80~ (wt%) of the active ingredient and 20~ of sodium lignin sulfonate.
0.1, 0.05 and 0.025~ (dry basis) spray liquors are used. After the spra~ed-on liquor has dried, tXe leaves are infected with a zoospore suspension o~ Plasmopara viticola. The plants are ~irst placed for 16 hours in a steam-saturated (moist)chamber at 20C, and then in a greenhouse for 8 day~ at from 20 to 30C. To accelerate and intensify the sporangicphore discharge, the plants are then again placed in the moist chamber ~or 16 hours. The spore sites on the underside of the lea~es are then counted; 0 denotes no ~ungus attack, graduated down to 5, which denotes total attack (control).
Active Leaf attack after spraying with liquor con-ingredient taining active ingredients in amounts of 0.1% 0.05% 0.025g . . ~
g 0 2 2 Control tuntreated~ 5 .. ....
~ . ... _ ~9605 O.Z. 0050/032590 EXA~LE 14 Phytophthora infestans in tomatoes Leaves of tomatoes of the "GroRe Fleischtomate" variety are sprayed with aqueous dispersions containing (dry basis) 80% (wt%) of active ingredient and 20% of soditlm lignin sulfonate. 0.1%
(dry basis) spray liquors are used. After the sprayed-on layer has dried, the leaves are infected with a zoospore suspension of Phytophthora infestansO The plants are then placed for 5 days in a steam-saturated (moist) chamber kept at 16C. After this period, the disease has spread on the untreated control plants to such an extent that from 80 to 100~ of the leaf surface is covered.
Active Leaf attack after spraying with liquor con-in~redient taining 0.1% of active ingredient A (prior art) 2 B (prior art) 2 Control (untreated) 4 . .
O = no ~ungus atta~k, graduated down to 5 = total attack Botrytis cinerea in pimientos Pimiento seedl.ings of the "Neusiedler ldeal Elite" variety with 4 to 5 well developed leaves were sprayed to runaff with 0.1% (wt~) aqueous spray liquors containing (dry basis) 80% of active ingredient and 20% of sodium lignin sulfonate~ After the 60~
O.Z. 0050/032590 sprayed-on layer had dried, the plants were sprayed with a conidial suspension o~ the fungus Botrytis clnerea and placed, at 22 to 24C, in a high-humidity chamber to obtain optimum conditions for fungus growth. After 5 days, the disease had spread on the untreated plants to such an extent that the necroses covered most of the leaf surface.
Active ingredient Leaf necroses a~ter spraying with 0.1% l'iquor ~ _ .
7 o o A (prior art) 5 B (prior art) 5 Control (untreated) 5 . . _ 0 = no necroses, graduated down to 5 = 2/3 of lea~ ~urface covered with necroses EXAk~LE 16 Septoria nodorum in wheat Leaves of pot-grown wheat plants of the l'Jubilar" variety are sprayed to runoff with aqueous liquors containing 0.2 and 0.1% (wt%) of active ingredient in emulsi~ied ~orm. After the sprayed-on layer ha~ dried, the plants are sprayed with a spore suspension of the ~ungus Septoria nodorum and placed, at 16 to 18C, in a high-humidity chamber to obtain optimum conditions for fungus growth. After 14 days, the disease has spread on the untreated control plants to such an extent that the lea~ blotches cover m st o~ the lea~ surface.
3o - ~2 -~ s O.Z~ 0050/032590 Active ingredient Leaf attack a~ter spraying with liquor containing active ingredient in amounts of 0.2% 0.1%
2 3.5 3.5 ~ 2 2 8 _ 2.5 2 3.5 11 2.5 3.5 12 - 2.5 A (prior art) 5.5 5.5 B (prior art) 4~5 4 Control (untreated) 5.5 , 0 = no blotches, graduated down to 7 - more than 2/3 of leaf surface covered with blotches Pythium spec. in pea seedling~
Pea seeds of the "Senator'l variety are ehoroughly dusted with a disin~ectant formulation containing, in triturated ~orm, 40~ (wt%) of active ingredient and 60~ of talc, in amounts of O.3 g per 100 g of seed. The seeds treated in this manner are ~; -placed, in pots, in 30il heavily infected with Pythium. After 21 days, the dam2ge c~used by the disease is compared with that on the untreated control plan~s.
O~
O.Z. 0050/032590 Active ingredient Percentages of diseased pea plants (21 day~ after emergence) A (prior art) 85 B (prior art) 90 Control (untreated) 90 EX~MPLE 18 Aspergillus niger The active ingredients are added to a nutrient solution ideally 3uited for promoting the growth of the fungus Aspergillus niger, in amounts of 100, 50, 25 and 10 parts by weight per million parts of nutrient solution. 20 ml lots of the nutrient soluti~n treated in thi manner are placed in 100 ml glass fla~ks and in~
oculated with 0.3 mg of Aspergillus spores. The flasks are incubated at 36 C for 120 hour~ and the extent of fungus spread - pre-dominantly on the surface of the nutrient solutions - is then asse~sed.
C = no fungus growth, graduated down to ~:
5 = uncontrolled ~ungus growth (surface of nutrient solution completely covered by fungus~
Active ingredientAmount of active ingredient in nutrient so.ution in ppm 4 0 0 2 5 : :
Active ingredientAmount of active ingredient in nutrient so.ution in ppm 4 0 0 2 5 : :
6 0 0 0 4 A (prior art) 5 5 5 5 B (prior art) 5 5 5 5 Control (un~reated) 5 O.Z. 0050/032590 90 parts by weight of compound 1 is mixed with 10 parts by weight of N-methyl-~-pyrrolidone. A mixture is obtained which is suitable ~or application in the form of very fine drops.
20 parts by weight of compound 2 is dissolved in a mixture consisting of 80 parts by weight of xylene, 10 parts by weight of the adduct of 8 to 10 moles o~ ethylene oxide to 1 mole of oleic acid-N-monoethanolamide, 5 parts by weight of the calcium salt of dodecylbenzene~ulfonic acid, and 5 parts by weight of the adduct of 40 moles of ethylene oxide to 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and uniformly distributing it therein, an aqueous dis-persion is obtained containing 0.02~ by weight of the active ingredient.
EX~PLE 21 20 parts by weight of compound 3 is dissol~ed in a mix-ture consisting of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the adduct of 7 moles of ethylene oxide to 1 mole of isooctyl-phenolg and 10 parts by weight of the adduct of 40 moles o~
ethylene oxide to 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and finely distributing it therein, an aqueous di~persion i obtained containing 0.02%
by weight of the ac.tive ingredient.
20 parts by weight of compound 4 is dissolved in a mix-ture consisting of 25 parts by weight of cyclohexanol, 65 parts by weight of a mine~ral oil fraction having a boiling point between 210 and 280C, ~nd 10 parts by weight of the adduct of 40 moles of ethylene oxide to 1 mole of castor oil. By pouring the solution into 100,000 parts by weight o~ water and uniformly g~ii(35 O.Z. 0050/032590 distributing it therein, an aqueous di~persion is obtained containing 0.02~ by weight of the active ingredient.
20 parts by weight of compound 5 is well mixed with 3 parts by weight o~ the sodium salt of diisobutylnaphthalene--~-sulfonic acid, 17 parts by weight of the sodium salt of a lignin-sulfonic acid obtained from a sulfite waste liquor, and 60 parts by weight of powdered silica gel, and triturated in a hammer mill. By uniformly distributing the mixture in 20,000 parts by weight of water, a spray liquor is obtained containing 0.1% by weight o~ the active ingredient.
3 parts by weight o~ compound 6 is intimately mixed with 97 parts by weight of particulate kaolin. A dust is obtained containing 3% by weight o~ the active ingredient.
30 parts by waight of compound 7 is intimat~ly mixed with a mixture consisting of 92 parts by weight of powdered silica gel and ~ parts by weight of paraffin oil which has been sprayed onto the surface o~ this silica gelO A formulation of the active ingredient is obtained having good adherence.
40 parts by weight o~ compound 1 is intimately mixed with 10 parts of the sodium salt of a phenolsulfonic acid-urea-form-aldehyde condensate, 2 parts of silica gel and 48 parts of water. Dilution in 100,000 parts by weight of water gives an aqueous dispersion containing 0.04 wt~ of active ingredient.
g~o~
O.Z. 0050/032590 20 parts of compound 2 is intima.tely mixed with 2 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 68 parts of a paraffinic mineral oil. A stable oily dispersion is obtained.
!
. - 17 -
20 parts by weight of compound 2 is dissolved in a mixture consisting of 80 parts by weight of xylene, 10 parts by weight of the adduct of 8 to 10 moles o~ ethylene oxide to 1 mole of oleic acid-N-monoethanolamide, 5 parts by weight of the calcium salt of dodecylbenzene~ulfonic acid, and 5 parts by weight of the adduct of 40 moles of ethylene oxide to 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and uniformly distributing it therein, an aqueous dis-persion is obtained containing 0.02~ by weight of the active ingredient.
EX~PLE 21 20 parts by weight of compound 3 is dissol~ed in a mix-ture consisting of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the adduct of 7 moles of ethylene oxide to 1 mole of isooctyl-phenolg and 10 parts by weight of the adduct of 40 moles o~
ethylene oxide to 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and finely distributing it therein, an aqueous di~persion i obtained containing 0.02%
by weight of the ac.tive ingredient.
20 parts by weight of compound 4 is dissolved in a mix-ture consisting of 25 parts by weight of cyclohexanol, 65 parts by weight of a mine~ral oil fraction having a boiling point between 210 and 280C, ~nd 10 parts by weight of the adduct of 40 moles of ethylene oxide to 1 mole of castor oil. By pouring the solution into 100,000 parts by weight o~ water and uniformly g~ii(35 O.Z. 0050/032590 distributing it therein, an aqueous di~persion is obtained containing 0.02~ by weight of the active ingredient.
20 parts by weight of compound 5 is well mixed with 3 parts by weight o~ the sodium salt of diisobutylnaphthalene--~-sulfonic acid, 17 parts by weight of the sodium salt of a lignin-sulfonic acid obtained from a sulfite waste liquor, and 60 parts by weight of powdered silica gel, and triturated in a hammer mill. By uniformly distributing the mixture in 20,000 parts by weight of water, a spray liquor is obtained containing 0.1% by weight o~ the active ingredient.
3 parts by weight o~ compound 6 is intimately mixed with 97 parts by weight of particulate kaolin. A dust is obtained containing 3% by weight o~ the active ingredient.
30 parts by waight of compound 7 is intimat~ly mixed with a mixture consisting of 92 parts by weight of powdered silica gel and ~ parts by weight of paraffin oil which has been sprayed onto the surface o~ this silica gelO A formulation of the active ingredient is obtained having good adherence.
40 parts by weight o~ compound 1 is intimately mixed with 10 parts of the sodium salt of a phenolsulfonic acid-urea-form-aldehyde condensate, 2 parts of silica gel and 48 parts of water. Dilution in 100,000 parts by weight of water gives an aqueous dispersion containing 0.04 wt~ of active ingredient.
g~o~
O.Z. 0050/032590 20 parts of compound 2 is intima.tely mixed with 2 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 68 parts of a paraffinic mineral oil. A stable oily dispersion is obtained.
!
. - 17 -
Claims (4)
1. A 1,3-bis-(trihalomethylsulfenyl)-imidazoline-2,4-dione of the formula , where X and Y are idential or different and each denotes chlorine or fluorine, and R1 and R2 are identical or different and each denotes hydrogen or lower alkyl, or R1 and R2 are directly linked with each other, or together denote the radical -(CH2)n-, n deno-ting one of the integers 1, 2, 3, 4, 5 and 6.
2. A 1,3-bis-(trihalomethylsulfenyl)-imidazoline-2,4-dione as claimed in claim 1, where X denotes fluorine, Y denotes fluorine, R1 denotes lower alkyl and R2 denotes hydrogen.
3. A 1,3-bis-(trihalomethylsulfenyl)-imidazoline-2,4-dione selected from the group consisting of 1-dichlorofluoromethylthio--3-trichloromethylthioimidazoline-2,4-dione, 1-trichloromethyl-thio-3-dichlorofluoromethylthioimidazoline-2,4-dione, and 1,3-bis-(dichlorofluoromethylsulfenyl)-imidazoline-2,4-dione.
4. A process for combating fungi, wherein the objects to be protected against fungus attack are treated with an effective amount of a 1,3-bis-(trihalomethylsulfenyl)-imidazoline-2,4-dione of the formula , where X and Y are idential or different and each denotes chlorine or fluorine, and R1 and R2 are identical or different and each denotes hydrogen or lower alkyl, or R1 and R2 are directly linked with each other, or together denote the radical -(CH2)n-, n denoting one of the integers 1, 2, 3, 4, 5 and 6.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000323847A CA1119605A (en) | 1979-03-20 | 1979-03-20 | L,3-bis-(trihalomethylsulfenyl)-imidazoline-2,4- diones |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000323847A CA1119605A (en) | 1979-03-20 | 1979-03-20 | L,3-bis-(trihalomethylsulfenyl)-imidazoline-2,4- diones |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1119605A true CA1119605A (en) | 1982-03-09 |
Family
ID=4113793
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000323847A Expired CA1119605A (en) | 1979-03-20 | 1979-03-20 | L,3-bis-(trihalomethylsulfenyl)-imidazoline-2,4- diones |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1119605A (en) |
-
1979
- 1979-03-20 CA CA000323847A patent/CA1119605A/en not_active Expired
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