IL25946A - Fungicidal and bactericidal compositions containing 5-amino-1,2-dithiol-3-one derivatives - Google Patents

Description

>*pn**m m»"»o'» mVeipn maiiyn Fungicidal and bactericidal compositions containing 5-awino-lf 2-dithiol-^-ene derivativee A&RIPAT 3.A. 0J-24730 S.A. 1 (Schweiz/Switzerland) 2197* Fungicidal and bactericidal compositions The present invention concerns new fungicidal and bactericidal compositions which contain 5-amino-l, 2-dithiol- 3-ones as active ingredients, also processes for the production of such compositions as well as processes for combatting injurious fungi on plants and organic materials and for the protection of organic materials and objects from attack by injurious and destructive fungi and bacteria using such 5-amino-l, 2-dithiol-3-ones or compositions containing them. It also concerns the materials and objects so protected.

Representatives from the class of 1, 2-dithiol- 3-ones , namely 1, 2-dithiol- 3-ones chlorinated in the 5-position such as 4, -dichloro-l, -dithiol- 3-one (Deutsche Auslegeschrift No. 1Ί02Ί74) and 4-aryl-5-chloro-l,2-dithiol-3-ones (Deutsche Auslegeschrift No. 1' 126' 668) have already been described in the literature as pesticidal or fungicidal active substances. But these compounds are either inactive against phytopathogenic fungi and their spores or they are unsuitable as fungicides because of their high phytotoxicity.

It has been found that fungicidal and bactericidal agents which contain, as active ingredients, 5-amino-l, 2-dithiol- 3-onfes of the general formula I: wherein and R^ independently of each other each represent hydrogen or an alkyl radical having from 1 to 14 carbon atoms optionally substituted as herein defined, or R^ and R^ together with the adjacent nitrogen atom repreent an optionally substituted - to 7-membered saturated heterocyclic radical, and represents halogen or a phenyl radical optionally substituted by low alkyl, are excellently suitable for the combatting of injurious fungi and bacteria euch as phytopathogenic fungi and fungi or bacteria which injure and destroy organic materials and objects and for the protection of such materials and objects from attack by such fungi and bacteria.

The alkyl radicals symbolised by and R^ in general formula I may be substituted by hydroxy, amino, car oxy, carbamoyl, alkoxy, alk lthio, alkylamino, dialkylamino, alkoxy-carbonyl or fi-alkyl- or Κ,Κ-dialkyl- carbamoyl groups. One of the radicals or can also represent a methyl or ethyl radical substituted by the phenyl radical j the phenyl radical can be substituted by low alkyl or halogen. Heterocyclic radicals represented by and together with the nitrogen atom are, e.g. the pyrrolidino, piperidino, hexamethylenimino, morpholino or piperazino radical. These radicals can be raono-or poly- substituted, e.g. by an alkyl, alkoxy, alkox carbonyl, N-alkylcarbamoyl, Κ,Ιί-dialkylcarbamoyl, aminoalkyl, carbamoyl nitroso or cyano group. The active substances of the general formula I can be obtained by reacting 4, 5-dichloro-l, 2-dithiol-3-one or a 5-chloro-l, 2-dithiol-3-one substituted in the 4-position by phenyl, with a corresponding amine.

The compounds of general formula I contained in the new agents as active substances are active against numerous phyto-pathogenic fungi. The agents serve to protect plants or parts thereof such as blossom} seeds, fruit, roots, stems and foliage from attack by fungi and to combat fungi on these parts of plants. In part they also work on some types of true mildew which usually are difficult to combat. The 5-amino-l, 2-dithiol-3-ones of general formula I are not phytotoxic and are very well tolerated by the plants. In addition, the active substances have a systemic action, for which reason the plants treated with the agent according to the present invention are given wider and more protracted protection from attack by fungi and bacteria. The agents are also suitable for the treatment of seeds without germination being affected. In plant protection, the new agents are so applied that the concentration of active ingredient usually lies between 0.01 and 2%.

Example 1 The activity of the active substances of general formula I against spores of phytopathogenic fungi was determined by a germination test on spores of the following types of fungi Alternaria tenuis Botrytis cinerea Clasterosporium c.

Coniothyrium dipl.

Fusarium culmorum ψ Mucor spec.

Penicillium spec.

Stemphylium cons. 1 ccm of a 1%, 0.1% and 0.01$ acetone solution of the active ingredient is placed on two glass slides (26x76 mm) under the same conditions. The solvent is evaporated off and a uniform coating of active ingredient is obtained on the glass slides. The slides are inoculated with spores of the above fungi and then kept in dishes at room temperature in an atmosphere which is almost saturated with steam. After 2 - 3 and 4 - 5 days, the germinated spores are counted.

The results are summarized in the following Table: + means an at least 90% inhibition of germination effected by the residue of 1 ccm of a 1% acetone solution of active ingredient, ++ means the same effect by the residue of 1 ccm of a 0.1% acetone solution of the active ingredient, +++ means an at least 90% inhibition of germination attained by the residue of 1 ccm of a 0.01 acetone solution of active ingredient, means no inhibition of germination with the concentrations of active ingredient given above.

Spore Germination Test w Example 2 The phytofungicldal activity was determined by comparative tests on a) beans and b) cucumbers. a) Leaves of bean plants (Phaseolus vulgaris) in the two-leaf stage were sprayed with an aqueous suspension containing 0.1$ of active substance.

The suspension is obtained from the \ % wettable powder ' described as form for application below, by diluting with water. After drying, the leaves are infested with a fresh suspension of spores of Uromyces appendiculatus , The plants are then left for one day in a moist room and then kept in a greenhouse . b) Cucumber (Cucumis sativus) leaves are treated analogously to the description given under a), then sprayed with a fresh suspension of spores of Erysiphe cichoracearum, then kept for one day in a moist room and then placed in a greenhouse.

After about 7 to 10 days and about 7 days respectively the tests are evaluated according to the following comparative scale: 0 = no infestation 1 - 9 = inhibition of infestation according to its extent = inactive x = great injuries to leaves or destruction of plants.

The 5-amino-l, 2-dithiol- 3-ones of general formula I have good to very good fungistatic and bacteriostatic activity against fungi and bacteria such as Aspergillus niger ATCC, Penicillium exp., Fusarium oxysporum, Candida albicans etc. i which injure and destroy organic materials such as wood, leather synthetic plastics, fabrics, coating agents etc.

On impregnating with solutions or dispersion?', of active substance containing at least 1 g/litre of active substance, the materials treated are given a good and long lasting protection.

For this purpose, the active substances can also be applied in combination with other substances suitable for the Example 3 In order to secure an effective, broad and long lasting protection against mould formation on, e.g. a painted surface the following procedure should be used: 3 Parts of active substance are dissolved in 5 parts of a mixture (1:1) of dimethyl formamide and ethylene glycol monomethyl ether. 87 Parts of a commercial dispersion colour based on polyvinyl acetate-ethyl acrylate copolymer are stirred in, 5 parts of water are added and the whole is stirred until homogeneity is attained. Two other solutions are prepared in exactly the same way except that one contains 1 part of active ingredient and 39 parts of the commercial dispersion colour and the other contains 0.3 parts of active ingredient and 89.7 parts of dispersion colour. In this way, three ready-for-use paints are obtained which contain 3, 1 and 0.3$by weight of active ingredient respectively. c The fungistatic and bacteriostatic activity of these paints is tested by laying them on filter paper, e.g. Whatman 3 MM and by exposing the papers so prepared, first for 3 days at 20°C and then for 8 days at 65°C and 80-90$ relative humidity.

Circular samples of 2 cm diameter are cut from these filter papers and laid in Petri dishes (painted side upwards) 3 on 20 cm of Sabouraud-Maltose agar inoculated with spores of Pellularia pullulans, Paecylomydes varioti, Penicillium cyclopium and Candida albicans and then stored for 7 days at 28°C. The following Table shows the concentrations of active substance with which no mould has formed either on the upper or lower surface of the papers.

T a l e Example 4 Textile material may be given a bactericidal and fungicidal finishing which exhibits remarkable fastness to washing as follows: g of the active substance to be tested are dissolved in 1 litre of ethylene glycol monomethyl ether. Strips of 2 cotton fabric (weight of 1 m = 85 g) which has been washed at the boil are dipped in this solution and then mangled to 40% by weight liauor content. The concentration of active substance on the fabric is thus 1% by weight. The strips of fabric are hung for 5 minutes in circulating steam and dried. ψ The strips of fabric are then washed twice at 40° for 15 minutes each time with 5 g of soap per litre of water, rinsed twice with cold water for 3 minutes each time and dried. The effectiveness of this treatment was determined by the following tests: a) Inhibition test Circular samples of 2 cm diameter are cut from the strips of said fabric and placed in Petri dishes on agar culture-medium which has been inoculated in the usual way with A) Staphylococcus aureus SG 511 B) Escherichia col NTC S196 C) Candida albicans D) Aspergillus niger EMPA 1 The dishes containing agar A), B) and C) are stored for 24 hours at 37° and D) for 3 days at 23°. The effectiveness of the active substances is determined by counting the number of germs and colonies growth either on or under the samples. b) Maceration test Circular samples of 4 cm diameter are cut from the fabric treated as described above and subjected to maceration in compost consisting of 50% cow dung, 30% compost and 20% sand (all % by weight). The earth has 30% relative humidity and is kept at 28° C. After 10 days, the samples are disinterred, cleaned and conditioned at 24°C and 65% relative humidity. The tensile strength after the maceration is compared with that of the fabric after the treatment above described which has been determined before the maceration. It is expressed in percentages of the initial tensile strength after the treatment above described. c) Mildew spot test Circular samples of S cm diameter are cut from the fabric treated as described above and placed on sterile Worth agar plates prepared according to Difco Manual, 9th Edition p. 244 by spreading 15 ml of Worth agar in Petri dishes of cm diameter and leaving them to solidify.

The samples are placed on the agar which is then inoculated with a spore suspension containing spores of the fungi Chaetomium globosum, Aspergillus niger and Trichoderma viride.

The Petri dishes are stored for 5 days at 28°C and then the growth of mould is determined.

Results a) Inhibition test In the following table the abbreviations signify: + = growth of bacteria and fungi on and under the fabric sample - = no growth A Staphylococcus aureus SG 511 B Escherichia coli NTC S196 C Candida albicans D Aspergillus niger EMPA 1 Compound A B C D 4-chloro- -piperidino-l , 2-dithiol- 3-one - - - - 4-chloro- 5-pyrrolidino-l, 2-dithiol- 3-one - + - - 4-phenyl- 5- chloro-1, 2-dithiol- 3-one (Deutsche Auslegeschrift 1*126*668) + + + + 4, 5-dichloro-1, 2-dithiol- 3-one (Deutsche Auslegeschrift 1*102*174) + + + + b) Maceration and mildew spot test In the following table the abbreviations signify: + = mildew spot and mould growth = no growth of mildew spot and mould The fungicidal and bacteriocidal agents according to the invention are produced in the known way by intimately mixing and milling the active substances of general formula I with suitable carriers, optionally with the addition of dispersing agents or solvents which are inert to the active substances. The active compounds may be used according to the invention in the following preparations: Solid forms: dusts, sprinkling agents, granulates such as coated granules, impregnated granules, homogeneous granules, Water dispersible concentrates of active substances: wettable powders, pastes, emulsions, Liquid forms: solutions.

To produce the solid forms for use (dusts, sprinkling agents, granulates), the active substances are mixed with solid carriers. Examples of carriers are kaolin, talcum, bole, loess, chalk, limestone, ground limestone, ataclay, dolomite, diatomaceous earth, precipitated silicid acid, alkaline earth silicates, sodium and potassium aluminium silicates (feldspar and mica), calcium and magnesium sulphates, magnesium oxide, milled synthetic plastics, fertilisers such as ammonium sulphate, ammonium phosphates, ammonium nitrate, urea, ground vegetable products such as bran, bark dust, sawdust, ground nutshells, cellulose powder, residues of plant extractions, active charcoal etc. These carriers can be used alone or admixed with each other.

The particle size of the carriers is, for dusts up to about 100 μ, for sprinkling agents from about 75 μ - 0.2 mm and for granulates from 0.2 mm - 1 mm or coaser.

As a general rule, the concentrations of active substances in the solid preparations is from 0.5 - 80%.

To these mixtures can also be added additives which stabilise the active substance and/or non-ionogenic, anionically and cationically active substances which, for example, improve the adhesion of the active substances on plants and parts of plants (glues and adhesives) and/or attain better wettability (wetting agents) and dispersibility (dispersing agents) of the active substances.

The concentrates of active substance which can be dis-persed in water (wettable powders), pastes and emulsion concentrates, are agents which can be diluted with water to any concentration desired. They consist of active substance, carrier, optionally additives which stabilise the active substance, surface active substances, and anti-foam agents, and 9 optionally5 solvents. The concentration of active substance in these agents is 5-80$.

Wettable powders and pastes are obtained by mixing and milling the active substances with dispersing agents and pul-verulent carriers in suitable mixers and milling machines until homogeneity is attained. Carriers are, for example, those mentioned in the paragraph dealing with solid forms for application. In some cases it is advantageous to use mixtures of different carriers. Commercially available surface active substances can also be used as dispersing agents.

Examples of anti-foaming agents are, e.g. silicones and "Antifoam A".

The active substances are so mixed, milled, sieved and strained with the additives mentioned above that the solid particle size in wettable powders is 20-40 μ and in pastes is not more than 3 jx. To produce emulsion concentrates and pastes, dispersing agents such as "thTJse given in the previous paragraphs, organic solvents and water are used. Examples of solvents are as follows: alcohols, benzene, xylenes, toluene, dimethyl sulphoxide and mineral oil fractions boiling between 120° and 350°. The solvents must be almost odorless, not phytotoxic, inert to the active substances and not easily inflammable .

In addition, the agents according to the invention can be in the form of and be used as solutions. For this purpose the active substance or several active substances of general formula I are dissolved in suitable organic solvents, mixtures of solvents or in water. Aliphatic and aromatic hydrocarbons, chlorinated derivatives thereof, alkyl naphthalenes, alone or mixed with each other can be used as organic solvents. The solutions should contain the active substances in a concentration from 1 - 20%.

The application forms described of the agents according to the invention can be mixed with other biocidally active compounds or with agents containing such compounds. Thus, to broaden the range of action of agents according to the invention other active substances such as insecticides, fungicides, bactericides, fungistatics, bacteriostatics or nematicides can be incorporated thereinto. The agents according to the invention can also contain fertilisers, trace alements etc.

The following examples serve to illustrate the present invention; where not otherwise expressly stated, by "parts" are meant parts by weight, Example 5 Dusts To produce a) a 10$ and b) a 2% dust, the components given below are used: a) 10 parts of 4-chloro-5-dimethylamino-l, 2-dithiol- 3-one 5 parts of highly dispersed silicic acid 85 parts of talcum b) 2 parts of 4-chloro-5-hexamethylenemino-l, 2-dithiol- 3-one, 1 part of highly dispersed silicic acid 97 parts of talcum The above carriers are intimately mixed and milled with the active substances. The fungicidal dusts so obtained serve for the treatment of seed beds or for dusting plants.

Example 6 Seed Dressing a) 10 parts of 4-chloro-5-diethylamino-l, 2-dithiol-3-one parts of kieselguhr , 1 part of liquid paraffin 84 parts of talcum b) 60 parts of 4-chloro-5-morpholino-l, 2-dithiol 3-one parts of kieselguhr 1 part of liquid paraffin 24 parts of talcum are used to produce a) a 10$ and b) a 60% seed dressing.

The active substances mentioned are intimately mixed and then milled with the carriers given and the paraffin as distributing agent. The pulverulent dressings obtained serve for the treatment of seeds of all types.

Example 7 Granulates To produce a) a 2.5% and b) a 5% granulate, the following components are used: a) 2.5 parts of 4-chloro-5- (N'-ethoxycarbonyl)-piperazino- 1,2-dithiol- 3-one 2.5 parts of kieselguhr parts of polyethylene glycol 89.3 parts of ground limestone (0.4 - 0.8 mm diameter) 0.7 parts of silicic acid. b) 5 parts of 4-chloro-5'- -hydroxyethylamino-l , 2-dithiol 3-one 1.5 parts of kieselguhr 0.5 parts of cetyl polyglycol ether parts of polyethylene glycol 1 part of silicic acid.

The ground limestone in each formulation is impregnated with the polyethylene glycol or the cetyl polyglycol ether and then mixed with a mixture of the active substance -mentioned , the kieselguhr and silicic acid. These granulates are particularly suitable for the disinfection of seed beds.

Example 8 Wettable powders To produce a) a 25 , b) and c) 50% and d) a 10% wet-table powder, the following components are used: a) 25 parts of 4-chloro-5-morpholino-l, 2-dithiol- 3-one parts of kieselguhr 2 parts of hexadecyl glycol ether sulphate 1 part of sodium lauryl sulphonate 7 parts of sodium lignin sulphonate 40 parts of kaolin. b) 50 parts of 4-chloro-5- (N'-methyl)-piperazino-l, 2-di- thiol- 3-one 3 parts of oleyl methyl tauride sodium salt 2 parts of sodium lauryl sulphonate parts of sodium lignin sulphonate 2 parts of kaolin/polyvinyl alcohol mixture (1:1) 38 parts of silicic acid (precipitated) c) 50 parts of 4- The active substances mentioned are mixed and finely milled with the carriers and distributing agents. Wettable powders are obtained which have excellent wettability and suspendability. From such wettable powders with water, suspensions are obtained of any concentratibn of active substance desired. They serve for the treatment of cultivated plants. They can also be used for the impregnation of organic materials of all types.

Example 9 Emulsion concentrates To produce a) a 5$, b) a 10$ and c) a 15% emulsion concentrate, the following components are used: a) 5 parts of 4-chloro-5- (Ν' -ethoxycarbonyD-piperazino- 1, 2-dithiol- 3-one 40 parts of dimethyl formamide 50 parts of petroleum (boiling range 230-270°) parts of composite emulsifyer consisting of the Ca salt of dodecylbenzene sulphonic acid and a condensation product of ethylene oxide and ricinus oil (e.g. "Emullat WK" , Union Chimique Beige S.A., Brussels) b) 10 parts of 4-chloro-5-benzylamino-l, 2-dithiol-3-one 50 parts of petroleum (boiling range 230-270°) parts of composite emulsifyer consisting of the Ca salt of dodecylbenzene sulphonic acid and a condensation product of ethylene oxide and ricinus oil (e.g. "Emullat WK" , Union Chimique S.A., Brussels) c) 15 parts of 4-chloro-5-piperidino-l, 2-dithiol-3-one 27 parts of dimethyl formamide 53 parts of petroleum (boiling range 230-270°) parts of composite emulsifyer consisting of the Ca salt of dodecylbenzene sulphonic acid and a condensation product of ethylene oxide and ricinus oil (e.g. "Emullat WK" , Union Chimique S.A., Brussels), The active ingredient" used is dissolved in petroleum or dimethyl formamide and the composite emulsifyer is added to this solution. Emulsion concentrates are obtained which can be diluted with water to any concentration desired. Such emulsions are suitable for the treatment of cultivated plants and also for the impregnation of organic materials such as tex-tiles, wood, leather, synthetic plastics etc.

In addition to the active compounds used in the above examples 5 to 9 the following compounds can be used as active substance instead of those mentioned therein: 4-chloro-5-benzylamino-l,2-dithiol-3-one, M.P. 141°C 4-chloro-5-n-dodecylamino-l, 2-dithiol-3-one, M.P. 62°C 4-chloro-5-methylamino-l, 2-dithiol-3-one, M.P. 168°C. -20- 25*46/2 * , 3

Claims (20)

1. Fungicidal and bactericidal composition comprising as active substance a 5-amino-l,2-dithiol-3-one of the general formula It S S wherein JL^ and independently of each other each represent hydrogen or an alkyl radical having from 1 to 14 carbon atoms optionally substituted as herein defined, or and R2 together with the adjacent nitrogen atom represent a 5- to 7-meo ered saturated heterocyclic radical, and represents halogen or a phenyl radical optionally substituted by low alkyl, preferably in admixture with acceptable carriers therefor.

2. Fungicidal and bactericidal composition according to Claim 1 wherein and independently of each other each represent hydrogen, an alkyl radiafl. having from 1 to 4 carbon atoms, an hydrox alkyl radical having from 1 to 4 carbon atoms, or and together with the adjacent nitrogen atom represent an optionally substituted 5- to 7- membered saturated heterocyclic radical and represents halogen.

3. Fungicidal and bactericidal composition according to Claim 1 or 2, wherein represents hydrogen, the methyl or ethyl radical, represents the methyl or ethyl radical or the β-hydroayethyl radical or and together with the adjacent nitrogen atom represent the pyrrolidlno, plperidino, the hexamethyleneimino radical and Rg is chlorine.

4. Fungicidal and bactericidal composition according to claim 1 wherein 4-chloro-5-pyrrolidino-l, 2-dithiol-3-one is used as active substance.

5. Fungicidal and bactericidal composition according to claim 1 wherein 4-chloro-5-piperidino-l, 2-dithiol-3-one is used as active substance.

6. Fungicidal and bactericidal composition according to claim 1 wherein 4-chloro-5-morpholino-l, 2-dithiol-3-one is used as active substance.

7. Fungicidal and bactericidal composition according to claim 1 wherein 4-chloro-5-hexamethyleneimino-l, 2-dithiol-3-one is used as active substance.

8. Process for the production of fungicidal and bacteri-cidal compositions according to claim 1, which comprises mixing a 5-amino-l , -dithiol-3-one of the general formula I defined in claim 1 with an acceptable carrier therefor.

9. Process for combatting phytopathogenic fungi and organic materials and objects injuring fungi and bacteria which comprises contacting plants or organic materials and objects with a 5-amino-l, 2-dithiol-3-one of the general formula I defined in claim 1 or with a composition according to claim 1.

10. Fungicidal composition comprising as active substance a 5-amino-l, 2-dithiol-3-one of the general formula I _ 22 - 25946/2 •wherein and R2 independently ex e c other each represent hydrogen or an alkyl radical havi g from 1 to 14 carbon atons optionally su stituted as herein defined, or and R2 toge er with the adjacent nitrogen atom represent a 5- to 7-~.embe ed saturated heterocyclic rad ical , and B5 represents halogen or a phenyl radical optionally substituted by low alkyl, preferably In admixture with acceptable carriers therefor.

11. Fungicidal composition according to claim 10 wherein and R2 independently of each other each represent hydrogen, an alkyl radical having from 1 to 4 carbon atoms, an hydroxy- alkyl radical having from 1 to 4 carbon atoms, or ^ and 2 together with the adjacent nitrogen atom represent an optionally substituted 5- to 7-membered saturated, heterocyclic radical and 3 represent halogen.

12. ,. Fungicidal composition according to claim 10 or 11 wherein R-L represents hydrogen, the methyl or ethyl radical., .. R2 represents the methyl or ethyl radical or the β-hydroxy- ethyl radical or and R2 together with the adjacent nitrogen atom represent the pyrrolidino, piperidino, morpholino, N'- methylpiperaz'ino, N '-ethoxycarbonylpiperazino or the hexa- methyleneimino radical and R3 is chlorine. .

13. Fungicidal composition according to claim 10 wherein 4-chloro-5-pyrrolidino-l, 2-dithiol-3-one is used as active substance.

14. Fungicidal composition according to claim 10 wherein 4'Chloro-5-piperidino-l, 2-dithiol-3-one is used as active substance.

15. Fungicidal composition according to claim 10 wherein 4-chloro-5-morpholino-l,2-dithiol-3- one is used as active substance.

16. Fungicidal composition according to claim 10 wherein 4-chloro-5-hexamethyleneimino-l, 2-dithiol-3-one is used as active substance.

17. Process for the production of fungicidal compositions according to claim 10 which comprises mixing a 5-amino-l,2-dithiol-3-one of the general formula I defined in claim 10 with an acceptable carrier therefor,

18. IS. Process for combatting phytopathogenic fungi and organic materials and objects injuring fungi which comprises contacting plants or organic materials and objects with a 5-amino-l,2-dithiol-3-one of the general formula I defined in claim 10 or with a composition according to claim 10.

19. Organic materials and objects protected from attack by injurious fungi and bacteria according to the process as claimed in claim 9.

20. Organic materials and objects protected from attack by injurious fungi according to the process as claimed in claim 18.