SE202811C1

SE202811C1 -

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Publication number: SE202811C1
Authority: SE
Publication date: 1965-01-01

Description

Uppfinnare: H Lehmann, F Grown och W Lautenschlager Prioritet begtird !ran den 28 december 1960 (Forbundsrepubliken Tyskland) Fran den amerikanska patentskriften 2 317 765 dro alkylen-bis-ditiokarbaminsura salter kanda, vilka utmarkas av en god fungicid verkan. I denna patentskrift beskrives bl. a., aft man med utgang Iran propylendiamin, natronlut ()eh kolsvaida erhailer en forening av ovannamnt slag med god verkan. Inventors: H. Lehmann, F. Grown and W. Lautenschlager Priority application dated December 28, 1960 (Federal Republic of Germany) From U.S. Pat. No. 2,317,765, alkylene-bis-dithiocarbamic acid salts are known, which are characterized by good fungicidal activity. This patent specification describes i.a. a., aft man with starting Iran propylenediamine, sodium hydroxide solution () eh carbon dioxide erhailer an association of the above kind with good effect.

I ett arbete av Raymond W. Barrett och James G. Horsf all, Connecticut Agricultural Experiment Station, New Haven, Bulletin 508, June 1947, ))Fungicidal Action of Metallic Alkyl Bisdithiocarbamates» finnes vidare pa sid. 7 dinatriumsaltet av isopropen-bis-ditiokarbaminsyra beskrivet och av tabellen pa sid. 9 framgar, att natriumsaltet av eten-bis-ditiokarbaminsyra ar flera ganger verksammare an natriumsaltet av isopropen-bisditiokarbaminsyran. In a work by Raymond W. Barrett and James G. Horsf all, Connecticut Agricultural Experiment Station, New Haven, Bulletin 508, June 1947,)) Fungicidal Action of Metallic Alkyl Bisdithiocarbamates »can be found further on p. 7 the disodium salt of isopropylene-bis-dithiocarbamic acid described and by the table on p. 9 shows that the sodium salt of ethylene-bis-dithiocarbamic acid is several times more effective than the sodium salt of the isopropylene-bisdithiocarbamic acid.

Pet liar nu befunnits, att isopropen-bis-ditiokarbaminsura salter av zink och mangan, framfOrallt i jamforelse med de i ovannamnda patent-shift beskrivna foreningarna, utmarkas av en sardeles god verkan. Verkan av dessa isopropenforeningar är flera ganger storm an verkan far de i den ovannamnda amerikanska patentskriften namnda, normala propenforeningarna. It has now been found that isopropylene-bis-dithiocarbamic acid salts of zinc and manganese, especially in comparison with the compounds described in the above-mentioned patent shift, are marked by a very good effect. The effect of these isopropylene compounds is several times greater than that of the normal propylene compounds mentioned in the aforementioned U.S. Patents.

Pet maste anses sarskilt overraskande, att zinkoch mangansalterna av isopropen-bis-ditiokarbaminsyra besitta dessa ovanliga egenskaper, framforallt pd. grand av det faktum, att det genom det ovannamnda arbetet av Barratt & Horsfall är kant, att forliallandet cia det &ler natriumsalterna är det raid motsatta. Pet must be considered particularly surprising that the zinc and manganese salts of isopropylene-bis-dithiocarbamic acid possess these unusual properties, especially pd. grand of the fact that through the above-mentioned work of Barratt & Horsfall it is edge, that the forliallandet cia it & ler sodium salts is the raid opposite.

Framstallningen av de fOreningar, som i enlighet med uppfinningen komma till anvandning, sker pa i princip kant satt, dvs. genom omsattning av 1,2-propendiamin med kolsvavla, foretradesvis i Dupl. kl. 45 1: 9/20; 45 1: 13/00 narvaro av alkali- resp. ammoniumhydroxid, samt fortsatt reaktion med salter av zink eller mangan. The preparation of the compounds which are used in accordance with the invention takes place in a principle, ie. by reacting 1,2-propenediamine with carbon sulfur, preferably in Dupl. at 45 1: 9/20; 45 1: 13/00 narvaro of alkali resp. ammonium hydroxide, as well as continued reaction with salts of zinc or manganese.

De i enlighet med uppfinningen till anvandning kommande fOreningarna arc framforallt verksamma med avseende pa skadliga organismer av svampkaraktar, mot vilka aven de hittills brukliga ditiokarbaminsura salterna kommit till anvandning, dvs. framforallt mot Phytophthora infestans, Cladosporium fulvum eller Alternaria solani pd. tomater och potatis, mot Peronspora (= Plasmopara viticola) pa vin, Venturia inaequalis karnfrukt avensom mot liknande sjukdomsframkallare av svampkaraktar p6. andra planter och. vaxter. The compounds which come into use in accordance with the invention are primarily active with respect to harmful organisms of fungal character, against which also the hitherto customary dithiocarbamic acid salts have come into use, i.e. especially against Phytophthora infestans, Cladosporium fulvum or Alternaria solani pd. tomatoes and potatoes, against Peronspora (= Plasmopara viticola) on wine, Venturia inaequalis buttercup in addition to similar pathogens of fungal character p6. other plants and. plants.

De i enlighet med uppfinningen till anvandning kommande foreningarna anvandas pa i princip kant satt, dvs. foretradesvis tillsammans med lampliga fasta eller flytande fyllnads- eller utspadningsmedel, eventuellt i narvaro av lampliga emulgatorer eller vatmedel. Foretradesvis komma fOreningarna till anvandning i utspadning med vatten tillsammans med icke-jonogena emulgatorer och/ eller vdtmedel avensom eventuellt tillsammans med ett inert, fast hjalpmedel. Anvandning av foreningarna tillsammans med andra fungicider och/eller insekticider är mojlig. The compounds which come into use in accordance with the invention are used in principle in a manner, ie. preferably together with suitable solid or liquid fillers or diluents, optionally in the presence of suitable emulsifiers or wetting agents. Preferably the compounds are used in dilution with water together with non-ionic emulsifiers and / or wetting agents as well as optionally together with an inert, solid excipient. Use of the compounds together with other fungicides and / or insecticides is possible.

Framstallningen av de i enlighet med uppfinningen till anvandning kommande foreningarna kommer i korthet att beskrivas nedan. 0,225 kg 1,2-propendiamin upplostes i 1,87 liter vatten. Darefter tilldroppades 0,55 kg kolsvavla, varpa 0,555 kg 46-procentig natronlut tillsattes. The preparation of the compounds for use in accordance with the invention will be briefly described below. 0.225 kg of 1,2-propenediamine was dissolved in 1.87 liters of water. Then 0.55 kg of carbon sulfur was added dropwise, warp 0.555 kg of 46% sodium hydroxide solution was added.

Den sa erhallna losningen (0,833 kg 100-procentig) omsattes darefter med a) en zinksaltlOsning (zinksulfat) 2 Utbyte: 0,900 kg metyletylen-bis-(ditiokarbaminsur)-zink med en halt av 87,2 % (efter avspaltningsbar CS2). en mangan(II)saltslosning (mangansulfat) Utbyte: 0,426 kg metyletylen-bis-(ditiokarbaminsurt)-mangan med en halt av 51,7 % (efter avspaltningsbar CS2). en mangan-zinksaltliisning (8 : 2) (mangansulf at och zinksulf at) Utbyte: 0,705 kg blandfallning av metyletylenbis-(ditiokarbaminsur)-mangan/zink (c:a 8: 2) med en halt av 43,7 % (efter avspaltningsbar CS2). The solution thus obtained (0.833 kg 100%) was then reacted with a) a zinc salt solution (zinc sulphate). 2 Yield: 0.900 kg of methylethylene-bis- (dithiocarbamic acid) -zinc with a content of 87.2% (after cleavable CS2). a manganese (II) salt solution (manganese sulphate) Yield: 0.426 kg of methylethylene-bis- (dithiocarbamic acid) -mangan with a content of 51.7% (after cleavable CS2). a manganese-zinc salt solution (8: 2) (manganese sulphate and zinc sulphate) Yield: 0.705 kg mixture of methylethylenebis- (dithiocarbamic acid) -mangan / zinc (approx. 8: 2) with a content of 43.7% (after cleavable bar CS2).

Man kan ocksa enligt ett foredraget framstallningsforfarande framstalla de i enlighet med uppfinningen till anvandning kommande fOreningarna direkt fran propendiklorid, sasom framgar av foljande kortfattade framstallningsforeskrift. 37,7 g propendiklorid och 396,0 g 35,8-procentig ammoniaklOsning (NH4OH) omsattes under 32 timmar och omroring i en autoklav vid en ternperatur av 78-80° C, tills propenkloriden forsvunnit. Losningen indunstades till torrhet i vakuum och aterstoden upptogs i 210 ml vatten. It is also possible, according to a preferred preparation process, to prepare the compounds for use in accordance with the invention directly from propylene dichloride, as is apparent from the following brief preparation instructions. 37.7 g of propylene dichloride and 396.0 g of 35.8% ammonia solution (NH 4 OH) were reacted for 32 hours and stirred in an autoclave at a temperature of 78-80 ° C until the propylene chloride disappeared. The solution was evaporated to dryness in vacuo and the residue was taken up in 210 ml of water.

Denna vattenlosning forsattes vid en temperatur av 38-40° C (under innehallande av ett pHvarde understigande 10) Mom loppet av c:a 8 timmar med 80 g 46-procentig natronlut och 54 g kolsvavla. Efter tillsats av nagot kiselgur avsegs lOsningen. Derma losning forsattes med en vattenhaltig losning av zinksulfat och det utfallda zinksaltet avsogs och torkades. This aqueous solution was continued at a temperature of 38-40 ° C (while maintaining a pH below 10) for about 8 hours with 80 g of 46% sodium hydroxide solution and 54 g of carbon sulfur. After adding some diatomaceous earth, the solution is discarded. This solution was continued with an aqueous solution of zinc sulphate and the precipitated zinc salt was filtered off with suction and dried.

Utbyte: 50 g 85-procentig (efter avspaltningsbar CS2) metyletylen-bis-(ditiokarbaminsur)-zink. Yield: 50 g of 85% (after cleavable CS2) methylethylene-bis- (dithiocarbamic acid) zinc.

I stallet f6r den rena propenkloriden kan likasa en propenkloridhaltig biprodukt Iran petrokemin anvandas. Instead of the pure propylene chloride, a propylene chloride-containing by-product Iran petrochemical can also be used.

Nedanstaende exempel avser att narmare belysa egenskaperna for de i enlighet med uppfinningen till anvandning kommande foreningarna. The following examples are intended to further illustrate the properties of the compounds which will be used in accordance with the invention.

Exempel. I nedanstaende tabeller jamforas verkan for det i enlighet med uppfinningen till anvandning kommande zinksaltet av isopropen-bisditiokarbaminsyra med verkan f Or propen-bisditiokarbaminsyra, eten-bis-ditiokarb aminsyra och tetrametylen-bis-ditiokarbaminsyra. Example. The following tables compare the action of the zinc salt of isopropene-bisdithiocarbamic acid used in accordance with the invention with the action of propylene-bisdithiocarbamic acid, ethylene-bis-dithiocarbamic acid and tetramethylene-bis-dithiocarbamic acid.

I sin akuta verkan är betraffande samtliga provade svampar foreningen enligt uppfinningen betydligt overlagsen zinketen-bis-ditiokarbamat. Anmarkningsvard Ar regnfastheten for ett sprutpulver av foreningen enligt uppfinningen, som Overraskande nog overtraffar verkan f6r en pa liknande satt framstalld komposition av zinketen-bis-ditiokarbamatet. Sarskilt pafallande fir den i jamforelse med zinketen-bis-ditiokarbamat hoga verkan med avseende pa Peronospora pa via. Sarskilt overraskande är ocksa verkan mot akta mjoldagg (Erysiphe) pa gurkor. For zinketenbisditiokarbamat Ar det karat, att detta efter langre tids anvandning indirekt beframjar angreppet av akta mjoldagg. In their acute action, with regard to all the tested fungi, the compound according to the invention is considerably superior to zinc ketene bis-dithiocarbamate. Remarkable value is the rainfastness of a spray powder of the compound of the invention, which surprisingly surpasses the effect of a similarly prepared composition of the zinc ketene bis-dithiocarbamate. Particularly striking is the high effect with respect to Peronospora on via in comparison with zinc-bis-dithiocarbamate. Particularly surprising is also the effect against cautious powdery mildew (Erysiphe) on cucumbers. For zinc ketene bisdithiocarbamate Is it carat, that after long-term use it indirectly promotes the attack of cautious powdery mildew.

Av tabellerna framgar tydligt, att isopropenfOreningen ar vida Overlagsen etenfOreningen, propenforeningen och tetrametylenfOreningen. The tables clearly show that the isopropylene compound is broadly superior to the ethylene compound, the propylene compound and the tetramethylene compound.

Provsvamp Phythopthora Angreppsgrad yid en koneentration av den verksamma bestandsdelen av; (i jamfbrelse med obehandlat kontrollprov100) 0,1% 0,025% 0,0125% 0,0062% 0,0031% 0,00155% pa tomater 0 1 37 6 1 2 17 43 Peronospora 0 pa vin 2 41 Cladosporium pA tomater 3 8 18 63 Alternaria pa tomater 0 0 1 12 Erysiphe pa gurkor 0 53 Forming Zinkisopropylen-his-ditiokarbamat Zinketylen-bis-ditio- ' karbamat Zinkisopropylen-bis-ditiokarbamat som 75 %-igt sprutpulver i vatten suspenderat med emulgator av handelskvalitet (nonylfenolpolyglykole ter) (A) Zinketylen-bis-ditiokarbamat som 7%-igt sprutpulver i vatten suspenderat med emulgator av handelskvalitet (nonylfenolpolyglykoleter) (B) A A A A FOreningBestrilningsprov Provsvamp Zinkisopropylen-bis-ditiokarbamat som 75-procentigt sprutpulver i vatten suspenderat med emulgator Phytophora av handelskvalitet (nonylfenolpo- pa tomater lyglykoleter) Zinketylen-bis-ditiokarbamat som 75-procentigt sprutpulver i vatten suspenderat med emulgator av handelskvalitet (nonylfenolpoly- glykoleter) Obehandlat kontrollprov Bestrilat 6 ganger med 24 timmars intervall obestrilat mellan varje gang, varje gang med 6,25 mm. Halt av verksarn komponent 0,09 % (1000 1/ha = 0,9 kg/ha) 0,214 30,18 % (1000 I/ha x 1,8 kg/ha) 100 FOreningProvsvampAngreppsgrad vid en koncentration av den verksamma bestandsdelen av: Zinkisopropylen-bis-ditiokarbamat Phytophthora pa tomater Zinketylen-bis-ditiokarbamat Zinkpropylenbisclitiokarbamat Zinkisopropylen-bis-ditiokarbamat 75-procentig beredning Zinketylenbis-ditiokarbamat 75- procentig beredning Zinkpropylenbis-ditiokarbamat 75- procentig beredning Zinkisopropylen-bis-ditiokarbamat Zinketylenbisditiokarbamat Zinktetrametylen-bis-ditiokarbamat Zinkisopropylen-bis-ditiokarbamat 75-procentig beredning Zinketylen-bis-ditiokarbamat 75-procentig beredning Zinktetrametylen-bis-ditiokarbamat 75-procentig beredning Obehandlat kontrollprov Phytopthora pa tomater 0,1 %0,025 % 0,0125 0%0,0062% 8 0,0031% 18T 4 17 43 29 44 7 2 6 4 37 6 43 8 18 4 17 43 37 39 60 2 6 4 37' 6 13 54 100 Betraffande Phytophthora infestans, Alternaria solani och Cladosporium fulvum besprutades unga tomatplantor (Bonny Best) i 4-5 bladsstadium med preparaten i form av vattenhaltig emulsion (verksam bestandsdel) resp. i form av vattenhaltig suspension (sprutpulverberedningar). Efter det aft plantorna fâtt torka under 24 timmar overstrilades de med uppslamningar av sporer av de ovannamnda svamparna och infordes i en fuktkammare med en luftfuktighel: av c:a 100 %. Efter tillandalupen inkubationstid (olika lang for de olika plantorna) faststalldes angreppet genom bedomning av de enskilda fjaderbladen enligt en skala fran 0 (fri fran angrepp) till 5 (bladet angripet av svamp Over hela sin yta eller forstort av svampen), och angreppsgraden uttrycktes i fOrhallande till de obehandlade kontrollplantorna, vilkas angreppsvarde sattes lika med 100. Sample fungus Phythopthora Influence rate yid a concentration of the active ingredient of; (in comparison with untreated control sample100) 0.1% 0.025% 0.0125% 0.0062% 0.0031% 0.00155% on tomatoes 0 1 37 6 1 2 17 43 Peronospora 0 on wine 2 41 Cladosporium on tomatoes 3 8 18 63 Tomato alternaria 0 0 1 12 Cucumber erysiphas 0 53 Formation Zinc isopropylene-his-dithiocarbamate Zinc ethylene-bis-dithio-carbamate Zinc isopropylene-bis-dithiocarbamate as 75% aqueous spray powder suspended with commercial grade emulsifier (A) Zinc ethylene bis-dithiocarbamate as 7% aqueous powder in suspension suspended with commercial grade emulsifier (nonylphenol polyglycol ether) (B) AAAA Compound Irradiation test - on tomatoes lyglycol ethers) Zinc ethylene bis-dithiocarbamate as 75% spray powder in water suspended with commercial grade emulsifier (nonylphenol polyglycol ether) Untreated control sample Irradiated 6 times with 24 hours March interval unstrilled between each time, each time by 6.25 mm. Content of the plant component 0.09% (1000 1 / ha = 0.9 kg / ha) 0.214 30.18% (1000 I / ha x 1.8 kg / ha) 100 FOUNRINGSample fungus Influence rate at a concentration of the active ingredient of: Zinkisopropylen-bis-dithiocarbamate Phytophthora on tomato zinc ethylene bis-dithiocarbamate Zinkpropylenbisclitiokarbamat Zinkisopropylen bis dithiocarbamate 75 percent zinc ethylenebisdithiocarbamate preparation 75- percent formulation Zinkpropylenbis dithiocarbamate 75- percent formulation Zinkisopropylen-bis-dithiocarbamate, zinc ethylenebisdithiocarbamate Zinktetrametylen-bis-dithiocarbamate Zinkisopropylen- bis-dithiocarbamate 75% preparation Zinc ethylene bis-dithiocarbamate 75% preparation Zinc tetramethylene bis-dithiocarbamate 75% preparation Untreated control sample Phytopthora on tomatoes 0.1% 0.025% 0.0125 0% 0.0062% 8 0.0031% 18T 4 17 43 29 44 7 2 6 4 37 6 43 8 18 4 17 43 37 39 60 2 6 4 37 '6 13 54 100 Concerning Phytophthora infestans, Alternaria solani and Cladosporium fulvum, young tomato plants were sprayed r (Bonny Best) in 4-5 leaf stage with the preparations in the form of aqueous emulsion (active ingredient) resp. in the form of aqueous suspension (powder for injection). After allowing the plants to dry for 24 hours, they were sprinkled with slurry of spores of the above-mentioned fungi and introduced into a humidity chamber with a humidity of about 100%. After the incubation period (different lengths for the different plants), the infestation was determined by judging the individual feather leaves according to a scale from 0 (free from infestation) to 5 (the leaf infested with fungus all over its surface or enlarged by the fungus), and the degree of infestation was expressed in Relationship to the untreated control plants, whose infestation value was set equal to 100.

Betraffande Peronospora (Plasmopara viticola) pa vin inympades unga, i kruka placerade vinrankor av sorten MiiIler-Thurgau 24 timmar efter appliceringen av preparaten pa liknande Mit som oven angivits med avseende pa tomatplantorna med sporer av svampen. BedOmningen genomfordes analogt med det fOr tomatplantorna beskrivna forfarandet Betraffande erysiphe ph gurkor Overpudrades tont unga gurkplantor i 4-bladsstadium av sorten »Beste von Allen, 24 timmar efter behandlingen med preparaten med konidier av svampen och fingo kvarsta i vaxthus vid en luftfuktighet av 70-80 %. Resultaten faststalldes genom bedomfling av bladen pa lilmande satt som beskrivits ovan med avseende pa tomatplantorna. Regarding Peronospora (Plasmopara viticola) on wine, young, pot-placed vines of the variety MiiIler-Thurgau were inoculated 24 hours after the application of the preparations on similar Mit as indicated above with respect to the tomato plants with spores of the fungus. The assessment was carried out analogously to the procedure described for the tomato plants. Concerning erysiphe ph cucumbers. Tons of young cucumber plants were over-powdered »Best von Allen, 24 hours after treatment with the preparations with conidia of the fungus and were left in greenhouses at 70-80 humidity %. The results were determined by judging the leaves in a fragrant manner as described above with respect to the tomato plants.

For undersOkning av regnhallfastheten (bestrilningsprov) besprutades tomatplantor (Bonny Best) med 6 mellanblad med de angivna vatskemangderna per ytenhet. Efter 24 timmars torkning 4 I varthus genomfordes den f orsta bestrilningen. Plantorna placerades pa ett roterbart bord och besprutades under 9 minuter med destillerat vatten genom 2 munstycken snett ovanifran och snett underifran, varvid genom den vid besprutningen anvanda, stora luftmangden bladen pa plantorna forsattes i kraftig Mrelse. Denna bestrilning genomfordes sammanlagt 6 ganger med 24 timmars uppehall mellan varje gang, varunder plantorna stodo i vax.thus. Vid varje bestrilning foil 6,25 mm regn, sá att pa sá satt plantoma totalt efter 6 gangers bestrilning hade erhallit 37,5 mm regn. Av samma plantmaterial utbildades ocksa efter besprutningen flied samma preparatkompositioner obestrilade kontrollplantor. 24 timmar efter den sista bestrilningen inympades samtliga plantor — bestrilade, obestrilade och obehandlade kontrollplantor — gemensamt med en sporuppslamning av Phytophthora infestans i fuktkammare. Bedornningen skedde darefter pa samma satt som ovan beskrivits med avseende pa tomatplantorna. For examination of the rainforest strength (irradiation test), tomato plants (Bonny Best) were sprayed with 6 intermediate leaves with the specified water levels per unit area. After drying for 24 hours, the first irradiation was carried out in the warehouse. The plants were placed on a rotatable table and sprayed for 9 minutes with distilled water through 2 nozzles obliquely from above and obliquely from below, whereby through the large amount of air used in the spraying the leaves on the plants were continued in vigorous Mrelse. This irradiation was carried out a total of 6 times with a 24 hour break between each time, during which the plants stood in a greenhouse. At each irrigation foil 6.25 mm of rain, so that on it sat the plants in total after 6 times irradiation had received 37.5 mm of rain. The same plant material was also formed after spraying with the same preparation compositions as unirradiated control plants. 24 hours after the last irradiation, all plants - irradiated, unirradiated and untreated control plants - were inoculated together with a spore slurry of Phytophthora infestans in a moisture chamber. The pollination then took place in the same way as described above with respect to the tomato plants.

Claims

Patent claim:

Fungicidal agent, characterized in that it contains, in addition to a solid or liquid diluent or the like as an active ingredient, zinc and / or manganese salts of isopropylene-bisdithiocarbamic acid.

A fungicidal agent according to claim 1, characterized in that the active ingredient is present in a solvent.

A fungicidal agent according to claim 1, characterized in that the active ingredient is in the form of an aqueous emulsion. Cited publications: