SE176991C1

SE176991C1 -

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Publication number: SE176991C1
Authority: SE
Publication date: 1961-01-01

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Uppfinnare: J Bindler och E Model Prioritet begard !ran den 20 juli 1955 (Schweiz) Foreliggande uppfinning avser skyddsmedel for organiskt material mot svampangrepp och skador genom forruttnelse avensom industriell framstallfling av organiskt material, som med hj alp harav ãr skyddat for svampangrepp och/eller forruttnelse. Det har visat sig, att halogenerade bensazolf&eningar med den allmanna formeln NH (Hal)n C = Y aro speciellt lampliga sasom skyddsmedel for organiskt material mot svampangrepp och skador genom forruttnelse. Dessa egenskaper betecknas i det fOljande som fungicid verkan och de verksamma substanserna som fungicida medel, varvid attrycket »fungicid» eventuellt aven skall avse en fungistatisk verkan. I denna formel beteckna ettdera av X och Y en tvavard syreatom, den andra en tvavard syre- eller svavelatom, Hal halogen, foretradesvis klor eller aven brom, och n ett heft tal med vardet 1-3, foretradesvis 2 eller 3. Med denna formel avses aven de tautomera formerna, som uppsta under vtiteforskjutiiing fran ringkvavet mot Y, d.vensom salter av dessa tautomera former, speciellt alkalimetallsalterna eller aven ammoniumsalterna. Sasom verksam substans i de fungicida medlen enligt uppfinningen ifragakomma: vid bensenringen halogensubstituerade 2,3- -dihydrobensoxazol-2-oner och de tautomera 2- -oxibensoxalonerna respektive salter darav, vid bensenringen halogensubstituerade 2,3-dihydro-benstiazol-2-oner och de tautomera 2-oxibenstiazolerna och deras salter, dessutom vid bensenringen halogensubstituerade 2,3-dihydro-bensoxazol-2-tioner och de tautomera 2-merkaptobensoxazolerna och deras salter. Inventors: J Bindler and E Model Priority Claimed July 20, 1955 (Switzerland) The present invention relates to organic matter protection agents against fungal infections and damage by decay as well as industrial production of organic materials which have been aided by fungal infections and / or decay. It has been found that halogenated benzazole compounds of the general formula NH (Hal) n C = Y are particularly suitable as protective agents for organic material against fungal attack and damage by decay. These properties are hereinafter referred to as fungicidal action and the active substances as fungicidal agents, the term "fungicidal" possibly also referring to a fungistatic action. In this formula, each of X and Y represents a divalent oxygen atom, the other a divalent oxygen or sulfur atom, Hal halogen, preferably chlorine or also bromine, and n a number number having the value 1-3, preferably 2 or 3. With this formula It also refers to the tautomeric forms which arise during the displacement of the ring nitrogen towards Y, i.e. also salts of these tautomeric forms, in particular the alkali metal salts or also the ammonium salts. The following active substances in the fungicidal compositions according to the invention are: in the benzene ring halogen-substituted 2,3--dihydrobenzoxazol-2-ones and the tautomeric 2 -oxybenzoxalones and salts thereof, in the benzene ring halogen-substituted 2,3-dihydro-benzothiazol-2-ones the tautomeric 2-oxybenziazoles and their salts, in addition to the benzene ring halogen-substituted 2,3-dihydrobenzoxazole-2-ions and the tautomeric 2-mercaptobenzoxazoles and their salts.

De ringhalogenerade bensazolforeningarna, som enligt uppfinningen komma till anvandning, aro delvis kanda sasom mellansteg vid framstallning av mellanprodukter for fargamnen, delvis Oro de nya amnen, vilka latt kunna framstallas enligt i och for sig kanda forfaranden. Man erhaller dem exempelvis ur ringhalogenerade o-aminfenoler vid omsattningen med fosgen eller tiofosgen, avensom ur ringhalogenerade o-amintiofenoler vid omsattningen med fosgen. Man kan eventuellt liven forst senare infOra halogen, t. ex. i 2,3-dihydro-bensoxazol-2-on med fri 6-stallning. De utgara i allmanhet farglosa till svagt gulfargade, fasta amnen, som i varmt vatten ha en mycket liten loslighet. Mycket lattare losliga Oro alkalimetallsalterna, t. ex. litium-, natrium- och kaliumsalterna, likasa magnesium- och kalciumsalterna, dessutom ammoniumsalterna av starka oorganiska eller organiska kvavebaser. De enligt uppfinningen anvandbara halogenerade bensenforeningarna kunna tack vare dessa loslighetsegenskaper och pa grund av sin forhallandevis goda stabilitet mot alkalier infOras i textilbehandlingsbaden, speciellt ytaktiva tvattbad, som jamte syntetiska, tvattaktiva substanser och/eller jamte tvalar i gangse mening aven kunna innehalla saval vanliga fyllmedel, sasom natriumkarbonat, natriumsilikater och alkali-mono- och polyfosfater, som ytterligare i tvattmedel vanliga substanser. Man kan direkt blanda dem i dylika tvatt- och rengoringsmedel, sasom aven tval, och erhaller med det salunda sammansatta rengoringsmedlet tvattbad, som skydda det armed behandlade ma terialet for svampangrepp och svampskador. Den tillfredsstallande losligheten av de verksamma substanserna i sadana organiska losningsmedel, som finna anvandning vid s. k. kemisk tvatt, medger deras anvandning i dylika rengoringsmedel, som best h av alifatiska eller aromatiska, eventuellt ldorerade kolvaten och mestadels aven innehalla oljelosliga kalisalter av anjonaktiva vat- och rengoringsmedel, avensom vid framstallningen av s. k. >Sprays». Man kan dessutom blanda in dem i behandlingsbad for papper eller i tryckningsfortjockningar av starkelse- eller cellulosapro- 2— — dukter eller anvanda dem for impregnering av tra. Aven saval i peparat av polyvinylklorid, exempel-vis folier, som i lacker och pastrykningsfarger, som aro framstallda pa kaseinbas eller innehalla kasein, uppnas med de enligt uppfinningen anvandbara substanserna ett verksamt skydd mot svampangrepp. De insattas dessutom framgangsrikt for skydd av fotterna mot svanpangrepp, t. ex. genom behandling av skodonen, inlaggsulorna eller strumporna. Ett ytterligare anvandningsomrade utgor behandlingen av tvatt i hotell- och restaurangbranschen. Alla dessa kompositioner, som kannetecknas av en halt av fungicida substanser med den ovan angivna allmanna formeln skola betraktas sasom liggande inom ramen for fOrfarandet enligt uppfinningen. The ring halogenated benzazole compounds which are used according to the invention are partly known as intermediates in the preparation of intermediates for the dyes, and are partly known as the new substances which can easily be prepared according to per se known processes. They are obtained, for example, from ring halogenated o-aminophenols on the reaction with phosgene or thiophosgene, as well as from ring halogenated o-amintiophenols on the reaction with phosgene. It is possible that life can only be introduced later by halogen, e.g. in 2,3-dihydro-benzoxazol-2-one with free 6-position. They generally turn colorless to pale yellow solid solids, which in warm water have a very slight looseness. Much easier soluble Oro the alkali metal salts, e.g. the lithium, sodium and potassium salts, as well as the magnesium and calcium salts, in addition the ammonium salts of strong inorganic or organic nitrogen bases. Due to these solubility properties and due to their relatively good stability against alkalis, the halogenated benzene compounds which can be used according to the invention can be incorporated into textile treatment baths, especially surfactant baths, which, together with synthetic, detergent substances and / or whey, can also contain fillers. such as sodium carbonate, sodium silicates and alkali mono- and polyphosphates, as further substances common in detergents. They can be directly mixed in such detergents and detergents, as well as soap, and obtained with the saline compound detergent baths, which protect the armed treated material from fungal infestation and fungal damage. The satisfactory solubility of the active substances in such organic solvents, which find use in so-called chemical washing, allows their use in such detergents, which consist of aliphatic or aromatic, optionally diluted hydrocarbons and mostly also contain oil-soluble potassium salts and anion-active aqueous detergents. , except in the production of so-called> Sprays ». They can also be mixed in paper treatment baths or in printing thickeners of starch or cellulose products or used for impregnating wood. Also saval in preparations of polyvinyl chloride, for example foils, as in varnishes and paste printing paints, which are produced on a casein-based basis or contain casein, an effective protection against fungal attack is achieved with the substances usable according to the invention. They are also used successfully to protect the feet against swan infestation, e.g. by treating the footwear, insoles or socks. An additional area of use is the treatment of laundry in the hotel and restaurant industry. All these compositions, which may be characterized by a content of fungicidal substances of the above general formula, should be considered as being within the scope of the process of the invention.

Enligt uppfinningen kan man exempelvis, sasom verksamma amnen, anvanda: 5-klor-2,3-dihydro-bensoxazol-2-on, 5,6-diklor - 2,3 - dihydro- bensoxazol-2-on, 5.7-diklor-2,3-dihydro-bensoxazol-2-on, 5-klor-6-brom-2,3-dihydro-b ensoxazol on, 4,5,7-triklor-2,3-dihydro-bensoxazol-2-on, 5- -klor-2,3-dihydro-b ensoxazol - 2- tion, 5,6-diklor-2,3-dihydro-bensoxazol-2-tion, 5,6-diklor-2,3-dihydrobenstiazol-2-on, 4,5,6-triklor - 2,3 - dihydro-benstiazol-2-on, 4,6,7-triklor-2,3-dihydro-b enstiaz ol-2-on. Framfor de kanda, liknande foreningarna, som redan fiireslagits och anvants for samma andamal, t. ex. framfor 2-merkaptobenstiazoler, ha de enligt uppfinningen anvanda, verksamma amnena fordelen av en mycket rnindre farg, vilken egenskap for dem oppnar manga anvandningsomraden, som limo uteslutna for de kanda foreningarna pa. grund av deras farg. I detta avseende aro 2-oxoforeningarna speciellt lampliga, verksamma amnen enligt uppfinningen och de foredragas darfor och pa grund av sin lattare tillganglighet framfor 2-tionerna. Speciellt stabila i lj us och svagt fargade aro de enligt uppfinningen anvanda oxazolerna, som aven fOredragas framfor tiozolerna pa grund av, att de am o sarskilt lAtt tiligangliga ur de vanliga fargainnesmellanprodukterna. Anbringandet av de fungicida amnena pa det organiska material som skall skyddas, sker mestadels antingen genom inblandning, besprutning eller impregnering med organiska, vattenhaltiga eller vattenhaltigtalkaliska losningar av de verksamma amnena eller med tvatt- rengorings- eller skoljbad, som innehalla det verksamma amnet lost eller dispergerat. Halter av 0,5 till 10 g verksam substans per liter behandlingsbad aro i allmanhet tillrackliga for ett verksamt skydd av det behandlade materialet. Tvattaktheten av det fungicida medlet pa det behandlade materialet kan eventuellt hojas ytterligare genom efterbehandling med medel, som avge en tung metal Sasom sadant medel kunna exempelvis kopparsaIter anvandas. Sasom organiskt material, som skall skyddas, ifragakomma i forsta hand cellulosamaterial, sasom textilier, cellull, tra och papper osv. Till anvandbarheten i tryckpastor eller i lacker pa kaseinbas har redan hamvisats. According to the invention, there can be used, for example, as active substances: 5-chloro-2,3-dihydro-benzoxazol-2-one, 5,6-dichloro-2,3-dihydro-benzoxazol-2-one, 5,7-dichloro- 2,3-dihydro-benzoxazol-2-one, 5-chloro-6-bromo-2,3-dihydro-benzoxazolone, 4,5,7-trichloro-2,3-dihydro-benzoxazol-2-one, 5-chloro-2,3-dihydro-benzoxazole-2-thione, 5,6-dichloro-2,3-dihydro-benzoxazole-2-thione, 5,6-dichloro-2,3-dihydrobenstiazole-2- one, 4,5,6-trichloro-2,3-dihydro-benstiazol-2-one, 4,6,7-trichloro-2,3-dihydro-benstiazol-2-one. In front of the kanda, similar associations, which have already been proposed and used for the same purpose, e.g. over 2-mercaptobenzothiazoles, the active substances used according to the invention have the advantage of a much lower color, the property of which opens up many areas of application, which limo excludes for the known compounds. because of their color. In this respect, the 2-oxo compounds are particularly suitable, active substances according to the invention and are therefore preferred and due to their easier access to the 2-ions. Particularly stable in light and weakly colored are the oxazoles used according to the invention, which are also preferred over the thiozoles due to the fact that they are particularly readily available from the usual color intermediates. The application of the fungicidal substances to the organic material to be protected takes place either by mixing, spraying or impregnation with organic, aqueous or aqueous alkaline solutions of the active substances or with water-cleaning or rinsing baths containing the active substance dissolved or dispersed. . Concentrations of 0.5 to 10 g of active substance per liter of treatment bath are generally sufficient for effective protection of the treated material. The water density of the fungicidal agent on the treated material can possibly be further increased by post-treatment with agents which release a heavy metal. As such agent, for example, copper salts can be used. As organic material to be protected, cellulosic materials, such as textiles, cellulose, wood and paper, etc., come into play in the first place. The usability of printing pastes or casein-based paints has already been referred to.

Foljande exempel askadliggora uppfinningen. I dessa beteckna delar, savida intet annat ar ut tryckligt anmarkt, viktdelar. Temp eraturerna aro angivna i celsiusgrader.Viktdelarna forhalla sig till volymdelar som g till ml. The following examples illustrate the invention. In these parts, unless otherwise expressly stated, denote parts by weight. The temperatures are given in degrees Celsius. The weight parts relate to volume parts that go to ml.

Exempel 1. Man loser 20 delar 5,6-diklor-2,3- -dihydro-benstiazol-2-on i 320 delar etylalkohol under tillsats av 3,8 delar natriumhydroxid och framstaller med denna stamlosning genom spadning med vatten ett behandlingsbad, som per liter innehaller 1 g verksam substans. Med detta behandlingsbad behandlas bomullskalika i 30 mina-ter vid 60° C i ett badforhallande av 1: 20, centrifugeras och torkas. Det salunda behandlade materialet dr skyddat mot bildning av mogelflackar och forruttnelse, sasom visas av fOljande prov. Example 1. 20 parts of 5,6-dichloro-2,3-dihydro-benstiazol-2-one are dissolved in 320 parts of ethyl alcohol with the addition of 3.8 parts of sodium hydroxide and with this stock solution is prepared by spreading with water a treatment bath which per liter contains 1 g of active substance. With this treatment bath, cotton calico is treated for 30 minutes at 60 ° C in a bath ratio of 1:20, centrifuged and dried. The thus treated material is protected against the formation of mold flakes and decay, as shown by the following samples.

Mogelflacksprovning: Cirkelformat utskurna vavnadsbitar med 9 cm diameter laggas pa en naringsplatta av agar i petriskalar och ympas med suspensionen av en sporblandning fran Penicillium expansum, Stachybotrys atra och Aspergillus niger, vilken blandning innehaller 40 000 sporer/ml. De slutna petriskalarna odlas 10 dygn vid 28° och sedan raknas antalet svampkolonier. Mug flake test: Circularly cut 9 cm diameter tissue pieces are placed on a feeding plate of agar in petri dishes and inoculated with the suspension of a spore mixture from Penicillium expansum, Stachybotrys atra and Aspergillus niger, which mixture contains 40,000 spores / ml. The closed petri dishes are grown for 10 days at 28 ° and then the number of fungal colonies is shaved.

Forruttnelseprov: Cirkelformiga, utskurna vavnadsbitar med 3,8 cm diameter laggas pa en naringsplatta av agar i petriskalar, vilken platta ar ympad med 0,5 ml av en sporsuspension av Chaetomium globosum, vilken suspension innehaller cirka 700 000 sporer/ ml. Man odlar 10 dygn vid 28°, avbryter sedan sporutvecklingen med en alkoholisk tomyllosning, spolar de utskurna tygstyckena och torkar dem. Genomslagshallfastheten provas sedan i en genomslagsapparat enligt R. Burgess (Microorganismus and Textiles: The Journal of Applied Bacteriology 17, 241 (1954)). Decay test: Circular, cut pieces of tissue 3.8 cm in diameter are placed on a feeding plate of agar in petri dishes, which plate is inoculated with 0.5 ml of a spore suspension of Chaetomium globosum, which suspension contains about 700,000 spores / ml. It is grown for 10 days at 28 °, then the spore development is interrupted with an alcoholic tomyll solution, the cut pieces of fabric are rinsed and dried. The impact hall strength is then tested in a breakthrough apparatus according to R. Burgess (Microorganism and Textiles: The Journal of Applied Bacteriology 17, 241 (1954)).

Jordnedgravningsprovning: Cirkelformigt utskurna vavnadsbitar med 3,8 cm diameter gravas under 14 dygn ned i en lordblandning, som har en fuktighetshalt av 0A och en temperatur av 28° och Ar framstalld av 50% kompostjord, 30 % kogodsel och 20 V„ sand. Va.vnaderna spolas och torkas sedan. De hallfasthetsprovas nu i en genomslagsapparat enligt Burgess. Vid forruttnelse- och jordnedgravningsproven anvandes genomsnittsvardet av 10 prov. Hallfastheten angives i % av den ursprungliga vavnadens hallfasthet. Resultatet av dessa provningar ar sammanfattat i tabellen i anslutning till exempel 12. Soil burial test: Circularly cut pieces of fabric with a diameter of 3.8 cm are buried for 14 days in a soil mixture, which has a moisture content of 0A and a temperature of 28 ° and Ar produced from 50% compost soil, 30% cow manure and 20 V sand. The fabrics are rinsed and then dried. They are now tested for resistance in a breakthrough device according to Burgess. In the decay and soil excavation tests, the average value of 10 samples was used. The half strength is stated in% of the half strength of the original fabric. The results of these tests are summarized in the table in connection with Example 12.

Exempel 2. Man loser 20 delar 6-klor-2,3-dihydrobenstiazol-2-on under tillsats av 4,33 delar natriumhydroxid i 160 delar etylalkohol och framstaller darav genom spadning med vatten ett behandlingsbad, som per liter innehaller 1 g verksam substans. Med detta behandlingsbad behandlas bomullskalika, sasom beskrivits i exempel 1. Det salunda behandlade materialet ar skyddat mot mogelflackar och forruttnelse, sasom framgar av tabell. Provningarna skedde sasom utforligt beskrivits i exempel 1. — —3 Exempel 3. 5,6-diklor - 2,3 - dihydrobenstiazol-2-on (substans a) respektive 6-klor-2,3-dihydrobenstiazol-2-on (substans b) losas i etylenglykolmonometyleter i koncentrationerna 1 g/liter respektive 10 g/liter. I badforhallandet 1: 20 doppas bomullskalikdremsor dari i 30 sekunder vid rumstemperatur, urpressas till 100 % och torkas. Det salunda behandlade materialet Eir skyddat mot bildning av mbgelflackar och forruttnelse. Det underkastas mOgelfld.ckprovet, forruttnelseprovet on jordnedgrdyningsprovet enligt exempel 1. Resultaten framga av tabell. Example 2. 20 parts of 6-chloro-2,3-dihydrobenstiazol-2-one are dissolved with the addition of 4.33 parts of sodium hydroxide in 160 parts of ethyl alcohol and a treatment bath containing 1 g of active substance is prepared by diluting with water. . With this treatment bath, cotton scales are treated, as described in Example 1. The thus treated material is protected against mold flakes and rot, as shown in the table. The tests were carried out as described in detail in Examples 1. - 3 Examples 3. 5,6-Dichloro-2,3-dihydrobenstiazol-2-one (substance a) and 6-chloro-2,3-dihydrobenstiazol-2-one (substance) b) dissolved in ethylene glycol monomethyl ether at concentrations of 1 g / liter and 10 g / liter respectively. In the bath ratio 1:20, cotton scale strips are dipped for 30 seconds at room temperature, extruded to 100% and dried. The thus treated material Eir protected against the formation of furniture flakes and decay. It is subjected to the mogelfld.ck test, the decay test and the soil degradation test according to example 1. The results are shown in table.

Exempel 4. 10 delar 5,6-diklor-2,3-dihydro-bensoxazol-2-tion lOsas i 80 delar etylalkohol under tillsats av 1,9 delar natriumhydroxid. Man spdder nu med vatten, sa att ett behandlingsbad bildas, som per liter innehaller 1 g verksam substans. Med detta behandlingsbad behandlas bornullskalika sasom i exempel 1. Det sã behandlade materialet dr skyddat mot bildning av mogelflackar och forruttnelse. Det underkastas mogelflacks-, forruttnelse- och jordnedgrdvningsproven, shsom beskrives i exempel 1. Resultaten framga'r av tabell. Example 4. 10 parts of 5,6-dichloro-2,3-dihydro-benzoxazole-2-thione are dissolved in 80 parts of ethyl alcohol with the addition of 1.9 parts of sodium hydroxide. It is now diluted with water, so that a treatment bath is formed, which per liter contains 1 g of active substance. With this treatment bath, boron wool scales are treated as in Example 1. The material thus treated is protected against the formation of mold flakes and decay. It is subjected to the mud flake, decay and soil sedimentation tests, as described in Example 1. The results are shown in Table.

Exempel 5. 20 delar 5-klor-2,3-dihydrobensoxazol-2-tion (substans a) respektive 6-klor-2,3-dihydrobensoxazol-2-tion (substans b) losas i 360 delar etylalkohol under tillsats av 4,33 delar natriumhydroxid. Man framstdller av denna stamlosning genom spadning med vatten ett behandlingsbad, som per liter innehaller 4 g respektive 10 gverksam substans. Med detta behandlingsbad behandlas bomullskalikh, sasom i exempel 1. Det sa behandlade materialet dr skyddat mot Midning av mogelflackar cola forruttnelse. Resultaten av provningarna framga av tabell. Example 5. 20 parts of 5-chloro-2,3-dihydrobenzoxazole-2-thione (substance a) and 6-chloro-2,3-dihydrobenzoxazole-2-thione (substance b) are dissolved in 360 parts of ethyl alcohol with the addition of 4, 33 parts of sodium hydroxide. This stock solution is prepared by diluting with water a treatment bath which contains 4 g and 10 of active substance per liter, respectively. With this treatment bath, cotton calico is treated, as in Example 1. The treated material is protected against the contamination of mold flakes cola decay. The results of the tests are shown in the table.

Exempel 6. 5,6-diklor-2,3-dihydrobensoxazol-2-tion (substans a) respektive 5-klor-2,3-dihydrobensoxazol-2-tion (substans b) respektive 6-klor2,3-dihydrobensoxazol-2-tion (substans c) losas i etylenglykolmonometyleter i koncentrationerna 4 g/liter, 8 g/liter respektive 10 g/liter. I badforhallandet I: 20 doppas bomullskalika dari ii minut i kallt tillstand, avpressas till 100 % och torkas. Det sa behandlade materialet dr skyddat mot bildning av mogelflackar och forruttnelse. Det utsattes for mogelflacks- forruttnelse- och jordnedgravningsproven, sasom utforligt beskrivits i exempe11. Resultaten framgá av tabellen. Om man i exemplet ovan i stallet for 5,6-diklor-2,3-dihydrobensoxazol-2-tion anvhnder 5,6- dibrom-2,3 - dihydrobensoxazol-2-tion och i stallet for 5-klor2,3-dihydrobensoxazol-2-tion anvander 5- brom 2,3-dihydrobensoxazol-2-tion, erhaller man ett behandlingsbad, som anbragt pa bomullskalika pd ovan angivet Ott ger ett lika gott skydd mot bildning av mdgelflackar och fOrruttnelse. Example 6. 5,6-Dichloro-2,3-dihydrobenzoxazole-2-thione (substance a) and 5-chloro-2,3-dihydrobenzoxazole-2-thione (substance b) respectively 6-chloro2,3-dihydrobenzoxazole-2 -tion (substance c) is dissolved in ethylene glycol monomethyl ether in the concentrations 4 g / liter, 8 g / liter and 10 g / liter respectively. In the bath ratio I: 20, cotton scales are dipped for 1 minute in a cold state, pressed to 100% and dried. The so-treated material there protected against the formation of mold flakes and decay. It was subjected to the mud flake, decay and soil excavation tests, as described in detail in Example 11. The results are shown in the table. If in the example above instead of 5,6-dichloro-2,3-dihydrobenzoxazole-2-thione 5,6-dibromo-2,3-dihydrobenzoxazole-2-thione is used and instead of 5-chloro2,3-dihydrobenzoxazole -2-thione uses 5-bromo 2,3-dihydrobenzoxazole-2-thione, a treatment bath is obtained, which is applied to cotton scales on the above-mentioned otters, providing equally good protection against the formation of mold flakes and decay.

Exempel 7. Man loser 10 delar 4,5,7-triklor-2,3 -dihydrobensoxazol-2-on i 80 delar etylalkohol under tillsats av 1,77 delar natriumhydroxid och framstaller darav genom spadning med vatten ett behandlingsbad, som per liter innehaller 4 g verksam substans. I denna losning doppas bomulls kalikâ vid ett badforhallande av 1: 20 i 1 minut i kallt tillstand, urpressas till 100 % och torkas. Det sã behandlade materialet ãr skyddat mot bildning av mogelflackar och forruttnelse. Det utsattes for mogelfldeks-, fOrruttnelse- och jordnedgrdvningsproven. Resultaten framgâ av tabell. Example 7. 10 parts of 4,5,7-trichloro-2,3-dihydrobenzoxazol-2-one are dissolved in 80 parts of ethyl alcohol with the addition of 1.77 parts of sodium hydroxide and a treatment bath containing per liter is prepared, which is diluted with water. 4 g of active substance. In this solution, cotton kalikâ is dipped at a bath ratio of 1:20 for 1 minute in a cold state, squeezed out to 100% and dried. The material thus treated is protected against the formation of mold flakes and decay. It was subjected to the mud cover, decay and soil testing tests. The results are shown in the table.

Exempel 8. 20 delar 5,6-diklor-2,3-dihydrobensoxazol-2-on losas 1160 delar etylalkohol under tillsats av 4,1 delar natriumhydroxid och darav framstalles genom spadning med vatten ett behandlingsbad, sam per liter innehaller 1 g verksam substans. Bomullskalika doppas ddri i 1 minut i kallt tillstand, urpressas till 100 % och torkas. Det sá behandlade materialet ar skyddat mot bildning av mogelflackar och forruttnelse. D et utsattes for mogelfldcks- och forruttnelseproven, sasom beskrivits i exempel 1. Resultaten framga av tabell. Example 8. 20 parts of 5,6-dichloro-2,3-dihydrobenzoxazol-2-one are dissolved in 1160 parts of ethyl alcohol with the addition of 4.1 parts of sodium hydroxide and from this a treatment bath is prepared by diluting with water, co per liter containing 1 g of active substance . Cotton shells are dipped in it for 1 minute in a cold state, squeezed out to 100% and dried. The material thus treated is protected against the formation of mold flakes and decay. It was subjected to the mudflow and decay tests, as described in Example 1. The results are shown in Table.

Exempel 9. 4,5,7-triklor-2,3-dihydrobensoxazol-2-on (substans a) respektive 5,6-diklor-2,3- -dihydrobensoxazol-2-on (substans b) losas i sh mycket etylalkohol, att koncentrationerna uppga till 2 g per liter. Bomullskalikdremsor doppas ddri I badforhallandet 1: 20 under 30 sekunder i kallt tillstand, avpressas till 100 % och torkas. Det sa behandlade materialet dr skyddat mot bildning av mogelfldckar och fOrruttnelse. Det underkastas mogelflacks- och forruttnelseproven. Metodiken dr beskriven i exempel 1. Resultaten framgá av tabell. Example 9. 4,5,7-Trichloro-2,3-dihydrobenzoxazol-2-one (substance a) and 5,6-dichloro-2,3-dihydrobenzoxazol-2-one (substance b) are dissolved in a large amount of ethyl alcohol , that the concentrations amount to 2 g per liter. Cotton scale strips are dipped in the bath ratio 1:20 for 30 seconds in the cold state, pressed to 100% and dried. The so-treated material there protected against the formation of mold patches and decay. It is subjected to the mold and rot tests. The methodology described in example 1. The results are shown in table.

Exempel 10. 10 delar 4,5,7-triklor-2,3-dihydrobensoxazol-2-on blandas med lika manga delar tv5.1 och blandningen loses 1140 delar alkohol under tillsats av 1,77 delar natronlut. Man spader nu sd mycket med vatten, att en losning bildas, som per liter innehaller 2,g verksam substans. I en tvattmaskin behandlas i detta bad finare bomullskalika i 30 minuter vid 40°. Sedan skoljes 3 minuter, centrifugeras och torkas. De sâ preparerade vavnaderna dro skyddade emot bildning av mogelflackar och forruttnelse. De underkastas mogelflacks- och forruttnelserpoven. Resultaten framgd av tabell. Example 10. 10 parts of 4,5,7-trichloro-2,3-dihydrobenzoxazol-2-one are mixed with equal parts of tv5.1 and the mixture is dissolved 1140 parts of alcohol with the addition of 1.77 parts of sodium hydroxide solution. You now shovel so much with water that a solution is formed, which per liter contains 2 g of active substance. In a washing machine, finer cotton calico is treated in this bath for 30 minutes at 40 °. Then rinse for 3 minutes, centrifuge and dry. The well-prepared tissues were protected against the formation of mold flakes and decay. They are subjected to mold and rot tests. The results are shown in the table.

Exempel 11. 6-brom-2,3-dihydrobensoxazol-2- -on (substans a) respektive 5-klor-6-brom-2,3-dihydrobensoxazol-2-on (substans b) losas i sd mycket etylenglykol-monometyleter, att koncentrationerna bli 5 g respektive 10 g per liter. I dessa losningar doppas i kallt tillstand bomullskalikaremsor i badforhallandet 1: 20 under 30 sekunder, avpressas till 100 % och torkas. Det sa behandlade mateialet dr skyddat mot bildning av mogelflackar och fOrruttnelse. Det provas enligt den i exempel 1 beskrivna metoden. Resultaten framgh av tabell. Example 11. 6-Bromo-2,3-dihydrobenzoxazol-2-one (substance a) and 5-chloro-6-bromo-2,3-dihydrobenzoxazol-2-one (substance b) are dissolved in a large amount of ethylene glycol monomethyl ether , that the concentrations be 5 g and 10 g per liter, respectively. In these solutions, in the cold state, cotton scale strips are dipped in the bath ratio 1:20 for 30 seconds, extruded to 100% and dried. The treated material there is protected against the formation of mold flakes and decay. It is tested according to the method described in Example 1. The results are shown in the table.

Exempel 12. 5,6-dibrom-2,3-dihydrobensoxazol-2-on (substans a) rspektive 4,5,7-tribrom-2,3- -dihydrobensaxazol-2-on (substans b) losas i etylalkohol i koncentrationerna 4 g per liter. I dessa behandlingsbad doppas bomullskalika i forhallandet 1: 20 i kallt tillstand, urpressas till 100 % och torkas. Det sa behandlade materialet an skyddat mot bildning av mogelflackar och fOrruttnelse. Resultaten av provningen, som foretagits sasom beskrivits i exempel 1, framga av tabell. Example 12. 5,6-Dibromo-2,3-dihydrobenzoxazol-2-one (substance a) and 4,5,7-tribromo-2,3-dihydrobenzaxazol-2-one (substance b) are dissolved in ethyl alcohol in the concentrations 4 g per liter. In these treatment baths, cotton calico is dipped in the ratio 1:20 in the cold state, extruded to 100% and dried. This treated material is protected against the formation of mold flakes and decay. The results of the test, carried out as described in Example 1, are shown in Table.

— — Tabell. - - Chart.

Provningsresultat, exempel 1-12. „;;,eiilackspro_ Forrutt- Jordned- Halt "'nelse- gravnings- p Antal svam- beh.-prov/ge- prov/ge- Substanskolonier badetnomslags- nomslags- glitter Pen. Stach. Asp. exp.a.n. hall- fasthet hall- fasthet EX. 1 1 0 0 0 99% 100% Ex. 2 1 0 0 0 97% 97% Ex. 3 Subst. a 1 0 0 0 97 % 96 % b 0 0 0 100% 97% Ex. 4 1 0 0 0 86% 97% Ex. Test results, examples 1-12. „;;, eiilackspro_ Forrutt- Jordned- Halt" 'nelse- gravnings- p Antal svam- beh.-prov / ge- prov / ge- Substanskolonier badetnomslags- nomslags- glitter Pen. Stach. Asp. Exp.an hall- fasthet hall - strength EX 1 1 0 0 0 99% 100% Ex 2 1 0 0 0 97% 97% Ex 3 Substance a 1 0 0 0 97% 96% b 0 0 0 100% 97% Ex 4 1 0 0 0 86% 97% Ex.

Subst. a 4 0 0 0 100% 98 % b 0 0 0 99% 98% Ex. 6 Subst. a 4 0 0 0 100 % 100 % b 8 0 0 0 100% 96% »c 0 0 0 96% 94% Ex. 7 4 0 0 0 100% 97% Ex. 8 1 0 0 0 100% Ex. 9 Subst. a 9 0 0 0 100% »b 9 0 0 0 100% Ex. 2,0 0 0 100% Ex. 11 Subst. a 0 0 0 100 % 98 % b 0 0 0 100% 86% Ex. 12 Subst. a 4 0 0 0 98 % 95 % b 4 0 0 0 96% 97% Blindprov 0 co a) co 3 % 7 % Exempel 13. Till ett kolofoniumlim med 10 % torrsubstans sattas 0,5 % av totalvikten 5,6-diklor-2,3-dihydrubensoxazol-2-on respektive 4,5,7- triklor-2,3-dihydrobensoxazol-2-on. Med detta lim limmas filtrerpapper pa ytan pa sâ sat, att 2 % av papperets totalvikt efter torkning bestar av kolofoniumlimmets torrvikt. Det fardiga papperet innehaller saledes 0,04 % verksam substans och Sr tack vare denna halt skyddad mot bildning av mogelflackar och mogling. For provning laggas runda stycken av detta papper med en diameter av 9 cm i en petriskal pa olvortsagar och ympas i mitten med Trichoderma viride, Aspergillus niger, Fusarium oxysporum respektive Penicillium expansium och odlas 5 dygn vid 28'. Na mattes ympstallenas utbredning i mm. Alla fOrsok genomfordes som dubbelprov. Subst. a 4 0 0 0 100% 98% b 0 0 0 99% 98% Ex. 6 Subst. a 4 0 0 0 100% 100% b 8 0 0 0 100% 96% »c 0 0 0 96% 94% Ex. 7 4 0 0 0 100% 97% Ex. 8 1 0 0 0 100% Ex. 9 Subst. a 9 0 0 0 100% »b 9 0 0 0 100% Ex. 2.0 0 0 100% Ex. 11 Subst. a 0 0 0 100% 98% b 0 0 0 100% 86% Ex. 12 Subst. a 4 0 0 0 98% 95% b 4 0 0 0 96% 97% Blind sample 0 co a) co 3% 7% Example 13. To a rosin adhesive with 10% dry matter is added 0.5% of the total weight of 5,6-dichloro -2,3-dihydrubenzoxazol-2-one and 4,5,7-trichloro-2,3-dihydrobenzoxazol-2-one, respectively. With this glue, filter paper is glued to the surface in such a way that 2% of the total weight of the paper after drying consists of the dry weight of the rosin glue. The finished paper thus contains 0.04% of active substance and Sr thanks to this content is protected against the formation of mold flakes and molding. For testing, round pieces of this 9 cm diameter paper are placed in a petri dish on olive saws and inoculated in the middle with Trichoderma viride, Aspergillus niger, Fusarium oxysporum and Penicillium expansium respectively and grown for 5 days at 28 '. Now the distribution of the inputs in mm. All tests were performed as a duplicate test.

FOljande resultat erholls: Tricho- derma Asper- gillus Fu- sarium hum 1. 2. 1.2. 1. 2. 1. 2. The following result was obtained: Trichoderma Aspergillus Fusarium hum 1. 2. 1.2. 1. 2. 1. 2.

Utan 26 22 17 17 9 5,6-diklor- -2,3-dihydro-bensoxaz ol- -2-on 0 0 0 0 0 0 0 0 4,5,7-triklor- -2,3-dihydro-bensoxazol- -2-on 0 0 0 0 0 0 0 0 Exempel 14. I skokram inarbetades 1 % 5,6- -diklor- eller 4,5,7-triklor-2,3-dihydroxazol-2-on. Om lader behandlas med denna skokram,ar det skyddat mot mogling. Without 26 22 17 17 9 5,6-dichloro--2,3-dihydro-benzoxazol--2-one 0 0 0 0 0 0 0 0 4,5,7-trichloro-2,3-dihydro-benzoxazole -2-one 0 0 0 0 0 0 0 0 0 Example 14. 1% of 5,6--dichloro- or 4,5,7-trichloro-2,3-dihydroxazol-2-one were incorporated into the shoe frame. If the drawer is treated with this shoe frame, it is protected against mold.

For prOvning av denna egenskap hos den nya skokramen anvandes cirkelrunda laderstycken av ostindiskt getskinn vegetabiliskt garvat med sumakextrakt. Be hade en diameter av 3,8 cm och vagde 400 mg. Sasom pastrykning anvandes 100 mg, vilket, raknat pt ladervikten, motsvarar 2,5 % verksam substans. De sa beredda laderstyckena ympades, sasom beskrivits i exempel 11, odlades och uppmattes. Alla forsoken utfOrdes sasom dubbelprov. To test this property of the new shoe frame, circular loader pieces of East Indian goatskin were used vegetable tanned with suma extract. Be had a diameter of 3.8 cm and weighed 400 mg. As paste paste, 100 mg was used, which, based on the charge weight, corresponds to 2.5% of active substance. The thus prepared loader pieces were inoculated, as described in Example 11, cultured and measured. All experiments were performed as duplicate.

Foljande resultat erhollos: Tillsats Tricho- derma Fusa- rium Peniell- hum Asper- gnus I. 2. 1. 2. 1. 2. 1. 2. The following results were obtained: Additive Trichoderma Fusarium Peniell- hum Asper- gnus I. 2. 1. 2. 1. 2. 1. 2.

Utan 38 38 5,6-diklor- -2,3-dihydro-bensoxazol- -2-on 0 0 0 0 0 0 4,5,7-triklor- -2,3-dihydro-bensoxazol- -2-on 3 2 0 0 0 0 3 0 Exempel 15. 1-procentiga bensenlOsningar av5,6-diklor-2,3-dihydrobensoxazol-2-on respektive 4,5,6-triklor-2,3-dihydrobensoxazol-2-on blandades med latex i forhallandet 1: 9, och dessa blandningar halides ut pa glasplattor. Efter torkning bildas pa sa satt latexskikt, som innehalla cirka 1 % verksam substans. Tack vare denna halt aro de skyddade mot mogling. FOr provning av denna egenskap ympas dc med sporsuspensioner av Stemphylium botryosum, Penicillium solitum, Aspergillus niger respektive Trichoderma viride. Mediet for sporsuspensionerna Sr en mineralsaltlosning. De ympade latexplattorna fiirvaras 14 dygn i fuktiga rum vid 28°. Na faststalles, om organismer kunde och vilka som kande utveckla sig. Without 38 38 5,6-dichloro--2,3-dihydro-benzoxazol--2-one 0 0 0 0 0 0 4,5,7-trichloro-2,3-dihydro-benzoxazol--2-one 3 Example 15. 1% benzene solutions of 5,6-dichloro-2,3-dihydrobenzoxazol-2-one and 4,5,6-trichloro-2,3-dihydrobenzoxazol-2-one, respectively, were mixed with latex in the ratio 1: 9, and these mixtures are halied out on glass plates. After drying, latex layers are formed, which contain about 1% of active substance. Thanks to this content, they are protected against ripening. To test this property, inoculate dc with spore suspensions of Stemphylium botryosum, Penicillium solitum, Aspergillus niger and Trichoderma viride respectively. The medium for the spore suspensions is a mineral salt solution. The grafted latex plates are stored for 14 days in humid rooms at 28 °. It is determined whether organisms could and which ones could develop.

Tillsats p hSyt lelmi cPi 1 el it A sPerg' Trichoderma Utan +--H +++ 5,6-diklor-2,3-di-hydrobensoxazol- -2-on 0 0 0 0 4,5,7-triklor-2,3- -dihydrobensoxa - zol-2-on 0 0 0 0 0 Icke nagon tillvaxt ±± mattlig ±± stark Exempel 16. Skydd av polyvinylkloridfolier mot svampangrepp med anvandning av 5,6-diklor-2,3-dihydrobensoxazol-2-on sasom fungistatiskt medel. Additive to hSyt lelmi cPi 1 el it A sPerg 'Trichoderma Utan + - H +++ 5,6-dichloro-2,3-di-hydrobenzoxazol--2-one 0 0 0 0 4,5,7-trichloro- 2,3- -dihydrobenzoxa - zol-2-one 0 0 0 0 0 No growth ± ± matt ± ± strong Example 16. Protection of polyvinyl chloride films against fungal attack using 5,6-dichloro-2,3-dihydrobenzoxazol-2 -on as a fungistatic agent.

Folier med foljande sammansattning anvdndes: 7delar polyvinylklorid med ett K-varde enligt Sikentscher av 70 till 72 — — 25 delar dioktylsebakat (sasom mjukningsmedel) 2 delar dibutyltennlaurat 0,1 delar 5,6-diklor-2,3-dihydrobensoxazol-2-on. Films with the following composition were used: 7 parts polyvinyl chloride with a K-value according to Sikentscher of 70 to 72 - - 25 parts dioctyl sebacate (as plasticizer) 2 parts dibutyltin laurate 0.1 parts 5,6-dichloro-2,3-dihydrobenzoxazol-2-one .

Sasom jamforelse tjanade lika sammansatta folier men utan tillsats av 5,6-diklor-2,3-dihydrobensoxazol-2-on. Folietjockleken uppgick till 0,2 mm, Verkan av del fungistatiska medlet faststalldes i foljande forsok: Polyvinylkloridfolier (1 x 3 cm) doppades 10 minuter vid 30° i en 1-procentig losning av kondensationsprodukten av diamylfenol och 15 mol etylenoxid i vatten och lades nu 2 timmar pa i forvag odlad mineralsaltagar med sammansattningen 2,0 g NaNG, 0,5 g KC1 0,5 g MgS0, 0,05 g FeSO, 1,0 g KH,P0, 0,05 g MnSO, 30,0 g agar Tillsats Aspergillus utan + 6,25° = 58% med —9,25° = 100% = bevuxen — = joke bevuxen Utskurna polyvinylkloridfoliestycken nedgravdes 30 dygn vid 28° i en jordblandning, som hade en fuktighetshalt av 30 % och bestod av 50 % kompost, 30 % kogodsel och 20 % sand. Folierna provades nu pa bbjhallfasthet, sasom beskrivits under 1. Foljande resultat erholls: Utan tillsats 2,125° = 19 % Med tillsats 8,25° = 92 % As a comparison, equally complex films served without the addition of 5,6-dichloro-2,3-dihydrobenzoxazol-2-one. The foil thickness was 0.2 mm. The effect of some of the fungistatic agent was determined in the following experiment: Polyvinyl chloride films (1 x 3 cm) were dipped for 10 minutes at 30 ° in a 1% solution of the condensation product of diamylphenol and 15 moles of ethylene oxide in water and now added 2 hours pa in pre-grown mineral salt agar with the composition 2.0 g NaNG, 0.5 g KCl 0.5 g MgSO 4, 0.05 g FeSO, 1.0 g KH, PO, 0.05 g MnSO 4, 30.0 g agar Additive Aspergillus without + 6.25 ° = 58% with -9.25 ° = 100% = overgrown - = joke overgrown Cut polyvinyl chloride foil pieces were buried for 30 days at 28 ° in a soil mixture with a moisture content of 30% and consisted of 50 % compost, 30% cow manure and 20% sand. The films were now tested for adhesive strength, as described in 1. The following results were obtained: Without addition 2.125 ° = 19% With addition 8.25 ° = 92%

Claims

Patentanspr

1. A process for the protection of organic material against mold and decay, characterized in that benzazole compounds of the general formula are used as protective agents up to 1000 g with distilled water, pH 6.2-6.5, which was inoculated with Aspergillus niger EMPA, Penicillium citrinum and Pseudomomas pyocyanea, respectively. The films were now grown for 10 days at 28 °, rinsed with distilled water at 30 ° and dried for 4 days in a conditioned room (24 °, 60% relative humidity). On the material thus treated, the buoyancy strength was determined as follows: The foils were clamped in one narrow duct and loaded for 15 seconds in the other duct with g. This bending served as starting position (a). The foils now relieved and the stall was determined again after 15 seconds of unloading (b). The differences between the two angular positions (a — b) are referred to as bialloic strength and are given in angular degrees. By being overgrown with microorganisms, the buoyancy strength is lost as a result of fungal attack on the plasticizer. The non-grafted new foils have a buoyancy strength of 9.25 ° = - 100%. For the 5,6-dichloro-2,3-dihydrobenzoxazol-2-one protected and comparative films, Milo's results are as follows: Penicillium Pseudomonas + 6.75 ° = 63% ± 7.25 ° = 78% -9.0 ° = 98% —8.75 ° = 95% / \, NH \ (Hal). CYX / van in either of X and Y represents a divalent oxygen atom, the other a divalent oxygen or sulfur atom, Hal denotes halogen and n an integer from 1 to 2. 3. Process according to claim 1, characterized in & ray, that the halogen in the preservative is of chlorine. 4. A method according to claim 1 or 2, characterized in that n in the general formula has

2. Request publications: Patent patent ter! Ran U. S. A. 1 962 109, 2 724 678. Stockholm 1961. Hungi. Boktr. P. A. Norstedt &: Soner. 010089