NO800302L - DILUTABLE BENZIMIDAZOLCARBAMIC ACID COOLESTER FORMULATION, PROCEDURE FOR THEIR PREPARATION AND THEIR USE AS BIOZIDE - Google Patents

DILUTABLE BENZIMIDAZOLCARBAMIC ACID COOLESTER FORMULATION, PROCEDURE FOR THEIR PREPARATION AND THEIR USE AS BIOZIDE

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Publication number
NO800302L
NO800302L NO800302A NO800302A NO800302L NO 800302 L NO800302 L NO 800302L NO 800302 A NO800302 A NO 800302A NO 800302 A NO800302 A NO 800302A NO 800302 L NO800302 L NO 800302L
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Norway
Prior art keywords
carbon atoms
formulation
carbamic acid
molar amount
acid alkyl
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Application number
NO800302A
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Norwegian (no)
Inventor
Hans Gattner
Karl Wagner
Original Assignee
Riedel De Haen Ag
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Publication date
Application filed by Riedel De Haen Ag filed Critical Riedel De Haen Ag
Publication of NO800302L publication Critical patent/NO800302L/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D235/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings
    • C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
    • C07D235/04—Benzimidazoles; Hydrogenated benzimidazoles
    • C07D235/24—Benzimidazoles; Hydrogenated benzimidazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2
    • C07D235/30—Nitrogen atoms not forming part of a nitro radical
    • C07D235/32—Benzimidazole-2-carbamic acids, unsubstituted or substituted; Esters thereof; Thio-analogues thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/18—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, directly attached to a heterocyclic or cycloaliphatic ring
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
    • B27K3/34—Organic impregnating agents
    • B27K3/343—Heterocyclic compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
    • B27K3/34—Organic impregnating agents
    • B27K3/38—Aromatic compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
    • B27K3/34—Organic impregnating agents
    • B27K3/50—Mixtures of different organic impregnating agents

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  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Plant Pathology (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Plural Heterocyclic Compounds (AREA)

Abstract

For the Contracting States : CH, DE, FR, GB, NL, SE 1. Dilutable benzimidazole carbamic acid alkyl ester formulation, obtainable by chemical reaction of a benzimidazole carbamic acid alkyl ester of the general formula (I) see diagramm : EP0014443,P8,F1 wherein R means a lower alkyl group with at least twice molar amount of an aliphatic mono- or dialdehyde having 1 to 10 carbon atoms or benzaldehyde in the presence of at least the twice molar amount of a primary, secondary or tertiary alcohol having 1 to 18 carbon atoms. For the Contracting State AT 1. Process for the manufacture of a dilutable benzimidazole carbamic acid alkyl ester formulation, characterized in that a benzimidazole carbamic acid alkyl ester of the formula (I) see diagramm : EP0014443,P8,F1 wherein R means a lower alkyl group is suspended in at least the twice molar amount of a primary, secondary or tertiary alcohol having 1 to 18 carton carbon atoms, is treated with at least the twice molar amount of an aliphatic mono- or dialdehyde alcohol having 1 to 10 carbon atoms or benzaldehyde under permanent agitation at 40 to 150 degrees C, and is kept at this temperature to complete dissolution.

Description

Oppfinnelsen vedrører en fortynnbar benzimidazolkarbaminsyrealkylesterformulering, en fremgangsmåte til dens fremstilling og dens anvendelse som biozid. The invention relates to a dilutable benzimidazole carbamic acid alkyl ester formulation, a method for its preparation and its use as a biocide.

Benzimidazolkarbaminsyrealkylester, i det følgende betegnet med BCAE, er kjent som fungicider for plantebeskyttelse og for beskyttelse av tekniske materialer mot mikrobiell Benzimidazole carbamic acid alkyl esters, hereinafter denoted by BCAE, are known as fungicides for plant protection and for the protection of technical materials against microbial

.nedbrytning..decomposition.

Deres anvendelse begrenses-imidlertid sterkt, ved den omstendighet at de er praktisk talt uoppløselige i vann og i de vanlige oppløsningsmidler. Por å fjerne denne ulempe ble det foreslått å anvende BCAE til bekjempelse av soppan-grep på levende planter i meget finfordelt form, dvs. en par-tikkelstørrelse på 5 ym (DE-OS 16 20 175), fordi partikler Their use is, however, severely limited by the fact that they are practically insoluble in water and in the usual solvents. In order to remove this disadvantage, it was proposed to use BCAE to combat fungal attacks on living plants in very finely divided form, i.e. a particle size of 5 ym (DE-OS 16 20 175), because particles

av denne størrelsesorden.henger'ved overflaten av plante-deler. En inntrengning av faste partikler i overflaten av materialer som skal behandles er imidlertid ikke å vente, således at den fastslåtte ulempe(ikke fjernes ved den fore-slåtte forhåndsregel. of this order of magnitude. hangs on the surface of plant parts. Penetration of solid particles into the surface of materials to be treated is not to be expected, however, so that the established disadvantage is not removed by the proposed advance rule.

Det forelå derfor den oppgave å tilveiebringeThere was therefore the task of providing

en BCAE-holdig formulering som er fortynnbar.a BCAE-containing formulation that is dilutable.

For lø.sning av denne oppgave ble det forsøkt å oppløseliggjøre BCAE ved innbygning av substituenter, To solve this problem, an attempt was made to solubilize BCAE by incorporating substituents,

f.eks. ved omsetning med isocyanater til 1-karbamoyl-BCAE-derivater (DE-OS 17 45 784). Disse karbamoylderivater har riktignok lignende gunstig virkningsspektrum som BCAE, adskiller seg imidlertid også bare litt i oppløs.elighetsf or-hold. e.g. by reaction with isocyanates to 1-carbamoyl-BCAE derivatives (DE-OS 17 45 784). Although these carbamoyl derivatives have a similar beneficial spectrum of action as BCAE, they also only differ slightly in terms of solubility.

Andre derivater er 1-aminometyl-BCAE-derivater (DE-OS 22 30 l82), som imidlertid i oppløsningsmidler ikke Other derivatives are 1-aminomethyl-BCAE derivatives (DE-OS 22 30 l82), which, however, in solvents do not

gir noen stabile oppløsninger og som tenderer til dissosia-sjon i utgangskomponentene. gives some stable solutions and which tend to dissociate into the starting components.

Det samme gjelder for 2-triazino-benzimidazolerThe same applies to 2-triazino-benzimidazoles

som oppstar ved reaksjon av BCAE med et primært amin og den dobbelte molare mengde formaldehyd (DE-OS 22 24 244). which arises from the reaction of BCAE with a primary amine and the double molar amount of formaldehyde (DE-OS 22 24 244).

Vesentlig bedre oppløselig i polare oppløsnings-midler er salter av BCAE med sterke syrer (DE-OS 17 92 688). Disse produkter anvendes derfor også i trebeskyttelse som middel mot sopp som gir tre en blåfarge. De har imidlertid'' den ulempe at de i formuleringer som inneholder upolare opp-løsningsmidler som f.eks. prøvebensin, tenderer til utfelling av de virksomme stoffer. Videre er de meget følsomme ovenfor hydrolyse. Allerede'små vannspor fører til utfelling av det tungt oppløselige BCAE-legemet. Salts of BCAE with strong acids are substantially more soluble in polar solvents (DE-OS 17 92 688). These products are therefore also used in wood protection as an agent against fungi that give wood a blue colour. However, they have the disadvantage that in formulations containing non-polar solvents such as e.g. test petrol, tends to precipitate the active substances. Furthermore, they are very sensitive to hydrolysis. Even small traces of water lead to precipitation of the poorly soluble BCAE body.

Oppfinnelsen vedrører nå en fortynnbar BCAE-formulering som er oppnåelig ved omsetning av en benzimidazolkarbå-minsyrealkylester"(BCAE) med den generelle formel (1) The invention now relates to a dilutable BCAE formulation which is obtainable by reacting a benzimidazole carboamic acid alkyl ester"(BCAE) with the general formula (1)

hvori R betyr en lavere alkylgruppe med minst den dobbelt molare mengde av et aldehyd med 1-10 karbonatomer i nærvær av minst den dobbe.lt molare mengde av en hydroksylgruppeholdig forbindelse.. Symbolet R betyr fortrinnsvis en alkylgruppe med 1-4 karbonatomer. wherein R means a lower alkyl group with at least twice the molar amount of an aldehyde with 1-10 carbon atoms in the presence of at least twice the molar amount of a hydroxyl group-containing compound. The symbol R preferably means an alkyl group with 1-4 carbon atoms.

BCAE-formuleringene ifølge, oppfinnelsen er produkter som er stabile i oppløsning. De har dessuten, videre fordeler: a) BCAE-formuleringene ifølge oppfinnelsen er godt forenlig med trebeskyttelsesmiddelformuleringer på basis; av up oiar e__„ oppløsningsmidler, f. e.ks . prøvebensin. Riktignok kan også forbindelser i henhold til teknikkens stand, f.eks. BCAE-n-dodecylbenzolsulfonat oppløst i etylglykol og tilsettes trebeskyttelsesmiddelformuleringer på basis av upolare oppløsningsmidler imidlertid adskiller det seg hyppig i løpet av noen uker en bunnavsetning av BCAE, hvorved virkningen av trebeskyttelsesmidlet mot The BCAE formulations according to the invention are products which are stable in solution. They also have further advantages: a) the BCAE formulations according to the invention are well compatible with base wood preservative formulations; of up oiar e__„ solvents, e.g. test fuel. Admittedly, connections according to the state of the art, e.g. BCAE-n-dodecylbenzenesulfonate dissolved in ethyl glycol and added to wood preservative formulations based on non-polar solvents, however, a bottom deposit of BCAE often separates within a few weeks, whereby the effect of the wood preservative against

blåsopp påvirkes.blue fungus is affected.

b) Videre har trebeskyttelsesformuleringer som inneholder BCAE-formuleringene ifølge oppfinnelsen inntrengnings- dybder i tre på .flere milimeter som ikke oppnås med BCAE-forbindelser i henhold til teknikkens stand, b) Furthermore, wood protection formulations containing the BCAE formulations according to the invention have penetration depths in wood of several millimeters which are not achieved with BCAE compounds according to the state of the art,

c) Dessuten lar det seg med BCAE-formuleringene ifølge oppfinnelsen fremstille kombinerte tr.ebeskyttelsesmidler i c) In addition, it is possible with the BCAE formulations according to the invention to produce combined wood preservatives i

oppløsningsform som virker så vel mot treødeleggende sopp og treødeleggende insekter som også mot blåsopp, f.eks. et flytende virksomt stoffkonsentrat med f.eks. tributyl-innoksyd mot treødeleggende sopp-og f.eks. endosulfan mot treødeleggende insekter. Det er ikke mulig med BCAE-for-bindelsene i henhold til teknikkens stand. solution form that works as well against wood-destroying fungi and wood-destroying insects as also against blue fungus, e.g. a liquid active substance concentrate with e.g. tributyl inoxide against wood-destroying fungi and e.g. endosulfan against wood-destroying insects. It is not possible with the BCAE connections according to the state of the art.

Benzimidazolkarbaminsyrealkylestere står til disposisjon som handelsprodukter. De er fremstillbare f.eks. ifølge.cyana-midfremgangsmåten (De-OS 16 68 557 )• For oppfinnelsen egner det seg fortrinnsvis BCAE-forbindelser med 1-4 karbonatomer i alkylgruppen. Spesielt kommer det i betraktning benzimidazolkarbaminsyremetylestere (.BCM). Benzimidazole carbamic acid alkyl esters are available as commercial products. They can be produced e.g. according to the cyanamide method (De-OS 16 68 557 )• BCAE compounds with 1-4 carbon atoms in the alkyl group are preferably suitable for the invention. In particular, benzimidazole carbamic acid methyl esters (.BCM) come into consideration.

Som aldehyder med 1-10 karbonatomer egner det seg spesielt alifatiske mono- eller dialdehyder med fortrinnsvis 1-5 karbonatomer, f.eks. formaldehyd, paraformaldehyd, acetaldehyd, propionaldehyd, glutardialdehyd, gly-oksal, glyoksylsyre og acrolin samt benzaldehyd. Aliphatic mono- or dialdehydes with preferably 1-5 carbon atoms are particularly suitable as aldehydes with 1-10 carbon atoms, e.g. formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde, glutardialdehyde, glyoxal, glyoxylic acid and acrolin as well as benzaldehyde.

Som hydroksylgruppeholdige forbindelser kommer det.i betraktning alkanoler med 1-18 karbonatomer, fortrinnsvis 1-10 karbonatomer, glykoler, glykoletere og polyalkoksylerte- alkyl.fenoler. Det er spesielt egnet rettlinjede eller forgrenede, primære, sekundære eller tertiære alkoholer Examples of hydroxyl group-containing compounds include alkanols with 1-18 carbon atoms, preferably 1-10 carbon atoms, glycols, glycol ethers and polyalkylated alkyl phenols. Straight or branched, primary, secondary or tertiary alcohols are particularly suitable

med 1-18 karbonatomer, f.eks. metanol., etanol, propanol, isopropanol, butanol, isobutanol, 3-metylbutanol- 2-etyl-.heksanol, isoamylalkohol, isodecylalkohol, isotridecylalko-hol, isooktadecylalkohol, 3-metoksybutanol, 4-metyl-4^hy-droksy-pentanon-(2)- og glykolsyre-n-butylester, videre glykoler, f.eks. etylenglykol, glycerin, dietylenglykol og trietylenglykol, samt glykoletere, f.eks. metylglykol, etylglykol, butylglykol, metyldiglykol, etyldiglykol og butyldiglykol, og også polyalkoksylerte produkter av alkyl-erte fenoler og etylenoksyd eller propylenoksyd, f.eks. omsetningsproduktet av nonylfenol og 10 ekvivalenter etylen-'oksyd. with 1-18 carbon atoms, e.g. methanol., ethanol, propanol, isopropanol, butanol, isobutanol, 3-methylbutanol- 2-ethyl-.hexanol, isoamyl alcohol, isodecyl alcohol, isotridecyl alcohol, iso-octadecyl alcohol, 3-methoxybutanol, 4-methyl-4^hydroxy-pentanone- (2)- and glycolic acid n-butyl ester, further glycols, e.g. ethylene glycol, glycerin, diethylene glycol and triethylene glycol, as well as glycol ethers, e.g. methylglycol, ethylglycol, butylglycol, methyldiglycol, ethyldiglycol and butyldiglycol, and also polyalkylated products of alkylated phenols and ethylene oxide or propylene oxide, e.g. the reaction product of nonylphenol and 10 equivalents of ethylene oxide.

Valget av den anvendte hydroksylgruppeholdige forbindelse retter seg etter det foreskrevne anvendelsesformål. Formuleringer som skal anvendes i systemer som inneholder upolare oppløsningsmidler, f.eks. bensin, fremstilles fortrinnsvis på basis av butylglykol. For formuleringer som skal være vannoppløselige er det_som J^yjiroksylgruppeholdige forbindelser, bedre egnet^metylgiykpl^pg^etylglykoj^.; Også polyglykoleter-forbindels"er lar seg anvende med fordel. Således er formuleringen av BCAE, formaldehyd og- et handelsvanlig omsetnings-'produkt av nonylfenol og 10 mol etylenoksyd meget godt egnet til å fremstille vandige dispersjoner. The choice of the hydroxyl group-containing compound used depends on the prescribed purpose of use. Formulations to be used in systems containing non-polar solvents, e.g. petrol, is preferably produced on the basis of butyl glycol. For formulations that are to be water-soluble, it is_like J^yjiroxyl group-containing compounds, better suited^methylgyykpl^pg^ethylglycoj^.; Polyglycol ether compounds can also be used with advantage. Thus, the formulation of BCAE, formaldehyde and a commercially available reaction product of nonylphenol and 10 mol of ethylene oxide is very well suited to preparing aqueous dispersions.

Fortrinnsvis anvendes bare et aldehyd og barePreferably only one aldehyde is used and only

en hydroksylgruppeholdig forbindelse fra de angitte grupper. a hydroxyl group-containing compound from the indicated groups.

Man kan imidlertid også anvende blandinger avHowever, it is also possible to use mixtures of

• to aldehyder eller av to hydroksylgruppeholdige forbindelser. Fortrinnsvis anvendes et større overskudd aldehyd og/eller • two aldehydes or of two compounds containing hydroxyl groups. A larger excess of aldehyde and/or is preferably used

av den hydroksylgruppeholdige forbindelse.of the hydroxyl group-containing compound.

Det er derfor foretrukket formuleringer hvor mengden av forbindelse (1) utgjør 10-20 vekt-% av den sam- Formulations are therefore preferred where the amount of compound (1) constitutes 10-20% by weight of the combined

lede reaksjonsblanding.conduct reaction mixture.

Ved fremstillingen av formuleringen ifølge oppfinnelsen må det påsees at denne foretas hurtigst mulig og ved ikke for høye temperaturer.. Ellers vil virkningen' lide. When preparing the formulation according to the invention, it must be ensured that this is carried out as quickly as possible and at temperatures that are not too high. Otherwise, the effect will suffer.

Formuleringene ifølge oppfinnelsen lar seg fremstille etter en fremgangsmåte hvor BCAE med den generelle formel (1) suspenderes i minst den dobbelt molare mengde av minst en hydroksylgruppeholdig forbindelse, blandes under stadig bevegelse ved 40-150°C, fortrinnsvis 8b-110°C, The formulations according to the invention can be prepared according to a method where BCAE with the general formula (1) is suspended in at least twice the molar amount of at least one hydroxyl group-containing compound, mixed under constant stirring at 40-150°C, preferably 8b-110°C,

med minst den dobbelt -molare mengde av minst ett aldehyd med 1-10 karbonatomer og holdes til fullstendig oppløsning ved denne temperatur. Bevegelsen og gjennomblandingen av reaksjonsdeltagerene gjennomføres fortrinnsvis ved røring eller også rysting. with at least the double-molar amount of at least one aldehyde with 1-10 carbon atoms and kept until complete dissolution at this temperature. The movement and thorough mixing of the reaction participants is preferably carried out by stirring or shaking.

Det anvendte BCAE bør for oppnåelse av en kort omsetningstid være mest mulig findelt. Fortrinnsvis anven- In order to achieve a short turnover time, the BCAE used should be as finely divided as possible. Preferably use

des produkter med en gjennomsnittelig kornstørrelse frades products with an average grain size from

2-10 ym. Gassformede og sterkt gassende, flytende reaksjons-deltagere kan med et dypperør innføres i reaksjonsblandingen. 2-10 etc. Gaseous and strongly gassing, liquid reaction participants can be introduced into the reaction mixture with a dip tube.

Formuleringene ifølge oppfinnelsen anvendes som biozider i plantebeskyttelse og til beskyttelse av tekniske materialer mot mikrobiell nedbrytning. De anvendes direkte eller i oppløsningsmiddelholdige eller vandige plantebeskytt- . elsesmidler eller konserveringsmidler. Spesielt egner de seg til å-forebygge eller behandling_av muggsoppangrep på tekstiler, lær og papir og i påstrykningsmidler og andre be-legningsmidler. The formulations according to the invention are used as biocides in plant protection and for the protection of technical materials against microbial degradation. They are used directly or in solvent-based or water-based plant protection products. additives or preservatives. In particular, they are suitable for preventing or treating mold attacks on textiles, leather and paper and in iron-on agents and other coating agents.

For disse anvendelsesformål kan de benyttes i kombinasjon med andre fungizider og med bakterizider eller algizider. Hertil kommer f.eks. på tale: tinnorganiske forbindelser, ditiokarbamater, isotiazoloner, benzisotia-zol-3-on, heksahydrotriazin, kloracetamid, N-triklormetyl-tiotetrahydroftalimid (kaptan), N-triklormetyltioftalimid (folpet), fluorfolpet, 3"(3',4'-diklorfényl)-l,1-dimetyl-. urinstoff (diuron), pentaklornitr'6benzol (folsan), 1-n-butyl-aminokarbonyl-2-metoksykarbonylaminobenzimidazol og N-diklorfluormetyltio-N',N'-dimetylaminosulfonsyreanilid. For these application purposes, they can be used in combination with other fungicides and with bactericides or algicides. In addition, e.g. in question: organotin compounds, dithiocarbamates, isothiazolones, benzisothiazol-3-one, hexahydrotriazine, chloroacetamide, N-trichloromethyl-thiotetrahydrophthalimide (captan), N-trichloromethylthiophthalimide (folpet), fluorofolpet, 3"(3',4'-dichlorophenyl )-1,1-dimethyl-.urea (diuron), pentachloronitro-6benzene (folsan), 1-n-butyl-aminocarbonyl-2-methoxycarbonylaminobenzimidazole and N-dichlorofluoromethylthio-N',N'-dimethylaminosulfonic acid anilide.

Som anvendelsesmengder kommer det i betraktning 0,001-15 vekt-%, fortrinnsvis 0,3_5 vekt-% av formuleringen ifølge oppfinnelsen, eventuelt i blanding med andre virksomme stoffer (referert til mengden av påstryknings- eller belegningsmiddel som skal utrustes med biozid). Amounts to be used are 0.001-15% by weight, preferably 0.3-5% by weight, of the formulation according to the invention, possibly in admixture with other active substances (referred to the amount of coating or coating agent to be equipped with biocide).

Oppfinnelsen skal forklares ved hjelp av noen eksempler, hvor prosentangivelsene refererer seg til vekt. Eksemp_el_l The invention will be explained with the help of some examples, where the percentages refer to weight. Example_el_l

100 g (0,524 mol) benzimidazolkarbaminsyremetylester (BCM) 100 g (0.524 mol) benzimidazole carbamic acid methyl ester (BCM)

og and

200 g _( 6,667_mol) ;paraformaldehyd innføres under omrøring i 700 g (5,932 mol) butylglykol og oppvarmes til 100°C. Etter ca. 1 time er.det dannet en klar oppløs-ning. 200 g _(6.667_mol) paraformaldehyde is introduced with stirring into 700 g (5.932 mol) butyl glycol and heated to 100°C. After approx. After 1 hour, a clear solution was formed.

Eksempel_2Example_2

200 g (1,047 mol) BCM og200 g (1.047 mol) BCM and

200 g (6,667 mol) paraformaldehyd innføres under omrøring i 200 g (6.667 mol) of paraformaldehyde are introduced with stirring in

600 g (5,085 mol) butylglykol og oppvarmes til 100°C. Etter 600 g (5.085 mol) butyl glycol and heated to 100°C. After

ca. 1 time har de faste stoffer oppløst seg. about. After 1 hour, the solids have dissolved.

Eksemp_el_3Example_el_3

200 g (1,047 mol) BCM og200 g (1.047 mol) BCM and

320 g (10,667 mol) paraformaldehyd innføres under omrøring i 480 g (4,068 mol) butylglykol og oppvarmes til 90°C. Etter 320 g (10.667 mol) of paraformaldehyde are introduced with stirring into 480 g (4.068 mol) of butyl glycol and heated to 90°C. After

ca. 1 time har alt oppløst seg. about. 1 hour everything has dissolved.

Eksemp_el_4Example_el_4

200 g .(1,047 mol) BCM og200 g .(1.047 mol) BCM and

24 0 g (8,000 mol) paraformaldehyd innføres under omrøring i 560 g (4,746"mol) butylglykol og oppvarmes til 105°C Etter 50 minutter er de faste stoffer gått i 240 g (8,000 mol) of paraformaldehyde is introduced with stirring into 560 g (4,746" mol) of butyl glycol and heated to 105°C. After 50 minutes, the solids have gone into

oppløsning.resolution.

. De ifølge eksemplene 1-4 dannede formuleringer lar seg hver gang fortynne med 500 g prøvebensin uten at det inntrer noen utfelling.Eksemgel_5 ■ . ' , > . The formulations formed according to examples 1-4 can each be diluted with 500 g of test petrol without any precipitation occurring.Example_5 ■ . ' , >

154 kg av et nutsjfuktig produkt av en teknisk 154 kg of a nut-moist product of a technical

blanding tilsvarenedemixture equivalents

100,1 kg (0,524 kmol) BCM og100.1 kg (0.524 kmol) BCM and

50,05 kg (0,833 kmol) isopropanol og50.05 kg (0.833 kmol) isopropanol and

3,85 kg (0,214 kmol) vann innføres under omrøring i3.85 kg (0.214 kmol) of water are introduced while stirring i

646 kg (5,475 kmol) butylglykol.646 kg (5.475 kmol) of butyl glycol.

Etter tilsetning avAfter the addition of

200 kg (6,667 kmol) paraformaldehyd oppvarmes under omrør-ing ved 100°C. Etter forløp av 1 time har alt oppløst seg. 200 kg (6.667 kmol) of paraformaldehyde is heated with stirring at 100°C. After 1 hour everything has dissolved.

Eksempel_6Example_6

100 g (0,524 mol) BCM og100 g (0.524 mol) BCM and

200 g (6,667 mol) paraformaldehyd innføres under omrøring i 540 g (6,000 mol) etylglykol og oppvarmes til 100°C. Etter 200 g (6.667 mol) of paraformaldehyde are introduced with stirring into 540 g (6.000 mol) of ethyl glycol and heated to 100°C. After

70 minutter er oppløsning inntrådt. Eksemp_el_2 After 70 minutes, resolution has occurred. Example_el_2

100 g (0,524 mol) BCM og100 g (0.524 mol) BCM and

200 g (6,667 mol) paraformaldehyd innføres under.omrøring i 350 g (5,645 mol) etylenglykol og oppvarmes til 110°C. Etter 200 g (6.667 mol) paraformaldehyde is introduced with stirring into 350 g (5.645 mol) ethylene glycol and heated to 110°C. After

ca. 1 time har de faste stoffer oppløst seg. Eksem<gel_8>about. After 1 hour, the solids have dissolved. Eczema<gel_8>

100 g (0,524 mol) BCM og100 g (0.524 mol) BCM and

200 g (6,667 mol) paraformaldehyd innføres under omrøring i 600 g (5,521 mol) glycerin og'oppvarmes til 110°C. Etter ca. 200 g (6.667 mol) of paraformaldehyde are introduced with stirring into 600 g (5.521 mol) of glycerin and heated to 110°C. After approx.

80 minutter er alt oppløst.80 minutes everything is resolved.

Eksem<pe>l_9_Eczema<pe>l_9_

•100 g (0,524 mol) BCM og•100 g (0.524 mol) BCM and

200 g.(6,667 mol) paraf ormaldehyd innføres under omrøring i 400 g (5,405 mol) n-butanol og oppvarmes til 105°C. Etter 200 g (6.667 mol) of paraformaldehyde are introduced with stirring into 400 g (5.405 mol) of n-butanol and heated to 105°C. After

_70 minutter er alt oppløst._70 minutes everything is dissolved.

De etter eksemplene 6-9 blandede formuleringer kan fortynnes med hver gang 500 g vann uten at det inntrer noen utfelling. The formulations mixed according to examples 6-9 can be diluted each time with 500 g of water without any precipitation occurring.

Til sammenligning: Oppløseligheten av BCM ut-gjør i vann 6 ppm og i butanol 600 ppm. For comparison: The solubility of BCM in water is 6 ppm and in butanol 600 ppm.

På samme måte fremstilles følgende formuleringer: In the same way, the following formulations are produced:

Eksempel_17_ Example_17_

100 g (0 ,'524 mol) BCM suspenderes i100 g (0.524 mol) of BCM are suspended in

200 g (2,703 mol) butanol og oppvarmes til 8o°C. Under om-røring innføres i løpet av 1 time 200 g (2.703 mol) butanol and heated to 8o°C. With stirring, it is introduced during 1 hour

200 g (3,448 mol) propionaldehyd gjennom et dypperør. For fullstendig oppløsning oppvarmes enda i 20 minutter ved 100°C. 200 g (3.448 mol) of propionaldehyde through a dipping tube. For complete dissolution, heat for a further 20 minutes at 100°C.

Eksemp_el_l8Example_el_l8

100 g (0,524 mol) BCM suspenderes i100 g (0.524 mol) BCM is suspended in

300 g (2,542 mol) butylglykol og oppvarmes til 80°C. Under 300 g (2.542 mol) butyl glycol and heated to 80°C. Under

omrøring innføres i løpet av 1 timestirring is introduced during 1 hour

200 g (3,448 mol) propionaldehyd gjennom et dypperør. 200 g (3.448 mol) of propionaldehyde through a dipping tube.

Etter avsluttet innføring oppvarmes 20 minutter ved 100°C. After completion of introduction, heat for 20 minutes at 100°C.

Ek§em£el_19_Ek§em£el_19_

200 g (1,047 mol) BCM suspenderes under omrøring i 300 g (6,522 mol) etanol og oppvarmes til 75°C. 200 g (1.047 mol) of BCM are suspended with stirring in 300 g (6.522 mol) of ethanol and heated to 75°C.

> — > —

150 g '(-2,5^5 mol) acrolein, 95^-ig, innføres i løpet av 80 150 g '(-2.5^5 mol) acrolein, 95^-ig, is introduced during 80

minutter gjennom et dypperør. Etter ytter*-ligere 20 minutters omrøring ved 75°C og avkjøling filtreres den-svakt uklare oppløs-ning. minutes through a dipping tube. After a further 20 minutes of stirring at 75°C and cooling, the slightly cloudy solution is filtered.

Acroleinets stikkende lukt er fullstendig forsvunnet. The acrolein's pungent smell has completely disappeared.

Eksemp_el_20Example_el_20

200 g (1,047 mol) BCM suspenderes under omrøring i 300 g (4,054 mol) butanol og oppvarmes til 80°C. 200 g (1.047 mol) of BCM are suspended with stirring in 300 g (4.054 mol) of butanol and heated to 80°C.

1,50 g (2,545-mol) acrolein, 95$-ig, innføres i løpet av 20 1.50 g (2.545-mol) acrolein, 95$-ig, introduced during 20

minutter gjennom et dypperør. Den svakt uklare reaksjonsoppløsning filtreres etter avkjøling. Den stikkende lukt av minutes through a dipping tube. The slightly cloudy reaction solution is filtered after cooling. The pungent smell of

acroleinet er helt forsvunnet.the acrolein has completely disappeared.

Eksemgel_21Eczema gel_21

200 g (1,047 mol) BCM suspenderes'''under omrøring i 300 g (33333 mol) etylglykol og oppvarmes til 80°C. 200 g (1.047 mol) of BCM are suspended with stirring in 300 g (33333 mol) of ethyl glycol and heated to 80°C.

150 g (2,545 mol) acrolein, 95#-ig, innføres i løpet av150 g (2.545 mol) acrolein, 95#-ig, is introduced during

~80 minutter gjennom et dypperør. Den 'svakt uklare reaksjonsoppløsning filtreres etter avkjøling. Acroleinets stikkende ~80 minutes through a dip tube. The 'slightly cloudy reaction solution is filtered after cooling. Acrolein's stinging

■lukt er fullstendig forsvunnet. Eksemp_el_22 ■odor has completely disappeared. Example_el_22

150 g (5,000 mol) paraformaldehyd suspenderes under omrøring i 750 g (1,136 mol) av omsetningsproduktet av nonylfenol med 150 g (5,000 mol) of paraformaldehyde are suspended with stirring in 750 g (1,136 mol) of the reaction product of nonylphenol with

10 ekvivalenter etylenoksyd og oppvarmes 10 equivalents of ethylene oxide and heated

til 100°C. Derved løser paraformaldehyd seg praktisk talt fullstendig. to 100°C. Thereby, paraformaldehyde dissolves practically completely.

100 g (0,524 mol) BCM innføres og oppløses ved 100°C i løpet 100 g (0.524 mol) BCM is introduced and dissolved at 100°C in the

av 80 minutter.of 80 minutes.

Eksem£§l_23_Eczema£§l_23_

Den fungizide virkning av midlet ifølge oppfinnelsen undersøkes etter kjente fremgangsmåter i næringsbunn-plateprøven. Det anvendes en soppnæringsbunn av 3% malt- ekstrakt, 3% agar-agar og 9H% vann. Pr. 20 ml næringsbunn dannes ved avtrinnede mengder av prøveblandingene og fylles under sterile betingelser i standard Petri-skåler av 9 cm diameter. Det podes ved sporesuspensjoner av skrogrørkulturer. Hver Petri-skål blandes med ca. 100.000 kimer av den prøve-organisme. Det dyrkes. 2 uker ved en optimal veksttemperatur på 28°C og 75% relativ- luftfuktighet. The fungicidal effect of the agent according to the invention is examined according to known methods in the nutrient base plate test. A mushroom nutrient base of 3% malt extract, 3% agar-agar and 9H% water is used. Each 20 ml nutrient base is formed by graduated quantities of the sample mixtures and filled under sterile conditions in standard Petri dishes of 9 cm diameter. It is inoculated by spore suspensions of hull tube cultures. Each Petri dish is mixed with approx. 100,000 germs of the test organism. It is cultivated. 2 weeks at an optimal growth temperature of 28°C and 75% relative humidity.

I tabell 2 er det oppført den minimale hemmekon-sentrasjon (MHK-verdi), referert til vekten av næringsbunnene. Ved disse konsentrasjoner hemmes soppveksten fullstendig. Table 2 lists the minimum heme concentration (MHK value), referred to the weight of the nutrient bases. At these concentrations, fungal growth is completely inhibited.

Ved den nest lavere konsentrasjon inntrer riktignok enda tydelig hemmevirkning, imidlertid allerede i løpet av 1 uke' flatevekst av prøvesoppen. Admittedly, at the next lower concentration, a clear inhibitory effect occurs, however already within 1 week' of surface growth of the test fungus.

For sammenligningen av virkningen mot i praksis av den blåskyttelse virksomme sopp anvendes følgende stoffer: The following substances are used for the comparison of the effect against, in practice, the fungus that is active in the blue shoot:

I Produkt ifølge eksempel 5In Product according to example 5

II Benzimidazolkarbaminsyremetylester (som sammenligning ) II Benzimidazolecarbamic acid methyl ester (as comparison)

III Benzimidazolkarbaminsyremetylester-n-dodecyl-.-benzolsulfonat (som sammenligning). III Benzimidazolecarbamic acid methyl ester-n-dodecyl-.-benzenesulfonate (for comparison).

Eksemgel_24 25 vektdeler av et produkt ifølge eksempel 1 settes til 975 vektdeler av et vanlig trebeskyttelsesmiddelformulering'som er sammensatt av 140 vektdeler av en handelsvanlig alkyd-harpiks, 4 vektdeler zinknaftenat som tørker, 4 vektdeler av et handelsvanlig hudinnbringningsmiddel, 30 vektdeler butyldiglykol<q>g 797 vektdeler prøvebensin 60. Eksemgel_24 25 parts by weight of a product according to example 1 is added to 975 parts by weight of a common wood preservative formulation which is composed of 140 parts by weight of a commercial alkyd resin, 4 parts by weight of zinc naphthenate which dries, 4 parts by weight of a commercial skin application agent, 30 parts by weight butyldiglycol<q>g 797 parts by weight test petrol 60.

Virkningen av de således "b-iozid . utrustede trebe-skyttelsesmiddelf ormuleringer mot sopp som bevirker blåfarging av tre undersøkes etter Mundener-strippemetoden ^H. Butin, Farbe und Lack, 71 (1965), 3731- Det fremkommer en vekstfri inntrengningsdybde på 3-4 mm. The effect of the wood preservative formulations thus equipped with "b-iozide" against fungi that cause blue staining of wood is examined according to the Mundener stripping method ^H. Butin, Farbe und Lack, 71 (1965), 3731- A growth-free penetration depth of 3- 4 mm.

Til sammenligning blandes den ovennevnte vanlige trebeskyttelsesmiddelformulering med 0,25$ benzimidazolkarbaminsyremetylester og undersøkes under samme betingelser. For comparison, the above common wood preservative formulation is mixed with 0.25% benzimidazole carbamic acid methyl ester and tested under the same conditions.

Det fastslås bare inntrengningsdybde på 0,5 mm..Only a penetration depth of 0.5 mm is determined.

Eksempel_25Example_25

50 vektdeler av et ifølge eksempel 5 fremstilt produkt blandes med 23 vektdeler butylglykol, 25 vektdeler tributyltinnoksyd-og 2 vektdeler endosulfan (a, 3, 1,2,3,4, 7,7-heksaklorbicyklo-(2,2,1)-nepten-(2)-bisoksometylen-(5,6)-sulfit). Det oppstår en klar homogen oppløsning som er. stabil over et tidsrom på minst 10 uker. 5 vektdeler av en slik virksom stoff-formulering settes til 95 vektdeler av en handelsvanlig upigmentert trebeskyttelsesmiddelformulering slik den omtales i eksempel 24 uten at det oppstår uklarheter eller utfellinger. Også 50 parts by weight of a product prepared according to example 5 is mixed with 23 parts by weight of butyl glycol, 25 parts by weight of tributyltin oxide and 2 parts by weight of endosulfan (a, 3, 1,2,3,4, 7,7-hexachlorobicyclo-(2,2,1)- neptene-(2)-bisoxomethylene-(5,6)-sulphite). A clear homogeneous solution is produced which is stable over a period of at least 10 weeks. 5 parts by weight of such an active ingredient formulation are added to 95 parts by weight of a commercially available unpigmented wood preservative formulation as described in example 24 without any turbidity or precipitation occurring. Also

et slikt bruksferdig kombinert trebeskyttelsesmiddel viser seg stabilt over et tidsrom på minst 10 uker. such a ready-to-use combined wood preservative proves stable over a period of at least 10 weeks.

Claims (10)

1. Fortynnbar benzimidazolkarbaminsyrealkylesterformulering, oppnåelig ved omsetning av en benzimidazolkarbaminsyrealkylester med den generelle formel (I) 1. Dilutable benzimidazole carbamic acid alkyl ester formulation, obtainable by reacting a benzimidazole carbamic acid alkyl ester of the general formula (I) hvori R betyr en lavere alkylgruppe, med minst den dobbelt molare mengde av et aldehyd med 1-10 karbonatomer i nærvær av minst den dobbelt molare mengde av en hydroksylgruppeholdig forbindelse.. ,i.wherein R means a lower alkyl group, with at least twice the molar amount of an aldehyde with 1-10 carbon atoms in the presence of at least twice the molar amount of a hydroxyl group-containing compound.. ,i. 2. Formulering ifølge krav 1, karakterisert ved at det som aldehyd er blitt anvendt en alifatisk mono- eller dialdehyd med fortrinnsvis 1-5 karbonatomer.2. Formulation according to claim 1, characterized in that an aliphatic mono- or dialdehyde with preferably 1-5 carbon atoms has been used as aldehyde. 3- Formulering ifølge krav 1, karakterisert ved at det som hydroksylgruppeholdig forbindelse er blitt anvendt en primær, sekundær eller tertiær alkohol med 1-18 karbonatomer.3- Formulation according to claim 1, characterized in that a primary, secondary or tertiary alcohol with 1-18 carbon atoms has been used as a compound containing hydroxyl groups. 4. Formulering ifølge krav 1, karakterisert ved at mengden av forbindelsen med formel I utgjør 10-20 vekt-% av den samlede reaksjonsblanding.4. Formulation according to claim 1, characterized in that the amount of the compound of formula I constitutes 10-20% by weight of the overall reaction mixture. 5- Fremgangsmåte til fremstilling av en. fortynnbar benzimidazolkarbaminsyrealkylesterformulering, karakterisert ved at benzimidazolkarbaminsyrealkylester med den generelle formel (I) suspenderes i minst den dobbelt molare mengde av minst en hydroksylgruppeholdig forbindelse, blandes under stadig bevegelse ved 40-150°C med minst den dobbelt, molare mengde av minst ett aldehyd med 1-10 karbonatomer og holdes til fullstendig oppløsning ved denne temperatur.5- Method for producing a. dilutable benzimidazole carbamic acid alkyl ester formulation, characterized in that benzimidazole carbamic acid alkyl ester with the general formula (I) is suspended in at least twice the molar amount of at least one hydroxyl group-containing compound, mixed with constant stirring at 40-150°C with at least twice the molar amount of at least one aldehyde with 1 -10 carbon atoms and is kept until complete dissolution at this temperature. 6. Fremgangsmåte ifølge krav 5, karakterisert ved at det som aldehyd anvendes et alifatisk mono- eller dialdehyd med 1-5 karbonatomer'.6. Method according to claim 5, characterized in that an aliphatic mono- or dialdehyde with 1-5 carbon atoms is used as aldehyde. '7 . Fremgangsmåte ifølge krav 5, karakterisert ved at det som aldehydgruppeholdig forbindelse anvendes en primær, sekundær eller tertiær alkohol med 1-18 karbonatomer..'7. Method according to claim 5, characterized in that a primary, secondary or tertiary alcohol with 1-18 carbon atoms is used as a compound containing aldehyde groups. 8. Fremgangsmåte ifølge krav 5, k a r a k t e r i sert ved at forbindelsen med den generelle formel (I) anvendes i en mengde som utgjør 10-20 vekt-% av den samlede reaksjonsblanding.8. Method according to claim 5, characterized in that the compound with the general formula (I) is used in an amount that constitutes 10-20% by weight of the overall reaction mixture. 9. Anvendelse av formulering ifølge krav 1 som biozid i plantebeskyttelse og som middel til beskyttelse av tekniske materialer mot mikrobiell nedbrytning.9. Use of the formulation according to claim 1 as a biocide in plant protection and as a means of protecting technical materials against microbial degradation. 10. Anvendelse ifølge krav 9 i kombinasjon med andre fungizider, bakterizider eller algizider.10. Use according to claim 9 in combination with other fungicides, bactericides or algicides.
NO800302A 1979-02-06 1980-02-05 DILUTABLE BENZIMIDAZOLCARBAMIC ACID COOLESTER FORMULATION, PROCEDURE FOR THEIR PREPARATION AND THEIR USE AS BIOZIDE NO800302L (en)

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DE3141505A1 (en) * 1981-10-20 1983-04-28 Dr. Wolman Gmbh, 7573 Sinzheim WOOD PRESERVATIVES
AT390442B (en) * 1988-05-30 1990-05-10 Vianova Kunstharz Ag METHOD FOR THE PRODUCTION OF N- (2-BENZIMIDAZOLYL) -CARBAMIDSAEUREALKYLESTER PR PARATIONS AND THE USE THEREOF FOR WOOD PROTECTIVE VARNISHES
DE4201391C2 (en) * 1992-01-21 1995-07-13 Schuelke & Mayr Gmbh Stabilized aldehydic disinfectant and preservative
DE4402043C2 (en) * 1994-01-25 1999-09-09 Hermania Dr Schirm Gmbh Process for reducing unwanted by-products in the production of carbendazim

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