NO144963B - MICROBICID EFFECTIVE HALOGENACYLANILIDES AND THE USE OF THESE TO COMBAT PHYTOPATHOGEN SOPHES - Google Patents
MICROBICID EFFECTIVE HALOGENACYLANILIDES AND THE USE OF THESE TO COMBAT PHYTOPATHOGEN SOPHES Download PDFInfo
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- NO144963B NO144963B NO751087A NO751087A NO144963B NO 144963 B NO144963 B NO 144963B NO 751087 A NO751087 A NO 751087A NO 751087 A NO751087 A NO 751087A NO 144963 B NO144963 B NO 144963B
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Classifications
-
- 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
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof
- A01N37/22—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof the nitrogen atom being directly attached to an aromatic ring system, e.g. anilides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C233/00—Carboxylic acid amides
- C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C233/45—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by carboxyl groups
- C07C233/46—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by carboxyl groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom
- C07C233/47—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by carboxyl groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom having the carbon atom of the carboxamide group bound to a hydrogen atom or to a carbon atom of an acyclic saturated carbon skeleton
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Description
Foreliggende oppfinnelse vedrører mikrobicid virksomme haloaen-acylanilider med formel The present invention relates to microbicidally active haloaene-acylanilides with formula
hvor where
Z betyr hydrogen eller metyl, Z means hydrogen or methyl,
Z, betyr metyl eller etyl og Z, means methyl or ethyl and
7^ 2 betyr én ved et klor-, brom- eller jodatom substituert C2-C4 alkylgruppe, 7^ 2 means one C2-C4 alkyl group substituted by a chlorine, bromine or iodine atom,
samt anvendelse av forbindelsene med formel I for bekjempelse av phytopathogene sopper og bakterier. as well as the use of the compounds of formula I for combating phytopathogenic fungi and bacteria.
Under C2-C^-alkylgrupper er etyl, n-propyl, isopropyl, n-butyl, isobutyl> sek. butyl å forstå. Under C2-C3-alkyl groups are ethyl, n-propyl, isopropyl, n-butyl, isobutyl> sec. butyl to understand.
I DOS nr. 2.212.268 blir det i generell form angitt at N-haloacylerte anilinoalkankarboksylsyreestere har selektiv herbicid virkning. Det blir dog kun nevnt et par N-haloacylerte 2,6-di-alkylanilinoeddiksyrer og deres estere med navn og bevist som herbicider. Henvisninger til mikrobicid, spesielt plantefungicid virkning blir ikke gitt. In DOS No. 2,212,268, it is stated in general form that N-haloacylated anilinoalkanecarboxylic acid esters have selective herbicidal action. However, only a couple of N-haloacylated 2,6-di-alkylanilinoacetic acids and their esters are mentioned with names and proven herbicides. References to microbicide, especially plant fungicide action are not given.
Gruppen N-(11-metoksykarbonyletyl)-N-haloacyl-2, 6-dialkyl-aniliner med formel I ifolge denne oppfinnelsen er til nå The group N-(11-methoxycarbonylethyl)-N-haloacyl-2,6-dialkyl-anilines of formula I according to this invention is to date
ikke beskrevet i litteraturen og derfor nye. Usedvanlig over-raskende er at. denne gruppen i motsetning til de for beskrevne anilinoeddiksyrene og -eddiksyreestere i DOS 2.212.268 oppviser sterke plantefungicide egenskaper. not described in the literature and therefore new. What is extraordinarily surprising is that. this group, in contrast to the previously described anilinoacetic acids and acetic acid esters in DOS 2,212,268, exhibits strong plant fungicidal properties.
Således besitter forbindelsene med den karakteristiske Thus the compounds with the characteristic possess
kjemiske strukturen til formel I såvel ofylaktisk som kurativ virkning mot phytopathogene sopper på kulturplanter som eksempelvis korn. mais, ris, gronnsaker, sukkerroer, soja, jordnotter, på frukttrær, prydplanter, forst og fremst på vinranker, humle, argurkvekster (Agurker, gresskar, meloner) og solanaceen som poteter, tobakk og to amt er , såvel som på bananer-, kakao- og kautsjukplanter. the chemical structure of formula I both ophilactic and curative effect against phytopathogenic fungi on cultivated plants such as grain. maize, rice, vegetables, sugar beet, soya, peanuts, on fruit trees, ornamental plants, primarily on vines, hops, cucurbits (cucumbers, pumpkins, melons) and the solanaceae such as potatoes, tobacco and two counties, as well as on bananas, cocoa and rubber plants.
Med disse virksomme stoffer kan opptredende soppvekst stanses eller tilintetgjøres på planter eller plantedeler ( frukter, blomster, lovverk, stilker, knoller, rotter), hv.orved også senere til-voksende plantedeler blir forskånet fra slike sopper. De virksomme stoffene er virksomme mot de phytopathogene sopper tilhorende de folgende klasser: Ascomycetes (Erysiphaceae), Basidiomycetes som forst og fremst rustsopp, Fungi imperfecti ( som Moniliales), så spesielt mot Oomycetes tilhorende klassen Phycomycetes som With these active substances, fungal growth occurring on plants or plant parts (fruits, flowers, stems, stems, tubers, rots) can be stopped or destroyed, whereby later growing plant parts are also protected from such fungi. The active substances are effective against the phytopathogenic fungi belonging to the following classes: Ascomycetes (Erysiphaceae), Basidiomycetes such as primarily rust fungi, Fungi imperfecti (such as Moniliales), especially against Oomycetes belonging to the class Phycomycetes such as
Phytophthora, Peronospora, Pseudoperonospora, Pythium eller Phytophthora, Peronospora, Pseudoperonospora, Pythium or
. Plasmopara, Utover dette virker forbindelsene av formel I systemisk. . Plasmopara, In addition to this, the compounds of formula I act systemically.
De kan ytterligere anvendes som beisemiddel for behandling av sæd ( frukter, knoller, korn) og plantestiklinger til beskyttelse for soppinfeksjoner samt mot phytopathogene sopper som opptrår i jordsmonnet. They can also be used as a mordant for the treatment of seeds (fruits, tubers, grains) and plant cuttings to protect against fungal infections and against phytopathogenic fungi that occur in the soil.
For å utvide eller forandre virkningsspektret, kan To expand or change the spectrum of action, can
de virksomme stoffer av formel I blandes med ytterligere tidlige-re kjente fungicider, baktericider, fungistatika, bakteriostatika, men også med insekticider, akaricider, herbicider, og på grunn av deres systemiske virkning, som tillater jordsmonnapplikasjon, også med nematicider, molluskicider eller rodenticider, hvorved delvis synergistisk forsterket virkning blir oppnådd. the active substances of formula I are mixed with further previously known fungicides, bactericides, fungistatics, bacteriostatics, but also with insecticides, acaricides, herbicides, and due to their systemic effect, which allows soil application, also with nematicides, molluscicides or rodenticides, whereby a partially synergistically enhanced effect is achieved.
En mikrobicid foretrukket gruppe av forbindelser er de av A microbicidally preferred group of compounds are those of
formel I, hvori betyr metyl. Disse vil kalles . forbindelsesgruppe Ia. formula I, wherein is methyl. These will be called . connection group Ia.
En annen mikrobicid viktig gruppe av forbindelser av formel I Another microbicidally important group of compounds of formula I
er slike hvor Z betyr hydrogen og Z-^ betyr metyl eller etyl, are those where Z means hydrogen and Z-^ means methyl or ethyl,
mens Z„ står for én gruppe -CH-R, hvori R er metyl eller etyl og Y betyr v while Z„ stands for one group -CH-R, in which R is methyl or ethyl and Y means v
klor eller brom. Disse blir kalt forbindelsesgruppe Ib. chlorine or bromine. These are called connection group Ib.
Forbindelsene med formel I har et asymmetrisk karbonatom The compounds of formula I have an asymmetric carbon atom
i propionester-sidekjeden. Forbindelsene med formel I, Ia og Ib i D-konfigurasjonen besitter den sterkere mikrobicide virkning og er derfor foretrukket.I halogenalkylsidékjeden kan det ved en del av forbindelsene, ettersom hvordan substitusjonen in the propionester side chain. The compounds of formula I, Ia and Ib in the D configuration possess the stronger microbicidal effect and are therefore preferred.
er, foreligge et andre asymmetrisk karbonatom. Blir det ved fremstilling ikke anvendt noen optisk aktive utgangsmater- is, there is a second asymmetric carbon atom. If no optically active output feeders are used during production,
ialer, får man nødvendigvis en diastereomerblanding. ials, a mixture of diastereomers is necessarily obtained.
Hvis det*! ikke er nevnt noe annet i den folgende del, menes If it*! is not mentioned otherwise in the following part, is understood
når et av de virksomme stoffer av formel I nevnes, alltid diastereomerblandingen. when one of the active substances of formula I is mentioned, always the diastereomer mixture.
Fremstilling av forbindelsene gjennomfores eksempelvis Preparation of the compounds is carried out, for example
forst ved reaksjon av et anilin med formel II first by reaction of an aniline with formula II
med den onskede a-halogenpropionsyremetylester III og omsetning av forbindelsen med formel IV with the desired α-halopropionic acid methyl ester III and reaction of the compound of formula IV
medrden onskede halogenalkankarboksylsyre HOOC-Z2 hhv. with the desired haloalkane carboxylic acid HOOC-Z2 or
dens reaktive syrehalogenid, syreanhydrid, ester eller amid, fortrinnsvis med halogenidet eller anhydridet av den aktuelle påtalekommende klor-, brom- eller jodalkankarboksylsyre. its reactive acid halide, acid anhydride, ester or amide, preferably with the halide or anhydride of the appropriate chloro, bromo or iodocane carboxylic acid.
I de ovenfor nevnte formler har Z, Z, og Z0 de for formel I angitte betydninger, mens "Hal" står i formel III for halogen, fortrinnsvis for klor eller brom. Som syrehalogenider er syrekloridene eller syrebromidene foretrukket. In the above-mentioned formulas, Z, Z, and Z0 have the meanings given for formula I, while "Hal" stands in formula III for halogen, preferably for chlorine or bromine. As acid halides, the acid chlorides or acid bromides are preferred.
Omsetningen kan gjennomføres i nær- eller fravær av overfor reaktantene inerte oppløsnings- eller fortynningsmidler. Det kommer eksempelvis de folgende på tale: alifatiske eller aromatiske hydrokarboner som benzen, toluen, xylen, petroleter, halogenerte hydrokarboner som klorbenzen, metylenklorid, etylenklorid, kloroform, eter og eterartige forbindelser som dialkyleter, dioksan, tetrahydrofuran, The reaction can be carried out in the presence or absence of solvents or diluents inert to the reactants. Examples include the following: aliphatic or aromatic hydrocarbons such as benzene, toluene, xylene, petroleum ether, halogenated hydrocarbons such as chlorobenzene, methylene chloride, ethylene chloride, chloroform, ether and ether-like compounds such as dialkyl ether, dioxane, tetrahydrofuran,
nitriler som acetonitril, N,N-dialkylerte amider som dimetylformamid, vannfrie eddiksyrer, dimetylsulfoksyd, ketoner som metyletylketon og blandinger av slike opplbsningsmidler med hverandre. nitriles such as acetonitrile, N,N-dialkylated amides such as dimethylformamide, anhydrous acetic acids, dimethyl sulfoxide, ketones such as methyl ethyl ketone and mixtures of such solvents with each other.
Reaksjonstemperaturen ligger mellom 0° og 18o°C, fortrinnsvis mellom 2o° og 12o°C. I mange tilfeller, spesielt ved anvendelsen av halogenacylhalogemider, blir a-halogenacyleringen gjennomfort i nærvær av et syrebindende middel hhv. kondensasjonsmiddel. Som slike kommer tertiære aminer som trialkylaminer ( f.eks. trietyl-amin), pyridin og pyridinbaser, eller uorganiske baser, som oksydene og hydroksydene, hydrogenkarbonatene og karbonatene av alkali- og jordalkalimetaller samt natriumacetat i betraktning. The reaction temperature is between 0° and 18°C, preferably between 2° and 12°C. In many cases, especially when using haloacyl halides, the α-halogenacylation is carried out in the presence of an acid-binding agent or condensation agent. As such, tertiary amines such as trialkylamines (e.g. triethylamine), pyridine and pyridine bases, or inorganic bases, such as the oxides and hydroxides, the hydrogen carbonates and carbonates of alkali and alkaline earth metals and sodium acetate come into consideration.
Som syrebindende middel kan dessuten et overskudd av det As an acid-binding agent, an excess of it can also
aktuelle anilinderivatet av formel II tjene. relevant aniline derivative of formula II serve.
Reaksjonen kan også gjennomfores uten syrebindende middel, hvorved det i enkelte tilfeller er nbdvendig med gjennomledning av nitrogen for å fordrive det dannede hydrogenhalogenid. Blir reaksjonen gjennomfort uten syrebindende middel, virker dimetylformamid som regel katalyserende. The reaction can also be carried out without an acid-binding agent, whereby it is necessary in some cases to pass through nitrogen to expel the formed hydrogen halide. If the reaction is carried out without an acid-binding agent, dimethylformamide usually acts as a catalyst.
Enkeltheter for fremstillingen av mellomproduktene av formel Details of the preparation of the intermediates of formula
IV kan se av metodene som blir generelt anvendt for fremstillingen av anilino-alkansyreestere, beskrevet i de-folgende publikasjonsorganer: IV can be seen from the methods that are generally used for the preparation of anilino-alkanoic acid esters, described in the following publications:
J. Org. Chem. 3o, 41ol )(1965), J. Org. Chem. 3o, 41ol )(1965),
Tetrahedron 1967. 487, Tetrahedron 1967. 487,
Tetrahedron 1967, 493. Tetrahedron 1967, 493.
For fremstilling av de rene optiske former av formel I frem-stiller man f.eks. fra anilinet av formel II og a-halogenpro-pionsyren, f.eks. a-brompropionsyren, den tilsvarende racemiske anilinopropionsyren av formel V For the production of the pure optical forms of formula I, e.g. from the aniline of formula II and the α-halopropionic acid, e.g. the α-bromopropionic acid, the corresponding racemic anilinopropionic acid of formula V
og omsetter den på i og for seg kjent måte med en N-holdig optisk aktiv base. Ved fraksjonert krystallisasjon av det erholdte saltet og etterfølgende frigjoring av den optiske D-antipoden, eventuelt også repetering av reaksjonen med den optisk aktive basen, vinner man en av de enantiomere former til tilsvarende forbindelse av formel V. Fra denne lar det . and reacts it in a manner known per se with an N-containing optically active base. By fractional crystallization of the obtained salt and subsequent release of the optical D antipode, possibly also repeating the reaction with the optically active base, one obtains one of the enantiomeric forms to the corresponding compound of formula V. From this it allows .
seg danne på vanlig måte, f.eks. i nærvær av HCl eller t^SO^, med metanol den optisk aktive esteren IV. På analog måte lar seg også de for dannelsen av anilider av formel I nodvendige form in the usual way, e.g. in the presence of HCl or t^SO^, with methanol the optically active ester IV. In an analogous way, those required for the formation of anilides of formula I can also be used
halogenalkankarboksylsyrer av formel HOOC-Z2 overfore til en av de begge enantiomere former med hjelp av en N-holdig optisk aktiv base, så lenge de disponerer over et asymmetrisk karbonatom, hvilke på sin side kan bringes til reaksjon med en optisk aktiv ester.av formel.IV. Således kan de forskjellige diastereomerer av formel I målrettet fremstilles. haloalkanecarboxylic acids of formula HOOC-Z2 can be converted into one of the two enantiomeric forms with the help of an N-containing optically active base, as long as they have an asymmetric carbon atom, which in turn can be reacted with an optically active ester of formula .IV. Thus, the various diastereomers of formula I can be purposefully prepared.
Som optisk aktiv organisk base kommer f.eks. a-fenyletylamin på tale. As an optically active organic base, e.g. a-phenylethylamine in speech.
I stedet for fraksjonert krystallisasjon kan de enantiomere D-former av formel IV også fremstilles, hvis man diazoterer aminogruppen i naturlig forekommende L-alariin i nærvær av f.eks. HCl eller HBr og derved utbytter L-konfigurasjonen mot halogen under ^-avspalting og under retentsjon, deretter forestrer med metanol og så-omsetter med anilinet av formel II, hvorved inntrer overveiende inversjon til D-konfigurasjonene av formel IV ( J. Am. Chem. Soc. 75, 6o56). Instead of fractional crystallization, the enantiomeric D forms of formula IV can also be prepared, if one diazotizes the amino group in naturally occurring L-alariin in the presence of e.g. HCl or HBr thereby exchanging the L-configuration for halogen under ^-cleavage and retention, then esterifying with methanol and then reacting with the aniline of formula II, whereby predominantly inversion occurs to the D-configurations of formula IV ( J. Am. Chem . Soc. 75, 6o56).
Fremstillingen av de virksomme stoffer av formel I blir The production of the active substances of formula I is
vist ved de folgende eksempler 1 og 2. Temperaturen er oppgitt i°C shown by the following examples 1 and 2. The temperature is stated in °C
EKSEMPEL 1 EXAMPLE 1
N-(11-metoksykarbonyl-etyl)-N-a-klorpropionyl-2,6-dimetylanilin (D,L). a) Fremstilling av mellomproduktet a-(2,6-dimetylanilino)-propionsyremetylester. N-(11-methoxycarbonyl-ethyl)-N-α-chloropropionyl-2,6-dimethylaniline (D,L). a) Preparation of the intermediate α-(2,6-dimethylanilino)-propionic acid methyl ester.
67 g 2,6-dimetylanilin, 125 g a-brompropionsyremetylester og 67 g of 2,6-dimethylaniline, 125 g of α-bromopropionic acid methyl ester and
53 g NaHCO^ ble omrort ved en oljebadtemperatur på 14o° i 17 timer og etter avkjoling. fortynnet med 3oo ml eter. Etter 2 ganger vasking med vann,ble eterékstraktet torket over natriumsulfat.og filtrert. Etter avdestillering av eteren og overskuddet av a-brompropionsyremetylester i vannstråle-vakumm, ble råproduktet destiller, Kp. 98°/o,8 Torr. b) 51,8 g av den ifolge a) fremstilte propionsyreéster og 35 g a-klorpropionsyreklorid ble blandet sammen under roring 1 3po ml klorbenzen, hvorved temperaturen pa réaksjoris-blandingen steg til 4o°:. 53 g of NaHCO 3 were stirred at an oil bath temperature of 14o° for 17 hours and after cooling. diluted with 3oo ml of ether. After washing twice with water, the ether extract was dried over sodium sulfate and filtered. After distilling off the ether and the excess of α-bromopropionic acid methyl ester in a water jet vacuum, the crude product was distilled, Kp. 98°/o.8 Torr. b) 51.8 g of the propionic acid ester produced according to a) and 35 g of a-chloropropionic acid chloride were mixed together with stirring in 1 3po ml of chlorobenzene, whereby the temperature of the reaction mixture rose to 4o°.
Etter tilsetning av 2 m-l dimetylformamid ble det oppvarmet i After adding 2 ml of dimethylformamide, it was heated in
2 timer under tilbakelopsbetingelser og klorbenzet ble avdestillert i vakuum. Ved gnidning med petroleter ble.råproduktet brakt til krystallisasjon. 2 hours under reflux conditions and the chlorobenzene was distilled off in vacuo. By rubbing with petroleum ether, the crude product was brought to crystallization.
Etter omkrystallisering i toluen smeltet diastereomerblandingen, som var forhånden i forholdet ca. 2:3 ifolge NMR-spekteret i den omkrystalliserte provén , mellom lo8 - llo° (forbindelse nr. 1). After recrystallization in toluene, the diastereomer mixture, which was obtained in the ratio of ca. 2:3 according to the NMR spectrum in the recrystallized sample, between 108 - 110° (compound no. 1).
EKSEMPEL 2 EXAMPLE 2
Fremstilling av Manufacture of
N- (11 -metoksykarbonyletyl) -N-"( |3-kloretylkarbonyl)-2, 6-dimetylanilin ( forb. nr. 13). N-(11-methoxycarbonylethyl)-N-(|3-chloroethylcarbonyl)-2, 6-dimethylaniline (compound no. 13).
Til 74 g N-(1-metoksykarbonyletyl)-2,6-dimetylanilin i 3oo ml klorbenzen ble 57 g 3-klorpropionsyreklorid i 2oo ml klorbenzen tildryppet. Etter avslutning av den svakt eksoterme reaksjonen ble 2 ml dimetylformamid tilsatt og blandingen ble oppvarmet 4 timer under tilbakelopsbetingelser. Etter avkjoling ble reaksjonsblandingen vasket to ganger med fortynnet sodaopplbsning og to ganger medvann, torket over natriumsulfat, filtrert og opplosningsmiddelet avdestillert på rotasjonsfor-damper. Etter omkrystallisasjonen fra petroleter hadde forbindelsen et smeltepunkt på 69 - 71°. To 74 g of N-(1-methoxycarbonylethyl)-2,6-dimethylaniline in 300 ml of chlorobenzene, 57 g of 3-chloropropionic acid chloride in 200 ml of chlorobenzene were added dropwise. After completion of the slightly exothermic reaction, 2 ml of dimethylformamide was added and the mixture was heated for 4 hours under reflux conditions. After cooling, the reaction mixture was washed twice with dilute soda solution and twice with water, dried over sodium sulfate, filtered and the solvent distilled off on a rotary evaporator. After recrystallization from petroleum ether, the compound had a melting point of 69-71°.
På analog måte til eksempel la) ble også folgende propionsyre-metylestere fremstilt som mellomprodukter: In an analogous manner to example la), the following propionic acid methyl esters were also prepared as intermediates:
På denne måten eller etter en av de oven angitte., metoder blir folgende forbindelser av formel I fremstilt, hvorved de som jordfungicide og/eller beisemidler spesielt egnede jodholdige forbindelser eksempelvis kan fremstilles fra de klor-holdige forbindelser ved halogenutbytte med alkalijodid ( Z^= 6-stilling). In this way or according to one of the methods indicated above, the following compounds of formula I are prepared, whereby the iodine-containing compounds particularly suitable as soil fungicides and/or mordants can, for example, be prepared from the chlorine-containing compounds by halogen extraction with alkali iodide (Z^= 6 position).
Forbindelsene av formel I kan anvendes med andre egnede pesti-cider eller plantevekstfremmende virksomme stoffer for å gjore deres virkningsspektrum videre. The compounds of formula I can be used with other suitable pesticides or plant growth-promoting active substances to extend their spectrum of action.
Forbindelsene av formel I kan anvendes for seg selv eller The compounds of formula I can be used by themselves or
sammen med egnede bærerer og/eller andre tilsetningsstoffer. Egnede bærer eller tilsetningsstoffer kan være faste eller flytende og tilsvarer de i formuleringsteknikken vanlige stoffer, som f.eks. naturlig eller regenererte mineralske stoffer, opplosnings-, dispergerings-, nett-, "hefte-, fortyknings-, binde- eller gjodningsmidler. together with suitable carriers and/or other additives. Suitable carriers or additives can be solid or liquid and correspond to the usual substances in the formulation technique, such as e.g. natural or regenerated mineral substances, dissolving, dispersing, netting, binding, thickening, binding or fertilizing agents.
Innholdet av virksomt stoff i handelsferdige midler ligger The content of active substance in commercially ready products lies
mellom o,l - 9o%. between o.l - 9o%.
For applikasjon kan forbindelsene av formel I foreligge For application, the compounds of formula I may be present
i de folgende opparbeidede former (hvorved vekt-% angivelsen i parantes viser fordelaktige mengder av virksomt stoff): Faste opparbeidede former: Stovemiddel og stromiddel ( opp til lo%), granulater, omhyllingsgranulater, impregnerings-granulater og homogengranulater ( 1 - 80%), in the following processed forms (whereby the weight-% indication in parentheses shows advantageous amounts of active substance): Solid processed forms: Stumping agent and strobing agent (up to lo%), granules, coating granules, impregnation granules and homogenous granules (1 - 80%) ,
Flytende opparbeidede former: Liquid processed forms:
a) I vann dispergerbare virksomt stoff konsentrater: a) Water-dispersible active ingredient concentrates:
Sproytepulver (wettable powders) og pastaer (25 -9o% Spray powders (wettable powders) and pastes (25 -9o%
i handelspakningen, o,ol - 15% i bruksferdig opplosning), emulsjons- og opplosningskonsentrater (lo -5o%, in the commercial packaging, o,ol - 15% in ready-to-use solution), emulsion and solution concentrates (lo -5o%,
o,ol til 15% i bruksferdig opplosning), o,ol to 15% in ready-to-use solution),
b) Opplosninger ( o,1 - 2o%), b) Solutions (o.1 - 2o%),
De virksomme stoffer av formel I ifolge foreliggende oppfinnelse The active substances of formula I according to the present invention
kan eksempelvis formuleres som folger: can, for example, be formulated as follows:
Stovemiddel: For fremstilling av et a) 5%'ig og b) 2%'ig Stove agent: For the production of a) 5% and b) 2%
stovemiddel blir de folgende stoffer anvendt: stoking agent, the following substances are used:
a) 5 deler virksomt stoff a) 5 parts active substance
95 deler talkum, 95 parts talc,
b) 2 deler virksomt stoff b) 2 parts active substance
1 del hoydispers kiselsyre, 1 part highly dispersed silicic acid,
97 deler talkum. 97 parts talc.
De virksomme stoffer blir blandet med bærerstoffene og malt The active substances are mixed with the carrier substances and ground
og kan i denne form forstdveser for anvendelse. and can in this form be understood for use.
Granulat: For fremstilling av et 5%'ig granulat ble de folgende stoffer anvendt: Granulate: For the production of a 5% granulate, the following substances were used:
5 deler virksomt stoff 5 parts active substance
o,25 deler epiklorhydrin, o.25 parts epichlorohydrin,
o,25 deler cetylpolyglykoleter, o.25 parts cetyl polyglycol ether,
3,5o deler polyetylenglykol 3.5o parts polyethylene glycol
91 deler kaolin ( partikkelstorrelse o,3 - o,8 mm). Aktivsubstansene blir blandet medepiklorhydrin og opplost med 6 deler aceton, heretter blir polyetylenglykol og cetylpolyglykoleter tilsatt. Den således erholdte opplosning blir sproytet på kaolin og deretter blir acetonet fordampet i aceton. Et slikt mikrogranulat blir anvendt fordelaktig for bekjempning av jordsopp. 91 parts kaolin (particle size o.3 - o.8 mm). The active substances are mixed with epichlorohydrin and dissolved with 6 parts acetone, then polyethylene glycol and cetyl polyglycol ether are added. The solution thus obtained is sprayed onto kaolin and then the acetone is evaporated in acetone. Such a microgranulate is advantageously used for combating soil fungi.
Sproytepulver: For fremstilling av et a) 7o%'ig b) 4o%'ig Spray powder: For the production of a) 7o%'ig b) 4o%'ig
c) og d) 25%'ig e) lo%'ig sproytepulver blir folgende bestanddeler anvendt: c) and d) 25% e) 10% spray powder, the following ingredients are used:
a) 7o deler virksomt stoff a) 7o shares active substance
5 deler natriumdibutyliraftylsulfonat 5 parts sodium dibutyl naphthyl sulfonate
3 deler naftalinsulfonsyre-fenolsulfonsyre-formaldehyd-kondensat 3:2:1 3 parts naphthalene sulphonic acid-phenol sulphonic acid-formaldehyde condensate 3:2:1
lo deler kaolin, lo parts kaolin,
12 deler champagne-kritt, 12 parts champagne chalk,
b) 4o deler virksomt stoff b) 4o parts active substance
5 deler ligninsulfonsyre-natriumsalt. 5 parts lignin sulfonic acid sodium salt.
1 del dibutylnaftalinsulfonsyre-natriumsalt 1 part dibutyl naphthalene sulfonic acid sodium salt
54 deler kiselsyre. 54 parts silicic acid.
c) 25 deler virksomt stoff 4,5 deler kalsium-ligningsulfonat c) 25 parts active ingredient 4.5 parts calcium-equal sulfonate
1,9 deler champagne-kritt/hydroksyetylcellulose-blanding (1:1), 1.9 parts champagne chalk/hydroxyethyl cellulose mixture (1:1),
1,5 deler natrium-dibutyl-naftalinsulfonat, 1.5 parts sodium dibutyl naphthalene sulfonate,
19,5 deler kiselsyre, 19.5 parts silicic acid,
19,5 deler champagne-kritt 19.5 parts champagne chalk
28,1 deler kaolin 28.1 parts kaolin
d) 25 deler virksomt stoff 2,5 deler isooctylfenoksy-polyoksyetylen-etanol d) 25 parts active substance 2.5 parts isooctylphenoxy-polyoxyethylene-ethanol
1,7 deler champagne-kritt/hydroksyetylcellulose-blanding (1:1) 1.7 parts champagne chalk/hydroxyethyl cellulose mixture (1:1)
8,3 deler natriumaluminiumsilikat 8.3 parts sodium aluminum silicate
16,5 deler kiselgur 16.5 parts diatomaceous earth
46 deler kaolin 46 parts kaolin
e) lo deler virksomt stoff e) lo parts active substance
3 deler blanding av natriumsaltene av 3 parts mixture of the sodium salts
mettet fettalkoholsulfater saturated fatty alcohol sulfates
• 5 deler naftålinsulfonsyre/formaldehyd-kondensat • 5 parts naphthalene sulfonic acid/formaldehyde condensate
82 deler kaolin 82 parts kaolin
De virksomme stoffer blir.grundig blandet i egnede blandere med tilsetningsstoffene og malt på tilsvarende moller og valser. Man erholder sproytepulver av meget god benettbarhet og svevedyktighet, som lar seg fortynne med vann til suspensjoner av en hver onsk€>t konsentrasjon og som spesielt kan. anvendes til bladapplikasjon. The active substances are thoroughly mixed in suitable mixers with the additives and ground on corresponding molds and rollers. One obtains spray powder of very good wettability and suspension ability, which can be diluted with water to form suspensions of any desired concentration and which in particular can. used for foliar application.
Emulgerbare konsentrater: For. fremstilling av et 25%'ig emulgerbart konsentrat blir de folgende stoffer anvendt: Emulsifiable concentrates: For. production of a 25% emulsifiable concentrate, the following substances are used:
25 deler virksom stoff 25 parts active substance
2,5 deler epoksydert planteolje 2.5 parts epoxidized vegetable oil
lo deler av en alkylarylsulfonat/fettalkoholpoly-glykoleter-blanding lo parts of an alkylaryl sulfonate/fatty alcohol polyglycol ether mixture
5 deler dimetylformamid 5 parts dimethylformamide
57,5 deler xylen. 57.5 parts xylene.
Fra slike konsentrater kan ved fortynning med vann emulsjoner av en hver onsket konsentrasjon fremstilles, som er spesielt egnet for bladapplikasjon. From such concentrates, by diluting with water, emulsions of any desired concentration can be prepared, which are particularly suitable for foliar application.
EKSEMPEL 3 EXAMPLE 3
Virkning mot Phytophthora infestans på Solanum lycopersicum Effect against Phytophthora infestans on Solanum lycopersicum
(= tomater). (= tomatoes).
Ia) Residual-preventiv virkning. Ia) Residual-preventive effect.
Solanum lycopersicum-planter av arten "Roter Gnom" ble etter 3-ukers kultur etter besproytning med en o,o5% aktivsubstans-innholdende suppe ( fremstilt fra virkésubstansen opparbeidet til et sproytepulver) og torking, infisert med én zoospore-^ suspensjon av Phytophthora infestans. De blir deretter holdt i 6 dager i -et klimakammer ved 18 - 2o° og hoy luftfuktighet, som blir fremkalt ved hjelp av en kunstig sproytetåke. Etter denne tid viser det seg typiske bladflekker. Deres antall og storrelse er vurderingsnorm for den provede substans. Solanum lycopersicum plants of the species "Roter Gnom" were after 3 weeks of culture after spraying with a 0.05% active substance-containing soup (made from the wood substance worked up into a spray powder) and drying, infected with one zoospore suspension of Phytophthora infestans . They are then kept for 6 days in a climate chamber at 18 - 2o° and high humidity, which is induced by means of an artificial spray mist. After this time, typical leaf spots appear. Their number and size is the standard of assessment for the substance provided.
Ib) Kurativ virkning. Ib) Curative effect.
Tomatplanter av arten "Roter Gnom" blir etter tre ukers kultur sproytet med en zoosporesuspensjon av soppen og inkubert i en kabin ved 18 - 2o° og mettet luftfuktighet. Avbrekk av befuktningen etter 24 timer. Etter torking av plantene blir disse sproytet med en suppe, som inneholder virkésubstansen formulert som sproytepulver i en konsentrasjon på o,o5%. B Etter torking av sproytebelegget, blir plantene igjen satt After three weeks of culture, tomato plants of the species "Roter Gnom" are sprayed with a zoospore suspension of the fungus and incubated in a cabin at 18 - 2o° and saturated humidity. Discontinue humidification after 24 hours. After drying the plants, they are sprayed with a soup containing the wood substance formulated as spray powder in a concentration of o.o5%. B After drying the spray coating, the plants are planted again
i fuktighetskabinen i 4 dager. Antall og storrelse av typiske bladflekker som opptrer etter denne tid er vurderingsnormer for virksomheten til de provede substanser. in the humidity cabinet for 4 days. The number and size of typical leaf spots that appear after this time are assessment standards for the activity of the substances tested.
II) Preventiv-systemisk virkning. II) Preventive-systemic effect.
Virkésubstansen formulert som sproytepulver blir gitt i en konsentrasjon på 6,o5 % ( med ref. til jordvolumet) på jord-overflaten til.tre uker gamle pottede tomatplanter av arten "Roter Gnom". Etter en ventetid på 3 dager blir plantenes bladunderside sproytet med en zoosporesuspensjon av Phytophthora infestans. De blir deretter holdt i en sproyte-kabin ved 18-2o° og mettet luftfuktighet. Etter denne tid danner det seg typiske bladflekker, hvilke antall og storrelse tjener sfor vurdering av virksomheten til de provede substanser. The active substance formulated as a spray powder is given in a concentration of 6.05% (with reference to the soil volume) on the soil surface of three-week-old potted tomato plants of the species "Roter Gnom". After a waiting period of 3 days, the underside of the plants' leaves is sprayed with a zoospore suspension of Phytophthora infestans. They are then kept in a spray booth at 18-2o° and saturated humidity. After this time, typical leaf spots form, the number and size of which serve to assess the activity of the substances provided.
I disse tre forsokene viser forbindelsene av formel I den i den folgende tabell viste sterke bladfungicide virkning. Forbindelsen nr. 1 minsket i det samme forsøk ved anvendelses-konsentrasjon på bare o, o2% soppangrepet til. \2o%. In these three tests, the compounds of formula I show the strong foliar fungicidal action shown in the following table. Compound No. 1 reduced the fungal attack in the same experiment at an application concentration of only 0.02%. \2o%.
EKSEMPEL 4 EXAMPLE 4
Virkning mot Plasmopara viticola ( Bert.: et Curt.) (Berl. et DeToni) på vinranker. Action against Plasmopara viticola (Bert.: et Curt.) (Berl. et DeToni) on grapevines.
a) Residual-preventiv virkning. a) Residual-preventive effect.
I drivhus ble vinrankestiklinger av arten "Ghasselas" dyrket. In greenhouses, vine cuttings of the species "Ghasselas" were grown.
I lo-blad-stadiumet ble.3 planter sproytet med fra virkésubstansen formulert som sproytepulver suppe (o,o5%;virksomt stoff). In the down-leaf stage, 3 plants were sprayed with from the active substance formulated as spray powder soup (o.o5%; active substance).
Etter torkning av sproytebelegget ble plantene infisert jevnt på bladundersiden med sporesuspensjonen av soppen. Plantene ble deretter holdt i et fuktighetskammer.. Etter denne tid viste seg tydelige sykdomssymptomer på kontrollplantene. Antall og storrelse av infeksjonsstedene til de behandlede planter tjente som vurderingsnormer for virksomheten til de provede substanser. After drying the spray coating, the plants were infected evenly on the underside of the leaves with the spore suspension of the fungus. The plants were then kept in a humidity chamber. After this time, clear disease symptoms appeared on the control plants. The number and size of the infection sites of the treated plants served as assessment norms for the activity of the tested substances.
b) Kurativ virkning. b) Curative effect.
Vinrankestiklinger av arten "Chasselas" ble dyrket i drivhus Vine cuttings of the species "Chasselas" were grown in greenhouses
og infisert med en sporesuspensjon av Plasmopara viticola på bladuridersiden i lo-blad-stadiumet. Etter 24 timers opphold i fuktighetskabinen ble plantene sproytet med en o,o5%'ig suppe av virksomt stoff, som var fremstilt av et sproytepulver av det virksomme stoff. Deretter ble plantene holdt i 7 dager i fuktighetskabinen. Etter denne tid viste det seg sykdomssymptomer på kontrollplantene. Antall og storrelse av infeksjonsstedene på de behandlede planter tjente som vurderingsnorm for virksomheten av de provede substanser. and infected with a spore suspension of Plasmopara viticola on the foliar side in the down-leaf stage. After a 24-hour stay in the humidity cabin, the plants were sprayed with a 0.05% soup of active substance, which was prepared from a spray powder of the active substance. The plants were then kept for 7 days in the humidity cabinet. After this time, disease symptoms appeared on the control plants. The number and size of the infection sites on the treated plants served as an assessment norm for the activity of the tested substances.
I begge disse forsokene i eksempel 4 viser forbindelsene av formel I sterk fungicid virkning ved folgende konsentrasjoner: In both of these experiments in example 4, the compounds of formula I show strong fungicidal activity at the following concentrations:
Forbindelsene nr. 1, 3, 9, lo, 13, 14 og 34 minsker i de samme forsok ved anvendelseskonsentrasjoner på bare o,o2% soppangrepet til \2o%. D-formen til forbindelsene 1,3,9,13 og 34 som avledes fra D-konfigurasjonen til N-(1'-metoksykarbonyl-etyl)-2,6-dimetylanilin minsker ved anvendelseskonsentrasjoner på o,o2% soppangrepet til o-lo%. Compounds Nos. 1, 3, 9, 10, 13, 14 and 34 reduce in the same experiments at application concentrations of only o.o2% the fungal attack to \2o%. The D-form of compounds 1,3,9,13 and 34 which is derived from the D-configuration of N-(1'-methoxycarbonyl-ethyl)-2,6-dimethylaniline decreases at application concentrations of o.o2% the fungal attack to o-lo %.
EKSEMPEL 5 EXAMPLE 5
Virkning mot Pythium debaryanum på Beta vulgaris ( sukkerroe). Effect against Pythium debaryanum on Beta vulgaris (sugar beet).
a) Virkning etter jordapplikasjon. a) Effect after soil application.
Soppen blir kultivert på sterile havrekorn og tilsatt en The fungus is cultivated on sterile oat grains and a
jord/sand-opplosning. Den således infiserte jorden blir fyllt soil/sand solution. The soil thus infected is filled
i blomsterpotter og sådd med sukkerroefro. Rett etter utsåingen blir forsokpreparatene formulert som sproytepulver heilt over jorden som vandig suspensjon (o,oo2% virksomt stoff med ref. til jordvolumet). Pottene blir deretter satt i 2 - 3 in flowerpots and sown with sugar beet seed. Immediately after sowing, the trial preparations are formulated as spray powder completely over the soil as an aqueous suspension (o.oo2% active substance with reference to the soil volume). The pots are then put in 2 - 3
uker i drivhus ved 2o - 24°C. Jorden blir herved holdt jevnt fuktig ved lett sproyting med vann. Ved vurderingen av forsoket blir veksten åv sukkerroeplantene såvel som andelen av friske og syke planter bestemt. weeks in a greenhouse at 2o - 24°C. The soil is thereby kept evenly moist by lightly sprinkling with water. When evaluating the experiment, the growth of the sugar beet plants as well as the proportion of healthy and diseased plants is determined.
b) Virkning etter beiseapplikasjon. b) Effect after stain application.
Soppen ble kultivert på sterile havrekorn og tilsatt en The fungus was cultivated on sterile oat grains and added a
jord-sand-blanding. Den således infiserte jorden blir fyllt i blomsterpotter og sådd med sukkerroefro, som var blitt beiset med forsokspreparater formulert som beisepulver ( o,l% virksomt, stoff med ref. til frovekten). De besådde potter ble satt i 2-3 uker i drivhus ved 2o - 24°C. Jorden ble derved holdt jevnt fuktig ved lett sproyting med vann. soil-sand mixture. The thus infected soil is filled in flowerpots and sown with sugar beet seed, which had been stained with trial preparations formulated as staining powder (o.l% effective, substance with ref. to the seed weight). The sown pots were placed for 2-3 weeks in a greenhouse at 2o - 24°C. The soil was thereby kept evenly moist by light sprinkling with water.
Ved vurderingen ble oppveksten av sukkerroeplantene såvel During the assessment, the growth of the sugar beet plants was as well
som andelen.av sunde og syke planter bestemt. as the proportion.of healthy and diseased plants determined.
Under betingelsene såvel fra forsoket a) som også b) vokste Under the conditions from trial a) as well as b) grew
etter behandling med et av virkestoffene av formel I over 8o% av sukkerroeplantene opp og hadde et jevnt sundt utseende. Ved behandling med en av de jodholdige virkestoffer nr. 2o, 21, 22, 23, 24, 38 og 4o vokste mer enn 9o% og mer av sukkerroeplantene sundt opp. Ved de ubehandlede kontroller vokste mindre enn 2o% av plantene med til dels syklig utseende opp. after treatment with one of the active substances of formula I over 80% of the sugar beet plants rose and had a uniformly healthy appearance. When treated with one of the iodine-containing active substances No. 2o, 21, 22, 23, 24, 38 and 4o, more than 9o% or more of the sugar beet plants grew up healthy. In the untreated controls, less than 2o% of the plants with a partially diseased appearance grew up.
Claims (1)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CH450974A CH587605A5 (en) | 1974-04-01 | 1974-04-01 | |
CH178575A CH599749A5 (en) | 1974-04-01 | 1975-02-13 |
Publications (3)
Publication Number | Publication Date |
---|---|
NO751087L NO751087L (en) | 1975-10-02 |
NO144963B true NO144963B (en) | 1981-09-07 |
NO144963C NO144963C (en) | 1981-12-16 |
Family
ID=25688666
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
NO751087A NO144963C (en) | 1974-04-01 | 1975-03-26 | MICROBICID EFFECTIVE HALOGENACYLANILIDES AND THE USE OF THESE TO COMBAT PHYTOPATHOGEN SOPHES |
Country Status (19)
Country | Link |
---|---|
AR (1) | AR206017A1 (en) |
BG (1) | BG26355A3 (en) |
CS (1) | CS183786B2 (en) |
DD (1) | DD118789A5 (en) |
DK (1) | DK142077B (en) |
EG (1) | EG12051A (en) |
ES (1) | ES436151A1 (en) |
FI (1) | FI61475C (en) |
HU (1) | HU175452B (en) |
IE (1) | IE41330B1 (en) |
IL (1) | IL46970A (en) |
IT (1) | IT1049393B (en) |
NO (1) | NO144963C (en) |
PH (1) | PH11151A (en) |
PL (1) | PL98630B1 (en) |
SE (1) | SE411449B (en) |
SU (1) | SU793353A3 (en) |
TR (1) | TR18470A (en) |
YU (1) | YU81475A (en) |
-
1975
- 1975-01-01 AR AR258180A patent/AR206017A1/en active
- 1975-03-26 NO NO751087A patent/NO144963C/en unknown
- 1975-03-26 DK DK136175AA patent/DK142077B/en unknown
- 1975-03-26 SE SE7503515A patent/SE411449B/en unknown
- 1975-03-26 FI FI750918A patent/FI61475C/en not_active IP Right Cessation
- 1975-03-27 IE IE697/75A patent/IE41330B1/en unknown
- 1975-03-27 HU HU75CI1560A patent/HU175452B/en not_active IP Right Cessation
- 1975-03-28 IT IT21854/75A patent/IT1049393B/en active
- 1975-03-30 EG EG176/75A patent/EG12051A/en active
- 1975-03-31 PH PH16993A patent/PH11151A/en unknown
- 1975-03-31 ES ES436151A patent/ES436151A1/en not_active Expired
- 1975-03-31 BG BG7529501A patent/BG26355A3/xx unknown
- 1975-03-31 YU YU00814/75A patent/YU81475A/en unknown
- 1975-03-31 DD DD185112A patent/DD118789A5/xx unknown
- 1975-03-31 IL IL46970A patent/IL46970A/en unknown
- 1975-04-01 PL PL1975179256A patent/PL98630B1/en unknown
- 1975-04-01 SU SU752118251A patent/SU793353A3/en active
- 1975-04-01 TR TR18470A patent/TR18470A/en unknown
- 1975-04-01 CS CS7500002210A patent/CS183786B2/en unknown
Also Published As
Publication number | Publication date |
---|---|
BG26355A3 (en) | 1979-03-15 |
IL46970A0 (en) | 1975-05-22 |
NO751087L (en) | 1975-10-02 |
IE41330B1 (en) | 1979-12-05 |
FI61475C (en) | 1982-08-10 |
EG12051A (en) | 1978-06-30 |
HU175452B (en) | 1980-08-28 |
IE41330L (en) | 1975-10-01 |
AR206017A1 (en) | 1976-06-23 |
PL98630B1 (en) | 1978-05-31 |
IL46970A (en) | 1978-08-31 |
DK136175A (en) | 1975-10-02 |
NO144963C (en) | 1981-12-16 |
DD118789A5 (en) | 1976-03-20 |
SE7503515L (en) | 1975-10-02 |
IT1049393B (en) | 1981-01-20 |
PH11151A (en) | 1977-10-27 |
ES436151A1 (en) | 1977-02-01 |
TR18470A (en) | 1977-02-24 |
FI61475B (en) | 1982-04-30 |
CS183786B2 (en) | 1978-07-31 |
DK142077B (en) | 1980-08-25 |
DK142077C (en) | 1981-01-19 |
YU81475A (en) | 1983-04-27 |
FI750918A (en) | 1975-10-02 |
SU793353A3 (en) | 1980-12-30 |
SE411449B (en) | 1979-12-27 |
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