NO141340B - ANILIDES FOR USE AS MICROBICIDES - Google Patents

ANILIDES FOR USE AS MICROBICIDES Download PDF

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NO141340B
NO141340B NO751084A NO751084A NO141340B NO 141340 B NO141340 B NO 141340B NO 751084 A NO751084 A NO 751084A NO 751084 A NO751084 A NO 751084A NO 141340 B NO141340 B NO 141340B
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parts
plants
acid
formula
compounds
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NO751084A
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NO141340C (en
NO751084L (en
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Adolf Hubele
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Ciba Geigy Ag
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom 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 to ring carbon atoms
    • C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/81—Amides; Imides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D239/30—Halogen atoms or nitro radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
    • C07D307/18—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members 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 to ring carbon atoms
    • C07D307/24—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members 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 to ring carbon atoms
    • C07D307/68—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
    • C07D309/16—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D309/28—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member 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 to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D327/00—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms
    • C07D327/02—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms one oxygen atom and one sulfur atom
    • C07D327/06—Six-membered rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/26—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom 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 to ring carbon atoms
    • C07D333/38—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Furan Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Heterocyclic Compounds Containing Sulfur Atoms (AREA)
  • Pyridine Compounds (AREA)
  • Pyrane Compounds (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)

Description

Foreliggende oppfinnelse vedrører anilider for anvendelse som mikrobicider The present invention relates to anilides for use as microbicides

hvori R betyr hydrogen eller metyl. wherein R means hydrogen or methyl.

Bakterie- og soppsykdommer på nytteplanter blir begunstiget Bacterial and fungal diseases on useful plants are favoured

ved to faktorer. For det første tilsiktes i første linje ut-byttestigning og kvalitetsforbedringer ved plantedyrkning. by two factors. Firstly, the first line aims to increase yields and improve quality in plant cultivation.

Herved går dog en del av den naturlige motstandskraften mot In doing so, however, part of the natural resistance goes against it

parasitter hos plantene tapt. For det andre har erfaringene vist at bakterier og skadesopp i tidens løp har utviklet resistens mot de kjente pesticider i stor utstrekning. parasites in the plants lost. Secondly, experience has shown that bacteria and harmful fungi have, over time, developed resistance to the known pesticides to a large extent.

Det består derfor et stort behov for mikrobicider, som er There is therefore a great need for microbicides, which are

fordraglige for kulturplantene og som utsletter deres direkte parasitter. tolerable for the cultivated plants and which wipe out their direct parasites.

Slike kulturplanter er eksempelvis korn, mais, ris, grønnsaker, sukkerroer, soja, jordnøtter, frukttrær, prydplanter, først og fremst vinranker, humle, agurkvekster (agurker, gresskar, Such cultivated plants are, for example, cereals, maize, rice, vegetables, sugar beet, soya, peanuts, fruit trees, ornamental plants, primarily vines, hops, cucumber crops (cucumbers, pumpkins,

meloner) , solanacener som poteter, tobakk og" tomater, samt også banan-, kakao- og naturkautsjukplanter. melons), solanaceous plants such as potatoes, tobacco and tomatoes, as well as banana, cocoa and natural rubber plants.

Det er nå blitt overraskende funnet at disse og beslektede nyttekulturer med det virksomme stoffet av formel I på planter eller plantedeler (frukter, blomster, løvverket, stilker, knoller, røtter) hemmer eller dreper de opptredende sopper, hvorved også senere voksende plantedeler blir forskånt for slike sopper. Virkestoffene er virksomme mot phytopathogene sopper fra følgende klasser: ' Ascomycetes (f.eks. erysiphaceae), Basidiomycetes som først og fremst rustsopp, Fungi imperfecti, men spesielt mot. Oomycetes som tilhører klassen Phycomycetes som Phytophthora, Peronspora, Psudopero-nospora, Pythium eller Plasmopara. Utover dette virker forbindelsene av formel I systemisk. It has now surprisingly been found that these and related beneficial cultures with the active substance of formula I on plants or plant parts (fruits, flowers, foliage, stems, tubers, roots) inhibit or kill the appearing fungi, whereby later growing plant parts are also spared such mushrooms. The active ingredients are effective against phytopathogenic fungi from the following classes: ' Ascomycetes (e.g. erysiphaceae), Basidiomycetes which are primarily rust fungi, Fungi imperfecti, but especially against. Oomycetes belonging to the class Phycomycetes such as Phytophthora, Peronspora, Psudopero-nospora, Pythium or Plasmopara. In addition, the compounds of formula I act systemically.

De kan ytterligere anvendes som beisemiddel for behandling They can further be used as a mordant for treatment

av sæd (frukter, knoller, korn) og plantestiklinger for beskyttelse mot soppinfeksjoner samt mot i jorden opptredende phytopathogene sopper. of seeds (fruits, tubers, grains) and plant cuttings for protection against fungal infections as well as against phytopathogenic fungi occurring in the soil.

N-(subst.fenyl)-N-furanoyl-alanin-metylester av formel I forestiller en til;nå ukjent klasse av nye mikrobicid-virke-stoffer, som er de vanlige handelspreparatene tydelig over-legne på deres anvendelsesområde. N-(subst.phenyl)-N-furanoyl-alanine methyl ester of formula I represents a hitherto unknown class of new microbicide active substances, which are clearly superior to the usual commercial preparations in their field of application.

2,5-dimetyl-furan-3-karbonsyre-anilid som er kjent fra DAS 17 68 686 og dets tilsvarende 2'-toluidid er et slikt plantefungicid. Virkningsgrensene for denne forbindelses-typen fremgår av sammenligningsforsøkene. 2,5-dimethyl-furan-3-carboxylic acid anilide which is known from DAS 17 68 686 and its corresponding 2'-toluidide is such a plant fungicide. The effect limits for this type of connection are evident from the comparison tests.

I DOS 20 06 471 angis et stort antall furan-3-karbonsyreamider som fungicider og insekticider. Særlig betones deres virkning mot rustsopper. De sterke strukturelt sammenlign-bare eller mest virksomme beskrevne forbindelser benyttes likeledes som sammenligning. In DOS 20 06 471, a large number of furan-3-carboxylic acid amides are specified as fungicides and insecticides. Their effect against rust fungi is particularly emphasised. The strong structurally comparable or most effective described compounds are also used as a comparison.

Forbindelsene av formel I kan fremstilles ved acylering av The compounds of formula I can be prepared by acylation of

en forbindelse av formel II a compound of formula II

med furan-(2)-karboksylsyre, dens syrehalogenid, syreanhydrid eller ester, i enkelte tilfeller også med et furan-(2)-karbonamid (omamidering). Etter en annen metode kan forbindelsene med formel1I også fremstilles ved å overføre acylanilidene med formel III with furan-(2)-carboxylic acid, its acid halide, acid anhydride or ester, in some cases also with a furan-(2)-carbonamide (omamidation). According to another method, the compounds of formula 1I can also be prepared by transferring the acylanilides of formula III

med butyl-litium eller Na-hydrid til det tilsvarende alkali-saltet, hvilket så fører til det ønskede sluttprodukt ved omsetning med a-halogenpropionsyremestylesteren eller med ct-halogenpropionsyremetylester i nærvær av et alkalikarbonat som I^CO^ som protonakseptor, fortrinnsvis under tilsetning av katalytiske mengder alkalijodid, f.ekS, KJ. with butyl lithium or Na hydride to the corresponding alkali salt, which then leads to the desired end product by reaction with the α-halopropionic acid methyl ester or with the α-halopropionic acid methyl ester in the presence of an alkali carbonate such as I^CO^ as proton acceptor, preferably with the addition of catalytic amounts of alkali iodide, e.g. S, KJ.

I formlene II og III står R for hydrogen eller metyl, uttrykket syrehalogenid betyr fortrinnsvis syreklorid eller syrebromid og halogenato met i oc-halogenpropionsyremetylesteren er fortrinnsvis klor eller brom. Omsetningen kan gjennomfores i nær- eller fravær av ovenfornevnte reaktanter i inerte oppløsnings-eller fortynningsmidler. Eksempelvis kommer de folgende på tale: alifatiske eller aromatiske hydrokarboner som benzen, toluen, xylener, petroleter, halogenerte hydrokarboner som klorbenzen, metylenklorid, etylenklord, kloroform, etere og forbindelser . som dialkyleter, dioksan, tetrahydrofuran, nitriler som Jacetonitril, N,N-dialkylerte amider som dimetylformamid, vannfrie eddiksyre, dimetylsulfoksyd, ketoner som metyl-etylketon og blandinger av slike opplosningsmidler med hverandre. In formulas II and III, R stands for hydrogen or methyl, the term acid halide preferably means acid chloride or acid bromide and the halogen atom in the oc-halopropionic acid methyl ester is preferably chlorine or bromine. The reaction can be carried out in the presence or absence of the above-mentioned reactants in inert solvents or diluents. Examples include the following: aliphatic or aromatic hydrocarbons such as benzene, toluene, xylenes, petroleum ether, halogenated hydrocarbons such as chlorobenzene, methylene chloride, ethylene chloride, chloroform, ethers and compounds. such as dialkyl ether, dioxane, tetrahydrofuran, nitriles such as Jacetonitrile, N,N-dialkylated amides such as dimethylformamide, anhydrous acetic acid, 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°. I mange tilfeller er anvendelsen av syrebindende midler hhv. kondensasjonsmidler fordelaktig. Som slike kommer tertiære aminer som trialkylamin (f.eks. tri-etylamin), pyridin og pyridinbaser, eller uorganiske baser som oksydene og hydroksydene, hydrogenkarbonater og karbonater av alkali- og joralkalimetaller som natriumacetat på tale. The reaction temperature is between 0° and 18°C, preferably between 2° and 12°. In many cases, the use of acid-binding agents or condensing agents beneficial. As such, tertiary amines such as trialkylamine (e.g. tri-ethylamine), pyridine and pyridine bases, or inorganic bases such as the oxides and hydroxides, hydrogen carbonates and carbonates of alkali and non-alkali metals such as sodium acetate are mentioned.

Som syrebindende middel kan desforuten et overskudd av det aktuelle anillnderivatet av formel II tjene. An excess of the appropriate anilne derivative of formula II can also serve as an acid-binding agent.

Fremstillingsmetode som går ut fra forbindelser med formel II kan også gjennomføres uten syrebindende middel, hvorved i noen tilfeller gjennomledning av nitrogen anvendes for å fjerne det i dannede hydrogenhalogenid. i andre tilfeller er en tilsetning av dimetylfomamid som reaksjonskatalysator meget fordelaktig. A production method starting from compounds of formula II can also be carried out without an acid-binding agent, whereby in some cases the passage of nitrogen is used to remove it in the hydrogen halide formed. in other cases, an addition of dimethylfomamide as a reaction catalyst is very advantageous.

Enkeltheter for fremstilling av mellomproduktene av formel II kan man finne i metodene som er generelt beskrevet for fremstilling av anilino-alkansyreestere i de folgende publika-sjonsorganer: Details for the preparation of the intermediate products of formula II can be found in the methods that are generally described for the preparation of anilino-alkanoic acid esters in the following publications:

J. Org. Chem. 2S2^ 41ol (1965), J. Org. Chem. 2S2^ 41ol (1965),

Tetrahedron 1967, 487, Tetrahedron 1967, 487,

Tetrahedron 1967, 493, Tetrahedron 1967, 493,

Forbindelsene med formel I har i propionsyreesterkjeden The compounds of formula I have in the propionic acid ester chain

et asymmetrisk karbonatom og kan spaltes på vanlig måte i optiske antipoder.Blant disse har den enantiomere D-formen den sterkere mikrobicide virkning. an asymmetric carbon atom and can be cleaved in the usual way into optical antipodes. Among these, the enantiomeric D form has the stronger microbicidal effect.

Følgelig foretrekkes de forbindelser, som har D-konfigurasjonen av formel I. Denne D-formen har i etanol eller aceton en negativ dreiningsvinkel. Accordingly, those compounds which have the D-configuration of formula I are preferred. This D-form has in ethanol or acetone a negative angle of rotation.

For fremstilling av de rene optiske D-antipoder blir f.eks. Iden racemiske forbindelsen med formel IV For the production of the pure optical D antipodes, e.g. Whereas the racemic compound of formula IV

fremstilt og så omsatt på i og for seg kjent måte med en N-holdig optisk aktiv base til det tilsvarende salt. prepared and then reacted in a manner known per se with an N-containing optically active base to the corresponding salt.

Gjennom fraksjonert krystallisering av saltet og etterfolgende frigjoring av syren med formel IV anriket med den optiske D-antipoden og eventuelt gjentagelse (også flere gangers gjentagelse) av saltdannelsen, krystallisering og frigjoring av a-anilinopropionsyren av formel IV får man gradvis: den rene D-formen. Fra denne får man på vanlig måte, f.eks. i nærvær av HC1 eller H2S04< den optiske D-konf igurasjonen av esteren med formel II med metanol. Som optisk aktiv organisk base kommer f.eks. a-fenyletylamin på tale. Through fractional crystallization of the salt and subsequent release of the acid of formula IV enriched with the optical D-antipode and possibly repetition (also several times of repetition) of the salt formation, crystallization and release of the α-anilinopropionic acid of formula IV, one gradually obtains: the pure D- the shape. From this you get in the usual way, e.g. in the presence of HCl or H 2 SO 4 < the optical D configuration of the ester of formula II with methanol. As an optically active organic base, e.g. a-phenylethylamine in speech.

I stedet for den fraksjonerte krystallisasjon kan man få den enantiomere D-formen av formel IV også gjennom utbytning av hydroksylgruppen i den naturlige forekommende L(+)melkesyre mot halogen og en videreomsetning av dette produktet under konfigurasjonsforandring ■til det onskede 2, 6-dimetylanilin hhv. 2,3,6-trimetylanilin. Instead of the fractional crystallization, the enantiomeric D form of formula IV can also be obtained by exchanging the hydroxyl group in the naturally occurring L(+)lactic acid for halogen and a further reaction of this product with a change of configuration ■to the desired 2, 6-dimethylaniline respectively 2,3,6-trimethylaniline.

Ved siden av den optiske isomeri opptrer når R = CH-^ved furanoyleringen i forbindelsen II (eller ved omsetning av forbindelsen III med a-halogenpropionsyremetylester) en atropisomeri rundt fenyl N aksen, betinget av den steriske hindring av begge ytterligere innforte rester på N-atomet til trimetylanilinet. Hvis syntesen ikke tilstreber å isolere rene isomerer, dannes den nedenfornevnte forbindelse nr. 2 under fremstillingen som blanding av 4 isomerer. Den gunstige fungicide virkningen av den enantiomere D-form (i sammenligning med D,L-formen eller med L-formen) blir likevel bibeholdt og blir ikke nevneverdig påvirket av atropisomerien. In addition to the optical isomerism, when R = CH-^ upon furanoylation in compound II (or upon reaction of compound III with α-halopropionic acid methyl ester) an atropisomerism occurs around the phenyl N axis, conditioned by the steric hindrance of both further introduced residues on N- atom of the trimethylaniline. If the synthesis does not aim to isolate pure isomers, the below-mentioned compound No. 2 is formed during the preparation as a mixture of 4 isomers. The beneficial fungicidal effect of the enantiomeric D-form (in comparison with the D,L-form or with the L-form) is nevertheless maintained and is not significantly affected by the atropisomerism.

i in

Fremstilling av de virksomme forbindelser med formel I illustreres ved eksemplene 1 og 2 (temperaturangivelser i °C). Preparation of the active compounds of formula I is illustrated by examples 1 and 2 (temperature indications in °C).

EKSEMPEL 1 EXAMPLE 1

Fremstilling av Manufacture of

N-(1'-metoksykarbonyletyl)-N-(furan-(2")-karbonyl)-2,6-dimetylanilin. N-(1'-methoxycarbonylethyl)-N-(furan-(2")-carbonyl)-2,6-dimethylaniline.

Til 18,2. g N-(1-metoksykarbonyletyl)-2,6-dimetylanilin i lo Until 18.2. g N-(1-methoxycarbonylethyl)-2,6-dimethylaniline in lo

ml vannfri toluen og o,2 ml dimetylformamid dryppet man under roring 12,6 g furan-2-karboksylsyreklorid. Etter den svakt eksoterme reaksjonen, oppvarmet man i 5 timer under 'tilbake-løpsbehandling, og det dannede klorhydrogenet ble fullstendig fjernet ved gjennomblåsing med nitrogen. ml of anhydrous toluene and 0.2 ml of dimethylformamide, 12.6 g of furan-2-carboxylic acid chloride were added dropwise while stirring. After the slightly exothermic reaction, heating was carried out for 5 hours under reflux, and the hydrogen chloride formed was completely removed by purging with nitrogen.

Etter fjerning av opplosningsmiddelet . destillerte man i vakuum: kp. = 166 - 168°/o,o6 Torr. Det stivnede slutt- After removing the solvent. distilled in vacuum: bp. = 166 - 168°/o,o6 Torr. The congealed end-

produktet smelter etter omkrystallisering fra toluen/ the product melts after recrystallization from toluene/

petroleter mellom 81 - 84°C. Rontgenpulverdiagramm viser at forbindelsen er polymorf. En av de to modifikasjoner smelter ved 85°. petroleum ether between 81 - 84°C. X-ray powder diagram shows that the compound is polymorphic. One of the two modifications melts at 85°.

Den enantiomere D-konfigurasjoen og dens mellomprodukter har: følgende fysikalske data: EKSEMPEL 2 The enantiomeric D-configuration ion and its intermediates have: the following physical data: EXAMPLE 2

0 0

N-(l'-metoksykarbonyl-etyl)-N-(furan-(2")-karbony^-2,3, 6-trimetylanilin. N-(1'-Methoxycarbonyl-ethyl)-N-(furan-(2")-carbonyl-2,3,6-trimethylaniline.

a) En suspensjon av 51,5 g (o,382 mol) 2,3,6-trimetylanilin, a) A suspension of 51.5 g (0.382 mol) of 2,3,6-trimethylaniline,

135,3 g NaHCO^ og 126 ml (1,15 mol)2-brompropionsyremetylester 135.3 g NaHCO^ and 126 ml (1.15 mol) 2-bromopropionic acid methyl ester

1 blir rort i 6 timer ved en badtemperatur på 13o , deretter 1 is stirred for 6 hours at a bath temperature of 13o, then

avkjolt, filtrert fra salt og destillert:67,3 g a-(2,3,6-trimetyl-anilino)-propionsyremetylester, kp. 144° - 146° C/9 Torr. cooled, filtered from salt and distilled: 67.3 g α-(2,3,6-trimethyl-anilino)-propionic acid methyl ester, b.p. 144° - 146° C/9 Torr.

b) en suspensjon av 33,5 g (o,152 mol) ester erholdt ifolge b) a suspension of 33.5 g (0.152 mol) ester obtained as follows

a) og 18 g (o,17 mol) natriumkarbonat i 200 ml abs. benzen, a) and 18 g (o.17 mol) sodium carbonate in 200 ml abs. benzene,

tilsettes dråpevis 16,7 ml (o,17 mol) furan-2-karboksylsyre-klorid ved 6o - 7o° og temperaturen holdes 4 timer. Etter avkjøling, filtrering og inndampning av filtratet kystalliseres slutt-produktet fra isopropyleter, smp. 98-lo2°C. 16.7 ml (0.17 mol) of furan-2-carboxylic acid chloride are added dropwise at 6o - 7o° and the temperature is maintained for 4 hours. After cooling, filtering and evaporating the filtrate, the final product is crystallized from isopropyl ether, m.p. 98-12°C.

Når man acylerer D-formen av a-(2,3,6-trimetylanilino)-propion-syremetylester med furan-(2)-karboksylsyre eller en av dens reaktive derivater, får man D-formen av forbindelsen 2 som blanding av atropiomerer (=forb. nr. 2a). Den prosentuelle mengde som dannes av hver av disse isomerene er avhengig avAa aktuelle fremgangsmåtebetingelsene • When acylating the D-form of α-(2,3,6-trimethylanilino)-propionic acid methyl ester with furan-(2)-carboxylic acid or one of its reactive derivatives, the D-form of compound 2 is obtained as a mixture of atropiomers ( =prob. no. 2a). The percentage amount formed by each of these isomers depends on the relevant process conditions •

Forbindelsene med formel I kan anvendes sammen med andre egnede pesticide eller plantevekstfremmende virksomme stoffer, for å gjore deres virkningsspektrum bredere. The compounds of formula I can be used together with other suitable pesticides or plant growth-promoting active substances, in order to make their spectrum of action wider.

Forbindelsene av formel I kan anvendes alene eller sammen The compounds of formula I can be used alone or together

med egnede bærere og/eller andre tilsetningstoffer. Egnede bærere eller tilsetningsstoffer kan være faste eller flytende with suitable carriers and/or other additives. Suitable carriers or additives may be solid or liquid

og tilsvarer de i formuleringsteknikken vanlige stoffer, som and correspond to the usual substances in the formulation technique, such as

f.eks. naturlige eller regenerte mineralske stoffer, e.g. natural or regenerated mineral substances,

opplosnings-, dispergerings-, nett-, hefte-, fortyknings-, dissolving, dispersing, netting, binding, thickening,

binde- eller gjodningsmidler. binders or fertilisers.

Innholdet av virksomt stoff i -anvendelsespraparater ligger The content of active substance in -use preparations lies

mellom o,l - 9o%. between o.l - 9o%.

For applikasjon kan forbindelsene av formel I anvendes i For application, the compounds of formula I can be used in

de folgende formuleringer ( hvorved vekt-%-andelen i parantes viser fordelaktige mengder av virksom forbindelse): Faste opparbeidede former: stovemidler og stromidler (opp til lo%), the following formulations (whereby the % by weight in parentheses shows advantageous amounts of active compound): Solid processed forms: cooking agents and strobing agents (up to lo%),

granulater, omhylningsgranulater, impregnerings-granulater og homogengranulater ( 1 - 8o%), granules, coating granules, impregnation granules and homogenous granules ( 1 - 8%

Flytende formuleringer: Liquid formulations:

a) i vann dispergerbare virksomt stoffkonsentrater: sproytepulver (wettable powders) og pastaer ( 25-9o% a) water-dispersible active substance concentrates: spray powders (wettable powders) and pastes (25-9o%

i handelspakningen, o,ol - 15% i bruksferdig opplbsning), 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 - 15% i bruksferdig opplosning), o,ol - 15% in ready-to-use solution),

b) oppløsninger ( o,l - 2o%), b) solutions (o,l - 2o%),

De virksomme stoffer av formel I kan eksempelvis formuleres The active substances of formula I can, for example, be formulated

som folger: as follows:

Stbvemidler: for fremstilling av et a) 5%'ig og b) 2%'ig Starch agents: 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 nr. 2 a) 5 parts active ingredient no. 2

95 deler talkum, 95 parts talc,

b) 2 deler virksomt stoff nr. 1 b) 2 parts active ingredient no. 1

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 forstoves for anvendelse. and in this form can be steamed for use.

Granulat: For fremstilling av et 5%'ig granulat .blir de folgende stoffer anvendt: Granulate: For the production of a 5% granulate, the following substances are used:

5 deler virksomt stoff nr. 1 5 parts active substance No. 1

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 (kornstorrelse o,3 - o,8 mm). 91 parts kaolin (grain size o.3 - o.8 mm).

Aktivsubstansene ble blandet med epiklorhydrin og opplost med The active substances were mixed with epichlorohydrin and dissolved with

6 deler aceton, heretter ble polyetylenglykol og cetylpolyglykoleter tilsatt. Den således erholdte opplosning ble sproytet på kaolin og deretter ble acetonet fordampet i vakuum. Et slikt mikrogranulat ble anvendt med godt resultat for bekjempelse av jordsopper. 6 parts acetone, then polyethylene glycol and cetyl polyglycol ether were added. The solution thus obtained was sprayed onto kaolin and then the acetone was evaporated in a vacuum. Such a microgranulate was used with good results to combat soil fungi.

Sproytepulver: For fremstilling av et a) 7o%'ig, b) 4o%'ig, Spryte powder: For the production of a) 7o%'ig, b) 4o%'ig,

c) og d) 25%'ig, e) lo%'ig sproytepulver anvendes de folgende bestanddeler a) 7o deler N-(1<1->metoksykarbonyl-etyl)-N-/furan-(2")-karbonyl/-2,6-dimetylanilin, virksomt stoff nr. la (D-form) ifolge foreliggende oppfinnelse 5 deler natriumdibutylnaftylsulfonat, 3 deler naftalinsulfonsyre-fenolsulfonsyre-formaldehyd-kondensat 3:2:1, c) and d) 25%, e) 10% spray powder, the following components are used a) 70 parts N-(1<1->methoxycarbonyl-ethyl)-N-/furan-(2")-carbonyl/ -2,6-dimethylaniline, active substance no. la (D-form) according to the present invention 5 parts sodium dibutylnaphthylsulfonate, 3 parts naphthalene sulfonic acid-phenolsulfonic acid-formaldehyde condensate 3:2:1,

lo deler kaolin lint parts kaolin

12 deler champagne-kritt 12 parts champagne chalk

b) 4o deler virksomt stoff nr. 2 b) 4o parts active substance no. 2

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 nr. 2a (D-form) c) 25 parts active ingredient no. 2a (D-form)

4,5 deler kalsium-ligninsulfonat, 4.5 parts calcium lignin sulfonate,

1,9 deler champagne-kritt/hydroksyetylcellulose-blanding (1:1), 1.9 parts champagne chalk/hydroxyethyl cellulose mixture (1:1),

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 nr. 2 d) 25 parts active ingredient no. 2

2,5 deler isooktylfenoksy-polyoksyetylen-etanol 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 nr. la (D-form) e) lo parts active substance no. la (D-form)

3 deler blanding av natriumsaltene til mettede fett-alkoholsulfater 3 parts mixture of the sodium salts of saturated fat-alcohol sulphates

5 deler naftalinsulfonsyre/formaldehyd-kondensat 5 parts naphthalene sulfonic acid/formaldehyde condensate

82 deler kaolin. 82 parts kaolin.

De virksomme forbindelser blir grundig blandet i egnede blandere med tilsetningstoffene og malt på tilsvarende møller og valser. Man erholder sprøytepulver med fremragende fuktbarhet og sveve-evne, som lar seg fortynne med vann til suspensjoner med enhver ønsket konsentrasjon og spesielt lar seg anvende til bladapplikasjon. The active compounds are thoroughly mixed in suitable mixers with the additives and ground on corresponding mills and rollers. A spray powder with excellent wettability and floating ability is obtained, which can be diluted with water to form suspensions of any desired concentration and can especially be used for foliar application.

Emulgerbare konsentrater: For fremstilling av et 25'ig emul-gerbart konsentrat blir følgende stoffer anvendt: Emulsifiable concentrates: To produce a 25% emulsifiable concentrate, the following substances are used:

25 deler virksomt stoff nr.l 25 parts active substance no.l

2,5 deler epoksydert planteolje 2.5 parts epoxidized vegetable oil

10 deler av en alkylarylsulfonat/fettalkoholpoly-glykoleter-blanding 10 parts of an alkylaryl sulfonate/fatty alcohol polyglycol ether mixture

5 deler dimetylformamid 5 parts dimethylformamide

57,5 deler xylen. 57.5 parts xylene.

Av slike konsentrasjoner kan ved fortynning med vann fremstilles emulsjoner av enhver ønsket konsentrasjon, som er spesielt egnet til bladapplikasjon. Such concentrations can be diluted with water to produce emulsions of any desired concentration, which are particularly suitable for foliar application.

FORSØK I EXPERIMENT I

Virkning mot Phytophthora infestans på tomater. Effect against Phytophthora infestans on tomatoes.

Som sammenligningssubstanser anvendes de følgende forbindelser: The following compounds are used as comparison substances:

En soppinfeksjon på over 50 % karakteriserer den gjeldende anvendte aktivsubstans (=AS) som virkningsløs for praktiske formål. Det foretas derfor ingen ytterligere differensiering. A fungal infection of more than 50% characterizes the currently used active substance (=AS) as ineffective for practical purposes. No further differentiation is therefore made.

a) Kurativ virkning a) Curative effect

Tomatplanter av sorten "Roter Gnom" sprøytes etter tre ukers Tomato plants of the variety "Roter Gnom" are sprayed after three weeks

vekst med en Zoosporersuspensjon av soppen og inkuberes i en beholder ved 18 - 20 °C og mettet luftfuktighet. Avbrudd av befuktning etter 24 timer. Etter tørkingen av plantene sprøy-tes disse med en suppe som inneholder forbindelsen som skal undersøkes formulert som sprøytepulver i en av dé!angitte forsøkskonsentrasjoner. Etter tørking av sprøytebelegget stil-les plantene igjen i fuktebeholderen i 4 dager. Antall og størrelse av de typiske bladflekker som opptrer etter dette tidsrom er bedømmelsesmålestokken for virkningen av de under-søkte substanser. Som referansemålestokk tjener infiserte men ubehandlede kontrollplanter. growth with a Zoosporer suspension of the fungus and incubated in a container at 18 - 20 °C and saturated humidity. Interruption of humidification after 24 hours. After the plants have been dried, they are sprayed with a soup containing the compound to be examined, formulated as a spray powder in one of the test concentrations indicated. After drying the spray coating, put the plants back in the moisture container for 4 days. The number and size of the typical leaf spots that appear after this period of time is the evaluation scale for the effect of the investigated substances. Infected but untreated control plants serve as a reference yardstick.

b) Forebyggende systemisk virkning b) Preventive systemic effect

Forbindelsen som skal undersøkes formulert som sprøytepulver The compound to be investigated is formulated as a spray powder

gis i form av en sprøytesuppe i det øverste jordskikte av tre uker gamle tomatplanter av sorten "Roter Gnom" i potter slik at en konsentrasjon på 0.006 % hhv. 0.002 % av virkestoffet (beregnet på jordvolumet) foreligger i rotområdet. Det legges vekt på at sprøytesuppa ikke kommer i berøring med de plantedeler som er over jorden. Etter 48 timer infiseres de behandlede plantene med en Sporangien-suspensjon av soppen. Vurderingen av soppinfeksjonen skjer etter en inkubasjon av de infiserte planter i 5 dager ved 20° og mettet luftfuktighet. Antall og størrelse av bladflekkene som opptrer på dette tidspunkt tjener som målestokk for virkningen til substansen som undersøkes i sammenligning med infiserte men ubehandlede kontrollplanter. is given in the form of a spray soup in the top soil layer of three-week-old tomato plants of the variety "Roter Gnom" in pots so that a concentration of 0.006% or 0.002% of the active substance (calculated on the soil volume) is present in the root area. It is emphasized that the spray soup does not come into contact with the plant parts that are above the ground. After 48 hours, the treated plants are infected with a Sporangien suspension of the fungus. The assessment of the fungal infection takes place after an incubation of the infected plants for 5 days at 20° and saturated humidity. The number and size of the leaf spots appearing at this time serves as a measure of the effect of the substance under investigation in comparison with infected but untreated control plants.

FORSØK II EXPERIMENT II

Virkning mot Plasmopara viticola (Bert•etCurt.) Action against Plasmopara viticola (Bert•etCurt.)

(Berl.etDeToni) på druer. (Berl.etDeToni) on grapes.

a) Residualforebyggende virkning a) Residual prevention effect

I drivhus dyrkes druestiklinger av sorten "Chasselas". I Grape cuttings of the "Chasselas" variety are grown in greenhouses. IN

10-bladstadiet ble 3 planter sprøytet med en suppe fremstilt av en sprøytepulverformulering av forbindelsen som skal undersøkes. Etter tørking av sprøytebelaget ble plantene jevnt infisert på bladundersiden med sporer.suspensjonen av soppen. Plantene ble deretter i 8 dager holdt i et fuktig kammer. Etter denne tiden viste tydelig sykdomssymptomene seg på kontrollplantene. Antall og størrelse av infeksjonsstedene på de behandlede plantene tjente som bedømmelsesmålestokk for virkningen av de At the 10-leaf stage, 3 plants were sprayed with a soup prepared from a spray powder formulation of the compound to be investigated. After drying the spray coating, the plants were uniformly infected on the underside of the leaves with spores. The suspension of the fungus. The plants were then kept in a moist chamber for 8 days. After this time, the disease symptoms clearly appeared on the control plants. The number and size of the infection sites on the treated plants served as a yardstick for their effectiveness

undersøkte substanser. investigated substances.

De i forsøk 1 nevnte tidligere kjente forbindelser ble anvendt som sammenligning. The previously known compounds mentioned in experiment 1 were used as a comparison.

b) Kurativ virkning b) Curative effect

Druestiklinger av typen "Chasselas" ble dyrket i drivehus og Grape cuttings of the "Chasselas" type were grown in greenhouses and

i 10-bladstadiet infisert med en sporesuspensjon av Plasmopara viticola på bladundersiden. Etter 24 timers opphold i fukt-beholderen ble plantene sprøytet med en virkestoffsuppe som var fremstilt av et sprøytepulver av forbindelsen som skal undersøkes. Deretter ble plantene videre holdt 7 dager i fuktkammeret. Etter denne tiden viste sykdomssymptomene seg på kontrollplantene. Antall og størrelse av infeksjonsstedene på de behandlede plantene tjente som vurderingsmålestokk for virkningen av de undersøkte substanser. in the 10-leaf stage infected with a spore suspension of Plasmopara viticola on the leaf underside. After a 24-hour stay in the moisture container, the plants were sprayed with an active substance soup that was prepared from a spray powder of the compound to be investigated. The plants were then kept for 7 days in the humidity chamber. After this time the disease symptoms appeared on the control plants. The number and size of the infection sites on the treated plants served as an evaluation scale for the effect of the investigated substances.

FORSØK III EXPERIMENT III

Virkning mot Pythium debaryanum på Beta vulgaris (sukkerroer). Effect against Pythium debaryanum on Beta vulgaris (sugar beet).

a) Virkning etter jordapplikasjon a) Effect after soil 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 sukkerroesåkorn. Rett etter ut-såingen blir forsøkspreparatene formulert som sprøytepulver heilt over jorden som vandig suspensjon (0.002 % virksomt stoff med ref. til jordvolumet.) . Pottene blir deretter satt i drivhus ved 20 - 24 °C i 2 - 3 uker. Jorden blir derved holdt jevnt fuktig ved en lett sprøytning med vann. Ved vurderingen av forsøkene blir veksten av sukkerroeplantene såvel som andelen av sunde og syke planter bestemt. soil/sand mixture. The thus infected soil is filled in flower pots and sown with sugar beet seed. Immediately after sowing, the experimental preparations are formulated as spray powder completely over the soil as an aqueous suspension (0.002% active substance with reference to the soil volume). The pots are then placed in a greenhouse at 20 - 24 °C for 2 - 3 weeks. The soil is thereby kept evenly moist by a light spraying with water. When assessing the trials, 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 blir kultivert på sterile havrekorn og tilsatt en The fungus is cultivated on sterile oat grains and a

jord/sand-blanding. Den således infiserte jorden blir fyllt i blomsterpotter og sådd med sukkerroesåkorn, som er blitt beiset med forsøkspreparatene, som er formulert som beisepulver (0.1 % virksomt stoff med ref. til såkornvekten). De besådde pottene står i drivhuset ved 20 - 24 °C i 2 - 3 uker. Jorden blir holdt jevnt fuktig ved lett sprøytning av vann. Ved vurderingen blir veksten av sukkerroeplantene såvel som andelen av sunde og syke planter bestemt. soil/sand mixture. The thus infected soil is filled in flower pots and sown with sugar beet seed, which has been stained with the experimental preparations, which are formulated as a staining powder (0.1% active substance with reference to the seed weight). The sown pots are kept in the greenhouse at 20 - 24 °C for 2 - 3 weeks. The soil is kept evenly moist by light spraying of water. During the assessment, the growth of the sugar beet plants as well as the proportion of healthy and diseased plants is determined.

Under betingelsene såvel for forsøk a) som b) vokste etter behandlingen med ett av de virksomme stoffer 1, la, 2 eller 2a over 85 % av sukkerroeplantene opp og hadde et jevnt sundt utseende. Ved de ubehandlede kontrollene vokste mindre enn 20 % av plantene qpp med til dels syklig utseende. Under the conditions for both experiments a) and b), after the treatment with one of the active substances 1, 1a, 2 or 2a, more than 85% of the sugar beet plants grew up and had a uniformly healthy appearance. In the untreated controls, less than 20% of the plants grew qpp with a partially diseased appearance.

Claims (2)

1. Anilider for anvendelse som mikrobicider karakterisert ved at de har formelen I1. Anilides for use as microbicides characterized in that they have the formula I hvori R betyr hydrogen eller metyl-. wherein R means hydrogen or methyl-. 2. Anilider ifølge krav 1 karakterisert ved at de foreligger i D-konfigurasjon.2. Anilides according to claim 1, characterized in that they are in D-configuration.
NO751084A 1974-04-02 1975-03-26 ANILIDES FOR USE AS MICROBICIDES NO141340C (en)

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CH457274A CH590608A5 (en) 1974-04-02 1974-04-02 N-Furoyl-N-aryl-alanine esters - prepd. e.g. by reacting N-aryl-alanine esters with 2-furoic acid or its derivs.
CH159175A CH603041A5 (en) 1974-04-02 1975-02-10 N-Furoyl-N-aryl-alanine esters

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BR122019020347B1 (en) 2007-02-06 2020-08-11 Basf Se MIXTURES, PESTICIDE COMPOSITION AND METHODS TO CONTROL HARMFUL PHYTOPATHOGENIC FUNGI, TO PROTECT PLANTS FROM ATTACK OR INFESTATION BY INSECTS, ACARIDES OR NEMATODES AND TO PROTECT SEED
EP2000030A1 (en) 2007-06-06 2008-12-10 Bayer CropScience AG Fungicidal active agent compounds
EP2000028A1 (en) 2007-06-06 2008-12-10 Bayer CropScience Aktiengesellschaft Fungicidal active agent compounds
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EP2910126A1 (en) 2015-05-05 2015-08-26 Bayer CropScience AG Active compound combinations having insecticidal properties
CN115557887A (en) * 2022-11-10 2023-01-03 南京林业大学 Synthesis of trifluoromethyl pyridine derivative based on Ugi reaction and biological activity research of trifluoromethyl pyridine derivative

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PH13072A (en) 1979-11-23
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IE41140B1 (en) 1979-10-24
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