NO145617B - 3-PHENYL-5-SUBSTITUTED 4 (1H) -PYRIDONES (TIONS) FOR USE AS HERBICIDES - Google Patents

3-PHENYL-5-SUBSTITUTED 4 (1H) -PYRIDONES (TIONS) FOR USE AS HERBICIDES Download PDF

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NO145617B
NO145617B NO752942A NO752942A NO145617B NO 145617 B NO145617 B NO 145617B NO 752942 A NO752942 A NO 752942A NO 752942 A NO752942 A NO 752942A NO 145617 B NO145617 B NO 145617B
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phenyl
pyridone
alkyl
methyl
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Harold Mellon Taylor
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Lilly Co Eli
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    • 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
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    • 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
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
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    • 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
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    • 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
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  • Chemical & Material Sciences (AREA)
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Description

Foreliggende oppfinnelse angår 3-fenyl-5-substituerte 4(1H)-pyridoner(tioner) for bruk som før-spirings- og etter-spiringsherbicider. Siden bekjempelse av ugress, som kjent, The present invention relates to 3-phenyl-5-substituted 4(1H)-pyridones (thiones) for use as pre-emergence and post-emergence herbicides. Since weed control, as is known,

er av avgjørende betydning for å oppnå de beste høstings-utbytter, er ugressdrepende midler nå oppfattet som viktige redskaper for gårdbrukeren, og det er stadig behov for nye og forbedrede ugressmidler.. is of crucial importance for achieving the best harvest yields, herbicides are now perceived as important tools for the farmer, and there is a constant need for new and improved herbicides.

Til tross for den utstrakte forskning som har vært .gjennomført på området landbrukskjemi, har aktive stoffer som er nær beslektet med de foreliggende forbindelser med formel I hit-til ikke vært funnet. Poly-halogenpyridoner, som har to eller flere kloratomer samt andre alkyl- og halogen-substituenter på pyridinringen er kjente ugressmidler, men er klart forskjellige fra forbindelser med formel I. Despite the extensive research which has been carried out in the field of agricultural chemistry, active substances which are closely related to the present compounds of formula I have not yet been found. Polyhalopyridones, which have two or more chlorine atoms as well as other alkyl and halogen substituents on the pyridine ring, are known herbicides, but are clearly different from compounds of formula I.

Den organiske kjemi har gransket pyridonene temme-lig nøye. For eksempel beskriver Ishibe og medarbeidere i J. Organic chemistry has scrutinized the pyridones quite carefully. For example, Ishibe and colleagues describe in J.

Am. Chem. Soc. 95, 3396-3397 (<1>973), en omleiring av 3,5-difen-yl-l,2,6-trimetyl-4(lH)-pyridon. Slike forbindelser er imidlertid ikke ugressmidler. Leonard et al, J. Am. Chem. Soc. 77 > I852-I<8>55 (1955)» beskriver syntese av 3,5-dibenzyl-l-metyl-4(1H)-pyridoner som heller ikke har herbicid virkning. Den samme hoved-forfatter beskriver også 3»5~di(substituert benzyl-iden)tetrahydro-4-pyridoner i J. Am. Chem. Soc. 79» 156-160 (19-57). Heller ikke disse stoffer har ugressdrepende virkning. Am. Chem. Soc. 95, 3396-3397 (<1>973), a rearrangement of 3,5-diphen-yl-1,2,6-trimethyl-4(1H)-pyridone. However, such compounds are not herbicides. Leonard et al., J. Am. Chem. Soc. 77 > I852-I<8>55 (1955)" describes the synthesis of 3,5-dibenzyl-1-methyl-4(1H)-pyridones which also have no herbicidal effect. The same lead author also describes 3,5-di(substituted benzylidene)tetrahydro-4-pyridones in J. Am. Chem. Soc. 79» 156-160 (19-57). Nor do these substances have a weed-killing effect.

Light og medarbeidere i J. Org. Chem. 25, 538-546 (I96O), omtaler en rekke 4-Pvridon-forbindelser inklusive 2,6-difenylrl-metyl-4(lH)-pyridon og beslektede stoffer som bærer substituenter på fenyl-ringen, hvorav ingen er ugressdrepende. Light and colleagues in J. Org. Chem. 25, 538-546 (1960), discusses a number of 4-Pvridone compounds including 2,6-diphenyl-1-methyl-4(1H)-pyridone and related substances bearing substituents on the phenyl ring, none of which are herbicidal.

En interessant nylig artikkel ble publisert av An interesting recent article was published by

El-Kholy et al. i J. Hetero. Chem. 10, 665-667 (7. september, 1973). El-Kholy beskriver en syntese av 3>5-difenyl-l-metyl-4(lH)-pyridon og beslektede forbindelser ved omsetning mellom metylamin og natriumsaltet av 1,5-dihydroksy-2,4-difenyl-1,4-pentadien-3-on. El-Kholy et al. in J. Hetero. Chem. 10, 665-667 (September 7, 1973). El-Kholy describes a synthesis of 3>5-diphenyl-1-methyl-4(1H)-pyridone and related compounds by reaction between methylamine and the sodium salt of 1,5-dihydroxy-2,4-diphenyl-1,4-pentadiene -3-on.

En fremgangsmåte for fremstilling av en serie nye 3-fenyl-4(lH)-pyridoner(tioner) som er ugressdrepende midler og er aktive mot et uvanlig bredt spektrum av ugress, blir beskrevn-et i det følgende. Nye metoder og sammensetninger for påføring av de ugressdrepende midler, særlig egnet for bruk på bomullsmarker, beskrives også. A method for the production of a series of new 3-phenyl-4(1H)-pyridones(thiones) which are herbicides and are active against an unusually broad spectrum of weeds, is described in the following. New methods and compositions for applying the herbicides, particularly suitable for use on cotton fields, are also described.

Fremgangsmåten for fremstilling av forbindelser med formel I i det følgende er en analogi-fremgangsmåte. Benary og Bitter i Ber. 6l, IO58 (I928) beskriver syntese av et dinatrium-mellomprodukt av 1,5-dihydroksy-2,4-difenyl-1,4-pentadien-3-on ved kondensasjon av 1,3-difenyl-2-propanon med etylformiat i nærvær av natriummet.oksyd. Pentadienon-mellomproduktet nøy-traliseres med sterk syre og danner 3>5-difenyl-4-pyron. Omsetning av pyronet med ammoniumacetat ved forhøyet temperatur gir 3,5-difenyl-4(1H)-pyridon. The process for the preparation of compounds of formula I in the following is an analogical process. Benary and Bitter in Ber. 6l, IO58 (I928) describes the synthesis of a disodium intermediate of 1,5-dihydroxy-2,4-diphenyl-1,4-pentadien-3-one by condensation of 1,3-diphenyl-2-propanone with ethyl formate in presence of sodium methoxide. The pentadienone intermediate is neutralized with strong acid to form 3>5-diphenyl-4-pyrone. Reaction of the pyronet with ammonium acetate at elevated temperature gives 3,5-diphenyl-4(1H)-pyridone.

Analogt kan 3»5-difenyl-4(lH)-pyridoner fremstilles ved omsetning av,en egnet ring-substituert 1,3-difenyl-2-propanon med formamid og formamidin-acetat. Omsetning ved til-bakeløpstemperatur gir det tilsvarende 3»5-difenyl-4(1H)-pyridon som omsettes med et halogenid av den ønskede 1-substituent i nærvær av en egnet sterk base, for fremstilling av den ønskede forbindelse med formel I. Analogously, 3'5-diphenyl-4(1H)-pyridones can be prepared by reacting a suitable ring-substituted 1,3-diphenyl-2-propanone with formamide and formamidine acetate. Reaction at reflux temperature gives the corresponding 3'5-diphenyl-4(1H)-pyridone which is reacted with a halide of the desired 1-substituent in the presence of a suitable strong base, to produce the desired compound of formula I.

Ifølge1 oppfinnelsen tilveiebringes nye, herbicid aktive forbindelser med generell formel: According to the invention, new, herbicidally active compounds are provided with the general formula:

hvor: where:

X betegner oksygen eller svovel; R betegner hydroksy, (C^-C^alkyl; C^-C^-alkyl substituert med halogen, cyan, karboksy eller metoksykarbonyl; C^C^-alkenyl; C2-C -alkynyl; C^-C^-alkoksy; acetoksy; eller dimetylamino; forutsatt at R ikke inneholder mer enn 3 C-atomer; R"*"- gruppene uavhengig av hverandre, betegner halogen; C-^-Cg-alkyl; C-^Cg-alkyl substituert med halogen; C^-Cg.-alkyl mono-substituert med fenyl, cyan eller C-^-C^-alkoksy; Cp-Cg-alkenyl; C2-Cg-alkenyl substituert med halogen; C2-Cg-alkynyl; Cg-Cg-alkynyl substituert med halogen; C^-Cg-cykloal-kyl; C^-Cg-cykloalkenyl; C^-Cg-cykloalkylalkyl; C-^-C^-alkanoyloksy; C-^-C^-alkylsulf onyloksy; fenyl; fenyl-monosubstituert med halogen, C^-C^-alkyl, C-^-C^-alkoksy eller nitro; nitro; cyano; karboksy; hydroksy; C-^-C^-alkoksykarbonyl; -O-R<3>; -S-R<3>; -SO-R<3> eller -S02-r<3>; X denotes oxygen or sulphur; R denotes hydroxy, (C^-C^alkyl; C^-C^-alkyl substituted with halogen, cyan, carboxy or methoxycarbonyl; C 1 -C 2 -alkenyl; C 2 -C alkynyl; C 1 -C 4 -Alkoxy; acetoxy; or dimethylamino; provided that R contains no more than 3 C atoms; The R"*" groups, independently of each other, denote halogen; C 1 -C 8 alkyl; C 1 -C 8 alkyl substituted with halogen; C 1 -C 6 -alkyl mono-substituted with phenyl, cyano or C 1 -C 6 -alkyl; C 1 -C 8 alkenyl; C 2 -C 8 alkenyl substituted with halogen; C 2 -C 8 alkynyl; C 6 -C 8 -alkynyl substituted with halogen; C 1 -C 8 -cycloalkyl; C 1 -C 8 cycloalkenyl; C 1 -C 8 cycloalkylalkyl; C 1 -C 4 -alkanoyloxy; C 1 -C 4 -alkylsulfonyloxy; phenyl; phenyl monosubstituted with halogen, C 1 -C 4 -alkyl, C 1 -C 4 -alkyl or nitro; nitro; cyano; carboxy; hydroxy; C 1 -C 4 -Alkoxycarbonyl; -O-R<3>; -S-R<3>; -SO-R<3> or -SO2-r<3>;

R<3> betegner C-^-C-^-alkyl; C-L-C-L2-alkyl substituert med halogen; R<3> denotes C 1 -C 1 -alkyl; C-L-C-L2 alkyl substituted with halogen;

C-^-C-^-alkyl-monosubstituert med fenyl, cyano eller C-^-C^-alkoksy; fenyl; fenyl-monosubstituert med halogen, C-^-C^-alkyl, C1-C^-alkoksy eller med nitro; C^-Cg-cykloalkyl; C^-Cg-cykloalkylalkyl; C2-C12-alkenyl; C2-C12-alkenyl substituert med halogen; <Cg->C^g-alkynyl; eller C2-C12-alkynyl C 1 -C 4 -alkyl monosubstituted with phenyl, cyano or C 1 -C 4 -alkyl; phenyl; phenyl monosubstituted with halogen, C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy or with nitro; C 1 -C 8 cycloalkyl; C 1 -C 8 cycloalkylalkyl; C 2 -C 12 alkenyl; C 2 -C 12 alkenyl substituted with halogen; <C 8 ->C 8 -C 8 -alkynyl; or C 2 -C 12 alkynyl

substituert med halogen; når R<3> omfatter høyst 12 C-atomer; R betegner halogen; hydrogen; cyan; C-^-C^-alkoksykarbonyl; substituted with halogen; when R<3> comprises at most 12 C atoms; R denotes halogen; hydrogen; cyan; C 1 -C 4 -Alkoxycarbonyl;

C^-Cg-alkyl; C-^-Cg-alkyl substituert med halogen eller C-^-C^-alkoksy; Cg-Cg-alkenyl; Cg-Cg-alkenyl substituert med halogen eller C-^-C^-alkoksy; C2-Cg-alkynyl; C^-Cg-cyklo-alkyl; C^-Cg-cykloalkyl substituert, med halogen, C-^-C^-alkyl eller C^C^-alkoksy; C^-Cg-cykloalkenyl; C^-Cg-cykloalk-ylalkyl; fenyl-C1-C^-alkyl; furyl; naftyl; tienyl; -0-R^; C 1 -C 8 alkyl; C 1 -C 8 -alkyl substituted with halogen or C 1 -C 6 -alkyl; C 6 -C 8 alkenyl; C 8 -C 8 -alkenyl substituted with halogen or C 1 -C 6 -alkyloxy; C 2 -C 8 alkynyl; C 1 -C 8 cycloalkyl; C 1 -C 8 -cycloalkyl substituted, with halogen, C 1 -C 4 -alkyl or C 1 -C 4 -alkoxy; C 1 -C 8 cycloalkenyl; C 1 -C 8 -cycloalkylalkyl; phenyl-C 1 -C 4 alkyl; furyl; naphthyl; thienyl; -O-R^;

-S-R<4>; -SO-R<4>; -SOg-R<4>, eller -S-R<4>; -SO-R<4>; -SOg-R<4>, or

R^ betegner C-^-C^-alkyl; C-^-C^-alkyl substituert med halogen; R 1 denotes C 1 -C 4 alkyl; C 1 -C 4 -alkyl substituted with halogen;

Cg-C^-alkenyl; Cg-C^-alkenyl substituert med haloen; benzyl; fenyl; eller fenyl substituert med halogen, C-^-C^-alkyl eller C-^-C^-alkoksy; C 6 -C 6 alkenyl; C 6 -C 6 alkenyl substituted with the halo; benzyl; phenyl; or phenyl substituted with halogen, C 1 -C 4 -alkyl or C 1 -C 4 -alkoxy;

R^- gruppene uavhengig av hverandre .betegner halogen; C-^-C<g->The R^- groups independently of each other denote halogen; C-^-C<g->

alkyl; C-^-Cg-alkyl substituert med halogen; C-^-C<g->alkyl monosubstituert med fenyl, cyano eller C-^-C^-alkoksy; Cg-Cg-alkenyl, Cg-Cg-alkenyl substituert med halogen; Cg-Cg-alkynyl; Cg-Cg-alkynyl'substituert med halogen; C^-Cg-cyk-loalkyl; C^-Cg-cyckloalkenyl; C^-Cg-cykloalkylalkyl; C-^-C^-alkanoyloksy; C-^-C^-alkylsulfonyloksy; fenyl; fenyl mono-substituert med 'halogen, C-^-C^-alkyl, C-^-C^-alkoksy eller nitro; nitro; cyano; karboksy; hydroksy; C-^-C^-alkoksykarb-onyl; -O-R6; -S-R6; -SO-R6; eller -S02-R6; alkyl; C 1 -C 8 alkyl substituted with halogen; C 1 -C 6 -alkyl monosubstituted with phenyl, cyano or C 1 -C 6 -alkyl; C 8 -C 8 -alkenyl, C 8 -C 8 -alkenyl substituted with halogen; C 6 -C 8 -alkynyl; C 8 -C 8 -alkynyl substituted with halogen; C 1 -C 8 cycloalkyl; C 1 -C 8 cycloalkenyl; C 1 -C 8 cycloalkylalkyl; C 1 -C 4 -alkanoyloxy; C 1 -C 4 -alkylsulfonyloxy; phenyl; phenyl mono-substituted with halogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy or nitro; nitro; cyano; carboxy; hydroxy; C 1 -C 4 -Alkoxycarbonyl; -O-R6; -S-R6; -SO-R6; or -SO 2 -R 6 ;

R6 betegner C-^-C-^g-alkyl; C-^-C-^-alkyl substituert med halogen; R 6 denotes C 1 -C 6 -alkyl; C 1 -C 4 alkyl substituted with halogen;

Cl~^12 a-Lky1 monosubstituert med fenyl, cyano eller C-^-C^-alkoksy; fenyl; 'fenyl monosubstituert med halogen, C-^-C^-alkyl, C-^-C^-alkbksy eller med nitro; C^-Cg-cykloalkyl; C^-Cg-cykloalkylalkyl; C2-C12-alkenyl; C2-C12-alkenyl substituert med halogen; Cg-C-^-alkynyl; eller Cg-C-^-alkynyl substituert med halogen; når R<6> inneholder høyst 12 C-atomer; Cl~^12 α-Lky1 monosubstituted with phenyl, cyano or C1-3-C4-alkoxy; phenyl; 'phenyl monosubstituted with halogen, C 1 -C 4 alkyl, C 1 -C 4 alkyl or with nitro; C 1 -C 8 cycloalkyl; C 1 -C 8 cycloalkylalkyl; C 2 -C 12 alkenyl; C 2 -C 12 alkenyl substituted with halogen; C 6 -C 6 -alkynyl; or C 6 -C 6 -alkynyl substituted with halogen; when R<6> contains at most 12 C atoms;

m og n uavhengig av hverandre betegner 0, 1 eller 2, forutsatt at når X betegner ; oksygen, R er metyl og R 2er usubstituert fenyl, så er m lik 1 eller 2; m and n independently denote 0, 1 or 2, provided that when X denotes ; oxygen, R is methyl and R 2 is unsubstituted phenyl, then m equals 1 or 2;

samt deres syreaddisjonssalter. Disse forbindelser kan fremstilles ved at man ringslutter en forbindelse med formelen: as well as their acid addition salts. These compounds can be prepared by ring-closing a compound with the formula:

hvor R 1 , R 2og m har betydning som tidligere angitt, where R 1 , R 2 and m have meanings as previously indicated,

med et formyleringsmiddel eller with a formylating agent or

et aminoformyleringsmiddel, an aminoformylating agent,

når en av gruppene Q1 ; og Q 2betegner 2 hydrogenatomer og den andre betegner =CHNHY hvor Y utgjør hydrogen; hydroksy; C-^-C^-alkyl; C-^-C^-alkyl substituert med halogen, cyan, karboksy eller metoksykarbonyl; ; C2-C^-alkenyl; C2-C^-alkynyl; C-^-C^-alkoksy eller dimetylamino; forutsatt at Y inneholder høyst 3 C-atomer; og med en forbindelse med formel when one of the groups Q1 ; and Q 2 denotes 2 hydrogen atoms and the other denotes =CHNHY where Y constitutes hydrogen; hydroxy; C 1 -C 4 alkyl; C 1 -C 4 -alkyl substituted with halogen, cyano, carboxy or methoxycarbonyl; ; C 2 -C 4 alkenyl; C 2 -C 4 -alkynyl; C 1 -C 4 -Alkoxy or dimethylamino; provided that Y contains no more than 3 C atoms; and with a compound of formula

YNH2YNH2

hvor Y har betydningen-som tidligere angitt eller dens syreaddisjonssalt, når bade Q 1 og Q 2 uavhengig av hverandre betegner where Y has the meaning-as previously indicated or its acid addition salt, when both Q 1 and Q 2 independently of each other denote

eller or

hvor R^-gruppene uavhengig av hverandre betegner C-,-CQ-alkyl, where the R₂ groups independently of each other denote C-,-C₂-alkyl,

q ->q ->

eller hvor R^-gruppene sammen med nitrogenatomet som de er bundet til danner en pyrrolidin-, piperidin-, morfolin- eller N-metylpiperazin-gruppe, or where the R^ groups together with the nitrogen atom to which they are attached form a pyrrolidine, piperidine, morpholine or N-methylpiperazine group,

under dannelse av en forbindelse med formel while forming a compound of formula

fulgt av alkylering eller forestring av den således fremstilte forbindelse, hvor Y betegner hydrogen eller hydroksy, respektivt, for fremstilling av den tilsvarende forbindelse hvor Y er lik R, og followed by alkylation or esterification of the compound thus prepared, where Y denotes hydrogen or hydroxy, respectively, to produce the corresponding compound where Y is equal to R, and

når man ønsker forbindelser med formel I hvor when one wants compounds of formula I where

X betegner svovel, behandles forbindelser med formel I hvor X denotes sulphur, compounds of formula I are treated where

X er lik oksygen med P X equals oxygen with P

Således kan forbindelser' med formel I fremstilles ved å ringslutte en forbindelse med formel Thus, compounds of formula I can be prepared by ring-closing a compound of formula

1 2 1 2

hvor R , R og m har betydningen som tidligere angitt, where R , R and m have the meaning as previously indicated,

med en forbindelse med formel with a compound of formula

YNH2YNH2

hvor Y har betydning som tidligere angitt, eller dens syreaddisjonssalt, where Y has the meaning as previously indicated, or its acid addition salt,

når både Q 1 og Q 2 uavhengig av hverandre betegner when both Q 1 and Q 2 independently denote

eller or

hvor r" har betydningen som tidligere angitt, for fremstilling av en forbindelse med formel V; fulgt av alkylering eller forestring av den således fremstilte forbindelse, hvor Y betegner hydrogen eller hydroksy, respektivt, for fremstilling av den tilsvarende forbindelse hvor Y er lik R, og når man vil fremstille forbindelser med formel I hvor X er lik svovel,: behandling av forbindelser med formel I hvor X er lik oksygen med Pg^* Man kan således fremstille forbindelser med formel I ved å ringslutte en forbindelse med formel where r" has the meaning previously indicated, for the preparation of a compound of formula V; followed by alkylation or esterification of the compound thus prepared, where Y denotes hydrogen or hydroxy, respectively, for the preparation of the corresponding compound where Y is equal to R, and when one wants to prepare compounds of formula I where X is equal to sulphur: treatment of compounds of formula I where X is equal to oxygen with Pg^* One can thus prepare compounds of formula I by ring-closing a compound of formula

1 2 1 2

hvor R , R og m har betydningen som tidligere, where R , R and m have the meaning as before,

med et formyleringsmiddel eller et aminoformyleringsmiddel with a formylating agent or an aminoformylating agent

12 12

når en av gruppene Q i og Q betegner 2 hydrogenatomer og den andre betegner -CHNHY!, hvor Y har betydningen som tidligere, for fremstilling av en forbindelse med formel V, when one of the groups Q i and Q denotes 2 hydrogen atoms and the other denotes -CHNHY!, where Y has the meaning as before, for the preparation of a compound of formula V,

fulgt av alkylering eller forestring av den fremstilte forbindelse, hvor Y er lik hydrogen eller hydroksy, respektivt, under dannelse-av den tilsvarende forbindelse hvor Y er lik R, og followed by alkylation or esterification of the compound prepared, where Y is equal to hydrogen or hydroxy, respectively, to form the corresponding compound where Y is equal to R, and

når man ønsker forbindelser med formel I hvor X er lik svovel, behandling av forbindelser med formel I hvor X er lik oksygen med P2^5*when compounds of formula I where X is equal to sulfur are desired, treatment of compounds of formula I where X is equal to oxygen with P2^5*

En utførelse av ringslutningsprosessen som er beskrevet ovenfor består i å omsette en forbindelse med formel IV One embodiment of the cyclization process described above consists in reacting a compound of formula IV

ol 2 ' or 2'

hvor både Q og Q betegner 2 hydrogenatomer, med formamid eller 1,3,5_triazin under dannelse av et mellomprodukt med formel V hvor Y betegner hydrogen, fulgt av alkylering under dannelse av den tilsvarende forbindelse med formel I. Denne utførelse omfatter også bruk av formamid med formamidin-acetat. where both Q and Q represent 2 hydrogen atoms, with formamide or 1,3,5_triazine to form an intermediate of formula V where Y represents hydrogen, followed by alkylation to form the corresponding compound of formula I. This embodiment also includes the use of formamide with formamidine acetate.

i in

Den foretrukne utførelse av syntesen av forbindelser med formel I er tilpasset ut fra metoden beskrevet av Benary og Bitter og El-Kholy et al, nevnt ovenfor. Et egnet substituert 1-fenyl-2-propanon formyleres ved lav temperatur med natrium-metoksyd og etyl-formiat i eter, og produktet behandles -med et aminsalt av den ønskede R-substituent i vandig medium. Det resulterende mellomproduktet er overveiende et 1-(R-amino)-2-fenyl-l-buten-3-on med formel VII. Endel pyridon dannes allerede under dette trinn som beskrevet av El-Kholy et al. Butenonet re-formyleres som ovenfor, og ringslutter spont-ant til 1-substituert 3-fenyl-4(lH)-pyridon med formel I. The preferred embodiment of the synthesis of compounds of formula I is adapted from the method described by Benary and Bitter and El-Kholy et al, mentioned above. A suitable substituted 1-phenyl-2-propanone is formylated at low temperature with sodium methoxide and ethyl formate in ether, and the product is treated with an amine salt of the desired R-substituent in an aqueous medium. The resulting intermediate is predominantly a 1-(R-amino)-2-phenyl-1-buten-3-one of formula VII. Endel pyridone is already formed during this step as described by El-Kholy et al. The butenone is re-formylated as above, and ring-closes spontaneously to 1-substituted 3-phenyl-4(1H)-pyridone of formula I.

En foretrukket gruppe av forbindelser har formel A preferred group of compounds has the formula

hvor: X betegner oksygen eller svovel,° where: X denotes oxygen or sulphur,°

R°betegner C-^-C^-alkyl; Cg-C^-alkenyl; acetoksy eller R° denotes C 1 -C 4 -alkyl; C 6 -C 6 alkenyl; acetoxy or

metoksy; methoxy;

q og p betegner uavhengig av hverandre 0, 1 eller 2, R71-gruppene betegner uavhengig av hverandre halogen; q and p independently represent 0, 1 or 2, the R71 groups independently represent halogen;

C-^-C^-alkyl; trifluormetyl; eller C-^-C^-alkoksy; R^-gruppene betegner uavhengig av hverandre halogen; C-^-C^-alkyl; trif luormetyl eller C-^-C^-alkoksy; eller to R^-grupper som inntar naboplaserte o- og m-stillinger forbindes med fenylringen som de er bundet til under dannelse av en 1-naftylgruppe, forutsatt at når X er oksygen, R° er metyl og p er 0, så er q lik 1 eller 2. C 1 -C 4 alkyl; trifluoromethyl; or C 1 -C 4 -alkyloxy; The R 1 groups independently denote halogen; C 1 -C 4 alkyl; trifluoromethyl or C 1 -C 4 alkoxy; or two R^ groups occupying adjacent o- and m-positions join the phenyl ring to which they are attached to form a 1-naphthyl group, provided that when X is oxygen, R° is methyl and p is 0, then q equal to 1 or 2.

En annen foretrukket forbindelsesgruppe har formelen: Another preferred connecting group has the formula:

hvor de forskjellige symboler har betydning som tidligere angitt. De aller mest foretrukne forbindelser er slike som har formel III, hvor R betegner trifluormetyl. where the different symbols have meaning as previously stated. The very most preferred compounds are those of formula III, where R denotes trifluoromethyl.

I ovenstående formel benyttes de generelle kjem-iske betegnelser under deres normale betydninger. For eksempel refererer betegnelsene C-^-C^-alkyl, Cg-C^-alkenyl, Cg-C^-alkynyl, C^-.C^-alkoksy, C-^-Cg-alkyl, Cg-Cg-alkenyl, Cg-Cg-alkynyl, C-^-Cg-alkyl, Cg-Cg-alkenyl og Cg-Cg-alkynyl seg til grupper som metyl, etyl, isopropyl,i vinyl, allyl, metoksy, isopropoksy, propargyl, isobutyl, heksyl, oktyl, 1,1-dimetylpentyl, 2-okten-yl, pentyl, 3-heksynyl,■l-etyl-2-heksenyl, 3-°ktynyl, 5-hepten-yl, l-propyl-3-butynyl og krotyl. In the above formula, the general chemical designations are used under their normal meanings. For example, the designations refer to C 1 -C 4 -alkyl, C 8 -C 4 -alkenyl, C 8 -C 4 -alkynyl, C 1 -C 4 -alkyl, C 1 -C 4 -alkyl, C 8 -C 8 -alkenyl, Cg-Cg-alkynyl, C-^-Cg-alkyl, Cg-Cg-alkenyl and Cg-Cg-alkynyl to groups such as methyl, ethyl, isopropyl, vinyl, allyl, methoxy, isopropoxy, propargyl, isobutyl, hexyl, octyl, 1,1-dimethylpentyl, 2-octen-yl, pentyl, 3-hexynyl, ■1-ethyl-2-hexenyl, 3-octynyl, 5-hepten-yl, 1-propyl-3-butynyl and crotyl.

Betegnelsene C^-Cg-cykloalkyl og C^-Cg-cykloalk-enyl omfatter grupper som cyklopropyl, cyklobutyl, cykloheksyl, cyklobutenyl, cyklopentenyl og cykloheksadienyl. The terms C 1 -C 8 -cycloalkyl and C 1 -C 8 -cycloalkenyl include groups such as cyclopropyl, cyclobutyl, cyclohexyl, cyclobutenyl, cyclopentenyl and cyclohexadienyl.

Betegnelsene C^-Cg-cykloalkylalkyl refererer seg til grupper som cyklopropylmetyl, cyklobutylmetyl, cykloheksyl-metyl og cykloheksyletyl. The terms C 1 -C 8 cycloalkylalkyl refer to groups such as cyclopropylmethyl, cyclobutylmethyl, cyclohexylmethyl and cyclohexylethyl.

C-^-C^-alkanoyloksy kan f. eks. betegne grupper som C-^-C^-alkanoyloxy can e.g. denote groups which

formyloksy, acetoksy og propionyloksy. formyloxy, acetoxy and propionyloxy.

Betegnelsen C^-C^-alkoksykarbonyl omfatter f.eks. grupper som metoksykarljonyl, etoksykarbonyl og isopropoksykarb-onyl. The term C₁-C₁-Alkoxycarbonyl includes e.g. groups such as methoxycarbonyl, ethoxycarbonyl and isopropoxycarbonyl.

Uttrykket; C-^-C^-alkylsulfonyloksy refererer seg The expression; C-3-C4-alkylsulfonyloxy refers

f.eks. til grupper som metylsulfonyloksy og propylsulfonyloksy. e.g. to groups such as methylsulfonyloxy and propylsulfonyloxy.

Halogen omfatter fluor, klor, brom og jod. Halogen includes fluorine, chlorine, bromine and iodine.

De forbindelser som er beskrevet ovenfor kan danne syreaddisjonssalter; og slike salter er egnede produkter av oppfinnelsen. Foretrukne salter er hydrogenhalogenider som hydrogenjodider, hydrogenbromider, hydrogenklorider og hydro-genfluorider. Salter av sulfonsyrer er også gunstige. Slike salter omfatter sulfonater, metylsulfonater og toluensulfonater. The compounds described above can form acid addition salts; and such salts are suitable products of the invention. Preferred salts are hydrogen halides such as hydrogen iodides, hydrogen bromides, hydrogen chlorides and hydrogen fluorides. Salts of sulfonic acids are also beneficial. Such salts include sulfonates, methyl sulfonates and toluene sulfonates.

Det er irnilig å fremstille mellomproduktet 1-usubstituert pyridon ved å'benytte NH^ i stedet for YNHg under metoden, eller ved å benytte fremgangsmåten til Benary og Bitter. Pyridonet blir da alkylert i 1-stilling med et halogenid av R, eller med et dialkylsulfat etter vanlige metoder, og gir forbindelser med formel T. It is possible to prepare the intermediate 1-unsubstituted pyridone by using NH 2 instead of YNH 2 during the method, or by using the method of Benary and Bitter. The pyridone is then alkylated in the 1-position with a halide of R, or with a dialkyl sulphate according to usual methods, and gives compounds of formula T.

En annen1 alkyleringsmetode er å omdanne 1-usubstituert pyridon til 4-halogen- eller 4-alkoksy-derivater ved omsetning med et halogeneringsmiddel eller et .alkyleringsmiddel. Egnede halogeneringsmidler er f.eks. POCl^, POBr^, PCl^ og lignende.' O-alkyleringsmidler omfatter reagenser som metyl-trifluormetansulfonat, metyl-fluorsulfonat og lignende, samt alkyl-halogenider i nærvær av base. I neste trinn omsettes 4~ halogen- eller 4-alkoksy-forbindelsen med et halogenid av R, og danner 1-R-substituert, 4-substituert pyridiniumsalt. Dette saltet hydrolyseres derpå med enten en mineralsyre eller et alkalimetallhydroksyd til det ønskede produkt. Se f.eks. Takahashi et al., Pharm. Bull. (Japan) 1, 70-74 (1953). Another 1 alkylation method is to convert 1-unsubstituted pyridone into 4-halogen or 4-alkoxy derivatives by reaction with a halogenating agent or an alkylating agent. Suitable halogenating agents are e.g. POCl^, POBr^, PCl^ and the like.' O-alkylating agents include reagents such as methyl trifluoromethanesulfonate, methyl fluorosulfonate and the like, as well as alkyl halides in the presence of base. In the next step, the 4~ halogen or 4-alkoxy compound is reacted with a halide of R, forming a 1-R-substituted, 4-substituted pyridinium salt. This salt is then hydrolysed with either a mineral acid or an alkali metal hydroxide to the desired product. See e.g. Takahashi et al., Pharm. Bull. (Japan) 1, 70-74 (1953).

Som ventet, kan aminene, RNHg, brukes i form av salter, fortrinnsvis hydrohalogenidsalter, omfattende hydro-klorider, hydrobromider og lignende. Slike salter er ofte mer hensiktsmessige å benytte enn de frie aminer. As expected, the amines, RNHg, can be used in the form of salts, preferably hydrohalide salts, including hydrochlorides, hydrobromides and the like. Such salts are often more appropriate to use than the free amines.

Formyleringsmidlene som benyttes i metoden velges blant vanlige reagenser som brukes til slike reaksjoner. De foretrukne formyleringsmidler er estere av maursyre med formelen The formylating agents used in the method are selected from common reagents used for such reactions. The preferred formylating agents are esters of formic acid of the formula

Lignende formyleringsmetoder beskrives i Organic Syntheses 300-02 (Samlebind III 1955). Similar formylation methods are described in Organic Syntheses 300-02 (Collection III 1955).

Estrene brukes i nærvær av sterke baser, hvorav alkalimetall-alkoksyder foretrekkes, av typen natrium-metoksyd, kalium-etoksyd og litium-propoksyd. Andre baser kan brukes, som alkalimetallhydrider, alkalimetallamider og uorganiske baser som alkalimetallkarbonater og -hydroksyder. Sterke organiske baser som diazabicyklononan og diazabicykloundekan kan også brukes. The esters are used in the presence of strong bases, of which alkali metal alkoxides are preferred, of the type sodium methoxide, potassium ethoxide and lithium propoxide. Other bases may be used, such as alkali metal hydrides, alkali metal amides, and inorganic bases such as alkali metal carbonates and hydroxides. Strong organic bases such as diazabicyclononane and diazabicycloundecane can also be used.

Reaksjonene med formyleringsmidlene gjennomføres i aprotiske oppløsningsmidler av den typen som vanligvis brukes til kjemisk syntese. Etyleter er vanligvis det foretrukne opp-løsningsmiddel. Etere generelt, inklusive oppløsningsmidler som etylpropyleter, etylbutyleter, 1,2-dimetoksyetan og t'etra-hydrofuran, aromatiske oppløsningsmidler som benzen og xylen, og alkaner som heksan og oktan kan brukes som formylerings-oppløs-ningsmidler. The reactions with the formylating agents are carried out in aprotic solvents of the type usually used for chemical synthesis. Ethyl ether is usually the solvent of choice. Ethers in general, including solvents such as ethyl propyl ether, ethyl butyl ether, 1,2-dimethoxyethane and tetrahydrofuran, aromatic solvents such as benzene and xylene, and alkanes such as hexane and octane can be used as formylation solvents.

På grunn ay de sterke baser som benyttes til for-myleringsreaksjonene, gir lave temperaturer de beste resultater. Reaksjoner ved temperaturer me Hom ca. -25°C og +10°C foretrekkes. Reaksjonsblandingen kan tillates å varme seg opp til romtemperatur, men fortrinnsvis først etter at reaksjonen er p'å vei mot avslutningen. Reaksjonstider fra ca. 1 til 24 timer er til-strekkelig for å oppnå økonomiske utbytter under formylerings-reaksjonene. Due to the strong bases used for the formylation reactions, low temperatures give the best results. Reactions at temperatures with Hom approx. -25°C and +10°C are preferred. The reaction mixture can be allowed to warm to room temperature, but preferably only after the reaction is on its way to completion. Reaction times from approx. 1 to 24 hours is sufficient to obtain economic yields during the formylation reactions.

Det valgte, aminoformyleringsmiddel som brukes til disse synteser kan være alle forbindelser som kan reagere med en aktiv metylengruppe og innføre en =CHN(R^)^-gruppe, eller dens syreaddisjonssalt. i Slike midler velges blant ortoform- The chosen aminoformylating agent used for these syntheses can be any compound which can react with an active methylene group and introduce a =CHN(R^)^ group, or its acid addition salt. i Such agents are chosen from orthoform-

amider, amides,

formiat-ester-aminaler, formate ester aminals,

formamid-acetaler, tris(formylamino)metaner, og formiminium-halogenider, formamide acetals, tris(formylamino)methanes, and formiminium halides,

Q<3> i ovenstående struktur betegner oksygen eller svovel, og R<10> betegner C^-Cg-alkyl eller -fenyl. Q<3> in the above structure denotes oxygen or sulphur, and R<10> denotes C 1 -C 8 alkyl or -phenyl.

Nyttige henvisninger til aminoformyleringsmidler er blant andre DeWolfe, Carboxylic Acid Derivatives 420-506 Useful references for aminoformylation agents include DeWolfe, Carboxylic Acid Derivatives 420-506

(Academic Press 1970), og Ulrich, Chemistry of Imidoyl Halides 87-96 (Plenum Press I968). Bredereck et al. har skrevet mange publikasjoner om slike midler og reaksjoner, hvorav følgende er typiske: Ber. 101, 4048-56 (1968); Ber. 104, 2709-26 (I97I); Ber. 106, 373<2->42 (1973); Ber. 97, 3397-406 (I964); Ann. 762, 62-72 (1972); Ber. 97, 3407-17 (I964); Ber. 103, 210-21 (1970); Angew. Chem. 78, 147 (1966); Ber. 98, 2887-96 (I965); Ber. 96, I5O5-I4 (1963); Ber. 104, 3475-85 (I97D; Ber. 101, 41-50 (19-68); Ber. 106, 3725-31 (1973); og Angew. Chem. Int'l. Ed. 5, 132 (I966). Andre nyttige publikasjoner på området er Kreutz-berger et al., Arch. der Pharm. 301, 88I-96 (I968), og 302, 362-75 (I969), og Weingarten et al., J. Org. Chem. 32, 3293-94 (Academic Press 1970), and Ulrich, Chemistry of Imidoyl Halides 87-96 (Plenum Press I968). Bredereck et al. has written many publications on such agents and reactions, of which the following are typical: Ber. 101, 4048-56 (1968); Pray. 104, 2709-26 (197I); Pray. 106, 373<2->42 (1973); Pray. 97, 3397-406 (1964); Ann. 762, 62-72 (1972); Pray. 97, 3407-17 (1964); Pray. 103, 210-21 (1970); Angew. Chem. 78, 147 (1966); Pray. 98, 2887-96 (1965); Pray. 96, 1505-14 (1963); Pray. 104, 3475-85 (197D; Ber. 101, 41-50 (19-68); Ber. 106, 3725-31 (1973); and Angew. Chem. Int'l. Ed. 5, 132 (1966). Other useful publications in the field are Kreutzberger et al., Arch. der Pharm. 301, 881-96 (1968), and 302, 362-75 (1969), and Weingarten et al., J. Org. Chem. 32 , 3293-94

(1967). (1967).

Aminoformyleringer gjennomføres vanligvis uten oppløsningsmiddel, ved forhøyet temperatur mellom ca. 50°C og 200°C. Oppløsningsmidler som dimetylformamid benyttes enkelte ganger, men særlig når det er ønskelig å øke blandingens koke-punkt . Aminoformylations are usually carried out without a solvent, at an elevated temperature between approx. 50°C and 200°C. Solvents such as dimethylformamide are sometimes used, but especially when it is desired to increase the boiling point of the mixture.

Ved aminoformylering med formiminium-halogenider benyttes imidlertid aprotiske oppløsningsmidler som ovenfor beskrevet, i forbindelse med formylerings-oppløsningsmidler, ved temperaturer mellom ca. 0°C og 50°C, og fortrinnsvis ved romtemperatur. Halogenerte oppløsningsmidler som kloroform og metylenklorid kan også brukes under slike aminoformyleringer, om ønsket. In aminoformylation with formiminium halides, however, aprotic solvents are used as described above, in connection with formylation solvents, at temperatures between approx. 0°C and 50°C, and preferably at room temperature. Halogenated solvents such as chloroform and methylene chloride can also be used during such aminoformylations, if desired.

Utvekslings-reaksjonene med YNHg gjennomføres best i protiske oppløsningsmidler, hvorav alkanoler foretrekkes og etanol er best egnet. Temperaturer fra ca. -20°C til 100°C kan brukes. Romtemperatur er tilfredsstillende og foretrekkes derfor. The exchange reactions with YNHg are best carried out in protic solvents, of which alkanols are preferred and ethanol is most suitable. Temperatures from approx. -20°C to 100°C can be used. Room temperature is satisfactory and is therefore preferred.

Utgangsstoffer med formel IV fremstilles ved å omsette en forbindelse med formel Starting substances of formula IV are prepared by reacting a compound of formula

1 2 hvor: R , R og m har betydning som tidligere angitt, med et formyleringsmiddel eller et aminoformyleringsmiddel. Når man benytter formyleringsmiddel dannes et keton-mellomprodukt med formel 1 2 where: R , R and m have the meanings previously indicated, with a formylating agent or an aminoformylating agent. When a formylating agent is used, a ketone intermediate with the formula is formed

Omsetning med et aminoformyleringsmiddel gir et enaminoketon som X nedenfor. Reaction with an aminoformylating agent gives an enaminoketone as X below.

Kjemikere vil forstå at selv om formel IX og X viser den første formylering eller aminoformylering slik den foregår på en bestemt side av ketonet, kan formyleringen finne sted på den andre siden av ketonet, avhengig av aktiverings-egenskapene hos R 1 og R 2. Reaksjonsforløpet er det samme i begge tilfeller. Man vil også forstå at produktet av formyleringen eller aminoformyleringen i mange tilfeller i virkelig-heten vil være en blanding som inneholder de to mulige monosubstituerte forbindelser og den disubstituerte forbindelse. Chemists will appreciate that although formulas IX and X show the first formylation or aminoformylation as occurring on a particular side of the ketone, the formylation may occur on the other side of the ketone, depending on the activation properties of R 1 and R 2 . is the same in both cases. It will also be understood that the product of the formylation or aminoformylation will in many cases in reality be a mixture containing the two possible monosubstituted compounds and the disubstituted compound.

Det monosubstituerte produkt formyleres eller aminoformyleres igjen og utveksles med et amin med formel YNHg. Trinnene kan gjennomføres i ønsket rekkefølge. Hvis utvekslin-gen gjennomføres først, er mellomproduktet et enaminoketon med formel The monosubstituted product is formylated or aminoformylated again and exchanged with an amine of formula YNHg. The steps can be carried out in the desired order. If the exchange is carried out first, the intermediate product is an enamino ketone of formula

Formylering eller aminoformylering av ovenstående enaminoketon, som også kan gjengis med formel VII, danner pyridon-produktet, idet mellomproduktet ringsluttes så snart den andre gruppen innføres på den andre metylengruppen. Formylation or aminoformylation of the above enaminoketone, which can also be represented by formula VII, forms the pyridone product, the intermediate product being ring-closed as soon as the second group is introduced onto the second methylene group.

Enten forbindelse IX eller X kan formyleres eller aminoformyleres til mellomprodukter i henhold til form-lene nedenfor: Either compound IX or X can be formylated or aminoformylated to intermediates according to the formulas below:

Det vil være klart at en forbindelse i likhet med XIII, hvor formyl- og aminoformyl-gruppene er ombyttet, er ekvivalent på alle måter til forbindelsen XIII. Pyridoner dannes ut fra alle ovenstående tre mellomprodukter som alle kan representeres ved formel VI, ved kontakt mellom mellomproduktet og et amin med formel YNHg. It will be clear that a compound like XIII, where the formyl and aminoformyl groups are interchanged, is equivalent in all respects to compound XIII. Pyridones are formed from all of the above three intermediates, all of which can be represented by formula VI, by contact between the intermediate and an amine of formula YNHg.

2-propanon-utgangsstoffene med formel VIII kan fremstilles ved kjente litteratursynteser.■ Se for eksempel, Coan et al., J. Am. Chem. Soc. 76, 501 (1954)» Sullivan et al., "Disodium Tetracarbonylferrate", American Laboratory 49-56 The 2-propanone starting materials of formula VIII can be prepared by known literature syntheses. See, for example, Coan et al., J. Am. Chem. Soc. 76, 501 (1954)» Sullivan et al., "Disodium Tetracarbonylferrate", American Laboratory 49-56

(Juni I974); Collman et al., "Synthesis of Hemifluorinated Ketones using Disodium Tetracarbonylferrate", (syntese av halv-fluorerte ketoner med dinatrium-tetrakarbonylferrat), J. Am. Chem. Soc. 95, 2689-91 (1973), Collman et al., "Acyl and Alkyl Tetracarbonylferrate Complexes as Intermediates in the Synthesis of Aldehydes and Ketones" (acyl- og alkyl-tetrakarbonylferrat-komplekser som mellomprodukter ved syntese av aldehyder og ketoner), J. Am. Chem. Soc. 94, 25l6-l8 (I972). (June I974); Collman et al., "Synthesis of Hemifluorinated Ketones using Disodium Tetracarbonylferrate", J. Am. Chem. Soc. 95, 2689-91 (1973), Collman et al., "Acyl and Alkyl Tetracarbonylferrate Complexes as Intermediates in the Synthesis of Aldehydes and Ketones", J Am. Chem. Soc. 94, 2516-18 (1972).

Forbindelser med formel X kan også fremstilles - slik: Compounds of formula X can also be prepared - like this:

Det vil være klart at reaksjon (A) også kan utføres på motsatt måte, som nedenfor: It will be clear that reaction (A) can also be carried out in the opposite way, as below:

Det er også mulig å danne utgangsstoffene med formel VI hvor både Q 1 og Q 2 er identiske ved å bruke fosgen som karbonylhalogenid når 3- og 5-substituentene på pyridon-produktet -med formel I er like. It is also possible to form the starting materials of formula VI where both Q 1 and Q 2 are identical by using phosgene as the carbonyl halide when the 3- and 5-substituents on the pyridone product -of formula I are the same.

Generelt, blir mellomproduktene under syntesen ikke renset, men benyttes fortløpende etter separasjon ved ekstraksjon, nøytralisasjon eller fjerning av overskudd av opp-løsningsmiddel eller reaktant. In general, the intermediate products during the synthesis are not purified, but are used continuously after separation by extraction, neutralization or removal of excess solvent or reactant.

Enamin-acylerings-reaksjonene A-C utføres i nærvær av baser som tertiære aminer, alkalimetallkarbonater, mag-nesiumoksyder og lignende, og i aprotiske oppløsningsmidler som beskrevet ovenfor. The enamine acylation reactions A-C are carried out in the presence of bases such as tertiary amines, alkali metal carbonates, magnesium oxides and the like, and in aprotic solvents as described above.

Som kjemikere vil forstå, er det i enkelte tilfeller nødvendig å tilføye andre syntesetrinn etter at pyridon-forbindelsen er fremstilt. For eksempel er det gunstig å fremstille forbindelser med alkoksy-, alkanoyloksy- og lignende R"'"-og R^-substituenter ved først å fremstille den tilsvarende hydroksy-substituerte forbindelsen, og deretter substituere på As chemists will appreciate, in some cases it is necessary to add other synthetic steps after the pyridone compound has been prepared. For example, it is advantageous to prepare compounds with alkoxy, alkanoyloxy and similar R"'"- and R^-substituents by first preparing the corresponding hydroxy-substituted compound, and then substituting on

oksygenatomet. the oxygen atom.

Pyridintioner med formel I fremstilles enkelt ved behandling av de tilsvarende pyridoner med ?2^5 ^ Pyridin ved tilbakeløpstemperatur, etter kjente metoder. Pyridine ions of formula I are easily prepared by treating the corresponding pyridones with ?2^5 ^ pyridine at reflux temperature, according to known methods.

1-acetoksy-forbindelser med formel I fremstilles ved først å lage den tilsvarende 1-hydroksypyridon med NHgOH som amin, og forestre med eddiksyre-anhydrid. De andre 1-sub-st ituenter fremstilles ved egnede Y-substituenter på aminene, YNHg, som brukes for fremstilling av pyridonene. 1-acetoxy compounds of formula I are prepared by first making the corresponding 1-hydroxypyridone with NHgOH as amine, and esterifying with acetic anhydride. The other 1-substituents are prepared by suitable Y-substituents on the amines, YNHg, which are used for the preparation of the pyridones.

De følgende fremstillingseksempler gis for at fagfolk på området skal kunne fremstille en hvilken som helst ønsket forbindelse med formel I. The following preparation examples are given so that those skilled in the art will be able to prepare any desired compound of formula I.

Eksemplene viser de forskjellige metoder for fremstilling av forbindelser med formel I.- Det vil imidlertid være klart at alle fremgangsmåtene kan brukes, med egnede vari-asjoner, for fremstilling av en hvilken som helst forbindelse med formel I. The examples show the different methods for the preparation of compounds of formula I. It will be clear, however, that all methods can be used, with suitable variations, for the preparation of any compound of formula I.

Det er angitt at mange eksempelforbindelser kan fremstilles etter den generelle metode for fremstilling av en foregående eksempelforbindelse. I slike tilfeller vi 1 en van-■ lig organisk kjemiker lett se de mindre forandringer fra eks-empelmetoden som er nødvendig for å fremstille den andre forbindelsen. It is indicated that many exemplary compounds can be prepared according to the general method for preparing a preceding exemplary compound. In such cases, an ordinary organic chemist can easily see the minor changes from the example method that are necessary to prepare the second compound.

Temperaturene er oppgitt i °C. NMR-spektra ble målt på et 60 mH instrument med tetrametylsilan som egenrefer-anse og er oppgitt i perioder pr. sekund (cycles per second = CPS). Smeltepunkter (sm.p.) ble bestemt i en måleblokk. The temperatures are given in °C. NMR spectra were measured on a 60 mH instrument with tetramethylsilane as a self-reference and are given in periods per second (cycles per second = CPS). Melting points (m.p.) were determined in a measuring block.

Det første eksempel nedenfor illustrerer fremstilling av en forbindelse etter den foretrukne syntesemetode ut fra en forbindelse med formel VII. The first example below illustrates the preparation of a compound according to the preferred synthesis method from a compound of formula VII.

Eksempel. 1 Example. 1

Til en oppløsning av 4 1 tetrahydrofuran og 284 g natriummetoksyd tilsatte man 556 g 1-(3-trifluormetylfenyl)~3-fenyl-2-propanon ved 10^-15°C i løpet av 20 minutter. Reaksjonsblandingen ble omrørt i.15 minutter. Derpå tilsatte man 370 g etyl-formiat i løpet av 30 minutter, og blandingen ble omrørt i 1 time ved 10-15°C. Til blandingen satte man ytterligere 296 g etyl-formiat i løpet av 30 minutter. Reaksjonsblandingen ble hensatt til oppvarming til romtemperatur under røring over natten. Derpå tilsatte man en oppløsning av 336 g metylamin-hydroklorid i 1 liter vann. Den 2-fasige blanding ble omrørt ved 30°C i 30 minutter., Blandingen ble derpå ekstrahert med metylenklorid, og ekstraktene slått sammen og konsentrert i vakuum, hvilket ga en oljeaktig rest som besto av en blanding inneholdende l-metylamino-2-fenyl-4-(3-trifluormetylfenyl)-1-buten-3-on og l-metylamino-4-feny1-2-(3-trifluormetylfenyl)-1-buten-3-on. To a solution of 4 1 of tetrahydrofuran and 284 g of sodium methoxide, 556 g of 1-(3-trifluoromethylphenyl)~3-phenyl-2-propanone were added at 10°-15°C over the course of 20 minutes. The reaction mixture was stirred for 15 minutes. 370 g of ethyl formate were then added over 30 minutes, and the mixture was stirred for 1 hour at 10-15°C. A further 296 g of ethyl formate were added to the mixture over the course of 30 minutes. The reaction mixture was allowed to warm to room temperature with stirring overnight. A solution of 336 g of methylamine hydrochloride in 1 liter of water was then added. The 2-phase mixture was stirred at 30°C for 30 minutes. The mixture was then extracted with methylene chloride, and the extracts combined and concentrated in vacuo to give an oily residue consisting of a mixture containing 1-methylamino-2-phenyl -4-(3-trifluoromethylphenyl)-1-buten-3-one and 1-methylamino-4-phenyl-2-(3-trifluoromethylphenyl)-1-buten-3-one.

Inndampningsresten ble omsatt etter samme metode som ovenfor. Etter oppløsning i metylenklorid ble blandingen vasket med vann og tørket. Etter tørking og fjernelse av opp-løsningsmidlet viste det seg at det faste produktet veide 430 g, utbytte 65%. Produktet ble omkrystallisert fra etyleter, og det rensede produktet identifisert som l-metyl-3-fenyl-5-(3_ trifluormetylfenyl)-4(1H)-pyridon, sm.p. 153-155°C, ved IR-spektra, NMR-spektrumog tynnsjiktskromatografiske analyser. Elementæranalysen var som følger: The evaporation residue was reacted using the same method as above. After dissolution in methylene chloride, the mixture was washed with water and dried. After drying and removal of the solvent, the solid product was found to weigh 430 g, yield 65%. The product was recrystallized from ethyl ether and the purified product identified as 1-methyl-3-phenyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, m.p. 153-155°C, by IR spectra, NMR spectrum and thin-layer chromatographic analyses. The elemental analysis was as follows:

Fremgangsmåten ifølge Eksempel 1 ble også brukt for fremstilling av de nedenstående eksempelforbindelser. Eksempel 2 The method according to Example 1 was also used for the preparation of the example compounds below. Example 2

l-metyl-3,5-bis(3-trifluormetylfenyl)-4(1H)-pyridon, sm.p. 152-154°C, utbytte 39%. 1-methyl-3,5-bis(3-trifluoromethylphenyl)-4(1H)-pyridone, m.p. 152-154°C, yield 39%.

1 1

1 1

Eksempel 3 Example 3

3-fenyl-1-(2,2,2-trifluoretyl)-5-(3-trifluor-metylf enyl) -4 (1H) -pyridon, NMR-kvartett sentrert ved 256 CPS, aromatiske protoner ved 420-468 CPS, utbytte 46%. 3-phenyl-1-(2,2,2-trifluoroethyl)-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, NMR quartet centered at 256 CPS, aromatic protons at 420-468 CPS, dividend 46%.

Eksempel 4 Example 4

3-(3-bromfenyl)-5-(3-klorfenyl)-l-metyl-4(lH)-pyridon, sm.p. 192°C, utbytte 23$. Eksempel 5 3-(3-bromophenyl)-5-(3-chlorophenyl)-1-methyl-4(1H)-pyridone, m.p. 192°C, yield 23$. Example 5

3-(3-klorfenyl)-5-(4-klor fenyl)-l-métyl-4(1H)-pyridon, sm.p. 170-172°C, utbytte 26$. 3-(3-chlorophenyl)-5-(4-chlorophenyl)-1-methyl-4(1H)-pyridone, m.p. 170-172°C, yield 26$.

Eksempel 6 Example 6

3-(2-fluorfenyl)-l-metyl-5-(3-trifluormetyl-fenyl)-4(lH)-pyridon, sm.p. 152-154°C, utbytte 20$. 3-(2-fluorophenyl)-1-methyl-5-(3-trifluoromethyl-phenyl)-4(1H)-pyridone, m.p. 152-154°C, yield 20$.

Eksempel 7_ Example 7_

3-(2-klorfenyl)-5-(3-klorfenyl)-l-metyl-4(lH)-pyridon, sm.p. l60-l6l°C, utbytte 15$. 3-(2-chlorophenyl)-5-(3-chlorophenyl)-1-methyl-4(1H)-pyridone, m.p. l60-l6l°C, yield 15$.

Eksempel 8. Example 8.

3-(3-metoksyfenyl)-l-metyl-5-(3-trifluormetyl-fenyl)-4(1H)-pyridon, sm.p. 113-115°C, utbytte 7$. 3-(3-Methoxyphenyl)-1-methyl-5-(3-trifluoromethyl-phenyl)-4(1H)-pyridone, m.p. 113-115°C, yield 7$.

Eksempel 9 Example 9

3-(4-klorfenyl)-l-metyl-5-(3-trifluormetylfenyl)-4(1H)-pyridon, sm.p. 153-155°C, utbytte 26$. 3-(4-chlorophenyl)-1-methyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, m.p. 153-155°C, yield 26$.

Eksempel 10 Example 10

l-allyl-3-fenyl-5-(3-trifluormetylfenyl)-4(1H)-pyridon, sm.p. 107-109°C, utbytte 38$. 1-allyl-3-phenyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, m.p. 107-109°C, yield 38$.

Eksempel 11 Example 11

3-(4-isopropylfenyl)-l-metyl-5-fenyl-4(1H)-pyridon, sm.p. 159°C, utbytte 60$. 3-(4-isopropylphenyl)-1-methyl-5-phenyl-4(1H)-pyridone, m.p. 159°C, yield 60$.

Eksempel 12 Example 12

3-(2-klorfenyl)-l-metyl-5-(3-trifluormetylfenyl)-4(1H)-pyridon, sm.p. 191-193°C, utbytte 14$. 3-(2-chlorophenyl)-1-methyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, m.p. 191-193°C, yield 14$.

Eksempel 13 Example 13

3-(3-fluorfenyl)-l-metyl-5-(3-trifluormetyl-fenyl)-4(lH)-pyridon, sm.<p>. 94-96°C, utbytte 13$. 3-(3-fluorophenyl)-1-methyl-5-(3-trifluoromethyl-phenyl)-4(1H)-pyridone, sm.<p>. 94-96°C, yield 13$.

Eksempel 14 Example 14

3-(4-fluorfenyl)-l-metyl-5-(3-trifluormetylfen-yl)-4(lH)-pyridon, sm.p. 133-134°C, utbytte 29$. 3-(4-fluorophenyl)-1-methyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, m.p. 133-134°C, yield 29$.

Eksempel 15 Example 15

3-(4-metoksyfenyl)-l-metyl-5-(3-trifluormetyl-fenyl)-4(1H)-pyridon, sm.p. l62-l65°C, utbytte 33$. 3-(4-Methoxyphenyl)-1-methyl-5-(3-trifluoromethyl-phenyl)-4(1H)-pyridone, m.p. l62-l65°C, yield 33$.

Neste eksempel illustrerer en syntese hvor enaminoketonet med formel X først omsettes med et amin under dannelse av en forbindelse mgd formel VII, og deretter med et aminoformyleringsmiddel for fremstilling av det ønskede pyridon med formel I. The next example illustrates a synthesis where the enaminoketone of formula X is first reacted with an amine to form a compound of formula VII, and then with an aminoformylating agent to produce the desired pyridone of formula I.

Eksempel 16 Example 16

Et enaminoketon, 2-fenyl-l-dietylamino-4-(3-métyltiofenyl)-l-buten-3-on ble fremstilt som angitt i første trinn fra Eksempel 73» up fra 17,5 g N,N-dietylstyrylamin og An enamino ketone, 2-phenyl-1-diethylamino-4-(3-methylthiophenyl)-1-buten-3-one was prepared as indicated in the first step from Example 73" up from 17.5 g of N,N-diethylstyrylamine and

15 g (3-metyltiofenyl)acietyl-klorid. Enaminoketonet ble opp-løst i 300 ml etanol, blandet med 20 g metylamin-hydroklorid 15 g of (3-methylthiophenyl)acetyl chloride. The enamino ketone was dissolved in 300 ml of ethanol, mixed with 20 g of methylamine hydrochloride

og omrørt i ca. 24 timer,. Oppløsningsmidlet ble avdampet, residuet ekstrahert med etyleter og oppløsningen vasket med vann. Det organiske sjiktet tørket over vannfri natriumsulfat, og den tørkede oppløsning avdampet til tørrhet, hvilket ga l-metylamino-4-(3-metyltiofenyl)-2-fenyl-l-buten-3-on. and stirred for approx. 24 hours,. The solvent was evaporated, the residue extracted with ethyl ether and the solution washed with water. The organic layer was dried over anhydrous sodium sulfate and the dried solution evaporated to dryness to give 1-methylamino-4-(3-methylthiophenyl)-2-phenyl-1-buten-3-one.

Residuet ble blandet med 50 ml dimetylformamid-dimetylacetal og oppvarmet ved tilbakeløpstemperatur i 20 timer. Reaksjonsblåndingen ble heilt opp i vann og blandingen ekstrahert først med eter og deretter med metylenklorid. Begge ekstrakter ble vasket med vann, tørket og inndampet til tørrhet. Produktet var 9 g l-metjfl-3- (3-metyltiof enyl)-5-fenyl-4(lH)-pyridon, som ble identifisert ved hjelp av "NMR, som viste topper ved 144 og 227 CPS, med aromatiske protoner ved 420-440 og 442-458 CPS. The residue was mixed with 50 ml of dimethylformamide-dimethyl acetal and heated at reflux temperature for 20 hours. The reaction mixture was poured into water and the mixture extracted first with ether and then with methylene chloride. Both extracts were washed with water, dried and evaporated to dryness. The product was 9 g of 1-methyl-3-(3-methylthiophenyl)-5-phenyl-4(1H)-pyridone, which was identified by "NMR, showing peaks at 144 and 227 CPS, with aromatic protons at 420-440 and 442-458 CPS.

Etter en lignende fremgangsmåte fremstilte man de nedenstående forbindelser. Eksempelforbindelsene 17 og 18 ble' fremstilt ved oksydasjon av forbindelsen fra Eksempel 16 med m-klorperbenzosyre. Following a similar procedure, the following compounds were prepared. Example compounds 17 and 18 were prepared by oxidation of the compound from Example 16 with m-chloroperbenzoic acid.

Eksempel 17 Example 17

l-metyl-3-(3-metylsulfinylfenyl)-5-fenyl-4(1H) - pyridon, sm.p. l6l-l64°C, utbytte 57$- 1-methyl-3-(3-methylsulfinylphenyl)-5-phenyl-4(1H)-pyridone, m.p. l6l-l64°C, yield 57$-

Eksempel 18 Example 18

l-metyl-3<i>(3-metylsulfonylfenyl)-5-fenyl-4(1H)-pyridon, sm.p. 176-l8l°C, utbytte 31$. 1-methyl- 3<i>(3-methylsulfonylphenyl)-5-phenyl-4(1H)-pyridone, m.p. 176-l8l°C, yield 31$.

Eksempel 19 Example 19

l-metyl-3^fenyl-5-(4-trifluormetylfenyl)-4(lH)-pyridon, sm.p. l64-l66°C, utbytte 16%. 1-methyl-3-phenyl-5-(4-trifluoromethylphenyl)-4(1H)-pyridone, m.p. l64-l66°C, yield 16%.

Følgende eksempel illustrerer en variasjon av fremgangsmåten som begynner med et karbonylhalogenid, hvorved enaminoketonet med formel X først utveksles med et amin for fremstilling av en forbindelse med formel VII, og pyridonet med formel I derpå fremstilles ved formylering av mellomprodukt et. The following example illustrates a variation of the process starting with a carbonyl halide, whereby the enamino ketone of formula X is first exchanged with an amine to produce a compound of formula VII, and the pyridone of formula I is then prepared by formylation of intermediate et.

Eksempel 20 Example 20

Man fremstilte et enaminoketon, nemlig 4-(3-benzyloksyfenyl)-l-dietylamino-2-fenyl-l-buten-3-on, idet man fulgte første trinn fra fremgangsmåten i Eksempel 73» ut ?Ta 14,4 g (3-benzyloksyfenyl)acetylklorid og 9>6 S N,N-dietylstyryl-amin. En 13 g porsjon av enaminoketonet ble oppløst i 100 ml metanol og 26 g metylaminhydroklorid tilsatt. Reaksjonsblandingen ble oppvarmet ved tilbakeløpstemperatur over natten. Oppløsningsmidlet ble avdampet i vakuum, 100 ml vann tilsatt, An enaminoketone, namely 4-(3-benzyloxyphenyl)-1-diethylamino-2-phenyl-1-buten-3-one, was prepared by following the first step from the procedure in Example 73. Take 14.4 g (3 -benzyloxyphenyl)acetyl chloride and 9>6 S N,N-diethylstyrylamine. A 13 g portion of the enaminoketone was dissolved in 100 ml of methanol and 26 g of methylamine hydrochloride added. The reaction mixture was heated at reflux overnight. The solvent was evaporated in vacuo, 100 ml of water added,

og blandingen ekstrahert med metylenklorid. Ekstraktet ble vasket med fortynnet saltsyre og derpå med vann, og det organiske sjiktet separert, tørket, filtrert og avdampet til tørrhet. Det danne"de mellomprodukt, 4- (3-benzyloksyfenyl)-l-metylamino-2-fenyl-l-buten-3-on, ble oppløst i 125 ml etyleter. and the mixture extracted with methylene chloride. The extract was washed with dilute hydrochloric acid and then with water, and the organic layer separated, dried, filtered and evaporated to dryness. The resulting intermediate, 4-(3-benzyloxyphenyl)-1-methylamino-2-phenyl-1-buten-3-one, was dissolved in 125 ml of ethyl ether.

Oppløsningen ble avkjølt til 5°C, og 12 g riatrium-metoksyd tilsatt. Mens reaksjonsblandingen ble holdt på ca. 5°C tilsatte man langsomt 50 ml etylformiat. Blandingen ble derpå omrørt under langsom oppvarming til romtemperatur. Reaksjonsblandingen ble avdampet til tørrhet, inndampningsresten ekstrahert med kloroform og ekstraktet vasket med vann og tørket. Produktet ble renset ved kromatografering på silikagel og eluert med 50:50-blanding av etylacetat:heksan. De produkt-holdige fraksjoner ble oppsamlet, slått sammen og avdampet. Produktet ble krystallisert fra etylacetat og ga 1,5 g 3-(3-benzyloksy-fenyl)-l-metyl-5-fenyl-4(lH)-pyridon, sm.p. 158-l60°C. The solution was cooled to 5°C, and 12 g of sodium methoxide added. While the reaction mixture was kept at approx. 5°C, 50 ml of ethyl formate was added slowly. The mixture was then stirred while slowly warming to room temperature. The reaction mixture was evaporated to dryness, the evaporation residue extracted with chloroform and the extract washed with water and dried. The product was purified by chromatography on silica gel and eluted with a 50:50 mixture of ethyl acetate:hexane. The product-containing fractions were collected, pooled and evaporated. The product was crystallized from ethyl acetate to give 1.5 g of 3-(3-benzyloxy-phenyl)-1-methyl-5-phenyl-4(1H)-pyridone, m.p. 158-160°C.

De følgende eksempelforbindelser ble også fremstilt etter fremgangsmåten fra Eksempel 20 ovenfor._ The following example compounds were also prepared according to the procedure from Example 20 above._

Eksempel 21 Example 21

l-metyl-3-fenyl-5-(2-tienyl)-4(1H)-Dyridon, sm.p. 147-148°C, utbytte 6$. 1-methyl-3-phenyl-5-(2-thienyl)-4(1H)-Dyridone, m.p. 147-148°C, yield 6$.

Eksempel 22 Example 22

3- (3-isobutylf enyl) -l-metyl-5-f enyl-4(1H)-pyridon., NMR-dubletter ved 54 og 147 CPS, en septett ved 113 CPS, aromatiske protoner ved 420-460 CPS. 3-(3-isobutylphenyl)-1-methyl-5-phenyl-4(1H)-pyridone., NMR doublets at 54 and 147 CPS, a septet at 113 CPS, aromatic protons at 420-460 CPS.

Eksempel 2 3 Example 2 3

l-metyl-3-(3-nitrofenyl)-5-fenyl-4(1H)-pyridon, smp. 135-136,5°C, utbytte 33%. 1-methyl-3-(3-nitrophenyl)-5-phenyl-4(1H)-pyridone, m.p. 135-136.5°C, yield 33%.

Eksempel 23A Example 23A

l-metyl-3-allyltio-5-(3-trifluormetylfenyl)-4(1H)-pyridon, smp. 74-75°C, utbytte 5%. 1-methyl-3-allylthio-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, m.p. 74-75°C, yield 5%.

Eksempel 23B Example 23B

3-(4-klor-3-trifluormetylfenyl)-l-metyl-5-fenoksy-4(1H)-pyridon, smp. 130-131°C, utbytte 27%. Eksempel 23C 3-(4-chloro-3-trifluoromethylphenyl)-1-methyl-5-phenoxy-4(1H)-pyridone, m.p. 130-131°C, yield 27%. Example 23C

l-metyl-3-fenyl-5-allyltio-4(1H)-pyridon, smp. 136-13 8°C, utbytte 15%. 1-methyl-3-phenyl-5-allylthio-4(1H)-pyridone, m.p. 136-13 8°C, yield 15%.

De følgende eksempler demonstrerer fremstilling av et pyridon ved formamidin-acetat-prosessen, fulgt av alkylering i 1-stilling. The following examples demonstrate the preparation of a pyridone by the formamidine-acetate process, followed by alkylation at the 1-position.

Eksempel 24 Example 24

10 g l-(2>,4-diklorfenyl)-3-fenyl-2-propanon ble oppvarmet ved tilbakeløjp med 10 g formamidinacetat i 75 ml formamid i 3 timer. Blandingen ble heilt på is og vann tilsatt. Etter at isen var smeltet ble blandingen filtrert og de utskil-te faste stoffer vasket med etyleter. De faste stoffer ble oppløst i etanol, avfarget med aktivkull og omkrystallisert til 1,3 g 3-(2,4-diklorfenyl)-5-fenyl-4(lH)-pyridon, som ble identifisert ved IR- og NMR-spektra. 10 g of 1-(2,4-dichlorophenyl)-3-phenyl-2-propanone was refluxed with 10 g of formamidine acetate in 75 ml of formamide for 3 hours. The mixture was completely on ice and water was added. After the ice had melted, the mixture was filtered and the separated solids washed with ethyl ether. The solids were dissolved in ethanol, decolorized with activated charcoal and recrystallized to give 1.3 g of 3-(2,4-dichlorophenyl)-5-phenyl-4(1H)-pyridone, which was identified by IR and NMR spectra.

Ovenstående pyridon ble satt til en oppløsning The above pyridone was added to a solution

av 0,5 g 50%-ig natriumhydrid i 60 ml DMSO og oppvarmet til pyridonet var oppløst.: Overskudd av metyljodid ble tilsatt og blandingen omrørt i en halv time. Derpå ble den heilt ut i vann og filtrert. De faste stoffer .ble ekstrahert med metylenklorid som ble tørket med magnesiumsulfat og inndampet til tørrhet. Inndampningsresten ble omkrystallisert fra benzen-heksan og ga 1,1 g 3-(2,4-diklorfenyl)-l-metyl-5-fenyl-4(1H)-pyridon, sm.p. 202-204°C, som ble identifisert ved NMR- og IR-analyser. Resultatene; av elementæranalysene var som følger: of 0.5 g of 50% sodium hydride in 60 ml of DMSO and heated until the pyridone was dissolved.: Excess methyl iodide was added and the mixture stirred for half an hour. It was then poured into water and filtered. The solids were extracted with methylene chloride which was dried with magnesium sulfate and evaporated to dryness. The evaporation residue was recrystallized from benzene-hexane to give 1.1 g of 3-(2,4-dichlorophenyl)-1-methyl-5-phenyl-4(1H)-pyridone, m.p. 202-204°C, which was identified by NMR and IR analyses. The results; of the elementary analyzes were as follows:

De følgende "eksempelforbindelser ble fremstilt etter den generelle metoden beskrevet i Eksempel 24• I enkelte tilfeller ble mellomprodukter av 1-usubstituert pyridon fremstilt etter den kjente metoden til Benary og Bitter, som tidligere er nevnt. The following "example compounds were prepared according to the general method described in Example 24• In some cases intermediate products of 1-unsubstituted pyridone were prepared according to the known method of Benary and Bitter, which has been previously mentioned.

Eksempel 25 Example 25

3,5-difenyl-l-etyl-4(lH)-pyridon, sm.p. 171°C, utbytte 75$. 3,5-diphenyl-1-ethyl-4(1H)-pyridone, m.p. 171°C, yield 75$.

Eksempel 26 Example 26

1-ally1-3,5-difenyl-4(1H)-pyridon, sm.p. 174°C, utbytte 79$. 1-ally1-3,5-diphenyl-4(1H)-pyridone, m.p. 174°C, yield 79$.

Eksempel 27 Example 27

3,5-difenyl-1-isopropy1-4(1H)-pyridon, sm.p. 152°C, utbytte 15$. 3,5-diphenyl-1-isopropyl-4(1H)-pyridone, m.p. 152°C, yield 15$.

Eksempel 28 Example 28

1-cyanomety1-3,5-difenyl-4(1H)-pyridon, sm.p. 221-224°C, utbytte 55$. 1-cyanomethyl-3,5-diphenyl-4(1H)-pyridone, m.p. 221-224°C, yield 55$.

Det neste eksempel illustrerer en variasjon av formuleringsmetoden hvorved utgangs-ketonet med formel VIII di-formyleres til en forbindelse med formel VI, og pyridonet fremstilles ved utveksling med et amin. The next example illustrates a variation of the formulation method whereby the starting ketone of formula VIII is di-formylated to a compound of formula VI, and the pyridone is prepared by exchange with an amine.

Eksempel 29 Example 29

100 g 1,3-difenyl-2-propanon ble oppløst i 35 g etylformiat og tilsatt til 25 g natrium-metoksyd i 500 ml etyleter ved 0-5°C i løpet av en 30 minutters periode. Reaksjonsblandingen ble hensatt for oppvarming til romtemperatur under røring, over natten. Blandingen ble filtrert og ga 46O g di-natriumsalt av 1,5-dihydroksy-2,4-difenyl-1,4-pentadien~3-on, som ble brukt til neste trinn uten rensing. 100 g of 1,3-diphenyl-2-propanone was dissolved in 35 g of ethyl formate and added to 25 g of sodium methoxide in 500 ml of ethyl ether at 0-5°C over a 30 minute period. The reaction mixture was allowed to warm to room temperature with stirring overnight. The mixture was filtered to give 460 g of the disodium salt of 1,5-dihydroxy-2,4-diphenyl-1,4-pentadien~3-one, which was used for the next step without purification.

Et parti på 20 g av det urensede saltet ovenfor ble satt til en oppløsning av 20 g propylamin og 5 ml konsentrert saltsyre i 75 ml vann. Blandingen ble omrørt i en halv time ved romtemperatur. Reaksjonsblandingen ble ekstrahert med etyleter og vannsjiktet inndampet til tørrhet. Inndampningsresten ble ekstrahert med kloroform, de samlede organiske ekstrakter avdampet tiljtørrhet og residuet omkrystallisert fra benzen-heksan til 3>05 g 3»5-difenyl-l-propyl-4(lH)-pyridon, sm.p. 172-174°C. ' A 20 g portion of the above crude salt was added to a solution of 20 g propylamine and 5 ml concentrated hydrochloric acid in 75 ml water. The mixture was stirred for half an hour at room temperature. The reaction mixture was extracted with ethyl ether and the aqueous layer evaporated to dryness. The evaporation residue was extracted with chloroform, the combined organic extracts evaporated to dryness and the residue recrystallized from benzene-hexane to give 3.05 g of 3'5-diphenyl-1-propyl-4(1H)-pyridone, m.p. 172-174°C. '

De følgende typiske forbindelser ble også fremstilt etter den generelle metode fra Eksempel 29: The following typical compounds were also prepared by the general method of Example 29:

Eksempel 3. 0 1Example 3. 0 1

3,5-difenyl-l-metoksy-4(lH)-pyridon, sm.p. l65°C, utbytte 95$. 3,5-diphenyl-1-methoxy-4(1H)-pyridone, m.p. l65°C, yield 95$.

1 1

Eksempel 31 Example 31

3-(3-fluorfenyl)-l-metyl-5-fenyl-4(1H)-pyridon, sm.p. 133,5°C, utbytte 69$. 3-(3-fluorophenyl)-1-methyl-5-phenyl-4(1H)-pyridone, m.p. 133.5°C, yield 69$.

Eksempel 32 Example 32

3-(4-bromfenyl)-l-metyl-5-fenyl-4(1H)-pyridon, sm.p. 172°C, utbytte 63$. 3-(4-bromophenyl)-1-methyl-5-phenyl-4(1H)-pyridone, m.p. 172°C, yield 63$.

Eksempel 33 Example 33

3-(4-metdksyfenyl)-l-metyl-5-fenyl-4(1H)-pyridon, sm.p. 165°C, utbytte 32$. 3-(4-Methoxyphenyl)-1-methyl-5-phenyl-4(1H)-pyridone, m.p. 165°C, yield 32$.

Eksempel 34 Example 34

3-(3-klorfenyl)-l-metyl-5-fenyl-4(1H)-pyridon, sm.p. 172,5°C, utbytte 27$. 3-(3-chlorophenyl)-1-methyl-5-phenyl-4(1H)-pyridone, m.p. 172.5°C, yield 27$.

Eksempel 35 Example 35

3-(4-klorfenyl)-l-metyl-5-fenyl-4(1H)-pyridon, sm.p. 141,5°C, utbytte 76$. 3-(4-chlorophenyl)-1-methyl-5-phenyl-4(1H)-pyridone, m.p. 141.5°C, yield 76$.

Eksempel 36 l-raetyl-3:-(l-naftyl)-5-fenyl-4(lH)-pyridon, NMR-topper ved 204 og 483 CPS, aromatiske protoner ved 430-470 CPS, utbytte 12$. Example 36 1-Raethyl-3:-(1-naphthyl)-5-phenyl-4(1H)-pyridone, NMR peaks at 204 and 483 CPS, aromatic protons at 430-470 CPS, yield 12$.

Eksempel 37 Example 37

3»5-bis(3-klorfenyl)-l-metyl-4(lH)-pyridon, sm.p. 164-167°C, utbytte 59%i. 3'5-bis(3-chlorophenyl)-1-methyl-4(1H)-pyridone, m.p. 164-167°C, yield 59%i.

Eksempel 38 Example 38

l-metyl-3-(3-metylfenyl)-5-fenyl-4(1H)-pyridon (kompleks inneholdende! 1/2 mol benzen)sm.p. 79»5°C, utbytte 25$. 1-methyl-3-(3-methylphenyl)-5-phenyl-4(1H)-pyridone (complex containing 1/2 mol benzene) m.p. 79»5°C, yield 25$.

Eksempel 39 Example 39

l-metyl-3-(4-metylfenyl)-5-fenyl-4(1H)-pyridon, sm.p. 144,5°C, utbytte, 28$. 1-methyl-3-(4-methylphenyl)-5-phenyl-4(1H)-pyridone, m.p. 144.5°C, yield, 28$.

Eksempel 40 Example 40

l-metyl-3-(2-metylfenyl)-5-fenyl-4(1H)-pyridon, 1-methyl-3-(2-methylphenyl)-5-phenyl-4(1H)-pyridone,

NMR-topper ved 133 og 201 CPS, aromatiske protoner ved 420-440 og 442-46O CPS, utbytte 16$. NMR peaks at 133 and 201 CPS, aromatic protons at 420-440 and 442-46O CPS, yield 16$.

Eksempel 41 Example 41

3-(4-fluorfenyl)-l-metyl-5-fenyl-4(1H)-pyridon, sm.p. 166°C, utbytte 60$. 3-(4-Fluorophenyl)-1-methyl-5-phenyl-4(1H)-pyridone, m.p. 166°C, yield 60$.

00

Eksempel 42 Example 42

l-metyl-3-fenyl-5-(3-trifluormetylfenyl)-4(1H)-pyridon, sm.p. 152-156°C, utbytte 52$. 1-methyl-3-phenyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, m.p. 152-156°C, yield 52$.

Eksempel 43 Example 43

3-(3-metoksyfenyl)-l-metyl-5-fenyl-4(1H)-pyridon, NMR-topper ved 200 og 220 CPS, aromatiske protoner ved 420-440 og 442-46O CPS, utbytte 33$. 3-(3-Methoxyphenyl)-1-methyl-5-phenyl-4(1H)-pyridone, NMR peaks at 200 and 220 CPS, aromatic protons at 420-440 and 442-460 CPS, yield 33$.

Eksempel 44 Example 44

3-(3,4-diklorfenyl)-l-metyl-5-fenyl-4(lH)-pyridon, sm.p. 166,5°C, utbytte 54$- 3-(3,4-dichlorophenyl)-1-methyl-5-phenyl-4(1H)-pyridone, m.p. 166.5°C, yield 54$-

Eksempel 45 Example 45

3-(2,5-diklorfenyl)-1-metyl-5-fenyl-4(1H)-pyridon, sm.p. 155,5°C, utbytte 22$. 3-(2,5-dichlorophenyl)-1-methyl-5-phenyl-4(1H)-pyridone, m.p. 155.5°C, yield 22$.

Eksempel 46 Example 46

3-(2-klorfenyl)-l-metyl-5-fenyl-4(1H)-pyridon, sm.p. 145°C, utbytte 29$. 3-(2-chlorophenyl)-1-methyl-5-phenyl-4(1H)-pyridone, m.p. 145°C, yield 29$.

Eksempel 47 Example 47

3»5-bis(3-fluorfenyl)-l-metyl-4(lH)-pyridon, sm. p. 149-151°C, utbytte 60$. 3'5-bis(3-fluorophenyl)-1-methyl-4(1H)-pyridone, sm. mp 149-151°C, yield 60$.

Eksempel 48 Example 48

3-(3-klorfenyl)-5-(3-fluorfenyl)-l-metyl-4(1H)-pyridon, sm.p. 145-146°C, utbytte 64$. 3-(3-chlorophenyl)-5-(3-fluorophenyl)-1-methyl-4(1H)-pyridone, m.p. 145-146°C, yield 64$.

Eksempel 49 Example 49

3-(3,5-diklorfenyl)-l-metyl-5-fenyl-4(1H)-pyridon, sm.p. 131-135°C, utbytte 28$. 3-(3,5-dichlorophenyl)-1-methyl-5-phenyl-4(1H)-pyridone, m.p. 131-135°C, yield 28$.

Eksempel 50 Example 50

3,5-bis(3-bromfenyl)-l-metyl-4(lH)-pyridon, sm. p. 216,5°C, utbytte 43$. 3,5-bis(3-bromophenyl)-1-methyl-4(1H)-pyridone, sm. at 216.5°C, yield 43$.

Eksempel 51 Example 51

3-(3-bromfenyl)-l-metyl-5-fenyl-4(1H)-pyridon, sm.p. 172°C, utbytte 38$. 3-(3-bromophenyl)-1-methyl-5-phenyl-4(1H)-pyridone, m.p. 172°C, yield 38$.

Eksempel 52 Example 52

3-(2-fluorfenyl)-l-metyl-5-fenyl-4(lH)-pyridon, sm.p. 165°C, utbytte 19$. 3-(2-Fluorophenyl)-1-methyl-5-phenyl-4(1H)-pyridone, m.p. 165°C, yield 19$.

Eksempel 53 Example 53

3-(3-bromfényl)-l-metyl-5-(3-trifluormetylfenyl)-4(1H)-pyridon, sm.p. 151-153°C, utbytte 37$. 3-(3-bromophenyl)-1-methyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, m.p. 151-153°C, yield 37$.

Eksempel 54 Example 54

1-(1-karboksyetyl)-3-fenyl-5-(3-trifluormetyl-fenyl)-4(1H)-pyridon, smj.p. 236-237°C, utbytte 13$. 1-(1-carboxyethyl)-3-phenyl-5-(3-trifluoromethyl-phenyl)-4(1H)-pyridone, m.p. 236-237°C, yield 13$.

Eksempel 55 Example 55

l-dimetylamino-3,5-difenyl-4(1H)-pyridon, sm.p. 143°C, utbytte 94<$.>1-dimethylamino-3,5-diphenyl-4(1H)-pyridone, m.p. 143°C, yield 94<$.>

Eksempel 56 Example 56

l-metyl-3-(2-naftyl)-5-fenyl-4(lH)-pyridon, sm.p. 101-105°C, utbytte 45<$.>1-methyl-3-(2-naphthyl)-5-phenyl-4(1H)-pyridone, m.p. 101-105°C, yield 45<$.>

Eksempel 57 Example 57

l-etyl-3-fenyl-5-(3-trifluormetylfenyl)-4(1H)-pyridon, sm.p. 98-100°C, utbytte 66$. 1-ethyl-3-phenyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, m.p. 98-100°C, yield 66$.

Eksempel 58 Example 58

3-f enyl-l-propyl-5-.( 3-trif luormetylf enyl)-4 (1H)-pyridon, NMR-triplett ved 60 og 230 CPS, og en sekstett ved 114 CPS, utbytte 42$. 3-phenyl-1-propyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, NMR triplet at 60 and 230 CPS, and a sextet at 114 CPS, yield 42$.

Eksempel 59 Example 59

l-metoksy-r3-f enyl-5- (3-trif luormetylf enyl) -4 (1H) - pyridon, NMR-topp ved 2|8 CPS. 1-Methoxy-[3]-phenyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, NMR peak at 2|8 CPS.

Eksempel 60 Example 60

3-(3-klorfenyl)-l-metyl-5-(3-trifluormetylfenyl)-4(1H)-pyridon, sm.p. 133-135°C, utbytte 28$. 3-(3-chlorophenyl)-1-methyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, m.p. 133-135°C, yield 28$.

Eksempel 61 Example 61

3-(4-bifenylyl)-l-metyl-5-fenyl-4(1H)-pyridon, sm.p. 186-190°C, utbytte 1$. 3-(4-biphenylyl)-1-methyl-5-phenyl-4(1H)-pyridone, m.p. 186-190°C, yield 1$.

Lksempel 62 Example 62

3- (3-bif e,hylyl) -l-metyl-5-f enyl-4 (1H) -pyridon, sm.p. 186-190°C, utbytte 2$. 3-(3-biphenyl)-1-methyl-5-phenyl-4(1H)-pyridone, m.p. 186-190°C, yield 2$.

Følgende eksempel illustrerer syntesen av pyridoner ved di(aminoformylering) av ketoner, fulgt av utveksling med aminer. The following example illustrates the synthesis of pyridones by di(aminoformylation) of ketones, followed by exchange with amines.

Eksempel 63 Example 63

En blanding av 26,8 g fenylaceton og 71,4 g dimetylformamid-dimetylacetal i 100 ml vannfri dimetylformamid ble kokt ved tilbakeløp i 5 dager. Reaksjonsblandingen ble inndampet til tørrhet i vakuum. Analyse av den gjenværende mørkerøde olje viste at den besto av ca. 75$ av det ønskede 1, 5-bis(dimetylamino)-2-fenyl-1,4-pentadien-3-on og ca. 25$ tilsvarende monoaminoformylert forbindelse. Utbyttet var 30 g, og mellomproduktet ble brukt videre uten rensing. A mixture of 26.8 g of phenylacetone and 71.4 g of dimethylformamide-dimethyl acetal in 100 ml of anhydrous dimethylformamide was refluxed for 5 days. The reaction mixture was evaporated to dryness in vacuo. Analysis of the remaining dark red oil showed that it consisted of approx. 75$ of the desired 1, 5-bis(dimethylamino)-2-phenyl-1,4-pentadien-3-one and approx. 25$ corresponding monoaminoformylated compound. The yield was 30 g, and the intermediate product was used further without purification.

Forbindelsen ovenfor ble oppløst i 100 ml denaturert etanol og 30 g metylaminhydroklorid tilsatt. Blandingen ble kokt ved tilbakeløp over natten, og oppløsningsmidlet avdampet i vakuum. Residuet ble oppløst i metylenklorid og opp-løsningen vasket med vann og mettet vandig natriumkloridopp-løsning. Det vaskede organiske sjikt ble tørket på magnesiumsulfat og oppløsningsmidlet avdampet i vakuum. Den gjenværende olje ble rystet med etyleter. Det faste produkt som felte seg ut fra eteren ble vasket med mer eter og lufttørket. Produktet ble omkrystallisert fra isopropyleter-metylenklorid og ga 10 g renset l-metyl-3-fenyl-4(1H)-pyridon, sm.p. 123-125°C. The above compound was dissolved in 100 ml of denatured ethanol and 30 g of methylamine hydrochloride was added. The mixture was refluxed overnight and the solvent evaporated in vacuo. The residue was dissolved in methylene chloride and the solution washed with water and saturated aqueous sodium chloride solution. The washed organic layer was dried over magnesium sulfate and the solvent evaporated in vacuo. The remaining oil was shaken with ethyl ether. The solid product that precipitated from the ether was washed with more ether and air dried. The product was recrystallized from isopropyl ether-methylene chloride to give 10 g of purified 1-methyl-3-phenyl-4(1H)-pyridone, m.p. 123-125°C.

Eksempel 64 Example 64

En 3 g porsjon av produktet fra Eksempel 63 ble oppløst i 100 ml vann og vandig brom tilsatt dråpevis til det ikke dannet seg mere felling ved videre tilsetning. Fellingen ble frafiltrert, vasket med vann og lufttørket. Produktet ble omkrystallisert fra etanol og ga 3 g 3-brom-l-metyl-5-fenyl-4(1H)-pyridon, sm.p. 195-197°C. A 3 g portion of the product from Example 63 was dissolved in 100 ml of water and aqueous bromine added dropwise until no more precipitate formed upon further addition. The precipitate was filtered off, washed with water and air dried. The product was recrystallized from ethanol to give 3 g of 3-bromo-1-methyl-5-phenyl-4(1H)-pyridone, m.p. 195-197°C.

Fremgangsmåten fra Eksempel 63 og eventuelt Eksempel 64 ble brukt for fremstilling av følgende forbindelser: Eksempel 65 The procedure from Example 63 and possibly Example 64 was used for the preparation of the following compounds: Example 65

3-brom-l-metyl-5-(3-trifluormetylfenyl)-4(1H)-pyridon, sm.p. l67-l69°C, utbytte 76$. 3-bromo-1-methyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, m.p. 167-169°C, yield 76$.

Eksempel 66 Example 66

l-metyl-3-(3-trifluormetylfenyl)-4(1H)-pyridon, sm.p. 122-123°C, utbytte 16$. 1-methyl-3-(3-trifluoromethylphenyl)-4(1H)-pyridone, m.p. 122-123°C, yield 16$.

Eksempel 67 Example 67

3-klor-l-metyl-5-(3-trifluormetylfenyl)-4(lH)-pyridon, sm.p. r70-172°C, utbytte 67$. 3-chloro-1-methyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, m.p. r70-172°C, yield 67$.

Eksempel 68 Example 68

3-(3-karboksyfenyl)-l-metyl-5-fenyl-4(1H)-pyridon .- hydroklorid , sm.p. 266-268°C, utbytte 10$. 3-(3-carboxyphenyl)-1-methyl-5-phenyl-4(1H)-pyridone hydrochloride, m.p. 266-268°C, yield 10$.

Eksempel 69 Example 69

3-(3-cyanofenyl)-l-metyl-5-fenyl-4(1H)-pyridon, sm.p. 164-166°C, utbytte 33$. 3-(3-cyanophenyl)-1-methyl-5-phenyl-4(1H)-pyridone, m.p. 164-166°C, yield 33$.

Eksempel 70 Example 70

3- (3-etoksykarbo.nylfenyl) -l-metyl-5-f enyl-4 (1H) -pyridon, smp. 167-168°C, utbytte 11%. 3-(3-ethoxycarbonylphenyl)-1-methyl-5-phenyl-4(1H)-pyridone, m.p. 167-168°C, yield 11%.

Eksempel 71 Example 71

3,5-bis(3-cyanofenyl)-l-metyl-4(1H)-pyridon, smp. 3,5-bis(3-cyanophenyl)-1-methyl-4(1H)-pyridone, m.p.

322-327°C, utbytte 22%. [ 322-327°C, yield 22%. [

Eksempel 7 2 Example 7 2

l-metyl-3-fenyl-5-(3-tienyl)-4(1H)-pyridon, NMR-topper ved 204 og 495 CPS, aromatiske protoner ved 430-460. CPS, utbytte 34%. 1-methyl-3-phenyl-5-(3-thienyl)-4(1H)-pyridone, NMR peaks at 204 and 495 CPS, aromatic protons at 430-460. CPS, yield 34%.

Eksempel 7 2A Example 7 2A

l-metyl-3-(2-metylfenyl)-5-(3-trifluormetylfenyl)-4(1H)-pyridon, smp. 144-147°C, utbytte 5%. 1-methyl-3-(2-methylphenyl)-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, m.p. 144-147°C, yield 5%.

Eksempel 72B Example 72B

l-metyl-3-(3-metylfenyl)-5-(3-trifluormetylfenyl)-4(1H)-pyridon, smp. 155rl57°C, utbytte 2,4%. 1-methyl-3-(3-methylphenyl)-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, m.p. 155rl57°C, yield 2.4%.

Eksempel 72C Example 72C

l-metyl-3-(4-metylfenyl)-5-(3-trifluormetylfenyl) - 4(1H)-pyridon, smp. 154^156°C, utbytte 6%. 1-methyl-3-(4-methylphenyl)-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, m.p. 154^156°C, yield 6%.

Eksempel 72D Example 72D

5- (3-metoksykarbonylfenyl)-l-metyl-3-(4-metylfenyl)-4(1H)-pyridon, smp. 85-88°C, utbytte 5%. 5-(3-methoxycarbonylphenyl)-1-methyl-3-(4-methylphenyl)-4(1H)-pyridone, m.p. 85-88°C, yield 5%.

Eksempel 72E Example 72E

5-(3-metoksykarbonylfenyl)-l-metyl-3-(3-metylfenyl)-4(1H)-pyridon, smp. 180-183°C, utbytte 1%. 5-(3-methoxycarbonylphenyl)-1-methyl-3-(3-methylphenyl)-4(1H)-pyridone, m.p. 180-183°C, yield 1%.

Eksempel 7 2F Example 7 2F

3-metoksy-l-metyl-5-(3-trifluormetylfenyl)-4(1H)-pyridon, smp. 173-175°C, utbytte 18%. 3-methoxy-1-methyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, m.p. 173-175°C, yield 18%.

Eksempel 72G Example 72G

3-(4-bromfenyl)-l-metyl-5-(3-metylfenyl)-4(1H)-pyridon, smp. 201-204°C, utbytte 21%. 3-(4-bromophenyl)-1-methyl-5-(3-methylphenyl)-4(1H)-pyridone, m.p. 201-204°C, yield 21%.

Eksempel 72H i Example 72H i

3-(3,4-diklorfenyl)-l-metyl-5-(3-trifluormetylfenyl)-4(1H)-pyridon, smp. 10?-112°C, utbytte 4%. 3-(3,4-dichlorophenyl)-1-methyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, m.p. 10?-112°C, yield 4%.

Eksempel 721 Example 721

3,5-bis(3,5-diklorfenyl)-l-metyl-4(1H)-pyridon, smp. 275-278°C, utbytte 14%. 3,5-bis(3,5-dichlorophenyl)-1-methyl-4(1H)-pyridone, m.p. 275-278°C, yield 14%.

Eksempel 72J Example 72J

3-(3,4-diklorfenyl)-l-metyl-5-(3-metylfenyl)-4(1H)-pyridon, massespektroskopi MI, 342, utbytte 10%. 3-(3,4-dichlorophenyl)-1-methyl-5-(3-methylphenyl)-4(1H)-pyridone, mass spectroscopy MI, 342, yield 10%.

Eksempel K Example K

3-(3,4-diklorfenyl)-5-(3,4-dimetylfenyl)-l-metyl-4(1H)-pyridon, smp. 150-152°C, utbytte 6%. 3-(3,4-dichlorophenyl)-5-(3,4-dimethylphenyl)-1-methyl-4(1H)-pyridone, m.p. 150-152°C, yield 6%.

Eksempel 72L Example 72L

3-(3-klorfenyl)-l-metyl-5-(2-metylfenyl)-4(1H)-pyridon, smp. 171-173°C, utbytte 12%. 3-(3-chlorophenyl)-1-methyl-5-(2-methylphenyl)-4(1H)-pyridone, m.p. 171-173°C, yield 12%.

Eksempel 7 2M Example 7 2M

3-(4-bromfenyl)-l-metyl-5-(3-triflurometylfenyl)-4(1H)-pyridon, smp. 144-146°C, utbytte 30%. 3-(4-bromophenyl)-1-methyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, m.p. 144-146°C, yield 30%.

Følgende forbindelse ble fremstilt ved tilbakeløpskoking av forbindelsen ovenfor, i 60% svovelsyre. The following compound was prepared by refluxing the above compound in 60% sulfuric acid.

Eksempel 7 2N Example 7 2N

3-(4-bromfenyl)-5-(3-karboksyfenyl)-metyl-4(1H)-pyridon, smp. 259-263°C, utbytte 50%. 3-(4-bromophenyl)-5-(3-carboxyphenyl)-methyl-4(1H)-pyridone, m.p. 259-263°C, yield 50%.

Følgende forbindelser ble fremstilt ifølge fremgangsmåten i eksempel 63. The following compounds were prepared according to the procedure of Example 63.

Eksempel 7 20 Example 7 20

3-(3-klorfenyl)-l-metyl-5-(4-trifluormetylfenyl)-4(1H)-pyridon, smp. 147-151°C, utbytte 2%. 3-(3-chlorophenyl)-1-methyl-5-(4-trifluoromethylphenyl)-4(1H)-pyridone, m.p. 147-151°C, yield 2%.

Eksempel 72P Example 72P

3-(2-metylfenyl)-5-(4-metylfenyl)-l-metyl-4(1H)-pyridon, smp. 151-154°C, utbytte 6%. 3-(2-methylphenyl)-5-(4-methylphenyl)-1-methyl-4(1H)-pyridone, m.p. 151-154°C, yield 6%.

Eksempel 72Q Example 72Q

3-(3-metylfenyl)-5-(4-metylfenyl)-l-metyl-4(1H)-pyridon, smp. 155-157°C, utbytte 28%. 3-(3-methylphenyl)-5-(4-methylphenyl)-1-methyl-4(1H)-pyridone, m.p. 155-157°C, yield 28%.

Eksempel 72R Example 72R

3-(2-klorfenyl)-5-(2-metylfenyl)-l-metyl-4(1H)-pyridon, smp. 87-91°C, utbytte 1%. 3-(2-chlorophenyl)-5-(2-methylphenyl)-1-methyl-4(1H)-pyridone, m.p. 87-91°C, yield 1%.

Eksempel 72S Example 72S

l-metyl-3,5-bis(4-metylfenyl)-4(1H)-pyridon, smp. 212-214°C, utbytte 3%. 1-methyl-3,5-bis(4-methylphenyl)-4(1H)-pyridone, m.p. 212-214°C, yield 3%.

Eksempel 72T • Example 72T •

l-metyl-3-(3-klorfenyl)-5-(3,4-diklorfenyl)-4(1H)-pyridon, smp. 107-110°C, utbytte 10%. 1-methyl-3-(3-chlorophenyl)-5-(3,4-dichlorophenyl)-4(1H)-pyridone, m.p. 107-110°C, yield 10%.

I IN

Eksempel 72U Example 72U

l-metyl-3-(3,4-diklorfenyl)-5-(2-metylfenyl)-4(1H)-pyridon, smp. 103-106°C, utbytte 10%. 1-methyl-3-(3,4-dichlorophenyl)-5-(2-methylphenyl)-4(1H)-pyridone, m.p. 103-106°C, yield 10%.

Eksempel 72V Example 72V

l-metyl-3-(2-klorfenyl)-5-(3,4-diklorfenyl)-4(1H)-pyridon, smp. 169-171°C,:utbytte 25%. 1-methyl-3-(2-chlorophenyl)-5-(3,4-dichlorophenyl)-4(1H)-pyridone, m.p. 169-171°C,: yield 25%.

Eksempel 72W i Example 72W i

l-metyl-3-(3-bromfenyl)-5-(3,4-diklorfenyl)-4(1H)-pyridon, smp. 152-154°C,<;>utbytte 10%. 1-methyl-3-(3-bromophenyl)-5-(3,4-dichlorophenyl)-4(1H)-pyridone, m.p. 152-154°C,<;>yield 10%.

Eksempel 72X Example 72X

l-metyl-3-(3,5-diklorfenyl)-5-(3-trifluormetylfenyl)-4(1H)-pyridon, smp. 156-160°C, utbytte 30%. 1-methyl-3-(3,5-dichlorophenyl)-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, m.p. 156-160°C, yield 30%.

Eksempel 72Y Example 72Y

l-metyl-3-(3-bromfenyl)-5-(3-metylfenyl)-4(1H)-pyridon, spm. 144-147°C, utbytte 3%. 1-methyl-3-(3-bromophenyl)-5-(3-methylphenyl)-4(1H)-pyridone, sp. 144-147°C, yield 3%.

Eksempel 72Z Example 72Z

l-metyl-3,5-bis(3-metylfenyl)-4(1H)-pyridon, smp. 148-150°C, utbytte 8%. 1-methyl-3,5-bis(3-methylphenyl)-4(1H)-pyridone, m.p. 148-150°C, yield 8%.

Eksempel 72AA Example 72AA

l-metyl-3-(3-fluorfenyl)-5-(2,5-dimetylfenyl)-4(1H)-pyridon, massespektroskopi MI, 307, utbytte 10%. Eksempel 72BB 1-methyl-3-(3-fluorophenyl)-5-(2,5-dimethylphenyl)-4(1H)-pyridone, mass spectroscopy MI, 307, yield 10%. Example 72BB

3-(3-bromfenyl)-l-metyl-5-(2-metylfenyl)-4(1H)-pyridon, massespektroskopi MI, 353, utbytte 2%. 3-(3-Bromophenyl)-1-methyl-5-(2-methylphenyl)-4(1H)-pyridone, mass spectroscopy MI, 353, yield 2%.

Eksempel 72CC Example 72CC

3-(3-bromfenyl)-5-(2-klorfenyl)-l-metyl-4(1H)-pyridon, smp. 177-179°C, utbytte :10%. 3-(3-bromophenyl)-5-(2-chlorophenyl)-1-methyl-4(1H)-pyridone, m.p. 177-179°C, yield: 10%.

Eksempel 72DD Example 72DD

3- (2-bromfenyl) -rl-metyl-5- (3-trif lourmetylf enyl) - 4(1H)-pyridon, smp. 197-199°C, utbytte 15%. 3-(2-bromophenyl)-1-methyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, m.p. 197-199°C, yield 15%.

Eksempel 72EE Example 72EE

3-(2,3-dimetoksyfenyl)-l-metyl-5-(3-trifluormetylfenyl)-4(1H)-pyridon, smp. 153-155°C, utbytte 20%. 3-(2,3-dimethoxyphenyl)-1-methyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, m.p. 153-155°C, yield 20%.

I IN

Eksempel 7 2FF Example 7 2FF

3-(2-metoksyfenyl)-l-metyl-5-(3-trifluormetylfenyl)-4(1H)-pyridon, smp. 193-196°C, utbytte 10%. 3-(2-Methoxyphenyl)-1-methyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, m.p. 193-196°C, yield 10%.

Eksempel 72GG Example 72GG

3- (2-etylfenyl) i-l-metyl-5- (3-trif luormetylf enyl) -4 (1H) - pyridon, smp. 123-125°C, utbytte 15%. 3-(2-ethylphenyl)-1-methyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, m.p. 123-125°C, yield 15%.

Eksempel 72HH Example 72HH

3- (3-brom-4-metylfenyl)-l-metyl-5-(3-trifluormetylfenyl)-4 (1H)-pyridon, smp. 158-161°C, utbytte 30%. 3-(3-bromo-4-methylphenyl)-1-methyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, m.p. 158-161°C, yield 30%.

Eksempel 7211 Example 7211

3- (3-etoksy-4-metoksyfenyl)-l-metyl-5-(3-trifluormetyl-fenyl)-4(1H)-pyridon, massespektroskopi MI, 403, utbytte 10%. Eksempel 72JJ 3-(3-ethoxy-4-methoxyphenyl)-1-methyl-5-(3-trifluoromethyl-phenyl)-4(1H)-pyridone, mass spectroscopy MI, 403, yield 10%. Example 72JJ

3-(1-hydroksyetyl)-l-metyl-5-(3-trifluormetylfenyl)-4(1H)-pyridon, massespektroskopi MI, 297, utbytte 1%. 3-(1-hydroxyethyl)-1-methyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, mass spectroscopy MI, 297, yield 1%.

Eksempel 72KK Example 72KK

3-(1-metoksyetyl)-l-metyl-5-(3-trifluormetylfenyl)-4(1H)-pyridon, massespektroskopi MI, 311, utbytte 1%. 3-(1-Methoxyethyl)-1-methyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, mass spectroscopy MI, 311, yield 1%.

Følgende eksempel demonstrerer en syntese hvor den tilsvarende enaminoketon med formel X aminoformyleres til en forbindelse med formel VI, og pyridonet fremstilles ved utveksling med et amin. The following example demonstrates a synthesis where the corresponding enaminoketone of formula X is aminoformylated to a compound of formula VI, and the pyridone is prepared by exchange with an amine.

Eksempel 73 Example 73

En blanding av 1,92 g dimetylaminoakrylnitril og 1,6 g pyridin ble oppløst i 25 ml etyleter ved 0°C. 3,08 g fenylacetylklorid i 25 ml tørr eter ble tilsatt dråpevis og blandingen omrørt i 2 timer ved 0°C etter avsluttet tilsetning. Blandingen ble inndampet til tørrhet i vakuum. Inndampningsresten ble oppløst i metylenklorid, vasket med vann, tørket og inndampet til tørrhet pånytt. Ved henstand begynte blandingen å krystallisere, og de faste stoffer ble frafiltrert og omkrystallisert fra isopropanol og ga 400 mg 2-cyan-l-dimetylamino-4-fenyl-l-buten-3-on. A mixture of 1.92 g of dimethylaminoacrylonitrile and 1.6 g of pyridine was dissolved in 25 ml of ethyl ether at 0°C. 3.08 g of phenylacetyl chloride in 25 ml of dry ether was added dropwise and the mixture was stirred for 2 hours at 0°C after the addition had been completed. The mixture was evaporated to dryness in vacuo. The evaporation residue was dissolved in methylene chloride, washed with water, dried and evaporated to dryness again. On standing, the mixture began to crystallize, and the solids were filtered off and recrystallized from isopropanol to give 400 mg of 2-cyano-1-dimethylamino-4-phenyl-1-buten-3-one.

En porsjon på 300 mg av ovenstående enaminoketon og 10 ml dimetylformamid-dimetylacetal ble oppvarmet ved tilbakeløpstemperatur i 12 timer. Blandingen ble inndampet i vakuum. Til residuet satte man 25 ml denaturert etanol og 1 g metylaminhydroklorid. Etanoloppløsningen ble oppvarmet ved tilbakeløp i 12 timer ytterligere og inndampet til tørrhet, og residuet tatt opp i metylenklorid. Etter vasking med vann og tørking ble den organiske oppløsning inndampet til tørrhet og inndampningsresten gnidd ut i etyleter og filtrert. De faste stoffer ble omkrystallisert fra isopropyleter-aceton og ga 260 mg 3-cyan-l-metyl-5-fenyl-4(lH)-pyridon, sm.p. 209-210°C. A 300 mg portion of the above enamino ketone and 10 ml of dimethylformamide-dimethyl acetal was heated at reflux for 12 hours. The mixture was evaporated in vacuo. 25 ml of denatured ethanol and 1 g of methylamine hydrochloride were added to the residue. The ethanol solution was heated at reflux for a further 12 hours and evaporated to dryness, and the residue taken up in methylene chloride. After washing with water and drying, the organic solution was evaporated to dryness and the evaporation residue was triturated in ethyl ether and filtered. The solids were recrystallized from isopropyl ether-acetone to give 260 mg of 3-cyano-1-methyl-5-phenyl-4(1H)-pyridone, m.p. 209-210°C.

De følgende eksempelforbindelser ble fremstilt The following exemplary compounds were prepared

i henhold til fremgangsmåten fra Eksempel 73 ovenfor. according to the procedure from Example 73 above.

Eksempel 74 Example 74

1,3-dimetyl-5-(3-trifluormetylfenyl)-4(1H)-pyridon, sm.p. 130-131°C, utbytte 12$. 1,3-dimethyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, m.p. 130-131°C, yield 12$.

Eksempel 75 Example 75

1,3-dimetyl-5-fenyl-4(1H)-pyridon, sm.p. 111-113°C, utbytte 8$. 1,3-dimethyl-5-phenyl-4(1H)-pyridone, m.p. 111-113°C, yield 8$.

Eksempel 76 Example 76

3-(3-klorfényl)-1,5~dimetyl-4(1H)-pyridon, sm.p. <1>43-143,5°C, utbytte 6$. : Eksempel 77 3-(3-chlorophenyl)-1,5-dimethyl-4(1H)-pyridone, m.p. <1>43-143.5°C, yield 6$. : Example 77

3-ety1-1-mety1-5-(3-trifluormetylfenyl)-4(1H)-pyridon, sm.p. 95,5~96,5°C, utbytte 7%. 3-ethyl-1-methyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, m.p. 95.5~96.5°C, yield 7%.

Eksempel 78 i Example 78 i

3-cykloheksyl-l-metyl-5-(3-trifluormetylfenyl)-4(1H)-pyridon, sm.<p>. 174-175°C, utbytte 40$. 3-cyclohexyl-1-methyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, sm.<p>. 174-175°C, yield 40$.

Eksempel 79 Example 79

3-isopropy1-1-mety1-5-(3-trifluormetylfenyl)-4(1H)-pyridon, s<m.p.> 98,5-99,5°C, utbytte 10$. Eksempel 80 3-isopropyl-1-methyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, mp 98.5-99.5°C, yield 10$. Example 80

3-heksyl-l-mety1-5-(3-trifluormetylfenyl)-4(1H)-pyridon, smp. 89,5-90,5°C, utbytte 7$. 3-hexyl-1-methyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, m.p. 89.5-90.5°C, yield 7$.

Eksempel 81 Example 81

3-benzyl-l-^mety 1-5-(3-trif luormetylf enyl)-4 (1H)-pyridon, sm.p. 98-100°C,:utbytte 18$. Eksempel 82 3-benzyl-1-[methyl]-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, m.p. 98-100°C,:yield 18$. Example 82

3-buty1-l-metyl-5-(3-trifluormetylfenyl)-4(1H)-pyridon, sm.p. 82,5-84°Ci utbytte 9$. 3-Butyl-1-methyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, m.p. 82.5-84°Ci yield 9$.

Eksempel 83 Example 83

3-(3-cykloheksenyl)-l-metyl-5-(3-trifluormetyl-fenyl)-4(1H)-pyridon, sm.p. 194-195°C, utbytte 43$. Eksempel 84 3-(3-cyclohexenyl)-1-methyl-5-(3-trifluoromethyl-phenyl)-4(1H)-pyridone, m.p. 194-195°C, yield 43$. Example 84

1-mety1-3-propy1-5-(3-trifluormetylfenyl)-4(1H)-pyridon, sm.p. 45-47°C, utbytte 3$- 1-methyl-3-propyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, m.p. 45-47°C, yield 3$-

Eksempel 85 Example 85

l-metyl-3-(4-nitrofenyl)-5-fenyl-4(1H)-pyridon, sm.p. 212-214°C, utbytte<1>48$. 1-methyl-3-(4-nitrophenyl)-5-phenyl-4(1H)-pyridone, m.p. 212-214°C, yield<1>48$.

Eksempel 86 i Example 86 i

3,5-bis(3,4-dimetoksyfenyl)-l-metyl-4(1H)-pyridon, sm.p. l82-l84°C, utbytte 1$. 3,5-bis(3,4-dimethoxyphenyl)-1-methyl-4(1H)-pyridone, m.p. l82-l84°C, yield 1$.

Eksempel 87 Example 87

3-etoksykarbony1-1-mety1-5-fenyl-4(1H)-pyridon, sm.p. 107-108°C, utbytte 68$. 3-ethoxycarbonyl-1-methyl-5-phenyl-4(1H)-pyridone, m.p. 107-108°C, yield 68$.

Eksempel 88 Example 88

3-(2-furyl)-l-metyl-5-fenyl-4(1H)-pyridon, sm.p. igi_192°C, utbytte 69$. 3-(2-furyl)-1-methyl-5-phenyl-4(1H)-pyridone, m.p. igi_192°C, yield 69$.

Eksempel 89 Example 89

3-cyano-l-metyl-5-(3-trifluormetylfenyl)-4(1H)-pyridon, sm.p. 228-229°C, utbytte 40$. 3-cyano-1-methyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, m.p. 228-229°C, yield 40$.

Eksempel 90 Example 90

3-(3,4-dimetoksyfenyl)-l-metyl-5-fenyl-4(1H)-pyridon, sm.p. 154-157°C> utbytte 4$« 3-(3,4-dimethoxyphenyl)-1-methyl-5-phenyl-4(1H)-pyridone, m.p. 154-157°C> yield 4$«

Eksempel 91 Example 91

3_(314-dibromcykloheksyl)-l-metyl-5-(3-trifluor-metylf enyl)-4(lH)-pyridonThydrobromid, sm.p. 196-198°C, utbytte 26$, fremstilt ved bromering av den tilsvarende 3~(3-cykloheksenyl)-forbindelse. 3_(314-Dibromocyclohexyl)-1-methyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridone Thydrobromide, m.p. 196-198°C, yield 26$, prepared by bromination of the corresponding 3~(3-cyclohexenyl)-compound.

Eksempel 92 Example 92

3- (3-isopropenylfenyl)-l-metyl-5-fer'yl-4(lH)-pyridon, NMR-topper ved 125, 214, 302 og 327 CPS, aromatiske protoner ved 420-470 CPS, utbytte 4$. 3-(3-isopropenylphenyl)-1-methyl-5-ferr'yl-4(1H)-pyridone, NMR peaks at 125, 214, 302 and 327 CPS, aromatic protons at 420-470 CPS, yield 4$.

Eksempel 93 Example 93

3-(3-etylfenyl)-l-metyl-5-fenyl-4(1H)-pyridon, sm.p. 135-137°C, utbytte 5$. 3-(3-ethylphenyl)-1-methyl-5-phenyl-4(1H)-pyridone, m.p. 135-137°C, yield 5$.

Eksempel 94 Example 94

3-(3-heksylfenyl)-l-metyl-5-fenyl-4(lH)jipyridon, sm.p. 93-95°C, utbytte 6$. 3-(3-hexylphenyl)-1-methyl-5-phenyl-4(1H)pyridone, m.p. 93-95°C, yield 6$.

Eksempel 95 Example 95

3-(4-etylfenyl)-l-metyl-5-fenyl-4(lH)-pyridon, sm.p. 143-145°C, utbytte 6$. 3-(4-ethylphenyl)-1-methyl-5-phenyl-4(1H)-pyridone, m.p. 143-145°C, yield 6$.

Eksempel 96 Example 96

3-(3-cykloheksylmetylfenyl)-l-metyl-5-fenyl-4(1H)-pyridon, sm.p. 147-148°C, utbytte 9$. 3-(3-cyclohexylmethylphenyl)-1-methyl-5-phenyl-4(1H)-pyridone, m.p. 147-148°C, yield 9$.

Eksempel 97 Example 97

l-metyl-3-fenyl-5-benzyltio-4(1H)-pyridon, sm.p. 155-157°C, utbytte 36$. 1-methyl-3-phenyl-5-benzylthio-4(1H)-pyridone, m.p. 155-157°C, yield 36$.

Eksempel 98 Example 98

l-metyl-3-fenyl-5-fenyltio-4(lH)-pyridon, sm.p. I64-165°C, utbytte l8$. 1-methyl-3-phenyl-5-phenylthio-4(1H)-pyridone, m.p. I64-165°C, yield l8$.

Eksempel 99 Example 99

l-metyl-3-fenoksy-5-fenyl-4(1H)-pyridon, smp. 176-177°C, utbytte 19%. 1-methyl-3-phenoxy-5-phenyl-4(1H)-pyridone, m.p. 176-177°C, yield 19%.

Eksempel 100 Example 100

l-metyl-3-fenyl-5-fenylsulfonyl-4(1H)-pyridon, smp. 218-220°C, utbytte 50%, fremstilt ved oksydasjon av den tilsvarende fenyltioforbindelse med mr-klorperbenzosyre. 1-methyl-3-phenyl-5-phenylsulfonyl-4(1H)-pyridone, m.p. 218-220°C, yield 50%, prepared by oxidation of the corresponding phenylthio compound with m-chloroperbenzoic acid.

Eksempel 100B Example 100B

3-(4-metoksy-3-metylfenyl)-l-metyl-5-fenyl-4(1H) - pyridon, smp. 157-160°C, utbytte 2,5%. 3-(4-methoxy-3-methylphenyl)-1-methyl-5-phenyl-4(1H)-pyridone, m.p. 157-160°C, yield 2.5%.

Eksempel 100C Example 100C

3-(3-brom-4-metylfenyl)-l-metyl-5-fenyl-4(1H)-pyridon, smp. 168-170°C, utbytte 13%. 3-(3-bromo-4-methylphenyl)-1-methyl-5-phenyl-4(1H)-pyridone, m.p. 168-170°C, yield 13%.

Eksempel 100D Example 100D

l-metyl-3-(3-nitrbfenyl)-5-(3-trifluormetylfenyl)-4(1H)-pyridon, smp. 209-211°C, utbytte 51%. 1-methyl-3-(3-nitrophenyl)-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, m.p. 209-211°C, yield 51%.

Eksempel 100E Example 100E

l-metyl-3-fenyl-5-(3-fenyltiofenyl)-4(1H)-pyridon, massespektroskopi MI, 369, utbytte 8%. 1-methyl-3-phenyl-5-(3-phenylthiophenyl)-4(1H)-pyridone, mass spectroscopy MI, 369, yield 8%.

Følgende forbindelse ble fremstilt ved oksydasjon av forbindelsen ovenfor med hydrogenperoksyd i eddiksyre. The following compound was prepared by oxidation of the above compound with hydrogen peroxide in acetic acid.

Eksempel 100F Example 100F

l-metyl-3-fenyl-5-(3-fenylsulfonylfenyl)-4(1H)-pyridon, smp. 65-72°C, utbytte 48%. 1-methyl-3-phenyl-5-(3-phenylsulfonylphenyl)-4(1H)-pyridone, m.p. 65-72°C, yield 48%.

Eksempel 100G Example 100G

3-(2-klor-4-fluorfenyl)-l-metyl-5-fenyl-4(1H)-pyridon, smp. 190-192°C, utbytte 5%. 3-(2-chloro-4-fluorophenyl)-1-methyl-5-phenyl-4(1H)-pyridone, m.p. 190-192°C, yield 5%.

Eksempel 100H I Example 100H I

3-(3,4-dimetylfenyl)-l-metyl-5-fenyl-4(1H)-pyridon, smp. 108-111°C, utbytte 5%. 3-(3,4-dimethylphenyl)-1-methyl-5-phenyl-4(1H)-pyridone, m.p. 108-111°C, yield 5%.

Eksempel 1001 Example 1001

3-(3,5-dimetylfenyl)-l-metyl-5-fenyl-4(1H) -pyridon, smp. 148-150°C, utbytte 10%. 3-(3,5-dimethylphenyl)-1-methyl-5-phenyl-4(1H)-pyridone, m.p. 148-150°C, yield 10%.

Eksempel 100J Example 100J

3-(3-butylfenyl)-l-metyl-5-fenyl-4(1H)-pyridon, smp. 87-89°C, utbytte 6%. 3-(3-butylphenyl)-1-methyl-5-phenyl-4(1H)-pyridone, m.p. 87-89°C, yield 6%.

Eksempel 100K Example 100K

3-(2,5-dimetylfenyl)-l-metyl-5-fenyl-4(1H)-pyridon, smp. 188-190°C, utbytte 4%. 3-(2,5-dimethylphenyl)-1-methyl-5-phenyl-4(1H)-pyridone, m.p. 188-190°C, yield 4%.

Eksempel 100L Example 100L

3-(2,4-dimetylfenyl)-l-metyl-5-fenyl-4(1H)-pyridon, smp. 153-155°C, utbytte 3%. 3-(2,4-dimethylphenyl)-1-methyl-5-phenyl-4(1H)-pyridone, m.p. 153-155°C, yield 3%.

Eksempel 10QM Example 10QM

l-metyl-3-fenoksy-5-(3-trifluormetylfenyl)-4(1H)-pyridon, smp. 144-145°C, utbytte 15%. 1-methyl-3-phenoxy-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, m.p. 144-145°C, yield 15%.

Eksempel 100N Example 100N

3-etoksykarbonyl-l-metyl-5-(3-trifluormetylfenyl)-4(1H)-pyridon, smp. 151-152°C, utbytte 62%. 3-ethoxycarbonyl-1-methyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, m.p. 151-152°C, yield 62%.

Eksempel 100O Example 100O

l-metyl-3-(3-trifluormetylfenyl)-5-fenyltio-4(1H)-pyridon, smp. 164-165°C, utbytte 18%. 1-methyl-3-(3-trifluoromethylphenyl)-5-phenylthio-4(1H)-pyridone, m.p. 164-165°C, yield 18%.

Eksempel 100P Example 100P

3-(2,4-diklorfenoksy)-l-metyl-5-(3-trifluormetylfenyl)-4(1H)-pyridon, smp. 129-130°C, utbytte 40%: Eksempel 100Q 3-(2,4-dichlorophenoxy)-1-methyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, m.p. 129-130°C, yield 40%: Example 100Q

l-metyl-3-(2-tienyl)-5-(3-trifluormetylfenyl)-4(1H)-pyridon,» smp. 185-186°C, utbytte 84%. 1-methyl-3-(2-thienyl)-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, m.p. 185-186°C, yield 84%.

Eksempel 100R Example 100R

3-etyltio-l-metyl-5-fenyl-4(1H)-pyridon, smp. 94-95°C, utbytte 40%. 3-ethylthio-1-methyl-5-phenyl-4(1H)-pyridone, m.p. 94-95°C, yield 40%.

Eksempel 100S Example 100S

3-etyltio-l-metyl-5-(3-trifluormetylfenyl)-4(1H)-pyridon, smp. 84-85°C, utbytte 40%. 3-ethylthio-1-methyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, m.p. 84-85°C, yield 40%.

Eksempel 100T Example 100T

3-(5-brom-2-fluorfenyl)-l-metyl-5-fenyl-4(1H)-pyridon, smp. 148-150°C, utbytte 6%. 3-(5-bromo-2-fluorophenyl)-1-methyl-5-phenyl-4(1H)-pyridone, m.p. 148-150°C, yield 6%.

Eksempel 100U Example 100U

l-metyl-3-(5-nitro-2-metylfenyl)-5-fenyl-4(1H)-pyridon, smp. 185-187°C, utbytte 5%. 1-methyl-3-(5-nitro-2-methylphenyl)-5-phenyl-4(1H)-pyridone, m.p. 185-187°C, yield 5%.

Eksempel 100V Example 100V

3-cyano-5-(2,5-dimetoksyfenyl)-l-metyl-4(1H)-pyridon, smp. 209-211°C, utbytte 4%. 3-cyano-5-(2,5-dimethoxyphenyl)-1-methyl-4(1H)-pyridone, m.p. 209-211°C, yield 4%.

Eksempel 100W Example 100W

3-(2,6-diklorfenyl)-l-metyl-5-fenyl-4(1H)-pyridon, smp. 223-226°C, utbytte 20%. 3-(2,6-dichlorophenyl)-1-methyl-5-phenyl-4(1H)-pyridone, m.p. 223-226°C, yield 20%.

Eksempel 100X Example 100X

3-etoksykarbonyl-l-metyl-5-fenyl-4(1H)-pyridon, smp. 107-108°C, utbytte 68%. 3-ethoxycarbonyl-1-methyl-5-phenyl-4(1H)-pyridone, m.p. 107-108°C, yield 68%.

Eksempel 100Y Example 100Y

l-metyl-3-propyltio-5-(3-trifluormetylfenyl)-4(1H)-pyridon, smp. 101-102°C, utbytte 25%. 1-methyl-3-propylthio-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, m.p. 101-102°C, yield 25%.

Eksempel lOOAA Example lOOAA

l-metyl-3-metyltib-5-(3-trifluormetylfenyl)-4(1H)-pyridon, smp. 121-122°C, utbytte 20%. 1-methyl-3-methyltib-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, m.p. 121-122°C, yield 20%.

Eksempel 100BB . l-metyl-3-(3-trifluormetylfenyl)-5-(4-trifluormetylfenyl) - 4(1H)-pyridon, smp. 110-ll3°C, utbytte 10%. Example 100BB. 1-methyl-3-(3-trifluoromethylphenyl)-5-(4-trifluoromethylphenyl)-4(1H)-pyridone, m.p. 110-113°C, yield 10%.

Eksempel 100DD Example 100DD

3- (3,4-dimetoksyfényl)-l-metyl-5-(3-trifluormetylfenyl)-4(1H)-pyridon, smp. 148-150°C, utbytte 10%. 3-(3,4-dimethoxyphenyl)-1-methyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, m.p. 148-150°C, yield 10%.

Eksempel 100EE Example 100EE

Blanding av 3-(5-fluor-2-jodfenyl)-l-metyl-5-fenyl-4(1H)-pyridon og 3-(2-brom-5-fluorfenyl)-l-metyl-5-fenyl-4(1H)-pyridon, blandet smp. 211-214°c, utbytte 7%. Mixture of 3-(5-fluoro-2-iodophenyl)-1-methyl-5-phenyl-4(1H)-pyridone and 3-(2-bromo-5-fluorophenyl)-1-methyl-5-phenyl-4 (1H)-pyridone, mixed m.p. 211-214°c, yield 7%.

Eksempel 100FF Example 100FF

3-benzyltio-l-metyl-5-(3-trifluormetylfenyl)-4(1H) - pyridon, smp. 121-122°C, utbytte 40%. Eksempel 100GG 3-benzylthio-1-methyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, m.p. 121-122°C, yield 40%. Example 100GG

1,3-dietyl-5-(3-trifluormetylfenyl)-4(1H)-pyridon, smp. 67-70°C, utbytte 3%.. 1,3-diethyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, m.p. 67-70°C, yield 3%..

Eksempel 100HH Example 100HH

3-(4-klor-3-trifluormetylfenyl)-5-etoksy-l-metyl-4(1H) - pyridon, smp. 158-159°C, utbytte 15%. 3-(4-chloro-3-trifluoromethylphenyl)-5-ethoxy-1-methyl-4(1H)-pyridone, m.p. 158-159°C, yield 15%.

Eksempel 100II Example 100II

l-metyl-3-isppropyltio-5- (3-trif luormetylf enyl) -4 (.1H) - pyridon, smp. 93-94°C, utbytte 32%. 1-methyl-3-isopropylthio-5-(3-trifluoromethylphenyl)-4(.1H)-pyridone, m.p. 93-94°C, yield 32%.

Eksempel 100JJ Example 100JJ

3-(4-klor-3-trifluormetylfenyl)-5-etyltio-l-metyl-4(1H) - pyridon, smp. 115-116°C, utbytte 11%. 3-(4-chloro-3-trifluoromethylphenyl)-5-ethylthio-1-methyl-4(1H)-pyridone, m.p. 115-116°C, yield 11%.

Eksempel 100KK Example 100KK

3(4-klor-3-trifluormetylfenyl)-l-metyl-5-fenyl-4(1H) - pyridon, smp. 154-155°C, utbytte 17%. 3(4-chloro-3-trifluoromethylphenyl)-1-methyl-5-phenyl-4(1H)-pyridone, m.p. 154-155°C, yield 17%.

Eksempel 100LL Example 100LL

3-(4-benzyloksyfenyl)-l-metyl-5-(3-trifluormetylfenyl)-4(1H)-pyridon, amorft, utbytte 10%. 3-(4-Benzyloxyphenyl)-1-methyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, amorphous, yield 10%.

Forbindelsen nedenunder ble fremstilt ved hydrogenering av forbindelsen i eksempel 100LL i eddiksyre i nærvær av en The compound below was prepared by hydrogenating the compound in Example 100LL in acetic acid in the presence of a

hydrogeneringskatalysator av 5% palladium på karbon. hydrogenation catalyst of 5% palladium on carbon.

Eksempel 100MM Example 100MM

3-(4-hydroksyfenyl)-l-metyl-5-(3-trifluormetylfenyl)-4(1H)-pyridon, smp. 162-163°C, utbytte 50%. 3-(4-hydroxyphenyl)-1-methyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, m.p. 162-163°C, yield 50%.

Eksempel 100NN Example 100NN

3-(2,5-dimetylfenyl)-l-metyl-5-(3-trifluormetylfenyl)-4(1H)-pyridon, smp. 165-167°C, utbytte 2%. 3-(2,5-dimethylphenyl)-1-methyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, m.p. 165-167°C, yield 2%.

Eksempel 100OO Example 100OO

"3-(3,5-dimetylfenyl)-l-metyl-5-(3-trifluormetylfenyl)-4(1H)-pyridon, smp. 160-163°C, utbytte 6%. "3-(3,5-dimethylphenyl)-1-methyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, m.p. 160-163°C, yield 6%.

Eksempel 100PP Example 100PP

3-(2,4-diklorfenyl)-l-metyl-5-(3-trifluormetylfenyl)-4(1H)-pyridon, smp. 139-142°C, utbytte 11%. Eksempel 100QQ , 3-(2,4-dichlorophenyl)-1-methyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, m.p. 139-142°C, yield 11%. Example 100QQ,

l-metyl-3-fenyl-5-(2-trifluormetylfenyl)-4(1H)-pyridon, smp. 168-171°C, utbytte 14%. 1-methyl-3-phenyl-5-(2-trifluoromethylphenyl)-4(1H)-pyridone, m.p. 168-171°C, yield 14%.

Eksempel 100RR Example 100RR

l-metyl-3-(2-trifluormetylfenyl)-5-(3-trifluormetylfenyl)-4(1H)-pyridon, smp. 135-138°C, utbytte 24%. 1-methyl-3-(2-trifluoromethylphenyl)-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, m.p. 135-138°C, yield 24%.

Eksempel 100SS Example 100SS

3-(3,4-dimetylfenyl)-l-metyl-5-(3-trifluormetylfenyl)-4(1H)-pyridon, smp. 150-153°C, utbytte 15%. 3-(3,4-dimethylphenyl)-1-methyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, m.p. 150-153°C, yield 15%.

Eksempel 100TT Example 100TT

3-(3-jodfenyl)-l-metyl-5-(3-trifluormetylfenyl)-4(1H)-pyridon,' smp. 178-181°C, utbytte 15%. 3-(3-iodophenyl)-1-methyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, m.p. 178-181°C, yield 15%.

Eksempel 100UU Example 100UU

3-etyl-l-metyl-5-(3-metoksyfenyl)-4(1H)-pyridon, utbytte 5%, massespektroskopi MI, 243. 3-Ethyl-1-methyl-5-(3-methoxyphenyl)-4(1H)-pyridone, yield 5%, mass spectroscopy MI, 243.

Eksempel 100W Example 100W

l-metyl-3-(3-jodfenyl)-5-fenyl-4(1H)-pyridon, smp. 190-193°C, utbytte 8%. 1-methyl-3-(3-iodophenyl)-5-phenyl-4(1H)-pyridone, m.p. 190-193°C, yield 8%.

Eksempel 100WW Example 100WW

l-metyl-3-(4-metoksyfenoksy)-5-(3-trifluormetylfenyl)-4(1H)-pyridon, smp. 119-120°C, utbytte 25%. 1-methyl-3-(4-methoxyphenoxy)-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, m.p. 119-120°C, yield 25%.

Eksempel 100XX Example 100XX

l-metyl-3-(2-klor-4-fluorfenyl)-5-(3-trifluormetylfenyl)-4(1H)-pyridon, smp. 183-186°C, utbytte 20%. 1-methyl-3-(2-chloro-4-fluorophenyl)-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, m.p. 183-186°C, yield 20%.

Følgende forbindelse ble fremstilt ved oksydasjon av forbindelsen i eksempel 10OS med hydrogenperoksyd i metylen-diklorid ved omkring 0°CL The following compound was prepared by oxidation of the compound in Example 10OS with hydrogen peroxide in methylene dichloride at about 0°C

Eksempel 100YY Example 100YY

3-etylsulfonyl-l-mety1-5-(3-trifluormetylfenyl)-4(1H)-pyridon, smp. 196-198°C, utbytte 70%. 3-ethylsulfonyl-1-methyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, m.p. 196-198°C, yield 70%.

Eksempel 100ZZ Example 100ZZ

l-metyl-3-(4-klor-3-trifluormetylfenyl)-5-trifluormetyl-4(1H)-pyridon, smp. 164-165°C, utbytte 2%. 1-methyl-3-(4-chloro-3-trifluoromethylphenyl)-5-trifluoromethyl-4(1H)-pyridone, m.p. 164-165°C, yield 2%.

Eksempel 100AB Example 100AB

l-metyl-3-(4-klor-3-trifluormetylfenyl)-5-propyl-4(1H)-pyridon, smp. 141-142°C, utbytte 8%. 1-methyl-3-(4-chloro-3-trifluoromethylphenyl)-5-propyl-4(1H)-pyridone, m.p. 141-142°C, yield 8%.

Eksempel 100AC Example 100AC

l-metyl-3-isopropyltio-5-(4-klor-3-trifluormetylfenyl)-4(1H)-pyridon, smp. 127-l29°C, utbytte 15%. 1-methyl-3-isopropylthio-5-(4-chloro-3-trifluoromethylphenyl)-4(1H)-pyridone, m.p. 127-129°C, yield 15%.

Eksempel 100AD Example 100AD

l-metyl-3-(4-klor-3-trifluormetylfenyl)-5-propyltio-4(1H)-pyridon, smp. 128-130°C, utbytte 15%. 1-methyl-3-(4-chloro-3-trifluoromethylphenyl)-5-propylthio-4(1H)-pyridone, m.p. 128-130°C, yield 15%.

Eksempel 100AE Example 100AE

l-metyl-3-(4-klor-3-trifluormetylfenyl)-5-(2-tienyl)-4(1H)-pyridon, smp. 166-168°C, utbytte 10%. 1-methyl-3-(4-chloro-3-trifluoromethylphenyl)-5-(2-thienyl)-4(1H)-pyridone, m.p. 166-168°C, yield 10%.

Eksempel 100AF <1>Example 100AF <1>

3-etyl-l-metyl-5-(4-klor-3-trifluormetylfenyl)-4(1H)-pyridon, smp. 121-123°C,; utbytte 1%. 3-ethyl-1-methyl-5-(4-chloro-3-trifluoromethylphenyl)-4(1H)-pyridone, m.p. 121-123°C; dividend 1%.

Eksempel 10PAG Example 10 PAG

l-metyl-3- (2, 4-d'imetylf enyl) -5- (3-trif luormetylf enyl) - 4 (1H)-pyridon, smp. 128-<!>131°C, utbytte 6%. 1-methyl-3-(2,4-dimethylphenyl)-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, m.p. 128-<!>131°C, yield 6%.

Eksempel 100AH Example 100AH

3-isopropoksy-l-metyl-5-(3-trifluormetylfenyl)-4(1H)-pyridon, massespektroskopi MI, 311, utbytte 1%. 3-isopropoxy-1-methyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, mass spectroscopy MI, 311, yield 1%.

Eksempel 100AI Example 100AI

l-metyl-3-(4-kldrfenoksy)-5-(3-trifluormetylfenyl)-4(1H)-pyridon, smp. 90-91°C, utbytte 15%. 1-methyl-3-(4-chlorophenoxy)-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, m.p. 90-91°C, yield 15%.

Eksempel 100AJ Example 100AJ

l-metyl-3-(3-metyltiofenyl)-5-(3-trifluormetylfenyl)-4(1H)-pyridon, smp. 150-153°C, utbytte 25%. 1-methyl-3-(3-methylthiophenyl)-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, m.p. 150-153°C, yield 25%.

Følgende forbindelse ble fremstilt ved oksydasjon av forbindelsen i eksempel 10OAJ med hydrogenperoksyd i pyridin ved romtemperatur. The following compound was prepared by oxidation of the compound in example 10OAJ with hydrogen peroxide in pyridine at room temperature.

Eksempel 100AK Example 100AK

l-metyl-3-(3-metylsylfonylfenyl)-5-(3-trifluormetylfenyl)-4(1H)-pyridon, smp. 180-183°C, utbytte 20%. 1-methyl-3-(3-methylsulfonylphenyl)-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, m.p. 180-183°C, yield 20%.

Følgende forbindelse ble fremstilt ved oksydasjon av forbindelsen i eksempel 100S med natriumperjodat i vandig etanol ved romtemperatur i 16 timer. The following compound was prepared by oxidation of the compound in Example 100S with sodium periodate in aqueous ethanol at room temperature for 16 hours.

Elsempel 100AL Electricity example 100AL

3-etyl-sulfinyl-l-metyl-5-(3-trifluormetylfenyl)-4(1H)-pyridon, smp. 146-148°C, utbytte 82%. 3-ethyl-sulfinyl-1-methyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, m.p. 146-148°C, yield 82%.

Eksempel 100AM Example 100AM

l-metyl-3-(3-trifluormetylfenoksy)-5-(3-trifluormetyl-fenyl)-4(1H)-pyridon, smp. 93-95°C, utbytte 40%. 1-methyl-3-(3-trifluoromethylphenoxy)-5-(3-trifluoromethyl-phenyl)-4(1H)-pyridone, m.p. 93-95°C, yield 40%.

Eksempel 100AN Example 100AN

3-(4-metoksyfenyl)-l-metyl-5-(3-trifluormetylfenyl)-4(1H)-pyridon, smp. 160-162°C, utbytte 40%. 3-(4-Methoxyphenyl)-1-methyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, m.p. 160-162°C, yield 40%.

Eksempel 100AO Example 100AO

3-(2,3-diklorfenoksy)-l-metyl-5-(3-trifluormetylfenyl)-4(1H)-pyridon, smp. 200-202°C, utbytte 30%. 3-(2,3-dichlorophenoxy)-1-methyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, m.p. 200-202°C, yield 30%.

Eksempel 100AP Example 100AP

3-(3,5-diklorfenoksy)-l-metyl-5-(3-trifluormetylfenyl)-4(1H)-pyridon, smp. 128-130°C, utbytte 30%. 3-(3,5-dichlorophenoxy)-1-methyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, m.p. 128-130°C, yield 30%.

Eksempel 100AQ Example 100AQ

3-(3,4-diklorfenoksy)-l-metyl-5-(3-trifluormetylfenyl)-4(1H)-pyridon, smp. 127-129°C, utbytte 20%. 3-(3,4-dichlorophenoxy)-1-methyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, m.p. 127-129°C, yield 20%.

Eksempel 100AR Example 100AR

3-(4-klor-3-trifluormetylfenyl)-l-metyl-5-isopropyl-4(1H)-pyridon, smp. 85-87°C, utbytte 25%. 3-(4-chloro-3-trifluoromethylphenyl)-1-methyl-5-isopropyl-4(1H)-pyridone, m.p. 85-87°C, yield 25%.

Eksempel 10OAS Example 10OAS

3-(2,5-diklorfenoksy)-l-metyl-5-(3-trifluormetylfenyl)-4(1H)-pyridon, smp. 162-164°C, utbytte 28%. 3-(2,5-dichlorophenoxy)-1-methyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, m.p. 162-164°C, yield 28%.

Eksempel 100AT Example 100AT

l-metyl-3-(4-metyltiofenoksy)-5-(3-trifluormetylfenyl)-4(1H)-pyridon, smp. 138-140°C, utbytte 17%. 1-methyl-3-(4-methylthiophenoxy)-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, m.p. 138-140°C, yield 17%.

Eksempel 100AU Example 100AU

3-isobutyltio-l-metyl-5-(3-trifluormetylfenyl)-4(1H)-pyridon, massespektroskopi MI, 341, utbytte 1%. 3-isobutylthio-1-methyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, mass spectroscopy MI, 341, yield 1%.

Eksempel 100AV Example 100AV

3-t-butyltio-l-metyl-5-(3-trifluormetylfenyl)-4(1H)-pyridon, smp. 124-125°C, utbytte 1%. 3-t-butylthio-1-methyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, m.p. 124-125°C, yield 1%.

Eksempel 100AW Example 100AW

3-s-butyltio-l-metyl-5-(3-trifluormetylfenyl)-4(1H)-pyridon, massespektroskopi MI, 341, utbytte 1%. 3-s-Butylthio-1-methyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, mass spectroscopy MI, 341, yield 1%.

Eksempel 100AX Example 100AX

l-metyl-3-(4-nitrpfenoksy)-5-(3-trifluormetylfenyl)-4(1H)-pyridon, smp. 160-161°C, utbytte 21%. 1-methyl-3-(4-nitrophenoxy)-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, m.p. 160-161°C, yield 21%.

Eksempel 100AY Example 100AY

3-etyl-l-hydroksy-5-(3-trifluormetylfenyl)-4(1H)-pyridon, smp. 134-136°C, utbytte 1%. 3-ethyl-1-hydroxy-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, m.p. 134-136°C, yield 1%.

Eksempel 100AZ Example 100AZ

l-metyl-3-trif luoirmetylsulf onyl-5- (3-trif luormetylf enyl) - 4(1H)-pyridon, smp. 155-157°C, utbytte 1%. 1-methyl-3-trifluoromethylsulfonyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, m.p. 155-157°C, yield 1%.

Eksempel 100BA Example 100BA

l-metyl-3-(3-trifluormetylfenyl)-5-(3-trifluormetyltio-fenyl)-4(1H)-pyridon, NMRi multiplet ved 8,0-7,1 ppm, singlet ved 3,27 ppm, utbytte 1%.'1-methyl-3-(3-trifluoromethylphenyl)-5-(3-trifluoromethylthio-phenyl)-4(1H)-pyridone, NMRi multiplet at 8.0-7.1 ppm, singlet at 3.27 ppm, yield 1 %.'

Eksempel 100BC i Example 100BC i

l-metyl-3-(3-trifluormetylfenyl)-5-(3-trifluormetylsul-fonylf enyl)-4 (1H)-pyridoni, smp. 164-166°C, utbytte 1%. 1-methyl-3-(3-trifluoromethylphenyl)-5-(3-trifluoromethylsulfonylphenyl)-4(1H)-pyridone, m.p. 164-166°C, yield 1%.

Eksempel 100BD Example 100BD

l-metyl-3-(2,2,2-trifluoretoksy)-5-(3-trifluormetylfenyl)-4(1H)-pyridon, NMR multiplet ved 8,0-7,1 ppm, kvartet ved 4,6 ppm, singlet ved 3,7 ppm, utbytte 1%. 1-methyl-3-(2,2,2-trifluoroethoxy)-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, NMR multiplet at 8.0-7.1 ppm, quartet at 4.6 ppm, singlet at 3.7 ppm, yield 1%.

Eksempel 10QBE Example 10QBE

l-metyl-3-(2-nitrofenyl)-5-(3-trifluormetylfenyl)-4(1H)-pyridon, smp. 230-232°C, utbytte 10%. 1-methyl-3-(2-nitrophenyl)-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, m.p. 230-232°C, yield 10%.

Eksempel 100BF Example 100BF

l-metyl-3-(3-trifluormetylfenyl)-5-trifluormetyltio-4(1H)-pyridon, smp. 122-124°C, utbytte 21%. 1-methyl-3-(3-trifluoromethylphenyl)-5-trifluoromethylthio-4(1H)-pyridone, m.p. 122-124°C, yield 21%.

Det neste eksempel illustrerer en fremgangsmåte hvor enaminoketonet med formel X først formyleres til en forbind- The next example illustrates a method where the enaminoketone of formula X is first formylated to a compound

else med formel VI og derpå utveksles med aminet under dann- reaction with formula VI and then exchanged with the amine to form

else av pyridonet. else of the pyridone.

Eksempel 101 Example 101

Man fremstilte et enaminoketon ut fra 3,5 g N,N-dietyl-styrylamin og 2,16 g metoksyacetylklorid i nærvær av 2 g 1-dietylamino-4-metoksy-2-fenyl-l-buten-3-on. An enamino ketone was prepared from 3.5 g of N,N-diethyl-styrylamine and 2.16 g of methoxyacetyl chloride in the presence of 2 g of 1-diethylamino-4-methoxy-2-phenyl-1-buten-3-one.

Ovennevnte enaminoketon ble blandet med 3,2 g natrium-metoksyd i 50 ml tørr tetrahydrofuran ved 0°C, og 4,4 g etylformiat tilsatt dråpevis. Etter at blandingen var omrørt i tre timer, tilsatte man 25 ml 40%-ig vandig metylamin fulgt av 5 g metylaminhydroklorid. Blandongen ble omrørt over natten ved romtiemperatur og oppløsningsmidlene fjernet i vakuum. Residuet ble oppløst i metylenklorid, vasket med vann og mettet natriumkloridoppløsning og tørket. Oppløsningsmidlet ble fjernet i vakuum og residuet gnidd ut med etyleter. De faste stoffer ble «omkrystallisert fra isopropyleter-metylenklorid og ga 1 g 3-metoksy-l-metyl-5-fenyl-4(lH)-pyridon, sm.p. 153-i55°c The above-mentioned enamino ketone was mixed with 3.2 g of sodium methoxide in 50 ml of dry tetrahydrofuran at 0°C, and 4.4 g of ethyl formate added dropwise. After the mixture had been stirred for three hours, 25 ml of 40% aqueous methylamine was added followed by 5 g of methylamine hydrochloride. The mixture was stirred overnight at room temperature and the solvents removed in vacuo. The residue was dissolved in methylene chloride, washed with water and saturated sodium chloride solution and dried. The solvent was removed in vacuo and the residue triturated with ethyl ether. The solids were recrystallized from isopropyl ether-methylene chloride to give 1 g of 3-methoxy-1-methyl-5-phenyl-4(1H)-pyridone, m.p. 153-155°C

Eksempel 101A Example 101A

3-etoksy-l-mety1-5-(3-trifluormetylfenyl)-M(1H)-pyridon, smp. 131-133°C, utbytte 17%. 3-Ethoxy-1-methyl-5-(3-trifluoromethylphenyl)-M(1H)-pyridone, m.p. 131-133°C, yield 17%.

De følgende eksempler illustrerer fremstilling • av 3-bydroksyfenyl-substituerte forbindelser hvorfra andre substituerte forbindelser fremstilles i de følgende eksempler. Eksempel 102 1 g produkt fra Eksempel 20 ble oppløst i 250 ml eddiksyre og 1 g 5$-ig palladium/kull ble tilsatt. Blandingen ble hydrogenert i ca. 45 minutter, filtrert, og filtratet inndampet til tørrhet. Produktet ble omkrystallisert fra etylacetat-heksan og ga 0,45 g 3-(3-hydroksyfenyl)-l-metyl-5-fenyl-4(1H)-pyridon, smp. 223-225°C. The following examples illustrate the preparation • of 3-byhydroxyphenyl-substituted compounds from which other substituted compounds are prepared in the following examples. Example 102 1 g of product from Example 20 was dissolved in 250 ml of acetic acid and 1 g of 5% palladium/charcoal was added. The mixture was hydrogenated for approx. 45 minutes, filtered, and the filtrate evaporated to dryness. The product was recrystallized from ethyl acetate-hexane to give 0.45 g of 3-(3-hydroxyphenyl)-1-methyl-5-phenyl-4(1H)-pyridone, m.p. 223-225°C.

Samme forbindelse ble også fremstilt ved spalt-ing med pyridin-hydroklorid som følger: 2 g 3-(3-metoksyfenyl)-l-metyl-5-fenyl-4(1H)-pyridon ble blandet med 15 g pyridin-hydroklorid og blandingen oppvarmet ved tilbakeløp i ca. 1 time. Derpå ble den heilt opp i en stor mengde vann og de utfelte stoffer frafiltrert. De frafUtrerte faste stoffer ble omkrystallisert fra etanol-etyleter og ga 1,1 g 3-(3-hydroksyfenyl)-l-metyl-5-fenyl-4(1H)-pyridon. Ytterligere 0,65 g ble utvunnet ved konsentrering av ovennevnte filtrat. Produktet var identisk med produktet fra tidligere avsnitt. The same compound was also prepared by cleavage with pyridine hydrochloride as follows: 2 g of 3-(3-methoxyphenyl)-1-methyl-5-phenyl-4(1H)-pyridone was mixed with 15 g of pyridine hydrochloride and the mixture heated by reflux for approx. 1 hour. It was then poured into a large amount of water and the precipitated substances filtered off. The filtered solids were recrystallized from ethanol-ethyl ether to give 1.1 g of 3-(3-hydroxyphenyl)-1-methyl-5-phenyl-4(1H)-pyridone. A further 0.65 g was recovered by concentration of the above filtrate. The product was identical to the product from the previous section.

Følgende forbindelse ble fremstilt i henhold til metoden fra Eksempel 102: Eksempel 103 The following compound was prepared according to the method of Example 102: Example 103

3-cykloheksyl-5-(3-hydroksyfenyl)-l-metyl-4(1H)-pyridon, sm.p. 155-l65°C, utbytte 13$. 3-cyclohexyl-5-(3-hydroxyphenyl)-1-methyl-4(1H)-pyridone, m.p. 155-l65°C, yield 13$.

Eksempel 104 Example 104

3,2 g produkt fra Eksempel 102 ble satt til en suspensjon av 0,86 g natriumhydrid i 50 ml dimetylsulfoksyd. 3.2 g of product from Example 102 was added to a suspension of 0.86 g of sodium hydride in 50 ml of dimethyl sulfoxide.

i in

Blandingen ble omrørt ved romtemperatur og 3,5 g etyljodid tilsatt. Blandingen ble omrørt i 2.1/2 time, heilt opp i vann og den vandige blanding ekstrahert med etylacetat. Ekstraktet ble vasket med fortynnet saltsyre og derpå med vann og tørket. Det tørkede ekstrakt ble filtrert og konsentrert til tørrhet i vakuum. Produktet besto !av 2,2 g 3- (3-et°ksyfenyl)-l-metyl-5-fenyl-4(lH)-pyridon, sm.p. 133-135°C. The mixture was stirred at room temperature and 3.5 g of ethyl iodide added. The mixture was stirred for 2.1/2 hours, poured into water and the aqueous mixture extracted with ethyl acetate. The extract was washed with dilute hydrochloric acid and then with water and dried. The dried extract was filtered and concentrated to dryness in vacuo. The product consisted of 2.2 g of 3-(3-ethoxyphenyl)-1-methyl-5-phenyl-4(1H)-pyridone, m.p. 133-135°C.

De nedenstående eksempler ble fremstilt i henhold til metoder analoge med Eksempel 104• The examples below were prepared according to methods analogous to Example 104•

Eksempel 105 Example 105

3-(3-allyloksyfenyl)-1-mety1-5-fenyl-4(1H)-pyridon, NMR-topper ved 211 og 270 CPS, brede bånd ved 296-328, 34I-378 og 399-458 CPS, utbytte 10$. 3-(3-allyloxyphenyl)-1-methyl-5-phenyl-4(1H)-pyridone, NMR peaks at 211 and 270 CPS, broad bands at 296-328, 34I-378 and 399-458 CPS, yield 10 $.

Eksempel 106 Example 106

3-/"3-(l-fluor-2-jodvinyloksy)fenyl_7-l-metyl-5-fenyl-4(lH)-pyridon, NMR-topper ved 2l8 CPS, bred topp ved 27O-316 CPS, aromatiske protoner ved 416-464 CPS, utbytte 67$. Eksempel 107 3-/"3-(1-Fluoro-2-iodovinyloxy)phenyl_7-1-methyl-5-phenyl-4(1H)-pyridone, NMR peaks at 218 CPS, broad peak at 270-316 CPS, aromatic protons at 416-464 CPS, dividend $67 Example 107

3-(3-isopropoksyfenyl)-1-mety1-5-fenyl-4(1H)-pyridon, NMR-topper ved 8l, 209 og 276 CPS, aromatiske protoner ved 401-468 CPS, utbytte l8$. 3-(3-Isopropoxyphenyl)-1-methyl-5-phenyl-4(1H)-pyridone, NMR peaks at 81, 209 and 276 CPS, aromatic protons at 401-468 CPS, yield l8$.

Eksempel 108 Example 108

3-(3-cyanmetoksyfenyl)-l-metyl-5-fenyl-4(lH)-pyridon, NMR.-topper ved 207 og 275 OPS, aromatiske protoner ved 396-456 CPS, utbytte 6$.' 3-(3-cyanomethoxyphenyl)-l-methyl-5-phenyl-4(lH)-pyridone, NMR.-peaks at 207 and 275 OPS, aromatic protons at 396-456 CPS, yield 6$.'

Eksempel 109 i Example 109 i

3-(3-dodecyloksyfenyl)-l-metyl-5-fenyl-4(1H)-pyridon, NMR-topper ved 52, 207 og 234 CPS, bred topp ved 60-122 CPS, aromatiske protoner ved 396-461 CPS, utbytte 26$. ' Eksempel 110 3-(3-dodecyloxyphenyl)-1-methyl-5-phenyl-4(1H)-pyridone, NMR peaks at 52, 207 and 234 CPS, broad peak at 60-122 CPS, aromatic protons at 396-461 CPS, dividend 26$. ' Example 110

l-metyl-3-/~3-(4-nitrofenoksy)fenyl_7-5-feny1-4(1H)-pyridon, NMR-topper ved 222 og 488,5 CPS, aromatiske protoner ved 414-463 CPS<1>, utbytte 14$. 1-methyl-3-/~3-(4-nitrophenoxy)phenyl_7-5-phenyl-4(1H)-pyridone, NMR peaks at 222 and 488.5 CPS, aromatic protons at 414-463 CPS<1>, dividend 14$.

Eksempel 111 Example 111

l-metyl-3-(3-metylsulfonyloksyfenyl)-5-fenyl-4(1H)-pyridon, NMR-topper ved 185 og 213 CPS, aromatiske pro- 1-methyl-3-(3-methylsulfonyloxyphenyl)-5-phenyl-4(1H)-pyridone, NMR peaks at 185 and 213 CPS, aromatic pro-

toner ved 422-472 CPS, utbytte 20%. toner at 422-472 CPS, yield 20%.

Eksempel 112 Example 112

l-metyl-3-fenyl-5-/~3-(l,l,2,2-tetrafluoretoksy)-fenyl_7-4(lH)-pyridon, sm.p. liq-121°C, utbytte 84$, fremstilt med tetrafluoretylen, i nærvær av kaliumhydroksyd. 1-methyl-3-phenyl-5-[3-(1,1,2,2-tetrafluoroethoxy)-phenyl_7-4(1H)-pyridone, m.p. liq-121°C, yield 84$, prepared with tetrafluoroethylene, in the presence of potassium hydroxide.

Eksempel 113 Example 113

3-(3-acetoksyfenyl)-l-metyl-5-fenyl-4(1H)-pyridon, NMR-topper ved 134 og 210 CPS, aromatiske protoner ved 415-466 CPS, utbytte 28%, fremstilt med eddiksyreanhydrid. Eksempel 114 3-(3-acetoxyphenyl)-1-methyl-5-phenyl-4(1H)-pyridone, NMR peaks at 134 and 210 CPS, aromatic protons at 415-466 CPS, yield 28%, prepared with acetic anhydride. Example 114

3-(3-heksyloksyfenyl)-l-metyl-5-fenyl-4(1H)-pyridon, NMR-topper ved 53, 214 og 239 CPS, bred topp ved 60-120 CPS, aromatiske protoner ved 402-465 CPS, utbytte 55%. Eksempel 115 3-(3-hexyloxyphenyl)-1-methyl-5-phenyl-4(1H)-pyridone, NMR peaks at 53, 214 and 239 CPS, broad peak at 60-120 CPS, aromatic protons at 402-465 CPS, dividend 55%. Example 115

3-(3-decykloksyfenyl)-l-metyl-5-fenyl-4(1H)-pyridon, NMR-topper ved 53, 211 og 239 CPS, bred topp ved 62-123 CPS, aromatiske protoner ved 404-467 CPS, utbytte 24%. Eksempel ll6 3-(3-Decyclooxyphenyl)-1-methyl-5-phenyl-4(1H)-pyridone, NMR peaks at 53, 211 and 239 CPS, broad peak at 62-123 CPS, aromatic protons at 404-467 CPS, dividend 24%. Example ll6

1-mety1-3-fenyl-5-(3-propoksyfenyl)-441H)-pyridon, NMR-topper ved 54, 101,5, 208 og 232 CPS, aromatiske pro-' toner ved 4OO-463 CPS, utbytte 31%. 1-methyl-3-phenyl-5-(3-propoxyphenyl)-441H)-pyridone, NMR peaks at 54, 101.5, 208 and 232 CPS, aromatic protons at 400-463 CPS, yield 31% .

Eksempel 117 Example 117

1-mety1-3-fenyl-5-(3-ProPargyloksyfenyl)-4(1H)-. pyridon, NMR-topper ved 150 og 215 CPS, bred topp ved 280-285 CPS, aromatiske protoner ved 430-470»CPS, utbytte 6%. Eksempel ll8 1-Methyl-3-phenyl-5-(3-ProPargyloxyphenyl)-4(1H)-. pyridone, NMR peaks at 150 and 215 CPS, broad peak at 280-285 CPS, aromatic protons at 430-470 »CPS, yield 6%. Example ll8

3-(3-cykloheksylmetoksyfenyl)-l-metyl-5-fenyl-4(1H)-pyridon, NMR-topper ved 214 og 226 CPS, bred topp ved 35-124 CPS, aromatiske protoner ved 402-466 CPS, utbytte 16%. Eksempel 119 3-(3-Cyclohexylmethoxyphenyl)-1-methyl-5-phenyl-4(1H)-pyridone, NMR peaks at 214 and 226 CPS, broad peak at 35-124 CPS, aromatic protons at 402-466 CPS, yield 16 %. Example 119

l-metyl-3-(3-oktyloksyfenyl)-5-fenyl-4(1H)-pyridon, NMR-topper ved 52, 218 og 239 CPS, bred topp ved 58-122 CPS, aromatiske protoner ved 403-467 CPS, utbytte 19%. Eksempel 120 1-methyl-3-(3-octyloxyphenyl)-5-phenyl-4(1H)-pyridone, NMR peaks at 52, 218 and 239 CPS, broad peak at 58-122 CPS, aromatic protons at 403-467 CPS, dividend 19%. Example 120

l-metyl-3-(3-fenoksyfenyl)-5-fenyl-4(1H)-pyridon, NMR-topp ved 214 CPS, aromatiske protoner ved 4IO-47O CPS, utbytte 34%. 1-methyl-3-(3-phenoxyphenyl)-5-phenyl-4(1H)-pyridone, NMR peak at 214 CPS, aromatic protons at 410-470 CPS, yield 34%.

Følgende eksempel demonstrerer en syntese ut fra et keton, hvor utgangsstoffet først formyleres til en forbindelse med formel IX, derpå aminoformyleres til en forbindelse med formel VI og til slutt utveksles med et amin for fremstilling av pyridonet. The following example demonstrates a synthesis from a ketone, where the starting material is first formylated to a compound of formula IX, then aminoformylated to a compound of formula VI and finally exchanged with an amine to produce the pyridone.

Eksempel 121 Example 121

12 g natriummetoksyd ble suspendert i 150 ml etyleter. Suspensjonen ble avkjølt i isbad og 28 g l-fenyl-3-(3-trifluormetylfenyl)-2-propanon ble tilsatt. 14 g etylformiat ble tilsatt dråpevis ,til den omrørte blanding. Mens reaksjonsblandingen ble stadig omrørt, ble den hensatt til langsom oppvarming til romtemperatur over natten. Om morgenen ble blandingen ekstrahert med vann og vannsjiktet surgjort med fortynnet saltsyre, samt'ekstrahert med metylenklorid. Det organiske sjiktet ble ekstrahert med fortynnet vandig natrium-hydroksyd og vannsjikteti igjen surgjort med fortynnet saltsyre og ekstrahert med metylenklorid. Det organiske sjikt ble tør-ket og inndampet til tørrhet i vakuum til en olje som overveiende besto av l-hydroksy^2-fenyl-4-(3-trifluormetylfenyl)-l-buten-3-on. 11 g av dette mellomproduktet ble oppvarmet på dampbad med 20 ml dimetylformamid-dimetylacetal i 16 timer. Reaksjonsblandingen ble avdampet til tørrhet i vakuum og av-dampningsresten oppløst i 150 ml etanol. 10 g metylamin-hydroklorid og 20 ml 40%-ig vandig metylamin ble tilsatt og • blandingen omrørt ved tilbakeløpstemperatur over natten. Reaksjonsblandingen ble inndampet i vakuum til en olje. Oljen ble tatt opp i kloroform og oppløsningen vasket med vann og tørket over natriumsulfat• Oppløsningsmidlet ble avdampet i vakuum og resten gnidd ut med etyleter. Eteren ble filtrert til l-metyl-3-feny1-5-(3rtrifluormetylfenyl)-4(lH)-pyridon, sm. 12 g of sodium methoxide was suspended in 150 ml of ethyl ether. The suspension was cooled in an ice bath and 28 g of 1-phenyl-3-(3-trifluoromethylphenyl)-2-propanone was added. 14 g of ethyl formate was added dropwise to the stirred mixture. While the reaction mixture was continuously stirred, it was allowed to slowly warm to room temperature overnight. In the morning, the mixture was extracted with water and the aqueous layer acidified with dilute hydrochloric acid, as well as extracted with methylene chloride. The organic layer was extracted with dilute aqueous sodium hydroxide and the aqueous layer again acidified with dilute hydrochloric acid and extracted with methylene chloride. The organic layer was dried and evaporated to dryness in vacuo to an oil consisting predominantly of 1-hydroxy 2-phenyl-4-(3-trifluoromethylphenyl)-1-buten-3-one. 11 g of this intermediate product was heated on a steam bath with 20 ml of dimethylformamide-dimethyl acetal for 16 hours. The reaction mixture was evaporated to dryness in vacuo and the evaporation residue dissolved in 150 ml of ethanol. 10 g of methylamine hydrochloride and 20 ml of 40% aqueous methylamine were added and • the mixture stirred at reflux temperature overnight. The reaction mixture was evaporated in vacuo to an oil. The oil was taken up in chloroform and the solution washed with water and dried over sodium sulfate• The solvent was evaporated in vacuo and the residue was triturated with ethyl ether. The ether was filtered to 1-methyl-3-phenyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, m.p.

p. 153-155°C j Eksempel 121A mp 153-155°C j Example 121A

1-hydroksy-3-fenyl-5-(3-trifluormetylfenyl)-4(1H)-pyridon, smp. 240-2M3°C,' utbytte 10%. 1-hydroxy-3-phenyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, m.p. 240-2M3°C,' yield 10%.

Følgende eksempler viser syntese av et pyridon ut fra et keton, ved suksessiv aminoformylering til en for-■bindelse med formel X, formylering til en forbindelse med formel VI og utveksling med et amin. The following examples show the synthesis of a pyridone from a ketone, by successive aminoformylation to a compound of formula X, formylation to a compound of formula VI and exchange with an amine.

Eksempel 122 Example 122

28 g 1-(3-trifluormetylfenyl)-3-feny1-2 -propanon ble blandet med 12 g diro1et<y>lformamid-dimet<y>laceta<l> og oppvarmet på dampbad under en kjølefelle som fjernet etanol etter hvert som denne dannet seg. Man fortsatte oppvarmingen over natten, hvoretter reaksjonsblandingen ble avdampet til en olje som hovedsakelig var en blanding av l-dimetylamino-4-fenyl-2-(3-trifluormetylfenyl)-l-buten-3-on og l-dimetylamino-2-fenyl-4-(3-trifluormetylfenyl)-l-buten-3-on. 5 g av d"ette mellomproduktet ble formylert med etylformiat i nærvær av natriummetoksyd i henhold til metoden fra Eksempel 121. Formylerings-produktet ble oppløst i etanol og behandlet med 5 g metylamin-hydroklorid og 20 ml 40%-ig vandig metylamin. Blandingen ble omrørt over natten ved til-bakeløpstemperatur, hvoretter oppløsningsmidlet ble fjernet i vakuum, 100 ml vann tilsatt til inndampningsresten og oppløs-ningen ekstrahert med etyleter. Eteroppløsningen ble tørket over .natriumsulfat og avdampet til tørrhet og ga da 1-metyl-3-fenyl-5-(3-trifluormetylfenyl)-4(1H)-pyridon, sm.p. 153-155°C. 28 g of 1-(3-trifluoromethylphenyl)-3-phenyl-2-propanone were mixed with 12 g of diro1eth<y>lformamide-dimeth<y>laceta<l> and heated on a steam bath under a cooling trap which removed ethanol as this formed. Heating was continued overnight, after which the reaction mixture evaporated to an oil which was mainly a mixture of 1-dimethylamino-4-phenyl-2-(3-trifluoromethylphenyl)-1-buten-3-one and 1-dimethylamino-2-phenyl -4-(3-trifluoromethylphenyl)-1-buten-3-one. 5 g of this intermediate product was formylated with ethyl formate in the presence of sodium methoxide according to the method from Example 121. The formylation product was dissolved in ethanol and treated with 5 g of methylamine hydrochloride and 20 ml of 40% aqueous methylamine. The mixture was stirred overnight at reflux temperature, after which the solvent was removed in vacuo, 100 mL of water added to the residue, and the solution extracted with ethyl ether. The ether solution was dried over sodium sulfate and evaporated to dryness to give 1-methyl-3-phenyl- 5-(3-trifluoromethylphenyl)-4(1H)-pyridone, mp 153-155°C.

Det følgende eksempel illustrerer syntese av en usubstituert pyridon ved omsetning av et keton med trisffor-mylamino)metan. For fremstilling av en forbindelse med formel I blir dette produktet alkylert. The following example illustrates the synthesis of an unsubstituted pyridone by reaction of a ketone with trisformylamino)methane. To prepare a compound of formula I, this product is alkylated.

Eksempel 123 Example 123

1,4 g 1,3-difenyl-2-propanon ble blandet med 1.4 g of 1,3-diphenyl-2-propanone was mixed with

1,0 g tris(formylamino)metan i 20 ml dimetylformamid. Reaksjonsblandingen ble omrørt ved tilbakeløpstemperatur i 3 timer. Blandingen ble derpå avkjølt til omtrent romtemperatur og heilt opp i vann. De utfelte faste stoffer ble frafiltrert og suspendert i kloroform. Kloroformen ble filtrert, og de gjenværende faste stoffer ble vasket først med vann og derpå med kloroform. Utbyttet var ca. 100 mg 3,5-difenyl-4(lH)-pyridon, sm.p. over 335°C 1.0 g of tris(formylamino)methane in 20 ml of dimethylformamide. The reaction mixture was stirred at reflux temperature for 3 hours. The mixture was then cooled to approximately room temperature and poured into water. The precipitated solids were filtered off and suspended in chloroform. The chloroform was filtered and the remaining solids were washed first with water and then with chloroform. The yield was approx. 100 mg 3,5-diphenyl-4(1H)-pyridone, m.p. above 335°C

Det følgende eksempel viser syntese av et pyridon med formel I ved formylering av et keton til en forbindelse med formel IX, fulgt av utveksling med et amin til en forbindelse med formel VII, og aminoformylering. The following example shows the synthesis of a pyridone of formula I by formylation of a ketone to a compound of formula IX, followed by exchange with an amine to a compound of formula VII, and aminoformylation.

Eksempel 124 Example 124

Man gjennomførte formylering av 1-fenyl-3-(3-tri-fluormetylfenyl)-2-propanon i henhold til metoden beskrevet i Eksempel 121. 5 g av dette produkt ble oppløst i 50 ml etanol og 20 ml 40%-ig vandig metylamin tilsatt. Blandingen ble hensatt over natt ved romtemperatur. Derpå ble den inndampet til tørrhet i vakuum, og etterlot en tung viskøs olje. Oljen ble blandet med 10 ml dimetylformamid-dimetylacetal og oppvarmet på dampbad over natten under en kjølefelle som fjernet etanol etterhvert som den dannet seg. Neste dag inndampet man reaksjonsblandingen til tørrhet i vakuum og inndampningsresten ble gnidd ut med eter. Eteroppløsningen ble filtrert og de faste stoffer omkrystallisert fra aceton-etyleter til l-metyl-3-fenyl-5- (3-trifluormetylfenyl)-4(1H)-pyridon, sm.p. 153-155°C. Eksempel 121A l-hydroksy-3-fenyl-5- (3-trif luormetylf enyl) -4 (1H) - pyridon, smp. 240-243°C, utbytte 10%. Formylation of 1-phenyl-3-(3-trifluoromethylphenyl)-2-propanone was carried out according to the method described in Example 121. 5 g of this product was dissolved in 50 ml of ethanol and 20 ml of 40% aqueous methylamine added. The mixture was left overnight at room temperature. It was then evaporated to dryness in vacuo, leaving a heavy viscous oil. The oil was mixed with 10 ml of dimethylformamide-dimethylacetal and heated on a steam bath overnight under a cold trap which removed ethanol as it formed. The next day, the reaction mixture was evaporated to dryness in vacuo and the evaporation residue was triturated with ether. The ether solution was filtered and the solids recrystallized from acetone-ethyl ether to give 1-methyl-3-phenyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, m.p. 153-155°C. Example 121A 1-hydroxy-3-phenyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, m.p. 240-243°C, yield 10%.

Eksempel 124A Example 124A

l-metyl-3-(1-metylbutyltio)-5-(3-trifluormetylfenyl)-4(1H)-pyridon, massespektroskopi MI, 3 55, utbytte 10%. Eksempel 124B 1-methyl-3-(1-methylbutylthio)-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, mass spectroscopy MI, 3 55, yield 10%. Example 124B

3-(2-hydroksypropyl)-l-metyl-5-(3-trifluormetylfenyl)-4(1H)-pyridon, smp. 99-102°C, utbytte 10%. 3-(2-Hydroxypropyl)-1-methyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, m.p. 99-102°C, yield 10%.

Eksempel 124C Example 124C

l-metyl-3-(2-metyl-2-propenyltio)-5-(3-trifluormetylfenyl)-4(1H)-pyridon, smp. 86-88°C, utbytte 10%. 1-methyl-3-(2-methyl-2-propenylthio)-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, m.p. 86-88°C, yield 10%.

Eksempel 124D Example 124D

3-etyltio-5-(2-klor-5-trifluormetylfenyl)-l-metyl-4(1H)-pyridon, smp. 127-129°C, utbytte 15%. 3-ethylthio-5-(2-chloro-5-trifluoromethylphenyl)-1-methyl-4(1H)-pyridone, m.p. 127-129°C, yield 15%.

Eksempel 124E Example 124E

3-(2-klor-5-trifluormetylfenyl)-l-metyl-5-fenyl-4(1H)-pyridon, smp. 150-152°C, utbytte 30%. 3-(2-chloro-5-trifluoromethylphenyl)-1-methyl-5-phenyl-4(1H)-pyridone, m.p. 150-152°C, yield 30%.

Eksempel 124 F i Example 124 F i

3-(2-klor-5-trifluormetylfenyl)-l-metyl-5-(3-trifluor-metylf enyl) -4 (1H) -pyridon, NMR topper, en multiplet ved 8,0-7,2 ppm, en singlet ved 3,57 ppm, utbytte 40%. 3-(2-Chloro-5-trifluoromethylphenyl)-1-methyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, NMR peaks, a multiplet at 8.0-7.2 ppm, a singlet at 3.57 ppm, yield 40%.

Det følgende eksempel illustrerer syntesen av forbindelser med formel I ved 4-klorering av et 1-usubstituert pyridon, fulgt av 1-alkylering og hydrolyse. The following example illustrates the synthesis of compounds of formula I by 4-chlorination of a 1-unsubstituted pyridone, followed by 1-alkylation and hydrolysis.

Eksempel 125 Example 125

39 g 3-fenyl-5-(3-trifluormetylfenyl)-4(lH)-pyridon fremstilt i henhold til Benary og Bitter, ble kokt ved tilbakeløp med 100 ml POpl^ og 5 ml dimetylformamid i tre timer. Overskuddet av POCl^ ble fjernet i vakuum og inndampningsresten tatt opp i kloroform. Oppløsningen ble heilt opp i isvann og blandingen omrørt til den nådde romtemperatur. Den vandige blanding ble ekstrahert med kloroform og den organiske oppløsning vasket med fortynnet natriumhydroksydoppløsning og tørket. Den organiske oppløsning ble inndampet til tørrhet i vakuum og inndampningsresten omkrystallisert fra heksan til 39 g of 3-phenyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, prepared according to Benary and Bitter, was refluxed with 100 ml of PO1^ and 5 ml of dimethylformamide for three hours. The excess of POCl^ was removed in vacuo and the evaporation residue taken up in chloroform. The solution was poured into ice water and the mixture stirred until it reached room temperature. The aqueous mixture was extracted with chloroform and the organic solution washed with dilute sodium hydroxide solution and dried. The organic solution was evaporated to dryness in vacuo and the evaporation residue recrystallized from hexane to

4-klor-3-fenyl-5-(3-trifluormetylfenyl)pyridin. 4-chloro-3-phenyl-5-(3-trifluoromethylphenyl)pyridine.

2 g av ovennevnte forbindelse ble oppløst i 20 ml kloroform og 10 ml metyljodid tilsatt. Blandingen ble hensatt fire' dager. Derpå ble den inndampet til tørrhet og residuet omkrystallisert fra kloroform-heksan til rent 4-klor-3-fenyl-5-(3-trifluormetylfenyl)-1-metylpyridiniumjodid. 2 g of the above compound was dissolved in 20 ml of chloroform and 10 ml of methyl iodide added. The mixture was kept for four days. It was then evaporated to dryness and the residue recrystallized from chloroform-hexane to give pure 4-chloro-3-phenyl-5-(3-trifluoromethylphenyl)-1-methylpyridinium iodide.

En porsjon av ovennevnte mellomprodukt ble opp-løst i metanol og oppløsningen gjort basisk med vandig natrium-hydroksydoppløsning. Den basiske blanding ble oppvarmet ved tilbakeløp i en time, avkjølt, og de faste stoffer frafiltrert. Produktet var l-metyl-3-fenyl-5-(3-trifluormetylfenyl)-4(lH)-pyridon, sm.p. 153-155 C. A portion of the above-mentioned intermediate was dissolved in methanol and the solution made basic with aqueous sodium hydroxide solution. The basic mixture was heated at reflux for one hour, cooled, and the solids filtered off. The product was 1-methyl-3-phenyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, m.p. 153-155C.

Det følgende eksempel illustrerer 1-alkylering av et 1-usubstituert pyridon ved omsetning med et metylerings-middel. The following example illustrates 1-alkylation of a 1-unsubstituted pyridone by reaction with a methylating agent.

Eksempel 126 Example 126

8 g 3-fenyl-1-(3-trifluormetylfenyl)-4(lH)-pyridon ble suspendert i 30 ml kloroform og 6 g metyltrifluormetan-sulfonat tilsatt. Reaksjonsblandingen ble omrørt i 3 timer, man tilsatte 10 g sulfonat i tillegg og blandingen ble omrørt over natten. Om morgenen ble reaksjonsblandingen heilt opp i vandig natriumkarbonatoppløsning. Den vandige blanding ble filtrert og fellingen vasket med mer kloroform. Det organiske sjiktet av filtratet ble separert, tørket på magnesiumsulfat og avdampet til tørrhet. Residuet var en oljeaktig gummimasse 8 g of 3-phenyl-1-(3-trifluoromethylphenyl)-4(1H)-pyridone was suspended in 30 ml of chloroform and 6 g of methyl trifluoromethane sulfonate added. The reaction mixture was stirred for 3 hours, 10 g of sulfonate were added in addition and the mixture was stirred overnight. In the morning, the reaction mixture was poured into aqueous sodium carbonate solution. The aqueous mixture was filtered and the precipitate washed with more chloroform. The organic layer of the filtrate was separated, dried over magnesium sulfate and evaporated to dryness. The residue was an oily gummy mass

som ved NMR-analyse ble identifisert som i det vesentlige ren 3-fenyl-5-(3-trifluormetylfenyl)-l-metyl-4-metoksypyridinium-trifluormetansulfonat. which was identified by NMR analysis as substantially pure 3-phenyl-5-(3-trifluoromethylphenyl)-1-methyl-4-methoxypyridinium trifluoromethanesulfonate.

Denne inndampningsresten ble blandet med 30 ml 'etanol og 3 ml konsentrert saltsyre og blandingen kokt ved tilbakeløp i 2 timer. Reaksjonsblandingen ble konsentrert under vakuum til en olje som ble tatt opp i metylenklorid. Denne ble vasket med vandig natriumkarbonatoppløsning og det organiske sjiktet igjen inndampet til tørrhet.i vakuum. Inndampningsresten ble gnidd ut med etylacetat som etterlot en rest som ble oppsamlet og kombinert med et senere utseparert produkt. Etylacetatoppløsningen ble konsentrert i vakuum, inndampningsresten blandet med 30 ml etanol og 10 ml 10%-ig natriumhydroksydoppløsning, og blandingen kokt ved tilbakeløp i to timer. Reaksjonsblandingen ble heilt opp i vann, det uoppløselige produktet frafiltrert og de faste stoffer omkrystallisert fra aceton. Produktet var l-metyl-3-fenyl-5-(3-tri-fluormetylfenyl)-4(1H)-pyridon, sm.p. 152-156°C. This evaporation residue was mixed with 30 ml of ethanol and 3 ml of concentrated hydrochloric acid and the mixture was refluxed for 2 hours. The reaction mixture was concentrated in vacuo to an oil which was taken up in methylene chloride. This was washed with aqueous sodium carbonate solution and the organic layer was again evaporated to dryness in vacuo. The evaporation residue was triturated with ethyl acetate which left a residue which was collected and combined with a later separated product. The ethyl acetate solution was concentrated in vacuo, the evaporation residue mixed with 30 ml of ethanol and 10 ml of 10% sodium hydroxide solution, and the mixture refluxed for two hours. The reaction mixture was poured into water, the insoluble product filtered off and the solids recrystallized from acetone. The product was 1-methyl-3-phenyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, m.p. 152-156°C.

Det følgende eksempel illustrerer bruk av form-iatester-aminal som aminoformyleringsmiddel. The following example illustrates the use of formate ester aminal as an aminoformylating agent.

Eksempel 127 Example 127

15 g i-fenyl-3-(3-trifluormetylfenyl)-2-propanon ble tilsatt til en etyleteroppløsning ved isbadtemperatur, inneholdende 70 g (t-butoksy)-di(dimetylamino)metan. Blandingen ble oppvarmet for avdampning av eteren og oppvarmet videre på dampbad i 2 timer. De flyktige stoffer ble avdampet i vakuum og inndampningsresten blandet med 15 g metylaminhydroklorid, 40 ml 40%-ig vandig metylamin og 200 ml etanol. Reaksjonsblandingen ble oppvarmet på dampbad i 6 timer og inndampet til tørrhet. Inndampningsresten ble tatt opp i vann og 15 g of i-phenyl-3-(3-trifluoromethylphenyl)-2-propanone was added to an ethyl ether solution at ice bath temperature, containing 70 g of (t-butoxy)-di(dimethylamino)methane. The mixture was heated to evaporate the ether and further heated on a steam bath for 2 hours. The volatile substances were evaporated in vacuo and the evaporation residue mixed with 15 g of methylamine hydrochloride, 40 ml of 40% aqueous methylamine and 200 ml of ethanol. The reaction mixture was heated on a steam bath for 6 hours and evaporated to dryness. The evaporation residue was taken up in water and

ekstrahert med metylenklorid. Det organiske sjiktet ble vasket med vann, tørket og kromatografert på silikagelkolonne med etylacetat:benzen. Oppsamling og inndamping av produktholdige fraksjoner ga ca. 0,9 g l-metyl-3-fenyl-5-(3-trifluormetyl-fenyl)-4(1H)-pyridon, smJp. 152-156°C. extracted with methylene chloride. The organic layer was washed with water, dried and chromatographed on a silica gel column with ethyl acetate:benzene. Collection and evaporation of product-containing fractions gave approx. 0.9 g of 1-methyl-3-phenyl-5-(3-trifluoromethyl-phenyl)-4(1H)-pyridone, m.p. 152-156°C.

Det neste eksempel viser bruk av et formiminium-halogenid for aminoformylering av utgangs-propanonet. The next example shows the use of a formiminium halide for the aminoformylation of the starting propanone.

Eksempel 128 Example 128

Aminoformyleringsmidlet ble fremstilt ved å sette 30 S dimetylformamid dråpevis til 20 g fosgen i 150 ml kloroform ved 0°C. En porsjon på 10 g l,3-bis-(3-klorfenyl)-2- propanon i 50 ml kloroform ble derpå tilsatt. Blandingen ble omrørt i 3 timer, hvoretter 50 ml 40%-ig vandig metylamin ble tilsatt. Kloroformen ble derpå avdampet og 200 ml etanol samt 50 ml 40%-ig vandigimetylamin tilsatt. Derpå ble blandingen kokt ved tilbakeløp over natten. Om morgenen ble produktet ekstrahert som beskrevet i ovenstående eksempel, og kromatografert på silikagel med etylacetat som inneholdt øk-ende mengder metanol. Produktet var 3,5-bis-(3-klorfenyl)-l-metyl-4(lH)-pyridon, 0,85 g, sm.p. l64-l67°C. The aminoformylating agent was prepared by adding 30 S dimethylformamide dropwise to 20 g phosgene in 150 ml chloroform at 0°C. A portion of 10 g of 1,3-bis-(3-chlorophenyl)-2-propanone in 50 ml of chloroform was then added. The mixture was stirred for 3 hours, after which 50 ml of 40% aqueous methylamine was added. The chloroform was then evaporated and 200 ml of ethanol and 50 ml of 40% aqueous dimethylamine added. The mixture was then refluxed overnight. In the morning, the product was extracted as described in the above example, and chromatographed on silica gel with ethyl acetate containing increasing amounts of methanol. The product was 3,5-bis-(3-chlorophenyl)-1-methyl-4(1H)-pyridone, 0.85 g, m.p. 164-167°C.

Fortsatt eluering av kolonnen med metanol elu-erte en forbindelse identifisert ved NMR som 4_klor-3,5-bis-(3-klorfenyl)-1-metylpyridiniumklorid. Hydrolyse av forbindelsen med vandig etanolisk natriumhydroksydoppløsning ved til-bakeløpstemperatur ga mer pyridon ved fortynning med vann, filtrering og omkrystallisasjon fra aceton-etyleter. Further elution of the column with methanol eluted a compound identified by NMR as 4-chloro-3,5-bis-(3-chlorophenyl)-1-methylpyridinium chloride. Hydrolysis of the compound with aqueous ethanolic sodium hydroxide solution at reflux temperature gave more pyridone upon dilution with water, filtration and recrystallization from acetone-ethyl ether.

Neste eksempel illustrerer hvorledes 1-acetoksy-forbindelser av formel I fremstilles. The next example illustrates how 1-acetoxy compounds of formula I are prepared.

Eksempel 129 Example 129

2»4 g 3»5-difenyl-l-hydroksy-4(lH)-pyridon ble fremstilt i henhold til Eksempel 29, med hydroksylamin som amineringsmiddel. Pyridonet ble satt til 25 ml eddiksyre-anhydrid og blandingen oppvarmet på dampbad i ca. 1 time. De flyktige stoffer ble avdampet i vakuum og inndampningsresten vasket med benzen og omkrystallisert, først fra benzen og derpå fra kloroform-heksan. Utbyttet var 2,1 g l-acetoksy-3,5-di-fenyl-4(lH)-pyridon, sm.p. 197-199°C. 2,4 g of 3,5-diphenyl-1-hydroxy-4(1H)-pyridone was prepared according to Example 29, with hydroxylamine as aminating agent. The pyridone was added to 25 ml of acetic anhydride and the mixture heated on a steam bath for approx. 1 hour. The volatile substances were evaporated in vacuo and the evaporation residue washed with benzene and recrystallized, first from benzene and then from chloroform-hexane. The yield was 2.1 g of 1-acetoxy-3,5-di-phenyl-4(1H)-pyridone, m.p. 197-199°C.

Følgende forbindelse ble fremstilt ved hjelp av fremgangsmåten i eksempel 129. The following compound was prepared using the procedure of Example 129.

Eksempel 129A Example 129A

l-acetoksy-3-fenyl-5-(3-trifluormetylfenyl)-4(1H)-pyridon, smp. 232-235°C, utbytte. 1-acetoxy-3-phenyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, m.p. 232-235°C, yield.

Eksemplet som følger er typisk for fremstilling av pyridintioner med formel I. The example that follows is typical for the preparation of pyridine ions of formula I.

Eksempel 130 Example 130

10 g 3.5-difenyl-l-metyl-4(lH)-pyridon fremstilt som angitt i Eksempel 1 ble blandet med 10 g P,,S^ i 100 ml pyridin og blandingen oppvarmet ved tilbakeløp i 2 timer, hvoretter den ble heilt opp i en stor mengde vann og omrørt i 1 time. Blandingen ble filtrert og de faste stoffer omkrystallisert fra etanol og ga 9,8 g 3,5-difenyl-l-metyl-4(lH)-pyridintion, sm.p. l68-171°C. 10 g of 3,5-diphenyl-1-methyl-4(1H)-pyridone prepared as indicated in Example 1 was mixed with 10 g of P,,S^ in 100 ml of pyridine and the mixture heated at reflux for 2 hours, after which it was poured in a large amount of water and stirred for 1 hour. The mixture was filtered and the solids recrystallized from ethanol to give 9.8 g of 3,5-diphenyl-1-methyl-4(1H)-pyridinethione, m.p. 168-171°C.

Eksempel 130A~ Example 130A~

3-(3-bromfenyl)-1-mety1-5-fenyl-4(1H)-pyridintion, 3-(3-bromophenyl)-1-methyl-5-phenyl-4(1H)-pyridinethione,

smp. 185-188°C, utbytte 59%. m.p. 185-188°C, yield 59%.

Eksempel 130B Example 130B

l-metyl-3-(4-klorfenyl)-5-(3-trifluormetylfenyl)-4(1H)-pyridintion, smp. 239-242°C, utbytte 25%. 1-methyl-3-(4-chlorophenyl)-5-(3-trifluoromethylphenyl)-4(1H)-pyridinethione, m.p. 239-242°C, yield 25%.

Eksempel 130C Example 130C

l-metyl-3-(3-metylfenyl)-5-(3-trifluormetylfenyl)-4(1H)-pyridintion, smp. 193-196°C, utbytte 50%. 1-methyl-3-(3-methylphenyl)-5-(3-trifluoromethylphenyl)-4(1H)-pyridinethione, m.p. 193-196°C, yield 50%.

Eksempel 130D Example 130D

l-metyl-3-(2-metylfenyl)-5-(3-trifluormetylfenyl)-4 (1H)-pyridintion, smp. 1:93-195°C, utbytte 35%. Eksempel 130E 1-methyl-3-(2-methylphenyl)-5-(3-trifluoromethylphenyl)-4(1H)-pyridinethione, m.p. 1:93-195°C, yield 35%. Example 130E

l-metyl-3-propyl-i5- (3-trif luormetylf enyl) -4 (1H) -pyridin-tion, smp. 145-148°C, utbytte 40%. 1-methyl-3-propyl-15-(3-trifluoromethylphenyl)-4(1H)-pyridine-thione, m.p. 145-148°C, yield 40%.

Eksempel 130F Example 130F

l-metyl-3-fenoksy-5-(3-trifluormetylfenyl)-4(1H)-pyridintion, smp. 127-13l°C, utbytte 40%. 1-methyl-3-phenoxy-5-(3-trifluoromethylphenyl)-4(1H)-pyridinethione, m.p. 127-131°C, yield 40%.

Eksempel 130G Example 130G

3-etyltio-l-metyl-5-(3-trifluormetylfenyl)-4(1H) - pyridintion, smp. 136-138°C, utbytte 55%. 3-ethylthio-1-methyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridinethione, m.p. 136-138°C, yield 55%.

Eksempel 130H Example 130H

3-etoksy-l-metyl-5-(3-trifluormetylfenyl)-4(1H)-pyridintion, smp. 153-155°C, utbytte 5%. 3-ethoxy-1-methyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridinethione, m.p. 153-155°C, yield 5%.

Følgende typiske pyridintioner ble fremstilt i henhold til den generelle metode fra eksempel 130. The following typical pyridine ions were prepared according to the general method of Example 130.

Eksempel 131 Example 131

3,5-bis(3-klorfenyl)-l-metyl-4(1H)-pyridintion, smp. 210-212°C, utbytte 86%. 3,5-bis(3-chlorophenyl)-1-methyl-4(1H)-pyridinethione, m.p. 210-212°C, yield 86%.

Eksempel 132 Example 132

3-(3-klorfenyl)-l-metyl-5-fenyl-4(1H)-pyridintion, smp. 190-193°C, utbytte 71%. 3-(3-Chlorophenyl)-1-methyl-5-phenyl-4(1H)-pyridinethione, m.p. 190-193°C, yield 71%.

Eksempel 133 Example 133

l-metyl-3-fenyl-5-(3-trifluormetylfenyl)-4(1H)-pyri-dintion, smp. 210°C, utbytte 70%. 1-methyl-3-phenyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridinethione, m.p. 210°C, yield 70%.

Følgende forbindelse ble fremstilt fra forbindelsen The following compound was prepared from the compound

i eksempel 1 ved tilbakeløpskoking i 4 timer i 60% svovelsyre. Eksempel 133A in example 1 by refluxing for 4 hours in 60% sulfuric acid. Example 133A

3-(3-karboksyfenyl)-l-metyl-5-fenyl-4(1H)-pyridon, smp. 265-367°C, utbytte 75%. 3-(3-carboxyphenyl)-1-methyl-5-phenyl-4(1H)-pyridone, m.p. 265-367°C, yield 75%.

Eksempel 134 Example 134

Forbindelser med formel I fremstilt i henhold til eksempel 1-23 kan også fremstilles etter metoden beskrevet i eksempel 29. Compounds of formula I prepared according to examples 1-23 can also be prepared according to the method described in example 29.

Eksempel 13 5 Example 13 5

Forbindelsene med formel I fremstilt i Eksempel 24-122 kan også fremstilles som angitt i Eksempel 1. The compounds of formula I prepared in Examples 24-122 can also be prepared as indicated in Example 1.

Forbindelser med formel I beskrevet i det foregående er undersøkt i en rekke ugressdrepende forsøkssystemer for å finne rekkevidden eller området for deres herbicide birk-ning. De fremstående resultater som ble oppnådd med de foreliggende forbindelser ved representative forsøk som fremgår nedenfor er eksempler på forbindelsenes virkning. Compounds of formula I described above have been tested in a variety of herbicidal test systems to determine the range or range of their herbicidal activity. The outstanding results obtained with the present compounds in representative experiments which appear below are examples of the effects of the compounds.

Utsprøytingsmengder er uttrykt i kg forbindelse pr. hektar dyrket mark (kg/ha) i foreliggende beskrivelse og krav. Spray quantities are expressed in kg compound per hectares of cultivated land (kg/ha) in the present description and requirements.

Åpne plasser i de følgende tabeller viser at forbindelsen ikke ble undersøkt overfor den angitte planteart. I enkelte tilfeller er det oppført middelverdier fra gjen-tatte forsøk. Open spaces in the following tables show that the compound was not tested against the indicated plant species. In some cases, mean values from repeated trials are listed.

Ubehandlede kontrollplanter eller forsøksfelter ble inkludert i alle forsøk. Virkningen av forsøksforbindel-sene ble bedømt ved sammenligning med ubehandlede kontrollplanter. Untreated control plants or experimental plots were included in all experiments. The effect of the test compounds was assessed by comparison with untreated control plants.

I forsøkene som inngår i Eksempel 136-140 ble plantene bedømt på en skala 1-5> hvor 1 angir normale planter og 5 angir døde planter eller ingen spiring. En 0-10-skala hvor 0 angir normale planter og 10 angir døde planter eller ingen spiring, ble benyttet til Eksempel 141-143 og 146-148, og forsøkene Eksempel 144-145 og 150 ble bedømt som prosentvis bekjempelse av plantene. Bedømmelses-målestokken som ble benyttet til forsøk i Eksempel 149 er angitt i beskrivelsen av eksempelet. In the experiments included in Examples 136-140, the plants were judged on a scale of 1-5> where 1 indicates normal plants and 5 indicates dead plants or no germination. A 0-10 scale where 0 indicates normal plants and 10 indicates dead plants or no germination was used for Examples 141-143 and 146-148, and the trials Examples 144-145 and 150 were judged as percent control of the plants. The assessment yardstick that was used for testing in Example 149 is indicated in the description of the example.

Eksempel 136 * Bredspektret veksthusforsøk Example 136 * Broad spectrum greenhouse trial

Firkantede plastpotter ble fylt med sterilisert sandjord og plantet med frø av tomater, fingeraks og kvinoa. Hver potte ble gjødslet individuelt. Square plastic pots were filled with sterilized sandy soil and planted with seeds of tomatoes, finger millet and quinoa. Each pot was fertilized individually.

Forsøksforbindelsene ble påført etter spiring The test compounds were applied after germination

på noen potter og før spiring på andre. Etterspiringsforsøk-ene skjedde ved at plantene ble sprøytet ca. 12 dager etter on some pots and before germination on others. The post-sprouting experiments took place by spraying the plants approx. 12 days after

at frøene var satt ut. Førspiringsforsøk skjedde ved at jorden ble sprøytet dagen etter; at frøene var satt ut. that the seeds had been planted. Pre-germination experiments were carried out by spraying the soil the following day; that the seeds had been planted.

Hver forsøksforbindelse ble oppløst i 1:1 aceton: etanol i en mengde på 2 <g pr. 100 ml. Oppløsningen inneholdt også ca. 2 g pr. 100 ml overflateaktiv blanding anionisk/ikke-ionisk. 1 ml oppløsning ble fortynnet til 4 ml med jonefritt vann, og 1,5 ml av den resulterende oppløsning påført hver potte, hvilket var ekvivalent til 16,8 kg/ha forsøksforbindelse. Each test compound was dissolved in 1:1 acetone:ethanol in an amount of 2 µg per 100 ml. The solution also contained approx. 2 g per 100 ml surfactant mixture anionic/non-ionic. 1 ml of solution was diluted to 4 ml with deionized water, and 1.5 ml of the resulting solution applied to each pot, which was equivalent to 16.8 kg/ha of test compound.

Etter at forbindelsene var påført ble pottene flyttet til veksthuset, vannet når nødvendig og observert og bedømt ca. 10-13 dager etter sprøytingen. Ubehandlede kontrollplanter ble brukt som standard ved hvert forsøk. After the compounds were applied, the pots were moved to the greenhouse, watered when necessary and observed and judged approx. 10-13 days after spraying. Untreated control plants were used as a standard in each experiment.

Den følgende tabell gjengir resultatene fra for-søk med typiske forbindelser med formel I. Forbindelsene iden-tifiseres med deres eksempelnummer. The following table reproduces the results of trials with typical compounds of formula I. The compounds are identified by their example number.

Eksempel 137_ Example 137_

Veksthusforsøk med syv arter Greenhouse experiments with seven species

Forsøket ble gjennomført generelt på samme måten The experiment was generally carried out in the same way

som i Eksempel 136. Frøene ble sådd i flate metållbegere i stedet for i potter. Forbindelsene ble påført'i samme blanding som ovenfor, bortsett fra at ca. 6 g pr. 100 ml forbindelse ble opp-løst i oppløsningsmiddel inneholdende overflateaktivt middel og ca. 1 del av den organiske oppløsning ble fortynnet med 12 deler vann før sprøyting i begrene. Forbindelsene ble påført i en mengde på 9,0 kg/ha, og resultatene for bekjempelsen av nedenstående arter fremgår av tabellen. as in Example 136. The seeds were sown in flat metal cups instead of in pots. The compounds were applied in the same mixture as above, except that approx. 6 g per 100 ml of compound was dissolved in solvent containing surfactant and approx. 1 part of the organic solution was diluted with 12 parts of water before spraying into the cups. The compounds were applied in a quantity of 9.0 kg/ha, and the results for the control of the species below appear in the table.

Eksempel 138'Example 138'

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Veksthusforsøk med mange_ arter Greenhouse experiments with many_ species

Generelt fulgte; man samme forsøksmetode som i det foregående forsøk. Forskjellige forbindelser med formel I ble prøvet før og etter spiring i forskjellige mengder som fremgår av den følgende tabell. Mån trakk inn en rekke andre ugras-og nyttevekster ved førspiringsprøvene som vist i tabellen. Generally followed; the same experimental method as in the previous experiment. Different compounds of formula I were tested before and after germination in different amounts as shown in the following table. Mån pulled in a number of other weeds and beneficial plants in the pre-germination tests as shown in the table.

Eksempel 13 9 Example 13 9

Forsøk med " yellow nutsedge" Experiment with "yellow nutsedge"

Typiske forbindelser med formel I ble undersøkt i veksthuset mot "yellow nutsedge" ved en forsøksmetode som generelt var som i Eksempel 136, bortsett fra at man benyttet en aceton-etanol-oppløsning inneholdende ca. 1,5 g/100 ml forsøks-forbindelse, og at én del av den organiske oppløsning ble fortynnet med 9 deler vann før påføring. Både førspirings- og etterspiringsforsøk ble foretatt under en sprøytemengde på 9>0 kg/ha. Man finner resultatene med typiske forbindelser i følg-ende tabell. Typical compounds of formula I were examined in the greenhouse against "yellow nutsedge" by an experimental method which was generally the same as in Example 136, except that an acetone-ethanol solution containing approx. 1.5 g/100 ml test compound, and that one part of the organic solution was diluted with 9 parts of water before application. Both pre-germination and post-germination trials were carried out at a spray rate of 9>0 kg/ha. You can find the results with typical compounds in the following table.

Eksempel 14 0 Example 14 0

Forsøk mot bredbladet ugress Trials against broadleaf weeds

En rekke typiske forbindelser med formel I ble prøvet i veksthuset mot bredbladet ugress som er typiske for familier av ugress som har stor motstandsevne mot mange kjente ugressdrepende midler. Fremgangsmåten var den samme som i Eksempel 139, men man foretok bare førspiringsforsøk. Alle forbindelsene ble prøvet i sprøytemengder på 9»0 kg/ha. A number of typical compounds of formula I were tested in the greenhouse against broadleaf weeds which are typical of families of weeds which have high resistance to many known herbicides. The procedure was the same as in Example 139, but only pre-germination tests were carried out. All the compounds were tested in spray quantities of 9.0 kg/ha.

Eksempel 141 Example 141

Jord- innblandingsprøve moti 14- prøvers test Soil mixing test versus 14-sample test

Forsøket ble utført for å bedømme typiske forbindelser med formel I for<1>virkning mot en rekke ugress- og nyttevekstarter. Forbindelsene ble undersøkt i veksthuset ved forskjellige sprøytemengder som fremgår av tabellen som følger. I alle tilfeller ble forsøksforbindelsene påført før spiring ved innblanding i jorden før frøene ble sådd. Man gikk frem med hensyn til sammensetning av forbindelsene og såing og observasjon av plantene som i Eksempel 139, bortsett fra at forbindelsene ble oppløst i aceton-etanol i en mengde på 1 g/100 ml før fortynning med vann. The experiment was carried out to assess typical compounds of formula I for <1>activity against a number of weeds and useful plant species. The compounds were examined in the greenhouse at different spray rates as shown in the table that follows. In all cases, the test compounds were applied before germination by mixing into the soil before the seeds were sown. One proceeded with regard to composition of the compounds and sowing and observation of the plants as in Example 139, except that the compounds were dissolved in acetone-ethanol in an amount of 1 g/100 ml before dilution with water.

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Eksempel 14 2 Example 14 2

Veksthusforsøk med 14 arter Greenhouse experiment with 14 species

Ved dette forsøk påførte man forsøksforbindelser med formel I på jordoverflaten før spiring. Man gikk frem generelt som i Eksempel 13 9. De forskjellige sprøytemengder fremgår av tabellen som følger, samt de oppnådde resultater. Det ble brukt forskjellige plantearter for undersøkelse av forskjellige forbindelser . In this experiment, test compounds of formula I were applied to the soil surface before germination. The procedure was generally as in Example 13 9. The different spray amounts appear in the table that follows, as well as the results obtained. Different plant species were used to investigate different compounds.

Eksempel 143 Example 143

Jordinnblandingsprøve Soil mixing test

Ved dette forsøk ble forbindelser med formel I innarbeidet i jorden før frøene ble sådd. Fremgangsmåten fra Eksempel 139 ble fulgt. Forskjellige forbindelser ble prøvet med en rekke forskjellige sprøytemengder og de forskjellige forbindelsene undersøkt mot flere- plantearter. In this experiment, compounds of formula I were incorporated into the soil before the seeds were sown. The procedure from Example 139 was followed. Different compounds were tested with a number of different spray amounts and the different compounds were tested against several plant species.

Eksempel 144 Example 144

Forsøk med overf la te- sprøyt ing; og flere planteslag Experiments with surface spraying; and several plant species

Representative forbindelser med formel I ble prøvet mot en rekke representative nyttevekster på forsøksområder hvor feltene var kunstig sådd med ugress. Frø av nyttevekstene som det fremgår av tabellen som følger, ble plantet i rekker i mid-dels tung midt-vest-jord (U.S.A.). Forbindelsene som er oppført i tabellen ble sprøytet i bånd på tvers av radene og ble påført umiddelbart etter såing. Båndene var ca. 1 meter brede, slik at hvert forsøksfelt omfattet en 1 meters lengde omfattende en rekke av hver vekst som fremgår av tabellen. Forbindelsene ble dusjet på jordoverflaten som en vanndispersjon, i likhet med hva som er beskrevet i Eksempel 137. Representative compounds of formula I were tested against a number of representative crops on trial areas where the fields were artificially sown with weeds. Seeds of the beneficial crops as shown in the following table were planted in rows in medium-heavy mid-west soil (U.S.A.). The compounds listed in the table were sprayed in bands across the rows and applied immediately after sowing. The tapes were approx. 1 meter wide, so that each experimental field comprised a 1 meter length including a row of each growth as shown in the table. The compounds were showered onto the soil surface as a water dispersion, similar to what is described in Example 137.

Alle feltene ble oversådd med kvinoa og revehirse umiddelbart før feltene ble tilsådd og behandlet med de aktuelle forbindelser. Ubehandlede sammenligningsfelter ble også oppret-tet . All the fields were sown with quinoa and foxtail millet immediately before the fields were sown and treated with the relevant compounds. Untreated comparison fields were also created.

En plantespesialist undersøkte feltene 39 dager etter såing og behandling og bedømte prosentvis bekjempelse av ugresset og prosentvis ødeleggelse av nyttevekstene. Resultatene fremgår av tabellen. A plant specialist examined the fields 39 days after sowing and treatment and assessed the percentage control of the weeds and the percentage destruction of the beneficial crops. The results appear in the table.

Eksempel 145 Example 145

Forsøk med , j ordinnb land ing og flere vekster Experiment with , soil planting and more crops

Man gjentok fremgangsmåten fra Eksempel 144, bortsett fra at forbindelser med formel I ble innført i jorden med en jordbearbeidingsmaskin umiddelbart etter påføring. Frø av ugress og nyttevekster ble sådd straks etter sprøyting og inn-arbeiding av forbindelsene. The procedure of Example 144 was repeated, except that compounds of formula I were introduced into the soil with a tillage machine immediately after application. Seeds of weeds and useful crops were sown immediately after spraying and incorporating the compounds.

Eksempel 146 Example 146

Forsøk med flerårige ugressplanter Experiment with perennial weed plants

Forbindelsen fra Eksempel 1 ble undersøkt overfor typiske flerårige ugress. Sprøytemiddelet ble sammensatt som beskrevet i Eksempel 136. Preparatene ble sprøytet på plastpotter med drivhusjord plantet med Convolvulus, Bermudagress, durragress og kveke. Rotstokker av Convolvulus og durragress og kveke-rhizomer av kvikkgress fikk man fra frilandsplanter og Bermudagress-utløpere fra drivhusdyrkede Bermudagressfelter. The compound from Example 1 was tested against typical perennial weeds. The spray agent was composed as described in Example 136. The preparations were sprayed on plastic pots with greenhouse soil planted with Convolvulus, Bermuda grass, sorghum grass and quack. Rootstocks of Convolvulus and sorghum grass and quack rhizomes of quickgrass were obtained from field plants and Bermuda grass shoots from greenhouse-grown Bermuda grass fields.

Forsøksforbindelsene sammensatt som preparat ble sprøytet jevnt over pottene umiddelbart etter at ugressene var plantet og ble lett vannet ned i jorden. Pottene ble gjødslet individuelt noen dager etter behandling. The test compounds composed as a preparation were sprayed evenly over the pots immediately after the weeds had been planted and were lightly watered into the soil. The pots were fertilized individually a few days after treatment.

Pottene ble lagret i drivhuset og plantene observert 5 uker etter påføring av forbindelsene. Ugressbekjempelsen ble bedømt på en skala 0-10. The pots were stored in the greenhouse and the plants observed 5 weeks after application of the compounds. Weed control was rated on a scale of 0-10.

Samme forbindelse ble også undersøkt mot samme ugress, hvorunder ugress-sortene ble dyrket 30-60 dager etter såing eller utsetting før forbindelsene ble påført. Før sprøyting med forbindelsene ble plantene skåret tilbake til en høyde på 10-20 cm, og Convolulus-utløperne ble skåret tilbake til kanten av potten. Plantene ble bedømt 4 uker etter behandling. Resultatene var som følger: The same compound was also tested against the same weeds, under which the weed varieties were grown 30-60 days after sowing or setting out before the compounds were applied. Before spraying with the compounds, the plants were cut back to a height of 10-20 cm and the Convolulus shoots were cut back to the edge of the pot. The plants were assessed 4 weeks after treatment. The results were as follows:

Eksempel 14 7 Example 14 7

Forsøk mot flerårige ugress. Trials against perennial weeds.

Ved dette typiske eksperiment var ugress-sorter og forhold som i Eksempel: 146. Man benyttet en rekke eksempelforbindelser med formel I|. Ugresset ble bedømt 4 uker etter sprøyting med forbindelsene. Førspiringsforsøkene var som det fremgår av tabellen. In this typical experiment, weed varieties and conditions were as in Example: 146. A number of example compounds with formula I| were used. The weeds were assessed 4 weeks after spraying with the compounds. The pre-germination experiments were as shown in the table.

Resultater jav etterspiringsforsøk som følger: Results jav post-sprouting test as follows:

Eksempel 148 Example 148

Mesqu. it e- f orsøk Mesqu. it e-f oresearch

Typiske forbindelser med formel I ble bedømt for bekjempelse mot mesquite-trær dyrket i veksthus. Trærne ble omplantet når de var 15-30 cm høye til 4 liters metallpotter. Etterat trærne hadde begynt å vokse kraftig i pottene ble for-søksforbindelsene påført som en jorddrenering. Forbindelsene ble preparert for påføring ved oppløsning i aceton:etanol som beskrevet i Eksempel 136, og dispergering av den riktige mengde oppløsning i 25 ml vann for påføring på hver potte. Mesquite-trærne ble bedømt ca. 90 dager etter påføring av forbindelsene, og bekjempelsen gradert på en 0-10 skala. Typical compounds of formula I were evaluated for control of mesquite trees grown in greenhouses. The trees were transplanted when they were 15-30 cm high into 4 liter metal pots. After the trees had started to grow vigorously in the pots, the trial compounds were applied as a soil drainage. The compounds were prepared for application by dissolving in acetone:ethanol as described in Example 136, and dispersing the appropriate amount of solution in 25 ml of water for application to each pot. The mesquite trees were rated approx. 90 days after application of the compounds, and the control graded on a 0-10 scale.

Eksempel 149 Example 149

Forsøk med grapefrukt. Experiment with grapefruit.

Forbindelsen fra Eksempel 1 ble prøvet i en grape-fruktlund i tropisk klima.. Jorden var sandaktig og trærne ble dyrket med underjordisk,vanning. Trærne var omtrent 2 år gamle når forbindelsen ble påført. The compound from Example 1 was tested in a grapefruit grove in a tropical climate. The soil was sandy and the trees were grown with underground irrigation. The trees were about 2 years old when the compound was applied.

Forbindelsen ble preparert i henhold til Eksempel 136 og preparatet påført som en overflatedusj på en flate på The compound was prepared according to Example 136 and the preparation applied as a surface shower to a surface of

p p

1 m omkring foten av hvert tre. 1 m around the base of each tree.

Beskadigelse av trærne etter sprøytingen ble bedømt på en skala 0-10 etter 14 uker, med følgende resultater: Damage to the trees after the spraying was assessed on a scale of 0-10 after 14 weeks, with the following results:

Man bedømte også ugressbekjempelsen 14 uker etter påføring av forsøksforbindelsen. Man fikk følgende resultater uttrykt som prosentvis bekjempelse basert på ugressmengden på ubehandlede områder. Weed control was also assessed 14 weeks after application of the test compound. The following results were obtained expressed as percentage control based on the amount of weeds in untreated areas.

Eksempel 150 Example 150

Bekjempelse av " purple nutsedge" i bomullsfelter Control of "purple nutsedge" in cotton fields

Forbindelsen fra Eksempel 1 ble prøvet på bomullsfelter infisert med "purple nutsedge". Bomullen ble dyrket på leirjord som flatekultur uten vanning og i subtropisk klima. Forsøksforbindelsen ble påført som et vanndispergert 80%-ig fuktbart pulver og ble innarbeidet i jorden umiddelbart før utplanting av bomullen. Nyttevekst-beskadigelse og ugressbekjempelse ble bedømt som prosentvis beskadigelse eller bekjempelse omkring 8 uker etter påføring av det ugressdrepende middel. Resultatene var: The compound from Example 1 was tested on cotton fields infected with purple nutsedge. Cotton was grown on clay soil as a surface crop without irrigation and in a subtropical climate. The test compound was applied as a water-dispersed 80% wettable powder and was incorporated into the soil immediately before planting the cotton. Crop damage and weed control were assessed as percentage damage or control approximately 8 weeks after application of the herbicide. The results were:

Eksempel 151 Example 151

Ugressbek. jempelse på kaffe- felter Weed pitch. cultivation in coffee fields

Forbindelsen fra Eksempel 1 ble også sprøytet på kaffe-felter i lignende eksperimenter som ovenfor, bortsett fra at forbindelsen ble sprøytet på overflaten. Påføring av mengder på opp til 2 kg/ha viste ingen beskadigelse av kaffe-plantene ved observasjon seks uker og deretter ca. fire måneder etter på-føring. Fremragende bekjempelse av enårig gress, enårig bredbladet ugress, Paraguay-borre, vanlig borre, marigull, sand-borre og "purple nutsedge" ble observert under eksperimentet. The compound of Example 1 was also sprayed on coffee fields in similar experiments as above, except that the compound was sprayed on the surface. Application of amounts of up to 2 kg/ha showed no damage to the coffee plants during observation for six weeks and then approx. four months after application. Outstanding control of annual grass, annual broadleaf weeds, Paraguay burdock, common burdock, marigold, sand burdock and purple nutsedge was observed during the experiment.

Den fremragende bredspektrede virkning av forbindelsene med formel I vil fremgå klart av de foregående eksempler. Eksemplene viser virkningen av forbindelsene mot enårig gress, de relativt sårbare bredbladede gress som kvinoa og de vanske-lig bekjempbare bredbladede ugress som solanum, Ambrosia og A. Canadensis. Videre, bekjemper forbindelsene slike flerårige ugress som durragress, kveke, convolvulus, bermudagress og "nutsedge", som er meget vanskelige å bekjempe. Forbindelsene bekjemper også alger og plantevekster som "coontail", hydrilla og lignende. Videre, dreper de aktuelle forbindelser treaktige planter som mesquite, som er et økonomisk sett skadelig ugress i tørt klima. Således vil plantespesialister erkjenne at forbindelsene kan brukes til bekjempelse av uønskede treaktige planter. Man vil videre se at forbindelsenes aktivitetsområde som vist demonstrerer virkning mot alle typer ugress. The outstanding broad-spectrum effect of the compounds of formula I will be clear from the preceding examples. The examples show the effect of the compounds against annual grasses, the relatively vulnerable broadleaf grasses such as quinoa and the difficult-to-control broadleaf weeds such as Solanum, Ambrosia and A. Canadensis. Furthermore, the compounds control such perennial weeds as sorghum, quack, convolvulus, bermudagrass and nutsedge, which are very difficult to control. The compounds also combat algae and plant growth such as "coontail", hydrilla and the like. Furthermore, the compounds in question kill woody plants such as mesquite, which is an economically harmful weed in dry climates. Thus, plant specialists will recognize that the compounds can be used to control unwanted woody plants. You will also see that the compounds' activity range, as shown, demonstrates effectiveness against all types of weeds.

En foretrukket utførelse av den herbicide fremgangsmåte er imidlertid bruk av metoden til selektiv utryddelse av planteugress. However, a preferred embodiment of the herbicidal method is the use of the method for the selective eradication of plant weeds.

Høyst uvanlig er forbindelser med formel I herbicid effektive både før og etter spiring. Forbindelsene kan således påføres på jorden for å drepe frø mens disse spirer under og over bakken, ogjkan også brukes til utryddelse av opp-kommet ugress ved direkte kontakt med de synlige deler av ugresset. Når forbindelsene brukes som førspiringsbehandling blir ugresset drept enten under spiring eller kort etter. Most unusually, compounds of formula I are herbicidally effective both before and after germination. The compounds can thus be applied to the soil to kill seeds while they are germinating below and above ground, and can also be used to eradicate emerging weeds by direct contact with the visible parts of the weeds. When the compounds are used as a pre-germination treatment, the weeds are killed either during germination or shortly after.

Forbindelsene føres effektivt i kontakt med vandig ugress enten ved suspensjon eller oppløsning av forbindelsen i det vannet hvor ugresset;vokser eller ved påføring av forbindelsene på den underjordiske jorden hvor ugresset har røtter. The compounds are effectively brought into contact with aquatic weeds either by suspending or dissolving the compound in the water where the weed grows or by applying the compounds to the underground soil where the weed has roots.

På grunn av den fremragende virkning av de aktuelle forbindelser, kan de;anvendes for selektiv utryddelse av ugress, hvorved, ugressett,føres i kontakt med en ugressdrepende effektiv mengde av minst 1 én av forbindelsene med formel I ovenfor. I foreliggende sammenheng blir ugressfrø som føres i kontakt med de aktuelle forbindelser før frøene spirer, betraktet som ugress. Due to the outstanding effect of the compounds in question, they can be used for the selective eradication of weeds, whereby the weeds are brought into contact with a herbicidally effective amount of at least one of the compounds of formula I above. In the present context, weed seeds that are brought into contact with the compounds in question before the seeds germinate are considered weeds.

Førspirings-behandling med forbindelsene er effektiv som eksemplene viser, enten forbindelsene påføres jordoverflaten eller innarbeides i jorden. Pre-germination treatment with the compounds is effective as the examples show, whether the compounds are applied to the soil surface or incorporated into the soil.

Som ovenstående eksempler illustrerer, er mange As the above examples illustrate, many are

av forbindelsene sikre i;bruk mot en rekke nyttevekster som peanøtter, soyabønner, durra, hvete, ris og nyttetrær når de påføres i riktige mengder og på riktige tidspunkter. Det skal fremheves at forbindelsene er særlig og bemerkelsesverdig of the compounds safe in use against a variety of crops such as peanuts, soybeans, sorghum, wheat, rice and crops when applied in the right amounts and at the right times. It must be emphasized that the connections are special and remarkable

uskadelige overfor bomull som påvist i eksemplene. På grunn av den sikkerhet hvormed bomull kan behandles med de aktuelle ugressdrepende midler, er bruk av denne fremgangsmåten for utryddelse av ugress på bomullsmarker en foretrukket utførelse av oppfinnelsen. harmless to cotton as demonstrated in the examples. Due to the safety with which cotton can be treated with the appropriate herbicides, use of this method for the eradication of weeds in cotton fields is a preferred embodiment of the invention.

Forbindelsene kan også brukes i egnede mengder for totalbekjempelse av vegetasjonen. Slik bekjempelse (regulering) er ofte ønsket for å holde dyrket mark brakk i en tid eller ønsket på industrielt område eller ut fra spesiell lovgivning (rights-of-way). De aktuelle forbindelsenes evne til bekjempelse av flerårige ugress og treaktige planter gjør dem særlig egnet som totalbekjempelsesmiddel. The compounds can also be used in suitable quantities for total control of the vegetation. Such control (regulation) is often desired to keep cultivated land fallow for a time or desired in industrial areas or based on special legislation (rights-of-way). The ability of the relevant compounds to combat perennial weeds and woody plants makes them particularly suitable as a total control agent.

Metoden er bemerkelsesverdig for dens evne til selektivt å drepe ugress. Betegnelsen ugress brukes i denne forbindelse ikke restriktivt, men skal omfatte uønskede planter i større forstand. For eksempel, kan metoden benyttes på bomullsmarker for utryddelse av ikke bare planter som i og for seg er uønsket, som durragress og Ambrosia, men også nyttevekster som er uønsket på bomullsmarker. Man vil innse at riktige sprøytemengder må brukes for å oppnå denne selektive regulering eller bekjempelse av ugress, hvilket fagfolk er klar over. The method is notable for its ability to selectively kill weeds. In this context, the term weed is not used restrictively, but must include unwanted plants in a broader sense. For example, the method can be used on cotton fields to eradicate not only plants that are in and of themselves undesirable, such as sorghum grass and ragweed, but also beneficial plants that are undesirable on cotton fields. It will be appreciated that proper spray rates must be used to achieve this selective control or control of weeds, which those skilled in the art are aware of.

Den relative mengde ugress som drepes ved påføring av en av forbindelsene med formel 1 avhenger av ugressarten og type og mengde påført ugressmiddel. I mange tilfeller blir naturligvis hele ugressbefolkningen drept. I andre tilfeller blir en del av ugresset drept og endel skadet, hvilket endel av de ovennevnte eksemplene illustrerer. Man vil også innse at bruk av de aktuelle forbindelser er nyttig, selv om bare en del av ugressveksten drepes og ytterligere en del skades. The relative amount of weeds killed by application of one of the compounds of formula 1 depends on the weed species and the type and amount of herbicide applied. In many cases, of course, the entire weed population is killed. In other cases, some of the weeds are killed and some damaged, as some of the above examples illustrate. One will also realize that the use of the relevant compounds is useful, even if only a part of the weed growth is killed and a further part is damaged.

En slik beskadigelse av ugress er gunstig, fordi den omgivende nyttevekst som vokser normalt vil skygge over og drepe den langsomtvoksende, skadede ugressplante. Such damage to weeds is beneficial, because the surrounding beneficial vegetation that grows normally will shade over and kill the slow-growing, damaged weed plant.

Den beste påføringsmengde for en gitt forbindelse med formel I til bekjempelse av et gitt ugress vil naturligvis variere med påføringsmetoden, klima, jordtype, vanninnhold og innhold av organisk stoff i jorden og andre faktorer som er kjent for plantefagfolk. Den optimale påføringsmengde ligger imidlertid oftest mellom ca. 0,1 til 20 kg/ha i praktisk talt alle tilfeller. Den optimale mengde vil forøvrig vanligvis finnes innenfor et foretrukket område på fra 0,1 til 5 kg/ha. The best application rate for a given compound of formula I to control a given weed will, of course, vary with the method of application, climate, soil type, water content and organic matter content of the soil and other factors known to those skilled in the art of plants. However, the optimal amount of application is usually between approx. 0.1 to 20 kg/ha in practically all cases. Incidentally, the optimum quantity will usually be found within a preferred range of from 0.1 to 5 kg/ha.

Tidspunktet for sprøyting eller påføring av de aktuelle forbindelser på jorden eller ugresset varierer sterkt, siden forbindelsene er effektive både før og etter spiring (pre-emergens og post-emergens). I det minste en viss ugressbekjempelse vil oppnås ved å benytte forbindelsene på et hvilket som helst tidsrom hvor ugresset vokser eller spirer. Forbindelsene kan også påføres jorden i en hvileperiode for på denne måten å drepe frø som spirer under følgende varme vekstsesong. The timing of spraying or applying the compounds in question to the soil or the weeds varies greatly, since the compounds are effective both before and after germination (pre-emergence and post-emergence). At least some weed control will be achieved by using the compounds at any time during which the weed is growing or germinating. The compounds may also be applied to the soil during a dormant period to thereby kill seeds germinating during the following hot growing season.

Når forbindelsene benyttes til ugressbekjempelse innenfor en årsvekst er det vanligvis best å påføre forbindelsen før spiring på det tidspunkt veksten såes. Hvis forbindelsen skal innarbeides i jorden, vil den vanligvis påføres og innarbeides umiddelbart før såing (planting). Hvis forbindelsen skal påføres på overflaten, er det vanligvis enklest å på-føre den umiddelbart etter såing. When the compounds are used for weed control within an annual crop it is usually best to apply the compound before germination at the time the crop is sown. If the compound is to be incorporated into the soil, it will usually be applied and incorporated immediately before sowing (planting). If the compound is to be applied to the surface, it is usually easiest to apply it immediately after sowing.

Forbindelsene påføres jorden eller de spirede ugress på vanlig måte innen; landbruket. De kan påføres på bakken i form av vanndispergerte eller granulære preparater, deres fremstilling skal omtales senere. Vanligvis vil man velge vanndispergerte preparater, for påføring av forbindelsene på spiret ugress. Preparatene påføres ved hjelp av en av de mange typer sprøytemaskiner eller spredeapparater som er i utstrakt bruk til fordeling av landbrukskjemikalier på bakken eller på stående vekster. Når en forbindelse skal innarbeides i jorden, kan det benyttes alle vanlige jordbearbeidende maskiner som skiveharv, roterende hakke og lignende. The compounds are applied to the soil or the sprouted weeds in the usual way within; agriculture. They can be applied to the ground in the form of water-dispersed or granular preparations, their preparation will be discussed later. Usually, one will choose water-dispersed preparations, for applying the compounds to germinated weeds. The preparations are applied using one of the many types of sprayers or spreaders that are widely used for distributing agricultural chemicals on the ground or on standing plants. When a compound is to be incorporated into the soil, all common tillage machines such as disc harrows, rotary hoe and the like can be used.

Forbindelsene påføres vanligvis i form av ugressdrepende preparater og et slikt preparat omfatter en forbindelse med formel I og et inært bærestoff. Generelt, sammensettes preparatene på kjent måte og er nye bare på grunn av det nødvendige nærvær av dé nye herbicide stoffer. The compounds are usually applied in the form of weed-killing preparations and such a preparation comprises a compound of formula I and an inert carrier. In general, the preparations are composed in a known manner and are new only because of the necessary presence of the new herbicidal substances.

Oftest prepareres de aktuelle forbindelser som konsentrerte sammensetninger som påføres på bakken eller blad-verket i form av vanndispersjoner eller emulsjoner som inneholder mellom 0,1 til 5% ugressdrepende forbindelse. Vann-dispergerbare eller -emulgerbare preparater er enten faste stoffer, vanligvis kjent som fuktbare pulvere, eller væsker som ofte betegnes emulgerbare konsentrater. Disse konsentrerte preparater benyttes innenfor områdene: Most often, the compounds in question are prepared as concentrated compositions that are applied to the ground or foliage in the form of water dispersions or emulsions containing between 0.1 and 5% weed killer compound. Water-dispersible or -emulsifiable preparations are either solids, usually known as wettable powders, or liquids which are often referred to as emulsifiable concentrates. These concentrated preparations are used in the following areas:

Nevnte fuktbare pulvere består av en omhyggelig finfordelt blanding av den aktuelle forbindelse, et inert bærestoff og overflateaktive midler. Konsentrasjonen av forbindelsen er vanligvis fra ca. 10 til 90%. Det inerte bærestoffet er vanligvis valgt blant attapulgittleirer, kaolinleirer, mont-morillonittleirer og diatomejord eller rensede silikater. Effektive overflateaktive midler som inneholder fra ca. 0,5 til ca. 10 prosent fuktbare pulvere, finner man blant sulfonerte ligniner, kondenserte naftalensulfonater, naftalensulfonater, alkylbenzensulfonater, alkylsulfater og ikke-ioniske overflateaktive midler som etylenoksydaddukter av fenol. Said wettable powders consist of a carefully finely divided mixture of the compound in question, an inert carrier and surfactants. The concentration of the compound is usually from approx. 10 to 90%. The inert carrier is usually selected from attapulgite clays, kaolin clays, mont-morillonite clays and diatomaceous earth or purified silicates. Effective surfactants containing from approx. 0.5 to approx. 10 percent wettable powders, are found among sulfonated lignins, condensed naphthalene sulfonates, naphthalene sulfonates, alkylbenzene sulfonates, alkyl sulfates and non-ionic surfactants such as ethylene oxide adducts of phenol.

Typiske emulgerbare konsentrater av forbindelser med formel I omfatter en egnet konsentrasjon av forbindelsen, f.eks. fra ca. 100 til 500 g pr. liter væske, oppløst i et inert bærestoff som er en blanding av et oppløsningsmiddel som ikke er blandbart 'med vann og emulgatorer. Brukbare organiske oppløsningsmidler er aromatiske væsker som spesielt xylener og jordoljefraksjoner, særlig høytkokende naftalen- og olefin-fraksjoner. Mange andre organiske oppløsningsmidler kan brukes som f.eks. terpen-oppløsningsmidler, og sammensatte alkoholer som 2-etoksyetanol. Egnede emulgatorer for emulgerbare konsentrater velges blant de samme typer overflateaktive midler som brukes til fuktbare pulvere. Typical emulsifiable concentrates of compounds of formula I comprise a suitable concentration of the compound, e.g. from approx. 100 to 500 g per liter of liquid, dissolved in an inert carrier which is a mixture of a solvent which is not miscible with water and emulsifiers. Usable organic solvents are aromatic liquids such as xylenes in particular and petroleum fractions, particularly high-boiling naphthalene and olefin fractions. Many other organic solvents can be used such as e.g. terpene solvents, and compound alcohols such as 2-ethoxyethanol. Suitable emulsifiers for emulsifiable concentrates are chosen from the same types of surfactants used for wettable powders.

Når en forbindelse skal påføres på bakken, som f. eks. som førspiringspreparat, er det hensiktsmessig å benytte When a compound is to be applied to the ground, such as as a pre-germination preparation, it is appropriate to use

et granulatpreparat. Et slikt granulatpreparat omfatter typisk den aktuelle forbindelse dispergert på et granulatformet a granule preparation. Such a granule preparation typically comprises the compound in question dispersed on a granule form

inert bærestoff som grovmalt leire. Partikkelstørrelsen for granulatene ligger vanligvis mellom ca. 0,1 og 3 mm- Den vanlige prepareringsprosess består i oppløsning av forbindelsen i et billig oppløsningsmiddel og påføring av oppløsningen på bærestoffet i en egnet tørrstoffblander. Granulære preparater inert carrier such as coarsely ground clay. The particle size for the granules is usually between approx. 0.1 and 3 mm- The usual preparation process consists in dissolving the compound in a cheap solvent and applying the solution to the carrier in a suitable dry matter mixer. Granular preparations

sammensettes vanligvis med følgende blandeforhold: are usually composed with the following mixing ratio:

På en noe mindre økonomisk måte kan forbindelsene dispergeres som en deig^bestående av fuktig leire eller annet inert bærestoff som derpå tørkes og grovmales til det ønskede granulære produkt. In a somewhat less economical way, the compounds can be dispersed as a paste consisting of moist clay or other inert carrier material which is then dried and coarsely ground into the desired granular product.

Claims (3)

1. 3-fenyl-5-substituerte-MlH)-pyridoner(tioner) til anvendelse som herbicid, karakterisert ved at de har formelen: hvor: X betegner oksygen eller svovel; R betegner hydroksy, C^-C^-alkyl, C^-C^-alkyl substituert med halogen, cyan, karboksy- eller metoksykarbonyl; Cg-C^-alkenyl; Cg-C^-alkynyl; C-^-C^-alkoksy; acetoksy; eller dimetylamino; forutsatt at R omfatter ikke mer enn 3 karbonatomer; R^-gruppene uavhengig av hverandre betegner halogen; C-^-Cg-alkyl; C-^-Cg-alkyl substituert med halogen; C^-Cg-alkyl mono-substituert med fenyl, cyan eller C-^-C^-alkoksy, C2-Cg-alkenyl; C2-Cg-alkenyl substituert med halogen; Cg-Cg-alkynyl; Cg-Cg-alkynyl substituert med halogen; C^-Cg-cykloalkyl; C^-Cg-cyklo-alkenyl; C^-Cg-cykloalkylalkyl; C-j^-C^-alkanoyloksy; C-^-C^-alk-ylsulfonyloksy; fenyl; fenyl-monosubstituert med halogen, C-^-C^-alkyl, C-^-C^-alkoksy eller nitro; nitro; cyan; karboksy; hydroksy; C^-C^-alkoksykarbonyl; -0-R^; -S-R^; -SO-R^ eller -S02-R3; ' ; R^ betegner C-^-C-^-alkyl; C-^-C-^-alkyl substituert med halogen; C-^-C-j^-alkyl-monosubstituert med fenyl, cyan eller C^-C^-alkoksy; fenyl; fenyl-monosubstituert med halogen, C-^-C^-alkyl, C^-C^-.alkoksy eller med nitro; C^-Cg-cykloalkyl; C^-Cg-cyklo-alkylalkyl; C2-C-^2-alkenyl; Cg-C-^-alkenyl substituert med halogen; Cg-C^p-alkynyl; eller C2-C12-alkynyl substituert med halogen; når omfatter høyst 12 karbonatomer; R pbetegner halogen; hydrogen; cyan; C-^-C^-alkoksykarbonyl; C-^-Cg-alkyl; C-^-Cg-alkyl substituert med halogen eller C-^-C^-alkoksy; C2-Cg-alkenyl; C^-Cg-alkenyl substituert med halogen eller C-^-C^-alkoksy; C2-Cg-alkynyl; C^-Cg-cykloalkyl; C^-Cg-cykloalkyl substituert med halogen, C-^-C^-alkyl eller C-^-C^-alkoksy; C^-Cg-cykloalkenyl; C^-Cg-cykloalkylalkyl; fenyl-C^-C^-alkyl; furyl; naftyl; tienyl; -O-R<4>"; -S-R<4>; -SO-R<4>"; -S02-r<4>, eller R^ betegner C-^-C^-alkyl; C-^-C^-alkyl substituert med halogen; Cg-C^-alkenyl; Cg-C^-alkenyl substituert med halogen; benzyl; fenyl; eller fenyl substituert med halogen, C-^-C^-alkyl eller C,-C^-alkoksy; R -gruppene uavhengig av hverandre betegner halogen; C-^-Cg-alkyl; C-^-Cg-alkyl substituert med halogen; C-^-C<g->alkyl mono-substituert med fenyl, cyan eller C-^-C^-alkoksy; C2-Cg-alkenyl, Cg-Cg-alkenyl substituert med halogen; Cg-Cg-alkynyl; Cg-Cg-alkynyl substituert med halogen; C^-Cg-cykloalkyl; C^-Cg-cyklo-alkenyl; C^-Cg-cykloalkylalkyl; C-^-C^-alkanoyloksy; C-^-C^-alkylsulfonyloksy; fenyl; fenyl monosubstituert med halogen, G-^-G^-alkyl, C-^-C^-alkoksy eller nitro; nitro; cyan; karboksy; hydroksy; C-j-C^-alkoksykarbonyl; -0-R^; -S-R^; -SO-R^; eller -S02-R6; R betegner C-^-C-^-alkyl; C-^-C-^2-alkyl substituert med halogen; C-^-C-^2-alkyl monosubstituert med fenyl, cyan eller C-^-C^-alkoksy; fenyl; fenyl monosubstituert med halogen, C-^-C^-alkyl, C-^-C^-alkoksy eller nitro ; C^-Cg-cykloalkyl; C^-Cg-cyklo-alkylalkyl; C2-C-^2-alkenyl; Cg-C-^-alkenyl substituert med halogen; C2-C-^2-alkynyl; eller Cg-C-^-alkynyl substituert med halogen; når inneholder 'høyst 12 karbonatomer; m og n er lik 0,1 eller 2, .forutsatt at når X er oksygen, R er metyl og R er usubstituert fenyl, er m 1 eller 2, og deres syreaddisjonssaltér.1. 3-phenyl-5-substituted-MlH)-pyridones(thiones) for use as herbicide, characterized in that they have the formula: where: X represents oxygen or sulfur; R denotes hydroxy, C 1 -C 4 -alkyl, C 1 -C 4 -alkyl substituted by halogen, cyano, carboxy or methoxycarbonyl; C 6 -C 6 alkenyl; C 6 -C 6 -alkynyl; C 1 -C 4 -Alkoxy; acetoxy; or dimethylamino; provided that R comprises no more than 3 carbon atoms; The R₁ groups independently of each other denote halogen; C 1 -C 8 alkyl; C 1 -C 8 alkyl substituted with halogen; C 1 -C 8 alkyl mono-substituted with phenyl, cyano or C 1 -C 4 alkoxy, C 2 -C 8 alkenyl; C 2 -C 8 alkenyl substituted with halogen; C 6 -C 8 -alkynyl; C 6 -C 8 -alkynyl substituted with halogen; C 1 -C 8 cycloalkyl; C 1 -C 8 cycloalkenyl; C 1 -C 8 cycloalkylalkyl; C 1 -C 4 -alkanoyloxy; C 1 -C 4 -alkylsulfonyloxy; phenyl; phenyl monosubstituted with halogen, C 1 -C 4 -alkyl, C 1 -C 4 -alkyl or nitro; nitro; cyan; carboxy; hydroxy; C 1 -C 4 -Alkoxycarbonyl; -O-R^; -S-R^; -SO-R 3 or -SO 2 -R 3 ; ' ; R 1 denotes C 1 -C 1 -alkyl; C 1 -C 4 alkyl substituted with halogen; C 1 -C 14 -alkyl monosubstituted with phenyl, cyano or C 1 -C 4 -alkoxy; phenyl; phenyl monosubstituted with halogen, C 1 -C 4 -alkyl, C 1 -C 4 -alkyl or with nitro; C 1 -C 8 cycloalkyl; C 1 -C 8 cycloalkylalkyl; C 2 -C 12 -alkenyl; C 6 -C 6 -alkenyl substituted with halogen; C 6 -C 16 -alkynyl; or C 2 -C 12 alkynyl substituted with halogen; when comprises no more than 12 carbon atoms; R p denotes halogen; hydrogen; cyan; C 1 -C 4 -Alkoxycarbonyl; C 1 -C 8 alkyl; C 1 -C 8 -alkyl substituted with halogen or C 1 -C 6 -alkyl; C 2 -C 8 alkenyl; C 1 -C 8 -alkenyl substituted with halogen or C 1 -C 6 -alkyloxy; C 2 -C 8 alkynyl; C 1 -C 8 cycloalkyl; C 1 -C 8 -cycloalkyl substituted with halogen, C 1 -C 4 -alkyl or C 1 -C 4 - alkoxy; C 1 -C 8 cycloalkenyl; C 1 -C 8 cycloalkylalkyl; phenyl-C 1 -C 4 -alkyl; furyl; naphthyl; thienyl; -O-R<4>"; -S-R<4>; -SO-R<4>"; -SO2-r<4>, or R^ denotes C-1-C4-alkyl; C 1 -C 4 -alkyl substituted with halogen; C 6 -C 6 alkenyl; C 6 -C 6 alkenyl substituted with halogen; benzyl; phenyl; or phenyl substituted with halogen, C 1 -C 4 alkyl or C 1 -C 4 alkoxy; The R groups independently of each other denote halogen; C 1 -C 8 alkyl; C 1 -C 8 alkyl substituted with halogen; C 1 -C 6 -alkyl mono-substituted with phenyl, cyano or C 1 -C 6 -alkyl; C 2 -C 8 alkenyl, C 8 -C 8 alkenyl substituted with halogen; C 6 -C 8 -alkynyl; C 6 -C 8 -alkynyl substituted with halogen; C 1 -C 8 cycloalkyl; C 1 -C 8 cycloalkenyl; C 1 -C 8 cycloalkylalkyl; C 1 -C 4 -alkanoyloxy; C 1 -C 4 -alkylsulfonyloxy; phenyl; phenyl monosubstituted with halogen, C 1 -C 4 -alkyl, C 1 -C 4 -alkyl or nitro; nitro; cyan; carboxy; hydroxy; C 1 -C 4 -Alkoxycarbonyl; -O-R^; -S-R^; -SO-R^; or -SO 2 -R 6 ; R represents C 1 -C 4 -alkyl; C 1 -C 2 alkyl substituted with halogen; C 1 -C 2 -alkyl monosubstituted with phenyl, cyano or C 1 -C 4 -alkoxy; phenyl; phenyl monosubstituted with halogen, C 1 -C 4 -alkyl, C 1 -C 4 -alkyl or nitro; C 1 -C 8 cycloalkyl; C 1 -C 8 cycloalkylalkyl; C 2 -C 12 -alkenyl; C 6 -C 6 -alkenyl substituted with halogen; C 2 -C 2 -alkynyl; or C 6 -C 6 -alkynyl substituted with halogen; when contains 'not more than 12 carbon atoms; m and n are equal to 0.1 or 2, provided that when X is oxygen, R is methyl and R is unsubstituted phenyl, m is 1 or 2, and their acid addition salts. 2. Forbindelser som angitt i krav 1, karakteri- i sert ved den generelle formel i hvor: X betegner oksygen eller svovel; R° betegner C-^-C^-alkyl; C2-C^-alkenyl; acetoksy; eller metoksy; q og p uavhengig av hverandre er lik 0, 1 eller 2; R^-gruppene uavhengig av hverandre betegner halogen; C-^-C^-alkyl; trif luormetyl; eller C-^-C^-alkoksy; R^-gruppene uavhengig av hverandre betegner halogen; C^-C^-alkyl; trif luormetyl; eller C-^-C^-alkoksy; eller to R^-grupper som opptar naboplaserte o- og m-stillinger forbin-der seg med fenylringen som de er bundet til og danner en 1-naftyl-gruppe, forutsatt åt når X er oksygen, R° er metyl, og p er 0, er q lik 1 eller 2.2. Compounds as specified in claim 1, charac- in determined by the general formula in where: X represents oxygen or sulfur; R 0 denotes C 1 -C 4 -alkyl; C 2 -C 4 alkenyl; acetoxy; or methoxy; q and p independently equal 0, 1 or 2; The R₁ groups independently of each other denote halogen; C 1 -C 4 alkyl; trifluoromethyl; or C 1 -C 4 -alkyloxy; The R₁ groups independently of each other denote halogen; C 1 -C 4 alkyl; trifluoromethyl; or C 1 -C 4 -alkyloxy; or two R^ groups occupying neighboring o- and m-positions combine with the phenyl ring to which they are attached to form a 1-naphthyl group, provided that when X is oxygen, R° is methyl, and p is 0, q is equal to 1 or 2. 3. Forbindelser som angitt i krav 1, karakterisert ved følgende generelle formel:3. Compounds as specified in claim 1, characterized by the following general formula:
NO752942A 1974-08-28 1975-08-27 3-PHENYL-5-SUBSTITUTED 4 (1H) -PYRIDONES (TIONS) FOR USE AS HERBICIDES. NO145617C (en)

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JPS5151520A (en) 1976-05-07
JPS611401B2 (en) 1986-01-17
AT365577B (en) 1982-01-25
IE42444L (en) 1976-02-28
PL111873B1 (en) 1980-09-30

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