NO139861B - PROCEDURE FOR THE PREPARATION OF 1-HYDROXY-2-PYRIDONES - Google Patents

PROCEDURE FOR THE PREPARATION OF 1-HYDROXY-2-PYRIDONES Download PDF

Info

Publication number
NO139861B
NO139861B NO1205/73A NO120573A NO139861B NO 139861 B NO139861 B NO 139861B NO 1205/73 A NO1205/73 A NO 1205/73A NO 120573 A NO120573 A NO 120573A NO 139861 B NO139861 B NO 139861B
Authority
NO
Norway
Prior art keywords
methyl
atoms
hydroxy
pyrone
radical
Prior art date
Application number
NO1205/73A
Other languages
Norwegian (no)
Other versions
NO139861C (en
Inventor
Gerhard Lohaus
Walter Dittmar
Original Assignee
Hoechst Ag
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from DE19722214608 external-priority patent/DE2214608C3/en
Application filed by Hoechst Ag filed Critical Hoechst Ag
Publication of NO139861B publication Critical patent/NO139861B/en
Publication of NO139861C publication Critical patent/NO139861C/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/89—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 with hetero atoms directly attached to the ring nitrogen atom
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P31/00—Antiinfectives, i.e. antibiotics, antiseptics, chemotherapeutics
    • A61P31/04—Antibacterial agents
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D221/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00
    • C07D221/02—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00 condensed with carbocyclic rings or ring systems
    • C07D221/04—Ortho- or peri-condensed ring systems
    • C07D221/06—Ring systems of three rings
    • C07D221/10—Aza-phenanthrenes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D221/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00
    • C07D221/02—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00 condensed with carbocyclic rings or ring systems
    • C07D221/20—Spiro-condensed ring systems

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
  • Pharmacology & Pharmacy (AREA)
  • Communicable Diseases (AREA)
  • Animal Behavior & Ethology (AREA)
  • Oncology (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Pyridine Compounds (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Other In-Based Heterocyclic Compounds (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Medicinal Preparation (AREA)

Description

Oppfinnelsens gjenstand er en fremgangsmåte til The object of the invention is a further method

fremstilling av l-hydroksy-2-pyridoner med den generelle formel: preparation of l-hydroxy-2-pyridones with the general formula:

hvori in which

R^ betyr en eventuelt forgrenet alkylrest med 1 til 17 R^ means an optionally branched alkyl residue with 1 to 17

C-atomer, en alkenylrest med 2 til 17*C-atomer, C atoms, an alkenyl radical with 2 to 17*C atoms,

en cykloalkylrest med 3 til 8 C-atomer, en cyklohexylalkylrest, hvor alkylresten har 1-4 C-atomer, en even- a cycloalkyl radical with 3 to 8 C atoms, a cyclohexylalkyl radical, where the alkyl radical has 1-4 C atoms, an even

tuelt til den aromatiske kjerne med en eller flere alkyl-, alkoksy-, dialkylamino-, nitro-, alkoksy- tually to the aromatic core with one or more alkyl-, alkoxy-, dialkylamino-, nitro-, alkoxy-

karbonyl-, cyangrupper eller halogenatomer substituert fenyl-, fenylalkyl-, fenylalkenyl-, benzhydryl-, fenoksymetyl-, fenylmerkaptometyl-, fenylsulfonyl- carbonyl, cyano groups or halogen atoms substituted by phenyl-, phenylalkyl-, phenylalkenyl-, benzhydryl-, phenoxymethyl-, phenylmercaptomethyl-, phenylsulfonyl-

metylrest, en furyl- eller furylalkenylrest, hvor methyl residue, a furyl or furylalkenyl residue, where

alkyl-, alkenyl- og alkoksygrupper kan ha 1-4 C-atomer alkyl, alkenyl and alkoxy groups can have 1-4 C atoms

1*2 betyr hydrogen, en alkyl-, alkenyl- eller alkynylrest 1*2 means hydrogen, an alkyl, alkenyl or alkynyl residue

alle med 1-4 C-atomer, eller en benzylrest, idet også all with 1-4 C atoms, or a benzyl residue, as well

1*2 sammen med R^ eller R^ kan danne en fem- eller 1*2 together with R^ or R^ can form a five-or

seksleddet karbocyklisk ring, six-membered carbocyclic ring,

R^ betyr hydrogen, en alkylrest med 1-4 C-atomer eller R^ means hydrogen, an alkyl radical with 1-4 C atoms or

fenylresten, the phenyl residue,

R4 betyr hydrogen, en alkyl- eller alkenylrest, begge med R 4 means hydrogen, an alkyl or alkenyl radical, both with

1-4 C-atomer, en metoksymetyl- eller en benzylrest, 1-4 C atoms, a methoxymethyl or a benzyl residue,

et klor- eller bromatom, a chlorine or bromine atom,

ved omsetning av 2-pyroner med den generelle formel: by reaction of 2-pyrones with the general formula:

hvori R^, R2, R3 og R4 har ovennevnte betydning, med hydroksylamin eller dets salter i nærvær av aminer, idet fremgangsmåten er karakterisert ved at man som aminer anvender monoaminopyridin som eventuelt er 1-2 ganger substituert i kjernen med alkylgrupper med 1-4 C-atomer,eller imidazol. in which R 1 , R 2 , R 3 and R 4 have the above meaning, with hydroxylamine or its salts in the presence of amines, the method being characterized by using as amines monoaminopyridine which is optionally 1-2 times substituted in the nucleus with alkyl groups with 1-4 C atoms, or imidazole.

Foretrukket under de ovennevnte for R_ til R. nevnte Preferred among the above for R_ to R. mentioned

2 4 alkylrester er generelt de lavere alkylrester med 1 eller 2 C-atomer. 2 4 alkyl residues are generally the lower alkyl residues with 1 or 2 C atoms.

Av representanter av denne generelle type er det kjent gode antibakterielle og antimykotiske virkninger (US-patenter nr. 2.540.218, 3.269.904, belgisk patent nr. 738.288). Good antibacterial and antifungal effects are known from representatives of this general type (US patents no. 2,540,218, 3,269,904, Belgian patent no. 738,288).

Det er i noen tilfeller omtalt omdannelsen av 2-pyroner i l-hydroksy-2-pyridoner ved behandling med hydroksylamin-hydroklorid i pyridin (J.Am.Chiem.Soc. 78, 2393 (1956), J.Chem.Soc. In some cases the conversion of 2-pyrones into 1-hydroxy-2-pyridones by treatment with hydroxylamine hydrochloride in pyridine has been reported (J.Am.Chiem.Soc. 78, 2393 (1956), J.Chem.Soc.

(London) 1961, 4490). Denne fremgangsmåte er imidlertid begren-set til bestemte substituenter på a-pyronringen og ikke generaliserbar. Forsøker man nemlig å overføre på andre substituerte a-pyroner, så fastslår man at utbyttene av hydroksy-pyridoner er liten og deres fremstilling på denne måte praktisk talt ikke er gjennomførbar. (London) 1961, 4490). However, this method is limited to specific substituents on the α-pyrone ring and is not generalizable. Namely, if one tries to transfer to other substituted α-pyrones, it is determined that the yields of hydroxypyridones are small and their production in this way is practically not feasible.

Overraskende ble det nå funnet at man ifølge oppfinnelsen kan omdanne 2-pyroner i en generaliserbar fremgangsmåte i gode utbytter og under milde betingelser i l-hydroksy-2-pyridoner av høy renhet, når man omsetter dem med hydroksylamin eller dets salter i nærvær av 2-, 3- eller 4-aminopyridin eller imidazol eller ved i ringen med alkylrester med 1-4 C-atomer substituert aminopyridin. Således får man f.eks. av 4^-metyl-6-cyklohexyl-2-pyron ved 8 timers oppvarming med hydroksylamin-hydroklorid i pyridin ved 80°C tilsvarende 1-hydroksy-pyridon i et utbytte på 2,6% av det teoretiske. Med a-picolin i stedet for pyridin utgjør vitbyttet 3,0%. Erstatter man imidlertid under ellers like reaksjonsbetingelser pyridinet med aminene ifølge oppfinnelsen, ut-gjør utbyttene av det ønskede reaksjonsprodukt omtrent det 20-dobbelte, f.eks. med 2-aminopyridin 4 9%, med 2-amino-6-metylpyri-din 47%, med 2-amino-4-metylpyridin 53%, med imidazol 47% av det teoretiske. Dessuten viser det seg at ved fremgangsmåten ifølge oppfinnelsen fremstilte produkter utmerker seg ved en spesiell høy renhetsgrad. Tilsvarende ligger forholdet også med andre a-pyroner. . Som aminer som anvendes skal det eksempelvis nevnes: 2-aminopyridin, 3-aminopyridin, 4-aminopyridin, 2-metylamino-pyridin, 2-etylaminopyridin, 2-amino-4-metyl-pyridin, 2-amino-6-metylpyridin, 2-amino-4-etyl-pyridin, 2-amino-4,6-dimetyl-pyridin, 3-amino-6-metyl-pyridin, imidazol. Foretrukket er vanligvis de usubstituerte aminopyridiner eller de med en metylgruppe substituerte representanter av aminopyridin, spesielt på grunn av deres lette tekniske tilgjengelighet, deres lavere molekylvekt og deres høye oppløsningsevne for reaksjonsdeltagerne, nemlig ikke bare for de organiske komponenter, men også saltene av hydroksylamin. Da de fleste av disse forbindelser er faste ved værelsestemperatur, kan det være fordelaktig å anvende flytende blandinger av disse forbindelser, når man vil gjennomføre omsetningen ved lave temperaturer, f.eks. 20°C. Surprisingly, it was now found that, according to the invention, one can convert 2-pyrones in a generalizable process in good yields and under mild conditions into 1-hydroxy-2-pyridones of high purity, when one reacts them with hydroxylamine or its salts in the presence of 2 -, 3- or 4-aminopyridine or imidazole or by aminopyridine substituted in the ring with alkyl residues with 1-4 C atoms. Thus, you get e.g. of 4^-methyl-6-cyclohexyl-2-pyrone by heating for 8 hours with hydroxylamine hydrochloride in pyridine at 80°C corresponding to 1-hydroxypyridone in a yield of 2.6% of the theoretical. With a-picoline instead of pyridine, the white yield amounts to 3.0%. If, however, under otherwise identical reaction conditions, the pyridine is replaced with the amines according to the invention, the yields of the desired reaction product are approximately 20-fold, e.g. with 2-aminopyridine 4 9%, with 2-amino-6-methylpyridine 47%, with 2-amino-4-methylpyridine 53%, with imidazole 47% of the theoretical. Furthermore, it turns out that products produced by the method according to the invention are distinguished by a particularly high degree of purity. The relationship is similar with other a-pyrones. . Examples of amines that are used are: 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2-methylaminopyridine, 2-ethylaminopyridine, 2-amino-4-methylpyridine, 2-amino-6-methylpyridine, 2 -amino-4-ethyl-pyridine, 2-amino-4,6-dimethyl-pyridine, 3-amino-6-methyl-pyridine, imidazole. Preferred are usually the unsubstituted aminopyridines or the representatives of aminopyridine substituted with a methyl group, especially because of their easy technical availability, their lower molecular weight and their high solubility for the reaction participants, namely not only for the organic components, but also for the salts of hydroxylamine. As most of these compounds are solid at room temperature, it can be advantageous to use liquid mixtures of these compounds, when you want to carry out the reaction at low temperatures, e.g. 20°C.

Omsetningen kan gjennomføres innen vide temperatur-grenser, f .eks mellom værelsestemperatur og 150°C eller enda høyere. I de fleste tilfeller oppnås tilfredsstillende reaksjons-hastigheter mellom 50° og 120°C, dette er således et foretrukket temperaturområde. The conversion can be carried out within wide temperature limits, for example between room temperature and 150°C or even higher. In most cases, satisfactory reaction rates are achieved between 50° and 120°C, this is thus a preferred temperature range.

Tilsetningen av under reaksjonsbetingelsene inerte oppløsningsmidler resp. fortynningsmidler er mulig, imidlertid vanligvis ikke nødvendig. I spesielle tilfeller kan det imidlertid være fordelaktig. Slike oppløsnings- eller fortynningsmidler kan være polare eller upolare, de kan være blandbare eller ikke blandbare med vann. The addition of solvents inert under the reaction conditions or diluents are possible, but usually not necessary. In special cases, however, it can be beneficial. Such solvents or diluents can be polar or non-polar, they can be miscible or immiscible with water.

Aminene anvendes hensiktsmessig i minst ekvimolar mengde, referert til hydroksylaminsaltet. Riktignok kan man erstatte en del ved andre syreakseptorer av organisk eller uorga-nisk natur, imidlertid fører dette under tiden til merkelig langsomgjøring av reaksjonen, også kan gjenvinning av aminet, som vanligvis f.eks. er lett mulig ved destillering eller ekstrak-sjon, vanskeliggjøres ved slike tilsetninger. På den annen side har anvendelsen av et stort overskudd av aminopyridin eller imidazol, f.eks. 20-ganger molare mengder, referert til hydrok-sylaminsalt, ingen uheldig innvirkning på reaksjonsforløpet. The amines are suitably used in at least an equimolar amount, referred to the hydroxylamine salt. Admittedly, one can replace a part with other acid acceptors of an organic or inorganic nature, however, in the meantime this leads to a strange slowing down of the reaction, recovery of the amine, which usually e.g. is easily possible by distillation or extraction, is made difficult by such additions. On the other hand, the use of a large excess of aminopyridine or imidazole, e.g. 20 times molar amounts, referred to hydroxylamine salt, no adverse effect on the course of the reaction.

Hydroksylaminet resp. dets salter må selvsagt anvendes i ekvimolare mengder, referert til 2-pyron, som skal omsettes for å aksellerere reaksjonen . For å øke utbyttene kan det imidlertid også anvendes i overskudd, f.eks. inntil 5 eller 10 mol, referert til ett mol pyron. Det kan også være hensiktsmessig å tilsette hydroksylaminsaltet i flere porsjoner iløpet av reaksjonen. The hydroxylamine resp. its salts must of course be used in equimolar amounts, referred to 2-pyrone, which must be reacted to accelerate the reaction. In order to increase yields, however, it can also be used in excess, e.g. up to 5 or 10 moles, referred to one mole of pyrone. It may also be appropriate to add the hydroxylamine salt in several portions during the reaction.

a-pyronene som skal anvendes som utgangsprodukter er lett tilgjengelige etter forskjellige fremgangsmåter (f.eks. R.C. Elderfield, Heterocyclic Compounds, 2. opplag, volum 1, side 354 og følgende, J. Wiley & Sons, Inc., New York 1959? Chemische Berichte 100, 658 (1967)). The α-pyrones to be used as starting products are readily available by various methods (eg, R.C. Elderfield, Heterocyclic Compounds, 2nd ed., vol. 1, p. 354 et seq., J. Wiley & Sons, Inc., New York 1959? Chemische Berichte 100, 658 (1967)).

Eksempel 1 Example 1

2 g 4-metyl-6-cyklohexyl-2-pyron oppvarmes med 1 g hydroksylaminhydroklorid og 5 g 2-aminopyridin i 8 timer ved 80°C. Deretter opptar man i metylenklorid, fjerner aminet ved utryst-ning med fortynnet saltsyre, ekstraherer fra den organiske fase reaksjonsproduktet med fortynnet natronlut og surgjør den alka-liske oppløsning med eddiksyre til pH 6. l-hydroksy-4-metyl-6-cyklohexyl-2-pyridon fremkommer krystallinsk. Det suges fra, vaskes med vann og tørkes. 2 g of 4-methyl-6-cyclohexyl-2-pyrone is heated with 1 g of hydroxylamine hydrochloride and 5 g of 2-aminopyridine for 8 hours at 80°C. It is then taken up in methylene chloride, the amine is removed by shaking with dilute hydrochloric acid, the reaction product is extracted from the organic phase with dilute caustic soda and the alkaline solution is acidified with acetic acid to pH 6. 1-hydroxy-4-methyl-6-cyclohexyl- 2-pyridone appears crystalline. It is sucked off, washed with water and dried.

Utbyttet utgjør 1,05 g (4 9% av det teoretiske), The yield amounts to 1.05 g (4 9% of the theoretical),

smp. 143°C (beregnet: 6,8% N, funnet: 6,8% N). m.p. 143°C (calculated: 6.8% N, found: 6.8% N).

Under forøvrig like reaksjonsbetingelser får man ved anvendelse av 2-amino-4-metylpyridin 1,15 g (53%),med 2-amino-6-metyl-pyridin 1,01 g (47%), med 3-aminopyridin 0,52 g(24%), med imidazol 1,01 g (47%), derimot med pyridin 0,056 g (2,6%) og med Under otherwise identical reaction conditions, using 2-amino-4-methylpyridine 1.15 g (53%), with 2-amino-6-methyl-pyridine 1.01 g (47%), with 3-aminopyridine 0, 52 g (24%), with imidazole 1.01 g (47%), on the other hand with pyridine 0.056 g (2.6%) and with

a-picolin 0,065 g (3,0%) av hydroksypyridonet. α-picoline 0.065 g (3.0%) of the hydroxypyridone.

E ksempel 2 Example 2

2 g 3-benzyl-4,6-dimetyl-2-pyron, 6 g 2-aminopyridin og 1 g hydroksylamin-hydroklorid oppvarmes i 8 timer ved 70°C. Etter den i Eks. 1 omtalte opparbeidelse får man 0,6 5 g (30%) l-hydroksy-3-benzyl-4,6-dimetyl-2-pyridon av smeltepunkt 2 g of 3-benzyl-4,6-dimethyl-2-pyrone, 6 g of 2-aminopyridine and 1 g of hydroxylamine hydrochloride are heated for 8 hours at 70°C. After the one in Ex. 1 mentioned preparation yields 0.65 g (30%) of 1-hydroxy-3-benzyl-4,6-dimethyl-2-pyridone of melting point

148°C (beregnet: 6,1% N, funnet: 6,1% N). 148°C (calculated: 6.1% N, found: 6.1% N).

Anvender man under ellers like betingelser pyridin i stedet for aminopyridin, fåes intet hydroksypyridon. If, under otherwise identical conditions, pyridine is used instead of aminopyridine, no hydroxypyridone is obtained.

Eksempel 3 Example 3

2 g 4-metyl-6-benzyl-2-pyron, 6 g 2-aminopyridin og 1 g hydroksylaminhydroklorid oppvarmes 5 timer ved 80°C. Etter 2 g of 4-methyl-6-benzyl-2-pyrone, 6 g of 2-aminopyridine and 1 g of hydroxylamine hydrochloride are heated for 5 hours at 80°C. After

den vanlige opparbeidelse isolerer man 1,41 g (66%) 1-hydroksy-4-metyl-6-benzyl-2-pyridon av smeltepunkt 135°C (beregnet: 6,5% N, funnet 6,6% N). the usual work-up isolates 1.41 g (66%) of 1-hydroxy-4-methyl-6-benzyl-2-pyridone of melting point 135°C (calculated: 6.5% N, found 6.6% N).

Erstatter man under ellers like betingelser aminopyri-dinet med imidazol, så utgjør utbyttet 1,33 g (62%), med pyridin derimot bare 0,26 g (12%). Dessuten er de med aminopyridin og imidazol dannede produkter rent hvite, mens det med pyridin If, under otherwise identical conditions, the aminopyridine is replaced by imidazole, the yield is 1.33 g (62%), with pyridine, on the other hand, only 0.26 g (12%). Moreover, the products formed with aminopyridine and imidazole are pure white, while with pyridine

dannede preparat er farvet gulaktig. formed preparations are colored yellowish.

E ksempel 4 Example 4

a) 2 g 4,6-dimetyl-5-benzyl-2-pyron, 4g 2-aminopyridin og 0,9 g hydroksylamin-hydroklorid oppvarmes 5 timer ved 80°C. a) 2 g of 4,6-dimethyl-5-benzyl-2-pyrone, 4 g of 2-aminopyridine and 0.9 g of hydroxylamine hydrochloride are heated for 5 hours at 80°C.

Etter dén vanlige opparbeidelse får man 0,89 g (42%) 1-hydroksy-4,6-dimetyl-5-benzyl-2-pyridon av smeltepunkt 165°C (beregnet: After the usual work-up, 0.89 g (42%) of 1-hydroxy-4,6-dimethyl-5-benzyl-2-pyridone of melting point 165°C is obtained (calculated:

6,1%, funnet 6,1% N). 6.1%, found 6.1% N).

Under sammenlignbare betingelser vil man Under comparable conditions one will

b) av 4-metyl-6-fenylsulfonylmetyl-2-pyron få 1-hydroksy-4-metyl-6-fenylsulfonylmetyl-2-pyridon av smeltepunt ca. 260°C b) from 4-methyl-6-phenylsulfonylmethyl-2-pyrone obtain 1-hydroxy-4-methyl-6-phenylsulfonylmethyl-2-pyridone of melting point approx. 260°C

(36%, beregnet: 5,0% N, funnet: 5,1% N), (36%, calculated: 5.0% N, found: 5.1% N),

c) av 4-etyl-5,6-dimetyl-2-pyron få l-hydroksy-4-etyl-5,6-dimetyl-2-pyridon av smeltepunkt 139°C (33%, beregnet: 8,4% N, c) from 4-ethyl-5,6-dimethyl-2-pyrone obtain l-hydroxy-4-ethyl-5,6-dimethyl-2-pyridone of melting point 139°C (33%, calculated: 8.4% N ,

funnet: 8,2% N) , found: 8.2% N) ,

d) av 3-brom-4,6-dimetyl--2-pyron få l-hydroksy-3-brom-4,6-dimetyl-2-pyridon av smeltepunkt 220°C (37%, beregnet: 6,4% N, d) from 3-bromo-4,6-dimethyl-2-pyrone obtain l-hydroxy-3-bromo-4,6-dimethyl-2-pyridone of melting point 220°C (37%, calculated: 6.4% N,

funnet: 6,3% N), found: 6.3% N),

e) av 4-metyl-6-isobutenyl-2-pyron få l-hydroksy-4-metyl-6-isobutenyl-2-pyridon av smeltepunkt 116°C (24%, beregnet: e) from 4-methyl-6-isobutenyl-2-pyrone obtain 1-hydroxy-4-methyl-6-isobutenyl-2-pyridone of melting point 116°C (24%, calculated:

7,8% N, funnet: 7,7% N), 7.8% N, found: 7.7% N),

f) av 3,4-dimetyl-6-(4-tolyl)-2-pyron få 1-hydroksy-3,4-dimetyl-6-(4-tolyl)-2-pyrldon av smeltepunkt 125°C (41%, f) from 3,4-dimethyl-6-(4-tolyl)-2-pyrone obtain 1-hydroxy-3,4-dimethyl-6-(4-tolyl)-2-pyrldone of melting point 125°C (41% ,

beregnet: 6,1% N, funnet: 5,8% N), calculated: 6.1% N, found: 5.8% N),

g) av 4-metyl-5-etyl-6-(4-tolyl)-2-pyron få 1-hydroksy-4-metyl-5-etyl-6-(4-tolyl)-2-pyridon av smeltepunkt 180°C (49%, g) from 4-methyl-5-ethyl-6-(4-tolyl)-2-pyrone obtain 1-hydroxy-4-methyl-5-ethyl-6-(4-tolyl)-2-pyridone of melting point 180° C (49%,

beregnet: 5,8% N, funnet: 5,8% N), calculated: 5.8% N, found: 5.8% N),

h) av 4-metyl-6-(4-klorfenoksymetyl)-2-pyron få 1-hydroksy-4-metyl-6-(4-klorfenoksymetyl)-2-pyridon av smeltepunkt h) from 4-methyl-6-(4-chlorophenoxymethyl)-2-pyrone obtain 1-hydroxy-4-methyl-6-(4-chlorophenoxymethyl)-2-pyridone of melting point

161°C (37%, beregnet: 5,3% N, funnet: 5,6% N), 161°C (37%, calculated: 5.3% N, found: 5.6% N),

i) av 4-metyl-6-fenylmerkaptometyl-2-pyron få 1-hydroksy-4-metyl-6-fenylmerkaptometyl-2-pyridon av smeltepunkt 126°C (43%, beregnet: 5,7% N, funnet: 5,8% N), i) from 4-methyl-6-phenylmercaptomethyl-2-pyrone obtain 1-hydroxy-4-methyl-6-phenylmercaptomethyl-2-pyridone of melting point 126°C (43%, calculated: 5.7% N, found: 5 .8% N),

k) av 4,6-dimetyl-2-pyron få l-hydroksy-4,6-dimetyl-2-pyridon av smeltepunkt 135°C (46%, beregnet: 10,0% N, funnet: k) from 4,6-dimethyl-2-pyrone obtain l-hydroxy-4,6-dimethyl-2-pyridone of melting point 135°C (46%, calculated: 10.0% N, found:

10,1% N), 1) av 3,4,6-trimetyl-2-pyron få l-hydrokso-3,4,6-tri-metyl-2-pyridon av smeltepunkt 130°C (41%, beregnet: 9,2% N, funnet: 9,4% N), 10.1% N), 1) from 3,4,6-trimethyl-2-pyrone obtain l-hydroxo-3,4,6-tri-methyl-2-pyridone of melting point 130°C (41%, calculated: 9.2% N, found: 9.4% N),

m) av 6-metyl-2-pyron få l-hydroksy-6-metyl-2-pyridon av smeltepunkt 141°C (34%, beregnet: 1,2% N, funnet: 11,0% N), m) from 6-methyl-2-pyrone obtain l-hydroxy-6-methyl-2-pyridone of melting point 141°C (34%, calculated: 1.2% N, found: 11.0% N),

n) av 4-metyl-6-heptyl-2-pyron få l-hydroksy-4-metyl-6-heptyl-2-pyridon av smeltepunkt 48°C (38%, beregnet: 6,3% N, funnet: 6,0% N), n) from 4-methyl-6-heptyl-2-pyrone obtain l-hydroxy-4-methyl-6-heptyl-2-pyridone of melting point 48°C (38%, calculated: 6.3% N, found: 6 .0% N),

o) av 4-metyl-6-undecyl-2-pyron få l-hydroksy-4-metyl-6-undecyl-2-pyridon av smeltepunkt 63°C (33%, beregnet: 5,0% N, funnet: 5,4% N), o) from 4-methyl-6-undecyl-2-pyrone obtain l-hydroxy-4-methyl-6-undecyl-2-pyridone of melting point 63°C (33%, calculated: 5.0% N, found: 5 .4% N),

p) av 4,5-trimetylen-6-metyl-2-pyron få l-hydroksy-4,5-trimetylen-6-metyl-2-pyridon av smeltepunkt 177°C (44%, beregnet: p) of 4,5-trimethylene-6-methyl-2-pyrone obtain l-hydroxy-4,5-trimethylene-6-methyl-2-pyridone of melting point 177°C (44%, calculated:

8,5% N, funnet 8,4% N), 8.5% N, found 8.4% N),

q) av 4-metyl-6-(4-klorfenyl)-2-pyron få l-hydroksy-4-metyl-6-(4-klorfenyl)-2-pyridon med smeltepunkt 123°C (26%, beregnet: 6,0% N, funnet: 6,1% N), q) from 4-methyl-6-(4-chlorophenyl)-2-pyrone obtain 1-hydroxy-4-methyl-6-(4-chlorophenyl)-2-pyridone with melting point 123°C (26%, calculated: 6 .0% N, found: 6.1% N),

r) av 4,6-difenyl-2-pyron få l-hydroksy-4,6-difenyl-2-pyridon av smeltepunkt 16o°C (91%, beregnet: 5,3% N, funnet:5,3% N), r) from 4,6-diphenyl-2-pyrone obtain l-hydroxy-4,6-diphenyl-2-pyridone of melting point 16o°C (91%, calculated: 5.3% N, found: 5.3% N ),

ti ten

s) av 4-metyl-6-(a- ifuryl)-2-pyron få l-hydroksy-4-metyl-6-(a-furyl)-2-pyridon av smeltepunkt 147°C (26%, beregnet: 7,3% N, funnet: 7,6% N), s) of 4-methyl-6-(α-furyl)-2-pyrone obtain 1-hydroxy-4-methyl-6-(α-furyl)-2-pyridone of melting point 147°C (26%, calculated: 7 .3% N, found: 7.6% N),

t) av 4-metyl-6-/2-(a-furyl)-vinyl/-2-pyron få 1-hydroksy-4-metyl-6-/2-(a-furyl)-vinyl7~2-pyridon av smeltepunkt 166°C t) from 4-methyl-6-/2-(α-furyl)-vinyl/-2-pyrone obtain 1-hydroxy-4-methyl-6-(α-furyl)-vinyl7~2-pyridone from melting point 166°C

(28%, beregnet: 6,5%-N, funnet: 6,4% N), (28%, calculated: 6.5%-N, found: 6.4% N),

u) av 4-fenyl-6-metyl-2-pyron få l-hydroksy-4-fenyl-6-metyl-2-pyridon av smeltepunkt 185°C (62%, beregnet: 7,0% N, funnet: 6,7% N), u) from 4-phenyl-6-methyl-2-pyrone obtain l-hydroxy-4-phenyl-6-methyl-2-pyridone of melting point 185°C (62%, calculated: 7.0% N, found: 6 .7% N),

v) av 4-metyl-6-styryl-2-pyron få l-hydroksy-4-metyl-6-styryl-2-pyridon av smeltepunkt 176°C (34%, beregnet: 6,2% N, funnet: 6,0% N), v) from 4-methyl-6-styryl-2-pyrone obtain l-hydroxy-4-methyl-6-styryl-2-pyridone of melting point 176°C (34%, calculated: 6.2% N, found: 6 .0% N),

w) av 4-metyl-6-/4-fenyl-butadien-(1)-yl7-2-pyron få 1- hydroksy-4-metyl-6-/4-fenyl-butadien-(1)-y lj-2-pyridon av smeltepunkt 220°C (39%, beregnet: 5,5% N, funnet: 5,5% N), w) from 4-methyl-6-/4-phenyl-butadiene-(1)-yl7-2-pyrone get 1-hydroxy-4-methyl-6-/4-phenyl-butadiene-(1)-y lj- 2-pyridone of melting point 220°C (39%, calculated: 5.5% N, found: 5.5% N),

x) av 4-metyl-6-(4-nitrofenyl)-2-pyron få 1-hydroksy-4-metyl-6-(4-nitrofenyl)-2-pyridon av smeltepunkt 190°C (18%, beregnet: 11,4% N, funnet: 10,9% N). x) from 4-methyl-6-(4-nitrophenyl)-2-pyrone obtain 1-hydroxy-4-methyl-6-(4-nitrophenyl)-2-pyridone of melting point 190°C (18%, calculated: 11 .4% N, found: 10.9% N).

E ksempel 5 Example 5

1 g 4-metyl-6-(4-tolyl)-2-pyron, 0,6 g hydroksylamin-hydroklorid og 4 g 2-aminopyridin oppvarmes i en time ved 80°C. Etter den vanlige opparbeidelse isolerer man 0,173 g (16,1%) 1-hydroksy-4-metyl-6-(4-tolyl)-2-pyridon av smeltepunkt 125°C (beregnet: 6,5% N, funnet: 6,6% N). Anvender man under ellers like betingelser pyridin i stedet for aminopyridin, utgjør utbyttet bare 0,012 g (1,1%). 1 g of 4-methyl-6-(4-tolyl)-2-pyrone, 0.6 g of hydroxylamine hydrochloride and 4 g of 2-aminopyridine are heated for one hour at 80°C. After the usual work-up, 0.173 g (16.1%) of 1-hydroxy-4-methyl-6-(4-tolyl)-2-pyridone of melting point 125°C is isolated (calculated: 6.5% N, found: 6 .6% N). If, under otherwise identical conditions, pyridine is used instead of aminopyridine, the yield is only 0.012 g (1.1%).

Under samme betingelse vil man av 4-metyl-6-fenyl-2-pyron få l-hydroksy-4-metyl-6-fenyl-2-pyridon av smeltepunkt 135°C (beregnet: 7,0% N, funnet: 7,0% N) med 2-aminopyridin i et utbytte på 17,2%, med pyridin derimot bare med et utbytte på 1,3%. Under the same conditions, 4-methyl-6-phenyl-2-pyrone will yield l-hydroxy-4-methyl-6-phenyl-2-pyridone of melting point 135°C (calculated: 7.0% N, found: 7 .0% N) with 2-aminopyridine in a yield of 17.2%, with pyridine on the other hand only with a yield of 1.3%.

E ksempel 6 Example 6

1 g 4-metyl-6-(4-dimetylaminostyryl)-2-pyron, 3 g 2- aminopyridin og 0,4 g hydroksylamin-hydroklorid oppvarmes 10 timer på 70°C og oppfylles deretter reaksjonsproduktet ved til-setning av vann. Smp. ca. 250°C, 0,91 g (86%, beregnet: 10,4% N, funnet: 10,0% N). 1 g of 4-methyl-6-(4-dimethylaminostyryl)-2-pyrone, 3 g of 2-aminopyridine and 0.4 g of hydroxylamine hydrochloride are heated for 10 hours at 70°C and the reaction product is then filled by adding water. Temp. about. 250°C, 0.91 g (86%, calculated: 10.4% N, found: 10.0% N).

E ksempel 7 Example 7

Det arbeides som angitt i Eks. 4, imidlertid anvendes i stedet for 2-aminopyridin 2-amino-6-metyl-pyridin. Man vil: a) av 4-metyl-6-cyklohexylmetyl-2-pyron få 1-hydroksy-4-metyl-6-cyklohexylmetyl-2-pyridon av smeltepunkt 131°C (44%, Work is carried out as indicated in Ex. 4, however, instead of 2-aminopyridine 2-amino-6-methyl-pyridine is used. One will: a) from 4-methyl-6-cyclohexylmethyl-2-pyrone obtain 1-hydroxy-4-methyl-6-cyclohexylmethyl-2-pyridone of melting point 131°C (44%,

beregnet: 6,3% N, funnet: 6,5% N), calculated: 6.3% N, found: 6.5% N),

b) av 4-metyl-6-isopropyl-2-pyron få l-hydroksy-4-metyl-6-isopropyl-2-pyridon av smeltepunkt 110°C (47%, beregnet: 8,4% N, b) from 4-methyl-6-isopropyl-2-pyrone obtain l-hydroxy-4-methyl-6-isopropyl-2-pyridone of melting point 110°C (47%, calculated: 8.4% N,

funnet: 8,2% N), found: 8.2% N),

c) av 4-metyl-6-(4-metoksyfenyl)-2-pyron få 1-hydroksy-4-mety1-6-(4-metoksyfenyl)-2-pyridon av smeltepunkt 174°C (23%, c) from 4-methyl-6-(4-methoxyphenyl)-2-pyrone obtain 1-hydroxy-4-methyl-6-(4-methoxyphenyl)-2-pyridone of melting point 174°C (23%,

beregnet: 6,1% N, funnet: 5,9% N), calculated: 6.1% N, found: 5.9% N),

d) av 4-metyl-6-fenyl-5,2'-(2-metyletylen)-2-pyron få l-hydroksy-4-metyl-6-fenyl-5,2'-(2-metyletylen)-2-pyridon av d) from 4-methyl-6-phenyl-5,2'-(2-methylethylene)-2-pyrone obtain 1-hydroxy-4-methyl-6-phenyl-5,2'-(2-methylethylene)-2 -pyridone of

smeltepunkt 174°C (26%, beregnet: 5,8% N, funnet: 5,6% N), melting point 174°C (26%, calculated: 5.8% N, found: 5.6% N),

e) av 4-metyl-6-(3-nitrofenoksymetyl)-2-pyron få 1-hydroksy-4-metyl-6-(3-nitrofenoksymetyl)-2-pyridon av smeltepunkt e) from 4-methyl-6-(3-nitrophenoxymethyl)-2-pyrone obtain 1-hydroxy-4-methyl-6-(3-nitrophenoxymethyl)-2-pyridone of melting point

216°C (34%, beregnet: 10,2% N, funnet: 10,0% N), 216°C (34%, calculated: 10.2% N, found: 10.0% N),

f) av 4-metyl-6-etyl-2-pyron få l-hydroksy-4-metyl-6-etyl-2-pyridon av smeltepunkt llo°C (41%, beregnet: 9,2% N, f) from 4-methyl-6-ethyl-2-pyrone obtain 1-hydroxy-4-methyl-6-ethyl-2-pyridone of melting point llo°C (41%, calculated: 9.2% N,

funnet: 9,4% N) , found: 9.4% N) ,

g) av 3-etyl-4-metyl-6-(4-tolyl)-2-pyron få 1-hydroksy-3- etyl-4-mety1-6-(4-tolyl)-2-pyridon av smeltepunkt 100°C (29%, g) from 3-ethyl-4-methyl-6-(4-tolyl)-2-pyrone obtain 1-hydroxy-3-ethyl-4-methyl-6-(4-tolyl)-2-pyridone of melting point 100° C (29%,

beregnet: 5,8% N, funnet: 5,5% N), calculated: 5.8% N, found: 5.5% N),

h) av 3-metoksymetyl-4-metyl-6-(4-tolyl)-2-pyron få l-hydroksy-3-metoksymetyl-4-metyl-6-(4-tolyl)-2-pyridon av smeltepunkt 130°C (51%, beregnet: 5,4% N, funnet: 5,4% N), h) from 3-methoxymethyl-4-methyl-6-(4-tolyl)-2-pyrone obtain 1-hydroxy-3-methoxymethyl-4-methyl-6-(4-tolyl)-2-pyridone of melting point 130° C (51%, calculated: 5.4% N, found: 5.4% N),

i) av 4-mety1-6-(3-cyklohexyletyl)-2-pyron få 1-hydroksy-4- metyl-6-(8-cyklohexyletyl)-2-pyridon av smeltepunkt 90°C (41%, beregnet: 6,0% N, funnet: 5,8% N), i) from 4-methyl-6-(3-cyclohexylethyl)-2-pyrone obtain 1-hydroxy-4-methyl-6-(8-cyclohexylethyl)-2-pyridone of melting point 90°C (41%, calculated: 6 .0% N, found: 5.8% N),

k) av 4-metyl-6-benzhydryl-2-pyron få l-hydroksy-4-metyl-6-benzhydryl-2-pyridon av smeltepunkt 191°C (33%, beregnet: 4,7% N, funnet: 4,7% N). k) from 4-methyl-6-benzhydryl-2-pyrone obtain l-hydroxy-4-methyl-6-benzhydryl-2-pyridone of melting point 191°C (33%, calculated: 4.7% N, found: 4 .7% N).

Eksempel 8 Example 8

a) lg 4-metyl-5-propargyl-6-fenyl-2-pyron, l,5g hydroksylamin-hydroklorid og 3 g 2-amino-4-metyl-pyridin oppvarmes a) 1 g of 4-methyl-5-propargyl-6-phenyl-2-pyrone, 1.5 g of hydroxylamine hydrochloride and 3 g of 2-amino-4-methyl-pyridine are heated

9 timer ved 80°C. Etter den vanlige opparbeidelse får man 0,82 g (7.7%) l-hydroksy-4-metyl-5-propargyl-6-fenyl-2-pyridon av smelte- 9 hours at 80°C. After the usual work-up, 0.82 g (7.7%) of 1-hydroxy-4-methyl-5-propargyl-6-phenyl-2-pyridone is obtained from melting

punkt 200°C (beregnet: 5,9% N, funnet: 5,8% N) . point 200°C (calculated: 5.9% N, found: 5.8% N) .

Under samme betingelser vil man: Under the same conditions, one will:

b) av 3-allyl-4-metyl-6-fenyl-2-pyron få 1-hydroksy-3-allyl-4-metyl-6-fenyl-2-pyridon av smeltepunkt 115°C (60%, b) from 3-allyl-4-methyl-6-phenyl-2-pyrone obtain 1-hydroxy-3-allyl-4-methyl-6-phenyl-2-pyridone of melting point 115°C (60%,

beregnet: 5,8% N, funnet: 5,7% N), calculated: 5.8% N, found: 5.7% N),

c) av 4-metyl-5-allyl-6-fenyl-2-pyron få l-hydroksy-4-metyl-5-allyl-6-fenyl-2-pyridon av smeltepunkt 176°C (56%, c) from 4-methyl-5-allyl-6-phenyl-2-pyrone obtain 1-hydroxy-4-methyl-5-allyl-6-phenyl-2-pyridone of melting point 176°C (56%,

beregnet: 5,8% N, funnet: 5,5% N) . calculated: 5.8% N, found: 5.5% N).

Eksempel 9 Example 9

5 g 4-metyl-6-(4-klorbenzyl)-2-pyron, 2,5 g' hydroksylamin-hydroklorid og 10 g 2-aminopyridin oppvarmes 16 timer ved 60°C. Etter den vanlige opparbeidelse får man 3,3 g (62%) 1-hydroksy-4-metyl-6-(4-klorbenzyl)-2-pyridon av smeltepunkt 142°C (beregnet: 5,6% N, funnet: 5,9% N) . 5 g of 4-methyl-6-(4-chlorobenzyl)-2-pyrone, 2.5 g of hydroxylamine hydrochloride and 10 g of 2-aminopyridine are heated for 16 hours at 60°C. After the usual work-up, 3.3 g (62%) of 1-hydroxy-4-methyl-6-(4-chlorobenzyl)-2-pyridone of melting point 142°C are obtained (calculated: 5.6% N, found: 5 .9% N).

Eksempel 10 Example 10

10 g 4-metyl-6-(2,4,4-trimetylpentyl)-2-pyron, 5 g hydroksylamin-hydroklorid og 20 g 2-aminopyridin oppvarmes 26 timer ved 70°C, idet det etter 17 timer tilsettes ytterligere 2 g hydroksylamin0 Det opparbeides på vanlig måte og man får 7,1 g (67%) l-hydroksy-4-métyl-6-(2,4,4-trimetylpentyl)-2-pyridon av smeltepunkt 108°C (beregnet: 5,9% N, funnet: 5,9% N). 10 g of 4-methyl-6-(2,4,4-trimethylpentyl)-2-pyrone, 5 g of hydroxylamine hydrochloride and 20 g of 2-aminopyridine are heated for 26 hours at 70°C, adding after 17 hours a further 2 g hydroxylamine0 It is worked up in the usual way and 7.1 g (67%) of 1-hydroxy-4-methyl-6-(2,4,4-trimethylpentyl)-2-pyridone of melting point 108°C (calculated: 5, 9% N, found: 5.9% N).

Eksempel 11 Example 11

2 g 4-metyl-6-cyklohexyl-2-pyron og 1 g hydroksylamin oppløses i en blanding av 1,5 g 2-aminopyridin og 4,5 g 2-amino-6-metylpyridin og oppbevates 9 dager ved værelsestemperatur. Etter den vanlige opparbeidelse får man 0,79 g (37%) 1-hydroksy-4-metyl-6-cyklohexyl-2-pyridon av smeltepunkt 143°C. 2 g of 4-methyl-6-cyclohexyl-2-pyrone and 1 g of hydroxylamine are dissolved in a mixture of 1.5 g of 2-aminopyridine and 4.5 g of 2-amino-6-methylpyridine and stored for 9 days at room temperature. After the usual work-up, 0.79 g (37%) of 1-hydroxy-4-methyl-6-cyclohexyl-2-pyridone of melting point 143°C is obtained.

Eksempel 12 Example 12

1 g 3,4-dimetyl-6-(2,4-dimetylbenzyl)-2-pyron, 0,5 g hydroksylamin-hydroklorid og 3 g imidazol oppvarmes 8 timer ved 75°C og opparbeides deretter på vanlig måte. Man får 0,63 g (59%) l-hydroksy-3,4-dimetyl-6-(2,4-dimetylbenzyl)-2-pyridon av smeltepunkt 141°C (beregnet: 5,4% N, funnet: 5,6% N). Anvender man under ellers like betingelser pyridin i stedet for imidazol, 1 g of 3,4-dimethyl-6-(2,4-dimethylbenzyl)-2-pyrone, 0.5 g of hydroxylamine hydrochloride and 3 g of imidazole are heated for 8 hours at 75°C and then worked up in the usual way. 0.63 g (59%) of 1-hydroxy-3,4-dimethyl-6-(2,4-dimethylbenzyl)-2-pyridone of melting point 141°C is obtained (calculated: 5.4% N, found: 5 .6% N). If, under otherwise identical conditions, pyridine is used instead of imidazole,

så utgjør utbyttet 0,003 g (0,3%). then the yield amounts to 0.003 g (0.3%).

E ksempel 13 Example 13

20 g 4-metyl-6-cyklohexyl-2-pyron, 8 g hydroksylamin-sulfat og 50 g imidazol oppvarmes ved 90°C. Iløpet av 3 timer tilsettes ytterligere 10 g hydroksylamin-sulfat porsjonsvis. Etter tilsammen 5 timers reaksjonstid opparbeides. Det fåes 20 g of 4-methyl-6-cyclohexyl-2-pyrone, 8 g of hydroxylamine sulfate and 50 g of imidazole are heated at 90°C. During 3 hours, a further 10 g of hydroxylamine sulphate is added in portions. After a total of 5 hours of reaction time, it is worked up. It is available

11,8 g l-hydroksy-4-metyl-6-cyklohexyl-2-pyridon av smeltepunkt 143°C. 11.8 g of 1-hydroxy-4-methyl-6-cyclohexyl-2-pyridone of melting point 143°C.

Eksempel 14 Example 14

2 g 4-metyl-6-cyklohexyl-2-pyron, 1,2 g hydroksylamin-sulfat og 5 g imidazol oppvarmes i 1 time ved ilO°C. Utbyttet av det til 143°C smeltende l-hydroksy-4-metyl-6-cyklo-hexyl-2-pyridon utgjør 1,01 g. 2 g of 4-methyl-6-cyclohexyl-2-pyrone, 1.2 g of hydroxylamine sulfate and 5 g of imidazole are heated for 1 hour at 110°C. The yield of the 1-hydroxy-4-methyl-6-cyclohexyl-2-pyridone melting at 143°C amounts to 1.01 g.

Gjennomfører man reaksjonen ved 15 minutters oppvarming ved 150°C, utgjør utbyttet 0,94 g. If the reaction is carried out by heating for 15 minutes at 150°C, the yield is 0.94 g.

Eksempel 15 Example 15

1 g 4-metyl-6-cyklohexyl-2-pyron, 0,5 g hydroksylamin-hydroklorid, 2 g aminopyridin og 1 g toluen oppvarmes 5 timer ved 80°C. Etter ca. 1 time blir det til å begynne med tofasede system homogent. Utbyttet av hydroksypyridon utgjør 0,44 g. Til-setter man i stedet for toluen 1 g glyklolmonometyleter, utgjør utbyttet 0,47 g. 1 g of 4-methyl-6-cyclohexyl-2-pyrone, 0.5 g of hydroxylamine hydrochloride, 2 g of aminopyridine and 1 g of toluene are heated for 5 hours at 80°C. After approx. 1 hour, the two-phase system initially becomes homogeneous. The yield of hydroxypyridone is 0.44 g. If 1 g of glycol monomethyl ether is added instead of toluene, the yield is 0.47 g.

Claims (1)

Fremgangsmåte til fremstilling av l-hydroksy-2-pyridoner med den generelle formel:Process for the preparation of l-hydroxy-2-pyridones with the general formula: hvori R1 betyr en eventuell forgrenet alkylrest med 1 tiH7 C-atomer, en alkenylrest med 2 til 17 C-atomer, en cykloalkylrest med 3 til 8 C-atomer, en cyklohexylalkylrest, hvor alkylresten har 1-4 C-atomer, en eventuelt til den aromatiske kjerne med en eller flere alkyl-, alkoksy-, < dialkylamino-, nitro-, r alkoksykarbonyl-, cyangrupper eller halogenatomer substituert fenyl-, fenylalkyl-, fenylalkenyl-, benzhydryl-, fenoksymetyl-, fenylmerkaptometyl-, fenylsulfonylmetylrest, en furyl- eller furylalkenylrest, hvor alkyl-, alkenyl- og alkoksygrupper kan ha 1-4 C-atomer, 1*2 betyr hydrogen, en alkyl-, alkenyl- eller alkynyl rest alle med 1-4 G-atomer, eller en benzylrest, idet også R2 sammen med R^ eller R^ kan danne en fem- eller seksleddet karbocyklisk ring, R^ betyr hydrogen, en alkylrest med 1-4 C-atomer eller en fenylrest, R^ betyr hydrogen, en alkyl- eller alkenylrest, begge med 1-4 C-atomer, en metoksymetyl- eller en benzylrest, et klor- eller bromatom, ved omsetning av 2-pyroner med den generelle formel: hvori R^, R^ r R-j og R^ har ovenfor nevnte betydninger, med hydroksylamin eller dets salter i nærvær av aminer, karakterisert ved at man som aminer anvender monoaminopyridin som eventuelt er 1-2 ganger substituert i kjernen med alkylgriipper med 1-4 C-atomer,eller imidazol.in which R1 means an optional branched alkyl radical with 1 to H7 C atoms, an alkenyl radical with 2 to 17 C atoms, a cycloalkyl radical with 3 to 8 C atoms, a cyclohexylalkyl radical, where the alkyl radical has 1 to 4 C atoms, an optional the aromatic nucleus with one or more alkyl, alkoxy, < dialkylamino, nitro, r alkoxycarbonyl, cyano groups or halogen atoms substituted phenyl, phenylalkyl, phenylalkenyl, benzhydryl, phenoxymethyl, phenylmercaptomethyl, phenylsulfonylmethyl radical, a furyl or furylalkenyl radical, where alkyl, alkenyl and alkoxy groups can have 1-4 C atoms, 1*2 means hydrogen, a alkyl, alkenyl or alkynyl residues all with 1-4 G atoms, or a benzyl residue, since R2 together with R^ or R^ can also form a five- or six-membered carbocyclic ring, R^ means hydrogen, an alkyl residue with 1-4 C atoms or a phenyl radical, R 1 means hydrogen, an alkyl or alkenyl radical, both with 1-4 C atoms, a methoxymethyl or a benzyl residue, a chlorine or bromine atom, by reaction of 2-pyrones with the general formula: in which R^, R^ r R-j and R^ have the meanings mentioned above, with hydroxylamine or its salts in the presence of amines, characterized in that monoaminopyridine is used as amines which is optionally 1-2 times substituted in the nucleus with alkyl groups with 1-4 C atoms, or imidazole.
NO1205/73A 1972-03-25 1973-03-23 PROCEDURE FOR THE PREPARATION OF 1-HYDROXY-2-PYRIDONES NO139861C (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE19722214608 DE2214608C3 (en) 1972-03-25 Process for the preparation of J-hydroxy-2-pyridones

Publications (2)

Publication Number Publication Date
NO139861B true NO139861B (en) 1979-02-12
NO139861C NO139861C (en) 1979-05-23

Family

ID=5840130

Family Applications (1)

Application Number Title Priority Date Filing Date
NO1205/73A NO139861C (en) 1972-03-25 1973-03-23 PROCEDURE FOR THE PREPARATION OF 1-HYDROXY-2-PYRIDONES

Country Status (27)

Country Link
JP (1) JPS5233B2 (en)
KR (1) KR780000095B1 (en)
AR (1) AR219038A1 (en)
AT (1) AT327190B (en)
BE (1) BE797346A (en)
BG (2) BG22814A3 (en)
CA (1) CA979449A (en)
CH (1) CH579050A5 (en)
CS (1) CS183686B2 (en)
DD (1) DD105612A5 (en)
DK (1) DK139966C (en)
EG (1) EG10850A (en)
ES (1) ES412847A1 (en)
FI (1) FI55331C (en)
FR (1) FR2177963B1 (en)
GB (1) GB1416397A (en)
HU (1) HU166579B (en)
MY (1) MY7800114A (en)
NL (1) NL175177C (en)
NO (1) NO139861C (en)
PH (1) PH9480A (en)
PL (1) PL91738B1 (en)
RO (1) RO62622A (en)
SE (1) SE383151B (en)
SU (1) SU468418A3 (en)
YU (1) YU35583B (en)
ZA (1) ZA732042B (en)

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4178242A (en) * 1975-11-11 1979-12-11 Anic S.P.A. Method for the purification of sewage waters which contain organic compounds of an anionic character
JPS5323145A (en) * 1976-07-20 1978-03-03 Kurita Water Ind Ltd Method of dehydrating sludge
JPS54144759A (en) * 1978-04-29 1979-11-12 Tobata Tekko Kk Method of decoloring waste water containing dyestuffs
US4912118A (en) * 1983-09-23 1990-03-27 National Research Development Corporation Pharmaceutical compositions
GB8325496D0 (en) * 1983-09-23 1983-10-26 Hider R C Pharmaceutical compositions
USRE34313E (en) * 1983-09-23 1993-07-13 National Research Development Corporation Pharmaceutical compositions
US5817825A (en) * 1994-11-02 1998-10-06 Hoechst Aktiengesellschaft Process for the preparation of 1-hydroxy-2-pyridones
JP4556241B2 (en) * 2003-02-05 2010-10-06 日本曹達株式会社 Novel 6-fluoroalkyl-2 (1H) -pyridinone, 6-fluoroalkylpyridine compound and process for producing the same
US11753379B2 (en) * 2018-05-30 2023-09-12 Clariant International Ltd Process for forming 2-hydroxypyridine-1-oxide or derivatives thereof
EP4122918A1 (en) * 2021-07-19 2023-01-25 Clariant International Ltd Process for the preparation of n-hydroxypyridone compounds
WO2024104987A2 (en) * 2022-11-16 2024-05-23 Clariant International Ltd Process for the crystallization or precipitation of piroctone
WO2024115319A1 (en) * 2022-11-28 2024-06-06 Clariant International Ltd Process for the preparation of n-hydroxypyridone compounds

Also Published As

Publication number Publication date
SE383151B (en) 1976-03-01
NL175177C (en) 1984-10-01
CA979449A (en) 1975-12-09
ZA732042B (en) 1974-01-30
FR2177963A1 (en) 1973-11-09
CS183686B2 (en) 1978-07-31
GB1416397A (en) 1975-12-03
NL7303870A (en) 1973-09-27
CH579050A5 (en) 1976-08-31
YU78473A (en) 1980-09-25
JPS5233B2 (en) 1977-01-05
YU35583B (en) 1981-04-30
FI55331C (en) 1979-07-10
MY7800114A (en) 1978-12-31
HU166579B (en) 1975-04-28
DK139966C (en) 1979-11-05
AR219038A1 (en) 1980-07-31
AU5363073A (en) 1974-09-26
RO62622A (en) 1978-05-15
DD105612A5 (en) 1974-05-05
NO139861C (en) 1979-05-23
ATA262473A (en) 1975-04-15
BE797346A (en) 1973-09-26
NL175177B (en) 1984-05-01
AT327190B (en) 1976-01-26
PL91738B1 (en) 1977-03-31
JPS495976A (en) 1974-01-19
DK139966B (en) 1979-05-28
FR2177963B1 (en) 1976-11-05
SU468418A3 (en) 1975-04-25
PH9480A (en) 1976-01-08
BG22817A3 (en) 1977-04-20
FI55331B (en) 1979-03-30
KR780000095B1 (en) 1978-04-08
EG10850A (en) 1976-06-30
ES412847A1 (en) 1976-01-01
DE2214608B2 (en) 1977-03-31
BG22814A3 (en) 1977-04-20
DE2214608A1 (en) 1973-10-04

Similar Documents

Publication Publication Date Title
NO139861B (en) PROCEDURE FOR THE PREPARATION OF 1-HYDROXY-2-PYRIDONES
US3972888A (en) Process for the preparation of 1-hydroxy-pyridones
DK157296B (en) 2-CHLORO-PYRIDE COMPOUNDS FOR USE AS BASIC MATERIALS IN THE PREPARATION OF HERBICIDE PYRIDE COMPOUNDS
Katritzky 464. The preparation of some substituted pyridine 1-oxides
Fife et al. Cyanation in the pyridine series: Synthetic applications of the Reissert-Henze and related reactions
NO811240L (en) PROCEDURE FOR THE PREPARATION OF ANTIHYPERTENSIVE AMINES
El-Hiti et al. Directed lithiation and substitution of pyridine derivatives
Piepers et al. Synthesis of ‘crown ether’macrocyclic bislactones using caesium carboxylates of pyridine and of benzene dicarboxylic acids
SU475768A3 (en) The method of obtaining (5-nitrofuryl-2) -pyridine
DK169671B1 (en) Process for the preparation of pyridine-2,3-dicarboxylic acids
US3635995A (en) 2-(2-imidazolin-2-yl)methylthiopyridine-n-oxide and derivatives thereof
JPH0717605B2 (en) Production of 4-substituted pyridines
US3666765A (en) Synthesis of 2-pyridones and derivatives thereof
GB822592A (en) Carbazole derivatives and process for the production thereof
US3290320A (en) Benzoyl pyridine oximino ethers and methods for their manufacture
US3600396A (en) Alpha-dilower alkyl amino - 2,6 -di-(p-chlorophenyl) - 4-pyridine methanols and derivatives thereof
KR100355291B1 (en) Manufacturing method of pyridine-2,3-dicarboxylic acid
US5070204A (en) Process for preparation of fluoromethyl-substituted pyridine dicarboxylates
AU632911B2 (en) Process for preparation of fluoromethyl-substituted pyridine dicarboxylates
Sammes et al. Synthetic applications of N–N linked heterocycles. Part 16. Reactions between carbanions derived from carbon acids with p K a 7–14 and N-(2, 6-dimethyl-4-oxopyridin-1-yl) pyridinium tetrafluoroborate: synthesis of 4-substituted pyridines, and observation of pyridine ringopening reactions
Matsumura et al. The synthesis of 1-methyl-2-pyridones from 2-chloromethylpyridines
US3882132A (en) Preparation of 1-alkyl-1,4-dihydro-7-substituted-4-oxo-1,8-naphthyridine-3-carboxylic acids via the 3-aminomethyl analogs
US3530141A (en) Process for preparing 1,1&#39;-dialkyl-4,4&#39;-bipyridylium compounds
NO143534B (en) ANALOGY PROCEDURE FOR THE PREPARATION OF THERAPEUTICALLY EFFECTIVE DERIVATIVES OF OXATIINO (1,4) (2,3-C) PYRROL
US3354167A (en) Pyrazolone derivatives and process for their preparation