NO150561B - PROCEDURE FOR MANUFACTURING GAMMA PYRONS - Google Patents
PROCEDURE FOR MANUFACTURING GAMMA PYRONS Download PDFInfo
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- NO150561B NO150561B NO772193A NO772193A NO150561B NO 150561 B NO150561 B NO 150561B NO 772193 A NO772193 A NO 772193A NO 772193 A NO772193 A NO 772193A NO 150561 B NO150561 B NO 150561B
- Authority
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- Norway
- Prior art keywords
- formula
- maltol
- alkyl
- hydrogen
- carbon atoms
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 11
- 238000004519 manufacturing process Methods 0.000 title description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 8
- 150000002431 hydrogen Chemical group 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 5
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 239000000460 chlorine Substances 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 230000007062 hydrolysis Effects 0.000 claims description 4
- 238000006460 hydrolysis reaction Methods 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- CVQUWLDCFXOXEN-UHFFFAOYSA-N Pyran-4-one Chemical compound O=C1C=COC=C1 CVQUWLDCFXOXEN-UHFFFAOYSA-N 0.000 claims description 3
- 230000002378 acidificating effect Effects 0.000 claims description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052794 bromium Chemical group 0.000 claims description 3
- 150000007524 organic acids Chemical class 0.000 claims description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- 150000007522 mineralic acids Chemical class 0.000 claims description 2
- XPCTZQVDEJYUGT-UHFFFAOYSA-N 3-hydroxy-2-methyl-4-pyrone Chemical compound CC=1OC=CC(=O)C=1O XPCTZQVDEJYUGT-UHFFFAOYSA-N 0.000 description 32
- HYMLWHLQFGRFIY-UHFFFAOYSA-N Maltol Natural products CC1OC=CC(=O)C1=O HYMLWHLQFGRFIY-UHFFFAOYSA-N 0.000 description 14
- 229940043353 maltol Drugs 0.000 description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YIKYNHJUKRTCJL-UHFFFAOYSA-N Ethyl maltol Chemical compound CCC=1OC=CC(=O)C=1O YIKYNHJUKRTCJL-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229940093503 ethyl maltol Drugs 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 239000013067 intermediate product Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- VEYIMQVTPXPUHA-UHFFFAOYSA-N 3-hydroxypyran-4-one Chemical compound OC1=COC=CC1=O VEYIMQVTPXPUHA-UHFFFAOYSA-N 0.000 description 2
- DSEPAHSEUBGYDG-UHFFFAOYSA-N 4-bromo-2-hydroxy-6-methyl-2h-pyran-5-one Chemical compound CC1OC(O)C=C(Br)C1=O DSEPAHSEUBGYDG-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 125000001246 bromo group Chemical group Br* 0.000 description 2
- 239000003623 enhancer Substances 0.000 description 2
- 239000000796 flavoring agent Substances 0.000 description 2
- 235000019634 flavors Nutrition 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000002304 perfume Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- UABXUIWIFUZYQK-UHFFFAOYSA-N 1-(furan-2-yl)ethanol Chemical compound CC(O)C1=CC=CO1 UABXUIWIFUZYQK-UHFFFAOYSA-N 0.000 description 1
- MGVKFOXKPFXROH-UHFFFAOYSA-N 2-ethyl-3-hydroxy-6-methylpyran-4-one Chemical compound CCC=1OC(C)=CC(=O)C=1O MGVKFOXKPFXROH-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- DHPZIGNTAGIVKP-UHFFFAOYSA-N 4-chloro-2-methoxy-6-methyl-2h-pyran-5-one Chemical compound COC1OC(C)C(=O)C(Cl)=C1 DHPZIGNTAGIVKP-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 241000723343 Cichorium Species 0.000 description 1
- 235000007542 Cichorium intybus Nutrition 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 241000218652 Larix Species 0.000 description 1
- 235000005590 Larix decidua Nutrition 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 238000005904 alkaline hydrolysis reaction Methods 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000001719 carbohydrate derivatives Chemical class 0.000 description 1
- 229920001429 chelating resin Polymers 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000000686 essence Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 235000013379 molasses Nutrition 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- UCSJYZPVAKXKNQ-HZYVHMACSA-N streptomycin Chemical class CN[C@H]1[C@H](O)[C@@H](O)[C@H](CO)O[C@H]1O[C@@H]1[C@](C=O)(O)[C@H](C)O[C@H]1O[C@@H]1[C@@H](NC(N)=N)[C@H](O)[C@@H](NC(N)=N)[C@H](O)[C@H]1O UCSJYZPVAKXKNQ-HZYVHMACSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
- C07D309/32—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
- C07D309/34—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
- C07D309/36—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with oxygen atoms directly attached to ring carbon atoms
- C07D309/40—Oxygen atoms attached in positions 3 and 4, e.g. maltol
Description
Foreliggende oppfinnelse gjelder fremgangsmåte for fremstilling av gamma-pyroner ved hydrolyse av visse mellomprodukter, av hvilke noen er nye, hvilke mellomprodukter fremstilles fra passende furfurylalkoholer ved bruk av halogen-holdige oksydasjons-midler. The present invention relates to a process for the production of gamma-pyrones by hydrolysis of certain intermediate products, some of which are new, which intermediate products are produced from suitable furfuryl alcohols using halogen-containing oxidizing agents.
Maltol (2-metyl-3-hydroksy-4H-pyran-4-on) er en naturlig forekommende substans funnet i barken hos unge lerketrær, furu-nåler og sikori. Tidlig kommersiell produksjon foregikk ved de-struktiv destillasjon av ved. Syntesen av maltol fra 3-hydroksy-2-(l-piperidylmetyl)-l,4-pyron ble omtalt av Spielman og Freifelder i J.Am. Chem. Soc., 69, 2908 (1947). Schenck og Spielman, J. Am. Chem. Soc, 67, 2267 (1945) oppnådde maltol ved alkalisk hydrolyse av streptomycinsalter. Chawla og McGonigal, J. Org. Chem., Maltol (2-methyl-3-hydroxy-4H-pyran-4-one) is a naturally occurring substance found in the bark of young larch trees, pine needles and chicory. Early commercial production took place by destructive distillation of wood. The synthesis of maltol from 3-hydroxy-2-(1-piperidylmethyl)-1,4-pyrone was discussed by Spielman and Freifelder in J. Am. Chem. Soc., 69, 2908 (1947). Schenck and Spielman, J. Am. Chem. Soc, 67, 2267 (1945) obtained maltol by alkaline hydrolysis of streptomycin salts. Chawla and McGonigal, J. Org. Chem.,
39, 3281 (1974) og Lichtenthaler og Heidel, Angew. Chem., 81, 39, 3281 (1974) and Lichtenthaler and Heidel, Angew. Chem., 81,
998 (1969), omtalte syntese av maltol fra beskyttende karbohydrat-derivater. Shono og Matsumura, Tetrahedron Letters nr. 17, 1363 998 (1969), discussed the synthesis of maltol from protective carbohydrate derivatives. Shono and Matsumura, Tetrahedron Letters No. 17, 1363
(1976), beskrev en fem trinns syntese av maltol utgående fra metylfurfurylalkohol. (1976), described a five-step synthesis of maltol starting from methylfurfuryl alcohol.
Isoleringen av 6-metyl-2-etyl-3-hydroksy-4H-pyran-4-on The isolation of 6-methyl-2-ethyl-3-hydroxy-4H-pyran-4-one
som en av de karakteristiske søt-aromabestanddelene i raffinert, ferdig melasse ble omtalt av Hiroshi ito i Agr. Biol. Chem., 40 (5), 827-832 (1976). Denne forbindelse ble tidligere syntetisert ved hjelp av den fremgangsmåte som er beskrevet i US-patent 3.468.915. as one of the characteristic sweet-aroma constituents in refined, finished molasses was discussed by Hiroshi ito in Agr. Biol. Chem., 40 (5), 827-832 (1976). This compound was previously synthesized using the method described in US patent 3,468,915.
Synteser av gamma-pyroner som f.eks. pyromekonsyre, maltol, etylmaltol og andre 2-substituerte -3-hydroksy-gamma-pyroner er beskrevet i US-patenter 3.130.204, 3.133.089, 3.140.239, 3.159.652, 3.365.469, 3.376.317, 3.440.183, 3.446.629 og 3.468.915. Syntheses of gamma pyrones such as Pyromeconic acid, maltol, ethyl maltol and other 2-substituted-3-hydroxy-gamma-pyrones are described in US patents 3,130,204, 3,133,089, 3,140,239, 3,159,652, 3,365,469, 3,376,317, 3,440. 183, 3,446,629 and 3,468,915.
Maltol og etylmaltol øker smak og aroma for forskjellige næringsmidler. I tillegg brukes disse forbindelser som ingredi-enser i parfymer og essenser. De 2-alkenylpyromekonsyrer som er beskrevet i US-patent 3.644.635, og de 2-arylmetylpyromekonsyrer som er beskrevet i US-patent 3.365.469, hindrer vekst av bakterier og sopper og er anvendbare som smaks- og aromaøkende midler i næringsmidler og drikker, og aromaøkende midler i parfymer. Maltol and ethyl maltol increase the flavor and aroma of various foodstuffs. In addition, these compounds are used as ingredients in perfumes and essences. The 2-alkenylpyromeconic acids described in US patent 3,644,635 and the 2-arylmethylpyromeconic acids described in US patent 3,365,469 prevent the growth of bacteria and fungi and are useful as flavor and aroma enhancers in foodstuffs and beverages , and aroma enhancers in perfumes.
Det er nå funnet frem til en mer effektiv og økonomisk fremgangsmåte for fremstilling av maltol, etylmaltol og andre maltolanaloger fra nye mellomprodukter som selv kan fremstilles fra lett tilgjengelige utgangsmaterialer. A more efficient and economical method has now been found for the production of maltol, ethyl maltol and other maltol analogues from new intermediate products which can themselves be produced from readily available starting materials.
Foreliggende oppfinnelse tilveiebringer en fremgangsmåte for fremstilling av et gamma-pyron med formelen. The present invention provides a method for producing a gamma pyrone with the formula.
som omfatter hydrolyse ved oppvarming i sur, vandig løsning, fortrinnsvis ved en temperatur i området 70 til 160°, av et 4-halogen-dihydropyran med formel (II) eller et 6,6'-oksybis [4-halogen-2H-pyran-3(6H)-on] med formel (V): hvor R er hydrogen, alkyl med 1 til 4 karbonatomer, fenyl eller benzyl, R' er hydrogen, alkyl med 1 til 4 karbonatomer eller -COR", hvor R" er metyl, etyl eller fenyl, R"' er hydrogen eller alkyl med 1 til 4 karbonatomer og X er klor eller brom. which comprises hydrolysis by heating in acidic aqueous solution, preferably at a temperature in the range of 70 to 160°, of a 4-halo-dihydropyran of formula (II) or a 6,6'-oxybis[4-halo-2H-pyran -3(6H)-one] of formula (V): where R is hydrogen, alkyl of 1 to 4 carbon atoms, phenyl or benzyl, R' is hydrogen, alkyl of 1 to 4 carbon atoms or -COR", where R" is methyl, ethyl or phenyl, R"' is hydrogen or alkyl of 1 to 4 carbon atoms and X is chlorine or bromine.
Den syre som kreves for hydrolysen kan tilsettes til reaksjonsblandingen, f.eks. ved å oppløse mellomproduktet med formel (II) eller (V) i en vandig, uorganisk eller organisk syre før oppvarmingen; eller alternativt kan syren genereres in situ under fremstillingen av mellomproduktene. The acid required for the hydrolysis can be added to the reaction mixture, e.g. by dissolving the intermediate of formula (II) or (V) in an aqueous, inorganic or organic acid prior to heating; or alternatively, the acid may be generated in situ during the preparation of the intermediates.
Mellomproduktene med formel (II) og (V) kan fremstilles som beskrevet i henholdsvis de avdelte ansøkninger 8 21850 og 821851. The intermediates of formula (II) and (V) can be prepared as described in the separate applications 8 21850 and 821851, respectively.
Følgende eksempler illustrerer fremstillingen av gamma-pyronene ved fremgangsmåten ifølge oppfinnelsen. The following examples illustrate the preparation of the gamma pyrones by the method according to the invention.
Eksempel 1 Example 1
En løsning av 4-brom-6-hydroksy-2-metyl-2H-pyran-3(6H)-on ble fremstilt ved å oppløse forbindelsen enten i en vandig uorganisk eller vandig organisk syre. Løsningen ble så oppvarmet til tilbakeløp, avkjølt til romtemperatur, pH justert til 2,1 med 6n NaOH og reaksjonsblandingen ekstrahert med kloroform. Konsentrering gav maltol. Syrene, reaksjonstidene og utbyttene av maltol var som følger: A solution of 4-bromo-6-hydroxy-2-methyl-2H-pyran-3(6H)-one was prepared by dissolving the compound in either an aqueous inorganic or aqueous organic acid. The solution was then heated to reflux, cooled to room temperature, pH adjusted to 2.1 with 6N NaOH and the reaction mixture extracted with chloroform. Concentration gave maltol. The acids, reaction times and yields of maltol were as follows:
Alternativt kan organiske løsningsmidler som f.eks. benzen og toluen sammen med sure materialer som f.eks. p-toluensulfon-syre og "Amberlite" IR-120, brukes. Alternatively, organic solvents such as e.g. benzene and toluene together with acidic materials such as e.g. p-toluenesulfonic acid and "Amberlite" IR-120, are used.
Eksempel 2 Example 2
En løsning av 4-brom-6-hydroksy-2-metyl-2H-pyran-3(6H)-on(0,0025 mol) i 20 ml 35%-ig fosforsyre ble tilbakeløpsbehandlet i ca. 5 timer. Reaksjonsblandingen ble så filtrert varm, avkjølt, pH justert til 2,2 og reaksjonsblandingen avkjølt til 5°C. Krystallisasjon og filtrering ga rått 3-hydroksy-2-metyl-gamma-pyron (maltol). Det vandige filtratet ble ekstrahert med kloroform slik at det ble oppnådd en andre høst av maltol. Destillasjon av de kombinerte faststoffer og omkrystallisasjon fra metanol ga 34% utbytte av rent hvitt maltol, smp. 159,5 til 160,5°C. A solution of 4-bromo-6-hydroxy-2-methyl-2H-pyran-3(6H)-one (0.0025 mol) in 20 ml of 35% phosphoric acid was refluxed for approx. 5 hours. The reaction mixture was then filtered hot, cooled, pH adjusted to 2.2 and the reaction mixture cooled to 5°C. Crystallization and filtration gave crude 3-hydroxy-2-methyl-gamma-pyrone (maltol). The aqueous filtrate was extracted with chloroform to give a second crop of maltol. Distillation of the combined solids and recrystallization from methanol gave a 34% yield of pure white maltol, m.p. 159.5 to 160.5°C.
Eksempel 3 Example 3
En forbindelse med formelen: A compound with the formula:
hvor R er hydrogen, metyl, etyl, propyl, butyl, fenyl eller benzyl, og X er brom eller klor behandles ved hjelp av fremgangsmåten fra eksempel 2 slik at det oppnås en forbindelse med formelen: where R is hydrogen, methyl, ethyl, propyl, butyl, phenyl or benzyl, and X is bromine or chlorine is treated using the method from example 2 so that a compound with the formula is obtained:
hvor R er som ovenfor definert. where R is as defined above.
Eksempel 4 Example 4
Til en rundkolbe utstyrt med en magnetrører og en kjøler ble tilsatt 4-klor-6-metoksy-2-metyl-2H-pyran-3(6H)-on og eddiksyre og reaksjonsblandingen oppvarmet til tilbakeløp i 1 time. Maltol (65%) ble oppnådd ved avkjøling. To a round bottom flask equipped with a magnetic stirrer and a condenser were added 4-chloro-6-methoxy-2-methyl-2H-pyran-3(6H)-one and acetic acid and the reaction mixture heated to reflux for 1 hour. Maltol (65%) was obtained on cooling.
Eksempel 5 Example 5
Fremgangsmåten fra eksempel 4 ble gjentatt med sammen-lignbare resultater ved å bruke maursyre istedenfor eddiksyre. The procedure from Example 4 was repeated with comparable results using formic acid instead of acetic acid.
Eksempel 6 Example 6
Fremgangsmåten fra eksempel 4 ble gjentatt utgående fra en forbindelse med formelen: hvor R er hydrogen, alkyl med 1 til 4 karbonatomer, fenyl eller benzyl, R<*> er alkyl med 1 til 4 karbonatomer eller -COR" hvor R" er metyl, etyl eller fenyl og X er brom eller klor for å gi en forbindelse med formelen: The procedure from example 4 was repeated starting from a compound with the formula: where R is hydrogen, alkyl with 1 to 4 carbon atoms, phenyl or benzyl, R<*> is alkyl with 1 to 4 carbon atoms or -COR" where R" is methyl, ethyl or phenyl and X is bromo or chlorine to give a compound of the formula:
hvor R er hydrogen, alkyl med 1 til 4 karbonatomer, fenyl eller benzyl. where R is hydrogen, alkyl of 1 to 4 carbon atoms, phenyl or benzyl.
Claims (3)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US71090176A | 1976-08-02 | 1976-08-02 | |
| US05/721,885 US4082717A (en) | 1976-08-02 | 1976-09-09 | Preparation of gamma-pyrones |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| NO772193L NO772193L (en) | 1978-02-03 |
| NO150561B true NO150561B (en) | 1984-07-30 |
| NO150561C NO150561C (en) | 1984-11-07 |
Family
ID=27108548
Family Applications (7)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NO772193A NO150561C (en) | 1976-08-02 | 1977-06-22 | PROCEDURE FOR MANUFACTURING GAMMA PYRONS |
| NO821850A NO821850L (en) | 1976-08-02 | 1982-06-03 | PROCEDURE FOR THE PREPARATION OF 4-HALOGEN-DIHYDROPYRANE DERIVATIVES |
| NO821848A NO150043C (en) | 1976-08-02 | 1982-06-03 | PROCEDURE FOR MANUFACTURING GAMMA PYRONS |
| NO821851A NO150560C (en) | 1976-08-02 | 1982-06-03 | 6,6`-OXYBIS HALOGEN-SUBSTITUTED PYRON DERIVATIVES AND PROCEDURES FOR PREPARING THEREOF |
| NO821849A NO150559C (en) | 1976-08-02 | 1982-06-03 | 4-HALOGEN-DIHYDROPYRANE COMPOUNDS AND PROCEDURES FOR PREPARING THEREOF |
| NO821847A NO150042C (en) | 1976-08-02 | 1982-06-03 | PROCEDURE FOR MANUFACTURING GAMMA PYRONS |
| NO834236A NO151365C (en) | 1976-08-02 | 1983-11-18 | PROCEDURE FOR THE PREPARATION OF 4-HALOGEN-DIHYDROPYRANE DERIVATIVES. |
Family Applications After (6)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NO821850A NO821850L (en) | 1976-08-02 | 1982-06-03 | PROCEDURE FOR THE PREPARATION OF 4-HALOGEN-DIHYDROPYRANE DERIVATIVES |
| NO821848A NO150043C (en) | 1976-08-02 | 1982-06-03 | PROCEDURE FOR MANUFACTURING GAMMA PYRONS |
| NO821851A NO150560C (en) | 1976-08-02 | 1982-06-03 | 6,6`-OXYBIS HALOGEN-SUBSTITUTED PYRON DERIVATIVES AND PROCEDURES FOR PREPARING THEREOF |
| NO821849A NO150559C (en) | 1976-08-02 | 1982-06-03 | 4-HALOGEN-DIHYDROPYRANE COMPOUNDS AND PROCEDURES FOR PREPARING THEREOF |
| NO821847A NO150042C (en) | 1976-08-02 | 1982-06-03 | PROCEDURE FOR MANUFACTURING GAMMA PYRONS |
| NO834236A NO151365C (en) | 1976-08-02 | 1983-11-18 | PROCEDURE FOR THE PREPARATION OF 4-HALOGEN-DIHYDROPYRANE DERIVATIVES. |
Country Status (36)
| Country | Link |
|---|---|
| JP (7) | JPS5318578A (en) |
| AR (1) | AR216080A1 (en) |
| AT (3) | AT362790B (en) |
| BE (1) | BE855965A (en) |
| BG (4) | BG28849A3 (en) |
| BR (1) | BR7703970A (en) |
| CA (3) | CA1095921A (en) |
| CH (4) | CH625798A5 (en) |
| CS (3) | CS203921B2 (en) |
| DD (1) | DD132494A5 (en) |
| DE (3) | DE2760220C2 (en) |
| DK (4) | DK153483C (en) |
| EG (1) | EG13080A (en) |
| ES (5) | ES459994A1 (en) |
| FI (6) | FI72722C (en) |
| FR (1) | FR2372821A1 (en) |
| GB (5) | GB1538372A (en) |
| GR (1) | GR68938B (en) |
| HK (5) | HK30481A (en) |
| HU (4) | HU186026B (en) |
| IE (5) | IE45643B1 (en) |
| IT (1) | IT1106258B (en) |
| LU (1) | LU77600A1 (en) |
| MX (1) | MX4597E (en) |
| MY (3) | MY8100267A (en) |
| NL (5) | NL170955C (en) |
| NO (7) | NO150561C (en) |
| NZ (1) | NZ184342A (en) |
| PH (5) | PH13557A (en) |
| PL (4) | PL215008A1 (en) |
| PT (1) | PT66694B (en) |
| RO (4) | RO78951A2 (en) |
| SE (6) | SE433079B (en) |
| SU (2) | SU955859A3 (en) |
| TR (1) | TR19652A (en) |
| YU (4) | YU40166B (en) |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1095921A (en) | 1976-08-02 | 1981-02-17 | Thomas M. Brennan | Preparation of gamma-pyrones |
| JPS5444675A (en) * | 1977-09-12 | 1979-04-09 | Shin Etsu Chem Co Ltd | Production of 3-hydroxy-4-pyrone analog |
| FR2402654A1 (en) * | 1977-09-12 | 1979-04-06 | Shinetsu Chemical Co | Tetra:hydro-pyranone derivs. - useful as intermediates for cpds. used as food flavours |
| JPS5741226U (en) * | 1980-08-20 | 1982-03-05 | ||
| JPS59135008U (en) * | 1983-02-28 | 1984-09-10 | 松下電工株式会社 | Distribution board device |
| JPS6050245A (en) * | 1983-08-29 | 1985-03-19 | Nissan Motor Co Ltd | Fuel injection device in internal-combustion engine |
| JPH0226945Y2 (en) * | 1985-09-11 | 1990-07-20 | ||
| JP2586607B2 (en) * | 1987-10-30 | 1997-03-05 | 日産化学工業株式会社 | Production method of optically active alcohol |
| WO2008116301A1 (en) | 2007-03-28 | 2008-10-02 | Apotex Technologies Inc. | Fluorinated derivatives of deferiprone |
| UA102254C2 (en) | 2008-04-25 | 2013-06-25 | Апотекс Технолоджис Инк. | Normal;heading 1;heading 2;heading 3;LIQUID FORMULATION FOR DEFERIPRONE WITH PALATABLE TASTE |
| MA33985B1 (en) | 2009-07-03 | 2013-02-01 | Apotex Technologies Inc | FLUORINATED DERIVATIVES OF 3-HYDROXYPYRIDIN-4-ONES |
| WO2017168309A1 (en) * | 2016-03-29 | 2017-10-05 | Dr. Reddy’S Laboratories Limited | Process for preparation of eribulin and intermediates thereof |
| CN108609456B (en) * | 2016-12-13 | 2021-03-12 | 奥的斯电梯公司 | Openable expansion panel and elevator suspended ceiling, elevator car and elevator system with same |
| CN111606879A (en) * | 2020-05-25 | 2020-09-01 | 安徽金禾实业股份有限公司 | Method for preparing 2-hydroxymethyl-3-alkoxy-4H-pyran-4-ketone by one-pot method |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3491122A (en) * | 1966-09-14 | 1970-01-20 | Monsanto Co | Synthesis of 4-pyrones |
| US3547912A (en) * | 1968-07-29 | 1970-12-15 | American Home Prod | Derivatives of 2h-pyran-3(6h)-ones and preparation thereof |
| JPS5145565B1 (en) * | 1968-10-12 | 1976-12-04 | ||
| US3621063A (en) * | 1968-12-24 | 1971-11-16 | Monsanto Co | Unsaturated acyclic ketones |
| US3832357A (en) * | 1971-05-26 | 1974-08-27 | Daicel Ltd | Process for preparation of 3-hydroxy-2-alkyl-4-pyrone |
| JPS5212166A (en) * | 1975-07-17 | 1977-01-29 | Tatsuya Shono | Process for preparation of 4-pyron derivatives |
| IE42789B1 (en) * | 1975-08-28 | 1980-10-22 | Pfizer | Preparation of gamma-pyrones |
| CA1095921A (en) * | 1976-08-02 | 1981-02-17 | Thomas M. Brennan | Preparation of gamma-pyrones |
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1977
- 1977-06-06 CA CA279,922A patent/CA1095921A/en not_active Expired
- 1977-06-08 NZ NZ184342A patent/NZ184342A/en unknown
- 1977-06-09 GR GR53666A patent/GR68938B/el unknown
- 1977-06-13 YU YU1469/77A patent/YU40166B/en unknown
- 1977-06-15 MX MX775807U patent/MX4597E/en unknown
- 1977-06-16 JP JP7157277A patent/JPS5318578A/en active Granted
- 1977-06-16 SE SE7707035A patent/SE433079B/en not_active IP Right Cessation
- 1977-06-17 PH PH19887A patent/PH13557A/en unknown
- 1977-06-20 BR BR7703970A patent/BR7703970A/en unknown
- 1977-06-21 FI FI771934A patent/FI72722C/en not_active IP Right Cessation
- 1977-06-21 NL NLAANVRAGE7706811,A patent/NL170955C/en not_active IP Right Cessation
- 1977-06-21 BE BE1008209A patent/BE855965A/en not_active IP Right Cessation
- 1977-06-22 DE DE2760220A patent/DE2760220C2/de not_active Expired
- 1977-06-22 DK DK276177A patent/DK153483C/en active
- 1977-06-22 EG EG371/77A patent/EG13080A/en active
- 1977-06-22 CH CH765877A patent/CH625798A5/en not_active IP Right Cessation
- 1977-06-22 DE DE2760221A patent/DE2760221C2/de not_active Expired
- 1977-06-22 ES ES459994A patent/ES459994A1/en not_active Expired
- 1977-06-22 DE DE2728499A patent/DE2728499C2/en not_active Expired
- 1977-06-22 TR TR19652A patent/TR19652A/en unknown
- 1977-06-22 PT PT66694A patent/PT66694B/en unknown
- 1977-06-22 AT AT0440477A patent/AT362790B/en not_active IP Right Cessation
- 1977-06-22 LU LU77600A patent/LU77600A1/xx unknown
- 1977-06-22 NO NO772193A patent/NO150561C/en unknown
- 1977-06-23 AR AR268164A patent/AR216080A1/en active
- 1977-06-23 IT IT49950/77A patent/IT1106258B/en active
- 1977-06-23 DD DD7700199657A patent/DD132494A5/en not_active IP Right Cessation
- 1977-06-23 FR FR7719250A patent/FR2372821A1/en active Granted
- 1977-07-14 CS CS774705A patent/CS203921B2/en unknown
- 1977-07-14 BG BG7736892A patent/BG28849A3/en unknown
- 1977-07-14 BG BG7742606A patent/BG28988A4/en unknown
- 1977-07-14 BG BG7942608A patent/BG29136A3/en unknown
- 1977-07-14 BG BG7942607A patent/BG28989A4/en unknown
- 1977-07-20 RO RO7799825A patent/RO78951A2/en unknown
- 1977-07-20 RO RO7799830A patent/RO78953A/en unknown
- 1977-07-20 RO RO7791106A patent/RO74367A/en unknown
- 1977-07-20 RO RO7799826A patent/RO78952A/en unknown
- 1977-07-21 GB GB4240/78A patent/GB1538372A/en not_active Expired
- 1977-07-21 GB GB30759/77A patent/GB1538371A/en not_active Expired
- 1977-07-21 PL PL21500877A patent/PL215008A1/en unknown
- 1977-07-21 PL PL1977199798A patent/PL115586B1/en unknown
- 1977-07-21 GB GB4243/78A patent/GB1538375A/en not_active Expired
- 1977-07-21 HU HU82156A patent/HU186026B/en unknown
- 1977-07-21 PL PL1977215007A patent/PL115496B1/en unknown
- 1977-07-21 GB GB4242/78A patent/GB1538374A/en not_active Expired
- 1977-07-21 SU SU772508256A patent/SU955859A3/en active
- 1977-07-21 HU HU82157A patent/HU185687B/en unknown
- 1977-07-21 PL PL1977215006A patent/PL115497B1/en unknown
- 1977-07-21 HU HU77PI584A patent/HU180040B/en unknown
- 1977-07-21 GB GB4241/78A patent/GB1538373A/en not_active Expired
- 1977-07-21 HU HU82155A patent/HU185686B/en unknown
- 1977-07-29 IE IE585/79A patent/IE45643B1/en not_active IP Right Cessation
- 1977-07-29 IE IE584/79A patent/IE45642B1/en not_active IP Right Cessation
- 1977-07-29 IE IE1587/77A patent/IE45641B1/en not_active IP Right Cessation
- 1977-07-29 IE IE587/79A patent/IE45645B1/en not_active IP Right Cessation
- 1977-07-29 IE IE586/79A patent/IE45644B1/en not_active IP Right Cessation
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1978
- 1978-02-03 PH PH20745A patent/PH15185A/en unknown
- 1978-02-03 PH PH20746A patent/PH13926A/en unknown
- 1978-05-25 JP JP6281978A patent/JPS5436268A/en active Pending
- 1978-05-25 JP JP6281878A patent/JPS5436267A/en active Granted
- 1978-05-25 JP JP6281778A patent/JPS5436266A/en active Pending
- 1978-05-25 JP JP6282278A patent/JPS5436271A/en active Granted
- 1978-05-25 JP JP53062820A patent/JPS5814433B2/en not_active Expired
- 1978-05-25 JP JP6282178A patent/JPS5436270A/en active Granted
- 1978-06-07 CS CS783706A patent/CS203923B2/en unknown
- 1978-06-07 CS CS783705A patent/CS203922B2/en unknown
- 1978-06-13 ES ES470744A patent/ES470744A1/en not_active Expired
- 1978-06-13 ES ES470745A patent/ES470745A1/en not_active Expired
- 1978-06-13 ES ES470743A patent/ES470743A1/en not_active Expired
- 1978-06-13 ES ES470746A patent/ES470746A1/en not_active Expired
- 1978-07-05 SU SU782631651A patent/SU1015826A3/en active
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1979
- 1979-02-01 PH PH22150A patent/PH13874A/en unknown
- 1979-02-01 PH PH22149A patent/PH14625A/en unknown
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1980
- 1980-03-06 AT AT0124380A patent/AT364356B/en not_active IP Right Cessation
- 1980-03-06 AT AT0124480A patent/AT363470B/en not_active IP Right Cessation
- 1980-10-24 CA CA363,273A patent/CA1110254A/en not_active Expired
- 1980-10-24 CA CA000363274A patent/CA1117541A/en not_active Expired
- 1980-10-30 CH CH808580A patent/CH625235A5/en not_active IP Right Cessation
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1981
- 1981-02-20 CH CH116081A patent/CH626357A5/en not_active IP Right Cessation
- 1981-02-20 CH CH116181A patent/CH626358A5/en not_active IP Right Cessation
- 1981-07-02 HK HK304/81A patent/HK30481A/en unknown
- 1981-07-02 HK HK306/81A patent/HK30681A/en unknown
- 1981-07-02 HK HK305/81A patent/HK30581A/en unknown
- 1981-07-02 HK HK307/81A patent/HK30781A/en unknown
- 1981-07-02 HK HK303/81A patent/HK30381A/en unknown
- 1981-12-09 NL NLAANVRAGE8105538,A patent/NL182477C/en not_active IP Right Cessation
- 1981-12-09 NL NLAANVRAGE8105537,A patent/NL182476C/en not_active IP Right Cessation
- 1981-12-09 NL NLAANVRAGE8105540,A patent/NL182805C/en not_active IP Right Cessation
- 1981-12-09 NL NLAANVRAGE8105539,A patent/NL182478C/en not_active IP Right Cessation
- 1981-12-30 MY MY267/81A patent/MY8100267A/en unknown
- 1981-12-30 MY MY262/81A patent/MY8100262A/en unknown
- 1981-12-30 MY MY287/81A patent/MY8100287A/en unknown
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1982
- 1982-01-29 SE SE8200522A patent/SE444565B/en not_active IP Right Cessation
- 1982-01-29 SE SE8200520A patent/SE444564B/en not_active IP Right Cessation
- 1982-01-29 SE SE8200519A patent/SE445042B/en not_active IP Right Cessation
- 1982-01-29 SE SE8200518A patent/SE445041B/en not_active IP Right Cessation
- 1982-01-29 SE SE8200521A patent/SE452616B/en not_active IP Right Cessation
- 1982-06-03 NO NO821850A patent/NO821850L/en unknown
- 1982-06-03 NO NO821848A patent/NO150043C/en unknown
- 1982-06-03 NO NO821851A patent/NO150560C/en unknown
- 1982-06-03 NO NO821849A patent/NO150559C/en unknown
- 1982-06-03 NO NO821847A patent/NO150042C/en unknown
- 1982-12-07 YU YU02703/82A patent/YU270382A/en unknown
- 1982-12-13 YU YU2747/82A patent/YU42613B/en unknown
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1983
- 1983-05-16 FI FI831704A patent/FI72721C/en not_active IP Right Cessation
- 1983-05-16 FI FI831703A patent/FI73424C/en not_active IP Right Cessation
- 1983-05-16 FI FI831702A patent/FI72720C/en not_active IP Right Cessation
- 1983-05-16 FI FI831701A patent/FI72723C/en not_active IP Right Cessation
- 1983-05-16 FI FI831700A patent/FI72119C/en not_active IP Right Cessation
- 1983-08-08 YU YU1663/83A patent/YU43190B/en unknown
- 1983-11-18 NO NO834236A patent/NO151365C/en unknown
-
1986
- 1986-07-09 DK DK325986A patent/DK153484C/en active
- 1986-07-09 DK DK326186A patent/DK154079C/en active
- 1986-07-09 DK DK326086A patent/DK153401C/en not_active IP Right Cessation
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