NO150559B - 4-halogen-dihydropyran-forbindelser og fremgangsmaate for fremstilling derav - Google Patents
4-halogen-dihydropyran-forbindelser og fremgangsmaate for fremstilling derav Download PDFInfo
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- NO150559B NO150559B NO821849A NO821849A NO150559B NO 150559 B NO150559 B NO 150559B NO 821849 A NO821849 A NO 821849A NO 821849 A NO821849 A NO 821849A NO 150559 B NO150559 B NO 150559B
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- Prior art keywords
- carbon atoms
- formula
- bromine
- hydrogen
- alkyl
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- 238000000034 method Methods 0.000 title claims description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 11
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 11
- 229910052794 bromium Chemical group 0.000 claims description 11
- 229910052801 chlorine Inorganic materials 0.000 claims description 11
- 239000000460 chlorine Substances 0.000 claims description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 7
- 229910052736 halogen Inorganic materials 0.000 claims description 7
- 150000002367 halogens Chemical class 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 239000007800 oxidant agent Substances 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- CODNYICXDISAEA-UHFFFAOYSA-N bromine monochloride Chemical compound BrCl CODNYICXDISAEA-UHFFFAOYSA-N 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 230000020477 pH reduction Effects 0.000 claims description 5
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 claims description 3
- 150000001408 amides Chemical class 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000006184 cosolvent Substances 0.000 claims description 3
- 150000002009 diols Chemical class 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 239000013067 intermediate product Substances 0.000 claims description 3
- 150000002576 ketones Chemical class 0.000 claims description 3
- 150000002825 nitriles Chemical class 0.000 claims description 3
- 238000002360 preparation method Methods 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 16
- HYMLWHLQFGRFIY-UHFFFAOYSA-N Maltol Natural products CC1OC=CC(=O)C1=O HYMLWHLQFGRFIY-UHFFFAOYSA-N 0.000 description 7
- 229940043353 maltol Drugs 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 6
- 239000000543 intermediate Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- -1 furfural alcohols Chemical class 0.000 description 4
- 238000011065 in-situ storage Methods 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- VEYIMQVTPXPUHA-UHFFFAOYSA-N 3-hydroxypyran-4-one Chemical compound OC1=COC=CC1=O VEYIMQVTPXPUHA-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- UABXUIWIFUZYQK-UHFFFAOYSA-N 1-(furan-2-yl)ethanol Chemical compound CC(O)C1=CC=CO1 UABXUIWIFUZYQK-UHFFFAOYSA-N 0.000 description 2
- YIKYNHJUKRTCJL-UHFFFAOYSA-N Ethyl maltol Chemical compound CCC=1OC=CC(=O)C=1O YIKYNHJUKRTCJL-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- CVQUWLDCFXOXEN-UHFFFAOYSA-N Pyran-4-one Chemical compound O=C1C=COC=C1 CVQUWLDCFXOXEN-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- SKCNIGRBPJIUBQ-UHFFFAOYSA-N chloroform;ethyl acetate Chemical compound ClC(Cl)Cl.CCOC(C)=O SKCNIGRBPJIUBQ-UHFFFAOYSA-N 0.000 description 2
- 239000003623 enhancer Substances 0.000 description 2
- 229940093503 ethyl maltol Drugs 0.000 description 2
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000002304 perfume Substances 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- DQYZMWTXNWIUNS-UHFFFAOYSA-N 4-bromo-2-hydroxy-2h-pyran-5-one Chemical compound OC1OCC(=O)C(Br)=C1 DQYZMWTXNWIUNS-UHFFFAOYSA-N 0.000 description 1
- 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 1
- TXCADDUIVINZSC-UHFFFAOYSA-N 4-bromo-6-ethyl-2-hydroxy-2h-pyran-5-one Chemical compound CCC1OC(O)C=C(Br)C1=O TXCADDUIVINZSC-UHFFFAOYSA-N 0.000 description 1
- IGMQAWRMDKAASU-UHFFFAOYSA-N 4-chloro-2-hydroxy-2h-pyran-5-one Chemical compound OC1OCC(=O)C(Cl)=C1 IGMQAWRMDKAASU-UHFFFAOYSA-N 0.000 description 1
- UIYKATFGIGUNGC-UHFFFAOYSA-N 4-chloro-2-hydroxy-6-methyl-2h-pyran-5-one Chemical compound CC1OC(O)C=C(Cl)C1=O UIYKATFGIGUNGC-UHFFFAOYSA-N 0.000 description 1
- IBSOWVDZAXZPTI-UHFFFAOYSA-N 4-chloro-6-ethyl-2-hydroxy-2h-pyran-5-one Chemical compound CCC1OC(O)C=C(Cl)C1=O IBSOWVDZAXZPTI-UHFFFAOYSA-N 0.000 description 1
- MALOBWMOORWUQW-UHFFFAOYSA-N 4h-pyran-3-one Chemical class O=C1COC=CC1 MALOBWMOORWUQW-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
- HYBBIBNJHNGZAN-UHFFFAOYSA-N Furaldehyde Natural products O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 1
- 241000218652 Larix Species 0.000 description 1
- 235000005590 Larix decidua Nutrition 0.000 description 1
- 229910019093 NaOCl Inorganic materials 0.000 description 1
- 235000019502 Orange oil 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
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 238000005904 alkaline hydrolysis reaction Methods 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- DKSMCEUSSQTGBK-UHFFFAOYSA-N bromous acid Chemical compound OBr=O DKSMCEUSSQTGBK-UHFFFAOYSA-N 0.000 description 1
- 150000001719 carbohydrate derivatives Chemical class 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000000686 essence Substances 0.000 description 1
- 239000002024 ethyl acetate extract Substances 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000001475 halogen functional group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical group 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 235000013379 molasses Nutrition 0.000 description 1
- 239000010502 orange oil Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Inorganic materials [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M sodium chloride Inorganic materials [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000003756 stirring Methods 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
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pyrane Compounds (AREA)
- Pyridine Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Cosmetics (AREA)
- Plural Heterocyclic Compounds (AREA)
- Furan Compounds (AREA)
- Saccharide Compounds (AREA)
- Transforming Electric Information Into Light Information (AREA)
- Picture Signal Circuits (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
- Processing Of Color Television Signals (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
- Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
- Seasonings (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Control Of El Displays (AREA)
Description
Foreliggende oppfinnelse gjelder nye 4-halogen-dihydropyran-mellomprodukter som er nyttige for fremstilling av gamma-pyroner. Videre angår oppfinnelsen en fremgangsmåte for fremstilling av mellomproduktene fra passende furfuralalkoholer ved bruk av halogenholdige oksydasjonsmidler.
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 destruktiv destillasjon av ved. Syntesen av maltol fra 3-hydroksy~ 2-(1-piperidylmetyl)-1,4-pyron ble omtalt av Spielman og Frei-felder i J. Am. Ohem. 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., 39, 3281 (1974) og Lichtenthaler og Heidel,
Angew. Chem., 81, 998 (1969), omtalte syntese av maltol fra beskyttende karbohydrat-derivater. Shono og Matsumura, Tetrahedron Letters nr. 17, 1363 (1976), beskrev en fem trinns syntese av maltol utgående fra metylfurfurylalkohol.
Isoleringen av 6-metyl-2-etyl-3-hydroksy-4H-pyran-
4-on 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.
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.
Maltol og etylmaltol øker smak og aroma for for-skjellige næringsmidler. I tillegg brukes disse forbindelser som ingredienser i parfymer og essenser. De 2-alkenylpyromekon-syrer som er beskrevet i US-patent 3.644.635 og de 2-arylmetyl-pyromekonsyrer 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.
Patentsøknad 77.2193 beskriver en fremgangsmåte for fremstilling av et 3-hydroksy-4-pyron-derivat ved syrehydrolyse av et 3-pyron-derivat. -Ved fremgangsmåten fremstilles.et gamma-pyron med formelen
hvor R bl.a. er hydrogen eller alkyl med 1-4 karbonatomer, og R* *• er hydrogen eller alkyl med 1-4 karbonatomer, ved å starte med et 4-halogendihydropyran med formel (II) eller et 6,6'-oksybis[4-halogen-2H-pyran-3(6H)-on] med formel (V):
hvor R og R"1 er som angitt ovenfor, R' er hydrogen, alkyl med 1 til 4 karbonatomer eller -COR", hvor R" er metyl, etyl eller fenyl, og X er klor eller brom.
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 oppvarmningen; eller alternativt kan syren genereres in situ under fremstillingen av mellomproduktene som beskrevet senere.
Mellomproduktet med formel (II) kan fremstilles ved
å omsette en forbindelse med formelen:
hvor R, R' og R" 1 er som ovenfor definert, i et løsningsmiddel ved en temperatur på -50 til 50°C, fortrinnsvis ved romtemperatur, med minst én ekvivalent av et halogenholdig oksydasjonsmiddel valgt blant klor, brom, bromklorid, underklorsyrling, underbromsyrling eller blandinger derav inntil reaksjonen er i hoved-sak fullstendig.
Eksempler på egnede løsningsmidler for denne reaksjon
er vann, en alkanol eller diol med 1 til 4 karbonatomer, fortrinnsvis metanol, en eter med 2 til 10 karbonatomer, fortrinnsvis tetrahydrofuran eller isopropyleter, et keton med lav molekylvekt, fortrinnsvis aceton, et nitril, en ester eller et amid med lave molekylvekter.
Noen av 4-halogen-dihydropyran-mellomproduktene er nye, nemlig de med formel (II<1>) nedenfor, og ifølge oppfinnelsen til-veiebringes også en fremgangsmåte for fremstilling av disse 4-halogendihydropyran-forbindelser med formelen: hvor R er hydrogen eller alkyl med 1 til 4 karbonatomer, R'<*>' er hydrogen eller alkyl med 1 til 4 karbonatomer, og X er klor eller brom, og fremgangsmåten karakteriseres ved at en forbindelse med formelen:
hvor R og R"1 er som angitt ovenfor, omsettes i vandig opp-
løsning ved en temperatur på -50 til 50°C, med minst to ekvivalenter av et halogen-holdig oksydasjonsmiddel valgt fra klor, brom, bromklorid, underklorsyrling, underbromsyrling eller blandinger derav inntil omsetningen er tilnærmet fullstendig.
Omsetningen kan fortrinnsvis utføres i nærvær av et ko-løsningsmiddel som er en alkanol eller diol med 1 til 4 karbonatomer, en eter med 2 til 10 karbonatomer, eller et lavmolekylært keton, nitril, ester eller amid.
Foretrukne ko-løsningsmidler er metanol, tetrahydrofuran, isoprcpyleter eller aceton.
Det halogen-holdige oksydasjonsmidlet velges blant
klor, brom, bromklorid, underklor- eller underbrom-syrling eller blandinger derav. Bromklorid er en kommersielt tilgjengelig gass. Den kan fremstilles in situ ved tilsetning av klor til en løsning av natrium- eller kaliumbromid eller ved tilsetning av brom til en løsning av natrium- eller kaliumklorid. Underklor- og underbromsyrling kan hensiktsmessig genereres in situ ved tilsetning av vandig syre (HC1, H2S0^ eller HBr) til en løsning av alkalimetall- eller jordalkalimetall-hypohalogenitt, f..eks. NaOCl, K0C1 eller Ca(0Cl)2. De foretrukne halogen-holdige oksydasjonsmidler, basert på kostnadsfaktorer, er klor- og bromklorid fremstilt in situ.
Ved en foretrukket utførelsesform for oppfinnelsen omsettes en furfurylalkohol i vandig løsning, eventuelt sammen med et ko-løsningsmiddel, ved- 10 til 10°C med to ekvivalenter av et halogen-holdig oksydasjonsmiddel. Efter omrøring ved romtemperatur i 30 minutter, reguleres reaksjonsblandingens pH-verdi til 2 med en sterk base, og reaksjo^nsblandingen ekstra-heres med et løsningsmiddel så som etylacetat. Fjernelse av løsningsmidlet gir det ønskede 4-halogen-6-hydroksy-2H-pyran-3(6H)-on med formel (II').
Følgende eksempler illustrerer fremstillingen av 4-halogen-dihydropyran-mellomproduktene ved fremgangsmåten ifølge oppfinnelsen.
I eksemplene, der det gis spektraldata, er kjemiske NMR-skift-data angitt ved hjelp av konvensjonell litteratur-symbolisme og alle skift er uttrykt som 6-enheter fra tetrametyl-silan:
s = singlett
d = dublett
t = triplett
q = kvartett
m = multiplett
br= bred
Eksempel 1
4- brom- 6- hyd roksy- 2- metyl- 2H- pyran- 3( 6H)- on
Til en løsning av 25 g 1-(2-f uryl)-1-etano.l i 125 ml tetrahydrofuran og 125 ml vann ved 0 til 5°C ble tilsatt dråpe-vis 2,2 ekvivalenter brom. Under tilsetningen ble løsningen omrørt ved romtemperatur i 30 minutter og pH justert til 2,1 med 2N NaOH-løsning. Reaksjonsblandingen ble ekstrahert med etylacetat (3 x 100 ml). Etylacetatekstraktene ble kombinert, tørket over MgS04, filtrert og inndampet til tørrhet. Residuet ble kromatografert på silikagel og eluert med kloroform-etylacetat (95:5). Produktet var en oransje olje som ble omkromatografert på silikagel og eluert med kloroform-etylacetat (95:5) .
NMR (CDC13, 6) 7,3 (1H, d); 5,6 (1H, d); 4,7-5,0 (1H, q); 1,1-1,5 (3H, m).
Eksempel 2
Fremgangsmåten fra eksempel 1 ble gjentatt med en furfurylalkohol med formelen: for å gi en forbindelse med formelen:
hvor R er hydrogen eller etyl.
Etylforbindelse:: 4-brom-6-hydroksy-2-etyl-2H-pyran-3(6H)-on NMR (CDC13, 6) 7,4 (1H, d,); 4,6-4,9 (1H, m); 1,8-2,2 (2H, m) ; 1,0-1,3 (3H, t).
Hydrogenforbindelse: 4-brom-6-hydroksy-2H-pyran-3(6H)-on
NMR (CDC13, 6) 7,4 (1H, d; 5,5 (1H, d); 4,6 (2H, d av d).
Eksempel 3
Fremgangsmåten fra eksempel 1 ble gjentatt under anvendelse av klor istedenfor brom og passende furfurylalkoholer for å fremstille følgende forbindelser:
Metyl:
4-klor-6-hydroksy-2-metyl-2H-pyran-3-(6H)-on
NMR (CDC13, 6): 7,1 (1H, d); 5,8 (1H, d); 4,6-5,0 (1H, m);
4,4 (1H, br. s.); 1,2-1,5 (3H, m).
Etyl:
4-klor-6-hydroksy-2-etyl-2H-pyran-3(6H)-on
NMR (CDC13, 6): 7,0-7,1 (1H, d); 5,6-6,0 (2H, m); 4,4-5,0
(1H, m); 1,6-2,1 (2H, m); 0,9-1,1 (3H, t).
Hydrogen:
4-klor-6-hydroksy-2H-pyran-3(6H)-on
NMR (CDC13, 6): 7,1-7,2 (1H, d); 5,6 (1H, d); 4,4-4,9 (2H,
d av d) (D20 tilsatt).
Claims (4)
1. 4-halogen-dihydropyran-forbindelse for anvendelse som . mellomprodukt ved fremstilling av gamma-pyroner méd formel
hvor R er hydrogen eller alkyl med 1 til 4 karbonatomer, og R''<1> er hydrogen eller alkyl med 1 til 4 karbonatomer, karakterisert ved formelen:
hvor R og R1" er som ovenfor angitt, og X er klor eller brom.
2. Fremgangsmåte for fremstilling av en 4-halogen-dihydropyran-f orbindelse med formelen:
hvor R er hydrogen eller alkyl med 1 til 4 karbonatomer, R''' er hydrogen eller alkyl med 1 til 4 karbonatomer, og X er klor eller brom, karakterisert ved at en forbindelse med formelen:
hvor R og R'" er som angitt ovenfor, omsettes i vandig opp-løsning ved en temperatur på -50 til 50°C med minst to ekvivalenter av et halogenholdig oksydasjonsmiddel valgt fra klor, brom, bromklorid, underklorsyriing, underbromsyrling eller blandinger derav.
3. Fremgangsmåte ifølge krav 2,
karakterisert ved at omsetningen utføres i nærvær av et ko-løsningsmiddel som er en alkanol eller diol med 1 til 4 karbonatomer, en eter med 2 til 10 karbonatomer, eller et lavmolekylært keton, nitril, ester eller amid.
4. Fremgangsmåte ifølge krav 2,
karakterisert ved at det som løsningsmiddel anvendes metanol, tetrahydrofuran, isopropyleter eller aceton.
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 |
|---|---|
| NO821849L NO821849L (no) | 1978-02-03 |
| NO150559B true NO150559B (no) | 1984-07-30 |
| NO150559C NO150559C (no) | 1984-11-07 |
Family
ID=27108548
Family Applications (7)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NO772193A NO150561C (no) | 1976-08-02 | 1977-06-22 | Fremgangsmaate for fremstilling av gamma-pyroner |
| NO821849A NO150559C (no) | 1976-08-02 | 1982-06-03 | 4-halogen-dihydropyran-forbindelser og fremgangsmaate for fremstilling derav |
| NO821851A NO150560C (no) | 1976-08-02 | 1982-06-03 | 6,6`-oksybis-halogensubstituert-pyron-derivater og fremgangsmaae for fremstilling derav |
| NO821848A NO150043C (no) | 1976-08-02 | 1982-06-03 | Fremgangsmaate for fremstilling av gamma-pyroner |
| NO821850A NO821850L (no) | 1976-08-02 | 1982-06-03 | Fremgangsmaate for fremstilling av 4-halogen-dihydropyran-derivater |
| NO821847A NO150042C (no) | 1976-08-02 | 1982-06-03 | Fremgangsmaate for fremstilling av gamma-pyroner |
| NO834236A NO151365C (no) | 1976-08-02 | 1983-11-18 | Fremgangsmaate for fremstilling av 4-halogen-dihydropyran-derivater. |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NO772193A NO150561C (no) | 1976-08-02 | 1977-06-22 | Fremgangsmaate for fremstilling av gamma-pyroner |
Family Applications After (5)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NO821851A NO150560C (no) | 1976-08-02 | 1982-06-03 | 6,6`-oksybis-halogensubstituert-pyron-derivater og fremgangsmaae for fremstilling derav |
| NO821848A NO150043C (no) | 1976-08-02 | 1982-06-03 | Fremgangsmaate for fremstilling av gamma-pyroner |
| NO821850A NO821850L (no) | 1976-08-02 | 1982-06-03 | Fremgangsmaate for fremstilling av 4-halogen-dihydropyran-derivater |
| NO821847A NO150042C (no) | 1976-08-02 | 1982-06-03 | Fremgangsmaate for fremstilling av gamma-pyroner |
| NO834236A NO151365C (no) | 1976-08-02 | 1983-11-18 | Fremgangsmaate for fremstilling av 4-halogen-dihydropyran-derivater. |
Country Status (36)
| Country | Link |
|---|---|
| JP (7) | JPS5318578A (no) |
| AR (1) | AR216080A1 (no) |
| AT (3) | AT362790B (no) |
| BE (1) | BE855965A (no) |
| BG (4) | BG28849A3 (no) |
| BR (1) | BR7703970A (no) |
| CA (3) | CA1095921A (no) |
| CH (4) | CH625798A5 (no) |
| CS (3) | CS203921B2 (no) |
| DD (1) | DD132494A5 (no) |
| DE (3) | DE2728499C2 (no) |
| DK (4) | DK153483C (no) |
| EG (1) | EG13080A (no) |
| ES (5) | ES459994A1 (no) |
| FI (6) | FI72722C (no) |
| FR (1) | FR2372821A1 (no) |
| GB (5) | GB1538371A (no) |
| GR (1) | GR68938B (no) |
| HK (5) | HK30381A (no) |
| HU (4) | HU186026B (no) |
| IE (5) | IE45645B1 (no) |
| IT (1) | IT1106258B (no) |
| LU (1) | LU77600A1 (no) |
| MX (1) | MX4597E (no) |
| MY (3) | MY8100287A (no) |
| NL (5) | NL170955C (no) |
| NO (7) | NO150561C (no) |
| NZ (1) | NZ184342A (no) |
| PH (5) | PH13557A (no) |
| PL (4) | PL115496B1 (no) |
| PT (1) | PT66694B (no) |
| RO (4) | RO78951A2 (no) |
| SE (6) | SE433079B (no) |
| SU (2) | SU955859A3 (no) |
| TR (1) | TR19652A (no) |
| YU (4) | YU40166B (no) |
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 |
| FR2402654A1 (fr) * | 1977-09-12 | 1979-04-06 | Shinetsu Chemical Co | Nouveaux derives de x tetrahydropyrannone(5) |
| JPS5444675A (en) * | 1977-09-12 | 1979-04-09 | Shin Etsu Chem Co Ltd | Production of 3-hydroxy-4-pyrone analog |
| JPS5741226U (no) * | 1980-08-20 | 1982-03-05 | ||
| JPS59135008U (ja) * | 1983-02-28 | 1984-09-10 | 松下電工株式会社 | 分電盤装置 |
| JPS6050245A (ja) * | 1983-08-29 | 1985-03-19 | Nissan Motor Co Ltd | 内燃機関の燃料噴射装置 |
| JPH0226945Y2 (no) * | 1985-09-11 | 1990-07-20 | ||
| JP2586607B2 (ja) * | 1987-10-30 | 1997-03-05 | 日産化学工業株式会社 | 光学活性アルコールの製造法 |
| TWI404533B (zh) * | 2007-03-28 | 2013-08-11 | Apotex Technologies Inc | 去鐵酮（ｄｅｆｅｒｉｐｒｏｎｅ）之氟化衍生物 |
| UA102254C2 (ru) | 2008-04-25 | 2013-06-25 | Апотекс Технолоджис Инк. | Жидкий состав для деферипрона с приятным вкусом |
| CN102712591B (zh) | 2009-07-03 | 2014-06-25 | 阿普泰克斯科技公司 | 3-羟基吡啶-4-酮的氟化衍生物 |
| WO2017168309A1 (en) * | 2016-03-29 | 2017-10-05 | Dr. Reddy’S Laboratories Limited | Process for preparation of eribulin and intermediates thereof |
| CN108609456B (zh) * | 2016-12-13 | 2021-03-12 | 奥的斯电梯公司 | 可打开扩展面板及具有其的电梯吊顶，轿厢和系统 |
| CN111606879A (zh) * | 2020-05-25 | 2020-09-01 | 安徽金禾实业股份有限公司 | 一锅法制备2-羟甲基-3-烷氧基-4h-吡喃-4-酮的方法 |
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 (no) * | 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 |
-
1977
- 1977-06-06 CA CA279,922A patent/CA1095921A/en not_active Expired
- 1977-06-08 NZ NZ184342A patent/NZ184342A/xx unknown
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- 1977-06-13 YU YU1469/77A patent/YU40166B/xx unknown
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- 1977-06-16 JP JP7157277A patent/JPS5318578A/ja active Granted
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- 1977-06-23 AR AR268164A patent/AR216080A1/es active
- 1977-06-23 FR FR7719250A patent/FR2372821A1/fr active Granted
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- 1977-07-14 BG BG7742606A patent/BG28988A4/xx unknown
- 1977-07-20 RO RO7799825A patent/RO78951A2/ro unknown
- 1977-07-20 RO RO7799826A patent/RO78952A/ro unknown
- 1977-07-20 RO RO7799830A patent/RO78953A/ro unknown
- 1977-07-20 RO RO7791106A patent/RO74367A/ro unknown
- 1977-07-21 SU SU772508256A patent/SU955859A3/ru active
- 1977-07-21 GB GB30759/77A patent/GB1538371A/en not_active Expired
- 1977-07-21 HU HU82156A patent/HU186026B/hu unknown
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- 1977-07-21 HU HU82155A patent/HU185686B/hu unknown
- 1977-07-21 PL PL1977215007A patent/PL115496B1/pl unknown
- 1977-07-21 PL PL21500877A patent/PL215008A1/xx unknown
- 1977-07-21 GB GB4242/78A patent/GB1538374A/en not_active Expired
- 1977-07-21 PL PL1977199798A patent/PL115586B1/pl unknown
- 1977-07-21 PL PL1977215006A patent/PL115497B1/pl unknown
- 1977-07-21 GB GB4243/78A patent/GB1538375A/en not_active Expired
- 1977-07-21 GB GB4240/78A patent/GB1538372A/en not_active Expired
- 1977-07-21 GB GB4241/78A patent/GB1538373A/en not_active Expired
- 1977-07-21 HU HU77PI584A patent/HU180040B/hu unknown
- 1977-07-29 IE IE587/79A patent/IE45645B1/en not_active IP Right Cessation
- 1977-07-29 IE IE1587/77A patent/IE45641B1/en not_active IP Right Cessation
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- 1977-07-29 IE IE585/79A patent/IE45643B1/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 PH20746A patent/PH13926A/en unknown
- 1978-02-03 PH PH20745A patent/PH15185A/en unknown
- 1978-05-25 JP JP6281778A patent/JPS5436266A/ja active Pending
- 1978-05-25 JP JP6281978A patent/JPS5436268A/ja active Pending
- 1978-05-25 JP JP6282178A patent/JPS5436270A/ja active Granted
- 1978-05-25 JP JP53062820A patent/JPS5814433B2/ja not_active Expired
- 1978-05-25 JP JP6282278A patent/JPS5436271A/ja active Granted
- 1978-05-25 JP JP6281878A patent/JPS5436267A/ja active Granted
- 1978-06-07 CS CS783706A patent/CS203923B2/cs unknown
- 1978-06-07 CS CS783705A patent/CS203922B2/cs unknown
- 1978-06-13 ES ES470743A patent/ES470743A1/es not_active Expired
- 1978-06-13 ES ES470746A patent/ES470746A1/es not_active Expired
- 1978-06-13 ES ES470745A patent/ES470745A1/es not_active Expired
- 1978-06-13 ES ES470744A patent/ES470744A1/es not_active Expired
- 1978-07-05 SU SU782631651A patent/SU1015826A3/ru 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/de not_active IP Right Cessation
- 1980-03-06 AT AT0124480A patent/AT363470B/de not_active IP Right Cessation
- 1980-10-24 CA CA363,273A patent/CA1110254A/en not_active Expired
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1981
- 1981-02-20 CH CH116181A patent/CH626358A5/fr not_active IP Right Cessation
- 1981-02-20 CH CH116081A patent/CH626357A5/fr not_active IP Right Cessation
- 1981-07-02 HK HK303/81A patent/HK30381A/xx unknown
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1982
- 1982-01-29 SE SE8200519A patent/SE445042B/sv not_active IP Right Cessation
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- 1982-06-03 NO NO821849A patent/NO150559C/no unknown
- 1982-06-03 NO NO821851A patent/NO150560C/no unknown
- 1982-06-03 NO NO821848A patent/NO150043C/no unknown
- 1982-06-03 NO NO821850A patent/NO821850L/no unknown
- 1982-06-03 NO NO821847A patent/NO150042C/no unknown
- 1982-12-07 YU YU02703/82A patent/YU270382A/xx unknown
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1983
- 1983-05-16 FI FI831702A patent/FI72720C/fi not_active IP Right Cessation
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- 1983-11-18 NO NO834236A patent/NO151365C/no unknown
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1986
- 1986-07-09 DK DK326186A patent/DK154079C/da active
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