NO146572B - PROCEDURE FOR PREPARING BETA PYRONS - Google Patents
PROCEDURE FOR PREPARING BETA PYRONS Download PDFInfo
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- NO146572B NO146572B NO803832A NO803832A NO146572B NO 146572 B NO146572 B NO 146572B NO 803832 A NO803832 A NO 803832A NO 803832 A NO803832 A NO 803832A NO 146572 B NO146572 B NO 146572B
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- 238000000034 method Methods 0.000 title claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 125000003342 alkenyl group Chemical group 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- MALOBWMOORWUQW-UHFFFAOYSA-N 4h-pyran-3-one Chemical class O=C1COC=CC1 MALOBWMOORWUQW-UHFFFAOYSA-N 0.000 claims 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 15
- XPCTZQVDEJYUGT-UHFFFAOYSA-N 3-hydroxy-2-methyl-4-pyrone Chemical compound CC=1OC=CC(=O)C=1O XPCTZQVDEJYUGT-UHFFFAOYSA-N 0.000 description 14
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 14
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 12
- 239000000243 solution Substances 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 8
- 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 7
- HYMLWHLQFGRFIY-UHFFFAOYSA-N Maltol Natural products CC1OC=CC(=O)C1=O HYMLWHLQFGRFIY-UHFFFAOYSA-N 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 7
- 235000019253 formic acid Nutrition 0.000 description 7
- 229940043353 maltol Drugs 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- -1 methyl glycosides Chemical class 0.000 description 4
- HTSGKJQDMSTCGS-UHFFFAOYSA-N 1,4-bis(4-chlorophenyl)-2-(4-methylphenyl)sulfonylbutane-1,4-dione Chemical compound C1=CC(C)=CC=C1S(=O)(=O)C(C(=O)C=1C=CC(Cl)=CC=1)CC(=O)C1=CC=C(Cl)C=C1 HTSGKJQDMSTCGS-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 239000000284 extract Substances 0.000 description 3
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- VEYIMQVTPXPUHA-UHFFFAOYSA-N 3-hydroxypyran-4-one Chemical compound OC1=COC=CC1=O VEYIMQVTPXPUHA-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-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
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 235000011089 carbon dioxide Nutrition 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- 229940093503 ethyl maltol Drugs 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 238000001030 gas--liquid chromatography Methods 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 239000002304 perfume Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 238000003756 stirring 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
- PYOKUURKVVELLB-UHFFFAOYSA-N trimethyl orthoformate Chemical compound COC(OC)OC PYOKUURKVVELLB-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
- JKTCBAGSMQIFNL-UHFFFAOYSA-N 2,3-dihydrofuran Chemical compound C1CC=CO1 JKTCBAGSMQIFNL-UHFFFAOYSA-N 0.000 description 1
- WXFWXFIWDGJRSC-UHFFFAOYSA-N 2,5-dimethoxy-2,5-dihydrofuran Chemical class COC1OC(OC)C=C1 WXFWXFIWDGJRSC-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 241000723343 Cichorium Species 0.000 description 1
- 235000007542 Cichorium intybus Nutrition 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 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
- 239000002841 Lewis acid Substances 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
- CVQUWLDCFXOXEN-UHFFFAOYSA-N Pyran-4-one Chemical compound O=C1C=COC=C1 CVQUWLDCFXOXEN-UHFFFAOYSA-N 0.000 description 1
- 241000220317 Rosa Species 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 238000005904 alkaline hydrolysis reaction Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 150000001719 carbohydrate derivatives Chemical class 0.000 description 1
- 229920001429 chelating resin Polymers 0.000 description 1
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 1
- 229940106681 chloroacetic acid Drugs 0.000 description 1
- 229960004106 citric acid Drugs 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000000686 essence Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 229930182470 glycoside Natural products 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
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 229940116315 oxalic acid Drugs 0.000 description 1
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000003586 protic polar solvent Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007921 spray 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
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 description 1
- 238000004809 thin layer chromatography Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/26—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D307/30—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/32—Oxygen atoms
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L27/00—Spices; Flavouring agents or condiments; Artificial sweetening agents; Table salts; Dietetic salt substitutes; Preparation or treatment thereof
- A23L27/20—Synthetic spices, flavouring agents or condiments
- A23L27/205—Heterocyclic compounds
- A23L27/2052—Heterocyclic compounds having oxygen or sulfur as the only hetero atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/60—Two oxygen atoms, e.g. succinic anhydride
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
- C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
- C07D493/04—Ortho-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B9/00—Essential oils; Perfumes
- C11B9/0069—Heterocyclic compounds
- C11B9/0073—Heterocyclic compounds containing only O or S as heteroatoms
- C11B9/008—Heterocyclic compounds containing only O or S as heteroatoms the hetero rings containing six atoms
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nutrition Science (AREA)
- Food Science & Technology (AREA)
- Polymers & Plastics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Epoxy Compounds (AREA)
- Saccharide Compounds (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
- Pyrane Compounds (AREA)
- Plural Heterocyclic Compounds (AREA)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
- Compounds Of Unknown Constitution (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
- Pyridine Compounds (AREA)
- Picture Signal Circuits (AREA)
- Electroluminescent Light Sources (AREA)
- Transforming Electric Information Into Light Information (AREA)
Description
Denne oppfinnelse angår en fremgangsmåte for fremstilling av Ø-pyroner med formelen: hvor R er hydrogen, lavere alkyl med 1 til 6 karbonatomer, lavere alkenyl med 2 til 6 karbonatomer, fenyl eller benzyl, og R' er lavere alkyl med 1 til 6 karbonatomer, og den karakteriseres ved at en forbindelse med formelen: This invention relates to a process for the production of Ø-pyrones with the formula: where R is hydrogen, lower alkyl with 1 to 6 carbon atoms, lower alkenyl with 2 to 6 carbon atoms, phenyl or benzyl, and R' is lower alkyl with 1 to 6 carbon atoms , and it is characterized by the fact that a compound with the formula:
hvor R og R<1> er som angitt ovenfor, omsettes med en tilnærmet vannfri syre med en pKa på 4 eller lavere. where R and R<1> are as indicated above, is reacted with an approximately anhydrous acid with a pKa of 4 or lower.
Fra Tetrahedron, bind 27 (1971), s 1973-1996 er det kjent From Tetrahedron, volume 27 (1971), pp 1973-1996 it is known
en fremgangsmåte for omvandling av furanderivater over 2,3-didesoksy-DL-alk-2-enopyranos-4-uloser til metyl-2,3-didesoksy-DL-alk-2-enopyranosider, hvor først f.eks. furfuryl-alkohol eller 1-(2-furyl)-etanol ved behandling med brom i metanol omdannes til det tilsvarende 2,5-dimetoksy-2,5-dihydro-furan-derivat, som derefter hydrolyseres med fortynnet svovelsyre til 2,3-didesoksy-DL-pent-2-enopyranos-4-ulose resp. 2,3,6-tridesoksy-DL-heks-2-enopyranos-4-ulose. Disse forbindelser har en ved hydrolysen dannet fri hydroksylgruppe som før videre omsetning igjen må forestres ved behandling med metylortoformiat i nærvær av Lewis syrer. Ved denne kjente fremgangsmåte oppnås således fra 2,5-dimetoksy-2,5-dihydro-furan-derivater i to trinn, dvs. ved hydrolyse og derefter fornyet forestring, slike metylglykosider som ifølge foreliggende oppfinnelse dannes direkte i ett trinn under anvendelse av en tilnærmet vannfri sterk syre. Foreliggende fremgangsmåte er, fordi den kan utføres i ett trinn, enklere enn den kjente a method for converting furan derivatives via 2,3-dideoxy-DL-alk-2-enopyranos-4-uloses to methyl-2,3-dideoxy-DL-alk-2-enopyranosides, where first e.g. furfuryl alcohol or 1-(2-furyl)ethanol on treatment with bromine in methanol is converted to the corresponding 2,5-dimethoxy-2,5-dihydro-furan derivative, which is then hydrolyzed with dilute sulfuric acid to 2,3- dideoxy-DL-pent-2-enopyranos-4-ulose resp. 2,3,6-tridesoxy-DL-hex-2-enopyranos-4-ulose. These compounds have a free hydroxyl group formed during the hydrolysis which, before further reaction, must again be esterified by treatment with methyl orthoformate in the presence of Lewis acids. In this known method, such methyl glycosides as according to the present invention are formed directly in one step using a nearly anhydrous strong acid. The present method is, because it can be carried out in one step, simpler than the known one
fremgangsmåte, og dessuten kan den også utføres med vesentlig bedre utbytter på over 80%, mens det bare i annet trinn av den kjente fremgangsmåte oppnås et utbytte på høyst 45%. Dannelse av et tilsvarende hydroksylderivat, som er meget ubestandig, unngås. method, and furthermore it can also be carried out with significantly better yields of over 80%, while only in the second step of the known method a yield of at most 45% is achieved. Formation of a corresponding hydroxyl derivative, which is very unstable, is avoided.
Dihydrofuran-utgangsmaterialene med formel II er enten kjente forbindelser, f.eks. fra US-patentskrift nr. 2.714.576, Acta. Chem. Scand., 6, 545 (1952), Annalen der Chemie, 516, The dihydrofuran starting materials of formula II are either known compounds, e.g. from US Patent No. 2,714,576, Acta. Chem. Scand., 6, 545 (1952), Annalen der Chemie, 516,
231 (1935), Acta. Chem. Scand., 9, 17 (1955) og Tetrahedron, 231 (1935), Acta. Chem. Scand., 9, 17 (1955) and Tetrahedron,
27, 1973-1996 (1971), eller de kan fremstilles ved de metoder som allerede er beskrevet, f.eks. en forbindelse med formel II hvor R er etyl. 27, 1973-1996 (1971), or they can be produced by the methods already described, e.g. a compound of formula II wherein R is ethyl.
Behandlingen av forbindelsen II med en sterk organisk syre er ny, og den frembringer det ønskede 6-alkoksy-derivat I direkte med høyt utbytte og unngår dannelse av det tilsvarende hydroksyderivat som er svært ustabilt til ytterligere om-setninger. Forbindelsen II blir bragt i kontakt med en syre som fortrinnsvis i alt vesentlig er vannfri, selv om det er virkelig tjenlig med nærvær av et protisk oppløsningsmiddel, The treatment of compound II with a strong organic acid is new, and it produces the desired 6-alkoxy derivative I directly in high yield and avoids the formation of the corresponding hydroxy derivative which is very unstable to further reactions. The compound II is brought into contact with an acid which is preferably substantially anhydrous, although the presence of a protic solvent is really useful,
så som en alkohol, eller en liten mengde vann. Ved å følge denne behandling blir produktet i en renhetstilstand som er egnet for omdannelse til forbindelsen I separert fra det sure medium ved konvensjonell ekstraheringsteknikk. Selv om det er foretrukket med maursyre og trifluoreddiksyre, vil enhver syre med en pKa på tilnærmet 4 eller lavere omdanne forbindelsen II til den ønskede forbindelse I. Andre egnede organiske syrer innbefatter p-toluensulfonsyre, metansulfonsyre, sitronsyre, oksalsyre og kloreddiksyre, og egnede mineralsyrer innbefatter svovelsyre, saltsyre og fosforsyre. Sure harpikser, så som "Amberlite GC-120" og "Dowex 50W", kan også anvendes. such as an alcohol, or a small amount of water. Following this treatment, the product in a state of purity suitable for conversion to compound I is separated from the acidic medium by conventional extraction techniques. Although formic acid and trifluoroacetic acid are preferred, any acid with a pKa of approximately 4 or less will convert compound II to the desired compound I. Other suitable organic acids include p-toluenesulfonic acid, methanesulfonic acid, citric acid, oxalic acid, and chloroacetic acid, and suitable mineral acids includes sulfuric acid, hydrochloric acid and phosphoric acid. Acidic resins, such as "Amberlite GC-120" and "Dowex 50W", can also be used.
Ø-pyronene kan utnyttes ved fremstilling av y-pyroner, f.eks. maltol. Maltol er en naturlig forekommende substans som man finner i bark av unge lerketrær, i furunåler og i sikori. Den tidlige kommersielle produksjon var fra den destruktive destillering av tre. Syntese av maltol fra. 3-hydroksy-2-(1-piperidylmetyl)-1,4-pyron ble omtalt av Spielman og Freifelder i J. Am. Chem. Soc. , 69^, 2908 (1947). Schenck og Spielman, J. Am. Chem. Soc, 67, 2276 (1945), erholdt maltol ved alkalisk hydrolyse av streptomycin-salter. Chawla The ø-pyrones can be utilized in the production of y-pyrones, e.g. maltol. Maltol is a naturally occurring substance found in the bark of young larch trees, in pine needles and in chicory. The early commercial production was from the destructive distillation of wood. 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, 2276 (1945), obtained maltol by alkaline hydrolysis of streptomycin salts. Chawla
og McGonigal, J. Org. Chem., 39, 3281 (1974), og Lichtenthaler og Heidel, Angew. Chem., 81, 999 (1969), skrev om syntese av maltol fra beskyttende karbohydrat-derivater. and McGonigal, J. Org. Chem., 39, 3281 (1974), and Lichtenthaler and Heidel, Angew. Chem., 81, 999 (1969), wrote on the synthesis of maltol from protective carbohydrate derivatives.
Synteser av y-pyroner, så som pyromekonsyre, maltol, etylmaltol og andre 2-substituerte-3-hydroksy-y-pyroner, er beskrevet i US-patenter 3.130.204, 3.133.089, 3.140.239, 3.159.652, 3.376.317, 3.468.915, 3.440.183 og 3.446.629. Syntheses of γ-pyrones, such as pyromeconic acid, maltol, ethyl maltol and other 2-substituted-3-hydroxy-γ-pyrones, are described in US Patents 3,130,204, 3,133,089, 3,140,239, 3,159,652, 3,376 .317, 3,468,915, 3,440,183 and 3,446,629.
Maltol og etylmaltol gir en økning i smak og aroma til en rekke matprodukter. Dessuten anvendes disse materialer som bestanddeler i parfymer og essenser. 2-alkenylpyromekonsyrene omtalt i US-patent 3.644.635 og 2-arylmetylpyromekonsyrene beskrevet i US-patent 3.365.469 inhiberer vekst av bakterier og sopp og er nyttige til å gi øket smak og aroma i mat og drikke og øket aroma i parfymer. Maltol and ethyl maltol give an increase in taste and aroma to a number of food products. These materials are also used as ingredients in perfumes and essences. The 2-alkenylpyromeconic acids mentioned in US patent 3,644,635 and the 2-arylmethylpyromeconic acids described in US patent 3,365,469 inhibit the growth of bacteria and fungi and are useful for giving increased taste and aroma in food and drink and increased aroma in perfumes.
Eksempel 1 Example 1
Til en 2-liters, 3-halset kolbe med rund bunn og forsynt med en magnetisk rører, dråpetrakt og et termometer, ble det satt 400 ml maursyre og 20 ml metanol. Til denne oppløsning ble det satt en oppløsning av mellomprodukt II (R = CH3, R'=CH3) To a 2-liter, 3-necked round-bottom flask equipped with a magnetic stirrer, dropping funnel and a thermometer, 400 ml of formic acid and 20 ml of methanol were added. To this solution was added a solution of intermediate II (R = CH3, R'=CH3)
(104,4 g, 0,6 mol) i 40 ml metanol. Til den dråpevise til-setning var det nødvendig med 15 minutter. Reaksjonsblandingen ble hellet inn i 1 liter vann og ekstrahert 3 ganger med 500 ml porsjoner av kloroform. De samlede kloroform-væsker ble vasket med en vandig oppløsning av natriumbikarbonat og med saltoppløsning. Kloroform-oppløsningen ble inndampet til et urenset utbytte på 76 g (89%) av forbindelse I (R = CH3'(104.4 g, 0.6 mol) in 40 mL of methanol. 15 minutes were required for the dropwise addition. The reaction mixture was poured into 1 liter of water and extracted 3 times with 500 ml portions of chloroform. The combined chloroform liquids were washed with an aqueous solution of sodium bicarbonate and with saline. The chloroform solution was evaporated to a crude yield of 76 g (89%) of compound I (R = CH3'
R' = CH^) som et lysebrunt produkt. Det urensede materiale R' = CH^) as a light brown product. The impure material
kan anvendes som sådant eller destilleres ved et trykk på 2 mm, 50-52°C [82-85°/30 mm, Tetrahedron, 27, 1973 (1971)]. can be used as such or distilled at a pressure of 2 mm, 50-52°C [82-85°/30 mm, Tetrahedron, 27, 1973 (1971)].
Utbytte 61,6 g (69%). Yield 61.6 g (69%).
Eksempel 2 Example 2
Metoden fra eksempel 1 ble gjentatt med analogt mellomprodukt II (R = H, R<1> = CH3) for å oppnå forbindelse I (R = H, R" = CH3) , k.p. 60-66°/14 mm [76-81°/23 mm, Tetrahedron, 2J7, 1973 (1971)]. Utbytte av udestillert produkt 45%. The method from Example 1 was repeated with analogous intermediate II (R = H, R<1> = CH3) to obtain compound I (R = H, R" = CH3), b.p. 60-66°/14 mm [76-81 °/23 mm, Tetrahedron, 2J7, 1973 (1971)].Yield of undistilled product 45%.
Eksempel 3 Example 3
Fremgangsmåten fra eksempel 1 ble gjentatt med mellomprodukt II (R = CH2CH3, R' = CH3) for å oppnå forbindelse I The procedure from Example 1 was repeated with intermediate II (R = CH2CH3, R' = CH3) to obtain compound I
(R = CH2CH3, R' = CH3), k.p. 79-80°/14 mm. Utbytte av udestillert produkt 86%, og utbytte av destillert produkt 57%. (R = CH2CH3, R' = CH3), b.p. 79-80°/14mm. Yield of undistilled product 86%, and yield of distilled product 57%.
Eksempel 4 Example 4
I en 3-halset kolbe med rund bunn og forsynt med en til-setningstrakt, et lavtemperatur-termometer og en rørestang ble det dannet en oppløsning av 5,0 g (0,02 9 mol) av mellomprodukt II (R = CH3, R' = CH3) i dietyleter (10 ml), og opp-løsningen ble avkjølt til -40°C. Til denne oppløsning ble det dråpevis satt 1,6 ml konsentrert svovelsyre og den svarte blanding ble rørt i 5 minutter ved -40°C, hellet inn i vann og det ønskede produkt I (R = CH3, R' = CH3) ble isolert ved metoden fra eksempel 1. Utbyttet av udestillert produkt var 3,64 g (89%) og av destillert produkt 2,35 g (57%). In a 3-neck round-bottom flask equipped with an addition funnel, a low-temperature thermometer and a stirring bar, a solution of 5.0 g (0.029 mol) of intermediate II (R = CH3, R ' = CH 3 ) in diethyl ether (10 mL), and the solution was cooled to -40°C. To this solution 1.6 ml of concentrated sulfuric acid was added dropwise and the black mixture was stirred for 5 minutes at -40°C, poured into water and the desired product I (R = CH3, R' = CH3) was isolated by the method from example 1. The yield of undistilled product was 3.64 g (89%) and of distilled product 2.35 g (57%).
I alt vesentlig samme resultater ble oppnådd ved å erstatte svovelsyre med saltsyre eller fosforsyre. Substantially the same results were obtained by replacing sulfuric acid with hydrochloric or phosphoric acid.
Eksempel 5 Example 5
I en polyetylenbeholder, under nitrogen, ble en oppløsning av mellomprodukt II (R = CH3, R<1> = CH3), 7,2 g, i 15 ml aceton omrørt mens den ble holdt nedsenket i et isbad ved -10°C. I løpet av ca. 1-2 minutter ble en kold (-10°C) oppløsning av flussyre (3 ml) i 5 ral aceton tilsatt fra en polyetylen-spruteflaske. Reaksjonsblandingen ble en brun oppløsning kort efter tilsetningen, og omsetningen ble ved tynnskikt-kromatografi funnet å være tilnærmet fullstendig.efter 20-30 minutter ved denne temperatur (-10°C). Under omrøring i totalt 2 timer steg temperaturen i isbadet langsomt til 16°C. Reaksjonsblandingen ble fortynnet med 200 ml metylenklorid, vasket med 100 ml vann og derefter med 50 ml vann. De samlede vannekstrakter ble vasket med 50 ml frisk metylenklorid. De samlede metylenkloridekstrakter ble omrørt kraftig med 200 ml vann, og pH-verdien ble regulert til 7,6 med 0,5N natrium-hydroksydoppløsning. Lagene ble adskilt, og den vandige del ble vasket med 50 ml metylenklorid. Metylenkloridekstraktene ble samlet og tørret over vannfritt natriumsulfat som det var satt en liten mengde aktivt kull til. Blandingen ble filtrert og konsentrert til en gul olje, 7,43 g. Den urensede olje ble destillert under høyvakuum i en kulerørovn ved nedsenkning av kolben inneholdende den urensede olje ved 110°C. Det destillerte materiale ble oppsamlet i en ballong som ble avkjølt ved å pakke den i bomull dyppet i tørris/aceton ved -72°C. Vekten av det destillerte oljeprodukt I (R = CH3, R<1> = CH3) som ble oppnådd (produktet krystalliserte ved avkjøling med tørris/aceton) var 5,34 g. In a polyethylene container, under nitrogen, a solution of intermediate II (R = CH 3 , R<1 > = CH 3 ), 7.2 g, in 15 mL of acetone was stirred while immersed in an ice bath at -10°C. During approx. 1-2 minutes, a cold (-10°C) solution of hydrofluoric acid (3 mL) in 5 mL of acetone was added from a polyethylene spray bottle. The reaction mixture became a brown solution shortly after the addition, and the reaction was found to be almost complete by thin-layer chromatography after 20-30 minutes at this temperature (-10°C). While stirring for a total of 2 hours, the temperature in the ice bath rose slowly to 16°C. The reaction mixture was diluted with 200 ml of methylene chloride, washed with 100 ml of water and then with 50 ml of water. The combined water extracts were washed with 50 ml of fresh methylene chloride. The combined methylene chloride extracts were stirred vigorously with 200 ml of water, and the pH value was adjusted to 7.6 with 0.5N sodium hydroxide solution. The layers were separated and the aqueous portion was washed with 50 ml of methylene chloride. The methylene chloride extracts were collected and dried over anhydrous sodium sulfate to which a small amount of activated charcoal had been added. The mixture was filtered and concentrated to a yellow oil, 7.43 g. The crude oil was distilled under high vacuum in a bubble tube furnace by immersing the flask containing the crude oil at 110°C. The distilled material was collected in a balloon which was cooled by wrapping it in cotton dipped in dry ice/acetone at -72°C. The weight of the distilled oil product I (R = CH3, R<1> = CH3) which was obtained (the product crystallized on cooling with dry ice/acetone) was 5.34 g.
Eksempel 6 Example 6
Fremgangsmåten ifølge eksempel 1 ble gjentatt med mellomprodukt II (R = CH3, R' = isopropyl) for å danne forbindelse I (R = CH3, R' = isopropyl). Utbyttet av udestillert produkt var 67% av det teoretiske, PNMR/CDCl3/6 6,75 (H, d av d), 6,05 The procedure of Example 1 was repeated with intermediate II (R = CH 3 , R' = isopropyl) to form compound I (R = CH 3 , R' = isopropyl). The yield of undistilled product was 67% of the theoretical, PNMR/CDCl3/6 6.75 (H, d of d), 6.05
(1H, d) , 5,25 (1H, d) , 4,55 (1H, q) , 3,9-4,3 (1H, m), (1H, d) , 5.25 (1H, d) , 4.55 (1H, q) , 3.9-4.3 (1H, m),
1,1-1,6 (9H, m). 1.1-1.6 (9H, m).
Eksempel 7 Example 7
Fremgangsmåten ifølge eksempel 6 ble gjentatt under anvendelse av trifluoreddiksyre istedenfor maursyre. Utbyttet av produktet var 76%, PNMR som ovenfor. The procedure according to Example 6 was repeated using trifluoroacetic acid instead of formic acid. The yield of the product was 76%, PNMR as above.
Fremgangsmåten ifølge eksempel 3 ble gjentatt under anvendelse av trifluoreddiksyre istedenfor maursyre. Utbyttet av udestillert produkt var det teoretiske. Utbyttet av destillert produkt var 37%, k.p. som ovenfor. The procedure according to example 3 was repeated using trifluoroacetic acid instead of formic acid. The yield of undistilled product was the theoretical. The yield of distilled product was 37%, k.p. as above.
Fremgangsmåten ifølge eksempel 1 ble gjentatt under anvendelse av 5% vekt/volum sitronsyre i maursyre istedenfor maursyre. Utbyttet av udestillert produkt var 87%, og utbyttet ved gass-væske-kromatografi-måling var 7 9%. The procedure according to example 1 was repeated using 5% weight/volume citric acid in formic acid instead of formic acid. The yield of undistilled product was 87%, and the yield by gas-liquid chromatography measurement was 79%.
Fremgangsmåten ifølge eksempel 1 ble gjentatt under anvendelse av trifluoreddiksyre istedenfor maursyre. Utbyttet av udestillert produkt var 88%, og utbyttet ved gass-væske-kromatograf i var 83%. The procedure according to example 1 was repeated using trifluoroacetic acid instead of formic acid. The yield of undistilled product was 88%, and the yield by gas-liquid chromatography was 83%.
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| Application Number | Priority Date | Filing Date | Title |
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| US60845275A | 1975-08-28 | 1975-08-28 |
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| NO762449A NO145952C (en) | 1975-08-28 | 1976-07-13 | PROCEDURE FOR MANUFACTURING GAMMA PYRONS |
| NO803831A NO147245C (en) | 1975-08-28 | 1980-12-17 | COMPOUNDS FOR USE AS BASIC MATERIAL IN THE PREPARATION OF ETHYL MALTOL |
| NO803832A NO146572C (en) | 1975-08-28 | 1980-12-17 | PROCEDURE FOR PREPARING BETA PYRONS |
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| NO762449A NO145952C (en) | 1975-08-28 | 1976-07-13 | PROCEDURE FOR MANUFACTURING GAMMA PYRONS |
| NO803831A NO147245C (en) | 1975-08-28 | 1980-12-17 | COMPOUNDS FOR USE AS BASIC MATERIAL IN THE PREPARATION OF ETHYL MALTOL |
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| CA1095921A (en) * | 1976-08-02 | 1981-02-17 | Thomas M. Brennan | Preparation of gamma-pyrones |
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| US3476778A (en) * | 1966-05-16 | 1969-11-04 | Monsanto Co | Gamma-pyrone synthesis |
| US3491122A (en) * | 1966-09-14 | 1970-01-20 | Monsanto Co | Synthesis of 4-pyrones |
| JPS5145565B1 (en) * | 1968-10-12 | 1976-12-04 | ||
| JPS5212166A (en) * | 1975-07-17 | 1977-01-29 | Tatsuya Shono | Process for preparation of 4-pyron derivatives |
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