SE444564B - 4-HALOGENE DIHYDROPYRANE COMPOUNDS FOR USE AS INTERMEDIATE IN THE PREPARATION OF GAMMA PYRONS AND PROCEDURE FOR PREPARING THEREOF - Google Patents
4-HALOGENE DIHYDROPYRANE COMPOUNDS FOR USE AS INTERMEDIATE IN THE PREPARATION OF GAMMA PYRONS AND PROCEDURE FOR PREPARING THEREOFInfo
- Publication number
- SE444564B SE444564B SE8200520A SE8200520A SE444564B SE 444564 B SE444564 B SE 444564B SE 8200520 A SE8200520 A SE 8200520A SE 8200520 A SE8200520 A SE 8200520A SE 444564 B SE444564 B SE 444564B
- Authority
- SE
- Sweden
- Prior art keywords
- carbon atoms
- bromine
- hydrogen
- formula
- preparation
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 8
- 238000002360 preparation method Methods 0.000 title claims description 7
- BUDQDWGNQVEFAC-UHFFFAOYSA-N Dihydropyran Chemical class C1COC=CC1 BUDQDWGNQVEFAC-UHFFFAOYSA-N 0.000 title 1
- 125000004432 carbon atom Chemical group C* 0.000 claims description 15
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 13
- 229910052794 bromium Chemical group 0.000 claims description 13
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- 229910052801 chlorine Inorganic materials 0.000 claims description 11
- 239000000460 chlorine Substances 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group 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
- 238000006243 chemical reaction Methods 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- CODNYICXDISAEA-UHFFFAOYSA-N bromine monochloride Chemical compound BrCl CODNYICXDISAEA-UHFFFAOYSA-N 0.000 claims description 6
- 239000007800 oxidant agent Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 claims description 5
- 230000001590 oxidative effect Effects 0.000 claims description 5
- DKSMCEUSSQTGBK-UHFFFAOYSA-N bromous acid Chemical compound OBr=O DKSMCEUSSQTGBK-UHFFFAOYSA-N 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
- 150000002576 ketones Chemical class 0.000 claims description 3
- 150000002825 nitriles Chemical class 0.000 claims description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 239000000543 intermediate Substances 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- 238000011065 in-situ storage 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
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- XPCTZQVDEJYUGT-UHFFFAOYSA-N 3-hydroxy-2-methyl-4-pyrone Chemical compound CC=1OC=CC(=O)C=1O XPCTZQVDEJYUGT-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
- 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
- -1 ethyl compound Chemical class 0.000 description 2
- 229940093503 ethyl maltol Drugs 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 239000000499 gel Substances 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-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
- 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
- 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
- 241000233866 Fungi Species 0.000 description 1
- HYMLWHLQFGRFIY-UHFFFAOYSA-N Maltol Natural products CC1OC=CC(=O)C1=O HYMLWHLQFGRFIY-UHFFFAOYSA-N 0.000 description 1
- GXCLVBGFBYZDAG-UHFFFAOYSA-N N-[2-(1H-indol-3-yl)ethyl]-N-methylprop-2-en-1-amine Chemical compound CN(CCC1=CNC2=C1C=CC=C2)CC=C GXCLVBGFBYZDAG-UHFFFAOYSA-N 0.000 description 1
- 229910019093 NaOCl Inorganic materials 0.000 description 1
- 235000019502 Orange oil Nutrition 0.000 description 1
- CVQUWLDCFXOXEN-UHFFFAOYSA-N Pyran-4-one Chemical compound O=C1C=COC=C1 CVQUWLDCFXOXEN-UHFFFAOYSA-N 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
- 239000011260 aqueous acid Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000001246 bromo group Chemical group Br* 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
- 125000004122 cyclic group Chemical group 0.000 description 1
- 239000003623 enhancer 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
- 235000013355 food flavoring agent Nutrition 0.000 description 1
- 239000007789 gas Substances 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
- 229940043353 maltol Drugs 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils 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
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 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
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 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)
- Saccharide Compounds (AREA)
- Furan Compounds (AREA)
- Picture Signal Circuits (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Transforming Electric Information Into Light Information (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
- Processing Of Color Television Signals (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
- Seasonings (AREA)
- Control Of El Displays (AREA)
Description
_., ,...,.,,..W,.,..,,Ww , 8 2 0 0 5 2 0 ~ 8 2 Synteser av gamma-pyroner såsom pyromekonsyra, maltol, etyl~ maltol och andra 2-substituerade 3-hydroxi-gamma-pyroner be- skrives i de amerikanska patentskrifterna 3.130.204; 3.133.089; 3.140.239; 3.159.652; 3.365.469; 3.376.317; 3.468.915; 3.440.183; och 3.446.629. Synthesis of gamma-pyrones such as pyromeconic acid, maltol, ethyl-maltol and other 2-. substituted 3-hydroxy-gamma-pyrones are described in U.S. Pat. Nos. 3,130,204; 3,133,089; 3,140,239; 3,159,652; 3,365,469; 3,376,317; 3,468,915; 3,440,183; and 3,446,629.
Maltol och etylmaltol förstärker aromen och smaken hos en mång- fald olikartade livsmedelsprodukter. Dessutom användes dessa föreningar såsom komponenter i parfymer och essenser. 2-alkenyl~ pyromekonsyrorna rapporteras i den amerikanska patentskriften 3.644.635 och 2-arylmetylpyromekonsyrorna beskrives i den ameri- kanska patentskriften 3.365.469, vilka inhiberar tillväxt av bakterier och svampar och är användbara såsom arom- och smak- förstärkande medel i livsmedel och drycker och såsom luktför- stärkande medel i parfymer.Malt oil and ethyl maltol enhance the aroma and taste of a variety of different food products. In addition, these compounds were used as components in perfumes and essences. The 2-alkenyl pyromeconic acids are reported in U.S. Pat. No. 3,644,635 and the 2-arylmethylpyromeconic acids are described in U.S. Pat. No. 3,365,469, which inhibit the growth of bacteria and fungi and are useful as flavoring and flavoring agents in foods and beverages. and as odor enhancers in perfumes.
Stampatentet 433 079 avser ett förfarande för framställning av ett 3-hydroxi-4-pyronderivat genom syrahydrolys av ett 3-pyronderivat, vilket utmärkes av att en gamma-pyron, som har formeln framställes, vari R är väte eller alkyl med l-4 kolatomer och R"' är väte eller alkyl med l-4 kolatomer, med utgång från en 4-halo-dihydropyran med formeln (II) eller en 6,6'~oxibisjÄ- halo-2H-pyran-3(6H)-on] med formeln (V): X ' X \ x /'O eller O*\ \\\ (V) 8200520-8 vari R och R'f' har angiven betydelse och R' är väte, alkyl med l-4 kolatomer eller -COR", vari R" är metyl, etyl eller fenyl och X är klor eller brom.The parent patent 433 079 relates to a process for the preparation of a 3-hydroxy-4-pyrone derivative by acid hydrolysis of a 3-pyrone derivative, which is characterized in that a gamma-pyrone having the formula is prepared in which R is hydrogen or alkyl having 1-4 carbon atoms and R "'is hydrogen or alkyl of 1-4 carbon atoms, starting from a 4-halo-dihydropyran of formula (II) or a 6,6'-oxybis-halo-2H-pyran-3 (6H) -one] with the formula (V): X 'X \ x /' O or O * \ \\\ (V) 8200520-8 wherein R and R'f 'have the meaning given and R' is hydrogen, alkyl having 1-4 carbon atoms or -COR ", wherein R" is methyl, ethyl or phenyl and X is chlorine or bromine.
Den syra som erfordras för hydrolysen kan sättas till reaktions- iblandningen, t.ex. genom upplösning av intermediatföreningen med formeln (II) eller (V) i en vattenhaltig oorganisk eller organisk syra före upphettning; eller alternativt kan syran. bildas in situ under framställningen av intermediaten såsom nedan beskrives.The acid required for the hydrolysis can be added to the reaction mixture, e.g. by dissolving the intermediate compound of formula (II) or (V) in an aqueous inorganic or organic acid before heating; or alternatively the acid may. formed in situ during the preparation of the intermediates as described below.
Den intermediära föreningen enligt formeln (II) ovan kan framställas genom reaktion av en förening, som har formeln //I w ¿;O RIII . The intermediate compound of formula (II) above can be prepared by reacting a compound having the formula // I w ¿; O RIII.
R'O/ ~O- R vari R, R' och R"' har ovan angiven betydelse, i ett lösnings- medel vid en temperatur av -50 till 50°C, företrädesvis vid rumstemperatur, med minst en ekvivalent av en halogenhaltig oxidant utvald bland klor, brom, bromklorid, hypoklorsyrlig- het, hypobromsyrlighet eller blandningar därav, tills reak- tionen är väsentligen fullständig.R'O / -O- R wherein R, R 'and R "' have the meaning given above, in a solvent at a temperature of -50 to 50 ° C, preferably at room temperature, with at least one equivalent of a halogen-containing oxidant selected from chlorine, bromine, bromine chloride, hypochlorous acid, hypobromic acid or mixtures thereof, until the reaction is substantially complete.
Exempel på lämpliga lösningsmedel för denna reaktion är vatten, en alkanol eller diol med 1-4 kolatomer, företrädes- vis metanol, en eter med 2-10 kolatomer, företrädesvis tetra- hydrofuran eller isopropyleter, en lågmolekylär keton, före- trädesvis aceton, en lågmolekylär nitril, ester eller amid.Examples of suitable solvents for this reaction are water, an alkanol or diol having 1-4 carbon atoms, preferably methanol, an ether having 2-10 carbon atoms, preferably tetrahydrofuran or isopropyl ether, a low molecular weight ketone, preferably acetone, a low molecular weight nitrile, ester or amide.
Vissa av 4-halo-dihydropyranintermediatföreningarna, som identi- fieras med formeln (II') nedan, är nya och uppfinningen avser följaktligen ett förfarande för framställning av en 4-halo- dihydropyranförening, som har formeln RI!! X _. (Iln) :~:o O n' ' vari R är väte eller alkyl med l-4 kolatomer, R"' är väte eller alkyl med l-4 kolatomer och X är klor eller brom, vilket förfarande utmärkes därav, att det innefattar reaktion av en förening, som har formeln OH R||| R g ' vari R och R"' har ovan angiven betydelse, i vattenlösning vid en temperatur från -50°C till 50°C, med minst två ekviva- lenter av en halogenhaltig oxidant utvald bland klor, brom, bromklorid, hypoklorsyrlighet, hypobromsyrlighet eller bland- ningar därav, tills reaktionen är väsentligen fullständig.Some of the 4-halo-dihydropyran intermediate compounds identified by formula (II ') below are novel and the invention therefore relates to a process for the preparation of a 4-halo-dihydropyran compound having the formula RI !! X _. (Iln): ~: o O '"wherein R is hydrogen or alkyl of 1-4 carbon atoms, R"' is hydrogen or alkyl of 1-4 carbon atoms and X is chlorine or bromine, which process is characterized in that it comprises reaction of a compound having the formula OH R ||| R g 'wherein R and R "' are as defined above, in aqueous solution at a temperature from -50 ° C to 50 ° C, with at least two equivalents of a halogenated oxidant selected from chlorine, bromine, bromine chloride, hypochlorous acid, hypobromic acid or mixtures thereof, until the reaction is substantially complete.
Företrädesvis kan reaktionen genomföras i närvaro av ett sam- lösningsmedel, som utgöres av en alkanol eller diol med l-4 kolatomer, en eter med 2-10 kolatomer, en lågmolekylär keton, nitril, ester eller amid.Preferably, the reaction may be carried out in the presence of a co-solvent consisting of an alkanol or diol having 1 to 4 carbon atoms, an ether having 2 to 10 carbon atoms, a low molecular weight ketone, nitrile, ester or amide.
Föredragna samlösningsmedel är metanol, tetrahydrofuran, isopropyleter eller aceton.Preferred co-solvents are methanol, tetrahydrofuran, isopropyl ether or acetone.
Den halogenhaltiga oxidanten utväljes bland klor, brom, brom- klorid, hypoklorsyrlighet eller hvpobromsyrlighet eller bland- ningar därav. Bromklorid är en kommersiellt tillgänglig gas.The halogen-containing oxidant is selected from chlorine, bromine, bromine chloride, hypochlorous acid or hpbromic acid or mixtures thereof. Bromine chloride is a commercially available gas.
Den kan framställas in situ genom tillsats av klor till en lösning av natrium- eller kaliumbromid eller genom tillsats av brom till en lösning av natrium- eller'kaliumklorid. Hypo- klorsyrlighet och hypobromsyrlighet kan lämpligen bildas in situ genom tillsats av vattenhaltig syra (HCl, HZSO4 eller Hßr) 82Û052Û~8 till en lösning av en alkalimetall- eller jordalkalimetall- Vhypohalit, t.ex. NaOCl, KOCI eller Ca(OCl)2. De föredragna halogenhaltiga oxidanterna, baserat_på kostnadsfaktorn, är klor- och bromklorid framställda in situ.It can be prepared in situ by adding chlorine to a solution of sodium or potassium bromide or by adding bromine to a solution of sodium or potassium chloride. Hypochlorous acid and hypobromic acid can be conveniently formed in situ by the addition of aqueous acid (HCl, H 2 SO 4 or Hßr) to a solution of an alkali metal or alkaline earth metal Vhypohalite, e.g. NaOCl, KOCl or Ca (OCl) 2. The preferred halogen-containing oxidants, based on the cost factor, are chlorine and bromine chloride produced in situ.
Vid en föredragen utföringsform av uppfinningen bringas en furfurylalkohol i vattenlösning tillsammans med ett even- tuellt närvarande samlösningsmedel att reagera vid -lOOC till IOQC med två ekvivalenter av en halogenhaltig oxidant. Efter omröring vid rumstemperatur i 30 minuter inställes reaktionens pH på 2 med en stark bas och reaktionsblandningen extraheras med ett lösningsmedel såsom etylacetat. Avlägsning av lösnings- medlet ger den önskade 4-halo-6-hydroxi-2H-pyran-3(6H)-onen med formeln (II').In a preferred embodiment of the invention, a furfuryl alcohol in aqueous solution together with any co-solvent present is reacted at -10 ° C to 100 ° C with two equivalents of a halogen-containing oxidant. After stirring at room temperature for 30 minutes, the pH of the reaction is adjusted to 2 with a strong base and the reaction mixture is extracted with a solvent such as ethyl acetate. Removal of the solvent gives the desired 4-halo-6-hydroxy-2H-pyran-3 (6H) -one of formula (II ').
Följande exempel belyser framställningen av de intermediära 4-halo-dihydropyranföreningarna medelst förfarandet enligt uppfinningen.The following examples illustrate the preparation of the intermediate 4-halo-dihydropyran compounds by the process of the invention.
I de exempel vari spektraldata förekommer anges NMR-kemiska data medelst i litteraturen konventionellt använda symboler » och alla förändringar uttryckes såsom S-enheter från tetra- metylsilan: s = singlett d = dublett t = triplett q = kvartett m = multiplett br = bred Exempel l 4-bromo-6-hydroxi-2-metyl-2H-pyran-3(6H)-on Till en lösning av 25 g l-(2-furyl)-l-etanol i 125 ml tetrahydro- furan och 125 ml vatten vid O-SOC sattes droppvis 2,2 ekviva- lenter brom. Under hela tillsatsen hölls temperaturen vid 5-l0°C. Efter bromtillsatsen omrördes lösningen vid rums- temperatur i 30 minuter och pH inställdes på 2,1 med 2N NaOH- lösning. Reaktionsblandningen extraherades med etylacetat (3 x s20o520~s 6 lOO ml). Etylacetatextrakten kombinerades, torkados över MgSO4, filtrerades och indunstades till torrhet. Återstoden kromato- graferades på kiselgel och eluerades med kloroform/etylacetat (95:5). Produkten var en orangefärgad olja, som på nytt kromato- graferades på kiselgel och eluerades med kloroform/etylacetat (95:5). V NMR (cnc13,¿ ) 7,3 (ln, a>; 5,6 (ln, a); 4,7-s,o (ln, q); 1,1-l,5 (3H, m).In the examples in which spectral data occur, NMR chemical data are given by means of symbols conventionally used in the literature »and all changes are expressed as S-units from tetramethylsilane: s = singlet d = doublet t = triplet q = quartet m = multiplet br = broad Example 4-Bromo-6-hydroxy-2-methyl-2H-pyran-3 (6H) -one To a solution of 25 g of 1- (2-furyl) -1-ethanol in 125 ml of tetrahydrofuran and 125 ml of water at O-SOC, 2.2 equivalents of bromine were added dropwise. Throughout the addition, the temperature was maintained at 5-10 ° C. After the bromine addition, the solution was stirred at room temperature for 30 minutes and the pH was adjusted to 2.1 with 2N NaOH solution. The reaction mixture was extracted with ethyl acetate (3 x 520520 ~ s 600 ml). The ethyl acetate extracts were combined, dried over MgSO 4, filtered and evaporated to dryness. The residue was chromatographed on silica gel eluting with chloroform / ethyl acetate (95: 5). The product was an orange oil, which was again chromatographed on silica gel eluting with chloroform / ethyl acetate (95: 5). 1 H NMR (cnc13, δ) 7.3 (ln, a>; 5.6 (ln, a); 4,7-s, o (ln, q); 1,1-1,5 (3H, m) .
Exemgel 2 Försöket i exempel l upprepades med en furfurylalkohol, som R hade formeln: A för erhållande av en förening, som har formeln / /Å //l\\O,/^\\n vari R är väte eller etyl.Example Gel 2 The experiment of Example 1 was repeated with a furfuryl alcohol having R had the formula: A to give a compound having the formula / wherein R is hydrogen or ethyl.
HO Etylföreningen: 4-bromo-6-hydroxi-2-etyl-2H-pyran-3(6H)-on NMR (cnc13,5)= 7,4 (ln, d); 4,6-4,9 (ln, m); 1,8-2,2 (zu, m>; 1,0-1,3 (sn, t). _» Väteföreningen: 4-bromoeö-hydroxi-2H-pyran-3(GH)-on NMR (cnc13,6')= 7,4 (la, d); 5,5 (ln, a); 4,6 (zu, d avla).HO The ethyl compound: 4-bromo-6-hydroxy-2-ethyl-2H-pyran-3 (6H) -one NMR (cnc13.5) = 7.4 (1n, d); 4.6-4.9 (ln, m); 1.8-2.2 (zu, m>; 1.0-1.3 (sn, t). The hydrogen compound: 4-bromo-hydroxy-2H-pyran-3 (GH) -one NMR (cnc13, 6 ') = 7.4 (la, d); 5.5 (ln, a); 4.6 (zu, d avla).
Försöket 1 exefleí 1 upprepades med användning av klo: íseäíier för brom och motsvarande furfurylalkoholer för framställning av följande föreningar: Metyl: 4-kloro-6-hydroxi-2-metyl-ZH-pyran-3(GR)-on mm (cncly 5); 1.1 un, du s.s (m. du 4.6-5.o' un. m).- 414 112-'1/5 m)- 8200520-8 7 Etyl: 4-kloro-6-hydroxi-2-etyl-2H~pyran-3(6H)-on NMR (cpc13, 5)= 7,0-7,1 (ln, dy; 5,6-6,0 (zu, m); 4,4-5,0 (ln, m); 1,6-2,1 (zu, m); o,9-1,1 (su, t). väte: 4~kloro-6-hydroxi~2H-pyran-3(6H)~on NMR (CDCl3, §): 7,l-7,2 (lH, d); 5,6 (lH, d); 4,4-4,9 (2H, d av d) (D20 tillsatt).Experiment 1 was repeated using bromine chloroforms and corresponding furfuryl alcohols to prepare the following compounds: Methyl: 4-chloro-6-hydroxy-2-methyl-ZH-pyran-3 (GR) -one mm (cyclic 5 ); 1.1 μm, du ss (m. Du 4.6-5.o 'un. M) .- 414 112-'1 / 5 m) - 8200520-8 7 Ethyl: 4-chloro-6-hydroxy-2-ethyl-2H Pyran-3 (6H) -one NMR (cpc13.5) = 7.0-7.1 (ln, dy; 5.6-6.0 (zu, m); 4.4-5.0 (ln , m); 1.6-2.1 (zu, m); 0,9-1.1 (su, t) .hydrogen: 4-chloro-6-hydroxy-2H-pyran-3 (6H) -one NMR (CDCl 3, δ): 7.1-7.2 (1H, d); 5.6 (1H, d); 4.4-4.9 (2H, d of d) (D 2 O added).
Exemgel 4 Försöket i exempel l upprepades för erhållande av en förening, som har førmeln vari R är propyl eller butyl, X är brom eller klor.Example Gel 4 The experiment of Example 1 was repeated to give a compound having the formula wherein R is propyl or butyl, X is bromine or chlorine.
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| US71090176A | 1976-08-02 | 1976-08-02 | |
| US05/721,885 US4082717A (en) | 1976-08-02 | 1976-09-09 | Preparation of gamma-pyrones |
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| SE7707035A SE433079B (en) | 1976-08-02 | 1977-06-16 | PROCEDURE FOR MANUFACTURING V-PYRONS |
| SE8200519A SE445042B (en) | 1976-08-02 | 1982-01-29 | PROCEDURE FOR MANUFACTURING GAMMA PYRONS |
| SE8200520A SE444564B (en) | 1976-08-02 | 1982-01-29 | 4-HALOGENE DIHYDROPYRANE COMPOUNDS FOR USE AS INTERMEDIATE IN THE PREPARATION OF GAMMA PYRONS AND PROCEDURE FOR PREPARING THEREOF |
| SE8200521A SE452616B (en) | 1976-08-02 | 1982-01-29 | PROCEDURE FOR PREPARATION OF 4-HALO-2H-PYRANE-3 (6H) -ON COMPOUNDS |
| SE8200522A SE444565B (en) | 1976-08-02 | 1982-01-29 | 6,6'-OXIBIS / 4-HALO-2H-PYRANE-3 (6H) -ON / COMPOUNDS FOR USE AS INTERMEDIATE IN THE PREPARATION OF GAMMA PYRONS AND PROCEDURE FOR PREPARING THEREOF |
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| SE8200522A SE444565B (en) | 1976-08-02 | 1982-01-29 | 6,6'-OXIBIS / 4-HALO-2H-PYRANE-3 (6H) -ON / COMPOUNDS FOR USE AS INTERMEDIATE IN THE PREPARATION OF GAMMA PYRONS AND PROCEDURE FOR PREPARING THEREOF |
| SE8200518A SE445041B (en) | 1976-08-02 | 1982-01-29 | PROCEDURE FOR MANUFACTURING GAMMA PYRONS |
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| CA1095921A (en) | 1976-08-02 | 1981-02-17 | Thomas M. Brennan | Preparation of gamma-pyrones |
| FR2402654A1 (en) * | 1977-09-12 | 1979-04-06 | Shinetsu Chemical Co | Tetra:hydro-pyranone derivs. - useful as intermediates for cpds. used as food flavours |
| JPS5444675A (en) * | 1977-09-12 | 1979-04-09 | Shin Etsu Chem Co Ltd | Production of 3-hydroxy-4-pyrone analog |
| 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 |
| CN102014904B (en) | 2008-04-25 | 2013-02-06 | 阿普泰克斯科技公司 | Liquid formulation of deferiprone with palatable taste |
| AU2010268666B2 (en) | 2009-07-03 | 2014-07-24 | Apotex 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 |
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| 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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