SE444565B - 6,6'-oxibis/4-halo-2h-pyran-3(6h)-on/-foreningar till anvendning sasom intermediat vid framstellning av gamma-pyroner samt forfarande for framstellning derav - Google Patents
6,6'-oxibis/4-halo-2h-pyran-3(6h)-on/-foreningar till anvendning sasom intermediat vid framstellning av gamma-pyroner samt forfarande for framstellning deravInfo
- Publication number
- SE444565B SE444565B SE8200522A SE8200522A SE444565B SE 444565 B SE444565 B SE 444565B SE 8200522 A SE8200522 A SE 8200522A SE 8200522 A SE8200522 A SE 8200522A SE 444565 B SE444565 B SE 444565B
- Authority
- SE
- Sweden
- Prior art keywords
- preparation
- halo
- formula
- gamma
- oxibis
- Prior art date
Links
- 150000001875 compounds Chemical class 0.000 title claims description 14
- 238000002360 preparation method Methods 0.000 title claims description 9
- 238000000034 method Methods 0.000 title claims description 7
- 239000000460 chlorine Substances 0.000 claims description 7
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052794 bromium Chemical group 0.000 claims description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052801 chlorine Inorganic materials 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 4
- 230000018044 dehydration Effects 0.000 claims description 3
- 238000006297 dehydration reaction Methods 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- XPCTZQVDEJYUGT-UHFFFAOYSA-N 3-hydroxy-2-methyl-4-pyrone Chemical compound CC=1OC=CC(=O)C=1O XPCTZQVDEJYUGT-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- VEYIMQVTPXPUHA-UHFFFAOYSA-N 3-hydroxypyran-4-one Chemical compound OC1=COC=CC1=O VEYIMQVTPXPUHA-UHFFFAOYSA-N 0.000 description 2
- YIKYNHJUKRTCJL-UHFFFAOYSA-N Ethyl maltol Chemical compound CCC=1OC=CC(=O)C=1O YIKYNHJUKRTCJL-UHFFFAOYSA-N 0.000 description 2
- HYMLWHLQFGRFIY-UHFFFAOYSA-N Maltol Natural products CC1OC=CC(=O)C1=O HYMLWHLQFGRFIY-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229940093503 ethyl maltol Drugs 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 229940043353 maltol Drugs 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000002304 perfume Substances 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000007858 starting material Substances 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
- 241000894006 Bacteria Species 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 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
- 230000002378 acidificating effect Effects 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- CODNYICXDISAEA-UHFFFAOYSA-N bromine monochloride Chemical compound BrCl CODNYICXDISAEA-UHFFFAOYSA-N 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
- 239000006184 cosolvent Substances 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
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000013355 food flavoring agent Nutrition 0.000 description 1
- 150000002431 hydrogen Chemical group 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000010502 orange oil Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000007787 solid Substances 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
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical group C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-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
8200522-4 Chem., 49 (5), 827-832 (1976). Denna föreing syntetiserades tidigare enligt det förfarande som beskrives i den amerikanska §_ patentskriften 3.468.915.
Synteser av gamma-pyroner såsom pyromekonsyra, maltol, etyl- maltol och andra 2-substituerad 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.
Maltol och etylmaltol förstärker aromen och smaken hos en mång- bald 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 inhlberar tillväxt av bakterier och svampar och är användbara såsom arom- och smak- förstärkande medel i livsmedel och drycker och såsom lukt-2 förstärkande medel i parfymer.
Svenska patentet 433 079 anger ett förfarande för framställ- ning av en gamma-pyron, som har formeln: J? o' ¥ ,- ..
O! ° R ' ff RI I I vilket innefattar upphettning i sur vattenhaltig lösning, företrädesvis vid en temperatur inom intervallet 70-l60°C tills hydrolysen är väsentligen fullständig, av en 6,6'-oxa- E bis-LÃ-halo-2H-pyran-3(6H)-on] som har formeln (V): (I) e. 8200522-4 vari R betecknar väte eller alkyl med l-4 kolatomer, R"' betecknar väte eller alkyl med l-4 kolatomer och X betecknar klor eller brom.
Den syra som erfordras för hydrolysen kan sättas till reaktions- blandningen, t.ex. genom upplösning av den intermediära före- ningen med formeln (V) i»en vattenhaltig oorganisk eller orga- nisk syra före upphettningen; eller alternativt kan syran bildas in situ under framställningen av lntermediatet såsom beskrives nedan.
Enligt föreliggande uppfinning åstadkommas ett förfarande för framställning av en ny intermediär förening enligt formeln (V) ovan, vilket utmärkas därav, att man dehydratiserar en före- ning, som har formeln X ff/ /,.Û (IJ-ll) HC O R vari R och X har ovan angiven betydelse.
Dehydratiaeringen genomföras företrädesvis genom upphettning av föreningen med formeln (II") vid en temperatur av 4000 i 16 timmar.
Såsom beskrives i det svenska patentet 433 079 kan utgångs- föreningen med formeln (II") framställas genom reaktion av en furfurylalkohol i vattenlösning med ett optionellt Samlösningsmeflel vid -lO°C till +lO°C med användning av två ekvivalenter av en halogenhaltig oxidant. Den föredragna halogen- haltiga oxidanten är klor eller bromklorid. Efter omröring vid rumstemperatur i 30 minuter inställes reaktionsblandningens pH på 2 med en stark bas och reaktionsblandningen extraheras med ett lösningsmedel såsom etylacetat. Avlägsning av lösnings- medlet ger 4-halo-6-hydroxi-2H-pyran-3(6H)-onen med formeln (II"), som kan dehydratiseras genom upphettning under vakuum ._ v., ....-_.le._.-r...,..«-.--=~=~«»-~f--=«-f~=~" f* 8200522-4 för erhållande av 6,6'-oxibis[4-halo-2H-pyran-3(6H)-onf.
Följande exempel belyser framställningen av de nya intermediära föreningarna enligt förfarandet enligt uppfinningen.
I de spektraldata som anges i exempel l(a) anges NMR-kemiska data i enlighet med inom litteraturen konventionella symboler och alla skiftningar uttryckes såsom X-enheter från tetrametyl- silan: _ _ _ ¿ d = dublett I q = kvartett m = multiplett Exempel l (a) Framställning av 4-bromo-6-hydroxi-2-metyl-EH-pyran-3(6d)- on (utgångsförening) _ ' Till en lösning av 25 g l-(2-furyl)-l-etanol i l25 ml tetra- hydrofuran och l25 ml vatten vid O-SOC sattes droppvis 2,2 ckvivalenter brom. Under hela tillsatsen hölls temperaturen vid 5-lO°C. Efter bromtillsatsen omrördes lösningen vid rums- tempertur i 30 minuter och pH inställdes på 2,1 med 2N Naom- lösning. Reaktionsblandningen extraherades med etylacetat (3 x 100 ml). Etylacetatextrakten kombinerades, torkades över MgS04, flltrerades och indunstades till torrhet. Återstoden É- kromatograferades på kiselgel och eluerades med kloroform/etyl- acetat (95:5). Produkten var en orangefärgad olja som på - ~ nytt kromatograferades pà kiselgel och eluerades med kloroform/ i etylacetat (95:5).
NMR (CDCI3, 5) 7,3 (lH, d); 5,6 (lH, d); 4,7-5,0 (lH, q); 1,1-1,5 (BH, m). v¿ (b) Framställning av slutprodukt 4-bromo-6-hydroxi-2-metyl-2H-pyran-3(6H)-on upphettades under vakuum i l6 timmar vid 40°C. Den resulterande oljeartade fasta substansen kristalliserades ur isopropylalkohol för erhållning av 6,6'-oxibis[Ä-bromo-2-metyl-2H-pyran-3(GH)-onj, smältpunkt 12500. -ww-»n-W-A. _." ., _ . . ywwlwwwwv-É-fl “www fy fl 8200522-4 Exemgel 2 Försöket i exempel l upprepades med utgång från en förening, som har formeln >: /0“ / / , Ho “ o R för erhållande av en förening, som har formeln X f O¿2~ \\~ //1 íç n o\o\o 'R vari R är väte, etyl, propyl eller butyl och X är brom eller klor. 3 § smältgunkt (OC) CH3 Cl 177-179 CH CH Cl 132-135 2 3
Claims (3)
1. En 6,6'~oxibis[Ä-halo-2H-pyran~3(6H)-on]-förening för användning såsom ett intermediat vid framställning av gamma- pyroner, k ä n n e t e c k n a_d därav, att den har formeln 0% X f fo (V) R \o o \o R » vari R är väte eller alkyl med l-4 kolatomer och X är klor eller brom.
2. Förfarande för framställning av en 6,6'-oxibis[4~halo-2H- pyran-3(6H)-on]-förening, som har formeln >'~ - >: CN/g / 40 i J (vi ' n \\o, \o vari R är väte eller alkyl med 1-4 kolatomer och X är klor eller brom, k ä n n e t e c k n a t därav, att det innefattar dehydratisering av en förening, som har formeln X \\ n) Ho i R i vari R och X har ovan angiven betydelse. s20os22-4
3. Förfarande enligt patentkravet'2Q k ä n n e t e c k n a t därav, att dehydratiseringen genomföras genom upphettning av föreningen med formeln (II") vid en temperatur av 40oC i 16 timmar.
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 (2)
| Publication Number | Publication Date |
|---|---|
| SE8200522L SE8200522L (sv) | 1982-01-29 |
| SE444565B true SE444565B (sv) | 1986-04-21 |
Family
ID=27108548
Family Applications (6)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| SE7707035A SE433079B (sv) | 1976-08-02 | 1977-06-16 | Forfarande for framstellning av v-pyroner |
| SE8200519A SE445042B (sv) | 1976-08-02 | 1982-01-29 | Forfarande for framstellning av gamma-pyroner |
| SE8200520A SE444564B (sv) | 1976-08-02 | 1982-01-29 | 4-halogen-dihydropyranforeningar for anvendning sasom intermediat vid framstellning av gamma-pyroner samt forfarande for framstellning derav |
| SE8200521A SE452616B (sv) | 1976-08-02 | 1982-01-29 | Forfarande for framstellning av 4-halo-2h-pyran-3(6h)-on-foreningar |
| SE8200522A SE444565B (sv) | 1976-08-02 | 1982-01-29 | 6,6'-oxibis/4-halo-2h-pyran-3(6h)-on/-foreningar till anvendning sasom intermediat vid framstellning av gamma-pyroner samt forfarande for framstellning derav |
| SE8200518A SE445041B (sv) | 1976-08-02 | 1982-01-29 | Forfarande for framstellning av gamma-pyroner |
Family Applications Before (4)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| SE7707035A SE433079B (sv) | 1976-08-02 | 1977-06-16 | Forfarande for framstellning av v-pyroner |
| SE8200519A SE445042B (sv) | 1976-08-02 | 1982-01-29 | Forfarande for framstellning av gamma-pyroner |
| SE8200520A SE444564B (sv) | 1976-08-02 | 1982-01-29 | 4-halogen-dihydropyranforeningar for anvendning sasom intermediat vid framstellning av gamma-pyroner samt forfarande for framstellning derav |
| SE8200521A SE452616B (sv) | 1976-08-02 | 1982-01-29 | Forfarande for framstellning av 4-halo-2h-pyran-3(6h)-on-foreningar |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| SE8200518A SE445041B (sv) | 1976-08-02 | 1982-01-29 | Forfarande for framstellning av gamma-pyroner |
Country Status (36)
| Country | Link |
|---|---|
| JP (7) | JPS5318578A (sv) |
| AR (1) | AR216080A1 (sv) |
| AT (3) | AT362790B (sv) |
| BE (1) | BE855965A (sv) |
| BG (4) | BG28989A4 (sv) |
| BR (1) | BR7703970A (sv) |
| CA (3) | CA1095921A (sv) |
| CH (4) | CH625798A5 (sv) |
| CS (3) | CS203921B2 (sv) |
| DD (1) | DD132494A5 (sv) |
| DE (3) | DE2760221C2 (sv) |
| DK (4) | DK153483C (sv) |
| EG (1) | EG13080A (sv) |
| ES (5) | ES459994A1 (sv) |
| FI (6) | FI72722C (sv) |
| FR (1) | FR2372821A1 (sv) |
| GB (5) | GB1538373A (sv) |
| GR (1) | GR68938B (sv) |
| HK (5) | HK30381A (sv) |
| HU (4) | HU185686B (sv) |
| IE (5) | IE45644B1 (sv) |
| IT (1) | IT1106258B (sv) |
| LU (1) | LU77600A1 (sv) |
| MX (1) | MX4597E (sv) |
| MY (3) | MY8100267A (sv) |
| NL (5) | NL170955C (sv) |
| NO (7) | NO150561C (sv) |
| NZ (1) | NZ184342A (sv) |
| PH (5) | PH13557A (sv) |
| PL (4) | PL115586B1 (sv) |
| PT (1) | PT66694B (sv) |
| RO (4) | RO78953A (sv) |
| SE (6) | SE433079B (sv) |
| SU (2) | SU955859A3 (sv) |
| TR (1) | TR19652A (sv) |
| YU (4) | YU40166B (sv) |
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 (sv) * | 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 (sv) * | 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 |
| WO2008116301A1 (en) * | 2007-03-28 | 2008-10-02 | Apotex Technologies Inc. | Fluorinated derivatives of deferiprone |
| CN102014904B (zh) | 2008-04-25 | 2013-02-06 | 阿普泰克斯科技公司 | 具有适口味道的去铁酮液体配制品 |
| 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 (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 (sv) * | 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
- 1977-06-09 GR GR53666A patent/GR68938B/el unknown
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- 1977-06-21 FI FI771934A patent/FI72722C/sv not_active IP Right Cessation
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- 1977-06-22 DE DE2760221A patent/DE2760221C2/de not_active Expired
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- 1977-06-22 EG EG371/77A patent/EG13080A/xx active
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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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- 1977-07-20 RO RO7799826A patent/RO78952A/ro unknown
- 1977-07-20 RO RO7799825A patent/RO78951A2/ro unknown
- 1977-07-21 GB GB4241/78A patent/GB1538373A/en not_active Expired
- 1977-07-21 SU SU772508256A patent/SU955859A3/ru active
- 1977-07-21 GB GB4242/78A patent/GB1538374A/en not_active Expired
- 1977-07-21 GB GB4240/78A patent/GB1538372A/en not_active Expired
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- 1977-07-21 GB GB4243/78A patent/GB1538375A/en not_active Expired
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1978
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- 1978-06-13 ES ES470746A patent/ES470746A1/es not_active Expired
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- 1978-07-05 SU SU782631651A patent/SU1015826A3/ru active
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1979
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1980
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1981
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- 1981-07-02 HK HK303/81A patent/HK30381A/en unknown
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1982
- 1982-01-29 SE SE8200519A patent/SE445042B/sv not_active IP Right Cessation
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1983
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- 1983-08-08 YU YU1663/83A patent/YU43190B/xx unknown
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1986
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