StartseiteMCPWorkbenchSkills
StartseiteWorkbenchBenachrichtigungenMein Bereich
llms.txt · MCP-AnleitungDatenschutz · Nutzungsbedingungen · Supportv1.8.0
  1. Startseite
  2. /Reaktion

Citric Acid → [1,1'-Biphenyl]-4-carboxylic acid (3aR,4R,5R,6aS)-hexahydro-2-oxo-4-[(1E)-3-oxo-4-[3-(trifluoromethyl)phenoxy]-1-buten-1-yl]-2H-cyclopenta[b]furan-5-yl ester

HRID 1375233
Notizen
Druckvorschau

Reaktionsgleichung

Reaktionsgleichung von HRID 1375233
[CH2:1]1[C@@H:9]([O:10][C:11]([C:13]2[CH:18]=[CH:17][C:16]([C:19]3[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=3)=[CH:15][CH:14]=2)=[O:12])[C@H:8]([CH2:25]O)[C@H:3]2[CH2:4][C:5]([O:7][C@@H:2]12)=[O:6].[Na+].[Br-].C([O-])(O)=O.[Na+].CC(O)C.[O-]Cl.[Na+].[C:41]([C:45]1[CH:46]=[C:47]([O:51][CH2:52][C:53]([CH2:55]P(OC)(OC)=O)=[O:54])[CH:48]=[CH:49][CH:50]=1)([F:44])([F:43])[F:42].[OH-].[Na+].C(O)(=O)CC(CC(O)=O)(C(O)=O)O>C(Cl)Cl.O.CC1(C)N([O])C(C)(C)CCC1>[O:54]=[C:53]([CH2:52][O:51][C:47]1[CH:48]=[CH:49][CH:50]=[C:45]([C:41]([F:42])([F:43])[F:44])[CH:46]=1)/[CH:55]=[CH:25]/[C@@H:8]1[C@@H:3]2[C@@H:2]([O:7][C:5](=[O:6])[CH2:4]2)[CH2:1][C@H:9]1[O:10][C:11](=[O:12])[C:13]1[CH:18]=[CH:17][C:16]([C:19]2[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=2)=[CH:15][CH:14]=1
KomponentenVersuchsvorschriftAufarbeitungQuellen und NachweiseNotizen zur Reaktion

Komponenten

12

Edukt 8

HCID 311Citric AcidHCID 3776IsopropanolHCID 14798Sodium HydroxideHCID 253881Sodium BromideHCID 516892Sodium BicarbonateHCID 2724295(1,1'-Biphenyl)-4-carboxylic acid, (3aR,4S,5R,6aS)-hexahydro-4-(hydroxymethyl)-2-oxo-2H-cyclopenta(b)furan-5-yl ester
HCID 15003092
Dimethyl {2-oxo-3-[3-(trifluoromethyl)phenoxy]propyl}phosphonate
HCID 23665760Sodium Hypochlorite

Produkt 1

HCID 11834868[1,1'-Biphenyl]-4-carboxylic acid (3aR,4R,5R,6aS)-hexahydro-2-oxo-4-[(1E)-3-oxo-4-[3-(trifluoromethyl)phenoxy]-1-buten-1-yl]-2H-cyclopenta[b]furan-5-yl esterAusbeute 80,3 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 2724126TempoKatalysatorHCID 962WaterLösungsmittelHCID 6344DichloromethaneLösungsmittel2×

Versuchsvorschrift

A solution of (−)-Corey lactone 5-(4-phenylbenzoate) (17.6 g, 50.0 mmol) and TEMPO (0.16 g, 1.0 mmol) in CH2Cl2 (100 mL) was added to a mixture of NaBr (0.5 g, 5.0 mmol), NaHCO3 (12.6 g, 150.0 mmol) and IPA (6.0 g, 100.0 mmol) in water (100 mL). 5% aq. NaOCl (about 150 mL) was added dropwise to the stirred mixture at −5 to 0° C. until disappearance of Corey lactone (TLC monitoring). The obtained mixture was stirred for 0.5 h at the same temperature. The aqueous layer was separated and extracted with CH2Cl2 (50 mL). The combined organic layer was added dropwise over 1 hour to a stirred mixture of a solution of m-CF3C6H4OCH2COCH2PO(OMe)2 (19.6 g, 60.0 mmol) in CH2Cl2 (20 mL) and 30% NaOH (8.0 g, 60.0 mmol) at 0 to −5° C. The mixture was stirred 1 h at the same temperature and treated with 10% aq. citric acid (100 mL). The aqueous layer was separated and extracted with CH2Cl2 (50 mL). The combined organic layer was dried over Na2SO4, filtered through short silica gel column and concentrated in vacuo. The oily residue (26.96 g) was dissolved in refluxed MeOH (150 mL) and cooled in ice bath. The precipitate was filtered off, washed with cold MeOH and dried in vacuo to give 22.1 g (80%) of (3aR,4R,5R,6aS)-4-[3-oxo-4-[3-(trifluoromethyl)phenoxy]-1E-butenyl]-5-(4-phenylbenzoyloxy)-hexahydro-2H-cyclopenta[b]furan-2-one with 99.1% purity by HPLC: mp 115–116° C.; [α]D20 −118.4° (c 1.0, CHCl3). 1H NMR (CDCl3) δ: 8.02 (d, J=8 Hz, 2H), 7.58 (m, 4H), 7.40 (m, 4H), 7.22 (d, J=8 Hz, 1H), 7.10 (s, 1H), 6.94 (m, 2H), 6.57 (d, J=15.7 Hz, 1H), 5.35 (q, J=5.5 Hz, 1H), 5.09 (t, J=5.5 Hz, 1H), 4.71 (s, 2H), 2.92 (m, 3H), 2.56 (m, 3H).

Aufarbeitung

  1. customThe aqueous layer was separated
  2. extractionextracted with CH2Cl2 (50 mL)
  3. stirringThe mixture was stirred 1 h at the same temperature
  4. customThe aqueous layer was separated
  5. extractionextracted with CH2Cl2 (50 mL)
  6. dry with materialThe combined organic layer was dried over Na2SO4
  7. filtrationfiltered through short silica gel column
  8. concentrationconcentrated in vacuo
  9. dissolutionThe oily residue (26.96 g) was dissolved in refluxed MeOH (150 mL)
  10. temperaturecooled in ice bath
  11. filtrationThe precipitate was filtered off
  12. washwashed with cold MeOH
  13. customdried in vacuo

Quellen und Nachweise

ORD-Eintrag
ord-730690e5f85a4226844fd253b0644a6a
Quelldatensatz
uspto-grants-2007_01
DOI
10.6084/m9.figshare.5104873.v1
Patentnummer
US07166730B2

Notizen zur Reaktion

Wird geladen…

Auf dieser SeiteKomponentenVersuchsvorschriftAufarbeitungQuellen und NachweiseNotizen zur Reaktion