(+)-8-Phenylmenthol → HCID 69303668, Verbindung

HRID 635977

Reaktionsgleichung

Reaktionsgleichung von HRID 635977
[Br:1][C:2]1[CH:3]=[C:4]([CH:9]2[C:14]3[S:15](=[O:19])(=[O:18])[CH2:16][CH2:17][C:13]=3[NH:12][C:11]3[CH2:20][O:21][CH2:22][C:23](=[O:24])[C:10]2=3)[CH:5]=[CH:6][C:7]=1[F:8].CC(C)([O-])C.[K+].Cl[C:32]([O:34][CH:35]1[CH:40]([C:41]([C:44]2[CH:49]=[CH:48][CH:47]=[CH:46][CH:45]=2)([CH3:43])[CH3:42])[CH2:39][CH2:38][CH:37]([CH3:50])[CH2:36]1)=[O:33].C1(C(C)(C)C2CCC(C)CC2O)C=CC=CC=1>C1COCC1.C(Cl)Cl>[Br:1][C:2]1[CH:3]=[C:4]([CH:9]2[C:14]3[S:15](=[O:18])(=[O:19])[CH2:16][CH2:17][C:13]=3[N:12]([C:32]([O:34][C@@H:35]3[CH2:36][C@H:37]([CH3:50])[CH2:38][CH2:39][C@H:40]3[C:41]([CH3:42])([C:44]3[CH:49]=[CH:48][CH:47]=[CH:46][CH:45]=3)[CH3:43])=[O:33])[C:11]3[CH2:20][O:21][CH2:22][C:23](=[O:24])[C:10]2=3)[CH:5]=[CH:6][C:7]=1[F:8]

Komponenten

7

Edukt 4

HCID 577105(+)-8-PhenylmentholHCID 9887983(+)-9-(3-Bromo-4-fluorophenyl)-2,3,5,9-tetrahydro-4h-pyrano[3,4-b]thieno[2,3-e]pyridin-8(7h)-one 1,1-dioxideHCID 145714908-Phenylmenthol chloroformateHCID 23665647Potassium tert-butoxide

Produkt 1

HCID 69303668HCID 69303668, Verbindung

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 6344DichloromethaneLösungsmittelHCID 8028TetrahydrofuranLösungsmittel3×

Versuchsvorschrift

To a suspension of the product from Example 11D (1.58 g, 3.7 mmol) in THF (40 mL) at 0° C. under a nitrogen atmosphere was added a 1M solution of potassium tert-butoxide in THF (4.1 mL) dropwise over 5 minutes. The mixture was stirred at ambient temperature for 30 minutes, cooled to 0° C., treated with a solution of 8-phenylmenthol chloroformate prepared from (−)-8-phenylmenthol as described in (Yamamoto, Y., J. Amer. Chem. Soc. (1992), 114, 121-125) (1.31 g, 4.4 mmol) in THF (20 mL) over 5 minutes, stirred at ambient temperature for 16 hours, diluted with methylene chloride (150 mL) and washed with aqueous sodium bicarbonate (30 mL). The layers were separated and the aqueous layer was extracted with methylene chloride (50 mL). The combined organic layers were dried (MgSO4), filtered and concentrated. The residue was purified by flash chromatography over silica gel (3:2:1 chloroform/hexanes/diethyl ether) to provide 0.98 g of the less polar diasteriomer.

Aufarbeitung

  1. temperaturecooled to 0° C.
  2. stirringstirred at ambient temperature for 16 hours
  3. washwashed with aqueous sodium bicarbonate (30 mL)
  4. customThe layers were separated
  5. extractionthe aqueous layer was extracted with methylene chloride (50 mL)
  6. dry with materialThe combined organic layers were dried (MgSO4)
  7. filtrationfiltered
  8. concentrationconcentrated
  9. customThe residue was purified by flash chromatography over silica gel (3:2:1 chloroform/hexanes/diethyl ether)
  10. customto provide 0.98 g of the less polar diasteriomer

Quellen und Nachweise

ORD-Eintrag
ord-73265167ee1d421db5dd781435b3ae12
Quelldatensatz
uspto-grants-2001_02
Patentnummer
US06191140B1

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