Allyl bromide → 2-[4,5-Dimethoxy-2-(morpholine-4-sulfonyl)-phenyl]-pent-4-enoic acid benzyl ester

HRID 23583Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 23583
[CH2:1]([O:8][C:9](=[O:30])[CH2:10][C:11]1[CH:16]=[C:15]([O:17][CH3:18])[C:14]([O:19][CH3:20])=[CH:13][C:12]=1[S:21]([N:24]1[CH2:29][CH2:28][O:27][CH2:26][CH2:25]1)(=[O:23])=[O:22])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.C[Si]([N-][Si](C)(C)C)(C)C.[Li+].[CH2:41](Br)[CH:42]=[CH2:43].[Cl-].[NH4+]>O1CCCC1>[CH2:1]([O:8][C:9](=[O:30])[CH:10]([C:11]1[CH:16]=[C:15]([O:17][CH3:18])[C:14]([O:19][CH3:20])=[CH:13][C:12]=1[S:21]([N:24]1[CH2:25][CH2:26][O:27][CH2:28][CH2:29]1)(=[O:23])=[O:22])[CH2:43][CH:42]=[CH2:41])[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

Komponenten

6

Edukt 4

HCID 7841Allyl bromideHCID 25517Ammonium ChlorideHCID 2733832Lithium HexamethyldisilazideHCID 69732356[4,5-Dimethoxy-2-(morpholine-4-sulfonyl)-phenyl]-acetic acid benzyl ester

Produkt 1

HCID 697313012-[4,5-Dimethoxy-2-(morpholine-4-sulfonyl)-phenyl]-pent-4-enoic acid benzyl esterAusbeute 99,4 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 8028TetrahydrofuranLösungsmittel2×

Reaktionsbedingungen

Temperatur
-78 °C

Versuchsvorschrift

To a stirred mixture of [4,5-dimethoxy-2-(morpholine-4-sulfonyl)-phenyl]-acetic acid benzyl ester (3.00 g, 6.89 mmol) in anhydrous tetrahydrofuran (50 cm3) under an atmosphere of dry nitrogen cooled to −78° C. in an dry ice/acetone bath was added a 1 M solution of lithium bis(trimethylsilyl)amide (7.60 cm3, 7.60 mmol) in tetrahydrofuran dropwise over 5 minutes. The mixture was warmed to 0° C. in an ice bath for 30 minutes to dissolve all solids and cooled again to −78° C. in an dry ice/acetone bath. Neat allyl bromide (0.720 cm3, 8.27 mmol) was added at −78° C. over 5 minutes and the solution warmed to ambient temperature over 2 hours. Saturated ammonium chloride solution (30 cm3) was added and extracted with ethyl acetate (3×40 cm3). The combined ethyl acetate extracts were washed with brine solution (30 cm3), dried over sodium sulfate, vacuum filtered and the filtrate volatile fractions removed in vacuo to afford the title compound as a golden oil (3.25 g, 99.4%) with a positive ion ESI (M+H)+476.3.

Aufarbeitung

  1. temperatureThe mixture was warmed to 0° C. in an ice bath for 30 minutes
  2. dissolutionto dissolve all solids
  3. temperaturecooled again to −78° C. in an dry ice/acetone bath
  4. temperaturethe solution warmed to ambient temperature over 2 hours
  5. extractionextracted with ethyl acetate (3×40 cm3)
  6. washThe combined ethyl acetate extracts were washed with brine solution (30 cm3)
  7. dry with materialdried over sodium sulfate, vacuum
  8. filtrationfiltered
  9. customthe filtrate volatile fractions removed in vacuo

Quellen und Nachweise

ORD-Eintrag
ord-44b7ae648e6d493da47fdbfcca587ba7
Quelldatensatz
uspto-grants-2005_02
Patentnummer
US06852713B2

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