Sodium Bicarbonate → chloromethyl methyl (3S,3aS,6R,6aS)-6-(nitrooxy)hexahydrofuro[3,2-b]furan-3-yl phosphate

HRID 222538Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 222538
C(=O)(O)[O-].[Na+].[P:6](O)([O:10][C@H:11]1[CH2:15][O:14][C@@H:13]2[C@H:16]([O:19][N+:20]([O-:22])=[O:21])[CH2:17][O:18][C@H:12]12)([O:8][CH3:9])=[O:7].S(Cl)([O:27][CH2:28][Cl:29])(=O)=O>S([O-])(O)(=O)=O.C([N+](CCCC)(CCCC)CCCC)CCC.ClCCl.O>[P:6]([O:10][C@H:11]1[CH2:15][O:14][C@@H:13]2[C@H:16]([O:19][N+:20]([O-:22])=[O:21])[CH2:17][O:18][C@H:12]12)([O:8][CH3:9])([O:27][CH2:28][Cl:29])=[O:7]

Komponenten

7

Edukt 3

HCID 516892Sodium BicarbonateHCID 2733556Chloromethyl chlorosulfateHCID 86652098methyl (3S,3aS,6R,6aS)-6-(nitrooxy)hexahydrofuro[3,2-b]furan-3-yl hydrogen phosphate

Produkt 1

HCID 86652100chloromethyl methyl (3S,3aS,6R,6aS)-6-(nitrooxy)hexahydrofuro[3,2-b]furan-3-yl phosphate

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 94433Tetrabutylammonium hydrogen sulfateKatalysatorHCID 962WaterLösungsmittelHCID 6344DichloromethaneLösungsmittel2×

Reaktionsbedingungen

Temperatur
0 °C

Versuchsvorschrift

Sodium bicarbonate (289 mg, 3.44 mmol) followed by tetrabutylammonium hydrogensulfate (29.2 mg, 0.086 mmol) were added to a vigorously stirred 0° C. mixture of methyl (3S,3aS,6R,6aS)-6-(nitrooxy)hexahydrofuro[3,2-b]furan-3-yl hydrogen phosphate (245 mg, 0.859 mmol) in dichloromethane (5 mL) and water (7.5 mL), and the mixture was stirred at 0° C. for 10 minutes. Chloromethyl chlorosulfate (0.106 mL, 1.03 mmol) in dichloromethane (2.5 mL) was added, and the mixture was stirred at room temperature for overnight. The organic phase was removed, dried and concentrated. Chromatography over silica, eluting with 20-60% ethyl acetate/hexane afforded the title compound as a colorless oil. 1H NMR (500 MHz, CDCl3) δ 5.72-5.64 (m, 2H), 5.36 (td, J=5.5, 2.8 Hz, 1H), 5.02 (t, J=5.2 Hz, 1H), 4.93 (quintet, J=3.6 Hz, 1H), 4.63 (dd, J=12.1, 4.8 Hz, 1H), 4.18 (dd, J=11.0, 7.3 Hz, 1H), 4.00 (dd, J=11.4, 2.8 Hz, 1H), 3.94 (dq, J=11.1, 2.4 Hz, 1H), 3.90 (dd, J=11.3, 5.6 Hz, 1H), 3.83 (d, J=11.4 Hz, 3H); LC-MS: m/z 334.0 (M+H).

Aufarbeitung

  1. stirringthe mixture was stirred at room temperature for overnight
  2. customThe organic phase was removed
  3. customdried
  4. concentrationconcentrated
  5. washChromatography over silica, eluting with 20-60% ethyl acetate/hexane

Quellen und Nachweise

ORD-Eintrag
ord-df771f6cfde6455bb2c2829d401b9f94
Quelldatensatz
uspto-grants-2012_06
Patentnummer
US08207208B2

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