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Epichlorohydrin → (r,s)-4-[2-Hydroxy-3-(3-pentylbicyclo[3.2.1]oct-8-yl)-propyl]-4h-benzo[1,4]oxazin-3-one

HRID 2103239
Notizen
Druckvorschau

Reaktionsgleichung

Reaktionsgleichung von HRID 2103239
[CH2:1]([CH:3]1[O:5][CH2:4]1)Cl.[C:6]([O-])([O-])=O.[Cs+].[Cs+].[O:12]1[C:17]2[CH:18]=[CH:19][CH:20]=[CH:21][C:16]=2[NH:15][C:14](=[O:22])[CH2:13]1.[CH2:23]([CH:28]1[CH2:34][CH:33]2N[CH:30]([CH2:31][CH2:32]2)[CH2:29]1)[CH2:24][CH2:25][CH2:26][CH3:27]>CCOCC.CN(C=O)C>[OH:5][C@H:3]([CH2:1][CH:6]1[CH:33]2[CH2:32][CH2:31][C@H:30]1[CH2:29][CH:28]([CH2:23][CH2:24][CH2:25][CH2:26][CH3:27])[CH2:34]2)[CH2:4][N:15]1[C:16]2[CH:21]=[CH:20][CH:19]=[CH:18][C:17]=2[O:12][CH2:13][C:14]1=[O:22]
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Komponenten

7

Edukt 4

HCID 7835EpichlorohydrinHCID 10796Cesium carbonate2×HCID 727572H-1,4-benzoxazin-3(4H)-oneHCID 219898523-Pentyl-8-azabicyclo[3.2.1]octane

Produkt 1

HCID 68912783(r,s)-4-[2-Hydroxy-3-(3-pentylbicyclo[3.2.1]oct-8-yl)-propyl]-4h-benzo[1,4]oxazin-3-oneAusbeute 47,2 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 3283Diethyl EtherLösungsmittel2×HCID 6228DimethylformamideLösungsmittel2×

Reaktionsbedingungen

Temperatur
65 °C

Versuchsvorschrift

Epichlorohydrin (0.48 g, 5.2 mmol), Cs2CO3 (2.3 g, 7.0 mmol), 4H-benzo[1,4]oxazin-3-one (0.52 g, 3.5 mmol) were stirred with dry DMF (7 mL) for 22 h. Thereafter the mixture was diluted with ether (50 mL) washed with water (10 mL) and then brine (10 mL). The organic phase was dried over Na2SO4, filtered, concentrated under reduced pressure and the residue was purified by flash CC (SiO2; CH2Cl2/acetone/MeOH 95:3:2). Of the resulting oil (0.060 g, 0.29 mmol) was dissolved in DMF (1.5 mL), 3-pentyl-8-azabicyclo[3.2.1]octane (0.060 g, 0.33 mmol) and Cs2CO3 (0.30 g, 0.81 mmol) were added and the mixture was shaken at 65° C. for 72 h. The mixture was then poured into ether (25 mL) washed with water (10 mL) and the water phase was extracted with ether (20 mL). The combined organic phase was washed with brine (10 mL), dried over Na2SO4, filtered, concentrated under reduced pressure and the residue was purified by cation exchange CC, followed by flash CC (SiO2; CH2Cl2:acetone:MeOH 85/10/5) to yield the title compound (0.060 g, 33% (from 4H-benzo[1,4]oxazin-3-one)). 1H NMR (CDCl3) δ 7.42 (dm, J=7.2 Hz, 1H), 7.05-6.94 (m, 3H), 4.60 (ABq, J=14.8, 16.8 Hz, 2H), 4.15 (dd, J=3.2, 14.0 Hz, 1H), 3.86-3.78 (m, 3H), 3.14 (m, 2H), 2.54 (dd, J=4.8, 12.5 Hz, 1H), 2.22 (dd, J=9.2, 12.4 Hz), 2.16-1.98 (m, 2H), 1.98-1.83 (m, 2H), 1.72-1.55 (m, 3H), 1.43-1.34 (m, 2H), 1.42-1.15 (m, 8H), 0.87 (t, J=7.2 Hz). 13C NMR (CDCl3) δ 165.3, 145.5, 129.7, 124.2, 122.9, 117.0, 116.6, 67.9, 67.4, 60.9, 58.6, 56.7, 46.7, 38.3, 36.7, 36.5, 28.5, 28.3, 28.2, 27.1, 22.9, 14.3. HPLC-MS (ammonium acetate) [M+H]+=387.3.

Aufarbeitung

  1. washwashed with water (10 mL)
  2. dry with materialThe organic phase was dried over Na2SO4
  3. filtrationfiltered
  4. concentrationconcentrated under reduced pressure
  5. customthe residue was purified by flash CC (SiO2; CH2Cl2/acetone/MeOH 95:3:2)
  6. washwashed with water (10 mL)
  7. extractionthe water phase was extracted with ether (20 mL)
  8. washThe combined organic phase was washed with brine (10 mL)
  9. dry with materialdried over Na2SO4
  10. filtrationfiltered
  11. concentrationconcentrated under reduced pressure
  12. customthe residue was purified by cation exchange CC

Quellen und Nachweise

ORD-Eintrag
ord-da8b80dae2544e8489b90d6bb9d9d199
Quelldatensatz
uspto-grants-2009_08
DOI
10.6084/m9.figshare.5104873.v1
Patentnummer
US07576100B2

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