Benzyl Bromide → 5-((Benzyloxy)methyl)-2,2-dimethyl-1,3-dioxane

HRID 546165Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 546165
[H-].[Na+].[CH3:3][C:4]1([CH3:12])[O:9][CH2:8][CH:7]([CH2:10][OH:11])[CH2:6][O:5]1.[CH2:13](Br)[C:14]1[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1>O1CCCC1.[I-].C([N+](CCCC)(CCCC)CCCC)CCC.C(OCC)(=O)C>[CH2:13]([O:11][CH2:10][CH:7]1[CH2:8][O:9][C:4]([CH3:12])([CH3:3])[O:5][CH2:6]1)[C:14]1[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1

Komponenten

7

Edukt 3

HCID 7498Benzyl BromideHCID 24758Sodium hydrideHCID 3584869(2,2-Dimethyl-1,3-dioxan-5-yl)methanol

Produkt 1

HCID 232952655-((Benzyloxy)methyl)-2,2-dimethyl-1,3-dioxaneAusbeute 80 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 67553Tetrabutylammonium IodideKatalysatorHCID 8028TetrahydrofuranLösungsmittel2×HCID 8857Ethyl AcetateLösungsmittel

Reaktionsbedingungen

Temperatur
25 °C

Versuchsvorschrift

To a stirred suspension of sodium hydride (2.0 g, 42.02 mmol, 50% dispersion in oil) in tetrahydrofuran (20.0 ml) was added dropwise a solution of (2,2-dimethyl-[1,3]dioxan-5-yl)-methanol (4.09 g, 28.01 mmol) in tetrahydrofuran (10 ml) at 0° C. it was then stirred at 0° C. for 10 min and at 25° C. for 20 min. After that time, the reaction was cooled back to 0° C. and benzyl bromide (4.7 ml, 39.22 mmol) and tetrabutylammonium iodide (0.1 g, 0.27 mmol) were added. The reaction was stirred overnight at 25° C. After such time, the reaction was diluted with ethyl acetate and washed with water. The organic layer was dried over magnesium sulfate, filtered and then concentrated in vacuo. Purification on an AnaLogix Intelliflash system (120 g column, 15% ethyl acetate/hexanes to 25% ethyl acetate/hexanes) afforded 5-benzyloxymethyl-2,2-dimethyl-[1,3]dioxane (5.28 g, 80%) as a clear oil: 1H NMR (300 MHz, CDCl3) δ ppm 1.40 (s, 3H, CH3), 1.43 (s, 3H, CH3), 1.97-2.09 (m, 1H, CH), 3.53 (d, J=6.8 Hz, 2H, OCH2), 3.79 (dd, Jgem=11.9 Hz, J=6.4 Hz, 2H, 2×OCH of 2×OCH2), 3.98 (dd, Jgem=11.9 Hz, J=4.3 Hz, 2H, 2×OCH of 2×OCH2), 4.52 (s, 2H, OCH2Ar), 7.27-7.39 (m, 5H, Ar).

Aufarbeitung

  1. temperatureAfter that time, the reaction was cooled back to 0° C.
  2. stirringThe reaction was stirred overnight at 25° C
  3. washwashed with water
  4. dry with materialThe organic layer was dried over magnesium sulfate
  5. filtrationfiltered
  6. concentrationconcentrated in vacuo
  7. customPurification on an AnaLogix Intelliflash system (120 g column, 15% ethyl acetate/hexanes to 25% ethyl acetate/hexanes)

Quellen und Nachweise

ORD-Eintrag
ord-4f7d88a9ed884751ba63f65dbb3dc0c4
Quelldatensatz
uspto-grants-2011_05
Patentnummer
US07935699B2

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