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

HRID 546165ノート

反応式

HRID 546165 の反応式
[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

参加物

7

反応物 3

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

生成物 1

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

試薬・触媒・溶媒 3

HCID 67553Tetrabutylammonium Iodide触媒HCID 8028Tetrahydrofuran溶媒2 回HCID 8857Ethyl Acetate溶媒

反応条件

温度
25 °C

実験手順

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).

後処理

  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)

出典と根拠

ORDレコード
ord-4f7d88a9ed884751ba63f65dbb3dc0c4
出典データセット
uspto-grants-2011_05
特許番号
US07935699B2

反応ノート

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