1-Octanol → Pentanoic acid, 5-(octyloxy)-

HRID 1461008ノート

反応式

HRID 1461008 の反応式
Br[CH2:2][CH2:3][CH2:4][CH2:5][C:6]([OH:8])=[O:7].[OH-].[K+].[CH2:11]([OH:19])[CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][CH3:18]>>[CH2:11]([O:19][CH2:2][CH2:3][CH2:4][CH2:5][C:6]([OH:8])=[O:7])[CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][CH3:18]

参加物

4

反応物 3

HCID 9571-OctanolHCID 14797Potassium HydroxideHCID 163685-Bromovaleric acid

生成物 1

HCID 452109Pentanoic acid, 5-(octyloxy)-収率 9%

反応条件

温度
97 °C

実験手順

5-bromopentanoic acid (2g, 11.0 mmol) was added to a solution of potassium hydroxide (2.48 g, 44.2 mmol) in 1-octanol (20 mL) and stirred at 97° C. for 27 hrs. After cooling, the product was extracted at pH=1 with ethyl acetate and water. The organic phase was dried over sodium sulfate and solvent was removed. 1-octanol was removed by short path (Kugelrohr) distillation (50-70° C., 0.5 mm Hg). To ensure complete cleavage of the octyl ester, the residue was stirred 3 hrs with methanol/water/KOH (50%/50%/2.5 g, 40 mL) at 25° C. 1-octanol was extracted into ethyl acetate at pH=12. 5-(octyloxy)pentanoic acid was extracted from the aqueous phase into ethyl acetate after adjusting the pH to 1.5 with HCl. After drying over sodium sulfate, the solvent was removed at reduced pressure. Silica column chromatography in 10% ethyl acetate/ hexane/0.3% formic acid, yielded 5-(octyloxy)pentanoic acid (235 mg, 9%): mp <30° C.; 1H NMR (300 MHz, CDC13) δ 0.88 (t, 3H, J=6.6), 1.18-1.39 (bm, 10H, methylene envelope), 1.48-1.77 (bm, 6H, CH2CH2OCH2CH2, CH2CH2COOH), 2.39 (t, 2H, J=7.1, CH2COOH), 3.34-3.49 (bm, 4H, CH2OCH2), 10.66 (br, 1H, COOH); 13 C NMR (75.4 MHz, CDC13) 14.18, 21.59, 22.73, 26.22, 29.03, 29.32, 29.51, 29.72, 31.89, 33.85, 70.22, 71.07, 179.55; m/z 231 (M+H).

後処理

  1. temperatureAfter cooling
  2. extractionthe product was extracted at pH=1 with ethyl acetate and water
  3. dry with materialThe organic phase was dried over sodium sulfate and solvent
  4. customwas removed
  5. custom1-octanol was removed by short path (Kugelrohr) distillation (50-70° C., 0.5 mm Hg)
  6. stirringthe residue was stirred 3 hrs with methanol/water/KOH (50%/50%/2.5 g, 40 mL) at 25° C
  7. extraction1-octanol was extracted into ethyl acetate at pH=12
  8. extraction5-(octyloxy)pentanoic acid was extracted from the aqueous phase into ethyl acetate
  9. dry with materialAfter drying over sodium sulfate
  10. customthe solvent was removed at reduced pressure

出典と根拠

ORDレコード
ord-8351a755be22486b88d52f2dfc4c4031
出典データセット
uspto-grants-1991_12
特許番号
US05073571

反応ノート

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