Water → HCID 86665239、化合物

HRID 1028086ノート

反応式

HRID 1028086 の反応式
[OH-].[Na+].[CH2:3]([OH:21])[CH2:4]/[CH:5]=[CH:6]\[CH2:7]/[CH:8]=[CH:9]\[CH2:10]/[CH:11]=[CH:12]\[CH2:13]/[CH:14]=[CH:15]\[CH2:16]/[CH:17]=[CH:18]\[CH2:19][CH3:20].[C:22]([O:26][C:27](=[O:32])[CH:28](Br)[CH2:29][CH3:30])([CH3:25])([CH3:24])[CH3:23].O>S(=O)(=O)(O)[O-].C([N+](CCCC)(CCCC)CCCC)CCC.C1(C)C=CC=CC=1.CCCCCCC>[CH2:3]([O:21][CH:28]([CH2:29][CH3:30])[C:27]([O:26][C:22]([CH3:25])([CH3:24])[CH3:23])=[O:32])[CH2:4]/[CH:5]=[CH:6]\[CH2:7]/[CH:8]=[CH:9]\[CH2:10]/[CH:11]=[CH:12]\[CH2:13]/[CH:14]=[CH:15]\[CH2:16]/[CH:17]=[CH:18]\[CH2:19][CH3:20]

参加物

8

反応物 4

HCID 962WaterHCID 14798Sodium HydroxideHCID 13124118tert-Butyl 2-bromobutanoate2 回HCID 86665240HCID 86665240、化合物

生成物 1

HCID 86665239HCID 86665239、化合物収率 60.4%

試薬・触媒・溶媒 3

HCID 94433Tetrabutylammonium hydrogen sulfate触媒HCID 1140Toluene溶媒HCID 8900Heptane溶媒

反応条件

温度
50 °C

実験手順

An aqueous solution of sodium hydroxide (50% (w/w), 6 mL) was added portionwise to a mixture of (3Z,6Z,9Z,12Z,15Z)-octadeca-3,6,9,12,15-pentaen-1-ol (1.66 g, 6.37 mmol), tert-butyl-2-bromobutyrat (2.86 g, 12.8 mmol) and tetrabutylammonium bisulfate (0.65 g, 1.91 mmol) in toluene (12 ml). The reaction mixture was vigorously stirred under N2-atmosphere and warmed to 50° C. The reaction mixture was stirred at 50° C. for a total of 25 hrs. Additional tert-butyl-2-bromobutyrat (1.43 g, 6.41 mmol) and (1.42 g, 6.38 mmol) was added after 1½ hrs and 3 hrs respectively. The mixture was cooled to room temperature and added water (30 mL) and heptane (50 mL), the resulting two phases were separated and the organic phase was dried (Na2SO4), filtered and evaporated under reduced pressure. Flash chromatography on silica gel (30 g) eluting with heptane-heptane/EtOAc (99:1) yielded 1.55 g of the title compound as a liquid. 1H NMR (300 MHz, CDCl3) δ 0.96 (t, 3H), 0.97 (t, 3H), 1.48 (s, 9H), 1.64-1.86 (m, 2H), 2.03-2.12 (m, 2H), 2.39 (dd, J=12.1, 6.7 Hz, 2H), 2.79-2.86 (m, 8H), 3.29-3.37 (m, 1H), 3.57-3.66 (m, 2H), 5.27-5.49 (m, 10H).

後処理

  1. stirringThe reaction mixture was stirred at 50° C. for a total of 25 hrs
  2. temperatureThe mixture was cooled to room temperature
  3. customthe resulting two phases were separated
  4. dry with materialthe organic phase was dried (Na2SO4)
  5. filtrationfiltered
  6. customevaporated under reduced pressure
  7. washFlash chromatography on silica gel (30 g) eluting with heptane-heptane/EtOAc (99:1)

出典と根拠

ORDレコード
ord-dc0563c60dea463bbaf7cdb41592ef5f
出典データセット
uspto-grants-2014_05
特許番号
US08735436B2

反応ノート

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