Hydroxylamine, sulfate (1:1) → ((R)-1-benzyloxymethyl-3-butenyloxy)acetaldehyde oxime

HRID 68388

反応式

HRID 68388 の反応式
C(O[CH:4](OCC)[CH2:5][O:6][C@H:7]([CH2:17][CH:18]=[CH2:19])[CH2:8][O:9][CH2:10][C:11]1[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=1)C.S(O)(O)(=O)=O.[NH2:28][OH:29].C([O-])(=O)C.[Na+]>C(O)=O.O.C(O)C>[CH2:10]([O:9][CH2:8][C@H:7]([O:6][CH2:5][CH:4]=[N:28][OH:29])[CH2:17][CH:18]=[CH2:19])[C:11]1[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=1

参加物

7

反応物 3

HCID 159255Hydroxylamine, sulfate (1:1)HCID 517045Sodium AcetateHCID 59281174[(R)-2-(2,2-diethoxyethoxy)-4-pentenyloxymethyl]benzene

生成物 1

HCID 86640913((R)-1-benzyloxymethyl-3-butenyloxy)acetaldehyde oxime収率 123.7%

試薬・触媒・溶媒 3

HCID 284Formic Acid溶媒2 回HCID 702Ethanol溶媒HCID 962Water溶媒2 回

実験手順

A solution of ({[(2R)-2-(2,2-diethoxyethoxy)pent-4-en-1-yl]oxy}methyl)benzene (C2) (234 g, 0.759 mol) in formic acid (400 mL) and water (100 mL) was stirred at room temperature for 2 hours. As LCMS analysis revealed a small amount of remaining starting material, formic acid (50 mL) was added and the reaction mixture was stirred for a further 30 minutes. The reaction mixture was diluted with ethanol (1 L) and water (400 mL). Hydroxylamine sulfate (435 g, 2.65 mol) and sodium acetate (217 g, 2.64 mol) were added and the reaction was stirred at room temperature for 18 hours. The reaction mixture was then filtered and concentrated in vacuo; the residue was partitioned between ethyl acetate (500 mL) and water (1 L), and the aqueous layer was extracted with ethyl acetate (3×500 mL). The combined organic layers were washed with saturated aqueous sodium chloride solution (2×500 mL), dried over magnesium sulfate, filtered, and concentrated under reduced pressure to provide the product as an orange oil (234 g), which was taken directly to the following step. By 1H NMR, this material consisted of a roughly 1:1 mixture of oxime isomers. LCMS m/z 250.1 [M+H+]. 1H NMR (400 MHz, CDCl3), characteristic peaks: δ [7.52 (t, J=5.5 Hz) and 6.96 (t, J=3.6 Hz), total 1H], 7.28-7.39 (m, 5H), 5.74-5.87 (m, 1H), 5.04-5.14 (m, 2H), 4.55 and 4.56 (2 s, total 2H), {4.45-4.55 (m) and [4.27 (dd, half of ABX pattern, J=13.2, 5.4 Hz) and 4.21 (dd, half of ABX pattern, J=13.2, 5.6 Hz)], total 2H}, 2.30-2.37 (m, 2H).

後処理

  1. additionwas added
  2. stirringthe reaction was stirred at room temperature for 18 hours
  3. filtrationThe reaction mixture was then filtered
  4. concentrationconcentrated in vacuo
  5. customthe residue was partitioned between ethyl acetate (500 mL) and water (1 L)
  6. extractionthe aqueous layer was extracted with ethyl acetate (3×500 mL)
  7. washThe combined organic layers were washed with saturated aqueous sodium chloride solution (2×500 mL)
  8. dry with materialdried over magnesium sulfate
  9. filtrationfiltered
  10. concentrationconcentrated under reduced pressure

出典と根拠

ORDレコード
ord-1f9197f9961c48a1aa5fe46126c0d2a8
出典データセット
uspto-grants-2014_09
特許番号
US08822456B2

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