Dimethyl Sulfoxide → (R)-2-(Trityl-amino)-butyraldehyde

HRID 1432389ノート

反応式

HRID 1432389 の反応式
CS(C)=O.C(Cl)(=O)C(Cl)=O.[C:11]([NH:30][C@H:31]([CH2:34][CH3:35])[CH2:32][OH:33])([C:24]1[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=1)([C:18]1[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=1)[C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1.CCN(CC)CC>C(Cl)Cl.CCCCCC.CCOCC>[C:11]([NH:30][C@H:31]([CH2:34][CH3:35])[CH:32]=[O:33])([C:18]1[CH:19]=[CH:20][CH:21]=[CH:22][CH:23]=1)([C:24]1[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=1)[C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1

参加物

7

反応物 4

HCID 679Dimethyl SulfoxideHCID 8471TriethylamineHCID 65578Oxalyl chlorideHCID 57395035(2R)-2-[(Triphenylmethyl)amino]butan-1-ol

生成物 1

HCID 57714153(R)-2-(Trityl-amino)-butyraldehyde収率 52.1%

試薬・触媒・溶媒 2

HCID 6344Dichloromethane溶媒4 回HCID 21584099Diethylether hexane溶媒

反応条件

温度
-45 °C

実験手順

To a stirred solution of DMSO (3.0 mL, 42.28 mmol) in CH2Cl2 (30 mL) under Ar at −45° C., was added oxalyl chloride (2 M in CH2Cl2, 10.56 mL, 21.12 mmol) dropwise. The reaction mixture was stirred at −45° C. for 1 h, after which time a solution of (R)-2-(trityl-amino)-butan-1-ol (5 g, 15.08 mmol) in CH2Cl2 (30 mL) was added dropwise with stirring. The reaction mixture was sired at this temperature for 3 h, when TLC (8:2 hexane/Et2O) indicated that the reaction had gone to completion. Et3N (10.5 mL, 75.33 mmol) in CH2Cl2 (30 mL) was added and the solution was allowed to warm to RT over 16 h. It was diluted with more CH2Cl2 (200 mL) and washed with H2O (250 mL). The aqueous phase was extracted with CH2Cl2 (3×50 mL) and the combined organic phases washed with brine (50 mL), dried (MgSO4), and evaporated in vacuo. The residue was dissolved in Et2O (30 mL), the solid precipitate was removed by filtration, and the filtrate was evaporated in vacuo. The residue was dissolved in hexane (50 mL), the solid precipitate was removed by filtration, and the filtrate was evaporated in vacuo to afford the title compound as a light yellow oil (2.59 g, 52%). 1H-NMR (d6-DMSO, 250 MHz): δ 0.77 (t, 3H, J=7.42 Hz, —NHCH(CH2CH3)CHO), 1.34-1.61 (m, 2H, —NHCH(CH2CH3)CHO), 2.92 (m, 1H, —NHCH(CH2CH3)CHO), 3.62 (d, 1H, J=8.21 Hz, —NHCH(CH2CH3)CHO), 7.16-7.46 (m, 15H, 3×Bz), 8.77 (d, 1H, J=3.00 Hz, —NHCH(CH2CH3)CHO).

後処理

  1. stirringwith stirring
  2. waitThe reaction mixture was sired at this temperature for 3 h
  3. temperatureto warm to RT over 16 h
  4. washwashed with H2O (250 mL)
  5. extractionThe aqueous phase was extracted with CH2Cl2 (3×50 mL)
  6. washthe combined organic phases washed with brine (50 mL)
  7. dry with materialdried (MgSO4)
  8. customevaporated in vacuo
  9. dissolutionThe residue was dissolved in Et2O (30 mL)
  10. customthe solid precipitate was removed by filtration
  11. customthe filtrate was evaporated in vacuo
  12. dissolutionThe residue was dissolved in hexane (50 mL)
  13. customthe solid precipitate was removed by filtration
  14. customthe filtrate was evaporated in vacuo

出典と根拠

ORDレコード
ord-6e146b74ea2e4dc5b428b27b8d6a8f5d
出典データセット
uspto-grants-2009_11
特許番号
US07612079B2

反応ノート

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