Dimethyl Sulfate → N-Boc-2-Methyl-Piperidine

HRID 840680

反応式

HRID 840680 の反応式
[C:1]([N:8]1[CH2:13][CH2:12][CH2:11][CH2:10][CH2:9]1)([O:3][C:4]([CH3:7])([CH3:6])[CH3:5])=[O:2].[CH3:14]N(CCN(C)C)C.[Li]C(CC)C.S(OC)(OC)(=O)=O>CCOCC.O>[C:1]([N:8]1[CH2:9][CH2:10][CH2:11][CH2:12][CH:13]1[CH3:14])([O:3][C:4]([CH3:7])([CH3:6])[CH3:5])=[O:2]

参加物

7

反応物 4

HCID 6497Dimethyl SulfateHCID 8037N,N,N',N'-TetramethylethylenediamineHCID 7010304N-(tert-butoxycarbonyl)piperidineHCID 178418400CID 53628100

生成物 1

HCID 4578077N-Boc-2-Methyl-Piperidine収率 99.2%

試薬・触媒・溶媒 2

HCID 962Water溶媒HCID 3283Diethyl Ether溶媒2 回

反応条件

温度
-78 °C

実験手順

A solution of N-Boc-Piperidine (15.0 g, 80.95 mmol) in ether (160 mL) was cooled to −78° C. and treated with TMEDA (15.9 mL, 105.2 mmol) followed by sec-BuLi (85 mL, 105.2 mmol) dropwise. The mixture was stirred for 3 h at −78° C. and then treated with a solution of dimethyl sulfate (15.3 mL, 161.9 mmol) in 65 mL of ether. The mixture was warmed to room temperature and then was diluted with water and extracted with ether. The combined extracts were dried over K2CO3 and then concentrated to give a crude product as a colorless oil. The product was purified by column chromatography on silca gel with 5% EtOAc/hexane to afford 16.0 g (81%) of product as a clear oil which was homogeneous by TLC analysis. 1H NMR (300 MHz) 67 4.33 (m, 1 H), 3.92-3.81 (pair of br. d, 1 H), 2.81-2.72 (dt, 1H), 1.60-1.36 (m, 15 H), 1.09-1.07 (d, 3 H); 13C NMR (75 MHz) 154.9 (s), 78.6 (s), 45.9 (s), 38.6 (s), 29.9 (s), 28.4 (s), 25.6 (s), 18.6 (s), 15.6 (s), ppm.

後処理

  1. temperatureThe mixture was warmed to room temperature
  2. extractionextracted with ether
  3. dry with materialThe combined extracts were dried over K2CO3
  4. concentrationconcentrated
  5. customto give a crude product as a colorless oil
  6. customThe product was purified by column chromatography on silca gel with 5% EtOAc/hexane

出典と根拠

ORDレコード
ord-04bcec3d8e0849d38352a346ae5610cd
出典データセット
uspto-grants-2002_04
特許番号
US06369078B1

関連ノート

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