Dimethyl Sulfate → N-Boc-2-Ethyl-6-methylPiperidine

HRID 1919723

反応式

HRID 1919723 の反応式
[C:1]([N:8]1[CH2:13][CH2:12][CH2:11][CH2:10][CH:9]1[CH2:14][CH3:15])([O:3][C:4]([CH3:7])([CH3:6])[CH3:5])=[O:2].[CH3:16]N(CCN(C)C)C.[Li]C(CC)C.S(OC)(OC)(=O)=O>CCOCC.O>[C:1]([N:8]1[CH:13]([CH3:16])[CH2:12][CH2:11][CH2:10][CH:9]1[CH2:14][CH3:15])([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 12170201tert-Butyl 2-Ethylpiperidine-1-carboxylateHCID 178418400CID 53628100

生成物 1

HCID 22620148N-Boc-2-Ethyl-6-methylPiperidine収率 59%

試薬・触媒・溶媒 2

HCID 962Water溶媒HCID 3283Diethyl Ether溶媒2 回

反応条件

温度
-20 °C

実験手順

A solution of N-Boc-2-ethylpiperidine (1.5 g, 7.0 mmol) in 28 mL of ether was cooled to −60° C. and treated with TMEDA (1.6 mL, 10.85 mmol), followed by sec-BuLi (8.5 mL, 10.85 mmol) dropwise. The mixture was slowly warmed to −20° C., stirred for 30 min, and then cooled to −78° C. The mixture was treated with a solution of dimethyl sulfate (1.6 mL, 16.69 mmol) in ether and slowly warmed to room temperature. The mixture was diluted with water and then extracted with ether. The combined extracts were dried over K2CO3 and concentrated to give a crude product as an oil which was chromatographed on silica with 5% EtOAc/hexane to give 0.88 g (59%) of the product which was homogeneous by TLC analysis. 1H NMR (250 MHz) δ 3.91-3.87 (m, 1H), 3.69-3.65 (m, 1H), 1.83-1.41 (m, 17H), 1.21-1.19 (d, 3H), 0.85-0.82 (t, 3H); 13C NMR (62.7 MHz) 155.2 (s), 78.6 (s), 53.0 (s), 46.8 (s), 28.5 (s), 27.2 (s), 26.7 (s), 22.4 (s), 20.7 (s), 13.4 (s), 11.4 (s) ppm.

後処理

  1. temperaturecooled to −78° C
  2. temperatureslowly warmed to room temperature
  3. extractionextracted with ether
  4. dry with materialThe combined extracts were dried over K2CO3
  5. concentrationconcentrated
  6. customto give a crude product as an oil which
  7. customwas chromatographed on silica with 5% EtOAc/hexane

出典と根拠

ORDレコード
ord-a2c66eea1a8b437ea6a106e794bad348
出典データセット
uspto-grants-2012_05
特許番号
US08168657B2

関連ノート

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