Dimethyl Sulfate → 1,1-Dimethylethyl 2-ethyl-6-methyl-1-piperidinecarboxylate

HRID 840687

반응식

HRID 840687 반응식
[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]

참가 물질

7

반응물 4

HCID 6497Dimethyl SulfateHCID 8037N,N,N',N'-TetramethylethylenediamineHCID 12170201tert-Butyl 2-Ethylpiperidine-1-carboxylateHCID 178418400CID 53628100

생성물 1

HCID 226201481,1-Dimethylethyl 2-ethyl-6-methyl-1-piperidinecarboxylate수율 59%

시약·촉매·용매 2

HCID 962Water용매HCID 3283Diethyl Ether용매2회

반응 조건

온도
-20 °C

실험 절차

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) δ3.91-3.87 (m, 1 H), 3.69-3.65 (m, 1 H), 1.83-1.41 (m, 17 H), 1.21-1.19 (d, 3 H), 0.85-0.82 (t, 3 H); 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.

후처리

  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

출처 및 근거

ORD 기록
ord-d626dcd95d644f5fb17e8d5c02714a69
출처 데이터셋
uspto-grants-2002_04
특허 번호
US06369078B1

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