Diethyl allylmalonate → Diethyl 2-(2-methoxyethyl)-2-allylmalonate

HRID 322616

반응식

HRID 322616 반응식
[Na].[CH2:2]([CH:5]([C:11]([O:13][CH2:14][CH3:15])=[O:12])[C:6]([O:8][CH2:9][CH3:10])=[O:7])[CH:3]=[CH2:4].[CH3:16][O:17][CH2:18][CH2:19]Br>C(O)C.O>[CH3:16][O:17][CH2:18][CH2:19][C:5]([CH2:2][CH:3]=[CH2:4])([C:11]([O:13][CH2:14][CH3:15])=[O:12])[C:6]([O:8][CH2:9][CH3:10])=[O:7]

참가 물질

6

반응물 3

HCID 74900Diethyl allylmalonateHCID 809722-Bromoethyl methyl etherHCID 5360545Sodium

생성물 1

HCID 22011257Diethyl 2-(2-methoxyethyl)-2-allylmalonate수율 87%

시약·촉매·용매 2

HCID 702Ethanol용매3회HCID 962Water용매

실험 절차

Metallic sodium (15 g, 230 mmol) was dissolved in dry ethanol (250 mL) with cooling in an ice bath, under nitrogen, and diethyl allylmalonate (Lancaster Synthesis, Windham, Mass.) (105 g, 525 mmol) in absolute ethanol (50 mL) was added dropwise under nitrogen. The mixture was stirred at room temperature for 1 h. and 2-bromoethyl methyl ether (87.57 g, 630 mmol) in absolute ethanol (50 mL) was then added dropwise. The mixture was heated at reflux for 3 h and then cooled to room temperature. The precipitate solid was filtered and washed with ethanol (2×100 mL). The residue obtained upon concentration of the filtrate was diluted with water (1 L). The mixture was extracted with ether (2×150 mL), dried over MgSO4 and concentrated to give the diester ether 2 (118 g, 87%) as a viscous liquid. IR (KBr) υmax 3069, 2971, 2927, 1734, 1640, 1459, 1443, 1382, 1361, 1284, 1223, 1196, 1119, 1077, 1031, 922, 856 cm−1: 1HNMR (CDCl3) δ1.24 t, J=7.0 Hz, 6 H), 2.17 (t, J=6.4 Hz, 2 H), 2.68 (d, J=7.1 Hz, 2 H), 3.2 (s, 3 H), 3.41 (t, J=6.5 Hz, 2 H), 4.17 (dis q, 4 H), 5.04-5.12 (m, 2 H), 5.63-5.79 (m, 1 H); 13CNMR (CDCl3) δ13.98, 32.05, 37.31, 55.08, 58.52, 61.13, 68.34, 118.93, 132.49, 170.17; mass spectrum (EI), m/z (rel itensity) 259 (M++1.16), 227 (20), 213 (19), 200 (37), 185 (13), 167 (17), 154 (25), 153 (65), 139 (38), 125 (25), 108 (100), 81 (30), 79 (31), 67 (23), 59 (23), 53 (23).

후처리

  1. temperaturewith cooling in an ice bath, under nitrogen
  2. temperatureThe mixture was heated
  3. temperatureat reflux for 3 h
  4. temperaturecooled to room temperature
  5. filtrationThe precipitate solid was filtered
  6. washwashed with ethanol (2×100 mL)
  7. customThe residue obtained upon concentration of the filtrate
  8. extractionThe mixture was extracted with ether (2×150 mL)
  9. dry with materialdried over MgSO4
  10. concentrationconcentrated

출처 및 근거

ORD 기록
ord-b7106348a3e84313a2abe2c00a83fa31
출처 데이터셋
uspto-grants-2001_04
특허 번호
US06211360B1

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