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

HRID 322616

反応式

HRID 322616 の反応式
[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]

参加物

6

反応物 3

HCID 74900Diethyl allylmalonateHCID 809722-Bromoethyl methyl etherHCID 5360545Sodium

生成物 1

HCID 22011257Diethyl 2-(2-methoxyethyl)-2-allylmalonate収率 87%

試薬・触媒・溶媒 2

HCID 702Ethanol溶媒3 回HCID 962Water溶媒

実験手順

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).

後処理

  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

出典と根拠

ORDレコード
ord-b7106348a3e84313a2abe2c00a83fa31
出典データセット
uspto-grants-2001_04
特許番号
US06211360B1

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