Ammonium Chloride → Ethyl 2-cyano-3,3-dimethyl-4-(3-methoxyphenyl)butanoate

HRID 1274161ノート

反応式

HRID 1274161 の反応式
[C:1]([C:3](=[C:9]([CH3:11])[CH3:10])[C:4]([O:6][CH2:7][CH3:8])=[O:5])#[N:2].[CH3:12][O:13][C:14]1[CH:15]=[C:16]([CH:20]=[CH:21][CH:22]=1)[CH2:17][Mg]Cl.COC1C=C(C=CC=1)CCl.[NH4+].[Cl-]>C1COCC1.CCOCC>[C:1]([CH:3]([C:9]([CH3:10])([CH3:11])[CH2:17][C:16]1[CH:20]=[CH:21][CH:22]=[C:14]([O:13][CH3:12])[CH:15]=1)[C:4]([O:6][CH2:7][CH3:8])=[O:5])#[N:2]

参加物

7

反応物 4

HCID 25517Ammonium ChlorideHCID 699943-Methoxybenzyl chlorideHCID 1365732-Cyano-3-methyl-but-2-enoic acid ethyl esterHCID 178490222HCID 178490222、化合物

生成物 1

HCID 22120417Ethyl 2-cyano-3,3-dimethyl-4-(3-methoxyphenyl)butanoate収率 51%

試薬・触媒・溶媒 2

HCID 3283Diethyl Ether溶媒2 回HCID 8028Tetrahydrofuran溶媒

実験手順

A solution of ethyl 2-cyano-3-methylcrotonate (10.8 g, 0.07 mol) in THF (100 mL) was added dropwise to a stirred ethereal solution of 3-methoxybenzylmagnesium chloride (prepared by adding a solution of 3-methoxybenzyl chloride (9.3 mL, 0.064 mol) in ether (48 mL) to a slurry of Mg (1.7 g, 0.07 mol) in ether (20 mL)). After addition the mixture was stirred at room temperature for a further 2 h then NH4Cl (sat., 50 mL) was added. The solution was partitioned between EtOAc (200 mL) and water (200 mL) and the organic layer separated and dried (MgSO4). The solvent was evaporated and the residue chromatographed on silica gel, eluting with petrol:EtOAc (5:1). The title compound (9.0 g, 51%) was isolated as a colourless oil. 1H NMR (360 MHz, CDCl3) δ 1.10 (3H, s), 1.20 (3H, s), 1.33 (3H, t, J=7.1 Hz), 2.74 (1H, d, J=13.5 Hz), 2.78 (1H, d, J=13.5 Hz), 3.33 (1H, s), 3.81 (3H, s), 4.26 (2H, q, J=7.1 Hz), 6.72-6.82 (3H, m), 7.22 (1H, t, J=7.8 Hz). MS (ES+) 276 (M+1).

後処理

  1. customprepared
  2. additionAfter addition the mixture
  3. customThe solution was partitioned between EtOAc (200 mL) and water (200 mL)
  4. customthe organic layer separated
  5. dry with materialdried (MgSO4)
  6. customThe solvent was evaporated
  7. customthe residue chromatographed on silica gel
  8. washeluting with petrol:EtOAc (5:1)

出典と根拠

ORDレコード
ord-35eed30291f64c64883b60c527406f0c
出典データセット
uspto-grants-2000_12
特許番号
US06156761

反応ノート

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