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

HRID 1274161노트

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HRID 1274161 반응식
[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]

참가 물질

7

반응물 4

HCID 25517Ammonium ChlorideHCID 699943-Methoxybenzyl chlorideHCID 1365732-Cyano-3-methyl-but-2-enoic acid ethyl esterHCID 178490222HCID 178490222, 화합물

생성물 1

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

시약·촉매·용매 2

HCID 3283Diethyl Ether용매2회HCID 8028Tetrahydrofuran용매

실험 절차

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).

후처리

  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)

출처 및 근거

ORD 기록
ord-35eed30291f64c64883b60c527406f0c
출처 데이터셋
uspto-grants-2000_12
특허 번호
US06156761

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