3-Nitrophenol → Tert-butyl 2-(3-nitrophenoxy)acetate

HRID 2181180노트

반응식

HRID 2181180 반응식
[N+:1]([C:4]1[CH:5]=[C:6]([OH:10])[CH:7]=[CH:8][CH:9]=1)([O-:3])=[O:2].Br[CH2:12][C:13]([O:15][C:16]([CH3:19])([CH3:18])[CH3:17])=[O:14].C(=O)([O-])[O-].[K+].[K+]>CC(C)=O>[N+:1]([C:4]1[CH:5]=[C:6]([CH:7]=[CH:8][CH:9]=1)[O:10][CH2:12][C:13]([O:15][C:16]([CH3:19])([CH3:18])[CH3:17])=[O:14])([O-:3])=[O:2]

참가 물질

5

반응물 3

HCID 111373-NitrophenolHCID 11430Potassium CarbonateHCID 79177tert-Butyl bromoacetate

생성물 1

HCID 309909Tert-butyl 2-(3-nitrophenoxy)acetate수율 92%

시약·촉매·용매 1

HCID 180Acetone용매

실험 절차

A mixture of 3 g (21.56 mmol) of 3-nitrophenol, 4.3 g (22 mmol) of tert-butyl bromoacetate, 3.2 g of anhydrous potassium carbonate and 50 ml of acetone is stirred overnight at room temperature. The mixture is filtered and washed with acetone and both the filtrate and the washing product are evaporated to give a yellow oil. The oil is purified on a silica gel chromatography column using an EtOAc/cyclohexane mixture (50/50) as the eluent to give 5 g (92%) of tert-butyl 3-nitrophenoxyacetate (colourless oil). 2 g of Pd/C (10%) are added to a solution of 4.8 g (18.95 mmol) of tert-butyl 3-nitrophenoxyacetate in 20 ml of ethanol and the mixture is hydrogenated overnight at one atmosphere. The catalyst is filtered off. The solvent is evaporated off to give 3.38 g (80%) of tert-butyl 3-amidophenoxyacetate, which is chromatographed on a silica gel column using an EtOAc/cyclohexane mixture (50/50) as the eluent. A mixture of the resulting amine (0.5 g, 2.24 mmol) and 1,2-epoxy-3-phenoxypropane is heated at 70° C. overnight. After cooling, the product is washed with ethanol and the precipitate is filtered off to give 0.6 g of the tert-butyl ester. 0.6 g of this ester and 15 ml of 6 N HCl are mixed overnight at 80° C. The solvent is evaporated off and the residue is washed with an EtOH/CH3CN mixture and then recrystallized from CH3CN to give 0.36 g of a salt with the following characteristics: melting point 138-139° C.; 1H NMR (DMSO-d6) δ 3.82 (m, 2H), 3.96 (m, 4H), 4.06 (m, 1H), 4.72 (s, 2H), 6.88-7.00 (n, 5H Ar), 7.24-7.45 (m, 4H Ar).

후처리

  1. filtrationThe mixture is filtered
  2. washwashed with acetone and both the filtrate
  3. customthe washing product are evaporated
  4. customto give a yellow oil
  5. customThe oil is purified on a silica gel chromatography column

출처 및 근거

ORD 기록
ord-62af25a365e544f7b5b7745c455c29e5
출처 데이터셋
uspto-grants-2005_05
특허 번호
US06890955B2

반응 노트

불러오는 중…