Potassium Carbonate → Diethyl 2-(3-ethynylphenylamino)ethylphosphonate

HRID 1782175ノート

反応式

HRID 1782175 の反応式
[C:1]([C:3]1[CH:4]=[C:5]([CH:7]=[CH:8][CH:9]=1)[NH2:6])#[CH:2].Br[CH2:11][CH2:12][P:13](=[O:20])([O:17][CH2:18][CH3:19])[O:14][CH2:15][CH3:16].C(=O)([O-])[O-].[K+].[K+]>C(#N)C>[C:1]([C:3]1[CH:4]=[C:5]([NH:6][CH2:11][CH2:12][P:13](=[O:20])([O:17][CH2:18][CH3:19])[O:14][CH2:15][CH3:16])[CH:7]=[CH:8][CH:9]=1)#[CH:2]

参加物

5

反応物 3

HCID 11430Potassium CarbonateHCID 79218Diethyl (2-bromoethyl)phosphonateHCID 104682Benzenamine, 3-ethynyl-

生成物 1

HCID 57588428Diethyl 2-(3-ethynylphenylamino)ethylphosphonate収率 7.2%

試薬・触媒・溶媒 1

HCID 6342Acetonitrile溶媒

実験手順

3-Ethynyl aniline (2.36 g, 22.1 mmol), diethyl 2-bromoethylphosphonate (5.41 g, 22.1 mmol) and potassium carbonate (3.1 gm, 22.1 mmol) were heated at 90° C. in anhydrous acetonitrile (40 mL) for 26 h. The solvent was removed under reduced pressure and the residue was partitioned between ethyl acetate and water. The organic layer was separated, washed with brine, dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure. The resulting residue was purified by flash column chromatography on silica gel, eluting with 1:1 ethyl acetate:hexanes followed by 97:3 methylene chloride:methanol to provide diethyl 2-(3-ethynylphenylamino)ethylphosphonate (450 mg) as a yellow oil. 1H NMR (CDCl3) δ 7.15 (t, 1H), 6.83 (d, 1H), 6.70 (br s, 1H), 6.60 (m, 1H), 4.10 (m, 4H), 3.41 (m, 2H), 3.00 (s, 1H), 2.10 (m, 2H), 1.35 ppm (m, 6H). MW=281 confirmed by LC-MS, tr=11.65 min (Method Y) MH+=282.

後処理

  1. customThe solvent was removed under reduced pressure
  2. customthe residue was partitioned between ethyl acetate and water
  3. customThe organic layer was separated
  4. washwashed with brine
  5. dry with materialdried over anhydrous sodium sulfate
  6. filtrationfiltered
  7. concentrationconcentrated under reduced pressure
  8. customThe resulting residue was purified by flash column chromatography on silica gel
  9. washeluting with 1:1 ethyl acetate

出典と根拠

ORDレコード
ord-8afee5cf262241de8d877b4321071517
出典データセット
uspto-grants-2009_03
特許番号
US07498353B2

反応ノート

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