Phosphorus oxychloride → 7-Bromo-4-[(2,4-dichloro-5-methoxyphenyl)amino]-6-methoxy-3-quinolinecarbonitrile

HRID 1593778ノート

反応式

HRID 1593778 の反応式
[Br:1][C:2]1[CH:3]=[C:4]([CH:23]=[CH:24][C:25]=1[O:26][CH3:27])[NH:5][CH:6]=[C:7]([C:21]#[N:22])[C:8]([NH:10][C:11]1[CH:16]=[C:15]([O:17][CH3:18])[C:14]([Cl:19])=[CH:13][C:12]=1[Cl:20])=O.P(Cl)(Cl)(Cl)=O>C(#N)C>[Br:1][C:2]1[CH:3]=[C:4]2[C:23]([C:8]([NH:10][C:11]3[CH:16]=[C:15]([O:17][CH3:18])[C:14]([Cl:19])=[CH:13][C:12]=3[Cl:20])=[C:7]([C:21]#[N:22])[CH:6]=[N:5]2)=[CH:24][C:25]=1[O:26][CH3:27]

参加物

4

反応物 2

HCID 24813Phosphorus oxychlorideHCID 693135643-bromo-4-methoxyanilino-N-(2,4-dichloro-5-methoxyphenyl)-2-cyano-2-propenamide

生成物 1

HCID 115181097-Bromo-4-[(2,4-dichloro-5-methoxyphenyl)amino]-6-methoxy-3-quinolinecarbonitrile収率 44.9%

試薬・触媒・溶媒 1

HCID 6342Acetonitrile溶媒

実験手順

A suspension of 3-bromo-4-methoxyanilino-N-(2,4-dichloro-5-methoxyphenyl)-2-cyano-2-propenamide (4.00 g, 8.50 mmol) in 200 mL of acetonitrile was heated to reflux and phosphorous oxychloride (5.0 mL) was added dropwise, via syringe. The reaction mixture was heated at reflux overnight, then cooled to room temperature and concentrated in vacuo. The residue was cooled to 0° C. and saturated aqueous sodium bicarbonate was added. The mixture was stirred for 1 hour and then extracted with a large volume of ethyl acetate. The organic layer was washed with saturated aqueous sodium bicarbonate, dried over magnesium sulfate and filtered. The filtrate was reduced in volume until solids appeared. The solids were collected by filtration, washed with diethyl ether and hexanes to provide 1.73 g of 7-bromo-4-[(2,4-dichloro-5-methoxyphenyl)amino]-6-methoxy-3-quinolinecarbonitrile as a light tan solid, mp >250° C. 1H NMR (400 MHz, DMSO-d6) δ 3.87 (s, 3H), 4.04 (s, 3H), 7.41 (s, 1H), 7.78 (s, 1H), 7.99(s, 1H), 8.22 (s, 1H), 8.48 (s, 1H), 9.93 (s, 1H); MS (ES) m/z449.9, 451.9, 453.9 (M−H)−

後処理

  1. temperaturewas heated
  2. temperatureto reflux
  3. temperatureThe reaction mixture was heated
  4. temperatureat reflux overnight
  5. concentrationconcentrated in vacuo
  6. temperatureThe residue was cooled to 0° C.
  7. additionsaturated aqueous sodium bicarbonate was added
  8. extractionextracted with a large volume of ethyl acetate
  9. washThe organic layer was washed with saturated aqueous sodium bicarbonate
  10. dry with materialdried over magnesium sulfate
  11. filtrationfiltered
  12. filtrationThe solids were collected by filtration
  13. washwashed with diethyl ether and hexanes

出典と根拠

ORDレコード
ord-e16ac575d24c48099f9add2f638c906c
出典データセット
uspto-grants-2007_11
特許番号
US07297795B2

反応ノート

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