Diethyl Ether → 2-Amino-4'-methoxybenzophenone

HRID 593484ノート

反応式

HRID 593484 の反応式
[Mg].Br[C:3]1[CH:8]=[CH:7][C:6]([O:9][CH3:10])=[CH:5][CH:4]=1.[NH2:11][C:12]1[CH:19]=[CH:18][CH:17]=[CH:16][C:13]=1[C:14]#N.C([O:22]CC)C>BrC(Br)C>[NH2:11][C:12]1[CH:19]=[CH:18][CH:17]=[CH:16][C:13]=1[C:14]([C:3]1[CH:8]=[CH:7][C:6]([O:9][CH3:10])=[CH:5][CH:4]=1)=[O:22]

参加物

6

反応物 4

HCID 3283Diethyl Ether3 回HCID 77304-BromoanisoleHCID 729132-AminobenzonitrileHCID 5462224Magnesium

生成物 1

HCID 122064592-Amino-4'-methoxybenzophenone収率 81%

試薬・触媒・溶媒 1

HCID 112011,1-Dibromoethane触媒

実験手順

To a 250 mL round-bottomed flask charged with magnesium (1.646 g, 67.7 mmol) and ethyl ether (47.0 ml) was added two drops of dibromoethane and the mixture was heated to reflux for 15 minutes. p-Bromoanisole (6.35 ml, 50.8 mmol) in diethyl ether (47.0 ml) was slowly added through an addition funnel while a refluxing temperature was maintained. The resulting mixture was heated for 3 hrs, and then cooled to room temperature. A solution of 2-aminobenzonitrile (2 g, 16.93 mmol) in diethyl ether (47.0 ml) was added dropwise over 15 min. After the addition, the mixture was refluxed for 16 hrs. The volume was then reduced by half under reduced pressure and the resulting mixture was quenched slowly with ice (100 g). Next, 6N HCl (10 mL) was then added and the mixture was stirred at room temperature for 16 hrs. The pH was adjusted to pH 8 with 5N NaOH and diluted with saturated NaHCO3 (50 ml). The phases were separated and the aqueous layer was back extracted with ethyl acetate (2×200 mL). The combined organic layers were dried (MgSO4), filtered and concentrated. The crude material was purified by flash chromatography (Teledyne ISCO CombiFlash Rf, 0% to 70% solvent A/B=heptane/EtOAc, REDISEP® SiO2 120 g). Concentration of the appropriate fractions provided Intermediate 6A (3.13 g, 81%). 1H NMR (400 MHz, DMSO-d6) δ 7.62-7.55 (m, 2H), 7.34-7.22 (m, 2H), 7.09-7.01 (m, 2H), 6.87-6.78 (m, 3H), 6.53 (ddd, J=8.0, 7.0, 1.1 Hz, 1H), 3.85 (s, 3H).

後処理

  1. temperaturethe mixture was heated
  2. temperatureto reflux for 15 minutes
  3. temperaturewas maintained
  4. temperatureThe resulting mixture was heated for 3 hrs
  5. additionAfter the addition
  6. temperaturethe mixture was refluxed for 16 hrs
  7. customthe resulting mixture was quenched slowly with ice (100 g)
  8. additionNext, 6N HCl (10 mL) was then added
  9. additiondiluted with saturated NaHCO3 (50 ml)
  10. customThe phases were separated
  11. extractionthe aqueous layer was back extracted with ethyl acetate (2×200 mL)
  12. dry with materialThe combined organic layers were dried (MgSO4)
  13. filtrationfiltered
  14. concentrationconcentrated
  15. customThe crude material was purified by flash chromatography (Teledyne ISCO CombiFlash Rf, 0% to 70% solvent A/B=heptane/EtOAc, REDISEP® SiO2 120 g)

出典と根拠

ORDレコード
ord-13e2f82f42264992b6f3ea91dcdcafa2
出典データセット
uspto-grants-2016_01
特許番号
US09242940B2

反応ノート

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