2-Nitropropane → 4-(1,1,1,2,3,3,3-Heptafluoropropan-2-yl)benzaldehyde

HRID 19769

反応式

HRID 19769 の反応式
[F:1][C:2]([F:17])([F:16])[C:3]([F:15])([C:8]1[CH:13]=[CH:12][C:11]([CH3:14])=[CH:10][CH:9]=1)[C:4]([F:7])([F:6])[F:5].BrN1C(=[O:24])CCC1=O.C(OOC(=O)C1C=CC=CC=1)(=O)C1C=CC=CC=1.[N+](C(C)C)([O-])=O.[Na]>ClC(Cl)(Cl)Cl.C(O)C>[F:15][C:3]([C:8]1[CH:13]=[CH:12][C:11]([CH:14]=[O:24])=[CH:10][CH:9]=1)([C:4]([F:7])([F:6])[F:5])[C:2]([F:16])([F:17])[F:1]

参加物

8

反応物 5

HCID 3982-NitropropaneHCID 7187Benzoyl PeroxideHCID 67184N-bromobutanimideHCID 1375814-(Heptafluoroisopropyl)tolueneHCID 5360545Sodium

生成物 1

HCID 860937714-(1,1,1,2,3,3,3-Heptafluoropropan-2-yl)benzaldehyde収率 30%

試薬・触媒・溶媒 2

HCID 702Ethanol溶媒HCID 5943Carbon Tetrachloride溶媒

反応条件

温度
0 °C

実験手順

A solution of 3.5 g of 4-(heptafluoroisopropyl)-toluene (13.4 mmol) in 100 ml tetrachloromethane was heated to reflux. Then 2.63 g of N-bromosuccinimide (14.8 mmol) and 326 mg of dibenzoyl peroxide (1.34 mmol) were added in small portions. After 5 h the mixture was cooled to 0° C., filtered and the solvent was evaporated. The remaining residue was dissolved in 15 ml ethanol and was added to a suspension that had been prepared by addition of 2-nitropropane (1.4 ml, 15.5 mmol) to a solution of 340 mg sodium (14.8 mmol) in ethanol. This mixture was stirred for 3 days. Then it was filtered, the solvent was removed and the remaining residue was dissolved in EtOAc and washed with 1 N sodium hydroxide solution, 1 N HCl solution, saturated NaHCO3 solution and with brine. The EtOAc layer was then dried with magnesium sulfate, filtered and concentrated. Purification of the residue (silica gel; c-hexane/EtOAc 10:1) gave 1.1 g (30%) of 4-(1,2,2,2-tetrafluoro-1-trifluoromethyl-ethyl)-benzaldehyde as a light yellow oil. 1H-NMR (CDCl3, 300 MHz: δ 7.82 (d, J=8 Hz, 2H), 8.03 (d, J=8 Hz, 2H), 10.11 (s, 1H).

後処理

  1. filtrationfiltered
  2. customthe solvent was evaporated
  3. dissolutionThe remaining residue was dissolved in 15 ml ethanol
  4. additionwas added to a suspension that
  5. filtrationThen it was filtered
  6. customthe solvent was removed
  7. dissolutionthe remaining residue was dissolved in EtOAc
  8. washwashed with 1 N sodium hydroxide solution, 1 N HCl solution, saturated NaHCO3 solution and with brine
  9. dry with materialThe EtOAc layer was then dried with magnesium sulfate
  10. filtrationfiltered
  11. concentrationconcentrated
  12. customPurification of the residue (silica gel; c-hexane/EtOAc 10:1)

出典と根拠

ORDレコード
ord-e6d81247fd784eafbacc72fb4e7e2380
出典データセット
uspto-grants-2010_06
特許番号
US07745477B2

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