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

HRID 855292Notes

Reaction equation

HRID 855292 reaction equation
[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]

Participants

8

Reactant 5

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

Product 1

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

Reagents, catalysts & solvents 2

HCID 702EthanolSolventHCID 5943Carbon TetrachlorideSolvent

Conditions

Temperature
0 °C

Procedure

A solution of 3.5 g of 4-(heptafluoroisopropyl)-toluene (13.4 mmol) in 100 ml tetra-chloromethane 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).

Workup

  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)

Sources & evidence

ORD record
ord-499c5272ce284c43928129726b99d9a9
Source dataset
uspto-grants-2007_08
Patent number
US07259183B2

Reaction notes

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