Acetaldehyde → 1-Fluoro-4-nitro-2-(prop-1-en-1-yl)benzene

HRID 85222Notes

Reaction equation

HRID 85222 reaction equation
C[Si]([N-][Si](C)(C)C)(C)C.[Na+].[Br-].[F:12][C:13]1[CH:38]=[CH:37][C:36]([N+:39]([O-:41])=[O:40])=[CH:35][C:14]=1[CH2:15][P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.[CH:42](=O)[CH3:43].O>O1CCOCC1>[F:12][C:13]1[CH:38]=[CH:37][C:36]([N+:39]([O-:41])=[O:40])=[CH:35][C:14]=1[CH:15]=[CH:42][CH3:43]

Participants

6

Reactant 4

HCID 177AcetaldehydeHCID 962WaterHCID 2724254Sodium bis(trimethylsilyl)amideHCID 86643536(2-Fluoro-5-nitrobenzyl)(triphenyl)phosphonium bromide

Product 1

HCID 684983641-Fluoro-4-nitro-2-(prop-1-en-1-yl)benzene

Reagents, catalysts & solvents 1

HCID 312751,4-DioxaneSolvent2×

Procedure

At 10° C., 5.99 g (32.7 mmol) sodium bis(trimethylsilyl)amide are added dropwise to a solution of 13.5 g (27.3 mmol) of the compound from Example 47A in 145 ml of dioxane. The mixture is stirred at this temperature for 1 h. A solution of 2.40 g (54.5 mmol) of acetaldehyde in 5 ml of dioxane is then added, and the reaction is stirred at RT for 1 h. 400 ml of water are then added, the mixture is extracted three times with dichloromethane and the combined organic phases are washed twice with saturated aqueous sodium chloride solution. After drying over sodium sulphate and subsequent filtration, the solvent is removed under reduced pressure. The product is purified by chromatography on silica gel (mobile phase: cyclohexane/ethyl acetate=40:1). This gives 5.2 g (100% of theory) of the desired product as an E/Z isomer mixture.

Workup

  1. stirringthe reaction is stirred at RT for 1 h
  2. extractionthe mixture is extracted three times with dichloromethane
  3. washthe combined organic phases are washed twice with saturated aqueous sodium chloride solution
  4. dry with materialAfter drying over sodium sulphate and subsequent filtration
  5. customthe solvent is removed under reduced pressure
  6. customThe product is purified by chromatography on silica gel (mobile phase: cyclohexane/ethyl acetate=40:1)

Sources & evidence

ORD record
ord-078512f7c64840d5811245054e50967e
Source dataset
uspto-grants-2014_09
Patent number
US08846934B2

Reaction notes

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