Acetic Acid → HCID 57799941, compound

HRID 2100650Notes

Reaction equation

HRID 2100650 reaction equation
[F:1][C:2]1[C:3]([CH3:30])=[C:4]([CH:8]([CH2:19][C:20]([C:22]2[CH:27]=[CH:26][CH:25]=[C:24]([O:28][CH3:29])[CH:23]=2)=[O:21])[CH2:9][C:10]([C:12]2[CH:17]=[CH:16][CH:15]=[CH:14][C:13]=2[F:18])=[O:11])[CH:5]=[CH:6][CH:7]=1.[CH3:31][N+:32]([CH3:34])=[CH2:33].[I-].[C:36](O)(=O)C>>[CH3:33][N:32]([CH2:34][CH:9]([CH:8]([C:4]1[CH:5]=[CH:6][CH:7]=[C:2]([F:1])[C:3]=1[CH3:30])[C:19](=[CH2:36])[C:20]([C:22]1[CH:27]=[CH:26][CH:25]=[C:24]([O:28][CH3:29])[CH:23]=1)=[O:21])[C:10]([C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][C:13]=1[F:18])=[O:11])[CH3:31]

Participants

4

Reactant 3

HCID 176Acetic AcidHCID 2724133Dimethyl(methylene)ammounium iodide2×HCID 57799935HCID 57799935, compound

Product 1

HCID 57799941HCID 57799941, compound

Conditions

Temperature
120 °C

Procedure

A mixture of 3-(3-fluoro-2-methylphenyl)-1-(2-fluorophenyl)-5-(3-methoxyphenyl)pentane-1,5-dione (8.4 g, 20.6 mmol) and Eschenmoser's salt (17.6 g, 94.9 mmol) in acetic acid (86 mL) was stirred at 120° C. under nitrogen for 16 h. An additional 3.8 g (20 mmol) of Eschenmoser's salt was added and the mixture heated an additional 5 h. The solution was allowed to cool to room temperature and concentrated in vacuo. The residue was dissolved in EtOAc (30 mL) and 9:1 hexanes/EtOAc, and then treated with 10% NaOH until the pH reached 11 (150 mL). After 30 min, the resulting brown solid was collected by filtration, triturated with EtOAc (3×50 mL), and dried under vacuum at 40° C. to give 2-((dimethylamino)methyl)-3-(3-fluoro-2-methylphenyl)-1-(2-fluorophenyl)-5-(3-methoxyphenyl)-4-methylenepentane-1,5-dione product (7.5 g, 76% crude yield) as a yellow solid (characterized by LCMS and 1H NMR, LRMS (M+H+) m/z=478.7.

Workup

  1. temperaturethe mixture heated an additional 5 h
  2. temperatureto cool to room temperature
  3. concentrationconcentrated in vacuo
  4. dissolutionThe residue was dissolved in EtOAc (30 mL)
  5. addition9:1 hexanes/EtOAc, and then treated with 10% NaOH until the pH
  6. waitAfter 30 min
  7. filtrationthe resulting brown solid was collected by filtration
  8. customtriturated with EtOAc (3×50 mL)
  9. customdried under vacuum at 40° C.

Sources & evidence

ORD record
ord-542552d919cc42a5a934c73087c73d04
Source dataset
uspto-grants-2009_08
Patent number
US07572814B2

Reaction notes

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