Acetic Acid → HCID 57799945, compound

HRID 2100647Notes

Reaction equation

HRID 2100647 reaction equation
[F:1][C:2]1[C:3]([CH3:31])=[C:4]([CH:8]([CH2:20][C:21]([C:23]2[CH:28]=[CH:27][CH:26]=[C:25]([O:29][CH3:30])[CH:24]=2)=[O:22])[CH2:9][C:10]([C:12]2[CH:17]=[CH:16][CH:15]=[C:14]([O:18][CH3:19])[CH:13]=2)=[O:11])[CH:5]=[CH:6][CH:7]=1.[CH3:32][N+:33]([CH3:35])=[CH2:34].[I-].O.[OH-].[Na+].[C:40](O)(=O)C>CCOC(C)=O>[CH3:34][N:33]([CH2:35][CH:20]([CH:8]([C:4]1[CH:5]=[CH:6][CH:7]=[C:2]([F:1])[C:3]=1[CH3:31])[C:9](=[CH2:40])[C:10]([C:12]1[CH:17]=[CH:16][CH:15]=[C:14]([O:18][CH3:19])[CH:13]=1)=[O:11])[C:21]([C:23]1[CH:28]=[CH:27][CH:26]=[C:25]([O:29][CH3:30])[CH:24]=1)=[O:22])[CH3:32]

Participants

7

Reactant 5

HCID 176Acetic AcidHCID 962WaterHCID 14798Sodium Hydroxide2×HCID 2724133Dimethyl(methylene)ammounium iodideHCID 57799927HCID 57799927, compound

Product 1

HCID 57799945HCID 57799945, compound

Reagents, catalysts & solvents 1

HCID 8857Ethyl AcetateSolvent2×

Conditions

Temperature
120 °C

Procedure

A mixture of 3-(3-fluoro-2-methylphenyl)-1,5-bis(3-methoxyphenyl)pentane-1,5-dione (71.6 g, 170 mmol) and (145 g, 782 mmol) in acetic acid (300 mL) was stirred at 120° C. under nitrogen for 16 h. An additional 5 g (27.0 mmol) of Eschenmoser's salt was added and the mixture heated an additional 2 h. The solution was allowed to cool to room temperature and concentrated in vacuo to give a brown solid. The residue slurried with water and then treated with NaOH (s) until the pH reached 10. EtOAc (100 mL) was added, and the pH was adjusted to 10 with NaOH (s). The vigorously stirred mixture was diluted with 200 mL of EtOAc followed by 300 mL of hexanes. The pale yellow solid was isolated by filtration, washed with water (200 mL), hexanes (200 mL), and ethyl acetate (100 mL), and dried under vacuum at 45° C. overnight to give 91 g of desired 2-((dimethylamino)methyl)-3-(3-fluoro-2-methylphenyl)-1,5-bis(3-methoxyphenyl)-4-methylenepentane-1,5-dione product as a crude yellow solid, (characterized by LCMS and 1H NMR), LRMS (M+H+) m/z=490.5.

Workup

  1. temperaturethe mixture heated an additional 2 h
  2. temperatureto cool to room temperature
  3. concentrationconcentrated in vacuo
  4. customto give a brown solid
  5. customThe pale yellow solid was isolated by filtration
  6. washwashed with water (200 mL), hexanes (200 mL), and ethyl acetate (100 mL)
  7. customdried under vacuum at 45° C. overnight

Sources & evidence

ORD record
ord-bb9bae1f06f84dca98cc257104ed388a
Source dataset
uspto-grants-2009_08
Patent number
US07572814B2

Reaction notes

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