Water → Methyl 4-(2-fluoro-4-nitrophenyl)butanoate

HRID 1192865Notes

Reaction equation

HRID 1192865 reaction equation
[F:1][C:2]1[CH:7]=[C:6]([N+:8]([O-:10])=[O:9])[CH:5]=[CH:4][C:3]=1[C:11](C(OC)=O)([C:18]([O:20][CH3:21])=[O:19])[CH2:12][CH2:13][C:14]([O:16][CH3:17])=[O:15].[Cl-].[Na+].O>CS(C)=O>[F:1][C:2]1[CH:7]=[C:6]([N+:8]([O-:10])=[O:9])[CH:5]=[CH:4][C:3]=1[CH2:11][CH2:12][CH2:13][C:14]([O:16][CH3:17])=[O:15].[F:1][C:2]1[CH:7]=[C:6]([N+:8]([O-:10])=[O:9])[CH:5]=[CH:4][C:3]=1[CH:11]([CH2:12][CH2:13][C:14]([O:16][CH3:17])=[O:15])[C:18]([O:20][CH3:21])=[O:19]

Participants

6

Reactant 3

HCID 962Water2×HCID 5234Sodium ChlorideHCID 68733963Trimethyl 1-(2-fluoro-4-nitrophenyl)propane-1,1,3-tricarboxylate

Product 2

HCID 57672627Dimethyl 2-(2-fluoro-4-nitrophenyl)pentanedioateYield 38%HCID 57672633Methyl 4-(2-fluoro-4-nitrophenyl)butanoateYield 45%

Reagents, catalysts & solvents 1

HCID 679Dimethyl SulfoxideSolvent

Conditions

Temperature
21 °C

Procedure

A solution of compound Trimethyl 1-(2-fluoro-4-nitrophenyl)propane-1,1,3-tricarboxylate (85) (0.23 g, 0.63 mmol), sodium chloride (0.11 g, 1.90 mmol) and water (0.15 mL) in distilled dimethylsulfoxide (4 mL) was heated to 155° C. overnight. The reaction mixture was allowed to cool to 21° C. and then worked up by adding water and extracting with ethyl acetate (2×50 mL). The organic layer was dried over MgSO4, concentrated and the residue was purified with silica gel column chromatography (hexane:ethyl acetate, 8:1) to give desired Methyl 4-(2-fluoro-4-nitrophenyl)butanoate (84) (69 mg, 45%) and dimethyl 2-(2-fluoro-4-nitrophenyl)pentanedioate (83) (72 mg, 38%): 1H NMR of (10) δ 8.04 (dd, 1H, J=8.5, 2.2 Hz), 7.95 (dd, 1H, J=9.5, 2.2 Hz), 7.53 (dd, 1H, J=8.5, 7.1 Hz), 4.08 (t, 1H, J=7.6 Hz) 3.71 (s, 3H), 3.66 (s, 3H), 2.43-2.52 (m, 1H), 2.31-2.35 (m, 2H), 2.06-2.14 (m, 1H); 1H NMR of (84) δ 7.98 (dd, 1H, J=8.4, 2.2 Hz), 7.90 (dd, 1H, J=9.5, 2.2 Hz), 7.38 (dd, 1H, J=8.4, 7.3 Hz), 3.68 (s, 3H), 2.79 (t, 2H, J=7.7 Hz) 2.38 (t, 2H, J=7.3 Hz) 1.94-2.02 (m, 2H).

Workup

  1. extractionextracting with ethyl acetate (2×50 mL)
  2. dry with materialThe organic layer was dried over MgSO4
  3. concentrationconcentrated
  4. customthe residue was purified with silica gel column chromatography (hexane:ethyl acetate, 8:1)

Sources & evidence

ORD record
ord-a8fd445aac2c4d008317315328349d1d
Source dataset
uspto-grants-2014_03
Patent number
US08680291B2

Reaction notes

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