Potassium Nitrate → Ethyl 3-(5-cyclopentyl-4-methoxycarbonyloxy-2-nitro-phenyl)propanoate

HRID 383382Notes

Reaction equation

HRID 383382 reaction equation
[CH:1]1([C:6]2[CH:7]=[C:8]([CH2:17][CH2:18][C:19]([O:21][CH2:22][CH3:23])=[O:20])[CH:9]=[CH:10][C:11]=2[O:12][C:13]([O:15][CH3:16])=[O:14])[CH2:5][CH2:4][CH2:3][CH2:2]1.[N+:24]([O-])([O-:26])=[O:25].[K+]>OS(O)(=O)=O>[CH:1]1([C:6]2[C:11]([O:12][C:13]([O:15][CH3:16])=[O:14])=[CH:10][C:9]([N+:24]([O-:26])=[O:25])=[C:8]([CH2:17][CH2:18][C:19]([O:21][CH2:22][CH3:23])=[O:20])[CH:7]=2)[CH2:2][CH2:3][CH2:4][CH2:5]1

Participants

4

Reactant 2

HCID 24434Potassium NitrateHCID 59395019Ethyl 3-(3-cyclopentyl-4-methoxycarbonyloxy-phenyl)propanoate

Product 1

HCID 59395000Ethyl 3-(5-cyclopentyl-4-methoxycarbonyloxy-2-nitro-phenyl)propanoateYield 78.9%

Reagents, catalysts & solvents 1

HCID 1118Sulfuric AcidSolvent

Conditions

Temperature
-2 °C

Procedure

Ethyl 3-(3-cyclopentyl-4-methoxycarbonyloxy-phenyl)propanoate (920 mg, 2.87 mmol) was dissolved in H2SO4 (2.2 mL) and the reaction mixture was cooled to −2° C. internal temperature. KNO3 (348 mg, 3.45 mmol) was added in portions over 1 h maintain the internal temperature at 0° C. After 1 h at 0° C. the reaction mixture was poured over ice (30 mL) and partitioned between dichloromethane/water and separated. The organic layer was washed twice with a saturated aqueous NaHCO3, dried over Na2SO4, filtered and concentrated. Purification by silica gel chromatography (0-40% ethyl acetate/hexanes) afforded ethyl 3-(5-cyclopentyl-4-methoxycarbonyloxy-2-nitro-phenyl)propanoate (827 mg, 76% yield). 1H NMR (400.0 MHz, DMSO-d6) δ 7.96 (s, 1H), 7.53 (s, 1H), 4.04 (q, J=7.1 Hz, 2H), 3.86 (s, 3H), 3.11 (t, J=7.6 Hz, 3H), 2.68 (t, J=7.6 Hz, 2H), 1.99-1.91 (m, 2H), 1.82-1.75 (m, 2H), 1.69-1.61 (m, 2H), 1.58-1.53 (m, 2H), 1.15 (t, J=7.1 Hz, 3H).

Workup

  1. temperaturemaintain the internal temperature at 0° C
  2. custompartitioned between dichloromethane/water
  3. customseparated
  4. washThe organic layer was washed twice with a saturated aqueous NaHCO3
  5. dry with materialdried over Na2SO4
  6. filtrationfiltered
  7. concentrationconcentrated
  8. customPurification by silica gel chromatography (0-40% ethyl acetate/hexanes)

Sources & evidence

ORD record
ord-63084b58aedc4871a3af48896b24d96c
Source dataset
uspto-grants-2013_02
Patent number
US08367660B2

Reaction notes

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