3-Nitrophthalic anhydride → 3-(3-Nitrophthalimido)-3-methylpiperidine-2,6-dione

HRID 1937441Notes

Reaction equation

HRID 1937441 reaction equation
Cl.[NH2:2][C:3]1([CH3:11])[CH2:9][CH2:8][C:7](=[O:10])[NH:6][C:4]1=[O:5].[N+:12]([C:15]1[CH:25]=[CH:24][CH:23]=[C:17]2[C:18]([O:20][C:21](=O)[C:16]=12)=[O:19])([O-:14])=[O:13].C([O-])(=O)C.[Na+]>C(O)(=O)C>[N+:12]([C:15]1[CH:25]=[CH:24][CH:23]=[C:17]2[C:18]([N:2]([C:3]3([CH3:11])[CH2:9][CH2:8][C:7](=[O:10])[NH:6][C:4]3=[O:5])[C:21](=[O:20])[C:16]=12)=[O:19])([O-:14])=[O:13]

Participants

5

Reactant 3

HCID 216313-Nitrophthalic anhydrideHCID 517045Sodium AcetateHCID 219282523-Amino-3-methylpiperidine-2,6-dione hydrochloride

Product 1

HCID 155520373-(3-Nitrophthalimido)-3-methylpiperidine-2,6-dioneYield 68%

Reagents, catalysts & solvents 1

HCID 176Acetic AcidSolvent

Procedure

A stirred mixture of α-amino-α-methylglutarimide hydrochloride (1.2 g, 6.7 mmol), 3-nitrophthalic anhydride (1.3 g, 6.7 mmol), and sodium acetate (0.6 g, 7.4 mmol) in acetic acid (30 mL) was heated to reflux under nitrogen for 6 hours. The mixture then was cooled and concentrated in vacuo. The resulting solid was slurried in water (30 mL) and methylene chloride (30 mL) for 30 min. The suspension was filtered, the solid was washed with methylene chloride, and dried in vacuo (60° C., <1 mm) to afford 1.44 g (68%) of 3-(3-nitrophthalimido)-3-methylpiperidine-2,6-dione as a off-white solid: mp 265-266.5° C.; 1H NMR (DMSO-d6) δ11.05 (s, 1H), 8.31 (dd, J=1.1 and 7.9 Hz, 1H), 8.16-8.03 (m, 2H), 2.67-2.49 (m, 3H), 2.08-2.02 (m, 1H), 1.88 (s, 3H); 13C NMR (DMSO-d6) δ172.20 171.71, 165.89, 163.30, 144.19, 136.43, 133.04, 128.49, 126.77, 122.25, 59.22, 28.87, 28.49, 21.04; HPLC, Water Nova-Pak/C18 column, 4 micron, 1 mL/min, 240 nm, 20/80 CH3CN/0.1% H3PO4(aq), 7.38 min(98%). Anal. Calcd For C14H11N3O6: C, 53.00; H, 3.49; N, 13.24. Found: C, 52.77; H, 3.29; N, 13.00.

Workup

  1. temperaturewas heated
  2. temperatureto reflux under nitrogen for 6 hours
  3. temperatureThe mixture then was cooled
  4. concentrationconcentrated in vacuo
  5. filtrationThe suspension was filtered
  6. washthe solid was washed with methylene chloride
  7. customdried in vacuo (60° C., <1 mm)

Sources & evidence

ORD record
ord-7bd85fa6bcfe4b53906e2608c0141e2a
Source dataset
uspto-grants-2002_05
Patent number
US06395754B1

Reaction notes

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