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

HRID 429222Notes

Reaction equation

HRID 429222 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) δ 11.05 (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) (s, 3H); 13C NMR (DMSO-d6) δ 172.20, 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 C14HB11N3O6: 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-46e6e054eb3343d194f324fbf2a5efba
Source dataset
uspto-grants-2001_11
Patent number
US06316471B1

Reaction notes

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