Phthalic Anhydride → 5-(Tert-butyldimethylsilyloxy)-2-phthalimido-1-nitrobenzene

HRID 395814Notes

Reaction equation

HRID 395814 reaction equation
[N+:1]([C:4]1[CH:10]=[C:9]([O:11][Si:12]([C:15]([CH3:18])([CH3:17])[CH3:16])([CH3:14])[CH3:13])[CH:8]=[CH:7][C:5]=1[NH2:6])([O-:3])=[O:2].[C:19]1(=O)[O:24][C:22](=[O:23])[C:21]2=[CH:25][CH:26]=[CH:27][CH:28]=[C:20]12.C(N(C(C)C)CC)(C)C>C1(C)C=CC=CC=1>[Si:12]([O:11][C:9]1[CH:8]=[CH:7][C:5]([N:6]2[C:22](=[O:23])[C:21]3=[CH:25][CH:26]=[CH:27][CH:28]=[C:20]3[C:19]2=[O:24])=[C:4]([N+:1]([O-:3])=[O:2])[CH:10]=1)([C:15]([CH3:18])([CH3:17])[CH3:16])([CH3:13])[CH3:14]

Participants

5

Reactant 3

HCID 6811Phthalic AnhydrideHCID 81531DiisopropylethylamineHCID 120422994-(Tert-butyldimethylsilyl)oxy-2-nitroaniline

Product 1

HCID 181744725-(Tert-butyldimethylsilyloxy)-2-phthalimido-1-nitrobenzeneYield 80%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

A mixture of 2-nitro-4-(tert-butyldimethylsilyloxy)aniline (10.3 g, 38.5 mmol) and phthalic anhydride (6.50 g, 41.5 mmol) in toluene (30 mL) was refluxed for 18 h. A Dean-Stark apparatus was fitted to the flask, diisopropylethylamine (0.1 mL) was added and water was removed azeotropically over the next 24 h. About 20 mL of solvent was removed by distillation and the resultant solution allowed to cool to room temperature. The residue was diluted with methylene chloride and passed through a plug of silica gel eluting with methylene chloride. The desired fractions were combined and concentrated in vacuo. Recrystallization from methylene chloride-hexane provided 12.2 g (80%) of the title compound in two crops.

Workup

  1. temperaturewas refluxed for 18 h
  2. additionwas added
  3. customwater was removed azeotropically over the next 24 h
  4. customAbout 20 mL of solvent was removed by distillation
  5. additionThe residue was diluted with methylene chloride
  6. concentrationconcentrated in vacuo
  7. customRecrystallization from methylene chloride-hexane

Sources & evidence

ORD record
ord-50aff6e8a9ad4efebff0cb77262d093c
Source dataset
uspto-grants-2003_08
Patent number
US06605626B2

Reaction notes

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