Water → HCID 68729664, compound

HRID 509508Notes

Reaction equation

HRID 509508 reaction equation
[CH3:1][O:2][C:3](=[O:15])[C:4]1[CH:9]=[CH:8][C:7]([CH2:10]Br)=[CH:6][C:5]=1[N+:12]([O-:14])=[O:13].[NH:16]([C:24]([O:26][C:27]([CH3:30])([CH3:29])[CH3:28])=[O:25])[C:17]([O:19][C:20]([CH3:23])([CH3:22])[CH3:21])=[O:18].C(=O)([O-])[O-].[Cs+].[Cs+].O>CC(=O)CC.[Cl-].[Na+].O.[I-].[Li+].C(OCC)(=O)C>[CH3:1][O:2][C:3](=[O:15])[C:4]1[CH:9]=[CH:8][C:7]([CH2:10][N:16]([C:17]([O:19][C:20]([CH3:23])([CH3:22])[CH3:21])=[O:18])[C:24]([O:26][C:27]([CH3:28])([CH3:29])[CH3:30])=[O:25])=[CH:6][C:5]=1[N+:12]([O-:14])=[O:13]

Participants

9

Reactant 4

HCID 962WaterHCID 10796Cesium carbonateHCID 279800Di-tert-butyl IminodicarboxylateHCID 19777981HCID 19777981, compound

Product 1

HCID 68729664HCID 68729664, compoundYield 96.7%

Reagents, catalysts & solvents 4

HCID 66321Lithium iodideCatalystHCID 6569Methyl Ethyl KetoneSolventHCID 8857Ethyl AcetateSolventHCID 57417360Sodium chloride; waterSolvent

Conditions

Temperature
100 °C

Procedure

A stirred mixture of 4-bromomethyl-2-nitro-benzoic acid methyl ester (66.3 g, 241.9 mmol), di-tert-butyl iminodicarboxylate (52.72 g, 242.6 mmol), cesium carbonate (161.58 g, 495.9 mmol), and lithium iodide (1.62 g, 12 mmol) in 2-butanone (700 mL) was heated to reflux in a 100° C. oil bath for 12 hours while stirred with a mechanical stirrer. The mixture was allowed to cool to room temperature. To the mixture, was added brine (300 mL), water (300 mL), and ethyl acetate (600 mL), and the mixture was stirred for 10 minutes. The suspension was filtered through a pad of Celite. The two layers were separated, and the organic layer was evaporated to a less volume. The aqueous layer was extracted with ethyl acetate (2×150 mL). The combined organic layers were washed with brine (1×500 mL), dried over magnesium sulfate while de-colored at the same time by charcoal at room temperature with stirring for 30 minutes. The black mixture was filtered through a pad of Celite, and the filtrate was evaporated to give 4-(di-tert-butoxycarbonylamino-methyl)-2-nitro-benzoic acid methyl ester as a brown oil (96.0 g, 96.7% yield). The product was used in the next step without further purification.

Workup

  1. temperaturewas heated
  2. temperatureto cool to room temperature
  3. stirringthe mixture was stirred for 10 minutes
  4. filtrationThe suspension was filtered through a pad of Celite
  5. customThe two layers were separated
  6. customthe organic layer was evaporated to a less volume
  7. extractionThe aqueous layer was extracted with ethyl acetate (2×150 mL)
  8. washThe combined organic layers were washed with brine (1×500 mL)
  9. dry with materialdried over magnesium sulfate while de-colored at the same time by charcoal at room temperature
  10. stirringwith stirring for 30 minutes
  11. filtrationThe black mixture was filtered through a pad of Celite
  12. customthe filtrate was evaporated

Sources & evidence

ORD record
ord-2bfd717f828f41c8b54faa6f2547b7b4
Source dataset
uspto-grants-2015_08
Patent number
US09096573B2

Reaction notes

Loading…