Water → HCID 66643089, compound

HRID 1409628Notes

Reaction equation

HRID 1409628 reaction equation
[CH3:1][O:2][C:3](=[O:15])[C:4]1[C:9]([N+:10]([O-:12])=[O:11])=[CH:8][CH:7]=[CH:6][C:5]=1[CH2:13]Br.[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[C:9]([N+:10]([O-:12])=[O:11])=[CH:8][CH:7]=[CH:6][C:5]=1[CH2:13][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]

Participants

9

Reactant 4

HCID 962WaterHCID 10796Cesium carbonateHCID 279800Di-tert-butyl IminodicarboxylateHCID 21708527Methyl 2-(bromomethyl)-6-nitrobenzoate

Product 1

HCID 66643089HCID 66643089, compoundYield 94%

Reagents, catalysts & solvents 4

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

Conditions

Temperature
100 °C

Procedure

A stirred mixture of 2-bromomethyl-6-nitro-benzoic acid methyl ester (36.6 g, 134 mmol), di-tert-butyl iminodicarboxylate (29.1 g, 134 mmol), cesium carbonate (89.3 g, 274 mmol), and lithium iodide (0.89 g, 6.7 mmol) in 2-butanone (400 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 add brine (300 mL), water (300 mL), ethyl acetate (750 mL) and stirred for 10 minutes, then the suspension was filtered through a pad of Celite. The two layers were separated, and the organic layer was evaporated to a less volume and the aqueous layer was extracted with ethyl acetate (2×150 mL). The combined organic layers were washed with brine (500 mL), dried over magnesium sulfate while de-colored at the same time with charcoal at room temp for 30 minutes. The black mixture was filtered through a pad of Celite. The filtrate was evaporated to give 2-(di-tert-butoxycarbonylamino-methyl)-6-nitro-benzoic acid methyl ester as a brown oil (51.53 g, 94% yield). The product was used in the next step without further purification.

Workup

  1. temperaturewas heated
  2. temperatureto cool to room temperature
  3. stirringstirred 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 (500 mL)
  9. dry with materialdried over magnesium sulfate while de-colored at the same time with charcoal at room temp for 30 minutes
  10. filtrationThe black mixture was filtered through a pad of Celite
  11. customThe filtrate was evaporated

Sources & evidence

ORD record
ord-0ce9eb3ad69743739c25e047a2ab3eec
Source dataset
uspto-grants-2014_12
Patent number
US08921385B2

Reaction notes

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