Sodium hydride → HCID 59799799, compound

HRID 240670Notes

Reaction equation

HRID 240670 reaction equation
[C:1]([O:5][C:6](=[O:9])[NH:7][CH3:8])([CH3:4])([CH3:3])[CH3:2].[H-].[Na+].[CH3:12][O:13][C:14](=[O:27])[C:15]1[C:16](=[C:21]([CH2:25]Br)[CH:22]=[CH:23][CH:24]=1)[C:17]([O:19][CH3:20])=[O:18]>CN(C=O)C>[CH3:12][O:13][C:14](=[O:27])[C:15]1[C:16](=[C:21]([CH2:25][N:7]([C:6]([O:5][C:1]([CH3:4])([CH3:3])[CH3:2])=[O:9])[CH3:8])[CH:22]=[CH:23][CH:24]=1)[C:17]([O:19][CH3:20])=[O:18]

Participants

5

Reactant 3

HCID 24758Sodium hydrideHCID 527635tert-Butyl methylcarbamateHCID 22464988Dimethyl 3-(bromomethyl)phthalate

Product 1

HCID 59799799HCID 59799799, compoundYield 60.1%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent2×

Procedure

A solution of methyl-carbamic acid t-butyl ester (5.0 g, 38.0 mmol) in DMF (50 mL) was chilled in an ice bath, and NaH (60%, 1.7 g, 41.8 mmol) was added in portions at 10C. The mixture was stirred for an additional 30 minutes. A solution of 3-bromomethyl-phthalic acid dimethyl ester (10.9 g, 38.0 mmol) in DMF (20 mL) was slowly added, keeping the temperature at 10-15° C. The resulting mixture was stirred at room temperature overnight. The mixture was poured into ice water (400 mL) and extracted with EtOAc (4×70 mL). The combined EtOAc extracts were washed with water (3×50 mL) and brine (50 mL), and dried (MgSO4). The solvent was removed in vacuo, and the residue was purified by flash chromatography (SiO2, Hexane:EtOAc 8:2) to give 3-[(t-butoxycarbonyl-methyl-amino)-methyl]-phthalic dimethyl ester (7.7 g, 60%) as an oil: 1H NMR (CDCl3) δ 7.93-7.89 (m, 1H), 7.49-7.46 (m, 2H), 4.46 (s, 2H), 3.94 (s, 3H), 3.89 (s, 3H), 2.87-2.76 (b, 3H), 1.49-1.42 (b, 9H).

Workup

  1. customat 10-15° C
  2. stirringThe resulting mixture was stirred at room temperature overnight
  3. extractionextracted with EtOAc (4×70 mL)
  4. washThe combined EtOAc extracts were washed with water (3×50 mL) and brine (50 mL)
  5. dry with materialdried (MgSO4)
  6. customThe solvent was removed in vacuo
  7. customthe residue was purified by flash chromatography (SiO2, Hexane:EtOAc 8:2)

Sources & evidence

ORD record
ord-86932436053840a19abaab41239a35e9
Source dataset
uspto-grants-2014_02
Patent number
US08648096B2

Reaction notes

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