Triphenylphosphine → Methyl 5-bromo-2-{[2-({[(1,1-dimethylethyl)oxy]carbonyl}amino)ethyl]oxy}benzoate

HRID 1514233Notes

Reaction equation

HRID 1514233 reaction equation
CC(OC(/N=N/C(OC(C)C)=O)=O)C.[Br:15][C:16]1[CH:17]=[CH:18][C:19]([OH:26])=[C:20]([CH:25]=1)[C:21]([O:23][CH3:24])=[O:22].O[CH2:28][CH2:29][NH:30][C:31](=[O:37])[O:32][C:33]([CH3:36])([CH3:35])[CH3:34].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>C1COCC1>[Br:15][C:16]1[CH:17]=[CH:18][C:19]([O:26][CH2:28][CH2:29][NH:30][C:31]([O:32][C:33]([CH3:36])([CH3:35])[CH3:34])=[O:37])=[C:20]([CH:25]=1)[C:21]([O:23][CH3:24])=[O:22]

Participants

6

Reactant 4

HCID 11776Triphenylphosphine2×HCID 77683Methyl 5-bromosalicylateHCID 2733206tert-butyl N-(2-hydroxyethyl)carbamateHCID 5363146Diisopropyl azodicarboxylate2×

Product 1

HCID 59403467Methyl 5-bromo-2-{[2-({[(1,1-dimethylethyl)oxy]carbonyl}amino)ethyl]oxy}benzoateYield 55%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

DIAD (9.62 g, 47.6 mmol) was added to a mixture of methyl 5-bromo-2-hydroxybenzoate (10 g, 43.3 mmol), 1,1-dimethylethyl (2-hydroxyethyl)carbamate (6.98 g, 43.3 mmol) and triphenylphosphine (12.47 g, 47.6 mmol) in THF (250 ml) and stirred at RT for 2.5 hr. Additional triphenylphosphine (2.5 g) was added followed by DIAD (4 ml) and the mixture left standing overnight. Evaporation and purification by flash chromatography eluting with 25% EtOAc/hexane gave the title compound as a yellow oil (8.92 g). MS (ES): C15H2081BrNO5 requires 375; found 276 [M+H−100]+.

Workup

  1. waitthe mixture left
  2. waitstanding overnight
  3. customEvaporation and purification by flash chromatography
  4. washeluting with 25% EtOAc/hexane

Sources & evidence

ORD record
ord-14dceb52d08549bd9af67b4195858526
Source dataset
uspto-grants-2012_07
Patent number
US08222245B2

Reaction notes

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