1,4-Dioxane → HCID 57532238, compound
Reaction equation
C1(P(N=[N+]=[N-])(C2C=CC=CC=2)=[O:8])C=CC=CC=1.[Br:18][C:19]1[C:27]([CH3:28])=CC(C(O)=O)=C[C:20]=1[N+:29]([O-:31])=[O:30].C([N:35]([CH:38]([CH3:40])[CH3:39])[CH2:36]C)(C)C.[CH3:41][Si:42](C(O)C)([CH3:44])[CH3:43].[O:48]1CCO[CH2:50][CH2:49]1>>[CH3:41][Si:42]([CH3:44])([CH3:43])[CH2:50][CH2:49][O:48][C:36](=[O:8])[NH:35][C:38]1[CH:39]=[C:20]([N+:29]([O-:31])=[O:30])[C:19]([Br:18])=[C:27]([CH3:28])[CH:40]=1Participants
Conditions
- Temperature
- 90 °C
Procedure
Diphenylphosphorylazide (4.31 mL, 20 mmol) was added to a stirred solution of 4-bromo-3-methyl-5-nitro-benzoic acid (Example 294: step b (5.2 g, 20 mmol)) and diisopropylethylamine (3.66 mL, 21 mmol) in 1,4-dioxane (80 mL) at rt. After 30 minutes at rt, the reaction was heated to 90° C. for 5 min. Trimethylsilylethanol (5.73 mL, 40 mmol) was added and the solution was stirred for 16 h at 95° C. The solvents were removed in vacuo and the residue was partitioned between EtOAc (100 mL) and water (30 mL). The organic layer was further extracted with aq citric acid (3×30 mL), NaHCO3, (2×30 mL) and brine (50 mL). Purification by column chromatography (9:1 Hex/EtOAc) yielded the title compound as a yellow solid. 1H NMR (CDCl3) δ 7.73 (d, 1H, J=2.4 Hz), 7.41 (br d, 1H, J=1.7 Hz), 7.01 (s, 1H), 4.24 (m, 2H), 2.43 (s, 3H), 1.02 (m, 2H), 0.04 (s, 9H).
Workup
- customThe solvents were removed in vacuo
- customthe residue was partitioned between EtOAc (100 mL) and water (30 mL)
- extractionThe organic layer was further extracted with aq citric acid (3×30 mL), NaHCO3, (2×30 mL) and brine (50 mL)
- customPurification by column chromatography (9:1 Hex/EtOAc)
Sources & evidence
- ORD record
- ord-6a92529ffc344aa2afceac2f29e66c70
- Source dataset
- uspto-grants-2006_11
- Patent number
- US07138530B2
Reaction notes
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