Acetic Anhydride → HCID 71060717, compound

HRID 528964Notes

Reaction equation

HRID 528964 reaction equation
O[CH:2]([C:11]1[CH:23]=[CH:22][C:14]([C:15]([O:17][C:18]([CH3:21])([CH3:20])[CH3:19])=[O:16])=[CH:13][C:12]=1[C:24]([N:26]1[CH2:35][CH2:34][C:33]2[C:28](=[CH:29][CH:30]=[CH:31][CH:32]=2)[CH2:27]1)=[O:25])[CH:3]([N+:8]([O-:10])=[O:9])[CH2:4][CH2:5][CH2:6][CH3:7].C(OC(=O)C)(=O)C>C1COCC1.CN(C1C=CN=CC=1)C.C(Cl)Cl>[N+:8]([C:3]([CH2:4][CH2:5][CH2:6][CH3:7])=[CH:2][C:11]1[CH:23]=[CH:22][C:14]([C:15]([O:17][C:18]([CH3:21])([CH3:20])[CH3:19])=[O:16])=[CH:13][C:12]=1[C:24]([N:26]1[CH2:35][CH2:34][C:33]2[C:28](=[CH:29][CH:30]=[CH:31][CH:32]=2)[CH2:27]1)=[O:25])([O-:10])=[O:9]

Participants

6

Reactant 2

HCID 7918Acetic AnhydrideHCID 71062457HCID 71062457, compound

Product 1

HCID 71060717HCID 71060717, compoundYield 80%

Reagents, catalysts & solvents 3

HCID 142844-(Dimethylamino)pyridineCatalyst2×HCID 6344DichloromethaneSolventHCID 8028TetrahydrofuranSolvent

Procedure

To a solution of tert-butyl 4-(1-hydroxy-2-nitrohexyl)-3-(1,2,3,4-tetrahydroisoquinoline-2-carbonyl)benzoate (632 mg, 1.31 mmol) in THF (3 mL) was added acetic anhydride (0.136 mL, 1.44 mmol) and a crystal of DMAP (−5 mg). After stirring at room temperature for 30 min, the reaction mixture was concentrated in vacuo. The residue was suspended in DCM (3.0 mL) and DMAP (192 mg, 1.57 mmol) was added. After stirring at room temperature overnight, the reaction mixture was diluted with DCM and washed with brine. The aqueous layer was back-extracted with DCM and the pooled organic layers were dried over anhydrous sodium sulfate and concentrated in vacuo. The residue was purified by flash chromatography (Isco 40 g column eluting with 0-25% EtOAc/hexanes) to give the title compound (485 mg, 80%) as a colorless oil. 1H NMR (CDCl3, 1:1 mixture of amide rotamers) δ 8.12-8.09 (m, 1H), 8.01-8.00 (m, 1H), 7.97 (s, 0.5H), 7.81 (s, 0.5H), 7.46 (d, J=8 Hz, 0.5H), 7.39 (d, J=8 Hz, 0.5H), 7.24-6.79 (m, 4H), 4.94 (s, 1H), 4.31 (s, 1H), 3.47 (t, J=6 Hz, 1H), 3.00-2.47 (m, 5H), 1.65-1.31 (m, 4H), 1.63 (s, 9H), 0.95-0.86 (m, 3H); MS(ESI+) m/z 465.3 (M+H)+.

Workup

  1. concentrationthe reaction mixture was concentrated in vacuo
  2. stirringAfter stirring at room temperature overnight
  3. washwashed with brine
  4. extractionThe aqueous layer was back-extracted with DCM
  5. dry with materialthe pooled organic layers were dried over anhydrous sodium sulfate
  6. concentrationconcentrated in vacuo
  7. customThe residue was purified by flash chromatography (Isco 40 g column eluting with 0-25% EtOAc/hexanes)

Sources & evidence

ORD record
ord-7a71df2eb5df4d408cb32e86de78c391
Source dataset
uspto-grants-2016_05
Patent number
US09346795B2

Reaction notes

Loading…