ethyl 5-hydroxy-1-tosyl-2,3-dihydro-1H-benzo[b]azepine-4-carboxylate → 1-Tosyl-3,4-dihydro-1H-benzo[b]azepin-5(2H)-one

HRID 2389547Notes

Reaction equation

HRID 2389547 reaction equation
[OH:1][C:2]1[C:3]2[CH:27]=[CH:26][CH:25]=[CH:24][C:4]=2[N:5]([S:14]([C:17]2[CH:23]=[CH:22][C:20]([CH3:21])=[CH:19][CH:18]=2)(=[O:16])=[O:15])[CH2:6][CH2:7][C:8]=1C(OCC)=O>C(O)(=O)C.Cl.C(O)C.S(=O)(=O)(O)O>[S:14]([N:5]1[CH2:6][CH2:7][CH2:8][C:2](=[O:1])[C:3]2[CH:27]=[CH:26][CH:25]=[CH:24][C:4]1=2)([C:17]1[CH:23]=[CH:22][C:20]([CH3:21])=[CH:19][CH:18]=1)(=[O:15])=[O:16]

Participants

6

Reactant 1

HCID 54718720ethyl 5-hydroxy-1-tosyl-2,3-dihydro-1H-benzo[b]azepine-4-carboxylate

Product 1

HCID 2668521-Tosyl-3,4-dihydro-1H-benzo[b]azepin-5(2H)-oneYield 552.1%

Reagents, catalysts & solvents 4

HCID 176Acetic AcidSolventHCID 313Hydrochloric AcidSolventHCID 702EthanolSolventHCID 1118Sulfuric AcidSolvent

Procedure

To a suspension of ethyl 5-hydroxy-1-tosyl-2,3-dihydro-1H-benzo[b]azepine-4-carboxylate (30 g, 8.04 mmol) in glacial acetic acid (180 mL), conc. hydrochloric acid (30 mL), ethanol (60 mL) water (30 mL) and conc. sulphuric acid (15 mL) were added at 10-15° C. The reaction mixture was warmed to room temperature and then heated to reflux for 15-16 h. The reaction mixture was cooled to room temperature and poured on to ice. A precipitate formed which was filtered and washed with water (200 mL×3) and dried under reduced pressure to afford 1-tosyl-3,4-dihydro-1H-benzo[b]azepin-5(2H)-one (14 g, 56%). 1H NMR: (400 MHz, CDCl3) δ: 7.71-7.69 (1H, d, J=9.6 Hz), 7.60 (2H, d, J=8.4 Hz), 7.54 (1H, t, J=8.4 Hz), 7.48 (1H, d, J=7.2 Hz), 7.40 (1H, t, J=7.2 Hz), 7.28 (2H, d, J=8.4 Hz), 3.87 (2H, t, J=6.4 Hz), 2.42 (3H, s), 2.42 (2H, m), 1.98 (2H, m).

Workup

  1. additionwere added at 10-15° C
  2. temperatureheated
  3. temperatureto reflux for 15-16 h
  4. temperatureThe reaction mixture was cooled to room temperature
  5. additionpoured on to ice
  6. customA precipitate formed which
  7. filtrationwas filtered
  8. washwashed with water (200 mL×3)
  9. customdried under reduced pressure

Sources & evidence

ORD record
ord-89412a0f80904f4c8ca8c0e1e4133db0
Source dataset
uspto-grants-2012_09
Patent number
US08273754B2

Reaction notes

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