Triethylsilane → 7-methoxy-3-(toluene-4-sulfonyl)-2,3,4,5-tetrahydro-1H-benzo[d]azepine

HRID 1686910Notes

Reaction equation

HRID 1686910 reaction equation
[CH3:1][O:2][C:3]1[CH:24]=[CH:23][C:6]2[C:7](=O)[CH2:8][N:9]([S:12]([C:15]3[CH:20]=[CH:19][C:18]([CH3:21])=[CH:17][CH:16]=3)(=[O:14])=[O:13])[CH2:10][CH2:11][C:5]=2[CH:4]=1.C([SiH](CC)CC)C>FC(F)(F)C(O)=O>[CH3:1][O:2][C:3]1[CH:24]=[CH:23][C:6]2[CH2:7][CH2:8][N:9]([S:12]([C:15]3[CH:16]=[CH:17][C:18]([CH3:21])=[CH:19][CH:20]=3)(=[O:13])=[O:14])[CH2:10][CH2:11][C:5]=2[CH:4]=1

Participants

4

Reactant 2

HCID 12052TriethylsilaneHCID 578537987-Methoxy-3-(toluene-4-sulfonyl)-2,3,4,5-tetrahydro-benzo[d]azepin-1-one

Product 1

HCID 222509407-methoxy-3-(toluene-4-sulfonyl)-2,3,4,5-tetrahydro-1H-benzo[d]azepine

Reagents, catalysts & solvents 1

HCID 6422Trifluoroacetic acidSolvent

Conditions

Temperature
0 °C

Procedure

7-Methoxy-3-(toluene-4-sulfonyl)-2,3,4,5-tetrahydro-benzo[d]azepin-1-one (8.0 g/23 mmol; prepared in 4 steps as described by Kanao et al. Chem. Pharm. Bull., 1982, 30, 180-188) was dissolved in trifluoroacetic acid (10 mL) and cooled to 0° C. Triethylsilane (ca. 20 mL/230 mmol) was then added via syringe (mild exotherm) and the reaction allowed to warm to room temperature overnight. The reaction was concentrated and the residue partitioned between diethyl ether and 1 M aqueous sodium hydroxide (100 mL). The organic layer was washed with brine (100 mL), dried (magnesium sulfate), filtered and concentrated onto silica gel. Chromatography on silica gel (eluting with 0→30% ethyl acetate/hexanes) afforded 7-Methoxy-3-(toluene-4-sulfonyl)-2,3,4,5-tetrahydro-1H-benzo[d]azepine as a white solid (4.0 g/55%). 1H NMR (400 MHz, CDCl3) δ 7.62 (d, J=8.0 Hz, 2H), 7.25 (d, J=8.0 Hz, 2H), 6.98 (d, J=9.1 Hz, 1H), 6.68 (m, 2H), 3.78 (s, 3H), 3.28 (m, 4H), 2.94 (m, 4H), 2.39 (s, 3H).

Workup

  1. temperatureto warm to room temperature overnight
  2. concentrationThe reaction was concentrated
  3. customthe residue partitioned between diethyl ether and 1 M aqueous sodium hydroxide (100 mL)
  4. washThe organic layer was washed with brine (100 mL)
  5. dry with materialdried (magnesium sulfate)
  6. filtrationfiltered
  7. concentrationconcentrated onto silica gel

Sources & evidence

ORD record
ord-53175e3e63c54ff38d2098b6cda34099
Source dataset
uspto-grants-2012_04
Patent number
US08148391B2

Reaction notes

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