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

HRID 1040602Notes

Reaction equation

HRID 1040602 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-cb6497b4280a4d4da5a6b7e8a9416302
Source dataset
uspto-grants-2013_10
Patent number
US08552186B2

Reaction notes

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