Stannous Chloride → 3-prop-2-ynyl-2,3,4,5-tetrahydro-1H-benzo[d]azepin-7-ylamine

HRID 1040818Notes

Reaction equation

HRID 1040818 reaction equation
[N+:1]([C:4]1[CH:17]=[CH:16][C:7]2[CH2:8][CH2:9][N:10]([CH2:13][C:14]#[CH:15])[CH2:11][CH2:12][C:6]=2[CH:5]=1)([O-])=O.[Sn](Cl)Cl>C(OCC)(=O)C.C(O)C>[CH2:13]([N:10]1[CH2:11][CH2:12][C:6]2[CH:5]=[C:4]([NH2:1])[CH:17]=[CH:16][C:7]=2[CH2:8][CH2:9]1)[C:14]#[CH:15]

Participants

5

Reactant 2

HCID 24479Stannous ChlorideHCID 866338797-Nitro-3-prop-2-ynyl-2,3,4,5-tetrahydro-1H-benzo[d]azepine

Product 1

HCID 866338783-prop-2-ynyl-2,3,4,5-tetrahydro-1H-benzo[d]azepin-7-ylamineYield 95%

Reagents, catalysts & solvents 2

HCID 702EthanolSolventHCID 8857Ethyl AcetateSolvent

Procedure

7-Nitro-3-prop-2-ynyl-2,3,4,5-tetrahydro-1H-benzo[d]azepine (589 mg, 2.56 mmol) was dissolved in ethyl acetate (80 mL) and ethanol (30 mL). Tin (II) chloride dehydrate (2.88 g, 12.80 mmol, 5.0 eq) was added and the reaction was heated at reflux for 18 hours. The reaction was allowed to cool to room temperature and was then concentrated under reduced pressure. The residue was taken up in EtOAc (100 mL) and washed with 10% aqueous KF (70 mL). The organic layer was dried (sodium sulfate), filtered, and concentrated under reduced pressure to obtain 3-prop-2-ynyl-2,3,4,5-tetrahydro-1H-benzo[d]azepin-7-ylamine as a yellow solid (487 mg, 95%). An analytical sample was purified by prep-HPLC using a gradient of 0-30% acetonitrile/water. LCMS (m/e) 201 (M+1); 1H-NMR (CDCl3, 400 MHz) δ 6.91 (d, 1H, J=7.7 Hz), 6.52-6.46 (m, 2H), 3.43 (d, 2H, J=2.3 Hz), 2.91-2.82 (m, 4H), 2.78-2.64 (m, 4H), 2.24-2.19 (m, 1H).

Workup

  1. temperaturethe reaction was heated
  2. temperatureat reflux for 18 hours
  3. concentrationwas then concentrated under reduced pressure
  4. washwashed with 10% aqueous KF (70 mL)
  5. dry with materialThe organic layer was dried (sodium sulfate)
  6. filtrationfiltered
  7. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-39c0b0a5e1a940d196de110a2b1e8438
Source dataset
uspto-grants-2013_10
Patent number
US08552186B2

Reaction notes

Loading…