Lawesson's reagent → 2-Phenyl-1,3,4,5-tetrahydro-azepino[5,4,3-cd]indole-6-thione

HRID 489525Notes

Reaction equation

HRID 489525 reaction equation
[C:1]1([C:7]2[NH:8][C:9]3[CH:10]=[CH:11][CH:12]=[C:13]4[C:19](=O)[NH:18][CH2:17][CH2:16][C:15]=2[C:14]=34)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.COC1C=CC(P2(SP(C3C=CC(OC)=CC=3)(=S)S2)=[S:30])=CC=1>C1(C)C=CC=CC=1.O>[C:1]1([C:7]2[NH:8][C:9]3[CH:10]=[CH:11][CH:12]=[C:13]4[C:19](=[S:30])[NH:18][CH2:17][CH2:16][C:15]=2[C:14]=34)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1

Participants

5

Reactant 2

HCID 87949Lawesson's reagentHCID 102208822-Phenyl-3,10-diazatricyclo[6.4.1.04,13]trideca-1,4,6,8(13)-tetraen-9-one

Product 1

HCID 118327522-Phenyl-1,3,4,5-tetrahydro-azepino[5,4,3-cd]indole-6-thioneYield 68.7%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 1140TolueneSolvent

Procedure

Compound 12 (48.6 mg, 0.18 mmol) in toluene (2 mL) was treated with Lawesson's reagent (75 mg, 0.18 mmol) at room temperature. The solution was heated at reflux for 2 h, then allowed to cool to room temperature and diluted with water. The mixture was extracted with EtOAc (3×5 mL). The organic solution was washed with water and brine, dried (Na2SO4), filtered, and concentrated. The crude product was crystallized (CH2Cl2/hexanes) to give the thioamide 34.4 mg (68%) as a yellow solid. mp 223-226° C. (dec.); 1H NMR (300 MHz, d6-DMSO) δ 3.10 (m, 2H), 3.50 (m, 2H), 7.23 (app t, 1H, J=7.8 Hz), 7.57 (m, 1H), 7.61 (m, 3H), 7.69 (m, 2H), 8.19 (d, 1H, J=7.6 Hz), 10.56 (br t, 1H), 11.68 (br s, 1H); HRMS (FAB, MH+) Calcd for C17H15N2S: 279.0956, Found: 279.0952; Anal. (C17H14N2S.0.25 H2O) C, H, N, S.

Workup

  1. temperatureThe solution was heated
  2. temperatureat reflux for 2 h
  3. extractionThe mixture was extracted with EtOAc (3×5 mL)
  4. washThe organic solution was washed with water and brine
  5. dry with materialdried (Na2SO4)
  6. filtrationfiltered
  7. concentrationconcentrated
  8. customThe crude product was crystallized (CH2Cl2/hexanes)

Sources & evidence

ORD record
ord-c4ceca698552464da43a86931056396b
Source dataset
uspto-grants-2005_12
Patent number
US06977298B2

Reaction notes

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