Sodium Carbonate → 2-Phenyl-3,10-diazatricyclo[6.4.1.04,13]trideca-1,4,6,8(13)-tetraen-9-one

HRID 2298886Notes

Reaction equation

HRID 2298886 reaction equation
Br[C:2]1[NH:3][C:4]2[CH:5]=[CH:6][CH:7]=[C:8]3[C:14](=[O:15])[NH:13][CH2:12][CH2:11][C:10]=1[C:9]=23.C([O-])([O-])=O.[Na+].[Na+].[Li+].[Cl-].[C:24]1(B(O)O)[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=1>C1(C)C=CC=CC=1.CCO.O>[C:24]1([C:2]2[NH:3][C:4]3[CH:5]=[CH:6][CH:7]=[C:8]4[C:14](=[O:15])[NH:13][CH2:12][CH2:11][C:10]=2[C:9]=34)[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=1

Participants

8

Reactant 4

HCID 10340Sodium CarbonateHCID 66827Phenylboronic AcidHCID 433294Lithium ChlorideHCID 99432302-Bromo-3,4,5,6-tetrahydro-1H-azepino[5,4,3-cd]indol-6-one

Product 1

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

Reagents, catalysts & solvents 3

HCID 702EthanolSolventHCID 962WaterSolvent2×HCID 1140TolueneSolvent

Procedure

Tricyclic bromide 11 (0.2 g, 0.75 mmol) in toluene (20 mL) and EtOH (10 mL) was treated with solid Na2CO3 (0.199 g, 1.88 mmol), LiCl (0.095 g, 2.25 mmol), phenylboronic acid (0.138 g, 1.13 mmol), and water (0.50 mL). The solution was degassed and tetrakis(triphenylphosphine)palladium(0) (43 mg, 5 mol %) was added. The solution was heated at reflux for 5 h, and then cooled to ambient temperature and diluted with water (20 mL). The aqueous layer was adjusted to pH=7-8 with saturated aqueous K2CO3 and extracted with EtOAc (20 mL×3). The organic solution was washed with water and brine, and dried (Na2SO4), filtered, and concentrated. The crude product was recrystallized (CH2Cl2/MeOH/hexanes) to yield the 2-phenyltricycle as a pale-yellow solid, 183 mg (93%). mp 249-255° C. (dec); 1H NMR (CDCl3/CD4OD) δ3.14 (m, 2H), 3.53 (m, 2H), 7.23 (t, 1H, J=7.7 Hz), 7.33 (m, 1H), 7.44 (m, 2H), 7.55 (m, 3H), 7.83 (d, 1H, J=7.7 Hz); HRMS (M+H) Calcd for C17H14N2O+H: 263.1184, Found: 263.1189; Anal. (C17H14N2O.0.8 H2O) C, H, N.

Workup

  1. customThe solution was degassed
  2. additiontetrakis(triphenylphosphine)palladium(0) (43 mg, 5 mol %) was added
  3. temperatureThe solution was heated
  4. temperatureat reflux for 5 h
  5. additiondiluted with water (20 mL)
  6. extractionextracted with EtOAc (20 mL×3)
  7. washThe organic solution was washed with water and brine
  8. dry with materialdried (Na2SO4)
  9. filtrationfiltered
  10. concentrationconcentrated
  11. customThe crude product was recrystallized (CH2Cl2/MeOH/hexanes)
  12. customto yield the 2-phenyltricycle as a pale-yellow solid, 183 mg (93%)

Sources & evidence

ORD record
ord-452f5c77991b432baadd4898f33e3338
Source dataset
uspto-grants-2002_12
Patent number
US06495541B1

Reaction notes

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