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

HRID 33283

Reaction equation

HRID 33283 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) δ 3.14 (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-57b7dd231f264c7992b6af664dc905d3
Source dataset
uspto-grants-2008_09
Patent number
US07429578B2

Linked notes

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