Triethylamine → 5-carbomethoxy-1,2-dihydro-2-(4-trifluoromethylphenyl)-9H-carbazol-4(3H)-one

HRID 567244Notes

Reaction equation

HRID 567244 reaction equation
[C:1]([C:5]1[C:6](Br)=[C:7]([CH:26]=[CH:27][CH:28]=1)[NH:8][C:9]1[CH2:14][CH:13]([C:15]2[CH:20]=[CH:19][C:18]([C:21]([F:24])([F:23])[F:22])=[CH:17][CH:16]=2)[CH2:12][C:11](=[O:25])[CH:10]=1)([O:3][CH3:4])=[O:2].C1(C)C=CC=CC=1P(C1C=CC=CC=1C)C1C=CC=CC=1C.C(N(CC)CC)C>C(#N)C.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[C:1]([C:5]1[CH:28]=[CH:27][CH:26]=[C:7]2[C:6]=1[C:10]1[C:11](=[O:25])[CH2:12][CH:13]([C:15]3[CH:20]=[CH:19][C:18]([C:21]([F:24])([F:23])[F:22])=[CH:17][CH:16]=3)[CH2:14][C:9]=1[NH:8]2)([O:3][CH3:4])=[O:2]

Participants

6

Reactant 3

HCID 8471TriethylamineHCID 80271Tri-o-tolylphosphineHCID 227395153-(3-Carbomethoxy-2-bromoanilino)-5-(4-trifluoromethylphenyl)-cyclohex-2-en-1-one

Product 1

HCID 227385975-carbomethoxy-1,2-dihydro-2-(4-trifluoromethylphenyl)-9H-carbazol-4(3H)-oneYield 87.1%

Reagents, catalysts & solvents 2

HCID 167845palladium(II) acetateCatalystHCID 6342AcetonitrileSolvent

Procedure

A suspension of 3-(3-carbomethoxy-2-bromoanilino)-5-(4-trifluoromethylphenyl)-cyclohex-2-en-1-one (2.18 g, 4.66 mM), palladium acetate (0.10 g, 0.47 mM), tri-o-tolylphosphine (0.28 g, 0.93 mM), and triethylamine (0.8 ml, 5.78 mM) in 12 mL acetonitrile was heated at reflux for 3 hours. The solvent was removed in vacuo. The residue was dissolved in methylene chloride, washed with 1 N HCl, then with saturated brine, dried over anhydrous sodium sulfate, filtered, and concentrated to afford 2.21 g. Purification by HPLC on silica gel (elution with gradient methylene chloride/ethyl acetate) afforded 1.57 g (87%) of the 5-carbomethoxy-1,2-dihydro-2-(4-trifluoromethylphenyl)-9H-carbazol-4(3H)-one. 1H NMR (CDCl3) δ 9.2 (bs, 1H), 7.6 (d, J=8 Hz, 2H), 7.45-7.35 (m, 5H), 7.25 (d, J=8 Hz, 2H), 3.55 (m, 1H), 3.2-3.0 (m, 2H), 2.7 (m, 2H). MS (ES) m/e 356, 388.

Workup

  1. temperaturewas heated
  2. temperatureat reflux for 3 hours
  3. customThe solvent was removed in vacuo
  4. dissolutionThe residue was dissolved in methylene chloride
  5. washwashed with 1 N HCl
  6. dry with materialwith saturated brine, dried over anhydrous sodium sulfate
  7. filtrationfiltered
  8. concentrationconcentrated
  9. customto afford 2.21 g
  10. customPurification by HPLC on silica gel (elution with gradient methylene chloride/ethyl acetate)

Sources & evidence

ORD record
ord-eaaaa16435244876846b52c03a5fb499
Source dataset
uspto-grants-2001_01
Patent number
US06177440B1

Reaction notes

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