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

HRID 51316Notes

Reaction equation

HRID 51316 reaction equation
[C:1]([C:5]1[C:6](Br)=[C:7]([CH:17]=[CH:18][CH:19]=1)[NH:8][C:9]1[CH2:14][CH:13]([CH3:15])[CH2:12][C:11](=[O:16])[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:19]=[CH:18][CH:17]=[C:7]2[C:6]=1[C:10]1[C:11](=[O:16])[CH2:12][CH:13]([CH3:15])[CH2:14][C:9]=1[NH:8]2)([O:3][CH3:4])=[O:2]

Participants

6

Reactant 3

HCID 8471TriethylamineHCID 80271Tri-o-tolylphosphineHCID 227402023-(3-Carbomethoxy-2-bromoanilino)-5-methyl-cyclohex-2-en-1-one

Product 1

HCID 227387155-Carbomethoxy-1,2-dihydro-2-methyl-9H-carbazol-4(3H)-oneYield 75.1%

Reagents, catalysts & solvents 2

HCID 167845palladium(II) acetateCatalystHCID 6342AcetonitrileSolvent

Procedure

A suspension of 3-(3-carbomethoxy-2-bromoanilino)-5-methyl-cyclohex-2-en-1-one (9.98 g, 29.5 mM), palladium acetate (0.66 g, 2.95 mM), tri-o-tolylphosphine (1.8 g, 5.9 mM), and triethylamine (5.10 ml, 36.6 mM) in 75 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 11 g of crude product. Purification by HPLC on silica gel (elution with gradient methylene chloride/ethyl acetate) afforded 5.7 g (75%) of 5-carbomethoxy-1,2-dihydro-2-methyl-9H-carbazol-4(3H)-one. 1H NMR (CDCl3) δ9.5 (bs, 1H), 7.4 (d, J=8 Hz, 1H), 7.35 (d, J=8 Hz, 1H), 7.2 (dd, J=8 and 8 Hz, 1H), 4.0 (s, 3H), 2.9 (dd, J=13 and 4 Hz, 1H), 2.55 (m, 2H), 2.4 (m, 1H), 2.25 (dd, J=15 and 9 Hz, 1H), 1.05 (d, J=7 Hz, 3H). MS (ES) m/e 226, 258.

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 11 g of crude product
  10. customPurification by HPLC on silica gel (elution with gradient methylene chloride/ethyl acetate)

Sources & evidence

ORD record
ord-b4f96111203c42ca881ea69c30403b1d
Source dataset
uspto-grants-2004_03
Patent number
US06713645B1

Reaction notes

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