반응 #79594

반응 방정식

3-(3-carbomethoxy-2-bromoanilino)-5-methyl-cyclohex-2-en-1-one

tri-o-tolylphosphine

triethylamine

→

5-carbomethoxy-1,2-dihydro-2-methyl-9H-carbazol-4(3H)-one

수율 75.1%

용매

acetonitrile

반응 조건

후처리

1. 1
   온도was heated
2. 2
   온도at reflux for 3 hours
3. 3
   기타The solvent was removed in vacuo
4. 4
   workup.DISSOLUTIONThe residue was dissolved in methylene chloride
5. 5
   세척washed with 1 N HCl
6. 6
   건조with saturated brine, dried over anhydrous sodium sulfate
7. 7
   여과filtered
8. 8
   농축concentrated
9. 9
   기타to afford 11 g of crude product
10. 10
    기타Purification by HPLC on silica gel (elution with gradient methylene chloride/ethyl acetate)

실험 절차

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.

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