Acetic Acid → Dimethyl indole-2,3-dicarboxylate

HRID 1912627ノート

反応式

HRID 1912627 の反応式
[NH2:1][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[C:8]([O:16][CH3:17])(=[O:15])[C:9]#[C:10][C:11]([O:13][CH3:14])=[O:12].C(O)(=O)C.O=O>CN(C)C(=O)C.CC([O-])=O.CC([O-])=O.[Pd+2]>[NH:1]1[C:2]2[C:7](=[CH:6][CH:5]=[CH:4][CH:3]=2)[C:10]([C:11]([O:13][CH3:14])=[O:12])=[C:9]1[C:8]([O:16][CH3:17])=[O:15]

参加物

7

反応物 4

HCID 176Acetic AcidHCID 977Oxygen2 回HCID 6115AnilineHCID 12980Dimethyl acetylenedicarboxylate

生成物 1

HCID 143197Dimethyl indole-2,3-dicarboxylate収率 54.9%

試薬・触媒・溶媒 2

HCID 167845palladium(II) acetate触媒HCID 31374Dimethylacetamide溶媒

反応条件

温度
115 °C

実験手順

A solution of aniline (3.91 ml, 43.0 mmol) and dimethyl but-2-ynedioate (5.28 ml, 43.0 mmol) in N,N-dimethylacetamide (DMA) (194 ml)/acetic acid (64.8 ml) was degassed with O2 for 5 min and treated with Pd(OAc)2 (0.964 g, 4.30 mmol). The reaction mixture was heated to 115° C. and placed under and atmosphere of O2. After 18 h, the reaction was cooled to ambient temperature, filtered through a pad of Celite™, diluted with EtOAc and washed with H2O. The organic was washed with brine, dried (MgSO4), filtered and concentrated. The residue was purified by ISCO (0-50% EtOAc-hexanes: 220 g SiO2) to afford dimethyl 1H-indole-2,3-dicarboxylate (5.5 g, 23.58 mmol, 54.9% yield) as a yellow solid: 1H NMR (400 MHz, CHLOROFORM-d) δ=9.32 (br. s., 1 H), 8.08 (d, J=8.2 Hz, 1 H), 7.48-7.44 (m, 1 H), 7.42-7.37 (m, 1 H), 7.29 (s, 1 H), 4.01 (d, J=2.0 Hz, 6 H); LCMS (m/z) ES+=234 (M+1).

後処理

  1. temperaturethe reaction was cooled to ambient temperature
  2. filtrationfiltered through a pad of Celite™
  3. additiondiluted with EtOAc
  4. washwashed with H2O
  5. washThe organic was washed with brine
  6. dry with materialdried (MgSO4)
  7. filtrationfiltered
  8. concentrationconcentrated
  9. customThe residue was purified by ISCO (0-50% EtOAc-hexanes: 220 g SiO2)

出典と根拠

ORDレコード
ord-240f4a4cf9cb41f29e4cbed1891e8b31
出典データセット
uspto-grants-2013_12
特許番号
US08609653B2

反応ノート

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