4-Vinylphenol → trans-4-[2-(4-hydroxyphenyl) vinyl]-1H-indole-2,3-dione

HRID 1935493ノート

反応式

HRID 1935493 の反応式
I[C:2]1[CH:10]=[CH:9][CH:8]=[C:7]2[C:3]=1[C:4](=[O:12])[C:5](=[O:11])[NH:6]2.C1(C)C=CC=CC=1P(C1C=CC=CC=1C)C1C=CC=CC=1C.[CH:35]([C:37]1[CH:42]=[CH:41][C:40]([OH:43])=[CH:39][CH:38]=1)=[CH2:36]>C(O)C(O)C.C(#N)C.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[OH:43][C:40]1[CH:41]=[CH:42][C:37](/[CH:35]=[CH:36]/[C:2]2[CH:10]=[CH:9][CH:8]=[C:7]3[C:3]=2[C:4](=[O:12])[C:5](=[O:11])[NH:6]3)=[CH:38][CH:39]=1

参加物

7

反応物 3

HCID 624534-VinylphenolHCID 80271Tri-o-tolylphosphineHCID 106359514-Iodoindoline-2,3-dione

生成物 1

HCID 10934362trans-4-[2-(4-hydroxyphenyl) vinyl]-1H-indole-2,3-dione収率 13%

試薬・触媒・溶媒 3

HCID 167845palladium(II) acetate触媒HCID 1030Propylene Glycol溶媒HCID 6342Acetonitrile溶媒

反応条件

温度
100 °C

実験手順

A mixture of 1.0 g (3.6 mmol) of 4-iodo-1H-indole-2,3-dione (Snow, et al., Journal of the American Chemical Society 1977, 99, 373444), 0.42 g (4.2 mmol) of TEA, 0.06 g (0.27 mmol) of palladium(II) acetate, 0.16 g (0.54 mmol) of trio-tolylphosphine and 5.0 g (4.2 mmol) of a 10% solution of 4-vinylphenol in propylene glycol was suspended in 15 mL of dry acetonitrile in a pyrex sealed tube and heated to 100° C. for 4 h. The mixture was cooled to rt, quenched with 50 mL of 10% hydrochloric acid and extracted with two 100 mL-portions of EtOAc. The combined extracts were dried over MgSO4 and concentrated to give a brown solid, which was subjected to chromatography on silica gel, eluting with hexane:EtOAc (3:1), to yield 0.125 g (13%) of trans4-[2-(4-hydroxyphenyl) vinyl]-1H-indole-2,3-dione as a red solid: 1H NMR (DMSO-d6): δ 6.6-7.6 (m, 8H), 7.77 (d, J=16.4 Hz, 1H), 9.85 (bs, 1H), 11.00 (bs, 1H); APCI−MS m/z 264 (M−1)−. Condensation of trans4-[2-(4-hydroxyphenyl)vinyl]-1H-indole-2,3-dione and 4-sulfonamidophenylhydrazine hydrochloride according to Procedure G gave the title compound in 27% yield as an orange solid: 1H NMR (DMSO-d6): δ 6.78 (d, J=7.8 Hz, 1H), 6.88 (d, J=8.7 Hz, 2H), 7.26 (t, J=7.8 Hz, 1H), ), 7.29 (s, 2H), 7.36 (d, J=16.5 Hz, 1H), 7.47 (d, J=7.8 Hz, 1H), 7.53 (d, J=8.7 Hz, 2H), 7.57 (d, J=8.7 Hz, 2H), ), 7.81 (d, J=8.7 Hz, 2H), 8.03 (d, J=16.5 Hz 1H), 9.78 (s, 1H), 11.17 (s, 1H), 13.02 (s, 1H); APCI−MS m/z 433 (M−1)−.

後処理

  1. temperatureThe mixture was cooled to rt
  2. customquenched with 50 mL of 10% hydrochloric acid
  3. extractionextracted with two 100 mL-portions of EtOAc
  4. dry with materialThe combined extracts were dried over MgSO4
  5. concentrationconcentrated
  6. customto give a brown solid, which
  7. washeluting with hexane:EtOAc (3:1)

出典と根拠

ORDレコード
ord-82e84deb329244a28ee6e6eaf479010f
出典データセット
uspto-grants-2002_05
特許番号
US06387919B1

反応ノート

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