Ammonium Chloride → tert-Butyl 5-ethenyl-1H-indole-1-carboxylate

HRID 252054ノート

反応式

HRID 252054 の反応式
[Li][CH2:2]CCC.[C:6]([O:10][C:11]([N:13]1[C:21]2[C:16](=[CH:17][C:18]([CH:22]=O)=[CH:19][CH:20]=2)[CH:15]=[CH:14]1)=[O:12])([CH3:9])([CH3:8])[CH3:7].[Cl-].[NH4+]>[Br-].C[P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.C1COCC1>[C:6]([O:10][C:11]([N:13]1[C:21]2[C:16](=[CH:17][C:18]([CH:22]=[CH2:2])=[CH:19][CH:20]=2)[CH:15]=[CH:14]1)=[O:12])([CH3:9])([CH3:8])[CH3:7]

参加物

6

反応物 3

HCID 25517Ammonium ChlorideHCID 11172622tert-Butyl 5-formyl-1H-indole-1-carboxylateHCID 178418339Butyllithium

生成物 1

HCID 66890900tert-Butyl 5-ethenyl-1H-indole-1-carboxylate収率 130.5%

試薬・触媒・溶媒 2

HCID 74505Methyltriphenyliphosphonium bromide触媒HCID 8028Tetrahydrofuran溶媒2 回

実験手順

T a suspension of methyltriphenylphosphonium bromide (8.1 g, 22.7 mmol) in THF (140 mL) at 0° C. was added nBuLi (1.6 M in hexanes, 14.2 mL, 22.7 mmol) dropwise over 10 min. After 20 min of stirring, a solution of the 5-formyl-indole-1-carboxylic acid tert-butyl ester (4.63 g, 14.8 mmol) in THF (20 mL) was introduced slowly over 20 min. The reaction was warmed slowly to room temperature, stirred 30 min. The reaction mixture was poured into saturated ammonium chloride and the separated aqueous phase was extracted with ethylacetate (3×100 mL). The combined organic phase was dried over sodium sulfate, filtered and concentrated. The residue was purified by chromatography (methylene chloride to 1% acetone-methylene chloride) to give 5-vinyl-indole-1-carboxylic acid tert-butyl ester (4.7 g, 100%) or similarly 6-vinyl-indole-1-carboxylic acid tert-butyl ester.

後処理

  1. stirringstirred 30 min
  2. extractionthe separated aqueous phase was extracted with ethylacetate (3×100 mL)
  3. dry with materialThe combined organic phase was dried over sodium sulfate
  4. filtrationfiltered
  5. concentrationconcentrated
  6. customThe residue was purified by chromatography (methylene chloride to 1% acetone-methylene chloride)

出典と根拠

ORDレコード
ord-40aa9bff163f4b89bcb9aad58780af5c
出典データセット
uspto-grants-2011_01
特許番号
US07868002B2

反応ノート

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