Lithium Chloride → methyl 4-acetyl-1-(3-chloropyridin-2-yl)-1H-pyrrole-2-carboxylate

HRID 874190ノート

反応式

HRID 874190 の反応式
Br[C:2]1[CH:3]=[C:4]([C:14]([O:16][CH3:17])=[O:15])[N:5]([C:7]2[C:12]([Cl:13])=[CH:11][CH:10]=[CH:9][N:8]=2)[CH:6]=1.[CH2:18]([O:20]C([Sn](CCCC)(CCCC)CCCC)=C)[CH3:19].[Cl-].[Li+]>C1COCC1.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[C:18]([C:2]1[CH:3]=[C:4]([C:14]([O:16][CH3:17])=[O:15])[N:5]([C:7]2[C:12]([Cl:13])=[CH:11][CH:10]=[CH:9][N:8]=2)[CH:6]=1)(=[O:20])[CH3:19]

参加物

6

反応物 3

HCID 433294Lithium ChlorideHCID 619414Stannane, tributyl(1-ethoxyethenyl)-HCID 66659078methyl 4-bromo-1-(3-chloropyridin-2-yl)-1H-pyrrole-2-carboxylate

生成物 1

HCID 67125231methyl 4-acetyl-1-(3-chloropyridin-2-yl)-1H-pyrrole-2-carboxylate

試薬・触媒・溶媒 2

HCID 178418397HCID 178418397、化合物触媒HCID 8028Tetrahydrofuran溶媒

実験手順

Under argon, 5.0 g (15.6 mmol) of methyl 4-bromo-1-(3-chloropyridin-2-yl)-1H-pyrrole-2-carboxylate were dissolved in THF, and 8.2 g (21.9 mmol) of (1-ethoxyvinyl)tributylstannane, 2.1 g of lithium chloride and 0.9 g (0.8 mmol) of tetrakis(triphenylphosphine)palladium were added at room temperature and the mixture was stirred under reflux for 48 h. The solvent was then distilled off, and the residue was taken up in 200 ml of THF and stirred in the presence of 12 ml of 2N hydrochloric acid at RT for a further 24 h. Once more, the solvent was distilled off, and the residue was dissolved in 120 ml of methyl tert-butyl ether and, at RT, stirred vigorously with 120 ml of saturated potassium fluoride solution for 1 h. The organic phase was separated off and concentrated. The desired product was isolated by chromatographic purification.

後処理

  1. temperatureunder reflux for 48 h
  2. distillationThe solvent was then distilled off
  3. stirringstirred in the presence of 12 ml of 2N hydrochloric acid at RT for a further 24 h
  4. distillationOnce more, the solvent was distilled off
  5. dissolutionthe residue was dissolved in 120 ml of methyl tert-butyl ether and, at RT
  6. stirringstirred vigorously with 120 ml of saturated potassium fluoride solution for 1 h
  7. customThe organic phase was separated off
  8. concentrationconcentrated

出典と根拠

ORDレコード
ord-63fa5adf343e49718d8e0bc5c181e19d
出典データセット
uspto-grants-2015_03
特許番号
US08980886B2

反応ノート

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