Triacetoxyperiodinane → Methyl 2-formylisonicotinate

HRID 1963246ノート

反応式

HRID 1963246 の反応式
[OH:1][CH2:2][C:3]1[CH:4]=[C:5]([CH:10]=[CH:11][N:12]=1)[C:6]([O:8][CH3:9])=[O:7].CC(OI1(OC(C)=O)(OC(C)=O)OC(=O)C2C=CC=CC1=2)=O.[Na]>ClCCl.C([O-])(O)=O.[Na+]>[CH:2]([C:3]1[CH:4]=[C:5]([CH:10]=[CH:11][N:12]=1)[C:6]([O:8][CH3:9])=[O:7])=[O:1]

参加物

6

反応物 3

HCID 159087TriacetoxyperiodinaneHCID 5360545SodiumHCID 13276248Methyl 2-(hydroxymethyl)pyridine-4-carboxylate2 回

生成物 1

HCID 19744506Methyl 2-formylisonicotinate収率 85%

試薬・触媒・溶媒 2

HCID 6344Dichloromethane溶媒2 回HCID 516892Sodium Bicarbonate溶媒

実験手順

Methyl 2-(hydroxymethyl)isonicotinate (8.36 g, 50 mmol) (from reference compound 38, step 1) was dissolved in dichloromethane (150 mL). Dess-Martin periodinane (25 g, 58.94 mmol) was added and the mixture stirred at room temperature for 2 h 30 min. Sodium sulfothioate (59.3 g, 375.00 mmol) was dissolved in satd NaHCO3 and added to the reaction mixture. The suspension was vigorously stirred at room temperature for 15 min, DCM was added and the phases were separated. The aqueous phase was extracted with DCM twice and the combined organic layers were dried over MgSO4 and evaporated. The residue was purified by automated flash chromatography on a Biotage® KP-SIL 340 g column. Gradient heptanes/EtOAc 80:20 to 65:35 over 5 CV was used as mobile phase. Methyl 2-formylisonicotinate (7 g, 85%) was isolated as an off-white solid. 1H NMR (400 MHz, cdcl3) δ 4.00 (s, 3H), 8.09 (dd, 1H), 8.49 (s, 1H), 8.95 (d, 1H), 10.15 (s, 1H). MS m/z 165 (M)+

後処理

  1. additionadded to the reaction mixture
  2. stirringThe suspension was vigorously stirred at room temperature for 15 min
  3. customthe phases were separated
  4. extractionThe aqueous phase was extracted with DCM twice
  5. dry with materialthe combined organic layers were dried over MgSO4
  6. customevaporated
  7. customThe residue was purified by automated flash chromatography on a Biotage® KP-SIL 340 g column

出典と根拠

ORDレコード
ord-695ae9c9ca1c446cbd0ad2e1e22ff7fc
出典データセット
uspto-grants-2013_04
特許番号
US08415378B2

反応ノート

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