Iodine → 3-iodo-N-phenylisonicotinamide

HRID 31391

反応式

HRID 31391 の反応式
[C:1]1([NH:7][C:8](=[O:15])[C:9]2[CH:14]=[CH:13][N:12]=[CH:11][CH:10]=2)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[Li]CCCC.[I:21]I.S(S([O-])=O)([O-])(=O)=O.[K+].[K+]>C(Cl)Cl.C1COCC1>[C:1]1([NH:7][C:8](=[O:15])[C:9]2[CH:14]=[CH:13][N:12]=[CH:11][C:10]=2[I:21])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1

参加物

7

反応物 4

HCID 807IodineHCID 28019Potassium MetabisulfiteHCID 220840N-PhenylisonicotinamideHCID 178418339Butyllithium2 回

生成物 1

HCID 70988573-iodo-N-phenylisonicotinamide

試薬・触媒・溶媒 2

HCID 6344Dichloromethane溶媒HCID 8028Tetrahydrofuran溶媒2 回

反応条件

温度
-69 °C

実験手順

Into a 4-necked RBF equipped with an overhead stirrer and a J-Kem internal temperature probe was placed N-phenylisonicotinamide (35.1 g, 0.18 mol) and anhydrous THF (700 ml). All material appeared to go into solution. This mixture was cooled to −69° C. in a dry ice/IPA bath. To this was slowly added nBuLi (156 ml of a 2.5 M in Hexanes) in two portions. While adding the first equivalent of nBuLi, an exotherm was observed raising the temperature to approx. −41° C. The orange reaction mixture was slightly heterogeneous. This was allowed to slowly warm to 12° C. over 2 h. This mixture was re-cooled to −70° C. At this point, a THF solution (175 ml) of iodine (47.2 g, 0.19 mol) was added. This was allowed to warm and stirred at room temperature for 14 h. To this solution was added 150 ml of a saturated solution of potassium meta-bisulfite and diluted with CH2Cl2. The two layers were separated and the organic layer was extracted with brine. The two layers were separated and the organic layer was dried over MgSO4, filtered and concentrated under reduced pressure to give a black oil. This material was purified by SiO2 column chromatography using 40% ethyl acetate/Hexane as eluent. Concentration gave 38.6 g (67% th) of an off-white solid.

後処理

  1. customInto a 4-necked RBF equipped with an overhead stirrer
  2. temperaturean exotherm was observed raising the temperature to approx. −41° C
  3. temperatureto slowly warm to 12° C. over 2 h
  4. temperatureThis mixture was re-cooled to −70° C
  5. temperatureto warm
  6. customThe two layers were separated
  7. extractionthe organic layer was extracted with brine
  8. customThe two layers were separated
  9. dry with materialthe organic layer was dried over MgSO4
  10. filtrationfiltered
  11. concentrationconcentrated under reduced pressure
  12. customto give a black oil
  13. customThis material was purified by SiO2 column chromatography
  14. concentrationConcentration
  15. customgave 38.6 g (67% th) of an off-white solid

出典と根拠

ORDレコード
ord-7fb238d34ebb4b1d9b429d580c801468
出典データセット
uspto-grants-2008_09
特許番号
US07425639B2

関連ノート

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