1,4,7,10-Tetraoxacyclododecane → 2-chloro-5-cyano-N,N-dimethylnicotinamide

HRID 2294127ノート

反応式

HRID 2294127 の反応式
[Cl:1][C:2]1[N:12]=[CH:11][C:10](I)=[CH:9][C:3]=1[C:4]([N:6]([CH3:8])[CH3:7])=[O:5].[C-:14]#[N:15].[Li+].O1CCOCCOCCOCC1>C1C=CC=CC=1.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>[Cl:1][C:2]1[N:12]=[CH:11][C:10]([C:14]#[N:15])=[CH:9][C:3]=1[C:4]([N:6]([CH3:8])[CH3:7])=[O:5]

参加物

6

反応物 3

HCID 92691,4,7,10-TetraoxacyclododecaneHCID 75478Lithium cyanideHCID 108287932-chloro-5-iodo-N,N-dimethylnicotinamide

生成物 1

HCID 107509252-chloro-5-cyano-N,N-dimethylnicotinamide収率 54.4%

試薬・触媒・溶媒 2

HCID 178418397HCID 178418397、化合物触媒HCID 241Benzene溶媒

反応条件

温度
40 °C

実験手順

A mixture of 2-chloro-5-iodo-N,N-dimethylnicotinamide (1.54 g, 5 mmol), prepared as in Example 14, and lithium cyanide (0.5M in DMF, 20 mL, 10 mmol) was distilled at reduced pressure. The residue was suspended in 1,4,7,10-tetraoxacyclo-dodecane (0.2 mL, 1.25 mmol) in 50 mL of benzene and the mixture was distilled under nitrogen until a forefraction of approximately 5 mL had collected. The suspension was allowed to cool and then tetrakis(triphenylphosphine)palladium(0) (2.44 g, 2.1 mmol) was added. The mixture was stirred at 40° C. under nitrogen for 1 week, allowed to cool to room temperature and partitioned between aqueous sodium bicarbonate and ethyl acetate. The aqueous layer was extracted with diethyl ether and the extract was washed with brine, dried (Na2 SO4) and concentrated. The residue was purified on silica gel by column chromatography eluting with hexanes/ethyl acetate (5:1) to give 2-chloro-5-cyano-N,N-dimethylnicotinamide (0.57 g, 2.72 mmol), m.p. 148°-153° C.

後処理

  1. distillationwas distilled at reduced pressure
  2. distillationthe mixture was distilled under nitrogen until a forefraction of approximately 5 mL
  3. customhad collected
  4. temperatureto cool
  5. temperatureto cool to room temperature
  6. custompartitioned between aqueous sodium bicarbonate and ethyl acetate
  7. extractionThe aqueous layer was extracted with diethyl ether
  8. washthe extract was washed with brine
  9. customdried (Na2 SO4)
  10. concentrationconcentrated
  11. customThe residue was purified on silica gel by column chromatography
  12. washeluting with hexanes/ethyl acetate (5:1)

出典と根拠

ORDレコード
ord-aa35a15c97f14838b8be959e195efa38
出典データセット
uspto-grants-1997_11
特許番号
US05688795

反応ノート

読み込み中…