Dimethylformamide → 5-acetyl-3-(N-allyl-N-n-propylamino)chroman

HRID 1684724

反応式

HRID 1684724 の反応式
[CH2:1]([N:4]([CH:8]1[CH2:17][C:16]2[C:11](=[CH:12][CH:13]=[CH:14][C:15]=2OS(C(F)(F)F)(=O)=O)[O:10][CH2:9]1)[CH2:5][CH2:6][CH3:7])[CH:2]=[CH2:3].[Li+].[Cl-].[CH3:28][Sn](C)(C)C.CN([CH:36]=[O:37])C>C1COCC1.CCCCCC.Cl[Pd]Cl.C(C1C=C(C)C=C(C(C)(C)C)C=1O)(C)(C)C>[C:36]([C:15]1[CH:14]=[CH:13][CH:12]=[C:11]2[C:16]=1[CH2:17][CH:8]([N:4]([CH2:1][CH:2]=[CH2:3])[CH2:5][CH2:6][CH3:7])[CH2:9][O:10]2)(=[O:37])[CH3:28]

参加物

8

反応物 4

HCID 6228DimethylformamideHCID 11661TetramethyltinHCID 433294Lithium ChlorideHCID 190282203-(N-Allyl-N-n-propylamino)-5-trifluoromethane-sulfonyloxychroman

生成物 1

HCID 190280895-acetyl-3-(N-allyl-N-n-propylamino)chroman収率 39%

試薬・触媒・溶媒 3

HCID 24290Palladium Chloride触媒HCID 314042,6-Di-tert-butyl-4-methylphenol触媒HCID 21883165Tetrahydrofuran hexane溶媒

反応条件

温度
120 °C

実験手順

3-(N-Allyl-N-n-propylamino)-5-trifluoromethanesulfonyloxychroman (0.28 g, 0.74 mmol), LiCl (0.097 g, 2.3 mmol), PdCl2 (dppf) (0.031 g, 0.04 mmol) and 2.6-di-t-butyl-4-methylphenol (0.005 g) were dissolved in DMF (5.0 mL) in a three-necked round-bottom flask (50 mL) with a magnetic stirrer. The flask was evacuated, followed by inlet of CO (three times). Tetramethyltin (0.12 mL, 0.89 mmol) was added and then the mixture was stirred under an atmosphere of CO (1 atm) at 120° C. (oilbath temp) for 4 hours. The solvent was evaporated, the residue was partitioned between aqueous NH3 (2M) and CH2Cl2 (3×15 mL) and the organic phases were dried (Na2SO4), filtered and concentrated in vacuo. Column chromatography on silica with THF-n-hexane (1:9) as eluent afforded 5-acetyl-3-(N-allyl-N-n-propylamino)chroman (0.078 g, 39% yield) as an oil. The base was precipitated from an ether solution by adding a slight excess of HCl (approx. 3M in ether). The crude salt was collected and dried in vacuo at 40° C. to give a white amorphous powder. Mp 125°-127° C. PdCl2 (dppf)=dichloro[1,1'-bis(diphenylphosphino)ferrocene]-palladium (II).

後処理

  1. customThe flask was evacuated
  2. customfollowed by inlet of CO (three times)
  3. customThe solvent was evaporated
  4. customthe residue was partitioned between aqueous NH3 (2M) and CH2Cl2 (3×15 mL)
  5. dry with materialthe organic phases were dried (Na2SO4)
  6. filtrationfiltered
  7. concentrationconcentrated in vacuo

出典と根拠

ORDレコード
ord-97c343a3e49a4dd18d3bb1c73c0b696a
出典データセット
uspto-grants-1997_06
特許番号
US05641807

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