Dimethylacetamide → 4-(4-Aminobenzoyl)benzonitrile

HRID 926470

反応式

HRID 926470 の反応式
CN1[C:6]([C:7]([C:9]2[CH:14]=[CH:13][C:12]([N+:15]([O-])=O)=[CH:11][CH:10]=2)=[O:8])=[CH:5]N=C1.C1(P(C2CCCCC2)[C:25]2C=CC=C[C:26]=2[C:31]2[C:36](C(C)C)=CC(C(C)C)=C[C:32]=2C(C)C)CCCCC1.CC([N:55](C)C)=O>C(OCC)(=O)C.[C-]#N.[Zn+2].[C-]#N.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd].[Zn]>[NH2:15][C:12]1[CH:11]=[CH:10][C:9]([C:7]([C:6]2[CH:5]=[CH:36][C:31]([C:32]#[N:55])=[CH:26][CH:25]=2)=[O:8])=[CH:14][CH:13]=1

参加物

8

反応物 3

HCID 31374DimethylacetamideHCID 111557942-Dicyclohexylphosphino-2',4',6'-triisoprophylbiphenylHCID 86715600(1-Methyl-1H-imidazol-5-yl)(4-nitrophenyl)methanone2 回

生成物 1

HCID 198022084-(4-Aminobenzoyl)benzonitrile

試薬・触媒・溶媒 4

HCID 11186Zinc cyanide (Zn(CN)2)触媒HCID 23994Zinc触媒HCID 9811564Bis(dibenzylideneacetone)palladium触媒HCID 8857Ethyl Acetate溶媒

反応条件

温度
120 °C

実験手順

A mixture containing (4-aminophenyl)(4-chlorophenyl)methanone (2.5 g, 11 mmol, Intermediate 16: step b), zinc cyanide (1.65 g, 14.0 mmol), tris(dibenzylideneacetone)dipalladium (692 mg, 0.755 mmol), zinc powder (141 mg, 2.16 mmol), 2-dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl (XPhos, 371 mg, 0.755 mmol), and dimethylacetamide (54 mL, sparged with nitrogen for 45 minutes) was heated to 120° C. After 2 hours, the flask was allowed to cool to 23° C. The mixture was diluted with ethyl acetate (150 mL) and then filtered through Celite®. The filtrate was washed with saturated aqueous sodium chloride solution (2×100 mL). The organic phase was dried over sodium sulfate and then filtered. Silica gel (8 g) was added to the filtrate and the solvent was removed by rotary evaporation to afford a free-flowing powder. The powder was loaded onto a column of silica gel for purification. Elution with dichloromethane initially, grading to 5% methanol-dichloromethane provided the title compound as a solid.

後処理

  1. temperatureto cool to 23° C
  2. filtrationfiltered through Celite®
  3. washThe filtrate was washed with saturated aqueous sodium chloride solution (2×100 mL)
  4. dry with materialThe organic phase was dried over sodium sulfate
  5. filtrationfiltered
  6. additionSilica gel (8 g) was added to the filtrate
  7. customthe solvent was removed by rotary evaporation
  8. customto afford a free-flowing powder
  9. customThe powder was loaded onto a column of silica gel for purification
  10. washElution with dichloromethane initially

出典と根拠

ORDレコード
ord-981720d70fbb48f2848e2d08a4c622fd
出典データセット
uspto-grants-2016_03
特許番号
US09284308B2

関連ノート

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