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Dimethylacetamide → HCID 89700014、化合物

HRID 1055753
ノート
印刷プレビュー

反応式

HRID 1055753 の反応式
[C:1]([C:5]1[CH:6]=[C:7]([CH:32]=[C:33](Cl)[N:34]=1)[C:8]([NH:10][C:11]1[CH:16]=[CH:15][C:14]([CH3:17])=[C:13]([N:18]2[C:25]3[N:21]([N:22]=[C:23]([C:26]4[CH:27]=[N:28][CH:29]=[CH:30][CH:31]=4)[CH:24]=3)[CH:20]=[CH:19]2)[CH:12]=1)=[O:9])([CH3:4])([CH3:3])[CH3:2].C(P(C(C)(C)C)C1C=CC2C(=CC=CC=2)C=1C1C2C(=CC=CC=2)C=CC=1)(C)(C)C.[CH3:65][N:66](C)C(=O)C>C(OCC)(=O)C.FC(F)(F)C([O-])=O.[Pd+2].FC(F)(F)C([O-])=O.[Zn].[C-]#N.[Zn+2].[C-]#N>[C:1]([C:5]1[CH:6]=[C:7]([CH:32]=[C:33]([C:65]#[N:66])[N:34]=1)[C:8]([NH:10][C:11]1[CH:16]=[CH:15][C:14]([CH3:17])=[C:13]([N:18]2[C:25]3[N:21]([N:22]=[C:23]([C:26]4[CH:27]=[N:28][CH:29]=[CH:30][CH:31]=4)[CH:24]=3)[CH:20]=[CH:19]2)[CH:12]=1)=[O:9])([CH3:4])([CH3:3])[CH3:2]
参加物反応条件実験手順後処理出典と根拠反応ノート

参加物

8

反応物 3

HCID 31374DimethylacetamideHCID 2734941(1,1'-Binaphthalen)-2-yldi-tert-butylphosphineHCID 89699945HCID 89699945、化合物

生成物 1

HCID 89700014HCID 89700014、化合物

試薬・触媒・溶媒 4

HCID 11186Zinc cyanide (Zn(CN)2)触媒HCID 23994Zinc
触媒
HCID 2733347Palladium(II) trifluoroacetate触媒
HCID 8857Ethyl Acetate溶媒

反応条件

温度
95 °C

実験手順

Under argon, a mixture of 137 mg (0.28 mmol) of the compound of Example 65, 4.04 mg (0.012 mmol) of palladium(II) trifluoroacetate, 9.91 mg (0.025 mmol) of racemic 2-di-tert-butylphosphino-1,1′-binaphthyl, 3.51 mg (0.054 mmol) of zinc flakes and 18.6 mg (0.16 mmol) of zinc cyanide in 1.5 ml N,N-dimethylacetamide was stirred at 95° C. for 20 hours. After cooling, the mixture was diluted with 80 ml of ethyl acetate and the mixture was washed in each case once with 10 ml of water and 10 ml saturated sodium chloride solution. The organic phase was dried over sodium sulphate and, after filtration, concentrated under reduced pressure. The residue obtained in this manner was purified by chromatography on a Biotage system (25 g Snap column; mobile phase gradient ethyl acetate/hexane, starting with 70% ethyl acetate, then increasing rapidly to 100% ethyl acetate). Further purification was by preparative thick-layer chromatography (2 mm layer thickness with concentration zone, mobile phase ethyl acetate, elution with methylene chloride/methanol 7:3). This gave 56 mg (38% of theory) of the title compound.

後処理

  1. temperatureAfter cooling
  2. washthe mixture was washed in each case once with 10 ml of water and 10 ml saturated sodium chloride solution
  3. dry with materialThe organic phase was dried over sodium sulphate
  4. filtrationafter filtration
  5. concentrationconcentrated under reduced pressure
  6. customThe residue obtained in this manner
  7. customwas purified by chromatography on a Biotage system (25 g Snap column
  8. temperatureincreasing rapidly to 100% ethyl acetate)
  9. customFurther purification
  10. concentrationwas by preparative thick-layer chromatography (2 mm layer thickness with concentration zone, mobile phase ethyl acetate, elution with methylene chloride/methanol 7:3)

出典と根拠

ORDレコード
ord-e7f88f5b5e144a79b254d62dd1ac8cf0
出典データセット
uspto-grants-2016_07
DOI
10.6084/m9.figshare.5104873.v1
特許番号
US09394309B2

反応ノート

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