Cesium carbonate → 7-(Cyclopropylamino)-5-(3,5-difluorophenylamino)pyrazolo[1,5-a]pyrimidine-3-carbaldehyde

HRID 624695ノート

反応式

HRID 624695 の反応式
[F:1][C:2]1[CH:3]=[C:4]([CH:6]=[C:7]([F:9])[CH:8]=1)[NH2:5].C([O-])([O-])=O.[Cs+].[Cs+].Cl[C:17]1[CH:22]=[C:21]([N:23]([CH:31]2[CH2:33][CH2:32]2)C(=O)OC(C)(C)C)[N:20]2[N:34]=[CH:35][C:36]([CH:37]=[O:38])=[C:19]2[N:18]=1.C1C=CC(P(C2C(C3C(P(C4C=CC=CC=4)C4C=CC=CC=4)=CC=C4C=3C=CC=C4)=C3C(C=CC=C3)=CC=2)C2C=CC=CC=2)=CC=1>O1CCOCC1.C([O-])(=O)C.[Pd+2].C([O-])(=O)C.CCOCC>[CH:31]1([NH:23][C:21]2[N:20]3[N:34]=[CH:35][C:36]([CH:37]=[O:38])=[C:19]3[N:18]=[C:17]([NH:5][C:4]3[CH:3]=[C:2]([F:1])[CH:8]=[C:7]([F:9])[CH:6]=3)[CH:22]=2)[CH2:32][CH2:33]1

参加物

8

反応物 4

HCID 10796Cesium carbonateHCID 965953,5-DifluoroanilineHCID 634876Binap, (A+-)-HCID 58196421Tert-butyl 5-chloro-3-formylpyrazolo[1,5-a]pyrimidin-7-yl(cyclopropyl)carbamate

生成物 1

HCID 583143057-(Cyclopropylamino)-5-(3,5-difluorophenylamino)pyrazolo[1,5-a]pyrimidine-3-carbaldehyde収率 80%

試薬・触媒・溶媒 3

HCID 167845palladium(II) acetate触媒HCID 3283Diethyl Ether溶媒HCID 312751,4-Dioxane溶媒

実験手順

3,5-Difluoroaniline (29 mg, 0.22 mmol), Cs2CO3 (67 mg, 0.21 mmol) were added to Tert-butyl 5-chloro-3-formylpyrazolo[1,5-a]pyrimidin-7-yl(cyclopropyl)carbamate (50 mg, 0.15 mmol) dissolved in 1,4-dioxane (1 mL). Racemic BINAP (6 mg, 0.06 mmol) and palladium(II) acetate (4 mg, 0.04 mmol) were then added. The mixture was sealed and irradiated at 110° C. for 20 min in the microwave. Et2O (3 mL) was added and the solution was filtered. The filtrate was concentrated in vacuo. The crude residue was dissolved in dichloromethane (1.5 mL) and trifluoroacetic acid (1.5 mL). After 1 h, the solution was concentrated under a stream of air. The residue was triturated with 20% 2-propanol/hexanes. The product was filtered to yield 7-(cyclopropylamino)-5-(3,5-difluorophenylamino)pyrazolo[1,5-a]pyrimidine-3-carbaldehyde (39 mg, 80%). LCMS (M+1=330)

後処理

  1. customThe mixture was sealed
  2. customirradiated at 110° C. for 20 min in the microwave
  3. filtrationthe solution was filtered
  4. concentrationThe filtrate was concentrated in vacuo
  5. dissolutionThe crude residue was dissolved in dichloromethane (1.5 mL)
  6. concentrationthe solution was concentrated under a stream of air
  7. customThe residue was triturated with 20% 2-propanol/hexanes
  8. filtrationThe product was filtered

出典と根拠

ORDレコード
ord-38813bad27a24948b4906a13d92a2a86
出典データセット
uspto-grants-2016_04
特許番号
US09303033B2

反応ノート

読み込み中…