Dimethylformamide → (E)-tert-butyl 4-(3-(3-methoxy-3-oxoprop-1-enyl)-1-(4-methoxybenzyl)-5-phenyl-1H-pyrazolo[3,4-b]pyridin-4-yl)piperazine-1-carboxylate

HRID 387548노트

반응식

HRID 387548 반응식
I[C:2]1[C:10]2[C:5](=[N:6][CH:7]=[C:8]([C:24]3[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=3)[C:9]=2[N:11]2[CH2:16][CH2:15][N:14]([C:17]([O:19][C:20]([CH3:23])([CH3:22])[CH3:21])=[O:18])[CH2:13][CH2:12]2)[N:4]([CH2:30][C:31]2[CH:36]=[CH:35][C:34]([O:37][CH3:38])=[CH:33][CH:32]=2)[N:3]=1.C(N(CC)CC)C.CN(C=O)C.[C:51]([O:55][CH3:56])(=[O:54])[CH:52]=[CH2:53]>CCOC(C)=O.O.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].C1(C)C=CC=CC=1P(C1C=CC=CC=1C)C1C=CC=CC=1C>[CH3:56][O:55][C:51](=[O:54])/[CH:52]=[CH:53]/[C:2]1[C:10]2[C:5](=[N:6][CH:7]=[C:8]([C:24]3[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=3)[C:9]=2[N:11]2[CH2:16][CH2:15][N:14]([C:17]([O:19][C:20]([CH3:23])([CH3:22])[CH3:21])=[O:18])[CH2:13][CH2:12]2)[N:4]([CH2:30][C:31]2[CH:36]=[CH:35][C:34]([O:37][CH3:38])=[CH:33][CH:32]=2)[N:3]=1

참가 물질

9

반응물 4

HCID 6228DimethylformamideHCID 7294Methyl AcrylateHCID 8471TriethylamineHCID 68760648tert-butyl 4-(3-iodo-1-(4-methoxybenzyl)-5-phenyl-1H-pyrazolo[3,4-b]pyridin-4-yl)piperazine-1-carboxylate

생성물 1

HCID 68763880(E)-tert-butyl 4-(3-(3-methoxy-3-oxoprop-1-enyl)-1-(4-methoxybenzyl)-5-phenyl-1H-pyrazolo[3,4-b]pyridin-4-yl)piperazine-1-carboxylate수율 84%

시약·촉매·용매 4

HCID 80271Tri-o-tolylphosphine촉매HCID 9811564Bis(dibenzylideneacetone)palladium촉매HCID 962Water용매HCID 8857Ethyl Acetate용매

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온도
100 °C

실험 절차

A 50 mL round bottom flask charged with tert-butyl 4-(3-iodo-1-(4-methoxybenzyl)-5-phenyl-1H-pyrazolo[3,4-b]pyridin-4-yl)piperazine-1-carboxylate (500 mg, 0.8 mmol), tri(o-tolyl)phosphine (18.25 mg, 0.06 mmol), Pd2dba3 (18.3 mg, 0.02 mmol), triethylamine (334 μL, 2.4 mmol), and DMF (7 mL) was purged under N2 (3 cycles). Next, methyl acrylate (216 μL, 2.4 mmol) was added, and the mixture was stirred at 100° C. under N2 atmosphere for 18 hours. The reaction mixture was cooled to room temperature, diluted with EtOAc (50 mL) and water (100 mL) was added. The phases were separated, and the organic layer was washed with water (3×30 mL), dried (MgSO4), filtered, and concentrated in vacuo. The residue obtained was crystallized from CH3CN to provide (E)-tert-butyl 4-(3-(3-methoxy-3-oxoprop-1-enyl)-1-(4-methoxybenzyl)-5-phenyl-1H-pyrazolo[3,4-b]pyridin-4-yl)piperazine-1-carboxylate (390 mg, 84% yield) as a solid. LCMS (APCI+) m/z 584.2 (M+H)+, Retention time=4.96 minutes.

후처리

  1. customwas purged under N2 (3 cycles)
  2. temperatureThe reaction mixture was cooled to room temperature
  3. additionwas added
  4. customThe phases were separated
  5. washthe organic layer was washed with water (3×30 mL)
  6. dry with materialdried (MgSO4)
  7. filtrationfiltered
  8. concentrationconcentrated in vacuo
  9. customThe residue obtained
  10. customwas crystallized from CH3CN

출처 및 근거

ORD 기록
ord-63d3173b2ecd43a39c21da5a76d7222d
출처 데이터셋
uspto-grants-2013_02
특허 번호
US08372842B2

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