Cyclopentylamine → 1-[7-(Cyclopentylamino)-2-(4-fluorophenyl)pyrazolo[1,5-a]pyridin-3-yl]ethanone

HRID 896767

反応式

HRID 896767 の反応式
Cl[C:2]1[N:7]2[N:8]=[C:9]([C:14]3[CH:19]=[CH:18][C:17]([F:20])=[CH:16][CH:15]=3)[C:10]([C:11](=[O:13])[CH3:12])=[C:6]2[CH:5]=[CH:4][CH:3]=1.C(=O)([O-])[O-].[Cs+].[Cs+].[CH:27]1([NH2:32])[CH2:31][CH2:30][CH2:29][CH2:28]1.CCOCC>C1(C)C=CC=CC=1.C([O-])(=O)C.[Pd+2].C([O-])(=O)C.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>[CH:27]1([NH:32][C:2]2[N:7]3[N:8]=[C:9]([C:14]4[CH:19]=[CH:18][C:17]([F:20])=[CH:16][CH:15]=4)[C:10]([C:11](=[O:13])[CH3:12])=[C:6]3[CH:5]=[CH:4][CH:3]=2)[CH2:31][CH2:30][CH2:29][CH2:28]1

参加物

8

反応物 4

HCID 2906CyclopentylamineHCID 3283Diethyl EtherHCID 10796Cesium carbonateHCID 223500461-(7-Chloro-2-(4-fluorophenyl)pyrazolo[1,5-a]pyridin-3-yl)ethanone

生成物 1

HCID 121025001-[7-(Cyclopentylamino)-2-(4-fluorophenyl)pyrazolo[1,5-a]pyridin-3-yl]ethanone収率 96.7%

試薬・触媒・溶媒 3

HCID 167845palladium(II) acetate触媒HCID 634876Binap, (A+-)-触媒HCID 1140Toluene溶媒

実験手順

To a solution of 1-[7-chloro-2-(4-fluorophenyl)pyrazolo[1,5-a]pyridin-3-yl]ethanone (2.7 g, 9.5 mmol) in toluene (50 mL) was added successively racemic-BINAP (378 mg, 0.6 mmol), cesium carbonate (4.7 g, 14.3 mmol), cyclopentylamine (4.7 mL, 47.5 mmol), and palladium(II) acetate (86 mg, 0.4 mmol). The resultant mixture was heated to 95° C. for 2.5 hours at which time the reaction was judged complete by thin layer chromatography. The solution was cooled to room temperature and ether was added. The organic layer was washed with water and brine. The aqueous layer was extracted with ether and the combined organics dried over magnesium sulfate. Filtration and concentration followed by flash chromatography (4:1 hexanes-ethyl acetate) provided 1-[7-(cyclopentylamino)-2-(4-fluorophenyl)pyrazolo[1,5-a]pyridin-3-yl]ethanone (3.1 g, 95%) as a yellow solid. 1H NMR (CDCl3): δ 7.62 (d, 1 H), 7.55 (dd, 2 H), 7.40 (t, 1 H), 7.15 (t, 2 H), 6.10 (d, 1 H), 5.99 (d, 1 H), 3.94 (m, 1 H), 2.09 (s, 3 H), 2.12-2.04 (m, 2 H), 1.78-1.58 (m, 6 H); 13C NMR (CDCl3) δ 192.63, 163.28 (d, JCF=247.3 Hz), 154.89, 142.65, 142.38, 131.66 (d, JCF=8.3 Hz) 131.09, 130.03 (d, JCF=3.8 Hz), 115.33 (d, JCF=22.0 Hz), 111.32, 105.41, 91.97, 53.81, 33.21, 30.10, 23.96; 19F NMR (CDCl3) δ −112.70; MS m/z 338 (M+1).

後処理

  1. washThe organic layer was washed with water and brine
  2. extractionThe aqueous layer was extracted with ether
  3. dry with materialthe combined organics dried over magnesium sulfate
  4. filtrationFiltration and concentration

出典と根拠

ORDレコード
ord-3f4c762d124a4767918290059c80384b
出典データセット
uspto-grants-2005_07
特許番号
US06919352B2

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