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

HRID 1373394

반응식

HRID 1373394 반응식
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

참가 물질

8

반응물 4

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

생성물 1

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

시약·촉매·용매 3

HCID 167845palladium(II) acetate촉매HCID 634876Binap, (A+-)-촉매HCID 1140Toluene용매

실험 절차

To a solution of 1-[7-chloro-2-(4-fluorophenyl)pyrazolo[1,5-α]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-α]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).

후처리

  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

출처 및 근거

ORD 기록
ord-e437c05d1258455c9f445d4d80b77a20
출처 데이터셋
uspto-grants-2007_01
특허 번호
US07160897B2

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