Sodium Azide → 3-[2-(3-azidoanilino)-4-pyrimidinyl]-N-cyclopentyl-2-(4-methoxyphenyl)pyrazolo[1,5-a]pyridin-7-amine

HRID 896790

反応式

HRID 896790 の反応式
[CH:1]1([NH:6][C:7]2[N:12]3[N:13]=[C:14]([C:30]4[CH:35]=[CH:34][C:33]([O:36][CH3:37])=[CH:32][CH:31]=4)[C:15]([C:16]4[CH:21]=[CH:20][N:19]=[C:18]([NH:22][C:23]5[CH:24]=[C:25]([NH2:29])[CH:26]=[CH:27][CH:28]=5)[N:17]=4)=[C:11]3[CH:10]=[CH:9][CH:8]=2)[CH2:5][CH2:4][CH2:3][CH2:2]1.N([O-])=O.[Na+].[N-:42]=[N+:43]=[N-].[Na+].C(=O)(O)[O-].[Na+]>C(O)(=O)C.O.O.CCOCC>[N:29]([C:25]1[CH:24]=[C:23]([CH:28]=[CH:27][CH:26]=1)[NH:22][C:18]1[N:17]=[C:16]([C:15]2[C:14]([C:30]3[CH:31]=[CH:32][C:33]([O:36][CH3:37])=[CH:34][CH:35]=3)=[N:13][N:12]3[C:7]([NH:6][CH:1]4[CH2:5][CH2:4][CH2:3][CH2:2]4)=[CH:8][CH:9]=[CH:10][C:11]=23)[CH:21]=[CH:20][N:19]=1)=[N+:42]=[N-:43]

参加物

8

反応物 4

HCID 33557Sodium Azide2 回HCID 516892Sodium BicarbonateHCID 10141279N'-{[7-(cyclopentylamino)-2-(4-methoxyphenyl)pyrazolo[1,5-a]pyridin-3-yl]-2-pyrimidinyl}-1,3-benzenediamineHCID 23668193Sodium Nitrite2 回

生成物 1

HCID 102795183-[2-(3-azidoanilino)-4-pyrimidinyl]-N-cyclopentyl-2-(4-methoxyphenyl)pyrazolo[1,5-a]pyridin-7-amine収率 23%

試薬・触媒・溶媒 3

HCID 962Water溶媒2 回HCID 3283Diethyl Ether溶媒HCID 21899381Acetic acid--water (1/1)溶媒

反応条件

温度
0 °C

実験手順

The following transformation was performed in the dark. To a cold (0° C.) solution of N′-{[7-(cyclopentylamino)-2-(4-methoxyphenyl)pyrazolo[1,5-a]pyridin-3-yl]-2-pyrimidinyl}-1,3-benzenediamine (16.5 mg, 0.03 mmol) in acetic acid/water (80/20, 1 mL) was added aqueous sodium nitrite (0.32 mL of a stock solution prepared by dissolving 200 mg of sodium nitrite in 25 mL water, 0.04 mmol). The resultant dark solution was stirred at 0° C. for 15 minutes. Aqueous sodium azide (0.11 mL of a stock solution prepared by dissolving 200 mg of sodium azide in 10 mL of water, 0.04 mmol) was added and the resultant solution was stirred for 1.5 hours over which time it was allowed to warm to room temperature. Ether was added and the solution made basic by dropwise addition of saturated aqueous sodium bicarbonate. The organic layer was washed with brine. The aqueous layer was extracted with ethyl acetate and the combined organics were dried over magnesium sulfate. Filtration and concentration gave a solid residue which was purified by flash chromatography (4:1 to 2:1 hexanes-ethyl acetate) to provide 3-[2-(3-azidoanilino)-4-pyrimidinyl]-N-cyclopentyl-2-(4-methoxyphenyl)pyrazolo[1,5-a]pyridin-7-amine (4 mg, 23%) as a tinted solid. 1H NMR (CDCl3): δ 8.12 (d, 1 H), 7.71 (d, 1 H), 7.60-7.56 (m, 3 H), 7.33-7.25 (m, 3 H), 6.98 (d, 2H), 6.70 (d, 1 H), 6.54 (d, 1 H), 6.05-6.04 (m, 2 H), 4.00 (m, 1 H), 3.87 (s, 3 H), 2.13 (m, 2 H), 1.85-1.58 (m, 6 H); MS m/z 518 (M+1).

後処理

  1. additionwas added
  2. temperatureto warm to room temperature
  3. washThe organic layer was washed with brine
  4. extractionThe aqueous layer was extracted with ethyl acetate
  5. dry with materialthe combined organics were dried over magnesium sulfate
  6. filtrationFiltration and concentration
  7. customgave a solid residue which
  8. customwas purified by flash chromatography (4:1 to 2:1 hexanes-ethyl acetate)

出典と根拠

ORDレコード
ord-cb46d31ddeaf40d29c64c6639034dc0b
出典データセット
uspto-grants-2005_07
特許番号
US06919352B2

関連ノート

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