Ammonium Chloride → 1-benzenesulfonyl-N*4*-((R)-1-benzyl-piperidin-3-yl)-1H-pyrrolo[2,3-b]pyridine-4,5-diamine

HRID 1257575ノート

反応式

HRID 1257575 の反応式
[C:1]1([S:7]([N:10]2[C:14]3=[N:15][CH:16]=[C:17]([N+:33]([O-])=O)[C:18]([NH:19][C@@H:20]4[CH2:25][CH2:24][CH2:23][N:22]([CH2:26][C:27]5[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=5)[CH2:21]4)=[C:13]3[CH:12]=[CH:11]2)(=[O:9])=[O:8])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[Cl-].[NH4+]>C(O)C.O.[Fe]>[C:1]1([S:7]([N:10]2[C:14]3=[N:15][CH:16]=[C:17]([NH2:33])[C:18]([NH:19][C@@H:20]4[CH2:25][CH2:24][CH2:23][N:22]([CH2:26][C:27]5[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=5)[CH2:21]4)=[C:13]3[CH:12]=[CH:11]2)(=[O:8])=[O:9])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1

参加物

5

反応物 2

HCID 25517Ammonium ChlorideHCID 58395364(1-benzenesulfonyl-5-nitro-1H-pyrrolo[2,3-b]pyridin-4-yl)-((R)-1-benzyl-piperidin-3-yl)amine

生成物 1

HCID 583947461-benzenesulfonyl-N*4*-((R)-1-benzyl-piperidin-3-yl)-1H-pyrrolo[2,3-b]pyridine-4,5-diamine収率 85.3%

試薬・触媒・溶媒 2

HCID 23925Iron触媒HCID 19096565Water ethanol溶媒

実験手順

A mixture of (1-benzenesulfonyl-5-nitro-1H-pyrrolo[2,3-b]pyridin-4-yl)-((R)-1-benzyl-piperidin-3-yl)amine (about 0.77 mmol), iron powder (129 mg, 2.31 mmol) and ammonium chloride (206 mg, 3.85 mmol) in ethanol/water (8 ml, 3:1) was heated to reflux for 4 hours. After cooling the mixture was filtered through CELITE®, thoroughly washing the filter cake with ethanol. The filtrate and washings were combined and concentrated under vacuum. The resulting residue was partitioned between ethyl acetate and water, and the organic layer dried with sodium sulfate and concentrated under vacuum. Purification by column chromatography on silica gel (gradient: 0 to 10% methanol in DCM) gave a residue, which was purified by column chromatography on silica gel (gradient: 0 to 5% methanol in ethyl acetate) affording 303 mg (84%) of 1-benzenesulfonyl-N*4*-((R)-1-benzyl-piperidin-3-yl)-1H-pyrrolo[2,3-b]pyridine-4,5-diamine. LCMS (Method B, ESI): RT=2.48-2.68 min, m+H=462.6; 1H NMR (400 MHz, CDCl3) δ: 8.12-8.08 (m, 2H), 7.79 (s, 1H), 7.55-7.49 (m, 1H), 7.46-7.38 (m, 3H), 7.37-7.22 (m, 5H), 6.47 (s, 1H), 5.32-5.26 (br m, 1H), 4.00-3.87 (br m, 1H), 3.58-3.46 (br m, 2H), 2.94-2.28 (br m, 6H), 1.82-1.67 (br m, 2H).

後処理

  1. temperaturewas heated
  2. temperatureto reflux for 4 hours
  3. temperatureAfter cooling the mixture
  4. filtrationwas filtered through CELITE®
  5. washthoroughly washing the filter cake with ethanol
  6. concentrationconcentrated under vacuum
  7. customThe resulting residue was partitioned between ethyl acetate and water
  8. dry with materialthe organic layer dried with sodium sulfate
  9. concentrationconcentrated under vacuum
  10. customPurification by column chromatography on silica gel (gradient: 0 to 10% methanol in DCM)
  11. customgave a residue, which
  12. customwas purified by column chromatography on silica gel (gradient: 0 to 5% methanol in ethyl acetate)

出典と根拠

ORDレコード
ord-fc01f74ebdd84098a1569f96d8f93c60
出典データセット
uspto-grants-2013_06
特許番号
US08461328B2

反応ノート

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