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Hydrochloric Acid → 1-benzenesulfonyl-5-bromo-2-{[cyanomethyl-(toluene-4-sulfonyl)amino]methyl}-1H-pyrrolo[2,3-b]pyridine-3-carboxylic acid methyl ester

HRID 60214
ノート
印刷プレビュー

反応式

HRID 60214 の反応式
[H-].[Na+].[CH3:3][O:4][C:5]([C:7]1[C:15]2[C:10](=[N:11][CH:12]=[C:13]([Br:16])[CH:14]=2)[N:9]([S:17]([C:20]2[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=2)(=[O:19])=[O:18])[C:8]=1[CH2:26]Br)=[O:6].[C:28]([CH2:30][NH:31][S:32]([C:35]1[CH:40]=[CH:39][C:38]([CH3:41])=[CH:37][CH:36]=1)(=[O:34])=[O:33])#[N:29].Cl>CN(C=O)C>[CH3:3][O:4][C:5]([C:7]1[C:15]2[C:10](=[N:11][CH:12]=[C:13]([Br:16])[CH:14]=2)[N:9]([S:17]([C:20]2[CH:21]=[CH:22][CH:23]=[CH:24][CH:25]=2)(=[O:18])=[O:19])[C:8]=1[CH2:26][N:31]([CH2:30][C:28]#[N:29])[S:32]([C:35]1[CH:36]=[CH:37][C:38]([CH3:41])=[CH:39][CH:40]=1)(=[O:34])=[O:33])=[O:6]
参加物反応条件実験手順後処理出典と根拠反応ノート

参加物

6

反応物 4

HCID 313Hydrochloric AcidHCID 24758Sodium hydrideHCID 3113400N-Cyanomethyl-4-methyl-benzenesulfonamideHCID 582663771H-Pyrrolo[2,3-b]pyridine-3-carboxylic acid, 5-bromo-2-(bromomethyl)-1-(phenylsulfonyl)-, methyl ester

生成物 1

HCID 582666181-benzenesulfonyl-5-bromo-2-{[cyanomethyl-(toluene-4-sulfonyl)amino]methyl}-1H-pyrrolo[2,3-b]pyridine-3-carboxylic acid methyl ester
収率 94%

試薬・触媒・溶媒 1

HCID 6228Dimethylformamide溶媒

反応条件

温度
0 °C

実験手順

Sodium hydride (11.7 g, 60% dispersion in mineral oil, 293 mmol) was added portionwise to a cooled (0° C.) solution of 1-benzenesulfonyl-5-bromo-2-bromomethyl-1H-pyrrolo[2,3-b]pyridine-3-carboxylic acid methyl ester (130 g, 266 mmol) and N-cyanomethyl-4-methyl-benzenesulfonamide (61.5 g, 293 mmol) in DMF (1.25 L). The reaction mixture was stirred at 0° C. for 15 minutes, then allowed to warm to ambient temperature and stirred for 1 hour. The reaction mixture was poured into a cooled, stirred solution of 2M hydrochloric acid (1.25 L). The resultant precipitate was collected by filtration (slow) and the cake washed with water, followed by methanol and then diethyl ether. The resulting cake was dried to afford the title compound as a grey solid (154 g, 94%). LCMS (Method B): RT=4.28 min, M+H+=617/619. 1H NMR (400 MHz, CDCl3): 8.49 (d, J=2.3 Hz, 1H), 8.42 (d, J=2.3 Hz, 1H), 8.33-8.33 (m, 2H), 7.78-7.76 (m, 2H), 7.64-7.64 (m, 1H), 7.55-7.54 (m, 2H), 7.34 (d, J=8.1 Hz, 2H), 5.43 (s, 2H), 4.28 (s, 2H), 3.96 (s, 3H), 2.43 (s, 3H).

後処理

  1. temperatureto warm to ambient temperature
  2. stirringstirred for 1 hour
  3. additionThe reaction mixture was poured into a cooled
  4. filtrationThe resultant precipitate was collected by filtration (slow)
  5. washthe cake washed with water
  6. customThe resulting cake was dried

出典と根拠

ORDレコード
ord-853fb808fe3e4691bfb5ee8dc879afb1
出典データセット
uspto-grants-2016_09
DOI
10.6084/m9.figshare.5104873.v1
特許番号
US09440976B2

反応ノート

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