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

HRID 60231ノート

反応式

HRID 60231 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]([Cl: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]([Cl: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][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

6

反応物 4

HCID 313Hydrochloric AcidHCID 24758Sodium hydrideHCID 3113400N-Cyanomethyl-4-methyl-benzenesulfonamideHCID 583651731-Benzenesulfonyl-5-chloro-2-bromomethyl-1H-pyrrolo[2,3-b]pyridine-3-carboxylic acid methyl ester

生成物 1

HCID 583650861-Benzenesulfonyl-5-chloro-2-{[cyanomethyl-(toluene-4-sulfonyl)amino]-methyl}-1H-pyrrolo[2,3-b]pyridine-3-carboxylic acid methyl ester収率 75.2%

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 (4.1 g, 60% dispersion in mineral oil, 101 mmol) was added portionwise to a cooled (0° C.) solution of 1-benzenesulfonyl-5-chloro-2-bromomethyl-1H-pyrrolo[2,3-b]pyridine-3-carboxylic acid methyl ester (40.8 g, 91.9 mmol) and N-cyanomethyl-4-methyl-benzenesulfonamide (21.3 g, 101 mmol) in DMF (400 mL). 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 (400 mL). 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 tan solid (39.6 g, 75%). LCMS (Method B: RT=4.58 min, M+H+=573/575. 1H NMR (400 MHz, CDCl3): 8.40 (d, J=2.4 Hz, 1H), 8.33-8.33 (m, 2H), 8.27 (d, J=2.4 Hz, 1H), 7.78 (d, J=8.2 Hz, 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-1dcabfb8ad264b8cbc1fd616290d5ded
出典データセット
uspto-grants-2016_09
特許番号
US09440976B2

反応ノート

読み込み中…