p-Toluenesulfonic acid → tert-butyl 2-{[1-(chloromethyl)-3-({5-[2-(dimethylamino)ethoxy]indol-2-yl}carbonyl)-5-nitro-1,2-dihydro-3H-benzo[e]indol-7-yl]sulfonyl}hydrazinecarboxylate

HRID 2238377ノート

反応式

HRID 2238377 の反応式
[Cl:1][CH2:2][CH:3]1[C:11]2[C:10]3[CH:12]=[CH:13][C:14]([S:16]([NH:19][NH:20][C:21]([O:23][C:24]([CH3:27])([CH3:26])[CH3:25])=[O:22])(=[O:18])=[O:17])=[CH:15][C:9]=3[C:8]([N+:28]([O-:30])=[O:29])=[CH:7][C:6]=2[NH:5][CH2:4]1.Cl.[CH3:32][N:33]([CH3:49])[CH2:34][CH2:35][O:36][C:37]1[CH:38]=[C:39]2[C:43](=[CH:44][CH:45]=1)[NH:42][C:41]([C:46](O)=[O:47])=[CH:40]2.CCN=C=NCCCN(C)C.CC1C=CC(S(O)(=O)=O)=CC=1>CC(N(C)C)=O>[Cl:1][CH2:2][CH:3]1[C:11]2[C:10]3[CH:12]=[CH:13][C:14]([S:16]([NH:19][NH:20][C:21]([O:23][C:24]([CH3:26])([CH3:27])[CH3:25])=[O:22])(=[O:17])=[O:18])=[CH:15][C:9]=3[C:8]([N+:28]([O-:30])=[O:29])=[CH:7][C:6]=2[N:5]([C:46]([C:41]2[NH:42][C:43]3[C:39]([CH:40]=2)=[CH:38][C:37]([O:36][CH2:35][CH2:34][N:33]([CH3:49])[CH3:32])=[CH:45][CH:44]=3)=[O:47])[CH2:4]1

参加物

6

反応物 4

HCID 6101p-Toluenesulfonic acidHCID 159081-Ethyl-3-(3'-dimethylaminopropyl)carbodiimideHCID 686908585-[2-(Dimethylamino)ethoxy]indole-2-carboxylic acid hydrochlorideHCID 68691139tert-butyl 2-{[1-(chloromethyl)-5-nitro-1,2-dihydro-3H-benzo[e]indol-7-yl]sulfonyl}hydrazinecarboxylate

生成物 1

HCID 68697420tert-butyl 2-{[1-(chloromethyl)-3-({5-[2-(dimethylamino)ethoxy]indol-2-yl}carbonyl)-5-nitro-1,2-dihydro-3H-benzo[e]indol-7-yl]sulfonyl}hydrazinecarboxylate収率 94%

試薬・触媒・溶媒 1

HCID 31374Dimethylacetamide溶媒

実験手順

A mixture of 119 (59.4 mg, 0.13 mmol), 5-[2-(dimethylamino)ethoxy]indole-2-carboxylic acid hydrochloride (48 mg, 0.17 mmol), EDCI (100 mg, 0.52 mmol), and TsOH (4.5 mg, 0.03 mmol) in DMA (2 mL) was stirred at room temperature for 4.5 h and then cooled to 0° C. Ice-cold aqueous NaHCO3 was added and the precipitate was filtered off, washed with water, and dried to give tert-butyl 2-{[1-(chloromethyl)-3-({5-[2-(dimethylamino)ethoxy]indol-2-yl}carbonyl)-5-nitro-1,2-dihydro-3H-benzo[e]indol-7-yl]sulfonyl}hydrazinecarboxylate (120) (84 mg, 94%) as a yellow solid: mp 175-180° C. (dec.); 1H NMR [(CD3)2SO] δ 11.72 (d, J=1.8 Hz, 1H), 9.85 (br s, 1H), 9.30 (v br s, 1H), 9.29 (s, 1H), 8.83 (d, J=1.5 Hz, 1H), 8.44 (d, J=8.9 Hz, 1H), 7.98 (dd, J=8.9, 1.7 Hz, 1H, 7.42 (d, J=8.9 Hz, 1H), 7.21 (d, J=1.6 Hz, 1H), 7.18 (d, J=2.4H, 1H), 6.95 (dd, J=8.9, 2.4 Hz, 1H), 5.02-4.96 (1,1H), 4.72 (dd, J=10.9, 2.4 Hz, 1H), 4.70-4.64 (m, 1H), 4.17-4.09 (m, 2H), 4.07 (t, J=5.9 Hz, 2H), 2.66 (t, J=5.7 Hz, 2H), 2.25 (s, 6H), 1.10 (br s, 9H). HRMS (FAB) calcd. for C3H3635ClN6O8S (MH+) m/z 687.2004, found 687.2002.

後処理

  1. temperaturecooled to 0° C
  2. additionIce-cold aqueous NaHCO3 was added
  3. filtrationthe precipitate was filtered off
  4. washwashed with water
  5. customdried

出典と根拠

ORDレコード
ord-b9de637e5fb143eea3a604a6fe10e200
出典データセット
uspto-grants-2010_05
特許番号
US07718688B2

反応ノート

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