Water → methyl 1-(chloromethyl)-5-nitro-3-[(5,6,7-trimethoxyindol-2-yl)carbonyl]-1,2-dihydro-3H-pyrrolo[3,2-e]indole-7-carboxylate

HRID 366838

反応式

HRID 366838 の反応式
[Cl:1]P(Cl)(C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.O[CH2:23][CH:24]1[C:28]2=[C:29]3[C:33](=[C:34]([N+:36]([O-:38])=[O:37])[CH:35]=[C:27]2[N:26]([C:43]([C:45]2[NH:46][C:47]4[C:52]([CH:53]=2)=[CH:51][C:50]([O:54][CH3:55])=[C:49]([O:56][CH3:57])[C:48]=4[O:58][CH3:59])=[O:44])[CH2:25]1)[NH:32][C:31]([C:39]([O:41][CH3:42])=[O:40])=[CH:30]3.O>N1C=CC=CC=1>[Cl:1][CH2:23][CH:24]1[C:28]2=[C:29]3[C:33](=[C:34]([N+:36]([O-:38])=[O:37])[CH:35]=[C:27]2[N:26]([C:43]([C:45]2[NH:46][C:47]4[C:52]([CH:53]=2)=[CH:51][C:50]([O:54][CH3:55])=[C:49]([O:56][CH3:57])[C:48]=4[O:58][CH3:59])=[O:44])[CH2:25]1)[NH:32][C:31]([C:39]([O:41][CH3:42])=[O:40])=[CH:30]3

参加物

5

反応物 3

HCID 962WaterHCID 260420Triphenylphosphine dichloride2 回HCID 10577983methyl 1-hydroxymethyl-5-nitro-3-[(5,6,7-trimethoxyindol-2-yl)carbonyl]-1,2-dihydro-3H-pyrrolo[3,2-e]indole-7-carboxylate

生成物 1

HCID 394852methyl 1-(chloromethyl)-5-nitro-3-[(5,6,7-trimethoxyindol-2-yl)carbonyl]-1,2-dihydro-3H-pyrrolo[3,2-e]indole-7-carboxylate収率 64%

試薬・触媒・溶媒 1

HCID 1049Pyridine溶媒

反応条件

温度
20 °C

実験手順

Dichlorotriphenylphosphorane (1.65 g, 5.1 mmol) was added to a solution of 56 (1.34 g, 2.55 mmol) in pyridine (75 mL) and the solution stirred at 20° C. After 10 min more dichlorotriphenylphosphorane (2.06 g, 6.4 mmol) was added, and after a further 10 min the solution was poured into H2O and the mixture stirred for 5 min. The precipitated solid was filtered off, washed with H2O, and redissolved in CH2Cl2 (400 mL). This solution was filtered through Celite, eluting with CH2Cl2, and the filtrate was dried (Na2SO4) and evaporated. The resulting orange solid was recrystallized from CH2Cl2 giving methyl 1-(chloromethyl)-5-nitro-3-[(5,6,7-trimethoxyindol-2-yl)carbonyl]-1,2-dihydro-3H-pyrrolo[3,2-e]indole-7-carboxylate (31) as an orange powder (0.88 g, 64%), mp 246-247.5° C. The mother liquor was evaporated onto silica and purified by chromatography (50% EtOAc-petroleum ether) to give further 31 (0.50 g, 36%). 1H NMR (CDCl3) δ 10.39 (s, 1 H, NH), 9.42 (s, 1 H, NH), 9.39 (s, 1 H, H-4), 7.31 (d, J=2.2 Hz, 1 H, H-8), 6.97 (d, J=2.4 Hz, 1 H, H-3'), 6.86 (s, 1 H, H-4'), 4.80 (t, J=10.0 Hz, 1 H, H-2), 4.69 (dd, J=10.8, 4.4 Hz, 1 H, H-2), 4.32-42.3 (m, 1 H, H-1). 4.09 (s, 3 H, OMe), 4.05 (dd, J=11.4, 3.9 Hz, 1 H, CH2Cl), 4.02 (s, 3 H, OMe), 3.95 (s, 3 H, OMe), 3.91 (s, 3 H, OMe), 3.77 (dd, J=11.4, 8.8 Hz, 1 H, CH2Cl); 13C NMR [(CD3)2SO] δ 160.5, 160.0, 149.2, 140.0, 139.0, 137.5, 133.6, 132.1, 131.3, 130.2, 127.7, 126.1, 125.5, 123.2, 111.3, 107.5, 106.4, 97.9, 61.1, 60.9, 55.9, 54.1, 52.3, 47.0, 42.0. Anal. Calculated for C25H23ClN4O8 : C, 55.3; H, 4.3; N, 10.3. Found: C, 55.4; H, 4.1; N, 10.3%.

後処理

  1. stirringthe mixture stirred for 5 min
  2. filtrationThe precipitated solid was filtered off
  3. washwashed with H2O
  4. dissolutionredissolved in CH2Cl2 (400 mL)
  5. filtrationThis solution was filtered through Celite
  6. washeluting with CH2Cl2
  7. dry with materialthe filtrate was dried (Na2SO4)
  8. customevaporated
  9. customThe resulting orange solid was recrystallized from CH2Cl2

出典と根拠

ORDレコード
ord-e945557f9e46429fbb718e25989a417a
出典データセット
uspto-grants-2000_10
特許番号
US06130237

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