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

반응식

HRID 366838 반응식
[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

참가 물질

5

반응물 3

HCID 962WaterHCID 260420Triphenylphosphine dichloride2회HCID 10577983methyl 1-hydroxymethyl-5-nitro-3-[(5,6,7-trimethoxyindol-2-yl)carbonyl]-1,2-dihydro-3H-pyrrolo[3,2-e]indole-7-carboxylate

생성물 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-carboxylate수율 64%

시약·촉매·용매 1

HCID 1049Pyridine용매

반응 조건

온도
20 °C

실험 절차

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%.

후처리

  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

출처 및 근거

ORD 기록
ord-e945557f9e46429fbb718e25989a417a
출처 데이터셋
uspto-grants-2000_10
특허 번호
US06130237

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