Diisobutylaluminum hydride → 3-(tert-butyloxycarbonyl)-1-hydroxymethyl-5-nitro,1,2-dihydro-3H-benz[e]indole

HRID 366803노트

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HRID 366803 반응식
[C:1]([O:5][C:6]([N:8]1[C:16]2[CH:15]=[C:14]([N+:17]([O-:19])=[O:18])[C:13]3[CH:20]=[CH:21][CH:22]=[CH:23][C:12]=3[C:11]=2[CH:10]([C:24](OC)=[O:25])[CH2:9]1)=[O:7])([CH3:4])([CH3:3])[CH3:2].CC(C[AlH]CC(C)C)C>C1COCC1.C1(C)C=CC=CC=1>[C:1]([O:5][C:6]([N:8]1[C:16]2[CH:15]=[C:14]([N+:17]([O-:19])=[O:18])[C:13]3[CH:20]=[CH:21][CH:22]=[CH:23][C:12]=3[C:11]=2[CH:10]([CH2:24][OH:25])[CH2:9]1)=[O:7])([CH3:4])([CH3:3])[CH3:2]

참가 물질

5

반응물 2

HCID 14487Diisobutylaluminum hydrideHCID 105713133-(tert-butyloxycarbonyl)-1-methoxycarbonyl-5-nitro-1,2-dihydro-3H-benz[e]indole

생성물 1

HCID 107124643-(tert-butyloxycarbonyl)-1-hydroxymethyl-5-nitro,1,2-dihydro-3H-benz[e]indole수율 61.1%

시약·촉매·용매 2

HCID 1140Toluene용매HCID 8028Tetrahydrofuran용매2회

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온도
0 °C

실험 절차

The crude ester 11 (0.85 g, 2.28 mmol) from the preceding procedure was dissolved in THF (25 mL) and added dropwise over 20 min to a stirred solution of DIBAL (9.1 mL of a 1M solution in toluene, 9.1 mmol) in THF (30 mL) under N2 at 0° C. The mixture was stirred for a further 30 min at 0° C., then poured into ice-cold 2 N HCl (40 mL) and extracted twice with EtOAc. The combined extracts were dried (Na2SO4) and concentrated under reduced pressure below 30° C. and the residue was chromatographed on silica gel. Elution with CH2Cl2EtOAc (4:1) afforded a crude product which was crystallised from CH2Cl2 /iPr2O/petroleum ether to give 3-(tert-butyloxycarbonyl)-1-hydroxymethyl-5-nitro,1,2-dihydro-3H-benz[e]indole (12) (0.48 g, 61%). A sample recrystallised from iPr2O/petroleum ether had mp 176° C. 1H NMR (CDCl3) δ(br s, 1 H, H-9), 8.42 (br s, 1 H, H-7), 7.88 (d, J=7.9 Hz, 1 H, H-4), 7.62-7.51 (m, 2 H, H5,6), 4.30 (m, 1 H, H-2), 4.17 (dd, J=11.4, 9.5 Hz, 1 H, H-2), 4.04-3.93 (m, 2 H, H-3, CHHOH), 383-3.74 (m, 1 H, CHHOH), 1.61 (s, 9 H, C(CH3)3).

후처리

  1. extractionextracted twice with EtOAc
  2. dry with materialThe combined extracts were dried (Na2SO4)
  3. concentrationconcentrated under reduced pressure below 30° C.
  4. customthe residue was chromatographed on silica gel
  5. washElution with CH2Cl2EtOAc (4:1)
  6. customafforded a crude product which
  7. customwas crystallised from CH2Cl2 /iPr2O/petroleum ether

출처 및 근거

ORD 기록
ord-def6bc64745d4a6cae8a6164e7d98bd3
출처 데이터셋
uspto-grants-2000_10
특허 번호
US06130237

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