Triethylamine → 4-Ethylthio-3-(3-methanesulfonyloxy-1-propyl)-5-(4-methyl-1,2-dioxocyclobut-3-en-3-yl)amino indole

HRID 441102Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 441102
[CH2:1]([S:3][C:4]1[C:12]([NH:13][C:14]2[C:15](=[O:20])[C:16](=[O:19])[C:17]=2[CH3:18])=[CH:11][CH:10]=[C:9]2[C:5]=1[C:6]([CH2:21][CH2:22][CH2:23][OH:24])=[CH:7][NH:8]2)[CH3:2].CCN(CC)CC.[CH3:32][S:33](Cl)(=[O:35])=[O:34]>C1COCC1.C(Cl)Cl.C(Cl)Cl>[CH2:1]([S:3][C:4]1[C:12]([NH:13][C:14]2[C:15](=[O:20])[C:16](=[O:19])[C:17]=2[CH3:18])=[CH:11][CH:10]=[C:9]2[C:5]=1[C:6]([CH2:21][CH2:22][CH2:23][O:24][S:33]([CH3:32])(=[O:35])=[O:34])=[CH:7][NH:8]2)[CH3:2]

Komponenten

6

Edukt 3

HCID 8471TriethylamineHCID 31297Methanesulfonyl chlorideHCID 224057163-(4-Ethylthio-5-(4-methyl-1,2-dioxocyclobut-3-en-3-yl)amino-3-indolyl)1-propanol

Produkt 1

HCID 224056664-Ethylthio-3-(3-methanesulfonyloxy-1-propyl)-5-(4-methyl-1,2-dioxocyclobut-3-en-3-yl)amino indole

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 6344DichloromethaneLösungsmittelHCID 21919333Tetrahydrofurane dichloromethaneLösungsmittel

Reaktionsbedingungen

Temperatur
23 °C

Versuchsvorschrift

A cold (5° C.) mixture of 3-(4-ethylthio-5-(4-methyl-1,2-dioxocyclobut-3-en-3-yl) amino-3-indolyl)1-propanol (0.708 g, 2.1 mmol) and Et3N (0.697 ml, 5.0 mmol) in THF:CH2Cl2 (1:2, 45 ml) mixture kept under argon atm. was treated dropwise with MsCl (0.387 ml, 5.0 mmol) and stirred at 23° C. for 1.5 h. The reaction mixture was diluted with CH2Cl2 (40ml) and washed with H2O (10ml) and saturated NaHCO3 solution. The organic phase was dried (MgSO4) and concentrated in vacuo. The crude material was purified on silica gel dry column using a mixture of CH2Cl2 :EtOAc (7.3) as eluting solvent. Appropriate fractions were concentrated in vacuo giving a yellow oil, 0.70 g, 79%. 1H NMR (DMSO-d6) δ (ppm): 11.26, 11.20, 10.81 and 10.53 (4 br s, 2H, indolic NH and 5-NH), 7.42 (br s, 1H), 7.32 (s, 1H), 7.09 (d, J=8.2 Hz, 1H), 4.27 (t, J=6.4 Hz, 2H, CH2OSO2), 3.17 (s, 3H, CH3SO2), 3.11 (t, J=7 Hz, 2H, CH2CH2CH2O), 2.67 (br s, 2H, CH3CH2S), 2.28 (br, s, 1H, CH3 of dioxocyclobutene), 2.0-2.15 (m, 2H, CH2CH2CH2O), 1.59 (br s, 2H CH3 of dioxocyclobutene), 0.9-1.1 (m, 3H, CH3CH2S). IR (film) n:3710, 3180, 1783, 1728, 1590, 1340 and 1170 cm-1.

Aufarbeitung

  1. washwashed with H2O (10ml) and saturated NaHCO3 solution
  2. dry with materialThe organic phase was dried (MgSO4)
  3. concentrationconcentrated in vacuo
  4. customThe crude material was purified on silica gel
  5. customdry column
  6. additiona mixture of CH2Cl2
  7. washEtOAc (7.3) as eluting solvent
  8. concentrationAppropriate fractions were concentrated in vacuo
  9. customgiving a yellow oil, 0.70 g, 79%

Quellen und Nachweise

ORD-Eintrag
ord-d52bd4e513cb4a59a20f3a78ffee7fff
Quelldatensatz
uspto-grants-1996_05
Patentnummer
US05521188

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