Methylhydrazine → (2R,3R,4S,5R)-2-(6,7-dichloro-3-methyl-pyrazolo[3,4-b]indol-4-yl)-5-(hydroxymethyl)tetrahydrofuran-3,4-diol

HRID 28357

Reaktionsgleichung

Reaktionsgleichung von HRID 28357
Cl[C:2]1[N:3]([C@@H:15]2[O:21][C@H:20]([CH2:22][OH:23])[C@@H:18]([OH:19])[C@H:16]2[OH:17])[C:4]2[C:9]([C:10]=1[CH:11]=O)=[CH:8][C:7]([Cl:13])=[C:6]([Cl:14])[CH:5]=2.[CH3:24][NH:25][NH2:26].CO.O>CO>[Cl:13][C:7]1[CH:8]=[C:9]2[C:4](=[CH:5][C:6]=1[Cl:14])[N:3]([C@@H:15]1[O:21][C@H:20]([CH2:22][OH:23])[C@@H:18]([OH:19])[C@H:16]1[OH:17])[C:2]1[N:25]([CH3:24])[N:26]=[CH:11][C:10]2=1

Komponenten

5

Edukt 3

HCID 6061MethylhydrazineHCID 3011610FtcriHCID 22242641Methanol--water (1/1)

Produkt 1

HCID 3012226(2R,3R,4S,5R)-2-(6,7-dichloro-3-methyl-pyrazolo[3,4-b]indol-4-yl)-5-(hydroxymethyl)tetrahydrofuran-3,4-diolAusbeute 33 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 887MethanolLösungsmittel

Versuchsvorschrift

2,5,6-Trichloro-3-formyl-1-(β-D-ribofuranosyl)indole (4.3, 82 mg, 0.22 mmol) was dissolved in methanol (4 mL) to which was added methylhydrazine (0.5 mL). The solution was stirred at room temperature for 16 h, then the solvent was removed under vacuum. The residue was suspended in 20 mL of brine and extracted with EtOAc (2×20 mL). The combined organic extracts were dried over MgSO4, filtered and evaporated to yield a yellow oil. The oil was subjected to column chromatography (40×350 mm) on C18-reverse phase silica gel with 75% MeOH/water. Fractions containing product were pooled and evaporated to yield 29 mg (33%) of 4.36 as a pale yellow solid: mp 135-138° C.; Rf 0.6 (20% MeOH/CHCl3); 1H-NMR (500 MHz, DMSO-d6): δ 8.25 (s, 1H), 7.94 (s, 1H), 7.73 (s, 1H), 5.95 (d, 1H), 5.38 (d, 1H, D2O exch.), 5.25 (m, 2H, D2O exch.), 4.21 (q, 1H), 4.13 (m, 1H), 4.05 (s, 3H), 3.97 (m, 1H), 3.74 (m, 2H). 13C-NMR (125 MHz, DMSO-d6): δ 146.23, 139.94, 128.98, 123.94, 122.80, 120.16, 119.24, 115.28, 109.15, 88.91, 85.71, 71.94, 68.75, 60.89, 37.81. HRMS (ES) m/z calcd. for C15H15Cl2N3O4·Na·MeOH 426.0599, found 426.0593. Anal calcd for C15H15Cl2N3O4: C, 48.40; H, 4.06; N, 11.29. Found: C, 48.13; H, 4.16; N, 11.12.

Aufarbeitung

  1. customthe solvent was removed under vacuum
  2. extractionextracted with EtOAc (2×20 mL)
  3. dry with materialThe combined organic extracts were dried over MgSO4
  4. filtrationfiltered
  5. customevaporated
  6. customto yield a yellow oil
  7. additionFractions containing product
  8. customevaporated

Quellen und Nachweise

ORD-Eintrag
ord-543229d5e34a4a068f53bbfe3b25a6eb
Quelldatensatz
uspto-grants-2008_09
Patentnummer
US07419963B2

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