Reaktion #93937

ord-678d938fe117450c94947b855d5556e4

Reaktionsgleichung

CNC(=O)NC[C@H]1O[C@@H](n2cc(C)c(=O)[nH]c2=O)C[C@@H]1O
4
CNC(=O)NC[C@H]1O[C@@H](n2cc(C)c(=O)[nH]c2=O)C[C@@H]1O
5'-(3-Methylureido)-5'-deoxythymidine
O=N[O-].[Na+]
sodium nitrite
→
Cc1cn([C@H]2C[C@H](O)[C@@H](CNC(=O)N(C)N=O)O2)c(=O)[nH]c1=O
white fine needles
Ausbeute 70.2%
Cc1cn([C@H]2C[C@H](O)[C@@H](CNC(=O)N(C)N=O)O2)c(=O)[nH]c1=O
5'-(3-Methyl-3-nitrosoureido)-5'-deoxythymidine
Ausbeute 70.2%

Edukte

CNC(=O)NC[C@H]1O[C@@H](n2cc(C)c(=O)[nH]c2=O)C[C@@H]1O
4
CNC(=O)NC[C@H]1O[C@@H](n2cc(C)c(=O)[nH]c2=O)C[C@@H]1O
5'-(3-Methylureido)-5'-deoxythymidine
O=N[O-].[Na+]
sodium nitrite

Reagenzien

Keine

Lösungsmittel

CC(=O)O
acetic acid

Reaktionsbedingungen

Detaillierte Bedingungen
See reaction.notes.procedure_details.

Aufarbeitung

  1. 1
    Sonstigewas kept at 0°
  2. 2
    Sonstigeto precipitate out
  3. 3
    FiltrationThe product was collected by filtration
  4. 4
    Waschenwashed with water
  5. 5
    Temperaturcooled methanol, ether
  6. 6
    Sonstigedried
  7. 7
    EinengenThe filtrate was concentrated
  8. 8
    Sonstigean additional fraction of crystals was obtained
  9. 9
    SonstigeThe combined product was recrystallized from methanol

Vorschrift

To a solution of 4 (1.00 g, 3.35 mmol) in 50% aqueous acetic acid at 0°, sodium nitrite (0.31 g, 4.55 mmol) was added slowly. The reaction mixture was kept at 0° with stirring for 3 h, during which time crystals started to precipitate out. The product was collected by filtration, washed with water, cooled methanol, ether, and dried. The filtrate was concentrated and an additional fraction of crystals was obtained. The combined product was recrystallized from methanol to yield 0.77 g (70%) of white fine needles: mp 159°-160° dec.: uvλmaxEtOH 264 nm (ε11,000); uvλminEtOH 235 nm. Anal. (C12H17N5O6) C, H, N.

Quelle

DOI: 10.6084/m9.figshare.5104873.v1Patent: US04128639uspto-grants-1978_12