Réaction #93937

ord-678d938fe117450c94947b855d5556e4

Équation de réaction

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
Rendement 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
Rendement 70.2%

Réactifs

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

Réactifs

Aucun

Solvants

CC(=O)O
acetic acid

Conditions de réaction

Conditions détaillées
See reaction.notes.procedure_details.

Traitement

  1. 1
    Autrewas kept at 0°
  2. 2
    Autreto precipitate out
  3. 3
    FiltrationThe product was collected by filtration
  4. 4
    Lavagewashed with water
  5. 5
    Températurecooled methanol, ether
  6. 6
    Autredried
  7. 7
    ConcentrationThe filtrate was concentrated
  8. 8
    Autrean additional fraction of crystals was obtained
  9. 9
    AutreThe combined product was recrystallized from methanol

Mode opératoire

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.

Source

DOI: 10.6084/m9.figshare.5104873.v1Brevet: US04128639uspto-grants-1978_12