Reaction #93937

ord-678d938fe117450c94947b855d5556e4

Reaction equation

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
Yield 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
Yield 70.2%

Reactants

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

Reagents

None

Solvents

CC(=O)O
acetic acid

Conditions

Detailed conditions
See reaction.notes.procedure_details.

Workup

  1. 1
    Otherwas kept at 0°
  2. 2
    Otherto precipitate out
  3. 3
    FiltrationThe product was collected by filtration
  4. 4
    Washwashed with water
  5. 5
    Temperaturecooled methanol, ether
  6. 6
    Otherdried
  7. 7
    ConcentrationThe filtrate was concentrated
  8. 8
    Otheran additional fraction of crystals was obtained
  9. 9
    OtherThe combined product was recrystallized from methanol

Procedure

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.v1Patent: US04128639uspto-grants-1978_12