Benzyl Alcohol → 2-Amino-4-benzyloxy-5-nitropyrimidine

HRID 2270991Notes

Reaction equation

HRID 2270991 reaction equation
[NH2:1][C:2]1[N:7]=[C:6](Cl)[C:5]([N+:9]([O-:11])=[O:10])=[CH:4][N:3]=1.[Na].[CH2:13]([OH:20])[C:14]1[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1>>[NH2:1][C:2]1[N:7]=[C:6]([O:20][CH2:13][C:14]2[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=2)[C:5]([N+:9]([O-:11])=[O:10])=[CH:4][N:3]=1

Participants

4

Reactant 3

HCID 244Benzyl AlcoholHCID 3199954-chloro-5-nitropyrimidin-2-amineHCID 5360545Sodium

Product 1

HCID 102639222-Amino-4-benzyloxy-5-nitropyrimidine

Conditions

Temperature
130 °C

Procedure

2-Amino-4-chloro-5-nitropyrimidine (0.70 g, 4.0 mmol) was added to a solution of sodium (0.12 g, 5.2 mmol) in benzyl alcohol (8 mL) under argon. The solution was heated in a 130° C. oil bath for 3 h, and approximately half of the benzyl alcohol was evaporated under reduced pressure. The residue was poured into water (50 mL) with constant stirring for 10 min. After neutralization with glacial acetic acid, a brown precipitate formed which was collected by filtration and washed with water. This solid was crystallized from benzene to give 5a as a golden crystalline solid: yield, 126 mg (13%); mp 164-167° C.; UV (pH 1) 1max 262 nm (e=0.879×104), 295 (sh) (0.571×104); (pH 6.9) 235 (sh) (0.448×104), 273 (0.360×104), 326 (1.085×104); (pH 13) 273 (0.404×104), 327 (1.055×104); 1H NMR d 5.51 (s, 2 H, ArCH2), 7.35-7.54 (m, 5 H, ArH), 8.05 (d, 2 H, NH2, exchange with D2O), 8.92 (s, 1 H, H-6) MS (EI) calcd. m/z for C11H10N4O3 246.0752, found 246.0758; Anal. (C11H10N4O3) C, H, N.

Workup

  1. customapproximately half of the benzyl alcohol was evaporated under reduced pressure
  2. additionThe residue was poured into water (50 mL)
  3. customAfter neutralization with glacial acetic acid, a brown precipitate formed which
  4. filtrationwas collected by filtration
  5. washwashed with water
  6. customThis solid was crystallized from benzene

Sources & evidence

ORD record
ord-e932795bc70042398d6f6ba803e9815f
Source dataset
uspto-grants-2001_12
Patent number
US06333331B1

Reaction notes

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