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

HRID 619221Notes

Reaction equation

HRID 619221 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) lmax 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-6d14562e12b6474989bfe471b4b273eb
Source dataset
uspto-grants-1999_09
Patent number
US05958932

Reaction notes

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