Benzyl Alcohol → 2-Amino-4-benzyloxy-5-nitropyrimidine
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]=1Participants
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) λmax 262 nm (ε=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 δ 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 C11H10 N4O3 246.0752, found 246.0758; Anal. (C11H10N4O3) C, H, N.
Workup
- customapproximately half of the benzyl alcohol was evaporated under reduced pressure
- additionThe residue was poured into water (50 mL)
- customAfter neutralization with glacial acetic acid, a brown precipitate formed which
- filtrationwas collected by filtration
- washwashed with water
- customThis solid was crystallized from benzene
Sources & evidence
- ORD record
- ord-380d49c5623e4ea186235c1188191c26
- Source dataset
- uspto-grants-2001_10
- Patent number
- US06303604B1
Reaction notes
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