Benzyl Alcohol → 6-Benzyloxy-5-nitro-pyrimidine-2,4-diamine

HRID 565267Notes

Reaction equation

HRID 565267 reaction equation
[NH2:1][C:2]1[N:7]=[C:6]([NH2:8])[C:5]([N+:9]([O-:11])=[O:10])=[C:4](Cl)[N:3]=1.[Na].[CH2:14]([OH:21])[C:15]1[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=1>>[NH2:1][C:2]1[N:7]=[C:6]([NH2:8])[C:5]([N+:9]([O-:11])=[O:10])=[C:4]([O:21][CH2:14][C:15]2[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=2)[N:3]=1

Participants

4

Reactant 3

HCID 244Benzyl AlcoholHCID 2504496-Chloro-5-nitropyrimidine-2,4-diamineHCID 5360545Sodium

Product 1

HCID 98600036-Benzyloxy-5-nitro-pyrimidine-2,4-diamine

Conditions

Temperature
160 °C

Procedure

2,4-Diamino-6-chloro-5-nitropyrimidine (O'Brien et. al., J. Med. Chem., 9, 573-575 (1966)) (1.0 g, 5.28 mmol) was added to a solution of sodium (0.14 g, 6.08 mmol) in benzyl alcohol (9 mL). The solution was heated in a 160° C. oil bath for 3.5 h and the solvent was evaporated under reduced pressure to provide a yellow solid. This solid was washed with water, and air dried. Crystallization from benzene/ether gave a pale yellow filamentous solid: yield, 0.69 g (50%); mp 194-195° C. (171° C.; Kosary et. al., Acta. Pharm. Hung. , 49, 241-247 (1989)); UV (pH 1) λmax 236 nm (sh) (e=1.452×104), 264 (0.522×104), 321 (1.294×104); (pH 6.9) 242 (sh) (0.965×104), 337 (1.493×104); (pH 13) 242 (sh) (0.952×104), 338 (1.479×104); 1H NMR δ 5.43 (s, 2H, ArCH2), 7.26 (br s, 2H, NH2, exchange with D2O), 7.33-7.51 (m, 5H, ArH), 7.93 (br s, 2H, NH2, exchange with D2O); MS (EI) calcd. m/z for C11H11N5O3 261.0861, found 261.0866; Anal. (C11H11N5O3).

Workup

  1. customthe solvent was evaporated under reduced pressure
  2. customto provide a yellow solid
  3. washThis solid was washed with water, and air
  4. customdried
  5. customCrystallization from benzene/ether
  6. customgave a pale yellow filamentous solid
  7. customyield
  8. custommp 194-195° C. (171° C.; Kosary et. al., Acta. Pharm. Hung. , 49, 241-247 (1989))

Sources & evidence

ORD record
ord-a39323156832495dab824b3b9dc426d6
Source dataset
uspto-grants-2001_01
Patent number
US06172070B2

Reaction notes

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