Benzyl Alcohol → 6-(Benzyloxy)-5-bromopyrimidine-2,4-diamine

HRID 2270989Notes

Reaction equation

HRID 2270989 reaction equation
[NH2:1][C:2]1[N:7]=[C:6]([NH2:8])[C:5]([Br:9])=[C:4](Cl)[N:3]=1.[Na].[CH2:12]([OH:19])[C:13]1[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1>>[NH2:1][C:2]1[N:7]=[C:6]([NH2:8])[C:5]([Br:9])=[C:4]([O:19][CH2:12][C:13]2[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=2)[N:3]=1

Participants

4

Reactant 3

HCID 244Benzyl AlcoholHCID 2517365-bromo-6-chloropyrimidine-2,4-diamineHCID 5360545Sodium

Product 1

HCID 144796176-(Benzyloxy)-5-bromopyrimidine-2,4-diamine

Conditions

Temperature
130 °C

Procedure

2,4-Diamino-5-bromo-6-chloropyrimidine (Phillips et. al., J. Org. Chem., 29, 1488-1490 (1963)) (2.3 g, 10 mmol) was added to a solution of sodium (0.29 g, 12.5 mmol) in benzyl alcohol (10 mL) under argon. The solution was heated in a 130° C. oil bath for 3 h and the benzyl alcohol was evaporated under reduced pressure to give a white solid. This solid was washed with water, and air dried. Crystallization from 50% aqueous ethanol gave white crystalline needles of 3f: yield, 2.32 g (76%); mp 165-166° C. (lit. 136° C.; Kosary et. al., Acta Pharm. Hung., 49, 241-247 (1989)); UV (pH 1) 1max 236 nm (e=0.873×104), 291 (1.388×104); (pH 6.9) 236 (0.850×104), 277 (0.835×104); (pH 13) 234 (0.869×104), 277 (0. 827×104); 1H NMR d 5.30 (s, 2 H, ArCH2), 6.15 (s, 2 H, NH2, exchange with D2O), 6.32 (s, 2 H, NH2, exchange with D2O), 7.31-7.45 (m, 5 H, ArH); MS (EI) calcd. m/z for C11H11N4O79Br 294.0115, found 294.0127; calcd. m/z for C11H11N4O81Br 296.0094, found 296.0083; Anal. (C11H11N4OBr) C, H, N.

Workup

  1. customthe benzyl alcohol was evaporated under reduced pressure
  2. customto give a white solid
  3. washThis solid was washed with water, and air
  4. customdried
  5. customCrystallization from 50% aqueous ethanol

Sources & evidence

ORD record
ord-3f43dd3f3af143bfac1396f0c9605dad
Source dataset
uspto-grants-2001_12
Patent number
US06333331B1

Reaction notes

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