Acetic Acid → 2-Amino-4-benzyloxy-6-methyl-5-nitropyrimidine

HRID 260052Notes

Reaction equation

[NH2:1][C:2]1[N:7]=[C:6](Cl)[C:5]([N+:9]([O-:11])=[O:10])=[C:4]([CH3:12])[N:3]=1.[Na].O.C(O)(=O)C.[CH2:19]([OH:26])[C:20]1[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=1>>[NH2:1][C:2]1[N:7]=[C:6]([O:26][CH2:19][C:20]2[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=2)[C:5]([N+:9]([O-:11])=[O:10])=[C:4]([CH3:12])[N:3]=1

Participants

Reactant 5

HCID 176Acetic Acid

HCID 244Benzyl Alcohol

HCID 962Water

HCID 2521884-chloro-6-methyl-5-nitropyrimidin-2-amine

HCID 5360545Sodium

Product 1

HCID 102443402-Amino-4-benzyloxy-6-methyl-5-nitropyrimidine

Conditions

Temperature: 135 °C

Procedure

2-Amino-4-chloro-6-methyl-5-nitropyrimidine (Boon et al., J. Chem. Soc., 96-102 (1951)) (1.24 g, 6.58 mmol) was added to a solution of sodium (0.21 g, 9.13 mmol) in benzyl alcohol (14 mL) under argon. The solution was heated in a 135° C. oil bath for 3.5 h, and was poured into water (70 mL) with constant stirring for 10 min. After neutralization with glacial acetic acid, a yellow precipitate formed which was collected by filtration and washed with water. This solid was crystallized from benzene to give 5b as a bright yellow crystalline solid: yield, 0.57 g (33%); mp 159°-160° C.; UV (pH 1) λmax 268 nm (ε=0.783×104), 345 (sh) (0.104×104); (pH 6.9) 282 (0.564×104), 345 (sh) (0.338×104); (pH 13) 282 (0.549×104), 345 (sh) (0.332×104); 1H NMR δ2.35 (s, 3H, CH3), 5.44 (s, 2H, ARCH2), 7.34-7.46 (m, 5H, ArH), 7.64 (b s, 2H, NH2, exchange with D2O); MS (EI) calcd. m/z for C12H12N4O3 260.0908, found 260.0913; Anal. (C12H12N4O3) C, H, N.

Workup

filtrationwas collected by filtration
washwashed with water
customThis solid was crystallized from benzene

Sources & evidence

ORD record: ord-f2220df515334be0bc19d4a97947d668
Source dataset: uspto-grants-1996_06
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US05525606

Reaction notes

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