Triethylamine → 4-Chloro-6-(ethylbutylamino)-2-methyl-5-nitropyrimidine

HRID 2184765Notes

Reaction equation

HRID 2184765 reaction equation
Cl[C:2]1[C:7]([N+:8]([O-:10])=[O:9])=[C:6]([Cl:11])[N:5]=[C:4]([CH3:12])[N:3]=1.C(N(CC)CC)C.[CH2:20]([NH:22][CH2:23][CH2:24][CH2:25][CH3:26])[CH3:21]>C(O)C>[Cl:11][C:6]1[C:7]([N+:8]([O-:10])=[O:9])=[C:2]([N:22]([CH2:20][CH3:21])[CH2:23][CH2:24][CH2:25][CH3:26])[N:3]=[C:4]([CH3:12])[N:5]=1

Participants

5

Reactant 3

HCID 8471TriethylamineHCID 25914ButylethylamineHCID 831924,6-Dichloro-2-methyl-5-nitropyrimidine

Product 1

HCID 105401554-Chloro-6-(ethylbutylamino)-2-methyl-5-nitropyrimidineYield 92%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent2×

Procedure

Part A. A solution of 4,6-dichloro-2-methyl-5-nitropyrimidine (prepared using the methods of Albert, et al., J. Chem. Soc. 1954, p. 3832) (2.77 g, 13.3 mmol) in absolute ethanol (25 mL) was cooled to 0° C., and treated with triethylamine (2.00 mL, 14.3 mmol). Then, a solution of ethylbutylamine (1.80 mL, 13.2 mmol) in ethanol (3 mL) was added dropwise with stirring. The mixture was allowed to stir and warm to ambient temperature overnight, then was partitioned between water and ethyl acetate (100 mL each). The organic phase was seperated, washed with satd. aq. brine (100 mL), dried over anhydrous sodium sulfate, filtered and evaporated. The residue was separated by column chromatography (silica gel, dichloromethane) to afford 4-chloro-6-(ethylbutylamino)-2-methyl-5-nitropyrimidine as an oil (3.34 g, 12.2 mmol, 92%). Spectral data: TLC RF 0. 59 (dichloromethane). 1H NMR (300 MHz, CDCl3): δ 3.45 (2H, q, J=7.0 Hz), 3.38 (2H, t, J=7.7 Hz), 2.50 (3H, s), 1.62-1.52 (2H, m), 1.38-1.26 (2H, m), 1.20 (3H, t, J=7.0 Hz), 0.94 (3H, t, J=7.3 Hz). MS (NH3—CI): m/e 276 (4), 275 (40), 274 (16), 273 (100).

Workup

  1. stirringto stir
  2. customwas partitioned between water and ethyl acetate (100 mL each)
  3. customThe organic phase was seperated
  4. washwashed with satd
  5. dry with materialaq. brine (100 mL), dried over anhydrous sodium sulfate
  6. filtrationfiltered
  7. customevaporated
  8. customThe residue was separated by column chromatography (silica gel, dichloromethane)

Sources & evidence

ORD record
ord-43f9f51ec74440df85cfdd3215c44b57
Source dataset
uspto-grants-2002_06
Patent number
US06399609B1

Reaction notes

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