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

HRID 2287351Notes

Reaction equation

HRID 2287351 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.[CH2:13]([NH:15][CH2:16][CH2:17][CH2:18][CH3:19])[CH3:14]>C(O)C>[Cl:11][C:6]1[C:7]([N+:8]([O-:10])=[O:9])=[C:2]([N:15]([CH2:13][CH3:14])[CH2:16][CH2:17][CH2:18][CH3:19])[N:3]=[C:4]([CH3:12])[N:5]=1

Participants

4

Reactant 2

HCID 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 rising 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 triethylatine (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 separated, 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): δ3.45 (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. additiontreated with triethylatine (2.00 mL, 14.3 mmol)
  2. stirringto stir
  3. customwas partitioned between water and ethyl acetate (100 mL each)
  4. customThe organic phase was separated
  5. washwashed with satd
  6. dry with materialaq. brine (100 mL), dried over anhydrous sodium sulfate
  7. filtrationfiltered
  8. customevaporated
  9. customThe residue was separated by column chromatography (silica gel, dichloromethane)

Sources & evidence

ORD record
ord-db1de48536bc413ca21f7bfb75625edd
Source dataset
uspto-grants-2000_07
Patent number
US06083948

Reaction notes

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