Benzoyl Peroxide → HCID 59383483, compound

HRID 2188630Notes

Reaction equation

HRID 2188630 reaction equation
[Cl:1][C:2]1[N:7]=[CH:6][C:5]([CH2:8][CH3:9])=[CH:4][N:3]=1.[Br:10]N1C(=O)CCC1=O.C(OOC(=O)C1C=CC=CC=1)(=O)C1C=CC=CC=1>C(Cl)(Cl)(Cl)Cl>[Br:10][CH:8]([C:5]1[CH:4]=[N:3][C:2]([Cl:1])=[N:7][CH:6]=1)[CH3:9]

Participants

5

Reactant 3

HCID 7187Benzoyl PeroxideHCID 67184N-bromobutanimideHCID 35727632-Chloro-5-ethylpyrimidine

Product 1

HCID 59383483HCID 59383483, compoundYield 36%

Reagents, catalysts & solvents 1

HCID 5943Carbon TetrachlorideSolvent

Procedure

A solution of 2-chloro-5-ethylpyrimidine (1.15 g, 8.1 mmol) in 20 mL of carbon tetrachloride was treated with N-bromosuccinimide (1.50 g, 8.4 mmol) and a catalytic amount (about 1 mol percent based on reactants) of benzoyl peroxide and then heated to 75° C. After several hours and additional catalyst, the starting material was completely consumed. The solids were removed and the filtrate was concentrated. The resulting residue was further purified by flash column chromatography on silica gel using a mixture of ethyl acetate (EtOAc) and petroleum ether as the eluant. The solvents were removed under reduced pressure to yield 0.64 g (36%) of 5-(1-bromoethyl)-2-chloropyrimidine (A) as a clear liquid: 1H NMR (CDCl3) δ 8.70 (s, 2H), 5.15 (q, J=8.0 Hz, 1H), 2.10 (d, J=8.0 Hz, 3H); GCMS (FID) m/z 222 (M+). Some of the corresponding dibromo compound 0.44 g (18%) was also isolated, as a white solid: mp 84-85° C.; 1H NMR (CDCl3) d 9.00 (s, 2H), 3.00 (s, 3H); LC-MS (ESIMS) m/z 298 (M+H).

Workup

  1. waitAfter several hours
  2. customadditional catalyst, the starting material was completely consumed
  3. customThe solids were removed
  4. concentrationthe filtrate was concentrated
  5. customThe resulting residue was further purified by flash column chromatography on silica gel using
  6. additiona mixture of ethyl acetate (EtOAc) and petroleum ether as the eluant
  7. customThe solvents were removed under reduced pressure

Sources & evidence

ORD record
ord-c43630a93f8d40e589374405d9fd601e
Source dataset
uspto-grants-2012_12
Patent number
US08324209B2

Reaction notes

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