N-bromobutanimide → 4-(Bromomethyl)-2-methoxybenzonitrile

HRID 8920Notes

Reaction equation

HRID 8920 reaction equation
[CH3:1][O:2][C:3]1[CH:10]=[C:9]([CH3:11])[CH:8]=[CH:7][C:4]=1[C:5]#[N:6].[Br:12]N1C(=O)CCC1=O>C(Cl)(Cl)(Cl)Cl.C(OCC)C.C(OOC(=O)C1C=CC=CC=1)(=O)C1C=CC=CC=1>[Br:12][CH2:11][C:9]1[CH:8]=[CH:7][C:4]([C:5]#[N:6])=[C:3]([O:2][CH3:1])[CH:10]=1

Participants

6

Reactant 2

HCID 67184N-bromobutanimideHCID 124953732-Methoxy-4-methylbenzonitrile

Product 1

HCID 219850074-(Bromomethyl)-2-methoxybenzonitrileYield 68.3%

Reagents, catalysts & solvents 3

HCID 7187Benzoyl PeroxideCatalystHCID 3283Diethyl EtherSolventHCID 5943Carbon TetrachlorideSolvent

Procedure

To a solution of 2-methoxy-4-methylbenzonitrile (0.438 g, 2.98 mmol) in CCl4 (6 mL) was added recrystallized N-bromosuccinimide (0.544 g, 3.05 mmol) followed by benzoyl peroxide (47 mg, 0.19 mmol). The resultant mixture was heated to reflux for 45 minutes then cooled to room temperature. The mixture was diluted with diethyl ether (30 mL), filtered through filter paper, and the filtrate was concentrated. Purification of the crude material by column chromatography (6:1 hexanes-EtOAc) provided 0.46 g (68%) of 4-(bromomethyl)-2-methoxybenzonitrile as a white solid. 1H NMR (CDCl3) δ 3.96 (s, 3H), 4.45 (s, 2H), 6.99 (s, 1H), 7.03 (d, 1H, J=9 Hz), 7.53 (d, 1H, J=9 Hz).

Workup

  1. temperatureto reflux for 45 minutes
  2. filtrationfiltered
  3. filtrationthrough filter paper
  4. concentrationthe filtrate was concentrated
  5. customPurification of the crude material by column chromatography (6:1 hexanes-EtOAc)

Sources & evidence

ORD record
ord-99fb53d680b64d348c12f770dc6887ea
Source dataset
uspto-grants-2006_08
Patent number
US07091217B2

Reaction notes

Loading…