Azobisisobutyronitrile → (3-Bromo-4-(bromomethyl)phenyl)(4-ethoxyphenyl)methanone

HRID 1716947Notes

Reaction equation

HRID 1716947 reaction equation
[Br:1][C:2]1[CH:3]=[C:4]([C:9]([C:11]2[CH:16]=[CH:15][C:14]([O:17][CH2:18][CH3:19])=[CH:13][CH:12]=2)=[O:10])[CH:5]=[CH:6][C:7]=1[CH3:8].C1C(=O)N([Br:27])C(=O)C1.N(C(C)(C)C#N)=NC(C)(C)C#N>C(Cl)(Cl)(Cl)Cl>[Br:1][C:2]1[CH:3]=[C:4]([C:9]([C:11]2[CH:12]=[CH:13][C:14]([O:17][CH2:18][CH3:19])=[CH:15][CH:16]=2)=[O:10])[CH:5]=[CH:6][C:7]=1[CH2:8][Br:27]

Participants

5

Reactant 3

HCID 6547Azobisisobutyronitrile2×HCID 67184N-bromobutanimide2×HCID 59013436(3-Bromo-4-methylphenyl)(4-ethoxyphenyl)methanone

Product 1

HCID 59013439(3-Bromo-4-(bromomethyl)phenyl)(4-ethoxyphenyl)methanoneYield 50.1%

Reagents, catalysts & solvents 1

HCID 5943Carbon TetrachlorideSolvent

Conditions

Temperature
100 °C

Procedure

To a stirred solution of (3-bromo-4-methylphenyl)(4-ethoxyphenyl)methanone (0.864 g, 2.71 mmol) in CCl4 (3.5 mL) were added N-bromosuccimide (0.506 g, 2.84 mmol) and 2,2′-azobis(isobutyronitrile) (20 mg, 0.14 mmol). After being vigorously stirred under reflux at an external temperature of 100° C. for 110 min, additional N-bromosuccimide (0.1 g, 0.56 mmol) and 2,2′-azobis(isobutyronitrile) (20 mg, 0.14 mmol) were added. The mixture was stirred for another 30 min, then cooled with ice-water. The resulting precipitates were collected by filtration and washed with ethyl acetate. The filtrate was washed 3× with 5% citric acid, and dried over Na2SO4. Concentration under reduced pressure gave the crude product which was recrystallized from ethyl acetate to yield 0.54 g of the title compound. 1H NMR (CDCl3, 300 MHz: δ 7.96 (s, 1H), 7.80 (d, J=8.8 Hz, 2H), 7.66 (d, J=8.0 Hz, 1H), 7.56 (d, J=8.0 Hz, 1H), 6.96 (d, J=8.4 Hz, 2H), 4.64 (s, 2H), 4.13 (q, J=6.8 Hz, 2H), 1.46 (t, J=6.8 Hz, 3H); MS ESI (m/z) 397 (M+1)+, calc. 396.

Workup

  1. stirringThe mixture was stirred for another 30 min
  2. customThe resulting precipitates
  3. filtrationwere collected by filtration
  4. washwashed with ethyl acetate
  5. washThe filtrate was washed 3× with 5% citric acid
  6. dry with materialdried over Na2SO4
  7. concentrationConcentration under reduced pressure
  8. customgave the crude product which
  9. customwas recrystallized from ethyl acetate

Sources & evidence

ORD record
ord-f98ae9607e504a058905a40020c46e70
Source dataset
uspto-grants-2010_09
Patent number
US07803778B2

Reaction notes

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