Bromine → 2-Bromo-1-[3,5-di(tert-butyl)-4-hydroxyphenyl]ethan-1-one

HRID 1441135Notes

Reaction equation

HRID 1441135 reaction equation
[C:1]([C:5]1[CH:6]=[C:7]([C:16](=[O:18])[CH3:17])[CH:8]=[C:9]([C:12]([CH3:15])([CH3:14])[CH3:13])[C:10]=1[OH:11])([CH3:4])([CH3:3])[CH3:2].[Br:19]Br>CCOCC.C(Cl)(Cl)Cl>[Br:19][CH2:17][C:16]([C:7]1[CH:6]=[C:5]([C:1]([CH3:4])([CH3:2])[CH3:3])[C:10]([OH:11])=[C:9]([C:12]([CH3:15])([CH3:14])[CH3:13])[CH:8]=1)=[O:18]

Participants

5

Reactant 2

HCID 24408BromineHCID 6162963',5'-Bis(tert-butyl)-4'-hydroxyacetophenone

Product 1

HCID 6161612-Bromo-1-[3,5-di(tert-butyl)-4-hydroxyphenyl]ethan-1-one

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 6212ChloroformSolvent2×

Procedure

A mixture of (3,5-Di-t-butyl-4-hydroxyphenyl)ethanone (EXAMPLE 58, 800 mg) in ether (15 ml) and chloroform (10 ml) is cooled to 0° and then treated in a dropwise manner with a mixture containing 0. 17 ml of bromine dissolved in 5 ml of chloroform. The reaction mixture is allowed to warm to 20°-25° and stirred for 1 hr. Standard work-up gives the crude product (1.21 g) which is chromatographed on 180 g of silica gel. The column is packed and eluted with chloroform. An initial fraction of 200 ml is collected, followed by 7 ml fractions. Based on their TLC homogeneity, fractions 36-65 are combined and concentrated. Recrystallization from hexane gives the title compound, mp 105°-106°; IR (mineral oil) 3590, 2955, 2925, 2871, 2856, 1685, 1594, 1581, 1466, 1459, 1451, 1438, 1426, 1366, 1328, 1302, 1282, 1242, 1194, 1153, 1139, 1121, 860 and 615 cm-1 ; NMR (CDCl3 ; TMS) 7.88, 5.85, 4.40 and 1.47δ; CMR (CDCl3 ; TMS) 190.6, 159.0, 135.9, 126.8, 125.6, 34.2, 30.6 and 29.9δ; MS (m/z) M+ found=327, other ions at m/z 326, 311,233, 219, 203, 189, 175, 115, 101, 87, 57 and 40.

Workup

  1. temperatureis cooled to 0°
  2. additiontreated in a dropwise manner with a mixture
  3. additioncontaining 0
  4. temperatureto warm to 20°-25°
  5. customStandard work-up gives the crude product (1.21 g) which
  6. customis chromatographed on 180 g of silica gel
  7. washeluted with chloroform
  8. customAn initial fraction of 200 ml is collected
  9. concentrationconcentrated
  10. customRecrystallization from hexane

Sources & evidence

ORD record
ord-d965d01617094c85bd517efec2542657
Source dataset
uspto-grants-1996_03
Patent number
US05502187

Reaction notes

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