Sulfuric Acid → 2-(1-Adamantyl)-4-bromophenol

HRID 860542Notes

Reaction equation

HRID 860542 reaction equation
[Br:1][C:2]1[CH:7]=[CH:6][C:5]([OH:8])=[CH:4][CH:3]=1.[C:9]12(O)[CH2:18][CH:13]3[CH2:14][CH:15]([CH2:17][CH:11]([CH2:12]3)[CH2:10]1)[CH2:16]2.OS(O)(=O)=O.C([O-])(O)=O.[Na+]>C(Cl)Cl>[C:9]12([C:6]3[CH:7]=[C:2]([Br:1])[CH:3]=[CH:4][C:5]=3[OH:8])[CH2:18][CH:13]3[CH2:14][CH:15]([CH2:17][CH:11]([CH2:12]3)[CH2:10]1)[CH2:16]2

Participants

6

Reactant 4

HCID 1118Sulfuric AcidHCID 78084-BromophenolHCID 641521-AdamantanolHCID 516892Sodium Bicarbonate

Product 1

HCID 46704942-(1-Adamantyl)-4-bromophenolYield 74%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

To a mixture of 4-bromophenol (34.60 g, 200 mmol) and 1-adamantanol (30.45 g, 200 mmol) in 100 mL of anhydrous CH2Cl2 at room temperature was added dropwise over 10–15 minutes concentrated H2SO4 (11 mL). After 1.5 hours a thick suspension resulted and the reaction was allowed to continue for a total of 24 hours. The suspension was carefully poured into ice water and neutralized with solid NaHCO3. The resulting layers were separated and the aqueous layer extracted with CH2Cl2 (2×). The combined organics were washed with brine, dried (MgSO4) and filtered. The solvent was removed under reduced pressure and the resulting solid was purified on silica gel (hexane:ethyl acetate 85:15), the impure fractions were further purified by recrystallization from hexane and the two lots combined to give 45.2 g (74%) of 2-(1-adamantyl)-4-bromophenol. 1H NMR (300 MHz; CDCl3): δ 1.77 (s, 6H), 2.08 (s, 9H), 4.81 (s, 1H), 6.53 (d, J=8.4 Hz, 1H), 7.14 (dd, J1=8.7 Hz, J2=2.4 Hz, 1H), 7.29 (d, J=2.4 Hz, 1H).

Workup

  1. customAfter 1.5 hours a thick suspension resulted
  2. customto continue for a total of 24 hours
  3. customThe resulting layers were separated
  4. extractionthe aqueous layer extracted with CH2Cl2 (2×)
  5. washThe combined organics were washed with brine
  6. dry with materialdried (MgSO4)
  7. filtrationfiltered
  8. customThe solvent was removed under reduced pressure
  9. customthe resulting solid was purified on silica gel (hexane:ethyl acetate 85:15)
  10. customthe impure fractions were further purified by recrystallization from hexane

Sources & evidence

ORD record
ord-5a4622f891a548c98eb10df6253c73b0
Source dataset
uspto-grants-2006_12
Patent number
US07153875B2

Reaction notes

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