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

HRID 860578Notes

Reaction equation

HRID 860578 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 81,786.5%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

A 2.0 L three-neck flask attached with a power-stirrer was charged with 4-bromophenol (340.8 g, 1.97 mmol) and 1-adamantanol (300.0 g, 1.97 mmol) in 1.0 L of anhydrous CH2Cl2 at room temperature. Stirring was initiated and once all the reagents were solubilized then concentrated H2SO4 (105 mL, 193.2 g, 1.97 mmol, 1.0 eq) was added dropwise over 15–30 minutes. After approximately 1.0 hour a 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 suspended in a minimal amount of hexanes. After stirring at room temperature for an hour the solid was collected via filtration and dried under reduced pressure to give 495.0 g (77%) of 2-adamantan-1-yl-4-bromophenol as a white solid. 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. customA 2.0 L three-neck flask attached with a power-stirrer
  2. customAfter approximately 1.0 hour a suspension resulted
  3. customto continue for a total of 24 hours
  4. customThe resulting layers were separated
  5. extractionthe aqueous layer extracted with CH2Cl2 (2×)
  6. washThe combined organics were washed with brine
  7. dry with materialdried (MgSO4)
  8. filtrationfiltered
  9. customThe solvent was removed under reduced pressure
  10. stirringAfter stirring at room temperature for an hour the solid
  11. filtrationwas collected via filtration
  12. customdried under reduced pressure

Sources & evidence

ORD record
ord-a71e556c4d7a4f6094a14139269a30a8
Source dataset
uspto-grants-2006_12
Patent number
US07153875B2

Reaction notes

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