4-Bromophenol → 2-(4-Bromophenoxy)tetrahydro-2H-pyran

HRID 1940229Notes

Reaction equation

HRID 1940229 reaction equation
[Br:1][C:2]1[CH:7]=[CH:6][C:5]([O:8][CH:9]2[CH2:14][CH2:13][CH2:12][CH2:11][O:10]2)=[C:4](C(C)(C)C)[CH:3]=1.BrC1C=CC(O)=CC=1.C1(C)C=CC(S([O-])(=O)=O)=CC=1.[NH+]1C=CC=CC=1.O1C=CCCC1>ClCCl>[Br:1][C:2]1[CH:7]=[CH:6][C:5]([O:8][CH:9]2[CH2:14][CH2:13][CH2:12][CH2:11][O:10]2)=[CH:4][CH:3]=1

Participants

6

Reactant 4

HCID 78084-Bromophenol2×HCID 80803,4-dihydro-2H-pyranHCID 466102Benzenesulfonic acid, 4-methyl-, compd. with pyridine (1:1)HCID 158188564-Bromo-2-t-butyl-1-(2-tetrahydropyranoxy)benzene2×

Product 1

HCID 46464362-(4-Bromophenoxy)tetrahydro-2H-pyran

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

Using the same general procedure as for the preparation of 4-bromo-2-t-butyl-1-(2-tetrahydropyranoxy)benzene (Compound H), but instead using 15.00 g (86.7 mmol) of 4-bromophenol, 2.18 g (8.7 mmol) of pyridinium p-toluenesulfonate and 10.94 g (11.9 ml, 130.1 mmol) of 3,4-dihydro-2H-pyran and 75 ml of dichloromethane produced a clear, slightly yellow oil. Purification by flash chromatography (silica, 5% ethyl acetate in hexane) yielded a mixture of 4-bromophenol and the desired THP-ether. This mixture was separated by diluting with 300 ml of 1N aqueous NaOH solution, stirring at room temperature followed by ether extraction. The organic phase was dried over K2CO3, filtered and concentrated in vacuo to give the title compound as a white solid. PMR (CDCl3): d 1.5-2.1 (6H, m), 3.5-3.7 (1H, m), 3.8-3.95 (1H, m), 5.37 (1H, t, J=3.2 Hz), 6.9-6.96 (2H, m), 7.34-7.39 (2H, m).

Workup

  1. customproduced a clear, slightly yellow oil
  2. customPurification by flash chromatography (silica, 5% ethyl acetate in hexane)
  3. customyielded
  4. customThis mixture was separated
  5. additionby diluting with 300 ml of 1N aqueous NaOH solution
  6. extractionfollowed by ether extraction
  7. dry with materialThe organic phase was dried over K2CO3
  8. filtrationfiltered
  9. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-8a5e1780b1c04b1da7918e4c83dd1815
Source dataset
uspto-grants-1997_12
Patent number
US05698700

Reaction notes

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