2,6-Dimethylphenol → 5-(4-hydroxy-3,5-dimethylphenyl)-5H-dibenzo[b,d]thiophenium bromide

HRID 1841856Notes

Reaction equation

HRID 1841856 reaction equation
CS(O)(=O)=O.O=P12OP3(OP(OP(O3)(O1)=O)(=O)O2)=O.[CH:20]1[C:28]2[C:27]3[CH:29]=[CH:30][CH:31]=[CH:32][C:26]=3[S:25](=O)[C:24]=2[CH:23]=[CH:22][CH:21]=1.[CH3:34][C:35]1[CH:40]=[CH:39][CH:38]=[C:37]([CH3:41])[C:36]=1[OH:42].[Br-:43].[K+]>ClCCl.C(OCC)(=O)C.O>[Br-:43].[OH:42][C:36]1[C:37]([CH3:41])=[CH:38][C:39]([S+:25]2[C:24]3[CH:23]=[CH:22][CH:21]=[CH:20][C:28]=3[C:27]3[CH:29]=[CH:30][CH:31]=[CH:32][C:26]2=3)=[CH:40][C:35]=1[CH3:34]

Participants

8

Reactant 4

HCID 113352,6-DimethylphenolHCID 13898Dibenzothiophene sulfoxideHCID 253877Potassium BromideHCID 86584057Phosphorus Pentoxide-Methanesulfonic Acid

Product 1

HCID 867124575-(4-hydroxy-3,5-dimethylphenyl)-5H-dibenzo[b,d]thiophenium bromideYield 17,474.801%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 6344DichloromethaneSolventHCID 8857Ethyl AcetateSolvent

Procedure

Eaton's Reagent (100 mL) was added dropwise to a solution of dibenzothiophene oxide (15.0 g, 74.9 mmol) and 2,6-dimethylphenol (9.15 g, 74.9 mmol) in dichloromethane (200 mL) at 0° C. The reaction was warmed to r.t. and stirred for 4 h, then cooled to 0° C. and quenched with the slow addition of water (200 mL) keeping the reaction temperature below 20° C. The aqueous phase was extracted with ethyl acetate (3×100 mL) and potassium bromide (17.9 g, 0.150 mmol) in water (50 mL) was added to the aqueous layer under vigorous stirring. The slurry was stirred at r.t. for 1 h, filtered and washed with water (3×200 mL), MTBE (3×200 mL) and the residue dried in vacuo to afford the title compound (10.1 g, 35%) as an off-white solid. 1H NMR (300 MHz, (CD3)2CO) δ: 9.77 (brs, 10H), 8.52 (d, J=8.1 Hz, 2H), 8.27 (8.1 Hz, 2H), 7.95 (t, J=7.8 Hz, 2H), 7.74 (t, J=7.8 Hz, 2H), 7.20 (s, 2H), 2.12 (s, 6H).

Workup

  1. temperaturecooled to 0° C.
  2. customquenched with the slow addition of water (200 mL)
  3. customthe reaction temperature below 20° C
  4. additionwas added to the aqueous layer under vigorous stirring
  5. stirringThe slurry was stirred at r.t. for 1 h
  6. filtrationfiltered
  7. washwashed with water (3×200 mL), MTBE (3×200 mL)
  8. customthe residue dried in vacuo

Sources & evidence

ORD record
ord-e6537cb6ec8448d2acd9c448d3d82661
Source dataset
uspto-grants-2015_02
Patent number
US08945814B2

Reaction notes

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