Sodium Carbonate → 4-[[4'-(Methylsulfonyl)-4-biphenylyl](3,3,5,5-tetramethylcyclohexylidene)methyl]phenol

HRID 1716091Notes

Reaction equation

HRID 1716091 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([C:8](=[C:16]2[CH2:21][C:20]([CH3:23])([CH3:22])[CH2:19][C:18]([CH3:25])([CH3:24])[CH2:17]2)[C:9]2[CH:14]=[CH:13][C:12]([OH:15])=[CH:11][CH:10]=2)=[CH:4][CH:3]=1.[CH3:26][S:27]([C:30]1[CH:35]=[CH:34][C:33](B(O)O)=[CH:32][CH:31]=1)(=[O:29])=[O:28].C([O-])([O-])=O.[Na+].[Na+]>C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.COCCOC>[CH3:26][S:27]([C:30]1[CH:35]=[CH:34][C:33]([C:2]2[CH:3]=[CH:4][C:5]([C:8](=[C:16]3[CH2:17][C:18]([CH3:25])([CH3:24])[CH2:19][C:20]([CH3:23])([CH3:22])[CH2:21]3)[C:9]3[CH:10]=[CH:11][C:12]([OH:15])=[CH:13][CH:14]=3)=[CH:6][CH:7]=2)=[CH:32][CH:31]=1)(=[O:29])=[O:28]

Participants

6

Reactant 3

HCID 10340Sodium CarbonateHCID 27343644-(Methanesulfonyl)phenylboronic acidHCID 686543984-[(4-Bromophenyl)(3,3,5,5-tetramethylcyclohexylidene)methyl]phenol

Product 1

HCID 111557414-[[4'-(Methylsulfonyl)-4-biphenylyl](3,3,5,5-tetramethylcyclohexylidene)methyl]phenolYield 53%

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 80711,2-DimethoxyethaneSolvent

Procedure

To a round-bottomed flask were added 4-[(4-bromophenyl)(3,3,5,5-tetramethylcyclohexylidene)methyl]phenol (14) (85% pure—contains 15% 3,3,5,5-tetramethylcyclohexanone) (0.117 g, 0.25 mmoL), 4-(methanesulphonyl)benzeneboronic acid (0.165 g, 0.82 mmoL), tetrakis(triphenylphosphine)palladium (0) (0.026 g, 0.023 mmoL), 2 M Na2CO3 (3 mL), and ethylene glycol dimethyl ether (8 mL). The stirred reaction mixture was heated at reflux under a nitrogen atmosphere for 3.5 h. The oil bath was removed and the reaction mixture was allowed to cool at RT. The reaction mixture was transferred to a separatory funnel and partitioned between H2O and EtOAc. The organic phase was separated and the aqueous phase was extracted with EtOAc. The organic extracts were combined, dried over MgSO4, filtered, and the filtrate was concentrated in vacuo to give a brown oil. The crude product was purified by flash chromatography on silica gel using a hexanes:EtOAc gradient (100:0 to 75:25) to give 0.063 g (53%) of compound 163 as a white solid. 1H NMR (400 MHz, DMSO-d6): δ 0.89 (s, 12H), 1.26 (s, 2H), 1.93 (s, 4H), 3.23 (s, 3H), 6.67 (d, J=8.5 Hz, 2H), 6.95 (d, J=8.4 Hz, 2H), 7.25 (d, J=8.2 Hz, 2H), 7.67 (d, J=8.3 Hz, 2H), 7.91 (d, J=8.6 Hz, 2H), 7.95 (d, J=8.6 Hz, 2H), 9.29 (s, 1H). HRMS (ESI) Calcd for C30H33O3S: 473.2150 (M−H)−. Found: 473.2168.

Workup

  1. customThe stirred reaction mixture
  2. temperaturewas heated
  3. temperatureat reflux under a nitrogen atmosphere for 3.5 h
  4. customThe oil bath was removed
  5. customThe reaction mixture was transferred to a separatory funnel
  6. custompartitioned between H2O and EtOAc
  7. customThe organic phase was separated
  8. extractionthe aqueous phase was extracted with EtOAc
  9. dry with materialdried over MgSO4
  10. filtrationfiltered
  11. concentrationthe filtrate was concentrated in vacuo
  12. customto give a brown oil
  13. customThe crude product was purified by flash chromatography on silica gel using a hexanes

Sources & evidence

ORD record
ord-2ffd8ed67c6b414eb5fb5c48f166fd8a
Source dataset
uspto-grants-2010_09
Patent number
US07799828B2

Reaction notes

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