Sodium Carbonate → Methyl 4'-[(4-hydroxyphenyl)(3,3,5,5-tetramethylcyclohexylidene)methyl]-2-biphenylcarboxylate

HRID 2100208

Reaction equation

HRID 2100208 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][O:27][C:28]([C:30]1[CH:35]=[CH:34][CH:33]=[CH:32][C:31]=1B(O)O)=[O:29].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>[OH:15][C:12]1[CH:11]=[CH:10][C:9]([C:8](=[C:16]2[CH2:21][C:20]([CH3:22])([CH3:23])[CH2:19][C:18]([CH3:24])([CH3:25])[CH2:17]2)[C:5]2[CH:6]=[CH:7][C:2]([C:31]3[C:30]([C:28]([O:27][CH3:26])=[O:29])=[CH:35][CH:34]=[CH:33][CH:32]=3)=[CH:3][CH:4]=2)=[CH:14][CH:13]=1

Participants

6

Reactant 3

HCID 10340Sodium CarbonateHCID 27734962-(Methoxycarbonyl)benzeneboronic acidHCID 686543984-[(4-Bromophenyl)(3,3,5,5-tetramethylcyclohexylidene)methyl]phenol

Product 1

HCID 68654495Methyl 4'-[(4-hydroxyphenyl)(3,3,5,5-tetramethylcyclohexylidene)methyl]-2-biphenylcarboxylateYield 68%

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 80711,2-DimethoxyethaneSolvent

Conditions

Temperature
160 °C

Procedure

A sealed tube containing 4-[(4-bromophenyl)(3,3,5,5-tetramethylcyclohexylidene)methyl]phenol (14) (0.30 g, 0.75 mmol), (2-methoxycarbonylphenyl)boronic acid (0.29 g, 1.50 mmol), Pd(PPh3)4 (87 mg, 0.08 mmol), 2 M Na2CO3 (4 mL) and DME (4 mL) was heated at 160° C. for 25 minutes. Cooled to room temperature, the mixture was extracted with EtOAc. The EtOAc extracts were combined and washed with water, brine, dried over Na2SO4, filtered, and the filtrate was concentrated to give the crude product as dark brown oil. The crude product was purified by chromatography on a silica gel column eluted with a gradient from hexanes to 20% EtOAc in hexanes to give 0.23 g (68%) of the title compound (248) as off-white solid. mp 177-178° C. 1H NMR (400 MHz, CDCl3): δ 0.96 (s, 6H), 0.97 (s, 6H), 1.32 (s, 2H), 2.03 (s, 4H), 3.57 (s, 3H), 4.60 (s, 1H), 6.78 (d, J=8.5 Hz, 2H), 7.10 (d, J=8.5 Hz, 2H), 7.15-7.25 (m, 4H), 7.36-7.44 (m, 2H), 7.48-7.56 (m, 1H), 7.76-7.82 (m, 1H). LCMS (ESI): m/z 455 (M+H)+, 453 (M−H)−.

Workup

  1. temperatureCooled to room temperature
  2. extractionthe mixture was extracted with EtOAc
  3. washwashed with water, brine
  4. dry with materialdried over Na2SO4
  5. filtrationfiltered
  6. concentrationthe filtrate was concentrated
  7. customto give the crude product as dark brown oil
  8. customThe crude product was purified by chromatography on a silica gel column
  9. washeluted with a gradient from hexanes to 20% EtOAc in hexanes

Sources & evidence

ORD record
ord-02e7cea3e3744fd3850aaefdefd36efe
Source dataset
uspto-grants-2009_08
Patent number
US07569601B2

Linked notes

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