Ethanol → 843661-24-5

HRID 2100042Notes

Reaction equation

HRID 2100042 reaction equation
[OH:1][C:2]1[CH:7]=[CH:6][C:5]([C:8](=[C:19]2[CH2:24][C:23]([CH3:26])([CH3:25])[CH2:22][C:21]([CH3:28])([CH3:27])[CH2:20]2)[C:9]2[CH:18]=[CH:17][C:12]([C:13]([O:15]C)=[O:14])=[CH:11][CH:10]=2)=[CH:4][CH:3]=1.CCO.[OH-].[Na+]>C1COCC1>[OH:1][C:2]1[CH:3]=[CH:4][C:5]([C:8](=[C:19]2[CH2:20][C:21]([CH3:28])([CH3:27])[CH2:22][C:23]([CH3:26])([CH3:25])[CH2:24]2)[C:9]2[CH:18]=[CH:17][C:12]([C:13]([OH:15])=[O:14])=[CH:11][CH:10]=2)=[CH:6][CH:7]=1

Participants

5

Reactant 3

HCID 702EthanolHCID 14798Sodium HydroxideHCID 68654149HCID 68654149, compound

Product 1

HCID 11199337843661-24-5Yield 79%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
65 °C

Procedure

To a round-bottomed flask was added methyl 4-[(4-hydroxyphenyl)(3,3,5,5-tetramethylcyclohexylidene)methyl]benzoate (25) (8.06 g, 21 mmoL), EtOH (100 mL), and THF (100 mL). To the solution was added 1 N aqueous NaOH (200 mL). The reaction mixture was stirred at 65° C. under a nitrogen atmosphere for 3 h. The reaction mixture was partially concentrated in vacuo to remove the EtOH and THF. The aqueous mixture was cooled in an ice-water bath and 1 N aqueous HCl was slowly added to pH ˜1. The acidic aqueous suspension was extracted with CH2Cl2 (1×) followed by EtOAc (3×). Those EtOAc extracts that contained the majority of product, as indicated by TLC, were independently washed with brine, combined, dried over MgSO4, filtered, and the filtrate was concentrated to give 6.0 g of the crude product as a pale tan solid. The CH2Cl2 extract noted above was concentrated to give 1.9 g of the crude product as an off-white solid. The two crops of crude product were combined and purified by flash chromatography on silica gel with CH2Cl2:MeOH (95:5) to give 6.07 g (79%) of compound 26 as a white solid. A portion of the product was dried under vacuum at 90° C. to give the following 1H NMR data. 1H NMR (400 MHz, DMSO-d6): δ 0.86 (s, 6 H), 0.88 (s, 6 H), 1.24 (s, 2 H), 1.85 (s, 2 H), 1.92 (s, 2 H), 6.66 (d, J=8.5 Hz, 2 H), 6.93 (d, J=8.4 Hz, 2 H), 7.22 (d, J=8.3 Hz, 2 H), 7.84 (d, J=8.3 Hz, 2 H), 9.30 (s, 2 H), 12.78 (br s, 1 H). The compound was silylated prior to EI analysis. HRMS (EI) Calcd for C30H44O3Si2: 508.2829 (M+). Found: 508.2833.

Workup

  1. concentrationThe reaction mixture was partially concentrated in vacuo
  2. customto remove the EtOH and THF
  3. temperatureThe aqueous mixture was cooled in an ice-water bath
  4. addition1 N aqueous HCl was slowly added to pH ˜1
  5. extractionThe acidic aqueous suspension was extracted with CH2Cl2 (1×)
  6. washwere independently washed with brine
  7. dry with materialdried over MgSO4
  8. filtrationfiltered
  9. concentrationthe filtrate was concentrated
  10. customto give 6.0 g of the crude product as a pale tan solid
  11. extractionThe CH2Cl2 extract
  12. concentrationabove was concentrated
  13. customto give 1.9 g of the crude product as an off-white solid
  14. custompurified by flash chromatography on silica gel with CH2Cl2:MeOH (95:5)

Sources & evidence

ORD record
ord-2692385f76bf4a7fac8cf6ffc7fb39b8
Source dataset
uspto-grants-2009_08
Patent number
US07569601B2

Reaction notes

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