Toluene → 3-Methyl-1,1-bis(4-methylphenyl)-2-butanone

HRID 227844

Reaction equation

HRID 227844 reaction equation
CC([O-])(C)C.[Na+].Cl[C:8]1[CH:13]=[CH:12][C:11]([CH3:14])=[CH:10][CH:9]=1.[CH3:15][CH:16]([CH3:20])[C:17](=[O:19])[CH3:18].[C:21]1([CH3:27])[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1>C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd]>[CH3:27][C:21]1[CH:26]=[CH:25][C:24]([CH:18]([C:8]2[CH:13]=[CH:12][C:11]([CH3:14])=[CH:10][CH:9]=2)[C:17](=[O:19])[CH:16]([CH3:20])[CH3:15])=[CH:23][CH:22]=1

Participants

6

Reactant 4

HCID 1140TolueneHCID 78104-ChlorotolueneHCID 112513-Methyl-2-butanoneHCID 23676156Sodium t-butoxide

Product 1

HCID 120407443-Methyl-1,1-bis(4-methylphenyl)-2-butanoneYield 79%

Reagents, catalysts & solvents 1

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalyst

Conditions

Temperature
80 °C

Procedure

An oven-dried Schlenk tube was cooled under an argon purge and charged with Pd2(dba)3 (13.7 mg, 0.015 mmol, 3 mol % Pd), 2 (14.1 mg, 0.036 mmol, 3.6 mol %), and NaOtBu (211 mg, 2.2 mmol). The flask was purged with argon, and toluene (3 mL) was added with stirring. The flask was then charged with 4-chlorotoluene (0.24 mL, 2.0 mmol), 3-methyl-2-butanone (0.105 mL, 1.0 mmol), and additional toluene (3 mL). The reaction mixture was stirred at room temperature for 2 min, then heated to 80° C. with stirring for 22 h at which time GC analysis showed the starting aryl chloride had been completely consumed. The reaction mixture was cooled to room temperature, quenched with saturated aqueous NH4Cl (5 mL), diluted with ether (20 mL), and poured into a separatory funnel. The layers were separated and the aqueous phase was extracted with ether (10 mL). The combined organic fractions were dried over anhydrous magnesium sulfate, filtered, and concentrated in vacuo. The crude material was purified by flash chromatography on silica gel to give 210 mg (79%) of a white solid: mp 48-51° C.; 1H NMR (300 MHz, CDCl3), δ 7.00-7.18 (m, 8H), 5.22 (s, 1H), 2.79 (p, 1H, J=6.8 Hz), 2.31 (s, 6H), 1.10 (d, 6H, J=6.8 Hz); 13C NMR (125 MHz, CDCl3), δ 212.3, 136.6, 135.8, 129.24, 129.16, 128.9, 128.7, 61.4, 40.7, 21.0, 18.6; IR (neat, cm−1), 2972, 1718, 1513, 1038, 803. Anal Calcd for C14H20O: C, 85.67; H, 8.32. Found: C, 86.02; H, 8.59.

Workup

  1. temperatureAn oven-dried Schlenk tube was cooled under an argon
  2. custompurge
  3. customThe flask was purged with argon, and toluene (3 mL)
  4. additionwas added
  5. stirringThe reaction mixture was stirred at room temperature for 2 min
  6. stirringwith stirring for 22 h at which time GC analysis
  7. customhad been completely consumed
  8. temperatureThe reaction mixture was cooled to room temperature
  9. customquenched with saturated aqueous NH4Cl (5 mL)
  10. additiondiluted with ether (20 mL)
  11. additionpoured into a separatory funnel
  12. customThe layers were separated
  13. extractionthe aqueous phase was extracted with ether (10 mL)
  14. dry with materialThe combined organic fractions were dried over anhydrous magnesium sulfate
  15. filtrationfiltered
  16. concentrationconcentrated in vacuo
  17. customThe crude material was purified by flash chromatography on silica gel

Sources & evidence

ORD record
ord-256c20251579404ea06c1eef4b60010f
Source dataset
uspto-grants-2009_07
Patent number
US07560582B2

Linked notes

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