Hydrochloric Acid → HCID 18402861, compound

HRID 1017152Notes

Reaction equation

HRID 1017152 reaction equation
[C:1]1([C:7]2[CH:8]=[C:9]3[C:13](=[CH:14][CH:15]=2)[CH2:12][CH:11]=[CH:10]3)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[C:16]([C:20]1[CH:21]=[C:22](Br)[CH:23]=[C:24]([C:26]([CH3:29])([CH3:28])[CH3:27])[CH:25]=1)([CH3:19])([CH3:18])[CH3:17].C([O-])(=O)C.[Na+].Cl>[Cl-].C1([P+](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C(#N)C.C(#N)C.Cl[Pd]Cl.CN1CCCC1=O>[C:16]([C:20]1[CH:21]=[C:22]([C:11]2[CH2:12][C:13]3[C:9]([CH:10]=2)=[CH:8][C:7]([C:1]2[CH:2]=[CH:3][CH:4]=[CH:5][CH:6]=2)=[CH:15][CH:14]=3)[CH:23]=[C:24]([C:26]([CH3:29])([CH3:28])[CH3:27])[CH:25]=1)([CH3:19])([CH3:18])[CH3:17]

Participants

8

Reactant 4

HCID 313Hydrochloric AcidHCID 517045Sodium AcetateHCID 6201361-Bromo-3,5-di-tert-butylbenzeneHCID 17829233HCID 17829233, compound2×

Product 1

HCID 18402861HCID 18402861, compoundYield 99.9%

Reagents, catalysts & solvents 3

HCID 164911Tetraphenylphosphonium ChlorideCatalystHCID 6093782Bis(acetonitrile)dichloropalladiumCatalystHCID 13387N-methyl-2-pyrrolidoneSolvent

Conditions

Temperature
60 °C

Procedure

A 100 mL three-neck round bottom flask equipped with a condenser, magnetic stir bar, thermometer, and a nitrogen inlet was dried, purged with nitrogen, then charged with 5-phenylindene (5.8 g, 0.03 mol), 3,5-di-tert-butylbromobenzene (8.1 g, 0.03 mol), sodium acetate (4.9 g, 0.06 mol), dichloropalladium (II) bis(acetonitrile) (0.026 g, 0.10 mmol), tetraphenylphosphonium chloride (0.225 g, 0.60 mmol), and anhydrous 1-methyl-2-pyrrolidinone (45 mL). The reaction mixture was heated to 60° C. for 24 hours without any conversion of starting materials. The temperature was then raised to 140° C. for 16 hours after which GC analysis showed >95% conversion of 5-phenylindene. The reaction mixture was cooled, mixed with chilled 5% aqueous HCl (250 mL) and extracted with diethyl ether (3×100 mL). The combined diethyl ether extracts were water washed and then dried over anhydrous magnesium sulfate. Rotary evaporation gave crude product (12.5 g) as a viscous red-brown oil. Crystals of 2-(3,5-di-tert-butylphenyl)-5-phenylindene (6.4 g) precipitated from a concentrated solution (˜50%) of the crude product in acetone-methanol (70:30). Three consecutive recrystallizations from acetone-methanol yielded 2-(3,5-di-tert-butylphenyl)-5-phenylindene (3.2 g, 99.9% purity by GC) as pale tan crystals (mp 122-3° C.). 1HNMR (CD2Cl2, 500MHz) 40:60 mixture of isomeric alkenes; δ7.65-7.25 (mults, 12H); 3.82, 3.80 (s, 2H); 1.30 (s, 18H).

Workup

  1. customA 100 mL three-neck round bottom flask equipped with a condenser, magnetic stir bar
  2. customthermometer, and a nitrogen inlet was dried
  3. custompurged with nitrogen
  4. temperatureThe temperature was then raised to 140° C. for 16 hours after which GC analysis
  5. temperatureThe reaction mixture was cooled
  6. additionmixed
  7. extractionextracted with diethyl ether (3×100 mL)
  8. washwashed
  9. dry with materialdried over anhydrous magnesium sulfate
  10. customRotary evaporation
  11. customgave crude product (12.5 g) as a viscous red-brown oil
  12. customCrystals of 2-(3,5-di-tert-butylphenyl)-5-phenylindene (6.4 g) precipitated from a concentrated solution (˜50%) of the crude product in acetone-methanol (70:30)
  13. customThree consecutive recrystallizations from acetone-methanol

Sources & evidence

ORD record
ord-d66701b699b54c91a83460bbbf6c332d
Source dataset
uspto-grants-2002_11
Patent number
US06479424B1

Reaction notes

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