5-bromo-1H-indene → HCID 17829233, compound

HRID 1017151Notes

Reaction equation

HRID 1017151 reaction equation
Br[C:2]1[CH:3]=[C:4]2[C:8](=[CH:9][CH:10]=1)[CH2:7][CH:6]=[CH:5]2.[C:11]1([Mg]Br)[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=1>C1C=CC(P(C2C=CC=CC=2)CCP(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.Cl[Ni]Cl.C(OCC)C>[C:11]1([C:2]2[CH:3]=[C:4]3[C:8](=[CH:9][CH:10]=2)[CH2:7][CH:6]=[CH:5]3)[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=1

Participants

5

Reactant 2

HCID 27475715-bromo-1H-indeneHCID 178418255HCID 178418255, compound

Product 1

HCID 17829233HCID 17829233, compound

Reagents, catalysts & solvents 2

HCID 2734542[1,2-Bis(diphenylphosphino)ethane]dichloronickel(II)CatalystHCID 3283Diethyl EtherSolvent

Conditions

Temperature
10 °C

Procedure

A dry 100 mL three-neck round bottom flask equipped with a condenser, magnetic stir bar, thermometer, and a nitrogen inlet was charged with 5-bromoindene (99+% purity, 9.65 g, 50 mmol), diethyl ether (anhydrous, 60 mL), and phenylmagnesium bromide (18.0 mL 3M in diethyl ether, 54 mmol). The mixture was chilled to 10° C. and [1,2-bis(diphenylphosphino)ethane]nickel(II) chloride (0.1 g, 0.2 mmol) was added. The reaction mixture was warmed gradually to reflux. As the reaction progressed the clear solution became turbid from the precipitation of magnesium bromide by-product. After 4 hours at reflux the reaction mixture was quenched in chilled 5% aqueous HCl (200 mL). Additional diethyl ether (100 mL) was added and the organic phase was separated, water washed, and dried over anhydrous magnesium sulfate. Evaporation of diethyl ether followed by vacuum distillation (90° C./0.5 mm Hg) gave 5-phenylinene (8.4 g, 97% purity by GC) as pale yellow crysta1s. 1HNMR (CD2Cl2, 500 MHz) 50:50 mixture of isomers; δ7.72 (s, 1H); 7.62 (m, 5H); 7.52 (t, J=8 Hz, 2H); 7.43 (m, 6H); 7.32 (m, 2H); 6.93 (m, 2H); 6.61 (m, 2H); 3.47 (s, 2H); 3.44 (s, 2H).

Workup

  1. customA dry 100 mL three-neck round bottom flask equipped with a condenser, magnetic stir bar
  2. temperatureThe reaction mixture was warmed gradually
  3. temperatureto reflux
  4. customfrom the precipitation of magnesium bromide by-product
  5. temperatureAfter 4 hours at reflux the reaction mixture
  6. customwas quenched in chilled 5% aqueous HCl (200 mL)
  7. additionAdditional diethyl ether (100 mL) was added
  8. customthe organic phase was separated
  9. washwater washed
  10. dry with materialdried over anhydrous magnesium sulfate
  11. customEvaporation of diethyl ether
  12. distillationfollowed by vacuum distillation (90° C./0.5 mm Hg)
  13. customgave 5-phenylinene (8.4 g, 97% purity by GC) as pale yellow crysta1s

Sources & evidence

ORD record
ord-f06289c808f143b1a8fe94a5eba5abb1
Source dataset
uspto-grants-2002_11
Patent number
US06479424B1

Reaction notes

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