1,2,3,4-Tetraphenylcyclopenta-1,3-diene → HCID 86680257, compound

HRID 921048Notes

Reaction equation

HRID 921048 reaction equation
C([C:5]1[N:10]=[CH:9][C:8]([C:11]2[NH:12][C:13]3[CH:19]=[CH:18][CH:17]=[CH:16][C:14]=3[N:15]=2)=[CH:7][N:6]=1)(C)(C)C.[C:20]1(C2CC(C3C=CC=CC=3)=C(C3C=CC=CC=3)C=2C2C=CC=CC=2)C=CC=C[CH:21]=1>CN(C=O)C.C[Rh](Cl)(C)(C)(C)(C)C1C=CC=C1.O.C([O-])(=O)C.[Cu+2].C([O-])(=O)C>[CH:9]1[C:8]2[C:11]3[N:15]([CH:20]=[CH:21][C:7]=2[N:6]=[CH:5][N:10]=1)[C:14]1[C:13](=[CH:19][CH:18]=[CH:17][CH:16]=1)[N:12]=3

Participants

6

Reactant 2

HCID 849911,2,3,4-Tetraphenylcyclopenta-1,3-dieneHCID 67996031HCID 67996031, compound

Product 1

HCID 86680257HCID 86680257, compound

Reagents, catalysts & solvents 3

HCID 165397Cupric acetate monohydrateCatalystHCID 178477783HCID 178477783, compoundCatalystHCID 6228DimethylformamideSolvent

Conditions

Temperature
100 °C

Procedure

Preparation analogous to N. Umeda et al., Angew. Chem. Int. Ed. 2008, 47, 4019: a solution of 25.2 g (100 mmol) of 2-(2-tert-butylpyrimidin-5-yl)benzimidazole (S48) and 110 mmol of the alkyne in 400 ml of DMF is initially introduced in a pressure Schlenk tube, 1.5 g (4 mmol) of tetraphenylcyclopentadiene, 547 mg (1 mmol) of pentamethylcyclopentadienyl-rhodium chloride dimer and 21.0 (105 mmol) of copper(II) acetate monohydrate are added, and the mixture is stirred in the sealed tube at 100° C. for 18 h. After cooling, the DMF is removed in vacuo, the residue is taken up in 1000 ml of THF and filtered through a short silica-gel column. After removal of the THF in vacuo, the oily residue is taken up in hot methanol (about 75 ml). After cooling, the crystals formed are filtered off with suction and recrystallised again from methanol with addition of a little ethyl acetate. The solids obtained in this way are freed from low-boiling components and non-volatile secondary components by sublimation (p about 1×10−5 mbar, T about 180-220° C.). Purity according to 1H-NMR typically >99.5%.

Workup

  1. customPreparation analogous to N
  2. temperatureAfter cooling
  3. customthe DMF is removed in vacuo
  4. filtrationfiltered through a short silica-gel column
  5. customAfter removal of the THF in vacuo
  6. temperatureAfter cooling
  7. customthe crystals formed
  8. filtrationare filtered off with suction
  9. customrecrystallised again from methanol with addition of a little ethyl acetate
  10. customThe solids obtained in this way
  11. customare freed from low-boiling components and non-volatile secondary components by sublimation (p about 1×10−5 mbar, T about 180-220° C.)

Sources & evidence

ORD record
ord-b533c4fed56a4e65aefd0ce3a20f5c05
Source dataset
uspto-grants-2016_03
Patent number
US09273080B2

Reaction notes

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