Water → 2,5-Di([1,1'-biphenyl]-3-yl)-3,4-bis(4-bromophenyl)cyclopenta-2,4-dienone

HRID 57308Notes

Reaction equation

HRID 57308 reaction equation
[Br:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]([C:10]([C:12]2[CH:17]=[CH:16][C:15]([Br:18])=[CH:14][CH:13]=2)=O)=O)=[CH:4][CH:3]=1.[C:19]1([C:41]2[CH:46]=[CH:45][CH:44]=[CH:43][CH:42]=2)[CH:24]=[CH:23][CH:22]=[C:21]([CH2:25][C:26](=[O:40])[CH2:27][C:28]2[CH:29]=[C:30]([C:34]3[CH:39]=[CH:38][CH:37]=[CH:36][CH:35]=3)[CH:31]=[CH:32][CH:33]=2)[CH:20]=1.[OH-].C([N+](CCCC)(CCCC)CCCC)CCC.O>C(O)(C)(C)C>[C:30]1([C:34]2[CH:39]=[CH:38][CH:37]=[CH:36][CH:35]=2)[CH:31]=[CH:32][CH:33]=[C:28]([C:27]2[C:26](=[O:40])[C:25]([C:21]3[CH:20]=[C:19]([C:41]4[CH:42]=[CH:43][CH:44]=[CH:45][CH:46]=4)[CH:24]=[CH:23][CH:22]=3)=[C:8]([C:5]3[CH:6]=[CH:7][C:2]([Br:1])=[CH:3][CH:4]=3)[C:10]=2[C:12]2[CH:17]=[CH:16][C:15]([Br:18])=[CH:14][CH:13]=2)[CH:29]=1

Participants

6

Reactant 4

HCID 962WaterHCID 964304,4'-DibromobenzilHCID 2723671Tetrabutylammonium HydroxideHCID 577828671,3-Di(biphenyl-3-yl)propan-2-one

Product 1

HCID 895341902,5-Di([1,1'-biphenyl]-3-yl)-3,4-bis(4-bromophenyl)cyclopenta-2,4-dienoneYield 53.1%

Reagents, catalysts & solvents 1

HCID 6386tert-ButanolSolvent

Conditions

Temperature
80 °C

Procedure

To a degassed solution of 2.84 g of 4,4′-dibromobenzil (7.73 mmol) and 2.80 g of 1,3-di(biphenyl-3-yl)propan-2-one (7, 7.73 mmol) in 30 ml of tert-butanol was added, at 80° C., a methanolic tetrabutylammonium hydroxide solution (1 M, 2.84 ml, 2.84 mmol). The reaction solution was stirred at 80° C. for 20 minutes and then stopped by adding water. Extraction was effected three times with dichloromethane, and the collected organic phases were washed with saturated sodium chloride solution and dried over magnesium sulfate before the solvent was distilled off under reduced pressure. The crude product was purified by column chromatography (silica gel, eluent: hexane with 20% DCM) and gave 2.85 g of the tetraarylcyclopentadienone 8a as a violet wax (53%, 4.10 mmol). Elemental analysis measured: C 70.5; H 3.3% (calculated for C41H26Br2O: C, 70.9; H, 3.8%); 1H NMR (700 MHz, d8-THF) δ=7.51-7.49 (m, 4H, CH), 7.49-7.46 (m, 4H, CH), 7.41 (dd, J=8.2, 1.1 Hz, 4H, CH), 7.36 (t, J=7.8 Hz, 4H, CH), 7.32 (t, J=8.0 Hz, 2H, CH), 7.29-7.25 (m, 2H, CH), 7.25-7.22 (m, 2H, CH), 7.01-6.99 (m, 4H, CH); 13C NMR (175 MHz, d8-THF) δ=154.28, 141.92, 141.83, 133.58, 132.72, 132.34, 132.30, 132.12, 129.99, 129.89, 129.71, 129.53, 128.26, 127.80, 127.21, 126.74, 123.92; MS (FD, 8 kV): m/z (%): 693.8 (100) [M+] (calculated for C41H26Br2O: 694.0); Rf (hexane with 6% ethyl acetate)=0.47.

Workup

  1. extractionExtraction
  2. washthe collected organic phases were washed with saturated sodium chloride solution
  3. dry with materialdried over magnesium sulfate before the solvent
  4. distillationwas distilled off under reduced pressure
  5. customThe crude product was purified by column chromatography (silica gel, eluent: hexane with 20% DCM)

Sources & evidence

ORD record
ord-242888ab43b04b3a8422c0692622ff10
Source dataset
uspto-grants-2016_09
Patent number
US09434619B2

Reaction notes

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