4-Bromobenzophenone → HCID 68505673, compound

HRID 2241020Notes

Reaction equation

HRID 2241020 reaction equation
[C:1]1(=O)[CH2:7][CH2:6][CH2:5][CH2:4][CH2:3][CH2:2]1.[Br:9][C:10]1[CH:23]=[CH:22][C:13]([C:14]([C:16]2[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=2)=O)=[CH:12][CH:11]=1>C1COCC1.[Zn].Cl[Ti](Cl)(Cl)Cl>[Br:9][C:10]1[CH:11]=[CH:12][C:13]([C:14](=[C:1]2[CH2:7][CH2:6][CH2:5][CH2:4][CH2:3][CH2:2]2)[C:16]2[CH:17]=[CH:18][CH:19]=[CH:20][CH:21]=2)=[CH:22][CH:23]=1

Participants

6

Reactant 2

HCID 70304-BromobenzophenoneHCID 10400Cycloheptanone

Product 1

HCID 68505673HCID 68505673, compound

Reagents, catalysts & solvents 3

HCID 23994ZincCatalystHCID 24193Titanium TetrachlorideCatalystHCID 8028TetrahydrofuranSolvent2×

Procedure

To a stirred suspension of Zn powder (4.80 g, 73.5 mmol) and THF (100 mL) under N2 was added TiCl4 (3.9 mL, 35.7 mmol), dropwise. The resulting yellow suspension was stirred at RT for 45 min followed by reflux for 2.5 h. A solution of cycloheptanone (3.42 g, 30.6 mmol) and 4-bromobenzophenone (2.54 g, 9.75 mmol) in THF (40 mL) was added dropwise to the refluxing reaction over 15 min. After 2 h the reaction was cooled to RT and then quenched by sequential dropwise addition of water (75 mL) and 10% aqueous Na2CO3 (75 mL). The mixture was stirred overnight at RT then diluted with EtOAc (300 mL) and filtered through a celite pad. The celite pad was rinsed with EtOAc (250 mL) and the colorless filtrates transferred to a separatory funnel. The organic fraction was washed with brine (300 mL), dried (Na2SO4) and concentrated to 6.50 g of a colorless oil. The oil was purified by column chromatographed on silica gel (150 g) with hexanes followed by 2% EtOAc:hexanes and the product 1 isolated as a colorless oil that solidified on standing (2.54 g, 76%). 1H NMR (300 MHz, DMSO-d6): δ 1.59 (s, 8H), 2.27 (br s, 4H), 7.15-7.39 (m, 7H), 7.55 (d, J=8.3 Hz, 2H).

Workup

  1. temperatureby reflux for 2.5 h
  2. temperatureAfter 2 h the reaction was cooled to RT
  3. customquenched by sequential dropwise addition of water (75 mL) and 10% aqueous Na2CO3 (75 mL)
  4. stirringThe mixture was stirred overnight at RT
  5. additionthen diluted with EtOAc (300 mL)
  6. filtrationfiltered through a celite pad
  7. washThe celite pad was rinsed with EtOAc (250 mL)
  8. customthe colorless filtrates transferred to a separatory funnel
  9. washThe organic fraction was washed with brine (300 mL)
  10. dry with materialdried (Na2SO4)
  11. concentrationconcentrated to 6.50 g of a colorless oil
  12. customThe oil was purified by column
  13. customchromatographed on silica gel (150 g) with hexanes

Sources & evidence

ORD record
ord-2c942774b36941bfb29dcb750b65f937
Source dataset
uspto-grants-2010_05
Patent number
US07723393B2

Reaction notes

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