Acetyl chloride → 7-Acetyl-5-(3-bromopropylidene)-5,11-dihydro[1]benzoxepino[2,3-b]pyridine

HRID 1010875Notes

Reaction equation

HRID 1010875 reaction equation
[Br:1][CH2:2][CH2:3][CH:4]=[C:5]1[C:15]2[C:10](=[N:11][CH:12]=[CH:13][CH:14]=2)[O:9][C:8]2[CH:16]=[CH:17][CH:18]=[CH:19][C:7]=2[CH2:6]1.[Cl-].[Al+3].[Cl-].[Cl-].[C:24](Cl)(=[O:26])[CH3:25]>ClCCl>[C:24]([C:19]1[C:7]2[CH2:6][C:5](=[CH:4][CH2:3][CH2:2][Br:1])[C:15]3[C:10]([O:9][C:8]=2[CH:16]=[CH:17][CH:18]=1)=[N:11][CH:12]=[CH:13][CH:14]=3)(=[O:26])[CH3:25]

Participants

5

Reactant 3

HCID 6367Acetyl chlorideHCID 6451240Aluminum(III) ChlorideHCID 667575595-(3-Bromopropylidene)-5,11-dihydro[1]benzoxepino[2,3-b]pyridine

Product 1

HCID 667578367-Acetyl-5-(3-bromopropylidene)-5,11-dihydro[1]benzoxepino[2,3-b]pyridine

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Conditions

Temperature
0 °C

Procedure

A dry 3 L three-necked, round-bottomed flask was fitted with a magnetic stirring bar, a glass stopper, a rubber septum, and an argon inlet. Under an argon atmosphere, 94.0 g. of 5-(3-Bromopropylidene)-5,11-dihydro[1]benzoxepino[2,3-b]pyridine (0.30 mole) and 900 mL of dry dichloromethane were added to the flask and the flask was cooled with an ice bath. To the solution was slowly added 78.5 g. of aluminum chloride (0.83 mole), followed by 17.8 mL of acetyl chloride (0.25 mole), and the mixture was stirred for an hour at 0° C. The reaction mixture was poured to 1500 g of ice, and the layers were separated. The aqueous layer was extracted with three 400 mL portions of ethyl acetate. Dichloromethane layer and the organic extracts were combined and washed successively with 1 μL of saturated aqueous sodium bicarbonate and 1 L of saturated aqueous sodium chloride. The organic solution was dried with anhydrous magnesium sulfate, filtered, and evaporated (aspirator vacuum, ca. 30° C.). The oily residue was chromatographed on 800 g. of Silica gel 60 by eluting with 5:1-1:1 (v/v) hexane-ethyl acetate mixture. The elution was evaporated, giving the titled compound as a pale yellow solid.

Workup

  1. customA dry 3 L three-necked, round-bottomed flask was fitted with a magnetic stirring bar
  2. temperaturethe flask was cooled with an ice bath
  3. customthe layers were separated
  4. extractionThe aqueous layer was extracted with three 400 mL portions of ethyl acetate
  5. washwashed successively with 1 μL of saturated aqueous sodium bicarbonate and 1 L of saturated aqueous sodium chloride
  6. dry with materialThe organic solution was dried with anhydrous magnesium sulfate
  7. filtrationfiltered
  8. customevaporated (aspirator vacuum, ca. 30° C.)
  9. customThe oily residue was chromatographed on 800 g
  10. washof Silica gel 60 by eluting with 5:1-1:1 (v/v) hexane-ethyl acetate mixture
  11. washThe elution
  12. customwas evaporated

Sources & evidence

ORD record
ord-27c9750a8a8b4451b0bec690369288bb
Source dataset
uspto-grants-2011_07
Patent number
US07977350B2

Reaction notes

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