Acetic Acid → 5-(3-Bromopropylidene)-5,11-dihydro[1]benzoxepino[2,3-b]pyridine

HRID 1010874Notes

Reaction equation

HRID 1010874 reaction equation
[CH:1]1([C:4]2(O)[C:14]3[C:9](=[N:10][CH:11]=[CH:12][CH:13]=3)[O:8][C:7]3[CH:15]=[CH:16][CH:17]=[CH:18][C:6]=3[CH2:5]2)[CH2:3][CH2:2]1.C(O)(=O)C.[BrH:24]>O>[Br:24][CH2:3][CH2:2][CH:1]=[C:4]1[C:14]2[C:9](=[N:10][CH:11]=[CH:12][CH:13]=2)[O:8][C:7]2[CH:15]=[CH:16][CH:17]=[CH:18][C:6]=2[CH2:5]1

Participants

5

Reactant 3

HCID 176Acetic AcidHCID 260Hydrogen BromideHCID 231311475-Cyclopropyl-5,11-dihydro[1]benzoxepino[2,3-b]pyridin-5-ol

Product 1

HCID 667575595-(3-Bromopropylidene)-5,11-dihydro[1]benzoxepino[2,3-b]pyridine

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Conditions

Temperature
60 °C

Procedure

To a 2 L eggplant flask with a magnetic stirring bar was added 75.0 g. of 5-Cyclopropyl-5,11-dihydro[1]benzoxepino[2,3-b]pyridin-5-ol (0.30 mole) and 75 mL of acetic acid. The solution was cooled with water (ca. 10° C.), 120 ml of 47% aqueous hydrobromic acid was added over a period of 5 minutes. The reaction mixture was warmed to 60° C., stirred for an hour, and evaporated (aspirator vacuum, ca. 50° C.) to ca. 200 mL. The reaction mixture was poured to 1500 mL of saturated aqueous sodium bicarbonate, the mixture is extracted with two 800 mL portions of ethyl acetate, and the combined organic extracts are washed with 500 mL 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 500 g. of Silica gel 60 by eluting with 5:1-4:1 (v/v) hexane-ethyl acetate mixture. The elution was evaporated, giving the titled compound as a pale yellow oil.

Workup

  1. additionTo a 2 L eggplant flask with a magnetic stirring bar was added 75.0 g
  2. additionwas added over a period of 5 minutes
  3. customevaporated (aspirator vacuum, ca. 50° C.) to ca. 200 mL
  4. additionThe reaction mixture was poured to 1500 mL of saturated aqueous sodium bicarbonate
  5. extractionthe mixture is extracted with two 800 mL portions of ethyl acetate
  6. washthe combined organic extracts are washed with 500 mL of saturated aqueous sodium chloride
  7. dry with materialThe organic solution was dried with anhydrous magnesium sulfate
  8. filtrationfiltered
  9. customevaporated (aspirator vacuum, ca. 30° C.)
  10. customThe oily residue was chromatographed on 500 g
  11. washof Silica gel 60 by eluting with 5:1-4:1 (v/v) hexane-ethyl acetate mixture
  12. washThe elution
  13. customwas evaporated

Sources & evidence

ORD record
ord-1566d23c0b694f6db065447517c37755
Source dataset
uspto-grants-2011_07
Patent number
US07977350B2

Reaction notes

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