Potassium Iodide → HCID 13808684, compound

HRID 648707Notes

Reaction equation

HRID 648707 reaction equation
[CH3:1][O:2][C:3]1[CH:18]=[CH:17][C:6]2[CH2:7][CH2:8][C:9](=[O:16])[CH:10]([C:12]([O:14][CH3:15])=[O:13])[O:11][C:5]=2[CH:4]=1.Br[CH2:20][CH2:21][CH2:22][Cl:23].[I-].[K+].C(=O)([O-])[O-].[K+].[K+]>C(#N)C>[Cl:23][CH2:22][CH2:21][CH2:20][C:10]1([C:12]([O:14][CH3:15])=[O:13])[C:9](=[O:16])[CH2:8][CH2:7][C:6]2[CH:17]=[CH:18][C:3]([O:2][CH3:1])=[CH:4][C:5]=2[O:11]1

Participants

6

Reactant 4

HCID 4875Potassium IodideHCID 80061-Bromo-3-chloropropaneHCID 11430Potassium CarbonateHCID 13808681HCID 13808681, compound

Product 1

HCID 13808684HCID 13808684, compoundYield 93.1%

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Procedure

A solution of 15 g of methyl 3-(4-methoxy-2-methoxy-carbonylmethyloxyphenyl)propionate in 200 ml of toluene is added dropwise to a suspension of 5.6 g of 60% oily sodium hydride in 200 ml of toluene to which 0.4 ml of tert-butanol is added, for a period of 8 hours with heating under refluxing. The reaction mixture is heated under refluxing for 30 minutes and allowed to stand overnight, and then poured into ice water containing 10 ml of acetic acid. The organic layer is separated, washed with water, dried and evaporated under reduced pressure. The residue is purified by column chromatography on silica gel (eluant: hexane:ethyl acetate=4:1) to give 9.5 g of methyl 8-methoxy-3-oxo-2,3,4,5-tetrahydro-1-benzoxepin-2-carboxylate as a colorless oil. A mixture of 7.4 g of methyl 8-methoxy-3-oxo-2,3,4,5-tetrahydro-1-benzoxepin-2-carboxylate, 10.9 g of 1-bromo-3-chloropropane, 1.5 g of potassium iodide, 10 g of anhydrous potassium carbonate and 300 ml of acetonitrile is heated under refluxing with stirring for 5 hours. After cooling, the inorganic substances are filtered off and the filtrate is concentrated under reduced pressure. The residue is purified by column chromatography on silica gel (eluant: hexane:ethyl acetate=8:1) to give 9 g of methyl 2-(3-chloropropyl)-8-methoxy-3-oxo-2,3,4,5-tetrahydro-1-benzoxepin-2-carboxylate as an oil. In 100 ml of methanol is dissolved 9 g of methyl 2-(3-chloropropyl)-8-methoxy-3-oxo-2,3,4,5-tetrahydro-1-benzoxepin-2-carboxylate, and 0.6 g of sodium borohydride is added in small portions to the solution under ice-cooling with stirring. The reaction mixture is concentrated under reduced pressure, and the residue is treated with water and extracted with ethyl acetate. The organic layer is washed with water, dried and evaporated under reduced pressure, and the residue is purified by column chromatography on silica gel (eluant: hexane:ethyl acetate=3:1) to give 3.3 g of methyl trans-2-(3-chloropropyl)-3-hydroxy-8-methoxy-2,3,4,5-tetrahydro-1-benzoxepin-2-carboxylate as a colorless oil from the first fraction eluted.

Workup

  1. temperatureis heated
  2. temperatureunder refluxing
  3. temperatureAfter cooling
  4. filtrationthe inorganic substances are filtered off
  5. concentrationthe filtrate is concentrated under reduced pressure
  6. customThe residue is purified by column chromatography on silica gel (eluant: hexane:ethyl acetate=8:1)

Sources & evidence

ORD record
ord-1ab2f89a21e141e2bd4bbf42482dee32
Source dataset
uspto-grants-1988_04
Patent number
US04736031

Reaction notes

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