Ammonium Chloride → 6-Cyclopropyl-5-vinyl-2-benzofuran-1(3H)-one

HRID 1474340Notes

Reaction equation

HRID 1474340 reaction equation
[CH:1]1([C:4]2[C:5]([CH2:14][CH2:15]O)=[CH:6][C:7]3[CH2:11][O:10][C:9](=[O:12])[C:8]=3[CH:13]=2)[CH2:3][CH2:2]1.CS(Cl)(=O)=O.[Cl-].[NH4+].C1CCN2C(=NCCC2)CC1>O.ClCCl>[CH:1]1([C:4]2[C:5]([CH:14]=[CH2:15])=[CH:6][C:7]3[CH2:11][O:10][C:9](=[O:12])[C:8]=3[CH:13]=2)[CH2:3][CH2:2]1

Participants

7

Reactant 4

HCID 25517Ammonium ChlorideHCID 31297Methanesulfonyl chlorideHCID 811841,8-Diazabicyclo(5.4.0)undec-7-eneHCID 666466836-Cyclopropyl-5-(2-hydroxyethyl)-2-benzofuran-1(3H)-one

Product 1

HCID 666463936-Cyclopropyl-5-vinyl-2-benzofuran-1(3H)-one

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6344DichloromethaneSolvent

Procedure

To a 100 ml flask containing a stir bar was added compound 6-cyclopropyl-5-(2-hydroxyethyl)-2-benzofuran-1(3H)-one, (0.5 g, 2.29 mmol), TEA (20 mL) followed by addition of dichloromethane (25 mL). The flask was placed in a cool bath of ° C., and slowly treated with methanesulfonyl chloride (6.5 mL, 83 mmol). The resulting mixture was then stirred for 20 min. TLC (hexanes/EtOAc=1/1) indicated completion of the reaction. The mixture was poured into saturated ammonium chloride and extracted with DCM. The combined organics were washed with 1 N HCl, saturated sodium bicarbonate solution, and brine, then dried (Na2SO4) and concentrated in vacuo. The residue (LC/MS: [(M+1)]+=297; tR=1.01 min) was dissolved in dichloromethane (25 mL) and treated with DBU (0.7 mL, 4.72 mmol) and stirred for 2 h. TLC monitoring showed conversion to the olefin. The reaction mixture was diluted with water and extracted with dichloromethane. The combined organics were washed with 1N HCl, saturated sodium bicarbonate solution, and brine, then dried (Na2SO4) and concentrated in vacuo. The material was used in the next step without further purification.

Workup

  1. additionTo a 100 ml flask containing a stir bar
  2. customThe flask was placed in a cool bath of ° C
  3. customcompletion of the reaction
  4. extractionextracted with DCM
  5. washThe combined organics were washed with 1 N HCl, saturated sodium bicarbonate solution, and brine
  6. dry with materialdried (Na2SO4)
  7. concentrationconcentrated in vacuo
  8. dissolutionThe residue (LC/MS: [(M+1)]+=297; tR=1.01 min) was dissolved in dichloromethane (25 mL)
  9. stirringstirred for 2 h
  10. extractionextracted with dichloromethane
  11. washThe combined organics were washed with 1N HCl, saturated sodium bicarbonate solution, and brine
  12. dry with materialdried (Na2SO4)
  13. concentrationconcentrated in vacuo
  14. customThe material was used in the next step without further purification

Sources & evidence

ORD record
ord-efa36289ccfb44f18697c92d7a21135d
Source dataset
uspto-grants-2015_04
Patent number
US09018211B2

Reaction notes

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