Allyl chloride → 2,3-Dihydro-2,5-dimethyl-4-chloro-7-nitrobenzofuran

HRID 1981628Notes

Reaction equation

HRID 1981628 reaction equation
[Cl:1][C:2]1[CH:3]=[C:4]([OH:12])[C:5]([N+:9]([O-:11])=[O:10])=[CH:6][C:7]=1[CH3:8].[OH-].[Na+].Cl[CH2:16][CH:17]=[CH2:18]>CS(C)=O>[CH3:16][CH:17]1[CH2:18][C:3]2[C:2]([Cl:1])=[C:7]([CH3:8])[CH:6]=[C:5]([N+:9]([O-:11])=[O:10])[C:4]=2[O:12]1

Participants

5

Reactant 3

HCID 7850Allyl chlorideHCID 14798Sodium HydroxideHCID 135603035-Chloro-4-methyl-2-nitrophenol

Product 1

HCID 135756772,3-Dihydro-2,5-dimethyl-4-chloro-7-nitrobenzofuran

Reagents, catalysts & solvents 1

HCID 679Dimethyl SulfoxideSolvent

Conditions

Temperature
190 °C

Procedure

A mixture of 93.4 g of 1B, 750 ml of DMSO, 48 g of 50% aqueous sodium hydroxide and 45.9 g of 3-chloropropene was stirred for 8 hours at 75°-80° C., then for 16 hours at room temperature. The resulting mixture was added to 3 liters of ice water, and the resulting mixture was extracted with methylene chloride. The extract was washed with water, dried (MgSO4) and evaporated to dryness. The residue, in a nitrogen atmosphere, was heated slowly to 190° C. (one hour) and held at 185°-195° C. for two hours, cooled to room temperature, and dissolved in 250 ml of acetic acid. To this solution, 150 ml of 48% aqueous hydrogen bromide solution was added, and the mixture was stirred at reflux for three hours mixed with 2 liters of ice water and the resulting mixture was extracted with a 1:1 v:v mixture of hexane and ether. The extract was washed with water, 5% aqueous sodium bicarbonate solution, dried (MgSO4), charcoaled and concentrated to dryness. The residue was crystallized from 500 ml of 9:1 v:v hexane/-ether mixture, giving 2,3-dihydro-2,5-dimethyl-4-chloro-7-nitrobenzofuran (1C), m.p.: 114°-116° C.

Workup

  1. waitfor 16 hours at room temperature
  2. extractionthe resulting mixture was extracted with methylene chloride
  3. washThe extract was washed with water
  4. dry with materialdried (MgSO4)
  5. customevaporated to dryness
  6. waitheld at 185°-195° C. for two hours
  7. temperaturecooled to room temperature
  8. dissolutiondissolved in 250 ml of acetic acid
  9. additionTo this solution, 150 ml of 48% aqueous hydrogen bromide solution was added
  10. stirringthe mixture was stirred
  11. temperatureat reflux for three hours
  12. additionmixed with 2 liters of ice water
  13. extractionthe resulting mixture was extracted with a 1:1 v
  14. additionv mixture of hexane and ether
  15. washThe extract was washed with water, 5% aqueous sodium bicarbonate solution
  16. dry with materialdried (MgSO4)
  17. concentrationconcentrated to dryness
  18. customThe residue was crystallized from 500 ml of 9:1 v

Sources & evidence

ORD record
ord-e3a3d046e6354b74a93fcd8ec703823f
Source dataset
uspto-grants-1986_06
Patent number
US04593109

Reaction notes

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