4-Nitrophenol → HCID 21525735, compound

HRID 1658837Notes

Reaction equation

HRID 1658837 reaction equation
[C:1](Cl)(Cl)=[O:2].[N:5]1([C:10]2[C:15]3[CH:16]=[CH:17][CH:18]=[CH:19][C:14]=3[S:13](=[O:21])(=[O:20])[CH2:12][CH:11]=2)[CH2:9][CH2:8][CH2:7][CH2:6]1.C(N(CC)CC)C.[CH:29]1[C:34]([N+:35]([O-:37])=[O:36])=[CH:33][CH:32]=[C:31]([OH:38])[CH:30]=1>C1C=CC=CC=1.O1CCCC1>[N:5]1([C:10]2[C:15]3[CH:16]=[CH:17][CH:18]=[CH:19][C:14]=3[S:13](=[O:21])(=[O:20])[CH2:12][C:11]=2[C:1]([O:38][C:31]2[CH:32]=[CH:33][C:34]([N+:35]([O-:37])=[O:36])=[CH:29][CH:30]=2)=[O:2])[CH2:9][CH2:8][CH2:7][CH2:6]1

Participants

7

Reactant 4

HCID 9804-NitrophenolHCID 6371PhosgeneHCID 8471Triethylamine2×HCID 214134244-(Pyrrolidin-1-yl)-1-benzothiopyran-1,1(2H)-dione

Product 1

HCID 21525735HCID 21525735, compoundYield 62.7%

Reagents, catalysts & solvents 2

HCID 241BenzeneSolventHCID 8028TetrahydrofuranSolvent3×

Procedure

A solution of 6.0 g (0.06 mol) of phosgene in 55 ml of benzene was diluted with 30 ml of tetrahydrofuran and cooled to -10°. To this was added over a period of 30 min, a solution of 12.6 g (0.05 mol) of 4-(1-pyrrolidinyl)-2H-1-benzothiopyran 1,1-dioxide and 10 ml of triethylamine in 400 ml of tetrahydrofuran and the reaction mixture was stirred at room temperature for 3 hr. It was cooled to -40° and a solution of 7.7 g (0.055 mol) of p-nitrophenol and 12 ml of triethylamine in 50 ml of tetrahydrofuran was added. The mixture was stirred at room temperature for 16 hr, refluxed for 3 hr, and most of the solvent was evaporated. It was treated with ice-water and extracted ith dichloromethane. The dried dichloromethane phase was evaporated to an oily residue which became a gummy semisolid on trituration with several portions of ether. This gum was dissolved in dichloromethane. Slow distillation resulted in the crystallization of 13.0 g of product, mp 171°-174° dec. Recrystallization from a mixture of 250 ml of tetrahydrofuran and 250 ml of isopropyl ether gave 10.7 g of material, mp 175°-178° dec.

Workup

  1. temperaturecooled to -10°
  2. additionTo this was added over a period of 30 min
  3. temperatureIt was cooled to -40°
  4. temperaturerefluxed for 3 hr
  5. custommost of the solvent was evaporated
  6. additionIt was treated with ice-water
  7. extractionextracted ith dichloromethane
  8. customThe dried dichloromethane phase was evaporated to an oily residue which
  9. dissolutionThis gum was dissolved in dichloromethane
  10. distillationdistillation

Sources & evidence

ORD record
ord-00c5ca465bc247489779cea1c4133af4
Source dataset
uspto-grants-1976_06
Patent number
US03966765

Reaction notes

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