Hydrogen Sulfide → 2,3-Di-p-anisyl-5-p-tolylthiophene

HRID 46655Notes

Reaction equation

HRID 46655 reaction equation
[CH2:1]([C:10](=O)[C:11]([CH2:22][C:23]1[CH:28]=[CH:27][C:26]([O:29][CH3:30])=[CH:25][CH:24]=1)=[CH:12][C:13]([C:15]1[CH:20]=[CH:19][C:18]([CH3:21])=[CH:17][CH:16]=1)=O)[C:2]1[CH:7]=[CH:6][C:5]([O:8][CH3:9])=[CH:4][CH:3]=1.P12(SP3(SP(SP(S3)(S1)=S)(=S)S2)=S)=[S:33].S.[OH-].[Na+]>C(O)C.C1(C)C(C)=CC=CC=1>[CH2:1]([C:10]1[S:33][C:13]([C:15]2[CH:20]=[CH:19][C:18]([CH3:21])=[CH:17][CH:16]=2)=[CH:12][C:11]=1[CH2:22][C:23]1[CH:28]=[CH:27][C:26]([O:29][CH3:30])=[CH:25][CH:24]=1)[C:2]1[CH:7]=[CH:6][C:5]([O:8][CH3:9])=[CH:4][CH:3]=1

Participants

7

Reactant 4

HCID 402Hydrogen Sulfide2×HCID 14798Sodium HydroxideHCID 14817Phosphorus sulfide (P2S5)HCID 57279740HCID 57279740, compound

Product 1

HCID 203866722,3-Di-p-anisyl-5-p-tolylthiophene

Reagents, catalysts & solvents 2

HCID 702EthanolSolventHCID 7237O-XyleneSolvent

Procedure

In a 1-liter stainless steel autoclave equipped with stirrer were placed 40.6 g (0.105 mole) of 1,2-di-p-anisyl-4-p-tolylbutene-1,4-dione, 100 ml of xylene and 25 g (0.056 mole) of phosphorus pentasulfide. The vessel was chilled with a Dry Ice-acetone bath and charged with 130 g (3.81 moles) of hydrogen sulfide. The autoclave was then heated with stirring for 215 minutes at 158°-165° C. (1250-1360 psig). After cooling the vessel, the hydrogen sulfide was allowed to vent into a sodium hydroxide solution. The residue was treated with 150 ml of absolute ethanol to destroy unreacted phosphorus pentasulfide. After removal of the ethanol there remained 70.5 g of crude product. Recrystallization from ethanol-dioxane (70:30) gave 20 g (49.3%) of pure 2,3-di-p-anisyl-5-p-tolythiophene, m.p. 99°-102° C. and a second crop of 6.5 g (16.0%) m.p. 92°-96° C.

Workup

  1. temperatureThe vessel was chilled with a Dry Ice-acetone bath
  2. temperatureThe autoclave was then heated
  3. temperatureAfter cooling the vessel
  4. customto destroy unreacted phosphorus pentasulfide
  5. customAfter removal of the ethanol there remained 70.5 g of crude product
  6. customRecrystallization from ethanol-dioxane (70:30)
  7. customgave 20 g (49.3%) of pure 2,3-di-p-anisyl-5-p-tolythiophene, m.p. 99°-102° C.

Sources & evidence

ORD record
ord-cbf44bfcc2da40f6a16f47af255540fa
Source dataset
uspto-grants-1979_11
Patent number
US04174405

Reaction notes

Loading…