Hydrogen Sulfide → Triarathene

HRID 46654Notes

Reaction equation

HRID 46654 reaction equation
[C:1]1([C:7](=O)[CH:8]([C:19]2[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=2)[CH2:9][C:10]([C:12]2[CH:17]=[CH:16][C:15]([Cl:18])=[CH:14][CH:13]=2)=O)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.P12(SP3(SP(SP(S3)(S1)=S)(=S)S2)=S)=[S:27].S.[OH-].[Na+]>C(O)C.C1(C)C(C)=CC=CC=1>[C:1]1([C:7]2[S:27][C:10]([C:12]3[CH:17]=[CH:16][C:15]([Cl:18])=[CH:14][CH:13]=3)=[CH:9][C:8]=2[C:19]2[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=2)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1

Participants

7

Reactant 4

HCID 402Hydrogen Sulfide2×HCID 14798Sodium HydroxideHCID 14817Phosphorus sulfide (P2S5)HCID 113255221,4-Butanedione, 4-(4-chlorophenyl)-1,2-diphenyl-

Product 1

HCID 6450825TriaratheneYield 134.7%

Reagents, catalysts & solvents 2

HCID 702EthanolSolventHCID 7237O-XyleneSolvent

Procedure

In a 1-liter stainless steel autoclave equipped with stirrer were placed 76.9 g (0.220 mole) of 1,2-diphenyl4-p-chlorophenylbutane-1,4-dione, 100 ml of xylene and 45 g (0.101 mole) of phosphorus pentasulfide. The autoclave was cooled with a Dry Ice-acetone bath and charged with 120 g (3.52 moles) of hydrogen sulfide. The autoclave was heated with stirring for 200 minutes at 155°-178° C. (1000-2000 psig). The autoclave was cooled and the hydrogen sulfide allowed to escape into a sodium hydroxide solution. The residue was stirred with 150 ml of absolute ethanol. Filtration and drying gave a crude product of 61.2 g (80.2%) m.p. 115°-117°. Recrystallization from 190 ml of toluene and 625 ml of ethanol gave 47.2 g (61.9%) of pure 2,3-diphenyl-5-p-chlorophenylthiophene, m.p. 121°-122° C.

Workup

  1. temperatureThe autoclave was cooled with a Dry Ice-acetone bath
  2. temperatureThe autoclave was heated
  3. temperatureThe autoclave was cooled
  4. filtrationFiltration
  5. customdrying
  6. customgave a crude product of 61.2 g (80.2%) m.p. 115°-117°
  7. customRecrystallization from 190 ml of toluene and 625 ml of ethanol

Sources & evidence

ORD record
ord-3023d7c751fc477492f211786f8263c2
Source dataset
uspto-grants-1979_11
Patent number
US04174405

Reaction notes

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