Quinone → 2-Thioxonaphth[2,3-d] [1,3]dithiol-5,8-dione

HRID 41605

Reaction equation

HRID 41605 reaction equation
Br[CH2:2][C:3]1[S:4][C:5](=[S:10])[S:6][C:7]=1[CH2:8]Br.[C:11]1(=[O:18])[CH:16]=[CH:15][C:14](=[O:17])[CH:13]=[CH:12]1.ClC1C(=O)C(C#N)=C(C#N)C(=O)C=1Cl>[I-].C([N+](CC)(CC)CC)C.C(#N)C>[S:10]=[C:5]1[S:4][C:3]2[CH:2]=[C:12]3[C:13](=[CH:8][C:7]=2[S:6]1)[C:14](=[O:17])[CH:15]=[CH:16][C:11]3=[O:18]

Participants

6

Reactant 3

HCID 4650QuinoneHCID 67752,3-Dichloro-5,6-dicyano-1,4-benzoquinoneHCID 110884794,5-Bis(bromomethyl)-1,3-dithiol-2-thione

Product 1

HCID 154688092-Thioxonaphth[2,3-d] [1,3]dithiol-5,8-dioneYield 78%

Reagents, catalysts & solvents 2

HCID 6225Tetraethylammonium IodideCatalystHCID 6342AcetonitrileSolvent

Procedure

In a vessel, the 4,5-bis(bromomethyl)-1,3-dithiol-2-thione: 1-3 (1.10 g), tetraethylammonium iodide (0.38 g), p-benzoquinone (2.77 g), and acetonitrile (60 mL) were charged, and then refluxed for 1 hour. Thereafter, dichloro dicyano benzoquinone (1.62 g) was added in the resultant mixture, and then refluxed for 7 hours. After completion of the reflux, the solvent was distilled away, and methanol was added in the vessel, and then the precipitate was recovered through filtration. The precipitate was washed with methanol, distilled water, and ether in this order, the obtained residue was dissolved in chloroform, and then filtered. The obtained filtrate was recrystallized, to thereby obtain 2-thioxonaphth[2,3-d] [1,3]dithiol-5,8-dione: 1-4 in a yield of 78%. The target compound was identified through NMR analysis: 1H-NMR (CDCl3, TMS) σ: 7.04 (s, 2H), 8.15 (s, 2H).

Workup

  1. temperaturerefluxed for 1 hour
  2. temperaturerefluxed for 7 hours
  3. distillationAfter completion of the reflux, the solvent was distilled away
  4. additionmethanol was added in the vessel
  5. filtrationthe precipitate was recovered through filtration
  6. washThe precipitate was washed with methanol
  7. distillationdistilled water, and ether in this order
  8. dissolutionthe obtained residue was dissolved in chloroform
  9. filtrationfiltered
  10. customThe obtained filtrate was recrystallized

Sources & evidence

ORD record
ord-52e73abbae0745c5ae679ecdd815abf1
Source dataset
uspto-grants-2013_09
Patent number
US08530673B2

Linked notes

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