Dichloromethane → 2,7-Di-tert-butyl-9H-thioxanthen-9-one

HRID 1462314Notes

Reaction equation

HRID 1462314 reaction equation
[C:1]([C:5]1[CH:10]=[CH:9][C:8]([S:11][C:12]2[CH:17]=[CH:16][C:15]([C:18]([CH3:21])([CH3:20])[CH3:19])=[CH:14][CH:13]=2)=[CH:7][CH:6]=1)([CH3:4])([CH3:3])[CH3:2].C(Cl)Cl.Cl[Sn](Cl)(Cl)Cl.[CH3:30][O:31]C(Cl)Cl>O>[C:1]([C:5]1[CH:10]=[CH:9][C:8]2[S:11][C:12]3[C:13](=[CH:14][C:15]([C:18]([CH3:21])([CH3:20])[CH3:19])=[CH:16][CH:17]=3)[C:30](=[O:31])[C:7]=2[CH:6]=1)([CH3:4])([CH3:3])[CH3:2]

Participants

6

Reactant 4

HCID 6344DichloromethaneHCID 21004Methane, dichloromethoxy-HCID 24287Tin tetrachlorideHCID 133451781,1'-Sulfanediylbis(4-tert-butylbenzene)

Product 1

HCID 133451802,7-Di-tert-butyl-9H-thioxanthen-9-oneYield 37%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Procedure

To a mixture of 12 g of bis-(4-t-butylphenyl)-sulfide, 100 mL of dry CH2Cl2 and 21 g of SnCl4 cooled in an ice bath for a period of 30 min., a solution of 9.27 g of α,α-dichloromethyl methyl ether in 50 mL of CH2CH2 was added dropwise. After addition was complete, a deep red mixture was obtained which was allowed to warm slowly to room temperature, stirred for 2 hours and then slowly poured into water. Extraction with CHCl3, followed by washing of the extracts successively with H2O, 5% NaHCO3, H2O and saturated NaCl solution, drying over (MgSO4), and evaporation of solvent gave a red oil which was chromatographed on silica gel. Elution by means of hexane-ethyl acetate (95/5) removed 4.6 g (37% of 2,7-di-t-butylthioxanthene after which there was obtained 4.65 g (37%) of the ketone which was recrystallized from hexane --CH2Cl2 as yellow crystals, m.p. 176°-178°, 'NMR (CDCl3) δ 1.35 (s, 18H, CH3), 7.5 (m, 4H, aryl), 8.75 (d, 2H, CHCCO). Anal. calculated for C21H24OS: C, 77.73; H, 7.46; S, 9.88. Found C, 77.83; H, 7.58; S, 9.75.

Workup

  1. temperaturecooled in an ice bath for a period of 30 min.
  2. additionAfter addition
  3. customa deep red mixture was obtained which
  4. extractionExtraction with CHCl3
  5. washby washing of the extracts successively with H2O, 5% NaHCO3, H2O and saturated NaCl solution
  6. dry with materialdrying over (MgSO4), and evaporation of solvent
  7. customgave a red oil which
  8. customwas chromatographed on silica gel
  9. washElution by means of hexane-ethyl acetate (95/5)
  10. customremoved 4.6 g (37% of 2,7-di-t-butylthioxanthene after which there

Sources & evidence

ORD record
ord-9c29d536806a4ca4b26a7291d2c035dd
Source dataset
uspto-grants-1984_07
Patent number
US04460501

Reaction notes

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