Diethyl Ether → 2,7-Di-tert-butyl-9H-thioxanthene

HRID 1462315Notes

Reaction equation

HRID 1462315 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].[H-].[Al+3].[Li+].[H-].[H-].[H-].[CH3:28]COCC>>[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)[CH2:28][C:7]=2[CH:6]=1)([CH3:4])([CH3:3])[CH3:2]

Participants

4

Reactant 3

HCID 3283Diethyl Ether2×HCID 133451781,1'-Sulfanediylbis(4-tert-butylbenzene)HCID 21226445Aluminium lithium hydride

Product 1

HCID 133451792,7-Di-tert-butyl-9H-thioxantheneYield 72%

Procedure

The red oil obtained as described above from 12 g of bis-(4-t-butylphenyl)-sulfide was dissolved in 100 mL of dry ether, and the solution added dropwise over 15 min. to a suspension of 2.5 g of lithium aluminum hydride in 100 mL of dry ether while cooling in an ice bath. The mixture was refluxed for 3 hours, cooled and excess hydride destroyed by means of saturated ammonium chloride solution. The ether layer was washed with H2O and saturated NaCl solution, dried over MgSO4, and then evaporated to a white solid which was recrystallized from CH2Cl2 -hexane to give 9.0 g (72%) of the thioxanthene as white crystals, m.p. 152°-154°, 'H NMR (CDCl3) δ 1.28 (s, 18H, CH3), 3.84 (s, 2H, CH2), 7.31 (m, 6H, aryl). Anal. calculated for C21H26S: C, 81.23; H, 8.44; S, 10.33. Found: C, 81.45; H, 8.61; S, 10.24.

Workup

  1. customThe red oil obtained
  2. temperaturewhile cooling in an ice bath
  3. temperatureThe mixture was refluxed for 3 hours
  4. temperaturecooled
  5. customexcess hydride destroyed by means of saturated ammonium chloride solution
  6. washThe ether layer was washed with H2O and saturated NaCl solution
  7. dry with materialdried over MgSO4
  8. customevaporated to a white solid which
  9. customwas recrystallized from CH2Cl2 -hexane

Sources & evidence

ORD record
ord-d194e6d608a4466a8307bd096dc57b2f
Source dataset
uspto-grants-1984_07
Patent number
US04460501

Reaction notes

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