Water → 4a'-methyl-(4'H,5'H,7'H)-spiro[1,3-dithiolane-2,2'-naphthalen]-5'(6'H)-one

HRID 551302Notes

Reaction equation

HRID 551302 reaction equation
[CH3:1][C:2]12[C:12](=[O:13])[CH2:11][CH2:10][CH2:9][C:8]1=[CH:7][C:5](=O)[CH2:4][CH2:3]2.C1(C)C=CC(S(O)(=O)=O)=CC=1.[CH2:25]([SH:28])[CH2:26][SH:27].O>C(O)(=O)C>[CH3:1][C:2]12[C:12](=[O:13])[CH2:11][CH2:10][CH:9]=[C:8]1[CH2:7][C:5]1([S:28][CH2:25][CH2:26][S:27]1)[CH2:4][CH2:3]2

Participants

6

Reactant 4

HCID 962WaterHCID 6101p-Toluenesulfonic acidHCID 109021,2-EthanedithiolHCID 89262(+-)-Wieland-Miescher ketone

Product 1

HCID 873063524a'-methyl-(4'H,5'H,7'H)-spiro[1,3-dithiolane-2,2'-naphthalen]-5'(6'H)-oneYield 87.3%

Reagents, catalysts & solvents 1

HCID 176Acetic AcidSolvent

Procedure

To a solution of Wieland-Miescher ketone (5.87 g, 33.0 mmol) in glacial acetic acid (40 mL) was added p-toluenesulfonic acid (2.94 g) followed by dropwise addition of 1,2-ethanedithiol over a 1 hour period. The reaction mixture was stirred at room temperature for another 4 hours, poured into 30 mL water, and stirred for 15 minutes. The white solid was filtered off, washed successively with water, diluted with NaHCO3 solution and water, and then dried to yield thioketal 239 (7.33 g, 87.3%) as a white solid. 1H NMR (CDCl3) δ 1.50-2.70 (m, 10H), 3.20-3.40 (m, 4H), 5.67 (s, 1H); 13C NMR (CDCl3) 212.92, 141.23, 128.04, 64.81, 49.43, 40.11, 39.62, 37.92, 37.57, 30.81, 30.69, 24.73, 24.57.

Workup

  1. stirringstirred for 15 minutes
  2. filtrationThe white solid was filtered off
  3. washwashed successively with water
  4. additiondiluted with NaHCO3 solution and water
  5. customdried

Sources & evidence

ORD record
ord-cc142728007f45cdbfed7e77cd79e7d2
Source dataset
uspto-grants-2011_05
Patent number
US07947726B2

Reaction notes

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