2,2,6,6-Tetramethylbenzo[1,2-d:4,5-d']-bis(1,3)dithiole → Bis-(2,2,6,6-tetramethylbenzo[1,2-d:4,5-d']-bis(1,3)dithiole-4-yl)-mono-(2,2,6,6-tetramethylbenzo[1,2-d:4,5-d']-bis(1,3)dioxol-4-yl)methanol

HRID 2594Notes

Reaction equation

HRID 2594 reaction equation
[CH3:1][C:2]1([CH3:16])[S:6][C:5]2[CH:7]=[C:8]3[S:12][C:11]([CH3:14])([CH3:13])[S:10][C:9]3=[CH:15][C:4]=2[S:3]1.[CH2:17]([Li])[CH2:18][CH2:19][CH3:20].C[O:23][C:24]([C:26]1[C:36]2[O:37][C:38]([CH3:41])([CH3:40])[O:39][C:35]=2[CH:34]=[C:28]2[O:29][C:30]([CH3:33])([CH3:32])[O:31][C:27]=12)=O>C1COCC1>[CH3:13][C:11]1([CH3:14])[S:10][C:9]2[C:15]([C:24]([C:17]3[C:5]4[S:6][C:2]([CH3:16])([CH3:1])[S:3][C:4]=4[CH:20]=[C:19]4[S:12][C:11]([CH3:13])([CH3:14])[S:10][C:18]=34)([C:26]3[C:27]4[O:31][C:30]([CH3:32])([CH3:33])[O:29][C:28]=4[CH:34]=[C:35]4[O:39][C:38]([CH3:40])([CH3:41])[O:37][C:36]=34)[OH:23])=[C:4]3[S:3][C:2]([CH3:16])([CH3:1])[S:6][C:5]3=[CH:7][C:8]=2[S:12]1

Participants

5

Reactant 3

HCID 111969402,2,6,6-Tetramethylbenzo[1,2-d:4,5-d']-bis(1,3)dithioleHCID 206693184-Methoxycarbonyl-2,2,6,6-tetramethylbenzo[1,2-d:4,5-d']-bis-(1,3)-dioxoleHCID 178418339Butyllithium

Product 1

HCID 86752294Bis-(2,2,6,6-tetramethylbenzo[1,2-d:4,5-d']-bis(1,3)dithiole-4-yl)-mono-(2,2,6,6-tetramethylbenzo[1,2-d:4,5-d']-bis(1,3)dioxol-4-yl)methanolYield 44%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

2,2,6,6-Tetramethylbenzo[1,2-d:4,5-d']bis(1,3)dithiole (2.86 g, 10 mmol; prepared according to WO-91/12024) was dissolved in anhydrous THF (75 mL) and cooled to -70° C. n-Butyllithium (4.4 mL, 2.5M in hexane) was added. The reaction mixture was allowed to reach ambient temperature. 4-Methoxycarbonyl-2,2,6,6-tetramethylbenzo-[1,2-d:4,5-d')-bis-(1,3)-dioxole (1.4 g, 5 mmol) was added as a solid. After 1 hour, the mixture was quenched with saturated aqueous NaH2PO4. The aqueous phase was discarded and the organic layer evaporated. The residue was dissolved in dichloromethane, washed with water and dried (Na2SO4). The product was purified by column chromatography (dichloromethane:heptane, 1:1) giving 1.8 g (44%) of pure product.

Workup

  1. customprepared
  2. additionwas added
  3. customto reach ambient temperature
  4. customthe mixture was quenched with saturated aqueous NaH2PO4
  5. customthe organic layer evaporated
  6. dissolutionThe residue was dissolved in dichloromethane
  7. washwashed with water
  8. dry with materialdried (Na2SO4)
  9. customThe product was purified by column chromatography (dichloromethane:heptane, 1:1)

Sources & evidence

ORD record
ord-6735643c3b9e41779184084c922223ce
Source dataset
uspto-grants-1998_03
Patent number
US05728370

Reaction notes

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