2,2,6,6-Tetramethylbenzo[1,2-d:4,5-d']bis([1,3]dioxole) → Tris(2,2,6,6-tetramethylbenzo[1,2-d:4,5-d']bis(1,3)dioxole-4-yl)methanol

HRID 1450040Notes

Reaction equation

HRID 1450040 reaction equation
[CH3:1][C:2]1([CH3:16])[O:6][C:5]2[CH:7]=[C:8]3[O:12][C:11]([CH3:14])([CH3:13])[O:10][C:9]3=[CH:15][C:4]=2[O:3]1.C([Li])CCC.[CH3:22][C:23]1([CH3:55])[O:27][C:26]2[C:28]([C:37]([C:39]3[C:49]4[O:50][C:51]([CH3:54])([CH3:53])[O:52][C:48]=4[CH:47]=[C:41]4[O:42][C:43]([CH3:46])([CH3:45])[O:44][C:40]=34)=[O:38])=[C:29]3[O:33][C:32]([CH3:35])([CH3:34])[O:31][C:30]3=[CH:36][C:25]=2[O:24]1>C1COCC1>[CH3:13][C:11]1([CH3:14])[O:10][C:9]2[C:15]([C:37]([C:28]3[C:26]4[O:27][C:23]([CH3:55])([CH3:22])[O:24][C:25]=4[CH:36]=[C:30]4[O:31][C:32]([CH3:35])([CH3:34])[O:33][C:29]=34)([C:39]3[C:49]4[O:50][C:51]([CH3:53])([CH3:54])[O:52][C:48]=4[CH:47]=[C:41]4[O:42][C:43]([CH3:45])([CH3:46])[O:44][C:40]=34)[OH:38])=[C:4]3[O:3][C:2]([CH3:16])([CH3:1])[O:6][C:5]3=[CH:7][C:8]=2[O:12]1

Participants

5

Reactant 3

HCID 109220852,2,6,6-Tetramethylbenzo[1,2-d:4,5-d']bis([1,3]dioxole)HCID 18943092Bis(2,2,6,6-tetramethylbenzo-(1,2-d:4,5-d']bis(1,3)dioxole-4-yl)ketoneHCID 178418339Butyllithium

Product 1

HCID 10952571Tris(2,2,6,6-tetramethylbenzo[1,2-d:4,5-d']bis(1,3)dioxole-4-yl)methanol

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

2,2,6,6-Tetramethylbenzo[1,2-d:4,5-d']bis(1,3)dioxole (8.80 g, 40.00 mmol, Example 5) was dissolved in THF (100 mL) and cooled to -20° C. n-Butyllithium (25.0 mL, 40.0 mmol, 1.6M) was added and the temperature was adjusted to ambient temperature over a period of 30 minutes and then recooled to -20° C. Bis(2,2,6,6-tetramethylbenzo-[1,2-d:4,5-d']bis(1,3)dioxole-4-yl)ketone (18.80 g, 39.83 mmol, Example 57) was added and the temperature was once more adjusted to room temperature and the mixture was stirred for 18 hours. The mixture was then poured on water/AcOH (100 mL, 2% AcOH) and extracted with diethyl ether (2×100 mL). The organic phase was washed with water (2×100 ml) and dried (Na2SO4). The solvent was evaporated and the product was washed with petroleum ether (20 mL, 40°-60° C.). Yield 10.80 g (64.1%). Spectral data see example 44.

Workup

  1. additionwas added
  2. customrecooled to -20° C
  3. customwas once more adjusted to room temperature
  4. additionThe mixture was then poured on water/AcOH (100 mL, 2% AcOH)
  5. extractionextracted with diethyl ether (2×100 mL)
  6. washThe organic phase was washed with water (2×100 ml)
  7. dry with materialdried (Na2SO4)
  8. customThe solvent was evaporated
  9. washthe product was washed with petroleum ether (20 mL, 40°-60° C.)

Sources & evidence

ORD record
ord-3b59da73ed354d938dfa020edd1ffbe0
Source dataset
uspto-grants-1997_02
Patent number
US05599522

Reaction notes

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