Carbon Dioxide → 2,2,6,6-Tetramethylbenzo [1,2-d:4,5-d']-bis(1,3)dioxole-4-carboxylic Acid

HRID 2592Notes

Reaction equation

HRID 2592 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.[C:22](=[O:24])=[O:23].[OH-].[Na+]>C1COCC1.CCCCCC.O>[CH3:13][C:11]1([CH3:14])[O:10][C:9]2[C:15]([C:22]([OH:24])=[O:23])=[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

8

Reactant 4

HCID 280Carbon DioxideHCID 14798Sodium HydroxideHCID 109220852,2,6,6-Tetramethylbenzo[1,2-d:4,5-d']bis([1,3]dioxole)HCID 178418339Butyllithium

Product 1

HCID 211891412,2,6,6-Tetramethylbenzo [1,2-d:4,5-d']-bis(1,3)dioxole-4-carboxylic Acid

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 8028TetrahydrofuranSolventHCID 8058HexaneSolvent

Conditions

Temperature
-20 °C

Procedure

2,2,6,6-Tetramethylbenzo[1,2-d:4,5-d']-bis(1,3)dioxole (10.0 g, 45.0 mmol; prepared according to WO-91/12024) was dissolved in dry THF (200 mL) under an argon atmosphere. The solution was cooled to -20° C. and n-butyllithium (20.0 mL, 50.0 mmol) in hexane was added. After attaining ambient temperature, the reaction mixture was transferred onto solid carbon dioxide (150 g) and allowed to stand overnight. Water (200 mL) was added and pH was adjusted to 10 using 2M aqueous NaOH. After washing with ether, the aqueous phase was acidified with 2M hydrochloric acid to pH 2 and extracted with ether (2*300 mL). The organic phases were dried (Na2SO4) and evaporated to give the pure product.

Workup

  1. customprepared
  2. customAfter attaining ambient temperature
  3. washAfter washing with ether
  4. extractionextracted with ether (2*300 mL)
  5. dry with materialThe organic phases were dried (Na2SO4)
  6. customevaporated
  7. customto give the pure product

Sources & evidence

ORD record
ord-ccded561afe0424fa8a1fedcae175ed7
Source dataset
uspto-grants-1998_03
Patent number
US05728370

Reaction notes

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