2,2-Dimethoxypropane → HCID 21993607, compound

HRID 1978318Notes

Reaction equation

HRID 1978318 reaction equation
[H-].[Al+3].[Li+].[H-].[H-].[H-].O=[C:8]1[C:16]2[C:11](=[CH:12][C:13]([C:17]([OH:19])=O)=[CH:14][CH:15]=2)[C:10](=[O:20])[O:9]1.CO[C:23](OC)([CH3:25])[CH3:24].CC1(C)[C@]2(CS(O)(=O)=O)C(C[C@H]1CC2)=O>O1CCCC1.CN(C)C=O.[OH-].[Na+].CC(C)=O.O.C(OCC)(=O)C>[CH3:24][C:23]1([CH3:25])[O:20][CH2:10][C:11]2[CH:12]=[C:13]([CH2:17][OH:19])[CH:14]=[CH:15][C:16]=2[CH2:8][O:9]1

Participants

11

Reactant 4

HCID 64952,2-DimethoxypropaneHCID 11089Trimellitic anhydrideHCID 65617D-Camphorsulfonic AcidHCID 21226445Aluminium lithium hydride2×

Product 1

HCID 21993607HCID 21993607, compound

Reagents, catalysts & solvents 6

HCID 180AcetoneSolventHCID 962WaterSolventHCID 6228DimethylformamideSolventHCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolventHCID 14798Sodium HydroxideSolvent

Procedure

To a suspension of 25.1 g (661 mM) of lithium aluminum hydride in 1300 ml of tetrahydrofuran was added 50.77 g (264.2 mM) of 1,3-dioxo-1,3-dihydroisobenzofuran-5-carboxylic acid (trimellitic anhydride) in small portions under ice-cooling and the mixture was stirred at room temperature for one day. To this reaction mixture was added ethyl acetate with ice-cooling to decompose the excess lithium aluminum hydride and water was added until a white precipitate had formed. The precipitate was filtered off with the aid of celite and the celite was washed with ethyl acetate and ethanol. The filtrate and washes were pooled and the solvent was distilled off under reduced pressure. The crude [2,4-bis(hydroxymethyl)-phenyl]methanol thus obtained was dissolved in 100 ml of N,N-dimethylformamide. Then, 100 ml of acetone, 70 ml of 2,2-dimethoxypropane, and 5 g of DL-10-camphorsulfonic acid were added and the mixture was stirred at room temperature overnight. This reaction mixture was diluted with aqueous solution of sodium hydroxide and extracted with 6 portions of ethyl acetate. The pooled organic solution was dried over MgSO4 and the solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (hexane/ethyl acetate=3/1 to 1/1) to provide the title compound.

Workup

  1. temperaturecooling
  2. temperaturecooling
  3. additionwas added until a white precipitate
  4. customhad formed
  5. filtrationThe precipitate was filtered off with the aid of celite
  6. washthe celite was washed with ethyl acetate and ethanol
  7. distillationthe solvent was distilled off under reduced pressure
  8. customThe crude [2,4-bis(hydroxymethyl)-phenyl]methanol thus obtained
  9. stirringthe mixture was stirred at room temperature overnight
  10. extractionextracted with 6 portions of ethyl acetate
  11. dry with materialThe pooled organic solution was dried over MgSO4
  12. distillationthe solvent was distilled off under reduced pressure
  13. customThe residue was purified by silica gel column chromatography (hexane/ethyl acetate=3/1 to 1/1)

Sources & evidence

ORD record
ord-956d4fd9424545b391b584dcae3a7158
Source dataset
uspto-grants-2001_05
Patent number
US06235731B1

Reaction notes

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