Sodium Iodide → 3-(Tert-butyl-dimethylsilanyloxy)-2-formyl-5-methoxy-6-methyl-benzoic acid methyl ester

HRID 234222Notes

Reaction equation

HRID 234222 reaction equation
[C:1]([Si:5]([CH3:8])([CH3:7])Cl)([CH3:4])([CH3:3])[CH3:2].[I-].[Na+].[CH3:11][O:12][C:13](=[O:26])[C:14]1[C:19]([CH3:20])=[C:18]([O:21][CH3:22])[CH:17]=[C:16]([OH:23])[C:15]=1[CH:24]=[O:25].C(N(CC)CC)C>C(#N)C>[CH3:11][O:12][C:13](=[O:26])[C:14]1[C:19]([CH3:20])=[C:18]([O:21][CH3:22])[CH:17]=[C:16]([O:23][Si:5]([C:1]([CH3:4])([CH3:3])[CH3:2])([CH3:8])[CH3:7])[C:15]=1[CH:24]=[O:25]

Participants

6

Reactant 4

HCID 5238Sodium IodideHCID 8471TriethylamineHCID 28928tert-Butyldimethylsilyl chlorideHCID 538818172-Formyl-3-hydroxy-5-methoxy-6-methylbenzoic acid methyl ester

Product 1

HCID 544446373-(Tert-butyl-dimethylsilanyloxy)-2-formyl-5-methoxy-6-methyl-benzoic acid methyl esterYield 61.5%

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Procedure

A mixture of 10.0 g of tert-butyl-dimethyl-chlorosilane and 10.0 g of sodium iodide in 50 ml of acetonitrile was stirred at room temperature for 1 h. The mixture was cooled to 0° C. and 14.0 g of 2-formyl-3-hydroxy-5-methoxy-6-methylbenzoic acid methyl ester were added at once followed by dropwise addition of 6.7 g of triethylamine over 15 min. The mixture was allowed to warm to room temperature and stirred for 2 h. The reaction mixture was partitioned between water and ethyl acetate. The organic layer was washed successively with 2N potassium hydrogensulfate, saturated sodium bicarbonate and brine, dried over magnesium sulfate and evaporated in vacuo. The solid residue was recrystallized from ethyl acetate/hexane to-give 13.0 g of 3-(tert-butyl-dimethylsilanyloxy)-2-formyl-5-methoxy-6-methyl-benzoic acid methyl ester as white crystals, m.p; 125°-131° C.

Workup

  1. temperatureThe mixture was cooled to 0° C.
  2. temperatureto warm to room temperature
  3. stirringstirred for 2 h
  4. customThe reaction mixture was partitioned between water and ethyl acetate
  5. washThe organic layer was washed successively with 2N potassium hydrogensulfate, saturated sodium bicarbonate and brine
  6. dry with materialdried over magnesium sulfate
  7. customevaporated in vacuo
  8. customThe solid residue was recrystallized from ethyl acetate/hexane

Sources & evidence

ORD record
ord-d983d6762b86486385a9d5f7726cbc38
Source dataset
uspto-grants-1997_01
Patent number
US05594135

Reaction notes

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