Iodine → 2-[3-(Trimethylsilyl)phenyl]-2-methyl-1,3-dioxolane

HRID 1870537Notes

Reaction equation

HRID 1870537 reaction equation
[Mg].II.Br[C:5]1[CH:6]=[C:7]([C:11]2([CH3:16])[O:15][CH2:14][CH2:13][O:12]2)[CH:8]=[CH:9][CH:10]=1.[CH3:17][Si:18](Cl)([CH3:20])[CH3:19].[NH4+].[Cl-]>C1COCC1>[CH3:17][Si:18]([CH3:20])([CH3:19])[C:5]1[CH:6]=[C:7]([C:11]2([CH3:16])[O:15][CH2:14][CH2:13][O:12]2)[CH:8]=[CH:9][CH:10]=1

Participants

7

Reactant 5

HCID 807IodineHCID 6397ChlorotrimethylsilaneHCID 25517Ammonium ChlorideHCID 5462224MagnesiumHCID 109992182-(3-Bromophenyl)-2-methyl-1,3-dioxolane

Product 1

HCID 186966022-[3-(Trimethylsilyl)phenyl]-2-methyl-1,3-dioxolane

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
65 °C

Procedure

A three-neck flask was charged with magnesium pieces (2.0 g) and tetrahydrofuiran (12 mL) under a nitrogen atmosphere. A small quantity of iodine was added and the mixture turned yellow. To this yellow mixture was added dropwise a solution of the title compound of Step A (20.0 g) in 30 mL of THF. The reaction mixture was warmed to 65° C. during the addition and then was heated at reflux for 1.5 h after the addition was complete. After cooling the reaction to 60° C., a solution of trimethylsilyl chloride (10.4 mL) in THF (12 mL) was added and the mixture was heated at reflux for two hours and then was allowed to stir overnight at room temperature. The reaction mixture was poured into saturated aqueous NH4Cl and the aqueous layer was extracted twice with diethyl ether and then once with ethyl acetate. The combined organic layers were dried over MgSO4, filtered and the was solvent removed to give an oil (20.0 g) which crystallized upon standing. This solid was then recrystallized from pentane to afford 11.2 g of the title compound of Step B as a white solid melting at 54-55° C. 1H NMR (CDCl3): δ 7.63 (s,1H), 7.44 (m,2H), 7.33 (t,1H), 4.0 (m,2H), 3.78 (m,2H), 1.67 (s,3H), 0.27 (s,8H).

Workup

  1. temperaturewas heated
  2. temperatureat reflux for 1.5 h
  3. additionafter the addition
  4. temperatureAfter cooling
  5. customthe reaction to 60° C.
  6. temperaturethe mixture was heated
  7. temperatureat reflux for two hours
  8. extractionthe aqueous layer was extracted twice with diethyl ether
  9. dry with materialThe combined organic layers were dried over MgSO4
  10. filtrationfiltered
  11. customthe was solvent removed

Sources & evidence

ORD record
ord-66aecd33a9284119bc2f690c15349357
Source dataset
uspto-grants-2000_08
Patent number
US06096895

Reaction notes

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