Hydrochloric Acid → 8-t-Butoxy-2,2,6,6-tetramethylbenzo[1,2-d;5,4-d']bis(1,3)oxathiole

HRID 1940460Notes

Reaction equation

HRID 1940460 reaction equation
[CH3:1][C:2]1([CH3:16])[S:6][C:5]2=[CH:7][C:8]3[S:9][C:10]([CH3:15])([CH3:14])[O:11][C:12]=3[CH:13]=[C:4]2[O:3]1.[Li]CCCC.[Mg+2].[Br-].[Br-].[C:25]([O:29]OC(=O)C1C=CC=CC=1)([CH3:28])([CH3:27])[CH3:26].Cl>C(OCC)C.CCCCCC>[C:25]([O:29][C:13]1[C:4]2[O:3][C:2]([CH3:16])([CH3:1])[S:6][C:5]=2[CH:7]=[C:8]2[S:9][C:10]([CH3:15])([CH3:14])[O:11][C:12]=12)([CH3:28])([CH3:27])[CH3:26]

Participants

8

Reactant 5

HCID 313Hydrochloric AcidHCID 11966tert-Butyl peroxybenzoateHCID 82241Magnesium BromideHCID 187852282,2,6,6-Tetramethylbenzo[1,2-d:5,4-d']bis(1,3)oxathioleHCID 178418339Butyllithium

Product 1

HCID 867517528-t-Butoxy-2,2,6,6-tetramethylbenzo[1,2-d;5,4-d']bis(1,3)oxathiole

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolvent3×HCID 8058HexaneSolvent

Conditions

Temperature
-78 °C

Procedure

2,2,6,6-Tetramethylbenzo[1,2-d:5,4-d']bis(1,3)oxathiole (300 mg, 1.18 mmol) was dissolved in dry diethyl ether (30 mL) and the solution was cooled to -78° C. A solution of n-BuLi in hexane (2.5M, 0.52 mL) was added and the reaction was allowed to attain room temperature. After stirring for 1 hour, the mixture was cooled to -78° C. and transferred into a solution of MgBr2 in dry ether (prepared from magnesium, 60 mg and 1,2-dibromoethane, 0.2 mL in 2 mL ether) kept at -78° C. The mixture was stirred for 30 minutes at 0° C. and then, a solution of t-butylperbenzoate (0.24 mL, 0.12 mmol) in dry ether (2 mL) was added. After stirring for 1 hour at 0° C., the mixture was poured onto a mixture of ice and 0.1M aqueous HCl. The aqueous phase was extracted three times with ether and the combined organic phases were washed with aqueous NaHSO3, 2M NaOH, dried (MgSO4) and evaporated. The product was purified by preparative HPLC (RP-18, CH3CN: H2O 80:20). Yield 124 mg (32%).

Workup

  1. customto attain room temperature
  2. temperaturethe mixture was cooled to -78° C.
  3. customkept at -78° C
  4. stirringThe mixture was stirred for 30 minutes at 0° C.
  5. stirringAfter stirring for 1 hour at 0° C.
  6. extractionThe aqueous phase was extracted three times with ether
  7. washthe combined organic phases were washed with aqueous NaHSO3, 2M NaOH
  8. dry with materialdried (MgSO4)
  9. customevaporated
  10. customThe product was purified by preparative HPLC (RP-18, CH3CN: H2O 80:20)

Sources & evidence

ORD record
ord-54bf8c0f644d47ee99c8017beb3bc539
Source dataset
uspto-grants-1997_12
Patent number
US05700448

Reaction notes

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