Magnesium Bromide → HCID 10810945, compound

HRID 1460104Notes

Reaction equation

HRID 1460104 reaction equation
Br[C:2]1[CH:3]=[C:4]([CH:13]=[CH:14][CH:15]=1)[O:5][Si:6]([C:9]([CH3:12])([CH3:11])[CH3:10])([CH3:8])[CH3:7].C([Li])CCC.[Br-].[Mg+2].[Br-].[Br:24][C:25]1[CH:26]=[C:27]([CH:30]=[O:31])[S:28][CH:29]=1>O1CCCC1.CCCCCC.ClCCl>[Br:24][C:25]1[CH:26]=[C:27]([CH:30]([OH:31])[C:2]2[CH:15]=[CH:14][CH:13]=[C:4]([O:5][Si:6]([C:9]([CH3:12])([CH3:11])[CH3:10])([CH3:8])[CH3:7])[CH:3]=2)[S:28][CH:29]=1

Participants

8

Reactant 4

HCID 82241Magnesium BromideHCID 877924-Bromothiophene-2-carbaldehydeHCID 11254705(3-Bromophenoxy)(tert-butyl)dimethylsilaneHCID 178418339Butyllithium

Product 1

HCID 10810945HCID 10810945, compoundYield 48.2%

Reagents, catalysts & solvents 3

HCID 6344DichloromethaneSolventHCID 8028TetrahydrofuranSolvent3×HCID 8058HexaneSolvent2×

Conditions

Temperature
-78 °C

Procedure

3-Bromophenoxy-tert-butyldimethylsilane (30.2 g, 0.105 mol), prepared as in Example 1, was dissolved in 300 mL of dry tetrahydrofuran under nitrogen and cooled to -78° C. A solution of 1.6M n-butyllithium in hexane (66 mL, 0.105 mol) was added dropwise at a rate to maintain a temperature below -65° C. The reaction was stirred for thirty minutes after the addition was complete and the cold solution was transferred to another vessel containing a room temperature solution of magnesium bromide (20.2 g, 0.11 mol) in 400 mL of dry tetrahydrofuran under nitrogen. The resulting solution was allowed to warm to 15° C. while stirring. After one hour a solution of 4-bromo-2-thiophenecarboxaldehyde (20.0 g, 0.105 mol) in 100 mL of dry tetrahydrofuran was added slowly at a rate to maintain a temperature below 25° C. The resulting solution was stirred for three hours at room temperature, then washed three times with aqueous ammonium chloride, dried over sodium sulfate and evaporated to give a yellow oil. Chromatography on silica gel with dichloromethane:hexane/50:50 gave 20.23 g (48.2%) of α-(4-bromo-2-thienyl)-3-((tert-butyldimethylsilyl)-oxy)benzyl alcohol as a viscous yellow oil.

Workup

  1. temperatureto maintain a temperature below -65° C
  2. additionafter the addition
  3. customthe cold solution was transferred to another vessel
  4. temperatureto warm to 15° C.
  5. stirringwhile stirring
  6. temperatureto maintain a temperature below 25° C
  7. stirringThe resulting solution was stirred for three hours at room temperature
  8. washwashed three times with aqueous ammonium chloride
  9. dry with materialdried over sodium sulfate
  10. customevaporated
  11. customto give a yellow oil

Sources & evidence

ORD record
ord-6844229dee214cd4a9d7e48a8e06e9ec
Source dataset
uspto-grants-1998_12
Patent number
US05854249

Reaction notes

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