3-Thiophenecarboxaldehyde → HCID 10543725, compound

HRID 2258350Notes

Reaction equation

HRID 2258350 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-].[S:24]1[CH:28]=[CH:27][C:26]([CH:29]=[O:30])=[CH:25]1>O1CCCC1.ClCCl.CCCCCC>[Si:6]([O:5][C:4]1[CH:3]=[C:2]([CH:15]=[CH:14][CH:13]=1)[CH:29]([OH:30])[C:26]1[CH:27]=[CH:28][S:24][CH:25]=1)([C:9]([CH3:12])([CH3:11])[CH3:10])([CH3:8])[CH3:7]

Participants

8

Reactant 4

HCID 681353-ThiophenecarboxaldehydeHCID 82241Magnesium BromideHCID 11254705(3-Bromophenoxy)(tert-butyl)dimethylsilaneHCID 178418339Butyllithium

Product 1

HCID 10543725HCID 10543725, compoundYield 69%

Reagents, catalysts & solvents 3

HCID 6344DichloromethaneSolventHCID 8028TetrahydrofuranSolvent3×HCID 8058HexaneSolvent2×

Conditions

Temperature
-78 °C

Procedure

3-Bromophenoxy-tert-butyldimethylsilane (57.5 g, 0.20 mol, Example 1, infra) was dissolved in 300 mL of dry tetrahydrofuran under nitrogen and cooled to -78° C. A solution of 1.6M n-butyllithium in hexane (125 mL, 0.20 mol) was added dropwise at a rate to maintain a temperature below -70° C. The reaction was stirred for thirty minutes after the addition was complete and the cold solution was transferred to another vessel containing a -40° C. solution of magnesium bromide (37.8 g, 0.205 mol) in 600 mL of dry tetrahydrofuran under nitrogen. The resulting solution was allowed to warm to -15° C. while stirring. After one hour a solution of thiophene-3-carboxaldehyde (22.4 g, 0.20 mol) in 200 mL of dry tetrahydrofuran was added slowly at a rate to maintain a temperature below 25° C. The resulting solution was stirred for 30 minutes at room temperature, then washed twice with aqueous ammonium chloride, dried over sodium sulfate and evaporated to give a brown oil. Chromatography on silica gel with hexane:dichloromethane (gradient from 3:1 to 1:1) gave 44.1 g (69%) of 3-((tert-butyldimethylsilyl)oxy)-α-(3-thienyl)benzyl alcohol as a viscous yellow oil.

Workup

  1. temperatureto maintain a temperature below -70° 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 30 minutes at room temperature
  8. washwashed twice with aqueous ammonium chloride
  9. dry with materialdried over sodium sulfate
  10. customevaporated
  11. customto give a brown oil

Sources & evidence

ORD record
ord-48dca76d72f1470f908a880ed97cb3dc
Source dataset
uspto-grants-1997_08
Patent number
US05658908

Reaction notes

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