N,N,N',N'-Tetramethylethylenediamine → 2-bromo-6-tert-butylthiophenol

HRID 2292693Notes

Reaction equation

HRID 2292693 reaction equation
CN(C)CCN(C)C.[Li]CCCC.[C:14]([C:18]1[CH:23]=[CH:22][CH:21]=[CH:20][C:19]=1[SH:24])([CH3:17])([CH3:16])[CH3:15].[Li]C(CC)C.[Br:30]C(F)(F)C(F)(F)Br>C1CCCCC1.C1COCC1>[Br:30][C:20]1[CH:21]=[CH:22][CH:23]=[C:18]([C:14]([CH3:17])([CH3:15])[CH3:16])[C:19]=1[SH:24]

Participants

8

Reactant 5

HCID 8037N,N,N',N'-TetramethylethylenediamineHCID 313011,2-Dibromo-1,1,2,2-tetrafluoroethaneHCID 27950322-tert-butylbenzenethiolHCID 178418339ButyllithiumHCID 178418400CID 53628100

Product 1

HCID 107528662-bromo-6-tert-butylthiophenol

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolventHCID 8078CyclohexaneSolvent2×

Conditions

Temperature
0 °C

Procedure

To a solution of tetramethylethylenediamine (198.4 mmol, 30 mL) in cyclohexane (140 mL) is slowly added n-BuLi (198.4 mmol, 99.2 mL; 2M solution in cyclohexane) at 23° C. The resulting solution is cooled to 0° C. A solution of 2-tert-butylthiophenol (15.0 g, 90.2 mmol) in cyclohexane (40 mL) is then added at a rate such that the temperature stays below 10° C. The reaction is then stirred at 0° C. for 5 h and is then allowed to warm to 23° C. overnight. To the resulting yellow solution at 23° C. is added sec-BuLi (90.2 mmol, 69.4 mL of 1.3M solution in cyclohexane) over 0.5 h. The resulting solution gradually turns orange. After 1.5 h, the orange, cloudy reaction mixture is cannulated into a stirring solution of 1,2-dibromotetrafluoroethane (180.4 mmol, 21.5 mL) in THF (50 mL) over 1 h. After addition is complete, the resulting reaction mixture is quenched with 1N HCl (80 mL), and extracted with hexanes (3×100 mL). The hexanes are dried (MgSO4) and evaporated to a dark oil (29.48 g). This oil is taken up in 1N NaOH (100 mL), and extracted with CH2 Cl2 (3×50 mL). The organic phase is discarded, and the aqueous phase is acidified with 12N HCl, and extracted with CH2Cl2 (3×100 mL). The organic phase is dried (MgSO4) and evaporated to provide the title compound as a yellow oil.

Workup

  1. customat 23° C
  2. customstays below 10° C
  3. temperatureto warm to 23° C. overnight
  4. waitAfter 1.5 h
  5. customthe orange, cloudy reaction mixture
  6. additionAfter addition
  7. customthe resulting reaction mixture
  8. customis quenched with 1N HCl (80 mL)
  9. extractionextracted with hexanes (3×100 mL)
  10. dry with materialThe hexanes are dried (MgSO4)
  11. customevaporated to a dark oil (29.48 g)
  12. extractionextracted with CH2 Cl2 (3×50 mL)
  13. extractionextracted with CH2Cl2 (3×100 mL)
  14. dry with materialThe organic phase is dried (MgSO4)
  15. customevaporated

Sources & evidence

ORD record
ord-e1db080cad584b6c8df35d9a95c68f97
Source dataset
uspto-grants-1997_11
Patent number
US05684041

Reaction notes

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