N,N,N',N'-Tetramethylethylenediamine → 2-bromo-6-tert-butylthiophenol
Reaction equation
CN(C)CCN(C)C.C([Li])CCC.[C:14]([C:18]1[CH:23]=[CH:22][CH:21]=[CH:20][C:19]=1[SH:24])([CH3:17])([CH3:16])[CH3:15].C([Li])(CC)C.[Br:30]C(F)(F)C(F)(F)Br>C1CCCCC1.O1CCCC1>[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
Reactant 5
Product 1
Reagents, catalysts & solvents 2
Conditions
- Temperature
- 0 °C
Procedure
To a solution of freshly distilled tetramethylethylenediamine (7.5 mL, 50 mmol) in dry cyclohexane (35 mL) is added dropwise at 24° C. a solution of n-butyl lithium in hexanes (31 mL, 50 mmol). After addition is complete, the reaction mixture is cooled to 0° C. A solution of 2-tert-butylthiophenol (3.77 g, 22.7 mmol) in dry cyclohexane (10 mL) is added at a rate such that the reaction temperature stays below 10° C. The reaction is allowed to stir at 24° C. for 14 h. A solution of sec-butyl lithium in hexanes (17.5 mL, 22.7 mmol) is added at this temperature, and the color of the reaction changes from yellow to orange. After 1 h, the reaction mixture is added at -78° C. to a solution of 1,2-dibromotetrafluoroethane (5.4 mL, 45.4 mmol) in dry tetrahydrofuran (100 mL). The mixture is allowed to warm to 24° C., and is partitioned against 0.1N HCl (100 mL). The organic phase is dried (MgSO4), filtered and evaporated to give 2-bromo-6-tert-butylthiophenol as a yellow oil.
Workup
- additionAfter addition
- customstays below 10° C
- customthe color of the reaction changes from yellow to orange
- waitAfter 1 h
- temperatureto warm to 24° C.
- customis partitioned against 0.1N HCl (100 mL)
- dry with materialThe organic phase is dried (MgSO4)
- filtrationfiltered
- customevaporated
Sources & evidence
- ORD record
- ord-82d1258e2f9a4e92b699846a33a90b06
- Source dataset
- uspto-grants-1997_08
- Patent number
- US05656661
Reaction notes
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