Chlorotrimethylsilane → (4-Bromo-2-fluorophenyl)trimethylsilane

HRID 407202

Reaction equation

HRID 407202 reaction equation
C([Li])CCC.Br[C:7]1[CH:12]=[CH:11][C:10]([Br:13])=[CH:9][C:8]=1[F:14].Cl[Si:16]([CH3:19])([CH3:18])[CH3:17].C(=O)=O.CC(C)=O>C(OCC)C.O>[Br:13][C:10]1[CH:11]=[CH:12][C:7]([Si:16]([CH3:19])([CH3:18])[CH3:17])=[C:8]([F:14])[CH:9]=1

Participants

7

Reactant 4

HCID 6397ChlorotrimethylsilaneHCID 1370041,4-Dibromo-2-fluorobenzeneHCID 18522661Acetone cardiceHCID 178418339Butyllithium

Product 1

HCID 11831745(4-Bromo-2-fluorophenyl)trimethylsilaneYield 71%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 3283Diethyl EtherSolvent

Conditions

Temperature
-78 °C

Procedure

A solution of n-butyllithium (n-BuLi, 2.5 Molar (M) in hexanes; 900 microliters (μL), 2.2 millimoles (mmol), 1.1 equivalents (equiv)) was added to a stirred solution of 1,4-dibromo-2-fluorobenzene (500 milligrams (mg), 2.0 mmol, 1.0 equiv) in diethyl ether (Et2O; 10 milliliters (mL)) at −78° C. The resulting pale yellow solution was stirred at −78° C. for 2 hours (h). Chlorotrimethylsilane (TMSCl; 300 μL, 2.4 mmol, 1.2 equiv) was added, and the resulting pale yellow solution was allowed to slowly warm to 23° C., by allowing the dry ice/acetone bath to melt, and was stirred for 72 h. The reaction mixture was diluted with water (H2O; 50 mL) and was extracted with dichloromethane (CH2Cl2; 3×50 mL). The combined organic layers were dried over magnesium sulfate (MgSO4), gravity filtered, and concentrated by rotary evaporation to afford the title compound as a pale yellow oil (350 mg, 71%): IR (thin film) 3068 (w), 2955 (m), 2927 (m), 2855 (w), 1598 (w), 1567 (w) cm−1; 1H NMR (400 MHz, DMSO-d6) δ 7.38-7.49 (m, 3H), 0.30 (s, 9H).

Workup

  1. temperatureto slowly warm to 23° C.
  2. stirringwas stirred for 72 h
  3. extractionwas extracted with dichloromethane (CH2Cl2; 3×50 mL)
  4. dry with materialThe combined organic layers were dried over magnesium sulfate (MgSO4), gravity
  5. filtrationfiltered
  6. concentrationconcentrated by rotary evaporation

Sources & evidence

ORD record
ord-b7525fc90abc4bff8c7d1e4e74a8c488
Source dataset
uspto-grants-2014_06
Patent number
US08754229B2

Linked notes

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