Chlorotrimethylsilane → HCID 11075297, compound

HRID 392882Notes

Reaction equation

HRID 392882 reaction equation
[CH3:1][Si:2](Cl)([CH3:4])[CH3:3].[C:6]1([S:12][C:13](Br)([F:15])[F:14])[CH:11]=[CH:10][CH:9]=[CH:8][CH:7]=1>CN(C=O)C>[CH3:1][Si:2]([C:13]([S:12][C:6]1[CH:11]=[CH:10][CH:9]=[CH:8][CH:7]=1)([F:15])[F:14])([CH3:4])[CH3:3]

Participants

4

Reactant 2

HCID 6397ChlorotrimethylsilaneHCID 11322389bromodifluoromethyl phenyl sulfide

Product 1

HCID 11075297HCID 11075297, compoundYield 85%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

Into a mixture of 0.22 g (9.2 mmol) Mg turnings, 1.99 g (18.3 mmol) of TMSCl and 20 ml DMF at room temperature, was added 1.1 g (4.6 mmol) bromodifluoromethyl phenyl sulfide (24). The reaction was stirred at room temperature for another 1 h. Excess TMSCl was removed under vacuum (˜10 mmHg). The residue was washed with ice water and then extracted with dichloromethane (20 mL×3). The organic phase was further washed with brine and water successively, and dried over MgSO4. After solvent removal, the crude product was further purified by silica gel chromatography (pentane as eluent) to give 905 mg (85% yield) product 21 as colorless liquid, b.p. 86˜87° C./4 Torr. 1H NMR (500 MHz, CDCl3): δ0.25 (s, 9H); 7.37 (m, 3H); 7.59 (d, 2H). 13C NMR (125 MHz, CDCl3): δ−4.2; 126.3 (t, 3JC-F=4.1 Hz); 128.8; 129.3; 134.0 (t, 1JC-F=300.1 Hz); 136.2. 19F NMR (470 MHz, CDCl3): δ−88.1 (s). 29Si NMR (99 MHz, CDCl3): 7.7 (t, 2JSi-F=31.28 Hz). IR (neat): 3064; 2965; 2904; 1884; 1585; 1475; 1441; 1414; 1307; 1255; 1076; 1025; 962; 884; 850; 825; 744; 703; 690; 631; 607; 496 cm−1. GC-MS (m/z): 232 (M+), 109 (PhS+), 73 (Me3Si+). HRMS (DEI): m/z calculated for C10H14F2SSi (M+) 232.0553, found 232.0545.

Workup

  1. customExcess TMSCl was removed under vacuum (˜10 mmHg)
  2. washThe residue was washed with ice water
  3. extractionextracted with dichloromethane (20 mL×3)
  4. washThe organic phase was further washed with brine and water successively
  5. dry with materialdried over MgSO4
  6. customAfter solvent removal
  7. customthe crude product was further purified by silica gel chromatography (pentane as eluent)

Sources & evidence

ORD record
ord-e03b7e26344e4d8d8aea618f3ea56110
Source dataset
uspto-grants-2004_10
Patent number
US06803477B2

Reaction notes

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