Methyl iodide → Tert-butyl-(2,3-difluoro-4-methyl-benzyloxy)-dimethyl-silane

HRID 1266362Notes

Reaction equation

HRID 1266362 reaction equation
CN([CH2:4][CH2:5]N(C)C)C.C([Li])(CC)C.[C:14]([Si:18]([O:21][CH2:22][C:23]1[CH:28]=[CH:27]C=[C:25]([F:29])[C:24]=1[F:30])([CH3:20])[CH3:19])([CH3:17])([CH3:16])[CH3:15].CI>C1COCC1>[C:14]([Si:18]([O:21][CH2:22][C:23]1[CH:28]=[CH:27][C:4]([CH3:5])=[C:25]([F:29])[C:24]=1[F:30])([CH3:20])[CH3:19])([CH3:17])([CH3:15])[CH3:16]

Participants

6

Reactant 4

HCID 6328Methyl iodideHCID 8037N,N,N',N'-TetramethylethylenediamineHCID 18549933Tert-butyl-(2,3-difluoro-benzyloxy)-dimethyl-silaneHCID 178418400CID 53628100

Product 1

HCID 18550272Tert-butyl-(2,3-difluoro-4-methyl-benzyloxy)-dimethyl-silaneYield 105.3%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent3×

Procedure

To a solution of TMEDA (3.9 mL, 3.0 g, 26 mmol) in THF (33 mL) at −78° C. was added sec butyllithium (20 mL, 1.3 M in hexane, 26 mmol). After stirring for 20 minutes, a solution of tert-butyl-(2,3-difluoro-benzyloxy)-dimethyl-silane (6.0 g, 23 mmol) in 17 mL of THF was added dropwise. After stirring for 1 hour, the solution was added dropwise to a solution of methyl iodide (8 mL) in THF (40 mL) at −20° C. After stirring for 18 hours, the mixture was quenched with saturated aqueous NH4Cl, extracted 3× into ether, and the combined organic layers were dried over MgSO4, filtered and concentrated in vacuo, giving 6.6 g of tert-butyl-(2,3-difluoro-4-methyl-benzyloxy)-dimethyl-silane as a light yellow oil. 1H NMR (400 MHz, CDCl3) δ 7.07 (app. t, 1H, J=7.2 Hz), 6.89 (app. t, 1H, J=7.3 Hz), 4.74 (s, 2H), 2.26 (d, 3H, J=1.9 Hz), 0.87 (s, 9H), 0.07 (s, 6H) ppm.

Workup

  1. stirringAfter stirring for 1 hour
  2. stirringAfter stirring for 18 hours
  3. customthe mixture was quenched with saturated aqueous NH4Cl
  4. extractionextracted 3× into ether
  5. dry with materialthe combined organic layers were dried over MgSO4
  6. filtrationfiltered
  7. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-f63d948ab7ad442c8ab7a8222616fa85
Source dataset
uspto-grants-2003_04
Patent number
US06548526B2

Reaction notes

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