DI-TERT-BUTYLDIFLUOROSILANE → Di-tert-butyl(1-ethoxyvinyl)methylsilane

HRID 1926552Notes

Reaction equation

HRID 1926552 reaction equation
[C:1]([Si:5]([C:11]([CH3:14])([CH3:13])[CH3:12])([C:7](O)([CH3:9])C)C)([CH3:4])([CH3:3])[CH3:2].[C:15]([Si:19]([C:22]([CH3:25])([CH3:24])[CH3:23])([F:21])[F:20])([CH3:18])([CH3:17])[CH3:16].[CH2:26]([O:28]C=C[Li])[CH3:27].C[Li]>C1COCC1>[C:22]([Si:19]([C:15]([CH3:18])([CH3:17])[CH3:16])([F:21])[F:20])([CH3:25])([CH3:24])[CH3:23].[C:11]([SiH:5]([C:1]([CH3:2])([CH3:3])[CH3:4])[CH2:7][C:9]([O:28][CH2:26][CH3:27])=[CH2:15])([CH3:12])([CH3:13])[CH3:14]

Participants

7

Reactant 4

HCID 11275379DI-TERT-BUTYLDIFLUOROSILANEHCID 46900817HCID 46900817, compoundHCID 178418348HCID 178418348, compoundHCID 178506908HCID 178506908, compound

Product 2

HCID 11275379DI-TERT-BUTYLDIFLUOROSILANEHCID 131729726Di-tert-butyl(1-ethoxyvinyl)methylsilaneYield 14%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

Di-tert-butyldifluorosilane was prepared according to the procedure of B. Rempfer et al., J. Am. Chem. Soc. 1986, 108, 3893-3897. Following the general procedure of Example 7, di-tert-butyl(1-hydroxy-1-methylethyl)methylsilane was prepared from di-tert-butyldifluorosilane (11.8 g, 65.4 mmol), ethoxyvinyl lithium (prepared from ethyl vinyl ether (4.68 g, 64.9 mmol) and tert-butyl lithium (1.6 M in pentane, 40.6 ml, 65.0 mmol)) in THF (100 ml)) and methyl lithium (1.6 M in Et2O, 280 ml, 448 mmol). The crude product was distilled twice to furnish at 57° C./1.7 mbar 2.10 g (14%) of di-tert-butyl(1-ethoxyvinyl)methylsilane, of which 2.00 g (8.76 mmol) were hydrolysed with acetone/1 N HCl (2:1, 10 ml). Purification by silica-gel chromatography (silica-gel 35-70 μm, hexane/EtOAc, 9:1) followed by bulb-to-bulb distillation (120° C., 80 mbar) afforded 0.93 g (53%) of acetyl(di-tert-butyl)methylsilane (m.p. 35° C.), of which 0.90 g (4.49 mmol) was reacted with methyl lithium (1.6 M in Et2O, 60.0 ml, 96.0 mmol) according to Example 1 to furnish after purification by repeated silica-gel flash chromatography (silica-gel 15-40 μm, hexane/EtOAc, 9:1) 204 mg (21%) of the odoriferous title compound (m.p. 122-123° C.).

Workup

  1. distillationThe crude product was distilled twice

Sources & evidence

ORD record
ord-22200b28f1b24e5db7190d12893bb78f
Source dataset
uspto-grants-2012_05
Patent number
US08182781B2

Reaction notes

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