Tetrahydrofuran → (3,3,4,4,5,5,6,6,6-Nonafluorohexyldiisopropylsilyl)acetylene

HRID 1408491Notes

Reaction equation

HRID 1408491 reaction equation
[F:1][C:2]([F:19])([C:9]([F:18])([F:17])[C:10]([F:16])([F:15])[C:11]([F:14])([F:13])[F:12])[CH2:3][CH2:4][Si:5](Cl)(Cl)Cl.[CH:20]([Li])([CH3:22])[CH3:21].[C:24]([Mg]Br)#[CH:25].[CH2:28]1[CH2:32]OC[CH2:29]1>>[F:1][C:2]([F:19])([C:9]([F:18])([F:17])[C:10]([F:16])([F:15])[C:11]([F:14])([F:13])[F:12])[CH2:3][CH2:4][Si:5]([C:24]#[CH:25])([CH:28]([CH3:32])[CH3:29])[CH:20]([CH3:22])[CH3:21]

Participants

5

Reactant 4

HCID 8028TetrahydrofuranHCID 11811026NonafluorohexyltrichlorosilaneHCID 178418486HCID 178418486, compoundHCID 178506895HCID 178506895, compound

Product 1

HCID 86663262(3,3,4,4,5,5,6,6,6-Nonafluorohexyldiisopropylsilyl)acetyleneYield 31%

Conditions

Temperature
50 °C

Procedure

To an oven-dried 250-mL round bottom flask was added 3,3,4,4,5,5,6,6,6-nonafluorohexyltrichlorosilane (4.52 g, 11.9 mmol) and anhydrous THF (20 mL). Isopropyllithium (34 mL, 24 mmol, 0.7 M in pentane) was added dropwise over 1 hr, then stirring was continued for 4 hr. Ethynylmagnesium bromide (32 mL, 16 mmol, 0.5 M in THF) was added slowly, then the reaction mixture was heated to 50° C. for 12 hr. The reaction was quenched with water and dilute sulfuric acid to dissolve the salts, then hexane was added and the organic layer was separated. The organic layer was washed with water (5×20 mL), dried over magnesium sulfate, filtered, and concentrated under vacuum to yield the crude product mixture. Purification by silica chromatography with hexane as an eluant (Rf˜0.6 in hexane) yielded 1.8 g (4.6 mmol, 31%) of the desired product as a colorless liquid. Analysis of the colorless product provided the following data: 1H-NMR (200 MHz, CDCl3) δ=2.4 (s, 1H), 2.2 (m, 2H), 1.1 (m, 14H), 0.8 (m, 2H).

Workup

  1. customThe reaction was quenched with water and dilute sulfuric acid
  2. dissolutionto dissolve the salts
  3. additionhexane was added
  4. customthe organic layer was separated
  5. washThe organic layer was washed with water (5×20 mL)
  6. dry with materialdried over magnesium sulfate
  7. filtrationfiltered
  8. concentrationconcentrated under vacuum
  9. customto yield the crude product mixture
  10. customPurification by silica chromatography with hexane as an eluant (Rf˜0.6 in hexane)

Sources & evidence

ORD record
ord-e4e71c85d4484350bcf70877aaf1f82f
Source dataset
uspto-grants-2014_12
Patent number
US08920679B2

Reaction notes

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