13465-73-1 → HCID 86663269, compound

HRID 1408497Notes

Reaction equation

HRID 1408497 reaction equation
Br[SiH3].[F:3][C:4]([F:22])([C:15]([F:21])([F:20])[C:16]([F:19])([F:18])[F:17])[CH2:5][CH2:6][Si:7](Br)([CH:11]([CH3:13])[CH3:12])[CH:8]([CH3:10])[CH3:9].[C:23]([Mg]Br)#[CH:24]>C1COCC1>[F:3][C:4]([F:22])([C:15]([F:21])([F:20])[C:16]([F:19])([F:18])[F:17])[CH2:5][CH2:6][Si:7]([C:23]#[CH:24])([CH:11]([CH3:13])[CH3:12])[CH:8]([CH3:10])[CH3:9]

Participants

5

Reactant 3

HCID 6162113465-73-1HCID 86663270HCID 86663270, compoundHCID 178418486HCID 178418486, compound

Product 1

HCID 86663269HCID 86663269, compoundYield 90%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
40 °C

Procedure

In an oven dried round bottom flask, (3,3,4,4,5,5,5-heptafluoropentyl)diisopropylsilane (10 g, 32 mmol) was dissolved in allyl bromide (20 mL) and the flask was flushed with N2. PdCl2 (40 mg) was added and the solution was heated to 60° C. for 12 hr. Solvent was removed on a rotary evaporator to yield a brown suspension that was taken up in pentane and filtered. Solvent removal yielded the bromosilane as a brown liquid (12.1 g). The bromosilane, (3,3,4,4,5,5,5-heptafluoropentyldiisopropylsilyl)bromide, was treated with ethynylmagnesium bromide (70 mL, 35 mmol, 0.5 M in THF) in anhydrous THF (20 mL) and heated to 40° C. for 4 hr. After cooling, the reaction was quenched by the slow addition of water (20 mL) and dilute sulfuric acid sufficient to dissolve the magnesium salts. Pentane was added and the organic layer was separated. The aqueous layer was extracted with pentane an additional time, then the organic layers were combined, washed with water (5×10 mL) and brine, dried over MgSO4, and filtered. Solvent was removed and the crude product was taken up in hexane and rinsed through a thin pad of silica. Solvent removal yielded the product as a colorless liquid (9.7 g, 29 mmol, 90%). Analysis of the product provided the following data: 1H-NMR (400 MHz, CDCl3) δ=2.4 (s, 1H), 2.2 (m, 2H), 1.0 (m, 14H), 0.8 (m, 2H).

Workup

  1. temperatureAfter cooling
  2. customthe reaction was quenched by the slow addition of water (20 mL) and dilute sulfuric acid sufficient
  3. dissolutionto dissolve the magnesium salts
  4. additionPentane was added
  5. customthe organic layer was separated
  6. extractionThe aqueous layer was extracted with pentane an additional time
  7. washwashed with water (5×10 mL) and brine
  8. dry with materialdried over MgSO4
  9. filtrationfiltered
  10. customSolvent was removed
  11. washrinsed through a thin pad of silica
  12. customSolvent removal

Sources & evidence

ORD record
ord-6ec3754b138a4b079fd1b6cc168750ef
Source dataset
uspto-grants-2014_12
Patent number
US08920679B2

Reaction notes

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