Triethylamine → 10-(Ethenesulfonyl)-1,1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8-heptadecafluorodecane

HRID 462841Notes

Reaction equation

HRID 462841 reaction equation
Cl[CH2:2][CH2:3][S:4]([CH2:7][CH2:8][C:9]([F:33])([F:32])[C:10]([F:31])([F:30])[C:11]([F:29])([F:28])[C:12]([F:27])([F:26])[C:13]([F:25])([F:24])[C:14]([F:23])([F:22])[C:15]([F:21])([F:20])[C:16]([F:19])([F:18])[F:17])(=[O:6])=[O:5].C(N(CC)CC)C.[Cl-].C([NH+](CC)CC)C>O1CCCC1>[CH:3]([S:4]([CH2:7][CH2:8][C:9]([F:33])([F:32])[C:10]([F:30])([F:31])[C:11]([F:28])([F:29])[C:12]([F:26])([F:27])[C:13]([F:24])([F:25])[C:14]([F:22])([F:23])[C:15]([F:20])([F:21])[C:16]([F:19])([F:18])[F:17])(=[O:6])=[O:5])=[CH2:2]

Participants

5

Reactant 3

HCID 8471TriethylamineHCID 12698378Triethylazanium chlorideHCID 20397543HCID 20397543, compound

Product 1

HCID 2039753810-(Ethenesulfonyl)-1,1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8-heptadecafluorodecaneYield 14.3%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

2-(Perfluorooctyl)ethanyl 2-chloroethanyl sulfone (RF =C8F17, 5.74 g, 10.0 mmole) was dissolved in 40 ml of tetrahydrofuran (THF) at 45°, while stirring in a constant temperature oil bath. Triethylamine (1.52 g, 2.10 ml, 15.0 mmole) in 10 ml of THF was added and an exotherm carried the temperature to 51°. A precipitate of white solid triethylammonium chloride immediately began to form. After 1 hour at 45° the slurry was filtered while hot (Buchner funnel), rinsed with diethyl ether twice, and the clear filtrate evaporated on a rotary evaporator. The dry solid Et3N HCl weighed 1.35 g, 98.8% of theory. The evaporated solid 2-(perfluoro-octyl)ethanyl vinyl sulfone was taken to 40°/15 mm and weighed 5.38 g, 100% of theory; mp sinter 92° melt 93°-94.5°. The sulfone was heated further to 155° without evidence of decomposition. The sulfone was soluble in chloroform, and insoluble in carbon tetrachloride, benzene or ligroine (bp 60°-70°). The sulfone dissolved in hot benzene, but was insoluble in hot ligroine. A 1.00 g sample was dissolved in 8.0 ml of benzene by heating on a steam bath, with care to prevent foaming over; 8.0 ml of ligroine was added and the clear, colorless solution when cool gave 0.77 g of solid, mp sinter 94° melt 95°-96°. When concentrated to 4.0 ml volume a fraction, 0.11 g, mp 96°-97° was obtained. The original sample gave a single spot in TLC analysis. The infrared spectrum was identical to that of the C6 homolog of Example 1. The NMR spectrum was consistent with the proposed structure and resembled closely that obtained from the C6 homolog.

Workup

  1. customto 51°
  2. customto form
  3. filtrationAfter 1 hour at 45° the slurry was filtered while hot (Buchner funnel)
  4. washrinsed with diethyl ether twice
  5. customthe clear filtrate evaporated on a rotary evaporator
  6. customwas taken to 40°
  7. custommp sinter 92°
  8. custommelt 93°-94.5°
  9. temperatureThe sulfone was heated further to 155° without evidence of decomposition
  10. dissolutionThe sulfone dissolved in hot benzene
  11. dissolutionA 1.00 g sample was dissolved in 8.0 ml of benzene
  12. temperatureby heating on a steam bath, with care
  13. addition8.0 ml of ligroine was added
  14. temperaturethe clear, colorless solution when cool

Sources & evidence

ORD record
ord-cac0b12459594649965ac1acb979e40f
Source dataset
uspto-grants-1985_05
Patent number
US04517384

Reaction notes

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