3,3,4,4,5,5,6,6,6-Nonafluoro-1-hexene → (E)-3,3,4,4,5,5,6,6,6-Nonafluoro-1-[4-(pentafluorosulfanyl)phenyl]-hex-1-ene

HRID 926096Notes

Reaction equation

HRID 926096 reaction equation
F[B-](F)(F)F.[F:6][S:7]([F:19])([F:18])([F:17])([F:16])[C:8]1[CH:13]=[CH:12][C:11]([N+]#N)=[CH:10][CH:9]=1.[F:20][C:21]([F:34])([C:24]([F:33])([F:32])[C:25]([F:31])([F:30])[C:26]([F:29])([F:28])[F:27])[CH:22]=[CH2:23]>C(O)C.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[F:20][C:21]([F:34])([C:24]([F:32])([F:33])[C:25]([F:30])([F:31])[C:26]([F:27])([F:29])[F:28])/[CH:22]=[CH:23]/[C:11]1[CH:12]=[CH:13][C:8]([S:7]([F:19])([F:18])([F:17])([F:16])[F:6])=[CH:9][CH:10]=1

Participants

5

Reactant 2

HCID 880543,3,4,4,5,5,6,6,6-Nonafluoro-1-hexeneHCID 1222352754-(Pentafluorosulfanyl)phenyldiazonium Tetrafluoroborate

Product 1

HCID 118656369(E)-3,3,4,4,5,5,6,6,6-Nonafluoro-1-[4-(pentafluorosulfanyl)phenyl]-hex-1-eneYield 81%

Reagents, catalysts & solvents 2

HCID 167845palladium(II) acetateCatalystHCID 702EthanolSolvent

Procedure

Palladium(II) acetate (0.5 mg, 0.002 mmol) was added to a solution of 1 (15.0 mg, 0.0472 mmol) and 3,3,4,4,5,5,6,6,6-nonafluorohex-1-ene (8.9 mg, 0.089 mmol) in 0.44 g of 95% aqueous ethanol. The reaction mixture was stirred at room temperature for 1 d and filtered through a pad of Celite 545. Removal of the solvent gave a pale yellow oil which was purified by SiO2 column chromatography with hexane to give 7a as colorless oil (17.1 mg; 81%): IR (ATR): {tilde over (v)}=2918, 2849, 1663, 1234, 1134, 844 cm−1. MS (GC, EI): m/z=448 [M+], 429 [M+-F], 302 [M+-SF6], 279 [M+-C3F7], 152 [M+-C3F12S]. 1H NMR (500 MHz, CDCl3): δ=7.80 (d, J=8.7 Hz, 2H), 7.57 (d, J=8.7 Hz, 2H), 7.20 (d, J=16.2 Hz, 1H), 6.30 (dt, J=16.2, 12.0 Hz, 1H) ppm. 13C NMR (125 MHz, CDCl3): δ=154.7 (C), 137.7 (CH), 136.5 (C), 127.8 (2CH), 126.7 (2CH), 117.7 (CH) ppm. 19F NMR (470 MHz, CDCl3): δ=83.4 (quint, J=150 Hz, 1 F), 62.6 (d, J=150 Hz, 4 F), −81.0 (s, 3 F), −112.0 (s, 2 F), −124.0 (s, 2 F), −125.7 (s, 2 F) ppm.

Workup

  1. filtrationfiltered through a pad of Celite 545
  2. customRemoval of the solvent
  3. customgave a pale yellow oil which
  4. customwas purified by SiO2 column chromatography with hexane

Sources & evidence

ORD record
ord-9896d801203843d6acac69a4e5182c66
Source dataset
uspto-grants-2016_03
Patent number
US09284336B1

Reaction notes

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