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General Procedure
for the Direct Fluorination of Ketones in SDS Aqueous Micellar System
Ketone
(1 mmol) was placed in a glass flask (25 mL) equipped with a magnetic
stirrer. Then, H2O (5 mL) was added and stirred for a
few minutes. An appropriate amount of SDS (144 mg, 0.5 mmol or 288
mg, 1 mmol; see Table
[³]
) was
then added to the heterogeneous reaction system and heated to 80 ˚C
during rapid stirring. When the reaction system reached 80 ˚C,
F-TEDA-BF4 (390 mg, 1.1 mmol) was added in two portions
over an interval of 1 h, and stirred and held at 80 ˚C
until the KI test showed consumption of the fluorinating reagent.
When reaction was complete, the reaction system was cooled to r.t.,
and the resulting suspension was extracted with Et2O
(2 × 15 mL). The combined ether phases
were dried over anhyd Na2SO4. After the removal
of the solvent under reduced pressure, the crude products obtained
were identified with ¹H NMR, ¹9F
NMR, and MS analysis and purified by silica gel column chromatography
or preparative TLC (SiO2, CH2Cl2,
and a few drops of EtOH) to afford pure α-fluoro ketones.
The spectroscopic data of the products were in agreement with those
reported in the literature.
Spectroscopic
Data for Representative Compounds
1-Fluoro-1-phenylpropan-2-one
²²
(21)
Liquid product. ¹H
NMR (300 MHz, CDCl3): δ = 2.23
(d, J = 4.0
Hz, 3 H, Me), 5.68 (d, J = 48.7
Hz, 1 H, CHF), 7.40 (br s, 5 H, ArH). ¹9F NMR
(285 MHz, CDCl3): δ = -183.14 (dq, J = 48.7,
4.0 Hz). ¹³C NMR (76.2 MHz, CDCl3): δ = 25.13
(Me), 95.84 (d, J = 187.8
Hz, C-1), 126.00 (d, J = 7.0
Hz), 128.9, 129.36 (d, J = 2.3
Hz), 133.94 (d, J = 20.6 Hz),
204.55 (d, J = 26.7
Hz, CO). MS (EI, 70eV):
m/z (%) = 152
(6) [M+], 110 (10), 109 (100),
83 (20).
1-Fluoro-1,1-diphenyl-propan-2-one
²³
(23)
Mp
58.5-60.0 ˚C. ¹H
NMR (300 MHz, CDCl3): δ = 2.41
(d, J = 5.9 Hz, 3 H, Me), 7.37
(br s, 10 H, ArH). ¹9F NMR (285 MHz, CDCl3): δ = -143.62
(q, J = 5.9
Hz). ¹³C NMR (76.2 MHz, CDCl3): δ = 26.71
(Me), 102.17 (d, J = 185.8
Hz,
C-1), 126.64 (d, J = 7.4
Hz), 128.34, 128.77 (d, J = 2.0
Hz), 137.54 (d, J = 22.8
Hz), 206.43 (d, J = 32.7
Hz, CO).
MS (EI, 70eV): m/z (%) = 185
(100) [M+ - COMe],
151 (11).
3-Fluoro-4-phenylbutan-2-one
²4
(27)
Liquid
product. ¹H NMR (300 MHz, CDCl3): δ = 2.13
(d, J = 4.9
Hz, 3 H, Me), 3.01-3.21 (m, 2 H, CH2), 4.93
(ddd, J = 48.5,
6.0, 3.0 Hz, 1 H, CHF), 7.21-7.34 (m, 5 H, ArH). ¹9F
NMR (285 MHz, CDCl3): δ = -188.66
(dtq, J = 48.5, 23.2,
5.0 Hz). ¹³C NMR (76.2 MHz, CDCl3): δ = 26.42 (Me),
38.10 (d, J = 20.6
Hz, C-4), 95.89 (d, J = 187.3
Hz,
C-3), 127.10, 128.57, 129.49, 135.28, 209.98 (d, J = 26.7 Hz,
CO). MS (EI, 70eV): m/z (%) = 166
(100) [M+], 146 (100), 123
(15), 91 (77), 77 (41).
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