heptadecafluorodecanol (2.32 g, 5 mmol) were added to the
mixture with stirring at 0 ЊC, and the mixture was allowed to
warm to room temperature and stirred for 12 h. After the
solvent was removed under reduced pressure to dryness,
the resulting white solid was washed with water and dried
under vacuum. The pure compound was obtained after
column chromatography on SiO2 with hexane–ethyl acetate
(6:1) as eluent (2.48 g, 4.3 mmol, 86%) as a white solid;
mp 47.2–48.0 ЊC; IR (KBr) 1722, 1590, 1298, 1202, 1147, 746,
705, 660 cmϪ1; δH(300 MHz, CDCl3) 2.63 (tt, JH-F = 18.2 Hz,
JH-H = 6.3 Hz, 2H), 4.67 (t, J = 6.3 Hz, 2H), 7.41 (dd, J = 7.9,
5.0 Hz, 1H), 8.29 (d, J = 7.9 Hz, 1H), 8.81 (d, J = 5.0 Hz, 1H),
658, 560, 529 cmϪ1; δH(300 MHz, CDCl3) 2.42–2.56 (m, 4H),
3.04 (dd, J = 16.7, 5.0 Hz, 1H), 3.13 (dd, J = 16.7, 6.6 Hz, 1H),
4.44–4.61 (m, 4H), 5.75 (dd, J = 6.6, 5.0 Hz, 1H), 7.41 (dd,
J = 7.8, 4.5 Hz, 1H), 8.29 (d, J = 7.8 Hz, 1H), 8.81 (d, J = 4.5
2
Hz, 1H), 9.24 (s, 1H); δC(100 MHz, CDCl3) 30.3 (t, JC-F = 22
Hz), 30.3 (t, 2JC–F = 22 Hz), 35.7, 57.1, 57.8, 68.6, 105–122 (m),
123.6, 125.2, 138.0, 150.4, 153.2, 163.8, 167.8, 168.4. Anal. Calc.
for C30H15F34NO6: C, 31.85; H, 1.34. Found: C, 31.55; H, 1.21%.
Pyridine-3-carbaldehyde bis(3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-
heptadecafluorodecyl) acetal (IV)
2
A mixture of pyridine-3-carbaldehyde (0.32 g, 3 mmol), 3,3,4,4,
5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecanol (4.18 g, 9
mmol) and trifluoromethanesulfonic acid (0.1 ml, 1.1 mmol) in
1,2-dichloroethane (30 mL) was stirred at reflux in a 50 ml
flask equipped with a dropping funnel, the top of which was
attached with a reflux condenser, and 1,2-dichloroethane
pooled in the dropping funnel was added dropwise to the reac-
tion mixture. After 6 h, the reaction mixture was cooled to
room temperature and then triethylamine (2 mL) was added to
the solution, and the mixture was diluted with diethyl ether. The
organic layer was washed with water and dried over MgSO4.
The solvent was removed under vacuum and the residue was
subjected to column chromatography on SiO2 with hexane–
ethyl acetate (4:1) as eluent to give IV (2.85 g, 2.8 mmol, 94%)
as a colorless oil; IR (neat) 1204, 1148, 1064, 980, 877, 787, 704,
657, 564, 529 cmϪ1; δH(400 MHz, CDCl3) 2.46 (tt, JH-F = 18.6
Hz, JH-H = 6.4 Hz, 4H), 3.77–3.81 (m, 4H), 5.67 (s, 1H), 7.34
(dd, J = 7.8, 4.9 Hz, 1H), 7.77 (d, J = 7.8 Hz, 1H), 8.62
(d, J = 4.9 Hz, 1H), 8.70 (s, 1H); δC(75.5 MHz, CDCl3) 31.4
(t, 2JC-F = 21 Hz), 57.4, 100.0, 105–122 (m), 123.3, 132.5, 134.3,
148.5, 150.3. Anal. Calc. for C26H13F34NO2: C, 30.70; H, 1.29.
Found: C, 30.41; H, 1.54%.
9.23 (s, 1H); δC(100 MHz, CDCl3) 30.7 (t, JC-F = 22 Hz), 57.4,
105–122 (m), 123.5, 125.7, 137.2, 151.1, 153.9, 165.0. Anal.
Calc. for C16H8F17NO2: C, 33.76; H, 1.42. Found: C, 33.53; H,
1.19%.
Bis(3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl)
pyridine-3,5-dicarboxylate(II)
A mixture of pyridine-3,5-dicarboxylic acid (0.33 g, 2 mmol)
and thionyl chloride (2.2 mL) was stirred at 90 ЊC. After 6 h, the
excess thionyl chloride was removed under reduced pressure
and the resulting yellow–white solid was dissolved in CH2Cl2
(10 mL). Then, triethylamine (12 mL), 3,3,4,4,5,5,6,6,7,7,8,8,
9,9,10,10,10-heptadecafluorodecanol (2.04 g, 4.4 mmol) and
CH2Cl2 (4 mL) were added to the mixture with stirring at 0 ЊC,
and the mixture was allowed to warm to room temperature and
stirred. After 24 h, water was added and the mixture was diluted
with CHCl3. The organic layer was washed with water and
dried over MgSO4. The solvent was removed under reduced
pressure and the residue was subjected to column chromato-
graphy on SiO2 with hexane–ethyl acetate (7:3) as eluent to give
a white solid. A small amount of impurities was removed by
washing the solid with hexane and diethyl ether to give the pure
compound as a white solid (0.54 g, 0.51 mmol, 26%); mp 123.5–
124.5 ЊC; IR (KBr) 1730, 1602, 1205, 1147, 1115, 753, 703, 661,
561, 533 cmϪ1; δH(270 MHz, CDCl3) 2.65 (tt, JH-F = 18.1 Hz,
JH-H = 6.2 Hz, 4H), 4.71 (t, J = 6.2 Hz, 4H), 8.84 (s, 1H), 9.50
(br s, 2H). Anal. Calc. for C27H11F34NO4: C, 30.61; H, 1.05.
Found: C, 30.33; H, 0.91%.
Typical procedure for the palladium(II)-catalysed oxidation of
alcohols under an oxygen atmosphere in a fluorous biphase
system
To a mixture of Pd(OAc)2 (5.6 mg, 0.025 mmol) and toluene
(1.5 mL) in a glass tube (φ 15 mm × 180 mm) was added ligand
IV (101 mg, 0.1 mmol) under vigorous stirring. After a few
minutes, perfluorodecalin (2 mL) and molecular sieves were
added and oxygen gas was introduced into the glass tube
equipped with an O2 balloon, and then the alcohol (0.5 mmol)
in toluene (0.5 mL) was added. After stirring at 80 ЊC for the
appropriate time under an atmospheric pressure of oxygen, the
mixture was cooled to 0 ЊC in an ice bath and allowed to stand
for ca. 5 min, and then the toluene phase was separated using
a pipette. The amount of product was determined by GLC
analysis using bibenzyl or cyclododecane as an internal stand-
ard. For isolation of the product the solvent was evaporated
and the residue was purified by column chromatography on
silica gel using hexane–ethyl acetate (95:5) as eluent.
Bis(3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl)
malate
A mixture of ( )-malic acid (0.40 g, 5 mmol), toluene-p-
sulfonic acid (50 mg), and 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-
heptadecafluorodecanol (3.06 g, 6.6 mmol) in toluene (30 mL)
was stirred at 130 ЊC using a Dean–Stark distillation apparatus.
After 18 h, the mixture was allowed to cool to room temper-
ature and the resulting solid was purified by column chromato-
graphy on SiO2 using hexane–ethyl acetate (7:3) as eluent to
give a white solid (1.03 g, 1.0 mmol, 33%); mp 64.6–65.3 ЊC; IR
(KBr) 1749, 1200, 1142, 708, 666, 561, 536 cmϪ1; δH(400 MHz,
acetone-d6) 2.59–2.85 (m, 7H), 4.42–4.60 (m, 5H). Anal. Calc.
for C24H12F34O5: C, 28.09; H, 1.18. Found: C, 28.09; H, 0.99%.
Typical procedure for catalyst recycling
After the reaction as described above, octane (2 mL) was added
at 0 ЊC and the mixture was allowed to stand for ca. 5 min
without stirring, and then the toluene phase was separated
using a pipette. The resulting fluorous phase (containing 3 Å
molecular sieves) was ready for further runs: that is, the alcohol
(0.5 mmol) in toluene (2 mL) was added to the fluorous phase
and the mixture was stirred at 80 ЊC under O2. The amount
of palladium which had leached into the toluene phase in
the oxidation of 1-phenylethanol under the conditions shown
in Table 4 was estimated by ICP atomic emission analysis
for a nitric acid solution of the residue after removing the
solvent and the product from the separated toluene phase
under reduced pressure (0.2 µmol, 0.8% based on Pd(OAc)2
employed).
Bis(3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl)
1-(pyridin-3-ylcarbonyloxy)succcinate (III)
To a mixture of nicotinoyl chloride prepared as described above
(3 mmol) and triethylamine (1 mL) in CH2Cl2 (10 mL) was
added bis(3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluoro-
decyl) malate (1.03 g, 1 mmol) at 0 ЊC and the mixture was
allowed to warm to room temperature and stirred for 12 h. The
solvent was removed under reduced pressure and the resulting
white solid was washed with water and CH2Cl2 and then dried
under vacuum. The pure compound was obtained after column
chromatography on SiO2 with hexane–ethyl acetate (7:3) as
eluent (0.34 g, 0.3 mmol, 30%) as a white solid; mp 74.0–
75.0 ЊC; IR (KBr) 1770, 1739, 1723, 1592, 1204, 1147, 741, 714,
4304
J. Chem. Soc., Perkin Trans. 1, 2000, 4301–4305