´
J. Paterova et al. / Journal of Fluorine Chemistry 131 (2010) 1338–1343
1342
4.5. Potassium 8,8,8,7,7,6,6,5,5,4,4,3,3-tridecafluorooctyl sulfate (7b)
4.9. Attempted preparation of potassium 7,7,7,6,6,5,5,4,4-
nonafluoroheptyl sulfate
From 450 mg (1.01 mmol) of iodide 1b, 0.44 ml (1.32 mmol)
of EtMgBr solution and 200 mg (1.54 mmol) of cyclic sulfate 5,
266 mg (55.2%) of sulfate 7b was obtained after 6 h reaction
(white crystals, m.p. 200–204 8C). 1H NMR (299.97 MHz,
A flask was charged with iodide 1a (340 mg, 1.00 mmol), diethyl
ether (20 ml), the solution was cooled to À78 8C by a solid CO2/
ethanol bath and ethylmagnesium bromide (3 M solution in diethyl
ether, 0.44 ml, 1.32 mmol) was dropwise added to it. The mixture
was stirred for 30 min, during which time the temperature was
allowed to rise to À40 8C, and then recooled to À78 8C. 1,3,2-
Dioxathiane-2,2-dioxide (8, 230 mg, 1.54 mmol) and DMPU (1.5 ml)
weredissolvedin1 mlofdiethyletherandthesolutionwasdropwise
added to the preformed fluoro Grignard reagent 2a. The mixture was
allowed to warm to À40 8C and stirred at this temperature for 6 h.
The mixture was allowed to warm to 0 8C and water (5–10 ml) was
added to it. According to 19F NMR analysis the reaction mixture
contained 8% of starting iodide 1a, 73% of 1,1,1,2,2,3,3,4,4-
nonafluorobutane and 19% of dimerization product, perfluorooctane
with the NMR spectrum corresponding to the published data [29].
3
3
acetone-d6)
d 2.65 (tt, 2H, H-2, JHF = 18.5 Hz; JHH = 6.0 Hz);
4.25 (t, 2H, H-1, 3JHH = 6.0 Hz). 13C NMR (75.44 MHz, acetone-d6)
2
3
d
33.9 (t, 1C, C-2; JCF = 21.0 Hz); 54.1 (t, 1C, C-1, JCF = 5.0 Hz);
100–126 m, 6C (C-3–C-8). 19F NMR (282.23 MHz, acetone-d6)
d
À81.4 (m, 3F, F-8); À113.7 (m, 2F); À122.2 (m, 2F); À123.2 (m,
2F); À123.9 (m, 2F); À126.5 (m, 2F). MS (ESIÀ), m/z (%): 925
(64%) [(C6F13C2H4OSO3)2 K]À; 443 (100%) [C6F13C2H4OSO3]À.
HRMS (ESIÀ), m/z (%): calcd. for C8H4F13O4S [M]À, 442.96282;
found 442.96247.
4.6. Potassium 10,10,10,9,9,8,8,7,7,6,6,5,5,4,4,3,3-
heptadecafluorodecyl sulfate (7c)
From 270 mg (0.50 mmol) of iodide 1c, 0.22 ml (0.66 mmol) of
EtMgBr solution and 100 mg (0.77 mmol) of cyclic sulfate 5,
155 mg (53.3%) of sulfate 7c was obtained after 6 h reaction (white
4.10. Hydrolysis of sulfates 7 to alcohols 9 with hydrochloric acid.
General procedure
crystals, m.p. 195–198 8C). 1H NMR (299.97 MHz, acetone-d6)
d
Potassium fluoroalkyl sulfate 7 (ca. 40 mmol) was dissolved in
3
3
2.57 (tt, 2H, H-2, JHF = 18.5 Hz; JHH = 6.0 Hz); 4.22 (t, 2H, H-1,
3JHH = 6.0 Hz). 13C NMR (75.44 MHz, acetone-d6)
34.0 (t, 1C, C-2;
2JCF = 21.0 Hz); 54.1 (t, 1C, C-1, 3JCF = 5.0 Hz); 100–126 m, 8C (C-3–
C-10). 19F NMR (282.23 MHz, acetone-d6)
water (5 ml), sufficient amount of 35% HCl was added until pH 0–1
was reached and the mixture was heated to 70 8C for 25 h. The
reaction mixture was extracted with diethyl ether (2 Â 5 ml), the
organic parts were combined, dried with anhydrous MgSO4 and
diethyl ether was removed on a rotary vacuum evaporator (30 8C/
1 h/1 kPa) to afford the target alcohol 9.
d
d
À81.3 (m, 3F, F-10);
À113.9 (m, 2F); À122.2 (m, 2F); À122.4 (m, 4F); À123.3 (m, 2F);
À124.0 (m, 2F); À126.8 (m, 2F). MS (ESIÀ), m/z (%): 1125 (100%)
[(C8F17C2H4OSO3)2 K]À; 543 (81%) [C8F17C2H4OSO3]À. HRMS
(ESIÀ), m/z (%): calcd. for C10H4F17O4S [M]À, 542.95643; found
542.95631.
4.11. Hydrolysis of sulfate 7a to 6,6,6,5,5,4,4,3,3-nonafluorohexan-1-
ol (9a)
4.7. Potassium 12,12,12,11,11,10,10,9,9,8,8,7,7,6,6,5,5,4,4,3,3-
From 15 mg (39 mmol) of sulfate 7a, 9.0 mg (87%) of
heneicosafluorododecyl sulfate (7d)
fluoroalcohol 9a (colourless liquid) was obtained with NMR
spectra identical with the published data [22].
From 700 mg (1.08 mmol) of iodide 1d, 0.44 ml (1.32 mmol)
of EtMgBr solution and 200 mg (1.54 mmol) of cyclic sulfate 5,
360 mg (52.8%) of sulfate 7d was obtained after 7 h reaction
(white crystals, sublimes 220–240 8C). 1H NMR (299.97 MHz,
4.12. Hydrolysis of sulfate 7b to 8,8,8,7,7,6,6,5,5,4,4,3,3-
tridecafluorooctan-1-ol (9b)
acetone-d6)
d
2.57 (tt, 2H, H-2, 3JHF = 18.5 Hz; 3JHH = 6.0 Hz); 4.22
From 20 mg (41 mmol) of sulfate 7b, 14 mg (90%) of fluor-
oalcohol 9b (colourless liquid) was obtained with NMR spectra
identical with the published data [22].
3
(t, 2H, H-1, JHH = 6.0 Hz). 13C NMR (75.44 MHz, acetone-d6)
d
2
3
34.0 (t, 1C, C-2; JCF = 21.0 Hz); 54.1 (t, 1C, C-1, JCF = 5.0 Hz);
100–126 m, 10C (C-3–C-12). 19F NMR (282.23 MHz, acetone-d6)
d
À81.3 (m, 3F, F-12); À113.9 (m, 2F); À122.2 (m, 2F); À122.4
4.13. Hydrolysis of sulfate 7c to 10,10,10,9,9,8,8,7,7,6,6,5,5,4,4,3,3-
heptadecafluorodecan-1-ol (9c)
(m, 4F); À123.3 (m, 2F); À124.0 (m, 2F); À126.8 (m, 2F).
MS (ESIÀ), m/z (%): 643 (100%) [C10F21C2H4OSO3]À. HRMS (ESIÀ),
m/z (%): calcd. for
C
10H4F17O4S [M]À, 642.95004; found
From 25 mg (43 mmol) of sulfate 7c, 17 mg (83%) of fluor-
642.94968.
oalcohol 9c (white wax) was obtained with NMR spectra identical
with the published data [22].
4.8. Potassium
14,14,14,13,13,12,12,11,11,10,10,9,9,8,8,7,7,6,6,5,5,4,4,3,3-
4.14. Hydrolysis of sulfate 7d to 12,12,12,11,11,10,10,9,9,8,8,7,7,6,6,
5,5,4,4,3,3-heneicosafluorododecan-1-ol (9d)
pentacosafluorotetradecyl sulfate (7e)
From 800 mg (1.08 mmol) of iodide 1e, 0.44 ml (1.32 mmol) of
EtMgBr solution and 200 mg (1.54 mmol) of cyclic sulfate 5,
391 mg (50.0%) of sulfate 7e was obtained after 7 h reaction (white
crystals, sublimes 220–250 8C). 1H NMR (299.97 MHz, acetone-d6)
From 30 mg (44
mmol) of sulfate 7d, 22 mg (89%) of fluor-
oalcohol 9d (white wax) [30] was obtained. 1H NMR (299.97 MHz,
3
3
acetone-d6)
d 2.40 (tt, 2H, H-2, JHF = 19.0 Hz; JHH = 6.4 Hz); 3.82
3
(t, 2H, H-1, JHH = 6.4 Hz). 19F NMR (282.23 MHz, acetone-d6)
d
3
3
d
2.58 (tt, 2H, H-2, JHF = 18.5 Hz; JHH = 6.0 Hz); 4.20 (t, 2H, H-1,
À81.3 (m, 3F, F-12); À114.0 (m, 2F); À122.0 (m, 8F); À123.0 (m,
3JHH = 6.0 Hz). 13C NMR (75.44 MHz, acetone-d6)
d 33.9 (t, 1C, C-2;
4F); À124.0 (m, 2F); À126.5 (m, 2F).
2JCF = 21.0 Hz); 54.0 (t, 1C, C-1, JCF = 5.0 Hz); 100–126 m, 12C (C-
3–C-14). 19F NMR (282.23 MHz, acetone-d6)
3
d
À81.3 (m, 3F, F-14);
4.15. Hydrolysis of sulfate 7e to 12,12,12,11,11,10,10,9,9,8,8,7,7,6,6,5,
5,4,4,3,3-heneicosafluorododecan-1-ol (9e)
À113.8 (m, 2F); À121.2 (m, 2F); À121.9 (m, 10F); À122.9 (m, 4F);
À123.4 (m, 2F); À126.4 (m, 2F). MS (ESIÀ), m/z (%): 743 (100%)
[C12F25C2H4OSO3]À. HRMS (ESIÀ), m/z (%): calcd. for C14H4F25O4S
[M]À, 742.94366; found 742.94297.
From 35 mg (45
oalcohol 9e (white wax) [31] was obtained. 1H NMR (299.97 MHz,
mmol) of sulfate 7e, 26 mg (89%) of fluor-