T. Takagi et al. / Journal of Fluorine Chemistry 128 (2007) 133–138
137
bromide and lithium acetylide of 9-decyn-1-ol [20]. All other
chemicals and reagents were commercially available.
Water for interfacial chemical measurements was prepur-
ified with a homemade purification system (RO membrane, ion-
exchange column, and 0.22 mm filter) and was further purified
with a Milli-Q Labo system (Millipore Corp., Bedford, MA)
and distillation in an all-glass still [21]. Its resistivity was higher
than 18 MV cm.
m), 1.60 (4H, m), 1.35–1.29 (12H, m). 19F NMR (CDCl3-
CD3OD) ppm: ꢀ18.01 (3F, t, J = 10.04 Hz), ꢀ51.72 (2F, m),
ꢀ59.21 (6F, brs), ꢀ60.02 (2F, brs), ꢀ60.83 (2F, brs), 63.40 (2F,
brs). IR (neat) vmax: 2927, 1482, 1243, 1197, 1149, 1081 and
968 cmꢀ1
.
4: colorless waxy solid. [a] + 0.0094 (c 0.1, MeOH). FAB-
MS m/z: 1366 (M + H)+. HRMS (FAB) calcd for
1
C44H51O6NF34P (M + H)+ 1366.2911: Found: 1366.2905. H
NMR (CDCl3-CD3OD) d: 4.28 (2H, bs), 3.89 (2H, t,
J = 5.63 Hz), 3.68 (2H, m), 3.64–3.52 (4H, m), 3.48–3.38
(3H, m), 3.28 (9H, s), 2.35 (4H, quin, J = 6.40 Hz), 1.61–1.52
(8H, m), 1.39 (4H, m), 1.29 (12H, bs). 19F NMR (CDCl3-
CD3OD) ppm: ꢀ18.03 (6F, t, J = 10.71 Hz), ꢀ33.36 (4F, bs),
ꢀ58.34 (4F, bs), ꢀ59.13 (8F, bs), ꢀ59.78 (4F, bs), ꢀ59.95 (4F,
bs), ꢀ63.34 (4F, m). IR (neat) vmax: 2931, 2859, 2258, 1671,
15: colorless waxy solid. FAB-MS m/z: 432 (M + H)+.
HRMS (FAB) calcd for C23H47O4NP (M + H)+ 432.3243:
Found: 432.3246. 1H NMR (CDCl3-CD3OD) d: 4.26 (2H, bs),
3.84 (2H, q, J = 6.70 Hz), 3.66 (2H, m), 3.26 (9H, s), 2.13 (4H,
t, J = 6.55 Hz), 1.61 (2H, quin, J = 7.08 Hz), 1.47 (4H, m),
3.3. General procedure for the synthesis of phosphocholine
Alcohol (1.0 equiv.) was treated with 2-bromoethylpho-
sphorodichloridate (1.5 equiv.) in benzene containing triethy-
lamine (1.5 equiv.) at room temperature for 18 h, and then the
reaction mixture was evaporated. The residue was extracted
with CHCl3 after being treated with water. The solvent was
removed under atmospheric pressure to afford the phosphoryl
intermediate. Me3N aq. was added to the intermediate in a
mixture of CHCl3/i-PrOH/CH3CN (3/5/5). The solution was
stirred at 60 8C for 18 h. After the removal of the solvent, the
crude compound was purified by column chromatography
(SiO2 (Merck, 7734): CHCl3/MeOH/H2O = 3/2/0 to 65/35/4
and Sephadex LH20: MeOH) to give the phosphocholine
compound in a high yield [10].
1236, 1205, 1147, 1093, 968 and 894 cmꢀ1
.
1.36–1.28 (18H, m), 0.88 (3H, t, J = 6.85 Hz). IR (neat) vmax
2927, 2854, 1463, 1236, 1089 and 968 cmꢀ1
:
.
16: colorless sticky solid. FAB-MS m/z: 436 (M + H)+.
HRMS (FAB) calcd for C23H51O4NP (M + H)+ 436.3556:
Found: 436.3557. 1H NMR (CDCl3-CD3OD) d: 4.26 (2H, bs),
3.84 (2H, q, J = 6.70 Hz), 3.69 (2H, m), 3.28 (9H, bs), 1.61 (2H,
quin, J = 7.01 Hz), 1.25 (30H, m), 0.88 (3H, t, J = 7.01 Hz). IR
Z-1: colorless waxy solid. FAB-MS m/z: 740 (M + H)+.
HRMS (FAB) calcd for C23H32O4NF17P (M + H)+ 740.1797;
1
Found: 740.1806. H NMR (CDCl3-CD3OD) d: 6.12 (1H, dtt,
J = 11.88, 7.92, 2.23 Hz), 5.49 (1H, td, J = 15.68, 11.88 Hz),
4.25 (2H, m), 3.85 (2H, q, J = 6.71 Hz), 3.66 (2H, m), 3.26 (9H,
s), 2.30 (2H, m), 1.61 (2H, m), 1.40 (2H, m), 1.33–1.30 (8H, m).
19F NMR (CDCl3-CD3OD) ppm: ꢀ18.05 (3F, t, J = 10.70 Hz),
ꢀ43.86 (2F, m), ꢀ58.71 (2F, bs), ꢀ59.18 (4F, bs), ꢀ59.96 (2F,
bs), ꢀ60.98 (2F, bs), ꢀ63.37 (2F, bs). IR (neat) vmax: 2929,
(neat) vmax: 2915, 2848, 1471, 1243, 1149, 1079 and 968 cmꢀ1
.
3.3.1. Synthesis of 13
The compound (12) was obtained from D-1,2-O-isopro-
pylidene-sn-glycerol according to the method described in
the literature [12]. To a solution of 12 and perfluorooctyl
iodide (1.870 g, 3.42 mmol) in CH3CN/H2O (2/1) was added
to NaHCO3 (0.249 g, 2.96 mmol) and 85% Na2S2O4
(0.578 g, 2.88 mmol), and the mixture was stirred at room
temperature for 4 h. The mixture was poured into ice, and
extracted with CH2Cl2. The CH2Cl2 layer was washed with
saturated NaCl and dried over MgSO4. After the solvent was
evaporated under atmospheric pressure, the residue was
separated by column chromatography (SiO2, EtOAc:n-
hexane = 3:7) to give a E/Z mixture (E/Z = 7/3) of 13
(1.210 g, 54%).
2857, 1662,1481, 1203, 1147, 1085 and 968 cmꢀ1
.
E-1: colorless sticky solid. FAB-MS m/z: 740 (M + H)+.
HRMS (FAB) calcd for C23H32O4NF17P (M + H)+ 740.1797;
1
Found: 740.1797. H NMR (CDCl3-CD3OD) d: 6.40 (1H, dtt,
J = 15.84, 7.01, 2.13 Hz), 5.59 (1H, dt, J = 15.84, 11.86 Hz),
4.26 (2H, bs), 3.84 (2H, q, J = 6.40 Hz), 3.72 (2H, m), 3.31 (9H,
s), 2.19 (2H, m), 1.61 (2H, m), 1.44 (2H, m), 1.35–1.29 (8H, m).
19F NMR (CDCl3-CD3OD) ppm: ꢀ18.03 (3F, t, J = 9.72 Hz),
ꢀ48.50 (2F, m), ꢀ58.73 (2F, bs), ꢀ59.25 (4F, bs), ꢀ60.01 (2F,
bs), ꢀ60.82 (2F, bs), ꢀ63.40 (2F, bs). IR (neat) vmax: 2935,
2859, 1674, 1488, 1238, 1201, 1149, 1076 and 970 cmꢀ1
.
1
2: colorless waxy solid. FAB-MS m/z: 738 (M + H)+. HRMS
(FAB) calcd for C23H30O4NF17P (M + H)+ 738.1641: Found:
E-13: H NMR (CDCl3-CD3OD) d: 7.26 (2H, dt, J = 8.83,
2.13 Hz), 6.87 (2H, dt, J = 8.83, 2.13 Hz), 6.31 (2H, t,
J = 14.41 Hz), 4.47 (2H, s), 3.80 (3H, s), 3.60–3.39 (9H, m),
2.61 (4H, m), 1.56 (10H, m), 1.30 (14H, bs). 19F NMR (CDCl3)
ppm: ꢀ18.08 (9F, t, J = 9.71 Hz), ꢀ42.70 (3F, m), ꢀ58.81 (4F,
bs), ꢀ59.25 (8F, bs), ꢀ60.06 (4F, m), ꢀ60.60 (4F, bs), ꢀ63.46
(4F, m).
Z-13: 1H NMR (CDCl3) d: 7.26 (2H, dt, J = 8.83, 2.13 Hz),
6.87 (2H, dt, J = 8.83, 2.13 Hz), 6.22 (2H, t, J = 11.35 Hz), 4.47
(2H, s), 3.80 (3H, s), 3.60–3.39 (9H, m), 2.64 (4H, m), 1.56
(10H, m), 1.30 (14H, bs). 19F NMR (CDCl3) ppm: ꢀ18.08 (6F,
t, J = 9.71 Hz), ꢀ45.78 (4F, m), ꢀ58.81 (4F, bs), ꢀ59.25 (8F,
bs), ꢀ60.06 (4F, m), ꢀ60.60 (4F, bs), ꢀ63.46 (4F, m).
1
738.1639. H NMR (CDCl3-CD3OD) d: 4.27 (2H, bs), 3.84
(2H, q, J = 6.60 Hz), 3.71 (2H, bs), 3.29 (9H, s), 2.35 (2H, quin,
J = 6.45 Hz), 1.62–1.53 (4H, m), 1.43–1.25 (8H, m). 19F NMR
(CDCl3-CD3OD) ppm: ꢀ18.08 (3F, t, J = 10.04 Hz), ꢀ33.43
(2F, m), ꢀ58.44 (2F, brs), ꢀ59.24 (4F, brs), ꢀ59.86 (2F, brs),
ꢀ60.06 (2F, brs), ꢀ63.43 (2F, brs). IR (neat) vmax: 2933, 2859,
2256, 1484,1238, 1205, 1149, 1087 and 968 cmꢀ1
.
3: colorless sticky solid. FAB-MS m/z: 742 (M + H)+.
HRMS (FAB) calcd for C23H34O4NF17P (M + H)+ 742.1954:
Found: 742.1946. 1H NMR (CDCl3-CD3OD) d: 4.27 (2H, brs),
3.83 (2H, q, J = 6.69 Hz), 3.75 (2H, brs), 3.33 (9H, s), 2.04 (2H,