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acid. FA methyl esters were extracted with 1 mL of hexane,
washed with saturated sodium chloride solution, dried with
MgSO4 and analysed by GC.
RT 6.65 min). The chemical structure was confirmed by 1H and
13C NMR spectroscopy. The spectroscopic data was in accor-
dance with those reported in literature.[33]
CLA 1c
1,2-Dilinoleoyl-sn-glycero-3-phosphocholine 3b
CLA was prepared from LA (6 g, 21.4 mmol, 99.9 % purity)
according to the procedure described previously[6] to give a
colourless oil (5.96 g, 99 %,) which contained a mixture of
isomers (percentage according to GC): 0.7 % LA (RT 8.94 min),
48.5 % cis-9,trans-11 (RT 10.89 min), 48.3 % trans-10,cis-12
(RT 11.03 min), 2.5 % other CLA isomers (RT 11.11–11.84 min),
purity (percentage according to GC) 97 %. dH (300 MHz,
CDCl3) 6.28 (m, 2H, H-11a, and H-11b), 5.94 (m, 2H, H-10a,
H-12b), 5.65 (m, 2H, H-12a, H-10b), 5.30 (m, 2H, H-9a, H-13b),
2.35 (t, J 7.4, 4H, H-2a, and H-2b), 2.17–2.13 (m, 4H, H-8a,
H-14b), 2.10–2.07 (m, 4H, H-13a, H-9b), 1.66–1.58 (m, 4H,
H-3a, andH-3b), 1.40–1.27(m, 32H, H-4a–7a, H-14a–17a,H-4b–
8b, and H-15b–17b), 0.89 (t, J 6.9, 6H, H-18a, and H-18b).
dC (75 MHz, CDCl3) 179.72 (C-1a and C-1b), 135.12 (C-12a),
134.74 (C-10b), 130.32 (C-13b), 130.05 (C-9a), 128.83 (C-10a),
128.69 (C-12b), 125.78 (C-11b), 125.68 (C-11a), 34.09 (C-2a
and C-2b), 33.04 (C-13a), 33.00 (C-9b), 31.88 (C-16a), 31.62
(C-16b), 29.78 (C-14a), 29.56 (C-15b), 29.65–29.21 (C-5a–7a
and C-5b–8b), 29.17 (C-4a and C-4b), 29.06 (C-15a), 27.80
(C-14b), 27.77 (C-8a), 24.79 (C-3a and C-3b), 22.77 (C-17a),
22.70 (C-17b), 14.25 (C-18a), 14.21 (C-18b). Note: signals
labelled ‘a’ are from the cis-9,trans-11 isomer of CLA, and those
labelled ‘b’ are from the trans-10,cis-12 isomer. m/z (HR-ESI)
Calc. for C18H32O2: 279.2330 [M ꢀ H]ꢀ. Found: 279.2325.
The title compound was obtained as a colourless greasy solid
(764 mg, 84 %), with 98 % purity (according to HPLC, RT
6.97 min). dH (300 MHz, 2 : 1 CDCl3/CD3OD (v/v)) 5.21–5.04
(m, 8H, H-9a–10a, H-12a–13a), 5.01 (m, 1H, H-2), 4.17 (m, 1H,
one of H-1), 4.07–3.98 (m, 2H, H-a), 3.93 (dd, J 12.0, 7.0, 1H,
one of H-1), 3.83–3.70 (m, 2H, H-3), 3.42–3.34 (m, 2H, H-b),
2.99 (s, 9H, N(CH3)3), 2.55 (t, J 5.6, 4H, H-11a), 2.16–2.03 (m,
4H, H-2a), 1.89–1.75 (m, 8H, H-8a, H-14a), 1.45–1.31 (m, 4H,
H-3a), 1.19–1.00 (m, 28 H, H-4a–7a, H-15a–17a), 0.67 (t, J 6.8,
6H, H-18a). dC (75 MHz, 2 : 1 CDCl3/CD3OD (v/v)) 173.75
(C-1a in sn-2), 173.39 (C-1a in sn-1), 129.96 (C-12a), 129.72
(C-10a), 127.86 (C-9a), 127.68 (C-13a), 70.25 (C-2), 70.15
(C-2), 66.29 (C-b), 63.43 (C-3), 63.36 (C-3), 62.50 (C-1),
58.83 (C-a), 58.76 (C-a), 53.91 (–N(CH3)3), 33.98 (C-2a in
sn-2), 33.83 (C-2a in sn-1), 31.28 (C-16a), 29.39 (C-15a),
29.18–28.61 (C-4a-7a, C-14a), 26.94 (C-8a), 25.37 (C-11a),
24.66 (C-3a in sn-2), 24.61 (C-3a in sn-1), 22.30 (C-17a), 13.66
(C-18a). Note: signals labelled ‘a’ are from the LA moiety, and
those labelled ‘a,b’ are from the choline moiety. dP (121 MHz,
2 : 1 CDCl3/CD3OD (v/v)) ꢀ0.19. m/z (HR-ESI) Calc. for
C44H80NO9P: 782.5694 [M þ H]þ. Found: 782.5678.
1,2-Di(conjugated)linoleoyl-sn-glycero-3-
phosphocholine 3c
The title compound was obtained as a colourless greasy solid
(746 mg, 82 %), with 98 % purity (according to HPLC, RT
6.95 min). dH (300 MHz, 2 : 1 CDCl3/CD3OD (v/v)) 6.06 (m,
2H, H-11a, and H-11b), 5.71 (m, 2H, H-10a, and H-12b), 5.41
(dtd, J 9.7, 6.9, 2.7, 2H, H-12a, and H-10b), 5.11–4.95 (m, 3H,
H-9a, H-13b, and H-2), 4.19 (m, 1H, one of H-1), 4.07–3.97 (m,
2H, H-a), 3.93 (dd, J 12.0, 7.0, 1H, one of H-1), 3.83–3.72 (m,
2H, H-3), 3.41–3.33 (m, 2H, H-b), 2.98 (s, 9H, N(CH3)3), 2.15–
2.04 (m, 4H, H-2a, and H-2b), 1.97–1.77 (m, 8H, H-8a, H-13a,
H-9b, and H-14b), 1.45–1.29 (m, 4H, H-3a, and H-3b), 1.21–
1.00 (m, 32H, H-4a–7a, H-14a–17a, H-4b–8b, and H-15b–17b),
0.69–0.60 (m, 6H, H-18a, and H-18b). dC (75 MHz, 2 : 1 CDCl3/
CD3OD (v/v)) 173.79 (C-1a and C-1b in sn-2), 173.42 (C-1a and
C-1b in sn-1), 134.54 (C-12a), 134.27 (C-10b), 129.86 (C-13b),
129.54 (C-9a), 128.55 (C-10a), 128.40 (C-12b), 125.51 (C-11b),
125.39 (C-11a), 70.27 (C-2), 70.16 (C-2), 66.32 (C-b), 63.45
(C-3), 63.38 (C-3), 62.52 (C-1), 58.84 (C-a), 58.78 (C-a), 53.94
(–N(CH3)3), 34.00 (C-2a and C-2b in sn-2), 33.85 (C-2a and
C-2b in sn-1), 32.63 (C-13a and C-9b), 31.51 (C-16a), 31.24
(C-16b), 29.59–28.56 (C-4a–7a, C-14a–15a, C-4b–8b, and
C-15b), 27.40 (C-8a and C-14b) 24.67 (C-3a and C-3b in
sn-2), 24.62 (C-3a and C-3b in sn-1), 22.37 (C-17a), 22.30
(C-17b), 13.69 (C-18a), 13.71 (C-18b). Note: signals labelled
‘a’ are from the cis-9,trans-11 CLA moiety, those labelled ‘b’
are from the trans-10,cis-12 CLA moiety, and those labelled
‘a,b’ are from the choline moiety. dP (121 MHz, 2 : 1 CDCl3/
MeOD (v/v)) 0.01. m/z (HR-ESI) Calc. for C44H80NO9P:
782.5694 [M þ H]þ. Found: 782.5679.
GPC Cadmium Chloride Complex
GPC (10 g, 38.7 mmol) was dissolved in methanol (65 mL) and
added slowly to a solution of CdCl2ꢃ21/2H2O (8.88 g,
38.7 mmol) in 30 mL of cold water. The mixture was stirred for
4 h at 08C. The GPC–CdCl2 precipitate was filtered, lyophilised,
and then dried in an Abderhalden’s drying pistol over P2O5 at
the boiling temperature of acetone to give white powder
(15.63 g, 91 %).
General Procedure of 1,2-Diacyl-sn-glycero-3-
phosphocholines Synthesis
PA, LA, or CLA (4.5 mmol) was dried by repeated co-
evaporation with an anhydrous CH2Cl2/benzene mixture (1 : 1
v/v) and then dissolved in anhydrous CH2Cl2 (35 mL). The
GPC–CdCl2 complex (0.5 g, 1.14 mmol), DMAP (278 mg,
2.28 mmol), and finally a solution of DCC (985 mg, 4.8 mmol)
in 10 mL of CH2Cl2 were added. The reaction mixture was
stirred at room temperature under a nitrogen atmosphere. The
course of the reaction was monitored by TLC (65 : 25 : 4 CHCl3/
CH3OH/H2O, (v/v/v)). After 40 h, the precipitate that was
formed in the reaction mixture was removed using a Shott’s
funnel. Ion-exchange resin (DOWEX 50W X8, Hþ form) was
added to the filtrate and mixed for 30 min to dislodge the cad-
mium chloride and DMAP. DOWEX was filtered off and the
solvent was evaporated under vacuum. The crude PC was
purified on a silica-gel column (65 : 25 : 4 CHCl3/CH3OH/H2O
(v/v/v)). Product-containing fractions of RF 0.4 were collected
and evaporated under vacuum (458C).
1-Palmitoyl-sn-glycero-3-phosphocholine 5
1,2-Dipalmitoyl-sn-glycero-3-phosphocholine 3a
GPC (700 mg, 2.7 mmol) and dibutyltin oxide (710 mg,
2.85mmol) were suspended in 30 mL of anhydrous propan-2-ol
and refluxed for 1 h. The reaction mixture was cooled to an
The title compound was obtained as a colourless greasy
solid (744 mg, 87 %), with 99 % purity (according to HPLC,