ethyl acetate (9:1→8:2), giving 8 (225 mg, yield 40%). The
2.83 (m, 10H, C8, C11, C14, C17, C20-CH ), 5.35 (m, 12H, all
2
olefin protons).
characterization data are given in ref. 6.
6
2-O-tert-Butyldimethylsilyl-1-tetracosa (all Z)-6,9,12,15,18,21-
1
hexaenoyl-sn-glycerol (8): H NMR (500 MHz, CDCl ): δ 0.08 (s,
3
Introduction of choline phosphate into 8
6
1
4
H, Si(CH ) ), 0.85 (s, 9H, C(CH ) ), 0.95 (t, J = 7.8, 3H, C24-CH ),
3
2
3
3
3
.40 (m, 2H, C4-CH ), 1.63 (dd, J = 7.1, 7.1, 2H, C3-CH ), 2.05 (m,
2
2
To phosphoric trichloride (26.3 ml) in nitrogen atmosphere was
H, C5, C23-CH ), 2.33 (m, 2H, C2-CH ), 2.83 (m, 10H, C8, C11,
2
2
added a solution of 8 (100 mg, 0.18 mmol) and Et N (33.0 ml)
3
C14, C17, C20-CH ), 3.58–4.10 (m, 5H, protons on glycerol struc-
2
in ethanol-free distilled CHCl (2.0 ml) at 0 ЊC in the presence
ϩ
3
ture), 5.35 (m, 12H, all olefin protons). Found (ES) m/z: (M ϩ H )
45.4; C H O Si requires: 544.9. [α] Ϫ2.7 (c 22.5, CHCl ). Yield
of a trace of BHT and the solution was stirred for 0.5 h at this
temperature, then, at room temperature for an additional 1 h.
Dry choline tosylate (100 mg) and freshly distilled pyridine
rt
D
5
3
3
56
4
3
2
5%.
7 2-O-tert-Butyldimethylsilyl-1-tetracosa (a1 ll Z)-6,9,12,15,18,21-
hexaenoyl-sn-glycerophosphocholine (9): NMR (500 MHz,
CDCl ): δ 0.08 (s, 6H, Si(CH ), 0.85 (s, 9H, N(CH ), 0.95 (t,
J = 7.8, 3H, C24-CH ), 1.40 (m, 2H, C4-CH ), 1.62 (dd, J = 7.1, 7.1,
(
75 ml) were added successively, and the reaction mixture was
H
stirred at room temperature for 48 h. The reaction mixture was
3
3
)
2
)
3 3
poured into a mixture of CHCl –methanol (2:1) to extract the
3
2
3
2
2
3
H, C3-CH ), 2.05 (m, 4H, C5, C23-CH ), 2.30 (m, 2H, C2-CH ),
2
2
2
product into the organic phase. The extract was concentrated
and the residue was chromatographed on silica gel eluted with
CH OH–CHCl –28% aq. NH (30:60:5) giving 9. The charac-
.85 (m, 10H, C8, C11, C14, C17, C20-CH ), 3.35 (s, 9H, N(CH ) ),
2
3 3
.78 (br, 2H, OCH CH N), 3.80–4.10 (m, 5H, protons on glycerol
2
2
3
3
3
structure), 4.30 (br, 2H, OCH CH N), 5.25 (m, 12H, all olefin
protons). Found (ES) m/z: (M ϩ H ) 711.1; C H NO PSi requires:
7
2
2
terization data are given in ref. 7.
ϩ
3
8
68
7
rt
10.1. [α] Ϫ0.12 (c 6.0, CHCl ). Yield 46%.
D
3
8
1-Tetracosa (all Z)-6,9,12,15,18,21-hexaenoyl-sn-lysophosphocholine
1
Acknowledgements
(10): H NMR (500 MHz, CDCl ): δ 0.95 (t, J = 7.8, 3H, C24-CH ),
3
3
1
.40 (m, 2H, C4-CH ), 1.60 (dd, J = 7.1, 7.1, 2H, C3-CH ), 2.05 (m,
2
2
We are grateful to Venture Business Laboratory and SC-NMR
Laboratory of Okayama University for H NMR.
4H, C5, C23-CH ), 2.30 (m, 2H, C2 and C2Ј-CH ), 2.85 (m, 10H,
2
2
1
C8, C11, C14, C17, C20, C6Ј, C9Ј, C12Ј, C15Ј, C18Ј-CH ), 3.30
2
(
s, 9H, N(CH ) ), 3.75 (br, 2H, O CH CH N), 3.80–4.40 (m, 5H,
3
3
2
2
protons on glycerol structure), 4.25 (br, 2H, OCH CH N), 5.30
2
2
ϩ
(
m, 12H, all olefin protons). Found (ES) m/z: (M ϩ H ): 596.4;
Notes and references
rt
C H NO P requires: 595.4. [α] Ϫ0.05 (c 4.5, CHCl ). Yield 92%.
3
2
54
7
D
3
1
M. I. Aveldano, J. Biol. Chem., 1987, 262, 1172; M. I. Aveldano and
H. Sprecher, J. Biol. Chem., 1987, 262, 1180; M. I. Aveldano,
Biochemistry, 1988, 27, 1229; T. S. Wiedmann, R. D. Pates,
J. M. Beach, A. Salmon and M. F. Brown, Biochemistry, 1988, 27,
9 2-Docosahexaenoyl-1-tetracosa (all Z)-6,9,12,15,18,21-hexaenoyl-sn-
1
glycerophosphocholine: (11): H NMR (500 MHz, CDCl ): δ 0.90
3
(t, J = 7.8, 6H, C24-CH and C22Ј-CH ), 1.35 (m, 2H, C4-CH ),
3
3
2
1.55 (dd, J = 7.1, 7.1, 2H, C3-CH ), 2.00 (m, 8H, C3-CH ), 2.25 (m,
2
2
6
469.
4H, C2 and C2Ј-CH ), 2.75 (m, 10H, C5, C11, C14, C17, C20, C6Ј,
2
2
(a) N. Baba, T. Akiyama, S. Tahara and S. Nakajima, Biosci.
Biotechnol. Biochem., 1995, 59, 353; (b) S. S. Haider, M. Tanaka,
Md. K. Alam, S. Nakajima, N. Baba and S. Shimizu, Chem. Lett.,
C9Ј, C12Ј, C15Ј, C18Ј-CH ), 3.30 (s, 9H, N(CH ) ), 3.75 (br, 2H,
2
3 3
OCH CH N), 3.80–4.40 (m, 5H, protons on glycerol structure), 4.25
2
2
(br, 2H, OCH CH N), 5.30 (m, 24H, all olefin protons). Found (ES)
2
2
ϩ
rt
1
998, 175.
G. H. Dodd and B. T. Golding, J. Chem. Soc., Perkin Trans. 1, 1976,
273.
m/z: (M ϩ H ) 906.6; C H NO P requires: 905.6. [α] Ϫ0.5 (c 2,
54 84 8 D
3
4
CHCl ). Yield 36%.
3
2
10 (a) Y. Terao, M. Murata and K. Achiwa, Tetrahedron Lett., 1988, 29,
5173; (b) Y.-F. Wang, J. J. Lalonde, M. Momonga, D. E. Bergbreiter
and C.-H. Wong, J. Am. Chem. Soc., 1988, 110, 7200.
11 D. Breitgoff, K. Laumen and M. P. Schneider, J. Chem. Soc., Chem.
Commun., 1986, 1523; K. Prasad, H. Estermann, C.-C. Chen,
R. Oljan and G. E. Hardtmann, Tetrahedron: Asymmetry, 1990, 1,
421.
N. Baba, K. Yoneda, S. Tahara, J. Iwasa, T. Kaneko and
M. Matsuo, J. Chem. Soc., Chem. Commun., 1990, 1281; N. Baba,
S. Tahara, K. Yoneda and J. Iwasa, Chem. Express., 1991, 6, 423.
1
5
Tetracosahexaenoate (5): H NMR (500 MHz, CDCl ): δ 0.95 (t,
3
J = 7.8, 3H, C24-CH ), 1.26 (m, 2H, C4-CH ), 1.65 (dd, J = 7.1, 7.1,
3
2
2
H, C3-CH ), 2.05 (m, 4H, C5, C23-CH ), 2.35 (m, 2H, C2-CH ),
2
2
2
J. Chem. Soc., Perkin Trans. 1, 2001, 221–223
223