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J. Matikainen et al. / Tetrahedron 59 (2003) 567–573
2.3.9. E,6Z-Nonadienal (21). Ph3PvCHCHO (4.0 g,
13.2 mmol) and the aldehyde (20) (0.5 g, 4.5 mmol) were
refluxed overnight in benzene (30 ml) under Ar. Benzene
was evaporated and the residue extracted with CH2Cl2/
hexane (1:1). Flash chromatography of the concentrate
(elution with CH2Cl2/hexane 4:3) yielded 0.28 g (45%) of
crude (21) containing 15–20% of the 2E,6Z-nonadienal
(m, 8H, H-20, H-30, H-40, H-50), 1.36 (m, 2H, H-10), 1.39 (m,
1H, H-1b), 1.41 (m, 1H H-2b), 1.50 (m, 2H, H-3a and
H-3b), 1.62 (m, 1H, H-2a), 1.63 (m, 2H, H-60), 1.79 (m, 1H,
H-1a), 1.90 (m, H-4a), 2.10 (qd, J¼9.0, 4.5 Hz, 01H, H-3a),
2.18 (m, 1H, H-5a), 2.32 (t, J¼7.5 Hz, 2H, H-7 ), 2.57 (m,
1H, H-7a), 3.67 (s, 3H, H-90), 5.39 (ddd, J¼9.9, 2.0, 1.8 Hz,
1H, H-7), 5.65 (ddd, J¼9.9, 4.8, 2.4 Hz, 1H, H-6). 13C NMR
d 16.2 (C-100), 24.6, 25.0 (C-60), 26.3 (C-3), 27.5, 29.2, 29.3,
29.8, 31.5 (C-5), 32.3, 32.7 (C-1), 34.1 (C-70), 36.8 (C-4),
39.5 (C-7a), 41.60 (C-3a), 51.4 (C-90), 130.2 (C-7), 132.3
(C-6), 174.2 (C-8 ). HRMS: C19H32O2 requires 292.2402,
found 292.2399.
1
isomer as byproduct. H NMR d 0.96 (3H, t, J¼7.6 Hz,
H-9), 2.04 (2H, quintet of multiplets J¼7.4 Hz, H-8), 2.26
(2H, brq, J¼7.0 Hz, H-5), 2.40 (2H, qm, J¼7.1 Hz, H-4),
5.31 (1H, dtt, J¼10.7, 7.0, 1.5 Hz, H-6), 5.45 (1H, ddm,
J¼10.7, 7.2 Hz, H-7), 6.13 (1H, ddt, J¼15.6, 7.8, 1.5 Hz,
H-2), 6.25 (1H, dt, J¼15.6, 6.6 Hz, H-3), 9.50 (1H, d,
J¼7.8 Hz, H-1). 13C NMR d 14.5 (C-9), 20.8 (C-8), 25.7
(C-5), 33.0 (C-4), 127.0 (C-6), 133.5 (C-2), 133.6 (C-7),
158.4 (C-3), 194.4 (C-1).
2.4.3. CL3. 1H NMR d 0.93 (t, J¼7.5 Hz, 3H, H-20), 1.10–
1.90 (m, 17 H), 1.81 (m, 1H, H-4), 1.98 (m, 1H, H-5), 2.16
(m, 1H, H-3a) 2.31 (t, J¼7.5 Hz, 2H, H-600), 2.58 (m, 1H,
H-7a), 3.67 (s, 3H, H-800), 5.45 (ddm, 1H, J¼10.0, 5.0 Hz,
H-7), 5.82 (ddd, J¼10.0, 5.0, 2.0 Hz, 1H, H-6). 13C NMR d
12.4 (C-20), 24.8, 24.9, 25.0, 26.7, 29.0, 29.2, 29.7, 33.0,
2.3.10. Methyl 9Z,11E,15Z-octadecatrienoate (5). The
phosphonium salt from 9-bromononanoic acid methyl ester
(16) (1.8 g, 3.5 mmol), K2CO315(0.5 g), the 5E,7E-non-
adienal (17) (0.44 g, 3.2 mmol), 1,4-dioxane (8.0 ml) and
H2O (4 drops) were stirred overnight under argon at ca.
958C. Flash chromatography of the concentrate yielded
50 mg (14%) of crude (5). The (5) was isolated in pure
00
34.1 (C-6 ), 37.0, 38.1, 39.8 (C-7a), 40.1 (C-4), 41.1 (C-3a),
00
51.4 (C-8 ), 130.4 (C-6), 130.9 (C-7), 174.3 (C-700).
2.4.4. CL4. 1H NMR d 0.88 (t, J¼7.0 Hz, 3H, H-20), 1.10–
1.90 (m, 17 H), 1.29 (m, 1H, H-4), 2.02 (m, 1H, H-3a), 2.12
(m, 1H, H-5), 2.31 (t, J¼7.5 Hz, 2H, H-600), 2.37 (qm,
J¼6 Hz, 1H, H-7a), 3.67 (s, 3H, H-800), 5.58 (ddd, J¼10.0,
5.0, 1.5 Hz, 1H, H-7), 5.65 0(ddd, J¼10.0, 4.5, 2.5 Hz, 1H,
H-6). 13C NMR d 12.1(C-2 ), 21.4, 24.9, 25.0, 27.5, 29.2,
29.7, 30.7, 30.9, 32.8, 34.1 (C-600), 34.2 (C-5), 38.2 (C-7a),
38.6 (C-3a), 41.5 (C-4), 51.4 (C-800), 130.4 (C-6), 130.7
(C-7), 174.3 (C-700).
1
state by argentation chromatography. H NMR d 0.96 (t,
J¼7.5 Hz, 3H, H-18),1.32 (br s, 6H, H-4, H-5 and H-6),
1.34 (br quintet, J¼7.5 Hz, 2H, H-7), 1.62 (br quintet,
J¼7.5 Hz, 2H, H-3), 2.05 (quintet, J¼7.5 Hz, 2H, H-17),
2.15 (m, 6H, H-8, H-13 and H-14), 2.30 (t, J¼7.5 Hz, 2H,
H-2), 3.65 (s, 3H, H-10), 5.36 (m, 3H, H-9, H-15 and H-16),
5.66 (dt, J¼15.1, 7.2 Hz, 1H, H-12), 5.94 (dd, J¼11.2,
10.2 Hz, 1H, H-10), 6.32 (dd, J¼15.1, 11.2 Hz, 1H, H-11).
13C NMR d 14.3 (C-18), 20.6 (C-17), 24.9 (C-3), 27.0, 27.7,
29.0, 29.1(2C), 29.6 C-4), 33.0, 34.1, 51.4 (C-10), 125.9,
128.3, 128.6, 130.2, 132.1 (C-16), 133.9, 174.3 (C-1).
HRMS: C19H32O2 requires 292.2402, found 292.2400.
2.4.5. CL5. 1H NMR d 0.98 (d, J¼7.1 Hz, 3H, H-100), 1.00–
1.77 (m, 17H), 1.31 (m, 1H, H-4a), 1.80 (m, 1H, H-5b),
2.16 (m, 1H, H-3a), 2.31 (t, J¼7.5 Hz, 2H, H-70), 2.51 (m,
1H, H-7a), 3.68 (s, 3H, H-90), 5.33 (dt, J¼10.0, 2.6 Hz, 1H,
H-7), 5.38 (dt, J¼10.0, 2.1 Hz, 1H, H-6). 13C NMR d 20.0,
23.0, 23.2, 24.9, 27.1, 29.2, 29.3, 29.8, 31.1, 31.7, 31.8,
34.1, 40.00, 40.04, 41.8, 51.4, 130.5, 133.8, 174.3.
2.4. Cyclization experiments, general procedure
The methyl octadecatrienoates 2,4 or 5 in about 5% solution
in decalin under Ar were heated overnight in a sealed
ampoule at 260–2708C. The reaction product was then
chromatographed over silica (elution with dichloro-
methane/hexane 1:1). The cyclic compounds were isolated
by argentation chromatography (elution with 5% ethyl
acetate in dichloromethane or alternatively 5–10% diethyl
ether in hexane).
2.4.6. CL6. 1H NMR d 0.92 (t, J¼7.6 Hz, 3H, H-20), 1.14–
1.69 (m, 17H), 1.35 (m, 1H, H-4a), 1.75 (m, 1H, H-5b),
2.20 (m, 1H, H-3a), 2.31 (t, J¼7.5 Hz, 2H, H-600), 2.50 (m,
1H, H-7a), 3.67 (s, 3H, H-90), 5.37 (dt, J¼10.0, 2.2 Hz, 1H,
H-7), 5.49 (dt, J¼10.0, 2.0 Hz, 1H, H-6). 13C NMR d 11.9,
22.9, 23.0, 24.3, 25.0, 25.9, 29.2, 29.8, 31.8, 32.8, 34.1,
35.8, 39.4, 39.8, 40.3, 51.4, 130.4, 131.1, 174.3.
00
1
2.4.1. CL1. H NMR d 1.03 (d, J¼7.2 Hz, 3H, H-1 ), 1.11
(m, 01H, H-1b), 1.200–1.60 (m, 10H, H-3a0 and H-3b, H-10,
H-2 , H-30 and H-4 ), 1.38 (m, 2H, H-5 ), 1.44 (m, 1H,
H-40b), 1.52 (m, 1H, H-3ab), 1.63 (quintet, 2H, J¼7.0 Hz,
H-6 ), 1.71 (m, 2H, H-2a and H-2b), 1.81 (m, 1H, H-1a),
1.82 (m, 1H, H-7a), 2.20 (m, H-5a), 2.33 (t, 2H, J¼7.5 Hz,
H-70), 3.67 (s, 3H, H-90), 5.44 (ddd, 1H, J¼9.8, 2.4, 1.0 Hz,
H-6), 5.76 (br d, 1H, J¼9.08 Hz, H-7). 13C NMR0 d 22.2
(C-100), 22.4 (C-2), 25.0 (C-6 ), 25.9 (C-3), 27.3 (C-1 ), 28.1,
29.2 (C-1), 29.3 (2C), 29.9, 34.1 (C-70), 35.7 (C-5) 38.5
(C-7a), 41.0 (C-4), 43.3 (C-3a), 51.4 (C-90), 129.1 (C-7),
132.3 (C-6), 174.3 (C-80). HRMS: C19H32O2 requires
292.2402, found 292.2410.
References
¨ ¨ ¨
1. Matikainen, J.; Kaltia, S.; Hamalainen, M.; Hase, T.
Tetrahedron 1997, 53, 4531–4538.
2. Potteau, B.; Dubois, P.; Rigaud, J. Ann. Technol. Agric. 1978,
27(3), 655–679.
3. Eckert, W. R.; Scharmann, H.; Zeman, A. Fette Seifen
Anstrichm. 1969, 71, 468–471.
4. Mikusch, J. D.; Sagredos, A. N. Fette Seifen Anstrichm. 1971,
73, 384–393.
5. Sagredos, A. N. Fette Seifen Anstrichm. 1974, 76, 8–16.
6. (a) Hase, A.; Stowell, L. Effect of bicyclic fatty acids in the
diet of growing rats. ISF Congress, New York, May 5–10,
00
1
2.4.2. CL2. H NMR d 0.97 (d, J¼7.6 Hz, 3H, H-1 ), 1.33