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T. Rezanka et al. / Chemistry and Physics of Lipids 159 (2009) 104–113
112
4.9. (S)-9-Cycloheptyl-2-methylnonan-1-ol (13).
4.12. (S)-Picolinyl 11-cycloheptyl-4-methylundecanoate (16)
(Rezanka, 1990).
p-Toluenesulfonic acid monohydrate (0.03 g, catalytic amount)
was added to a solution of 12 (112 mg, 0.33 mmol) in methanol
(10 mL), and stirring was continued for 4 h under reflux. After neu-
tralization with potassium carbonate, the mixture was poured into
brine and extracted with ether. The ethereal extract was washed
with brine, dried, and concentrated in vacuo. The residue was
chromatographed on TLC with hexane–ether (7:1) with a yield
of 75 mg of 13 (89%). 1H NMR (CDC13) ı 0.88 (3H, d, J = 6.9 Hz),
1.10–2.10 (28H, m), 3.47 (2H, m); 13C NMR (CDC13) ı 17.2 (q),
26.4 (t), 26.8 (t), 28.4 (t), 28.5 (t), 29.0 (t), 29.1 (t), 29.3 (t), 30.1
(t), 30.4 (t), 33.1 (d), 33.5 (t), 33.6 (t), 34.0 (t), 35.4 (t), 37.7 (d),
67.6 (t); HRMS: calcd. for C17 H34O 254.2610 [M]+; found 254.2611
(ꢀ = 0.1 ppm).
A solution of potassium tert-butoxide in THF (0.5 mL, 1.0 M) was
added to nicotinyl alcohol (1 mL). After mixing, the appropriate
methyl ester 1 (30 mg) in dry dichloromethane (1 mL) was added,
and the mixture was held at 40 ◦C for 30 min in a closed vial. After
cooling to room temperature, water and hexane were added, and
the organic phase was collected, dried over anhydrous sodium sul-
fate, and evaporated.
Feeding experiment was carried out in fermentor culture as
described above. The labeled precursor (13CH3CH2COONa) (485 mg,
i.e. 5 mM) was added to 10 mL sterile aqueous solutions adjusted to
pH 5.0 as three equal parts at intervals of 4 h starting at 0 h. Cells
were harvested after 24 h. Because of the high 13C content of the pre-
cursors (13C: 99%) the enrichment in the labeled products is given
and not converted into incorporation rates.
Acknowledgements
To a solution of 50 L (0.57 mmol) of oxalyl chloride in 5 mL of
CH2Cl2 at −70 ◦C was added 51 L (0.72 mmol) of dimethyl sul-
foxide in 1 mL of CH2Cl2, according to the procedure described for
different compounds (Oikawa et al., 1995). The mixture was stirred
for 10 min, 71 mg (0.28 mmol) of 13 in 5 mL of CH2Cl2 was intro-
duced and the resulting mixture stirred for 30 min. To this was
added 0.28 mL (2 mmol) of triethylamine. The mixture was fur-
ther stirred at ambient temperature for 30 min and quenched with
30 mL of 5% aqueous NaHSO4. The aqueous layer was separated and
extracted with ether (2× 10 mL). The combined organic extracts
were washed with 10 mL of brine, dried, filtered, and concentrated
in vacuo. The crude aldehyde 14 thus obtained was used without
further purification.
The research was supported by projects of the Ministry of Edu-
cation, Youth and Sports of the Czech Republic (nos. 1M06011 and
MSM6046137305), and by Institutional Research Concept AV 0Z 502
0910.
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4.11. (S)-Methyl 11-cycloheptyl-4-methylundecanoate (1).
The methyl ester 1 was prepared in a similar manner as com-
pound 8. From 80 mg (0.26 mmol) of 15 was obtained 79 mg (98%)
of 1. The final product was purified by TLC (EtOAc-hexane, 5:95).
[˛]D −0.75; IR (neat): 1729 (C O); 1H NMR (CDC13) ı 0.88 (3H,
24
d, J = 6.8 Hz), 1.04–1.75 (30H, m), 2.44 (t, J = 7.6, H-2, 2H), 3.61
(s, 3H); 13C NMR (CDC13) ı 174.2 (C1), 51.2 (OMe), 32.1 (C2),
31.6 (C3), 36.7 (C4), 37.0 (C5), 27.4 (C6), 28.3–29.6 (C7,8,9,4ꢀ,5ꢀ),
27.4 (C10), 38.1 (C11), 21.4 (C12), 39.5 (C1ꢀ), 34.7 (C2ꢀ,7ꢀ), 26.6
(C3ꢀ,6ꢀ); HRMS: calcd. for C20H38O2 310.2872 [M]+; found 310.2875
(ꢀ = 0.3 ppm).
Hsu, F.F., Turk, J., 2005. Electrospray ionization with low-energy collisionally acti-
vated dissociation tandem mass spectrometry of complex lipids: structural