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HELVETICA CHIMICA ACTA – Vol. 88 (2005)
250 ml), washed with H2O (4×300 ml), dried (Na2SO4), and evaporated in vacuo. The crude product was puri-
fied by CC (SiO2; PE/AcOEt 7:1) to afford pure 8 (2.0 g, 95.5%). Colorless oil. IR (film): 2932, 2828, 1469, 1427,
1393, 1348, 1159, 1057, 1024, 975, 935. 1H-NMR (400 MHz, CDCl3): 1.91 (s, Me of side chain)2), 2.16 (s, MeAr);
3.42 (d, 3J=6.4, ArCH2); 3.57, 3.59 (2s, 2 MeOCH2); 3.86, 3.88 (2s, 2 MeOAr); 3.96 (s, BrCH2); 5.05, 5.07 (2s, 2
OCH2O); 5.54 (t, 3J=6.0, C=CH of side chain). EI-MS: 420/418 (4, M+), 294 (25), 263 (25), 249 (64), 233 (5), 217
(17), 45 (100). HR-EI-MS: 420.0966/418.0985 (M+, C18H27BrO6þ ; calc. 420.0971/418.0991).
1-{(2E,6E,10E,14E,18E,22E,26E,30E,34E)-3,7,11,15,19,23,27,31,35,39-Decamethyl-5-[(4-methylphenyl)-
sulfonyl]tetraconta-2,6,10,14,18,22,26,30,34,38-decaen-1-yl}-3,4-dimethoxy-2,5-bis(methoxymethoxy)-6-methyl-
benzene (10)3). BuLi (1.0 ml of a 1.6
M soln. in hexane) was added dropwise to a soln. of solanesyl p-tolylsulfone
(9; 0.913 g, 1.19 mmol) and HMPA (2.64 ml) in THF ( 8.0 ml) at ꢀ708 over 30 min under N2. The resulting yel-
low mixture was stirred at ꢀ708 for 30 min. A soln. of the bromide 8 (0.333 g, 0.795 mmol) in THF (1.0 ml) was
added dropwise, and the mixture was warmed up to 08 over a period of 2 h, and finally taken up in Et2O (3×
50 ml). The mixture was washed with 1N aq. HCl (50 ml) and H2O (3×25 ml), dried (Na2SO4), and the org.
layer was evaporated in vacuo. The crude product was purified by CC (SiO2; PE/AcOEt 8 :1) to afford pure
10 (0.750 g, 85.3%). Colorless oil. IR (film): 2923, 2854, 1450, 1428, 1146, 1056, 978. 1H-NMR (400 MHz,
CDCl3): 1.21 (s, MeC=); 1.58–1.60 (br. s, 8 MeC=); 1.68, 1.69 (2s, 2 MeC=); 1.85–2.16 (m, 8 (CH2)2CH=,
2
3
2
MeAr); 2.22 (q, J=ꢀ12.8, J=12.4, 1 H of CH2(4) of side chain); 2.42 (s, Me of Ts); 2.89 (br. d, J=ꢀ12.8,
1 H of CH2(4) of Ar); 3.28 (dd, 2J=ꢀ15.1, 3J=6.4, 1 H of CH2(1) of side chain); 3.35 (dd, 2J=ꢀ15.1,
3J=6.4, 1 H of CH2(1) of side chain); 3.53, 3.57 (2s, 2 MeOCH2O); 3.84 (s, 2 MeOAr); 3.88 (m, HꢀC(5) of
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side chain); 4.84 (d, J=10.1, C=C(H); 5.00, 5.02 (2s, 2 OCH2O); 5.04–5.13 (m, 9 C=CH); 7.28 (d, J=8.2, 2
arom. H of Ts); 7.69 (d, 3J=8.2, 2 arom. H of Ts). MALDI-MS: 1130 ([M+Na]+, C70H106NaO8S+).
1-[(2E,6E,10E,14E,18E,22E,26E,30E,34E)-3,7,11,15,19,23,27,31,35,39-Decamethyltetraconta-2,6,10,14,18,
22,26,30,34,38-decaen-1-yl]-3,4-dimethoxy-2,5-bis(methoxymethoxy)-6-methylbenzene (11). To a stirred soln. of
10 (0.553 g, 0.500 mmol) in THF (50 ml) was added dropwise sodium naphthalenide (2.5 ml of a 1M soln. in THF)
at ꢀ788 over 30 min. The resulting mixture was stirred for 30 min at this temp. Then, the excess sodium naph-
thalenide was destroyed by addition of MeOH (25 ml). The mixture was warmed to 08, poured into H2O (80 ml),
and extracted with Et2O (3×100 ml). The combined org. phase was washed with brine (3×50 ml), dried
(Na2SO4), and evaporated in vacuo. The crude product was purified by CC (SiO2; PE/AcOEt 15 :1) to afford
11 (0.475 g, 99.8%; >99.4% pure by HPLC). Colorless solid. M.p. 28.0–28.58. IR (KBr): 2923, 2853, 1450,
1
1428, 1391, 1349, 1159, 1056, 978. H-NMR (400 MHz, CDCl3): 1.58, 1.60, 1.68, 1.75 (4s, 11 MeC=C); 1.95–
2.10 (m, 9 (CH2)2CH=); 2.17 (s, MeAr); 3.37 (d, 3J=6.4, ArCH2); 3.58, 3.60 (2s, 2 MeOCH2); 3.86 (s, 2
MeOAr); 5.04, 5.05 (2s, 2 OCH2O); 5.04–5.13 (m, 10 C=CH). MALDI-MS: 975.6 ([M+Na]+, C63H100NaO6þ).
Coenzyme Q10 (1). A soln. of 11 (95.2 mg, 0.10 mmol) in MeOH/hexane 2 :1 (30 ml) containing one drop of
sat. aq. HCl was stirred at 408 for 4 h. After cooling to r.t., the soln. was neutralized with methanolic KOH to pH
7. Then, H2O (10 ml) was added, and the resulting mixture was extracted with hexane (3×50 ml). The combined
org. phase was washed with H2O (3×25 ml), dried (Na2SO4), and evaporated in vacuo. The crude product was
accompanied by a small amount of isomeric compounds (1.5% by HPLC). Purification by CC (SiO2; PE/AcOEt
15 :1) afforded 1 (80.2 mg, 93.0%). Orange oil, which gradually solidified. M.p. 49–49.58 (lit. m.p. 48–498 [5a]).
IR (KBr) : 2923, 2853, 1655, 1615, 1450, 1385, 1265, 1155. 1H-NMR (400 MHz, CDCl3): 1.58. 1.60 (2s, 9 MeC=C);
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1.68 (s, MeC=C); 1.74 (s, MeC=C); 2.01 (s, MeAr); 1.93–2.09 (m, 9 (CH2)2CH=); 3.18 (d, J=6.9, CH2(1) of
side chain); 3.98, 4.00 (2s, 2 MeOAr); 4.93 (t, 3J=7.3, HꢀC(2) of side chain); 5.04–5.13 (m, 9 C=CH).
MALDI-MS: 885.7 ([M+Na]+, C59H90NaO4þ).
REFERENCES
[1] K. Folkers, ‘Coenzyme Q: Biochemistry, Bioenergetics and Clinical Applications of Ubiquinone’, Ed. G.
Lenaz, Wiley-Interscience, New York, 1985, p. 457.
[2] L. Ernster, G. Dallner, Biochim. Biophys. Acta. 1995, 1271, 195; L. Ernster, P. Forsmark, K. Nordenbrand,
BioFactors 1992, 3, 241; V. Kagan, E. Serbinova, L. Packer, Biochem. Biophys. Res. Commun. 1990, 169,
851.
2
)
)
‘Side chain’ = 4-bromo-3-methylbut-2-enyl.
For clarity (similarity of atom numbering), the less-systematic parent name, (-benzene rather than -sulfone)
was chosen.
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