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Improved Synthesis of Vitamin K1
771
The above-obtained yellow oil 2 was dissolved in acetic acid
(ca. 30 mL) in the presence of dodecyltrimethylammonium bromide
(ca. 0.2 g) and heated at 90ꢀC under argon in the dark for 15 min. The
mixture was then cooled and concentrated with a rotary evaporator.
This residue was purified by column chromatography on silica gel with
n-hexane/diethyl ether (20:1) as eluent, thereby obtaining (E/Z )-isomeric
1 as a yellow oil in 80–91% yields (Table 2). UV (hexane): ꢁmax ¼ 243, 249,
261, 270, 327 nm; IR (film): ꢂ ¼ 2940, 2920, 2850, 1660, 1620, 1598,
1
718 cmÀ1; H NMR: ꢀ ¼ 0.81 (d, 3H, J ¼ 6.5 Hz, CHCH3), 0.82 (d, 3H,
J ¼ 6.5 Hz, CHCH3), 0.86 (d, 6H, J ¼ 6.5 Hz, CHCH3), 0.97–1.45 (m,
17H, CH and CH2), 1.52 (m, 2H, CH2 at C50), 1.68 (s, 3H, cis-CH3
at C30), 1.78 (s, 3H, trans-CH3 at C30), 1.94 (t, 2H, J ¼ 9 Hz, CH2 at C40),
2.19 (s, 3H, ring CH3), 3.37 (d, 2H, J ¼ 7 Hz, CH2 at C10), 5.00 (t, 1H,
J ¼ 7 Hz, ¼CH at C20), 7.69 (m, 2H, aromatic H ), 8.08 (m, 2H, aromatic
H ); EIMS m/z ¼ 450 (Mþ, 100), 435 (6), 224 (26), 197 (18), 185 (20%).
Anal. for C31H46O2, calcd. (%) C 82.61, H 10.29; found C 82.44, H 10.37.
REFERENCES
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Weiser, H. Synthesis of all four stereoisomers of (E )-vitamins K1
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