638
BADANYAN et al.
Table 7. GLC and TLC data and IR spectra of methoxydienes III and dienals IV
Comp.
no.
Retention time, min (oven temperature, C)
Rfa
E,Z: E,E
1
IR spectrum, , cm
Y: E,Z: X: E,E
IIIa
IIIb
IIIc
10.43: 11.04: 0: 0 (92)
15.64: 16.38: 0: 17.70 (90)
17.02: 17.76: 18.28: 19.48 (102)
0.23
0.25
0.27
970, 1065, 1080, 1130, 1160, 1195, 1620, 1660
960, 1060, 1075, 1125, 1160, 1195, 1620, 1650
970, 1065, 1080, 1095, 1110, 1130, 1180, 1195,
1630, 1670
IIId
IVa
17.19: 18.64: 19.71: 21.36 (125)
0: 9.6: 0: 0 (80)
0.32
0.10
980, 1030, 1070, 1110, 1190, 1620, 1660
975, 1600, 1620, 1680, 2710
IVb [13]
IVc
IVd [13]
0: 8.73: 0: 0 (90)
0: 11.21: 0: 11.31 (102)
0: 11.96: 0: 12.73 (125)
0.12: 0.10 957, 1010, 1595, 1620, 1680, 2720
0.19: 0.13 975, 1600, 1630, 1680, 2720
0.24: 0.18 980, 1600, 1628, 1675, 2730
a
Eluent ether hexane, 1:10.
of aldehyde I in 6 ml of dry THF was added drop-
wise. The mixture was stirred for 1 h at 78 C or for
30 min at 0 C and was treated as described above
in A and A . Some physical properties and spectral
parameters of the resulting dimethoxydienes III are
given in Tables 1, 4, 5, and 7.
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Schlosser olefination. To a suspension of 10 mmol
of alkyltriphenylphosphonium bromide II in 24 ml
of anhydrous THF and 12 ml of dry ether, stirred at
20 C under argon, we added dropwise 9.1 ml of
a 1.1 N solution of butyllithium in hexane (10 mmol).
The mixture was kept for 1 h at that temperature and
cooled to 78 C, and a solution of 10 mmol of alde-
hyde I in 12 ml of anhydrous THF and 6 ml of dry
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for 30 min at 78 C, 10 mmol of anhydrous methanol
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was stirred for 10 min at 20 C (the progress of the
reaction was monitored by TLC) and neutralized with
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dried over sodium sulfate. The solvent was removed,
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fraction was 750 mg (86%) of a mixture of (E,Z)- and
(E,E)-dienals IV at a ratio of 91:9; the second frac-
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dienals IV at a ratio of 15:85. Overall yield of
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RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 37 No. 5 2001