THE SYNTHESIS OF PHOSPHATES
63
O
O
COOK
COO(CH2)nI
I(CH2)nI
(VIII) n = 10
(IX) n = 22
(XI) n = 10
(XII) n = 22
OH
(X)
OH
O
OCH2C6H4CH3
COO(CH2)n OP O
OCH2C6H4CH3
AgOPO(OCH2C6H4CH3)2
(XIII) n = 10
(XIV) n = 22
OH
(Ib) n = 10 or (Ic) n = 22
Scheme.
sion of lithium aluminum hydride (0.2 g, 5.26 mmol) in (0.42 g, 62%) was obtained as a thick liquid, Rf 0.76,
ether (20 ml). The mixture was refluxed for 1 h, cooled,
treated with 10% ammonium chloride (2–3 ml), and
evaporated to dryness. The dry residue was loaded into
a Soxhlet apparatus, and glycol (IV) or (V) was
extracted with benzene or toluene, respectively. After
cooling, the respective crystals were precipitated from
the benzene and toluene solutions:
which was thickened and melted at 30°ë (cf. lit. mp
30°ë [5]), or diiodide (IX) (0.32 g, 71%), mp 66–68°ë
(acetone); 1H NMR: 0.95–2.0 (40H, m, CH2), 3.1 (4H,
t, J 7 Hz, Iëç2).
11-Deoxyprostaglandin E1 w-iodo-n-decyl ester
(XI) and w-iodo-n-docosyl ester (XII). A solution of
11-deoxyprostaglandin Ö1 (X) (0.34 g, 1 mmol) in
0.1 M potassium hydroxide (10 ml) in methanol was
evaporated dry in a vacuum. The residue was dissolved
in DMF (10–20 ml), and (VIII) (0.40 g, 1 mmol) or
(IX) (0.56 g, 1 mmol) was added; the mixture was kept
at room temperature for 1 day and evaporated. The res-
idue was dissolved in ether, and the ether solution was
washed, dried, and evaporated as described above. The
residue was chromatographed on a silica gel column
(20 g) to give a thick oily (XI); yield 0.3 g (50%);
Glycol (IV); 0.6 g (86%); mp 70–75°ë (from ben-
zene) (cf. lit. mp 72–75°ë [2]).
Glycol (V); 1.2 g (86%); mp 104–105°ë (from tolu-
ene) [3]); 1H NMR: 1.0–1.7 (40H, m, CH2), 3.55 (4H, t,
J 6 Hz, OCH2).
1,10-Dichlorodecane (VI) and 1,22-dichloro-
docosane (VII). Thionyl chloride [0.6 ml for dichloride
(VI) or 0.3 ml for dichloride (VII)] was added drop-
wise and stirred into a pyridine solution (0.16 ml) of
diol (IV) (0.35 g, 2 mmol) or diol (V) (0.34 g, 1 mmol),
respectively, cooled to 0°ë, and the reaction mixture
was kept for 1 h at room temperature. The mixture was
then refluxed for 1 h, cooled, treated with water (2 ml),
and extracted with ether. The extract was successively
washed with water, sodium bicarbonate solution, and
sodium chloride solution, dried with sodium sulfate,
and evaporated to give dichloride (VI) (0.36 g, 83%) as
a thick liquid; Rf 0.79; mp 15°ë (cf. [4], mp 15.6°ë), or
dichloride (VII), (0.3 g, 87%), mp 63–64°ë (acetone).
1H NMR: 0.95–2.0 (40H, m, CH2), 3.44 (4H, t, J 6 Hz,
ClCH2).
1
Rf 0.35; H NMR: 0.81 (3H, t, J 7 Hz, ëç3), 1.0–2.4
(42H, m, CH2 and CH), 3.1 (2H, t, J 7 Hz, ICH2), 4.0
(3H, m, OCH2 and H15), and 5.33 (2H, m, CH=CH) or
a thick oily (XII); yield 0.31 g (40.4%); Rf 0.41;
1H NMR: 0.81 (3H, t, J 7 Hz, ëç3), 1.0–2.4 (66H, m,
CH2 and CH), 3.1 (2H, t, J 7 Hz, ICH2), 4.0 (3H, m,
OCH2 and H15), and 5.33 (2H, m, CH=CH).
11-Deoxyprostaglandin E1 w-hydroxy-n-decyl
ester w-di(p-methylbenzyl) phosphate (XIII) and w-
hydroxy-n-docosyl ester w-di(p-methylbenzyl)
phosphate (XIV). A mixture of (XI) (0.3 g, 0.5 mmol)
or (XII) (0.31 g, 0.4 mmol) and silver salt of di(p-meth-
ylbenzyl) phosphate (0.2 g, 0.5 mmol) was refluxed in
benzene (3–5 ml) for 5 h, cooled, and applied onto a sil-
ica gel column (20 g). After chromatography, phos-
phate (XIII) (0.15 g, 38%) was obtained as a thick, low
1,10-Diiododecane (VIII) and 1,22-diiodo-
docosane (IX). A mixture of dichloride (VI) (0.36 g,
1.7 mmol) or dichloride (VII) (0.3 g, 0.8 mmol), ace-
tone (10–20 ml), and sodium iodide (1 g) was heated in
an autoclave at 125°ë for 6–8 h. After cooling, the reac-
tion mixture was diluted with ether, washed, and dried
as described above. After evaporation, diiodide (VIII)
1
mobile noncrystallizing oil; Rf 0.21; H NMR: 0.81
(3H, t, J 7 Hz, ëç3), 1.0–2.4 (42H, m, CH2 and CH),
3.8–4.1 (5H, m, OCH2 and H15), 4.9 (4H, d, J 7.6 Hz,
RUSSIAN JOURNAL OF BIOORGANIC CHEMISTRY Vol. 28 No. 1 2002