Cyclic phosphates derived from 2,2,6,6-tetrakis(hydroxymethyl)cyclohexanol acetals in the synthesis of new phospholipids

Full text of DOI:10.1023/A:1022537428919

Russian Journal of Organic Chemistry, Vol. 38, No. 10, 2002, pp. 1550 1551. Translated from Zhurnal Organicheskoi Khimii, Vol. 38, No. 10, 2002,
pp. 1599 1600.
Original Russian Text Copyright
2002 by Savin, Predvoditelev, Nifant’ev.
Cyclic Phosphates Derived
from 2,2,6,6-Tetrakis(hydroxymethyl)cyclohexanol Acetals
in the Synthesis of New Phospholipids*
G. A. Savin1, D. A. Predvoditelev2, and E. E. Nifant’ev2
1
Volgograd State Pedagogical University, pr. Lenina 27, Volgograd, 400131 Russia
2
Moscow State Pedagogical University, Moscow, Russia
Received April 26, 2002
The present communication describes the synthesis
of first representatives of hitherto unknown phospha-
tide acid analogs on the basis of cyclic phosphates
derived from 2,2,6,6-tetrakis(hydroxymethyl)cyclo-
hexanol. These compounds were synthesized with the
use of cyclic P(III) and P(V) derivatives which were
recently proved to be convenient reagents for lipid
chemistry [1, 2]. As initial alcohol we used readily
accessible protected polyol I which was treated with
cyclic phosphorous acid derivatives II and III to
obtain cyclic phosphite IV (Scheme 1). Phosphite IV
[
130 pp; Rf 0.6 (Silufol UV-254), hexane dioxane,
5:P1 (system A)] was converted in situ into phosphates
V VII by oxidation with iodosylbenzene or by the
action of sulfur or selenium. Phosphate V was isolated
by column chromatography on silica gel with hexane
Scheme 1.
II, Y = Cl; III, Y = NEt2; V X, R = C13H27; V, VIII, XI, X = O; VI, IX, XII, X = S; VII, X, XIII, X = Se.
____________
*
This study was financially supported by the Russian Founda-
tion for Basic Research (project no. 01-03-32459).
1070-4280/02/3810-1550$27.00 2002 MAIK Nauka/Interperiodica

CYCLIC PHOSPHATES DERIVED FROM 2,2,6,6-TETRAKIS-.. .
1551
dioxane (20 : 1) as eluent; thiophosphate VI and
selenophosphate VII were purified by recrystallization
from hexane.
phate IX, mp 54 55 C; Rf 0.45 (A); selenophosphate
X, mp 61 62 C; Rf 0.45 (A).
In the final stage, acylated phosphates VIII X
were treated with potassium stearate at 120 C (12 h).
The resulting potassium salts XI XIII were purified
by recrystallization from acetone (yield 50%). Com-
Phosphate V. Yield 56%; mp 114 116 C; Rf 0.25
[benzene dioxane, 5:1 (system B)];
6.3 ppm.
P
Thiophosphate VI. Yield 60%; mp 136 137 C;
Rf 0.7 (B); 62 ppm.
Selenophosphate VII. Yield 63%; mp 141 142 C;
Rf 0.7 (B);
68 ppm (1JP, Se = 990 Hz).
pound XI, mp 16 17 C, Rf 0.0 (B),
1 ppm; XII,
mp 57 58 C, Rf 0.0 (B),
57 ppm;P XIII, mp 63
P
64 C, Rf 0.0 (B), P 59 ppmP(1JP, Se = 790 Hz).
P
Phosphates V VII were subjected to direct acyla-
tion with myristoyl chloride at 20 C in the presence
of anhydrous zinc chloride. Tetramyristoyl derivatives
VIII X were isolated in up to 55% yield by column
chromatography on silica gel using hexane as eluent:
phosphate VIII, mp 48 50 C, Rf 0.3 (A); thiophos-
REFERENCES
1. Nifant’ev, E.E. and Predvoditelev, D.A., Usp. Khim.,
1994, vol. 63, no. 1, p. 73.
2. Predvoditelev, D.A. and Nifant’ev, E.E., Russ. J. Org.
Chem., 1995, vol. 31, no. 12, p. 1559.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 10 2002