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SERKOV, BEZUGLOV
389 ([M – HF – 2 × NO2]+, 3.8), 391 ([M – 2 × NO2–OH]+, on silica gel; yield 31.4 mg (73%); slight yellow vis-
2.6), 371 ([M – HF – 2 × NO2 – OH]+, 2.9), 343 ([M – F – cous oil; Rf 0.68 (100 : 10 : 1 chloroform–methanol–
CH2ONO2 – ONO2]+, 3.9), 318 ([M – (CH2ONO2)2COH]+, ammonia); UV-spectrum: λmax 217 nm, ε7200 (ethanol);
13.4), 315 ([M – (CH2ONO2)2C–HF]+, 37), 298 ([M – mass spectrum (CI), m/z: 390 ([M]+), 372 ([M – H2O]+).
(CH2ONO2)2COH – HF]+, 22.3), 190 (100).
Prostaglandin A2 1,3-bis(nitrooxy)prop-2-yl
ester (VIIIe) was synthesized from 100 mg of PG A2
(I) by the method B; yield 123.8 mg (83%); viscous
yellow oil, Rf 0.65 (40 : 10 : 1 benzene–dioxane–acetic
acid); UV-spectrum: λmax 218 nm, ε 7140 (ethanol);
mass spectrum (CI), m/z: 499 ([M + H]+), 481 ([M + H–
H2O]+).
Prostaglandin E2 amide (IXa) was synthesized
from 40 mg of PG E2 by the method B; yield 36.3 mg
(91%); colorless viscous oil, Rf 0.1 (1 : 1 chloroform–
aceton); mass spectrum of trimethylsilyl derivative
(EI), m/z: 568 ([M+ H]+, 0.9), 553 ([M+ H–CH3]+, 1.4), 523
([M + H – (CH3)3]+, 0.9), 495 ([M + H –(CH3)3Si]+, 12), 480
([M + H–(CH3)3Si–NH]+, 12), 424 ([M + H – (CH3)3Si –
C5H11]+, 67), 405 ([M–(CH3)3Si – (CH3)3SiOH]+, 58), 390
([M – CH3 – (CH3)3Si – (CH3)3SiOH]+, 22), 334 ([M –
((CH3)3Si)3 – H]+, 100).
Prostaglandin E2 tert-butyl ester (IXc) was syn-
thesized from 30 mg of PG E2 by the method B; yield
24.1 mg (72%); colorless viscous oil, Rf 0.68 (2 : 1 ben-
zene–ethyl acetate); mass spectrum (CI), m/z: 408
([M]+), 390 ([M – H2O]+).
Prostaglandin E2 1,3-bis(nitrooxy)prop-2-yl
ester (IXd) was synthesized from 100 mg of PG E2 by
method B; yield 108.5 mg (74%); colorless viscous oil;
Rf 0.39 (40 : 10 : 1 benzene–dioxane–acetic acid); mass
spectrum (CI), m/z: 517 ([M + H]+).
Prostaglandin F2a dimethylamide (Xb) was syn-
thesized from 40 mg of PG F2α by method B; yield
34.9 mg (81%); colorless viscous oil; Rf 0.31 (2 : 1 ben-
zene–ethyl acetate); mass spectrum (CI), m/z: 381
([M]+), 363 ([M – H2O]+).
Prostaglandin F2a tert-butyl ester (Xc) was syn-
thesized from 35 mg of PG F2α by method B; yield
26.4 mg (65%); colorless viscous oil; Rf 0.54 (2 : 1 ben-
zene–ethyl acetate); mass spectrum (CI), m/z : 410
([M]+), 392 ([M – H2O]+).
Prostaglandin F2a 1,3-bis(nitrooxy)prop-2-yl
ester (Xd) was synthesized from 100 mg of prostaglan-
din F2α by the method B; yield 115.6 mg (79%); color-
less viscous oil; Rf 0.25 (40 : 10 : 1 benzene–dioxane–
acetic acid); mass spectrum (CI), m/z: 519 ([M + H]+),
501 ([M + H – H2O]+).
15-(tert-Butyldimethyl)silyloxyprostaglandin A2
tert-butyldimethylsilyl ester (IVa) was synthesized
from 100 mg of prostaglandin A2 (I); yield of pros-
tanoid (IVa) 151.8 mg (89%), colorless viscous oil,
Rf 0.75 (7 : 1 benzene–ethyl acetate); UV-spectrum:
λmax 217 nm (ethanol); mass spectrum (EI), m/z: 562
([M]+, 20), 547 ([M – CH3]+, 4), 505 ([M – C4H9]+, 100),
491 ([M – C5H11]+, 5.5), 430 ([M – C6H15SiOH]+, 16), 373
([M – C6H15SiOH – t-C4H9]+, 70), 299 ([M – C6H15SiOH –
C6H15SiO]+, 54).
15-(tert-Butyldimethyl)silyloxyprostaglandin A2
(Va). 1 M HCl (150 µl) was added to a solution of dis-
ilyl derivative (IVa) (100 mg) in 1 ml THF and stirred
for 1.5 min at room temperature. The reaction mixture
was poured out in a mixture of chloroform of 4 ml and
2 ml of saturated water solution of NaHCO3. The
organic layer was separated, water acidified with 1 M
HCl to pH 3–4 and extracted with chloroform (3 × 10 ml).
The extract was washed with water, saturated NaCl,
dried by anhydrous Na2SO4, filtered, and filtrate was
evaporated. The residue was purified by column chro-
matography on silica gel in a gradient system benzene–
ethyl acetate. Prostaglandin (Va) was obtained; yield
71.5 mg (89%), colorless viscous oil, Rf 0.55 (3 : 1 ben-
zene–ethyl acetate); mass spectrum of methyl ester
(EI), m/z: 431 ([M – OCH3]+, 7), 405 ([M − C4H9]+, 100),
391 ([M – C5H11]+, 34), 373 ([M –C4H9 – OCH3]+, 40).
15-(tert-Butyldimethyl)silyloxyprostaglandin A2
fluoride (VIa) was synthesized from 70 mg of pros-
tanoid (Va) by the method A; yield 64.6 mg (85%); col-
orless viscous oil; Rf 0.77 (7 : 1 benzene–ethyl acetate);
mass spectrum (EI), m/z: 450 ([M]+, 20), 430 ([M – HF]+,
18), 393 ([M– C4H9]+, 100), 379 ([M– C5H11]+, 28), 393 ([M
– C4H9 – HF]+, 31).
Prostaglandin A2 amide (VIIIc) was synthesized
from 100 mg of prostaglandin Ä2 (I) by the method B;
yield 91.2 mg (92%); slight yellow viscous oil, Rf 0.29
(100 : 10 : 1 chloroform–methanol–ammonia), λmax
217 nm, ε 7800 (ethanol); mass spectrum (CI), m/z: 334
([M + ç]+), 316 ([M + ç – H2O]+).
Prostaglandin A2 tert-butyl ester (VIIId). Fluo-
ride (VIa) (50 mg) was dissolved in acetone (1 ml) tert-
butanol (100 µl) was added, and mixture was stirred for
15-Fluoro-15 deoxyprostaglandin E2 1,3-
5 h at room temperature. Solvent was evaporated, and bis(nitrooxy)prop-2-yl ester (XVI). Prostaglandin E2
the oily residue was dissolved in 0.5 ml THF, added (XI) (100 mg) was silylated by the method C. The tris-
1 ml of 67% aqueous acetic acid and 10 µl of 1 M silyl derivative (XII) was dissolved in THF (2 ml), 1 M
hydrochloric acid were added and the mixture was HCl (300 µl) was added and the mixture was stirred at
stirred for 18 h at room temperature. The reaction mix- room temperature for 5 min. The reaction mixture was
ture was diluted with water and extracted with etyl ace- treated as described for prostanoid (Va). The mixture of
tate (3 × 5 ml). The extract was washed with water, sat- 11- and 15-monosilyl derivatives of PG E2 was sepa-
urated water solution of NaCl, dried with anhydrous rated by column chromatography on silica gel in gradi-
Na2SO4, filtered, and filtrate was evaporated. The result- ent system benzene–ethyl acetate. The resulting
ing derivative was purified by column chromatography 11-BDMS derivative (XIII) was fluorinated by the
RUSSIAN JOURNAL OF BIOORGANIC CHEMISTRY Vol. 35 No. 1 2009