5
16
Buděšínský, Fajkoš, Günter, Kasal:
EXPERIMENTAL
Meltin g poin ts were determ in ed on a m eltin g poin t m icro apparatus Boetius (Germ an y) an d
are un corrected. An alytical sam ples were dried over ph osph orus pen toxide at 50 °C/100 Pa.
Optical rotation s were m easured in ch loroform usin g an Autopol IV (Rudolf Research An a-
–
1
2
–1
lytical, Flan ders, U.S.A.); [α]D values are given in 10 deg cm
solution s were recorded on a Bruker IFS 88 spectrom eter, wave n um bers are given in cm
NMR spectra were m easured on FT-NMR spectrom eters Bruker AVANCE-500 an d Varian
g . IR spectra of ch loroform
–
1
.
1
13
UNITY-500 ( H at 500 MHz, C at 125.7 MHz) in CDCl , CD COCD an d/or C D . Ch em i-
cal sh ifts ( H referen ced to TMS, C related to th e solven t peak δ(CDCl ) 77.0 or δ(C D )
3
3
3
6
6
1
13
3
6
6
1
28.0) are given in ppm (δ-scale), couplin g con stan ts (J) in Hz. Hom on uclear an d
h eteron uclear 2D-NMR experim en ts (H,H-COSY, H,H-ROESY, H,H-J-resolved, H,C-HSQC, an d
H,C-HMBC) were used for com plete structure assign m en ts of proton an d carbon sign als.
Th in -layer ch rom atograph y (TLC) was perform ed on silica gel (ICN Bioch em icals) or alu-
m in a con tain in g 5% of gypsum . Preparative TLC (PLC) was carried out on 200 × 200 m m
plates coated with a 0.7 m m th ick layer of th e sam e m aterial; before use, th e plates were
kept in atm osph ere of am m on ia for 2 h . Before evaporation on a rotary evaporator in
vacuum (bath tem perature 50 °C), solution s in organ ic solven ts were dried over an h ydrous
m agn esium sulfate. W h en ever solution s of potassium carbon ate, potassium h ydrogen -
carbon ate or h ydroch loric acid were used, th eir con cen tration was always 5%. For colum n
ch rom atograph y, 60–120 µm silica gel was used. Reversed-ph ase preparative HPLC was car-
ried out on Separon SGX RPS C-18 (10 µm ) in lin ear water–m eth an ol gradien t (40–60% dur-
in g 20 m in ).
Epoxidation of Estr-5(10)-en e-3,17-dion e (1)
A cooled (0 °C) solution of peroxyph th alic acid (7.0 g, 38.4 m m ol) in eth er (400 m l) was
slowly added to a stirred solution of estr-5(10)-en e-3,17-dion e (1; 10.0 g, 36.7 m m ol) in
ch loroform (50 m l). Th e m ixture was kept for at laboratory tem perature 2 h , th en wash ed
with th e solution of sodium carbon ate an d water an d con cen trated in vacuum . Th e product
(
a m ixture of 2 an d 3, 8.1 g, 78%) m elts at 102–144 °C (m eth an ol). TLC (alum in ium oxide
with 5% of gypsum pre-treated with am m on ia, developed with ch loroform wash ed with am -
1
13
m on ia): two spots with R 0.35 (2) an d 0.26 (3). For H an d C NMR data, see Tables I an d II.
F
1
0β-Hydroxyestr-4-en e-3,17-dion e (4) an d 5,10β-Dih ydroxy-5α-estran e-3,17-dion e (6)
Th e m ixture of epoxides 2 an d 3 (5.0 g, 17.3 m m ol) was dissolved in dioxan e (100 m l) an d
th e solution was treated with a solution of con cen trated sulfuric acid (0.02 m l) in water
(
20 m l). After 16 h , th e acid used was n eutralised with th e solution of potassium h ydrogen -
carbon ate an d dioxan e was distilled off un der reduced pressure. Th e product was extracted
with eth yl acetate, dried, an d con cen trated in vacuum . Ch rom atograph y on a colum n of sil-
ica gel (300 g) in ben zen e–eth er (9:1) with an in creasin g am oun t of m eth an ol (0 to 4%)
yielded com poun d 4 (1.3 g, 26%), m .p. 204–205 °C (ch loroform –eth er); [α] +153 (c 0.5)
D
1
1
1
13
(
lit. gives 206–207 °C an d [α]D +148). For H an d C NMR data, see Tables I an d II. Th e
m ore polar product was diol 6 (3.1 g, 58%), m .p. 222–228 °C (ch loroform –eth er); [α] +91.8
D
1
2
13
1
(
c 0.25) (lit. gives 223–225 °C an d [α]D +118, lit. gives 240–241 °C an d [α]D +97). For H
1
3
an d C NMR data, see Tables I an d II.
Collect. Czech. Chem. Commun. (Vol. 70) (2005)