1
20
B. Bednarczyk-Cwynar et al. / Journal of Molecular Structure 1053 (2013) 115–121
4
. Experimental
(CH
3
, COOCH
3
), 46.7 (C, C(17)); DEPT: 8 ꢁ CH
3
, 10 ꢁ CH , 4 ꢁ CH;
2
+Å
EIMS m/z: 483.0 (6.0%) M .
4.1. General experimental procedures
4.4. 3-Nitrile-3,4-secoolean-4(23),12-dien-28-oic acid methyl ester (5)
The thin layer chromatography (TLC) analyses (reactions pro-
and 3-oxo-3a-aza-A-homoolean-12-en-28-oic acid methyl ester (6)
gress and the level of compounds purity) was performed on HPTLC
aluminum sheets (Kieselgel 60 F245) with benzene and ethyl ace-
tate in different volume ratios as mobile phases. The chromato-
grams were visualized by spraying them with 10% ethanolic
solution of sulfuric acid and then heating the plates in temperature
about 110 °C during few minutes. The column chromatography
was performed using silicagel 60; 0.063–0.200 mm (70–
3
POCl (2.8 ml, 4.60 g, 0.03 mol) was dropwise added to a stirred
and cooled solution of 3-hydroxyiminoolean-12-en-28-oic acid
methyl ester 4 (4.84 g, 0.01 mol) in dried pyridine (200 ml). The re-
sulted solution was left at room temperature overnight. The
brownish mixture was then poured into 6-fold volume of water
with ice, slightly acidified with HCl. The resulted light-brown pre-
cipitate was filtered off, washed with water, dried (4.38 g), sub-
2
2 2
30 mesh), with CH Cl and next AcOEt as eluents. Melting points
were determined using open capillary method in Kofler apparatus
and were uncorrected. IR spectra were recorded using Specord IR-
jected to column chromatography on silicagel (CH
AcOEt) and crystallized.
2 2
Cl , next
7
5 spectrophotometer, for 0.5% mixtures of tested compounds and
Compound 5: yield: 1.16 g (25%); colorless needles (ethanol);
m.p.: 195–197 °C (lit. m.p.: 193–195 °C [19]); R : 0.87 (C :AcOEt,
: +78.6 (c 0.53, CHCl ); IR (KBr,
);
, 300 MHz, ppm) d: 5.30 (1H, t, J = 3.4 Hz, C(12)AH),
4.90 (1H, s, C(23)AH), 4.66 (1H, s, C(23)AH), 3.63 (3H, s, COOCH ),
2.88 (1H, dd, J = 4.0 and 13.6 Hz, C(18)AH ), 1.74 (3H, s, C(24),
CH
), 1.15, 0.93, 0.92, 0.90, 0.78 (15H, 5 ꢁ s, 5 ꢁ CH
(CHCl , 75 MHz, ppm) d: 178.1 (C, C(28)), 146.7 (C, C(4)), 143.9
C, C(13)), 121.6 (CH, C(12)), 120.1 (C, C(3)), 114.1 (CH , C(23)),
1.5 (CH , COOCH , 11 ꢁ CH
), 46.6 (C, C(17)); DEPT: 7 ꢁ CH
1
KBr. NMR spectra for hydrogen atoms ( H) and for carbon atoms
f
6 6
H
1
3
25
D
(
C) were recorder on Varian Gemini 300 VT apparatus with
9:1), 0.60 (CH
2
Cl
2
), purple spot; ½
aꢄ
3
1
ꢂ1
TMS as an internal standard. The multiplicities of signals in
H
cm
)
m
max: 3050 (C(4)@C(23)), 2230 (C„N), 1710 (C@O, COOCH
3
1
NMR spectra were marked as follows: s – singlet, br/s – broad sin-
glet, t – triplet, dd – doublet of doublets. Mass spectra (MS) were
recorded using AMD 402 spectrophotometer with electroionisa-
tion. The elucidation of the chemical structures was based on IR,
H NMR (CHCl
3
3
b
13
3
3
); C NMR
1
13
H NMR, C NMR and MS analysis.
3
(
2
5
3
3
3
2
,
+
Å
4.2. 3-Oxoolean-12-en-28-oic acid methyl ester (3)
4 ꢁ CH; EIMS m/z: 465.5 (10.4%) M .
Compound 6: yield: 2.89 g (60%); colorless needles (ethanol);
Jones’ reagent was added dropwise (to small excess) to a satu-
m.p.: 298–300.5 °C (lit. m.p.: 290–293 °C [19]); R : 0.35 (AcOEt),
f
2
5
rated and stirred solution of 3b-hydroxyolean-12-en-28-oic acid
methyl ester (2, 4.71 g, 0.01 mol) in acetone (140 ml) at room tem-
perature. The resulting yellow–green mixture was stirred to the to-
tal consumption of substrate (TLC control, about 30 min), then
isopropyl alcohol was added dropwise and the obtained green sus-
pension was filtered off; the filtrate was poured into a 5-fold vol-
ume of water. The formed white precipitate was filtered off,
washed with water, dried and crystallized. Yield: 4.22 g (90%); col-
0.29 (C H :AcOEt, 1:1), dark pink spot; [
a
]
D: +79.7 (c 0.59,
6
6
ꢂ1
CHCl ); IR (KBr, cm
3
) mmax: 3200 (NAH, lactam), 1710 (C@O,
1
COOCH ), 1670 (C@O, lactam); H NMR (CHCl , 300 MHz, ppm) d:
3
3
5.69 (1H, s, NAH, lactam), 5.30 (1H, t, J = 3.4 Hz, C(12)AH), 3.63
(3H, s, COOCH ), 2.87 (1H, dd, J = 3.8 and 13.7 Hz, C(18)AH ),
3
b
1
3
1.28, 1.27, 1.13, 1.10, 0.93, 0.90, 0.77 (21H, 7 ꢁ s, 7 ꢁ CH );
3
C
NMR (CHCl , 75 MHz, ppm) d: 178.3 (C, C(28)), 177.0 (C, C(3)),
3
143.8 (C, C(13)), 122.2 (CH, C(12)), 51.5 (CH , COOCH ), 46.7 (C,
3
3
orless needles (ethanol); m.p.: 185–186 °C; R
f
: 0.72 (C
6
H
6
:AcOEt,
),
C(17)); DEPT: 8 ꢁ CH , 10 ꢁ CH , 4 ꢁ CH; EIMS m/z: 483.4 (12.9%)
3
2
ꢂ1
+Å
9
:1), purple-brown spot; IR (KBr, cm
)
m
max: 1705 (C@O, COOCH
3
M .
1
1
685 (C@O, C(3))
;
H NMR (CHCl
3
, 300 MHz, ppm) d: 5.31 (1H, t,
), 2.88 (1H, dd, J = 3.8
), 1.14, 1.09, 1.05, 1.04, 0.93, 0.90, 0.78
J = 3.2 Hz, C(12)AH), 3.63 (3H, s, COOCH
and 13.7 Hz, C(18)AH
3
Conflict of interest
b
1
3
(
21H, 7 ꢁ s, 7 ꢁ CH
C(3)), 178.2 (C, C(28)), 143.8 (C, C(13)), 122.1 (CH, C(12)), 51.5
CH , COOCH , 10 ꢁ CH , 4 ꢁ CH;
), 46.8 (C, C(17)); DEPT: 8 ꢁ CH
EIMS m/z: 468.8 (11.2%) M .
3 3
); C NMR (CHCl , 75 MHz, ppm) d: 217.7 (C,
All authors declare no financial and no commercial conflicts of
interest.
(
3
3
3
2
+
Å
Appendix A. Supplementary material
4
.3. 3-Hydroxyiminoolean-12-en-28-oic acid methyl ester (4, the
accessing number: CCDC 912788)
9.006. These data include MOL files and InChiKeys of the most
important compounds described in this article.
Hydroxylamine hydrochloride (3.47 g, 0.05 mol) and sodium
acetate (6.56 g, 0.08 mol) were added to a saturated, hot solution
of 3-oxoolean-12-en-28-oic acid methyl ester (3, 4.69 g,
References
0
.01 mol) in ethanol (100 ml) and the resulting mixture was re-
fluxed to total consumption of substrate (TLC control, about
0 min), cooled and poured into a 5-fold volume of water. The
[
1] M.B. Smith, J. March, March’s Advanced Organic Chemistry. Reactions,
Mechanisms and Structure, fifth ed., John Wiley & Sons Incorporation, New
3
[
[
formed white precipitate was filtered off, washed with water, dried
and crystallized. Yield: 4.50 g (93%); colorless needles (ethanol);
m.p.: 247–249 °C; R
f
: 0.62 (C
H
6 6
:AcOEt, 9:1), purple spot; IR (KBr,
ꢂ1
1
cm
)
m
max: 3245 (OH, oxime), 1720 (C@O, COOCH
, 300 MHz, ppm) d: 9.37 (1H, br/s, oxime), 5.29 (1H, t,
J = 3.4 Hz, C(12)AH), 3.63 (3H, s, COOCH ), 2.90 (1H, dd, J = 4.0
and 13.6 Hz, C(18)AH ), 1.16, 1.11, 1.06, 1.03, 0.92, 0.90, 0.76
3
); H NMR
(
CHCl
3
[
[
[
3
b
1
3
(
21H, 7 ꢁ s, 7 ꢁ CH
3 3
); C NMR (CHCl , 75 MHz, ppm) d: 178.3 (C,
8] H. Takahashi, K. Tanabe, M. Aketa, R. Kishi, S. Furukawa, M. Nakano, J. Chem.
Phys. 126 (2007) 084508-1–10.
C(28)), 167.0 (C, C(3)), 143.8 (C, C(13)), 122.2 (CH, C(12)), 51.5