Synthesis of acylhydrazones from lupane and 19β,28-epoxy-18α- oleanane 2,3-seco-aldehydonitriles

Article abstract of DOI:10.1007/s10600-010-9520-x

2,3-seco-Triterpene acylhydrazones, which are interesting as new biologically active compounds, were prepared by reaction of lupane and 19β,28-epoxy-18α-oleanane 2,3-seco-aldehydonitriles with acylated hydrazines.

Full text of DOI:10.1007/s10600-010-9520-x

Chemistry of Natural Compounds, Vol. 46, No. 1, 2010
SYNTHESIS OF ACYLHYDRAZONES FROM LUPANE AND
19ꢀ,28-EPOXY-18ꢁ-OLEANANE 2,3-seco-ALDEHYDONITRILES
I. A. Tolmacheva, N. V. Galaiko, and V. V. Grishko*
UDC 547. 597:542.952.3+547.288.3
2,3-seco-Triterpene acylhydrazones, which are interesting as new biologically active compounds, were
prepared by reaction of lupane and 19ꢀ,28-epoxy-18ꢁ-oleanane 2,3-seco-aldehydonitriles with acylated
hydrazines.
Keywords: A-seco-triterpenoids, 2,3-seco-aldehydonitriles, betulin, betulinic acid, allobetulone, acylhydrazines,
hydrazones.
Lupane triterpenoids are a valuable source of new pharmacologically active derivatives among low-molecular-weight
compounds of plant origin. Functionalization of their more available representatives betulin and betulinic acid at C-3, C-28,
and C-30 produced numerous derivatives with anti-HIV, antitumor, immunostimulating, and anti-inflammatory activity [1].
More drastic changes of the C skeleton of betulin have been investigated much less frequently. Moreover, lupane
seco-derivatives were detected in extracts of medicinal plants [2, 3] and among cytotoxic products from microbial transformation
of betulin and betulinic acid [4]. High cytotoxic and antiviral activity was reported for semi-synthetic 2,3-seco-dicarboxylic
acids of the oleanane and lupane type [5, 6] and 2,3-seco-aldehydonitriles and their derivatives obtained from betulonic acid
and its methyl ester [7–9].
In continuation of research on chemical transformation of 2,3-seco-triterpenoids and in consideration of the reported
high anti-angiogenic and antiviral activity of betulonic acid hydrazones and hydrazides [10–12], we synthesized 2,3-seco-
triterpene acylhydrazones based on 2,3-seco-3-oxo-1-cyano lupane (1) and 19ꢀ,28-epoxy-18ꢁ-oleanane (2) derivatives.
Triterpene 2,3-seco-acylhydrazones 3a–e and 4a–e were prepared by reaction of acylated hydrazines with 2,3-seco-
aldehydonitriles 1 or 2 in EtOH in the presence of catalytic amounts of glacial acetic acid [13]. The reaction was carried out
at room temperature with yields of 20-68% of 3a–e and 4a–e after purification by chromatography.
29
20
30
26
19
17
21
13
27
11
25
5
COOCH
9
3
1
28
NC
RCOHNNH
2
NC
15
R CONHN HC
1
OHC3
C H OH, CH COOH
2
5
3
7
23
24
3a - e
1
29
19
30
21
O
13
11
26
7
25
5
17
15
1
9
28
RCOHNNH
2
NC
NC
OHC3
C H OH, CH COOH
27
R CONHN HC
1
2
5
3
23
24
2
4a - e
R = CH - (a); C H CH(C H )- (b); C
H
- (c); C
H
- (d); C H - (e)
1
3
4
9
2
5
10 21
14 29
6 5
Institute of Technical Chemistry, Ural Branch, Russian Academy of Sciences, 614013, Russia, Perm, ul. Akad.
Koroleva, 3, e-mail: grishko@aport.ru. Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 37–40, January–February,
2010. Original article submitted July 3, 2009.
©
0009-3130/10/4601-0039 2010 Springer Science+Business Media, Inc.
39

The structures of synthesized hydrazones 3a–e and 4a–e were confirmed by IR and NMR spectroscopy. IR spectra of
–1
the hydrazones contained absorption bands at 1653–1682, 2233–2244, and 3192–3236 cm that corresponded to stretching
vibrations of CH=N, C=N, and NH bonds, respectively. The PMR spectra showed resonances for protons typical of lupane or
19ꢀ,28-epoxy-18ꢁ-oleanane, an acyl substituent, a singlet for C-3 at 7.15–7.70 ppm, and a broad singlet for the amino proton
13
at 8.54–9.32. C NMR spectra exhibited characteristic resonances for nitrile (118.23–118.80 ppm), C-3 (154.16–160.64),
and the carbonyl C atom of the acyl substituent (163.62–176.57).
Thus, the studies resulted in the synthesis of 2,3-seco-triterpene acylhydrazones that are of interest as new biologically
active agents.
EXPERIMENTAL
IR spectra were recorded in mineral oil mulls on a Bruker IFS 66/S IR-Fourier spectrometer (Germany). PMR and
13
C NMR spectra were recorded in CDCl on a Varian Mercury+ spectrometer (USA) at operating frequency 300 or 75.5 MHz
3
with HMDS internal standard. Melting points were measured on a PTP melting-point apparatus (Russia). Specific optical
rotation was determined for CHCl solutions on a Perkin–Elmer 341 polarimeter (USA) at 589 nm. Elemental analyses (C, H,
3
N) were performed using a Leco CHNS-9321P analyzer (Netherlands) and agreed with those calculated.
Column chromatography (CC) was performed over silica gel (Merck, 0.35–0.70 mm) with a compound:sorbent ratio
of ꢂ 1:50 with elution by a mixture selected individually for each compound. TLC used Sorbfil plates (Russia) and detection
by spraying with an ethanol solution of phosphomolybdic acid (20%) and subsequent heating at 100–120°C for 2–3 min.
2,3-seco-Aldehydonitriles 1 and 2 were synthesized by the literature method [7].
General Method for Preparing Acylhydrazones (3a–e, 4a–e). A solution of 1 or 2 (0.44 mmol) in EtOH (15 mL)
was treated with acylhydrazine (0.44 mmol) and glacial acetic acid (2 drops) and left at room temperature for 7 h. The course
of the reaction was monitored by TLC. Solvent was evaporated. The solid was purified by CC.
Acetylhydrazone of 2,3-seco-28-methoxycarbonyl-1-cyanolup-20(29)-en-3-al (3a), C H N O . Yield after
33 51
3 3
21
purification by CC, 0.26 g (48%), R 0.34 (hexane:EtOAc, 5:1), mp 120–122°C (hexane:EtOAc, 5:1), [ꢁ] +9.5° (c 0.5,
f
D
–1
CHCl ). IR spectrum (ꢃ, cm ): 1653 (CH=NNHCO), 1726 (COOCH ), 2237 (CꢄN), 3236 (NH).
3
3
PMR spectrum (300 MHz, CDCl , ꢅ, ppm, J/Hz): 0.90, 0.92, 1.00, 1.16, 1.18 (5 ꢆ 3H, 5s, 5CH ), 1.67 (3H, s,
3
3
CH -30), 2.22 (3H, s, CH ), 2.29 and 2.56 (2H, 2d, J = 18.3, H -1, AB-system), 2.99 (1H, td, J = 10.5, 5.1, CH-19), 3.66
3
3
AB
2
(3H, s, COOCH ), 4.60 and 4.72 (2H, 2s, H -29), 7.21 (1H, s, H-3), 9.24 (1H, br.s, NH).
3
2
13
C NMR spectrum (75.5 MHz, CDCl , ꢅ, ppm): 14.54, 15.80, 18.43, 19.18, 20.15, 20.32, 21.77, 22.44, 25.46,
3
28.24, 29.58, 29.64, 30.41, 31.88, 33.33, 36.80, 38.17, 40.61, 42.32, 42.44, 42.74, 44.73, 46.85, 49.12, 51.27, 51.47, 56.46,
109.83 (C-29), 118.30 (C-2), 150.21 (C-20), 154.59 (C-3), 173.29 (CONH), 176.58 (C-28).
2-Ethylpentanoylhydrazone of 2,3-seco-28-methoxycarbonyl-1-cyanolup-20(29)-en-3-al (3b), C H N O . Yield
39 63
21
3 3
after purification by CC, 0.37 g (59%), R 0.4 (hexane:EtOAc, 7:3), mp 86–88°C (hexane:EtOAc, 7:3), [ꢁ] +2.0° (c 0.5,
f
D
–1
CHCl ). IR spectrum (ꢃ, cm ): 1666 (CH=NNHCO), 1725 (COOCH ), 2237 (CꢄN), 3202 (NH).
3
3
PMR spectrum (300 MHz, CDCl , ꢅ, ppm, J/Hz): 0.83, 0.86 (2 ꢆ 3H, 2t, J = 7.1, 2CH ), 0.89, 0.92, 1.00, 1.17, 1.19
3
3
(5 ꢆ 3H, 5s, 5CH ), 1.67 (3H, s, CH -30), 2.26 and 2.51 (2H, 2d, J = 18.0, H -1, AB-system), 2.98 (1H, td, J = 9.0, 5.7,
3
3
AB
2
H-19), 3.10–3.22 (1H, m, C H CH(C H )CONHN=CH), 3.66 (3H, s, COOCH ), 4.60 and 4.70 (2H, 2s, H -29), 7.20 (3H, s,
4
9
2
5
3
2
H-3), 9.25 (1H, br.s, NH).
13
C NMR spectrum (75.5 MHz, CDCl , ꢅ, ppm): 11.91, 12.01, 13.96, 14.03, 14.53, 15.79, 18.31, 19.18, 20.18, 21.79,
3
22.65, 22.70, 25.45, 28.26, 28.37, 29.62, 29.79, 30.42, 31.83, 31.88, 33.33, 36.80, 38.19, 40.62, 42.40, 42.56, 42.76, 44.68,
46.85, 49.14, 51.26, 51.40, 56.47, 109.82 (C-29), 118.23 (C-2), 150.19 (C-20), 154.16 (C-3), 176.57 (CONH), 178.77 (C-28).
Undecanoylhydrazone of 2,3-seco-28-methoxycarbonyl-1-cyanolup-20(29)-en-3-al (3c), C H N O . Yield after
42 69
3
3
21
purification by CC, 0.29 g (43%), R 0.41 (hexane:EtOAc, 10:1), mp 142–144°C (hexane:EtOAc, 10:1), [ꢁ] +5.4° (c 0.5,
f
D
–1
CHCl ). IR spectrum (ꢃ, cm ): 1670 (CH=NNHCO), 1725 (COOCH ), 2237 (CꢄN), 3211 (NH).
3
3
PMR spectrum (300 MHz, CDCl , ꢅ, ppm, J/Hz): 0.87 (3H, t, J = 7.5, CH ), 0.90, 0.93, 1.00, 1.16, 1.19 (5 ꢆ 3H, 5s,
3
3
5CH ), 1.67 (1H, s, CH -30), 2.29 and 2.56 (2H, 2d, J = 18.2, H -1, AB-system), 2.99 (1H, td, J = 10.2, 6.0, H-19), 3.66
3
3
AB
2
(3H, s, COOCH ), 4.60 and 4.73 (2H, 2s, H -29), 7.20 (1H, s, H-3), 9.21 (1H, br.s, NH).
3
2
40

13
C NMR spectrum (75.5 MHz, CDCl , ꢅ, ppm): 14.06, 14.54, 15.79, 18.39, 19.19, 20.21, 21.80, 22.55, 22.63,
3
24.84, 25.48, 28.22, 29.27, 29.29, 29.34, 29.36, 29.48, 29.53, 29.55, 29.60, 30.43, 31.86, 32.79,, 33.33, 36.80, 38.20, 40.63,
42.36, 42.44, 42.76, 44.72, 46.86, 49.15, 51.26, 51.43, 56.47, 109.83 (C-29), 118.25 (C-2), 150.20 (C-20), 154.44 (C-3),
176.22 (CONH), 176.57 (C-28).
Pentadecanoylhydrazone of 2,3-seco-28-methoxycarbonyl-1-cyanolup-20(29)-en-3-al (3d), C H N O . Yield
46 77
3 3
21
after purification by CC, 0.32 g (44%), R 0.44 (hexane:EtOAc, 10:1), yellow paste, [ꢁ] +3.1° (c 0.5, CHCl ). IR spectrum
f
D
3
–1
(ꢃ, cm ): 1670 (CH=NNHCO), 1730 (COOCH ), 2242 (CꢄN), 3202 (NH).
3
PMR spectrum (300 MHz, CDCl , ꢅ, ppm, J/Hz): 0.85 (3H, t, J = 6.9, CH ), 0.90, 0.93, 1.00, 1.16, 1.18 (5 ꢆ 3H, 5s,
3
3
5CH ), 1.67 (3H, s, CH -30), 2.26 and 2.56 (2H, 2d, J = 18.2, H -1, AB-system), 2.99 (1H, td, J = 11.1, 5.7, H-19), 3.66
3
3
AB
2
(3H, s, COOCH ), 4.60 and 4.72 (2H, 2s, H -29), 7.18 (3H, s, CH-3), 9.08 (1H, br.s, NH).
3
2
13
C NMR spectrum (75.5 MHz, CDCl , ꢅ, ppm): 14.07, 14.55, 15.81, 18.41, 19.20, 20.20, 21.80, 22.55, 22.65,
3
24.84, 25.49, 28.23, 29.32 (2C), 29.34 (2C), 29.37, 29.49, 29.60 (2C), 29.61 (2C), 29.65 (2C), 30.44, 31.88, 32.81, 33.36,
36.81, 38.21, 40.64, 42.37, 42.45, 42.77, 44.74, 46.86, 49.16, 51.26, 51.45, 56.48, 109.83 (C-29), 118.26 (C-2), 150.20
(C-20), 154.39 (C-3), 176.17 (CONH), 176.57 (C-28).
Benzoylhydrazone of 2,3-seco-28-methoxycarbonyl-1-cyanolup-20(29)-en-3-al (3e), C H N O . Yield after
38 53
3 3
21
purification by CC, 0.24 g (68%), R 0.26 (hexane:EtOAc, 5:1), mp 128–131°C (hexane:EtOAc, 10:1), [ꢁ] +4.2° (c 0.5,
f
D
–1
CHCl ). IR spectrum (ꢃ, cm ): 1653 (CH=NNHCO), 1726 (COOCH ), 2233 (CꢄN), 3236 (NH).
3
3
PMR spectrum (300 MHz, CDCl , ꢅ, ppm, J/Hz): 0.91 (2 ꢆ 3H, s, 2CH ), 0.99, 1.18, 1.25 (3 ꢆ 3H, 3s, 3CH ), 1.67
3
3
3
(3H, s, CH -30), 2.25 and 2.54 (2H, 2d, J
= 18.2, H -1, AB-system), 2.99 (1H, td, J = 10.7, 5.1, H-19), 3.66 (3H, s,
3
AB
2
COOCH ), 4.60 and 4.72 (2H, 2s, H -29), 7.42 (2H, t, J = 7.2, arom.), 7.50 (1H, t, J = 7.2, arom.), 7.70 (1H, s, H-3), 7.84 (2H,
3
2
d, J = 6.9, arom.), 9.32 (1H, br.s, NH).
13
C NMR spectrum (75.5 MHz, CDCl , ꢅ, ppm): 14.54, 15.79, 18.56, 19.21, 19.71, 21.63, 25.40, 28.50, 29.46,
3
29.57, 30.43, 31.89, 33.47, 36.81, 38.10, 40.63, 42.49, 42.73 (2C), 44.88, 46.84, 49.15, 51.28, 51.55, 56.46, 109.81 (C-29),
118.79 (C-2), 127.29 (2C arom.), 128.62 (2C arom.), 131.82 (arom.), 133.21 (arom.), 150.23 (C-20), 160.38 (C-3), 163.62
(CONH), 176.54 (C-28).
Acetylhydrazone of 1-cyano-2,3-seco-19ꢀ,28-epoxy-18ꢁ-olean-3-al (4a), C H N O . Yield 0.23 g (45%),
32 51
3 2
21
–1
R 0.12 (CHCl :EtOAc, 10:1), mp 65–67°C (CHCl :EtOAc, 10:1), [ꢁ] +30.0° (c 0.5, CHCl ). IR spectrum (ꢃ, cm ): 1676
f
3
3
D
3
(CH=N), 2240 (CꢄN), 3208 (NH).
PMR spectrum (300 MHz, CDCl , ꢅ, ppm, J/Hz): 0.78, 0.92, 0.95, 0.97, 1.17, 1.19, 1.24 (7 ꢆ 3H, 7s, 7CH ), 2.23
3
3
(3H, s, CH ), 2.32 and 2.60 (2H, 2d, J = 18.2, H -1, AB-system), 3.44 and 3.75 (2H, 2d, J = 7.8, H -28, AB-system), 3.52
3
AB
2
AB
2
(1H, s, H-19), 7.19 (1H, s, H-3), 8.87 (1H, br.s, NH).
13
C NMR spectrum (75.5 MHz, CDCl , ꢅ, ppm): 13.39, 15.70, 18.73, 20.17, 20.31, 21.88, 22.59, 24.50, 26.13,
3
26.35, 26.42, 28.18, 28.76, 29.85, 32.64, 32.88, 34.27, 36.24, 36.61, 40.55, 41.10, 41.45, 42.36, 42.51, 45.25, 46.58, 51.61,
71.23 (C-28), 87.83 (C-19), 118.28 (C-2), 154.61 (C-3), 173.37 (CONH).
2-Ethylpentanoylhydrazone of 1-cyano-2,3-seco-19ꢀ,28-epoxy-18ꢁ-olean-3-al (4b), C H N O . Yield 0.12 g
38 63
3 2
21
–1
(20%), R 0.4 (CHCl :EtOAc, 10:1), mp 73–75°C (CHCl :EtOAc, 10:1), [ꢁ] +18.6° (c 0.5, CHCl ). IR spectrum (ꢃ, cm ):
f
3
3
D
3
1668 (CH=N), 2244 (CꢄN), 3204 (NH).
PMR spectrum (300 MHz, CDCl , ꢅ, ppm, J/Hz): 0.78, 0.95, 0.97, 1.18, 1.19 (5 ꢆ 3H, 5s, 5CH ), 0.86 and 0.88
3
3
(2 ꢆ 3H, 2t, J = 6.6, 2CH ), 0.92 (2 ꢆ 3H, s, 2CH ), 2.30 and 2.58 (2H, 2d, J = 17.7, H -1, AB-system), 3.02–3.22 (1H, m,
3
3
AB
2
=NNHCOCH(C H )C H ), 3.44 and 3.75 (2H, 2d, J = 7.8, H -28, AB-system), 3.52 (1H, s, H-19), 7.15 (1H, s, H-3), 8.54
2
5
4
9
AB
2
(1H, br.s, NH).
13
C NMR spectrum (75.5 MHz, CDCl , ꢅ, ppm): 12.03, 13.38, 13.98, 15.67, 18.60, 20.13, 21.87, 22.65, 22.69,
3
24.48, 26.11, 26.32, 26.40, 28.34, 28.73, 29.62, 29.76, 31.68, 31.79, 32.62, 32.85, 34.24, 36.21, 36.59, 40.51, 41.07, 41.42,
42.41, 42.46, 42.54, 45.16, 46.54, 51.51, 71.20 (C-28), 87.81 (C-19), 118.23 (C-2), 154.28 (C-3), 178.97 (CONH).
Undecanoylhydrazone of 1-cyano-2,3-seco-19ꢀ,28-epoxy-18ꢁ-olean-3-al (4c), C H N O . Yield 0.32 g (50%),
41 69
3 2
21
–1
R 0.34 (CHCl :EtOAc, 10:1), mp 143–145°C (CHCl :EtOAc, 10:1), [ꢁ] +22.9° (c 0.5, CHCl ). IR spectrum (ꢃ, cm ):
f
3
3
D
3
1682 (CH=N), 2242 (CꢄN), 3196 (NH).
PMR spectrum (300 MHz, CDCl , ꢅ, ppm, J/Hz): 0.78, 0.95, 0.97, 1.17, 1.19 (5 ꢆ 3H, 5s, 5CH ), 0.86 (3H, t, J = 6.6,
3
3
CH ), 0.92 (2 ꢆ 3H, s, 2CH ), 2.31 and 2.59 (1H, d, J = 18.3, H-1), 2.58 (2H, t, J = 7.5, COCH (CH ) CH ), 3.44 and 3.75
3
3
AB
2
2 9
3
(2H, 2d, J = 7.7, H -28, AB-system), 3.52 (1H, s, H-19), 7.16 (1H, s, H-3), 8.67 (1H br.s, NH).
AB
2
41

13
C NMR spectrum (75.5 MHz, CDCl , ꢅ, ppm): 13.38, 14.07, 15.68, 18.67, 20.18, 21.87, 22.64, 24.48, 24.85,
3
26.12, 26.34, 26.42, 28.22, 28.74, 29.28, 29.35 (2C), 29.38, 29.49, 29.56 (2C), 29.79, 31.87, 32.63, 32.83, 34.26, 36.22,
36.60, 40.53, 41.08, 41.43, 42.35, 42.48, 45.20, 46.56, 51.54, 71.21 (C-28), 87.81 (C-19), 118.26 (C-2), 154.20 (C-3), 176.07
(CONH).
Pentadecanoylhydrazone of 1-cyano-2,3-seco-19ꢀ,28-epoxy-18ꢁ-olean-3-al (4d), C H N O . Yield 0.17 g (24%),
45 77
–1
3 2
21
R 0.4 (CHCl :EtOAc, 10:1), yellow paste, [ꢁ] +19.0° (c 0.5, CHCl ). IR spectrum (ꢃ, cm ): 1674 (CH=N), 2244 (CꢄN),
f
3
D
3
3200 (NH).
PMR spectrum (300 MHz, CDCl , ꢅ, ppm, J/Hz): 0.78, 0.95, 0.97, 1.17, 1.19 (5 ꢆ 3H, 5s, 5CH ), 0.87 (3H, t, J = 6.8,
3
3
CH ), 0.92 (2 ꢆ 3H, s, 2CH ), 2.31 and 2.60 (1H, d, J = 18.0, H -1), 2.55–2.64 (2H, m, COCH (CH ) CH ), 3.44 and 3.75
3
3
2
2
2 13
3
(2H, 2d, J = 8.0, H -28, AB-system), 3.52 (1H, s, H-19), 7.15 (1H, s, H-3), 8.60 (1H br.s, NH).
AB
13
2
C NMR spectrum (75.5 MHz, CDCl , ꢅ, ppm): 13.40, 14.09, 15.71, 18.72, 20.19, 21.89, 22.67, 24.50, 24.85,
3
26.14, 26.36, 26.44, 28.23, 28.76, 29.34 (2C), 29.37 (2C), 29.52, 29.64 (3C), 29.68 (3C), 29.81, 31.91, 32.66, 32.85, 34.29,
36.25, 36.63, 40.56, 41.11, 41.45, 42.39, 42.52, 45.23, 46.58, 51.55, 71.23 (C-28), 87.84 (C-19), 118.26 (C-2), 154.27 (C-3),
176.09 (CONH).
Benzoylhydrazone of 1-cyano-2,3-seco-19ꢀ,28-epoxy-18ꢁ-olean-3-al (4e), C H N O . Yield 0.25 g (43%),
37 53
3 2
21
–1
R 0.28 (CHCl :EtOAc, 10:1), mp 247–249°C (CHCl :EtOAc, 10:1), [ꢁ] +7.6° (c 0.5, CHCl ). IR spectrum (ꢃ, cm ): 1654
f
3
3
D
3
(CH=N), 2236 (CꢄN), 3192 (NH).
PMR spectrum (300 MHz, CDCl , ꢅ, ppm, J/Hz): 0.78, 0.92, 0.96, 1.21, 1.24 (5 ꢆ 3H, 5s, 5CH ), 0.98 (2 ꢆ 3H, s,
3
3
2CH ), 1.86 and 2.60 (1H, d, J = 18.1, H -1), 3.44 and 3.75 (2H, 2d, J = 18.0, H -28, AB-system), 3.51 (1H, s, H-19), 7.44
3
2
AB
2
(2H, t, J = 7.2, arom.), 7.52 (1H, t, J = 6.6, arom.), 7.70 (1H, s, H-3), 7.82 (2H, d, J = 7.5, arom.), 8.95 (1H, br.s, NH).
13
C NMR spectrum (75.5 MHz, CDCl , ꢅ, ppm): 13.39, 15.65, 18.85, 19.75, 20.64, 21.75, 24.48, 26.10, 26.31,
3
26.38, 28.44, 28.73, 29.65, 32.62, 33.00, 34.17, 36.21, 36.60, 40.30, 41.06, 41.42, 42.54, 42.75, 45,39, 46.50, 51.70, 71.19
(C-28), 87.81 (C-19), 118.80 (C-2), 127.33 (2C, arom.), 128.69 (2C, arom.), 131.89 (arom.), 133.20 (arom.), 160.64 (C-3),
164.15 (CONH).
ACKNOWLEDGMENT
The work was supported financially by the RFBR Grant No. 09-03-00642a and the Integrated Project for Basic
Research of the Ural Branch, RAS, in collaboration with scientists of the SB RAS.
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