Amino-derivatives of usninic acid

Article abstract of DOI:10.1007/s10600-010-9502-z

Products from the reaction of usninic acid and 4-(3-aminopropyl)-2,6-di-t- butylphenol, 4-(2-aminoethyl)-2,6-di-t-butylphenol, antipyrine, N,N-diethylaminoethylamine, p-chloroaniline, and p-bromoaniline in addition to the quaternary ammonium salt (E)-2-(1

Full text of DOI:10.1007/s10600-010-9502-z

Chemistry of Natural Compounds, Vol. 45, No. 6, 2009
AMINO-DERIVATIVES OF USNINIC ACID
A. A. Tazetdinova, O. A. Luzina,* M. P. Polovinka,
N. F. Salakhutdinov, and G. A. Tolstikov
UDC 547.992
Products from the reaction of usninic acid and 4-(3-aminopropyl)-2,6-di-t-butylphenol, 4-(2-aminoethyl)-
2,6-di-t-butylphenol, antipyrine, N,N-diethylaminoethylamine, p-chloroaniline, and p-bromoaniline in
addition to the quaternary ammonium salt (E)-2-(1-(6-acetyl-7,9-dihydroxy-8,9b-dimethyl-1,3-dioxo-1,9b-
dihydrodibenzo[b,d]furan-2(3H)-ylidene)ethylamino)-N,N-diethyl-N-methylethaneammonium iodide were
obtained.
Key words: usninic acid, enamines, Schiff bases, quaternary ammonium salt.
Usninic acid (1) is a major secondary metabolite of several lichens and possesses antiviral, antibiotic, fungicidal,
analgesic, antituberculosis, and other types of biological activity [1]. According to the literature [2], usninic acid can be used
as a synergist of insecticides based on entomopathogenic microorganisms. Considering the biological activity and availability
of usninic acid, it seemed advisable to expand the range of its synthetic transformations by including in the structure various
pharmacophores that could lead to the production of new biologically active compounds.
It is known that introducing amine groups of various structure into organic compounds produces or increases the
biological properties of the resulting compounds. Thus, it has been shown [3] that synthetic amino derivatives of 1 possess
antitumor activity. Native amino derivatives of usninic acid that were isolated from the antarctic lichen Stereocaulon alpinum
exhibited moderate antidiabetic activity [4].
It was observed previously that reaction of 1 with certain primary amines formed products from reaction of one or
two carbonyls to form enamine derivatives [5]. Derivatives of usninic acid with hydrazines [6] and several amino acids [7]
were produced.
Herein we present results from a study of the reactions of 1 with amines 2–7, each of which contains a fragment with
either its own biological activity or structural features allowing chemical modification of the products to continue.
12
OH
OH
O
O
O
15
RNH
2 - 7
2
9
10
1
11
11 NH
O
R
9a
9b
4a
5a
HO
O
OH
HO
7
O
3
13
13
O
O
14
19
17
8 - 13
1
16
18
20
1'
3'
1'
3'
16
N
3'
18
N
20
3'
R =
17
17
19
21
16
16
18 N
1'
OH
OH
Cl
Br
5'
5'
3'
1'
1'
O
17
5'
5'
5'
6, 12
5, 11
7, 13
2, 8
3, 9
4, 10
Scheme 1
Novosibirsk Institute of Organic Chemistry, Siberian Branch, Russian Academy of Sciences, 630090, Novosibirsk,
prosp. Akad. Lavrent′eva, 9, Russia, e-mail: luzina@nioch.nsc.ru. Translated from Khimiya Prirodnykh Soedinenii, No. 6,
pp. 672–675, November–December, 2009. Original article submitted June 2, 2009.
©
800
0009-3130/09/4506-0800 2009 Springer Science+Business Media, Inc.

Amines 2 and 3 contained a sterically hindered phenol group that exhibits antioxidant properties [8]; amines 4 and 5, fragments
enhancing antibacterial activity [9]. They all contain tertiary N atoms predisposed to quaternization. Aromatic amines 6 and
7 have single halogen atoms in the aromatic ring. This can not only increase substantially the biological activity of the
products [10] but also facilitate significantly the functionalization of the aromatic ring.
It was found that reaction of 1 with the aforementioned amines 2–7 taken in equimolar quantities produced enamine
derivatives 8–13 (Scheme 1). The reactions were carried out in alcohol under reflux for 3 h. The products precipitated upon
adding water to the cooled reaction mixture.
2RNH
2
14, 15
1
12
OH
O
15
9b
9
10
N
H
(CH )n
2
1
11
1'
9a
3'
7
4a
3
HO
O
O
OH
5'
13
N
14
(CH )n
5''
1''
2
HO
3''
14, 15
14:n = 3; 15: n = 2
Scheme 2
Schiff bases 14 and 15 formed upon adding to the reaction three equivalents of 2 and 3 (Scheme 2). Amines 4–7 did
13
not form similar compounds at the C =O carbonyl of usninic acid. Only enamines 10–13 were isolated from the reaction with
an excess of 4–7 or after prolonged reflux (Scheme 1).
Compounds 14 and 15 appeared together with 8 and 9, respectively, in the reaction mixture. Compounds 14 and 15
were isolated by column chromatography in 22 and 20% yields, respectively. The structures of 8–15 were established by
2
11
NMR and IR spectroscopy and mass spectrometry. The configuration of the C –C double bond was assigned based on the
literature [5].
It is known that a quaternized N atom both found in native alkaloids and produced by synthetic transformations of
organic compounds imparts to a molecule several important and interesting biological activities. Thus, compounds containing
this fragment exhibit myorelaxant [11], antitumor [12], spasmolytic [13], and several other activities.
Reaction of 11 with CH I produced quaternary ammonium salt 16 in 64% yield. The reaction occurred at room
3
temperature in CH Cl over 72 h. Amine 10 did not react with CH I even at elevated temperature.
2
2
3
18
19
CH
21
OH
O
16
N
3
22
N
H
17
20
HO
O
O
I
O
16
EXPERIMENTAL
13
PMR and C NMR spectra in CDCl and DMSO-d were recorded on BrukerAM-400 (operating frequencies 400.13
3
6
and 100.61 MHz) and AV-300 (300.13 and 75.47 MHz, respectively) instruments. Solvent resonances (δ 7.24 ppm and
H
δ 76.90 ppm for CHCl ; δ 2.50 and δ 39.50 ppm for DMSO-d ) were used as standards. IR spectra were recorded on a
C
3
H
C
6
Vector 22 spectrometer (KBr); mass spectra (ionizing electron energy 70 eV), in a DFS high-resolution mass spectrometer.
Usninic acid (1) was isolated from a mixture of lichens of the genus Usnea by the literature method [14]. The conversion of
usninic acid was monitored using PMR spectra. Silica gel (Merck, 70–230 mesh) was used for column chromatography.
Amines 4-(3-aminopropyl)-2,6-di-t-butylphenol (2), 4-(3-aminoethyl)-2,6-di-t-butylphenol (3), 4-aminoantipyrine
(4), N,N-diethylaminoethylamine (5), p-chloroaniline (6), and p-bromoaniline (7) were commercially available.
801

General Method for Reacting Usninic Acid (1) with an Equimolar Amount of Amines 2–7. Compound 1
(1 mmol) was treated with amine 2–7 (1.1 mmol), dissolved in ethanol (12 mL), refluxed on a water bath for 3 h, cooled, and
treated with distilled water (10 mL). A white precipitate formed. The precipitate from the reaction with 2 and 6 was finely
dispersed. Therefore, the reaction mixture was extracted with CHCl (3×). The extracts were dried over anhydrous MgSO .
3
4
The solvent was distilled in vacuo in a rotary evaporator. The precipitate from reaction with 3, 4, 5, and 7 was filtered off,
washed with water, and dried in air. This afforded 8-13.
(E)-6-Acetyl-2-(1-(3,5-di-t-butyl-4-hydroxyphenpropylamino)ethylidene)-7,9-dihydroxy-8,9b-
dimethyldibenzo[b,d]furan-1,3(2H,9bH)-dione (8). Yield 91%, mp 83–87°C. PMR spectrum (CDCl , δ, ppm, J/Hz): 1.43
3
t
(18H, s, H-Bu ), 1.69 (3H, s, H-15), 2.03 (2H, m, H-17), 2.09 (3H, s, H-10), 2.58 (3H, s, H-12), 2.67 (3H, s, H-14), 2.68 (2H,
t, J = 7.5, H-18), 3.46 (2H, dt, J = 7.2, 6.4, H-16), 5.10 (1H, s, OH-4′), 5.78 (1H, s, H-4), 6.96 (2H, s, H-2′, H-6′), 12.04 (s,
OH-9), 13.36 and 13.53 (s and br.s, NH and OH-7).
13
t
C NMR spectrum (CDCl , δ, ppm): 7.3 (C-10), 18.1 (C-12), 30.2 (6C-Bu ), 30.5 (C-17), 31.0 (C-14), 31.8 (C-15),
3
t
32.5 and 34.2 (C-16, C-18), 43.1 (2C-Bu ), 55.5 (C-9b), 101.3 (C-6), 102.4 (C-4), 102.4 (C-2), 105.9 (C-9a), 107.8 (C-8),
124.6 (C-2′ and C-6′), 130.4 (C-1′), 136.2 (C-5′ and C-3′), 152.2 (C-4′), 155.8 (C-5a), 158.3 (C-9), 163.4 (C-7), 173.9 (C-11),
174.7 (C-4a), 189.9 (C-3), 198.1 (C-1), 200.5 (C-13).
–1
IR spectrum (ν, cm ): 3635, 3433, 2955, 1699, 1557, 1469, 1435, 1371, 1289, 1189, 1139, 1057. Found:
+
m/z 589.3027 [M] C H O N. Calcd: M = 589.3034.
35 43
7
(E)-6-Acetyl-2-(1-(3,5-di-t-butyl-4-hydroxyphenethylamino)ethylidene)-7,9-dihydroxy-8,9b-
dimethyldibenzo[b,d]furan-1,3(2H,9bH)-dione (9). Yield 93%, mp 103–105°C. PMR spectrum (CDCl , δ, ppm, J/Hz):
3
t
1.42 (18H, s, H-Bu ), 1.68 (3H, s, H-15), 2.08 (3H, s, H-10), 2.46 (3H, s, H-12), 2.66 (3H, s, H-14), 2.91 (2H, t, J = 7.1, H-17),
3.68 (2H, dt, J = 6.1, 7.1, H-16), 5.17 (1H, s, OH-4′), 5.78 (1H, s, H-4), 6.99 (2H, s, H-2′ and H-6′), 12.08 (1H, s, OH-9), 13.36
and 13.59 (1H and 1H, s and br.s, NH and OH-7).
13
t
C NMR spectrum (CDCl , δ, ppm): 7.3 (C-10), 18.0 (C-12), 30.1 (6C-Bu ), 31.1 (C-14), 31.8 (C-15), 34.2 (C-17),
3
t
35.4 (C-16), 45.9 (2C-Bu ), 55.7 (C-9b), 101.5 (C-6), 102.4 (C-4), 102.9 (C-2), 106.0 (C-9a), 107.8 (C-8), 125.2 (C-2′ and
C-6′), 127.5 (C-1′), 136.3 (C-5′ and C-3′), 155.7 (C-4′), 152.8 (C-5a), 158.2 (C-9), 163.3 (C-7), 174.0 (C-11), 174.7 (C-4a),
189.9 (C-3), 198.3 (C-1), 200.5 (C-13).
–1
IR spectrum (ν, cm ): 3633, 2956, 1700, 1626, 1557, 1468, 1343, 1290, 1189, 1119, 1072. Found: m/z 575.2895
+
[M] C H O N. Calcd: M = 575.2883.
34 41
7
(E)-6-Acetyl-2-(1-(1,5-dimethyl-3-oxo-2-phenethyl-2,3-dihydro-1H-pyrazol-4-ylamino)ethylidene)-7,9-
dihydroxy-8,9b-dimethyldibenzo[b,d]furan-1,3(2H,9bH)-dione (10). Yield 72%, mp 195°C. PMR spectrum (CDCl , δ,
3
ppm, J/Hz): 1.77 (3H, s, H-15), 2.11 (3H, s, H-10), 2.33 (3H, s, H-19), 2.72 (6H, s, H-12 and H-14), 3.24 (3H, s, H-20), 5.88
(1H, s, H-4), 7.42 and 7.52 (3H, m and 2H, m, H-arom), 11.83 (1H, s, OH-9), 13.38 (1H, s, OH-7), 14.31 (1H, br.s, NH).
13
C NMR spectrum (CDCl , δ, ppm): 7.0 (C-10), 10.4 (C-19), 20.0 (C-12), 30.8 (C-14), 30.4 (C-15), 35.2 (C-20),
3
57.1 (C-9b), 100.9 (C-6), 101.8 (C-4), 102.8 (C-2), 104.6 (C-16), 107.4 (C-9a), 107.7 (C-8), 124.3 (C-5′ and C-3′), 127.3
(C-4′), 129.1 (C-6′ and C-2′), 133.6 (C-7′), 149.0 (C-17), 155.3 (C-5a), 157.8 (C-9), 159.7 (C-18), 163.1 (C-7), 174.3 (C-11),
176.3 (C-4a), 190.6 (C-3), 198.2 (C-1), 200.2 (C-13).
–1
+
IR spectrum (ν, cm ): 3436, 2924, 1706, 1545, 1362, 1272, 1133, 1069, 891. Found: m/z 529.1845 [M] C H O N .
29 27
7 3
Calcd: M = 529.1844.
(E)-6-Acetyl-2-(1-(2-(diethylamino)ethylidene)-7,9-dihydroxy-8,9b-dimethyldibenzo[b,d]furan-1,3(2H,9bH)-
dione (11). Yield 88%, mp 68°C. PMR spectrum (CDCl , δ, ppm, J/Hz): 1.16 (6H, t, J = 7.1, H-19 and H-21), 1.73 (3H, s,
3
H-15), 2.13 (3H, s, H-10), 2.67 (6H, s, H-12 and H-14), 2.69 (4H, q, J = 7.1, H-18 and H-20), 2.86 (2H, t, J = 6.0, H-17), 3.66
(2H, dt, J = 5.7, 6.0, H-16), 5.82 (1H, s, H-4), 12.01 (1H, br.s, OH-9), 13.36 and 13.39 (1H, s and 1H, s, NH, OH-7).
13
C NMR spectrum (CDCl , δ, ppm): 7.3 (C-10), 11.5 (C-19 and C-21), 18.7 (C-12), 31.8 (C-14), 31.9 (C-15), 42.3
3
(C-16), 46.7 (C-18 and C-20), 50.8 (C-17), 59.0 (C-9b), 102.5 (C-4), 101.2 (C-6), 105.0 (C-2), 105.1 (C-9a), 107.7 (C-8),
155.8 (C-5a), 158.2 (C-9), 163.7 (C-7), 173.7 (C-11), 174.3 (C-4a), 191.5 (C-3), 197.9 (C-1), 200.6 (C-13).
–1
+
IR spectrum (ν, cm ): 3387, 2926, 1701, 1627, 1555, 1370, 1287, 1061, 841. Found: m/z 442.2110 [M] C H O N .
24 30
6 2
Calcd: M = 442.2098.
(E)-6-Acetyl-2-(1-(4-chlorophenylamino)ethylidene)-7,9-dihydroxy-8,9b-dimethyldibenzo[b,d]furan-
1,3(2H,9bH)-dione (12). Yield 87%, mp 110°C. PMR spectrum (CDCl , δ, ppm, J/Hz): 1.71 (3H, s, H-15), 2.05 (3H, s,
3
802

H-10), 2.54 (3H, s, H-12), 2.64 (3H, s, H-14), 5.83 (1H, s, H-4), 7.14 (2H, d, J = 8.5, H-2′ and H-6′), 7.43 (2H, d, J = 8.5,
H-3′ and H-5′), 11.68 (1H, s, OH-9), 13.31 (1H, s, OH-7), 15.06 (1H, s, NH).
13
C NMR spectrum (CDCl , δ, ppm): 7.3 (C-10), 20.4 (C-12), 31.1 (C-14), 31.7 (C-15), 57.5 (C-9b), 101.2 (C-6),
3
102.0 (C-4), 102.7 (C-9a), 104.7 (C-2), 108.1 (C-8), 126.9 (C-2′ and C-6′), 129.7 (C-3′ and C-5′), 133.9 (C-4′), 134.5 (C-1′),
155.6 (C-5a), 157.9 (C-9), 163.4 (C-7), 173.7 (C-11), 174.7 (C-4a), 190.9 (C-3), 198.7 (C-1), 200.4 (C-13).
–1
IR spectrum (ν, cm ): 3455, 2927, 1698, 1630, 1546, 1462, 1367, 1280, 1205, 1136, 1065, 844. Found: m/z 453.0966
+
[M] C H O NCl. Calcd: M = 453.0971.
24 20
6
(E)-6-Acetyl-2-(1-(4-bromophenylamino)ethylidene)-7,9-dihydroxy-8,9b-dimethyldibenzo[b,d]furan-
1,3(2H,9bH)-dione (13). Yield 87%, mp 170°C. PMR spectrum (CDCl , δ, ppm, J/Hz): 1.76 (3H, s, H-15), 2.11 (3H, s,
3
H-10), 2.58 (3H, s, H-12), 2.69 (3H, s, H-14), 5.89 (1H, s, H-4), 7.11 (2H, d, J = 8.5, H-2′, H-6′), 7.61 (2H, d, J = 8.5, H-3′,
H-5′), 11.74 (1H, s, OH-9), 13.38 (1H, s, OH-7), 15.10 (1H, s, NH).
13
C NMR spectrum (CDCl , δ, ppm): 7.3 (C-10), 20.4 (C-12), 31.1 (C-14), 31.7 (C-15), 57.5 (C-9b), 101.2 (C-6),
3
102.0 (C-4), 102.7 (C-9a), 104.7 (C-2), 108.1 (C-8), 126.9 (C-2′ and C-6′), 129.7 (C-3′ and C-5′), 133.9 (C-4′), 134.5 (C-1′),
155.6 (C-5a), 157.9 (C-9), 163.4 (C-7), 173.7 (C-11), 174.7 (C-4a), 190.9 (C-3), 198.7 (C-1), 200.4 (C-13).
–1
IR spectrum (ν, cm ): 2925, 2725, 1698, 1634, 1543, 1462, 1365, 1276, 1206, 1137, 1065, 843. Found: m/z 497.04342
+
[M] C H O NBr. Calcd: M = 497.04590.
24 20
6
General Method for Reacting Usninic Acid with a Three-fold Excess of Amines 2 and 3. Compound 1 (1 mmol)
was treated with amines 2 and 3 (3 mmol), dissolved in alcohol (12 mL), refluxed on a water bath for 3 h, cooled, and treated
with distilled water (10 mL). The white precipitate that formed was filtered off, washed with water, and dried in air. The
reaction mixture was separated using column chromatography over silica gel with elution by CHCl to afford 14 and 15.
3
(E)-2-(1-3,5-Di-t-butyl-4-hydroxyphenylpropylamino)ethylidene)-6-((E)-1-(3,5-di-t-butyl-4-
hydroxyphenpropylamino)-7,9-dihydroxy-8,9b-dimethyldibenzo[b,d]furan-1,3(2H,9bH)-dione (14). Yield 22%, mp 92–
t
96°C. PMR spectrum (CDCl , δ, ppm, J/Hz): 1.42 (36H, s, H-Bu ), 1.74 (3H, s, H-15), 1.83 (2H, m, H-17), 2.09 (2H, m,
3
H-20), 2.10 (3H, s, H-10), 2.50 (2H, m, H-18 and 2H, m, H-21), 2.64 (3H, s, H-12), 2.67 (3H, s, H-14), 2.91 (2H, m, H-19),
3.29 (2H, m, H-16), 5.04 and 5.07 (1H, s and 1H, s, OH-4′ and OH-4′′), 5.94 (1H, s, H-4), 6.92–6.96 (4H, m, H-arom),
11.22 (1H, br.s, OH-9), 13.32 (1H, br.s, OH-7), 17.97 (1H, br.s, NH).
13
t
C NMR spectrum (CDCl , δ, ppm): 7.9 (C-10), 17.5 (C-14), 18.0 (C-12), 30.1 (12C-Bu ), 30.5, 31.3, 32.5, 32.9
3
t
(C-17, C-18, C-20, C-21), 31.9 (C-15), 34.1 (4C-Bu ), 42.9 (C-16), 45.3 (C-19), 57.2 (C-9b), 98.9 (C-6), 101.3 (C-4), 101.9
(C-2), 106.0 (C-9a), 108.6 (C-8), 124.5 and 124.6 (C-2′, C-6′, C-2′, C-6′), 130.4 and 131.3 (C-1′ and C-1′), 135.7 and 135.9
(C-5′, C-3′ and C-5′, C-3′), 151.7 and 152.0 (C-4′ and C-4′), 155.2 (C-5a), 158.3 (C-9), 170.4 (C-7), 170.5 (C-13), 174.4 and
174.6 (C-4a and C-11), 189.9 (C-3), 198.6 (C-1).
–1
IR spectrum (ν, cm ): 3639, 3431, 2955, 1697, 1623, 1558, 1466, 1436, 1369, 1235, 1189. Found: m/z 834.5161
+
[M] C H O N . Calcd: M = 834.5178.
52 70
7 2
(E)-2-(1-3,5-Di-t-butyl-4-hydroxyphenethylamino)ethylidene)-6-((E)-1-(3,5-di-t-butyl-4-
hydroxyphenethylamino)-7,9-dihydroxy-8,9b-dimethyldibenzo[b,d]furan-1,3(2H,9bH)-dione (15). Yield 20%, mp 85°C.
t
PMR spectrum (CDCl , δ, ppm, J/Hz): 1.40 and 1.42 (each 18H, s, H-Bu ), 1.65 (3H, s, H-15), 2.12 (3H, s, H-10), 2.27 (3H,
3
s, H-14), 2.46 (3H, s, H-12), 2.91 (2H, t, J = 7.2, H-19), 2.96 (2H, t, J = 7.0, H-17), 3.67 (2H, dt, J = 6.3, 7.0, H-16), 3.73 (2H,
t, J = 7.2, H-18), 5.11 and 5.17 (1H, s, OH-4′ and OH-4′), 5.68 (1H, s, H-4), 6.99–7.01 (4H, m, H-arom), 11.43 (1H, br.s,
OH-9), 13.56 (1H, br.s, OH-7), 17.97 (1H, br.s, NH).
13
t
C NMR spectrum (CDCl , δ, ppm): 7.9 (C-10), 17.3 (C-14), 17.9 (C-12), 30.1 (12C-Bu ), 32.0 (C-15), 34.1
3
t
(4C-Bu ), 35.5 (C-17), 36.4 (C-19), 45.9 (C-16), 48.4 (C-18), 57.2 (C-9b), 99.0 (C-6), 101.3 (C-4), 102.0 (C-2), 106.1 (C-9a),
108.6 (C-8), 125.2 and 125.5 (C-2′, C-6′, C-2′, C-6′), 127.7 and 129.2 (C-1′ and C-1′), 135.9 and 136.3 (C-5′, C-3′ and C-5′,
C-3′), 152.4 and 152.7 (C-4′ and C-4′), 155.1 (C-5a), 158.3 (C-9), 170.2 (C-7), 170.6 (C-13), 174.4 and 174.6 (C-4a and
C-11), 189.9 (C-3), 198.6 (C-1).
–1
IR spectrum (ν, cm ): 3639, 3433, 2957, 1697, 1623, 1558, 1466, 1436, 1370, 1235, 1189, 1076. Found:
+
m/z 806.4856 [M] C H O N . Calcd: M = 806.4865.
50 66
7 2
Reaction of 11 with Methyliodide. Amine 11 (1.1 mmol) in CH Cl (10 mL) was treated with CH I (3 mmol) and
2
2
3
stored for 3 d. The yellowish precipitate was filtered off, washed with CHCl , and dried in air to afford 16.
3
803

(E)-2-(1-(6-Acetyl-7,9-dihydroxy-8,9b-dimethyl-1,3-dioxo-1,9b-dihydrodibenzo[b,d]furan-2(3H)-
ylidene)ethylamino)-N,N-diethyl-N-methylethaneammonium Iodide (16). Yield 64%, mp 125°C. PMR spectrum
(DMSO-d , δ, ppm, J/Hz): 1.22 (6H, t, J = 7.1, 3H-19 and 3H-21), 1.60 (3H, s, H-15), 1.90 (3H, s, H-10), 2.57 (3H, s, H-12),
6
2.64 (3H, s, H-14), 3.05 (3H, s, H-22), 3.38 (4H, q, J = 7.1, H-18 and H-20), 3.59 (2H, t, J = 6.0, H-17), 4.04 (2H, dt,
J = 5.7, 6.0, H-16), 5.83 (1H, s, H-4), 12.06 (1H, s, OH-9), 12.97 and 13.32 (1H, s, NH and 1H, s, OH-7).
13
C NMR spectrum (CDCl , δ, ppm): 7.6 (C-10), 7.7 (C-19 and C-21), 18.6 (C-12), 31.2 and 31.8 (C-14 and C-15),
3
37.2 (C-16), 47.1 (C-22), 56.4, 56.6, 57.5 (C-17, C-18, C-20), 59.0 (C-9b), 100.1 (C-6), 102.4 (C-4), 102.4 (C-2), 105.4
(C-9a), 106.6 (C-8), 155.8 (C-5a), 157.6 (C-9), 162.6 (C-7), 173.3 (C-11), 176.2 (C-4a), 189.0 (C-3), 197.7 (C-1), 201.1
(C-13).
–1
IR spectrum (ν, cm ): 3440, 2976, 1700, 1629, 1556, 1369, 1288, 1060, 846.
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