Identification of unprecedented purine-containing compounds, the zingerines, from ginger rhizomes (Zingiber officinale Roscoe) using a phase-trafficking approach

Article abstract of DOI:10.1016/j.phytochem.2011.03.007

Three unprecedented purine-containing compounds, named [6]-, [8]-, and [10]-zingerines as they are 5-(6-amino-9H-purin-9-yl) analogs of [6]-, [8]-, and [10]-gingerols, respectively, were isolated from a methanolic extract of ginger rhizomes using a phase

Full text of DOI:10.1016/j.phytochem.2011.03.007

Phytochemistry 72 (2011) 935–941
Contents lists available at ScienceDirect
Phytochemistry
journal homepage: www.elsevier.com/locate/phytochem
Identification ofunprecedented purine-containing compounds, the zingerines, from
ginger rhizomes (Zingiber officinale Roscoe) using a phase-trafficking approach
⇑
Juan J. Araya, Huaping Zhang, Thomas E. Prisinzano, Lester A. Mitscher, Barbara N. Timmermann
Department of Medicinal Chemistry, University of Kansas, Lawrence, KS 66045, USA
a r t i c l e i n f o
a b s t r a c t
Article history:
Three unprecedented purine-containing compounds, named [6]-, [8]-, and [10]-zingerines as they are 5-
(6-amino-9H-purin-9-yl) analogs of [6]-, [8]-, and [10]-gingerols, respectively, were isolated from a
methanolic extract of ginger rhizomes using a phase trafficking-based method that utilizes solid phase
reagents allowing for fast and selective simultaneous separation of basic, acidic, and neutral components
of natural products extracts.
Received 10 November 2010
Received in revised form 22 January 2011
Available online 15 April 2011
Keywords:
Ginger
Ó 2011 Elsevier Ltd. All rights reserved.
Zingerines
Alkaloids
Phase-trafficking
Natural products
Fractionation
1. Introduction
gerines (Fig. 1), as they are 5-(6-amino-9H-purin-9-yl) analogs of
[6]-, [8]-, and [10]-gingerols, respectively. Although present in se-
Ginger, Zingiber officinale Roscoe (Zingiberaceae), is used world-
wide not only as a spice in food, but also in various traditional sys-
tems of medicine against different ailments such as arthritis,
rheumatism, infectious diseases, and vomiting (Afzal et al., 2001;
Ali et al., 2008). The chemistry of ginger has been extensively
investigated with over 100 compounds identified in both fresh
and dried samples (Jolad et al., 2004, 2005). Ginger’s numerous
biological activities have been attributed mainly to the gingerols
and shogaols, the major pungent principles found in both fresh
and dried ginger rhizomes (Funk et al., 2009; Lantz et al., 2004).
In the present article, the isolation and structural determination
of three novel purine-containing compounds (1–3) from dry pow-
dered ginger rhizomes are described using a new phase-trafficking
based method (Araya et al., 2010). The methanolic rhizome extract
was subjected to our separation protocol using ion-exchange resins
allowing for fast and selective resolution of the basic, acidic, and
neutral components. Solid-phase reagents (SSR) are often used to
facilitate and speed-up purification procedures in organic synthe-
sis, especially in combinatorial chemistry (Flynn, 1999; Solinas
and Taddei, 2007). However, application of SSR to natural products
research has been limited (Alexandratos, 2009; Vanrensen and
Veit, 1995; Zhao et al., 2008). Using this approach, the isolation
and identification of three new nitrogenous compounds from gin-
ger were carried out, and these were named [6]-, [8]-, and [10]-zin-
lected microbial and marine products, secondary metabolites that
contain a purine ring attached to a non-carbohydrate carbon skel-
eton are very rare in higher plants (Rosemeyer, 2004; Wang et al.,
2008).
2. Results and discussion
A methanolic extract of ginger rhizomes was submitted to the
separation scheme illustrated in Fig. 2 in order to explore the scope
of catch-and-release methodology for natural products resolution.
This allows for quick and solvent sparing simultaneous separation
of basic, acidic, and neutral components from a mixture taking
advantage of ionic-exchange resins physically confined into spa-
tially separated tea bags (Araya et al., 2010). As expected, the phe-
nolic compounds, including the main gingerols and shogaols, were
trapped by the basic resin (Fig. 3). Interestingly, the LCMS traces of
the basic fraction indicated the presence of several compounds
with odd number molecular weight values, which prompted us
to investigate further the nature of such components because, to
our knowledge, no nitrogen-containing basic metabolites have
been reported from ginger to date.
Initially, our small-scale separation protocol allowed for the iso-
lation of main compound 1 from the basic fraction after two addi-
tional purification steps: column chromatography on Sephadex
LH-20 followed by semi-preparative reverse phase HPLC. The
HRMS m/z 412.2362 [M + H]+ (calc. for C22H30N5O2 412.2349)
was consistent with the presence of five nitrogen atoms in the
⇑
Corresponding author. Tel.: +1 785 864 4844; fax: +1 785 864 5326.
E-mail address: btimmer@ku.edu (B.N. Timmermann).
0031-9422/$ - see front matter Ó 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.phytochem.2011.03.007

936
J.J. Araya et al. / Phytochemistry 72 (2011) 935–941
(m, H-1) to C-10 were established based on the correlations ob-
served in the HMBC spectrum (Fig. 5). Third, the chemical shift of
aromatic carbon C-40 (s, dC 145.8) suggested that this position
was oxygenated. Analogous to [6]-gingerol, two spin systems cor-
responding to a decanyl chain were identified in compound 1
based on 1H–1H COSY, HSQC and HMBC spectra, showing two dis-
tinctive structural features: a ketone group dC 209.6 (s, C-3) and a
methine proton dH 4.91 (m, H-5). Finally, with only two proton sig-
nals left dH 8.16 (brs, H-400) and 8.12 (brs, H-800), five nitrogen
atoms, and five carbon signals dC 153.4 (C-200), 150.6 (C-400),
120.4 (C-500), 157.3 (C-600), and 142.6 (C-800); the presence of an
adenine ring was proposed and supported by ESIMS/MS fragmen-
tation and HMBC spectra (Fig. 5). Furthermore, adenine substitu-
tion at the C-5 position explained satisfactorily the shift to lower
filed of H-5 (m, dH 4.91) when compared with the corresponding
signal of [6]-gingerol (Kim et al., 2008). This assignment was con-
firmed by synthesis (vide infra). After scaling-up the separation
protocol, compounds 2 and 3 were isolated showing similar frag-
mentation patterns in the ESIMS/MS, almost identical low field sig-
nals in 1H- and 13C NMR spectra (Table 1), and differing from
compound 1 only in the number of methylene groups in the ali-
phatic region. Accordingly, their structures 2 and 3 were assigned
relative to that previously described for compound 1.
Fig. 1. Structure of compounds 1–3.
molecular formula. The ESIMS/MS showed the neutral loss of m/z
276.2, leaving the stable charged purine fragment of m/z 136.1
(Fig. 4). Furthermore, the structure of 1 was deduced based on
analyses of the 1H, 13C NMR, 1H–1H COSY, HSQC and HMBC spectra
(Supplementary Figs. 1–4) and supported by IR and UV spectra.
First, the splitting pattern and coupling constants of the aromatic
protons in the 1H NMR dH 6.63 (d, J = 2.0 Hz, H-20), 6.59 (d,
J = 8.0 Hz, H-50) and 6.44 (dd, J = 8.0, 2.2 Hz, H-60) were consistent
with a 1,2,4-trisubstituted benzene ring system and the corre-
sponding aromatic carbons dC 133.7 (C-10), 113.0 (C-20), 148.9 (C-
30), 145.8 (C-40), 116.2 (C-50) and 121.6 (C-60) were readily assigned
with the assistance of correlations observed in the HSQC and
HMBC spectra (Fig. 5). Second, the attachments of the methoxy
group dH 3.76 (s, 30-OCH3) to C-30 and methylene group dH 2.67
Although purine is the most widely distributed N-heterocyclic
ring in nature, purine-containing plant secondary metabolites are
not common (Rosemeyer, 2004). Simple purine alkaloids, like caf-
feine or theanine, have a limited taxonomic distribution in the
plant kingdom and a purine ring attached to a non-carbohydrate
carbon skeleton, as in the case of compounds 1–3, is an unusual
structural feature. Among the limited reports of this class of natu-
ral products are the cucurbitane triterpenoids isolated from Cucur-
Fig. 2. General catch-and-release protocol scheme.

J.J. Araya et al. / Phytochemistry 72 (2011) 935–941
937
Fig. 3. HPLC trace (UV, 254 nm) of (A) methanolic extract, (B) acidic fraction, (C) basic fraction, and (D) neutral fraction.
Fig. 4. Proposed fragmentation of compounds 1–3.
ited number of examples from marine sponges (Appenzeller et al.,
2008; Wright et al., 2009; Yosief et al., 2000).
To the best of our knowledge, compounds 1–3 have not been
previously reported in the literature and they represent the first
basic nitrogen-containing secondary metabolites in ginger. We
named this family of compounds zingerines, as they are 5-(6-ami-
no-9H-purin-9-yl) analogs of gingerols. Compounds 1–3 were de-
tected in the original extract prior to any purification step using
targeted LCMS analysis as well as in two extracts prepared from
additional commercial samples of ginger rhizomes (Supplementary
Figs. 9–12). The results showed a strong evidence that the three
new compounds were not likely to be artifacts of our new isolation
process. Interestingly, we unsuccessfully attempted to obtain zin-
gerines using classic liquid/liquid partition protocols (data not
Fig. 5. Selected HMBC correlations of observed for compound 1.
bita pepo cv dayangua (Wang et al., 2008), alachalasine F–G from
the fungus Podospora vesticola (Zhang et al., 2008, 2009), and a lim-

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J.J. Araya et al. / Phytochemistry 72 (2011) 935–941
Table 1
1H NMR Spectroscopic data (500 MHz, CD3OD) for zingerines (1–3).a
No.
1
2
3
dC (mult)
dH (J in Hz)
dC
dH (J in Hz)
dC (mult)
dH (J in Hz)
1
2
3
30.4 t
45.7 t
209.6 s
47.7 t
2.67 m
2.67 m
-
3.39 dd (17.6, 8.8)
3.05 dd (17.6, 4.7)
4.91 m
1.82 m
2.08 m
0.98 m
1.20 m
1.20 m
1.20 m
0.81 t (6.9)
-
-
30.4 t
45.7 t
209.6 s
47.8 t
2.68 m
2.68 m
-
3.40 dd (17.8, 8.9)
3.05 dd (17.8, 4.8)
4.92 m
1.80 m
2.08 m
30.4 t
45.7 t
209.6 s
47.8 t
2.67 m
2.67 m
-
3.39 dd (17.9, 8.7)
3.05 dd (17.9, 4.9)
4.92 m
1.80 m
2.08 m
4a
4b
5
6a
6b
7a
7b
8
54.0 d
35.1 t
54.0 d
35.1 t
54.0 d
35.1 t
32.3 t
32.9 t
1.24 m
33.2 t
1.24 m
26.8 t
23.5 t
14.3 q
-
-
-
30.2 t
30.1 t
27.1 t
23.7 t
14.5 q
-
1.24 m
1.24 m
1.24 m
1.24 m
0.84 t (7.0)
-
-
-
6.63 d (1.8)
-
-
6.59 d (7.9)
6.45 dd (7.9, 1.8)
-
30.6 t
30.5 t
30.5 t
30.0 t
27.1 t
23.8 t
14.6 q
133.7 s
113.0 d
148.9 s
145.9 s
116.2 d
121.7 d
153.5 s
150.7 d
120.5 s
157.4 s
142.6 d
56.4 q
1.24 m
1.24 m
1.24 m
1.24 m
1.24 m
1.24 m
0.87 t (7.0)
-
6.63 d (1.9)
-
-
6.59 d (7.9)
6.45 dd (7.9, 1.9)
-
9
10
11
12
13
14
10
-
-
-
-
-
133.7 s
113.0 d
148.9 s
145.8 s
116.2 d
121.6 d
153.4 s
150.6 d
120.4 s
157.3 s
142.6 d
56.4 q
133.7 s
113.0 d
148.9 s
145.9 s
116.2 d
121.6 d
153.5 s
150.7 d
120.4 s
157.4 s
142.7 d
56.4 q
20
6.63 d (2.0)
-
-
6.59 d (8.0)
6.44 dd (8.0, 2.0)
30
40
50
60
200
400
500
600
800
30-OMe
8.16 br s
-
-
8.12 br s
3.76 s
8.16 br s
-
-
8.12 br s
3.76 s
8.16 br s
-
-
8.12 br s
3.76 s
a
br = Broad; s = singlet; d = doublet; dd = doublet of doublets; q = quartet; m = multiplet.
shown) presumably due to the acidic phenolic group they contain
that makes these compounds amphoteric and thus soluble in the
aqueous phase under basic conditions. It is believed that the
amphoteric behavior of the zingerines coupled with their strong
adsorption on silica gel are the two main reasons that have pre-
vented identification and isolation of these compounds in previous
phytochemical studies of ginger.
The presence of zingerines in the dried ginger rhizome extract
could in theory arise from a Michael-type reaction between shoga-
ols, dehydration products of gingerols during drying of ginger rhi-
zome, and adenine. To explore the feasibility of such a reaction, we
dissolved an equimolar mixture of [6]-shogaol and adenine in a
mixture of 1:1 MeOH:H2O and stirred the reaction mixture during
72 h at room temperature. The formation of [6]-zingerine was only
detected by means of LCMS analysis, but not using UV detection,
suggesting that only minute quantities of the compound is pro-
duced under those conditions (Supplementary Figs. 13 and 14).
As expected, basic and acidic catalysis increased the yield of the
desired product. Using basic conditions, the reaction was scaled-
up to 90 mg of [6]-shogaol and 45.2 mg (1.2 eq.) of adenine under
agitation for 72 h at room temperature to obtain compound 1 in
36% isolated yield. Similarly, [8]-shogaol (50 mg) and [10]-shogaol
(50 mg) were subjected to identical reaction conditions thereupon
we obtained compounds 2 and 3 in 28% and 30% isolated yield,
respectively (Fig. 6). The synthetically obtained products were
identical to the ones isolated from ginger plant material by means
of 1H- and 13C NMR spectra (Supplementary Figs. 15–20) and HPLC
traces (Supplementary Figs. 21–23). This confirmed the proposed
structures of the zingerines. In addition, both natural and synthetic
samples were optically inactive demonstrating that the com-
pounds were racemic mixtures. This was confirmed by means of
chiral HPLC resolution of both synthetic and natural [6]-zingerine,
showing two peaks with 1:1 area under the curve (AUC) ratio
(Fig. 7). Although natural [6]-zingerine was not optically active,
an enzymatic origin cannot be ruled out definitively because of
the possible operation of a retro Michael/Michael type reaction
equilibrium leading to racemization under experimental condi-
tions. Furthermore, identification of biosynthetic genes and their
enzymatic products responsible for the origin of zingerines would
definitely exclude an artificial genesis. Although gingerols are pres-
Fig. 6. Synthesis of compounds 1–3.

J.J. Araya et al. / Phytochemistry 72 (2011) 935–941
939
Fig. 7. HPLC chiral resolution of [6]-zingerine (1) (A) isolated from ginger rhizome and (B) obtained by synthesis.
ent in relatively high quantities in ginger rhizome, we were unable
to detect free adenine in the initial extract or basic fraction using
LCMS analysis (data not shown).
and UV detection using diode array. Preparative HPLC separations
were done using an Agilent 1100 HPLC system with a Varian Dyna-
max C8 (8
lm, 250 ꢀ 21.4 mm), flow rate of 15 mL/min (approx.
35 bar), injection volume of 800
lL (ca. 100 mg sample), and UV
detection using diode array.
3. Conclusions
Chiral HPLC analysis was performed using a Chiralcel OD-H col-
umn (No. ODHOCD-LH013) purchased from Chiral Technologies,
Inc. (West Chester, PA) in an Agilent 1100 system. The solvent sys-
tem used was isocratic hexanes:isopropanol 70:30 (v/v), the flow
The use of our new catch-and-release methodology allowed us
to isolate and identify three compounds new to the literature from
extensively studied ginger rhizomes. The new compounds contain
an adenine group attached to the gingerol-type carbon skeleton, an
unusual structural feature in higher plants. Experiments showed
that traditional solvent partition/chromatographic methods would
have missed these alkaloids. We believe that catch-and-release
methodology can be applied more widely to natural products res-
olution not only rapidly and conveniently to prepare high quality
samples for high throughput screening campaigns, but also for iso-
lation and structural determination of novel compounds present as
very minor components as demonstrated in this report. Biological
testing of the newly isolated compounds is currently underway
and will be reported in due course.
rate was 0.9 mL/min, the injection volume was 25
detection at 254 nm.
lL, and UV
Compounds and resins were purchased from Sigma–Aldrich (St.
Louis, MO): adenine 99%; cesium carbonate 99%, hydrochloric acid;
DowexTM MarathonTM WBA Anion-Exchange resin); DowexTM
MAC-3 ion exchange resin; Sephadex LH-20. RP-TLC plates (C-18)
were obtained from Sorbent Technologies (Atlanta, GA). Aromat-
reuÒ Finum tea filters were purchased from www.cheftools.com.
4.2. Plant material and extraction
Dry powdered ginger rhizomes (150 kg) were purchased from
Naturex (South Hackensack, NJ) Lot. # E99/03/B8. Plant material
(40 kg) was subjected to a first extraction using CH2Cl2 (130 L) twice
during48 h atroomtemperature. Removalof theorganicsolvent un-
der reduced pressure afforded a CH2Cl2 extract (1.7 kg, 4.3%). The
remaining plant material was then subjected to a second extraction
using MeOH (130 L) twice during 48 h. After concentration under re-
duce pressure, the MeOH extract residue (1.2 kg, 3.0%) was obtained.
In the same way, two smaller samples (100 g) of ginger powder ob-
tained from the same company (Lot # E99/01/B8 and # E94/01/B8)
were extracted sequentially with CH2Cl2 (500 mL) and MeOH
(500 mL) to afford CH2Cl2 and methanolic extracts, respectively.
4. Experimental section
4.1. General procedures
Melting points were recorded with an OptiMelt automatic
apparatus. Optical rotations were measured with a Rudolph RS
Autopol IV automatic polarimeter. IR spectra were obtained with
a Thermo Nicolet Avatar 380 FT-IR. UV–vis measurements were
conducted with a Varian Cary 50 UV–vis spectrophotometer. 1H
NMR, 13C NMR and two dimensional spectra were recorded with
a Bruker Avance AV-III 500 with a dual carbon/proton cryoprobe.
Agitation of samples was carried out with a New Brunswick Scien-
tific Excella E1 platform shaker. Semi-preparative HPLC was con-
ducted using an Agilent 1200 HPLC system with a Phenomenex
4.3. General catch-and-release procedure
Luna C18 column (5
(approx. 160 bar), injection volume of 50
l
m, 250 ꢀ 10 mm), flow rate of 4.5 mL/min
The procedure was carried out as described previously (Araya
et al., 2010) using the MeOH extract (5.0 g). The resulting basic,
l
L (ca. 10 mg sample),

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J.J. Araya et al. / Phytochemistry 72 (2011) 935–941
acidic and neutral fractions were analyzed by LCMS and purified by
semi-preparative HPLC.
4.10. HPLC MSn analyses
The on-line HPLC/MSn analyses of extracts and fractions were
performed using an Agilent 1200 Series liquid chromatography
system coupled to a Agilent IonTrap LCMS 6310 mass spectrome-
ter. The positive ion ESI-MS experimental conditions were as fol-
lows: HV capillary voltage, 3.5 kV; drying temperature, 350 °C;
drying gas, 12.0 L/min; nebulizer, 15 psi; and capillary exit voltage,
124.8 V. The Frag Ampl was set to 1.0 V and the smart fragmenta-
tion function was used (Smart Frag Ampl was 30–200%). Targeted
analysis of zingerines was programmed as follows: (a) for [6]-zin-
gerine, isolation and fragmentation of ions m/z 411–413, then iso-
lation and detection of ion m/z 136.1; (b) for [8]-zingerine,
isolation and fragmentation of ions m/z 439–441, then isolation
and detection of ion m/z 136.1; (c) for [10]-zingerine, isolation
and fragmentation of ions m/z 467–469, then isolation and detec-
tion of ion m/z 136.1. The HPLC separations were done using an
4.4. Scale-up catch-and-release procedure
The methanolic rhizome extract (100 g) was suspended in
MeOH:H2O 2 L, 1:1 (v/v). A total of 200 g of prewashed Dowex
MAC-3 resin was added to the mixture and left stirring overnight.
The resin was then removed by filtration, washed several times
with pure MeOH (until the filtrate was clear) and the resin was fi-
nally left overnight stirring in 2% NH3 2% in MeOH (2 L). The resin
was removed by filtration, and the filtrate concentrated under re-
duced pressure to afford 1.9% basic fraction residue (1.9 g).
4.5. Isolation of zingerines
The basic fractions from the general catch-and-release protocol
were then separated by Sephadex LH-20 CC (100 g) using MeOH as
eluent to give 80 fractions (10 mL each) that were combined into
seven fractions (A–G) according to RP-TLC. Fraction F (210 mg)
was then purified using semipreparative HPLC with a linear gradi-
ent program of CH3CN and H2O water from 25:75 (v/v) (t = 0 min)
to 35:65 (t = 5 min), then 55:45 (t = 15 min), 100:0 (t = 25 min),
and finally recovery to 25:75 (t = 35 min). Compound 1 (18.2 mg,
tR = 14.7 min), compound 2 (5.2 mg, tR = 19.1 min), and compound
3 (4.8 mg, tR = 22.5 min) were obtained after removal of the mobile
phase under reduce pressure.
Agilent Eclipse XDB-C18 column (5
l
m, 4.6 ꢀ 150 mm) and the
flow rate was 1.0 mL/min (approx. 80 bar). The mobile phase was
a linear gradient of acetonitrile and water from 25:75 (v/v)
(t = 0 min) to 35:65 (t = 5 min), then 55:45 (t = 15 min), 100:0
(t = 25 min), and finally recovery to 25:75 (t = 35 min).
4.11. General synthesis of zingerines
A mixture of shogaol (0.33 mmol) and adenine (0.40 mmol,
1.2 eq.) and Cs2CO3 (5 mg) in MeOH:H2O 1:1 (15 mL) was stirred
at room temperature for 72 h. Then, organic solvent was removed
under reduced pressure and filtration, the reaction mixtures were
purified by semi preparative HPLC to afford the corresponding zin-
gerine. Accordingly, [6]-zingerine (42.7 mg), [8]-zingerine
(19.4 mg), and [10]-zingerine (19.4 mg) were obtained in 36%,
28%, and 30% yields, respectively.
4.6. Large scale isolation of shogaols
Pure [6]-, [8]-, and [10]-shogaol were isolated as described pre-
viously and the structures of the shogaols were confirmed by spec-
troscopic methods (Kim et al., 2008; Sang et al., 2009).
Acknowledgments
4.7. [6]-Zingerine (1)
The chemistry work was supported by NCCAM/ODS Grant
1R21AT004182-01A2 from the National Institutes of Health (NIH)
and the University of Kansas Center for Research project
2506014-910/099 to B.N.T., J.A. thanks LASPAU-Fulbright program
and the University of Costa Rica for financial support. J.A. also
thanks Kimberly Lovell for assistance during chiral HPLC separa-
tions. The contents are solely the responsibilities of the authors
and do not necessarily represent the official views of the NIH.
5-(6-Amino-9H-purin-9-yl)-1-(4-hydroxy-3-methoxy-
phenyl)decan-3-one; pale yellow oil;
½
a D25
ꢁ
= ꢂ0.004 (c. 0.03,
MeOH); UV (MeOH, c = 0.5 mM) kmax nm: 208, 262; IR
m
cmꢂ1
:
3326 (NAH), 3153 (NAH), 1711 (conj.>C@O), 1514 (C@C); 1H
NMR(CD3OD, 500 MHz) and 13C NMR (CD3OD, 133 MHz) see Table
1; ESIMS m/z 412.3 [M + H]+; ESIMS/MS m/z 136.1 [M + H-276.2];
HRMS m/z 412.2362 [M + H]+ (calc. for C22H30N5O2 412.2349).
Appendix A. Supplementary data
4.8. [8]-Zingerine (2)
Supplementary data associated with this article can be found, in
the online version, at doi:10.1016/j.phytochem.2011.03.007.
5-(6-Amino-9H-purin-9-yl)-1-(4-hydroxy-3-methoxy-
phenyl)dodecan-3-one; pale yellow oil; ½a 2D5
ꢁ
= ꢂ0.002 (c. 0.02,
MeOH); UV (MeOH, c = 0.5 mM) kmax nm: 208, 262; IR
m
cmꢂ1
:
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3325 (NAH), 3153 (NAH), 1713 (conj.>C@O), 1513 (C@C); 1H
NMR (CD3OD, 500 MHz) and 13C NMR (CD3OD, 133 MHz) see Table
1; ESIMS m/z 440.3 [M + H]+; ESIMS/MS m/z 136.1 [M + H-304.2];
HRMS m/z 440.2695 [M + H]+ (calc. for C24H34N5O3 440.2662).
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4.9. [10]-Zingerine (3)
5-(6-Amino-9H-purin-9-yl)-1-(4-hydroxy-3-methoxy-
phenyl)tetradecan-3-one; pale yellow oil; ½a 2D5
ꢁ
= ꢂ0.001 (c. 0.02
MeOH); UV (MeOH, c = 0.5 mM) kmax nm: 208, 262; IR
m
cmꢂ1
:
3326 (NAH), 3152 (NAH), 1710 (conj.>C@O), 1513 (C@C); 1H
NMR (CD3OD, 500 MHz) and 13C NMR (CD3OD, 133 MHz) see Table
1; ESIMS m/z 468.3 [M + H]+; ESIMS/MS m/z 136.1 [M + H-332.2];
HRMS m/z 468.2921 [M + H]+ (calc. for C26H38N5O3 468.2975).

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