Regioselective synthesis and structural elucidation of 1,4-disubstituted 1,2,3-triazole derivatives using 1D and 2D NMR spectral techniques

Article abstract of DOI:10.1002/mrc.2820

Regioselective synthesis of 2-[1-(2-oxo-2-phenylethyl)-1H-[1,2,3]triazol-4- ylmethoxy]-benzaldehyde derivatives was achieved by [3 + 2] cycloaddition reaction of 2-(prop)-2-ynyloxy-benzaldehyde derivatives with phenacyl azide. The regiochemistry and the s

Full text of DOI:10.1002/mrc.2820

MRC Letter
Received: 30 June 2011
Revised: 18 August 2011
Accepted: 22 August 2011
Published online in Wiley Online Library
(wileyonlinelibrary.com) DOI 10.1002/mrc.2820
Regioselective synthesis and structural
elucidation of 1,4-disubstituted 1,2,3-triazole
derivatives using 1D and 2D NMR spectral
techniques
Thelagathoti Hari Babu,a B. V. N. Phani Kumar,b C. Rajeswaria and
Paramasivan T. Perumala*
Regioselective synthesis of 2-[1-(2-oxo-2-phenylethyl)-1H-[1,2,3]triazol-4-ylmethoxy]-benzaldehyde derivatives was achieved
by [3 + 2] cycloaddition reaction of 2-(prop)-2-ynyloxy-benzaldehyde derivatives with phenacyl azide. The regiochemistry
and the spectral assignments of the synthesized triazole derivatives were studied using both 1D and 2D NMR spectral techni-
ques in solution. Copyright © 2011 John Wiley & Sons, Ltd.
Supporting information may be found in the online version of this article.
Keywords: 1H NMR; 13C NMR; 2D NMR; 1,4-disubstituted 1,2,3-triazoles
converted to 2-prop-2-ynyloxy-benzaldehyde 3a via reaction
with propargyl bromide 2 in the presence of potassium carbon-
Introduction
The structural diversity and biological importance of nitrogen-
containing heterocycles have made them attractive targets for
synthesis over many years. They are found in various natural pro-
ducts and have been identified as products of chemical and bio-
logical importance.[1,2] During the last decades, 1,2,3-triazoles
have become one of the important synthesized classes for che-
mists as they display many interesting properties including
antibacterial,[3] herbicidal, fungicidal,[4] antiallergic,[5] anti-HIV,[6]
GSK-3 inhibiting,[7] and antineoplastic activities.[8] Moreover, they
have been widely used in various research fields, including bio-
logical science,[9] material chemistry,[10] medicinal chemistry,[11]
and synthetic organic chemistry.[12] Many methods have been
developed to synthesize 1,2,3-triazoles by now.[13] Traditionally,
the Huisgen 1,3-dipolar cycloaddition between organic azides
and terminal alkynes is a useful and extensively applicable
method for the synthesis of N-substituted triazoles. Recently,
we reported the regioselective synthesis and biological activity
of bisindolyl triazoles[14] and the one-pot synthesis and spectral
assignments of 6-(ferrocene-1-yl)-2-(indol-3-yl)pyridine and (1H-
indol-3-yl)-6-(2-thienyl)pyridine derivatives through 1D and 2D
NMR spectral techniques in solution.[15] In continuation of this
work, we herein report the regioselective synthesis and spectral
assignments of 2-[1-(2-oxo-2-phenylethyl)-1H-[1,2,3]triazol-4-
ylmethoxy]-benzaldehyde derivatives.
ate as a base in DMF at room temperature. Then, the alkyne
2-(prop)-2-ynyloxy-benzaldehyde 3a undergoes [3 + 2] cycloaddi-
tion reaction with phenacyl azide in the presence of CuI as a
catalyst to yield triazole derivative 5a. All the products (5a–g)
tabulated in Table 1 were obtained as white solids after purified
by silica gel column chromatography. The compounds were
characterized by IR, mass, and NMR spectroscopy.
NMR spectroscopic investigations
The NMR spectra of 5a–e, 5f, and 5g were almost similar because
of the structural similarity of these compounds and were num-
bered as shown in Fig. 1. The complete proton and carbon chem-
ical shift assignments were achieved by a combination of 1D and
2D NMR experiments. Unambiguous proton chemical shift
assignments of 5a–e, 5f, and 5g were made with the aid of mul-
tiplicity pattern of 1H resonances and on the use of homonuclear
double quantum filtered (DQF) COSY. With the proton reso-
nances of 5a–e, 5f, and 5g having been assigned, the chemical
shifts of the corresponding carbons were identified using the het-
eronuclear correlation (HETCOR) experiment. The quaternary car-
bons were tracked with the help of heteronuclear multiple-bond
correlation (HMBC) experiment.
*
Correspondence to: Paramasivan T. Perumal, Organic Chemistry Division,
Central Leather Research Institute, Adyar, Chennai 600 020, India. E-mail:
ptperumal@gmail.com
Results and Discussion
Synthesis
a Organic Chemistry Division, Central Leather Research Institute, Adyar, Chennai 600
020, India
The synthetic route of designed 2-[1-(2-oxo-2-phenylethyl)-1H-
[1,2,3]triazol-4-ylmethoxy]-benzaldehyde derivatives is shown in
Scheme 1. In brief, the 2-hydroxy-1-benzaldehyde 1a was
b Chemical Physics Laboratory, Central Leather Research Institute, Adyar, Chennai 600
020, India
Magn. Reson. Chem. 2011, 49, 824–829
Copyright © 2011 John Wiley & Sons, Ltd.

1,4-Disubstituted 1,2,3-triazoles
R1
R2
CHO
O
O
R1
R1
R4
R5
R2
N
R2
Br
CHO
O
CHO
OH
N
N3
K2CO3
DMF
+
N
4a-b
R3
O
CuI/Acetone
R3
R3
5a-g
3a-f
2
1a-f
R4
R5
Scheme 1. Synthesis of 2-[1-(2-oxo-2-phenylethyl)-1H-[1,2,3]triazol-4-ylmethoxy]-benzaldehyde derivatives.
The common feature in all the compounds 5a–e, 5f, and 5g
considered is that the 1D 1H NMR spectrum showed two singlets
at dH = 5.25–5.55 and 6.15–6.35 ppm, integrating for two protons;
these data suggested that these two signals belonged to O–CH2
and N–CH2, respectively. The HETCOR showed that O–CH2 corre-
lates with carbon at dC = 62.20–68.20 ppm, whereas the N–CH2
correlates with carbon at dC = 52.00–59.00 ppm. The long-range
HMBC, giving 2J and 3J CH coupling constants, allowed the as-
signment of a number of quaternary carbons. In particular, the
proton O–CH2 correlates with two quaternary carbons at dC =
141.00–143.00 and 159.00–162.00 ppm. Their only possible
assignments can be C-4 (dC = 141.00–143.00 ppm) and C-11 (dC =
159.00–162.00 ppm). The triazolic singlet proton was resonated
at dH = 8.15–8.25 ppm and exhibited long-range correlation with
C-4 of the triazole ring A. To differentiate between the aromatic
protons of two rings B and C of compounds 5a–e, we consider
13-H on ring B and 18-H on ring C. 13-H resonated at dH = 7.75
ppm as a doublet that showed long-range HMBC with aldehydic
carbon at dC = 188.02 ppm, whereas 18-H resonated at dH = 8.08
ppm as a doublet and correlated with the carbonyl carbon at
dC = 192.15 ppm. The remaining aromatic protons on both rings
were assigned using DQF COSY. All the proton and carbon chem-
ical shift values for 5a–e are documented in Tables 2 and 3,
respectively, whereas the HMBC data for 5a–e are depicted in
Table 4.
The 1H NMR spectrum of compound 5f contained 11 aromatic
methine resonances, four of which (9.05, 7.59, 7.42, and
7.91 ppm) were attributed to ring C, because of their splitting pat-
1
terns (two d’s and two t’s) and H–1H COSY interactions. These
protons were identified as 17-H, 18-H 19-H, and 20-H, respec-
tively. The chemical shift of the carbon atoms to which these pro-
tons were bonded was subsequently determined from the
HETCOR spectrum. The two aromatic methine protons of ring B
resonated at dH = 7.77 and dH = 8.25 ppm as two doublets and
Table 1. Synthesis of 2-[1-(2-oxo-2-phenylethyl)-1H-[1,2,3]triazol-4-ylmethoxy]-benzaldehyde derivatives
Alkyne
R1
R2
R3
Azide
R4
R5
Product
Time (h)
Yield (%)a
3a
3b
3c
3d
3e
3f
H
H
H
Br
Br
I
H
4a
4a
4a
4a
4a
4a
4b
H
H
H
H
H
H
H
5a
5b
5c
5d
5e
5f
6.0
5.5
4.0
4.5
5.0
4.3
5.2
57
65
60
67
62
68
55
H
OCH3
H
H
H
Br
I
H
H
H
H
H
R1, R2 = C4H4
H
H
H
3g
H
H
R4, R5 = C4H4
5g
aIsolated yield after column chromatography.
R1
18
28
O
22
O
13
17
13
19
20
O
26
R2
14
12 27
13
12
C
14
15
21
B
25
9
B
3
3
9
14
15
12
4
N
11
B
4
N
15
9
3
O
10
2
11
N
O
2
16
N
A
16
N
A
11
O
10
4
5
A
2
N
5
N
16
5
10
1
N
1
R3
N
1
8
O
6
O
8
6
O
6
7
8
7
17
17
7
22
21
21
18
19
18'
19'
18
19
C
22'
23'
C
22
23
D
23
24
5g
5a-e
5f
20
26
D
20
24
25
Figure 1. Numbering of 1,4-disubstituted 1,2,3-triazole derivatives.
Magn. Reson. Chem. 2011, 49, 824–829
Copyright © 2011 John Wiley & Sons, Ltd.
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T. H. Babuet al.
Table 2. 1H-NMR chemical shifts (d, ppm; J, Hz)a for compounds 5a–5e in DMSO-d6 at 298 K
Proton
5a
5b
5c
5d
5e
H-5
8.30 (s)
8.20 (s)
8.30 (s)
6.23 (s)
8.26 (s)
6.20
8.26 (s)
H-6
6.23 (s)
6.20 (s)
6.22 (s)
H-9
5.42 (s)
5.34 (s)
5.43 (s)
5.33
5.27 (s)
H-13
7.68–7.70 (m)c
7.12 (t); 7.65
7.74–7.76 (m)c
7.49 (d); 8.40
8.08 (d); 8.40
7.62 (t); 8.40
7.71–7.73 (m)c
10.37 (s)
7.24–7.27 (m)c
7.21–7.23 (m)c
7.43 (d); 7.65
—
7.75 (d); 2.3
—
7.79 (d); 2.3
—
7.46 (d); 2.25
—
H-14
H-15
7.86 (dd); 3.1, 6.1
7.50 (d); 8.4
8.08 (d); 6.9
7.61 (t); 7.65
7.73 (t); 6.9
10.26 (s)
8.26 (s)
—
8.49 (d); 2.25
—
H-16
H-18, H-18′
H-19, H-19′
H-20
8.08 (d); 8.40
7.61 (t); 7.65
7.74 (t); 6.90
10.19 (s)
8.06 (d); 6.9
6.59 (t); 7.65
7.01 (t); 7.65
9.99 (s)
—
8.08 (d); 6.9
7.61 (t); 7.65
7.73 (t); 7.65
9.96 (s)
H-21
H-24
—
3.94 (s)
—
—
aMultiplicity in parentheses.
bCoupling constants (J) in italics.
cOverlapped signals.
were assigned as 15-H and 16-H, respectively. 15-H showed long-
range correlation with two quaternary carbons observed at dC =
163.03 and 130.65 ppm, which were confirmed as C-11 and
C-13, respectively, whereas 16-H showed HMBC with two quater-
nary carbons identified as C-12 and C-14. The proton and carbon
chemical shift values along with HMBC correlations of compound
5f are shown in Table 5. Whereas the proton and carbon chemi-
cal shift values along with HMBC correlations of compound 5g
are shown in Table 6.
exhibited a three-bond correlation with the H-6 proton (Fig. 2).
Hence, the formed triazole derivatives were confirmed as 1,4-
regioisomers.
Conclusions
In summary, we have demonstrated a simple method for the syn-
thesis of 2-[1-(2-oxo-2-phenylethyl)-1H-[1,2,3]triazol-4-ylmethoxy]-
benzaldehyde derivatives via [3+ 2] cycloaddition reaction of
propargylated salicylaldehyde derivatives with phenacyl azide
and 2-azido-1-naphthalen-2-yl-ethanone. 1H and 13C NMR chemical
shift values for the newly synthesized 2-[1-(2-oxo-2-phenylethyl)-
1H-[1,2,3]triazol-4-ylmethoxy]-benzaldehyde derivatives and their
regiochemistry were assigned using 2D NMR techniques.
The one-dimensional 1H and 13C NMR spectra by them-
selves were not enough to assign the 1,4 regiochemistry of
the synthesized 1,2,3-triazoles; hence, it required a detailed in-
vestigation through HETCOR and 13C–1H HMBC experiments.
The HETCOR experiment exhibited the one bond correlation
of the triazolic proton resonated at d 8.23 ppm with triazolic
carbon observed at d 126.9 ppm. The comparison of the 13C–1H
HMBC spectra of the 1,4-disubstituted triazole derivative 5a in
the region between C-5 to C-6 showed that the C-5 carbon
Experimental Section
General
Table 3. 13C NMR chemical shifts (d in ppm) for compounds 5a-e in
DMSO-d6 at 298 K
All the substituted salicylaldehydes, propargyl bromide, phenacyl
bromide, copper iodide, and DMSO-d6 were purchased from
Aldrich Chemicals (Aldrich Chemicals, USA). IR measurements
were performed using KBr pellets for solids using Perkin Elmer
(Perkin Elmer, UK) RXI FT-IR.
Carbon
5a
5b
5c
5d
5e
C-4
143.32
126.43
59.99
142.46
126.68
55.92
141.97
126.54
55.98
141.33
127.30
55.98
141.33
127.19
55.93
All NMR experiments were made on a JEOL (JEOL, Japan) ECA-
500 MHz high resolution FT-NMR spectrometer operating at fre-
quencies 500.16 MHz (1H) and 125.77 MHz (13C). An amount of
30 mg of compounds was dissolved in 0.7 ml of DMSO-d6. Tetra-
methylsilane was used as an internal reference standard for the as-
signment of 1H and 13C chemical shifts. All the NMR spectra were
recorded at 298 K. JEOL-Delta software package (version 4.3.6) was
used for the purpose of NMR pulse sequences and data processing.
The experimental parameters chosen for 1D 1H/13C NMR were
as follows: spectral width 15/250 ppm, number of data points
16 384/32 768, number of scans 8/200, acquisition time 2.18/
1.04 s, relaxation delay 5/2 s, and 90ꢀ pulse width 12.62/12.25 ms.
Two-dimensional correlation spectra were recorded in order to
C-5
C-6
C-7
192.18
62.23
192.07
66.20
192.15
62.60
192.00
67.87
191.98
68.16
C-9
C-11
C-12
C-13
C-14
C-15
C-16
C-17
C-18
C-19
C-20
C-21
C-24
160.48
124.53
127.74
121.20
136.44
114.29
134.11
128.23
129.04
134.32
189.17
—
150.09
129.70
124.64
118.06
118.75
152.99
134.10
128.21
129.01
134.28
190.04
56.17
159.43
126.04
129.88
113.07
138.44
117.15
134.09
128.21
129.03
134.30
188.02
—
156.63
132.24
130.06
119.83
140.76
117.78
134.06
128.23
129.03
134.31
187.97
—
159.83
131.67
136.90
96.85
151.83
90.93
134.06
128.19
128.99
134.26
188.29
—
1
1
track H–1H and H–13C correlations. A relaxation delay of 1.5 s
was used in all the 2D experiments.
1H–1H COSY: COSY spectra were obtained using the gradient
version of DQF COSY pulse sequence. The spectra resulted
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1,4-Disubstituted 1,2,3-triazoles
Magn. Reson. Chem. 2011, 49, 824–829
Copyright © 2011 John Wiley & Sons, Ltd.
wileyonlinelibrary.com/journal/mrc

T. H. Babuet al.
Table 5. 1H and 13C NMR chemical shifts and heteronuclear multiple-bond correlation (HMBC) of compound 5f
Carbon numbering
13C chemical shift (d, ppm) 5f
Proton numbering
1H chemical shift (d, ppm; J, Hz)a 5f
HMBC
C-4
142.22
126.53
56.00
—
H-5
H-6
—
C-5
8.27 (s)
C-4
C-6
6.17 (s)
C-5, C-7
C-7
192.15
63.15
—
—
C-9
H-9
—
5.54 (s)
C-4, C-5, C-11
C-11
C-12
C-13
C-14
C-15
C-16
C-17
C-18
C-19
C-20
C-21
C-22
C-23
C-24
C-25
163.03
116.35
130.65
128.45
137.88
115.41
123.97
129.82
124.93
128.67
134.11
128.21
129.03
134.30
191.41
—
—
—
—
—
—
—
—
—
—
—
H-15
H-16
H-17
H-18
H-19
H-20
—
8.25 (d); 9.15
7.77 (d); 9.10
9.05 (d); 9.15
7.59 (t); 7.65
7.42 (t); 6.85
7.91 (d); 8.40
—
C-11, C-13, C-20
C-12, C-14
C-14, C-19
C-13, C-20
—
C-13, C-15
—
H-22
H-23
H-24
H-25
8.01 (d); 7.65
7.42 (t); 6.85
7.67 (t); 6.90
10.70 (s)
C-7, C-21, C-23, C-24,
C-21, C-22, C-24
C-22
C-13
aMultiplicity in parentheses.
bCoupling constants (J) in italics.
from 1024 (F2) Â 256 (F1) data matrix size with one scan per t1 in-
crement. A spectral width of 7 ppm was used in both F1 and F2
dimensions.
1H–13C HETCOR: HETCOR spectra were recorded using the
standard hector pulse program. The acquisition parameters were
as follows: spectra resulted from 1024 Â 128 data matrix size with
Table 6. 1H and 13C NMR chemical shifts and heteronuclear multiple-bond correlation (HMBC) of compound 5g
Carbon numbering
13C chemical shift (d, ppm) 5g
Proton numbering
1H chemical shift (d, ppm; J, Hz)a 5g
HMBC
C-4
142.34
126.45
55.98
—
H-5
—
8.32 (s)
C-5
C-4
C-6
H-6
6.34 (s)
C-5, C-7
C-7
192.07
62.27
—
—
C-9
H-9
5.41 (s)
C-4, C-5, C-11
C-11
C-12
C-13
C-14
C-15
C-16
C-17
C-18
C-19
C-20
C-21
C-22
C-23
C-24
C-25
C-26
C-27
160.48
124.55
127.74
121.20
136.43
114.32
132.09
130.54
135.48
131.43
129.23
123.34
129.72
127.32
127.86
128.69
189.17
—
—
—
—
H-13
H-14
H-15
H-16
—
7.67–7.68 (m)c
7.11 (t); 6.85
7.69–7.70 (m)c
7.48 (d); 8.40
—
C-11, C-21
C-12, C-13, C-16
C-11, C-13
C-12, C-14
H-18
—
8.83 (s)
C-7, C-19, C-22, C-20
—
—
—
H-21
H-22
H-23
H-24
H-25
H-26
H-27
7.71–7.72 (m)c
8.05 (d); 7.65
8.15 (d); 7.65
7.73–7.75 (m)c
8.03 (t); 6.85
8.09 (d); 8.40
10.36 (s)
—
C-7, C-17
C-20, C-25
—
C-20, C-23
C-19, C-20
C-13
aMultiplicity in parentheses.
bCoupling constants (J) in italics.
cOverlapped signals.
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1,4-Disubstituted 1,2,3-triazoles
CHO
O
3,5-Diiodo-2-[1-(2-oxo-2-phenylethyl)-1H[1,2,3]triazol-4-
ylmethoxy]-benzaldehyde (5e)
Pale yellow solid; mp 184–186 ꢀC; Rf 0.47 (30% AcOEt/
petroleum ether); IR (KBr): 1693, 1227, 959, 686 cmÀ1: MS (EI): m/z=
595.93 [M+ +Na+];
N
N
O
N
3-bond
connectivity
2-[1-(2-Oxo-2-phenylethyl)-1H-[1,2,3]triazol-4-ylmethoxy]-
naphthalene-1-carbaldehyde (5f)
H
Off-white solid: mp 176–178 ꢀC; Rf 0.46 (30% AcOEt/petroleum
HMBC
ether); IR (KBr): 3083, 1703, 1670, 1339, 1234, 1055, 810, 756 cmÀ1
MS (EI): m/z = 394.39 [M+ + Na+];
;
2-[1-(2-Naphthalen-2-yl-2-oxo-ethyl)-1H-[1,2,3]triazol-4-
ylmethoxy]-benzaldehyde (5g)
Pale yellow solid: mp 170–172 ꢀC; Rf 0.45 (30% AcOEt/petro-
leum ether); IR (KBr): 3078, 1701, 1677, 1347, 1274, 815,
768 cmÀ1; MS (EI): m/z = 394.13 [M+ + Na+];
1,4-Regioisomer
Figure 2. Heteronuclear multiple-bond correlation (HMBC) in 1,4-
regioisomer.
SUPPORTING INFORMATION
eight scans per t1 increment. A spectra width of 180 ppm in F2
and 7 ppm in F1 was recorded.
Supporting information may be found in the online version of
this article.
1H–13C HMBC: The gradient version of HMBC experiments was
recorded in order to sketch the long-range (two and three bonds)
1H–13C correlations. The long-range coupling constant (nJCH) op-
timized was 8 Hz. The spectra resulted from 2048 Â 256 data ma-
trix size with eight scans per t1 increment. A spectral width of
7 ppm in F2 and 180 ppm in F1 was recorded.
Acknowledgement
The authors thank the Council of Scientific and Industrial Re-
search (CSIR), New Delhi, India, for the financial assistance.
Mass spectra were recorded with Thermo Finnigan mass spec-
trometer (Thermo Finnigan mass spectrometer, Austria) using an
electrospray ionization method. Melting points were determined
in capillary tubes and are uncorrected. Analytical thin layer chro-
matography was performed on precoated plastic sheets of silica
gel G/UV-254 of 0.2-mm thickness (Macherey-Nagel, Düren,
Germany).
General procedure for the synthesis of 2-[1-(2-oxo-2-phe-
nylethyl)-1H-[1,2,3]triazol-4-ylmethoxy]-benzaldehyde deri-
vatives (5a-e)To a stirred solution of alkyne 3a (1 mmol) and
CuI in acetone at room temperature was added phenacyl azide
4a, with continued stirring until the specified time as mentioned
in Table 1. After the reaction was complete as indicated by thin
layer chromatography, the reaction mixture was filtered through
celite, and the filtrate was concentrated in vacuo. The crude prod-
uct was chromatographed, and appropriate isolated yield of the
pure product 5a is shown in Table 1.
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2-[1-(2-Oxo-2-phenylethyl)-1H-[1,2,3]triazol-4-ylmethoxy]-
benzaldehyde (5a)
Off-white solid: mp 172 ꢀC; Rf 0.40 (30% AcOEt/petroleum
ether); IR (KBr): 1682, 1597 1237, 1045, 762cmÀ1; MS (EI): m/z=
344.20 [M+ +Na+];
3-Methoxy-2-[1-(2-oxo-2-phenylethyl)-1H-[1,2,3]triazol-4-
ylmethoxy]-benzaldehyde (5b)
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Off-white solid: mp 154–156 ꢀC; Rf 0.45 (30% AcOEt/petroleum
ether); IR (KBr): 3062, 2932, 2846, 1686, 1586, 1480, 1240, 964,
766 cmÀ1; MS (EI): m/z = 374.07 [M+ + Na+];
5-Bromo-2-[1-(2-oxo-2-phenylethyl)-1H-[1,2,3]triazol-4-
ylmethoxy]-benzaldehyde (5c)
Off-white solid: mp 188–190 ꢀC; Rf 0.45 (30% AcOEt/petroleum
ether); IR (KBr): 3075, 2957, 1693 1577, 1433, 977, 687 cmÀ1; MS
(EI): m/z = 422.20 [M+ + Na+];
3,5-Dibromo-2-[1-(2-oxo-2-phenylethyl)-1H-[1,2,3]triazol-
4-ylmethoxy]-benzaldehyde (5d)
Yellow solid: mp 190–192 ꢀC; Rf 0.48 (30% AcOEt/petroleum
ether); IR (KBr): 3061, 2947, 1689, 1574, 1439, 962, 682 cmÀ1; MS
(EI): m/z = 501.93 [M+ + Na+];
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Journet, D. Cai, J. J. Kowal, R. D. Larsen, Tetrahedron Lett. 2001, 42,
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Kumar, P. T. Perumal, Magn. Reson. Chem. 2010, 48, 554.
Magn. Reson. Chem. 2011, 49, 824–829
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