A synthetic and structural study of arylselenoamides and 2,4-diaryl-1,3- selenazoles

Article abstract of DOI:10.1055/s-0034-1378525

The systematic preparation of 2,4-diaryl-1,3-selenazoles was carried out by two-component cyclization of the primary selenoamides with α-halo ketones. Selenoamides were obtained from the reaction of Woollins' reagent with arylnitrile, followed by hydrolys

Full text of DOI:10.1055/s-0034-1378525

LETTER
▌2189
lAetteSr ynthetic and Structural Study of Arylselenoamides and 2,4-Diaryl-1,3-
Selenazoles
Arylselenoamides and 2,4-Diaryl-1,3-Selenazoles
Guoxiong Hua, Junyi Du, Alexandra M. Z. Slawin, J. Derek Woollins*
EaStCHEM School of Chemistry, University of St Andrews, Fife, KY16 9ST, UK
Fax +44(1334)463384; E-mail: jdw3@st-and.ac.uk
Received: 30.04.2014; Accepted after revision: 20.06.2014
2,4-bis(phenyl)-1,3-diselenadiphosphetane-2,4-diselenide
Abstract: The systematic preparation of 2,4-diaryl-1,3-selenazoles
{[PhP(Se)(μ-Se)]2, Woollins’ reagent},20–27 followed by
was carried out by two-component cyclization of the primary sele-
treatment with water.28 By using this method, a series of
new primary selenoamides was prepared in excellent
noamides with α-halo ketones. Selenoamides were obtained from
the reaction of Woollins’ reagent with arylnitrile, followed by hy-
drolysis with water. Three selenoamides have close structural simi- yields. Herein, we report a very simple route to prepare a
larities along with intermolecular interactions such as the strong N–
H···O hydrogen bonding, the weak N–H···Se, C–H···O/N/Se inter-
molecular interactions and π–π stacking interactions; meanwhile,
new compounds have been fully characterized spectro-
the newly formed five-membered N–C–Se–C–C rings in ten 2,4-di-
aryl-1,3-selenazoles have either planar or near-planar conforma-
series of novel 2,4-diaryl-1,3-selenazoles from arylni-
triles, Woollins’ reagent/water, and α-halo ketones. The
scopically and by single-crystal X-ray structural studies.
tions along with the weak C–H···O/N/Se/Br/Cl intermolecular
interactions and π–π stacking interactions. In addition, the weak
Se···Se close contacts in four cases and the C–H···N intramolecular
interactions in two structures were also observed within the all solid
The reactions proceed at atmospheric pressure, and the
structures.
Refluxing toluene solution of arylnitriles with an equimo-
lar amount of Woollins’ reagent, followed by hydrolysis
with water afforded a series of arylselenoamides 1a–i.28
primary arylselenoamides are obtained in good to excel-
Key words: selenoamides, 1,3-selenazoles, Woollins’ reagent, X-
lent yields. The reaction can conveniently be performed
ray crystal structures, α-halo ketones
on a 1.0 mmol or larger scale. Arylselenoamides 1a–i
were allowed to react further with an equivalent of α-halo
ketones under nitrogen atmosphere with subsequent
workup in air resulting in a series of the corresponding
2,4-diaryl-1,3-selenazoles 2a–q in 83–99% yields (Table
1). It should be noted that arylselenoamides bearing high-
ly substituted groups, for example, selenoamides 1d and
1f result in lower yields than other selenoamides with less
or without any substituted group. The highest yield was
Selenium-containing heterocyclic compounds have re-
ceived considerable attention in recent years due to their
interesting reactivity and their potential pharmaceutical
applications,1,2 their uses in new materials,3 as well as re-
agents and catalysts.4 Among them, the selenazole deriv-
atives are of marked interest because of their antitumor,
antibacterial, and other notable activities.5–9 Therefore,
found for selenoamide 1a without any substituted group.
many synthetic approaches to selenazole derivatives have
As for as the synthesis of the 2,4-diaryl-1,3-selenazoles,
been extensively developed.10,11 However, encountering
the lowest yields were found in 2,4-diaryl-1,3-selenazoles
2g and 2j.
major problem is the availability of the starting material,
primary selenoamides, for the preparation of selenazoles.
The formation of 2,4-diaryl-1,3-selenazoles 2a–q can be
Many synthetic strategies for the preparation of primary
explained considering the mechanism depicted in Scheme
selenoamides have been documented so far, for example,
1. The intermediate A, the addition product of seleno-
by reaction of nitriles with the highly toxic selenating re-
amides and α-halo ketones, further carried on the cycliza-
agents H2Se or NaSeH, generated in situ from
NaBH4/Se,12 LiAlHSeH, formed in situ from LiAlH4/Se,13
Se/CO,14 P2Se5/H2O,15 and tris(trimethylsily)monoseleno-
phosphate.16 In addition, although some alternative
selenating reagents such as Al2Se3,17 (Me3Si)2Se,18 and 4-
methylselenobenzoate19 have also been applied in these
preparations in recent years, almost all of these methods
required prolonged reaction times, high temperature, and
inconvenient reaction conditions or could not always be
reproduced.15 We have previously reported a highly effi-
cient approach for the preparation of a series of primary
arylselenoamides from the reaction of arylnitriles with
tion reaction resulting in another intermediate B, which
subsequently lost one molecule of H2O leading to the for-
mation of compounds 2a–q.
The synthesis, characterization, and X-ray single-crystal
structures of arylselenoamides 1a–e have been reported
previously by us,28 thus, we will not mention them again
here. Arylselenoamides 1f–i and 2,4-diaryl-1,3-selenazoles
2a–q are stable to air or moisture for months without any
signs of degradation occurring (e.g., including reddening
of the powders due to the expulsion of elemental selenium
which is accompanied by the evolution of foul-smelling
gas). The characterization of arylselenoamides 1f–i and
2,4-diaryl-1,3-selenazoles 2a–q was performed by means
SYNLETT 2014, 25, 2189–2195
Advanced online publication: 28.07.2014
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of H NMR, C NMR, Se NMR, and IR spectroscopy
0
9
3
6
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5
2
1
4
1
4
3
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DOI: 10.1055/s-0034-1378525; Art ID: st-2014-b0355-l
© Georg Thieme Verlag Stuttgart · New York

2190
G. Hua et al.
LETTER
Table 1 Yields, Melting Points, and 77Se NMR Data for Compounds 1a–i and 2a–q
Compd
X
Ar1
Ar2
Yield (%)
mp (°C)
77Se NMR (δ, ppm)
1a
1b
1c
1d
1e
1f
4-BrC6H4
–
91
98
91
67
86
83
90
86
89
91
96
95
93
98
97
86
97
97
83
98
94
97
95
93
95
99
137–139
122–124
74–75
647.2
663.3
641.2
578.8
715.8
657.8
741.0
686.2
762.2
723.2
720.0
719.1
719.8
710.2
705.5
710.9
798.8
785.6
731.9
743.5
742.6
721.1
765.6
774.1
757.0
712.2
Ph
–
3-MeC6H4
–
3,4-(MeO)2C6H3
2,6-Cl2C6H3
2,4,6-(MeO)3C6H2
4-F3CC6H4
–
177–179
118–120
168–170
140–141
146–148
118–119
142–144
113–115
90–92
–
–
1g
1h
1i
–
naphthalen-2-yl
naphthalen-1-yl
4-BrC6H4
–
–
2a
2b
2c
2d
2e
2f
Br
Br
Br
Br
Br
Br
Cl
Br
Br
Br
Br
Cl
Br
Br
Br
Br
Br
4-ClC6H4
4-ClC6H4
4-ClC6H4
4-BrC6H4
4-ClC6H4
Ph
Ph
3-MeC6H4
3-MeC6H4
100–102
140–142
88–90
3,4-(MeO)2C6H3
3,4-(MeO)2C6H3
3,4-(MeO)2C6H3
2,6-Cl2C6H3
2,6-Cl2C6H3
4-F3CC6H4
2g
2h
2i
4-BrC6H4
4-O2NC6H4
4-ClC6H4
4-BrC6H4
4-O2NC6H4
Ph
150–152
96–98
54–56
2j
128–130
141–143
116–118
148–150
–
2k
2l
4-F3CC6H4
naphthalen-2-yl
naphthalen-2-yl
naphthalen-1-yl
naphthalen-1-yl
naphthalen-1-yl
naphthalen-2-yl
2m
2n
2o
2p
2q
4-ClC6H4
4-ClC6H4
3-O2NC6H4
4-MeC6H4
4-MeC6H4
–
–
152–154
and mass spectrometry in conjunction with single-crystal signals from the aromatic carbon backbones. The 77Se
X-ray crystallography.
NMR spectra of all compounds display singlet signals in
the range δ = 657.8–741.0 ppm, comparable to the related
selenoamides.28–33 It is worth noting that arylseleno-
amides 1e and 1g bearing the electron-withdrawing sub-
stituted CF3 and Cl groups on the phenyl ring have the
bigger 77Se NMR chemical shifts than arylselenoamide 1b
with nonsubstituted group, whilst arylselenoamides 1a,c–
f bearing the electron-releasing substituted Br, Me, and
MeO groups show smaller 77Se NMR chemical shifts than
arylselenoamide 1b with nonsubstituted group. In addi-
tion, the 77Se NMR chemical shifts display the big differ-
ence in naphthalenylselenoamides 1h and 1i, indicating
that the C(Se)–NH2 position apparently affects the 77Se
NMR chemical shift value. Furthermore, these 77Se NMR
All new compounds show the anticipated [M + H]+ or [M
+ Na]+ peak in their mass spectra, satisfactory accurate
mass measurements and appropriate isotopic distribu-
tions. The IR spectra of arylselenoamides 1f–i show
strong bands ranging from 1587–1656 cm–1 resulting
from the δ(N–H) accompanied with intense bands in the
range of 680–654 cm–1 being characteristic for the C=Se
group.28–30 Furthermore, the H NMR spectra exhibit all
1
the expected peaks including broad singlet signals be-
tween δ = 7.88–8.80 ppm assigned to the (C=Se)–NH2
group, which are in good agreement with literature val-
ues.28–33 The 13C NMR spectra have signals for the C=Se
group at δ = 206.5–207.5 ppm along with the expected
Synlett 2014, 25, 2189–2195
© Georg Thieme Verlag Stuttgart · New York

LETTER
Arylselenoamides and 2,4-Diaryl-1,3-Selenazoles
2191
for 1f and 1h in which the asymmetric unit contains two
independent molecules. Crystal data and structure refine-
ment for compounds 1f,h,i and 2b–g,m–p are summa-
rized in Tables S1–S3 and selected bond lengths and
angles are listed in Tables S4–S6 of the Supporting Infor-
mation.
Se
Woollins' reagent
H2O, toluene
Ar1
N
Ar1
NH2
reflux, 9 h
1a–i
O
Ar2
EtOH, reflux
1 h
Br
The structures of 1f and 1i both crystallize in the space
group P-1, whereas 1h crystallizes in the C2/c space
group. In 1f, 1h, and 1i the bond lengths of the C=Se dou-
ble bond range from 1.833(4)–1.843(6) Å and the C–N
bond lengths are in the range from 1.304(6)–1.310(7) Å
and are comparable to the literature values for the typical
C=Se double bond distances [1.81(5)–1.856(4) Å] and C–
N distances [1.270(7)–1.324(8) Å] in primary seleno-
amides.28,31 The selenoamide functionalities are not par-
ticularly coplanar with the aryl backbone, with the
dihedral angles between the Se(1)–C(1)–N(1) mean plane
and the aryl mean plane being 29.33(38.41), 25.31(20.41),
and 60.80°, respectively. The biggest angle is observed in
1i, suggesting the biggest spatial crowding effect from the
naphthalene ring plane with the selenium atom avoiding
any peri interaction (Figure 1).
Ar2
HO
N
Ar1
Se
cyclization
O
Ar1
Ar2
NH
Se
B
A
H2O
Ar2
N
Ar1
Se
2a–q
Scheme 1 Synthesis of compounds 1a–i and 2a–q (X, Ar1, and Ar2
groups are defined in Table 1)
Surprisingly, N–H···Se hydrogen bonding was not ob-
served in 1f,h,i unlike previous reports for similar seleno-
amides.28,37 However, there is the strong N–H···O
hydrogen-bond interaction occurring in 1f. The O atom
from the para position CH3O group on the phenyl ring
acts as hydrogen-bond acceptors towards the N–H groups
of a neighboring molecule giving rise of a ‘zigzag chain’
polymeric architecture as shown in Figure 2. The N–
H···OCH3 and N···O–CH3 distances are 2.20 [2.12] Å
and 2.986(6) [2.969(6)] Å, respectively, obviously, these
values are strong enough to challenge the classic intra-
backone N–H···O=C hydrogen bonds in the amide groups
and carbamate group [in which the N–H···O=C and
N···O=C lengths are 2.218 and 2.97 Å in amide group,
and the N–H···O=C and N···O=C lengths are 3.141 and
3.58 Å in the carbamate group].38 Furthermore, the N–
H···O at 48.27 [161.28]° angles in 1f are wider than that
in the amide group (the angle N–H···O 141°) and that in
the carbamate group (the angle N–H···O 79°).38 The re-
sults can confirm that the N–H···O–CH3 hydrogen bond-
ing in 1f appears to be significantly stronger than the N–
H···Se hydrogen bonding [N–H···Se distances ranging
from 2.48(9)–2.90(14) Å and Se···N lengths ranging from
3.403(3)–3.580(11) Å, with the angle N–H···Se ranging
from 115(1)–174(5)°] in the selenoamide groups,28,37 and
the N–H···S hydrogen bonding [N–H···S distances rang-
ing from 2.55–2.78 Å and S···N lengths ranging from
3.394(18)–3.605(3) Å, with the N–H···S angles ranging
from 158.0–173.0°] in the thioamide groups.39,40
chemical shifts are significantly bigger than that in ar-
ylselenoamide 1b, suggesting that the naphthalene ring
behaves as an electron-withdrawing functional group.
The IR spectra of 2,4-diaryl-1,3-selenazoles 2a–q reveal
an absorption band between 1480–1702 cm–1 due to the
ν(C–N) vibration whilst an absorption band in the range of
549–696 cm–1 can be assigned to the ν(Se–C) vibra-
tion.11,34,35 The 1H NMR spectra of 2,4-diaryl-1,3-
selenazoles 2a–q show singlet peaks in the range of δ =
8.06–8.81 ppm from the sole azole hydrogen atom pres-
ent. In the 13C NMR spectra of 2,4-diaryl-1,3-selenazoles
2a–q, the chemical shifts for the selenazole ring fall in the
range of δ = 170.7–190.1, 153.7–159.6, and 109.4–127.1
ppm, respectively. Interestingly, it is worth noting that
77Se NMR chemical shifts in 2,4-diaryl-1,3-selenazoles
2a–q are in the range of δ = 705.5–798.8 ppm, that is, at
higher chemical shifts than in their precursor seleno-
amides 1f–i (δ = 657.8–741.0 ppm). The 2,4-diaryl-1,3-
selenazoles bearing three electron-withdrawing groups
(Cl and NO2) on two peripheral phenyl rings in 2h and 2i
show much higher chemical shifts than the others with
electron-releasing groups or less electron-withdrawing
groups on two peripheral phenyl rings. 1,3-Selenazoles
2l–q having one peripheral naphthalene ring show signifi-
cantly bigger chemical shifts than 1,3-selenazoles 2a–g
bearing two peripheral phenyl rings, further confirming
that the naphthalene ring can act somehow as an electron-
withdrawing functional group in the molecule.
The supramolecular assembly in 1f, 1h, and 1i making up
the form of three-dimensional networks were built by the
slightly different hydrogen bonding and other intermolec-
ular interactions. The multisheeted supramolecular as-
sembly in 1f is formed by the strong intermolecular N–
H···O hydrogen bonds in conjunction with a series of
weak O–C–H···O/N/Se, C–H···O intermolecular interac-
Crystals of selenoamides 1f,h,i and 2,4-diaryl-1,3-
selenazoles 2b–g,m–p36 suitable for X-ray crystallo-
graphic analysis were obtained by the diffusion of hexane
into a dichloromethane solution of the compound at room
temperature in each case. The structures have a single
molecule of the compound in the asymmetric unit, except
© Georg Thieme Verlag Stuttgart · New York
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G. Hua et al.
LETTER
Figure 1 Single-crystal X-ray structures of 1f, 1h, and 1i
tions and π–π stacking interaction (Figure S1 of the Sup- by a combination of N–H···Se, C–H···Se, and C–H···N
porting Information). However, details of packing motif intermolecular interactions, and π–π stacking interaction,
reveal that intermolecular interactions in 1h and 1i are the latter involves π-systems such as phenyl rings and
somehow different from 1i: the neat-crossed-layer frame- naphthalene rings (Figures S2 and S3 of the Supporting
work in 1h and the multistaged network in 1i are formed Information). In the π–π stacking interactions in 1f, two
adjoining parking aryl rings have a dihedral angle of
25.78°, contributed from strong N–H···O hydrogen bonds
and weak N–H···Se, C–H···Se, and C–H···N intermolec-
ular interactions. Whilst, there are two sets of π–π stack-
ing interactions in the supramolecular assembly of 1h
with a dihedral angle of 57.49°, for each set of π–π stack-
ing interaction, the naphthalene rings of the molecules at
(x, y, z) and (x + 1, y + 1 z + 1), which are completely par-
allel, have an interplanar spacing of 3.643 Å, falling with-
in the conventional range [3.6197(19)–3.670(4) Å] for π-
interactions.41 However, the π–π stacking interactions in
1i are strictly parallel with the naphthalene rings of the
molecules at (x, y, z) and (x + 1, y + 1, z + 1) having an
interplanar spacing of 3.788 Å, which is slightly longer
than that in the structure of 1h. Furthermore, all selenium
atoms keep close contacts with pairs between neighboring
stacks in solid structure of 1h. As a result, a zigzag ar-
rangement of the selenium atoms occurs with the intermo-
lecular Se···Se distances d1 and d2 are respective 3.915
and 4.181 Å, the values are very closer than the van der
Waals distance between two selenium centers (4.0 Å).42
Figure 2 X-ray crystal structure of 1f showing ‘zigzag chain’ poly-
meric network built up with ‘head to tail’ linked by the strong N–
H···O hydrogen bonding
The short Se···Se contact is believed to play an important
role for the packing in the solid state.43
Synlett 2014, 25, 2189–2195
© Georg Thieme Verlag Stuttgart · New York

LETTER
Arylselenoamides and 2,4-Diaryl-1,3-Selenazoles
2193
On the molecular level (Figure 3), the newly formed five- from 1.02–20.38°, with the exceptions of the structures 2n
membered N(1)–C(2)–Se(3)–C(4)–C(5) rings in struc- and 2p, where the dihedral angles are 42.82° and 37.89°,
tures 2b–g and 2m–p possess similar near-planar confor- respectively. Due to the rotational symmetry, this leads to
mation with Se atom deviating from 0.000–0.012 Å, the planes of their phenyl rings being inclined from re-
respectively, from the selenazole mean planes. There are spective 5.46–49.66° with respect to each other. The C–Se
some differences in the dihedral angles between peripher- bond distances in 2b–g and 2m–p vary from 1.803(13)–
al ring planes and the selenazole ring mean planes ranging 1.909(3) Å, covering the range of C–Se bond lengths ob-
Figure 3 Single-crystal X-ray structures of 2b–g and 2m–p
© Georg Thieme Verlag Stuttgart · New York
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2194
G. Hua et al.
LETTER
served in the five-membered ring 1,3,4-selenadiazoles involve the aryl ring H atoms, azole ring H atoms, and the
[1.87–1.89 Å]37,41,44,45 and in 2,5-diarylselenophenes (ca. N, O, Se atoms in 2o (Figure S12) and the aryl ring H at-
1.86–1.89 Å),46 and are marginally shorter than that oms, azole ring H atoms, OCH3 group H atoms, and the N,
would be expected from the typical C–Se single-bond O, Se atoms in 2p (Figure S13). In addition, the weak in-
lengths [ca. 1.92–1.94 Å].47–49 Both C=N double-bond termolecular Se···Se close contacts between neighboring
distances [1.285(14)–1.309(11) Å] and C–N single-bond stacks with linear arrangement of the selenium atoms
distances [1.377(13)–1.403(11) Å] in these structures are were observed, the Se···Se distances d1 within a stack are
comparable with those in the reported 1,3-selenazoles respective 4.235, 4.417, and 3.937 Å, the values are very
[1.268(11) Å for C=N bond and 1.384(11) Å for C–N approximate to the van der Waals distance between two
bond],11 which are significantly shorter than the usual C– selenium centers (4.0 Å)42 in the structures of 2f, 2g, and
N single-bond length of 1.47 Å,50–52 indicating clearly that 2m leading to their structural conformation somewhat dif-
some degree of delocalization occurring in these newly ferent from each other.
formed selenazole rings. The C–Se–C angles in structures
2b–g and 2m–p differing from 84.24(15)–85.3(4)° are
In summary, Woollins’ reagent reacts with one equivalent
of arylnitrile, followed by water to give a series of primary
arylselenoamides 1a–i in good to excellent yields. The cy-
considerately wider than that in the reported similar struc-
ture [83.3(5)°],11 and that in 1,3,4-selenadiazoles
clization of primary arylselenoamides with α-halo ketones
[81.9(4)–82.7(2)°],37,41,44,45 and significantly smaller than
delivered a variety of new 2,4-diaryl-1,3-selenazoles 2a–
q in excellent yields. Thirteen single-crystal structures
were studied to reveal that three X-ray single-crystal
structures of selenoamides 1f, 1h, and 1i have very close
that in the 2,5-diarylselenophenes [87.8(8)°],46 indicating
the size order for the C–Se–C angles in the five-mem-
bered ring systems being: 1,3,4-selenadiazoles < 1,3-
selenazoles < 2,5-diarylselenophenes.
structural similarities along with similar intermolecular
Despite the similarities between compounds 2b–g and interactions, such as the strong N-H···O hydrogen bond-
2m–p in terms of their chemical constitution and their ing and the weak N–H···Se, C–H···O/N/Se intermolecu-
overall molecular shape, the intramolecular or intermolec- lar interactions, and π–π stacking interactions; 1,3-
ular interaction are somehow different for all these com- selenazoles 2b–g and 2m–p possess rather similar molec-
pounds to form supramolecular aggregation arrangements ular conformations and intermolecular interactions such
(Figures S4–S13 of the Supporting Information). The ag- as the newly formed five-membered N(1)–C(2)–Se(3)–
gregation in 2c, 2d, and 2m is dominated by C–H···X (X C(4)–C(5) rings being near planar with the weak C–
= Cl, Br) intermolecular interactions, C–H···Se intermo- H···O/N/Se/Br/Cl intermolecular interactions and π–π
lecular interactions, C–H···N intermolecular interactions, stacking interactions. Furthermore, the C–H···N intramo-
and π–π stacking interactions that lead to the formation of lecular interaction was found in two cases of 2,4-diaryl-
multistaged or multisheeted network structures; whilst the 1,3-selenazoles; the close contacts between Se atoms of
structure of the structure of 2b contains C–H···Cl inter- neighboring stacks in structures of 1h, 2f, 2g, and 2m
molecular interactions, C–H···Se intermolecular interac- were also observed. These intermolecular interactions,
tions, and C–···N intermolecular interactions leading to close contacts, and π–π stacking interactions play a major
the formation of a disordered multistaged aggregate, but role in stabilizing the crossed-layer supramolecular as-
the π–π stacking interactions are absent. Interestingly, the semblies in the solid state.
supramolecular structure of 2n consists of a combination
of C–H···N intermolecular interactions, C–H···Cl inter-
molecular interactions and π–π stacking interactions to
Acknowledgment
We are grateful to the University of St Andrews for financial sup-
port and the EPSRC National Mass Spectrometry Service Centre
(Swansea) for mass spectral measurements.
build-up a multilayered supramolecular assembly, how-
ever, the C–H···Se intermolecular interaction being ab-
sent. On the other hand, in compounds 2e and 2g, there is
a combination of multi C–H···O intermolecular interac-
tions, multi C–H···N intermolecular interactions, the
multi C–H···X (X = Cl, Br) intermolecular interactions, at
C–H···Se intermolecular interactions, and π–π stacking
interactions present, in which involve the aryl ring H at-
oms, azole ring H atoms, OCH3 group H atoms, and the N,
O, X (Cl, Br) atoms. The similar supramolecular assembly
as 2e and 2g was observed in compound 2f apart from the
multi C–H···X (X = Cl, Br) intermolecular interactions
being absent. Surprisingly, the C–H···N intramolecular
interactions are dominated in compounds 2o and 2p in
conjunction with a combination of C–H···N intermolecu-
lar interactions, the multiple C–H···O intermolecular in-
teractions, the multiple C–H···Se intermolecular
interactions, and π–π stacking interactions, in which also
Supporting Information for this article is available online
http://www.thieme-connect.com/products/ejournals/journal/
10.1055/s-00000083.SunogIpimrfiantoSuIpg
n
fonirtat
ori
References and Notes
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