Synthesis and characterization of new aromatic aldehyde/ketone 4-(β-d-glucopyranosyl)thiosemicarbazones

Article abstract of DOI:10.1016/j.carres.2009.05.010

A series of 22 aromatic aldehyde/ketone 4-(β-d-glucopyranosyl)thiosemicarbazones have been synthesized by condensation of 4-(per-O-acetylated-β-d-glucopyranosyl)thiosemicarbazide with an aldehyde or a ketone, and then, deacetylation of the resulting produ

Full text of DOI:10.1016/j.carres.2009.05.010

Carbohydrate Research 344 (2009) 1352–1364
Contents lists available at ScienceDirect
Carbohydrate Research
journal homepage: www.elsevier.com/locate/carres
Note
Synthesis and characterization of new aromatic aldehyde/ketone
4-(b-D-glucopyranosyl)thiosemicarbazones
b
c
Alia-Cristina Tenchiu (Deleanu) a, Ioannis D. Kostas a, , Dimitra Kovala-Demertzi , Aris Terzis
*
a National Hellenic Research Foundation, Institute of Organic and Pharmaceutical Chemistry, Vas. Constantinou 48, 116 35 Athens, Greece
b University of Ioannina, Department of Chemistry, Sector of Inorganic and Analytical Chemistry, 451 10 Ioannina, Greece
c NCSR Democritos, Institute of Materials Science, 153 10 Aghia Paraskevi Attikis, Greece
a r t i c l e i n f o
a b s t r a c t
Article history:
A series of 22 aromatic aldehyde/ketone 4-(b-
sized by condensation of 4-(per-O-acetylated-b-D-glucopyranosyl)thiosemicarbazide with an aldehyde
D
-glucopyranosyl)thiosemicarbazones have been synthe-
Received 22 January 2009
Received in revised form 4 May 2009
Accepted 8 May 2009
or a ketone, and then, deacetylation of the resulting product. The compounds were fully characterized
by spectroscopic techniques, elemental analysis, and for two derivatives by X-ray analysis. The data indi-
cate the b configuration, and the E configuration pertaining to the stereochemistry of the C@N bond.
However, a partial conversion of the E-form into the Z-form is possible in solution after several hours.
Ó 2009 Elsevier Ltd. All rights reserved.
Available online 22 May 2009
Dedicated to the memory of our colleague
and distinguished scientist Dr. Nikos
G. Oikonomakos
Keywords:
Carbohydrates
Thiosemicarbazones
Glucopyranosyl-thiosemicarbazones
Configuration
Crystal structure
Glucose derivatives are known to be selective and efficient cata-
lytic inhibitors of human liver glycogen phosphorylase, a target for
the design of type 2 diabetes therapeutics.1 In addition, since carbo-
hydrates are readily available, highly functionalized, and have sev-
eral stereogenic centres, they have widely been used as ligands in
transition-metal catalyzed asymmetric reactions.2 On the other
hand, thiosemicarbazone is a class of biochemically important com-
pounds possessing a wide range of biological activities, and is very
promising in the treatment of many diseases.3 Since these molecules
can also serve as phosphane-free multidentate ligands for transi-
tion-metal catalysis, recently, we found that they are efficient li-
gands for palladium-catalyzed coupling reactions, in air.4 Taking
into consideration the broad range of applications of glucose as well
as of thiosemicarbazone derivatives, we were interested in synthes-
ising new compounds bearing both of these moieties as part of our
ongoing research into glycogen phosphorylase inhibitors and tansi-
tion metal catalysis. In the past, only some sporadic papers have
been published for the synthesis of aldehyde 4-(per-O-acetylated-
able.5 Very recently, the synthesis and the spectroscopic character-
ization of a number of per-O-acetylated analogues were reported,
together with their evaluation as antioxidant and anti-dyslipidemic
agents.6 The main synthetic step for the synthesis of these molecules
is being the reaction of a glucosyl thiosemicarbazide with a carbonyl
compound. Other glucosyl thiosemicarbazones in which the glucose
anomeric centre is directly attached to the carbon atom of the C@N
double bond of the thiosemicarbazone moiety have also been pub-
lished, the synthesis of which was achieved by Raney-nickel–NaH2-
PO2 reduction of glucosyl cyanide to the corresponding
semicarbazone in the presence of semicarbazide, and subsequent
acid catalyzed transimination with thiosemicarbazide.7 In the
present paper, we report a systematic study for the synthesis and
characterization of
4-(b- -glucopyranosyl)thiosemicarbazones.
The synthesis of the title molecules is outlined in Scheme 1.
a series of 22 aromatic aldehyde/ketone
D
Condensation of 4-(per-O-acetylated-b-D-glucopyranosyl)thiosemi-
carbazide 15a,c–f with a number of aldehydes and ketones, by a
b-
D-glucopyranosyl)thiosemicarbazones and their corresponding
known procedure,5e,6 afforded aldehyde/ketone 4-(per-O-acetyl-
deacetylated analogues, but in most of these papers, the products
were not fully characterized, and detailed spectral data are not avail-
ated-b-D-glucopyranosyl)thiosemicarbazones 2. The acetyl protec-
tive groups of 2 were removed by the Zemplén method8 in absolute
methanol in the presence of sodium methoxide, yielding the target
molecules 3. In the FT-IR spectra, the bands corresponding to N–H,
C@N and C@S stretching vibration are observed at 3310–3350,
* Corresponding author. Tel.: +30 210 7273878; fax: +30 210 7273831.
E-mail address: ikostas@eie.gr (I.D. Kostas).
0008-6215/$ - see front matter Ó 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.carres.2009.05.010

A.-C. Tenchiu (Deleanu) et al. / Carbohydrate Research 344 (2009) 1352–1364
1353
OAc
O
H
N
H
N
AcO
AcO
NH2
OAc
S
1
ArC(R)=O
EtOH or MeOH
cat. AcOH
reflux, 4_48h
50_94%
OAc
OH
NaOMe
MeOH
r.t.
O
O
R
R
H
N
H
N
H
N
H
N
AcO
AcO
HO
HO
_92%
N
Ar
N
Ar
33
OAc
OH
3a_v
S
S
2a_v
o:
Ar = -C6H4-tBu-p; R = H
a:
h:
R = H
R = H
Ar = -C6H4-Cl-o; R = H
Ar = -C6H4-OH-o;
p: Ar = 2-pyridyl;
q: Ar = 3-pyridyl;
b: Ar = -C6H4-Cl-m;
i: Ar = -C6H4-OH-m;
R = H
R = H
R = H
c:
d:
j:
k:
Ar = -C6H4-Cl-p;
Ar = -C6H4-CF3-p; R = H
Ar = -C6H4-OH-p; R = H
R = H
r:
R = H
Ar = -C6H4-OMe-o;
Ar = 4-pyridyl;
R = H
R = H
s: Ar = ferrocenyl;
t: Ar = β-naphthyl;
e: Ar = -C6H4-NO2-o;
R = H l: Ar = -C6H4-OMe-m;R = H
f:
g:
Ar = -C6H4-NO2-m;R = H
R = H
m: Ar = -C6H4-OMe-p; R = H
u:
Ar = -C6H4-OMe-p;R = Me
Ar = -C6H4-NO2-p; R = H n:
Ar = -C6H4-Me-p; R = H
v: Ar = β-naphthyl;
R = Me
Scheme 1. Synthesis of aldehyde/ketone 4-(b-D-glucopyranosyl)thiosemicarbazones.
1525–1553 and 1031–1049 cmꢀ1, respectively. A band at the region
810–851 cmꢀ1 is also contributed to
(C@S). The characteristic
It has previously been published that thiosemicarbazone deriv-
m
atives pertaining to the stereochemistry of the C@N bond, can exist
in the E- or Z-form or as a mixture of E/Z isomers, usually with the
E-form being the major isomer.10 Variation in isomeric ratios is
dependent on the substituents on the thiosemicarbazone moiety
and the solvent. The correct configuration can be determined by
1H NMR spectroscopy, as the N(2)H appears at 9–12 ppm for the
E-form, and 14–15 ppm for the Z-form.10c In the 1H NMR spectra
of freshly prepared solutions of 2 and 3 in CDCl3 or DMSO-d6, only
one signal was observed for each hydrogen, indicating the presence
of only one isomer (E), since the N(2)H resonance was assigned in
the range 8.81–12.03 ppm. However, a partial conversion of the E-
form into the Z-form is possible for some compounds in solution
after a while. In Figure 1, we present the 1H NMR spectra of 2p
in CDCl3 at different times. In a freshly prepared solution, only
the E isomer exists (spectrum (a)), but after 24 h, all signals are
duplicated which indicates that both E and Z isomers coexist in
solution, with the E-form being the major isomer (spectrum (b)).
In the Z-form, an intramolecular hydrogen bond should be formed
between N(2)H and the pyridine nitrogen.10b,e After 48 h, the equi-
librium leads to the two forms in a ratio of about 1:1 (spectrum
(c)). The most characteristic signals indicating the formation of
the two forms are those for N(2)H (10.14 ppm for E, 14.63 ppm
for Z), N(4)H (8.45 ppm for E, 8.33 ppm for Z), the azomethine
hydrogen CH@N (7.96 ppm for E, 7.15 ppm for Z) and the anomeric
proton 1-H (5.72 ppm for E, 5.86 ppm for Z). 13C NMR spectra could
also provide information for the geometry of the molecules.11 The
most significant resonance for the geometry determination is that
of the azomethine carbon CH@N, presented as only one signal at
143.5 ppm in a short time 13C NMR experiment (H-decoupling)
of a freshly prepared solution of 2p in CDCl3, indicating the pres-
ence of only one isomer. However, in an overnight 13C NMR exper-
iment (H-coupling), the signal is duplicated as an evidence that
both E and Z isomers coexist in solution. In addition to the
bands at 1725–1753 cmꢀ1 due to the C@O stretching vibration of
the acetyl groups in compounds 2, vanish in the IR spectra of 3,
and a broad absorption band of the hydroxyl group appears at
3203–3597 cmꢀ1. The NMR chemical shift range for some charac-
teristic protons (N(2)H, N(4)H, CH@N, anomeric 1-H) in compounds
2 and 3, and the hydroxy protons of the glucose moiety in com-
pounds 3, as well as some characteristic carbons (C@S, C@N, 1-C)
in compounds 2 and 3 and the acetyl C@O in compounds 2, is pre-
sented in Table 1. The atom numbering used for the NMR data is as
shown for 2p (Fig. 1). In the 1H NMR spectra of 2 and 3, the anomeric
proton 1-H is represented as a doublet of doublets at the range
5.61–5.87 and 5.35–5.44 ppm, respectively, due to the coupling
with the N(4)H and the 2-H. The coupling constant J1-H,2-H (9.0–
9.6 Hz) is an evidence which confirms the b configuration in com-
pounds 2 and 3.5d,9
Table 1
NMR chemical shift range (in ppm) for some characteristic proton and carbon atoms
in compounds 2 and 3
2
3
1H NMR
N(2)H
N(4)H
8.81–11.72 (s)
7.81–8.50 (d)
10.47–12.03 (s)
8.18–8.80 (d)
J1-H,N(4)H 8.7–9.3 Hz
J1-H,N(4)H 8.4–9.3 Hz
CH@N
7.69–8.57 (s)a
7.95–8.53 (s)a
1-H
5.61–5.87 (dd)
J1-H,2-H 9.0–9.3 Hz
5.35–5.44 (dd)
J1-H,2-H 9.0–9.6 Hz
Glucose OH
4.45–5.13 (br s, m, t)b
13C NMR
C@S
C@O
C@N
1-C
177.0–179.6
169.3–170.0
138.8–149.9
81.2–82.5
177.5–179.6
138.0–149.1
83.7–84.3
1
above-mentioned signal with JC,H value of 167.0 Hz, the azome-
thine carbon resonance of the other isomer appeared at
137.5 ppm (1JC,H 164.4 Hz). The resonance at lower field is assigned
to the E-form, and that at the higher field to the Z-form.11b
a
This signal is absent in compounds 2u,v and 3u,v.
b
An exception: the OH groups in compound 3s are represented by a broad singlet
at 3.90 ppm.

1354
A.-C. Tenchiu (Deleanu) et al. / Carbohydrate Research 344 (2009) 1352–1364
3'
4'
3' 4'
OAc
OAc
5'
6'
N
2'
6
5
6
5
4
4
5'
6'
N
O
O
H
1'
(2)
N
H
N
H
N
2
2
AcO
N
AcO
2'
(3)
(3)
H
N
AcO
AcO
(1)
1'
N
(2)
1
1
OAc
3
(4)
H
3
(4)
OAc
H
(1)
S
S
2p (E)
2p (Z)
Figure 1. Part of the 1H NMR spectra (600 MHz) for 2p (E/Z isomers) in CDCl3 at different times: (a) 5 min; (b) 24 h and (c) 48 h.
Colourless crystals of the acetylated derivative 2d and the
tively. The compound 2d exhibits E, Z configuration in relation to
the C(8)–N(3) and N(1)–C(10) bond, respectively, and compound
3j exhibits the same configuration in relation to the C(7)–N(1)
and N(2)–C(8) bond, respectively. In both molecules, the thiosem-
icarbazone moiety is almost planar, due to the C@N double bond.
Meanwhile, in 2d, atoms N(2) and N(3) are involved in an intramo-
lecular N(2)–HꢁꢁꢁN(3) interaction, and in 3j, atoms N(3) and N(1)
are involved in N(3)–HꢁꢁꢁN(1) interaction, which also contributes
to the planarity of the thiosemicarbazone group. The formation
of these hydrogen bonds was favoured by the Z configuration in
relation to the N(1)–C(10) and N(2)–C(8) bond in 2d and 3j, respec-
tively. In both compounds, the S–C and the azomethine C–N bond
distances exhibit increased double bond character. The N–N and
both thioamide C–N bond distances indicate a considerable double
bond character. This is indicative of the greater conjugation and
more delocalized electron density of the thiosemicarbazone
moiety.13
deacetylated product 3j suitable for X-ray determination were ob-
tained by slow crystallization from ethanol and methanol, respec-
tively. The molecular structures of 2d and 3j are given in Figure 2.
Selected interatomic distances, bond angles and torsion angles are
collected in Table 2. In compound 2d, the three F atoms are disor-
dered. The pyranosyl ring adopts a chair conformation, with the
values of the puckering parameters being Q = 0.590(3) Å,
h = 176.6(3)°, u = 138(4)° (2d), and Q = 0.586(2) Å, h = 9.1(2)°,
u = 42(7)° (3j). In 2d, the atoms C(11) and C(14) deviate on oppo-
site sides from the mean plane formed by the other atoms (C(12),
C(13), C(15) and O(1)) by 0.232(2) and –0.241(3) Å, respectively. In
a similar way in 3j, the atoms C(9) and C(12) deviate by 0.287(2)
and ꢀ0.184(1) Å, respectively, from the mean plane through the
other atoms (C(10), C(11), C(13) and O(2)). For both compounds,
the aglycone occupies an equatorial position (in 2d, the torsion an-
gle N(2)–C(11)–C(12)–C(13) is –172.8(2)°; in 3j, the torsion angle
N(3)–C(9)–C(10)–C(11) is ꢀ180.0(2)°), which is assumed to be
the most stable form, and thus indicating the b-configuration. As
in other b-pyranoses,12 the orientation of the primary alcohol
group in 3j is gauche, with the torsion angle O(2)–C(13)–C(14)–
O(6) being 61.7(2)°. The dihedral angle between the phenyl ring
and the pyranosyl ring is 65.5(2) and 67.6(2)° for 2d and 3j, respec-
The two molecules are stabilized by intra- and intermolecular
interactions. The packing diagrams of 2d and 3j are presented in
Figure 3, and the intra and inter-molecular contacts are collected
in Table 3. The monomers of 2d are linked by two intermolecular
bonds C(8)–H(C8)ꢁꢁꢁO(7) and C(12)–H(C12)ꢁꢁꢁS(1). The monomers
of 3j are connected by strong and weak intermolecular hydrogen

A.-C. Tenchiu (Deleanu) et al. / Carbohydrate Research 344 (2009) 1352–1364
1355
Figure 2. Labelled ORTEP diagram of 2d ((a), top) and 3j ((b), bottom) with 40% thermal probability ellipsoids.
bonding interactions O–HꢁꢁꢁO, N–HꢁꢁꢁO, O–HꢁꢁꢁS and C–HꢁꢁꢁO into a
the plates were visualized under UV light or by gentle heating after
spraying with an ethanolic solution (5% H2SO4). Melting points
were measured on a Nikon 50i Pol microscope equipped with a
Linkam THMS600 hot stage and a TMS94 temperature controller
or on a Büchi melting point apparatus, and were not corrected.
Optical rotations were measured on a Perkin–Elmer polarimeter
at room temperature. IR measurements were made using a Bruker
Tensor 27 instrument. NMR measurements were made using a Var-
ian 300 (300.13 MHz and 75.47 MHz for 1H and 13C, respectively)
or 600 (599.83 MHz and 150.84 MHz for 1H and 13C, respectively).
The assignment of protons and carbons in the 1H and 13C NMR
spectra was performed by COSY, NOESY, DEPT, GHSQC and GHMBC
experiments. Atom numbering used for the NMR spectra is as
shown for 2p in Figure 1. Elemental analyses for C, H and N were
carried out on a Perkin–Elmer PE 2400 II instrument. The acetyl-
ated derivatives 2a,5g,h 2c,5b,g,h 2g,5a,g,h 2e,5g,h 2h,5c 2i,5c 2j,5a,c,e
2k5g,h and the deacetylated analogues 3c,5b 3g,5a 3h,5c 3i5c and
3j5a,c have been published in the past, but in most cases, without
detailed spectral data. In a very recent paper, NMR data were given
for compounds 2c,g,m,q,r, and although the data are mainly in
accordance with those given below, there are some differences,
three-dimensional framework.
1. Experimental
1.1. General
4-(2,3,4,6-Tetra-O-acetyl-b-D-glucopyranosyl)thiosemicarbazide
(1) was synthesized in accordance with a known procedure by
treatment of (2,3,4,6-tetra-O-acetyl-b-D-glucopyranosyl)isothiocy-
anate with dry hydrazine in ethanol.5e The only modification in
this procedure was the reaction temperature, which was kept at
5–10 °C in order to avoid the formation of a carbohydrate bearing
diacylhydrazine framework.14 The above-mentioned isothiocya-
nate was prepared by the reaction of (per-O-acetylated-
pyranosyl)bromide (prepared from
-glucose pentaacetate)15 with
potassium thiocyanate in the melt.16
-Glucose pentaacetate, alde-
a-D-gluco-
D
D
hydes and ketones ArC(R)@O were commercially available. All
reactions were carried out under an argon atmosphere with puri-
fied and dry reagents and solvents. Column chromatography was
performed using silica gel and TLC on Kieselgel 60 F254 plates;

1356
A.-C. Tenchiu (Deleanu) et al. / Carbohydrate Research 344 (2009) 1352–1364
Table 2
Table 3
Selected geometric parameters in compounds 2d and 3j
Inter- and intramolecular contacts (Å, °) for 2d and 3j
2d
3j
Donor (D)
H
Acceptor (A)
DꢁꢁꢁAa
HꢁꢁꢁA
D–HꢁꢁꢁA
(a) Bond distances (Å)
2d
C(8)
O(1)–C(15)
O(1)–C(11)
N(2)–C(11)
N(2)–C(10)
S(1)–C(10)
N(1)–C(10)
N(1)–N(3)
N(3)–C(8)
F(1)–C(1)
1.422(3)
1.427(3)
1.435(3)
1.336(4)
1.668(3)
1.359(4)
1.374(4)
1.274(4)
1.278(6)
O(2)–C(13)
O(2)–C(9)
N(3)–C(9)
N(3)–C(8)
S–C(8)
N(2)–C(8)
N(1)–N(2)
N(1)–C(7)
O(1)–C(1)
1.425(2)
1.426(2)
1.432(2)
1.346(2)
1.704(2)
1.335(2)
1.389(2)
1.284(2)
1.350(2)
H(C8)
O(7)i
S(1)ii
O(3)
N(3)
S(1)
O(3)
O(5)
O(7)
3.207(4)
3.765(3)
3.018(3)
2.592(3)
3.127(3)
2.696(3)
2.683(4)
2.688(4)
2.53(3)
2.78(3)
2.55(3)
2.14(3)
2.69(2)
2.33(2)
2.30(2)
2.24(3)
124(2)
165(2)
114(2)
111(2)
108(2)
100(2)
105(2)
109(2)
C(12)
N(2)
N(2)
C(11)
C(12)
C(13)
C(14)
H(C12)
H(N2)
H(N2)
H(C11)
H(C12)
H(C13)
H(C14)
3j
(b) Bond angles (°)
C(11)–O(1)–C(15)
O(1)–C(11)–N(2)
N(2)–C(11)–C(12)
C(10)–N(2)–C(11)
S(1)–C(10)–N(2)
S(1)–C(10)–N(1)
N(1)–C(10)–N(2)
N(3)–N(1)–C(10)
N(1)–N(3)–C(8)
N(3)–C(8)–C(5)
O(1)
N(2)
O(3)
O(4)
O(5)
O(6)
C(6)
C(7)
C(9)
N(3)
O(4)
H(O1)
H(N2)
H(O3)
H(O4)
H(O5)
H(O6)
H(C6)
H(C7)
H(C9)
H(N3)
H(O4)
O(6)iii
O(5)iv
Sv
2.817(2)
3.038(2)
3.168(2)
2.730(2)
2.643(2)
3.260(2)
3.203(2)
3.354(2)
3.043(26)
2.615(2)
2.917(2)
2.08(3)
2.23(2)
2.32(2)
1.97(2)
1.87(2)
2.48(3)
2.36(2)
2.53(2)
2.68(2)
2.20(2)
2.55(2)
156(3)
161(3)
176(2)
160(2)
164(2)
174(2)
152(2)
146(2)
103(2)
114(2)
110(2)
113.0(2)
107.2(2)
109.8(2)
124.2(2)
125.8(2)
120.3(2)
114.0(3)
120.2(3)
117.2(3)
121.2(3)
C(9)–O(2)–C(13)
O(2)–C(9)–N(3)
N(3)–C(9)–C(10)
C(8)–N(3)–C(9)
S–C(8)–N(3)
112.0(2)
107.3(2)
113.0(2)
121.8(2)
106.6(2)
121.2(2)
116.2(2)
119.3(2)
114.1(2)
122.5(2)
O(3)vi
O(4)vi
Svii
S–C(8)–N(2)
O(2)iii
O(5)iv
S
N(2)–C(8)–N(3)
N(1)–N(2)–C(8)
N(2)–N(1)–C(7)
N(1)–C(7)–C(4)
N(1)
O(5)
a
(c) Torsion angles (°)
Symmetry codes: (i) 1 ꢀ x, 1/2 + y, ꢀ7/2 ꢀ z; (ii) 1 ꢀ x, ꢀ1/2 + y, ꢀ7/2 ꢀ z; (iii) 1/
2 + x, 1/2 ꢀ y, 2 ꢀ z ; (iv) 3/2 ꢀ x, 1 ꢀ y, 1/2 + z; (v) 2 ꢀ x, ꢀ1/2 + y, 3/2 ꢀ z; (vi) ꢀ1/
2 + x, 1/2 ꢀ y, 1 ꢀ z; (vii) ꢀ1 + x, y, z.
O(1)–C(15)–C(22)–O(8)
O(1)–C(15)–C(14)–C(13)
C(15)–C(14)–C(13)–C(12)
C(14)–C(13)–C(12)–C(11)
C(13)–C(12)–C(11)–O(1)
C(12)–C(11)–O(1)–C(15)
N(2)–C(11)–O(1)–C(15)
N(2)–C(11)–C(12)–C(13)
C(11)–N(2)–C(10)–S(1)
C(11)–N(2)–C(10)–N(1)
N(2)–C(10)–N(1)–N(3)
C(10)–N(1)–N(3)–C(8)
N(1)–N(3)–C(8)–C(5)
ꢀ74.5(3)
ꢀ65.2(3)
ꢀ56.0(3)
53.9(3)
O(2)–C(13)–C(14)–O(6)
O(2)–C(13)–C(12)–C(11)
C(13)–C(12)–C(11)–C(10)
C(12)–C(11)–C(10)–C(9)
C(11)–C(10)–C(9)–O(2)
C(10)–C(9)–O(2)–C(13)
N(3)–C(9)–O(2)–C(13)
N(3)–C(9)–C(10)–C(11)
C(9)–N(3)–C(8)–S
C(9)–N(3)–C(8)–N(2)
N(3)–C(8)–N(2)–N(1)
C(8)–N(2)–N(1)–C(7)
N(2)–N(1)–C(7)–C(4)
61.7(2)
ꢀ51.8(2)
48.9(2)
ꢀ52.8(2)
61.3(2)
ꢀ55.5(3)
63.0(3)
ꢀ69.1(2)
168.6(2)
ꢀ180.0(2)
ꢀ15.1(2)
165.8(2)
ꢀ5.2(2)
ꢀ178.1(2)
ꢀ172.8(2)
7.9(4)
1.2. General procedure for the synthesis of aldehyde/ketone
4-(per-O-acetylated-b-D-glucopyranosyl)thiosemicarbazones 2
ꢀ172.9(3)
ꢀ2.1(4)
174.2(3)
177.4(3)
ꢀ174.6(20)
176.7(20)
A solution of aldehyde or ketone (2.38 mmol) in ethanol (5 mL)
was added dropwise to a solution of 4-(2,3,4,6–tetra-O-acetyl-b-
D-
glucopyranosyl)thiosemicarbazide (1) (1 g, 2.38 mmol) in ethanol
(80 mL). For the synthesis of 2o, 2p, 2q and 2r, methanol was used
as solvent. After the addition of a catalytic amount of AcOH, the
reaction mixture was refluxed for 4–48 h. The solution was kept
in fridge overnight to form a precipitate; in some cases the solution
was concentrated to the half volume at temperature below 40 °C,
and then water was added to precipitate a solid. The precipitate
in particular the assignment of 1-H and 3-H of the sugar ring in the
1H NMR spectra.6 The authors assigned 3-H to the lower field res-
onance compared to that for 1-H,6 whereas now, based on COSY
NMR experiments, we conclude that these assignments should be
reversed.
Figure 3. Packing diagram of 2d ((a), left) and 3j ((b), right) along the c- and a-axis, respectively.

A.-C. Tenchiu (Deleanu) et al. / Carbohydrate Research 344 (2009) 1352–1364
1357
was filtered off, washed with cold ethanol and in some cases with
ether and recrystallized from methanol (or ethanol for the com-
pounds 2p, 2q and 2r).
2H, Harom), 7.67 (d, 3J 8.4 Hz, 2H, Harom), 5.67 (dd, 3J1-H,2-H 9.0 Hz, 1H,
3
1-H), 5.42 (t, J2-H,3-H 9.3 Hz, 1H, 3-H), 5.20–5.10 (m, 2H, 2-H, 4-H),
4.40 (dd, 3J5-H,6-H 4.5 Hz, 2J6-H,6 -H 12.6 Hz, 1H, 6-H), 4.15 (dd, 3J5-H,6 -H
0
0
3
2.1 Hz, 1H, 60-H), 3.90 (ddd, J4-H,5-H 10.2 Hz, 1H, 5-H), 2.09, 2.05,
1.2.1. 2-Chloro-benzaldehyde 4-(2,3,4,6-tetra-O-acetyl-b-
glucopyranosyl)thiosemicarbazone (2a)
D
-
2.04 and 2.03 (4 ꢃ s, 1H, CH3); 13C NMR (75.47 MHz, CDCl3): d
179.0 (C@S), 171.1, 170.7, 169.9 and 169.6 (C@O), 141.9 (CH@N),
136.3, 132.3, 131.9, 127.8, 125.8, 125.8 and 121.9 (Carom and CF3),
82.2 (1-C), 73.5 (3-C), 72.5 (2-C), 70.5 (5-C5), 68.3 (4-C), 61.6 (6-C),
20.7, 20.6 and 20.6 (CH3). Anal. Calcd for C23H26F3N3O9S (577.53):
C, 47.83; H, 4.54; N, 7.28. Found: C, 48.18; H, 4.37; N, 6.99.
Yield 66%; mp 172–175 °C; Rf (Hex/EtOAc 1:1) 0.43; ½a D25
ꢂ
ꢀ103.0
(c 1.07, CHCl3); IR (KBr): m 3350 (N–H), 2975 (C–Harom), 1745 (C@O),
1533 (C@N), 1039 (C@S), 920 (1-C–H), 822 (C@S) cmꢀ1
;
1H NMR
3
(300.13 MHz, CDCl3): d 9.76 (s, 1H, N(2)H), 8.29 (d, J1-H,N(4)H
8.7 Hz, 1H, N(4)H), 8.26 (s, 1H, CH@N), 8.09–8.06 (m, 1H, Harom),
7.37–7.30 (m, 3H, Harom), 5.72 (dd, 3J1-H,2-H 9.3 Hz, 1H, 1-H), 5.41 (t,
1.2.5. 2-Nitro-benzaldehyde 4-(2,3,4,6-tetra-O-acetyl-b-D-
3J2-H,3-H 9.6 Hz, 1H, 3-H), 5.19–5.09 (m, 2H, 2-H, 4-H), 4.37 (dd,
glucopyranosyl)thiosemicarbazone (2e)
Yield 92%; mp 136–140 °C; Rf (Hex/EtOAc 1:1) 0.46; ½a D25
ꢀ49.2 (c
ꢂ
J5-H,6-H 4.5 Hz, 2J6-H,6 -H 12.6 Hz, 1H, 6-H), 4.13 (dd, 3J5-H,6 -H 2.1 Hz,
3
0
0
3
1H, 60-H), 3.89 (ddd, J4-H,5-H 9.9 Hz, 1H, 5-H), 2.07, 2.04, 2.03 and
1, CHCl3); IR (KBr): m 3320 (N–H), 2946 (C–Harom), 1745 (C@O), 1525
(C@N), 1035 (C@S), 916 (1-C–H), 822 (C@S) cmꢀ1
;
1H NMR
2.02 (4 ꢃ s, 12H, CH3); 13C NMR (75.47 MHz, DMSO-d6): d 178.5
(C@S), 170.0, 169.5, 169.4 and 169.3 (C@O), 139.7 (CH@N), 133.4,
131.6, 131.1, 129.8, 127.6 and 127.3 (Carom), 81.5 (1-C), 72.7 (3-C),
72.2 (2-C), 70.9 (5-C) 67.8 (4-C), 61.7 (6-C), 20.5, 20.4, 20.3 and
20.3 (CH3). Anal. Calcd for C22H26ClN3O9SꢁH2O (561.99): C, 47.02;
H, 5.02; N, 7.48. Found: C, 47.54; H, 4.86; N, 7.03.
(300.13 MHz, CDCl3): d 9.69 (s, 1H, N(2)H), 8.43 (s, 1H, CH@N), 8.30
(d, 3J1-H,N(4)H 9.0 Hz, 1H, N(4)H), 8.21 (dd, J 1.5 Hz, J 7.8 Hz, 1H, Harom),
8.06 (dd, J 1.2 Hz, J 8.1 Hz, 1H, Harom), 7.75–7.69 (m, 1H, Harom), 7.61–
7.55 (m, 1H, Harom), 5.73 (dd, 3J1-H,2-H 9.3 Hz, 1H, 1-H), 5.42 (dd, 3J2-H,3-H
3
9.3 Hz, J3-H,4-H 9.6 Hz, 1H, 3-H), 5.18–5.09 (m, 2H, 2-H, 4-H), 4.38
3
2
3
0
0
(dd, J5-H,6-H 4.5 Hz, J6-H,6 -H 12.6 Hz, 1H, 6-H), 4.14 (dd, J5-H,6 -H
3
2.16 Hz, 1H, 60-H), 3.92 (ddd, J4-H,5-H 10.2 Hz, 1H, 5-H), 2.09, 2.05,
1.2.2. 3-Chloro-benzaldehyde 4-(2,3,4,6-tetra-O-acetyl-b-D-
2.04 and 2.03 (4 ꢃ s, 12H, CH3); 13C NMR (75.47 MHz, CDCl3): d
179.3 (C@S), 171.3, 170.7, 169.9 and 169.7 (C@O), 148.3 (C–NO2),
138.8 (CH@N), 133.8, 130.8, 128.6 and 125.0 (Carom), 82.3 (1-C),
73.6 (3-C), 72.6 (2-C), 70.7 (5-C), 68.3 (4-C), 61.6 (6-C), 20.8 and
20.6 (CH3). Anal. Calcd for C22H26N4O11Sꢁ2H2O (590.56): C, 44.74;
H, 5.12; N, 9.49. Found: C, 45.01; H, 5.48; N, 9.23.
glucopyranosyl)thiosemicarbazone (2b)
Yield 66%; mp 192–196 °C; Rf (Hex/EtOAc 1:1) 0.60; ½a D25
ꢂ ꢀ82.7 (c
1, CHCl3); IR (KBr): m 3324 (N–H), 2995 (C–Harom), 1749 (C@O), 1549
(C@N), 1043 (C@S), 908 (1-C–H), 830 (C@S) cmꢀ1
;
1H NMR
3
(300.13 MHz, CDCl3): d 9.64 (s, 1H, N(2)H), 8.35 (d, 1H, J1-H,N(4)H
8.7 Hz, 1H, N(4)H), 7.77 (s, 1H, Harom), 7.74 (s, 1H, CH@N), 7.58 (d,
3J 6.9 Hz, 1H, Harom), 7.42–7.33 (m, 2H, Harom), 5.67 (dd, J1-H,2-H
3
1.2.6. 3-Nitro-benzaldehyde 4-(2,3,4,6-tetra-O-acetyl-b-D-
3
9.3 Hz, 1H, 1-H), 5.42 (dd, J3-H,4-H 9.6 Hz, 1H, 3-H), 5.22–5.11 (m,
glucopyranosyl)thiosemicarbazone (2f)
3
2
0
Yield 79%; mp 191–195 °C; Rf (Hex/EtOAc 1:1) 0.36; ½a D25
ꢂ
ꢀ84.8
2H, 2-H, 4-H), 4.38 (dd, J5-H,6-H 4.5 Hz, J6-H,6 -H 12.6 Hz, 1H, 6-H),
3
3
4.15 (dd, J5-H,6 -H 2.1 Hz, 1H, 60-H), 3.92 (ddd, J4-H,5-H 9.9 Hz, 1H,
5-H), 2.09 and 2.04 (2 ꢃ s, 12H, CH3); 13C NMR (75.47 MHz, CDCl3):
d 179.1 (C@S), 171.2, 170.7, 169.9 and 169.6 (C@O), 141.7 (CH@N),
135.0, 134.7, 130.7, 130.2, 127.3 and 126.0 (Carom), 82.4 (1-C), 73.5
(3-C), 72.5 (2-C), 70.6 (5-C), 68.4 (4-C), 61.6 (6-C), 20.8, 20.7 and
20.6 (CH3). Anal. Calcd for C22H26ClN3O9S (543.97): C, 48.57; H,
4.82; N, 7.72. Found: C, 48.78; H, 5.11; N, 8.04.
0
(c 1, CHCl3); IR (KBr):
m 3328 (N–H), 2979 (C–Harom), 1737 (C@O),
1529 (C@N), 1035 (C@S), 920 (1-C–H), 820 (C@S) cmꢀ1 1H NMR
;
(300.13 MHz, CDCl3): d 10.07 (s, 1H, N(2)H), 8.57 (s, 1H, CH@N),
3
8.43 (d, J1-H,N(4)H 9.0 Hz, 1H, N(4)H), 8.28 (d, J 1.28 Hz, 1H, Harom),
8.08 (d, J 7.8 Hz, 1H, Harom), 7.91 (s, 1H, Harom), 7.63 (t, J 8.1 Hz, 1H,
3
3
Harom), 5.65 (dd, J1-H,2-H 9.3 Hz, 1H, 1-H), 5.43 (t, J2-H,3-H 9.3 Hz,
3
1H, 3-H), 5.21–5.11 (m, 2H, 2-H, 4-H), 4.39 (dd, J5-H,6-H 4.5 Hz,
2
3
J6-H,6 -H 12.6 Hz, 1H, 6-H), 4.12 (dd, J5-H,6 -H 12.6 Hz, 1H, 60-H),
0
0
3
1.2.3. 4-Chloro-benzaldehyde 4-(2,3,4,6-tetra-O-acetyl-b-D-
3.93 (ddd, J4-H,5-H 10.2 Hz,1H, 5-H), 2.09, 2.05, 2.04 and 2.03
(4 ꢃ s, 12H, CH3); 13C NMR (75.47 MHz, CDCl3): d 179.2 (C@S),
171.3, 170.7, 169.9 and 169.6 (C@O), 148.8 (C–NO2), 140.5 (CH@N),
134.8, 132.8, 130.0, 125.0 and 122.5 (Carom), 82.4 (1-C), 73.6 (3-C),
72.5 (2-C), 70.7 (5-C), 68.4 (4-C), 61.6 (6-C), 21.0 and 20.8 (CH3).
Anal. Calcd for C22H26N4O11Sꢁ3H2O (608.57): C, 43.42; H, 5.30; N,
9.21. Found: C, 43.72; H, 5.68; N, 8.89.
glucopyranosyl)thiosemicarbazone (2c)
Yield 53%; mp 214–217 °C, lit.5b mp 216–218 °C, lit.6 mp 198–
200 °C; Rf (Hex/EtOAc 1:1) 0.58; ½a D25
ꢂ
ꢀ78.0 (c 1, CHCl3), lit.5b
½ ꢂ
a 2D5
ꢀ89 (c 1, CHCl3); IR (KBr):
m 3316 (N–H), 2983 (C–Harom), 1745
(C@O), 1549 (C@N), 1039 (C@S), 912 (1-C–H), 835 (C@S) cmꢀ1 1H
;
NMR (300.13 MHz, CDCl3): d 9.40 (s, 1H, N(2)H), 8.30 (d, 3J1-H,N(4)H
8.7 Hz, 1H, N(4)H), 7.72 (s, 1H, CH@N), 7.65 (d, 3J 8.4 Hz, 2H, Harom),
7.40 (d, 3J 8.4 Hz, 2H, Harom), 5.69 (dd, 3J1-H,2-H 9.3 Hz, 1H, 1-H), 5.41
1.2.7. 4-Nitro-benzaldehyde 4-(2,3,4,6-tetra-O-acetyl-b-D-
3
glucopyranosyl)thiosemicarbazone (2g)
(t, J3-H,4-H 9.6 Hz, 1H, 3-H), 5.20–5.10 (m, 2H, 2-H, 4-H), 4.36 (dd,
Yield 64%; mp 218–220 °C, lit.5a mp 207 °C, lit.6 mp 201–203 °C;
3
J5-H,6-H 4.5 Hz, 2J6-H,6 -H 12.3 Hz, 1H, 6-H), 4.12 (dd, 3J5-H,6 -H 2.1 Hz;
1H, 60-H), 3.91 (ddd, 3J4-H,5-H 10.2 Hz, 1H, 5-H), 2.09, 2.05, 2.04 and
2.03 and (4 ꢃ s, 12H, CH3); 13C NMR (75.47 MHz, CDCl3): d 178.9
(C@S), 171.1, 170.7, 169.9 and 169.6 (C@O), 142.7 (CH@N), 137.0,
131.6 129.4 and 129.0 (Carom), 82.3 (1-C), 73.7 (3-C), 72.8 (2-C),
70.7 (5-C), 68.6 (4-C), 61.8 (6-C), 20.7, 20.6, 20.6 and 20.6 (CH3). Anal.
Calcd for C22H26ClN3O9Sꢁ4H2O (616.04): C, 42.89; H, 5.56; N, 6.82.
Found: C, 43.12; H, 5.99; N, 6.44.
0
0
Rf (Hex/EtOAc1:1) 0.42;½a D25
ꢂ
ꢀ110.0 (c 1, CHCl3), lit.5a
½ ꢂ ꢀ114(c 1,
a 2D5
CHCl3); IR (KBr):
m 3314 (N–H), 2975 (C–Harom), 1741 (C@O), 1525
(C@N), 1031 (C@S), 920 (1-C–H), 826 (C@S) cmꢀ1
(300.13 MHz, CDCl3): d 10.11 (s, 1H, N(2)H), 8.42 (d, J1-H,N(4)H
9.3 Hz, 1H, N(4)H), 8.28 (d, J 8.7 Hz, 2H, Harom), 7.91 (d, J 9.0 Hz, 2H,
;
1H NMR
3
3
Harom), 7.90 (s, 1H, CH@N), 5.65 (dd, J1-H,2-H 9.0 Hz, 1H, 1-H), 5.43
(dd, 3J2-H,3-H 9.3 Hz, 3J3-H,4-H 9.6 Hz,1H, 3-H), 5.20–5.11 (m, 2H, 2-H,
3
2
0
4-H), 4.38 (dd, J5-H,6-H 4.5 Hz, J6-H,6 -H 12.6 Hz, 1H, 6-H), 4.12 (dd,
3
3
J5-H,6 -H 1.8 Hz, 1H, 60-H), 3.92 (ddd, J4-H,5-H 10.2 Hz, 1H, 5-H),
0
1.2.4. 4-Trifluoromethyl-benzaldehyde 4-(2,3,4,6-tetra-O-
2.09, 2.06 and 2.04 (3 ꢃ s, 12H, CH3); 13C NMR (75.47 MHz, CDCl3):
d 179.2 (C@S), 171.3, 170.7, 169.9 and 169.6 (C@O), 148.8 (C–NO2),
140.4 (CH@N), 138.9, 128.2 and 124.2 (Carom), 82.4 (1-C), 73.6 (3-
C), 72.4 (2-C), 70.6 (5-C), 68.4 (4-C), 61.6 (6-C), 20.8, 20.7 and 20.6
(CH3). Anal. Calcd for C22H26N4O11S (554.53): C, 47.65; H, 4.73; N,
10.10. Found: C, 47.98; H, 5.12; N, 10.76.
acetyl-b-D-glucopyranosyl)thiosemicarbazone (2d)
Yield 73%; mp 223–225 °C; Rf (Hex/EtOAc 1:1) 0.42; ½a D25
ꢂ
ꢀ80.2 (c
1.17, CHCl3); IR (KBr):
m 3334 (N–H), 2938 (C–Harom), 1749 (C@O),
1529 (C@N), 1031 (C@S), 912 (1-C–H), 830 (C@S) cmꢀ1
(300.13 MHz, CDCl3):
3J1-H,N(4)H 8.7 Hz, 1H, N(4)H), 7.84 (s, 1H, CH@N), 7.83 (d, 3J 8.7 Hz,
;
1H NMR
d
10.14 (s, 1H, N(2)H), 8.38 (d,

1358
A.-C. Tenchiu (Deleanu) et al. / Carbohydrate Research 344 (2009) 1352–1364
1.2.8. 2-Hydroxy-benzaldehyde 4-(2,3,4,6-tetra-O-acetyl-b-
D
-
7.8 Hz, 1H, Harom), 7.39 (t, J 7.8 Hz, 1H, Harom), 7.02 (t, J 7.5 Hz,
3
glucopyranosyl)thiosemicarbazone (2h)
1H, Harom), 6.90 (d, J 8.4 Hz, 1H, Harom), 5.78 (dd, J1-H,2-H 9.3 Hz,
Yield 85%; mp 200 °C (decomp.), lit.5c mp 158–160 °C; Rf (Hex/
1H, 1-H), 5.40 (t, J2-H,3-H 9.3 Hz, 1H, 3-H), 5.20–5.09 (m, 2H, 2-H,
3
EtOAc 1:1) 0.37; ½a D25
ꢂ
ꢀ147.0 (c 1, CHCl3); IR (KBr):
m
3330 (N–H),
4-H), 4.38 (dd, J5-H,6-H 4.5 Hz, J6-H,6 -H 12.6 Hz, 1H, 6-H), 4.10
3
2
0
3
3
(dd, J5-H,6 -H 2.1 Hz, 1H, 60-H), 3.88 (ddd, J4-H,5-H 10.2 Hz, 1H,
5-H), 3.86 (s, 3H, OCH3); 2.09, 2.04, 2.03 and 2.02 (4 ꢃ s, 12 H,
CH3CO); 13C NMR (75.47 MHz, CDCl3): d 178.8 (C@S), 170.9,
170.7, 169.9 and 169.6 (C@O), 158.4 (C–OMe), 139.8 (CH@N),
132.2, 126.6, 121.2, 121.1 and 111.0 (Carom), 82.3 (1-C), 73.5
(3-C), 72.7 (2-C), 70.5 (5-C), 68.3 (4-C), 61.6 (6-C), 55.6 (OCH3),
20.8, 20.7 and 20.6 (CH3CO). Anal. Calcd for C23H29N3O10Sꢁ7H2O
(665.66): C, 41.50; H, 6.51; N, 6.31. Found: C, 41.89; H, 7.02; N,
6.44.
0
2948 (C–Harom), 1745 (C@O), 1533 (C@N), 1022 (C@S), 920 (1-C–H),
830 (C@S) cmꢀ1
;
1H NMR (300.13 MHz, CDCl3): d 9.81 (s, 1H,
3
N(2)H), 8.90 (s, 1H, CH@N); 7.99 (s, 1H, Harom), 7.81 (d, J1-H,N(4)H
8.7 Hz, 1H, N(4)H), 7.33 (t, J 7.8 Hz, 1H, Harom) 7.06 (d, J 8.1 Hz,
3
1H, Harom), 6.69 (t, J 7.2 Hz, 1H, Harom), 5.68 (dd, J1-H,2-H 9.3 Hz,
3
1H, 1-H), 5.42 (t, J3-H,4-H 9.6 Hz, 1H, 3-H), 5.15–5.09 (m, 2H, 2-H,
3
2
0
4-H), 4.33 (dd, J5-H,6-H 4.5 Hz, J6-H,6 -H 12.6 Hz, 1H, 6-H), 4.12
3
3
(dd, J5-H,6 -H 2.1 Hz, 1H, 60-H), 3.90 (ddd, J4-H,5-H 10.2 Hz, 1H,
5-H), 2.09, 2.08, 2.05 and 2.04 (4 ꢃ s, 12H, CH3); 13C NMR
(75.47 MHz, CDCl3): d 177.7 (C@S), 172.1, 170.7, 169.9 and 169.6
(C@O), 157.2 (C–OH), 148.3 (CH@N), 132.8, 132.0, 120.2, 117.4
and 116.6 (Carom), 82.5 (1-C), 73.4 (3-C), 72.3 (2-C), 71.0 (5-C),
68.2 (4-C), 61.5 (6-C), 20.7, 20.6 and 20.5 (CH3). Anal. Calcd for
C22H27N3O10Sꢁ5H2O (615.61): C, 42.92; H, 6.06; N, 6.83. Found: C,
42.88; H, 6.43; N, 7.12.
0
1.2.12. 3-Methoxy-benzaldehyde 4-(2,3,4,6-tetra-O-acetyl-b-D-
glucopyranosyl)thiosemicarbazone (2l)
Yield 78%; mp 175–179 °C; Rf (Hex/EtOAc 1:1) 0.47; ½a D25
ꢂ
ꢀ102.0 (c 1.07, CHCl3); IR (KBr):
m 3338 (N–H), 2995 (C–Harom),
1737 (C@O), 1545 (C@N), 1035 (C@S), 912 (1-C–H), 830 (C@S)
cmꢀ1
;
1H NMR (300.13 MHz, DMSO-d6): d 10.22 (s, 1H, N(2)H),
3
1.2.9. 3-Hydroxy-benzaldehyde 4-(2,3,4,6-tetra-O-acetyl-b-
D
-
8.30 (d, J1-H,N(4)H 8.7 Hz, 1H, N(4)H), 7.77 (s, 1H, CH@N), 7.36 (s,
1H, Harom), 7.28–7.21 (m, 1H, Harom), 7.11 (d, J 7.5 Hz, 1H, Harom),
6.92 (d, J 8.1 Hz, 1H, Harom), 5.61 (dd, J1-H,2-H 9.3 Hz, 1H, 1-H),
glucopyranosyl)thiosemicarbazone (2i)
Yield 50%; mp 201–204 °C, lit.5c mp 206–208 °C; Rf (Hex/EtOAc
3
1:1) 0.22; ½a 2D5
ꢂ
ꢀ115.3 (c 1.33, CHCl3); IR (KBr):
m
3320 (N–H), 2950
5.36 (t, J3-H,4-H 9.6 Hz, 1H, 3-H), 5.16–5.04 (m, 2H, 2-H, 4-H),
3
3
2
0
(C–Harom) 1745 (C@O), 1537 (C@N), 1035 (C@S), 920 (1-C–H), 826
(C@S) cmꢀ1; 1H NMR (300.13 MHz, DMSO-d6): d 9.87 (s, 1H, N(2)H),
8.23 (d, 3J1-H,N(4)H 8.7 Hz, 1H, N(4)H), 7.74 (s, 1H, CH@N), 7.29–7.24
(m, 2H, Harom), 7.07 (d, J 7.8 Hz, 1H, Harom), 6.92 (dd, J 1.5 Hz, J
8.1 Hz, 1H, Harom), 5.71 (dd, 3J1-H,2-H 9.3 Hz, 1H, 1-H), 5.41 (t, 3J3-H,4-H
4.31 (dd, J5-H,6-H 4.5 Hz, J6-H,6 -H 12.6 Hz, 1H, 6-H), 4.06 (dd,
3
3
J5-H,6 -H 2.1 Hz, 1H, 60-H), 3.88 (ddd, J4-H,5-H 10.2 Hz, 1H, 5-H),
0
3.84 (s, 3H, OCH3), 2.00, 1.99, 1.97 and 1.94 (4 ꢃ s, 12H, CH3CO);
13C NMR (75.47 MHz, DMSO-d6): d 178.4 (C@S), 170.0, 169.6,
169.5 and 169.3 (C@O), 159.6 (C–OMe), 143.5 (CH@N), 135.1,
129.8, 120.8, 116.5 and 111.5 (Carom), 81.4 (1-C), 72.6 (3-C), 72.1
(2-C), 70.7 (5-C), 67.9 (4-C), 61.7 (6-C), 20.6, 20.4, 20.4 and 20.3
(CH3CO). Anal. Calcd for C23H29N3O10Sꢁ5H2O (629.63): C, 43.87;
H, 6.24; N, 6.67. Found: C, 44.14; H, 6.66; N, 6.93.
3
9.6 Hz, 1H, 3-H), 5.24–5.11 (m, 2H, 2-H, 4-H), 4.37 (dd, J5-H,6-H
2
3
4.5 Hz, J6-H,6 -H 12.6 Hz, 1H, 6-H), 4.13 (dd, J5-H,6 -H 2.1 Hz, 1H, 60-
0
0
3
H), 3.92 (ddd, J4-H,5-H 10.2 Hz, 1H, 5-H), 2.08, 2.06, 2.05 and 2.04
(4 ꢃ s, 12Y, CH3); 13C NMR (75.47 MHz, DMSO-d6): d 178.3 (C@S),
172.1, 170.1, 169.5 and 169.4 (C@O), 157.7 (C–OH), 144.3 (CH@N),
135.0, 129.7, 118.8, 117.5 and 114.0 (Carom), 81.5 (1-C), 72.8 (3-C),
72.3 (2-C), 71.0 (5-C), 68.0 (4-C), 61.8 (6-C), 21.0, 20.6, 20.4 and 20.3
(CH3). Anal. Calcd for C22H27N3O10S (525.53): C, 50.28; H, 5.18; N,
8.00. Found: C, 49.72; H, 5.39; N, 8.02.
1.2.13. 4-Methoxy-benzaldehyde 4-(2,3,4,6-tetra-O-acetyl-b-D-
glucopyranosyl)thiosemicarbazone (2m)
Yield 88%; mp 213–216 °C, lit.6 mp 182–183 °C; Rf (Hex/EtOAc
1:1) 0.34; ½a 2D5
ꢂ
ꢀ83.0 (c 1, CHCl3); IR (KBr):
m 3312 (N–H), 2975
(C–Harom), 1749 (C@O), 1541 (C@N), 1035 (C@S), 920 (1-C–H),
1.2.10. 4-Hydroxy-benzaldehyde 4-(2,3,4,6-tetra-O-acetyl-b-
D
-
822 (C@S) cmꢀ1 1H NMR (300.13 MHz, CDCl3): d 9.78 (s, 1H,
;
3
glucopyranosyl)thiosemicarbazone (2j)
N(2)H), 8.26 (d, J1-H,N(4)H 8.7 Hz, 1H, N(4)H), 7.70 (s, 1H, CH@N),
7.65 (d, J 9.0 Hz, 2H, Harom), 6.95 (d, J 8.7 Hz, 2 H, Harom), 5.72
Yield 82%; mp 200–202 °C, lit.5a mp 210 °C, lit.5c mp 216–
217 °C; Rf (Hex/EtOAc 1:2) 0.46; ½a D25
ꢂ
ꢀ104.8 (c 1, CHCl3), lit.5a
(dd, J1-H,2-H 9.3 Hz, 1H, 1-H), 5.40 (dd, J3-H,4-H 9.6 Hz, 1H, 3-H),
3
3
a 2D5
ꢂ
ꢀ81 (c 0.8, CHCl3); IR (KBr):
m
3314 (N–H), 2960 (C–Harom),
5.21–5.10 (m, 2H, 2-H, 4-H), 4.38 (dd, J5-H,6-H 4.5 Hz, J6-H,6 -H
3
2
0
½
3
12.6 Hz, H, 6-H), 4.14 (dd, J5-H,6 -H 1.8 Hz, 1H, 60-H), 3.90 (ddd,
0
1741 (C@O), 1508 (C@N), 1039 (C@S), 920 (1-C–H), 835 (C@S)
cmꢀ1
;
1H NMR (300.13 MHz, CDCl3): d 9.84 (s, 1H, N(2)H), 8.20
3J4-H,5-H 10.2 Hz, 1H, 5-H), 3.84 (s, 3H, OCH3), 2.08, 2.04, 2.03 and
2.02 (4 ꢃ s, 12H, CH3CO); 13C NMR (75.47 MHz, CDCl3): d 178.3
(C@S), 170.9, 170.7, 169.9 and 169.5 (C@O), 161.8 (C–OMe),
143.9 (CH@N), 129.6, 125.5 and 114.4 (Carom), 82.2 (1-C), 73.5
(3-C), 72.7 (2-C), 70.5 (5-C), 68.3 (4-C), 61.6 (6-C), 20.7, 20.6 and
20.6 (CH3CO). Anal. Calcd for C23H29N3O10S (539.56): C, 51.20; H,
5.42; N, 7.79. Found: C, 50.94; H, 5.67; N, 8.02.
3
(d, J1-H,N(4)H 8.7 Hz, 1H, N(4)H), 7.69 (s, 1H, CH@N), 7.51 (d, J
8.7 Hz, 2H, Harom), 6.68 (d, J 8.7 Hz, 2H, Harom), 5.77 (br s, 1H,
OH), 5.74 (dd, J1-H,2-H 9.0 Hz, 1H, 1-H), 5.41 (t, J3-H,4-H 9.6 Hz,
3
3
3
1H, 3-H), 5.23–5.10 (m, 2H, 2-H, 4-H), 4.36 (dd, J5-H,6-H 4.5 Hz,
2
3
J6-H,6 -H 12.6 Hz, 1H, 6-H), 4.14 (dd, J5-H,6 -H 2.1 Hz, 1H, 60-H),
0
0
3
3.92 (ddd, J4-H,5-H 10.2 Hz, 1H, 5-H), 2.08, 2.05, 2.04 and 2.02
(4 ꢃ s, 12H, CH3); 13C NMR (75.47 MHz, DMSO-d6): d 177.8
(C@S), 170.2, 169.7, 169.7 and 169.5 (C@O), 159.8 (C–OH), 144.3
(CH@N), 129.6, 124.8 and 115.8 (Carom), 81.5 (1-C), 72.9 (3-C),
72.3 (2-C), 71.0 (5-C), 68.1 (4-C), 61.9 (6-C), 20.7, 20.6, 20.6 and
20.5 (CH3). Anal. Calcd for C22H27N3O10Sꢁ2H2O (561.56): C, 47.05;
H, 5.56; N, 7.48. Found: C, 47.46; H, 5.36; N, 7.67.
1.2.14. 4-Methyl-benzaldehyde 4-(2,3,4,6-tetra-O-acetyl-b-D-
glucopyranosyl)thiosemicarbazone (2n)
Yield 69%; mp 198–201 °C; Rf (Hex/EtOAc 1:1) 0.43; ½a D25
ꢀ77.6
ꢂ
(c 1.03, CHCl3); IR (KBr):
m 3314 (N–H), 2991 (C–Harom), 1741
(C@O), 1553 (C@N), 1043 (C@S), 933 (1-C–H), 830 (C@S) cmꢀ1
;
1H NMR (300.13 MHz, CDCl3): d 9.73 (s, 1H, N(2)H), 8.25 (d,
3J1-H,N(4)H 8.7 Hz, 1H, N(4)H), 7.77 (s, 1H, CH@N), 7.60 (d, J 8.1 Hz,
1.2.11. 2-Methoxy-benzaldehyde 4-(2,3,4,6-tetra-O-acetyl-b-D-
3
glucopyranosyl)thiosemicarbazone (2k)
2H, Harom), 7.25 (d, J 7.8 Hz, 2H, Harom), 5.72 (dd, J1-H,2-H 9.3 Hz,
1H, 1-H), 5.41 (t, J3-H,4-H 9.6 Hz, 1H, 3-H), 5.21–5.10 (m, 2H, 2-H,
Yield 81%; mp 208 °C (decomp.); Rf (Hex/EtOAc 1:1) 0.32; ½a D25
ꢂ
3
3
2
0
ꢀ83.7 (c 0.7, CHCl3); IR (KBr):
m
3328 (N–H), 2946 (C–Harom),
4-H), 4.34 (dd, J5-H,6-H 4.5 Hz, J6-H,6 -H 12.3 Hz, 1H, 6-H), 4.11
3
3
(dd, J5-H,6 -H 1.8 Hz, 1H, 60-H), 3.89 (ddd, J4-H,5-H 10.2 Hz, 1H,
5-H), 2.38 (s, 3H, CH3–Ar), 2.10, 2.08, 2.04 and 2.03 (4 ꢃ s, 12H,
CH3CO); 13C NMR (75.47 MHz, DMSO-d6): d 178.1 (C@S), 170.0,
0
1745 (C@O), 1529 (C@N), 1039 (C@S), 910 (1-C–H), 826 (C@S)
cmꢀ1
;
1H NMR (300.13 MHz, CDCl3): d = 9.43 (s, 1H, N(2)H), 8.25
3
(d, J1-H,N(4)H 8.7 Hz, 1H, N(4)H), 8.21 (s, 1H, CH@N), 7.97 (d, J

A.-C. Tenchiu (Deleanu) et al. / Carbohydrate Research 344 (2009) 1352–1364
1359
169.5, 169.5 and 169.4 (C@O), 143.9 (CH3–Ar), 140.2 (CH@N),
1.2.18. 4-Pyridinecarboxaldehyde 4-(2,3,4,6-tetra-O-acetyl-b-D-
131.0, 129.3 and 127.6 (Carom), 81.4 (1-C), 72.7 (3-C), 72.2 (2-C),
69.9 (5-C), 67.9 (4-C), 61.8 (6-C), 20.5, 20.4 20.4 and 20.4 (CH3CO).
Anal. Calcd for C23H29N3O9Sꢁ2H2O (559.59): C, 49.37; H, 5.94; N,
7.51. Found: C, 48.88; H, 6.24; N, 7.87.
glucopyranosyl)thiosemicarbazone (2r)
Yield 64%; mp 196–200 °C, lit.6 102–103 °C; Rf (Hex/EtOAc 1:2)
0.14; ½a 2D5
ꢂ
ꢀ93.0 (c1.07, CHCl3); IR (KBr):
m3329(N–H), 2962 (C–Harom),
1737 (C@O), 1525 (C@N), 1031 (C@S), 896 (1-C–H), 830 (C@S) cmꢀ1
;
1H NMR (300.13 MHz, CDCl3): d 10.56 (s, 1H, N(2)H), 8.69 (d, J 5.4 Hz,
2H, Harom), 8.39 (d, 3J1-H,N(4)H 8.7 Hz, 1H, N(4)H), 7.81 (s, 1H, CH@N),
7.62 (d, J 5.4 Hz, 2H, Harom), 5.64. (dd, 3J1-H,2-H 9.0 Hz, 1H, 1-H), 5.41 (t,
3J3-H,4-H 9.6 Hz, 1H, 3-H), 5.19–5.09 (m, 2H, 2-H, 4-H) 4.35 (dd, 3J5-H,6-H
1.2.15. 4-tert-Butyl-benzaldehyde 4-(2,3,4,6-tetra-O-acetyl-b-D-
glucopyranosyl)thiosemicarbazone (2o)
Yield 77%; mp 210–213 °C; Rf (Hex/EtOAc 1:1) 0.64; ½a D25
ꢂ
4.5 Hz, 2J6-H,6 -H 12.6 Hz, 1H, 6-H), 4.10 (dd, 3J5-H,6 -H 2.1 Hz, 1H, 60-H),
3.90 (ddd, 3J4-H,5-H 10.2 Hz, 1H, 5-H), 2.09, 2.08, 2.04 and 2.03 (4 ꢃ s,
12H, CH3); 13C NMR (75.47 MHz, CDCl3): d 179.4 (C@S), 171.3, 170.7,
169.9 and 169.6 (C@O), 150.0 (Carom), 140.7 (CH@N), 140.5 and 121.4
(Carom), 82.2 (1-C), 73.5 (3-C), 72.5 (2-C), 70.6 (5-C), 68.3 (4-C), 61.6
(6-C), 20.8, 20.7, 20.7 and 20.6 (CH3). Anal. Calcd for
C21H26N4O9Sꢁ3H2O (564.56): C, 44.68; H, 5.71; N, 9.92. Found: C,
45.09; H, 5.83; N, 10.14.
0
0
ꢀ77.7 (c 1.27, CHCl3). IR (KBr):
m 3326 (N–H), 2958 (C–Harom)
1749 (C@O), 1533 (C@N), 1047 (C@S), 916 (1-C–H), 826 (C@S)
cmꢀ1
;
1H NMR (300.13 MHz, CDCl3): d 10.26 (s, 1 H, N(2)H),
3
8.29 (d, J1-H,N(4)H 8.7 Hz, 1H, N(4)H), 7.85 (s, 1H, CH@N), 7.65
(d, J 8.1 Hz, 2H, Harom), 7.44 (d, J 8.4 Hz, 2H, Harom), 5.71 (dd,
3J1-H,2-H 9.0 Hz, 1H, 1-H), 5.40 (dd, J3-H,4-H 9.6 Hz, 1H, 3-H),
3
3
2
0
5.21–5.09 (m, 2H, 2-H, 4-H), 4.37 (dd, J5-H,6-H 4.5 Hz, J6-H,6 -H
3
12.6 Hz, 1H, 6-H), 4.12 (dd, J5-H,6 -H 2.1 Hz, 1H, 60-H), 3.92
0
3
(ddd, J4-H,5-H 10.2 Hz, 1H, 5-H), 2.07, 2.04, 2.03 and 2.01 (4 ꢃ s,
1.2.19. 1-Ferrocenecarboxaldehyde 4-(2,3,4,6-tetra-O-acetyl-b-
12H, CH3CO), 1.32 (s, 9H, CH3(tBu)); 13C NMR (75.47 MHz,
CDCl3): d 178.7 (C@S), 170.9, 170.7, 169.9 and 169.6 (C@O),
154.4 (Carom–tBu), 143.9 (CH@N), 130.1, 127.5 and 125.9 (Carom),
82.2 (1-C), 73.4 (3-C), 72.7 (2-C), 70.4 (5-C), 68.3 (4-C), 61.6 (6-
C), 34.9 (CMe3), 31.1 (CH3(tBu)), 20.8, 20.6 and 20.6 (CH3CO).
Anal. Calcd for C26H35N3O9S (565.64): C, 55.21; H, 6.24; N,
7.43. Found: C, 55.35; H, 6.66; N, 7.84.
D-glucopyranosyl)thiosemicarbazone (2s)
Yield 90%; mp 212–215 °C; Rf (Hex/EtOAc 1:1) 0.5; IR (KBr):
m
3322 (N–H), 3073 (C–Harom), 1725 (C@O), 1525 (C@N), 1035 (C@S),
912 (1-C–H), 820 (C@S) cmꢀ1 1H NMR (300.13 MHz, DMSO-d6): d
;
3
11.72 (s, 1H, N(2)H), 8.38 (d, J1-H,N(4)H 9.0 Hz, 1H, N(4)H), 7.93 (s,
3
3
1H, CH@N), 5.87 (dd, J1-H,2-H 9.3 Hz, 1H, 1-H), 5.42 (t, J3-H,4-H
9.6 Hz, 1H, 3-H), 5.26 (t, J 9.3 Hz, 1H, 2-H), 4.96 (dd, 3J3-H,4-H 9.6 Hz,
3J4-H,5-H 9.9 Hz, 1H, 4-H), 4.84 (s, 1H, Fc), 4.73 (s, 1H, Fc), 4.49–4.45
1.2.16. 2-Pyridinecarboxaldehyde 4-(2,3,4,6-tetra-O-acetyl-b-D-
(m, 2H, Fc), 4.22 (s, 5H, Fc), 4.20 (dd, 3J5-H,6 -H 4.2 Hz, 1H, 60-H), 4.06
0
glucopyranosyl)thiosemicarbazone (2p)
(ddd, 3J5-H,6-H 1.8 Hz, 1H, 5-H), 3.97 (dd, 2J6-H,6 -H 12.3 Hz, 1H, 6-H),
0
Yield 67%; mp 70–73 °C; Rf (Hex/EtOAc 1:3) 0.17; ½a D25
ꢂ
ꢀ66.9 (c
2.01, 2.00, 1.97 and 1.96 (4 ꢃ s, 12H, CH3); 13C NMR (75.47 MHz,
DMSO-d6): d 177.0 (C@S), 170.0, 169.6, 169.5 and 169.3 (C@O),
145.0 (CH@N), 81.2 (1-C), 78.3 (C(Fc)–CH@N), 72.5 (3-C), 72.1 (2-
C), 70.7 (5-C), 70.3 (Fc), 69.0 (Fc), 68.1 (4-C), 67.9, 67.6 and 64.4
(Fc), 61.7 (6-C), 20.6, 20.4, 20.4 and 20.3 (CH3). Anal. Calcd for
C26H31FeN3O9S (617.45): C, 50.58; H, 5.06; N, 6.81. Found: C,
50.78; H, 4.65; N, 7.03.
1.23, CHCl3); IR (KBr):
m 3328 (N–H), 2967 (C–Harom), 1741 (C@O),
1529 (C@N), 1035 (C@S), 888 (1-C–H), 839 (C@S) cmꢀ1
;
1H NMR
(599.83 MHz, CDCl3): d 10.14 (s, 1H, N(2)H), 8.60 (d, J 4.2 Hz, 1H,
3
30-H), 8.45 (d, J1-H,N(4)H 8.7 Hz, 1H, N(4)H), 8.04 (d, J 7.8 Hz, 1H,
60-H), 7.96 (s, 1H, CH@N), 7.79–7.74 (m, 1H, 50-H), 7.33–7.28 (m,
3
3
1H, 40-H), 5.72 (dd, J1-H,2-H 9.0 Hz, 1H, 1-H), 5.41 (t, J3-H,4-H
3
9.6 Hz, 1H, 3-H), 5.21–5.10 (m, 2H, 2-H, 4-H), 4.37 (dd, J5-H,6-H
2
3
0
0
4.5 Hz, J6-H,6 -H 12.6 Hz, 1H, 6-H), 4.12 (dd, J5-H,6 -H 1.8 Hz, 1H,
1.2.20. b-Naphthalenecarboxaldehyde 4-(2,3,4,6-tetra-O-acetyl-
3
60-H), 3.90 (ddd, J4-H,5-H 10.2 Hz, 1H, 5-H), 2.11, 2.08, 2.04 and
b-D-glucopyranosyl)thiosemicarbazone (2t)
2.03 (4 ꢃ s, 12H, CH3); 13C NMR (150.84 MHz, CDCl3): d 179.4
(C@S), 171.1, 170.7, 169.9 and 169.6 (C@O), 152.2 and 149.5
(Carom), 143.5 (CH@N), 136.9, 124.6 and 121.1 (Carom), 82.2 (1-C),
73.5 (3-C), 72.7 (2-C), 70.6 (5-C), 68.3 (4-C), 61.6 (6-C), 20.8,
20.7, 20.6 and 20.6 (CH3). Anal. Calcd for C21H26N4O9S (510.52):
C, 49.41; H, 5.13; N, 10.97. Found: C, 49.82; H, 5.45; N, 11.12.
Yield 94%; mp 212–215 °C; Rf (Hex/EtOAc 1:1) 0.4; ½a D25
ꢂ ꢀ116.7 (c
1.05, CHCl3); IR (KBr):
m 3322 (N–H), 2950 (C–Harom) 1753 (C@O),
1533 (C@N), 1035 (C@S), 904 (1-C–H), 830 (C@S) cmꢀ1 1H NMR
;
3
(300.13 MHz, CDCl3): d 10.41 (s, 1H, N(2)H), 8.38 (d, J1-H,N(4)H
8.7 Hz, 1H, N(4)H), 7.98 (d, J 5.4 Hz, 3H, Hnaphth), 7.83 (d, J 9.3 Hz,
2H, Hnaphth), 7.82 (s, 1H, CH@N), 7.49–7.52 (m, 2H, Hnaphth), 5.72
3
3
(dd, J1-H,2-H 9.3 Hz, 1H, 1-H), 5.41 (t, J2-H,3-H 9.3 Hz, 1H, 3-H),
3
2
1.2.17. 3-Pyridinecarboxaldehyde 4-(2,3,4,6-tetra-O-acetyl-b-D-
0
5.25–5.10 (m, 2H, 2-H, 4-H), 4.37 (dd, J5-H,6-H 4.5 Hz, J6-H,6 -H
3
12.6 Hz, 1H, 6-H), 4.12 (dd, J5-H,6 -H 1.8 Hz, 1H, 60-H), 3.91 (ddd,
glucopyranosyl)thiosemicarbazone (2q)
0
Yield 80%; mp 129–131 °C, lit.6 mp 134–136 °C; Rf (Hex/EtOAc
3J4-H,5-H 10.2 Hz, 1H, 5-H), 2.08, 2.06 and 2.04 and 2.03 (4 ꢃ s, 12H,
CH3); 13C NMR (75.47 MHz, CDCl3): d 178.9 (C@S), 171.0, 170.8,
170.0 and 169.7 (C@O), 144.3 (CH@N), 134.5, 133.0, 130.7, 129.9,
128.8, 128.4, 127.9, 127.4, 126.7 and 122.8 (Cnaphth), 82.2 (1-C),
73.4 (3-C), 72.7 (2-C), 70.5 (5-C), 68.4 (4-C), 61.7 (6-C), 20.7, 20.7,
20.6 and 20.6 (CH3). Anal. Calcd for C26H29N3O9Sꢁ2H2O (595.62): C,
52.43; H, 5.58; N, 7.05. Found: C, 52.12; H, 5.97; N, 6.65.
1:3) 0.16; ½a 2D5
ꢂ
ꢀ82.2 (c 1, CHCl3); IR (KBr):
m 3320 (N–H), 2950
(C–Harom), 1745 (C@O), 1533 (C@N), 1031 (C@S), 928 (1-C–H),
826 (C@S) cmꢀ1 1H NMR (300.13 MHz, CDCl3): d 10.49 (s, 1H,
;
N(2)H), 8.81 (d, J 1.8 Hz, 1H, Harom), 8.64 (dd, J 1.5 Hz, J 4.8 Hz,
3
1H, Harom), 8.34 (d, J1-H,N(4)H 9.0 Hz, 1H, N(4)H), 8.16 (dt,
J 1.8 Hz, J 7.8 Hz, 1H, Harom), 7.89 (s, 1H, CH@N), 7.37 (dd, J
3
1.8 Hz, J 7.8 Hz, 1H, Harom), 5.68 (dd, J1-H,2-H 9.3 Hz, 1H, 1-H),
3
5.41 (t, J3-H,4-H 9.6 Hz, 1H, 3-H), 5.18–5.09 (m, 2H, 2-H, 4-H),
1.2.21. 4-Methoxy-acetophenone 4-(2,3,4,6-tetra-O-acetyl-b-D-
3
2
0
4.37 (dd, J5-H,6-H 4.5 Hz, J6-H,6 -H 12.6 Hz, 1H, 6-H), 4.14 (dd,
glucopyranosyl)thiosemicarbazone (2u)
3
3
J5-H,6 -H 1.8 Hz, 1H, 60-H), 3.90 (ddd, J4-H,5-H 10.2 Hz, 1H, 5-H),
Yield 78%; mp 192–198 °C; Rf (Hex/EtOAc 1:2) 0.64; ½a D25
ꢂ
ꢀ48.1
0
2.09, 2.07, 2.04 and 2.02 (4 ꢃ s, 12H, CH3); 13C NMR
(75.47 MHz, CDCl3): d 179.1 (C@S), 171.1, 170,7, 169.9 and
169.6 (C@O), 151.3 and 149.5 (Carom), 140.3 (CH@N), 133.7,
129.2 and 124.0 (Carom), 82.2 (1-C), 73.5 (3-C), 72.5 (2-C), 70.6
(5-C), 68.3 (4-C), 61.6 (6-C), 20.7, 20.7 and 20.6 (CH3). Anal. Calcd
for C21H26N4O9S (510.52): C, 49.41; H, 5.13; N, 10.97. Found: C,
49.86; H, 4.98; N, 11.15.
(c 1.05, CHCl3); IR (KBr):
m 3330 (N–H), 2950 (C–Harom), 1741
(C@O), 1529 (C@N), 1035 (C@S), 916 (1-C–H), 830 (C@S) cmꢀ1
;
1H NMR (300.13 MHz, CDCl3): d 8.81 (s, 1H, N(2)H), 8.38 (d,
3J1-H,N(4)H 9.0 Hz, 1H, N(4)H), 7.78 (d, J 9.0 Hz, 2H, Harom), 6.95 (d,
3
J 9.0 Hz, 2H, Harom), 5.76 (dd, J1-H,2-H 9.3 Hz, 1H, 1-H), 5.40 (t,
3J3-H,4-H 9.6 Hz, 1H, 3-H), 5.21–5.09 (m, 2Y, 2-H, 4-H), 4.36 (dd,
3
2
3
0
0
J5-H,6-H 4.5 Hz, J6-H,6 -H 12.6 Hz, 1H, 6-H), 4.14 (dd, J5-H,6 -H

1360
A.-C. Tenchiu (Deleanu) et al. / Carbohydrate Research 344 (2009) 1352–1364
3
2.1 Hz, 1H, 60-H), 3.90 (ddd, J4-H,5-H @ 10.2 Hz, 1H, 5-H), 3.85 (s,
3H, OCH3), 2.23 (s, 3H, CH3C@N), 2.08, 2.04 and 2.02 (3 ꢃ s, 12H,
CH3CO); 13C NMR (75.47 MHz, DMSO-d6): d 179.1 (C@S), 170.1,
169.9, 169.7 and 169.5 (C@O), 160.7 (Carom–O), 149.9 (C@N),
130.6, 129.8, 128.6, 113.6 and 113.5 (Carom), 81.4 (1-C), 72.6
(3-C), 72.3 (2-C), 71.0 (5-C), 68.2 (4-C), 61.9 (6-C), 55.3 (OCH3),
20.7, 20.7, 20.6 and 20.5 (CH3CO), 14.5 (CH3C@N). Anal. Calcd for
C24H31N3O10Sꢁ3H2O (607.63): C, 47.44; H, 6.14; N, 6.92. Found: C,
47.12; H, 5.98; N, 6.55.
3359 (OH), 2926 (C–Harom), 1537 (C@N), 1035 (C@S), 892 (1-C–
H), 830 (C@S) cmꢀ1
;
1H NMR (300.13 MHz, DMSO-d6): d 11.82
3
(s, 1H, N(2)H), 8.75 (d, J1-H,N(4)H 8.7 Hz, 1H, N(4)H), 8.08 (s, 2H,
CH@N and Harom), 7.71 (s, 1H, Harom), 7.46 (s, 2H, Harom), 5.40
3
(dd, J1-H,2-H 9.0 Hz, 1H, 1-H), 5.02 (s, 2H, OH), 4.90 (s, 1H, OH),
3
2
0
4.49 (s, 1H, OH), 3.65 (dd, J5-H,6-H 3.9 Hz, J6-H,6 -H 11.4 Hz, 1H,
6-H), 3.56–3.15 (m, 5H, 2-H, 3-H, 4-H, 5-H, 60-H); 13C NMR
(75.47 MHz, DMSO-d6): d 178.8 (C@S), 141.4 (CH@N), 136.2,
133.7, 130.5, 129.6, 126.8 and 126.3 (Carom), 84.1 (1-C), 78.7 (3-
C), 77.6 (2-C), 71.8 (5-C), 69.9 (4-C), 60.9 (6-C). Anal. Calcd for
C14H18ClN3O5Sꢁ5H2O (465.90): C, 36.09; H, 6.06; N, 9.02. Found:
C, 35.78; H, 5.89; N, 8.95.
1.2.22. 2-Acetonaphthanone 4-(2,3,4,6-tetra-O-acetyl-b-D-
glucopyranosyl)thiosemicarbazone (2v)
Yield 72%; mp 182–185 °C; Rf (Hex/EtOAc 1:2) 0.42; ½a D25
ꢀ61.5
ꢂ
(c 1.07, CHCl3); IR (KBr): m 3310 (N–H), 2950 (C–Harom), 1741 (C@O),
1.3.3. 4-Chloro-benzaldehyde 4-(b-D-glucopyranosyl)thiosemi-
1529 (C@N), 1035 (C@S), 916 (1-C–H), 835 (C@S) cmꢀ1
;
1H NMR
carbazone (3c)
(300.13 MHz, CDCl3, 25 °C):
d 9.18 (s, 1H, N(2)H), 8.50 (d,
Yield 53%; mp 169–171 °C (decomp., MeOH/H2O 1:1), lit.5b mp
3J1-H,N(4)H 8.7 Hz, 1H, N(4)H), 8.17 (s, 1H, Hnaphth), 8.05 (dd, J
1.8 Hz, J 8.7 Hz, 1H, Hnaphth), 7.93–7.83 (m, 3H, Hnaphth), 7.53–7.50
(m, 2H, Hnaphth), 5.76 (dd, 3J1-H,2-H 9.0 Hz, 1H, 1-H), 5.43 (t, 3J2-H,3-H
166–169 °C; Rf (CHCl3/MeOH 5:1) 0.51; ½a D25
ꢂ
+55.5 (c 1, MeOH),
lit.5b
½
a 2D5
ꢂ
+34.7 (DMF/H2O); IR (KBr):
m
3371 (OH), 2885 (C–Harom),
1537 (C@N), 1031 (C@S), 900 (1-C–H), 830 (C@S) cmꢀ1
;
1H NMR
3
9.6 Hz, 1H, 3-H), 5.26–5.11 (m, 2H, 2-H, 4-H), 4.34 (dd, J5-H,6-H
3
(300.13 MHz, DMSO-d6): d 11.78 (s, 1H, N(2)H), 8.62 (d, J1-H,N(4)H
9.0 Hz, 1H, N(4)H), 8.09 (s, 1H, CH@N), 7.90 (d, J 8.4 Hz, 2H, Harom),
2
3
4.5 Hz, J6-H,6 -H 12.6 Hz, 1H, 6-H), 4.12 (dd, J5-H,6 -H 2.1 Hz, 1H, 60-
0
0
3
H), 3.92 (ddd, J4-H,5-H 10.2 Hz, 1H, 5-H), 2.38 (s, 3H, CH3C@N),
3
7.48 (d, J 8.4 Hz, 2H, Harom), 5.38 (dd, J1-H,2-H 9.3 Hz, 1H, 1-H),
2.08, 2.06 and 2.05 (3 ꢃ s, 12H, CH3CO); 13C NMR (75.47 MHz,
CDCl3): d 179.6 (C@S), 171.0, 170.8, 169.9 and 169.6 (C@O), 148.0
(C@N), 134.1, 134.0, 133.0, 128.7, 128.3, 127.6, 127.2, 126.9, 126.5
and 123.4 (Cnaphth), 82.3 (1-C), 73.5 (3-C), 72.7 (2-C), 70.5 (5-C),
68.4 (4-C), 61.6 (6-C), 20.7, 20.7 and 20.6 (CH3CO), 13.2 (CH3C@N).
Anal. Calcd for C27H31N3O9Sꢁ3H2O (627.66): C, 51.67; H, 5.94; N,
6.69. Found: C, 52.01; H, 6.23; N, 6.67.
5.01–4.99 (m, 2H, OH), 4.90–4.88 (m, 1H, OH), 4.50–4.46 (m,
3
2
0
1H, OH), 3.65 (dd, J5-H,6-H 5.4 Hz, J6-H,6 -H 11.4 Hz, 1H, 6-H),
3.50–3.14 (m, 5H, 2-H, 3-H, 4-H, 5-H, 60-H); 13C NMR
(75.47 MHz, DMSO-d6): d 178.5 (C@S), 142.6 (CH@N), 135.0,
132.7, 129.3 and 129.0 (Carom), 83.9 (1-C), 78.4 (3-C), 77.2 (2-C),
71.8 (5-C), 69.7 (4-C), 60.8 (6-C). Anal. Calcd for C14H18ClN3O5S
(375.83): C, 44.74; H, 4.83; N, 11.18. Found: C, 44.34; H, 5.12;
N, 11.67.
1.3. General procedure for the deacetylation in compounds 2.
Synthesis of aldehyde/ketone 4-(b-D-glucopyranosyl)thiosemi-
carbazones 3
1.3.4. 4-Trifluoromethyl-benzaldehyde 4-(b-D-glucopyranosyl)-
thiosemicarbazone (3d)
Yield 76%; mp 160–165 °C (decomp., MeOH/H2O 1:1); Rf
Sodium methoxide as a powder (7.5 mmol) was added to a solu-
tion of 2 (1.5 mmol) in dry methanol (20 mL). The reaction mixture
was stirred at room temperature for 3 h and kept in fridge over-
night. Then, the solution was neutralized with Amberlist-15 (or
acetic acid for the compounds 2c, 2p, 2q and 2r), it was filtered
to remove sodium ions, and the solvent was evaporated by vacuum
at a temperature below 40 °C. Purification was carried out by
recrystallization. The N–H stretching vibration in the FT-IR spectra
of 3 has not been determined as it was obscured by the broad
absorption band of the hydroxyl group.
(CHCl3/MeOH 5:1) 0.44; ½a D25
ꢂ
+48.3 (c 1, MeOH); IR (KBr): m 3322
(OH), 2893 (C–Harom), 1541 (C@N), 1035 (C@S), 900 (1-C–H), 826
(C@S) cmꢀ1
;
1H NMR (300.13 MHz, DMSO-d6): d 11.92 (s, 1H,
N(2)H), 8.73 (d, J1-H,N(4)H 9.0 Hz, 1H, N(4)H), 8.16 (s, 1H, CH@N),
8.09 (d, J 8.1 Hz, 2H, Harom), 7.76 (d, J 8.1 Hz, 2H, Harom), 5.40 (dd,
3J1-H,2-H 9.0 Hz, 1H, 1-H), 5.08 (br s, 2H, OH), 4.96 (br s, 1H, OH),
4.52 (br s, 1H, OH), 3.66 (dd, J5-H,6-H 5.4 Hz, J6-H,6 -H 11.4 Hz, 1H,
6-H), 3.51–3.17 (m, 5H, 2-H, 3-H, 4-H, 5-H, 60-H); 13C NMR
(75.47 MHz, DMSO-d6): d 178.9 (C@S), 141.1 (CH@N), 138.0,
129.7, 129.3, 128.1, 125.5, 125.4 and 125.4 (Carom and CF3), 84.1
(1-C), 78.7 (3-C), 77.6 (2-C), 71.9 (5-C), 69.8 (4-C), 60.8 (6-C). Anal.
Calcd for C15H18F3N3O5Sꢁ2H2O (445.41): C, 40.45; H, 4.98; N, 9.43.
Found: C, 40.22; H, 4.73; N, 9.83.
3
3
2
0
1.3.1. 2-Chloro-benzaldehyde 4-(b-D-glucopyranosyl)thiosemi-
carbazone (3a)
Yield 50%; mp 204–208 °C (decomp., MeOH/H2O 1:1); Rf (CHCl3/
MeOH 5:1) 0.40; ½a D25
ꢂ
+41.4 (c 1, MeOH); IR (KBr): m 3525 (OH),
2873 (C–Harom), 1537 (C@N), 1039 (C@S), 916 (1-C–H), 830 (C@S)
1.3.5. 2-Nitro-benzaldehyde 4-(b-D-glucopyranosyl)thiosemi-
carbazone (3e)
cmꢀ1
;
1H NMR (300.13 MHz, DMSO-d6): d 11.93 (s, 1H, N(2)H),
3
Yield 55%; mp 194–198 °C (decomp., MeOH/H2O 1:1); Rf
8.66 (d, J1-H,N(4)H 9.0 Hz, 1H, N(4)H), 8.53 (s, 1H, CH@N), 8.36 (d,
(CHCl3/MeOH 5:1) 0.51; ½a D25
ꢂ
+42.5 (c 1.06, MeOH); IR (KBr): m
3355 (OH), 2918 (C–Harom), 1537 (C@N), 1035 (C@S), 896 (1-C–H),
3
J 7.5 Hz, 1H, Harom), 7.52–7.36 (m, 3H, Harom), 5.39 (dd, J1-H,2-H
9.0 Hz, 1H, 1-H), 5.03–5.00 (m, 2H, OH), 4.91 (s, H, OH), 4.50 (t, 3J
3
2
0
822 (C@S) cmꢀ1
1H, N(2)H), 8.68 (d, J1-H,N(4)H 9.0 Hz, 1H, N(4)H), 8.53 (s, 1H,
CH@N), 8.47 (dd, J 1.5 Hz, J 8.1 Hz, 1H, Harom), 7.79–7.74 (m, 1H,
;
1H NMR (300.13 MHz, DMSO-d6): d 12.03 (s,
5.6 Hz, 1H, OH), 3.66 (dd, J5-H,6-H 5.4 Hz, J6-H,6 -H 11.4 Hz, 1H, 6-
H), 3.55–3.14 (m, 5H, 2-H, 3-H, 4-H, 5-H, 60-H); 13C NMR
(75.47 MHz, DMSO-d6): d 178.8 (C@S), 138.9 (CH@N), 133.2,
131.4, 131.2, 129.8, 127.7 and 127.3 (Carom), 84.1 (1-C), 78.7 (3-
C), 77.6 (2-C), 71.9 (5-C), 69.8 (4-C), 60.8 (6-C). Anal. Calcd for
C14H18ClN3O5Sꢁ4H2O (447.89): C, 37.54; H, 5.85; N, 9.38. Found:
C, 37.68; H, 5.46; N, 9.03.
3
3
Harom), 7.68–7.62 (m, 1H, Harom), 5.39 (dd, J1-H,2-H 9.3 Hz, 1H,
1-H), 5.02–5.00 (m, 2H, OH), 4.90–4.88 (m, 1H, OH), 4.49 (t, 3J
3
2
0
5.8 Hz, 1H, OH), 3.65 (dd, J5-H,6-H 5.4 Hz, J6-H,6 -H 11.7 Hz, 1H, 6-
H), 3.53–3.15 (m, 5H, 2-H, 3-H, 4-H, 5-H, 60-H); 13C NMR
(75.47 MHz, DMSO-d6): d 179.0 (C@S), 148.3 (C–NO2), 138.0
(CH@N), 133.3, 130.5, 128.5, 128.2 and 124.5 (Carom), 84.1 (1-C),
78.7 (3-C), 77.5 (2-C), 71.9 (5-C), 69.8 (4-C), 60.8 (6-C). Anal. Calcd
for C14H18N4O7Sꢁ4H2O (458.44): C, 36.68; H, 5.72; N, 12.22. Found:
C, 36.42; H, 6.01; N, 11.95.
1.3.2. 3-Chloro-benzaldehyde 4-(b-D-glucopyranosyl)thiosemi-
carbazone (3b)
Yield 71%; mp 190–193 °C (decomp., MeOH/H2O 1:1); Rf
(CHCl3/MeOH 5:1) 0.45; ½a D25
ꢂ
+54.8 (c 1.33, MeOH); IR (KBr): m

A.-C. Tenchiu (Deleanu) et al. / Carbohydrate Research 344 (2009) 1352–1364
1361
1.3.6. 3-Nitro-benzaldehyde 4-(b-
D
-glucopyranosyl)thiosemi-
1.3.10. 4-Hydroxy-benzaldehyde 4-(b-D-glucopyranosyl)thio-
carbazone (3f)
semicarbazone (3j)
Yield 70%; mp 201–205 °C (decomp., MeOH/H2O 1:1); Rf (CHCl3/
Yield 76%; mp 228–230 °C (decomp., MeOH), lit.5a mp 218 °C,
MeOH 5:1) 0.52; ½a D25
ꢂ
+54.0 (c 0.75, MeOH/DMF 3:1); IR (KBr):
m
lit.5c mp 224–225 °C; Rf (CHCl3/MeOH 5:1) 0.12; ½a 2D5
ꢂ
+65.3 (c 1,
3250 (OH),
3416 (OH), 2987 (C–Harom), 1545 (C@N), 1035 (C@S), 910 (1-C–H),
MeOH), lit.5a
½
a 2D5
ꢂ
+37 (c 0.9, DMF/H2O); IR (KBr):
m
810 (C@S) cmꢀ1
;
1H NMR (300.13 MHz, DMSO-d6): d 11.91 (br s,
2909 (C–Harom), 1521 (C@N), 1018 (C@S), 909 (1-C–H), 839 (C@S)
1H, N(2)H), 8.80 (d, 3J1-H,N(4)H 8.7 Hz, 1H, N(4)H), 8.62 (s, 1H, Harom),
8.34 (d, J 7.5 Hz, 1H, Harom), 8.25–8.21 (m, 2H, Harom and CH@N),
7.72 (dd, J 7.5 Hz, J 8.1 Hz, 1H, Harom), 5.40 (dd, 3J1-H,2-H 9.3 Hz, 1H,
1-H), 5.05 (s, 2H, OH), 4.95 (s, 1H, OH), 4.53 (s, 1H, OH), 3.68 (dd,
cmꢀ1
;
1H NMR (300.13 MHz, DMSO-d6): d 11.56 (s, 1H, N(2)H),
3
9.92 (br s, 1H, OH), 8.38 (d, J1-H,N(4)H 9.0 Hz, 1H, N(4)H), 8.00 (s,
1H, CH@N), 7.62 (d, J 9.0 Hz, 2H, Harom), 6.78 (d, J 9.0 Hz, 2 H,
3
Harom), 5.35 (dd, J1-H,2-H 9.6 Hz, 1H, 1-H), 5.00 (s, 2H, OH), 4.88
3
2
3
2
0
0
J5-H,6-H 5.4 Hz, J6-H,6 -H 11.7 Hz, 1H, 6-H), 3.53–3.15 (m, 5H, 2-H,
(s, 1H, OH), 4.45 (s, 1H, OH), 3.64 (dd, J5-H,6-H 5.7 Hz, J6-H,6 -H
11.4 Hz, 1H, 6-H), 3.49–3.10 (m, 5H, 2-H, 3-H, 4-H, 5-H, 60-H);
13C NMR (75.47 MHz, DMSO-d6): d 178.0 (C@S), 160.3 (C–OH),
143.6 (CH@N), 129.3, 124.3 and 115.8 (Carom), 83.9 (1-C), 79.2 (3-
C), 78.6 (2-C), 72.0 (5-C), 69.8 (4-C), 60.8 (6-C). Anal. Calcd for
C14H19N3O6S (357.38): C, 47.05; H, 5.36; N, 11.76. Found: C,
46.98; H, 5.64; N, 11.55.
3-H, 4-H, 5-H, 60-H); 13C NMR (75.47 MHz, DMSO-d6): d 179.0
(C@S), 148.4 (C–NO2), 141.0 (CH@N), 136.0, 133.7, 130.3, 124.3
and 121.9 (Carom), 84.3 (1-C), 78.8 (3-C), 77.7 (2-C), 71.9 (5-C),
69.9 (4-C), 60.9 (6-C). Anal. Calcd for C14H18N4O7Sꢁ5H2O (476.46):
C, 35.29; H, 5.92; N, 11.76. Found: C, 34.96; H, 5.34; N, 12.06.
1.3.7. 4-Nitro-benzaldehyde 4-(b-D-glucopyranosyl)thiosemi-
1.3.11. 2-Methoxy-benzaldehyde 4-(b-D-glucopyranosyl)thio-
semicarbazone (3k)
carbazone (3g)
Yield 39%; mp 213–215 °C (decomp., DMF/MeOH 1:2), lit.5a mp
Yield 63%; mp172–175 °C (decomp., MeOH/H2O 1:1); Rf (CHCl3/
202 °C; Rf (CHCl3/MeOH 5:1) 0.34; ½a D25
ꢂ
+61.3 (c 0.75, MeOH/DMF
+31 (c 0.9, DMF/H2O); IR (KBr): m 3405 (OH), 2873
MeOH 5:1) 0.42; ½a D25
ꢂ
+37.8 (c 1, MeOH); IR (KBr): m 3559 (OH),
2897 (C–Harom), 1537 (C@N), 1026 (C@S), 892 (1-C–H), 830 (C@S)
3:1), lit.5a
½
a 2D5
ꢂ
(C–Harom), 1537 (C@N), 1035 (C@S), 892 (1-C–H), 822 (C@S)
cmꢀ1
;
1H NMR (300.13 MHz, DMSO-d6): d 11.73 (s, 1H, N(2)H),
cmꢀ1
;
1H NMR (300.13 MHz, DMSO-d6): d 11.97 (s, 1H, N(2)H),
3
8.51 (d, J1-H,N(4)H 9.0 Hz, 1H, N(4)H), 8.47 (s, 1H, CH@N), 8.14
(dd, J 1.8 Hz, J 7.8 Hz, 1H, Harom), 7.43–7.37 (m, 1H, Harom), 7.08–
3
8.79 (d, J1-H,N(4)H 9.0 Hz, 1H, N(4)H), 8.26–8.14 (m, 5H, Harom and
3
CH@N), 5.40 (dd, J1-H,2-H 9.0 Hz, 1H, 1-H), 5.03–5.01 (m, 2H, OH),
3
6.95 (m, 2H, Harom), 5.37 (dd, J1-H,2-H 9.0 Hz, 1H, 1-H), 5.02–4.99
4.91–4.90 (m, 1H, OH), 4.50 (t, 3J 5.7 Hz, 1H, OH), 3.65 (dd, J5-H,6-H
3
(m, 2H, OH), 4.89–4.88 (m, 1H, OH), 4.47 (t, 3J 5.8 Hz, 1H, OH),
2
0
5.4 Hz, J6-H,6 -H 11.7 Hz, 1H, 6-H), 3.54–3.15 (m, 5H, 2-H, 3-H,
3
2
0
3.84 (s, 3H, OCH3), 3.66 (dd, J5-H,6-H 5.7 Hz, J6-H,6 -H 11.4 Hz, 1H,
6-H), 3.51–3.43 (m, 2H) and 3.25–3.13 (m, 3H) (2-H, 3-H, 4-H, 5-
H, 60-H); 13C NMR (75.47 MHz, DMSO-d6): d 178.4 (C@S), 157.9
(C–OMe), 138.6 (CH@N), 131.6, 126.3, 121.9, 120.5 and 111.7 (Car-
om), 83.9 (1-C), 78.6 (3-C), 77.6 (2-C), 72.0 (5-C), 69.8 (4-C), 60.8 (6-
C), 55.7 (OCH3). Anal. Calcd for C15H21N3O6Sꢁ3H2O (425.45): C,
42.35; H, 6.40; N, 9.88. Found: C, 41.97; H, 6.67; N, 10.03.
4-H, 5-H, 60-H); 13C NMR (75.47 MHz, DMSO-d6): d 179.0 (C@S),
147.7 (C–NO2), 140.4 and 140.3 (CH@N and Carom), 128.5 and
123.8 (Carom), 84.1 (1-C), 78.7 (3-C), 77.6 (2-C), 71.9 (5-C), 69.9
(4-C), 60.8 (6-C). Anal. Calcd for C14H18N4O7Sꢁ4H2O (458.44): C,
36.68; H, 5.72; N, 12.22. Found: C, 36.98; H, 5.58; N, 12.84.
1.3.8. 2-Hydroxy-benzaldehyde 4-(b-D-glucopyranosyl)thiosemi-
carbazone (3h)
1.3.12. 3-Methoxy-benzaldehyde 4-(b-D-glucopyranosyl)thio-
semicarbazone (3l)
Yield 92%; very hygroscopic, lit.5c mp 180–182 °C; Rf (CHCl3/
MeOH 5:1) 0.22; ½a D25
ꢂ
+43.0 (c 1, MeOH); IR (KBr): m 3203 (OH),
Yield 77%; mp 184–187 °C (decomp., MeOH/H2O 1:1); Rf
2864 (C–Harom), 1553 (C@N), 1035 (C@S), 910 (1-C–H), 843 (C@S)
(CHCl3/MeOH 5:1) 0.41; ½a D25
ꢂ
+50.7 (c 1.14, MeOH); IR (KBr): m
3498 (OH), 2905 (C–Harom), 1557 (C@N), 1031 (C@S), 896 (1-C–
cmꢀ1
;
1H NMR (300.13 MHz, DMSO-d6): d 11.99 (s, 1H, N(2)H),
3
8.47 (d, J1-H,N(4)H 8.7 Hz, 1H, N(4)H), 8.43 (s, 1H, CH@N), 7.99 (d, J
H), 851 (C@S) cmꢀ1
;
1H NMR (300.13 MHz, DMSO-d6): d 11.76 (s,
7.5 Hz, 1H, Harom), 7.26–7.21 (m, 1H, Harom), 6.88–6.80 (m, 2H,
Harom), 5.37 (dd, J1-H,2-H 9.3 Hz, 1H, 1-H), 5.02–5.01 (m, 2H, OH),
3
1H, N(2)H), 8.59 (d, J1-H,N(4)H 9.0 Hz, 1H, N(4)H), 8.08 (s, 1H,
CH@N), 7.43–7.34 (m, 3H, Harom), 6.99 (d, J 7.5 Hz, 1H, Harom),
3
3
4.91–4.90 (m, 1H, OH), 4.51–4.47 (m, 1H, OH), 3.64 (dd, J5-H,6-H
3
5.37 (dd, J1-H,2-H 9.0 Hz, 1H, 1-H), 5.02 (br s, 2H, OH), 4.91 (br s,
5.4 Hz, 2J6-H,6 -H 11.7 Hz, 1H, 6-H), 3.48–3.12 (m, 5H, 2-H, 3-H, 4-H,
0
1H, OH), 4.47 (br s, 1H, OH), 3.81 (s, 3H, OCH3), 3.66 (d, J 11.4 Hz,
1H, 6-H), 3.53–3.14 (m, 5H, 2-H, 3-H, 4-H, 5-H, 60-H); 13C NMR
(75.47 MHz, DMSO-d6): d 178.6 (C@S), 159.6 (C–OMe), 143.0
(CH@N), 135.3, 129.8, 120.4, 115.9 and 112.2 (Carom), 84.0 (1-C),
78.6 (3-C), 77.6 (2-C), 71.9 (5-C), 69.8 (4-C), 60.8 (6-C), 55.3
(OCH3). Anal. Calcd for C15H21N3O6Sꢁ4H2O (443.47): C, 40.63; H,
6.59; N, 9.48. Found: C, 40.17; H, 7.01; N, 9.12.
5-H, 60-H); 13C NMR (75.47 MHz, DMSO-d6): d 178.3 (C@S), 156.6
(C–OH), 140.0 (CH@N), 131.4, 126.7, 120.3, 119.2 and 116.1 (Carom),
83.9 (1-C), 78.6 (3-C), 77.6 (2-C), 72.0 (5-C), 69.8 (4-C), 60.8 (6-C).
1.3.9. 3-Hydroxy-benzaldehyde 4-(b-D-glucopyranosyl)thio-
semicarbazone (3i)
Yield 74%; mp 188–194 °C (MeOH/H2O 1:1), lit.5c 170–172 °C; Rf
(CHCl3/MeOH 5:1) 0.30; ½a D25
ꢂ
+58.7 (c 1, MeOH); IR (KBr): m 3208
1.3.13. 4-Methoxy-benzaldehyde 4-(b-D-glucopyranosyl)thio-
semicarbazone (3m)
(OH), 2950 (C–Harom), 1553 (C@N), 1031 (C@S), 892 (1-C–H), 832
(C@S) cmꢀ1
;
1H NMR (300.13 MHz, DMSO-d6): d 11.69 (s, 1H,
Yield 68%; mp 187–190 °C (decomp., MeOH); Rf (CHCl3/MeOH
3
5:1) 0.33; ½a 2D5
ꢂ
+68.5 (c 1, MeOH); IR (KBr): m 3547 (OH), 2893
(C–Harom), 1549 (C@N), 1031 (C@S), 888 (1-C–H), 839 (C@S)
N(2)H), 9.61 (s, 1H, OH), 8.44 (d, J1-H,N(4)H 9.3 Hz, 1H, N(4)H),
8.02 (s, 1H, CH@N), 7.22–7.21 (m, 3H, Harom), 6.84–6.81 (m, 1H,
3
cmꢀ1
;
1H NMR (300.13 MHz, DMSO-d6): d 11.63 (s, 1H, N(2)H),
Harom), 5.37 (dd, J1-H,2-H 9.0 Hz, 1H, 1-H), 5.06–5.02 (m, 2H, OH),
4.92–4.91 (m, 1H, OH), 4.51 (t, 3J 5.7 Hz, 1H, OH), 3.64 (dd,
3
8.46 (d, J1-H,N(4)H 9.0 Hz, 1H, N(4)H), 8.06 (s, 1H, CH@N), 7.78 (d,
3
2
3
0
J5-H,6-H 5.7 Hz, J6-H,6 -H 11.4 Hz, 1H, 6-H), 3.48–3.14 (m, 5H, 2-H,
J 7.8 Hz, 2H, Harom), 6.98 (d, J 7.8 Hz, 2H, Harom), 5.37 (dd, J1-H,2-H
3-H, 4-H, 5-H, 60-H); 13C NMR (75.47 MHz, DMSO-d6): d 178.7
(C@S), 157.8 (C–OH), 144.3 (CH@N), 135.5, 130.4, 119.6, 118.0
and 113.8 (Carom), 84.2 (1-C), 78.8 (3-C), 77.6 (2-C), 72.3 (5-C),
70.1 (4-C), 61.1 (6-C). Anal. Calcd for C14H19N3O6Sꢁ2H2O (393.41):
C, 42.74; H, 5.89;N, 10.68. Found: C, 42.74; H, 5.89; N, 10.98.
9.3 Hz, 1H, 1-H), 5.01–4.99 (m, 2H, OH), 4.89–4.88 (m, 1H, OH),
3
4.47 (t, 3J 5.8 Hz, 1H, OH), 3.80 (s, 3H, OCH3), 3.63 (dd, J5-H,6-H
2
0
5.7 Hz, J6-H,6 -H 11.4 Hz, 1H, 6-H), 3.50–3.44 (m, 2H) and 3.26–
3.12 (m, 3H) (2-H, 3-H, 4-H, 5-H, 60-H); 13C NMR (75.47 MHz,
DMSO-d6): d 178.2 (C@S), 160.8 (C–OMe), 143.0 (CH@N), 129.2,

1362
A.-C. Tenchiu (Deleanu) et al. / Carbohydrate Research 344 (2009) 1352–1364
3
2
4.53 (t, 3J 5.6 Hz, 1H, OH), 3.65 (dd, J5-H,6-H 5.7 Hz, J6-H,6 -H
11.4 Hz, 1H, 6-H), 3.56–3.45 (m, 2H) and 3.27–3.14 (m, 3H) (2-H,
3-H, 4-H, 5-H, 60-H); 13C NMR (75.47 MHz, DMSO-d6): d 178.8
(C@S), 150.5 and 149.0 (Carom), 140.1 (CH@N), 134.2, 129.9 and
123.7 (Carom), 84.1 (1-C), 78.7 (3-C), 77.6 (2-C), 71.9 (5-C), 69.9
(4-C), 60.9 (6-C). Anal. Calcd for C13H18N4O5Sꢁ2H2O (378.40): C,
41.26; H, 5.86; N, 14.81. Found: C, 41.84; H, 5.53; N, 14.74.
0
126.4 and 114.2 (Carom), 84.0 (1-C), 78.6 (3-C), 77.6 (2-C), 72.0 (5-
C), 69.8 (4-C), 60.8 (6-C), 55.3 (OCH3). Anal. Calcd for
C15H21N3O6Sꢁ5H2O (461.49): C, 39.04; H, 6.77; N, 9.11. Found: C,
38.79; H, 6.34; N, 8.95.
1.3.14. 4-Methyl-benzaldehyde 4-(b-D-glucopyranosyl)thio-
semicarbazone (3n)
Yield 60%; mp 182–185 °C (decomp., MeOH/H2O 1:1); Rf
(CHCl3/MeOH 5:1) 0.40; ½a D25
ꢂ
+63.1 (c 1, MeOH); IR (KBr):
(OH), 2979 (C–Harom), 1553 (C@N), 1035 (C@S), 904 (1-C–H), 830
m
3322
1.3.18. 4-Pyridinecarboxaldehyde 4-(b-D-glucopyranosyl)thio-
semicarbazone (3r)
(C@S) cmꢀ1
;
1H NMR (300.13 MHz, DMSO-d6): d 11.67 (s, 1H,
Yield 33%; mp 201–205 °C (decomp., DMF/MeOH 3:1); Rf
N(2)H), 8.48 (d, J1-H,N(4)H 9.3 Hz, 1H, N(4)H), 8.06(s, 1H, CH@N),
7.72 (d, J 8.1 Hz, 2H, Harom), 7.23 (d, J 7.8 Hz, 2H, Harom), 5.37 (dd,
3J1-H,2-H 9.6 Hz, 1H, 1-H), 5.00–4.99 (m, 2H, OH), 4.88–4.87 (m,
(CHCl3/MeOH 5:1) 0.23; ½a D25
ꢂ
+49.6 (c 0.8, MeOH/DMF 3:1); IR
3
(KBr):
m 3597 (OH), 2848 (C–Harom), 1541 (C@N), 1035 (C@S),
896 (1-C–H), 830 (C@S) cmꢀ1
;
1H NMR (300.13 MHz, DMSO-d6):
1H, OH), 4.46 (t, 3J 5.7 Hz, 1H, OH), 3.63 (dd, J5-H,6-H 5.7 Hz,
d 11.99 (s, 1H, N(2)H), 8.75 (d, J1-H,N(4)H 8.7 Hz, 1H, N(4)H), 8.61
(dd, J 5.7 Hz, 2H, Harom), 8.07 (s, 1H, CH@N), 7.84 (d, J 5.7 Hz, 2H,
3
3
2
0
J6-H,6 -H 11.4 Hz, 1H, 6-H), 3.50–3.43 (m, 2H) and 3.23–3.12 (m,
3H) (2-H, 3-H, 4-H, 5-H, 60-H), 2.32 (s, 3H, CH3); 13C NMR
(75.47 MHz, DMSO-d6): d 178.4 (C@S), 143.1 (CH@N), 139.9,
131.2, 129.3 and 127.5 (Carom), 83.9 ((1-C), 78.6 (3-C), 77.6 (2-C),
72.0 (5-C), 69.8 (4-C), 60.8 (6-C). Anal. Calcd for C15H21N3O5Sꢁ2H2O
(391.44): C, 46.03; H, 6.44; N, 10.73. Found: C, 46.85; H, 6.29; N,
11.11.
Harom), 5.40 (dd, J1-H,2-H 9.0 Hz, 1H, 1-H), 5.03 (br s, 2H, OH),
3
3
4.91 (br s, 1H, OH), 4.49 (m, 1H, OH), 3.65 (dd, J5-H,6-H 4.8 Hz,
2
0
J6-H,6 -H 11.4 Hz, 1H, 6-H), 3.54–3.45 (m, 2H) and 3.27–3.14 (m,
3H) (2-H, 3-H, 4-H, 5-H, 60-H); 13C NMR (75.47 MHz, DMSO-d6):
d 179.0 (C@S), 150.1 (Carom), 141.4 (CH@N), 140.7 and 121.6
(Carom), 84.1 (1-C), 78.7 (3-C), 77.4 (2-C), 71.8 (5-C), 69.8 (4-C),
60.9 (6-C). Anal. Calcd for C13H18N4O5S (342.37): C, 45.61; H,
5.30; N, 16.36. Found: C, 45.02; H, 5.67; N, 16.78.
1.3.15. 4-tert-Butyl-benzaldehyde 4-(b-D-glucopyranosyl)thio-
semicarbazone (3o)
1.3.19. 1-Ferrocenecarboxaldehyde 4-(b-D-glucopyranosyl)thio-
semicarbazone (3s)
Yield 72%; mp 123–125 °C (decomp., DMF/MeOH 1:1); Rf (CHCl3/
MeOH 5:1) 0.53; ½a D25
ꢂ
+66.2 (c 1.14, MeOH); IR (KBr): m 3324 (OH),
Yield 74%; mp 185–191 °C (decomp., MeOH/iPrOH 1:1); Rf
2864 (C–Harom), 1541 (C@N), 1018 (C@S), 900 (1-C–H), 826 (C@S)
(CHCl3/MeOH 9:1) 0.90; ½a D25
ꢂ
+40.0 (c 1, DMF); IR (KBr):
m
3326
;
cmꢀ1
;
1H NMR (599.83 MHz, DMSO-d6): d 11.71 (s, 1H, N(2)H),
(OH), 1534 (C@N), 1024 (C@S), 891 (1-C–H), 822 (C@S) cmꢀ1
1H
3
8.48 (d, J1-H,N(4)H 9.0 Hz, 1H, N(4)H), 8.09 (s, 1H, CH@N), 7.75 (d, J
8.4 Hz, 2H, Harom), 7.44 (d, J 7.2 Hz, 2H, Harom), 5.38 (dd, J 9.0 Hz,
1H, 1-H), 5.03 (br s, 2H, OH), 4.90 (br s, 1H, OH), 4.48 (br s, 1H,
OH), 3.65 (d, J 11.4 Hz, 1H, 6-H), 3.49–3.10 (m, 5H, 2-H, 3-H, 4-H,
5-H, 60-H), 1.30 (s, 9H, CH3(tBu)); 13C NMR (75.47 MHz, DMSO-d6):
d 178.5 (C@S), 152.9 (Carom–tBu), 143.1 (CH@N), 131.3, 127.4 and
125.5 (Carom), 84.0 (1-C), 78.7 (3-C), 77.6 (2-C), 72.1 (5-C), 69.9
(4-C), 60.9 (6-C), 34.6 (CMe3), 31.0 (CH3(tBu)).
NMR (300.13 MHz, DMSO-d6): d 11.49 (s, 1H, N(2)H), 8.18 (d,
3
3J1-H,N(4)H 9.0 Hz, 1H, N(4)H), 7.95 (s, 1H, CH@N), 5.34 (dd, J1-H,2-
9.3 Hz, 1H, 1-H), 4.81 (d, J 1.8 Hz, 1H, Fc), 4.73 (d, J 2.4 Hz, 1H,
H
Fc), 4.44 (m, 2H, Fc), 4.22 (s, 5H, Fc), 3.90 (br s, 4H, OH), 3.65 (d,
J 11.1 Hz, 1H, 6-H), 3.50–3.38 (m, 3H), and 3.24–3.09 (m, 2H) (2-
H, 3-H, 4-H, 5-H, 60-H); 13C NMR (75.47 MHz, DMSO-d6): d 177.5
(C@S), 144.3 (CH@N), 83.7 (1-C), 78.6 (C(Fc)–CH@N), 78.5 (3-C),
77.6 (2-C), 72.0 (5-C), 70.2 (Fc), 70.1 (Fc), 69.8 (4-C), 68.9 (Fc),
68.2 (Fc), 67.3 (Fc), 60.7 (6-C). Anal. Calcd for C18H23FeN3O5S
(449.30): C, 48.12; H, 5.16; N, 9.35. Found: C, 48.11; H, 5.68; N,
9.12.
1.3.16. 2-Pyridinecarboxaldehyde 4-(b-D-glucopyranosyl)thio-
semicarbazone (3p)
Yield 85%; mp 179–182 °C (decomp., MeOH/H2O 1:1); Rf
(CHCl3/MeOH 9:1) 0.60; IR (KBr): 3416 (OH), 2832 (C–Harom),
1557 (C@N), 1039 (C@S), 896 (1-C–H), 830 (C@S) cmꢀ1 1H NMR
(300.13 MHz, DMSO-d6): d 11.94 (s, 1H, N(2)H), 8.73 (d, J1-H,N(4)H
9.0 Hz, 1H, N(4)H), 8.59–8.56 (m, 1H, Harom), 8.35 (d, J 8.1 Hz, 1H,
Harom), 8.15 (s, 1H, CH@N), 7.87–7.82 (m, 1H, Harom), 7.41–7.37
m
1.3.20. b-Naphthalenecarboxaldehyde 4-(b-D-glucopyranosyl)-
thiosemicarbazone (3t)
;
3
Yield 67%; mp 218–222 °C (MeOH); Rf (CHCl3/MeOH 5:1) 0.40;
½
a 2D5
ꢂ
+60.5 (c 1, MeOH); IR (KBr):
m 3399 (OH), 1525 (C@N), 1055
(C@S), 900 (1-C–H), 843 (C@S) cmꢀ1
;
1H NMR (599.83 MHz,
3
(m, 1H, Harom), 5.40 (dd, J1-H,2-H 9.3 Hz, 1H, 1-H), 5.05 (br s, 3H,
3
DMSO-d6): d 11.84 (s, 1H, N(2)H), 8.64 (d, J1-H,N(4)H 9.0 Hz, 1H,
N(4)H), 8.28 (s, 1H, Hnaphth), 8.24 (d, J 8.4 Hz, 1H, Hnaphth), 8.15
(s, 1H, CH@N), 7.99–7.97 (m, 1H, Hnaphth), 7.94 (d, J7.8 Hz, 2H, Hnaphth),
OH), 4.51 (br s, 1H, OH), 3.66 (d, J 11.4 HZ, 1H, 6-H), 3.55–3.43
(m, 2H) and 3.27–3.15 (m, 3H) (m, 5H, 2-H, 3-H, 4-H, 5-H, 60-H);
13C NMR (75.47 MHz, DMSO-d6): d 178.9 (C@S), 153.0 and 149.4
(Carom), 143.3 (CH@N), 136.5, 124.3 and 120.6 (Carom), 84.1 (1-C),
78.7 (3-C), 77.6 (2-C), 71.9 (5-C), 69.8 (4-C), 60.8 (6-C). Anal. Calcd
for C13H18N4O5S.3H2O (396.42): C, 39.39; H, 6.10; N, 14.13. Found:
C, 39.78; H, 6.45; N, 14.15.
3
7.56–7.55 (m, 2H, Hnaphth), 5.42 (dd, J1-H,2-H 9.3 Hz, 1H, 1-H),
5.05–5.03 (m, 2H, OH), 4.92–4.91 (m, 1H, OH), 4.50 (t, 3J 6.0 Hz, 1
3
2
0
H, OH), 3.66 (dd, J5-H,6-H 5.4 Hz, J6-H,6 -H 11.4 Hz, 1H, 6-H), 3.57–
3.54 (m, 1H), 3.51–3.47 (m, 1H) and 3.28–3.16 (m, 3H) (2-H, 3-H,
4-H, 5-H, 60-H); 13C NMR (75.47 MHz, DMSO-d6): d 178.6 (C@S),
143.2 (CH@N), 133.7, 132.8, 131.7, 129.3, 128.3, 127.8, 127.1,
126.7 and 123.2 8 (Cnaphth), 84.1 (1-C), 78.7 (3-C), 77.6 (2-C), 71.9
(5-C), 69.9 (4-C), 60.9 (6-C). Anal. Calcd for C18H21N3O5S
(391.44): C, 55.23; H, 5.41; N, 10.73. Found: C, 55.57; H, 5.12; N,
11.02.
1.3.17. 3-Pyridinecarboxaldehyde 4-(b-D-glucopyranosyl)thio-
semicarbazone (3q)
Yield 86%; mp 199–201 °C (decomp., MeOH/H2O 1:1); Rf
(CHCl3/MeOH 9:1) 0.90; IR (KBr): 3399 (OH), 2873 (C–Harom),
1537 (C@N), 1043 (C@S), 904 (1-C–H), 828 (C@S) cmꢀ1 1H NMR
m
;
(300.13 MHz, DMSO-d6): d 11.86 (br s, 1H, N(2)H), 8.97 (d, J
1.5 Hz, 1H, Harom), 8.69 (d, J1-H,N(4)H 9.0 Hz, 1H, N(4)H), 8.56 (dd,
1.3.21. 4-Methoxy-acetophenone 4-(b-D-glucopyranosyl)thio-
semicarbazone (3u)
3
J 4.8 Hz, J 1.8 Hz, 1H, Harom), 8.29 (dt, J 8.1 Hz, J 1.8 Hz, 1H, Harom),
8.11 (s, 1H, CH@N), 7.43 (dd, J 8.1 Hz, J 4.8 Hz, 1H, Harom), 5.37 (dd,
3J1-H,2-H 9.0 Hz, 1H, 1-H), 5.04 (br s, 2H, OH), 4.94 (br s, 1H, OH),
Yield 60%; mp 127–131 °C (MeOH/H2O 1:1); Rf (CHCl3/MeOH
5:1) 0.60; ½a 2D5
ꢂ
+45.6 (c 1, MeOH); IR (KBr):
m
3297 (OH), 1510
(C@N), 1018 (C@S), 900 (1-C–H), 835 (C@S) cmꢀ1
;
1H NMR

A.-C. Tenchiu (Deleanu) et al. / Carbohydrate Research 344 (2009) 1352–1364
1363
(599.83 MHz, DMSO-d6): d 10.47 (br s, 1H, N(2)H), 8.35 (d,
3J1-H,N(4)H 8.4 Hz, 1H, N(4)H), 7.85 (d, J 8.4 Hz, 2H, Harom), 6.96 (d,
J 8.4 Hz, 2H, Harom), 5.38 (dd, J1-H,2-H 9.0 Hz, 1H, 1-H), 5.01 (br s,
11° < 2h < 23° and they appear in Table 4. Intensity data were re-
corded using a h–2h scan. Three standard reflections monitored
every 97 reflections showed less than 3% variation and no decay.
Lorentz, polarization and absorption corrections were applied
using Crystal Logic software. Slow crystallization from MeOH
yielded colourless crystals of 3j (0.26 ꢃ 0.50 ꢃ 0.50 mm), which
were taken from the mother liquor and immediately cooled to
ꢀ93 °C. Diffraction measurements were made on a Rigaku R-AXIS
SPIDER Image Plate diffractometer using graphite monochromated
3
3H, OH), 4.52 (br s, 1H, OH), 3.79 (s, 3H, OCH3), 3.63 (d, J 11.4 Hz,
1H, 60-H), 3.48 (dd, J 4.2 Hz, J 12.0 Hz, 1H, 6-H), 3.39 (t, J 9.0 Hz,
1 H), 3.25 (t, J 8.4 Hz, 1 H), 3.17 (dd, J 9.0 Hz, J 9.6 Hz, 1H) and
3.15–3.12 (m, 1H) (2-H, 3-H, 4-H, 5-H), 2.30 (s, 3H, CH3C@N); 13C
NMR (150.84 MHz, DMSO-d6): d 179.3 (C@S), 160.4 (Carom–O),
149.1 (C@N), 130.5, 129.9, 128.2, 113.8 and 113.7 (Carom), 83.8
(1-C), 78.6 (3-C), 77.4 (2-C), 72.3 (5-C), 69.8 (4-C), 60.8 (6-C),
55.2 (OCH3), 14.3 (CH3C@N). Anal. Calcd for C16H23N3O6S.3H2O
(439.48): C, 43.73; H, 6.65; N, 9.56. Found: C, 43.57; H, 6.98; N,
10.01.
Cu Ka radiation. Data collection (x-scans) and processing (cell
refinement, data reduction and empirical absorption correction)
were performed using the CRYSTALCLEAR program package.17 The
structures were solved by direct methods using SHELXS-9718 and re-
fined by full-matrix least-squares methods on F2 with SHELXL-97.19
All non-hydrogen atoms were refined anisotropically. Hydrogen
atoms were located by difference maps and were refined isotropi-
cally (except those of the methyl groups in 2d which were intro-
duced at calculated positions as riding on bonded atoms).
1.3.22. 2-Acetonaphthanone 4-(b-D-glucopyranosyl)thiosemi-
carbazone (3v)
Yield 77%; mp 182–185 °C (MeOH/H2O 1:1); Rf (CHCl3/MeOH
5:1) 0.44; ½a 2D5
ꢂ
+52.4 (c 1.16, MeOH); IR (KBr): m 3379 (OH), 1562
(C@N), 1018 (C@S), 892 (1-C–H), 826 (C@S) cmꢀ1
;
1H NMR
3
(599.83 MHz, DMSO-d6): d 10.65 (s, 1H, N(2)H), 8.51(d, J1-H,N(4)H
9.0 Hz, 1H, N(4)H), 8.34 (s, 1H, Hnaphth), 8.24 (d, J 9.0 Hz, 1H,
Hnaphth), 8.01 (s, 1H, Hnaphth), 7.93–7.91 (m, 2H, Hnaphth), 7.56–
2. Supplementary data
Supplementary crystallographic data for the structural analysis
have been deposited with the Cambridge Crystallographic Data
Centre, CCDC-711876 (2d) and 711877 (3j). Copies of this informa-
tion may be obtained free of charge from the Director, Cambridge
Crystallographic Data Centre, 12 Union Road, Cambridge, CB2 1EZ,
UK. (fax: +44-1223-336033, e-mail: deposit@ccdc.cam.ac.uk or via:
www.ccdc.cam.ac.uk).
3
7.54 (m, 2H, Hnaphth), 5.44 (dd, J1-H,2-H 9.3 Hz, 1H, 1-H), 5.13–
5.12 (m, 1H, OH), 5.03–5.02 (m, 1H, OH), 4.92–4.91 (m, 1H, OH),
3
2
0
4.49–4.48 (m, 1H, OH), 3.67 (dd, J5-H,6-H 5.4 Hz, J6-H,6 -H 11.4 Hz,
1H, 6-H), 3.52–3.48 (m, 2H) and 3.28–3.19 (m, 3H) (2-H, 3-H,
4-H, 5-H, 60-H), 2.47 (s, 3H, CH3C@N); 13C NMR (75.47 MHz,
DMSO-d6): d 179.6 (C@S), 148.9 (C@N), 134.9, 133.3, 132.7,
128.6, 127.7, 127.5, 126.9, 126.8, 126.4 and 123.9 (Cnaphth), 84.0
(1-C), 78.6 (3-C), 77.5 (2-C), 72.1 (5-C), 69.8 (4-C), 60.8 (6-C),
14.2 (CH3). Anal. Calcd for C19H23N3O5Sꢁ2H2O (441.50): C, 51.69;
H, 6.16; N, 9.52. Found: C, 51.12; H, 5.98; N, 9.32.
Acknowledgement
This work was supported by the EST Marie Curie program
EURODESY, Contr. No. MEST-CT-2005-020575 (2006–2010).
1.4. X-Ray crystallographic study of 2d and 3j
References
Slow crystallization from EtOH yielded colourless crystals of 2d
(0.25 ꢃ 0.30 ꢃ 0.75 mm), which were mounted in air. Diffraction
measurements were made on a Crystal Logic Dual Goniometer dif-
fractometer using graphite monochromated Mo radiation. Unit cell
dimensions were determined and refined by using the angular set-
tings of 25 automatically centred reflections in the range
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Table 4
X-ray experimental data of compounds 2d and 3j
2d
3j
Empirical formula
Formula mass
Crystal system
Space group
C23H26F3N3O9S
577.54
C14H19N3O6S
357.39
Orthorhombic
P212121
17.608(4)
9.325(2)
17.738(4)
2912.5(11)
4
1.317
1200
0.181
298
Orthorhombic
P212121
7.5232(1)
12.6624(2)
17.4260(3)
1660.03(4)
4
1.430
752
2.068
180
a
(Å)
b (Å)
c (Å)
V (Å3)
Z
Dcalcd (gcmꢀ3
F(0 0 0)
)
l
(mmꢀ1
)
T (K)
k (Å)
Radiation
h limits
No. of data with I > 2r(I)
0.71073
Mo K
2.3/25.0
3891
1.54178
Cu Ka
6.8/65.0
2781
a
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440
293
0.0418
0.1191
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1.07
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1364
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