Synthesis of N-tetra-O-acetyl-β-d-glucopyranosyl-N′-(4′,6′-diarylpyrimidin-2′-yl)thioureas

Article abstract of DOI:10.1016/j.carres.2009.09.002

Some 2-amino-4,6-diarylpyrimidines 2 have been prepared from substituted benzylideneacetophenones and guanidine hydrochloride in the presence of alkali by conventional heating in alcoholic medium and microwave heating in solvent-free conditions. N-(2,3,4,

Full text of DOI:10.1016/j.carres.2009.09.002

Carbohydrate Research 344 (2009) 2399–2405
Contents lists available at ScienceDirect
Carbohydrate Research
journal homepage: www.elsevier.com/locate/carres
Note
Synthesis of N-tetra-O-acetyl-b-D-glucopyranosyl-
N0-(40,60-diarylpyrimidin-20-yl)thioureas
*
Nguyen Dinh Thanh , Nguyen Thi Thanh Mai
Faculty of Chemistry, College of Science, Hanoi National University, 19 Le Thanh Tong, Hanoi 10000, Viet Nam
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 20 June 2009
Received in revised form 30 August 2009
Accepted 1 September 2009
Available online 6 September 2009
Some 2-amino-4,6-diarylpyrimidines 2 have been prepared from substituted benzylideneacetophenones
and guanidine hydrochloride in the presence of alkali by conventional heating in alcoholic medium and
microwave heating in solvent-free conditions. N-(2,3,4,6-Tetra-O-acetyl-b-D
-glucopyranosyl)-N0-(40,60-
diarylpyrimidin-20-yl)thioureas 4 have been synthesized by reaction of per-O-acetylated glucopyranosyl
isothiocyanate 1 and substituted 2-amino-4,6-diarylpyrimidines 2. Two different methods have been
used, namely, refluxing in anhydrous dioxane and solvent-free microwave-assisted coupling. The second
procedure afforded higher yields in much shorter reaction times. The compounds 2 and 4 were tested for
their antibacterial and antifungal activities in vitro against Staphylococcus epidermidis, Enterobacter
aerogenes and Candida albicans by disc diffusion method.
Keywords:
Pyrimidine
Glucopyranosyl thiourea
Glucopyranosyl isothiocyanate
Microwave-assisted method
Ó 2009 Elsevier Ltd. All rights reserved.
The pyrimidine structural motif is a fundamental part of nucleic
acids and has been associated with a number of biological activi-
ties.1,2 Aminopyrimidine derivatives have displayed interesting
antibacterial, antitumour and HIV-I inhibiting activities.2 Both
pyrimidine and aminopyrimidine moieties occur in commercially
available drugs such as the anti-atherosclerotic AronixilÒ, the anti-
histaminic ThonzylamineÒ, the anti-anxiolytic BuspironeÒ, and in
other medicinally relevant compounds as well.3
In an other hand, sugar isothiocyanates are among the most
versatile synthetic intermediates in carbohydrate chemistry.4 They
play a pivotal role in the preparation of a broad series of functional
groups such as amide, isonitrile, carbodiimide and N-thiocarbonyl
derivatives allowing, simultaneously, the covalent coupling of a
quite unrestricted variety of structures to the saccharide part.5
Moreover, isothiocyanates are important reagents in heterocyclic
chemistry, which may be exploited in the synthesis of nucleosides
and other N-glycosyl structures.6,7
Glucopyranosyl thioureas containing heterocycles (such as thi-
azole, benzothiazole20 and thiadiazole21) were synthesized using
conventional heating method. We report herein the preparation
of some peracetylated glucopyranosyl thioureas containing the
pyrimidine nucleus both under classical heating and solvent-free
microwave irradiation conditions.
2-Aminopyrimidines were prepared previously by the reac-
tion of substituted benzylideneacetophenones22 with guanidine
under reflux in ethanol.3,23 For the purpose of this work, we
have prepared new 2-amino-4,6-diarylpyrimidines 2a–j by ring-
closure condensation of substituted benzylideneacetophenones
and guanidine hydrochloride in the presence of sodium hydrox-
ide under microwave-assisted conditions and compare the
results with the classical procedures (Scheme 1 and Table 1).
N-(2,3,4,6-Tetra-O-acetyl-b-
din-20-yl)thioureas 4a–j were subsequently synthesized by the
condensation of tetra-O-acetyl-b- -glucopyranosyl isothiocyanate
D
-glucopyranosyl)-N0-(40,60-diarylpyrimi-
D
One of the most popular and interesting approach in the context
of ‘green chemistry’ is employing microwave energy for conduct-
ing chemical transformations, which allows a higher speed of heat-
ing, shorter reaction times, is compatible with solvent-free
conditions and very often lead to higher selectivities.8–11
and the corresponding 2-aminopyrimidines 2a–j. We performed
O
NH2C(=NH)NH .HCl
2
Thioureas and derivatives are biologically important com-
pounds and are useful fungicides, herbicides12 and antibacterial
agents.13 They have also found use in organocatalysis.14,15 Thio-
ureas have been synthesized by the reaction of primary and sec-
ondary amines with thiophosgene and isothiocyanates.4,5,16–19
Home MW oven
R
R
N
N
1a-j
NH2
2a-j
1a-j
2a-j:
a b c d e
R= H ( ), p-F ( ), p-Cl ( ), m-Cl ( ), p-Br ( ),
and
f
g
h
i
j
p-Me ( ), p-iPr ( ), o-OH ( ), p-OMe ( ), m-OMe ( )
* Corresponding author. Tel.: +84 4 8261853; fax: +84 4 8241140.
E-mail address: nguyendinhthanh@hus.edu.vn (N.D. Thanh).
Scheme 1. Synthetic pathway for 2-amino-4,6-diarylpyrimidines (2a–j).
0008-6215/$ - see front matter Ó 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.carres.2009.09.002

2400
N. D. Thanh, N. T. T. Mai / Carbohydrate Research 344 (2009) 2399–2405
H disposition and a b-anomeric configuration. The 13C NMR spectra
Table 1
2-Amino-4,6-diarylpyrimidines (2a–j)
showed signals for the thiocarbonyl group at d = 181.3–
181.4 ppm.24 The mass spectra showed M+ peak at the respective
molecular weights of the compounds. Some of them were sub-
jected to HREIMS to obtain respective molecular weights.
Compounds 2 and 4 were screened for their antibacterial and
antifungal activities in vitro against Staphylococcus epidermidis,
Enterobacter aerogenes and Candida albicans by the disc diffusion
method. All amines 2 have significant biological activities against
E. aerogenes, S. epidermidis and C. albicans. Compounds 2a–j
showed highest antibacterial activity against S. Epidermidis (Table
3). Almost all compounds 4 have remarkable biological activity, ex-
cept compound 4b which exhibited no antifungal activity against
E. aerogenes and compound 4g against C. albicans. Especially, the
antibacterial activity against S. epidermidis was proved significantly
in these compounds (Table 4).
Entry
R
Yield (%)
B
Microwave irradiation time (min)
A
2a
2b
2c
2d
2e
2f
2g
2h
2i
H
p-F
p-Cl
m-Cl
p-Br
p-Me
p-iPr
o-OH
p-OMe
m-OMe
72
—
89
86
85
83
80
85
85
85
80
83
1
2
2
2
2
1
1
1
1
1
76
75
71
—
—
70
73
—
2j
A: by refluxing; B: under solvent-free condition in modified domestic microwave
oven.
In summary, the present new method of formation of 2-
amino-4,6-diarylpyrimidines 2 and N-(2,3,4,6-tetra-O-acetyl-b-D-
this reaction by using two methods: by refluxing in anhydrous
dioxane for 8–10 h and by irradiation in a domestic microwave
oven for a few minutes in solvent-free condition (Scheme 2
and Table 2). The last method accelerated the reactions and gave
higher yields.
We realized that 2-amino-4,6-diphenylpyrimidines with elec-
tron-withdrawing group (such NO2, except halogens) cannot be
formed; we tried to perform the reaction of benzylideneacetophe-
nones having nitro-group with guanidine, but the reactions were
unsuccessful.
glucopyranosyl)-N0-(40,60-diarylpyrimidin-20-yl)thioureas 4 under
microwave irradiation offers several advantages: faster reaction
rates (1–2 min for 2 and 5–7 min for 4) and high yields (80–89%
for 2 and 72–83% for 4), while the conventional method of forma-
tion of these thioureas involves longer reaction times (8–10 h and
60–68% for 4).
1. Experimental
1.1. General methods
In the refluxing cases, 2-aminopyrimidines 2 and peracetylated
glucopyranosyl isothiocyanate 3 were dissolved in anhydrous
dioxane. After the reaction, the solvent was distilled off, and the
resultant sticky residue was triturated with ethanol to afford thio-
ureas 4a–j that were recrystallized with 1:1 ethanol–toluene.
Using MW irradiation, a mixture of 2-aminopyrimidine and per-
acetylated glucopyranosyl isothiocyanate was grinded together
and irradiated in domestic MW oven (750 W). After first several
minutes of microwave irradiation (MWI), the reaction mixture
became pastry. The reaction yields increased using MW oven from
60–68% to 68–80%. All the obtained thioureas were soluble in com-
mon organic solvents (such as ethanol, methanol, toluene, benzene
and DMF). Their structures have been confirmed by spectral (IR,
NMR and MS) data.
Melting points were determined on a STUART SMP3 apparatus
(BIBBY STERILIN-UK). The FTIR-spectra were recorded on a Magna
Table 2
N-(2,3,4,6-Tetra-O-acetyl-b-D-glucopyranosyl)-N’-(4,6-diarylpyrimidin-2-yl)thioureas
(4a–j)
Entry
R
Yielda
(%)
Refluxing
time (h)
Yieldb
(%)
Microwave
irradiation
time (min)
4a
4b
4c
4d
4e
4f
4g
4h
4i
H
p-F
p-Cl
m-Cl
p-Br
p-Me
p-iPr
o-OH
p-OMe
m-OMe
60
—
8
—
9
10
9
8
8
9
8
—
75
87
76
72
76
80
79
80
77
83
5
5
6
7
5
7
6
6
6
6
68
67
66
60
68
60
68
—
The IR spectra showed characteristic bands at 3522–3410 (
1754–1748 ( C@O), 1594, 1578, 1526, 1495 ( C@C), 1364–1362
C@S), 1232–1222 and 1070–1041 cmꢀ1 COC). The 1H NMR spec-
mNH),
m
m
(m
(m
tra showed resonance signals which are specific for protons in
thiourea-NH groups at d = 11.16–12.04 ppm. Proton H-1 has its
chemical shift at d = 6.19–6.21 ppm (in triplet) with couple con-
stants J12 = 9.0–9.5 Hz. The resonance signal of H-2 appeared as a
triplet at d = 5.02–5.06 ppm with J12 = 9.0–9.5 Hz. The coupling
constant values for the pyranose ring agreed with trans-axial H–
4j
a
By refluxing.
By using microwave oven.
b
OAc
OAc
R
O
O
a
i or ii
N
N
b
NH
AcO
AcO
AcO
2a-j
NCS
AcO
NH
+
OAc
OAc
3
S
4a-j
2a-j
4a-j:
a b c d e
R= H ( ), p-F ( ), p-Cl ( ), m-Cl ( ), p-Br ( ),
and
f
g
h
i
j
p-Me ( ), p-iPr ( ), o-OH ( ), p-OMe ( ), m-OMe ( )
i: anhydrous dioxane, reflux 8-10 h
ii: solvent-free, MW irradiation 5-7 min
Scheme 2. Synthetic pathway for N-(2,3,4,6-tetra-O-acetyl-b-D
-glucopyranosyl)-N0-(4,6-diarylpyrimidin-2-yl)thioureas (4a–j).

N. D. Thanh, N. T. T. Mai / Carbohydrate Research 344 (2009) 2399–2405
2401
Table 3
Response of various micro-organisms to substituted amino-4,6-diarylpyrimidine 2a–j
1.2. General procedure for the synthesis of 2-amino-4,6-
diarylpyrimidines (2a–j)
Entry
R
Diameter of zone inhibitiona (mm)
Procedure A (under refluxing condition). A solution of substituted
benzylideneacetophenone 1 (10 mmol) in ethanol (5 mL) was
added to a solution of guanidine hydrochloride (15 mmol) and so-
dium hydroxide (45 mmol) in water (2 mL). The reaction mixture
was refluxed for 10 min in the modified domestic microwave oven.
The solvent was removed under reduced pressure and the residue
was triturated with water and the precipitate was filtered by
suction and washed with water until neutral to afford the title
compounds 2, which were recrystallized from 1:1 EtOH-toluene
to give ivory-white crystals.
E. aerogenes
S. epidermidis
C. albicans
2a
2b
2c
2d
2e
2f
2g
2h
2i
H
p-F
p-Cl
15
26
20
18
15
23
22
18
18
19
25b
30
30
29
30
28
27
26
23
29
25
25c
20
25
17
20
15
26
25
24
18
22
35d
m-Cl
p-Br
p-Me
p-iPr
o-OH
p-OMe
m-OMe
—
2j
Ref.
Procedure
B
(under microwave-assisted and solvent-free
c
d
Ref = b ampicillin; methicillin; clotrimazole.
conditions). Substituted benzylideneacetophenone 1 (10 mmol),
guanidine hydrochloride (15 mmol) and sodium hydroxide
(45 mmol) were mixed carefully with a little water. The obtained
mixture was irradiated under domestic microwave oven. After
1–2 min, the reaction mixture had become dark-yellow, and then
the irradiation was continued for the given time. Upon
completion, monitored by TLC, the reaction mixture was cooled
to room temperature and then triturated with water and the
formed precipitate was filtered by suction and washed
with water until neutral to afford the title compounds 2, which
were recrystallized from 1:1 EtOH-toluene to give ivory-white
crystals.
a
DMF used as control; concentration used = 100 lg/mL of DMF.
Table 4
Response of various micro-organisms to substituted N-(2,3,4,6-tetra-O-acetyl-b-D-
glucopyranosyl)-N’-(40,60-diarylpyrimidin-20-yl)thioureas 4a–j
Entry
R
Diameter of zone inhibition (mm)a
E. aerogenes
S. epidermidis
C. albicans
4a
4b
4c
4d
4e
4f
4g
4h
4i
H
p-F
p-Cl
15
17
0
27
28
30
28
30
28
29
27
29
24
35c
15
16
14
19
21
20
22
21
0
1.2.1. 2-Amino-4,6-diphenylpyrimidine (2a)
From benzylideneacetophenone (2.08 g, 10 mmol) and guani-
dine hydrochloride (1.43 g, 15 mmol). Recrystallized from EtOH/
toluene to yield a white solid, 1.78 g, 72% (procedure A); 2.20 g,
m-Cl
p-Br
p-Me
p-iPr
o-OH
p-OMe
m-OMe
—
13
18
20
22
20
23
22
35b
89% (procedure B); mp 118–119 °C; IR (KBr)
m
/cmꢀ1: 3469, 3320,
1
1601; H NMR (DMSO-d6): d 8.22–8.20 (m, 4H, H-30 & H50 and H-
300 & H-500), 7.70 (s, 1H, H-5), 7.53–7.52 (m, 6H, H-20, H-40 & H-60
and H-200, H-400 & H-600); HREIMS: calcd for C16H13N3: 247.1109,
found: 247.0929. Anal. Calcd for C16H12BrN3: C, 77.71; H, 5.30; N,
16.99. Found: 77.86; H, 5.46; N, 17.05.
4j
Ref.
22
45d
c
d
Ref = b ampicillin; methicillin; clotrimazole.
a
DMF used as control; concentration used = 100 lg/mL of DMF.
1.2.2. 2-Amino-4-(p-fluorophenyl)-6-phenylpyrimidine (2b)
From p-fluorobenzylideneacetophenone (2.26 g, 10 mmol) and
guanidine hydrochloride (1.43 g, 15 mmol). Recrystallized from
EtOH/toluene to yield a white solid, 2.78 g, 86% (procedure B);
760 FT-IR Spectrometer (NICOLET, USA) in KBr pellets. The 1H NMR
(500.13 MHz) and 13C NMR (125.77 MHz) spectra were recorded
on an AVANCE500 Spectrometer (BRUKER, Germany) in DMSO-d6
solution; d are in ppm compared to TMS as internal reference at
300 K. The assignments of 1H and 13C were confirmed using HMBC
and HSQC methods. The high-resolution mass spectra were re-
corded on AutoSpec Premier instrument (WATERS, USA) using EI.
Optical rotations were measured on a POLAX-2L polarimeter
(ATAGO-Japan) in DMSO solution. Analytical thin-layer chroma-
tography (TLC) was performed on Silica Gel 60F254 No. 5715
(Merck, Germany) with EtOAc and light petroleum (bp 60–90 °C).
The spots were visualized by exposure to UV light or by spraying
the plates with 10% (v/v) H2SO4 in EtOH, followed by heating.
mp 132–133 °C; IR (KBr)
m
/cmꢀ1: 3493, 3314, 1634; 1H NMR
(DMSO-d6): d 8.30 (s, 1H, H-20), 8.25–8.23 (m, 2H, H-300 & H-500),
8.20 (d, 1H, J = 7.5 Hz, H-40), 7.78 (s, 1H, H-5), 7.59–7.75 (m, 2H,
J = 7.5 Hz & 3.0 Hz, H-50 & H60), 7.53–7.52 (m, 3H, H-200, H-400
&
H-600), 6.80 (s, 2H, NH2). Anal. Calcd for C16H12FN3: C, 72.44; H,
4.56; N, 15.84. Found: C, 72.60; H, 4.60; N, 15.80.
1.2.3. 2-Amino-4-(p-chlorophenyl)-6-phenylpyrimidine (2c)
From p-chlorobenzylideneacetophenone (2.42 g, 10 mmol) and
guanidine hydrochloride (1.43 g, 15 mmol). Recrystallized from
EtOH/toluene to yield a white solid, 2.14 g, 76% (procedure A);
m :
/cmꢀ1
2,3,4,6-Tetra-O-acetyl-b-
D-glucopyranosyl isothiocyanate
3
was
2.25 g, 85% (procedure B); mp 160–161 °C; IR (KBr)
1
3493, 3314, 1634; H NMR (DMSO-d6): d 8.30 (s, 1H, H-20), 8.25–
8.23 (m, 2H, H-300 & H-500), 8.20 (d, 1H, J = 7.5 Hz, H-40), 7.78
(s, 1H, H-5), 7.59–7.75 (m, 2H, J = 7.5 Hz & 3.0 Hz, H-50 & H60),
7.53–7.52 (m, 3H, H-200, H-400 & H-600), 6.80 (s, 2H, NH2); HREIMS
calcd for C16H1235ClN3/C16H1237ClN3: 281.0719/283.0690, found:
281.0796/283.0660. Anal. Calcd for C16H12ClN3: C, 68.21; H, 4.29;
N, 14.91. Found: C, 68.45; H, 4.31; N, 14.84.
prepared by the reaction of per-O-acetylated-b-
D-glucopyranosyl
bromide25 with lead thiocyanate in dried toluene.20 Other reagents
were supplied by Merck and used as received.
In order to perform the reaction in a domestic microwave oven,
we have built a modified commercial microwave oven (Tiffany
MM17L, power 750 W) in which the round-bottomed flask was at-
tached to a condenser. This condenser was assembled with the
flask in microwave oven through a hole on the top. The condenser
was protected with a metallic wire mesh connected to the oven
body to avoid any microwave leakages. It is also possible to con-
duct the experiments under controlled atmosphere like nitrogen
(Fig. 1, see in Supplementary data).
1.2.4. 2-Amino-4-(m-chlorophenyl)-6-phenylpyrimidine (2d)
From m-chlorobenzylideneacetophenone (2.42 g, 10 mmol) and
guanidine hydrochloride (1.43 g, 15 mmol). Recrystallized from
EtOH/toluene to yield a white solid, 2.11 g, 75% (procedure A);

2402
N. D. Thanh, N. T. T. Mai / Carbohydrate Research 344 (2009) 2399–2405
2.34 g, 83% (procedure B); mp 118–119 °C; IR (KBr)
m
/cmꢀ1: 3491,
H-20 & H60), 6.61 (s, 2H, NH2), 3.84 (s, 3H, OCH3); HREIMS calcd
for C17H15N3O: 277.1215, found: 277.0977. Anal. Calcd for
C17H15N3O: C, 73.63; H, 5.45; N, 15.15. Found: C, 73.83; H, 5.35;
N, 15.35.
3315, 1634; 1H NMR (DMSO-d6): d 8.30 (s, 1H, H-20), 8.25–8.23 (m,
2H, H-300 & H-500), 8.20 (d, 1H, J = 7.5 Hz, H-40), 7.78 (s, 1H, H-5),
7.59–7.75 (m, 2H, J = 7.5 Hz & 3.0 Hz, H-50 & H60), 7.53–7.52 (m,
3H, H-200, H-400 & H-600), 6.80 (s, 2H, NH2); HREIMS calcd for
C16H1235ClN3/C16H1237ClN3: 281.0719/283.0690, found: 281.0724/
283.0745. Anal. Calcd for C16H12ClN3: C, 68.21; H, 4.29; N, 14.91.
Found: C, 68.55; H, 4.38; N, 14.87.
1.2.10. 2-Amino-4-(m-methoxyphenyl)-6-phenylpyrimidine
(2j)
From m-methoxybenzylideneacetophenone (2.38 g, 10 mmol)
and guanidine hydrochloride (1.43 g, 15 mmol). Recrystallized
from EtOH/toluene to yield a white solid, 2.29 g, 83% (procedure
1.2.5. 2-Amino-4-(p-bromophenyl)-6-phenylpyrimidine (2e)
From p-bromobenzylideneacetophenone (2.87 g, 10 mmol) and
guanidine hydrochloride (1.43 g, 15 mmol). Recrystallized from
EtOH/toluene to yield a white solid, 2.31 g, 71% (procedure A);
B); mp 139–140 °C; (KBr)
m
/cmꢀ1: 3491, 3315, 1634; 1H NMR
(DMSO-d6): d 8.30 (s, 1H, H-20), 8.25–8.23 (m, 2H, H-300 & H-500),
8.20 (d, 1H, J = 7.5 Hz, H-40), 7.78 (s, 1H, H-5), 7.59–7.75 (m, 2H,
2.61 g, 80% (procedure B); mp 171–172 °C; IR (KBr)
m
/cmꢀ1
:
J = 7.5 Hz & 3.0 Hz, H-50 & H60), 7.53–7.52 (m, 3H, H-200, H-400
&
3493, 3294, 3159, 1632; 1H NMR (DMSO-d6): d 8.22–8.20 (m, 2H,
H-300 & H-500), 8.18 (d, 2H, J = 8.5 Hz, H-30 & H50), 7.72 (s, 1H, H-
H-600), 6.80 (s, 2H, NH2), 3.92 (s, 3H, OCH3); Anal. Calcd for
C17H15N3O: C, 73.63; H, 5.45; N, 15.15. Found: C, 73.80; H, 5.31;
N, 15.39.
5), 7.72 (d, 2H, J = 8.5 Hz, H-20
&
H60), 7.53–7.51 (m, 3H,
J = 3.5 Hz, H-200, H-400 & H-600), 6.76 (s, 2H, NH2); HREIMS calcd for
C16H1279BrN3/C16H1281BrN3: 325.0215/327.0194, found: 325.3736/
327.3077. Anal. Calcd for C16H12BrN3: C, 58.91; H, 3.71; N, 12.88.
Found C, 59.11; H, 3.61; N, 12.85.
1.3. General procedure for the synthesis of N-(2,3,4,6-tetra-O-
acetyl-b-D
-glucopyranosyl)-N0-(40,60-diarylpyrimidin-20-
yl)thioureas (4a–j)
1.2.6. 2-Amino-4-(p-methylphenyl)-6-phenylpyrimidine (2f)
From p-methylbenzylideneacetophenone (2.22 g, 10 mmol) and
guanidine hydrochloride (1.43 g, 15 mmol). Recrystallized from
EtOH/toluene to yield a white solid, 2.22 g, 85% (procedure B);
Procedure A (under refluxing condition). A solution of 2-amino-
4,6-diarylpyrimidine 2 (2 mmol) in anhydrous dioxane (10 mL)
was added to a solution of 2,3,4,6-tetra-O-acetyl-b-D-glucopyrano-
syl isothiocyanate 3 (2 mmol) in anhydrous dioxane (10 mL). The
reaction mixture was heated at reflux for 8–10 h. Then the solvent
was removed under reduced pressure, and the residue was tritu-
rated with ethanol. The precipitate was filtered by suction and
recrystallized with 1:1 EtOH-water to afford the title compounds
4 as ivory-white crystals.
mp 127–128 °C; IR (KBr)
m
/cmꢀ1: 3363, 3327, 3191, 1642; 1H
NMR (DMSO-d6): d 8.20–8.18 (m, 2H, H-300 & H-500), 8.19 (d, 2H,
J = 9.0 Hz, H-30 & H50), 7.64 (s, 1H, H-5), 7.52–7.50 (m, 3H, H-200,
H-400 & H-600), 7.06 (d, 2H, J = 9.0 Hz, H-20 & H60), 6.61 (s, 2H,
NH2), 2.41 (s, 3H, CH3); Anal. Calcd for C17H15N3: C, 78.13; H,
5.79; N, 16.08. Found: C, 73.20; H, 5.30; N, 15.41.
Procedure B (under microwave-assisted and solvent-free condi-
tions). A mixture of 2-amino-4,6-diarylpyrimidine 2 (2 mmol)
1.2.7. 2-Amino-4-(p-isopropylphenyl)-6-phenylpyrimidine (2g)
From p-isopropylbenzylideneacetophenone (2.50 g, 10 mmol)
and guanidine hydrochloride (1.43 g, 15 mmol). Recrystallized
from EtOH/toluene to yield a white solid, 2.46 g, 85% (procedure
and 2,3,4,6-tetra-O-acetyl-b-D-glucopyranosyl isothiocyanate 3
(2 mmol) was grinded in a 5mL porcelain beaker. Then the mixture
was put into a domestic microwave oven (the power output is
750 W). The adjustor of the microwave oven was set to the proper
temperature (about 50 °C). The reactants were irradiated for a per-
iod of 5–7 min. The mixture became dark-yellow paste in reaction
process. The reaction was traced with thin-layer chromatography.
The reaction mixture was cooled to room temperature, triturated
with ethanol, filtered by suction and recrystallized with ethanol/
toluene (1:1) to afford the title compounds 4 as ivory-white
crystals.
B); mp 141–142 °C; IR (KBr) m
/cmꢀ1: 3363, 3327, 3191, 1642; 1H
NMR (DMSO-d6): d 8.20–8.18 (m, 2H, H-300 & H-500), 8.19 (d, 2H,
J = 9.0 Hz, H-30 & H50), 7.64 (s, 1H, H-5), 7.52–7.50 (m, 3H, H-200,
H-400 & H-600), 7.06 (d, 2H, J = 9.0 Hz, H-20 & H60), 6.61 (s, 2H,
NH2), 3.02 [septet, 1H, J = 12.0 Hz, 4000-CH(CH3)2], 1.28 [d, 6H,
J = 12.0 Hz, 4000-CH(CH3)2]; Anal. Calcd for C19H19N3: C, 78.86; H,
6.62; N, 14.52. Found: C, 78.74; H, 6.42; N, 14.72.
1.2.8. 2-Amino-4-(o-hydroxyphenyl)-6-phenylpyrimidine (2h)
From o-hydroxybenzylideneacetophenone (2.24 g, 10 mmol)
and guanidine hydrochloride (1.43 g, 15 mmol). Recrystallized
from EtOH/toluene to yield a white solid, 1.84 g, 70%, procedure
1.3.1. N-(2,3,4,6-Tetra-O-acetyl-b-D
-glucopyranosyl)-N0-(40,60-
diphenylpyrimidin-20-yl)thiourea (4a)
From 494 mg of 2a and 778 mg of 3. Recrystallized from EtOH-
toluene to yield ivory-white crystals, 763 mg, 60% (procedure A);
A; 2.24 g, 85% (procedure B); mp 181–182 °C; IR (KBr)
m
/cmꢀ1
:
954 mg, 75% (procedure B); mp 229–230 °C; ½a D25
ꢁ
+46.6 (c 1.0,
3519, 3362, 3204, 1629; 1H NMR (DMSO-d6): d 8.25–8.21 (m, 3H,
H-300, H-500 & H-30), 7.86 (s, 1H, H-5), 7.54–7.53 (m, 3H, H-200, H-
400 & H-600), 7.37–7.34 (td, 1H, J = 8.5 Hz & 1.25 Hz, H-60), 7.18 (br,
OH & NH2), 6.90 (t, 1H, J = 7.0 Hz, H-50), 6.90 (dd, 1H, J = 8.5 Hz &
1.25 Hz, H-40); HREIMS calcd for C16H13N3O: 263.1059, found:
263.0977. Anal. Calcd for C16H13N3O: C, 72.99; H, 4.98; N, 15.96.
Found: C, 72.69; H, 4.88; N, 15.67.
DMSO); IR (KBr) m
/cmꢀ1: 3529, 3422 (m, NH), 1754 (s, C@O),
1594, 1578, 1526, 1495 (Ar), 1362 (m, C@S),1231 and 1045 (m,
C–O–C); 1H NMR (DMSO-d6): d 12.18 (d, 1H, J = 9.5 Hz, Ha),
11.11 (s, 1H, Hb), 8.32–8.30 (m, 4H, H-200, H-600 & H-2000, H-6000),
8.29 (s, 1H, H-50), 7.65–7.60 (m, 6H, H-300, H-400, H-500 & H-3000,
H-4000, H-5000), 6.21 (t, 1H, J = 9.5 Hz, H-1), 5.53 (t, 1H, J = 9.5 Hz,
H-3), 5.04 (t, 1H, J = 9.25 Hz, H-2), 5.03 (t, 1H, J = 9.5 Hz, H-4),
4.23 (m, 1H, H-5), 4.23 (d, 1H, J = 10.0 Hz, H-6a), 4.07 (d, 1H,
J = 10.0 Hz, H-6b), 2.03, 1.99, 1.96, 1,95 (4s, 12H, 4 ꢂ CH3CO);
13C NMR (DMSO-d6): d 181.39 (C@S), 169.93, 169.57, 169.50,
1.2.9. 2-Amino-4-(p-methoxyphenyl)-6-phenylpyrimidine (2i)
From p-methoxybenzylideneacetophenone (2.38 g, 10 mmol)
and guanidine hydrochloride (1.43 g, 15 mmol). Recrystallized
from EtOH/toluene to yield a white solid, 2.02 g, 73% (procedure
169.35 (4C, 4 ꢂ CH3CO), 164.97 (C-40
&
C-60), 157.55 (C-20),
135.53 (C-100 & C-1000), 131.73 (C-400 & C-4000), 128.96 (C-300, C-500,
C-3000 & C5000), 127.49 (C-200, C-600, C-2000 & C-6000), 107.66 (C-50),
81.72 (C-1), 72.61 (C-5), 72.14 (C-3), 71.48 (C-2), 67.98 (C-4),
61.75 (C-6), 20.43, 20.40, 20.32, 20.23 (4C, 4 ꢂ CH3CO); EIMS:
m/z 635, [MꢀH]+Å.
A); 2.22 g, 80% (procedure B); mp 151–152 °C; IR (KBr) m :
/cmꢀ1
3363, 3327, 3191, 1642; 1H NMR (DMSO-d6): d 8.20–8.18 (m, 2H,
H-300 & H-500), 8.19 (d, 2H, J = 9.0 Hz, H-30 & H50), 7.64 (s, 1H, H-
5), 7.52–7.50 (m, 3H, H-200, H-400 & H-600), 7.06 (d, 2H, J = 9.0 Hz,

N. D. Thanh, N. T. T. Mai / Carbohydrate Research 344 (2009) 2399–2405
2403
1.3.2. N-(2,3,4,6-Tetra-O-acetyl-b-
D
-glucopyranosyl)-N0-[40-(p-
71.53 (C-2), 67.98 (C-4), 61.72 (C-6), 20.39, 20.39, 20.28, 20.17
(4C, 4 ꢂ CH3CO).
fluorophenyl)-60-phenyl-pyrimidin-20-yl]thiourea (4b)
From 638 mg of 2b and 778 mg of 3. Recrystallized from EtOH-
toluene to yield ivory-white crystals, 1076 mg, 76% (procedure B);
1.3.5. N-(2,3,4,6-Tetra-O-acetyl-b-D
-glucopyranosyl)-N0-[40-(p-
mp 223–224 °C ; ½a D25
ꢁ
+65.6 (c 1.0, DMSO); IR (KBr)
m
/cmꢀ1: 3291
bromophenyl)-60-phenyl-pyrimidin-20-yl]thiourea (4e)
From 652 mg of 2e and 778 mg of 3. Recrystallized from EtOH-
toluene to yield ivory-white crystals, 944 mg, 66% (procedure A);
(m, NH), 1755 (s, C@O), 1594, 1578, 1526, 1495 (Ar), 1368 (m,
C@S),1233 and 1045 (m, C–O–C); 1H NMR (DMSO-d6): d 12.07 (d,
1H, J = 9.0 Hz, Ha), 11.14 (s, 1H, Hb), 8.40 (qd, 2H, J = 8.5 Hz,
1087 mg, 76% (procedure B); mp 223–224 °C; ½a D25
ꢁ
+89.1 (c 1.0,
J = 1.75 Hz, H-2000
&
H-6000), 8.31 (s, 1H, H-50), 8.30 (m, 2H,
DMSO); IR (KBr) m
/cmꢀ1: 3410 (m, NH),1740 (s, C@O), 1594,
J = 8.5 Hz, H-200 & H-600), 7.65–7.60 (m, 3H, H-300, H-400 & H-500),
7.45 (d, 2H, J = 8.5 Hz, H-3000 & H-5000), 6.19 (t, 1H, J = 9.25 Hz, H-
1), 5.52 (t, 1H, J = 9.5 Hz, H-3), 5.04 (t, 1H, J = 9.5 Hz, H-2), 5.02 (t,
1H, J = 9.5 Hz, H-4), 4.22–4.20 (m, 2H, H-5 & H-6a), 4.05 (m, 1H,
H-6b), 2.03, 1.99, 1.96, 1.95 (4 ꢂ CH3CO); 13C NMR (DMSO-d6): d
181.35 (C@S), 169.92, 169.58, 169.49, 169.33 (4 ꢂ CH3CO), 165.33
1578, 1526, 1495 (Ar), 1363 (m, C@S),1223 and 1045 (m, C–O–
C); 1H NMR (DMSO-d6): d 12.03 (d, 1H, J = 9.5 Hz, Ha), 11.18 (s,
1H, Hb), 8.35 (s, 1H, H-500), 8.31 (dd, 2H, J = 8.5 Hz, J = 2.0 Hz, H-
2000 & H-6000), 8.28 (d, 2H, J = 9.0 Hz, H-200 & H-600), 7.83 (d, 2H,
J = 9.0 Hz, H-300 & H-500), 7.63 (m, 3H, H-3000, H-4000 & H-5000), 6.19 (t,
1H, J = 9.5 Hz, H-1), 5.52 (t, 1H, J = 9.5 Hz, H-3), 5.05 (t, 1H,
J = 9.5 Hz, H-2), 5.04 (t, 1H, J = 9.5 Hz, H-4), 4.22 (dd, 1H,
J = 14.5 Hz, H-6a), 4.21 (t, 1H J = 9.5 Hz, H-5), 4.05 (dd, 1H
J = 14.5 Hz, H-6b), 2.03, 1.99, 1.96, 1.95 (4s, 12H, 4 ꢂ CH3CO); 13C
NMR (DMSO-d6): d 181.31 (C@S), 169.90, 169.58, 169.48, 169.31
(4C, 4 ꢂ CH3CO), 165.06 (C-40), 163.93 (C-60), 157.48 (C-20),
135.41 (C-1000), 134.72 (C-100), 131.94 (C-300 & C-500), 131.80 (C-4000),
129.46 (C-3000 & C-5000), 128.95 (C-200 & C-600), 127.49 (C-2000 & C-
6000), 125.53 (C-400), 107.60 (C-50), 81.730 (C-1), 72.66 (C-5), 72.17
(C-3), 71.34 (C-2), 67.97 (C-4), 61.79 (C-6), 20.42, 20.38, 20.30,
20.21 (4C, 4 ꢂ CH3CO); EIMS: m/z 714/716 ([M]+Å).
(C-40), 164.83
&
164.09 (JC–F 371.5 Hz, C-4000), 163.34 (C-60),
157.47 (C-20), 135.48 (C-100), 132.09 (C-100), 131.76 (C-100), 130.12
& 130.04 (JC–F 36 Hz, C-2000 & C-6000), 128.97 (C-3000 & C-5000), 127.46
(C-2000 & C-6000), 116.04 & 115.86 (JC–F 86.5 Hz, C-3000 & C-5000),
107.52 (C-50), 81.74 (C-1), 72.66 (C-5), 72.19 (C-3), 71.39 (C-2),
68.01 (C-4), 61.79 (C-6), 20.41, 20.38, 20.30, 20.21 (4 ꢂ CH3CO).
1.3.3. N-(2,3,4,6-Tetra-O-acetyl-b-D
-glucopyranosyl)-N0-[40-(p-
chlorophenyl)-60-phenyl-pyrimidin-20-yl]thiourea (4c)
From 563 mg of 2c and 778 mg of 3. Recrystallized from EtOH-
toluene to yield ivory-white crystals, 912 mg, 68% (procedure A);
1019 mg, 76% (procedure B); mp 218–219 °C; ½a D25
ꢁ
+76.6 (c 1.0,
1.3.6. N-(2,3,4,6-Tetra-O-acetyl-b-D
-glucopyranosyl)-N0-[40-(p-
DMSO); IR (KBr)
m
/cmꢀ1: 3410 (m, NH), 1750 (s, C@O), 1594,
methylphenyl)-60-phenyl-pyrimidin-20-yl]thiourea (4f)
From 522 mg of 2f and 778 mg of 3. Recrystallized from EtOH-
toluene to yield ivory-white crystals, 780 mg, 60% (procedure A);
1578, 1526, 1495 (Ar), 1364 (m, C@S), 1222 and 1045 (m, C–O–
C); 1H NMR (DMSO-d6): d 12.04 (d, 1H, J = 9.0 Hz, Ha), 11.16 (s,
1H, Hb), 8.35 (d, 2H, J = 9.0 Hz, H-200 & H-600), 8.33 (s, 1H, H-50),
8.31 (dd, 2H, J = 8.0 Hz, J = 2.0 Hz, H-2000 & H-6000), 7.69 (d, 2H,
J = 9.0 Hz, H-300 & H-500), 7.63 (dd, 3H, J = 8.0 Hz, J = 7.5 Hz, H-3000,
H-4000 & H-5000), 6.20 (t, 1H, J = 9.0 Hz, H-1), 5.52 (t, 1H, J = 9.5 Hz,
H-3), 5.06 (t, 1H, J = 9.25 Hz, H-2), 5.04 (t, 1H, J = 9.5 Hz, H-4),
4.22 (t, 1H, J = 9.25 Hz, H-5), 4.21 (dd, 1H, J = 10.0 Hz, H-6a), 4.05
(dd, 1H, J = 10.0 Hz, H-6b), 2.03, 1.99, 1.96, 1.95 (4s, 12H,
4 ꢂ CH3CO); 13C NMR (DMSO-d6): d 181.32 (C@S), 169.88, 169.57,
169.47, 169.30 (4C, 4 ꢂ CH3CO), 165.02 (C-40), 163.82 (C-60),
157.46 (C-20), 136.56 (C-400), 135.40 (C-1000), 134.34 (C-100), 131.77
(C-4000), 129.25 (C-300 & C-500), 128.97 (C-200 & C-600), 128.93 (C-3000
& C-5000), 127.47 (C-2000 & C-6000), 107.62 (C-50), 81.17 (C-1), 72.67
(C-5), 72.20 (C-3), 71.38 (C-2), 67.99 (C-4), 61.79 (C-6), 20.39,
20.37, 20.29, 20.21 (4C, 4 ꢂ CH3CO); HREIMS calcd for
C31H3137ClN4O9S: 673.1544, found: 673.5450 [M+H]+Å.
1040 mg, 80% (procedure B); mp 209–210 °C; ½a D25
ꢁ
+56.3 (c 1.0,
DMSO); IR (KBr)
m
/cmꢀ1: 3427 (m, NH),1749 (s, C@O), 1596,
1578, 1529, 1514, 1494 (Ar), 1364 (s, C@S), 1245, 1222 and 1040
(s, C–O–C); 1H NMR (DMSO-d6): d 12.19 (d, 1H, J = 9.0 Hz, Ha),
11.05 (s, 1H, Hb), 8.30 (dd, 2H, J = 8.0 Hz, J = 1.75 Hz, H-2000 & H-
6000), 8.24 (s, 1H, H-5), 8.21 (d, 2H, J = 8.0 Hz, H-200 & H600), 7.60
(m, 3H, H-3000, H-4000 & H-5000), 7.41 (d, 2H, J = 8.0 Hz, H-3 & H-5),
6.2 (t, 1H, J = 9.25 Hz, H-1), 5.54 (t, 1H J = 9.5 Hz, H-3), 5.04 (t,
1H, J = 9.5 Hz, H-2), 5.03 (t, 1H, J = 9.25 Hz, H-4), 4.25–4.20 (m,
2H, H-6a & H-5), 4.07 (dd, 1H, J = 10.5 Hz, J = 3.5 Hz, H-6b), 2.41
(s, 3H, CH3), 2.03, 1.99, 1.98, 1.96 (4s, 12H, 4 ꢂ CH3CO); 13C NMR
(DMSO-d6): d 181.37 (C@S), 169.91, 169.55, 169.48, 169.33 (4C,
4 ꢂ CH3CO), 164.86 (C-40), 164.80 (C-60), 157.50 (C-20), 141.89 (C-
400), 135.57 (C-1000), 132.70 (C-100), 131.46 (C-4000), 129.55 (C-300
&
C-500), 128.92 (C-3000 & C-5000), 127.43 (C-2000 & C-6000), 127.41 (C-200
& C-600), 107.21 (C-50), 99.49 (4-CH3 Ar), 81.78 (C-1), 72.66 (C-5),
72.15 (C-3), 71.48 (C-2), 68.00 (C-4), 61.75 (C-6), 20.99, 20.39,
20.29, 20.20 (4C, 4 ꢂ CH3CO).
1.3.4. N-(2,3,4,6-Tetra-O-acetyl-b-D
-glucopyranosyl)-N0-[40-(m-
chlorophenyl)-60-phenyl-pyrimidin-20-yl]thiourea (4d)
From 563 mg of 2d and 778 mg of 3. Recrystallized from EtOH-
toluene to yield ivory-white crystals, 898 mg, 67% (procedure A);
1.3.7. N-(2,3,4,6-Tetra-O-acetyl-b-D
-glucopyranosyl)-N0-[40-(p-
966 mg, 72% (procedure B); mp 190–191 °C; ½a D25
ꢁ
+79.3 (c 1.0,
isopropylphenyl)-60-phenyl-pyrimidin-20-yl]thiourea (4g)
From 596 mg of 2g and 778 mg of 3. Recrystallized from EtOH-
toluene to yield ivory-white crystals, 922 mg, 68% (procedure A);
DMSO); IR (KBr)
m
/cmꢀ1: 3410 (m, NH),1750 (s, C@O), 1594,
1578, 1526, 1495 (Ar), 1364 (m, C@S),1223 and 1045 (m, C–O–
C); 1H NMR (DMSO-d6): d 12.16 (d, 1H, J = 9.5 Hz, Ha), 11.22 (s,
1071 mg, 79% (procedure B); mp 151–152 °C; ½a D25
ꢁ
+56.3 (c 1.0,
1H, Hb), 8.40 (s, 2H, H-200 & H-5), 8.35–8.32 (m, 3H, H-2000, H-4000
&
DMSO); IR (KBr) m
/cmꢀ1: 3184 (m, NH),1751 (s, C@O), 1594, 1578,
H-6000), 7.70 (m, 1H, H-600), 7.66–7.60 (m, 4H, H-400, H-500 & H-3000,
H-5000), 6.20 (t, 1H, J = 9.5 Hz, H-1), 5.56 (t, 1H, J = 9.5 Hz, H-3),
5.06 (t, 1H, J = 9.5 Hz, H-4), 5.05 (t, 1H, J = 9.5 Hz, H-2), 4.21 (octet,
1H, J = 9.5 Hz, J = 5.0 Hz, J = 2.0 Hz, H-5), 4.22 (dd, 1H, J = 12.5 Hz,
J = 4.75 Hz, H-6a), 4.05 (dd,1H, J = 12.5 Hz, J = 1.75 Hz, H-6b),
2.03, 1.99, 1.96, 1.95 (4s, 12H, 4 ꢂ CH3CO); 13C NMR (DMSO-d6):
d 181.30 (C@S), 169.90, 169.57, 169.45, 169.30 (4C, 4 ꢂ CH3CO),
165.45 (C-40), 163.14 (C-60), 157.46 (C-20), 137.53 (C-300), 135.39
(C-1000), 134.05 (C-100), 131.86 (C-200), 131.38 (C-500), 130.83 (C-4000),
128.95 (C-3000 & C-5000), 127.57 (C-2000 & C-6000), 127.09 (C-600),
126.16 (C-400), 107.81 (C-50), 81.63 (C-1), 72.57 (C-5), 71.88 (C-3),
1526, 1495 (Ar), 1363 (m, C@S),1220 and 1045 (m, C–O–C); 1H
NMR (DMSO-d6): d 12.19 (d, 1H, J = 9.0 Hz, Ha), 11.05 (s, 1H, Hb),
8.31 (dd, 2H, J = 9.0 Hz, J = 1.75 Hz, H-2000 & H-6000), 8.27 (s, 1H, H-
50), 8.26 (d, 2H, J = 8.5 Hz, H-200 & H-600), 7.64–7.60 (m, 3H, H-3000,
H-4000 & H-5000), 7.48 (d, 2H, J = 8.5 Hz, H-300 & H-500), 6.21 (t, 1H,
J = 9.0 Hz, H-1), 5.53 (t, 1H, J = 9.5 Hz, H-3), 5.05 (t, 1H, J = 9.5 Hz,
H-2), 5.05 (t, 1H, J = 9.25 Hz, H-4), 4.23–4.19 (m, 2H, H-5 & H-6a),
4.07 (m, 1H, H-6b), 3.89 (s, 3H, 400-OCH3), 3.02 [septet, 1H,
J = 12.0 Hz, 4000-CH(CH3)2], 2.04, 1.99, 1.96, 1.95 (4 ꢂ CH3CO), 1.28
[d, 6H, J = 12.0 Hz, 4000-CH(CH3)2]; 13C NMR (DMSO-d6): d 181.29
(C@S), 169.77, 169.43, 169.36, 169.22 (4 ꢂ CH3CO), 164.94 (C-40),

2404
N. D. Thanh, N. T. T. Mai / Carbohydrate Research 344 (2009) 2399–2405
164.71 (C-60), 157.45 (C-20), 152.47 (C-400), 135.53 (C-1000), 133.10 (C-
100), 131.55 (C-4000), 128.85 (C-3000 & C-5000), 127.53 (C-300 & C-500),
127.36 (C-2000 & C6000), 126.82 (C-200 & C-600), 107.27 (C-50), 81.75
(C-1), 72.59 (C-5), 72.47 (C-3), 72.13 (C-2), 67.96 (C-4), 61.69 (C-
6), 33.29 [4000-CH(CH3)2], 23.45 [4000-CH(CH3)2], 20.29, 20.28, 20.20,
20.12 (4 ꢂ CH3CO).
(d, 2H, J = 9.5 Hz, H-2 & H-4), 4.24 (ddd, 1H, J = 12.0 Hz, J = 2.5 Hz,
J = 2.0 Hz, H-6a), 4.19 (dd, 1H, J = 12.0 Hz, J = 5.0 Hz, H-5), 4.07
(dd, 1H, J = 12.0 Hz, J = 2.0 Hz, H-6b), 3.92 (s, 3H, OCH3), 2.04,
1.99, 1.950, 1.94 (4s, 12H, 4 ꢂ CH3CO); 13C NMR (DMSO-d6): d
181.24 (C@S), 169.79, 169.41, 169.34, 169.23 (4C, 4 ꢂ CH3CO),
165.08 (C-40), 164.56 (C-60), 159.82 (C-20), 157.39 (C-300), 136.87
(C-100), 135.48 (C-1000), 131.62 (C-500), 129.99 (C-4000), 128.47 (C-3000
& C-5000), 127.45 (C-2000 & C-6000), 119.80 (C-600), 117.28 (C-400),
112.80 (C-200), 107.67 (C-50), 81.70 (C-1), 72.57 (C-5), 71.97 (C-3),
71.54 (C-2), 68.01 (C-4), 61.70 (C-6), 55.34 (CH3O-Ar), 20.29,
20.27, 20.17, 20.08 (4C, 4 ꢂ CH3CO).
1.3.8. N-(2,3,4,6-Tetra-O-acetyl-b-D
-glucopyranosyl)-N0-[40-(o-
hydroxyphenyl)-60-phenyl-pyrimidin-20-yl]thiourea (4h)
From 526 mg of 2h and 778 mg of 3. Recrystallized from EtOH-
toluene to yield ivory-white crystals, 782 mg, 60% (procedure A);
1043 mg, 80% (procedure B); mp 248–249 °C; ½a D25
ꢁ
+76.3 (c 1.0,
DMSO); IR (KBr)
m
/cmꢀ1: 3585 (m, NH), 1754 (s, C@O), 1597,
Acknowledgement
1530, 1495 (Ar), 1368 (m, C@S), 1222 and 1059 (m, C–O–C); 1H
NMR (DMSO-d6): d 12.12 (d, 1H, J = 9.5 Hz, Ha), 11.85 (s, 1H, Hb),
11.83 (s, 1H, OH), 8.34 (s, 1H, H-50), 8.31 (dd, 1H, J = 8.5 Hz,
J = 1.5 Hz, H-600), 8.24–8.23 (m, 2H, H-3000 & H-5000), 7.68–7.62 (m,
3H, H-2000, H-4000 & H-6000), 7.55 (td, 1H, J = 8.0 Hz, J = 1.5 Hz, H-400),
7.02 (d, 1H, J = 7.5 Hz, H-500), 7.00 (d, 1H, J = 8.0 Hz, H-300), 6.20 (t,
1H, J = 9.25 Hz, H-1), 5.52 (t, 1H J = 9.5 Hz, H-3), 5.02 (m, 2H, H-2
& H-4), 4.23–4.18 (m, 2H, H-5 & H-6a), 4.05 (m, 1H, H-6b), 2.03,
2.00, 1.98, 1.95 (4s, 12H, 4 ꢂ CH3CO); 13C NMR (DMSO-d6): d
181.37 (C@S), 169.90, 169.51, 169.46, 169.31 (4C, 4 ꢂ CH3CO),
166.13 (C-40), 163.55 (C-60), 159.22 (C-20), 155.91 (C-200), 135.48
(C-1000), 133.68 (C-600), 131.77 (C-400), 129.14 (C-4000), 129.07 (C-3000
& C-5000), 127.37 (C-2000 & C-6000), 119.22 (C-500), 118.36 (C-100),
117.93 (C-300), 107.15 (C-50), 81.63 (C-1), 72.61 (C-5), 72.15 (C-3),
71.42 (C-2), 67.96 (C-4), 61.73 (C-6), 20.40, 20.36, 20.28, 20.20
(4 ꢂ CH3CO).
Financial support for this work was provided by Scientific Re-
search Fund-Hanoi National University (Grant QGTD.08.03).
Supplementary data
Supplementary data associated with this article can be found, in
the online version, at doi:10.1016/j.carres.2009.09.002.
References
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1.3.9. N-(2,3,4,6-Tetra-O-acetyl-b-D
-glucopyranosyl)-N0-[40-(p-
methoxyphenyl)-60-phenyl-pyrimidin-20-yl]thiourea (4i)
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ꢁ
+84.0 (c 1.0,
DMSO); IR (KBr)
m
/cmꢀ1: 3434 (m, NH), 1750 (s, C@O), 1594,
1578, 1526, 1495 (Ar), 1364 (m, C@S), 1223 and 1045 (m, C–O–
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164.68 (C-40), 164.38 (C-60), 162.26 (C-20), 157.49 (C-400), 135.66
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106.74 (C-50), 81.71 (C-1), 72.59 (C-5), 72.11 (C-3), 71.48 (C-2),
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