Synthesis of some N-galactosides of 3-aryl-5-benzyl (or substituted benzyl)-1,2,4-triazin-6(1H)-/ones or thiones of expected biological activity

Article abstract of DOI:10.1081/NCN-120023275

The 1-(2,3,4,6-tetra-O-acetyl-β-D-galactopyranosyl)-3-aryl-5-benzyl (or substituted benzyl)-1,2,4-triazin-6(1H)-/ones or thiones were prepared via galactosidation of 3-aryl-5-benzyl (or substituted benzyl)-1,2,4-triazin-6(1H)-/ones or thiones with 2,3,4,6-tetra-O-acetyl-α -D-galactopyranosyl bromide. The structure of the new galactosyl derivatives was based on both spectroscopic and chemical evidences.

Full text of DOI:10.1081/NCN-120023275

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Synthesis of Some N-Galactosides of 3-Aryl-5-benzyl
(or Substituted Benzyl)-1,2,4-triazin-6(1H)-/ones or
Thiones of Expected Biological Activity
Abdel Kader Mansour a c , Mohga M. Eid a & Nasser S. A. M. Khalil b
a Department of Chemistry , Faculty of Science , Cairo University , Giza, Egypt
b Central Laboratory for Food and Feed , Agricultural Research Center , Giza, Egypt
c Department of Chemistry , Faculty of Science , Cairo University , Giza, Egypt
Published online: 07 Feb 2007.
To cite this article: Abdel Kader Mansour , Mohga M. Eid & Nasser S. A. M. Khalil (2003) Synthesis of Some N-Galactosides
of 3-Aryl-5-benzyl (or Substituted Benzyl)-1,2,4-triazin-6(1H)-/ones or Thiones of Expected Biological Activity, Nucleosides,
Nucleotides and Nucleic Acids, 22:9, 1825-1833, DOI: 10.1081/NCN-120023275
To link to this article: http://dx.doi.org/10.1081/NCN-120023275
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NUCLEOSIDES, NUCLEOTIDES & NUCLEIC ACIDS
Vol. 22, No. 9, pp. 1825–1833, 2003
Synthesis of Some N-Galactosides of 3-Aryl-5-benzyl
(or Substituted Benzyl)-1,2,4-triazin-6(1H)-=ones
or Thiones of Expected Biological Activity
1
Abdel Kader Mansour,1, Mohga M. Eid,
*
and Nasser S. A. M. Khalil2
1Department of Chemistry, Faculty of Science,
Cairo University, Giza, Egypt
2Central Laboratory for Food and Feed,
Agricultural Research Center,
Giza, Egypt
ABSTRACT
The 1-(2,3,4,6-tetra-O-acetyl-b-d-galactopyranosyl)-3-aryl-5-benzyl (or substituted
benzyl)-1,2,4-triazin-6(1H)-=ones or thiones were prepared via galactosidation
of 3-aryl-5-benzyl (or substituted benzyl)-1,2,4-triazin-6(1H)-=ones or thiones
with 2,3,4,6-tetra-O-acetyl-a-d-galactopyranosyl bromide. The structure of the
new galactosyl derivatives was based on both spectroscopic and chemical evi-
dences.
Key Words: Synthesis; 1,2,4-Triazines; N-Galactosides.
*Correspondence: Abdel Kader Mansour, Department of Chemistry, Faculty of Science,
Cairo University, Giza, Egypt.
1825
DOI: 10.1081/NCN-120023275
Copyright # 2003 by Marcel Dekker, Inc.
1525-7770 (Print); 1532-2335 (Online)
www.dekker.com

1826
Mansour, Eid, and Khalil
INTRODUCTION
The reported biological activity of N-glycosides of 1,2,4-triazines (cytotoxics,
antivirals, enzyme inhibitors, immunosuppressives, antipsoriatics, bacteriostatics,
antitumors, as well as floor and wall disinfectants)[1–8] together with the fact that
2-(2,3,4,6-tetra-O-acetyl-b-d-galactopyranosyl)-6-benzyl-1,2,4-triazine-3,5-(2H,4H)-
dithione (1)[9] has shown anticancer activity against both MCF7 (Breast) and SF-268
(CNS) cell lines through a primary human anticancer screening (in vitro), prompted
us to study the synthesis of 1-galactosyl derivatives of some 1,2,4-triazin-6(1H)-=
ones and or thiones of expected interesting biolgical activity.
RESULTS AND DISCUSSION
Recently, an efficient procedure was described for the selective synthesis of N-gly-
cosyl derivatives of 3-thioxo-1,2,4-triazin-5(4H )-ones. This involves the reaction of the
appropriate 1,2,4-triazine derivative with the appropriate protected glycosyl halide in
basic medium (acetone=KOH or DMF=TEA or CH3CN=TEA).[9–15] Previously, Eid
et al.[12] reported that N-1 glucosidation takes place upon treatment of 3-phenyl-
5-benzyl (or substituted benzyl)-1,2,4-triazine-6(1H)-thiones with 2,3,4,6-tetra-O-
acetyl-a-d-glucopyranosyl bromide in aqueous acetone containing one equivalent of
potassium hydroxide to give the corresponding 1-(2,3,4,6-tetra-O-acetyl-b-d-gluco-
pyranosyl)-3-phenyl-5-benzyl (or substituted benzyl)-1,2,4-triazine-6(1H)-thiones.
We report here the results of our study for the reaction of 3-phenyl-5-benzyl (or
substituted benzyl)-1,2,4-triazin-6(1H)-=ones 4a–f or thiones 2a–d with 2,3,4,6-tetra-
O-acetyl-a-d-galactopyranosyl bromide (3) (Sch. 1). Thus, galactosidation of each
of 4a–f or 2a–d with compound 3 in N,N-dimethylformamide containing triethyl-
amine gave the corresponding 1-(2,3,4,6-tetra-O-acetyl-b-d-galactopyranosyl)-
3-phenyl-5-benzyl (or substituted benzyl)-1,2,4-triazin-6(1H)-=ones 6a–f or thiones

Synthesis of Some N-Galactosides
1827
Scheme 1.
7a–d, respectively. The structures assigned for compounds 6a–f, 7a–d were deduced
from the following facts:
1
(1) The b-configuration of compounds 6a–f, 7a–d is supported by their H
NMR spectra which revealed the anomeric proton at d 6.68–6.02 with
a coupling constant of 8.2–10.6 Hz consistent with similar reported
data.[9–15]
(2) The IR spectra of compounds 6a–f showed the amide carbonyl function at
1705–1666 cmꢀ1, which excludes the formation of the isomeric 3-O-galacto-
syl derivatives 5a–f.
(3) Thiation of compounds 6a–d gave the 6(1H)-thiones 7a–d.
The biological screening of the new compounds obtained in this work is still
under investigation.

1828
Mansour, Eid, and Khalil
EXPERIMENTAL
All melting points are uncorrected. IR spectra were recorded on a Perkin-Elmer
1430 spectrophotometer. 1H NMR spectra were recorded at 200 MHz with a Varian
GEMINI 200 spectrometer. Mass spectra (EI, 70eV) were recorded on a GCMS-QP
1000 EX spectrometer. Elemental analyses were carried out at the Microanalytical
Centre, Cairo University. The starting 3-phenyl-5-benzyl (or substituted benzyl)-
1,2,4-triazin-6(1H)-ones 4a–d were prepared as described by Nalepa et al.[16,17] on
the other hand, the new 3-phenyl-5-(3,4-dimethylbenzyl)-1,2,4-triazin-6(1H)-one
(4e) and 3-phenyl-5-(4-N,N-dimethylaminobenzyl)-1,2,4-triazin-6(1H)-ones (4f) are
now synthesized using the same procedure. The starting 3-phenyl-5-benzyl (or sub-
stituted benzyl)-1,2,4-triazine-6(1H)-thiones 2a–d[12] and 2,3,4,6-tetra-O-acetyl-a-d-
galactopyranosyl bromide[18] were prepared as reported.
3-Phenyl-5-(3,4-dimethylbenzyl)-1,2,4-triazin-6(1H)-one (4e). A suspension of
4-(3,4-dimethylbenzylidene)-2-phenyl-oxazol-5(4H)-one (12.3 g, 44.4 mmol) and hydra-
zine hydrate 99% (16 mL) in cold methanol (100 mL) was shaken till a clear solution
was obtained. After the reaction mixture started to become turbid, it was allowed to
stand at room temperature overnight. The formed colorless precipitate of the corre-
sponding hydrazide was collected by filtration, dried, (11.0 g, mp. 195–6ꢁC), then
heated at reflux in sodium hydroxide solution (4.4 g NaOH dissolved in 110 mL water)
for 5 min. The reaction mixture was cooled, acidified with concentrated hydrochloric
acid, and diluted with an ice-water mixture. After collection of the formed colorless
product by filtration, it was recrystallized from methanol to give colorless crystals of
1
4e (90%); mp. 180ꢁC; IR (KBr) 3125 (NH), 1659 (C ¼ O amide) cmꢀ1; H NMR
(CDCl3) d 11.8 (brs, 1H, NH, exchangeable), 8.09–6.96 (m, 8H, ArH’s), 4.26 (s, 2H,
3,4-(CH3)2-C6H3-CH2), 2.42, 2.29 (2s, 6H, 3,4(CH3)2-C6H3-CH2).
Anal. Calcd. for C18H17N3O: C, 74.2; H, 5.88; N, 14.42. Found: C, 74.2; H, 5.9;
N, 14.3.
3-Phenyl-5-(4-N,N-dimethylaminobenzyl)-1,2,4-triazin-6(1H)-one (4f). A sus-
pension of 4-(4-N,N-dimethylaminobenzylidene)-2-phenyl-oxazol-5(4H)-one (19.5 g,
66.8 mmol) and hydrazine hydrate 99% (17 mL) in cold methanol (100 mL) was
shaken till a clear solution was obtained. After the reaction mixture started to
become turbid, it was allowed to stand at room temperature overnight. The formed
pale yellow precipitate of the corresponding hydrazide was collected by filtration,
dried (16.5 g, mp. 188ꢁC), then it was heated at reflux in aqueous sodium hydroxide
solution (6.7 g NaOH dissolved in 167.5 mL water) for 5 min. The reaction mixture
was cooled, acidified with concentrated hydrochloric acid, and diluted with an ice-
water mixture. After collection of the formed precipitate by filtration, it was recrys-
tallized from methanol to give orange-yellow crystals of 4f (74%); mp. 320ꢁ C; IR
1
(KBr) 3421 (NH), 1655 (C¼O amide) cmꢀ1; HNMR (DMSO-d6) d 13.42 (s, 1H,
NH, exchangeable), 8.04–6.64 (m, 9 H, ArH’s), 4.0 (s, 2 H, 4-N(CH3)2-C6H4-CH2),
2.82 (s, 6H, 4-N(CH3)2-C6H4-CH2).
Anal. Calcd. for C18H18N4O: C, 70.57; H, 5.92; N, 18.29. Found: C, 70.6; H,
5.8; N, 18.4.

Synthesis of Some N-Galactosides
1829
1-(2,3,4,6-Tetra-O-acetyl-b-D-galactopyranosyl)-3-phenyl-5-benzyl (or substituted
benzyl)-1,2,4-triazin-6(1H)-ones 6a–f. General procedure: To a solution of each
of 4a–f (10 mmol) in N,N-dimethylformamide (5 mL) and triethylamine (2 mL,
14 mmol) was added 2,3,4,6-tetra-O-acetyl-a-d-galactopyranosyl bromide (3) (4.1 g,
10 mmol). The reaction mixture was shaken for 20 min and kept overnight at room
temperature. The mixture was cooled, acidified with acetic acid (1 mL), and diluted
with water. The precipitate was then collected by filtration, washed with water, and
dried at room temperature. Compounds 6a–f were extracted with ethyl acetate and
purified by preparative TLC (silica gel 60 GF254) using ethyl acetate as an eluent.
After extraction with chloroform on a soxhlet extractor, the chloroform extracts
of these products were then concentrated and diluted with petroleum ether (bp.
40–60ꢁC). The crude 6a–f were collected by filtration, dried at room temperature,
then recrystallized from diethyl ether=petroleum ether (bp. 40–60ꢁC) to give pale
yellow crystals of 6a–e and orange-yellow crystals of 6f.
1-(2,3,4,6-Tetra-O-acetyl-b-D-galactopyranosyl)-3-phenyl-5-benzyl-1,2,4-triazin-6(1H)-
one (6a). Using the general procedure, 4a gave 6a (45%); Rf ¼ 0.74; mp. 70ꢁC; IR (KBr)
1751 (C¼O acetate), 1674 (C¼O amide) cmꢀ1; MS m=z 594 (Mþ); 1H NMR (CDCl3) d
0
0
0
8.15–7.14 (m, 10H, ArH’s), 6.15 (d, 1H, JH-1 -H-2 ¼ 8.2 Hz, H-1 ), 5.84 (t, 1H, J¼
0
0
0
0
0
0
0
0
(JH-2 -H-1 þ JH-2 -H-3 )=2¼ 9.2 Hz, H-2 ), 5.44 (d, 1H, JH-4 -H-3 ¼ 3.2 Hz, H-4 ), 5.1 (dd,
0
0
0
00
0
0
0
0
1H, JH-3 -H-4 ¼ 3.4 Hz, JH-3 -H-2 ¼ 10.2 Hz, H-3 ), 4.4–4.08 (m, 3H, H-5 , H-6 , H-6 ), 4.27
(s, 2H, CH2Ph), 2.17–1.96 (4s, 12H, CH3CO).
Anal. Calcd. for C30H31N3O10: C, 60.70; H, 5.26; N, 7.08. Found: C, 60.7; H,
5.1; N, 7.2.
1-(2,3,4,6-Tetra-O-acetyl-b-D-galactopyranosyl)-3-phenyl-5-(4-methylbenzyl)-1,2,4-
triazin-6(1H)-one (6b). Using the general procedure, 4b gave 6b (40%); Rf ¼
0.75; mp. 80ꢁC; IR (KBr) 1751 (C¼O acetate), 1682 (C¼O amide) cmꢀ1
;
1H
0
0
0
NMR (CDCl3) d 8.45–6.9 (m, 9H, ArH’s), 6.22 (d, 1H, JH-1 -H-2 ¼ 8.2 Hz, H-1 ),
0
0
0
0
0
0
0
5.82 (t, 1H, J ¼ (JH-2 -H-1 þ JH-2 -H-3 ) =2 ¼ 9.0 Hz, H-2 ), 5.45 (d, 1H, JH-4 -H-3
¼
3.2 Hz, H-40), 5.14 (dd, 1H, JH-3 -H-4 ¼ 3.4 Hz, JH-3 -H-2 ¼ 10.1 Hz, H-3 ), .4.3–3.9
(m, 3H, H-50, H-60, H-60), 4.18 (s, 2H, 4-CH3C6H4CH2), 2.32 (s, 3H, CH3), 2.21–
1.99 (4s, 12H, CH3CO).
0
0
0
0
0
Anal. Calcd. for C31H33N3O10.: C, 61.28; H, 5.47. Found: C, 61.4; H, 5.6.
1-(2,3,4,6-Tetra-O-acetyl-b-D-galactopyranosyl)-3-phenyl-5-(4-methoxybenzyl)-1,2,4-
triazin-6(1H)-one (6c). Using the general procedure, 4c gave 6c (47%); Rf ¼ 0.70;
1
mp. 108ꢁC; IR (KBr) 1751 (C¼O acetate), 1674 (C¼O amide) cmꢀ1; H0 NMR
0
0
(CDCl3) d 8.3–6.87 (m, 9H, ArH’s), 6.68 (d, 1H, JH-1 -H-2 ¼ 8.2 Hz, H-1 ), 5.92
0
0
0
0
0
0
0
(t, 1H, J ¼ (JH-2 -H-1 þ JH-2 -H-3 )=2 ¼ 9.1 Hz, H-2 ), 5.48 (d, 1H, JH-4 -H-3 ¼ 3.4 Hz,
H-40), 5.14 (dd, 1H, JH-3 -H-4 ¼ 3.5 Hz, JH-3 -H-2 ¼ 10.0 Hz, H-3 ), 4.2-3.9 (m, 3H,
H-50, H-60, H-60), 3.89 (s, 2H, 4-CH3OC6H4CH2), 3.78 (s, 3H, OCH3), 2.15-2.0
(4s, 12H, CH3CO).
0
0
0
0
0
Anal. Calcd. for C31H33N3O11: C, 59.71; H, 5.33. Found: C, 59.5; H, 5.3.

1830
Mansour, Eid, and Khalil
1-(2,3,4,6-Tetra-O-acetyl-b-D-galactopyranosyl)-3-phenyl-5-(4-chlorobenzyl)-1,2,4-
triazin-6(1H)-one (6d). Using the general procedure, 4d gave 6d (48%); Rf ¼ 0.73; mp.
100ꢁC; IR (KBr) 1751 (C¼O acetate), 1666 (C¼O amide) cmꢀ1; 1H NMR (CDCl3) d
0
0
0
0
8.22–7.15 (m, 9H, ArH’s), 6.02 (d, 1H, JH-1 -H-2 ¼ 8.2 Hz, H-1 ), 5.8 (t, 1H,mJ ¼ (JH-2 -
0
0
0
0
0
0
H-10
þ JH-2 -H-3 )=2 ¼ 9.0 Hz, H-2 ), 5.48 (d, 1H, JH-4 -H-3 ¼ 3.2 Hz, H-4 ), 5.17 (dd, 1H,
0
0
0
00
0
0
0
0
JH-3 -H-4 ¼ 3.4 Hz, JH-3 -H-2 ¼ 10.2 Hz, H-3 ), 4.24–3.96 (m, 3H, H-5 , H-6 , H-6 ), 4.24
(s, 2H, 4-ClC6H4CH2), 2.2–1.98 (4s, 12H, CH3CO).
Anal. Calcd. for C30H30N3O10Cl: C, 57.37; H, 4.81. Found: C, 57.4; H, 4.7.
1-(2,3,4,6-Tetra-O-acetyl-b-D-galactopyranosyl)-3-phenyl-5-(3,4-dimethylbenzyl)-
1,2,4-triazin-6(1H)-one (6e). Using the general procedure, 4e gave 6e (63%);
1
Rf ¼ 0.71; mp. 84ꢁC; IR (KBr) 1751 (C¼O acetate), 1682 (C¼O amide) cmꢀ1; H
0
0
0
NMR (CDCl3) d 8.34–6.9 (m, 8H, ArH’s), 6.21 (d, 1H, JH-1 -H-2 ¼ 9 Hz, H-1 ), 6.1
0
0
0
0
0
0
0
(t, 1H, J ¼ (JH-2 -H-1 þ JH-2 -H-3 )=2 ¼ 9.2 Hz, H-2 ), 5.5 (d, 1H, JH-4 -H-3 ¼ 3.2 Hz,
H-40), 5.2 (dd, 1H, JH-3 -H-4 ¼ 3.4 Hz, JH-3 -H-2 ¼ 10.0 Hz, H-3 ), 4.24–4.00 (m, 5H,
0
0
0
0
0
H-50, H-60, H-600, 4-(CH3) C6H3CH2), 2.72, 2.39 (2s, 6H, 3,4-(CH3) C6H3CH2),
2.39–1.96 (4s, 12H, CH3CO).
2
2
Anal. Calcd. for C32H35N3O10: C, 61.83; H, 5.67; N, 6.76. Found: C, 62.0;
H, 5.7; N, 6.8.
1-(2,3,4,6-Tetra-O-acetyl-b-D-galactopyranosyl)-3-phenyl-5-(4-N,N-dimethylamino-
benzyl)-1,2,4-triazin-6(1H)-one (6f). Using the general procedure, 4f gave 6f (58%);
1
Rf ¼ 0.71; mp. 78ꢁC; IR (KBr) 1751 (C¼O acetate), 1705 (C¼O amide) cmꢀ1; H
0
0
0
NMR (DMSO-d6) d 8.06–6.69 (m, 9H, ArH’s), 6.58 (d, 1H, JH-1 -H-2 ¼ 9 Hz, H-1 ),
0
0
0
0
0
0
0
5.9 (t, 1H, J ¼ (JH-2 -H-1 þ JH-2 -H-3 )=2 ¼ 9.6 Hz, H-2 ), 5.61 (d, 1H, JH-4 -H-3 ¼ 3.1 Hz,
H-40), 5.3 (dd, 1H, JH-3 -H-4 ¼ 3.4 Hz, JH-3 -H-2 ¼ 10.1 Hz, H-3 ), 4.2–3.9 (m, 5H, H-5 ,
H-60, H-600), 4-(CH3) 2NC6H4CH2), 3.08 (s, 6H, 4-(CH3) 2NC6H4CH2), 2.14–1.92 (4s,
12H, CH3CO).
0
0
0
0
0
0
Anal. Calcd. for C32H36N4O10: C, 60.37; H, 5.70; N, 8.80. Found: C, 60.4; H,
5.6; N, 8.7.
1-(2,3,4,6-Tetra-O-acetyl-b-D-galactopyranosyl)-3-phenyl-5-benzyl (or substituted
benzyl)-1,2,4-triazine-6(1H)-thiones 7a–d. General Procedure (A): 2a–d (10 mmol)
in N,N-dimethylformamide (5 mL) and triethylamine (2 mL, 14 mmol) was added
2,3,4,6-tetra-O-acetyl-a-d-galactopyranosyl bromide (3) (4.1 g, 10 mmol). The reac-
tion mixture was shaken for 20 min and kept overnight at room temperature. The
mixture was cooled, acidified with acetic acid (1 mL), and diluted with water. The
precipitate was collected by filtration, washed several times with water, dried at
ambient temperature, extracted with ethyl acetate, and purified by preparative
TLC (silica gel 60 GF254) using ethyl acetate as an eluent. The products were then
extracted with chloroform on a soxhlet extractor, and the chloroform extracts of
these products were then concentrated and diluted with petroleum ether (bp. 40–
60ꢁC). After collection of the crude products by filtration, they were recystallized
from diethyl ether=petroleum ether (bp. 40–60ꢁC) to give yellow crystals of 7a–d.
General Procedure (B): To a solution of each of 6a–d (10 mmol) in dry pyridine
(5 mL) was added phosphorous pentasulfide (0.45 g, 2 mmol). The reaction mixture

Synthesis of Some N-Galactosides
1831
was heated at reflux for 6 h. After cooling, the products were extracted from the oily
materials with ethanol (10 mL). The supernatant solutions were decanted, acidified
with acetic acid (0.5 mL), concentrated, and diluted with water. The precipitates were
collected by filtration, dried at room temperature, dissolved in diethyl ether and
treated with charcoal (0.5 g), filtered, and the filtrates evaporated at room tempera-
ture. The resulting solids were recystallized from diethyl ether=petroleum ether
(bp. 40–60ꢁC) to give yellow crystals of 7a–d.
1-(2,3,4,6-Tetra-O-acetyl-b-D-galactopyranosyl)-3-phenyl-5-benzyl-1,2,4-triazine-
6(1H)-thione (7a). Using the general procedure (A=or B), 2a=or 6a gave 7a
(62%=or 50%); mp. 140ꢁC; IR (KBr) 1751 (C¼O acetate) cmꢀ1; MS m=z 610 (Mþ);
1H NMR (CDCl3) d 8.52–6.95 (m, 10H, ArH’s), 6.2 (d, 1H, JH-1 -H-2 ¼ 9 Hz, H-1 ),
0
0
0
0
0
0
0
0
0
0
5.95 (t, 1H, J ¼ (JH-2 -H-1 þ JH-2 -H-3 )=2 ¼ 9.6 Hz, H-2 ), 5.5 (d, 1H, JH-4 -H-3 ¼ 3.4 Hz,
0
H-40), 5.25 (dd, 1H, JH-3 -H-4 ¼ 3.4 Hz, JH-3 -H-2 ¼ 10.1 Hz, H-3 ), 4.25–3.9 (m,
3H, H-50, H-60, H-600), 3.85 (s, 2H, CH2Ph), 2.23–1.97 (4s, 12H, CH3CO).
Anal. Calcd. for C30H31N3O9S: C, 59.10; H, 5.12; N, 6.89. Found: C, 59.3;
H, 5.2; N, 7.0.
0
0
0
0
1-(2,3,4,6-Tetra-O-acetyl-b-D-galactopyranosyl)-3-phenyl-5-(4-methylbenzyl)-1,2,4-
triazine-6(1H)-thione (7b). Using the general procedure (A=or B), 2b=or 6b gave
7b (53% =or 48%); mp. 190ꢁC; IR (KBr) 1751 (C¼O acetate) cmꢀ1
;
1H NMR
0
0
0
(CDCl3) d 8.5–6.95 (m, 9H, ArH’s), 6.2 (d, 1H, JH-1 -H-2 ¼ 9 Hz, H-1 ), 6.0 (t, 1H,
0
0
0
0
0
0
0
0
0
J ¼ (JH-2 -H-1 þ JH-2 -H-3 )=2 ¼ 9.5 Hz, H-2 ), 5.51 (d, 1H, JH-4 -H-3 ¼ 3.2 Hz, H-4 ),
0
0
0
0
0
0
5.2 (dd, 1H, JH-3 -H-4 ¼ 3.5 Hz, JH-3 -H-2 ¼ 10.1 Hz, H-3 ), 4.2–4.0 (m, 3H, H-5 , H-6 ,
H-600), 3.85 (s, 2H, 4-CH3C6H4CH2), 2.28 (s, 3H, 4-CH3C6H4CH2), 2.2–1.95 (4s,
12H, CH3CO).
Anal. Calcd. for C31H33N3O9S: C, 59.70; H, 5.33; N, 6.74. Found: C, 59.6; H,
5.2; N, 6.6.
1-(2,3,4,6-Tetra-O-acetyl-b-D-galactopyranosyl)-3-phenyl-5-(4-methoxybenzyl)-1,2,4-
triazine-6(1H)-thione (7c). Using the general procedure (A=or B), 2c=or 6c gave 7c
(60% = or 52%); mp. 140ꢁC; IR (KBr) 1751 (C¼O acetate) cmꢀ1; 1H NMR (CDCl3)
0
0
0
d 8.5–6.99 (m, 9H, ArH’s), 6.19 (d, 1H, JH-1 -H-2 ¼ 10.6 Hz, H-1 ), 5.99 (t, 1H,
0
0
0
0
0
0
0
0
J ¼ (JH-2 -H-1 þ JH-2 -H-3 )=2 ¼ 9.7 Hz, H-2 ), 5.49 (d, 1H, JH-4 -H-3 ¼ 3.4 Hz, H-4 ),
0
0
0
0
0
0
5.19 (dd, 1H, JH-3 -H-4 ¼ 3.4 Hz, JH-3 -H-2 ¼ 10.1 Hz, H-3 ), 4.20–3.92 (m, 3H, H-5 ,
H-60, H-600), 3.85 (s, 2H, 4-CH3OC6H4CH2), 3.76 (s, 3H, OCH3), 2.18–1.98 (4s,
12H, CH3CO).
Anal. Calcd. for C31H33N3O10S: C, 58.21; H, 5.2. Found: C, 58.3; H, 5.2.
1-(2,3,4,6-Tetra-O-acetyl-b-D-galactopyranosyl)-3-phenyl-5-(4-chlorobenzyl)-1,2,4-
triazine-6(1H)-thione (7d). Using the general procedure (A=or B), 2d=or 6d gave
7d (85%=or 50%); mp. 150ꢁC; IR (KBr) 1751 (C¼O acetate) cmꢀ1
;
1H NMR
0
0
0
(CDCl3) d 8.4–7.0 (m, 9H, ArH’s), 6.22 (d, 1H, JH-1 -H-2 ¼ 9 Hz, H-1 ), 5.96
0
0
0
0
0
0
0
(t, 1H, J ¼ (JH-2 -H-1 þ JH-2 -H-3 )=2 ¼ 9.6 Hz, H-2 ), 5.51 (d, 1H, JH-4 -H-3 ¼ 3.4 Hz,
H-40), 5.22 (dd, 1H, JH-3 -H-4 ¼ 3.5 Hz, JH-3 -H-2 ¼ 10.2 Hz, H-3 ), 4.22–4.0 (m,
0
0
0
0
0
3H, H-50, H-60, H-600), 3.85 (s, 2H, 4-ClC6H4CH2), 2.22–1.94 (4s, 12H, CH3CO).

1832
Mansour, Eid, and Khalil
Anal. Calcd. for C30H30N3O9SCl: C, 55.94; H, 4.69; N, 6.52. Found: C, 56.1;
H, 4.7; N, 6.4.
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Synthesis of Some N-Galactosides
1833
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Received December 31, 2002
Accepted April 10, 2003