Selective synthesis and reactions of 6-substituted-2-β-galactosyl-1,2,4-triazines of potential anticancer activity

Article abstract of DOI:10.1081/NCN-120018621

Selective synthesis and reactions of different 6-substituted-2-β-D-galactosyl-3-thioxo-2,3-dihydro-1,2, 4-triazin-5(4H)-ones using the developed amino or aryl protecting group strategy were investigated. Primary human anticancer screening of twelve selected compounds (in vitro) resulted in an active compound against both MCF7 (Breast) and SF-268(CNS) cell lines.

Full text of DOI:10.1081/NCN-120018621

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Selective Synthesis and Reactions of 6-Substituted-
2-β-galactosyl-1,2,4-triazines of Potential Anticancer
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 Centre , 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) Selective Synthesis and Reactions
of 6-Substituted- 2-β-galactosyl-1,2,4-triazines of Potential Anticancer Activity, Nucleosides, Nucleotides and Nucleic Acids,
22:1, 21-44, DOI: 10.1081/NCN-120018621
To link to this article: http://dx.doi.org/10.1081/NCN-120018621
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NUCLEOSIDES, NUCLEOTIDES & NUCLEIC ACIDS
Vol. 22, No. 1, pp. 21–44, 2003
Selective Synthesis and Reactions of 6-Substituted-
2-b-galactosyl-1,2,4-triazines of Potential
Anticancer Activity
1
2
Abdel Kader Mansour,1, Mohga M. Eid, and Nasser S. A. M. Khalil
*
1Department of Chemistry, Faculty of Science, Cairo University, Giza, Egypt
2Central Laboratory for Food and Feed, Agricultural Research Centre,
Giza, Egypt
ABSTRACT
Selective synthesis and reactions of different 6-substituted-2-b-D-galactosyl-3-
thioxo-2,3-dihydro-1,2,4-triazin-5(4H)-ones using the developed amino or aryl
protecting group strategy were investigated. Primary human anticancer screening
of twelve selected compounds (in vitro) resulted in an active compound against
both MCF7 (Breast) and SF-268(CNS) cell lines.
Key Words: Synthesis; 1,2,4-Triazines; Galactosides; Anticancer activity.
INTRODUCTION
During the last five decades, extensive chemical and biological studies of N-
glycosides of 1,2,4-triazine-3,5-(2H, 4H)-diones (6-azauridine derivatives and their
3-thiones have been stimulated mainly by their cytotoxic, antiviral, enzyme inhibiting,
immunosuppressive, antiphlogestic, antipsoriatic, therapeutic, bacteriostatic and
*Correspondence: Abdel Kader Mansour, Department of Chemistry, Faculty of Science,
Cairo University, Giza, Egypt; E-mail: clff@intouch.com.
21
DOI: 10.1081/NCN-120018621
Copyright # 2003 by Marcel Dekker, Inc.
1525-7770 (Print); 1532-2335 (Online)
www.dekker.com

22
Mansour, Eid, and Khalil
antitumor activity.[1–7] Also, N-glycosyl derivatives of 3-substitiuted-1,2,4-triazin-
5(2H)-ones were reported to be useful as floor and wall disinfectants.[8] Moreover,
some glycosides of 6-vinyl-1,2,4-triazines were shown to exhibit antiviral activity.[9,10]
All these facts prompted us to selectively synthesize some new 2-b-D-galactosyl deri-
vatives of different 6-substituted-1,2,4-triazines of promising biological activity.
RESULTS AND DISCUSSION
Direct glycosidation of 4-amino-3-thioxo-2,3-dihydro-1,2,4-triazin-5(4H)-ones
followed by deamination was reported to offer a convenient selective synthesis of the
2-glycosyl derivatives.[11–13] Also, glycosidation of 4-aryl-3-thioxo-2,3-dihydro-1,2,4-
triazin-5(4H)-ones was reported to give the corresponding 2-glycosyl derivatives.[14]
In the present investigation we applied these strategies to selectively synthesize some
new 2-b-D-galactopyranosyl derivatives of 6-substituted-3-thioxo-2,3-dihydro-1,2,4-
triazin-5(4H)-ones. The starting 4-amino[15–17]=4-aryl[14,16]-6-substituted-3-thioxo-
2,3-dihydro-1,2,4-triazin-5(4H)-ones 3a–k=9a–h,k were prepared as reported. The
new 4-amino=4-aryl-6-b-(4-N,N-dimethylaminophenyl)vinyl-3-thioxo-2,3-dihydro-
1,2,4-triazin-5(4H)-ones (3l=9i,j) are now synthesized using the same procedures
starting with the appropriate a-ketocarboxylic acid 1l and thiocarbohydrazide (2)=
4-arylthiosemicarbazide 8a,b (Sch. 1).
Galactosidation of the 4-amino-6-substituted-3-thioxo-2,3-dihydro-1,2,4-tri-
azin-5(4H)-ones 3a–l with 2,3,4,6-tetra-O-acetyl-a-D-galactopyranosyl bromide (4)
in either N,N-dimethylformamide containing triethylamine or acetonitrile contain-
ing triethylamine afforded the corresponding 4-amino-2-(2,3,4,6-tetra-O-acetyl-b-
D-galactopyranosyl)-6-substituted-3-thioxo-2,3-dihydro-1,2,4-triazin-5(4H)-ones 5a–l.
Among the different possible monogalactosyl derivatives 5–7, the structure of 5a–l
is clearly assigned by 1H NMR spectral data which show the position of the anome-
0
0
ric proton at d 6.7 (J1 –2 ¼ 9–9.4 Hz) and NH2 protons at d 6.4 (s, 2H, exchangeable)
consistent with similar reported data.[11–13] Furthermore, the structure of 5a–l was
chemically established as will be seen later (Sch. 1).
Analogous glycosidation of the 4-aryl-6-substituted-3-thioxo-2,3-dihydro-1,2,
4-triazin-5(4H)-ones 9a–k gave the corresponding 4-aryl-2-(2,3,4,6-tetra-O-acetyl-
b-D-galactopyranosyl)-6-substituted-3-thioxo-2,3-dihydro-1,2,4-triazin-5(4H)-ones
10a–k. Assignment of the structure of compounds 10a–k rather than their isomeric
S-galactosyl derivatives 11a–k was established chemically and spectroscopically.
Thus, the 1H NMR spectral data of compounds 10a–k revealed the position
0
0
of the anomeric proton at d 6.8–6.68 (J1 –2 ¼ 8.4–9.3 Hz) in agreement with
that reported for analogous 4-aryl-2-(2,3,4,6-tetra-O-acetyl-b-D-glucopyranosyl)-6-
substitutedbenzyl-3-thioxo-2,3-dihydro-1,2,4-triazin-5(4H)-ones.[14] Also, the mass
spectrum of 10a showed the correct parent ion peak at m=z 625 (M+, 16.13%) (Sch. 1).
Deamination of 5a–j into the target 2-b-D-galactosyl derivatives 12a–j was
achieved in almost quantitative yields by the action of nitrous acid in acetic acid.
The structure of compounds 12a–j was inferred from their chemical and spectral evi-
1
dences. Thus, the H NMR spectra of compounds 12a–j showed absence of NH2
proton signal at d 6.4 and appearance of NH proton signal at d 10.3–9.4 (s, or
brs, 1H, exchangeable) (Sch. 2).

6-Substituted-2-b-galactosyl-1,2,4-triazines
23
Scheme 1.

24
Mansour, Eid, and Khalil
Methylation of compounds 12c,d,h–j with methyl iodide in N,N-dimethylform-
amide containing either sodium carbonate or triethylamine gave a mixture of the
3-SCH3 13a–e, 4-NCH3 14a–e, and 5-OCH3 15a–e derivatives. Identification of
the products 13–15 and their ratios was achieved from their 1H NMR spectral data.
Thus, 13a–e revealed 3-SCH3 signal at d 2.66–2.58, 14a–e revealed 4-NCH3 signal at
d 3.77–3.31, and 15a–e revealed 5-OCH3 signal at d 3.4–3.29. The position of
3-SCH3, 4-NCH3, and 5-OCH3 characteristic proton signals is consistent with that
reported for similar methylation products of some 2-b-D-glucopyranosyl-6-substi-
tuted-3-thioxo-2,3-dihydro-1,2,4-triazin-5(4H)-ones.[11,13,18] Table
1 shows the
action of methyl iodide on compounds 12c,d,h–j (Sch. 2).
Glycosidation of the 4-arylideneamino-6-substituted-3-thioxo-2,3-dihydro-
1,2,4-triazin-5(4H)-ones 16a–h[16,21] with compound 4 in acetonitrile containing
triethylamine gave the corresponding 4-arylideneamino-2-(2,3,4,6-tetra-O-acetyl-
b-D-galactopyra-nosyl)-6-substituted-3-thioxo-2,3-dihydro-1,2,4-triazin-5(4H)-ones
17a–h. The structure of compounds 17a–h was established chemically and spectro-
scopically. Thus, compound 17f was alternatively prepared via condensation of 5f
with benzaldehyde. Moreover, the 1H NMR spectra of 17a–h revealed the character-
istic N¼CH proton signal at d 8.33–8.44 consistent with similar reported data[11–13]
(Sch. 2).
Thiation of compounds 10a,g, and 12b–f,i with phosphorous pentasulfide in
pyridine afforded the corresponding 4-aryl-2-(2,3,4,6-tetra-O-acetyl-b-D-galacto-
pyranosyl)-6-substituted-1,2,4-triazine-3,5(2H,4H)-dithiones 18a,b, and 2-(2,3,4,
6-tetra-O-acetyl-b-D-galactopyranosyl)-6-substituted-1,2,4-triazine3,5(2H,4H)-dithi-
ones 19a–f, respectively. Structure assignment of compounds 18a,b and 19a–f was
inferred from their correct analytical and spectral data. Thus, the IR spectra of these
compounds showed the absence of the amide carbonyl function at 1715–1705 cmꢀ1
.
On the other hand, the mass spectrum of compound 19b showed the correct parent
1
ion peak at m=z 565 (Mþ, 20.7%). Also, the H NMR spectra of compounds 19a–f
revealed signals consistent with their structures (cf. experimental part). Moreover,
the IR and 1H NMR spectral data of compounds 19a–f are in agreement with those
reported for the analogous 2-(2,3,4,6-tetra-O-acetyl-b-D-glucopyranosyl)-6-substi-
tuted-1,2,4-triazine-3,5(2H,4H)-dithiones[13] (Sch. 3).
Treatment of the appropriate acetyl derivatives 5i, 10g, and 12g,i with methano-
lic ammonia led to the formation of the corresponding free glycosyl derivatives 20,
21, and 22a,b, respectively (Sch. 3).
Table 1. Action of methyl iodide on compounds 12c,d,h–j.
Compound
Reaction condition
Products (relative ratio %)
12c
12d
12h
12i
12i
12j
MeI=DMF=TEA
MeI=DMF=TEA
MeI=DMF=Na2CO3
MeI=DMF=TEA
MeI=DMF=Na2CO3
MeI=DMF=Na2CO3
13a (72.7), 14a (9.1), 15a (18.2)
13b (38.5), 14b (7.7), 15b (53.8)
13c (27.3), 14c (9.1), 15c (63.6)
14d (25.7), 15d (74.3)
13d (18.1), 14d (31.9), 15d (50)
13e (51.6), 14e (9.7), 15e (38.7)

6-Substituted-2-b-galactosyl-1,2,4-triazines
25
Scheme 2.

26
Mansour, Eid, and Khalil
Scheme 3.

6-Substituted-2-b-galactosyl-1,2,4-triazines
BIOLOGICAL EVALUATION
27
Compounds 5a–c,e,i,k, 12a,b,j, 19a,b, and 22b were tested for their human anti-
cancer activity using an in vitro model through a 3-cell line, one dose primary anti-
cancer assay consisting of MCF7 (Breast), NCI-H460 (lung) and SF-268 (CNS).
Among the previously mentioned tested compounds, only compound 19b was found
to be active against both MCF7 (Breast) and SF-268 (CNS) in this 3-cell line, one
dose primary human anticancer assay (Table 2).
EXPERIMENTAL
All melting points are uncorrected. IR spectra were recorded on a Perkin-Elmer
1
1430 spectrophotometer. H NMR spectra were measured with a Varian GEMINI
1
200 spectrometer (200 MHz H NMR). Mass spectra were recorded on a GCMS-
QP 1000 EX (70 EV) spectrometer. Elemental analyses were carried out at the
Microanalytical Centre, Cairo University. Anticancer screening of compounds 5a–
c,e,i,k, 12a,b,j, 19a,b, and 22b was carried out at the National Cancer Institute –
National Institutes of Health, Bethesda, Maryland, United States of America. The
starting 4-amino=4-aryl-6-substituted-3-thioxo-2,3-dihydro-1,2,4-triazin-5(4H)-ones
3a–k,[15–17]=9a–h,k,[14,16] and 2,3,4,6-tetra-O-acetyl-a-D-galactopyranosyl bromide
(4)[20] were prepared as reported. The 4-arylideneamino-6-substituted-3-thioxo-2,3-
dihydro-1,2,4-triazin-5(4H)-ones 16a–h were prepared after the method described
by Mansour[16] and Eid.[21]
4-Amino-6-b-(4-N,N-dimethylaminophenyl)vinyl-3-thioxo-2,3-dihydro-1,2,4-tri-
azin-5(4H)-one (3l). To a mixture of pyruvic acid (7 mL, 0.1 mol), 4-N,N-dimethyl-
aminobenzaldehyde (14.9 g, 0.1 mol), and methanol (10 mL), two thirds volume of a
Table 2. Human anticancer activity of compounds 5a–c,e,i,k, 12a,b,j, 19a,b and 22b.
Growth percentage
(Lung)
NCI-H460
(Breast)
MCF7
(CNS)
SF-268
Compound
Concentration
Activity
5a
5b
1.00E-04 M
1.00E-04 M
1.00E-04 M
5.00E-05 M
5.00E-05 M
1.00E-04 M
1.00E-04 M
1.00E-04 M
5.00E-05 M
1.00E-04 M
1.00E-04 M
1.00E-04 M
117
92
95
116
90
71
104
94
67
83
42
114
92
91
92
111
93
71
96
89
112
95
106
79
82
86
94
54
Inactive
Inactive
Inactive
Inactive
Inactive
Inactive
Inactive
Inactive
Inactive
Inactive
Active
5c
5e
5i
5k
12a
12b
12j
19a
19b
22b
94
36
89
ꢀ15
108
ꢀ38
90
91
Inactive

28
Mansour, Eid, and Khalil
solution of potassium hydroxide (10 g, 0.18 mol) in methanol (10 mL) was added at
0–5 ꢁC while shaking over a fifteen minutes period. The last third volume of the pre-
vious methanolic potassium hydroxide solution was then added in one pot with con-
stant shaking and the reaction mixture was allowed to stand at room temperature for
one hour. The precipitate was then collected, washed with cold methanol, and dried
at ambient temperature to give crude 4-N,N-dimethylaminobenzylidenepyruvic acid
potassium salt (13.3 g, 51.7%). A boiling solution of thiocarbohydrazide (5.48 g,
0.05 mole) in water (50 mL) was added dropwise while shaking to a boiling mixture
of 4-N,N-dimethylaminobenzylidene-pyruvic acid potassium salt (13.3 g, 0.05 mole),
acetic acid (10 mL), and water (30 mL). The reaction mixture was then heated under
reflux for six hours, cooled, and kept overnight at room temperature. After collec-
tion of the formed precipitate, it was washed several times with water, and recrystal-
lized from N,N-dimethylformamide as brown crystals of 3l (30.6%), mp. 220ꢁC
1
(decomp); IR (KBr) 3423 (NH), 3223, 3068 (NH2), 1662 (C¼O amide) cmꢀ1; H
NMR (DMDO-d6) d 9.38 (s, 1H, NH, exchangeable), 7.74, 6.85 (2d, 2H, J ¼ 16.3 Hz,
Hz, trans CH¼CH), 7.45, 6.70 (2d, 4H, ArH’s), 6.48 (s, 2H, NH2, exchangeable),
3.02 (s, 6H, N(CH3)2).
Anal. For C13H15N5OS Calcd.: C, 53.96; H, 5.22; N, 24.20. Found: C, 54.0; H,
5.1;N, 24.3.
4-Aryl-6-(4-N,N-dimethylaminobenzyl)-3-thioxo-2,3-dihydro-1,2,4-triazin-5(4H)-
ones 9i,j. General procedure: A solution of 4-(N,N-dimethylaminobenzylidene)-
2-phenyl-oxazol-5-one (29.2 g, 0.1 mol) in potassium hydroxide (17.5 g, 0.31 mol,
1M aqueous solution) was refluxed for 612 h to give in situ the corresponding 4-
N,N-dimethylaminophenylpyruvic acid 1m. After acidification with acetic acid, the
appropriate 4-arylthiosemicarbazide 8a,b (0.1 mol) was added, and the reaction
mixture was further refluxed for 8 h and left overnight at room temperature. The
formed precipitate was collected and recrystallized from ethanol into yellow crystals
of 9i,j.
4-Phenyl-6-(4-N,N-dimethylaminobenzyl)-3-thioxo-2,3-dihydro-1,2,4-triazin-5(4H)-
one (9i). Using the general procedure, 1m gave 9i (90%); mp. 165ꢁC; IR (KBr) 3279
(NH), 1689 (C¼O amide) cmꢀ1; 1H NMR (DMSO-d6) d 9.68 (s, 1H, NH, exchange-
able), 8–6.42 (m, 9H, ArH’s), 3.81 (s, 2H, 4-NMe2C6H4CH2), 2.91 (s, 6H, N(CH3)2).
Anal. For C18H18N4OS Calcd.: C, 63.88; H, 5.36; N, 16.55. Found: C, 64.0; H,
5.4; N, 16.7.
4-(4-Methylphenyl)-6-(4-N,N-dimethylaminobenzyl)-3-thioxo-2,3-dihydro-1,2,4-
triazin-5(4H)-one (9j). Using the general procedure, 1m gave 9j (95%); mp. 180ꢁC;
IR (KBr) 3275 (NH), 1691 (C¼O amide) cmꢀ1; 1H NMR (CDCl3) d 8.95 (s, 1H, NH,
exchangeable), 8–6.6 (m, 8H, ArH’s), 3.81 (s, 2H, 4-NMe2C6H4CH2), 2.99 (s, 6H,
N(CH3) ), 2.34 (s, 3H, 4-CH3C6H4N).
2
Anal. For C19H20N4OS Calcd.: C, 64.75; H, 5.72; N, 15.9. Found: C, 64.6; H,
5.7; N, 15.8.
4-Amino-2-(2,3,4,6-tetra-O-acetyl-b-D-galactopyranosyl)-6-substituted-3-thioxo-
2,3-dihydro-1,2,4-triazin-5(4H)-ones 5a–l. General procedure: To a solution of each

6-Substituted-2-b-galactosyl-1,2,4-triazines
29
of 3a–l (10 mmol) in N,N-dimethylformamide or acetonitrile (5 mL) and triethyl-
amine (2 mL, 14 mmol) was added 2,3,4,6-tetra-O-acetyl-a-D-galactopyranosyl bro-
mide (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, washed with
water, and dried at room temperature. Compound 5b was recrystallized from
EtOH=HCCl3. Compounds 5a,c–l were extracted from ethyl acetate and purified
by preparative TLC plates plates (silica gel 60 GF254) using ethyl acetate as an eluent.
Compounds 5a,c–l were then extracted from chloroform on a soxhlet extractor.
The chloroform extracts were then concentrated, and diluted with petroleum
ether (40–60ꢁC). After collection of crude 5a,c–l they were recrystallized from
diethylether=petroleum ether (40–60ꢁC) into colorless crystals of 5a,c,d,f and yellow
crystals of 5e,g–l.
4-Amino-2-(2,3,4,6-tetra-O-acetyl-b-D-galactopyranosyl)-6-methyl-3-thioxo-2,3-
dihydro-1,2,4-triazin-5(4H)-one (5a).a Using the general procedure, 3a gave 5a
(39.2%); Rf ¼ 0.71; mp. 115ꢁC; IR (KBr), 3325, 3228 (NH2), 1751 (C¼O acetate),
0
1
1697 (C¼O amide) cmꢀ1; H NMR (CDCl3) d 6.69 (d, 1H, H1 , J1 –2 ¼ 9 Hz), 6.42
0
0
0
(s, 2H, NH2, exchangeable), 5.89 (t, 1H, H2 , J ¼ (J2 –1 þ J2 –3 )=2 ¼ 8.6 Hz), 5.49
0
0
0
0
30
0
(d, 1H, H4 , J4 –3 ¼ 2.8 Hz), 5.24 (dd, 1H, H , J3 –4 ¼ 2.9, J3 –2 ¼ 10.3 Hz), 4.22–
0
0
0
0
0
0
0
0
4.1 (m, 3H, H5 , H6 ), 2.39 (s, 3H, CH3), 2.22, 2.06, 2.01, 1.95 (4s, 12H, CH3CO).
Anal. For C18H24N4O10S Calcd.: C, 44.26; H, 4.95; N, 11.47. Found: C, 44.3; H,
5.0; N, 11.3.
4-Amino-2-(2,3,4,6-tetra-O-acetyl-b-D-galactopyranosyl)-6-phenyl-3-thioxo-2,3-
dihydro-1,2,4-triazin-5(4H)-one (5b). Using the general procedure, 3b gave 5b
(42.9%); mp. 160ꢁC; IR (KBr), 3319, 3225 (NH2), 1761, 1751, 1736 (C¼O acetate),
1707 (C¼O amide) cmꢀ1; 1H NMR (CDCl3) d 8.18–7.48 (m, 5H, ArH’s), 6.86 (d, 1H,
0
0
J ¼ 9.2 Hz, H1 ), 6.03 (t, 1H, J ¼ 9.4 Hz, H2 ), 6.30 (s, 2H, NH2, exchangeable),
0
0
5.51 (d, 1H, J ¼ 3.4 Hz, H4 ), 5.24 (dd, 1H, J ¼ 3.5, 9.4 Hz, H3 ), 4.2–4.0 (m, 3H,
0
0
H5 , H6 ), 2.21–1.96 (4s, 12H, CH3CO).
Anal. For C23H26N4O10S Calcd.: C, 50.18; H, 4.76; N, 10.18. Found: C, 50.2; H,
4.8; N, 10.0.
4-Amino-2-(2,3,4,6-tetra-O-acetyl-b-D-galactopyranosyl)-6-benzyl-3-thioxo-2,3-
dihydro-1,2,4-triazin-5(4H)-one (5c). Using the general procedure, 3c gave 5c
(74.0%); Rf ¼ 0.70; mp. 85ꢁC; IR (KBr), 3321, 3223 (NH2), 1749 (C¼O acetate),
1
1690 (C¼O amide)0 cmꢀ1; H NMR (CDCl3) d 7.37–7.23 (m, 5H, ArH’s), 6.7 (d,
1H, J ¼ 9.2 Hz, H1 ), 6.30 (s, 2H, NH2, exchangeable), 5.97 (t, 1H, J ¼ 9.7 Hz,
0
0
0
H2 ), 5.5 (d, 1H, J ¼ 3.2 Hz, H4 ), 5.25 (dd, 1H, J ¼ 3.4, 10.2 Hz, H3 ), 4.23–3.92
0
0
(m, 5H, H5 , H6 , CH2Ph), 2.21, 2.04, 2.02, 1.9 (4s, 12H, CH3CO).
Anal. For C24H28N4O10S Calcd.: C, 51.06; H, 5.0; N, 9.92. Found: C, 51.1; H,
5.2; N, 10.1.
aCompound 5a is an illustrative example that shows how J values including coupling protons
assign different CH0 protons of the sugar moiety.

30
Mansour, Eid, and Khalil
4-Amino-2-(2,3,4,6-tetra-O-acetyl-b-D-galactopyranosyl)-6-(4-methylbenzyl)-3-
thioxo-2,3-dihydro-1,2,4-triazin-5(4H)-one (5d). Using the general procedure, 3d
gave 5d (74.0%); Rf ¼ 0.72; mp. 80ꢁC; IR (KBr), 3319, 3223 (NH2), 1751 (C¼O
1
acetate), 1693 (C¼O amide) cmꢀ1; H NMR (CDCl3) d 7.27, 7.2 (2d, 4H, ArH’s),
0
0
6.70 (d, 1H, J ¼ 9.2 Hz, H1 ), 6.30 (s, 2H, NH2), 5.98 (t, 1H, J ¼ 9.7 Hz, H2 ), 5.5
0
0
(d,0 1H, J ¼ 3.4 Hz, H4 ), 5.25 (dd, 1H, J ¼ 3.5, 10.1 Hz, H3 ), 4.25–3.88 (m, 5H,
0
H5 , H6 , 4-MeC6H4CH2), 2.31 (s, 3H, CH3), 2.21, 2.05, 2.03, 1.91 (4s, 12H, CH3CO).
Anal. For C25H30N4O10S Calcd.: C, 51.9; H, 5.22. Found: C, 52.0; H, 5.1.
4-Amino-2-(2,3,4,6-tetra-O-acetyl-b-D-galactopyranosyl)-6-(4-methoxybenzyl)-3-
thioxo-2,3-dihydro-1,2,4-triazin-5(4H)-one (5e). Using the general procedure, 3e
gave 5e (76.9%); Rf ¼ 0.70; mp. 86ꢁC; IR (KBr), 3335, 3238 (NH2), 1751 (C¼O acet-
ate), 1692 (C¼O amid0e) cmꢀ1; 1H NMR (CDCl3) d 7.31, 6.85 (2d, 4H, ArH’s), 6.70
0
(d, 1H, J ¼ 9.4 Hz, H1 ), 6.30 (s, 2H, NH2), 5.98 (t, 1H, J ¼ 9.5 Hz, H2 ), 5.5 (d, 1H,
0
0
0
0
J ¼ 3.4 Hz, H4 ), 5.24 (dd, 1H, J ¼ 3.4, 10.1 Hz, H3 ), 4.22–3.85 (m, 5H, H5 , H6 , 4-
MeOC6H4CH2), 3.78 (s, 3H, OCH3), 2.22, 2.05, 2.03, 1.92 (4s, 12H, CH3CO).
Anal. For C25H30N4O11S Calcd.: C, 50.5; H, 5.08. Found: C, 50.5; H, 5.1.
4-Amino-2-(2,3,4,6-tetra-O-acetyl-b-D-galactopyranosyl)-6-(4-chlorobenzyl)-3-thi-
oxo-2,3-dihydro-1,2,4-triazin-5(4H)-one (5f). Using the general procedure, 3f gave
5f (77.0%); Rf ¼ 0.74; mp. 104ꢁC (decomp.); IR (KBr), 3319, 3223 (NH2), 1751
1
(C¼O acetate), 1693 (C¼O amide) cmꢀ1; H NMR (CDCl3) d 7.36–7.25 (2d, 4H,
0
ArH’s), 6.71 (d, 1H, J ¼ 9.2 Hz, H1 ), 6.3 (s, 2H, NH2), 5.91 (t, 1H, J ¼ 9.7 Hz,
0
0
0
H2 ), 5.49 (d, 1H, J ¼ 3.4 Hz, H4 ), 5.24 (dd, 1H, J ¼ 3.5, 10.1 Hz, H3 ), 4.2–3.9 (m,
0
0
5H, H5 , H6 , 4-ClC6H4CH2), 2.2, 2.05, 2.02, 1.91 (4s, 12H, CH3CO).
Anal. For C24H27N4O10SCl Calcd.: C, 48.12; H, 4.54. Found: C, 48.2; H, 4.5.
4-Amino-2-(2,3,4,6-tetra-O-acetyl-b-D-galactopyranosyl)-6-(3,4-dimethoxybenzyl)-
3-thioxo-2,3-dihydro-1,2,4-triazin-5(4H)-one (5g). Using the general procedure, 3g
gave 5g (70%); Rf ¼ 0.75; mp. 98ꢁC; IR (KBr), 3321, 3223 (NH2),
1
1755 (C¼O acetate), 1693 (C¼O amide) cmꢀ1; H NMR (CDCl3) d 7.36–6.96 (m,
0
3H, ArH’s), 6.76 (d, 1H, J ¼ 9.2 Hz, H1 ), 6.32 (s, 2H, NH2), 6.02 (t, 1H, J ¼ 9.6 Hz,
0
0
0
Hz, H2 ), 5.37 (d, 1H, J ¼ 3 Hz, H4 ), 5.25 (dd, 1H, J ¼ 3.0, 10 Hz, H3 ), 4.2–3.9 (m,
0
0
3H, H5 , H6 ), 3.93 (s, 2H, 3,4-(CH3O) 2PhCH2), 2.41, 2.33 (2s, 6H, 3,4-
(CH3O)2PhCH2), 2.23, 2.07, 2.05, 2.0 (4s, 12H, CH3CO).
Anal. For C26H32N4O12S Calcd.: C, 50.0; H, 5.16. Found: C, 50.1; H, 5.20.
4-Amino-2-(2,3,4,6-tetra-O-acetyl-b-D-galactopyranosyl)-6-styryl-3-thioxo-2,3-
dihydro-1,2,4-triazin-5(4H)-one (5h). Using the general procedure, 3h gave 5h
(76.9%); Rf ¼ 0.74; mp. 102ꢁC; IR (KBr), 3321, 3221 (NH2), 1755 (C¼O acetate),
1693 (C¼O amide) cmꢀ1; 1H NMR (CDCl3) d 8.01, 7.15 (2d, 2H, J ¼ 16.4 Hz, trans
0
CH¼CH), 7.64–7.61 (m, 5H, ArH’s), 6.72 (d, 1H, J ¼ 9.4 Hz, H1 ), 6.5 (s, 2H, NH2),
0
0
6.04 (t, 1H, J ¼ 9.6 Hz, H2 ), 5.52 (0d, 1H, J ¼ 3.4 Hz, H4 ), 5.29 (dd, 1H, J ¼ 3.8,
0
0
10 Hz, H3 ), 4.2–3.9 (m, 3H, H5 , H6 ), 2.24, 2.06, 2.04, 1.99 (4s, 12H, CH3CO).
Anal. For C25H28N4O10S Calcd.: C, 52.08; H, 4.89; N, 9.72. Found: C, 52.2; H,
4.9; N, 9.8.

6-Substituted-2-b-galactosyl-1,2,4-triazines
31
4-Amino-2-(2,3,4,6-tetra-O-acetyl-b-D-galactopyranosyl)-6-b-(4-methylphenyl)vinyl-
3-thioxo-2,3-dihydro-1,2,4-triazin-5(4H)-one (5i). Using the general procedure, 3i
gave 5i (79.4%); Rf ¼ 0.72; mp. 112ꢁC; IR (KBr), 3323, 3223 (NH2), 1755 (C¼O acet-
1
ate), 1690 (C¼O amide) cmꢀ1; H NMR (CDCl3) d 7.97, 7.1 (2d, 2H, J ¼ 16.4 Hz,
0
trans CH¼CH), 7.51, 7.20 (2d, 4H, ArH’s), 6.7 (d, 1H, J ¼ 9.2 Hz, H1 ), 6.43 (s,
0
2H, NH2, exchangeable), 6.05 (t, 1H, J ¼ 9.7 Hz, H2 ), 5.53 (d, 1H, J ¼ 3.4 Hz,
0
0
0
0
H4 ), 5.27 (dd, 1H, J ¼ 3.4, 10.2 Hz, H3 ), 4.25–4.0 (m, 3H, H5 , H6 ), 2.37 (s, 3H,
CH3), 2.25, 2.06, 2.03, 1.95 (4s, 12H, CH3CO).
Anal. For C26H30N4O10S Calcd.: C, 52.87; H, 5.12. Found: C, 53.0; H, 5.1.
4-Amino-2-(2,3,4,6-tetra-O-acetyl-b-D-galactopyranosyl)-6-b-(4-methoxyphenyl)-
vinyl-3-thioxo-2,3-dihydro-1,2,4-triazin-5(4H)-one (5j). Using the general proce-
dure, 3j gave 5j (79.5%); Rf ¼ 0.70; mp. 188ꢁC; IR (KBr), 3327, 3238 (NH2), 1751
1
(C¼O acetate), 1697 (C¼O amide) cmꢀ1; H NMR (CDCl3) d 7.96, 7.02 (2d, 2H,
J ¼0 16.4 Hz, trans CH¼CH), 7.57, 6.92 (2d, 4H, ArH’s), 6.69 (d, 1H, J ¼ 9.2 Hz,
0
0
H1 ), 6.42 (s, 2H, NH2), 6.05 (t, 1H, J ¼ 9.7 Hz, H2 ), 5.52 (d, 1H, J ¼ 3.4 Hz, H4 ),
0
0
0
5.26 (dd, 1H, J ¼ 3.5, 10.1 Hz, H3 ), 4.25–4.1 (m, 3H, H5 , H6 ), 3.85 (s, 3H,
OCH3), 2.24, 2.06, 2.03, 1.95 (4s, 12H, CH3CO).
Anal. For C26H30N4O11S Calcd.: C, 51.48; H, 4.98. Found: C, 51.5; H, 5.0.
4-Amino-2-(2,3,4,6-tetra-O-acetyl-b-D-galactopyranosyl)-6-b-(4-chlorophenyl)-
vinyl-3-thioxo-2,3-dihydro-1,2,4-triazin-5(4H)-one (5k). Using the general proce-
dure, 3k gave 5k (82.6%); Rf ¼ 0.75; mp. 140ꢁC; IR (KBr), 3321, 3223 (NH2),
1
1753 (C¼O acetate), 1691 (C¼O amide) cmꢀ1; H NMR (CDCl3) d 7.97, 7.12 (2d,
2H, J ¼ 16.4 Hz, trans CH¼CH), 7.56, 7.37 (2d, 4H, ArH’s), 6.44 (s, 2H, NH2),
0
0
6.69 (d, 1H, J ¼ 9.4 Hz, H1 ), 6.04 (t, 1H, J ¼ 9.7 Hz, H2 ), 5.53 (d, 1H, J ¼ 3.4 Hz,
0
0
0
0
H4 ), 5.27 (dd, 1H, J ¼ 3.4, 10 Hz, H3 ), 4.22–4.05 (m, 3H, H5 , H6 ), 2.24, 2.06,
2.04, 1.96 (4s, 12H, CH3CO).
Anal. For C25H27N4O10SCl Calcd.: C, 49.14; H, 4.45. Found: C, 49.1; H, 4.5.
4-Amino-2-(2,3,4,6-tetra-O-acetyl-b-D-galactopyranosyl)-6-b-(4-N,N-dimethyl-
aminophenyl)vinyl-3-thioxo-2,3-dihydro-1,2,4-triazin-5(4H)-one (5l). Using the gen-
eral procedure, 3l gave 5l (75.6%); Rf ¼ 0.75; mp.100ꢁC; IR (KBr), 3318, 3226
1
(NH2), 1752 (C¼O acetate), 1680 (C¼O amide) cmꢀ1; H NMR (CDCl3) d 7.92,
6.94 (2d, 2H, J ¼ 16.2 Hz, trans CH¼CH), 7.52, 6.69 (2d,0 4H, ArH’s), 6.69 (d, 1H,
0
J ¼ 9 Hz, H1 ), 6.42 (s, 2H, NH2), 6.06 (t, 1H, J ¼ 9 Hz, H2 ), 5.52 (d, 1H, J ¼ 3.4 Hz,
0
0
0
0
Hz, H4 ), 5.24 (dd, 1H, J ¼ 3.4, 10 Hz, H3 ), 4.24–4.0 (m, 3H, H5 , H6 ), 3.03 (s, 6H,
N(CH3) ), 2.25, 2.06, 2.04, 1.94 (4s, 12H, CH3CO).
2
Anal. For C27H33N5O10S Calcd.: C, 52.33; H, 5.37; N, 11.3. Found: C, 52.3; H,
5.4; N, 11.2.
4-Aryl-2-(2,3,4,6-tetra-O-acetyl-b-D-galactopyranosyl)-6-substituted-3-thioxo-2,3-
dihydro-1,2,4-triazin-5(4H)-ones (10a–k). General procedure: To a solution of each
of 9a–k (10 mmol) in N,N-dimethylformamide oracetonitrile (5 mL) and triethyl-
amine (2 mL, 14 mmol) was added 2,3,4,6-tetra-O-acetyl-a-D-galactopyranosyl bro-
mide (4) (10 mmol). After shaking the reaction mixture for 20 min, it was kept at
room temperature overnight. The reaction mixture was then cooled, acidified with

32
Mansour, Eid, and Khalil
acetic acid (1 mL), and the formed precipitate was collected, washed with water, and
dried at room temperature. Compounds 10a–k were extracted from ethyl acetate,
and purified by preparative TLC plates plates (silica gel 60 GF254) using ethyl acetate
as an eluent. The eluted compounds were then extracted from chloroform on a
soxhlet extractor. The chloroform extracts were concentrated, and diluted with
petroleum ether (40–60ꢁC). After collection of crude 10a–k, they were recrystallized
from diethylether=petroleum ether (40–60ꢁC) as pale crystals of 10a–h, orange
yellow crystals of 10i,j, and yellow crystals of 10k.
4-Phenyl-2-(2,3,4,6-tetra-O-acetyl-b-D-galactopyranosyl)-6-benzyl-3-thioxo-2,3-
dihydro-1,2,4-triazin-5(4H)-one (10a). Using theþgeneral procedure, 9a gave 10a
(51.2%); Rf ¼ 0.72; mp. 104ꢁC; MS: m=z 625 (M , 16.13); IR (KBr), 1751 (C¼O
1
acetate), 1705 (C¼O amide) cmꢀ1; H NMR (CDCl3) d 7.54–7.14 (m, 10H, ArH’s),
0
0
0
6.8 (d, 1H, J ¼ 9.2 Hz, H1 ), 5.97 (t, 1H, J ¼ 9.6 Hz H2 ), 5.51 0(d, 1H, J ¼ 3.4 Hz H4 ),
0
0
5.25 (dd, 1H, J ¼ 3.5, 10.1 Hz, H3 ), 4.2–4.02 (m, 3H, H5 , H6 ), 3.98 (s, 2H, CH2Ph),
2.24–1.98 (4s, 12H, CH3CO).
Anal. For C30H31N3O10S Calcd.: C, 57.59; H, 4.99; N, 6.72. Found: C, 57.6; H,
5.1; N, 6.7.
4-(4-Methylphenyl)-2-(2,3,4,6-tetra-O-acetyl-b-D-galactopyranosyl)-6-benzyl-3-
thioxo-2,3-dihydro-1,2,4-triazin-5(4H)-one (10b). Using the general procedure, 9b
gave 10b (66.2%); Rf ¼ 0.75; mp. 94ꢁC; IR (KBr), 1751 (C¼O acetate), 1705 (C¼O
1
amide) cmꢀ1; H NMR (CDCl3) d 7.4–7.0 (m, 9H, ArH’s), 6.8 (d, 1H, J ¼ 9.2 Hz,
0
0
0
H1 ), 5.96 (t, 1H,0 J ¼ 9.9 Hz, H2 ), 5.5 (d, 1H, J ¼ 3.4 Hz, H4 ), 5.24 (dd, 1H,
0
0
J ¼ 3.3, 9.9 Hz, H3 ), 4.2–3.98 (m, 3H, H5 , H6 ), 3.95 (s, 2H, CH2Ph), 2.4 (s, 3H,
CH3), 2.22–1.98 (4s, 12H, CH3CO).
Anal. For C31H33N3O10S Calcd.: C, 58.21; H, 5.2. Found: C, 58.2; H, 5.1.
4-Phenyl-2-(2,3,4,6-tetra-O-acetyl-b-D-galactopyranosyl)-6-(4-methylbenzyl)-3-
thioxo-2,3-dihydro-1,2,4-triazin-5(4H)-one (10c). Using the general procedure, 9c
gave 10c (81.15%); Rf ¼ 0.74; mp. 102ꢁC; IR (KBr), 1751 (C¼O acetate), 1705
1
(C¼O amide) cmꢀ1; H NMR (CDCl3) d 7.53–7.11 (m, 9H, ArH’s), 6.79 (d, 1H,
0
0
0
J ¼ 9.2 Hz, H1 ), 5.98 (t, 1H, J ¼ 9.6 Hz, H2 ), 5.50 (d, 1H, J ¼ 3.6 Hz, H4 ), 5.24
0
0
0
(dd, 1H, J ¼ 3.4, 10 Hz, H3 ), 4.19–3.96 (m, 3H, H5 , H6 ), 3.93 (s, 2H, 4-CH3-
C6H4CH2), 2.32 (s, 3H, 4-CH3-C6H4CH2), 2.23–1.98 (4s, 12H, CH3CO).
Anal. For C31H33N3O10S Calcd.: C, 58.21; H, 5.2. Found: C, 58.1; H, 5.2.
4-(4-Methylphenyl)-2-(2,3,4,6-tetra-O-acetyl-b-D-galactopyranosyl)-6-(4-methyl-
benzyl)-3-thioxo-2,3-dihydro-1,2,4-triazin-5(4H)-one (10d). Using the general pro-
cedure, 9d gave 10d (80.7%); Rf ¼ 0.75; mp. 106ꢁC; IR (KBr), 1751 (C¼O acetate),
1705 (C¼O amide) cmꢀ1
5.25 (dd, 1H, J ¼ 3.5, 10.1 Hz, H3 ), 4.19–3.95 (m, 3H, H5 , H6 ), 3.92 (s, 2H,
4-CH3-C6H4CH2), 2.4 (s, 3H, 4-CH3-C6H4N), 2.32 (s, 3H, 4-CH3-C6H4CH2),
2.23–1.97 (4s, 12H, CH3CO).
;
1H NMR (CDCl3) d 7.033–7.03 (m, 8H, ArH’s), 6.81
0
0
(d, 1H, J ¼ 9.2 Hz, H1 ), 5.98 (t, 1H, J ¼ 9.6 Hz, H2 ), 5.5 (d, 1H, J ¼ 3.4 Hz, H4 ),
0
0
0
Anal. For C32H35N3O10S Calcd.: C, 58.79; H, 5.4. Found: C, 58.6; H, 5.4.

6-Substituted-2-b-galactosyl-1,2,4-triazines
33
4-Phenyl-2-(2,3,4,6-tetra-O-acetyl-b-D-galactopyranosyl)-6-(4-methoxybenzyl)-3-
thioxo-2,3-dihydro-1,2,4-triazin-5(4H)-one (10e). Using the general procedure, 9e
gave 10e (78.6%); Rf ¼ 0.71; mp. 106ꢁC; IR (KBr), 1751 (C¼O acetate), 1705
1
(C¼O amide) 0cmꢀ1; H NMR (CDCl3) d 7.54–6.83 (m, 9H, ArH’s), 6.79 (d, 1H,
0
0
J ¼ 9.2 Hz, H1 ), 5.96 (t, 1H, J ¼ 9.8 Hz, H2 ), 5.5 (d, 1H, J ¼ 3.2 Hz, H4 ), 5.24 (dd,
0
0
0
1H, J ¼ 3.5, 10.1 Hz, H3 ), 4.18–3.93 (m, 3H, H5 , H6 ), 3.9 (s, 2H, 4-CH3OC6H4CH2),
3.78 (s, 3H, 4-CH3OC6H4CH2), 2.22–1.97 (4s, 12H, CH3CO).
Anal. For C31H33N3O11S Calcd.: C, 56.79; H, 5.07. Found: C, 57.0; H, 5.0.
4-(4-Methylphenyl)-2-(2,3,4,6-tetra-O-acetyl-b-D-galactopyranosyl)-6-(4-meth-
oxybenzyl)-3-thioxo-2,3-dihydro-1,2,4-triazin-5(4H)-one (10f). Using the general
procedure, 9f gave 10f (72.1%); Rf ¼ 0.73; mp. 104ꢁC; IR (KBr), 1751 (C¼O acet-
1
ate), 1705 (C¼O amide) cmꢀ1; H NMR (CDCl3) d 7.35–6.83 (m, 8H, ArH’s), 6.8
0
0
0
(d, 1H, J ¼ 9.2 Hz, H1 ), 5.96 (t, 1H, J ¼ 9.7 Hz, H2 ), 5.5 (d, 1H, J ¼ 3.2 Hz, H4 ),
0
0
0
5.23 (dd, 1H, J ¼ 3.4, 10 Hz, H3 ), 4.2–3.92 (m, 3H, H5 , H6 ), 3.9 (s, 2H, 4-
CH3OC6H4CH2), 3.78 (s, 3H, 4-CH3OC6H4CH2), 2.4 (s, 3H, 4-CH3C6H4N),
2.22–1.97 (4s, 12H, CH3CO).
Anal. For C32H35N3O11S Calcd.: C, 57.39; H, 5.27. Found: C, 57.4; H, 5.3.
4-Phenyl-2-(2,3,4,6-tetra-O-acetyl-b-D-galactopyranosyl)-6-(4-chlorobenzyl)-3-
thioxo-2,3-dihydro-1,2,4-triazin-5(4H)-one (10g). Using the general procedure, 9g
gave 10g (79.5%); Rf ¼ 0.74; mp. 106ꢁC; IR (KBr), 1751 (C¼O acetate), 1705
1
(C¼O amide) 0cmꢀ1; H NMR (CDCl3) d 7.57–7.07 (m, 9H, ArH’s), 6.8 (d, 1H,
0
0
J ¼ 9.2 Hz, H1 ), 5.88 (t, 1H, J ¼ 9.6 Hz, H2 ), 5.49 (d, 1H, J ¼ 3.4 Hz, H4 ), 5.23
0
0
0
(dd, 1H, J ¼ 3.4, 10.2 Hz, H3 ), 4.17–3.96 (m, 3H, H5 , H6 ), 3.93 (s, 2H, 4-
ClC6H4CH2), 2.21–1.96 (4s, 12H, CH3CO).
Anal. For C30H30N3O10SCl Calcd.: C, 54.59; H, 4.58. Found: C, 54.7; H, 4.7.
4-(4-Methylphenyl)-2-(2,3,4,6-tetra-O-acetyl-b-D-galactopyranosyl)-6-(4-chloro-
benzyl)-3-thioxo-2,3-dihydro-1,2,4-triazin-5(4H)-one (10h). Using the general proce-
dure, 9h gave 10h (63%); Rf ¼ 0.73; mp. 124ꢁC; IR (KBr), 1751 (C¼O acetate),
1
1701 (C¼O amide) cmꢀ1; H NMR (CDCl3) d 7.6–7.03 (m, 8H, ArH’s), 6.8 (d,
0
0
0
1H, J ¼ 9.3 Hz, H1 ), 5.89 (t, 1H, J ¼ 8.7 Hz, H2 ), 5.48 (d, 1H0, J ¼ 3.3 Hz, H4 ),
0
0
5.23 (dd, 1H, J ¼ 3.4, 10.0 Hz, H3 ), 4.17-3.90 (m, 3H, H5 , H6 ), 3.92 (s, 2H, 4-
CH3C6H4CH2), 2.4 (s, 3H, 4-CH3C6H4CH2), 2.19–1.98 (4s, 12H, CH3CO).
Anal. For C31H32N3O10SCl Calcd.: C, 55.23; H, 4.78. Found: C, 55.1; H, 4.8
4-Phenyl-2-(2,3,4,6-tetra-O-acetyl-b-D-galactopyranosyl)-6-(4-N,N-dimethylami-
nobenzyl)-3-thioxo-2,3-dihydro-1,2,4-triazin-5(4H)-one (10i). Using the general pro-
cedure, 9i gave 10i (45.9%); Rf ¼ 0.75; mp. 114ꢁC; IR (KBr), 1751 (C¼O acetate),
1707 (C¼O amide) cmꢀ1
;
1H NMR (CDCl3) d 7.57–6.7 (m, 9H, ArH’s),
0
0
6.68 (d, 1H, J ¼ 9.3 Hz, H1 ), 5.99 (t, 1H, J ¼ 9.6 Hz, H2 ), 5.49 0 (d, 1H, J ¼ 3.3 Hz,
0
0
0
H4 ), 5.23 (dd, 1H, J ¼ 3.4, 10.0 Hz, H3 ), 4.16–3.89 (m, 3H, H5 , H6 ), 3.86 (s, 2H,
4-NMe2C6H4CH2), 2.92 (s, 6H, 4-N(CH3)2C6H4CH2), 2.22–1.96 (4s, 12H, CH3CO).
Anal. For C32H36N4O10S Calcd.: C, 57.47; H, 5.42. Found: C, 57.6; H, 5.4.

34
Mansour, Eid, and Khalil
4-(4-Methylphenyl)-2-(2,3,4,6-tetra-O-acetyl-b-D-galactopyranosyl)-6-(4-N,N-
dimethylaminobenzyl)-3-thioxo-2,3-dihydro-1,2,4-triazin-5(4H)-one (10j). Using the
general procedure, 9j gave 10j (36.1%); Rf ¼ 0.74; mp. 90ꢁC; IR (KBr), 1751 (C¼O
1
acetate), 1701 (C¼O amide) cmꢀ1; H NMR (CDCl3) d 7.57–6.7 (m, 8H, ArH’s),
0
0
6.68 (d, 1H, J ¼ 8.4 Hz, H1 ), 5.99 (t, 1H, J ¼ 9.6 Hz, H2 ), 5.49 0(d, 1H, J ¼ 3.0 Hz,
0
0
0
H4 ), 5.23 (dd, 1H, J ¼ 3.4, 10.0 Hz, H3 ), 4.17–3.88 (m, 3H, H5 , H6 ), 3.86 (s, 2H,
4-NMe2C6H4CH2), 2.92 (s, 6H, 4-N(CH3)2C6H4CH2), 2.39 (s, 3H, 4-CH3C6H4N),
2.29–1.96 (4s, 12H, CH3CO).
Anal. For C33H38N4O10S Calcd.: C, 58.05; H, 5.61. Found: C, 58.1; H, 5.6.
4-Phenyl-2-(2,3,4,6-tetra-O-acetyl-b-D-galactopyranosyl)-6-b-(4-chlorophenyl)-
vinyl-3-thioxo-2,3-dihydro-1,2,4-triazin-5(4H)-one (10k). Using the general proce-
dure, 9k gave 10k (63.3%); Rf ¼ 0.7; mp. 146ꢁC; IR (KBr), 1749 (C¼O acetate),
1707 (C¼O amide) cmꢀ1; 1H NMR (CDCl3) d 7.98, 7.12 (2d, 2H, J ¼ 16.4 Hz, trans
0
CH¼CH), 7.70–7.06 (m, 9H, ArH’s), 6.810 (d, 1H, J ¼ 9.2 Hz, H1 ), 6.02 (t, 1H,
0
J ¼ 9.6 Hz, H2 ), 5.53 (d, 1H, J ¼ 3 Hz, H4 ), 5.26 (dd, 1H, J ¼ 3.6, 10.2 Hz, H3 ),
0
0
4.2–4.0 (m, 3H, H5 , H6 ), 2.26–1.98 (4s, 12H, CH3CO).
Anal. For C31H30N3O10SCl Calcd.: C, 55.4; H, 4.5; N, 6.25. Found: C, 55.4; H,
4.6; N, 6.4.
2-(2,3,4,6-Tetra-O-acetyl-b-D-galactopyranosyl)-6-substituted-3-thioxo-2,3-di-
hydro-1,2,4-triazin-5(4H)-ones (12a–j). General procedure: To a solution of each
of 5a–f,h–j (10 mmol) in acetic acid (100 mL) was added a solution of sodium nitrite
(6 g in 6 mL water) dropwise with stirring and cooling at 0ꢁC over a period of one
hour and the reaction mixture was then kept in the refrigerator overnight. The next
day, the reaction mixture was diluted with ice-water mixture (400 g) and the formed
precipitate was collected and dried at room temperature. Crude 12c–j were chroma-
tographed over preparative TLC plates (silica gel 60 GF254) using ethyl acetate as an
eluent, extracted from chloroform on a soxhlet extractor, and the chloroform
extracts were then concentrated and diluted with petroleum ether (40–60ꢁC). The
formed precipitate of crude 12c–j were recrystallized from diethylether=petroleum
ether (40–60ꢁC) as colorless crystals of 12c,d,f, pale crystals of 12e and yellow crys-
tals of 12g–j. On the other hand, crude 12a,b were purified by recrystallization. Thus,
crude 12a was recrystallized from diethyl ether=peteroleum ether (40–60ꢁC), while
crude 12b was recrystallized from chloroform=ethanol, both as colorless crystals
of pure 12a,b.
2-(2,3,4,6-Tetra-O-acetyl-b-D-galactopyranosyl)-6-methyl-3-thioxo-2,3-dihydro-
1,2,4-triazin-5(4H)-one (12a). Using the general procedure, 5a gave 12a (10%);
mp. 117ꢁC; IR (KBr), 3423 (NH), 1751 (C¼O acetate), 1714 (C¼O amide) cmꢀ1
;
1H NMR (CDCl3) d 9.72 (brs, 1H, NH exchangeable), 6.63 (d, 1H, J ¼ 9.2 Hz,
0
0
0
H1 ), 5.83 (t, 1H,0 J ¼ 9.8 Hz, H2 ), 5.49 (0d, 1H, J ¼ 3 Hz, H4 ), 5.23 (dd, 1H,
0
J ¼ 3.2, 10 Hz, H3 ), 4.25–4.12 (m, 3H, H5 , H6 ), 2.33 (s, 3H, CH3), 2.22, 2.06,
2.01, 2.0 (4s, 12H, CH3CO).
Anal. For C18H23N3O10S Calcd.: C, 45.66; H, 4.9; N, 8.87. Found: C, 45.7; H,
4.9; N, 8.8.

6-Substituted-2-b-galactosyl-1,2,4-triazines
35
2-(2,3,4,6-Tetra-O-acetyl-b-D-galactopyranosyl)-6-phenyl-3-thioxo-2,3-dihydro-
1,2,4-triazin-5(4H)-one (12b). Using the general procedure, 5b gave 12b (75%); mp.
1
230ꢁC; IR (KBr), 3418 (NH), 1743 (C¼O acetate), 1715 (C¼O amide) cmꢀ1; H
NMR (CDCl3) d 10.31 (brs, 1H, NH), 8.18–7.48 (m, 5H, ArH’s), 6.8 (d, 1H,
0
0
0
J ¼ 9 Hz, H1 ), 5.96 (t, 1H, J ¼ 10.1 Hz, H2 ), 5.52 (d, 1H, J ¼ 3 Hz, H4 ), 5.27 (dd,
0
0
0
1H, J ¼ 3.4, 10.1 Hz, H3 ), 4.25–4.0 (m, 3H, H5 , H6 ), 2.2, 2.06, 2.04, 2.02 (4s,
12H, CH3CO).
Anal. For C23H25N3O10S Calcd.: C, 51.58; H, 4.7; N, 7.85. Found: C, 51.6; H,
4.5; N, 7.7.
2-(2,3,4,6-Tetra-O-acetyl-b-D-galactopyranosyl)-6-benzyl-3-thioxo-2,3-dihydro-
1,2,4-triazin-5(4H)-one (12c). Using the general procedure, 5c gave 12c (76%);
Rf ¼ 0.74; mp. 85ꢁC; IR (KBr), 3421 (NH), 1751 (C¼O acetate), 1713 (C¼O amide)
1
cmꢀ1; H NMR (CDCl3) d 10.04 (brs, 1H, NH), 7.36–7.3 (m, 5H, ArH’s), 6.66 (d,
0
0
0
1H, J ¼ 9.2 Hz, H1 ), 5.9 (t, 01H, J ¼ 9.3 Hz, H2 ), 5.5 (d, 1H, J ¼ 3.1 Hz, H4 ), 5.25
0
0
(dd, 1H, J ¼ 3.1, 9.8 Hz, H3 ), 4.23–3.9 (m, 5H, H5 , H6 , PhCH2), 2.21, 2.06, 2.03,
1.95 (4s, 12H, CH3CO).
Anal. For C24H27N3O10S Calcd.: C, 52.45; H, 4.95; N, 7.65. Found: C, 52.5; H,
5.0; N, 7.7.
2-(2,3,4,6-Tetra-O-acetyl-b-D-galactopyranosyl)-6-(4-methylbenzyl)-3-thioxo-2,3-
dihydro-1,2,4-triazin-5(4H)-one (12d). Using the general procedure, 5d gave 12d
(74%); Rf ¼ 0.74; mp. 94ꢁC; IR (KBr), 3217 (NH), 1751 (C¼O acetate), 1716
1
(C¼O amide) cmꢀ1; H NMR (CDCl3) d 9.55 (brs, 1H, NH), 7.26, 7.12 (2d, 4H,
0
0
ArH’s),6.65 (d, 1H, J ¼ 9.2 Hz, H1 ), 5.89 (t, 1H, J ¼ 9.3 Hz, H2 ), 5.490 (d, 1H,
0
0
0
J ¼ 3.2 Hz, H4 ), 5.25 (dd, 1H, J ¼ 3.2, 9.3 Hz, H3 ), 4.25–3.89 (m, 5H, H5 , H6 , 4-
CH3C6H4CH2), 2.31 (s, 3H, 4-CH3C6H4CH2), 2.21, 2.06, 2.03, 1.95 (4s, 12H,
CH3CO).
Anal. For C25H29N3O10S Calcd.: C, 53.28; H, 5.19. Found: C, 53.3; H, 5.2.
2-(2,3,4,6-Tetra-O-acetyl-b-D-galactopyranosyl)-6-(4-methoxybenzyl)-3-thioxo-2,3-
dihydro-1,2,4-triazin-5(4H)-one (12e). Using the general procedure, 5e gave 12e
(75%); Rf ¼ 0.75; mp. 100ꢁC; IR (KBr), 3225 (NH), 1747 (C¼O acetate), 1713
1
(C¼O amide) cmꢀ1; H NMR (CDCl3) d 9.7 (brs, 1H, NH), 7.28, 6.83 (2d, 4H,
0
0
ArH’s), 5.92 (d, 1H, J ¼ 9.2 Hz, H1 ), 5.89 (t, 1H, J ¼ 9 Hz, H2 ), 5.480 (d, 1H,
0
0
0
J ¼ 3.4 Hz, H4 ), 5.22 (dd, 1H, J ¼ 3.1, 9.3 Hz, H3 ), 4.25–3.86 (m, 5H, H5 , H6 , 4-
CH3OC6H4CH2), 3.77 (s, 3H, 4-CH3OC6H4CH2), 2.21, 2.04, 2.02, 1.91 (4s, 12H,
CH3CO).
Anal. For C25H29N3O11S Calcd.: C, 51.81; H, 5.04. Found: C, 51.8; H, 5.0.
2-(2,3,4,6-Tetra-O-acetyl-b-D-galactopyranosyl)-6-(4-chlorobenzyl)-3-thioxo-2,3-
dihydro-1,2,4-triazin-5(4H)-one (12f). Using the general procedure, 5f gave 12f
(77.3%); Rf ¼ 0.74; mp. 122ꢁC (decomp.); IR (KBr), 3223 (NH), 1751 (C¼O acetate),
1722 (C¼O amide) cmꢀ1; 1H NMR (CDCl3) d 9.86 (brs, 1H, NH), 7.3–7.25 (2d, 4H,
0
0
ArH’s), 6.67 (d, 1H, J ¼ 9.2 Hz, H1 ), 5.8 (t, 1H, J ¼ 10.1 Hz, H2 ), 5.48 (d, 1H,

36
Mansour, Eid, and Khalil
0
0
0
0
J ¼ 3.2 Hz, H4 ), 5.24 (dd, 1H, J ¼ 3.4, 10 Hz, H3 ), 4.25–3.88 (m, 5H, H5 , H6 , 4-
ClC6H4CH2), 2.19, 2.05, 2.04, 1.96 (4s, 12H, CH3CO).
Anal. For C24H26N3O10SCl Calcd.: C, 49.36; H, 4.49. Found: C, 49.4; H, 4.5.
2-(2,3,4,6-Tetra-O-acetyl-b-D-galactopyranosyl)-6-styryl-3-thioxo-2,3-dihydro-
1,2,4-triazin-5(4H)-one (12g). Using the general procedure, 5h gave 12g (70%);
Rf ¼ 0.73; mp. 170ꢁC; IR (KBr), 3229 (NH), 1755 (C¼O acetate), 1713 (C¼O amide)
1
cmꢀ1; H NMR (CDCl3) d 9.4 (brs, 1H, NH), 7.91, 7.11 (2d, 2H, J ¼ 16.4 Hz, trans
0
CH¼CH), 7.61–7.35 (m, 5H, ArH’s), 6.0 (d, 1H, J ¼ 9.6 Hz, H1 ), 5.95 (t, 1H,
0
0
0
J ¼ 9.9 Hz, H2 ), 5.53 (d,0 1H, J ¼ 3.2 Hz, H4 ), 5.55 (dd, 1H, J ¼ 3.3, 9.9 Hz, H3 ),
0
4.25–4.1 (m, 3H, H5 , H6 ), 2.25, 2.05, 2.04, 1.98 (4s, 12H, CH3CO).
Anal. For C25H27N3O10S Calcd.: C, 53.47; H, 4.84; N, 7.48. Found: C, 53.5; H,
4.8; N, 7.5.
2-(2,3,4,6-Tetra-O-acetyl-b-D-galactopyranosyl)-6-b-(4-methylphenyl)vinyl-3-thioxo-
2,3-dihydro-1,2,4-triazin-5(4H)-one (12h). Using the general procedure, 5i gave 12h
(78%); Rf ¼ 0.72; mp. 198ꢁC; IR (KBr), 3209 (NH), 1751 (C¼O acetate), 1736 (C¼O
1
amide) cmꢀ1; H NMR (CDCl3) d 9.8 (s, 1H, NH), 7.98, 7.05 (2d, 2H, J ¼ 16.6 Hz,
0
trans CH¼CH), 7.49, 7.2 (2d, 4H, ArH’s), 6.64 (d, 1H, J ¼ 9.6 Hz, H1 ), 5.95 0(t, 1H,
0
0
J ¼ 9.7 Hz, H2 ),05.510 (d, 1H, J ¼ 3 Hz, H4 ), 5.25 (dd, 1H, J ¼ 3.2, 9.7 Hz, H3 ), 4.3–
4.15 (m, 3H, H5 , H6 ), 2.37 (s, 3H, CH3), 2.24, 2.06, 2.03, 1.99 (4s, 12H, CH3CO).
Anal. For C26H29N3O10S Calcd.: C, 54.25; H, 5.08. Found: C, 54.2; H, 5.2.
2-(2,3,4,6-Tetra-O-acetyl-b-D-galactopyranosyl)-6-b-(4-methoxyphenyl)vinyl-3-
thioxo-2,3-dihydro-1,2,4-triazin-5(4H)-one (12i). Using the general procedure, 5j
gave 12i (73.8%); Rf ¼ 0.7; mp. 135ꢁC; IR (KBr), 3213 (NH), 1755 (C¼O acetate),
1
1705 (C¼O amide) cmꢀ1; H NMR (CDCl3) d 9.77 (s, 1H, NH), 7.96, 6.93 (2d,
2H, J ¼016.4 Hz, trans CH¼CH), 7.55, 6.91 (2d, 4H, ArH’s), 6.64 (d0, 1H, J ¼ 9.8 Hz,
0
Hz, H1 ), 5.96 (t, 1H, J ¼ 9.7 Hz, H2 ), 5.52 (d, 1H, J ¼ 3.2 Hz, H4 ), 5.25 (dd, 1H,
0
0
0
J ¼ 3.2, 10 Hz, H3 ), 4.25–4.13 (m, 3H, H5 , H6 ), 3.84 (s, 3H, OCH3), 2.24, 2.06,
2.03, 1.99 (4s, 12H, CH3CO).
Anal. For C26H29N3O11S Calcd.: C, 52.79; H, 4.94. Found: C, 52.8; H, 4.9.
2-(2,3,4,6-Tetra-O-acetyl-b-D-galactopyranosyl)-6-b-(4-chlorophenyl)vinyl-3-
thioxo-2,3-dihydro-1,2,4-triazin-5(4H)-one (12j). Using the general procedure, 5k
gave 12j (78%); Rf ¼ 0.73; mp. 118ꢁC; IR (KBr), 3224 (NH), 1756 (C¼O acetate),
1
1709 (C¼O amide) cmꢀ1; H NMR (CDCl3) d 9.96 (brs, 1H, NH), 7.96, 7.05 (2d,
2H, J ¼ 16.4 Hz, trans CH¼CH), 7.53, 7.36 (2d, 4H, ArH’s),06.64 (d, 1H, J ¼ 9.2 Hz,
0
0
H1 ), 5.940(t, 1H, J ¼ 9.6 Hz, H2 ),0 5.52 (d, 1H, J ¼ 3.4 Hz, H4 ), 5.26 (dd, 1H, J ¼ 3.2,
0
10 Hz, H3 ), 4.25–4.12 (m, 3H, H5 , H6 ), 2.24, 2.06, 2.03, 1.99 (4s, 12H, CH3CO).
Anal. For C25H26N3O10SCl Calcd.: C, 50.38; H, 4.4. Found: C, 50.4; H, 4.4.
Action of Methyl Iodide on Compounds 12c,d,h–j
General procedure (A): To a solution of each 12c,d,i (1 mmol) in N,N-dimethyl-
formamide (1 mL) was added triethylamine (0.28 mL, 2 mmol) and methyliodide

6-Substituted-2-b-galactosyl-1,2,4-triazines
37
(0.1 mL, 1.5 mmol). The reaction mixture was then shaken at 40–50ꢁC for 5 min.
After cooling and dilution with water, the precipitate was collected and recrystallized
from dilute N,N-dimethylformamide.
General procedure (B): To a solution of each 12h–j (1 mmol) in N,N-dimethyl-
formamide (5 mL) was added anhydrous sodium carbonate (0.6 g, 5.7 mmol) and
methyliodide (0.1 m, 1.5 mmol). The reaction mixture was then shaken at 40–50ꢁC
for 5 min. After cooling and dilution with water, the precipitate was collected, dried
at ambient temperature, and chromatographed over preparative TLC plates (silica
gel 60 GF254) using ethyl acetate as an eluent. The product was extracted from
chloroform on a soxhlet extractor and recrystallized from chloroform-petroleum
ether (40–60ꢁC).
Action of Methyl Iodide on 12c
Using general procedure (A), 12c gave a colorless mixture of 13a, 14a, and 15a in
1
a ratio of 72.7:9.1:18.2 respectively, as identified by H NMR (CDCl3) spectrum,
which showed signals at d 3.64 (s, 4-NCH3), 3.31 (s, 5-OCH3), 2.59 (s, 3-SCH3).
Anal. For C25H29N3O10S Calcd.: C, 53.28; H, 5.19; N, 7.46. Found: C, 53.3; H,
5.2; N, 7.6.
Action of Methyl Iodide on 12d
Using general procedure (A), 12d gave a colorless mixture of 13b, 14b, and 15b
1
in a ratio of 38.5:7.7:53.8 respectively, as identified by H NMR (CDCl3) spectrum,
which revealed signals at d 3.63 (s, 4-NCH3), 3.29 (s, 5-OCH3), 2.58 (s, 3-SCH3).
Anal. For C26H31N3O10S Calcd.: C, 54.06; H, 5.41. Found: C, 54.1; H, 5.5.
Action of Methyl Iodide on 12h
Using general procedure (B), 12h gave a yellow mixture of 13c, 14c,and 15c in a
ratio of 27.3:9.1:63.6 respectively, as identified by 1H NMR (CDCl3) spectrum,
which revealed signals at d 3.75 (s, 4-NCH3), 3.4 (s, 5-OCH3), 2.62 (s, 3-SCH3).
Anal. For C27H31N3O10S Calcd.: C, 55.0; H, 5.3. Found: C, 55.1; H, 5.4.
Action of Methyl Iodide on 12i
Using general procedure (B), 12i gave a yellow mixture of 13d, 14d, and 15d in a
ratio of 18.1:31.9:50 respectively=Using general procedure (A) 12i gave a yellow mix-
ture of 14d and 15d in a ratio of 25.7:74.3 respectively. The previous ratios were
identified by 1H NMR (CDCl3) spectra which revealed signals at d 3.77 (s, 4-
NCH3), 3.34 (s, 5-OCH3), 2.66 (s, 3-SCH3).
Anal. For C27H31N3O11S Calcd.: C, 53.55; H, 5.16. Found: C, 53.6; H, 5.2
(method A)=C, 53.5; H, 5.2 (method B).

38
Mansour, Eid, and Khalil
Action of Methyl Iodide on 12j
Using general procedure (B), 12j gave a yellow mixture of 13e, 14e, and 15e in a
1
ratio of 51.6:9.7:38.7 respectively. This ratio was determined by H NMR (CDCl3)
spectrum which revealed signals at d 3.75 (s, 4-NCH3), 3.4 (s, 5-OCH3), 2.66 (s,
3-SCH3).
Anal. For C26H28N3O10SCl Calcd.: C, 51.19; H, 4.63. Found: C, 51.2; H, 4.7.
4-Benzylideneamino-2-(2,3,4,6-tetra-O-acetyl-b-D-galactopyranosyl)-3-thioxo-2,3-
dihydro-1,2,4-triazin-5(4H)-ones 17a–h. General procedure (A): To a solution
of each of 16a–h (10 mmol) in acetonitrile (5 mL), triethylamine (2 mL, 14 mmol)
was added followed by 2,3,4,6-tetra-O-acetyl-a-D-galactopyranosyl bromide (4)
(15 mmol). The reaction mixture was stirred for 20 min and kept at room tempera-
ture for two days. The reaction mixture was diluted with ice-water mixture and acid-
ified with acetic acid (1 mL). The precipitate was then collected, washed with water,
dried at room temperature and then chromatographed over preparative TLC plates
(silica gel 60 GF254) using ethyl acetate as an eluent. The crude 17a–h were then
extracted from chloroform on a soxhlet extractor. The chloroform extracts were then
concentrated and diluted with petroleum ether (40–60ꢁC). After collecting the crude
17a–h, they were recrystallized from diethylether=petroleum ether (40–60ꢁC) as
colorless crystals of 17a–f, and yellow crystals of 17g,h.
General procedure (B): A mixture of 5f (15 mmol) and benzaldehyde (10 mL)
was heated at 150–160ꢁC in an oil bath for 15 min. This mixture was then heated
under reflux in methanol for further 30 min, cooled, and filtered. The solution of
17f in methanol was evaporated in vacuo, concentrated, and the remaining residue
was chromatographed over preparative TLC plates plates (silica gel 60 GF254) using
ethyl acetate as an eluent and extracted from chloroform on a soxhlet extractor. The
chloroform extract was then concentrated, diluted with petroleum ether (40–60ꢁC),
and finally recrystallized from diethylether=petroleum ether (40–60ꢁC) as colorless
crystals of 17f.
4-Benzylidineamino-2-(2,3,4,6-tetra-O-acetyl-b-D-galactopyranosyl)-6-methyl-3-
thioxo-2,3-dihydro-1,2,4-triazin-5(4H)-one (17a). Using the general procedure (A),
16a gave 17a (85.4%); Rf ¼ 0.72; mp. 80ꢁC; IR (KBr), 1751 (C¼O acetate), 1697
1
(C¼O amide) cmꢀ1; H NMR (CDCl3) d 8.37 (s, 1H, N¼CH), 7.95–7.37 (m, 5H,
0
0
ArH’s), 6.85 (d, 1H, J ¼ 9.2 Hz, H1 ), 5.96 (t, 1H, J ¼ 9.7 Hz, H2 ), 5.51 (d, 1H,
0
0
0
0
J ¼ 3.2 Hz, H4 ), 5.26 (dd, 1H, J ¼ 3.5, 12.7 Hz, H3 ), 4.25–4 (m, 3H, H5 , H6 ), 2.4
(s, 3H, CH3), 2.23, 2.06, 2.02, 2.0 (4s, 12H, CH3CO).
Anal. For C25H28N4O10S Calcd.: C, 52.08; H, 4.89; N, 9.72. Found: C, 52.1; H,
4.7; N, 9.5.
4-Benzylidineamino-2-(2,3,4,6-tetra-O-acetyl-b-D-galactopyranosyl)-6-phenyl-3-
thioxo-2,3-dihydro-1,2,4-triazin-5(4H)-one (17b). Using the general procedure (A),
16b gave 17b (78%); Rf ¼ 0.73; mp. 86ꢁC; IR (KBr), 1751 (C¼O acetate), 1701
(C¼O amide) cmꢀ1
;
1H NMR (CDCl3) d 8.44 (s, 1H, N¼CH), 8.23–7.37 (m,
0
0
10H, ArH’s),7.03 (d, 1H, J ¼ 9.2 Hz, H1 ), 6.07 (t, 1H, J ¼ 9.6 Hz, H2 ), 5.52

6-Substituted-2-b-galactosyl-1,2,4-triazines
39
0
0
0
0
(d, 1H, J ¼ 3.4 Hz, H4 ), 5.29 (dd, 1H, J ¼ 3.4, 10 Hz, H3 ), 4.2–4.1 (m, 3H, H5 , H6 ),
2.2–2.02 (4s, 12H, CH3CO).
Anal. For C30H30N4O10S Calcd.: C, 56.42; H, 4.73; N, 8.77. Found: C, 56.6; H,
4.9; N, 8.7.
4-Benzylidineamino-2-(2,3,4,6-tetra-O-acetyl-b-D-galactopyranosyl)-6-benzyl-3-
thioxo-2,3-dihydro-1,2,4-triazin-5(4H)-one (17c). Using the general procedure (A),
16c gave 17c (63.6%); Rf ¼ 0.7; mp. 146ꢁC; IR (KBr), 1751 (C¼O acetate), 1697
1
(C¼O amide) cmꢀ1; H NMR (CDCl3) d 8.33 (s, 1H, N¼CH), 7.91–7.23 (m, 10H,
0
0
ArH’s), 6.86 (d, 1H, J ¼ 9.2 Hz, H1 ), 6.1 (t, 1H, J ¼ 9.7 Hz, H2 ), 5.5 (d, 1H,
0
0
0
0
J ¼ 3.2 Hz, H4 ), 5.26 (dd, 1H, J ¼ 3.3, 10.1 Hz, H3 ), 4.25–3.95 (m, 3H, H5 , H6 ),
3.98 (s, 2H, PhCH2), 2.23–1.9 (s, 12H, CH3CO).
Anal. For C31H32N4O10S Calcd.: C, 57.05; H, 4.94; N, 8.58. Found: C, 57.2; H,
4.9; N, 8.7.
4-Benzylidineamino-2-(2,3,4,6-tetra-O-acetyl-b-D-galactopyranosyl)-6-(4-methyl-
benzyl)-3-thioxo-2,3-dihydro-1,2,4-triazin-5(4H)-one (17d). Using the general proce-
dure (A), 16d gave 17d (73.5%); Rf ¼ 0.74; mp. 102ꢁC; IR (KBr), 1751 (C¼O acet-
1
ate), 1697 (C¼O amide) cmꢀ1; H NMR (CDCl3) d 8.33 (s, 1H, N¼CH), 7.9–7.1
0
0
(m, 9H, ArH’s), 6.86 (d, 1H, J ¼ 9.4 Hz, H1 ), 6.03 (t, 1H, J ¼ 9.6 Hz, H2 ), 5.5 (d,
0
0
0
1H, J ¼ 3.2 Hz, H4 ), 5.27 (dd, 1H, J ¼ 3.5, 10.1 Hz, H3 ), 4.25–3.9 (m, 5H, H5 ,
0
H6 , 4-CH3-C6H4CH2), 2.32 (s, 3H, CH3), 2.23–1.92 (4s, 12H, CH3CO).
Anal. For C32H34N4O10S Calcd.: C, 57.65; H, 5.14. Found: C, 57.4; H, 4.9.
4-Benzylidineamino-2-(2,3,4,6-tetra-O-acetyl-b-D-galactopyranosyl)-6-(4-meth-
oxybenzyl)-3-thioxo-2,3-dihydro-1,2,4-triazin-5(4H)-one (17e). Using the general
procedure (A), 16e gave 17e (70.4%); Rf ¼ 0.73; mp. 124ꢁC; IR (KBr), 1751
(C¼O acetate), 1699 (C¼O amide) cmꢀ1; 1H NMR (CDCl3) d 8.33 (s, 1H, N¼CH),
0
7.91–6.83 (m, 9H, ArH’s), 6.86 (d, 1H, J ¼ 9.4 Hz, H1 ), 6.02 (t, 1H, J ¼ 9.6 Hz,
0
0
0
H2 ), 5.49 (d, 1H, J ¼ 3.3 Hz, H4 ), 5.23 (dd, 1H, J ¼ 3.3, 10.1 Hz, H3 ), 4.25–3.87
0
0
(m, 3H, H5 , H6 ), 3.95 (s, 2H, 4-CH3OC6H4CH2), 3.78 (s, 3H, 4-CH3OC6H4CH2),
2.23–1.97 (4s, 12H, CH3CO).
Anal. For C32H34N4O11S Calcd.: C, 56.3; H, 5.02. Found: C, 56.2; H, 5.0.
4-Benzylidineamino-2-(2,3,4,6-tetra-O-acetyl-b-D-galactopyranosyl)-6-(4-chloro-
benzyl)-3-thioxo-2,3-dihydro-1,2,4-triazin-5(4H)-one (17f). Using the general proce-
dure (A, B), 16f gave 17f (69.6%, 55%); Rf ¼ 0.71; mp. 128ꢁC; IR (KBr), 1751 (C¼O
1
acetate), 1697 (C¼O amide) cmꢀ1; H NMR (CDCl3) d 8.41 (s, 1H, N=CH), 7.91–
0
0
7.26 (m, 9H, ArH’s), 6.87 (d, 1H, J ¼ 9.4 Hz, H1 ), 5.96 (t, 1H, J ¼ 9.5 Hz, H2 ), 5.48
0
0
0
(d,0 1H, J ¼ 3.2 Hz, H4 ), 5.26 (dd, 1H, J ¼ 3.3, 10.1 Hz, H3 ), 4.25–3.95 (m, 3H, H5 ,
H6 ), 3.93 (s, 2H, 4-ClC6H4CH2), 2.22–1.96 (4s, 12H, CH3CO).
Anal. For C31H31N4O10SCl Calcd.: C, 54.19; H, 4.55. Found: C, 54.2; H, 4.6.
4-Benzylidineamino-2-(2,3,4,6-tetra-O-acetyl-b-D-galactopyranosyl)-6-styryl-3-
thioxo-2,3-dihydro-1,2,4-triazin-5(4H)-one (17g). Using the general procedure (A),
16g gave 17g (84%); Rf ¼ 0.73; mp. 102ꢁC; IR (KBr), 1751 (C¼O acetate), 1697
1
(C¼O amide) cmꢀ1; H NMR (CDCl3) d 8.42 (s, 1H, N¼CH), 8.02, 7.18 (2d, 2H,

40
Mansour, Eid, and Khalil
0
J ¼ 16.4 Hz, trans CH¼CH), 7.7–7.36 (m, 10H, ArH’s), 6.86 (d, 1H, J ¼ 9.4 Hz, H1 ),
0
0
6.09 (t, 1H, J ¼ 9.7 Hz, H2 ), 5.540 (d, 1H, J ¼ 3.4 Hz, H4 ), 5.28 (dd, 1H, J ¼ 3.2,
0
0
10.2 Hz, H3 ), 4.27–4.1 (m, 3H, H5 , H6 ), 2.26–2.0 (4s, 12H, CH3CO).
Anal. For C32H32N4O10S Calcd.: C, 57.82; H, 4.85; N, 8.43. Found: C, 57.9; H,
4.8; N, 8.5.
4-Benzylidineamino-2-(2,3,4,6-tetra-O-acetyl-b-D-galactopyranosyl)-6-b-(4-meth-
oxyphenyl)vinyl-3-thioxo-2,3-dihydro-1,2,4-triazin-5(4H)-one (17h). Using the gen-
eral procedure (A), 16h gave 17h (83.3%); Rf ¼ 0.74; mp. 134ꢁC; IR (KBr), 1751
(C¼O acetate), 1701 (C¼O amide) cmꢀ1; 1H NMR (CDCl3) d 8.41 (s, 1H, N¼CH),
7.97, 7.05 (2d, 2H, 0J ¼ 16.4 Hz, trans CH¼CH), 7.96–6.85 (m, 9H, ArH’s), 6.86 (d,
0
0
1H, J ¼ 9.2 Hz, H1 ), 6.09 (t, 1H, J ¼ 10.3 Hz, H2 ), 5.54 (d, 1H, J ¼ 3.3 Hz, H4 ),
0
0
0
5.28 (dd, 1H, J ¼ 3.5, 10.1 Hz, H3 ), 4.27–4.0 (m, 3H, H5 , H6 ), 3.85 (s, 3H,
OCH3), 2.26–1.95 (4S, 12H, CH3CO).
Anal. For C33H34N4O11S Calcd.: C, 57.05; H, 4.93. Found: C, 57.2; H, 4.9.
4-Aryl-2-(2,3,4,6-tetra-O-acetyl-b-D-galactopyranosyl)-6-substituted-1,2,4-tri-
azine-3,5(2H, 4H)dithiones 18a,b=2-(2,3,4,6-Tetra-O-acetyl-b-D-galactopyranosyl)-6-
substituted-1,2,4-tri-azine-3,5(2H,4H)dithiones 19a–f. General procedure: To a solu-
tion of each of 10a,g, 12b–f,i (1 mmol) in dry pyridine (5 mL) was added phosphor-
ous pentasulfide (0.45 g, 2 mmol). The reaction mixture was then heated under reflux
for 6 h. After cooling, the product was extracted from the oily materials with ethanol
(10 mL), and the supernatant solution was decanted, acidified with acetic acid
(0.5 mL), concentrated, and diluted with water. The precipitate was collected, dried
at room temperature, dissolved in diethylether for which was added charcoal (0.5 g),
filtered, and recrystallized from diethylether=petroleum ether (40–60ꢁC) as red crys-
tals of 18a, 19a,b and yellow crystals of 18b, 19c–f.
4-Phenyl-2-(2,3,4,6-tetra-O-acetyl-b-D-galactopyranosyl)-6-benzyl-1,2,4-triazine-
3,5(2H,4H)dithione (18a). Using the general procedure, 10a gave 18a (50%);
1
mp. 121ꢁC; IR (KBr), 1751 (C¼O acetate) cmꢀ1; H NMR (CDCl3) d 7.49–7.08
0
0
(m, 10H, ArH’s), 6.79 0 (d, 1H, J ¼ 9.2 Hz, H1 ), 5.95 (t, 1H, 0J ¼ 9.6 Hz, H2 ), 5.50
(d,0 1H, J ¼ 2.8 Hz, H4 ), 5.24 (dd, 1H, J ¼ 3.4, 10.2 Hz, H3 ), 4.28–3.97 (m, 5H,
0
H5 , H6 , PhCH2), 2.22–1.98 (4s, 12H, CH3CO).
Anal. For C30H31N3O9S2 Calcd.: C, 56.15; H, 4.87; N, 6.55. Found: C, 56.1; H,
4.9; N, 6.7.
4-Phenyl-2-(2,3,4,6-tetra-O-acetyl-b-D-galactopyranosyl)-6-(4-chlorobenzyl)-1,2,4-
triazine-3,5(2H,4H)dithione (18b). Using the general procedure, 10g gave 18b
1
(52%); mp. 123ꢁC; IR (KBr), 1751 (C¼O acetate) cmꢀ1; H NMR (CDCl3) d 7.6–
0
0
7.05 (m, 9H, ArH’s), 6.8 (d, 1H, J ¼ 9.2 Hz, H1 ), 5.88 (t, 1H, J ¼ 9.6 Hz, H2 ), 5.49
0
0
0
(d,0 1H, J ¼ 3.4 Hz, H4 ), 5.23 (dd, 1H, J ¼ 3.4, 10 Hz, H3 ), 4.25–3.8 (m, 5H, H5 ,
H6 , 4-Cl-C6H4-CH2), 2.21–1.99 (4s, 12H, CH3CO).
Anal. For C30H30N3O9S2Cl Calcd.: C, 53.29; H, 4.47. Found: C, 53.3; H, 4.5.
2-(2,3,4,6-Tetra-O-acetyl-b-D-galactopyranosyl)-6-phenyl-1,2,4-triazine-3,5(2H,
4H)dithione (19a). Using the general procedure, 12b gave 19a (50%); mp. 127ꢁC; IR

6-Substituted-2-b-galactosyl-1,2,4-triazines
41
(KBr), 3223 (NH), 1753 (C¼O acetate) cmꢀ1; 1H NMR (CDCl3) d 8.17–7.47 (m, 6H,
0
0
NH exchangeable, ArH’s), 6.71 (d, 1H, J ¼ 9 Hz, H1 ), 5.91 0(t, 1H, J ¼ 9.6 Hz, H2 ),
0
0
5.5 (d, 1H, J ¼ 3.4 Hz, H4 ), 5.29 (dd, 1H, J ¼ 3.4, 10 Hz, H3 ), 4.26–4.0 (m, 3H, H5 ,
0
H6 ), 2.2–2.0 (4s, 12H, CH3CO).
Anal. For C23H25N3O9S2 Calcd.: C, 50.08; H, 4.57; N, 7.62. Found: C, 50.1; H,
4.6; N, 7.7.
2-(2,3,4,6-Tetra-O-acetyl-b-D-galactopyranosyl)-6-benzyl-1,2,4-triazine-3,5(2H,
4H)dithione (19b). Using the general procedure, 12c gave 19b (45%); mp. 192ꢁC;
MS: m=z 565 (Mþ, 20.7%); IR (KBr), 3216 (NH), 1757 (C¼O acetate) cmꢀ1
;
1H NMR (CDCl3) d 11.2 (s, 1H, NH), 7.39–7.2 (m, 5H, ArH’s), 6.61 (d, 1H,
0
0
0
J ¼ 9.2 Hz, H1 ), 5.85 (t, 1H, J ¼ 9.3 Hz, H2 ), 5.49 (d, 1H, J ¼ 3.2 Hz, H4 ), 5.24
0
0
0
(dd, 1H, J ¼ 3.5, 10.1 Hz, H3 ), 4.25–4.0 (m, 5H, H5 , H6 , PhCH2), 2.19, 2.06,
2.02, 1.97 (4s, 12H, CH3CO).
Anal. For C24H27N3O9S2 Calcd.: C, 50.96; H, 4.81; N, 7.43. Found: C, 51.5; H,
4.8; N, 7.4.
2-(2,3,4,6-Tetra-O-acetyl-b-D-galactopyranosyl)-6-(4-methylbenzyl)-1,2,4-triazine-
3,5-(2H, 4H)dithione (19c). Using the general procedure, 12d gave 19c (47.5%); mp.
100ꢁC (decomp.); IR (KBr), 3169 (NH), 1755 (C¼O acetate) cmꢀ1
;
1H NMR
0
(CDCl3) d 7.27–7.08 (m, 5H, NH, ArH’s), 6.61 (d, 1H, J ¼ 9.2 Hz, H1 ), 5.88 (t,
0
0
1H, J ¼ 9.2 Hz, H2 ), 5.48 (d, 1H, J ¼ 3.4 Hz, H4 ), 5.24 (dd, 1H, J ¼ 3.5, 10.1 Hz,
0
0
0
H3 ), 4.22–4.0 (m, 5H, H5 , H6 , 4-CH3C6H4-CH2), 2.3 (s, 3H, 4-CH3C6H4-CH2),
2.19–1.95 (4s, 12H, CH3CO).
Anal. For C25H29N3O9S2 Calcd.: C, 51.8; H, 5.04. Found: C, 51.7; H, 5.0.
2-(2,3,4,6-Tetra-O-acetyl-b-D-galactopyranosyl)-6-(4-methoxybenzyl)-1,2,4-tri-
azine-3,5(2H, 4H)dithione (19d). Using the general procedure, 12e gave 19d (46.9%);
1
mp. 104ꢁC (decomp.); IR (KBr), 3165 (NH), 1751 (C¼O acetate) cmꢀ1;0 H NMR
(CDCl3) d 7.37–6.81 (m, 5H, NH, ArH’s), 6.62 (d, 1H, J ¼ 9.2 Hz, H1 ), 5.86 (t,
0
0
1H, J ¼ 9.6 Hz, H2 ), 5.48 (d, 1H, J ¼ 3.2 Hz, H4 ), 5.24 (dd, 1H, J ¼ 3.5, 10.1 Hz,
0
0
0
H3 ), 4.25–4.0 (m, 5H, H5 , H6 , 4-CH3OC6H4-CH2), 3.78 (s, 3H, 4-CH3OC6H4-
CH2), 2.2–1.96 (4s, 12H, CH3CO).
Anal. For C25H29N3O10S2 Calcd.: C, 50.41; H, 4.91. Found: C, 50.3; H, 4.9.
2-(2,3,4,6-Tetra-O-acetyl-b-D-galactopyranosyl)-6-(4-chlorobenzyl)-1,2,4-triazine-
3,5(2H, 4H)dithione (19e). Using the general procedure, 12f gave 19e (48.6%); mp.
122ꢁC (decomp.); IR (KBr), 3171 (NH), 1751 (C¼O acetate) cmꢀ1
;
1H NMR
0
(CDCl3) d 7.37–7.25 (m, 5H, NH, ArH’s), 6.62 (d, 1H, J ¼ 9.2 Hz, H1 ), 5.78 (t,
0
0
1H, J ¼ 9.6 Hz, H2 ), 5.48 (d,0 1H, J ¼ 3.4 Hz, H4 ), 5.23 (dd, 1H, J ¼ 3.4, 10 Hz,
0
0
H3 ), 4.23–4.0 (m, 5H, H5 , H6 , 4-ClC6H4-CH2), 2.19–1.96 (4s, 12H, CH3CO).
Anal. For C24H26N3O9S2Cl Calcd.: C, 48.04; H, 4.37. Found: C, 47.9; H, 4.4.
2-(2,3,4,6-Tetra-O-acetyl-b-D-galactopyranosyl)-6-b-(4-methoxyphenyl)vinyl-1,2,4-
triazine-3,5(2H,4H)dithione (19f). Using the general procedure, 12i gave 19f (60%);
1
mp. 110ꢁC; IR (KBr), 3217 (NH), 1751 (C¼O acetate) cmꢀ1; H NMR (CDCl3) d

42
Mansour, Eid, and Khalil
0
7.58–6.89 (m, 7H, NH, CH¼CH, ArH’s), 6.91 (d, 1H, J ¼ 9 Hz, H1 ), 5.89 (t, 1H,
0
0
0
J ¼ 9 Hz, H2 ), 5.52 (d, 1H, J ¼ 3.2 Hz, H4 ), 5.24 (dd, 1H, J ¼ 3.5, 9.9 Hz, H3 ),
0
0
4.26–3.85 (m, 3H, H5 , H6 ), 3.85 (s, 3H, OCH3), 2.24–1.98 (4s, 12H, CH3CO).
Anal. For C26H29N3O10S2 Calcd.: C, 51.39; H, 4.81; N, 6.91. Found: C, 51.4; H,
4.8; N, 6.8.
Action of Methanolic Ammonia on 5i, 10g, 12g,i
General procedure: A saturated methanolic ammonia solution (40 mL; pre-
pared by bubbling dry ammonia gas in absolute methanol at 0ꢁC) was added to each
of 5i, 10g, 12g,i (1 mmol). The reaction mixture was then left overnight at room tem-
perature in a stoppered flask (after which time all materials went into solution). The
solvent was then removed on rotavap at room temperature. Compounds 20 and 22a
were crystallized from chloroform=ethanol as yellow crystals. Compounds 21 and
22b were recrystallized from water. Compound 21 was obtained as colorless crystals,
while 22b was obtained as yellow crystals.
4-Amino-2-b-D-galactopyranosyl-6-b-(4-methylphenyl)vinyl-3-thioxo-2,3-dihydro-
1,2,4-triazin-5(4H)-one (20). Using the general procedure, 5i gave 20 (85.7%); mp.
189ꢁC; IR (KBr), 3500–3200 (OH, NH2), 1689 (C¼O amide) cmꢀ1
;
1H NMR
(DMSO-d6) d 7.92, 7.11 (2d, 2H, J ¼ 16.7 Hz, trans CH¼CH), 7.6, 7.26 (2d, 4H,
0
ArH’s), 6.78 (s, 2H, NH2, exchangeable), 6.35 (d, 1H, J ¼ 8.8 Hz, H1 ), 5.8–4.2
0
0
0
0
0
(4m, 4H, 4OH, exchangeable), 4.25–3.5 (m, 6H, H2 , H3 , H4 , H5 , H6 ), 2.31 (s,
3H, CH3).
Anal. For C18H22N4O6S Calcd.: C, 51.17; H, 5.25; N, 13.26. Found: C, 51.2; H,
5.1; N, 13.5.
4-Phenyl-2-b-D-galactopyranosyl-6-(4-chlorobenzyl)-3-thioxo-2,3-dihydro-1,2,4-
triazin-5(4H)-one (21). Using the general procedure, 10g gave 21 (85.7%); mp.
1
216ꢁC; IR (KBr), 3500–3200 (OH), 1685 (C¼O amide) cmꢀ0 1; H NMR (DMSO-
d6) d 7.46–7.19 (m, 9H, ArH’s), 5.42 (d, 1H, J ¼ 9 Hz, H1 ), 5.40, 4.8, 4.55, 4.81
0
0
0
0
0
(4d, 4H, 4OH, exchangeable), 4.1–3.3 (m, 6H, H2 , H3 , H4 , H5 , H6 ).
Anal. For C22H22N3O6SCl Calcd.: C, 53.71; H, 4.51; N, 8.54. Found: C, 53.7; H,
4.4; N, 8.6.
2-b-D-galactopyranosyl-6-styryl-3-thioxo-2,3-dihydro-1,2,4-triazin-5(4H)-one
(22a). Using the general procedure, 12g gave 22a (85.7%); mp. 168ꢁC; IR (KBr),
1
3500–3200 (OH, NH), 1697 (C¼O amide) cmꢀ1; H NMR (DMSO-d6) d 12.45 (s,
1H, NH, exchangeable), 7.84, 7.08 (2d, 2H,0 J ¼ 16.4 Hz, trans CH¼CH), 7.67–7.13
(m, 5H, ArH’s), 5.42 (d, 1H, J ¼0 9 Hz, H10 ), 5.06, 5.0, 4.71, 4.62 (4d, 4H, 4OH,
0
0
0
exchangeable), 4.3–3.3 (m, 6H, H2 , H3 , H4 , H5 , H6 ).
Anal. For C17H19N3O6S Calcd.: C, 51.9; H, 4.87; N, 10.68. Found: C, 52.0; H,
4.9; N, 10.6.

6-Substituted-2-b-galactosyl-1,2,4-triazines
43
2-b-D-galactopyranosyl-6-b-(4-methoxyphenyl)vinyl-3-thioxo-2,3-dihydro-1,2,4-
triazin-5(4H)-one (22b). Using the general procedure, 12i gave 22b (62.5%);
1
mp. >285ꢁC; IR (KBr), 3500–3200 (OH, NH), 1701 (C¼O amide) cmꢀ1; H NMR
(DMSO-d6) d 12.34 (s, 1H, NH, exchangeable), 7.76, 6.96 (2d, 2H0, J ¼ 16.3 Hz, trans
CH¼CH), 7.61, 6.98 (2d, 4H, ArH’s), 5.39 (d, 1H, J ¼ 9 Hz, H10 ), 5.02, 4.97, 4.68,
0
0
0
0
4.59 (4d, 4H, 4OH, exchangeable), 4.2–3.2 (m, 6H, H2 , H3 , H4 , H5 , H6 ), 3.81 (s,
3H, OCH3).
Anal. For C18H21N3O7S Calcd.: C, 51.06; H, 5.0; N, 9.92. Found: C, 51.1; H,
5.1; N, 9.8.
Biological Evaluation of Compounds 5a–c,e,i,k, 12a,b,j, 19a,b and 22b
An in vitro model[19] was used as a primary human anticancer screen of com-
pounds 5a–c,e,i,k, 12a,b,j, 19a,b,and 22b. A 3-cell line, one-dose assay consisting
of MCF 7 (Breast), NCI-H460 (Lung), SF-268 (CNS) was used for the evaluation
of the latter compounds. Each cell line was inoculated and preincubated on a micro-
titer plate. Test agents were then added at a single concentration and the culture were
incubated for 48 h. End point determination was made with sulforhodamine B,
a protein-binding dye. Results for each test agent were reported as the percent of
growth of the treated cells when compared to the untreated control cells. Com-
pounds which reduce the growth of any one of the cell lines to 32% or less (negative
numbers indicate cell kill) are active (Table 2).
ACKNOWLEDGMENTS
The authors are very grateful to Dr. V. L. Narayanan and Dr. Edward Sausvile,
National Cancer Institute=National Institutes of Health, Bethesda, Maryland, USA,
for their valuable anticancer testing.
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Received May 13, 2002
Accepted October 22, 2002