276 Letters in Drug Design & Discovery, 2012, 9, 276-281
1875-628X/12 $58.00+.00 © 2012 Bentham Science Publishers
Synthesis of New S-alkylated-3-mercapto-1,2,4-triazole Derivatives
Bearing Cyclic Amine Moiety as Potent Anticancer Agents
M.S.R. Murty*
,a
, Kesur R. Ram
a
, Rayudu Venkateswara Rao
a
, J.S. Yadav
a
, Janapala Venkateswara
Rao
b
, R. Pamanji
b
and L.R. Velatooru
b
a
Organic Chemistry Division-I;
b
Toxicology Unit, Biology Division, Indian Institute of Chemical Technology,
Hyderabad-500607, India
Received August 01, 2011: Revised November 04, 2011: Accepted November 28, 2011
Abstract: A series of 3-[3-[4-(Substituted)-1-cyclicamine]propyl]thio-5-substituted[1,2,4]triazoles (8a-j) were
synthesized with good yields starting from corresponding carboxylic acids. The cytotoxicity studies of these derivatives
were studied against five different human cancer cell lines. Three compounds had shown good anticancer activity. The
triazole derivatives, 8i and 8j were most potent particularly against U937 and HL-60 cells. The cytotoxic potency of the
compounds varied between the cell lines suggesting that a structural property of these compounds as possible
determinants of their biological activity.
Keywords: 1,2,4-Triazoles, Acid hydrazides, Piperazines, Anticancer.
INTRODUCTION
Cancer drug discovery has traditionally focused on
targeting DNA synthesis, angiogenesis and cell division [1].
Although existing drugs show efficacy, their lack of
selectivity for tumor cells over normal cells can lead to
severe side effects [2]. Design and synthesis of novel small
molecules which can specifically block some targets in
tumor cells are in perspective direction in modern medicinal
chemistry. Hence, there is an urgent need for the discovery
and development of new anticancer agents. From different
groups of heterocycles, many synthetic small molecules with
cytotoxic activity have been reported and several of them
have undergone the clinical trials [3].
The chemistry of 1,2,4-triazoles and their fused
heterocyclic derivatives has received considerable attention
in the last few decades, owing to their synthetic and effective
biological importance [4]. The 1H-1,2,4-triazole compounds
possess an important pharmacological activities such as,
anti-inflammatory, CNS stimulants sedatives, antianxiety,
antimicrobial [5,6], and antimycotic agents such as
fluconazole, intraconazole and voriconazole [7]. Also, there
are known drugs containing the 1,2,4-triazole group e.g.
Triazolam [8], Alprazolam [9], Etizolam, and Furacylin.
Moreover, sulphur containing heterocycles represent an
important group of compounds and these heterocycles i.e.,
the mercapto- and thione-substituted 1,2,4-triazole ring
systems exhibit biological activities, such as anticancer
[10,11], antitubercular [12], diuretic [13], antibacterial [14],
antifungal [15], antimycobacterial [16], and hypoglycemic
[17].
Several piperazine derivatives were synthesized in the
last decade, as useful chemotherapeutic agents for various
diseases, such as crivixan (indinavir sulphate) and
*Address correspondence to this author at the Organic Chemistry Division-
I, Indian Institute of Chemical Technology, Hyderabad-500607, India;
Fax: 91-40-27193189; E-mail: msrmurty@ymail.com
delaviridine (rescriptor), powerful inhibitors for the protease
and reverse transcriptase inhibitor of HIV enzymes,
respectively [18]. Some piperizinyl [1,2,4]triazole deriva-
tives were reported as 5-HT
1A
serotonin receptor ligands
[19].
In view of these facts, the aim of the present study was to
synthesize new compounds containing 1,2,4-triazole and
piperazine moieties in a single molecular framework as
possible anticancer agents. In the present work we have
described synthesis of 3-[3-[4-(substituted)-1-cyclicamine]
propyl]thio-5-substituted[1,2,4]triazoles (8). The cytotoxic
activity of these derivatives was studied against five different
types of human cancer cell lines i.e. U937, THP-1, Colo205,
MCF7 and HL-60.
RESULTS AND DISCUSSION
Chemistry
5-Substituted [1,2,4]triazole-3-thiones (5) were
synthesized by following reported sequence of the reactions
from corresponding aryl carboxylic acids (1) (Scheme 1).
The aryl carboxylic acids (1) were converted to
corresponding methyl esters (2) with catalytic amount of
sulfuric acid in methanol. This was confirmed by
disappearance of broad carboxylic acid peak in
1
H NMR
spectra and disappearance of broad ‘OH’ stretching of
carboxylic acid in IR spectra of the product. It was also
supported by appearance of OCH
3
peak in
1
H NMR spectra
of methyl esters (2). The methyl esters (2) were converted to
corresponding acid hydrazides (3) using hydrazine hydrate in
methanol [20]. This was confirmed by disappearance of -
OCH
3
peak and appearance of NH and NH
2
peaks in
1
H
NMR spectra of the product. It was also supported by the
appearance of NH stretching and C=O stretching of acid
hydrazide in IR spectra of the product. The acid hydrazides
(3) were reacted with potassium thiocyanate and
concentrated hydrochloric acid to produce corresponding
thiosemicarbazides (4) [21]. Appearance of additional NH