Some reactions of 4,6-diaminopyrimidinethione

Article abstract of DOI:10.1080/10426500701556981

Reaction of 4,6-diamino-2(1H)-pyrimidinethione (1) with p-toluene-sulfonyl hydrazine, nitrous acid and carbon disulfide afforded the compounds (2, 3) and (4) respectively. Compound (3) easily reacted with anthranilic acid, semicarbazide thiosemicarbazide

Full text of DOI:10.1080/10426500701556981

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Phosphorus, Sulfur, and Silicon
and the Related Elements
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Some Reactions of 4,6-
Diaminopyrimidinethione
Gamal A. Ahmed a
a Chemistry Department, Faculty of Science ,
Zagazig University , Zagazig, Egypt
Published online: 20 Feb 2008.
To cite this article: Gamal A. Ahmed (2007) Some Reactions of 4,6-
Diaminopyrimidinethione, Phosphorus, Sulfur, and Silicon and the Related Elements,
183:1, 69-73, DOI: 10.1080/10426500701556981
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Phosphorus, Sulfur, and Silicon, 183:69–73, 2008
Copyright © Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426500701556981
Some Reactions of 4,6-Diaminopyrimidinethione
Gamal A. Ahmed
Chemistry Department, Faculty of Science, Zagazig University,
Zagazig, Egypt
Reaction of 4,6-diamino-2(1H)-pyrimidinethione (1) with p-toluene-sulfonyl hy-
drazine, nitrous acid and carbon disulfide afforded the compounds (2, 3) and
(4) respectively. Compound (3) easily reacted with anthranilic acid, semicarbazide
thiosemicarbazide and acid hydrazides and gave the polynuclearheterocyclic com-
pounds (5, 6a,b) and (8a,b) respectively. Also, compound (4) yielded the tricyclic com-
pound 7 when reacted with ethylchloroformate. The purpose of this article is syn-
thesis of biologically active polynuclear heterocyclic compounds.
Keywords Tetrazopyrimidinethione; triazolopyridine; polynuclear heterocycle
INTRODUCTION
As an extension of our studies on pyrimidine and pyrimidine thione
derivatives, as synthons to prepare fused heterocyclic compounds,1,2
we have synthesized new compounds for use as antischitosomal, such
as tricyclic and hexacyclic compounds, since some of pyrimidine and
pyrimidinethione derivatives have provided to be active antiviral,3,4
antimicrobial,5,6 and anticancer.7
CHEMISTRY
Heating a ternary mixture of malononitrile and thiourea in presence
of sodium ethoxide in ethanol under reflux yielded 4,6-diamino-2(1H)-
pyrimidinthione (1).8
Reaction of (1) with p-toluenesulfonyl hydrazine gave 4,6-diamino-
(3-oxo-3-p-tolyl)-thia-(1,2,4)-triazolo-[5,4a]pyrimidine (2). The struc-
ture of (2) was elucidated from its correct spectral data (Table I).
Received 5 May 2007; accepted 5 June 2007.
Address correspondence to Gamal A. Ahmed, Chemistry Department, Faculty of
Science, Zagazig University, Zagazig, Egypt. E-mail: yehia 3@yahoo.com
69

70
G. A. Ahmed
SCHEME 1
On the other hand, when compound (1) was allowed to react
with nitrous acid and carbon disulfide, it afforded the unseparated
intermediates (3) and (4), respectively.1,2 Treatment of the tetrazonium
salt (3) with anthranilic acid yielded the polynuclear heterocyclic com-
pound 5 (Table I).

Reactions of Diaminopyrimidinethione
71
TABLE I Characterization Data of Products 2-8b
M.P.◦C
solvent
Compound
Yield %
52
IR cm−1
1H NMR (ppm)
2.5 (s, 3H, CH3),
7.5–8 (m, 4H, aromatic),
5.1–5.6 (broad, 4H, 2NH2)
2
280–281
n-butanol
1590 (C N),
1335 (S O),
1370–1325 (S N),
3300–3200 (NH2)
1660 (C O),
3190 (NH),
1460 (C S)
1450 (C S),
1470 (C S),
3195 (NH)
1440 (C S),
1650 (C O),
3180 (NH)
1670 (C O),
1650 (C O),
1635 (C O),
1455 (C S),
3180 (NH)
5
268–70
DMF
47
55
58
61
6.1 (s, 1H, NH),
7.2–7.9 (m, 8H, 2Ph),
6.8 (s, 1H pyrimidyl)
7.2 (s, 1H pyrimidyl),
6.8 (broad, 1H, NH)
6a=
6b
7
229
n-butanol
253
n-butanol
7.1 (s, 1H pyrimidyl),
10.1 (broad, 1H, NH)
218–20
ethanol
6.8 (broad, 1H, NH),
7.2 (s, 1H pyrimidyl)
8a
8b
261
A.A.
43
49
1450 (C S),
3200 (NH),
1580 (C N)
1455 (C S),
1590 (C N),
3190 (NH)
7.1 (s, 1H pyrimidyl),
6.8 (broad, 1H, NH),
7–7.8 (m, 5H, phenyl)
7.2 (s, 1H, pyrimidyl),
6.2 (broad, 1H, NH),
7.2–7.9 (m, 4H, phenyl)
273–5
A.A.
DMF: dimethyl formate; A.A.: acetic acid.
Also, compound (3) reacted with semicarbazide and thiosemicar-
bazide and gave the tricyclic compounds (6a,b); the structure of these
compounds was confirmed from their correct spectral data (Table I).
On the other hand when the dipotassium salt (4) was allowed to react
with ethylchloroformate it gave the tricyclic compound (7) (Table I).
Reaction of the tetrazonium salt (4) with benzoylhydrazine and p-
clorobenzoylhydrazine afforded the tricyclic compounds (8a,b) (Table I).
EXPERIMENTAL
All melting points were uncorrected and were determined on electric
melting point apparatus. 1H NMR spectra (DMSO-d6 and CDCl3), were
carried out on a Bruker Avance 300 MHz spectrometer using TMS as
internal reference chemical shift in δ, ppm).

72
G. A. Ahmed
Reaction of Compound (1) with p-Toluenesulfonyl
Hydrazine—Formation of (2)
A mixture of compound 1 (1.42 g, 0.01 mol) and p-toluenesulfonyl hy-
drazine (1.86 g, 0.01 mol) in n-butanol (30 ml) was heated under reflux
for 15 h; the solid produced after cooling was collected and crystallized
from n-butanol into compound (2) m.p. 289–80◦C.
Reaction of Compound (1) with Nitrous Acid—Formation
of the Intermediate (3)
To an ice-cold solution of (1) (3 g) in dilute hydrochloric acid (35 ml),
contained in 250 ml beaker, a solution of sodium nitrite (2.5 g) in cold
water (20 ml) was added slowly. The resulting tetrazonium salt solution
was stirred for 15 min at 0◦C and used in the next experiments without
isolation.
Reaction of 3 with Anthranilic Acid—Formation of (5)
To the tetrazonium salt solution 3 (2.2 g, 0.01 mol) anthranilic acid
was added (1.37 g, 0.01 mol) and the mixture was stirred for 8 h, con-
centrated by evaporation under vacuum. The solid produced was col-
lected and crystallized from dimethylformamide into compound (5), m.p
268◦C.
Reaction of (3) with Semicarbazide and
Thiosemicarbazide—Formation of (6a,b
)
To the tetrazonium salt solution (3) (2.2 g, 0.01 mol), semicarbazide
(0.75 g, 0.01 mol) and/or thiosemicarbazide (0.91 g, 0.01 mol) was added,
and the reaction mixture was stirred for 12 h; the solid produced was
collected and crystallized from n-butanol, 6a, m.p. 229◦C, 6b, m.p. 253◦C.
Reaction of 1 with Carbon Disulfide—Formation of the
Dipotassium Salt (4)
A mixture of (1), (1.42 g, 0.01 mol) and potassium hydroxide (0.39 g, 0.01
mol) in carbon disulfide (60 ml) was heated on water bath at 60◦C for 1
h; the reaction mixture was left to cool and used in the next experiment
without separation.

Reactions of Diaminopyrimidinethione
73
Reaction of the Dipotassium Salt (4) with
Ethylchloroformate—Formation of (7)
A mixture of (4), (3.7 g, 0.01 mol) and ethylchlorformate (0.96 g, 0.01
mol) was heated on water bath for 2 h; the solid produced after cooling
was collected and crystallized from ethanol into compound (7), m.p.
218◦C.
Reaction of the Tetrazonium Salt with Acid Hydrazide,
Formation of (8a,b
)
To the tetrazonium salt solution (4) (3.7 g, 0.01 mol), benzoylhydrazine
(1.3 g, 0.01 mol) and/or p-chlorobenzoylhydrazine (1.7 g, 0.01 mol) was
added, and the reaction mixture was stirred for 18 h at room temper-
ature, then concentrated by evaporation under reduced pressure, the
solid produced was collected, washed with water and recrystallized from
acetic acid into compounds 8a,b, m.p. of 8a 261◦C, m.p. of 8b 284◦C.
CONCLUSION
The above work enables us to synthesize some new biologically active
polynuclear heterocyclic compounds from simple monocyclic heteroyclic
compounds.
REFERENCES
[1] G. A. Ahmed and N. M. Abd El-Salam, Boll. Chim. Farmaco, 142 (3) (April 2003).
[2] G. A. Gamal, S. El-Bahai, and Abd El-Salam, Boll. Chim. Farmaco., 142 (2) (March
2003).
[3] R. Rrice, B. Brew, J. Sidtis, M. Rosenblum, A. Scheck, and P. Cleary, Science, 239,
586 (1988).
[4] A. S. Fauc, Science, 239, 617 (1988).
[5] S. El-Bahaie and M. G. Assy, Pharmazia, 45, 216 (1990).
[6] M. O. Fasoli and D. J. Kerridge, Gen. Microbial., 136, 1475 (1990).
[7] D. Ingram, M. Forman, and J. Murray, Am. J. Pathol., 140, 1081 (1992).
[8] D. M. Burness, J. Org. Chem., 21, 97 (1956).