CAS NO: 56-06-4

CAS NAME: 4(3H)-Pyrimidinone, 2,6-diamino-

STRUCTURE:
NH2

N NH

O NH2

SYNTHESIS REFERENCES:
DFT simulations and vibrational analysis of FT-IR and FT-Raman spectra of
2,4-diamino-6-hydroxypyrimidine. Subramanian, M. K.; Anbarasan, P. M.;
Manimegalai, S. Department of Physics, Thiruvalluvar Govt. Arts College,
Rasipuram, Namakkal, Tamilnadu, India. Spectrochimica Acta, Part A: Molecular and
Biomolecular Spectroscopy (2009), 73A(4), 642-649. Publisher: Elsevier B.V.,
Abstract - Quantum mech. calcns. of energies, geometries and vibrational
wavenumbers of 2,4-diamino-6-hydroxypyrimidine (2,4DA6HP) were carried out by
using ab initio HF and d. functional theory (DFT/B3LYP) method using 6-311G(d,p)
basis set. The optimized geometrical parameters obtained by B3LYP method show
good agreement with exptl. X-ray data. The best level of theory in order to
reproduce the exptl. wavenumbers is B3LYP method with the 6-311G(d,p) basis set.
The difference between the obsd. and scaled wavenumber values of most of the
fundamentals is very small. A detailed interpretation of the IR spectra of 2,4DA6HP
was also reported. The calcd. HOMO and LUMO energies show that charge transfer
occurs in the mol. The entropy of the title compd. is also performed at HF/6-
311G(d,p) and B3LYP/6-311G(d,p) levels of theory. The theor. spectrograms for FT-
IR and FT-Raman spectra of the title mol. have been constructed.

2,4-Diamino-6-hydroxypyrimidine. VanAllan, J. A. Eastman Kodak

Company, Rochester, NY, USA. Organic Syntheses (1952), 32 No pp. given.
Publisher: John Wiley & Sons, Inc.
Abstract - A review of the article 2,4-Diamino-6-hydroxypyrimidine.

RO104937 - Preparation of 2,4-diamino-6-hydroxypyrimidine via the

cyclocondensation of ethyl cyanoacetate with guanidinium nitrate.
Vasilioni, Virgil Gheorghe; Darabantu, Mircea; Fodor, Cristina; Serban, Gabriel;
Balint, Radu Dorin; Breazu, Dorin. (Intreprinderea de Medicamente "Terapia",
Rom.). Rom. (1994), 3 pp.
Abstract - 2,4-Diamino-6-hydroxypyrimidine is prepd. in high yield and purity by
dissolving guanidinium nitrate in methanolic or ethanolic NaOH (the molar ratio of
NaOH-alc. is 1:3.8) at 40, adding (at 70-72; the molar ratio of Et cyanoacetate-
guanidinium nitrate is 1:1.1), removing the alc. solvent, dissolving the intermediate
Na salt of 2,4-diamino-6-hydroxypyrimidine in H2O, neutralizing this aq. soln. with
37% aq. HCl, cooling the product-contg. soln. to 2, and filtering the 2,4-diamino-
6-hydroxypyrimidine.

EP304648 - Preparation of 2,4-diamino-6-piperidinopyrimidine 3-oxide

(minoxidil) and intermediates therefor. Maignan, Jean; Restle, Serge; Lang,
Gerard. (Oreal S. A., Fr.). Eur. Pat. Appl. (1989), 17 pp.
Abstract -The title compd. (I), a known antihypertensive, was prepd. from
pyrimidine derivs. II (X = halo, OH) and/or pyrimidine oxides III (X = OH, Cl, o-
tosyl, O-benzenesulfonyl; R1,R2 = H, RNHCO; R = C1-6 alkyl; one of R1 = R2 must
be other than H; n = 0 or 1). Reaction of 6-chloro-2,4-diaminopyrimidine with
BuNCO, followed by oxidn. with m-chloroperbenzoic acid, reaction with piperidine,
and deprotection by treatment with KOH, gave I.

X
X

N
N

R 1HN N NHR 2
H2N N NH 2 II On III

EP295218 - Process for the preparation of minoxidil via a pyrimidine N-

oxide. Botre, Claudio. (Italy). Eur. Pat. Appl. (1988), 6 pp.
Abstract - Minoxidil (I) is prepd. as an antihypertensive. Cyclocondensation of
H2NC(:NH)NH2.HCl with NCCHCO2Et in EtOH in the presence of MeONa gave 79.6%
2,6-diamino-4-hydroxypyrimidine, which was treated with POCl3 to afford 47.3% II
(n = 0). Treatment of the pyrimidine in MeOH with III gave 66.9% II (n = 1), which
was treated with an excess to piperidine to yield 75.9% I.
 Cl N NH 2
CO 3 H
NO n Mg 2+ ⋅ 6H 2 O

CO 2 -
NH 2 II 2 III

HU19770 - 6-Piperidino-2,4-diaminopyrimidine 3-oxide. Szentay, Csaba;

Balogh, Gyula; Horvath, Judit; Master, Tamas. (E. Gy. T. Gyogyszervegyeszeti Gyar,
Hung.). Hung. Teljes (1981), 18 pp.
Abstract - The title compd. (I) is prepd. from 6-hydroxy-2,4-diaminopyrimidine (II)
by sulfonylation with RSO2Cl (R = Ph, p-tolyl, Me), oxidn. with m-ClC6H4CO2OH
(III), and treatment with piperidine (IV). Thus, a soln. of II in 2.5 N NaOH and p-
MeC6H4SO2Cl in Me2CO were added simultaneously to Me2CO at room temp. and
pH 7, and the mixt. was stirred 3 h to give 95% 6-(p-tolylsulfonyloxy)-2,4-
diaminopyrimidine. Oxidn. of the latter with III in aq. EtOH at 0-5 gave 65% 6-(p-
tolylsulfonyloxy)-2,4-diaminopyrimidine 3-oxide, which on heating with piperidine 2
h at 100 gave 55% I.

GB2032434 - 6-Piperidino-2,4-diaminopyrimidine-3-oxide. Vedres, Andras;

Szantay, Csaba; Balogh, Gyula; Horvath, Judit; Mester, Tamas. (E. Gy. T.
Gyogyszervegyeszeti Gyar, Hung.). Ger. Offen. (1980), 33 pp.
Abstract - The title compd. (I), a known antihypertensive, was prepd. from 2,4-
diamino-6-pyrimidinol (II). Thus, II was O-tosylated with 4-MeC6H4SO2Cl, and the
product was treated with 3-ClC6H4CO3H to give III, which was treated with
piperidine at 0-5, followed by heating 3 h at 100 to give 64% I.

NH 2 Cl

Me SO 3 N O2 C
N
NH III

Vibrational spectra of biological molecules: 2,4-diamino-6-

hydroxypyrimidine. Goel, R. K.; Sharma, S. N. Dep. Phys., D. N. Coll.,
Meerut, India. Indian Journal of Pure and Applied Physics (1980), 18(3), 195-9.
CODEN: IJOPAU ISSN: 0019-5596. Journal written in English. CAN 92:210384
AN 1980:210384 CAPLUS (Copyright (C) 2010 ACS on SciFinder (R))
Abstract - The IR absorption spectra of 2,4-diamino-6-hydroxypyrimidine were
recorded on the Perkin Elmer-521 spectrophotometer in the region 250-4000 cm-1
by KBr pellet and Nujol mull techniques. The spectra were analyzed assuming C8
point-group symmetry for the mol. The fundamentals were compared with those of
pyrimidine. Assignments were proposed and discussed. Tautomerism is also
discussed.

SU517591 - N6-Substituted 2,6-diamino-4-hydroxypyrimidines. Zav'yalov,

S. I.; Ovechkina, L. F.; Pokhvisneva, G. V. (Zelinskii, N. D., Institute of Organic
Chemistry, USSR). U.S.S.R. (1976),
Abstract - The title compds. I (R1 = CH2CH2OH, cyclohexyl, Bu) were prepd. by
transamination of I with the corresponding R1NH2 in HOCH2CH2CH2OH contg.
Cu(OAc)2 at 170-200 .

HO

N
I, R=R 1
H2 N N NHR II, R=H