ISSN 0012-5016, Doklady Physical Chemistry, 2011, Vol. 437, Part 2, pp. 78–81. © Pleiades Publishing, Ltd., 2011.
Original Russian Text © A.G. Ogienko, E.V. Boldyreva, A.Yu. Manakov, V.V. Boldyrev, M.A. Mikhailenko, A.S. Yunoshev, A.A. Ogienko, A.I. Ancharov, A.F. Achkasov, A.V. Ildyakov,
A.A. Burdin, N.A. Tumanov, A. S. Stoporev, and N. V. Kutaev, 2011, published in Doklady Akademii Nauk, 2011, Vol. 437, No. 6, pp. 785–788.
78
Paracetamol (N-(p-hydroxyphenyl)acetamide) is a
widely used non-narcotic analgesic having also anti-
inflammatory and antipyretic action. Several crystal-
line polymorphs of paracetamol are known. One of
these (monoclinic form I) is thermodynamically stable
and is readily prepared but cannot be compressed to
tablets without excipients (fillers). Another poly-
morph (orthorhombic form II) can be readily com-
pressed to tablets without excipients [1, 2] and is better
soluble but its formation as a pure phase is not repro-
ducible, and, what is worse, it is metastable and is
spontaneously converted to the monoclinic form on
storage [1]. The idea of obtaining compressible forms
of paracetamol that would be stable on storage attracts
considerable attention of the scientific community
and pharmaceutical companies. For solving this prob-
lem, it has been proposed to use, instead of pure
paracetamol, its mixtures with polyvinylpyrrolidone
[3], carbohydrates [4], chitosan and sodium alginate
[5] or mixed crystals based on oxalic acid, naphthalene
and other compounds [6] or the inclusion compounds
with hydroxypropyl-β-cyclodextrin [7].
An attempt to prepare pure monoclinic paraceta-
mol suitable for direct compression has been under-
taken [8]. To this end, paracetamol was recrystallized
from a solution or suspension in 1,4- dioxane to give a
paracetamol solvate with dioxane (1 : 1/2) and then
the solvating dioxane was removed. This gave highly
porous paracetamol particles. It was noted [8] that a
considerable disadvantage of this method for the prep-
aration of paracetamol for tablet manufacture is the
high thermal stability of the solvate and also rather low
product yield in the case where saturated solutions are
used (~21 g of paracetamol from 1000 mL of a solution
saturated at 50°С). Meanwhile, the use of higher tem-
perature (80–90°С) with the same solvent increased
the product yield (200–300 g per 1000 mL of the solu-
tion). However, at higher temperature, paracetamol
may be partly oxidized. In the case of a suspension, the
yield was even higher (at 50°С, this was ~164 g from
1000 mL of a suspension containing 200 g of paraceta-
mol). Although the authors demonstrated some
improvement of the compressibility and dissolution
rate of the paracetamol samples they obtained as com-
pared with the starting reagent, the subsequent testing
was carried out with the standard excipients used to
prepare paracetamol tablets.
Instrumental methods for the preparation of fine
powders of pharmaceutical products based on spray or
freeze drying have been reported [9]. The use of high
cooling rates to give amorphous phases followed by the
removal of solvents by sublimation makes it possible to
avoid enlargement of the formed crystallites due to the
absence of contact with the liquid phase.
By the beginning of our studies, it was known that
a considerable increase in the paracetamol solubility is
attained when a binary mixture comprising a volatile
liquid (dioxane, ethanol, acetone) and water is used as
the solvent [10]. One more reason for using systems
with dioxane and acetone is the formation of clathrate
hydrates with cubic structure II at low temperatures
(CS II, the volatile liquid to water ratio is 1 : 17) [11].
Hence, only solid phases coexist over broad concen-
tration and temperature ranges. A favorable condition
PHYSICAL
CHEMISTRY
A New Method for Obtaining Fine Powders of Paracetamol
for Compression without Excipients
A. G. Ogienko
a, b
, E. V. Boldyreva
a, c
, A. Yu. Manakov
a, b
, Academician V. V. Boldyrev
a, c
,
M. A. Mikhailenko
a, c
, A. S. Yunoshev
a, d
, A. A. Ogienko
a, e
, A. I. Ancharov
a, c
, A. F. Achkasov
a
,
A. V. Ildyakov
b
, A. A. Burdin
b
, N. A. Tumanov
a
, A. S. Stoporev
a, b
, and N. V. Kutaev
a, b
Received December 3, 2010
DOI: 10.1134/S0012501611040063
a
Molecular Design and Environmentally Safe
Technologies Science and Educational Center,
Novosibirsk State University, ul. Pirogova 2,
Novosibirsk, 630090 Russia
b
Nikolaev Institute of Inorganic Chemistry,
Siberian Branch, Russian Academy of Sciences,
pr. Akademika Lavrent’eva 3, Novosibirsk,
630090 Russia
c
Institute of Solid State Chemistry and Mechanochemistry,
Siberian Branch, Russian Academy of Sciences,
ul. Kutateladze 18, Novosibirsk, 630128 Russia
d
Lavrent’ev Institute of Hydrodynamics,
Siberian Branch, Russian Academy of Sciences,
pr. Akademika Lavrent’eva 15, Novosibirsk,
630090 Russia
e
Institute of Cytology and Genetics, Siberian Division,
Russian Academy of Sciences,
pr. Akademika Lavrent’eva 10,
Novosibirsk, 630090 Russia