ISSN 1070-4272, Russian Journal of Applied Chemistry, 2014, Vol. 87, No. 12, pp. 1884−1889. © Pleiades Publishing, Ltd., 2014.
Original Russian Text © L.B. Romanova, L.S. Barinova, G.V. Lagodzinskaya, A.I. Kazakov, Yu.M. Mikhailov, 2014, published in Zhurnal Prikladnoi Khimii, 2014,
Vol. 87, No. 12, pp. 1809−1815.
ORGANIC SYNTHESIS AND INDUSTRIAL
Preparation and NMR Analysis
of β-Cyclodextrin Nitrates
L. B. Romanova, L. S. Barinova, G. V. Lagodzinskaya,
A. I. Kazakov, and Yu. M. Mikhailov
Institute of Problems of Chemical Physics, Russian Academy of Sciences,
pr. Akademika Semenova 1, Chernogolovka, Moscow oblast, 142432 Russia
Received December 29, 2014
Abstract—Cyclodextrin nitrates with different degrees of substitution of hydroxy groups by nitrate groups were
synthesized. A procedure based on analysis of
H NMR spectra was developed for determining the degree of
nitration and the composition of the product mixtures obtained.
Cyclodextrins (CDs) are cyclic glucose oligomers
with six, seven, and eight glucopyranose units (α-, β-, and
γ-CD, respectively). Their diverse derivatives have been
actively studied and widely used in the past decades .
Interest in these compounds is due to a speciﬁ c structure
of their macrocycles containing a nanosized hydrophobic
void allowing formation of inclusion complexes (ICs)
with hydrophobic molecules or their fragments of suitable
size. The formation of such host–guest complexes
inﬂ uences the properties of both components and is used
for modifying them in the direction required for practical
applications. CD derivatives with altered host properties
preserve this capability. Owing to the ability to form
host–guest complexes, CDs are widely used in diverse
ﬁ elds, from food, pharmaceutical, cosmetic, chemical,
and biochemical industry to rocket engineering [1, 2].
CDs are commercially produced in the world in large-
Although data on CDs are extremely ample, studies
concerning CD nitrates (CDNs) are relatively few. The
initial CDs coincide in the composition with cellulose, and
their nitrates coincide with cellulose nitrates. Therefore, it
is quite natural that attempts were made to use CDNs as
environmentally safe components of rocket propellants,
as indicated by a number of papers [3–5] and patents
[6–9]. The use of CDNs in airbags is also suggested
. It was shown, in particular, that the formation of
ICs of CDs and CD nitrates with such explosives as,
e.g., nitroglycerin, trimethylolethane trinitrate, and
1,2,4-butanetriol trinitrate enhances the stability and
reduces the sensitivity of energetic formulations based
on them [6, 11]. The possibility of using polymeric CD
derivatives for the delivery of nitrogen mononitrate into
living cells was examined .
Along with fully nitrated CD, partial CD nitrates
with the preset degree of nitration can also be of interest.
They can be used as reagents for further chemical
transformations. In addition, incomplete CD nitrates,
which are NO donors, are of potential interest of using
as drugs. The available data on partial CD nitrates
are insufficient. Therefore, it is necessary to study
physicochemical properties of the whole family of these
compounds, including mixtures with different degrees
and topologies of substitution.
In this study, we suggested a laboratory procedure
for preparing nitrates of β-CD (β-CDNs) and developed
a method for determining the degree of substitution and
the mean amount of glucopyranose units of different
compositions in the macrocycle of partial β-CD nitrates,
based on analysis of the NMR spectra.