Russian Journal of Applied Chemistry, 2012, Vol. 85, No. 10, pp. 1590−1591.
Pleiades Publishing, Ltd., 2012.
Original Russian Text © G.M. Butov, N.P. Pastukhova, E.A. Kamneva, K.R. Saad, 2012, published in Zhurnal Prikladnoi Khimii, 2012, Vol. 85, No. 10,
AND INDUSTRIAL ORGANIC CHEMISTRY
Method for Synthesis of 1-Adamantyl Esters
of Unsaturated Acids
G. M. Butov, N. P. Pastukhova, E. A. Kamneva, and K. R. Saad
Volzhskii Polytechnic Institute, Branch of Volgograd State Technical University, Volzhskii, Volgograd oblast, Russia
Received November 1, 2011
Abstract—New method for synthesis of adamantyl esters of acrylic, methacrylic, and cinnamic acids was devel-
oped. The reactions carried out under mild conditions in the absence of catalysts provide a high yield.
At present, a search for new ways to synthesize
monomer for manufacture of polymers possessing
increased heat resistance is an important task for organic
and polymer chemistry.
Polyhedral (meth)acrylates, such as 1-(meth)acryloyl
adamantanes have found application as monomers
for synthesis of macromolecular compounds via free-
radical polymerization [2, 3]. The polymers produced
using these polymers are used as, e.g., light-sensitive
materials in photolithography .
At present, the synthesis of acrylic and methacrylic
acid adamantyl esters is based on the interaction of the
corresponding acids or their chloroanhydrides with
adamantane hydroxy derivatives [2, 3]. Also known is
the method for production of polyhedral methacrylates
via reaction of the silver salt of methacrylic acid with
1-bromadamantane, with yields of up to 76%, depending
on the solvent used . It should be noted that the above
syntheses occur in multiple stages during a long time
(4–28 h), with a comparatively low yield of the target
products. In addition, the presence of various impurities
in the monomers adversely affects the properties of the
It is known that 1,3-dehydroadamantane (I) (1,3-
DHA) has a high proton afﬁ nity  and readily enters
into reactions with acetic acid  and those at the
hydroxy group of phenols and naphthols [8, 9]. Also
known is the reaction of spontaneous copolymerization
of 1,3-DHA with acrylonitrile . However, reactions
of 1,3-DHA at the carboxy group of unsaturated organic
acids have not been described in the literature.
A new method was developed for synthesis of
1-adamantyl esters of a number of unsaturated acids via
interaction of 1,3-DHA (I) with acrylic (IIa), methacrylic
(IIb), and cinnamic (IIc) acids. The reactions were
performed in absolutized diethyl ether during 0.5 h at
a temperature of 30–35°C at a reagent ratio 1,3-DHA :
unsaturated acid = 1 : 1.5 in an inert atmosphere:
HC C COOHR
HC C COOR
= H, R
= H (IIa, IIIa); R
= H, R
= H (IIc, IIIc).
After the reaction was complete, the ester solution
was washed ﬁ rst with a 5% solution of sodium hydroxide