Method for synthesis of 1-adamantyl esters of unsaturated acids

Article abstract of DOI:10.1134/S1070427212100199

New method for synthesis of adamantyl esters of acrylic, methacrylic, and cinnamic acids was developed. The reactions carried out under mild conditions in the absence of catalysts provide a high yield. Pleiades Publishing, Ltd., 2012.

Full text of DOI:10.1134/S1070427212100199

ISSN 1070-4272, 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,
pp. 1658−1659.
ORGANIC SYNTHESIS
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
e-mail: butov@volpi.ru
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.
DOI: 10.1134/S1070427212100199
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.
known is the reaction of spontaneous copolymerization
of 1,3-DHA with acrylonitrile [10]. 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
interactionof1,3-DHA(I)withacrylic(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:
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 [4].
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 [5]. 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
polymers obtained.
R1 HC
C
COOH
+
R2
IIa_IIc
I
R1 HC
C
COO
R2
IIIa_IIIc
where R1 = H, R2 = H (IIa, IIIa); R1 = H, R2 = CH3 (IIb,
IIIb); R1 = C6H5, R2 = H (IIc, IIIc).
It is known that 1,3-dehydroadamantane (I) (1,3-
DHA) has a high proton affinity [6] and readily enters
into reactions with acetic acid [7] and those at the
hydroxy group of phenols and naphthols [8, 9]. Also
After the reaction was complete, the ester solution
was washed first with a 5% solution of sodium hydroxide
1590

METHOD FOR SYNTHESIS OF 1-ADAMANTYL ESTERS
1591
Mass spectrum, m/z (intensity, %): 220 ([М]+,
20.8%), 205 ([М–СН3]+, 1.04%), 135 ([Ad]+, 100%).
and then with water. The ester layer was dried over
calcium chloride and the ether was evaporated, and the
residue was kept in a vacuum to remove diethyl ether and
the unreacted acids IIa and IIb. The target esters IIIa,
IIIb were purified on a column packed with silica gel,
and compound IIIc, by recrystallization. The individual
nature of the esters IIIa–IIIc was confirmed by TLC.
The (meth)acrylates synthesized are transparent viscous
fluids with a characteristic odor. In storage, IIIa and
IIIb readily polymerize to give a transparent glassy
polymer. The properties of compounds IIIa and IIIb
were in agreement with published data [2, 3, 5]. The
1-adamantyl cinnamate IIIc is a low-melting white
substance.
1-Adamantyl cinnamate (IIIc). Similarly to IIIa,
IIIc was produced from 1.60 g (0.0119 mol) of freshly
distilled 1,3-DHA and 2.65 g (0.0179 mol) of cinnamic
acid in an amount of 2.78 g (83%), mp 63–65°С.
Found (%): С 80.69, Н 7.97. С19Н22O2. Calculated
(%): С 80.82, Н 7.85. 1Н NMR spectrum, δ, ppm: 1.68–
2.15 m (15Н,Ad), 6.5 d (1Н, СН), 7.4 d (3Н, С6Н5), 7.55
d (1Н, СН–Ph), 7.68 d (2Н, С6 Н5). Mass spectrum, m/z
(intensity, %): 282 ([М]+, 53%), 151 ([AdО]+, 3.3%),
135 ([Ad]+, 100%), 131 ([C6H5CH=CHCO]+, 87.6%),
103 ([C6H5CH=CH]+, 53.7%), 77 ([C6H5]+, 47.9%).
The mass spectra were recorded with a Hewlett
Packard GC 5890 Series II/MSD 5972 Series chromato-
mass spectrometer. Thin layer chromatography was
performed on Silufol UV 254 plates, with benzene as the
eluent. The 1H NMR spectra were recorded with Varian
Mercury-300 instruments at a working frequency of
300 MHz, with CDCl3 (chloroform-D1) as the solvent.
Anew method was developed for high-yield synthesis
of acrylic, methacrylic, and cinnamic acid adamantyl
esters under mild conditions in the absence of catalysts.
The composition and structure of the compounds
obtained were confirmed by mass spectrometry and 1H
NMR spectroscopy.
REFERENCES
EXPERIMENTAL
1. Acar, H.Y., Jensen, J.J., Thigpen, K., et al.,
1-Acryloyl adamantane (IIIa). To 1.80
g
Macromolecules, 2000, vol. 33, pp. 3855–3859.
(0.0134 mol) of freshly distilled 1,3-DHA dissolved
in 20 mL of diethyl ether was added 1.44 g (0.02 mol)
of acrylic acid in the atmosphere of dry argon at room
temperature in the course of 30 min. Then the ester
solution was washed with a diluted NaOH solution
and water. The ester layer was dried with calcium
chloride, the ether was evaporated, and the residue was
kept in a vacuum. 1-Acryloyl adamantane was isolated
on a column packed with silica gel in an amount of
2.39 g (86%). Found (%):С 75.82, Н 8.76. С13Н18O2.
Calculated (%): С 75.69, Н 8.80.
2. Tomoki, O. and Yoshiki, C., Macromolecules, 2003,
vol. 36, pp. 654–660.
3. US Patent 3639362.
4. Pasini, D., Klopp, J.M., and Frechet, J.M., J. Chem.
Mater., 2001, vol. 13, pp. 4136–4146.
5. USSR Patent 490795.
6. Fokin, A.A., Schreiner, P.R., Schleyer, P.von R., and
Gunchenko, P.A., J. Org. Chem., 1998, vol. 63, pp. 6494–
6502.
7. Pincock, R.E. and Torupka, E.J., J. Am. Chem. Soc., 1969,
vol. 91, p. 4593.
Mass spectrum, m/z (intensity, %): 206 ([М]+, 5.0%),
135 ([Ad]+, 92.4%), 55 ([М–OAd]+, 100%).
8. Butov, G.M., Mokhov, V.M., Kamneva, E.A., and Saad,
K.R., Izv. Volgogradskii Gos. Tekh. Univ., Khim. Tekhnol.
Elementoorgan. Monomer. Polimer. Mater., 2008, no. 8,
pp. 39–41.
1-Methacryloyl adamantane (IIIb). Similarly
to IIIa, IIIb was produced from 1.30 g (0.0097 mol)
of freshly distilled 1,3-DHA and 1.25 g (0.0145) of
methacrylic acid in an amount of 1.79 g (84%), nD20
1.4984 (1.4984 [5]). Found (%): С 76.19, Н 9.32.
С14Н20O2. Calculated (%): С 76.33, Н 9.15.
9. Butov, G.M., Kamneva, E.A., and Saad, K.R., Zh. Prikl.
Khim., 2011, vol. 84, no. 4, pp. 695–696.
10. Matsuoka, S., Ogiwara, N., and Ishizone, T., J. Am. Chem.
Soc., 2006, vol. 128, pp. 8708–8709.
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 85 No. 10 2012