ISSN 1070-3632, Russian Journal of General Chemistry, 2006, Vol. 76, No. 2, pp. 331 332.
Pleiades Publishing, Inc., 2006.
Original Russian Text
V.A. Sokolenko, N.M. Svirskaya, N.I. Pavlenko, 2006, published in Zhurnal Obshchei Khimii, 2006, Vol. 76, No. 2, p. 348.
LETTERS
TO THE EDITOR
A New Route to N-(1-Adamantyl)nicotinamide
V. A. Sokolenko, N. M. Svirskaya, and N. I. Pavlenko
Institute of Chemistry and Chemical Technology, Siberian Division,
Russian Academy of Sciences, ul. K. Marksa 42, Krasnoyarsk, 660049 Russia
e-mail: wsokol@akadem.ru
Received June 9, 2005
DOI: 10.1134/S1070363206020320
N-(1-Adamantyl)nicotinamide I was prepared pre-
viously by the reaction of nicotinoyl chloride with
1-aminoadamantane on heating in anhydrous pyridine
[1] or by the Ritter reaction [2] from 1-hydroxyada-
mantane and nicotinonitrile in trifluoroacetic acid
acting as catalyst and solvent.
60 vol % [5]. Apparently, under severe conditions
1-hydroxyadamantane also generates an Ad-carbenium
ion with the assistance of water.
N-(1-Adamantyl)nicotinamide I. a. A mixture of
0.151 g of 1-aminoadamantane and 0.610 g of nicotin-
amide was heated on a sand bath to 210 215 C; until
the ammonia evolution started, the released gases
were passed through a bubbler. The mixture was kept
at 210 215 C for 30 40 min. After cooling, it was
treated with water, and the precipitate was dried. Ada-
mantylated nicotinamide was obtained in a yield of
0.233 g (91%); mp 164 166 C (published data: mp
We found that compound I can be prepared in 91%
yield by heating nicotinamide with 1-aminoadaman-
tane without solvent:
CONH2
+ NH3
CONH2
+ 1-NH2Ad
Ad =
,
N
.
1
N
164 167 C [1]). IR spectrum, , cm : 3345 (NH),
I
1
2909 2853 (CH2 of adamantane), 1662 (C=O). H
NMR spectrum (CDCl3), , ppm: 1.68 (6H ), 2.08
(3H + 6H ) (adamantane protons); 7.87 (NH), 7.44
(H5), 8.15 (H4), 8.67 (H6), 8.97 (H2) (pyridine pro-
tons). 13C NMR spectrum (CDCl3), C, ppm: 29.97
(C ), 37.15 (C ), 41.91 (C ), 52.85 (C ), 124.27 (C5),
132.43 (C3), 136.16 (C4), 149.54 (C6), 152.45 (C2),
165.63 (CO).
It is known that amides can act as acylating agents
toward amines [3]. Heating of amides with primary
amines is accompanied by exchange of amino group
(often without additional catalyst), but these reactions
go to completion only if the released amine is volatile.
It was also reported that 1-bromoadamantane reacts
amides R CONHR in the presence of Ag2SO4 at
100 C. With N-methylacetamide, the yield of the re-
action product, 1-N-methylacetamidoadamantane, is
43% [4].
b. A mixture of 1 mmol of 1-XAd [X = Br, OH]
and 5 mmol of nicotinamide was heated similarly to
procedure a. Compound I was isolated; yield 66
(from 1-BrAd, sample Ia) or 53% (from 1-HOAd,
sample Ib). The structure of Ia and Ib was proved by
NMR and IR spectroscopy and by comparison of their
physicochemical characteristics with the published
data [1, 2] and with the characteristics of the product
prepared by procedure a.
We found that nicotinamide can be adamantylated
with 1-bromoadamantane without adding a silver salt.
Also, we prepared compound I by adamantylation
of nicotinamide with 1-hydroxyadamantane in the
presence of traces of water. Protic solvents (water in
our case) exert an electrophilic accelerating effect on
SN1 reactions. It is known that the rate of solvolysis
of 1-BrAd in aqueous ethanol increases by a factor of
4900 with an increase in the water content from 10 to
The IR spectra were recorded on a Vector-22 IR
1
Fourier spectrometer in KBr pellets. The H and 13C
NMR spectra were recorded on a Bruker-Avance
DPX-200W spectrometer (Krasnoyarsk Regional
Center of Collective Use, Siberian Division, Russian
Academy of Sciences).
331
Sokolenko
