2263
ONE-POT SYNTHESIS OF POLYCARBOXYLIC ACIDS OF ADAMANTANE TYPE
The presence conformationally rigid adamantane
moiety and several carboxyl groups in the molecule of
the prepared compounds allows their application as
building blocks for further synthesis of new useful
materials.
1H and 13C NMR spectra of the solutions in DMSO-d6
were recorded with a Jeol JNM ECX-400 spectrometer
(400 MHz). IR spectra were registered with a
Shimadzu IR Affinity-1 spectrometer (KBr pellets).
Mass spectra were obtained with a ThermoFinnigan
DSQ gas chromatography–mass spectrometer with EI
at 70 eV, using a BPX-5 (30 × 0.32) capillary column
for separation. Elemental analysis was performed with
a EuroVector 3000 EA analyzer using L-cysteine as a
reference.
General procedure for synthesis of compounds
VI–IV. Freshly distilled 1,1-dichloroethylene, 0.045 mol,
was added dropwise to a solution of 0.03 mol of the
corresponding 1-hydroxyladamantane I–III in 50 mL
of 96% sulfuric acid upon vigorous stirring at 10–15°C.
After 1.5 h stirring, 0.09 mol of fuming nitric acid was
added dropwise to the reaction mixture at 25–30°C.
Then, the resulting mixture was incubated at room
temperature during 1 h. After addition of 0.09 mol of
100% formic acid, the reaction mixture was stirred
during 12 h and poured into 300 g of crushed ice. The
formed precipitate was filtered off and twice recrys-
tallized from glacial acetic acid.
ACKNOWLEDGMENTS
This work was financially supported by the
Ministry of Education and Science of Russian
Federation (agreement no. 14.574.21.0008, unique
project identifier RFMEFI57414X0008) and the
Russian Foundation for Basic Research (agreement no.
14-03-97075\14).
3-Carboxymethyl-1-adamantycarboxylic acid. Yield
61%, mp 229–231°C (mp 236°C [7]).
REFERENCES
1. Blazek, V., Mlinaric-Majerski, K., Qin, W., and
Basaric, N., J. Photochem. Photobiol. (A), 2012, vol. 229,
p. 1. DOI: 10.1016/j.jphotochem.2011.12.005.
5,7-Dimethyl-3-carboxymethyl-1-adamantyl-
carboxylic acid. Yield 81%, mp 199–201°C. IR spec-
trum, ν, cm–1: 2947, 2924, 2897 (СНAd), 1699 (C=О).
1H NMR spectrum, δ, ppm: 0.82 s (6Н, СН3), 1.04–
1.50 m (12Н, СН2Ad), 2.03 s (2Н, СН2), 12.00 s (2Н,
COОН). 13С NMR spectrum, δС, ppm: 30.44 (CH3),
31.62 (CCH3), 34.27 (CCH2COOH), 42.27 (CH2),
42.66 (CCOOH), 44.62 (CH2), 47.64 (CH2), 47.72
(CH2), 50.06 (CH2COOH), 172.92 (СН2COOH),
178.53 (COOH). Found, %: С 67.69; Н 8.35.
С15Н22О4. Calculated, %: С 67.65; Н 8.33. М 266.34.
Mass spectrum, m/z (Irel, %): 294 (10) [M]+, 235 (100),
221 (70), 203 (18), 161 (50), 119 (48).
2. Bagrii, E.I. and Maravin, G.B., Petroleum Chem., 2013,
vol. 53, no. 6, p. 418. DOI: 10.1134/S0965544113060029.
3. Mu, Y.J., Ma, X.L., Han, B., Qin, G.F., Niu, Y.Y., and
Lu, H.X., Polyhedron, 2014, vol. 67, p. 44. DOI:
10.1016/j.poly.2013.08.054.
4. Wanka, L., Cabrele, C., Vanejews, M., and Schreiner, P.,
Eur. J. Org. Chem., 2007, vol. 9, p. 1474. DOI:
10.1002/ejoc.200600975.
5. Moiseev, I.K., Stulin, N.V., Yudashkin, A.V., and Kli-
mochkin, Yu.N., Russ. J. Gen. Chem., 1985, vol. 55,
no. 7, p. 1655.
6. Šilhar, P., Silvaggi, N.R., Pellett, S., Capkova, K.,
Johnson, E.A., Allen, K.N., and Janda, K.D., Bioorg.
Med. Chem., 2013, vol. 21, p. 1344. DOI: 10.1016/
j.bmc.2012.12.001.
7. Butenko, L.N., Khardin, A.P., and Shraibert, A.I.,
Inventor’s Sertificate 483393, 1976; Ref. Zh. Khim.,
1977, 6 Н 129.
8. Butenko, L.N., Protopopov, P.A., Derbisher, V.E., and
Khardin, A.P., Synth. Commun., 1984, vol. 14, no. 2,
p. 113. DOI: 10.1080/ 00397918408062813.
9. Ivleva, E.A., Gnusarev, D.I., and Klimochkin, Yu.N.,
Russian Patent 2489417, 2012; Bull. Izobret., 2013,
no. 22.
3,5-Bis(carboxymethyl)-1-adamantylcarboxylic
acid. Yield 53%, mp 267–269°C. IR spectrum, ν, cm–1:
2937, 2912, 2856 (СНAd), 1730, 1691 (C=О). 1H NMR
spectrum, δ, ppm: 1.37–1.60 m (12Н, СН2Ad), 1.99 s
(2Н, СН2СООН), 2.04 s (1Н, СНAd), 11.50 br.s (3Н,
COОН). 13С NMR spectrum, δС, ppm: 28.63 (CH),
33.33 (CCH2COOH), 37.74 (CH2), 40.64 (CH2), 41.60
(CCOOH), 42.88 (CH2), 45.95 (CH2), 47.92 (CH2COOH),
172.85 (CH2COOH), 178.50 (COOH). Found, %: С
60.83; Н 6.84. С15Н20О6. Calculated, %: С 60.80; Н
6.80. М 296.32. Mass spectrum, m/z (Irel, %): 338 (17)
[M]+, 299 (55), 298 (30), 283 (62).
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 84 No. 11 2014