IVLEVA et al.
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3,5-Bis(carboxymethyl)-7-methyl-1-adamantane-
178.74 (C). Found, %: C 59.60; Н 6.45. С14Н18О6.
Calculated, %: C 59.57; Н 6.43.
carboxylic acid (13). Yield 79%, mp 228–230°C. IR
spectrum, ν, cm–1: 2943, 2908, 2854 (СНAd), 1693
5-Carboxymethyl-7-methyl-1,3-adamantane-
dicarboxylic acid (16). Yield 40%, mp 210–212°C. IR
spectrum, ν, cm–1: 2954, 2910 (СНAd), 1698 (C=О). 1Н
NMR spectrum, δ, ppm: 0.82 s (3Н, СН3), 1.13–1.21
m (6Н, 3СН2Ad), 1.29–1.37 m (4Н, 2СН2Ad), 1.43–1.51
m (2Н, СН2Ad), 2.04 s (2Н, СН2СООН), 11.48 br.s
(3Н, 3COОН). 13С NMR spectrum, δ, ppm: 28.92
(CH3), 33.48 (C), 34.94 (C), 37.41 (CH2), 41.53 (C),
42.11 (CH2), 43.88 (CH2), 44.42 (CH2), 46.12 (CH2),
47.37 (CH2), 171.50 (C), 178.28 (C). Found, %: C
60.78; Н 6.81. С15Н20О6. Calculated, %: C 60.80; Н
6.80.
1
(C=О). Н NMR spectrum, δ, ppm: 0.80 s (3Н, СН3),
1.12–1.23 m (4Н, 2СН2Ad), 1.28–1.53 m (8Н, 4СН2Ad),
2.11 s (4Н, 2СН2СООН), 11.53 br.s (3Н, 3COОН).
13С NMR spectrum, δ, ppm: 21.42 (CH3), 42.12 (C),
42.30 (CH2), 42.32 (C), 42.46 (C), 44.63 (CH2), 45.32
(CH2), 47.71 (CH2), 47.97 (CH2), 172.87 (C), 178.65
(C). Found, %: C 61.95; Н 7.18. С16Н22О6. Calculated,
%: C 61.92; Н 7.15.
3,5-Bis(carboxymethyl)-7-ethyl-1-adamantane-
carboxylic acid (14).Yield 77%, mp 240–242°C. IR
spectrum, ν, cm–1: 2912 (СНAd), 1697 (C=О). 1Н NMR
spectrum, δ, ppm: 0.70–0.74 t (3Н, СН3, J 7.5 Hz),
1.09–1.15 q (2Н, СН2СН3, J 7.5 Hz), 1.17–1.20 m
(4Н, 2СН2Ad), 1.27–1.38 m (4Н, 2СН2Ad), 1.50 s (4Н,
2СН2СООН), 2.02 s (2Н, СН2Ad), 8.09 br.s (3Н,
3COОН). 13С NMR spectrum, δ, ppm: 7.48 (CH3),
33.96 (C), 34.03 (C), 35.56 (CH2), 42.21 (CH2), 42.32
(C), 42.65 (CH2), 45.28 (CH2), 45.66 (CH2), 47.73
(CH2), 172.83 (C), 178.48 (C). Found, %: C 62.97; Н
7.49. С17Н24О6. Calculated, %: C 62.95; Н 7.46.
5-Carboxymethyl-7-ethyl-1,3-adamantane-
dicarboxylic acid (17). Yield 74%, mp 265–267°C. IR
spectrum, ν, cm–1: 2962, 2941 (СНAd), 1699 (C=О). 1Н
NMR spectrum, δ, ppm: 0.71–0.75 t (3Н, СН3, J 7.3 Hz),
1.12–1.18 q (2Н, СН2СН3, J 7.3 Hz), 1.20–1.21 m
(2Н, СН2Ad), 1.36–1.38 m (4Н, 2СН2Ad), 1.50–1.53 m
(4Н, 2СН2Ad), 1.70–1.71 m (2Н, СН2Ad), 2.08 s (2Н,
СН2СООН), 10.08 s (3Н, 3COОН). 13С NMR spec-
trum, δ, ppm: 7.42 (CH3), 33.72 (C), 33.84 (C), 35.42
(CH2), 39.59 (CH2), 42.06 (CH2), 42.46 (CH2), 45.01
(CH2), 47.46 (CH2), 170.81 (C), 178.19 (C). Found, %: C
61.96; Н 7.18. С16Н22О6. Calculated, %: C 61.92; Н 7.15.
Compounds 15–17. General method. To solution of
0.01 mol of the appropriate acid 5, 7, and 8 in 50 mL
of 96% sulfuric acid while stirring and cooling 0.05 mol
of fuming nitric acid was added dropwise maintaining
the temperature of the reaction mixture no higher than
50°C, the mixture was kept at the adjusted temperature
for 3 h, cooled, and 0.1 mol of 100% formic acid was
added dropwise at 25-30°C while stirring intensively.
The obtained solution was left standing for 24 h at
room temperature, poured on 250 g of crushed ice, and
left standing for 24 h more. The precipitate was filtered
off, washed with a little of ice water. The mother
liquor was neutralized to pH 4 using 30% aqueous
solution of NaOH. The precipitate of inorganic salts
was filtered off, the mother liquor was extracted with
butanol (10 × 20 mL), the solvent was evaporated in a
vacuum, the combined precipitates were recrystallized
from glacial acetic acid.
5,7-Bis(carboxymethyl)-1,3-adamantanedicar-
boxylic acid (18). To 0.073 mol of fuming nitric acid
while cooling was added by portions 22 mL of 35%
oleum. Into the obtained mixture while stirring was added
in one portion 7.3 mmol of the correspondding acid 11
and 13. The reaction mixture was heated to 75–80°C,
stirred intensively for 5 h, cooled to room temperature,
and 1.92 mol of 100% formic acid was slowly added
dropwise. The reaction mixture was kept for 12 h at room
temperature and poured on 100 g of crushed ice. The
obtained solution was neutralized to pH 4 using 30%
aqueous solution of NaOH. The precipitate of inorganic
salts was filtered off, the mother liquor was extracted
with butanol (10 × 20 mL), the solvent was evaporated in
a vacuum, the residue was recrystallized from glacial
acetic acid. Yield 64%, mp 249–250°S. IR spectrum, ν,
cm–1: 2912, 2862, 2829 (СНAd), 1697 (C=О). 1Н NMR
spectrum, δ, ppm: 1.36 s (2Н, СН2Ad), 1.53 s (8Н, 4СН2Ad),
1.69 s (2Н, СН2Ad), 2.05 s (4Н, 2СН2СООН), 8.98 br.s
(4Н, 4COОН). 13С NMR spectrum, δ, ppm: 33.71 (C),
39.28 (CH2), 41.91 (C), 42.14 (CH2), 45.09 (CH2), 47.31
(CH2), 172.74 (C), 177.97 (C). Found, %: C 56.50; Н
5.96. С16Н20О8. Calculated, %: C 56.47; Н 5.92.
5-Carboxymethyl-1,3-adamantanedicarboxylic
acid (15). Yield 47%, mp 223–225°C. IR spectrum, ν,
cm–1: 2941, 2912, 2860 (СНAd), 1695 (C=О). 1Н NMR
spectrum, δ, ppm: 1.37–1.79 m (12Н, 6СН2Ad), 2.02 s
(2Н, СН2СООН), 2.08–2.09 m (1Н, СНAd), 12.06 br.s
(3Н, 3COОН). 13С NMR spectrum, δ, ppm: 28.30
(CH), 32.61 (C) 35.78 (CH2), 38.36 (CH2), 40.87 (C),
41.32 (CH2), 43.45 (CH2), 48.31 (CH2), 172.92 (C),
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 51 No. 2 2015