Efficient synthesis of 1,3-adamantanedicarboxylic acid and 1,3-diaminoadamantane

Article abstract of DOI:10.14233/ajchem.2013.14057

1,3-Adamantane dicarboxylic acid was efficiently synthesized from 1-adamantane carboxylic acid by one-pot method. 1,3- Diaminoadamantane was synthesized from 1,3-adamantane dicarboxylic acid via amidation reaction and Hofmann degradation. The structure was confirmed by NMR spectra, etc.

Full text of DOI:10.14233/ajchem.2013.14057

Asian Journal of Chemistry; Vol. 25, No. 7 (2013), 4119-4120
http://dx.doi.org/10.14233/ajchem.2013.14057
NOTE
Efficient Synthesis of 1,3-Adamantanedicarboxylic Acid and 1,3-Diaminoadamantane
1
,*
2
HUA ZHU and XIN ZHONG
1
Department of Chemistry and Chemical Engineering, Sichuan University of Arts and Science, Dazhou 635000, P.R. China
Academic Affairs Office of Sichuan University of Arts and Science, Dazhou 635000, P.R. China
2
*
Corresponding author: E-mail: zhuhua2006@163.com
Received: 14 May 2012;
(
Accepted: 30 January 2013)
AJC-12774
1
,3-Adamantane dicarboxylic acid was efficiently synthesized from 1-adamantane carboxylic acid by one-pot method. 1,3-
Diaminoadamantane was synthesized from 1,3-adamantane dicarboxylic acid via amidation reaction and Hofmann degradation. The
structure was confirmed by NMR spectra, etc.
Key Words: Adamantane, 1,3-Adamantanedicarboxylic acid, 1,3-Diaminoadamantane, Synthesis.
It is well known that carboxylic acid and amino derivatives
The characteristic features of the involved compounds (1,
1
2) were confirmed by H NMR and C NMR. NMR spectra
13
of adamantane are widely used in drug industry, polymer
synthesis and fine chemicals as key intermediates. These kinds
of compounds are usually used as antidepressants or anti-
1
were obtained on aVarian Mercury-plus 400 spectrometer ( H
13
at 400 MHz, C at 100 MHz) and are referenced to solvent or
tetramethylsilane.
1
-3
parkinsonic drugs in clinical practice . In polymer manufac-
ture, they can improve the glass transition temperatures and
1,3-Adamantane dicarboxylic acid(1): 1-Adamantane
carboxylic acid (20 g), nitric acid (65 %, 20 mL) and sulfuric
acid (98 %, 160 mL) were placed in a three-necked round-
bottom flask fitted with an efficient magnetic stirrer and a
thermometer. Cooled to 0 ºC and held at 0 ºC, anhydrous formic
acid (80 %, 70 mL) was added dropwise in 5 h and reacted for
1 h. poured to crushed ice, filtered and then washed the preci-
pitate several times with water to give a white solid. Then the
white solid was dissolved in aqueous NaOH solution and the
upper clear solution was separated and acidified by HCl to pH
= 3. Filtered, washed with water, dried in vacuum, recrystallized
4
thermal stability of polymer . In fine chemistry, they can be
-8
produce surfactants, rare earth complex, imprint lithography
9-11
resin, etc. . Due to the bifunctional structure, 1,3-adamantane
dicarboxylic acid and 1,3-diaminoadamantane have great
potential application value. The low production efficiencies
will be the biggest hindrance in the application development.
Therefore, an efficient process was sought to synthesize
of 1,3-adamantane dicarboxylic acid and 1,3-diaminoadaman-
tane.
In this paper, an efficient method for synthesis of 1,3-
adamantane dicarboxylic acid and 1,3-diaminoadamantane
from 1-adamantane carboxylic acid was reported. The synthetic
procedure sketch is shown in Scheme-I.
from ethanol. White solid, yield 22.9 g (92 %). m.p.: 275-
1
276 ºC H NMR (DMSO-d
6
, 400 MHz) δ: 1.616 (m, 2H),
1.691-1.727 (m, 4H), 1.759-1.791 (m, 4H), 1.850-1.882 (m,
13
2
H), 2.059 (m, 1H), 12.062 (br, s, 2H, COOH); C NMR (100
MHz, DMSO-d ) δ 27.37 (C-5, C-7), 34.98 (C-6), 37.66 (C-4,
C-8, C-9, C-10), 39.78 (C-2), 39.89 (C-2, C-3), 177.76
COOH
COOH
CONH2
6
HCOOH
1,SOCl
2
-1
HNO3, H SO
2
COOH
NH2
(COOH). IR (KBr, νmax, cm ) : 2913, 2851, 2636, 1691, 1451,
410, 1344, 1249, 1103, 1084, 952, 743, 670, 528;Anal. calcd
: C 64.29, H 7.14; found C 64.55, H 7.22.
,3-Diaminoadamantane(2): 1,3-Adamantane dicar-
boxylic acid (12 g) was mixed with 50 mL of SOCl and the
mixture was refluxed for 3 h. Excessive SOCl was evaporated
and 1,3-adamantane dicarbonyl dichloride was obtained as
4
CONH2
2
,NH
3
1
1
16 4
for C12H O
Hofmann Degradation
1
NH2
2
2
2
Scheme-I: Synthesis of 1,3-adamantane dicarboxylic acid and 1,3-
diaminoadamantane

4
120 Zhu et al.
Asian J. Chem.
white solid, dissolved in dried benzene and added to cold
ammonia solution slowly, during which a white precipitate
was formed gradually filtered and then washed the precipitate
several times with water to give 1,3-disaminoacyladamantane
as white solid, recrystallized from ethanol. White solid, yield
1,3-adamantane dicarboxylic acid was 92 %. The waste acid
could be transformed to industrial salt or plaster by basified
with calcium oxide, sodium hydroxide, etc.
The amidation reaction and Hofmann degradation had
high yield without optimization, the yield was 89 % and 82 %,
respectively. The total yield of 1,3-diaminoadamantane was
73 %.
1
0.58 g (89 %).
Put 1,3-bisaminoacyladamantane (10.58 g) and aqueous
NaOH solution (10 %, 65 mL) into a 500 mL three-necked
round-bottom flask fitted with an efficient magnetic stirrer and
a thermometer, stirring at room temperature, a slurry was
formed, cooled to 0 ºC, the fresh sodium hypobromite solution,
which dissolved bromine (23 g) and sodium hydroxide (23 g)
in 150 mL water was added to the slurry at 0 ºC. stirring and
held at 0 ºC for 1 h, the mixture became a yellow transparent
solution, then heated to 80 ºC and reacted for 1 h, cooled to
room temperature, extracted by chloroform (3 × 50 mL),
Overall, each step had high efficiency and excellent yield,
the energy consumption and environmental impact were low.
The industrialization of this process was easily and the research
of application will be promoted.
Conclusion
1
,3-Adamantane dicarboxylic acid and 1,3-diaminoad-
amantane were synthesized from 1-adamantanecarboxylic acid
successively, each step had excellent yield, this method could
be industrialized and promoted the research of application of
combined the organic layer and dried over anhydrous MgSO
after removal of MgSO and chloroform, the crude 1,3-
diaminoadamantane was purified by sublimation; white solid,
4
,
1,3-adamantane dicarboxylic acid and 1,3-diaminoadamantane.
4
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3
.5 mL, under this ratio and reacted 6 h at 0 ºC, the yield of