5,7ꢀNonamethyleneꢀ1,3ꢀdiazaadamantanꢀ6ꢀone
Russ.Chem.Bull., Int.Ed., Vol. 65, No.10, October, 2016
2459
cyclododecanone with [15.21]adamanzane, 1,8ꢀnonameꢀ
Scheme 2
thyleneꢀ3,6ꢀdiazahomoadamantanꢀ9ꢀone (5) is formed.
Experimental
Solvents and reagents (produced in Russia, chemical grade)
were used as purchased. IR spectra were recorded with a Bruker
1
IFSv spectrophotometer in the KBr pellets. H and 13C NMR
spectra were run on a Bruker AMꢀ300 instrument (working freꢀ
quency of 300.13 MHz) in CDCl3. The chemical shifts are given in
the δ scale relative to SiMe4. Electron impact (70 eV) mass specꢀ
trometry was performed with a MSꢀ30 Kratos instrument using the
direct inlet, ion source temperature was 200 °C. Melting points
were determined with a PTPꢀM apparatus.
It was of interest to study the analogous condensation
of cyclododecanone (1) with pentamethyleneethyleneꢀ
tetramine ([15.21]adamanzane (6))16,17 and to find out
which product, 3 or 5, will be formed in the presence of
two nonꢀequivalent nitrogen atoms. The starting
[15.21]adamanzane (6) was synthesized in 70% yield by
condensation of ethylenediamine, ammonium hydrogen
carbonate, and formaldehyde (Scheme 3).
13,15ꢀDiazatetracyclo[9.5.1.11,13.111,15]nonadecanꢀ17ꢀone
(5,7ꢀnonamethyleneꢀ1,3ꢀdiazaadamantanꢀ6ꢀone (3)). A solution
of cyclododecanone (1) (2.18 g, 12 mmol), [16]adamanzane (2)
(1.4 g, 10 mmol), and acetic acid (1.5 g, 25 mmol) in BunOH
(20 mL) was gently refluxed for 4 h and then kept at room temperꢀ
ature for 24 h. The volatiles were removed in vacuo, the viscous
residue was extracted with hot heptane (4×30 mL), the extract was
filtered hot through a short layer of anhydrous alumina. Removal of
the solvent in vacuo and recrystallization of the residue from hepꢀ
tane afforded 0.41 g (15%) of compound 3, white crystals, m.p.
167—169 °C (from heptane). Found (%): C, 73.76; H, 10.10;
N, 10.21. C17H28N2O. Calculated (%): C, 73.87; H, 10.21;
N, 10.13. IR, ν/cm–1: 1710 (C=O). 1H NMR, δ: 1.03—1.55 (m, 18 H,
9 CH2); 2.25, 3.15 (both d, 8 H, 4 NCH2C, J = 10.6 Hz); 4.89
(s, 2 H, NCH2N). 13C NMR (CDCl3), δ: 218.30 C(O); 82.22
C(14); 56.38 (C(12), C(16), C(18) and C(19)); 53.48 (C(1) and
C(11)); 50.81, 39.44, 37.04, 29.83, 24.54 ((CH2)9). MS, m/z (Irel (%)):
276 [M]+ (18), 262 (18), 249 (30), 234 (66), 218 (10), 178 (10),
136 (15), 82 (18), 68 (15), 56 (65), 41 (100).
Scheme 3
13,16ꢀDiazatetracyclo[9.6.1.11,13.111,16]icosanꢀ18ꢀone (1,8ꢀ
nonamethyleneꢀ3,6ꢀdiazahomoadamantanꢀ9ꢀone (5)). A solution
of cyclododecanone (1) (2.18 g, 12 mmol), [15.21]adamanzane (6)
(1.54 g, 10 mmol), and AcOH (1.5 g, 25 mmol) in PriOH (20 mL)
was stirred at room temperature for 12 h and then kept for 24 h
without stirring. The reaction mixture was concentrated, the viscous
residue was extracted with hot heptane (4×30 mL), and the extract
was filtered hot through a short layer of anhydrous alumina. Reꢀ
moval of the solvent in vacuo and recrystallization of the residue
from heptane afforded 0.58 g (20%) of compound 5, white crystals,
m.p. 153—155 °C (from heptane; cf. Ref. 15: m.p. 153—154 °C).
Found (%): C, 74.85; H, 10.80; N, 9.31. C18H30N2O. Calculated
(%): C, 74.44; H, 10.41; N, 9.65.
[15.21]Adamanzane (1,3,6,8ꢀtetraazatricyclo[4.3.1.13,8]ꢀ
undecane) (6). To a stirred solution of ethylenediamine (6.0 g,
100 mmol) in water (10 mL), sodium hydrogen carbonate (15.8 g,
200 mmol) and paraformaldehyde (15 g, 500 mmol) were added in
small portions. After complete dissolution of paraformaldehyde, the
reaction mixture was stirred for additional 30 min. The volatiles
were removed in vacuo, the heavy residue was extracted with hot
heptane (4×25 mL). Removal of the solvent in vacuo and recrystalꢀ
lization of the residue from heptane afforded 10.8 g (70%) of
compound 6, m.p. 212—214 °C (cf. Ref. 16: m.p. 213—215 °C).
Found (%): C, 54.25; H, 9.29; N, 36.46. C7H14N4. Calculated (%):
C, 54.52; H, 9.15; N, 36.33.
i. AcOH, PriOH, 20 °C.
It was found that condensation of tetramine 6 and
cyclododecanone leads to 3,6ꢀdiazahomoadamantane 5
in 20% yield (see Scheme 3).
The two nitrogen atoms (nearly sp3 hybridized) of
compound 6 resemble nitrogen atoms of [16]adamanꢀ
zane and two others resemble those of [14.22]adamanꢀ
zane. Therefore, it is expectable that [15.21]adamanzane
6 would behave as a polyfunctional amine due apparently
to the different basicity of the two nitrogen atoms.18
Consequently, product 5 is likely formed via initial
protonation of [15.21]adamanzane 6 at the nitrogen
of highest sp3 character followed by intermolecular reacꢀ
tion of the protonated species with ketone. After
these transformations, only intramolecular reactions can
occur.
In summary, in the present work 5,7ꢀnonamethyleneꢀ
1,3ꢀdiazaadamantanꢀ6ꢀone (3) has been synthesized by
condensation of cyclododecanone with [16]adamanzane
(6). It has been also found that, in the condensation of