Synthesis of 1-benzyl-3,6-diazahomoadamantane

Article abstract of DOI:10.1134/S1070428013110183

By condensation of 4-phenylbutan-2-one with tetramethylenediethylenetetramine 1-benzyl-3,6- diazahomoadamantan -9-one was synthesized. Further nitration of 1-benzyl-3,6-diazahomoadamantan-9-one yielded 1-(4-nitrobenzyl)-3,6- diazahomoadamantan -9-one. The

Full text of DOI:10.1134/S1070428013110183

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2013, Vol. 49, No. 11, pp. 1670−1675. © Pleiades Publishing, Ltd., 2013.
Original English Text © A.I. Kuznetsov, I.M. Senan, R.T. Alasadi, A.Kh. Shukkur, T.M. Serova, 2013, published in Zhurnal Organicheskoi Khimii, 2013, Vol. 49,
No. 11, pp. 1683−1686.
Synthesis of 1-Benzyl-3,6-diazahomoadamantane
A. I. Kuznetsova, I. M. Senana, R. T. Alasadia,c, A. Kh. Shukkura, and T. M. Serovab
aLomonosov Moscow State University of Fine Chemical Technologies, Moscow,119571 Russia
e-mail: tetraza@mail.ru
bInstitute of Physiologically Active Compounds, Russian Academy of Sciences, Chernogolovka, Russia
cUniversity of Kerbala, Iraq
Received April 29, 2013
Abstract—By condensation of 4-phenylbutan-2-one with tetramethylenediethylenetetramine 1-benzyl-3,6-
diazahomoadamantan-9-one was synthesized. Further nitration of 1-benzyl-3,6-diazahomoadamantan-9-one yielded
1-(4-nitrobenzyl)-3,6-diазаhomoadamantan-9-one. The modification of the nitro and carbonyl groups resulted in
the formation of 1-benzyl-3,6-diazahomoadamantane and its derivatives with functional groups in the benzene
ring and at the bridge carbon atom С9.
DOI: 10.1134/S1070428013110183
We reported on the synthesis of some derivatives of
3,6-diazahomoadamantan-9-one with substituents at the
nodal atom С1 by the condensation of methyl ketones with
tetramethylenediethylenetetramine and on their further
transformations into 3,6-diazahomoadamantane [1] and
its derivatives [2].
two АВ systems of protons NCH2C, the multiplet of
the protons of the ethylene bridge NCH2CH2N, and the
broadened singlet at 2.65 ppm from the proton located in
the nodal position. The benzyl group signal appears as a
singlet of the methylene group protons at 2.85 ppm and
a multiplet of the benzene group protons in the region
7.10–7.35 ppm. In the IR spectrum the absorption bands
of the stretching vibrations of the carbonyl groups in
the region 1707 cm–1 and of benzene ring in the region
1605 cm–1 are observed. The mass spectrum contains the
molecular ion peak ([M]+ 256), whose main fragmentation
occurs as the framework decomposition and the formation
of cations with m/z 72 and 58.
In extension of the research on the synthesis of
new derivatives of 3,6-diazahomoadamantane we
obtained 1-benzyl-3,6-diazahomoadamantan-9-one
(I) by the condensation of 4-phenylbutan-2-one
1
with etramethylenediethylenetetramine. Its H NMR
spectrum contains the group of signals characteristic
of the diazahomoadamantane framework consisting of
O
O
N
CH3COOH
N
N
N
N
N
+
I
The hydrazone of ketone II was subjected to Kishner–
Wolff reduction into 1-benzyl-3,6-diazahomoadamantane
(III) [3]. In the mass spectrum of benzyldiazahomoada-
mantane (III) the molecular ion peak was present ([M]+
242), whose main fragmentation was governed by the
rupture of the bond between the benzyl substituent and
the framework and by the formation of cations with m/z
151 and 91. In the 1H NMR spectrum the proton in the
nodal position of the framework gave rise to a singlet at
1.85 ppm, two protons of the methylene from the benzyl
group appeared as a singlet at 2.35 ppm, the protons of
the ethylene fragment NCH2CH2N, as a multiplet at 3.05
ppm. Four doublets at 2.60, 2.95, 3.15, and 2.70 ppm cor-
respond to the protons of four methylene groups NCH2C.
1670

SYNTHESIS OF 1-BENZYL-3,6-DIAZAHOMOADAMANTANE
1671
H2N
N
H2NNH2
KOH
N
I
N
N
Δ
N
II
III
The protons of the methylene group of the framework
CCH2С are observed as a singlet at 1.60 ppm.
bands of stretching vibrations of azomethine and hydroxy
groups at 1630 and 3220 cm–1 respectively.
The treatment of ketone I with hydroxylamine
afforded 1-benzyl-3,6-diazahomoadamantan-9-one
oxime (IV) whose IR spectrum contained the absorption
Oxime IV was reduced with nickel–aluminum alloy
[4] (50 : 50) (Raney alloy) in water-alkaline medium into
1-benzyl-3,6-diazahomoadamantan-9-amine (V).
HO
N
NH2
NiRа_NaOH
NH2OH
I
N
N
V
N
N
IV
The comparison of the values of the chemical shifts
of protons attached to the atom C8 in the spectra of
hydrazone II and oxime IV and the other analogous
derivatives of diazahomoadamantane [3, 5] allows a
conclusion that the double bond in compounds II, IV
with a benzyl group possesses the E-configuration. When
a phenyl is present instead of the benzyl group, the π-bond
has the Z- configuration [5].
2.41 s
NH2
H
CH3
N
H
N
H
N
H
N
NH2
NH2
NH2
N
N
N
N
N
N
N
N
H
2.32 s
2.85 s
3.02 s
2.92 s
3.06 c
N
OH
N
H
CH3
N
H
N
H
OH
OH
OH
N
N
N
N
N
N
N
N
H
H
3.69 s
3.61 s
3.02 s
3.70 s
The nitration of benzyldiazahomoadamantanone
(I) with a mixture of potassium nitrate and sulfuric
acid [6] led to the formation of 1-(4-nitrobenzyl)-3,6-
diazahomoadamantan-9-one (VI) that was reduced with
tin in hydrochloric acid into 1-(4-aminobenzyl)-3,6-
diazahomoadamantan-9-one (VII).
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KUZNETSOV et al.
1672
O
O
NH2
(1) Sn_HCl
(2) NaOH
NO2
KNO3
H2SO4
N
N
I
N
N
VI
VII
The IR spectrum of nitroketone VI contains absorption
bands of the stretching vibrations of the nitro group in the
region 1514, 1350 cm–1 and the carbonyl group at 1697
cm–1. Mass spectra of compounds VI and VII contain the
molecular ion peaks ([M]+ 301) and ([M]+ 271), whose
main fragmentation occurs as the framework decomposi-
tion and the formation of cations with m/z 42, 58, and 72.
with alkali gave 4-[(3,6-diazahomoadamantan-1-yl)
methyl]-aniline (XI) that also was formed at the non-
catalytic reduction of nitrobenzyldiazahomoadamantane
(IX) with hydrazine.
In the mass spectra of compounds IX, XI molecular
ion peaks are observed as ([M]+ 287) and ([M]+ 257),
respectively. Their main fragmentation occurs as the
cleavage of the benzyl substituent and the formation of
the diazahomoadamantyl cation, m/z 151.
The reaction of nitroketone VI with hydrazine hydrate
furnishes two compounds depending on the temperature.
Below 50°C hydrazone of 1-(4-nitrobenzyl)-3,6-diazaho-
moadamantan-9-one (VIII) was obtained. It was reduced
by Kishner–Wolff procedure into 1-(4-nitrobenzyl)-3,6-
diazahomoadamantane (IX). The boiling of nitroketone
VI with hydrazine hydrate results in the noncatalytic
reduction of the nitro group into amino group [6] with
the formation of hydrazone of 1-(4-aminobenzyl)-3,6-
diazahomoadamantan-9-one (X). The latter at heating
The reduction of nitroketone VI with zinc and alkali
in 2-propanol provided (Е)-azobenzene-4,4'-bis{[(3,6-
diazahomoadamantan-1-yl)methyl]-9-one} (XII),
which was reduced with sodium borohydride into (Е)-
azobenzene-4,4'-bis{[1-(3,6-diazahomoadamantan-1-yl)
methyl]-9-ol} (XIII).
The IR spectrum of compound XII contained absorp-
tion bands of the stretching vibrations of the carbonyl
H2N
N
NO2
NO2
H2NNH2
KOH
N
N
Δ
N
N
100oC
VIII
IX
H2NNH2,
50oC
H2N
N
NH2
NH2
H2NNH2
100oC
KOH
N
N
VI
N
N
Δ
XI
X
N
N
N
N
Zn /NaOH
HO
O
NaBH4
N N
N N
OH
O
N
N
N
N
XII
XIII
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 11 2013

SYNTHESIS OF 1-BENZYL-3,6-DIAZAHOMOADAMANTANE
1673
and azo groups at 1707 and 1603 cm–1, respectively, the
spectrum of compound XIII contained two absorption
bands of hydroxy groups at 3536 and 3560 cm–1. In the
mass spectra of compounds XII, XIII strong molecular
ion peaks are observed as ([M]+ 538) and ([M]+ 542).
The synthesized derivatives of (Е)-azobenzene
XII, XIII under the UV-irradiation can transform into
Z-isomers and undergo the reverse conversion into E-
isomers at heating [7]. Consequently, they may serve as
molecular switches.
for 3 h. The reaction mixture was evaporated, the residue
was recrystallized from toluene. Yield 1.00 g (73%), white
crystals, mp 131–132°С. IR spectrum, ν, cm–1: 3315, 3180
1
(NH2), 1645 (С=N), 1613 (Ph). Н NMR spectrum, δ,
ppm: 2.85 br.s (1Н, СН), 2.85 s (2Н, СН2), 2.95 d (2H,
NCH2C, J 14.0 Hz), 3.00 d (2H, NCH2C, J 14.0 Hz),
3.05 s (4H, NCH2CH2N), 3.10 d (2H, NCH2C, J 14.0 Hz),
3.30 d (2H, NCH2C, J 14.0 Hz), 5.10 br.s (2Н, NH2),
7.10–7.35 m (5Н, Ph). Mass spectrum, m/z (Irel, %): 270
[M]+ (32), 269 (72), 254 (43), 112 (22), 184 (22), 115
(21), 91 (52), 85 (16), 72 (100), 58 (36), 43 (41). Found,
%: С 71.20; H 8.35; N 20.50. C16H22N4. Calculated, %:
С 71.07; H 8.20; N 20.72. M 270.37.
EXPERIMENTAL
IR spectra of the studied compounds were recorded on
a spectrophotometer Bruker IFSv from pellets with KBr.
1Н NMR spectra were registered on a spectrometer Bruker
WM-250 at operating frequency 250.13 MHzfrom solu-
tions of compounds in CDCl3, internal reference TMS.
Mass spectra were measured on an instrument Finnigan
MAT 90 with a direct admission into the ion source, ac-
celerating voltage 5.0 kV, cathode emission current 100
μА, ionizing electrons energy 70 eV, ionizing chamber
temperature 200°С.
1-Benzyl-3,6-diazahomoadamantane (III). A thor-
oughly stirred mixture of 0.54 g (2 mmol) of hydrazone
II and 0.60 g (11 mmol) of potassium hydroxide was
heated for 2 h at 220–240°С, then cooled and extracted
with toluene (3 × 20 ml). The solvent was evaporated,
the residue was recrystallized from toluene. Yield 0.30 g
(62%), white crystals, mp 61–62°С. IR spectrum, ν, cm–1:
1610 (Ph). 1Н NMR spectrum, δ, ppm: 1.60 s (2Н, СН2),
1.85 br.s (1Н, СН), 2.35 s (2Н, СН2), 2.60 d (2H, NCH2C,
J 14.0 Hz), 2.70 d (2H, NCH2C, J 14.0 Hz), 2.95 d (2H,
NCH2C, J 14.0 Hz), 3.05 s (4H, NCH2CH2N), 3.15 d (2H,
NCH2C, J 14.0 Hz), 7.10–7.15 m (5Н, Ph). Mass spec-
trum, m/z (Irel, %): 242 [M]+ (82), 198 (43), 184 (69), 151
(58), 108 (42), 91 (99), 85 (54), 73 (46), 65 (44), 57 (100),
43 (74). Found, %: С 79.15; H 9.30; N 11.30. C16H22N2.
Calculated, %: С 79.29; H 9.15; N 11.55. M 242.36.
1-Benzyl-3,6-diazahomoadamantan-9-one (I). A
mixture of 14.30 g (85 mmol) of tetramethylenediethy-
lenetetramine, 14.10 g (95 mmol) of 4-phenylbutan-2-
one, and 15.30 g (260 mmol) of acetic acid in 130 mL of
2-butanol was heated for 30 min at 60–70°С. The reac-
tion mixture was concentrated in a vacuum, the viscous
residue was treated with hot heptane (4 × 50 ml). The
warm extract was purified by filtration through a bed of
anhydrous aluminum oxide (10 g, II grade of activity)
placed on a glass frit filter. The solvent was distilled off,
the residue was recrystallized from heptane. Yield 7.00 g
(32%), white crystals, mp 102–104°С. IR spectrum, ν,
1-Benzyl-3,6-diazahomoadamantan-9-one oxime
(IV). To a solution of 1.30 g (5 mmol) of ketone I in 5 mL
of water was added 0.42 g (6 mmol) of hydroxylamine
hydrochloride. The mixture was heated at 60–70°С and
at continuous stirring was added by portions within
15 min a solution of 0.62 g (6 mmol) of Na2CO3 in 5 mL
of water. The mixture was stirred at this temperature for
10 min. The separated precipitate was filtered off, dried,
and recrystallized from toluene. Yield 1.10 g (81%), white
crystals, mp 236–238°С. IR spectrum, ν, cm–1: 3220
1
cm–1: 1707 (С=О), 1605 (Ph). Н NMR spectrum, δ,
ppm: 2.65 br.s (1Н, CН), 2.85 s (2Н, CH2), 2.90 d (2H,
NCH2C, J 14.0 Hz), 3.00 d (2H, NCH2C, J 14.0 Hz),
3.05 s (4Н, NCH2СН2N), 3.15 d (2H, NCH2C, J 14.0 Hz),
3.45 d (2H, NCH2C, J 14.0 Hz), 7.10–7.35 m (5Н, Ph).
Mass spectrum, m/z (Irel, %): 256 [M]+ (76), 213 (73),
165 (14), 137 (19), 131 (21), 122 (20), 101 (50), 91 (72),
72 (99), 58 (100), 43 (41). Found, %: С 74.95; H 8.05;
N 10.67. С16H20N2O. Calculated, %: С 74.96; H 7.86;
N 10.92. M 256.34.
1
(OH), 1630 (C=N), 1600 (Ph). Н NMR spectrum, δ,
ppm: 1.89 s (2Н, СН2), 2.85 m (4Н, NCH2CH2N), 2.95 d
(2H, NCH2C, J 13.9 Hz), 3.02 m (2H, NCH2C), 3.13 d
(2H, NCH2C, J 13.9 Hz), 3.30 d (2H, NCH2C, J 13.9 Hz),
3.69 s (1Н, СН), 7.10–7.15 m (2Н, Ph), 7.15–7.22 m (2Н,
Ph), 8.75 s (1Н, OН). Mass spectrum, m/z (Irel, %): 271
[M]+ (100), 254 (90), 211 (31), 154 (6), 120 (5), 106 (10),
91 (14), 72 (11), 57 (13), 43 (28). Found, %: С 70.85;
H 7.73; N 15.30. C16H21N3O. Calculated, %: С 70.82;
1-Benzyl-3,6-diazahomoadamantan-9-one hydra-
zone (II). A solution of 1.30 g (4.8 mmol) of ketone I in
10 mL of 80% solution of hydrazine hydrate was boiled
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KUZNETSOV et al.
1674
H 7.80; N 15.49. M 271.36.
ketone VI in 5 mL of hydrochloric acid was added 0.5 g
of tin in small granules, and the mixture was boiled for
1 h. The reaction mixture was cooled, 5 mL of water
was added, and the mixture was neutralized with NaOH
solution to pH 8. The reaction products were extracted
with toluene (3 × 20 ml), the solvent was distilled off,
the residue was recrystallized from toluene. Yield 0.35 g
(69%), white crystals, mp 118–119°С. IR spectrum, ν,
cm–1: 3400, 3319, 3211 (NH2), 1690 (С=O), 1612 (Ph).
1Н NMR spectrum, δ, ppm: 2.60 s (2Н, СН2), 2.70 d (2H,
NCH2C, J 14.0 Hz), 2.90 d (2H, NCH2C, J 14.0 Hz),
3.05 s (4H, NCH2CH2N), 3.10 d (2H, NCH2C, J 14.0 Hz),
3.40 d (2H, NCH2C, J 14.0 Hz), 3.60 br.s (2Н, NH2),
3.95 br.s (1Н, СН), 6.60–7.00 m (4Н, Ph). Mass spectrum,
m/z (Irel, %): 271 [M]+ (29), 262 (8), 228 (12), 200 (13),
170 (5), 140 (15), 106 (35), 84 (21), 72 (100), 55 (45), 43
(41). Found, %: С 70.65; H 7.30; N 14.70. C16H21N3O.
Calculated, %: С 70.82; H 7.80; N 15.48. M 271.36.
1-Benzyl-3,6-diazahomoadamantan-9-amine (V).
To a slurry of 0.50 g (1.84 mmol) of oxime IV and 1.84 g
of Ni–Al alloy (50:50) in 10 mL of water was added
dropwise at vigorous stirring within 1 h a solution of
1.84 g of sodium hydroxide in 15 mL of water, main-
taining the temperature of the reaction mixture below
50°C. The mixture was stirred for 2 h more, cooled, the
reaction products were extracted with ether (3 × 10 mL).
The ether solution was dried with potassium hydroxide
and evaporated. Yield 0.38 g (81%), white crystals, mp
118–120°С. IR spectrum, ν, cm–1: 3374 (NH), 1610 (Ph).
1Н NMR spectrum, δ, ppm: 1.40 s (2Н, NН2), 1.62 s (1Н,
СН), 2.31 d (1H, NCH2C, J 13.9 Hz), 2.45 d (1H, NCH2C,
J 13.2 Hz), 2.49 s (1H, CH2), 2.57 s (1H, CH2), 2.58 d
(1H, NCH2C, J 13.2 Hz), 2.75 s (1Н, СНN), 2.78 d (1H,
NCH2C, J 13.9 Hz), 2.84 d (1H, NCH2C, J 13.9 Hz),
2.94 s (4H, NCH2CH2N), 3.18 d (1H, NCH2C, J 13.9 Hz),
3.38 d (1H, CHNH2, J 11.7 Hz), 3.53 d (1H, NCH2C,
J 13.9 Hz), 7.02–7.10 m (2Н, Ph), 7.12–7.29 m (3Н, Ph).
Mass spectrum, m/z (Irel, %): 257 [M]+ (100), 239 (14),
227 (12), 213 (20), 199 (39), 170 (41), 120 (10), 91 (32),
72 (69), 56 (27), 43 (36). Found, %: С 74.51; H 9.30;
N 16.30. C16H23N3. Calculated, %: С 74.67; H 9.01;
N 16.33. M 257.37.
1-(4-Nitrobenzyl)-3,6-diazahomoаdаmаntаn-9-
one hydrazone (VIII). A solution of 0.60 g (2 mmol) of
nitro-ketone VI in a mixture of 10 mL of 80% hydrazine
hydrate and 10 mLof ethanol was heated for 3.5 h at 50°С
and evaporated to dryness. The residue was recrystallized
from toluene. Yield 0.35 g (56%), yellow crystals, mp
220–225°С (c разл.). IR spectrum, ν, cm–1: 3309, 3181
(NH2), 1603 (С=N), 1593 (Ph), 1513, 1343 (NO2).
1Н NMR spectrum, δ, ppm: 2.65 br.s (1Н, СН), 2.75 d
(2H, NCH2C, J 14.0 Hz), 2.90 s (2Н, СН2), 2.95 d (2H,
NCH2C, J 14.0 Hz), 3.05 s (4H, NCH2CH2N), 3.10 d
(2H, NCH2C, J 14.0 Hz), 3.25 d (2H, NCH2C, J 14.0 Hz),
5.10 br.s (2Н, NH2), 8.20–7.25 m (4Н, С6Н4). Mass
spectrum, m/z (Irel, %): 315 [M]+ (7), 254 (22), 211 (23),
183 (38), 168 (36), 106 (30), 101 (34), 91 (33), 72 (100),
56 (58), 43 (47). Found, %: С 59.72; H 6.91; N 22.57.
C16H21N5O2. Calculated, %: С 60.93; H 6.71; N 22.20.
M 315.37.
1-(4-Nitrobenzyl)-3,6-diazahomoadamantan-9-one
(VI). To a solution of 0.88 g (8.7 mmol) of potassium
nitrate in 18 mL of conc. H2SO4 cooled to 0–5°С was
added at stirring with small portions within 15 min 2.20 g
(8.7 mmol) of ketone I, the stirring without cooling was
continued for 2 h, the mixture was poured into 100 mL
of water ad neutralized with K2CO3 to pH 8–9. The
formed precipitate was filtered off, dried, and extracted
with toluene (3 × 20 ml). The solvent was distilled off,
the residue was recrystallized from toluene. Yield 1.90 g
(73%), yellow crystals, mp 195–196°С. IR spectrum,
ν, cm–1: 1697 (С=O), 1600 (Ph)1514, 1350 (NO2).
1Н NMR spectrum, δ, ppm: 2.65 br.s (1Н, СН), 2.85 d
(2H, NCH2C, J 14.0 Hz), 2.90 s (2Н, СН2), 3.00 d (2H,
NCH2C, J 14.0 Hz), 3.05 s (4H, NCH2CH2N), 3.10 d
(2H, NCH2C, J 14.0 Hz), 3.40 d (2H, NCH2C, J 14.0 Hz),
7.25–8.20 m (4Н, Ph). Mass spectrum, m/z (Irel, %): 301
[M]+ (96), 273 (25), 258 (21), 228 (14), 128 (15), 116 (36),
106 (20), 83 (50), 72 (73), 58 (81), 42 (100). Found, %:
С 63.40; H 6.49; N 13.31. C16H19N3O3. Calculated, %:
С 63.77; H 6.35; N 13.94. M 301.34.
1-(4-Nitrobenzyl)-3,6-diazahomoadamantane (IX)
was obtained similarly to compound III from 0.31 g (1
mmol) of hydrazone VIII and 0.3 g of powdered KOH.
Yield 0.22 g (65%), yellow crystals, mp 141–142°С. IR
spectrum, ν, cm–1: 1600 (Ph), 1512, 1349 (NO2). 1Н NMR
spectrum, δ, ppm: 1.60 br.s (2Н, СН2), 1.85 br.s (1Н, СН),
2.45 s (2Н, СН2), 2.60 d (2H, NCH2C, J 14.0 Hz), 2.70 d
(2H, NCH2C, J 14.0 Hz), 2.95 d (2H, NCH2C, J 14.0 Hz),
3.15 d (2H, NCH2C, J 14.0 Hz), 3.20 c (4H, NCH2CH2N),
8.20–7.20 m (4Н, Ph). Mass spectrum, m/z (Irel, %): 287
[M]+ (80), 243 (61), 229 (55), 215 (34), 151 (91), 128
(38), 95 (100), 84 (74), 72 (59), 57 (76), 42 (58). Found,
%: С 70.20; H 7.69; N 14.75. C16H21N3O2. Calculated,
1-(4-Aminobenzyl)-3,6-diazahomoadamantan-9-
one (VII). To a solution of 0.57 g (1.9 mmol) of nitro-
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SYNTHESIS OF 1-BENZYL-3,6-DIAZAHOMOADAMANTANE
1675
%: С 70.81; H 7.80; N 15.48. M 287.36.
in 15 mL of i-PrOH and 2 mL of water was added at
vigorous stirring 0.80 g (20 mmol) of zinc. The reaction
mixture was boiled for 3 h and on cooling the solution
was decanted, evaporated, and the residue was extracted
with toluene (3 × 10 ml) and recrystallized from heptane.
Yield 0.53 g (88%), yellow crystals, mp 254–256°С.
IR spectrum, ν, cm–1: 1603 (N=N, Ph), 1707 (С=О).
1Н NMR spectrum, δ, ppm: 2.65 s (2Н, 2CН), 2.89 s
(4Н, 2CH2Ph), 2.91–3.13 m (8H, 4NCH2C), 3.08 s (8Н,
2NCH2СН2N), 3.15 d (4H, 2NCH2C, J 14.3 Hz), 3.43 d
(4H, 2NCH2C, J 13.6 Hz), 7.21–8.19 m (8Н, Ph). Mass
spectrum, m/z (Irel, %): 538 [M]+ (59), 300 (26), 271 (39),
194 (11), 163 (7), 149 (8), 106 (20), 91 (39), 72 (100),
59 (29), 43 (58). Found, %: С 71.22; H 7.16; N 15.55.
C32H38N6O2. Calculated, %: С 71.35; H 7.11; N 15.60.
M 538.68.
1-(4-Aminobenzyl)-3,6-diazahomoadamantan-9-
one hydrazone (X). A solution of 0.75 g (2.5 mmol)
of nitroketone VI in 10 mL of 80% hydrazine hydrate
was heated for 3 h at 100°С. The reaction mixture was
evaporated, the residue was recrystallized from toluene.
Yield 0.6 g (85%), white crystals, mp 188–189°С. IR
spectrum, ν, cm–1: 3441, 3329 (NH2), 3215 (NH2Ph),
1
1632 (С=N), 1593 (Ph). Н NMR spectrum, δ, ppm:
2.35 br.s (1Н, СН), 2.70s(2Н, СН2), 2.80d (2H, NCH2C,
J 14.0 Hz), 2.90 d (2H, NCH2C, J 14.0 Hz), 3.00 s (4H,
NCH2CH2N), 3.15 d (2H, NCH2C, J 14.0 Hz), 3.25 d
(2H, NCH2C, J 14.0 Hz), 3.60 br.s (2Н, NH2 Ph),
5.05 br.s (2Н, NH2), 6.60 d (2Н, С6Н4), 6.85 d (2Н,
С6Н4). Mass spectrum, m/z (Irel, %): 285 [M]+ (19), 269
(80), 197 (60), 157 (59), 130 (37), 111 (42), 106 (92),
92 (66), 72 (100), 57 (25), 42 (26). Found, %: С 67.89;
H 8.59; N 23.34. C16H23N5. Calculated, %: С 67.33;
H 8.12; N 24.53. M 285.39.
(Е)-Azobenzene-4,4'-bis{[(3,6-diazahomo-
adamantan-1-yl)methyl]-9-ol} (XIII).Asolution of 0.30
g (0.6 mmol) of compound XII and 0.10 g (2.5 mmol)
of NaBH4 in 8 mL of EtOH was heated for 2 h at slight
boiling. The solvent was distilled off, several drops of
water was added till complete dissolution of the dry
residue, water was distilled off, the residue was extracted
with chloroform (4 × 40 ml). The extract was dried with
MgSO4, evaporated, the residue was recrystallized from
2-propanol. Yield 0.53 g (88%), yellow crystals, mp
272–274°С. IR spectrum, ν, cm–1: 3560, 3536 (OH), 1600
(N=N, Ar). Mass spectrum, m/z (Irel, %): 542 [M]+ (100),
471 (4), 273 (32), 201 (7), 184 (19), 167 (27), 149 (12),
106 (25), 91 (17), 72 (53), 60 (33), 43 (84). Found, %:
С 70.76; H 7.74; N 15.24. C32H42N6O2. Calculated, %:
С 70.82; H 7.80; N 15.49. M 542.72.
4-[(3,6-Diazahomoadamantan-1-yl)methyl]
aniline (XI). а. A thoroughly stirred mixture of 0.57
g (2 mmol) of hydrazone X and 0.60 g (11 mmol) of
powdered potassium hydroxide was heated for 2 h
220–240°С, cooled, and extracted with toluene (3 ×
20 ml). The solvent was distilled off, the residue was
recrystallized from toluene. Yield 0.30 g (59%), white
crystals, mp 153–154°С. IR spectrum, ν, cm–1: 3338,
1
3177 (NH2), 1611 (Ph). Н NMR spectrum, δ, ppm:
1.55 br.s (2Н, СН2), 1.80 br.s (1Н, СН), 2.25 s (2Н, СН2),
2.55 d (2H, NCH2C, J 14.0 Hz), 2.70 d (2H, NCH2C,
J 14.0 Hz), 2.90 d (2H, NCH2C, J 14.0 Hz), 3.00 s (4H,
NCH2CH2N), 3.15 d (2H, NCH2C, J 14.0 Hz), 3.60 br.s
(2Н, NH2), 6.60 d (2Н, С6Н4), 6.85 d (2Н, С6Н4). Mass
spectrum, m/z (Irel, %): 257 [M]+ (100), 213 (31), 199
(43), 185 (35), 151 (50), 106 (46), 99 (30), 82 (34),
72 (22), 57 (38), 42 (35). Found, %: С 73.95; H 9.68;
N 16.37. C16H23N3. Calculated, %: С 74.66; H 9.01;
N 16.32. M 257.37.
REFERENCES
1. Kuznetsov,A.I., Senan, I.M., Shukkur,A.Kh.,Azzheurova,
I.A., and Serova, T.M., Russ. J. Org. Chem., 2012, vol. 48,
p. 119.
2. Kuznetsov, A.I., Mazhed, G.M., and Serova, T.M., Russ.
J. Org. Chem.,2010, vol. 46, p. 380.
3. Kuznetsov, A.I., Vladimirova, I.A., and Serova, T.M.,
Moskovkin,A.S., Khim. Geterotsikl. Soedin., 1992, p. 653.
4. Kuznetsov, A.I., Vladimirova, I.A., and Serova, T.M.,
Moskovkin,A.S., Khim. Geterotsikl. Soedin., 1992, p. 643.
5. Kuznetsov, A.I., Barri, U., Mazhed, G., and Vladimiro-
va, I.A., Khim. Geterotsikl. Soedin., 1992, p. 1257.
6. Kuznetsov, A.I., Barri, U., and Serova, T.M., Khim.
Geterotsikl. Soedin., 1993, p. 1405.
b. A solution of 0.36 g (1.25 mmol) of nitrobenzyl-
diazahomoadamantane (XI) in 5 mL of 80% hydrazine
hydrate was boiled for 3.5 h, evaporated, the residue
was sublimated in a vacuum of water-jet pump, and
recrystallized from toluene. Yield 0.23 g (72%). The
reaction product was identical to the substance obtained
by method а.
(Е)-Azobenzene-4,4'-bis{[(3,6-diazahomo-
adamantan-1-yl)methyl]-9-one} (XII). To a solution
of 0.60 g (2 mmol) of nitroketone VI and 0.40 g of NaOH
7. Morgenstern, K., Progress in Surface Science, 2011,
vol. 86, p. 115.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 11 2013