Synthesis of 3,6-diazahomoadamantane

Article abstract of DOI:10.1134/S1070428012010198

Condensation of 1-phenylsulfanylpropan-2-one with 1,3,6,8- tetraazatricyclo[4.4.1.13,8]dodecane gave 1-phenylsulfanyl-3,6- diazahomoadamantan-9-one which was reduced to 1-phenylsulfanyl-3,6- diazahomoadamantane, and the latter was subjected to desulfurization over Raney nickel to obtain previously unknown 3,6-diazahomoadamantane. Heating of 9-phenyl-3,6-diazahomoadamantan-9-ols with Raney nickel resulted in reduction of the hydroxy group with formation of 9-phenyl-3,6-diazahomoadamantanes. Pleiades Publishing, Ltd., 2012.

Full text of DOI:10.1134/S1070428012010198

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2012, Vol. 48, No. 1, pp. 119–122. © Pleiades Publishing, Ltd., 2012.
Original Russian Text © A.I. Kuznetsov, I.M. Senan, A.Kh. Shukkur, I.A. Azzheurova, T.M. Serova, 2012, published in Zhurnal Organicheskoi Khimii, 2012,
Vol. 48, No. 1, pp. 124–127.
Synthesis of 3,6-Diazahomoadamantane
A. I. Kuznetsova, I. M. Senana, A. Kh. Shukkura, I. A. Azzheurovaa, and T. M. Serovab
a Lomonosov Academy of Fine Chemical Technology, pr. Vernadskogo 86, Moscow, 119571 Russia
e-mail: tetraza@mail.ru
b Institute of Physiologically Active Substances, Russian Academy of Sciences,
Chernogolovka, Moscow oblast, Russia
Received February 21, 2011
Abstract—Condensation of 1-phenylsulfanylpropan-2-one with 1,3,6,8-tetraazatricyclo[4.4.1.13,8]dodecane
gave 1-phenylsulfanyl-3,6-diazahomoadamantan-9-one which was reduced to 1-phenylsulfanyl-3,6-diazahomo-
adamantane, and the latter was subjected to desulfurization over Raney nickel to obtain previously unknown
3,6-diazahomoadamantane. Heating of 9-phenyl-3,6-diazahomoadamantan-9-ols with Raney nickel resulted in
reduction of the hydroxy group with formation of 9-phenyl-3,6-diazahomoadamantanes.
DOI: 10.1134/S1070428012010198
By condensation of methyl ketones with 1,3,6,8-
tetraazatricyclo[4.4.1.13,8]dodecane [1] and subsequent
Wolff–Kishner reduction of the resulting 3,6-diaza-
homoadamantan-9-ones we obtained a number of
3,6-diazahomoadamantane derivatives substituted at
the bridgehead position [2–4]. In the present com-
munication we report on the synthesis of 3,6-diaza-
homoadamantane in a similar way. For this purpose, as
initial ketone we used 1-phenylsulfanylpropan-2-one
(I); its condensation with 1,3,6,8-tetraazatricyclo-
[4.4.1.13,8]dodecane in propan-2-ol afforded more than
60% of 1-phenylsulfanyl-3,6-diazahomoadamantan-9-
one (II) (Scheme 1).
δC 65.63 and 59.45 ppm from four bridging methylene
carbon atoms.
Ketone II was reduced to 1-phenylsulfanyl-3,6-
diazahomoadamantane (V) in two ways: (1) through
1-phenylsulfanyl-3,6-diazahomoadamantan-9-one hy-
drazone (III) according to Wolff–Kishner and (2) by
reduction of 1-phenylsulfanyl-3,6-diazahomoadaman-
tan-9-one p-tolylsulfonylhydrazone (IV) with sodium
tetrahydridoborate in acetic acid [5] (Scheme 2). De-
sulfurization of 1-phenylsulfanyl-3,6-diazahomoada-
mantane (V) by heating over Raney nickel according
to the procedure described in [6, 7] gave previously
unknown unsubstituted 3,6-diazahomoadamantane
(VI) [8] which was isolated as a readily sublimable
white crystalline substance with mp 250–251°C.
Scheme 1.
O
N
1
In the H NMR spectrum of diazahomoadamantane
S
+
Me
VI, the NCH2CH2N ethylene fragment gave rise to
N
N
N
Scheme 2.
I
O
S
NNHR
O
S
H2NNHR
AcOH
N
N
N
N
Ph
S
N
N
II
III, IV
II
Ketone II displayed in the 13C NMR spectrum
a signal at δC 209.4 ppm from carbonyl carbon atom,
two signals at δC 62.3 and 54.1 ppm from the bridge-
head carbon atoms, a signal at δC 57.0 ppm from two
carbon atoms in the ethylene bridge, and two signals at
Raney Ni
N
N
Ph
N
N
S
V
VI
III, R = H; IV, R = 4-MeC6H4SO2.
119

KUZNETSOV et al.
120
a multiplet at δ 3.12 ppm, protons in the four NCH2C
methylene groups resonated as two doublets at δ 3.42
and 2.80 ppm, the singlet at δ 1.30 ppm was assigned
to the CH2C methylene group, and two protons in
the bridgehead positions gave a broadened singlet at
δ 1.85 ppm. The 13C NMR spectrum of compound VI
contained four signals at δC 57.3 (NCH2CH2N), 62.4
(NCH2C), 34.1 (CCH2C), and 29.8 ppm (bridgehead
carbon atoms).
EXPERIMENTAL
The IR spectra were recorded in KBr on a Bruker
1
IFS 66v/S spectrometer. The H NMR spectra were
measured from solutions in CDCl3 on a Bruker WM-
250 spectrometer at 250.13 MHz (for H) using tetra-
1
methylsilane as internal reference. The mass spectra
were obtained on a Finnigan MAT 90 instrument with
direct sample admission into the ion source (accelerat-
ing voltage 5.0 kV, cathode emission current 100 μA,
electron impact, 70 eV, ion source temperature 200°C).
Desulfurization of other derivatives of phenylsul-
fanyldiazahomoadamantane provides a synthetic route
to diazahomoadamantane derivatives which cannot be
obtained by other methods. While studying products of
desulfurization of 9-phenyl-1-phenylsulfanyl-3,6-di-
azahomoadamantan-9-ol (VII) we found that this reac-
tion is accompanied by reduction of the hydroxy group
with formation of 9-phenyl-3,6-diazahomoadamantane
(VIII) [9] (Scheme 3).
1-Phenylsulfanylpropan-2-one (I). A mixture of
13.80 g (125 mmol) of benzenethiol and 12.00 g
(130 mmol) of chloroacetone was slowly heated to the
boiling point and was kept boiling until hydrogen
chloride no longer evolved. The mixture was cooled
and diluted with a double volume of petroleum ether,
and the precipitate was filtered off. Yield 16.6 g (80%),
white crystals, mp 31–32°C. The spectral parameters
of the product were identical to those reported in [10].
Scheme 3.
1-Phenylsulfanyl-3,6-diazahomoadamantan-
9-one (II). A mixture of 3.66 g (20 mmol) of 1,3,6,8-
tetraazatricyclo[4.4.1.13,8]dodecane, 3.61 g (20 mmol)
of ketone I, and 3.27 ml (55 mmol) of glacial acetic
acid in 30 ml of isopropyl alcohol was stirred for 3 h at
room temperature and was left to stand for 12 h. The
precipitate was filtered off and recrystallized from
heptane. Yield 3.7 g (61%), white crystals, mp 133–
134°C. IR spectrum, ν, cm–1: 1695 (C=O), 1600
OH
Ph
Ph
PhLi
Raney Ni
II
N
N
SPh
N
N
VII
VIII
The developed scheme of synthesis of phenyldi-
azahomoadamantane VIII is also applicable to the
preparation of its derivatives. For instance, by heating
1-methyl- and 1,8-dimethyl-9-phenyl-3,6-diazahomo-
adamantan-9-ols Xa and Xb (obtained from 1-methyl-
and 1,8-dimethyl-3,6-diazahomoadamantan-9-ones
IXa and IXb [2]) over Raney nickel we synthesized
1-methyl- and 1,8-dimethyl-9-phenyl-3,6-diazahomo-
adamantanes XIa and XIb, respectively (Scheme 4).
1
(C=Carom). H NMR spectrum, δ, ppm: 2.78 s (1H,
CH), 3.02 m (4H, NCH2CH2N), 2.90–3.12 m (4H,
NCH2C), 3.41 d (2H, NCH2C, J = 14.0 Hz), 3.48 d
(2H, NCH2C, J = 14.0 Hz), 7.25–7.40 m (3H, Ph),
7.50 d (2H, Ph, J = 14.0 Hz). 13C NMR spectrum, δC,
ppm: 209.42 (C9); 137.81, 129.11, 128.80, 128.78
(Carom); 65.63 (C2, C10), 62.63 (C1), 59.45 (C7, C11),
57.00 (C4, C5), 54.11 (C8). Mass spectrum, m/z
(Irel, %): 274 (84) [M]+, 241 (24), 232 (20), 136 (25),
122 (55), 91 (67), 81 (60), 68 (44), 55 (100), 42 (58).
Found, %: C 65.64; H 6.81; N 10.31; S 11.50.
C15H18N2OS. Calculated, %: C 65.66; H 6.61; N 10.21;
S 11.69. M 274.38.
Scheme 4.
Me
Me
Ph
OH
O
R
PhLi
N
N
N
N
R
1-Phenylsulfanyl-3,6-diazahomoadamantan-9-
one hydrazone (III). A solution of 2.37 g (8.64 mmol)
of ketone II in 40 ml of a 66% solution of hydrazine
hydrate was heated for 3 h under reflux. The mixture
was cooled to 0°C, and the precipitate was filtered off
and recrystallized from isopropyl alcohol. Yield 2.0 g
(80%), white crystals, mp 189–190°C. IR spectrum, ν,
cm–1: 3300, 1560 (NH2); 1680 (C=N); 1600 (C=Carom).
1H NMR spectrum, δ, ppm: 2.88 m (4H, NCH2CH2N),
IXa, IXb
Xa, Xb
Me
Ph
Raney Ni
N
N
R
XIa, XIb
R = H (a), Me (b).
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SYNTHESIS OF 3,6-DIAZAHOMOADAMANTANE
121
2.70–3.00 m (4H, NCH2C), 3.21 d (2H, NCH2C, J =
14.0 Hz), 3.40 d (2H, NCH2C, J = 14.0 Hz), 3.16 s
(1H, CH), 5.11 br.s (2H, NH2), 7.15–7.45 m (3H, Ph),
7.46 d (2H, Ph, J = 14.0 Hz). 13C NMR spectrum, δC,
ppm: 155.21 (C9); 137.98, 129.90, 128.85, 128.57
(Carom); 64.92 (C2, C10), 57.20 (C7, C11), 57.16 (C4, C5),
53.78 (C1), 36.46 (C8). Mass spectrum, m/z (Irel, %):
288 (100) [M]+, 273 (11), 202 (9), 149 (11), 121 (23),
91 (24), 82 (16), 72 (87), 65 (28), 43 (67). Found, %:
C 62.26; H 6.77; N 19.78; S 11.19. C15H20N4S. Calcu-
lated, %: C 62.47; H 6.99; N 19.43; S 11.12. M 288.41.
IV in 5 ml of isopropyl alcohol. The mixture was
heated for 7 h under reflux, the solvent was distilled
off, the solid residue was treated with a small amount
of water, water was distilled off, and the residue was
recrystallized from heptane. Yield 0.07 g (68%).
3,6-Diazahomoadamantane (VI). Compound V,
0.40 g (2.33 mmol), was dissolved in 20 ml of iso-
propyl alcohol, 2 g of freshly prepared Raney nickel
was added, and the mixture was heated for 20 h under
reflux, additional 2-g portions of Raney nickel being
added every 7 h. The catalyst was filtered off and
washed with isopropyl alcohol, the solvent was
distilled off from the filtrate, and the residue was
recrystallized from heptane. Yield 0.18 g (76%), white
1-Phenylsulfanyl-3,6-diazahomoadamantan-9-
one 4-methylphenylsulfonylhydrazone (IV). 4-Meth-
ylbenzenesulfonohydrazide, 0.17 g (0.90 mmol), was
added to a solution of 0.14 g (0.90 mmol) of ketone II
in 10 ml of methanol, and the mixture was heated for
0.5 h under reflux. The solvent was distilled off, and
the residue was recrystallized from heptane. Yield
0.21 g (72%), mp 150–151°C. IR spectrum, ν, cm–1:
1
crystals, mp 250–251°C. H NMR spectrum, δ, ppm:
1.60 s (2H, CH2), 1.88 s (2H, CH), 2.65 d (4H,
NCH2C, J = 14.0 Hz), 3.19 d (4H, NCH2C, J =
14.0 Hz), 2.99 m (4H, NCH2CH2N). 13C NMR spec-
trum, δC, ppm: 29.75 (C1, C8), 33.82 (C9), 57.54 (C2,
C7, C10, C11), 57.64 (C4, C5). Mass spectrum, m/z
(Irel, %): 152 (97) [M]+, 108 (97), 95 (66), 85 (30), 72
(17), 60 (45), 55 (57), 57 (100), 42 (65). Found, %:
C 71.57; H 10.72; N 17.71. C9H16N2. Calculated, %:
C 71.01; H 10.59; N 18.40. M 152.24.
1
3300 (NH); 1640 (C=N), 1600 (C=Carom). H NMR
spectrum, δ, ppm: 1.90 s (1H, CH), 2.30 s (3H, CH3),
3.05 m (4H, NCH2CH2N), 2.70–3.30 m (8H, NCH2C),
7.00–7.70 m (9H, Harom), 8.30 br.s (1H, NH). Found,
%: C 58.65; H 5.89; N 12.33; S 14.03. C22H26N4O2S2.
Calculated, %: C 58.70; H 5.92; N 12.66; S 14.49.
M 442.60.
9-Phenyl-1-phenylsulfanyl-3,6-diazahomoada-
mantan-9-ol (VII). A solution of 6.12 g (38.96 mmol)
of bromobenzene in 15 ml of anhydrous diethyl ether
was slowly added under vigorous stirring to 0.54 g
(77.92 mmol) of metallic lithium (cut in small pieces)
in 30 ml of anhydrous diethyl ether. The mixture was
stirred for 40 min, 1.77 g (6.49 mmol) of ketone II was
added over a period of 20 min, and the mixture was
kept for 5.5 h at room temperature. The precipitate was
dissolved in 24 ml of 18% hydrochloric acid. The
aqueous layer was washed with diethyl ether (4×
15 ml), neutralized with potassium carbonate, and
extracted with chloroform (4×20 ml). The extract was
dried over anhydrous sodium sulfate, the solvent was
distilled off, and the residue was recrystallized from
ethanol. Yield 2.1 g (93%), white crystals, mp 182–
183°C. IR spectrum, ν, cm–1: 3432 (OH), 1636
1-Phenylsulfanyl-3,6-diazahomoadamantane
(V). a. A mixture of 1.90 g (6.59 mmol) of hydrazone
III and 1.75 g (31 mmol) of potassium hydroxide was
thoroughly stirred and heated for 2 h at 220–240°C.
The mixture was cooled and extracted with diethyl
ether (2×25 ml), the combined extracts were evaporat-
ed, and the reaidue was recrystallized from heptane.
Yield 1.30 g (76%), white crystals, mp 87–89°C. IR
1
spectrum: ν 1600 cm–1 (C=Carom). H NMR spectrum,
δ, ppm: 1.82 s (2H, CH2), 1.88 s (1H, CH), 2.96 m
(4H, NCH2CH2N), 2.66 d (2H, NCH2C, J = 14.0 Hz),
2.71 d (2H, NCH2C, J = 14.0 Hz), 3.15 d (2H, NCH2C,
J = 14.0 Hz), 3.25 d (2H, NCH2C, J = 14.0 Hz), 7.25–
7.40 m (3H, Ph), 7.47 d (2H, Ph, J = 14.0 Hz).
13C NMR spectrum, δC, ppm: 137.62, 129.22, 128.90,
128.57 (Carom); 62.78 (C2, C10), 57.38 (C7, C11), 56.73
(C4, C5), 45.17 (C1), 40.43 (C9), 33.17 (C8). Mass
spectrum, m/z (Irel, %): 260 (25) [M]+, 151 (100), 121
(44), 108 (51), 94 (50), 81 (32), 78 (50), 66 (70), 57
(61), 42 (69). Found, %: C 69.04; H 7.56; N 10.98;
S 12.42. C15H20N2S. Calculated, %: C 69.19; H 7.74;
N 10.76; S 12.31. M 260.40.
1
(C=Carom). H NMR spectrum, δ, ppm: 2.50 br.s (1H,
CH), 3.0 m (4H, NCH2CH2N), 2.05 d (2H, NCH2C,
J = 14.0 Hz), 2.85 d (2H, NCH2C, J = 14.0 Hz), 3.10 d
(2H, NCH2C, J = 14.0 Hz), 3.40 d (2H, NCH2C, J =
14.0 Hz), 4.40 br.s (1H, OH), 7.25–8.0 m (10H, Harom).
Mass spectrum, m/z (Irel, %): 352 (77) [M]+, 263 (27),
243 (51), 200 (38), 110 (69), 105 (100), 82 (42), 76
(70), 72 (41), 57 (37), 43 (49). Found, %: C 71.56;
H 7.05; N 8.04; S 9.08. C21H24N2OS. Calculated, %:
C 71.55; H 6.86; N 7.95; S 9.10. M 352.49.
b. A solution of 0.20 g (4.9 mmol) of sodium
tetrahydridoborate in 5 ml of glacial acetic acid was
added to a solution of 0.20 g (0.49 mmol) hydrazone
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 1 2012

KUZNETSOV et al.
122
pound VIII from 0.7 g (2.9 mmol) of alcohol Xa.
9-Phenyl-3,6-diazahomoadamantane (VIII). Al-
Yield 0.35 g (54%), white crystals, mp 94–95°C. IR
cohol VII, 0.51 g (1.46 mmol), was dissolved in 20 ml
of isopropyl alcohol, 2.0 g of freshly prepared Raney
nickel was added, and the mixture was heated for 20 h
under reflux, additional 2-g portions of Raney nickel
being added every 7 h. The catalyst was filtered off
and washed with isopropyl alcohol, the solvent was
distilled off from the filtrate, and the residue was
recrystallized from heptane. Yield 0.25 g (76%), white
crystals, mp 103–104°C. IR spectrum: ν 1535 cm–1
1
spectrum: ν 1600 cm–1 (C=Carom). H NMR spectrum,
δ, ppm: 0.60 s (3H, CH3), 1.85 br.s (1H, CH), 2.40–
3.75 m (8H, NCH2C), 3.15 m (4H, NCH2CH2N),
3.45 m (1H, CH), 7.20–7.50 m (5H, Ph). Mass spec-
trum, m/z (Irel, %): 242 (100) [M]+, 184 (66), 171 (39),
129 (44), 115 (51), 91 (78), 82 (41), 72 (18), 68 (34),
56 (56), 43 (67). Found, %: C 79.15; H 8.89; N 11.67.
C16H22N2. Calculated, %: C 79.29; H 9.14; N 11.55.
M 242.36.
1
(C=Carom). H NMR spectrum, δ, ppm: 2.30 br.s (2H,
CH), 3.05 m (4H, NCH2CH2N), 2.50 d (2H, NCH2C,
J = 14.0 Hz), 3.00 d (2H, NCH2C, J = 14.0 Hz), 3.15 d
(2H, NCH2C, J = 14.0 Hz), 3.40 d (2H, NCH2C, J =
14.0 Hz), 3.50 s (1H, CH), 7.20–7.40 m (5H, Ph).
Mass spectrum, m/z (Irel, %): 228 (100) [M]+, 200 (39),
184 (45), 170 (70), 156 (46), 115 (66), 91 (57), 82
(98), 72 (53), 58 (100), 43 (75). Found, %: C 79.16;
H 9.11; N 12.40. C15H20N2. Calculated, %: C 78.90;
H 8.83; N 12.27. M 228.33.
1,8-Dimethyl-9-phenyl-3,6-diazahomoadaman-
tane (XIb) was synthesized as described above for
compound VIII from 0.78 g (2.9 mmol) of alcohol Xb.
Yield 0.43 g (59%), white crystals, mp 184–185°C. IR
1
spectrum: ν 1535 cm–1 (C=Carom). H NMR spectrum,
δ, ppm: 0.5 s (6H, CH3), 3.10 m (4H, NCH2CH2N),
2.30 d (2H, NCH2C, J = 14.0 Hz), 2.55 d (2H, NCH2C,
J = 14.0 Hz), 3.75 d (2H, NCH2C, J = 14.0 Hz), 3.82 d
(2H, NCH2C, J = 14.0 Hz), 3.40 s (1H, CH), 7.20–
7.85 m (5H, Ph). Mass spectrum, m/z (Irel, %): 256 (90)
[M]+, 198 (22), 184 (46), 176 (41), 110 (32), 105 (76),
91 (32), 82 (96), 72 (100), 55 (94), 43 (28). Found, %:
C 79.06; H 9.10; N 12.25. C17H24N2. Calculated, %:
C 78.95; H 8.90; N 12.10. M 256.39.
1-Methyl-9-phenyl-3,6-diazahomoadamantan-
9-ol (Xa) was synthesized as described above for com-
pound VII from 1.17 g (6.49 mmol) of ketone IXa.
Yield 1.0 g (60%), white crystals, mp 141–142°C.
IR spectrum, ν, cm–1: 3100 (OH), 1535 (C=Carom).
1H NMR spectrum, δ, ppm: 0.95 s (3H, CH3), 2.05 br.s
(1H, CH), 2.40–3.45 m (8H, NCH2C), 3.05 m (4H,
NCH2CH2N), 4.0 m (1H, OH), 7.25–7.75 m (5H, Ph).
Mass spectrum, m/z (Irel, %): 258 (95) [M]+, 184 (46),
176 (41), 110 (32), 105 (76), 98 (41), 91 (32), 82 (96),
72 (100), 55 (94), 43 (28). Found, %: C 74.05; H 8.72;
N 10.92. C16H22N2O. Calculated, %: C 74.38; H 8.58;
N 10.84. M 258.36.
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1,8-Dimethyl-9-phenyl-3,6-diazahomoadaman-
tan-9-ol (Xb) was synthesized as described above for
compound VII from 1.26 g (6.49 mmol) of ketone
IXb. Yield 1.2 g (68%), white crystals, mp 217–
218°C. IR spectrum, ν, cm–1: 3320 (OH), 1535
(C=Carom). 1H NMR spectrum, δ, ppm: 0.5 s (6H, CH3),
2.05 s (1H, OH), 2.30 d (2H, NCH2C, J = 14.0 Hz),
2.50 d (2H, NCH2C, J = 14.0 Hz), 3.70 d (2H, NCH2C,
J = 14.0 Hz), 3.80 d (2H, NCH2C, J = 14.0 Hz),
3.15 m (4H, NCH2CH2N), 7.20–7.90 m (5H, Ph). Mass
spectrum, m/z (Irel, %): 272 (48) [M]+, 105 (43), 98
(100), 97 (15), 96 (64), 91 (33), 82 (30), 72 (68), 68
(52), 57 (48), 43 (62). Found, %: C 75.06; H 8.95;
N 10.53. C17H24N2O. Calculated, %: C 74.96; H 8.88;
N 10.28. M 272.39.
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1-Methyl-9-phenyl-3,6-diazahomoadamantane
(XIa) was synthesized as described above for com-
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 1 2012