Synthesis and dehydrogenation of spinaceamine and spinacine 4-hetaryl derivatives

Article abstract of DOI:10.1134/S1070428009080181

The reaction of histamine and histidine with various hetarylaldehydes under the conditions of the base-catalyzed Pictet-Spengler process affords 4-hetaryl-substituted derivatives of spinaceamine and spinacine. The dehydrogenation of the 4-hetaryl-substitu

Full text of DOI:10.1134/S1070428009080181

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2009, Vol. 45, No. 8, pp. 1219−1223. © Pleiades Publishing, Ltd., 2009.
Original Russian Text © N.N. Smolyar, M.G. Abramyants, T.I. Zavyazkina, D.I. Matveeva, Ya.S. Borodkin, I.A. Voloskii, 2009, published in Zhurnal
Organicheskoi Khimii, 2009, Vol. 45, No. 8, pp. 1228−1231.
Synthesis and Dehydrogenation of Spinaceamine and Spinacine
4-Hetaryl Derivatives
N. N. Smolyar, M. G. Abramyants, T. I. Zavyazkina, D. I. Matveeva,
Ya. S. Borodkin, and I.A. Voloskii
Litvinenko Institute of Physical Organic and Coal Chemistry,
National Academy of Sciences of Ukraine, Donetsk, 83114 Ukraine
e-mail: smolyar_nik@mail.ru
Received June 10, 2008
Abstract—The reaction of histamine and histidine with various hetarylaldehydes under the conditions of the
base-catalyzed Pictet–Spengler process affords 4-hetaryl-substituted derivatives of spinaceamine and spinacine.
The dehydrogenation of the 4-hetaryl-substituted spinaceamine derivatives using elemental sulfur in DMF at
120–130°C led to the formation of 4-hetaryl derivatives of imidazo[4,5-c]-pyridine. Under similar conditions the
4-hetaryl-substituted spinacine derivatives suffered both the dehydrogenation and oxidative decarboxylation
resulting in the products identical to the compounds obtained by the dehydrogenation of 4-hetaryl-substituted
spinaceamine.
DOI: 10.1134/S1070428009080181
Formerly we described by an example of 4-aryl-
substituted spinaceamine and spinacine their
dehydrogenation by elemental sulfur in DMF at 120–
150°C. The dehydrogenation of 4-aryl-substituted
spinaceamine provided 4-aryl derivatives of imidazo-
[4,5-c]pyridine, and the 4-aryl-substituted spinacine under
the same conditions underwent both aromatization and
oxidative decarboxylation giving products identical to
those obtained by dehydrogenation of the 4-aryl deriva-
tives of spinaceamine [1].
4-Hetaryl-substituted spinaceamines IIIa–IIIi and
spinacines IVa–IVk whose yields attained respectively
33–88 and 30–85% are colorless substances purified by
crystallization from water. Their composition and structure
were proved by elemental analysis and 1H NMR spectra.
The heating of 4-hetarylspinaceamines IIIa–IIIg in
DMF with elemental sulfur at 120–130°C for 2–7 h (till
the end of hydrogen sulfide evolution) resulted in 4-het-
aryl-substituted imidazo-[4,5-c]pyridines Va–Vg in 51–
61% yields. In the 1H NMR spectra of these compounds
alongside the signals of the imidazole proton H2 (7.81–
8.78 ppm) and of the protons from the hetaryl fragment
signals were present from protons H6 (7.87–9.89) and
H7 (7.33–8.61 ppm) of the pyridine ring with a coupling
constant of 5.3–8.0 Hz.
In extension of the study of these processes in the
series of spinaceamine derivatives we performed the
dehydrogenation of 4-hetaryl-substituted spinaceamines
and spinacines aiming at a development of a synthesis of
imidazo[4,5-c]pyridine 4-hetaryl derivatives that were
difficultly available and might be interesting as promising
synthons for the preparation of biologically active
substances.
In contrast to spinaceamines IIIa–IIIg compounds
IIIh and IIIi containing in the position 4 of the
tetrahydropyridine ring pyrrole and furan residues
respectively in the course of the dehydrogenation under
the chosen conditions suffered decomposition affording
tarry products whose structure we failed to establish.
The reaction of histamine (I) and histidine (II) with
various hetarylaldehydes afforded new hetaryl-
substituted spinaceamines IIIa–IIIi and spinacines IVa–
IVk containing in the position 4 of the tetrahydropyridine
ring pyridine, thiophene, quinoline, pyrazole, furan, pyrrole,
indole, and benzimidazole fragments (see the scheme).
At heating 4-hetarylspinacines IVa–IVg under
analogous conditions they underwent both aromatization
and oxidative decarboxylation giving products identical
1219

SMOLYAR et al.
1220
Scheme.
H
N
H
HOOC
N
NH2
NH2
N
N
II
I
Ht_CHO
HOOC
Ht_CHO
H
N
H
N
H
N
S, Δ
S, Δ
_
_
_
H2S, CO2
H2S
HN
N
N
HN
N
N
Ht
IIIа_IIIi
Ht
Vа_Vg
Ht
IVа_IVk
Ht = 3-pyridyl (IIIa–Va), 4-pyridyl (IIIb–Vb), 2-thienyl (IIIc–Vc), quinolin-8-yl (IIId–Vd), 1,3-dimethyl-2-oxobenzimidazol-5-
yl (IIIe–Ve), 1-phenyl-3-methylpyrazol-4-yl (IIIf–Vf), 1,3-diphenylpyrazol-4-yl (IIIg–Vg), N-methylpyrrol-2-yl (IIIh), 5-methyl-
2-furyl (IIIi), 1,3,5-trimethylpyrazol-4-yl (IVh), N-methylpyrrol-2-yl (IVi), N-methylindol-3-yl (IVj), N-benzylindol-3-yl (IVk).
to compounds Va–Vg obtained previously by
dehydrogenation of spinaceamines IIIa–IIIg. 4-Hetaryl-
substituted imidazo[4,5-c]pyridines Va–Vg formed at the
dehydrogenation with sulfur of spinaceamines IIIa–IIIg
and spinacines IVa–IVg have similar melting points and
1H NMR spectra.
The purity and homogeneity of the products obtained was
checked by TLC on Silufol UV-254 plates (eluents
ethanol, chloroform; spots visualization by iodine vapor
or under UV irradiation).
Spinaceamines IIIb and IIIc were obtained by
procedures [3] and [4] respectively. Spinacine ²Vb was
obtained as described in [5].
The attempts at the dehydrogenation under similar
conditions of spinacines IVh–IVk containing in the
position 4 of the tetrahydropyridine ring 1,3,5-tri-
methylpyrazole, pyrrole, and indole fragments led to tarry
reaction products whose structure we failed to establish.
Spinaceamine 4-hetaryl derivatives IIIa, IIId −
IIIi. To a solution of 10 mmol of histamine dihydrochloride
(I) in 20 ml of water were added solutions of 30 mmol of
NaOH in 10 ml of water and 10 mmol of an appropriate
aldehyde in 40 ml of ethanol. The reaction mixture was
heated for 5–7 h on a boiling water bath. On cooling the
separated pecipitate was filtered off and recrystallized
from water.
Hence the results obtained suggest a conclusion that
a new simple method was developed for the synthesis of
4-hetarylimidazo[4,5-c]pyridines Va–Vg by the
dehydrogenation of 4-hetaryl-substituted spinaceamines
IIIa–IIIg or spinacines IVa–IVg with elemental sulfur
in DMF at 120–130°C.
4-(3-Pyridyl)spinaceamine (IIIa). Yield 1.46 g
(73%), mp 171–173°C. 1H NMR spectrum CD3OD), δ,
ppm: 3.32 t (2H, 7-CH2), 3.62 t (2H, 6-CH2), 5.90 s (1H,
H4), 7.38–7.73 m (1H, H5'), 7.85 s (1H, H2), 8.11 d (1H,
H4', J 7.2 Hz), 8.55 d (1H, H6', J 7.2 Hz), 8.88 s (1H,
H2'). Found, %: C 65.93; H 6.07; N 27.80. C11H12N4.
Calculated, %: C 65.98; H 6.04; N 27.98.
The prepared new derivatives of spinaceamine IIIa–
IIIi, spinacine IVa–IVk, and imidazo[4,5-c]pyridine Va–
Vg may be interesting for pharmacology since among
analogous compounds of this series substances have
been revealed exhibiting a wide range of biological action
[2].
4-(Quinolin-8-yl)spinaceamine (II²d). Yield 1.2 g
1
(48%), mp 97–99°C. H NMR spectrum (CD3OD), δ,
EXPERIMENTAL
ppm: 2.73 t (2H, 7-CH2), 2.99 t (2H, 6-CH2), 6.19 s (1H,
H4), 7.24 d (1H, H7', J 7.2 Hz ), 7.40–7.53 m (3H,
H3',5',6'), 7.79 d (1H, H4', J 7.2 Hz), 8.09 d (1H, H2', J 7.2
Hz), 8.80s (1H, H2). Found, %: C 71.82; H 5.67; N 22.19.
C15H14N4. Calculated, %: C 71.98; H 5.64; N 22.39.
1H NMR spectra of compounds synthesized were
registered on a spectrometer Varian Gemini-200 at
operating frequency 200 MHz, internal reference HMDS.
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SYNTHESIS AND DEHYDROGENATION OF SPINACEAMINE
1221
(1H, H4), 7.46 q (1H, H5'), 7.58 s (1H, H2'), 7.80 d (1H,
H4', J 8.1 Hz), 8.61 d (1H, H6', J 8.1 Hz), 8.66 s (1H, H2).
Found, %: C 58.97; H 4.99; N 22.91. C12H12N4O2.
Calculated, %: C 59.01; H.95; N 22.93.
4-(1,3-Dimethyl-2-oxobenzimidazol-5-yl)spinace-
amine (IIIe). Yield 1.3 g (46%), mp 145–147°C. 1H NMR
spectrum (CD3OD), δ, ppm: 2.77 t (2H, 7-CH2), 3.10 t
(2H, 6-CH2), 3.31–3.35 m (6H, 2CH3), 5.08 s (1H, H4),
7.00–7.06 m (3H, H4',6',7'), 7.51 s (1H, H2). Found, %:
C 63.54; H 6.07; N 24.60. C15H17N5O. Calculated, %:
C 63.58; H 6.05; N.72.
4-(2-Thienyl)spinacine (IVc). Yield 2.12 g (85%),
1
mp 200–202°C. H NMR spectrum (CD3OD), δ, ppm:
3.12 q (2H, 7-CH2), 4.08 q (1H, H6), 5.96 s (1H, H4),
7.09 d (1H, H3', J 5.0 Hz), 7.28 q (1H, H4'), 7.54 d (1H,
H5', J 5.0 Hz), 7.81 s (1H, H2). Found, %: C 52.89; H 4.48;
N 16.78; S 12.81. C11H11N3O2S. Calculated, %: C 53.00;
H 4.45; N 16.86; S 12.86.
4-(3-Methyl-1-phenylpyrazol-4-yl)spinaceamine
1
(II²f). Yield 2.45 g (88%), mp 198–200°C. H NMR
spectrum (CD3COOD), δ, ppm: 2.34 s (3H, CH3), 3.20 t
(2H, 7-CH2), 3.73 t (2H, 6-CH2), 6.03 s (1H, H4), 7.26–
7.64 m (5H, C6H5), 8.15 s (1H, H2), 8.68 s (1H, H5').
Found, %: C 68.68; H 6.18; N 25.00. C16H17N5.
Calculated, %: C 68.79; H.14; N 25.07.
4-(Quinolin-8-yl)spinacine (²Vd). Yield 1.06 g
(36%), mp 178–180°C. 1H NMR spectrum (CD3COOD),
δ, ppm: 3.66 q (2H, 7-CH2), 4.41 d (1H, H6), 6.69 s (1H,
H4), 7.55–7.73 m (1H, H6'), 8.09 d (1H, H7', J 8.1 Hz),
8.15 d (1H, H5', J 8.1 Hz), 8.22 t (1H, H3'), 8.44 d (1H,
H4', J 8.1 Hz), 8.64 s (1H, H2), 8.88 d (1H, H2', J 8.1 Hz).
Found, %: C 65.19; H 4.80; N 18.90. C16H14N4O2.
Calculated, %: C 65.30; H 4.79; N 19.04.
4-(1,3-Diphenylpyrazol-4-yl)spinaceamine (II²g).
Yield 2.39 g (70%), mp 253–255°C. 1H NMR spectrum
(CD3COOD), δ, ppm: 3.19 t (2H, 7-CH2), 3.74 t (2H,
6-CH2), 6.22 s (1H, H4), 7.30–7.78 m (10H, 2C6H5),
8.37 s (1H, H5'), 8.69 s (1H, H2). Found, %: C.79;
H 5.66; N 20.39. C21H19N5. Calculated, %: C 73.88;
H 5.61; N 20.51.
4-(1,3-Dimethyl-2-oxobenzimidazol-5-yl)-
spinacine (²Ve). Yield 2.62 g (80%), mp 253–255°C
1
(decomp.). H NMR spectrum (CD3COOD), δ, ppm:
4-(N-Methylpyrrol-2-yl)spinaceamine (IIIh). Yield
1
3.40 s (3H, CH3), 3.46 s (3H, CH3), 3.53 q (2H, 7-CH2),
3.76 t (1H, H6), 4.36 s (1H, H4), 7.26 d (1H, H6',
J 8.1 Hz), 7.57 d (1H, H4'), 7.75 d (1H, H7', J 8.1 Hz),
8.78 s (1H, H2). Found, %: C 58.59; H 5.21; N 21.32.
C16H17N5O3. Calculated, %: C 58.70; H 5.24; N 21.40.
0.67 g (33%), mp 148–150°C. H NMR spectrum
(CD3COOD), δ, ppm: 3.21 s (2H, 7-CH2), 3.67 s (2H,
6-CH2), 3.75 s (3H, CH3), 5.99 s (1H, H4), 6.05–6.78 m
(3H, H3'-5'), 8.73 s (1H, H2). Found, %: C 65.25; H.06;
N 27.59. C11H14N4. Calculated, %: C 65.32; H 6.98;
N 27.70.
4-(3-Methyl-1-phenylpyrazol-4-yl)spinacine
(IVf). Yield 1.62 g (50%), mp 227–229°C (decomp.).
1H NMR spectrum (CD3COOD), δ, ppm: 2.39 s (3H,
CH3), 3.44 q (2H, 7-CH2), 4.61 t (1H, H6), 6.25 s (1H,
H4), 7.26–7.67 m (5H, C6H5), 8.14 s (1H, H2), 8.69 s
(1H, H5'). Found, %: C 62.99; H 5.33; N 21.39.
C17H17N5O2. Calculated, %: C 63.14; H 5.30; N 21.66.
4-(5-Methyl-2-furyl)spinaceamine (IIIi). Yield
1
1.22 g (60%), mp 87–88°C. H NMR spectrum
(CD3COOD), δ, ppm: 2.22 s (3H, CH3), 3.18 s (2H,
7-CH2), 3.67 s (2H, 6-CH2), 6.02 s (1H, H4), 6.08 s (1H,
H4'), 6.41 s (1H, H3'), 8.64 s (1H, H2). Found, %: C.83;
H 6.51; N 20.51. C11H14N4. Calculated, %: C 65.00;
H 6.45; N 20.68.
4-(1,3-Diphenylpyrazol-4-yl)spinacine (IVg). Yield
1
2.46 g (64%), mp 205–208°C (decomp.). H NMR
Spinacine 4-hetaryl derivatives IVa, IVc–IVk. To
a solution of 10 mmol L-hustidine hydrochloride
monohydrate (II) in 20 ml of water were added solutions
of 30 mmol of NaOH in 10 ml of water and 10 mmol of
an appropriate aldehyde in 40 ml of ethanol. The reaction
mixture was heated for 5–7 h on a boiling water bath.
Ethanol was distilled off in a vacuum, the residue was
cooled and acidified with 6N HCl till pH 4–5. The
separated pecipitate was filtered off and recrystallized
from water.
spectrum (DMSO-d6), δ, ppm: 2.95 q (2H, 7-CH2),
3.97 t (1H, H6), 5.17 s (1H, H4), 7.28–7.90 m (10H,
2C6H5), 8.14 s (1H, H5'), 8.57 s (1H, H2). Found, %:
C.54; H 5.00; N 18.02. C22H19N5O2. Calculated, %:
C 68.56; H 4.97; N 18.17.
4-(1,3,5-Trimethylpyrazol-4-yl)spinacine (IVh).
Yield 1.9 g (70%), mp 211–213°C (decomp.). 1H NMR
spectrum (DMSO-d6), δ, ppm: 1.83 s (3H, CH3), 1.97 C
(3H, CH3), 3.10 q (2H, 7-CH2), 3.60 s (3H, CH3), 4.10 d
(1H, H6), 5.44 s (1H, H4), 7.85 s (1H, H2). Found, %:
C 56.64; H 6.30; N 25.42. C13H17N5O2. Calculated, %:
C 56.71; H 6.23; N.44.
4-(3-Pyridyl)spinacine (²Va). Yield 1.24 g (51%),
mp 228–230°C (decomp.). 1H NMR spectrum (DMSO-
d6), δ, ppm: 2.98 q (2H, 7-CH2), 3.85 t (1H, H6), 5.31 s
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SMOLYAR et al.
1222
4-(N-Methylpyrrol-2-yl)spinacine (IVi). Yield 0.74 g
(30%), mp 215–217°C (decomp.). H NMR spectrum
b. Yield 1.2 g (61%), mp 273–275°C. Found, %:
C 67.23; H 4.13; N 28.49.
1
(CD3COOD), δ, ppm: 3.44 q (2H, 7-CH2), 3.77 s (3H,
CH3), 4.45 d (1H, H6), 5.98 s (1H, H4), 6.04–6.78 m
(3H, H3'–5'), 8.71 s (1H, H2). Found, %: C 58.50; H.71;
N 22.66. C12H14N4O2. Calculated, %: C 58.52; H 5.73;
N 22.75.
4-(2-Thienyl)imidazo[4,5-c]pyridine (Vc). a. Yield
1.11 g (55%), mp 198–200°C. H NMR spectrum
1
(DMSO-d6), δ, ppm: 7.36 t (1H, H4'), 7.86 d (1H, H7,
J 5.5 Hz), 8.03d (1H, H3', J 4.6 Hz), 8.30 d (1H, H6,
J 5.5 Hz), 8.41 d (1H, H5', J 4.6 Hz), 8.67 s (1H, H2).
Found, %: C 59.63; H 3.52; N 20.79; S 15.78. C10H7N3S.
Calculated, %: C 59.68; H 3.51; N 20.88; S 15.93.
4-(N-Methylindol-3-yl)spinacine (IVj). Yield
1
0.98 g (33%), mp 240–242°C (decomp.). H NMR
spectrum (CD3COOD), δ, ppm: 3.62 q (2H, 7-CH2),
3.85 s (3H, CH3), 3.93 d (1H, H6), 4.33 s (1H, H4), 6.77–
7.49 m (4H, C6H4), 7.55 s (1H, H2'), 8.71 C (1H, H2).
Found, %: C 64.80; H 5.47; N 18.82. C16H16N4O2.
Βû×θC-λενO, %: C 64.85; H 5.44; N.91.
b.Yield1.76g(88%), mp197–199°C. Found, %: C 59.59;
H 3.53; N 20.74; S 15.82.
4-(Quinolin-8-yl)imidazo[4,5-c]pyridine (Vd). a.
1
Yield 1.5 g (60%), mp >300°C. H NMR spectrum
(DMSO-d6), δ, ppm: 7.71–7.84 m (1H, H6'), 7.97 d (1H,
H7', J.5Hz), 8.20–8.27 m (2H, H4',5'), 8.55 d (1H, H7,
J 7.6 Hz), 8.76 s (1H, H2), 8.75–9.15 m (2H, H2',3'), 9.86 d
(1H, H6, J 7.6 Hz). Found, %: C 73.02; H 4.15; N 22.67.
C15H10N4. Calculated, %: C 73.15; H 4.09; N 22.75.
4-(N-Benzylindol-3-yl)spinacine (IVk). Yield 2.6 g
1
(70%), mp 200–202°C (decomp.). H NMR spectrum
(CD3COOD), δ, ppm: 3.55 q (2H, 7-CH2), 4.58 t (1H,
H6), 5.34 s (2H, CH2C6H5), 6.45 s (1H, H4), 7.05–
7.57 m (9H, C6H4, CH2C6H5), 8.50 s (1H, H2'), 8.74 s
(1H, H2). Found, %: C 70.89; H 5.50; N 14.96.
C22H20N4O2. Calculated, %: C 70.95; H5.41; N 15.05.
b. Yield 1.70 g (69%), mp > 300°C. Found, %: C 73.12;
H 4.13; N.67.
4-(1,3-Dimethyl-2-oxobenzimidazol-5-yl)-
imidazo[4,5-c]pyridine (Ve). a. Yield 1.70 g (60%),
mp 226–228°C. 1H NMR spectrum (DMSO-d6), δ, ppm:
3.33 s (6H, 2CH3), 7.30 d (1H, H7, J 8.0 Hz), 7.84 d (1H,
H6, J 8.0 Hz), 8.35–8.39 m (3H, C6H3), 8.78 s (1H, H2).
Found, %: C 64.43; H 4.72; N 24.97. C15H13N5O.
Calculated, %: C 64.50; H.69; N 25.08.
Imidazo[4,5-c]pyridine 4-hetaryl derivatives Va–
Vg. a. A mixture of 10 mmol of spinaceamine IIIa–IIIg
in 50 ml of DMF and 0.7 g (22 mmol) of elemental sulfur
was heated for 2–7 h at 120–130°C till the end of H2S
evolution. Then DMF was distilled off in a vacuum till
dryness, and the residue was recrystallized from water.
b. To a solution of 10 mmol of spinacine IVa–IVg in
50 ml of DMF was added 0.7 g (22 mmol) of elemental
sulfur. The mixture was treated as in procedure a.
b.Yield1.67g(63%), mp226–228OC. Found, %:C 64.41;
H 4.72; N 24.98.
4-(3-Methyl-1-phenylpyrazol-4-yl)imidazo[4,5-c]-
pyridine (Vf). a. Yield 1.68 g (61%), mp 103–105°C.
1H NMR spectrum (DMSO-d6), δ, ppm: 2.68 s (3H,
CH3), 7.20–7.80 m (6H, C6H5, H2), 8.20–8.42 m (2H,
H7, H5'), 9.33 d (1H, H6). Found, %: C 69.68; H 4.79;
N.37. C16H13N5. Calculated, %: C 69.80; H 4.76; N 25.44.
4-(3-Pyridyl)imidazo[4,5-c]pyridine (Va). a. Yield
1
1.0 g (51%), mp 252–254°C. H NMR spectrum
(DMSO-d6), δ, ppm: 7.63 t (1H, H5'), 7.69 d (1H, H7,
J 5.6 Hz), 8.54 d (1H, H6, J 5.6 Hz), 8.55 s (1H, H2),
8.72 d (1H, H4', J 7.2 Hz), 9.07 d (1H, H6', J 7.2 Hz),
9.94 C (1H, H2'). Found, %: C 67.26; H 4.12; N 28.43.
C11H8N4. Calculated, %: C 67.33; H 4.11; N 28.56.
b. Yield 1.62 g (57%), mp 102–103°C. Found, %: C.79;
H 4.81; N 25.33.
b.Yield 1.3 g (67%), mp 253–255°C. Found, %: C 67.24;
H 4.13; N 28.47.
4-(1,3-Diphenylpyrazol-4-yl)imidazo[4,5-c]-
pyridine (Vg). a. Yield 2.06 g (63%), mp 175–177°C.
1H NMR spectrum (DMSO-d6), δ, ppm: 7.30–7.75 m
(10H, 2C6H5), 7.82–8.00 m (2H, H2, H5'), 8.35 d (1H,
H7, J 7.5 Hz), 9.17 d (1H, H6, J 7.5 Hz). Found, %:
C 74.69; H 4.55; N 20.65. C21H15N5. Calculated, %:
C 74.75; H 4.48; N 20.76.
4-(4-Pyridyl)imidazo[4,5-c]pyridine (Vb). a. Yield
1
1.18 g (60%), mp 273–275°C. H NMR spectrum
(DMSO-d6), δ, ppm: 7.60 d (1H, H7, J 5.3 Hz), 8.43 d
(1H, H6, J5.3Hz), 8.47 s (1H, H2), 8.64 d (2H, H2',6'
,
J 4.5 Hz), 8.65 d (2H, H3',5', J 4.5 Hz). Found, %: C 67.29;
H 4.15; N 28.49. C11H8N4. Calculated, %: C 67.33; H 4.11;
N 28.56.
b. Yield 1.11 g (33%), mp 175–177°C. Found, %:
C 74.66; H 4.52; N 20.66.
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