Synthesis of pyridines from alcohols in the system 1,3,5-triazine- polyphosphoric acid

Full text of DOI:10.1134/S1070428009090206

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2009, Vol. 45, No. 9, pp. 1418–1419. © Pleiades Publishing, Ltd., 2009.
Original Russian Text © I.V. Aksenova, A.V. Aksenov, I.V. Malikova, S.V. Shcherbakov, 2009, published in Zhurnal Organicheskoi Khimii, 2009, Vol. 45,
No. 9, pp. 1431–1432.
SHORT
COMMUNICATIONS
Synthesis of Pyridines from Alcohols in the System
1
,3,5-Triazine–Polyphosphoric Acid
I. V. Aksenova, A. V. Aksenov, I. V. Malikova, and S. V. Shcherbakov
Stavropol State University, ul. Pushkina 1a, Stavropol, 355009 Russia
e-mail: k-biochem-org@stavsu.ru
Received July 2, 2008
DOI: 10.1134/S1070428009090206
We previously showed that the system 1,3,5-tri-
azine–polyphosphoric acid (PPA) is an efficient rea-
gent ensuring peri fusion of a pyridine ring to aza-
phenalenes [1, 2] and naphthalene-1,8-diamine [3].
The present communication reports on the reaction of
alcohols Ia–Id with 1,3,5-triazine (III) on heating in
PPA (prepared according to the procedure described in
dropyridines VIIa–VIId as a result of electrocyclic
reaction or electrophilic addition. Finally, elimination
of formamidine from compounds VIIa–VIId yields
pyridines VIIIa–VIIId.
General procedure for the synthesis of pyridines
VIIIa–VIIId. A mixture of 1 mmol of alcohol Ia–Id
and 3–4 g of polyphosphoric acid was vigorously
stirred for 15 min at 60–65°C, 0.12 g (1.5 mmol) of
[
4]; P O concentration 86%), which leads to the
2 5
formation of 3-substituted pyridines VIII.
1
,3,5-triazine (III) was added, and the mixture was
Presumably, the reaction occurs as follows. Dehy-
dration of alcohol Ia–Id by the action of PPA gives
alkenes IIa–IId which react with protonated 1,3,5-tri-
azine (III) to form cationic species IVa–IVd. The
latter undergo deprotonation to dihydrotriazines Va–
Vd, opening of the triazine ring in Va–Vd leads to
azapolyenes VIa–VId which are converted into dihy-
stirred first for 2 h at 70–75°C and then for 5 h at 120–
130°C. The mixture was cooled, poured under stirring
into 30 ml of cold water, made alkaline by adding 25%
aqueous ammonia, saturated with K CO , and extract-
2 3
ed with ethyl acetate (50×5 ml). The extract was evap-
orated, and the product was isolated by chromatog-
raphy (eluent ethyl acetate–petroleum ether, 1:1).
OH
OH
PPA
or
R
R'
R
R'
R
R'
Ib, Ic
Ia, Id
IIa–IId
R'
N
N
IIa–IId, PPA
N
NH
N
NH
N
NH2
R'
–H+
R'
N
N
N
N
R
R
R
III
IVa–IVd
Va–Vd
VIa–VId
NH2
N
N
N
PPA
–
HN=CH–NH2
R
R'
R
R'
VIIa–VIId
VIIIa–VIIId
R = H (a), pyridin-2-yl (b), pyridin-4-yl (c), quinolin-2-yl (d); R′ = Me (a), H (b, c, d).
1
418

SYNTHESIS OF PYRIDINES FROM ALCOHOLS
1419
1
3
-Methylpyridine (VIIIa). Yield 0.029 g (31%),
data [5]: mp 70–71°C. The H NMR spectrum was
consistent with that reported in [5]. Found, %:
C 81.28; H 4.71; N 13.53. C H N . Calculated, %:
+
yellow liquid. Mass spectrum, m/z (I , %): 93 [M]
100), 92 (31), 66 (44). Found, %: C 77.56; H 7.49;
rel
(
1
4
10
2
N 14.95. C H N. Calculated, %: C 77.38; H 7.58;
C 81.53; H 4.89; N 13.58.
6
7
N 15.04. M 93.13
,3′-Bipyridyl (VIIIb). Yield 0.056 g (36%),
1
The H NMR spectra were recorded on a Bruker
WP-200 spectrometer (200 MHz) using tetramethyl-
silane as internal reference. The mass spectra (electron
impact, 70 eV) were obtained on an MKh-1321A
instrument. The progress of reactions was monitored,
and the purity of products was checked, by TLC on
Silufol UV-254 plates using ethyl acetate–petroleum
ether (1:1) as eluent.
2
1
yellow oily substance. H NMR spectrum (CDCl ), δ,
3
ppm: 7.27 d.d (1H, 5′-H, J4′,5′ = 7.9, J5′,6′ = 4.9 Hz),
7
(
8
.39 d.d (1H, 5-H, J4,5 = 7.9, J5,6 = 4.9 Hz), 7.74 d
1H, 3-H, J3,4 = 7.9 Hz), 7.78 t (1H, 4-H, J = 7.9 Hz),
.31 d.d (1H, 4′-H, J4′,5′ = 7.9, J2′,4′ = 2.1 Hz), 8.64 d
(
1H, 6-H, J5, 6 = 4.9 Hz), 8.72 d (1H, 6′-H, J5′, 6′
=
4
.9 Hz), 9.18 d (1H, 2′-H, J2′,4′ = 2.1 Hz). Found, %:
C 77.08; H 5.11; N 17.81. C H N . Calculated, %:
C 76.90; H 5.16; N 17.94.
1
0
8
2
REFERENCES
3
,4′-Bipyridyl (VIIIc). Yield 0.055 g (35%),
1
. Aksenov, A.V., Borovlev, I.V., Aksenova, I.V., and
Kovalev, D.A., Khim. Geterotsikl. Soedin., 2007, p. 1590.
1
yellow oily substance. H NMR spectrum (CDCl ), δ,
3
ppm: 7.41 d.d (1H, 5-H, J4 = 7.9, J5′, 6′ = 4.9 Hz),
, 5
2. Aksenov, A.V., Borovlev, I.V., Aksenova, I.V., Pisaren-
ko, S.V., and Kovalev, D.A., Tetrahedron Lett., 2008,
vol. 49, p. 707.
7
.49 d (2H, 3′-H, 5′-H, J = 4.9 Hz), 7.74 d (1H, 3-H,
J3, 4 = 7.9 Hz), 7.91 d.d (1H, 4-H, J4, 5 = 7.9, J2, 4
=
2
2
2
.1 Hz), 8.67 d (1H, 6-H, J5 = 4.9 Hz), 8.70 d (2H,
,6
3. Borovlev, I.V., Aksenov, A.V., Aksenova, I.V., and Pisa-
renko, S.V., Izv. Ross. Akad. Nauk, Ser. Khim., 2007,
p. 2275.
′-H, 6′-H, J = 4.9 Hz), 8.88 d (1H, 2′-H, J2′, 4′
=
.1 Hz). Found, %: C 77.06; H 5.09; N 17.85.
C H N . Calculated, %: C 76.90; H 5.16; N 17.94.
4. Uhlig, F., Angew. Chem., 1954, vol. 66, p. 435.
1
0
8
2
2
-(3-Pyridyl)quinoline (VIIId). Yield 0.117 g
5. Ishikura, M., Oda, I., and Terashima, M., Heterocycles,
(
57%), mp 69–71°C (from petroleum ether); published
1985, vol. 23, p. 2375.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 45 No. 9 2009