Novel route for the synthesis of partially hydrogenated 1,2a,5a,8a-tetraazaacenaphthylenes and 1,4a,5,9,8a-pentaazafluorenes

Full text of DOI:10.1007/s10593-011-0750-z

Chemistry of Heterocyclic Compounds, Vol. 47, No. 2, May, 2011 (Russian Original Vol. 47, No. 2, February, 2011)
NOVEL ROUTE FOR THE SYNTHESIS OF PARTIALLY
HYDROGENATED 1,2a,5a,8a-TETRAAZAACENAPHTHYLENES
AND 1,4a,5,9,8a-PENTAAZAFLUORENES
A. N. Sokolov1, M. S. Mischenko1, E. S. Gladkov2, and V. M. Chernyshev2*
Keywords: [1,2,4]triazolo[1,5-a]pyrimidine, 3-chloropropionic acid chloride, heterocyclization, one-pot
synthesis.
Partially hydrogenated [1,2,4]triazolo[1,5-a]pyrimidines are polyfunctional compounds which can react
readily with electrophilic reagents [1-3]. Using this feature we now propose a one-pot method for the synthesis
of 5-oxo-4,5,7,8-tetrahydro-3H,6H-1,2a,5a-triaza-8a-azoniumacenaphthylene 3a,b and 2-oxo-1,2,3,4,5,6,7,8-
octahydro-1,4a,5,9-tetraaza-8a-azoniumfluorene chlorides 4a,b by treating the readily available 4,5,6,7-
tetrahydro[1,2,4]triazolo[1,5-a]pyrimidines 1a-d [1, 2] with 3-chloropropionic acid chloride (2).
R1
8
+
N
1
3
N
N
–
Cl
7
2
R2
1a,b
N
6
8b
O
R1
5
O
Cl
Cl
N
N
2
3a,b
N
R
R1
R2
DMF, Py
N
H
8
9
+
N
–
7
N
8a
H
N
Cl
1a–d
6
R2
1
1c,d
N
N
4b
O
5
H
2
4
3
4a,b
1 a, b R = H, c, d R = NH2; 1a,c, 3a, 4a, R1 = Ph, 1b, 3b R1 = 4-ClC6H4,
1d, 4b R1 = 4-MeOC6H4; 1a,b,d, 3a,b, 4b R2 = Ph, 1c, 4a R2 = Me
_______
* To whom correspondence should be addressed, e-mail:chern13@yandex.ru..
1South Russian State Technical University, 132 Prosveshcheniya St., Novocherkassk 346428, Russia.
chern13@yandex.ru.
2Institute for Single Crystals, Ukraine National Academy of Sciences, 60 Lenin St., Kharkiv 61001, Ukraine.
__________________________________________________________________________________________
Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 308-310, February, 2011. Original
article submitted January 28, 2011.
0009-3122/11/4702-0249©2011 Springer Science+Business Media, Inc.
249

The composition and structure of compounds 3 and 4 were confirmed by elemental analysis and from
spectroscopic data which included the NOESY spectrum of compound 3a (correlation of H-2 and NCH2
1
protons) and the H–13C HMBC spectra of compounds 3a,4a (correlation of the NCH2 group protons and both
carbon nuclei of the triazole ring) as well as through an X-ray structural analysis of compound 4a. The
crystallographic data was deposited in the Cambridge structural database, reference CCDC 811047. A detailed
report of the structure will be published separately.
1H and 13C NMR spectra were recorded on a Bruker Avance 600 instrument (600 and 150 MHz
respectively) using DMSO-d6 with TMS as internal standard. Mass spectra (EI) were obtained on a Finnigan
MAT Incos 50 spectrometer with direct introduction of the sample into the ion source and ionization energy of
70 eV. Elemental analysis was carried out on a Perkin-Elmer 2400 analyzer.
5-Oxo-6,8-diphenyl-4,5,7,8-tetrahydro-3H,6H-1,2a,5a-triaza-8a-azoniaacenaphthylene
Chloride
(3a). A solution of the acid chloride 2 (0.41 g, 3.3 mmol) in acetonitrile (2 ml) was added dropwise with stirring
to a mixture of amine 1a (0.83 g, 3.0 mmol), anhydrous DMF (5 ml), and pyridine (0.26 g, 3.3 mmol), stirred for
20 min at room temperature and then for 6 h at 80-90ºC. The precipitate formed on cooling was filtered off,
1
washed with acetone, and dried to give 0.68 g (62%) of the product with mp 212-213ºC (MeOH). H NMR
spectrum, , ppm (J, Hz): 2.65-2.85 (2H, m, H-7); 3.09 (2H, m, H-4); 4.52 (1H, m, H-3); 4.65 (1H, m, H-3);
5.39 (1H, m, H-6); 5.63 (1H, m, H-8); 7.13-7.36 (10H, m, 2Ph); 8.99 (1H, s, H-2). Mass spectrum, m/z (Irel, %):
331 [M-Cl]+ (4), 330 [M-HCl]+ (17), 275 (13), 197 (24), 193 (16), 171 (100), 115 (24), 104 (77). Found, %:
C 65.15; H 5.40; N 14.94. C20H19ClN4O. Calculated, %: C 65.48; H 5.22; N 15.27.
8-(4-Chlorophenyl)-5-oxo-6-phenyl-4,5,7,8-tetrahydro-3H,6H-1,2a,5a-triaza-8a-azoniaacenaphthy-
lene Chloride (3b) was prepared similarly to compound 3a from amine 1b and the acid chloride 2. Yield 0.78 g
1
(65%); mp 229-231ºC (MeOH). H NMR spectrum, , ppm: 2.73-2.78 (1H, m, H-7); 2.84-2.88 (1H, m, H-7);
3.16 (2H, m, H-4); 4.57 (1H, m, H-3); 4.70 (1H, m, H-3); 5.45 (1H, m, H-6); 5.74 (1H, m, H-8); 7.13-7.37 (9H,
m, Ar); 9.13 (1H, s H-2). 13C NMR spectrum, , ppm: 29.47 C(4), 37.41 C(7), 39.68 C(3), 54.24 C(6), 57.47
C(8), 125.61, 126.91, 127.83, 127.89, 128.86, 132.67, 134.46, 137.84, 140.29 C(2), 146.22 C(8b), 164.30 C(5).
Мass spectrum, m/z (Irel, %): 365 [M-Cl]+ (7), 364 [M-HCl]+ (19), 309 (27), 197 (17), 171 (67), 138 (34), 104
(33). Found, %: C 60.01; H 4.39; N 14.25. C20H18Cl2N4O. Calculated, %: C 59.86; H 4.52; N 13.96.
`
6-Methyl-2-oxo-8-phenyl-1,2,3,4,5,6,7,8-octahydro-1,4a,5,9-tetraaza-8a-azoniafluorene Chloride
(4a) was prepared similarly to compound 3a from amine 1c and the acid chloride 2. Yield 0.62 g (65%); mp
1
289-290ºC (MeOH). H NMR spectrum, , ppm (J, Hz): 1.33 (3H, d, J = 6.3, CH3); 1.88 (1H, m, H-7); 2.42
(1H, m, H-7); 2.83 (2H, m, H-3); 3.84 (1H, m, H-6); 4.24 (1H, m, H-4); 4.43 (1H, m, H-4); 5.25 (1H, dd,
J = 4.8, J = 11.0, H-8); 7.33-7.40 (5H, m, Ph); 10.40 (1H, s, NH); 11.71 (1H, s, NH). 13C NMR spectrum, ,
ppm: 19.40 (CH3); 28.80 C(3); 38.12 C(4); 38.68 C(7); 46.10 C(6); 58.82 C(8); 127.26, 128.31, 128.47, 137.59,
144.27 (C-9a); 146.05 (C-4b); 166.53 (C-2). Мass spectrum, m/z (Irel, %): 284 [M-Cl]+ (7), 283 [M-HCl]+ (58),
269 (13), 268 (100), 179 (23). Found, %: C 56.48; H 5.78; N 21.62. C15H18ClN5O. Calculated, %: C 56.34;
H 5.67; N 21.90.
8-(4-Methoxyphenyl)-2-oxo-6-phenyl-1,2,3,4,5,6,7,8-octahydro-1,4a,5,9-tetraaza-8a-azoniafluorene
Chloride (4b) was prepared similarly to compound 3a from the amine 1d and acid chloride 2. Yield 0.73 g;
(59%); mp 292-294ºC (MeOH). 1H NMR spectrum, , ppm (J, Hz): 2.30 (1H, m, H-7); 2.55 (1H, m, H-7); 2.83
(2H, m, H-3); 3.74 (3H, s, CH3O); 4.16 (1H, m, H-4); 4.32 (1H, m, H-4); 4.95 (1H, m, H-6); 5.36 (1H, dd,
J = 3.7, J = 10.3, H-8); 6.92 (2H, d, J = 8.5, Ar); 7.19 (2H, d, J = 8.5, Ar); 7.40-7.54 (5H, m, Ph); 9.95 (1H, br.
s, NH); 11.80 (1H, br. s, NH). 13C NMR spectrum, , ppm: 28.90, 37.96, 54.03, 55.27, 58.86, 113.97, 127.14,
128.51, 128.74, 128.77, 129.28, 139.10, 144.45, 146.48, 159.46, 166.62. Маss spectrum, m/z (Irel, %): 376
[M-Cl]+ (3), 375 [M-HCl]+ (8), 315 (26), 272 (18), 240 (100), 134 (90), 119 (14). Found, %: C 61.51; H 5.22;
N 16.73. C21H22ClN5O2. Calculated, %: C 61.24; H 5.38; N 17.00.
250

This work was carried out with the financial support of the Federal Target Program "Science, Academic
and Teaching Staff of Innovative Russia" (State contract No. P1297).
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