6(7)-Acylperimidines nitration and methods of peri-annelation on this base

Article abstract of DOI:10.1007/s10593-013-1335-9

A method has been developed for the nitration of 6(7)-acylperimidines using sodium nitrite in formic acid. The reaction gives a mixture of 4(9)-, 9(4)-, and 7(6)-nitro-6(7)-acylperimidines from which the latter can be separated by extraction with chloroform. Reduction of the 6(7)-acyl-7(6)-nitro- perimidines yields 1H-1,5,7-triazacyclopenta[cd]phenalenes. Subsequent Schmidt reaction and reduction give 1,3,6,8-tetraazapyrenes.

Full text of DOI:10.1007/s10593-013-1335-9

Chemistry of Heterocyclic Compounds, Vol. 49, No. 7, October, 2013 (Russian Original Vol. 49, No. 7, July, 2013)
6(7)-ACYLPERIMIDINES NITRATION AND
METHODS OF peri-ANNELATION ON THIS BASE
A. V. Aksenov1*, N. A. Aksenov1, A. S. Lyakhovnenko1,
A. N. Smirnov1, I. I. Levina2, and I. V. Aksenova1
A method has been developed for the nitration of 6(7)-acylperimidines using sodium nitrite in formic
acid. The reaction gives a mixture of 4(9)-, 9(4)-, and 7(6)-nitro-6(7)-acylperimidines from which the
latter can be separated by extraction with chloroform. Reduction of the 6(7)-acyl-7(6)-nitro-
perimidines yields 1H-1,5,7-triazacyclopenta[cd]phenalenes. Subsequent Schmidt reaction and
reduction give 1,3,6,8-tetraazapyrenes.
Keywords: formic acid, perimidines, polyphosphoric acid, sodium azide, sodium nitrite, 1,3,6,8-tetra-
azapyrenes, 1H-1,5,7-triazacyclopenta[cd]phenalenes, zinc, nitration, Schmidt reaction.
peri-Annelated polynuclear aromatic and heteroaromatic compounds have a series of useful properties.
Their derivatives include many organic luminophores, dyes [1-4], and effective medications [5-10], which
behave, in first place, as luminescent intercalators [11-14]. So called molecular machines have been built based
on such compounds [15, 16].
Despite the diversity of possible structures for azapyrenes and other peri-annelated heterocycles, only a
few have been synthesized at this time and these do not generally contain functional groups [17, 18]. This is
firstly connected to the absence of convenient methods for the peri-annelation of heterocyclic nuclei to
phenalenes and azaphenalenes, that is partly explained by the lack of methods for the introduction of a nitrogen
atom into azophenalene molecules. All this fully applies to perimidine derivatives. Despite a recently developed
series of methods for the introduction of an amino group into the peri position of perimidine [19-23] they all
have significant drawbacks, viz. the difficulty associated with the work up of large amounts of material when
using polyphosphoric acid (PPA) and the possible formation of hydrazoic acid.
The nitration of arenes is the most widely used method for the introduction of a nitrogen atom into the
target molecule [19]. This is due to the simplicity of carrying out the reaction and the ease of the subsequent
reduction of the nitro to an amino group. It is important that the reduction can be combined with other reactions,
e.g., the acylation of the amines formed.
_______
*To whom correspondence should be addressed, e-mail: alexaks05@rambler.ru.
1North Caucasus Federal University, 1 Pushkin St., Stavropol 355009, Russia.
2N. M. Emanuel Institute of Biochemical Physics, 4 Kosygin St., Moscow 119991, Russia; e-mail:
iilevina@rambler.ru.
________________________________________________________________________________________
Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 1052-1059, July, 2013. Original
article submitted July 1, 2012.
980
0009-3122/13/4907-0980©2013 Springer Science+Business Media New York

We have previously reported a method for the nitration of perimidines using nitric acid in acetic acid
[24]. The main drawback of this method is the low yield of the nitro derivative and the poor selectivity. Thus,
the main reaction products are 4(9)-nitroperimidines. The more efficient system for the preparation of nitro
derivatives turned out to be sodium nitrite in acetic acid [25].
While a series of nitroperimidines was known at the beginning of our studies the nitro derivatives of the
perimidine series aldehydes and ketones 2-4 have not been reported. We decided to apply the method of
perimidine nitration to the nitration of the carbonyl compounds 1a-i. It was found that nitration of these
compounds with sodium nitrite in formic acid led to a mixture of the nitro derivatives 2a-i, 3a-i, and 4a-i in a
1
ratio close, in all cases, to 1:3:6 (as judged by H NMR spectroscopy). The main products are the 6(7)-nitro
derivatives 4a-i in 46-62% yields.
R
R
R
R
N
NH
NH
N
NH
N
NH
N
NaNO2
HCOOH
H2O, 
O2N
NO2
+
+
NO2
R1
2a–i
R1
R1
3a–i
R1
1a–i
O
O
O
O
4a–i
a R = R1 = H; b R = Me, R1 = H; c R = Ph, R1 = H; d R = H, R1 = Me; e R = R1 = Me;
f R = Ph, R1 = Me; g R = H, R1 = Ph; h R = Me, R1 = Ph; i R = R1 = Ph
Compounds 4a-i can be readily purified from the o-isomers 2a-i and 3a-i by extraction with chloroform.
The latter compounds are extracted by the chloroform but the 6(7)-nitro derivatives 4a-i remain in the aqueous
formic acid. Compounds 3d,f-h can be separated from compounds 2d,f-h by treating the residue with acetone
after distillation of the chloroform. The residue contains almost pure nitro derivatives 3d,f-h. In some examples,
compounds 2 can be isolated by flash chromatography in pure from the remaining mixture of nitro derivatives
but, in most cases, they could not be separated due to the close chromatographic mobilities of compounds 3a-i
and 2a-i as well as the low yield of the latter. Using this method the nitro derivatives 2e,g,i were obtained, but
compounds 2a-d,f,h and 3a-c could not be isolated in a pure state.
We have further studied the reduction of the nitro derivatives 4a-i. It was found that the reaction of
these compounds with zinc dust in acetic or formic acids gave a quantitative yield of the 1H-1,5,7-tri-
azacyclopenta[cd]phenalenes 7a-i.
R
R
R
N
N
HN
N
HN
N
Zn
HCOOH
4a–i
–H2O
, 1 h
NH
NH
R1
R1
NH2
R1
O
7a–i
OH
5a–i
6a–i
a R = R1 = H; b R = Me, R1 = H; c R = Ph, R1 = H; d R = H, R1 = Me; e R = R1 = Me;
f R = Ph, R1 = Me; g R = H, R1 = Ph; h R = Me, R1 = Ph; i R = R1 = Ph
981

It seems likely that the amines 5a-i formed in the course of reduction can undergo nucleophilic attack
by the amino group at the carbonyl function to give the intermediate compounds 6a-i which can lose a molecule
of water to give the indoles 7a-i.
This reaction can be carried out as a one-pot procedure. In this case, the carbonyl compounds 1a-i are
first nitrated using sodium nitrite in formic acid, and the zinc dust is then added to the reaction mixture and
stirred for 1 h.
The indoles 7a-i were quite readily separated from by-products but it proved no less convenient to
separate the mixture after the nitration. Compounds 2a-i and 3a-i were separated by extraction from the aqueous
formic acid solution. The nitro compounds 4a-i remaining in the solution were not separated but could be
converted to the corresponding indoles 7a-i. The yields calculated on the starting ketones 1a-i are not
significantly changed.
Use of the Schmidt reaction and subsequent reduction of the nitro group allows the nitro ketones 4d-g,i
to be converted to the 1,3,6,8-tetraazapyrenes 11a-e. The reagent used was the sodium azide in PPA developed
previously in our laboratory. The reaction mixture from treatment of the Schmidt reaction products 6(7)-(acyl-
amino)-7(6)-nitroperimidines 8a-f with water can be reduced by zinc dust in phosphoric acid to give the
intermediates 9a-e which spontaneously cyclize to the dihydrotetraazapyrene derivatives 10a-e. Oxidation of
the latter, likely by atmospheric oxygen, forms the tetraazapyrenes 11a-e.
1) NaN3, РРА, 70–80°C, 1 h;
100–110°C, 30 min
4d–g,i
2) H2O
R
R
R
R
N
N
N
N
HN
N
HN
N
HN
N
[O]
Zn
, 1 h
NH NO2
NH2
NH
HN
N
R1
11a–e
R1
O
8a–e
R1
O
9a–e
R1
10a–e
8–11 a R = H, R1 = Me; b R = H, R1 = Ph; c R = R1 = Me; d R = R1 = Ph; e R = Ph, R1 = Me
Thus, a synthetic method has been developed for the preparation of 6(7)-acylperimidine nitro
derivatives, 1H-1,5,7-triazacyclopenta[cd]phenalenes, and 1,3,6,8-tetraazapyrenes based on 6(7)-acyl-
perimidines.
EXPERIMENTAL
IR spectra were recorded on a Hitachi 215 spectrometer for KBr pellets. 1H and 13C NMR spectra were
recorded on a JNM-ECX400 spectrometer (400 and 100 MHz, respectively) using DMSO-d6 with TMS as
internal standard. Elemental analysis was performed on a KOVO CHN-1 analyzer. Melting points were
determined on a Chimlaborpribor PTP-M apparatus. Monitoring of the reaction course and the purity of the
products was carried out by TLC on Silufol UV-254 plates using EtOAc as eluent. Column chromatography
was carried out on L 40/100 silica gel with EtOAc as eluent. In the experiments the PPA used was prepared by
method [26] and had an 86% P2O5 content.
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Nitration of Acylperimidines 1a-i (General Method). NaNO2 (0.104 g, 1.5 mmol) in water (0.2 ml)
was added in one aliquot to a stirred solution of the corresponding formyl- or acetyl(benzoyl)perimidines 1a-i
(1 mmol) in HCOOH (10 ml). The product was left for 5 min at room temperature, after which it was heated to
reflux and immediately cooled. The solution was diluted with water (10 ml), forming a precipitate, and extracted
with chloroform (5×30 ml). The aqueous formic acid layer with the precipitate was diluted with more water
(10 ml), neutralized with sodium carbonate solution, and extracted with ethyl acetate (550 ml). The extract was
evaporated to give the pure 6(7)-nitroperimidines 4a-i as dark-red crystals. The chloroform extracts were
combined and evaporated to give a mixture of the carbonyl compounds 2a-i and 3a-i with a small amount of the
6(7)-isomers of compounds 4a-i. The latter can be separated by flash chromatography. Virtually pure
compounds 3d,f-h can be isolated by treating the residue with acetone. The compounds 3d,f-h remain as the
residue and can be filtered off and recrystallized. Compounds 3d-i and 2e,g,i are brick-red crystals. Compounds
2e,g,i and 3e,g,i could be partially separated by flash chromatography, but compounds 2a-d,f,h and 3a-c could
not be prepared in a pure state.
7(6)-Acetyl-2-methyl-9(4)-nitroperimidine (2e). Yield 0.008 g (3%). Mp 165-170°C (EtOH–H2O).
IR spectrum, , cm-1: 1636 (C=O), 3845 (NH). 1Н NMR spectrum, , ppm (J, Hz): 2.53 (3H, s, 2-CH3); 2.64 (3H,
s, COCH3); 7.36 (1H, d, J = 8.0, H-4(9)); 7.85 (1H, dd, J = 8.4, J = 8.0, H-5(8)); 8.54 (1H, s, H-8(5)); 8.64
(1H, d, J = 8.4, H-6(7)); 12.61 (1H, br. s, NH). Found, %: C 62.54; H 4.07; N 15.54. C14H11N3O3. Calculated,
%: C 62.45; H 4.12; N 15.61.
7(6)-Benzoyl-9(4)-nitroperimidine (2g). Yield 0.023 g (7%). Mp 196-198°C (EtOH–H2O).
IR spectrum, , cm-1: 1643 (C=O), 3849 (NH). 1Н NMR spectrum, , ppm (J, Hz): 7.46 (1H, d, J = 8.0, H-4(9));
7.61-7.63 (3H, m, H-3,4,5 Ph); 7.80-7.84 (3H, m, H-5(8), H-2,6 Ph); 8.07 (1H, s, H-2); 8.54 (1H, s, H-8(5));
8.76 (1H, d, J = 8.4, H-6(7)); 12.60 (1H, br. s, NH). Found, %: C 68.28; H 3.43; N 13.21. C18H11N3O3.
Calculated, %: C 68.14; H 3.49; N 13.24.
7(6)-Benzoyl-9(4)-nitro-2-phenylperimidine (2i). Yield 0.006 g (1.5%). Mp 221-223°C (EtOAc –
petroleum ether). IR spectrum, , cm-1: 1643 (C=O), 3850 (NH). 1Н NMR spectrum, , ppm (J, Hz): 7.43 (1H, d,
J = 8.0, H-4(9)); 7.60-7.64 (6H, m, H-3,4,5 Ph, H-3,4,5 COPh); 7.82 (2H, d, J = 7.5, H-2,6 COPh); 7.84 (1H, dd,
J = 8.4, J = 8.0, H-5(8)); 8.12 (2H, d, J = 8.0, H-2,6 Ph); 8.54 (1H, s, H-8(5)); 8.76 (1H, d, J = 8.4, H-6(7));
12.60 (1H, br. s, NH). Found, %: C 73.47; H 3.74; N 10.62. C24H15N3O3. Calculated, %: C 73.27; H 3.84;
N 10.68.
6(7)-Acetyl-9(4)-nitroperimidine (3d). Yield 0.053 g (21%). Mp 234-236°C (EtOH–H2O).
1
IR spectrum, , cm-1: 1645 (C=O), 3848 (NH). Н NMR spectrum, , ppm (J, Hz): 2.63 (3H, s, COСН3); 7.21
(1H, d, J = 8.5, H-4(9)); 8.06 (1H, d, J = 9.9, H-7(6)); 8.12 (1H, s, H-2); 8.25 (1H, d, J = 9.9, H-8(5)); 8.34
(1H, d, J = 8.5, H-5(8)); 12.49 (1H, br. s, NH). Found, %: C 61.36; H 3.49; N 16.41. C13H9N3O3. Calculated, %:
C 61.18; H 3.55; N 16.46.
6(7)-Acetyl-2-methyl-9(4)-nitroperimidine (3e). Yield 0.012 g (4.5%). Mp 202-203°C (EtOH–H2O).
1
IR spectrum, , cm-1: 1644 (C=O), 3843 (NH). Н NMR spectrum, , ppm (J, Hz): 2.46 (3H, s, 2-СН3); 2.63
(3H, s, COСН3); 7.21 (1H, d, J = 8.5, H-4(9)); 8.06 (1H, d, J = 9.9, H-7(6)); 8.22 (1H, d, J = 9.9, H-8(5)); 8.31
(1H, d, J = 8.5, H-5(8)); 12.46 (1H, br. s, NH). Found, %: C 62.58; H 4.05; N 15.53. C14H11N3O3.
Calculated, %: C 62.45; H 4.12; N 15.61.
6(7)-Acetyl-9(4)-nitro-2-phenylperimidine (3f). Yield 0.041 g (12%). Mp 212-214°C (EtOH–H2O).
1
IR spectrum, , cm-1: 1636 (C=O), 3842 (NH). Н NMR spectrum, , ppm (J, Hz): 2.58 (3H, s, COСН3); 7.21
(1H, d, J = 8.5, H-4(9)); 7.59-7.63 (3H, m, Н-3,4,5 Ph); 8.09-8.12 (3H, m, H-7(6), Н-2,6 Ph); 8.22 (1H, d,
J = 9.9, H-8(5)); 8.31 (1H, d, J = 8.5, H-5(8)); 12.46 (1H, br. s, NH). Found, %: C 69.06; H 3.87; N 12.55.
C19H13N3O3. Calculated, %: C 68.88; H 3.95; N 12.68.
6(7)-Benzoyl-9(4)-nitroperimidine (3g). Yield 0.067 g (21%). Mp 257-258°C (EtOAc). IR spectrum,
1
, cm-1: 1638 (C=O), 3847 (NH). Н NMR spectrum, , ppm (J, Hz): 7.25 (1H, d, J = 8.5, H-4(9)); 7.58 (2H,
dd, J = 7.5, J = 7.1, H-3,5 Ph); 7.69 (1H, t, J = 7.1, H-4 Ph); 7.81 (2H, d, J = 7.5, H-2,6 Ph); 8.06 (1H, s, H-2);
983

8.09 (1H, d, J = 9.8, H-7(6)); 8.17 (1H, d, J = 9.8, H-8(5)); 8.31 (1H, d, J = 8.5, H-5(8)); 12.42 (1H, br. s, NH).
Found, %: C 68.26; H 3.42; N 13.22. C18H11N3O3. Calculated, %: C 68.14; H 3.49; N 13.24.
6(7)-Benzoyl-2-methyl-9(4)-nitroperimidine (3h). Yield 0.028 g (8.5%). Mp 276-278°C (EtOAc).
IR spectrum, , cm-1: 1642 (C=O), 3767 (NH). 1Н NMR spectrum, , ppm (J, Hz): 2.54 (3H, s, СН3); 7.32 (1H, d,
J = 8.5, H-4(9)); 7.57 (2H, dd, J = 7.4, J = 7.3, Н-3,5 Ph); 7.70 (1H, t, J = 7.4, Н-4 Ph); 7.79-7.84 (3H, m,
H-7(6), Н-2,6 Ph); 8.02-8.03 (2H, m, H-5,8); 12.04 (1H, br. s, NH). Found, %: C 69.03; H 3.88; N 12.59.
C19H13N3O3. Calculated, %: C 68.88; H 3.95; N 12.68.
6(7)-Benzoyl-9(4)-nitro-2-phenylperimidine (3i). Yield 0.018 g (5%). Mp 184-186°C (EtOAc –
petroleum ether). IR spectrum, , cm-1: 1638 (C=O), 3847 (NH). 1Н NMR spectrum, , ppm (J, Hz): 7.23 (1H,
d, J = 8.5, H-4(9)); 7.61-7.63 (6H, m, Н-3,4,5 Ph, Н-3,4,5 COPh); 7.82 (2H, d, J = 7.5, Н-2,6 COPh); 8.11-8.12
(3H, m, H-7(6), Н-2,6 Ph); 8.19 (1H, d, J = 9.8, H-8(5)); 8.34 (1H, d, J = 8.5, H-5(8)); 12.42 (1H, br. s, NH).
Found, %: C 73.43; H 3.76; N 10.64. C24H15N3O3. Calculated, %: C 73.27; H 3.84; N 10.68.
7(6)-Formyl-6(7)-nitroperimidine (4a). Yield 0.118 g (49%). Mp 257-259°C (EtOH–H2O).
IR spectrum, , cm-1: 1652 (C=O), 3167 (NH). 1Н NMR spectrum, , ppm (J, Hz): 6.95 (1H, d, J = 8.5, H-4(9));
7.01 (1H, d, J = 8.1, H-9(4)); 8.08 (1H, s, H-2); 8.14 (1H, d, J = 8.1, H-8(5)); 8.17 (1H, d, J = 8.5, H-5(8)); 9.76
(1H, s, CHO); 12.28 (1H, br. s, NH). Found, %: C 59.93; H 2.88; N 17.49. C12H7N3O3. Calculated, %: C 59.76;
H 2.93; N 17.42.
7(6)-Formyl-2-methyl-6(7)-nitroperimidine (4b). Yield 0.130 g (51%). Mp 241-243°C (EtOH–H2O).
IR spectrum, , cm-1: 1651 (C=O), 3211 (NH). 1Н NMR spectrum, , ppm (J, Hz): 2.29 (3H, s, СН3); 6.74 (1H,
d, J = 8.5, H-4(9)); 6.88 (1H, d, J = 8.1, H-9(4)); 8.01 (1H, d, J = 8.1, H-8(5)); 8.08 (1H, d, J = 8.5, H-5(8));
9.74 (1H, s, CHO); 12.14 (1H, br. s, NH). Found, %: C 61.31; H 3.49; N 16.41. C13H9N3O3. Calculated, %:
C 61.18; H 3.55; N 16.46.
7(6)-Formyl-6(7)-nitro-2-phenylperimidine (4c). Yield 0.146 g (46%). Mp 255-257°C (EtOH–H2O).
IR spectrum, , cm-1: 1658 (C=O), 3170 (NH). 1Н NMR spectrum, , ppm (J, Hz): 6.83 (1H, d, J = 8.5, H-4(9));
7.03 (1H, d, J = 8.1, H-9(4)); 7.60-7.62 (3H, m, Н-3,4,5 Ph); 8.08 (1H, d, J = 8.1, H-8(5)); 8.13-7.15 (3H, m,
H-5(8), Н-2,6 Ph); 9.77 (1H, s, CHO); 12.27 (1H, br. s, NH). Found, %: C 68.31; H 3.45; N 13.28. C18H11N3O3.
Calculated, %: C 68.14; H 3.49; N 13.24.
7(6)-Acetyl-6(7)-nitroperimidine (4d). Yield 0.150 g (59%). Mp 296-298°C (EtOH–H2O). IR spectrum,
, cm-1: 1638 (C=O), 3429 (NH). 1Н NMR spectrum, , ppm (J, Hz): 2.51 (3H, s, COСН3); 6.77 (1H, d, J = 8.5,
H-4(9)); 6.92 (1H, d, J = 8.1, H-9(4)); 7.94 (1H, s, H-2); 8.02 (1H, d, J = 8.1, H-8(5)); 8.08 (1H, d, J = 8.5,
H-5(8)); 12.22 (1H, br. s, NH). 13С NMR spectrum, , ppm: 27.7; 108.0; 111.1; 122.5; 123.4; 126.7 (2C); 129.9;
132.9 (2C); 138.1; 147.1; 198.7. Found, %: C 61.33; H 3.51; N 16.47. C13H9N3O3. Calculated, %: C 61.18;
H 3.55; N 16.46.
7(6)-Acetyl-2-methyl-6(7)-nitroperimidine (4e). Yield 0.167 g (62%). Mp 279-281°C (EtOH–H2O).
1
IR spectrum, , cm-1: 1636 (C=O), 3428 (NH). Н NMR spectrum, , ppm (J, Hz): 2.28 (3H, s, 2-СН3); 2.51
(3H, s, COСН3); 6.74 (1H, d, J = 8.5, H-4(9)); 6.88 (1H, d, J = 8.1, H-9(4)); 8.01 (1H, d, J = 8.1, H-8(5)); 8.08
(1H, d, J = 8.5, H-5(8)); 12.11 (1H, br. s, NH). 13С NMR spectrum, , ppm: 22.3; 27.7; 108.0; 111.2; 122.5;
123.3; 126.8 (2C); 130.0; 132.9 (2C); 138.1; 147.1; 198.8. Found, %: C 62.63; H 4.04; N 15.55. C14H11N3O3.
Calculated, %: C 62.45; H 4.12; N 15.61.
7(6)-Acetyl-6(7)-nitro-2-phenylperimidine (4f). Yield 0.182 g (55%). Mp 261-262°C (EtOH–H2O).
IR spectrum, , cm-1: 1633 (C=O), 3431 (NH). 1Н NMR spectrum, , ppm (J, Hz): 2.52 (3H, s, COСН3); 6.97
(1H, d, J = 8.4, H-4(9)); 7.11 (1H, d, J = 8.1, H-9(4)); 7.61 (2H, dd, J = 7.6, J = 7.1, Н-3,5 Ph); 7.66 (1H, t,
J = 7.1, Н-4 Ph); 8.07 (1H, d, J = 8.1, H-8(5)); 8.12-8.13 (3H, m, H-5(8), Н-2,6 Ph); 12.09 (1H, br. s, NH).
Found, %: C 69.04; H 3.89; N 12.57. C19H13N3O3. Calculated, %: C 68.88; H 3.95; N 12.68.
7(6)-Benzoyl-6(7)-nitroperimidine (4g). Yield 0.196 g (62%). Mp 206-207°C (EtOH–H2O).
IR spectrum, , cm-1: 1638 (C=O), 3427 (NH). 1Н NMR spectrum, , ppm (J, Hz): 6.79 (1H, d, J = 8.3, H-4(9));
6.92 (1H, d, J = 7.7, H-9(4)); 7.56-7.58 (3H, m, H-8(5), Н-3,5 Ph); 7.67 (1H, t, J = 7.0, Н-4 Ph); 7.84 (2H, d,
984

J = 7.2, Н-2,6 Ph); 7.99 (1H, s, H-2); 8.10 (1H, d, J = 8.3, H-5(8)); 12.10 (1H, br. s, NH). Found, %: C 68.22;
H 3.43; N 13.21. C18H11N3O3. Calculated, %: C 68.14; H 3.49; N 13.24.
7(6)-Benzoyl-2-methyl-6(7)-nitroperimidine (4h). Yield 0.162 g (49%). Mp 171-173°C (EtOH–H2O).
IR spectrum, , cm-1: 1634 (C=O), 3428 (NH). 1Н NMR spectrum, , ppm (J, Hz): 2.31 (3H, s, СН3); 6.77 (1H,
d, J = 8.5, H-4(9)); 6.88 (1H, d, J = 8.0, H-9(4)); 7.55 (2H, dd, J = 7.6, J = 7.1, Н-3,5 Ph); 7.56 (1H, d, J = 8.0,
H-8(5)); 7.67 (1H, t, J = 7.5, Н-4 Ph); 7.83 (2H, d, J = 7.0, Н-2,6 Ph); 8.10 (1H, d, J = 8.5, H-5(8)); 12.12 (1H,
br. s, NH). Found, %: C 69.01; H 3.90; N 12.56. C19H13N3O3. Calculated, %: C 68.88; H 3.95; N 12.68.
7(6)-Benzoyl-6(7)-nitro-2-phenylperimidine (4i). Yield 0.189 g (48%). Mp 174-176°C (EtOH–H2O).
IR spectrum, , cm-1: 1632 (C=O), 3429 (NH). 1Н NMR spectrum, , ppm (J, Hz): 6.98 (1H, d, J= 8.5, H-4(9)); 7.11
(1H, d, J = 8.1, H-9(4)); 7.54-7.71 (7H, m, H-8(5), Н-3,4,5 Ph, Н-3,4,5 COPh); 7.85 (2H, dd, J = 7.1, J = 1.3, Н-2,6
СОPh); 8.14 (1H, d, J = 8.5, H-5(8)); 8.17 (2H, dd, J = 7.0, J = 1.5, Н-2,6 Ph); 12.18 (1H, br. s, NH). Found, %:
C 73.44; H 3.77; N 10.61. C24H15N3O3. Calculated, %: C 73.27; H 3.84; N 10.68.
Preparation of 1H-1,5,7-Triazacyclopenta[cd]phenalenes 7a-i (General Method). A. NaNO2
(0.104 g, 1.5 mmol) in water (0.2 ml) was added in one aliquot to a stirred solution of the corresponding
acylperimidine 1a-i (1 mmol) in HCOOH (10 ml) and left for 5 min at room temperature. The solution was
diluted with water (10 ml) with formation of a precipitate and extracted with CHCl3 (5×30 ml). Zinc dust (0.320
g, 5.0 mmol) was added to the aqueous formic acid layer, stirred for 1 h at room temperature, and then refluxed
for a further 1 h. The product was diluted with water (10 ml), neutralized with ammonia solution, and extracted
with toluene (10×50 ml). The toluene extracts were combined, the solvent was evaporated, and the residue was
purified by recrystallization.
B. NaNO2 (0.104 g, 1.5 mmol) in water (0.2 ml) was added in one aliquot to a stirred solution of the
corresponding acylperimidine 1a-i (1 mmol) in HCOOH (10 ml) and left for 5 min at room temperature. Zinc
dust (0.320 g, 5.0 mmol) was added, and the reaction mixture was stirred for 1 h at room temperature and then
refluxed for a further 1 h. The product was diluted with water (10 ml), neutralized with ammonia solution, and
extracted with toluene (10×50 ml). The toluene extracts were combined, the solvent was evaporated, and the
residue was purified by recrystallization.
1H-1,5,7-Triazacyclopenta[cd]phenalene (7a). Yield 0.091 g (47%, method A), 0.089 g (46%, method
B). Mp 207-209°C (PhH) (mp 207-209°C [22, 27]). 1H NMR spectrum identical to that given in the work [22].
6-Methyl-1H-1,5,7-triazacyclopenta[cd]phenalene (7b). Yield 0.101 g (49%, method A), 0.097 g
(47%, method B). Mp 237-238°C (PhH) (mp 227-238°C [27]). 1H NMR spectrum identical to that given in the
work [27].
6-Phenyl-1H-1,5,7-triazacyclopenta[cd]phenalene (7c). Yield 0.121 g (45%, method A), 0.121 g
(45%, method B). Mp 201-203°C (PhH) (mp 201-203°C [22, 27]). 1H NMR spectrum identical to that given in
the work [22].
2-Methyl-1H-1,5,7-triazacyclopenta[cd]phenalene (7d). Yield 0.116 g (56%, mеthоd А), 0.110 g
1
(53%, method B). Mp 259-260°C (PhH) (mp 259-260°C [22]). H NMR spectrum identical to that given in the
work [22].
2,6-Dimethyl-1H-1,5,7-triazacyclopenta[cd]phenalene (7e). Yield 0.157 g (71%, method A), 0.150 g
(68%, method B). Mp 271-272°C (PhH) (mp 271-272°C [22]). 1H NMR spectrum identical to that given in the
work [22].
2-Methyl-6-phenyl-1H-1,5,7-triazacyclopenta[cd]phenalene (7f). Yield 0.150 g (53%, method A),
0.150 g (53%, method B). Mp 245-246°C (PhH–hexane) (mp 245-246°C [22, 27]). 1H NMR spectrum identical
to that given in the work [22].
2-Phenyl-1H-1,5,7-triazacyclopenta[cd]phenalene (7g). Yield 0.164 g (61%, method A), 0.160 g
(60%, method B). Mp 263-265°C (PhH) (mp 263-265°C [22, 27]). 1H NMR spectrum identical to that given in
the work [22].
985

6-Methyl-2-phenyl-1H-1,5,7-triazacyclopenta[cd]phenalene (7h). Yield 0.133 g (47%, method A),
0.127 g (45%, method B). Mp 291-292°C (PhH) (mp 291-292°C [22, 27]). 1H NMR spectrum identical to that
given in the work [22].
2,6-Diphenyl-1H-1,5,7-triazacyclopenta[cd]phenalene (7i). Yield 0.159 g (46%, method A), 0.145 g
(42%, method B). Mp 169-171°C (PhH–hexane) (mp 169-171°C [22, 27]). 1H NMR spectrum identical to that
given in the work [22].
Preparation of 1,3,6,8-Tetraazapyrenes 11a-e (General Method).
A
mixture of the
nitroacylperimidine 4d-g,i (1 mmol) and NaN3 (0.07 g, 1.07 mmol) in 86% PPA (2-3 g) was heated at 70-80ºC
with vigorous stirring for 1 h, and the temperature was then increased to 100-110ºC. The reaction mixture was
heated at this temperature for 0.5 h. The reaction mixture was diluted with water (50 ml), and zinc dust (0.45 g,
7.00 mmol) was added. The product was refluxed for 1 h, cooled, and neutralized with ammonia solution. The
product was then extracted with BuOH (3×50 ml), solvent was evaporated, and the compounds were purified by
recrystallization.
2-Methyl-1,3,6,8-tetraazapyrene (11a). Yield 0.191 g (87%). Mp >300°C (EtOH) (mp >300°C [28]).
1H NMR spectrum identical to that given in the work [28].
2-Phenyl-1,3,6,8-tetraazapyrene (11b). Yield 0.237 g (84%). Mp >300°C (BuOH). 1H NMR spectrum,
, ppm (J, Hz): 7.50-7.52 (3H, m, Н-3,4,5 Ph); 8.41-8.42 (2H, m, J = 9.4, H-5,9); 8.51 (2H, d, J = 9.4, H-4,10);
8.88-8.89 (2H, m, Н-2,6 Ph); 9.94 (1H, s, H-7). Found, %: C 76.73; H 3.54; N 19.73. C18H10N4. Calculated, %:
C 76.58; H 3.57; N 19.85.
2,7-Dimethyl-1,3,6,8-tetraazapyrene (11c). Yield 0.213 g (91%). Mp >300°C (EtOH) (mp >300°C
[28]). 1H NMR spectrum identical to that given in the work [28].
2,7-Diphenyl-1,3,6,8-tetraazapyrene (11d). Yield 0.315 g (88%). Mp >300°C (EtOH) (mp >300°C
[29]). 1H NMR spectrum identical to that given in the work [29].
2-Methyl-7-phenyl-1,3,6,8-tetraazapyrene (11e). Yield 0.258 g (87%). Mp >300°C (EtOH) (mp
>300°C [29]). 1H NMR spectrum identical to that given in the work [29].
This work was carried out with the financial support of the Russian Foundation for Basic Research
(grant 12-03-31646mol_a)
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