Heterocyclic analogs of pleiadicne. 69. Synthesis and oxidative hydroxylation of 1-alkyl-1,3-diazapyrenium salt

Article abstract of DOI:10.1023/A:1015030301555

1-Alkyl-1,3-diazapyrenium salts were prepared according to two procedures. Oxidative hydroxylation of these salts afforded 1-alkyl-1,3-diazapyren-2-ones. The spectral characteristics of the resulting compounds are discussed.

Full text of DOI:10.1023/A:1015030301555

Russian Chemical Bulletin, International Edition, Vol. 51, No. 1, pp. 139—143, January, 2002
139
Heterocyclic analogs of pleiadiene.
69.* Synthesis and oxidative hydroxylation of 1ꢀalkylꢀ1,3ꢀdiazapyrenium salts
a
b
c
I. V. Borovlev,a O. P. Demidov, A. V. Chernyshev, and A. F. Pozharskii

aDepartment of Biology and Chemistry, Stavropol State University,
1a ul. Pushkina, 355009 Stavropol, Russian Federation.
Fax:+7 (8652) 35 40 33. Eꢀmail: biochemꢀorg@stavsu.ru
bScientific Research Institute of Physical and Organic Chemistry of Rostov State University,
194/2 ul. Stachka, 344090 RostovꢀonꢀDon, Russian Federation.
Fax: +7 (8632) 28 56 67. Eꢀmail: photo@ipoc.rsu.ru
cDepartment of Chemistry, Rostov State University,
7 ul. Zorge, 344090 RostovꢀonꢀDon, Russian Federation.
Fax:+7 (8632) 22 39 58. Eꢀmail: apozharskii@chimfak.rsu.ru
1ꢀAlkylꢀ1,3ꢀdiazapyrenium salts were prepared according to two procedures. Oxidative
hydroxylation of these salts afforded 1ꢀalkylꢀ1,3ꢀdiazapyrenꢀ2ꢀones. The spectral characterisꢀ
tics of the resulting compounds are discussed.
Key words: 1,3ꢀdiazapyrene, quaternization, oxidative hydroxylation, luminescence.
Considerable recent attention has been given to
2,7ꢀdiazapyrenium salts2—6 because they combine the
properties of efficient luminophores, redox agents, phoꢀ
tographic agents, and intercalators. This interest is partly
extended to derivatives of other diazapyrenes.7
Until recently, data on the synthesis and properties of
1,3ꢀdiazapyrenes were virtually lacking. Earlier, we have
developed8 a convenient method for the preparation of
these compounds, including the parent compound.** The
present study was aimed at preparing 1,3ꢀdiazapyrenium
salts, examining their luminescence characteristics, and
investigating a number of their reactions.
polynuclear π system with a high contribution of canoniꢀ
cal structures 2″ and 2´´´ to the resonance hybrid. The
former structure is a combination of 1ꢀRꢀperimidine and
the phenalenium cation.
We studied another possible procedure for the syntheꢀ
sis of salts 2 based on the reactions of 1ꢀRꢀperimidines
with α,βꢀunsaturated carbonyl compounds in a medium
of polyphosphoric acid (PPA). In the absence of an oxiꢀ
dizing agent, the reaction of 1ꢀmethylperimidine (3) with
benzalacetophenone (chalcone) would be expected to afꢀ
ford intermediates of type 4 or 5 (Scheme 2). However, as
in the case of unsubstituted perimidine,8 these intermediꢀ
ates were not detected. At 70—75 °C, the reaction in PPA
gave rise to a salt, which we isolated as perchlorate 2h (the
yield was 73%). Salt 2h was also independently prepared
by the reaction of 2c with HClO4.
Results and Discussion
Quaternization of symmetrical 1,3ꢀdiazapyrenes 1a—c
with an excess of alkyl halides in MeCN proceeded readily
to give 1ꢀalkylꢀ1,3ꢀdiazapyrenium salts (2) (Scheme 1).***
Unlike virtually colorless starting amines, salts 2 were
obtained as yellow or red crystalline compounds. The
appearance of a deep color results, probably, from effiꢀ
cient delocalization of the positive charge throughout the
Since solutions of compounds 1 and 2 exhibit fluoresꢀ
cence, we recorded their absorption and fluorescence
spectra and measured the quantum yields of fluorescence
(Table 1).
On going from bases 1 to salts 2, the bathochromic
shifts of the longꢀwavelength absorption maxima and the
bathofloric shifts of the fluorescence maxima are observed
due, apparently, to the lowering of the energy of the lowꢀ
est unoccupied molecular orbital (LUMO, see Table 1).
As in other analogous cases,10 small structural changes
have a pronounced effect on luminescence properties.
Thus, the extension of the conjugated chain due to the
presence of two phenyl groups (on going from 1a to 1b)
leads to a visually noticeable sharp increase in the fluoresꢀ
* For Part 68, see Ref. 1.
** The detailed data will be published in Chemistry of Heterocyꢀ
clic Compounds in 2002.
*** Diquaternization of compounds 1a—c did not proceed unꢀ
der the action of alkylating agents used in the present study. We
plan to prepare the corresponding dications according to other
procedures in the future (cf. the lit. data2,9).
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 132—135, January, 2002.
1066ꢀ5285/02/5101ꢀ139 $27.00 © 2002 Plenum Publishing Corporation

140
Russ.Chem.Bull., Int.Ed., Vol. 51, No. 1, January, 2002
Borovlev et al.
Scheme 1
R1
H
Ph
Ph
H
R2
H
H
Me
H
H
Alk
—
—
—
Me
Et
Hal
—
—
—
I
R1
Ph
Ph
Ph
Ph
Ph
R2
H
H
H
H
Alk
Me
Et
Bn
All
Hal
I
I
Cl
Br
I
1a
1b
1c
2a
2b
2c
2d
2e
2f
H
I
2g
Me
Me
cence intensity under UV light. Analogous changes acꢀ
companied by substantial bathochromic and bathofloric
shifts are observed when comparing the properties of salts
2a,b and 2c—g. In the latter case, noteworthy are high
quantum yields. For all compounds, the Stokes shifts are
observed in a standard range. However, the Stokes shifts
for bases 1b and salts 2c—g (45—51 nm) are essentially
larger than the corresponding values for 2a,b (24—28 nm)
and depend only weakly on the solvent used. The nature
both of the Nꢀalkyl radical and the counterion affects
only slightly the values of λmax of the longꢀwavelength
absorption and fluorescence of compounds 2.
Table 1. UV and fluorescence spectra of compounds 1 and 2
Comꢀ UV spectrum Fluorescence UV spectrum Fluorescence
pound (EtOH),
(EtOH),
(CHCl3),
(CHCl3),
Scheme 2
λ
max/nm
λ
max/nm
λ
max/nm
λ
max/nm
(lgε)
(Φ )
(lgε)
(Φ )
fl
fl
1a
239 (4.53)
266 (4.22)
339 (4.17)
366 (3.61)
— (—)
267 (4.26)
336 (4.20)
367 (3.60)
— (—)
1b
2a
2b
243 (4.52)
278 (4.46)
375 (4.44)
426 (0.87) 281 (4.43)
374 (4.40)
415 (0.38)
— (—)
243 (—)
286 (—)**
387 (—)
415* (0.01) 287**
394
241 (4.36)
285 (4.00)
388 (4.26)
412* (0.016) 287 (—)**
393
— (—)
2c
2d
2e
2f
260 (shoulder) 477 (0.98) 434 (4.51)
427 (4.46)
478 (0.14)
263 (4.38)
429 (4.50)
477 (0.97) 270 (shoulder) 477 (0.12)
435 (4.46)
268 (4.32)
435 (4.42)
480 (0.88) 270 (4.34)
438 (4.41)
475 (0.13)
478 (0.15)
477 (0.15)
268 (4.33)
431 (4.39)
480 (0.84) 270 (4.40)
439 (4.48)
2g
427 (4.40)
474 (0.98) 433 (4.47)
* Lowꢀintensity fluorescence.
** The compound is poorly soluble.

Transformations of 1ꢀRꢀ1,3ꢀdiazapyrenium salts
Russ.Chem.Bull., Int.Ed., Vol. 51, No. 1, January, 2002
141
Taking into account high πꢀdeficiency of salts 2, the
latter would be expected to readily react with nucleophilic
agents. Actually, treatment of compounds 2c,f with aqueꢀ
ous alkali in the presence of K3[Fe(CN)6] afforded
products of oxidative hydroxylation at position 2, viz.,
1ꢀmethylꢀ and 1ꢀallylꢀ6,8ꢀdiphenylꢀ1,3ꢀdiazapyrenꢀ2ꢀ
ones (6a,b) in 85 and 32% yields, respectively (Scheme 3).
main initial direction of fragmentation of the molecular
ion involves elimination of the H2C=NH group (the inꢀ
tense signal [M – 29]), whereas elimination of the methyl
group at this stage does not take place at all (the signal
[M – 15] is absent).
To summarize, 1ꢀalkylꢀ1,3ꢀdiazapyrenium salts can
be prepared both by quaternization of 1,3ꢀdiazapyrenes
with alkyl halides and by the reactions of 1ꢀalkylperꢀ
imidines with chalcones in a medium of polyphosphoric
acid. Their oxidative hydroxylation affords the correꢀ
sponding 1ꢀalkylꢀ1,3ꢀdiazapyrenꢀ2ꢀones. Some of the
compounds synthesized have high quantum yields of fluoꢀ
rescence.
Scheme 3
Experimental
1
The H NMR spectra were recorded on a Bruker WPꢀ200
instrument with Me4Si as the internal standard. The assignment
of the signals was made using selective homodecoupling. The
mass spectra were measured on an MXꢀ1321A instrument
(70 eV, EI). The electronic absorption spectra were recorded on
a Specord Mꢀ40 spectrophotometer. The fluorescence spectra
were measured on a Shimadzu RF 5001 PC spectrofluoromꢀ
eter. The quantum yields of fluorescence were determined by
Parker—Rees's11 method with the use of quinine bisulfate in a
1 M solution of H2SO4 (Φ = 0.51, λ = 365 nm12) and
fl
ex
3ꢀmethoxybenzanthrone in toluene (Φ = 0.1, λ = 365 nm10
)
fl
ex
as the standard luminophores. The course of the reactions and
the purities of the compounds were monitored on Silufol UVꢀ254
plates. Column chromatography was carried out on silica gel
Chemapol L (40—100 µm).
Acetononitrile, dioxane, benzalacetophenone, and ethyl acꢀ
etate of chemical purity grade were used. Polyphosphoric acid
was prepared according to a known procedure.13 1ꢀMethylꢀ
perimidine and 1ꢀmethylperimidone were synthesized accordꢀ
ing to procedures reported previously.14,15
Synthesis of salts 2 (general procedure). A solution of comꢀ
pound 1a—c (1 mmol) and the corresponding alkyl halide
(3 mmol) in MeCN (20 mL) was refluxed for 4 h. Then the
reaction mixture was concentrated to 5 mL and benzene (15 mL)
was added. The precipitate that formed was filtered off, washed
with benzene and light petroleum, and dried.
We prepared compound 6a also by the reaction of
chalcone with 1ꢀmethylperimidone (7) in PPA. Undoubtꢀ
edly, the latter reaction proceeded analogously to that in
the case of perimidine. Hence, the proposed procedure
for the fusion of the periꢀring to perimidines has a rather
general character.
Compared to the signals for the protons of the diazaꢀ
1
pyrene ring in the H NMR spectra of bases, the correꢀ
sponding signals for salts 2 are shifted downfield even
more substantially and are observed at δ > 8.5, the largest
shift being characteristic of the H(2) proton (δ 10.2—10.4).
The protons at positions 4, 5, 9, and 10 are manifested as
two pairs of doublets, whereas the H(6) and H(8) protons
of the peripheral periꢀring of compounds 2a,b give one
twoꢀproton doublet. In the spectra of compounds 2c—g,
the phenyl groups located in the same positions give two
multiplet signals with the intensity ratio of 2 : 3, i.e., the
signals for the ortho protons are slightly shifted downfield
due, apparently, to anisotropy of the diazapyrene ring.
1ꢀMethylꢀ1,3ꢀdiazapyrenium iodide (2a). The yield was 56%.
1
Yellow crystals, m.p. 312—314 °C. H NMR (DMSOꢀd6), δ:
4.76 (s, 3 H, Me); 8.60 and 9.37 (both d, 1 H each, H(4), H(5),
J1 = J2 = 9.4 Hz); 8.67 (t, 1 H, H(7), J = 7.7 Hz); 8.80 and 9.50
(both d, 1 H each, H(10), H(9), J1 = J2 = 9.4 Hz); 9.20 (d, 2 H,
H(6), H(8), J6(8),7 = 7.7 Hz); 10.11 (s, 1 H, H(2)). Found (%):
C, 52.24; H, 3.32; N, 8.15. C15H11IN2. Calculated (%): C, 52.05;
H, 3.20; N, 8.09.
1ꢀEthylꢀ1,3ꢀdiazapyrenium iodide (2b). The yield was 48%.
1
Yellow crystals, m.p. 265—267 °C. H NMR (DMSOꢀd6), δ:
1.73 (t, 3 H, Me, J = 7.2 Hz); 5.24 (q, 2 H, CH2, J = 7.2 Hz);
8.60 and 9.36 (both d, 1 H each, H(4), H(5), J1 = J2 = 9.4 Hz);
8.67 (t, 1 H, H(7), J = 7.7 Hz); 8.80 and 9.49 (both d,
1 H each, H(10), H(9), J1 = J2 = 9.4 Hz); 9.20 (d, 2 H, H(6),
H(8), J6(8),7 = 7.7 Hz); 10.16 (s, 1 H, H(2)). Found (%):
C, 53.45; H, 3.33; N, 7.58. C16H13IN2. Calculated (%): C, 53.35;
H, 3.64; N, 7.78.
1
The H NMR spectra of compounds 6a,b are characterꢀ
ized by the large spinꢀspin coupling constants for the
ortho substituents (J4,5 = J9,10 = 9.4 Hz for both comꢀ
pounds). The mass spectrum of compound 6a has a proꢀ
nounced mediumꢀintensity molecular ion peak [M] and a
peak [M + 1] corresponding to the 13C1ꢀisotopomer. The

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Russ.Chem.Bull., Int.Ed., Vol. 51, No. 1, January, 2002
Borovlev et al.
1ꢀMethylꢀ6,8ꢀdiphenylꢀ1,3ꢀdiazapyrenium iodide (2c). The
uct was purified as described above. M.p. 287—288 °C. The
specimens of the salts prepared according to procedures A and B
did not give a melting point depression.
yield was 92%. Cherryꢀred crystals, m.p. 236—237 °C. 1H NMR
(DMSOꢀd6), δ: 5.00 (s, 3 H, Me); 7.75 (m, 6 H, mꢀ and pꢀH Ph);
7.89 (m, 4 H, oꢀH Ph); 8.64 and 9.30 (both d, 1 H each, H(4),
H(5), J1 = J2 = 9.4 Hz); 8.65 (s, 1 H, H(7)); 8.96 and 9.42
(both d, 1 H each, H(10), H(9), J1 = J2 = 9.4 Hz); 10.23 (s, 1 H,
H(2)). Found (%): C, 65.24; H, 4.01; N, 5.48. C27H19IN2.
Calculated (%): C, 65.07; H, 3.84; N, 5.62.
1ꢀMethylꢀ6,8ꢀdiphenylꢀ1,3ꢀdiazapyrenꢀ2ꢀone (6a). A. An
aqueous solution of KOH (0.13 g, 2.4 mmol) and K3[Fe(CN)6]
(0.40 g, 1.2 mmol) was added dropwise with stirring to a suspenꢀ
sion of 1ꢀmethylꢀ6,8ꢀdiphenylꢀ1,3ꢀdiazapyrenium iodide (2c)
(0.30 g, 0.6 mmol) in dioxane (20 mL) with heating to 80 °C for
10 min. The reaction mixture was stirred at this temperature for
1 h. Then water (30 mL) was added. After 30 min, the precipiꢀ
tate that formed was filtered off. The dry product was placed in a
Soxlet apparatus and extracted with AcOEt for 2 h. The solution
was concentrated until it became turbid. The precipitate that
formed upon cooling was filtered off and dried. The yield of
yellowꢀbrown crystals was 0.20 g (85%), m.p. 262—264 °C (from
a mixture of benzene and light petroleum).
1H NMR (CDCl3), δ: 4.03 (s, 3 H, Me); 7.60 (m, 10 H,
2 Ph); 7.63 and 8.32 (both d, 1 H each, H(10), H(9), J1 = J2 =
9.4 Hz); 7.73 and 8.60 (both d, 1 H each, H(4), H(5), J1 = J2 =
9.4 Hz); 7.88 (s, 1 H, H(7)). MS, m/z (Irel (%)): 387 [M + 1] (7),
386 [M] (26), 357 [M – H2C=NH] (44). Found (%): C, 83.82;
H, 4.81; N, 7.37. C27H18N2O. Calculated (%): C, 83.92;
H, 4.69; N, 7.25.
B. Benzalacetophenone (0.27 g, 1.3 mmol) was added
portionwise with stirring to a mixture of 1ꢀmethylperimidone
(7) (0.20 g, 1 mmol) and PPA (5 g), which was heated to 65 °C,
during 15 min. Then the reaction mixture was stirred at 65—70 °C
for 1.5 h, poured into cold water (50 mL), made alkaline (pH ≈ 8)
with a solution of NH3, and extracted with AcOEt (3Ѕ30 mL).
The solution was dried with Na2SO4, filtered, concentrated unꢀ
til the it became turbid, and cooled. The precipitate that formed
was separated by filtration and dried. The yield was 0.12 g (30%),
m.p. 262—264 °C (from a mixture of benzene and light petroꢀ
leum). The specimens of 6a prepared according to procedures A
and B did not give a melting point depression.
1ꢀEthylꢀ6,8ꢀdiphenylꢀ1,3ꢀdiazapyrenium iodide (2d). The
yield was 90%. Red crystals, m.p. 273—274 °C. 1H NMR
(DMSOꢀd6), δ: 1.71 (t, 3 H, Me, J = 7.1 Hz); 5.20 (q, 2 H, CH2,
J = 7.1 Hz); 7.65 (m, 6 H, mꢀ and pꢀH Ph); 7.82 (m, 4 H,
оꢀH Ph); 8.58 (s, 1 H, H(7)); 8.60 and 9.14 (both d, 1 H each,
H(4), H(5), J1 = J2 = 9.4 Hz); 8.87 and 9.19 (both d, 1 H each,
H(10), H(9), J1 = J2 = 9.7 Hz); 10.20 (s, 1 H, H(2)). Found (%):
C, 65.54; H, 4.17; N, 5.38. C28H21IN2. Calculated (%): C, 65.64;
H, 4.13; N, 5.47.
1ꢀBenzylꢀ6,8ꢀdiphenylꢀ1,3ꢀdiazapyrenium chloride (2e). The
yield was 34%. Yellow crystals, m.p. 192—194 °C. 1H NMR
(DMSOꢀd6), δ: 6.45 (s, 2 H, CH2); 7.40—7.49 (m, 5 H,
C6H5CH2); 7.70—7.84 (m, 10 H, 2 Ph); 8.56 (s, 1 H, H(7));
8.65 and 9.18 (both d, 1 H each, H(10), H(9), J1 = J2 = 9.4 Hz);
8.71 and 9.15 (both d, 1 H each, H(4), H(5), J1 = J2 = 9.4 Hz);
10.36 (s, 1 H, H(2)). Found (%): C, 82.12; H, 4.73; N, 5.87.
C33H23ClN2. Calculated (%): C, 82.06; H, 4.80; N, 5.80.
1ꢀAllylꢀ6,8ꢀdiphenylꢀ1,3ꢀdiazapyrenium bromide (2f). The
yield was 58%. Yellow crystals, m.p. 204—206 °C. 1H NMR
(CDCl3), δ: 5.41 and 5.45 (both br.d, 1 H each, CH2—CH=CH2,
Jcis = 9.8 Hz, Jtrans = 16.2 Hz); 6.35 (m, 1 H, CH2—CH=CH2);
6.43 (m, 2 H, CH2—CH=CH2); 7.65—7.68 (m, 10 H, 2 Ph);
8.47 (s, 1 H, H(7)); 8.49 and 9.12 (both d, 1 H each, H(4), H(5),
J1 = J2 = 9.4 Hz); 8.98 and 9.28 (both d, 1 H each, H(10), H(9),
J1 = J2 = 9.4 Hz); 10.29 (s, 1 H, H(2)). Found (%): C, 72.82;
H, 4.31; N, 5.67. C29H21BrN2. Calculated (%): C, 72.96;
H, 4.43; N, 5.87.
1,2ꢀDimethylꢀ6,8ꢀdiphenylꢀ1,3ꢀdiazapyrenium iodide (2g).
The yield was 50%. Yellowꢀbrown crystals, m.p. 254—256 °C.
1H NMR (DMSOꢀd6), δ: 3.34 (s, 3 H, C(2)Me); 4.60 (s, 3 H,
NMe); 7.71—7.84 (m, 10 H, 2 Ph); 8.47 and 9.07 (both d,
1 H each, H(4), H(5), J1 = J2 = 9.0 Hz); 8.51 (s, 1 H, H(7));
8.85 and 9.14 (both d, 1 H each, H(10), H(9), J1 = J2 = 9.8 Hz).
Found (%): C, 65.74; H, 4.31; N, 5.58. C28H21IN2. Calcuꢀ
lated (%): C, 65.64; H, 4.13; N, 5.47.
1ꢀMethylꢀ6,8ꢀdiphenylꢀ1,3ꢀdiazapyrenium perchlorate (2h).
A. Benzalacetophenone (0.30 g, 1.4 mmol) was added portionꢀ
wise with stirring to a mixture of 1ꢀmethylperimidine (3) (0.20 g,
1.1 mmol) and PPA (5 g), which was heated to 75 °C, during
30 min. Then the reaction mixture was stirred at the same temꢀ
perature for 1.5 h and poured into cold water (30 mL). The
precipitate that formed was half crystalline and half amorphous.
It was solidified in 30 min. Then the precipitate was separated by
filtration, dissolved in 60% HClO4 (20 mL) with heating, and
poured into cold water (50 mL). The precipitate of the salt that
formed was filtered off and washed with water until washings
became neutral. The product was dried and then refluxed with
AcOEt (20 mL) for 5 min to purify from soluble impurities.
After filtration, the yield was 0.36 g (73%), m.p. 286—288 °C.
B. Salt 2c (0.20 g) was dissolved in 60% HClO4 (10 mL) with
heating and the reaction mixture was poured into cold water
(30 mL). The precipitate that formed was filtered off, washed
with water until washings became neutral, and dried. The prodꢀ
1ꢀAllylꢀ6,8ꢀdiphenylꢀ1,3ꢀdiazapyrenꢀ2ꢀone (6b). An aqueous
solution of KOH (0.14 g, 2.4 mmol) and K3[Fe(CN)6] (0.40 g,
1.2 mmol) was added dropwise with stirring to a solution of
1ꢀallylꢀ6,8ꢀdiphenylꢀ1,3ꢀdiazapyrenium bromide (2f) (0.27 g,
0.6 mmol) in dioxane (10 mL) with heating to 80 °C during
10 min. Then the reaction mixture was stirred at the same temꢀ
perature for 1 h and extracted with AcOEt (3Ѕ30 mL). The
solution was concentrated to 20 mL and transferred to a chroꢀ
matographic column with silica gel. The yellow fraction was
eluted with AcOEt. Brown crystals were obtained in a yield of
0.07 g (32%), m.p. 178—180 °C (from a mixture of benzene and
light petroleum).
1H NMR (CDCl3), δ: 5.17 and 5.29 (both dd, 1 H each,
CH2—CH=CH2, both Jtrans = 15.7 Hz, both Jcis = 10.3 Hz,
both Jgem = 2.8 Hz); 5.23 (d, 2 H, CH2—CH=CH2, J = 5.3 Hz);
6.10 (m, 1 H, CH2—CH=CH2); 7.58—7.60 (m, 10 H, 2 Ph);
7.64 and 8.34 (both d, 1 H each, H(10), H(9), J1 = J2 = 9.4 Hz);
7.69 and 8.57 (both d, 1 H each, H(4), H(5), J1 = J2 = 9.4 Hz);
7.87 (s, 1 H, H(7)).
1H NMR (acetoneꢀd6), δ: 5.16—5.27 (m,
4 H,
CH2—CH=CH2); 6.13 (m, 1 H, CH2—CH=CH2); 7.51 and
8.58 (both d, 1 H each, H(10), H(9), J1 = J2 = 9.8 Hz);
7.60—7.75 (m, 10 H, 2 Ph); 7.87 (s, 1 H, H(7)); 7.98 and 8.31
(both d, 1 H each, H(4), H(5), J1 = J2 = 9.4 Hz). Found (%):
C, 84.62; H, 4.81; N, 6.47. C29H20N2O. Calculated (%):
C, 84.44; H, 4.89; N, 6.79.

Transformations of 1ꢀRꢀ1,3ꢀdiazapyrenium salts
Russ.Chem.Bull., Int.Ed., Vol. 51, No. 1, January, 2002
143
9. E. F. Lier, S. Hunig, and H. Quast, Angew. Chem., 1968,
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Received April 24, 2001;
in revised form September 10, 2001