Heterocyclic analogs of pleiadiene: LXXIV. peri-cyclizations in the perimidine series. Synthesis of 1,3-diazapyrene derivatives

Article abstract of DOI:10.1023/B:RUJO.0000044557.95160.e5

Reactions of perimidines and perimidin-2-ones with α,β- unsaturated carbonyl compounds gave various 1,3-diazapyrene derivatives. Acylation of 1-methylperimidine, perimidin-2-one, and 1-methylperi-midin-2-one with cinnamoyl chloride in the presence of AlBr₃ is accompanied by peri-fusion at the 6,7-position and dearylation of the intermediate product. Under analogous conditions, 1,3-dimethyl-2,3-dihydroperimidine gave rise to 6-cinnamoyl-1,3-dimethyl-2,3-dihydroperimidine. Reactions of perimidin-2-ones with 1,3-di-phenyl-2-propenone in polyphosphoric acid resulted in peri-fusion at the 6,7-position, and with acetylacetone, at the 1,9-position.

Full text of DOI:10.1023/B:RUJO.0000044557.95160.e5

Russian Journal of Organic Chemistry, Vol. 40, No. 6, 2004, pp. 895–901. Translated from Zhurnal Organicheskoi Khimii, Vol. 40, No. 6, 2004,
pp. 932–937.
Original Russian Text Copyright © 2004 by Borovlev, Demidov, Aksenov, Pozharskii.
Heterocyclic Analogs of Pleiadiene:
LXXIV.* peri-Cyclizations in the Perimidine Series.
Synthesis of 1,3-Diazapyrene Derivatives
I. V. Borovlev1, O. P. Demidov1, A. V. Aksenov1, and A. F. Pozharskii2
1 Stavropol’State University, ul. Pushkina 1, Stavropol’, 355009 Russia
e-mail: biochem-org@stavsu.ru
2 Rostov State University, Rostov-on-Don, Russia
Received May 13, 2003
Abstract—Reactions of perimidines and perimidin-2-ones with α,β-unsaturated carbonyl compounds gave
various 1,3-diazapyrene derivatives. Acylation of 1-methylperimidine, perimidin-2-one, and 1-methylperi-
midin-2-one with cinnamoyl chloride in the presence of AlBr3 is accompanied by peri-fusion at the 6,7-position
and dearylation of the intermediate product. Under analogous conditions, 1,3-dimethyl-2,3-dihydroperimidine
gave rise to 6-cinnamoyl-1,3-dimethyl-2,3-dihydroperimidine. Reactions of perimidin-2-ones with 1,3-di-
phenyl-2-propenone in polyphosphoric acid resulted in peri-fusion at the 6,7-position, and with acetylacetone,
at the 1,9-position.
We previously developed several one-step proce-
dures for 6,7-peri-fusion to perimidines, which
allowed us to synthesize various derivatives of poorly
studied 1,3-diazapyrene [2–6]. In particular, the acyla-
tion of perimidine (I) with cinnamoyl and p-bromo-
cinnamoyl chlorides in the presence of excess AlBr3
occurred at the 6(7)-position and was accompanied by
intramolecular cyclization at the adjacent peri-position
and dearylation to afford 1,3-diazapyren-6-ol (III) in
both cases [4, 6] (Scheme 1).
Scheme 1.
2
3N
N1
4
5
10
9
R = H
R
6
8
N
N
PhCH=CHCOCl
AlBr3/C2H4Cl2
17 HO
7
III
Me
Me
N
N
N
N
I, II
+
R = Me
39%
O
O
IV
3 : 1
V
I, R = H; II, R = Me.
* For communication LXXIII, see [1].
1070-4280/04/4006-0895 © 2004 MAIK “Nauka/Interperiodica”

BOROVLEV et al.
896
Scheme 2.
O
O
O
O
R
Me
Me
HO
N
NH
N
NH
N
N
N
N
PhCH=CHCOCl
AlBr3
PhCH=CHCOCl
AlBr3
+
R = H
R = Me
29%
HO
HO
VIII, 64%
VI, VII
IX
X
VI, R = H; VII, R = Me.
Scheme 3.
Me
Me
Me
Me
Me
Me
N
N
N
N
N
N
PhCH=CHCOCl
AlBr3
PPA, 110°C
O
Ph
O
Ph
XI
XII
XIII
The goal of the present work was to examine the
above and other peri-cyclizations in the series of
1-substituted perimidines, perimidin-2-ones, and 2,3-
dihydroperimidines. 1-Methylperimidine (II) reacted
with cinnamoyl chloride in the presence of AlBr3 even
at room temperature, yielding a mixture of isomeric
1-methyl-1,6-dihydro-1,3-diazapyren-6-one (IV) and
1-methyl-1,8-dihydro-1,3-diazapyren-8-one (V) (see
Scheme 1); we failed to separate this mixture.
1
According to the H NMR data, isomer IV was the
major product. Analogous tandem reactions were
observed for 2,3-dihydro-1H-perimidin-2-one (VI) and
1-methylperimidin-2(1H)-one (VII). In the first case,
6(8)-hydroxy-1,2-dihydro-1,3-diazapyren-2-one (VIII)
Scheme 4.
O
O
R
Me
Ph
Me
Ph
N
N
N
N
O
PPA
MeI
X–
VI, VII
+
Ph
Ph
R = Me
Ph
Ph
XIVa, XIVb
XVIa, XVIb
O
Me
Me
O
N
N
(1) PPA; (2) HClO4
+
Ph
Ph
XV
XIV, R = H (a), Me (b); XVI, X = ClO4 (a), I (b).
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 6 2004

HETEROCYCLIC ANALOGS OF PLEIADIENE: LXXIV.
897
was formed, and in the second, a mixture of isomeric
6- and 8-hydroxy-1-methyl-1,2-dihydro-1,3-diazapyr-
en-2-ones IX and X at a ratio of 9:1 (according to
resulted in formation of a complex mixture of unstable
products.
Such difunctional 1,3-electrophiles as β-keto acids,
β-diketones, and acetylenic acids also seemed to be
promising reagents for 6,7-peri-fusion of perimidine.
However, in contrast to 1,3-dialkyl derivatives of peri-
midin-2-one, perimidine-2-thione, and 2,3-dihydro-
perimidine [7], perimidine (I) failed to react with ethyl
acetoacetate in PPA at 70–80°C, while at higher tem-
perature decomposition occurred. Compound I reacted
with aceylacetone in polyphosphoric acid only above
100°C to give 4(9)-acetylperimidine in a poor yield
[3]. The reaction of I with 3-phenylpropynoic acid in
PPA at 120°C gave previously described 8-phenyl-1,3-
diazapyren-6-ol (XVIII) [6]. Presumably, as in the
reactions with cinnamic acid [6, 11], the process
involves alkylation of perimidine (I) with ambident
phenylpropynoyl cation (pathway b in Scheme 6).
Alternative pathway a seems to be improbable
because of unfavorable geometric structure of inter-
mediate A.
1
the H NMR data; Scheme 2). However, the reaction
of 1,3-dimethyl-2,3-dihydro-1H-perimidine (XI) with
cinnamoyl chloride in the presence of AlBr3 stops at
the stage of formation of 6-cinnamoyl-1,3-dimethyl-
2,3-dihydro-1H-perimidine (XII) (Scheme 3). A prob-
able reason is formation of a stable complex with
AlBr3 at the nitrogen atom, which hampers subsequent
intramolecular alkylation of compound XII. The latter
underwent cyclization only at 110°C in polyphosphoric
acid (PPA), i.e., under the conditions corresponding to
the formation of ketone XIII from compound XI and
cinnamic acid [7].
Like perimidine [3], reactions of perimidin-2-ones
VI and VII with 1,3-diphenyl-2-propenone (chalcone)
in PPA resulted in 6,7-peri-cyclizations with formation
of 6,8-diphenyl-1,2-dihydro-1,3-diazapyren-2-one
(XIVa) and its N-methyl derivative XIVb, respec-
tively. The reaction of 1,3-dimethylperimidin-2-one
(XV) with chalcone was accompanied by aromatiza-
tion, leading to 1,3-dimethyl-6,8-diphenyl-2-oxo-2,3-
dihydro-1,3-diazapyrenium cation which was isolated
as perchlorate XVIa (Scheme 4). The latter was also
obtained by quaternization of XIVb with methyl
iodide, followed by exchange of iodide ion for ClO4–.
Unlike yellow–green perchlorate, iodide XVIb is dark
violet, presumably due to formation of an autocomplex
between the cation of XVI and iodide ion in crystal.
Such complexes are known to be formed from other
heteroaromatic cations [8].
Scheme 6.
I
a
b
N
NH
N
NH
On heating with aqueous alkali, salt XVIa under-
goes hydrolysis to give N,N'-dimethyl-9-amino-4,6-
diphenyl-1H-phenalen-1-imine (XVII) (for structural
analogs, see [9, 10]; Scheme 5). Compounds XIVa and
XIVb did not change under similar conditions.
HO
O
O
A
Scheme 5.
H
Me
Me
N
N
NaOH/H2O
XVIa
N
N
Ph
Ph
XVII
HO
Ph
The reaction of 1,3-dimethyl-2,3-dihydro-1H-peri-
midine (XI) with chalcone in polyphosphoric acid
XVIII
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 6 2004

BOROVLEV et al.
898
Scheme 7.
chloride in 1 ml of dichloroethane was added dropwise
under stirring to a mixture of 6 ml of dichloroethane,
2.67 g (10 mmol) of AlBr3, and 0.18 g (1 mmol) of
1-methylperimidine, maintaining the temperature
below 30°C. When the addition was complete, the
mixture was stirred for 30 min at room temperature,
carefully poured into 10 ml of water, and cooled, and
10 ml of petroleum ether was added. The precipitate
was filtered off, dried, ground with 0.5 g of silica gel,
and transferred to a chromatographic column charged
with a small amount of silica gel (d = 2 cm, h =
1.5 cm). The column was eluted with methanol to
obtain a yellow fraction. Removal of the solvent gave
0.15 g of a mixture of compounds IV and V as red–
brown crystals (yield 39%).
O
Me
7
5
6
N
MeCOCH2COMe
PPA
4
8
9
N
VI
3
2
Me
10
11
1
XIX, 87%
Unexpected results were obtained in the reaction of
perimidin-2-one (VI) with acetylacetone in PPA. This
reaction afforded 7,9-dimethyl-5H-pyrido[1,2,3-cd]-
perimidin-5-one (XIX) via 1,9-peri-fusion (Scheme 7).
Compound XIX is readily soluble in dilute mineral
acids, and it forms yellow–green perchlorate which is
insoluble in water. The latter is unstable: it decom-
poses on attempted recrystallization from alcohol.
Neutral base XIX is also fairly unstable. It undergoes
gradual tarring on storage, and heating of XIX in
aqueous alkali for a short time or stirring in alcoholic
alkali at room temperature leads to formation of
10-amino-2,4-dimethylbenzo[h]quinolin-10-amine
(XX) or its N-ethoxycarbonyl derivative XXI, respec-
tively, in a low yield (both reactions are accompanied
by strong tarring; Scheme 8). 1,3-Dimethyl-2,3-di-
hydro-1H-perimidin-2-one (XV) also readily reacted
with acetylacetone in PPA, but the product was a green
crystalline oligomer.
1
Compound IV. H NMR spectrum (DMSO-d6), δ,
ppm: 6.83 d (1H, 10-H), 7.16 d (1H, 4-H), 7.52 d
(1H, 8-H), 8.09 d (1H, 9-H), 8.23 d (1H, 5-H), 8.65 d
(1H, 7-H); J9,10 = 9.5, J4,5 = 8.2, J7,8 = 8.5 Hz; 8.60 s
(1H, 2-H).
1
Compound V. H NMR spectrum (DMSO-d6), δ,
ppm: 6.83 d (1H, 10-H), 7.34 d (1H, 6-H), 7.39 d
(1H, 4-H), 8.12 d (1H, 9-H), 8.22 d (1H, 5-H), 8.67 d
(1H, 7-H); J9,10 = 9.5, J6,7 = 8.2, J4,5 = 8.2 Hz; 8.56 s
(1H, 2-H).
6(8)-Hydroxy-1,2-dihydro-1,3-diazapyren-2-one
(VIII). Aluminum bromide, 2.67 g (10 mmol), was
added to 5 ml of dichloroethane, the mixture was
cooled to room temperature, and 0.184 g (1 mmol) of
perimidinone VI and 0.216 g (1.3 mmol) of cinnamoyl
chloride were added in succession. The reaction was
complete in 1 h. The mixture was carefully poured into
15 ml of water, the remaining dichloroethane was
distiled off, and the precipitate was filtered off and
treated with several portions of boiling isopropyl
alcohol. The solvent was distilled off to obtain 0.15 g
(64%) of compound VIII as red–brown crystals with
mp 298–300°C (decomp., from isopropyl alcohol).
1H NMR spectrum (DMSO-d6), δ, ppm: 6.47 d (1H,
7-H), 6.71 d (1H, 10-H), 6.86 d (1H, 4-H), 7.67 d (1H,
8-H), 7.78 d (1H, 9-H), 8.32 d (1H, 5-H); J7,8 = 9.2,
EXPERIMENTAL
1
The H NMR spectra were recorded on a Bruker
WP-200 spectrometer with TMS as internal reference;
the signals were assigned using the double resonance
technique. The mass spectra were obtained on
an MKh-1321A instrument. The progress of reactions
and the purity of products were monitored by TLC on
Silufol UV-254 plates.
1-Methyl-1,6-dihydro-1,3-diazapyren-6-one (IV)
and 1-methyl-1,8-dihydro-1,3-diazapyren-8-one (V).
A solution of 0.216 g (1.3 mmol) of cinnamoyl
Scheme 8.
Me
O
Me
NH2
N
EtO
NH
N
KOH, H2O
KOH, EtOH
XIX
Me
Me
XX
XXI
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 6 2004

HETEROCYCLIC ANALOGS OF PLEIADIENE: LXXIV.
899
J9,10 = 8.2, J4,5 = 8.7 Hz. Found, %: C 71.32; H 3.36;
N 11.72. C14H8N2O2. Calculated, %: C 71.18; H 3.41;
N 11.86.
1,3-Dimethyl-8-phenyl-1,2,3,6,7,8-hexahydro-
1,3-diazapyren-6-one (XIII). A solution of 0.33 g
(1 mmol) of 1,3-dimethyl-6-cinnamoyl-2,3-dihydro-
1H-perimidine (XII) in 5 g of polyphosphoric acid was
stirred for 1.5 h at 110°C. The mixture was cooled
to 85°C, poured under vigorous stirring into ~30 ml
of cold water, and neutralized with aqueous ammonia
(pH ≈ 8). The precipitate was filtered off, washed with
water, and dried. The product was treated with 3 ml
of ethyl acetate, and the solution and the undissolved
material were applied to a column charged with Al2O3.
The column was eluted with benzene to isolate
a yellow fraction. Removal of the solvent from the
latter gave an oily substance which crystallized on
grinding with diethyl ether. Yield 0.23 g (69%). Yellow
crystals, mp 143–144°C (from benzene–petroleum
ether) (cf. [7]).
6-Hydroxy-1-methyl-1,2-dihydro-1,3-diaza-
pyren-2-one (IX) and 8-hydroxy-1-methyl-1,2-di-
hydro-1,3-diazapyren-2-one (X). Aluminum bromide,
2.67 g (10 mmol), was added to 5 ml of dichloro-
ethane, the mixture was cooled to room temperature,
and 0.198 g (1 mmol) of 1-methylperimidinone VII
and 0.216 g (1.3 mmol) of cinnamoyl chloride were
added in succession. The reaction was complete in 1 h.
The mixture was carefully poured into 15 ml of water,
the remaining dichloroethane was distilled off, and the
precipitate was filtered off and treated with several
portions of boiling isopropyl alcohol. The extract was
evaporated to dryness to obtain 0.09 g (29%) of
a mixture of compounds IX and X at a ratio of 9:1
(according to the 1H NMR data); red–brown crystals.
6,8-Diphenyl-1,2-dihydro-1,3-diazapyren-2-one
(XIVa). A mixture of 0.74 g (4 mmol) of perimidinone
VI, 1.66 g (8 mmol) of 1,3-diphenyl-2-propenone, and
7 g of polyphosphoric acid was stirred for 6 h at
65–70°C. The mixture was poured into water and
neutralized with aqueous ammonia to pH ≈ 8, and the
precipitate was filtered off, washed with water, dried,
and dissolved in 30 ml of ethanol on heating. The
solution was heated at the boiling point with addition
of charcoal, evaporated by half, and poured while hot
into 50 ml of water. After 2 h, the precipitate was
filtered off, washed with ethyl acetate, and dried. Yield
0.3 g (20%). Yellow crystals, mp 246–248°C (from
ethanol–ethyl acetate). 1H NMR spectrum (DMSO-d6–
CCl4), δ, ppm: 7.40–7.65 m (12H, 4-H, 10-H, 2C6H5),
7.76 s (1H, 7-H), 8.33 d (2H, 5-H, 9-H, J4,5 = 9.4,
1
Compound IX. H NMR spectrum (DMSO-d6), δ,
ppm: 6.56 d (1H, 7-H), 6.86 d (1H, 4-H), 6.88 d (1H,
10-H), 7.74 d (1H, 8-H), 7.92 d (1H, 9-H), 8.31 d (1H,
5-H); J7,8 = 8.5, J4,5 = 8.9, J9,10 = 8.2 Hz.
1
Compound X. H NMR spectrum (DMSO-d6), δ,
ppm: 6.46 d (1H, 7-H), 6.73 d (1H, 4-H), 7.13 d (1H,
10-H), 7.74 d (1H, 8-H), 7.79 d (1H, 5-H), 8.53 d (1H,
9-H); J7,8 = 8.1, J4,5 = 8.2, J9,10 = 8.5 Hz.
6-Cinnamoyl-1,3-dimethyl-2,3-dihydro-1H-peri-
midine (XII). Aluminum bromide, 2.67 g (10 mmol),
was added to 5 ml of dichloroethane, the mixture was
cooled to room temperature, and 0.197 g (1 mmol) of
1,3-dimethyl-2,3-dihydro-1H-perimidine and 0.216 g
(1.3 mmol) of cinnamoyl chloride were added in
succession. The reaction was complete in 30 min. The
mixture was carefully poured into 15 ml of water and
extracted with benzene (50 ml). The extract was
washed with 10% aqueous ammonia, concentrated to
a volume of 3 ml, and applied to a column charged
with aluminum oxide. The column was eluted with
benzene to isolate a yellow fraction. Removal of the
solvent from the eluate gave 0.12 g (37%) of com-
pound XII as orange–red crystals, mp 78–80°C (from
octane). 1H NMR spectrum (DMSO-d6), δ, ppm: 2.94 s
and 3.07 s (3H each, NMe), 4.31 s (2H, CH2), 6.55 d
J
9,10 = 9.4 Hz), 12.52 br.s (1H, NH). Found, %:
C 83.68; H 4.55; N 7.29. C26H16N2O. Calculated, %:
C 83.85; H 4.33; N 7.52.
1-Methyl-6,8-diphenyl-1,2-dihydro-1,3-diaza-
pyren-2-one (XIVb). A mixture of 0.20 g (1 mmol)
of 1-methylperimidinone VII, 0.27 g (1.3 mmol) of
1,3-diphenyl-2-propenone, and 5 g of polyphosphoric
acid was stirred for 1.5 h at 65°C. The mixture was
poured into 50 ml of water, neutralized with aqueous
ammonia to pH ≈ 8, and extracted with ethyl acetate
(3×30 ml). The extract was dried over sodium sulfate,
filtered, evaporated until it became turbid, and cooled.
The precipitate was filtered off and dried. Yield 0.12 g
(1H, 4-H, J4,5 = 8.2 Hz), 6.62 d (1H, 9-H, J8,9
7.9 Hz), 7.4 m (5H, C6H5), 7.41 d.d (1H, 7-H, J6,7
=
=
8.5, J7,8 = 7.9 Hz), 7.57 d (1H, =CH–, Jtrans = 15.6 Hz),
7.69 d (1H, =CHCO, Jtrans = 15.6 Hz), 8.11 d (1H, 5-H,
J4,5 = 8.2 Hz), 8.26 d (1H, 6-H, J6,7 = 8.5 Hz). Found,
%: C 79.86; H 6.93; N 8.46. C22H22N2O. Calculated,
%: C 79.97; H 6.71; N 8.48.
1
(30%), mp 262–264°C (from ethyl acetate). H NMR
spectrum (CDCl3), δ, ppm: 4.03 s (3H, NMe), 7.60 m
(10H, 2C6H5), 7.63 d (1H, 9-H, J9,10 = 9.4 Hz), 7.49 d
(1H, 5-H, J5,4 = 9.4 Hz), 7.88 s (1H, 7-H), 8.60 d (1H,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 6 2004

BOROVLEV et al.
900
4-H, J4,5 = 9.4 Hz), 8.32 d (1H, 10-H, J10,9 = 9.4 Hz),
10.29 s (1H, 2-H). Mass spectrum, m/z (Irel, %): 386
[M]+ (26), 387 [M + 1]+ (7), 357 [M – H2C=NH]+ (44).
Found, %: C 83.79; H 4.76; N 7.20. C27H18N2O. Cal-
culated, %: C 83.92; H 4.69; N 7.25.
0.27 g (72%), red crystals, mp 242–243°C (from
1
alcohol–benzene). H NMR spectrum (CDCl3), δ, ppm:
3.35 s (6H, 2Me), 7.18 d (2H, 2H, 8-H, J2(8),3(7)
=
9.4 Hz), 7.44 s (1H, 5-H), 7.50 m (10H, 2C6H5), 7.81 d
(2H, 3-H, 7-H, J3(7),2(8) = 9.4 Hz), 13.36 s (1H, NH).
Found, %: C 86.39; H 6.05; N 7.23. C27H22N2. Cal-
culated, %: C 86.60; H 5.92; N 7.48.
1,3-Dimethyl-2-oxo-6,8-diphenyl-1,2-dihydro-
1,3-diazapyrenium iodide (XVIb). A mixture of
0.38 g (1 mmol) of compound XIVb and 0.19 ml
(3 mmol) of methyl iodide in 20 ml of acetonitrile
was heated for 4 h under reflux. The solution was
evaporated to a volume of 3 ml, and 10–15 ml of
petroleum ether was added. An oily material separated
and slowly crystallized. It was separated from the
solution by decanting, ground (after solidification), and
heated in 20 ml of boiling ethyl acetate. The precipitate
was filtered off and washed with petroleum ether.
Yield 0.39 g (76%), dark violet crystals, mp 268–
270°C (from acetone). 1H NMR spectrum (DMSO-d6),
δ, ppm: 4.10 s (6H, 2NMe), 7.70 m (6H, m-H, p-H),
7.80 m (4H, o-H), 8.29 s (1H, 7-H), 8.37 d (2H, 4-H,
10-H), 8.97 d (2H, 5-H, 9-H), J4,5 = 9.3 Hz). Found, %:
C 63.35; H 3.95; N 5.58. C28H21N2IO. Calculated, %:
C 63.65; H 4.01; N 5.30.
8-Phenyl-1,3-diazapyren-6-ol (XVIII). A mixture
of 0.34 g (2 mmol) of perimidine (I), 0.44 g (3 mmol)
of 3-phenylpropynoic acid, and 5 g of polyphosphoric
acid was stirred for 3 h at 120°C. The mixture was
cooled to 80°C, poured into 30 ml of water, neutralized
with aqueous ammonia to pH ≈ 8, and extracted with
ethyl acetate (3×30 ml). The extract was evaporated
to a volume of 3 ml, and the precipitate was filtered
off. Yield 0.23 g (40%), orange crystals, mp 176–
178°C (decomp., from xylene). The product showed
no depression of the melting point on mixing with
a sample prepared as described in [6].
7,9-Dimethyl-5H-pyrido[1,2,3-cd]perimidin-5-
one (XIX). A mixture of 0.74 g (4 mmol) of perimidin-
2-one, 0.6 ml (6 mmol) of acetylacetone, and 7 g of
polyphosphoric acid was stirred for 5.5 h at 75–80°C.
The mixture was poured under vigorous stirring into
50 ml of water and filtered, the filtrate was neutralized
with aqueous ammonia to pH ~8–9, and the red
precipitate was filtered off, washed with water, and
dried. Yield 0.87 g (87%), red crystals, mp 146–147°C
(decomp., from isopropyl alcohol). The product was
relatively unstable, and it gradually darkened on
1,3-Dimethyl-2-oxo-6,8-diphenyl-1,2-dihydro-
1,3-diazapyrenium perchlorate (XVIa). a. A mixture
of 0.42 g (2 mmol) of 1,3-dimethylperimidinone XV,
0.64 g (3 mmol) of 1,3-diphenyl-2-propenone, and 6 g
of polyphosphoric acid was stirred for 4 h at 65–70°C.
The mixture was poured under vigorous stirring into
20 ml of 30% perchloric acid and then into 50 ml of
water, and the precipitate was filtered off and washed
with water. Yield 0.88 g (85%), yellow–green crystals,
mp 296–298°C (from alcohol).
1
storage. H NMR spectrum (CDCl3), δ, ppm: 2.92 s
and 3.44 s (3H each, 9-CH3, 7-CH3), 7.54 s (1H, 8-H),
7.58 br.d (1H, 1-H, J1,2 = 7.6 Hz), 7.68 br.d (1H, 3-H,
J3,2 = 8.0 Hz), 7.83 d (1H, 10-H, J10,11 = 9.2 Hz),
7.91 d.d (1H, 2-H, J2,1 = 7.6, J2,3 = 8.0 Hz), 7.97 d (1H,
11-H, J11,10 = 9.2 Hz). Mass spectrum, m/z (Irel, %):
248 [M]+ (100), 249 [M + 1]+ (40), 222 (28), 220 (76),
221 (38), 43 (87). Found, %: C 77.29; H 4.51; N 11.46.
C16H12N2O. Calculated, %: C 77.40; H 4.87; N 11.28.
b. A mixture of 0.2 g of iodide XVIb and 5 ml of
30% perchloric acid was stirred for 0.5 h at room tem-
perature. The precipitate was filtered off, thoroughly
washed with water, and dried. The yield was nearly
quantitative.
N,N'-Dimethyl-9-amino-4,6-diphenyl-1H-phena-
len-1-imine (XVII). A mixture of 0.52 g (1 mmol) of
perchlorate XVIa and 20 ml of a 10% solution of
sodium hydroxide was stirred for 10 min at the boiling
point. The mixture was cooled, and the precipitate was
filtered off, washed with water, dried, and treated with
10 ml of chloroform. The solution together with the
undissolved material was applied to a column charged
with ~50 g of Al2O3, and the column was eluted with
chloroform to collect the first orange–red fraction.
Removal of the solvent left a red oily substance which
crystallized on grinding with petroleum ether. Yield
10-Amino-2,4-dimethylbenzo[h]quinoline (XX).
A mixture of 0.25 g (1 mmol) of compound XIX and
10 ml of 10% aqueous sodium hydroxide was heated
for 10 min at the boiling point. The mixture was
cooled, and the brown precipitate was filtered off,
washed with water, and dried. Chloroform, 7 ml, was
added to the dry product, and the mixture was applied
to a chromatographic column charged with a small
amount of Al2O3. The column was eluted with chloro-
form to collect the first pale yellow fraction. Removal
of the solvent from the eluate left 0.04 g (19%) of
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 6 2004

HETEROCYCLIC ANALOGS OF PLEIADIENE: LXXIV.
901
compound XX. Yellow crystals, mp 282–283°C
(from benzene–petroleum ether). H NMR spectrum
7.7 Hz), 7.82 d (1H, 5-H, J5,6 = 9.3 Hz), 7.86 d (1H,
1
6-H, J6,5 = 9.3 Hz), 8.57 d.d (1H, 9-H, J9,8 = 7.7, J9,7
=
(CDCl3), δ, ppm: 2.61 s and 2.75 s (3H each, 2-Me,
2.2 Hz), 14.88 s (1H, NH···N). Found, %: C 73.69;
H 6.01; N 9.37. C18H18N2O2. Calculated, %: C 73.45;
H 6.16; N 9.52.
4-Me), 7.23 s (1H, 3-H), 7.56 br.d (1H, 7-H, J7,8
=
7.7 Hz), 7.70 d.d (1H, 8-H, J8,7 = 7.7, J8,9 = 8.3 Hz),
7.81 d (1H, 5-H, J5,6 = 9.3 Hz), 7.85 d (1H, 6-H, J6,5
=
9.3 Hz), 8.74 d.d (1H, 9-H, J9,8 = 8.3, J9,7 = 1.1 Hz),
15.02 s (1H, NH···N). Found, %: C 80.79; H 6.50;
N 12.34. C15H14N2. Calculated, %: C 81.05; H 6.35;
N 12.60.
REFERENCES
1. Borovlev, I.V., Demidov, O.P., and Pozharskii, A.F.,
Khim. Geterotsikl. Soedin., 2002, p. 1247.
2. Borovlev, I.V., Aksenov, A.V., and Pozharskii, A.F.,
Khim. Geterotsikl. Soedin., 1997, p. 1579.
3. Borovlev, I.V., Demidov, O.P., and Pozharskii, A.F.,
Khim. Geterotsikl. Soedin., 2002, p. 1109.
4. Demidov, O.P., Borovlev, I.V., and Pozharskii, A.F.,
10-Ethoxycarbonylamino-2,4-dimethylbenzo[h]-
quinoline (XXI). A mixture of 0.25 g (1 mmol) of
7,9-dimethyl-5H-pyrido[1,2,3-cd]perimidin-5-one
(XIX), 0.1 g of KOH, and 4 ml of ethanol was stirred
for 2 h at room temperature. The mixture was poured
into 30 ml of water, and the precipitate was filtered off,
washed with water, and dried. The dry product was
treated with 7 ml of chloroform, and the mixture was
applied to a chromatographic column charged with
a small amount of Al2O3. The column was eluted with
chloroform to collect the first pale yellow fraction.
Removal of the solvent from the eluate left 0.06 g
(21%) of compound XXI. Pale yellow crystals, mp 85–
Khim. Geterotsikl. Soedin., 2001, p. 1136.
5. Borovlev, I.V., Demidov, O.P., and Pozharskii, A.F.,
Khim. Geterotsikl. Soedin., 2002, p. 278.
6. Borovlev, I.V., Demidov, O.P., and Pozharskii, A.F., Izv.
Ross. Akad. Nauk, Ser. Khim., 2002, p. 794.
7. Borovlev, I.V. and Pozharskii, A.F., Khim. Geterotsikl.
Soedin., 1978, p. 833.
8. Feldman, M. and Winstein, S., Tetrahedron Lett., 1962,
p. 853.
1
86°C (from petroleum ether). H NMR spectrum
9. Neidlein, R. and Behzadi, Z., Chem.-Ztg., 1978,
(DMSO-d6), δ, ppm: 1.31 t (3H, CH3CH2, J = 7.2 Hz),
2.64 s and 2.66 s (3H each, 4-Me, 2-Me), 4.21 q (2H,
CH3CH2, J = 7.2 Hz), 7.37 s (1H, 3-H), 7.61 d (1H,
vol. 102, p. 150.
10. Franz, K.-D., Chem. Lett., 1979, p. 221.
11. Demidov, O.P., Borovlev, I.V., and Pozharskii, A.F.,
7-H, J7,8 = 7.7 Hz), 7.65 t (1H, 8-H, J8,7 = 7.7, J8,9
=
Khim. Geterotsikl. Soedin., 2001, p. 133.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 6 2004