864
Russ.Chem.Bull., Int.Ed., Vol. 51, No. 5, May, 2002
Borovlev et al.
7.35 and 7.63 (both d, 1 H each, —CH=CH—CO, Jtrans
=
115.94 (1 C); 116.88 (1 C); 121.74 (1 C); 121.83 (1 C); 123.27
(1 C); 123.41 (1 C); 130.59 (1 C); 131.67 (1 C); 135.97 (1 C);
152.89 (1 C); 154.96 (1 C); 157.71 (1 C—OH). Found (%):
C, 76.48; H, 3.59; N, 12.62. C14H8N2O. Calculated (%):
C, 76.35; H, 3.66; N, 12.72.
B. 6(7)ꢀCinnamoylperimidine (3a) (0.3 g, 1 mmol) was
added with stirring to a mixture of AlBr3 (1.34 g, 5 mmol) and
dichloroethane (5 mL) at ∼20 °C. Then the mixture was stirred
for 30 min. The subsequent isolation was carried out according
to the procedure A. The yield was 0.08 g (36%).
C. 6(7)ꢀ(pꢀBromocinnamoyl)perimidine (3b) (0.38 g,
1 mmol) was added with stirring to a mixture of AlBr3 (1.34 g,
5 mmol) and dichloroethane (5 mL) at ∼20 °C. Then the mixꢀ
ture was stirred for 30 min. The subsequent isolation was carried
out according to the procedure A. The yield was 0.13 g (60%).
D. 6(8)ꢀOxoꢀ8(6)ꢀphenylꢀ1,6,7,8ꢀtetrahydroꢀ1,3ꢀdiazaꢀ
pyrene (4a) (0.30 g, 1 mmol) was added with stirring to a
mixture of AlBr3 (0.80 g, 3 mmol) and dichlroethane (5 mL) at
∼20 °C. Then the mixture was stirred for 30 min. The subseꢀ
quent isolation was carried out according to the procedure A.
The yield was 0.12 g (55%).
16.0 Hz); 7.39 (br.dd, 1 H, H(8), J8—9 = 7.0 Hz, J8—7 = 8.2 Hz);
7.46 and 7.54 (both d, 2 H each, pꢀBrPh, J = 8.8 Hz); 8.25 (d,
1
1 H, H(7), J7—8 = 8.2 Hz). H NMR (acetoneꢀd6), δ: 6.58 and
8.08 (both d, 1 H each, H(4), H(5), J = 8.3 Hz); 6.84 (br.d,
1 H, H(9), J9—8 = 8.3 Hz); 7.42 (t, 1 H, H(8), J8—9 = 8.3 Hz,
J8—7 = 8.3 Hz); 7.61 (s, 1 H, H(2)); 7.62 and 7.76 (both d,
1 H each, —CH=CH—CO, Jtrans = 15.4 Hz); 7.64 and 7.76
(both d, 2 H each, pꢀBrPh, J = 8.3 Hz); 8.51 (br.d, 1 H, H(7),
J7—8 = 8.8 Hz). Found (%): C, 63.72; H, 3.28; N, 7.29.
C20H13BrN2O. Calculated (%): C, 63.68; H, 3.47; N, 7.43.
6(8)ꢀOxoꢀ8(6)ꢀphenylꢀ1,6,7,8ꢀtetrahydroꢀ1,3ꢀdiazapyrene
(4a). The yield (%) and synthetic procedure (in parentheses)
were: 55% (A). Orange crystals with the m.p. 156—157 °C
(from ethyl acetate). 1H NMR (DMSOꢀd6), δ: 2.96 (m, 2 H,
CH2(7)), 4.49 (br.t, 1 H, H(8), J = 6.4 Hz); 6.51 and 7.77
(both br.d, 1 H each, H(4), H(5), J = 8.1 Hz); 6.65 and 7.05
(both d, 1 H each, H(9), H(10), J = 7.7 Hz); 7.15 and 7.30
(both m, 5 H, Ph); 7.61 (s, 1 H, H(2)); 11.36 (br.s, 1 H, NH).
Found (%): C, 80.69; H, 4.88; N, 9.24. C20H14N2O. Calcuꢀ
lated (%): C, 80.52; H, 4.73; N, 9.39.
pꢀBromophenylꢀ6(8)ꢀoxoꢀ8(6)ꢀ1,6,7,8ꢀtetrahydroꢀ1,3ꢀdiꢀ
azapyrene (4b). The yield (%) and synthetic procedure (in paꢀ
rentheses) were: 61% (A). Yellowꢀorange crystals with the m.p.
E. pꢀBromophenylꢀ6(8)ꢀoxoꢀ8(6)ꢀ1,6,7,8ꢀtetrahydroꢀ1,3ꢀ
diazapyrene (4b) (0.38 g, 1 mmol) was added with stirring to a
mixture of AlBr3 (0.80 g, 3 mmol) and dichloroethane (5 mL)
at ∼20 °C. Then the mixture was stirred for 30 min. The subseꢀ
quent isolation was carried out according to the procedure A.
Mixed samples, which were prepared according to different
procedures, did not give a melting point depression.
6ꢀHydroxyꢀ8ꢀphenylꢀ1,3ꢀdiazapyrene (12). A mixture of
6(8)ꢀoxoꢀ8(6)ꢀphenylꢀ1,6,7,8ꢀtetrahydroꢀ1,3ꢀdiazapyrene (4a)
(0.60 g, 2 mmol), chloranil (0.49 g, 2 mmol), and toluene
(20 mL) was refluxed for 1 h. The redꢀbrown precipitate that
formed was cooled, filtered off, washed with benzene, and dried.
The yield was 0.57 g (95%). Orange crystals with the m.p.
176—178 °C (with decomposition, from xylene). IR (Nujol
mulls), ν/cm–1: 1580, 1590, 1600 (ring, C=N), 3400 (OH).
1H NMR (CD3CN), δ: 7.60 (s, 1 H, H(7)); 7.64 (m, 5 H, Ph);
7.87 and 8.45 (both d, 1 H each, H(10), H(9), J = 9.4 Hz);
8.04 and 8.90 (both d, 1 H each, H(4), H(5), J = 9.4 Hz); 9.48
(s, 1 H, H(2)). 1H NMR (DMSOꢀd6), δ: 7.60 (m, 5 H, Ph);
7.61 (s, 1 H, H(7)); 7.88 and 8.38 (both d, 1 H each, H(10),
H(9), J = 9.2 Hz); 8.04 and 8.91 (both d, 1 H each, H(4),
H(5), J = 9.2 Hz); 9.51 (s, 1 H, H(2)). Found (%): C, 80.88;
H, 4.17; N, 9.56. C20H12N2O. Calculated (%): C, 81.07;
H, 4.08; N, 9.45.
1
168—170 °C (from ethyl acetate). H NMR (CD3CN), δ: 2.92
and 3.01 (both dd, 1 H each, CH2(7), Jgem = 15.8 Hz, Jcis
=
6.4 Hz, Jtrans = 6.8 Hz); 4.49 (dd, 1 H, H(8), Jcis = 6.4 Hz,
Jtrans = 6.8 Hz); 6.53 and 7.83 (both d, 1 H each, H(4), H(5),
J = 7.7 Hz); 6.67 and 7.05 (both d, 1 H each, H(10), H(9), J =
7.7 Hz); 7.09 and 7.43 (both d, 2 H each, pꢀBrPh, J = 8.1 Hz);
7.42 (s, 1 H, H(2)). Found (%): C, 63.50; H, 3.62; N, 7.33.
C20H13BrN2O. Calculated (%): C, 63.68; H, 3.47; N, 7.43.
6ꢀHydroxyꢀ1,3ꢀdiazapyrene (8). A. A solution of cinnamoyl
chloride or pꢀbromocinnamoyl chloride (2 mmol) in dichloroꢀ
ethane (1 mL) was added dropwise with stirring to a mixture of
dichloroethane (6 mL), AlBr3 (10 mmol), and perimidine
(2 mmol); care was taken that the reaction mixture did not
warm up above 30 °C. Then the mixture was stirred at ∼20 °C
for 30 min, carefully poured into water (10 mL), and cooled
after which light petroleum (10 mL) was added. The precipiꢀ
tate that formed was filtered off and dried. The dry mixture was
crushed, treated with a concentrated aqueous ammonia soluꢀ
tion (50 mL), and filtered. The filtrate was concentrated to
5 mL. The precipitate that formed was filtered off, dissolved in
ethanol (20 mL), and chromatographed through a small layer
of silica gel to remove inorganic impurities, and the orange
zone was eluted with alcohol. After evaporation of the solvent,
compound 8 was obtained from cinnamoyl chloride and
pꢀbromocinnamoyl chloride in 45% and 57% yields, respecꢀ
tively. The resulting samples did not give a melting point deꢀ
pression. Redꢀbrown crystals with the m.p. 303—305 °C (with
decomposition; from ethanol). IR (Nujol mulls), ν/cm–1: 1570,
1590, 1605 (ring, C=N); 3350 (OH). 1H NMR (DMFꢀd7), δ:
7.84 and 8.56 (both d, 1 H each, H(7), H(8), J = 8.3 Hz); 7.99
and 8.68 (both d, 1 H each, H(10), H(9), J = 8.2 Hz); 8.12 and
9.00 (both d, 1 H each, H(4), H(5), J = 9.3 Hz); 9.63 (s, 1 H,
H(2)); 12.05 (br.s, 1 H, OH). 1H NMR (CDCl3), δ: 7.58 and
8.30 (both d, 1 H each, H(7), H(8), J = 8.3 Hz); 8.05 and 8.46
(both d, 1 H each, H(10), H(9), J = 9.0 Hz); 8.15 and 8.92
(both d, 1 H each, H(4), H(5), J = 9.3 Hz); 9.67 (s, 1 H,
H(2)). 13C NMR (DMSOꢀd6), δ: 95.49 (1 C); 115.35 (1 C);
6ꢀpꢀBromocinnamoylꢀ1,3ꢀdimethylperimidone (14). A mixꢀ
ture of 6ꢀacetylꢀ1,3ꢀdimethylperimidone (0.25 g, 1 mmol) and
pꢀbromobenzaldehyde (0.2 g, 1.1 mmol) was dissolved in a
minimum amount of ethanol (∼15 mL). Then finely dispersed
KOH (0.10 g) was added and the mixture was refluxed for
10 min. The precipitate that formed upon cooling was filtered
off, washed with cold alcohol (5 mL), and dried. The yield was
0.35 g (83%). Yellow crystals with the m.p. 232—233 °C (from
1
a mixture of alcohol and benzene). H NMR (CDCl3), δ: 3.49
(s, 3 H, N(1)—CH3); 3.51 (s, 3 H, N(3)—CH3); 6.61 and 7.90
(both d, 1 H each, H(4), H(5), J = 8.2 Hz); 6.74 (br.d,
1 H, H(9), J = 7.6 Hz); 7.34 and 7.61 (both d, 1 H each,
—CH=CH—CO, J = 15.8 Hz); 7.45 and 7.52 (both d, 2 H each,
pꢀBrPh, J = 8.5 Hz); 7.57 (br.t, 1 H, H(8)); 8.25 (br.d, 1 H,
H(7), J = 8.6 Hz). Found (%): C, 62.48; H, 4.17; N, 6.60.
C22H17BrN2O2. Calculated (%): C, 62.72; H, 4.07; N, 6.65.