1594
Russ.Chem.Bull., Int.Ed., Vol. 56, No. 8, August, 2007
Ryabova et al.
0.83 mmol) in dimethylformamide (7 mL). The mixture was
refluxed with stirring for 30 min. The hot precipitate was filtered
off, washed with dimethylformamide and methanol, and dried.
Compound 8а was obtained in a yield of 0.11 g.
A methanolic mother liquor was evaporated, and the residue
was subjected to column chromatography (SiO2, chloroform as
eluent) giving 3ꢀdimethylaminomethyleneaminoꢀ2ꢀcyanoꢀ9ꢀoxoꢀ
9Нꢀpyrrolo[1,2ꢀа]indole (4) (0.01 g, 4.5%), m.p. 244—245 °С
(cf. Ref. 1: m.p. 244—245 °С).
11ꢀBenzylꢀ1,11ꢀdihydroꢀ4Нꢀpyrimido[5´,4´:5,6]pyriꢀ
do[3,2ꢀb]indolꢀ4ꢀone (8b) was synthesized from benzylaminoꢀ
dieneamine 1b (0.23 g, 0.73 mmol) and DMF acetal 8a (0.22 mL,
1.46 mmol) similarly to compound 8а. Compound 8b was obꢀ
tained in a yield of 0.05 g. After cooling of the mother liquor, an
additional amount (0.05 g) of the same substance was obtained.
The total yield of compound 8b was 0.1 g.
(10 mL). The resulting solution was clarified with active carbon,
filtered, and evaporated to dryness. The residue was triturated
with acetone, and the precipitate was filtered off and washed
with acetone. Chlorides 9b and 9d were obtained in yields of
0.07 g and 0.068 g, respectively.
11ꢀ(4ꢀMethoxyphenyl)ꢀ1,6ꢀdihydroꢀ4ꢀoxoꢀ4Нꢀpyrimiꢀ
do[5´,4´:5,6]pyrido[3,2ꢀb]indoliumꢀ11 chloride (9с). A saturated
solution of HCl (0.1 mL) in EtOAc was added to a suspension of
compound 8c (0.06 g, 0.18 mmol) in methanol (2 mL). A soluꢀ
tion with immediate precipitation was formed. The precipitate
was filtered off and washed with methanol and acetone. Chloꢀ
ride 9с was obtained in a yield of 0.05 g.
References
1. S. Yu. Ryabova, L. M. Alekseeva, E. A. Lisitsa, N. S.
Masterova, S. S. Kiselev, M. I. Evstratova, andV. G. Granik,
Izv. Akad. Nauk, Ser. Khim., 2006, 2186 [Russ. Chem. Bull.,
Int. Ed., 2006, 55, 2271].
2. S. Yu. Ryabova, Yu. I. Trofimkin, L. M. Alekseeva,
I. F. Kerbnikova, G. Ya. Shvarts, and V. G. Granik,
Khim.ꢀFarm. Zh., 1995, No. 9, 2 [Pharm. Chem. J., 1995,
No. 9 (Engl. Transl.)].
11ꢀ(4ꢀMethoxyphenyl)ꢀ1,11ꢀdihydroꢀ4Нꢀpyrimiꢀ
do[5´,4´:5,6]pyrido[3,2ꢀb]indolꢀ4ꢀone (8с) was synthesized from
4ꢀmethoxyphenylaminodieneamine 1с (0.5 g, 1.5 mmol) and
DMF acetal (0.45 mL, 3 mmol) similarly to compound 8а.
Compound 8с was obtained in a yield of 0.12 g. The
mother liquor was evaporated, and the residue subjected to
column chromatography (SiO2, chloroform as eluent) gave
3ꢀ(4ꢀmethoxyphenyl)aminoꢀ2ꢀcyanoꢀ9ꢀoxoꢀ9Нꢀpyrrolo[1,2ꢀа]ꢀ
indole (5с) (0.01 g, ~5%), m.p. 220—225 °С, molecular weight
315. MS (EI), m/z Irel (%): 315 [M]+ (100), 300 [M – Me]+
(78), 272 [M – CONH]+ (15). 1Н NMR (DMSOꢀd6), δ: 3.74 (s,
3 Н, ОМе); 6.93, 7.15 (both m, 2 Н each, С6Н4), 7.32 (s, 1 Н,
Н(1)); 7.29, 7.60 (both m, 1 Н each, 3 Н, Н(6)—Н(8)); 9.29
(br.s, 1 Н, NH). We failed to obtain compound 5с in the anaꢀ
lytically pure form. н
11ꢀ(4ꢀNitrophenyl)ꢀ1,11ꢀdihydroꢀ4Нꢀpyrimido[5´,4´:5,6]ꢀ
pyrido[3,2ꢀb]indolꢀ4ꢀone (8d). DMF acetal (0.14 mL, 0.1 mmol)
was added to a solution of 2ꢀaminoꢀ3ꢀcarbamoylꢀ1ꢀ(4ꢀnitroꢀ
phenyl)ꢀ1Нꢀpyrido[3,2ꢀb]indole8 (10) (0.16 g, 0.46 mmol) in
dimethylformamide (4 mL). The mixture was refluxed with stirꢀ
ring for 1 h. The hot precipitate was filtered off, washed with
DMF and methanol, and dried. Compound 8d was obtained in a
yield of 0.11 g.
11ꢀ(Methyl)ꢀ1,6ꢀdihydroꢀ4ꢀoxoꢀ4Нꢀpyrimido[5´,4´:5,6]ꢀ
pyrido[3,2ꢀb]indoliumꢀ11 chloride (9а). A saturated solution of
HCl (0.4 mL) in ethyl acetate was added to a suspension of
compound 8а (0.11g) in methanol (20 mL), and the mixture was
heated to boiling. The solution formed was filtered and cooled.
The precipitate that formed was filtered off and washed with
methanol and acetone. Chloride 9а was obtained in a yield
of 0.09 g.
11ꢀ(Benzyl)ꢀ and 11ꢀ(4ꢀnitrophenyl)ꢀ1,6ꢀdihydroꢀ4ꢀoxoꢀ4Нꢀ
pyrimido[5´,4´:5,6]pyrido[3,2ꢀb]indoliumꢀ11 chlorides (9b,d).
A saturated solution of HCl (0.2 mL) in EtOAc was added to a
suspension of compound 8b or 8d (0.3 mmol) in methanol
3. S. Yu. Ryabova, L. M. Alekseeva, and V. G. Granik,
Khim.ꢀFarm. Zh., 1996, No. 9, 29 [Pharm. Chem. J., 1996,
30, No. 9, 579 (Engl. Transl.)].
4. S. Yu. Ryabova, L. M. Alekseeva, E. A. Lisitsa, A. S.
Shashkov, V. V. Chernyshev, G. B. Tikhomirova, M. S.
Goizman, and V. G. Granik, Izv. Akad. Nauk, Ser. Khim.,
2001, 1379 [Russ. Chem. Bull., Int. Ed., 2001, 50, 1449].
5. N. A. Lantsetti, S. Yu. Ryabova, L. M. Alekseeva, A. S.
Shashkov, and V. G. Granik, Izv. Akad. Nauk, Ser. Khim.,
2001, 470 [Russ. Chem. Bull., Int. Ed., 2002, 51, 506].
6. J. Elguero, C. Marzio, A.R. Katritzky, P. Lindo, The
Tautumerism of Heterocycles, Adv. in Heterocycl. Chem.
Supplement 1, Acad. Press, New York—San Francisco—Lonꢀ
don, 1976, 127.
7. Y. Hagiwara, M. Kurihara, and N. Yoda, Tetrahedron, 1969,
25, 783.
8. S. Yu. Ryabova, L. M. Alekseeva, and V. G. Granik, Khim.
Geterotsikl. Soedin., 2000, 362 [Chem. Heterocycl. Compd.,
2000, 36, 301 (Engl. Transl.)].
9. E. L. Eliel, Stereochemistry of Carbon Compounds, 1962,
McGrawꢀHill Book Company, Inc., New York—San Franꢀ
cisco—Toronto—London, 1962.
10. V. G. Granik, Usp. Khim., 1982, 51, 207 [Russ. Chem. Rev.,
1982, 51 (Engl Transl.)].
Received February 14, 2007