1038
Russ.Chem.Bull., Int.Ed., Vol. 56, No. 5, May, 2007
Golovko et al.
Table 5. Yields, melting points, and elemental analysis data for
compounds 3, 10a,b, 11a,b, 12, 14a,b, 15, 16a,b, 17, 19, 20a—d,
21, and 24
with ether. The resulting solution was concentrated to 1/3 of the
initial volume and cooled and the precipitate of compound 12
that formed was filtered off.
2ꢀDicyanomethylideneꢀ3ꢀdimethylaminomethylideneꢀ1,2,3,4ꢀ
tetrahydroquinoline (14a). A mixture of compound 10a (0.58 g,
3 mmol) and acetal 2 (0.53 g, 3.6 mmol) was stirred in toluene
(15 mL) at 90 °C for 30 min. Then an additional portion of
acetal 2 (0.3 g) was added and stirring was continued for 40 min.
The reaction mixture was cooled to 0 °C and the precipitate
of quinoline 14a that formed was filtered off. 13C NMR
(DMSOꢀd6), δ: 26.7 (C(4)); 38.6 (C(2´)); 43.8 (NMe2); 89.6
(C(3)); 117.1, 123.9, 127.3, 127.8 (C(5)—C(8)); 120.1 (CN);
124.8 (C(4a)); 136.0 (C(8a)); 153.3 (C(3´)); 164.1 (C(2)).
2ꢀDicyanomethylideneꢀ3ꢀdimethylaminomethylideneꢀ1Hꢀ
2,3,4,5ꢀtetrahydrobenz[b]azepine (14b). A mixture of compound
10b (1.04 g, 5 mmol), acetal 2 (5 mL), and a catalytic amount of
piperidine was heated at 80—90 °C for 30 min. The reaction
mixture was concentrated, the residue was successively trituꢀ
rated with light petroleum and ether—ethyl acetate, and the
precipitate of benzazepine 14b was filtered off.
2ꢀ{1ꢀCyanoꢀ1ꢀ[(dimethylamino)methylideneaminocarboꢀ
nyl]methylidene}ꢀ1,2,3,4ꢀtetrahydroquinoline (15). A mixture of
compound 11a (2.6 g, 12.2 mmol) and acetal 2 (2.14 g,
14.6 mmol) was refluxed in methanol (30 mL) for 1 h and then
with an additional portion of acetal 2 (0.5 g) for 2 h. The reacꢀ
tion mixture was filtered and cooled to ~15 °C. The precipitate
of quinoline 15 that formed was filtered off.
Hydrolysis of compound 15. Compound 15 (0.15 g, 0.7 mmol)
was refluxed in water (20 mL) for 30 min and filtered. On coolꢀ
ing, the precipitate of compound 11a that formed was filtered off.
Extraction from the aqueous mother liquor with chloroform
gave an additional crop of compound 11a.
4ꢀCyanoꢀ3ꢀoxoꢀ2,3,5,10ꢀtetrahydrobenzo[b][1,6]naphthyriꢀ
dine (16a). A. A mixture of compound 14a (9.77 g, 31.1 mmol)
and glacial acetic acid (115 mL) was stirred at 85—90 °C for 4 h.
On cooling, the precipitate of compound 16a was filtered off
and washed with water and isopropyl alcohol.
Comꢀ Yield
M.p./°C
(solvent)
Found
Calculated
Molecular
formula
(%)
N
poꢀ
(%)
und
C
H
3
22
90
91
97
90
23
67
34
52
83
202—205
(AcOEt)
71.19 7.20 13.74 C12H14N2O
71.26 6.98 13.85
10а
10b
11a
11b
12
233—234
(PriOH)
73.90 4.61 21.45 C12H9N3
73.83 4.65 21.53
229—230
(MeOH)
217—220a
(ЕtOH)
74.64 5.51 20.37 C13H11N3
74.62 5.30 20.08
67.37 5.20 19.48 C12H11N3O
67.59 5.20 19.71
160—165
(PriOH)
68.53 6.00 18.07 C13H13N3O
68.70 5.77 18.49
88—92
(Et2O)
69.50 6.00 11.32 C14H14N2O2
69.40 5.83 11.56
14a
14b
15
226—229
(PriOH)
72.00 5.67 22.44 C15H14N4
71.98 5.64 22.38
138—142
(PriOH)
72.43 6.45 20.98 C16H16N4
72.70 6.10 21.20
168—172
(PriOH)
66.86 6.02 20.80 C15H16N4O
67.14 6.01 20.88
16ab
>270
68.59 4.33 18.73 C13H9N3O•
(DMF—H2O, 68.56 4.21 18.75 •0.25 H2O
1 : 1)
16b
81
>270
70.94 4.77 17.75 C14H11N3O
(DMF—H2O, 70.87 4.67 17.71
1 : 1)
17
76
91
91
65
52
228—230
(MeCN)
245—249a
(MeCN)
70.86 4.68 17.64 C14H11N3O
70.87 4.67 17.71
B. Compound 15 (0.06 g) was heated at 185—190 °C for
45 min. The reaction mixture was triturated with isopropyl alcoꢀ
hol and the precipitate of quinolone 16a was filtered off.
4ꢀCyanoꢀ3ꢀoxoꢀ2Hꢀ3,5,10,11ꢀtetrahydrobenzo[ f ]pyriꢀ
do[4,3ꢀb]azepine (16b) was obtained analogously from comꢀ
pound 14b (method A, 95—100 °C, 4.5 h).
19 c
20a
20b
20c
64.44 3.42 17.47 C13H8ClN3
64.61 3.34 17.39
216—219
(MeCN)
76.43 5.32 18.21 C20H16N4
76.90 5.16 17.94
154—156
(AcOEt)
71.62 5.88 14.00 C23H22N4O2
71.48 5.74 14.50
4ꢀCyanoꢀ3ꢀmethoxyꢀ5,10ꢀdihydrobenzo[b][1,6]naphthyriꢀ
dine (17). Compound 14a (0.625 g, 2.5 mmol) was refluxed for
1.5 h in a methanolic solution of sodium methoxide prepared
from metallic sodium (0.06 g) and methanol (10 mL). On coolꢀ
108—110
(aqueous
45% PriOH)
70.92 7.15 21.75 C19H23N5
71.00 7.21 21.79
ing, the precipitate of compound 17 was filtered off. 13C NMR
1
(DMSOꢀd6), δ: 26.4 (split t, C(10)); 54.2 (q, OMe, JC,H
=
20d
21
53
59
90
126—129
(heptane)
260—263a
(МеОН)
73.26 6.34 20.02 C17H18N4
73.35 6.52 20.13
147.3 Hz); 77.5 (s, C(4)); 110.4 (m, C(10a)); 114.5 (s, CN);
120.2 (m, C(9a)); 116.2, 123.1, 127.6, 129.8 (C(6)—C(9)); 137.0
(t, C(5a)); 148.6 (dt, C(1), 1JC,H = 178.5 Hz); 150.6 (d, C(4a));
164.2 (m, C(3)).
3ꢀChloroꢀ4ꢀcyanoꢀ5,10ꢀdihydrobenzo[b][1,6]naphthyridine
(19). A mixture of compound 16a (7.2 g, 32.3 mmol), triethylꢀ
amine hydrochloride (3.82 g, 27.3 mmol), and POCl3 (65 mL)
was refluxed for 6 h. On cooling, the precipitate of compound 19
was filtered off and washed successively with water, aqueous
K2CO3, again water, and isopropyl alcohol.
70.10 4.49 25.35 C13H10N4
70.25 4.54 25.21
24
252—254
(MeCN)
69.27 5.35 25.00 C16H15N5
69.29 5.45 25.25
a Decomp.
b Found (%): H2O, 1.83. Calculated (%): H2O, 1.98.
c Found (%): Cl, 14.72. Calculated (%): Cl, 14.67.