3
02
Russ.Chem.Bull., Int.Ed., Vol. 67, No. 2, February, 2018
Sanin et al.
1
(
55%), m.p. 153—154 °C. H NMR (DMSOꢀd ), δ: 2.17 (s, 3 H,
3ꢀAcetylꢀ2ꢀ(3,4,5ꢀtrimethoxyphenyl)ꢀ2,3ꢀdihydropyrroloꢀ
6
CH ); 4.44 (d, 1 H, H(2), J = 7.7 Hz); 5.06 (d, 1 H, H(3),
J = 7.7 Hz); 5.40 (d, 1 H, H(6), J = 7.7 Hz); 5.72 (s, 1 H, H(10b));
[2,1ꢀa]isoquinolineꢀ1,1(10bH)ꢀdicarbonitrile (10f). The product
3
1
yield was 0.43 g (34%), m.p. 136—138 °C. H NMR (DMSOꢀd ),
6
6
7
.64 (d, 1 H, H(5), J = 7.7 Hz); 7.10 (d, 1 H, H(7), J = 7.5 Hz);
δ: 2.19 (s, 3H, CH CO); 3.70 (s, 3 H, CH ); 3.82 (s, 6 H,
3 3
.21 (m, 1 H, H(9)); 7.33 (m, 2 H, H(8), H(10)); 7.49 (m, 3 H,
2CH ); 4.39 (d, 1 H, H(2), J = 8.1 Hz); 5.09 (d, 1 H, H(3),
3
1
3
Ar); 7.60 (d, 2 H, Ar, J = 7.5 Hz). C NMR (DMSOꢀd ), δ:
2
1
J = 8.1 Hz); 5.42 (d, 1 H, H(6), J = 7.7 Hz); 5.68 (s, 1 H, H(10b));
6.63 (d, 1 H, H(5), J = 7.7 Hz); 6.87 (s, 2 H, Ar); 7.12 (d, 1 H,
H(7), J = 7.7 Hz); 7.22 (m, 1 H, H(9)); 7.32 (m, 2 H, H(8),
6
6.9, 50.0, 51.8, 68.4, 73.3, 98.7, 113.4, 123.3, 124.8, 125.9,
26.2, 128.6, 129.0, 129.1, 129.8, 132.5, 133.7, 135.4, 205.4.
H(10)). 1 C NMR (DMSOꢀd ), δ: 26.9, 50.0, 52.2, 56.1, 60.1,
3
Found (%): C, 77.82; H, 5.04; N, 12.35. C22H17N O. Calcꢀ
3
6
ulated (%): C, 77.86; H, 5.05; N, 12.38.
68.4, 73.1, 98.6, 106.2, 113.5, 123.3, 124.8, 126.0, 126.1, 129.1,
129.9, 132.6, 135.3, 153.1, 138.2, 205.3. Found (%): C, 70.00;
3
ꢀAcetylꢀ2ꢀ(pꢀtolyl)ꢀ2,3ꢀdihydropyrrolo[2,1ꢀa]isoquinolineꢀ
1
,1(10bH)ꢀdicarbonitrile (10b). The product yield was 0.74 g
H, 5.52; N, 9.86. C25H23N O . Calculated (%): C, 69.92.16;
H, 5.40; N, 9.78.
3 4
1
(
70%), m.p. 150—151 °C. H NMR (DMSOꢀd ), δ: 2.16 (s, 3 H,
6
CH CO); 2.35 (s, 3 H, CH ); 4.40 (d, 1 H, H(2), J = 8.1 Hz);
3ꢀAcetylꢀ2ꢀ(pyrenꢀ1ꢀyl)ꢀ2,3ꢀdihydropyrrolo[2.1ꢀa]isoquinꢀ
3
3
5
5
.02 (d, 1 H, H(3), J = 8.1 Hz); 5.40 (d, 1 H, H(6), J = 7.7 Hz);
.71 (s, 1 H, H(10b)), 6.63 (d, 1 H, H(5), J = 7.7 Hz); 7.11 (d, 1 H,
olineꢀ1,1(10bH)ꢀdicarbonitrile (10g). The isolated product yield
1
was 0.85 g (61%), m.p. 159—161 °C. H NMR (DMSOꢀd ), δ:
6
H(7), J = 7.3 Hz); 7.20 (m, 1 H, H(9)); 7.28—7.33 (m, 4 H,
2.21 (s, 3 H, CH ); 5.37 (d, 1 H, H(2), J = 7.3 Hz); 5.54
3
1
3
H(8), H(10), Ar); 7.47 (d, 2 H, Ar, J = 7.7 Hz). C NMR
DMSOꢀd ), δ: 21.0, 27.3, 50.4, 52.0, 68.7, 73.5, 98.9, 113.8,
(d, 1 H, H(3), J = 7.3 Hz); 5.86 (d, 1 H, H(6), J = 7.7 Hz); 5.98
(s, 1 H, H(10b)); 6.85 (d, 1 H, H(5), J = 7.7 Hz); 7.16—7.26
(m, 2 H, H(7), H(9)); 7.36 (m, 2 H, H(8), H(10)); 8.15 (m, 1 H,
Ar), 8.25 (m, 2 H, Ar), 8.35—8.45 (m, 5 H, Ar), 8.81 (d, 1 H,
(
6
1
1
23.7, 125.2, 126.3, 126.5, 128.8, 130.0, 130.2, 131.0, 132.9,
35.8, 135.9, 205.8. Found (%): C, 78.21; H, 5.44; N, 11.85.
Ar, J = 9.5 Hz). 1 C NMR (DMSOꢀd ), δ: 31.5, 45.9, 50.0,
3
C23H19N O. Calculated (%): C, 78.16; H, 5.42; N, 11.89.
3
6
Methyl 4ꢀ(3ꢀacetylꢀ1,1ꢀdicyanooꢀ1,2,3,10bꢀtetrahydroꢀ
68.1, 69.0, 98.93, 113.0, 113.2, 121.9, 123.7, 124.2, 124.6, 124.8,
125.1, 125.4, 125.9, 126.0, 126.3, 127.4, 127.5, 127.8, 128.1,
129.0, 129.6, 130.4 130.6, 131.6, 131.8, 134.3, 134.6, 135.11,
pyrrolo[2,1ꢀa]isoquinolineꢀ2ꢀyl)benzoate (10с). The isolated
1
product yield was 0.84 g (71%), m.p. 145—146 °C. H NMR
(
(
(
DMSOꢀd ), δ: 2.21 (s, 3 H, CH CO); 3.87 (s, 3 H, CH ); 4.57
d, 1 H, H(2), J = 7.5 Hz); 5.14 (d, 1 H, H(3), J = 7.7 Hz); 5.44
d, 1 H, H(6), J = 7.7 Hz); 5.76 (s, 1 H, H(10b)), 6.68 (d, 1 H,
199.4. Found (%): C, 83.06; H, 4.66; N, 9.12. C H N O.
32 21 3
Calculated (%): C, 82.92; H, 4.57; N, 9.07.
6
3
3
3ꢀAcetylꢀ2ꢀ(1Hꢀindolꢀ3ꢀyl)ꢀ2,3ꢀdihydropyrrolo[2.1ꢀa]isoꢀ
H(5), J = 7.7 Hz); 7.13 (d, 1 H, H(7), J = 7.7 Hz); 7.22 (m, 1 H,
H(9)); 7.33 (m, 2 H, H(8), H(10)); 7.74 (d, 2 H, Ar, J = 8.4 Hz);
quinolineꢀ1,1(10bH)ꢀdicarbonitrile (10h). The product yield was
1
0.59 g (52%), m.p. 135—136 °C. H NMR (DMSOꢀd ), δ: 2.17
6
1
3
8
.08 (d, 2 H, Ar, J = 8.4 Hz). C NMR (DMSOꢀd ), δ: 26.9,
(s, 3 H, CH ); 4.83 (d, 1 H, H(2), J = 8.1 Hz); 5.06 (d, 1 H,
6
3
4
1
2
9.9, 51.5, 52.3, 68.5, 73.4, 98.9, 113.2, 123.2, 124.9, 126.0,
26.3, 129.1, 129.8, 130.0, 132.5, 133.7, 135.4, 139.2, 165.7,
H(3), J = 8.1 Hz); 5.41 (d, 1 H, H(6), J = 7.7 Hz); 5.74 (s, 1 H,
H(10b)); 6.63 (d, 1 H, H(5), J = 7.7 Hz); 7.09—7.31 (m, 6 H,
H(7)—H(10), Ar); 7.44 (d, 1 H, Ar, J = 7.7 Hz); 7.77 (m, 2 H,
05.6. Found (%): C, 72.48; H, 4.79; N, 10.51. C24H19N O .
3 3
Ar); 11.40 (s, 1 H, NH). 1 C NMR (DMSOꢀd ), δ: 26.9, 44.7,
3
Calculated (%): C, 72.53; H, 4.82; N, 10.57.
6
3
ꢀAcetylꢀ2ꢀ(3ꢀbromoꢀ4ꢀmethoxyphenyl)ꢀ2,3ꢀdihydropyrroloꢀ
49.6, 68.2, 73.7, 98.4, 111.1, 112.0, 113.1, 118.6, 119.1, 121.9,
122.6, 123.6, 125.0, 126.1, 126.7, 128.3, 129.8, 132.6, 133.5,
[
2,1ꢀa]isoquinolineꢀ1,1(10bH)ꢀdicarbonitrile (10d). The isolatꢀ
ed product yield was 0.83 g (62%), m.p. 146—147 °C. H NMR
1
135.6, 205.2. Found (%): C, 76.28; H, 4.84; N, 14.90. C H N O.
24 18 4
(
(
(
DMSOꢀd ), δ: 2.17 (s, 3 H, CH CO); 3.39 (s, 3 H, CH ); 4.42
d, 1 H, H(2), J = 8.1 Hz); 5.05 (d, 1 H, H(3), J = 8.1 Hz); 5.39
d, 1 H, H(6), J = 7.7 Hz); 5.68 (s, 1 H, H(10b)); 6.61 (d, 1 H,
Calculated (%): C, 76.17; H, 4.79; N, 14.81.
6
3
3
1ꢀAcetylꢀ2ꢀphenylꢀ1,2ꢀdihydropyrrolo[1,2ꢀa]quinolineꢀ3,3ꢀ
(3aH)ꢀdicarbonitrile (11a). The product yield was 0.32 g (31%),
H(5), J = 7.7 Hz); 7.10 (d, 1 H, H(7), J = 7.3 Hz); 7.18—7.34
m.p. 165—167 °C. 1H NMR (DMSOꢀd ), δ:: 2.11 (s, 3 H,
6
(
m, 4 H, H(8), H(9), H(10), Ar); 7.59 (d, 1 H, Ar, J = 8.4);
CH ); 4.52 (d, 1 H, H(2), J = 8.8 Hz); 4.92 (d, 1 H, H(1),
3
7
5
1
.79 (s, 1 H, Ar). 13C NMR (DMSOꢀd ), δ: 29.9, 50.0, 50.7,
J = 8.8 Hz); 5.61 (m, 1 H, H(3a)); 5.87 (dd, 1 H, H(4), J = 10.3
Hz, J = 2.8 Hz); 6.34 (d, 1 H, H(9), J = 8.1 Hz); 6.70 (m, 1 H,
H(7)); 6.81 (d, 1 H, H(5), J = 10.3 Hz); 7.07 (m, 2 H,
H(8),H(6)); 7.50 (m, 3 H, Ar); 7.62 (d, 2 H, Ar, J = 5.5 Hz).
6
6.4, 68.2, 73.0, 98.5, 111.0, 113.0, 113.3, 123.2, 124.8, 126.0,
26.2, 127.0, 129.6, 129.9, 132.5, 132.7, 135.4, 156.0, 205.4.
Found (%): C, 61.68; H, 4.15; N, 9.41. C23H18BrN O . Calcꢀ
3
2
1
3
ulated (%): C, 61.62; H, 4.05; N, 9.37.
ꢀAcetylꢀ2ꢀ(2,5ꢀdimethoxyphenyl)ꢀ2,3ꢀdihydropyrrolo[2,1ꢀa]ꢀ
isoquinolineꢀ1,1(10bH)ꢀdicarbonitrile (10e). The product yield
C NMR (DMSOꢀd ), δ: 26.4, 48.9, 52.0, 68.2, 69.2,
6
3
110.1, 112.5, 115.5, 118.5, 118.6, 127.8, 128.7, 129.1, 129.4,
130.2, 130.3, 132.6, 141.4, 205.1. Found (%):C, 77.78; H, 4.99;
1
was 0.85 g (71%), m.p. 148—150 °C. H NMR (DMSOꢀd ), δ:
N, 12.32. C22H17N O. Calculated (%): C, 77.86; H, 5.05;
6
3
2
4
5
.22 (s, 3 H, CH CO); 3.74 (s, 3 H, CH ); 3.79 (s, 3 H, CH );
.71 (d, 1 H, H(2), J = 6.2 Hz); 5.15 (d, 1 H, H(3), J = 6.2 Hz);
.45 (d, 1 H, H(6), J = 7.3 Hz); 5.58 (s, 1 H, H(10b)); 6.73
N, 12.38.
3
3
3
The use of method B and bromoacetone as the alkylating
agent gave (see Table 3, entry 9) 0.44 g (43%) of tetrahydroꢀ
indolizine 11а, m.p. 165—167 °C.
(
d, 1 H, H(5), J = 7.3 Hz); 6.96 (m, 1 H, Ar); 7.05—7.15 (m, 3 H,
H(7), Ar); 7.20 (m, 1 H, H(9)); 7.31 (m, 2 H, H(8), H(10).
1ꢀAcetylꢀ2ꢀ(pꢀtolyl)ꢀ1,2ꢀdihydropyrrolo[2,1ꢀa]quinolineꢀ
1
3
C NMR (DMSOꢀd ), δ: 26.8, 45.5, 49.1, 55.5, 55.9, 68.6,
3,3(3aH)ꢀdicarbonitrile (11b). The product yield was 0.65 g
6
1
7
1
3.7, 99.1, 112.4, 113.5, 113.9, 115.5, 123.5, 123.6, 124.8, 125.9,
26.5, 129.8, 132.5, 135.5, 151.7, 153.1, 205.8. Found (%):
(62%), m.p. 162—164 °C. H NMR (DMSOꢀd ), δ: 2.09 (s, 3 H,
6
CH CO); 2.36 (s, 3 H, CH ); 4.47 (d, 1 H, H(2), J = 8.8 Hz);
3
3
C, 72.22; H, 5.39; N, 10.49. C24H21N O . Calculated (%):
C, 72.16; H, 5.30; N, 10.52.
4.89 (d, 1 H, H(1), J = 8.8 Hz); 5.59 (m, 1 H, H(3a)); 5.88 (dd,
1 H, H(4), J = 10.3 Hz, J = 2.6 Hz); 6.32 (d, 1 H, H(9),
3
2