Chemistry of Heterocyclic Compounds 2017, 53(11), 1228–1241
2-azaspiro[4.5]deca-1,6,9-trien-8-one (9g). The residue
2.67 (1Н, d, J = 16.8, 7-СН2); 4.82 (1H, s, NH); 6.33 (1H,
q, J = 1.2, H-4); 6.55 (1Н, d, J = 9.2, H-9); 8.05 (1H, dd,
J = 9.2, J =2.4, H-10); 8.81 (1Н, d, J = 2.4, H-12).
13C NMR spectrum, δ, ppm: 15.4; 24.1; 30.5; 31.3; 45.2;
47.8; 58.6; 59.1; 72.9; 113.6; 114.6; 124.2; 127.7; 133.8;
139.1; 144.9; 149.6; 163.3; 196.5. Mass spectrum, m/z (Irel, %):
339 [M]+ (63), 325 (21), 324 [M–СН3]+ (100), 296 (15),
284 (10), 256 (13), 242 (17). Found, %: C 67.15; H 6.11;
N 12.45. C19H21N3O3. Calculated, %: C 67.24; H 6.24;
N 12.38.
Compound 6i'. Rf 0.20 (petroleum ether – acetone, 3:1).
1H NMR spectrum, δ, ppm (J, Hz): 1.32 (3Н, d, J = 7.2,
7-СН3); 1.48 (3Н, s, 2-СН3); 1.54 (3Н, s, 2-СН3); 1.79 (3Н,
d, J = 1.6, 4-СН3); 2.06 (1Н, d, J = 14.4, 3-СН2); 2.20 (1Н,
d, J = 14.4, 3-СН2); 2.88 (1Н, qd, J = 6.8, J = 2.4, Н-7);
3.81 (1H, d, J = 2.4, 7а-CH); 4.71 (1Н, br. s, NH); 5.85
(1Н, d, J = 1.2, 5-CH); 6.55 (1Н, d, J = 9.2, H-9); 8.06 (1H,
dd, J = 8.8, J =2.8, H-10); 8.64 (1Н, d, J = 2.8, H-12).
Mass spectrum, m/z (Irel, %): 339 [M]+ (79), 325 (21), 324
[M–СН3]+ (100), 296 (125), 282 (17).
(3aS*,7S*,7aR*)-2,2,5,7-Tetramethyl-11-nitro-2,7,7a,8-
tetrahydropyrrolo[3,2-l]acridin-6(3H)-one (6jA) and
(3aS*,7R*,7aR*)-2,2,5,7-tetramethyl-11-nitro-2,7,7a,8-
tetrahydropyrrolo[3,2-l]acridin-6(3H)-one (6jВ). The
product was crystallized from acetone, providing
compound 6jA (298 mg). The residue was separated by
chromatography (eluent petroleum ether – acetone, 5:1),
giving a mixture of compounds 6jA and 6jВ (128 mg,
6jA:6jВ = 1:1 according to the data of 1Н NMR
spectroscopy).
Compound 6jA. Yield 298 mg (44%), yellow crystals,
mp 294°C (decomp.), Rf 0.45 (petroleum ether – acetone,
5:1). IR spectrum, ν, cm–1: 1302, 1316, 1616, 1628, 1665,
3098, 3197, 3256, 3361. 1H NMR spectrum, δ, ppm (J, Hz):
1.32 (3Н, d, J = 7.2, 7-СН3); 1.43 (3Н, s, 2-СН3); 1.50 (3Н,
s, 2-СН3); 1.74 (3Н, d, J = 1.6, 5-СН3); 2.10 (1Н, d,
J = 13.2, 3-СН2); 2.24 (1Н, d, J = 12.8, 3-СН2); 2.90 (1Н,
qd, J = 7.2, J = 2.4, 7-CH); 3.74 (1Н, t, J = 2.0, 7а-CH);
4.73 (1H, s, NH), 6.26 (1H, t, J =2.0, 4-CH); 6.58 (1Н, d,
J = 9.2, H-9); 8.05 (1H, dd, J = 9.2, J = 2.8, H-10); 8.77
(1Н, d, J = 2.8, Н-12). 13C NMR spectrum, δ, ppm: 11.3; 15.9;
29.9; 31.2; 41.9; 48.9; 54.5; 64.2; 72.9; 114.4; 114.8;
124.0; 127.5; 135.0; 139.3; 141.4; 150.5; 164.4; 197.7.
Mass spectrum, m/z (Irel, %): 339 [M]+ (82), 325 (20), 324
[M–СН3]+ (100), 296 (10), 282 (17), 204 (20). Found, %:
C 66.98; H 6.41; N 12.63. C19H21N3O3. Calculated, %:
C 67.24; H 6.24; N 12.38.
was separated by chromatography (eluent petroleum ether –
acetone, 5:1).
Compound 6g. Yield 370 mg (50%, from compound 1g),
379 mg (51%, from compound 1h), yellow crystals, mp 204°C
(decomp., acetone), Rf 0.26 (petroleum ether – acetone,
5:1). IR spectrum, ν, cm–1: 1317, 1324, 1616, 1637, 1664,
3057, 3091, 3115, 3147, 3234, 3283, 3332. 1H NMR
spectrum, δ, ppm (J, Hz): 0.86 (3Н, d, J = 6.8, СНСН3);
0.98 (3H, d, J = 6.8, СНСН3); 1.29 (3H, s, 7а-СН3); 1.47
(3Н, s, 2-СН3); 1.50 (3Н, s, 2-СН3); 1.96 (1Н, d, J = 13.6,
3-СН2); 2.29 (1Н, d, J = 13.6, 3-СН2); 2.67 (2Н, s, 7-СН2);
2.80 (1Н, sept, J = 6.8, СН(СН3)2); 5.72 (1H, br. s, NH);
6.26 (1Н, s, 4-CH); 6.64 (1Н, d, J = 9.2, H-9); 8.04 (1H,
dd, J = 9.2, J =2.8, H-10); 8.84 (1Н, d, J = 2.8, Н-12).
13C NMR spectrum, δ, ppm: 21.2; 21.7; 23.8; 26.1; 30.5;
31.3; 45.2; 47.9; 58.2; 58.5; 72.8; 113.0; 114.4; 124.3; 127.7;
138.5; 142.2; 143.6; 150.1; 163.7; 196.4. Mass spectrum,
m/z (Irel, %): 367 [M]+ (51), 352 [M–СН3]+ (100), 324 (16),
296 (29), 242 (13). Found, %: C 68.39; H 6.93; N 11.37.
C21H25N3O3. Calculated, %: C 68.64; H 6.86; N 11.44.
Compound 9g. Yield 150 mg (20%, from compound
1g), 120 mg (16%, from compound 1h), light-yellow
crystals, mp 159–161°C (EtOAc), Rf 0.34 (petroleum ether –
acetone, 5:1). IR spectrum, ν, cm–1: 1315, 1326, 1617,
1659, 2872, 2930, 2966, 3169, 3233, 3403. 1H NMR
spectrum, δ, ppm (J, Hz): 1.07 (3Н, d, J = 6.8, СНСН3);
1.11 (3Н, d, J = 6.8, СНСН3); 1.50 (3Н, s, 3-СН3); 1.56
(3Н, s, 3-СН3); 1.82 (3Н, d, J = 0.4, 6-СН3); 2.05 (1Н, d,
J = 13.6, 4-СН2); 2.19 (1Н, d, J = 13.6, 4-СН2); 3.11 (1H,
sept, J = 6.8, СН(СН3)2); 6.32 (1H, d, J = 0.8, 10-CH);
6.68 (1H, d, J = 9.2, Н-3'); 6.72 (1H, s, 7-CH); 7.53 (2Н,
br. s, NH2); 7.97 (1H, dd, J = 8.8, J = 2.0, Н-4'); 8.17 (1H, d,
J = 2.0, H-6'). 13C NMR spectrum, δ, ppm: 19.9; 20.9; 22.1;
26.1; 30.9; 31.7; 49.1; 65.0; 72.7; 112.2; 115.5; 126.4;
126.9; 128.6; 137.0; 143.4; 143.8; 154.2; 158.0; 166.7; 184.7.
Mass spectrum, m/z (Irel, %): 367 [M]+ (11), 218 (10), 204
(63), 189 (100), 175 (41), 163 (16), 161 (56), 149 (17), 147
(34), 133 (20), 121 (16), 117 (14), 115 (10), 104 (15), 91
(18), 77 (10), 41 (11). Found, %: С 68.33; Н 6.71; N 11.55.
C21H25N3O3. Calculated, %: C 68.64; H 6.86; N 11.44.
(3aS*,7aR*)-2,2,5,7a-Tetramethyl-11-nitro-2,7,7a,8-
tetrahydropyrrolo[3,2-l]acridin-6(3H)-one (6i) and
(3aS*,7aR*)-2,2,4,7-tetramethyl-11-nitro-2,7,7a,8-tetra-
hydropyrrolo[3,2-l]acridin-6(3H)-one (6i'). The product
was crystallized from EtOAc, resulting in 245 mg of
compound 6i. The residue was separated by chromato-
graphy (eluent petroleum ether – EtOAc, gradient from 5:1
to 3:1), providing additional amounts of compound 6i
(185 mg) and a mixture of compounds 6i and 6i' (40 mg,
Compound 6jВ. Rf 0.40 (petroleum ether – acetone, 5:1).
1H NMR spectrum, δ, ppm (J, Hz): 1.29 (3Н, d, J = 7.6,
7-СН3); 1.43 (3Н, s, 2-СН3); 1.50 (3Н, s, 2-СН3); 1.75 (3Н,
d, J = 1.2, 5-СН3); 2.13 (1Н, d, J = 13.2, 3-СН2); 2.30 (1Н,
d, J = 13.2, 3-СН2); 2.66 (1Н, qd, J = 7.2, J = 2.0, 7-CH);
3.77 (1Н, br. s, 7а-CH); 4.95 (1H, br. s, NH), 6.29 (1H, br. s,
4-CH); 6.61 (1Н, d, J = 9.2, H-9); 8.02 (1H, dd, J = 8.8,
J = 2.8, H-10); 8.78 (1Н, d, J = 2.8, Н-12). Mass spectrum,
m/z (Irel, %): 339 [M]+ (100), 325 (18), 324 [M–СН3]+ (81),
296 (12), 282 (18), 204 (44), 177 (18), 161 (20), 135 (15).
Preparation of compounds 7a–g,i,j (General method).
2-Amino-4-chlorobenzonitrile (4) (305 mg, 2 mmol) was
6i:6i'
=
3:1 according to the data of 1Н NMR
spectroscopy).
Compound 6i. Yield 430 mg (63%), yellow crystals,
mp 290°C (decomp.), Rf 0.26 (petroleum ether – acetone,
3:1). IR spectrum, ν, cm–1: 1322, 1615, 1640, 1664, 3049,
1
3091, 3325. H NMR spectrum, δ, ppm (J, Hz): 1.26 (3Н,
s, 7а-СН3); 1.46 (3Н, s, 2-СН3); 1.48 (3Н, s, 2-СН3); 1.74
(3Н, d, J = 1.6, 5-СН3); 1.99 (1Н, d, J = 13.6, 3-СН2); 2.25
(1Н, d, J = 13.6, 3-СН2); 2.60 (1Н, d, J = 16.8, 7-СН2);
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