AVETISYAN et al.
430
HCl). Found, %: C 47.64; H 5.61; N 15.31.
C11H15Cl2N3O. Calculated, %: C 47.83; H 5.43;
N 15.22.
0.26 ml (2 mmol) of ethyl acetoacetate, 1 ml of
ethanol, and 0.2 ml of concentrated sulfuric acid was
heated for 10–12 h on a water bath. The solvent was
distilled off, the residue was treated with water, the
aqueous phase was filtered, the filtrate was adjusted to
pH 9, and the precipitate was filtered off.
4-Hydrazino-2-methylquinolines IIIa–IIIe (gen-
eral procedure). 4-Hydrazino-2-methylquinoline dihy-
drochloride IIa–IIe, 1 mmol, was dissolved in water,
the solution was filtered and adjusted to pH 9, and the
precipitate was filtered off.
b. A mixture of 2 mmol of compound IIIa–IIIe,
0.3 ml of acetone, 1 ml of ethanol, and 0.2 ml of con-
centrated sulfuric acid was heated for 10–12 h on
a water bath. The mixture was then treated as de-
scribed above in a. Samples of compounds IVa–IVe
synthesized according to the two methods showed no
depression of the melting point on mixing.
4-Hydrazino-2-methylquinoline (IIIa). Yield
1.76 g (92%), mp 275°C (decomp.), Rf 0.52 (alcohol–
hexane, 3:1). IR spectrum, ν, cm–1: 3400, 3260 (NH,
1
NH2). H NMR spectrum, δ, ppm: 2.50 s (3H, CH3),
6.40 s (1H, Harom), 7.30–8.20 m (6H, Harom, NH2),
11.90 s (1H, NH). Found, %, C 69.24; H 6.49;
N 24.35. C10H11N3. Calculated, %: C 69.36; H 6.36;
N 24.28.
2,4-Dimethyl-1H-pyrrolo[3,2-c]quinoline (IVa).
Yield 0.28 g (72%, a, 0.34 g (88%, b), mp 155–156°C,
Rf 0.56 (alcohol–hexane, 2 : 1). IR spectrum:
1
ν 3220 cm–1 (NH). H NMR spectrum, δ, ppm: 2.80 s
4-Hydrazino-2,6-dimethylquinoline (IIIb). Yield
1.83 g (98%), mp 242°C (decomp.), Rf 0.52 (alcohol–
toluene, 1:2). IR spectrum, ν, cm–1: 3450, 3180 (NH,
(3H, 4-CH3), 3.00 s (3H, 2CH3), 6.70 s (1H, Harom),
7.30–8.30 m (4H, Harom), 8.80 s (1H, NH). Found, %:
C 79.64; H 6.04; N 14.39. C13H12N2. Calculated, %:
C 79.59; H 6.12; N 14.28.
1
NH2). H NMR spectrum, δ, ppm: 2.40 s (3H, 6-CH3),
2.65 s (3H, 2-CH3), 6.40 s (1H, Harom), 7.40–8.50 m
(5H, Harom, NH2), 9.70–10.50 s (1H, NH). Found, %:
C 70.72; H 6.79; N 22.34. C11H13N3. Calculated, %:
C 70.59; H 6.95; N 22.46.
2,4,8-Trimethyl-1H-pyrrolo[3,2-c]quinoline
(IVb). Yield 0.35 g (83%, a), 0.29 g (68%, b),
mp 252°C, Rf 0.63 (alcohol–toluene, 1:1). IR spec-
trum, ν, cm–1: 3340, 3185 (NH). 1H NMR spectrum, δ,
ppm: 2.45 s (3H, 8-CH3), 2.70 s (3H, 4-CH3), 3.00 s
(3H, 2-CH3), 6.80 s (1H, Harom), 7.80–8.80 m (3H,
4-Hydrazino-2,8-dimethylquinoline (IIIc). Yield
1.80 g (96%), mp 224–226°C (decomp.), Rf 0.50
(alcohol–toluene, 1:1). IR spectrum, ν, cm–1: 3295,
1
Harom), 10.15 s (1H, NH). Found, %: C 80.21; H 6.59;
3155 (NH, NH2). H NMR spectrum, δ, ppm: 2.45 s
N 13.45. C14H14N2. Calculated, %: C 80.00; H 6.67;
N 13.33.
(3H, 8-CH3), 2.75 s (3H, 2-CH3), 6.45 s (1H, Harom),
7.60–8.83 m (5H, Harom, NH2), 9.30–10.62 d (1H, NH).
Found, %: C 70.71; H 6.84; N 22.59. C11H13N3. Cal-
culated, %: C 70.59; H 6.95; N 22.46.
2,4,6-Trimethyl-1H-pyrrolo[3,2-c]quinoline
(IVc). Yield 0.30 g (70%, a), 0.21 g (50%, b), mp 147–
1
149°C, Rf 0.58 (alcohol–toluene, 1:1). H NMR spec-
4-Hydrazino-6-methoxy-2-methylquinoline
(IIId). Yield 1.97 g (97%), mp 218°C (decomp.), Rf
0.60 (alcohol–toluene, 1:1). IR spectrum, ν, cm–1:
trum, δ, ppm: 2.50 s (3H, 6-CH3), 2.70 s (3H, 4-CH3),
3.05 s (3H, 2-CH3), 6.70 s (1H, Harom), 7.35–8.40 m
(3H, Harom), 11.85 s and 12.45 s (1H, NH). Found, %:
C 79.83; H 6.78; N 13.19. C14H14N2. Calculated, %:
C 80.00; H 6.67; N 13.33.
1
3325, 3220 (NH, NH2). H NMR spectrum, δ, ppm:
2.65 s (3H, CH3), 4.00 s (3H, OCH3), 6.40 s (1H,
Harom), 7.30–8.90 m (6H, Harom, NH, NH2). Found, %:
C 65.21; H 6.19; N 20.80. C11H13N3O. Calculated, %:
C 65.02; H 6.40; N 20.69.
8-Methoxy-2,4-dimethyl-1H-pyrrolo[3,2-c]-
quinoline (IVd). Yield 0.33 g (73%, a), 0.30 g (65%,
b), mp 224–225°C, Rf 0.59 (alcohol–toluene, 1:1).
1H NMR spectrum, δ, ppm: 2.55 s (3H, 4CH3), 3.10 s
(3H, 2-CH3), 4.00 s (3H, OCH3), 6.80 s (1H, Harom),
7.30–8.40 m (3H, Harom), 10.90 s and 11.85 s (1H,
NH). Found, %: C 74.19; H 6.31; N 12.45. C14H14N2O.
Calculated, %: C 74.34; H 6.19; N 12.39.
4-Hydrazino-8-methoxy-2-methylquinoline
(IIIe). Yield 1.89 g (93%), mp 301°C (decomp.),
1
Rf 0.53 (alcohol–toluene, 1:1). H NMR spectrum, δ,
ppm: 2.53 s (3H, CH3), 3.93 s (3H, OCH3), 6.20 s (1H,
Harom), 7.40–8.90 m (6H, Harom, NH, NH2). Found, %:
C 64.87; H 6.57; N 20.53. C11H13N3O. Calculated, %:
C 65.02; H 6.40; N 20.69.
6-Methoxy-2,4-dimethyl-1H-pyrrolo[3,2-c]quin-
oline (IVe). Yield 0.30 g (66%, a), 0.24 g (52%, b),
mp 311°C, Rf 0.58 (alcohol–toluene, 1:1). IR spec-
trum, ν, cm–1: 3340, 3185 (NH). 1H NMR spectrum, δ,
2,4-Dimethyl-1H-pyrrolo[3,2-c]quinolines IVa–
IVd (general procedure). a. A mixture of 2 mmol of
substituted 4-hydrazino-2-methylquinoline IIIa–IIIe,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 3 2010