EPOXYMETHYLATION OF 2-ACYL-SUBSTITUTED NH HETEROCYCLES
1683
15.6, 2.8 Hz), 7.14 t (1H, Harom, J = 7.6 Hz), 7.35 t (1H,
Harom, J = 7.6 Hz), 7.51 t (2H, Harom, J = 7.6 Hz), 7.55–
7.66 m (3H, Harom), 7.78 d (2H, Harom, J = 8.0 Hz).
13C NMR spectrum, δC, ppm: 13.8 (CH3), 30.5 (CH2),
44.4 (CH2), 44.9 (CH2), 50.7 (CH), 60.0 (CH2), 110.8
(CH), 113.8, 120.2 (CH), 124.9 (CH), 126.3 (CH),
127.7, 127.3 (2C, CH), 128.4, 129.1 (2C, CH), 132.6
(CH), 138.0, 138.9, 169.6 (C=O), 188.9 (C=O).
(1.01 mmol) of compound 7a, 10 mL of water, and
2 mL of 85% H3PO4 was refluxed for 4 h with stirring.
The mixture was cooled to room temperature and
neutralized to pH ~7 with aqueous ammonia. The
aqueous phase was separated by decanting from the
yellow viscous oil, and the oil was washed with water
and dried at 110°C. Yield 0.30 g (94%), yellow viscous
1
oily material. H NMR spectrum, δ, ppm: 2.02 s (3H,
CH3), 3.27–3.36 m (2H, CH2O), 3.65–3.75 m (1H,
CH), 4.32 d.d (1H, CH2N, J = 14.8, 8.0 Hz), 4.48 d.d
(1H, CH2N, J = 14.4, 3.6 Hz), 7.10 t (1H, Harom, J =
7.2 Hz), 7.31 t (1H, Harom, J = 7.2 Hz), 7.48–7.59 m
(4H, Harom), 7.62 t (1H, Harom, J = 7.2 Hz), 7.83 d (2H,
Harom, J = 7.6 Hz). 13C NMR spectrum, δC, ppm: 10.6
(CH3), 46.4 (CH2), 63.6 (CH2), 70.9 (CH), 110.9 (CH),
116.5, 119.3 (CH), 119.9 (CH), 124.4 (CH), 127.0,
128.2 (2C, CH), 129.4 (2C, CH), 132.3 (CH), 133.8,
139.5, 189.7 (C=O). Found, %: C 73.81; H 6.21;
N 4.50; O 15.48. C19H19NO3. Calculated, %: C 73.77;
H 6.19; N 4.53; O 15.51. M 309.37.
6-Methyl-9-(oxiran-2-ylmethyl)-2,3,4,9-tetra-
hydro-1H-carbazol-1-one (8c). The crude product
was treated with 10 mL of methanol, the mixture was
heated to the boiling point with stirring and left
overnight, and the crystalline solid was filtered off and
washed with methanol. Yield 86%, colorless needles,
1
mp 77–78°C. H NMR spectrum, δ, ppm: 2.18 quint
(2H, CH2, J = 6.4 Hz), 2.43 s (3H, CH3), 2.51–2.60 m
(3H, CH2), 2.68 t (1H, CH2, J = 6.0 Hz), 2.96 t (2H,
CH2, J = 6.0 Hz), 3.16–3.24 m (1H, CH), 4.42 d.d (1H,
CH2N, J = 14.8, 5.2 Hz), 4.88 d.d (1H, CH2N, J = 14.8,
3.6 Hz), 7.16 d.d (1H, Harom, J = 8.4, 1.2 Hz), 7.36 d
(1H, Harom, J = 8.4 Hz), 7.38 s (1H, Harom). 13C NMR
spectrum, δC, ppm: 21.0 (CH3), 21.2 (CH2), 24.2
(CH2), 39.2 (CH2), 44.5 (CH2), 45.7 (CH2), 50.7 (CH),
110.7 (CH), 120.0 (CH), 1214.5, 128.2 (CH), 128.3,
128.7, 129.3, 137.8, 190 (C=O). Found, %: C 75.30;
H 6.73; N 5.52; O 12.45. C16H17NO2. Calculated, %:
C 75.27; H 6.71; N 5.49; O 12.53 M 255.32.
9-(2,3-Dihydroxypropyl)-2,3,4,9-tetrahydro-1H-
carbazol-1-one (11). A mixture of 1 g (3.9 mmol) of
compound 8c, 5 mL of 1,4-dioxane, 0.2 mL of water,
and 0.2 mL of H3PO4 was refluxed for 2 h. The mixture
was cooled to room temperature, 15 mL of water was
added, and a mobile oily material separated and crys-
tallized on grinding. The precipitate was filtered off
and washed with water. Yield 1 g (94%), colorless floc-
culent crystals, mp 117–118°C. The product required
[1-(2,3-Dihydroxypropyl)-3,4,5-trimethyl-1H-
pyrrol-2-yl](phenyl)methanone (9). A mixture of
150 mg (0.56 mmol) of compound 5 and 100 mg of
BTEAC in 8 mL of undried acetonitrile was refluxed
for 10 h. The solvent was distilled off, the residue was
treated with 5 mL of water, and the oily material
rapidly solidified. The precipitate was filtered off and
washed with water. The product required no further
purification. Yield 0.147 g (92%), fine colorless crys-
tals, mp 113–114°C. 1H NMR spectrum, δ, ppm: 1.55 s
(3H, CH3), 1.89 s (3H, CH3), 2.25 s (3H, CH3), 3.26–
3.34 m (2H, CH2OH), 3.63 sept (1H, CH, J = 4.4 Hz),
4.03 d.d (1H, CH2N, J = 14.0, 8.4 Hz), 4.28 d.d (1H,
CH2N, J = 14.0, 3.6 Hz), 4.37 t (1H, OH, J = 5.6 Hz),
4.73 d (1H, OH, J = 6.0 Hz), 7.43 t (2H, Harom, J =
7.2 Hz), 7.51 t (1H, Harom, J = 7.2 Hz), 7.59 t (2H,
Harom, J = 7.2 Hz). 13C NMR spectrum, δC, ppm: 9.0
(CH3), 10.3 (CH3), 12.0 (CH3), 47.4 (CH2), 63.7 (CH2),
71.7 (CH), 115.5, 126.9, 127.5, 127.8 (2C, CH), 128.6
(2C, CH), 130.8 (CH), 135.0, 141.3, 186.1 (C=O).
Found, %: C 71.01; H 7.42; N 4.82; O 16.75.
C17H21NO3. Calculated, %: C 71.06; H 7.37; N 4.87;
O 16.70. M 287.36.
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no further purification. H NMR spectrum, δ, ppm:
2.18 quint (2H, CH2, J = 5.6 Hz), 2.42 s (3H, CH3),
2.56 t (2H, CH2, J = 6.0 Hz), 2.96 t (2H, CH2, J =
5.6 Hz), 3.28–3.40 m (2H, CH2O), 3.72–3.83 m (1H,
CH), 4.35 d.d (1H. CH2N, J = 14.0, 6.8 Hz), 4.53 d.d
(1H, CH2N, J = 14.0, 5.2 Hz), 7.14 d (1Harom, J =
8.8 Hz), 7.36 s (1Harom), 7.43 d (1Harom, J = 8.4 Hz).
13C NMR spectrum, δC, ppm: 21.0 (CH3), 21.3 (CH2),
39.4 (CH2), 47.1 (CH2), 63.5 (CH2), 71.4 (CH), 111.2
(CH), 119.7 (CH), 124.3, 127.9 (CH), 128.0, 128.2,
129.7, 138.0, 190.4 (C=O). Found, %: C 70.34; H 7.04;
N 5.09; O 17.53. C16H19NO3. Calculated, %: C 70.31;
H 7.01; N 5.12; O 17.56. M 273.33.
9-[3-(3,5-Dimethyl-1H-pyrazol-1-yl)-2-hydroxy-
propyl]-2,3,4,9-tetrahydro-1H-carbazol-1-one (12)
and 9-(2-hydroxy-3-piperidin-1-ylpropyl)-2,3,4,9-
tetrahydro-1H-carbazol-1-one (13) (general proce-
dure). A mixture of 1 mmol of compound 8c and
1.5 mmol of 3,5-dimethyl-1H-pyrazole or piperidine in
2 mL of 2-ethoxyethanol was refluxed for 6 h. The
mixture was treated with 8 mL of water, an oily mate-
rial separated and was ground until complete crystal-
[1-(2,3-Dihydroxypropyl)-3-methyl-1H-indol-
2-yl](phenyl)methanone (10). A mixture of 0.3 g
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 56 No. 10 2020