OXIMATION OF 2-(R1-AMINO)-4-(R2-IMINO)NAPHTHALEN-1(4H)-ONES
83
of 10 mL of ethanol and 10 mL of dioxane. The
mixture was refluxed for 2 h and cooled to 60°C,
20 mL of water was added, and the mixture was heated
to the boiling point and cooled. The precipitate was
filtered off and washed with water, aqueous ethanol,
and ethanol. Yield 1.28 g (84%), orange crystals,
mp 122‒123°C (from EtOH‒DMF, 1:1). UV spec-
trum, λmax, nm (logε): 205 (4.41), 240 (4.42), 334
(3.71), 456 (3.79). IR spectrum, ν, cm–1: 3332 (N–H),
1654 (C=N), 1605 (C=O), 1335 (N–C). 1H NMR spec-
trum, δ, ppm: 0.78 t (3H, CH3, J = 7.3 Hz), 1.15‒
1.23 m (2H, CH2CH3), 1.38‒1.45 m (2H, CH2), 2.88 q
(2H, CH2NH, J = 6.0 Hz), 5.65 s (1H, 3-H), 6.90 d
(2H, o-H, J = 7.6 Hz), 6.93 t (1H, NH, J = 6.0 Hz),
7.12 t (1H, p-H, J = 7.6 Hz), 7.40 t (2H, m-H, J =
7.6 Hz), 7.71 t (1H, 6-H, J = 7.4 Hz), 7.81 t (1H, 7-H,
J = 7.7 Hz), 8.08 d (1H, 8-H, J = 7.7 Hz), 8.43 d (1H,
5-H, J = 7.7 Hz). 13C NMR spectrum, δC, ppm: 13.53
(CH3), 19.64 (CH2CH3), 29.28 (CH2CH2CH3), 41.21
(NHCH2), 92.63 (C3), 120.45 (Co), 123.36 (Cp), 124.88
(C5), 125.74 (C8), 128.25 (Cm), 130.09 (C4a), 130.58
(C6), 133.43 (C7), 135.40 (C8a), 144.00 (C2), 151.59
(Ci), 154.96 (C4), 181.01 (C1). Mass spectrum, m/z
(Irel, %): 304 (100) [M]+, 261 (22.1), 232 (24.1), 204
(24.4), 77 (31.7). Found, %: C 79.13; H 6.51; N 9.25.
C20H20N2O. Calculated, %: C 78.92; H 6.62; N 9.20.
M 304.40.
1.6 g (22 mmol), was added with stirring to a solution
of 2.63 g (10 mmol) of 4-(4-methylanilino)-1,2-naph-
thoquinone in 50 mL of ethanol. The mixture was
refluxed for 2 h and cooled to 60°C, 40 mL of water
was added, and the mixture was heated to the boiling
point and cooled. The precipitate was filtered off and
washed with water and ethanol. Yield 2.43 g (76%),
red crystals, mp 144‒145°C (from EtOH‒DMF, 1:1).
UV spectrum, λmax, nm (logε): 207 (4.45), 242 (4.44),
335 (3.71), 468 (3.81). IR spectrum, ν, cm–1: 3351
(N–H), 1654 (C=N), 1596 (C=O), 1338 (N–C).
1H NMR spectrum, δ, ppm: 0.81 d (6H, CH3, J =
6.7 Hz), 1.78‒1.85 m (1H, CH), 2.33 s (3H, CH3),
2.73 t (2H, CH2, J = 6.2 Hz), 5.73 s (1H, 3-H), 6.81 d
(2H, m-H, J = 8.1 Hz), 6.89 t (1H, NH, J = 6.2 Hz),
7.21 d (2H, o-H, J = 8.1 Hz), 7.70 t (1H, 6-H, J =
7.6 Hz), 7.79 t (1H, 7-H, J = 7.6 Hz), 8.08 d (1H, 8-H,
J = 7.6 Hz), 8.43 d (1H, 5-H, J = 7.6 Hz). 13C NMR
spectrum, δC, ppm: 20.29 [CH(CH3)2], 20.58 (CH3),
26.77 [CH(CH3)2], 49.31 (NCH2), 92.95 (C3), 120.65
(Co), 124.86 (C5), 125.73 (C8), 129.36 (Cm), 130.04
(C4a), 130.54 (C6), 132.47 (C8a), 135.42 (C7), 135.48
(Cp), 144.13 (C2), 148.81 (Ci), 181.08 (C1). Mass
spectrum, m/z (Irel, %): 318 (100) [M]+, 275 (40.8),
246 (19.5). Found, %: C 79.38; H 6.90; N 8.88.
C21H22N2O. Calculated, %: C 79.21; H 6.96; N 8.80.
M 318.42.
2-Anilino-4-(phenylimino)naphthalen-1(4H)-one
(6c). Aniline, 5 mL (55 mmol), was added to a solution
of 7.5 g (30 mmol) of 4-anilino-1,2-naphthoquinone in
80 mL of 2-ethoxyethanol. The mixture was refluxed
for 3 h and cooled to room temperature, and the
precipitate was filtered off and washed with water,
aqueous ethanol, and ethanol. Yield 7.25 g (75%), red
crystals, mp 184‒186°C (from EtOH‒DMF, 1:1). UV
spectrum, λmax, nm (logε): 208 (4.45), 254 (4.27), 283
(4.32), 472 (3.77). IR spectrum, ν, cm–1: 3346 (N–H),
1648 (C=N), 1599 (C=O), 1347 (N–C). 1H NMR spec-
trum, δ, ppm: 6.50 s (1H, 3-H), 6.93 d (2H, o-H, J =
7.5 Hz), 7.03 t (1H, p-H, J = 7.5 Hz), 7.11 t (2H, m-H,
J = 7.5 Hz), 7.23 d (2H, o′-H, J = 7.8 Hz), 7.27 t (2H,
m′-H, J = 7.8 Hz), 7.38 t (1H, p′-H, J = 7.8 Hz), 7.76 t
(1H, 6-H, J = 7.8 Hz), 7.84 t (1H, 7-H, J = 7.8 Hz),
8.16 d.d (1H, 5-H, J = 7.8, 1.1 Hz), 8.45 d.d (1H, 8-H,
J = 7.8, 1.1 Hz), 8.74 s (1H, NH). Mass spectrum, m/z
(Irel, %): 324 (100) [M]+, 323 (35.8), 247 (22.0), 77
(34.0). Found, %: C 81.39; H 4.86; N 8.47.
C22H16N2O. Calculated, %: C 81.46; H 4.97; N 8.64.
M 324.39.
2-(4-Methylanilino)-4-[(4-methylphenyl)imino]-
naphthalen-1(4H)-one (6e). p-Toluidine, 5.35 g
(50 mmol), was added to 7.89 g (30 mmol) of
4-(4-methylamino)-1,2-naphthoquinone in 80 mL of
2-ethoxyethanol. The mixture was refluxed for 3 h and
cooled to room temperature, and the precipitate was
filtered off and washed with water, aqueous ethanol,
and ethanol. Yield 9.5 g (90%), red–brown crystals,
mp 175‒177°C (from EtOH‒DMF, 1:1). UV spec-
trum, λmax, nm (logε): 209 (4.44), 254 (4.22), 281
(4.26), 480 (3.73). IR spectrum, ν, cm–1: 3332 (N–H),
1640 (C=N), 1594 (C=O), 1337 (N–C). 1H NMR spec-
trum, δ, ppm: 2.24 s (3H, CH3), 2.30 s (3H, CH3),
6.40 s (1H, 3-H), 6.84 d (2H, m-H, J = 8.0 Hz), 6.93 d
(2H, o-H, J = 8.0 Hz), 7.08 d (2H, m′-H, J = 8.5 Hz),
7.12 d (2H, o′-H, J = 8.5 Hz), 7.75 t (1H, 6-H, J =
7.6 Hz), 7.84 t (1H, 7-H, J = 7.6 Hz), 8.15 d.d (1H,
5-H, J = 7.9, 1.2 Hz), 8.44 d.d (1H, 8-H, J = 7.9,
1.2 Hz), 8.66 s (1H, NH). Mass spectrum, m/z (Irel, %):
352 (100) [M]+, 351 (22.8), 261 (12.41). Found, %:
C 81.42; H 5.58; N 7.93. C24H20N2O. Calculated, %:
C 81.79; H 5.72; N 7.95. M 352.44.
(4E)-4-[(4-Methylphenyl)imino]-2-(2-methyl-
propyl)naphthalen-1(4H)-one (6d). Isobutylamine,
(4E)-2-(Butylamino)-4-(butylimino)naphthalen-
1(4H)-one (6f). Sodium 1,2-dioxo-1,2-dihydronaph-
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 54 No. 1 2018