SHKLYAEV et al.
1430
3 ml of concentrated sulfuric acid. After removal of the
solvent, the residue was recrystallized from methylene
chloride–hexane (1.5:1). Yield 0.57 g (43%), mp 117–
ppm: 0.74 d (3H, 4′-CH3, J = 7.5 Hz), 1.16 t (3H,
CH2CH3, J = 7.5 Hz) 1.24 s and 1.45 s (3H each,
5′-CH3), 2.62 q (1H, 4′-H, J = 7.5 Hz), 3.99–4.06 m
(2H, OCH2), 4.01 s (1H, =CH), 6.48 d (1H, 3-H, J =
10.5 Hz), 6.90 d (1H, 2-H, J = 10.2 Hz), 7.38 d (1H,
8-H, J = 7.8 Hz), 7.38 t (1H, 7-H, J = 7.8 Hz), 7.55 t
(1H, 6-H, J = 7.8 Hz), 8.11 d (1H, 5-H, J = 7.8 Hz),
8.28 br.s (1H, NH). 13C NMR spectrum (CDCl3), δC,
ppm: 9.26 (4′-CH3), 14.30 (CH2CH3), 26.22 and 30.38
(5′-CH3), 56.30 (C4′), 58.23 (C1), 58.55 (OCH2), 62.55
(C5′), 79.11 (=CH), 125.81 (C5), 127.42 (C8), 128.28
(C7), 128.54 (C3), 132.01 (C4a), 132.85 (C6), 145.30
(C1a), 147.10 (C2), 165.66 (C2′), 170.59 (OC=O),
184.03 (C=O). Found, %: C 73.82; H 6.90; N 4.29.
C20H23NO3. Calculated, %: C 73.82; H 7.12; N 4.30.
1
118°C. H NMR spectrum (DMSO-d6), δ, ppm: 0.73 d
(3H, 4′-CH3, J = 6.9 Hz), 1.24 s and 1.45 s (3H each,
5′-CH3), 2.31 s (3H, SCH3), 2.63 q (1H, 4′-H, J =
7.5 Hz), 6.52 d (1H, 3-H, J = 10.8 Hz), 7.07 d (1H,
2-H, J = 10.8 Hz), 7.41 d (1H, 8-H, J = 8.1 Hz), 7.50 t
(1H, 7-H, J = 7.5 Hz), 7.70 t (1H, 6-H, J = 7.5 Hz),
8.02 d (1H, 5-H, J = 8.1 Hz). 13C NMR spectrum
(DMSO-d6), δC, ppm: 10.01 (4′-CH3), 13.23 (SCH3),
25.04 and 30.51 (5′-CH3), 59.34 (C4′), 65.54 (C1),
74.57 (C5′), 125.42 (C5), 127.87 (C8), 128.60 (C7),
129.27 (C3), 131.59 (C4a), 133.21 (C6), 143.96 (C1a),
148.29 (C2), 169.21 (C2′), 183.27 (C=O). Found, %:
C 71.53; H 6.62; N 4.91; S 11.25. C17H19NOS. Calcu-
lated, %: C 71.54; H 6.71; N 4.91; S 11.23.
Diethyl 3,3′-[(2,2-dimethylpropane-1,1-diyl)di-
imino]bis(3-oxopropanoate) (IX) was obtained in
a similar way by reaction of 0.93 g (5 mmol) of
2-bromoanisole with 0.86 g (10 mmol) of pivalalde-
hyde and 0.56 g (5 mmol) of ethyl cyanoacetate in
3 ml of concentrated sulfuric acid. After removal of the
solvent, the residue was recrystallized from ethanol.
Yield 0.21 g (13%), mp 149–150°C. IR spectrum, ν,
cm–1: 3276, 3127 (NH); 1732 (C=O, ester); 1653
Methyl (Z)-(4′,5′,5′-trimethyl-4-oxo-4′,5′-dihy-
dro-4H-spiro[naphthalene-1,3′-pyrrol]-2′-yl)acetate
(VII) was synthesized from 0.79 g (5 mmol) of
1-methoxynaphthalene, 0.86 g (10 mmol) of pivalal-
dehyde, and 0.49 g (5 mmol) of methyl cyanoacetate in
3 ml of concentrated sulfuric acid. After removal of the
solvent, the residue was recrystallized from ethanol.
Yield 0.76 g (49%), mp 187–188°C. IR spectrum, ν,
cm–1: 3350 (NH), 1671 (C=O, ester), 1663 (C=O),
1
(C=O). H NMR spectrum (CDCl3), δ, ppm: 0.96 s
(9H, t-Bu), 1.24 t (6H, CH2CH3, J = 6.9 Hz), 2.34 q
(4H, CH2, J = 16.2 Hz), 4.14 q (4H, OCH2, J =
7.5 Hz), 5.77 t (1H, CH, J = 9.3 Hz), 8.05 s and 8.08 s
(1H each, NH). 13C NMR spectrum (CDCl3), δC, ppm:
13.95 (CH2CH3), 25.20 [C(CH3)3], 35.61 [C(CH3)3],
41.87 (CH2), 61.18 (OCH2), 62.19 (CH), 165.21
(C=O), 168.21 (OC=O). Mass spectrum, m/z (Irel, %):
315 (0.6) [M – Me]+, 274 (12.9), 273 (100) [M – t-Bu]+,
200 (25.8), 159 (93.5), 115 (47.9), 113 (24.1), 88
(17.1), 86 (26.2), 71 (13.3), 70 (15.9), 69 (14.2), 57
(12.6), 45 (27.8), 43 (28.9), 42 (14.8), 41 (15.0), 29
(28.1). Found, %: C 55.21; H 7.55; N 8.37.
C15H26N2O6. Calculated, %: C 54.53; H 7.93; N 8.48.
1
1602 (C=C). H NMR spectrum (DMSO-d6), δ, ppm:
0.67 d (3H, 4′-CH3, J = 7.5 Hz), 1.30 s and 1.47 s (3H
each, 5′-CH3), 2.58 q (1H, 4′-H, J = 7.5 Hz), 3.44 s
(3H, OCOCH3), 3.62 s (1H, =CH), 6.45 d (1H, 3-H,
J = 10.5 Hz), 7.11 d (1H, 2-H, J = 10.8 Hz), 7.45 d
(1H, 8-H, J = 7.8 Hz), 7.48 t (1H, 7-H, J = 7.8 Hz),
7.66 t (1H, 6-H, J = 7.5 Hz), 7.99 d (1H, 5-H, J =
8.1 Hz), 8.55 br.s (1H, NH). 13C NMR spectrum
(DMSO-d6), δC, ppm: 9.18 (4′-CH3), 25.24 and 29.79
(5′-CH3), 49.60 (OCOCH3), 55.39 (C4′), 58.22 (C1),
63.20 (C5′), 77.25 (=CH), 125.16 (C5), 127.72 (C8),
127.84 (C7), 128.81 (C3), 131.62 (C4a), 133.26 (C6),
145.55 (C1a), 148.62 (C2), 165.21 (C2′), 169.11 (OC=O),
183.47 (C=O). Found, %: C 73.36; H 6.71; N 4.48.
C19H21NO3. Calculated, %: C 73.29; H 6.80; N 4.50.
The mass spectra were obtained on an Agilent
Technologies 6890N/5975B GC–MS system (HP-5MS
column, 30 m×0.25 mm, film thickness 0.25 μm,
carrier gas helium; electron impact, 70 eV). The
1H and 13C NMR (DEPT) spectra were recorded on
a Varian Mercury Plus instrument at 300.06 and
75.46 MHz, respectively, using hexamethyldisiloxane
as internal reference. The IR spectra were measured on
a Bruker IFS-66 spectrometer from samples dispersed
in mineral oil. The elemental compositions were deter-
mined on a Leco CHNS-932 analyzer. The progress of
reactions and the purity of products were monitored by
TLC on Silufol plates using ethyl acetate–hexane (1:1)
Ethyl (Z)-(4′,5′,5′-trimethyl-4-oxo-4′,5′-dihydro-
4H-spiro[naphthalene-1,3′-pyrrol]-2′-yl)acetate
(VIII) was synthesized in a similar way from 0.79 g
(5 mmol) of 1-methoxynaphthalene, 0.86 g (10 mmol)
of pivalaldehyde, and 0.56 g (5 mmol) of ethyl cyano-
acetate in 3 ml of concentrated sulfuric acid. After
removal of the solvent, the residue was recrystallized
from ethanol. Yield 0.66 g (40%), mp 206–207°C. IR
spectrum, ν, cm–1: 3340 (NH), 1667 (C=O, ester), 1656
1
(C=O), 1602 (C=C). H NMR spectrum (CDCl3), δ,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 9 2011