New Syntheses of Naphthostyryl Derivatives via Nucleophilic Vinylic Substitution

Article abstract of DOI:10.1134/S1070428018070163

New substituted naphthostyryl derivatives have been synthesized by nucleophilic vinylic substitution reactions and converted to the corresponding N-alkyl derivatives by treatment with alkyl halides.

Full text of DOI:10.1134/S1070428018070163

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2018, Vol. 54, No. 7, pp. 1071–1075. © Pleiades Publishing, Ltd., 2018.
Original Russian Text © A.Yu. Kashner, I.V. Dyachenko, Yu.V. Samusenko, Yu.I. Rozhinskii, V.D. Dyachenko, 2018, published in Zhurnal Organicheskoi
Khimii, 2018, Vol. 54, No. 7, pp. 1064–1068.
New Syntheses of Naphthostyryl Derivatives
via Nucleophilic Vinylic Substitution
A. Yu. Kashnera, I. V. Dyachenkob, Yu. V. Samusenkoc,
Yu. I. Rozhinskiid, and V. D. Dyachenkoe, f*
a Ukrainian Medical Stomatological Academy, ul. Shevchenko 23, Poltava, 36011 Ukraine
b Institute of Organic Chemistry, National Academy of Sciences of Ukraine, ul. Murmanskaya 5, Kiev, 02660 Ukraine
c Korolenko Poltava National Pedagogical University, ul. Ostrogradskogo 2, Poltava, 36003 Ukraine
d Institute of Chemical Technology and Industrial Ecology, pl. Khimikov 3, Rubezhnoe, Lugansk oblast, 93009 Ukraine
e Taras Shevchenko Lugansk National University, ul.Oboronnaya 2, Lugansk, 91011 Ukraine
*e-mail: dyachvd@mail.ru
f Kostroma State University, ul. Dzerzhinskogo 17, Kostroma, 156005 Russia
Received November 22, 2017
Abstract—New substituted naphthostyryl derivatives have been synthesized by nucleophilic vinylic substitu-
tion reactions and converted to the corresponding N-alkyl derivatives by treatment with alkyl halides.
DOI: 10.1134/S1070428018070163
Benzo[cd]indol-2(1H)-one (naphthostyryl) deriva-
tives were shown to initiate photopolymerization of
monomers containing acrylic acid fragments [1],
inhibit kinases [2, 3], and exhibit antitubercular [4, 5]
and antitumor activity [6–8].
well as of C=C (1179–1230 cm–1) and N–H bonds
(3247–3365 cm–1).
Introduction of an alkylating agent as the third
component into the SNVin reaction in DMF in the
presence of aqueous potassium hydroxide enabled one-
pot synthesis of N-alkyl-substituted naphthostyryls 14–
19 in good yields (Scheme 2). Compounds 14–19 are
potential 5-HT7R inhibitors [10]. The structure of 14–
19 was confirmed by spectral data. Unlike compounds
We previously synthesized naphthostyryl deriva-
tives via nucleophilic vinylic substitution [9]. We now
report the reactions of 2-(methylsulfanyl)benzo[cd]in-
dol-2-ium iodide (1) with CH acids 2–7. The reactions
were carried out by heating the reactants in anhydrous
ethanol in the presence of an equimolar amount of
triethylamine. As a result, we isolated the correspond-
ing nucleophilic vinylic substitution products, naph-
thostyryl derivatives 8–13 (Scheme 1). The structure of
1
8–13, the H NMR spectra of 14–19 displayed no NH
proton signal but signals belonging to the substituent
on that nitrogen atom appeared. In the spectrum of 19,
double signals from the ethyl substituent and the amino
group were present, obviously due to formation of
E and Z isomers.
1
8–13 was confirmed by spectral data. The H NMR
spectra of 8–13 contained signals from protons in the
naphthalene fragment with characteristic coupling con-
stants, a broadened singlet at δ 11.54–12.95 ppm due
to NH proton, and signals of the substituents (see
Experimental). The structures of 8–13 were consistent
with the number and position of carbon signals in their
13C NMR spectra. In the IR spectra of 8–13 we
observed absorption bands typical of stretching
vibrations of conjugated C≡N (2193–2204 cm–1), C=O
(1754 cm–1), and CONR groups (1575–1666 cm–1), as
EXPERIMENTAL
The H and 13C NMR spectra were recorded on
1
a Varian Mercury 400 spectrometer at 400.397 and
100 MHz, respectively, using DMSO-d6 as solvent and
tetramethylsilane as internal standard. The IR spectra
were measured in KBr on a Perkin Elmer Spectrum
One spectrometer. The mass spectra were obtained on
an Agilent 1100 Series LC/MSD instrument (samples
1071

KASHNER et al.
1072
Scheme 1.
Me
R
O
N
S
Ph
R
N
HN
S
N
O
S
S
O
S
HN
Me
O
N
S
2a, 2b
NHPh
5
HN
8a, 8b
11
NC
O
NHR
CN
CN
NC
Ph
CN
Ph
SMe
O
I– HN
NC
NHR
Me
HN
HN
6a, 6b
3
1
9
12a, 12b
O
S
OEt
Ph
O
N
OEt
N
O
O
N
Me
Ph
N
4
7
HN
S
HN
Me
10
13
2, 8, R = 2-MeOC6H4 (a), HO(CH2)2 (b); 6, 12, R = 1,3-thiazol-2-yl (a), pyridin-2-yl (b).
Scheme 2.
EtOOC
EtOOC
Et
COOEt
COOEt
Ph
N
N
CH2(COOEt)2, PhCH2Cl
CH2(COOEt)2, EtI
14
17
Ph
CN
CN
N
N
Ph
O
Et
Ph
4, PhCH2Cl
3, EtI
N
N
Me
1
15
18
CH2(CN)2
Cl
CN
H2N
NC
CN
CN
Br
H2N
Cl
, EtI
NC
CN
CN
O
Et
CN
N
N
O
16
19
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 54 No. 7 2018

NEW SYNTHESES OF NAPHTHOSTYRYL DERIVATIVES
1073
were introduced in acetic acid; electron impact,
70 eV). The elemental compositions were determined
with a Perkin Elmer CHN analyzer. The melting points
were measured on a Kofler hot stage. The progress of
reactions was monitored, and the purity of the isolated
compounds was checked, by TLC on Silufol UV-254
plates using acetone–hexane (3 :5) as eluent; spots
were visualized by treatment with iodine vapor and
under UV light.
spectrum, δ, ppm: 7.75 s (1H, CH=), 7.48–7.62 m (4H,
H
H
H
arom), 7.65–7.79 m (2H, Harom), 7.84–7.91 m (2H,
arom), 8.20 d (1H, Harom, J = 7.6 Hz), 8.40 d (1H,
arom, J = 6.2 Hz), 8.59 d (1H, Harom, J = 6.5 Hz). Mass
spectrum: m/z 320 (Irel 100%) [M + H]+. Found, %:
C 82.65; H 4.15; N 13.20. C22H13N3. Calculated, %:
C 82.74; H 4.10; N 13.16. M 319.365.
4-[Benzo[cd]indol-2(1H)-ylidene]-5-methyl-2-
phenyl-2,4-dihydro-3H-pyrazol-3-one (10). Yield
79%, red crystals, mp 232–234°C (from DMF). IR
spectrum, ν, cm–1: 3318 (N–H), 1590 (C=O), 1576
2-(Methylsulfanyl)benzo[cd]indol-1-ium iodide
(1) was synthesized as described in [11].
1
(C=C). H NMR spectrum, δ, ppm: 2.73 s (3H, Me),
Compounds 8–13 were synthesized according to
7.19–7.22 m (1H, Harom), 7.33–7.48 m (2H, Harom),
7.64 t (1H, Harom, J = 7.7 Hz), 7.69 d (1H, Harom, J =
7.2 Hz), 7.95 t (1H, Harom, J = 7.6 Hz), 8.07 t (2H,
the procedure reported in [9].
5-[Benzo[cd]indol-2(1H)-ylidene]-3-(2-methoxy-
phenyl)-2-sulfanylidene-1,3-thiazolidin-4-one (8a).
Yield 69%, red powder, mp 268–270°C (from BuOH).
IR spectrum, ν, cm–1: 3365 (N–H), 1601 (C=O), 1499
(C=C), 1230 (C=S). 1H NMR spectrum, δ, ppm: 3.76 s
(3H, Me), 7.13 t (1H, Harom, J = 7.0 Hz), 7.27 d (1H,
H
arom, J = 7.2 Hz), 8.33 d (1H, Harom, J = 8.0 Hz),
8.69 d (1H, Harom, J = 7.4 Hz), 9.99 d (1H, Harom, J =
13
7.3 Hz), 12.95 br.s (1H, NH). C NMR spectrum, δC,
ppm: 19.49, 100.16, 111.10, 112.35, 118.46, 118.64
(2C), 122.53, 124.41, 129.11, 129.77 (2C), 129.98,
130.10, 132.79, 139.50, 139.70, 146.64, 147.33,
153.58, 166.42. Mass spectrum: m/z 326 (Irel 100%)
[M + H]+. Found, %: C 77.40; H 4.58; N 12.88.
C21H15N3O. Calculated, %: C 77.52; H 4.65; N 12.91.
M 325.369.
H
H
arom, J = 7.9 Hz), 3.31–7.42 m (1H, Harom), 7.57 t (1H,
arom, J = 7.1 Hz), 7.61 t (1H, Harom, J = 7.1 Hz),
7.65 d (1H, Harom, J = 8.5 Hz), 7.90 t (1H, Harom, J =
7.4 Hz), 8.03 d (1H, Harom, J = 7.1 Hz), 8.20 t (1H,
H
arom, J = 8.0 Hz). 13C NMR spectrum, δC, ppm: 56.35,
93.05, 108.21, 109.56, 113.12, 120.26, 120.49, 121.24,
124.47, 125.10, 126.10, 129.95, 130.23, 130.27,
130.86, 131.57, 141.36, 144.05, 155.38, 165.93,
190.37. Mass spectrum: m/z 391 (Irel 100%) [M + H]+.
Found, %: C 64.42; H 3.55; N 7.12. C21H14N2O2S2.
Calculated, %: C 64.59; H 3.61; N 7.17. M 390.486.
2-[Benzo[cd]indol-2(1H)-ylidene]-2-[4-(4-methyl-
phenyl)-1,3-thiazol-2-yl]-N-phenylacetamide (11).
Yield 2.8 g (60%), dark red crystals, mp 198–200°C
(from EtOH). IR spectrum, ν, cm–1: 3293 (N–H), 1627
(C=O), 1589 (C=C). 1H NMR spectrum, δ, ppm: 2.33 s
(3H, Me), 7.18 t (1H, Harom, J = 7.7 Hz), 7.28 d (2H,
5-[Benzo[cd]indol-2(1H)-ylidene]-3-(2-hydroxy-
ethyl)-2-sulfanylidene-1,3-thiazolidin-4-one (8b).
Yield 88%, red crystals, mp 241–243°C (from BuOH).
IR spectrum, ν, cm–1: 3460 (OH), 3336 (N–H), 1650
H
arom, J = 6.8 Hz), 7.36 d (2H, Harom, J = 7.7 Hz),
7.45 t (3H, Harom, J = 8.1 Hz), 7.51 t (1H, Harom, J =
7.7 Hz), 7.70 d (1H, Harom, J = 7.2 Hz), 7.78 d (2H,
Harom, J = 7.7 Hz), 7.90 d (1H, Harom, J = 8.1 Hz),
7.96 s (1H, 5′-H), 8.04d (2H, Harom, J = 7.9 Hz),
10.97 br.s (1H, NHCO), 11.51 br.s (1H, NH).
13C NMR spectrum, δC, ppm: 21.37, 104.65, 105.93,
111.97, 118.05, 120.19 (2C), 122.88 (2C), 126.77,
128.10, 129.31 (2C), 129.53, 129.72, 129.86 (2C),
129.90, 129.98 (2C), 131.18, 131.87, 138.08, 139.77,
141.62, 143.05, 154.76, 165.36, 165.70. Mass spec-
trum: m/z 460 (Irel 100%) [M + H]+. Found, %:
C 75.68; H 4.55; N 8.88. C29H21N3OS. Calculated, %:
C 75.79; H 4.61; N 9.14. M 459.568.
1
(C=O), 1567 (C=C), 1179 (C=S). H NMR spectrum,
δ, ppm: 3.59–3.72 m (2H, CH2O), 4.15 t (2H, CH2, J =
5.9 Hz), 4.95 br.s (1H, OH), 7.35 d (1H, Harom, J =
6.8 Hz), 7.52–7.63 m (2H, Harom), 7.84 t (2H, Harom, J =
7.7 Hz), 7.93 d (1H, Harom, J = 7.2 Hz), 8.17 d (1H,
H
arom, J = 8.0 Hz), 11.64 br.s (1H, NH). 13C NMR
spectrum, δC, ppm: 46.50, 57.24, 92.72, 109.54,
120.17, 125.02, 125.86, 129.80, 130.16, 130.19,
130.70, 140.61, 141.31, 143.91, 166.45, 190.16. Mass
spectrum: m/z 329 (Irel 100%) [M + H]+. Found, %:
C 58.40; H 3.57; N 8.48. C16H12N2O2S2. Calculated,
%: C 58.52; H 3.68; N 8.53. M 328.415.
2-[Benzo[cd]indol-2(1H)-ylidene]-2-cyano-
N-(1,3-thiazol-2-yl)ethanamide (12a). Yield 2.6 g
(82%), yellow crystals, mp 231–233°C (from AcOH).
IR spectrum, ν, cm–1: 3298, 3116 (N–H), 2196 (C≡N),
[2-(Benzo[cd]indol-2(1H)-ylidene)-1-phenyl-
ethylidene]propanedinitrile (9). Yield 69%, red
powder, mp 218–220°C (from DMF). IR spectrum, ν,
cm–1: 3309 (N–H), 2205 (C≡N), 1584 (C=C). 1H NMR
1
1646 (C=O), 1530 (C=C). H NMR spectrum, δ, ppm:
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 54 No. 7 2018

KASHNER et al.
1074
7.10 d (1H, 4′-H or 5′-H, J = 3.3 Hz), 7.45 d (1H,
alkyl halide were added in succession with stirring.
The mixture was left to stand for 24 h and diluted with
15 mL of water, and the precipitate was filtered off and
washed with water, ethanol, and hexane.
H
arom, J = 6.7 Hz), 7.49 d (1H, 5′-H or 4′-H, J =
3.3 Hz), 7.60 t (1H, Harom, J = 7.1 Hz), 7.66 d (1H,
Harom, J = 8.2 Hz), 7.89 t (1H, Harom, J = 7.8 Hz),
8.23 d (1H, Harom, J = 7.8 Hz), 8.52 d (1H, Harom, J =
7.1 Hz), 12.17 br.s (1H, CONH), 12.67 br.s (1H, NH).
13C NMR spectrum, δC, ppm: 109.91, 119.54, 120.92,
125.04, 126.63, 129.67 (2C), 129.95 (2C), 130.03
(2C), 130.16 (2C), 131.53, 140.21, 156.48, 164.12.
Mass spectrum: m/z 319 (Irel 100%) [M + H]+. Found,
%: C 64.20; H 3.13; N 17.48. C17H10N4OS. Calculated,
%: C 64.14; H 3.17; N 17.60. M 318.356.
Diethyl 2-[1-benzylbenzo[cd]indol-2(1H)-
ylidene]propanedioate (14). Yield 2.9 g (71%),
orange crystals, mp 135–137°C (from EtOH). IR spec-
1
trum, ν, cm–1: 1678 (C=O), 1556 (C=C). H NMR
spectrum, δ, ppm: 1.17 t (6H, Me, J = 7.0 Hz), 3.09 q
(4H, CH2O, J = 7.0 Hz), 5.26 s (2H, NCH2), 7.01–
7.12 m (3H, Harom), 7.19–7.27 m (3H, Harom), 7.48 t
(1H, Harom, J = 7.5 Hz), 7.53 d (1H, Harom, J = 8.3 Hz),
7.71 t (1H, Harom, J = 7.8 Hz), 8.04 d (1H, Harom, J =
8.0 Hz), 8.09 d (1H, Harom, J = 7.4 Hz). 13C NMR
spectrum, δC, ppm: 9.15 (2C), 14.34 (2C), 46.32,
99.37, 106.51, 120.05, 125.01, 125.15, 125.22, 125.95
(2C), 127.05, 127.72, 127.91, 128.96 (2C), 129.02,
129.46, 129.51, 136.68, 143.96, 152.21, 166.50. Mass
spectrum: m/z 402 (Irel 100%) [M + H]+. Found, %:
C 74.70; H 5.68; N 3.35. C25H23NO4. Calculated, %:
C 74.80; H 5.77; N 3.49. M 401.462.
2-[Benzo[cd]indol-2(1H)-ylidene]-2-cyano-
N-(pyridin-2-yl)ethanamide (12b). Yield 2.6 g
(82%), light yellow crystals, mp 232–234°C (from
DMF). IR spectrum, ν, cm–1: 3391, 3300 (N–H), 2193
1
(C≡N), 1666 (C=O), 1570 (C=C). H NMR spectrum,
δ, ppm: 7.17 t (1H, Harom, J = 6.1 Hz), 7.48 d (1H,
H
arom, J = 7.0 Hz), 7.62 t (1H, Harom, J = 8.0 Hz),
7.73 d (1H, Harom, J = 8.1 Hz), 7.88 t (1H, Harom, J =
8.1 Hz), 7.92 t (1H, Harom, J = 7.6 Hz), 8.12 d (1H,
Harom, J = 8.2 Hz), 8.27 d (1H, Harom, J = 8.0 Hz),
8.37 d (1H, Harom, J = 6.2 Hz), 8.52 d (1H, Harom, J =
7.2 Hz), 9.19 br.s (1H, CONH), 12.13 br.s (1H, NH).
13C NMR spectrum, δC, ppm: 110.74, 113.92, 119.34,
120.21, 121.56, 124.61, 126.82, 129.74 (2C), 129.81,
129.88 (2C), 129.95, 138.73, 139.99, 148.68, 151.80,
156.97, 164.08. Mass spectrum: m/z 313 (Irel 100%)
[M + H]+. Found, %: C 72.95; H 3.76; N 17.84.
C19H12N4O. Calculated, %: C 73.07; H 3.87; N 17.94.
M 312.33.
4-[1-Benzylbenzo[cd]indol-2(1H)-ylidene]-
5-methyl-2-phenyl-2,4-dihydro-3H-pyrazol-3-one
(15). Yield 3.9 g (93%), dark red crystals, mp 223–
225°C (from BuOH). IR spectrum, ν, cm–1: 1623
(C=O), 1513 (C=C). 1H NMR spectrum, δ, ppm: 2.40 s
(3H, Me), 6.00 s (2H, CH2), 7.01–7.12 m (3H, Harom),
7.13–7.24 m (3H, Harom), 7.32–7.47 m (3H, Harom),
7.68 d (2H, Harom, J = 7.3 Hz), 7.76 d (1H, Harom, J =
7.8 Hz), 7.85–7.88 m (2H, Harom), 7.98 d (1H, Harom
,
13
J = 7.8 Hz), 8.38 d (1H, Harom, J = 8.0 Hz). C NMR
spectrum, δC, ppm: 17.25, 46.18, 95.11, 100.07,
101.13, 104.10, 105.06, 111.02, 113.29, 114.16,
117.19, 118.02, 119.03, 123.11, 123.40, 124.06, 127.13
(2C), 128.07, 128.75 (2C), 130.34, 131.52, 132.87,
133.92, 138.06, 139.99, 147.10. Mass spectrum:
m/z 416 (Irel 100%) [M + H]+. Found, %: C 80.87;
H 4.95; N 10.02. C28H21N3O. Calculated, %: C 80.94;
H 5.09; N 10.11. M 415.493.
2-(Benzo[cd]indol-2(1H)-ylidene)-5-ethoxy-
1-benzothiophen-3(2H)-one (13). Yield 2.6 g (78%),
dark red crystals, mp 234–236°C (from DMF). IR
spectrum, ν, cm–1: 3247 (N–H), 1595 (C=O), 1566
(C=C). 1H NMR spectrum, δ, ppm: 1.38 t (3H, Me, J =
6.5 Hz), 4.17 q (2H, OCH2, J = 6.5 Hz), 6.94 d (1H,
H
arom, J = 8.4 Hz), 7.28–7.33 m (2H, Harom), 7.51–
7.59 m (2H, Harom), 7.77 d (1H, Harom, J = 8.5 Hz),
7.89 t (1H, Harom, J = 7.3 Hz), 8.05 d (1H, Harom, J =
6.8 Hz), 8.13 d (1H, Harom, J = 8.0 Hz), 12.05 br.s (1H,
NH). Mass spectrum: m/z 334 (Irel 100%) [M + H]+.
Found, %: C 71.96; H 4.42; N 4.18. C21H15NO2S. Cal-
culated, %: C 72.05; H 4.54; N 4.20. M 333.412.
2-{1-[2-(4-Chlorophenyl)-2-oxoethyl]benzo[cd]-
indol-2(1H)-ylidene}propanedinitrile (16). Yield
2.7 g (74%), yellow powder, mp 241–243°C (from
dioxane). IR spectrum, ν, cm–1: 2205 (C≡N), 1702
(C=O), 1541 (C=C). 1H NMR spectrum, δ, ppm: 6.18 s
(2H, CH2), 7.65 br.s (2H, Harom), 7.72 d (2H, Harom, J =
7.9 Hz), 7.83 br.s (1H, Harom), 7.95 t (1H, Harom, J =
7.6 Hz), 8.13 d (2H, Harom, J = 7.9 Hz), 8.35 d (1H,
Compounds 14–19 (general procedure). A mixture
of 3.3 g (10 mmol) of salt 1, 10 mmol of the corre-
sponding CH acid, and 1.4 mL (10 mmol) of triethyl-
amine in 20 mL of ethanol was refluxed for 2 h. The
mixture was cooled to room temperature and diluted
with an equal volume of DMF, and 5.6 mL (10 mmol)
of 10% aqueous potassium hydroxide and 10 mmol of
H
arom, J = 7.9 Hz), 8.50 d (1H, Harom, J = 7.9 Hz).
13C NMR spectrum, δC, ppm: 51.84, 109.01, 115.43,
116.23, 122.64, 123.15, 126.96, 128.28, 129.15 (2C),
129.22, 129.35, 129.84, 130.51 (2C), 131.14, 132.64,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 54 No. 7 2018

NEW SYNTHESES OF NAPHTHOSTYRYL DERIVATIVES
1075
139.33, 140.17, 141.32, 158.06, 191.50. Mass
spectrum: m/z 370 (Irel 100%) [M + H]+. Found, %:
C 71.30; H 3.14; N 11.22. C22H12ClN3O. Calculated,
%: C 71.45; H 3.27; N 11.36. M 369.813.
(3H, Harom), 8.07–8.53 m (3H, Harom), 9.05 br.s and
9.35 br.s (2H, NH2). Mass spectrum: m/z 312
(Irel 100%) [M + H]+. Found, %: C 73.18; H 4.27;
N 22.55. C19H13N5. Calculated, %: C 73.30; H 4.21;
N 22.49. M 311.346.
Diethyl 2-[1-ethylbenzo[cd]indol-2(1H)-ylidene]-
propanedioate (17). Yield 2.3 g (67%), orange crys-
tals, mp 101–103°C (from MeOH). IR spectrum, ν,
cm–1: 1705 (C=O), 1553 (C=C). 1H NMR spectrum, δ,
ppm: 1.11–1.32 m (9H, Me), 3.94 q (2H, CH2N, J =
7.0 Hz), 4.24 q (4H, CH2O, J = 4.0 Hz), 7.17 d (1H,
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H
H
arom, J = 6.0 Hz), 7.52 br.s (2H, Harom), 7.68 t (1H,
arom, J = 7.6 Hz), 8.02 d (1H, Harom, J = 8.0 Hz),
8.16 d (1H, Harom, J = 7.4 Hz). 13C NMR spectrum, δC,
ppm: 12.83, 14.46 (2C), 46.25, 61.11 (2C), 98.17,
106.12, 119.96, 125.55, 126.37, 129.38 (2C), 129.44,
129.70, 129.99, 131.53, 143.11, 152.14, 166.80. Mass
spectrum: m/z 340 (Irel 100%) [M + H]+. Found, %:
C 61.82; H 6.18; N 4.05. C20H21NO4. Calculated, %:
C 61.94; H 6.24; N 4.13. M 339.392.
2-{2-[1-Ethylbenzo[cd]indol-2(1H)-ylidene]-1-
phenylethylidene}propanedinitrile (18). Yield 2.1 g
(61%), dark green crystals, mp 219–221°C (from
DMF). IR spectrum, ν, cm–1: 2199 (C≡N), 1544
(C=C). 1H NMR spectrum, δ, ppm: 1.38 t (3H, Me, J =
6.1 Hz), 4.25 q (2H, CH2, J = 6.1 Hz), 5.85 br.s (1H,
CH=), 6.43 s (1H, Harom), 7.18 t (1H, Harom, J =
6.8 Hz), 7.37 d (1H, Harom, J = 5.8 Hz), 7.46–7.61 m
(7H, Harom), 7.90 d (1H, Harom, J = 7.8 Hz). Mass spec-
trum: m/z 348 (Irel 100%) [M + H]+. Found, %:
C 82.87; H 4.96; N 12.17. C24H17N3. Calculated, %:
C 82.97; H 4.93; N 12.10. M 347.418.
7. Yin, H., Xu, Y., and Qian, X., Bioorg. Med. Chem.,
2007, vol. 15, p. 1356.
8. Li, X., Wang, Q., Qing, Y., Lin, Y., Zhang, Y., Qian, X.,
and Cui, J., Bioorg. Med. Chem., 2010, vol. 18, p. 3279.
9. Dyachenko, V.D., Kashner, A.Yu., and Samusen-
2-Amino-3-[1-ethylbenzo[cd]indol-2(1H)-
ylidene]prop-1-ene-1,1,3-tricarbonitrile (19). Yield
1.9 g (61%), dark powder, mp 242–244°C (from
BuOH). IR spectrum, ν, cm–1: 3344, 3330, 3211 (NH2),
2213, 2197, 2180 (C≡N), 1654 (δNH2), 1530 (C=C).
1H NMR spectrum, δ, ppm: 1.28 br.s and 1.40 br.s (3H,
Me), 4.09 br.s and 4.41 br.s (2H, CH2), 7.26–7.99 m
ko, Yu.V., Russ. J. Gen. Chem., 2014, vol. 84, p. 259.
10. Lopez-Rodrigues, M.L., Porras, E., Morcillo, M.J.,
Benhamu, B., Soto, L.J., Lavandera, J.L., Ramos, J.A.,
Olivella, M., Campillo, M., and Pardo, L., J. Med.
Chem., 2003, vol. 40, p. 5638.
11. Fry, D.J. and Kendall, J.D., J. Chem. Soc., 1951,
p. 1716.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 54 No. 7 2018