Synthesis and alkylation of 1-alkyl(aryl)-4-cyano-3-dicyanomethylene- substituted carbo[c]fused pyridines. Molecular and crystal structure of 2-(4-cyano-1-methyl-5,6,7,8-tetrahydroisoquinolin-3-yl)-2-(2-oxo-2-phenylethyl) malononitrile and 10-amino-8-phen

Article abstract of DOI:10.1134/S1070363213070141

Condensation of 2-acyl-1-(N-morpholinyl)cycloalkene with malononitrile dimer results in 1-alkyl-(aryl)-4-cyano-3-dicyanomethylene-substituted carbo[c]fused pyridines. Reaction of the latter with alkyl halides affords the corresponding 2-alkyl-2-(3-isoquin

Full text of DOI:10.1134/S1070363213070141

ISSN 1070-3632, Russian Journal of General Chemistry, 2013, Vol. 83, No. 7, pp. 1383–1393. © Pleiades Publishing, Ltd., 2013.
Original Russian Text © I.V. Dyachenko, E.B. Rusanov, A.V. Gutov, M.V. Vovk, 2013, published in Zhurnal Obshchei Khimii, 2013, Vol. 83, No. 7,
pp. 1132–1142.
Synthesis and Alkylation
of 1-Alkyl(aryl)-4-cyano-3-dicyanomethylene-Substituted
Carbo[c]fused Pyridines. Molecular and Crystal Structure
of 2-(4-Cyano-1-methyl-5,6,7,8-tetrahydroisoquinolin-3-yl)-
2-(2-oxo-2-phenylethyl)malononitrile
and 10-Amino-8-phenyl-5-(2-chlorophenyl)-1,2,3,4-tetrahydro-
7H-pyrido[2',3':3,4]cyclopenta[1,2-c]isoquinoline-
7,7,9-tricarbonitrile
I. V. Dyachenkoa, E. B. Rusanovb, A. V. Gutovb, and M. V. Vovkb
a Shevchenko Lugansk National University, ul. Oboronnaya 2, Lugansk, 91011 Ukraine
e-mail: ivladya87@e-mail.ua
b Institute of Organic Chemistry, National Academy of Sciences of Ukraine, Kiev, Ukraine
e-mail: mvovk@i.com.ua
Received June 7, 2013
Abstract—Condensation of 2-acyl-1-(N-morpholinyl)cycloalkene with malononitrile dimer results in 1-alkyl-
(aryl)-4-cyano-3-dicyanomethylene-substituted carbo[c]fused pyridines. Reaction of the latter with alkyl
halides affords the corresponding 2-alkyl-2-(3-isoquinolinyl)malononitrile, 1-amino-2-(4-bromobenzoyl)-5-(2-
chlorophenyl)-6,7,8,9-tetrahydro-3H-cyclopenta[c]isoquinoline-3,3-dicarbonitrile and 10-amino-8-phenyl-5-(2-
chlorophenyl)-1,2,3,4-tetrahydro-7H-pyrido[2',3':3,4]cyclopenta[1,2-c]isoquinoline-7,7,9-tricarbonitrile. Struc-
ture of the latter and of 2-(1-methyl-4-cyano-5,6,7,8-tetrahydroisoquinolin-3-yl)-2-(2-oxo-2-phenylethyl)-malo-
nonitrile was investigated by XRD.
DOI: 10.1134/S1070363213070141
Carbo[c]fused pyridine derivatives exhibit fungicidal
[1, 2] and bactericidal [3–5] activity and can be used as
poly(ADP-ribose)polymerase-1 inhibitor [6], anti-
epileptic drugs [7 8], and as intermediates in alkaloids
synthesis [9, 10]. Generally, a condensation of 2-acyl-
cycloalkanones with cyanoacetamide [11] and cyano-
thioacetamide [12, 13], cycloalkylidenemalononitrile
with arylmethylenecyanothioacetamide [14, 15] or
cyclopentylidenecyanoacetamide with benzaldehyde
[16] is used to form carbo[c]fused pyridine ring.
In this work we studied the previously unknown
representatives of compounds of this type, 1-alkyl(aryl)-
4-cyano-3-dicyanomethylene-substituted carbo[c]fused
pyridines Ia–Ii. Compounds Ia–Ii were obtained in
68–82% yields by the reaction of nucleophilic vinyl
substitution (SNVin) [17–19] of 2-acyl-1-(N-morpho-
linyl)cycloalkenes IIa–IIi with a malononitrile dimer
III. The reaction occurs at room temperature in an-
hydrous ethanol in the presence of sodium ethoxide.
Apparently, the reaction involves the formation of
intermediates A, which further undergo an intramole-
cular cyclization. The previously obtained compound
Іg (yield 47%) has been characterized only by
elemental analysis [20].
The structure of compounds Ia–Ii was confirmed
by the spectral characteristics. For example, their IR
spectra contain absorption bands of stretching vibra-
tions of conjugated cyano groups in the range of 2177–
1
2218 cm–1. In the H NMR spectra along with the
signals of the protons of R, R1, and R2 substituents
there are the proton signals of cycloalkane moiety in
the range of 1.73–3.25 ppm and of NH proton of
pyridine ring as a broad singlet at 8.70–12.55 ppm. In
some cases the signal of the NH-proton was not
1383

1384
DYACHENKO et al.
Table 1. Bond lengths in the structure of VIc
methyl-2-dicyanomethylene-3-cyano-1,2-dihydropyri-
dine, showing its planar structure and aromatic nature
[23].
Bond
d, Å
Bond
d, Å
C1–N1
C1–C2
C1–C6
C2–C3
C2–C17
C3–C4
C3–C18
C4–C5
C4–C21
C5–N1
C5–C22
C6–C8
C6–C7
C6–C9
C7–N2
C8–N3
C9–C10
C9–H9A
C9–H9B
C10–O1
C10–C11
C11–C12
C11–C16
C12–C13
1.321(3)
1.392(3)
1.550(3)
1.406(3)
1.438(3)
1.380(3)
1.514(3)
1.404(3)
1.506(3)
1.345(3)
1.493(3)
1.478(4)
1.487(3)
1.544(3)
1.138(3)
1.131(3)
1.514(3)
0.9700
C12–H12
C13–C14
C13–H13
C14–C15
C14–H14
C15–C16
C15–H15
C16–H16
C17–N4
C18–C19
C18–H18A
C18–H18B
C19–C20
C19–H19A
C19–H19B
C20–C21
C20–H20A
C20–H20B
C21–H21A
C21–H21B
C22–H22A
C22–H22B
C22–H22C
0.9300
1.376(4)
0.9300
1.381(4)
0.9300
1.380(3)
0.9300
0.9300
1.141(3)
1.517(3)
0.9700
0.9700
1.469(4)
0.9700
0.9700
1.525(3)
0.9700
0.9700
0.9700
0.9700
0.9600
0.9600
0.9600
The aromatization of 1,2-dihydropyridine core of
compounds Ia–Ii occurs in their reaction with halides
Va–Vh in a DMF solution in the presence of KOH.
Most likely, under the action of alkali carbanions B are
formed, which undergo C-alkylation to give deriva-
tives VIa–VIk. Note that on the basis of spectral data
it is not possible to confirm reliably that the reaction
involves an attack on the carbon atom of malononitrile
fragment rather than on an alternative nitrogen atom of
the pyridine ring (Scheme 1).
The structure of the alkylation products was un-
ambiguously determined by an example of compound
VIc using X-ray diffraction method (Fig. 1, Tables 1,
2). Such heterocyclic system was investigated by XRD
for the first time. The lengths of carbon–carbon bonds
in the pyridine ring N1–C1–5 are in the range of 1.380–
1.406(3) Å. As expected, the C–C bonds with the
nitrile groups are somewhat non-equivalent. Thus, the
C6–C7 and C6–C8 bonds are somewhat longer than the
C2–C17 bond, due to the different hybridization of the
C2 and C6 atoms. At the same time the C≡N bonds are
identical within 3σ. Phenyl ring C11–C16 is turned
relative to the central pyridine ring by 3.35(3)°, while
the atoms of the pyridine ring itself have a mean
deviation from the plane of 0.0236 Å.
0.9700
It is significant to stress that at the use of 2-(2-
bromo-1-phenylethylidene)malononitrile VII as an
alkylating agent the reaction acquires a cascade cha-
racter. Thus, the reaction of 2-[1-(2-chlorophenyl)-4-
cyano-5,6,7,8-tetrahydroisoquinolin-3(2H)-ylidene]malo-
nonitrile Id with malononitrile derivative VII in DMF
solution in the presence of an aqueous KOH solution at
20°C results in a new heterocyclic system, 10-amino-
8-phenyl-5-(2-chlorophenyl)-1,2,3,4-tetrahydro-7H-
pyrido[2',3':3,4]cyclopenta[1,2-c]isoquinoline-7,7,9-
tricarbonitrile VIII in a yield of 62%. Most likely, the
reaction proceeds through a carbanion formation. The
latter undergoes a domino process to give an inter-
mediate D followed by the conversion into the target
compound. This reaction pathway is confirmed by the
synthesis of 1-amino-2-(4-bromobenzoyl)-5-(2-chloro-
phenyl)-6,7,8,9-tetrahydro-3H-cyclopenta[c]isoquino-
line-3,3-dicarbonitrile IX as an analog of the
intermediate D by reacting compound Ie with 4-
bromophenacyl bromide Va via the formation of
carbanion D (Scheme 1).
1.214(2)
1.482(3)
1.385(3)
1.388(3)
1.373(3)
observed, apparently due to rapid deuterium exchange.
The latter indicates the NH-proton lability and the
ability of compounds Ia–Ii to undergo the prototropic
tautomerism to form aromatic forms IVa–IVi. This is
confirmed by the 13C NMR spectrum of compound Ia,
where a doubling of the signals of carbon atoms is
observed. Furthermore, unfused pyridines containing
dicyanomethylene moiety in the position 2 can exist as
NH- [21] or CH-prototropic tautomers [22]. An ease of
the proton elimination from the nitrogen atom of 1,2-
dihydropyridine core resulting in aromatization was
confirmed also by the X-ray analysis data of 5,6-di-
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 83 No. 7 2013

SYNTHESIS AND ALKYLATION OF 1-ALKYL(ARYL)-4-CYANO-3-DICYANOMETHYLENE-...
1385
Table 2. Bond angles in the structure of VIc
Angle
ω, deg
Angle
ω, deg
Angle
ω, deg
Angle
ω, deg
N1C1C2
122.6(2)
C13C14C15
120.4(2)
N2C7C6
175.0(3)
H19AC19H19B
107.8
112.2(2)
109.2
109.2
109.2
109.2
107.9
112.5(2)
109.1
109.1
109.1
109.1
107.8
109.5
109.5
109.5
109.5
109.5
109.5
118.21(19)
N1C1C6
C2C1C6
C1C2C3
C1C2C17
C3C2C17
C4C3C2
C4C3C18
C2C3C18
C3C4C5
C3C4C21
C5C4C21
N1C5C4
N1C5C22
C4C5C22
C8C6C7
C8C6C9
C7C6C9
C8C6C1
C7C6C1
C9C6C1
115.39(19)
122.0(2)
119.4(2)
121.4(2)
119.2(2)
118.1(2)
122.5(2)
119.5(2)
118.3(2)
121.5(2)
120.2(2)
123.1(2)
115.2(2)
121.7(2)
109.33(19)
109.20(18)
109.9(2)
108.6(2)
108.09(18)
111.65(18)
C13C14H14
C15C14H14
C14C15C16
C14C15H15
C16C15H15
C15C16C11
C15C16H16
C11C16H16
N4C17C2
119.8
N3C8C6
176.2(3)
C19C20C21
119.8
C10C9C6
113.52(19) C19C20H20A
119.9(3)
120.0
C10C9H9A
C6C9H9A
C10C9H9B
C6C9H9B
H9AC9H9B
O1C10C11
O1C10C9
108.9
C21C20H20A
C19C20H20B
C21C20H20B
H20AC20H20B
C4C21C20
108.9
120.0
108.9
120.0(2)
120.0
108.9
107.7
120.0
121.1(2)
120.2(2)
118.6(2)
119.3(2)
118.4(2)
122.4(2)
120.7(2)
119.7
C4C21H21A
C20C21H21A
C4C21H21B
C20C21H21B
H21AC21H21B
C5C22H22A
C5C22H22B
H22AC22H22B
C5C22H22C
H22AC22H22C
H22BC22H22C
C1N1C5
179.2(3)
113.0(2)
109.0
C3C18C19
C11C10C9
C12C11C16
C12C11C10
C16C11C10
C13C12C11
C13C12H12
C11C12H12
C12C13C14
C12C13H13
C14C13H13
C3C18H18A
C19C18H18A
C3C18H18B
C19C18H18B
H18AC18H18B
C20C19C18
C20C19H19A
C18C19H19A
C20C19H19B
C18C19H19B
109.0
109.0
109.0
107.8
112.5(2)
109.1
119.7
119.8(3)
120.1
109.1
109.1
120.1
109.1
The IR spectrum of compound IX contains the
absorption bands of stretching and bending vibrations
of amino group at 1641 and 3445 cm–1, respectively,
and the absorption band of the stretching vibrations of
the non-conjugated cyano and carbonyl groups at 2255
and 1687 cm–1, respectively. In the 1H NMR spectrum,
along with the signals of the protons of aromatic
substituents and tetramethylene, there is a broad singlet
of the protons of conjugated amino group at 8.80 ppm.
The 13C NMR spectrum of the heterocyclic system IX
contains the signals of all carbon atoms in their
respective areas.
Fig. 2. The central bipyridocyclopentane system is
planar within 0.05 Å (according Cambridge Structural
Database, similar structures have not been studied
In addition to the spectral methods the XRD
method was used to prove the structure of compound
VIII (Tables 3 and 4). The general view of the
molecule and the atom numbering scheme is shown in
Fig. 1. General view and the numbering of the atoms of the
molecule of VIc.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 83 No. 7 2013

1386
DYACHENKO et al.
Scheme 1.
R2
R2
R1
R1
CN
CN
n
n
CN
EtONa
CN
+
N
H2N
CN
CN
NH
O
O
O H2N
R
R
O
IIa_IIi
III
A
_H2O
Br
R2
R2
R1
R1
NH2
n
n
Cl
CN
CN
CN
CN
CN
O
N
CN
NC
R
N
H
R
N
H
CN
IX
IVa_IVi
Ia_Ii
H2O
KOH/DMF
R2
R2
R1
R1
N
n
C
Br
Hlg
X
CN
Cl
n
Va_Vh
Va
CN
CN
CN
_KHlg
N
R
N
X
NC CN
O
NC CN
VIa_VIk
R
N
E
B
Br
CN
CN
Ph
VII
N
NH
C
N
C
N
NH2
CN
Cl
Cl
CN
CN
Cl
CN
N
Ph
N
N
CN
NC CN
NC
NC CN
Ph
Ph
D
VIII
C
I, II: n = 0 (a, b), 1 (c–i); R = Me, R1 = R2 = H (a); R = Ph, R1 = R2 = H (b); R = Ph, R1 = H, R2 = Me (c); R = Me, R1 = Ph, R2 = H (d);
R = 2-ClC6H4, R1 = R2 = H (e); R = R2 = Me, R1 = H (f); R = Me, R1 = R2 = H (g); R = Ph, R1 = R2 = H (h); R = CH(Me)2,
R1 = R2 = H (i); V: Hlg = Br (a–g), Hlg = Cl (h); X = 4-BrC6H4CO (a), PhCO (b), C≡CH (c), coumarin-3-ylcarbonyle (d),
СН=СН2 (e), 3,4-(ОН)2С6Н3СО (f), 4-ClC6H4CO (g), Ph (h); VI: n = 0 (a), 1 (b–k), R = Ph, R1 = R2 = H, X = C≡CH (a); R = Me,
R1 = R2 = H, X = Ph (b); R = Me, R1 = R2 = H, X = PhСО (c); R = i-Pr, R1 = R2 = H, X = 4-BrC6H4СО (d); R = i-Pr, R1 = R2 = H,
X = C≡CH (e); R = i-Pr, R1 = R2 = H, X = coumarin-3-ylcarbonyle (f); R = 2-ClC6H4, R1 = R2 = H, X = C≡CH (g); R = Ph, R1 = R2 = H,
X = СН=СН2 (h); R = Ph, R1 = H, R2 = Ме, X = СН=СН2 (i); R = R2 = Ме, R1 =Н, X = 3,4-(ОН)2С6Н3СО (j); R = i-Pr, R1 = R2 = H,
X = 4-ClC6H4CO (k).
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 83 No. 7 2013

SYNTHESIS AND ALKYLATION OF 1-ALKYL(ARYL)-4-CYANO-3-DICYANOMETHYLENE-...
Table 3. Bond lengths in the structure of VIII
Table 4. Bond angles in the structure of VIII
1387
Angle
C14AC14B
N1C1C5
N1C1C11
C5C1C11
N1C2C3
N1C2C25
C3C2C25
C4C3C2
C4C3C12
C2C3C12
C3C4C5
C3C4C15
C5C4C15
C1C5C4
C1C5C6
C4C5C6
N2C6C10
N2C6C5
C10C6C5
N3C7N2
N3C7C8
N2C7C8
C9C8C24
C9C8C7
C24C8C7
C10C9C8
C10C9C18
C8C9C18
C6C10C9
C6C10C11
C9C10C11
C16C11C17
C16C11C10
C17C11C10
C16C11C1
C17C11C1
C10C11C1
C13C12C3
ω, deg
Angle
ω, deg
Bond
C1–N1
C1–C5
C1–C11
C2–N1
C2–C3
C2–C25
C3–C4
C3–C12
C4–C5
C4–C15
C5–C6
C6–N2
C6–C10
C7–N3
C7–N2
C7–C8
C8–C9
C8–C24
C9–C10
C9–C18
C10–C11
C11–C16
C11–C17
C12–C13
d, Å
Bond
C13–C14B
C13–C14A
C15–C14B
C15–C14A
C16–N5
d, Å
1.13(3)
C14BC13C14A
C14BC13C12
C14AC13C12
C14BC15C4
C14BC15C14A
C4C15C14A
N5C16C11
N4C17C11
C19C18C23
C19C18C9
47.8(11)
122.5(9)
112.7(8)
111.1(8)
42.7(10)
108.9(6)
177.0(4)
178.3(5)
118.6(4)
120.5(4)
120.8(4)
120.9(4)
120.2(5)
119.4(5)
121.2(5)
119.6(5)
174.3(5)
119.3(4)
123.1(4)
117.6(4)
115.1(5)
123.5(5)
121.7(5)
118.7(5)
121.6(5)
120.1(4)
118.3(4)
118.6(7)
118.8(9)
101.5(10)
62.9(12)
65.7(10)
109.4(8)
69.3(15)
71.6(13)
117.1(15)
115.4(3)
115.7(3)
1.314(5)
1.387(5)
1.550(5)
1.367(5)
1.403(6)
1.492(6)
1.397(6)
1.516(6)
1.397(5)
1.520(6)
1.469(5)
1.329(5)
1.389(5)
1.341(5)
1.349(5)
1.429(6)
1.400(5)
1.421(6)
1.395(5)
1.476(5)
1.520(5)
1.472(6)
1.484(6)
1.512(12)
1.35(2)
126.8(4)
122.7(3)
110.4(3)
122.5(4)
115.4(4)
121.9(4)
120.2(4)
120.9(4)
118.9(4)
116.9(4)
122.0(4)
121.0(4)
118.2(4)
108.5(3)
133.3(3)
125.8(4)
124.8(3)
109.3(3)
117.5(4)
120.2(4)
122.4(3)
121.5(4)
120.7(4)
117.7(4)
115.3(3)
122.9(3)
121.7(3)
120.0(3)
110.7(3)
129.2(3)
109.8(3)
113.7(3)
112.8(3)
108.9(3)
110.3(3)
101.0(3)
113.3(5)
1.423(17)
1.517(16)
1.578(12)
1.138(5)
1.137(5)
1.390(6)
1.394(6)
1.380(6)
1.376(7)
1.376(7)
1.386(7)
1.153(6)
1.370(7)
1.481(7)
1.381(7)
1.369(8)
1.340(7)
1.412(7)
1.721(5)
1.343(7)
1.399(11)
1.589(15)
1.439(15)
C17–N4
C18–C19
C18–C23
C19–C20
C20–C21
C21–C22
C22–C23
C24–N6
C23C18C9
C20C19C18
C21C20C19
C22C21C20
C21C22C23
C22C23C18
N6C24C8
C30C25C26
C30C25C2
C26C25C2
C27C26C25
C28C27C26
C29C28C27
C28C29C30
C25C30C29
C25C30Cl1
C29C30Cl1
O1C31C32
C31C32C33
C34C33C32
C14BC14AC13
C14BC14AC15
C13C14AC15
C14AC14BC13
C14AC14BC15
C13C14BC15
C1N1C2
C25–C30
C25–C26
C26–C27
C27–C28
C28–C29
C29–C30
C30–Cl1
C31–O1
C31–C32
C32–C33
C33–C34
previously). The atom С14 of alicyclic fragment of
compound VIII is disordered by two equally occupied
positions A and B (Fig. 2).
The solvate molecules of butanol bind the
neighboring molecules of VIII into endless zigzag
chains via the hydrogen bonds (N–H···O–H···N)
(Fig. 3). The butanol molecules occupy the cavities
between the molecules of VIII. Thus, it is possible to
assume the molecular recognition between the ali-
phatic part of butanol and alicyclic moiety of com-
pound VIII.
C6N2C7
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DYACHENKO et al.
placed geometrically and their positions were refined
in the rider model together with positions of the
carbon atoms.
In the refinement 1849 reflections were utilized
with I > 2σ(I) (244 refined parameters, 7.6 reflections
per parameter). The weight scheme used was w =
1/[σ2(Fo2) + (0.0388P)2] where P = (Fo2 + 2Fc2)/3, the
ratio to the error of the maximum (mean) shift in the
final cycle was 0.017 (0.002). The final values of the
divergence factors were R1(F) 0.0604, wR2(F2) 0.1090
for reflections with I>2σ(I), R1(F) 0.1421, wR2(F2)
01321, GOF 1.168 for all independent reflections. The
residual electron density for the difference Fourier
series after the final refinement cycle was 0.20 and
−0.20 e Å–3. A complete set of the X-ray diffraction
data was deposited at the Cambridge Structural
Database (CCDC 854872).
The XRD experiment on a single crystal of
compound VIII was performed on a CCD-diffract-
tometer Bruker Smart Apex (MoKα-radiation, λ
0.71069 Å, θmax 26.49°, spherical segment 0 ≤ h ≤ 15,
–17 ≤ k ≤ 17, –21 ≤ l ≤ 21) at a temperature of 173 K.
Overall number of 20418 reflections was collected,
among them 6118 were independent. Crystals of
compound VIII monoclinic, a 12.4004(17), b 14.013(2),
c 17.260(3) Å, β 99.912(4), V 2954.5(8) Å3, Z 4, dcalc
1.329 g cm–3, µ 0.17 cm–1, F(000) 1248, space group
Р21/n. The structure was solved by the direct method
and refined by the least squares method in the full-
matrix anisotropic approximation using a SHELX
program [24]. In refining 3090 reflections with I >
2σ(I) were used (453 refining parameters, 6.8
reflections per one parameter). Positions of most
hydrogen atoms (including the atoms involved into the
hydrogen bonds) were identified from the difference
Fourier series and refined isotropically. The final
values of the divergence factors are R1 0.086 и Rw
0.222, GOF 1.046. By the difference Fourier series, the
residual electron density is –0.65 and 0.66 e Å–3. A
Fig. 2. General view and the numbering of atoms of the
compound VIII molecule. Hydrogen bond with the solvate
butanol molecule is marked by dashed line.
EXPERIMENTAL
X-Ray diffraction analysis. The crystals of
compound VIс are monoclinic, C22H18N4O, M 354.4,
space group Р21/с, а 13.5802(9), b 9.3607(7), c
14.4475(11) Å, β 100.675(4)°, V 1804.8(2) Å3, Z 4,
d
calc 1.304 g cm–3, size 0.36×0.30×0.15 mm. The study
was carried out at room temperature on a Bruker Smart
Apex diffractometer ((λMoKα-radiation, graphite
monochromator, θmax 26.28°, –16 ≤ h ≤ 16, –10 ≤ k ≤
11, –17 ≤ l ≤ 17). 15818 reflections were collected,
3635of which were independent (R-factor is 0.0664).
The correction for extinction was done using SADABS
program by multiscanning method (Тmin/Tmax
=
0.650778). The structure was solved by the direct
method and refined by the least squares method in the
full-matrix anisotropic approximation using a Bruker
SHELXTL program [24]. All hydrogen atoms were
Fig. 3. Packing of molecules in the crystal of compound VIII.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 83 No. 7 2013

SYNTHESIS AND ALKYLATION OF 1-ALKYL(ARYL)-4-CYANO-3-DICYANOMETHYLENE-...
1389
complete set of the X-ray diffraction data was
deposited at the Cambridge Structural Database
(CCDC 874929).
1Н NMR spectrum, δ, ppm: 2.05 m (2Н, СН2), 2.88 t
(2Н, СН2, J 7.6 Hz), 3.05 t (2Н, СН2, J 7.4 Hz), 7.45–
7.72 m (5Н, Ph). The signal of NH-proton does not
occur, apparently due to fast deuterium exchange.
Mass spectrum, m/z (Irel, %): 285 (100) [M + 1]+.
Found, %: С 75.90; Н 4.11; N 19.92. С18Н12N4.
Calculated, %: С 76.04; Н 4.25; N 19.71. М 284.324.
The IR spectra were recorded on a SPECTRUM
ONE (Perkin Elmer) FIR-spectrometer from KBr
1
pellets. The H NMR spectra were taken on a Bruker
DR-500 spectrometer (500.13 MHz) in DMSO-d6,
internal reference TMS. The 13C NMR spectra were
registered on a Varian VXR-300 spectrometer (125.74
МHz) in DMSO-d6, internal reference TMS. Mass
spectra were recorded on a Chrommass GC/MC
(Hewlett Packard) 5890/5972 instrument (column HP-
5 MS, 70 eV) in CH2Cl2. Melting points were
determined on a Koeffler heating block. The reaction
progress and purity of compounds obtained were
monitored by TLC on Silufol UV-254 plates eluting
with an acetone–hexane mixture (3:5) and detecting
with iodine vapor or UV irradiation.
2-{4-Cyano-6-Methyl-1-phenyl-5,6,7,8-tetrahydro-
isoquinolin-3(2H)-ylidene}malononitrile (Ic). Yield
2.46 g (79%), yellow powder, fluoresces under UV
irradiation, mp 248–251°C (BuOH). IR spectrum, ν,
cm–1: 3230 (NH), 2180, 2207 (C≡N). 1Н NMR
spectrum, δ, ppm: 0.71 d (3Н, Ме, J 6.3 Hz), 1.05 m
(2Н, СН2), 1.58 m (1Н, С6Н), 1.77 m (2Н, СН2), 2.95
m (2Н, СН2), 7.49–7.54 m (5Н, Ph). The signal of NH-
proton does not occur, apparently due to fast deuterium
exchange. Mass spectrum, m/z (Irel, %): 313 (100)
[M + 1]+. Found, %: С 76.83; Н 5.15; N 18.02.
С20Н16N4. Calculated, %: С 76.90; Н 5.16; N 17.94.
М312.378.
1-Substituted 4-cyano-3-dicyanomethylenecarbo-
[c]fused pyridines (Ia–Ii). To a solution of 10 mmol
of enaminoketone II and 1.32 g (10 mmol) of malo-
nonitrile dimer III in 20 ml of anhydrous ethanol at
20°C was added sodium ethoxide solution (prepared
from 0.23 g of sodium metal and 10 ml of anhydrous
ethanol). The mixture was stirred for 30 min and kept
for 1 day. Then the reaction mixture was diluted with
10% aqueous hydrochloric acid to рН 3. The resulting
precipitate was filtered off, washed with water,
ethanol, and hexane.
2-{4-Cyano-1-Methyl-7-phenyl-5,6,7,8-tetrahydro-
isoquinolin-3(2H)-ylidene}malononitrile (Id). Yield
2.10 g (68%), yellow powder, mp 265–267°C (AcOH).
IR spectrum, ν, cm–1: 3314 (NH), 2196, 2205 (C≡N).
1Н NMR spectrum, δ, ppm: 1.25 s (3Н, Ме), 1.76–2.14
m (3Н, С6Н2 and С7Н), 2.66–2.91 m (4Н, С5Н2 and
С8Н2), 7.16–7.33 m (5Н, Ph). The signal of NH-proton
does not occur, apparently due to fast deuterium
exchange. 13С NMR spectrum, δC, ppm: 18.20, 28.08,
30.03, 32.43, 39.63, 98.01, 113.66, 118.34, 123.04,
126.94, 127.27, 128.95, 145.45, 151.41, 154.07,
159.68. Mass spectrum, m/z (Irel, %): 313 (100) [M +
1]+. Found, %: С 76.85; Н 5.27; N 17.88. С20Н16N4.
Calculated, %: С 76.90; Н 5.16; N 17.94. М312.378.
2-{4-Cyano-1-methyl-6,7-dihydro-2H-cyclopenta-
[c]pyridin-3(5H)-ylidene}malononitrile (Ia). Yield
1.73 g (78%), yellow powder, fluoresces under UV
irradiation, mp 230–232°C (AcOH). IR spectrum, ν,
cm–1: 3250 (NH), 2182, 2204 (C≡N). 1Н NMR
spectrum, δ, ppm: 2.08 t (2Н, СН2, J 7.3 Hz), 2.39 s
and 2.45 s (3Н, Ме), 2.79 m (2Н, СН2), 3.04 t (2Н,
СН2, J 7.4 Hz). The signal of NH-proton does not
occur, apparently due to fast deuterium exchange. 13С
NMR spectrum, δC, ppm: 17.75, 18.94, 21.43, 23.19,
28.29, 29.16, 32.51, 34.04, 94.06, 97.49, 113.38,
113.76, 117.51, 117.67, 128.42, 129.37, 149.47, 152.09,
152.70, 157.29, 159.32, 168.37. Mass spectrum, m/z
(Irel, %): 223 (100) [M + 1]+. Found, %: С 70.04; Н
4.44; N 25.52. С13Н10N4. Calculated, %: С 70.26; Н
4.53; N 25.21. М 222.252.
2-[1-(2-Chlorophenyl)-4-cyano-5,6,7,8-tetrahydro-
isoquinolin-3(2H)-ylidene]malononitrile (Ie). Yield
2.4 g (72%), yellow powder, fluoresces under UV
irradiation, mp 250°C (decomp.). IR spectrum, ν, cm–1:
1
3248(NH), 2192, 2210(C≡N). Н NMR spectrum, δ,
ppm: 1.52–1.64 m (2Н, СН2), 1.66–1.79 m (2Н, СН2),
2.09–2.21 m (2Н, СН2), 2.81–2.93 m (2Н, СН2), 7.48
d (1Н, Нarom, J 7.5 Hz), 7.51 t (1Н, Нarom, J 7.5 Hz),
7.57 t (1Н, Нarom, J 8.0 Hz), 7.63 d (1Н, Нarom, J 8.5 Hz).
The signal of NH-proton does not occur, apparently
due to fast deuterium exchange. 13С NMR spectrum,
δC, ppm: 20.82, 21.08, 24.72, 29.10, 38.39, 99.27,
113.57, 118.72, 122.68, 127.55, 129.45, 130.68,
131.58, 131.69, 132.81, 151.18, 152.79, 159.52. Mass
spectrum, m/z (Irel, %): 331 (100) [M – 1]+. Found, %:
2-{4-Cyano-1-phenyl-6,7-dihydro-2H-cyclopenta-
[c]pyridin-3(5H)-ylidene}malononitrile (Ib). Yield
2.24 g (79%), yellow powder, mp 263–265°C (AcOH).
IR spectrum, ν, cm–1: 2294 (NH), 2198, 2218 (C≡N).
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 83 No. 7 2013

1390
DYACHENKO et al.
1
С 68.42; Н 3.85; N 16.70. С19Н13ClN4. Calculated, %:
С 68.57; Н 3.94; N 16.84. М 332.796.
3335 (NH), 2175, 2202 (C≡N). Н NMR spectrum, δ,
ppm: 1.27 d (6Н, 2Ме, J 6.8 Hz), 1.74 m (4Н, 2СН2),
2.61 m (2Н, СН2), 2.84 m (2Н, СН2), 3.30 m (1Н,
СН), 8.70 br. s (1Н, NH). Mass spectrum, m/z (Irel, %):
265 (100) [M + 1]+. Found, %: С 72.65; Н 6.14; N
21.21. С16Н16N4. Calculated, %: С 72.70; Н 6.10; N
21.20. М 264.331.
2-[4-Cyano-1,6-dimethyl-5,6,7,8-tetrahydroiso-
quinolin-3(2H)-ylidene]malononitrile (If). Yield
1.88 g (75%), yellow powder, fluoresces under UV
irradiation, mp 250–252°C (BuOH). IR spectrum, ν,
cm–1: 3434 (NH), 2172, 2204 (C≡N). 1Н NMR
spectrum, δ, ppm: 1.05 d (3Н, Ме, J 6.4 Hz), 1.21–
1.36 m (1Н, С6Н), 1.73–1.81 m (2Н, СН2), 2.35–2.45
m (2Н, СН2), 2.48 s (3Н, Ме), 2.64 m (1Н, СН2), 2.95
m (1Н, СН2). The signal of NH-proton does not occur,
apparently due to fast deuterium exchange. 13С NMR
spectrum, δC, ppm: 17.68, 20.89, 23.79, 26.81, 28.91,
36.99, 97.52, 113.14, 117.94, 122.23, 150.88, 153.44,
159.38. Mass spectrum, m/z (Irel, %): 249 (100) [M – 1]
+. Found, %: С 71.90; Н 5.68; N 22.42. С15Н14N4.
Calculated, %: С 71.98; Н 5.64; N 22.38. М 250.306.
2-Acyl-1-(N-morpholinyl)cycloalkenes IIa–IIi were
prepared as described in [25].
Substituted 2-alkyl-2-(3-isoquinolinyl)malono-
nitriles VIa–VIk. To a stirred solution of 10 mmol of
compound I in 15 ml of DMF at 20°C were added in
succession 5.6 ml (10 mmol) of 10% aqueous KOH
and 10 mmol of alkylating agent V. The mixture was
stirred for 2 h and kept for 1 day. Then the reaction
mixture was diluted with an equal volume of water and
allowed to stand for 48 h. The formed precipitate was
filtered off, washed with water, ethanol and hexane.
2-[4-Cyano-1-methyl-5,6,7,8-tetrahydroisoquino-
lin-3(2H)-ylidene]malononitrile (Ig). Yield 1.82 g
(77%), yellow powder, fluoresces under UV irradia-
tion, mp 265–267°C (AcOH) (mp 310°C [20]). IR
2-(Prop-2-ynyl)-2-(4-cyano-1-phenyl-6,7-dihydro-
5H-cyclopenta[c]pyridin-3-yl)malononitrile (VIa).
Yield 2.01 g (64%), yellow needles, fluoresces under
UV irradiation, mp 161–163°C (BuOH). IR spectrum,
1
spectrum, ν, cm–1: 3256 (NH), 2177, 2202 (C≡N). Н
ν, cm–1: 3271 (≡C–Н), 2229 (С≡N). Н NMR spec-
1
NMR spectrum, δ, ppm: 1.73 m (4Н, 2СН2), 2.48 s
(3Н, Ме), 2.51 m (2Н, СН2), 2.82 m (2Н, СН2), 12.55
br. s (1Н, NH). 13С NMR spectrum, δC, ppm: 17.54,
20.51, 20.91, 23.91, 29.17, 97.67, 113.05, 117.83,
122.69, 150.62, 153.43, 159.94. Mass spectrum, m/z
(Irel, %): 235 (100) [M – 1]+. Found, %: С 71.22; Н
5.10; N 23.68. С14Н12N4. Calculated, %: С 71.17; Н
5.12; N 23.71. М 236.279.
trum, δ, ppm: 2.21 t (2Н, СН2, J 7.6 Hz), 3.24 t (2Н,
СН2, J 7.2 Hz), 3.29 t (2Н, СН2, J 7.6 Hz), 3.51 s (1Н,
≡CН), 3.81 s (2Н, СН2), 7.52–7.66 m (3Н, Ph), 7.93–
8.08 m (2Н, Ph). 13С NMR spectrum, δC, ppm: 24.46,
28.07, 32.50, 32.79, 43.45, 76.04, 77.57, 102.23,
112.78, 113.63, 128.63, 128.85, 130.30, 136.70,
139.54, 146.42, 154.51, 163.96. Mass spectrum, m/z
(Irel, %): 323 (100) [M + 1]+. Found, %: С 78.19; Н
4.35; N 17.46. С21Н14N4. Calculated, %: С 78.24; Н
4.38; N 17.38. М 322.373.
2-[4-Cyano-1-phenyl-5,6,7,8-tetrahydroisoquino-
lin-3(2H)-ylidene]malononitrile (Ih). Yield 2.41g
(81%), yellow powder, fluoresces under UV irradia-
tion, mp 265–268°C (AcOH). IR spectrum, ν, cm–1:
2-Benzyl-2-(4-cyano-1-methyl-5,6,7,8-tetrahydro-
isoquinolin-3-yl)malononitrile (VIb). Yield 2.12 g
(65%), yellow crystals, mp 140–143°C (BuOH). IR
1
3435 (NH), 2179, 2203 (C≡N). Н NMR spectrum, δ,
ppm: 1.62 m (2Н, СН2), 1.79 m (2Н, СН2), 2.38 m
(2Н, СН2), 2. 92 m (2Н, СН2), 7.38–7.64 m (5Н, Ph).
The signal of NH-proton is not observed apparently
due to fast deuterium exchange. 13С NMR spectrum,
δC, ppm: 20.70, 21.25, 25.52, 29.20, 98.95, 113.48,
118.45, 122.20, 128.41, 128.92, 130.06, 133.32,
152.10, 152.89, 159.81, 193.94. Mass spectrum, m/z
(Irel, %): 297 (100) [M – 1]+. Found, %: С 76.30; Н
4.83; N 18.87. С19Н14N4. Calculated, %: С 76.49; Н
4.73; N 18.78. М 298.351.
1
spectrum, ν, cm–1: 2228 (C≡N). Н NMR spectrum, δ,
ppm: 1.81 m (4Н, 2СН2), 2.51 s (3Н, Ме), 2.71 m (2Н,
СН2), 2.97 m (2Н, СН2), 3.82 s (2Н, СН2Ph), 7.39–
7.44 m (5Н, Ph). 13С NMR spectrum, δC, ppm: 20.56,
21.07, 22.39, 25.05, 28.09, 42.37, 46.73, 105.09,
112.99, 161.02. Mass spectrum, m/z (Irel, %): 327 (100)
[M + 1]+. Found, %: С 77.25; Н 5.59; N 17.16.
С21Н18N4. Calculated, %: С 77.28; Н 5.55; N 17.17. М
326.404.
2-[4-Cyano-1-isopropyl-5,6,7,8-tetrahydroiso-
quinolin-3(2H)-ylidene]malononitrile (Ii). Yield 2.16 g
(82%), yellow powder, fluoresces under UV irradia-
tion, mp 255–257°C (AcOH). IR spectrum, ν, cm–1:
2-(4-Cyano-1-methyl-5,6,7,8-tetrahydroisoquino-
lin-3-yl)-2-(2-oxo-2-phenylethyl)malononitrile (VIc).
Yield 2.37 g (67%), orange crystals, mp 215–217°C
(BuOH). IR spectrum, ν, cm–1: 2225 (C≡N), 1686
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 83 No. 7 2013

SYNTHESIS AND ALKYLATION OF 1-ALKYL(ARYL)-4-CYANO-3-DICYANOMETHYLENE-...
1391
1
(С=О). Н NMR spectrum, δ, ppm: 1.80 m (4Н,
Harom, J 8.0 Hz), 7.82 t (1Н, Harom, J 8.0 Hz), 8.02 d
13
2СН2), 2.32 s (3Н, Ме), 2.67 m (2Н, СН2), 2.99 m
(2Н, СН2), 4.69 s (2Н, СН2СО), 7.61 t (2Н, Ph, J 7.5
Hz), 7.74 t (1Н, Ph, J 7.5 Hz), 8.08 d (2Н, Ph, J 7.5
Hz). 13С NMR spectrum, δC, ppm: 20.54, 21.03, 22.18,
24.99, 28.08, 38.10, 43.01, 106.13, 113.33, 113.48,
128.13, 128.80, 133.68, 134.02, 135.15, 145.74,
152.27, 160.70, 193.45. Mass spectrum, m/z (Irel, %):
355 (100) [M + 1]+. Found, %: С 74.59; Н 5.11; N
15.79. С22Н18N4О. Calculated, %: С 74.56; Н 5.12; N
15.81. М 354.414.
(1Н, Harom, J 8.0 Hz), 8.90 s (1Н, С4Н, coumarin). С
NMR spectrum, δC, ppm: 20.99, 24.78, 28.99, 31.11,
31.22, 36.22, 39.74, 40.16, 46.96, 106.43, 113.75,
113.99, 116.75, 118.48, 122.72, 125.73, 131.75,
132.86, 135.92, 146.58, 149.59, 153.70, 155.32,
158.89, 162.72, 168.48, 190.58. Mass spectrum, m/z
(Irel, %): 451 (100) [M + 1]+. Found, %: С 71.85; Н
4.85; N 12.50. С27Н22N4О3. Calculated, %: С 71.99; Н
4.92; N 12.44. М 450.501.
2-(Prop-2-ynyl)-2-[1-(1-chlorophenyl)-4-cyano-
5,6,7,8-tetrahydroisoquinolin-3-yl]malononitrile
(VIg). Yield 2.44 g (66%), dark red crystals, mp 148–
150°C (BuOH). IR spectrum, ν, cm–1: 3304 (≡C–Н),
2-[2-(4-Bromophenyl)-2-oxoethyl]-2-(1-isopropyl-
4-cyano-5,6,7,8-tetrahydroisoquinolin-3-yl)-malono-
nitrile (VId). Yield 3.3 g (71%), white powder, mp
158–159°C (AcOH). IR spectrum, ν, cm–1: 2223
1
2225 (С≡N). Н NMR spectrum, δ, ppm: 1.72 m (2Н,
1
(C≡N), 1679 (С=О). Н NMR spectrum, δ, ppm: 0.89
СН2), 1.83 m (2Н, СН2), 2.47 m (2Н, СН2), 3.09 m
(2Н, СН2), 3.48 s (1Н, ≡СН), 3.72 s (2Н, СН2С≡),
7.45 d (1Н, Нarom, J 7.2 Hz), 7.51–7.58 m (2Н, Нarom),
7.65 d (1Н, Нarom, J 8.0 Hz). 13С NMR spectrum, δC,
ppm: 20.58, 20.84, 25.83, 28.08, 28.25, 43.46, 75.69,
77.76, 107.24, 112.65, 113.08, 127.54, 129.58, 130.30,
130.91, 131.14, 134.60, 136.46, 146.10, 154.53,
158.68. Mass spectrum, m/z (Irel, %): 371 (100) [M +
1]+. Found, %: С 71.14; Н 3.98; N 15.18. С22Н15ClN4.
Calculated, %: С 71.26; Н 4.08; N 15.11. М 370.845.
d (6Н, 2Ме, J 6.6 Hz), 1.79 m (4Н, 2СН2), 2.76 m
(2Н, СН2), 3.00 m (2Н, СН2), 3.11–3.26 m [1Н,
СН(Ме)2], 4.78 s (2Н, СН2СО), 7.83 d and 8.04 d
(4Н, 4-BrC6H4, J 8.0 Hz). 13С NMR spectrum, δC,
ppm: 28.14, 28.37, 28.82, 31.64, 35.54, 37.37, 43.92,
48.67, 107.62, 114.24, 114.40, 128.24, 129.91, 131.55,
131.80, 133.35, 144.23, 151.08, 164.78, 187.60. Mass
spectrum, m/z (Irel, %): 462 (100) [M + 1]+. Found, %:
С 62.30; Н 4.35; N 12.02. С24Н21BrN4О. Calculated,
%: С 62.49; Н 4.59; N 12.15. М 461.309.
2-Allyl-2-(4-cyano-1-phenyl-5,6,7,8-tetrahydro-
isoquinolin-3-yl)malononitrile (VIh). Yield 2.01 g
(60%), dark red crystals, mp 85–86°C (MeOH). IR
2-(4-Cyano-1-isopropyl-5,6,7,8-tetrahydroisoquino-
lin-3-yl)-2-(prop-2-ynyl)malononitrile (VIe). Yield
1.78 g (59%), yellow crystals, mp 140–141°C (BuOH).
1
spectrum, ν, cm–1: 2222 (С≡N). Н NMR spectrum, δ,
IR spectrum, ν, cm–1: 3338 (≡С–Н), 2228(C≡N). Н
ppm: 1.70 m (2Н, СН2), 1.87 m (2Н, СН2), 2.79 m
(2Н, СН2), 3.08 m (2Н, СН2), 3.38 d (2Н, СН2–СН=, J
7.0 Hz), 5.46 d (1Н, =СН2, Jcis 9.45 Hz), 5.54 d (1Н,
=СН2, Jtrans 17.38 Hz), 5.84–5.96 m (1Н, СН=), 7.54
m (3Н, Ph), 7.66 m (2Н, Ph). 13С NMR spectrum, δC,
ppm: 20.61, 21.33, 27.19, 28.35, 40.83, 44.53, 105.95,
112.96, 113.45, 123.50, 128.19, 128.86, 129.10,
129.36, 133.19, 137.53, 147.06, 154.38, 159.84,
199.50. Mass spectrum, m/z (Irel, %): 339 (100) [M +
1]+. Found, %: С 78.01; Н 5.25; N 16.74. С22Н18N4.
Calculated, %: С 78.08; Н 5.36; N 16.56. М 338.415.
1
NMR spectrum, δ, ppm: 1.22 d (6Н, 2Ме, J 6.8 Hz),
1.71–1.86 m (4Н, 2СН2), 2.74 m (2Н, СН2), 2.97 m
(2Н, СН2), 3.31–3.39 m [1Н, СН(Ме)2], 3.46 s (1Н,
≡СН), 3.71 s (2Н, СН2С≡). 13С NMR spectrum, δC,
ppm: 21.02, 21.55, 21.73, 24.77, 28.25, 28.97, 31.27,
43.94, 76.54, 77.94, 105.65, 113.27, 113.99, 132.98,
146.23, 146.25, 153.60, 168.64. Mass spectrum, m/z
(Irel, %): 303 (100) [M + 1]+. Found, %: С 75.38; Н
5.96; N 18.66. С19Н18N4. Calculated, %: С 75.47; Н
6.00; N 18.53. М 302.382.
2-(4-Cyano-1-isopropyl-5,6,7,8-tetrahydroisoquino-
lin-3-yl)-2-[2-(coumarin-3-yl)-2-oxoethyl]malono-
nitrile (VIf). Yield 3.2 g (72%), yellow crystals,
fluoresces under UV irradiation, mp 191–193°C
(BuOH). IR spectrum, ν, cm–1: 2228 (C≡N), 1715,
2-Allyl-2-(4-cyano-6-methyl-1-phenyl-5,6,7,8-
tetrahydroisoquinolin-3-yl)malononitrile (VIi).
Yield 2.57 g (73%), white powder, mp 96–99°C
1
(BuOH). IR spectrum, ν, cm–1: 2224 (C≡N). Н NMR
spectrum, δ, ppm: 1.11 d (3Н, СН3, J 6.4 Hz), 1.18–
1.30 m (1Н, СНМе), 1.86 m (1Н, СН2), 1.97 m (1Н,
СН2), 2.60–2.76 m (2Н, СН2), 2.87–3.17 m (1Н, СН2),
3.19–3.25 m (1Н, СН2), 3.37 d (2Н, СН2СН=, J 6.44 Hz),
5.44 d (1Н, =СН2, Jcis 9.55 Hz), 5.51 d (1Н, =СН2,
1
1691 (С=О). Н NMR spectrum, δ, ppm: 1.11 d (6Н,
2Ме, J 4.0 Hz), 1.82 m (4Н, 2СН2), 2.80 m (2Н, СН2),
3.01 m (2Н, СН2), 3.18–3.36 m (1Н, СНМе2), 4.70 s
(2Н, СН2СО), 7.47 t (1Н, Harom, J 8.0 Hz), 7.52 d (1Н,
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 83 No. 7 2013

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DYACHENKO et al.
Jtrans 17.41 Hz), 5.81–5.99 m (1Н, СН=), 7.45–7.56 m
(3Н, Ph), 7.61–7.73 m (2Н, Ph). 13С NMR spectrum,
δC, ppm: 21.14, 27.01, 27.09, 29.52, 36.49, 40.86,
44.56, 105.85, 112.97, 113.49, 123.57, 128.23, 128.89,
129.13, 129.41, 132.81, 137.63, 147.17, 154.25,
159.79. Mass spectrum, m/z (Irel, %): 353 (100) [M +
1]+. Found, %: С 78.27; Н 5.81; N 15.92. С23Н20N4.
Calculated, %: С 78.38; Н 5.72; N 15.90. М 352.442.
1 day. The reaction mixture was diluted with 20 ml of
water. The resinous product was separated by
decantation, dissolved in 20 ml of methanol, and
allowed to stand for 48 h. The formed precipitate was
filtered off, washed with ethanol and hexane, and
recrystallized from butanol. Yield 3.1g (62%), dark red
crystals, fluoresces under UV irradiation, mp 300–
303°C. IR spectrum, ν, cm–1: 3288–3442 (NH2), 2224,
1
2246 (С≡N), 1648 [δ(NH2)]. Н NMR spectrum, δ,
2-[2-(3,4-Dihydroxyphenyl)-2-oxoethyl]-2-(4-
cyano-1,6-dimethyl-5,6,7,8-tetrahydroisoquinolin-3-
yl)malononitrile (VIj). Yield 2.56 g (64%), white
powder, mp 199–201°C (BuOH). IR spectrum, ν, cm–1:
ppm: 1.21–1.34 m (2Н, СН2), 1.71–1.79 m (2Н, СН2),
1.81–1.96 m (2Н, СН2), 3.38–3.41 m (2Н, СН2), 7.45–
7.68 m (9Н, Нarom), 7.83 br. s (2Н, NH2). 13С NMR
spectrum, δC, ppm: 21.15, 21.75, 26.74, 26.96, 35.16,
60.87, 89.57, 112.79, 114.55, 115.92, 128.02, 128.77,
129.23, 129.52, 130.00, 130.70, 130.85, 131.02,
131.92, 133.02, 135.78, 137.97, 147.88, 153.48,
154.15, 159.52, 161.48, 162.85. Mass spectrum, m/z
(Irel, %): 497 (100) [M – 1]+. Found, %: С 72.15; Н
3.75; N 16.72. С30Н19ClN6. Calculated, %: С 72.21; Н
3.84; N 16.84. М 498.979.
1
3385 (ОН), 2214, 2252 (C≡N), 1677 (С=О). Н NMR
spectrum, δ, ppm: 1.07 d (3Н, Ме, J 6.4 Hz), 1.38 m
(1Н, СНМе), 1.81–1.99 m (2Н, СН2), 2.39 m (3Н,
Ме), 2.51–2.64 m (2Н, СН2), 2.81 m (1Н, СН2), 3.04–
3.09 m (1Н, СН2), 4.51 s (2Н, СН2СО) 6.89 d (1Н,
Н
arom, J 8.0 Hz), 7.40 s (1Н, Нarom), 7.74 d (1Н, Нarom, J
8.0 Hz), 9.53 br. s (1Н, ОН), 10.13 br. s (1Н, ОН). 13С
NMR spectrum, δC, ppm: 20.94, 22.47, 24.98, 26.87,
29.13, 30.76, 36.77, 43.13, 105.81, 113.57, 113.66,
114.84, 115.22, 121.93, 126.92, 133.27, 145.42,
146.41, 151.74, 152.00, 160.73, 162.29, 191.19. Mass
spectrum, m/z (Irel, %): 401 (100) [M + 1]+. Found, %:
С 68.88; Н 4.95; N 14.12. С23Н20N4О3. Calculated, %:
С 68.99; Н 5.03; N 13.99. М 400.44.
1-Amino-2-(4-bromobenzoyl)-5-(2-chlorophenyl)-
6,7,8,9-tetrahydro-3H-cyclopenta[c]isoquinoline-
3,3-dicarbonitrile (IX) was prepared similarly to
compound VI from 3.33 g (10 mmol) of compound Id
and 2.8 g (10 mmol) of 4-bromophenacylbromide Va.
Yield 3.49 g (66%), yellow crystals, fluoresce under
UV irradiation, mp 297–301°C (BuOH). IR spectrum,
ν, cm–1: 3445 (NH2), 2255 (С≡N), 1687 (С=О), 1641
2-(4-Cyano-1-isopropyl-5,6,7,8-tetrahydroisoquino-
lin-3-yl)-2-[2-(4-chlorophenyl)-2-oxoethyl]malono-
nitrile (VIk). Yield 3.2 g (76%), white crystals, mp
186–188°C (BuOH). IR spectrum, ν, cm–1: 2227
1
[δ(NH2)]. Н NMR spectrum, δ, ppm: 1.72 m (2Н,
СН2), 1.83 m (2Н, СН2), 2.46 m (2Н, СН2), 3.29 m
(2Н, СН2), 7.44 d (1Н, Нarom, J 7.5 Hz), 7.47–7.55 m
(2Н, Нarom), 7.59 d and 7.77 d (4Н, 4-BrC6Н4, J 8.4 Hz),
7.64 d (1Н, Нarom, J 8.5 Hz), 8.80 br. s (2Н, NH2). 13С
NMR spectrum, δC, ppm: 20.63, 20.79, 26.22, 26.72,
41.08, 98.88, 113.63, 113.69, 124.01, 127.24, 127.55,
128.73, 129.51, 130.22, 130.60, 131.26, 131.66, 134.95,
137.29, 138.95, 147.14, 152.54, 160.31, 161.20, 188.22.
Mass spectrum, m/z (Irel, %): 530 (100) [M + 1]+.
Found, %: С 61.11; Н 3.29; N 10.47. С27Н18BrClN4O.
Calculated, %: С 61.21; Н 3.42; N 10.58. М 529.827.
1
(C≡N), 1699 (С=О). Н NMR spectrum, δ, ppm: 0.90
d (6Н, 2Ме, J 5.0 Hz), 1.69–1.82 m (4Н, 2СН2), 2.66–
2.79 m (2Н, СН2), 2.88–3.05 m (2Н, СН2), 3.17–3.28
m (1Н, СНМе2), 4.78 s (2Н, СН2С=О), 7.69 d and
8.13 d (4Н, С6Н4, J 8.61 Hz). 13С NMR spectrum, δC,
ppm: 21.00, 21.22, 21.73, 24.77, 28.97, 30.96, 38.08,
40.10, 106.70, 113.84, 114.00, 129.53, 130.67, 132.77,
134.15, 137.71, 146.24, 153.56, 168.36, 192.71. Mass
spectrum, m/z (Irel, %): 417 (100) [M + 1]+. Found, %:
С 68.98; Н 4.97; N 13.33. С24Н21ClN4О. Calculated,
%: С 69.14; Н 5.08; N 13.45. М 416.914.
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tetrahydro-7H-pyrido[2',3':3,4]cyclopenta[1,2-c]-
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(10 mmol) of 2-aminoprop-1-ene-1,1,3-tricarbonitrile
VII. The mixture was stirred for 2 h and kept for
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