Heterocyclization of N,N′-disubstituted p-phenylenediamines with cyclich β-diketones and formaldehyde. Synthesis of new pyrido[2,3-g] quinoline derivatives

Article abstract of DOI:10.1134/S1070428011030158

Three-component condensation of N,N′-dibenzyl-p-phenylenediamines with cyclic β-diketones and formaldehyde under mild conditions resulted in selective formation of a series of new dispiro derivatives of pyrido[2,3-g]quinoline.

Full text of DOI:10.1134/S1070428011030158

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2011, Vol. 47, No. 3, pp. 412–416. © Pleiades Publishing, Ltd., 2011.
Original Russian Text © A.P. Kadutskii, N.G. Kozlov, Yu.D. Zhikharko, 2011, published in Zhurnal Organicheskoi Khimii, 2011, Vol. 47, No. 3,
pp. 419–423.
Heterocyclization of N,N′-Disubstituted p-Phenylenediamines
with Cyclich β-Diketones and Formaldehyde. Synthesis
of New Pyrido[2,3-g]quinoline Derivatives
A. P. Kadutskii, N. G. Kozlov, and Yu. D. Zhikharko
Institute of Physical Organic Chemistry, National Academy of Sciences of Belarus,
ul. Surganova 13, Minsk, 220072 Belarus
e-mail: loc@ifoch.bas-net.by
Received May 18, 2010
Abstract—Three-component condensation of N,N′-dibenzyl-p-phenylenediamines with cyclic β-diketones and
formaldehyde under mild conditions resulted in selective formation of a series of new dispiro derivatives of
pyrido[2,3-g]quinoline.
DOI: 10.1134/S1070428011030158
Three-component condensation of aromatic amines
with aldehydes and cyclic β-dicarbonyl compounds
provides a convenient one-step procedure for the syn-
thesis of fused polynuclear heterocyclic systems. This
reaction was successfully used to prepare various func-
tionalized derivatives of piperidine [1], benzo[f]quino-
line [2], benzoacridine [3, 4], phenanthroline [5], pyr-
azolo[3,4-b]quinoline [6], pyrimido[4,5-b]quinoline
[7], furo[3,4-e]pyrazolo[3,4-b]pyridine [8], and other
heterocyclic systems [9]. In all cases, the starting com-
pounds were electron-rich aromatic monoamines.
densation, giving rise to new polynuclear nitrogen-
containing heterocycles. To verify this assumption, we
synthesized a series of symmetric N,N′-disubstituted
p-phenylenediamines Ia–If and brought them into
three-component condensation with formaldehyde (II)
and cyclic β-diketones IIIa and IIIb of the cyclohex-
ane-1,3-dione series. The reactions were carried out in
ethanol by heating for a short time in the absence of
a catalyst. In fact, the products were those formed from
one aromatic diamine molecule and two β-diketone
and two formaldehyde molecules. On the basis of the
1H NMR data, the isolated compounds were assigned
the structure of pyrido[2,3-g]quinoline derivatives
VIa–VIl (Scheme 2). It should be noted that alter-
native isomeric heterocyclization products, 4,7-phen-
anthroline derivatives like VII, were not detected in
the reaction mixtures.
We previously showed that spiro compounds of the
1,2,3,4-tetrahydroquinoline series can readily be ob-
tained by condensation of N-monosubstituted anilines
I containing an electron-donating substituent R1 with
formaldehyde (II) and cyclic β-diketones III (Scheme 1)
[10]. We presumed that analogous three-component
condensation may be performed with aromatic di-
amines. In this case, the second amino group should
not only activate the reaction due to its pronounced
electron-donor properties but also participate in con-
A probable mechanism of the heterocyclization
process is shown in Scheme 3. Spirocyclic pyrido-
[2,3-g]quinoline derivatives VIa–VIl are formed via
initial reaction of formaldehyde (II) with β-diketone
Scheme 1.
R3
R3
O
O
R1
H
N
R2
+
CH2O +
R3
R3
N
O
R1
O
R2
I
II
III
IV
412

HETEROCYCLIZATION OF N,N′-DISUBSTITUTED p-PHENYLENEDIAMINES
413
Scheme 2.
R3
R3
R2
R3
R3
R3
R3
O
H
10'
O
O
N
R2
O
2
N
1''
9'
1'
II + III
2'
3'
8'
7'
6'
N
4'
O
O
3
4
1
6
R2
N
O
5'
R3
R3
H
N
N
5
O
R2
R2
R2
Va–Vf
VIa–VIl
VII
VI, R2 = 4-FC6H4, R3 = H (a); R2 = 2,3-Cl2C6H3, R3 = H (b); R2 = 4-BrC6H4, R3 = H (c); R2 = 4-MeOC6H4, R3 = H (d); R2 = 3-EtO-
4-HOC6H3, R3 = H (e); R2 = 4-Me2NC6H4, R3 = H (f); R2 = 4-FC6H4, R3 = Me (g); R2 = 2,3-Cl2C6H3, R3 = Me (h); R2 = 4-BrC6H4,
R3 = Me (i); R2 = 4-MeOC6H4, R3 = Me (j); R2 = 3-EtO-4-HOC6H3, R3 = Me (k); R2 = 4-Me2NC6H4, R3 = Me (l).
III to give α,β-unsaturated diketone A. Michael ad-
dition of one diketone A molecule at the activated
2-position of diamine V yields amino diketone B
which takes up in a similar way the second molecule of
diketone A. Insofar as position 3 in the initial diamine
is sterically shielded by two bulky substituents in the
neighboring positions, the second dioxocyclohexyl-
methyl fragment enters exclusively position 5 with
respect to the first amino group. Both amino groups in
bis(aminodiketone) C are then involved in intra-
molecular Mannich condensation to produce dispiro
compounds with the pyrido[2,3-g]quinoline fragment.
Alternatively, amino diketone B is capable of taking up
the second molecule of diketone A at the 6-position
with formation of intermediate E. However, position 5
is activated by both electron-donating amino group in
position 2 and dioxocyclohexylmethyl fragment
(which may be regarded as donor alkyl group), whereas
position 6 is activated only by the neighboring amino
group. Correspondingly, structure E is not formed. One
more alternative pathway is the formation of 4,7-phen-
anthroline derivatives like VII through bis-aminodi-
ketone D which could be generated under thermo-
dynamic control of the process, but structure VI seems
Scheme 3.
R3
R3
O
CH2
O
O
O
V
H
N
R2
II + III
R3
R3
N
R2
H
A
B
O
R2
O
NH
R3
O
A
R3
VI
R3
R3
HN
R2
O
C
R2
R2
R2
O
NH
R3
R3
O
HN
NH
O
O
R3
R3
A
A
B
VII
R3
R3
R3
R3
O
HN
R2
O
O
O
E
D
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 3 2011

KADUTSKII et al.
414
to more favorable from the viewpoints of both energy
and steric factors. Indirect proofs for the formation of
linear structure like VI under analogous conditions
were given in [11].
(0.3 mol) of glacial acetic acid was added dropwise on
cooling, and the mixture was kept for 24 h at room
temperature. The solvent was distilled off, the residue
was treated with a 10% aqueous solution of sodium
hydroxide, the oily material was extracted into diethyl
ether, and the extract was dried over anhydrous magne-
sium sulfate and evaporated.
The structure of compounds VIa–VIl was con-
firmed by their IR and NMR spectra. The IR spectra of
spiro-fused pyrido[2,3-g]quinoline derivatives VIa–
VIl characteristically contained strong absorption
bands due to two couples of nonequivalent carbonyl
groups at 1730 and 1690 cm–1. In the 1H NMR spectra
of VIa–VIl we observed a singlet at δ 6.0 ppm with
an intensity corresponding to two protons, which was
assigned to the equivalent 5-H and 10-H protons in the
central aromatic ring. Pyrido[2,3-g]quinolines VIa–
N,N′-Bis(4-fluorobenzyl)benzene-1,4-diamine
(Va). Yield 90%, mp 115–116°C. IR spectrum, ν, cm–1:
3403 (NH); 3069 (C–Harom); 2876, 2854 (C–Haliph);
1
1601, 1508 (C=Carom). H NMR spectrum, δ, ppm:
4.1 d (4H, NCH2Ar, J = 7 Hz), 5.20 d (1H, NH, J =
7 Hz), 5.23 d (1H, NH, J = 7 Hz), 6.41 s (4H,
NHC6H4NH), 6.85 d (4H, Harom, J = 9 Hz), 7.25 d (4H,
1
VIf also displayed in the H NMR spectra signals
Harom, J = 9 Hz). Found, %: C 74.13; H 5.72; N 8.75.
from protons in the R3 substituents, an 8H-multiplet at
δ 2.8 ppm due to 3-H, 3″-H, 5-H, and 5″-H, and three
multiplets each with an intensity of 4H at δ 3.10 (4′-H,
9′-H), 3.45 (4-H, 4″-H), and 3.65 ppm (2′-H, 7′-H).
Methylene protons in the NCH2Ar fragments gave
a multiplet at δ 4.30 ppm (4H). Unlike compounds
VIa–VIf, the spectra of pyrido[2,3-g]quinolines VIg–
VIl derived from dimedone (IIIb) contained two addi-
tional singlets belonging to protons in the four methyl
groups (δ 0.75 and 1.05 ppm).
C20H18F2N2. Calculated, %: C 74.04; H 5.59; N 8.64.
N,N′-Bis(2,3-dichlorobenzyl)benzene-1,4-di-
amine (Vb). Yield 86%, mp 130–132°C. IR spectrum,
ν, cm–1: 3442, 3410 (NH); 3066, 3013 (C–Harom); 2923,
1
2852 (C–Haliph); 1617, 1514 (C=Carom). H NMR spec-
trum, δ, ppm: 4.0 d (4H, NCH2Ar, J = 7 Hz), 5.20 d
(2H, NH), 6.4 s (4H, C6H4), 6.8 m (4H, Harom), 7.2 m
(2H, Harom). Found, %: C 56.51; H 4.01; Cl 33.39;
N 6.69. C20H16Cl4N2. Calculated, %: C 56.37; H 3.78;
Cl 33.28; N 6.57.
To conclude, we have developed a new one-step
procedure for the synthesis of dispiro pyrido[2,3-g]-
quinoline derivatives via three-component condensa-
tion of N,N′-dibenzyl-p-phenylenediamines with form-
aldehyde and cyclic β-diketones. We have demonstrat-
ed for the first time the possibility of using aromatic
diamines as substrates in such three-component con-
densations.
N,N′-Bis(4-bromobenzyl)benzene-1,4-diamine
(Vc). Yield 83%, mp 178–182°C. IR spectrum, ν, cm–1:
3442 (NH); 3065 (C–Harom); 2925, 2851 (C–Haliph);
1
1616, 1493 (C=Carom). H NMR spectrum, δ, ppm:
4.2 d (4H, NCH2Ar, J = 7 Hz), 5.25 d (2H, NH, J =
7 Hz), 6.4 s (4H, NHC6H4NH), 6.9 d (4H, Harom, J =
9 Hz), 7.2 d (4H, Harom, J = 9 Hz). Found, %: C 53.98;
H 4.23; N 6.35. C20H18Br2N2. Calculated, %: C 53.84;
H 4.07; N 6.28.
EXPERIMENTAL
N,N′-Bis(4-methoxybenzyl)benzene-1,4-diamine
(Vd). Yield 81%, mp 152°C. IR spectrum, ν, cm–1:
3376 (NH); 2959 (C–Harom); 2937, 2838 (C–Haliph);
The IR spectra were recorded in KBr on a Nicolet
Protégé-460 spectrometer with Fourier transform. The
1H NMR spectra were measured from solutions in
DMSO-d6 on Bruker Avance (500 MHz) and Tesla
BS-567 spectrometers (100 MHz) using tetramethyl-
silane as internal reference. The melting points were
determined on a Kofler melting point apparatus.
1
1612, 1512 (C=Carom). H NMR spectrum, δ, ppm:
3.71 s (6H, OCH3), 4.09 d (4H, NCH2Ar, J = 7 Hz),
5.20 d (1H, NH, J = 7 Hz), 5.25 d (1H, NH, J = 7 Hz),
6.39 s (4H, NHC6H4NH), 6.85 d (4H, Harom, J = 9 Hz),
7.25 d (4H, Harom, J = 9 Hz). Found, %: C 75.73;
H 7.02; N 8.15. C22H24N2O2. Calculated, %: C 75.83;
H 6.94; N 8.04.
N,N′-Dibenzyl-p-phenylenediamines Va–Vf
(general procedure). A solution of 0.02 mol of p-phen-
ylenediamine, 0.04 mol of the corresponding benzalde-
hyde, and 1 ml of acetic acid in 250 ml of benzene was
heated under reflux in a flask equipped with a Dean–
Stark trap until the required amount of water separated
(6–12 h). The mixture was cooled, 3.8 g (0.1 mol) of
sodium tetrahydridoborate was added in portions, 18 g
N,N′-Bis(3-ethoxy-4-hydroxybenzyl)benzene-1,4-
diamine (Ve). Yield 35%, mp 141°C. IR spectrum, ν,
cm–1: 3536, 3380 (NH); 2978 (C–Harom); 2932, 2852
1
(C–Haliph); 1609, 1515 (C=Carom). H NMR spectrum,
δ, ppm: 1.27 t (6H, CH2CH3, J = 7 Hz), 3.93 q (4H,
CH2CH3, J = 7 Hz), 3.96 d (4H, NCH2Ar, J = 7 Hz),
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HETEROCYCLIZATION OF N,N′-DISUBSTITUTED p-PHENYLENEDIAMINES
415
5.10 d (2H, NH, J = 7 Hz), 6.37 s (4H, C6H4), 6.66 m
(4H, Harom), 6.85 m (2H, Harom). Found, %: C 70.71;
H 7.04; N 7.05. C24H28N2O4. Calculated, %: C 70.57;
H 6.91; N 6.86.
1′,6′-Bis(4-bromobenzyl)-1′,2,2′,2″,4′,6,6′,6″,-
7′,9′-decahydrodispiro[cyclohexane-1,3′-pyrido-
[2,3-g]quinoline-8′,1″-cyclohexane]-2,2″,6,6″-tetra-
one (VIc). Yield 54%, mp >300°C (decomp.). IR spec-
trum, ν, cm–1: 2957 (C–Harom); 2922, 2828 (C–Haliph);
N,N′-Bis(4-dimethylaminobenzyl)benzene-1,4-
diamine (Vf). Yield 73%, mp 134°C. IR spectrum, ν,
cm–1: 3370 (NH); 3005 (C–Harom); 2884, 2853, 2801
1
1728, 1701 (C=O); 1608, 1513 (C=Carom). H NMR
spectrum, δ, ppm: 1.75 m (4H), 2.45 m (4H), 2.85 m
(4H), 3.2 m (4H), 3.4 m (4H), 4.33 d (4H, NCH2Ar,
J = 7 Hz), 6.3 s (2H, 5′-H, 10′-H), 7.1 d (4H, Harom, J =
9 Hz), 7.47 d (4H, Harom, J = 9 Hz). Found, %:
C 60.25; H 4.83; Br 22.33; N 3.98. C36H34Br2N2O4.
Calculated, %: C 60.18; H 4.77; Br 22.24; N 3.90.
1
(C–Haliph); 1614, 1517 (C=Carom). H NMR spectrum,
δ, ppm: 2.84 s (12H, NCH3), 4.10 d (4H, NCH2Ar, J =
7 Hz), 5.15 d (1H, NH, J = 7 Hz), 5.25 d (1H, NH, J =
7 Hz), 6.45 s (4H, NHC6H4NH), 6.70 d (4H, Harom, J =
9 Hz), 7.20 d (4H, Harom, J = 9 Hz). Found, %:
C 78.68; H 8.01; N 15.07. C24H30N4. Calculated, %:
C 76.97; H 8.07; N 14.96.
1′,6′-Bis(R-benzyl)-4,4,4″,4″-tetra-R2-1′,2,2′,2″,-
4′,6,6′,6″,7′,9′-decahydrodispiro[cyclohexane-1,3′-
pyrido[2,3-g]quinoline-8′,1″-cyclohexane]-2,2″,6,6″-
tetraones VIa–VIl (general procedure). Compound
Va–Vf, 2 mmol, and paraformaldehyde, 8 mmol, were
dissolved in 25 ml of ethanol under slight heating over
a period of 2–3 min, 4 mmol of cyclohexane-1,3-dione
(IIIa) or 5,5-dimethylcyclohexane-1,3-dione (IIIb)
was added in one portion, and the mixture was heated
for 45 min under reflux and left overnight at room
temperature. The precipitate was filtered off, washed
on a filter with ethanol (2×5 ml), dried, and recrystal-
lized from ethanol.
1′,6′-Bis(4-methoxybenzyl)-1′,2,2′,2″,4′,6,6′,6″,-
7′,9′-decahydrodispiro[cyclohexane-1,3′-pyrido-
[2,3-g]quinoline-8′,1″-cyclohexane]-2,2″,6,6″-tetra-
one (VId). Yield 54%, mp 266°C. IR spectrum, ν,
cm–1: 2955 (C–Harom); 2912, 2834 (C–Haliph); 1727,
1
1702 (C=O); 1610, 1511 (C=Carom). H NMR spec-
trum, δ, ppm: 1.70 m (4H), 2.4 m (4H), 2.9 m (4H),
3.2 m (4H), 3.4 m (4H), 3.75 s (6H, OCH3), 4.25 m
(4H, NCH2Ar), 6.3 s (2H, 5′-H, 10′-H), 6.84 d (4H,
Harom, J = 9 Hz), 7.15 d (4H, Harom, J = 9 Hz). Found,
%: C 73.49; H 6.37; N 4.29. C38H40N2O6. Calculated,
%: C 73.53; H 6.50; N 4.51.
1′,6′-Bis(3-ethoxy-4-hydroxybenzyl)-1′,2,2′,2″,-
4′,6,6′,6″,7′,9′-decahydrodispiro[cyclohexane-1,3′-
pyrido[2,3-g]quinoline-8′,1″-cyclohexane]-2,2″,6,6″-
tetraone (VIe). Yield 25%, mp 216°C. IR spectrum, ν,
cm–1: 2954 (C–Harom); 2926, 2869 (C–Haliph); 1728,
1697 (C=O); 1600, 1513 (C=Carom); 1253 (C–O–C);
1′,6′-Bis(4-fluorobenzyl)-1′,2,2′,2″4′,6,6′,6″,7′,9′-
decahydrodispiro[cyclohexane-1,3′-pyrido[2,3-g]-
quinoline-8′,1″-cyclohexane]-2,2″,6,6″-tetraone
(VIa). Yield 41%, mp 243°C. IR spectrum, ν, cm–1:
3050 (C–Harom); 2923, 2858 (C–Haliph); 1727, 1697
1
1077, 855. H NMR spectrum, δ, ppm: 1.25 t (6H,
CH2CH3, J = 7 Hz), 1.7 m (4H), 2.4 m (4H), 2.8 m
(4H), 3.1 m (4H), 3.4 m (4H), 3.95 q (4H, OCH2, J =
7 Hz), 4.2 d (4H, NCH2Ar, J = 7 Hz), 6.4 s (2H, 5′-H,
10′-H), 6.8 m (4H, Harom), 6.9 m (2H, Harom). Found,
%: C 70.48; H 6.39; N 4.27. C40H44N2O8. Calculated,
%: C 70.57; H 6.51; N 4.11.
1
(C=O); 1612, 1508 (C=Carom). H NMR spectrum, δ,
ppm: 1.64 m (4H), 2.43 m (4H), 2.80 m (4H), 3.2 m
(4H), 3.45 m (4H), 4.33 d (4H, NCH2Ar, J = 7 Hz),
6.3 s (2H, 5′-H, 10′-H), 7.1 d (4H, Harom, J = 9 Hz),
7.27 d (4H, Harom, J = 9 Hz). Found, %: C 72.54;
H 5.87; F 6.32; N 4.75. C36H34F2N2O4. Calculated, %:
C 72.47; H 5.74; F 6.37; N 4.70.
1′,6′-Bis(4-dimethylaminobenzyl)-1′,2,2′,2″,4′,6,-
6′,6″,7′,9′-decahydrodispiro[cyclohexane-1,3′-pyr-
ido[2,3-g]quinoline-8′,1″-cyclohexane]-2,2″,6,6″-
tetraone (VIf). Yield 74%, mp 238°C. IR spectrum, ν,
cm –1: 2918 (C–Harom); 2853, 2805 (C–Haliph); 1726,
1′,6′-Bis(2,3-dichlorobenzyl)-1′,2,2′,2″,4′,6,6′,6″,-
7′,9′-decahydrodispiro[cyclohexane-1,3′-pyrido-
[2,3-g]quinoline-8′,1″-cyclohexane]-2,2″,6,6″-tetra-
one (VIb). Yield 24%, mp >300°C (decomp.). IR spec-
trum, ν, cm–1: 2953(C–Harom); 2923, 2853 (C–Haliph);
1
1697 (C=O); 1617, 1521 (C=Carom). H NMR spec-
trum, δ, ppm: 1.75 m (4H), 2.4 m (4H), 2.85 s (12H,
NCH3), 2.9 m (4H), 3.2 m (4H), 3.4 m (4H), 4.21 d
(4H, NCH2Ar, J = 7 Hz), 6.37 s (2H, 5′-H, 10′-H),
6.65 d (4H, Harom, J = 9 Hz), 7.07 d (4H, Harom, J =
9 Hz). Found, %: C 74.35; H 7.21; N 8.74.
C40H46N4O4. Calculated, %: C 74.28; H 7.17; N 8.66.
1
1722, 1694 (C=O); 1614, 1518 (C=Carom). H NMR
spectrum, δ, ppm: 1.64 m (4H), 2.4 m (4H), 2.8 m
(4H), 3.2 m (4H), 3.5 m (4H), 3.6 m (4H), 4.3 d (4H,
NCH2Ar, J = 7 Hz), 6.0 s (2H, 5′-H, 10′-H), 7.2 m
(2H, Harom), 7.4 d (4H, Harom). Found, %: C 62.05;
H 4.73; Cl 20.35; N 4.19. C36H32Cl4N2O4. Calculated,
%: C 61.91; H 4.62; Cl 20.30; N 4.01.
1′,6′-Bis(4-fluorobenzyl)-4,4,4″,4″-tetramethyl-
1′,2,2′,2″,4′,6,6′,6″,7′,9′-decahydrodispiro[cyclo-
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KADUTSKII et al.
416
hexane-1,3′-pyrido[2,3-g]quinoline-8′,1″-cyclohex-
ane]-2,2″,6,6″-tetraone (VIg). Yield 43%, mp 281°C.
IR spectrum, ν, cm–1: 3070, 2951 (C–Harom); 2868,
2817 (C–Haliph); 1729, 1699 (C=O); 1509 (C=Carom).
1H NMR spectrum, δ, ppm: 0.73 s (6H, CH3), 1.03 s
(6H, CH3), 2.30 m (4H), 2.82 m (4H), 3.2 m (4H),
3.63 m (4H), 4.32 d (4H, NCH2Ar, J = 7 Hz), 6.21 s
(2H, 5′-H, 10′-H), 7.1 d (4H, Harom, J = 9 Hz), 7.2 d
(4H, Harom, J = 9 Hz). Found, %: C 73.41; H 6.37;
N 4.33. C40H42F2N2O4. Calculated, %: C 73.60;
H 6.49; N 4.29.
spiro[cyclohexane-1,3′-pyrido[2,3-g]quinoline-
8′,1″-cyclohexane]-2,2″,6,6″-tetraone (VIk). Yield
78%, mp 196–198°C. IR spectrum, ν, cm–1: 2954
(C–Harom); 2926, 2869 (C–Haliph); 1728, 1697 (C=O);
1
1600, 1513 (C=Carom). H NMR spectrum, δ, ppm:
0.75 s (6H, CH3), 1.05 s (6H, CH3), 1.25 t (6H,
CH2CH3, J = 7 Hz), 2.25 m (4H), 2.8 m (4H), 3.1 m
(4H), 3.45 m (4H), 3.95 q (4H, OCH2, J = 7 Hz),
4.21 d (4H, NCH2Ar, J = 7 Hz), 6.3 s (2H, 5′-H,
10′-H), 6.8 m (4H, Harom), 6.9 m (2H, Harom). Found,
%: C 71.56; H 7.21; N 3.94. C44H52N2O8. Calculated,
%: C 71.72; H 7.11; N 3.80.
1′,6′-Bis(2,3-dichlorobenzyl)-4,4,4″,4″-tetra-
methyl-1′,2,2′,2″,4′,6,6′,6″,7′,9′-decahydrodispiro-
[cyclohexane-1,3′-pyrido[2,3-g]quinoline-8′,1″-
cyclohexane]-2,2″,6,6″-tetraone (VIh). Yield 21%,
mp 269°C. IR spectrum, ν, cm–1: 3060 (C–Harom);
2926, 2870 (C–Haliph); 1728, 1697 (C=O); 1516
(C=Carom). 1H NMR spectrum, δ, ppm: 0.7 s (6H, CH3),
1.0 s (6H, CH3), 2.3 m (4H), 2.81 m (4H), 3.1 m (4H),
3.64 m (4H), 4.42 d (4H, NCH2Ar, J = 7 Hz), 6.01 s
(2H, 5′-H, 10′-H), 7.1 m (2H, Harom), 7.3 m (2H, Harom),
7.5 m (2H, Harom). Found, %: C 63.49; H 5.38;
Cl 18.99; N 3.83. C40H40Cl4N2O4. Calculated, %:
C 63.67; H 5.34; Cl 18.79; N 3.71.
1′,6′-Bis(4-dimethylaminobenzyl)-4,4,4″,4″-
tetramethyl-1′,2,2′,2″,4′,6,6′,6″,7′,9′-decahydrodi-
spiro[cyclohexane-1,3′-pyrido[2,3-g]quinoline-
8′,1″-cyclohexane]-2,2″,6,6″-tetraone (VIl). Yield
88%, mp 282°C. IR spectrum, ν, cm–1: 2951 (C–Harom);
2890, 2867, 2809 (C–Haliph); 1725, 1694 (C=O); 1619,
1
1517 (C=Carom). H NMR spectrum, δ, ppm: 0.75 s
(6H, CH3), 1.05 s (6H, CH3), 2.2 m (4H), 2.8 m (4H),
2.85 s (12H, NCH3), 3.1 m (4H), 3.5 m (4H), 4.25 d
(4H, NCH2Ar, J = 7 Hz), 6.35 s (2H, 5′-H, 10′-H),
6.7 d (4H, Harom, J = 9 Hz), 7.0 d (4H, Harom, J = 9 Hz).
Found, %: C 75.25; H 7.61; N 8.04. C44H54N4O4. Cal-
culated, %: C 75.18; H 7.74; N 7.97.
1′,6′-Bis(4-bromobenzyl)-4,4,4″,4″-tetramethyl-
1′,2,2′,2″,4′,6,6′,6″,7′,9′-decahydrodispiro[cyclo-
hexane-1,3′-pyrido[2,3-g]quinoline-8′,1″-cyclohex-
ane]-2,2″,6,6″-tetraone (VIi). Yield 71%, mp 278°C.
IR spectrum, ν, cm–1: 3050 (C–Harom); 2924, 2870
(C–Haliph); 1726, 1694 (C=O); 1517 (C=Carom). 1H NMR
spectrum, δ, ppm: 0.72 s (6H, CH3), 1.04 s (6H, CH3),
2.31 m (4H), 2.86 m (4H), 3.1 m (4H), 3.5 m (4H),
4.3 d (4H, NCH2Ar, J = 7 Hz), 6.1 s (2H, 5′-H, 10′-H),
7.1 m (4H, Harom), 7.4 m (4H, Harom). Found, %:
C 62.19; H 5.59; Br 20.97; N 3.74. C40H42Br2N2O4.
Calculated, %: C 62.02; H 5.47; Br 20.63; N 3.62.
REFERENCES
1. Kozlov, N.G. and Kadutskii, A.P., Tetrahedron Lett.,
2008, vol. 49, p. 4560.
2. Kozlov, N.S., 5,6-Benzokhinoliny (5,6-Benzoquino-
lines), Minsk: Nauka i Tekhnika, 1979, p. 99.
3. Cortés, E., Martínez, R., Avila, G.J., and Toscano, R.A.,
J. Heterocycl. Chem., 1988, vol. 25, p. 895.
4. Martinez, R., Cogordan, J.A., Mancera, C., and
Diaz, Ma.L., Il Farmaco, 2000, vol. 55, p. 631.
5. Kozlov, N.G., Pashkovskii, F.E., Tereshko, A.B., Lo-
kot’, I.P., Gusak, K.N., and Lakhvich, F.A., Russ. J.
Org. Chem., 2003, vol. 39, p. 115.
1′,6′-Bis(4-methoxybenzyl)-4,4,4″,4″-tetrameth-
yl-1′,2,2′,2″,4′,6,6′,6″,7′,9′-decahydrodispiro[cyclo-
hexane-1,3′-pyrido[2,3-g]quinoline-8′,1″-cyclohex-
ane]-2,2″,6,6″-tetraone (VIj). Yield 81%, mp 298°C.
IR spectrum, ν, cm–1: 2953 (C–Harom); 2928, 2868,
2833 (C–Haliph); 1728, 1697 (C=O); 1615, 1513
6. Quiroga, J., Insuasty, B., Hormaza, A., Saitz, C., and
Jullian, C., J. Heterocycl. Chem., 1998, vol. 35, p. 575.
7. Quiroga, J., Hormaza, A., Insuasty, B., Ortiz, A.J.,
Sanchez, A., and Nogueras, M., J. Heterocycl. Chem.,
1998, vol. 35, p. 231.
8. Shi, F., Wang, Q., Tu, S., Zhou, J., Jiang, B., Li, C.,
Zhou, D., Shao, Q., and Cao, L., J. Heterocycl. Chem.,
2008, vol. 41, p. 1103.
9. Chebanov, V.A., Saraev, V.E., Desenko, S.M., Chemen-
ko, V.N., Knyazeva, I.V., Groth, U., Glasnov, T.N., and
Kappe, C.O., J. Org. Chem., 2008, vol. 73, p. 5110.
1
(C=Carom). H NMR spectrum, δ, ppm: 0.75 s (6H,
CH3), 1.05 s (6H, CH3), 2.30 m (4H), 2.82 m (4H),
3.2 m (4H), 3.45 m (4H), 3.65 m (4H), 3.72 s (6H,
OCH3), 4.30 d (4H, NCH2Ar, J = 7 Hz), 6.35 s (2H,
5′-H, 10′-H), 6.85 d (4H, Harom, J = 9 Hz), 7.20 d (4H,
Harom, J = 9 Hz). Found, %: C 74.46; H 7.27; N 4.23.
C42H48N2O6. Calculated, %: C 74.53; H 7.15; N 4.14.
10. Kadutskii, A.P. and Kozlov, N.G., Synlett, 2006, p. 3349.
1′,6′-Bis(3-ethoxy-4-hydroxybenzyl)-4,4,4″,4″-
tetramethyl-1′,2,2′,2″,4′,6,6′,6″,7′,9′-decahydrodi-
11. Temme, O. and Laschat, S., J. Chem. Soc., Perkin
Trans. 1, 1995, p. 125.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 3 2011