Synthesis of pyrimidinocyclophanes having a bridging nitrogen atom

Article abstract of DOI:10.1134/S1070428008060183

Reactions of 1,3-bis(ω-bromoalkyl)-substituted uracils, quinazoline-2,4-dione, and 5-methyl-1,3,5-triazine-2,4,6-trione and 1,3-bis(m-bromomethylbenzyl)-5-bromouracil with amines (aliphatic amines, benzylamines, naphthylmethanamine, and anisidine) gave a series of macrocyclic compounds having one pyrimidine or triazine fragment and an azapolymethylene bridge connecting the N¹ and N³ atoms of the heteroring. The bridging nitrogen atom in some macrocyclic compounds was subjected to quaternization with methyl p-toluenesulfonate.

Full text of DOI:10.1134/S1070428008060183

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2008, Vol. 44, No. 6, pp. 882–890. © Pleiades Publishing, Ltd., 2008.
Original Russian Text © V.E. Semenov, A.E. Nikolaev, A.V. Kozlov, Yu.Ya. Efremov, Sh.K. Latypov, V.S. Reznik, 2008, published in Zhurnal Organicheskoi
Khimii, 2008, Vol. 44, No. 6, pp. 890–898.
Synthesis of Pyrimidinocyclophanes Having a Bridging
Nitrogen Atom
V. E. Semenov, A. E. Nikolaev, A. V. Kozlov, Yu. Ya. Efremov,
Sh. K. Latypov, and V. S. Reznik
Arbuzov Institute of Organic and Physical Chemistry, Kazan Research Center, Russian Academy of Sciences,
ul. Arbuzova 8, Kazan, 420088 Tatarstan, Russia
e-mail: sve@iopc.knc.ru
Received July 17, 2007
Abstract—Reactions of 1,3-bis(ω-bromoalkyl)-substituted uracils, quinazoline-2,4-dione, and 5-methyl-1,3,5-
triazine-2,4,6-trione and 1,3-bis(m-bromomethylbenzyl)-5-bromouracil with amines (aliphatic amines, benzyl-
amines, naphthylmethanamine, and anisidine) gave a series of macrocyclic compounds having one pyrimidine
or triazine fragment and an azapolymethylene bridge connecting the N1 and N3 atoms of the heteroring.
The bridging nitrogen atom in some macrocyclic compounds was subjected to quaternization with methyl
p-toluenesulfonate.
DOI: 10.1134/S1070428008060183
Macrocyclic structures in which the bridging frag-
ments contain heteroatoms, e.g., crown ethers, are
effective complexing agents capable of binding both
neutral and charged species [1]. Introduction of hetero-
aromatic fragments into such structures opens new
prospects in the application of macrocyclic com-
pounds, in particular in the design of new materials.
These prospects originate from the well known ability
of heteroaromatic compounds to form associates
through various interactions (π–π interactions, hydro-
gen bonding, interactions with charged or neutral sub-
strates). Pyrimidine derivatives can be used as hetero-
aromatic fragments.
In the present article we report on the synthesis of
a wide series of pyrimidinocyclophanes having hydro-
carbon bridges with different lengths and rigidity and
various substituents on the C5 and C6 atoms of the
pyrimidine ring and on the bridging nitrogen atom.
Ring closure of 1,3-bis(5-bromopentyl)- and 1,3-bis(6-
bromohexyl)uracils was accomplished via reactions
with both aliphatic amines and those containing an aro-
matic fragment. Pyrimidinocyclophanes VII–XIX con-
taining uracil, thymine, 6-methyluracil, and 5-nitro-
uracyl fragments were obtained at a heterocycle-to-
amine ratio of 1:1 to 1:3 in butan-1-ol in the presence
of K2CO3 and a catalytic amount of tetrabutylammo-
nium hydrogen sulfate (Scheme 1). As amines we used
benzylamine, substituted benzylamines having elec-
tron-donating and electron-withdrawing groups in the
ortho, meta, or para position of the benzene ring,
optically active (R)-(+)-1-phenylethanamine, anisidine,
1-naphthylmethanamine, 3-phenylpropan-1-amine,
and butan-1-amine. The polymethylene bridges
(CH2)nN(R)(CH2)n in the products included 10 or
12 CH2 groups (n = 5 or 6).
We previously synthesized macrocyclic compounds
incorporating two 6-methyl-2,4-dioxo-1,2,3,4-tetrahy-
dropyrimidine (6-methyluracil) fragments and a nitro-
gen atom in the bridge. Their structural specificity and
properties, in particular complex formation with elec-
tron-deficient substrates, were studied [2–4]. We also
reported on the synthesis, structure in crystal and in
solution, conformational behavior, and acid-promoted
aggregation of first representatives of macrocyclic
compounds consisting of a 5-methyluracyl (thymine)
or 6-methyluracil fragment in which the N1 and N3
atoms were linked through a (CH2)5N(R)(CH2)5 bridge,
where R is a butyl or benzyl group [5, 6]. These
macrocycles may be regarded as pyrimidine analogs of
cyclophanes.
Our attempts to synthesize pyrimidinocyclophanes
with a shorter bridge, (CH2)4N(R)(CH2)4 (n = 4) by
reaction of 1,3-bis(4-bromobutyl)thymine (I) with
amines were unsuccessful. According to the mass
spectral data (electron impact), the reaction mixtures
contained only traces of the target products.
882

SYNTHESIS OF PYRIMIDINOCYCLOPHANES
883
Scheme 1.
O
N
( )n–3
O
3N
R1
R2
(CH2)nBr
4
N
R3NH2, K2CO3, BuOH, 100°C
2
5
R1
O
N
R3
N1
6
O
R2
( )n–3
(CH2)nBr
I–VI
VII–XIX
I, n = 4, R1 = Me, R2 = H; II–V, VII–XVIII, n = 5; VI, XIX, n = 6; II, VI–X, XIX, R1 = Me, R2 = H; III, XI, XII, R1 = H, R2 = Me;
IV, XIII–XVII, R1 = R2 = H; V, XVIII, R1 = NO2, R2 = H; VII, XI, XVIII, XIX, R3 = PhCH2; VIII, R3 = 4-MeOC6H4CH2; IX, R3 =
Bu; X, R3 = Ph(CH2)3; XII, R3 = PhCH(Me); XIII, R3 = 4-MeOC6H4; XIV, R3 = 3-MeOC6H4CH2; XV, R3 = 1-naphthylmethyl;
XVI, R3 = 4-ClC6H4CH2; XVII, R3 = 2-ClC6H4CH2.
Scheme 2.
O
( )n –3
O
3N
(CH2)nBr
4
N
RNH2, K2CO3, BuOH, 100°C
2
5
9
O
N
R
6
N1
N
O
9
( )n –3
(CH2)nBr
7
8
XX, XXI
XXII–XXIV
XX, XXII, XXIII, n = 5; XXIV, n = 6; XXII, XXIV, R = PhCH2; XXIII, R = naphthalen-1-ylmethyl.
We also tried to use in the above condensations
uracil derivatives with a fused aromatic fragment, e.g.,
quinazoline-2,4-diones. By reaction of 1,3-bis(5-bro-
mopentyl)- and 1,3-bis(6-bromohexyl)quinazoline-2,4-
diones XX and XXI with benzylamine and 1-naph-
thylmethylamine we obtained the corresponding pyri-
midinocyclophanes XXII–XXIV (Scheme 2).
The progress of the above reactions was monitored
by TLC until complete disappearance of initial com-
pounds I–VI, XX, XXI, XXV, and XXVII (5–8 h).
The yields of macrocycles were fairly poor (5–20%).
The residue was a mixture of a large number of prod-
ucts (presumably oligomeric) which were difficult to
separate. With a view to improve the yield, we per-
formed the reactions under various conditions. How-
ever, variation of the solvent, the use of dilute solu-
tions, and addition of tetraalkylammonium or transi-
tion metal salts did not result in appreciable increase of
the yield of the target macrocyclic products. Neverthe-
less, the following conclusions can be drawn. The
reaction in acetonitrile gives a smaller amount of by-
products than in butan-1-ol, though the reaction time
considerably increases (15–20 h). Replacement of
K2CO3 by Cs2CO3 also favors more selective process.
Flexible polymethylene bridge can be replaced by
more rigid m-phenylenedimethylene linker. Scheme 3
illustrates the synthesis of macrocycle XXVI consist-
ing of m-CH2C6H4CH2N(CH2C6H4OMe-p)-CH2C6H4-
CH2-m and 5-bromouracil fragments. Other 1,3-diaza-
heterocycles may also be used instead of pyrimidine
fragment. For example, the reaction of 1,3-bis(5-
bromopentyl)-5-methylhexahydro-1,3,5-triazine-2,4,6-
trione (XXVII) with benzylamine gave macrocyclic
compound XXVIII (Scheme 4).
Scheme 3.
O
N
O
Br
Br
N
Br
N
4-MeOC6H4NH2, K2CO3
BuOH, 100°C
OMe
O
N
O
N
Br
XXV
XXVI
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 44 No. 6 2008

SEMENOV et al.
884
Scheme 4.
O
N
O
Me
O
(CH2)5Br
Me
O
PhCH2NH2, K2CO3, BuOH, 100°C
N
N
4
N5 3 N
2
6
1
N
O
O
N
(CH2)5Br
XXVII
XXVIII
The structure of the obtained macrocyclic com-
pounds was proved by high-resolution mass spectrom-
etry and NMR spectroscopy. The H NMR spectra of
XXIX which showed a moderate antimicrobial activity
[7]. We succeeded in effecting quaternization of the
bridging nitrogen atom in N-benzyl derivative XXII
only under severe conditions using methyl p-toluene-
sulfonate as both alkylating agent and solvent: as
a result, amphiphilic pyrimidinocyclophane XXX was
isolated. Macrocyclic compounds XXIX and XXX are
soluble in chloroform and water.
1
pyrimidinocyclophanes having m-CH2C6H4CH2 and
(CH2)5N(R)(CH2)5 bridging moieties, as well as of the
first representatives of this class of macroheterocycles
(compounds VII, IX, and XI) [5, 6], revealed magnetic
nonequivalence of all protons in the methylene groups
at the N1 and N3 atoms of the pyrimidine ring. These
Thus we synthesized a series of macrocyclic com-
pounds whose molecules consist of a pyrimidine frag-
ment and an aza polymethylene bridge connecting the
N1 and N3 atoms of the pyrimidine ring; substituents
in the pyrimidine ring, the length and rigidity of the
bridging fragment, and substituents on the bridging
nitrogen atom were varied. Quaternization of the
bridging nitrogen atom with decyl bromide and methyl
p-toluenesulfonate gave water-soluble amphiphilic
pyrimidinocyclophanes.
1
protons resonated in the H NMR spectra of VIII, X,
XII–XVIII, XXII, XXIII, and XXVI in the region δ
5.7–3.5 ppm, the distance between their signals being
δΔ = 0.2–0.4 ppm. Protons in the N1CH2 and N3CH2
groups of pyrimidinocyclophanes XIX and XXIV
having 12 methylene units in the bridge were equiv-
alent in pairs, and they resonated as two multiplets.
These findings are clearly related to the length of the
(CH2)nN(R)(CH2)n bridge which determines specificity
of the steric structure of the above compounds [5, 6].
We also tried to synthesize pyrimidinocyclophanes
with quaternized nitrogen atom in the bridge. How-
ever, our attempts to accomplish N-alkylation of com-
pounds having a benzyl group on the nitrogen were
unsuccessful, presumably because of steric hindrances.
By treatment of compound IX having a butyl substit-
uent on the bridging nitrogen atom with 1-bromo-
decane in acetonitrile we obtained quaternary salt
EXPERIMENTAL
The NMR spectra were recorded at 30°C on
1
a Bruker Avance-600 spectrometer (600 MHz for H
and 150.926 MHz for 13C) from solutions in CDCl3
using the solvent signals as reference (CHCl3,
δ 7.26 ppm; CDCl3, δC 77.0 ppm). The structure of the
products was determined on the basis of a series one-
and two-dimensional NMR correlation experiments
Me
1
1
1
(DEPT, H–1H COSY, H–13C HSQC, and H–13C
HMBC [8–10]). The electron-impact mass spectra
(70 eV) were obtained on a Finnigan MAT-212 mass
spectrometer at a resolution of 1000 using MSS
MASPEC II32 data processing system (direct sample
admission into the ion source, vaporizer temperature
20 to 300°C, electron emission current 1.0 mA).
N
O
N
O
N
(CH2)9Me
(CH2)9Me
Br–
XXIX
Me
N
The syntheses of compounds II [5], III [11], IV
[11], VII [5, 6], IX [6], XI [5], XXVII [12], and
XXXI [7] were reported previously.
O
N
O
N
Me
CH2Ph
1,3-Bis(ω-bromoalkyl)uracils (general proce-
dure). The corresponding uracil or quinazoline-2,4-di-
one, 1 equiv, was added to a solution of sodium but-
TsO–
XXX
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 44 No. 6 2008

SYNTHESIS OF PYRIMIDINOCYCLOPHANES
885
1
oxide prepared by dissolution of 2 equiv of metallic
sodium in butan-2-ol, and the mixture was stirred for
20 h on heating under reflux. The solvent was distilled
off, the residual alcohol was removed as azeotrope
with toluene, and the residue (disodium salt) was
thoroughly dried under reduced pressure. The disodi-
um salt, 1 equiv, was dispersed in dimethylformamide,
a solution of 8 equiv of the corresponding α,ω-di-
bromoalkane in DMF was added under stirring, and
the mixture was stirred for 50–60°C until neutral reac-
tion of an aqueous solution of a sample withdrawn
from the mixture (5–10 h). The solvent and excess
α,ω-dibromoalkane were distilled under reduced pres-
sure, the residue was treated with chloroform, the mix-
ture was filtered, and the filtrate was concentrated to
a volume of 10–15 ml and subjected to column chro-
matography on aluminum oxide.
(41%) of compound VI as an oily substance. H NMR
spectrum, δ, ppm: 7.02 s (1H, 6-H), 3.94 m (2H,
3-CH2), 3.72 m (2H, 1-CH2), 3.40 m (4H, CH2Br),
1.92 s (3H, 5-CH3), 1.89–1.83 m (4H, NCH2CH2),
1.73–1.61 m (4H, CH2CH2Br), 1.51–1.46 m (4H,
NCH2CH2CH2), 1.40–1.34 m (4H, CH2CH2CH2Br).
Found, %: C 45.28; H 6.21; Br 35.01; N 6.38.
C17H28Br2N2O2. Calculated, %: C 45.15; H 6.24;
Br 35.34; N 6.19.
1,3-Bis(5-bromopentyl)-1,2,3,4-tetrahydroquina-
zoline-2,4-dione (XX) was synthesized from 19.07 g
(92.59 mmol) of quinazoline-2,4-dione disodium salt
and 170.37 g (740.74 mmol) of 1,5-dibromopentane in
200 ml of DMF. The column was eluted in succession
with petroleum ether and diethyl ether–petroleum ether
(1:2). Elution with the solvent mixture gave 12.05 g
1
(28%) of compound XX with mp 52–54°C. H NMR
1,3-Bis(4-bromobutyl)-5-methyl-1,2,3,4-tetrahy-
dropyrimidine-2,4-dione (I) was synthesized from
10.85 g (63.82 mmol) of thymine disodium salt and
110.3 g (510.65 mmol) of 1,4-dibromobutane in
180 ml of DMF. The column was eluted in succession
with petroleum ether and diethyl ether–petroleum ether
(3:1). Elution with the solvent mixture gave 8.4 g
spectrum, δ, ppm: 8.22 d (1H, 8-H, J = 7.8 Hz), 7.67 t
(1H, 6-H, J = 7.3 Hz), 7.25 t (1H, 7-H, J = 8.6 Hz),
7.17 d (1H, 5-H, J = 7.5 Hz), 4.09 m (4H, NCH2),
3.42 m (4H, CH2Br), 1.93 m (4H, NCH2CH2), 1.73 m
(4H, CH2CH2Br), 1.60 m (4H, NCH2CH2CH2). Found,
%: C 47.09; H 5.19; Br 34.95; N 6.05. C18H24Br2N2O2.
Calculated, %: C 46.98; H 5.26; Br 34.73; N 6.09.
1
(33%) of compound I as an oily substance. H NMR
1,3-Bis(6-bromohexyl)-1,2,3,4-tetrahydroquina-
zoline-2,4-dione (XXI) was synthesized from 15.00 g
(72.82 mmol) of quinazoline-2,4-dione disodium salt
and 142.14 g (582.54 mmol) of 1,6-dibromohexane in
200 ml of DMF. The column was eluted in succession
with petroleum ether and diethyl ether–petroleum ether
(1:2). Elution with the solvent mixture gave 14.06 g
(36%) of compound XXI as an oily substance.
1H NMR spectrum, δ, ppm: 8.22 d (1H, 8-H, J =
7.8 Hz), 7.67 t (1H, 6-H, J = 8.6 Hz), 7.25 t (1H, 7-H,
J = 6.8 Hz), 7.17 d (1H, 5-H, J = 7.9 Hz), 4.09 m (4H,
NCH2), 3.40 m (4H, CH2Br), 1.86 m (4H, NCH2CH2),
1.72 m (4H, CH2CH2Br), 1.50–1.42 m (8H, CH2CH2).
Found, %: C 49.09; H 5.79; Br 32.92; N 5.66.
C20H28Br2N2O2. Calculated, %: C 49.20; H 5.78;
Br 32.73; N 5.74.
spectrum, δ, ppm: 6.98 s (1H, 6-H), 4.00 m (2H,
3-CH2), 3.75 m (2H, 1-CH2), 3.43 m (4H, CH2Br),
1.92 s (3H, 5-CH3), 1.87–1.78 m (8H, CH2CH2). Found,
%: C 39.64; H 4.99; Br 40.02; N 7.08. C13H20Br2N2O2.
Calculated, %: C 39.42; H 5.09; Br 40.34; N 7.07.
1,3-Bis(5-bromopentyl)-5-nitro-1,2,3,4-tetrahy-
dropyrimidine-2,4-dione (V) was synthesized from
12.8 g (63.69 mmol) of 5-nitrouracil disodium salt and
117.2 g (509.52 mmol) of 1,5-dibromopentane in
250 ml DMF. The column was eluted in succession
with petroleum ether and diethyl ether. Elution with
diethyl ether gave 12.4 g (43%) of compound V as
1
an oily substance. H NMR spectrum, δ, ppm: 8.70 s
(1H, 6-H), 4.00 m (2H, 3-CH2), 3.95 m (2H, 1-CH2),
3.43 m (4H, CH2Br), 1.97–1.47 m (12H, CH2CH2-
CH2). Found, %: C 36.84; H 4.69; Br 35.26; N 9.11.
C14H21Br2N3O4. Calculated, %: C 36.94; H 4.65;
Br 35.11; N 9.23.
5-Bromo-1,3-bis(3-bromomethylbenzyl)-1,2,3,4-
tetrahydropyrimidine-2,4-dione (XXV) was synthe-
sized from 4.2 g (17.87 mmol) of 5-bromouracil di-
sodium salt and 44.04 g (166.82 mmol) of 1,3-bis-
(bromomethyl)benzene in 120 ml of DMF. The mix-
ture was stirred at room temperature. The column was
eluted in succession with petroleum ether and diethyl
ether–petroleum ether (2:1). Elution with the solvent
mixture gave 8.1 g (81%) of compound XXV with
1,3-Bis(6-bromohexyl)-5-methyl-1,2,3,4-tetrahy-
dropyrimidine-2,4-dione (VI) was synthesized from
10.0 g (58.82 mmol) of thymine disodium salt and
100.0 g (409.84 mmol) of 1,6-dibromohexane in
220 ml of DMF. The column was eluted in succession
with petroleum ether and diethyl ether–petroleum ether
(2:1). Elution with the solvent mixture gave 10.9 g
1
mp 133–135°C. H NMR spectrum, δ, ppm: 7.52–
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 44 No. 6 2008

SEMENOV et al.
886
7.20 m (8H, Harom), 7.48 s (1H, 6-H), 5.17 s (2H,
3-CH2), 4.92 s (2H, 1-CH2), 4.47 s (4H, CH2Br). Mass
spectrum, m/z (Irel, %): 560 (34) [M + 6]+, 559 (23)
[M + 5]+, 558 (100) [M + 4]+, 557 (23) [M + 3]+, 556
(100) [M + 2]+, 554 (34) [M]+, 479 (52), 477 (88), 475
(52), 397 (90), 395 (83), 185 (61), 104 (100). Found,
%: C 43.06; H 3.04; Br 43.15; N 5.09. C20H17Br3N2O2.
Calculated, %: C 43.12; H 3.08; Br 43.03; N 5.03.
ol. The column was eluted in succession with petrole-
um ether and diethyl ether–petroleum ether (1:1.5 and
1.5:1). The product was eluted with the 1.5:1 solvent
1
mixture. Yield 0.13 g (5%), oily substance. H NMR
spectrum, δ, ppm: 7.17–7.11 m (5H, Harom), 6.87 s (1H,
6-H), 4.49 m (1H, 1-CH), 4.28 m (1H, 3-CH), 4.01 m
(1H, 3-CH), 3.16 m (1H, 1-CH), 2.49 m (2H, PhCH2),
2.29–2.26 m (6H, NCH2), 2.04 s (3H, 5-CH3), 1.78–
1.50 m (4H, N1(3)CH2CH2), 1.40–1.20 m (10H,
PhCH2CH2, NCH2CH2, N1(3)CH2CH2CH2). Mass spec-
trum, m/z (Irel, %): 398 (3) [M + 1]+, 397 (14) [M]+,
396 (3) [M – 1]+, 293 (19), 292 (100) [M – 105]+,
98 (10). Found, %: C 72.45; H 8.84; N 10.59.
C24H35N3O2. Calculated, %: C 72.51; H 8.87; N 10.57.
M 397.2729.
Macrocyclic compounds VIII, X, XII–XIX,
XXII–XXIV, XXVI, and XXVIII (general proce-
dure). The corresponding amine, 1.3 equiv, was dis-
solved in butan-1-ol, 4 equiv of potassium carbonate
and a catalytic amount of tetrabutylammonium hydro-
gen sulfate were added, the mixture was heated to
90°C, and a solution of 1 equiv of the corresponding
1,3-bis(ω-bromoalkyl)uracil in butan-1-ol was added.
The mixture was stirred at 100–110°C, the progress of
the reaction being monitored by TLC. When the reac-
tion was complete, the solvent was distilled off, 150–
250 ml of chloroform was added to the residue, the
mixture was filtered, and the filtrate was concentrated
to a volume of 10–20 ml and subjected to column
chromatography on silica gel.
16-Methyl-7-[(1R)-1-phenylethyl]-1,7,13-triaza-
bicyclo[11.3.1]heptadec-14-ene-16,17-dione (XII)
was synthesized from 2.00 g (4.72 mmol) of com-
pound III and 0.74 g (6.12 mmol) of (R)-α-phenyl-
ethylamine using 2.61 g (18.88 mmol) of K2CO3 in
150 ml of acetonitrile at 70–75°C. The column was
eluted in succession with petroleum ether and ethyl
acetate–petroleum ether (1.2:1). Elution with the sol-
vent mixture gave 0.16 g (9%) of compound XII with
7-(4-Methoxybenzyl)-15-methyl-1,7,13-triazabi-
cyclo[11.3.1]heptadec-14-ene-16,17-dione (VIII) was
synthesized from 2.50 g (5.90 mmol) of compound II
and 1.05 g (7.66 mmol) of p-methoxybenzylamine
using 3.25 g (23.58 mmol) of K2CO3 in 200 ml of
butan-1-ol. The column was eluted in succession with
petroleum ether and diethyl ether–petroleum ether
(2:1). Elution with the solvent mixture gave 0.65 g
(28%) of compound VIII as an oily substance.
1H NMR spectrum, δ, ppm: 7.05 m (2H, Harom), 6.95 s
(1H, 6-H), 6.78 m (2H, Harom), 4.48 m (1H, 1-CH),
4.27 m (1H, 3-CH), 4.03 m (1H, 3-CH), 3.79 s (3H,
OCH3), 3.34 m (2H, CH2C6H4), 3.15 m (1H, 1-CH),
2.28 m (4H, NCH2), 2.03 s (3H, 5-CH3) 1.92 m (1H,
1-CH2CH), 1.80 m (1H, 3-CH2CH), 1.66 m (1H,
3-CH2CH), 1.47 m (1H, 1-CH2CH), 1.30 m (4H,
NCH2CH2), 1.28 m (4H, NCH2CH2CH2). Mass spec-
trum, m/z (Irel, %): 400 (13) [M + 1]+, 399 (50) [M]+,
398 (7) [M – 1]+, 278 (41) [M – 121]+, 122 (19),
121 (100). Found, %: C69.05; H 8.24; N 10.57.
[M]+ 399.251. C23H33N3O3. Calculated, %: C 69.14;
H 8.33; N 10.52. M 399.252.
1
mp 90–91.5°C. H NMR spectrum, δ, ppm: 7.22 m
(5H, Harom), 5.67 s (1H, 5-H), 4.50 m (1H, 1-CH),
4.25 m (1H, 3-CH), 4.03 m (1H, 3-CH), 3.83 m (1H,
CHPh), 3.54 m (1H, 1-CH), 2.25–2.19 m (4H,
NCH2CH2), 2.16 s (3H, 6-CH3), 1.80–1.26 m (12H,
CH2CH2CH2), 1.25 s (3H, CHCH3). Mass spectrum,
m/z (Irel, %): 384 (12) [M + 1]+, 383 (47) [M]+, 369
(253) [M – 14]+, 368 (100) [M – 15]+, 278 (24) [M –
105]+, 264 (36) [M – 119]+, 105 (82). Found, %:
C 72.12; H 8.58; N 10.87. C23H33N3O2. Calculated, %:
C 72.03; H 8.67; N 10.96. M 383.2573.
7-(4-Methoxyphenyl)-1,7,13-triazabicyclo-
[11.3.1]heptadec-14-ene-16,17-dione (XIII). Sodium
hydride, 0.13 g (5.42 mmol), was added to a solution
of 0.31 g (2.52 mmol) of p-anisidine in 120 ml of
DMF, the mixture was stirred for 2 h at room tem-
perature, a catalytic amount of tetrabutylammonium
hydrogen sulfate and a solution of 1.00 g (2.44 mmol)
of compound IV in 70 ml of DMF were added, and the
mixture was stirred for 20 h at 70–75°C. The mixture
was cooled, the solvent was distilled off, 150 ml of
chloroform was added to the residue, the mixture was
filtered, and the filtrate was concentrated to a volume
of 10–20 ml and subjected to column chromatography
on silica gel. The column was eluted in succession
with petroleum ether and diethyl ether–petroleum ether
15-Methyl-7-(3-phenylpropyl)-1,7,13-triazabicy-
clo[11.3.1]heptadec-14-ene-16,17-dione (X) was syn-
thesized from 3.00 g (7.08 mmol) of compound II and
1.91 g (14.15 mmol) of 3-phenylpropan-1-amine using
3.91 g (28.33 mmol) of K2CO3 in 300 ml of butan-1-
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 44 No. 6 2008

SYNTHESIS OF PYRIMIDINOCYCLOPHANES
887
(1:1). Elution with the solvent mixture gave 0.01 g
(1%) of compound XIII as an oily substance. 1H NMR
spectrum, δ, ppm: 7.04 d (1H, 6-H), 6.78 d (2H, Harom),
6.63 m (2H, Harom), 5.70 d (1H, 5-H), 4.55 m (1H,
1-CH), 4.21 m (1H, 3-CH), 4.07 m (1H, 3-CH), 3.74 s
(3H, OCH3), 2.88 m (1H, 1-CH), 2.04 m (4H, NCH2),
1.88–1.46 m (4H, N1(3)CH2CH2), 1.41 m (4H,
NCH2CH2), 1.25 m (4H, NCH2CH2CH2). Mass spec-
trum, m/z (Irel, %): 371 (60) [M]+, 342 (10), 178 (26),
142 (100). Found, %: C 68.01; H 7.84; N 11.27.
C21H29N3O3. Calculated, %: C 67.90; H 7.87; N 11.31.
M 371.221.
2.41 m (4H, NCH2), 1.84 m (1H, 3-CH2CH), 1.83 m
(1H, 1-CH2CH), 1.66 m (1H, 3-CH2CH), 1.38 m (1H,
1-CH2CH), 1.41 m (4H, NCH2CH2), 1.40 m (4H,
NCH2CH2CH2). Mass spectrum, m/z (Irel, %): 406 (7)
[M + 1]+, 405 (25) [M]+, 404 (11) [M – 1]+, 264 (35)
[M – 141]+, 141 (100). Found, %: C 74.09; H 7.74;
N 10.27. C25H31N3O2. Calculated, %: C 74.04; H 7.70;
N 10.36. M 405.2416.
7-(4-Chlorobenzyl)-1,7,13-triazabicyclo[11.3.1]-
heptadec-14-ene-16,17-dione (XVI) was synthesized
from 3.00 g (7.32 mmol) of compound IV and 1.35 g
(9.54 mmol) of p-chlorobenzylamine using 4.04 g
(29.28 mmol) of K2CO3 in 150 ml of butan-1-ol. The
column was eluted in succession with petroleum ether
and diethyl ether–petroleum ether (3:1). Elution with
the solvent mixture gave 0.27 g (10%) of compound
7-(3-Methoxybenzyl)-1,7,13-triazabicyclo[11.3.1]-
heptadec-14-ene-16,17-dione (XIV) was synthesized
from 2.50 g (6.10 mmol) of compound IV and 1.09 g
(7.96 mmol) of m-methoxybenzylamine using 3.37 g
(24.42 mmol) of K2CO3 in 150 ml of butan-1-ol. The
column was eluted in succession with petroleum ether
and ethyl acetate–petroleum ether (1.2:1). Elution with
the solvent mixture gave 0.26 g (11%) of compound
1
XVI as an oily substance. H NMR spectrum, δ, ppm:
7.24 m (2H, Harom), 7.11 m (2H, Harom), 7.08 d (1H,
6-H), 5.81 d (1H, 5-H), 4.50 m (1H, 1-CH), 4.26 m
(1H, 3-CH), 4.00 m (1H, 3-CH), 3.70 m (2H,
CH2C6H4), 3.20 m (1H, 1-CH), 2.30 m (4H, NCH2),
1.93 m (1H, 1-CH2CH), 1.82 m (1H, 3-CH2CH),
1.65 m (1H, 3-CH2CH), 1.48 m (1H, 1-CH2CH),
1.33 m (4H, NCH2CH2CH2), 1.30 m (4H, NCH2CH2).
Mass spectrum, m/z (Irel, %): 392 (3) [M + 3]+, 391
(18) [M + 2]+, 390 (19) [M + 1]+, 389 (47) [M]+, 388
(32) [M – 1]+, 360 (22), 265 (21), 264 (99) [M – 125]+,
236 (27), 168 (14), 140 (13), 127 (36), 125 (100).
Found, %: C 64.66; H 7.21; Cl 9.15; N 10.77.
C21H28ClN3O2. Calculated, %: C 64.69; H 7.24;
Cl 9.09; N 10.78. M 389.1869.
1
XIV as an oily substance. H NMR spectrum, δ, ppm:
7.17 m (1H, Harom), 7.08 d (1H, 6-H), 6.78 m (2H,
Harom), 6.73 m (1H, Harom), 5.78 d (1H, 5-H), 4.50 m
(1H, 1-CH), 4.26 m (1H, 3-CH), 4.00 m (1H, 3-CH),
3.79 s (3H, OCH3), 3.39 m (2H, CH2C6H4), 3.20 m
(1H, 1-CH), 2.31 m (4H, NCH2), 1.95 m (1H,
1-CH2CH), 1.83 m (1H, 3-CH2CH), 1.63 m (1H,
3-CH2CH), 1.49 m (1H, 1-CH2CH), 1.33 m (4H,
NCH2CH2), 1.32 m (4H, NCH2CH2CH2). Mass spec-
trum, m/z (Irel, %): 386 (12) [M + 1]+, 385 (52) [M]+,
384 (34) [M – 1]+, 356 (23), 265 (17), 264 (100) [M –
121]+, 236 (18), 164 (12), 148 (10), 136 (13), 122
(26), 121 (95). Found, %: C 68.59; H 8.04; N 10.87.
C22H31N3O3. Calculated, %: C 68.54; H 8.11; N 10.90.
M 385.2365.
7-(2-Chlorobenzyl)-1,7,13-triazabicyclo[11.3.1]-
heptadec-14-ene-16,17-dione (XVII) was synthesized
from 2.05 g (5.00 mmol) of compound IV and 0.92 g
(6.50 mmol) of o-chlorobenzylamine using 5.52 g
(40.00 mmol) of K2CO3 in 150 ml of butan-1-ol. The
column was eluted in succession with petroleum ether
and diethyl ether–petroleum ether (1:1 and 2:1). Elu-
tion with the 2:1 solvent mixture gave 0.10 g (5%) of
7-(1-Naphthylmethyl)-1,7,13-triazabicyclo-
[11.3.1]heptadec-14-ene-16,17-dione (XV) was syn-
thesized from 4.20 g (10.24 mmol) of compound IV
and 1.83 g (11.66 mmol) of 1-naphthylmethanamine
using 5.66 g (41.01 mmol) of K2CO3 in 250 ml of
butan-1-ol. The column was eluted in succession with
petroleum ether and ethyl acetate–petroleum ether
(1.2:1). Elution with the solvent mixture gave 0.21 g
1
compound XVII, mp 118°C. H NMR spectrum, δ,
ppm: 7.32 m (1H, Harom), 7.28 m (1H, Harom), 7.19 m
(1H, Harom), 7.13 m (1H, Harom), 7.06 d (1H, 6-H),
5.79 d (1H, 5-H), 4.50 m (1H, 1-CH), 4.27 m (1H,
3-CH), 3.99 m (1H, 3-CH), 3.54 m (2H, CH2C6H4),
3.19 m (1H, 1-CH), 2.34 m (4H, NCH2), 1.94 m (1H,
1-CH2CH), 1.80 m (1H, 3-CH2CH), 1.64 m (1H,
3-CH2CH), 1.47 m (1H, 1-CH2CH), 1.31 m (4H,
NCH2CH2), 1.30 m (4H, NCH2CH2CH2). Mass spec-
trum, m/z (Irel, %): 392 (3) [M + 3]+, 391 (12) [M + 2]+,
390 (18) [M + 1]+, 389 (36) [M]+, 388 (34) [M – 1]+,
360 (23), 265 (17), 264 (100) [M – 125]+, 236 (28),
1
(5%) of compound XV, mp 120–122°C. H NMR
spectrum, δ, ppm: 8.13 m (1H, Harom), 7.81 m (1H,
Harom), 7.73 m (1H, Harom), 7.45 m (2H, Harom), 7.39 m
(1H, Harom), 7.37 m (1H, Harom), 6.95 d (1H, 6-H),
5.75 d (1H, 5-H), 4.46 m (1H, 1-CH), 4.06 m (1H,
C10H7CH), 4.00 m (1H, 3-CH), 3.72 m (1H,
C10H7CH), 3.70 m (1H, 3-CH), 3.12 m (1H, 1-CH),
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 44 No. 6 2008

SEMENOV et al.
888
168 (23), 154 (12), 127 (23), 125 (68). Found, %:
C 64.85; H 7.21; Cl 9.11; N 10.72. C21H28ClN3O2.
Calculated, %: C 64.69; H 7.24; Cl 9.09; N 10.78.
M 389.1869.
and diethyl ether–petroleum ether (4:1). Elution with
the solvent mixture gave 0.37 g (17%) of compound
XXII, mp 123–124°C. H NMR spectrum, δ, ppm:
1
8.36 d (1H, 8-H, J = 7.5 Hz), 7.67 t (1H, 6-H, J =
7.6 Hz), 7.29 t (1H, 7-H, J = 7.5 Hz), 7.24 d (1H, 5-H,
J = 8.3 Hz), 7.07 m (1H, Harom), 6.97 m (2H, Harom),
6.92 m (2H, Harom), 4.87 m (1H, 1-CH), 4.46 m (1H,
3-CH), 4.09 m (1H, 3-CH), 3.85 m (1H, 1-CH), 3.35 m
(1H, CHPh), 3.28 m (1H, CHPh), 2.31 m [2H,
1-(CH2)4CH2N], 2.29 m [2H, 3-(CH2)4CH2N], 1.93 m
(1H, 1-CH2CH), 1.72 m (2H, 3-CH2CH2), 1.69 m (1H,
1-CH2CH), 1.47 m (4H, NCH2CH2), 1.37 m [2H,
1-(CH2)3CH2], 1.33 m (2H, 3-(CH2)3CH2]. Mass spec-
trum, m/z (Irel, %): 406 (31) [M + 1]+, 405 (100) [M]+,
389 (12), 376 (18), 328 (32), 314 (58) [M – 91]+, 142
(23), 91 (68). Found, %: C 74.19; H 7.64; N 10.59.
C25H31N3O2. Calculated, %: C 74.04; H 7.70; N 10.36.
M 405.242.
7-Benzyl-15-nitro-1,7,13-triazabicyclo[11.3.1]-
heptadec-14-ene-16,17-dione (XVIII) was synthe-
sized from 3.00 g (6.59 mmol) of compound V and
1.40 g (13.08 mmol) of benzylamine using 3.64 g
(26.38 mmol) of K2CO3 in 200 ml of acetonitrile. The
column was eluted in succession with petroleum ether
and diethyl ether–petroleum ether (5:1). Elution with
the solvent mixture gave 0.10 g (4%) of compound
1
XVIII, mp 167–169°C. H NMR spectrum, δ, ppm:
8.64 s (1H, 6-H), 7.22 m (2H, Harom), 7.21 m (1H,
Harom), 7.09 m (2H, Harom), 4.65 m (1H, 1-CH), 4.39 m
(1H, 3-CH), 4.03 m (1H, 3-CH), 3.40 m (1H, 1-CH),
3.39 m (2H, CH2Ph), 2.31 m (4H, NCH2), 2.02 m (1H,
1-CH2CH), 1.79 m (1H, 3-CH2CH), 1.68 m (1H,
3-CH2CH), 1.55 m (1H, 1-CH2CH), 1.34 m (4H,
NCH2CH2), 1.32 m (4H, NCH2CH2CH2). Mass spec-
trum, m/z (Irel, %): 401 (9) [M + 1]+, 400 (33) [M]+,
384 (21) [M – 16]+, 383 (84) [M – 17]+, 371 (11), 344
(9), 91 (100). Found, %: C 63.05; H 7.01; N 14.02.
C21H28N4O4. Calculated, %: C 62.98; H 7.05; N 13.99.
M 400.2110.
7-(1-Naphthylmethyl)-14,15-benzo-1,7,13-triaza-
bicyclo[11.3.1]heptadec-14-ene-16,17-dione (XXIII)
was synthesized from 2.00 g (4.35 mmol) of com-
pound XX and 0.82 g (5.22 mmol) of 1-naphthyl-
methanamine using 2.40 g (17.39 mmol) of K2CO3 in
150 ml of butan-1-ol. The column was eluted in
succession with petroleum ether and diethyl ether–
petroleum ether (1:3). Elution with the solvent mixture
gave 0.19 g (10%) of compound XXIII as an oily sub-
8-Benzyl-17-methyl-1,8,15-triazabicyclo[13.3.1]-
nonadec-16-ene-18,19-dione (XIX) was synthesized
from 2.50 g (5.53 mmol) of compound VI and
1.20 g (11.21 mmol) of benzylamine using 3.10 g
(22.46 mmol) of K2CO3 in 350 ml of butan-1-ol. The
column was eluted in succession with petroleum ether
and diethyl ether–petroleum ether (1:5 and 2:1). Elu-
tion with the 2:1 solvent mixture gave 0.48 g (22%) of
1
stance. H NMR spectrum, δ, ppm: 8.37–7.15 m (9H,
Harom), 4.83 m (1H, 1-CH), 4.45 m (1H, 3-CH), 4.10 m
(1H, C10H7CH), 3.92 m (1H, 3-CH), 3.69 m (1H,
1-CH), 3.40 m (1H, C10H7CH), 2.43 m (4H, NCH2),
1.95–1.20 m (12H, CH2CH2CH2). Mass spectrum, m/z
(Irel, %): 456 (9) [M + 1]+, 455 (25) [M]+, 315 (10), 314
(51) [M – 141]+, 142 (14), 141 (100). Found, %:
C 76.29; H 7.36; N 9.36. C29H33N3O2. Calculated, %:
C 76.45; H 7.30; N 9.22. M 455.2573.
1
compound XIX, mp 82–83°C. H NMR spectrum, δ,
ppm: 7.26 m (5H, Harom), 6.94 s (1H, 6-H), 4.08 m
(2H, 1-CH2), 3.79 m (2H, 3-CH2), 3.48 m (2H,
CH2Ph), 2.32 m (4H, NCH2), 1.95 s (3H, 5-CH3),
1.72 m (4H, N1(3)CH2CH2), 1.57 m (4H, NCH2CH2),
1.40 m (4H, N1(3)CH2CH2CH2), 1.28 m (4H, NCH2-
CH2CH2). Mass spectrum, m/z (Irel, %): 398 (8) [M +
1]+, 397 (26) [M]+, 368 (13), 354 (35), 307 (12), 306
(58) [M – 91]+, 134 (14), 106 (15), 96 (16), 91 (100).
Found, %: C 72.38; H 8.81; N 10.68. C24H35N3O2.
Calculated, %: C 72.51; H 8.87; N 10.57. M 397.273.
8-Benzyl-16,17-benzo-1,8,15-triazabicyclo-
[13.3.1]nonadec-16-ene-18,19-dione (XXIV) was
synthesized from 2.50 g (5.12 mmol) of compound
XXI and 0.66 g (6.17 mmol) of benzylamine using
3.00 g (21.74 mmol) of K2CO3 in 500 ml of butan-1-
ol. The column was eluted in succession with petro-
leum ether and diethyl ether–petroleum ether (1:2).
Elution with the solvent mixture gave 0.24 g (11%) of
compound XXIV, mp 158–160°C. 1H NMR spectrum,
δ, ppm: 8.25 d (1H, 8-H, J = 6.5 Hz), 7.66 t (1H, 6-H,
J = 7.2 Hz), 7.24–7.19 m (7H, Harom), 4.29 m (2H,
1-CH2), 4.20 m (2H, 3-CH2), 3.49 m (2H, CH2Ph),
2.35 m (4H, NCH2), 1.78 m (4H, N1(3)CH2CH2), 1.43–
1.32 m (12H, CH2CH2CH2). Mass spectrum, m/z
(Irel, %): 434 (10) [M + 1]+, 433 (41) [M]+, 390 (25),
7-Benzyl-14,15-benzo-1,7,13-triazabicyclo-
[11.3.1]heptadec-14-ene-16,17-dione (XXII) was
synthesized from 2.50 g (5.43 mmol) of compound XX
and 1.16 g (10.84 mmol) of benzylamine using 3.00 g
(21.74 mmol) of K2CO3 in 380 ml of butan-1-ol. The
column was eluted in succession with petroleum ether
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 44 No. 6 2008

SYNTHESIS OF PYRIMIDINOCYCLOPHANES
889
356 (30), 342 (100) [M – 91]+, 314 (10), 202 (12), 188
(13), 174 (10), 160 (14), 132 (33), 106 (31), 91 (88).
Found, %: C 74.66; H 8.18; N 9.59. C27H35N3O2. Cal-
culated, %: C 74.79; H 8.14; N 9.69. M 433.2729.
the precipitate was separated by decanting, washed
with two additional portions of diethyl ether (the prod-
uct was separated each time by decanting), and dried
under reduced pressure. Yield 0.15 g (100%). 1H NMR
spectrum, δ, ppm: 7.80–7.35 m (9H, Harom), 7.02 s (1H,
6-H), 4.10 m (4H, 1-CH2, 3-CH2), 3.74 m (2H,
CH2Ph), 3.03 m (4H, NCH2), 2.64 s (3H, NCH3),
2.35 s (3H, C6H4CH3), 1.95 s (3H, 5-CH3), 1.94–
1.30 m (12H, CH2CH2CH2). Found, %: C 64.98;
H 7.49; N 7.44; S 5.63. C30H41N3O5S. Calculated, %:
C 64.84; H 7.44; N 7.56; S 5.77.
19-Bromo-9-(4-methoxybenzyl)-1,9,17-triaza-
tetracyclo[15.3.1.13,7.111,15]tricosa-3(4),5,7(22),-
11(12),13,15(23),19-heptaene-18,21-dione (XXVI)
was synthesized from 2.50 g (4.49 mmol) of com-
pound XXV and 0.80 g (5.84 mmol) of p-methoxy-
benzylamine using 2.48 g (17.97 mmol) of K2CO3 in
150 ml of butan-1-ol. The column was eluted in suc-
cession with petroleum ether and diethyl ether–petro-
leum ether (2:1). Elution with the solvent mixture
gave 0.09 g (4%) of compound XXVI, mp 74–76°C.
1H NMR spectrum, δ, ppm: 7.60 s (1H, 6-H), 7.38–
6.88 m (12H, Harom), 5.68 d (1H, 1-CH, J = 15.4 Hz),
5.48 d (1H, 3-CH, J = 14.9 Hz), 5.19 d (1H, 3-CH, J =
14.6 Hz), 4.35 d (1H, 1-CH, J = 15.1 Hz), 3.78 s (3H,
OCH3), 3.54 s (2H, CH2C6H4OMe), 3.41 m (4H,
NCH2). Mass spectrum, m/z (Irel, %): 533 (29)
[M + 2]+, 531 (29) [M]+, 426 (11), 412 (12) [M + 2 –
121]+, 410 (9) [M – 121]+, 237 (19), 122 (35), 121
(100), 105 (53), 104 (16). Found, %: C 63.06; H 4.99;
Br 15.19; N 7.82. C28H26BrN3O3. Calculated, %:
C 63.16; N 4.92; Br 15.01; N 7.89. M 531.1158.
This study was performed under financial support
by the Russian Foundation for Basic Research (project
nos. 05-03-32497a, 05-03-32558a, 07-03-00392a), by
the Presidium of the Russian Academy of Sciences
(program no. 8), and by the Joint Russian–American
Program “Basic Research and Higher Education (REC-
007). A.E. Nikolaev and Sh.K. Latypov thank the
Foundation for Support of the Russian Science for
financial support. The compounds were analyzed at the
NMR Department, Federal Spectral and Analytical
Center and Federal Center for Physicochemical
Studies of Substances and Materials (state contract
nos. 02.451.11.7036 and 02.451.11.7019 of the
Ministry of Education and Science of the Russian
Federation).
7-Benzyl-15-methyl-1,7,13,15-tetraazabicyclo-
[11.3.1]heptadecane-14,16,17-trione (XXVIII) was
synthesized from 3.30 g (7.48 mmol) of compound
XXVII and 1.04 g (9.72 mmol) of benzylamine using
4.13 g (29.93 mmol) of K2CO3 in 180 ml of butan-1-
ol. The column was eluted in succession with petro-
leum ether and ethyl acetate–petroleum ether (1.2:1).
Elution with the solvent mixture gave 0.37 g (13%) of
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1
compound XXVIII, mp 103.5–105°C. H NMR spec-
trum, δ, ppm: 7.28–7.15 m (5H, Harom), 4.07 t (4H,
1-CH2, 3-CH2), 3.44 m (5H, 5-CH3, CH2Ph), 2.32 m
(4H, NCH2), 1.75–1.63 m (4H, N1(3)CH2CH2), 1.54–
1.34 m (8H, CH2CH2). Mass spectrum, m/z (Irel, %):
387 (12) [M + 1]+, 386 (52) [M]+, 385 (10) [M – 1]+,
357 (17), 329 (10), 295 (62) [M – 91]+, 267 (16), 174
(13), 134 (14), 132 (18), 120 (32), 118 (20), 106
(35), 91 (100). Found, %: C 65.33; H 7.79; N 14.38.
C21H30N4O3. Calculated, %: C 65.26; H 7.82; N 14.50.
M 386.2318.
7-Benzyl-7,15-dimethyl-16,17-dioxo-1,13-diaza-
7-azoniabicyclo[11.3.1]heptadec-14-ene 4-methyl-
benzenesulfonate (XXX). A mixture of 0.10 g
(0.27 mmol) of compound VII and 4 g of methyl
p-toluenesulfonate was stirred for 6 h at 80°C. The
mixture was cooled and diluted with diethyl ether, and
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SEMENOV et al.
890
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