Synthesis and properties of (E)-4-[alkyl(aryl)iminomethyl]-2- methoxy(ethoxy)phenyl adamantane-1-carboxylates

Article abstract of DOI:10.1134/S107042801004010X

Condensation of 4-formyl-2-methoxy(ethoxy)phenyl adamantane-1-carboxylates with aliphatic, cycloaliphatic, and aromatic amines gave the corresponding adamantane-containing Schiff bases as E isomers with respect to the CH=N azomethine bond. The reaction of 2-methoxy-4-(naphthalen-2-yliminomethyl)phenyl adamantane-1-carboxylate with cyclohexane-1,3-dione and dimedone led to the formation of 2-methoxy-4-(11-oxo-7,8,9,10,11,12-hexahydrobenzo[a]acridin-12-yl) phenyl adamantane-1-carboxylates. Quantum-chemical calculations of the energies of formation of E and Z isomers of some of the synthesized Schiff bases were performed.

Full text of DOI:10.1134/S107042801004010X

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2010, Vol. 46, No. 4, pp. 506–516. © Pleiades Publishing, Ltd., 2010.
Original Russian Text © E.A. Dikusar, N.G. Kozlov, V.I. Potkin, 2010, published in Zhurnal Organicheskoi Khimii, 2010, Vol. 46, No. 4, pp. 517–526.
Synthesis and Properties of (E)-4-[Alkyl(aryl)iminomethyl]-
2-methoxy(ethoxy)phenyl Adamantane-1-carboxylates
E. A. Dikusar, N. G. Kozlov, and V. I. Potkin
Institute of Physical Organic Chemistry, National Academy of Sciences of Belarus,
ul. Surganova 13, Minsk, 220072 Belarus
e-mail: dikusar@ifoch.bas-net.by
Received February 18, 2009
Abstract—Condensation of 4-formyl-2-methoxy(ethoxy)phenyl adamantane-1-carboxylates with aliphatic,
cycloaliphatic, and aromatic amines gave the corresponding adamantane-containing Schiff bases as E isomers
with respect to the CH=N azomethine bond. The reaction of 2-methoxy-4-(naphthalen-2-yliminomethyl)phenyl
adamantane-1-carboxylate with cyclohexane-1,3-dione and dimedone led to the formation of 2-methoxy-4-(11-
oxo-7,8,9,10,11,12-hexahydrobenzo[a]acridin-12-yl)phenyl adamantane-1-carboxylates. Quantum-chemical
calculations of the energies of formation of E and Z isomers of some of the synthesized Schiff bases were
performed.
DOI: 10.1134/S107042801004010X
Nitrogen-containing adamantane derivatives exhibit
a broad spectrum of biological activity [1]. Com-
pounds possessing antiviral, curare-like, myorelaxant,
anticholine esterase, psychostimulating, neurotropic,
and local anesthetic properties were found in this series
[2]. Such efficient drugs as Midantan, Memantine,
Gludantan, Rimantadine, and Adapromine were devel-
oped on the basis of adamantane derivatives [3]. We
previously reported on the synthesis of a series of ada-
mantane derivatives containing pharmacophoric frag-
ments with a view to reveal among them new biologi-
cally active substances [4–8].
vanillin (Ia) and vanillal (Ib) with aliphatic, cycloali-
phatic, and aromatic primary amines IIa–IIt. The
reactions were carried out in anhydrous methanol on
heating under reflux over a period of 10–15 min, and
their mild conditions (the absence of catalyst) favored
conservation of labile ester groups. The products were
isolated in 85–92% yield, and their purity was 96±2%
1
according to the H NMR data. We thus synthesized
adamantane-containing Schiff bases IIIa–IIIt and
IVa–IVt, including those possessing two adamantane
fragments (compounds IIId and IVd) (Scheme 1).
Adamantane-containing Schiff bases IIIa–IIIt and
IVa–IVt were isolated as colorless or slightly colored
crystalline substances; they contained no impurities of
initial compounds and required no additional purifica-
The goal of the present work was to obtain new
adamantane-containing Schiff bases by condensation
of adamantane-1-carboxylic acid esters derived from
Scheme 1.
NR'
CHO
+
R'NH2
RO
RO
O
O
O
O
Ia, Ib
IIa–IIt
IIIa–IIIt, IVa–IVt
Ia, III, R = Me; Ib, IV, R = Et; R′ = Me(CH2)15 (a), Me(CH2)17 (b), cyclo-C6H11 (c), (1-Ad)CH(Me) (d), Ph (e), 4-MeC6H4 (f),
2-PhC6H4 (g), 4-PhC6H4 (h), 4-BrC6H4 (i), 2-HOC6H4 (j), 4-PhOC6H4 (k), 4-MeC(O)C6H4 (l), 4-EtC(O)C6H4 (m), 3-HOCOC6H4 (n),
4-HOCOC6H4 (o), 4-EtOCOC6H4 (p), 4-BuOCOC6H4 (q), 1-C10H7 (r), 2-C10H7 (s), 1-Br-2-C10H6 (t).
506

SYNTHESIS AND PROPERTIES OF (E)-4-[ALKYL(ARYL)IMINOMETHYL]-...
507
tion. Their structure was confirmed by the IR, UV, and
1H NMR spectra, elemental analyses, and cryoscopic
determination of the molecular weight. Protons in the
azomethine group (HC=N) in compounds IIIa–IIIt
ized aza heterocycles having a partly hydrogenated
quinoline fragment, which may be regarded as analogs
of quinoline antibiotics, pesticides, and compounds
possessing antitumor, bactericidal, and anti-enzyme
activity [3, 14–17].
1
and IVa–IVt resonated in the H NMR spectra as
singlets in the region δ 8.23–8.58 ppm, which is
typical of E isomers [9].
The condensation of aldehyde Ia with naphthalen-
2-amine and 1,3-diketone was carried out by heating
equimolar amounts of the reactants in ethanol in the
absence of a catalyst. Fused aza heterocycle is formed
as a result of a series of transformations including
initial reaction of aldehyde Ia with naphthalen-2-amine
(IIs) to give Schiff base IIIs which then takes up
cyclohexane-1,3-dione molecule at the CH=N carbon
atom, yielding intermediate amino diketone. The latter
undergoes hydramine fission into the corresponding
amine and 2-arylmethylidenecyclohexane-1,3-dione in
which the exocyclic double bond is activated due to
conjugation with two neighboring carbonyl groups.
Electrophilic substitution in the naphthalene ring at the
carbon atom in the α-position with respect to the amino
group leads to amino diketone whose oxidative intra-
molecular cyclization selectively affords compound Va
or Vb. By analogy with the data of [18], the trans-
formation of amino diketone may be regarded as
rearrangement like Hofmann–Martius (migration of
an alkyl substituent on the nitrogen atom in aniline
molecule into the ortho position of aromatic ring [19]).
Schiff bases III and IV can be used as initial com-
pounds for the synthesis of analogs of acridine alka-
loids containing adamantane fragments. Compound
IIIs reacted with an equimolar amount of cyclohexane-
1,3-dione or dimedone (5,5-dimethylcyclohexane-1,3-
dione) on heating in ethanol in the absence of a cata-
lyst to give 70–75% of 2-methoxy-4-(11-oxo-
7,8,9,10,11,12-hexahydrobenzo[a]acridin-12-yl)phenyl
adamantane-1-carboxylates Va and Vb, respectively
(Scheme 2). Compounds Va and Vb were also syn-
thesized by three-component condensation of aldehyde
Ia with naphthalen-2-amine and the corresponding di-
ketone. In the recent time, three-component condensa-
tions have become more and more important as ef-
ficient and selective synthetic routes to fused nitrogen-
containing heterocycles [10–13].
Heterocyclization of functionally substituted benz-
aldehyde Ia containing a methoxy group and adaman-
tanecarboxylic acid moiety opens a way to functional-
Scheme 2.
R
R
MeO
MeO
O
O
O
O
O
O
N
O
HN
+
R
O
R
IIIs
R
R
MeO
MeO
O
O
NH2
O
O
NH
R
O
O
O
R
Va, Vb
R = H (a), Me (b).
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 4 2010

DIKUSAR et al.
508
Scheme 3.
R
R
MeO
MeO
O
O
O
O
O
N
O
HN
+
R
O
R
IIIs
VIa, VIb
(Scheme 3). The ΔHf values were as follows, kcal/mol:
Va, –100.4; Vb, –89.9; VIa, –110.9; VIb, –102.3.
Thus compounds Va and Vb are thermodynamically
more stable than isomeric structures VIa and VIb by
8.6–10.5 kcal/mol. This means that the condensation
of IIIs with cyclohexane-1,3-diones should lead to
the formation of thermodynamically more stable prod-
ucts Va and Vb.
The structure of compounds Va and Vb was con-
firmed by their elemental compositions and H NMR
1
and IR spectra. The IR spectra of Va and Vb charac-
teristically contained absorption bands belonging to
stretching and bending vibrations of the NH bond in
the dihydropyridine fragment (3270–3260 and 1635–
1630 cm–1, respectively). Stretching vibrations of the
carbonyl group conjugated with the enamine fragment
appeared at 1645–1640 cm–1. In the 1H NMR spectra
of benzo[a]acridinones Va and Vb we observed sin-
glets from the 12-H and NH protons at δ 5.85 and
9.3 ppm (cf. [9, 10, 12]), as well as three broadened
singlets at δ 1.75 (6H, CH), 1.95 (6H, CH2), and
2.05 ppm (6H, CH2) which are typical of 1-substituted
adamantane fragment.
EXPERIMENTAL
The IR spectra were recorded in KBr on a Nicolet
Protégé-460 spectrometer with Fourier transform. The
UV spectra were measured on a Specord UV-Vis spec-
trophotometer from 1×10–4 M solutions in methanol.
1
The H NMR spectra were obtained on a Tesla BS-
As noted above, Schiff bases IIIa–IIIt and IVa–
IVt were assigned E configuration with respect to the
587A instrument at 100 MHz from 5% solutions in
chloroform-d or DMSO-d6 (δ 2.50 ppm); the chemical
shifts were determined relative to tetramethylsilane as
internal reference. The elemental compositions were
determined on an Elementar Vario EL-III C,H,N,O,S
analyzer with an accuracy of ±0.1%. The molecular
weights were determined by cryoscopy in benzene.
1
azomethine CH=N bond on the basis of the H NMR
data. With a view to confirm this assignment, we
calculated the heats of formation ΔHf of the E and Z
isomers of Schiff bases IIIe, IIIr, IIIs, and IVe. The
calculations were performed in terms of the MNDO
PM3 semiempirical approximation [20, 21] using
GAMESS program [22] with complete optimization of
all bond lengths and bond and dihedral angles. The
following ΔHf values were obtained (kcal/mol) for the
E isomers (the data for the Z isomers are given in
parentheses): IIIe, 66.8 (–65.8); IIIr, –48.2 (–47.1);
IIIs, –49.7 (–48.6); IVe, –71.7 (–70.4). It is seen that
in all cases the E isomer is more energetically favor-
able (by 1.0–1.3 kcal/mol) than the Z isomer. The E
isomer of Schiff base IIIs derived from naphthalen-2-
amine is more stable (by 1.5 kcal/mol) than its analog
E-IIIr derived from naphthalen-1-amine, which is con-
sistent with the data of [23].
Initial adamantane-1-carboxylates Ia and Ib were
synthesized as described in [5].
(E)-4-[Alkyl(aryl)iminomethyl]-2-methoxy-
(ethoxy)phenyl adamantane-1-carboxylates IIIa–
IIIt and IVa–IVt (general procedure). A solution of
5 mmol of 3-methoxy- or 3-ethoxy-4-(1-adamantyl-
oxycarbonyl)benzaldehyde Ia or Ib and 5 mmol of the
corresponding primary amine IIa–IIt in 30 ml of
anhydrous methanol was heated for 10–15 min under
reflux. The mixture was filtered while hot through
a folded filter paper, and the filtrate was cooled and
left to stand for 10–15 h at 5°C. The precipitate, Schiff
base IIIa–IIIt or IVa–IIIt, was filtered off through
a glass filter, washed with a small amount of methanol,
and dried in air.
Using the same calculation procedure, we estimated
the heats of formation of compounds Va and Vb
and alternative condensation products VIa and VIb
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SYNTHESIS AND PROPERTIES OF (E)-4-[ALKYL(ARYL)IMINOMETHYL]-...
509
1
221 (14000), 254 (9000), 300 (500). H NMR spec-
trum, δ, ppm: 1.14 d (3H, Me), 1.55–2.15 m (30H,
Ad), 2.84 q (1H, CH), 3.84 s (3H, MeO), 7.00–7.48 m
(3H, Harom), 8.18 s (1H, CH=N). Found, %: C 78.53;
H 8.75; N 2.77. M 462.0. C31H41NO3. Calculated, %:
C 78.28; H 8.69; N 2.94. M 475.7.
(E)-4-(Hexadecyliminomethyl)-2-methoxyphenyl
adamantane-1-carboxylate (IIIa). Yield 89%,
mp 62–63°C. IR spectrum, ν, cm–1: 3073, 3060, 3004
(C–Harom); 2955, 2918, 2850 (C–Haliph); 1752 (C=O);
1650 (C=N); 1606, 1508 (C=Carom); 1466, 1452 (CH2);
1277, 1264, 1218, 1195, 1151, 1119, 1099, 1052, 1033
(C–O); 878, 860, 818, 802, 770, 730, 725 (δC–Harom).
UV spectrum, λmax, nm (ε): 208 (14000), 220 (13000),
(E)-2-Methoxy-4-phenyliminomethylphenyl ada-
mantane-1-carboxylate (IIIe). Yield 88%, mp 124–
125°C. IR spectrum, ν, cm–1: 3090, 3070, 3030, 3020,
3004 (C–Harom); 2965, 2940, 2905, 2867, 2849
(C–Haliph); 1752 (C=O); 1629 (C=N); 1601, 1581,
1508, 1485 (C=Carom); 1465, 1450 (CH2); 1286, 1261,
1215, 1196, 1178, 1153, 1109, 1039 (C–O); 860, 852,
822, 803, 788, 765, 756, 740, 696 (δC–Harom). UV
spectrum, λmax, nm (ε): 202 (33000), 221 (23000), 269
1
253 (9000), 300 (400). H NMR spectrum, δ, ppm:
0.92 t (3H, Me), 1.10–2.15 m [43H, Ad, (CH2)14],
3.64 t (2H, CH2N), 3.82 s (3H, MeO), 7.06–7.48 m
(3H, Harom), 8.23 s (1H, CH=N). Found, %: C 78.35;
H 10.42; N 2.24. M 526.2. C35H55NO3. Calculated, %:
C 78.16; H 10.31; N 2.60. M 537.8.
(E)-2-Methoxy-4-(octadecyliminomethyl)phenyl
adamantane-1-carboxylate (IIIb). Yield 90%,
mp 63–64°C. IR spectrum, ν, cm–1: 3072, 3045, 3004
(C–Harom); 2917, 2850 (C–Haliph); 1753 (C=O); 1651
(C=N); 1603, 1513 (C=Carom); 1470, 1451 (CH2);
1275, 1219, 1197, 1170, 1160, 1119, 1112, 1054
(C–O); 867, 840, 822, 740, 723 (δC–Harom). UV spec-
trum, λmax, nm (ε): 207 (14000), 220 (13000), 254
1
(15 000), 316 (12000). H NMR spectrum, δ, ppm:
1.65–2.40 m (15H, Ad), 3.91 s (3H, MeO), 7.00–
7.72 m (8H, Harom), 8.40 s (1H, CH=N). Found, %:
C 77.38; H 7.12; N 3.25. M 372.8. C25H27NO3. Calcu-
lated, %: C 77.09; H 6.99; N 3.60. M 389.5.
(E)-2-Methoxy-4-[(4-methylphenyl)imino-
methyl]phenyl adamantane-1-carboxylate (IIIf).
Yield 88%, mp 141–142°C. IR spectrum, ν, cm–1:
3091, 3080, 3061, 3040, 3030, 3004 (C–Harom); 2955,
2917, 2904, 2887, 2849 (C–Haliph); 1750 (C=O); 1629
(C=N); 1600, 1583, 1508 (C=Carom); 1463, 1450
(CH2); 1288, 1261, 1218, 1184, 1156, 1110, 1041
(C–O); 873, 853, 816, 791, 735, 726, 718, 706, 676
(δC–Harom). UV spectrum, λmax, nm (ε): 201 (40000),
1
(9000), 300 (400). H NMR spectrum, δ, ppm: 0.92 t
(3H, Me), 1.10–2.14 m [47H, Ad, (CH2)16], 3.63 t (2H,
CH2N), 3.82 s (3H, MeO), 7.06–7.48 m (3H, Harom),
8.23 s (1H, CH=N). Found, %: C 78.86; H 10.58;
N 2.09. M 551.3. C37H59NO3. Calculated, %: C 78.53;
H 10.51; N 2.48. M 565.9.
(E)-4-(Cyclohexyliminomethyl)-2-methoxy-
phenyl adamantane-1-carboxylate (IIIc). Yield 85%,
mp 101–102°C. IR spectrum, ν, cm–1: 3070, 3015
(C–Harom); 2926, 2908, 2852 (C–Haliph); 1743 (C=O);
1643 (C=N); 1602, 1590, 1510 (C=Carom); 1469, 1450
(CH2); 1291, 1264, 1222, 1199, 1182, 1155, 1110,
1054, 1033 (C–O); 862, 849, 822, 801, 783, 730
(δC–Harom). UV spectrum, λmax, nm (ε): 208 (14000),
1
223 (37000), 270 (28000), 321 (28000). H NMR
spectrum, δ, ppm: 1.60–2.15 m (15H, Ad), 2.33 s (3H,
Me), 3.83 s (3H, MeO), 7.02–7.75 m (7H, Harom),
8.59 s (1H, CH=N). Found, %: C 77.64; H 7.29;
N 3.19. M 393.6. C26H29NO3. Calculated, %: C 77.39;
H 7.24; N 3.47. M 403.5.
1
220 (12000), 253 (9000), 300 (400). H NMR spec-
(E)-4-(Biphenyl-2yliminomethyl)-2-methoxy-
phenyl adamantane-1-carboxylate (IIIg). Yield 85%,
mp 142–143°C. IR spectrum, ν, cm–1: 3090, 3080,
3057, 3040, 3021 (C–Harom); 2925, 2902, 2846
(C–Haliph); 1745 (C=O); 1626 (C=N); 1602, 1586,
1511, 1503 (C=Carom); 1477, 1450 (CH2); 1293, 1158,
1109, 1057, 1030 (C–O); 872, 861, 850, 846, 821, 772,
748, 732, 699, 678 (δC–Harom). UV spectrum, λmax, nm
trum, δ, ppm: 1.10–2.15 m (26H, Ad, C6H11), 3.82 s
(3H, MeO), 7.02–7.48 m (3H, Harom), 8.22 s (1H,
CH=N). Found, %: C 76.15; H 8.57; N 3.18. M 387.6.
C25H33NO3. Calculated, %: C 75.91; H 8.41; N 3.54.
M 395.5.
(E)-4-[1-(1-Adamantyl)ethyliminomethyl]-2-
methoxyphenyl adamantane-1-carboxylate (IIId).
Yield 92%, mp 200–201°C. IR spectrum, ν, cm–1:
3080, 3030 (C–Harom); 2955, 2930, 2903, 2849, 2812
(C–Haliph); 1752 C=O; 1647 (C=N); 1602, 1503
(C=Carom); 1463, 1452 (CH2); 1274, 1215, 1193, 1154,
1121, 1051, 1045 (CO); 880, 840, 821, 785, 750, 731
(δC–Harom). UV spectrum, λmax, nm (ε): 208 (15000),
1
(ε): 205 (22000), 265 (13000), 318 (12000). H NMR
spectrum, δ, ppm: 1.67–2.40 m (15H, Ad), 3.92 s (3H,
MeO), 6.94–7.62 m (12H, Harom), 8.43 s (1H, CH=N).
Found, %: C 80.25; H 6.83; N 2.78. M 456.0.
C31H31NO3. Calculated, %: C 79.97; H 6.71; N 3.01.
M 465.6.
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DIKUSAR et al.
510
(C=N); 1600, 1587, 1577, 1510, 1496, 1486 (C=Carom);
(E)-4-(Biphenyl-4-yliminomethyl)-2-methoxy-
1468, 1450 (CH2); 1292, 1274, 1265, 1238, 1214,
1198, 1180, 1156, 1111, 1099, 1052, 1034 (C–O); 866,
860, 854, 841, 814, 790, 780, 760, 740, 691, 680
(δC–Harom). UV spectrum, λmax, nm (ε): 200 (51000),
phenyl adamantane-1-carboxylate (IIIh). Yield
87%, mp 164–165°C. IR spectrum, ν, cm–1: 3090,
3077, 3052, 3032, 3004 (C–Harom); 2930, 2904, 2848
C–Haliph); 1748 (C=O); 1631 (C=N); 1600, 1581, 1505
(C=Carom); 1465, 1451 (CH2); 1287, 1274, 1263, 1218,
1190, 1149, 1110, 1051, 1045, 1033 (C–O); 877, 848,
835, 819, 769, 740, 693, 670 (δC–Harom). UV spec-
trum, λmax, nm (ε): 204 (20000), 270 (14000), 320
1
224 (34000), 271 (20000), 327 (20000). H NMR
spectrum, δ, ppm: 1.60–2.24 m (15H, Ad), 3.88 s (3H,
MeO), 6.80–7.70 m (12H, Harom), 8.49 s (1H, CH=N).
Found, %: C 77.59; H 6.56; N 2.62. M 462.8.
C31H31NO4. Calculated, %: C 77.31; H 6.49; N 2.91.
M 481.6.
1
(10000). H NMR spectrum, δ, ppm: 1.68–2.42 m
(15H, Ad), 3.92 s (3H, MeO), 6.98–7.74 m (12H,
Harom), 8.44 s (1H, CH=N). Found, %: C 80.23;
H 6.88; N 2.76. M 454.2. C31H31NO3. Calculated, %:
C 79.97; H 6.71; N 3.01. M 465.6.
(E)-4-[(4-Acetylphenyl)iminomethyl]-2-methoxy-
phenyl adamantane-1-carboxylate (IIIl). Yield 85%,
mp 111–112°C. IR spectrum, ν, cm–1: 3070, 3045,
3002 (C–Harom); 2940, 2905, 2851 (C–Haliph); 1748,
1660 (C=O); 1627 (C=N); 1595, 1527, 1507 (C=Carom);
1468, 1452 (CH2); 1275, 1219, 1198, 1178, 1150,
1121, 1051, 1042 (C–O); 852, 840, 830, 800, 784, 749,
733, 680 (δC–Harom). UV spectrum, λmax, nm (ε): 204
(30000), 220 (20000), 255 (10000), 308 (15000).
1H NMR spectrum, δ, ppm: 1.56–2.25 m (15H, Ad),
3.73 s (3H, Me), 3.84 s (3H, MeO), 6.90–8.10 m (7H,
Harom), 8.46 s (1H, CH=N). Found, %: C 75.56;
H 6.84; N 3.03. M 412.9. C27H29NO4. Calculated, %:
C 75.15; H 6.77; N 3.25. M 431.5.
(E)-4-[(4-Bromophenyl)iminomethyl]-2-methoxy-
phenyl adamantane-1-carboxylate (IIIi). Yield 90%,
mp 145–146°C. IR spectrum, ν, cm–1: 3082, 3055,
3004 (C–Harom); 2940, 2909, 2852 (C–Haliph); 1738
(C=O); 1625 (C=N); 1601, 1582, 1577, 1511, 1480
(C=Carom); 1470, 1453 (CH2); 1289, 1265, 1217, 1197,
1181, 1157, 1111, 1055, 1029 (C–O); 871, 848, 824,
786, 767, 745, 736, 703, 676 (δC–Harom). UV spec-
trum, λmax, nm (ε): 205 (24000), 224 (23000), 268
1
(18000), 320 (18000). H NMR spectrum, δ, ppm:
1.55–2.15 m (15H, Ad), 3.83 s (3H, MeO), 7.01–
7.72 m (7H, Harom), 8.58 s (1H, CH=N). Found, %:
C 64.53; H 5.72; Br 16.75; N 2.63. M 455.9.
C25H26BrNO3. Calculated, %: C 64.11; H 5.60;
Br 17.06; N 2.99. M 468.4.
(E)-2-Methoxy-4-[4-(1-oxopropyl)phenylimino-
methyl]phenyl adamantane-1-carboxylate (IIIm).
Yield 87%, mp 110–111°C. IR spectrum, ν, cm–1:
3090, 3063, 3040, 3004 (C–Harom); 2980, 2938, 2904,
2850 (C–Haliph); 1749, 1685 (C=O); 1625 (C=N);
1596, 1583, 1557, 1514 (C=Carom); 1469, 1452, 1440
(CH2); 1240, 1230, 1184, 1170, 1129, 1054, 1031
(C–O); 882, 842, 806, 796, 750, 726, 880 (δC–Harom).
UV spectrum, λmax, nm (ε): 205 (28000), 221 (20000),
(E)-4-[(2-Hydroxyphenyl)iminomethyl]-2-me-
thoxyphenyl adamantane-1-carboxylate (IIIj). Yield
86%, mp 141–142°C. IR spectrum, ν, cm–1: 3407
(OH); 3077, 3040, 3026, 3004 (C–Harom); 2931, 2906,
2852 (C–Haliph); 1751 (C=O); 1624 (C=N); 1586,
1506, 1498 (C=Carom); 1484, 1453 (CH2); 1277, 1248,
1215, 1193, 1179, 1151, 1116, 1046, 1030, 1022
(C–O); 872, 845, 822, 815, 801, 782, 749, 735, 671
(δC–Harom). UV spectrum, λmax, nm (ε): 204 (34000),
1
254 (10000), 308 (14000). H NMR spectrum, δ, ppm:
1.25 t (3H, Me), 1.56–2.24 m (15H, Ad), 2.94 q (2H,
CH2), 3.88 s (3H, MeO), 6.90–8.04 m (7H, Harom),
8.44 s (1H, CH=N). Found, %: C 75.81; H 7.18;
N 2.88. M 432.6. C28H31NO4. Calculated, %: C 75.48;
H 7.01; N 3.14. M 445.6.
1
233 (15000), 284 (11000), 344 (10000). H NMR
spectrum, δ, ppm: 1.62–2.20 m (15H, Ad), 3.85 s (3H,
MeO), 6.50–7.90 m (7H, Harom), 8.68 s (1H, CH=N),
9.00 s (1H, OH). Found, %: C 74.47; H 7.01; N 3.04.
M 392.5. C25H27NO4. Calculated, %: C 74.05; H 6.71;
N 3.45. M 405.5.
3-{4-(E)-4-[(Adamantan-1-ylcarbonyloxy)-3-me-
thoxyphenyl]methylideneamino}benzoic acid (IIIn).
Yield 91%, mp 222–223°C. IR spectrum, ν, cm–1:
2100–3550 (O–H); 3083, 3076, 3062, 3036, 3005
(C–Harom); 2932, 2903, 2847 (C–Haliph); 1758, 1691,
1682 (C=O); 1629 (C=N); 1583, 1506 (C=Carom);
1460, 1452 (CH2); 1270, 1215, 1195, 1179, 1151,
1118, 1050, 1041 (C–O); 896, 870, 844, 816, 807, 792,
784, 763, 745, 730, 688, 671 (δC–Harom). UV spec-
(E)-2-Methoxy-4-[(4-phenoxyphenyl)iminometh-
yl]phenyl adamantane-1-carboxylate (IIIj). Yield
90%, mp 112–113°C. IR spectrum, ν, cm–1: 3078,
3065, 3055, 3040, 3021, 3006 (C–Harom); 2954, 2922,
2914, 2900, 2880, 2845 (C–Haliph); 1740 (C=O); 1624
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1
trum, λmax, nm (ε): 205 (17000), 222 (30000), 250
(10000), 306 (4000). H NMR spectrum, δ, ppm:
(15000). H NMR spectrum, δ, ppm: 1.00 t (3H, Me),
1.16–2.30 m (19H, CH2CH2, Ad), 3.92 s (3H, MeO),
4.34 q (2H, CH2O), 7.02–8.17 m (7H, Harom), 8.39 s
(1H, CH=N). Found, %: C 73.85; H 7.43; N 2.50.
M 475.7. C30H35NO5. Calculated, %: C 73.59; H 7.21;
N 2.86. M 489.6.
1
1.68–2.30 m (15H, Ad), 3.90 s (3H, MeO), 6.92–
8.02 m (7H, Harom), 8.58 s (1H, CH=N), 9.97 s (1H,
OH). Found, %: C 72.16; H 6.29; N 2.96. M 430.2.
C26H27NO5. Calculated, %: C 72.04; H 6.28; N 3.23.
M 433.5.
(E)-2-Methoxy-4-(naphthalen-1-yliminomethyl)-
phenyl adamantane-1-carboxylate (IIIr). Yield 87%,
mp 173–174°C. IR spectrum, ν, cm–1: 3090, 3055,
3048, 3006 (C–Harom); 2936, 2905, 2887, 2850
(CHaliph); 1751 (C=O); 1626 (C=N); 1600, 1584, 1569,
1531, 1510 (C=Carom); 1464, 1449 (CH2); 1285, 1261,
1216, 1197, 1180, 1157, 1109, 1042 (C–O); 896, 877,
856, 830, 804, 794, 776, 766, 740, 734, 680
(δC–Harom). UV spectrum, λmax, nm (ε): 210 (27000),
230 (26000), 260 (10000), 290 (6000), 310 (6000),
344 (6000). H NMR spectrum, δ, ppm: 1.69–2.42 m
(15H, Ad), 3.95 s (3H, MeO), 6.98–8.44 m (10H,
arom), 8.51 s (1H, CH=N). Found, %: C 79.63;
H 6.79; N 2.87. M 425.1. C29H29NO3. Calculated, %:
C 79.24; H 6.65; N 3.19. M 439.5.
4-{4-(E)-4-[(Adamantan-1-ylcarbonyloxy)-3-me-
thoxyphenyl]methylideneamino}benzoic acid (IIIo).
Yield 92%, mp 277–278°C. IR spectrum, ν, cm–1:
2300–3650 (OH); 3089, 3078, 3040, 3030, 3010
(C–Harom); 2970, 2940, 2908, 2851 (C–Haliph); 1744,
1677 (C=O); 1632 (C=N); 1598, 1581, 1568, 1513,
1508 (C=Carom); 1468, 1450 (CH2); 1284, 1263, 1219,
1194, 1170, 1158, 1150, 1111, 1102, 1040 (C–O); 871,
854, 816, 800, 770, 754, 756, 734, 700, 678
(δC–Harom). UV spectrum, λmax, nm (ε): 206 (24000),
220 (20000), 280 (22000), 294 (22000), 315 (15000).
1H NMR spectrum, δ, ppm: 1.64–2.30 m (15H, Ad),
3.90 s (3H, MeO), 6.42–8.08 m (7H, Harom), 8.56 s
(1H, CH=N), 9.95 s (1H, OH). Found, %: C 72.34;
H 6.68; N 2.85. M 431.4. C26H27NO5. Calculated, %:
C 72.04; H 6.28; N 3.23. M 433.5.
1
H
(E)-2-Methoxy-4-(naphthalen-2-yliminomethyl)-
phenyl adamantane-1-carboxylate (IIIs). Yield 88%,
mp 134–135°C. IR spectrum, ν, cm–1: 3095, 3070,
3053, 3011 (C–Harom); 2906, 2851 (C–Haliph); 1750
(C=O); 1626 (C=N); 1600, 1590, 1504 (C=Carom);
1464, 1451 (CH2); 1274, 1260, 1211, 1193, 1179,
1147, 1122, 1111, 1040 (C–O); 890, 872, 841, 819,
790, 745, 737, 678 (δC–Harom). UV spectrum, λmax, nm
(ε): 224 (28000), 270 (17000), 324 (11000), 356
(8000). 1H NMR spectrum, δ, ppm: 1.66–2.42 m (15H,
Ad), 3.95 s (3H, MeO), 6.90–8.46 m (10H, Harom),
8.50 s (1H, CH=N). Found, %: C 79.57; H 6.72;
N 2.80. M 428.4. C29H29NO3. Calculated, %: C 79.24;
H 6.65; N 3.19. M 439.5.
Ethyl 4-{4-(E)-4-[(adamantan-1-ylcarbonyloxy)-
3-methoxyphenyl]methylideneamino}benzoate
(IIIp). Yield 90%, mp 150–151°C. IR spectrum, ν,
cm–1: 3092, 3086, 3072, 3040, 3027 (C–Harom); 2942,
2904, 2851 (C–Haliph); 1749, 1698 (C=O); 1631
(C=N); 1600, 1593, 1504 (C=Carom); 1460 (CH2);
1274, 1215, 1192, 1184, 1160, 1148, 1118, 1101, 1043,
1033 (C–O); 868, 856, 836, 817, 804, 776, 740, 731,
699, 680 (C–Harom). UV spectrum, λmax, nm (ε): 205
(22000), 221 (20000), 280 (22000), 294 (21000), 315
1
(15000). H NMR spectrum, δ, ppm: 1.44 t (3H, Me),
1.66–2.30 m (15H, Ad), 3.92 s (3H, MeO), 4.42 q (2H,
CH2), 7.09–8.18 m (7H, Harom), 8.40 s (1H, CH=N).
Found, %: C 73.12; H 6.88; N 2.74. M 452.2.
C28H31NO5. Calculated, %: C 72.86; H 6.77; N 3.03.
M 461.5.
(E)-4-[(1-Bromonaphthalen-2-yl)iminomethyl]-
2-methoxyphenyl adamantane-1-carboxylate (IIIf).
Yield 92%, mp 178–179°C. IR spectrum, ν, cm–1:
3090, 3058, 3040, 3022, 3001 (C–Harom); 2940, 2903,
2850 (C–Haliph); 1746 (C=O); 1630 (C=N); 1615,
1600, 1588, 1504 (C=Carom); 1462, 1450 (CH2); 1276,
1259, 1218, 1189, 1151, 1119, 1050, 1041 (C–O); 864,
852, 810, 790, 760, 744, 730, 680 (δC–Harom). UV
spectrum, λmax, nm (ε): 204 (23000), 230 (42000), 244
(25000), 270 (24000), 310 (11000), 330 (10000).
1H NMR spectrum, δ, ppm: 1.64–2.42 m (15H, Ad),
3.96 s (3H, MeO), 7.04–8.40 m (9H, Harom), 8.49 s
(1H, CH=N). Found, %: C 67.52; H 5.63; Br 15.03;
N 2.28. M 499.3. C29H28BrNO3. Calculated, %:
C 67.18; H 5.44; Br 15.41; N 2.70. M 518.4.
Butyl 4-{4-(E)-4-[(adamantan-1-ylcarbonyloxy)-
3-methoxyphenyl]methylideneamino}benzoate
(IIIq). Yield 91%, mp 108–109°C. IR spectrum, ν,
cm–1: 3091, 3083, 3064, 3042, 3007 (C–Harom); 2959,
2932, 2920, 2905, 2850 (C–Haliph); 1756, 1712 (C=O);
1631 (C=N); 1590, 1504 (C=Carom); 1464, 1456 (CH2);
1274, 1217, 1193, 1180, 1150, 1116, 1094, 1045, 1038
(C–O); 869, 848, 819, 794, 780, 770, 741, 730, 702,
677 (C–Harom). UV spectrum, λmax, nm (ε): 204
(22000), 223 (20000), 280 (21000), 294 (21000), 314
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DIKUSAR et al.
512
1198, 1181, 1165, 1116, 1101, 1053, 1045 (C–O); 868,
(E)-2-Ethoxy-4-(hexadecyliminomethyl)phenyl
842, 818, 800, 788, 760, 731, 678 (δC–Harom). UV
spectrum, λmax, nm (ε): 207 (16000), 222 (14000), 254
(10000), 300 (500). H NMR spectrum, δ, ppm: 1.14 d
(3H, Me), 1.42 t (3H, Me), 1.60–2.25 m (30H, Ad),
2.84 q (1H, CH), 4.15 q (2H, CH2), 6.98–7.48 m (3H,
Harom), 8.19 s (1H, CH=N). Found, %: C 78.80;
H 8.93; N 2.34. M 470.3. C32H43NO3. Calculated, %:
C 78.49; H 8.85; N 2.68. M 489.7.
adamantane-1-carboxylate (IVa). Yield 86%, mp 67–
68°C. IR spectrum, ν, cm–1: 3072, 3053, 3008
(C–Harom); 2918, 2850 (C–Haliph); 1742 (C=O); 1646
(C=N); 1601, 1590, 1512 (C=Carom); 1470, 1453 (CH2);
1294, 1264, 1217, 1205, 1167, 1117, 1105, 1055, 1043
(C–O); 874, 846, 832, 824, 804, 783, 732, 725
(δC–Harom). UV spectrum, λmax, nm (ε): 208 (15000),
1
1
221 (13000), 253 (9000), 300 (400). H NMR spec-
trum, δ, ppm: 0.92 t (3H, Me), 1.10–2.16 m [46H, Ad,
Me, (CH2)14], 3.63 t (2H, CH2N), 4.14 q (2H, CH2),
7.06–7.50 m (3H, Harom), 8.23 s (1H, CH=N). Found,
%: C 78.76; H 10.46; N 2.19. M 537.6. C36H57NO3.
Calculated, %: C 78.35; H 10.41; N 2.54. M 551.8.
(E)-2-Ethoxy-4-(phenyliminomethyl)phenyl
adamantane-1-carboxylate (IVe). Yield 86%, mp 88–
89°C. IR spectrum, ν, cm–1: 3089, 3074, 3054, 3032,
3028, 3019, 3006 (C–Harom); 2986, 2906, 2851
(C–Haliph); 1746 (C=O); 1626 (C=N); 1599, 1585, 1511
(C=Carom); 1468, 1449 (CH2); 1291, 1274, 1214, 1180,
1159, 1118, 1105, 1042 (C–O); 872, 860, 853, 840,
828, 762, 755, 730, 693, 680 (δC–Harom). UV spec-
trum, λmax, nm (ε): 204 (32000), 222 (23000), 268
(E)-2-Ethoxy-4-(octadecyliminomethyl)phenyl
adamantane-1-carboxylate (IVb). Yield 91%,
mp 68–69°C. IR spectrum, ν, cm–1: 3081, 3042, 3008
(C–Harom); 2918, 2850 (C–Haliph); 1742 (C=O); 1647
(C=N); 1601, 1589, 1512 (C=Carom); 1470, 1453 (CH2);
1294, 1264, 1218, 1205, 1167, 1117, 1105, 1055, 1043
(C–O); 870, 848, 836, 819, 803, 788, 765, 730, 718,
680 (δ C–Harom). UV spectrum, λmax, nm (ε): 207
1
(14000), 316 (12000). H NMR spectrum, δ, ppm:
1.40 t (3H, Me), 1.63–2.36 m (15H, Ad), 4.16 q (2H,
CH2), 6.90–7.65 m (8H, Harom), 8.38 s (1H, CH=N).
Found, %: C 77.63; H 7.30; N 3.19. M 394.4.
C26H29NO3. Calculated, %: C 77.39; H 7.24; N 3.47.
M 403.5.
1
(14000), 222 (13000), 254 (8000), 300 (400). H NMR
spectrum, δ, ppm: 0.92 t (3H, Me), 1.08–2.14 m [50H,
Ad, Me, (CH2)16], 3.62 t (2H, CH2N), 4.14 q (2H,
CH2), 7.06–7.50 m (3H, Harom), 8.23 s (1H, CH=N).
Found, %: C 79.03; H 10.73; N 2.02. M 566.0.
C38H61NO3. Calculated, %: C 78.70; H 10.61; N 2.42.
M 579.9.
(E)-2-Ethoxy-4-[(4-methylphenyl)iminomethyl]-
phenyl adamantane-1-carboxylate (IVf). Yield 86%,
mp 149–150°C. IR spectrum, ν, cm–1: 3091, 3082,
3068, 3040, 3032, 3003 (C–Harom); 2855, 2922, 2906,
2846 (C–Haliph); 1742 (C=O); 1626 (C=N); 1601,
1581, 1511 (C=Carom); 1476, 1446 (CH2); 1290, 1265,
1216, 1194, 1160, 1116, 1104, 1053, 1046 (C–O); 866,
855, 840, 818, 796, 780, 771, 742, 731, 720, 709, 680
(C–Harom). UV spectrum, λmax, nm (ε): 202 (40000),
(E)-4-(Cyclohexyliminomethyl)-2-ethoxyphenyl
adamantane-1-carboxylate (IVc). Yield 87%, mp 93–
94°C. IR spectrum, ν, cm–1: 3080, 3059, 3005
(C–Harom); 2981, 2924, 2907, 2851 (C–Haliph); 1746
(C=O); 1644 (C=N); 1592, 1513 (C=Carom); 1476,
1448 (CH2); 1291, 1270, 1222, 1199, 1166, 1076,
1057, 1041 (C–O); 886, 866, 840, 835, 810, 789, 760,
740, 731, 677 (δC–Harom). UV spectrum, λmax, nm (ε):
207 (15000), 223 (12000), 254 (8000), 300 (400).
1H NMR spectrum, δ, ppm: 1.10–2.14 m (29H, Ad,
Me, C6H11), 4.14 q (2H, CH2), 7.02–7.46 m (3H,
Harom), 8.22 s (1H, CH=N). Found, %: C 76.57;
H 8.63; N 3.11. M 392.5. C26H35NO3. Calculated, %:
C 76.25; H 8.61; N 3.42. M 409.6.
1
224 (38000), 270 (28000), 322 (28000). H NMR
spectrum, δ, ppm: 1.40 t (3H, Me), 1.62–2.15 m (15H,
Ad), 2.33 s (3H, Me), 4.14 q (2H, CH2), 7.02–7.74 m
(7H, Harom), 8.58 s (1H, CH=N). Found, %: C 77.96;
H 7.63; N 3.04. M 409.2. C27H31NO3. Calculated, %:
C 77.67; H 7.48; N 3.35. M 417.5.
(E)-4-[(Biphenyl-2-yl)iminomethyl]-2-ethoxy-
phenyl adamantane-1-carboxylate (IVg). Yield 88%,
mp 39–40°C. IR spectrum, ν, cm–1: 3090, 3080, 3059,
3034, 3020 (C–Harom); 2929, 2906, 2852 (C–Haliph);
1752 (C=O); 1628 (C=N); 1599, 1588, 1509 (C=Carom);
1478, 1452 (CH2); 1276, 1212, 1193, 1170, 1158,
1120, 1043 (C–O); 872, 845, 820, 774, 752, 737, 699,
679 (δ C–Harom). UV spectrum, λmax, nm (ε): 204
(E)-4-[1-(1-Adamantyl)ethyliminomethyl]-2-
ethoxyphenyl adamantane-1-carboxylate (IVd).
Yield 90%, mp 153–154°C. IR spectrum, ν, cm–1:
3070, 3052, 3007 (C–Harom); 1980, 2935, 2905, 2850,
2811 (C–Haliph); 1748 (C=O); 1644 (C=N); 1600, 1589,
1511 (C=Carom); 1476, 1452 (CH2); 1290, 1263, 1215,
1
(23000), 264 (13000), 318 (12000). H NMR spec-
trum, δ, ppm: 1.41 t (3H, Me), 1.68–2.40 m (15H, Ad),
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4.14 q (2H, CH2), 6.92–7.62 m (12H, Harom), 8.45 s
(1H, CH=N). Found, %: C 80.47; H 7.08; N 2.65.
M 468.3. C32H33NO3. Calculated, %: C 80.14; H 6.94;
N 2.92. M 479.6.
mp 162–163°C. IR spectrum, ν, cm–1: 3091, 3074,
3066, 3053, 3040, 3010 (C–Harom); 2933, 2905, 2853
(C–Haliph); 1738 (C=O); 1624 (C=N); 1601, 1589,
1512 (C=Carom); 1488, 1453 (CH2); 1290, 1261, 1238,
1214, 1195, 1162, 1113, 1103, 1055, 1039 (C–O); 866,
858, 851, 829, 798, 772, 741, 694, 680 (C–Harom). UV
spectrum, λmax, nm (ε): 200 (50000), 225 (34000), 272
(E)-4-[(Biphenyl-4-yl)iminomethyl]-2-ethoxy-
phenyl adamantane-1-carboxylate (IVh). Yield 90%,
mp 168–169°C. IR spectrum, ν, cm–1: 3089, 3074,
3061, 3032 (C–Harom); 2940, 2021, 2904, 2851
(C–Haliph); 1743 (C=O); 1630 (C=N); 1601, 1582, 1511
(C=Carom); 1482, 1450 (CH2); 1289, 1250, 1216, 1195,
1180, 1160, 1115, 1103, 1043 (C–O); 868, 851, 837,
822, 782, 762, 740, 734, 699, 681 (δC–Harom). UV
spectrum, λmax, nm (ε): 204 (21000), 268 (14000), 318
1
(20000), 327 (20000). H NMR spectrum, δ, ppm:
1.42 t (3H, Me), 1.60–2.25 m (15H, Ad), 4.14 q (2H,
CH2), 6.80–7.68 m (12H, Harom), 8.49 s (1H, CH=N).
Found, %: C 77.86; H 6.83; N 2.57. M 483.7.
C32H33NO4. Calculated, %: C 77.55; H 6.71; N 2.83.
M 495.6.
1
(10000). H NMR spectrum, δ, ppm: 1.42 t (3H, Me),
(E)-4-[(4-Acetylphenyl)iminomethyl]-2-ethoxy-
phenyl adamantane-1-carboxylate (IVl). Yield 86%,
mp 77–78°C. IR spectrum, ν, cm–1: 3064, 3045, 3002
(C–Harom); 2977, 2942, 2906, 2852 (C–Haliph); 1749,
1681 (C=O); 1628 (C=N); 1593, 1509 (C=Carom);
1470, 1452 (CH2); 1271, 1216, 1199, 1180, 1157,
1120, 1042 (C–O); 855, 831, 787, 766, 743, 730, 676
(δC–Harom). UV spectrum, λmax, nm (ε): 204 (29000),
1.68–2.40 m (15H, Ad), 4.14 q (2H, CH2), 6.96–7.72 m
(12H, Harom), 8.45 s (1H, CH=N). Found, %: C 80.40;
H 7.12; N 2.72. M 466.6. C32H33NO3. Calculated, %:
C 80.14; H 6.94; N 2.92. M 479.6.
(E)-4-[(4-Bromophenyl)iminomethyl]-2-ethoxy-
phenyl adamantane-1-carboxylate (IVi). Yield 92%,
mp 166–167°C. IR spectrum, ν, cm–1: 3088, 3072,
3045, 3003 (C–Harom); 2924, 2906, 2848 (C–Haliph);
1740 (C=O); 1625 (C=N); 1602, 1589, 1575, 1510
(C=Carom); 1481, 1476, 1449 (CH2); 1290, 1264, 1216,
1194, 1180, 1160, 1115, 1105, 1060, 1054, 1007
(C–O); 865, 852, 829, 819, 778, 762, 740, 709, 881
(δC–Harom). UV spectrum, λmax, nm (ε): 204 (25000),
1
221 (20000), 254 (10000), 308 (14000). H NMR
spectrum, δ, ppm: 1.42 t (3H, Me), 1.55–2.25 m (15H,
Ad), 3.74 s (3H, Me), 4.14 q (2H, CH2), 6.90–8.12 m
(7H, Harom), 8.46 s (1H, CH=N). Found, %: C 75.59;
H 7.12; N 2.83. M 433.7. C28H31NO4. Calculated, %:
C 75.48; H 7.01; N 3.14. M 445.6.
1
224 (22000), 266 (18000), 320 (18000). H NMR
(E)-2-Ethoxy-4-[4-(1-oxopropyl)phenylimino-
methyl]phenyl adamantane-1-carboxylate (IVm).
Yield 85%, mp 87–88°C. IR spectrum, ν, cm–1: 3090,
3054, 3041, 3006 (C–Harom); 2980, 2940, 2902, 2851
(C–Haliph); 1752, 1652 (C=O); 1625 (C=N); 1594,
1585, 1558, 1520 (C=Carom); 1468, 1453, 1442 (CH2);
1241, 1184, 1170, 1135, 1079, 1039 (C–O); 880, 839,
810, 796, 750, 724, 878 (δC–Harom). UV spectrum,
λmax, nm (ε): 204 (29000), 222 (20000), 254 (11000),
spectrum, δ, ppm: 1.42 t (3H, Me), 1.54–2.16 m (15H,
Ad), 4.15 q (2H, CH2), 7.00–7.74 m (7H, Harom), 8.58 s
(1H, CH=N). Found, %: C 65.11; H 5.89; Br 16.21;
N 2.60. M 470.5. C26H28BrNO3. Calculated, %:
C 64.73; H 5.85; Br 16.56; N 2.90. M 482.4.
(E)-2-Ethoxy-4-[(2-hydroxyphenyl)iminomethyl]-
phenyl adamantane-1-carboxylate (IVj). Yield 86%,
mp 128–129°C. IR spectrum, ν, cm–1: 3425, 3407
(OH); 3089, 3077, 3042, 3002 (C–Harom); 2924, 2902,
2850 (C–Haliph); 1745 (C=O); 1624 (C=N); 1602,
1592, 1582, 1508 (C=Carom); 1485, 1477, 1449 (CH2);
1292, 1274, 1260, 1215, 1178, 1157, 1117, 1106, 1049,
1042 (C–O); 876, 870, 843, 822, 815, 750, 742, 730,
678 (δ C–Harom). UV spectrum, λmax, nm (ε): 204
(33000), 234 (15000), 284 (12000), 344 (10000).
1H NMR spectrum, δ, ppm: 1.42 t (3H, Me), 1.62–
2.22 m (15H, Ad), 4.14 q (2H, CH2), 6.54–7.88 m (7H,
1
306 (14000). H NMR spectrum, δ, ppm: 1.10–1.60 m
(6H, Me), 1.60–2.24 m (15H, Ad), 2.94 q (2H, CH2),
4.14 q (2H, CH2), 6.90–8.06 m (7H, Harom), 8.44 s (1H,
CH=N). Found, %: C 76.19; H 7.36; N 2.80. M 447.3.
C29H33NO4. Calculated, %: C 75.79; H 7.24; N 3.05.
M 459.6.
3-{(E)-[4-(Adamantan-1-ylcarbonyloxy)-
3-ethoxyphenyl]methylideneamino}benzoic acid
(IVn). Yield 90%, mp 197–198°C. IR spectrum, ν,
cm–1: 2050–3570 (O–H); 3087, 3065, 3045, 3032,
3005 (C–Harom); 2934, 2905, 2854 (C–Haliph); 1747,
1685 (C=O); 1629 (C=N); 1601, 1578, 1511 (C=Carom);
1477, 1449 (CH2); 1292, 1279, 1263, 1218, 1197,
Harom), 8.67 s (1H, CH=N), 8.96 s (1H, OH). Found,
%: C 74.48; H 7.08; N 2.98. M 404.8. C26H29NO4. Cal-
culated, %: C 74.44; H 6.97; N 3.34. M 419.5.
(E)-2-Ethoxy-4-[(4-phenoxyphenyl)iminomethyl]-
phenyl adamantane-1-carboxylate (IVk). Yield 88%,
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DIKUSAR et al.
514
1
1180, 1162, 1116, 1103, 1052, 1039 (C–O); 870, 854,
816, 758, 730, 687, 673 (δC–Harom). UV spectrum,
λmax, nm (ε): 204 (18000), 223 (30000), 250 (10000),
(21000), 294 (21000), 315 (15000). H NMR spec-
trum, δ, ppm: 0.90–1.62 t (6H, Me), 1.18–2.30 m
(19H, CH2CH2, Ad), 3.95–4.60 q (4H, CH2O), 7.04–
8.18 m (7H, Harom), 8.38 s (1H, CH=N). Found, %:
C 74.23; H 7.50; N 2.44. M 492.0. C31H37NO5. Cal-
culated, %: C 73.93; H 7.41; N 2.78. M 503.6.
1
306 (5000). H NMR spectrum, δ, ppm: 1.45 t (3H,
Me), 1.68–2.33 m (15H, Ad), 4.14 q (2H, CH2), 6.92–
8.04 m (7H, Harom), 8.58 s (1H, CH=N), 9.96 s (1H,
OH). Found, %: C 72.84; H 6.62; N 2.87. M 445.6.
C27H29NO5. Calculated, %: C 72.46; H 6.53; N 3.13.
M 447.5.
(E)-2-Ethoxy-4-(naphthalen-1-yliminomethyl)-
phenyl adamantane-1-carboxylate (IVr). Yield 85%,
mp 108–109°C. IR spectrum, ν, cm–1: 3088, 3065,
3051, 3003 (C–Harom); 2914, 2899, 2851 (C–Haliph);
1747 (C=O); 1626 (C=N); 1598, 1589, 1572, 1504
(C=Carom); 1474, 1452 (CH2); 1277, 1264, 1216, 1197,
1173, 1161, 1116, 1103, 1050, 1041 (C–O); 876, 840,
822, 812, 803, 789, 779, 771, 740, 678 (δC–Harom). UV
spectrum, λmax, nm (ε): 209 (27000), 232 (27000), 260
4-{(E)-[4-(Adamantan-1-ylcarbonyloxy)-
3-ethoxyphenyl]methylideneamino}benzoic acid
(IVo). Yield 88%, mp 267–268°C. IR spectrum, ν,
cm–1: 2200–3650 (O–H); 3080, 3068, 3040, 3006
(C–Harom); 2940, 2911, 2851 (C–Haliph); 1745, 1686
(C=O); 1635 (C=N); 1600, 1582, 1512 (C=Carom);
1480, 1451 (CH2); 1291, 1263, 1215, 1195, 1179,
1162, 1114, 1102, 1050, 1040 (C–O); 872, 849, 822,
812, 770, 756, 734, 700, 678 (δC–Harom). UV spec-
trum, λmax, nm (ε): 205 (23000), 220 (20000), 280
1
(10000), 290 (6000), 311 (6000), 344 (6000). H NMR
spectrum, δ, ppm: 1.42 t (3H, Me), 1.70–2.42 m (15H,
Ad), 4.14 q (2H, CH2), 6.96–8.44 m (10H, Harom),
8.52 s (1H, CH=N). Found, %: C 79.78; H 7.00;
N 2.65. M 441.8. C30H31NO3. Calculated, %: C 79.44;
H 6.89; N 3.09. M 453.6.
1
(22000), 295 (22000), 314 (15000). H NMR spec-
trum, δ, ppm: 1.45 t (3H, Me), 1.66–2.30 m (15H, Ad),
4.14 q (2H, CH2), 6.42–8.08 m (7H, Harom), 8.56 s (1H,
CH=N), 9.96 s (1H, OH). Found, %: C 72.73; H 6.60;
N 3.04. M 446.1. C27H29NO5. Calculated, %: C 72.46;
H 6.53; N 3.13. M 447.5.
(E)-2-Ethoxy-4-(naphthalen-2-yliminomethyl)-
phenyl adamantane-1-carboxylate (IVs). Yield 88%,
mp 133–134°C. IR spectrum, ν, cm–1: 3070, 3050,
3030 (C–Harom); 2032, 2904, 2951 (C–Haliph); 1751
(C=O); 1624 (C=N); 1598, 1579, 1506 (C=Carom);
1475, 1452 (CH2); 1288, 1261, 1248, 1214, 1196,
1171, 1154, 1116, 1102, 1041 (C–O); 884, 860, 828,
808, 749, 730, 678 (δC–Harom). UV spectrum, λmax, nm
(ε): 223 (27000), 272 (18000), 324 (12000), 355
Ethyl 4-{(E)-[4-(adamantan-1-ylcarbonyloxy)-
3-ethoxyphenyl]methylideneamino}benzoate (IVp).
Yield 87%, mp 112–113°C. IR spectrum, ν, cm–1:
3090, 3084, 3072, 3040, 3020 (C–Harom); 2944, 2905,
2854 (C–Haliph); 1744, 1716 (C=O); 1631 (C=N);
1600, 1585, 1514 (C=Carom); 1477, 1452 (CH2); 1274,
1218, 1193, 1188, 1164, 1114, 1100, 1054, 1041
(C–O); 866, 853, 838, 816, 804, 772, 760, 732, 699,
681 (C–Harom). UV spectrum, λmax, nm (ε): 204
(22000), 221 (19000), 280 (22000), 292 (21000), 314
(14000). 1H NMR spectrum, δ, ppm: 1.15–1.58 m (6H,
Me), 1.66–2.30 m (15H, Ad), 4.10–4.64 q (4H, CH2),
7.08–8.16 m (7H, Harom), 8.41 s (1H, CH=N). Found,
%: C 73.54; H 7.13; N 2.63. M 475.3. C29H33NO5. Cal-
culated, %: C 73.24; H 6.99; N 2.95. M 475.6.
1
(8000). H NMR spectrum, δ, ppm: 1.45 t (3H, Me),
1.64–2.42 m (15H, Ad), 4.14 q (2H, CH2), 6.90–
8.46 m (10H, Harom), 8.51 s (1H, CH=N). Found, %:
C 79.81; H 7.09; N 2.78. M 444.5. C30H31NO3. Cal-
culated, %: C 79.44; H 6.89; N 3.09. M 453.6.
(E)-4-[(1-Bromonaphthalen-2-yl)iminomethyl]-
2-ethoxyphenyl adamantane-1-carboxylate (IVt).
Yield 91%, mp 101–102°C. IR spectrum, ν, cm–1:
3092, 3064, 3040, 3003 (C–Harom); 2932, 2904, 2851
(C–Haliph); 1743 (C=O); 1628 (C=N); 1619, 1601,
1583, 1511 (C=Carom); 1477, 1448 (CH2); 1290, 1258,
1218, 1199, 1168, 1116, 1103, 1051, 1040 (C–O); 870,
858, 840, 799, 762, 740, 732, 678 (C–Harom). UV spec-
trum, λmax, nm (ε): 204 (24000), 230 (44000), 245
(25000), 270 (25000), 310 (11000), 332 (10000).
1H NMR spectrum, δ, ppm: 1.45 t (3H, Me), 1.65–
2.42 m (15H, Ad), 4.14 q (2H, CH2), 7.05–8.40 m
(9H, Harom), 8.50 s (1H, CH=N). Found, %: C 67.52;
H 5.63; Br 15.03; N 2.28. M 499.3. C29H28BrNO3.
Butyl 4-{(E)-[4-(adamantan-1-ylcarbonyloxy)-
3-ethoxyphenyl]methylideneamino}benzoate (IVq).
Yield 89%, mp 88–89°C. IR spectrum, ν, cm–1: 3090,
3082, 3062, 3040, 3008 (C–Harom); 2956, 2940, 2907,
2852 (C–Haliph); 1752, 1715 (C=O); 1631 (C=N);
1601, 1587, 1513 (C=Carom); 1464, 1452 (CH2); 1274,
1267, 1193, 1180, 1158, 1116, 1102, 1042 (C–O); 872,
846, 823, 770, 741, 730, 702, 675 (δC–Harom). UV
spectrum, λmax, nm (ε): 204 (23000), 224 (20000), 280
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SYNTHESIS AND PROPERTIES OF (E)-4-[ALKYL(ARYL)IMINOMETHYL]-...
515
Calculated, %: C 67.18; H 5.44; Br 15.41; N 2.70.
M 518.4.
2.30 m (2H, 10-H), 3.70 s (3H, OMe), 5.85 s (1H,
12-H), 6.50 d (1H, 5′-H, J = 9 Hz), 6.60 d (1H, 3′-H,
J = 9 Hz), 7.15 s (1H, 6′-H), 7.25 d (1H, 5-H, J =
9 Hz), 7.30 t (1H, 2-H, J = 9 Hz), 7.38 t (1H, 3-H, J =
9 Hz), 7.68 d (1H, 6-H, J = 9 Hz), 7.73 d (1H, 4-H, J =
9 Hz), 7.92 d (1H, 7-H, J = 9 Hz), 9.35 s (1H, NH).
Found, %: C 79.41; H 6.83; N 2.60. C37H39NO4. Cal-
culated, %: C 79.12; H 7.00; N 2.49.
Compounds Va and Vb (general procedure).
a. A mixture of 5 mmol of Schiff base IIIs, 5 mmol of
cyclohexane-1,3-dione or 5,5-dimethylcyclohexane-
1,3-dione (dimedone) in 20 ml of ethanol was heated
for 30 min under reflux. After cooling, the precipitate
was filtered off, washed on a filter with two portions of
diethyl ether to remove unreacted initial compounds,
and dried under reduced pressure. The product was
sufficiently pure, and no additional purification was
necessary.
REFERENCES
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b. A mixture of 5 mmol of aldehyde Ia, 5 mmol of
naphthalen-2-amine (IIs), and 5 mmol of the corre-
sponding diketone in 20 ml of ethanol was heated for
10–15 min under reflux. After cooling, the precipitate
was filtered off, washed on a filter with two portions of
diethyl ether to remove unreacted initial compounds,
and dried under reduced pressure.
2-Methoxy-4-(11-oxo-7,8,9,10,11,12-hexahydro-
benzo[a]acridin-12-yl)phenyl adamantane-1-car-
boxylate (Va). Yield 70 (a), 78% (b); mp 346–348°C.
IR spectrum, ν, cm–1: 3440 (NH), 3065 (C–Harom),
2960 (C–Haliph), 1730 (C=O), 1570, 1520, 1400, 1270
5. Dikusar, E.A., Kozlov, N.G., Potkin, V.I., and Kovgan-
ko, N.V., Khim. Prirodn. Soedin., 2003, p. 215.
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,
7. Dikusar, E.A. and Kozlov, N.G., Russ. J. Org. Chem.,
nm (ε): 216 (29000), 234 (34000), 269 (10000), 281
2007, vol. 43, p. 1263.
(14000), 290 (14000), 325 (3000), 340 (12000), 370
1
8. Dikusar, E.A., Kozlov, N.G., Tlegenov, R.T., and Ute-
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(Schiff Bases Derived from Vanilllin and Vanillal),
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tsionnoi spektroskopii organicheskikh soedinenii,
Moscow: Khimiya, 1970, p. 92.
(8000). H NMR spectrum (DMSO-d6), δ, ppm:
1.70 br.s (6H, CH2 in Ad), 1.95 br.s (6H, CH2 in Ad),
2.00 m (2H, 8-H), 2.05 br.s (3H, CH in Ad), 2.30 m
(2H, 9-H), 2.60 m (2H, 10-H), 3.70 s (3H, OMe),
5.90 s (1H, 12-H), 6.50 d (1H, 5′-H, J = 9 Hz), 6.60 d
(1H, 3′-H, J = 9 Hz), 7.20 s (1H, 6′-H), 7.28 d (1H,
5-H, J = 9 Hz), 7.30 t (1H, 2-H, J = 9 Hz), 7.38 t (1H,
3-H, J = 9 Hz), 7.66 d (1H, 6-H, J = 9 Hz), 7.72 d (1H,
4-H, J = 9 Hz), 7.90 d (1H, 7-H, J = 9 Hz), 9.45 s (1H,
NH). Found, %: C 78.52; H 6.43; N 2.40. C35H35NO4.
Calculated, %: C 78.77; H 6.61; N 2.62.
10. Kozlov, N.G., Gusak, K.N., Tereshko, A.B., Fir-
gang, S.I., and Shashkov, A.S., Russ. J. Org. Chem.,
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11. Kozlov, N.G., Basalaeva, L.I., Firgang, S.I., and Shash-
kov, A.S., Russ. J. Org. Chem., 2004, vol. 40, p. 518.
12. Kozlov, N.G., Basalaeva, L.I., and Tychinskaya, L.Yu.,
4-(9,9-Dimethyl-11-oxo-7,8,9,10,11,12-hexahydro-
benzo[a]acridin-12-yl)-2-methoxyphenyl adaman-
tane-1-carboxylate (Vb). Yield 75 (a), 84% (b);
mp 346–348°C. IR spectrum, ν, cm–1: 3445 (NH);
3070 (C–Harom); 2950 (C–Haliph); 1740 (C=O); 1565,
1520, 1410, 1280 (C–O); 1030, 850, 720 (δC–Harom).
UV spectrum, λmax, nm (ε): 218 (30000), 233 (35000),
270 (10000), 281 (15000), 290 (16000), 326 (3000),
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sak, K.N., Andreeva, E.I., and Rozhkova, N.G., Vestsi
Akad. Navuk BSSR, Ser. Khim. Navuk, 1988, no. 2,
p. 42.
1
340 (14 000), 370 (8000). H NMR spectrum
(DMSO-d6), δ, ppm: 0.95 s and 1.10 s (3H each,
9-Me), 1.75 br.s (6H, CH2 in Ad), 1.95 br.s (6H, CH2
in Ad), 2.05 br.s (3H, CH in Ad), 2.15 s (2H, 8-H),
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